JP2009001765A - Adhesive composition, circuit connection structure, and semiconductor device - Google Patents

Abstract

It is possible to obtain excellent adhesive strength even under low temperature and short time curing conditions, and to maintain excellent performance even after a reliability test (for example, left at 85 ° C. and 85% RH). The present invention also provides an adhesive composition having excellent storage stability.
An adhesive composition containing (a) a thermoplastic resin having a urethane bond and an ester bond in the same molecule, (b) a radical polymerizable compound, and (c) a radical polymerization initiator. The adhesive composition is characterized in that it contains two or more types of the above-mentioned (a) thermoplastic resins, and the glass transition temperature of at least one of the above-mentioned (a) thermoplastic resins is 40 ° C. or lower.
[Selection figure] None

Description

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

  2. Description of the Related Art Various adhesive compositions have been conventionally used in semiconductor elements and liquid crystal display elements for the purpose of bonding various members in the elements. The properties required for the adhesive composition are diverse, including adhesiveness, heat resistance, reliability in a high temperature and high humidity state, and the like.

In addition, the adherends used for bonding include printed wiring boards, organic substrates such as polyimide, metals such as copper and aluminum, and substrates having various surface states such as ITO, SiN, and SiO _2. A material is used. Therefore, the adhesive composition needs to have a molecular design tailored to each adherend.

  Conventionally, thermosetting resins such as epoxy resins having high adhesion and high reliability have been used as adhesive compositions for semiconductor elements and liquid crystal display elements (for example, see Patent Document 1). As a component of such an adhesive composition, a curing agent such as an epoxy resin, a phenol resin having reactivity with the epoxy resin, and a thermal latent catalyst that accelerates the reaction between the epoxy resin and the curing agent are generally used. Among these, the heat latent catalyst is an important factor for determining the curing temperature and the curing rate, and various compounds have been used from the viewpoints of storage stability at room temperature and curing rate during heating. Such an adhesive composition can obtain desired adhesion by thermosetting at a temperature of 170 to 250 ° C. for 1 to 3 hours.

  However, with the recent high integration of semiconductor elements and high definition of liquid crystal elements, the pitch between elements and wirings has narrowed, and there has been a risk of adversely affecting peripheral members due to heating during curing.

  Furthermore, in order to reduce the cost, there is a need to improve the throughput, and there is a demand for an adhesive composition that cures at a lower temperature and in a shorter time, in other words, an adhesive composition that is “low temperature fast cure”. Yes. In order to achieve low-temperature rapid curing of the adhesive composition, for example, a thermal latent catalyst having a low activation energy may be used, and in that case, it is extremely desirable to combine storage stability near room temperature. It is known to be difficult.

  In addition, as an adhesive composition that meets the requirements for low-temperature rapid curing, recently, radicals that use acrylate derivatives and methacrylate derivatives (hereinafter referred to as “(meth) acrylate derivatives”) and peroxides as radical polymerization initiators in combination. A curable adhesive is drawing attention. Such an adhesive composition can be cured in a short time because radicals that are reactive species are highly reactive (see, for example, Patent Document 2).

  On the other hand, a method using a thermoplastic resin having a specific functional group such as a silicon-modified polyimide resin or a polyester urethane resin has been proposed in order to improve the adhesive strength when using a radical curable adhesive (for example, patents). References 3 and 4).

Japanese Patent Laid-Open No. 1-113480 International Publication No. 98/44067 Pamphlet JP 2002-203427 A JP 2006-318990 A

  However, the radical curable adhesive described in Patent Document 2 has a problem that the adhesive strength is not always sufficient. In addition, when a radically polymerizable compound and a peroxide are used in combination, it is necessary to use a peroxide having a low activation energy in order to achieve sufficient low-temperature rapid curing, and storage stability near room temperature is required. May decrease. In addition, it is difficult to ensure sufficient moisture resistance reliability with adhesive strength.

  Further, even when a thermoplastic resin having a specific functional group as shown in Patent Documents 3 and 4 is used, when cured at a low temperature, the reaction of the radical polymerizable compound does not sufficiently proceed, It is difficult to show high adhesive strength.

  The present invention has been made in view of the above-described problems of the prior art, and can provide excellent adhesive strength even under low-temperature and short-time curing conditions. In addition, a reliability test (for example, 85 ° C., 85% An object of the present invention is to provide an adhesive composition that can maintain excellent performance even after RH leaving) and also has excellent storage stability, and a circuit connection structure and a semiconductor device using the adhesive composition. And

  In order to achieve the above object, the present invention comprises (a) a thermoplastic resin having a urethane bond and an ester bond in the same molecule, (b) a radical polymerizable compound, and (c) a radical polymerization initiator. An adhesive composition containing two or more types of the above-mentioned (a) thermoplastic resin, and at least one of the above-mentioned (a) thermoplastic resins has a glass transition temperature of 40 ° C. or lower. An adhesive composition is provided.

  According to such an adhesive composition, by having the above-described configuration, excellent adhesive strength can be obtained even under low temperature and short time curing conditions, and a reliability test (for example, left at 85 ° C. and 85% RH). ) Excellent performance can be maintained afterwards, and excellent storage stability can be obtained. In particular, by containing at least one thermoplastic resin (a) having a glass transition temperature of 40 ° C. or lower, excellent adhesive strength can be obtained not only immediately after connection but also after a reliability test.

  In the adhesive composition of the present invention, the glass transition temperature of at least one of the above-mentioned (a) thermoplastic resins is preferably 60 ° C. or higher. (A) A thermoplastic resin having a glass transition temperature of 60 ° C. or higher and (a) a thermoplastic resin having a glass transition temperature of 40 ° C. or lower in combination with (a) a thermoplastic resin to further secure the heat resistance of the adhesive composition. can do.

  The adhesive composition of the present invention preferably further contains (d) a vinyl compound having one or more phosphate groups in the molecule. Thereby, more excellent adhesive strength can be obtained under low temperature and short time curing conditions.

