JP4892923B2 - Adhesive composition, circuit terminal connection structure, and circuit terminal connection method - Google Patents

Adhesive composition, circuit terminal connection structure, and circuit terminal connection method Download PDF

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JP4892923B2
JP4892923B2 JP2005302939A JP2005302939A JP4892923B2 JP 4892923 B2 JP4892923 B2 JP 4892923B2 JP 2005302939 A JP2005302939 A JP 2005302939A JP 2005302939 A JP2005302939 A JP 2005302939A JP 4892923 B2 JP4892923 B2 JP 4892923B2
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connection terminal
connection
circuit
adhesive composition
resin
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JP2007077382A (en
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茂樹 加藤木
晋 川上
敏明 白坂
恵子 富澤
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Showa Denko Materials Co Ltd
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Hitachi Chemical Co Ltd
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Description

本発明は、接着材組成物と、回路端子の接続構造体及び回路端子の接続方法とに関する。   The present invention relates to an adhesive composition, a circuit terminal connection structure, and a circuit terminal connection method.

エポキシ樹脂系接着材は、高い接着強度が得られ、耐水性や耐熱性に優れること等から、電気・電子・建築・自動車・航空機等の各種用途に多用されている。中でも一液型エポキシ樹脂系接着材は、主剤と硬化剤との混合が不必要であり使用が簡便なことから、フィルム状、ペースト状、粉体状の形態で使用されている(例えば特許文献1)。この場合、エポキシ樹脂と硬化剤及び変性剤との多様な組合せにより、特定の性能を得ることが一般的である。しかしながら、このようなエポキシ樹脂系のフィルム状接着材は、作業性に優れるものの、低温速硬化性の点で不十分であった。   Epoxy resin adhesives are widely used in various applications such as electricity, electronics, architecture, automobiles and aircraft because they have high adhesive strength and are excellent in water resistance and heat resistance. Among them, one-pack type epoxy resin adhesives are used in the form of film, paste, and powder because they do not require mixing of the main agent and curing agent and are easy to use (for example, patent documents). 1). In this case, it is common to obtain specific performance by various combinations of epoxy resins, curing agents and modifiers. However, such an epoxy resin film-like adhesive is excellent in workability, but is insufficient in terms of low-temperature fast curing.

低温速硬化性の接着材として、ラジカル重合性接着材が知られている(例えば、特許文献2)が、低温硬化性を重視した場合、分解温度(半減期温度)の低い硬化剤(過酸化物等)が使用されるため、貯蔵安定性が低下する問題があった。また、光照射と低温加熱による硬化方法として光カチオン硬化が提案されているが(例えば特許文献3)、金属部材への腐食等で問題が生じる場合があった。
また、光塩基発生剤とエポキシ樹脂を併用して光照射と加熱によって硬化を行う方法が提案されている(例えば特許文献4)。これは、光照射によって光塩基発生剤から発生した塩基性化合物が、エポキシ樹脂とチオール化合物との硬化反応を低温で促進する原理を用いているが、使用可能なチオール化合物の構造が剛直であるために硬化物が脆化し、接着力の低下や剥離等で問題が生じる場合があった。
As a low-temperature fast-curing adhesive, a radical-polymerizable adhesive is known (for example, Patent Document 2). However, when low-temperature curability is emphasized, a curing agent (peroxidation) having a low decomposition temperature (half-life temperature) is known. Etc.), the storage stability is lowered. Further, although photocationic curing has been proposed as a curing method by light irradiation and low-temperature heating (for example, Patent Document 3), there may be a problem due to corrosion or the like on a metal member.
Further, a method has been proposed in which a photobase generator and an epoxy resin are used in combination to cure by light irradiation and heating (for example, Patent Document 4). This is based on the principle that a basic compound generated from a photobase generator by light irradiation accelerates the curing reaction between an epoxy resin and a thiol compound at a low temperature, but the structure of the usable thiol compound is rigid. For this reason, the cured product becomes brittle, which may cause problems such as a decrease in adhesion and peeling.

特開平1−113480号公報Japanese Patent Laid-Open No. 1-113480 国際公開第98/44067号パンフレットInternational Publication No. 98/44067 Pamphlet 特許第3392866号公報Japanese Patent No. 3392866 特開2001−279216号公報JP 2001-279216 A

本発明の目的は、低温速硬化性と貯蔵安定性に優れ、また接着力の低下や剥離等が改善された接着材組成物並びに回路端子の接続構造体及び回路端子の接続方法を提供することである。   An object of the present invention is to provide an adhesive composition that is excellent in low-temperature rapid curing properties and storage stability, and has improved adhesive strength reduction, peeling, etc., a circuit terminal connection structure, and a circuit terminal connection method. It is.

本発明者らは、上記課題に鑑み、鋭意研究した結果、エポキシ樹脂、分子内に1つ以上のエステル結合を持つチオール化合物と共に、光照射によって塩基を発生する光塩基発生剤を組み合わせることで、接着材の低温速硬化性及び接着性が向上し、かつ光を遮断した場合には貯蔵安定性に優れることを見出し、本発明を完成させた。   As a result of earnest research in view of the above problems, the present inventors combined an epoxy resin, a thiol compound having one or more ester bonds in the molecule, and a photobase generator that generates a base by light irradiation. The present inventors have found that the low-temperature fast curability and adhesiveness of the adhesive are improved and that the storage stability is excellent when light is blocked, and the present invention has been completed.

本発明は以下の通りである。
[1] (A)エポキシ樹脂、(B)分子内に1つ以上のエステル結合を持つチオール化合物、(C)光照射によって塩基を発生する光塩基発生剤、を含有する接着材組成物。
[2] (B)チオール化合物が、トリメチロールプロパントリスチオグリコレート、ペンタエリスリトールテトラキスチオグリコレート、トリメチロールプロパントリスチオプロピオネート、ペンタエリスリトールテトラキスチオプロピオネート、下記一般式(1)、(2)で示される化合物の群から選ばれる少なくとも一種類の化合物であることを特徴とする上記[1]記載の接着材組成物。
The present invention is as follows.
[1] An adhesive composition containing (A) an epoxy resin, (B) a thiol compound having one or more ester bonds in the molecule, and (C) a photobase generator that generates a base by light irradiation.
[2] (B) The thiol compound is trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthioglycolate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, the following general formula (1), ( The adhesive composition according to [1] above, which is at least one compound selected from the group of compounds represented by 2).

