JPH0721131B2 - Adhesive loss type pressure sensitive adhesive - Google Patents
Adhesive loss type pressure sensitive adhesiveInfo
- Publication number
- JPH0721131B2 JPH0721131B2 JP61174859A JP17485986A JPH0721131B2 JP H0721131 B2 JPH0721131 B2 JP H0721131B2 JP 61174859 A JP61174859 A JP 61174859A JP 17485986 A JP17485986 A JP 17485986A JP H0721131 B2 JPH0721131 B2 JP H0721131B2
- Authority
- JP
- Japan
- Prior art keywords
- sensitive adhesive
- pressure
- adhesive
- foaming
- curing
- 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.)
- Expired - Lifetime
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- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、光照射により硬化する感圧性接着剤と発泡剤
との配合物からなり、所定の処理でその接着力が低下な
いし消失する粘着シートなどに好適な硬化発泡タイプの
接着力消失型感圧性接着剤に関する。The present invention relates to a pressure-sensitive adhesive sheet, etc., which comprises a mixture of a pressure-sensitive adhesive which is cured by light irradiation and a foaming agent, and whose adhesive strength is reduced or disappears by a predetermined treatment. The present invention relates to a pressure-sensitive adhesive of the cured foaming type, which is suitable for use in pressure-sensitive adhesive loss.
従来の技術及び問題点 従来、仮止めなどに便益な接着力消失型粘着シート、す
なわち先ずは通例の粘着シートの如く被着体を貼着する
ことができ、その後所定の処理で接着力を低下せしめて
被着体の剥離を容易とした粘着シートにおける感圧性接
着剤としては、加熱硬化タイプのもの、紫外線硬化タイ
プのもの、発泡タイプのものが知られていた。また、感
圧性接着剤を加熱軟化する方式、ガラス転移点以下の温
度に冷凍する方式も知られていた。Conventional technology and problems Conventionally, an adhesive-dissipative pressure-sensitive adhesive sheet that is convenient for temporary fixing, etc., can be attached to an adherend like a conventional pressure-sensitive adhesive sheet, and then the adhesive strength is reduced by a predetermined process. As the pressure-sensitive adhesive in the pressure-sensitive adhesive sheet that at least allows easy peeling of the adherend, a heat-curing type, an ultraviolet-curing type, and a foaming type have been known. Further, a method of heating and softening the pressure-sensitive adhesive and a method of freezing to a temperature below the glass transition point have been known.
しかしながら、加熱硬化タイプのものにあっては、硬化
処理に要する時間が多いうえに処理後の接着力の低下度
も小さくて剥離容易性に乏しい難点があった。紫外線硬
化タイプのものにあっては、処理所要時間に難点はない
が、やはり剥離容易性に乏しい難点があった。発泡タイ
プのものにあっては、剥離容易性に乏しいうえに軟質組
成の感圧性接着剤の場合、発泡処理時の加熱による軟化
で剥離に要する力の上昇や発泡後の再接着などの難点が
あった。他方、加熱軟化方式、冷凍方式にあっては、処
理に要する時間が多い難点があった。However, the heat-curing type has a drawback that it takes a long time for the curing treatment and the degree of decrease in the adhesive strength after the treatment is small, resulting in poor peeling easiness. In the case of the UV-curing type, there is no difficulty in the processing time, but there is also a difficulty in the ease of peeling. In the foam type, in addition to being difficult to peel off, in the case of a pressure sensitive adhesive having a soft composition, there are problems such as an increase in the force required for peeling due to softening due to heating during the foaming process and re-adhesion after foaming. there were. On the other hand, the heat-softening method and the freezing method have a drawback in that a lot of time is required for processing.
従って、処理前には充分な接着力を有し、処理後は接着
力の消失性に優れて剥離容易性が良好で、しかも処理所
要時間の少ない接着力消失型感圧性接着剤は知られてい
なかった。殊に、例えばシート法（積層法）で形成され
た溶剤含有セラミック積層シートの切断チップのよう
に、接着性が良好な被着体を自然にあるいはその自重の
みで離去できる程度に剥離容易性の優れる接着力消失型
感圧性接着剤は知られていなかった。Therefore, there is known a pressure-sensitive adhesive with loss of adhesive force, which has a sufficient adhesive force before the treatment, is excellent in the disappearance of the adhesive force after the treatment, is easy in peeling, and has a short treatment time. There wasn't. In particular, it is easy to peel an adherend with good adhesiveness, such as a cutting chip of a solvent-containing ceramic laminated sheet formed by the sheet method (lamination method), to the extent that it can be separated naturally or only by its own weight. No excellent loss-of-adhesion-type pressure-sensitive adhesive of No. 1 has not been known.
