JP2011219617A - Easily releasable pressure sensitive adhesive sheet and easily releasable pressure sensitive adhesive tape - Google Patents

Easily releasable pressure sensitive adhesive sheet and easily releasable pressure sensitive adhesive tape Download PDF

Info

Publication number
JP2011219617A
JP2011219617A JP2010090092A JP2010090092A JP2011219617A JP 2011219617 A JP2011219617 A JP 2011219617A JP 2010090092 A JP2010090092 A JP 2010090092A JP 2010090092 A JP2010090092 A JP 2010090092A JP 2011219617 A JP2011219617 A JP 2011219617A
Authority
JP
Japan
Prior art keywords
sensitive adhesive
crystalline polymer
pressure
chain crystalline
adhesive sheet
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.)
Granted
Application number
JP2010090092A
Other languages
Japanese (ja)
Other versions
JP5551959B2 (en
Inventor
Keisuke Sako
圭輔 佐古
Shinichi Nakano
真一 仲野
Shinichiro Kawahara
伸一郎 河原
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.)
Nitta Corp
Original Assignee
Nitta Corp
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 Nitta Corp filed Critical Nitta Corp
Priority to JP2010090092A priority Critical patent/JP5551959B2/en
Publication of JP2011219617A publication Critical patent/JP2011219617A/en
Application granted granted Critical
Publication of JP5551959B2 publication Critical patent/JP5551959B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide an easily releasable pressure sensitive adhesive sheet and an easily releasable pressure sensitive adhesive tape, which are easily released.SOLUTION: The pressure sensitive adhesive sheet comprises a side-chain crystallizable polymer and has an adhesive strength decreased at a temperature that is less than the melting point of the side-chain crystallizable polymer, and the easily releasable pressure sensitive adhesive tape is characterized in that: the side-chain crystallizable polymer comprises a copolymer of at least one of reactive polysiloxane compounds and reactive fluorine compounds with another monomer composing the side-chain crystallizable polymer; an adhesive layer is placed on at least one side of a base film; the adhesive layer contains a side-chain crystallizable polymer and has an adhesive strength decreased at a temperature that is less than the melting point of the side-chain crystallizable polymer; and the side-chain crystallizable polymer comprises a copolymer of at least one of the reactive polysiloxane compounds and the reactive fluorine compounds with another monomer composing the side-chain crystallizable polymer.

Description

本発明は、易剥離性を有する粘着シートおよび粘着テープに関する。   The present invention relates to an easily peelable pressure-sensitive adhesive sheet and pressure-sensitive adhesive tape.

発光素子(LED)やフラットパネルディスプレイ(FPD)等の製造工程において、ガラス、プラスチック等からなる基板の固定に粘着シートや粘着テープを用いれば、基板を効率よく加工することができてよいと考えられる。   In the manufacturing process of light emitting elements (LEDs) and flat panel displays (FPDs), if an adhesive sheet or an adhesive tape is used to fix a substrate made of glass, plastic, etc., the substrate may be processed efficiently. It is done.

しかし、前記基板は、大型化および薄型化の傾向にあり、強度が低下している。そのため、粘着シートや粘着テープの粘着面が一般的なアクリル系粘着剤からなる場合には、これらを加工後の基板から剥離する際に、該基板に過度の力がかかり、基板を破損するという問題がある。この問題は、粘着シートや粘着テープとともに高温に曝された基板から粘着シートや粘着テープを剥離する場合に顕著である。   However, the substrate tends to be larger and thinner, and the strength is reduced. Therefore, when the pressure-sensitive adhesive sheet or the pressure-sensitive adhesive surface of the pressure-sensitive adhesive tape is made of a general acrylic pressure-sensitive adhesive, an excessive force is applied to the substrate when it is peeled off from the processed substrate, and the substrate is damaged. There's a problem. This problem is remarkable when the adhesive sheet or the adhesive tape is peeled from the substrate exposed to high temperature together with the adhesive sheet or the adhesive tape.

一方、本出願人は、粘着力を熱により可逆的に制御できる粘着テープとして、先に特許文献1に記載のような粘着テープを開発した。該粘着テープは、粘着剤層が側鎖結晶性ポリマーを含有しており、該側鎖結晶性ポリマーの融点未満の温度にまで冷却処理をすると、側鎖結晶性ポリマーが結晶化することによって粘着力が低下する。したがって、特許文献1に記載されている粘着テープを用いれば、粘着テープ剥離時に粘着力を低下させることができるので、基板への負荷を小さくすることができる。
しかし、特許文献1に記載されている粘着テープを用いても、加工後の基板から剥離する際に、基板を破損することがあった。
On the other hand, the present applicant has previously developed a pressure-sensitive adhesive tape as described in Patent Document 1 as a pressure-sensitive adhesive tape whose adhesive force can be reversibly controlled by heat. In the pressure-sensitive adhesive tape, the pressure-sensitive adhesive layer contains a side chain crystalline polymer, and when the side chain crystalline polymer is cooled to a temperature lower than the melting point of the side chain crystalline polymer, the side chain crystalline polymer is crystallized. Power is reduced. Therefore, if the adhesive tape described in Patent Document 1 is used, the adhesive force can be reduced when the adhesive tape is peeled off, so that the load on the substrate can be reduced.
However, even if the adhesive tape described in Patent Document 1 is used, the substrate may be damaged when it is peeled from the processed substrate.

特開平9−251923号公報JP-A-9-251923

本発明の課題は、剥離が容易な易剥離性粘着シートおよび易剥離性粘着テープを提供することである。   The subject of this invention is providing the easily peelable adhesive sheet and easily peelable adhesive tape which are easy to peel.

本発明者らは、上記課題を解決すべく鋭意研究を重ねた結果、以下の構成からなる解決手段を見出し、本発明を完成するに至った。
(1)側鎖結晶性ポリマーを含有し、該側鎖結晶性ポリマーの融点未満の温度で粘着力が低下する粘着シートであって、前記側鎖結晶性ポリマーは、反応性ポリシロキサン化合物および反応性フッ素化合物から選ばれる少なくとも1種と、側鎖結晶性ポリマーを構成する他のモノマーとの共重合体からなることを特徴とする易剥離性粘着シート。
(2)前記反応性ポリシロキサン化合物が、下記一般式(I)で表される変性ポリジメチルシロキサン化合物である前記(1)記載の易剥離性粘着シート。

