JPH0885780A - Heat-resistant adhesive and heat-shrinkable article prepared by using the same - Google Patents
Heat-resistant adhesive and heat-shrinkable article prepared by using the sameInfo
- Publication number
- JPH0885780A JPH0885780A JP6248687A JP24868794A JPH0885780A JP H0885780 A JPH0885780 A JP H0885780A JP 6248687 A JP6248687 A JP 6248687A JP 24868794 A JP24868794 A JP 24868794A JP H0885780 A JPH0885780 A JP H0885780A
- Authority
- JP
- Japan
- Prior art keywords
- adhesive
- heat
- catalyst
- epoxy resin
- epoxy
- 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
Links
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- Adhesives Or Adhesive Processes (AREA)
- Cable Accessories (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は主として熱収縮チューブ
等の熱収縮物品の内面に使用される耐熱接着剤、及び該
耐熱接着剤の層を内面に具えた熱収縮物品に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant adhesive mainly used for the inner surface of a heat-shrinkable article such as a heat-shrinkable tube, and a heat-shrinkable article having a layer of the heat-resistant adhesive on the inner surface.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来の
熱収縮チューブ等の熱収縮物品の内面に使用される接着
剤は、熱回復温度以下で軟化し、熱収縮物品と被被覆体
の間隙に入り込み、冷却後接着するホットメルト型の接
着剤が使用されている。ホットメルト型の接着剤として
は、酢酸ビニル系ホットメルト接着剤、ポリエステル系
ホットメルト接着剤、ポリアミド系ホットメルト接着剤
等が知られている。又粘着剤として、例えば、天然ゴ
ム、ブチルゴム等のゴム系粘着剤、アクリル酸エステル
共重合体のようなアクリル系粘着剤、アルキルビニルエ
ーテル共重合体のようなビニル系粘着剤、シリコーン系
粘着剤等が使用される。2. Description of the Related Art An adhesive used for the inner surface of a conventional heat-shrinkable article such as a heat-shrinkable tube softens at a heat recovery temperature or lower to cause a gap between the heat-shrinkable article and an object to be coated. A hot-melt type adhesive is used that penetrates and is bonded after cooling. Known hot melt adhesives include vinyl acetate hot melt adhesives, polyester hot melt adhesives, and polyamide hot melt adhesives. Examples of the adhesive include rubber-based adhesives such as natural rubber and butyl rubber, acrylic-based adhesives such as acrylic ester copolymers, vinyl-based adhesives such as alkyl vinyl ether copolymers, and silicone-based adhesives. Is used.
【０００３】上記のようなホットメルト型接着剤は、熱
収縮部品の収縮温度領域の近辺及びそれ以上の温度領域
で使用すると溶融し、充分な接着力を発揮しないととも
にズレを生じる。又高温領域でもズレを生じないような
高温軟化樹脂では、収縮温度領域で充分に溶融せずホッ
トメルト型接着剤として使用できない。粘着剤の場合で
も同様に、収縮温度領域の近辺及びそれ以上の温度領域
で使用すると溶融し、充分な接着力を発揮しないととも
にズレを生じる。The hot-melt type adhesive as described above is melted when used in the temperature range near the shrinking temperature range of the heat shrinkable component or in a temperature range higher than the shrinking temperature range, and does not exhibit a sufficient adhesive force and is displaced. Further, a high temperature softening resin which does not cause a deviation even in a high temperature region cannot be sufficiently melted in a shrinking temperature region and cannot be used as a hot melt type adhesive. Similarly, in the case of the pressure-sensitive adhesive, when it is used in the temperature range near the shrinkage temperature range and in the temperature range higher than the shrinkage temperature range, the pressure-sensitive adhesive melts, does not exhibit a sufficient adhesive force, and is displaced.
【０００４】一方、通常の熱硬化型接着剤を熱収縮物品
に適用する場合、収縮作業終了時に硬化すべく短時間熱
硬化型接着剤を用いる必要がある。ところが、このよう
な短時間熱硬化型接着剤を用いた場合、室温領域でも硬
化反応が進み、接着剤のポットライフが短くなり使用期
限に著しい制限を受けることになり、熱収縮部品に使用
することができない。On the other hand, when a normal thermosetting adhesive is applied to a heat-shrinkable article, it is necessary to use the thermosetting adhesive for a short time so as to cure it at the end of the shrinking work. However, when such a short-time thermosetting adhesive is used, the curing reaction proceeds even in the room temperature range, the pot life of the adhesive is shortened, and the expiration date is significantly limited. I can't.
【０００５】又、例えば特開平 - 号公報に示され
るように、短時間熱硬化型接着剤でポットライフが長い
接着剤が、フレキシブル印刷配線板用に開発されてい
る。このような接着剤を熱収縮物品の内層接着剤に用い
た場合、収縮温度領域の近辺及びそれ以上の温度領域で
も充分に溶融せず、熱収縮部品と被覆体の間隙に入り込
むことができないので、熱収縮物品の内層接着剤として
使用することができない。Further, as disclosed in, for example, Japanese Unexamined Patent Publication (Kokai) No. Hei 10 (1999) -163, a short-time thermosetting type adhesive having a long pot life has been developed for a flexible printed wiring board. When such an adhesive is used for the inner layer adhesive of a heat-shrinkable article, it does not melt sufficiently even in the vicinity of the shrinkage temperature range and in a temperature range higher than that, and cannot enter the gap between the heat-shrinkable part and the covering body. , Cannot be used as an inner layer adhesive for heat shrinkable articles.
