CN111995975B - Adhesive compositions and structures - Google Patents

Abstract

The invention provides an adhesive composition and a structure. An adhesive composition contains a silane compound having a structure represented by the following general formula (I). (wherein X represents an organic group, R ¹ And R ² Each independently represents an alkyl group, m represents an integer of 0 to 2, and s represents an integer of 6 or more. ) X-C _s H _2s ‑Si〔R ¹ 〕 _m 〔OR ² 〕 _3‑m …(I)。

Description

Adhesive compositions and structures

The present invention is a divisional application of the invention application with the application number 2016800633868, the application date is November 4, 2016, and the invention title is "adhesive composition and structure".

technical field

The present invention relates to adhesive compositions and structures.

Background technique

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

In addition, in recent years, with the high integration of semiconductor elements and the high-definition of liquid crystal display elements, the pitch between elements and wiring has been narrowed, and there is a concern that peripheral components may be adversely affected by heat during curing. Furthermore, in order to reduce the cost, it is necessary to increase the throughput, and low temperature (90 to 170° C.) and short time (within 1 hour, preferably within 10 seconds, more preferably within 5 seconds) bonding are required, in other words, low temperature is required. Short curing time (low temperature fast curing) bonding. 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 both storage stability near normal temperature.

盐的阳离子固化系粘接剂等。自由基固化系由于作为反应活性种的自由基非常富有反应性，因此可短时间固化，并且，在小于或等于自由基聚合引发剂的分解温度时，过氧化物稳定地存在，因此其是兼顾了低温短时间固化与储存稳定性(例如常温附近的储存稳定性)的固化系。阳离子固化系由于作为反应活性种的

盐富有反应性，因此可短时间固化，并且，在小于或等于

盐的分解温度时，阳离子种稳定地存在，因此其是兼顾了低温短时间固化与储存稳定性的固化系。Therefore, in recent years, attention has been paid to radical curing adhesives using (meth)acrylate derivatives and peroxides as radical polymerization initiators in combination, epoxy resins and cationic polymerization initiators in combination.

Salt cation-curable adhesives, etc. The free radical curing system can be cured in a short time because the free radical as a reactive species is very reactive, and when it is less than or equal to the decomposition temperature of the free radical polymerization initiator, the peroxide exists stably, so it is a combination of It is a curing system that achieves short-term curing at low temperature and storage stability (such as storage stability near room temperature). The cationic curing system is due to the reactive species

Salt is reactive and therefore cures for a short time and, at less than or equal to

At the decomposition temperature of salt, cationic species exist stably, so it is a curing system that takes into account both low-temperature short-time curing and storage stability.

On the other hand, in the above-mentioned adhesives, in order to achieve strong adhesion with the adherend, there are coupling agents or the like used as the covalent bond, hydrogen bond, van der Waals force due to hydrophobic interaction, etc. The case of low molecular weight additives capable of interacting with the adherend surface. As the coupling agent, for example, a silane coupling agent; a compound containing a phosphoric acid group, a carboxyl group, etc., etc. can be used. Especially when using organic functional groups incorporated into the resin matrix after curing (such as organic functional groups represented by epoxy groups, acryloyl groups, vinyl groups, etc.), and alkoxysilanes or alkoxysilanes that interact with the surface of the adherend In the case of a coupling agent (for example, a coupling agent having a functional group typified by a phosphoric acid group), the adherend and the adhesive can be bonded more firmly (for example, refer to the following Patent Document 1).

prior art literature

patent documents

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

Patent Document 2: International Publication No. 2009/063827

Contents of the invention

The problem to be solved by the invention

In addition, an adhesive composition containing a silane compound is required to have excellent adhesive strength after a reliability test maintained under high-temperature and high-humidity conditions such as 85° C. 85% RH and 60° C. 95% RH.

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

means of solving problems

The adhesive composition of the present invention contains a silane compound having a structure represented by the following general formula (I).

[chemical 1]

XC _s H _2s -Si〔R ¹ 〕 _m 〔OR ² 〕 _3-m …(I)

(In the formula, X represents an organic group, R1 and R2 independently represent ^an alkyl group, m represents an integer from 0 to ² , and s represents an integer greater than or equal to 6.)

In addition, conventionally, there have been cases where an adhesive containing a silane compound having an alkoxysilyl group and an organic group bonded to the alkoxysilyl group via an alkylene group has been used. In this regard, the present inventors have found the following knowledge about such silane compounds. That is, in conventional silane compounds, the number of carbon atoms in the alkylene group existing between Si and the organic group of the alkoxysilyl group is small (for example, the number of methylene groups (CH ₂ ) is as short as 3 or less). Therefore, when the first functional group of one of the alkoxysilyl group and the organic group reacts with one of the constituent components (resin, etc.) of the adhesive and the adherend, the alkoxysilyl group and the organic group react with each other. It is difficult to separate the radicals sufficiently, so the degree of steric freedom of the second functional group of the other of the alkoxysilyl group and the organic group is low, so the second functional group and the constituent components of the adhesive (resin, etc.) and the adherend The reaction of the other one cannot proceed sufficiently, and the effect as a silane compound cannot be fully exhibited. As a result, sufficient adhesive strength cannot be obtained, and there are problems such as that the adhesive strength decreases after being left in a reliability test under high-temperature and high-humidity conditions such as 85° C. 85% RH and 60° C. 95% RH.

On the other hand, the adhesive composition of the present invention has excellent adhesive strength after the reliability test. In addition, the adhesive composition of the present invention is effective for adherends made of various materials (for example, inorganic substances (oxides, metals, etc.), organic substances, and their composites) before and after the reliability test. Excellent bond strength.

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

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

The adhesive composition of the present invention may further contain a radical polymerizable compound and a curing agent that generates radicals by heat or light.

