JP6915544B2 - Adhesive composition and structure - Google Patents

Description

The present invention relates to adhesive compositions and structures.

In semiconductor elements and liquid crystal display elements (display display elements), various adhesives have been conventionally used for the purpose of binding various members in the elements. The properties required for adhesives range from adhesiveness to heat resistance and reliability in high temperature and high humidity conditions. As the adherend to be used in the adhesive, the printed wiring board, organic substrates (polyimide substrate and the like), a metal (titanium, copper, aluminum, etc.), ITO, IZO, _IGZO, SiN X, such as SiO ₂ A base material having a surface state or the like is used, and it is necessary to design the molecule 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 a constituent component of an adhesive using an epoxy resin, an epoxy resin and a latent curing agent that generates cation species or anion species having reactivity with the epoxy resin by heat or light are generally used. The latent curing agent is an important factor that determines the curing temperature and the curing rate, and various compounds have been used from the viewpoint of storage stability at room temperature and curing rate at the time of heating. In the actual step, for example, the desired adhesiveness was obtained by curing under curing conditions of 170 to 250 ° C. for 10 seconds to 3 hours.

Further, in recent years, with the high integration of semiconductor elements and the high definition of liquid crystal display elements, the pitch between elements and between wirings has become narrower, and the heat during curing may adversely affect peripheral members. Further, in order to reduce the cost, it is necessary to improve the throughput, and adhesion at a low temperature (90 to 170 ° C.) and a short time (within 1 hour, preferably within 10 seconds, more preferably within 5 seconds). In other words, adhesion by low temperature short time curing (low temperature fast curing) is required. 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 known that it is very difficult to combine storage stability near room temperature. ..

Therefore, in recent years, a radical curing adhesive or the like in which a (meth) acrylate derivative and a peroxide as a radical polymerization initiator are used in combination has attracted attention. In the radical curing system, radicals, which are reactive species, are extremely reactive, so that they can be cured in a short time, and peroxides are stably present below the decomposition temperature of the radical polymerization initiator. It is a curing system that achieves both low-temperature short-time curing and storage stability (for example, storage stability near room temperature). For example, a radical curing adhesive composition containing a silane compound (silane coupling agent, etc.) having a functional group ((meth) acryloyl group, vinyl group, etc.) capable of radical polymerization is known (for example, See Patent Document 1 below).

Japanese Unexamined Patent Publication No. 2013-191625 Japanese Unexamined Patent Publication No. 2006-22231 International Publication No. 2009/0638227

However, when a conventional adhesive composition (mixture) containing a silane compound having a functional group capable of radical polymerization is stored, the characteristics of the silane compound are significantly deteriorated, and the adhesiveness of the adhesive composition is lowered. Therefore, it is required to improve the storage stability of the conventional radical-curing adhesive composition.

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

The present inventor speculates that the factors that deteriorate the properties of the silane compound in the conventional adhesive composition are as follows. That is, when another initiator different from the silane compound initiates the polymerization reaction during storage of the adhesive composition, the silane compound is incorporated into the polymerization reaction to form a constituent material (resin, etc.) of the adhesive composition. It is taken into the inside of. It is presumed that this reduces the number of molecules that can act on the interface between the adhesive composition and the adherend, resulting in deterioration of the properties.

Further, the present inventor uses a highly active peroxide having a 1-minute half-life temperature of 120 ° C. or less in a radical polymerization-based (for example, (meth) acrylate radical-based) adhesive composition (that is,). In the case of low-temperature short-time curing such as 130 ° C. for 5 seconds, for which demand has been expanding in recent years), it was found that the above-mentioned deterioration in characteristics is particularly remarkable.

As a result of diligent studies to improve storage stability (pot life characteristics), the present inventor has made an adhesion containing a radically polymerizable compound and a peroxide having a one-minute half-life temperature of 120 ° C. or less. When the first silane compound having a radically polymerizable functional group and the second silane compound that reacts with the first silane compound are used in combination in the agent composition, the storage stability of the adhesive composition is improved. It was found to be significantly improved.

The adhesive composition of the present invention comprises a first silane compound having a radically polymerizable functional group, a second silane compound that reacts with the first silane compound, and a radically polymerizable compound (first silane compound). (Excluding compounds corresponding to) and peroxides having a 1-minute half-life temperature of 120 ° C. or lower.

The adhesive composition of the present invention has excellent storage stability as compared with the conventional ones. Such an adhesive composition can prevent the adhesiveness of the adhesive composition from deteriorating with time during storage.

The present inventor speculates that the factors for obtaining such an effect are as follows. That is, the presence of the first silane compound having a radically polymerizable functional group and the second silane compound that reacts with the first silane compound in the adhesive composition causes the first silane compound during storage. Even when the silane compound is radically polymerized and incorporated into the polymer, the second silane compound cross-links the first silane compound in the polymer with the adherend to form an adhesive composition or. It is presumed that the adhesiveness between the cured product and the adherend can be maintained.

By the way, in Patent Document 2, a silane coupling agent is used in the radical curing system for the purpose of improving the adhesion at the initial stage of connection and after the reliability test. However, in Patent Document 2, a peroxide having a high half-life temperature of 125 ° C. for 1 minute (in other words, a peroxide having high stability) is used, and as a result of examination by the present inventor, storage stability is achieved. It has been found that the effect of the silane coupling agent on sex may not be fully confirmed. Further, in Patent Document 2, it has been found that the connection condition is 150 ° C. for 10 seconds, and the curing reaction may not sufficiently occur under the connection condition of 130 ° C. for 5 seconds, which has been required in recent years. On the other hand, according to the adhesive composition of the present invention, it is possible to achieve low-temperature short-time curing (90 to 170 ° C. within 1 hour, preferably within 10 seconds, more preferably within 5 seconds). Sufficient curing can be achieved even under connection conditions such as 130 ° C. for 5 seconds.

The functional group of the first silane compound preferably contains at least one selected from the group consisting of a (meth) acryloyl group and a vinyl group. The second silane compound preferably has an epoxy group.

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

The adhesive composition of the present invention may be for circuit connection (adhesive composition for circuit connection).

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

The structure of the present invention is between a first circuit member having a first circuit electrode, a second circuit member having a second circuit electrode, and the first circuit member and the second circuit member. The first circuit electrode and the second circuit electrode are electrically connected to each other, and the circuit connecting member includes the adhesive composition or a cured product thereof. It may be an embodiment.

According to the present invention, it is possible to provide an adhesive composition having excellent storage stability as compared with the conventional one, and a structure using the same.

According to the present invention, it is possible to provide an application of an adhesive composition or a cured product thereof to a structure or its production. According to the present invention, it is possible to provide an application of an adhesive composition or a cured product thereof to a circuit connection. According to the present invention, it is possible to provide an application of an adhesive composition or a cured product thereof to a circuit connection structure or its production.