問題点を解決するための手段 本発明者らは上記した問題点に鑑み、接着性が良好な被
着体の場合にも良剥離容易性を示し、処理所要時間の短
い接着力消失型感圧性接着剤を開発するために鋭意研究
を重ねた結果、光照射により硬化する感圧性接着剤に発
泡剤を配合して硬化発泡タイプのものとすることによ
り、光硬化タイプ及び発泡タイプが有する処理所要時間
の短時間性を損なうことなく、両タイプの接着力低下機
構が相乗作用して予想外の剥離容易性を示すことを見出
し、本発明をなすに至った。Means for Solving the Problems In view of the above-mentioned problems, the inventors of the present invention show good easiness of peeling even in the case of an adherend having good adhesiveness, and a pressure-sensitive adhesive force-dissipating pressure-sensitive material having a short processing time. As a result of intensive research to develop adhesives, the pressure-sensitive adhesive that cures by light irradiation is mixed with a foaming agent to make it a cured foam type. The present invention has been completed by finding that both types of adhesive force lowering mechanisms act synergistically and exhibit unexpected ease of peeling without impairing the shortness of time.
すなわち、本発明は光照射により硬化し、その硬化物が
非水溶性の感圧性接着剤と、発泡剤との配合物からな
り、硬化後かつ発泡前におけるシェア硬度が30〜98度
で、かつ伸び率が10％以下であることを特徴とする硬化
発泡タイプの接着力消失型感圧性接着剤を提供するもの
である。That is, the present invention is cured by light irradiation, the cured product is composed of a mixture of a water-insoluble pressure-sensitive adhesive and a foaming agent, the shear hardness after curing and before foaming is 30 to 98 degrees, and Provided is a cured and foaming type adhesive strength erasing pressure-sensitive adhesive characterized by having an elongation rate of 10% or less.
作用 本発明の接着力消失型感圧性接着剤は、硬化によるノン
タック化で接着力が低下し、後続の発泡過程における加
熱軟化による接着力の上昇及び発泡後の再接着が抑制さ
れると共に、ノンタック化及び発泡による凹凸形状化な
いし有効接着面積の減少化のそれぞれによる接着力の低
下、さらに場合によっては発泡過程で発生した発泡ガス
の噴射による剥がし作用などが相乗作用して優れた接着
力消失化特性を示す。The pressure-sensitive adhesive of the present invention, which loses its adhesive strength, has a reduced tackiness due to non-tacking due to curing, and suppresses an increase in adhesiveness due to heat softening in the subsequent foaming process and re-adhesion after foaming, and a non-tack. Of adhesive strength due to unevenness and reduction of effective adhesive area due to foaming and foaming, and in some cases, exfoliation effect due to injection of foaming gas generated in foaming process synergistically eliminates excellent adhesive strength Show the characteristics.
発明の構成要素の例示 本発明の接着力消失型感圧性接着剤は、光照射により硬
化し、その硬化物が非水溶性の感圧性接着剤と発泡剤と
の配合物からなる硬化発泡タイプのものである。Examples of constituent elements of the invention The pressure-sensitive adhesive with loss of adhesive force of the present invention is a curable foaming type which is cured by irradiation with light and whose cured product is a mixture of a water-insoluble pressure-sensitive adhesive and a foaming agent. It is a thing.
光照射により硬化し、その硬化物が非水溶性の感圧性接
着剤、従って発泡処理後においても水溶性を示さない感
圧性接着剤としては公知のものを用いることができる。
例えば、ゴム系ないしアクリル系等の感圧性接着剤に光
重合性化合物すなわち、分子中に少なくとも２個の光重
合性炭素−炭素二重結合を有する低分子量化合物及び光
重合開始剤を配合してなる組成物などをあげることがで
きる。As the pressure-sensitive adhesive that is cured by irradiation with light and the cured product is water-insoluble, that is, a known pressure-sensitive adhesive that does not show water-solubility even after the foaming treatment can be used.
For example, a photopolymerizable compound, that is, a low molecular weight compound having at least two photopolymerizable carbon-carbon double bonds in a molecule and a photopolymerization initiator are mixed with a rubber-based or acrylic pressure-sensitive adhesive. And the like.
より具体的には、例えば天然ゴム、各種の合成ゴム等か
らなるゴム系ポリマ、あるいはアクリル酸ないしメタク
リル酸等のアルキルエステル系ポリマ又はアクリル酸な
いしメタクリル酸等のアルキルエステル約50〜99.5重量
％とこれと共重合可能な他の不飽和単量体約50〜0.5重
量％との共重合体等からなるアクリル系ポリマなど、そ
の重量平均分子量が5000〜3000000のものをベースポリ
マとし、これに必要に応じてポリイソシアネート化合
物、アルキルエーテル化メラミン化合物の架橋剤を配合
したものなどをあげることができる。なお、架橋剤を併
用する場合その配合量はベースポリマ100重量部あたり
約0.1〜10重量部が一般である。More specifically, for example, natural rubber, a rubber-based polymer made of various synthetic rubbers, or an alkyl ester-based polymer such as acrylic acid or methacrylic acid or an alkyl ester such as acrylic acid or methacrylic acid in an amount of about 50 to 99.5% by weight. Other unsaturated monomers copolymerizable with this, such as acrylic polymers consisting of copolymers with about 50-0.5% by weight of unsaturated monomers, whose weight average molecular weight is 5000-3000000 is used as the base polymer. A compound containing a cross-linking agent of a polyisocyanate compound or an alkyl etherified melamine compound can be used according to the above. When a crosslinking agent is used in combination, the compounding amount is generally about 0.1 to 10 parts by weight per 100 parts by weight of the base polymer.