The adhesive composition of this invention may contain electroconductive particle further.

The adhesive composition of this invention can be used for circuit connection (adhesive composition for circuit connections).

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

The structure of the present invention may also be in an aspect including: a first circuit member having a first circuit electrode; a second circuit member having a second circuit electrode; A 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 a cured product thereof.

The effect of the invention

According to the present invention, it is possible to provide an adhesive composition having excellent adhesive strength after a reliability test and a structure using the same. Also, according to the present invention, it is possible to provide an adhesive composition having excellent adhesive strength with respect to adherends made of various materials before and after a reliability test, and a structure using the same.

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

Description of drawings

FIG. 1 is a schematic cross-sectional view showing one 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.

Detailed ways

Hereinafter, although embodiment of this invention is described, this invention is not limited to these embodiment at all.

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)acryloyl" and "(meth)acryl". 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, unless otherwise specified, when a plurality of substances corresponding to each component exist in the composition. The numerical range represented by "-" shows the range which includes the numerical value described before and after "-" as a minimum value and a maximum value, respectively. The term "A or B" may include either one of A and B, or both. The term "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.

The adhesive composition of the present embodiment contains a silane compound (hereinafter referred to as "silane compound A" as the case may be) having a structure represented by the following general formula (I). According to the adhesive composition of this embodiment, the alkoxysilyl group and the organic group X are easily separated by substituting the conventional alkylene group having a small carbon number with an alkylene group having 6 or more carbon atoms. After the alkoxysilyl group reacts with one of the functional groups in the organic group X, the steric freedom of the other functional group can also be ensured, so it shows high adhesive strength to various adherends and has been tested in the reliability test. Also has sufficient adhesive strength. Such an adhesive composition can be suitably used as an adhesive composition for circuit connection.

[Chem 2]

XC _s H _2s -Si〔R ¹ 〕 _m 〔OR ² 〕 _3-m …(I)

(In the formula, X represents an organic group, R ¹ and R ² independently represent an alkyl group, m represents an integer of 0 to 2, and s represents an integer greater than or equal to 6. When there are multiple R ^1s , each R ¹ may be the same as or different from each other. When there are multiple R ^2s , each R ² may be the same or different from each other. Each of R ¹ , R ² and C _s H _2s may be branched.)

The alkylene group of the silane compound A may be any of a linear alkylene group and a branched chain alkylene group. When the number of carbon atoms between the alkoxysilyl group and the organic group X in the straight-chain alkylene group and the branched-chain alkylene group is the same, the straight-chain alkylene group is preferable from the viewpoint of easier securing the degree of steric freedom. base. In the case of using a silane compound A having a linear alkylene group, the number of short methylene groups is 6 or more, so that even after the reaction between the alkoxysilyl group and one of the functional groups in the organic group X, Since the steric freedom of the other functional group can also be ensured, it exhibits high adhesive strength to various adherends and has sufficient adhesive strength even after a reliability test.

Examples of the constituents of the adhesive composition of the present embodiment include: (a) epoxy resin (hereinafter referred to as “(a) component)” as the case may be, (b) latent curing agent (epoxy resin Latent curing agent. Hereinafter referred to as "(b) component)" depending on the situation), (c) radical polymerizable compound (hereinafter referred to as "(c) component" depending on the situation), and (d) by heat (heating ) or light (light irradiation) to generate radicals (free radicals) (hereinafter referred to as "(d) component" depending on the case). The first aspect of the adhesive composition of this embodiment contains (a) component and (b) component. The second aspect of the adhesive composition of this embodiment contains (c) component and (d) component. The third aspect of the adhesive composition of this embodiment contains (a) component, (b) component, (c) component, and (d) component.

Each component is demonstrated below.

(silane compound)

As the organic group X of the silane compound A having a structure represented by the formula (I), a group containing an ethylenically unsaturated bond (group containing an ethylenically unsaturated bond), a nitrogen atom-containing group (containing nitrogen atom group), sulfur atom-containing group (group containing sulfur atom), epoxy group and the like. As a group containing an ethylenically unsaturated bond, a (meth)acryloyl 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 (methylamino groups, etc.), benzylamino groups, phenylamino groups, cycloalkylamino groups (cyclohexylamino groups, etc.), and the like. As a disubstituted amino group, an acyclic disubstituted amino group, a cyclic disubstituted amino group, etc. are mentioned. As an acyclic disubstituted amino group, a dialkylamino group (dimethylamino group etc.) etc. are mentioned. As a cyclic disubstituted amino group, a morpholinyl group, a piperazinyl group, etc. are mentioned. As a sulfur atom-containing group, a mercapto group etc. are mentioned. An epoxy group may also be included in epoxy group-containing groups (groups containing epoxy groups), such as glycidyl and glycidyloxy groups. A (meth)acryloyl group may also be contained in a (meth)acryloyloxy group.

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

^The carbon number of the alkyl group of R1 and R2 is ^1-20 , for example. Specific examples of the above-mentioned alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, Trialkyl, 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. When the alkoxysilyl moiety reacts with the adherend, it is difficult to become a steric hindrance, and from the viewpoint of further improving the adhesiveness with the adherend, the carbon number of the alkyl group of R is preferably ¹ to 10, more preferably Preferably it is 1-5. The number of carbon atoms in the alkyl group of R ² is preferably 1-10, more preferably 1-5, from the viewpoint of further improving the adhesiveness to the adherend.

