JP6625079B2 - Sealing resin composition - Google Patents
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Description
本発明は、有機エレクトロルミネッセンス（以下「有機ＥＬ」と表記）などのような電子機器の封止材料として用いることができる封止樹脂組成物に関する。 The present invention relates to a sealing resin composition that can be used as a sealing material for electronic devices such as organic electroluminescence (hereinafter, referred to as “organic EL”).
有機ＥＬ素子は自発光型の薄型化可能な電子ディスプレイデバイスであり、平面表示にくわえ曲面表示も可能なデバイスとして期待されている。しかしながら、有機ＥＬ素子は水分にきわめて弱く、また空気中の酸素や素子駆動による熱の影響により、電極の酸化や有機材料が変性しやすい。その結果一定時間駆動した場合、発光輝度や発光効率、発光均一性の低下に加え、ダークスポットの発生や成長等の性能の劣化が大きな課題となっており、長期にわたって安定した発光特性を維持することができる技術改善が進められている。 The organic EL element is a self-luminous type electronic display device that can be made thinner, and is expected as a device that can display a curved surface as well as a flat display. However, the organic EL element is extremely weak to moisture, and the electrode is oxidized and the organic material is easily modified by the influence of oxygen in the air or heat generated by driving the element. As a result, when driven for a certain period of time, deterioration of performance such as generation and growth of dark spots in addition to deterioration of light emission luminance, light emission efficiency, and light emission uniformity has become a major issue, and stable light emission characteristics are maintained for a long time. Technical improvements that can be made.
その対応策として、水素添加オレフィン系ポリマーとポリイソブチレン樹脂を含む接着性封入用組成物が提案されている（特許文献１）。またジエン及び１つの炭素−炭素二重結合を含むオレフィン系化合物と炭素数３〜３０のアルキル基から誘導された多官能（メタ）アクリレートを含む粘着剤組成物が提案されている（特許文献）。しかしながら前者は耐溶剤性に劣り、後者はガラスへの粘着力が不充分という課題があり、改善の余地があった。 As a countermeasure, an adhesive encapsulating composition containing a hydrogenated olefin polymer and a polyisobutylene resin has been proposed (Patent Document 1). Further, an adhesive composition containing a diene, an olefinic compound containing one carbon-carbon double bond, and a polyfunctional (meth) acrylate derived from an alkyl group having 3 to 30 carbon atoms has been proposed (Patent Document). . However, the former has poor solvent resistance, and the latter has a problem that the adhesion to glass is insufficient, and there is room for improvement.
本発明は、優れたガラスへの粘着力と耐溶剤性を有し、水蒸気の透過率が低いため、有機ＥＬ等の電子デバイスで封止材料として用いた場合に、素子内への吸湿を抑制し、長期間にわたり安定な品質を維持する事が出来うる封止樹脂組成物を提供することにある。 The present invention has excellent adhesive strength to glass and solvent resistance, and has a low water vapor transmission rate. Therefore, when used as a sealing material in an electronic device such as an organic EL, it suppresses moisture absorption into the element. Another object of the present invention is to provide a sealing resin composition that can maintain stable quality for a long period of time.
請求項１記載の発明は、側鎖に不飽和基を有するエチレン−プロピレン共重合体（Ａ）と、多官能（メタ）アクリレート（Ｂ）と、水素添加環状オレフィン系ポリマー（Ｃ）と、光重合開始剤（Ｄ）と、を含み、全組成物に対する（Ａ）の比率が２５〜５５重量％で、（Ｂ）の比率が０．３〜１５重量％で、（Ｃ）の比率が３５〜７０重量％である電子機器用途の封止樹脂組成物を提供する。
The invention according to claim 1 provides an ethylene-propylene copolymer (A) having an unsaturated group in a side chain, a polyfunctional (meth) acrylate (B), a hydrogenated cyclic olefin-based polymer (C), the polymerization initiator (D), only contains, in proportion 25 to 55 wt% of to total composition (a), a ratio is 0.3 to 15 wt% of (B), the ratio of (C) Provided is a sealing resin composition for electronic equipment, which is 35 to 70% by weight .
請求項２記載の発明は、前記前記側鎖に不飽和基を有するエチレン−プロピレン共重合体（Ａ）がエチリデンノルボルネン−エチレン−プロピレン共重合体である請求項１記載の電子機器用途の封止樹脂組成物を提供する。 In the invention according to claim 2, the ethylene-propylene copolymer (A) having an unsaturated group in the side chain is an ethylidene norbornene-ethylene-propylene copolymer. A resin composition is provided.
