TWI811185B - Adhesive composition and structure - Google Patents

Abstract

An adhesive composition containing: (a) a thermoplastic resin, (b) a silane compound having a urethane bond and an alkoxysilyl group in the molecule, (c) a radically polymerizable compound, and (d) A radical polymerization initiator that contains (a) component, (c) component, (d) component, or a component other than (a) component, (b) component, (c) component, and (d) component. e) For compounds having urethane bonds, the average linear thermal expansion coefficient of the cured product at 30°C to 90°C is 800 ppm/K or less.

Description

Adhesive composition and structure

The present invention relates to an adhesive composition and structure.

In semiconductor elements and liquid crystal display elements (monitor display elements), various adhesives have been used for the purpose of bonding various members in the elements. The properties required of adhesives include adhesion, heat resistance, reliability under high temperature and high humidity conditions, and many other aspects. Furthermore, as adherends used for bonding, metals (titanium, copper, aluminum, etc.), including ITO, IZO, IGZO, etc. are used, including printed wiring boards, organic substrates (such as polyimide substrates), Base materials with various surface states such as SiN _x and SiO ₂ require molecular design of the adhesive according to each adherend.

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

Furthermore, in recent years, there has been a concern that as semiconductor elements have become more integrated and liquid crystal display elements have become more precise, the spacing between elements and between wirings has become narrower, causing adverse effects on peripheral components due to heat during curing. Furthermore, in order to reduce costs, it is necessary to increase throughput, and bonding at low temperature (90°C to 170°C) and in a short time (within 1 hour, preferably within 10 seconds, and more preferably within 5 seconds) is required. In other words, it requires low temperature and short time hardening (low temperature rapid hardening). It is known that in order to achieve this low-temperature and short-time hardening, it is necessary to use a thermal latent catalyst with low activation energy, but it is very difficult to achieve storage stability near room temperature.

Therefore, in recent years, attention has been paid to radical curing adhesives and the like that use a (meth)acrylate derivative in combination with a peroxide as a radical polymerization initiator. In the radical curing system, free radicals, which are reactive species, are very reactive, so they can be cured in a short time. If the temperature is below the decomposition temperature of the radical polymerization initiator, the peroxide exists stably, so It is a hardening system that combines low-temperature, short-time hardening with storage stability (for example, storage stability near room temperature).

However, in recent years, in the above-mentioned radical curable adhesives, there has been a problem that peeling occurs at the interface between the adherend and the adhesive after high temperature and high humidity treatment (high temperature and high humidity test) such as 85°C and 85% RH.

In this regard, a large number of experiments have been studied and reported so far to improve the adhesive force (interface adhesive force) of the interface between the adherend and the adhesive after the high-temperature and high-humidity treatment as described above, and to suppress the occurrence of peeling (for example, see the following Patent documents 1 to 6 mentioned above). [Prior Art Documents] [Patent Documents]

Patent Document 1: Japanese Patent Laid-Open No. 2007-177204 Patent Document 2: Japanese Patent Laid-Open No. 2010-111846 Patent Document 3: Japanese Patent Laid-Open No. 2003-282637 Patent Document 4: Japanese Patent Laid-Open No. 2003-277694 Patent Document 5: Japanese Patent Application Publication No. 2009-256619 Patent Document 6: Japanese Patent Application Publication No. 2013-191625

[Problems to be Solved by the Invention] However, adhesive compositions used as adhesives are required to further improve the effect of inhibiting peeling after high-temperature and high-humidity treatment.

The present invention was made in view of the above-mentioned facts, and an object thereof is to provide an adhesive composition capable of suppressing peeling after high-temperature and high-humidity treatment, and a structure using the same. [Means to solve the problem]

The inventors of the present invention conducted diligent research and found that in order to suppress peeling after high-temperature and high-humidity treatment, it is important that the adhesive composition contains a silane compound having a urethane bond and an alkoxysilyl group in the molecule. , and compounds having a urethane bond other than the silane compound; and the cured product of the adhesive composition has a low linear thermal expansion coefficient.

More specifically, the present inventors discovered that the adhesive composition contains a silane compound having a urethane bond and an alkoxysilyl group, and a silane compound having a urethane bond that is different from the silane compound. In the case of a compound, the effect of improving peeling by the silane compound is greatly enhanced. Furthermore, the present inventors found that by using these components, the linear thermal expansion coefficient of the cured material can be easily reduced, and further found that adjusting the average linear thermal expansion coefficient of the cured material at 30°C to 90°C to 800 ppm/K or less is effective. It is effective in inhibiting peeling after high temperature and high humidity treatment.

That is, the adhesive composition of the present invention contains: (a) a thermoplastic resin (hereinafter also referred to as "(a) component" as appropriate), (b) having a urethane bond and an alkoxysilane group in the molecule The silane compound (hereinafter also referred to as "(b) component" as the case may be), (c) radical polymerizable compound (hereinafter also referred to as "(c) component" as the case may be), and (d) radical polymerization starter agent (hereinafter also referred to as "(d) component" as appropriate), and as (a) component, (c) component, (d) component, or (a) component, (b) component, (c) component and (a) component, (b) component, (c) component and ( Components other than d), including (e) a compound having a urethane bond (hereinafter also referred to as "(e) component" as appropriate), average linear thermal expansion coefficient of the cured product at 30°C to 90°C (hereinafter also referred to as "average linear thermal expansion coefficient") is 800 ppm/K or less.

According to the adhesive composition of the present invention, peeling after high-temperature and high-humidity treatment can be suppressed. It is speculated that the inhibitory effect of such peeling is obtained by the improvement of interface adhesion after high-temperature and high-humidity treatment. Furthermore, the present inventors found that the peeling improving effect is sustained in the adhesive composition of the present invention. That is, the adhesive composition of the present invention has excellent storage stability.

However, the reasons for peeling after high-temperature and high-humidity treatment are considered to be insufficient reaction (insufficient hardening) of the adhesive due to the shortened low temperature and short time of installation, and the commercialization of display components including smartphones ( commodification), and the surface of adherends (display components, liquid crystal panels, etc.) is increasingly contaminated with cheap substances that easily cause subsequent inhibition; the use of silicon nitride with high hydrophilicity, high temperature and high humidity compared to silicon nitride previously used for insulating films There are an increase in the number of adherends (substrates such as blank glass) with surfaces that are prone to peeling off after treatment. In contrast, according to the adhesive composition of the present invention, even when such an adherend is used, peeling after high-temperature and high-humidity treatment can be suppressed.

The component (b) preferably further has at least one selected from the group consisting of (meth)acrylyl group and vinyl group. This can further suppress peeling after high-temperature and high-humidity treatment.

(e) The component preferably contains at least one selected from the group consisting of polyurethane, polyester urethane, and (meth)acrylic urethane. This can further suppress peeling after high-temperature and high-humidity treatment.

The content of component (c) is preferably 20 mass % or more based on the total mass of solid components in the adhesive composition. This can further suppress peeling after high-temperature and high-humidity treatment.

The adhesive composition of the present invention preferably further contains an inorganic filler with a primary particle size of 100 nm or less. This can further suppress peeling after high-temperature and high-humidity treatment.

The structure of the present invention contains the adhesive composition or a hardened product thereof.

