JP3804805B2 - Heat release type adhesive sheet - Google Patents

Heat release type adhesive sheet Download PDF

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JP3804805B2
JP3804805B2 JP2004146814A JP2004146814A JP3804805B2 JP 3804805 B2 JP3804805 B2 JP 3804805B2 JP 2004146814 A JP2004146814 A JP 2004146814A JP 2004146814 A JP2004146814 A JP 2004146814A JP 3804805 B2 JP3804805 B2 JP 3804805B2
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heat
sensitive adhesive
pressure
adhesive sheet
adhesive layer
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JP2004277749A (en
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秋桐 村田
俊幸 大島
幸生 有満
一之 木内
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Nitto Denko Corp
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本発明は任意なときに短時間の加熱処理により被着体から簡単に剥離できる加熱剥離型粘着シートに関する。   The present invention relates to a heat-peelable pressure-sensitive adhesive sheet that can be easily peeled off from an adherend by a short-time heat treatment at any time.

従来、基材上に熱膨張性微小球などの発泡剤又は膨張剤を含む感圧粘着剤層を設けた加熱剥離型粘着シートが知られている(特公昭50−13878号公報、特公昭51−24534号公報、特開昭56−61468号公報、特開昭56−61469号公報、特開昭60−252681号公報など)。この加熱剥離型粘着シートは、接着性と使用後の剥離性とを両立させた粘着シートであり、加熱により発泡剤等を発泡又は膨張させることで接着力が低下し、被着体より容易に剥離できるという特徴を有する。そのため、電子部品の製造工程時における仮固定手段やリサイクル用ラベルなどとして用いられている。   Conventionally, there has been known a heat-peelable pressure-sensitive adhesive sheet in which a pressure-sensitive adhesive layer containing a foaming agent such as thermally expandable microspheres or an expanding agent is provided on a substrate (Japanese Patent Publication No. 50-13878, Japanese Patent Publication No. 51). No. 24534, JP-A 56-61468, JP-A 56-61469, JP-A 60-252681, etc.). This heat-peelable pressure-sensitive adhesive sheet is a pressure-sensitive adhesive sheet that achieves both adhesiveness and peelability after use. Adhesion is reduced by foaming or expanding a foaming agent or the like by heating, making it easier than the adherend. It has the characteristic that it can peel. For this reason, it is used as a temporary fixing means or a recycling label in the manufacturing process of electronic parts.

近年、電子機器の軽薄短小化、小型軽量化が進み、これに伴い、搭載されるコンデンサやLEDなどの電子部品も小型化、チップ化が進んでいる。上記の加熱剥離型粘着シートは、これらの電子部品の切断加工時の仮固定用途にも使用されているが、上記小型化に伴い、チップ1個当たりの接着対象面積が減少するため、粘着シートとの有効接触面積を確保することが、チップ飛びやチッピングなどの不具合対策として重要となってくる。しかしながら、従来の加熱剥離型粘着シートでは、粘着層表面に添加している熱膨張性微小球のうち相対的に粒径の大きい粒子に起因する凹凸が少なからずあるため、粘着シートとチップ間の有効接着面積が確保できず、チップ飛びやチッピングが発生してしまう場合があった。   In recent years, electronic devices have been made lighter, thinner, smaller and lighter, and along with this, electronic components such as capacitors and LEDs are also becoming smaller and chips. The above heat-peelable pressure-sensitive adhesive sheet is also used for temporary fixing at the time of cutting of these electronic components. However, since the area to be bonded per chip decreases as the size is reduced, the pressure-sensitive adhesive sheet It is important to secure an effective contact area with the chip as a countermeasure against defects such as chip skipping and chipping. However, in the conventional heat-peelable pressure-sensitive adhesive sheet, since there are not a few irregularities due to relatively large particles among the thermally expandable microspheres added to the pressure-sensitive adhesive layer surface, In some cases, an effective bonding area could not be secured, and chip skipping or chipping might occur.

特公昭50−13878号公報Japanese Patent Publication No. 50-13878 特公昭51−24534号公報Japanese Patent Publication No.51-24534 特開昭56−61468号公報JP-A-56-61468 特開昭56−61469号公報JP-A-56-61469 特開昭60−252681号公報JP 60-252681 A

したがって、本発明の目的は、被着体の接着対象面積が小さくなる場合であっても、有効な接触面積を確保でき、チップ飛びなどの接着不具合の発生を防止できる加熱剥離型粘着シートを提供することにある。   Accordingly, an object of the present invention is to provide a heat-peelable pressure-sensitive adhesive sheet that can secure an effective contact area and prevent the occurrence of adhesion defects such as chip jumping even when the adhesion target area of the adherend is small. There is to do.

本発明者らは、前記目的を達成するため鋭意検討した結果、加熱前の熱膨張性粘着層表面の中心線平均粗さを特定の範囲に設定すると、小型チップ化に伴うチップ飛びなどの接着不良を抑制できることを見出し、本発明を完成した。   As a result of intensive studies to achieve the above object, the present inventors have determined that when the center line average roughness of the surface of the heat-expandable adhesive layer before heating is set to a specific range, adhesion such as chip jumping associated with downsizing of the chip The inventors found that defects can be suppressed and completed the present invention.

すなわち、本発明は、基材の少なくとも片側に熱膨張性微小球を含有する熱膨張性粘着層が設けられた加熱剥離型粘着シートの製造方法であって、「熱膨張性粘着層の厚さ≧該熱膨張性粘着層中の熱膨張性微小球の最大粒径」となるように、該熱膨張性粘着層の厚さと該熱膨張性粘着層に添加する熱膨張性微小球の粒径とを調整して熱膨張性粘着層を形成することにより、加熱前の熱膨張性粘着層表面の中心線平均粗さが0.4μm以下の加熱剥離型粘着シートを得ることを特徴とする電子部品切断時の仮固定用加熱剥離型粘着シートの製造方法を提供する。 That is, the present invention is a method for producing a heat-peelable pressure-sensitive adhesive sheet in which a heat-expandable pressure-sensitive adhesive layer containing heat-expandable microspheres is provided on at least one side of a substrate, ≧ maximum particle diameter of thermally expandable microspheres in the thermally expandable adhesive layer ”, and the thickness of the thermally expandable adhesive layer and the particle diameter of the thermally expandable microspheres added to the thermally expandable adhesive layer To obtain a heat-peelable pressure-sensitive adhesive sheet having a center line average roughness of 0.4 μm or less on the surface of the heat-expandable pressure-sensitive adhesive layer before heating. Provided is a method for producing a heat-peelable pressure-sensitive adhesive sheet for temporary fixing during component cutting .

本発明の加熱剥離型粘着シートによれば、チップなどの被着体の接着対象面積が小さくなる場合であっても、有効な接触面積を確保でき、チップ飛びなどの接着不具合の発生を防止することができる。   According to the heat-peelable pressure-sensitive adhesive sheet of the present invention, even when the adhesion target area of an adherend such as a chip is small, an effective contact area can be ensured, and the occurrence of adhesion failure such as chip jumping can be prevented. be able to.

以下に、本発明の実施の形態を、必要に応じて図面を参照しつつ、詳細に説明する。図1は本発明の加熱剥離型粘着シートの一例を示す概略断面図であり、図2は本発明の加熱剥離型粘着シートの他の例を示す概略断面図である。   Embodiments of the present invention will be described below in detail with reference to the drawings as necessary. FIG. 1 is a schematic cross-sectional view showing an example of the heat-peelable pressure-sensitive adhesive sheet of the present invention, and FIG. 2 is a schematic cross-sectional view showing another example of the heat-peelable pressure-sensitive adhesive sheet of the present invention.