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

Examples of the silane compound A include glycidyloxyalkyltrialkoxysilane, glycidyloxyalkyldialkoxysilane, (meth)acryloyloxyalkyltrialkoxysilane, (methyl) ) acryloxydialkyldialkoxysilane, alkenyltrialkoxysilane, styrylalkyltrialkoxysilane, N-2-(aminoethyl)-8-aminooctylmethyl Dimethoxysilane, N-2-(aminoethyl)-8-aminooctyltrimethoxysilane, 3-aminooctyltrimethoxysilane, 3-aminooctyltriethoxysilane, 3-tri Ethoxysilyl-N-(l,3-dimethylbutylene)octylamine, N-phenyl-8-aminooctyltrimethoxysilane, 8-ureidooctyltriethoxysilane , 8-mercaptooctylmethyldimethoxysilane, 8-mercaptooctyltrimethoxysilane, 8-isocyanatooctyltrimethoxysilane, 8-isocyanatooctyltriethoxysilane, etc.

Examples of the glycidoxyalkyltrialkoxysilane include 8-glycidyloxyoctyltrimethoxysilane and 8-glycidoxyoctyltriethoxysilane. Examples of the glycidoxyalkyldialkoxysilane include 8-glycidoxyoctylmethyldimethoxysilane, 8-glycidoxyoctylmethyldiethoxysilane, and the like. Examples of (meth)acryloyloxyalkyltrimethoxysilane include 8-(meth)acryloyloxyoctyltrimethoxysilane, 8-(meth)acryloyloxyoctyltriethoxy base silane, etc. Examples of (meth)acryloyloxydialkyldialkoxysilanes include 8-(meth)acryloyloxyoctylmethyldimethoxysilane, 8-(meth)acryloyloxy Octylmethyldiethoxysilane, etc. As alkenyltrialkoxysilane, octenyltrialkoxysilane, octenylalkyldialkoxysilane, etc. are mentioned. As octenyltrialkoxysilane, 7-octenyltrimethoxysilane, 7-octenyltriethoxysilane, etc. are mentioned. As octenylalkyldialkoxysilane, 7-octenylmethyldimethoxysilane, 7-octenylmethyldiethoxysilane, etc. are mentioned. As styrylalkyltrialkoxysilane, p-styryloctyltrimethoxysilane etc. are mentioned.

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

From the point of view that there is a tendency for the adhesive force at the interface between the adherend (circuit member, etc.) and the adhesive composition or its cured product (circuit connection member, etc.) to become stronger, the content of the silane compound A is determined by the adhesive The following ranges are preferable based on the total mass of the adhesive component in the adhesive composition (solid content other than the conductive particles in the adhesive composition. The same applies hereinafter). The content of the silane compound A is preferably 0.1% by mass or more, more preferably 0.25% by mass or more, and still more preferably 0.5% by mass or more. The content of the silane compound A is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less. From these viewpoints, the content of the silane compound A is preferably 0.1 to 20% by mass, more preferably 0.25 to 10% by mass, and still more preferably 0.5 to 5% by mass.

((a) component: epoxy resin)

Examples of the component (a) include bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, naphthalene epoxy resins, phenol novolac epoxy resins, and cresol novolac epoxy resins. Varnish type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, Hydantoin type epoxy resin, isocyanurate type epoxy resin, aliphatic chain epoxy resin, etc. The (a) component may be either halogenated or hydrogenated. (a) The component may be used individually by 1 type, and may use it in combination of 2 or more types.

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

((b) component: latent curing agent)

As (b) component, if it can harden an epoxy resin, it will not specifically limit. As (b) component, a curing agent capable of generating anionic species by heat or light (anionic polymerizable catalyst type curing agent, etc.), a curing agent capable of generating cationic species by heat or light (cationic polymerizable catalyst type curing agent, etc.) Type curing agent, etc.), polyaddition type curing agent, etc. (b) The component may be used individually by 1 type, and may use it in combination of 2 or more types. The component (b) is preferably a curing agent capable of generating anionic species or cationic species by heat or light, more preferably an anionically polymerizable or cationicly polymerizable catalyst type, from the viewpoint of excellent fast curing properties and no need to consider chemical equivalents. Hardener.

盐、锍盐等，也可使用它们的改性物。作为加聚型固化剂，可列举多胺类、聚硫醇类、多酚类、酸酐等。Examples of anionically polymerizable catalyst-type curing agents include imidazole-based curing agents, hydrazide-based curing agents, boron trifluoride-amine complexes, amine imides, tertiary amines, diaminomaleonitrile, melamine and Its derivatives, salts of polyamines, dicyandiamide, etc., and their modified products can also be used. Examples of cationic polymerizable catalyst-type curing agents include diazo

Salt, sulfonium salt, etc., and their modified products can also be used. Examples of the polyaddition curing agent include polyamines, polythiols, polyphenols, acid anhydrides, and the like.

When using tertiary amines, imidazole-based curing agents, etc. as anionically polymerizable catalyst-type curing agents, the epoxy resin can be cured by heating at a medium temperature of about 160 to 200°C for tens of seconds to several hours . Therefore, the service life (use period) can be made long.

盐(芳香族重氮

盐、芳香族锍盐等)。另外，作为除照射能量射线以外通过热进行活性化而使环氧树脂固化的固化剂，可列举脂肪族锍盐等。这样的固化剂因具有快速固化性而优选。As the cationic polymerizable catalyst-type curing agent, for example, a photosensitive resin capable of curing epoxy resin by irradiation with energy rays is preferable.

Salt (aromatic diazonium

salts, aromatic sulfonium salts, etc.). Moreover, aliphatic sulfonium salt etc. are mentioned as a hardening|curing agent which activates by heat other than irradiation of an energy ray, and hardens an epoxy resin. Such a curing agent is preferable because it has rapid curing properties.

A curing agent that coats and microencapsulates component (b) with a polymer material (polyurethane-based, polyester-based, etc.), metal (nickel, copper, etc.) thin film, inorganic material (calcium silicate, etc.) enables extended use life, so preferred.

