JP7214302B2 - thin support adhesive film - Google Patents
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- JP7214302B2 JP7214302B2 JP2018247034A JP2018247034A JP7214302B2 JP 7214302 B2 JP7214302 B2 JP 7214302B2 JP 2018247034 A JP2018247034 A JP 2018247034A JP 2018247034 A JP2018247034 A JP 2018247034A JP 7214302 B2 JP7214302 B2 JP 7214302B2
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- adhesive layer
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- sensitive adhesive
- adhesive film
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- 239000002313 adhesive film Substances 0.000 title claims description 33
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 53
- 239000010410 layer Substances 0.000 claims description 36
- 239000000853 adhesive Substances 0.000 claims description 33
- 230000001070 adhesive effect Effects 0.000 claims description 33
- 239000012790 adhesive layer Substances 0.000 claims description 27
- 239000000758 substrate Substances 0.000 claims description 24
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 22
- 125000000524 functional group Chemical group 0.000 claims description 20
- 239000011521 glass Substances 0.000 claims description 17
- 239000003999 initiator Substances 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 14
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- 239000004697 Polyetherimide Substances 0.000 claims description 7
- 230000001678 irradiating effect Effects 0.000 claims description 7
- 229920001601 polyetherimide Polymers 0.000 claims description 7
- 229920001721 polyimide Polymers 0.000 claims description 6
- 239000004642 Polyimide Substances 0.000 claims description 5
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 4
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 4
- 229920002312 polyamide-imide Polymers 0.000 claims description 3
- 239000004962 Polyamide-imide Substances 0.000 claims description 2
- 239000010408 film Substances 0.000 description 26
- 239000000463 material Substances 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 10
- 229920006255 plastic film Polymers 0.000 description 9
- 239000002985 plastic film Substances 0.000 description 9
- 238000001723 curing Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- -1 benzyl methyl Chemical group 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GQAGPAMZLWKSHA-UHFFFAOYSA-N 2-[2-(2-hydroxy-2-phenylacetyl)-6-methoxyphenyl]benzoic acid Chemical compound COC1=CC=CC(=C1C2=CC=CC=C2C(=O)O)C(=O)C(C3=CC=CC=C3)O GQAGPAMZLWKSHA-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- WVRHNZGZWMKMNE-UHFFFAOYSA-N 2-hydroxy-1-[2-(2-methylpropyl)phenyl]-2-phenylethanone Chemical compound CC(C)CC1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 WVRHNZGZWMKMNE-UHFFFAOYSA-N 0.000 description 1
- NACPTFCBIGBTSJ-UHFFFAOYSA-N 2-hydroxy-2-phenyl-1-(2-propan-2-ylphenyl)ethanone Chemical compound CC(C)C1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 NACPTFCBIGBTSJ-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229940105570 ornex Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Liquid Crystal (AREA)
- Electroluminescent Light Sources (AREA)
- Surface Treatment Of Glass (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、薄膜基板や薄膜シートを使用する部品の製造や加工において、加熱工程を含む工程中の部品の取り扱いを容易にするために、薄膜基板や薄膜シートの補強の為に用いられる粘着フィルムに関する。 The present invention is an adhesive film used for reinforcing thin film substrates and thin film sheets in order to facilitate handling of parts during processes including heating processes in the manufacture and processing of parts using thin film substrates and thin film sheets. Regarding.
近年、太陽電池（ＰＶ）、液晶パネル（ＬＣＤ）、有機ＥＬパネル（ＯＬＥＤ）などのデバイス（電子機器）の薄型化、軽量化が進行しており、これらのデバイスに用いる部品としてのガラス基板の薄膜化が進行している。薄膜化によりガラス基板の強度が不足すると、デバイスの製造や加工工程において、ガラス基板の取り扱いが困難になる。 In recent years, devices (electronic devices) such as solar cells (PV), liquid crystal panels (LCD), and organic EL panels (OLED) are becoming thinner and lighter. Thinning is progressing. If the strength of the glass substrate is insufficient due to thinning, it becomes difficult to handle the glass substrate in device manufacturing and processing steps.
また、半導体や、回路基板などの製造や加工工程においても薄膜化の要求があり、前記のガラス基板と同様に強度不足による製造や加工工程での取り扱いが困難となる。具体的には半導体チップそのものや、半導体チップを載せてボンディングを行う為の基板や、主にポリイミドやいわゆるガラスエポキシからなる電子回路のフレキシブル基板などの薄膜化が進行している。 In addition, there is a demand for a thin film in the manufacturing and processing steps of semiconductors, circuit boards, and the like. Specifically, semiconductor chips themselves, substrates on which semiconductor chips are mounted and bonded, and flexible substrates for electronic circuits mainly made of polyimide or so-called glass epoxy are becoming thinner.
これら薄膜化した部品の取り扱いを容易にするためには、薄膜化した部品をサポートするために、粘着剤を基材に積層した粘着フィルムをサポートフィルムとして貼着して強度を確保した上で作業を行い、作業終了後に前記粘着フィルムを剥がす方法が考えられる。例えば特許文献１には薄膜化したガラス基板のハンドリング性や加工性を改善するための易剥離性のプラスチックフィルムが開示されている。また特許文献２には薄膜化したポリイミドフィルムを作製する際の補強用フィルムの例が開示されている。 In order to facilitate the handling of these thinned parts, in order to support the thinned parts, an adhesive film laminated with an adhesive is attached as a support film to secure the strength before working. and peel off the adhesive film after the work is completed. For example, Patent Literature 1 discloses an easily peelable plastic film for improving the handleability and workability of a thin glass substrate. Further, Patent Document 2 discloses an example of a reinforcing film for producing a thin polyimide film.