本発明の封止樹脂組成物は、優れたガラスへの粘着力と耐溶剤性を有し、水蒸気の透過率が低いため、例えば有機ＥＬ素子の封止材料として用いた場合、素子内への吸湿を抑制し、素子内の電極酸化や有機物の変性等を抑えることでダークスポットの発生および成長を抑制し、長期間にわたり安定な品質を維持することが出来る効果がある。 The sealing resin composition of the present invention has excellent adhesion to glass and solvent resistance, and has a low water vapor transmission rate. For example, when used as a sealing material for an organic EL element, By suppressing moisture absorption and suppressing electrode oxidation and denaturation of organic substances in the device, the generation and growth of dark spots are suppressed, and there is an effect that stable quality can be maintained for a long period of time.
以下本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明の組成物の構成は、側鎖に不飽和基を有するエチレン−プロピレン共重合体（Ａ）と、多官能（メタ）アクリレート（Ｂ）と、水素添加環状オレフィン系ポリマー（Ｃ）と、光重合開始剤（Ｄ）である。なお、本明細書において（メタ）アクリレートとは、アクリレートとメタクリレートの双方を包含する。 The composition of the composition of the present invention comprises an ethylene-propylene copolymer (A) having an unsaturated group in a side chain, a polyfunctional (meth) acrylate (B), a hydrogenated cyclic olefin-based polymer (C), It is a photopolymerization initiator (D). In addition, in this specification, (meth) acrylate includes both acrylate and methacrylate.
本発明で使用する側鎖に不飽和基を有するエチレン−プロピレン共重合体（Ａ）は、防湿絶縁層を構成するベースポリマーである。エチレン等の含有比率を変化させることで、引張強度や硬度等の性状を変化させることが可能であり、エチレンの含有比率は６５％以下が好ましく、６０％以下が更に好ましい。６５％超ではポリマーの硬度が高くなり、ガラスへの剥離強度が低下する。 The ethylene-propylene copolymer (A) having an unsaturated group in a side chain used in the present invention is a base polymer constituting a moisture-proof insulating layer. By changing the content ratio of ethylene and the like, properties such as tensile strength and hardness can be changed, and the content ratio of ethylene is preferably 65% or less, more preferably 60% or less. If it exceeds 65%, the hardness of the polymer increases, and the peel strength to glass decreases.
前記側鎖に不飽和基を有するエチレン−プロピレン共重合体（Ａ）としては、エチリデンノルボルネン（以下「ＥＮＢ」と表記）−エチレン−プロピレン共重合体が好ましい。ＥＮＢを共重合させた場合は、ポリマーの主鎖が化学的に安定な飽和炭化水素から構成されるため、紫外線やオゾンへの耐性および耐薬品性などが向上する。重量平均分子量は３０万以下が好ましく、市販のエチレン・プロピレン・ＥＮＢ共重合ポリマー（以下「ＥＰＤＭ」と表記）としては、ＥＰシリーズ（商品名：ＪＳＲ社製）、ＥＰＴシリーズ（商品名：三井化学社製）などがある。なお重量平均分子量（以下「Ｍｗ．」と表記）はゲル透過クロマトグラフィー法により、スチレンジビニルベンゼン基材のカラムでテトラハイドロフラン展開溶媒を用いて、標準ポリスチレン換算の分子量を測定、算出した。 As the ethylene-propylene copolymer (A) having an unsaturated group in the side chain, an ethylidene norbornene (hereinafter referred to as “ENB”)-ethylene-propylene copolymer is preferable. When ENB is copolymerized, the main chain of the polymer is composed of a chemically stable saturated hydrocarbon, so that resistance to ultraviolet rays and ozone, chemical resistance, and the like are improved. The weight average molecular weight is preferably 300,000 or less, and commercially available ethylene / propylene / ENB copolymer (hereinafter referred to as “EPDM”) includes EP series (trade name: manufactured by JSR Corporation) and EPT series (trade name: Mitsui Chemicals, Inc.) Company). The weight-average molecular weight (hereinafter referred to as “Mw.”) Was measured and calculated by standard gel permeation chromatography using a column of styrenedivinylbenzene as a standard polystyrene-equivalent molecular weight using a developing solvent of tetrahydrofuran.