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

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

((c) component: radical polymerizable compound)

(c) A component is a compound which has a radically polymerizable functional group. As (c) component, a (meth)acrylate compound, a maleimide compound, a citraconimide resin, a nadic imide resin, etc. are mentioned. The term "(meth)acrylate compound" means a compound having a (meth)acryloyl group. (c) The component may be used in the form of a monomer or an oligomer, and a monomer and an oligomer may be used together. (c) A component 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)acryloyloxypropane, 2,2-bis[4-((meth)acryloyloxymethoxy)phenyl]propane, 2,2-bis[4- ((meth)acryloyloxypolyethoxy)phenyl]propane, dicyclopentenyl (meth)acrylate, tricyclodecanyl (meth)acrylate, tris((methyl)isocyanurate Acryloyloxyethyl) ester, EO modified di(meth)acrylate, urethane (meth)acrylate, etc. As a radically polymerizable compound other than a (meth)acrylate compound, the compound described in patent document 2 (International Publication No. 2009/063827) can be used suitably, for example. The (meth)acrylate compounds may be used alone or in combination of two or more.

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

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

[Chem 3]

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

The radically polymerizable compound which has the said phosphate ester structure can be obtained by making phosphoric anhydride and 2-hydroxyethyl (meth)acrylate react, for example. Specific examples of the above-mentioned radically polymerizable compound having a phosphate ester structure include mono(2-(meth)acryloyloxyethyl)acid phosphate, bis(2-(meth)acryloyloxyethyl) Ethyl) acid phosphate, 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 further improving the adhesiveness to the adherend, the content of the radically polymerizable compound having a phosphate ester structure represented by the formula (II) relative to the radically polymerizable compound (equivalent to the radically polymerizable compound The total amount of the components) is preferably 0.1 to 1000 parts by mass, more preferably 1 to 100 parts by mass, per 100 parts by mass. From the viewpoint of further improving the adhesiveness to the adherend, the content of the radically polymerizable compound having a phosphate ester structure represented by formula (II) relative to the radically polymerizable compound and the film-forming material (if necessary) The total of 100 parts by mass of components used) is preferably 0.01 to 50 parts by mass, more preferably 0.5 to 10 parts by mass.

The above-mentioned radically polymerizable compound may contain allyl (meth)acrylate. In this case, the content of allyl (meth)acrylate is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass.

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

((d) component: curing agent that generates radicals by heat or light)

As the (d) component, (d1) a curing agent that generates free radicals by heat (hereinafter referred to as "(d1) component") or (d2) a curing agent that generates free radicals by light ( Hereinafter, it is referred to as "(d2) component" depending on the case). The component (d1) is a curing agent that is decomposed by heat to generate free radicals. As (d1) component, a peroxide (organic peroxide etc.), an azo compound, etc. are mentioned. From the standpoint of high reactivity and improved service life, the component (d1) is preferably an organic peroxide having a 10-hour half-life temperature of 40° C. or higher and a 1-minute half-life temperature of 180° C. or lower, more preferably a 10-hour half-life temperature of 180° C. or higher. Organic peroxides equal to 60°C and having a half-life temperature of 1 minute less than or equal to 170°C.

Specific examples of the component (d1) include diacyl peroxides (benzoyl peroxide, etc.), peroxydicarbonates, peroxyesters, peroxyketals, dialkyl peroxides, hydroperoxides, Silyl peroxide, etc.

As the component (d1), from the viewpoint of inhibiting corrosion of electrodes (circuit electrodes, etc.), a curing agent containing chloride ions and organic acids at a concentration of 5000 ppm or less is preferable, and it is more preferable to generate less organic acids after thermal decomposition. curing agent. Specific examples of such a component (d1) include peroxyesters, dialkyl peroxides, hydroperoxides, and silyl peroxides. From the viewpoint of obtaining high reactivity, peroxyesters are more preferred. .

Examples of peroxyesters include cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl-1- Methyl ethyl ester, tert-hexyl peroxyneodecanoate, tert-butyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy 2-ethylhexanoate, 2,5- Dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 2-ethylhexanoic acid-1-cyclohexyl-1-methylethyl peroxide, 2-ethylhexyl peroxide tert-hexyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisobutyrate, 1,1-bis(tert-butylperoxy)cyclohexane, tert-butyl peroxyisopropyl monocarbonate Hexyl peroxide, tert-butyl 3,5,5-trimethylhexanoate, tert-butyl peroxylaurate, 2,5-dimethyl-2,5-di(m-methylbenzoyl peroxide ) hexane, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxy 2-ethylhexyl monocarbonate, tert-hexyl peroxybenzoate, tert-butyl peroxyacetate, etc. As (d1) component other than the said peroxyester, the compound described in patent document 2 (International publication 2009/063827) can be used suitably, for example. One type of peroxyester may be used alone, or two or more types may be used in combination.

The component (d2) is a curing agent that is decomposed by light to generate free radicals. As the component (d2), a compound that generates free radicals upon irradiation with light having a wavelength of 150 to 750 nm can be used. As such a compound, for example, from the viewpoint of high sensitivity to light irradiation, it is preferable to use it in photoinitiation, photopolymerization, and photocuring (Photoinitiation, Photopolymerization, and Photocuring), J.-P.Fouassier, Hanser Publishers (1995), p17 α-Acetaminophenone derivatives and phosphine oxide derivatives described in ~p35. (d2) The component may be used individually by 1 type, and may use it in combination of 2 or more types. (d2) component and (d1) component (the said peroxide, an azo compound, etc.) can also be used in combination. The component (d1) or the component (d2) can also be used in combination with a curing agent that generates free radicals by ultrasonic waves, electromagnetic waves, or the like.

(d) The components can be appropriately selected according to the target connection temperature, connection time, service life, and the like. (d) The component may be used individually by 1 type, and may use it in combination of 2 or more types. The component (d) can also be used in combination with a decomposition accelerator, a decomposition inhibitor, and the like. In addition, the component (d) may be coated with a polyurethane-based or polyester-based polymer substance and microencapsulated. Microencapsulated curing agents are preferred for their extended lifetime.

