JP2019077836A - Resin composition for sealing - Google Patents
Resin composition for sealing Download PDFInfo
- Publication number
- JP2019077836A JP2019077836A JP2017207742A JP2017207742A JP2019077836A JP 2019077836 A JP2019077836 A JP 2019077836A JP 2017207742 A JP2017207742 A JP 2017207742A JP 2017207742 A JP2017207742 A JP 2017207742A JP 2019077836 A JP2019077836 A JP 2019077836A
- Authority
- JP
- Japan
- Prior art keywords
- sealing
- resin composition
- less
- weight
- average molecular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
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出来る封止用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, thin-type electronic display device, and is expected as a device capable of performing a curved surface display as well as a flat surface display. However, the organic EL element is extremely weak to moisture, and the oxidation of the electrode and the organic material are likely to be denatured by the influence of oxygen in the air and heat from the element drive. As a result, when driving for a fixed time, degradation of performance such as generation of dark spots and growth becomes a major issue in addition to deterioration of light emission luminance, light emission efficiency and light emission uniformity, and stable light emission characteristics are maintained for a long time The technical improvement that can be done is advanced.
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（特許文献１）や、重量平均分子量が異なる２種類のポリイソブチレン系樹脂と軟化点が９０〜１３５℃の水素化石油樹脂を含む粘着性組成物（特許文献）が提案されており、これらの樹脂組成物はいずれも粘着力やその保持力は高く、また水蒸気の透過率も低いことから封止能力の高いものであった。しかしながらこれらの樹脂組成物を高温高湿下に暴露した場合は、封止樹脂層の内部に細かな気泡が発生する場合があり、結果として有機ＥＬ素子の品質低下を招くため改善の余地があった。 As a countermeasure, a composition for adhesive encapsulation containing a hydrogenated olefin polymer and a polyisobutylene resin (Patent Document 1), two kinds of polyisobutylene resins having different weight average molecular weights, and a softening point of 90 to 135 ° C. Adhesive compositions containing a hydrogenated petroleum resin (patent document) have been proposed, and all of these resin compositions have high adhesion and retention, and low permeability to water vapor, and therefore they have a sealing ability. It was expensive. However, when these resin compositions are exposed to high temperature and high humidity, fine bubbles may be generated in the inside of the sealing resin layer, and as a result, the quality of the organic EL element is deteriorated, so there is room for improvement. The
本発明は、優れた粘着力とアルミ板への密着性を有し、耐発泡性を有し水蒸気の透過率も低いため、例えば有機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用樹脂組成物を提供することにある。 The present invention has excellent adhesion and adhesion to an aluminum plate, has foam resistance and low permeability to water vapor, so when used as a sealing material in an electronic device such as an organic EL, It is an object of the present invention to provide a sealing resin composition which can suppress moisture absorption into a device and maintain stable quality over a long period of time.
請求項１記載の発明は、重量平均分子量が１，０００，０００以上であるポリイソブチレン（Ａ）と、重量平均分子量が１０，０００以下であるポリオレフィン（Ｂ）と、を含み、組成物全体に対する（Ａ）の含有量が５０〜９０重量％であることを特徴とする電子機器用封止用樹脂組成物を提供する。 The invention according to claim 1 comprises a polyisobutylene (A) having a weight average molecular weight of at least 1,000,000 and a polyolefin (B) having a weight average molecular weight of at most 10,000, for the entire composition. The sealing resin composition for electronic devices is characterized in that the content of (A) is 50 to 90% by weight.
また、請求項２記載の発明は、前記重量平均分子量が１０，０００以下であるポリオレフィン（Ｂ）が、２３℃で液状のポリブテンまたは石油樹脂から選択される少なくとも1種を有していることを特徴とする請求項１記載の電子機器用封止用樹脂組成物を提供する。 The invention according to claim 2 is that the polyolefin (B) having a weight average molecular weight of 10,000 or less has at least one selected from polybutene or petroleum resin which is liquid at 23 ° C. The resin composition for sealing for electronic devices according to claim 1 characterized by the above-mentioned.
また、請求項３記載の発明は、前記石油樹脂が、脂肪族、芳香族または水素添加された石油樹脂であることを特徴とする請求項１または２記載の電子機器用封止用樹脂組成物を提供する。 The invention according to claim 3 is that the petroleum resin is an aliphatic, aromatic or hydrogenated petroleum resin. The resin composition for sealing an electronic device according to claim 1 or 2, I will provide a.
また、請求項４記載の発明は、厚さ５０μｍにシート状に硬化した状態で４０℃、相対湿度９０％の環境下，シートの厚み方向における水蒸気透過率が２０ｇ／ｍ２・２４ｈｒ未満である、請求項１〜３いずれか記載の電子機器用封止用樹脂組成物を提供する。 In the invention according to claim 4, the water vapor transmission rate in the thickness direction of the sheet is less than 20 g / m 2 · 24 hr under an environment of 40 ° C and a relative humidity of 90% in a state cured to a thickness of 50 μm. The resin composition for electronic device sealing in any one of Claims 1-3 is provided.