Figure 2011219617
[式中、R1はアルキル基を示す。R2は基:CH2=CHCOOR3−またはCH2=C(CH3)COOR3−(式中、R3はアルキレン基を示す。)を示す。nは5〜200の整数を示す。]
(3)前記反応性フッ素化合物が、下記一般式(II)で表される化合物である前記(1)または(2)記載の易剥離性粘着シート。
Figure 2011219617
[式中、R4は基:CH2=CHCOOR5−またはCH2=C(CH3)COOR5−(式中、R5はアルキレン基を示す。)を示す。]
(4)貼着した被着体を、100〜220℃の温度に曝した後、前記融点未満の温度で取り外す前記(1)〜(3)のいずれかに記載の易剥離性粘着シート。
(5)基材フィルムの少なくとも片面に粘着剤層を設けており、該粘着剤層は、側鎖結晶性ポリマーを含有し、かつ該側鎖結晶性ポリマーの融点未満の温度で粘着力が低下し、前記側鎖結晶性ポリマーは、反応性ポリシロキサン化合物および反応性フッ素化合物から選ばれる少なくとも1種と、側鎖結晶性ポリマーを構成する他のモノマーとの共重合体からなることを特徴とする易剥離性粘着テープ。
なお、本発明における前記「シート」は、シート状のみに限定されるものではなく、本発明の効果を損なわない限りにおいて、シート状ないしフィルム状をも含む概念である。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found a solution means having the following constitution and have completed the present invention.
(1) A pressure-sensitive adhesive sheet containing a side-chain crystalline polymer and having reduced adhesive strength at a temperature lower than the melting point of the side-chain crystalline polymer, wherein the side-chain crystalline polymer comprises a reactive polysiloxane compound and a reaction An easily peelable pressure-sensitive adhesive sheet comprising a copolymer of at least one selected from a polymerizable fluorine compound and another monomer constituting a side chain crystalline polymer.
(2) The easily peelable pressure-sensitive adhesive sheet according to (1), wherein the reactive polysiloxane compound is a modified polydimethylsiloxane compound represented by the following general formula (I).
Figure 2011219617
[Wherein R 1 represents an alkyl group. R 2 represents a group: CH 2 ═CHCOOR 3 — or CH 2 ═C (CH 3 ) COOR 3 — (wherein R 3 represents an alkylene group). n shows the integer of 5-200. ]
(3) The easily peelable pressure-sensitive adhesive sheet according to (1) or (2), wherein the reactive fluorine compound is a compound represented by the following general formula (II).
Figure 2011219617
[Wherein R 4 represents a group: CH 2 ═CHCOOR 5 — or CH 2 ═C (CH 3 ) COOR 5 — (wherein R 5 represents an alkylene group). ]
(4) The easily peelable pressure-sensitive adhesive sheet according to any one of (1) to (3), wherein the adhered adherend is exposed to a temperature of 100 to 220 ° C. and then removed at a temperature lower than the melting point.
(5) A pressure-sensitive adhesive layer is provided on at least one surface of the base film, and the pressure-sensitive adhesive layer contains a side chain crystalline polymer, and the adhesive strength decreases at a temperature lower than the melting point of the side chain crystalline polymer. The side chain crystalline polymer comprises a copolymer of at least one selected from a reactive polysiloxane compound and a reactive fluorine compound and another monomer constituting the side chain crystalline polymer. Easy to peel adhesive tape.
The “sheet” in the present invention is not limited to a sheet shape, and is a concept including a sheet shape or a film shape as long as the effects of the present invention are not impaired.

本発明によれば、温度変化に対応して結晶状態と流動状態とを可逆的に起こす側鎖結晶性ポリマーを含有するので、粘着力を熱により可逆的に制御することができる。したがって、被着体から剥離する際には、粘着シートまたは粘着テープの温度を所定温度にすれば、粘着力を低下させることができる。   According to the present invention, since the side chain crystalline polymer that reversibly causes a crystalline state and a fluid state corresponding to a temperature change is contained, the adhesive force can be reversibly controlled by heat. Therefore, when peeling from the adherend, the adhesive strength can be reduced by setting the temperature of the adhesive sheet or adhesive tape to a predetermined temperature.

しかも、前記側鎖結晶性ポリマーは、反応性ポリシロキサン化合物および反応性フッ素化合物から選ばれる少なくとも1種をモノマーの1つとする共重合体からなるので、側鎖結晶性ポリマーによる粘着力の低下に加えて、ポリシロキサン化合物やフッ素化合物に起因する離型性も加わる。したがって、本発明によれば、粘着力を十分に低下させることができるので、被着体から容易に剥離することができるという効果がある。また、側鎖結晶性ポリマーの相変化を利用するものであるため、繰り返し使用することができる。   In addition, since the side chain crystalline polymer is made of a copolymer having at least one selected from a reactive polysiloxane compound and a reactive fluorine compound as one of the monomers, the side chain crystalline polymer reduces the adhesive force. In addition, releasability due to polysiloxane compounds and fluorine compounds is added. Therefore, according to the present invention, since the adhesive force can be sufficiently reduced, there is an effect that it can be easily peeled off from the adherend. Moreover, since it utilizes the phase change of the side chain crystalline polymer, it can be used repeatedly.

<易剥離性粘着シート>
本発明にかかる易剥離性粘着シート(以下、「粘着シート」と言うことがある。)は、側鎖結晶性ポリマーを含有する。該側鎖結晶性ポリマーは、融点未満の温度で結晶化しかつ融点以上の温度で流動性を示すポリマーである。すなわち、側鎖結晶性ポリマーは、温度変化に対応して結晶状態と流動状態とを可逆的に起こすポリマーである。
<Easily peelable adhesive sheet>
The easily peelable pressure-sensitive adhesive sheet according to the present invention (hereinafter sometimes referred to as “pressure-sensitive adhesive sheet”) contains a side chain crystalline polymer. The side chain crystalline polymer is a polymer that crystallizes at a temperature below the melting point and exhibits fluidity at a temperature above the melting point. That is, the side chain crystalline polymer is a polymer that reversibly causes a crystalline state and a fluid state in response to a temperature change.

前記粘着シートは、前記融点未満の温度で側鎖結晶性ポリマーが結晶化した際に粘着力が低下する割合で側鎖結晶性ポリマーを含有する。つまり、前記粘着シートは、側鎖結晶性ポリマーを主成分として含有する。これにより、被着体から粘着シートを剥離する際には、粘着シートを側鎖結晶性ポリマーの融点未満の温度に冷却すれば、側鎖結晶性ポリマーが結晶化することによって粘着力が低下する。また、粘着シートを側鎖結晶性ポリマーの融点以上の温度に加熱すれば、側鎖結晶性ポリマーが流動性を示すことによって粘着力が回復するので、繰り返し使用することができる。   The pressure-sensitive adhesive sheet contains the side-chain crystalline polymer in such a ratio that the adhesive strength decreases when the side-chain crystalline polymer is crystallized at a temperature lower than the melting point. That is, the pressure-sensitive adhesive sheet contains a side chain crystalline polymer as a main component. Thereby, when peeling an adhesive sheet from a to-be-adhered body, if an adhesive sheet is cooled to the temperature below melting | fusing point of a side chain crystalline polymer, adhesive force will fall by crystallizing a side chain crystalline polymer. . Further, if the pressure-sensitive adhesive sheet is heated to a temperature equal to or higher than the melting point of the side-chain crystalline polymer, the side-chain crystalline polymer exhibits fluidity, and thus the adhesive strength is recovered. Therefore, it can be used repeatedly.

前記融点とは、ある平衡プロセスにより、最初は秩序ある配列に整合されていた重合体の特定部分が無秩序状態となる温度を意味し、示差熱走査熱量計(DSC)により10℃/分の測定条件で測定して得られる値である。前記融点としては0℃以上、好ましくは10〜60℃であるのがよい。前記融点を所定の値とするには、側鎖結晶性ポリマーの組成等を変えることによって任意に行うことができる。   The melting point means a temperature at which a specific portion of the polymer originally aligned in an ordered arrangement becomes disordered by an equilibrium process, and is measured by a differential thermal scanning calorimeter (DSC) at 10 ° C./min. It is a value obtained by measuring under conditions. The melting point is 0 ° C. or higher, preferably 10 to 60 ° C. The melting point can be arbitrarily set to a predetermined value by changing the composition of the side chain crystalline polymer.

前記側鎖結晶性ポリマーは、反応性ポリシロキサン化合物および反応性フッ素化合物から選ばれる少なくとも1種と、側鎖結晶性ポリマーを構成する他のモノマーとの共重合体からなる。したがって、粘着シートを側鎖結晶性ポリマーの融点未満の温度に冷却すれば、側鎖結晶性ポリマーによる粘着力の低下に加えて、ポリシロキサン化合物やフッ素化合物に起因する離型性も加わるので、粘着力を十分に低下させることができ、被着体から容易に剥離することができる。   The side chain crystalline polymer is composed of a copolymer of at least one selected from a reactive polysiloxane compound and a reactive fluorine compound and another monomer constituting the side chain crystalline polymer. Therefore, if the pressure-sensitive adhesive sheet is cooled to a temperature lower than the melting point of the side chain crystalline polymer, in addition to the decrease in adhesive strength due to the side chain crystalline polymer, the releasability due to the polysiloxane compound and the fluorine compound is also added. The adhesive force can be sufficiently reduced and can be easily peeled off from the adherend.