  Moreover, it is preferable that the adhesive composition of this invention contains (e) electroconductive particle further. Thereby, since electroconductivity or anisotropic conductivity can be provided to an adhesive composition, it becomes possible to use an adhesive composition suitably for the connection use etc. of the circuit members which have a circuit electrode. . Moreover, the connection resistance between the circuit electrodes electrically connected through the adhesive composition can be sufficiently reduced.

  The present invention also provides a pair of circuit members disposed opposite to each other, and the circuit members provided between the pair of circuit members so that the circuit electrodes of the pair of circuit members are electrically connected to each other. A circuit connection structure, wherein the connection member is made of a cured product of the adhesive composition of the present invention.

  In such a circuit connection structure, since the connection member for connecting the pair of circuit members is composed of the cured product of the adhesive composition of the present invention, the adhesive strength between the circuit members can be sufficiently increased. And even if it is a case where it is left for a long time in a high-temperature, high-humidity environment, the fall of adhesive strength can fully be suppressed.

  The present invention further includes a semiconductor element, a substrate on which the semiconductor element is mounted, and a connection member that is provided between the semiconductor element and the substrate and electrically connects and bonds the semiconductor element and the substrate. A semiconductor device in which the connecting member is made of a cured product of the adhesive composition of the present invention is provided.

  In such a semiconductor device, since the connecting member for connecting the semiconductor element and the substrate is made of the cured product of the adhesive composition of the present invention, the bonding strength between the semiconductor element and the substrate is sufficiently increased. Even if it is a case where it is left for a long time in a high-temperature and high-humidity environment, it is possible to sufficiently suppress the decrease in the adhesive strength.

  According to the present invention, excellent adhesive strength can be obtained even under low-temperature and short-time curing conditions, and excellent performance can be maintained even after a reliability test (for example, at 85 ° C. and 85% RH). In addition, it is possible to provide an adhesive composition excellent in storage stability, a circuit connection structure using the adhesive composition, and a semiconductor device.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted. In the present invention, (meth) acrylic acid indicates acrylic acid or methacrylic acid corresponding thereto, (meth) acrylate means acrylate or methacrylate corresponding thereto, and (meth) acryloyl group means acryloyl group or Means a methacryloyl group;

  The adhesive composition of the present invention is an adhesive containing (a) a thermoplastic resin having a urethane bond and an ester bond in the same molecule, (b) a radical polymerizable compound, and (c) a radical polymerization initiator. A composition comprising two or more types of the above-mentioned (a) thermoplastic resin, and at least one of the above-mentioned (a) thermoplastic resins has a glass transition temperature of 40 ° C. or lower. It is. Hereinafter, each component will be described in detail.

  The thermoplastic resin (a) having a urethane bond and an ester bond in the same molecule (hereinafter sometimes referred to as “polyester urethane resin”) used in the present invention can be obtained, for example, by a reaction between a polyester polyol and a diisocyanate. (A) As a weight average molecular weight of a polyester urethane resin, 5,000-150,000 are preferable and 10,000-80,000 are more preferable. If this value is less than 5,000, the film formability tends to be inferior when used in the form of a film, and if it exceeds 150,000, the compatibility with other components tends to be poor.

  The polyester polyol used for the synthesis | combination of a polyester urethane resin can be obtained by reaction of dicarboxylic acid and diol, for example. Specific examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, adipic acid, and sebacic acid. Specific examples of the diol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, triethylene glycol, and the like. These can be used alone or in combination.

  Further, the diisocyanate compound specifically includes 2,4-tolylene diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, naphthalene-1,5-diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, 4,4′-diphenylmethane diisocyanate, Dicyclohexylmethane-4,4′-diisocyanate, toluene-2,6-diisocyanate, toluene-2,4-diisocyanate, triethylhexamethylene diisocyanate, m-xylene diisocyanate Such as over doors and the like. These can be used alone or in combination.

  The adhesive composition of the present invention comprises two or more types of (a) polyester urethane resins, and has at least one glass transition temperature of 40 ° C. or lower. When the (a) polyester urethane resin having a glass transition temperature of 40 ° C. or lower is not included, the adhesive strength is significantly lowered after the moisture resistance test.

  The glass transition temperature of the (a) polyester urethane resin having a glass transition temperature of 40 ° C. or lower is more preferably 0 to 35 ° C., and particularly preferably 5 to 30 ° C. When the glass transition temperature is less than 0 ° C., the heat resistance of the adhesive composition tends to be remarkably lowered.

  Here, the ratio of the (a) polyester urethane resin having a glass transition temperature of 40 ° C. or less in the entire two or more types of (a) polyester urethane resins is 5 to 5% on the basis of the amount of the whole (a) polyester urethane resin. It is preferably 60% by mass, more preferably 10 to 40% by mass. If this ratio is less than 5% by mass, the adhesive strength tends to decrease after the moisture resistance test, and if it exceeds 60% by mass, the heat resistance of the adhesive composition tends to decrease.

  Moreover, it is preferable that the glass transition temperature of at least 1 type (a) polyester urethane resin is 60 degreeC or more among the 2 or more types (a) polyester urethane resins of the adhesive composition of this invention. When the (a) polyester urethane resin having a glass transition temperature of 60 ° C. or higher is not included, it tends to be difficult to ensure sufficient heat resistance.

  The glass transition temperature of the (a) polyester urethane resin having a glass transition temperature of 60 ° C. or higher is more preferably 60 to 90 ° C., and particularly preferably 65 to 85 ° C. When the glass transition temperature exceeds 90 ° C., the fluidity of the adhesive composition tends to decrease.

  Here, the ratio of the (a) polyester urethane resin having a glass transition temperature of 60 ° C. or higher in the entire two or more types of (a) polyester urethane resins is 40 to 40% on the basis of the amount of the whole (a) polyester urethane resins. It is preferably 95% by mass, and more preferably 60 to 90% by mass. If this ratio is less than 40% by mass, it tends to be difficult to ensure sufficient heat resistance, and if it exceeds 95% by mass, the adhesive strength tends to decrease after the moisture resistance test.