【０００６】上述のように、従来の接着剤を使用した場
合には、充分に長いポットライフを持ち、収縮作業時に
は充分な流れ性を持った、さらに収縮作業終了時に硬化
反応が進み、再び高温時にさらされた時に充分な接着力
を有し、ズレ等を生じることのない接着剤を得ることが
できなかった。As described above, when the conventional adhesive is used, it has a sufficiently long pot life and has sufficient flowability during the shrinking work, and further the curing reaction proceeds at the end of the shrinking work, and the high temperature is restored again. It has not been possible to obtain an adhesive that has sufficient adhesive force when exposed to the occasion and does not cause a shift or the like.
【０００７】[0007]
【課題を解決するための手段】本発明は上述の問題点を
解消した、主として熱収縮物品の内層用として使用され
る耐熱接着剤と該接着剤を用いた熱収縮物品を提供する
もので、その特徴は、（Ａ）熱可塑性樹脂又は熱可塑性
エラストマーからなるホットメルト接着剤、（Ｂ）１分
子内に２個以上のエポキシ基を有するエポキシ樹脂、
（Ｃ）硬化剤、（Ｄ）（ａ）カチオン重合型触媒と、
（ｂ）平均粒径が５μｍ以下のマイクロカプセル化され
た触媒もしくは平均粒径が30μｍ以下である粉末状触媒
とを組合せた硬化促進剤を必須成分とする。耐熱接着剤
と、該接着剤の層を内面に具えている熱収縮物品にあ
る。DISCLOSURE OF THE INVENTION The present invention provides a heat-resistant adhesive mainly used for the inner layer of a heat-shrinkable article and a heat-shrinkable article using the adhesive, which solves the above-mentioned problems. Its features are (A) a hot-melt adhesive composed of a thermoplastic resin or a thermoplastic elastomer, (B) an epoxy resin having two or more epoxy groups in one molecule,
(C) curing agent, (D) (a) cationic polymerization type catalyst,
(B) A curing accelerator combined with a microencapsulated catalyst having an average particle size of 5 μm or less or a powdery catalyst having an average particle size of 30 μm or less is an essential component. A heat-shrinkable article having a heat resistant adhesive and a layer of the adhesive on the inner surface.
【０００８】[0008]
【作用】本発明者らは前述の課題について種々検討の結
果、ホットメルト接着剤（Ａ）に対して、カチオン重合
触媒（ａ）とマイクロカプセル化された触媒もしくは粉
末状触媒（ｂ）を組合せて硬化促進剤（Ｄ）として用い
ることにより、長いポットライフを保持したまま、短時
間熱硬化接着が可能となり、熱収縮物品の内層接着剤と
して好適であることを見出した。As a result of various studies on the above-mentioned problems, the present inventors combined the hot-melt adhesive (A) with the cationic polymerization catalyst (a) and the microencapsulated catalyst or powdered catalyst (b). It has been found that when used as a curing accelerator (D), thermosetting adhesion can be performed for a short time while maintaining a long pot life, and it is suitable as an inner layer adhesive for heat-shrinkable articles.
【０００９】本発明に用いるホットメルト接着剤は、熱
収縮物品を構成する組成物、被覆体を構成する組成物に
よって選択する必要があるが、酢酸ビニル系ホットメル
ト接着剤、ポリエステル系ホットメルト接着剤、ポリア
ミド系ホットメルト接着剤、アイオノマー系ホットメル
ト接着剤等通常用いられているホットメルト接着剤を単
独、もしくは混合することによって、熱収縮物品を構成
する組成物及び被覆体を構成する組成物のいずれにも接
着し、熱回復温度領域で溶融するホットメルト接着剤を
任意に選ぶことができる。The hot-melt adhesive used in the present invention must be selected according to the composition constituting the heat-shrinkable article and the composition constituting the coating, but a vinyl acetate hot-melt adhesive or a polyester hot-melt adhesive. Agent, polyamide-based hot melt adhesive, ionomer-based hot melt adhesive and other commonly used hot melt adhesives, either alone or mixed, to form a composition for forming a heat-shrinkable article and a composition for forming a coating. Any hot-melt adhesive that adheres to any of the above and melts in the heat recovery temperature range can be selected.
【００１０】本発明で用いるホットメルト接着剤の軟化
点は 180℃以下である必要があり、好ましくは 170℃以
下のものを用いるのがよい。熱収縮物品に使用する接着
剤は、ドライヤー等で加熱するために 180℃で５分程度
で収縮作業を完了することが好ましい。使用するホット
メルト接着剤の軟化点が 180℃以上であると、溶融する
以前に熱硬化反応が起こり、接着剤としては使用できな
い。The softening point of the hot melt adhesive used in the present invention must be 180 ° C. or lower, preferably 170 ° C. or lower. The adhesive used for the heat-shrinkable article is preferably heated at 180 ° C. for about 5 minutes so that the shrinking operation is completed in order to heat it with a dryer or the like. If the softening point of the hot-melt adhesive used is 180 ° C or higher, a thermosetting reaction occurs before it melts and it cannot be used as an adhesive.