また、請求項５記載の発明は、厚さ５０μｍにシート状に硬化した状態の全光線透過率が９０％以上で、ヘイズが１．０％以下である請求項１〜４いずれか記載の電子機器用封止用樹脂組成物を提供する。 The invention according to claim 5 is the electron according to any one of claims 1 to 4, wherein the total light transmittance is 90% or more and the haze is 1.0% or less when the sheet is cured to a thickness of 50 μm. Provided is a resin composition for device sealing.
本発明の封止樹脂組成物は、優れた粘着力と耐発泡性を有し、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 and resistance to foaming and has a low water vapor transmission rate, so when used as a sealing material for an organic EL element, for example, it suppresses moisture absorption into the element. By suppressing the electrode oxidation and the organic substance modification in the element, generation and growth of dark spots can be suppressed, and stable quality can be maintained over a long period of time.
以下本発明について詳細に説明する。 The present invention will be described in detail below.
本発明の組成物の構成は、重量平均分子量が１，０００，０００以上であるポリイソブチレン（Ａ）と、重量平均分子量が１０，０００以下であるポリオレフィン（Ｂ）である。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し、算出した。 The composition of the composition of the present invention is polyisobutylene (A) having a weight average molecular weight of 1,000,000 or more and polyolefin (B) having a weight average molecular weight of 10,000 or less. The weight average molecular weight (hereinafter referred to as "Mw.") Was calculated by measuring the molecular weight in terms of standard polystyrene using gel permeation chromatography and using a tetrahydrofuran-developing solvent on a styrene vinyl benzene-based column. .
本発明に使用されるポリイソブチレンは（Ａ）は、粘着性組成物の主成分であり、凝集力を上げ靭性を付与すると共に、水蒸気の透過率を低下させる。Ｍｗ．は１、０００，０００以上であり、１，０００，０００〜１、８００，０００が好ましく、１，０００，０００〜１、６００，０００が更に好ましい。Ｍｗ．が１，０００，０００未満では耐発泡性が低下する。またＭｗ．が１，８００，０００以下とすることで被着体への追従性を確保できる。市販のポリイソブチレン（Ａ）としてはＯＰＰＡＮＯＬＮ８０およびＮ１００（商品名：ＢＡＳＦジャパン社製）などがある。 The polyisobutylene used in the present invention (A) is a main component of the adhesive composition, which enhances cohesion and imparts toughness and lowers the water vapor transmission rate. Mw. Is 1,000,000 or more, preferably 1,000,000 to 1,800,000, and more preferably 1,000,000 to 1,600,000. Mw. If it is less than 1,000,000, the foam resistance is lowered. Also, Mw. By setting the value of 1,800,000 or less, the followability to the adherend can be secured. Commercially available polyisobutylene (A) includes OPPANOL 80 and N100 (trade name: manufactured by BASF Japan Ltd.).
組成物全体に対する（Ａ）の含有量は５０〜９０重量％であり、５５〜８５重量％が好ましく、５５〜８０重量％が更に好ましい。５０重量％未満では皮膜の凝集力が不足すると共に水蒸気透過率が上昇し、９０重量％超では皮膜の柔軟性が低下して被着体への密着力が低下する。 The content of (A) to the whole composition is 50 to 90% by weight, preferably 55 to 85% by weight, and more preferably 55 to 80% by weight. When the amount is less than 50% by weight, the cohesion of the film is insufficient and the water vapor transmission rate is increased. When the amount is more than 90% by weight, the flexibility of the film is reduced and the adhesion to the adherend is reduced.
本発明で使用するポリイソブチレンは、Ｍｗ．が１，０００，０００以上のもの（Ａ）に、Ｍｗ．が１，０００，０００未満のもの（ａ）を組み合わせて使用しても良く、その場合（Ａ）と（ａ）の混合比率（Ａ）：（ａ）は、１００：０〜７０：３０が好ましい。この範囲とすることで、耐発泡性に優れた皮膜の形成が可能となる。 The polyisobutylene used in the present invention is Mw. Is 1,000,000 or more (A), Mw. (A) having a ratio of less than 1,000,000 may be used in combination, in which case the mixing ratio of (A) to (a) (A): (a) is 100: 0 to 70:30. preferable. By setting it as this range, formation of the film excellent in foaming resistance is attained.
