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JP2000017242A - Hot-melt adhesive composition, pressure-sensitive adhesive film and method for bonding with hot-melt adhesive composition - Google Patents

Hot-melt adhesive composition, pressure-sensitive adhesive film and method for bonding with hot-melt adhesive composition

Info

Publication number
JP2000017242A
JP2000017242A JP10182091A JP18209198A JP2000017242A JP 2000017242 A JP2000017242 A JP 2000017242A JP 10182091 A JP10182091 A JP 10182091A JP 18209198 A JP18209198 A JP 18209198A JP 2000017242 A JP2000017242 A JP 2000017242A
Authority
JP
Japan
Prior art keywords
adhesive composition
hot
film
melt adhesive
copolymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP10182091A
Other languages
Japanese (ja)
Inventor
Koichiro Kawate
恒一郎 川手
Shigeyoshi Ishii
栄美 石井
Perez Mario
マリオ・ペレス
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Co
Original Assignee
Minnesota Mining and Manufacturing Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Priority to JP10182091A priority Critical patent/JP2000017242A/en
Priority to PCT/US1999/013468 priority patent/WO2000000566A1/en
Priority to US09/355,602 priority patent/US6265460B1/en
Publication of JP2000017242A publication Critical patent/JP2000017242A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L24/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09J123/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/06—Polymers
    • H01L2924/078—Adhesive characteristics other than chemical
    • H01L2924/07802—Adhesive characteristics other than chemical not being an ohmic electrical conductor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/095—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00 with a principal constituent of the material being a combination of two or more materials provided in the groups H01L2924/013 - H01L2924/0715
    • H01L2924/097—Glass-ceramics, e.g. devitrified glass
    • H01L2924/09701—Low temperature co-fired ceramic [LTCC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/11—Device type
    • H01L2924/14—Integrated circuits

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain a hot-melt adhesive composition having high storage stability and a high curing rate and being capable of a curing reaction without the necessity for water and capable of film molding without the necessity for a solvent by mixing a polyethylene copolymer having epoxy groups in the molecule with a cationic polymerization catalyst and a thermoplastic polymer having no epoxy groups in the molecule. SOLUTION: The polyethylene copolymer (A) having epoxy groups in the molecule is exemplified by a copolymer of glycidyl (meth)acrylate with ethylene or a terpolymer of such monomers with vinyl acetate. The thermoplastic polymer (B) having no epoxy groups in the molecule is desirably an ethylene/alkyl acrylate copolymer such as an ethylene/ethyl acrylate copolymer. The amounts of components A and B used are usually about 40-80 wt.% and about 15-55 wt.% based on the total weight of the composition, respectively. The cationic polymerization catalyst used is usually about 0.01-10 wt.% based on the entire composition.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、電子部品の接着や
集積回路（ＩＣ）パッケージの作製に特に適した、ホッ
トメルト接着剤組成物、熱圧着性フィルム、およびホッ
トメルト接着剤組成物を用いた接着方法に関する。本発
明の接着剤組成物は、反応性（熱硬化性）の熱接着タイ
プの接着剤として利用できる。The present invention relates to a hot-melt adhesive composition, a thermocompression-bondable film, and a hot-melt adhesive composition which are particularly suitable for bonding electronic components and for producing integrated circuit (IC) packages. The bonding method used. The adhesive composition of the present invention can be used as a reactive (thermosetting) heat bonding type adhesive.

【０００２】[0002]

【従来の技術】熱接着に利用できる、いわゆるホットメ
ルト接着剤の一種として、耐熱性等の性能の向上を目的
として、接着後の硬化（架橋）反応を可能にした、いわ
ゆる反応性（硬化性）ホットメルト接着剤が知られてい
る。従来の反応性ホットメルト接着剤の例としては、次
の（１）〜（６）の接着剤を挙げることができる。 （１）イソシアネート基を有する高分子を含有する湿気
硬化型ホットメルト接着剤（米国特許第５，４１８，２
８８号（特開平６−１５８０１７号公報に対応）等に開
示。） （２）シリル基を有する高分子を含有するシラノール縮
合型ホットメルト接着剤（特開平５−３２０６０８号公
報等に開示）。 （３）アクリロイル基を有する高分子を含有するラジカ
ル重合型ホットメルト接着剤（特開昭６３−２３０７８
１号公報等に開示）。 （４）グリシジル基を有する高分子とフェノール樹脂と
を含有する熱硬化型ホットメルト接着剤（特開平６−１
７２７３１号公報等に開示。） （５）熱接着後に放射線照射により架橋させるホットメ
ルト接着剤（特開平６−３０６３４６号公報等に開
示）。 （６）エチレン、α，β−不飽和カルボン酸およびα，
β−不飽和カルボン酸エステルの三元共重合体と、エチ
レン−グリシジルメタクリレート共重合体と、架橋剤と
してのジアリルフタレート化合物とからなる架橋性樹脂
組成物（特開平４−４５１２３号公報に開示）。 一方、エポキシ成分としてのエポキシ樹脂と、カチオン
重合触媒と、その他の成分とを含んでなり、紫外線等の
光の照射を含む重合操作により重合可能な樹脂組成物
が、米国特許４４０１５３７号、米国特許５７０９９４
８号、米国特許５７２１２８９号等に開示されている。
これら組成物は、光照射により硬化可能な接着剤として
利用できるが、これは、光照射により活性化されたカチ
オン重合触媒が、エポキシ樹脂の反応速度を極めて大き
くするからである。上記その他の成分としては、アクリ
ル系ポリマー等のフリーラジカル的に重合されたポリマ
ー（米国特許５７２１２８９号に開示。）や、熱可塑性
ポリオレフィン（米国特許５７０９９４８号に開示。）
等である。上記の様な組成物は、すぐれた反応性を有す
る、硬化性の粘着剤（米国特許５７２１２８９号）や光
硬化性接着剤（米国特許４４０１５３７号）等として利
用できる。また、ポリエチレン系共重合体を接着成分と
して含有するホットメルト接着剤が、電気分野で好適に
使用されている。この様なポリエチレン系ホットメルト
接着剤は、化学的に安定で、半導体製品などに課せられ
るプレッシャークッカーテスト等の過酷な条件下でのテ
ストでも、その安定性が証明されている。しかし、通常
のポリエチレン系ホットメルト接着剤は、ポリエチレン
系共重合体の分子間での架橋反応（硬化反応）を意図し
ていない。したがって、耐熱性に劣り、ホットメルト接
着剤の接着原理から容易に理解されるように、接着温度
以上の高温度では十分な接着力を発現できない。このよ
うな耐熱性の低さは、電気分野での用途を著しく制限し
ている。例えば、かかる接着剤をＩＣのリードフレーム
のリードピンを固定するための接着性テープとして利用
する場合、テープを１８０℃程度の温度で熱圧着した後
に半田浴に漬け、さらに２３０〜２６０℃の熱環境に放
置する様な条件では使用できない。2. Description of the Related Art As a kind of so-called hot-melt adhesive which can be used for thermal bonding, a so-called reactive (curable) which enables a curing (crosslinking) reaction after bonding for the purpose of improving performance such as heat resistance. ) Hot melt adhesives are known. Examples of conventional reactive hot melt adhesives include the following adhesives (1) to (6). (1) A moisture-curable hot melt adhesive containing a polymer having an isocyanate group (US Pat. No. 5,418,2)
No. 88 (corresponding to JP-A-6-158017). (2) A silanol-condensed hot melt adhesive containing a polymer having a silyl group (disclosed in JP-A-5-320608). (3) Radical polymerization type hot melt adhesive containing a polymer having an acryloyl group (JP-A-63-23078)
No. 1). (4) A thermosetting hot melt adhesive containing a polymer having a glycidyl group and a phenol resin (Japanese Patent Laid-Open No. 6-1)
It is disclosed in, for example, US Pat. (5) A hot-melt adhesive which is crosslinked by radiation irradiation after thermal bonding (disclosed in JP-A-6-306346). (6) ethylene, α, β-unsaturated carboxylic acid and α,
Crosslinkable resin composition comprising a terpolymer of β-unsaturated carboxylic acid ester, an ethylene-glycidyl methacrylate copolymer, and a diallyl phthalate compound as a crosslinking agent (disclosed in JP-A-4-45123) . On the other hand, a resin composition containing an epoxy resin as an epoxy component, a cationic polymerization catalyst, and other components and polymerizable by a polymerization operation including irradiation of light such as ultraviolet light is disclosed in US Pat. No. 4,401,537 and US Pat. 570994
No. 8, US Pat. No. 5,712,289 and the like.
These compositions can be used as an adhesive curable by light irradiation, because a cationic polymerization catalyst activated by light irradiation extremely increases the reaction rate of an epoxy resin. Examples of the other components include polymers polymerized by free radicals such as acrylic polymers (disclosed in U.S. Pat. No. 5,712,289) and thermoplastic polyolefins (disclosed in U.S. Pat. No. 5,709,948).
And so on. The composition as described above can be used as a curable pressure-sensitive adhesive (US Pat. No. 5,712,289) or a photo-curable adhesive (US Pat. No. 4,401,537) having excellent reactivity. A hot melt adhesive containing a polyethylene copolymer as an adhesive component is suitably used in the electric field. Such a polyethylene-based hot-melt adhesive is chemically stable, and its stability has been proved even under severe conditions such as a pressure cooker test applied to semiconductor products. However, ordinary polyethylene hot melt adhesives do not intend a cross-linking reaction (curing reaction) between the molecules of the polyethylene copolymer. Therefore, it is inferior in heat resistance and, as easily understood from the bonding principle of the hot melt adhesive, cannot exhibit sufficient adhesive strength at a high temperature higher than the bonding temperature. Such low heat resistance has severely limited applications in the electrical field. For example, when such an adhesive is used as an adhesive tape for fixing lead pins of an IC lead frame, the tape is thermocompression-bonded at a temperature of about 180 ° C., then immersed in a solder bath, and further subjected to a thermal environment of 230 to 260 ° C. It cannot be used under conditions where it is left unattended.