【００１１】ホットメルト接着剤（Ａ）はエポキシ樹脂
（Ｂ）に対して固形分重量比で１／１〜10／１の範囲で
あり、好ましくは２／１〜６／１が好ましい。ホットメ
ルト接着剤（Ａ）の配合量が１／１より少ない場合に
は、熱回復過程に充分に溶融せず、熱収縮物品と被覆体
の間隙を充分に満たすことができず、さらに熱収縮物品
及び被覆体に充分接着しない。又熱架橋反応後の接着剤
が剛直となるため、可撓性が得られず不適切である。又
10／１より多い場合には溶融接着後、充分に接着剤が硬
化せず再び温度が上昇した場合にホットメルト接着剤が
再び溶融し、接着力の不足、ズレ等を防ぐことができず
不適切である。The hot melt adhesive (A) is in the range of 1/1 to 10/1 in terms of solid content weight ratio to the epoxy resin (B), preferably 2/1 to 6/1. When the content of the hot-melt adhesive (A) is less than 1/1, the hot-melt adhesive does not melt sufficiently in the heat recovery process, the gap between the heat-shrinkable article and the covering cannot be sufficiently filled, and further the heat shrinkage occurs. Does not adhere well to articles and coatings. Further, since the adhesive after the thermal crosslinking reaction becomes rigid, flexibility is not obtained and it is inappropriate. or
If it is more than 10/1, the hot-melt adhesive will melt again when the adhesive does not harden sufficiently and the temperature rises again after fusion bonding, and insufficient adhesive strength, deviation, etc. cannot be prevented. Appropriate.
【００１２】本発明に用いるエポキシ樹脂（Ｂ）は特に
限定されないが、一般には１分子内に２個以上のエポキ
シ基を有するものであればよい。例えばビスフェノール
Ａ型エポキシ樹脂、フェノールノボラック型エポキシ樹
脂、臭素化エポキシ樹脂等が挙げられる。The epoxy resin (B) used in the present invention is not particularly limited, but generally, one having two or more epoxy groups in one molecule may be used. Examples thereof include bisphenol A type epoxy resin, phenol novolac type epoxy resin, and brominated epoxy resin.
【００１３】硬化剤（Ｃ）は特に限定されないが、一般
に使用される脂肪族ポリアミン、酸無水物、芳香族アミ
ン等が挙げられる。硬化剤（Ｃ）の配合量は、エポキシ
樹脂（Ｂ）中の官能基量に対して（エポキシ）当量〜１
／２（エポキシ）当量が好ましい。硬化剤（Ｃ）の配合
量が１／２（エポキシ）当量未満であると充分な硬化度
が得られず、高温時の接着力不足、ズレ等の問題を起こ
すおそれがあり、（エポキシ）当量を越えて添加して
も、加熱時に分解ガス等を発生して好ましくない。The curing agent (C) is not particularly limited, but examples thereof include generally used aliphatic polyamines, acid anhydrides, aromatic amines and the like. The compounding amount of the curing agent (C) is (epoxy) equivalent to 1 with respect to the amount of functional groups in the epoxy resin (B).
1/2 (epoxy) equivalent is preferred. If the compounding amount of the curing agent (C) is less than 1/2 (epoxy) equivalent, a sufficient degree of curing cannot be obtained, which may cause problems such as insufficient adhesive strength at high temperature and deviation. If added over the range, decomposition gas and the like are generated during heating, which is not preferable.
【００１４】硬化促進剤（Ｄ）を構成するカチオン重合
型触媒（ａ）としては、例えばＢＦ 3 −ＭＥＡ，ＳｂＦ
5 −ＭＥＡ，ＦｅＣｌ3 ，ＰＦ5 −ＭＥＡ，ＡｌＣｌ3
等第４級アンモニウム塩、第４級スルホニウム塩、有機
弱酸のアルカリ金属塩等を挙げることができる。カチオ
ン重合型触媒（ａ）の添加量は、エポキシ樹脂（Ｂ）に
対して 0.5〜5.0 重量％、好ましくは 1.0〜3.0 重量％
である。カチオン重合型触媒（ａ）の配合量が 0.5重量
％未満であると、ポットライフが長くなるものの熱回復
過程時に充分に熱硬化反応が進まず、ズレ等の問題を起
こすおそれがある。一方、 5.0重量％を超えるとポット
ライフの低下を伴い、事実上使用できない。Cationic polymerization constituting the curing accelerator (D)
Examples of the type catalyst (a) include BF 3 -MEA, SbF
Five -MEA, FeCl3 , PFFive -MEA, AlCl3
Quaternary ammonium salt, quaternary sulfonium salt, organic
Examples thereof include alkali metal salts of weak acids. Katio
Polymerization type catalyst (a) is added to epoxy resin (B)
0.5 to 5.0% by weight, preferably 1.0 to 3.0% by weight
Is. The amount of the cationic polymerization catalyst (a) is 0.5% by weight.
If it is less than%, the pot life becomes longer, but heat recovery
During the process, the thermosetting reaction does not proceed sufficiently, causing problems such as misalignment.
There is a risk of rubbing. On the other hand, if it exceeds 5.0% by weight, the pot
It has a reduced life and is virtually unusable.
【００１５】マイクロカプセル化触媒もしくは粉末状触
媒（ｂ）の添加量は、エポキシ樹脂（Ｂ）に対して、
1.0〜10.0重量部、好ましくは 3.0〜6.0 重量％であ
る。マイクロカプセル化触媒もしくは粉末状触媒（ｂ）
の添加量が 1.0重量％未満であると、硬化促進剤として
の初期性能を充分に発揮できず、10.0重量％を越えて添
加すると、ポットライフが低下するので好ましくない。The amount of the microencapsulated catalyst or powdery catalyst (b) added is based on the epoxy resin (B).
It is 1.0 to 10.0 parts by weight, preferably 3.0 to 6.0% by weight. Microencapsulated catalyst or powdered catalyst (b)
If the amount added is less than 1.0% by weight, the initial performance as a curing accelerator cannot be sufficiently exhibited, and if it is added more than 10.0% by weight, the pot life is reduced, which is not preferable.
