WO2017090659A1

WO2017090659A1 - Adhesive composition for circuit connection, and structure

Info

Publication number: WO2017090659A1
Application number: PCT/JP2016/084747
Authority: WO
Inventors: 智樹森尻; 松田　和也; 田中　勝; 立澤　貴; 研吾篠原; 泰典川端
Original assignee: 日立化成株式会社
Priority date: 2015-11-25
Filing date: 2016-11-24
Publication date: 2017-06-01
Also published as: JP6870618B2; CN108291114A; KR102615097B1; TW202402994A; CN118291047A; KR20180084929A; JPWO2017090659A1; TWI836720B; TW201728721A; TW202313896A

Abstract

This adhesive composition for circuit connection contains (A) a radical-polymerizable compound, (B) a radical generator, and (C) particles including at least one type of metal compound selected from the group consisting of metal hydroxides and metal oxides. The metal compound includes at least one element selected from the group consisting of aluminum, magnesium, zirconium, bismuth, calcium, tin, manganese, antimony, silicon, and titanium.

Description

Adhesive composition for circuit connection and structure

The present invention relates to an adhesive composition for circuit connection and a structure using the same.

In recent years, various adhesives have been used in the fields of semiconductors, liquid crystal displays, and the like to fix electronic components or connect circuits. In these applications, higher density or higher definition is required, and high adhesiveness or reliability is required for the adhesive. In particular, circuit connection materials include connection between liquid crystal display and TCP, connection between FPC and TCP, connection between FPC and printed wiring board, connection between semiconductor silicon chip and substrate, connection between FPC and touch panel module, FPC An anisotropic conductive adhesive containing conductive particles is used for connection between the FPC and the FPC.

Conventionally, thermosetting resins (epoxy resin, acrylic resin, etc.) exhibiting high adhesion and high reliability have been used in the adhesive. As a constituent component of an adhesive using an epoxy resin, a latent curing agent that generates an epoxy resin and a cationic species or anionic species having reactivity with the epoxy resin by heat or light is generally used. The latent curing agent is an important factor for determining the curing temperature and the curing rate, and various compounds have been used from the viewpoint of storage stability at normal temperature and curing rate during heating. In the actual process, for example, desired adhesiveness was obtained by curing under a curing condition of a temperature of 170 to 250 ° C. for 10 seconds to 3 hours.

In recent years, with high integration of semiconductor elements and high definition of display elements, the pitch between elements and wirings is narrowed, and there is a possibility that the peripheral members may be adversely affected by heat during curing. Further, in order to reduce the cost, it is necessary to improve the throughput, and adhesion at a low temperature (90 to 170 ° C.) and in a short time (within 1 hour, preferably within 40 seconds, more preferably within 20 seconds) In other words, adhesion by low temperature short time curing (low temperature rapid curing) is required. In order to achieve this low-temperature and short-time curing, it is necessary to use a thermal latent catalyst with low activation energy, but it is known that it is very difficult to combine storage stability near normal temperature. .

Therefore, in recent years, a radical curing adhesive (for example, a radical curing adhesive using a (meth) acrylate derivative and a peroxide as a radical polymerization initiator) has attracted attention. The radical curing system is capable of curing for a short time because radicals that are reactive species are very reactive, and the adhesive is stable below the decomposition temperature of the radical polymerization initiator. It is a curing system that achieves both short-time curing and storage stability (for example, storage stability near normal temperature). In addition, radical curing systems do not use ionic polymerization such as epoxy curing systems such as cation-epoxy curing systems and anion-epoxy curing systems. It is characterized by excellent corrosion resistance when performed. On the other hand, in a cation-epoxy curable adhesive or an anion-epoxy curable adhesive, the corrosion may be suppressed by adding a metal hydroxide, a metal oxide or the like (for example, see Patent Documents 1 to 4 below). ).

JP 2006-199778 A JP 2012-46756 A JP 2012-46757 A JP 2012-41544 A International Publication No. 2009/063827

In recent years, wearable terminals (terminals to be worn) and display terminals (smartphones, tablets, smart watches, etc.) having high durability as an added value are increasing. For circuit connection materials for the components of these terminals, it is excellent even when the structure obtained using the circuit connection material is exposed to salt water, assuming salt water such as sweat and seawater. Connection reliability, that is, excellent salt water resistance (resistance to salt water).

An object of the present invention is to provide an adhesive composition for circuit connection capable of obtaining a structure having excellent salt water resistance, and a structure using the same.

The present invention contains (A) a radical polymerizable compound, (B) a radical generator, and (C) particles containing at least one metal compound selected from the group consisting of metal hydroxides and metal oxides. In addition, the present invention relates to an adhesive composition for circuit connection, wherein the metal compound contains at least one selected from the group consisting of aluminum, magnesium, zirconium, bismuth, calcium, tin, manganese, antimony, silicon and titanium.