【０００３】[0003]

【発明が解決しようとする課題】しかしながら、上記従
来の反応性ホットメルト接着剤は、以下に記載するよう
な《１》〜《７》の問題点の１つまたは２つ以上をいま
だ有している。 《１》あるホットメルト接着剤は、一般に硬化反応が遅
く、長時間のポストキュアが必要である。（たとえば、
上記（１）、（２）の接着剤） 《２》あるホットメルト接着剤は、硬化反応の際に水分
を必要とし、外気と接触しにくい部分の接着には不向き
である。（たとえば、上記（１）の接着剤） 《３》あるホットメルト接着剤は、反応副生成物として
水分を発生し、接着力の経時劣化等の悪影響を及ぼす。
（たとえば、上記（２）の場合） 《４》いくつかのホットメルト接着剤は、フィルム状に
成形するために溶剤を必要とし、接着完了後の残留溶剤
が悪影響を及ぼす。（たとえば、上記（１）〜（４）の
場合） 《５》いくつかのホットメルト接着剤は、一般に常温
（約２５℃）で保存した場合でも硬化反応が徐々に進
み、貯蔵安定性が低い。（たとえば、上記（１）〜
（３）の場合） 《６》放射線架橋タイプのものは、放射線が照射できな
いか、若しくは照射しにくい部分の接着には不向きであ
る。（上記（５）の場合） 《７》接着剤（組成物）のあるものは、はじめから活性
な状態で含まれる硬化剤等の硬化成分が必須であるた
め、フィルム等の所定の形状への成形工程において、加
熱による組成物のゲル化を防止するのが困難であり、実
質的には連続生産ができない。（上記（４）および
（６）の場合） 一方、前述のエポキシ樹脂は、通常、常温（約２５℃）
で液状である。また、加熱により液化する固体状のもの
もあるが、加熱時の流動性（たとえば、後述するＭＦＲ
で表される性質）は比較的大きい。したがって、エポキ
シ樹脂単体をホットメルト接着剤として使用することは
できない。また、エポキシ樹脂の高反応性は、エポキシ
樹脂を含有する組成物において、光照射後に、熱硬化性
と加熱時の流動性とを共に良好に維持し、ホットメルト
接着剤として利用することを困難にしていた。さらに、
エポキシ樹脂を含む組成物は、ホットメルト接着剤とし
て高温で圧着した場合、エポキシ樹脂がその他の成分と
分離するおそれがあり、また、アウトガスの発生も懸念
される。分離したエポキシ樹脂は、大き過ぎる流れ性、
低接着力、被着体の汚染、環境汚染の原因になり得る。
また、エポキシ樹脂が分離した場合、熱硬化後の組成物
の弾性率を十分に増大させることができない。さらに、
前述のエポキシ樹脂とカチオン重合触媒とを含んでなる
樹脂組成物では、ポリエチレン系共重合体は必須成分で
はない。したがって、前述のポリエチレン系ホットメル
ト接着剤に比べて、化学的に安定性に乏しい。すなわ
ち、本発明の目的は、従来の反応性ホットメルト接着剤
の有する上記問題点《１》〜《７》のすべてと、エポキ
シ樹脂を含む組成物の持つホットメルト接着剤としての
問題点と、通常のポリエチレン系ホットメルト接着剤の
問題点とを同時に解決できる、ホットメルト接着剤組成
物を提供することにある。However, the conventional reactive hot melt adhesive described above still has one or more of the following problems <1> to <7>. I have. << 1 >> Some hot melt adhesives generally have a slow curing reaction and require a long post cure. (For example,
(Adhesives of the above (1) and (2)) << 2 >> Some hot melt adhesives require moisture at the time of curing reaction, and are not suitable for adhesion of parts that are hardly contacted with outside air. (For example, the adhesive of the above (1)) << 3 >> Some hot melt adhesives generate moisture as a reaction by-product and have an adverse effect such as deterioration with time of the adhesive strength.
(For example, in the case of (2) above) << 4 >> Some hot melt adhesives require a solvent in order to form a film, and a residual solvent after the completion of the adhesion has a bad influence. (For example, in the case of (1) to (4) above) << 5 >> Some hot-melt adhesives generally undergo a gradual curing reaction even when stored at room temperature (about 25 ° C.), and have low storage stability. . (For example, the above (1)-
(Case (3)) << 6 >> The radiation cross-linking type is not suitable for bonding to a portion where radiation cannot be applied or where irradiation is difficult. (In the case of (5) above) << 7 >> Some adhesives (compositions) require a curing component such as a curing agent contained in an active state from the beginning. In the molding step, it is difficult to prevent the composition from gelling due to heating, and substantially no continuous production is possible. (Cases of (4) and (6) above) On the other hand, the aforementioned epoxy resin is usually at room temperature (about 25 ° C).
Liquid. Further, there is a solid state which is liquefied by heating, but the fluidity during heating (for example, MFR described later)
Is relatively large. Therefore, an epoxy resin alone cannot be used as a hot melt adhesive. In addition, the high reactivity of the epoxy resin makes it difficult to use the epoxy resin-containing composition as a hot-melt adhesive in a composition containing the epoxy resin, after the light irradiation, both maintain good thermosetting properties and fluidity during heating. I was further,
When a composition containing an epoxy resin is pressure-bonded at a high temperature as a hot melt adhesive, the epoxy resin may be separated from other components, and there is a concern about outgassing. Separated epoxy resin has too much flowability,
It can cause low adhesion, adherend contamination, and environmental pollution.
Further, when the epoxy resin is separated, the elastic modulus of the composition after heat curing cannot be sufficiently increased. further,
In the resin composition containing the epoxy resin and the cationic polymerization catalyst, the polyethylene copolymer is not an essential component. Therefore, it is chemically less stable than the above-mentioned polyethylene-based hot melt adhesive. That is, the object of the present invention is to provide all of the above problems << 1 >> to << 7 >> of conventional reactive hot melt adhesives, and problems as hot melt adhesives having a composition containing an epoxy resin, An object of the present invention is to provide a hot melt adhesive composition that can simultaneously solve the problems of ordinary polyethylene hot melt adhesives.

【０００４】[0004]

【課題を解決するための手段】本発明は、上記課題を解
決するために、エポキシ成分として、分子内にエポキシ
基を有するポリエチレン系共重合体を含んでなる熱硬化
性のホットメルト接着剤組成物において、さらにカチオ
ン重合触媒と、分子内にエポキシ基を持たない熱可塑性
ポリマーとを含んでなることを特徴とする、ホットメル
ト接着剤組成物、そのホットメルト接着剤組成物のホッ
トメルトコーティングフィルムであって紫外線照射によ
り活性化され、熱硬化可能な熱圧着性フィルム、および
そのホットメルトコーティングフィルムを用いた接着方
法を提供する。SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention provides a thermosetting hot melt adhesive composition comprising a polyethylene copolymer having an epoxy group in a molecule as an epoxy component. Hot melt adhesive composition, further comprising a cationic polymerization catalyst and a thermoplastic polymer having no epoxy group in the molecule, and a hot melt coating film of the hot melt adhesive composition In addition, the present invention provides a thermocompression bonding film which is activated by ultraviolet irradiation and can be thermoset, and a bonding method using the hot melt coating film.