  In the adhesive composition of the present invention, the total content of two or more types of (a) polyester urethane resins is preferably 2.5 to 60% by mass based on the total amount of the adhesive composition, and is preferably 5 to 55%. More preferably, it is mass%. If the amount added is less than 2.5% by mass, the adhesive strength tends to decrease after the moisture resistance test, and if it exceeds 60% by mass, the fluidity may decrease.

  As the radically polymerizable compound (b) used in the present invention, known compounds can be used without any particular limitation. The (b) radical polymerizable compound can be used in either a monomer or oligomer state, and a monomer and an oligomer may be mixed and used.

  (B) Specific examples of the radical polymerizable compound include epoxy (meth) acrylate oligomers, urethane (meth) acrylate oligomers, polyether (meth) acrylate oligomers, polyester (meth) acrylate 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, di Pentaerythritol hexa (meth) acrylate, isocyanuric acid modified bifunctional (meth) acrylate, isocyanuric acid modified trifunctional (meth) acrylate, bisphenol fluor (Meth) acryloyloxy group is introduced into compounds in which ethylene glycol or propylene glycol is added to the glycidyl group of bisphenol fluorenediglycidyl ether. And the compounds represented by the following general formulas (1) and (2). These compounds can be used individually by 1 type or in mixture of 2 or more types.

［式中、Ｒ^１及びＲ^２は各々独立に水素原子又はメチル基を示し、ｋ及びｌは各々独立に１〜８の整数を示す。なお、式中、Ｒ^１同士及びＲ^２同士はそれぞれ同一でも異なっていてもよい。］

[Wherein, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and k and l each independently represent an integer of 1 to 8. In the formula, R ¹ and R ² may be the same or different. ]

［式中、Ｒ^３及びＲ^４は各々独立に水素原子又はメチル基を示し、ｍ及びｎは各々独立に０〜８の整数を示す。なお、式中、Ｒ^３同士及びＲ^４同士はそれぞれ同一でも異なっていてもよい。］

[Wherein, R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and m and n each independently represents an integer of 0 to 8. In the formula, R ³ and R ⁴ may be the same or different. ]

  The adhesive composition of the present invention preferably contains a compound having two or more (meth) acryloyl groups in the molecule as the radically polymerizable compound (b).

  Moreover, the adhesive composition of this invention may contain monofunctional (meth) acrylate as a (b) radically polymerizable compound for the purpose of adjustment of fluidity | liquidity. Examples of monofunctional (meth) acrylates include pentaerythritol (meth) acrylate, 2-cyanoethyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate. 2- (2-ethoxyethoxy) ethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-hexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxy Propyl (meth) acrylate, isobornyl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, n-lauryl (meth) acrylate, 2-methoxyethyl (meth) acrylate Rate, 2-phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (Meth) acrylate, (meth) acryloylmorpholine, etc. are mentioned. These compounds may be used alone or in combination with a plurality of compounds in addition to the use of one kind alone.

  Furthermore, for the purpose of improving the crosslinking rate, the adhesive composition of the present invention is an allyl group, a maleimide group, a vinyl group in addition to the compound having the (meth) acryloyl group as the radical polymerizable compound (b). A compound having a functional group that is polymerized by an active radical, such as, may be added as appropriate. Specifically, N-vinylimidazole, N-vinylpyridine, N-vinylpyrrolidone, N-vinylformamide, N-vinylcaprolactam, 4,4′-vinylidenebis (N, N-dimethylaniline), N-vinylacetamide N, N-dimethylacrylamide, N-isopropylacrylamide, N, N-diethylacrylamide and the like.

  In the adhesive composition of the present invention, the content of the (b) radical polymerizable compound is preferably 50 to 250 parts by mass, and 60 to 150 parts by mass with respect to 100 parts by mass of the (a) polyester urethane resin. It is more preferable that When this content is less than 50 parts by mass, there is a concern about a decrease in heat resistance after curing, and when it exceeds 250 parts by mass, the film forming property is used when the adhesive composition is formed into a film. May decrease.

  As the radical polymerization initiator (c) used in the present invention, known compounds such as conventionally known peroxides and azo compounds can be used. From the viewpoint 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. Here, “one-minute half-life temperature” refers to the temperature at which the half-life is 1 minute, and “half-life” refers to the time until the concentration of the compound decreases to half of the initial value.

  (C) Specific examples of radical polymerization initiators include 1,1,3,3-tetramethylbutylperoxyneodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate, and di (2-ethylhexyl). ) Peroxydicarbonate, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, dilauroyl peroxide, 1-cyclohexyl-1-methylethylperoxyneodecano Ate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hex Luperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneoheptanoate, t-amylperoxy-2-ethylhexanoate, di-t-butyl Peroxyhexahydroterephthalate, t-amylperoxy-3,5,5-trimethylhexanoate, 3-hydroxy-1,1-dimethylbutylperoxyneodecanoate, 1,1,3,3-tetramethyl Butylperoxy-2-ethylhexanoate, t-amylperoxyneodecanoate, t-amylperoxy-2-ethylhexanoate, 3-methylbenzoyl peroxide, 4-methylbenzoyl peroxide, di ( 3-methylbenzoyl) peroxide, dibenzoyl peroxide, di (4-me Rubenzoyl) peroxide, 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 mono Carbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxybenzoate, dibutylperoxytrimethyladipate, t-amylperoxynormal octoate, t -Amyl peroxy isononanoate, t-amyl peroxybenzoate, etc. are mentioned. These compounds may be used alone or in combination of two or more compounds.

  Moreover, as (c) radical polymerization initiator, the compound which generate | occur | produces a radical by light irradiation with a wavelength of 150-750 nm can be used. As such a compound, a known compound can be used without any particular limitation. For example, Photoinitiation, Photopolymerization, and Photocuring, J. Biol. -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 alone or in combination with the above peroxides or azo compounds.

