JP5236144B2 - Adhesive composition, circuit connection structure, and semiconductor device - Google Patents

Description

  The present invention relates to an adhesive composition, a circuit 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 adhesives are required to have various properties such as adhesiveness, heat resistance, reliability in a high temperature and high humidity state. In addition, adherends used for bonding include organic substrates such as printed wiring boards and polyimides, metals such as copper and aluminum, and substrates having various surface states such as ITO, SiN, and SiO _2. The molecular design of the adhesive used for each adherend is required.
Conventionally, a thermosetting resin using an epoxy resin having high adhesiveness and high reliability has been used as an adhesive for the semiconductor element and the liquid crystal display element (for example, see Patent Document 1). As a component of the thermosetting resin, 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. The thermal 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 (25 ° C.) and curing rate during heating. The curing conditions in the actual process were that desired adhesion was obtained by curing 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. Further, in order to reduce the cost, it is necessary to improve the throughput, and adhesion at low temperature (100 to 170 ° C.), 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, and it is known that it is very difficult to combine storage stability near room temperature.
Recently, a radical curable adhesive using an acrylate derivative or a methacrylate derivative (hereinafter referred to as a (meth) acrylate derivative) and a peroxide as a radical polymerization initiator has attracted attention. Radical curing can be cured for a short time because radicals that are reactive species are rich in reactivity (see, for example, Patent Document 2).

Japanese Patent Laid-Open No. 1-113480 JP 2002-203427 A

  However, since radical curing type adhesives are highly reactive, the process margin is narrow, and characteristics such as adhesive strength and connection resistance cannot be stably obtained due to variations in curing temperature and curing time.

  The present invention provides an adhesive composition having a wide process margin, stable performance and excellent storage stability, a circuit connection structure using the same, and a semiconductor device while being a radical curing system It is.

The present invention provides [1] (a) phenoxy resin , (b) a radical polymerizable compound having two or more (meth) acryloyl groups in the molecule, (c) a radical polymerization initiator, (d) 1 in the molecule. A compound having one or more nitroso groups, and a conductive particle, wherein (d) the compound having one or more nitroso groups in the molecule is represented by formula (A), formula (C), or formula (D): (B) 50 to 250 parts by weight of a radically polymerizable compound having two or more (meth) acryloyl groups in the molecule with respect to 100 parts by weight of the phenoxy resin (a) c) a radical polymerization initiator 0.05 to 30 parts by weight, connection circuit according to claim Rukoto such containing compound 0.01 to 10 parts by weight with one or more nitroso groups in (d) molecules An anisotropic conductive adhesive composition.

（ここでＲ^１、R^２は、水素、炭素数１〜１０のアルキル基、アリール基、アミド基、または一般式（Ｂ）を表す。）

(Here, R ¹ and R ² represent hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group, an amide group, or general formula (B).)

（ここでＲ^３は、カルボキシル基、水酸基を表す。Ｋは、１〜５の整数を表す。）

(Here, R ³ represents a carboxyl group or a hydroxyl group. K represents an integer of 1 to 5.)

（ここでＲ^４、Ｒ^５は、炭素数１〜３のアルキレン基、Ｘは、メチレン基、または２価の酸素原子を表す。）

(Here, R ⁴ and R ⁵ represent an alkylene group having 1 to 3 carbon atoms, and X represents a methylene group or a divalent oxygen atom.)

（ここでＲ^６は、アリール基、Ｌは１〜３の整数、ＭはＬ価の陽イオンまたはアンモニウム塩を表す。）
また、本発明は、［２］（ｃ）ラジカル重合開始剤が、１分間半減期温度９０〜１７５℃で、分子量１８０〜１,０００のパーオキシエステルである上記［１］に記載の接着剤組成物である。
また、本発明は、［３］（ａ）フェノキシ樹脂１００重量部に対して、導電粒子０．５〜３０重量部を含有してなる上記［１］に記載の接着剤組成物である。
また、本発明は、［４］相対向する回路電極を有する基板間に上記［１］ないし上記［３］のいずれか一項に記載の接着剤組成物を介在させ、相対向する回路電極を有する基板を加圧して加圧方向の電極間を電気的に接続した回路接続構造体である。
また、本発明は、［５］半導体素子の電極と搭載用基板の回路電極の間に上記［1］ないし上記［３］のいずれか一項に記載の接着剤組成物を介在させ、相対向する電極を有する基板を加圧して加圧方向の電極間を電気的に接続した半導体装置である。