本発明に使用される重量平均分子量が１０，０００以下であるポリオレフィン（Ｂ）は、（Ａ）と良好な相溶性を持ち、粘着力を向上させる役割を担う。オレフィンモノマー由来の骨格を有するものであれば特に限定されず、またホモポリマーだけでなくコポリマー等の共重合でも良い。例えばポリエチレン樹脂、ポリプロピレン樹脂、ポリブテン樹脂、エチレン-プロピレン共重合体、エチレン-プロピレン−非共役ジエン共重合体、石油樹脂等があり、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、粘着性の付与や透湿性の観点から、ポリブテン樹脂及び石油樹脂が好ましい。 The polyolefin (B) having a weight average molecular weight of 10,000 or less used in the present invention has good compatibility with (A) and plays a role of improving the adhesive strength. It is not particularly limited as long as it has a skeleton derived from an olefin monomer, and not only a homopolymer but also a copolymer such as a copolymer may be used. For example, there are polyethylene resin, polypropylene resin, polybutene resin, ethylene-propylene copolymer, ethylene-propylene-non-conjugated diene copolymer, petroleum resin and the like, and they can be used alone or in combination of two or more. Among these, polybutene resins and petroleum resins are preferable from the viewpoint of imparting tackiness and moisture permeability.
ポリオレフィン（Ｂ）として好ましいポリブテン樹脂は、２３℃で液状の長鎖状炭化水素の分子構造を持つ無色の樹脂であり、皮膜を可塑化することで被着体に対する濡れ性を高めることが出来る。Ｍｗ．は５００〜５，０００が好ましく、８００〜３，０００が更に好ましい。Ｍｗ．を５００〜５，０００とすることで充分な皮膜の可塑化が可能となり、被着体へのぬれ性が向上する。市販のポリブテンとしては、ＨＶ−５０，ＨＶ−１００、ＨＶ−３００、ＨＶ−１９００（商品名：ＪＸＴＧエネルギー社製）などがある。 The polybutene resin preferable as the polyolefin (B) is a colorless resin having a molecular structure of long-chain hydrocarbon liquid at 23 ° C., and the wettability to an adherend can be enhanced by plasticizing the film. Mw. Is preferably 500 to 5,000, and more preferably 800 to 3,000. Mw. By setting the value of 500 to 5,000, sufficient film plasticization becomes possible, and the wettability to the adherend is improved. Commercially available polybutenes include HV-50, HV-100, HV-300, HV-1900 (trade name: manufactured by JXTG Energy Co., Ltd.).
同じくポリオレフィン（Ｂ）として好ましい石油樹脂は、ナフサ分解の副生油である主にＣ５〜Ｃ９留分を重合させたもので、（Ａ）への添加により粘着性を高めることが出来る。透明性が高くまた水蒸気のバリア特性が良好であり、その構造により脂肪族系、芳香族系、脂環族系（水素添加した芳香族系含む）などの種類が挙げられ、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、特に黄変が少ない点で脂肪族石油樹脂が好ましい。 The petroleum resin which is also preferable as the polyolefin (B) is one obtained by polymerizing mainly a C5 to C9 fraction which is a by-product oil of naphtha decomposition, and the tackiness can be enhanced by the addition to (A). It has high transparency and good barrier properties of water vapor, and depending on its structure, types such as aliphatics, aromatics, alicyclics (including hydrogenated aromatics), etc. may be mentioned, alone or in combination of two or more Can be used in combination. Among these, aliphatic petroleum resins are preferable in that yellowing is particularly small.
市販の石油樹脂としては、脂肪族系としてＱｕｉｎｔｏｎ１００シリーズ（商品名：日本ゼオン社製）、芳香族系としてＥＮＤＥＸ１５５（商品名：イーストマン社製）、脂環族系としてＥｓｃｏｒｅｚ５３００シリーズ（商品名：エクソンモービル社製）、Ｑｕｉｎｔｏｎ１３２５（商品名：日本ゼオン社製）、水添石油樹脂系としてアルコンＰシリーズ（商品名：荒川化学社製）、Ｔ−ＲＥＴＨＡシリーズ（商品名：ＪＸＴＧエネルギー社製）などが挙げられる。 Commercially available petroleum resins include Quinton 100 series (trade name: manufactured by Nippon Zeon Co., Ltd.) as an aliphatic type, ENDEX 155 (trade name: manufactured by Eastman) as an aromatic type, and Escorez 5300 series (trade name: Exxon as an alicyclic type). Mobil Co., Quinton 1325 (trade name: Nippon Zeon Co., Ltd.), Alcon P series (trade name: Arakawa Chemical Co., Ltd.), T-RETHA series (trade name: JXTG Energy Co.) as a hydrogenated petroleum resin system, etc. It can be mentioned.