【００１６】粉末状触媒としては、例えばキュアゾール
２ＰＨＺ（四国化成社製、商品名）、キュアゾールＣ17
Ｚ（四国化成社製、商品名）、キュアゾールＦＦＺ（四
国化成社製、商品名）等を挙げることができる。粉末状
触媒の平均粒径は30μｍ以下、好ましくは３〜15μｍに
微細化されていることが望ましい。粉末状触媒の平均粒
径が30μｍを越えると、接着剤組成物を構成する樹脂組
成物と接触する面積が減少するために、接着に高温、長
時間を要し、又平均粒径があまりに小さくなりすぎる
と、カチオン重合型触媒との接触面積が大きくなりすぎ
てポットライフが短くなる。As the powdery catalyst, for example, Curesol 2PHZ (trade name of Shikoku Kasei Co., Ltd.), Curesol C17
Z (manufactured by Shikoku Kasei Co., Ltd., trade name), Curesol FFZ (manufactured by Shikoku Kasei Co., Ltd., trade name) and the like can be mentioned. The average particle size of the powdery catalyst is 30 μm or less, preferably 3 to 15 μm. If the average particle size of the powdery catalyst exceeds 30 μm, the area in contact with the resin composition that constitutes the adhesive composition is reduced, so that the bonding requires high temperature and long time, and the average particle size is too small. If too much, the contact area with the cationic polymerization catalyst becomes too large and the pot life becomes short.
【００１７】マイクロカプセル化触媒の平均粒径５μｍ
以下、好ましくは１〜３μｍに微粉化されていることが
望ましい。マイクロカプセル化触媒の平均粒径が５μｍ
を越えると、接着剤組成物を構成する樹脂組成物と接触
する面積が減少するために、接着に高温、長時間を要
し、又平均粒径があまりに小さすぎると、カチオン重合
型触媒との接触面積が大きくなりすぎてポットライフが
短くなる。マイクロカプセル化触媒とは、圧力又は温度
をかけて容易にマイクロカプセル化が壊れる程度に、ポ
リウレタン等の被覆材で薄層に被覆したものであり、例
えばノバキュアＨＸ−3612，−3722，−3741，−3748
（旭化成社製、商品名）等が挙げられる。The average particle size of the microencapsulated catalyst is 5 μm.
Hereafter, it is desirable that the powder is pulverized to a size of preferably 1 to 3 μm. The average particle size of the microencapsulated catalyst is 5 μm
If it exceeds the above, the area in contact with the resin composition constituting the adhesive composition is reduced, so that high temperature and long time are required for the adhesion, and if the average particle size is too small, it becomes The contact area becomes too large and the pot life becomes short. The microencapsulated catalyst is a thin layer coated with a coating material such as polyurethane to the extent that the microencapsulation is easily broken under pressure or temperature. For example, Novacure HX-3612, -3722, -3741, −3748
(Manufactured by Asahi Kasei Corp., trade name) and the like.
【００１８】本発明接着剤に用いる溶剤としては、メチ
ルエチルケトン、アセトン、ジオキサン、トルエン等及
びそれらの混合物が使用できる。本発明の耐熱接着剤を
熱収縮物品の内層接着剤として使用する場合には、この
接着剤組成物をまず公知の混合手段で混合した後、溶媒
に溶解し、溶液状態で塗布し、常温で乾燥する。As the solvent used for the adhesive of the present invention, methyl ethyl ketone, acetone, dioxane, toluene and the like and mixtures thereof can be used. When the heat-resistant adhesive of the present invention is used as the inner layer adhesive of a heat-shrinkable article, this adhesive composition is first mixed by a known mixing means, then dissolved in a solvent, and applied in a solution state at room temperature. dry.
【００１９】[0019]
【実施例】以下に実施例及び比較例を挙げて、本発明を
さらに具体的に説明するが、本発明はこれらの実施例の
みに限定されるものではない。なお、物性の評価方法は
次の通りである。 （１）埋まり性：収縮作業終了後サンプルを切断して観
察し、隙間がなければ良好（○）、あれば不良（×）と
した。 （２）高温剪断剥離力： 200℃の恒温槽中でチューブと
電線をつかんで、引張速度50mm／分で引張ったときの引
張強度を測定して評価した。引張強度１kg以上を
（○）、１kg未満を（×）とした。 （３）接着力：サンプルを長手方向に半円筒状に切断
し、内層接着剤付き熱収縮チューブ先端部を電線から剥
離して 180度に折り返し、その先端部をつかんで引張速
度50mm／分で電線から引き剥がしたときの剥離強度を測
定し、評価した。剥離強度１kg以上を（○）、１kg未満
を（×）とした。 （４）ポットライフ：常温（23℃）で接着力が１kg未満
になるまでの時間で、２ケ月以上を（◎）、１ケ月以
上、２ケ月未満を（○）、１ケ未満を（×）とした。EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. The evaluation methods of physical properties are as follows. (1) Fillability: After the shrinking work was completed, the sample was cut and observed. If there was no gap, it was evaluated as good (◯), and if there was no gap, it was evaluated as bad (x). (2) High temperature shear peeling force: The tube and the electric wire were grabbed in a constant temperature bath at 200 ° C., and the tensile strength when pulled at a pulling speed of 50 mm / min was measured and evaluated. Tensile strength of 1 kg or more was (◯), and less than 1 kg was (x). (3) Adhesive strength: The sample was cut into a semi-cylindrical shape in the longitudinal direction, the tip of the heat-shrinkable tube with the inner layer adhesive was peeled from the wire and folded back at 180 degrees, and the tip was grasped at a pulling speed of 50 mm / min. The peel strength when peeled from the electric wire was measured and evaluated. A peel strength of 1 kg or more was (◯), and less than 1 kg was (x). (4) Pot life: The time until the adhesive strength becomes less than 1 kg at room temperature (23 ° C.), for 2 months or more (◎), for 1 month or more and less than 2 months (○), for less than 1 month (×) ).
