JP2008239684A - Pressure-sensitive adhesive sheet - Google Patents
Pressure-sensitive adhesive sheet Download PDFInfo
- Publication number
- JP2008239684A JP2008239684A JP2007078932A JP2007078932A JP2008239684A JP 2008239684 A JP2008239684 A JP 2008239684A JP 2007078932 A JP2007078932 A JP 2007078932A JP 2007078932 A JP2007078932 A JP 2007078932A JP 2008239684 A JP2008239684 A JP 2008239684A
- Authority
- JP
- Japan
- Prior art keywords
- sensitive adhesive
- pressure
- adhesive layer
- adherend
- 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
Links
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 164
- 239000010410 layer Substances 0.000 claims abstract description 77
- 239000000853 adhesive Substances 0.000 claims abstract description 58
- 230000001070 adhesive effect Effects 0.000 claims abstract description 58
- 239000000463 material Substances 0.000 claims abstract description 36
- 239000003431 cross linking reagent Substances 0.000 claims description 48
- 229920000103 Expandable microsphere Polymers 0.000 claims description 47
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 32
- 239000012790 adhesive layer Substances 0.000 claims description 30
- 239000011347 resin Substances 0.000 claims description 25
- 229920005989 resin Polymers 0.000 claims description 25
- 239000000758 substrate Substances 0.000 claims description 23
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- 238000012545 processing Methods 0.000 abstract description 19
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000010186 staining Methods 0.000 abstract 1
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Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、所定の温度以上に加熱した場合に粘着性が低下又は消滅する粘着シートに関する。更に詳しくは、加熱した場合であっても粘着剤層が基材から剥離し難く、被着体に糊残りの生じ難い粘着シートに関する。 The present invention relates to an adhesive sheet whose adhesiveness is reduced or disappears when heated to a predetermined temperature or higher. More specifically, the present invention relates to a pressure-sensitive adhesive sheet in which the pressure-sensitive adhesive layer is hardly peeled off from the substrate even when heated, and adhesive residue is hardly generated on the adherend.
適度な粘着力で被着体に貼り付けることができるとともに、使用目的を終え不要となった後には簡単に剥離することのできる再剥離性粘着シートは、例えば、封筒や精密機械収納用ケース等のシール部分、壁紙、ラベル、車のバンパーや電線等の取り付け、フレキシブルプリント基板（ＦＰＣ）製造工程における裏打用シートやメッキ工程でのマスク材、並びに半導体ウェハの切断工程、及び積層セラミックコンデンサーの小片化加工工程における仮止めシート等として、電気・電子業界において広く用いられている。このような再剥離性シートとしては、基材上に熱膨張性微小球を含有する粘着剤層を設けた粘着シート（例えば、特許文献１〜４参照）等が提案され、用いられている。 A releasable adhesive sheet that can be attached to an adherend with an appropriate adhesive force and can be easily peeled off after it has been used and is no longer needed, such as an envelope or a case for storing precision machines. Seal parts, wallpaper, labels, mounting of car bumpers, electric wires, etc., backing sheet in flexible printed circuit board (FPC) manufacturing process, mask material in plating process, semiconductor wafer cutting process, and monolithic ceramic capacitor pieces It is widely used in the electrical and electronic industry as a temporary fixing sheet in the chemical processing step. As such a releasable sheet, a pressure-sensitive adhesive sheet (for example, see Patent Documents 1 to 4) provided with a pressure-sensitive adhesive layer containing thermally expandable microspheres has been proposed and used.
特許文献１〜４において開示されたタイプの粘着シートは、被着体と粘着剤層との界面に凹凸を発生させることにより被着体との接触面積が小さくなり、粘着力が低下するものである。従って、他のタイプの粘着シートに比べて、被着体を容易に剥離させることができる。また、再剥離性粘着シートのなかでも、初期剥離力を高くすることができる。従って、被着体を加工する際に、強い力が加わる工程、例えば、積層セラミックコンデンサーの小片化加工工程や処理液等に浸漬させるような工程、例えばメッキ工程等、各種工程で用いられている。 The pressure-sensitive adhesive sheet of the type disclosed in Patent Documents 1 to 4 has a reduced contact area with the adherend by generating irregularities at the interface between the adherend and the pressure-sensitive adhesive layer, and the adhesive strength is reduced. is there. Therefore, the adherend can be easily separated as compared with other types of pressure-sensitive adhesive sheets. Moreover, an initial peeling force can be made high also in a releasable adhesive sheet. Therefore, when processing an adherend, it is used in various processes such as a process in which a strong force is applied, for example, a process for slicing a multilayer ceramic capacitor, a process of immersing in a processing solution, etc. .
しかしながら、粘着シートの初期剥離力が高過ぎる場合には、被着体の貼り直し作業や積層セラミックコンデンサーの小片化加工の際に、粘着剤層が基材から剥離する場合があった。基材から剥離した粘着剤層は、被着体側に付着して、いわゆる糊残りを生じ易く、作業効率や加工精度の低下を生ずる場合があった。
本発明は、このような従来技術の有する問題点に鑑みてなされたものであり、その課題とするところは、基材と粘着剤層との密着性、及び被着体との密着性に優れ、被着体の貼り直しが容易であるとともに、被着体について高精度の加工を行うことができ、かつ、加工完了後は、被着体に糊残り等による汚染を生ずることなく容易に剥離可能な粘着シートを提供することにある。 The present invention has been made in view of such problems of the prior art, and the problem is that the adhesion between the substrate and the pressure-sensitive adhesive layer and the adhesion to the adherend are excellent. In addition to easy reattachment of the adherend, high-precision processing can be performed on the adherend, and after completion of processing, the adherend is easily peeled off without causing contamination due to adhesive residue, etc. The object is to provide a pressure-sensitive adhesive sheet.
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、粘着剤層が基材から剥離するという現象は、貼り直し時や加工時に粘着剤層に負荷される外部からの力を、粘着剤層が十分に吸収できないことに起因する現象であることを見出した。そして、粘着剤層の弾性率を所定の範囲に限定することにより、粘着剤層が、負荷される外部からの力を十分に吸収可能となり、上記課題を解決可能であることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that the phenomenon that the pressure-sensitive adhesive layer is peeled off from the base material is caused by an external force applied to the pressure-sensitive adhesive layer during re-sticking or processing. It was found that this is a phenomenon caused by the pressure-sensitive adhesive layer not being able to absorb sufficiently. Then, by limiting the elastic modulus of the pressure-sensitive adhesive layer to a predetermined range, the pressure-sensitive adhesive layer can sufficiently absorb the external force applied, and the above-described problems can be solved. It came to complete.
即ち、本発明によれば、以下に示す粘着シートが提供される。 That is, according to this invention, the adhesive sheet shown below is provided.
［１］フィルム状又はシート状の基材と、前記基材の少なくとも一方の面上に配設される、熱膨張性微小球を含有する粘着剤層と、を備えた粘着シートであって、前記粘着剤層の２５℃における弾性率が、１．０×１０５Ｐａ以上、１．０×１０６Ｐａ以下である粘着シート。 [1] A pressure-sensitive adhesive sheet comprising a film-like or sheet-like base material, and a pressure-sensitive adhesive layer containing thermally expandable microspheres disposed on at least one surface of the base material, The adhesive sheet whose elastic modulus in 25 degreeC of the said adhesive layer is 1.0 * 10 < 5 > Pa or more and 1.0 * 10 < 6 > Pa or less.
［２］前記粘着剤層が、前記熱膨張性微小球、酸価が３０以上のアクリル系粘着剤、前記アクリル系粘着剤と反応し得る架橋剤、及び軟化点が１４０℃以上の粘着付与樹脂を含有する粘着剤組成物が、前記基材の少なくとも一方の面上に層状に塗布されて形成されたものである前記［１］に記載の粘着シート。 [2] The pressure-sensitive adhesive layer is the thermally expandable microsphere, an acrylic pressure-sensitive adhesive having an acid value of 30 or more, a cross-linking agent capable of reacting with the acrylic pressure-sensitive adhesive, and a tackifying resin having a softening point of 140 ° C. or higher. The pressure-sensitive adhesive sheet according to the above [1], wherein the pressure-sensitive adhesive composition containing is coated and formed in a layered manner on at least one surface of the substrate.
［３］前記粘着剤組成物に含有される前記架橋剤の割合が、前記アクリル系粘着剤に対する割合で、０．５当量以下である前記［２］に記載の粘着シート。 [3] The pressure-sensitive adhesive sheet according to [2], wherein a ratio of the crosslinking agent contained in the pressure-sensitive adhesive composition is a ratio with respect to the acrylic pressure-sensitive adhesive and is 0.5 equivalent or less.
［４］下記剥離試験により測定される初期剥離力が、２Ｎ／２５ｍｍ以上、２５Ｎ／２５ｍｍである前記［１］〜［３］のいずれかに記載の粘着シート。
［剥離試験］：ＳＵＳ３０４板をＪＩＳ Ｋ ０２３７に従って処理して得られた被着体の表面に、２３℃、６５％ＲＨの条件下、２０ｍｍ幅の粘着シートを貼付し、０．５時間放置した後、２３℃、６５％ＲＨの条件下、１８０°剥離力を測定し、測定された１８０°剥離力の値を、２５ｍｍ幅の粘着シートを用いた場合の値（Ｎ／２５ｍｍ）に換算する。
[4] The pressure-sensitive adhesive sheet according to any one of [1] to [3], wherein an initial peel force measured by the following peel test is 2 N / 25 mm or more and 25 N / 25 mm.
[Peeling Test]: A 20 mm wide adhesive sheet was applied to the surface of an adherend obtained by treating a SUS304 plate according to JIS K 0237 under conditions of 23 ° C. and 65% RH and left for 0.5 hours. Thereafter, the 180 ° peel force is measured under the conditions of 23 ° C. and 65% RH, and the measured 180 ° peel force value is converted to a value (N / 25 mm) when a 25 mm wide adhesive sheet is used. .
本発明の粘着シートは、基材と粘着剤層との密着性に優れたものであるとともに、被着体との貼り直しも容易であり、かつ、被着体から剥離後も、被着体に糊残り等による汚染が生じ難いものである。また、本発明の粘着シートは、被着体との密着性に優れたものである。従って、被着体の加工時には、被着体と強固に密着可能であるために、高精度の加工を行うことができる。更に、加工完了後は、容易に被着体から剥離可能なものである。 The pressure-sensitive adhesive sheet of the present invention is excellent in adhesion between the substrate and the pressure-sensitive adhesive layer, and can be easily re-attached to the adherend, and even after being peeled off from the adherend. In addition, contamination due to adhesive residue or the like hardly occurs. Moreover, the adhesive sheet of this invention is excellent in adhesiveness with a to-be-adhered body. Accordingly, when processing the adherend, since it can be firmly adhered to the adherend, high-precision processing can be performed. Furthermore, after completion of the processing, it can be easily peeled off from the adherend.