When the connection time is 25 seconds or less, the content of the component (d) is preferably in the following range from the viewpoint of easily obtaining a sufficient reaction rate. The content of (d) component is preferably at least 0.1 mass part with respect to 100 mass parts of (c) component, more preferably at least 1 mass part. The content of (d) component is preferably 40 parts by mass or less with respect to 100 parts by mass of component (c), more preferably 20 parts by mass or less. From these viewpoints, the content of (d) component is preferably 0.1 to 40 parts by mass with respect to 100 parts by mass of component (c), more preferably 1 to 20 parts by mass.

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

From the viewpoint of easily obtaining a sufficient reaction rate, the content of the component (d) is preferably in the following range when the connection time is not limited. The content of the component (d) is preferably at least 0.01 parts by mass with respect to 100 parts by mass of the component (c), more preferably at least 0.1 parts by mass. The content of (d) component is preferably 30 parts by mass or less with respect to 100 parts by mass of component (c), more preferably 15 parts by mass or less. From these viewpoints, the content of the component (d) is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 15 parts by mass, relative to 100 parts by mass of the component (c).

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

(film forming material)

The adhesive composition of this embodiment may contain a film forming material as needed. When the liquid adhesive composition is solidified into a film, the film-forming material can improve the handleability of the film under normal conditions (at normal temperature and pressure), and can impart a film that is hard to crack, hard to break, and hard to stick. and other characteristics. Examples of the film forming material include phenoxy resin, polyvinyl formal, polystyrene, polyvinyl butyral, polyester, polyamide, xylene resin, polyurethane and the like. Among these, phenoxy resins are 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 resins obtained by polyaddition of bifunctional epoxy resins and bifunctional phenols, and resins obtained by reacting bifunctional phenols with epihalohydrin until polymerized. Phenoxy resins can be obtained, for example, by reacting 1 mole of bifunctional phenols with 0.985 to 1.015 moles of epihalohydrin in a non-reactive solvent in the presence of a catalyst such as an alkali metal hydroxide at a temperature of 40 to 120°C. . As the phenoxy resin, from the viewpoint of excellent mechanical properties and thermal properties of the resin, it is particularly preferable to set the compounding equivalent ratio of the bifunctional epoxy resin to the bifunctional phenol to be epoxy group/phenolic hydroxyl group=1/0.9～ 1/1.1, in the presence of catalysts such as alkali metal compounds, organophosphorus compounds, and cyclic amine compounds, organic solvents (amides, ethers, ketones, lactones, alcohols, etc.) with a boiling point greater than or equal to 120°C system, etc.), the resin obtained by heating to 50-200° C. under the condition that the reaction solid content is less than or equal to 50% by mass to carry out polyaddition reaction. The phenoxy resins may be used alone or in combination of two or more.

Bifunctional epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, biphenyl diglycidyl ether, methyl Substitute biphenyl diglycidyl ether, etc. Bifunctional phenols are compounds having two phenolic hydroxyl groups. Bifunctional phenols include hydroquinones, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, bisphenol fluorene (4,4'-(9-fluorenylene)diphenol, etc.) , methyl-substituted bisphenol fluorene, dihydroxybiphenyl, methyl-substituted dihydroxybiphenyl and other bisphenols, etc. Phenoxy resins can also be modified with free radical polymerizable functional groups, or other reactive compounds (such as epoxy modification).

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

(conductive particles)

The adhesive composition of the present embodiment may further contain conductive particles. Metals, such as gold (Au), silver (Ag), nickel (Ni), copper (Cu), solder, carbon, etc. are mentioned as a constituent material of an electroconductive particle. Moreover, the coated conductive particle which uses nonconductive resin, glass, ceramics, plastics, etc. as a core and coat|covers the said metal (metal particle etc.) or carbon on this core may be used. Coated conductive particles or hot-melt metal particles have the property of being deformed by heat and pressure, so that the height variation of circuit electrodes can be eliminated during connection, and the contact area with electrodes can be increased during connection, so reliability is improved, so it is preferable.

From the viewpoint of being excellent in dispersibility and conductivity, the average particle diameter of the conductive particles is preferably 1 to 30 μm. The average particle diameter of an electrically-conductive particle can be measured, for example using equipment analysis, such as a laser diffraction method. From the viewpoint of excellent conductivity, the content of the conductive particles is preferably at least 0.1 part by mass, more preferably at least 1 part by mass, based on 100 parts by mass of the adhesive component of the adhesive composition. From the viewpoint of easily suppressing short-circuiting of electrodes (circuit electrodes, etc.), the content of conductive particles is preferably 100 parts by mass or less, more preferably 100 parts by mass or less, with respect to 100 parts by mass of the adhesive component of the adhesive composition. 50 parts by mass.

(other ingredients)

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

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

The adhesive composition of this embodiment may contain the coated fine particle which coated the surface of the said electroconductive particle with a polymer resin etc. FIG. When such coated fine particles are used in combination with the above-mentioned conductive particles, even if the content of the conductive particles increases, it is easy to suppress the short circuit caused by the contact of the conductive particles, so that the insulation between adjacent circuit electrodes can be improved. sexual enhancement. The above-mentioned coated fine particles may be used alone without using conductive particles, or may be used in combination with coated fine particles and conductive particles.

The adhesive composition of this embodiment may also contain rubber particles, fillers, softeners, accelerators, anti-aging agents, colorants, flame retardants, thixotropic agents, coupling agents, phenolic resins, melamine resins, isocyanates, etc. The adhesive composition of the present embodiment may suitably contain additives such as an adhesion improving agent (excluding a coupling agent), a thickener, a leveling agent, a colorant, and a weather resistance improving agent.