It is a schematic cross-sectional view which shows one Embodiment of the structure of this invention. It is a schematic cross-sectional view which shows the other embodiment of the structure of this invention.

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

As used herein, the term "(meth) acrylate" means at least one of an acrylate and a corresponding methacrylate. The same applies to other similar expressions such as "(meth) acryloyl" and "(meth) acrylic acid". Unless otherwise specified, the materials exemplified below may be used alone or in combination of two or more. The content of each component in the composition means the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified. The numerical range indicated by using "~" indicates a range including the numerical values before and after "~" as the minimum value and the maximum value, respectively. "A or B" may include either A or B, or both. "Room temperature" means 25 ° C.

In the numerical range described stepwise in the present specification, the upper limit value or the lower limit value of the numerical range of one step may be replaced with the upper limit value or the lower limit value of the numerical range of another step. Further, in the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.

<Adhesive composition>
The adhesive composition of the present embodiment contains a silane compound, a radically polymerizable compound (radical polymerizable substance), and a curing agent. The adhesive composition of the present embodiment is a first silane compound having a radically polymerizable functional group (a functional group involved in a radical polymerization reaction of a curing system; a functional group capable of being polymerized in a radical polymerization system) as a silane compound. And a second silane compound that reacts with the first silane compound (excluding the compound corresponding to the first silane compound). The adhesive composition of the present embodiment contains a peroxide having a half-life temperature of 120 ° C. or less for 1 minute as the curing agent. The adhesive composition of the present embodiment is a radical curing type (radical polymerization type) adhesive composition. The adhesive composition of the present embodiment can be suitably used as an adhesive composition for circuit connection. Hereinafter, each component will be described.

(Silane compound)
The adhesive composition of the present embodiment contains a first silane compound having a radically polymerizable functional group and a second silane compound that reacts with the first silane compound. The second silane compound is a compound that does not correspond to the first silane compound and does not have a radically polymerizable functional group. The silane compound may be a silane coupling agent.

Examples of the radically polymerizable functional group include ethylenically unsaturated bond-containing groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and a maleimide group. The radically polymerizable functional group is preferably at least one selected from the group consisting of (meth) acryloyl group and vinyl group, and more preferably (meth) acryloyl group, from the viewpoint of obtaining more excellent storage stability and adhesiveness. ..

The second silane compound may have a functional group that does not participate in the radical polymerization reaction. Functional groups that are not involved in the radical polymerization reaction include alkyl groups, phenyl groups, alkoxysilyl groups, amino groups, alkylamino groups (methylamino groups, etc.), benzylamino groups, phenylamino groups, cycloalkylamino groups (cyclohexylamino groups). Etc.), morpholino group, piperazino group, isocyanato group, imidazole group, ureido group, dialkylamino group (dimethylamino group, etc.), epoxy group and the like. The epoxy group may be contained in an epoxy group-containing group (group containing an epoxy group) such as a glycidyl group and a glycidoxy group. 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, from the viewpoint of obtaining more excellent storage stability.

［式中、Ｘは、有機基を示し、Ｒ^１及びＲ^２は、それぞれ独立にアルキル基を示し、ｍは、０〜２の整数を示し、ｓは、０以上の整数を示す。Ｒ^１が複数存在する場合、各Ｒ^１は、互いに同じであってもよく、異なっていてもよい。Ｒ^２が複数存在する場合、各Ｒ^２は、互いに同じであってもよく、異なっていてもよい。Ｒ^１、Ｒ^２及びＣ_ｓＨ_２ｓのそれぞれは、分岐していてもよい。］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 organochlorosilane with an alcohol.

[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 0 or more. When there are a plurality of ^{R 1 , each R 1} may be the same as or different from each other. When there are a plurality of ^{R 2 , 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 be branched. ]

Examples of the organic group X include an ethylenically unsaturated bond-containing group (a group containing an ethylenically unsaturated bond), a nitrogen atom-containing group (a group containing a nitrogen atom), a sulfur atom-containing group (a group containing a sulfur atom), and an epoxy group. And so on. Examples of the ethylenically unsaturated bond-containing group include a (meth) acryloyl group, a vinyl group, and a styryl group. Examples of the nitrogen atom-containing group include an amino group, a mono-substituted amino group, a di-substituted amino group, an isocyanato group, an imidazole group, a ureido group, a maleimide group and the like. Examples of the mono-substituted amino group include an alkylamino group (methylamino group and the like), a benzylamino group, a phenylamino group, a cycloalkylamino group (cyclohexylamino group and the like) and the like. Examples of the di-substituted amino group include an acyclic di-substituted amino group and a cyclic di-substituted amino group. Examples of the acyclic di-substituted amino group include a dialkylamino group (dimethylamino group and the like). Examples of the cyclic di-substituted amino group include a morpholino group and a piperazino group. Examples of the sulfur atom-containing group include a mercapto 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 glycidoxy group. The (meth) acryloyl group may be included in the (meth) acryloyloxy group.

The alkyl groups of R ¹ and R ² have, for example, 1 to 20 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group and a tetradecyl group. , Pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecil group, icosyl group and the like. 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 from the viewpoint that the alkoxysilyl group portion is less likely to cause steric hindrance when reacting with the adherend and further excellent adhesion to the adherend is obtained. ~ 5 is more preferable. The carbon number of the alkyl group of R ^2, from the viewpoint of obtaining more excellent adhesion to an adherend, 10 is preferably 1 to 5 is more preferable.

m is an integer from 0 to 2. m is preferably 0 to 1, more preferably 0, from the viewpoint that the alkoxysilyl group portion is less likely to cause steric hindrance when reacting with the adherend and further excellent adhesiveness to the adherend is obtained. s is an integer greater than or equal to 0. For s, an integer of 1 to 20 is preferable, and an integer of 1 to 10 is more preferable, from the viewpoint of obtaining more excellent storage stability.