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

The present invention can provide an adhesive composition capable of suppressing peeling after high-temperature and high-humidity treatment, and a structure using the same.

The present invention can provide applications of the adhesive composition or its hardened product in structures or their manufacture. The present invention can provide an application of the adhesive composition or its hardened product in circuit connection. The present invention can provide applications of the adhesive composition or its cured product in circuit connection structures or their manufacture.

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

In this specification, "(meth)acrylate" means at least one of acrylate and its corresponding methacrylate. The same applies to other similar expressions such as "(meth)acrylyl" and "(meth)acrylic acid". Unless otherwise specified, one type of materials exemplified below may be used alone or two or more types may be used in combination. The content of each component in the composition, when there are multiple substances corresponding to each component in the composition, means the total amount of the multiple substances present in the composition unless otherwise specified. The numerical range expressed using "～" indicates the range including the numerical values described before and after "～" as the minimum value and the maximum value respectively. The so-called "A or B" only needs to include either A or B, or both. The so-called "room temperature" means 25℃.

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

In this specification, "adhesion", "adhesion", "adhesion strength" and "interface adhesion" have the same meaning. For example, the term "high adhesion strength after high temperature and high humidity treatment" means high interfacial adhesion strength after high temperature and high humidity treatment. In this specification, "the total mass of the solid content in the adhesive composition" means the total mass of the adhesive composition when the adhesive composition does not contain a solvent. When the adhesive composition contains a solvent, it means the total mass of the adhesive composition. The following shows the mass after subtracting the mass of the solvent from the total mass of the adhesive composition. In addition, when the adhesive composition contains conductive particles, the "total mass of solid components in the adhesive composition" does not include the mass of the conductive particles, and the "total volume of solid components in the adhesive composition" does not include The volume of conductive particles (that is, "the total mass of the solid components in the adhesive composition" means "the total mass of the solid components in the adhesive composition (excluding conductive particles)," "the total mass of the solid components in the adhesive composition" "Total volume of solid content" means "the total volume of solid content (excluding conductive particles) in the adhesive composition").

<Adhesive composition> The adhesive composition of this embodiment contains: (a) thermoplastic resin, (b) silane compound having a urethane bond and an alkoxysilyl group in the molecule, (c) free radicals A polymerizable compound and (d) a radical polymerization initiator as (a) component, (c) component, (d) component, or (a) component, (b) component, (c) component and (d) ) components other than (e) a compound having a urethane bond. The adhesive composition of this embodiment is, for example, a radical curable adhesive composition.

[(a) Component] Examples of the component (a) include polyimide, polyamide, phenoxy resin, (meth)acrylic resin, polyester, polyurethane, and polyester amine. At least one resin from the group consisting of polyether urethane, polyether urethane and polyvinyl butyraldehyde. (a) The component can be used individually by 1 type or in combination of 2 or more types.

From the viewpoint of suppressing peeling after high-temperature and high-humidity treatment, the component (a) preferably contains a phenoxy resin. Similarly, from the viewpoint of suppressing peeling after high-temperature and high-humidity treatment, component (a) preferably contains a thermoplastic resin having a urethane bond. Examples of such thermoplastic resins include polyurethane, polyester urethane, polyether urethane, and the like.

For the purpose of stress relaxation and further improvement of adhesion after high temperature and high humidity treatment, a rubber component may be used as component (a). Examples of the rubber component include acrylic rubber, polyisoprene, polybutadiene, carboxyl-terminated polybutadiene, hydroxyl-terminated polybutadiene, 1,2-polybutadiene, and carboxyl-terminated 1,2- Polybutadiene, hydroxyl-terminated 1,2-polybutadiene, styrene-butadiene rubber, hydroxyl-terminated styrene-butadiene rubber, carboxylated nitrile rubber, hydroxyl-terminated poly(oxypropylene), Alkoxysilyl-terminated poly(oxypropylene) glycol, poly(oxytetramethylene) glycol, polyolefin glycol and poly-ε-caprolactone. From the viewpoint of further improving the adhesiveness after high-temperature and high-humidity treatment, the rubber component preferably has a cyano group or a carboxyl group as a highly polar group as a side chain group or terminal group. A rubber component may be used individually by 1 type or in combination of 2 or more types.

From the viewpoint of further improving the adhesive strength of the adhesive composition, the weight average molecular weight (Mw) of the component (a) is preferably 5,000 or more, more preferably 10,000 or more. From the viewpoint that good compatibility with other components tends to be easily obtained and appropriate fluidity of the adhesive composition is easily obtained, the weight average molecular weight (Mw) of the component (a) is preferably 1,000,000 or less, more preferably It is 500,000 or less, and more preferably, it is 400,000 or less. From these viewpoints, the weight average molecular weight of component (a) is preferably 5,000 to 1,000,000, more preferably 5,000 to 500,000, and still more preferably 10,000 to 400,000.

Furthermore, the weight average molecular weight can be measured, for example, by gel permeation chromatography (GPC) using a calibration curve of standard polystyrene. More specifically, the measurement can be performed under the conditions described in the Examples.

From the viewpoint of further improving the adhesive strength of the adhesive composition and improving the film-forming properties of the adhesive composition, (a) The content of the component is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and still more preferably 35 parts by mass or more. From the viewpoint of easily obtaining appropriate fluidity of the adhesive composition, the content of component (a) is preferably 80 parts by mass or less based on 100 parts by mass of the total amount of component (a) and component (c). More preferably, it is 70 parts by mass or less, and still more preferably, it is 65 parts by mass or less. From these viewpoints, the content of component (a) is preferably from 20 parts by mass to 80 parts by mass, more preferably from 30 parts by mass to 100 parts by mass of the total amount of component (a) and component (c). 70 parts by mass, and more preferably 35 parts by mass to 65 parts by mass.

As mentioned above, (a) component may contain the thermoplastic resin which has a urethane bond. In other words, component (a) may also include component (e). When component (a) contains component (e), from the viewpoint of further suppressing peeling after high-temperature and high-humidity treatment, an amine must be present relative to 100 parts by mass of the total of component (a) and component (c). The content C _a1 of the component (a) of the formate bond is preferably in the following range. Content C _a1 is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and still more preferably 35 parts by mass or more. Content C _a1 is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 65 parts by mass or less. From these viewpoints, content C _a1 is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass, and further preferably 35 to 65 parts by mass.

[(b) Component] The adhesive composition of this embodiment contains a silane compound having a urethane bond and an alkoxysilyl group in the molecule as the (b) component. (b) The component may be used alone or in combination of two or more.

The component (b) may be a compound having a urethane bond and a hydrolyzable alkoxysilyl group having 1 to 2 carbon atoms in the molecule. From the viewpoint of suppressing peeling after high-temperature and high-humidity treatment, component (b) is preferably a compound represented by the following formula (1).

[Chemical 1] [In formula (1), m represents an integer of 1 to 3, R ¹¹ represents a hydrogen atom, a methyl group or an ethyl group, R ¹² represents an arbitrary monovalent organic group, and R ¹³ represents an arbitrary divalent organic group. Multiple R ¹¹ in the same molecule can be the same or different]

From the viewpoint of further suppressing peeling after high-temperature and high-humidity treatment, component (b) preferably further has a reactive functional group. That is, as the component (b), an alkoxysilane compound having a reactive functional group and a urethane bond in the molecule is preferred. For example, when component (b) is a compound represented by the formula (1), R ¹² is preferably an organic group having a reactive functional group. From the viewpoint of further suppressing peeling after high-temperature and high-humidity treatment, the reactive functional group may be at least one functional group selected from the group consisting of (meth)acrylyl group and vinyl group. R ¹³ may be a group represented by the following formula.