さらに、これらのデバイスや部品の製造や加工工程においては、例えば半導体を封止したり、回路を固定したり、保護層を形成したりする際に基板上に設置された樹脂の熱硬化を行うことがあり、例えば１８０℃程度の高温加熱が行われる。 Furthermore, in the manufacturing and processing processes of these devices and parts, for example, when semiconductors are sealed, circuits are fixed, and protective layers are formed, the resin placed on the substrate is thermally cured. For example, high temperature heating of about 180° C. is performed.
このような高温加熱を受ける部品をサポートする粘着フィルムとしては、基材および粘着剤が十分な耐熱性を持ち、かつ高温環境を通過後、粘着フィルムの剥離時に部品側に粘着剤が付着する、いわゆる糊残りを起こさないことが必要となる。しかしながら特許文献１には、前記のような耐熱性に配慮した内容は記載されていない。 As an adhesive film that supports parts subjected to such high temperature heating, the base material and adhesive have sufficient heat resistance, and after passing through a high temperature environment, the adhesive adheres to the part side when the adhesive film is peeled off. It is necessary not to cause so-called adhesive residue. However, Patent Literature 1 does not describe the consideration of heat resistance as described above.
また、特許文献２には耐熱性を配慮した粘着剤層の記載があり、実施例でシリコーン粘着剤の例が開示されている。しかしながら前記のデバイスや部品においては、部品上の残留シリコーンを嫌う場合もある。この場合にはシリコーン粘着剤は使用できないが、特許文献２においてはシリコーン粘着剤以外に耐熱性があり、補強用フィルムに使用可能な粘着剤は開示されていない。 Further, Patent Document 2 describes a pressure-sensitive adhesive layer considering heat resistance, and discloses an example of a silicone pressure-sensitive adhesive in Examples. However, in the above devices and parts, there are cases where residual silicone on the parts is undesirable. In this case, a silicone pressure-sensitive adhesive cannot be used, but Patent Document 2 does not disclose any heat-resistant pressure-sensitive adhesive that can be used for the reinforcing film, other than the silicone pressure-sensitive adhesive.
本発明は、被着体に貼着後、光硬化を行うことで高温環境を経ても被着体から糊残りなく容易に剥離可能なアクリル系粘着フィルムを提供する。また、前記粘着フィルムを用いた被着体の加工方法に関する。 The present invention provides an acrylic pressure-sensitive adhesive film that can be easily peeled off from an adherend without adhesive residue even in a high-temperature environment by performing photocuring after being adhered to the adherend. Moreover, it is related with the processing method of the to-be-adhered body using the said adhesive film.
本発明者は、鋭意検討を行った結果、基材にＴｇが８５℃以上の樹脂を用い、前記基材の一方の面に粘着剤層を設置した粘着フィルムにおいて、前記粘着剤層が多官能ウレタンアクリレートと光重合開始剤およびイソボルニルアクリレートモノマー（ＩＢＸＡ）を含有し、前記多官能ウレタンアクリレート１分子当たりの官能基数、および重量平均分子量と１分子当たりの官能基数の比率を特定の範囲とすることで、被着体に貼着、光硬化を行った後に高温環境を経ても被着体から糊残りなくスムーズに剥離可能な粘着フィルムを提供できるようになった。
As a result of intensive studies, the present inventors have found that in a pressure-sensitive adhesive film in which a resin having a Tg of 85° C. or higher is used as a substrate and an adhesive layer is provided on one surface of the substrate, the pressure-sensitive adhesive layer is multifunctional. It contains a urethane acrylate, a photopolymerization initiator and an isobornyl acrylate monomer (IBXA), and the number of functional groups per molecule of the polyfunctional urethane acrylate and the ratio of the weight average molecular weight and the number of functional groups per molecule are within specific ranges. As a result, it is possible to provide a pressure-sensitive adhesive film that can be smoothly peeled off from an adherend without leaving an adhesive residue even after being subjected to a high-temperature environment after being adhered to the adherend and photocured.
第１発明は、Ｔｇ８５℃以上の樹脂からなる基材の一方の面に粘着剤層を設置した粘着フィルムであって、前記粘着剤層が多官能ウレタンアクリレートと光重合開始剤およびイソボルニルアクリレートモノマー（ＩＢＸＡ）を含有し、前記多官能ウレタンアクリレート１分子当たりの官能基数が２～２８であり、かつ前記多官能ウレタンアクリレートの重量平均分子量（ＭＷ）と１分子当たりの官能基数の比率が重量平均分子量／官能基数＝２０００～６５００であり、かつ前記粘着剤層中に前記多官能ウレタンアクリレートを４７～９０重量％含有、および前記イソボルニルアクリレートモノマーを７～４５重量％含有する粘着フィルムであって、前記粘着フィルムの粘着剤層をガラス板に貼着後、前記光重合開始剤が反応する波長の光を照射して粘着剤層を硬化した後の粘着力が０．０２Ｎ／ｃｍ以上８．０Ｎ／ｃｍ以下である粘着フィルムである。
A first invention is a pressure-sensitive adhesive film having a pressure-sensitive adhesive layer on one side of a substrate made of a resin having a Tg of 85° C. or higher, wherein the pressure-sensitive adhesive layer comprises a polyfunctional urethane acrylate, a photopolymerization initiator, and isobornyl acrylate. It contains a monomer (IBXA), the number of functional groups per molecule of the polyfunctional urethane acrylate is 2 to 28, and the ratio of the weight average molecular weight (MW) of the polyfunctional urethane acrylate to the number of functional groups per molecule is weight An adhesive film having an average molecular weight/functional group number of 2000 to 6500, and containing 47 to 90% by weight of the polyfunctional urethane acrylate and 7 to 45% by weight of the isobornyl acrylate monomer in the adhesive layer. After the adhesive layer of the adhesive film is attached to the glass plate, the adhesive layer is cured by irradiating light with a wavelength at which the photopolymerization initiator reacts, and the adhesive strength is 0.02 N / cm or more. The pressure-sensitive adhesive film is 8.0 N/cm or less.