光重合性化合物としては、通常その分子量が10000以下
のものが適当である。硬化処理による感圧性接着剤の三
次元網状構造の形成効率の点よりは分子量が5000以下で
分子中に光重合性炭素−炭素二重結合を２〜６個、就中
３〜６個有するものが好ましい。好ましい光重合性化合
物の代表例としては、トリメチロールプロパントリアク
リレート、ペンタエリスリトールトリアクリレート、ペ
ンタエリスリトールテトラアクリレート、ジペンタエリ
スリトールモノヒドロキシペンタアクリレート、ジペン
タエリスリトールヘキサアクリレートなどをあげること
ができる。その他の光重合性化合物の例としては、1,4
−ブタンジオールジアクリレート、1,6−ヘキサンジオ
ールジアクリレート、ポリエチレングリコールジアクリ
レートや市販のオリゴエステルアクリレートなどをあげ
ることができる。As the photopolymerizable compound, those having a molecular weight of 10,000 or less are usually suitable. From the viewpoint of forming efficiency of three-dimensional network structure of pressure-sensitive adhesive by curing treatment, the molecular weight is 5000 or less and 2 to 6 photopolymerizable carbon-carbon double bonds are contained in the molecule, especially 3 to 6 Is preferred. Typical examples of preferable photopolymerizable compounds include trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol monohydroxypentaacrylate and dipentaerythritol hexaacrylate. Examples of other photopolymerizable compounds include 1,4
Examples thereof include butanediol diacrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, and commercially available oligoester acrylate.
光重合性化合物は１種のみを用いてもよいし、２種以上
を併用してもよい。その配合量としては通常、上記ベー
スポリマ100重量部あたり１〜100重量部が適当である。
配合量が過少であると感圧性接着剤の光照射による三次
元網状化が不充分で硬化による接着力の低下が過小であ
ったり、硬化処理後発泡処理前における状態が柔らかす
ぎて発泡処理過程中に流動現象を起こして発泡による表
面の凹凸化を阻害したり、発生ガスが抜けたりして発泡
状態が形成されなかったりして好ましくない。他方、配
合量が過多であると感圧性接着剤の可塑化が著しく充分
な接着力が得られなくなったり、硬化により硬くなりす
ぎて発泡が阻害されたりして好ましくない。The photopolymerizable compound may be used alone or in combination of two or more. The compounding amount is usually 1 to 100 parts by weight per 100 parts by weight of the base polymer.
If the compounding amount is too small, the three-dimensional reticulation of the pressure-sensitive adhesive due to light irradiation is insufficient and the decrease in the adhesive strength due to curing is too small, or the condition after the curing process before the foaming process is too soft and the foaming process It is not preferable because a flow phenomenon occurs therein to hinder the unevenness of the surface due to foaming, or the generated gas escapes so that a foamed state is not formed. On the other hand, if the blending amount is too large, the pressure-sensitive adhesive will be remarkably plasticized and a sufficient adhesive force cannot be obtained, or it will become too hard by curing to hinder foaming, which is not preferable.
本発明の感圧性接着剤においては硬化後かつ発泡前にお
けるシェア硬度が30〜98度、好ましくは70〜90度、伸び
率が10％以下となる組成が適当である。In the pressure-sensitive adhesive of the present invention, a composition having a shear hardness of 30 to 98 degrees, preferably 70 to 90 degrees and an elongation of 10% or less after curing and before foaming is suitable.
なお、ベースポリマはその分子中に光重合性炭素−炭素
二重結合を有するものであってもよく、この場合には、
前記した光重合性化合物を配合しなくても満足できる程
度の硬化処理（接着力の低下）を施しうるときもある。The base polymer may have a photopolymerizable carbon-carbon double bond in its molecule, and in this case,
In some cases, a satisfactory degree of curing treatment (decrease in adhesive strength) can be performed without blending the photopolymerizable compound.
光重合開始剤としては、例えばイソプロピルベンゾイン
エーテル、イソブチルベンゾインエーテル、ベンゾフェ
ノン、ミヒラー氏ケトン、クロロチオキサントン、ドデ
シルチオキサントン、ジメチルチオサントン、ジエチル
チオキサントン、アセトフェノンジエチルケタール、ベ
ンジルジメチルケタール、α−ヒドロキシシクロヘキシ
ルフェニルケトン、２−ヒドロキシメチルフェニルプロ
パンなどをあげることができる。Examples of the photopolymerization initiator include isopropyl benzoin ether, isobutyl benzoin ether, benzophenone, Michler's ketone, chlorothioxanthone, dodecylthioxanthone, dimethylthiosanthone, diethylthioxanthone, acetophenone diethyl ketal, benzyl dimethyl ketal, α-hydroxycyclohexyl phenyl ketone, 2-hydroxymethyl phenyl propane etc. can be mentioned.
光重合開始剤は１種を単独で用いてもよいし、２種以上
を併用してもよい。その配合量は上記ベースポリマ100
重量部あたり0.1〜５重量部が適当である。配合量が過
少であると感圧性接着剤の光照射による三次元網状化が
不充分となり、接着力の低下が過小となって好ましくな
い。他方、配合量が過多であると被着体に光重合開始剤
が残留することがあったりして、被着体によっては不都
合な場合がある。The photopolymerization initiators may be used alone or in combination of two or more. The blending amount is the above base polymer 100.