Examples of the first silane compound include (meth) acryloxyalkyltrialkoxysilane, (meth) acryloxydialkyldialkoxysilane, (meth) acryloxitrialkylalkoxysilane, alkenyltrialkoxysilane, styryltrialkoxysilane, and styrylalkyl. Examples thereof include trialkoxysilane. As the first silane compound, at least one selected from the group consisting of (meth) acryloxyalkyltrialkoxysilane and (meth) acryloxydialkyldialkoxysilane from the viewpoint of obtaining more excellent storage stability and adhesiveness. Is preferable. Examples of the (meth) acryloxyalkyltrialkoxysilane include 3- (meth) acryloxipropyltrimethoxysilane, 3- (meth) acryloxipropyltriethoxysilane, 8- (meth) acryloxyoctyltrimethoxysilane, and 8- (Meta) Acryloxyoctyltriethoxysilane and the like can be mentioned. Examples of the (meth) acryloxydialkyldialkoxysilane include 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 8- (meth) acryloxyoctylmethyldimethoxysilane, and 8 -(Meta) acryloxyoctylmethyldiethoxysilane and the like can be mentioned. Examples of the alkenyl trialkoxysilane include vinyltrialkoxysilane, octenyltrialkoxysilane, and octenylalkyldialkoxysilane. Examples of the vinyltrialkoxysilane include vinyltrimethoxysilane and vinyltriethoxysilane. Examples of the octenyltrialkoxysilane include 7-octenyltrimethoxysilane and 7-octenyltriethoxysilane. Examples of the octenylalkyldialkoxysilane include 7-octenylmethyldimethoxysilane and 7-octenylmethyldiethoxysilane. Examples of the styryltrialkoxysilane include p-styryltrimethoxysilane. Examples of the styrylalkyltrialkoxysilane include p-styryloctyltrialkoxysilane. The first silane compound may be used alone or in combination of two or more.

Examples of the second silane compound include glycidoxyalkyltrialkoxysilanes (3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 8-glycidoxyoctyltrimethoxysilane, 8-glycid). Xioctyltriethoxysilane, etc.), Glycydoxydialkyldialkoxysilane (3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 8-glycidoxyoctylmethyldimethoxysilane, 8-glyci Sidoxyoctylmethyldiethoxysilane, etc.), N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (amino) Ethyl) -8-aminooctylmethyldimethoxysilane, N-2- (aminoethyl) -8-aminooctyltrimethoxysilane, 3-aminooctyltrimethoxysilane, 3-aminooctyltriethoxysilane, 3-triethoxysilyl- N- (1,3-dimethylbutylidene) octylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-8-aminooctyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 8-ureidooctyl Triethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 8-mercaptooctylmethyldimethoxysilane, 8-mercaptooctylmethyldimethoxysilane, 3-isocyanuppropyltrimethoxysilane, 3-isocyanuppropyltriethoxysilane Examples thereof include silane, 8-isocyanate octyl dimethoxysilane, and 8-isocyanate octyl diethoxysilane. The second silane compound is preferably at least one selected from the group consisting of glycidoxyalkyltrialkoxysilane and glycidoxydialkyldialkoxysilane from the viewpoint of obtaining more excellent storage stability, and 3-glycidoxy is preferable. At least one selected from the group consisting of propyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane is more preferable. 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 the formula (I) include tetraalkoxysilane, alkyltrialkoxysilane, and dialkyldialkoxysilane. Examples of such a second silane compound include methyltrimethoxysilane, methyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, dimethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, and phenyltrimethoxy. Examples thereof include silane and phenyltriethoxysilane. As the second silane compound other than the compound represented by the formula (I), at least one selected from the group consisting of alkyltrialkoxysilanes and tetraalkoxysilanes is preferable from the viewpoint of obtaining more excellent storage stability. At least one selected from the group consisting of methyltrimethoxysilane, ethyltriethoxysilane, tetramethoxysilane and tetraethoxysilane is more preferable. The silane compound other than the second compound represented by the 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 the adherend (circuit member, etc.) and the adhesive composition or a cured product thereof (the cured product thereof). From the viewpoint of easily suppressing the generation of exfoliated bubbles at the interface with the circuit connection member, etc.), the total mass of the adhesive component (solid content other than conductive particles in the adhesive composition; the same applies hereinafter) of the adhesive composition is used as a reference. The following range is preferable. The content of the silane compound is preferably 0.1% by mass or more, more preferably 0.25% by mass or more, further preferably 0.5% by mass or more, and 1% by mass or more. It is particularly preferable that the content is 2% by mass or more, and 3% by mass or more is very preferable. The content of the silane compound is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less. From these viewpoints, the content of the silane compound is preferably 0.1 to 20% by mass, more preferably 0.25 to 15% by mass, and preferably 0.5 to 10% by mass. Further preferably, it is particularly preferably 1 to 5% by mass, extremely preferably 2 to 5% by mass, and very preferably 3 to 5% by mass.

The content of the first silane compound is an adhesive from the viewpoint of easily suppressing the generation of exfoliated bubbles at the interface between the adherend (circuit member, etc.) and the adhesive composition or its cured product (circuit connection member, etc.). The following range is preferable based on the total mass of the adhesive component of the composition. The content of the first silane compound is preferably 0.1% by mass or more, more preferably 0.25% by mass or more, further preferably 0.5% by mass or more, and 1% by mass. % Or more is particularly preferable, and 1.5% by mass or more is extremely preferable. The content of the first silane compound is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, and preferably 5% by mass or less. It is particularly preferable, and it is extremely preferable that it is 3% by mass or less. From these viewpoints, the content of the first silane compound is preferably 0.1 to 20% by mass, more preferably 0.25 to 15% by mass, and 0.5 to 10% by mass. It is more preferably 1 to 5% by mass, and extremely preferably 1.5 to 3% by mass.

The content of the second silane compound is an adhesive from the viewpoint of easily suppressing the generation of exfoliated bubbles at the interface between the adherend (circuit member, etc.) and the adhesive composition or its cured product (circuit connection member, etc.). The following range is preferable based on the total mass of the adhesive component of the composition. The content of the second silane compound is preferably 0.1% by mass or more, more preferably 0.25% by mass or more, further preferably 0.5% by mass or more, and 1% by mass. % Or more is particularly preferable, and 1.5% by mass or more is extremely preferable. The content of the second silane compound is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, and preferably 5% by mass or less. It is particularly preferable, and it is extremely preferable that it is 3% by mass or less. From these viewpoints, the content of the second silane compound is preferably 0.1 to 20% by mass, more preferably 0.25 to 15% by mass, and 0.5 to 10% by mass. It is more preferably 1 to 5% by mass, and extremely preferably 1.5 to 3% by mass.

The ratio of the content of the first silane compound to the content of the second silane compound (mass ratio; relative value to the content 1 of the second silane compound) is a viewpoint for obtaining further excellent storage stability and adhesiveness. Therefore, 0.01 or more is preferable, 0.1 or more is more preferable, 0.2 or more is further preferable, 0.5 or more is particularly preferable, and 1 or more is extremely preferable. 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 extremely preferably 2 or less.

(Radical polymerizable compound)
The radically polymerizable compound is a compound having a radically polymerizable functional group and does not correspond to the first silane compound. Examples of such radically polymerizable compounds include (meth) acrylate compounds, maleimide compounds, citraconimide resins, and nadiimide resins. The "(meth) acrylate compound" means a compound having a (meth) acryloyl group. The radically polymerizable compound may be used in the state of a monomer or an oligomer, and the monomer and the oligomer may be used in combination. The radically polymerizable compound may be used alone or in combination of two or more.

Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, ethylene glycol di (meth) acrylate, and diethylene glycol di (meth) acrylate. Trimethylol Propane Tri (meth) Acrylate, Tetramethylol Methantetra (Meta) Acrylate, 2-Hydroxy-1,3-di (Meta) Acryloxy Propane, 2,2-Bis [4-((Meta) Acryloxymethoxy) Phenyl] propane, 2,2-bis [4-((meth) acryloxypolyethoxy) phenyl] propane, dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, tris ((meth) acryloyloxy) Examples thereof include ethyl) isocyanurate, urethane (meth) acrylate, isocyanuric acid EO-modified di (meth) acrylate, and 9,9-bis- [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene. As the radically polymerizable compound other than the (meth) acrylate compound, for example, the compound described in Patent Document 3 (International Publication No. 2009/0638227) can be preferably used. The (meth) acrylate compound may be used alone or in combination of two or more.

As the radically polymerizable compound, a (meth) acrylate compound is preferable, and a urethane (meth) acrylate is more preferable, from the viewpoint of obtaining more excellent storage stability. 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 tricyclodecanyl group and a triazine ring.

Further, as the radically polymerizable compound, it is preferable to use a radically polymerizable compound having a phosphoric acid ester structure represented by the following general formula (II), and the radically polymerizable compound such as a (meth) acrylate compound and the formula ( It is more preferable to use it in combination with a radically polymerizable compound having a phosphoric acid ester structure represented by II). In these cases, the adhesive strength to the surface of the inorganic substance (metal or the like) is improved, so that it is suitable for adhesion between circuit electrodes, for example.

［式中、ｐは１〜３の整数を示し、Ｒは、水素原子又はメチル基を示す。］

[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 a 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) acid phosphate, di (2- (meth) acryloyloxyethyl) acid phosphate and the like. .. The radically polymerizable compound having a phosphoric acid ester structure represented by the formula (II) may be used alone or in combination of two or more.

The content of the radically polymerizable compound having a phosphoric acid ester structure represented by the formula (II) is the total amount of the radically polymerizable compound (the total amount of the components corresponding to the radically polymerizable compound) from the viewpoint of obtaining more excellent adhesiveness. Similarly) 1 to 100 parts by mass is preferable, 1 to 50 parts by mass is more preferable, and 1 to 10 parts by mass is further preferable with respect to 100 parts by mass. The content of the radically polymerizable compound having a phosphoric acid ester structure represented by the formula (II) is the content of the radically polymerizable compound and the film forming material (components used as necessary) from the viewpoint of obtaining more excellent adhesiveness. With respect to 100 parts by mass in total, 0.01 to 50 parts by mass is preferable, 0.5 to 10 parts by mass is more preferable, and 0.5 to 5 parts by mass is further preferable.

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

The content of the radically polymerizable compound is preferably in the following range based on the total mass of the adhesive component of the adhesive composition from the viewpoint of obtaining more excellent adhesiveness. The content of the radically polymerizable compound is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 40% by mass or more. preferable. The content of the radically polymerizable compound is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 70% by mass or less, and particularly preferably 60% by mass or less. It is preferably 50% by mass or less, which is extremely preferable. From these viewpoints, the content of the radically polymerizable compound is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, further preferably 30 to 70% by mass, and 40. It is particularly preferably to 60% by mass, and extremely preferably 40 to 50% by mass.

(Hardener)
As the curing agent, a curing agent that generates free radicals by heat (heating), a curing agent that generates free radicals by light, a curing agent that generates free radicals by ultrasonic waves, electromagnetic waves, or the like can be used.

A curing agent that generates free radicals by heat is a curing agent that decomposes by heat to generate free radicals. Examples of such a curing agent include peroxides (organic peroxides and the like), azo compounds and the like. The curing agent is appropriately selected according to the target connection temperature, connection time, pot life, and the like. The adhesive composition of the present embodiment contains a peroxide having a half-life temperature of 120 ° C. or less for 1 minute (hereinafter referred to as "peroxide A") as the curing agent. The 1-minute half-life temperature of peroxide A is preferably 40 ° C. or higher from the viewpoint that low-temperature connection can be more easily achieved.
The half-life is the time until the concentration of peroxide is reduced to half of the initial value, and the 1-minute half-life temperature indicates the temperature at which the half-life is 1 minute. As the 1-minute half-life temperature, the value published in the catalog (organic peroxide (10th edition, February 2015)) published by NOF CORPORATION can be used.

Specific examples of the curing agent that generates free radicals by heat include diacyl peroxide, peroxydicarbonate, peroxyester, peroxyketal, dialkyl peroxide, hydroperoxide, silyl peroxide and the like.

As the curing agent, from the viewpoint of suppressing corrosion of electrodes (circuit electrodes, etc.), a curing agent having a concentration of chloride ions and organic acids of 5000 ppm or less is preferable, and a curing agent having a small amount of organic acids generated after thermal decomposition is preferable. More preferred. Specific examples of such a curing agent include peroxyester, dialkyl peroxide, hydroperoxide, silyl peroxide and the like, and peroxyester is more preferable from the viewpoint of obtaining high reactivity.

Peroxyesters include cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, and t-hexyl. Peroxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2-) Ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate Ate, t-butylperoxyisobutyrate, 1,1-bis (t-butylperoxy) cyclohexane, t-hexylperoxyisopropylmonocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate , T-Butylperoxylaurate, 2,5-dimethyl-2,5-di (m-toluoleperoxy) hexane, t-Butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate , T-Hexylperoxybenzoate, t-butylperoxyacetate and the like. As the curing agent other than the peroxy ester that generates free radicals by heat, for example, the compound described in Patent Document 3 (International Publication No. 2009/0638227) can be preferably used. The peroxy ester may be used alone or in combination of two or more.

Examples of peroxide A include di-n-propylperoxydicarbonate (1 minute half-life temperature: 94.0 ° C.), diisopropylperoxydicarbonate (1 minute half-life temperature: 88.3 ° C.), and di (4). -T-Butylcyclohexyl) peroxydicarbonate (1 minute half-life temperature: 92.1 ° C), di (2-ethylhexyl) peroxydicarbonate (1 minute half-life temperature: 90.6 ° C), t-hexylper Oxyneodecanoate (1 minute half-life temperature: 100.9 ° C.), t-butylperoxyneoheptanoate (1 minute half-life temperature: 104.6 ° C.), t-hexyl peroxypivalate (1 minute) Half-life temperature: 109.1 ° C.), t-butyl peroxypivalate (1 minute half-life temperature: 110.3 ° C.), di (3,5,5-trimethylhexanoyl) peroxide (1 minute half-life temperature) : 112.6 ° C.), dilauroyl peroxide (1 minute half-life temperature: 116.4 ° C.), 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane (1 minute half-life) Temperature: 118.8 ° C.) and the like. High reactivity can be obtained by using these peroxides A. Peroxide A may be used alone or in combination of two or more.