以下、本発明の実施の最良の形態について説明するが、本発明は以下の実施の形態に限定されるものではなく、本発明の趣旨を逸脱しない範囲で、当業者の通常の知識に基づいて、以下の実施の形態に対し適宜変更、改良等が加えられたものも本発明の範囲に入ることが理解されるべきである。 BEST MODE FOR CARRYING OUT THE INVENTION The best mode for carrying out the present invention will be described below, but the present invention is not limited to the following embodiment, and is based on the ordinary knowledge of those skilled in the art without departing from the gist of the present invention. It should be understood that modifications and improvements as appropriate to the following embodiments also fall within the scope of the present invention.
本発明の粘着シートの一実施形態は、フィルム状又はシート状の基材と、基材の少なくとも一方の面上に配設される熱膨張性微小球を含有する粘着剤層と、を備えた粘着シートであり、粘着剤層の２５℃における弾性率が、１．０×１０５Ｐａ以上、１．０×１０６Ｐａ以下のものである。以下、その詳細について説明する。 One embodiment of the pressure-sensitive adhesive sheet of the present invention includes a film-like or sheet-like base material, and a pressure-sensitive adhesive layer containing thermally expandable microspheres disposed on at least one surface of the base material. It is an adhesive sheet, and the elastic modulus at 25 ° C. of the adhesive layer is 1.0 × 10 5 Pa or more and 1.0 × 10 6 Pa or less. The details will be described below.
本実施形態の粘着シートを構成する基材の材質は特に制約されず、粘着シートの利用分野に応じて適宜選択することができる。例えば、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリエチレン、ポリカーボネート、トリアセチルセルロース、セロハン、ポリイミド、ポリアミド、ポリフェニレンスルフィド、ポリエーテルイミド、ポリエーテルスルホン、芳香族ポリアミド、ポリスルホン等の合成樹脂によって基材を構成することができる。基材は、透明であっても、各種顔料や染料を配合して着色したものであってもよい。また、その表面がマット状に加工された基材を用いることもできる。 The material of the base material which comprises the adhesive sheet of this embodiment is not restrict | limited in particular, According to the utilization field of an adhesive sheet, it can select suitably. For example, the base material is composed of a synthetic resin such as polyethylene terephthalate, polyethylene naphthalate, polyethylene, polycarbonate, triacetylcellulose, cellophane, polyimide, polyamide, polyphenylene sulfide, polyetherimide, polyethersulfone, aromatic polyamide, polysulfone, etc. Can do. The substrate may be transparent or may be colored by blending various pigments and dyes. Moreover, the base material by which the surface was processed into the mat shape can also be used.
粘着シートが５０〜９０℃程度の温度となる環境で長時間さらされる分野で使用する場合には、寸法変化やカール発生等を回避すべく、ＪＩＳ Ｃ ２３１８で定義される加熱収縮率が０．５％以下の基材を用いることが好ましく、０．２％以下の基材を用いることが更に好ましい。具体的には、ポリエチレンテレフタレートフィルム、及びポリエチレンナフタレートフィルムのうちから、加熱収縮率が０．２％以下であるのものを選択するとよい。 When used in a field where the pressure-sensitive adhesive sheet is exposed to an environment where the temperature is about 50 to 90 ° C. for a long time, the heat shrinkage rate defined by JIS C 2318 is 0.00 to avoid dimensional change and curling. It is preferable to use a substrate of 5% or less, and it is more preferable to use a substrate of 0.2% or less. Specifically, a polyethylene terephthalate film and a polyethylene naphthalate film having a heat shrinkage of 0.2% or less may be selected.
基材の厚さは、粘着シートの利用分野に応じて適宜選択することができる。基材の厚さは、具体的には、２５〜２５０μｍであることが好ましい。粘着シートの用途が、切断及び小片化加工時の被着体保持の用途である場合、基材の厚さは２５〜２５０μｍであることが好ましい。但し、被着体がセラミック系シートであり、このセラミック系シートを小片化加工する際の保持に粘着シートを用いる場合には、基材の厚さは１００〜１８８μｍであることが好ましい。 The thickness of a base material can be suitably selected according to the utilization field of an adhesive sheet. Specifically, the thickness of the substrate is preferably 25 to 250 μm. When the use of the pressure-sensitive adhesive sheet is a use for holding an adherend during cutting and fragmentation, the thickness of the substrate is preferably 25 to 250 μm. However, when the adherend is a ceramic sheet, and the pressure-sensitive adhesive sheet is used for holding when the ceramic sheet is cut into pieces, the thickness of the base material is preferably 100 to 188 μm.
基材には、公知の添加剤、耐熱安定剤、耐酸化安定剤、耐候安定剤、紫外線吸収剤、帯電防止剤等を含有させることができる。また、基材と粘着剤層との密着性を向上させるために、基材の粘着剤層が配設される面に表面処理を施すこと、及び／又は、基材と粘着層との間に接着性を有する中間層を介在させることが好ましい。表面処理としては、例えば（１）コロナ放電処理やグロー放電処理等の放電処理、（２）プラズマ処理、（３）火炎処理、（４）オゾン処理、（５）紫外線処理や電子線、放射線処理等の電離活性線処理、（６）サンドマット処理やヘアライン処理等の粗面化処理、（７）化学薬品処理等を挙げることができる。また、中間層としては、例えば、粘着剤層から熱膨張性微小球を含有しない粘着剤層等の、基材との密着性が膨張性微小球含有粘着層よりも高いものが用いることができる。なお、中間層の厚さは、１〜１００μｍであることが好ましく、基材との密着性、生産性の観点からは、１０〜５０μｍであることが更に好ましい。 The substrate can contain known additives, heat stabilizers, oxidation stabilizers, weathering stabilizers, ultraviolet absorbers, antistatic agents, and the like. Moreover, in order to improve the adhesiveness of a base material and an adhesive layer, surface treatment is performed to the surface where the adhesive layer of a base material is arrange | positioned, and / or between a base material and an adhesive layer. It is preferable to interpose an intermediate layer having adhesiveness. Examples of the surface treatment include (1) discharge treatment such as corona discharge treatment and glow discharge treatment, (2) plasma treatment, (3) flame treatment, (4) ozone treatment, and (5) ultraviolet treatment, electron beam, and radiation treatment. Ionizing active ray treatment such as (6) surface roughening treatment such as sand mat treatment and hairline treatment, and (7) chemical treatment. Moreover, as an intermediate | middle layer, what has higher adhesiveness with a base material, such as an adhesive layer which does not contain a thermally expansible microsphere from an adhesive layer, can use the expandable microsphere containing adhesive layer. . In addition, it is preferable that the thickness of an intermediate | middle layer is 1-100 micrometers, and it is still more preferable that it is 10-50 micrometers from a viewpoint of adhesiveness with a base material and productivity.
本実施形態の粘着シートは、基材の少なくとも一方の面上に、熱膨張性微小球を含有する粘着剤層が配設された積層構造を有するものである。この粘着剤層の、２５℃における弾性率は、１．０×１０５Ｐａ以上、１．０×１０６Ｐａ以下、好ましくは１．０×１０５Ｐａ以上、１．０×１０６Ｐａ未満、更に好ましくは２．０×１０５Ｐａ以上、１．０×１０６Ｐａ未満である。 The pressure-sensitive adhesive sheet of this embodiment has a laminated structure in which a pressure-sensitive adhesive layer containing thermally expandable microspheres is disposed on at least one surface of a substrate. The elastic modulus at 25 ° C. of this pressure-sensitive adhesive layer is 1.0 × 10 5 Pa or more and 1.0 × 10 6 Pa or less, preferably 1.0 × 10 5 Pa or more and less than 1.0 × 10 6 Pa. More preferably, it is 2.0 × 10 5 Pa or more and less than 1.0 × 10 6 Pa.
なお、本発明で弾性率の測定温度を２５℃とするのは、この粘着シートと被着体との貼り合わせが通常２３℃から２５℃（作業温度）で行われることが多いためであり、この作業温度で弾性率を測定することにより、実際の作業時での基材と粘着剤層との密着性を把握することができるからである。 In the present invention, the elastic modulus measurement temperature is set to 25 ° C. because the adhesion between the pressure-sensitive adhesive sheet and the adherend is usually performed at 23 ° C. to 25 ° C. (working temperature). This is because by measuring the elastic modulus at this working temperature, it is possible to grasp the adhesion between the base material and the pressure-sensitive adhesive layer during actual work.
また、粘着剤層の２５℃における弾性率が１．０×１０５Ｐａ未満であると、粘着シートの初期剥離力が低下したり、加熱発泡させても表面にべたつきが残る。この初期剥離力の低下は、被着体との密着性の低下につながり、加熱発泡後であっても表面にべたつきが残ることは、粘着シートと被着体との剥離性の低下につながる。 Moreover, when the elastic modulus at 25 ° C. of the pressure-sensitive adhesive layer is less than 1.0 × 10 5 Pa, the initial peeling force of the pressure-sensitive adhesive sheet is reduced, or stickiness remains on the surface even when heated and foamed. This decrease in the initial peel force leads to a decrease in adhesion to the adherend, and stickiness on the surface even after heat foaming leads to a decrease in the peelability between the adhesive sheet and the adherend.
また、粘着シートとして、微粘着性のものとの差別化が困難となり、剥離性の面で熱膨張性微小球を用いる利点がなくなる。一方、粘着剤層の２５℃における弾性率が１．０×１０６Ｐａを超えると、基材と粘着剤層との密着性が低下してしまい、粘着剤層上に貼付した被着体の貼り直しや、加工の際に加わる力を十分に吸収することができなくなる。このために、粘着剤層の一部又は全部が基材から剥離し易くなり、被着体に粘着剤層が付着してしまうために好ましくない。 In addition, it becomes difficult to differentiate the adhesive sheet from the slightly adhesive one, and the advantage of using the heat-expandable microsphere in terms of peelability is lost. On the other hand, when the elastic modulus at 25 ° C. of the pressure-sensitive adhesive layer exceeds 1.0 × 10 6 Pa, the adhesion between the base material and the pressure-sensitive adhesive layer decreases, and the adherend adhered on the pressure-sensitive adhesive layer The force applied during re-sticking or processing cannot be absorbed sufficiently. For this reason, it becomes unpreferable because a part or all of an adhesive layer becomes easy to peel from a base material, and an adhesive layer adheres to a to-be-adhered body.
本実施形態の粘着シートの初期剥離力は、２Ｎ／２５ｍｍ以上、２５Ｎ／２５ｍｍ以下であることが好ましく、２．５〜７．５Ｎ／２５ｍｍであることが更に好ましく、３〜７Ｎ／２５ｍｍであることが特に好ましい。初期剥離力が２Ｎ／２５ｍｍ未満であると、被着体との間で十分な密着性が発揮され難くなる傾向にある。 The initial peel force of the pressure-sensitive adhesive sheet of this embodiment is preferably 2 N / 25 mm or more and 25 N / 25 mm or less, more preferably 2.5 to 7.5 N / 25 mm, and 3 to 7 N / 25 mm. It is particularly preferred. When the initial peeling force is less than 2 N / 25 mm, sufficient adhesion to the adherend tends to be difficult to be exhibited.