According to the adhesive composition for circuit connection according to the present invention, it is possible to obtain a structure having excellent salt water resistance (excellent connection reliability even when exposed to salt water (sweat, seawater, etc.)). it can. Therefore, excellent reliability can be obtained even in severe environments such as wearable applications. Moreover, according to the adhesive composition for circuit connection which concerns on this invention, a low temperature short time connection can also be achieved. Therefore, it is possible to use an adherend made of a material having low heat resistance such as polyethylene terephthalate (PET) or polycarbonate (PC), so that the options for the adherend can be expanded.

As a method for evaluating salt water resistance (resistance to salt water), JIS Z 2371 (2000 salt spray test method); ISO 9227 (2006 Corrosion tests in artificial atmospheres-Salt spray tests.); A method of putting it in a high-temperature and high-humidity tank after soaking in salt water is performed. As a result of the verification by the present inventors, for the structure obtained by connecting with the adhesive composition for circuit connection, when performing the test relating to salt water resistance, the radical curing system adhesive composition for circuit connection is: It was found that the salt water resistance was lower than that of the cation-epoxy curable or anion-epoxy curable adhesive composition for circuit connection. Since the radical curing type adhesive composition for circuit connection is low in polarity and the adhesiveness at the interface between the adherend (substrate etc.) and the adhesive composition is low, the ionic component in the salt water is easily present at the interface. It is thought that invasion and adhesion inhibition occur. For example, when a polymer of a radical polymerizable compound has a carbon-carbon bond (C—C) as a main skeleton, the polarity tends to be low. In particular, when the adherend has an insulating material portion containing an insulating material such as SiO ₂ or SiN _x , the insulating material portion has a large number of hydroxyl groups on the surface and is easily wetted with water (such as salt water). On the other hand, since it is difficult to get wet with the radical-curing adhesive composition for circuit connection, adhesion inhibition is likely to occur, and the reliability of the structure is significantly reduced.

As a result of intensive studies, the present inventors have found that in a radical-curing adhesive composition for circuit connection, by using particles containing a metal hydroxide or metal oxide containing a specific metal element, It has been found that the salt water resistance of can be significantly improved. This is because the metal hydroxide or metal oxide increases the polarity of the adhesive composition itself, and the metal hydroxide or metal oxide captures ionic components that cause adhesion inhibition, thereby suppressing adhesion inhibition. This is considered to be a factor.

The component (C) may contain the metal hydroxide. The average primary particle size of the component (C) is preferably 10 μm or less.

The adhesive composition for circuit connection according to the present invention may further contain a silane coupling agent. The adhesive composition for circuit connection according to the present invention may further contain conductive particles.

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

The structure of the present invention includes a first circuit member having a first circuit electrode, a second circuit member having a second circuit electrode, and between the first circuit member and the second circuit member. And 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. An aspect may be sufficient.

According to the present invention, it is possible to provide an adhesive composition for circuit connection capable of obtaining a structure having excellent salt water resistance, and a structure using the same.

According to the present invention, an application of an adhesive composition or a cured product thereof to a structure (circuit connection structure or the like) or production thereof can be provided. ADVANTAGE OF THE INVENTION According to this invention, the application of the adhesive composition or its hardened | cured material can be provided for circuit connection. ADVANTAGE OF THE INVENTION According to this invention, the application of the structure to a wearable use can be provided.

It is a schematic cross section which shows one Embodiment of the structure of this invention. It is a schematic cross section which shows other one Embodiment of the structure of this invention.

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

In the present specification, “(meth) acrylate” means at least one of acrylate and methacrylate corresponding thereto. The same applies to other similar expressions such as “(meth) acryloyl” and “(meth) acrylic acid”. The materials exemplified below may be used alone or in combination of two or more unless otherwise specified. The content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. The numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. “A or B” only needs to include either A or B, and may include both. “Normal temperature” means 25 ° C.

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

<Adhesive composition>
The adhesive composition of the present embodiment comprises (A) a radical polymerizable compound (radical polymerizable substance, radical reactive component), (B) a radical generator, and (C) a metal hydroxide and a metal oxide. An adhesive composition for circuit connection, comprising particles containing at least one metal compound selected from the group consisting of: Hereinafter, each component will be described.

(Radically polymerizable compound)
The radical polymerizable compound is a compound having a radical polymerizable functional group. Examples of such radically polymerizable compounds include (meth) acrylate compounds, maleimide compounds, citraconimide compounds, nadiimide compounds, and the like. “(Meth) acrylate compound” means a compound having a (meth) acryloyl group. A radically polymerizable compound may be used in the state of a monomer or an oligomer, and can also use a monomer and an oligomer together. A radically polymerizable compound may be used individually by 1 type, and may be used in combination of 2 or more type.

Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, Trimethylolpropane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, 2-hydroxy-1,3-di (meth) acryloxypropane, 2,2-bis [4-((meth) acryloxymethoxy) Phenyl] propane, 2,2-bis [4-((meth) acryloxypolyethoxy) phenyl] propane, dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, tris ((meth) acryloyloxy Chill) isocyanurate, isocyanuric acid EO-modified di (meth) acrylate, isocyanuric acid EO-modified tri (meth) acrylate, urethane (meth) acrylate. As radically polymerizable compounds other than (meth) acrylate compounds, for example, compounds described in Patent Document 5 (International Publication No. 2009/063827) can be preferably used. A (meth) acrylate compound may be used individually by 1 type, and may be used in combination of 2 or more type.