The adhesive composition of the present embodiment may further contain a curing agent other than peroxide A. That is, the peroxide A and the peroxide having a half-life temperature of more than 120 ° C. for 1 minute may be used in combination. In this case, even better low temperature activity and storage stability tend to be obtained. Hardeners other than peroxide A have a half-life of 40 ° C. or higher and a 1-minute half-life temperature of 180 ° C. or lower from the viewpoint of obtaining high reactivity and further improving pot life. An organic peroxide having a half-life temperature of 40 ° C. or higher for 10 minutes and a half-life temperature of 160 ° C. or lower for 1 minute is more preferable.

A curing agent that generates free radicals by light is a curing agent that decomposes by light to generate free radicals. As such a curing agent, a compound that generates free radicals by irradiation with light having a wavelength of 150 to 750 nm can be used. Examples of such a compound include Photoinitiation, Photopolymerization, and Photocuring, J. et al., From the viewpoint of high sensitivity to light irradiation. -P. The α-acetaminophenone derivatives and phosphine oxide derivatives described in Foausier, Hanser Publishers (1995), p17-p35 are preferred.

The curing agent may be used alone or in combination of two or more. A curing agent may be used in combination with a decomposition accelerator, a decomposition inhibitor, or the like. Further, the curing agent may be coated with a polyurethane-based or polyester-based polymer substance or the like and microencapsulated. Microencapsulated hardeners are preferred because of their extended pot life.

The content of peroxide A is preferably in the following range from the viewpoint that a sufficient reaction rate can be easily obtained when the connection time is 25 seconds or less. The content of peroxide A is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and 3 parts by mass or more with respect to 100 parts by mass of the radically polymerizable compound. Is more preferable, 5 parts by mass or more is particularly preferable, and 10 parts by mass or more is extremely preferable. The content of peroxide A is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and further preferably 30 parts by mass or less with respect to 100 parts by mass of the radically polymerizable compound. It is preferably 20 parts by mass or less, and extremely 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, based on 100 parts by mass of the radically polymerizable compound. It is more preferably 3 to 30 parts by mass, particularly preferably 5 to 20 parts by mass, and extremely preferably 10 to 15 parts by mass.

The content of peroxide A is preferably in the following range from the viewpoint that a sufficient reaction rate can be easily obtained when the connection time is 25 seconds or less. The content of peroxide A is preferably 2 parts by mass or more, preferably 3 parts by mass or more, based on 100 parts by mass of the total of the radically polymerizable compound and the film forming material (components used if necessary). More preferably, it is more preferably 4 parts by mass or more, and particularly preferably 5 parts by mass or more. The content of peroxide A is preferably 10 parts by mass or less, preferably 8 parts by mass or less, based on 100 parts by mass of the total of the radically polymerizable compound and the film forming material (components used if necessary). It is more preferably 7 parts by mass or less, and particularly preferably 6 parts by mass or less. From these viewpoints, the content of peroxide A is preferably 2 to 10 parts by mass with respect to 100 parts by mass in total of the radically polymerizable compound and the film forming material (components used if necessary). It is more preferably 3 to 10 parts by mass, further preferably 4 to 8 parts by mass, particularly preferably 5 to 7 parts by mass, and extremely preferably 5 to 6 parts by mass.

The content of peroxide A when the connection time is not limited is preferably in the following range from the viewpoint that a sufficient reaction rate can be easily obtained. The content of peroxide A is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, and 1 part by mass or more with respect to 100 parts by mass of the radically polymerizable compound. It is more preferably 3 parts by mass or more, very preferably 5 parts by mass or more, and very preferably 10 parts by mass or more. The content of peroxide A is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and further preferably 30 parts by mass or less with respect to 100 parts by mass of the radically polymerizable compound. It is preferably 20 parts by mass or less, and extremely 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, based on 100 parts by mass of the radically polymerizable compound. It is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, extremely preferably 5 to 15 parts by mass, and very preferably 10 to 15 parts by mass. ..

The content of peroxide A when the connection time is not limited is preferably in the following range from the viewpoint that a sufficient reaction rate can be easily obtained. The content of peroxide A is preferably 0.01 part by mass or more, preferably 0.1 part by mass, based on 100 parts by mass of the total of the radically polymerizable compound and the film forming material (components used if necessary). It is more preferably parts or more, more preferably 2 parts by mass or more, particularly preferably 3 parts by mass or more, extremely preferably 4 parts by mass or more, and preferably 5 parts by mass or more. Very preferred. The content of peroxide A is preferably 100 parts by mass or less, preferably 50 parts by mass or less, based on 100 parts by mass of the total of the radically polymerizable compound and the film forming material (components used as necessary). More preferably, it is more preferably 10 parts by mass or less, particularly preferably 8 parts by mass or less, extremely preferably 7 parts by mass or less, and very preferably 6 parts by mass or less. From these viewpoints, the content of peroxide A is 0.01 to 100 parts by mass with respect to 100 parts by mass in total of the radically polymerizable compound and the film forming material (components used as necessary). It is preferably 0.1 to 50 parts by mass, more preferably 2 to 10 parts by mass, particularly preferably 3 to 8 parts by mass, and extremely preferably 4 to 7 parts by mass. It is preferably 5 to 6 parts by mass, which is very preferable.

(Film forming material)
The adhesive composition of the present embodiment may contain a film-forming material, if necessary. The film-forming material improves the handleability of the film under normal conditions (normal temperature and pressure) when the liquid adhesive composition is solidified into a film, and has characteristics such as resistance to tearing, resistance to cracking, and resistance to stickiness. Can be applied to the film. Examples of the film forming material include phenoxy resin, polyvinyl formal, polystyrene, polyvinyl butyral, polyester, polyamide, xylene resin, polyurethane and the like. Among these, a phenoxy resin is preferable from the viewpoint of excellent 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 a resin obtained by double-adding a bifunctional epoxy resin and a bifunctional phenol, and a resin obtained by reacting the bifunctional phenol and epihalohydrin until they are polymerized. Can be mentioned. The phenoxy resin contains, for example, 1 mol of bifunctional phenols and 0.985 to 1.015 mol of epihalohydrin at a temperature of 40 to 120 ° C. in a non-reactive solvent in the presence of a catalyst such as an alkali metal hydroxide. It can be obtained by reacting. As the phenoxy resin, from the viewpoint of excellent mechanical properties and thermal properties of the resin, in particular, the compounding equivalent ratio of the bifunctional epoxy resin and the bifunctional phenols is set to epoxy group / phenol hydroxyl group = 1 / 0.9 to It is set to 1 / 1.1, and in the presence of a catalyst such as an alkali metal compound, an organic phosphorus compound, or a cyclic amine compound, an organic solvent having a boiling point of 120 ° C. or higher (amide-based, ether-based, ketone-based, lactone-based, alcohol-based) Etc.), a resin obtained by heating to 50 to 200 ° C. under the condition that the reaction solid content is 50% by mass or less and performing a heavy addition reaction is preferable. The phenoxy resin may be used alone or in combination of two or more.