The rubber particles preferably have an average particle diameter less than or equal to twice the average particle diameter of the conductive particles, and have a storage modulus at room temperature less than or equal to the storage modulus of the conductive particles and the adhesive composition at room temperature. 1/2 of the particles. Especially when the material of the rubber particles is silicone, acrylic latex, SBR, NBR, or polybutadiene rubber, the rubber particles are preferably used alone or in combination of two or more. The three-dimensionally crosslinked rubber microparticles have excellent solvent resistance and are easily dispersed in the adhesive composition.

The filler can improve electrical characteristics (connection reliability, etc.) between circuit electrodes. As the filler, for example, particles having an average particle diameter equal to or less than 1/2 of the average particle diameter of the conductive particles can be suitably used. When using non-conductive particles together with a filler, particles equal to or smaller than the average particle diameter of the non-conductive particles can be used as the filler. The content of the filler is preferably 5 to 60 parts by mass relative 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 the said content being less than or equal to 60 mass parts. There exists a tendency for the addition effect of a filler to be fully acquired by the said content being 5 mass parts or more.

The adhesive composition of the present embodiment can be used in a paste form when it is liquid at normal temperature. When it is solid at normal temperature, it can also gelatinize using a solvent other than heating and using. Usable solvents are not particularly limited as long as they have no reactivity with the adhesive composition and additives and exhibit sufficient solubility, but solvents with a boiling point of 50 to 150°C under normal pressure are preferred. If the boiling point is 50° C. or higher, the solvent is less volatile at normal temperature, so even an open system can be used. If 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 be in the form of a film. A solution obtained by adding a solvent or the like to the adhesive composition as needed can be applied to a fluororesin film, a polyethylene terephthalate film, or a release substrate (release paper, etc.), Then the solvent and the like are removed to obtain a film. In addition, a film can also be obtained by impregnating a base material such as a nonwoven fabric with the above-mentioned solution and mounting it on a peelable base material, and then removing the solvent or the like. If it is used in a film form, it is more convenient from the viewpoint of being excellent in workability and the like.

The adhesive composition of the present embodiment can be bonded by applying pressure while heating or irradiating with light. By using heating and light irradiation in combination, bonding can be performed at a low temperature and in a short time. Light irradiation preferably irradiates light in a wavelength region of 150 to 750 nm. Low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps (ultra-high pressure mercury lamps, etc.), xenon lamps, metal halide lamps, etc. can be used for curing at an irradiation dose of 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 is within a range that does not damage the adherend, but is preferably 0.1 to 10 MPa. Heating and pressurization are preferably performed within a range of 0.5 seconds to 3 hours.

The adhesive composition of the present embodiment can be used as an adhesive for different types of adherends having different coefficients of thermal expansion. Specifically, it can be used as a circuit connection material represented by anisotropic conductive adhesive, silver paste, silver film, etc.; semiconductor element bonding represented by CSP elastomer, CSP underfill material, LOC tape, etc. materials etc. The adhesive composition of the present embodiment has excellent performance for adherends made of various materials (such as inorganic substances (oxides, metals, etc.), organic substances, and their composites) before and after the reliability test. of bond strength.

<Structure and its manufacturing method>

The structured body of the present embodiment includes the adhesive composition of the present embodiment or a cured product thereof. The structure of the present embodiment is, for example, a semiconductor device such as a circuit-connected structure. As one form 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 member has, for example, a first substrate and first circuit electrodes arranged on the first substrate. The second circuit member has, for example, a second substrate and second circuit electrodes arranged 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 hardened|cured material. The structure according to this embodiment only needs to include the adhesive composition according to this embodiment or its cured product, and instead of the circuit member of the above-mentioned circuit-connected structure, a member (substrate, etc.) that does not have a circuit electrode may be used. .

The manufacturing method of the structure of this embodiment is equipped with the process of hardening the adhesive composition of this embodiment. As one form of the method for manufacturing the structure of the present embodiment, the method for manufacturing the circuit-connected structure includes an arrangement step of disposing between a first circuit member having a first circuit electrode and a second circuit member having a second circuit electrode. Arranging the adhesive composition of this embodiment; and a 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 combining the adhesive The substance is heated to make it solidify. In the arranging step, the first circuit electrodes and the second circuit electrodes may be arranged so as to face each other. In the heating and pressing step, the first circuit member and the second circuit member may be pressed in the opposing direction.

Hereinafter, the circuit connection structure which is one form of this embodiment, and its manufacturing method are demonstrated using drawing. FIG. 1 is a schematic cross-sectional view showing one embodiment of a structure. The circuit connection structure 100a shown in FIG. The circuit connection member 10. The circuit connection member 10 contains the hardened|cured material of the adhesive composition of this embodiment.

The circuit member 20 includes a substrate (first substrate) 21 and circuit electrodes (first circuit electrodes) 22 arranged on the principal surface 21 a of the substrate 21 . An insulating layer (not shown) may be arranged on the main surface 21a of the substrate 21 as the case may be.

The circuit member 30 includes a substrate (second substrate) 31 and circuit electrodes (second circuit electrodes) 32 arranged on the principal surface 31 a of the substrate 31 . An insulating layer (not shown) may be arranged on the main surface 31 a of the substrate 31 as the case may be.