As the radical polymerizable compound, a (meth) acrylate compound is preferable and urethane (meth) acrylate is more preferable from the viewpoint of obtaining further excellent salt water resistance. From the viewpoint of improving heat resistance, the (meth) acrylate compound preferably has at least one substituent selected from the group consisting of a dicyclopentenyl group, a tricyclodecanyl group, and a triazine ring.

Further, as the radical polymerizable compound, a radical polymerizable compound having a phosphate structure represented by the following general formula (I) is preferably used, and the radical polymerizable compound such as a (meth) acrylate compound and the formula ( It is more preferable to use together with a radically polymerizable compound having a phosphate ester structure represented by I). In these cases, since the adhesive strength with respect to the surface of an inorganic substance (metal etc.) improves, it is suitable for adhesion | attachment of circuit electrodes, for example.

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

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

The content of the radical polymerizable compound having a phosphate ester structure represented by the formula (I) is a radical polymerizable compound (total amount of components corresponding to the radical polymerizable compound. From the viewpoint of obtaining further excellent salt water resistance. Similarly) 20 mass parts or less are preferable with respect to 100 mass parts, and 10 mass parts or less are more preferable. The content of the radically polymerizable compound having a phosphate ester structure represented by the formula (I) is such that the radically polymerizable compound and the film-forming material (components used as necessary) are from the viewpoint of obtaining excellent salt water resistance. 20 mass parts or less are preferable with respect to a total of 100 mass parts, and 10 mass parts or less are more preferable.

The radical 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 with respect to 100 parts by mass in total of the radical polymerizable compound and the film forming material (components used as necessary). 5 to 5 parts by mass is more preferable.

The content of the radical polymerizable compound is based on the total mass of the adhesive component of the adhesive composition (solid content other than the conductive particles in the adhesive composition; the same applies hereinafter) from the viewpoint of obtaining further excellent salt water resistance. The following ranges are preferred. The content of the radical polymerizable compound is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more. The content of the radical polymerizable compound is preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less. From these viewpoints, the content of the radical polymerizable compound is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 30 to 70% by mass.

(Radical generator)
The radical generator is a curing agent (radical polymerization initiator or the like) that generates free radicals by being decomposed by heat, light (UV, etc.), ultrasonic waves, electromagnetic waves, or the like.

Examples of the radical generator include peroxides (such as organic peroxides) and azo compounds. The radical generator is appropriately selected depending on the intended connection temperature, connection time, pot life, and the like. The 10 minute half-life temperature of the radical generator is preferably 40 ° C. or higher, more preferably 60 ° C. or higher, from the viewpoint of high reactivity and pot life improvement. The 1 minute half-life temperature of the radical generator is preferably 180 ° C. or lower, more preferably 170 ° C. or lower, from the viewpoint of high reactivity and improvement of pot life. The radical generator is preferably an organic peroxide having a 10-minute half-life temperature of 40 ° C. or higher and a 1-minute half-life temperature of 180 ° C. or lower from the viewpoint of high reactivity and pot life, and a 10-minute half-life. An organic peroxide having a temperature of 60 ° C. or higher and a 1 minute half-life temperature of 170 ° C. or lower is more preferable.

Specific examples of peroxides that are curing agents that generate free radicals when heated include diacyl peroxides (benzoyl peroxide, etc.), peroxydicarbonates, peroxyesters, peroxyketals, dialkyl peroxides, hydroperoxides And silyl peroxide.

As the radical generator, from the viewpoint of suppressing corrosion of electrodes (circuit electrodes, etc.), a curing agent having a concentration of contained chlorine ions and organic acids of 5000 ppm or less is preferable, and a curing agent that generates less organic acids after thermal decomposition. Is more preferable. Specific examples of such curing agents include diacyl peroxides, peroxydicarbonates, peroxyesters, dialkyl peroxides, hydroperoxides, silyl peroxides, and the like from the viewpoint of obtaining high reactivity. At least one selected from the group consisting of peroxide, peroxydicarbonate and peroxyester is preferred. Curing agents that generate free radicals by heat may be used singly or in combination of two or more.

Peroxyesters include cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, and t-hexyl. Peroxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2- Ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate Ate, t-butylperoxyisobutyrate, 1,1-bis (t-butylperoxy) cyclohexane t-hexylperoxyisopropyl monocarbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (m-toluoyl) Peroxy) hexane, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, t-butyl peroxyacetate and the like. A peroxy ester may be used individually by 1 type, and may be used in combination of 2 or more type. As the curing agent that generates free radicals by heat other than the peroxyester, for example, the compounds described in Patent Document 5 (International Publication No. 2009/063827) can be suitably used.