[Chemicalization 2] [In the formula, n represents any integer]

From the viewpoint of suppressing peeling after high-temperature and high-humidity treatment, m is preferably 2 or 3, more preferably 3. From the viewpoint of suppressing peeling after high-temperature and high-humidity treatment, n is preferably 0 to 15, more preferably 1 to 10, and still more preferably 1 to 5.

Specific examples of the compound represented by the formula (1) include compounds represented by the following formulas (1a) to (1k). These compounds can be used individually by 1 type or in combination of 2 or more types. From the viewpoint of suppressing peeling after high-temperature and high-humidity treatment, the compound represented by formula (1) is preferably a compound in which R ^1b in formula (1b) is a hydrogen atom.

[Chemical 3]

[Chemical 4]

[Chemistry 5]

[Chemical 6]

[Chemical 7]

Here, R ^1a represents a C1-C10 alkyl group or a cyclic alkyl group. R ^1b , R ^1c and R ^1d each represent a hydrogen atom or a methyl group. R ^1e , R ^11f , R ^1g , R ^1h , R ¹ⁱ and R ^1j respectively represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group, an alkoxy group, a hydroxyl group or a hydroxyl group. R ^12f represents an alkylene group having 1 to 3 carbon atoms. Et represents ethyl group and Me represents methyl group. p represents an integer from 1 to 5.

From the viewpoint of further suppressing peeling after high-temperature and high-humidity treatment (for example, further suppressing the generation of peeling bubbles at the interface between the circuit member and the circuit connection material), based on the total mass of the solid content in the adhesive composition, (b) The content of the component is preferably in the following range. The content of the component (b) is preferably 0.2 parts by mass or more, more preferably 0.5 parts by mass or more, further preferably 1 part by mass or more, and particularly preferably 5 parts by mass or more. The content of the component (b) is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, further preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less. From these viewpoints, the content of component (b) is preferably 0.2 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, further preferably 1 to 15 parts by mass, and particularly preferably 5 parts Parts by mass ~ 10 parts by mass.

From the viewpoint of suppressing peeling after high-temperature and high-humidity treatment, the content of component (b) is preferably in the following range based on 100 parts by mass of component (a). The content of the component (b) is preferably more than 5 parts by mass, more preferably 7.5 parts by mass or more, further preferably 10 parts by mass or more, and particularly preferably 15 parts by mass or more. The content of the component (b) is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, still more preferably 60 parts by mass or less, particularly preferably 40 parts by mass or less, and most preferably 30 parts by mass or less. From these viewpoints, the content of component (b) is preferably more than 5 parts by mass and 100 parts by mass or less, more preferably 7.5 to 80 parts by mass, and still more preferably 10 to 60 parts by mass, especially The optimum range is 15 to 40 parts by mass, and the optimum range is 15 to 30 parts by mass.

[(c) Component] The adhesive composition of this embodiment may contain a radically polymerizable compound (excluding a compound corresponding to component (b)) as component (c). As (c) component, a monomer and/or an oligomer can be used.

The component (c) may be a radically polymerizable compound having two or more (meth)acrylyl groups in the molecule. As component (c), a polyfunctional (meth)acrylate compound having two or more (meth)acryloxy groups in the molecule is preferred. In this case, by fully exerting the cohesive force after curing and suppressing curing shrinkage, there is a tendency to further improve the adhesiveness and further suppress peeling after high-temperature and high-humidity treatment. Examples of such (meth)acrylate compounds include epoxy (meth)acrylate, (meth)acrylic urethane, polyether (meth)acrylate, and polyester (meth)acrylate. ester, trimethylolpropane tri(meth)acrylate, polyalkylene glycol di(meth)acrylate (polyethylene glycol di(meth)acrylate, etc.), neopentyl glycol di(meth)acrylate, etc. base) acrylate, dipentaerythritol hexa(meth)acrylate, isocycyanuric acid-modified 2-functional (meth)acrylate, isocycyanuric acid-modified 3-functional (meth)acrylate, etc. (c) The component may be used alone or in combination of two or more.

Examples of the epoxy (meth)acrylate include those obtained by adding (meth)acrylic acid to two glycidyl groups of bisphenol benzene diglycidyl ether; toward bisphenol Epoxy (meth)acrylate, etc., are compounds in which ethylene glycol or propylene glycol is added to two glycidyl groups of benzene diglycidyl ether, and a (meth)acryloxy group is introduced therein.

The component (c) preferably contains a radically polymerizable compound having two or more (meth)acrylyl groups in the molecule and a urethane bond. In this case, the compatibility between the component (b) and the component (c) tends to be good, and peeling after the high-temperature and high-humidity treatment is further suppressed. Examples of such radically polymerizable compounds include (meth)acrylic urethane.

The adhesive composition of this embodiment may contain a monofunctional (meth)acrylate compound as the component (c) for the purpose of adjusting fluidity or the like.

Examples of the monofunctional (meth)acrylate compound include pentaerythritol (meth)acrylate, 2-cyanoethyl (meth)acrylate, cyclohexyl (meth)acrylate, and di(meth)acrylate. Cyclopentenyl ester, dicyclopentenoxyethyl (meth)acrylate, 2-(2-ethoxyethoxy)(meth)acrylic acid ethyl ester, (meth)acrylic acid 2-ethoxyethyl Ester, 2-ethylhexyl (meth)acrylate, n-hexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, isobornyl (meth)acrylate , isodecyl (meth)acrylate, isooctyl (meth)acrylate, n-lauryl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-benzene (meth)acrylate Oxyethyl ester, tetrahydrofurfuryl (meth)acrylate, 2-(meth)acryloyloxyethyl phosphate, N,N-dimethylaminoethyl (meth)acrylate, (methyl) N,N-dimethylaminopropyl acrylate, glycidyl group-containing (methyl) obtained by reacting (meth)acrylic acid with one glycidyl group of an epoxy resin having multiple glycidyl groups ) acrylate, and (meth)acryloylmorpholine. A monofunctional (meth)acrylate compound can be used individually by 1 type or in combination of 2 or more types.

For the purpose of increasing the crosslinking rate, etc., the adhesive composition of this embodiment may contain a compound having a radically polymerizable functional group such as an allyl group, a maleimide group, or a vinyl group as the component (c). Examples of such compounds include N-vinylimidazole, N-vinylpyridine, N-vinylpyrrolidone, N-vinylformamide, N-vinylcaprolactam, 4,4' - Vinylidene bis(N,N-dimethylaniline), N-vinyl acetamide, N,N-dimethylacrylamide, N-isopropylacrylamide and N,N-diethyl Acrylamide.

For the purpose of improving the adhesive strength, the adhesive composition of this embodiment preferably contains a radically polymerizable compound having a phosphate group (hereinafter also referred to as "(c1) component" as the case may be) as the (c) component. Examples of the component (c1) include compounds represented by the following formula (2a), formula (2b) or formula (2c).