前記（Ａ）の全配合量に対する比率は２５〜５５重量％が好ましく、２８〜５０重量％が更に好ましい。２５重量％以上とすることで充分な耐溶剤性および光学特性を確保でき、５５重量％以下とすることで充分な透湿度とガラスへの粘着力を確保できる。 The ratio of (A) to the total amount is preferably 25 to 55% by weight, more preferably 28 to 50% by weight. When the content is 25% by weight or more, sufficient solvent resistance and optical characteristics can be secured, and when the content is 55% by weight or less, sufficient moisture permeability and adhesive strength to glass can be secured.
本発明で使用する多官能（メタ）アクリレート（Ｂ）は、共重合体（Ａ）と（Ｃ）を含む混合物を硬化・架橋させる役割を担う。単官能（メタ）アクリレートでは硬化物の分子量を大きく出来ないため，多官能（メタ）アクリレートを使用するが、硬化収縮を抑えるため２官能が好ましい。アクリル系のモノマーに加えて、ポリエステル系アクリレートオリゴマー、ウレタン系アクリレートオリゴマー、エポキシ系アクリレートオリゴマーなどがあり、単独あるいは２種類以上を組み合わせて使用できる。アクリレートオリゴマーの中では、耐衝撃性や柔軟性を有するウレタン系のアクリレートオリゴマーが好ましい。 The polyfunctional (meth) acrylate (B) used in the present invention has a role of curing and crosslinking a mixture containing the copolymers (A) and (C). Polyfunctional (meth) acrylates are used because monofunctional (meth) acrylates cannot increase the molecular weight of the cured product, but bifunctional is preferred to suppress curing shrinkage. In addition to acrylic monomers, there are polyester-based acrylate oligomers, urethane-based acrylate oligomers, epoxy-based acrylate oligomers, and the like, and these can be used alone or in combination of two or more. Among acrylate oligomers, urethane acrylate oligomers having impact resistance and flexibility are preferable.
２官能の（メタ）アクリル系モノマーとしては、エチレングリコールジメタクリレート、ジエチレングリコールジメタクリレート、トリエチレングルコールジアクリレート、ポリエチレングリコールジアクリレート、ジプロピレングリコールジアクリレート、トリプロピレングリコールジアクリレート、ポリプロピレングリコールジアクリレート、１．４−ブタンジオールジ（メタ）アクリレート、４．６−ヘキサンジオールジ（メタ）アクリレート、１．９−ノナンジオールジ（メタ）アクリレート、１．１０−デカンジオールジ（メタ）アクリレート、ネオペンチルグリコールジメタクリレート、３−メチル−１．５ペンタンジオールジアクリレート、２−ヒドロキシ−３−アクリロイロキシプロピルメタクリレート、ジメチロールトリシクロデカンジアクリレート、ジシクロペンタニルジアクリレート、ジオキサングリコールジアクリレートなどがあり、単独あるいは２種類以上を組み合わせて使用できる。これらの中ではポリマーとの相溶性の観点で、環状骨格をもつジメチロールトリシクロデカンジアクリレート、ジオキサングリコールジアクリレートが好ましい。 As bifunctional (meth) acrylic monomers, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 1.4-butanediol di (meth) acrylate, 4.6-hexanediol di (meth) acrylate, 1.9-nonanediol di (meth) acrylate, 1.10-decanediol di (meth) acrylate, neopentyl Glycol dimethacrylate, 3-methyl-1.5 pentanediol diacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, dimethylol triacrylate Black diacrylate, dicyclopentanyl diacrylate, include dioxane glycol diacrylate, it can be used either individually or in combination of two or more. Among these, dimethylol tricyclodecane diacrylate and dioxane glycol diacrylate having a cyclic skeleton are preferable from the viewpoint of compatibility with the polymer.
ウレタン系のアクリレートオリゴマーは、ポリオールとポリイソシアネートとの付加反応物に、末端に残るイソシアネート基を水酸基含有アクリレートと反応させてアクリル基を分子末端に持つ構造であり、構成する原料により芳香族系と脂肪族系に大別されるが、優れた力学的な特性を維持しつつ、粘度が比較的低く黄変しない脂肪族系が好ましい。市販の脂肪族ウレタンアクリレートとしてはＣＮ９０１４ＮＳ（商品名：サートマー社製）などがある。 Urethane-based acrylate oligomers have a structure in which an addition reaction product of a polyol and a polyisocyanate reacts an isocyanate group remaining at the end with a hydroxyl-containing acrylate to have an acrylic group at a molecular end. Although it is roughly classified into an aliphatic system, an aliphatic system having a relatively low viscosity and not yellowing while maintaining excellent mechanical properties is preferable. Commercially available aliphatic urethane acrylates include CN9014NS (trade name, manufactured by Sartomer).