Examples of azo compounds which are curing agents that generate free radicals by heat include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis. (Cyclohexane-1-carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2 ′ -Azobis (2-methylpropionate), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-hydroxymethylpropionitrile), 2,2'-azobis [2 -(Imidazolin-2-yl) propane] and the like.

As the curing agent that generates free radicals by light, a compound that generates radicals by light having a wavelength of 150 to 750 nm can be used. As such compounds, Photoinitiation, Photopolymerization, and Photocuring, J.A. -P. Α-Acetaminophenone derivatives and phosphine oxide derivatives described in Fouassier, Hanser Publishers (1995), p17 to p35 are preferred. Curing agents that generate free radicals by light may be used singly or in combination of two or more.

The radical generator may be used alone or in combination of two or more. A curing agent that generates free radicals by heat (peroxide, azo compound, etc.) and a curing agent that generates free radicals by light may be used in combination. You may use together a radical generator, a decomposition accelerator, a decomposition inhibitor, etc. Alternatively, the radical generator may be microencapsulated by coating with a polyurethane-based or polyester-based polymer substance or the like. A microencapsulated curing agent is preferred because the pot life is extended.

The content of the radical generator is preferably in the following range from the viewpoint that a sufficient reaction rate can be easily obtained when the connection time is 25 seconds or less. The content of the radical generator is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more with respect to 100 parts by mass of the radical polymerizable compound, and 1 part by mass or more. More preferably. The content of the radical generator is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 20 parts by mass or less with respect to 100 parts by mass of the radical polymerizable compound. . From these viewpoints, the content of the radical generator is preferably 0.1 to 40 parts by mass, more preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the radical polymerizable compound. More preferably, it is 1 to 30 parts by mass.

The content of the radical generator is preferably in the following range from the viewpoint that a sufficient reaction rate can be easily obtained when the connection time is 25 seconds or less. The content of the radical generator is preferably 0.1 parts by mass or more with respect to 100 parts by mass in total of the radical polymerizable compound and the film forming material (components used as necessary), and 0.5 parts by mass. More preferably, it is more preferably 1 part by mass or more. The content of the radical generator is preferably 40 parts by mass or less, and 30 parts by mass or less, with respect to 100 parts by mass in total of the radical polymerizable compound and the film forming material (components used as necessary). Is more preferable, and it is still more preferable that it is 20 mass parts or less. From these viewpoints, the content of the radical generator is preferably 0.1 to 40 parts by mass with respect to 100 parts by mass in total of the radical polymerizable compound and the film forming material (components used as necessary). 0.5 to 30 parts by mass is more preferable, and 1 to 20 parts by mass is even more preferable.

The content of the radical generator in the case where the connection time is not limited is preferably in the following range from the viewpoint that a sufficient reaction rate can be easily obtained. The content of the radical generator is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more with respect to 100 parts by mass of the radical polymerizable compound, and 1 part by mass or more. More preferably. The content of the radical generator is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 15 parts by mass or less with respect to 100 parts by mass of the radical polymerizable compound. . From these viewpoints, the content of the radical generator is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the radical polymerizable compound. More preferably, it is 1 to 15 parts by mass.

The content of the radical generator in the case where the connection time is not limited is preferably in the following range from the viewpoint that a sufficient reaction rate can be easily obtained. The content of the radical generator is preferably 0.1 parts by mass or more with respect to 100 parts by mass in total of the radical polymerizable compound and the film forming material (components used as necessary), and 0.5 parts by mass. More preferably, it is more preferably 1 part by mass or more. The content of the radical generator is preferably 30 parts by mass or less, and 20 parts by mass or less, with respect to 100 parts by mass in total of the radical polymerizable compound and the film-forming material (components used as necessary). Is more preferably 15 parts by mass or less. From these viewpoints, the content of the radical generator is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass in total of the radical polymerizable compound and the film forming material (components used as necessary). 0.5 to 20 parts by mass is more preferable, and 1 to 15 parts by mass is even more preferable.

(Particles containing metal hydroxide or metal oxide)
The adhesive composition of this embodiment contains particles (hereinafter sometimes referred to as “component (C)”) containing at least one metal compound selected from the group consisting of metal hydroxides and metal oxides. The component (C) may contain a metal hydroxide or a metal oxide. The metal compound includes at least one selected from the group consisting of aluminum, magnesium, zirconium, bismuth, calcium, tin, manganese, antimony, silicon, and titanium as a metal hydroxide or a metal element constituting the metal oxide.

The metal hydroxide is preferably at least one selected from the group consisting of aluminum hydroxide, magnesium hydroxide and calcium hydroxide from the viewpoint of obtaining further excellent salt water resistance. The oxide is preferably at least one selected from the group consisting of silicon oxide, aluminum oxide, magnesium oxide, antimony oxide, tin oxide, titanium oxide, manganese oxide, and zirconium oxide, from the viewpoint of obtaining superior salt water resistance. . (C) A component may be used individually by 1 type and may be used in combination of 2 or more type. You may use together the particle | grains containing a metal hydroxide, and the particle | grains containing a metal oxide.

