JP5265319B2 - Protective sheet - Google Patents
Protective sheet Download PDFInfo
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- JP5265319B2 JP5265319B2 JP2008310809A JP2008310809A JP5265319B2 JP 5265319 B2 JP5265319 B2 JP 5265319B2 JP 2008310809 A JP2008310809 A JP 2008310809A JP 2008310809 A JP2008310809 A JP 2008310809A JP 5265319 B2 JP5265319 B2 JP 5265319B2
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- epoxy resin
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- protective sheet
- conductive
- layer
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- 230000001681 protective effect Effects 0.000 title claims abstract description 36
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 48
- 239000003822 epoxy resin Substances 0.000 claims abstract description 47
- 239000010410 layer Substances 0.000 claims abstract description 34
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000126 substance Substances 0.000 claims abstract description 22
- 239000012790 adhesive layer Substances 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 16
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 15
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920000767 polyaniline Polymers 0.000 claims abstract description 5
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 5
- 229920000123 polythiophene Polymers 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 16
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 239000004020 conductor Substances 0.000 claims description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 8
- 239000011347 resin Substances 0.000 abstract description 8
- 239000004593 Epoxy Substances 0.000 abstract 1
- 230000006866 deterioration Effects 0.000 abstract 1
- 238000007740 vapor deposition Methods 0.000 abstract 1
- 239000011342 resin composition Substances 0.000 description 9
- -1 polyethylene Polymers 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- GWZFJHOXDUSPDA-UHFFFAOYSA-N 2-butoxyethanol;2-(2-ethoxyethoxy)ethanol Chemical compound CCCCOCCO.CCOCCOCCO GWZFJHOXDUSPDA-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- WVRNUXJQQFPNMN-VAWYXSNFSA-N 3-[(e)-dodec-1-enyl]oxolane-2,5-dione Chemical compound CCCCCCCCCC\C=C\C1CC(=O)OC1=O WVRNUXJQQFPNMN-VAWYXSNFSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 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
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、耐薬品性、導電性及び透明性に優れた電子部品用の保護シートである。 The present invention is a protective sheet for electronic components that is excellent in chemical resistance, conductivity, and transparency.
電子部品用の保護シートは、製造時に受けやすい傷、異物付着、薬品による汚染から保護するために用いられている。 Protective sheets for electronic components are used to protect from scratches, foreign matter adhesion, and chemical contamination that are easily received during manufacturing.
保護シートは、一般に、シート状の基材層と粘着層で形成されている。粘着材としては天然ゴム系やアクリル系の素材が広く使用されているが、これらは耐熱性が低く、通常１５０℃を超えるような環境下では樹脂の劣化が起こり、シート剥離時の樹脂残りが生じていた。 The protective sheet is generally formed of a sheet-like base material layer and an adhesive layer. Natural rubber and acrylic materials are widely used as adhesives, but these have low heat resistance and usually deteriorate in an environment exceeding 150 ° C. It was happening.
保護シートに高い導電性を付与したい場合、一般に導電性フィラーと呼ばれる無機物質を数１０質量部程度添加する必要があるが、この場合、保護シートの透明性は著しく低くなっていた。 When it is desired to impart high conductivity to the protective sheet, it is necessary to add about several tens of parts by mass of an inorganic substance generally called a conductive filler. In this case, the transparency of the protective sheet is extremely low.
電子部品に薬品による処理を行う際、保護シートで局所的に保護する場合がある。この薬品処理をすると、従来の保護シートでは、保護シートの劣化や剥離が生じ、次工程に移る際、保護シートを貼り替える必要があった。（特許文献１） When processing electronic parts with chemicals, they may be locally protected with a protective sheet. When this chemical treatment is performed, in the conventional protective sheet, the protective sheet is deteriorated or peeled off, and it is necessary to replace the protective sheet when moving to the next step. (Patent Document 1)
本発明は、耐薬品性、導電性、かつ透明性をバランスよく付与した保護シートを提供することにある。 An object of the present invention is to provide a protective sheet imparted with a good balance of chemical resistance, conductivity, and transparency.