  Further, in order to suppress corrosion of the connection terminals of the circuit member, the amount of chlorine ions and organic acids contained in the radical polymerization initiator (c) is preferably 5000 ppm or less, and further, an organic matter generated after thermal decomposition. Those with less acid are more preferred. In addition, since the stability of the produced circuit connecting material is improved, it is preferable to use a radical polymerization initiator (c) having a mass retention of 20% by mass or more after being left open at room temperature and normal pressure for 24 hours.

  Examples of the vinyl compound having one or more phosphate groups in the molecule (d) used as necessary in the present invention include compounds represented by the following general formulas (3) to (5).

［式中、Ｒ^５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。なお、式中、Ｒ^５同士、Ｒ^６同士、ｗ同士及びｘ同士はそれぞれ同一でも異なっていてもよい。］

[Wherein, R ⁵ represents a (meth) acryloyl group, R ⁶ represents a hydrogen atom or a methyl group, and w and x each independently represents an integer of 1 to 8. In the formula, R ^{5 s} , R ^{6 s} , w s, and x s may be the same or different. ]

［式中、Ｒ^７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。なお、式中、Ｒ^７同士、ｙ同士及びｚ同士はそれぞれ同一でも異なっていてもよい。］

Wherein, ^{R 7} represents a (meth) acryloyl group, y and z each independently represents a 1-8 integer. In the formula, R ^{7 s} , y s, and z s may be the same or different. ]

［式中、Ｒ^８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、ａ及びｂは各々独立に１〜８の整数を示す。なお、式中、Ｒ^９同士及びａ同士はそれぞれ同一でも異なっていてもよい。］

[Wherein, R ⁸ represents a (meth) acryloyl group, R ⁹ represents a hydrogen atom or a methyl group, and a and b each independently represents an integer of 1 to 8. In the formulas, R ⁹ and between a each other may be the same as or different from each other. ]

  (D) Specific examples of vinyl compounds having one or more phosphate groups in the molecule include acid phosphooxyethyl methacrylate, acid phosphooxyethyl acrylate, acid phosphooxypropyl methacrylate, and acid phosphooxypolyoxyethylene glycol monomethacrylate. Acid phosphooxypolyoxypropylene glycol monomethacrylate, 2,2′-di (meth) acryloyloxydiethyl phosphate, EO-modified phosphate dimethacrylate, phosphate-modified epoxy acrylate, vinyl phosphate and the like.

  In the adhesive composition of the present invention, (d) the content of the vinyl compound having one or more phosphate groups in the molecule is 0.1 to 15 masses per 50 mass parts of the (a) polyester urethane resin. Part, preferably 0.5 to 10 parts by weight. When this content is less than 0.1 parts by mass, high adhesive strength tends to be difficult to obtain, and when it exceeds 15 parts by mass, the physical properties of the adhesive composition after curing are likely to deteriorate, and the reliability May be reduced.

  Examples of the conductive particles (e) used as necessary in the present invention include metal particles such as Au, Ag, Ni, Cu, and solder, and carbon particles. Further, (e) the conductive particles may have non-conductive glass, ceramic, plastic or the like as a core, and the core is coated with the metal, metal particles, carbon or the like. (E) In the case where the conductive particles are made of plastic as a core and the core is coated with the above metal, metal particles, carbon, or the like, or a hot-melt metal particle, the circuit member is deformable by heating and pressing. When connecting each other, the contact area between the conductive particles and the electrode is increased, which is preferable because the reliability is improved.

  In addition, the fine particles with the surface of these conductive particles coated with a polymer resin or the like suppress short circuit due to contact between particles when the amount of the conductive particles is increased, and provide insulation between circuit electrodes. Can be improved. The particle | grains which coat | covered the surface of the electroconductive particle with polymeric resin etc. can be used individually or in mixture with another electroconductive particle.

  (E) It is preferable that the average particle diameter of electroconductive particle is 1-18 micrometers from a viewpoint of obtaining favorable dispersibility and electroconductivity.

  When such (e) conductive particles are contained, the adhesive composition can be suitably used as an anisotropic conductive adhesive composition.

  The content of the conductive particles (e) in the adhesive composition of the present invention is not particularly limited, but is preferably 0.1 to 30% by volume based on the total volume of the adhesive composition. More preferably, it is made into 10 volume%. When this content is less than 0.1% by volume, the conductivity tends to be inferior, and when it exceeds 30% by volume, a short circuit between circuit electrodes tends to occur. In addition, (e) Content (volume%) of electroconductive particle is determined based on the volume of each component before hardening at 23 degreeC. In addition, the volume of each component can be calculated | required by converting mass into a volume using specific gravity. Also, put an appropriate solvent (water, alcohol, etc.) that can wet the component well without dissolving or swelling the component whose volume is to be measured. It is also possible to obtain the volume increased by charging as the volume of the component.

  Moreover, in addition to (a) polyester urethane resin mentioned above, the adhesive composition of this invention can mix and use the well-known thermoplastic resin which does not have a restriction | limiting in particular.

  As a known thermoplastic resin, polyimide resin, polyamide resin, phenoxy resin, poly (meth) acrylate resin, polyimide resin, polyurethane resin, polyester resin, polyvinyl butyral resin, or the like can be used.

  Furthermore, these thermoplastic resins may contain siloxane bonds or fluorine substituents. These can be suitably used as long as the resins to be mixed are completely compatible with each other or microphase separation occurs and becomes cloudy. The larger the molecular weight of the resin, the easier it is to obtain film formability, and the melt viscosity that affects the fluidity as an adhesive can be set over a wide range. The molecular weight is not particularly limited, but a general weight average molecular weight is preferably 5,000 to 150,000, and more preferably 10,000 to 80,000. If this value is less than 5,000, the film formability tends to be inferior, and if it exceeds 150,000, the compatibility with other components tends to deteriorate.

  A stabilizer may be added to the film-like adhesive composition of the present invention in order to control the curing rate and impart storage stability. As such a stabilizer, known compounds can be used without particular limitation, but 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 1,6,6-tetramethylpiperidine-1-oxyl and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and hindered amine derivatives such as tetramethylpiperidyl methacrylate.

