JP5140996B2 - Adhesive composition, circuit connection material, circuit member connection structure, and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive composition which allows a fairly rapid curing at a low temperature and stably yields properties such as bonding strength and connection resistance and a circuit connection material, a connection structure of circuit members and a semiconductor device using the adhesive composition. <P>SOLUTION: The adhesive composition comprises a compound having a carbon-carbon double bond in the molecule, a compound having not less than 2 mercapto groups in the molecule and a radical polymerization initiator. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to an adhesive composition, a circuit connection material, a circuit member connection structure, and a semiconductor device.

  In the semiconductor element and the liquid crystal display element, various adhesives are conventionally used for the purpose of bonding various members in the element. The properties required for adhesives are diverse, including adhesiveness, heat resistance, reliability in high temperature and high humidity conditions, and the like.

  Conventionally, as an adhesive for a semiconductor element or a liquid crystal display element, a thermosetting resin such as an epoxy resin having excellent adhesiveness and particularly excellent adhesiveness even under high temperature and high humidity conditions has been used (for example, patents). Reference 1). As a constituent component of the adhesive, a curing agent such as an epoxy resin, a phenol resin having reactivity with the epoxy resin, and a thermal latent catalyst for promoting the reaction between the epoxy resin and the curing agent are generally used. The heat latent catalyst is an important factor for determining the curing temperature and curing rate of the adhesive, and various compounds are used from the viewpoint of storage stability at room temperature and curing rate during heating. Such an adhesive is usually cured by heating at a temperature of 170 to 250 ° C. for 1 to 3 hours, whereby adhesiveness is obtained.

  In recent years, with the high integration of semiconductor elements and the high definition of liquid crystal elements, the pitch between elements and between wirings is becoming narrower. When the above-described adhesive is used for such a semiconductor element, the heating temperature at the time of curing is high, and the curing speed is slow. There is a tendency to cause damage to members. In order to further reduce the cost, it is necessary to improve the throughput, and adhesion at a low temperature (100 to 170 ° C.), a short time (within 1 hour), in other words, “low temperature rapid curing” is required. In order to achieve this low temperature rapid curing, it is necessary to use a thermal latent catalyst having a low activation energy. However, it is very difficult for a heat latent catalyst with low activation energy to have storage stability near room temperature.

In recent years, attention has been focused on radical curable adhesives in which acrylate derivatives and methacrylate derivatives (hereinafter referred to as (meth) acrylate derivatives), which are radical polymerizable substances, and peroxides, which are radical polymerization initiators, are used in combination. . In radical curing, radicals that are reactive species are rich in reactivity, and thus can be cured in a shorter period of time compared to the epoxy resin system (for example, see Patent Document 2). On the other hand, it has been found that a radical-curing adhesive is inferior in adhesive strength due to large curing shrinkage during curing. As a method for improving the adhesive strength, a method has been proposed in which a urethane acrylate compound imparted with flexibility and flexibility by an ether bond is used as a radical polymerizable compound (see, for example, Patent Documents 3 and 4).
Japanese Patent Laid-Open No. 01-113480 JP 2002-203427 A JP 2001-262079 A JP 2002-285128 A

  However, even with radical curing using a (meth) acrylate derivative as a radical polymerizable substance, the curing rate of the (meth) acrylate derivative is not always sufficient, and the curing reaction is caused by oxygen present in the atmosphere. There is a problem that it is easily disturbed. Therefore, in the case of the conventional radical curable adhesive, there is still room for improvement in order to be put to practical use, such as it is difficult to stably obtain characteristics such as adhesive strength and connection resistance.

  The present invention has been made in view of the above-described problems of the prior art, and can perform a curing process sufficiently quickly at a low temperature and can stably obtain characteristics such as adhesive strength and connection resistance. It is an object to provide an agent composition, a circuit connection material using the adhesive composition, a circuit member connection structure, and a semiconductor device.

In order to solve the above problems, the present invention provides (A) a compound having a carbon-carbon double bond in the molecule, (B) a compound having two or more mercapto groups in the molecule, and (C) a radical. An anisotropic conductive adhesive composition containing a polymerization initiator and conductive particles is provided.

  By combining the components (A), (B) and (C), the adhesive composition of the present invention can be cured sufficiently quickly at a low temperature, and has a wide process margin, adhesive strength and connection. It is possible to stably obtain characteristics such as resistance. Therefore, even if the adhesive composition of the present invention narrows the pitch between elements such as semiconductor elements and liquid crystal elements and between arrangements, the peripheral member is damaged by heating not only the desired connection portion but also the peripheral member. It is useful as an adhesive that can prevent the above problems and can improve the throughput.

（式（１）、（２）中、ｍ及びｎは各々独立に１〜５の整数を示す。） In the adhesive composition of the present invention, (B) a compound having two or more mercapto groups in the molecule is p-xylene dithiol, m-xylene dithiol, trimethylolpropane tristhioglycolate, pentaerythritol tetrakis. It is preferably at least one selected from thioglycolate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, and a compound represented by the following general formula (1) or (2). By using such a compound, it is possible to effectively achieve excellent low-temperature rapid curability and to obtain properties such as adhesive strength and connection resistance more reliably.

(In formulas (1) and (2), m and n each independently represent an integer of 1 to 5.)

  Moreover, when the adhesive composition of this invention is an adhesive agent for semiconductor elements or a liquid crystal display element, it is preferable that the said adhesive composition further contains a thermoplastic resin. Furthermore, the thermoplastic resin is preferably at least one selected from phenoxy resin, polyester resin, polyurethane resin, polyester urethane resin, butyral resin, acrylic resin, and polyimide resin.

Moreover, the anisotropic conductive adhesive composition of the present invention contains conductive particles. When the adhesive composition contains conductive particles, the adhesive composition itself can easily have conductivity, so that it is effective as a conductive adhesive in the field of electrical or electronic industries such as circuit electrodes and semiconductors. Can be used. Furthermore, in this case, the adhesive composition for electrically conductive, it is possible to lower the connection resistance after curing.

  The present invention also provides a circuit connecting material for electrically connecting opposing circuit electrodes, the circuit connecting material containing the adhesive composition of the present invention.

  The circuit connection material of the present invention can bond the facing circuit electrodes to each other in a sufficiently short time even at a low temperature, and can widen the process margin. Furthermore, the cured product obtained from such a circuit connection material can have a stable adhesive strength even when the process temperature and time at which the cured product is obtained are changed. A decrease in the adhesive strength of the cured product over time can be suppressed.

  The present invention also provides a film adhesive formed by forming the adhesive composition of the present invention into a film. Moreover, this invention provides the film-form circuit connection material formed by forming the circuit connection material of the said invention in the shape of a film. Since the film-like adhesive and circuit connection material are excellent in handleability, the throughput can be further improved.

  Further, according to the present invention, a first circuit member having a first circuit electrode formed on the main surface of the first circuit board and a second circuit electrode formed on the main surface of the second circuit board are provided. The second circuit member is provided between the main surface of the first circuit board and the main surface of the second circuit board, and the first circuit electrode and the second circuit electrode are arranged to face each other. And a circuit connection member that is electrically connected to the circuit connection member. The circuit connection member provides a circuit member connection structure that is a cured product of the circuit connection material of the present invention.

  The circuit member connection structure of the present invention can effectively use electrically connected circuit electrodes. That is, since the circuit connection material described above is used so that the first circuit electrode and the second circuit electrode can be electrically connected, the circuit member having the connection structure of the present invention has a small variation in quality and is sufficiently Stable characteristics can be shown. Furthermore, when the hardened | cured material of a circuit connection material contains electroconductive particle, connection resistance can be made low. By blending the conductive particles, electrical connection between desired members can be easily performed.