第２発明は、前記基材がポリイミド、ポリアミドイミド、ポリエーテルイミド、ポリフェニレンサルファイドから選ばれた１種である第１発明に記載の粘着フィルムである。 A second invention is the adhesive film according to the first invention, wherein the substrate is one selected from polyimide, polyamideimide, polyetherimide, and polyphenylene sulfide.
第３発明は、前記粘着フィルムを被着体に貼着後、粘着フィルム側から前記光重合開始剤が反応する波長の光を照射して粘着剤層を光硬化させた後に、被着体に粘着フィルムを貼着した状態で加工を行い、粘着フィルムが不要となったときに粘着フィルムを被着体から剥離する、第１発明または第２発明のいずれかに記載の粘着フィルムを用いた被着体の加工方法である。 In the third invention, after the adhesive film is attached to the adherend, the adhesive layer is irradiated with light having a wavelength at which the photopolymerization initiator reacts from the adhesive film side, and the adhesive layer is photocured. The substrate using the adhesive film according to either the first or second invention, wherein the adhesive film is processed in a state of being attached, and the adhesive film is peeled off from the adherend when the adhesive film is no longer required. It is a processing method of an adherent.
本発明の粘着フィルムは、Ｔｇ８５℃以上の樹脂からなる基材上に粘着剤層を設置してなり、前記粘着剤層が多官能ウレタンアクリレートと光重合開始剤およびイソボルニルアクリレートモノマーを含有し、前記多官能ウレタンアクリレート１分子当たりの官能基数、および重量平均分子量と１分子当たりの官能基数の比率を特定の範囲とすることで、粘着剤層を被着体と貼着した後に、前記粘着剤層を光硬化しても被着体との粘着を維持し、かつ製造工程中の高温環境に耐えて使用後に被着体から糊残りなくスムーズに剥離することを可能とするものである。
The pressure-sensitive adhesive film of the present invention comprises a base material made of a resin having a Tg of 85° C. or higher and a pressure-sensitive adhesive layer provided thereon. The pressure-sensitive adhesive layer contains a polyfunctional urethane acrylate, a photopolymerization initiator, and an isobornyl acrylate monomer. , by setting the number of functional groups per molecule of the polyfunctional urethane acrylate and the ratio of the weight average molecular weight to the number of functional groups per molecule in specific ranges, after the adhesive layer is attached to the adherend, the adhesive Even if the agent layer is photo-cured, it maintains adhesion to the adherend, withstands high-temperature environments during manufacturing processes, and can be smoothly peeled off from the adherend after use without adhesive residue.
以下に本発明の粘着フィルムを、その構成要素に基づいて、さらに詳しく説明する。 The pressure-sensitive adhesive film of the present invention will be described in more detail below based on its constituent elements.
（全体構成）
本発明の粘着フィルムは、基材をＴｇが８５℃以上の樹脂からなるものとし、粘着剤層が多官能ウレタンアクリレートと光重合開始剤およびイソボルニルアクリレートモノマーを含有し、前記多官能ウレタンアクリレート１分子当たりの官能基数と、重量平均分子量と１分子当たりの官能基数との比率を特定の範囲として、前記基材に前記粘着剤層を設置してなる粘着フィルムである。
(overall structure)
In the pressure-sensitive adhesive film of the present invention, the base material is made of a resin having a Tg of 85° C. or higher, the pressure-sensitive adhesive layer contains a polyfunctional urethane acrylate, a photopolymerization initiator and an isobornyl acrylate monomer, and the polyfunctional urethane acrylate The pressure-sensitive adhesive film is obtained by disposing the pressure-sensitive adhesive layer on the base material while setting the number of functional groups per molecule and the ratio of the weight average molecular weight to the number of functional groups per molecule within specific ranges.
（基材）
本発明の粘着フィルムの構成要素のうち、基材となる樹脂は、耐熱性があり高温加熱に耐えられるような樹脂が用いられる。具体的にはＴｇが８５℃以上の樹脂が良好に使用でき、ポリイミド（ＰＩ）、ポリアミドイミド（ＰＡＩ）、ポリエーテルイミド（ＰＥＩ）、ポリフェニレンサルファイド（ＰＰＳ）等の樹脂が挙げられる。この内耐熱性や粘着剤層との密着性、基材としてのフィルムの入手性から特にポリエーテルイミドが良好に使用される。
(Base material)
Among the constituent elements of the pressure-sensitive adhesive film of the present invention, a resin that is heat-resistant and can withstand high-temperature heating is used as the base resin. Specifically, resins having a Tg of 85° C. or higher can be favorably used, and resins such as polyimide (PI), polyamideimide (PAI), polyetherimide (PEI), and polyphenylene sulfide (PPS) can be mentioned. Of these, polyetherimide is particularly favorably used because of its heat resistance, adhesiveness with the pressure-sensitive adhesive layer, and availability of films as substrates.