(Here, R ⁶ is an aryl group, L is an integer of 1 to 3, and M is an L-valent cation or ammonium salt.)
The present invention also provides [2] (c) the adhesive according to [1], wherein the radical polymerization initiator is a peroxy ester having a 1 minute half-life temperature of 90 to 175 ° C. and a molecular weight of 180 to 1,000. It is a composition .
Also, the present invention is an adhesive composition according to [3] (a) a phenoxy against 100 parts by weight of the resin comprising the conductive particles 0.5 to 30 parts by weight of the [1].
Moreover, this invention interposes the adhesive composition as described in any one of said [1] thru | or said [ 3 ] between the board | substrates which have a circuit electrode which [ 4 ] opposes, and circuit electrode which opposes mutually. A circuit connection structure in which a substrate having pressure is pressed to electrically connect electrodes in a pressing direction.
The present invention also provides [ 5 ] the adhesive composition according to any one of [1] to [ 3 ] described above between the electrode of the semiconductor element and the circuit electrode of the mounting substrate. A semiconductor device in which a substrate having electrodes to be pressed is pressed and the electrodes in the pressing direction are electrically connected.

  According to the present invention, it is possible to provide an adhesive composition, a circuit connection structure, and a semiconductor device that are radical curing systems, have a wide process margin, have stable performance, and are excellent in storage stability. .

  As the (a) thermoplastic resin used in the present invention, known resins can be used without any particular limitation. As such thermoplastic resins, polyimide resins, polyamide resins, phenoxy resins, poly (meth) acrylate resins, polyimide resins, polyurethane resins, polyester resins, polyvinyl butyral resins, and the like can be used. These can be used alone or in admixture of two or more. 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 from 5,000 to 150,000, particularly preferably from 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.

  As the radically polymerizable compound (b) having two or more (meth) acryloyl groups in the molecule used in the present invention, known compounds can be used without particular limitation.

  Specifically, epoxy (meth) acrylate oligomer, urethane (meth) acrylate oligomer, polyether (meth) acrylate oligomer, oligomer such as polyester (meth) acrylate oligomer, 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) acrylate, 2,2'-di (meth) acryloyloxydiethyl phosphate Polyfunctional (meth) acrylate compounds such as 2- (meth) acryloyloxyethyl acid phosphate. These compounds may be used alone or in combination as required.

  (B) The addition amount of the radical polymerizable compound having two or more (meth) acryloyl groups in the molecule is 50 to 250 parts by weight, preferably 60 to 100 parts by weight per 100 parts of the thermoplastic resin. 150 parts by weight. When the addition amount is less than 60 parts by weight, there is a concern about a decrease in heat resistance after curing, and when it is 150 parts by weight or more, the film formability may be lowered when used as a film.

As the radical polymerization initiator (c) used in the present invention, known compounds such as conventionally known peroxides and azo compounds can be used. Specific compounds of the peroxide can be selected from diacyl peroxide, peroxydicarbonate, peroxyester, peroxyketal, dialkyl peroxide, hydroperoxide, silyl peroxide, and the like. From the viewpoints of stability, reactivity, and compatibility, peroxy ester derivatives having a 1 minute half-life temperature of 90 to 175 ° C. and a molecular weight of 180 to 1,000 are preferred.
Specifically, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxynoedecanoate, t-hexylper Oxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl -2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneohepta Noate, t-amylperoxy-2-ethylhexanoate, di-t-butylperoxyhexahydroterephthalate, t-amino Peroxy-3,5,5-trimethylhexanoate, 3-hydroxy-1,1-dimethylbutylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate , T-amylperoxyneodecanoate, t-amylperoxy-2-ethylhexanoate, 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- Tilperoxymaleic 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) hexane, t-butylperoxybenzoate, dibutylperoxytrimethyl Examples include adipate, t-amyl peroxy normal octoate, t-amyl peroxy isononanoate, t-amyl peroxybenzoate and the like.
These compounds may be used alone or as a mixture of two or more compounds.