前記（Ｂ）の前配合量に対する比率は０．３〜１５重量％が好ましく、０．５〜１０重量％が更に好ましい。０．３重量％以上とすることで充分な硬化性を確保でき、１５重量％以下とすることで充分なガラス密着力を確保できる。 The ratio of (B) to the pre-blended amount is preferably from 0.3 to 15% by weight, more preferably from 0.5 to 10% by weight. When the content is 0.3% by weight or more, sufficient curability can be secured, and when the content is 15% by weight or less, sufficient glass adhesion can be secured.
本発明で使用する水素添加環状オレフィン系ポリマー（Ｃ）は、粘着力の向上，水分透過性を減少させる役割を担う。特に水素添加したＣ５系、Ｃ９系、ジシクロペンタジエン（以下「ＤＣＰＤ」と表記）系およびこれらを混合した石油樹脂は水分の透過性が低く、粘着性を向上させることができると共に、（Ａ）との相溶性も良好で好適である。 The hydrogenated cyclic olefin-based polymer (C) used in the present invention has a role of improving the adhesive strength and reducing the moisture permeability. In particular, hydrogenated C5 type, C9 type, dicyclopentadiene (hereinafter referred to as “DCPD”) type and petroleum resin obtained by mixing these have low moisture permeability, can improve the adhesiveness, and (A) And good compatibility.
前記（Ｃ）の軟化点は８０〜１５０℃が好ましく、８０℃以上で充分な熱安定性を持ち、１５０℃以下で充分な粘着力を確保できる。またＭｗ．は３００〜２，０００が好ましく、５００〜１，０００が更に好ましい。１，０００以下で（Ａ）との相溶性と充分な粘着力を確保できる。市販のＣ５系、Ｃ９系、ＤＣＰＤ系およびこれらを混合した水添石油樹脂としては、アルコンＰシリーズ（商品名：荒川化学社製）、Ｔ−ＲＥＺ−Ｈシリーズ（商品名：東燃ゼネラル社製）、ＥＳＣＯＲＥＺ（商品名：エクソンケミカル社製）、ＥＡＳＴＯＴＡＣ（商品名：イーストマンケミカル社製）などがある。 The softening point of (C) is preferably from 80 to 150 ° C, has sufficient thermal stability at 80 ° C or higher, and secures sufficient adhesive strength at 150 ° C or lower. Mw. Is preferably from 300 to 2,000, more preferably from 500 to 1,000. When it is 1,000 or less, compatibility with (A) and sufficient adhesive strength can be secured. Commercially available C5 series, C9 series, DCPD series, and hydrogenated petroleum resins obtained by mixing these are Alcon P series (trade name: Arakawa Chemical Co., Ltd.) and T-REZ-H series (trade name: TonenGeneral Co., Ltd.) , ESCOREZ (trade name: manufactured by Exxon Chemical Co., Ltd.), and EASTOTAC (trade name: manufactured by Eastman Chemical Co., Ltd.).
前記（Ｃ）の前配合量に対する比率は３５〜７０重量％が好ましく、４０〜６５重量％が更に好ましい。３５重量％以上とすることで水分の透過性を低減することができ、７０重量％以下とすることで充分な光学特性を維持できる。 The ratio of the (C) to the pre-blended amount is preferably 35 to 70% by weight, and more preferably 40 to 65% by weight. When the content is 35% by weight or more, the permeability of water can be reduced, and when the content is 70% by weight or less, sufficient optical characteristics can be maintained.
本発明で使用される光重合開始剤（Ｄ）は、紫外線や電子線などの照射でラジカルを生じ、そのラジカルが重合反応のきっかけとなるもので、汎用の光重合開始剤で良い。具体的には２−ヒロドキシ−１−｛４−［４−（２−ヒドロキシ−２−メチル−プロピオニル）−ベンジル］フェニル｝−２−メチル−プロパン−１−オン、１−ヒドロキシ−シクロヘキシル−フェニル−ケトン、ビス（２，４，６‐トリメチルベンゾイル）‐フェニルフォスフィンオキサイド、２，４，６-トリメチルベンゾイル-ジフェニル-フォスフィンオキサイド、２-ヒドロキシ-２-メチル-１-フェニル-プロパン-１-オン、１-[４-(２-ヒドロキシエトキシ)-フェニル]-２-ヒドロキシ-２-メチル-１-プロパン-１-オン等があり、単独または２種以上を組み合わせて使用できる。ラジカル重合性成分に対して、１〜１０重量％配合することが好ましい。 The photopolymerization initiator (D) used in the present invention generates radicals upon irradiation with ultraviolet rays or electron beams, and the radicals trigger the polymerization reaction, and may be general-purpose photopolymerization initiators. Specifically, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl -Ketone, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2-hydroxy-2-methyl-1-phenyl-propane-1 -One, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one and the like, which can be used alone or in combination of two or more. It is preferable to add 1 to 10% by weight to the radical polymerizable component.