Figure 0004892923

(一般式(1)、(2)において、m、nは独立に1〜5の整数を示す)
Figure 0004892923

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

[3] (C)光塩基発生剤が、アミンイミド誘導体、イミダゾリウム塩誘導体、4級アンモニウム塩誘導体、カルバミン酸エステル誘導体、オキシムエステル誘導体、α−アミノケトン誘導体からなる群より選ばれる一以上の化合物であることを特徴とする上記[1]または上記[2]記載の接着材組成物。
[4] さらに、熱可塑性樹脂を含有する上記[1]ないし上記[3]のいずれかに記載の接着材組成物。
[5] 前記熱可塑性樹脂が、フェノキシ樹脂、ポリエステル樹脂、ポリウレタン樹脂、ポリエステルウレタン樹脂、ブチラール樹脂、アクリル樹脂から選ばれることを特徴とする上記[4]に記載の接着材組成物。
[6] さらに、導電性粒子を含有する上記[1]ないし上記[5]のいずれかに記載の接着材組成物。
[7] 第一の接続端子を有する第一の回路部材と、第二の接続端子を有する第二の回路部材とが、第一の接続端子と第二の接続端子を対向して配置されており、前記対向配置した第一の接続端子と第二の接続端子の間に上記[1]ないし上記[6]のいずれかに記載の接着材組成物が介在されており、前記対向配置した第一の接続端子と第二の接続端子のみが電気的に接続されている回路端子の接続構造体。
[8] 第一の接続端子を有する第一の回路部材上に上記[1]ないし上記[6]のいずれかに記載の接着材組成物を配置させ、接着材組成物の上方から光照射を行った後、第二の接続端子を有する第二の回路部材を対向して配置し、加熱しながら加圧して対向配置した第一の接続端子と第二の接続端子のみを電気的に接続させる回路端子の接続方法。
[9] 第一の接続端子を有する第一の回路部材と、第二の接続端子を有する第二の回路部材とを、第一の接続端子と第二の接続端子を対向して配置し、前記対向配置した第一の接続端子と第二の接続端子の間に上記[1]ないし上記[6]のいずれかに記載の接着材組成物を介在させ、光照射と同時に加熱しながら加圧して前記対向配置した第一の接続端子と第二の接続端子のみを電気的に接続させる回路端子の接続方法。
[3] (C) The photobase generator is one or more compounds selected from the group consisting of amine imide derivatives, imidazolium salt derivatives, quaternary ammonium salt derivatives, carbamic acid ester derivatives, oxime ester derivatives, and α-aminoketone derivatives. The adhesive composition according to the above [1] or [2], which is characterized in that it exists.
[4] The adhesive composition according to any one of [1] to [3], further including a thermoplastic resin.
[5] The adhesive composition according to [4], wherein the thermoplastic resin is selected from phenoxy resin, polyester resin, polyurethane resin, polyester urethane resin, butyral resin, and acrylic resin.
[6] The adhesive composition according to any one of [1] to [5], further including conductive particles.
[7] A first circuit member having a first connection terminal and a second circuit member having a second connection terminal are arranged to face the first connection terminal and the second connection terminal. The adhesive composition according to any one of [1] to [6] is interposed between the first connection terminal and the second connection terminal arranged opposite to each other, and A circuit terminal connection structure in which only one connection terminal and the second connection terminal are electrically connected.
[8] The adhesive composition according to any one of [1] to [6] is disposed on a first circuit member having a first connection terminal, and light irradiation is performed from above the adhesive composition. After performing, arrange | positioning the 2nd circuit member which has a 2nd connection terminal facing, and pressurizing while heating, and electrically connecting only the 1st connection terminal and 2nd connection terminal which were opposingly arranged How to connect circuit terminals.
[9] A first circuit member having a first connection terminal and a second circuit member having a second connection terminal are disposed so that the first connection terminal and the second connection terminal face each other. The adhesive composition according to any one of the above [1] to [6] is interposed between the first connection terminal and the second connection terminal arranged to face each other, and the pressure is applied while heating simultaneously with light irradiation. A circuit terminal connection method for electrically connecting only the first connection terminal and the second connection terminal arranged opposite to each other.

本発明によれば、低温速硬化性と貯蔵安定性に優れ、また、接着性にも優れた接着材組成物並びに回路端子の接続構造体及び回路端子の接続方法を提供できる。   According to the present invention, it is possible to provide an adhesive composition, a circuit terminal connection structure, and a circuit terminal connection method that are excellent in low-temperature fast-curing property and storage stability and excellent in adhesiveness.

本発明において用いる(A)エポキシ樹脂としては、分子内に2個以上のエポキシ基を有するものであれば特に制限なく、公知のものを使用することができる。このような分子内に少なくとも2個以上のエポキシ基を有する化合物としては、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールAノボラック型エポキシ樹脂、ビスフェノールFノボラック型エポキシ樹脂、脂環式エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、ヒダントイン型エポキシ樹脂、イソシアヌレート型エポキシ樹脂、脂肪族鎖状エポキシ樹脂等があり、これらのエポキシ樹脂はハロゲン化されていてもよく、水素添加されていてもよい。これらのエポキシ樹脂は、2種以上を併用してもよい。   The (A) epoxy resin used in the present invention is not particularly limited as long as it has two or more epoxy groups in the molecule, and known ones can be used. Examples of the compound having at least two epoxy groups in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol. A novolac type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, aliphatic chain epoxy resin, etc. Yes, these epoxy resins may be halogenated or hydrogenated. Two or more of these epoxy resins may be used in combination.

また、本発明におけるエポキシ基を有する化合物として、エポキシ当量43から10000程度のエポキシ基を有する化合物を用いてもよい。エポキシ当量が43以上であれば架橋密度の低下を防止することができ、また10000以下であれば反応速度が低下する傾向を抑制できる。   In addition, as the compound having an epoxy group in the present invention, a compound having an epoxy group with an epoxy equivalent of about 43 to 10,000 may be used. If the epoxy equivalent is 43 or more, the crosslinking density can be prevented from decreasing, and if it is 10,000 or less, the tendency of the reaction rate to decrease can be suppressed.

本発明において用いる(B)チオール化合物としては、分子内に1つ以上のエステル結合を持つチオール化合物であれば特に制限なく、公知のものを使用することができる。本発明において用いる(B)チオール化合物は、極性の高いエステル結合を分子内に持つことによって良好な接着性を示すことが特長である。分子内に1つ以上のエステル結合を持つチオール化合物を以下、(B)チオール化合物と略す。   The (B) thiol compound used in the present invention is not particularly limited as long as it is a thiol compound having one or more ester bonds in the molecule, and known compounds can be used. The (B) thiol compound used in the present invention is characterized by showing good adhesiveness by having a highly polar ester bond in the molecule. Hereinafter, the thiol compound having one or more ester bonds in the molecule is abbreviated as (B) thiol compound.

このような(B)チオール化合物としては、チオール化合物の分子量をチオール化合物1分子当りのメルカプト基の官能基数で割った値であるメルカプト基当量(以下SH当量と略す)が100以上のものが好ましく、エステル結合とともに分子内に2つ以上のメルカプト基を有し、かつSH当量が100以上のチオール化合物が、接着性の観点からより好ましい。
具体的には、トリメチロールプロパンやペンタエリスリトールのOH基を変性したトリメチロールプロパントリスチオグリコレート、ペンタエリスリトールテトラキスチオグリコレート、トリメチロールプロパントリスチオプロピオネート、ペンタエリスリトールテトラキスチオプロピオネートや下記一般式(1)、(2)で示されるイソシアヌレート変性チオール化合物、4,4’−チオジベンゼンチオール等が挙げられ、接着性、耐熱性の観点からイソシアヌレート変性チオール化合物が特に好ましい。これらのチオール化合物は、1種または2種以上を使用してもよい。
Such (B) thiol compound preferably has a mercapto group equivalent (hereinafter referred to as SH equivalent) of 100 or more, which is a value obtained by dividing the molecular weight of the thiol compound by the number of functional groups of the mercapto group per molecule of thiol compound. A thiol compound having an ester bond and two or more mercapto groups in the molecule and an SH equivalent of 100 or more is more preferable from the viewpoint of adhesiveness.
Specifically, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthioglycolate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate modified with OH group of trimethylolpropane or pentaerythritol, Examples include isocyanurate-modified thiol compounds represented by general formulas (1) and (2), 4,4′-thiodibenzenethiol, and isocyanurate-modified thiol compounds are particularly preferable from the viewpoints of adhesiveness and heat resistance. These thiol compounds may be used alone or in combination of two or more.

Figure 0004892923

(一般式(1)、(2)において、m、nは独立に1〜5の整数を示す)
Figure 0004892923

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

(B)チオール化合物の使用量は、(A)エポキシ樹脂に対して、SH当量/エポキシ当量の比で0.3/1.7〜1.7/0.3の比率となるようにすることが好ましく、0.8/1.2〜1.2/0.8の比率となるようにすることがより好ましい。この比率が、0.3/1.7から1.7/0.3の範囲内であれば、未反応のチオール基やエポキシ基が硬化物中に多量に残存することを防止でき、硬化物の機械特性の低下傾向を抑制できる。   The amount of (B) thiol compound used should be a ratio of 0.3 / 1.7 to 1.7 / 0.3 in the ratio of SH equivalent / epoxy equivalent to (A) epoxy resin. Is preferable, and a ratio of 0.8 / 1.2 to 1.2 / 0.8 is more preferable. If this ratio is in the range of 0.3 / 1.7 to 1.7 / 0.3, it is possible to prevent a large amount of unreacted thiol groups and epoxy groups from remaining in the cured product. It is possible to suppress the tendency of the mechanical properties to decrease.