  (C) The addition amount of the radical polymerization initiator is 0.05 to 30 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts of (a) the thermoplastic resin. When the addition amount is less than 0.05 parts by weight, there is a concern about insufficient curing, and when it is 30 parts by weight or more, the standing stability may be lowered.

  As the compound having one or more nitroso groups in the molecule (d) used in the present invention, known compounds can be used without particular limitation as long as they are compounds containing at least one nitroso group in the molecule. . In particular, a nitrosamine compound represented by any one of the following general formulas (A), (C), and (D) is preferable.

（ここでＲ^１、Ｒ^２は、水素、炭素数１〜１０のアルキル基、アリール基、アミド基、または一般式（Ｂ）を表す。）

(Here, R ¹ and R ² represent hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group, an amide group, or general formula (B).)

（ここでＲ^３は、カルボキシル基、水酸基を表す。Ｋは、１〜５の整数を表す。）

(Here, R ³ represents a carboxyl group or a hydroxyl group. K represents an integer of 1 to 5.)

（ここでＲ^４、Ｒ^５は、炭素数１〜３のアルキレン基、Ｘはメチレン基、または２価の酸素原子を表す。）

(Here, R ⁴ and R ⁵ represent an alkylene group having 1 to 3 carbon atoms, and X represents a methylene group or a divalent oxygen atom.)

（ここでＲ^６は、アリール基、Ｌは１〜３の整数、ＭはＬ価の陽イオンまたはアンモニウム塩を表す。）
具体的には、ジフェニルニトロソアミン、メチルニトロソアニリン、エチルニトロソアニリン、ジメチルニトロソアミン、ジエチルニトロソアミン、ジブチルニトロソアミン、ジヘキシルニトロソアミン、ブチルエチルニトロソアミン、ｔ−ブチルエチルニトロソアミン、等が挙げられる。この他に、下記一般式に示す化合物（１）〜(１４)や、ポリアミン、ポリエステル、ポリアクリレート等の側鎖に前記一般式（Ａ）で示される置換基が導入されたポリマーが挙げられる。
これらの化合物は、単独で用いる他に、２種以上の化合物を混合して用いても良い。

(Here, R ⁶ is an aryl group, L is an integer of 1 to 3, and M is an L-valent cation or ammonium salt.)
Specific examples include diphenylnitrosamine, methylnitrosoaniline, ethylnitrosoaniline, dimethylnitrosamine, diethylnitrosamine, dibutylnitrosamine, dihexylnitrosamine, butylethylnitrosamine, t-butylethylnitrosamine, and the like. In addition, compounds (1) to (14) represented by the following general formula, and polymers in which the substituent represented by the general formula (A) is introduced into the side chain of polyamine, polyester, polyacrylate, and the like can be given.
These compounds may be used alone or as a mixture of two or more compounds.

  (D) The addition amount of the compound having one or more nitroso groups in the molecule is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts per 100 parts by weight of the thermoplastic resin (a). Parts by weight. If the addition amount is less than 0.01 parts by weight, the effect of addition may be remarkably reduced, and if it is 10 parts by weight or more, the compatibility with other components may be reduced.

Moreover, the adhesive composition of the present invention can contain conductive particles.
Examples of the conductive particles used in the present invention include metal particles such as Au, Ag, Ni, Cu, and solder, and carbon. Further, non-conductive glass, ceramic, plastic, or the like may be used as a core, and the core, metal particles, or carbon may be coated on the core. In the case where the conductive particles are made of plastic as a core and the core is coated with the metal, metal particles or carbon, or hot-melt metal particles, the contact area with the electrode at the time of connection increases because it is deformable by heating and pressing. This is preferable because reliability is improved. In addition, fine particles with the surface of these conductive particles coated with a polymer resin or the like suppress short-circuiting due to contact between particles when the amount of conductive particles is increased, and improve insulation between electrode circuits. Therefore, it may be used alone or mixed with conductive particles as appropriate.