図1の例では、基材1の一方の面に熱膨張性粘着層3が設けられ、その上にセパレータ4が積層されている。図2の例では、基材1の一方の面に、ゴム状有機弾性層2を介して、熱膨張性粘着層3が設けられ、さらにその上にセパレータ4が積層されている。   In the example of FIG. 1, a heat-expandable pressure-sensitive adhesive layer 3 is provided on one surface of a substrate 1, and a separator 4 is laminated thereon. In the example of FIG. 2, a heat-expandable adhesive layer 3 is provided on one surface of the substrate 1 via a rubbery organic elastic layer 2, and a separator 4 is further laminated thereon.

基材1は、熱膨張性粘着層3等の支持母体となるもので、一般にはプラスチックのフィルムやシートが用いられるが、紙、布、不織布、金属箔など、又はこれらとプラスチックとの積層体、プラスチックフィルム(又はシート)同士の積層体などの適宜な薄葉体を用いうる。基材1の厚さは、一般には500μm以下、好ましくは1〜300μm、さらに好ましくは5〜250μm程度であるが、これらに限定されない。基材1の表面は、熱膨張性粘着層3等との密着性を高めるため、慣用の表面処理、例えば、クロム酸処理、オゾン暴露、火炎暴露、高圧電撃暴露、イオン化放射線処理等の化学的又は物理的方法による酸化処理等が施されていてもよく、また、熱膨張性粘着層3等との剥離性を付与するため、例えば、シリコーン系樹脂やフッ素系樹脂等の剥離剤などによるコーティング処理が施されていてもよい。   The base material 1 is a support base for the heat-expandable adhesive layer 3 and the like, and plastic films and sheets are generally used. However, paper, cloth, nonwoven fabric, metal foil, etc., or a laminate of these and plastic An appropriate thin leaf body such as a laminate of plastic films (or sheets) can be used. The thickness of the substrate 1 is generally 500 μm or less, preferably 1 to 300 μm, more preferably about 5 to 250 μm, but is not limited thereto. The surface of the substrate 1 is chemically treated by conventional surface treatments such as chromic acid treatment, ozone exposure, flame exposure, high piezoelectric impact exposure, ionizing radiation treatment, etc., in order to improve the adhesion to the thermally expandable adhesive layer 3 and the like. Alternatively, it may be subjected to an oxidation treatment by a physical method, and in order to impart releasability from the heat-expandable adhesive layer 3 or the like, for example, coating with a release agent such as a silicone resin or a fluorine resin Processing may be performed.

基材1には、低接着性基材及び強接着性基材が含まれる。低接着性基材としては、ポリエチレン、ポリプロピレンなどのオレフィン系樹脂等の無極性ポリマーからなる基材、表面が前記剥離剤でコーティング処理された基材などが例示できる。また、強接着性基材としては、ポリエステルなどの極性の高いポリマー等からなる基材、表面が前記化学的又は物理的方法により酸化処理等が施された基材などが挙げられる。   The substrate 1 includes a low adhesion substrate and a strong adhesion substrate. Examples of the low-adhesive substrate include a substrate made of a nonpolar polymer such as an olefin resin such as polyethylene and polypropylene, and a substrate whose surface is coated with the release agent. Examples of the strong adhesive substrate include a substrate made of a highly polar polymer such as polyester, and a substrate whose surface has been subjected to an oxidation treatment or the like by the chemical or physical method.

前記低接着性基材は、基材と基材上の層とが容易に剥離できる基材剥離型粘着シート用基材として用いられる。基材剥離型粘着シートは、例えば、1つの被着体aに貼り付けた後、基材を剥離して熱膨張性粘着層を被着体aに残し、この熱膨張性粘着層に他の被着体bを貼り合わせるといった仮止め接着剤として使用できる。この場合、接着状態を解除したいときには、加熱処理することにより容易に被着体a及びbを分離できる。一方、前記強接着性基材は、基材と基材上の層とが強接着した基材固着型粘着シート用基材として使用される。このような基材固着型粘着シートでは、接着時には被着体に予め設定した接着力で接着できると共に、接着状態を解除したいときには、加熱処理により容易に剥離又は分離できる。   The low-adhesive base material is used as a base material for a base-peelable pressure-sensitive adhesive sheet from which the base material and the layer on the base material can be easily peeled off. For example, after the base material release type adhesive sheet is attached to one adherend a, the base material is peeled off to leave the thermally expandable adhesive layer on the adherend a, It can be used as a temporary fixing adhesive such as bonding the adherend b. In this case, when it is desired to release the bonded state, the adherends a and b can be easily separated by heat treatment. On the other hand, the strongly adhesive substrate is used as a substrate for a substrate-fixed adhesive sheet in which a substrate and a layer on the substrate are strongly bonded. In such a substrate-fixed pressure-sensitive adhesive sheet, it can be adhered to an adherend with a predetermined adhesive force during adhesion, and can be easily peeled or separated by heat treatment when it is desired to release the adhesion state.

ゴム状有機弾性層2は、加熱剥離型粘着シートを被着体に接着する際に、前記粘着シートの表面を被着体の表面形状に良好に追従させて、接着面積を大きくするという機能と、前記粘着シートを被着体から加熱剥離する際に、熱膨張性層の加熱膨張を高度に(精度よく)コントロールし、熱膨張性層を厚さ方向へ優先的に且つ均一に膨張させるという機能とを有する。   The rubber-like organic elastic layer 2 has a function of increasing the adhesion area by causing the surface of the pressure-sensitive adhesive sheet to follow the surface shape of the adherend when the heat-peelable pressure-sensitive adhesive sheet is bonded to the adherend. When the pressure-sensitive adhesive sheet is heated and peeled off from the adherend, the heat expansion of the heat-expandable layer is controlled to a high degree (accurately), and the heat-expandable layer is expanded preferentially and uniformly in the thickness direction. With functions.

ゴム状有機弾性層2は、上記機能を具備させるため、例えば、ASTM D−2240に基づくD型シュアーD型硬度が、50以下、特に40以下の天然ゴム、合成ゴム又はゴム弾性を有する合成樹脂により形成することが好ましい。   In order to provide the rubbery organic elastic layer 2, for example, natural rubber, synthetic rubber, or synthetic resin having rubber elasticity having a D-type Sure D-type hardness of 50 or less, particularly 40 or less based on ASTM D-2240. It is preferable to form by.

前記合成ゴム又はゴム弾性を有する合成樹脂としては、例えば、ニトリル系、ジエン系、アクリル系などの合成ゴム;ポリオレフィン系、ポリエステル系などの熱可塑性エラストマー;エチレン−酢酸ビニル共重合体、ポリウレタン、ポリブタジエン、軟質ポリ塩化ビニルなどのゴム弾性を有する合成樹脂などが挙げられる。なお、ポリ塩化ビニルなどのように本質的には硬質系ポリマーであっても、可塑剤や柔軟剤等の配合剤との組み合わせによりゴム弾性が発現しうる。このような組成物も、前記ゴム状有機弾性層の構成材料として使用できる。また、後述の熱膨張性粘着層3を構成する粘着剤等の粘着性物質などもゴム状有機弾性層2の構成材料として好ましく用いうる。   Examples of the synthetic rubber or the synthetic resin having rubber elasticity include nitrile-based, diene-based, and acrylic-based synthetic rubbers; polyolefin-based and polyester-based thermoplastic elastomers; ethylene-vinyl acetate copolymer, polyurethane, polybutadiene, and the like. And a synthetic resin having rubber elasticity such as soft polyvinyl chloride. Even if it is essentially a hard polymer such as polyvinyl chloride, rubber elasticity can be manifested in combination with compounding agents such as plasticizers and softeners. Such a composition can also be used as a constituent material of the rubbery organic elastic layer. In addition, an adhesive substance such as an adhesive constituting the later-described thermally expandable adhesive layer 3 can be preferably used as a constituent material of the rubbery organic elastic layer 2.