Examples of the bifunctional epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, biphenyl diglycidyl ether, and methyl-substituted biphenyl diglycidyl ether. Bifunctional phenols are compounds having two phenolic hydroxyl groups. Examples of bifunctional phenols include bisphenols such as hydroquinones, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, bisphenol fluorene, methyl-substituted bisphenol fluorene, dihydroxybiphenyl, and methyl-substituted dihydroxybiphenyl. The phenoxy resin may be modified (for example, epoxy-modified) with a radically polymerizable functional group or other reactive compound.

The content of the film forming material is preferably 10 to 90 parts by mass, more preferably 20 to 60 parts by mass, and 30 to 50 parts by mass with respect to 100 parts by mass of the adhesive component of the adhesive composition. It is more preferably a part.

(Conductive particles)
The adhesive composition of the present embodiment may further contain conductive particles. Examples of the constituent materials of the conductive particles include gold (Au), silver (Ag), nickel (Ni), copper (Cu), metals such as solder, and carbon. Further, coated conductive particles in which a non-conductive resin, glass, ceramic, plastic or the like is used as a core and the core is coated with the metal (metal particles or the like) or carbon may be used. Since the coated conductive particles or the heat-melted metal particles are deformable by heating and pressurizing, the height variation of the circuit electrode is eliminated at the time of connection, and the contact area with the electrode is increased at the time of connection, so that the reliability is improved. preferable.

The average particle size of the conductive particles is preferably 1 to 30 μm from the viewpoint of excellent dispersibility and conductivity. The average particle size of the conductive particles can be measured using, for example, instrumental analysis such as laser diffraction. From the viewpoint of excellent conductivity, the content of the conductive particles is preferably 0.1% by volume or more, more preferably 1% by volume or more, based on the total volume of the adhesive components of the adhesive composition. The content of the 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, from the viewpoint of easily suppressing short-circuiting of electrodes (circuit electrodes, etc.). Preferably, 10% by volume or less is more preferable, 5% by volume or less is particularly preferable, and 3% by volume or less is extremely preferable. From these viewpoints, the content of the conductive particles is preferably 0.1 to 50% by volume, more preferably 0.1 to 20% by volume, further preferably 1 to 20% by volume, and particularly preferably 1 to 10% by volume. , 1 to 5% by volume is extremely preferable, and 1 to 3% by volume is very preferable. The "volume%" is determined based on the volume of each component before curing at 23 ° C., and the volume of each component can be converted from mass to volume by using the specific gravity. In addition, the volume of the target component is increased by putting the target component in a container containing an appropriate solvent (water, alcohol, etc.) that does not dissolve or swell the target component and wets the target component well. Can also be obtained as.

(Other ingredients)
The adhesive composition of the present embodiment may appropriately contain a polymerization inhibitor such as hydroquinone and methyl ether hydroquinone, if necessary.

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

The adhesive composition of the present embodiment may contain coated fine particles in which the surface of the conductive particles is 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, it is easy to suppress a short circuit due to contact between the conductive particles. Can be improved. 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 the present embodiment may also contain rubber fine particles, a filler (silica particles, etc.), a softening agent, an accelerator, an antiaging agent, a coloring agent, a flame retardant, a thixotropic agent, and the like. The adhesive composition of the present embodiment may appropriately contain additives such as a thickener, a leveling agent, a colorant, and a weather resistance improver.

The rubber fine particles have an average particle size of 2 times or less the average particle size 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 are preferred. In particular, when the material of the rubber fine particles is silicone, acrylic emulsion, SBR, NBR or polybutadiene rubber, it is preferable to use the rubber fine particles alone or in combination of two or more. The three-dimensionally crosslinked rubber fine particles have excellent solvent resistance and are easily dispersed in the adhesive composition.

The filler can improve the electrical characteristics (connection reliability, etc.) between the circuit electrodes. As the filler, for example, particles having an average particle size of 1/2 or less of the average particle size of the conductive particles can be preferably used. When non-conductive particles are used in combination with a filler, particles having an average particle size or less of the non-conductive particles can be used as the 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. When the content is 60 parts by mass or less, the effect of improving the connection reliability tends to be more sufficiently obtained. When the content is 0.1 part by mass or more, the effect of adding the filler tends to be sufficiently obtained.

The adhesive composition of the present embodiment can be used in the form of a paste when it is liquid at room temperature. When the adhesive composition is solid at room temperature, it may be used by heating or may be made into a paste by using a solvent. The solvent that can be used is not particularly limited as long as it is a solvent that is not reactive with the components in the adhesive composition and exhibits sufficient solubility. The solvent is preferably a solvent having a boiling point of 50 to 150 ° C. at normal pressure. When the boiling point is 50 ° C. or higher, the solvent is poorly volatile at room temperature, so that it can be used even in an open system. When the boiling point is 150 ° C. or lower, it is easy to volatilize the solvent, so that good reliability can be obtained after bonding.

The adhesive composition of the present embodiment may be in the form of a film. If necessary, an adhesive composition containing a solvent or the like is applied onto a fluororesin film, a polyethylene terephthalate film, or a releaseable base material (release paper, etc.), and then the solvent or the like is removed to form a film-like adhesive. The composition can be obtained. Further, a film-like adhesive composition can be obtained by impregnating a base material such as a non-woven fabric with the solution, placing the solution on the peelable base material, and then removing the solvent or the like. When the adhesive composition is used in the form of a film, it is excellent in handleability and the like. The thickness of the film-like adhesive composition may be 1 to 100 μm or 5 to 50 μm.

The adhesive composition of the present embodiment can be adhered by pressurizing with heating or light irradiation. By using both heating and light irradiation, adhesion can be performed at a lower temperature in a short time. The light irradiation preferably irradiates light in the wavelength range of 150 to 750 nm. As the light source, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp (ultra-high pressure mercury lamp, etc.), a xenon lamp, a metal halide lamp, or the like can be used. The irradiation amount may be 0.1 to 10 J / cm ^2. The heating temperature is not particularly limited, but is preferably a temperature of 50 to 170 ° C. The pressure is not particularly limited as long as it does not damage the adherend, but is preferably 0.1 to 10 MPa. Heating and pressurization are preferably performed 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 type of adherends, or may be used as an adhesive for different types of adherends having different coefficients of thermal expansion. Specifically, it is used as a circuit connection material typified by an anisotropic conductive adhesive, a silver paste, a silver film, etc .; an elastomer for CSP, an underfill material for CSP, a semiconductor element adhesive material typified by LOC tape, etc. be able to.