請求項１に記載の発明は、粘着層、基材層、導電層の順に積層され、粘着層がエポキシ樹脂組成物であり、エポキシ樹脂が、シリコーンとビスフェノールＡ型エポキシ樹脂の共重合体６４〜９６質量％と、エーテル結合又はエステル結合を分子内に含む硬化剤４〜３６質量％との複合体である保護シートである。
請求項２に記載の発明は、シリコーンが、エポキシ樹脂全体の３５〜６５質量％である請求項１記載の保護シートである。
請求項３に記載の発明は、ビスフェノールＡ型エポキシ樹脂が、エポキシ系樹脂の末端部に配置されたことを特徴とする請求項１又は２記載の保護シートである。
請求項４に記載の発明は、導電層がＩＴＯ（Ｉｎｄｉｕｍ Ｔｉｎ Ｏｘｉｄｅ）やアルミニウムなどの導電性物質の蒸着、又はポリピロールやポリチオフェン、ポリアニリンなどの導電性高分子による被覆、又はＩＴＯやＡＴＯ（Ａｎｔｉｍｏｎｙ Ｔｒｉｏｘｉｄｅ）、カーボンブラック、カーボンファイバーなどの導電性物質を添加したトリアジン骨格を有するエポキシ樹脂硬化体からなる請求項１乃至３のいずれか記載の保護シートであ
る。
In the invention according to claim 1, the adhesive layer, the base material layer, and the conductive layer are laminated in this order, the adhesive layer is an epoxy resin composition, and the epoxy resin is a copolymer of silicone and bisphenol A type epoxy resin 64- It is a protective sheet which is a composite of 96% by mass and 4 to 36% by mass of a curing agent containing an ether bond or an ester bond in the molecule.
Invention of Claim 2 is a protective sheet of Claim 1 whose silicone is 35-65 mass% of the whole epoxy resin.
The invention according to claim 3 is the protective sheet according to claim 1 or 2, characterized in that the bisphenol A type epoxy resin is disposed at the end of the epoxy resin.
According to a fourth aspect of the present invention, the conductive layer is formed by depositing a conductive material such as ITO (Indium Tin Oxide) or aluminum, or coating with a conductive polymer such as polypyrrole, polythiophene, or polyaniline, or ITO or ATO (Antimony Trioxide). 4) The protective sheet according to any one of claims 1 to 3, comprising a cured epoxy resin having a triazine skeleton to which a conductive substance such as carbon black or carbon fiber is added.
本発明の保護シートは、上記構成により、耐薬品性、導電性、かつ透明性をバランスよく付与した保護シートである。 The protective sheet of the present invention is a protective sheet imparted with a good balance of chemical resistance, conductivity, and transparency by the above configuration.
以下、本発明について詳細に説明する。
請求項１に記載の発明は、粘着層、基材層、導電層の順に積層され、粘着層がエポキシ樹脂組成物であり、エポキシ樹脂が、シリコーンとビスフェノールＡ型エポキシ樹脂の共重合体６４〜９６質量％と、エーテル結合又はエステル結合を分子内に含む硬化剤の複合体４〜３６質量％である保護シートである。
請求項２に記載の発明は、シリコーンが、エポキシ樹脂全体の３５〜６５質量％である請求項１記載の保護シートである。
請求項３に記載の発明は、ビスフェノールＡ型エポキシ樹脂が、エポキシ系樹脂の末端部に配置されたことを特徴とする請求項１又は２記載の保護シートである。
請求項４に記載の発明は、導電層がＩＴＯ（Ｉｎｄｉｕｍ Ｔｉｎ Ｏｘｉｄｅ）やアルミニウムなどの導電性物質の蒸着、又はポリピロールやポリチオフェン、ポリアニリンなどの導電性高分子による被覆、又はＩＴＯやＡＴＯ（Ａｎｔｉｍｏｎｙ Ｔｒｉｏｘｉｄｅ）、カーボンブラック、カーボンファイバーなどの導電性物質を添加したトリアジン骨格を有するエポキシ樹脂硬化体からなる請求項１乃至３のいずれか記載の保護シートである。
Hereinafter, the present invention will be described in detail.