特に、本発明の粘着シートは、貼着した被着体を100〜220℃の温度に曝した後、前記融点未満の温度で取り外す粘着シートとして使用するのが好ましい。すなわち、粘着シートは、その用途によっては、被着体を貼着した状態で100〜220℃の温度に曝されることがある。このような高い温度に粘着シートを曝すと、粘着シートが柔軟になって被着体表面に存在する凹凸形状によく追従するようになる。その結果、雰囲気温度が下がった際に、いわゆるアンカー効果が発現し、粘着シートの粘着力が初期粘着力よりも高くなる。それゆえ、粘着シートが一般的なアクリル系粘着剤からなる場合には、剥離不良を生じることが多い。   In particular, the pressure-sensitive adhesive sheet of the present invention is preferably used as a pressure-sensitive adhesive sheet that is removed at a temperature lower than the melting point after the adhered adherend is exposed to a temperature of 100 to 220 ° C. That is, the pressure-sensitive adhesive sheet may be exposed to a temperature of 100 to 220 ° C. with the adherend adhered, depending on the application. When the pressure-sensitive adhesive sheet is exposed to such a high temperature, the pressure-sensitive adhesive sheet becomes flexible and follows the uneven shape present on the adherend surface well. As a result, when the ambient temperature is lowered, a so-called anchor effect is exhibited, and the adhesive strength of the adhesive sheet becomes higher than the initial adhesive strength. Therefore, when the pressure-sensitive adhesive sheet is made of a general acrylic pressure-sensitive adhesive, a peeling failure often occurs.

本発明の粘着シートは、100〜220℃の温度に曝されることで粘着力が初期粘着力より高くなったとしても、前記融点未満の温度にまで冷却すれば、前記した理由から粘着力が十分に低下するので、被着体を簡単に取り外すことができる。前記被着体としては、特に限定されないが、LEDやFPD等における大型化および薄型化されたガラス、プラスチック等からなる基板が好適である。   Even if the pressure-sensitive adhesive sheet of the present invention is exposed to a temperature of 100 to 220 ° C. and the pressure-sensitive adhesive strength becomes higher than the initial pressure-sensitive adhesive strength, the pressure-sensitive adhesive sheet has an adhesive strength for the reasons described above if it is cooled to a temperature below the melting point. Since it drops sufficiently, the adherend can be easily removed. The adherend is not particularly limited, but a substrate made of glass, plastic or the like that is enlarged and thinned in an LED, FPD, or the like is preferable.

ここで、前記反応性ポリシロキサン化合物とは、反応性を示す官能基を有し、かつ主鎖にシロキサン結合を有するポリシロキサン化合物のことを意味する。反応性ポリシロキサン化合物は、室温(23℃)でワックス状でもよいが、効率よく重合させる上で、室温で流動性を示すオイル状、すなわちシリコーンオイルが好ましい。   Here, the reactive polysiloxane compound means a polysiloxane compound having a reactive functional group and having a siloxane bond in the main chain. The reactive polysiloxane compound may be in the form of a wax at room temperature (23 ° C.), but an oil that exhibits fluidity at room temperature, that is, a silicone oil, is preferable for efficient polymerization.

前記反応性を示す官能基としては、例えばビニル基、アリル基、(メタ)アクリル基、(メタ)アクリロイル基、(メタ)アクリロキシ基等のエチレン性不飽和二重結合を有する基;エポキシ基(グリシジル基およびエポキシシクロアルキル基を含む)、メルカプト基、カルビノール基、カルボキシル基、シラノール基、フェノール基、アミノ基、水酸基等が挙げられる。   Examples of the functional group exhibiting reactivity include a group having an ethylenically unsaturated double bond such as vinyl group, allyl group, (meth) acryl group, (meth) acryloyl group, (meth) acryloxy group; epoxy group ( Glycidyl group and epoxycycloalkyl group), mercapto group, carbinol group, carboxyl group, silanol group, phenol group, amino group, hydroxyl group and the like.

これらの官能基は、主鎖が有する側鎖に導入してもよく、主鎖の両末端または片末端に導入してもよい。すなわち、反応性ポリシロキサン化合物は、導入される官能基の結合位置によって、いわゆる側鎖型、両末端型、片末端型および側鎖両末端型の4種類が挙げられ、特に、優れた離型性が得られる上で片末端型、すなわち片末端反応性ポリシロキサン化合物が好ましい。   These functional groups may be introduced into the side chain of the main chain, or may be introduced into both ends or one end of the main chain. That is, there are four types of reactive polysiloxane compounds, so-called side chain type, double-ended type, single-ended type, and double-ended side chain type, depending on the bonding position of the functional group to be introduced. From the standpoint of obtaining good performance, one-end type, that is, one-end reactive polysiloxane compound is preferred.

片末端反応性ポリシロキサン化合物の具体例としては、前記一般式(I)で表される変性ポリジメチルシロキサン化合物等が挙げられる。前記一般式(I)中、R1はアルキル基を示し、該アルキル基としては、例えばメチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、イソブチル基、s−ブチル基、t−ブチル基、ペンチル基、イソペンチル基、ネオペンチル基、ヘキシル基等の炭素数1〜6の直鎖または分岐したアルキル基が挙げられる。 Specific examples of the one-terminal reactive polysiloxane compound include a modified polydimethylsiloxane compound represented by the general formula (I). In the general formula (I), R 1 represents an alkyl group, and examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, Examples thereof include linear or branched alkyl groups having 1 to 6 carbon atoms such as a t-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and a hexyl group.

また、前記一般式(I)中、R2は基:CH2=CHCOOR3−またはCH2=C(CH3)COOR3−(式中、R3はアルキレン基を示す。)を示し、前記アルキレン基としては、例えばメチレン基、エチレン基、トリメチレン基、メチルエチレン基、プロピレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基等の炭素数1〜6の直鎖または分枝したアルキレン基等が挙げられる。前記一般式(I)中、nは5〜200の整数を示す。 In the general formula (I), R 2 represents a group: CH 2 ═CHCOOR 3 — or CH 2 ═C (CH 3 ) COOR 3 — (wherein R 3 represents an alkylene group), and Examples of the alkylene group include linear or branched alkylene groups having 1 to 6 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, a methylethylene group, a propylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. Is mentioned. In the general formula (I), n represents an integer of 5 to 200.

前記一般式(I)で表される変性ポリジメチルシロキサン化合物の具体例としては、下記一般式(Ia)で表される化合物等が挙げられる。

Figure 2011219617
[式中、R1,R3,nは、前記と同じである。] Specific examples of the modified polydimethylsiloxane compound represented by the general formula (I) include compounds represented by the following general formula (Ia).
Figure 2011219617
[Wherein R 1 , R 3 and n are the same as defined above. ]

変性ポリジメチルシロキサン化合物は、市販のものを用いることができ、具体例としては、例えばいずれも信越化学工業(株)製の片末端反応性シリコーンオイル「X−22−2404」、「X−24−8201」、「X−22−174DX」、「X−22−2426」等が挙げられる。   As the modified polydimethylsiloxane compound, a commercially available product can be used. Specific examples thereof include, for example, single-end reactive silicone oils “X-22-2404” and “X-24” manufactured by Shin-Etsu Chemical Co., Ltd. -8201 "," X-22-174DX "," X-22-2426 "and the like.

一方、前記反応性フッ素化合物とは、反応性を示す官能基を有するフッ素化合物のことを意味する。前記反応性を示す官能基としては、前記反応性ポリシロキサン化合物で例示したのと同じ官能基が挙げられる。   On the other hand, the reactive fluorine compound means a fluorine compound having a reactive functional group. Examples of the functional group showing the reactivity include the same functional groups as exemplified for the reactive polysiloxane compound.

前記反応性フッ素化合物の具体例としては、前記一般式(II)で表される化合物等が挙げられる。前記一般式(II)中、R4は基:CH2=CHCOOR5−またはCH2=C(CH3)COOR5−(式中、R5はアルキレン基を示す。)を示し、前記アルキレン基としては、前記一般式(I)で例示したのと同じアルキレン基が挙げられる。 Specific examples of the reactive fluorine compound include compounds represented by the general formula (II). In the general formula (II), R 4 represents a group: CH 2 ═CHCOOR 5 — or CH 2 ═C (CH 3 ) COOR 5 — (wherein R 5 represents an alkylene group), and the alkylene group Examples of the alkylene group include the same alkylene groups as those exemplified in the general formula (I).