[Chemical 8] [In the formula (2a), R ^21a represents a hydrogen atom or a methyl group, R ^22a represents a (meth)acryloxy group, and w and x each independently represent an integer of 1 to 8. Furthermore, multiple R ^21a , R ^22a , w and x in the same molecule may be the same or different respectively]

[Chemical 9] [In the formula (2b), R ^2b represents a (meth)acryloxy group, and y and z each independently represent an integer of 1 to 8. Multiple R ^2b , y and z in the same molecule may be the same or different]

[Chemical 10] [In the formula (2c), R ^21c represents a hydrogen atom or a methyl group, R ^22c represents a (meth)acryloxy group, and b and c each independently represent an integer of 1 to 8. Multiple R ^21c and b in the same molecule may be the same or different]

Examples of the component (c1) include 2,2'-di(meth)acryloyloxydiethyl phosphate, ethylene oxide (Ethylene Oxide, EO) modified phosphate di(meth)acrylate, ( Methacrylic acid phosphoryloxyethyl ester, (meth)acrylic acid phosphoryloxypropyl acrylate, acidic phosphoryloxypolyoxyethylene glycol mono(meth)acrylate, acidic phosphoryloxypropyl acrylate Oxypolyoxypropylene glycol mono(meth)acrylate, phosphoric acid modified epoxy (meth)acrylate and vinyl phosphate.

From the viewpoint of improving heat resistance, the content of component (c) is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, based on 100 parts by mass of the total amount of component (a) and component (c). Furthermore, it is more preferably 35 parts by mass or more, particularly preferably 40 parts by mass or more, and extremely preferably 45 parts by mass or more. From the viewpoint of greater effect in suppressing peeling after high-temperature and high-humidity treatment, the content of component (c) is preferably 80 parts by mass or less based on 100 parts by mass of the total amount of component (a) and component (c). , more preferably 70 parts by mass or less, still more preferably 65 parts by mass or less, particularly preferably 60 parts by mass or less, and extremely preferably 55 parts by mass or less. From these viewpoints, the content of component (c) is preferably 20 to 80 parts by mass, and more preferably 30 to 30 parts by mass relative to 100 parts by mass of the total amount of component (a) and component (c). 70 parts by mass, more preferably 35 parts by mass to 65 parts by mass, particularly preferably 40 parts by mass to 60 parts by mass, and most preferably 45 parts by mass to 55 parts by mass.

From the viewpoint of easily obtaining high bonding strength, the content of component (c1) is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass, based on 100 parts by mass of the total amount of component (a) and component (c). parts by mass or more, more preferably 1 part by mass or more, particularly preferably 2 parts by mass or more. From the viewpoint that the physical properties of the cured product of the adhesive composition are less likely to decrease and the effect of improving connection reliability can be favorably obtained, (c1 ) component is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, further preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less. From these viewpoints, the content of component (c1) is preferably 0.1 to 15 parts by mass, more preferably 0.5 to 15 parts by mass, based on 100 parts by mass of the total amount of component (a) and component (c). 10 parts by mass, more preferably 1 to 5 parts by mass, and particularly preferably 2 to 3 parts by mass.

From the viewpoint of inhibiting peeling after high-temperature and high-humidity treatment, the content of component (c) is preferably 20 mass % or more, more preferably 30 mass % or more, based on the total mass of solid components in the adhesive composition. , and more preferably 40% by mass or more. From the viewpoint of suppressing peeling after high-temperature and high-humidity treatment, the content of component (c) is preferably 90 mass % or less, more preferably 80 mass % or less, based on the total mass of solid components in the adhesive composition. , more preferably 70 mass% or less, particularly preferably 60 mass% or less. From these viewpoints, based on the total mass of solid components in the adhesive composition, the content of component (c) is preferably 20 mass% to 90 mass%, more preferably 30 mass% to 80 mass%, and further Preferably, it is 40 mass % - 70 mass %, Especially preferably, it is 40 mass % - 60 mass %.

As mentioned above, (c) component may contain the radical polymerizable compound which has a urethane bond. In other words, component (c) may also include component (e). When component (c) contains component (e), from the viewpoint of further suppressing peeling after high-temperature and high-humidity treatment, an amine must be present relative to 100 parts by mass of the total of component (a) and component (c). The content C _b1 of the component (c) of the formate bond is preferably in the following range. Content C _b1 is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and still more preferably 40 parts by mass or more. Content C _b1 is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, further preferably 70 parts by mass or less, particularly preferably 60 parts by mass or less, and extremely preferably 50 parts by mass or less. From these viewpoints, the content C _b1 is preferably 20 to 90 parts by mass, more preferably 30 to 80 parts by mass, further preferably 40 to 70 parts by mass, and particularly preferably 40 to 40 parts by mass. 60 parts by mass, preferably 40 parts by mass to 50 parts by mass.

When component (c) contains component (e), from the viewpoint of suppressing peeling after high-temperature and high-humidity treatment, content C _b1 is determined relative to content C _b2 of component (c) that does not have a urethane bond. The mass ratio C _b1 /C _b2 is preferably in the following range. The mass ratio C _b1 /C _b2 is preferably at least 0.01, more preferably at least 0.1, further preferably at least 1, particularly preferably at least 2, and extremely preferably at least 3. The mass ratio C _b1 /C _b2 may be 50 or less.

[(d) Component] The adhesive composition of this embodiment contains a radical polymerization initiator as the (d) component. As the component (d), any compound can be selected from compounds such as peroxides and azo compounds. From the viewpoint of excellent stability, reactivity, and compatibility, component (d) is preferably a peroxide with a 1-minute half-life temperature of 90°C to 175°C and a molecular weight of 180 to 1,000. The so-called "half-life temperature of 1 minute" refers to the temperature at which the half-life of peroxide is 1 minute. The so-called "half-life" refers to the time it takes for the concentration of a compound to reduce to half of its initial value at a given temperature. (d) The component may be used alone or in combination of two or more.

The component (d) may be, for example, selected from the group consisting of 1,1,3,3-tetramethylbutyl peroxyneodecanoate, di(4-tert-butylcyclohexyl)peroxydicarbonate, and dicarbonate peroxide. Di(2-ethylhexyl) carbonate, cumyl peroxyneodecanoate, dilauryl peroxide, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, terthexyl neodecanoate peroxide Ester, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 2,5-di Methyl-2,5-di(2-ethylhexylperoxy)hexane, tert-hexyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl neoheptanoate peroxide, tert-pentyl peroxy-2-ethylhexanoate, di-tert-butyl peroxide hexahydroterephthalate, 3,5,5-trimethyl peroxide Third amyl hexanoate, 3-hydroxy-1,1-dimethylbutyl peroxyneodecanoate, third amyl peroxyneodecanoate, 3-methylbenzoyl peroxide, 4 -Tolyl peroxide, bis(3-methylbenzoyl) peroxide, dibenzoyl peroxide, bis(4-methylbenzoyl)peroxide, 2, 2'-Azobis-2,4-dimethylvaleronitrile, 1,1'-Azobis(1-acetyloxy-1-phenylethane), 2,2'-Azobisiso Butyronitrile, 2,2'-Azobis(2-methylbutyronitrile), 4,4'-Azobis(4-cyanovaleric acid), 1,1'-Azobis(1-cyclohexane) Alkanecarbonitrile), tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxymaleate, tert-butyl peroxy-3,5,5-trimethylhexanoate, peroxy tert-butyl laurate, 2,5-dimethyl-2,5-di(peroxy-3-methylbenzyl)hexane, tert-butyl peroxy-2-ethylhexylmonocarbonate, tert-hexyl peroxybenzoate, 2,5-dimethyl-2,5-di(benzoyl peroxide)hexane, tert-butyl peroxybenzoate, trimethyladipic acid peroxide At least one compound in the group consisting of dibutyl ester, third amyl peroxyn-octanoate, third amyl peroxyisononanoate and third amyl peroxybenzoate.