The average primary particle size of the component (C) is the viewpoint of obtaining excellent dispersibility in the adhesive composition and high adhesion to the adherend, the viewpoint of preventing the adherend from being corroded, and the capture of the ionic component. From the viewpoint of obtaining performance, and from the viewpoint of suppressing short circuit due to large particles (short circuit when the component (C) becomes a foreign substance), it is preferably 10 μm or less, more preferably 5 μm or less, and 1 μm or less. More preferably it is. The effect of obtaining high adhesion to the adherend due to the increase in the specific surface area of the entire component (C) in the adhesive composition by reducing the average primary particle size of the component (C), corrosion of the adherend It is considered that the effect of preventing the ionic component and the effect of obtaining the ion component capturing ability can be obtained. The average primary particle size of the component (C) may be 0.5 μm or more, or 1 μm or more. The average primary particle size of the component (C) can be measured by, for example, a scanning electron microscope.

The content of the component (C) is preferably in the following range based on the total mass of the adhesive component of the adhesive composition. The content of the component (C) is preferably 0.1% by mass or more, more preferably 1% by mass or more, and more preferably 2% by mass or more from the viewpoint of obtaining further excellent saltwater resistance. More preferably, it is 3% by mass or more, particularly preferably 4% by mass or more. The content of the component (C) is preferably 50% by mass or less, and preferably 10% by mass or less from the viewpoint that short circuiting caused by aggregated particles is easily suppressed by obtaining excellent dispersibility. More preferred is 5% by mass or less. From these viewpoints, the content of the component (C) is preferably 0.1 to 50% by mass, more preferably 1 to 50% by mass, and still more preferably 2 to 10% by mass. It is particularly preferably 3 to 10% by mass, and very preferably 4 to 5% by mass.

The content of the component (C) is preferably in the following range with respect to 100 parts by mass of the radical polymerizable compound. The content of the component (C) is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and more preferably 2 parts by mass or more from the viewpoint of obtaining further excellent salt water resistance. More preferably, it is 3 parts by mass or more, particularly preferably 4 parts by mass or more, very preferably 5 parts by mass or more, and even more preferably 7 parts by mass or more. The content of the component (C) is preferably 200 parts by mass or less and preferably 100 parts by mass or less from the viewpoint of easily suppressing short circuit due to the aggregated particles by obtaining excellent dispersibility. More preferably, it is more preferably 50 parts by mass or less, particularly preferably 30 parts by mass or less, particularly preferably 20 parts by mass or less, and very preferably 10 parts by mass or less. From these viewpoints, the content of component (C) is preferably 0.1 to 200 parts by mass, more preferably 1 to 200 parts by mass, and even more preferably 2 to 100 parts by mass. It is particularly preferably 3 to 50 parts by weight, very preferably 4 to 30 parts by weight, very preferably 5 to 20 parts by weight, and even more preferably 7 to 10 parts by weight. .

(Silane coupling agent)
The adhesive composition of this embodiment may contain a silane coupling agent. By using a silane coupling agent, the adhesive force of the adhesive composition (adhesive force to glass, etc.) can be increased. Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3- (meth) acryloxypropylmethyldimethoxy. Silane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, N-2- (aminoethyl) -3- Aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and condensates thereof And the like.

The content of the silane coupling agent is preferably 0.1 to 10% by mass, more preferably 0.25 to 5% by mass, based on the total mass of the adhesive component of the adhesive composition. If content of a silane coupling agent is 0.1 mass% or more, there exists a tendency for the effect which suppresses generation | occurrence | production of the peeling bubble of the interface of a circuit member and a circuit connection material to become still larger. There exists a tendency for the pot life of an adhesive composition to become long that content of a silane coupling agent is 10 mass% or less.

(Film forming material)
The adhesive composition of the present embodiment may contain a film forming material as necessary. Film-forming material improves the handling of the film under normal conditions (normal temperature and normal pressure) when the liquid adhesive composition is solidified into a film, and is difficult to tear, hard to break, and sticky Can be imparted to the film. Examples of the film forming material include phenoxy resin, polyvinyl formal, polystyrene, polyvinyl butyral, polyester, polyamide, xylene resin, and polyurethane. Among these, a phenoxy resin is preferable from the viewpoint of excellent adhesiveness, compatibility, heat resistance, and mechanical strength. A film forming material may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the phenoxy resin include a resin obtained by polyaddition of a bifunctional epoxy resin and a bifunctional phenol, and a resin obtained by reacting the bifunctional phenol and epihalohydrin until they are polymerized. Can be mentioned. For example, the phenoxy resin contains 1 mol of a bifunctional phenol and 0.985 to 1.015 mol of epihalohydrin in the presence of a catalyst such as an alkali metal hydroxide at a temperature of 40 to 120 ° C. in a non-reactive solvent. It can be obtained by reacting. As the phenoxy resin, from the viewpoint of excellent mechanical properties and thermal properties of the resin, in particular, the blending equivalent ratio of the bifunctional epoxy resin and the bifunctional phenol is epoxy group / phenol hydroxyl group = 1 / 0.9˜ An organic solvent (amide type, ether type, ketone type, lactone type, alcohol type) having a boiling point of 120 ° C. or higher in the presence of a catalyst such as an alkali metal compound, an organic phosphorus type compound, a cyclic amine type compound, etc. Etc.), a resin obtained by heating to 50 to 200 ° C. under a condition that the reaction solid content is 50% by mass or less and performing a polyaddition reaction is preferable. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