また、前記一般式(II)で表される化合物の具体例としては、下記式(IIa),(IIb)で表される化合物等が挙げられる。

Figure 2011219617
Specific examples of the compound represented by the general formula (II) include compounds represented by the following formulas (IIa) and (IIb).
Figure 2011219617

反応性フッ素化合物は、市販のものを用いることができ、具体例としては、例えばいずれも大阪有機化学工業(株)製の「ビスコート3F」、「ビスコート3FM」、「ビスコート4F」、「ビスコート8F」、「ビスコート8FM」、共栄社化学(株)製の「ライトエステルM−3F」等が挙げられる。   As the reactive fluorine compound, a commercially available product can be used, and specific examples include, for example, “Biscoat 3F”, “Biscoat 3FM”, “Biscoat 4F”, “Biscoat 8F” manufactured by Osaka Organic Chemical Industry Co., Ltd. ”,“ Biscoat 8FM ”,“ Light Ester M-3F ”manufactured by Kyoeisha Chemical Co., Ltd., and the like.

側鎖結晶性ポリマーを構成する前記他のモノマーとしては、例えば炭素数16以上の直鎖状アルキル基を有する(メタ)アクリレート、炭素数1〜6のアルキル基を有する(メタ)アクリレート、極性モノマー等が挙げられる。   Examples of the other monomer constituting the side chain crystalline polymer include (meth) acrylate having a linear alkyl group having 16 or more carbon atoms, (meth) acrylate having an alkyl group having 1 to 6 carbon atoms, and a polar monomer. Etc.

前記炭素数16以上の直鎖状アルキル基を有する(メタ)アクリレートとしては、例えばセチル(メタ)アクリレート、ステアリル(メタ)アクリレート、エイコシル(メタ)アクリレート、ベヘニル(メタ)アクリレート等の炭素数16〜22の線状アルキル基を有する(メタ)アクリレートが挙げられ、前記炭素数1〜6のアルキル基を有する(メタ)アクリレートとしては、例えばメチル(メタ)アクリレート、エチル(メタ)アクリレート、ブチル(メタ)アクリレート、ヘキシル(メタ)アクリレート等が挙げられ、前記極性モノマーとしては、例えばアクリル酸、メタクリル酸、クロトン酸、イタコン酸、マレイン酸、フマル酸等のカルボキシル基含有エチレン不飽和単量体;2−ヒドロキシエチル(メタ)アクリレート、2−ヒドロキシプロピル(メタ)アクリレート、2−ヒドロキシヘキシル(メタ)アクリレート等のヒドロキシル基を有するエチレン不飽和単量体等が挙げられ、これらは1種または2種以上を混合して用いてもよい。   Examples of the (meth) acrylate having a linear alkyl group having 16 or more carbon atoms include 16 to 16 carbon atoms such as cetyl (meth) acrylate, stearyl (meth) acrylate, eicosyl (meth) acrylate, and behenyl (meth) acrylate. (Meth) acrylate having 22 linear alkyl groups can be mentioned. Examples of the (meth) acrylate having 1 to 6 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) ) Acrylate, hexyl (meth) acrylate and the like. Examples of the polar monomer include carboxyl group-containing ethylenically unsaturated monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid; 2 -Hydroxyethyl (meth) acrylate, 2- Mud hydroxypropyl (meth) acrylate, 2-hydroxyhexyl (meth) ethylenically unsaturated monomer having a hydroxyl group such as acrylate and the like, which may be used alone or in combination.

側鎖結晶性ポリマーの組成としては、前記反応性ポリシロキサン化合物および反応性フッ素化合物から選ばれる少なくとも1種と、側鎖結晶性ポリマーを構成する前記他のモノマーとを、重量比で1:99〜20:80、好ましくは1:99〜10:90の割合で重合させた共重合体がよい。   As for the composition of the side chain crystalline polymer, at least one selected from the reactive polysiloxane compound and the reactive fluorine compound and the other monomer constituting the side chain crystalline polymer are in a weight ratio of 1:99. A copolymer polymerized in a ratio of ˜20: 80, preferably 1:99 to 10:90 is preferable.

また、前記反応性ポリシロキサン化合物および反応性フッ素化合物から選ばれる少なくとも1種を1〜20重量部、好ましくは1〜10重量部と、前記炭素数16以上の直鎖状アルキル基を有する(メタ)アクリレート10〜99重量部、好ましくは20〜99重量部と、前記炭素数1〜6のアルキル基を有する(メタ)アクリレート0〜60重量部と、前記極性モノマー0〜10重量部と、を重合させた共重合体が好ましい。特に、炭素数16以上の直鎖状アルキル基を有する(メタ)アクリレートの割合を多くすると、易剥離性が向上する傾向にあるので好ましい。   Further, at least one selected from the reactive polysiloxane compound and the reactive fluorine compound has 1 to 20 parts by weight, preferably 1 to 10 parts by weight, and the linear alkyl group having 16 or more carbon atoms (meta ) 10 to 99 parts by weight of acrylate, preferably 20 to 99 parts by weight, 0 to 60 parts by weight of (meth) acrylate having an alkyl group having 1 to 6 carbon atoms, and 0 to 10 parts by weight of the polar monomer. A polymerized copolymer is preferred. In particular, it is preferable to increase the proportion of the (meth) acrylate having a linear alkyl group having 16 or more carbon atoms, since the easy peelability tends to be improved.

重合方法としては、特に限定されるものではなく、例えば溶液重合法、塊状重合法、懸濁重合法、乳化重合法等が採用可能である。例えば溶液重合法を採用する場合には、前記で例示したモノマーを溶剤に混合し、40〜90℃程度で2〜10時間程度攪拌することによって前記モノマーを重合させることができる。   The polymerization method is not particularly limited, and for example, a solution polymerization method, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method and the like can be employed. For example, when the solution polymerization method is employed, the monomer can be polymerized by mixing the monomer exemplified above in a solvent and stirring at about 40 to 90 ° C. for about 2 to 10 hours.

前記側鎖結晶性ポリマーの重量平均分子量は100,000以上、好ましくは300,000〜900,000であるのがよい。前記重量平均分子量があまり小さいと、被着体から粘着シートを剥離する際に粘着シートが被着体上に残る、いわゆる糊残りが多くなるおそれがある。また、前記重量平均分子量があまり大きいと、側鎖結晶性ポリマーを融点未満の温度にしても結晶化し難くなるので、粘着力が低下し難くなる。前記重量平均分子量は、側鎖結晶性ポリマーをゲルパーミエーションクロマトグラフィ(GPC)で測定し、得られた測定値をポリスチレン換算した値である。   The side chain crystalline polymer has a weight average molecular weight of 100,000 or more, preferably 300,000 to 900,000. If the weight average molecular weight is too small, the adhesive sheet may remain on the adherend when the adhesive sheet is peeled off from the adherend, and so-called adhesive residue may increase. On the other hand, if the weight average molecular weight is too large, it is difficult to crystallize even if the side chain crystalline polymer is at a temperature lower than the melting point. The weight average molecular weight is a value obtained by measuring a side chain crystalline polymer by gel permeation chromatography (GPC) and converting the obtained measurement value to polystyrene.

前記粘着シートの厚さとしては、15〜400μmであるのが好ましく、120〜150μmであるのがより好ましい。粘着シートの厚さがあまり薄いと、粘着力が低下し、加工時に被着体を固定し難くなるので好ましくない。また、粘着シートの厚さがあまり大きいと、粘着シートの厚さにバラツキを生じるおそれがあるので好ましくない。   The thickness of the pressure-sensitive adhesive sheet is preferably 15 to 400 μm, and more preferably 120 to 150 μm. If the thickness of the pressure-sensitive adhesive sheet is too thin, the pressure-sensitive adhesive force is lowered, and it is difficult to fix the adherend during processing, which is not preferable. Moreover, since the thickness of an adhesive sheet may produce variation when the thickness of an adhesive sheet is too large, it is unpreferable.