<Structure and its manufacturing method>
The structure of the present embodiment includes the adhesive composition of the present embodiment or a cured product thereof. The structure of this embodiment is, for example, a semiconductor device such as a circuit connection structure. As one aspect 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 first circuit member. And a circuit connecting member arranged between the second circuit members. The first circuit member includes, for example, a first substrate and a first circuit electrode arranged on the first substrate. The second circuit member has, 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 opposed to each other and are electrically connected to each other. The circuit connection member contains the adhesive composition of the present embodiment or a cured product thereof. The structure according to the present embodiment may include the adhesive composition according to the present embodiment or a cured product thereof, and instead of the circuit member of the circuit connection structure, a member having no circuit electrode ( A substrate or the like) may be used.

The method for producing a structure of the present embodiment includes a step of curing the adhesive composition of the present embodiment. As one aspect of the method for manufacturing the structure of the present embodiment, the method for manufacturing the circuit connection structure includes a first circuit member having a first circuit electrode and a second circuit member having a second circuit electrode. The arrangement step of arranging the adhesive composition of the present embodiment between the two, and the first circuit member and the second circuit member are pressurized to electrically press the first circuit electrode and the second circuit electrode. It is provided with a heating and pressurizing step of heating and curing the adhesive composition. In the arrangement step, the first circuit electrode and the second circuit electrode can be arranged so as to face each other. In the heating and pressurizing step, the first circuit member and the second circuit member can be pressurized in opposite directions.

Hereinafter, a circuit connection structure and a method for manufacturing the same will be described as one aspect of the present embodiment with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an embodiment of the structure. The circuit connection structure 100a shown in FIG. 1 includes a circuit member (first circuit member) 20 and a circuit member (second circuit member) 30 facing each other, and is between the circuit member 20 and the circuit member 30. A circuit connecting member 10 for connecting these is arranged in the. The circuit connection member 10 contains a cured product of the adhesive composition of the present embodiment.

The circuit member 20 includes a substrate (first substrate) 21 and a circuit electrode (first circuit electrode) 22 arranged on the main surface 21a of the substrate 21. In some cases, an insulating layer (not shown) may be arranged on the main surface 21a of the substrate 21.

The circuit member 30 includes a substrate (second substrate) 31 and a circuit electrode (second circuit electrode) 32 arranged on the main surface 31a of the substrate 31. In some cases, an insulating layer (not shown) may be arranged on the main surface 31a of the substrate 31.

The circuit connection member 10 contains an insulating substance (cured product of components other than conductive particles) 10a and conductive particles 10b. The conductive particles 10b are arranged at least between the circuit electrodes 22 and the circuit electrodes 32 that face each other. 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 members 20 and 30 have one or more circuit electrodes (connection terminals). As the circuit members 20 and 30, for example, members having electrodes that require electrical connection can be used. As the circuit member, chip parts such as a semiconductor chip (IC chip), a resistor chip, and a capacitor chip; a printed circuit board, a substrate such as a semiconductor mounting substrate, and the like can be used. Examples of the combination of the circuit members 20 and 30 include a semiconductor chip and a semiconductor mounting substrate. 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; and composites of glass and epoxy. The substrate may 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 configuration as the circuit connection structure 100a except that the circuit connection member 10 does not contain the conductive particles 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 and are electrically connected to each other without using conductive particles.

The circuit connection structures 100a and 100b can be manufactured, for example, by the following methods. 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 and drying the adhesive composition. When the adhesive composition is in the form of a film, the resin layer containing the adhesive composition is arranged on the circuit member 20 by attaching the film-like adhesive composition to the circuit member 20. Subsequently, 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 so as to face each other. Then, by heat-treating or irradiating the resin layer containing the adhesive composition with light, the adhesive composition is cured to obtain a cured product (circuit connection member 10). From the above, the circuit connection structures 100a and 100b can be obtained.

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

(Polyurethane synthesis)
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), which is a diol having an ether bond, and methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.) After adding 4000 parts by mass of solvent), the reaction solution was prepared by stirring at 40 ° C. for 30 minutes. After raising the temperature of the reaction solution to 70 ° C., 0.0127 parts by mass of dimethyltin laurate (catalyst) was added. Then, 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 to this reaction solution over 1 hour. Then, stirring was continued at the above temperature until no ^{absorption peak (2270 cm -1} ) derived from the isocyanate group was observed by an infrared spectrophotometer (manufactured by JASCO Corporation) to obtain a polyurethane methyl ethyl ketone solution. Next, the amount of solvent was adjusted so that the solid content concentration (concentration of polyurethane) of this solution was 30% by mass. The weight average molecular weight of the obtained polyurethane (urethane resin) was 320,000 (standard polystyrene conversion value) as a result of measurement by GPC (gel permeation chromatography). Table 1 shows the measurement conditions of GPC.

(Synthesis of urethane acrylate)
In a 2 L (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, number average molecular weight 2000) and 2-hydroxyethyl A reaction solution was prepared by charging 238 parts by mass of acrylate, 0.49 parts by mass of hydroquinone monomethyl ether, and 4.9 parts by mass of a tin-based catalyst. 666 parts by mass of isophorone diisocyanate (IPDI) was uniformly added dropwise over 3 hours to the reaction solution heated to 70 ° C. to react. After the completion of the dropping, the reaction was continued for 15 hours, and the time when the NCO% (NCO content) became 0.2% by mass or less was regarded as the end of the reaction, and urethane acrylate was obtained. NCO% was confirmed by a potential difference automatic titrator (trade name: AT-510, manufactured by Kyoto Denshi Kogyo Co., Ltd.). As a result of analysis by GPC, the weight average molecular weight of urethane acrylate was 8500 (standard polystyrene conversion value). The analysis by GPC was performed under the same conditions as the analysis of the weight average molecular weight of the polyurethane.

(Preparation of conductive particles)
A nickel layer having a thickness of 0.2 μm was formed on the surface of the polystyrene particles. Further, a gold layer having a thickness of 0.04 μm was formed on the outside of the nickel layer. As a result, conductive particles having an average particle size of 4 μm were produced.

(Preparation of film-like adhesive)
The components shown in Tables 2 and 3 were mixed at the mass ratio (solid content) shown in Tables 2 and 3 to obtain a mixture. The conductive particles were dispersed in this 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 liquid for forming a film-like adhesive. This coating liquid was applied to a polyethylene terephthalate (PET) film having a thickness of 50 μm using a coating device. The coating film was dried with hot air at 70 ° C. for 10 minutes to form a film-like adhesive having a thickness of 18 μm.