  The addition amount of the stabilizer is preferably 0.01 to 30 parts by mass and more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the (a) polyester urethane resin. When this addition amount is less than 0.01 parts by mass, the effect of addition tends to be insufficient, and when it exceeds 30 parts by mass, the compatibility with other components may be reduced.

  To the adhesive composition of the present invention, a bonding aid such as a coupling agent represented by an alkoxysilane derivative or a silazane derivative, an adhesion improver, or a leveling agent may be appropriately added. Specifically, a compound represented by the following general formula (6) is preferable as such an adhesion assistant. These adhesion assistants can be used alone or in combination of two or more.

［式中、Ｒ^１０、Ｒ^１１及びＲ^１２は各々独立に、水素原子、炭素数１〜５のアルキル基、炭素数１〜５のアルコキシ基、炭素数１〜５のアルコキシカルボニル基、又は、アリール基を示し、Ｒ^１３は（メタ）アクリロイル基、ビニル基、イソシアナート基、イミダゾール基、メルカプト基、アミノ基、メチルアミノ基、ジメチルアミノ基、ベンジルアミノ基、フェニルアミノ基、シクロヘキシルアミノ基、モルホリノ基、ピペラジノ基、ウレイド基、又は、グリシジル基を示し、ｃは１〜１０の整数を示す。］

[Wherein R ¹⁰ , R ¹¹ and R ¹² are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxycarbonyl group having 1 to 5 carbon atoms, or R ¹³ represents an aryl group, and R ¹³ represents a (meth) acryloyl group, a vinyl group, an isocyanate group, an imidazole group, a mercapto group, an amino group, a methylamino group, a dimethylamino group, a benzylamino group, a phenylamino group, a cyclohexylamino group, A morpholino group, a piperazino group, a ureido group, or a glycidyl group is shown, and c represents an integer of 1 to 10. ]

  A rubber component may be added to the adhesive composition of the present invention for the purpose of stress relaxation and improved adhesion. Specific examples of the rubber component include polyisoprene, polybutadiene, carboxyl-terminated polybutadiene, hydroxyl-terminated polybutadiene, 1,2-polybutadiene, carboxyl-terminated 1,2-polybutadiene, hydroxyl-terminated 1,2-polybutadiene, acrylic rubber, styrene- Butadiene rubber, hydroxyl-terminated styrene-butadiene rubber, acrylonitrile-butadiene rubber, carboxyl group, hydroxyl group, (meth) acryloyl group or morpholine group-containing acrylonitrile-butadiene rubber, carboxylated nitrile rubber, hydroxyl-terminated poly (oxypropylene) ), Alkoxysilyl group-terminated poly (oxypropylene), poly (oxytetramethylene) glycol, polyolefin glycol, and poly-ε-caprolactone.

  As the rubber component, a rubber component containing a cyano group or a carboxyl group, which is a highly polar group, in the side chain or terminal is preferable from the viewpoint of improving adhesiveness, and liquid rubber is more preferable from the viewpoint of improving fluidity. Specific examples of the rubber component include liquid acrylonitrile-butadiene rubber, liquid acrylonitrile-butadiene rubber containing a carboxyl group, a hydroxyl group, a (meth) acryloyl group or a morpholine group at the polymer terminal, and a liquid carboxylated nitrile rubber. In these rubber components, the acrylonitrile content, which is a polar group, is preferably 10 to 60% by mass. These compounds can be used individually by 1 type or in mixture of 2 or more types.

  The adhesive composition of the present invention can be used in the form of a paste when it is liquid at normal temperature (25 ° C.). In the case of a solid at normal temperature (25 ° C.), it may be used by heating, or by pasting it with a solvent. Here, the solvent that can be used is not particularly limited as long as it is not reactive with the adhesive composition (including additives) and can sufficiently dissolve the adhesive composition, but it has a boiling point at normal pressure. Is preferably from 50 to 150 ° C. If the boiling point is less than 50 ° C., it may volatilize if left at room temperature (25 ° C.), which limits the use in an open system. On the other hand, if the boiling point exceeds 150 ° C., it is difficult to volatilize the solvent, which may adversely affect the reliability after bonding.

  The adhesive composition of the present invention can be formed into a film and used as a film adhesive. When forming a film-like adhesive, a solution obtained by adding a solvent or the like to the adhesive composition as necessary is placed on a peelable substrate such as a fluororesin film, a polyethylene terephthalate film, or a release paper. It can be formed into a film by applying or impregnating a base material such as a nonwoven fabric with the above solution and placing it on a peelable base material and removing the solvent and the like. When used as a film adhesive, it is more convenient from the viewpoint of handleability.

  FIG. 1 is a schematic cross-sectional view showing an embodiment of a film adhesive comprising the adhesive composition of the present invention. The film adhesive 1 shown in FIG. 1 is formed by forming the above-described adhesive composition into a film. According to this film adhesive, it is easy to handle, can be easily installed on the adherend, and can be easily connected. Moreover, the film adhesive 1 may have a multilayer structure (not shown) which consists of 2 or more types of layers. Moreover, when the film adhesive 1 contains the said (e) electroconductive particle (not shown), it can use suitably as an anisotropic conductive film.

  The adhesive composition and the film adhesive of the present invention can usually adhere adherends together using heating and pressurization. The heating temperature is not particularly limited, but is preferably 100 to 250 ° C. The pressure is not particularly limited as long as it does not damage the adherend, but it is generally preferably 0.1 to 10 MPa. These heating and pressurization are preferably performed in the range of 0.5 seconds to 120 seconds. According to the adhesive composition and the film-like adhesive of the present invention, for example, adherends can be sufficiently bonded to each other even under short-time heating and pressurization for 10 seconds under conditions of 150 to 200 ° C. and 3 MPa. Is possible.

  The adhesive composition and film adhesive of the present invention can be used as an adhesive for different types of adherends having different thermal expansion coefficients. Specifically, it is used as a semiconductor element adhesive material typified by anisotropic conductive adhesive, silver paste, silver film, etc., circuit connection material, CSP elastomer, CSP underfill material, LOC tape, etc. Can do.