石油樹脂のＭｗ．は３００〜５，０００が好ましく、５００〜４，０００が更に好ましい。この範囲とすることで耐熱性と粘着性とのバランスを取ることが出来る。また軟化点については７０〜１５０℃が好ましく、８０〜１３０℃が更に好ましい。この範囲とすることで粘着性と長期耐久性のバランスを取ることが出来る。なお軟化点は公知の方法により測定することができ、例えば熱機械分析（ＴＭＡ）法などが例示出来る。 Mw of petroleum resin. Is preferably 300 to 5,000, and more preferably 500 to 4,000. The heat resistance and the adhesiveness can be balanced by setting it as this range. The softening point is preferably 70 to 150 ° C., and more preferably 80 to 130 ° C. By setting it as this range, the balance of adhesiveness and long-term durability can be taken. The softening point can be measured by a known method, and for example, a thermal mechanical analysis (TMA) method can be exemplified.
組成物全体に対する（Ｂ）の含有量は５〜３５重量％が好ましく、１０〜３０重量％が更に好ましい。５重量％未満では皮膜の可塑化が充分できず粘着力が低下し、３５重量％超では皮膜の凝集力が低下して粘着力が低下し、水蒸気の透過率も高くなる。 5 to 35 weight% is preferable with respect to the whole composition, and 10 to 30 weight% is still more preferable. When the amount is less than 5% by weight, the film is not sufficiently plasticized and the adhesion is reduced. When the amount is more than 35% by weight, the cohesion of the film is reduced to decrease the adhesion and the water vapor permeability is also increased.
更に加えて本発明の封止用樹脂組成物は、性能を損なわない範囲で、必要に応じ可塑剤、乾燥剤、酸化防止剤、難燃剤、紫外線吸収剤、消泡剤剤、シランカップリング剤、着色剤、無機粒子、有機粒子等の添加剤を含有してもよい。 Furthermore, the resin composition for sealing of the present invention may, if necessary, be a plasticizer, a desiccant, an antioxidant, a flame retardant, an ultraviolet absorber, an antifoam agent, a silane coupling agent, as long as the performance is not impaired. And additives such as colorants, inorganic particles, and organic particles.
粘着性組成物を基材へ塗布する際は、封止用樹脂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。有機溶媒は封止材組成物に含まれるポリイソブチレン、ポリオレフィンを溶解出来れば公知のものを使用でき、例えばベンゼン、トルエン、キシレンなどの芳香族類、イソプロピルアルコールやブチルアルコール等のアルコール類、酢酸エチル、酢酸ブチル等の酢酸エステル類、アセトン、メチルエチルケトン、シクロヘキサノンなどのケトン類、エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル（以下「ＰＧＭ」と表記）などのエーテル類を挙げることができ、単独あるいは２種類以上を組み合わせて使用できる。これらの中では溶解性の観点で、トルエンが好ましい。 When the adhesive composition is applied to a substrate, the sealing resin composition is dissolved in an organic solvent such as toluene, for example, and diluted to a viscosity at which application is possible. The organic solvent may be polyisobutylene contained in the encapsulant composition or any known one capable of dissolving polyolefin, for example, benzene, aromatics such as toluene and xylene, alcohols such as isopropyl alcohol and butyl alcohol, ethyl acetate And acetates such as butyl acetate, ketones such as acetone, methyl ethyl ketone and cyclohexanone, and ethers such as ethylene glycol monobutyl ether and propylene glycol monomethyl ether (hereinafter referred to as "PGM"). It can use combining the above. Among these, toluene is preferred from the viewpoint of solubility.
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封止用樹脂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。 Although 10 to 30 weight% is illustrated as solid content at the time of dilution with the organic solvent, it is not particularly limited to this and can be freely selected. After the sealing resin composition diluted with the organic solvent is applied to the substrate, it is dried, for example, through a heating and drying furnace to remove the solvent.
封止用樹脂組成物の塗布方法としては、特に制限はなく公知の方法を用いることができ、例えばスプレーコート法、ナイフコート法、ダイコート法、グラビアコート法が挙げられる。溶剤乾燥後の塗布厚みとしては２０〜５０μｍ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。 There is no restriction | limiting in particular as a coating method of the resin composition for sealing, A well-known method can be used, For example, the spray coat method, the knife coat method, the die coat method, the gravure coat method is mentioned. Although 20-50 micrometers is illustrated as application | coating thickness after solvent drying, it is not specifically limited to this and can be selected freely.
本発明の封止用樹脂組成物を厚み５０μｍにシート化した粘着性シートの水蒸気透過率は、４０℃、相対湿度９０％の環境下において、２０ｇ／ｍ２・２４ｈｒ以下が好ましく、１５／ｍ２・２４ｈｒ以下がより好ましい。２０ｇ／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 water vapor transmission rate of the adhesive sheet obtained by forming the sealing resin composition of the present invention into a sheet having a thickness of 50 μm is preferably 20 g / m 2 · 24 hr or less under the environment of 40 ° C and 90% relative humidity, 15 / m It is more preferable that it is 2 · 24 hr or less. By setting the amount to 20 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.