In the invention according to claim 1, the adhesive layer, the base material layer, and the conductive layer are laminated in this order, the adhesive layer is an epoxy resin composition, and the epoxy resin is a copolymer of silicone and bisphenol A type epoxy resin 64- The protective sheet is 96% by mass and 4 to 36% by mass of a complex of a curing agent containing an ether bond or an ester bond in the molecule.
Invention of Claim 2 is a protective sheet of Claim 1 whose silicone is 35-65 mass% of the whole epoxy resin.
The invention according to claim 3 is the protective sheet according to claim 1 or 2, characterized in that the bisphenol A type epoxy resin is disposed at the end of the epoxy resin.
According to a fourth aspect of the present invention, the conductive layer is formed by depositing a conductive material such as ITO (Indium Tin Oxide) or aluminum, or coating with a conductive polymer such as polypyrrole, polythiophene, or polyaniline, or ITO or ATO (Antimony Trioxide). 4) The protective sheet according to any one of claims 1 to 3, comprising a cured epoxy resin having a triazine skeleton to which a conductive substance such as carbon black or carbon fiber is added.
本発明の保護シートは、粘着層、基材層、導電層の順に積層された構成をとり、このような構成をとることにより、粘着層による被着体への粘着機能、基材層によるシート強度増加、導電処理によるシート表面の導電化が達成できる。 The protective sheet of the present invention has a structure in which an adhesive layer, a base material layer, and a conductive layer are laminated in this order. By taking such a configuration, the adhesive function to the adherend by the adhesive layer, the sheet by the base material layer Increase in strength and electrical conductivity of the sheet surface by conductive treatment can be achieved.
基材層としては、ポリエチレン、ポリプロピレン、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、ポリスチレン、ポリメチルペンテン、ポリエーテルスルホン、ポリエーテルイミド、ポリエーテルエーテルケトン、もしくはこれらの一部を化学修飾した樹脂を使用することができる。 As the base material layer, use polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polystyrene, polymethylpentene, polyethersulfone, polyetherimide, polyetheretherketone, or a resin obtained by chemically modifying a part thereof. Can do.
エポキシ系樹脂は、シリコーンとビスフェノールＡ型エポキシ樹脂の共重合体と、エーテル結合又はエステル結合を分子内に含む硬化剤の複合体であり、前記共重合体が６４〜９６質量％、硬化剤４〜３６質量％である。硬化剤の添加量は、少ないとエポキシ樹脂硬化が発揮されない傾向にあり、多いと反応しない硬化剤が系内に残ってしまう傾向にある。そのため、粘着層のエポキシ樹脂１００質量部に対する硬化剤の添加量の下限は、好ましくは５質量部以上、より好ましくは７質量部以上であり、上限は好ましくは５６質量部以下、より好ましくは４２質量部以下である。 The epoxy resin is a composite of a copolymer of silicone and bisphenol A type epoxy resin and a curing agent containing an ether bond or an ester bond in the molecule. The copolymer is 64 to 96% by mass, and the curing agent 4 It is -36 mass%. When the addition amount of the curing agent is small, the epoxy resin curing tends not to be exhibited, and when the addition amount is large, the non-reactive curing agent tends to remain in the system. Therefore, the lower limit of the addition amount of the curing agent with respect to 100 parts by mass of the epoxy resin of the adhesive layer is preferably 5 parts by mass or more, more preferably 7 parts by mass or more, and the upper limit is preferably 56 parts by mass or less, more preferably 42 parts. It is below mass parts.
シリコーンがエポキシ系樹脂全体の３５〜６５質量％であるのが好ましく、シリコーンが少なくなると室温での弾性率が高くなる傾向にあって被着体への粘着性が悪くなる。シリコーンが多くなると硬化剤との相溶性が悪くなって硬化が十分に進まないという傾向にある。 Silicone is preferably 35 to 65% by mass of the entire epoxy resin. When the amount of silicone decreases, the elastic modulus at room temperature tends to increase and the adhesion to the adherend deteriorates. If the amount of silicone increases, the compatibility with the curing agent will deteriorate and curing will not proceed sufficiently.