【０００５】本発明のホットメルト接着剤組成物（以
下、「接着剤組成物」と呼ぶ場合もある。）は、ポリエ
チレン系共重合体を必須成分とするので、化学的に安定
である。また、エポキシ基を有するポリエチレン系共重
合体の分子間架橋反応により組成物が硬化するので、耐
熱性もすぐれている。本発明のホットメルト接着剤組成
物は、はじめから活性化された状態の硬化剤を含まな
い。したがって、熱に対して安定であり、たとえば、１
５０℃以下の温度において、加熱による組成物のゲル化
を生じることなくホットメルトコーティングしてフィル
ム状に加工でき、熱圧着性の接着フィルムや、ホットメ
ルトフィルムを容易に連続生産できる。また、この様に
して得られたフィルムは、紫外線照射により活性化され
た後は、たとえば、１２０℃以上の温度で熱硬化可能で
あるので、通常の熱硬化型の熱圧着性フィルムやホット
メルトフィルムと同様に、貼り付け後は放射線架橋を必
要とすることなく熱硬化できるので、上記《６》の課題
を解決できる。また、エポキシ成分として、分子内にエ
ポキシ基を有するポリエチレン系共重合体を含むので、
紫外線照射後に、熱硬化可能なホットメルト接着剤とし
て利用することができる。すなわち、分子内にエポキシ
基を有するポリエチレン系共重合体が、紫外線照射後の
組成物の、ホットメルト時の流動性と熱硬化性（therma
l curability）とを良好にすることができる。また、エ
ポキシ樹脂の分離に由来する問題（大き過ぎる流れ性、
低接着力等）と、アウトガスの問題も解決できる。した
がって、この様な観点からは、エポキシ成分が、エポキ
シ樹脂を実質的に含まず、エポキシ基を有するポリエチ
レン系共重合体から実質的になるのが好適である。The hot melt adhesive composition of the present invention (hereinafter sometimes referred to as "adhesive composition") is chemically stable because it contains a polyethylene copolymer as an essential component. Further, since the composition is cured by an intermolecular crosslinking reaction of a polyethylene-based copolymer having an epoxy group, the composition has excellent heat resistance. The hot melt adhesive composition of the present invention does not contain a curing agent in an activated state from the beginning. Therefore, it is stable to heat, for example, 1
At a temperature of 50 ° C. or less, the composition can be hot-melt coated and formed into a film without causing gelation of the composition by heating, and a thermocompression bonding film or a hot-melt film can be easily and continuously produced. After the film obtained in this manner is activated by ultraviolet irradiation, it can be thermoset at a temperature of, for example, 120 ° C. or more. As in the case of the film, the film can be heat-cured after the application without radiation crosslinking, so that the problem of <6> can be solved. Also, as an epoxy component, a polyethylene-based copolymer having an epoxy group in the molecule is included,
After irradiation with ultraviolet rays, it can be used as a hot-melt adhesive that can be thermoset. In other words, the polyethylene-based copolymer having an epoxy group in the molecule is used for the flowability and thermosetting properties of the composition after ultraviolet irradiation during hot melt (therma).
l curability). In addition, problems arising from the separation of epoxy resin (flowing too large,
And low outgassing) can solve the problem of outgassing. Therefore, from such a viewpoint, it is preferable that the epoxy component substantially does not contain an epoxy resin and is substantially composed of a polyethylene-based copolymer having an epoxy group.

【０００６】[0006]

【発明の実施の形態】ホットメルト接着剤組成物 本発明のホットメルト接着剤組成物は、紫外線活性化前
およびその後において常温（約２５℃。以下「常温」と
いう用語は、すべて約２５℃を意味する。）で固体であ
るが、所定の温度にて、比較的低圧、短時間（たとえ
ば、１００〜２００℃にて、０．１〜４０ｋｇ／ｃ
ｍ2、０．１〜３０秒間）で熱圧着できる。BEST MODE FOR CARRYING OUT THE INVENTION Hot-melt adhesive composition The hot-melt adhesive composition of the present invention can be used at room temperature (about 25 ° C. before and after UV activation). At a predetermined temperature, at a relatively low pressure for a short time (for example, 0.1 to 40 kg / c at 100 to 200 ° C.).
m 2 , 0.1 to 30 seconds).

【０００７】紫外線活性化後は、圧着時の加熱または圧
着後の加熱（ポストキュア）により、水分を必要とせず
に硬化（架橋）させることができる。したがって、熱圧
着−熱硬化タイプの接着剤として有用に使用でき、その
ように使用した場合、放射線架橋型および湿気硬化（架
橋）型ホットメルト接着剤が有する上記の様な問題が解
決できる。熱硬化を行う時の加熱温度は通常１２０℃以
上である。熱硬化反応は、実質的に、エチレン−グリシ
ジル（メタ）アクリレート共重合体の「エポキシ基」ど
うしの反応であるので、水分等の反応副生成物が発生し
ない。なお、この様な反応は、カチオン重合触媒により
効果的に触媒される。本発明の接着剤組成物は、たとえ
ば、１２０℃以上の温度で溶融し、ほとんどゲル化する
ことなく容易にホットメルトコーティングできる。ま
た、ホットメルト時の流動性が比較的高く、コーティン
グまたはフィルム状に成形するために溶剤を必要としな
い。なお、紫外線活性化後の接着剤組成物は、室温（約
２５℃）でも徐々に硬化が進むので、硬化時間を特に短
縮する必要がない場合、１２０℃未満の温度で熱硬化さ
せたり、室温硬化型ホットメルト接着剤として使用する
こともできる。[0007] After activation by ultraviolet light, the film can be cured (crosslinked) without the need for moisture by heating during compression or heating after the compression (post cure). Therefore, it can be usefully used as a thermocompression-thermosetting type adhesive, and when used as such, the above-mentioned problems of the radiation-crosslinking type and moisture-curing (crosslinking) type hot melt adhesives can be solved. The heating temperature when performing thermosetting is usually 120 ° C. or higher. Since the thermosetting reaction is substantially a reaction between "epoxy groups" of the ethylene-glycidyl (meth) acrylate copolymer, no reaction by-product such as moisture is generated. In addition, such a reaction is effectively catalyzed by a cationic polymerization catalyst. The adhesive composition of the present invention can be melted at a temperature of, for example, 120 ° C. or more, and can be easily subjected to hot melt coating with almost no gelation. Moreover, the fluidity at the time of hot melt is relatively high, and a solvent is not required for forming a coating or a film. Note that the adhesive composition after the UV activation is gradually cured even at room temperature (about 25 ° C.). Therefore, when it is not necessary to particularly shorten the curing time, the adhesive composition may be thermally cured at a temperature lower than 120 ° C. It can also be used as a curable hot melt adhesive.

【０００８】一方、接着完了後（すなわち、硬化反応完
了後）の接着剤組成物の弾性率（通常、貯蔵弾性率
（Ｇ’）で表される）は、２８０℃において通常１０6
ｄｙｎｅ／ｃｍ2以上、好適には１０7ｄｙｎｅ／ｃｍ2
以上である。弾性率が１０6ｄｙｎｅ／ｃｍ2未満である
と、ハンダ耐熱性が低下し、電子部品の接着やＩＣパッ
ケージの作製に適さないおそれがある。また、弾性率が
低すぎると、ワイアーボンディングが良好に行なえない
おそれがある。上記弾性率は次のように定義される。す
なわち、紫外線照射後の接着剤組成物（接着フィルム
等）を試料とし、動的粘弾性測定装置を用い、試料の温
度を８０℃から２８０℃まで、昇温速度５℃／分にて昇
温させ、剪断速度６．２８ｒａｄ／秒にて測定した時の
２８０℃における値であると定義する。On the other hand, the elastic modulus (usually represented by storage elastic modulus (G ')) of the adhesive composition after the completion of the adhesion (that is, after the completion of the curing reaction) is usually 10 6 at 280 ° C.
dyne / cm 2 or more, preferably 10 7 dyne / cm 2
That is all. If the elastic modulus is less than 10 6 dyne / cm 2 , the heat resistance of the solder will be reduced, which may not be suitable for bonding electronic components or manufacturing IC packages. If the elastic modulus is too low, wire bonding may not be performed well. The elastic modulus is defined as follows. That is, the adhesive composition (adhesive film or the like) after irradiation with ultraviolet light is used as a sample, and the temperature of the sample is raised from 80 ° C. to 280 ° C. at a rate of 5 ° C./min using a dynamic viscoelasticity measuring device. And defined as the value at 280 ° C. when measured at a shear rate of 6.28 rad / sec.