  Hereinafter, using the adhesive composition and the film-like adhesive of the present invention as an anisotropic conductive adhesive composition and an anisotropic conductive film, circuit members having circuit electrodes formed on the main surface of a circuit board. An example of connection will be described. That is, an anisotropic conductive adhesive composition or an anisotropic conductive film is disposed between circuit electrodes facing each other on a circuit board, and heated and pressed to thereby connect the electrical connection between the facing circuit electrodes and the circuit board. The circuit members can be connected with each other. Here, as a circuit board for forming a circuit electrode, a substrate made of an inorganic substance such as a semiconductor, glass or ceramic, a board made of an organic substance such as polyimide or polycarbonate, a board formed by combining an inorganic substance such as glass / epoxy and an organic substance, or the like. Can be used. Moreover, when using the adhesive composition and film adhesive of this invention for the use as such a circuit connection material, it is preferable to make these contain electroconductive particle.

  FIG. 2 is a schematic cross-sectional view showing an embodiment of the circuit connection structure (circuit member connection structure) of the present invention. As shown in FIG. 2, the circuit member connection structure of the present embodiment includes a first circuit member 20 and a second circuit member 30 that are opposed to each other. A circuit connection member 10 is provided between the circuit member 30 and the circuit member 30.

  The first circuit member 20 includes a circuit board (first circuit board) 21 and a circuit electrode (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 circuit board (second circuit board) 31 and a circuit electrode (second circuit electrode) 32 formed on the main surface 31 a of the 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 and second circuit members 20 and 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. Used in combination accordingly. Thus, in the present embodiment, including the material composed of organic material such as a printed circuit board, polyimide, copper, aluminum or the like metal or ITO (indium tin oxide), silicon nitride _(SiN x), silicon dioxide _(SiO 2) Circuit members having various surface states such as inorganic materials such as the above can be used.

  The circuit connecting member 10 is made of a cured product of the adhesive composition or film adhesive of the present invention. The circuit connection member 10 contains an insulating material 11 and conductive particles 7. The conductive particles 7 are disposed not only between the circuit electrode 22 and the circuit electrode 32 facing each other but also between the main surfaces 21a and 31a. In the circuit member connection structure, the circuit electrodes 22 and 32 are electrically connected via the conductive particles 7. That is, the conductive particles 7 are in direct contact with both the circuit electrodes 22 and 32.

  Here, the conductive particles 7 are (e) the conductive particles described above, and the insulating substance 11 is a cured component of each of the insulating components constituting the adhesive composition or film adhesive of the present invention. It is a thing.

  In the circuit member connection structure, as described above, the circuit electrode 22 and the circuit electrode 32 facing each other are electrically connected via the conductive particles 7. For this reason, the connection resistance between the circuit electrodes 22 and 32 is sufficiently reduced. Therefore, the flow of current between the circuit electrodes 22 and 32 can be made smooth, and the functions of the circuit can be fully exhibited. When the circuit connecting member 10 does not contain the conductive particles 7, the circuit electrode 22 and the circuit electrode 32 are in direct contact with each other to be electrically connected.

  Since the circuit connecting member 10 is composed of the adhesive composition of the present invention or a cured product of the film adhesive, the adhesive strength of the circuit connecting member 10 with respect to the circuit member 20 or 30 is sufficiently high, and reliability. Stable performance (adhesive strength and connection resistance) can be maintained even after the test (high temperature and high humidity test).

  Next, an example of the manufacturing method of the circuit member connection structure described above will be described. First, the first circuit member 20 described above and a film adhesive (film circuit connection material) 40 are prepared (see FIG. 3A). The film-like circuit connection material 40 is formed by molding an adhesive composition (circuit connection material) into a film shape, and contains the conductive particles 7 and 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 NCP (Non-Conductive Paste). Further, when the circuit connecting material contains the conductive particles 7, the circuit connecting material may be referred to as ACP (Anisotropic Conductive Paste).

  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 it exceeds 50 μm, the adhesive composition between the circuit electrodes 22 and 32 cannot be sufficiently removed, and it is 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.3 (a), and the film-form circuit connection material 40 is temporarily connected to the 1st circuit member 20 (refer FIG.3 (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. 3C, the second circuit member 30 is placed on the film-like circuit connection material 40 so that the second circuit electrode faces 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.3 (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 connecting material 40 is cured to perform the main connection, and a circuit member connection structure as shown in FIG. 2 is obtained.

  Here, as described above, the connection conditions are preferably a heating temperature of 100 to 250 ° C., a pressure of 0.1 to 10 MPa, and a connection time of 0.5 seconds to 120 seconds. 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.

  By manufacturing the circuit member connection structure 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. , 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 obtained circuit member connection structure, since the circuit connection member 10 is made of a cured product of the circuit connection material made of the adhesive composition of the present invention, the circuit connection member 10 for the circuit member 20 or 30 is used. In addition, the bonding strength between the electrically connected circuit electrodes can be sufficiently reduced. Moreover, even when it is left for a long time in a high temperature and high humidity environment, it is possible to sufficiently suppress a decrease in adhesive strength and an increase in connection resistance.

  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, when the film-like circuit connecting material 40 is cured, light irradiation may be performed instead of heating. 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.

  In addition, in the manufacturing method of the circuit member connection structure, in addition to the radical polymerization initiator that generates radicals by heating or light irradiation, a radical polymerization initiator that generates radicals by ultrasonic waves, electromagnetic waves, or the like is used as necessary. May be.

  FIG. 4 is a schematic cross-sectional view showing an embodiment of the semiconductor device of the present invention. As shown in FIG. 4, the semiconductor device 2 includes a semiconductor element 50 and a substrate 60 that serves as a semiconductor support member, and a semiconductor that electrically connects between the semiconductor element 50 and the substrate 60. An element connection member 80 is provided. 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 devices such as GaSb, InSb, GaN, AlN, InGaN, InNAsP, II-VI group compound semiconductor devices 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, 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.