  The present invention also includes a semiconductor element, a substrate on which the semiconductor element is mounted, and a semiconductor element connection member that is provided between the semiconductor element and the substrate and electrically connects the semiconductor element and the substrate. The element connection member provides a semiconductor device that is a cured product of the adhesive composition of the present invention.

  In the semiconductor device of the present invention, since the semiconductor element and the substrate are electrically connected via the semiconductor element connecting member that is a cured product of the adhesive composition of the present invention, there is little variation in quality and sufficient Stable characteristics can be shown. Furthermore, when the hardened | cured material of adhesive composition contains electroconductive particle, connection resistance can be made low enough and electroconductivity can fully be ensured between the semiconductor element and board | substrate which oppose. .

  According to the present invention, an adhesive composition that can be cured sufficiently quickly at a low temperature and can stably obtain characteristics such as adhesive strength and connection resistance, and the adhesive composition are used. It is possible to provide a circuit connection material, a circuit member connection structure, and a semiconductor device.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left, and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios. In addition, “(meth) acrylate” in the present specification means “acrylate” and “methacrylate” corresponding thereto. Similarly, “(meth) acryl” means “acryl” and its corresponding “methacrylate”, and “(meth) acryloyl” means “acryloyl” and its corresponding “methacryloyl”.

(Adhesive composition)
The adhesive composition of the present invention comprises (A) a compound having a carbon-carbon double bond in the molecule, (B) a compound having two or more mercapto groups in the molecule, and (C) a radical polymerization initiator. Containing.

  As the compound having a carbon-carbon double bond in the molecule (A) used in the present invention, vinyl group, allyl group, styryl group, alkenyl group, (meth) acryloyl group, maleimide, maleic acid, fumaric acid, butadiene Any known compound can be used without particular limitation as long as it is a compound having an unsaturated bond typified by norbornene or the like in the molecule.

  (A) As a compound which has a carbon-carbon double bond in a molecule | numerator, specifically, an epoxy (meth) acrylate oligomer, a urethane (meth) acrylate oligomer, a polyether (meth) acrylate oligomer, polyester (meth) acrylate Oligomers such as oligomers, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, Neopentyl glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, isocyanuric acid modified bifunctional (meth) acrylate, isocyanuric acid modified trifunctional (meth) acrean , 2,2′-di (meth) acryloyloxydiethyl phosphate, polyfunctional (meth) acrylate compounds such as 2- (meth) acryloyloxyethyl acid phosphate, 1-methyl-2,4-bismaleimidebenzene, m -Phenylene bismaleimide, p-phenylene bismaleimide, m-toluylene bismaleimide, 4,4'-biphenylene bismaleimide, 4,4 '-(3,3'-dimethyl-biphenylene) bismaleimide, 4,4'- (3,3′-dimethyldiphenylmethane) bismaleimide, 4,4 ′-(3,3′-diethyldiphenylmethane) bismaleimide, 4,4′-diphenylmethane bismaleimide, 4,4′-diphenylpropane bismaleimide, 4, 4'-diphenyl ether bismaleimide, 3,3'-diphenyl Lufone bismaleimide, 2,2′-bis (4- (4-maleimidophenoxy) phenyl) propane, 1,1-bis (4- (4-maleimidophenoxy) phenyl) decane, 4,4′-cyclohexylidene- Maleimide compounds such as bis (1- (4 maleimidophenoxy) -2-cyclohexylbenzene, 2,2′-bis (4- (4-maleimidophenoxy) phenyl) hexafluoropropane, diethylene glycol divinyl ether, dipropylene glycol divinyl ether, Vinyl ether compounds such as cyclohexanedimethanol divinyl ether and trimethylolpropane trivinyl ether, allyl compounds such as 1,3-diallyl phthalate, 1,2-diallyl phthalate and triallyl isocyanurate, styrene derivatives, acrylic Examples thereof include amide derivatives, nadiimide derivatives, natural rubber, isoprene rubber, butyl rubber, nitrile rubber, butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, and carboxylated nitrile rubber. Moreover, the compound which introduce | transduced the vinyl group, the allyl group, and the (meth) acryloyl group into the terminal or side difference of thermoplastic resins, such as a polyacrylate, a phenoxy resin, and a polyurethane resin, can be used. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Moreover, higher adhesiveness can be provided by using the said compound and the phosphate ester (meth) acrylate shown by the following general formula (3), (4) or (5) together.

（式（３）中、Ｒ^５はアクリロイル基又はメタアクリロイル基を示し、Ｒ^６は水素原子又はメチル基を示し、ｗ及びｘは各々独立に１〜８の整数を示す。）

(In Formula (3), R ⁵ represents an acryloyl group or a methacryloyl group, R ⁶ represents a hydrogen atom or a methyl group, and w and x each independently represent an integer of 1 to 8.)

（式（４）中、Ｒ^７はアクリロイル基又はメタアクリロイル基を示し、ｙ及びｚは各々独立に１〜８の整数を示す。）

(In formula (4), R ⁷ represents an acryloyl group or a methacryloyl group, and y and z each independently represents an integer of 1 to 8.)

（式（５）中、Ｒ^８はアクリロイル基又はメタアクリロイル基を示し、Ｒ^９は水素原子又はメチル基を示し、ｐ及びｑは各々独立に１〜８の整数を示す。）

(In Formula (5), R ⁸ represents an acryloyl group or a methacryloyl group, R ⁹ represents a hydrogen atom or a methyl group, and p and q each independently represent an integer of 1 to 8)

  As the compound having two or more mercapto groups in the molecule (B) used in the present invention, known compounds can be used without any particular limitation, but the elastic modulus and glass transition of the adhesive composition after curing can be used. From the viewpoint of temperature and mechanical properties, a compound having a rigid skeleton such as a benzene ring or an isocyanuric ring in the molecule, or a compound having three or more mercapto groups in one molecule is preferable.

  (B) Preferred examples of the compound having two or more mercapto groups in the molecule include p-xylene dithiol, m-xylene dithiol, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthioglycolate, trimethylolpropane tris. Examples thereof include thiopropionate, pentaerythritol tetrakisthiopropionate, isocyanurate-modified thiol compound represented by the following general formula (1) or (2), and 4,4′-thiodibenzenethiol, adhesiveness, heat resistance From the viewpoint of properties, isocyanurate-modified thiol compounds are particularly preferred. (B) The compound which has two or more mercapto groups in a molecule | numerator may be used individually by 1 type, and may be used in combination of 2 or more type.

（式（１）、（２）中、ｍ及びｎは各々独立に１〜５の整数を示す。）

(In formulas (1) and (2), m and n each independently represent an integer of 1 to 5.)

  The content of the compound having two or more mercapto groups in the molecule (B) in the adhesive composition of the present invention is (A) based on 100 parts by weight of the compound having a carbon-carbon double bond in the molecule. 5-300 weight part is preferable and 10-200 weight part is more preferable. (B) When the compound having two or more mercapto groups in the molecule is 5 parts by weight or more, a decrease in the elastic modulus after curing can be suppressed, and when it is 300 parts by weight or less, the storage stability tends to be improved. It is in.

  In the adhesive composition of the present invention, (C) a radical generated from a radical polymerization initiator, (A) a carbon-carbon double bond of a compound having a carbon-carbon double bond in the molecule, and (B) molecule By promoting the reaction of the compound having two or more mercapto groups with the mercapto group, the curing reaction of the entire adhesive composition proceeds promptly even at low temperatures, and as a result, the low-temperature fast curability is improved. To do.