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

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

(Conductive particles)
The adhesive composition of this embodiment may further contain conductive particles. Examples of the constituent material of the conductive particles include gold (Au), silver (Ag), nickel (Ni), copper (Cu), metals such as solder, carbon, and the like. Alternatively, coated conductive particles in which a nonconductive resin, glass, ceramic, plastic, or the like is used as a core and the metal (metal particles or the like) or carbon is coated on the core may be used. Covered conductive particles (for example, conductive particles with plastic as the core) or hot-melt metal particles are deformable by heating and pressurization, so the circuit electrode height variation is eliminated during connection, and the contact area with the electrode during connection Since the reliability increases, it is preferable.

The average particle diameter of the conductive particles is preferably 1 to 30 μm from the viewpoint of excellent dispersibility and conductivity. The average particle diameter of the conductive particles can be measured using instrumental analysis such as laser diffraction. The content of the conductive particles is preferably 0.1 parts by mass or more and more preferably 1 part by mass or more with respect to 100 parts by mass of the adhesive component of the adhesive composition from the viewpoint of excellent conductivity. The content of the conductive particles is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, with respect to 100 parts by mass of the adhesive component of the adhesive composition, from the viewpoint of easily suppressing the short circuit of the electrode (circuit electrode or the like). preferable. From these viewpoints, the content of the conductive particles is preferably 0.1 to 100 parts by mass, and more preferably 1 to 50 parts by mass.

(Other ingredients)
The adhesive composition of this embodiment may contain a polymerization inhibitor such as hydroquinone and methyl ether hydroquinone as needed.

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

The adhesive composition of the present embodiment may contain coated fine particles obtained by coating the surfaces of the conductive particles with a polymer resin or the like. When such coated fine particles are used in combination with the conductive particles, even if the content of the conductive particles is increased, it is easy to suppress short circuit due to contact between the conductive particles, so that insulation between adjacent circuit electrodes Can be improved. The coated fine particles may be used alone without using conductive particles, or the coated fine particles and conductive particles may be used in combination.

The adhesive composition of the present embodiment comprises rubber fine particles, a filler (excluding the component (C)), a softener, an accelerator, an anti-aging agent, a colorant, a flame retardant, a thixotropic agent, a coupling agent, A phenol resin, a melamine resin, isocyanates, etc. can also be contained. The adhesive composition of the present embodiment may appropriately contain additives such as an adhesion improver (excluding a coupling agent), a thickener, a leveling agent, a colorant, and a weather resistance improver.

The rubber fine particles have an average particle size not more than twice the average particle size of the conductive particles, and the storage elastic modulus at normal temperature is 1/2 of the storage elastic modulus at normal temperature of the conductive particles and the adhesive composition. The following particles are preferred. In particular, when the material of the rubber fine particles is silicone, acrylic emulsion, SBR, NBR or polybutadiene rubber, the rubber fine particles are preferably used alone or in admixture of two or more. The three-dimensionally cross-linked rubber fine particles have excellent solvent resistance and are easily dispersed in the adhesive composition.

The filler can improve the electrical characteristics (connection reliability, etc.) between the circuit electrodes. As the filler, for example, particles having an average particle size of 1/2 or less of the average particle size of the conductive particles can be suitably used. When particles having no conductivity are used in combination with a filler, particles having an average particle size not more than the particles having no conductivity can be used as the filler. The content of the filler is preferably 5 to 60% by mass based on the total mass of the adhesive component of the adhesive composition. When the content is 60% by mass or less, the effect of improving connection reliability tends to be obtained more sufficiently. When the content is 5% by mass or more, the effect of adding the filler tends to be sufficiently obtained.

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

The adhesive composition of the present embodiment may be in the form of a film. If necessary, a solution of an adhesive composition containing a solvent or the like is applied onto a fluororesin film, a polyethylene terephthalate film, a peelable substrate (release paper, etc.), and then the solvent is removed to remove the solvent. An adhesive composition can be obtained. Moreover, after making a base material, such as a nonwoven fabric, impregnate the above solution and placing it on a peelable base material, a film-like adhesive composition can be obtained by removing the solvent and the like. Use of the adhesive composition in the form of a film is more convenient from the viewpoint of excellent handleability. The thickness of the film adhesive composition may be 1 to 100 μm or 5 to 50 μm.