The circuit connection member 10 contains an insulating substance (cured product of components other than conductive particles) 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 members 20 and 30 have a single or a plurality of circuit electrodes (connection terminals). As the circuit members 20 and 30 , for example, members including electrodes requiring electrical connection can be used. As the circuit member, chip components such as semiconductor chips (IC chips), resistor chips, and capacitor chips; substrates such as printed boards and semiconductor mounting substrates, and the like can be used. As a combination of the circuit members 20 and 30, for example, a semiconductor chip and a substrate for mounting a semiconductor can be cited. Examples of substrate materials include inorganic substances such as semiconductors, glass, and ceramics; organic substances such as polyimide, polyethylene terephthalate, polycarbonate, (meth)acrylic resin, and cyclic olefin resin; Compounds of glass/epoxy, etc. The substrate may 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 electrode 22 and the circuit electrode 32 contact directly without interposing conductive particles, and are electrically connected.

The circuit connection structures 100a and 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 . 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 affixing the film-like adhesive composition to the circuit member 20 . Next, the circuit member 30 is placed on the resin layer arranged on the circuit member 20 so that the circuit electrode 22 and the circuit electrode 32 are arranged to face each other. Then, the adhesive composition is cured by heat-processing or light-irradiating the resin layer containing an adhesive composition, and hardened|cured material (circuit connection member 10) is obtained. From the above, the circuit-connected structural bodies 100a and 100b are obtained.

Example

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

<Preparation of film adhesive composition>

[Example 1]

A phenoxy resin is synthesized from a bisphenol A type epoxy resin and a phenol compound (4,4'-(9-fluorenylene)-diphenol) having a fluorene ring structure in the molecule. This phenoxy resin was dissolved in a mixed solution of toluene/ethyl acetate=50/50 (mass ratio) to prepare a solution having a solid content of 40% by mass. Next, prepare acrylic rubber (a copolymer of 40 parts by mass of butyl acrylate-30 parts by mass of ethyl acrylate-30 parts by mass of acrylonitrile-3 parts by mass of glycidyl methacrylate, with a weight average molecular weight of 800,000) as a rubber component. This acrylic rubber was dissolved in a mixed solution of toluene/ethyl acetate=50/50 (mass ratio) to prepare a solution having a solid content of 15% by mass. In addition, prepare a liquid curing agent containing a microcapsule-type latent curing agent (microencapsulated amine-based curing agent), bisphenol F-type epoxy resin, and naphthalene-type epoxy resin in a mass ratio of 34:49:17. epoxy resin (epoxy equivalent weight: 202). Separately, 8-glycidyloxyoctyltrimethoxysilane (product name: KBM4803, manufactured by Shin-Etsu Chemical Co., Ltd.) was prepared as a silane compound.

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

[Comparative example 1]

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

[Example 2]

50 g of phenoxy resin (product name: PKHC, manufactured by Union Carbide Co., Ltd., weight average molecular weight 45000) was dissolved in a mixed solution of toluene/ethyl acetate=50/50 (mass ratio) to prepare a solid content of 40% by mass. Phenoxy resin solution. As the radically polymerizable compound, EO-modified isocyanuric acid diacrylate (product name: M-215, manufactured by Toagosei Co., Ltd.), 2-(meth)acryloyloxyethyl phosphate (product name : P-2M, manufactured by Kyoeisha Chemical Co., Ltd.) and urethane acrylate (product name: U-2PPA, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). As a silane compound, 7-octenyltrimethoxysilane (product name: KBM1083, manufactured by Shin-Etsu Chemical Co., Ltd.) was prepared. Benzoyl peroxide (product name: NYPER-BMT-K40, manufactured by NOF Corporation) was prepared as a radical generator.

The mass ratio (solid Components) were blended with these materials at 50:19:3:20:3:5 to prepare varnish B1 (solution containing an adhesive composition). Furthermore, 5 mass parts of electroconductive particles A were mix|blended with respect to 100 mass parts of solid content of varnish B1, and varnish B2 (solution containing a circuit connection material) was prepared. On a polyethylene terephthalate (PET) film with a thickness of 50 μm that has been surface-treated on one side, apply the varnish B2 using a coating tool, and then dry it with hot air at 70°C for 3 minutes. A film-like adhesive composition with a thickness of 20 μm was formed on it.

[Comparative example 2]

Except for using vinyltrimethoxysilane (product name: KBM103, manufactured by Shin-Etsu Chemical Co., Ltd.) as the silane compound instead of 7-octenyltrimethoxysilane, a film-like adhesive was produced in the same manner as in Example 2. agent composition.

[Example 3]

Except for using 8-methacryloyloxyoctyltrimethoxysilane (product name: KBM5803, manufactured by Shin-Etsu Chemical Co., Ltd.) as the silane compound instead of 7-octenyltrimethoxysilane, it was the same as in Example 2. Operate accordingly to produce a film-like adhesive composition.

[Comparative example 3]

Except for using 3-methacryloxypropyltrimethoxysilane (product name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) as the silane compound instead of 7-octenyltrimethoxysilane, the same as in Example 2 Operate accordingly to produce a film-like adhesive composition.

<Evaluation of Adhesive Strength>

As a first circuit member, a flexible printed circuit (FPC) having 500 copper circuits having a line width of 75 μm, a pitch of 150 μm, and a thickness of 18 μm was prepared. As the second circuit member, glass (thickness: 0.7 mm) glass in which a silicon nitride (SiN _x ) thin layer was formed with a thickness of 0.5 μm was prepared. In the state where the film adhesive composition of Examples 1 to 3 or Comparative Examples 1 to 3 is interposed between the first circuit member and the second circuit member, a thermocompression bonding device (heating method: constant temperature type, Toray Engineering Co., Ltd.) was heated and pressurized at 170° C. and 3 MPa for 20 seconds to connect with a width of 2 mm to produce a circuit-connected structure (connected body).

For this circuit connection structure, the adhesive strength immediately after bonding (after heating and pressing at 170° C. and 3 MPa for 20 seconds) and the bonding strength at 85° C. and 85% RH were measured by the 90-degree peeling method in accordance with JIS Z0237. Adhesive strength after being placed in a constant temperature and humidity chamber for 100 hours. Here, Tensilon UTM-4 (peeling speed 50 mm/min, 25 degreeC) manufactured by Toyo Baldwin Co., Ltd. was used as the measuring apparatus of adhesive strength.