【０００９】本発明の接着剤組成物は、紫外線活性化前
は、熱的に極めて安定であるので、比較的高温でメルト
コーティングまたはエクストルージョン成形により、フ
ィルムに容易に加工できる。すなわち、この様な工程に
おける加熱温度での、ポリエチレン系共重合体の分子間
の硬化反応は極めて緩やかであり、接着剤組成物がゲル
化したり、その粘性（複素弾性率）が、連続生産が困難
になる様なレベルまで上昇することはない。また、紫外
線活性化前には、９０℃未満では硬化反応は実質的には
進行しないので、接着剤組成物の貯蔵安定性を高めるこ
とができる。一方、紫外線活性化後も、３０℃以下の温
度での貯蔵が可能であり、約１ヶ月間は熱硬化性の接着
剤として使用可能である。Since the adhesive composition of the present invention is extremely stable before being activated by ultraviolet light, it can be easily processed into a film by melt coating or extrusion molding at a relatively high temperature. In other words, the curing reaction between the molecules of the polyethylene copolymer at the heating temperature in such a process is extremely slow, and the adhesive composition gels or its viscosity (complex elastic modulus) decreases in continuous production. It does not rise to levels that would be difficult. In addition, before the UV activation, the curing reaction does not substantially proceed at a temperature lower than 90 ° C., so that the storage stability of the adhesive composition can be improved. On the other hand, even after activation by ultraviolet light, it can be stored at a temperature of 30 ° C. or less, and can be used as a thermosetting adhesive for about one month.

【００１０】本発明の接着剤組成物は、分子内にエポキ
シ基を有するポリエチレン系共重合体に加えて、分子内
にエポキシ基を持たない熱可塑性ポリマーを必須成分と
する。これにより、紫外線照射後の接着剤組成物（熱圧
着性フィルム等）の接着性を容易に高めることができ
る。この様な熱可塑性ポリマーとしては、好適には分子
内にエポキシ基を持たないポリエチレン系共重合体であ
り、特に好適にはエチレン−エチルアクリレート共重合
体等のエチレン−アルキルアクリレート共重合体であ
る。この様なポリエチレン系共重合体は、分子内にエポ
キシ基を有するポリエチレン系共重合体との相溶性が高
く、接着性を損なうことなく、接着剤組成物の熱圧着性
やメルトコーティング性を効果的に高めることができ
る。分子内にエポキシ基を有するポリエチレン系共重合
体の含有量は、組成物全重量に対して、通常４０〜８０
重量％、好適には４５〜７５重量％の範囲である。ま
た、これに対応して、分子内にエポキシ基を持たない熱
可塑性ポリマーの含有量は、組成物全重量に対して、通
常１５〜５５重量％、好適には２４〜５０重量％の範囲
である。上記熱可塑性ポリマーの含有量が少なすぎる
と、上記効果が得られないおそれがあり、反対に上記熱
可塑性ポリマーの含有量が多すぎると、反応性（熱硬
化）が低下するおそれがある。また、本発明の接着剤組
成物は、本発明の効果を損なわない限り、上記２種類の
ポリエチレン系共重合体以外の他のポリマーを含むこと
もできる。The adhesive composition of the present invention contains, as an essential component, a thermoplastic polymer having no epoxy group in the molecule, in addition to the polyethylene copolymer having an epoxy group in the molecule. Thereby, the adhesiveness of the adhesive composition (thermocompression-bondable film or the like) after ultraviolet irradiation can be easily increased. Such a thermoplastic polymer is preferably a polyethylene copolymer having no epoxy group in the molecule, and particularly preferably an ethylene-alkyl acrylate copolymer such as an ethylene-ethyl acrylate copolymer. . Such a polyethylene-based copolymer has high compatibility with a polyethylene-based copolymer having an epoxy group in a molecule, and has an effect on the thermocompression bonding property and the melt coating property of the adhesive composition without deteriorating the adhesiveness. Can be increased. The content of the polyethylene-based copolymer having an epoxy group in the molecule is usually 40 to 80 with respect to the total weight of the composition.
%, Preferably in the range of 45-75% by weight. Correspondingly, the content of the thermoplastic polymer having no epoxy group in the molecule is usually 15 to 55% by weight, preferably 24 to 50% by weight based on the total weight of the composition. is there. If the content of the thermoplastic polymer is too small, the above effects may not be obtained. Conversely, if the content of the thermoplastic polymer is too large, the reactivity (thermosetting) may decrease. Further, the adhesive composition of the present invention can also contain a polymer other than the above-mentioned two types of polyethylene-based copolymer, as long as the effects of the present invention are not impaired.

【００１１】接着剤組成物の調製は、通常、その原料と
なる成分を、混練または混合装置を用いて行い、実質的
に均一になるまで混合する。この様な装置としては、通
常の混練または混合装置、例えばニーダー、ロールミ
ル、エクストルーダー、プラネタリーミキサー、ホモミ
キサー等が使用できる。混合時の温度および時間は、ポ
リエチレン系共重合体の反応が実質的に進行しない様に
選択され、通常２０〜１２０℃の範囲の温度、１分〜２
時間の範囲の時間で行う。[0011] The preparation of the adhesive composition is usually carried out by kneading or mixing the components as raw materials until the mixture becomes substantially uniform. As such a device, a usual kneading or mixing device, for example, a kneader, a roll mill, an extruder, a planetary mixer, a homomixer or the like can be used. The temperature and time for mixing are selected so that the reaction of the polyethylene copolymer does not substantially proceed, and the temperature is usually in the range of 20 to 120 ° C, and 1 minute to 2 minutes.
Perform in the time range of time.

【００１２】ポリエチレン系共重合体および熱可塑性ポ
リマー 分子内にエポキシ基を有するポリエチレン系共重合体
は、たとえば、エチレン−グリシジル（メタ）アクリレ
ート共重合体である。エチレン−グリシジル（メタ）ア
クリレート共重合体（以下、「共重合体（ａ）」と呼ぶ
こともある。）は、紫外線活性化後の接着剤組成物を所
定の温度にて加熱したときに硬化反応し、硬化物の凝集
力を高める働きをする。この様な高凝集力は、接着剤組
成物の剥離接着力等の接着性能を向上させるのに有利で
ある。一方、共重合体（ａ）は、接着剤組成物の前駆体
を比較的低温で溶融させ、メルトコーティングを容易に
する作用も有する。また、接着剤組成物に良好な熱接着
性（溶融して被着体に密着した後、冷却、固化した段階
での被着体に対する接着性を意味する。）を付与する。[0012] Polyethylene copolymer and thermoplastic resin
The polyethylene copolymer having an epoxy group in the limmer molecule is, for example, an ethylene-glycidyl (meth) acrylate copolymer. Ethylene-glycidyl (meth) acrylate copolymer (hereinafter sometimes referred to as “copolymer (a)”) is cured when the adhesive composition after UV activation is heated at a predetermined temperature. It reacts and acts to increase the cohesive strength of the cured product. Such a high cohesive force is advantageous for improving the adhesive performance such as the peel adhesive force of the adhesive composition. On the other hand, the copolymer (a) has a function of melting the precursor of the adhesive composition at a relatively low temperature and facilitating melt coating. In addition, good thermal adhesion (meaning adhesion to the adherend at the stage of being cooled and solidified after being melted and closely adhered to the adherend) is imparted to the adhesive composition.

【００１３】共重合体（ａ）は、たとえば、（ｉ）グリ
シジル（メタ）アクリレートモノマーと、（ii）エチレ
ンモノマーとを含んでなるモノマー混合物を出発モノマ
ーとして重合して得ることができる。また、本発明の効
果を損なわない限り、上記のモノマーに加えて、他のモ
ノマーとして、プロピレン、アルキル（メタ）アクリレ
ート、酢酸ビニル等を使用してよい。この場合、アルキ
ル（メタ）アクリレートのアルキル基の炭素数は、通常
１〜８の範囲である。The copolymer (a) can be obtained, for example, by polymerizing a monomer mixture containing (i) a glycidyl (meth) acrylate monomer and (ii) an ethylene monomer as a starting monomer. As long as the effects of the present invention are not impaired, propylene, alkyl (meth) acrylate, vinyl acetate, and the like may be used as other monomers in addition to the above monomers. In this case, the alkyl group of the alkyl (meth) acrylate generally has a carbon number of 1 to 8.

【００１４】共重合体（ａ）の好適な具体例としては、 １：グリシジル（メタ）アクリレートとエチレンの２元
共重合体、 ２：グリシジル（メタ）アクリレート、酢酸ビニル、お
よびエチレンの３元共重合体、および ３：グリシジル（メタ）アクリレート、エチレン、およ
びアルキル（メタ）アクリレートの３元共重合体を挙げ
ることができる。この様な共重合体は、グリシジル（メ
タ）アクリレートとエチレンとからなるモノマー混合物
を重合させて形成される繰り返し単位を、高分子全体に
対して、通常少なくとも５０重量％含み、好適には少な
くとも７５重量％含む。上記繰り返し単位中の、グリシ
ジル（メタ）アクリレート（Ｇ）とエチレン（Ｅ）の重
量比（Ｇ：Ｅ）は、通常５０：５０〜１：９９、好適に
は２０：８０〜５：９５の範囲である。また、共重合体
（ａ）は、１種単独または２種以上の混合物として使用
することができる。Preferred examples of the copolymer (a) include: a tertiary copolymer of glycidyl (meth) acrylate and ethylene, and a tertiary copolymer of glycidyl (meth) acrylate, vinyl acetate and ethylene. And terpolymers of 3: glycidyl (meth) acrylate, ethylene, and alkyl (meth) acrylate. Such a copolymer usually contains at least 50% by weight, preferably at least 75% by weight, of a repeating unit formed by polymerizing a monomer mixture composed of glycidyl (meth) acrylate and ethylene, based on the whole polymer. % By weight. The weight ratio (G: E) of glycidyl (meth) acrylate (G) and ethylene (E) in the above repeating unit is usually in the range of 50:50 to 1:99, preferably 20:80 to 5:95. It is. Further, the copolymer (a) can be used alone or as a mixture of two or more.