The adhesive composition of the present embodiment can be adhered by, for example, applying pressure together with heating or light irradiation. By using heating and light irradiation in combination, it can be bonded at a lower temperature in a shorter time. The light irradiation is preferably performed in the wavelength region of 150 to 750 nm. As the light source, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp (extra-high-pressure mercury lamp, etc.), a xenon lamp, a metal halide lamp, or the like can be used. The irradiation dose may be 0.1-10 J / cm ² . The heating temperature is not particularly limited, but a temperature of 50 to 170 ° C. is preferable. The pressure is not particularly limited as long as it does not damage the adherend, but is preferably 0.1 to 10 MPa. Heating and pressurization are preferably performed in the range of 0.5 seconds to 3 hours.

The adhesive composition of the present embodiment may be used as an adhesive for the same type of adherend, or as an adhesive for different types of adherends having different thermal expansion coefficients. Specifically, it is used as a circuit connecting material represented by anisotropic conductive adhesive, silver paste, silver film, etc .; semiconductor device adhesive material represented by CSP elastomer, CSP underfill material, LOC tape, etc. be able to.

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

The structure manufacturing method of the present embodiment includes a step of curing the adhesive composition of the present embodiment. As one aspect of the structure manufacturing method of the present embodiment, the circuit connection structure manufacturing method includes a first circuit member having a first circuit electrode, and a second circuit member having a second circuit electrode. Between the step of arranging the adhesive composition of the present embodiment, and pressurizing the first circuit member and the second circuit member to electrically connect the first circuit electrode and the second circuit electrode. And a heating and pressing step of heating and curing the adhesive composition. In the arranging step, the first circuit electrode and the second circuit electrode can be arranged to face each other. In the heating and pressurizing step, the first circuit member and the second circuit member can be pressurized in the opposite directions. In the manufacturing method of the structure of the present embodiment, the adhesive composition of the present embodiment is interposed between the circuit electrodes of the semiconductor elements facing each other and the circuit electrodes of the semiconductor mounting substrate, and the circuit electrodes facing each other are added. A mode in which the electrodes in the pressurizing direction are electrically connected by pressing is also possible.

Hereinafter, a circuit connection structure and a manufacturing method thereof will be described as an aspect of the present embodiment with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an embodiment of a structure. A circuit connection structure 100 a shown in FIG. 1 includes a circuit member (first circuit member) 20 and a circuit member (second circuit member) 30 that are opposed to each other, and between the circuit member 20 and the circuit member 30. The circuit connection member 10 which connects these is arrange | positioned. The circuit connection member 10 includes a cured product of the adhesive composition of the present embodiment.

The circuit member 20 includes a substrate (first substrate) 21 and a circuit electrode (first circuit electrode) 22 disposed on the main surface 21 a of the substrate 21. An insulating layer (not shown) may be disposed 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 a circuit electrode (second circuit electrode) 32 disposed on the main surface 31 a of the substrate 31. An insulating layer (not shown) may be disposed on the main surface 31a of the substrate 31 in some cases.

The circuit connecting member 10 contains an insulating substance (cured product of components excluding conductive particles) 10a and conductive particles 10b. The conductive particles 10b are disposed at least between the circuit electrode 22 and the circuit electrode 32 facing each other. In the circuit connection structure 100a, the circuit electrode 22 and the circuit electrode 32 are electrically connected via the conductive particles 10b.

The

circuit members

20 and 30 have one or a plurality of circuit electrodes (connection terminals). As the

circuit members

20 and 30, for example, members having electrodes that require electrical connection can be used. As the circuit member, a chip component such as a semiconductor chip (IC chip), a resistor chip, or a capacitor chip; a substrate such as a printed board or a semiconductor mounting board can be used. Examples of the combination of the

circuit members

20 and 30 include a semiconductor chip and a semiconductor mounting substrate. Examples of the material of the substrate include inorganic substances such as semiconductor, glass, and ceramic; organic substances such as polyimide, polyethylene terephthalate, polycarbonate, (meth) acrylic resin, and cyclic olefin resin; and composites of glass and epoxy. The substrate may be a plastic substrate.

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

The

circuit connection structures

100a and 100b can be manufactured, for example, by the following method. First, when the adhesive composition is in a paste form, the resin layer containing the adhesive composition is disposed on the circuit member 20 by applying and drying the adhesive composition. When the adhesive composition is in the form of a film, the resin layer containing the adhesive composition is disposed on the circuit member 20 by sticking the film-like adhesive composition to the circuit member 20. Subsequently, the circuit member 30 is placed on the resin layer disposed on the circuit member 20 so that the circuit electrode 22 and the circuit electrode 32 are opposed to each other. And a heat treatment or light irradiation is performed to the resin layer containing an adhesive composition, an adhesive composition hardens | cures and hardened | cured material (circuit connection member 10) is obtained. Thus,

circuit connection structures

100a and 100b are obtained.