  The average particle diameter of the conductive particles is preferably 1 to 18 μm from the viewpoint of dispersibility and conductivity. The amount of the conductive particles used is not particularly limited, but (a) it is preferable to contain 0.5 to 30 parts by weight of the conductive particles with respect to 100 parts by weight of the thermoplastic resin. It is preferable to set it as 0.1-30 volume% with respect to adhesive composition total 100 volume, and it is more preferable to set it as 0.1-10 volume%. If this value is less than 0.1% by volume, the conductivity tends to be inferior, and if it exceeds 30% by volume, a short circuit tends to occur.

  To the adhesive composition of the present invention, an adhesion assistant 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, compounds represented by the following general formula are preferable.

（ここでＲ^６、Ｒ^７、Ｒ^８は独立に、水素、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、アリール基、Ｒ^９は水素、メチル基、Ｎは１〜１０の整数を示す。）

(Where R ⁶ , R ⁷ and R ⁸ are independently hydrogen, 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, an aryl group, R ⁹⁾ Represents hydrogen, a methyl group, and N represents an integer of 1 to 10.)

In particular, in the above general formula, a compound in which R ⁶ is an alkyl group or aryl group having 1 to 5 carbon atoms, R ⁷ and R ⁸ are alkoxy groups having 1 to 3 carbon atoms, and N is 2 to 4 is highly adhesive. Is more preferable from the viewpoint of reliability and electrical reliability.
These compounds may be used alone or in admixture of two or more compounds.

  The adhesive composition of the present invention has an allyl group, a maleimide group, in addition to the radically polymerizable compound (b) having two or more (meth) acryloyl groups in the molecule for the purpose of improving the crosslinking rate. You may add suitably the compound which has a functional group superposed | polymerized by active radicals, such as a vinyl group. 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, acrylamide and the like.

  The adhesive composition of the present invention may be used in combination with a monofunctional (meth) acrylate for the purpose of improving fluidity. Specifically, pentaerythritol (meth) acrylate, 2-cyanoethyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 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, hydroxypropyl (meth) acrylate, Isobornyl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, n-lauryl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl ( ) Acrylate, tetrahydrofurfuryl (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, Examples thereof include N-dimethylaminopropyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and (meth) acryloylmorpholine.

The adhesive composition of the present invention may be used in combination with a rubber component for the purpose of stress relaxation and adhesion improvement. Specifically, 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, acrylonitrile-butadiene rubber, carboxylated nitrile rubber, hydroxyl-terminated poly (oxypropylene), alkoxy containing carboxyl group, hydroxyl group, (meth) acryloyl group or morpholine group at the polymer end Examples include silyl 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 include liquid acrylonitrile-butadiene rubber, liquid acrylonitrile-butadiene rubber containing a carboxyl group, hydroxyl group, (meth) acryloyl group or morpholine group at the polymer end, and liquid carboxylated nitrile rubber. Acrylonitrile which is a polar group The content is preferably 10 to 60% by weight.
These compounds may be used alone or in admixture of two or more compounds.

  To the adhesive composition of the present invention, for the purpose of imparting storage stability, additives such as polymerization inhibitors represented by t-butylpyrocatechol, t-butylphenol, p-methoxyphenol and the like may be appropriately added. Good.

  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 room temperature, it may be heated and used, or may be made into a paste using a solvent. The solvent that can be used is not particularly limited as long as it is not reactive with the adhesive composition and additives, and exhibits sufficient solubility, but has a boiling point of 50 to 150 ° C. at normal pressure. Those are preferred. If the boiling point is less than 50 ° C., it may volatilize if left at room temperature, 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 also be used in the form of a film. A solution prepared by adding a solvent or the like to the adhesive composition as necessary is applied to a peelable substrate such as a fluororesin film, a polyethylene terephthalate film, or a release paper, or a substrate such as a nonwoven fabric is impregnated with the solution. Can be used as a film after removing the solvent and the like. Use in the form of a film is more convenient from the viewpoint of handleability.

  The adhesive composition of the present invention can be bonded by using heating and pressurization together. The heating temperature is not particularly limited, but a temperature of 50 to 190 ° C. is preferable. The pressure is not particularly limited as long as it does not damage the adherend, but 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, preferably 1 second to 10 seconds.