  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 of the present invention. From this, the adhesive strength of the semiconductor element connection member 80 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 is sufficiently small. Moreover, even when it is left for a long time in a high temperature and high humidity environment, it is possible to sufficiently suppress a decrease in adhesive strength and an increase in connection resistance. Further, the semiconductor element connection member 80 can be formed by a heat treatment at a low temperature for a short time. Therefore, the semiconductor device 2 can have higher reliability than before.

  Further, the semiconductor device 2 uses the substrate 60 and the semiconductor element 50 for the first and second circuit members 20 and 30 in the method for manufacturing the circuit member connection structure described above, and the method for manufacturing the circuit member connection structure described above. It can be manufactured by the same method.

  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.

(Method for preparing polyester polyol)
A dicarboxylic acid and a diol are charged at a predetermined ratio into a stainless steel autoclave equipped with a heater equipped with a stirrer, a thermometer, a condenser, a vacuum generator, and a nitrogen gas introduction pipe, and antimony trioxide as a catalyst is further added to the above dicarboxylic acid. Choline hydroxide as a surfactant was added at a ratio of 0.003 mol per 100 mol of acid at a ratio of 4 mol per 100 mol of the dicarboxylic acid. Subsequently, it heated up to 250 degreeC over 2.5 hours under 0.35 Mpa nitrogen pressure, and stirred as it was for 1 hour. Thereafter, the pressure was reduced to atmospheric pressure (760 mmHg) at 30 mmHg / min, and the mixture was stirred at 250 ° C. for 3 hours. Next, after cooling to 25 ° C., a white precipitate was taken out, washed with water, and vacuum dried to obtain a polyester polyol.

(Preparation method of polyester urethane resin)
After sufficiently drying the polyester polyol obtained by the reaction of the dicarboxylic acid and the diol described above, it is dissolved in toluene and charged into a four-necked flask equipped with a stirrer, dropping funnel, reflux condenser and nitrogen gas inlet tube. did. Further, dibutyltin laurate was added as a catalyst in an amount of 0.02 parts by mass with respect to 100 parts by mass of the polyester polyol.

  On the other hand, diisocyanate was dissolved in toluene and placed in the dropping funnel. Heating was started after the reaction system was replaced with dry nitrogen, and when refluxing started, the solution in the dropping funnel was added half at a time and stirred vigorously. The remaining solution was added dropwise over 3 hours, and the mixture was further stirred for 1 hour after the addition. Subsequently, the precipitate obtained by cooling to 25 ° C. was dissolved in dimethylformamide, methanol was added in an amount equal to dimethylformamide, and the mixture was left overnight in a refrigerator (5 ° C.). The target polyester urethane resin was obtained by vacuum-drying the precipitate obtained after leaving to stand.

(Synthesis of polyester urethane resins A to E)
Various polyester urethanes were used according to the above procedure, using terephthalic acid, isophthalic acid or adipic acid as digalbonic acid, neopentyl glycol as diol, and 4,4'-diphenylmethane diisocyanate as diisocyanate so as to have the mass ratio shown in Table 1, respectively. Resins A to E were obtained. 60 g of each obtained polyester urethane resin was melt | dissolved in 90 g of methyl ethyl ketone, and the 40 mass% polyester urethane resin solution was prepared.

(Measurement of glass transition temperature of polyester urethane resins A to E)
The glass transition temperature of each obtained polyester urethane resin was measured on condition of the following using DSC. 0.01 g of each polyester urethane resin was weighed and measured using DSC7 (trade name) manufactured by PerkinElmer Co., Ltd. under a nitrogen atmosphere at a temperature range of 25 to 200 ° C. and a heating rate of 10 ° C./min. The straight line before and after the inflection point of the obtained endothermic curve was extended, and the temperature at which the endothermic curve intersected with a half line between the two extended lines was defined as the glass transition temperature. The measurement results are shown in Table 2.

(Measurement of weight average molecular weight of polyester urethane resins A to E)
The weight average molecular weight of each obtained polyester urethane resin was measured using gel permeation chromatography. The column was GelpackGL-R440 + GL-R450 + GL-R400M, the solvent was tetrahydrofuran, and the flow rate was 2.05 ml / min, the injection amount was 200 μl, and the pressure was 519.4 MPa (53 kgf / cm ² ). As the detector, L-3300RI manufactured by Hitachi, Ltd. was used. The weight average molecular weight of each polyester urethane resin was calculated from a calibration curve using polystyrene. The results are shown in Table 3.

(Preparation of conductive particles)
A layer made of nickel was provided on the surface of the polystyrene particles so as to have a thickness of 0.2 μm, and a layer made of gold was provided on the surface of the layer made of nickel so as to have a thickness of 0.04 μm. . Thus, conductive particles having an average particle diameter of 10 μm were produced.

(Examples 1-5 and Comparative Examples 1-2)
40 mass% polyester urethane resins A to E solutions as thermoplastic resins, isocyanuric acid EO-modified diacrylate (trade name: M-215, manufactured by Toagosei Co., Ltd.), urethane acrylate (trade name: AT-600) as radical polymerizable compounds , Manufactured by Kyoeisha Chemical Co., Ltd.), 2- (meth) acryloyloxyethyl phosphate (trade name: Light Ester P-2M, manufactured by Kyoeisha Chemical Co., Ltd.), and hydrocarbon dilution 50 mass% t- as a radical polymerization initiator Hexyl peroxy-2-ethylhexanoate (trade name: Perhexyl O, 1 minute half-life temperature: 133 ° C., manufactured by Nippon Oil & Fats Co., Ltd.) is blended in the blending amounts (unit: parts by mass) shown in Table 4, and the above An amount of 3% by volume of the conductive particles was added and uniformly dispersed to obtain a dispersion for coating. In addition, the compounding quantity in a table | surface shows the compounding quantity of solid content. Next, the obtained dispersion was applied to a PET film (thickness 80 μm) having a surface treated on one side using a coating apparatus and dried with hot air at 70 ° C. for 10 minutes to form a film-like circuit connection material having a thickness of 18 μm. (Adhesive composition) was obtained.