The component (d) may also contain a radical polymerization initiator having a urethane bond. In other words, component (d) may also include component (e).

From the viewpoint of inhibiting corrosion of electrodes (for example, connection terminals (circuit electrodes) of circuit members), the amount of chloride ions or organic acids contained in the radical polymerization initiator is preferably 5000 ppm or less. Furthermore, from the same viewpoint, the radical polymerization initiator is more preferably a compound that generates less organic acid after decomposition. Furthermore, from the viewpoint of improving the storage stability of the adhesive composition, it is preferable to use a radical polymerization initiator that has a mass retention rate of 20 mass % or more after being left open at room temperature and normal pressure for 24 hours.

From the viewpoint of obtaining good reactivity in a short time, the content of component (d) is preferably 1 part by mass or more, more preferably 100 parts by mass in total of component (a) and component (c). 2.5 parts by mass or more, more preferably 3 parts by mass or more, particularly preferably 4 parts by mass or more. From the viewpoint of better storage stability, the content of component (d) is preferably 15 parts by mass or less, more preferably 10 parts by mass, based on 100 parts by mass of the total amount of component (a) and component (c). or less, and more preferably 5 parts by mass or less. From these viewpoints, the content of component (d) is preferably 1 to 15 parts by mass, and more preferably 2.5 to 15 parts by mass relative to 100 parts by mass of the total amount of component (a) and component (c). 10 parts by mass, more preferably 3 parts by mass to 10 parts by mass, particularly preferably 4 parts by mass to 5 parts by mass.

[(e)Component] The adhesive composition of this embodiment may contain component (e) as component (a), component (c) or component (d), or component (a) or component (b). ) component, (c) component and (d) component and contains (e) component. Examples of other components other than the (a) component, (b) component, (c) component, and (d) component include urethane particles.

From the viewpoint of inhibiting peeling after high-temperature and high-humidity treatment, component (e) is preferably selected from the group consisting of polyurethane, polyester urethane, and (meth)acrylic urethane. at least one ingredient in the group.

(e) The component can be used individually by 1 type or in combination of 2 or more types. For example, the adhesive composition of this embodiment may contain two or more components (a) having a urethane bond, or may contain component (a) having a urethane bond and a component having a urethane bond. (c) component of ester bond. From the viewpoint of further suppressing peeling after high-temperature and high-humidity treatment, the adhesive composition of the present embodiment preferably contains (a) component having a urethane bond and (c) having a urethane bond. Element.

From the viewpoint of further suppressing peeling after high-temperature and high-humidity treatment, the content of component (e) is preferably in the following range based on the total mass of solid components in the adhesive composition. The content of the component (e) is preferably 5 mass% or more, more preferably 10 mass% or more, and still more preferably 15 mass% or more. The content of the component (e) is preferably 95 mass% or less, more preferably 90 mass% or less, and still more preferably 85 mass% or less. From these viewpoints, the content of component (e) is preferably 5% by mass to 95% by mass, more preferably 10% by mass to 90% by mass, and further preferably 15% by mass to 85% by mass.

From the viewpoint of suppressing peeling after high-temperature and high-humidity treatment, the content of component (e) is preferably in the following range based on 100 parts by mass of component (b). The content of the component (e) is preferably 10 parts by mass or more, more preferably 100 parts by mass or more, further preferably 200 parts by mass or more, and particularly preferably 300 parts by mass or more. The content of the component (e) is preferably 2,000 parts by mass or less, more preferably 1,000 parts by mass or less, further preferably 750 parts by mass or less, and particularly preferably 500 parts by mass or less. From these viewpoints, the content of component (e) is preferably 10 to 2000 parts by mass, more preferably 100 to 1000 parts by mass, further preferably 200 to 750 parts by mass, and particularly preferably 300 parts by mass. Parts by mass ~ 500 parts by mass.

According to the adhesive composition of this embodiment, it is estimated that the effect of improving the interfacial adhesion force obtained by the silane compound is greatly improved, and excellent interfacial adhesion force can be obtained compared with the conventional adhesive composition. The reason for this effect is not clear, but it is thought that the component (b) having a urethane bond is compatible with the component (e), and the component (b) is less likely to localize in the adhesive composition or its cured product. It exists, thereby suppressing the phenomenon that the component (b) bleeds out to the surface of the adhesive composition or its hardened product, thereby suppressing the deactivation of the component (b).

[Other Components] (Silane Compound Other than Component (b)) The adhesive composition of this embodiment may contain any silane compound different from component (b). Examples of such silane compounds include vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldiethoxy Silane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxysilane Propylmethyldiethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy Silane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane Silanes and their condensates.

Based on the total mass of solid components in the adhesive composition, the content of the silane compound is preferably 0.1% to 30% by mass, more preferably 0.25% to 20% by mass. When the content of the silane compound is within the above range, peeling after high-temperature and high-humidity treatment is further suppressed (for example, the generation of peeling bubbles at the interface between the circuit member and the circuit connection material is further suppressed).

From the viewpoint of further suppressing peeling after high-temperature and high-humidity treatment, the content of the silane compound in the adhesive composition of the present embodiment (including the component (b)) is determined based on the total mass of solid components in the adhesive composition. The total amount of silane compounds) may be 0.1 mass% or more, 1 mass% or more, or 5 mass% or more. As the content of the silane compound increases, the average linear thermal expansion coefficient of the hardened material tends to decrease. From the viewpoint of excellent film formation properties, the content of the silane compound in the adhesive composition of this embodiment may be 30 mass% or less, 20 mass% or less, or 15 mass% or less.

(Insulating filler) The adhesive composition of this embodiment may contain at least one selected from the group consisting of inorganic fillers and organic fillers as an insulating filler. Examples of the inorganic filler include metal oxide fine particles such as silica fine particles, alumina fine particles, silica-alumina fine particles, titanium dioxide fine particles, and zirconium oxide fine particles; and inorganic fine particles such as nitride fine particles. Examples of the organic filler include organic fine particles such as silicone fine particles, methacrylate-butadiene-styrene fine particles, acrylic-silicone fine particles, polyamide fine particles, and polyimide fine particles. The microparticles may have a uniform structure or a core-shell structure. From the viewpoint of further suppressing peeling after high-temperature and high-humidity treatment, the adhesive composition of the present embodiment preferably contains an inorganic filler. In addition, when an organic filler contains (a) component, this organic filler is classified as (a) component.

From the viewpoint of suppressing peeling after high-temperature and high-humidity treatment, the respective contents of the organic filler and the inorganic filler are preferably in the following ranges based on 100 parts by mass of the total amount of the component (a) and the component (c). The content is preferably 1 part by mass or more, more preferably 5 parts by mass or more. From the viewpoint of reducing the coefficient of linear thermal expansion, the higher the content of the inorganic filler, the better. The content may be 50 parts by mass or less.