ビスフェノールＡ型エポキシ樹脂がエポキシ系樹脂の末端部に配置することが好ましい。これにより、架橋点間の分子量を大きくすることができ、粘着層の低弾性率化が達成され、被着体への粘着性が向上する。 The bisphenol A type epoxy resin is preferably disposed at the end of the epoxy resin. Thereby, the molecular weight between cross-linking points can be increased, the elastic modulus of the adhesive layer can be lowered, and the adhesiveness to the adherend is improved.
導電層を設けることにより、本発明の保護シートを貼り付けた電子部品は製造工程中で電気的な搬送を行うことができる。導電層にはＩＴＯ（Ｉｎｄｉｕｍ Ｔｉｎ Ｏｘｉｄｅ）やアルミニウムなどの導電性物質の蒸着などによる被覆、ポリピロールやポリチオフェン、ポリアニリンなどの導電性高分子による被覆、ＩＴＯやＡＴＯ（Ａｎｔｉｍｏｎｙ Ｔｒｉｏｘｉｄｅ）、カーボンブラック、カーボンファイバーなどの導電性物質を添加した樹脂による被覆などがあげられる。 By providing the conductive layer, the electronic component attached with the protective sheet of the present invention can be electrically conveyed during the manufacturing process. The conductive layer is coated with a conductive material such as ITO (Indium Tin Oxide) or aluminum, coated with a conductive polymer such as polypyrrole, polythiophene, or polyaniline, ITO, ATO (Antimony Trioxide), carbon black, or carbon fiber. For example, coating with a resin to which a conductive substance such as the above is added is possible.
保護シートの耐薬品性を評価する際の溶剤として、メチルアルコール、エチルアルコール、イソプロピルアルコール、N−メチル−２−ピロリドン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテルジエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、ジメチルスルホキシド、モノエタノールアミン、テトラメチルアンモニウムハイドロキサイドと水の混合溶媒、テトラメチルアンモニウムハイドロキサイドと水及びジメチルスルホキシドの混合溶媒から選ばれるいずれか一種以上が用いられる。 As solvents for evaluating the chemical resistance of protective sheets, methyl alcohol, ethyl alcohol, isopropyl alcohol, N-methyl-2-pyrrolidone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether diethylene glycol monoethyl ether , Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dimethyl sulfoxide, monoethanolamine, a mixed solvent of tetramethylammonium hydroxide and water, a mixed solvent of tetramethylammonium hydroxide, water and dimethyl sulfoxide One or more are used.
（実施例１）
〈基材層の導電処理〉
ポリエチレンテレフタレート２５μｍ（帝人デュポンフィルム社製）の基材の片面に導電性ポリマー（丸菱油化工業社製ＰＰＹ−１２）成分が膜厚１μｍになるように塗布した。
Example 1
<Conductive treatment of base material layer>
A conductive polymer (PPY-12 manufactured by Maruhishi Yuka Kogyo Co., Ltd.) component was applied on one side of a base material of polyethylene terephthalate 25 μm (manufactured by Teijin DuPont Films) so as to have a film thickness of 1 μm.
〈粘着層の樹脂組成物の作製〉
シリコーンとビスフェノールＡ型エポキシ樹脂の共重合体であるエポキシ樹脂（ｎａｎｏｒｅｓｉｎｓ社製ａｌｂｉｆｌｅｘ３４８（登録商標））と前記エポキシ樹脂１００質量部に対してアミン系硬化剤（三井ファインケミカル社製ジェファーミンＴ４０３（登録商標））を７質量部添加し、これらにより粘着層の樹脂組成物を作製した。
<Preparation of resin composition for adhesive layer>
Epoxy resin (albiflex 348 (registered trademark) manufactured by nanoresins) which is a copolymer of silicone and bisphenol A type epoxy resin and 100 parts by mass of the epoxy resin are amine-based curing agents (Jeffamine T403 (registered trademark) manufactured by Mitsui Fine Chemical Co., Ltd.). )) Was added in an amount of 7 parts by mass, and thereby a resin composition for the adhesive layer was produced.