(Comparative Example 3)
The procedure was carried out except that 60 g of the polyester polyol (glass transition temperature: −5 ° C.) used in the synthesis of the polyester urethane resin A was dissolved in 90 g of methyl ethyl ketone to form a 40 mass% solution, and then blended in the blending amounts shown in Table 1. In the same manner as in Examples 1 to 5 and Comparative Examples 1 and 2, a film-like circuit connecting material (adhesive composition) was obtained.

(Measurement of adhesive strength and connection resistance 1)
Using the film-like circuit connecting materials obtained in Examples 1 to 5 and Comparative Examples 1 to 3, a flexible circuit board (FPC) having 500 copper circuits having a line width of 25 μm, a pitch of 50 μm, and a thickness of 18 μm, and a thickness A glass (thickness 1.1 mm, surface resistance 20Ω / □) on which a thin layer of indium oxide (ITO) having a thickness of 0.2 μm is formed, and a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.) Was used for 10 seconds at 3 MPa at a temperature of 160 ° C. Thereby, the connection body (circuit connection structure) which connected the FPC board and the ITO board | substrate with the hardened | cured material of the film-form circuit connection material over width 2mm was produced.

  The resistance value (connection resistance) between adjacent circuits of this connection body was measured with a multimeter. The resistance value was shown as an average of 37 resistances between adjacent circuits. Moreover, the adhesive strength of this connection body was measured and evaluated by a 90-degree peeling method according to JIS-Z0237. Here, Tensilon UTM-4 (peeling speed 50 mm / min, 25 ° C.) manufactured by Toyo Baldwin Co., Ltd. was used as an adhesive strength measuring device. The connection resistance and adhesive strength were measured immediately after connection and after being held in a high-temperature and high-humidity tank at 85 ° C. and 85% RH for 168 hours. The results are shown in Table 5.

  As is apparent from the results shown in Table 5, the adhesive compositions obtained in Examples 1 to 5 were heated immediately after connection and at 85 ° C. under a curing condition of a heating temperature of 160 ° C., a low temperature of 10 seconds and a short time. After holding in an 85% RH high-temperature and high-humidity tank for 168 hours, it was confirmed to show good connection resistance and adhesive strength. On the other hand, in Comparative Examples 1 and 2 that do not include a polyester urethane resin having a glass transition temperature of 40 ° C. or lower, the adhesive strength immediately after connection is high, but adhesion is performed after 168 hours in a 85 ° C., 85% RH high-temperature and high-humidity tank. It was confirmed that the strength was greatly reduced. Moreover, it replaced with the polyester urethane resin whose glass transition temperature is 40 degrees C or less, and it was confirmed that the adhesive strength immediately after a connection is low in the comparative example 3 using the polyester polyol whose glass transition temperature is -5 degreeC.

(Examples 6 to 7)
The film-like circuit connecting material obtained in Examples 1 and 3 was vacuum packaged and left at 40 ° C. for 3 days, and then the film-like circuit connecting material after this standing was used in the same manner as described above for the FPC board and ITO. The substrate was thermocompression bonded at 160 ° C., 3 MPa, and 10 seconds. Table 6 shows the measurement results of the connection resistance and the adhesive strength of the connection body produced before and after being left as described above.

  As is apparent from the results shown in Table 6, the adhesive compositions obtained in Examples 6 to 7 were 40 ° C./3 days under a curing condition of a heating temperature of 160 ° C., a low temperature of 10 seconds and a short time. It showed good connection resistance and adhesive strength before and after being left, and was excellent in storage stability.

It is a schematic cross section which shows one Embodiment of the film adhesive which consists of an adhesive composition of this invention. It is a schematic cross section which shows one Embodiment of the connection structure of the circuit member of this invention. (A)-(c) is a series of process drawings which connect a circuit member, respectively. It is a schematic cross section showing one embodiment of a semiconductor device of the present invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Film adhesive, 2 ... Semiconductor device, 5 ... Adhesive component, 7 ... Conductive particle, 10 ... Circuit connection member, 11 ... Insulating substance, 20 ... First circuit member, 21 ... Circuit board (first One circuit board), 21a ... main surface, 22 ... circuit electrode (first circuit electrode), 30 ... second circuit member, 31 ... circuit board (second circuit board), 31a ... main surface, 32 ... Circuit electrode (second circuit electrode), 40 ... film-like circuit connecting material, 50 ... semiconductor element, 60 ... substrate, 61 ... circuit pattern, 70 ... sealing material, 80 ... semiconductor element connecting member.

Claims (6)

(A) a thermoplastic resin having a urethane bond and an ester bond in the same molecule;
(B) a radically polymerizable compound;
(C) a radical polymerization initiator;
An adhesive composition comprising:
An adhesive composition comprising two or more types of (a) thermoplastic resins, and at least one of the (a) thermoplastic resins having a glass transition temperature of 40 ° C. or lower.   The adhesive composition according to claim 1, wherein the glass transition temperature of at least one kind of the thermoplastic resin (a) is 60 ° C. or higher.   Furthermore, (d) the vinyl compound which has a 1 or more phosphate group in a molecule | numerator is contained, The adhesive composition of Claim 1 or 2 characterized by the above-mentioned.   Furthermore, (e) electroconductive particle is contained, The adhesive composition as described in any one of Claims 1-3 characterized by the above-mentioned. A pair of circuit members disposed opposite to each other;
A connecting member that is provided between the pair of circuit members, and that bonds the circuit members such that the circuit electrodes of the pair of circuit members are electrically connected;
With
The circuit connection structure which the said connection member consists of the hardened | cured material of the adhesive composition as described in any one of Claims 1-4. A semiconductor element;
A substrate on which the semiconductor element is mounted;
A connecting member provided between the semiconductor element and the substrate, for electrically connecting and bonding the semiconductor element and the substrate;
With
The semiconductor device in which the said connection member consists of hardened | cured material of the adhesive composition as described in any one of Claims 1-4.

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