Using the adhesive composition of the present invention, an adhesive composition is interposed between substrates having circuit electrodes facing each other, and a substrate having circuit electrodes facing each other is pressed to electrically connect the electrodes in the pressing direction. The circuit connection structure can be obtained by connecting to the circuit. The substrate having a circuit electrode is composed of a substrate and an electrode, and the substrate is not particularly limited as long as an electrode requiring electrical connection is formed, but ITO or the like used for a liquid crystal display There are glass or plastic substrates on which electrodes are formed, printed wiring boards, ceramic wiring boards, flexible wiring boards, semiconductor silicon chips, etc., which are used in combination as required.
The circuit electrodes of the substrate having circuit electrodes are arranged to face each other, the adhesive composition of the present invention (preferably in the form of a film) is interposed between the circuit electrodes arranged to face each other, and the connecting terminals arranged to face each other are heated and pressed. Are connected to form a circuit connection structure. By heating and pressurizing, the circuit electrodes arranged opposite to each other can be electrically connected by direct contact or via conductive particles in the adhesive composition. The adhesive composition of the present invention is interposed between the electrode of the semiconductor element and the circuit electrode of the mounting substrate, and the electrodes facing each other (the electrode of the semiconductor element and the circuit electrode of the mounting substrate) are pressed in the pressing direction. A semiconductor device can be obtained by electrically connecting the electrodes.

  The adhesive composition 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.

  Below, an example of the connection of the anisotropic conductive film produced using the adhesive composition and conductive particle of this invention, and an electrode is demonstrated. An anisotropic conductive film is present between the opposing electrodes on the substrate and heated and pressed to obtain contact between the electrodes and adhesion between the substrates, thereby connecting the electrodes. As the substrate for forming the electrodes, semiconductors, inorganic substances such as glass and ceramics, organic substances such as polyimide and polycarbonate, and combinations of these composites such as glass / epoxy can be applied.

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

Example 1
(A) As a thermoplastic resin, 40 g of phenoxy resin (PKHC, trade name of Union Carbide, average molecular weight 45,000) was dissolved in 60 g of methyl ethyl ketone to obtain a solution having a solid content of 40% by weight. (B) Isocyanuric acid EO-modified diacrylate (M-215, trade name, manufactured by Toagosei Co., Ltd.), urethane acrylate (AT-600, trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and 2- (meth) as radical polymerizable compounds Acryloyloxyethyl phosphate (light ester P-2M, trade name, manufactured by Kyoeisha Chemical Co., Ltd.), (c) t-hexylperoxy-2-ethylhexanoate (perhexyl O, 1 minute half-life temperature as radical polymerization initiator) 132.6 ° C., trade name manufactured by NOF Corporation), (d) a nitrosoamine compound which has one or more nitroso groups in the molecule, a nitrosophenylhydroxyamine aluminum salt (NPAL, trade name manufactured by ALBEMARLE) And blended as shown in Table 1 in terms of solid weight ratio, and further conductive particles 1.5. The composition was dispersed in volume%, applied to a fluororesin film having a thickness of 80 μm using a coating apparatus, and dried with hot air at 70 ° C. for 10 minutes to obtain a film adhesive having a thickness of 15 μm. The conductive particles are provided with a nickel layer having a thickness of 0.2 μm on the surface of particles having polystyrene as a core, and an average particle size of 4 μm and a specific gravity of 2.5 having a gold layer having a thickness of 0.02 μm outside the nickel layer. The conductive particles were prepared and used.

[Measurement of Adhesive Strength and Connection Resistance] 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 0.2 μm A glass (thickness 1.1 mm, surface resistance 20Ω / □) on which a thin layer of indium oxide (ITO) is formed is 165 ° C. using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.) A circuit connection structure (connected body) was manufactured by applying heat and pressure at 3 MPa for 10 seconds and connecting over a width of 2 mm. The resistance value between adjacent circuits of this connection body was measured with a multimeter immediately after bonding and after being held in a high-temperature and high-humidity bath at 80 ° C. and 95% RH for 120 hours. The resistance value was shown by the average of 150 resistances between adjacent circuits (x + 3σ, average value; x, σ: standard deviation).

  Moreover, the adhesive strength of this circuit connection structure (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.

(Example 2)
In the same manner as in Example 1, except that 0.01 part by weight of N, N-diphenylnitrosamine (DPNA, trade name, manufactured by Wako) was used instead of NPAL used as the nitrosamine compound of Example 1, film-like adhesion An agent was prepared and evaluated.