また本発明の封止用樹脂組成物を厚み５０μｍにシート化した粘着性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％以下が好ましく、０．３以下がより好ましい。全光線透過率を９０％以上、ヘイズを１％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。 Moreover, 90% or more is preferable as a total light transmittance, and, as for the optical characteristic of the adhesive sheet which sheet-formed the resin composition for sealing of this invention to 50 micrometers in thickness, 91% or more is more preferable. The haze is preferably 1% or less, more preferably 0.3 or less. By setting the total light transmittance to 90% or more and the haze to 1% or less, sufficient image transmittance can be secured, and it can be used as a sealing material for an organic EL element.
本発明の封止用樹脂組成物は、Ｍｗ．が１，０００，０００以上と非常に大きなポリイソブチレン（Ａ）を用いることで、発泡性を大幅に低減できる。Ｍｗ，が１，０００，０００未満のものだけ、あるいは（Ａ）：（ａ）の配合比率が０：１００〜３０：７０のものを用いると、高温高湿環境下、例えば８５℃、８５％ＲＨで２４時間放置すると、封止樹脂層内に目視で確認できるレベルの気泡が発生するため、有機ＥＬ素子の長期信頼性が低下する虞がある。 The resin composition for sealing of the present invention has Mw. By using polyisobutylene (A) having a very large value of 1,000,000 or more, the foamability can be greatly reduced. When using only one having Mw, less than 1,000,000, or one having a compounding ratio of (A) :( a) of 0: 100 to 30: 70, for example, 85 ° C., 85% under high temperature and high humidity environment When left at RH for 24 hours, air bubbles of a level that can be visually confirmed are generated in the sealing resin layer, and thus the long-term reliability of the organic EL element may be reduced.
有機ＥＬ素子の封止剤として、本発明の封止用樹脂組成物を粘着性シートとして用いる場合の構成例を図１に示す。基板１１上に形成された積層体１２（発光層、金属電極等）の上から粘着性シート１３が積層され、更にカラーフィルター１４と封止用キャップ１５で覆われている。基板１１の材料としてはガラスの他に、屈曲性があるＰＥＴやシクロオレフィン系ポリマー等のプラスチックシートが用いられる場合がある。プラスチックシートを用いる場合は、ポリシザラン化合物、ポリカルボシラン化合物、ポリシラン化合物等によるガスバリア層が形成されることが多い。 The structural example in the case of using the resin composition for sealing of this invention as an adhesive sheet as sealing agent of organic EL element is shown in FIG. An adhesive sheet 13 is laminated on a laminate 12 (a light emitting layer, a metal electrode or the like) formed on a substrate 11 and is further covered with a color filter 14 and a sealing cap 15. As a material of the substrate 11, a plastic sheet such as flexible PET or cycloolefin polymer may be used in addition to glass. When a plastic sheet is used, a gas barrier layer is often formed of a polycisalane compound, a polycarbosilane compound, a polysilane compound or the like.
本発明の封止用樹脂組成物による粘着性シートは、被着体を限定せず比較的高い粘着力を示すが、特にガラスやアルミニウム基材に対して優れた粘着性を発現する。アルミニウム基材と易接着ＰＥＴフィルム（厚み５０μｍ）との剥離強度では、２３℃で５Ｎ／２５ｍｍ以上の強度があれば、ガラス基材の有機ＥＬ素子封止材として充分使用が可能であるが、７Ｎ／２５ｍｍ以上であればより好ましい。 Although the adhesive sheet by the sealing resin composition of the present invention exhibits a relatively high adhesive strength without limiting the adherend, it exhibits excellent adhesiveness particularly to glass and aluminum substrates. With regard to the peel strength between the aluminum substrate and the easy-to-adhere PET film (thickness 50 μm), if it has a strength of 5 N / 25 mm or more at 23 ° C, it can be used sufficiently as an organic EL element sealing material for glass substrate, It is more preferable if it is 7 N / 25 mm or more.
以下，実施例及び比較例にて本出願に係る封止用樹脂組成物について説明するが、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。 Hereinafter, although the sealing resin composition which concerns on this application with an Example and a comparative example is demonstrated, a specific example is shown and it does not specifically limit to these.