ゴム状有機弾性層2の厚さは、一般的には500μm以下(例えば、1〜500μm)、好ましくは3〜300μm、さらに好ましくは5〜150μm程度である。   The thickness of the rubbery organic elastic layer 2 is generally 500 μm or less (for example, 1 to 500 μm), preferably 3 to 300 μm, and more preferably about 5 to 150 μm.

ゴム状有機弾性層2の形成は、例えば、前記天然ゴム、合成ゴム又はゴム弾性を有する合成樹脂などの弾性層形成材を含むコーティング液を基材1上に塗布する方式(コーティング法)、前記弾性層形成材からなるフィルム、又は予め1層以上の熱膨張性粘着層3上に前記弾性層形成材からなる層を形成した積層フィルムを基材1と接着する方式(ドライラミネート法)、基材1の構成材料を含む樹脂組成物と前記弾性層形成材を含む樹脂組成物とを共押出しする方式(共押出し法)などの適宜な方式で行うことができる。   The rubber-like organic elastic layer 2 is formed, for example, by applying a coating liquid containing an elastic layer forming material such as natural rubber, synthetic rubber or synthetic resin having rubber elasticity on the substrate 1 (coating method), A method in which a film made of an elastic layer forming material or a laminated film in which a layer made of the elastic layer forming material is previously formed on one or more thermally expandable adhesive layers 3 is bonded to the substrate 1 (dry laminating method), The resin composition containing the constituent material of the material 1 and the resin composition containing the elastic layer forming material can be co-extruded (co-extrusion method).

なお、ゴム状有機弾性層2は、天然ゴムや合成ゴム又はゴム弾性を有する合成樹脂を主成分とする粘着性物質で形成されていてもよく、また、かかる成分を主体とする発泡フィルム等で形成されていてもよい。発泡は、慣用の方法、例えば、機械的な攪拌による方法、反応生成ガスを利用する方法、発泡剤を使用する方法、可溶性物質を除去する方法、スプレーによる方法、シンタクチックフォームを形成する方法、焼結法などにより行うことができる。ゴム状有機弾性層2は単層であってもよく、2以上の層で構成してもよい。   The rubbery organic elastic layer 2 may be formed of a sticky substance mainly composed of natural rubber, synthetic rubber, or synthetic resin having rubber elasticity, and may be a foam film or the like mainly composed of such a component. It may be formed. Foaming is a conventional method, for example, a method using mechanical stirring, a method using a reaction product gas, a method using a foaming agent, a method for removing soluble substances, a method using a spray, a method for forming a syntactic foam, It can be performed by a sintering method or the like. The rubbery organic elastic layer 2 may be a single layer or may be composed of two or more layers.

熱膨張性粘着層3は、粘着性を付与するための粘着剤、及び熱膨張性を付与するための熱膨張性微小球(マイクロカプセル)を含んでいる。そのため、粘着シートを被着体に貼着した後、任意なときに熱膨張性粘着層3を加熱して、熱膨張性微小球を発泡及び/又は膨張処理することにより、熱膨張性粘着層3と被着体との接着面積を減少させて、粘着シートを容易に剥離することができる。マイクロカプセル化していない発泡剤では、良好な剥離性を安定して発現させることができない。   The heat-expandable pressure-sensitive adhesive layer 3 includes a pressure-sensitive adhesive for imparting tackiness and a heat-expandable microsphere (microcapsule) for imparting heat-expandability. Therefore, after the adhesive sheet is attached to the adherend, the thermally expandable adhesive layer 3 is heated at any time to foam and / or expand the thermally expandable microspheres, whereby the thermally expandable adhesive layer The adhesion area of 3 and a to-be-adhered body can be reduced, and an adhesive sheet can be peeled easily. With a foaming agent that is not microencapsulated, good peelability cannot be stably exhibited.

前記粘着剤としては、加熱時に熱膨張性微小球の発泡及び/又は膨張を可及的に拘束しないようなものが好ましい。該粘着剤として、例えば、ゴム系粘着剤、アクリル系粘着剤、ビニルアルキルエーテル系粘着剤、シリコーン系粘着剤、ポリエステル系粘着剤、ポリアミド系粘着剤、ウレタン系粘着剤、スチレン−ジエンブロック共重合体系粘着剤、これらの粘着剤に融点が約200℃以下の熱溶融性樹脂を配合したクリ−プ特性改良型粘着剤などの公知の粘着剤を1種又は2種以上組み合わせて用いることができる(例えば、特開昭56−61468号公報、特開昭61−174857号公報、特開昭63−17981号公報、特開昭56−13040号公報等参照)。粘着剤は、粘着性成分(ベースポリマー)のほかに、架橋剤(例えば、ポリイソシアネート、アルキルエーテル化メラミン化合物など)、粘着付与剤(例えば、ロジン誘導体樹脂、ポリテルペン樹脂、石油樹脂、油溶性フェノール樹脂など)、可塑剤、充填剤、老化防止剤などの適宜な添加剤を含んでいてもよい。   The pressure-sensitive adhesive is preferably one that does not restrain foaming and / or expansion of the thermally expandable microspheres as much as possible during heating. Examples of the pressure sensitive adhesive include rubber pressure sensitive adhesive, acrylic pressure sensitive adhesive, vinyl alkyl ether pressure sensitive adhesive, silicone pressure sensitive adhesive, polyester pressure sensitive adhesive, polyamide pressure sensitive adhesive, urethane pressure sensitive adhesive, and styrene-diene block copolymer. One or a combination of two or more known pressure-sensitive adhesives such as system pressure-sensitive adhesives and those having a melting point of about 200 ° C. or less and a melt-melting resin having a melting point of about 200 ° C. or less can be used. (See, for example, JP-A-56-61468, JP-A-61-174857, JP-A-63-17981, JP-A-56-13040, etc.). In addition to the adhesive component (base polymer), the adhesive is a crosslinking agent (eg, polyisocyanate, alkyl etherified melamine compound, etc.), tackifier (eg, rosin derivative resin, polyterpene resin, petroleum resin, oil-soluble phenol) Resin, etc.), plasticizers, fillers, anti-aging agents and other suitable additives may be included.

一般には、前記粘着剤として、天然ゴムや各種の合成ゴムをベースポリマーとしたゴム系粘着剤;(メタ)アクリル酸アルキルエステル(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、2−エチルヘキシルエステル、イソオクチルエステル、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、ヘキサデシルエステル、ヘプタデシルエステル、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などのC1-20アルキルエステルなど)の1種又は2種以上を単量体成分として用いたアクリル系重合体(単独重合体又は共重合体)をベースポリマーとするアクリル系粘着剤などが用いられる。 In general, the pressure-sensitive adhesive is a rubber-based pressure-sensitive adhesive based on natural rubber or various synthetic rubbers; (meth) acrylic acid alkyl esters (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, 2-ethylhexyl ester, isooctyl ester, isodecyl ester, dodecyl ester, tridecyl ester, pentadecyl ester, hexa decyl ester, heptadecyl ester, octadecyl ester, nonadecyl ester, Accession used as monomer components one or more of C, such as 1-20 alkyl ester) such as eicosyl ester Such as acrylic adhesive is used to Le-based polymer (homopolymer or copolymer) as a base polymer.