〈粘着層の形成・保護シートの作製〉
作製された基材層の導電処理付設面とは反対面上に、粘着層の樹脂組成物を１５μｍになるように塗布し、１３０℃１２０分加熱乾燥し、これにより保護シートを作製した。
<Adhesion layer formation / protection sheet preparation>
On the surface opposite to the surface provided with the conductive treatment of the prepared base material layer, the resin composition of the adhesive layer was applied so as to have a thickness of 15 μm and dried by heating at 130 ° C. for 120 minutes, thereby preparing a protective sheet.
この保護シートについて、以下に示す方法で（１）表面抵抗率（２）耐薬品性（３）光透過率を測定、評価した。 About this protective sheet, (1) Surface resistivity (2) Chemical resistance (3) Light transmittance was measured and evaluated by the method shown below.
（１）表面抵抗率
保護シートの表面抵抗率は、基材層に対してアジデントテクノロジー社製のＲ８３４０Ａを使用し、ＪＩＳ K ６９１１、５．１３に準拠し、表面抵抗率を測定した。
(1) The surface resistivity of the surface resistivity protective sheet was measured based on JIS K 6911, 5.13 using R8340A manufactured by Azident Technology Co., Ltd. with respect to the base material layer.
（２）耐薬品性
幅２０ｍｍ、長さ５０ｍｍの帯状に切り出した保護シートの粘着層面をソーダガラスに室温で貼り付けしたのち、３０℃に設定した表１に示す各種溶剤中に１０分間浸漬し、耐薬品性は浸漬中の剥離の有無で評価した。表１の○は、試験中に剥離がなく形状維持がなされたことを意味し、×は膨潤又は剥離が生じたことを意味する。
(2) The adhesive layer surface of the protective sheet cut into a strip shape having a chemical resistance width of 20 mm and a length of 50 mm is attached to soda glass at room temperature, and then immersed in various solvents shown in Table 1 set at 30 ° C. for 10 minutes. The chemical resistance was evaluated by the presence or absence of peeling during immersion. “◯” in Table 1 means that the shape was maintained without peeling during the test, and “X” means that swelling or peeling occurred.
（３）光透過率
保護シートの透過率は、島津製作所社製ＵＶ−２４００を使用し、波長４００nm〜７００nmにおける光透過率を測定した。これらの結果を表１に示す。
(3) The light transmittance of the protective sheet for light transmittance was measured using a UV-2400 manufactured by Shimadzu Corporation, and the light transmittance at a wavelength of 400 nm to 700 nm was measured. These results are shown in Table 1.
（実施例２）
基材層の導電処理としてアルミニウムを１００Å蒸着させておこなう他は実施例１と同様に試験した。結果を表１に示す。
(Example 2)
The test was conducted in the same manner as in Example 1 except that 100% of aluminum was deposited as the conductive treatment of the base material layer. The results are shown in Table 1.
（実施例３）
〈導電層の樹脂組成物の作製〉
トリアジン骨格を含むエポキシ樹脂（日産化学工業社製ＴＥＰＩＣ−ＰＡＳ２６（登録商標））と前記エポキシ樹脂１００質量部に対して酸無水物系硬化剤 （新日本理化社製ＴＨ）を１２０質量部添加し、硬化促進剤としてイミダゾール系化合物（四国化成社製キュアゾール２E４ＭＺ（登録商標））を０．５質量部用いた。炭素繊維フィラー（昭和電工社製ＶＧＣＦ−Ｓ（登録商標））を導電樹脂１００質量部に対して０．６質量部添加し、この配合部材に添加剤としてカップリング剤（信越化学工業社製ＫＢＭ４０３）を１質量部添加し、これらによって導電層の樹脂組成物を作製した。
(Example 3)
<Preparation of resin composition of conductive layer>
Add 120 parts by mass of an acid anhydride curing agent (TH by Nippon Nippon Chemical Co., Ltd.) to 100 parts by mass of an epoxy resin containing a triazine skeleton (TEPIC-PAS26 (registered trademark) manufactured by Nissan Chemical Industries, Ltd.) and the epoxy resin. In addition, 0.5 part by mass of an imidazole compound (Curazole 2E4MZ (registered trademark) manufactured by Shikoku Kasei Co., Ltd.) was used as a curing accelerator. A carbon fiber filler (VGCF-S (registered trademark) manufactured by Showa Denko KK) is added in an amount of 0.6 parts by mass with respect to 100 parts by mass of the conductive resin, and a coupling agent (KBM403 manufactured by Shin-Etsu Chemical Co., Ltd.) is added as an additive to this blended member. ) Was added in an amount of 1 part by mass, and thereby a resin composition for the conductive layer was produced.