Appropriately 0.1 to 5 parts by weight per part by weight. If the blending amount is too small, three-dimensional reticulation of the pressure-sensitive adhesive due to light irradiation becomes insufficient and the decrease in adhesive strength becomes too small, which is not preferable. On the other hand, if the compounding amount is too large, the photopolymerization initiator may remain on the adherend, which may be inconvenient depending on the adherend.
なお、本発明においては例えばトリエチルアミン、テト
ラエチルペンタミン、ジメチルアミノエタノールのよう
なアミン化合物で代表される光重合促進剤を併用しても
よい。In the present invention, a photopolymerization accelerator represented by an amine compound such as triethylamine, tetraethylpentamine and dimethylaminoethanol may be used in combination.
本発明においては通例、自然状態下に使用するものであ
るので保管時、使用時等における硬化の進行を防止する
点で紫外線硬化型の組成とすることが好ましいが、これ
に限定するものでない。In the present invention, since it is generally used under natural conditions, it is preferable to use an ultraviolet curable composition from the viewpoint of preventing the progress of curing during storage, use, etc., but the invention is not limited to this.
本発明において用いられる発泡剤としては、例えば炭酸
アンモニウム、炭酸水素アンモニウム、炭酸水素ナトリ
ウム、亜硝酸アンモニウム、水素化ホウ素ナトリウム、
アジト類などで代表される無機系のもの、アゾビスイソ
ブチロニトリル、アゾジカルボンアミド、バリウムアゾ
ジカルボキシレート等のアゾ系化合物、トルエンスルホ
ニルヒドラジド、ジフェニルスルホン−3,3′−ジスル
ホヒドラジン、4,4′−オキシビス（ベンゼンスルボヒ
ドラジド）、アリルビス（スルホヒドラジド）等のヒド
ラジン系化合物、ρ−トルイレンスルホニルセミカルバ
ジド、4,4′−オキシビス（ベンゼンスルホニルセミカ
ルバジド）等のセミカルバジド系化合物、５−モルホリ
ル−1,2,3,4−チアトリアゾール等のトリアゾール系化
合物、N,N′−ジニトロソペンタメチレンテトラミン、
N,N′−ジメチル−N,N′−ジニトロソテレフタルアミド
等のＮ−ニトロソ系化合物などで代表される有機系のも
の等、公知のものをあげることができる。なお、発泡剤
はマイクロカプセルに封入されたものが感圧性接着剤中
への分散性などの点で好ましく用いられている。マイク
ロカプセル化発泡剤としては、マイクロフェアー（Ｆ−
30,F−50,F−70;商品名、松本油脂社製）などを市販品
をあげることができる。Examples of the foaming agent used in the present invention include ammonium carbonate, ammonium hydrogen carbonate, sodium hydrogen carbonate, ammonium nitrite, sodium borohydride,
Inorganic compounds represented by azides, azobisisobutyronitrile, azodicarbonamide, azo compounds such as barium azodicarboxylate, toluenesulfonylhydrazide, diphenylsulfone-3,3'-disulfohydrazine, Hydrazine compounds such as 4,4′-oxybis (benzenesulfohydrazide) and allylbis (sulfohydrazide), ρ-toluylenesulfonylsemicarbazide, semicarbazide compounds such as 4,4′-oxybis (benzenesulfonylsemicarbazide), 5- Triazole compounds such as morpholyl-1,2,3,4-thiatriazole, N, N′-dinitrosopentamethylenetetramine,
Known compounds such as organic compounds represented by N-nitroso compounds such as N, N'-dimethyl-N, N'-dinitrosoterephthalamide can be used. The foaming agent encapsulated in microcapsules is preferably used in terms of dispersibility in the pressure-sensitive adhesive. As the microencapsulated foaming agent, Microsphere (F-
30, F-50, F-70; trade names, manufactured by Matsumoto Yushi Co., Ltd.) and the like can be mentioned as commercially available products.
発泡剤の配合量は、上記したベースポリマ100重量部あ
たり５〜300重量部が一般であるが、付図のように使用
発泡剤の種類、あるいは加熱条件等により発泡特性が比
較的大きく異なるので適宜に決定され、これに限定され
ない。The blending amount of the foaming agent is generally 5 to 300 parts by weight per 100 parts by weight of the above-mentioned base polymer, but the foaming characteristics are relatively large depending on the type of the foaming agent used, the heating conditions, etc. as shown in the attached figure. However, the present invention is not limited to this.
本発明の接着力消失型感圧性接着剤の接着力消失化処理
は、光照射による硬化処理と、発泡処理からなる。使用
発泡剤が加熱発泡型の場合、その発泡処理は加熱処理か
らなる。硬化処理の開始と発泡処理の開始との時間的前
後はいずれが先であってもよいし、両処理を同時に開始
してもよい。しかし、感圧性接着剤の層における少なく
とも表面層が硬化した後に発泡状態が形成されるように
処理することが、発泡ガスの噴射を被着体の剥がしに有
効に作用せしめて接着力消失性を高める点で望ましい。
このようにすれば、被着体をその発泡時に感圧性接着剤
層より自然に離れさすことができる場合もある。The adhesive force loss treatment of the adhesive force loss type pressure-sensitive adhesive of the present invention comprises a curing process by light irradiation and a foaming process. When the foaming agent used is a heat-foaming type, the foaming treatment consists of heat treatment. Either before or after the start of the curing treatment and the start of the foaming treatment, either may be started first, or both treatments may be started simultaneously. However, treating at least the surface layer of the pressure-sensitive adhesive layer so that a foamed state is formed after the layer is cured, the injection of the foaming gas effectively acts on the peeling of the adherend and the adhesive force disappearance property is reduced. It is desirable to increase it.
In this case, the adherend may be naturally separated from the pressure-sensitive adhesive layer when foaming.
本発明の接着力消失型感圧性接着剤は仮止め等の先ずは
被着体を接着保持してその被着体に所定の処理を施し、
処理後は被着体の保持が不要で容易に被着体を離去でき
ることが望まれる用途に適している。その例としては、
セラミック積層シート（未焼結物）、半導体ウエハ等を
小片に切断してチップ化する際の固定用粘着シート、パ
ターン形成用マスキングの貼着糊、片面のみに所定の処
理を施す必要のある被処理物の２枚を重合せて接着する
ための糊ないし両面粘着テープ、チップ等のユニットを
一時的に連設するためのテープなどがあげられる。The pressure-sensitive adhesive with loss of adhesive force according to the present invention is such that first, such as temporary fixing, the adherend is adhered and held, and the adherend is subjected to a predetermined treatment,
It is suitable for applications where it is desired that the adherend can be easily separated after the treatment without the need to hold the adherend. For example,
Ceramic laminated sheet (unsintered material), adhesive sheet for fixing when cutting semiconductor wafer into chips into chips, adhesive paste for masking for pattern formation, and objects that need to be subjected to predetermined treatment only on one side Examples thereof include glue or a double-sided adhesive tape for polymerizing and adhering two processed products, and a tape for temporarily connecting units such as chips.
本発明の接着力消失型感圧性接着剤の実用途において
は、層状態のものとされるのが通例であるが、その際、
上記したように硬化状態の形成は感圧性接着剤層の表面
層のみであってもよい。従って、通例の感圧性接着剤層
の上に、あるいは発泡剤を含有する感圧性接着剤層の上
に本発明の感圧性接着剤の層を設けた方式のものであっ
てもよい。好ましい方式は本発明の感圧性接着剤で接着
層の全部を構成して発泡ガス等の発泡性物質を接着剤層
より抜けやすくする方式である。In practical use of the pressure-sensitive adhesive with loss of adhesive force of the present invention, it is usually in a layered state.
As described above, the cured state may be formed only on the surface layer of the pressure-sensitive adhesive layer. Therefore, a system in which the layer of the pressure-sensitive adhesive of the present invention is provided on the usual pressure-sensitive adhesive layer or on the pressure-sensitive adhesive layer containing a foaming agent may be used. A preferred method is a method in which the pressure-sensitive adhesive of the present invention constitutes the entire adhesive layer so that a foaming substance such as foaming gas can be more easily removed from the adhesive layer.
また、粘着シート等のように支持基材の上に感圧性接着
剤層を設ける方式のものにあっては、被着体が光透過性
である場合は格別、光透過性でない場合は硬化処理を可
能とするための支持基材を光透過性のものとすることが
必要である。前記したセラミック積層シート、半導体ウ
エハ等を小片に切断してチップ化する際の固定用粘着シ
ートを形成する場合にあっては光透過性、強度等の点よ
りポリエステルフィルムやポリプロピレンフィルムなど
の比較的硬いフィルムが好ましく、その厚さは25〜500
μｍが適当である。Further, in the case of a system in which a pressure-sensitive adhesive layer is provided on a supporting base material such as a pressure-sensitive adhesive sheet, it is exceptional when the adherend is light transmissive, and a curing treatment when it is not light transmissive. It is necessary that the supporting base material for enabling the above is transparent. In the case of forming an adhesive sheet for fixing when the ceramic laminated sheet, the semiconductor wafer, etc. are cut into small pieces and made into chips, in view of light transmission, strength, etc. A hard film is preferred and its thickness is 25-500
μm is suitable.
発明の効果 本発明の接着力消失型感圧性接着剤は、光照射により硬
化する感圧性接着剤と発泡剤との配合物からなる硬化発
泡タイプのものであるので、硬化発泡処理前における接
着性に優れると共に、硬化発泡処理後の接着力消失性に
も優れており、その接着力消失性は、セラミックコンデ
ンサ形成用の溶剤含有セラミック積層シートの切断チッ
プをその自重によりあるいは発泡時に自然に離去するこ
とができる程度のものである。EFFECTS OF THE INVENTION Since the pressure-sensitive adhesive with loss of adhesive force of the present invention is a curing and foaming type composed of a mixture of a pressure-sensitive adhesive which is cured by light irradiation and a foaming agent, the adhesiveness before curing and foaming treatment is improved. In addition to its excellent adhesiveness, it also has excellent adhesive strength disappearance properties after curing and foaming treatment. The adhesive strength disappearance property is such that the cutting tip of the solvent-containing ceramic laminated sheet for ceramic capacitor formation is naturally separated by its own weight or during foaming. It is something that can be done.
実施例 実施例１ アクリル酸ブチル100部（重量部、以下同様）、アクリ
ル酸２部、アクリロニトリル５部からなる共重合体（重
量平均分子量約80万）100部、ポリイソシアネート系架
橋剤10部、マイクロフェアー（Ｆ−30）60部、ジペンタ
エリスリトールモノヒドロキシペンタアクリレート80部
及びα−ヒドロキシシクロヘキシルフェニルケトン２部
を混合して接着力消失型感圧性接着剤を調製した。Examples Example 1 100 parts of a butyl acrylate 100 parts (parts by weight, the same below), 2 parts of acrylic acid, 5 parts of acrylonitrile (weight average molecular weight of about 800,000), 100 parts of polyisocyanate crosslinking agent, Adhesion loss type pressure-sensitive adhesive was prepared by mixing 60 parts of Microsphere (F-30), 80 parts of dipentaerythritol monohydroxypentaacrylate and 2 parts of α-hydroxycyclohexyl phenyl ketone.
実施例２ 発泡剤としてはマイクロフェアーＦ−70を用いたほかは
実施例１に準じて接着力消失型感圧性接着剤を調製し
た。Example 2 A pressure-sensitive adhesive with loss of adhesive force was prepared in the same manner as in Example 1 except that Microsphere F-70 was used as the foaming agent.
実施例３ マイクロフェアーＦ−30を120部用いたほかは実施例１
に準じて接着力消失型感圧性接着剤を調製した。Example 3 Example 1 except that 120 parts of Microsphere F-30 was used.
A pressure-sensitive adhesive with loss of adhesive strength was prepared according to
実施例４ マイクロフェアーＦ−70を120部用いたほかは実施例２
に準じて接着力消失型感圧性接着剤を調製した。Example 4 Example 2 except that 120 parts of Microfare F-70 was used.
A pressure-sensitive adhesive with loss of adhesive strength was prepared according to
比較例１ マイクロフェアーＦ−30を用いないほかは実施例１に準
じて光硬化タイプの感圧性接着剤を調製した。Comparative Example 1 A photocurable pressure-sensitive adhesive was prepared in the same manner as in Example 1 except that Microsphere F-30 was not used.
比較例２ 光重合開始剤のα−ヒドロキシシクロヘキシルフェニル
ケトンを用いないほかは実施例１に準じて発泡タイプの
感圧性接着剤を調製した。Comparative Example 2 A foaming type pressure-sensitive adhesive was prepared in the same manner as in Example 1 except that the photopolymerization initiator α-hydroxycyclohexyl phenyl ketone was not used.
比較例３ 実施例１で用いた共重合体100部とポリイソシアネート
系架橋剤10部とからなる非接着力消失型の感圧性接着剤
を調製した。Comparative Example 3 A non-adhesive loss type pressure-sensitive adhesive comprising 100 parts of the copolymer used in Example 1 and 10 parts of a polyisocyanate crosslinking agent was prepared.
評価試験 ［剥れ試験］ 実施例及び比較例で得た感圧性接着剤を、易接着処理し
た厚さ100μｍのポリエステルフィルムの面上に乾燥後
の厚さが30μｍとなるように塗布し、70℃で５分間乾燥
処理して粘着シートを作製した。Evaluation Test [Peeling Test] The pressure-sensitive adhesive obtained in each of Examples and Comparative Examples was applied onto the surface of a 100 μm-thick polyester film that had been subjected to an easy-adhesion treatment so that the dry thickness would be 30 μm, and A pressure-sensitive adhesive sheet was prepared by drying at 5 ° C. for 5 minutes.
次に、合計65部のBaTiO3とCaTiO3、15部のメチルメタア
クリレート系共重合体及び合計20部のトリオールとブタ
ノールの組成からなり、厚さ0.05mm、大きさ100mm×100
mmのセラミックコンデンサ形成用のシートの定位置に内
部電極を印刷しながらその20枚を、粘着シートの感圧性
接着剤層の上に重ね置いて圧着した後パターンに沿って
ナイフでポリエステルフィルム部分まで切り込みながら
大きさ1.5mm×2.5mm角のチップに切断した。Next, a total of 65 parts BaTiO 3 and CaTiO 3 , consisting of 15 parts of methyl methacrylate copolymer and a total of 20 parts of triol and butanol, thickness 0.05 mm, size 100 mm × 100
While printing internal electrodes in place on the sheet for forming ceramic capacitors of 20 mm, 20 of them are laid on top of the pressure-sensitive adhesive layer of the adhesive sheet and crimped, then follow the pattern to the polyester film part with a knife While cutting, it was cut into 1.5 mm × 2.5 mm square chips.
ついで、ポリエステルフィルム側より高圧水銀ランプに
て60mj、160mj又は260mjの光を照射し硬化処理を施した
（前記成分より明らかな如く硬化物は非水溶性であ
る）。Then, the polyester film was irradiated with light of 60 mj, 160 mj or 260 mj from a high pressure mercury lamp to carry out a curing treatment (as is clear from the above components, the cured product is water-insoluble).
続いて、系を45度の角度に傾斜させてこれに100℃で１
分間、又は150℃で１分間加熱して発泡処理し、この傾
斜状態でチップが自動的に剥れるか否かを調べ、チップ
のすべてが剥れた場合を○、そうでない場合を×として
評価した。結果を表に示した。Then tilt the system at an angle of 45 degrees and
For 1 minute or at 150 ° C for 1 minute to perform foaming treatment, and check whether the chips will peel off automatically in this inclined state. If all of the chips peel off, it is evaluated as ○, and if not, it is evaluated as ×. did. The results are shown in the table.
［シェア硬度］ JIS Ｋ 6301のスプリング式硬さ試験（Ａ形）に従い2
0℃で測定した。試験片は実施例及び比較例で得た感圧
性接着剤を、シリコーンで剥離性処理したポリエステル
フィルムの面上に乾燥後の厚さが30μｍとなるように塗
布し、70℃で５分間乾燥処理して粘着シートを作製し、
これより感圧性接着剤層を剥がして12mmの厚さになるよ
う、かつ気泡が入り込まないよう積み重ねて作製した。
なお、硬化処理はポリエステルフィルム側より高圧水銀
ランプにて60mj、160mj又は260mjの光を照射することに
より行った。前記発泡処理前における結果を表に示し
た。[Shear hardness] 2 according to JIS K 6301 spring hardness test (A type)
It was measured at 0 ° C. The test piece was prepared by applying the pressure-sensitive adhesive obtained in Examples and Comparative Examples on the surface of a polyester film which was release-treated with silicone so that the thickness after drying would be 30 μm, and drying treatment at 70 ° C. for 5 minutes. To make an adhesive sheet,
From this, the pressure-sensitive adhesive layer was peeled off so as to have a thickness of 12 mm and stacked so as not to entrap air bubbles.
The curing treatment was performed by irradiating the polyester film side with light of 60 mj, 160 mj or 260 mj from a high pressure mercury lamp. The results before the foaming treatment are shown in the table.
［伸び率］ 実施例及び比較例で得た感圧性接着剤を、シリコーンで
剥離性処理したポリエステルフィルムの面上に乾燥後の
厚さ30μｍとなるように塗布し、70℃で５分間乾燥処理
して粘着シートを作製し、ポリエステルフィルム側より
高圧水銀ランプにて60mj、160mj又は260mjの光を照射す
ることにより硬化処理し、これより大きさ5mm×50mmの
ものを切り出してその感圧性接着剤層のみにつき20℃で
引張試験（引張速度300mm/分）し、破断するまでの伸び
より算出した。前記発泡処理前における結果を表に示し
た。[Elongation rate] The pressure-sensitive adhesive obtained in each of Examples and Comparative Examples was applied onto the surface of a polyester film which was release-treated with silicone so as to have a dry thickness of 30 µm, and dried at 70 ° C for 5 minutes. To prepare a pressure-sensitive adhesive sheet, and cure it by irradiating light of 60 mj, 160 mj or 260 mj with a high pressure mercury lamp from the polyester film side, cut out a size of 5 mm × 50 mm and cut the pressure-sensitive adhesive Tensile test (pulling speed: 300 mm / min) was carried out at 20 ° C. for only the layer, and the elongation was calculated before breaking. The results before the foaming treatment are shown in the table.
なお、表にはチップに対する感圧性接着剤層の初期接着
力（180度ピール値、引張速度300mm/分）も示した。 The table also shows the initial adhesive strength of the pressure-sensitive adhesive layer to the chip (180 degree peel value, tensile speed 300 mm / min).
図はマイクロフェアの発泡特性を示したグラフである。 The figure is a graph showing the foaming characteristics of microspheres.
Claims (4)
性の感圧性接着剤と、発泡剤との配合物からなり、硬化
後かつ発泡前におけるシェア硬度が30〜98度で、かつ伸
び率が10％以下であることを特徴とする硬化発泡タイプ
の接着力消失型感圧性接着剤。1. A cured product obtained by irradiation with light, wherein the cured product comprises a mixture of a water-insoluble pressure-sensitive adhesive and a foaming agent, and has a shear hardness of 30 to 98 degrees after curing and before foaming, and A cured and foaming adhesive strength erasing pressure-sensitive adhesive characterized by having an elongation of 10% or less.
第１項記載の接着力消失型感圧性接着剤。2. The pressure-sensitive adhesive of the adhesive strength erasing type according to claim 1, which is of an ultraviolet curing type.
の状態にある特許請求の範囲第１項記載の接着力消失型
感圧性接着剤。3. The pressure-sensitive adhesive composition of claim 1, which is attached to the support sheet in layers and is in the state of an adhesive sheet.