本発明に用いる(C)光照射によって塩基を発生する光塩基発生剤は、光照射によって塩基を発生する化合物であれば特に制限は受けないが、アミンイミド誘導体、イミダゾリウム塩誘導体、4級アンモニウム塩誘導体、カルバミン酸エステル誘導体、オキシムエステル誘導体、α−アミノケトン誘導体が、光照射に対して効率よく塩基を発生する観点から、より好ましい。
本発明における光塩基発生剤の役割としては、光照射によって発生した塩基性化合物が硬化触媒として作用し、前記エポキシ樹脂と前記チオール化合物の硬化を促進することを前提としている。このため、前記光塩基発生効率とともに、光照射によって発生した化合物の塩基性が重要となる。光塩基発生剤から発生する塩基性化合物としては、例えば塩基性の指標とされるpKaが5以上の化合物が好ましい。このような化合物としては例えば、イミダゾール誘導体、1級アミン、2級アミン、3級アミン、DABCO(トリエチレンジアミン)やDBU(1,8−ジアザビシクロ[5,4,0]ウンデカ−7−エン)、DBN(2,6−ジクロロベンゾニトリル)等が挙げられる。このような塩基性化合物を発生する光塩基発生剤としては、例えば、Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints,Ed.by G. Bradley,John Wiley and Sons Ltd.(1998年)、p479〜p545に記載されているカルバミン酸エステル誘導体やオキシムエステル誘導体、4級アンモニウム塩誘導体、が挙げられる。また、特開平11−71450号公報に記載されているα−アミノアセトフェノン誘導体や国際公開第2002/051905号パンフレットに記載されているアミンイミド誘導体、特開2003−212856号公報に記載されているイミダゾリウム塩誘導体が挙げられる。
(C) The photobase generator that generates a base by light irradiation used in the present invention is not particularly limited as long as it is a compound that generates a base by light irradiation, but it is an amine imide derivative, an imidazolium salt derivative, a quaternary ammonium salt. Derivatives, carbamic acid ester derivatives, oxime ester derivatives, and α-aminoketone derivatives are more preferable from the viewpoint of efficiently generating a base with respect to light irradiation.
The role of the photobase generator in the present invention is based on the premise that a basic compound generated by light irradiation acts as a curing catalyst and promotes curing of the epoxy resin and the thiol compound. For this reason, the basicity of the compound generated by light irradiation is important along with the photobase generation efficiency. As the basic compound generated from the photobase generator, for example, a compound having a pKa of 5 or more, which is a basic index, is preferable. Examples of such compounds include imidazole derivatives, primary amines, secondary amines, tertiary amines, DABCO (triethylenediamine) and DBU (1,8-diazabicyclo [5,4,0] undec-7-ene), DBN (2,6-dichlorobenzonitrile) etc. are mentioned. Examples of photobase generators that generate such basic compounds include Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints, Ed. by G. Bradley, John Wiley and Sons Ltd. (1998), p479 to p545, carbamic acid ester derivatives, oxime ester derivatives, and quaternary ammonium salt derivatives. Further, α-aminoacetophenone derivatives described in JP-A No. 11-71450, amine imide derivatives described in WO 2002/051905 pamphlet, and imidazolium described in JP-A No. 2003-212856. And salt derivatives.

本発明で用いる(C)光塩基発生剤の添加量は、(A)エポキシ樹脂100重量部に対して0.01〜200重量部が好ましく、0.02〜150重量部がさらに好ましい。光塩基発生剤が0.01重量部以上であれば耐熱性の低下を抑制でき、200重量部以下であれば、フィルム物性が良好である。   The amount of the (C) photobase generator used in the present invention is preferably 0.01 to 200 parts by weight, more preferably 0.02 to 150 parts by weight, based on 100 parts by weight of the (A) epoxy resin. If the photobase generator is 0.01 parts by weight or more, the heat resistance can be prevented from decreasing, and if it is 200 parts by weight or less, the film properties are good.

本発明の接着材組成物は、さらに熱可塑性樹脂を含むことができる。熱可塑性樹脂としては、特に制限は受けないが、樹脂の主鎖骨格あるいは側鎖に水酸基、エーテル基、エステル基、ウレタン基、アミド基、イミド基、カルボキシル基、等の極性基を含有する樹脂が接着性の観点から好ましい。具体的には、フェノキシ樹脂、ポリエステル樹脂、ポリウレタン樹脂、ポリエステルウレタン樹脂、ポリビニルブチラール樹脂、ポリビニルホルマール樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリアクリル樹脂、等が使用できる。また前記ポリマーを反応性官能基であるエポキシ基やアクリロイル基、メタクリロイル基、カルボキシル基等で変性したものは耐熱性が向上するためより好ましい。   The adhesive composition of the present invention can further contain a thermoplastic resin. The thermoplastic resin is not particularly limited, but a resin containing a polar group such as a hydroxyl group, an ether group, an ester group, a urethane group, an amide group, an imide group, or a carboxyl group in the main chain skeleton or side chain of the resin. Is preferable from the viewpoint of adhesiveness. Specifically, phenoxy resin, polyester resin, polyurethane resin, polyester urethane resin, polyvinyl butyral resin, polyvinyl formal resin, polyamide resin, polyimide resin, polyacrylic resin, and the like can be used. In addition, a polymer obtained by modifying the polymer with an epoxy group, an acryloyl group, a methacryloyl group, a carboxyl group or the like, which is a reactive functional group, is more preferable because heat resistance is improved.

これらの樹脂の分子量は特に制限を受けるものではないが、一般的な重量平均分子量としては5,000〜150,000が好ましく、10,000〜80,000が特に好ましい。この値が、5,000以上であれば、十分なフィルム形成性を得ることができ、また150,000以下であれば他の成分との相溶性が悪くなる傾向を抑制できる。使用量としては(A)エポキシ樹脂100重量部に対して20〜320重量部とすることが好ましい。
なお、本発明で規定する重量平均分子量とは、以下の条件に従ってゲルパーミエイションクロマトグラフィー法(GPC)により標準ポリスチレンによる検量線を用いて測定したもののことをいう。
〈GPC条件〉使用機器:日立L−6000型〔(株)日立製作所〕、カラム :ゲルパックGL−R420+ゲルパックGL−R430+ゲルパックGL−R440(計3本)〔日立化成工業(株)製商品名〕、溶離液:テトラヒドロフラン、測定温度:40℃、流量:1.75ml/min、検出器:L−3300RI〔(株)日立製作所〕
The molecular weight of these resins is not particularly limited, but the 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 5,000 or more, sufficient film formability can be obtained, and if it is 150,000 or less, the tendency for compatibility with other components to deteriorate can be suppressed. The amount used is preferably 20 to 320 parts by weight per 100 parts by weight of the (A) epoxy resin.
In addition, the weight average molecular weight prescribed | regulated by this invention means what was measured using the analytical curve by a standard polystyrene by the gel permeation chromatography method (GPC) according to the following conditions.
<GPC conditions> Equipment used: Hitachi L-6000 type [Hitachi, Ltd.], Column: Gel Pack GL-R420 + Gel Pack GL-R430 + Gel Pack GL-R440 (3 in total) [trade name, manufactured by Hitachi Chemical Co., Ltd.] , Eluent: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1.75 ml / min, detector: L-3300RI [Hitachi, Ltd.]

本発明の接着材組成物は、回路接続材料に使用する場合などではさらに導電性粒子を含むことができる。本発明の接着材組成物は、接続時に相対向する回路電極の直接接触により接続が得られるが、導電性粒子を含有した場合、より安定した接続が得られる。導電性粒子としては、Au、Ag、Ni、Cu、はんだ等の金属粒子やカーボン等があり、十分なポットライフを得るためには、表層はAu、Ag、白金族の貴金属類が好ましくAuがより好ましい。   The adhesive composition of the present invention may further contain conductive particles when used as a circuit connection material. The adhesive composition of the present invention can be connected by direct contact of circuit electrodes facing each other at the time of connection, but more stable connection can be obtained when it contains conductive particles. Examples of the conductive particles include metal particles such as Au, Ag, Ni, Cu, and solder, carbon, and the like. In order to obtain a sufficient pot life, the surface layer is preferably Au, Ag, or a platinum group noble metal, preferably Au. More preferred.