The phenoxy resins shown in Tables 2 and 3 were used in the form of a 40% by mass solution prepared 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. As the polyurethane, the polyurethane synthesized as described above was used. As the radically polymerizable compound A, urethane acrylate synthesized as described above was used. As the radically polymerizable compound B, isocyanuric acid EO-modified diacrylate (trade name: M-215, manufactured by Toagosei Co., Ltd.) was used. As the radically polymerizable compound C (phosphate ester), 2-methacryloyloxyethyl acid phosphate (trade name: light ester P-2M, manufactured by Kyoeisha Chemical Co., Ltd.) was used. As the radically polymerizable compound D, 9,9-bis- [4- (2-acryloyloxyethoxy) phenyl] fluorene (trade name: A-BPEF, manufactured by Shin-Nakamura Chemical Co., Ltd.) was used.

The following components were used as the silane compound (first silane compound) having a radically polymerizable functional group (functional group involved in the radical polymerization reaction of the curing system). 3-methacryloxypropylmethyldimethoxysilane (trade name: KBM-502, manufactured by Shin-Etsu Chemical Co., Ltd.) as silane compound A1, 3-methacryloxypropyltrimethoxysilane (trade name: KBM-503, Shin-Etsu Chemical) as silane compound A2. 3-Acryloxypropyltrimethoxysilane (trade name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane compound A3 (manufactured by Kogyo Co., Ltd.).

As a silane compound (second silane compound) having a functional group not involved in the radical polymerization reaction of the curing system and not having a radically polymerizable functional group (functional group involved in the radical polymerization reaction of the curing system) , The following components were used. 3-glycidoxypropylmethyldimethoxysilane (trade name: KBM-402, manufactured by Shin-Etsu Chemical Co., Ltd.) as silane compound B1, 3-glycidoxypropyltrimethoxysilane (trade name: KBM-403,) as silane compound B2. Methyltrimethoxysilane (trade name: KBM-13, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane compound B3 (manufactured by Shin-Etsu Chemical Co., Ltd.).

As a radical polymerization initiator, dilauroyl peroxide (peroxide A1, trade name: parloyl L, manufactured by Nichiyu Co., Ltd., 1-minute half-life temperature: 116.4 ° C.), t-butylperoxypivalate (peroxide). Product A2, trade name: Perbutyl PV, manufactured by Nichiyu Co., Ltd., 1-minute half-life temperature: 110.3 ° C), and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate) Peroxide B, trade name: Perocta O, manufactured by Nichiyu Co., Ltd., 1 minute half-life temperature: 124.3 ° C.) was used.

10 g of silica particles (trade name: R104, manufactured by Nippon Aerosil Co., Ltd.), which are inorganic particles, are dispersed in a mixed solvent of 45 g of toluene and 45 g of ethyl acetate to prepare a 10% by mass dispersion, which is then added to the coating solution. Formulated.

(Making a connection)
Using the film-like adhesives shown in Tables 2 and 3, a flexible circuit board (FPC) having 2200 copper circuits having a line width of 75 μm, a pitch of 150 μm (space 75 μm), and a thickness of 18 μm, a glass substrate, and glass. _{A SiN x} substrate (thickness 0.7 mm) having a thin layer of _{silicon nitride (SiN x} ) having a thickness of 0.2 μm formed on the substrate was connected. The connection was made by heating and pressurizing at 130 ° C. and 3 MPa for 5 seconds or 170 ° C. and 3 MPa for 5 seconds using a thermocompression bonding device (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.). _{As a result, a connector was produced in which the FPC and the SiN x} substrate were connected by a cured product of a film-like adhesive over a width of 1.5 mm. The pressure of pressurization was calculated assuming that the crimping area was 0.495 cm ^2.

(Peeling evaluation)
Using an optical microscope, the connection appearance immediately after the production of the connection body and the connection appearance after the connection body was left in a constant temperature and humidity chamber at 85 ° C. and 85% RH for 250 hours (after a high temperature and high humidity test) were used. I observed it. The area where peeling occurred (peeling area) at the interface between the _{SiN x} substrate and the cured product in the space portion was measured, and the presence or absence of peeling was evaluated. When the ratio of the peeled area to the entire space exceeded 30%, it was evaluated as "B" (with peeling), and when the ratio of the peeled area was 30% or less, it was evaluated as "A" (without peeling). The evaluation results are shown in Tables 2 and 3. Regarding the appearance of the connection immediately after the production of the connection body, there was no peeling in all the examples and comparative examples.

(Evaluation of storage stability (pot life characteristics))
The film-like adhesive was treated in a constant temperature bath at 40 ° C. for one day. Using this film-like adhesive, a high-temperature and high-humidity test was performed after preparing a connector by the same method as described above. The evaluation results are shown in Tables 2 and 3.

From Tables 2 and 3, it was confirmed that the film-like adhesives of Examples can be connected at low temperature for a short time (particularly, connection at 130 ° C. for 5 seconds) as compared with Comparative Examples. Further, the film-like adhesive of the example can maintain good adhesion to the surface of the substrate (inorganic substrate) even after high-temperature and high-humidity treatment as compared with the comparative example, and is excellent in storage stability. Was confirmed.

10 ... Circuit connection member, 10a ... Insulating material, 10b ... Conductive particles, 20 ... First circuit member, 21 ... First substrate, 21a ... Main surface, 22 ... First circuit electrode, 30 ... Second Circuit member, 31 ... second substrate, 31a ... main surface, 32 ... second circuit electrode, 100a, 100b ... circuit connection structure.

Claims (7)

A first silane compound having a radically polymerizable functional group and
A second silane compound that reacts with the first silane compound,
Radical-polymerizable compounds (excluding compounds corresponding to the first silane compound) and
Containing a peroxide having a half-life temperature of 120 ° C. or less for 1 minute ,
The content of the first silane compound, Ru der least 0.5% by weight based on the total weight of the adhesive component of the adhesive composition, the adhesive composition for circuit connection. Contains more filler,
The adhesive composition according to claim 1, wherein the content of the filler is 0.1 to 60 parts by mass with respect to 100 parts by mass of the adhesive component of the adhesive composition. The adhesive composition according to claim 1 or 2 , wherein the functional group of the first silane compound contains at least one selected from the group consisting of a (meth) acryloyl group and a vinyl group. The adhesive composition according to any one of claims 1 to 3, wherein the second silane compound has an epoxy group. The adhesive composition according to any one of claims 1 to 4 , further containing conductive particles. A structure comprising the adhesive composition according to any one of claims 1 to 5 or a cured product thereof. A first circuit member having a first circuit electrode and
A second circuit member having a second circuit electrode and
A circuit connecting member arranged between the first circuit member and the second circuit member is provided.
The first circuit electrode and the second circuit electrode are electrically connected to each other.
A structure in which the circuit connecting member contains the adhesive composition according to any one of claims 1 to 5 or a cured product thereof.

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