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

<Production of film-like circuit connection material>
Example 1
50 g of phenoxy resin (trade name: PKHC, manufactured by Union Carbide Co., Ltd., weight average molecular weight 45000) is dissolved in a mixed solvent of toluene / ethyl acetate (mass ratio: 50/50) to obtain a phenoxy resin having a solid content of 40% by mass. A solution was prepared. As radical polymerizable compounds, isocyanuric acid EO-modified diacrylate (trade name: M-215, manufactured by Toa Gosei Co., Ltd.), 2-methacryloyloxyethyl acid phosphate (phosphate ester, trade name: light ester P-2M, Kyoeisha) Chemical Co., Ltd.) and urethane acrylate (trade name: U-2PPA, Shin-Nakamura Chemical Co., Ltd.) were used. As a silane coupling agent, 3-methacryloxypropyltrimethoxysilane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.) was prepared. Benzoyl peroxide (trade name: Nyper BMT-K40, manufactured by NOF Corporation, 1 minute half-life temperature: 131.1 ° C., 10 minute half-life temperature: 73 ° C.) was prepared as a radical generator. As component (C), aluminum hydroxide (Al (OH) ₃ ) particles having an average primary particle size of 1 μm were prepared.

50 g / 27 g / 5 g / 20 g of phenoxy resin / isocyanuric acid EO-modified diacrylate / 2-methacryloyloxyethyl acid phosphate / urethane acrylate / silane coupling agent / radical generator / (C) component The mixture was mixed at a ratio of / 3 g / 3 g / 5 g to prepare an adhesive composition-containing liquid A. Furthermore, conductive particles having an average particle diameter of 5 μm and a specific gravity of 2.5 having a nickel layer having a thickness of 0.2 μm on the surface of polystyrene particles (nuclei) were prepared. 5 parts by mass of conductive particles were dispersed in 100 parts by mass of the adhesive composition-containing liquid A to prepare a circuit connection material-containing liquid.

Using a coating apparatus, the circuit connection material-containing liquid is applied on a PET film having a thickness of 50 μm, which is surface-treated on one side, and then dried with hot air at 70 ° C. for 3 minutes, thereby forming a film having a thickness of 20 μm on the PET film. The circuit connection material was obtained.

(Example 2)
A film-like circuit connection material was produced in the same manner as in Example 1 except that the component (C) was changed to magnesium hydroxide (Mg (OH) ₃ ) particles having an average primary particle size of 1 μm.

(Example 3)
A film-like circuit connection material was produced in the same manner as in Example 1 except that the component (C) was changed to magnesium oxide (Mg ₂ O ₃ ) particles having an average primary particle size of 1 μm.

Example 4
A film-like circuit connection material was produced in the same manner as in Example 1 except that the component (C) was changed to zirconium oxide (ZrO ₂ ) particles having an average primary particle size of 1 μm.

(Comparative Example 1)
A film-like circuit connection material was produced in the same manner as in Example 1 except that the component (C) was not used.

<Peeling evaluation (evaluation of salt spray test)>
A flexible circuit board (FPC) having 500 copper circuits having a line width of 75 μm, a pitch of 150 μm, and a thickness of 18 μm, and a silicon nitride (SiN _x ) having a thickness of 0.5 μm through the film-like circuit connecting material obtained by the above-described manufacturing method A glass plate (thickness 0.7 mm) on which a thin layer was formed was heated and pressurized at 170 ° C. and 3 MPa for 20 seconds using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.). And connected over a width of 2 mm to produce a circuit connection structure. Using a salt spray tester (manufactured by Suga Test Instruments Co., Ltd.), a salt spray test was performed on the circuit connection structure in accordance with JIS Z 2371 for 24 hours. The appearance of the connection part before and after the test was observed and the presence or absence of peeling was evaluated. The case where peeling was not observed was evaluated as “A”, and the case where peeling was observed was evaluated as “B”. The evaluation results are shown in Table 1.

From the above, it is confirmed that the adhesiveness (salt water resistance) to the surface of the adherend (inorganic substrate) can be favorably maintained even after spraying with salt water in the example in comparison with the comparative example. Moreover, in an Example, it is confirmed that adhesiveness (salt water tolerance) can be maintained favorable, achieving a low-temperature short-time connection.

DESCRIPTION OF SYMBOLS 10 ... Circuit connection member, 10a ... Insulating substance, 10b ... Conductive particle, 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

(A) a radical polymerizable compound, (B) a radical generator, and (C) particles containing at least one metal compound selected from the group consisting of metal hydroxides and metal oxides,
An adhesive composition for circuit connection, wherein the metal compound contains at least one selected from the group consisting of aluminum, magnesium, zirconium, bismuth, calcium, tin, manganese, antimony, silicon, and titanium.
The adhesive composition for circuit connection according to claim 1, wherein the component (C) contains the metal hydroxide.
The adhesive composition for circuit connection according to claim 1 or 2, wherein the average primary particle size of the component (C) is 10 µm or less.
The adhesive composition for circuit connection according to any one of claims 1 to 3, further comprising a silane coupling agent.
The adhesive composition for circuit connection according to any one of claims 1 to 4, further comprising conductive particles.
A structure comprising the adhesive composition for circuit connection according to any one of claims 1 to 5 or a cured product thereof.
A first circuit member having a first circuit electrode;
A second circuit member having a second circuit electrode;
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;
A structure in which the circuit connecting member comprises the adhesive composition for circuit connection according to any one of claims 1 to 5 or a cured product thereof.