  As the (C) radical polymerization initiator used in the present invention, known compounds such as conventionally known peroxides and azo compounds can be used, but from the viewpoints of stability, reactivity, and compatibility, 1 Peroxides having a minute half-life temperature of 90 to 175 ° C. and a molecular weight of 180 to 1,000 are preferred. Specifically, 1,1,3,3-tetramethylbutylperoxyneodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, cumylper Oxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, dilauroyl peroxide, 1-cyclohexyl-1-methylethylperoxynoedecanoate, t-hexylperoxyneo Decanoate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2 , 5-Di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexyl Noate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneoheptanoate, t-amylperoxy-2-ethylhexanoate, di-t-butylperoxyhexahydroterephthalate, t -Amylperoxy-3,5,5-trimethylhexanoate, 3-hydroxy-1,1-dimethylbutylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethyl Hexanoate, t-amylperoxyneodecanoate, t-amylperoxy-2-ethylhexanoate, di (3-methylbenzoyl) peroxide, dibenzoyl peroxide, di (4-methylbenzoyl) per Oxide, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis 1-acetoxy-1-phenylethane), 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyronitrile 4,4′-azobis (4-cyanovaleric acid), 1,1′-azobis (1-cyclohexanecarbonitrile), t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy -3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (3-methylbenzoylperoxy) hexane, t-butylperoxy-2-ethylhexyl Monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) Examples include hexane, t-butyl peroxybenzoate, dibutyl peroxytrimethyl adipate, t-amyl peroxy normal octoate, t-amyl peroxy isononanoate, t-amyl peroxybenzoate and the like. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  Moreover, the compound which generate | occur | produces a radical by 150-750 nm light irradiation can be used as (C) radical polymerization initiator. Such a compound is not particularly limited, and a known compound can be used. For example, Photoinitiation, Photopolymerization, and Photocuring, J. Mol. -P. The α-acetaminophenone derivatives and phosphine oxide derivatives described in Fouassier, Hanser Publishers (1995), p17 to p35 are more preferable because of their high sensitivity to light irradiation. These compounds may be used individually by 1 type, and may be used in combination of 2 or more type. Furthermore, you may use combining the said compound, said peroxide, and an azo compound.

  The content of the (C) radical polymerization initiator in the adhesive composition of the present invention is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the compound (A) having a carbon-carbon double bond in the molecule. 1 to 30 parts by weight is more preferable. When the radical polymerization initiator is 0.1 part by weight or more, a decrease in heat resistance can be suppressed, and when it is 50 parts by weight or less, storage stability tends to be improved.

  The form of energy applied in the present invention is not particularly limited, and examples thereof include heat, electron beam, gamma ray, ultraviolet ray, infrared ray, visible light, and microwave.

  The adhesive composition of the present invention can further contain a thermoplastic resin. Although it does not restrict | limit especially as a thermoplastic resin, Resin containing polar groups, such as a hydroxyl group, an ether group, an ester group, a urethane group, an amide group, an imide group, a carboxyxyl group, in the principal chain skeleton or a side chain of resin is used. It is preferable from the viewpoint of adhesiveness. Specifically, phenoxy resin, polyester resin, polyurethane resin, polyester urethane resin, butyral resin, polyimide resin, acrylic resin, and the like can be suitably used. Moreover, what modified | denatured the said resin by the epoxy group which is a reactive functional group, an acryloyl group, a methacryloyl group, a carboxyl group, etc. is more preferable since heat resistance improves.

The molecular weight of the thermoplastic resin is not particularly limited, but the weight average molecular weight is preferably 5,000 to 150,000, and particularly preferably 10,000 to 80,000. When the weight average molecular weight of the thermoplastic resin is 5,000 or more, the film formability tends to be improved, and when it is 150,000 or less, the deterioration of compatibility with other components tends to be suppressed. . In addition, the weight average molecular weight as used in the field of this invention means the value measured using the standard polystyrene calibration curve by the gel permeation chromatography method (GPC) according to the following conditions.
<GPC conditions>
Equipment used: Hitachi L-6000 type [Hitachi, Ltd.], Column: Gel Pack GL-R42
0 + Gel Pack GL-R430 + Gel Pack GL-R440 (3 in total) [Hitachi Chemical Industry (
Product name], eluent: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1.75 ml
/ Min, detector: L-3300RI [Hitachi, Ltd.]

  When the adhesive composition of this invention contains a thermoplastic resin, it is preferable that content of the said thermoplastic resin shall be 20-320 weight part with respect to 100 weight part of (A) epoxy resin.

  When using the adhesive composition of this invention for uses, such as a circuit connection material, the said adhesive composition can further contain electroconductive particle. Even when the adhesive composition of the present invention does not contain conductive particles, both can be electrically connected by direct contact of the circuit electrodes facing each other, but the adhesive composition of the present invention By containing conductive particles in the adhesive composition, the adhesive composition of the present invention effectively exhibits the function as a conductive adhesive, and can perform more stable connection.

  The conductive particles are not particularly limited as long as they have conductivity capable of obtaining electrical connection, and examples thereof include metal particles such as Au, Ag, Ni, Cu, and solder, and carbon. Further, the core may be made of conductive glass, ceramic, plastic (polystyrene, etc.), and the core is coated with the metal particles or carbon. Among these, those in which the metal itself is a heat-meltable metal, or those in which plastic is used as a core and coated with metal or carbon are preferable. In these cases, since it becomes easier to deform the cured product of the adhesive composition by heating or pressurization, the contact area between the electrode and the adhesive composition is increased when the electrodes are electrically connected to each other. And the conductivity between the electrodes can be improved.

  Furthermore, the adhesive composition of this invention may contain the layered particle | grains which coat | covered the surface of the said electroconductive particle with polymer resin. When conductive particles are added to the adhesive composition in the form of layered particles, the surface of the conductive particles is coated with a resin even when the amount of the conductive particles is increased. Generation | occurrence | production of the short circuit by contact can be suppressed more reliably, and the insulation between electrode circuits can also be improved. In addition, electroconductive particle or layered particle can be used individually by 1 type or in combination of 2 or more types.

  The average particle diameter of the conductive particles is preferably 1 to 18 μm from the viewpoint of dispersibility and conductivity. Moreover, it is preferable to set it as 0.1-30 volume% with respect to 100 volume% of adhesive compositions, and, as for the mixture ratio of electroconductive particle, it is more preferable to set it as 0.1-10 volume%. If the blending ratio of the conductive particles is less than 0.1% by volume, the conductivity improving effect due to the blending of the conductive particles tends to be insufficient, and if it exceeds 30% by volume, a short circuit tends to occur. There is a tendency. In addition, the compounding ratio (volume%) of electroconductive particle is determined based on the volume of each component before hardening the adhesive composition in 23 degreeC. The volume% of each component is introduced into a container such as a graduated cylinder containing a suitable solvent (water, alcohol, etc.) that wets the component well, such as a method that converts the weight to volume using specific gravity, It can be obtained by a method of calculating from the increased volume.

  The adhesive composition of the present invention can further contain a stabilizer for the purpose of controlling the curing rate and improving storage stability. The stabilizer is not particularly limited, and known compounds can be used. However, quinone derivatives such as benzoquinone and hydroquinone, phenol derivatives such as 4-methoxyphenol and 4-t-butylcatechol, 2,2, Preferred are aminoxyl derivatives such as 6,6-tetramethylpiperidine-1-oxyl and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and hindered amine derivatives such as tetramethylpiperidyl methacrylate.

  The blending ratio of the stabilizer is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 10 parts by weight based on 100 parts by weight of the compound (A) having a carbon-carbon double bond in the molecule. Parts by weight. When the addition amount is less than 0.01 parts by weight, there is a concern that the addition effect is remarkably reduced, and when it is 30 parts by weight or more, the compatibility with other components may be reduced.