Table 1 shows the results of the measurement performed as described above.

[Table 1]

From the above, it was confirmed that each of Examples 1 to 3 has higher adhesive strength immediately after bonding than Comparative Examples 1 to 3, and also can maintain the substrate well after the reliability test (high temperature and high humidity treatment). (inorganic substrate) surface adhesion.

Symbol Description

10: circuit connection member; 10a: insulating substance; 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 (10)

1. An adhesive composition which comprises a silane compound having a structure represented by the following general formula (I), at least one of the following (A) and (B), and a film-forming material, and which is in the form of a film,

(A) Epoxy resins and latent curing agents;

(B) A radically polymerizable compound and a curing agent that generates radicals by heat or light,

when the epoxy resin is contained, the content of the epoxy resin is not less than 15% by mass based on the total mass of the adhesive components of the adhesive composition,

when the epoxy resin is contained, the adhesive composition contains an acrylic rubber which is a copolymer obtained by polymerizing glycidyl (meth) acrylate having a glycidyl ether group,

when the radical polymerizable compound is contained, the content of the radical polymerizable compound is 20% by mass or more based on the total mass of the adhesive components of the adhesive composition,

[ solution 1]

X-C _s H _2s -Si〔R ¹ 〕 _m 〔OR ² 〕 _3-m …(I)

In the formula, X represents a group containing an ethylene unsaturated bond, a nitrogen atom-containing group, a sulfur atom-containing group or an epoxy group, the nitrogen atom-containing group is an amino group, a mono-substituted amino group, a di-substituted amino group, an isocyanate group, an imidazolyl group, a ureido group or a maleimide group, the sulfur atom-containing group is a mercapto group, R is a hydroxyl group, and ¹ and R ² Each independently represents an alkyl group, m represents an integer of 0 to 2, and s represents an integer of 6 or more.

2. The adhesive composition according to claim 1, further comprising conductive particles.

3. An adhesive composition comprising a silane compound having a structure represented by general formula (I), at least one of the following (A) and (B), and conductive particles,

(A) Epoxy resins and latent curing agents;

(B) A radically polymerizable compound and a curing agent that generates radicals by heat or light,

when the epoxy resin is contained, the content of the epoxy resin is not less than 15% by mass based on the total mass of the adhesive components of the adhesive composition,

when the epoxy resin is contained, the adhesive composition contains an acrylic rubber which is a copolymer obtained by polymerizing glycidyl (meth) acrylate having a glycidyl ether group,

when the radical polymerizable compound is contained, the content of the radical polymerizable compound is 20% by mass or more based on the total mass of the adhesive components of the adhesive composition,

[ solution 2]

X-C _s H _2s -Si〔R ¹ 〕 _m 〔OR ² 〕 _3-m …(I)

In the formula, X represents a group containing an ethylene unsaturated bond, a nitrogen atom-containing group, a sulfur atom-containing group or an epoxy group, the nitrogen atom-containing group is an amino group, a mono-substituted amino group, a di-substituted amino group, an isocyanate group, an imidazolyl group, a ureido group or a maleimide group, the sulfur atom-containing group is a mercapto group, R is a hydroxyl group, and ¹ and R ² Each independently represents an alkyl group, m represents an integer of 0 to 2, s represents an integer of 6 or more,

the conductive particles are metal particles or metal-coated conductive particles.

4. The adhesive composition according to claim 2 or 3, wherein the content of the conductive particles is 100 parts by mass or less with respect to 100 parts by mass of the adhesive component of the adhesive composition.

5. The adhesive composition according to claim 1 or 3, further comprising an epoxy resin and a latent curing agent.

6. The adhesive composition according to claim 1 or 3, further comprising a radically polymerizable compound and a curing agent that generates radicals by heat or light.

7. The adhesive composition according to claim 3, further comprising a film-forming material.

8. The adhesive composition according to claim 1 or 3, further comprising fine rubber particles.

9. A structure comprising the adhesive composition according to claim 1 or 3 or a cured product thereof.

10. A structure body is provided with: a first circuit member having a first circuit electrode, a second circuit member having a second circuit electrode and disposed so that the first circuit electrode and the second circuit electrode face each other, and a circuit connecting member disposed between the first circuit member and the second circuit member,

the first circuit electrode and the second circuit electrode are electrically connected,

the circuit connecting member comprises an adhesive composition or a cured product thereof,

the adhesive composition contains a silane compound having a structure represented by the following general formula (I) and at least one of the following (A) and (B),

(A) Epoxy resin and latent curing agent;

(B) A radically polymerizable compound and a curing agent that generates radicals by heat or light,

when the epoxy resin is contained, the content of the epoxy resin is not less than 15% by mass based on the total mass of the adhesive components of the adhesive composition,

when the epoxy resin is contained, the adhesive composition contains an acrylic rubber which is a copolymer obtained by polymerizing glycidyl (meth) acrylate having a glycidyl ether group,

when the radical polymerizable compound is contained, the content of the radical polymerizable compound is 20% by mass or more based on the total mass of the adhesive components of the adhesive composition,

[ solution 3]

X-C _s H _2s -Si〔R ¹ 〕 _m 〔OR ² 〕 _3-m …(I)

Wherein X represents a group containing an ethylenically unsaturated bond, a nitrogen atom-containing group which is an amino group, a mono-substituted amino group, a di-substituted amino group, an isocyanate group, an imidazole group, a ureido group or a maleimide group, a sulfur atom-containing group which is a mercapto group, R ¹ And R ² Each independently represents an alkyl group, m represents an integer of 0 to 2, and s represents an integer of 6 or more.

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