【００１５】本発明で使用する、分子内にエポキシ基を
有するポリエチレン系共重合体、および分子内にエポキ
シ基を持たないポリエチレン系共重合体等の熱可塑性ポ
リマーの加熱時の流動性は、ホットメルトコーティング
の条件（温度やコーティング方法等）によって適宜決定
できる。例えば、１９０℃におけるメルトフローレート
（ＭＦＲ）を通常１〜１，０００ｇ／１０分、好適には
１０〜７００ｇ／１０分、特に好適には１００〜５００
ｇ／１０分である様にする。ＭＦＲが小さすぎると、所
望の厚さの熱圧着フィルムやホットメルトフィルムの連
続生産が困難になるおそれがあり、反対にＭＦＲが多き
すぎると、熱圧着操作の際に不要に大きく流動し、接着
剤組成物が被着体の間からはみ出したり、接着剤の層の
厚みが小さくなりすぎて接着性能が低下するおそれがあ
る。ここで、「ＭＦＲ」は、ＪＩＳ Ｋ ６７６０の規
定に従い測定された値である。また、ポリエチレン系共
重合体の重量平均分子量は、ＭＦＲが上記の様な範囲に
なる様に選択される。The fluidity of a thermoplastic polymer used in the present invention, such as a polyethylene copolymer having an epoxy group in a molecule and a polyethylene copolymer having no epoxy group in a molecule, upon heating is hot. It can be appropriately determined according to the conditions of the melt coating (temperature, coating method, etc.). For example, the melt flow rate (MFR) at 190 ° C. is usually 1 to 1,000 g / 10 minutes, preferably 10 to 700 g / 10 minutes, and particularly preferably 100 to 500 g.
g / 10 minutes. If the MFR is too small, continuous production of a thermocompression-bonded film or a hot-melt film having a desired thickness may be difficult. On the other hand, if the MFR is too large, it may flow unnecessarily large during the thermocompression bonding operation and adhere. The adhesive composition may protrude from between the adherends, or the thickness of the adhesive layer may become too small, and the adhesive performance may be reduced. Here, “MFR” is a value measured in accordance with JIS K 6760. The weight average molecular weight of the polyethylene copolymer is selected so that the MFR falls within the above range.

【００１６】分子内にエポキシ基を有するポリエチレン
系共重合体、および分子内にエポキシ基を持たないポリ
エチレン系共重合体の合計の割合は、接着剤組成物全体
に対して、通常５０〜９９．９重量％の範囲が好適であ
る。上記ポリエチレン系共重合体の含有割合が少なすぎ
ると、化学的安定性および耐熱性を効果的に高められな
いおそれがある。The total proportion of the polyethylene copolymer having an epoxy group in the molecule and the polyethylene copolymer having no epoxy group in the molecule is usually 50 to 99. A range of 9% by weight is preferred. If the content of the polyethylene copolymer is too small, the chemical stability and heat resistance may not be effectively improved.

【００１７】カチオン重合触媒 カチオン重合触媒は、紫外線が照射されると、ルイス酸
等のカチオン性活性種を生成してエポキシ環の開環反応
を触媒する化合物である。カチオン重合触媒の具体例と
しては、たとえば、シクロペンタジエニルアニオン、イ
ンデニルアニオン、（キシレン）ヘキサフルオロアンチ
モネートアニオン、ヘキサフルオロホスフェートアニオ
ン等の配位子と、鉄、クロム、モリブデン、タングステ
ン、マンガン、レニウム、ルテニウム、オスミウム等の
金属カチオンとからなる有機金属錯体塩や、弗化ホウ素
系錯体などを挙げることができる。カチオン重合触媒の
含有割合は、接着剤組成物全体に対して通常０．０１〜
１０重量％の範囲である。 Cationic Polymerization Catalyst A cationic polymerization catalyst is a compound which generates a cationic active species such as a Lewis acid when irradiated with ultraviolet rays to catalyze the ring opening reaction of an epoxy ring. Specific examples of the cationic polymerization catalyst include, for example, ligands such as cyclopentadienyl anion, indenyl anion, (xylene) hexafluoroantimonate anion, and hexafluorophosphate anion, and iron, chromium, molybdenum, tungsten, and manganese. Organic metal complex salts comprising a metal cation such as rhenium, ruthenium, osmium and the like, and boron fluoride-based complexes. The content of the cationic polymerization catalyst is usually 0.01 to
It is in the range of 10% by weight.

【００１８】熱圧着性フィルム 本発明の熱圧着性フィルムは、上記接着剤組成物のホッ
トメルトコーティングフィルムであり、紫外線照射によ
り活性化され、熱硬化可能な状態のフィルム接着剤であ
る。熱圧着性フィルムは、熱接着タイプの接着材料とし
て有利な使用形態あり、同時に前述の従来のホットメル
ト接着剤が有する欠点を解決できる。 Thermocompression-bondable film The thermocompression-bondable film of the present invention is a hot-melt coating film of the above-mentioned adhesive composition, and is a film adhesive which is activated by ultraviolet irradiation and is in a thermosetting state. The thermocompression bonding film has an advantageous use form as a heat bonding type bonding material, and at the same time, can solve the above-mentioned disadvantages of the conventional hot melt adhesive.

【００１９】熱圧着性フィルムは、たとえば、２枚の被
着体の間にそれを挟み、所定の温度で熱圧着を行うだけ
で容易に熱接着し、さらに所定温度、所定時間のポスト
キュア処理を施すことにより、すぐれた接着性能を発揮
する。硬化反応は、１２０℃以上の範囲の温度で進行
し、１分〜２４時間の範囲の時間の加熱（圧着時の加熱
またはポストキュア）により、十分な接着力（たとえ
ば、１〜１５ｋｇ／２５ｍｍ以上）を発現可能である。
１２０℃の温度での硬化反応速度は、緩やかであるもの
の、十分な時間（たとえば、１０時間以上）をかければ
所望の接着性能を発揮させることが可能である。また、
硬化時間を短縮するには、１３０〜３００℃の範囲にて
加熱すれば良い。The thermocompression-bondable film is easily heat-bonded, for example, by sandwiching it between two adherends and performing thermocompression bonding at a predetermined temperature, and is further post-cured at a predetermined temperature for a predetermined time. By exerting excellent adhesive performance. The curing reaction proceeds at a temperature in the range of 120 ° C. or more, and a sufficient adhesive force (for example, 1 to 15 kg / 25 mm or more) is obtained by heating (heating during pressure bonding or post-curing) for a time in the range of 1 minute to 24 hours. ) Can be expressed.
Although the curing reaction rate at a temperature of 120 ° C. is slow, it is possible to exhibit desired adhesive performance if a sufficient time (for example, 10 hours or more) is applied. Also,
In order to shorten the curing time, heating may be performed in the range of 130 to 300 ° C.

【００２０】熱圧着性フィルムは、たとえば、次のよう
にして製造することができる。まず、接着剤組成物を、
基材の上にメルトコーティングし、フィルム状の前駆体
を形成する。このフィルム状の前駆体を紫外線により照
射し、活性化させて熱圧着性フィルムを得る。上記基材
としては、ライナー、または接着される被着体のうちの
一方の被着体を用いる。ライナーには、剥離紙、剥離フ
ィルム等の通常のものが使用できる。The thermocompression bonding film can be manufactured, for example, as follows. First, the adhesive composition
Melt coating on a substrate to form a film-like precursor. The film-like precursor is irradiated with ultraviolet rays to activate it, thereby obtaining a thermocompression-bondable film. As the base material, a liner or one of the adherends to be bonded is used. A normal liner such as a release paper or a release film can be used for the liner.