更に加えて本発明の封止樹脂組成物は、性能を損なわない範囲で、必要に応じシランカップリング剤、可塑剤、酸化防止剤、難燃剤、紫外線吸収剤、染料、顔料、充填剤等の添加剤を含有してもよい。 In addition, the sealing resin composition of the present invention, as long as the performance is not impaired, a silane coupling agent, a plasticizer, an antioxidant, a flame retardant, an ultraviolet absorber, a dye, a pigment, a filler, etc., if necessary. It may contain additives.
封止樹脂組成物を基材へ塗布する際は、粘着性組成物を例えばトルエン等の有機溶媒に溶かし、塗布が可能な粘度まで希釈する。有機溶媒で希釈する際の固形分としては、１０〜３０重量％が例示されるが、特にこれに限られるものではなく自由に選定できる。有機溶剤で希釈された粘着性組成物を基材に塗布した後は、例えば加熱乾燥炉に通して乾燥し溶剤を除去する。 When applying the sealing resin composition to the substrate, the adhesive composition is dissolved in an organic solvent such as toluene, for example, and diluted to a viscosity at which application is possible. The solid content when diluted with an organic solvent is exemplified by 10 to 30% by weight, but is not particularly limited thereto and can be freely selected. After applying the adhesive composition diluted with the organic solvent to the substrate, the composition is passed through, for example, a heating and drying oven to be dried to remove the solvent.
本発明の封止樹脂組成物を厚さ１００μｍのシート状に硬化したシート厚み方向における平均水蒸気透過率は、４０℃、相対湿度９０％の環境下において１０ｇ／ｍ２・２４ｈｒ以下が好ましく、８．５ｇ／ｍ２・２４ｈｒ以下がより好ましい。１０ｇ／ｍ２・２４ｈｒ以下とすることで、有機ＥＬ素子の封止材として使用した場合でも、素子内への吸湿を抑制し、長期間にわたり安定した品質を維持する事が出来る。 The average water vapor permeability at the cured sheet thickness direction sealing resin composition in a thickness 100μm sheet of the present invention, 40 ° C., preferably not more than 10g / m 2 · 24hr at relative humidity of 90%, 8 .5g / m 2 · 24hr or less is more preferable. By setting it to 10 g / m 2 · 24 hr or less, even when used as a sealing material for an organic EL element, moisture absorption into the element can be suppressed and stable quality can be maintained for a long period of time.
また本発明の封止樹脂組成物を厚さ１００μｍのシート状に硬化したシートの光学特性は、全光線透過率として９０％以上が好ましく、９１％以上がより好ましい。またヘイズについては１．０％以下が好ましく、０．５以下がより好ましい。全光線透過率を９０％以上、ヘイズを１．０％以下とすることで、充分な画像の透過性を確保でき、有機ＥＬ素子の封止材として使用することができる。 The optical characteristics of a sheet obtained by curing the sealing resin composition of the present invention into a sheet having a thickness of 100 μm are preferably 90% or more, more preferably 91% or more, as a total light transmittance. The haze is preferably 1.0% or less, more preferably 0.5 or less. By setting the total light transmittance to 90% or more and the haze to 1.0% or less, sufficient image transparency can be ensured, and it can be used as a sealing material for an organic EL element.
以下、本発明を実施例、比較例に基づき詳細に説明するが、具体例を示すものであって特にこれらに限定するものではない。なお表記が無い場合は、室温は２３℃相対湿度５０％の条件下で測定を行った。 Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but it shows specific examples and does not particularly limit the present invention. In addition, when there was no description, the measurement was performed on condition of room temperature of 23 degreeC and 50% of relative humidity.