また、Ni等の遷移金属類の表面をAu等の貴金属類で被覆したものでもよい。また、非導電性のガラス、セラミック、プラスチック(ポリスチレン等)等に前記した導通層を被覆等により形成し、最外層を貴金属類、核をプラスチックとした場合や、熱溶融金属粒子の場合、加熱加圧により変形性を有するので接続時に電極との接触面積が増加し信頼性が向上するので好ましい。   Further, the surface of a transition metal such as Ni may be coated with a noble metal such as Au. In addition, the conductive layer described above is formed by coating or the like on non-conductive glass, ceramic, plastic (polystyrene, etc.), the outermost layer is precious metal, the core is plastic, and in the case of hot-melt metal particles, heating Since it has deformability by pressurization, it is preferable because the contact area with the electrode is increased at the time of connection and the reliability is improved.

導電性粒子の使用量は、接着材組成物100体積に対して0.1〜30体積%とすることが好ましく、0.1〜10体積%とすることがより好ましい。この値が、0.1体積%以上であれば導電性を得ることができ、30体積%以下であれば回路の短絡を抑制できる。尚、体積%は23℃での硬化前の各成分の体積をもとに決定されるが、各成分の体積は、比重を利用して重量から体積に換算することができる。   It is preferable to set it as 0.1-30 volume% with respect to 100 volume of adhesive composition, and, as for the usage-amount of electroconductive particle, it is more preferable to set it as 0.1-10 volume%. If this value is 0.1% by volume or more, conductivity can be obtained, and if it is 30% by volume or less, a short circuit of the circuit can be suppressed. The volume% is determined based on the volume of each component before curing at 23 ° C., but the volume of each component can be converted from weight to volume using specific gravity.

本発明の接着材組成物は、光塩基発生剤の塩基発生効率を向上させることを目的に、増感剤を併用してもよい。使用する増感剤としては、硬化性組成物に悪影響を及ぼさない限り、公知の一重項増感剤、三重項増感剤を用いることができる。例えば、ナフタレン、アントラセン、ピレン等の芳香族化合物誘導体、カルバゾール誘導体、ベンゾフェノン誘導体、チオキサントン誘導体、クマリン誘導体等が好適に用いられる。増感剤の使用量は、増感剤の吸収波長及びモル吸光係数を参考にする必要があるが、一般的にイミダゾリウム塩化合物1重量部に対して0.01〜5重量部が好ましく、0.1〜2重量部が特に好ましい。増感剤が0.01重量部以上であれば光吸収の効率向上効果を得ることができ、5重量部以下であれば硬化性組成物全体に光が届かない状況を防ぐことができる。   The adhesive composition of the present invention may be used in combination with a sensitizer for the purpose of improving the base generation efficiency of the photobase generator. As a sensitizer to be used, a known singlet sensitizer and triplet sensitizer can be used as long as they do not adversely affect the curable composition. For example, aromatic compound derivatives such as naphthalene, anthracene, and pyrene, carbazole derivatives, benzophenone derivatives, thioxanthone derivatives, and coumarin derivatives are preferably used. The amount of the sensitizer used is required to refer to the absorption wavelength and molar extinction coefficient of the sensitizer, but is generally preferably 0.01 to 5 parts by weight with respect to 1 part by weight of the imidazolium salt compound. 0.1 to 2 parts by weight is particularly preferred. If the sensitizer is 0.01 parts by weight or more, the effect of improving the light absorption efficiency can be obtained, and if it is 5 parts by weight or less, a situation where light does not reach the entire curable composition can be prevented.

本発明の接着材組成物では、接着力の更なる向上を目的にエポキシ基やメルカプト基、アミノ基、イミダゾール基等の有機官能基を骨格中に有するシランカップリング剤やテトラアルコキシチタネート誘導体やポリジアルキルチタネート誘導体に代表されるカップリング剤を含有することもできる。さらに、充填材、軟化剤、促進剤、老化防止剤、着色剤、難燃化剤、チキソトロピック剤を含有することもできる。   In the adhesive composition of the present invention, a silane coupling agent having a functional group such as an epoxy group, a mercapto group, an amino group, or an imidazole group in the skeleton, a tetraalkoxy titanate derivative or a polysiloxane is used for the purpose of further improving the adhesive strength. A coupling agent typified by a dialkyl titanate derivative can also be contained. Furthermore, a filler, a softener, an accelerator, an anti-aging agent, a colorant, a flame retardant, and a thixotropic agent can also be contained.

本発明の接着材組成物では、(C)光塩基発生剤から光照射によって発生した塩基性化合物がエポキシ樹脂とチオール化合物の硬化を促進することにより、接着材組成物全体の反応を進め、その結果、低温速硬化性が向上する。さらに分子内に1つ以上のエステル結合を持つチオール化合物を含有することで、接着性に優れた接着材組成物の提供が可能となる。   In the adhesive composition of the present invention, (C) the basic compound generated by light irradiation from the photobase generator promotes the curing of the epoxy resin and the thiol compound, thereby promoting the reaction of the entire adhesive composition, As a result, the low temperature fast curability is improved. Furthermore, by including a thiol compound having one or more ester bonds in the molecule, it is possible to provide an adhesive composition having excellent adhesiveness.

本発明の回路端子の接続方法は、第一の接続端子を有する第一の回路部材と、第二の接続端子を有する第二の回路部材とを、第一の接続端子と第二の接続端子を対向して配置し、前記対向配置した第一の接続端子と第二の接続端子の間に本発明の接続材料(好ましくはフィルム状接着材)を介在させ、前記対向配置した第一の接続端子と第二の接続端子のみを電気的に接続させる。このような回路部材としては半導体チップ、抵抗体チップ、コンデンサチップ等のチップ部品、プリント基板等の基板等が用いられる。回路部材には接続端子が通常は多数(場合によっては単数でもよい)設けられている。   The circuit terminal connection method of the present invention includes a first circuit member having a first connection terminal and a second circuit member having a second connection terminal, the first connection terminal and the second connection terminal. Are arranged opposite to each other, and the connection material of the present invention (preferably a film-like adhesive) is interposed between the first connection terminal and the second connection terminal arranged opposite to each other, and the first connection arranged oppositely. Only the terminal and the second connection terminal are electrically connected. As such a circuit member, a chip component such as a semiconductor chip, a resistor chip or a capacitor chip, a substrate such as a printed circuit board, or the like is used. The circuit member is usually provided with a large number of connection terminals (or a single connection terminal in some cases).

より良好な電気的接続を得るためには、回路電極(接続端子)の少なくとも一方の表面を、金、銀、錫及び白金族から選ばれる金属にすることが好ましい。表面層は金、銀、白金族、又は錫のいずれかから選択され、これらを組み合わせて用いてもよい。また、銅/ニッケル/金のように複数の金属を組み合わせて多層構成としてもよい。   In order to obtain better electrical connection, it is preferable that at least one surface of the circuit electrode (connection terminal) is made of a metal selected from gold, silver, tin, and a platinum group. The surface layer is selected from gold, silver, platinum group, or tin, and these may be used in combination. Moreover, it is good also as a multilayer structure combining several metals like copper / nickel / gold.

接続方法としては、第一の接続端子を有する第一の回路部材上に接着材組成物を配置させた後、接着材組成物の上方から光照射を行った後、第二の接続端子を有する第二の回路部材を対向して配置し、加熱しながら加圧し、光照射と加熱及び加圧を逐次的に行って接着させることができる。   As a connection method, after arranging an adhesive composition on a first circuit member having a first connection terminal, after irradiating light from above the adhesive composition, it has a second connection terminal. The second circuit member can be disposed to face and pressurize while heating, and can be bonded by sequentially performing light irradiation, heating and pressurization.