なお、前記アクリル系重合体は、凝集力、耐熱性、架橋性などの改質を目的として、必要に応じて、前記(メタ)アクリル酸アルキルエステルと共重合可能な他の単量体成分に対応する単位を含んでいてもよい。このような単量体成分として、例えば、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、クロトン酸などのカルボキシル基含有モノマー;無水マレイン酸、無水イコタン酸などの酸無水物モノマー;(メタ)アクリル酸ヒドロキシエチル、(メタ)アクリル酸ヒドロキシプロピル、(メタ)アクリル酸ヒドロキシブチル、(メタ)アクリル酸ヒドロキシヘキシル、(メタ)アクリル酸ヒドロキシオクチル、(メタ)アクリル酸ヒドロキシデシル、(メタ)アクリル酸ヒドロキシラウリル、(4−ヒドロキシメチルシクロヘキシル)メチルメタクリレートなどのヒドロキシル基含有モノマー;スチレンスルホン酸、アリルスルホン酸、2−(メタ)アクリルアミド−2−メチルプロパンスルホン酸、(メタ)アクリルアミドプロパンスルホン酸、スルホプロピル(メタ)アクリレート、(メタ)アクリロイルオキシナフタレンスルホン酸などのスルホン酸基含有モノマー;(メタ)アクリルアミド、N,N−ジメチル(メタ)アクリルアミド、N−ブチル(メタ)アクリルアミド、N−メチロール(メタ)アクリルアミド、N−メチロールプロパン(メタ)アクリルアミドなどの(N−置換)アミド系モノマー;(メタ)アクリル酸アミノエチル、(メタ)アクリル酸N,N−ジメチルアミノエチル、(メタ)アクリル酸t−ブチルアミノエチルなどの(メタ)アクリル酸アミノアルキル系モノマー;(メタ)アクリル酸メトキシエチル、(メタ)アクリル酸エトキシエチルなどの(メタ)アクリル酸アルコキシアルキル系モノマー;N−シクロヘキシルマレイミド、N−イソプロピルマレイミド、N−ラウリルマレイミド、N−フェニルマレイミドなどのマレイミド系モノマー;N−メチルイタコンイミド、N−エチルイタコンイミド、N−ブチルイタコンイミド、N−オクチルイタコンイミド、N−2−エチルヘキシルイタコンイミド、N−シクロヘキシルイタコンイミド、N−ラウリルイタコンイミドなどのイタコンイミド系モノマー;N−(メタ)アクリロイルオキシメチレンスクシンイミド、N−(メタ)アクルロイル−6−オキシヘキサメチレンスクシンイミド、N−(メタ)アクリロイル−8−オキシオクタメチレンスクシンイミドなどのスクシンイミド系モノマー;酢酸ビニル、プロピオン酸ビニル、N−ビニルピロリドン、メチルビニルピロリドン、ビニルピリジン、ビニルピペリドン、ビニルピリミジン、ビニルピペラジン、ビニルピラジン、ビニルピロール、ビニルイミダゾール、ビニルオキサゾール、ビニルモルホリン、N−ビニルカルボン酸アミド類、スチレン、α−メチルスチレン、N−ビニルカプロラクタムなどのビニル系モノマー;アクリロニトリル、メタクリロニトリルなどのシアノアクリレートモノマー;(メタ)アクリル酸グリシジルなどのエポキシ基含有アクリル系モノマー;(メタ)アクリル酸ポリエチレングリコール、(メタ)アクリル酸ポリプロピレングリコール、(メタ)アクリル酸メトキシエチレングリコール、(メタ)アクリル酸メトキシポリプロピレングリコールなどのグリコール系アクリルエステルモノマー;(メタ)アクリル酸テトラヒドロフルフリル、フッ素(メタ)アクリレート、シリコーン(メタ)アクリレートなどの複素環、ハロゲン原子、ケイ素原子などを有するアクリル酸エステル系モノマー;ヘキサンジオールジ(メタ)アクリレート、(ポリ)エチレングリコールジ(メタ)アクリレート、(ポリ)プロピレングリコールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、ペンタエリスリトールジ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、エポキシアクリレート、ポリエステルアクリレート、ウレタンアクリレートなどの多官能モノマー;イソプレン、ブタジエン、イソブチレンなどのオレフィン系モノマー;ビニルエーテルなどのビニルエーテル系モノマー等が挙げられる。これらの単量体成分は1種又は2種以上使用できる。   The acrylic polymer may be mixed with other monomer components copolymerizable with the (meth) acrylic acid alkyl ester as necessary for the purpose of modifying cohesion, heat resistance, crosslinkability, and the like. Corresponding units may be included. Examples of such monomer components include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid; maleic anhydride, itaconic anhydride Acid anhydride monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, (meth) Hydroxyl group-containing monomers such as hydroxydecyl acrylate, hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl methacrylate; styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylic Sulfonic acid group-containing monomers such as mid-2-methylpropanesulfonic acid, (meth) acrylamidepropanesulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalenesulfonic acid; (meth) acrylamide, N, N-dimethyl (N-substituted) amide monomers such as (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide; aminoethyl (meth) acrylate, (meta ) (Meth) acrylic acid aminoalkyl monomers such as N, N-dimethylaminoethyl acrylate, t-butylaminoethyl (meth) acrylate; methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, etc. (Meta) Acry Acid alkoxyalkyl monomers; maleimide monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-phenylmaleimide; N-methylitaconimide, N-ethylitaconimide, N-butylitaconimide, N -Itacimide monomers such as octylitaconimide, N-2-ethylhexylitaconimide, N-cyclohexylitaconimide, N-laurylitaconimide; N- (meth) acryloyloxymethylenesuccinimide, N- (meth) acryloyl-6-oxy Succinimide monomers such as hexamethylene succinimide and N- (meth) acryloyl-8-oxyoctamethylene succinimide; vinyl acetate, vinyl propionate, N-vinyl pyrrolide , Methyl vinyl pyrrolidone, vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piperazine, vinyl pyrazine, vinyl pyrrole, vinyl imidazole, vinyl oxazole, vinyl morpholine, N-vinyl carboxylic acid amides, styrene, α-methyl styrene, N-vinyl Vinyl monomers such as caprolactam; cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; epoxy group-containing acrylic monomers such as glycidyl (meth) acrylate; polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, ( Glycol acrylic ester monomers such as (meth) acrylic acid methoxyethylene glycol and (meth) acrylic acid methoxypolypropylene glycol; Acrylic acid ester monomers having heterocycles such as tetrahydrofurfuryl acrylate, fluorine (meth) acrylate, silicone (meth) acrylate, halogen atoms, silicon atoms, etc .; hexanediol di (meth) acrylate, (poly) ethylene glycol di (Meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Polyfunctional monomers such as dipentaerythritol hexa (meth) acrylate, epoxy acrylate, polyester acrylate, urethane acrylate; isoprene, butadiene, iso Examples thereof include olefin monomers such as butylene; vinyl ether monomers such as vinyl ether. These monomer components can be used alone or in combination of two or more.