前記基材の厚みは、１２～２００μｍが良好であり、２５～１２５μｍがより良好である。基材厚が１２μｍ未満では、加工時のサポートフィルムとしては強度不足となる。２００μｍより厚くなると、柔軟性が無くなって被着体からの剥離が困難となる。また剥離時に被着体を損傷する場合があり、価格も高くなる。 The thickness of the substrate is preferably 12-200 μm, more preferably 25-125 μm. If the thickness of the base material is less than 12 μm, the strength as a support film during processing is insufficient. If it is thicker than 200 μm, it loses its flexibility and becomes difficult to peel off from the adherend. Moreover, the adherend may be damaged during peeling, resulting in a high price.
前記基材には、所望に応じて粘着剤層を設置する表面にコロナ放電処理、紫外線照射処理、プラズマ処理、火炎処理を行ってもよく、必要に応じてアンカー層等を設置してもよい。アンカー層等を設置する方法としては、製膜時に設置するいわゆるインライン法、または製膜したフィルムに設置するいわゆるオフライン法のいずれでもよい。 The base material may be subjected to corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, or flame treatment on the surface on which the pressure-sensitive adhesive layer is to be provided, if desired, and may be provided with an anchor layer or the like as necessary. . The method for installing the anchor layer or the like may be a so-called in-line method in which it is installed during film formation, or a so-called offline method in which it is installed on the formed film.
（粘着剤層）
本発明の粘着フィルムの粘着剤層としては、被着体に確実に貼着し、高温環境を経たあとでも、糊残りなく剥離可能であることが必要である。これらの条件を満たす為に、本発明においては、粘着剤層が多官能ウレタンアクリレートと光重合開始剤およびイソボルニルアクリレートモノマーを含有し、前記多官能ウレタンアクリレート１分子当たりの官能基数と、重量平均分子量と１分子当たりの官能基数との比率を特定の範囲とした。この粘着剤層を基材上に設置して粘着フィルムとなし、前期粘着フィルムを被着体に貼着した後に、前記光重合開始剤の反応する波長の光を照射して前記粘着剤層を硬化することで、硬化後も被着体との粘着を維持し、高温環境を経た後でも被着体から糊残りなくスムーズに剥離することができる。
(Adhesive layer)
The pressure-sensitive adhesive layer of the pressure-sensitive adhesive film of the present invention needs to be able to adhere reliably to an adherend and be peelable without adhesive residue even after being exposed to a high-temperature environment. In order to satisfy these conditions, in the present invention, the pressure-sensitive adhesive layer contains a polyfunctional urethane acrylate, a photopolymerization initiator, and an isobornyl acrylate monomer, and the number and weight of functional groups per molecule of the polyfunctional urethane acrylate and weight . The ratio between the average molecular weight and the number of functional groups per molecule was defined as a specific range. This pressure-sensitive adhesive layer is placed on a substrate to form a pressure-sensitive adhesive film, and after the pressure-sensitive adhesive film is adhered to an adherend, light having a wavelength at which the photopolymerization initiator reacts is irradiated to remove the pressure-sensitive adhesive layer. By curing, it maintains adhesion to the adherend even after curing, and can be peeled off smoothly from the adherend without adhesive residue even after passing through a high-temperature environment.
（多官能ウレタンアクリレート）
前記の多官能ウレタンアクリレートとしては、１分子当たりの官能基数が２～２８のものが好適に使用できる。官能基数が２未満の場合、粘着剤層の硬化後の凝集力が低くなり、耐熱性が低くなったり、糊残りのおそれがある。官能基数が２８を超える場合は、硬化後の硬度が高くなりすぎ、被着体への粘着力が低くなる。
(polyfunctional urethane acrylate)
As the polyfunctional urethane acrylate, those having 2 to 28 functional groups per molecule can be preferably used. If the number of functional groups is less than 2, the cohesive force after curing of the pressure-sensitive adhesive layer may be low, the heat resistance may be low, and there may be adhesive residue. If the number of functional groups exceeds 28, the hardness after curing becomes too high and the adhesive strength to adherends becomes low.
また、前記の多官能ウレタンアクリレートは、重量平均分子量（ＭＷ）と前記１分子当たりの官能基数の比率が、ＭＷ／官能基数＝２０００～６５００のものが好適に使用できる。比率が２０００未満の場合は、硬化後の架橋密度が高くなりすぎて粘着剤層の粘着力が低くなり、被着体の加工中に粘着フィルムが剥がれてしまうおそれがある。比率が６５００を超える場合は、架橋密度が低くなりすぎて粘着剤層の凝集力が低くなり、被着体からの剥離時に糊残りが発生するおそれがある。 Moreover, the above polyfunctional urethane acrylate having a weight average molecular weight (MW) to the number of functional groups per molecule ratio of MW/number of functional groups of 2000 to 6500 can be suitably used. If the ratio is less than 2,000, the crosslink density after curing becomes too high and the adhesive strength of the adhesive layer becomes low, which may cause the adhesive film to peel off during processing of the adherend. If the ratio exceeds 6500, the crosslink density becomes too low, the cohesive force of the pressure-sensitive adhesive layer becomes low, and adhesive residue may occur when peeled from the adherend.