From the viewpoint of suppressing peeling after high-temperature and high-humidity treatment, the primary particle diameter of the inorganic filler is preferably 100 nm or less, more preferably 75 nm or less, and still more preferably 50 nm or less. As the primary particle size of the inorganic filler decreases, the total area of the interface between the inorganic filler and the resin (for example, component (a)) increases and the linear thermal expansion coefficient tends to decrease when the same amount is used. The primary particle size of the inorganic filler can be 5 nm or more. Furthermore, the primary particle size of the inorganic filler can be measured by a scanning electron microscope.

(Conductive Particles) The adhesive composition of this embodiment may contain conductive particles. The adhesive composition containing conductive particles can be particularly suitably used as an anisotropic conductive adhesive.

Examples of conductive particles include metal particles such as gold (Au), silver (Ag), palladium (pd), nickel (Ni), copper (Cu), and solder; carbon particles, etc. The metal particles may be a combination of multiple metals. For example, the metal particles may be particles having copper particles and a silver layer covering the copper particles. Moreover, the conductive particles may also be composite particles having core particles containing non-conductive materials such as glass, ceramics, and plastics, and conductive layers such as metal, metal particles, and carbon covering the core particles. The core particles of the composite particles are preferably plastic particles.

Composite particles using the plastic particles as core particles have deformability that can be deformed by heating and pressure. Therefore, compared with the case of using other conductive particles, when the composite particles are used, for example, when circuit members are connected to each other, the contact area between the circuit electrodes of the circuit member and the conductive particles can be increased. Therefore, according to the adhesive composition containing the said composite particle as a conductive particle, a circuit connection structure which is more excellent in terms of connection reliability can be obtained.

The adhesive composition of this embodiment may contain insulating-coated conductive particles having the conductive particles and an insulating layer or insulating particles covering at least a part of the surface of the conductive particles. That is, at least part of the surface of the conductive particles may be covered with an insulating layer or insulating particles. The insulating layer can be provided by hybridization or other methods. The insulating layer or insulating particles are formed of insulating materials such as polymer resin. The insulating particles may be the above-mentioned organic fillers or inorganic fillers. By coating the conductive particles with such insulation, short circuits between adjacent conductive particles are less likely to occur.

From the viewpoint of obtaining good dispersibility and conductivity, the average particle diameter of the conductive particles is preferably 1 μm to 30 μm. Furthermore, the average particle diameter of the conductive particles can be measured by a laser diffraction particle size distribution meter.

Based on the total volume of solid components in the adhesive composition, the content of the conductive particles is preferably 0.1% to 30% by volume, more preferably 0.1% to 10% by volume, and further preferably 0.5% to 7.5% by volume. Volume %. When the content of the conductive particles is 0.1% by volume or more, the conductivity tends to be improved. When the content of the conductive particles is 30% by volume or less, short circuits between electrodes (circuit electrodes, etc.) tend to be less likely to occur. The content (volume %) of conductive particles is determined based on the volume of each component constituting the adhesive composition before curing at 23°C. The volume of each component can be found by converting mass into volume using specific gravity. The volume of each component can also be measured using an appropriate solvent (water, alcohol, etc.) that does not dissolve or swell the component to be measured and that can fully wet the component. Specifically, the solvent can be placed in a graduated cylinder or the like, a component to be measured can be introduced therein, and the increased volume can be determined as the volume of the component.

The adhesive composition of this embodiment may contain a thiol compound. The adhesive composition of this embodiment may also suitably contain an adhesion improver (excluding the component (b) and silane compounds other than component (b)), a tackifier, a leveling agent, a colorant, a weather resistance improver, etc. Additives.

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

The average linear thermal expansion coefficient at 30°C to 90°C of the cured product of the adhesive composition of this embodiment is 800 ppm/K or less. When the average linear thermal expansion coefficient is greater than 800 ppm/K, it is difficult to obtain the effect of suppressing peeling after high-temperature and high-humidity treatment. From the viewpoint of suppressing peeling after high-temperature and high-humidity treatment, the average linear thermal expansion coefficient is preferably 750 ppm/K or less, more preferably 700 ppm/K or less. The lower limit of the average linear thermal expansion coefficient may be, for example, 10 ppm/K or more. The average linear thermal expansion coefficient of the hardened material can be measured using, for example, a thermomechanical analysis device (manufactured by Shimadzu Corporation). Specifically, it can be measured by the method described in the Examples.

As a method of reducing the average linear thermal expansion coefficient, for example, the following methods can be cited: (1) using a thermoplastic resin with a higher Tg; (2) reducing the content of low molecular weight reactive components relative to the low molecular weight reactive components. The solid content mass ratio meter uses relatively more oligomer-sized reactive components; (3) uses inorganic fillers; (4) increases the content of silane compounds, etc. Examples of low molecular weight reactive components include EO isocyanurate modified di(meth)acrylate. Examples of the oligomer-sized reactive component include (meth)acrylic urethane.

However, the linear thermal expansion coefficients of glass and polyimide, which are the main materials of each of liquid crystal panels and flexible printed circuits (FPC), are generally about 10 ppm/K. Compared with this, existing radical polymerization methods The linear thermal expansion coefficient of the circuit connection material is above 1000 ppm/K. Therefore, when a structure is produced by connecting a liquid crystal panel and an FPC using an existing radical polymerization-based circuit connection material (that is, when a flexible board on glass (FOG) is connected), when When the structure is processed under high temperature and high humidity conditions of 85°C and 85% RH, due to the different degrees of thermal expansion of each component, strains are generated at the interface between the FPC and the circuit connection material, and at the interface between the circuit connection material and the liquid crystal panel. If the stress caused by this strain exceeds the adhesion force of the interface, peeling will occur. Not only in the case of FOG connection as mentioned above, but also in the case of Chip On Glass (COG) connection where the driver integrated circuit (IC) is mounted on the liquid crystal panel, and when FPC is connected to FPC When a flexible board is connected to a flexible board (Flex on Flex, FOF), there is also a tendency for peeling caused by the same mechanism. On the other hand, in the adhesive composition of this embodiment, the average linear thermal expansion coefficient of the cured product at 30°C to 90°C is 800 ppm/K or less, so it is estimated that it can be used under high temperature and high humidity conditions of 85°C and 85%RH. Even when the structure is processed under such conditions, it is not easy to produce strain at the interface, so that peeling is not easy to occur.

When the adhesive composition of this embodiment is liquid at room temperature, it can be used in a paste form. When the adhesive composition is solid at room temperature, in addition to heating and using it, the adhesive composition can also be gelatinized using the solvent.

The adhesive composition of this embodiment may be in a film form. If necessary, apply a solution of an adhesive composition containing a solvent or the like on a fluororesin film, a polyethylene terephthalate film, or a releasable base material (release paper, etc.), and then remove the solvent or the like. A film-like adhesive composition is obtained. Furthermore, after impregnating a base material such as a nonwoven fabric with the solution and placing it on a releasable base material, a film-like adhesive composition can be obtained by removing the solvent or the like. If the adhesive composition is used in a film form, it is more convenient from the viewpoint of excellent workability and the like. The thickness of the film-like adhesive composition may be 1 μm to 100 μm, or may be 5 μm to 50 μm.