なお、加熱処理前の適度な接着力と加熱処理後の接着力の低下性のバランスの点から、より好ましい粘着剤は、動的弾性率が常温から150℃において5万〜1000万dyn/cm2の範囲にあるポリマーをベースとした感圧接着剤である。 In addition, from the point of balance of moderate adhesive force before heat treatment and lowering of adhesive force after heat treatment, more preferable pressure-sensitive adhesives have a dynamic elastic modulus of 50,000 to 10,000,000 dyn / cm from room temperature to 150 ° C. A pressure sensitive adhesive based on polymers in the range of 2 .

熱膨張性微小球としては、例えば、イソブタン、プロパン、ペンタンなどの加熱により容易にガス化して膨張する物質を、弾性を有する殻内に内包させた微小球であればよい。前記殻は、熱溶融性物質や熱膨張により破壊する物質で形成される場合が多い。前記殻を形成する物質として、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、ポリスルホンなどが挙げられる。熱膨張性微小球は、慣用の方法、例えば、コアセルベーション法、界面重合法などにより製造できる。なお、熱膨張性微小球には、例えば、マイクロスフェア[商品名、松本油脂製薬(株)製]などの市販品もある。   The heat-expandable microsphere may be a microsphere in which a substance that easily expands by gasification by heating, such as isobutane, propane, or pentane, is encapsulated in an elastic shell. The shell is often 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. Thermally expandable microspheres can be produced by a conventional method such as a coacervation method or an interfacial polymerization method. Examples of the thermally expandable microsphere include a commercially available product such as a microsphere [trade name, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.].

加熱処理により粘着層の接着力を効率よく低下させるため、体積膨張率が5倍以上、なかでも7倍以上、特に10倍以上となるまで破裂しない適度な強度を有する熱膨張性微小球が好ましい。   In order to efficiently reduce the adhesive force of the pressure-sensitive adhesive layer by heat treatment, thermally expandable microspheres having an appropriate strength that does not rupture until the volume expansion coefficient is 5 times or more, especially 7 times or more, particularly 10 times or more are preferable. .

熱膨張性微小球の配合量は、粘着層の膨張倍率や接着力の低下性などに応じて適宜設定しうるが、一般には熱膨張性粘着層3を形成するベースポリマー100重量部に対して、例えば1〜150重量部、好ましくは10〜130重量部、さらに好ましくは25〜100重量部である。   The blending amount of the thermally expandable microspheres can be appropriately set according to the expansion ratio of the adhesive layer, the lowering of the adhesive force, etc., but generally the amount is 100 parts by weight of the base polymer forming the thermally expandable adhesive layer 3. For example, it is 1-150 weight part, Preferably it is 10-130 weight part, More preferably, it is 25-100 weight part.

熱膨張性粘着層3は、例えば、必要に応じて溶媒を用いて粘着剤、熱膨張性微小球を含むコーティング液を調製し、これを基材1又はゴム状有機弾性層2上に塗布する方式、適当なセパレータ(剥離紙など)上に前記コーティング液を塗布して熱膨張性粘着層を形成し、これを基材1又はゴム状有機弾性層2上に転写(移着)する方法など、慣用の方法により形成できる。熱膨張性粘着層3は単層、複層の何れであってもよい。   For the heat-expandable pressure-sensitive adhesive layer 3, for example, a coating liquid containing a pressure-sensitive adhesive and heat-expandable microspheres is prepared using a solvent as necessary, and this is applied onto the substrate 1 or the rubbery organic elastic layer 2. A method, a method in which the coating liquid is applied on an appropriate separator (such as release paper) to form a thermally expandable adhesive layer, and this is transferred (transferred) onto the substrate 1 or the rubbery organic elastic layer 2. Can be formed by conventional methods. The thermally expandable pressure-sensitive adhesive layer 3 may be either a single layer or multiple layers.

本発明の重要な特徴は、加熱前の熱膨張性粘着層表面の中心線平均粗さが0.4μm以下(例えば0.02〜0.4μm程度)である点にある。前記中心線平均粗さは、好ましくは0.3μm以下(例えば0.02〜0.3μm程度)、さらに好ましくは0.2μm以下(例えば0.02〜0.2μm程度)である。また、加熱前の熱膨張性粘着層表面の最大粗さは5μm以下(例えば、0.1〜5μm程度)であるのが好ましく、さらに好ましくは3μm以下(例えば、0.5〜3μm程度)である。   An important feature of the present invention is that the center line average roughness of the surface of the thermally expandable pressure-sensitive adhesive layer before heating is 0.4 μm or less (for example, about 0.02 to 0.4 μm). The center line average roughness is preferably 0.3 μm or less (for example, about 0.02 to 0.3 μm), more preferably 0.2 μm or less (for example, about 0.02 to 0.2 μm). The maximum roughness of the surface of the thermally expandable pressure-sensitive adhesive layer before heating is preferably 5 μm or less (for example, about 0.1 to 5 μm), more preferably 3 μm or less (for example, about 0.5 to 3 μm). is there.

前記加熱前の熱膨張性粘着層表面の中心線平均粗さ及び最大粗さは、熱膨張性粘着層3の厚さと該粘着層に添加する熱膨張性微小球の粒径を適宜選択することにより調整することができる。   The centerline average roughness and maximum roughness of the surface of the thermally expandable adhesive layer before heating are appropriately selected from the thickness of the thermally expandable adhesive layer 3 and the particle size of the thermally expandable microspheres added to the adhesive layer. Can be adjusted.

熱膨張性微小球の粒径は、加熱前の熱膨張性粘着層表面の中心線平均粗さ0.4μm以下、さらには加熱前の熱膨張性粘着層表面の最大粗さ5μm以下を確保するため、「熱膨張性粘着層3の厚さ≧熱膨張性微小球の粒径」の関係であることが望ましい。熱膨張性微小球の粒径が熱膨張性粘着層3の厚さよりも大きいと、熱膨張性粘着層3の表面粗さが大きくなり、被着体との有効接着面積が小さくなる。なお、基材1と熱膨張性粘着剤層3との間にゴム状有機弾性層2を設ける場合には、熱膨張性粘着層3の厚さより熱膨張性微小球の粒径が若干大きくても、ゴム状有機弾性層2への吸収効果が期待できるため、この限りではない。熱膨張性微小球の粒径調整は、熱膨張性微小球の生成過程で行ってもよく、又、生成後の分級などの手段で行ってもよい。   The particle diameter of the heat-expandable microspheres is ensured such that the centerline average roughness of the surface of the heat-expandable adhesive layer before heating is 0.4 μm or less, and further the maximum roughness of the surface of the heat-expandable pressure-sensitive adhesive layer before heating is 5 μm or less. Therefore, the relationship of “thickness of thermally expandable pressure-sensitive adhesive layer 3 ≧ particle diameter of thermally expandable microspheres” is desirable. When the particle size of the thermally expandable microsphere is larger than the thickness of the thermally expandable pressure-sensitive adhesive layer 3, the surface roughness of the heat-expandable pressure-sensitive adhesive layer 3 increases, and the effective adhesion area with the adherend decreases. When the rubber-like organic elastic layer 2 is provided between the base material 1 and the heat-expandable pressure-sensitive adhesive layer 3, the particle diameter of the heat-expandable microsphere is slightly larger than the thickness of the heat-expandable pressure-sensitive adhesive layer 3. However, this is not the case because an absorption effect on the rubber-like organic elastic layer 2 can be expected. The particle size adjustment of the thermally expandable microspheres may be performed during the process of generating the thermally expandable microspheres, or may be performed by means such as classification after the generation.