【００２１】メルトコーティングは、通常６０〜１５０
℃の範囲の温度にて行う。コーティングには、ナイフコ
ーター、ダイコーター等の通常の塗布手段を用いる。ま
た、エクストルージョン法により基材を用いずにフィル
ム状前駆体を形成することもできる。紫外線の照射量
は、通常１００〜１０，０００ｍＪ／ｃｍ2（３６０ｎ
ｍでの積算量）の範囲である。The melt coating is usually 60 to 150
Perform at a temperature in the range of ° C. Conventional coating means such as a knife coater and a die coater are used for coating. Further, a film-like precursor can be formed by an extrusion method without using a substrate. The irradiation amount of the ultraviolet ray is usually 100 to 10,000 mJ / cm 2 (360 n
(integrated amount in m).

【００２２】通常は、熱圧着性フィルムの接着面の片面
または両面をライナーで保護して製品化する。また、接
着面の粘着性が比較的低い場合、ライナーを備え付ける
ことなく製品化することもできる。熱圧着性フィルムの
厚みは、好適には０．００１〜５ｍｍ、特に好適には
０．００５〜０．５ｍｍの範囲である。厚みが薄すぎる
と、熱圧着性フィルムとしての取り扱いが困難になる傾
向があり、反対に厚すぎると、厚さ方向で効果が不均一
になり、接着剤としての信頼性が低下するおそれがあ
る。Usually, one or both of the adhesive surfaces of the thermocompression-bondable film are protected with a liner to produce a product. In addition, when the adhesiveness of the adhesive surface is relatively low, it is possible to produce a product without providing a liner. The thickness of the thermocompression-bondable film is preferably in the range of 0.001 to 5 mm, particularly preferably 0.005 to 0.5 mm. If the thickness is too thin, it tends to be difficult to handle as a thermocompression-bondable film, while if it is too thick, the effect becomes uneven in the thickness direction, and the reliability as an adhesive may decrease. .

【００２３】前述の様にして得られるライナー付き熱圧
着性フィルムは、たとえば、次のようにして使用する。
まず、ライナー付き接着フィルムからライナーを除去
し、第１の被着体と、第２の被着体との間に接着フィル
ムを挟み、第１の被着体、熱圧着性フィルム、および第
２の被着体とがこの順に積層された積層体を形成する。
続いて、その積層体を８０〜３００℃の範囲の温度、
０．１〜１００ｋｇ／ｃｍ2の範囲の圧力にて熱圧着操
作を行い、これら３者が互いに密着した接着構造を形成
する。この方法によれば、２つの被着体を、０．１〜３
０秒の範囲の時間で十分な接着力で接着することができ
る。The thermocompression-bondable film with a liner obtained as described above is used, for example, as follows.
First, the liner is removed from the adhesive film with the liner, the adhesive film is sandwiched between the first adherend and the second adherend, and the first adherend, the thermocompression bonding film, and the second Are formed in this order to form a laminated body.
Subsequently, the laminate is heated to a temperature in the range of 80 to 300 ° C.,
A thermocompression bonding operation is performed at a pressure in the range of 0.1 to 100 kg / cm 2 to form an adhesive structure in which the three members are in close contact with each other. According to this method, the two adherends are set to 0.1 to 3
The bonding can be performed with a sufficient bonding force in a time in the range of 0 second.

【００２４】本発明の熱圧着性フィルムは、上記の様な
熱圧着だけでも十分な接着力を発揮するのはいうまでも
ないが、さらに接着力を高めたい場合はポストキュアを
行う。すなわち、上記の接着方法において、上記接着構
造に対して通常１２０℃以上、好適には１３０〜３００
℃の範囲の温度、１分〜２４時間の範囲の時間にてポス
トキュアを施す。ポストキュア工程の時間短縮のため、
特に好適な条件は１４０〜２００℃、３０分〜１２時間
である。この方法は、本発明の熱圧着性フィルムを用い
た接着方法として最良の実施形態の１つである。また、
上記熱圧着性フィルムに換えて、第１または第２の被着
体の表面に、接着剤組成物を直接コーティングし、紫外
線を照射して接着剤組成物の層を形成し、上記接着構造
を形成することもできる。Needless to say, the thermocompression bonding film of the present invention exhibits a sufficient adhesive strength only by the thermocompression bonding as described above. However, if it is desired to further increase the adhesive strength, post-curing is performed. That is, in the above bonding method, the bonding structure is usually 120 ° C. or more, preferably 130 to 300 ° C.
Post cure is performed at a temperature in the range of 1 ° C and a time in the range of 1 minute to 24 hours. To shorten the time of the post cure process,
Particularly preferred conditions are 140 to 200 ° C. for 30 minutes to 12 hours. This method is one of the best embodiments as a bonding method using the thermocompression bonding film of the present invention. Also,
Instead of the thermocompression-bondable film, the surface of the first or second adherend is directly coated with an adhesive composition, and irradiated with ultraviolet rays to form a layer of the adhesive composition. It can also be formed.

【００２５】その他の材料 本発明の接着剤組成物は、本発明の効果を損なわない限
り、上記の成分以外に種々の添加剤を含むことができ
る。この様な添加剤としては、酸化防止剤、充填材（無
機フィラー、導電性粒子等）、ワックス等の滑剤、ゴム
成分、粘着付与剤、架橋剤、硬化促進剤、着色剤（顔
料、染料等）などが挙げられる。 Other Materials The adhesive composition of the present invention may contain various additives in addition to the above components, as long as the effects of the present invention are not impaired. Such additives include antioxidants, fillers (inorganic fillers, conductive particles, etc.), lubricants such as waxes, rubber components, tackifiers, crosslinking agents, curing accelerators, coloring agents (pigments, dyes, etc.). ).

【００２６】用途 本発明の接着剤組成物または熱圧着性フィルムは、ＩＣ
部品とプリント回路基板との接着などの、電子部品の接
着に特に好適に用いることができる。この他、ポリアミ
ド、ポリイミド、ポリエーテルイミド、ポリカーボネー
ト、ポリエチレン、ポリプロピレン、ポリエステル（例
えばポリエチレンテレフタレートなど）、エポキシ、Ｂ
Ｔレジン等のプラスチックどうし、または、プラスチッ
クと他の材料（繊維、金属、シリコン等の半導体、セラ
ミック、ガラス等）からなる物品との接着にも好適に使
用できる。金属の具体例としては、銅、鉄、ステンレス
鋼、ニッケル、金、銀、アルミニウム、タングステン、
モリブデン、白金等を挙げることができる。 Use The adhesive composition or thermocompression-bondable film of the present invention can be used for an IC.
It can be particularly suitably used for bonding electronic components, such as bonding between components and printed circuit boards. In addition, polyamide, polyimide, polyetherimide, polycarbonate, polyethylene, polypropylene, polyester (for example, polyethylene terephthalate), epoxy, B
It can also be suitably used for bonding between plastics such as T-resin or between plastics and articles made of other materials (semiconductors such as fibers, metals, silicon, ceramics, glass, etc.). Specific examples of metals include copper, iron, stainless steel, nickel, gold, silver, aluminum, tungsten,
Molybdenum, platinum and the like can be mentioned.

【００２７】本発明の接着剤組成物の製造では、出発原
料にモノマーを用いた重合工程が含まれない。したがっ
て、組成物中に残存する、未反応モノマーやモノマー由
来の揮発性有機物を可及的に少なくすることができる。
すなわち、ハンダリフロー時に生じる揮発性成分による
発泡や、使用者が比較的不快に感じるモノマー臭気の発
生を効果的に防止することができる。一方、本発明の接
着剤組成物を、プラスチックフィルム、繊維布、金属箔
等の基材に固着させた接着剤層として使用すれば、熱圧
着可能な接着テープとして使用できる。また、本発明に
よる接着剤組成物は、接着剤用途の他、シール材として
も使用できる。The production of the adhesive composition of the present invention does not include a polymerization step using a monomer as a starting material. Therefore, unreacted monomers and volatile organic substances derived from monomers remaining in the composition can be reduced as much as possible.
That is, it is possible to effectively prevent foaming due to volatile components generated at the time of solder reflow and generation of a monomer odor that is relatively unpleasant for a user. On the other hand, if the adhesive composition of the present invention is used as an adhesive layer fixed to a base material such as a plastic film, a fiber cloth, or a metal foil, it can be used as a thermocompression bonding tape. Further, the adhesive composition according to the present invention can be used as a sealing material in addition to an adhesive application.