The adhesive composition of this embodiment can be adhered by pressing together with heating or light irradiation. By combining heating and light irradiation, bonding can be performed at low temperature and in a short time. It is preferable to irradiate light with light in the wavelength range of 150 nm to 750 nm. The light source can use low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps (ultra-high-pressure mercury lamps, etc.), xenon lamps, metal halide lamps, etc. The irradiation dose can be 0.1 J/cm ² to 10 J/cm ² . The heating temperature is not particularly limited, but a temperature of 50°C to 170°C is preferred. The pressure is not particularly limited as long as it does not cause damage to the adherend, but is preferably 0.1 MPa to 10 MPa. It is preferable to perform heating and pressurization in the range of 0.5 seconds to 3 hours.

The adhesive composition of this embodiment can be used as an adhesive for the same type of adherends, or can be used as an adhesive for different types of adherends with different thermal expansion coefficients. Specifically, it can be used as circuit connection materials represented by anisotropic conductive adhesives, silver pastes, silver films, etc.; elastomers for chip scale packages (CSP), underfill materials for CSP, and lead wires on wafers. It is used to adhere semiconductor components represented by on Chip, LOC) tape, etc. to materials, etc.

<Structure and its manufacturing method> The structure of this embodiment contains the adhesive composition of this embodiment or its hardened product. The structure of this embodiment is, for example, a semiconductor device such as a circuit connection structure. As one embodiment of the structure of this embodiment, the circuit connection structure includes a first circuit member having a first circuit electrode, a second circuit member having a second circuit electrode, and a circuit member disposed between the first circuit member and the second circuit. Circuit connecting components between components. The first circuit member includes, for example, a first substrate and a first circuit electrode arranged on the first substrate. The second circuit member includes, for example, a second substrate and a second circuit electrode arranged on the second substrate. The first circuit electrode and the second circuit electrode face each other and are electrically connected. The circuit connection member contains the adhesive composition of this embodiment or its cured product. The structure of this embodiment only needs to include the adhesive composition of this embodiment or its hardened product, and a member (such as a substrate) that does not have circuit electrodes may be used instead of the circuit member of the circuit connection structure.

The manufacturing method of the structure of this embodiment includes the step of hardening the adhesive composition of this embodiment. As one embodiment of the method of manufacturing a structure of this embodiment, the method of manufacturing a circuit connection structure includes the step of arranging a first circuit member having a first circuit electrode and a second circuit member having a second circuit electrode. The adhesive composition of this embodiment is arranged between the two, and the heating and pressurizing step pressurizes the first circuit member and the second circuit member to electrically connect the first circuit electrode and the second circuit electrode, and the adhesive composition is Heating and hardening. In the arranging step, the first circuit electrode and the second circuit electrode may be arranged in such a manner that they face each other. In the heating and pressing step, the first circuit member and the second circuit member may be pressurized in opposite directions.

Hereinafter, the circuit connection structure and its manufacturing method will be described as one embodiment of this embodiment using drawings. FIG. 1 is a schematic cross-sectional view showing one embodiment of the structure. The circuit connection structure 100a shown in FIG. 1 includes an opposing circuit member (first circuit member) 20 and a circuit member (second circuit member) 30, and a connection between the circuit member 20 and the circuit member 30 is arranged to connect these circuit members. The circuit connection component 10 of the component. The circuit connection member 10 contains a cured product of the adhesive composition of this embodiment.

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

The circuit member 30 includes a substrate (second substrate) 31 and a circuit electrode (second circuit electrode) 32 arranged on the main surface 31 a of the substrate 31 . An insulating layer (not shown) may be provided on the main surface 31a of the substrate 31 according to circumstances.

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

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

FIG. 2 is a schematic cross-sectional view showing another embodiment of the structure. The circuit connection structure 100b shown in FIG. 2 has the same structure as the circuit connection structure 100a except that the circuit connection member 10 does not contain the conductive 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 without via conductive particles, and are electrically connected.

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

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

<Synthesis of Silane Compound 1> 25 g of 3-isocyanatopropyltriethoxysilane (trade name: KBE9007, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and 2-hydroxyethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd. ) 17 g, dibutyltin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd.) 60 mg (0.1 mol%) were added to methyl ethyl ketone (trade name: 2-butanone, manufactured by Wako Pure Chemical Industries, Ltd. , purity 99%) to prepare the reaction solution in 50 g. The reaction liquid was heated and refluxed for 120 minutes to obtain silane compound 1 represented by the following formula. Furthermore, FT-IR (Fourier transform infrared spectrophotometer) was used to confirm the disappearance of the absorption peak (2270 cm ^-1 ) derived from the isocyanate group (NCO group), thereby confirming the completion of the reaction. An infrared spectrophotometer (manufactured by JASCO Corporation) was used for the measurement of FT-IR. Furthermore, temperature control during heating and reflow is performed using an oil bath (device name: HOB-50D, manufactured by ASONE Co., Ltd.).

[Chemical 11]

<Synthesis of polyurethane> In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, polypropylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., number average molecular weight) which is a diol having an ether bond Mn=2000) 1000 parts by mass and 4000 parts by mass of methyl ethyl ketone (solvent), stirred at 40°C for 30 minutes to prepare a reaction liquid. After the reaction solution was heated to 70°C, 0.0127 parts by mass of dimethyltin laurate (catalyst) was added. Next, a solution prepared by dissolving 125 parts by mass of 4,4'-diphenylmethane diisocyanate in 125 parts by mass of methyl ethyl ketone was added dropwise to the reaction liquid over 1 hour. Thereafter, stirring was continued at the above temperature until the absorption peak (2270 cm ^-1 ) derived from the isocyanate group could not be seen with an infrared spectrophotometer (manufactured by Japan Spectroscopic Co., Ltd.), and the polyurethane was obtained. Methyl ethyl ketone solution. Next, the solvent amount was adjusted so that the solid content concentration (polyurethane concentration) of the solution would become 30 mass %. The weight average molecular weight of the obtained polyurethane was measured by GPC (gel permeation chromatography), and was 320,000 (standard polystyrene conversion value). Table 1 shows the measurement conditions of GPC.

[Table 1]

<Synthesis of acrylic urethane> In a 2 L (liter) four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser, polycarbonate diol (Aldrich ) company, quantity average molecular weight Mw=2000) 4000 parts by mass, 238 parts by mass of 2-hydroxyethyl acrylate, 0.49 parts by mass of hydroquinone monomethyl ether, and 4.9 parts by mass of tin-based catalyst were prepared. To the reaction liquid heated to 70° C., 666 parts by mass of isophorone diisocyanate (IPDI) was uniformly dropped and reacted over 3 hours. After completion of the dropwise addition, the reaction was continued for 15 hours, and the time when NCO% (NCO content) became 0.2 mass % or less was regarded as the end of the reaction, and acrylic urethane was obtained. NCO% can be confirmed with a potential difference automatic titration device (trade name: AT-510, manufactured by Kyoto Electronics Industry Co., Ltd.). The result of GPC analysis is that the weight average molecular weight of acrylic urethane is 8500 (standard polystyrene conversion value). In addition, 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 with a thickness of 0.2 μm was formed on the surface of the polystyrene particles. Furthermore, a gold layer with a thickness of 0.04 μm was formed outside the nickel layer. In this way, conductive particles with an average particle diameter of 4 μm were produced.