実施例１
側鎖に不飽和基を有するエチレン−プロピレン共重合体（Ａ）としてＥＰ Ｔ７１４１（商品名：ＪＳＲ社製、ＥＰＤＭ、エチレン含有量４９％）を、多官能（メタ）アクリレート（Ｂ）としてライトアクリレートＤＣＰ−Ａ（商品名：共栄社化学社製、ジメチロールトリシクロデカンジアクリレート）を、水素添加環状オレフィン系ポリマー（Ｃ）としてアルコンＰ−９０（商品名：荒川化学社製、水添石油樹脂）を、光重合開始剤（Ｄ）としてＥｓａｃｕｒｅＴＺＴ（商品名：ｉＧＭ社製）を用い、表１記載の配合で不揮発分が２０％となるようにトルエンを加え、均一に溶解するまで撹拌、脱泡し実施例１の封止樹脂組成物を調整した。
Example 1
EP T7141 (trade name: EPDM, ethylene content 49%) as an ethylene-propylene copolymer (A) having an unsaturated group in a side chain, and light acrylate as a polyfunctional (meth) acrylate (B) DCP-A (trade name: Kyoeisha Chemical Co., Ltd., dimethylol tricyclodecane diacrylate) is used as a hydrogenated cyclic olefin polymer (C) as Alcon P-90 (trade name, Arakawa Chemical Co., hydrogenated petroleum resin). Using EsacureTZT (trade name: manufactured by iGM) as a photopolymerization initiator (D), toluene was added so that the nonvolatile content was 20% in the composition shown in Table 1, and the mixture was stirred and defoamed until homogeneously dissolved. Then, the sealing resin composition of Example 1 was prepared.
実施例２〜１４
実施例１で用いた材料の他、（Ａ）としてＥＰ２２（商品名：ＪＳＲ社製、ＥＰＤＭ、同５４％）およびＥＰ９３（商品名：ＪＳＲ社製、ＥＰＤＭ、同５５％）およびＥＰ２５１（商品名：ＪＳＲ社製、ＥＰＤＭ、同５７．５％）およびＥＰＴ２０８０Ｍ（商品名：三井化学社製、ＥＰＤＭ、同５５％）およびＥＰＴ８０３０Ｍ（商品名：三井化学社製、ＥＰＤＭ、同４７％）を、（Ｂ）としてＮＫエステルＡ−ＤＯＧ（商品名：新中村化学工業社製、ジオキサングリコールジアクリレート）およびＣＮ９０１４ＮＳ（商品名：サートマー社製、脂肪族系ウレタンアクリレート、２官能）を、（Ｃ）としてアルコンＰ−１２５（商品名：荒川化学工業社製、水添石油樹脂）およびＴ−ＲＥＺＨＡ−８５（商品名：東燃ゼネラル社製、水添石油樹脂、Ｍｗ．５５０）およびＴ−ＲＥＺＨＡ−１２５（商品名：東燃ゼネラル社製、水添石油樹脂、Ｍｗ．３２０）およびＴ−ＲＥＺＨＢ−８５（商品名：東燃ゼネラル社製、水添石油樹脂、Ｍｗ．６５０）を、シランカップリング剤としてＫＲ−５１３（商品名：信越化学工業社製、アクリル基含有シリコーンオリゴマー）を用い、表１記載の配合で不揮発分が２０％となるようにトルエンを加え、均一に溶解するまで撹拌、脱泡し実施例２〜１４の封止樹脂組成物を調整した。
Examples 2 to 14
In addition to the materials used in Example 1, (A) as EP22 (trade name: JSR, EPDM, 54%) and EP93 (trade name: JSR, EPDM, 55%) and EP251 (trade name) : EPDM, 57.5% manufactured by JSR Corporation and EPT2080M (trade name: EPDM, 55% manufactured by Mitsui Chemicals) and EPT8030M (trade name: EPDM, 47% manufactured by Mitsui Chemicals, Inc.) NK ester A-DOG (trade name: manufactured by Shin-Nakamura Chemical Co., dioxane glycol diacrylate) and CN9014NS (trade name: manufactured by Sartomer, aliphatic urethane acrylate, bifunctional) as B); P-125 (trade name: hydrogenated petroleum resin manufactured by Arakawa Chemical Industries) and T-REZHA-85 (trade name: manufactured by TonenGeneral Co., Ltd., hydrogenated petroleum) Fat, Mw. 550) and T-REZHA-125 (trade name: hydrogenated petroleum resin, manufactured by Tonen General Co., Ltd., Mw. 320) and T-REZHB-85 (trade name: manufactured by Tonen General Co., hydrogenated petroleum resin, Mw.650) and KR-513 (trade name: manufactured by Shin-Etsu Chemical Co., Ltd., acrylic group-containing silicone oligomer) as a silane coupling agent, and toluene was added to the composition shown in Table 1 so that the nonvolatile content was 20%. In addition, the mixture was stirred and defoamed until it was uniformly dissolved to prepare the sealing resin compositions of Examples 2 to 14.