実施例１
Ｍｗ．が１，０００，０００以上であるポリイソブチレン（Ａ）としてＯＰＰＡＮＯＬ Ｎ １００（商品名：ＢＡＳＦジャパン社製、Ｍｗ．１，５５０，０００）を、Ｍｗ．が１０，０００以下であるポリオレフィン（Ｂ）としてポリブテンＨＶ−１９００（商品名：ＪＸＴＧエネルギー社製、Ｍｗ．２，９００）を、そしてポリイソブチレンとしてＯＰＰＡＮＯＬＢ １５ＳＦＮ（商品名：ＢＡＳＦジャパン社製、Ｍｗ．７５，０００）を表１記載の配合で撹拌容器に入れ、固形分が２０重量％の割合になるようにトルエンで希釈し、均一に溶解するまで撹拌脱泡した。
Example 1
Mw. As a polyisobutylene (A) having a Mw of 1,000,000 or more, MOP. 100 (trade name: manufactured by BASF Japan Ltd., Mw. 1, 550,000); Polybutene HV-1900 (trade name: manufactured by JXTG Energy, Mw. 2,900) as a polyolefin (B) having a Mw of 10,000 or less, and OPPANOLB 15 SFN (trade name: manufactured by BASF Japan Ltd., Mw.) As polyisobutylene. 75,000) was placed in a stirred vessel according to the formulation shown in Table 1, diluted with toluene to a solid content of 20% by weight, and stirred to defoam until uniformly dissolved.
実施例２〜１１
実施例１で用いた材料の他、（Ａ）としてＯＰＰＡＮＯＬ Ｎ ８０（商品名：ＢＡＳＦジャパン社製、Ｍｗ．１，０５０，０００）を、（Ｂ）としてポリブテンＨＶ−１００（商品名：ＪＸエネルギー社製、Ｍｗ．９８０）、脂肪族系石油樹脂ＱｕｉｎｔｏｎＲ−１００（商品名：日本ゼオン社製、Ｍｗ．２，１００）、Ｑｕｉｎｔｏｎ Ａ−１００（商品名：日本ゼオン社製、Ｍｗ．３，３００）、水添石油樹脂Ｔ−ＲＥＺ ＨＡ−０８５（商品名：ＪＸＴＧエネルギー社製、Ｍｗ．５５０）、Ｔ−ＲＥＺＨＡ−１２５（商品名：ＪＸＴＧエネルギー社製、Ｍｗ．６５０）、アルコンＰ−９０（商品名：荒川化学工業社製、Ｍｗ．１，１００）を表１記載の配合で撹拌容器に入れ、固形分が２０重量％の割合になるようにトルエンで希釈し、均一に溶解するまで撹拌脱泡した。
Examples 2 to 11
In addition to the materials used in Example 1, OPPANOL N 80 (trade name: manufactured by BASF Japan Ltd., Mw. 1, 050,000) as (A), polybutene HV-100 (trade name: JX energy) as (B) Corporation, Mw. 980), Aliphatic petroleum resin Quinton R-100 (trade name: manufactured by Nippon Zeon, Mw. 2, 100), Quinton A-100 (trade name: manufactured by Nippon Zeon, Mw. 3, 300) ), Hydrogenated petroleum resin T-REZ HA-085 (trade name: manufactured by JXTG Energy, Mw. 550), T-REZHA-125 (trade name: manufactured by JXTG Energy, Mw. 650), Alcon P-90 (trade name: Brand name: Arakawa Chemical Industries, Ltd., Mw. 1, 100) is put in a stirring vessel according to the composition shown in Table 1, diluted with toluene so that the solid content becomes 20% by weight, Stir degas until dissolved into one.
比較例１〜６
実施例で用いた材料の他、ポリイソブチレンとしてＯＰＰＡＮＯＬＮ ５０ＳＦ（商品名：ＢＡＳＦジャパン社製、Ｍｗ．５６５，０００）を、表１記載の配合で撹拌容器に入れ、固形分が２０重量％の割合になるようにトルエンで希釈し、均一に溶解するまで撹拌脱泡した。
Comparative Examples 1 to 6
In addition to the materials used in the examples, OPPANOLN 50SF (trade name: manufactured by BASF Japan Ltd., Mw. 565,000) as polyisobutylene was put in a stirring vessel according to the composition described in Table 1, and the solid content was 20% by weight The mixture was diluted with toluene to be stirred, and degassed with stirring until uniform dissolution.
評価項目及び評価方法Evaluation item and evaluation method
粘着性シートの作製
上記で得られた粘着性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及び２５μｍ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、粘着シート性を作成した。
Preparation of adhesive sheet The diluted toluene solution of the adhesive composition obtained above was dried to a release film E7004 (trade name: manufactured by Toyobo Co., Ltd., 75 μm thick, made of PET) and the film thickness was 50 μm. And 25 μm with an applicator and dried at 120 ° C. for 90 seconds. Thereafter, it was laminated with release films E7002 (trade name: manufactured by Toyobo Co., Ltd., thickness 50 μm, manufactured by PET) having different peeling forces to prepare adhesive sheet properties.