また、第一の回路部材が紫外域から可視域にかけて透明な基材の場合には、第一の接続端子を有する第一の回路部材上に接着材組成物を配置させた後、第二の接続端子を有する第二の回路部材を対向して配置し、第二の回路部材上から加熱、加圧と同時に第一の回路部材下方から光照射を行っても接着させることができる。硬化条件は、通常、加熱の場合、0.1〜10MPaの加圧下で、100〜200℃で1秒〜120秒であるが、これに限定されるものでない。光照射は、150〜750nmの波長域の照射光が好ましく、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ、メタルハライドランプを使用することができ、光照射量としては365nm照度換算で0.01〜10J/cmであるが、これに限定されるものでない。 In the case where the first circuit member is a transparent substrate from the ultraviolet region to the visible region, after the adhesive composition is disposed on the first circuit member having the first connection terminal, the second circuit member A second circuit member having a connection terminal can be disposed oppositely, and can be bonded even if light irradiation is performed from below the first circuit member simultaneously with heating and pressurization from the second circuit member. The curing condition is usually 1 to 120 seconds at 100 to 200 ° C. under a pressure of 0.1 to 10 MPa in the case of heating, but is not limited thereto. The light irradiation is preferably in the wavelength range of 150 to 750 nm, and a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, or a metal halide lamp can be used. Although it is 0.01-10 J / cm < 2 >, it is not limited to this.

本発明の接着材組成物は、常温(25℃)で液状である場合にはペースト状で使用することができる。室温(25℃)で固体の場合には、加熱して使用する他、溶剤を使用してペースト化してもよい。使用できる溶剤としては、硬化性に悪影響を及ぼさず、かつ十分な溶解性を示すものであれば、特に制限は受けないが、常圧での沸点が50〜150℃であるものが好ましい。沸点が50℃以上であれば、室温(25℃)で放置した場合の揮発を防止することができ、開放系での使用が可能となる。また、沸点が150℃以下であれば、溶剤の除去が容易となる。   The adhesive composition of the present invention can be used in the form of a paste when it is liquid at room temperature (25 ° C.). In the case of a solid at room temperature (25 ° C.), in addition to heating, it may be pasted using a solvent. The solvent that can be used is not particularly limited as long as it does not adversely affect the curability and exhibits sufficient solubility, but a solvent having a boiling point of 50 to 150 ° C. at normal pressure is preferable. When the boiling point is 50 ° C. or higher, volatilization when left at room temperature (25 ° C.) can be prevented, and use in an open system is possible. Moreover, if a boiling point is 150 degrees C or less, the removal of a solvent will become easy.

本発明の接着材組成物はフィルム状にして用いることもできる。接着材組成物に必要により溶剤等を加えた溶液を、フッ素樹脂フィルム、ポリエチレンテレフタレートフィルム、離形紙等の剥離性基材上に塗布し、あるいは不織布等の基材に前記溶液を含浸させて剥離性基材上に載置し、溶剤等を除去してフィルムとして使用することができる。フィルムの形状で使用すると取扱性等の点から一層便利である。   The adhesive composition of the present invention can be used in the form of a film. A solution in which a solvent or the like is added to the adhesive composition as necessary is applied onto 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. It can be placed on a peelable substrate and 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.

以下に、本発明を実施例に基づいて具体的に説明するが、本発明はこれに限定されるものではない。   Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

(アミンイミドの合成)
100mlの三つ口フラスコ中にp−ニトロ安息香酸メチルエステル(2.00g、11mmol)、N,N−ジメチルヒドラジン(0.66g、11mmol)、フェニルグリシジルエーテル(1.66g、11mmol)、tert−ブタノール(15.0g)を加え、窒素ガスを送りながら50℃で10時間攪拌した後、さらに室温(25℃)で48時間攪拌したところ、白色沈殿が生成した。この得られた沈殿物を濾別した後、酢酸エチルで2度洗浄し、真空乾燥機(装置名:LHV−112、TABAI社製)で乾燥させてアミンイミド化合物を得た。収量3.67g、収率85%であった。
(Synthesis of amine imide)
P-Nitrobenzoic acid methyl ester (2.00 g, 11 mmol), N, N-dimethylhydrazine (0.66 g, 11 mmol), phenylglycidyl ether (1.66 g, 11 mmol), tert- Butanol (15.0 g) was added, stirred for 10 hours at 50 ° C. while feeding nitrogen gas, and further stirred for 48 hours at room temperature (25 ° C.). As a result, a white precipitate was formed. The obtained precipitate was filtered off, washed twice with ethyl acetate, and dried with a vacuum dryer (device name: LHV-112, manufactured by Tabai) to obtain an amine imide compound. The yield was 3.67 g, and the yield was 85%.

(イミダゾリウム塩の合成)
100mlの三つ口フラスコ中にp−ニトロフェナシルブロマイド(2.00g、8.2mmol)をアセトン(20g)に溶解させ、これにアセトン(5g)に溶解させた1,2−ジメチルイミダゾール(0.79g、8.2mmol)の溶液をゆっくり添加し、この後、室温(25℃)で2時間攪拌したところ、白色結晶が析出した。この得られた結晶をろ過し、アセトンで2度洗浄を行った後、真空下60℃で5時間乾燥して、イミダゾリウム・ブロマイド塩を得た(収量2.62g)。上記イミダゾール・ブロマイド塩(2.00g、5.8mmol)を、メタノール/水(15g/15g)溶液に溶解させ、これに水(5.0g)に溶解させたテトラフェニルほう酸ナトリウム塩(2.01g、5.8mmol)の溶液をゆっくり添加した。
添加とともに、白色スラリー状の析出が認められ、添加後、さらに室温(25℃)で5時間攪拌した。この得られた析出物をろ過し、アセトン(20g)に溶解させて再結晶を行い、目的のイミダゾリウム・テトラフェニルほう酸塩(イミダゾリウム塩)を得た(収量3.23g)。
なお、攪拌はすべてマグネティックスターラー(F202SC,Fine社製)で行い、温度制御はオイルバス(装置名:FWB−240,Fine社製)によって行った。
(Synthesis of imidazolium salt)
In a 100 ml three-necked flask, p-nitrophenacyl bromide (2.00 g, 8.2 mmol) was dissolved in acetone (20 g), and 1,2-dimethylimidazole (0 g) dissolved in acetone (5 g) was dissolved therein. .79 g, 8.2 mmol) was slowly added, and then stirred at room temperature (25 ° C.) for 2 hours to precipitate white crystals. The obtained crystals were filtered, washed twice with acetone, and then dried under vacuum at 60 ° C. for 5 hours to obtain an imidazolium bromide salt (yield 2.62 g). The above-mentioned imidazole bromide salt (2.00 g, 5.8 mmol) was dissolved in a methanol / water (15 g / 15 g) solution, and tetraphenylborate sodium salt (2.01 g) dissolved in water (5.0 g). 5.8 mmol) solution was added slowly.
A white slurry-like precipitation was observed with the addition, and the mixture was further stirred at room temperature (25 ° C.) for 5 hours. The obtained precipitate was filtered, dissolved in acetone (20 g) and recrystallized to obtain the target imidazolium tetraphenylborate (imidazolium salt) (yield 3.23 g).
In addition, all stirring was performed with the magnetic stirrer (F202SC, the Fine company make), and temperature control was performed with the oil bath (device name: FWB-240, the Fine company make).