比較例１〜４
実施例で用いた材料の他、イソブチレン系ポリマーとしてＪＳＲ Ｂｕｔｙｌ２６８（商品名：ＪＳＲ社製、イソブチレンイソプレン共重合ポリマー）およびＯＰＰＡＮＯＬＮ５０ＳＦ（商品名：ＢＡＳＦ社製、ポリイソブチレンポリマー、Ｍｗ．３４万）を、単官能アクリレートとしてライトエステルＩＢ−Ｘ（商品名：共栄社化学社製、イソボルニルメタクリレート）を、シランカップリング剤としてＫＢＭ−５０３（商品名：信越化学工業社製、３−メタクリロキシプロピルトリメトキシシラン）を用い、表１記載の配合で不揮発分が２０％となるようにトルエンを加え、均一に溶解するまで撹拌、脱泡し比較例１〜４の封止樹脂組成物を調整した。
Comparative Examples 1-4
In addition to the materials used in the examples, JSR Butyl268 (trade name: manufactured by JSR, isobutylene isoprene copolymerized polymer) and OPPANOLN50SF (trade name: manufactured by BASF, polyisobutylene polymer, Mw.340,000) were used as isobutylene-based polymers. Light ester IB-X (trade name: Kyoeisha Chemical Co., Ltd., isobornyl methacrylate) as a monofunctional acrylate, and KBM-503 (trade name: Shin-Etsu Chemical Co., Ltd., 3-methacryloxypropyltrimethoxy) as a silane coupling agent Using silane), toluene was added so that the nonvolatile content was 20% in the formulation shown in Table 1, and the mixture was stirred and defoamed until uniformly dissolved to prepare sealing resin compositions of Comparative Examples 1 to 4.
表１
Table 1
評価方法は以下の通りとした。 The evaluation method was as follows.
粘着シートの作成
上記で得られた封止樹脂組成物のトルエン希釈物を、離型フィルムＥ７００４（商品名：東洋紡社製、厚み７５μｍ、ＰＥＴ製）に乾燥後の膜厚が５０μｍまたは１００μｍとなるようにアプリケーターで塗布し、１２０℃×９０秒で乾燥させた。その後剥離力の異なる離型フィルムＥ７００２（商品名：東洋紡社製、厚み５０μｍ、ＰＥＴ製）でラミネートし、ラミネートした面から１，２００ｍＷ／ｃｍ２、６００ｍＪ／ｃｍ２、ＦｕｓｉｏｎＨ ｂｕｌｂで紫外線を照射し、２種類の離型フィルムにラミネートされた粘着シートを作成した。
Preparation of pressure-sensitive adhesive sheet The toluene dilution of the sealing resin composition obtained above was dried on a release film E7004 (trade name: Toyobo Co., Ltd., thickness: 75 μm, made by PET) to have a thickness of 50 μm. Alternatively, it was applied with an applicator so as to have a thickness of 100 μm, and dried at 120 ° C. for 90 seconds. Thereafter, lamination was performed with release films E7002 (trade name: manufactured by Toyobo Co., thickness: 50 μm, manufactured by PET) having different peeling forces, and ultraviolet rays were irradiated from the laminated surface with 1,200 mW / cm 2 , 600 mJ / cm 2 , and Fusion H bulb. An adhesive sheet laminated on two types of release films was prepared.
ガラス粘着力：上記で作成した５０μｍの粘着シートを用い片面の離型フィルムを剥離し、易接着ＰＥＴフィルムＡ４３００（東洋紡社製、厚み２３μｍ）に貼り合わせた後、残りの離型フィルムを剥離し、粘着シート面をガラスに貼り合わせ、１ｋｇの加重をかけて１５０ｍｍ×２５ｍｍの試験片とした。測定はＴｅｃｈｎｏＧｒａｐｈ製の引張り試験機ＴＧＩ−１ｋＮを用い、クロスヘッドスピード３００ｍｍ／ｍｉｎ．で、ガラス面に対し１８０°の剥離強度を測定し、５Ｎ／２５ｍｍ以上を○、未満を×とした。 Glass adhesive strength: using the 50 μm pressure-sensitive adhesive sheet prepared above, peeling off the release film on one side, bonding the film to an easy-adhesion PET film A4300 (manufactured by Toyobo Co., thickness 23 μm), and peeling off the remaining release film. Then, the pressure-sensitive adhesive sheet surface was bonded to glass, and a 1 kg load was applied to form a 150 mm × 25 mm test piece. The measurement was carried out using a tensile tester TGI-1kN manufactured by TechnoGraph, at a crosshead speed of 300 mm / min. Then, the peel strength at 180 ° with respect to the glass surface was measured.