  Moreover, the adhesive composition of this invention can further contain a coupling agent for the purpose of the further improvement of adhesive force. Examples of the coupling agent include silane coupling agents having a functional group such as (meth) acryloyl group, mercapto group, amino group, and imidazole group in the skeleton, tetraalkoxy titanate derivatives, polydialkyl titanate derivatives, and the like. Furthermore, a filler, a softening agent, an accelerator, a deterioration inhibitor colorant, a flame retardant, a thixotropic agent, and the like can also be contained.

  The adhesive composition of the present invention can be used in the form of a paste when it is liquid at room temperature. In the case of a solid at normal temperature, it can be made into a paste using a solvent in addition to being made into a paste by heating. The solvent that can be used is not particularly limited as long as it does not react with the adhesive composition and exhibits sufficient solubility, but a solvent having a boiling point of 50 to 150 ° C. at normal temperature is preferable. When the boiling point of the solvent is less than 50 ° C., the solvent easily volatilizes at room temperature, and the workability when producing a film described later tends to deteriorate. Moreover, when the boiling point of a solvent exceeds 150 degreeC, it will become difficult for a solvent to volatilize and it exists in the tendency for the adhesive strength after adhesion | attachment to fall with the remaining solvent.

  The adhesive composition of the present invention can also be used in the form of a film. Thus, when the adhesive composition is in the form of a film, the handleability is excellent and it is more convenient. This film adhesive is obtained by applying a mixed solution obtained by adding a solvent or the like to an adhesive composition on a peelable substrate such as a fluororesin film, a polyethylene terephthalate film, or a release paper, or on a substrate such as a nonwoven fabric. It can be obtained by impregnating the mixed solution and placing it on a peelable substrate and removing the solvent.

  Moreover, when conductive particles are added to the adhesive composition of the present invention to produce a film, an anisotropic conductive film can be obtained. This anisotropic conductive film is, for example, disposed between opposing electrodes on a substrate, and heated and pressed to enable both electrodes to be bonded and electrically connected. Here, as the substrate on which the electrode is formed, an inorganic material such as a semiconductor, glass or ceramic, an organic material such as polyimide or polycarbonate, a combination of an inorganic material such as glass / epoxy and an organic material, or the like is applicable.

Moreover, the adhesive composition of this invention can be adhere | attached using heating and pressurization together. The heating temperature is not particularly limited, but is preferably 50 to 190 ° C. Moreover, the pressure should just be a range which does not damage an adherend, and generally 0.1-10 MPa is preferable. The heating and pressurizing time is preferably 0.5 to 120 seconds. For example, when the first circuit member is a transparent substrate from the ultraviolet region to the visible region, after the adhesive composition is disposed on the first circuit member having the first connection terminal, the second The second circuit member having the connection terminals can be arranged to face each other, and can be heated and pressurized from the second circuit member side, and can be bonded by performing light irradiation from the first circuit member side. The light irradiation is preferably in the wavelength range of 150 to 750 nm, and a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, or a metal halide lamp can be used. Although it is 0.01-10 J / cm < ² >, it is not limited to this.

  According to the adhesive composition of the present invention having the above-described configuration, the curing process can be performed sufficiently quickly at a low temperature, and the process margin when performing the curing process can be widened, such as the adhesive strength and the connection resistance. It is possible to stably obtain the above characteristics at a high level.

  Since the adhesive composition of the present invention has the above-described excellent characteristics, it can be suitably used as a circuit connection material. For example, when the circuit electrode of the first circuit member and the second circuit member are electrically connected, the adhesive composition of the present invention is applied to one of the circuit electrodes in a state where these circuit members are arranged to face each other. Then, it can be electrically connected to the other circuit electrode by radical polymerization reaction. As described above, when the adhesive composition of the present invention is used as a circuit connection material, electrical connection can be performed in a short time, and even if the process temperature and time during connection vary, the connection strength and connection resistance And the like can be stabilized. In addition, it is possible to suppress deterioration of the characteristics of the circuit connection material over time. Furthermore, when this circuit connection material contains conductive particles, it can exhibit anisotropy of electrical connection and can also be used as an anisotropic conductive circuit connection material for circuit electrodes.

  The above circuit connection material can also be used as a circuit connection material of different types of adherends having different thermal expansion coefficients. Specifically, it is used as a semiconductor element adhesive material used for circuit connecting materials such as anisotropic conductive adhesive, silver paste, silver film, CSP elastomer, CSP underfill material, LOC tape, etc. be able to.

(Circuit member connection structure)
Next, a preferred embodiment of the circuit member connection structure of the present invention will be described. FIG. 1 is a schematic cross-sectional view showing an embodiment of a circuit member connection structure of the present invention. As shown in FIG. 1, the circuit member connection structure 1 of the present embodiment includes a first circuit member 20 and a second circuit member 30 that face each other. Between these circuit members 30, a circuit connection member 10 is provided for electrically connecting them. The first circuit member 20 includes a first circuit board 21 and a first circuit electrode 22 formed on the main surface 21 a of the circuit board 21. Note that an insulating layer (not shown) may be formed on the main surface 21a of the circuit board 21 in some cases.

  On the other hand, the second circuit member 30 includes a second circuit board 31 and a second circuit electrode 32 formed on the main surface 31 a of the second circuit board 31. In addition, an insulating layer (not shown) may be formed on the main surface 31a of the circuit board 31 according to circumstances.

The first circuit member 20 and the second circuit member 30 are not particularly limited as long as electrodes that require electrical connection are formed. Specific examples include glass or plastic substrates with electrodes formed of ITO or the like used for liquid crystal displays, printed wiring boards, ceramic wiring boards, flexible wiring boards, semiconductor silicon chips, and the like. They can be used in combination. As described above, in the present embodiment, a material made of an organic material such as a printed wiring board or polyimide, a metal such as copper or aluminum, ITO (indium tin oxide), silicon nitride (Si _x N _y ), silicon dioxide (SiO 2). Circuit members having various surface states such as inorganic materials such as ₂ ) can be used.

  The circuit connecting member 10 contains an insulating material 11 and conductive particles 7. The conductive particles 7 are disposed not only between the first circuit electrode 22 and the second circuit electrode 32 facing each other but also between the main surfaces 21a and 31a. In the circuit member connection structure 1 of the present embodiment, the first circuit electrode 22 and the second circuit electrode 32 are electrically connected via the conductive particles 7. For this reason, the connection resistance between the first circuit electrode 22 and the second circuit electrode 32 is sufficiently reduced. Therefore, the flow of current between the first circuit electrode 22 and the second circuit electrode 32 can be made smooth, and the functions of the circuit can be sufficiently exhibited. Moreover, it is also possible to show the anisotropy of electrical connection by setting the conductive particles 7 to the above-described mixing ratio.

  In addition, when the circuit connection member 10 does not contain the conductive particles 7, they are in direct contact with each other so that a desired amount of current flows between the first circuit electrode 22 and the second circuit electrode 32. It is electrically connected by making it close or sufficiently close.

  Since the circuit connection member 10 is composed of a cured product of a circuit connection material containing the adhesive composition, the adhesive strength of the circuit connection member 10 to the first circuit member 20 or the second circuit member 30 is sufficient. In addition, the connection resistance is sufficiently low, and this state can be maintained for a long period of time. Therefore, the long-term reliability of the electrical characteristics between the first circuit electrode 22 and the second circuit electrode 32 can be sufficiently increased.

(Method for manufacturing circuit member connection structure)
Next, a method for manufacturing the circuit member connection structure described above will be described with reference to FIG.