粘着シートの両面には、離型処理を施したフィルム、すなわち離型フィルムを設けるのが好ましい。前記離型フィルムとしては、例えばポリエチレンテレフタレート等からなるフィルム表面に、シリコーン等の離型剤を塗布したものが挙げられる。粘着シートの両面に離型フィルムを設けるには、例えば側鎖結晶性ポリマーを溶剤に加えた塗布液を、離型フィルム上に塗布して乾燥させて粘着シートを得、この粘着シートの表面に離型フィルムを配置すればよい。   It is preferable to provide a release-treated film, that is, a release film, on both sides of the pressure-sensitive adhesive sheet. Examples of the release film include a film surface made of polyethylene terephthalate or the like and a release agent such as silicone applied thereto. In order to provide release films on both sides of the pressure-sensitive adhesive sheet, for example, a coating solution obtained by adding a side chain crystalline polymer to a solvent is applied onto the release film and dried to obtain a pressure-sensitive adhesive sheet. A release film may be disposed.

前記塗布液には、例えば架橋剤、タッキファイヤー、可塑剤、老化防止剤、紫外線吸収剤等の各種の添加剤を添加することができる。前記塗布は、一般的にナイフコーター、ロールコーター、カレンダーコーター、コンマコーター等により行うことができる。また、塗工厚みや塗布液の粘度によっては、グラビアコーター、ロッドコーター等により行うこともできる。なお、粘着シートは、前記塗布の他、例えば押し出し成形やカレンダー加工によってシート状に成形することもできる。   Various additives such as a crosslinking agent, a tackifier, a plasticizer, an anti-aging agent, and an ultraviolet absorber can be added to the coating solution. The application can be generally performed by a knife coater, a roll coater, a calendar coater, a comma coater or the like. Further, depending on the coating thickness and the viscosity of the coating solution, a gravure coater, a rod coater or the like can be used. In addition to the application, the pressure-sensitive adhesive sheet can be formed into a sheet shape by, for example, extrusion molding or calendering.

<易剥離性粘着テープ>
本発明にかかる易剥離性粘着テープ(以下、「粘着テープ」と言うことがある。)は、基材フィルムの少なくとも片面に粘着剤層を設けてなる。該粘着剤層は、側鎖結晶性ポリマーを含有し、該側鎖結晶性ポリマーの融点未満の温度で粘着力が低下する。そして、前記側鎖結晶性ポリマーは、前記した粘着シートと同様に、反応性ポリシロキサン化合物および反応性フッ素化合物から選ばれる少なくとも1種と、側鎖結晶性ポリマーを構成する他のモノマーとの共重合体からなる。したがって、本発明の粘着テープは、前記した本発明の粘着シートと同様の効果を奏するとともに、基材フィルムを含む分、粘着シートよりも剛性が高く、取り扱い性に優れるという効果を奏する。
<Easily peelable adhesive tape>
The easily peelable pressure-sensitive adhesive tape according to the present invention (hereinafter sometimes referred to as “pressure-sensitive adhesive tape”) is provided with a pressure-sensitive adhesive layer on at least one surface of a base film. The pressure-sensitive adhesive layer contains a side chain crystalline polymer, and the adhesive strength is reduced at a temperature lower than the melting point of the side chain crystalline polymer. The side chain crystalline polymer is a co-polymer of at least one selected from a reactive polysiloxane compound and a reactive fluorine compound and another monomer constituting the side chain crystalline polymer, as in the above-described adhesive sheet. It consists of a polymer. Therefore, the pressure-sensitive adhesive tape of the present invention has the same effects as the pressure-sensitive adhesive sheet of the present invention described above, and has the effect that it is higher in rigidity than the pressure-sensitive adhesive sheet and excellent in handleability because it includes the base film.

前記基材フィルムとしては、例えばポリエチレン、ポリエチレンテレフタレート、ポリプロピレン、ポリエステル、ポリアミド、ポリイミド、ポリカーボネート、エチレン酢酸ビニル共重合体、エチレンエチルアクリレート共重合体、エチレンポリプロピレン共重合体、ポリ塩化ビニル等の合成樹脂フィルムが挙げられる。   Examples of the base film include synthetic resins such as polyethylene, polyethylene terephthalate, polypropylene, polyester, polyamide, polyimide, polycarbonate, ethylene vinyl acetate copolymer, ethylene ethyl acrylate copolymer, ethylene polypropylene copolymer, and polyvinyl chloride. A film is mentioned.

前記基材フィルムは、単層体または複層体からなるものであってもよく、厚さは、通常、25〜250μm程度である。基材フィルムの表面には、粘着剤層に対する密着性を向上させるため、例えばコロナ放電処理、プラズマ処理、ブラスト処理、ケミカルエッチング処理、プライマー処理等の表面処理を施すことができる。   The said base film may consist of a single layer body or a multilayer body, and thickness is about 25-250 micrometers normally. The surface of the base film can be subjected to surface treatment such as corona discharge treatment, plasma treatment, blast treatment, chemical etching treatment, and primer treatment in order to improve the adhesion to the pressure-sensitive adhesive layer.

基材フィルムの片面に粘着剤層を設けるには、前記した側鎖結晶性ポリマーを溶剤に加えた塗布液を、基材フィルムの片面に塗布して乾燥させればよい。粘着剤層の厚さはとしては、5〜60μmであるのが好ましく、10〜60μmであるのがより好ましく、10〜40μmであるのがさらに好ましい。   In order to provide the pressure-sensitive adhesive layer on one side of the base film, a coating solution obtained by adding the aforementioned side chain crystalline polymer to the solvent may be applied to one side of the base film and dried. As thickness of an adhesive layer, it is preferable that it is 5-60 micrometers, it is more preferable that it is 10-60 micrometers, and it is further more preferable that it is 10-40 micrometers.

一方、前記粘着テープは、基材フィルムの他面にも粘着剤層を設けて両面粘着テープの形態で使用することもできる。他面の粘着剤層としては、特に限定されるものではなく、例えば片面の粘着剤層と同様に、前記側鎖結晶性ポリマーを含有する粘着剤層を用いることもできる。この場合、片面の粘着剤層と他面の粘着剤層とは、その組成や厚さが互いに同じであってもよいし、異なっていてもよい。その他の構成は、前記した粘着シートと同様である。   Meanwhile, the pressure-sensitive adhesive tape may be used in the form of a double-sided pressure-sensitive adhesive tape by providing a pressure-sensitive adhesive layer on the other surface of the base film. The pressure-sensitive adhesive layer on the other side is not particularly limited, and for example, a pressure-sensitive adhesive layer containing the side chain crystalline polymer can be used in the same manner as the pressure-sensitive adhesive layer on one side. In this case, the pressure-sensitive adhesive layer on one side and the pressure-sensitive adhesive layer on the other side may be the same or different in composition and thickness. Other configurations are the same as those of the above-described pressure-sensitive adhesive sheet.

以下、合成例および実施例を挙げて本発明を詳細に説明するが、本発明は以下の合成例および実施例のみに限定されるものではない。なお、以下の説明で「部」は重量部を意味する。   EXAMPLES Hereinafter, although a synthesis example and an Example are given and this invention is demonstrated in detail, this invention is not limited only to the following synthesis examples and Examples. In the following description, “part” means part by weight.

合成例に使用した反応性ポリシロキサン化合物および反応性フッ素化合物は、次の通りである。
・反応性ポリシロキサン化合物:前記一般式(Ia)で表される信越化学工業(株)製の「X−22−174DX」を用いた。
・反応性フッ素化合物(A):前記式(IIa)で表される大阪有機化学工業(株)製の「ビスコート3F」を用いた。
・反応性フッ素化合物(B):前記式(IIb)で表される大阪有機化学工業(株)製の「ビスコート3FM」を用いた。
The reactive polysiloxane compound and the reactive fluorine compound used in the synthesis examples are as follows.
Reactive polysiloxane compound: “X-22-174DX” manufactured by Shin-Etsu Chemical Co., Ltd. represented by the above general formula (Ia) was used.
Reactive fluorine compound (A): “Biscoat 3F” manufactured by Osaka Organic Chemical Industry Co., Ltd. represented by the formula (IIa) was used.
Reactive fluorine compound (B): “Biscoat 3FM” manufactured by Osaka Organic Chemical Industry Co., Ltd. represented by the above formula (IIb) was used.