【００２８】[0028]

【実施例】実施例１ エチレン−グリシジルメタクリレート共重合体（住友化
学（株）社製「（品名）ボンドファストＣＧ５００１；
ＭＦＲ＝３５０ｇ／１０分、エチレン単位：グリシジル
メタクリレート単位（重量比）＝８２：１２」）７０重
量部、エチレン−エチルアクリレート共重合体（日本ユ
ニカー（株）社製「（品名）ＮＵＣ−ＥＥＡ ６０７
０」）２９．５重量部、およびカチオン重合触媒（Ａｒ
3ＳＳＢＦ6／ここで、「Ａｒ」は芳香族官能基）０．５
重量部を、混練装置を用いて均一になるまで混合し、本
例の接着剤組成物を形成した。なお、混合操作は、１１
０℃、１０分間の条件で行った。EXAMPLES Example 1 Ethylene-glycidyl methacrylate copolymer (manufactured by Sumitomo Chemical Co., Ltd., "(trade name) Bondfast CG5001;
MFR = 350 g / 10 min, ethylene unit: glycidyl methacrylate unit (weight ratio) = 82: 12) 70 parts by weight, ethylene-ethyl acrylate copolymer (“NUC-EEA 607” manufactured by Nippon Unicar Co., Ltd.)
0 ") 29.5 parts by weight, and a cationic polymerization catalyst (Ar
3 SSBF 6 / where “Ar” is an aromatic functional group) 0.5
The parts by weight were mixed until uniform using a kneading apparatus to form an adhesive composition of this example. Note that the mixing operation is performed in 11
The test was performed at 0 ° C. for 10 minutes.

【００２９】─接着剤組成物の熱安定性─ 本例の接着剤組成物を試料として、レオメトリックス
（株）社製の動的粘弾性装置（型番：ＲＤＡII）を用
い、１２０℃、６．２８ｒａｄ／秒の剪断速度にて、初
期、および２時間加熱後の複素弾性率η*（粘性の指
標）を測定した。その結果、初期の複素弾性率η*は３
５４８ｐｏｉｓｅ、２時間加熱後の複素弾性率η*は３
７９４ｐｏｉｓｅであり、増加率は８％であった。この
結果から、２時間加熱後も安定であり、メルトコーティ
ング等の成形工程において支障を来たすことなく、連続
生産が容易に行えることが分かった。{Heat Stability of Adhesive Composition} Using the adhesive composition of the present example as a sample, a dynamic viscoelasticity device (model number: RDAII) manufactured by Rheometrics Co., Ltd. was used at 120 ° C. and 6. At a shear rate of 28 rad / sec, the complex modulus η * (index of viscosity) was measured initially and after heating for 2 hours. As a result, the initial complex modulus η * is 3
548 poise, complex modulus η * after heating for 2 hours is 3
794 poise, and the increase rate was 8%. From these results, it was found that the product was stable even after heating for 2 hours, and that continuous production could be easily performed without any trouble in a molding process such as melt coating.

【００３０】─熱圧着性フィルムの形成─ 本例の接着剤組成物を２枚のＰＥＴフィルム（剥離フィ
ルム）の間に挟み、１４０℃に加熱したナイフギャップ
の間を通し、厚さ０．１ｍｍのフィルム状前駆体を得
た。この前駆体に、２０ｃｍ離れた位置から２０Ｗ／ｃ
ｍの高圧水銀灯を用いて紫外線を照射し、熱圧着性フィ
ルムを形成した。なお、紫外線照射は、６３０ｍＪ／ｃ
ｍ2および１５４０ｍＪ／ｃｍ2の２つの照射量で行っ
た。これらの熱圧着性フィルムの各温度における、貯蔵
弾性率（Ｇ’）を表１に示す。なお、貯蔵弾性率は、紫
外線照射後２５分後の熱圧着性フィルムを試料とし、試
料の温度を８０℃から２８０℃まで昇温速度５℃／分に
て昇温させ、剪断速度６．２８ｒａｄ／秒にて測定した
時の各温度における値である。参考のため、紫外線照射
前のこの熱圧着性フィルム（前駆体）の貯蔵弾性率も同
表に示す（参考例）。実施例１の熱圧着性フィルムは、
１２０℃以上の温度で容易に熱硬化し、２８０℃におけ
る貯蔵弾性率は、いずれの照射量の場合も１０6ｄｙｎ
ｅ／ｃｍ2以上であった。{Formation of Thermocompression Bondable Film} The adhesive composition of this example was sandwiched between two PET films (peeling films) and passed through a knife gap heated to 140 ° C. to a thickness of 0.1 mm. Was obtained. 20 W / c from a position 20 cm away from this precursor
m was irradiated with ultraviolet light using a high-pressure mercury lamp to form a thermocompression-bondable film. In addition, ultraviolet irradiation is 630 mJ / c.
Two doses of m 2 and 1540 mJ / cm 2 were performed. Table 1 shows the storage elastic modulus (G ') of each of these thermocompression bonding films at each temperature. The storage elastic modulus was measured using a thermocompression-bondable film 25 minutes after ultraviolet irradiation as a sample. The temperature of the sample was increased from 80 ° C. to 280 ° C. at a rate of 5 ° C./min, and the shear rate was 6.28 rad. It is a value at each temperature when measured in / sec. For reference, the storage elastic modulus of this thermocompression-bondable film (precursor) before ultraviolet irradiation is also shown in the same table (Reference Example). The thermocompression-bondable film of Example 1 is
It is easily thermoset at a temperature of 120 ° C. or more, and has a storage elastic modulus at 280 ° C. of 10 6 dyn at any irradiation amount.
e / cm 2 or more.

【００３１】─接着試験─ 前述のフィルム前駆体を、３３０ｍＪ／ｃｍ2の照射量
で紫外線照射して得た熱圧着性フィルムを用い、次のよ
うにして接着試験を行った。銅板（長さ３０ｍｍ×幅２
５ｍｍ×厚み０．３ｍｍ）と、銅箔（長さ１００ｍｍ×
幅１０ｍｍ×厚み０．０５ｍｍ）との間に、長さ３０ｍ
ｍ×幅１０ｍｍ×厚み０．１ｍｍの熱圧着性フィルム
を、銅箔の幅と熱圧着性フィルムの幅とを揃えて挟んだ
後、１８０℃、３０ｋｇ／ｃｍ2、１０秒間の熱圧着操
作を行って積層体を形成した。上記の銅板／熱圧着性フ
ィルム／銅箔からなる積層体を試料とし、銅箔の長さ方
向に沿って、９０度方向に剥離した時の剥離力を測定し
た。引張速度は５０ｍｍ／分であった。各測定における
剥離力（銅箔と熱圧着性フィルムとの界面剥離）の最大
値をもって接着力とした。測定結果は１．２ｋｇ／ｃｍ
であり、十分な接着力を示すことが分かった。{Adhesion Test} An adhesion test was performed as follows using a thermocompression bonding film obtained by irradiating the above-mentioned film precursor with ultraviolet rays at an irradiation amount of 330 mJ / cm 2 . Copper plate (length 30mm x width 2)
5mm x thickness 0.3mm) and copper foil (length 100mm x
(Width 10mm x thickness 0.05mm) and length 30m
After sandwiching a thermocompression bonding film of mx 10 mm width x 0.1 mm thickness with the width of the copper foil and the width of the thermocompression bonding film aligned, a thermocompression bonding operation of 180 ° C, 30 kg / cm 2 , and 10 seconds was performed. To form a laminate. Using a laminate composed of the above-mentioned copper plate / thermocompression-bondable film / copper foil as a sample, the peeling force when peeled in the direction of 90 degrees along the length direction of the copper foil was measured. The tensile speed was 50 mm / min. The maximum value of the peeling force (interfacial peeling between the copper foil and the thermocompression bonding film) in each measurement was defined as the adhesive force. The measurement result is 1.2 kg / cm
It was found that the composition exhibited sufficient adhesive strength.

【００３２】実施例２ エチレン−グリシジルメタクリレート共重合体：エチレ
ン−エチルアクリレート共重合体：カチオン重合触媒の
重量比を、５０：４９．５：０．５に換えた以外は、実
施例１と同様にして、本例の接着剤組成物を形成した。
また、本例の接着剤組成物を用い、実施例１と同様にし
て本例の熱圧着性フィルムを形成した。なお、紫外線照
射量は１５４０ｍＪ／ｃｍ2であった。この熱圧着性フ
ィルムの各温度における貯蔵弾性率を、実施例１と同様
にして測定した。結果を表１に示す。Example 2 Same as Example 1 except that the weight ratio of ethylene-glycidyl methacrylate copolymer: ethylene-ethyl acrylate copolymer: cationic polymerization catalyst was changed to 50: 49.5: 0.5. Thus, the adhesive composition of this example was formed.
Further, using the adhesive composition of this example, a thermocompression-bondable film of this example was formed in the same manner as in Example 1. In addition, the ultraviolet irradiation amount was 1540 mJ / cm 2 . The storage modulus at each temperature of this thermocompression bonding film was measured in the same manner as in Example 1. Table 1 shows the results.