  First, the first circuit member 20 and the film-like circuit connecting material 40 described above are prepared (see FIG. 2A). The film-like circuit connection material 40 is formed by forming a circuit connection material into a film shape. The circuit connection material contains an adhesive component 5 and conductive particles 7. Here, the adhesive component according to the present invention described above is used for the adhesive component 5. Even when the circuit connecting material does not contain the conductive particles 7, the circuit connecting material can be used for anisotropic conductive bonding as an insulating adhesive, and is sometimes called NCA (Non-Conductive Adhesive). When the circuit connecting material contains conductive particles 7, the circuit connecting material may be called ACA (Anisotropic Conductive Adhesive).

  The thickness of the film-like circuit connecting material 40 is preferably 10 to 50 μm. If the thickness of the film-like circuit connecting material 40 is less than 10 μm, the circuit connecting material tends to be insufficiently filled between the circuit electrodes 22 and 32. On the other hand, when the thickness exceeds 50 μm, the adhesive composition between the circuit electrodes 22 and 32 cannot be sufficiently removed, and it tends to be difficult to ensure conduction between the circuit electrodes 22 and 32.

  Next, the film-like circuit connecting material 40 is placed on the surface of the first circuit member 20 on which the circuit electrodes 22 are formed. When the film-like circuit connecting material 40 is attached on a support (not shown), the film-like circuit connecting material 40 side is directed to the first circuit member 20 so that the first circuit is connected. Place on member 20. At this time, the film-like circuit connecting material 40 is film-like and easy to handle. For this reason, the film-like circuit connecting material 40 can be easily interposed between the first circuit member 20 and the second circuit member 30, and the first circuit member 20 and the second circuit member 30 Connection work can be performed easily.

  And the film-form circuit connection material 40 is pressurized to the arrow A and B direction of Fig.2 (a), and the film-form circuit connection material 40 is temporarily connected to the 1st circuit member 20 (refer FIG.2 (b)). . At this time, you may pressurize, heating. However, the heating temperature is a temperature at which the adhesive composition in the film-like circuit connecting material 40 is not cured, that is, a temperature lower than the temperature at which the radical polymerization initiator generates radicals.

  Subsequently, as shown in FIG. 2 (c), the second circuit member 30 is placed on the film-like circuit connection material 40 with the second circuit electrode facing the first circuit member 20. In addition, when the film-form circuit connection material 40 has adhered on the support body (not shown), after peeling a support body, the 2nd circuit member 30 is mounted on the film-form circuit connection material 40. FIG.

  And it heats through the 1st and 2nd circuit members 20 and 30 to the arrow A and B direction of FIG.2 (c), heating the film-form circuit connection material 40. FIG. The heating temperature at this time is a temperature at which the radical polymerization initiator can generate radicals. As a result, radicals are generated in the radical polymerization initiator, and polymerization of the radical polymerizable compound is started. In this way, the film-like circuit connection material 40 is cured and the main connection is performed, and a circuit member connection structure as shown in FIG. 1 is obtained.

  The heating temperature is, for example, 90 to 200 ° C., and the connection time is, for example, 1 second to 10 minutes. These conditions are appropriately selected depending on the application to be used, the adhesive composition, and the circuit member, and may be post-cured as necessary.

  When the circuit member connection structure is manufactured as described above, in the circuit member connection structure obtained, the conductive particles 7 can be brought into contact with both of the circuit electrodes 22 and 32 facing each other. The connection resistance between 32 can be sufficiently reduced.

  Further, by heating the film-like circuit connecting material 40, the adhesive component 5 is cured to become the insulating substance 11 in a state where the distance between the circuit electrode 22 and the circuit electrode 32 is sufficiently small, and the first circuit member is obtained. 20 and the second circuit member 30 are firmly connected via the circuit connection member 10. That is, in the circuit member connection structure obtained, the circuit connection member 10 is made of a cured product of the circuit connection material containing the adhesive composition, so that the circuit connection member 10 is connected to the circuit member 20 or 30. Adhesive strength is sufficiently high, and the connection resistance between the circuit electrodes 22 and 32 can be sufficiently reduced. The circuit member connection structure can maintain such a state for a long period of time. Therefore, the circuit member connection structure obtained is sufficiently prevented from changing with time in the distance between the circuit electrodes 22 and 32 and is excellent in long-term reliability of the electrical characteristics between the circuit electrodes 22 and 32.

  The adhesive component 5 may include at least a radical polymerization initiator that generates radicals by heating. Instead of this radical polymerization initiator, a radical polymerization initiator that generates radicals only by light irradiation may be used. Good. In this case, when the film-like circuit connecting material 40 is cured, light irradiation may be performed instead of heating. In addition, a radical polymerization initiator that generates radicals by ultrasonic waves, electromagnetic waves, or the like may be used as necessary. Moreover, you may use an epoxy resin and a latent hardener as a sclerosing | hardenable component in the adhesive agent component 5. FIG.

  Moreover, in the said embodiment, although the connection structure of a circuit member is manufactured using the film-form circuit connection material 40, it replaces with the film-form circuit connection material 40, and uses the circuit connection material which is not formed in the film form. May be. Even in this case, if the circuit connection material is dissolved in a solvent and the solution is applied to either the first circuit member 20 or the second circuit member 30 and dried, the first and second circuit members 20 are used. , 30 can interpose a circuit connecting material.

  Further, instead of the conductive particles 7, other conductive materials may be used. Examples of other conductive materials include particulate or short fiber carbon, metal wires such as Au-plated Ni wire, and the like.

(Semiconductor device)
Next, embodiments of the semiconductor device of the present invention will be described. FIG. 3 is a schematic cross-sectional view showing an embodiment of the semiconductor device of the present invention. As shown in FIG. 3, the semiconductor device 2 of this embodiment includes a semiconductor element 50 and a substrate 60 that serves as a semiconductor support member, and these are electrically connected between the semiconductor element 50 and the substrate 60. A semiconductor element connection member 80 is provided to connect to the semiconductor device. The semiconductor element connection member 80 is stacked on the main surface 60 a of the substrate 60, and the semiconductor element 50 is further stacked on the semiconductor element connection member 80.

  The substrate 60 includes a circuit pattern 61, and the circuit pattern 61 is electrically connected to the semiconductor element 50 via the semiconductor connection member 80 on the main surface 60 a of the substrate 60 or directly. And these are sealed with the sealing material 70, and the semiconductor device 2 is formed.

  The material of the semiconductor element 50 is not particularly limited, but silicon, germanium group 4 semiconductor element, GaAs, InP, GaP, InGaAs, InGaAsP, AlGaAs, InAs, GaInP, AlInP, AlGaInP, GaNAs, GaNP, GaInNAs, GaInNP, III-V group compound semiconductor elements such as GaSb, InSb, GaN, AlN, InGaN, InNAsP, II-VI group compound semiconductor elements such as HgTe, HgCdTe, CdMnTe, CdS, CdSe, MgSe, MgS, ZnSe, ZeTe, and Various materials such as CuInSe (ClS) can be used.

  The semiconductor element connection member 80 contains the insulating substance 11 and the conductive particles 7. The conductive particles 7 are disposed not only between the semiconductor element 50 and the circuit pattern 61 but also between the semiconductor element 50 and the main surface 60a. In the semiconductor device 2 of the present embodiment, the semiconductor element 50 and the circuit pattern 61 are electrically connected via the conductive particles 7. For this reason, the connection resistance between the semiconductor element 50 and the circuit pattern 61 is sufficiently reduced. Therefore, the current flow between the semiconductor element 50 and the circuit pattern 61 can be made smooth, and the functions of the semiconductor can be fully exhibited. Moreover, it is also possible to show the anisotropy of electrical connection by setting the conductive particles 7 to the above-described mixing ratio.