<Preparation of film-like adhesive> (Examples 1 to 6 and Comparative Examples 1 to 6) The components shown in Table 2 were mixed at the mass ratio shown in Table 2. The conductive particles were dispersed therein at a ratio of 1.5% by volume (based on the total volume of solid content in the adhesive composition) to obtain a coating liquid (adhesive composition) for producing a film-like adhesive. The coating liquid was coated on a polyethylene terephthalate (PET) film with a thickness of 50 μm using a coating device. The coating film was hot air dried at 70° C. for 10 minutes to prepare a film-like adhesive (film-like adhesive composition) with a thickness of 18 μm. The content of each component of the film adhesive agent shown in Table 2 is the solid content.

"Polyurethane", "silane compound 1" and "acrylic polyurethane" shown in Table 2 are components synthesized as described above. "PKHC" is phenoxy resin (trade name: PKHC, manufactured by Union Carbide, weight average molecular weight: 45,000). PKHC was used in the form of a 40% by mass solution prepared by dissolving 40 g of PKHC in 60 g of methyl ethyl ketone. "KBM503" is 3-methacryloxypropyltrimethoxysilane (trade name: KBM-503, manufactured by Shin-Etsu Chemical Industry Co., Ltd.). "EBECRYL 436" is polyester acrylate (radically polymerizable compound, trade name: EBECRYL 436, manufactured by Daicel-Allnex Co., Ltd.). "M-215" is isocyanuric acid EO modified diacrylate (radical polymerizable compound, trade name: M-215, manufactured by Toa Gosei Co., Ltd.). "P-2M" is 2-methacryloxyethyl phosphate (phosphate ester, trade name: Light ester P-2M, manufactured by Kyeisha Chemical Co., Ltd.). "PEROYL L" is dilauryl peroxide (trade name: PEROYL L, manufactured by NOF Co., Ltd., molecular weight: 398.6, 1-minute half-life temperature: 116°C). "R104" is silica particles (inorganic fine particles, trade name: R104, manufactured by Japan AEROSIL Co., Ltd., primary particle size: 12 nm). R104 was used in the form of a 10 mass% dispersion liquid prepared by dispersing 10 g of R104 in a mixed solvent of 45 g of toluene and 45 g of ethyl acetate.

<Measurement of Average Linear Thermal Expansion Coefficient> A plurality of sheets of the film-like adhesive were prepared. These film-like adhesives were bonded together using a laminator so that the thickness became 100±20 μm, and then processed in an oven at 180° C. for 1 hour to prepare a hardened product sample. The average linear thermal expansion coefficient of the produced sample at 30°C to 90°C was measured with a thermomechanical analysis device (manufactured by Shimadzu Corporation). For a sample with a length of 10 mm and a width of 4 mm, the measurement was carried out under the conditions of a load of 5 gf (in terms of cross-sectional area per 0.4 mm ² ) and a heating rate of 5°C/min. The results are shown in Table 2.

[Table 2]

<Preparation of Connector> Using the film-like adhesive, a flexible circuit board (FPC) having approximately 2,200 copper circuits with a line width of 75 μm, a pitch of 150 μm (a gap of 75 μm), and a thickness of 18 μm was formed. ) is connected (attached) to a glass (SiO ₂ ) substrate (trade name: SLIDE GLASS S7224, manufactured by Matsunami Glass Industry Co., Ltd.). Connection (adhesion) is performed by using a thermocompression bonding device (heating method: constant temperature type, manufactured by Toray Engineering Co., Ltd.) to heat and pressurize at 140°C, 3 MPa, and 5 seconds. This creates a connection body in which the FPC and the glass substrate are connected with a width of 1.5 mm using the hardened product of the film-like adhesive. Calculate the pressurizing pressure by setting the crimping area to 0.495 cm ² .

<Evaluation of Peeling at the Glass Interface> The connection appearance immediately after the preparation of the connection body was observed using an optical microscope, and after the connection body was placed in a constant temperature and humidity chamber of 85°C and 85% RH for 250 hours (high temperature and high humidity) appearance of the connection after testing). The area where peeling occurs at the interface between the glass substrate and the hardened material in the gap portion (peeling area) is measured, and the presence or absence of peeling at the glass interface is evaluated. When the ratio of the peeling area to the entire gap exceeds 30%, it is evaluated that there is peeling, and when the ratio of the peeling area is 30% or less, it is evaluated that there is no peeling. The results are shown in Table 3.

[table 3]

From the above, it was confirmed that in Examples 1 to 6, compared with Comparative Examples 1 to 6, even after high-temperature and high-humidity treatment, there was no peeling of the interface between the glass substrate and the cured product, and good quality was maintained. Appearance.

10‧‧‧Circuit connection member 10a‧‧‧Insulating material 10b‧‧‧Conductive particles 20‧‧‧First circuit member 21‧‧‧First substrate 21a, 31a‧‧‧Main surface 22‧‧‧First circuit Electrode 30‧‧‧Second circuit member 31‧‧‧Second substrate 32‧‧‧Second circuit electrodes 100a, 100b‧‧‧Circuit connection structure

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.

10‧‧‧Circuit connection components

10a‧‧‧Insulating substances

10b‧‧‧Conductive Particles

20‧‧‧First circuit component

21‧‧‧First substrate

21a, 31a‧‧‧Main surface

22‧‧‧First circuit electrode

30‧‧‧Second circuit component

31‧‧‧Second substrate

32‧‧‧Second circuit electrode

100a‧‧‧Circuit connection structure

Claims (7)

An adhesive composition containing: (a) a thermoplastic resin, (b) a silane compound having a urethane bond and an alkoxysilyl group in the molecule, (c) a radically polymerizable compound, and (d) ) radical polymerization initiator, and (c) component contains (e) a compound having a urethane bond, and the content C _b1 of the component (c) having a urethane bond is relative to The mass ratio C _b1 /C _b2 of the content C _b2 of the component (c) having a urethane bond is 1 or more, and the average line of the cured product of the adhesive composition at 30°C to 90°C The thermal expansion coefficient is 800 ppm/K or less, and the content of the component (b) exceeds 5 parts by mass relative to 100 parts by mass of the component (a). The adhesive composition according to claim 1, wherein the component (b) further has at least one selected from the group consisting of (meth)acrylyl and vinyl. The adhesive composition described in Item 1 or 2 of the patent application, wherein the component (e) is selected from the group consisting of polyurethane, polyester urethane and (meth)acrylic acid. At least one of the group consisting of urethanes. The adhesive composition described in claim 1 or 2, wherein the content of component (c) is 20 based on the total mass of solid components in the adhesive composition. Quality% or more. The adhesive composition described in claim 1 or 2 further contains an inorganic filler with a primary particle size of 100 nm or less. A structure including the adhesive composition or a hardened product thereof as described in any one of items 1 to 5 of the patent application. A structure including a first circuit member having a first circuit electrode, a second circuit member having a second circuit electrode, and a circuit connection member disposed between the first circuit member and the second circuit member. , the first circuit electrode and the second circuit electrode are electrically connected, and the circuit connection member includes the adhesive composition or its hardened product as described in any one of items 1 to 5 of the patent application scope. .