アルミ粘着力：上記で作成した２５×１５０ｍｍの粘着性シート（２５μｍ厚）の片面の離型フィルムを剥離し、易接着ＰＥＴフィルムＡ４３００（商品名：東洋紡社製、厚み５０μｍ）と貼り合わせ、その後残りの離型フィルムを剥離し、粘着性シートを５０×１５０×ｔ：２ｍｍのアルミ板（日本軽金属製Ａ１０５０Ｐ）に貼り合わせ、１ｋｇの加重でローラー圧締し、測定サンプルとした。
Ｔｅｃｈｎｏ Ｇｒａｐｈ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．で環境温度２３℃における、アルミ面に対し１８０°の剥離強度を測定し、５Ｎ／２５ｍｍ以上を○、未満を×とした。
Aluminum adhesive force: The release film on one side of the 25 × 150 mm adhesive sheet (25 μm thick) prepared above is peeled off, and it is pasted to easy-adhesion PET film A4300 (trade name: manufactured by Toyobo Co., Ltd., thickness 50 μm) The remaining release film was peeled off, the adhesive sheet was bonded to a 50 × 150 × t: 2 mm aluminum plate (A1050P made by Nippon Light Metal Co., Ltd.), and roller compression was carried out with a 1 kg weight to obtain a measurement sample.
Using a tensile tester TGI-1 kN manufactured by Techno Graph, a crosshead speed of 300 mm / min. The peel strength at 180 ° with respect to the aluminum surface was measured at an environmental temperature of 23 ° C., and 5 N / 25 mm or more was ○, less than x.
透湿度：上記で作成した直径７０ｍｍの粘着性シート（５０μｍ厚）から両面の離型フィルムを剥離し、ＪＩＳ Ｚ 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、透湿度が２０ｇ／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 adhesive sheet (50 μm thickness) with a diameter of 70 mm prepared above, and measured for 72 hours under the conditions of 40 ° C. and 90% relative humidity by the cup method according to JIS Z 0208 The average value of the measured values every 24 hours was calculated, and those with a moisture permeability of 20 g / m 2 · 24 hr or less as ○, and those exceeding it were considered as ×.
耐発泡性：５０×５０ｍｍにカットした上記粘着シート（５０μｍ厚）を、離型フィルムを剥がして２ｍｍのアルミ板に貼り合せ、８５℃×８５％ＲＨの環境下で１２時間放置後、目視で発泡の有無を確認し、発泡がない場合を○、ある場合を×とした。 Foam resistance: The above-mentioned adhesive sheet (50 μm thickness) cut into 50 × 50 mm is peeled off from the mold release film and attached to a 2 mm aluminum plate, and left for 12 hours under an environment of 85 ° C. × 85% RH visually The presence or absence of foaming was confirmed, and the case where there was no foaming was marked with ○, and the case with x.
全光線透過率／ヘイズ：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粘着シート（２５μｍ厚）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％未満を○、以上を×とした。 Total light transmittance / Haze: based on JISK7361-1, using Haze-GARD2 manufactured by Toyo Seiki Seisakusho, the measurement sample peel off the release film of the adhesive sheet (25 μm thickness) prepared above, and a white board of 1 mm thickness It bonded and produced on both surfaces of the adhesive sheet with glass (brand name: made by Matsunami Glass Industrial Co., Ltd.). 90% or more of the total light transmittance was ○, less than x, and less than 1% was ○, more than x.
評価結果
評価結果を表２に示す。
Evaluation Results Evaluation results are shown in Table 2.
実施例の各粘着性組成物はガラス粘着力、透湿度、光学特性のいずれも良好な結果を得た。 Each adhesive composition of the example obtained good results in all of glass adhesion, moisture permeability and optical properties.
（Ｂ）を配合していない比較例１は、耐アルミ粘着力及び透湿度が劣り、Ｍｗ．が１，０００，０００未満のポリイソブチレンを用いた比較例２〜６は全て発泡性に劣り、いずれも本願発明に適さないものであった。 The comparative example 1 which does not mix | blend (B) is inferior in aluminum-proof adhesive force and moisture permeability, and Mw. All of Comparative Examples 2 to 6 using a polyisobutylene of less than 1,000,000 were inferior in foamability, and all were not suitable for the present invention.
本発明は、優れた粘着力と低発泡性を有し、水蒸気の透過率が低いため、有機ＥＬ素子等の電子デバイスの封止材料として有用である。 INDUSTRIAL APPLICABILITY The present invention is useful as a sealing material for an electronic device such as an organic EL element because it has excellent adhesion and low foamability and low water vapor transmission rate.