  When the semiconductor element connection member 80 does not contain the conductive particles 7, the semiconductor element 50 and the circuit pattern 61 are brought into direct contact with each other so that a desired amount of current flows or sufficiently close to the electric current. Connected.

  The semiconductor element connection member 80 is made of a cured product of the adhesive composition containing the adhesive component. From this, the adhesive strength of the semiconductor element connection member 40 to the semiconductor element 50 and the substrate 60 is sufficiently high, and the connection resistance between the semiconductor element 50 and the circuit pattern 61 can be sufficiently reduced. And this state can be maintained over a long period of time. Therefore, the long-term reliability of the electrical characteristics between the semiconductor element 50 and the substrate 60 can be sufficiently increased.

(Method for manufacturing semiconductor device)
Next, a method for manufacturing the semiconductor device described above will be described.

  First, a substrate 60 on which a circuit pattern 61 is formed and a film-like semiconductor element connecting material are prepared. The film-like semiconductor element connection material is formed by forming a semiconductor element connection material into a film shape. The semiconductor element connecting material contains an adhesive component 5 and conductive particles 7. Here, the adhesive component according to the present invention described above is used for the adhesive component 5.

  The thickness of the film-like semiconductor element connecting material is preferably 10 to 50 μm. If the thickness of the film-like semiconductor element connecting material is less than 10 μm, the semiconductor element connecting material tends to be insufficiently filled between the circuit pattern 61 and the semiconductor element 50. On the other hand, when the thickness exceeds 50 μm, the adhesive composition between the circuit pattern 61 and the semiconductor element 50 cannot be sufficiently removed, and there is a tendency that it is difficult to ensure conduction between the circuit pattern 61 and the semiconductor element 50.

  Next, the film-like semiconductor element connecting material is placed on the surface of the substrate 60 on which the circuit pattern 61 is formed. When the film-like semiconductor element connecting material is attached on a support (not shown), the film-like semiconductor element connecting material is placed on the substrate 60 so that the film-like semiconductor element connecting material side faces the substrate 60. At this time, the film-like semiconductor element connecting material is film-like and easy to handle. For this reason, the film-like semiconductor element connecting material can be easily interposed between the substrate 60 and the semiconductor element 50, and the connection work between the substrate 60 and the semiconductor element 50 can be easily performed.

  Then, the film-like semiconductor element connecting material is pressurized, and the film-like semiconductor element connecting material is temporarily connected to the substrate 60. At this time, you may pressurize, heating. However, the heating temperature is a temperature at which the adhesive composition in the film-like semiconductor element connecting material is not cured, that is, a temperature lower than the temperature at which the radical polymerization initiator generates radicals.

  Subsequently, the semiconductor element 50 is placed on the film-like semiconductor element connecting material. In addition, when the film-form semiconductor element connection material has adhered on the support body (not shown), after peeling a support body, the semiconductor element 50 is mounted on a film-form semiconductor element connection material.

  And it pressurizes through the board | substrate 60 and the semiconductor element 50, heating a film-form semiconductor element connection material. The heating temperature at this time is a temperature at which the radical polymerization initiator can generate radicals. As a result, radicals are generated in the radical polymerization initiator, and polymerization of the radical polymerizable compound is started. In this way, the film-like semiconductor element connecting material is cured and the main connection is performed.

  The heating temperature is, for example, 90 to 200 ° C., and the connection time is, for example, 1 second to 10 minutes. These conditions are appropriately selected depending on the application to be used, the adhesive composition, and the substrate, and may be post-cured as necessary.

  Next, the semiconductor element is sealed with resin as necessary. At this time, the resin sealing material is formed on the surface of the substrate, but the resin sealing material may also be formed on the surface opposite to the surface of the substrate. Thereby, a semiconductor device as shown in FIG. 3 is obtained.

  When the semiconductor device is manufactured as described above, in the obtained semiconductor device, the conductive particles 7 can be brought into contact with both the circuit pattern 61 and the semiconductor element 50 facing each other, and between the circuit pattern 61 and the semiconductor element 50. Can be sufficiently reduced.

Further, by heating the film-like semiconductor element connecting material, the adhesive component 5 is cured to become the insulating substance 11 in a state where the distance between the circuit pattern 61 and the semiconductor element 50 is sufficiently small, and the substrate 60 and the semiconductor element 50 are firmly connected to each other through the semiconductor element connecting member 80. That is, in the obtained semiconductor device, since the semiconductor element connection member 80 is made of a cured product of the semiconductor element connection material containing the adhesive composition, the semiconductor element connection member 80 for the substrate 50 or the semiconductor element 50 is used. Is sufficiently high, and the connection resistance between the semiconductor element 50 and the circuit pattern 61 is sufficiently reduced. Further, in this semiconductor device, such a state is maintained for a long time. Therefore, the obtained semiconductor device is sufficiently prevented from changing with time in the distance between the circuit pattern 61 and the semiconductor element 50, and is excellent in long-term reliability of electrical characteristics between the circuit pattern 61 and the semiconductor element 50.

  In the above embodiment, the adhesive component 5 includes at least a radical polymerization initiator that generates radicals by heating. Instead of this radical polymerization initiator, radicals are generated only by light irradiation. A radical polymerization initiator may be used. In this case, light irradiation may be performed in place of heating when the film-like semiconductor element connecting material is cured. In addition, a radical polymerization initiator that generates radicals by ultrasonic waves, electromagnetic waves, or the like may be used as necessary. Moreover, you may use an epoxy resin and a latent hardener as a sclerosing | hardenable component in the adhesive agent component 5. FIG.

  Moreover, in the said embodiment, although the semiconductor device is manufactured using the film-form semiconductor element connection material, it replaces with a film-form semiconductor element connection material, and even if it uses the semiconductor element connection material which is not formed in the film form Good. Even in this case, if the semiconductor element connection material is dissolved in a solvent and the solution is applied to either the substrate 60 or the semiconductor element 50 and dried, the semiconductor element connection material is interposed between the substrate 60 or the semiconductor element 50. be able to.

  Further, instead of the conductive particles 7, other conductive materials may be used. Examples of other conductive materials include particulate or short fiber carbon, metal wires such as Au-plated Ni wire, and the like.

  As mentioned above, although preferred embodiment of this invention was described, this invention is not restrict | limited to this.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.

(Preparation of phenoxy resin solution)
40 parts by weight of phenoxy resin (trade name: PKHM-30, manufactured by InChem) was dissolved in 60 parts by weight of methyl ethyl ketone (trade name: 2-butanone, manufactured by Wako Pure Chemical Industries, Ltd., purity 99%) to obtain a solid content of 40 weights. % Phenoxy resin solution was prepared.

(Preparation of butyral resin solution)
40 parts by weight of butyral resin (trade name: Denka Butyral 3000-1, manufactured by Denki Kagaku Kogyo Co., Ltd.) was dissolved in 60 parts by weight of methyl ethyl ketone (trade name: 2-butanone, manufactured by Wako Pure Chemical Industries, Ltd., purity 99%). A butyral resin solution having a solid content of 40% by weight was prepared.

(Preparation of polyester urethane resin solution)
A polyester urethane resin solution (trade name: UR-3500, manufactured by Toyobo Co., Ltd., solid content: 30% by weight) was prepared.

(Synthesis of urethane resin)
450 parts by weight of polybutylene adipate diol (manufactured by Aldrich, average molecular weight 2000), 450 parts by weight of polyoxytetramethylene glycol (manufactured by Aldrich, average molecular weight 2000) and 100 parts by weight of 1,4-butylene glycol (manufactured by Aldrich) It melt | dissolved in 4000 weight part of methyl ethyl ketone (Product name: 2-butanone, Wako Pure Chemical Industries Ltd. make, purity 99%). To this solution, 390 parts by weight of diphenylmethane diisocyanate (Aldrich) was added and reacted at 70 ° C. for 60 minutes to obtain a urethane resin. The temperature control at this time was performed using an oil bath (device name: FWB-240, manufactured by Fine). It was 120,000 when the weight average molecular weight of the obtained urethane resin was measured by the gel permeation chromatography method (GPC).

(Preparation of compounds having a carbon-carbon double bond in the molecule)
As compounds having a carbon-carbon double bond in the molecule, isocyanuric acid EO-modified diacrylate (trade name: M-215, manufactured by Toa Gosei Co., Ltd.), triallyl isocyanurate (trade name: TAIC, Nippon Synthetic Chemical Co., Ltd.) And 2- (meth) acryloyloxyethyl phosphate (trade name: Light Ester P-2M, manufactured by Kyoeisha Co., Ltd.).

(Preparation of compounds having two or more mercapto groups in the molecule)
As compounds having two or more mercapto groups in the molecule, pentaerythritol tetrakisthiopropionate (trade name: PETP, manufactured by Tokyo Chemical Industry Co., Ltd.), isocyanurate-modified thiol compound (trade name: THEIC-BMPA, Sakai Chemical) Prepared).

(Preparation of radical polymerization initiator)
T-Hexylperoxy-2-ethylhexanoate (trade name: Perhexyl O, manufactured by NOF Corporation) was prepared as a radical polymerization initiator.

(Preparation of conductive particles)
On the surface of the polystyrene particles, a layer made of nickel is provided so that the thickness of the layer becomes 0.2 μm, and further, a layer made of gold so that the thickness of the layer becomes 0.02 μm is formed on the nickel layer. Provided. In this way, conductive particles having an average particle diameter of 4 μm and a specific gravity of 2.5 were produced.

Example 1
100 parts by weight of the above phenoxy resin solution (containing 40 parts by weight of phenoxy resin), 10 parts by weight of the urethane resin, 28 parts by weight of isocyanuric acid EO-modified diacrylate (trade name: M-215, manufactured by Toa Gosei Co., Ltd.) 1 part by weight of 2- (meth) acryloyloxyethyl phosphate (trade name: Light Ester P-2M, manufactured by Kyoeisha Co., Ltd.), pentaerythritol tetrakisthiopropionate (trade name: PETP, manufactured by Tokyo Chemical Industry Co., Ltd.) 22 parts by weight and 3 parts by weight of t-hexylperoxy-2-ethylhexanoate (trade name: Perhexyl O, manufactured by Nippon Oil & Fats Co., Ltd.) are blended, and the above conductive particles are blended and dispersed to adhere. An agent composition was obtained. The mixture ratio of the electroconductive particle in the obtained adhesive composition was 1.5 volume% with respect to the whole quantity of an adhesive composition.

  Next, the obtained adhesive composition was applied to a fluororesin film having a thickness of 80 μm using a coating device (device name: SNC-S3.0, manufactured by Yasui Seiki Co., Ltd.) to form a coating film. Obtained. Next, the coating film was dried with hot air at 70 ° C. for 10 minutes, and a film-like circuit connecting material having a thickness of 20 μm as the adhesive layer (integrated film adhesive and fluororesin film; the same applies hereinafter). Obtained.

(Example 2)
Preparation of adhesive composition and film-like circuit in the same manner as in Example 1 except that 100 parts by weight of the above butyral resin solution (containing 40 parts by weight of butyral resin) was used instead of 100 parts by weight of the phenoxy resin solution A connecting material was produced.

(Example 3)
Preparation of adhesive composition and film in the same manner as in Example 1 except that 133 parts by weight of the above polyester urethane resin solution (containing 40 parts by weight of polyester urethane resin) was used instead of 100 parts by weight of the phenoxy resin solution. A circuit-connecting material was prepared.

Example 4
The blending amount of the isocyanuric acid EO-modified diacrylate was changed from 28 parts by weight to 25 parts by weight, and isocyanurate-modified thiol compound (trade name: THEIC-BMPA, 淀) instead of 22 parts by weight of pentaerythritol tetrakisthiopropionate Chemical Co., Ltd.) An adhesive composition was prepared and a film-like circuit connecting material was prepared in the same manner as in Example 1 except that 25 parts by weight were used.

(Example 5)
Instead of 28 parts by weight of isocyanuric acid EO-modified diacrylate, 15 parts by weight of triallyl isocyanurate (trade name: TAIC, manufactured by Nippon Synthetic Chemical Co., Ltd.) was used, and instead of 22 parts by weight of pentaerythritol tetrakisthiopropionate. Preparation of adhesive composition and production of film-like circuit connecting material in the same manner as in Example 1 except that 35 parts by weight of isocyanurate-modified thiol compound (trade name: THEIC-BMPA, Sakai Chemical Co., Ltd.) was used. Went.

(Example 6)
Using 100 parts by weight of the above butyral resin solution (containing 40 parts by weight of butyral resin) instead of 100 parts by weight of the phenoxy resin solution, isocyanuric acid EO-modified diacrylate (trade name: M-215, manufactured by Toa Gosei Co., Ltd.) ) Was changed from 28 parts by weight to 25 parts by weight, and isocyanurate-modified thiol compound (trade name: THEIC-BMPA, Sakai Chemical Co., Ltd.) 25 instead of 22 parts by weight of pentaerythritol tetrakisthiopropionate An adhesive composition was prepared and a film-like circuit connecting material was prepared in the same manner as in Example 1 except that parts by weight were used.

(Example 7)
Instead of 100 parts by weight of the phenoxy resin solution, 133 parts by weight of the above polyester urethane resin solution (containing 40 parts by weight of the polyester urethane resin) was used. Instead of 28 parts by weight of isocyanuric acid EO-modified diacrylate, triallyl isocyanurate ( Trade name: TAIC, manufactured by Nippon Synthetic Chemical Co., Ltd.) 15 parts by weight, and isocyanurate-modified thiol compound (trade name: THEIC-BMPA, Sakai Chemical Co., Ltd.) instead of 22 parts by weight of pentaerythritol tetrakisthiopropionate Company) An adhesive composition was prepared and a film-like circuit connecting material was prepared in the same manner as in Example 1 except that 35 parts by weight were used.

(Comparative Example 1)
Adhesive composition in the same manner as in Example 1 except that the blending amount of the isocyanuric acid EO-modified diacrylate was changed from 28 parts by weight to 50 parts by weight and that the pentaerythritol tetrakisthiopropionate was not blended. And a film-like circuit connecting material were prepared.

(Comparative Example 2)
The blending amount of the urethane resin was changed from 10 parts by weight to 15 parts by weight. Instead of 28 parts by weight of isocyanuric acid EO-modified diacrylate, 50 parts by weight of triallyl isocyanurate (trade name: TAIC, manufactured by Nippon Synthetic Chemical Co., Ltd.) The adhesive composition was prepared and the film-like circuit connecting material was prepared in the same manner as in Example 1 except that Pt was used and that pentaerythritol tetrakisthiopropionate was not blended.

  Tables 1 and 2 show the blending ratio of each component in the adhesive compositions of Examples 1 to 7 and Comparative Examples 1 and 2.

[Circuit member connection structure]
Using each film-like circuit connecting material of Examples 1 to 7 and Comparative Examples 1 and 2, a circuit member connecting structure was manufactured as follows. First, a flexible circuit board (FPC board) having 500 copper circuit lines having a line width of 25 μm, a pitch of 50 μm, and a thickness of 18 μm, and a glass (ITO substrate, thickness) having a thin film of 0.2 μm indium oxide (ITO) formed on the entire surface. 1.1 mm, surface resistance 20Ω / □). Next, a film-like circuit connecting material is placed between the FPC substrate and the ITO substrate, and using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.), at 140 ° C. and 3 MPa, Heating and pressing for 20 seconds were performed in the laminating direction. At this time, the adhesive surface of the film-like circuit connecting material is pasted on the ITO glass in advance, and is temporarily connected by heating and pressing at 70 ° C. and 0.5 MPa for 5 seconds, and then the fluororesin film is removed from the film-like circuit connecting material. It peeled and connected with the FPC board which is another adherend. In this manner, a circuit member connection structure was obtained in which the FPC board and the ITO board were electrically connected with a cured product of a film adhesive over a width of 2 mm.

  The resistance value between adjacent circuits in the connection structure of the obtained circuit members was measured with a multimeter immediately after bonding and after being kept in a high-temperature and high-humidity bath at 60 ° C. and 90% RH for 48 hours. The resistance value was shown as an average of 37 resistances between adjacent circuits. The obtained results are shown in Table 3.

  Moreover, the adhesive strength in the connection structure of the obtained circuit members was measured by a 90-degree peeling method according to JIS-Z0237 immediately after bonding and after being held in a high-temperature and high-humidity bath at 60 ° C. and 90% RH for 48 hours. did. Here, Tensilon UTM-4 (peeling speed 50 mm / min, 25 ° C.) manufactured by Toyo Baldwin Co., Ltd. was used as a measuring device for adhesive strength. The obtained results are shown in Table 3.

  In Examples 1 to 7, at a heating temperature of 140 ° C., immediately after bonding and after being held in a high-temperature and high-humidity bath at 60 ° C. and 90% RH for 48 hours, good connection resistance and bonding strength are exhibited, and heating over a wide area It was found that it exhibits good characteristics with respect to temperature. On the other hand, in Comparative Example 1 in which no mercapto compound is used, the connection resistance value after the high-temperature and high-humidity treatment is high, and in Comparative Example 2, curing does not proceed by heating at 140 ° C., the connection resistance is open, and the adhesive strength Measurement could not be performed.

(Example 8)
Instead of perhexyl O used as a radical polymerization initiator, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure 819, trade name of Ciba Specialty Chemicals), which is a photo radical initiator, was used. A film-like circuit connecting material was produced in the same manner as in Example 3 except that 5 parts by weight of the solid weight ratio was used.

  Next, using the obtained film-like circuit connecting material, a circuit member connecting structure was manufactured as follows. First, a flexible circuit board (FPC board) having 500 copper circuit lines having a line width of 25 μm, a pitch of 50 μm, and a thickness of 18 μm, and a glass (ITO substrate, thickness) having a thin film of 0.2 μm indium oxide (ITO) formed on the entire surface. 1.1 mm, surface resistance 20Ω / □). Next, a film-like circuit connecting material is placed between the FPC substrate and the ITO substrate, and using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.), at 130 ° C. and 2 MPa, Heating and pressing for 20 seconds were performed in the laminating direction. At this time, the adhesive surface of the film-like circuit connecting material is pasted on the ITO glass in advance, and is temporarily connected by heating and pressing at 70 ° C. and 0.5 MPa for 5 seconds, and then the fluororesin film is removed from the film-like circuit connecting material. It peeled and connected with the FPC board which is another adherend. In addition, when heating and pressurizing for 20 seconds, only heating and pressurization is started, and after 3 seconds have elapsed, ultraviolet irradiation for 17 seconds is started, and after 20 seconds of heating and pressing, two steps of heating and pressurizing and ultraviolet irradiation are simultaneously performed. I ended it. In this manner, a circuit member connection structure was obtained in which the FPC board and the ITO board were electrically connected with a cured product of a film adhesive over a width of 2 mm. When the adhesion strength and connection resistance of the obtained circuit member connection structure were measured in the same manner as described above, the adhesion strength was 790 N / m, the connection resistance was 1.7Ω, and curing at 130 ° C. was possible. Was confirmed.

It is a fragmentary sectional view showing one embodiment of a circuit member connection structure of the present invention. (A)-(c) is a series of process drawings which connect a circuit member, respectively. It is a fragmentary sectional view showing one embodiment of a semiconductor device of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Circuit member connection structure, 2 ... Semiconductor device, 5 ... Adhesive component, 7 ... Conductive particle, 10 ... Circuit connection member, 11 ... Insulating substance, 20 ... 1st circuit member, 21 ... 1st Circuit board, 22 ... first circuit electrode, 30 ... second circuit member, 31 ... second circuit board, 32 ... second circuit electrode, 40 ... film-like circuit connecting member, 50 ... semiconductor element, 60 ... Board | substrate, 61 ... Circuit pattern, 70 ... Sealing material, 80 ... Semiconductor element connection member.

Claims (11)

  An anisotropic conductive adhesive composition comprising a compound having a carbon-carbon double bond in the molecule, a compound having two or more mercapto groups in the molecule, a radical polymerization initiator, and conductive particles. The anisotropic conductive adhesive composition according to claim 1, wherein the compound having two or more mercapto groups in the molecule is a compound further having a benzene ring or an isocyanuric ring in the molecule. The anisotropic conductive adhesive composition according to claim 1 or 2, wherein the compound having two or more mercapto groups in the molecule is a compound having three or more mercapto groups in the molecule. The compound having two or more mercapto groups in the molecule is p-xylene dithiol, m-xylene dithiol, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthioglycolate, trimethylolpropane tristhiopropionate, penta Erythritol tetrakisthiopropionate, 4,4′-thiobenzenethiol, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, The anisotropic conductive adhesive composition according to any one of claims 1 to 3, which is at least one selected from 5H) -trione and a compound represented by the following general formula (1) or (2).

(In formulas (1) and (2), m and n each independently represent an integer of 1 to 5.) The anisotropic conductive adhesive composition according to any one of claims 1 to 4 , further comprising a thermoplastic resin. The anisotropic conductive adhesive composition according to claim 5 , wherein the thermoplastic resin is at least one selected from phenoxy resin, polyester resin, polyurethane resin, polyester urethane resin, butyral resin, acrylic resin, and polyimide resin. A circuit connection material for electrically connecting opposing circuit electrodes, the circuit connection material comprising the anisotropic conductive adhesive composition according to any one of claims 1 to 6 . The film adhesive formed by forming the anisotropic conductive adhesive composition as described in any one of Claims 1-6 in a film form. A film-like circuit connecting material formed by forming the circuit connecting material according to claim 7 into a film shape. A first circuit member having a first circuit electrode formed on the main surface of the first circuit board;
A second circuit member having a second circuit electrode formed on the main surface of the second circuit board;
It is provided between the main surface of the first circuit board and the main surface of the second circuit board, and is electrically in a state where the first circuit electrode and the second circuit electrode are arranged to face each other. A circuit connection member to be connected;
With
The circuit member connection structure according to claim 7 , wherein the circuit connection member is a cured product of the circuit connection material according to claim 7 . A semiconductor element;
A substrate on which the semiconductor element is mounted;
A semiconductor element connecting member that is provided between the semiconductor element and the substrate and electrically connects the semiconductor element and the substrate;
With
The said semiconductor element connection member is a semiconductor device which is a hardened | cured material of the anisotropically conductive adhesive composition as described in any one of Claims 1-6 .

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