透湿度：上記で作成した１００μｍの粘着シートから両面の離型フィルムを剥離し、ＪＩＳＺ ０２０８に準拠したカップ法により４０℃、相対湿度９０％の条件で７２時間測定し、２４時間ごとの測定値の平均値を算出し、１００μｍについては透湿度が１０ｇ／ｍ２・２４ｈｒ以下を○、超えるものを×とした。 Moisture permeability: The release film on both sides was peeled off from the 100 μm pressure-sensitive adhesive sheet prepared above, and measured for 72 hours at 40 ° C. and 90% relative humidity by a cup method in accordance with JISZ 0208, and measured every 24 hours The average value was calculated, and for 100 μm, the moisture permeability was rated as ○ when it was 10 g / m 2 · 24 hr or less, and as × when the moisture permeability exceeded 100 g / m 2.24 hr.
耐溶剤性：上記で作成した５０μｍの粘着シートを用い片面の離型フィルムを剥離した後、トルエンに１分浸漬後取り出し、１０秒放置後に粘着シートの表面を指で擦り、成膜状態を維持している場合を○、溶解あるいは形状維持が出来ていない場合を×とした。 Solvent resistance: Using the 50 μm pressure-sensitive adhesive sheet prepared above, peeling off the release film on one side, immersing it in toluene for 1 minute, removing it, leaving it for 10 seconds, rubbing the surface of the pressure-sensitive adhesive sheet with a finger, and maintaining the film formation state場合 indicates that the sample was melted, and X indicates that the sample was not dissolved or maintained.
光学特性：ＪＩＳＫ７３６１−１に準拠し、東洋精機製作所製のＨａｚｅ−ＧＡＲＤ２を用い、測定サンプルは上記で作成した１００μｍの粘着シートの離型フィルムを剥がし、厚さ１ｍｍの白板ガラス（商品名：松波硝子工業社製）で粘着性シートの両面に貼合わせて作製した。全光線透過率は９０％以上を○、未満を×、ヘイズは１．０％未満を○、以上を×とした。 Optical properties: Haze-GARD2 manufactured by Toyo Seiki Seisaku-Sho, Ltd. was used in accordance with JIS K7361-1, and the release film of the 100 μm adhesive sheet prepared above was peeled off as a measurement sample, and a 1 mm thick white plate glass (trade name: Matsunami (Manufactured by Glass Industry Co., Ltd.). Regarding the total light transmittance, 90% or more was evaluated as ○, less than ×, and the haze was evaluated as ○ when less than 1.0% and as x.
評価結果
表２
Evaluation results Table 2
実施例の各封止樹脂組成物はガラス粘着力、透湿度、耐溶剤性、光学特性のいずれも良好な結果を得た。 Each of the sealing resin compositions of Examples obtained good results in all of glass adhesive strength, moisture permeability, solvent resistance and optical properties.
一方、（Ａ）の代わりにポリイソブチレンを使用した比較例１および（Ｂ）の代わりに単官能モノマーを使用した比較例４は耐溶剤性が劣り、（Ａ）の代わりにイソブチレンとイソプレンの共重合体を使用した比較例２と３はガラス密着力が劣り、更に比較例３はついては光学特性も×評価となりいずれも本願発明に適さないものであった。 On the other hand, Comparative Example 1 in which polyisobutylene was used in place of (A) and Comparative Example 4 in which a monofunctional monomer was used in place of (B) had poor solvent resistance, and the copolymer of isobutylene and isoprene instead of (A). Comparative Examples 2 and 3 using the polymer were inferior in glass adhesion, and Comparative Example 3 was evaluated as poor in optical properties, and neither was suitable for the present invention.
本発明は、優れたガラスへの粘着力と耐溶剤性を有し、水蒸気の透過率が低いため、有機ＥＬ等の電子デバイスで封止樹脂組成物として有用である。
INDUSTRIAL APPLICABILITY The present invention has excellent adhesive strength to glass and solvent resistance, and has a low water vapor transmission rate, and thus is useful as a sealing resin composition in electronic devices such as organic EL.
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