熱膨張性粘着層3の厚さは、300μm以下、特に100μm以下であることが好ましい。厚さが過大であると、加熱処理後の剥離時に凝集破壊が生じて粘着剤が被着体に残存し、被着体が汚染されやすくなる。一方、粘着剤の厚さが過小では、加熱処理による熱膨張性粘着層3の変形度が小さく、接着力が円滑に低下しにくくなったり、添加する熱膨張性微小球の粒径を過度に小さくする必要が生じる。かかる点より、熱膨張性粘着層3の厚さは5μm以上、なかでも10μm以上、特に15μm以上であるのが好ましい。   The thickness of the heat-expandable pressure-sensitive adhesive layer 3 is preferably 300 μm or less, particularly preferably 100 μm or less. If the thickness is excessive, cohesive failure occurs at the time of peeling after the heat treatment, the adhesive remains on the adherend, and the adherend tends to be contaminated. On the other hand, if the thickness of the pressure-sensitive adhesive is too small, the degree of deformation of the heat-expandable pressure-sensitive adhesive layer 3 due to heat treatment is small, and the adhesive force is difficult to decrease smoothly, or the particle diameter of the heat-expandable microspheres to be added is excessively increased. It is necessary to make it smaller. From this point, the thickness of the thermally expandable pressure-sensitive adhesive layer 3 is preferably 5 μm or more, more preferably 10 μm or more, and particularly preferably 15 μm or more.

セパレータ4としては、慣用の剥離紙などを使用できる。セパレータ4は熱膨張性粘着層3の保護材として用いられ、粘着シートを被着体に貼着する際に剥がされる。セパレータ4は必ずしも設けなくてもよい。   As the separator 4, a conventional release paper or the like can be used. The separator 4 is used as a protective material for the heat-expandable pressure-sensitive adhesive layer 3, and is peeled off when the pressure-sensitive adhesive sheet is attached to an adherend. The separator 4 is not necessarily provided.

なお、熱膨張性粘着層3は基材1の片面のみならず、両面に形成することもできる。また、必要に応じて、ゴム状有機弾性層2も基材1の片面又は両面に介在させることができる。さらに、基材1の一方の面に熱膨張性粘着層3を設け、他方の面に熱膨張性微小球を含まない通常の接着層を設けることもできる。なお、基材1とゴム状有機弾性層2との間、ゴム状有機弾性層2と熱膨張性粘着層3との間などに下塗り層、接着剤層などの中間層を設けてもよい。   The thermally expandable pressure-sensitive adhesive layer 3 can be formed not only on one side of the substrate 1 but also on both sides. Moreover, the rubber-like organic elastic layer 2 can also be interposed on one side or both sides of the substrate 1 as necessary. Furthermore, the heat-expandable pressure-sensitive adhesive layer 3 can be provided on one surface of the substrate 1, and a normal adhesive layer that does not contain heat-expandable microspheres can be provided on the other surface. An intermediate layer such as an undercoat layer or an adhesive layer may be provided between the base material 1 and the rubbery organic elastic layer 2 or between the rubbery organic elastic layer 2 and the heat-expandable pressure-sensitive adhesive layer 3.

本発明の加熱剥離型粘着シートでは、加熱前の熱膨張性粘着層表面の中心平均粗さが小さいので、例えば、電子部品切断時の仮固定用テープとして用い、より小型チップ化するときなど接着対象面積が小さくなる場合においても、ワークとの有効接触面積を十分に確保できるため、チップ飛びやズレ等の接着力不足に起因する不具合の発生を抑制できる。そのため、生産性や歩留まり等の低下を防止することができる。   In the heat-peelable pressure-sensitive adhesive sheet of the present invention, since the center average roughness of the surface of the heat-expandable pressure-sensitive adhesive layer before heating is small, for example, it is used as a temporary fixing tape when cutting electronic components and is bonded when making smaller chips. Even when the target area is small, an effective contact area with the work can be sufficiently ensured, so that it is possible to suppress the occurrence of defects due to insufficient adhesive force such as chip fly and displacement. Therefore, it is possible to prevent a decrease in productivity, yield, and the like.

また、基材と熱膨張性粘着層との間にゴム状有機弾性層が設けられた加熱剥離型粘着シートでは、粘着シートを被着体に接着する際には、ゴム状有機弾性層の弾性により、粘着シートの表面が被着体の表面形状に良好に追従して大きな接着面積が得られ、接着強度を高めることができると共に、加熱剥離させる際には、熱膨張性層の膨張(体積変化)を精度よくコントロールでき、厚さ方向に優先して且つ均一に膨張させることができ、剥離が一層容易となる。また、熱膨張性粘着層に含まれる熱膨張性微小球の粒径が多少大きくても、それに起因する凹凸がゴム状有機弾性層により吸収されるので、熱膨張性粘着層の表面粗さを小さく抑制できる。   Further, in the heat-peelable pressure-sensitive adhesive sheet in which the rubber-like organic elastic layer is provided between the base material and the thermally expandable pressure-sensitive adhesive layer, the elasticity of the rubber-like organic elastic layer is required when the pressure-sensitive adhesive sheet is bonded to the adherend. As a result, the surface of the pressure-sensitive adhesive sheet satisfactorily follows the surface shape of the adherend, so that a large adhesion area can be obtained, and the adhesive strength can be increased. (Change) can be controlled with high precision, and can be uniformly expanded in preference to the thickness direction, and peeling becomes easier. Moreover, even if the particle size of the thermally expandable microspheres contained in the thermally expandable adhesive layer is somewhat large, the unevenness resulting therefrom is absorbed by the rubber-like organic elastic layer, so that the surface roughness of the thermally expandable adhesive layer is reduced. Can be kept small.

本発明の加熱剥離型粘着シートは、適宜な物品からなる被着体を永久的に接着しておく用途に用いることもできるが、被着体を所定期間接着すると共に、接着目的を達成した後には、その接着状態を解除することが要求される又は望まれる用途に好適に使用される。特に、従来の加熱剥離型粘着シートでは接着困難となりやすい、より小型のチップ部品の製造、例えば、半導体ウエハやチップ、セラミックコンデンサや発振子などの電子部品のより小型チップ化工程に最適である。   The heat-peelable pressure-sensitive adhesive sheet of the present invention can be used for applications in which an adherend made of an appropriate article is permanently bonded, but after adhering the adherend for a predetermined period and achieving the bonding purpose Is suitably used for applications where it is required or desired to release the adhesive state. In particular, it is most suitable for the manufacture of smaller chip components that are difficult to bond with conventional heat-peelable pressure-sensitive adhesive sheets, for example, for the process of making smaller chips for electronic components such as semiconductor wafers, chips, ceramic capacitors, and oscillators.

本発明の粘着シートを被着体より容易に剥離できるようにするための加熱処理条件は、被着体の表面状態や熱膨張性微小球の種類等による接着面積の減少性、基材や被着体の耐熱性や加熱方法等の条件により適宜設定できる。一般的な加熱処理条件は、温度100〜250℃で、1〜90秒間(ホットプレートなど)または5〜15分間(熱風乾燥器など)である。かかる加熱条件で、通例、粘着層の熱膨張性微小球が膨張及び/又は発泡して粘着層が膨張変形し、接着力が低下ないし喪失する。なお、加熱処理は使用目的に応じて適宜な段階で行うことができる。また、加熱源としては、赤外線ランプや加熱水を用いることができる場合もある。   The heat treatment conditions for allowing the pressure-sensitive adhesive sheet of the present invention to be easily peeled off from the adherend include the reduction in the adhesion area due to the surface state of the adherend and the type of thermally expandable microspheres, the substrate and the covering. It can be appropriately set depending on conditions such as the heat resistance of the adherend and the heating method. General heat treatment conditions are a temperature of 100 to 250 ° C. and a time of 1 to 90 seconds (hot plate or the like) or 5 to 15 minutes (hot air dryer or the like). Under such heating conditions, the heat-expandable microspheres of the pressure-sensitive adhesive layer usually expand and / or foam and the pressure-sensitive adhesive layer expands and deforms, and the adhesive force is reduced or lost. Note that the heat treatment can be performed at an appropriate stage depending on the purpose of use. In some cases, an infrared lamp or heated water can be used as the heating source.

以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例により何ら限定されるものではない。なお、粒径測定は、レーザー散乱・回折式粒度分布測定装置SALD−2000J型((株)島津製作所製)を用いた。   Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The particle size measurement was performed using a laser scattering / diffraction particle size distribution analyzer SALD-2000J (manufactured by Shimadzu Corporation).

実施例1
熱膨張性微小球A(マツモトマイクロスフェアF−50D:松本油脂製薬(株)製:平均粒子径13.4μm、最大粒径63μm)を遠心力型風力分級機を用いて分級し、分級済み熱膨張性微小球B(平均粒子径12.3μm、最大粒径42μm)を得た。
一方、アクリル酸2−エチルヘキシル−アクリル酸エチル−メチルメタクリレート(30重量部−70重量部−5重量部)共重合体系感圧接着剤100重量部(ポリウレタン系架橋剤2重量部配合)に、前記分級済み熱膨張性微小球B30重量部を配合してなるトルエン溶液を調製し、これを、厚さ100μmのポリエステルフィルム上に乾燥後の厚みが45μmとなるように塗布、乾燥して、加熱剥離型粘着シートを得た。
次に、上記の加熱剥離型粘着シートの粘着面に120mm×100mm×厚さ0.5mmのセラミックシート(焼成前)を仮固定し、それをダイシングリングに装着固定して回転刃を介し、0.6mm×0.3mmのチップにフルカットした。前記カット後、ダイシングリングに装着固定したままの状態で130℃×60秒の加熱処理をホットプレート上で行い、冷却後、反転振動させてチップを回収した。
Example 1
Thermally expandable microspheres A (Matsumoto Microsphere F-50D: Matsumoto Yushi Seiyaku Co., Ltd .: average particle size 13.4 μm, maximum particle size 63 μm) are classified using a centrifugal force classifier, and classified heat Expandable microspheres B (average particle size 12.3 μm, maximum particle size 42 μm) were obtained.
On the other hand, 2-ethylhexyl acrylate-ethyl acrylate-methyl methacrylate (30 parts by weight-70 parts by weight-5 parts by weight) copolymer-based pressure-sensitive adhesive 100 parts by weight (containing 2 parts by weight of a polyurethane-based crosslinking agent) Prepare a toluene solution containing 30 parts by weight of classified thermally expandable microspheres B, apply this onto a 100 μm thick polyester film, dry it to a thickness of 45 μm, dry it, and heat peel A mold pressure-sensitive adhesive sheet was obtained.
Next, a 120 mm × 100 mm × 0.5 mm thick ceramic sheet (before firing) is temporarily fixed to the adhesive surface of the heat-peelable adhesive sheet, and the ceramic sheet is attached and fixed to a dicing ring, through a rotary blade, 0 Full cut into 6 mm × 0.3 mm chips. After the cutting, a heat treatment at 130 ° C. for 60 seconds was performed on a hot plate while being attached and fixed to the dicing ring, and after cooling, the chip was collected by inverting vibration.

参考例1
厚さ100μmのポリエステルフィルム上に、アクリル酸2−エチルヘキシル−アクリル酸エチル−メチルメタクリレート共重合体系感圧接着剤(ポリウレタン系架橋剤1重量部配合)を含むトルエン溶液を、乾燥後の厚さが10μmとなるように塗布、乾燥してゴム状有機弾性層を形成した。
実施例1と同様にして、アクリル酸2−エチルヘキシル−アクリル酸エチル−メチルメタクリレート共重合体系感圧接着剤100重量部(ポリウレタン系架橋剤2重量部配合)に、分級済み熱膨張性微小球B30重量部を配合してなるトルエン溶液を調製し、これを、セパレータ上に乾燥後の厚みが35μmとなるように塗布、乾燥して粘着層を形成した後、上記ゴム状有機弾性層を形成したポリエステルフィルムのゴム状有機弾性層側に貼り合わせ、加熱剥離性粘着シートを得た。
次に、上記の加熱剥離型粘着シートの粘着面に120mm×100mm×厚さ0.5mmのセラミックシート(焼成前)を仮固定し、それをダイシングリングに装着固定して回転刃を介し、0.6mm×0.3mmのチップにフルカットした。前記カット後、ダイシングリングに装着固定したままの状態で130℃×60秒の加熱処理をホットプレート上で行い、冷却後、反転振動させてチップを回収した。
Reference example 1
On a polyester film having a thickness of 100 μm, a toluene solution containing 2-ethylhexyl acrylate-ethyl acrylate-methyl methacrylate copolymer pressure sensitive adhesive (containing 1 part by weight of a polyurethane-based cross-linking agent) has a thickness after drying. The rubber-like organic elastic layer was formed by applying and drying to a thickness of 10 μm.
In the same manner as in Example 1, 100 parts by weight of 2-ethylhexyl acrylate-ethyl acrylate-methyl methacrylate copolymer pressure-sensitive adhesive (containing 2 parts by weight of a polyurethane-based crosslinking agent) and classified thermally expandable microspheres B30 A toluene solution prepared by blending parts by weight was prepared, and this was coated on the separator so that the thickness after drying was 35 μm, dried to form an adhesive layer, and then the rubbery organic elastic layer was formed. The polyester film was bonded to the rubbery organic elastic layer side to obtain a heat-peelable pressure-sensitive adhesive sheet.
Next, a 120 mm × 100 mm × 0.5 mm thick ceramic sheet (before firing) is temporarily fixed to the adhesive surface of the heat-peelable adhesive sheet, and the ceramic sheet is attached and fixed to a dicing ring, through a rotary blade, 0 Full cut into 6 mm × 0.3 mm chips. After the cutting, a heat treatment at 130 ° C. for 60 seconds was performed on a hot plate while being attached and fixed to the dicing ring, and after cooling, the chip was collected by inverting vibration.

実施例2
分級済み熱膨張性微小球Bの代わりに熱膨張性微小球C(マツモトマイクロスフェアF−301D:松本油脂製薬(株)製:平均粒子径11.6μm、最大粒径42μm)を粘着層に添加するとともに、チップ切断後の加熱処理条件を100℃×60秒とした以外は、実施例1と同様の操作を行った。
Example 2
Instead of classified thermally expandable microspheres B, thermally expandable microspheres C (Matsumoto Microsphere F-301D: manufactured by Matsumoto Yushi Seiyaku Co., Ltd .: average particle size 11.6 μm, maximum particle size 42 μm) are added to the adhesive layer In addition, the same operation as in Example 1 was performed except that the heat treatment condition after cutting the chip was set to 100 ° C. × 60 seconds.

比較例1
分級済み熱膨張性微小球Bの代わりに熱膨張性微小球A(マツモトマイクロスフェアF−50D:松本油脂製薬(株)製:平均粒子径13.4μm、最大粒径63μm)を粘着層に添加した以外は、実施例1と同様の操作を行った。
Comparative Example 1
Instead of classified thermally expandable microspheres B, thermally expandable microspheres A (Matsumoto Microsphere F-50D: manufactured by Matsumoto Yushi Seiyaku Co., Ltd .: average particle size 13.4 μm, maximum particle size 63 μm) are added to the adhesive layer Except that, the same operation as in Example 1 was performed.

比較例2
分級済み熱膨張性微小球Bの代わりに熱膨張性微小球A(マツモトマイクロスフェアF−50D:マツモト油脂製薬(株)製:平均粒子径13.4μm、最大粒径63μm)を粘着層に添加した以外は、参考例1と同様の操作を行った。
Comparative Example 2
Instead of classified thermally expandable microspheres B, thermally expandable microspheres A (Matsumoto Microsphere F-50D: manufactured by Matsumoto Yushi Seiyaku Co., Ltd .: average particle size 13.4 μm, maximum particle size 63 μm) are added to the adhesive layer The same operation as in Reference Example 1 was performed except that.

評価試験
実施例及び比較例で得られた粘着シートの加熱前の粘着層表面の中心線平均粗さ及び最大粗さ、並びにチップ切断時のチップ保持率を表1に示した。粘着層表面の中心線平均粗さと最大粗さは、ZYGO社製、非接触三次元表面粗さ計により測定した。なお、実施例、比較例の何れの場合にも、加熱剥離回収後のチップ剥離面に糊残りは認められなかった。
Evaluation Test Table 1 shows the centerline average roughness and maximum roughness of the pressure-sensitive adhesive layer surface before heating of the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples, and the chip retention rate at the time of chip cutting. The center line average roughness and maximum roughness of the adhesive layer surface were measured with a non-contact three-dimensional surface roughness meter manufactured by ZYGO. In either case of the example or the comparative example, no adhesive residue was observed on the chip peeling surface after heat peeling recovery.

Figure 0003804805
Figure 0003804805

本発明の加熱剥離型粘着シートの一例を示す概略断面図である。It is a schematic sectional drawing which shows an example of the heat peeling type adhesive sheet of this invention. 本発明の加熱剥離型粘着シートの他の例を示す概略断面図である。It is a schematic sectional drawing which shows the other example of the heat peeling type adhesive sheet of this invention.

符号の説明Explanation of symbols

1 基材
2 ゴム状有機弾性層
3 熱膨張性粘着層
4 セパレータ
1 Base material
2 Rubbery organic elastic layer
3 Thermally expandable adhesive layer
4 Separator

Claims (7)

基材の少なくとも片側に熱膨張性微小球を含有する熱膨張性粘着層が設けられた加熱剥離型粘着シートの製造方法であって、「熱膨張性粘着層の厚さ≧該熱膨張性粘着層中の熱膨張性微小球の最大粒径」となるように、該熱膨張性粘着層の厚さと該熱膨張性粘着層に添加する熱膨張性微小球の粒径とを調整して熱膨張性粘着層を形成することにより、加熱前の熱膨張性粘着層表面の中心線平均粗さが0.4μm以下の加熱剥離型粘着シートを得ることを特徴とする電子部品切断時の仮固定用加熱剥離型粘着シートの製造方法A method for producing a heat-peelable pressure-sensitive adhesive sheet in which a heat-expandable pressure-sensitive adhesive layer containing heat-expandable microspheres is provided on at least one side of a substrate , wherein “the thickness of the heat-expandable pressure-sensitive adhesive layer ≧ the heat-expandable pressure-sensitive adhesive layer” Adjusting the thickness of the heat-expandable adhesive layer and the particle diameter of the heat-expandable microspheres added to the heat-expandable adhesive layer so that the maximum particle diameter of the heat-expandable microspheres in the layer is reached. Temporary fixing at the time of cutting an electronic component, characterized in that a heat-peelable pressure-sensitive adhesive sheet having a center line average roughness of 0.4 μm or less on the surface of the heat-expandable pressure-sensitive adhesive layer before heating is obtained by forming an expandable pressure-sensitive adhesive layer Of manufacturing a heat-peelable pressure-sensitive adhesive sheet . 熱膨張性微小球の粒径を分級により調整する請求項1記載の電子部品切断時の仮固定用加熱剥離型粘着シートの製造方法。The method for producing a heat-peelable pressure-sensitive adhesive sheet for temporarily fixing when cutting an electronic component according to claim 1, wherein the particle size of the thermally expandable microsphere is adjusted by classification. 分級を遠心力型風力分級機を用いて行う請求項2記載の電子部品切断時の仮固定用加熱剥離型粘着シートの製造方法。The method for producing a heat-peelable pressure-sensitive adhesive sheet for temporary fixing at the time of cutting an electronic component according to claim 2, wherein the classification is performed using a centrifugal air classifier. 基材として表面処理が施された基材を用いる請求項1〜3の何れかの項に記載の電子部品切断時の仮固定用加熱剥離型粘着シートの製造方法。The method for producing a heat-fixable pressure-sensitive adhesive sheet for temporary fixing at the time of cutting an electronic component according to any one of claims 1 to 3, wherein a base material that has been surface-treated is used as the base material. 加熱前の熱膨張性粘着層表面の最大粗さが5μm以下の加熱剥離型粘着シートを得る請求項1〜4の何れかの項に記載の電子部品切断時の仮固定用加熱剥離型粘着シートの製造方法。The heat-peelable pressure-sensitive adhesive sheet for temporary fixing at the time of cutting an electronic component according to any one of claims 1 to 4, wherein a heat-peelable pressure-sensitive adhesive sheet having a surface roughness of 5 µm or less is obtained. Manufacturing method. 基材と熱膨張性粘着層との間にゴム状有機弾性層を設ける請求項1〜5の何れかの項に記載の電子部品切断時の仮固定用加熱剥離型粘着シートの製造方法。The method for producing a heat-fixable pressure-sensitive adhesive sheet for temporary fixing at the time of cutting an electronic component according to any one of claims 1 to 5, wherein a rubbery organic elastic layer is provided between the base material and the thermally expandable pressure-sensitive adhesive layer. ゴム状有機弾性層を粘着性物質で形成する請求項6記載の電子部品切断時の仮固定用加熱剥離型粘着シートの製造方法。The method for producing a heat-fixable pressure-sensitive adhesive sheet for temporary fixing at the time of cutting an electronic component according to claim 6, wherein the rubbery organic elastic layer is formed of an adhesive substance.
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JP5047724B2 (en) * 2007-07-31 2012-10-10 日東電工株式会社 A method for processing an adherend using a heat-peelable pressure-sensitive adhesive sheet.
CN109072022B (en) * 2016-05-12 2022-10-28 索马龙株式会社 Adhesive sheet and method for producing adherend laminate
WO2019187249A1 (en) * 2018-03-30 2019-10-03 リンテック株式会社 Multilayer body for preventing warp of cured sealed body and method for producing cured sealed body
JP7126424B2 (en) * 2018-10-09 2022-08-26 日東シンコー株式会社 Insulating heat radiation sheet with release sheet

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