また、初期剥離力が２５Ｎ／２５ｍｍを超えると被着体との密着性が強くなりすぎるため、加熱発泡後、被着体が剥離し難くなるので好ましくない。なお、本明細書にいう「初期剥離力」は、以下に示す剥離試験によって測定される物性値をいう。 In addition, if the initial peeling force exceeds 25 N / 25 mm, the adherence to the adherend becomes too strong, and thus the adherend becomes difficult to peel after heating and foaming, which is not preferable. The “initial peel force” in the present specification refers to a physical property value measured by the following peel test.
［剥離試験］：ＳＵＳ３０４板をＪＩＳ Ｋ ０２３７に従って処理して得られた被着体の表面に、２３℃、６５％ＲＨの条件下、２０ｍｍ幅の粘着シートを貼付し、０．５時間放置した後、２３℃、６５％ＲＨの条件下、１８０°剥離力を測定し、測定された１８０°剥離力の値を、２５ｍｍ幅の粘着シートを用いた場合の値（Ｎ／２５ｍｍ）に換算する。 [Peeling Test]: A 20 mm wide adhesive sheet was applied to the surface of an adherend obtained by treating a SUS304 plate according to JIS K 0237 under conditions of 23 ° C. and 65% RH and left for 0.5 hours. Thereafter, the 180 ° peel force is measured under the conditions of 23 ° C. and 65% RH, and the measured 180 ° peel force value is converted to a value (N / 25 mm) when a 25 mm wide adhesive sheet is used. .
粘着剤層は、所定の粘着剤組成物を、基材上の少なくとも一方の面上に層状に塗布することにより形成することができる。粘着剤組成物には、（ａ）熱膨張性微小球の他に、例えば（ｂ）粘着剤、（ｃ）架橋剤、及び（ｄ）所望により用いられる粘着付与樹脂等の成分が含有される。なお、これら各成分の種類及び／又は含有割合を適宜調製することにより、形成される粘着剤層の弾性率を前述の所定の範囲内とすることができる。 The pressure-sensitive adhesive layer can be formed by applying a predetermined pressure-sensitive adhesive composition in a layered manner on at least one surface on the substrate. In addition to (a) thermally expandable microspheres, the adhesive composition contains components such as (b) an adhesive, (c) a crosslinking agent, and (d) an optional tackifier resin. . In addition, the elasticity modulus of the adhesive layer formed can be made into the above-mentioned predetermined range by adjusting suitably the kind and / or content rate of each of these components.
（ａ）熱膨張性微小球
熱膨張性微小球としては、弾性を有する殻内に、加熱により容易にガス化して膨張する物質を内包させた微小球を好適例として挙げることができる。加熱により容易にガス化して膨張する物質としては、例えばイソブタン、プロパン、ペンタン等を挙げることができる。また、殻は、熱溶融性物質や熱膨張により破壊する物質等で形成されたものを好適例として挙げることができる。殻を形成する物質としては、例えば、塩化ビニリデン−アクリロニトリル共重合体、ポリビニルアルコール、ポリビニルブチラール、ポリメチルメタクリレート、ポリアクリロニトリル、ポリ塩化ビニリデン、ポリスルホン等を挙げることができる。熱膨張性微小球の市販品としては、例えば「マイクロスフェア」（商品名、松本油脂製薬社製）等を挙げることができる。
(A) Thermally expandable microsphere As a thermally expandable microsphere, the microsphere which included the substance which expands easily by gasifying by heating in the shell which has elasticity can be mentioned as a suitable example. Examples of the substance that easily gasifies and expands by heating include isobutane, propane, and pentane. A preferable example of the shell is a shell formed of a hot-melt material or a material that is destroyed by thermal expansion. Examples of the substance forming the shell include vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene chloride, and polysulfone. Examples of commercially available products of thermally expandable microspheres include “Microsphere” (trade name, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.).
熱膨張性微小球は、粘着シートの使用温度を考慮して、そのガス化温度（熱膨張温度）が好適なものを適宜選択すればよい。具体的には、グリーンシートや半導体装置、及び電子部品パッケージなどの切断加工、小片化加工等を行う場合、その熱膨張温度が、その加工温度よりも、２５℃以上高い温度のものを用いることが好ましい。また、熱膨張性微小球の体積膨張率は、５倍以上であることが好ましく、７倍以上であることが更に好ましく、１０倍以上であることが特に好ましい。熱膨張性微小球の体積膨張率が５倍以上であると、加熱処理することによって粘着層の粘着力を効率よく低下させることができる。なお、熱膨張性微小球の殻は、前記体積膨張率となるまで膨張した場合であっても破裂しない、適度な強度を有するものであることが好ましい。熱膨張性微小球の大きさは、粘着シートの用途により適宜選択すればよい。具体的には、質量平均粒径で５〜５０μｍであることが好ましい。 The heat-expandable microspheres may be appropriately selected in consideration of the use temperature of the pressure-sensitive adhesive sheet and having a suitable gasification temperature (thermal expansion temperature). Specifically, when cutting or cutting a green sheet, a semiconductor device, or an electronic component package, the thermal expansion temperature should be 25 ° C. higher than the processing temperature. Is preferred. Further, the volume expansion coefficient of the thermally expandable microsphere is preferably 5 times or more, more preferably 7 times or more, and particularly preferably 10 times or more. When the volume expansion coefficient of the thermally expandable microsphere is 5 times or more, the adhesive force of the adhesive layer can be efficiently reduced by heat treatment. In addition, it is preferable that the shell of the thermally expandable microsphere has an appropriate strength that does not rupture even when the shell expands to the volume expansion coefficient. What is necessary is just to select the magnitude | size of a thermally expansible microsphere suitably by the use of an adhesive sheet. Specifically, the mass average particle size is preferably 5 to 50 μm.
熱膨張性微小球は単独でも用いてもよいが、二種以上を組み合わせて用いることもできる。二種以上の組み合わせとしては、（１）ガス（内包される物質）が異なる組み合わせ、（２）質量平均粒径が異なる組み合わせ、（３）殻を構成する材質が異なる組み合わせ、（４）殻の厚さが異なる組み合わせ、（５）前記（１）〜（４）相互の組み合わせ、を挙げることができる。 Thermally expandable microspheres may be used alone or in combination of two or more. As combinations of two or more, (1) combinations with different gases (encapsulated substances), (2) combinations with different mass average particle sizes, (3) combinations with different materials constituting the shell, (4) Combinations with different thicknesses can be mentioned: (5) (1) to (4) mutual combinations.
一般に、粘着シートの剥離に要する時間は、配合される熱膨張性微小球の種類によって定まる。例えば、熱膨張性微小球が、１２０℃、３０分間で膨張のピークに到達する場合、剥離に際しての加熱条件は、通常、１２０℃、３０分となる。但し、作業工程やスケジュール等により、加熱時間が３０分を超える場合がある。加熱時間が３０分を超えると、膨張した粘着剤層が萎んでくる。例えば、１２０℃、３０分間加熱した場合、粘着剤層の膨張倍率は約３倍であるのに対し、１２０℃、９０分間加熱した場合、粘着剤層の膨張倍率は約１．５倍である。粘着剤層の萎みは、被着体と粘着剤層との再密着性の原因となり、被着体が粘着シートから容易に剥離できなくなる場合がある。 Generally, the time required for peeling off the adhesive sheet is determined by the type of thermally expandable microspheres to be blended. For example, when the thermally expandable microspheres reach the peak of expansion at 120 ° C. for 30 minutes, the heating condition for peeling is usually 120 ° C. for 30 minutes. However, the heating time may exceed 30 minutes depending on the work process and schedule. When the heating time exceeds 30 minutes, the expanded adhesive layer is deflated. For example, when heated at 120 ° C. for 30 minutes, the expansion ratio of the pressure-sensitive adhesive layer is about 3 times, whereas when heated at 120 ° C. for 90 minutes, the expansion ratio of the pressure-sensitive adhesive layer is about 1.5 times. . The wrinkle of the pressure-sensitive adhesive layer causes re-adhesion between the adherend and the pressure-sensitive adhesive layer, and the adherend may not be easily peeled from the pressure-sensitive adhesive sheet.
ここで、二種以上の熱膨張性微小球を組み合わせると、粘着剤層の萎みを抑制することが可能となるために好ましい。具体的には、第一の熱膨張性微小球と、この第一の熱膨張性微小球に比してその質量平均粒径が大きい第二の熱膨張性微小球を組み合わせて使用することが更に好ましく、第二の熱膨張性微小球１００質量部に対して、５〜５０質量部の第一の熱膨張性微小球を配合することが特に好ましい。 Here, it is preferable to combine two or more kinds of thermally expandable microspheres because it is possible to suppress the wrinkling of the pressure-sensitive adhesive layer. Specifically, the first thermally expandable microsphere and the second thermally expandable microsphere having a mass average particle size larger than that of the first thermally expandable microsphere may be used in combination. More preferably, it is particularly preferable to blend 5 to 50 parts by mass of the first thermally expandable microsphere with respect to 100 parts by mass of the second thermally expandable microsphere.
また、熱膨張性微小球は、その粒度分布を調整してから使用することが好ましい。熱膨張性微小球の粒度分布を調整して用いることにより、形成される粘着剤層の表面の平滑性を向上させることができるとともに、熱膨張性微小球の膨張時における粘着剤層の表面凹凸を均一にすることができる。粒度分布の調整は、使用する熱膨張性微小球に含まれる比較的の大きな粒径のものを、遠心力型風力分級機、乾式分級機、篩過機等で分級して除去すればよい。平均粒径に比して大きな粒径粒子を除去することにより、形成される粘着剤層の表面の平滑性を向上させることができる。 Further, it is preferable to use the thermally expandable microsphere after adjusting its particle size distribution. By adjusting the particle size distribution of the heat-expandable microspheres, the surface smoothness of the formed pressure-sensitive adhesive layer can be improved, and the surface irregularities of the pressure-sensitive adhesive layer when the heat-expandable microspheres expand Can be made uniform. The particle size distribution may be adjusted by classifying and removing particles having a relatively large particle size contained in the heat-expandable microspheres to be used with a centrifugal air classifier, a dry classifier, a sieving machine, or the like. By removing particles having a larger particle size than the average particle size, the smoothness of the surface of the pressure-sensitive adhesive layer to be formed can be improved.
また、熱膨張性微小球を分級することにより、形成される粘着剤層の厚さを調整し易くなる。例えば、粘着剤層の厚さを２０μｍ程度にする場合、質量平均粒径が８μｍ程度の熱膨張性微小球を使用することの他、質量平均粒径が１５μｍ程度のものから、大粒径（例えば、粒径が２０μｍ以上）のものを分級して除去した熱膨張性微小球を使用することができる。このように熱膨張性微小球を分級する方法によれば、これまで使用していた熱膨張性微小球をそのまま使用することができる。従って、膨張特性、挙動等を新たに把握する必要がなく、開発時間を短縮し、開発効率を向上させることができる。 Moreover, it becomes easy to adjust the thickness of the adhesive layer formed by classifying a thermally expansible microsphere. For example, when the thickness of the pressure-sensitive adhesive layer is set to about 20 μm, in addition to using thermally expandable microspheres having a mass average particle size of about 8 μm, those having a mass average particle size of about 15 μm, For example, thermally expandable microspheres obtained by classifying and removing particles having a particle diameter of 20 μm or more can be used. Thus, according to the method of classifying thermally expandable microspheres, the thermally expandable microspheres used so far can be used as they are. Therefore, it is not necessary to newly grasp expansion characteristics, behavior, etc., and development time can be shortened and development efficiency can be improved.