(4級アンモニウム塩1の合成)
100mlの三つ口フラスコ中にp−ニトロフェナシルブロマイド(2.00g、8.2mmol)をアセトン(20g)に溶解させ、これにアセトン(5g)に溶解させたN,N−ジメチルベンジルアミン(1.10g、8.2mmol)の溶液をゆっくり添加し、この後、室温(25℃)で2時間かくはんしたところ、白色結晶が析出した。これをろ過し、アセトンで2度洗浄を行った後、真空下60℃で5時間乾燥して、アンモニウム・ブロマイド塩1を得た(収量2.73g)。200mlの三つ口フラスコ中に上記アンモニウム・ブロマイド塩1(2.00g、5.3mmol)を、メタノール/水(15g/15g)溶液に溶解させ、これにメタノール/水(2.5g/2.5g)に溶解させたテトラフェニルほう酸ナトリウム塩(1.84g、5.3mmol)の溶液をゆっくり添加した。添加とともに、白色スラリー状の析出が認められ、添加後、さらに室温(25℃)で5時間かくはんした。これをろ過し、アセトン(20g)に溶解させて再結晶を行い、目的の4級アンモニウム塩を得た(収量2.98g)。
(4級アンモニウム塩2の合成)
200mlの三つ口フラスコ中に2−(ブロモアセチル)ナフタレン(3.00g、12.0mmol)、メチルエチルケトン(30g)を加え、これにメチルエチルケトン(10g)に溶解させた1,8−ジアザ−ビシクロ(5,4,0)−ウンデセン−7(1.83g、12.0mmol)の溶液をゆっくり添加し、この後、0℃で4時間かくはんしたところ、白色結晶が析出した。これをろ過し、アセトンで2度洗浄を行った後、真空下60℃で5時間乾燥して、アンモニウム・ブロマイド塩2を得た(収量3.15g)。
200mlの三つ口フラスコ中に上記アンモニウム・ブロマイド塩2(3.00g、7.5mmol)を、メタノール/水(50g/50g)溶液に溶解させ、これにメタノール/水(5g/5g)に溶解させたテトラフェニルほう酸ナトリウム塩(2.56g、7.5mmol)の溶液をゆっくり添加した。添加とともに、白色スラリー状の析出が認められ、添加後、さらに室温で5時間かくはんした。これをろ過し、アセトン(20g)に溶解させて再結晶を行い、目的の4級アンモニウム塩2を得た(収量3.80g)。
(Synthesis of quaternary ammonium salt 1)
In a 100 ml three-necked flask, p-nitrophenacyl bromide (2.00 g, 8.2 mmol) was dissolved in acetone (20 g), and N, N-dimethylbenzylamine (5 g) was dissolved in acetone (5 g). A solution of 1.10 g, 8.2 mmol) was slowly added, and then stirred at room temperature (25 ° C.) for 2 hours to precipitate white crystals. This was filtered, washed twice with acetone, and then dried under vacuum at 60 ° C. for 5 hours to obtain ammonium bromide salt 1 (yield 2.73 g). The ammonium bromide salt 1 (2.00 g, 5.3 mmol) was dissolved in a methanol / water (15 g / 15 g) solution in a 200 ml three-necked flask, and methanol / water (2.5 g / 2. A solution of sodium tetraphenylborate (1.84 g, 5.3 mmol) dissolved in 5 g) was added slowly. A white slurry-like precipitation was observed with the addition, and the mixture was further stirred at room temperature (25 ° C.) for 5 hours. This was filtered, dissolved in acetone (20 g) and recrystallized to obtain the desired quaternary ammonium salt (yield 2.98 g).
(Synthesis of quaternary ammonium salt 2)
2- (Bromoacetyl) naphthalene (3.00 g, 12.0 mmol) and methyl ethyl ketone (30 g) were added to a 200 ml three-necked flask, and 1,8-diaza-bicyclo (dissolved in methyl ethyl ketone (10 g) was added thereto. A solution of 5,4,0) -undecene-7 (1.83 g, 12.0 mmol) was slowly added, followed by stirring at 0 ° C. for 4 hours to precipitate white crystals. This was filtered, washed twice with acetone, and then dried under vacuum at 60 ° C. for 5 hours to obtain ammonium bromide salt 2 (yield 3.15 g).
Ammonium bromide salt 2 (3.00 g, 7.5 mmol) is dissolved in a methanol / water (50 g / 50 g) solution in a 200 ml three-necked flask, and dissolved in methanol / water (5 g / 5 g). A solution of tetraphenylborate sodium salt (2.56 g, 7.5 mmol) was added slowly. A white slurry-like precipitation was observed with the addition, and the mixture was further stirred at room temperature for 5 hours. This was filtered, dissolved in acetone (20 g) and recrystallized to obtain the desired quaternary ammonium salt 2 (yield 3.80 g).

(カルバミン酸エステルの合成)
100mlの三つ口フラスコ中に2,4−ジニトロベンジルアルコール(2.00g、10mmol)および1,8−ジアザ−ビシクロ(5,4,0)ウンデセン−7(0.10g、0.6mmol)、テトラヒドロフラン20gを加え、シクロヘキシルイソシアネート(1.27g、10mmol)を室温(25℃)で滴下した。滴下終了後室温(25℃)で48時間攪拌したところ、白色沈殿が生成した。これを濾別した後、酢酸エチルで再結晶を行い、真空乾燥機で乾燥させてカルバミン酸エステル化合物を得た。収量2.23g、収率68%であった。
(Synthesis of carbamate)
2,4-dinitrobenzyl alcohol (2.00 g, 10 mmol) and 1,8-diaza-bicyclo (5,4,0) undecene-7 (0.10 g, 0.6 mmol) in a 100 ml three-necked flask, Tetrahydrofuran (20 g) was added, and cyclohexyl isocyanate (1.27 g, 10 mmol) was added dropwise at room temperature (25 ° C.). After completion of the dropwise addition, the mixture was stirred at room temperature (25 ° C.) for 48 hours, and a white precipitate was formed. This was filtered off, recrystallized with ethyl acetate, and dried with a vacuum dryer to obtain a carbamate compound. The yield was 2.23 g and the yield was 68%.

(オキシムエステルの合成)
100mlの三つ口フラスコ中に9−フルオレノンオキシム(2.00g、10mmol)およびピリジン(0.80g、10mmol)をテトラヒドロフラン20g中に溶解し、ジエチルカルバモイルクロリド(1.36g、10mmol)を氷浴で冷却しながらで滴下した。滴下終了後室温(25℃)で24時間攪拌したところ、白色沈殿が生成した。これに水を200g加えると淡黄色沈殿が析出した。これを濾別した後、アセトンで再結晶を行い、真空乾燥機で乾燥させてオキシムエステル化合物を得た。収量2.58g、収率88%であった。
(Synthesis of oxime ester)
In a 100 ml three-necked flask, 9-fluorenone oxime (2.00 g, 10 mmol) and pyridine (0.80 g, 10 mmol) were dissolved in 20 g of tetrahydrofuran, and diethylcarbamoyl chloride (1.36 g, 10 mmol) was dissolved in an ice bath. It was added dropwise while cooling. After completion of the dropwise addition, the mixture was stirred at room temperature (25 ° C.) for 24 hours, and a white precipitate was formed. When 200 g of water was added thereto, a pale yellow precipitate was deposited. This was filtered off, recrystallized with acetone, and dried with a vacuum dryer to obtain an oxime ester compound. The yield was 2.58 g and the yield was 88%.