【００３３】比較例１ エチレン−エチルアクリレート共重合体を用いず、エチ
レン−グリシジルメタクリレート共重合体：カチオン重
合触媒の重量比を、９９．５：０．５にした以外は、実
施例１と同様にして、本例の接着剤組成物を形成した。
また、本例の接着剤組成物を用い、実施例１と同様にし
て本例の熱圧着性フィルムを形成した。なお、紫外線照
射量は１５４０ｍＪ／ｃｍ2であった。この熱圧着性フ
ィルムの各温度における貯蔵弾性率を、実施例１と同様
にして測定した。結果を表１に示す。本例の組成物は、
耐熱性および化学的安定性はすぐれているが、熱圧着性
フィルムとして使用するには、紫外線照射後の接着性が
不十分であった。Comparative Example 1 The same as Example 1 except that the ethylene-glycidyl methacrylate copolymer: cationic polymerization catalyst weight ratio was 99.5: 0.5 without using the ethylene-ethyl acrylate copolymer. Thus, the adhesive composition of this example was formed.
Further, using the adhesive composition of this example, a thermocompression-bondable film of this example was formed in the same manner as in Example 1. In addition, the ultraviolet irradiation amount was 1540 mJ / cm 2 . The storage modulus at each temperature of this thermocompression bonding film was measured in the same manner as in Example 1. Table 1 shows the results. The composition of this example is
Although excellent in heat resistance and chemical stability, the adhesiveness after ultraviolet irradiation was insufficient for use as a thermocompression bonding film.

【００３４】実施例３ カチオン重合触媒を、シクロペンタジエニル鉄（II）
（キシレン）ヘキサフルオロアンチモネートに換えた以
外は、実施例１と同様にして、本例の接着剤組成物を形
成した。また、本例の接着剤組成物を用い、実施例１と
同様にして本例の熱圧着性フィルムを形成した。なお、
紫外線照射は６１０ｍＪ／ｃｍ2および１５４０ｍＪ／
ｃｍ2の２つの照射量で行なった。これら熱圧着性フィ
ルムの各温度における貯蔵弾性率を、実施例１と同様に
して測定した。結果を表１に示す。実施例２〜４の熱圧
着性フィルムは、１２０℃以上の温度で容易に熱硬化
し、２８０℃における貯蔵弾性率は、いずれの場合も１
０6ｄｙｎｅ／ｃｍ2以上であった。Example 3 The cationic polymerization catalyst was cyclopentadienyl iron (II)
An adhesive composition of this example was formed in the same manner as in Example 1 except that (xylene) hexafluoroantimonate was used. Further, using the adhesive composition of this example, a thermocompression-bondable film of this example was formed in the same manner as in Example 1. In addition,
UV irradiation at 610 mJ / cm 2 and 1540 mJ /
Two doses of cm 2 were performed. The storage elastic modulus of each of these thermocompression bonding films at each temperature was measured in the same manner as in Example 1. Table 1 shows the results. The thermocompression-bondable films of Examples 2 to 4 were easily thermoset at a temperature of 120 ° C. or higher, and the storage elastic modulus at 280 ° C. was 1 in each case.
It was 0 6 dyne / cm 2 or more.

【００３５】実施例４ 紫外線照射後（１５４０ｍＪ／ｃｍ2の照射量）、常温
（約２５℃）で２５時間保存した以外は、実施例１と同
様にして熱圧着性フィルムを製造し、貯蔵弾性率を測定
した。結果を表１に示す。本発明の熱圧着性フィルム
は、活性後も安定に保存でき、１２０℃以上の温度で容
易に熱硬化し、２８０℃における貯蔵弾性率は１０6ｄ
ｙｎｅ／ｃｍ2以上であった。Example 4 A thermocompression-bondable film was produced in the same manner as in Example 1 except that the film was stored at normal temperature (about 25 ° C.) for 25 hours after irradiation with ultraviolet rays (irradiation amount of 1540 mJ / cm 2 ). The rate was measured. Table 1 shows the results. The thermocompression-bondable film of the present invention can be stored stably even after activation, is easily thermoset at a temperature of 120 ° C. or higher, and has a storage modulus at 280 ° C. of 10 6 d.
yne / cm 2 or more.

【００３６】比較例２ エチレン−アクリル酸エステル−無水マレイン酸共重合
体（住友アトケム（株）社製「（品名）ボンダイン（Bo
ndine）ＨＸ８２１０」５０重量部、実施例１で用いた
エチレン−グリシジルメタクリレート共重合体（「（品
名）ボンドファストＣＧ５００１」５０重量部、および
フタル酸ジアリルエステル（架橋剤）１重量部を用いた
以外は、実施例１と同様にして本例の接着剤組成物を形
成した。この接着剤組成物を１２０℃で加熱すると、３
０分以内にゲル化することが分かった。これは、上記架
橋剤による熱架橋反応が、１２０℃で容易に進行するか
らであった。Comparative Example 2 Ethylene-acrylate-maleic anhydride copolymer (manufactured by Sumitomo Atchem Co., Ltd., “(Product name) Bondyne (Bo
ndine) except that 50 parts by weight of HX8210 ”, 50 parts by weight of the ethylene-glycidyl methacrylate copolymer used in Example 1 (“ (trade name) Bondfast CG5001 ”, and 1 part by weight of diallyl phthalate (crosslinking agent)) were used. Formed an adhesive composition of this example in the same manner as in Example 1. When this adhesive composition was heated at 120 ° C.,
It was found to gel within 0 minutes. This is because the thermal crosslinking reaction by the crosslinking agent easily proceeds at 120 ° C.

【００３７】[0037]

【表１】 [Table 1]

フロントページの続き (72)発明者 マリオ・ペレス アメリカ合衆国55144−1000ミネソタ州セ ント・ポール、スリーエム・センター、ミ ネソタ・マイニング・アンド・マニュファ クチャリング・カンパニー内 Ｆターム(参考） 4J040 DA061 DA062 DF041 DF042 EC231 EC232 GA11 JA01 JA09 JB01 JB02 JB08 KA14 LA05 LA08 NA20 PA30 PA32 PA33 Continued on the front page (72) Inventor Mario Perez F-term in the Minnesota Mining and Manufacturing Company, St. Paul, Minnesota 55144-1000 Minnesota F-term (reference) 4J040 DA061 DA062 DF041 DF042 EC231 EC232 GA11 JA01 JA09 JB01 JB02 JB08 KA14 LA05 LA08 NA20 PA30 PA32 PA33

Claims (3)

【特許請求の範囲】[Claims] 【請求項１】 エポキシ成分として、分子内にエポキシ
基を有するポリエチレン系共重合体を含んでなる熱硬化
性のホットメルト接着剤組成物において、さらに、カチ
オン重合触媒と、分子内にエポキシ基を持たない熱可塑
性ポリマーとを含んでなることを特徴とする、ホットメ
ルト接着剤組成物。1. A thermosetting hot melt adhesive composition comprising a polyethylene copolymer having an epoxy group in a molecule as an epoxy component, further comprising a cationic polymerization catalyst and an epoxy group in the molecule. A hot-melt adhesive composition comprising a thermoplastic polymer having no hot-melt adhesive. 【請求項２】 請求項１のホットメルト接着剤組成物の
ホットメルトコーティングフィルムであって、紫外線照
射により活性化され、熱硬化可能な熱圧着性フィルム。2. A hot-melt coating film of the hot-melt adhesive composition according to claim 1, which is activated by irradiation with ultraviolet rays and can be thermoset. 【請求項３】 （ａ）請求項１のホットメルト接着剤組
成物のホットメルトコーティングフィルムを用意し、
（ｂ）そのコーティングフィルムに紫外線を照射して活
性化させ、（ｃ）活性化されたコーティングフィルムを
第１および第２の被着体の間に挟み、上記第１被着体、
上記コーティングフィルムおよび上記第２被着体をこの
順に積層してなる積層体を形成し、（ｄ）この積層体に
加熱しながら圧力を加えて、第１および第２の被着体を
接着させる、接着方法。3. A hot melt coating film of the hot melt adhesive composition according to claim 1 is prepared,
(B) activating the coating film by irradiating it with ultraviolet light; (c) sandwiching the activated coating film between the first and second adherends;
A laminate is formed by laminating the coating film and the second adherend in this order, and (d) applying pressure while heating the laminate to bond the first and second adherends. , Bonding method.
JP10182091A 1998-06-29 1998-06-29 Hot-melt adhesive composition, pressure-sensitive adhesive film and method for bonding with hot-melt adhesive composition Pending JP2000017242A (en)

Priority Applications (3)

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JP10182091A JP2000017242A (en) 1998-06-29 1998-06-29 Hot-melt adhesive composition, pressure-sensitive adhesive film and method for bonding with hot-melt adhesive composition
PCT/US1999/013468 WO2000000566A1 (en) 1998-06-29 1999-06-15 Hot-melt adhesive composition, heat-bonding film adhesive and adhering method using hot-melt adhesive composition
US09/355,602 US6265460B1 (en) 1998-06-29 1999-06-15 Hot-melt adhesive composition, heat-bonding film adhesive and adhering method using hot-melt adhesive composition

Applications Claiming Priority (1)

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