(合成例1)
ベヘニルアクリレート(日油社製)を50部、メチルアクリレート(日本触媒社製)を40部、反応性ポリシロキサン化合物を5部、アクリル酸を5部およびパーブチルND(日油社製)を0.3部の割合で、それぞれ酢酸エチル230部に加えて混合し、55℃で4時間撹拌して、これらのモノマーを重合させた。得られた共重合体である側鎖結晶性ポリマーの重量平均分子量は650,000、融点は56℃であった。
(Synthesis Example 1)
50 parts of behenyl acrylate (manufactured by NOF Corporation), 40 parts of methyl acrylate (manufactured by Nippon Shokubai Co., Ltd.), 5 parts of reactive polysiloxane compound, 5 parts of acrylic acid and 0.02 part of perbutyl ND (manufactured by NOF Corporation). In a proportion of 3 parts, each was added to 230 parts of ethyl acetate, mixed, and stirred at 55 ° C. for 4 hours to polymerize these monomers. The obtained side chain crystalline polymer, which is a copolymer, had a weight average molecular weight of 650,000 and a melting point of 56 ° C.

(合成例2)
ベヘニルアクリレート(日油社製)を45部、メチルアクリレート(日本触媒社製)を45部、反応性フッ素化合物(A)を5部、アクリル酸を5部およびパーブチルND(日油社製)を0.3部の割合で、それぞれ酢酸エチル230部に加えて混合し、55℃で4時間撹拌して、これらのモノマーを重合させた。得られた共重合体である側鎖結晶性ポリマーの重量平均分子量は630,000、融点は55℃であった。
(Synthesis Example 2)
45 parts of behenyl acrylate (manufactured by NOF Corporation), 45 parts of methyl acrylate (manufactured by Nippon Shokubai Co., Ltd.), 5 parts of reactive fluorine compound (A), 5 parts of acrylic acid and perbutyl ND (manufactured by NOF Corporation) Each of these monomers was polymerized in a proportion of 0.3 part by adding to 230 parts of ethyl acetate and mixing at 55 ° C. for 4 hours. The obtained side chain crystalline polymer, which is a copolymer, had a weight average molecular weight of 630,000 and a melting point of 55 ° C.

(合成例3)
反応性フッ素化合物(A)5部に代えて、反応性フッ素化合物(B)を5部にした以外は、前記合成例2と同様にしてモノマーを重合させた。得られた共重合体である側鎖結晶性ポリマーの重量平均分子量は610,000、融点は55℃であった。
(Synthesis Example 3)
The monomer was polymerized in the same manner as in Synthesis Example 2 except that 5 parts of the reactive fluorine compound (B) was used instead of 5 parts of the reactive fluorine compound (A). The obtained side chain crystalline polymer, which was a copolymer, had a weight average molecular weight of 610,000 and a melting point of 55 ° C.

(比較合成例1)
ベヘニルアクリレート(日油社製)を45部、メチルアクリレート(日本触媒社製)を50部、アクリル酸を5部およびパーブチルND(日油社製)を0.3部の割合で、それぞれ酢酸エチル230部に加えて混合し、55℃で4時間撹拌して、これらのモノマーを重合させた。得られた共重合体である側鎖結晶性ポリマーの重量平均分子量は640,000、融点は56℃であった。
(Comparative Synthesis Example 1)
45 parts of behenyl acrylate (manufactured by NOF Corporation), 50 parts of methyl acrylate (manufactured by Nippon Shokubai Co., Ltd.), 5 parts of acrylic acid and 0.3 part of perbutyl ND (manufactured by NOF Corporation), each in ethyl acetate In addition to 230 parts, it mixed, and it stirred at 55 degreeC for 4 hours, and polymerized these monomers. The obtained side chain crystalline polymer, which is a copolymer, had a weight average molecular weight of 640,000 and a melting point of 56 ° C.

前記合成例1〜3および比較合成例1の各共重合体を表1に示す。なお、前記重量平均分子量は、共重合体をGPCで測定し、得られた測定値をポリスチレン換算した値である。前記融点は、DSCを用いて10℃/分の測定条件で測定した値である。   The copolymers of Synthesis Examples 1 to 3 and Comparative Synthesis Example 1 are shown in Table 1. In addition, the said weight average molecular weight is a value which measured the copolymer by GPC and converted the obtained measured value into polystyrene. The said melting | fusing point is the value measured on 10 degree-C / min measurement conditions using DSC.

Figure 2011219617
Figure 2011219617

[実施例1〜3および比較例1]
<粘着テープの作製>
まず、前記合成例で得られた各共重合体を、酢酸エチルを用いて固形分が30%になるよう調整して各共重合体溶液を得た。ついで、前記共重合体溶液100部に対して固形分換算で多官能アジリジン系架橋剤(日本触媒社製の「PZ−33」)を0.8部添加して得た粘着剤溶液を、厚さ100μmのポリエチレンテレフタレートフィルムの片面に塗布して乾燥させ、厚さ40μmの粘着剤層が形成された粘着テープを得た。
[Examples 1 to 3 and Comparative Example 1]
<Production of adhesive tape>
First, each copolymer obtained in the above synthesis example was adjusted to have a solid content of 30% using ethyl acetate to obtain each copolymer solution. Subsequently, a pressure-sensitive adhesive solution obtained by adding 0.8 part of a polyfunctional aziridine-based crosslinking agent (“PZ-33” manufactured by Nippon Shokubai Co., Ltd.) in terms of solid content to 100 parts of the copolymer solution was obtained. The film was applied to one side of a 100 μm thick polyethylene terephthalate film and dried to obtain a pressure sensitive adhesive tape on which a pressure sensitive adhesive layer having a thickness of 40 μm was formed.

<評価>
得られた粘着テープについて、180°剥離強度を評価した。評価方法を以下に示すとともに、その結果を表2に示す。
<Evaluation>
About the obtained adhesive tape, 180 degree peeling strength was evaluated. The evaluation method is shown below, and the results are shown in Table 2.

(180°剥離強度)
得られた粘着テープについて、80℃および23℃の各雰囲気温度におけるガラス基板に対する180°剥離強度をJIS Z0237に準拠して測定した。具体的には、以下の条件で粘着テープをガラス基板に貼着した後、ロードセルを用いて300mm/分の速度で180°剥離した(n=2)。
(180 ° peel strength)
About the obtained adhesive tape, 180 degree peel strength with respect to the glass substrate in each atmospheric temperature of 80 degreeC and 23 degreeC was measured based on JISZ0237. Specifically, the adhesive tape was attached to the glass substrate under the following conditions, and then peeled 180 ° at a rate of 300 mm / min using a load cell (n = 2).

(80℃)
80℃の雰囲気温度で粘着テープをガラス基板に貼着して20分間静置した後、180°剥離した。
(23℃)
80℃の雰囲気温度で粘着テープをガラス基板に貼着し、雰囲気温度を180℃に上げ、この雰囲気温度で20分間静置した後、雰囲気温度を23℃に下げ、この雰囲気温度で20分間静置した後、180°剥離した。
(80 ° C)
The adhesive tape was attached to a glass substrate at an atmospheric temperature of 80 ° C. and allowed to stand for 20 minutes, and then peeled 180 °.
(23 ° C)
Adhesive tape is attached to a glass substrate at an ambient temperature of 80 ° C., the ambient temperature is increased to 180 ° C., and the mixture is allowed to stand for 20 minutes at this ambient temperature. Then, the ambient temperature is lowered to 23 ° C. After placing, it peeled 180 °.

また、各雰囲気温度における破壊状態を目視にて評価した。表2中、「界面破壊」は、粘着剤層とガラス基板との間で剥離したことを示す。「スティックスリップ」は、粘着テープをガラス基板から剥離する際に、断続的に剥離が進行したことを示す。スティックスリップが発生すると、被着体にかかる負荷が局所的に大きくなるため、被着体を破損しやすい。   Moreover, the destruction state in each atmospheric temperature was evaluated visually. In Table 2, “interfacial fracture” indicates that peeling occurred between the pressure-sensitive adhesive layer and the glass substrate. “Stick slip” indicates that the peeling progressed intermittently when peeling the adhesive tape from the glass substrate. When stick-slip occurs, the load applied to the adherend increases locally, so that the adherend is easily damaged.

前記ガラス基板としては、厚さ0.7mm、250mm×140mmの形状を有する日本電気硝子社製の無アルカリガラス「AO−10G」を24時間かけてアルカリ洗浄したものを用いた。   As the glass substrate, an alkali-free glass “AO-10G” manufactured by Nippon Electric Glass Co., Ltd. having a thickness of 0.7 mm and a shape of 250 mm × 140 mm was used for 24 hours.

Figure 2011219617
Figure 2011219617

表2から明らかなように、実施例1〜3は、80℃の180°剥離強度において、比較例1よりも高い値を示しており、被着体の固定力に優れているのがわかる。また、実施例1〜3は、側鎖結晶性ポリマーの融点未満の温度である23℃の180°剥離強度において、比較例1よりも粘着力が低下しているとともに、破壊状態にも優れているのがわかる。   As is apparent from Table 2, Examples 1 to 3 show higher values than Comparative Example 1 in the 180 ° peel strength at 80 ° C., indicating that the adherend is excellent in fixing force. Moreover, in Examples 1-3, in 180 degree peel strength of 23 degreeC which is the temperature below melting | fusing point of a side chain crystalline polymer, while the adhesive force is falling rather than the comparative example 1, it is excellent also in a fracture state. I can see that

Claims (5)

側鎖結晶性ポリマーを含有し、該側鎖結晶性ポリマーの融点未満の温度で粘着力が低下する粘着シートであって、
前記側鎖結晶性ポリマーは、反応性ポリシロキサン化合物および反応性フッ素化合物から選ばれる少なくとも1種と、側鎖結晶性ポリマーを構成する他のモノマーとの共重合体からなることを特徴とする易剥離性粘着シート。
A pressure-sensitive adhesive sheet containing a side-chain crystalline polymer, the adhesive strength of which decreases at a temperature below the melting point of the side-chain crystalline polymer,
The side chain crystalline polymer is composed of a copolymer of at least one selected from a reactive polysiloxane compound and a reactive fluorine compound and another monomer constituting the side chain crystalline polymer. Peelable adhesive sheet.
前記反応性ポリシロキサン化合物が、下記一般式(I)で表される変性ポリジメチルシロキサン化合物である請求項1記載の易剥離性粘着シート。
Figure 2011219617
[式中、R1はアルキル基を示す。R2は基:CH2=CHCOOR3−またはCH2=C(CH3)COOR3−(式中、R3はアルキレン基を示す。)を示す。nは5〜200の整数を示す。]
The easily peelable pressure-sensitive adhesive sheet according to claim 1, wherein the reactive polysiloxane compound is a modified polydimethylsiloxane compound represented by the following general formula (I).
Figure 2011219617
[Wherein R 1 represents an alkyl group. R 2 represents a group: CH 2 ═CHCOOR 3 — or CH 2 ═C (CH 3 ) COOR 3 — (wherein R 3 represents an alkylene group). n shows the integer of 5-200. ]
前記反応性フッ素化合物が、下記一般式(II)で表される化合物である請求項1または2記載の易剥離性粘着シート。
Figure 2011219617
[式中、R4は基:CH2=CHCOOR5−またはCH2=C(CH3)COOR5−(式中、R5はアルキレン基を示す。)を示す。]
The easily peelable pressure-sensitive adhesive sheet according to claim 1 or 2, wherein the reactive fluorine compound is a compound represented by the following general formula (II).
Figure 2011219617
[Wherein R 4 represents a group: CH 2 ═CHCOOR 5 — or CH 2 ═C (CH 3 ) COOR 5 — (wherein R 5 represents an alkylene group). ]
貼着した被着体を、100〜220℃の温度に曝した後、前記融点未満の温度で取り外す請求項1〜3のいずれかに記載の易剥離性粘着シート。   The easily peelable adhesive sheet according to any one of claims 1 to 3, wherein the adhered adherend is exposed to a temperature of 100 to 220 ° C and then removed at a temperature lower than the melting point. 基材フィルムの少なくとも片面に粘着剤層を設けてなり、
該粘着剤層は、側鎖結晶性ポリマーを含有し、かつ該側鎖結晶性ポリマーの融点未満の温度で粘着力が低下し、
前記側鎖結晶性ポリマーは、反応性ポリシロキサン化合物および反応性フッ素化合物から選ばれる少なくとも1種と、側鎖結晶性ポリマーを構成する他のモノマーとの共重合体からなることを特徴とする易剥離性粘着テープ。
An adhesive layer is provided on at least one side of the base film,
The pressure-sensitive adhesive layer contains a side chain crystalline polymer, and the adhesive strength is reduced at a temperature lower than the melting point of the side chain crystalline polymer,
The side chain crystalline polymer is composed of a copolymer of at least one selected from a reactive polysiloxane compound and a reactive fluorine compound and another monomer constituting the side chain crystalline polymer. Peelable adhesive tape.
JP2010090092A 2010-04-09 2010-04-09 Easy peelable adhesive sheet and easy peelable adhesive tape Active JP5551959B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2010090092A JP5551959B2 (en) 2010-04-09 2010-04-09 Easy peelable adhesive sheet and easy peelable adhesive tape

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2010090092A JP5551959B2 (en) 2010-04-09 2010-04-09 Easy peelable adhesive sheet and easy peelable adhesive tape

Publications (2)

Publication Number Publication Date
JP2011219617A true JP2011219617A (en) 2011-11-04
JP5551959B2 JP5551959B2 (en) 2014-07-16

Family

ID=45037009

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2010090092A Active JP5551959B2 (en) 2010-04-09 2010-04-09 Easy peelable adhesive sheet and easy peelable adhesive tape

Country Status (1)

Country Link
JP (1) JP5551959B2 (en)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015141294A1 (en) * 2014-03-18 2015-09-24 ニッタ株式会社 Temperature sensitive adhesive
JP2017179004A (en) * 2016-03-28 2017-10-05 ニッタ株式会社 Temperature-sensitive adhesive
KR20180000693A (en) * 2016-06-23 2018-01-03 니타 가부시키가이샤 Thermosensitive resin, thermosensitive adhesive and thermosensitive adhesive composition
KR20180000694A (en) * 2016-06-23 2018-01-03 니타 가부시키가이샤 Thermosensitive resin, thermosensitive adhesive and thermosensitive adhesive composition
JP2019031662A (en) * 2017-08-07 2019-02-28 Agc株式会社 Water-repellent composition, and article
US11787979B2 (en) 2018-07-27 2023-10-17 Lg Chem, Ltd. Adhesive composition, adhesive film comprising same, back plate film comprising adhesive film and plastic organic light-emitting display comprising adhesive film
US11993734B2 (en) 2018-07-27 2024-05-28 Lg Chem, Ltd. Adhesive composition, adhesive film comprising same, backplate film comprising adhesive film, and plastic organic light-emitting display comprising adhesive film
US11993736B2 (en) 2018-07-27 2024-05-28 Lg Chem, Ltd. Adhesive composition, adhesive film comprising adhesive composition, back plate film comprising adhesive film, and plastic organic light emitting display comprising adhesive film
US12006449B2 (en) 2018-07-27 2024-06-11 Lg Chem, Ltd. Adhesive composition, adhesive film comprising same, back plate film comprising adhesive film and plastic organic light-emitting display comprising adhesive film
US12006456B2 (en) 2018-07-27 2024-06-11 Lg Chem, Ltd. Adhesive composition, adhesion film comprising same, backplate film comprising adhesion film, and plastic organic light-emitting display comprising adhesion film
US12012535B2 (en) 2018-07-27 2024-06-18 Lg Chem, Ltd. Adhesive composition, adhesive film comprising same, backplate film comprising adhesive film, and plastic organic light emitting display comprising adhesive film
US12018190B2 (en) 2018-07-27 2024-06-25 Lg Chem, Ltd. Adhesive composition, adhesive film comprising same, backplate film comprising adhesive film, and plastic organic light-emitting display comprising adhesive film
US12018188B2 (en) 2018-07-27 2024-06-25 Lg Chem, Ltd. Adhesive composition, adhesive film comprising same, backplate film comprising adhesive film, and plastic organic light emitting display comprising adhesive film

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201905139A (en) * 2017-06-23 2019-02-01 日商道康寧東麗股份有限公司 剥离Adhesive stripper composition and release film

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09251272A (en) * 1996-03-14 1997-09-22 Nitta Ind Corp Easily peelable label and its peeling method
JPH09251923A (en) * 1996-03-15 1997-09-22 Nitta Ind Corp Temporarily holding adhesive tape for laminate ceramic capacitor laminating process and laminate ceramic capacitor manufacturing method
JP2006241387A (en) * 2005-03-07 2006-09-14 Nitta Ind Corp Method for producing adhesive sheet and laminated ceramic electronic component
JP2007091818A (en) * 2005-09-27 2007-04-12 Fujifilm Corp Ultraviolet-curing type removable pressure bonding composition and removable adhesive converted paper
JP2008179744A (en) * 2007-01-26 2008-08-07 Nitta Ind Corp Adhesive agent
JP2009067824A (en) * 2007-09-10 2009-04-02 Nitta Ind Corp Thermosensitive resin, thermosensitive adhesive, and thermosensitive adhesive tape

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09251272A (en) * 1996-03-14 1997-09-22 Nitta Ind Corp Easily peelable label and its peeling method
JPH09251923A (en) * 1996-03-15 1997-09-22 Nitta Ind Corp Temporarily holding adhesive tape for laminate ceramic capacitor laminating process and laminate ceramic capacitor manufacturing method
JP2006241387A (en) * 2005-03-07 2006-09-14 Nitta Ind Corp Method for producing adhesive sheet and laminated ceramic electronic component
JP2007091818A (en) * 2005-09-27 2007-04-12 Fujifilm Corp Ultraviolet-curing type removable pressure bonding composition and removable adhesive converted paper
JP2008179744A (en) * 2007-01-26 2008-08-07 Nitta Ind Corp Adhesive agent
JP2009067824A (en) * 2007-09-10 2009-04-02 Nitta Ind Corp Thermosensitive resin, thermosensitive adhesive, and thermosensitive adhesive tape

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106103627B (en) * 2014-03-18 2019-01-01 霓达株式会社 Thermal adhesive
JP2015178539A (en) * 2014-03-18 2015-10-08 ニッタ株式会社 Temperature-sensitive adhesive
CN106103627A (en) * 2014-03-18 2016-11-09 霓达株式会社 Thermal adhesive
WO2015141294A1 (en) * 2014-03-18 2015-09-24 ニッタ株式会社 Temperature sensitive adhesive
JP2017179004A (en) * 2016-03-28 2017-10-05 ニッタ株式会社 Temperature-sensitive adhesive
KR102328925B1 (en) 2016-06-23 2021-11-19 니타 가부시키가이샤 Thermosensitive resin, thermosensitive adhesive and thermosensitive adhesive composition
JP7007550B2 (en) 2016-06-23 2022-01-24 ニッタ株式会社 Temperature Sensitive Resin, Temperature Sensitive Adhesive and Thermosensitive Adhesive Composition
KR20180000694A (en) * 2016-06-23 2018-01-03 니타 가부시키가이샤 Thermosensitive resin, thermosensitive adhesive and thermosensitive adhesive composition
JP2018003008A (en) * 2016-06-23 2018-01-11 ニッタ株式会社 Temperature-sensitive resin, temperature-sensitive adhesive and temperature-sensitive adhesive composition
KR102328928B1 (en) 2016-06-23 2021-11-19 니타 가부시키가이샤 Thermosensitive resin, thermosensitive adhesive and thermosensitive adhesive composition
KR20180000693A (en) * 2016-06-23 2018-01-03 니타 가부시키가이샤 Thermosensitive resin, thermosensitive adhesive and thermosensitive adhesive composition
JP7103017B2 (en) 2017-08-07 2022-07-20 Agc株式会社 Water repellent compositions and articles
JP2019031662A (en) * 2017-08-07 2019-02-28 Agc株式会社 Water-repellent composition, and article
US11787979B2 (en) 2018-07-27 2023-10-17 Lg Chem, Ltd. Adhesive composition, adhesive film comprising same, back plate film comprising adhesive film and plastic organic light-emitting display comprising adhesive film
US11993734B2 (en) 2018-07-27 2024-05-28 Lg Chem, Ltd. Adhesive composition, adhesive film comprising same, backplate film comprising adhesive film, and plastic organic light-emitting display comprising adhesive film
US11993736B2 (en) 2018-07-27 2024-05-28 Lg Chem, Ltd. Adhesive composition, adhesive film comprising adhesive composition, back plate film comprising adhesive film, and plastic organic light emitting display comprising adhesive film
US12006449B2 (en) 2018-07-27 2024-06-11 Lg Chem, Ltd. Adhesive composition, adhesive film comprising same, back plate film comprising adhesive film and plastic organic light-emitting display comprising adhesive film
US12006456B2 (en) 2018-07-27 2024-06-11 Lg Chem, Ltd. Adhesive composition, adhesion film comprising same, backplate film comprising adhesion film, and plastic organic light-emitting display comprising adhesion film
US12012535B2 (en) 2018-07-27 2024-06-18 Lg Chem, Ltd. Adhesive composition, adhesive film comprising same, backplate film comprising adhesive film, and plastic organic light emitting display comprising adhesive film
US12018190B2 (en) 2018-07-27 2024-06-25 Lg Chem, Ltd. Adhesive composition, adhesive film comprising same, backplate film comprising adhesive film, and plastic organic light-emitting display comprising adhesive film
US12018188B2 (en) 2018-07-27 2024-06-25 Lg Chem, Ltd. Adhesive composition, adhesive film comprising same, backplate film comprising adhesive film, and plastic organic light emitting display comprising adhesive film

Also Published As

Publication number Publication date
JP5551959B2 (en) 2014-07-16

Similar Documents

Publication Publication Date Title
JP5551959B2 (en) Easy peelable adhesive sheet and easy peelable adhesive tape
JP5714349B2 (en) Easy peelable adhesive sheet and easy peelable adhesive tape
JP5231775B2 (en) Temperature-sensitive resin, temperature-sensitive adhesive, and temperature-sensitive adhesive tape
JP6734010B2 (en) Temperature-sensitive adhesive sheet and temperature-sensitive adhesive tape
JP5639446B2 (en) Easy peelable adhesive sheet and easy peelable adhesive tape
JP6109932B2 (en) Temperature sensitive adhesive
JP6542562B2 (en) Temperature sensitive adhesive
JP6289960B2 (en) Temperature sensitive adhesive
JP5639438B2 (en) Temperature sensitive adhesive
JP6546910B2 (en) Temperature sensitive adhesive
JP2018178060A (en) Temperature-sensitive adhesive
KR102655512B1 (en) Temperature-sensitive adhesive, temperature-sensitive adhesive sheet and temperature-sensitive adhesive tape
JP2008031208A (en) Polymer for adhesive and adhesive composition
JP6479540B2 (en) Temperature sensitive adhesive
JP6440407B2 (en) TSV wafer manufacturing method
KR20170113269A (en) Temperature-sensitive adhesive
TW201843275A (en) Temperature-sensitive adhesive
WO2016158414A1 (en) Temperature-sensitive adhesive tape and temperature-sensitive adhesive sheet

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20130322

A977 Report on retrieval

Free format text: JAPANESE INTERMEDIATE CODE: A971007

Effective date: 20140219

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20140225

A521 Written amendment

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20140421

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20140513

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20140523

R150 Certificate of patent or registration of utility model

Ref document number: 5551959

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150