前記の多官能ウレタンアクリレートとしては、水酸基含有単官能（メタ）アクリレートモノマーと各種ジイソシアネートとの２:１付加体（２官能）、ジペンタエリスリトールペンタ（メタ）アクリレートとヘキサメチレンジイソシアネートとの２：１付加体（１０官能）、ペンタエリスリトールトリ（メタ）アクリレートとイソホロンジイソシアネートとの２：１付加体（６官能）等が挙げられる。市販品としては、例えば例えば日本合成化学（株）の紫光ＵＶ３３００Ｂ（２官能）、根上工業（株）のＵＮ－５５００（１３．３官能）、ダイセルオルネクス（株）のＥＢＥＣＲＹＬ２３０、ＫＲＭ８９０１（２官能）等が挙げられるが、これらに限定されるものではない。 Examples of the polyfunctional urethane acrylate include a 2:1 adduct (bifunctional) of a hydroxyl group-containing monofunctional (meth)acrylate monomer and various diisocyanates, and a 2:1 adduct (bifunctional) of dipentaerythritol penta(meth)acrylate and hexamethylene diisocyanate. An adduct (10-functional), a 2:1 adduct (6-functional) of pentaerythritol tri(meth)acrylate and isophorone diisocyanate, and the like can be mentioned. Commercially available products include, for example, Shikou UV3300B (bifunctional) manufactured by Nippon Synthetic Chemical Industry Co., Ltd., UN-5500 (13.3 functional) manufactured by Neagari Kogyo Co., Ltd., EBECRYL230 and KRM8901 (bifunctional) manufactured by Daicel Ornex Co., Ltd. ) and the like, but are not limited to these.
（光重合開始剤）
本発明の粘着剤層に使用可能な光重合開始剤は、紫外線、または可視光を照射することで多官能ウレタンアクリレートおよびイソボルニルアクリレートモノマーの官能基を重合して粘着剤層を硬化する作用を持つものであれば、特に制限無く使用可能であるが、取り扱い上からは、紫外線で反応する紫外線重合開始剤が好適に使用可能である。
(Photoinitiator)
The photopolymerization initiator that can be used in the pressure-sensitive adhesive layer of the present invention has the action of curing the pressure-sensitive adhesive layer by polymerizing the functional groups of the polyfunctional urethane acrylate and isobornyl acrylate monomers by irradiating with ultraviolet light or visible light. However, from the point of view of handling, an ultraviolet polymerization initiator that reacts with ultraviolet rays can be preferably used.
前記光重合開始剤の粘着剤層中の含有量は、０．５～５．０重量％が好適である。含有量が０．５重量％未満であれば、粘着剤層の硬化不足となり、被着体からの剥離時に糊残りをおこすおそれがある。含有量が５．０重量％を超えた場合は架橋密度が高くなりすぎて、被着体との粘着力が低くなるおそれがある。 The content of the photopolymerization initiator in the adhesive layer is preferably 0.5 to 5.0% by weight. If the content is less than 0.5% by weight, the adhesive layer will be insufficiently hardened, and may leave an adhesive residue when peeled from the adherend. If the content exceeds 5.0% by weight, the crosslink density may become too high, and the adhesive strength to the adherend may become low.
前記光重合開始剤としては、例えばベンゾインエ－テル系（イソピロピルベンゾインエ－テル、イソブチルベンゾインエ－テル、ベンゾインエチルエ－テル、ベンゾインメチルエ－テル）、ベンジルケタ－ル系（ヒドロシクロヘキシルフェニルケトン、ベンジルメチルケタ－ル）、ケトンベンゾフェノン系（ベンジル、メチル－Ｏ－ベンゾインベンゾエ－ト、２－クロロチオキサントン、メチルトオオキサントン）、ベンゾフェノン系（ベンゾフェノン）、アシルホスフィンオキサイド系等が特に制限無く使用可能であるが、基材にポリエーテルイミドを用いて、粘着剤層硬化のための紫外線を基材側から照射する場合は、ポリエーテルイミドが４００ｎｍより短い波長の紫外線を透過しないので、４００ｎｍよりも長波長の紫外線を使用する必要がある。このような場合には、４００ｎｍよりも長波長の紫外線で反応が可能な重合開始剤、例えばビス（２、４、６トリメチルベンゾイル）フェニルホスフィンオキサイド（以下ＢＡＰＯ：ビスアシルホスフィンオキサイドと略す場合あり）や４、４´ビス（ジエチルアミノ）ベンゾフェノン等が好適に用いられる。また、紫外線を照射する光源も波長４００ｎｍの紫外線を照射可能なメタルハライドランプ等が好適に用いられる。 Examples of the photopolymerization initiator include benzoin ether (isopropyl benzoin ether, isobutyl benzoin ether, benzoin ethyl ether, benzoin methyl ether), benzyl ketal (hydrocyclohexylphenyl ketone , benzyl methyl ketal), ketone benzophenones (benzyl, methyl-O-benzoinbenzoate, 2-chlorothioxanthone, methylthoxanthone), benzophenones (benzophenone), acylphosphine oxides, etc. are used without particular restrictions. Although it is possible, when polyetherimide is used for the base material and ultraviolet rays for curing the adhesive layer are irradiated from the base side, polyetherimide does not transmit ultraviolet rays with a wavelength shorter than 400 nm. also need to use long-wave ultraviolet light. In such a case, a polymerization initiator capable of reacting with ultraviolet light having a wavelength longer than 400 nm, such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (hereinafter abbreviated as BAPO: bisacylphosphine oxide) and 4,4'bis(diethylamino)benzophenone are preferably used. As a light source for irradiating ultraviolet rays, a metal halide lamp or the like capable of irradiating ultraviolet rays having a wavelength of 400 nm is preferably used.
（イソボルニルアクリレートモノマー）
また、本発明の粘着剤層には、多官能ウレタンアクリレートと光重合開始剤に加えて、イソボルニルアクリレートモノマーを含有することで、被着体からの剥離をスムーズにすることが可能である。
(isobornyl acrylate monomer)
In addition to the polyfunctional urethane acrylate and the photopolymerization initiator, the pressure-sensitive adhesive layer of the present invention contains an isobornyl acrylate monomer, thereby enabling smooth peeling from the adherend. .
粘着剤層にイソボルニルアクリレートモノマーを含有すると、紫外線照射による硬化後の粘着剤層が柔軟になるが、粘着力は適度な状態とすることができるので、被着体からの剥離がスムーズになる。前記イソボルニルアクリレートモノマーの粘着剤層中の含有量は、７～４５重量％が好適であり、１０～３５重量％がより好適である。含有量が７重量％未満では所望の性能がえられづらい。含有量が４５重量％を超えると粘着剤層の凝集力が低くなり、糊残りをおこすおそれがある。 When the isobornyl acrylate monomer is contained in the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer becomes flexible after being cured by UV irradiation, but the adhesive strength can be kept in a moderate state, so that it can be peeled off smoothly from the adherend. Become. The content of the isobornyl acrylate monomer in the adhesive layer is preferably 7 to 45% by weight, more preferably 10 to 35% by weight. If the content is less than 7% by weight, it is difficult to obtain the desired performance. If the content exceeds 45% by weight, the cohesive strength of the pressure-sensitive adhesive layer will be low, and there is a risk of causing adhesive residue.
本発明における粘着剤層の粘着力は、粘着フィルムを被着体に貼着し、前記光重合開始剤の反応する波長の光を照射して粘着剤層を硬化させた後の剥離力で、０．０２Ｎ／ｃｍ以上８.０Ｎ／ｃｍ以下が好適であり、０．４Ｎ／ｃｍ以上４.０Ｎ／ｃｍ以下が更に好適である。剥離力が０．０２Ｎ／ｃｍ未満では、被着体に粘着フィルムを貼着した状態での加工作業中に、粘着フィルムが被着体から剥がれてしまうおそれがある。粘着力が８．０Ｎ／ｃｍを超えると、被着体からの剥離時に、被着体を破損するおそれがある。 The adhesive force of the adhesive layer in the present invention is the peel force after the adhesive film is adhered to the adherend and the adhesive layer is cured by irradiating light with a wavelength at which the photopolymerization initiator reacts. 0.02 N/cm or more and 8.0 N/cm or less is preferable, and 0.4 N/cm or more and 4.0 N/cm or less is more preferable. If the peeling force is less than 0.02 N/cm, the adhesive film may be peeled off from the adherend during the processing operation with the adhesive film attached to the adherend. If the adhesive strength exceeds 8.0 N/cm, the adherend may be damaged during peeling from the adherend.
本発明における粘着剤層の厚みは、５μｍ～１００μｍが好適であり、１０μｍ～５０μ
ｍがより好適である。粘着剤層の厚みが５μｍ未満では、十分な粘着力を発揮できない。
厚みが１００μｍを超えると、剥離が困難になったり、糊残りを起こすおそれがある。
The thickness of the pressure-sensitive adhesive layer in the present invention is preferably 5 μm to 100 μm, more preferably 10 μm to 50 μm.
m is more preferred. If the thickness of the pressure-sensitive adhesive layer is less than 5 μm, sufficient adhesive force cannot be exhibited.
If the thickness exceeds 100 μm, it may become difficult to peel off or leave an adhesive residue.
本発明における粘着剤層の形成方法としては、粘着剤層を構成する樹脂を有機溶剤に溶解し粘度を調整した樹脂溶液を塗工する方法や、粘着剤層を構成する樹脂を水に分散し塗工する方法等の公知の方法を用いることができる。前記有機溶剤としては一般の有機溶剤を特に制限無く用いることができる。例えば、トルエン、キシレン、アセトン、メチルエチルケトン等の有機溶剤が挙げられるが、これらに限定されるものではない。 As a method for forming the adhesive layer in the present invention, there is a method of dissolving the resin constituting the adhesive layer in an organic solvent and applying a resin solution whose viscosity is adjusted, or a method of dispersing the resin constituting the adhesive layer in water. A known method such as a coating method can be used. As the organic solvent, a general organic solvent can be used without particular limitation. Examples include, but are not limited to, organic solvents such as toluene, xylene, acetone, and methyl ethyl ketone.
本発明の粘着剤層の塗工方法としては、コンマナイフコーター、ダイコーター、リバースコーターなどが挙げられる。 Examples of the coating method of the pressure-sensitive adhesive layer of the present invention include a comma knife coater, a die coater and a reverse coater.
（セパレータ）
本発明においては、粘着剤層の表面の汚れや異物付着を防いだり、粘着フィルムのハンドリングを向上させる目的で、プラスチックフィルムからなるセパレータを粘着剤層面に貼り合わせて用いることが好適である。前記セパレータは、剥離性の高いプラスチックフィルムよりなり、所望により、前記プラスチックフィルムの表面に剥離剤を形成したものが使用される。
(separator)
In the present invention, it is preferable to use a separator made of a plastic film attached to the surface of the pressure-sensitive adhesive layer for the purpose of preventing stains and adhesion of foreign substances on the surface of the pressure-sensitive adhesive layer and improving the handling of the pressure-sensitive adhesive film. The separator is made of a highly releasable plastic film, and if desired, a release agent is formed on the surface of the plastic film.
前記セパレータのプラスチックフィルムとしては、例えば、セロハンフィルム、ポリエステルフィルム、ポリプロピレンフィルム、ポリエチレンフィルム、ポリカーボネートフィルム、ポリスチレンフィルム等を挙げることができる。プラスチックフィルムの厚さとしては、２５～２００μｍが好ましく用いられる。厚さが２５μｍ未満だとフィルム強度が不足して十分な保護性能が得られなかったり、剥離時にセパレータが破れる等の問題が発生する。また、２００μｍより厚いと取り扱いが困難になったり、プラスチックフィルム自体が高価になる等の問題が発生する。 Examples of the plastic film for the separator include cellophane film, polyester film, polypropylene film, polyethylene film, polycarbonate film, and polystyrene film. The thickness of the plastic film is preferably 25-200 μm. If the thickness is less than 25 μm, the film strength is insufficient, and sufficient protective performance cannot be obtained. On the other hand, if the thickness is more than 200 μm, problems such as difficulty in handling and an increase in the cost of the plastic film itself occur.
前記剥離剤としては、一般的に剥離効果の高いシリコーン系剥離剤が使用可能だが、本発明の粘着フィルムを残留シリコーンを嫌う用途に使用する場合は、シリコーン系以外の材料、例えばポリエチレンやポリプロピレン等のポリオレフィン系や、フッ素系等の剥離効果の高い材料を用いることができる。 As the release agent, it is generally possible to use a silicone-based release agent that has a high release effect. A polyolefin-based material, a fluorine-based material, or the like, having a high peeling effect can be used.
前記剥離剤のプラスチックフィルムへの形成方法は、前記粘着剤層の基材への形成方法と同様の方法を用いることができる。またこれらの剥離剤を前記プラスチックフィルムに形成する面は、所望により片面でも、両面でもよい。 As a method for forming the release agent on the plastic film, the same method as the method for forming the pressure-sensitive adhesive layer on the substrate can be used. Moreover, the surface on which the release agent is formed on the plastic film may be either one surface or both surfaces, as desired.
以下、実施例と比較例を示して本発明を詳細に説明するが、本発明は下記の実施例に制限されるものではない。なお、各実施例中の「部」は特に断ることのない限り重量部を示したものである。 EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In addition, "parts" in each example indicate parts by weight unless otherwise specified.
（実施例１～１５、比較例１～４）
表１および表２の実施例１～１５、比較例１～４の各基材の片面にコロナ放電処理を行い、表１および表２に記載の処方にて混合した各実施例、比較例の各粘着剤層塗工液を、乾燥後の厚みが表１および表２記載の各々の値になるように調整して、各基材のコロナ放電処理した面に塗工し、１００℃で２分間有機溶剤を除去する為に加熱乾燥して各粘着剤層を形成して実施例１～１５、比較例１～４の粘着フィルムを作製した。作製した各粘着フィルムを幅２５ｍｍに切断して、厚み２００μｍのガラス板に各粘着フィルムの粘着剤層を貼着し、照射光量１２０Ｗ／ｃｍのメタルハライドランプにて紫外線を積算光量で２０００ｍｊ／ｃｍ２照射して粘着剤層を硬化した後に、１８０℃で２分間加熱して室温まで冷却し、ガラス板に各粘着フィルムを貼着した積層物を作製した。
(Examples 1 to 15, Comparative Examples 1 to 4)
One side of each base material of Examples 1 to 15 and Comparative Examples 1 to 4 in Tables 1 and 2 was subjected to corona discharge treatment and mixed according to the formulations shown in Tables 1 and 2. Each pressure-sensitive adhesive layer coating solution was adjusted so that the thickness after drying would be each of the values shown in Tables 1 and 2, and was applied to the corona discharge-treated surface of each substrate, followed by heating at 100°C for 2 hours. In order to remove the organic solvent, each adhesive layer was formed by heating and drying for a minute to prepare adhesive films of Examples 1 to 15 and Comparative Examples 1 to 4. Each prepared adhesive film was cut to a width of 25 mm, the adhesive layer of each adhesive film was attached to a glass plate with a thickness of 200 μm, and the integrated light intensity of ultraviolet rays was 2000 mj / cm 2 with a metal halide lamp with an irradiation light intensity of 120 W / cm. After the adhesive layer was cured by irradiation, it was heated at 180° C. for 2 minutes and cooled to room temperature to prepare a laminate in which each adhesive film was adhered to a glass plate.
各実施例、比較例の材料構成比、評価結果を表１および表２に、各評価方法を下記に示す。 Tables 1 and 2 show the material composition ratios and evaluation results of each example and comparative example, and each evaluation method is shown below.
（評価方法）
（粘着力評価）
上記ガラス板と粘着フィルムの積層物において、粘着フィルムを速度３００ｍｍ／ｍｉｎにて１８０°剥離を行い、剥離に要する力を測定して粘着力とした。
評価基準
◎：粘着力が０．４Ｎ／ｃｍ以上４．０Ｎ／ｃｍ以下。
○：粘着力が０．０２Ｎ／ｃｍ以上０．４Ｎ／ｃｍ未満、または４．０Ｎ／ｃｍを超えて８．０Ｎ／ｃｍ以下。
×：粘着力が０．０２Ｎ／ｃｍ未満、または８．０Ｎ／ｃｍを超える。
(Evaluation method)
(Adhesive strength evaluation)
In the laminate of the glass plate and the adhesive film, the adhesive film was peeled off at 180° at a speed of 300 mm/min, and the force required for peeling was measured and used as the adhesive strength.
Evaluation Criteria A: Adhesive strength is 0.4 N/cm or more and 4.0 N/cm or less.
◯: The adhesive strength is 0.02 N/cm or more and less than 0.4 N/cm, or more than 4.0 N/cm and 8.0 N/cm or less.
x: Adhesive strength is less than 0.02 N/cm or more than 8.0 N/cm.
（粘着剤層の耐熱、糊残り性評価）
前記粘着力評価を行った、粘着フィルム剥離後のガラス板上への粘着剤層の付着を、目視確認する方法にて糊残りの評価を行った。
評価基準
○：粘着剤層のガラス板上への付着がない。
×：粘着剤層のガラス板上への付着がある。
(Evaluation of heat resistance and adhesive residue property of adhesive layer)
Adhesion of the adhesive layer on the glass plate after peeling of the adhesive film, which was used for the adhesive strength evaluation, was visually confirmed to evaluate the amount of adhesive residue.
Evaluation Criteria ◯: No adhesion of the pressure-sensitive adhesive layer to the glass plate.
x: Adhesion of the pressure-sensitive adhesive layer to the glass plate is observed.
（剥離性評価）
前記実施例１～１５、比較例１～４の積層体作製において、被着体をガラス板から１００μｍ厚のガラスエポキシ基板に変更した他は同じ方法にて積層体を作製し、作製した各積層体を２５ｍｍ幅に切断してから、粘着フィルムを速度３００ｍｍ／ｍｉｎにて１８０°剥離を行った際に、粘着フィルムがガラスエポキシ基板と貼り付き、基板が折れるかどうかを目視で確認し、剥離性の評価を行った。
評価基準
○：貼り付きの発生が無く、スムーズに剥離できた。ガラスエポキシ基板の折れは発生しなかった。
△：貼り付きが発生し、スムーズに剥離できなかったが、ガラスエポキシ基板の折れは発生しなかった。
×：貼り付きが発生し、ガラスエポキシ基板に折れが発生した。
(Peelability evaluation)
Laminates were produced in the same manner as in the production of the laminates of Examples 1 to 15 and Comparative Examples 1 to 4, except that the adherend was changed from a glass plate to a glass epoxy substrate with a thickness of 100 μm. After cutting the body to a width of 25 mm, peel off the adhesive film at a speed of 300 mm/min at 180°. sex was evaluated.
Evaluation criteria ◯: Smooth peeling without occurrence of sticking. No breakage of the glass epoxy substrate occurred.
Δ: Sticking occurred and could not be peeled off smoothly, but the glass epoxy substrate did not break.
x: Sticking occurred and breakage occurred in the glass epoxy substrate.
Claims (3)
A pressure-sensitive adhesive film having a pressure-sensitive adhesive layer on one side of a substrate made of a resin having a Tg of 85° C. or higher, wherein the pressure-sensitive adhesive layer comprises a polyfunctional urethane acrylate, a photopolymerization initiator, and an isobornyl acrylate monomer (IBXA). and the number of functional groups per molecule of the polyfunctional urethane acrylate is 2 to 28, and the ratio of the weight average molecular weight (MW) of the polyfunctional urethane acrylate to the number of functional groups per molecule is weight average molecular weight/number of functional groups = 2000 to 6500, and contains 47 to 90% by weight of the polyfunctional urethane acrylate and 7 to 45% by weight of the isobornyl acrylate monomer in the adhesive layer, wherein the adhesive After the adhesive layer of the film is attached to the glass plate, the adhesive layer is cured by irradiating light with a wavelength at which the photopolymerization initiator reacts, and the adhesive strength is 0.02 N/cm or more and 8.0 N/cm. Adhesive film which is below.
After the adhesive film is attached to the adherend, the adhesive layer is cured by irradiating the adhesive film with light having a wavelength at which the photopolymerization initiator reacts, and then the adherend is processed. 3. The method for processing an adherend using the adhesive film according to claim 1, wherein the adhesive film is peeled off from the adherend when the film is no longer needed.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012144726A (en) | 2011-01-12 | 2012-08-02 | Dongwoo Fine-Chem Co Ltd | Optical adhesive composition |
| WO2012165368A1 (en) | 2011-05-27 | 2012-12-06 | 電気化学工業株式会社 | Pressure-sensitive adhesive sheet |
| JP2018024785A (en) | 2016-08-10 | 2018-02-15 | 株式会社有沢製作所 | Uv curable type resin composition |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012144726A (en) | 2011-01-12 | 2012-08-02 | Dongwoo Fine-Chem Co Ltd | Optical adhesive composition |
| WO2012165368A1 (en) | 2011-05-27 | 2012-12-06 | 電気化学工業株式会社 | Pressure-sensitive adhesive sheet |
| JP2018024785A (en) | 2016-08-10 | 2018-02-15 | 株式会社有沢製作所 | Uv curable type resin composition |
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