(実施例1〜12)
熱可塑性樹脂として、フェノキシ樹脂及びウレタン樹脂を使用した。フェノキシ樹脂(PKHC、ユニオンカーバイト社製商品名、平均分子量45,000)40gを、ガラス製の容器に入れたメチルエチルケトン(製品名:2−ブタノン、和光純薬工業(株)社製、純度99%)60gに溶解して、固形分40重量%の溶液とした。また、ウレタン樹脂は、平均分子量2000のポリブチレンアジペートジオール(製品名:ポリブチレンアジペートジオール、Aldrich社製)450重量部と平均分子量2000のポリオキシテトラメチレングリコール(製品名:ポリオキシテトラメチレングリコール、Aldrich社製)450重量部、1,4−ブチレングリコール(製品名:1,4−ブチレングリコール、Aldrich社製)100重量部をメチルエチルケトン(製品名:2−ブタノン、和光純薬工業(株)社製、純度99%)4000重量部中で溶解し、ジフェニルメタンジイソシアネート(製品名:ジフェニルメタンジイソシアネート、Aldrich社製)390重量部を加えて70℃にて60分間反応させて得た。なお、この時の温度制御はオイルバス(装置名:FWB−240,Fine社製)により行った。得られたウレタン樹脂の重量平均分子量をゲルパーミエイションクロマトグラフィー法(GPC)によって測定したところ、12万であった。
エポキシ樹脂(A)としてフェノールノボラック型エポキシ樹脂(エピコート152、ジャパンエポキシレジン株式会社製商品名)、チオール化合物(B)としてペンタエリスリトールテトラキスチオプロピオネート(PETP、東京化成工業株式会社製)又はイソシアヌレート変性チオール化合物(THEIC−BMPA、淀化学株式会社製品名)、シランカップリング剤として3−グリシドキシプロピルトリメトキシシラン(SZ6040、東レ・ダウコーニング・シリコーン株式会社製商品名)、光塩基発生剤(C)として表1に示す化合物を用いた。またポリスチレンを核とする粒子の表面に、厚み0.2μmのニッケル層を設け、このニッケル層の外側に、厚み0.02μmの金層を設け、平均粒径4μm、比重2.5の導電性粒子を作製した。
(Examples 1-12)
As the thermoplastic resin, a phenoxy resin and a urethane resin were used. Methyl ethyl ketone (product name: 2-butanone, manufactured by Wako Pure Chemical Industries, Ltd., purity 99) in which 40 g of phenoxy resin (PKHC, trade name of Union Carbide, average molecular weight 45,000) is put in a glass container. %) Was dissolved in 60 g to obtain a solution having a solid content of 40% by weight. The urethane resin is composed of 450 parts by weight of polybutylene adipate diol having an average molecular weight of 2000 (product name: polybutylene adipate diol, manufactured by Aldrich) and polyoxytetramethylene glycol having an average molecular weight of 2000 (product name: polyoxytetramethylene glycol, Aldrich) 450 parts by weight, 1,4-butylene glycol (product name: 1,4-butylene glycol, Aldrich) 100 parts by weight methyl ethyl ketone (product name: 2-butanone, Wako Pure Chemical Industries, Ltd.) The product was obtained by dissolving in 4000 parts by weight of a product (purity 99%), adding 390 parts by weight of diphenylmethane diisocyanate (product name: diphenylmethane diisocyanate, manufactured by Aldrich) and reacting at 70 ° C. for 60 minutes. In addition, temperature control at this time was performed by an oil bath (device name: FWB-240, manufactured by Fine). It was 120,000 when the weight average molecular weight of the obtained urethane resin was measured by the gel permeation chromatography method (GPC).
Phenol novolac type epoxy resin (Epicoat 152, trade name of Japan Epoxy Resin Co., Ltd.) as the epoxy resin (A), pentaerythritol tetrakisthiopropionate (PETP, manufactured by Tokyo Chemical Industry Co., Ltd.) or Isocyan as the thiol compound (B) Nurate modified thiol compound (THEIC-BMPA, Sakai Chemical Co., Ltd. product name), 3-glycidoxypropyltrimethoxysilane (SZ6040, trade name of Toray Dow Corning Silicone Co., Ltd.) as a silane coupling agent, photobase generation The compounds shown in Table 1 were used as the agent (C). Further, a nickel layer having a thickness of 0.2 μm is provided on the surface of a particle having polystyrene as a nucleus, and a gold layer having a thickness of 0.02 μm is provided outside the nickel layer, and the conductive material has an average particle diameter of 4 μm and a specific gravity of 2.5. Particles were made.

固形重量比で表1に示すように配合し、さらに導電性粒子を1.5体積%配合分散させ、厚み80μmのフッ素樹脂フィルムに塗工装置(装置名:SNC−S3.0、康井精機(株)社製)を用いて塗布し、70℃、10分の熱風乾燥によって接着材層の厚みが20μmのフィルム状接着材を得た。   It mix | blends as shown in Table 1 by solid weight ratio, Furthermore, 1.5 volume% of electroconductive particles are mix-dispersed, and it applies to a fluororesin film of 80 micrometers in thickness (apparatus name: SNC-S3.0, Yasui Seiki). And a film adhesive having an adhesive layer thickness of 20 μm was obtained by hot air drying at 70 ° C. for 10 minutes.

Figure 0004892923
Figure 0004892923

(接着強度、接続抵抗の測定)
上記製法によって得たフィルム状接着材を用いて、ライン幅50μm、ピッチ100μm、厚み18μmの銅回路を500本有するフレキシブル回路板(FPC)と、0.2μmの酸化インジウム(ITO)の薄層を形成したガラス(厚み1.1mm、表面抵抗20Ω/□)とを、140℃、3MPaで30秒間加熱加圧して幅2mmにわたり接続した。
この時、あらかじめITOガラス上に、フィルム状回路接続材料の接着面を70℃、0.5MPaで3秒間加熱加圧して仮接続した後、フッ素樹脂フィルムを剥離し、回路接続用組成物からなるフィルム面に、高圧水銀ランプを有する紫外線照射装置(ウシオ電機株式会社製)を用いて2.0J/cmの紫外線を照射した。その後、もう一方の被着体であるFPCと接続し接続体を作製した。この接続体の隣接回路間の抵抗値を、接着直後と、85℃、85%RHの高温高湿槽中に168時間保持した後にマルチメータ(装置名:TR6848、アドバンテスト社製)で測定した。抵抗値は隣接回路間の抵抗37点の平均で示した。
(Measurement of adhesive strength and connection resistance)
Using the film-like adhesive obtained by the above manufacturing method, a flexible circuit board (FPC) having 500 copper circuits having a line width of 50 μm, a pitch of 100 μm, and a thickness of 18 μm, and a thin layer of 0.2 μm of indium oxide (ITO) The formed glass (thickness 1.1 mm, surface resistance 20Ω / □) was heated and pressurized at 140 ° C. and 3 MPa for 30 seconds to be connected over a width of 2 mm.
At this time, the adhesive surface of the film-like circuit connecting material is preliminarily connected to the ITO glass by heating and pressurizing at 70 ° C. and 0.5 MPa for 3 seconds, and then the fluororesin film is peeled off to form the circuit connecting composition. The film surface was irradiated with ultraviolet rays of 2.0 J / cm 2 using an ultraviolet irradiation device (USHIO INC.) Having a high-pressure mercury lamp. Then, it connected with FPC which is another to-be-adhered body, and produced the connection body. The resistance value between adjacent circuits of this connection body was measured with a multimeter (device name: TR6848, manufactured by Advantest) immediately after bonding and after being held in a high-temperature and high-humidity bath at 85 ° C. and 85% RH. The resistance value was shown as an average of 37 resistances between adjacent circuits.

また、この接続体の接着強度をJIS−Z0237に準じて90度剥離法で測定し、評価した。ここで、接着強度の測定装置は東洋ボールドウィン株式会社製テンシロンUTM−4(剥離速度50mm/min、25℃)を使用した。   Moreover, the adhesive strength of this connection body was measured by a 90-degree peeling method according to JIS-Z0237 and evaluated. Here, Tensilon UTM-4 (peeling speed 50 mm / min, 25 ° C.) manufactured by Toyo Baldwin Co., Ltd. was used as a measuring device for adhesive strength.

(比較例1)
光塩基発生剤(C)であるイミダゾリウム塩の代わりに1,2−ジメチルイミダゾールを使用した以外は実施例3と同様の配合でフィルム状接着材を作製し、実施例3と同様に接続体を作製した。
(Comparative Example 1)
A film-like adhesive was prepared in the same manner as in Example 3 except that 1,2-dimethylimidazole was used in place of the imidazolium salt as the photobase generator (C). Was made.

(比較例2)
チオール化合物(B)であるPETPの代わりに分子内にエステル結合を持たないSH当量が85であるp−キシレンジチオール(SH当量85、固形重量比で25)を使用した以外は実施例4と同様の配合でフィルム状接着材を作製し、実施例4と同様に接続体を作製した。
(Comparative Example 2)
Similar to Example 4 except that p-xylenedithiol (SH equivalent 85, solid weight ratio 25) having an SH equivalent of 85 and having no ester bond in the molecule was used instead of PETP which is a thiol compound (B). A film-like adhesive was prepared with the above composition, and a connection body was prepared in the same manner as in Example 4.