１１ 基板
１２ 積層体
１３ 粘着性シート
１４ カラーフィルター
１５ 封止用キャップ
11 substrate 12 laminate 13 adhesive sheet 14 color filter
15 Cap for sealing
Claims (5)
The resin composition for electronic device sealing according to any one of claims 1 to 4, wherein the total light transmittance in a state of being cured in a sheet shape to a thickness of 50 μm is 90% or more and the haze is 1.0% or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017207742A JP7007157B2 (en) | 2017-10-27 | 2017-10-27 | Encapsulating resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017207742A JP7007157B2 (en) | 2017-10-27 | 2017-10-27 | Encapsulating resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2019077836A true JP2019077836A (en) | 2019-05-23 |
| JP7007157B2 JP7007157B2 (en) | 2022-01-24 |
Family
ID=66627318
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2017207742A Active JP7007157B2 (en) | 2017-10-27 | 2017-10-27 | Encapsulating resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP7007157B2 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009524705A (en) * | 2006-01-24 | 2009-07-02 | スリーエム イノベイティブ プロパティズ カンパニー | Adhesive encapsulating composition film and organic electroluminescence device |
| WO2011062167A1 (en) * | 2009-11-18 | 2011-05-26 | 味の素株式会社 | Resin composition |
| WO2015146935A1 (en) * | 2014-03-27 | 2015-10-01 | リンテック株式会社 | Sealing sheet, and sealing structure and device |
| JP2015197969A (en) * | 2014-03-31 | 2015-11-09 | 古河電気工業株式会社 | Resin composition for sealing organic electronic device element, resin sheet for sealing organic electronic device element, organic electroluminescent element and image display device |
| JP2017027941A (en) * | 2015-07-21 | 2017-02-02 | 味の素株式会社 | Sealing resin composition |
-
2017
- 2017-10-27 JP JP2017207742A patent/JP7007157B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009524705A (en) * | 2006-01-24 | 2009-07-02 | スリーエム イノベイティブ プロパティズ カンパニー | Adhesive encapsulating composition film and organic electroluminescence device |
| WO2011062167A1 (en) * | 2009-11-18 | 2011-05-26 | 味の素株式会社 | Resin composition |
| WO2015146935A1 (en) * | 2014-03-27 | 2015-10-01 | リンテック株式会社 | Sealing sheet, and sealing structure and device |
| JP2015197969A (en) * | 2014-03-31 | 2015-11-09 | 古河電気工業株式会社 | Resin composition for sealing organic electronic device element, resin sheet for sealing organic electronic device element, organic electroluminescent element and image display device |
| JP2017027941A (en) * | 2015-07-21 | 2017-02-02 | 味の素株式会社 | Sealing resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP7007157B2 (en) | 2022-01-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6226070B2 (en) | Polyolefin adhesive composition | |
| US20100148127A1 (en) | Method For Encapsulating An Electronic Arrangement | |
| KR102087145B1 (en) | Adhesive agent having adhesive blend of acrylate and styrene block copolymer | |
| EP2652060B1 (en) | Pressure sensitive adhesives for low surface energy substrates | |
| US10287427B2 (en) | Compositions based on acrylic block copolymer blends | |
| JP6353464B2 (en) | Modified polyolefin resin, composition, adhesive, primer, binder and laminate | |
| JP6446776B2 (en) | Modified polyolefin resin | |
| JP2014231586A (en) | Adhesive composition and adhesive sheet using the same | |
| JP7066507B2 (en) | Photocurable adhesive resin composition and adhesive tape using it | |
| WO2017199985A1 (en) | Adhesive, adhesive resin composition and laminate comprising same | |
| KR101622751B1 (en) | Resin composition comprising polyalkyene carbonate and self adhesive film produced therefrom | |
| JP2009062522A (en) | Water-based adhesive | |
| JP2019077836A (en) | Resin composition for sealing | |
| JP2015007242A (en) | Adhesive tape | |
| KR101530660B1 (en) | Coating composition for moisture-proof and method of manufacturing the same | |
| CN108504024B (en) | Interpenetrating network polymer for low-temperature heat-sealing film and low-temperature heat-sealing PE film | |
| JP2013010854A (en) | Primer composition for polycarbonate and polycarbonate | |
| CA3152676A1 (en) | Modified polyolefin resin and dispersion composition thereof | |
| JP6595440B2 (en) | Adhesive composition and adhesive sheet | |
| KR100406623B1 (en) | Pressure-sensitive adhesive and surface-protective material | |
| KR100905934B1 (en) | A pressure-sensitive adhesive for protection film of light functionalized sheet | |
| JP2014070189A (en) | Adhesive for polyolefin multilayer film, master batch for adhesive for polyolefin multilayer film and polyolefin multilayer film | |
| KR19990078394A (en) | Pressure-sensitive adhesive and surface protective material | |
| JP7362028B2 (en) | Modified polyolefin resin | |
| EP3587106A1 (en) | Plasticiser-free polyvinyl butyral dispersion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20201001 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20210714 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20210729 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20210811 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20211228 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20220106 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7007157 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |