JP3633802B2 - Curable composition for light emitting display body sealing material and method for producing light emitting display body - Google Patents

Description

などで示される鎖状、環状のものが挙げられる。
【００２４】
さらに上記ヒドロシリル基含有硬化剤のうち、（Ａ）成分との相溶性が良いという点から、特に下記のものが好ましい。
【００２５】
【化２】

また、これらの（Ｂ）成分中に含まれるヒドロシリル基は少なくとも１分子中に２個あれば良いが、２〜４０個が好ましい。本発明の組成物をヒドロシリル化反応により硬化させる場合には、該ヒドロシリル基の個数が２より少ないと、硬化が遅く硬化不良を起こす場合が多い。また、該ヒドロシリル基の個数が４０より多くなると、（Ｂ）成分である硬化剤の安定性が悪くなるほか、ヒドロシリル基の反応性が低くなり、未反応のヒドロシリル基が硬化物中に残存し、ボイドやクラックの原因となる。
【００２６】
本発明の（Ｃ）成分であるヒドロシリル化触媒については、特に制限はなく、任意のものが使用できる。
【００２７】
具体的に例示すれば、塩化白金酸、白金の単体、アルミナ、シリカ、カ−ボンブラック等の担体に固体白金を担持させたもの；
白金ービニルシロキサン錯体｛例えば、Ｐｔ_ｎ（ＶｉＭｅ_２ＳｉＯＳｉＭｅ_２Ｖｉ）ｎ、Ｐｔ〔（ＭｅＶｉＳｉＯ）_４〕_ｍ｝；
白金ーホスフィン錯体｛例えば、Ｐｔ（ＰＰｈ_３）_４、Ｐｔ（ＰＢｕ_３）_４｝；
白金ーホスファイト錯体｛例えば、 Ｐｔ〔Ｐ（ＯＰｈ）_３〕_４、Ｐｔ〔Ｐ（ＯＢｕ）_３〕_４
（式中、Ｍｅはメチル基、Ｂｕはブチル基、Ｖｉはビニル基、Ｐｈはフェニル基を表し、ｎ、ｍは整数を表す）、Ｐｔ（ａｃａｃ）_２、また、Ａｓｈｂｙらの米国特許第３１５９６０１及び３１５９６６２号明細書中に記載された白金−炭化水素複合体、並びにＬａｍｏｒｅａｕｘらの米国特許第３２２０９７２号明細書中に記載された白金アルコラ−ト触媒も挙げられる。
【００２８】
また、白金化合物以外の触媒の例としては、ＲｈＣｌ（ＰＰｈ_３）_３、ＲｈＣｌ_３、Ｒｈ／Ａｌ_２Ｏ_３、ＲｕＣｌ_３、ＩｒＣｌ_３、ＦｅＣｌ_３、ＡｌＣｌ_３、ＰｄＣｌ_２・２Ｈ_２Ｏ、ＮｉＣｌ_２、ＴｉＣｌ_４、等が挙げられる。これらの触媒は単独で使用してもよく、２種以上併用しても構わない。触媒活性の点から塩化白金酸、白金−オレフィン錯体、白金−ビニルシロキサン錯体、Ｐｔ（ａｃａｃ）_２等が好ましい。触媒量としては特に制限はないが、（Ａ）成分中のアルケニル基１ｍｏｌに対して１０^−１〜１０^−８ｍｏｌの範囲で用いるのがよい。好ましくは１０^−２〜１０^−６ｍｏｌの範囲で用いるのがよい。また、ヒドロシリル化触媒は、一般に高価で腐食性であり、また、水素ガスを大量に発生して硬化物が発泡してしまう場合があるので１０^−１モル以上用いない方がよい。
【００２９】
本発明の（Ｄ）成分である炭素数６〜２０のα−オレフィンは、硬化前の組成物の粘度を低下させるとともに、硬化反応時には（Ｂ）成分である硬化剤のＳｉ−Ｈ基とヒドロシリル化反応により結合し、結局構造内に取り込まれるものである。
【００３０】
また、（Ｄ）成分として、硬化養生中に揮発し得るような低沸点の化合物を用いた場合は、硬化前後で形状変化を起こしたり、揮発物により環境にも悪影響を及ぼすことから、炭素数が８以上が特に好ましい。
【００３１】
また、分子中に少なくとも２個のヒドロシリル化反応可能なアルケニル基あるいはアルキニル基を有する化合物を用いた場合上記の効果に加えて、（Ｂ）成分とヒドロシリル化反応することにより架橋点の官能基数を稼ぐことができる。この場合、分子中に少なくとも２個のヒドロシリル化反応可能なアルケニル基あるいはアルキニル基を有する化合物を多量に配合すると、硬化物の引張弾性率が大きくなり、堅く脆いものとなるため、その最適な配合量は比較的少ない。
【００３２】
また、炭素数６〜２０のα−オレフィンと分子中に少なくとも２個のヒドロシリル化反応可能なアルケニル基あるいはアルキニル基を有する化合物を併用すると、硬化前の組成物の粘度を低下させ、架橋点をかせぐことができるため、これらの併用が好ましい。
【００３４】
（Ｄ）成分の添加量は、（Ａ）成分であるイソブチレン系重合体と（Ｂ）成分である硬化剤とのヒドロシリル化反応による３次元的架橋構造の形成を妨げない範囲であれば、特に制限はない。すなわち、（Ｄ）成分の添加量が過剰になった場合、（Ｂ）成分のＳｉ−Ｈ基は（Ｄ）成分の不飽和基とのヒドロシリル化反応により消費されてしまい、（Ａ）成分による３次元的架橋構造の形成が不十分となることがある。
【００３５】
（Ｄ）成分は（Ａ）成分の重合体１００重量部に対し０．１〜１００重量部、好ましくは０．５〜７０重量部、特には１〜５０重量部用いることが好ましい。
【００３６】
本発明の（Ｅ）成分であるカーボンブラックは、発光表示体封止材用硬化性組成物を黒く着色させるために用いられる。発光表示体の封止材として硬化性組成物を用いる場合、発光素子の発光を際立たせ、明確に見せるために、下地となる封止材は、黒色であることが好ましい。従って、発光表示体封止材用硬化性組成物を黒く着色させる必要が有り、（Ｅ）成分としてカーボンブラックを添加する。（Ｅ）成分としては、通常、ゴムの添加剤やインキ、塗料、樹脂の着色剤、トナー等に用いられる一般のカーボンブラックであれば、特に限定されるものではない。
【００３７】
（Ｅ）成分の添加量は、着色させるという目的達することができれば特に限定されるものではないが、硬化性樹脂組成物の硬化前の粘度を著しく増粘させたり、硬化性を著しく阻害しない範囲で用いるのが好ましく、（Ａ）成分の重合体１００重量部に対し０．１〜３０重量部、好ましくは０．２〜１０重量部、特には０．５〜５重量部用いることが好ましい。
【００３８】
また、本発明においては、硬化物の表面の艶消しを目的に、（Ｆ）成分として艶消し剤を用いることができる。艶消し剤としては、硬化物表面の直線光反射率を低下させる添加剤であれば特に限定されるものではないが、例えば、有機または無機系の微粒子が例示される。
【００３９】
（Ｆ）成分の具体例としては、ウレタン系微粒子、アクリル系樹脂微粒子、メタクリル系樹脂微粒子、スチレン系樹脂微粒子、ポリオレフィン系樹脂微粒子、ポリ塩化ビニル系樹脂微粒子、メタクリル−ブタジエン−スチレン系樹脂微粒子、ステアリン酸アルミニウム、炭酸マグネシウム、ポリエチレンワックス、微粉ケイ酸（シリカ）、シリカアルミナ粒子などが例示される。
【００４０】
（Ｆ）成分の粒子径としては、艶消しの目的が達せられれば特に限定はないが、好ましくは、０．１μｍ〜１００μｍ、さらに好ましくは、１μｍ〜５０μｍである。（Ｆ）成分の添加量も上記目的を達せられれば特に限定はないが、硬化性樹脂組成物の硬化前の粘度を著しく増粘させたり、硬化性を著しく阻害しない範囲で用いるのが好ましく、（Ａ）成分の重合体１００重量部に対し０．１〜５０重量部、好ましくは０．２〜２０重量部、特には０．５〜１０重量部用いることが好ましい。
【００４１】
また、本発明において艶消し剤を用いずとも、硬化性組成物が硬化後、サンドペーパーなどで表面に物理的に傷をつけて、艶消し表面を形成しても良い。
【００４２】
また、本発明の硬化性組成物には保存安定性を改良する目的で、保存安定性改良剤を使用することができる。この保存安定性改良剤は、本発明の（Ｂ）成分の保存安定性改良剤として一般に知られている安定剤であり、所期の目的を達成するものであればよく、特に限定されるものではない。
【００４３】
具体的には、脂肪族不飽和結合を含有する化合物、有機リン化合物、有機硫黄化合物、窒素含有化合物、スズ系化合物、有機過酸化物等を好適に用いることができる。さらに具体的には、２−ベンゾチアゾリルサルファイド、ベンゾチアゾ−ル、チアゾ−ル、ジメチルアセチレンダイカルボキシレ−ト、ジエチルアセチレンダイカルボキシレ−ト、ＢＨＴ、ブチルヒドロキシアニソ−ル、ビタミンＥ、２−（４−モルフォジニルジチオ）ベンゾチアゾ−ル、３−メチル−１−ブテン−３−オ−ル、アセチレン性不飽和基含有オルガノシロキサン、アセチレンアルコ−ル、３−メチル−１−ブチル−３−オ−ル、ジアリルフマレ−ト、ジアリルマレエ−ト、ジエチルフマレ−ト、ジエチルマレエ−ト、ジメチルマレエ−ト、２−ペンテンニトリル、２，３−ジクロロプロペン等が挙げられ、特にポットライフ／速硬化性の両立という点でチアゾール、ベンゾチアゾール、ジメチルマレエートが好ましいが、これらに限定されるわけではない。
【００４４】
また、本発明の硬化性組成物には、酸化防止剤、紫外線吸収剤、顔料、界面活性剤等を適宜添加することができる。これらの使用にあたっては、ヒドロシリル化反応に対する影響を考慮しなければならない。
【００４５】
また、本発明の組成物には、接着性を付与する目的で接着付与剤を添加することができる。接着付与剤の例としては、各種シランカップリング剤やエポキシ樹脂等があげられる。特にエポキシ基、メタクリロイル基、ビニル基等の官能基を有するシランカップリング剤は、硬化性に及ぼす影響も小さく、接着性の発現にも効果が大きく使いやすい。但し、使用できるシランカップリング剤としてこれらに限定されるものではない。また、シランカップリング剤やエポキシ樹脂と併用してこれらの反応触媒を添加することができる。
【００４６】
本発明の硬化性組成物を作製するにあたっては、通常使用される各種混合装置が使用できる。このようにして得られる組成物を使用するにあたっては、各種脱泡装置を用いて脱泡した後、注型、ポッティング、コーティングといった各種加工方法に適用すればよい。
【００４７】
次に、本発明の発光表示体（ＬＥＤパネル）の製造方法を説明する。但し、本発明は配線基板に多数の発光素子を配設し、これを任意の形状のパネルに装着し、形成する発光表示体において、発光素子の発光部のみを露出させ、その他の部分を発光表示体封止材用硬化性組成物で封止させるものであればよく、以下の例に限定されるものではない。
【００４８】
配線基板上に、▲１▼一定間隔をおいてＬＥＤを規則的に配設し、▲２▼この基板を並べて発光表示体パネルを形成する。▲３▼開口部を有する樹脂製箱状成形体にＬＥＤ発光部を箱状成形体の開口部側にして挿入し、固定する。▲４▼開口部裏面には基板に配設したＬＥＤに通電するための配線を取り出す。▲５▼この箱状成形体の開口部をすべて覆い、ＬＥＤの発光部のみを露出させた状態となるように、発光表示体封止材用硬化性組成物を流し込み、▲６▼加熱硬化させて発光表示体パネルを製造する。
【００４９】
【実施例】
次に実施例を挙げて、本発明をより一層明らかにするが、実施例により本発明は何ら限定されるものではない。
（実施例１）
（Ａ）成分としては、特開平８−１３４２２０に記載されている方法により合成した下記の構造を示す化合物Ａ（分析値は表１に示す）を使用した。
【００５０】
【化３】

【００５１】
【表１】

まず、（Ａ）成分１００重量部に対して、（Ｄ）成分としてオクタデセン（出光石油化学製 リニアレン１８）３５重量部及びビスフェノールＡジアリルエーテル（三井化学社製）２０重量部、（Ｅ）成分としてカーボンブラック（三菱化学社製 ＭＡ６００）１重量部、及び酸化防止剤としてＭＡＲＫ ＡＯ−５０（旭電化製）１重量部を混合し、ロールにて３回混練した。ついで、この混合物に下記に構造を示す（Ｂ）成分である化合物Ｂ
【００５２】
【化４】

を（Ａ）成分１００重量部に対し６０重量部混合した。更に、（Ｃ）成分としてビス（１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン）白金錯体触媒（１７．９×１０^−５ｍｍｏｌ／μｌ、キシレン溶液）を白金が（Ａ）成分及び（Ｄ）成分のアルケニル基量のモル数に対して５×１０^−４当量及び保存安定性改良剤としてジメチルマレエートを白金に対し３モル当量を秤量し、均一混合した。該組成物を５ｃｍ×５ｃｍの金型に流し込み、約１ＭＰａの圧力をかけて８０℃の温度で３０分間硬化させた。得られた硬化物の吸水率をプレッシャークッカー（１２１℃−２気圧）中、２４時間放置前後の重量変化から測定した。
（実施例２）
実施例１の配合物に（Ｆ）成分として微粉ケイ酸（水澤化学社製 Ｍｉｚｕｋａｓｉｌ Ｐ−５２６）を（Ａ）成分１００重量部に対し、１０部配合した以外は同様の組成物で硬化物を作成し、実施例１と同様の評価を行った。更に、実施例２では、組成物をガラス上に塗布し、８０℃の温度で３０分硬化させ光沢度計を用いて、６０°でのグロスを測定した。
（比較例１）
市販シリコーン樹脂（ＴＳＥ３２５１，東芝シリコーン製）を用いて、実施例１と同様に成形体作成およびガラス上に塗布し、実施例１、２と同様の評価を行った。
【００５３】
【表２】

表２の結果より、本発明における発光表示体封止材用硬化性組成物は、吸水率が低く、湿気、水分による基板内部への水分の進入を抑え得ることができる。さらに、艶消し剤の添加により艶消し効果も得られた。
【００５４】
【発明の効果】
本発明によって得られる発光表示体封止材用硬化性組成物は吸水率が低く、耐湿性にも優れる組成物である。また、艶消し剤の添加により、艶消しもできた。 従って、発光表示体封止材用硬化性組成物として、配線基板に多数の発光素子を配設し、これを任意の形状のパネルに装着し、形成する発光表示体において、発光素子の発光部のみを露出させ、その他の部分を封止して製造する発光表示体に用いることにより、非常に優れた信頼性を得ることができる。
【００５５】
さらに本発明により、このような発光表示体の製造方法も提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention is used to expose a light emitting part of a light emitting element and seal other parts in a light emitting display formed by mounting a plurality of light emitting elements arranged on a wiring board on a panel. The present invention relates to a curable composition for a light-emitting display body sealing material and a method for producing a light-emitting display body using the same.
[0002]
[Prior art]
A light-emitting display body (LED panel) using an LED light-emitting element is covered with glass or a transparent resin to be used as a display body indoors, and with a sealing resin formed by curing a liquid curable composition. In some cases, sealing is performed with only the light emitting portion exposed, and it is used as it is outdoors. In a light emitting display (LED panel) using such LED light emitting elements for outdoor use, a silicone resin has been used as a panel sealing material.
[0003]
However, since the silicone resin has high moisture permeability, there has been a problem that, when used in outdoor applications, due to rain or the like, water absorption of the sealing material, insulation failure due to moisture absorption, and the like occur.
[0004]
In addition, the silicone resin has a high linear light reflectivity on the resin surface after curing, and has a so-called shine on the surface, and when used as a sealing material for a light-emitting display, a method such as physically scratching the surface after curing It is necessary to perform matting.
[0005]
[Problems to be solved by the invention]
The present invention has been made in view of such a situation, and provides a curable composition for a sealing material for a light-emitting display body having low hygroscopicity and excellent moisture resistance, and a method for producing a light-emitting display body using the same. To do.
[0006]
[Means for Solving the Problems]
The present inventors have repeated intensive studies to solve the above problems,
(A) Isobutylene polymer containing at least one hydrosilylation-reactive alkenyl group in the molecule (B) Curing agent containing at least two hydrosilyl groups in the molecule (C) Hydrosilylation catalyst (D) Carbon The present inventors have found that a resin composition comprising an α-olefin (E) carbon black of several 6 to 20 has low hygroscopicity and excellent moisture resistance after curing, and has led to the present invention.
[0007]
That is, the present invention relates to (1) a curable composition for a light emitting display sealing material comprising the following components as essential components.
(A) Isobutylene polymer containing at least one hydrosilylation-reactive alkenyl group in the molecule (B) Curing agent containing at least two hydrosilyl groups in the molecule (C) Hydrosilylation catalyst (D) Carbon The α-olefin (E) carbon black of several 6 to 20 Further , the present invention provides (2) light emission in a light emitting display formed by mounting a plurality of light emitting elements arranged on a wiring board on a panel. The present invention relates to the curable composition for a light-emitting display element sealing material according to (1), wherein the light-emitting portion of the element is exposed.
[0008]
The present invention also provides:
(3) The curable composition for a light-emitting display element sealing material according to (1) or (2), wherein an alkenyl group capable of hydrosilylation reaction in the polymer of component (A) is contained at the end of the polymer. .
[0009]
The present invention also provides:
(4) The curable composition for a light-emitting display element sealing material according to (1) to (3), wherein the total amount of repeating units derived from isobutylene in the polymer of component (A) is 50% by weight or more.
[0010]
The present invention also provides:
(5) The curable composition for a light-emitting display body sealing material according to (1) to (4), wherein the curing agent of component (B) is an organohydrogenpolysiloxane containing at least two hydrosilyl groups in the molecule. .
[0014]
The present onset Ming, as (6) (F) component, a light emitting display body sealing material curable composition characterized by adding a matting agent (1) to (5).
[0015]
Moreover, this invention relates to the manufacturing method of the light emission display body characterized by using the curable composition for light emission display body sealing materials which uses the following component as an essential component ( 7 ).
(A) Isobutylene polymer containing at least one hydrosilylation-reactive alkenyl group in the molecule (B) Curing agent containing at least two hydrosilyl groups in the molecule (C) Hydrosilylation catalyst (D) Carbon [ Alpha] -olefin (E) carbon black of several 6 to 20
DETAILED DESCRIPTION OF THE INVENTION
The component (A) used in the present invention is an isobutylene polymer having at least one alkenyl group capable of hydrosilylation reaction in the molecule. Here, the isobutylene-based polymer means that the monomer unit constituting the polymer skeleton is mainly composed of isobutylene units. In this case, all of the monomers may be formed from isobutylene units, and the monomer units having copolymerizability with isobutylene are preferably 50% (% by weight, the same applies hereinafter) or less of isobutylene-based polymers. May be contained in a range of 30% or less, particularly preferably 20% or less. However, in these polymer skeletons, from the viewpoint of moisture resistance, weather resistance, and heat resistance, the repeating unit constituting the main chain excluding the alkenyl group does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring. It is particularly preferred that it is composed of saturated hydrocarbons. Further, the isobutylene polymer used as the component (A) in the present invention includes butadiene, isoprene, 1,13-tetradecadiene, 1,9-decadiene, 1,5-deoxydiene as long as the object of the present invention is achieved. A small amount of a unit monomer such as a polyene compound such as hexadiene that leaves a double bond after polymerization may be contained, preferably in the range of 10% or less.
[0017]
Specific examples of the copolymer component constituting the main chain skeleton of such an isobutylene polymer include, for example, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, 4 -Methyl-1-pentene, hexene, vinylcyclohexane, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methyl styrene, dimethyl styrene, pt-butoxy styrene, p-hexenyloxy styrene, p -Allyloxystyrene, p-hydroxystyrene, β-pinene, indene, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1,3,3-tetramethyldi Siloxane, trivinylmethylsilane, tetravinylsila , Allyldimethylmethoxysilane, allyltrimethylsilane, diallyldimethoxysilane, diallyldimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and the like.
[0018]
The alkenyl group capable of hydrosilylation is not particularly limited as long as it is a group containing a carbon-carbon double bond that is active for hydrosilylation. Alkenyl groups include vinyl, allyl, methylvinyl, propenyl, butenyl, pentenyl, hexenyl and other aliphatic unsaturated hydrocarbon groups, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl. And cyclic unsaturated hydrocarbon groups such as In the present invention, the component (A) preferably has 1 to 10 alkenyl groups in one molecule.
[0019]
The number average molecular weight (GPC method, in terms of polystyrene) of the isobutylene polymer is preferably about 500 to 100,000, and in particular, a liquid substance having a fluidity of about 1000 to 40,000 and fluidity are preferable from the viewpoint of ease of handling. .
[0020]
As the method for producing the component (A) of the present invention, it can be produced by the method described in JP-A-8-134220.
[0021]
The curing agent which is the component (B) of the present invention is not particularly limited as long as it contains at least two hydrosilyl groups in the molecule. Here, one hydrosilyl group refers to one Si-H bond. Therefore, when two hydrogen atoms are bonded to the same Si, it is calculated as two hydrosilyl groups.
[0022]
As the component (B), organohydrogenpolysiloxane is preferred in view of the simplicity and stability of the synthesis method. The organohydrogenpolysiloxane here refers to a polysiloxane having a hydrocarbon group or a hydrogen atom on a silicon atom.
[0023]
[Chemical 1]

Examples of such chain-like and cyclic ones are shown below.
[0024]
Furthermore, among the above hydrosilyl group-containing curing agents, the following are particularly preferable from the viewpoint of good compatibility with the component (A).
[0025]
[Chemical formula 2]

Moreover, the hydrosilyl group contained in these (B) components should just be at least 2 in 1 molecule, but 2-40 are preferable. When the composition of the present invention is cured by a hydrosilylation reaction, if the number of hydrosilyl groups is less than 2, curing is often slow and poor curing is often caused. Further, when the number of hydrosilyl groups exceeds 40, the stability of the curing agent as component (B) is deteriorated, the reactivity of the hydrosilyl groups is lowered, and unreacted hydrosilyl groups remain in the cured product. Cause voids and cracks.
[0026]
There is no restriction | limiting in particular about the hydrosilylation catalyst which is (C) component of this invention, Arbitrary things can be used.
[0027]
For example, solid platinum supported on a carrier such as chloroplatinic acid, platinum alone, alumina, silica, carbon black;
Platinum-vinylsiloxane complex {eg, Pt _n (ViMe ₂ SiOSiMe ₂ Vi) n, Pt [(MeViSiO) ₄ ] _m };
Platinum-phosphine complexes {eg, Pt (PPh ₃ ) ₄ , Pt (PBu ₃ ) ₄ };
Platinum-phosphite complex {eg, Pt [P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄
(Wherein Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, Ph represents a phenyl group, and n and m represent integers), Pt (acac) ₂ , and Ashby et al., US Pat. No. 3,159,601. And the platinum-hydrocarbon complexes described in US Pat. No. 3,159,662 and the platinum alcohol catalysts described in US Pat. No. 3,220,972 to Lamoreaux et al.
[0028]
Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , RhCl ₃ , Rh / Al ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl _2. , TiCl ₄ , and the like. These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-olefin complex, platinum-vinylsiloxane complex, Pt (acac) _{2 and the} like are preferable. Although there is no restriction | limiting in particular as a catalyst amount, It is good to use in the range of 10 ^{< -1} > ^-10 <^-8> mol with respect to ¹ mol of alkenyl groups in (A) component. It is preferable to use in the range of 10 ⁻² to 10 ⁻⁶ mol. The hydrosilylation catalysts are generally expensive and corrosive, also is better does not use 10 ^-1 mol or more because if the cured product generate a large amount of hydrogen gas resulting in foaming.
[0029]
The α-olefin having 6 to 20 carbon atoms which is the component (D) of the present invention lowers the viscosity of the composition before curing, and at the time of the curing reaction, the Si—H group and hydrosilyl of the curing agent which is the component (B). It binds by the chemical reaction and is eventually taken into the structure .
[0030]
In addition, when a low boiling point compound that can be volatilized during curing and curing is used as the component (D), it may cause a change in shape before and after curing or adversely affect the environment due to volatiles. It is particularly preferably on an 8 or more.
[0031]
Also, when using a compound having at least two hydrosilylatable alkenyl group or alkynyl group in the molecular addition to the above effects, functional groups of the crosslinking points by reacting components hydrosilylation (B) Can earn. In this case, when a large amount of the compound having at least two hydrosilylatable alkenyl group or alkynyl group in the molecular, the tensile modulus increases of the cured product, since becomes stiff and brittle, such that optimum The amount is relatively small.
[0032]
In addition, when an α-olefin having 6 to 20 carbon atoms and a compound having at least two alkenyl groups or alkynyl groups capable of hydrosilylation in the molecule are used in combination, the viscosity of the composition before curing is lowered, and the crosslinking point is reduced. Since these can be earned, these combinations are preferred.
[0034]
The amount of component (D) added is not particularly limited as long as it does not interfere with the formation of a three-dimensional crosslinked structure by hydrosilylation reaction between the isobutylene polymer as component (A) and the curing agent as component (B). There is no limit. That is, when the addition amount of the component (D) becomes excessive, the Si—H group of the component (B) is consumed by the hydrosilylation reaction with the unsaturated group of the component (D), and depends on the component (A). The formation of a three-dimensional crosslinked structure may be insufficient.
[0035]
(D) Ingredient 0.1-100 parts by weight per 100 parts by weight of the polymer of component (A), preferably 0.5 to 70 parts by weight, particularly preferably used 1 to 50 parts by weight.
[0036]
Carbon black which is the component (E) of the present invention is used for coloring the curable composition for a light-emitting display body sealing material black. In the case of using a curable composition as a sealing material for a light-emitting display body, it is preferable that the sealing material as a base is black in order to make the light emission of the light-emitting element stand out and clearly show. Therefore, it is necessary to color the curable composition for a light-emitting display body sealing material black, and carbon black is added as the component (E). The component (E) is not particularly limited as long as it is a general carbon black used for rubber additives, inks, paints, resin colorants, toners and the like.
[0037]
The amount of component (E) added is not particularly limited as long as the purpose of coloring can be achieved, but it does not significantly increase the viscosity of the curable resin composition before curing or does not significantly impair the curability. It is preferable to use 0.1 to 30 parts by weight, preferably 0.2 to 10 parts by weight, particularly 0.5 to 5 parts by weight, based on 100 parts by weight of the polymer of component (A).
[0038]
In the present invention, a matting agent can be used as the component (F) for the purpose of matting the surface of the cured product. The matting agent is not particularly limited as long as it is an additive that reduces the linear light reflectance on the surface of the cured product, and examples thereof include organic or inorganic fine particles.
[0039]
Specific examples of the component (F) include urethane fine particles, acrylic resin fine particles, methacrylic resin fine particles, styrene resin fine particles, polyolefin resin fine particles, polyvinyl chloride resin fine particles, methacryl-butadiene-styrene resin fine particles, Examples thereof include aluminum stearate, magnesium carbonate, polyethylene wax, finely divided silicic acid (silica), silica alumina particles and the like.
[0040]
The particle size of the component (F) is not particularly limited as long as the object of matting can be achieved, but is preferably 0.1 μm to 100 μm, more preferably 1 μm to 50 μm. The amount of the component (F) is not particularly limited as long as the above purpose can be achieved, but it is preferable to use it in a range that significantly increases the viscosity before curing of the curable resin composition or does not significantly inhibit the curability, It is preferable to use 0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight, particularly 0.5 to 10 parts by weight based on 100 parts by weight of the polymer of component (A).
[0041]
In the present invention, the matte surface may be formed by physically scratching the surface with sandpaper or the like after the curable composition is cured without using a matting agent.
[0042]
In the curable composition of the present invention, a storage stability improving agent can be used for the purpose of improving storage stability. This storage stability improver is a stabilizer that is generally known as a storage stability improver for the component (B) of the present invention, and is not particularly limited as long as it achieves the intended purpose. is not.
[0043]
Specifically, a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin compound, an organic peroxide, or the like can be preferably used. More specifically, 2-benzothiazolyl sulfide, benzothiazol, thiazole, dimethylacetylene dicarboxylate, diethylacetylene dicarboxylate, BHT, butylhydroxyanisole, vitamin E, 2 -(4-morphodinyldithio) benzothiazol, 3-methyl-1-butene-3-ol, acetylenically unsaturated group-containing organosiloxane, acetylene alcohol, 3-methyl-1-butyl-3 -All, diallyl fumarate, diallyl maleate, diethyl fumarate, diethyl maleate, dimethyl maleate, 2-pentenenitrile, 2,3-dichloropropene, etc. In this respect, thiazole, benzothiazole, and dimethyl maleate are preferable. But it is not limited to.
[0044]
In addition, an antioxidant, an ultraviolet absorber, a pigment, a surfactant and the like can be appropriately added to the curable composition of the present invention. In their use, the impact on the hydrosilylation reaction must be considered.
[0045]
Moreover, the adhesion imparting agent can be added to the composition of the present invention for the purpose of imparting adhesiveness. Examples of the adhesion imparting agent include various silane coupling agents and epoxy resins. In particular, a silane coupling agent having a functional group such as an epoxy group, a methacryloyl group, or a vinyl group has a small effect on curability and has a great effect on expression of adhesiveness and is easy to use. However, the silane coupling agent that can be used is not limited to these. These reaction catalysts can be added in combination with a silane coupling agent or an epoxy resin.
[0046]
In preparing the curable composition of the present invention, various commonly used mixing devices can be used. In using the composition thus obtained, after defoaming using various defoaming apparatuses, it may be applied to various processing methods such as casting, potting and coating.
[0047]
Next, the manufacturing method of the light emission display body (LED panel) of this invention is demonstrated. However, in the present invention, a large number of light emitting elements are arranged on a wiring board, and this is mounted on a panel having an arbitrary shape. In the light emitting display body to be formed, only the light emitting portion of the light emitting element is exposed and the other portions emit light. What is necessary is just to seal with the curable composition for display body sealing materials, and it is not limited to the following examples.
[0048]
On the wiring board, (1) LEDs are regularly arranged at regular intervals, and (2) the board is arranged to form a light emitting display panel. (3) Insert and fix the LED light-emitting portion on the side of the opening of the box-shaped molded body in a resin-shaped box-shaped molded body having an opening. (4) A wiring for energizing the LED disposed on the substrate is taken out from the back of the opening. (5) Pour the curable composition for a light-emitting display body sealing material so as to cover all the openings of the box-shaped molded body and expose only the light-emitting part of the LED, and (6) heat cure. A light-emitting display panel is manufactured.
[0049]
【Example】
EXAMPLES Next, although an Example is given and this invention is clarified further, this invention is not limited at all by an Example.
(Example 1)
As the component (A), a compound A (analytical values shown in Table 1) having the following structure synthesized by the method described in JP-A-8-134220 was used.
[0050]
[Chemical 3]

[0051]
[Table 1]

First, for 100 parts by weight of component (A), 35 parts by weight of octadecene (Linearene 18 made by Idemitsu Petrochemical) and 20 parts by weight of bisphenol A diallyl ether (made by Mitsui Chemicals) as component (D), One part by weight of carbon black (MA600 manufactured by Mitsubishi Chemical Corporation) and 1 part by weight of MARK AO-50 (manufactured by Asahi Denka) as an antioxidant were mixed and kneaded three times with a roll. Next, compound B as component (B) having the following structure is added to this mixture.
[0052]
[Formula 4]

Was mixed with 60 parts by weight per 100 parts by weight of component (A). Further, as component (C), bis (1,3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum complex catalyst (17.9 × 10 ⁻⁵ mmol / μl, xylene solution) is replaced with platinum ( 5 × 10 ⁻⁴ equivalents with respect to the number of moles of the alkenyl groups in the components A) and (D), and 3 mole equivalents of dimethyl maleate as a storage stability improver with respect to platinum were weighed and uniformly mixed. The composition was poured into a 5 cm × 5 cm mold and cured at a temperature of 80 ° C. for 30 minutes under a pressure of about 1 MPa. The water absorption of the obtained cured product was measured from the change in weight before and after being left for 24 hours in a pressure cooker (121 ° C.-2 atm).
(Example 2)
A cured product with the same composition except that 10 parts of fine powdered silicic acid (Mizukasil P-526, manufactured by Mizusawa Chemical Co., Ltd.) is added to 100 parts by weight of the component (A) in the composition of Example 1. The same evaluation as in Example 1 was performed. Furthermore, in Example 2, the composition was applied on glass, cured at a temperature of 80 ° C. for 30 minutes, and the gloss at 60 ° was measured using a gloss meter.
(Comparative Example 1)
Using a commercially available silicone resin (TSE3251, manufactured by Toshiba Silicone), a molded body was prepared and applied onto glass in the same manner as in Example 1, and the same evaluation as in Examples 1 and 2 was performed.
[0053]
[Table 2]

From the result of Table 2, the curable composition for light emitting display body sealing material in this invention has a low water absorption, and can suppress the penetration | invasion of the water | moisture content inside a board | substrate by moisture and a water | moisture content. Further, a matting effect was obtained by adding a matting agent.
[0054]
【The invention's effect】
The curable composition for a light-emitting display body sealing material obtained by the present invention is a composition having a low water absorption rate and excellent moisture resistance. Moreover, matting was also possible by adding a matting agent. Accordingly, as a curable composition for a light emitting display body sealing material, a light emitting portion of a light emitting element is provided in a light emitting display body in which a large number of light emitting elements are disposed on a wiring board and mounted on a panel of an arbitrary shape. By using it for a light-emitting display that is manufactured by exposing only the other part and sealing the other part, very excellent reliability can be obtained.
[0055]
Furthermore, according to the present invention, a method for manufacturing such a light-emitting display body can also be provided.

Claims (7)

The curable composition for light emitting display body sealing materials which uses the following component as an essential component.
(A) Isobutylene polymer containing at least one hydrosilylation-reactive alkenyl group in the molecule (B) Curing agent containing at least two hydrosilyl groups in the molecule (C) Hydrosilylation catalyst (D) Carbon Α-olefin (E) carbon black of 6 to 20 The light-emitting display body according to claim 1, wherein a light-emitting portion of the light-emitting element is exposed in a light-emitting display body formed by mounting a plurality of light-emitting elements disposed on a wiring board on a panel. Curable composition for sealing materials. The curable composition for a light-emitting display member sealing material according to claim 1, wherein an alkenyl group capable of hydrosilylation in the polymer of component (A) is contained at the end of the polymer. The curable composition for a light-emitting display element sealing material according to any one of claims 1 to 3 , wherein the total amount of repeating units derived from isobutylene in the polymer of component (A) is 50% by weight or more. The curable composition for sealing materials for light-emitting display bodies according to any one of claims 1 to 4 , wherein the curing agent of component (B) is an organohydrogenpolysiloxane containing at least two hydrosilyl groups in the molecule . A matting agent is added as (F) component, The curable composition for light emitting display body sealing materials in any one of Claims 1-5 characterized by the above-mentioned. The manufacturing method of the light emission display body characterized by using the curable composition for light emission display body sealing materials which uses the following component as an essential component.
(A) Isobutylene polymer containing at least one hydrosilylation-reactive alkenyl group in the molecule (B) Curing agent containing at least two hydrosilyl groups in the molecule (C) Hydrosilylation catalyst (D) Carbon Α-olefin (E) carbon black of 6 to 20