【００２０】サンプルの作製は次の通り行った。ＥＶＡ
樹脂（ＭＩ＝３ｇ／10分、酢酸ビニル含量＝25重量％）
を用いて、外径６mmφ、内径５mmφのチューブを作製し
た。このチューブに１ＭＶの電子線を15Mrad照射して架
橋した。ついで得られたチューブを 150℃の恒温槽中で
内径８mmφとなるように膨張させて熱収縮チューブを作
製した。実施例及び比較例で示される接着剤を、上記熱
収縮チューブの内面に接着剤溶液を固形分で約 300μｍ
厚になるように塗布し、室温で１日乾燥した。その後、
外径５mmφのポリエステル被覆電線、ＥＶＡ（酢酸ビニ
ル含量＝25重量％）電線のそれぞれに被せ、ホットガン
で３分間加熱し収縮させた。The sample was prepared as follows. EVA
Resin (MI = 3g / 10min, vinyl acetate content = 25wt%)
Was used to prepare a tube having an outer diameter of 6 mmφ and an inner diameter of 5 mmφ. This tube was cross-linked by irradiating 1 MV electron beam with 15 Mrad. Then, the obtained tube was expanded in a constant temperature bath at 150 ° C. so as to have an inner diameter of 8 mmφ to produce a heat-shrinkable tube. The adhesive shown in Examples and Comparative Examples was applied to the inner surface of the heat-shrinkable tube to obtain an adhesive solution having a solid content of about 300 μm.
It was applied so as to be thick and dried at room temperature for 1 day. afterwards,
A polyester-coated electric wire having an outer diameter of 5 mmφ and an EVA (vinyl acetate content = 25% by weight) electric wire were covered, respectively, and heated with a hot gun for 3 minutes to shrink.
【００２１】表１に実施例１〜６、表２及び３に比較例
１〜９の配合と評価結果を示す。なお、表１〜３に用い
た材料１〜18の銘柄は次の通りである。 （１）ホットメルト接着剤：ユニチカ（株）製、商品名 （２）ホットメルト接着剤：三井・デュポン・ポリケミ
カル（株）製、商品名 （３）アクリルエラストマー：帝国化学産業（株）製、
商品名 （４）エポキシ樹脂：油化シェルエポキシ社製、商品名 （５）エポキシ樹脂：油化シェルエポキシ社製、商品名 （６）エポキシ樹脂：油化シェルエポキシ社製、商品名 （７）芳香族ポリアミン：住友化学（株）製、商品名 （８）芳香族ポリアミン：住友化学（株）製、商品名 （９）芳香族ポリアミン：住友化学（株）製、商品名 （10）カチオン重合触媒：橋本化成（株）製、商品名 （11）カチオン重合触媒：橋本化成（株）製、商品名 （12）カチオン重合触媒：橋本化成（株）製、商品名 （13）マイクロカプセル化硬化促進剤：旭化成工業
（株）製、商品名 （14）マイクロカプセル化硬化促進剤：旭化成工業
（株）製、商品名 （15）マイクロカプセル化硬化促進剤：旭化成工業
（株）製、商品名 （16）硬化促進剤：四国化成（株）製、商品名、粒径25
μｍ （17）硬化促進剤：四国化成（株）製、商品名、粒径20
μｍ （18）硬化促進剤：四国化成（株）製、商品名、粒径18
〜30μｍTable 1 shows the compositions and evaluation results of Examples 1 to 6 and Tables 2 and 3 of Comparative Examples 1 to 9. The brands of materials 1 to 18 used in Tables 1 to 3 are as follows. (1) Hot melt adhesive: manufactured by Unitika Ltd., product name (2) Hot melt adhesive: manufactured by Mitsui DuPont Polychemical Co., Ltd., product name (3) Acrylic elastomer: Teikoku Chemical Industry Co., Ltd. ,
Product name (4) Epoxy resin: Yuka Shell Epoxy Company, trade name (5) Epoxy resin: Yuka Shell Epoxy company, trade name (6) Epoxy Resin: Yuka Shell Epoxy company, trade name (7) Aromatic polyamine: Sumitomo Chemical Co., Ltd., trade name (8) Aromatic polyamine: Sumitomo Chemical Co., Ltd., trade name (9) Aromatic polyamine: Sumitomo Chemical Co., Ltd., trade name (10) Cationic polymerization Catalyst: Hashimoto Kasei Co., Ltd., trade name (11) Cationic polymerization catalyst: Hashimoto Kasei Co., Ltd., trade name (12) Cationic polymerization catalyst: Hashimoto Kasei Co., Ltd., trade name (13) Microcapsule hardening Accelerator: Asahi Kasei Kogyo Co., Ltd., trade name (14) Micro-encapsulation hardening accelerator: Asahi Kasei Kogyo Co., Ltd., trade name (15) Micro-encapsulation hardening accelerator: Asahi Kasei Kogyo Co., Ltd., trade name (16) Curing accelerator: Shikoku Kasei Co., Ltd. , Trade name, particle size 25
μm (17) Curing accelerator: Shikoku Kasei Co., Ltd., trade name, particle size 20
μm (18) Curing accelerator: Shikoku Kasei Co., Ltd., trade name, particle size 18
~ 30 μm
【００２２】[0022]
【表１】 [Table 1]
【００２３】[0023]
【表２】 [Table 2]
【００２４】[0024]
【表３】 [Table 3]
【００２５】実施例１：ホットメルト接着剤ＨＰＲＶＲ
105 ／エリーテルＵＥ3500＝50／50をメチルエチルケト
ン／トリエン＝１／１に溶解し20重量％溶液を作製し
た。この溶液を93.5部、エポキシ樹脂としてエピュート
828 を6.25部、芳香族ポリアミンとして４，4'−ジアミ
ノジフェニルメタン0.7 部、硬化促進剤としてカチオン
重合型触媒ＢＦ3 −ＭＥＡ0.125 部と粒径５μｍのマイ
クロカプセル化された触媒ノバキュアＨＸ−3741（ポリ
ウレタンで被覆した変成イミダゾール）0.60部を混合撹
拌して粘稠な接着剤溶液とした。Example 1: Hot melt adhesive HPRVR
105 / Elitel UE3500 = 50/50 was dissolved in methyl ethyl ketone / triene = 1/1 to prepare a 20 wt% solution. Epute this solution as 93.5 parts epoxy resin
6.25 parts of 828, 0.7 parts of 4,4'-diaminodiphenylmethane as an aromatic polyamine, 0.125 parts of a cationic polymerization catalyst BF 3 -MEA as a curing accelerator, and Novacure HX-3741 (a microencapsulated catalyst having a particle size of 5 μm). 0.60 part of modified imidazole coated with polyurethane) was mixed and stirred to obtain a viscous adhesive solution.
【００２６】実施例２：エポキシ樹脂としてエピコート
154 、芳香族ポリアミンとして４，4'−ジアミノジフェ
ニルスルホン、硬化促進剤としてカチオン重合触媒Ｓｂ
5 −ＭＥＡとマイクロカプセル化された触媒ノバキュア
ＨＸ−3742を用いた以外は、実施例と同様に行った。 実施例３：エポキシ樹脂としてエピコート1004、芳香族
ポリアミンとして４，4'−ジアミノジフェニルエーテ
ル、硬化促進剤としてカチオン重合触媒ＰＦ5 −ＭＥＡ
とマイクロカプセル化された触媒ノバキュアＨＸ−3721
を用いた以外は、実施例１と同様に行った。Example 2: Epicoat as epoxy resin
154, 4,4′-diaminodiphenyl sulfone as an aromatic polyamine, and a cationic polymerization catalyst Sb as a curing accelerator.
The procedure was as in the example, except that 5- MEA and the microcapsulated catalyst Novacure HX-3742 were used. Example 3: Epicoat 1004 as an epoxy resin, 4,4′-diaminodiphenyl ether as an aromatic polyamine, and a cationic polymerization catalyst PF 5 -MEA as a curing accelerator.
And microencapsulated catalyst Novacure HX-3721
The same procedure as in Example 1 was carried out except that was used.
【００２７】実施例４：硬化促進剤としてカチオン重合
触媒ＢＦ3 −ＭＥＡとキュアゾールＣ17Ｚを用いた以外
は、実施例１と同様に行った。 実施例５：エポキシ樹脂としてエピコート154 、芳香族
ポリアミンとして４，4'−ジアミノジフェニルスルホ
ン、硬化促進剤としてカチオン重合触媒Ｓｂ5 −ＭＥＡ
とキュアゾール２ＰＨＺを用いた以外は、実施例１と同
様に行った。 実施例６：エポキシ樹脂としてエピコート1004、芳香族
ポリアミンとして４，4'−ジアミノジフェニルエーテ
ル、硬化促進剤としてカチオン重合触媒ＰＦ5 −ＭＥＡ
とキュアゾール２ＭＺ−Ａを用いた以外は、実施例１と
同様に行った。Example 4 The procedure of Example 1 was repeated except that the cationic polymerization catalyst BF 3 -MEA and Curezol C 17 Z were used as the curing accelerator. Example 5: Epicoat 154 as an epoxy resin, 4,4′-diaminodiphenyl sulfone as an aromatic polyamine, and a cationic polymerization catalyst Sb 5 -MEA as a curing accelerator.
Example 1 was repeated except that Curezol 2PHZ was used. Example 6: Epicoat 1004 as an epoxy resin, 4,4′-diaminodiphenyl ether as an aromatic polyamine, and a cationic polymerization catalyst PF 5 -MEA as a curing accelerator.
Was performed in the same manner as in Example 1 except that Curezol 2MZ-A was used.
【００２８】比較例１：ホットメルト接着剤のみ使用
し、実施例１と同様に行った。 比較例２：ホットメルト接着剤の代わりにアクリルゴム
ＳＧ90を用い、実施例１と同様に行った。 比較例３〜９：各配合剤の種類、配合量は表２及び表３
の如く使用し、実施例１と同様に行った。Comparative Example 1 The same procedure as in Example 1 was carried out using only the hot melt adhesive. Comparative Example 2: The same procedure as in Example 1 was performed using acrylic rubber SG90 instead of the hot melt adhesive. Comparative Examples 3 to 9: Tables 2 and 3 show the types and amounts of each compounding agent.
The same procedure as in Example 1 was performed.
【００２９】実施例１〜３はポットライフ２ケ月以上
で、内層の接着剤層の埋まり性が良好で、被覆体との接
着性、高温での剪断接着性等にすぐれている。又実施例
４〜６については、ポットライフが若干短くなり１〜２
ケ月になるが、内層接着剤層の埋まり性、被覆体との接
着性、高温での剪断接着性等はすぐれている。In Examples 1 to 3, the pot life is 2 months or more, the filling property of the adhesive layer as the inner layer is good, and the adhesive property with the covering body and the shear adhesive property at high temperature are excellent. For Examples 4 to 6, the pot life was slightly shortened to 1-2.
Although it may be a month, the burying property of the inner adhesive layer, the adhesive property with the coating, the shear adhesive property at high temperature, etc. are excellent.
【００３０】一方、比較例１は従来のホットメルト接着
剤であり、高温での剪断接着性に劣る。又ホットメルト
接着剤の代りにエラストマーであるアクリルゴムを使用
した比較例２は、収縮温度領域での流れ性が悪く、埋ま
り性、接着性が悪い。比較例３はポットライフが短く、
使用期限に制限を受ける。比較例４はカチオン系重合触
媒が配合されていないために、収縮作業時に熱硬化反応
が充分に進まず、高温での剪断接着性が劣る。On the other hand, Comparative Example 1 is a conventional hot melt adhesive and is inferior in shear adhesiveness at high temperature. In Comparative Example 2 in which an acrylic rubber, which is an elastomer, is used instead of the hot melt adhesive, the flowability in the shrinking temperature range is poor, and the filling and adhesive properties are poor. Comparative Example 3 has a short pot life,
Limited by expiration date. In Comparative Example 4, since the cationic polymerization catalyst was not blended, the thermosetting reaction did not proceed sufficiently during the shrinking work, and the shear adhesiveness at high temperature was poor.
【００３１】比較例５，６はエポキシ成分が多すぎるた
めに、熱硬化後可撓性がなく接着力が充分でない。比較
例７は粉末状触媒が含まれていないため、又比較例８は
カチオン重合触媒が含まれていないため、いずれも高温
の剪断接着力が充分でない。比較例９はエポキシ成分が
多すぎるために、熱硬化後可撓性がなく接着力が充分に
出ない。In Comparative Examples 5 and 6, since the amount of epoxy component is too large, there is no flexibility after thermosetting and the adhesive force is not sufficient. Comparative Example 7 does not contain a powdery catalyst, and Comparative Example 8 does not contain a cationic polymerization catalyst, so that the shear adhesive strength at high temperature is not sufficient. In Comparative Example 9, since the epoxy component is too much, it has no flexibility after thermosetting and the adhesive force is not sufficiently obtained.
【００３２】[0032]
【発明の効果】以上説明したように、本発明の耐熱接着
剤によれば、収縮作業時にはホットメルト接着剤と同様
な良好な流れ特性を示し、収縮作業後には熱硬化するた
めに、高温雰囲気下においても溶融することなく、ズレ
等を生じることがない。従って、本発明の接着剤を熱収
縮物品に用いることで高耐熱性の熱回復物品が得られ
る。As described above, according to the heat-resistant adhesive of the present invention, it exhibits the same good flow characteristics as the hot-melt adhesive during shrinking work, and is heat-cured after shrinking work. It does not melt even below, and does not cause misalignment. Therefore, by using the adhesive of the present invention in a heat-shrinkable article, a heat recovery article having high heat resistance can be obtained.
Claims (3)
トマーからなるホットメルト接着剤、（Ｂ）１分子内に
２個以上のエポキシ基を有するエポキシ樹脂、（Ｃ）硬
化剤、（Ｄ）（ａ）カチオン重合型触媒と（ｂ）平均粒
径が５μｍ以下のマイクロカプセル化された触媒もしく
は平均粒径が30μｍ以下である粉末状触媒とを組合せた
硬化促進剤を必須成分とすることを特徴とする耐熱接着
剤。1. A hot melt adhesive comprising (A) a thermoplastic resin or a thermoplastic elastomer, (B) an epoxy resin having two or more epoxy groups in one molecule, (C) a curing agent, and (D) ( A curing accelerator comprising an a) cationic polymerization type catalyst and (b) a microencapsulated catalyst having an average particle size of 5 μm or less or a powdered catalyst having an average particle size of 30 μm or less as an essential component. Heat resistant adhesive to
脂（Ｂ）の配合比が固形分重量比で１／１〜10／１の範
囲であり、硬化剤（Ｃ）の配合比がホットメルト接着剤
（Ａ）とエポキシ樹脂（Ｂ）中の官能基（エポキシ基を
含む）量に対して（エポキシ）当量〜１／２（エポキ
シ）当量であり、硬化促進剤（Ｄ）中のカチオン重合触
媒（ａ）の重量がエポキシ樹脂（Ｂ）の固形分重量に対
して 0.5〜5.0 重量％であり、かつマイクロカプセル化
触媒もしくは粉末状触媒（ｂ）の重量がエポキシ樹脂
（Ｂ）の固形分重量に対して 1.0〜10.0重量％であるこ
とを特徴とする請求項１記載の耐熱接着剤。2. The compounding ratio of the hot melt adhesive (A) and the epoxy resin (B) is in the range of 1/1 to 10/1 in terms of solid content weight ratio, and the compounding ratio of the curing agent (C) is hot melt. Cationic polymerization in the curing accelerator (D) is (epoxy) equivalent to 1/2 (epoxy) equivalent based on the amount of functional groups (including epoxy group) in the adhesive (A) and the epoxy resin (B). The weight of the catalyst (a) is 0.5 to 5.0% by weight with respect to the solid content of the epoxy resin (B), and the weight of the microencapsulated catalyst or powdery catalyst (b) is the solid content of the epoxy resin (B). The heat-resistant adhesive according to claim 1, which is 1.0 to 10.0% by weight based on the weight.
に具えていることを特徴とする熱収縮物品。3. A heat-shrinkable article, which comprises a layer of the heat-resistant adhesive according to claim 1 or 2 on its inner surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6248687A JPH0885780A (en) | 1994-09-16 | 1994-09-16 | Heat-resistant adhesive and heat-shrinkable article prepared by using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6248687A JPH0885780A (en) | 1994-09-16 | 1994-09-16 | Heat-resistant adhesive and heat-shrinkable article prepared by using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0885780A true JPH0885780A (en) | 1996-04-02 |
Family
ID=17181848
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6248687A Pending JPH0885780A (en) | 1994-09-16 | 1994-09-16 | Heat-resistant adhesive and heat-shrinkable article prepared by using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0885780A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6057382A (en) * | 1998-05-01 | 2000-05-02 | 3M Innovative Properties Company | Epoxy/thermoplastic photocurable adhesive composition |
| US6077601A (en) * | 1998-05-01 | 2000-06-20 | 3M Innovative Properties Company | Coated abrasive article |
| US6136398A (en) * | 1998-05-01 | 2000-10-24 | 3M Innovative Properties Company | Energy cured sealant composition |
| US6228133B1 (en) | 1998-05-01 | 2001-05-08 | 3M Innovative Properties Company | Abrasive articles having abrasive layer bond system derived from solid, dry-coated binder precursor particles having a fusible, radiation curable component |
| US6274643B1 (en) | 1998-05-01 | 2001-08-14 | 3M Innovative Properties Company | Epoxy/thermoplastic photocurable adhesive composition |
| US6649259B1 (en) * | 2000-02-29 | 2003-11-18 | National Starch And Chemical Investment Holding Corporation | Adhesives for thermally shrinkable films or labels |
| JP2007246855A (en) * | 2006-03-20 | 2007-09-27 | Fujitsu Ltd | Epoxy resin composition and manufacturing method for semiconductor apparatus using same |
| JP2012025839A (en) * | 2010-07-22 | 2012-02-09 | Dainippon Printing Co Ltd | Adhesive composition and adhesive sheet |
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-
1994
- 1994-09-16 JP JP6248687A patent/JPH0885780A/en active Pending
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6372336B1 (en) | 1998-05-01 | 2002-04-16 | 3M Innovative Properties Company | Coated abrasive article |
| US6228133B1 (en) | 1998-05-01 | 2001-05-08 | 3M Innovative Properties Company | Abrasive articles having abrasive layer bond system derived from solid, dry-coated binder precursor particles having a fusible, radiation curable component |
| US6057382A (en) * | 1998-05-01 | 2000-05-02 | 3M Innovative Properties Company | Epoxy/thermoplastic photocurable adhesive composition |
| US6136384A (en) * | 1998-05-01 | 2000-10-24 | 3M Innovative Properties Company | Epoxy/thermoplastic photocurable adhesive composition |
| US6441058B2 (en) | 1998-05-01 | 2002-08-27 | 3M Innovative Properties Company | Abrasive articles having abrasive layer bond system derived from solid, dry-coated binder precursor particles having a fusible, radiation curable component |
| US6258138B1 (en) | 1998-05-01 | 2001-07-10 | 3M Innovative Properties Company | Coated abrasive article |
| US6274643B1 (en) | 1998-05-01 | 2001-08-14 | 3M Innovative Properties Company | Epoxy/thermoplastic photocurable adhesive composition |
| US6753359B2 (en) | 1998-05-01 | 2004-06-22 | 3M Innovative Properties Company | Abrasive articles having abrasive layer bond system derived from solid, dry-coated binder precursor particles having a fusible, radiation curable component |
| US6136398A (en) * | 1998-05-01 | 2000-10-24 | 3M Innovative Properties Company | Energy cured sealant composition |
| US6077601A (en) * | 1998-05-01 | 2000-06-20 | 3M Innovative Properties Company | Coated abrasive article |
| US6359027B1 (en) | 1998-05-01 | 2002-03-19 | 3M Innovative Properties Company | Coated abrasive article |
| US6649259B1 (en) * | 2000-02-29 | 2003-11-18 | National Starch And Chemical Investment Holding Corporation | Adhesives for thermally shrinkable films or labels |
| JP2007246855A (en) * | 2006-03-20 | 2007-09-27 | Fujitsu Ltd | Epoxy resin composition and manufacturing method for semiconductor apparatus using same |
| JP2012025839A (en) * | 2010-07-22 | 2012-02-09 | Dainippon Printing Co Ltd | Adhesive composition and adhesive sheet |
| KR20150115839A (en) * | 2013-01-29 | 2015-10-14 | 에보니크 데구사 게엠베하 | Adhesion promoter compositions and primer compositions for metal-plastic hybrid components |
| US10273390B2 (en) | 2013-01-29 | 2019-04-30 | Evonik Degussa Gmbh | Adhesion promoter compositions and primer compositions for metal-plastic hybrid components |
| US11078390B2 (en) | 2013-01-29 | 2021-08-03 | Evonik Operations Gmbh | Adhesion promoter compositions and primer compositions for metal-plastic hybrid components |
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