以上のようにして行った接続体の接着強度、接続抵抗の測定の結果を表2に示した。   Table 2 shows the results of measurement of the adhesive strength and connection resistance of the connection body performed as described above.

Figure 0004892923
Figure 0004892923

実施例1〜12で得られた接着材組成物は、加熱温度140℃において、接着直後及び85℃、85%RHの高温高湿槽中に168時間保持した後で、良好な接続抵抗及び接着強度を示し、良好な特性を示すことが分かった。一方、光塩基発生剤の代わりに1,2−ジメチルイミダゾールを添加した比較例1では、フィルム作製時の乾燥(70℃、10分)時に硬化が進行し、接続体を得ることができなかった。また、分子内にエステル結合を持たないチオール化合物を用いた比較例2では接着直後の接続抵抗値が高く、85℃、85%RHの高温高湿槽中で168時間保持した後では、急激な接続抵抗の上昇と接着力低下が顕在化した。   The adhesive compositions obtained in Examples 1 to 12 had good connection resistance and adhesion at a heating temperature of 140 ° C. immediately after adhesion and after being held in a high-temperature and high-humidity tank at 85 ° C. and 85% RH for 168 hours. It was found to show strength and good properties. On the other hand, in Comparative Example 1 in which 1,2-dimethylimidazole was added instead of the photobase generator, curing progressed during drying (70 ° C., 10 minutes) during film production, and a connection body could not be obtained. . Moreover, in Comparative Example 2 using a thiol compound having no ester bond in the molecule, the connection resistance value immediately after adhesion is high, and after holding in a high-temperature and high-humidity tank at 85 ° C. and 85% RH, it is abrupt. An increase in connection resistance and a decrease in adhesive strength became apparent.

(実施例13)
実施例7で得られたフィルム状接着材を、真空包装を施して、40℃で3日間放置した後、実施例7と同様にFPCとITOとを140℃、3MPa、30sで加熱圧着を行った。以上のようにして行った接続体の接着強度、接続抵抗を測定したところ、接着強度は790N/m、接続抵抗は1.7Ωを示し、放置安定性に優れることが分かった。


(Example 13)
The film adhesive obtained in Example 7 was vacuum packaged and allowed to stand at 40 ° C. for 3 days, and then FPC and ITO were thermocompression bonded at 140 ° C., 3 MPa, 30 s in the same manner as in Example 7. It was. As a result of measuring the adhesive strength and connection resistance of the connected body as described above, it was found that the adhesive strength was 790 N / m and the connection resistance was 1.7Ω, which was excellent in storage stability.


Claims (8)

(A)エポキシ樹脂、(B)分子内に1つ以上のエステル結合を持つチオール化合物、(C)光照射によって塩基を発生する光塩基発生剤及び導電性粒子を含有し、
(B)チオール化合物が、トリメチロールプロパントリスチオグリコレート、ペンタエリスリトールテトラキスチオグリコレート、トリメチロールプロパントリスチオプロピオネート、ペンタエリスリトールテトラキスチオプロピオネート、下記一般式(1)、(2)で示される化合物の群から選ばれる少なくとも一種類の化合物であることを特徴とする回路接続用接着材組成物。
Figure 0004892923
(一般式(1)、(2)において、m、nは独立に1〜5の整数を示す)
(A) an epoxy resin, (B) a thiol compound having one or more ester bonds in the molecule, (C) a photobase generator that generates a base by light irradiation and conductive particles ,
(B) The thiol compound is trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthioglycolate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, represented by the following general formulas (1) and (2): An adhesive composition for circuit connection, which is at least one compound selected from the group of compounds shown .
Figure 0004892923
(In general formulas (1) and (2), m and n each independently represents an integer of 1 to 5)
(B)チオール化合物が、前記一般式(1)又は(2)で示される化合物であることを特徴とする請求項1記載の回路接続用接着材組成物。 The adhesive composition for circuit connection according to claim 1, wherein the (B) thiol compound is a compound represented by the general formula (1) or (2) . (C)光塩基発生剤が、アミンイミド誘導体、イミダゾリウム塩誘導体、4級アンモニウム塩誘導体、カルバミン酸エステル誘導体、オキシムエステル誘導体、α−アミノケトン誘導体からなる群より選ばれる一以上の化合物であることを特徴とする請求項1または2記載の回路接続用接着材組成物。 (C) The photobase generator is one or more compounds selected from the group consisting of amine imide derivatives, imidazolium salt derivatives, quaternary ammonium salt derivatives, carbamic acid ester derivatives, oxime ester derivatives, and α-aminoketone derivatives. The adhesive composition for circuit connection according to claim 1 or 2, characterized in that: さらに、熱可塑性樹脂を含有する請求項1乃至3いずれか一項に記載の回路接続用接着材組成物。 Furthermore, the adhesive composition for circuit connections as described in any one of Claims 1 thru | or 3 containing a thermoplastic resin. 前記熱可塑性樹脂が、フェノキシ樹脂、ポリエステル樹脂、ポリウレタン樹脂、ポリエステルウレタン樹脂、ブチラール樹脂、アクリル樹脂から選ばれることを特徴とする請求項4記載の回路接続用接着材組成物。 The adhesive composition for circuit connection according to claim 4, wherein the thermoplastic resin is selected from phenoxy resin, polyester resin, polyurethane resin, polyester urethane resin, butyral resin, and acrylic resin. 第一の接続端子を有する第一の回路部材と、第二の接続端子を有する第二の回路部材とが、第一の接続端子と第二の接続端子を対向して配置されており、前記対向配置した第一の接続端子と第二の接続端子の間に請求項1乃至のいずれか一項記載の回路接続用接着材組成物が介在されており、前記対向配置した第一の接続端子と第二の接続端子のみが電気的に接続されている回路端子の接続構造体。 The first circuit member having the first connection terminal and the second circuit member having the second connection terminal are arranged to face the first connection terminal and the second connection terminal, and The adhesive composition for circuit connection according to any one of claims 1 to 5 is interposed between a first connection terminal and a second connection terminal arranged opposite to each other, and the first connection arranged opposite to the first connection terminal. A circuit terminal connection structure in which only the terminal and the second connection terminal are electrically connected. 第一の接続端子を有する第一の回路部材上に請求項1乃至のいずれか一項記載の回路接続用接着材組成物を配置させ、接着材組成物の上方から光照射を行った後、第二の接続端子を有する第二の回路部材を対向して配置し、加熱しながら加圧して対向配置した第一の接続端子と第二の接続端子のみを電気的に接続させる回路端子の接続方法。 After arrange | positioning the adhesive composition for circuit connections as described in any one of Claims 1 thru | or 5 on the 1st circuit member which has a 1st connection terminal, and performing light irradiation from the upper direction of an adhesive composition The second circuit member having the second connection terminal is disposed oppositely, and the first connection terminal and the second connection terminal that are disposed opposite to each other by applying pressure while heating are electrically connected to each other. Connection method. 第一の接続端子を有する第一の回路部材と、第二の接続端子を有する第二の回路部材とを、第一の接続端子と第二の接続端子を対向して配置し、前記対向配置した第一の接続端子と第二の接続端子の間に請求項1乃至のいずれか一項記載の回路接続用接着材組成物を介在させ、光照射と同時に加熱しながら加圧して前記対向配置した第一の接続端子と第二の接続端子のみを電気的に接続させる回路端子の接続方法。 A first circuit member having a first connection terminal and a second circuit member having a second connection terminal are disposed so that the first connection terminal and the second connection terminal are opposed to each other, and the opposed arrangement is performed. The adhesive composition for circuit connection according to any one of claims 1 to 5 is interposed between the first connection terminal and the second connection terminal, and the facing is performed by applying pressure while heating simultaneously with light irradiation. A circuit terminal connection method for electrically connecting only the arranged first connection terminal and second connection terminal.
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