(Comparative Example 1)
A film adhesive was prepared and evaluated in the same manner as in Example 1 except that the nitrosamine compound NPAL was not used in Example 1.

(Comparative Example 2)
Instead of perhexyl O used as the radical polymerization initiator of Example 1, diisopropyl peroxydicarbonate (Perroyl IPP, manufactured by NOF Corporation), which is a peroxydicarbonate derivative having a half-life temperature of 88.3 ° C. A film-like adhesive was produced and evaluated in the same manner as in Example 1 except that 3 parts by weight of the name) was used and no nitrosamine compound was used.

  Table 2 shows the results of measuring the adhesive strength and connection resistance of the circuit connection structure (connection body) performed as described above.

  The adhesive compositions obtained in Examples 1 and 2 have a low connection resistance and adhesion immediately after bonding at a heating temperature of 160 ° C. and after being held in a high-temperature and high-humidity bath at 80 ° C. and 95% RH for 120 hours. It showed good characteristics with high strength and good characteristics over a wide range of heating temperatures. On the other hand, in the case where the nitrosamine compound in the present invention is not used (Comparative Examples 1 and 2), an increase in connection resistance and a decrease in adhesive strength are observed even immediately after connection as compared to the Examples used, After holding for 120 hours in a high-temperature and high-humidity bath at 80 ° C. and 95% RH, the increase in connection resistance and the decrease in adhesive strength became significant. In addition, the value of the connection resistance varies greatly with a wide range of heating temperatures.

(Example 3)
The film adhesive obtained in Example 1 was vacuum packaged and allowed to stand at 40 ° C. for 3 days, and then FPC and ITO were thermocompression bonded at 160 ° C., 3 MPa, and 10 seconds as in Example 1. went. When the adhesion strength and connection resistance of the circuit connection structure (connection body) thus obtained were measured, the adhesion strength was 880 N / m, the connection resistance was 2.3 Ω, and the standing stability (storage stability) was improved. outstanding.

Claims (5)

(a) a phenoxy resin , (b) a radical polymerizable compound having two or more (meth) acryloyl groups in the molecule, (c) a radical polymerization initiator, (d) having one or more nitroso groups in the molecule. A compound, and conductive particles,
The compound (d) having one or more nitroso groups in the molecule is a nitrosamine compound represented by any one of the general formula (A), the general formula (C), and the general formula (D),
(A) 100 parts by weight of phenoxy resin, (b) 50 to 250 parts by weight of a radically polymerizable compound having two or more (meth) acryloyl groups in the molecule, and (c) a radical polymerization initiator of 0.05 to 30 parts by weight, (d) Rukoto circuit connection anisotropic conductive adhesive composition, characterized in that it contains a compound from 0.01 to 10 parts by weight with one or more nitroso groups in the molecule.

(Here, R ¹ and R ² represent hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group, an amide group, or general formula (B).)

(Here, R ³ represents a carboxyl group or a hydroxyl group. K represents an integer of 1 to 5.)

(Here, R ⁴ and R ⁵ represent an alkylene group having 1 to 3 carbon atoms, and X represents a methylene group or a divalent oxygen atom.)

(Here, R ⁶ is an aryl group, L is an integer of 1 to 3, and M is an L-valent cation or ammonium salt.)   (C) The adhesive composition according to claim 1, wherein the radical polymerization initiator is a peroxyester having a half-life temperature of 90 to 175 ° C for 1 minute and a molecular weight of 180 to 1,000. The adhesive composition according to claim 1 , comprising 0.5 to 30 parts by weight of conductive particles with respect to 100 parts by weight of (a) phenoxy resin . 4. The adhesive composition according to any one of claims 1 to 3 is interposed between substrates having circuit electrodes opposed to each other, and a substrate having circuit electrodes opposed to each other is pressed to apply an electrode in a pressing direction. A circuit connection structure that electrically connects the two. The adhesive composition according to any one of claims 1 to 3 is interposed between an electrode of a semiconductor element and a circuit electrode of a mounting substrate, and a substrate having electrodes facing each other is pressurized and pressurized. A semiconductor device in which electrodes in a direction are electrically connected.