求の範囲第３項記載の接着力消失型感圧性接着剤。4. The pressure-sensitive adhesive with loss of adhesive force according to claim 3, wherein the support sheet is light-transmissive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61174859A JPH0721131B2 (en) | 1986-07-25 | 1986-07-25 | Adhesive loss type pressure sensitive adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61174859A JPH0721131B2 (en) | 1986-07-25 | 1986-07-25 | Adhesive loss type pressure sensitive adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6330581A JPS6330581A (en) | 1988-02-09 |
| JPH0721131B2 true JPH0721131B2 (en) | 1995-03-08 |
Family
ID=15985901
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61174859A Expired - Lifetime JPH0721131B2 (en) | 1986-07-25 | 1986-07-25 | Adhesive loss type pressure sensitive adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0721131B2 (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2727092B2 (en) * | 1988-11-21 | 1998-03-11 | 株式会社スリーボンド | Processing of small articles |
| JP2808290B2 (en) * | 1988-11-22 | 1998-10-08 | 株式会社スリーボンド | Adhesive composition for temporary fixing |
| JP4673965B2 (en) * | 2000-09-13 | 2011-04-20 | 株式会社スリオンテック | Heat-peelable adhesive tape / sheet and method for producing the same |
| JP2002088320A (en) * | 2000-09-13 | 2002-03-27 | Sliontec Corp | Heat-peeling off type adhesive tape/sheet and method for producing the same |
| JP2003171645A (en) * | 2001-12-04 | 2003-06-20 | Sekisui Chem Co Ltd | Adhesive substance, adhesive article, and connected structure |
| JP3566710B2 (en) * | 2001-11-15 | 2004-09-15 | 積水化学工業株式会社 | Adhesive substance, method for removing adhesive substance, and adhesive tape |
| JP2003147282A (en) * | 2001-11-15 | 2003-05-21 | Sekisui Chem Co Ltd | Adhering substance, method for peeling off adhering substance and joined structural material |
| US20050173051A1 (en) * | 2001-11-15 | 2005-08-11 | Munehiro Hatai | Adhesive material, method for peeling adhesive material, and pressure-sensitive adhesive tape |
| CN100334689C (en) * | 2002-04-11 | 2007-08-29 | 积水化学工业株式会社 | Method for manufacturing semiconductor chip |
| US7534498B2 (en) | 2002-06-03 | 2009-05-19 | 3M Innovative Properties Company | Laminate body, method, and apparatus for manufacturing ultrathin substrate using the laminate body |
| JP4565804B2 (en) * | 2002-06-03 | 2010-10-20 | スリーエム イノベイティブ プロパティズ カンパニー | Laminate including ground substrate, method for producing the same, method for producing ultrathin substrate using laminate, and apparatus therefor |
| WO2004003094A1 (en) * | 2002-06-28 | 2004-01-08 | Sumitomo Chemical Company, Limited | Heat-resistant temporary adhesive |
| JP2004043732A (en) * | 2002-07-15 | 2004-02-12 | Three M Innovative Properties Co | Foaming adhesive composition |
| US6864295B2 (en) | 2002-07-23 | 2005-03-08 | Asahi Kasei Chemicals Corporation | Gas-generating, pressure-sensitive adhesive composition |
| JP4669649B2 (en) * | 2002-11-29 | 2011-04-13 | 積水化学工業株式会社 | Thermally expandable microcapsule and adhesive sheet |
| JP4405246B2 (en) | 2003-11-27 | 2010-01-27 | スリーエム イノベイティブ プロパティズ カンパニー | Manufacturing method of semiconductor chip |
| JP4711783B2 (en) * | 2005-09-08 | 2011-06-29 | 日東電工株式会社 | Ultraviolet curable heat-peelable pressure-sensitive adhesive sheet and method for separating and collecting cut pieces |
| JP5173166B2 (en) * | 2006-08-14 | 2013-03-27 | スリーエム イノベイティブ プロパティズ カンパニー | Adhesive film peeling method |
| JP5004655B2 (en) * | 2007-05-18 | 2012-08-22 | 日東電工株式会社 | Method for producing photopolymer layer |
| JP5273248B2 (en) * | 2009-07-01 | 2013-08-28 | 旭硝子株式会社 | Method for manufacturing article having fine concavo-convex structure on surface and method for manufacturing wire grid type polarizer |
| JP2013067744A (en) * | 2011-09-26 | 2013-04-18 | Hitachi Ltd | Adhesive agent and method for disassembling adhered structure |
| WO2015098919A1 (en) * | 2013-12-27 | 2015-07-02 | 積水化学工業株式会社 | Method for removing cells, cell-supporting substrate, and method for culturing cells |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5661468A (en) * | 1979-10-23 | 1981-05-26 | Matsumoto Yushi Seiyaku Kk | Releasable adhesive |
| JPS5893765A (en) * | 1981-11-30 | 1983-06-03 | Toobi:Kk | Ultraviolet-curable adhesive and ultraviolet-curable label |
| JPS59126488A (en) * | 1983-01-08 | 1984-07-21 | Nitto Electric Ind Co Ltd | Method for forming surface-protection layer |
| JPS61287976A (en) * | 1985-06-14 | 1986-12-18 | Three Bond Co Ltd | Adhesive composition for temporary fixation |
-
1986
- 1986-07-25 JP JP61174859A patent/JPH0721131B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6330581A (en) | 1988-02-09 |
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