（ｂ）アクリル系粘着剤
アクリル系粘着剤としては、形成される粘着剤層の弾性率を好ましい範囲に調整できるものであれば、特に制限はない。但し、その酸価が３０以上のアクリル系粘着剤を用いることが好ましい。アクリル系粘着剤の酸価を３０以上とすることにより、架橋剤を用いて架橋した場合に十分な架橋密度とすることができる。また、架橋剤と反応しなかった未反応の官能基が基材と反応し易くなるため、基材と粘着剤層との密着性が向上するために好ましい。なお、未反応の官能基は、被着体とも反応し易くなる。従って、高温条件下においても被着体との密着性が十分に発揮されるとともに、熱膨張性微小球の膨張後においては、基材と粘着剤層との密着性が向上する。
(B) Acrylic pressure-sensitive adhesive The acrylic pressure-sensitive adhesive is not particularly limited as long as the elastic modulus of the formed pressure-sensitive adhesive layer can be adjusted within a preferable range. However, it is preferable to use an acrylic pressure-sensitive adhesive having an acid value of 30 or more. By setting the acid value of the acrylic pressure-sensitive adhesive to 30 or more, a sufficient crosslinking density can be obtained when crosslinking is performed using a crosslinking agent. Moreover, since the unreacted functional group which did not react with a crosslinking agent becomes easy to react with a base material, since the adhesiveness of a base material and an adhesive layer improves, it is preferable. Note that the unreacted functional group easily reacts with the adherend. Accordingly, the adhesion with the adherend is sufficiently exhibited even under high temperature conditions, and the adhesion between the base material and the pressure-sensitive adhesive layer is improved after the expansion of the thermally expandable microspheres.
基材や被着体との密着性向上の観点からは、アクリル系粘着剤の酸価は、４０〜５０であることが更に好ましい。なお、本明細書にいう「酸価」とは、試料（アクリル系粘着剤）１ｇ中に含まれる遊離脂肪酸や樹脂酸を中和するのに要する水酸化カリウムの量（ｍｇ）をいい、ＪＩＳ Ｋ ００７０に準拠して測定され、下記式（１）から中和滴定法により算出することができる。 From the viewpoint of improving the adhesion to the substrate or adherend, the acid value of the acrylic pressure-sensitive adhesive is more preferably 40 to 50. As used herein, “acid value” refers to the amount (mg) of potassium hydroxide required to neutralize free fatty acids and resin acids contained in 1 g of a sample (acrylic adhesive). It is measured according to K 0070 and can be calculated by the neutralization titration method from the following formula (1).
［数１］
酸価（Ａ）＝Ｂ×Ｆ×５．６１１／Ｓ （１）
〔Ｂ：測定に用いた０．１ｍｏｌ／Ｌ水酸化カリウムのエタノール溶液の量（ｍＬ）、Ｆ：０．１ｍｏｌ／Ｌ水酸化カリウムのエタノール溶液のファクター、Ｓ：試料の質量（ｇ）、５．６１１：水酸化カリウムの式量（５６．１１×１／１０）〕
[Equation 1]
Acid value (A) = B × F × 5.661 / S (1)
[B: amount of 0.1 mol / L potassium hydroxide ethanol solution used for measurement (mL), F: factor of 0.1 mol / L potassium hydroxide ethanol solution, S: mass of sample (g), 5 .611: Formula weight of potassium hydroxide (56.11 × 1/10)]
アクリル系粘着剤の重量平均分子量は、１万〜２００万であることが好ましく、１０万〜１５０万であることが更に好ましく、２０万〜１００万であることが特に好ましい。アクリル系粘着剤の重量平均分子量が上記範囲内であると、高精度の加工を行なうのに十分な剥離力を有し、かつ被着体への粘着剤層の付着もなく、加工後の剥離性も良好である。 The weight average molecular weight of the acrylic pressure-sensitive adhesive is preferably 10,000 to 2,000,000, more preferably 100,000 to 1,500,000, and particularly preferably 200,000 to 1,000,000. When the weight average molecular weight of the acrylic pressure-sensitive adhesive is within the above range, it has sufficient peeling force to perform high-precision processing, and there is no adhesion of the pressure-sensitive adhesive layer to the adherend, and peeling after processing The property is also good.
アクリル系粘着剤は、架橋剤と反応し得るものである。このアクリル系粘着剤には、アクリル酸アルキルエステル及び／又はメタクリル酸アルキルエステルと、架橋剤と反応し得る官能基を有する単量体との共重合体が包含される。アクリル酸アルキルエステル、及びメタクリル酸アルキルエステルの「アルキルエステル」としては、例えば、メチルエステル、エチルエステル、プロピルエステル、イソプロピルエステル、ブチルエステル、イソブチルエステル、ｓ−ブチルエステル、ｔ−ブチルエステル、ペンチルエステル、ヘキシルエステル、ヘプチルエステル、オクチルエステル、イソオクチルエステル、２−エチルヘキシルエステル、イソデシルエステル、ドデシルエステル、トリデシルエステル、ペンタデシルエステル、オクタデシルエステル、ノナデシルエステル、エイコシルエステル等を挙げることができる。架橋剤と反応し得る官能基としては、カルボキシル基、ヒドロキシル基を挙げることができる。 The acrylic pressure-sensitive adhesive can react with the crosslinking agent. The acrylic pressure-sensitive adhesive includes a copolymer of an acrylic acid alkyl ester and / or a methacrylic acid alkyl ester and a monomer having a functional group capable of reacting with a crosslinking agent. Examples of the "alkyl ester" of acrylic acid alkyl ester and methacrylic acid alkyl ester include, for example, methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, s-butyl ester, t-butyl ester, pentyl ester. Hexyl ester, heptyl ester, octyl ester, isooctyl ester, 2-ethylhexyl ester, isodecyl ester, dodecyl ester, tridecyl ester, pentadecyl ester, octadecyl ester, nonadecyl ester, eicosyl ester, etc. . Examples of the functional group capable of reacting with the crosslinking agent include a carboxyl group and a hydroxyl group.
架橋剤と反応し得る官能基がカルボキシル基である単量体としては、アクリル酸、メタクリル酸、カルボキシエチルアクリレート、カルボキシペンチルアクリレート、イタコン酸、マレイン酸、フマル酸、クロトン酸等を挙げることができる。また、架橋剤と反応し得る官能基がヒドロキシル基である単量体としては、アクリル酸ヒドロキシエチル、メタクリル酸ヒドロキシエチル、アクリル酸ヒドロキシプロピル、メタクリル酸ヒドロキシプロピル、アクリル酸ヒドロキシブチル、メタクリル酸ヒドロキシブチル、アクリル酸ヒドロキシヘキシル、メタクリル酸ヒドロキシヘキシル、アクリル酸ヒドロキシオクチル、メタクリル酸ヒドロキシオクチル、アクリル酸ヒドロキシデシル、メタクリル酸ヒドロキシデシル、アクリル酸ヒドロキシラウリル、メタクリル酸ヒドロキシラウリル等を挙げることができる。 Examples of the monomer whose functional group capable of reacting with the crosslinking agent is a carboxyl group include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid. . Moreover, as a monomer whose functional group which can react with a crosslinking agent is a hydroxyl group, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate And hydroxyhexyl acrylate, hydroxyhexyl methacrylate, hydroxyoctyl acrylate, hydroxyoctyl methacrylate, hydroxydecyl acrylate, hydroxydecyl methacrylate, hydroxylauryl acrylate, and hydroxylauryl methacrylate.
架橋剤と反応し得る官能基を有する単量体は、単独で又は二種以上を組み合わせて用いることができる。（メタ）アクリル酸アルキルエステルと、架橋剤と反応し得る官能基を有する単量体との比は、質量比で、９２：８〜９８：２の範囲であることが好ましい。この範囲よりも、架橋剤と反応し得る官能基を有する単量体の配合比が少ないと、熱膨張性微小球が膨張した場合に、被着体と粘着剤層との剥離性が損なわれる傾向にある。一方、この範囲よりも、架橋剤と反応し得る官能基を有する単量体の配合比が多いと、被着体と粘着剤層との粘着力が乏しくなる傾向にある。被着体と粘着剤層との粘着性及び剥離性を向上させるという観点からは、（メタ）アクリル酸アルキルエステルと、架橋剤と反応し得る官能基を有する単量体との比は、質量比で、９５：５〜９３：７であることが更に好ましい。 Monomers having a functional group capable of reacting with a crosslinking agent can be used alone or in combination of two or more. The ratio between the (meth) acrylic acid alkyl ester and the monomer having a functional group capable of reacting with the crosslinking agent is preferably in the range of 92: 8 to 98: 2 in terms of mass ratio. If the blending ratio of the monomer having a functional group capable of reacting with the crosslinking agent is less than this range, the peelability between the adherend and the adhesive layer is impaired when the thermally expandable microspheres expand. There is a tendency. On the other hand, when there are many compounding ratios of the monomer which has a functional group which can react with a crosslinking agent than this range, it exists in the tendency for the adhesive force of a to-be-adhered body and an adhesive layer to become scarce. From the viewpoint of improving the adhesion and peelability between the adherend and the pressure-sensitive adhesive layer, the ratio between the (meth) acrylic acid alkyl ester and the monomer having a functional group capable of reacting with the crosslinking agent is More preferably, the ratio is 95: 5 to 93: 7.
なお、所望により、（メタ）アクリル酸アルキルエステル、及び架橋剤と反応し得る官能基を有する単量体以外のその他の単量体を併用することもできる。その他の単量体としては、例えば、スチレン、酢酸ビニル、アクリロニトリル、アクリルアミド、ポリエチレングリコールアクリレート、Ｎ−ビニルピロリドン、テトラフルフリルアクリレート等を挙げることができる。 If desired, other monomers other than the (meth) acrylic acid alkyl ester and the monomer having a functional group capable of reacting with the crosslinking agent may be used in combination. Examples of other monomers include styrene, vinyl acetate, acrylonitrile, acrylamide, polyethylene glycol acrylate, N-vinyl pyrrolidone, and tetrafurfuryl acrylate.
アクリル系粘着剤は、上記の単量体成分をラジカル共重合させることによって得ることができる。この場合の共重合法は従来公知であり、乳化重合法、溶液重合法、塊状重合法、懸濁重合法、光重合法等を挙げることができる。また、アクリル系粘着剤のガラス転移温度は、−５０〜−２０℃であることが好ましい。ガラス転移温度が−２０℃超であると、被着体と粘着剤層との粘着力が低下する傾向にある。一方、ガラス転移温度が−５０℃未満であると、加熱処理後の剥離時に糊残りを生じ易くなり、剥離性が良好になり難くなる傾向にある。被着体と粘着剤層との粘着性及び剥離性を向上させるという観点からは、アクリル系粘着剤のガラス転移温度は、−４０℃〜−２５℃であることが更に好ましい。 The acrylic pressure-sensitive adhesive can be obtained by radical copolymerization of the above monomer components. The copolymerization method in this case is conventionally known, and examples thereof include an emulsion polymerization method, a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and a photopolymerization method. Moreover, it is preferable that the glass transition temperature of an acrylic adhesive is -50--20 degreeC. When the glass transition temperature is higher than -20 ° C, the adhesive force between the adherend and the pressure-sensitive adhesive layer tends to decrease. On the other hand, when the glass transition temperature is less than −50 ° C., adhesive residue tends to be generated at the time of peeling after the heat treatment, and the peelability tends to be difficult. From the viewpoint of improving the adhesion and peelability between the adherend and the pressure-sensitive adhesive layer, the glass transition temperature of the acrylic pressure-sensitive adhesive is more preferably −40 ° C. to −25 ° C.
（ｃ）架橋剤
形成された粘着剤層中において、アクリル系粘着剤は、所定の（ｃ）架橋剤で架橋されている。架橋剤は、用いるアクリル系粘着剤の種類に合せて適宜選択すればよく、特に制約はない。架橋剤の具体例としては、イソシアネート系架橋剤、金属キレート架橋剤、エポキシ系架橋剤等を挙げることができる。これらのなかでも、熱膨張性微小球が膨張する温度への加熱後における、被着体からの剥離性を向上させ、被着体への糊残りを防止するといった観点から、エポキシ系架橋剤を用いることが好ましい。エポキシ系架橋剤としては、例えば、ビスフェノール系エポキシ樹脂（例えば、ビスフェノールＡ型、ビスフェノールＦ型、ビスフェノールＡＤ型）、フェノールノボラック型エポキシ樹脂、エチレングリコールジグリシジルエーテル、１，６−ヘキサンジオールグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ジグリシジルアニリン、ジグリシジルアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル−ｍ−キシレンジアミン、１，３−ビス（Ｎ，Ｎ’−ジグリシジルアミノメチル）シクロヘキサン等を挙げることができる。
(C) Crosslinking agent In the formed adhesive layer, the acrylic adhesive is crosslinked with a predetermined (c) crosslinking agent. The crosslinking agent may be appropriately selected according to the type of acrylic pressure-sensitive adhesive to be used, and is not particularly limited. Specific examples of the crosslinking agent include an isocyanate crosslinking agent, a metal chelate crosslinking agent, and an epoxy crosslinking agent. Among these, from the viewpoint of improving the peelability from the adherend after heating to a temperature at which the thermally expandable microspheres expand, and preventing the adhesive residue on the adherend, an epoxy crosslinking agent is used. It is preferable to use it. Examples of the epoxy crosslinking agent include bisphenol epoxy resins (for example, bisphenol A type, bisphenol F type, bisphenol AD type), phenol novolac type epoxy resins, ethylene glycol diglycidyl ether, 1,6-hexanediol glycidyl ether, Trimethylolpropane triglycidyl ether, diglycidylaniline, diglycidylamine, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane Etc.
常温における被着体との粘着性、及び熱膨張性微小球の膨張後における被着体からの剥離性の面で、多官能のエポキシ系架橋剤が好ましく、４官能のエポキシ系架橋剤が更に好ましい。具体的には、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル−ｍ−キシレンジアミン、１，３−ビス（Ｎ，Ｎ’−ジグリシジルアミノメチル）シクロヘキサンを挙げることができる。但し、これらのエポキシ系架橋剤は、架橋反応速度が遅くなる傾向にある。このため架橋反応が不十分である場合には、粘着剤層の凝集力が低くなり、被着体表面に糊残り等が発生し易くなる場合がある。従って、架橋反応を促進するために、（１）アミン等の触媒を添加する、（２）粘着剤の構成成分としてアミン系官能基を持つ単量体を用いる、（３）架橋剤にアジリジン系架橋剤を併用する、ことが望ましい。特に、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル−ｍ−キシレンジアミン等の架橋剤に、触媒効果を有する３級アミンを添加することが好ましい。 In terms of adhesiveness to the adherend at normal temperature and releasability from the adherend after expansion of the thermally expandable microspheres, a polyfunctional epoxy crosslinking agent is preferable, and a tetrafunctional epoxy crosslinking agent is further provided. preferable. Specific examples include N, N, N ′, N′-tetraglycidyl-m-xylenediamine and 1,3-bis (N, N′-diglycidylaminomethyl) cyclohexane. However, these epoxy crosslinking agents tend to have a slow crosslinking reaction rate. For this reason, when a crosslinking reaction is inadequate, the cohesive force of an adhesive layer becomes low and it may become easy to generate | occur | produce adhesive residue etc. on a to-be-adhered body surface. Accordingly, in order to accelerate the crosslinking reaction, (1) a catalyst such as amine is added, (2) a monomer having an amine functional group is used as a constituent of the pressure-sensitive adhesive, and (3) an aziridine type is used as the crosslinking agent. It is desirable to use a crosslinking agent in combination. In particular, it is preferable to add a tertiary amine having a catalytic effect to a crosslinking agent such as N, N, N ′, N′-tetraglycidyl-m-xylenediamine.
架橋剤は、単独で用いても、二種以上を組み合わせて用いてもよい。架橋剤の配合割合は、前述の熱膨張性微小球、アクリル系粘着剤、及び所望により用いられる、後述する粘着付与樹脂とともに、粘着剤層が好ましい弾性率となるように適宜選択すればよく、特に制限はない。但し、粘着剤組成物に含有される架橋剤の割合は、アクリル系粘着剤に対する割合で、０．５当量以下とするのが基材との密着性が向上するために好ましい。架橋剤の割合が、アクリル系粘着剤に対する割合で０．５当量を超えると、被着体との粘着力が低下し易くなり、熱膨張性微小球を加熱膨張させる前に、被着体と粘着剤層とが剥離し易くなる傾向にあるために好ましくない。基材及び被着体との密着性の面から、粘着剤組成物に含有される架橋剤の割合は、アクリル系粘着剤に対する割合で、１×１０−３〜０．３当量とすることが更に好ましい。 A crosslinking agent may be used independently or may be used in combination of 2 or more type. The blending ratio of the cross-linking agent may be appropriately selected so that the pressure-sensitive adhesive layer has a preferable elastic modulus together with the above-described thermally expandable microspheres, the acrylic pressure-sensitive adhesive, and a tackifier resin described later, if desired. There is no particular limitation. However, the ratio of the crosslinking agent contained in the pressure-sensitive adhesive composition is preferably a ratio with respect to the acrylic pressure-sensitive adhesive and 0.5 equivalent or less because adhesion with the substrate is improved. When the ratio of the cross-linking agent exceeds 0.5 equivalent in terms of the acrylic pressure-sensitive adhesive, the adhesive strength with the adherend tends to decrease, and the thermally expandable microsphere is heated and expanded before the adherend and This is not preferable because the adhesive layer tends to peel off. From the standpoint of adhesion to the substrate and the adherend, the ratio of the crosslinking agent contained in the pressure-sensitive adhesive composition is a ratio with respect to the acrylic pressure-sensitive adhesive, and is 1 × 10 −3 to 0.3 equivalent. Further preferred.
（ｄ）粘着付与樹脂
粘着剤層の２５℃における弾性率を、１．０×１０５Ｐａ以上、１．０×１０６Ｐａ以下の範囲とすると、初期剥離力が低下する傾向にあるため、被着体との密着性が低下する場合がある。このため、被着体の加工精度や加工歩留りが低下する場合も想定される。従って、粘着剤層を形成する粘着剤組成物に（ｄ）粘着付与樹脂を含有させることが、常温付近における被着体との密着性の調整が容易となるために好ましい。粘着付与樹脂としては、その軟化点が１４０℃以上であるものが好ましい。粘着付与樹脂の具体例としては、α−ピネン系、β−ピネン系、ジペンテン系、テルペンフェノール系等のテルペン系樹脂；ガム系、ウッド系、トール油系等の天然系ロジン；これらの天然系ロジンに水素化、不均化、重合、マレイン化、エステル化等の処理をしたロジン系誘導体等のロジン系樹脂；石油樹脂；クマロン−インデン樹脂等を挙げることができる。
(D) Tackifying resin When the elastic modulus at 25 ° C. of the pressure-sensitive adhesive layer is in the range of 1.0 × 10 5 Pa or more and 1.0 × 10 6 Pa or less, the initial peeling force tends to decrease. Adhesion with the adherend may be reduced. For this reason, the case where the processing accuracy of a to-be-adhered body and a process yield fall is also assumed. Therefore, it is preferable that the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer contains (d) a tackifying resin because it is easy to adjust the adhesion to the adherend near normal temperature. The tackifying resin preferably has a softening point of 140 ° C. or higher. Specific examples of tackifying resins include α-pinene-based, β-pinene-based, dipentene-based, terpene-phenol-based terpene-based resins; gum-based, wood-based, tall oil-based natural rosins; Examples thereof include rosin resins such as rosin derivatives obtained by subjecting rosin to hydrogenation, disproportionation, polymerization, maleation, esterification, etc .; petroleum resins; coumarone-indene resins.
これらのなかでも、軟化点が１４０〜１７０℃の範囲内であるものが更に好ましく、１５０〜１６０℃の範囲であるものが特に好ましい。軟化点が上記の範囲内である粘着付与樹脂を用いると、被着体への汚染、糊残りが少ないばかりでなく、作業環境下における被着体との密着性をさらに向上させることが可能となる。また、粘着剤層の弾性率を、所望とする所定の範囲内に調整し易く、しかも粘着剤層の弾性率が１．０×１０６Ｐａ以下であっても初期剥離力を高くすることができるので好ましい。更に、粘着付与樹脂としてテルペンフェノール系の粘着付与樹脂を用いると、被着体への汚染、糊残りが少ないばかりか、５０〜９０℃の環境下での被着体との粘着性が向上するとともに、熱膨張性微小球の膨張後は、被着体から更に容易に剥離可能となる。 Among these, those having a softening point in the range of 140 to 170 ° C are more preferable, and those having a softening point in the range of 150 to 160 ° C are particularly preferable. When a tackifying resin having a softening point within the above range is used, not only is there little contamination and adhesive residue on the adherend, but it is possible to further improve the adhesion to the adherend in the work environment. Become. Moreover, it is easy to adjust the elastic modulus of the pressure-sensitive adhesive layer within a desired predetermined range, and even if the elastic modulus of the pressure-sensitive adhesive layer is 1.0 × 10 6 Pa or less, the initial peeling force can be increased. It is preferable because it is possible. Furthermore, when a terpene phenol-based tackifying resin is used as the tackifying resin, not only the adherend is contaminated and the adhesive residue is small, but also the tackiness with the adherend in an environment of 50 to 90 ° C. is improved. At the same time, after expansion of the thermally expandable microspheres, it can be more easily peeled off from the adherend.
粘着付与樹脂の配合割合は、粘着剤層の弾性率を所望とする所定の数値範囲内に調整することができるように適宜選択すればよく、特に制限はない。但し、粘着剤層の弾性率と初期剥離力の面から、アクリル系粘着剤１００質量部に対して、１０〜１００質量部とすることが好ましい。粘着付与樹脂の配合割合が、アクリル系粘着剤１００質量部に対して、１０質量部未満であると、作業時の被着体の密着性が低下する傾向にある。一方、１００質量部超であると、常温における被着体との貼り付け性が低下する。被着体との密着性、及び常温における貼り付け性の面から、粘着付与樹脂の配合割合を、アクリル系粘着剤１００質量部に対して、１５〜５０質量部とすることが更に好ましい。また、粘着付与樹脂の水酸基価は、３０以上、好ましくは５０〜３００、更に好ましくは１００〜２５０であることが好ましい。粘着付与樹脂の水酸基価が３０未満であると、剥離時に被着体に糊残りが生じ易くなる場合がある。 The blending ratio of the tackifying resin may be appropriately selected so that the elastic modulus of the pressure-sensitive adhesive layer can be adjusted within a desired numerical range, and is not particularly limited. However, it is preferable to set it as 10-100 mass parts with respect to 100 mass parts of acrylic adhesive from the surface of the elasticity modulus of an adhesive layer and initial stage peeling force. When the mixing ratio of the tackifying resin is less than 10 parts by mass with respect to 100 parts by mass of the acrylic pressure-sensitive adhesive, the adherence of the adherend during work tends to decrease. On the other hand, when it is more than 100 parts by mass, the sticking property with the adherend at room temperature decreases. From the standpoint of adhesion to the adherend and stickability at normal temperature, the blending ratio of the tackifier resin is more preferably 15 to 50 parts by mass with respect to 100 parts by mass of the acrylic adhesive. Further, the hydroxyl value of the tackifier resin is 30 or more, preferably 50 to 300, and more preferably 100 to 250. If the hydroxyl value of the tackifying resin is less than 30, adhesive residue may easily occur on the adherend during peeling.
本実施形態の粘着シートを得るには、先ず、前述の各成分を含有する粘着剤組成物を適当な溶剤に溶解又は分散させ、その固形分濃度が２０〜５０質量％の粘着剤層形成塗工液を調製する。次いで、調製した粘着剤層形成塗工液を、基材の少なくとも一方の面上に直接、又は適当な中間層を介して、常法に従って塗布及び乾燥することにより、例えば１０〜１００μｍの厚みの粘着剤層を形成する。なお、粘着剤層の厚みが１００μｍ超であると、加熱処理後の剥離時に凝集破壊が起こり易くなり、良好な剥離性が得られなくなる場合がある。一方、粘着剤層の厚みが１０μｍ未満であると、被着体との十分な粘着力を得難くなる場合がある。 In order to obtain the pressure-sensitive adhesive sheet of this embodiment, first, a pressure-sensitive adhesive composition containing the above-described components is dissolved or dispersed in a suitable solvent, and the pressure-sensitive adhesive layer-forming coating having a solid content concentration of 20 to 50% by mass is prepared. Prepare a working solution. Subsequently, the prepared pressure-sensitive adhesive layer-forming coating solution is applied and dried in accordance with a conventional method directly on at least one surface of the substrate or via an appropriate intermediate layer, for example, with a thickness of 10 to 100 μm. An adhesive layer is formed. In addition, when the thickness of the pressure-sensitive adhesive layer is more than 100 μm, cohesive failure tends to occur at the time of peeling after heat treatment, and good peelability may not be obtained. On the other hand, if the thickness of the pressure-sensitive adhesive layer is less than 10 μm, it may be difficult to obtain sufficient adhesive strength with the adherend.
また、粘着剤層中に残存する揮発分の量（残存揮発分量）によっては、粘着剤層と基材との粘着性や、加熱後における被着体からの剥離性、糊残り性に影響を及ぼす場合がある。従って、粘着剤層中の残存揮発分量を４質量％以下とすることが好ましく、２質量％以下とすることが更に好ましい。なお、粘着剤層形成塗工液には、従来慣用されている各種添加剤、例えば、界面活性剤、潤滑剤、安定剤、粘度調整剤等を添加することができる。 In addition, depending on the amount of volatile matter remaining in the pressure-sensitive adhesive layer (residual volatile matter amount), it may affect the adhesiveness between the pressure-sensitive adhesive layer and the substrate, the peelability from the adherend after heating, and the adhesive residue. May affect. Accordingly, the residual volatile content in the pressure-sensitive adhesive layer is preferably 4% by mass or less, and more preferably 2% by mass or less. In addition, various conventionally used additives such as surfactants, lubricants, stabilizers, viscosity modifiers, and the like can be added to the pressure-sensitive adhesive layer forming coating solution.
以下、本発明を実施例に基づいて具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、以下の実施例において使用する各種物性値の測定方法、及び諸特性の評価方法を次に示す。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In addition, the measurement method of various physical property values and the evaluation method of various properties used in the following examples are shown below.
［弾性率］：粘着シートを構成する粘着剤層の、２０℃および２５℃における弾性率（Ｐａ）を測定した。具体的には、先ず、試料となる粘着剤組成物を所定のシリコーンシート上に塗工・乾燥後に剥離させることにより、厚さ０．１ｍｍ×幅３ｍｍ×長さ１５ｍｍの試料シートを作製した。次いで、作製した試料シートの長手方向の一方の端部を固定式チャックに、他方の端部を可動式チャックに、それぞれ把持した。この状態で、ＴＭＡ４０００Ｓ（ＭＡＣ ＳＣＩＥＮＣＥ社製）を用いて、ＴＭＡ引張モード法により−０．２〜−０．５ｇの荷重を負荷して弾性率（Ｐａ）を測定した。 [Elastic modulus]: The elastic modulus (Pa) at 20 ° C. and 25 ° C. of the pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive sheet was measured. Specifically, first, a sample sheet having a thickness of 0.1 mm, a width of 3 mm, and a length of 15 mm was prepared by peeling a pressure-sensitive adhesive composition as a sample after coating and drying on a predetermined silicone sheet. Next, one end of the prepared sample sheet in the longitudinal direction was held by a fixed chuck, and the other end was held by a movable chuck. In this state, using TMA4000S (manufactured by MAC SCIENCE), the elastic modulus (Pa) was measured by applying a load of -0.2 to -0.5 g by the TMA tensile mode method.
［初期剥離力（ＳＵＳ）］：ＳＵＳ３０４板をＪＩＳ Ｋ ０２３７に従って処理して得られた被着体の表面に、２３℃、６５％ＲＨの条件下、２０ｍｍ幅の粘着シートを貼付し、０．５時間放置して測定用サンプルを用意した。この測定用サンプルを放冷後、２３℃、６５％ＲＨの条件下で１８０°剥離力を測定した。測定した１８０°剥離力の値を、２５ｍｍ幅の粘着シートを用いた場合の値（Ｎ／２５ｍｍ）に換算した。 [Initial peeling force (SUS)]: A 20 mm wide adhesive sheet was applied to the surface of an adherend obtained by treating a SUS304 plate according to JIS K 0237 under conditions of 23 ° C. and 65% RH. A sample for measurement was prepared by leaving for 5 hours. The sample for measurement was allowed to cool, and then the 180 ° peeling force was measured under the conditions of 23 ° C. and 65% RH. The measured 180 ° peeling force value was converted to a value (N / 25 mm) when a 25 mm width adhesive sheet was used.
［剥離性］：ポリビニルブチラール４．４質量部、酸化チタン４４質量部、フタル酸ジエチル２．２質量部、トルエン２４．７質量部、エチルアルコール２４．７質量部を均一に混合・溶解し、塗工液を調製した。この塗工液をシリコーンシート上に塗工・乾燥し厚さ２０μｍの塗工層を形成させ、この塗工層を積層し厚さ３００μｍの積層体を作製した。この積層体を被着体として使用し、その表面に粘着シートを貼付した後、１３０℃のホットプレート上で５分間加熱した。放冷後、室温（２３℃）にて、粘着シートの粘着剤層が被着体から剥離しているか否かを評価数１０で評価し、それらの評価の平均から次の評価基準により評価した。
◎：放冷後、何も力を加えずに被着体より粘着シートが剥離した。
○：粘着シートに指を触れた後、被着体より剥離した。
△：粘着シートに力を加え、剥離した。
×：被着体から剥離が困難であった。
[Peelability]: 4.4 parts by mass of polyvinyl butyral, 44 parts by mass of titanium oxide, 2.2 parts by mass of diethyl phthalate, 24.7 parts by mass of toluene, and 24.7 parts by mass of ethyl alcohol are uniformly mixed and dissolved. A coating solution was prepared. This coating solution was applied and dried on a silicone sheet to form a coating layer having a thickness of 20 μm, and this coating layer was laminated to prepare a laminate having a thickness of 300 μm. This laminate was used as an adherend, an adhesive sheet was attached to the surface, and then heated on a hot plate at 130 ° C. for 5 minutes. After standing to cool, at room temperature (23 ° C.), whether or not the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet was peeled off from the adherend was evaluated with an evaluation number of 10 and evaluated based on the following evaluation criteria from the average of these evaluations. .
A: After cooling, the pressure-sensitive adhesive sheet peeled off from the adherend without applying any force.
○: After touching the adhesive sheet with a finger, it peeled off from the adherend.
(Triangle | delta): Force was applied to the adhesive sheet and it peeled.
X: It was difficult to peel from the adherend.
［汚染性］：前述の「剥離性」の評価において、粘着シートを剥離した被着体の表面の汚染性を評価数１０で評価し、それらの評価の平均から次の評価基準で評価した。
○：全ての評価において、被着体に変色、糊残りが認められない。
△：評価数の１〜４割で被着体に変色又は糊残りが認められる。
×：評価数の５割以上で被着体に変色又は糊残りが認められる。
[Contamination]: In the above-mentioned evaluation of “peelability”, the contamination of the surface of the adherend from which the pressure-sensitive adhesive sheet was peeled was evaluated with an evaluation number of 10, and the average of those evaluations was evaluated according to the following evaluation criteria.
○: No discoloration or adhesive residue was observed on the adherend in all evaluations.
Δ: Discoloration or adhesive residue is observed on the adherend in 10 to 40% of the evaluation number.
X: Discoloration or adhesive residue is observed on the adherend when the evaluation number is 50% or more.
［基材との密着性］：被着体としてガラス板を使用し、その表面に２３℃、６５％ＲＨの環境下で２０ｍｍ幅の粘着シートを貼付し、０．５時間放置してサンプルを用意した。２３℃、６５％ＲＨの環境下で粘着シートをガラス板より剥離し、その際の粘着シートの状態を目視で観察して以下の基準により評価した。
○：基材と粘着剤層とが密着しており、被着体に粘着剤層の付着が認められない。
△：基材と粘着剤層との境界面で部分的に剥離が認められる。
×：基材と粘着剤層との境界面で剥離が認められ、被着体に粘着剤層の付着が認められる。
[Adhesion with substrate]: A glass plate is used as the adherend, and a 20 mm wide adhesive sheet is pasted on the surface in an environment of 23 ° C. and 65% RH. Prepared. The adhesive sheet was peeled from the glass plate in an environment of 23 ° C. and 65% RH, and the state of the adhesive sheet at that time was visually observed and evaluated according to the following criteria.