〈導電層の形成〉
基材層の導電処理として、導電層の樹脂組成物を１０μｍの厚さで塗布し、１３０℃で９０分加熱するほかは実施例１と同様に試験した。結果を表１に示す。
<Formation of conductive layer>
As the conductive treatment of the base material layer, the same test as in Example 1 was conducted except that the resin composition of the conductive layer was applied to a thickness of 10 μm and heated at 130 ° C. for 90 minutes. The results are shown in Table 1.
（実施例４）
粘着層の樹脂を、シリコーンとビスフェノールＡ型エポキシ樹脂の共重合体であるエポキシ樹脂（ｎａｎｏｒｅｓｉｎｓ社製ａｌｂｉｆｌｅｘ３４８（登録商標））と前記エポキシ樹脂１００質量部に対して酸無水物系硬化剤（新日本理化社製リカシッドＨＦ−８０（登録商標））を１２質量部、酸無水物系硬化剤（新日本理化社製リカシッドＤＤＳＡ（登録商標））を１２質量部用いるほかは実施例１と同様に試験した。結果を表１に示す。
Example 4
The resin of the adhesive layer is an epoxy resin (albiflex 348 (registered trademark) manufactured by nanoresins), which is a copolymer of silicone and bisphenol A type epoxy resin, and an acid anhydride curing agent (Shin Nihon). Tested in the same manner as in Example 1 except that 12 parts by mass of Rikashido HF-80 (registered trademark) manufactured by Rika Co., Ltd. and 12 parts by mass of acid anhydride-based curing agent (Rikacid DDSA (registered trademark) manufactured by Shin Nippon Rika Co., Ltd.) were used. did. The results are shown in Table 1.
（比較例１）
〈導電層の樹脂組成物の作製〉
トリアジン骨格を含むエポキシ樹脂（日産化学工業社製ＴＥＰＩＣ−ＰＡＳ ２６（登録商標））と前記エポキシ樹脂１００質量部に対して酸無水物系硬化剤（新日本理化社製ＴＨ）を１２０質量部添加し、硬化促進剤としてイミダゾール系化合物（四国化成社製キュアゾール２E４MZ（登録商標））を０．５質量部用いた。カーボンブラック（電気化学工業社製デンカブラック（登録商標））を導電樹脂１００質量部に対して１７質量部添加し、この配合部材に添加剤としてカップリング剤（信越化学工業社製ＫＢＭ４０３）を１質量部添加し、これらによって導電層の樹脂組成物を作製した。
(Comparative Example 1)
<Preparation of resin composition of conductive layer>
120 parts by mass of an acid anhydride-based curing agent (THN manufactured by Shin Nippon Rika Co., Ltd.) is added to 100 parts by mass of an epoxy resin containing a triazine skeleton (TEPIC-PAS 26 (registered trademark) manufactured by Nissan Chemical Industries, Ltd.) and the epoxy resin. Then, 0.5 parts by mass of an imidazole compound (Curazole 2E4MZ (registered trademark) manufactured by Shikoku Kasei Co., Ltd.) was used as a curing accelerator. Carbon black (Denka Black (registered trademark) manufactured by Denki Kagaku Kogyo Co., Ltd.) is added in an amount of 17 parts by mass with respect to 100 parts by mass of the conductive resin, and a coupling agent (KBM403 manufactured by Shin-Etsu Chemical Co., Ltd.) is added as an additive to this blended member. The resin composition of the conductive layer was produced by adding parts by mass.
〈導電層の形成〉
基材層の導電処理として、導電層の樹脂組成物を１０μｍの厚さで塗布し、１３０℃で９０分加熱するほかは実施例１と同様に試験した。結果を表１に示す。比較例１は、光透過率が５％以下となり、透明性が著しく損なわれた。
<Formation of conductive layer>
As the conductive treatment of the base material layer, the same test as in Example 1 was conducted except that the resin composition of the conductive layer was applied to a thickness of 10 μm and heated at 130 ° C. for 90 minutes. The results are shown in Table 1. In Comparative Example 1, the light transmittance was 5% or less, and the transparency was significantly impaired.
（比較例２）
粘着層の樹脂を、ビスフェノールＡ型エポキシ樹脂（ジャパンエポキシレジン社製ｅｐ８２８）と前記エポキシ樹脂１００質量部に対してアミン系硬化剤（三井ファインケミカル社製ジェファーミンＴ４０３（登録商標））を４０質量部用いるほかは実施例１と同様に試験した。結果を表１に示す。比較例２は、ガラスへ接着せず、接着性が足りなかった。
(Comparative Example 2)
Resin for the adhesive layer is 40 parts by mass of bisphenol A type epoxy resin (ep828 manufactured by Japan Epoxy Resin Co., Ltd.) and 100 parts by mass of the epoxy resin with an amine-based curing agent (Jeffamine T403 (registered trademark) manufactured by Mitsui Fine Chemical Co., Ltd.). The test was conducted in the same manner as in Example 1 except that it was used. The results are shown in Table 1. Comparative Example 2 did not adhere to glass and lacked adhesion.
（比較例３）
粘着層の樹脂を、シリコーンとビスフェノールＡ型エポキシ樹脂の共重合体であるエポキシ樹脂（ｎａｎｏｒｅｓｉｎｓ社製ａｌｂｉｆｌｅｘ348（登録商標））と前記エポキシ樹脂１００質量部に対してアミン系硬化剤（日本合成化工社製アクメックスＨ８４Ｂ（登録商標））を５質量部用いるほかは実施例１と同様に試験した。結果を表１に示す。比較例３は、耐薬品性および接着性が十分でなかった。
(Comparative Example 3)
The resin for the adhesive layer is an epoxy resin (albiflex 348 (registered trademark) manufactured by nanoresins), which is a copolymer of silicone and bisphenol A type epoxy resin, and an amine-based curing agent (Nippon Synthetic Chemical Co., Ltd.) with respect to 100 parts by mass of the epoxy resin. The test was conducted in the same manner as in Example 1 except that 5 parts by mass of Acmex H84B (registered trademark) was used. The results are shown in Table 1. In Comparative Example 3, chemical resistance and adhesion were not sufficient.
本発明の保護シートは、導電性、接着性、耐薬品性の低下が少ない。このため、使用の制限がなくなり、作業性がよく、かつしっかりと電子部品を保護できる。 The protective sheet of the present invention has little decrease in conductivity, adhesiveness, and chemical resistance. For this reason, there are no restrictions on use, workability is good, and electronic components can be securely protected.
Claims (4)
The conductive layer is formed by depositing a conductive material such as ITO (Indium Tin Oxide) or aluminum, or coating with a conductive polymer such as polypyrrole, polythiophene, or polyaniline, or ITO, ATO (Antimony Trioxide), carbon black, carbon fiber, or the like. The protective sheet according to any one of claims 1 to 3, comprising a cured epoxy resin having a triazine skeleton to which a conductive substance is added.
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| CN104231993A (en) * | 2014-09-26 | 2014-12-24 | 江南大学 | Modified inorganic nanoparticle toughening epoxy resin pouring sealant and preparation method thereof |
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| JPH03258827A (en) * | 1990-03-06 | 1991-11-19 | Toray Ind Inc | Silicone-modified epoxy resin composition and electroconductive adhesive prepared therefrom |
| JPH0948957A (en) * | 1995-08-07 | 1997-02-18 | Sony Chem Corp | Manufacture of double-face adhesive tape |
| JP2004143389A (en) * | 2002-10-22 | 2004-05-20 | Hitachi Kasei Polymer Co Ltd | Pressure sensitive self-adhesive tape for fixing veneer having high adhesion difficulty |
| JP4611868B2 (en) * | 2004-11-24 | 2011-01-12 | 大日精化工業株式会社 | Protective film for optics |
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