○: The substrate and the pressure-sensitive adhesive layer are in close contact, and adhesion of the pressure-sensitive adhesive layer is not observed on the adherend.
(Triangle | delta): Peeling is recognized partially in the interface of a base material and an adhesive layer.
X: Peeling is observed at the interface between the base material and the pressure-sensitive adhesive layer, and adhesion of the pressure-sensitive adhesive layer is observed on the adherend.
［粘着剤層の膨張率］：熱風乾燥機を使用して、粘着シートを、（１）温度１２０℃、３０分間で加熱した後の粘着剤層の厚さ、及び（２）温度１２０℃、９０分間加熱した後の粘着剤層の厚さ、をそれぞれ測定した。加熱する前の粘着剤層の厚さから、それぞれの条件で加熱した後の膨張率を算出した。 [Expansion coefficient of pressure-sensitive adhesive layer]: Using a hot air dryer, the pressure-sensitive adhesive sheet was heated (1) at a temperature of 120 ° C. for 30 minutes, and (2) at a temperature of 120 ° C. The thickness of the adhesive layer after heating for 90 minutes was measured. From the thickness of the pressure-sensitive adhesive layer before heating, the expansion coefficient after heating under each condition was calculated.
（実施例１）
熱膨張性微小球（松本油脂製薬社製、商品名「マイクロスフェアＦ５０Ｄ」、平均粒径：１５μｍ）６質量部、アクリル系粘着剤（アクリル酸−アクリル酸ブチル共重合体、質量平均分子量：５１万、ガラス転移温度：−３２℃、酸価：４６）２７質量部、テルペンフェノール系粘着付与樹脂（軟化点：１５０℃、水酸基価：１３０）５質量部、エポキシ系架橋剤（Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル−ｍ−キシレンジアミン）０．１５質量部、及びトルエン６１．８５質量部を均一に混合、溶解し、粘着剤層形成塗工液を調製した。この粘着剤層形成塗工液のエポキシ系架橋剤のアクリル系粘着剤に対する割合は０．０８当量であった。この塗工液を、厚さ１００μｍのポリエチレンテレフタレートシート上にベーカー式アプリケーターにて塗布し、８０℃にて十分乾燥することにより、厚さ５０μｍの粘着剤層を有する再剥離性の粘着シートを作製した。この粘着シートの物性値の測定結果、及び各種特性の評価結果を表１に示す。
Example 1
Thermally expandable microspheres (manufactured by Matsumoto Yushi Seiyaku Co., Ltd., trade name “Microsphere F50D”, average particle size: 15 μm) 6 parts by mass, acrylic adhesive (acrylic acid-butyl acrylate copolymer, mass average molecular weight: 51 Glass transition temperature: −32 ° C., acid value: 46) 27 parts by mass, terpene phenol-based tackifier resin (softening point: 150 ° C., hydroxyl value: 130), 5 parts by mass, epoxy crosslinking agent (N, N, N ', N'-tetraglycidyl-m-xylenediamine) 0.15 parts by mass and 61.85 parts by mass of toluene were uniformly mixed and dissolved to prepare an adhesive layer forming coating solution. The ratio of the epoxy-based crosslinking agent to the acrylic pressure-sensitive adhesive in the pressure-sensitive adhesive layer forming coating solution was 0.08 equivalent. This coating solution is applied to a 100 μm thick polyethylene terephthalate sheet with a baker-type applicator and sufficiently dried at 80 ° C. to produce a releasable pressure sensitive adhesive sheet having a 50 μm thick adhesive layer. did. Table 1 shows the measurement results of the physical property values of this pressure-sensitive adhesive sheet and the evaluation results of various properties.
（実施例２）
熱膨張性微小球として、平均粒径８μｍの熱膨張性微小球（松本油脂製薬社製、商品名「マイクロスフェアＦ８０ＧＳＤ」）２質量部と、前述の実施例１で使用した平均粒径１５μｍの熱膨張性微小球４質量部とを混合したものを用いたこと以外は、前述の実施例１と同様にして粘着シートを作製した。この粘着シートの物性値の測定結果、及び各種特性の評価結果を表１に示す。
(Example 2)
As the thermally expandable microspheres, 2 parts by mass of thermally expandable microspheres having an average particle diameter of 8 μm (manufactured by Matsumoto Yushi Seiyaku Co., Ltd., trade name “Microsphere F80GSD”) and the average particle diameter of 15 μm used in Example 1 described above. A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that a mixture of 4 parts by mass of thermally expandable microspheres was used. Table 1 shows the measurement results of the physical property values of this pressure-sensitive adhesive sheet and the evaluation results of various properties.
（実施例３）
エポキシ系架橋剤（Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル−ｍ−キシレンジアミン）０．３１質量部、テルペンフェノール系粘着付与樹脂（軟化点：１５０℃、水酸基価：１３０）６．６質量部とした以外は、前述の実施例２と同様にして粘着シートを作製した。ここで使用した粘着剤層形成塗工液のエポキシ系架橋剤のアクリル系粘着剤に対する割合は０．１６当量であった。この粘着シートの物性値の測定結果、及び各種特性の評価結果を表１に示す。
(Example 3)
Epoxy crosslinking agent (N, N, N ′, N′-tetraglycidyl-m-xylenediamine) 0.31 part by mass, terpenephenol tackifying resin (softening point: 150 ° C., hydroxyl value: 130) 6.6 A pressure-sensitive adhesive sheet was produced in the same manner as in Example 2 except that the content was changed to parts by mass. The ratio of the epoxy-based crosslinking agent to the acrylic pressure-sensitive adhesive in the pressure-sensitive adhesive layer forming coating solution used here was 0.16 equivalent. Table 1 shows the measurement results of the physical property values of this pressure-sensitive adhesive sheet and the evaluation results of various properties.
（実施例４）
熱膨張性微小球（松本油脂製薬社製、商品名「マイクロスフェアＦ５０Ｄ」、平均粒径：１５μｍ）５質量部、熱膨張性微小球（松本油脂製薬社製、商品名「マイクロスフェアＦ８０ＧＳ」、平均粒径：８μｍ）２．５質量部、アクリル系粘着剤（アクリル酸−アクリル酸ブチル共重合体、質量平均分子量：４８万、ガラス転移温度：−３５℃、酸価：２１）３３質量部、テルペンフェノール系粘着付与樹脂（軟化点：１２５℃、水酸基価：２００）１０質量部、エポキシ系架橋剤（Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル−ｍ−キシレンジアミン）０．１８質量部、及びトルエン４９．３２質量部を均一に混合、溶解し、粘着剤層形成塗工液を調製した。この粘着剤層形成塗工液のエポキシ系架橋剤のアクリル系粘着剤に対する割合は０．２０当量であった。この塗工液を用いたこと以外は、前述の実施例１と同様にして粘着シートを作製した。この粘着シートの物性値の測定結果、及び各種特性の評価結果を表１に示す。
Example 4
Thermally expandable microspheres (trade name “Microsphere F50D”, manufactured by Matsumoto Yushi Seiyaku Co., Ltd., average particle size: 15 μm) (Average particle diameter: 8 μm) 2.5 parts by mass, acrylic pressure-sensitive adhesive (acrylic acid-butyl acrylate copolymer, mass average molecular weight: 480,000, glass transition temperature: −35 ° C., acid value: 21) 33 parts by mass , Terpene phenol tackifying resin (softening point: 125 ° C., hydroxyl value: 200) 10 parts by mass, epoxy crosslinking agent (N, N, N ′, N′-tetraglycidyl-m-xylenediamine) 0.18 mass And 49.32 parts by mass of toluene were uniformly mixed and dissolved to prepare an adhesive layer forming coating solution. The ratio of the epoxy-based cross-linking agent to the acrylic pressure-sensitive adhesive in the pressure-sensitive adhesive layer forming coating solution was 0.20 equivalent. A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that this coating solution was used. Table 1 shows the measurement results of the physical property values of this pressure-sensitive adhesive sheet and the evaluation results of various properties.
（比較例１）
熱膨張性微小球（松本油脂製薬社製、商品名「マイクロスフェアＦ５０Ｄ」、平均粒径：１５μｍ）５質量部、熱膨張性微小球（松本油脂製薬社製、商品名「マイクロスフェアＦ８０ＧＳ」、平均粒径：８μｍ）２．５質量部、アクリル系粘着剤（アクリル酸−アクリル酸ブチル共重合体、質量平均分子量：８１万、ガラス転移温度：−６４℃、酸価：２３）２５質量部、テルペンフェノール系粘着付与樹脂（軟化点：１２５℃、水酸基価：２００）１５質量部、エポキシ系架橋剤（Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル−ｍ−キシレンジアミン）０．１１質量部、及びトルエン５２．３９質量部を均一に混合、溶解し、粘着剤層形成塗工液を調製した。この粘着剤層形成塗工液のエポキシ系架橋剤のアクリル系粘着剤に対する割合は０．１４当量であった。この塗工液を用いたこと以外は、前述の実施例１と同様にして粘着シートを作製した。この粘着シートの物性値の測定結果、及び各種特性の評価結果を表１に示す。
(Comparative Example 1)
Thermally expandable microspheres (trade name “Microsphere F50D” manufactured by Matsumoto Yushi Seiyaku Co., Ltd., average particle size: 15 μm) (Average particle diameter: 8 μm) 2.5 parts by mass, acrylic adhesive (acrylic acid-butyl acrylate copolymer, mass average molecular weight: 810,000, glass transition temperature: −64 ° C., acid value: 23) 25 parts by mass , Terpene phenol tackifying resin (softening point: 125 ° C., hydroxyl value: 200) 15 parts by mass, epoxy crosslinking agent (N, N, N ′, N′-tetraglycidyl-m-xylenediamine) 0.11 mass Part and 52.39 parts by mass of toluene were uniformly mixed and dissolved to prepare an adhesive layer forming coating solution. The ratio of the epoxy-based crosslinking agent to the acrylic pressure-sensitive adhesive in the pressure-sensitive adhesive layer forming coating solution was 0.14 equivalent. A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that this coating solution was used. Table 1 shows the measurement results of the physical property values of this pressure-sensitive adhesive sheet and the evaluation results of various properties.
（比較例２）
エポキシ系架橋剤（Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル−ｍ−キシレンジアミン）を１．３６質量部（エポキシ系架橋剤のアクリル系粘着剤に対する割合は０．７当量）とした以外は、前述の実施例３と同様にして粘着シートを作製した。この粘着シートの物性値の測定結果、及び各種特性の評価結果を表１に示す。
(Comparative Example 2)
Except for setting the epoxy-based crosslinking agent (N, N, N ′, N′-tetraglycidyl-m-xylenediamine) to 1.36 parts by mass (the ratio of the epoxy-based crosslinking agent to the acrylic pressure-sensitive adhesive is 0.7 equivalent). Was a pressure-sensitive adhesive sheet as in Example 3 described above. Table 1 shows the measurement results of the physical property values of this pressure-sensitive adhesive sheet and the evaluation results of various properties.
表１の結果から、実施例１〜３の粘着シートは、粘着剤層に貼付した被着体を貼り直したり、被着体に力を加えて加工したりしても、粘着剤層が基材から剥離し難く、粘着剤層が被着体に付着する等の不具合も生じ難いものであることが分かる。また、実施例４の粘着シートは、実施例１〜３と比べると基材との密着性が低くなっているものの、比較例の粘着シートに比べれば十分基材との密着性は向上していることが分かる。従って、実施例１〜４の粘着シートは、被着体へ貼り付ける際、何度でも貼り直しができる、しかも貼り付け後は、十分被着体と密着性しているので、被着体加工性に優れ、その結果、加工精度や加工歩留り等、生産性が向上できることが予想される。 From the results shown in Table 1, the pressure-sensitive adhesive sheets of Examples 1 to 3 are based on the pressure-sensitive adhesive layer even when the adherend adhered to the pressure-sensitive adhesive layer is re-attached or processed by applying force to the adherend. It turns out that it is hard to peel from a material and it is hard to produce malfunctions, such as an adhesive layer adhering to a to-be-adhered body. Moreover, although the adhesive sheet of Example 4 has low adhesiveness with a base material compared with Examples 1-3, compared with the adhesive sheet of a comparative example, adhesiveness with a base material has improved sufficiently. I understand that. Therefore, the pressure-sensitive adhesive sheets of Examples 1 to 4 can be re-applied any number of times when being applied to the adherend, and after adhering, the adhesive sheet is sufficiently adhered to the adherend. As a result, it is expected that productivity such as processing accuracy and processing yield can be improved.
また、実施例３は実施例１〜２及び実施例４のものに比べ、剥離性に優れていることが分かる。このことにより、実施例１〜２及び実施例４のものは、被着体を剥がす際、指で触れることにより被着体（例えば、チップなど）が破損する可能性がある。 Moreover, it turns out that Example 3 is excellent in peelability compared with the thing of Examples 1-2 and Example 4. Thus, in Examples 1-2 and Example 4, when the adherend is peeled off, the adherend (for example, a chip) may be damaged by touching with a finger.
さらに、比較例２は、初期剥離力が低すぎるため、被着体を貼り付けた際、被着体と粘着シートとの密着性が低くなる。その結果、加工精度が低下することが予想される。 Furthermore, since the initial peeling force is too low in Comparative Example 2, the adhesion between the adherend and the adhesive sheet is low when the adherend is attached. As a result, it is expected that the processing accuracy will decrease.
また、基材との密着性の面から粘着剤層の２５℃の弾性率が１．０×１０６Ｐａ以下であるのが実施例１〜４と比較例１との比較から分かる。 Moreover, it can be seen from a comparison between Examples 1 to 4 and Comparative Example 1 that the elastic modulus at 25 ° C. of the pressure-sensitive adhesive layer is 1.0 × 10 6 Pa or less from the viewpoint of adhesion to the substrate.
本発明の粘着シートは、被着体と強固に密着させること可能であるとともに、加熱により被着体から容易に剥離可能である。しかも、被着体を貼り直しや加工時に加わる圧力等によっても粘着剤層が基材から剥離し難く、被着体に粘着剤層が付着し難いものであるため、被着体の加工精度や生産性（歩留まり）の向上が期待される。従って、本発明の粘着シートは、各種被着体の加工時の裏打用シート等として好適である。 The pressure-sensitive adhesive sheet of the present invention can be firmly adhered to an adherend and can be easily peeled off from the adherend by heating. Moreover, since the pressure-sensitive adhesive layer is difficult to peel off from the substrate even when the adherend is re-applied or processed, the pressure-sensitive adhesive layer is difficult to adhere to the adherend. Improvement of productivity (yield) is expected. Therefore, the pressure-sensitive adhesive sheet of the present invention is suitable as a backing sheet for processing various adherends.
Claims (4)
前記粘着剤層の２５℃における弾性率が、１．０×１０５Ｐａ以上、１．０×１０６Ｐａ以下である粘着シート。 A pressure-sensitive adhesive sheet comprising a film-like or sheet-like base material, and a pressure-sensitive adhesive layer containing thermally expandable microspheres disposed on at least one surface of the base material,
The adhesive sheet whose elastic modulus in 25 degreeC of the said adhesive layer is 1.0 * 10 < 5 > Pa or more and 1.0 * 10 < 6 > Pa or less.
［剥離試験］：ＳＵＳ３０４板をＪＩＳ Ｋ ０２３７に従って処理して得られた被着体の表面に、２３℃、６５％ＲＨの条件下、２０ｍｍ幅の粘着シートを貼付し、０．５時間放置した後、２３℃、６５％ＲＨの条件下、１８０°剥離力を測定し、測定された１８０°剥離力の値を、２５ｍｍ幅の粘着シートを用いた場合の値（Ｎ／２５ｍｍ）に換算する。 The pressure-sensitive adhesive sheet according to any one of claims 1 to 3, wherein an initial peeling force measured by the following peeling test is 2 N / 25 mm or more and 25 N / 25 mm or less.
[Peeling Test]: A 20 mm wide adhesive sheet was applied to the surface of an adherend obtained by treating a SUS304 plate according to JIS K 0237 under conditions of 23 ° C. and 65% RH and left for 0.5 hours. Thereafter, the 180 ° peel force is measured under the conditions of 23 ° C. and 65% RH, and the measured 180 ° peel force value is converted to a value (N / 25 mm) when a 25 mm wide adhesive sheet is used. .
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| JP2007078932A JP5150118B2 (en) | 2007-03-26 | 2007-03-26 | Adhesive sheet |
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| JP2007078932A JP5150118B2 (en) | 2007-03-26 | 2007-03-26 | Adhesive sheet |
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| JP5150118B2 JP5150118B2 (en) | 2013-02-20 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011225668A (en) * | 2010-04-16 | 2011-11-10 | Sekisui Chem Co Ltd | Expandable adhesive and expandable adhesive tape |
| KR20130084629A (en) | 2012-01-17 | 2013-07-25 | 닛토덴코 가부시키가이샤 | Polymer for pressure sensitive adhesive, pressure sensitive adhesive composition and heat-peelable pressure sensitive adhesive sheet |
| JP2015021082A (en) * | 2013-07-19 | 2015-02-02 | 日東電工株式会社 | Thermal peeling type adhesive tape for cutting-off electronic component and cutting-off method of electronic component |
| JP2015028108A (en) * | 2013-07-30 | 2015-02-12 | ソマール株式会社 | Adhesive composition and pressure-sensitive adhesive sheet |
| JP2015034302A (en) * | 2014-11-11 | 2015-02-19 | 日東電工株式会社 | Re-releasable adhesive composition, adhesive sheet and tape |
| JP2019168539A (en) * | 2018-03-22 | 2019-10-03 | スリーエム イノベイティブ プロパティズ カンパニー | Decorative sheet |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07324183A (en) * | 1994-05-31 | 1995-12-12 | Mitsubishi Chem Corp | Self-adhesive composition |
| JP2001072956A (en) * | 1999-09-08 | 2001-03-21 | Nippon Synthetic Chem Ind Co Ltd:The | Adhesive composition |
| JP2003160765A (en) * | 2001-11-26 | 2003-06-06 | Somar Corp | Re-peelable self-adhesive sheet |
| JP2004018604A (en) * | 2002-06-13 | 2004-01-22 | Somar Corp | Adhesive, heat-peeling type adhesive sheet using the same |
| JP2004200451A (en) * | 2002-12-19 | 2004-07-15 | Nitto Denko Corp | Protection sheet for semiconductor wafer processing |
| JP2005097386A (en) * | 2003-09-24 | 2005-04-14 | Somar Corp | Adhesive composition and removable adhesive sheet using the same |
| JP2005303068A (en) * | 2004-04-13 | 2005-10-27 | Nitto Denko Corp | Pressure sensitive adhesive sheet for holding and protecting semiconductor wafer, and rear face grinding method of semiconductor wafer |
| JP2005330407A (en) * | 2004-05-21 | 2005-12-02 | Somar Corp | Repeelable adhesive sheet and method for processing adherend by using the same |
| JP2005330406A (en) * | 2004-05-21 | 2005-12-02 | Somar Corp | Repeelable adhesive composition and repeelable adhesive sheet using the same |
| JP2007091862A (en) * | 2005-09-28 | 2007-04-12 | Somar Corp | Adhesive sheet |
-
2007
- 2007-03-26 JP JP2007078932A patent/JP5150118B2/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07324183A (en) * | 1994-05-31 | 1995-12-12 | Mitsubishi Chem Corp | Self-adhesive composition |
| JP2001072956A (en) * | 1999-09-08 | 2001-03-21 | Nippon Synthetic Chem Ind Co Ltd:The | Adhesive composition |
| JP2003160765A (en) * | 2001-11-26 | 2003-06-06 | Somar Corp | Re-peelable self-adhesive sheet |
| JP2004018604A (en) * | 2002-06-13 | 2004-01-22 | Somar Corp | Adhesive, heat-peeling type adhesive sheet using the same |
| JP2004200451A (en) * | 2002-12-19 | 2004-07-15 | Nitto Denko Corp | Protection sheet for semiconductor wafer processing |
| JP2005097386A (en) * | 2003-09-24 | 2005-04-14 | Somar Corp | Adhesive composition and removable adhesive sheet using the same |
| JP2005303068A (en) * | 2004-04-13 | 2005-10-27 | Nitto Denko Corp | Pressure sensitive adhesive sheet for holding and protecting semiconductor wafer, and rear face grinding method of semiconductor wafer |
| JP2005330407A (en) * | 2004-05-21 | 2005-12-02 | Somar Corp | Repeelable adhesive sheet and method for processing adherend by using the same |
| JP2005330406A (en) * | 2004-05-21 | 2005-12-02 | Somar Corp | Repeelable adhesive composition and repeelable adhesive sheet using the same |
| JP2007091862A (en) * | 2005-09-28 | 2007-04-12 | Somar Corp | Adhesive sheet |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011225668A (en) * | 2010-04-16 | 2011-11-10 | Sekisui Chem Co Ltd | Expandable adhesive and expandable adhesive tape |
| KR20130084629A (en) | 2012-01-17 | 2013-07-25 | 닛토덴코 가부시키가이샤 | Polymer for pressure sensitive adhesive, pressure sensitive adhesive composition and heat-peelable pressure sensitive adhesive sheet |
| JP2015021082A (en) * | 2013-07-19 | 2015-02-02 | 日東電工株式会社 | Thermal peeling type adhesive tape for cutting-off electronic component and cutting-off method of electronic component |
| JP2015028108A (en) * | 2013-07-30 | 2015-02-12 | ソマール株式会社 | Adhesive composition and pressure-sensitive adhesive sheet |
| JP2015034302A (en) * | 2014-11-11 | 2015-02-19 | 日東電工株式会社 | Re-releasable adhesive composition, adhesive sheet and tape |
| JP2019168539A (en) * | 2018-03-22 | 2019-10-03 | スリーエム イノベイティブ プロパティズ カンパニー | Decorative sheet |
| JP7063667B2 (en) | 2018-03-22 | 2022-05-09 | スリーエム イノベイティブ プロパティズ カンパニー | Decorative sheet |
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