JP2008069302A - Photocurable sealant composition and component with sealing layer - Google Patents
Photocurable sealant composition and component with sealing layer Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
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- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
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- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09K2200/0625—Polyacrylic esters or derivatives thereof
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- C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
- C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09K2200/0632—Polystyrenes
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Abstract
Description
本発明は、光硬化性のシール剤組成物、又はこの光硬化性シール剤組成物を使用したシール層、特にハードディスクドライブをはじめとする電子回路素子や電子部品を内在した電子部品ケースのシール技術に関するものである。 The present invention relates to a photocurable sealant composition, or a seal layer using this photocurable sealant composition, in particular, a sealing technique for an electronic component case containing an electronic circuit element or electronic component such as a hard disk drive. It is about.
ハードディスクドライブをはじめとする電子回路素子や電子部品を内在した電子部品ケースにおいては塵など侵入を防ぐため封止用のシール材料が使用されている。シール材料としてはゴムのシートを打ち抜いて接着する方法などが採られてきたが、量産性が低くまた設計変更には新規の金型が必要となるため設計の自由度が低いものであった。 In an electronic component case including an electronic circuit element and an electronic component such as a hard disk drive, a sealing material for sealing is used to prevent entry of dust and the like. As a sealing material, a method of punching and bonding a rubber sheet has been adopted, but the mass productivity is low, and a new mold is required to change the design, so the degree of freedom in design is low.
また、近年では電子部品の小型化が進み、そのため構成部材の一体化や複合化が必要となっている。加えて信頼性の向上のためより高度な耐透湿性などのシール機能の向上が求められるようになってきている。これらの要求を満たすため、従来からあるゴム製パッキンに替え、部材上でシール剤組成物を硬化させてシール層を形成するという封止方法（ＣＩＰＧ）がとられるようになってきている。 In recent years, electronic components have been miniaturized, and therefore, it has become necessary to integrate and combine components. In addition, in order to improve reliability, improvements in sealing functions such as higher moisture permeability have been demanded. In order to satisfy these requirements, a sealing method (CIPG) in which a sealing layer is formed by curing a sealing agent composition on a member instead of a conventional rubber packing has been adopted.
封止方法として一般に、封止する部材間に液状シール剤を狭持したのち、適当な方法でシール剤を硬化させるという方法（ＦＩＰＧ）が知られている。ハードディスクドライブをはじめとする電子機器部材のシールにおいてＦＩＰＧを用いると、シール剤の硬化時に発生する副生物や未反応物ガス等がシールした部材の内部に滞留し、これが電子回路素子や電子部品に悪影響を及ぼすことがある。そのため、電子機器部材のシールにおいてはＦＩＰＧよりもＣＩＰＧの方が作業性、信頼性の点から好ましい。また、シール剤の硬化方法としては、熱や光などのエネルギーを付与する方法が知られているが、電子回路素子や電子部品等に及ぼす影響が少なく、生産性に優れ、かつ硬化時にシール剤が形状を保持しやすい方法として光硬化が好ましい。 As a sealing method, there is generally known a method (FIPG) in which a liquid sealing agent is held between members to be sealed and then the sealing agent is cured by an appropriate method. When FIPG is used to seal electronic device members such as hard disk drives, by-products and unreacted gases generated during the curing of the sealant stay inside the sealed member, and this is retained in electronic circuit elements and electronic components. May have adverse effects. Therefore, CIPG is more preferable than FIPG in terms of workability and reliability in sealing electronic device members. Further, as a method for curing the sealing agent, a method of imparting energy such as heat or light is known, but it has little influence on electronic circuit elements and electronic components, has excellent productivity, and the sealing agent at the time of curing. However, photocuring is preferable as a method of easily maintaining the shape.
従来よりある光硬化性シール剤組成物として、不飽和ポリエステル樹脂やエポキシ（メタ）アクリレート、ウレタン（メタ）アクリレートなどのアクリル系樹脂に光重合開始剤を添加したものや、エポキシ樹脂に光重合開始剤を添加したものが用いられている。特にウレタン（メタ）アクリレートを使用したものは硬化物に柔軟性を付与しやすいため、光硬化性シール剤組成物として使用することが提案されている（特許文献１）。ウレタン（メタ）アクリレートを使用した光硬化性シール剤組成物は、量産性、設計の自由度、硬化物の伸び率などに優れており、防塵を目的とするシール材料としては優れたものである。一方で、耐透湿性は十分に高いものではなく、電子部品ケースにおいて優れた耐湿シール機能を実現することができなかった。 Conventional photo-curable sealant compositions include acrylic resins such as unsaturated polyester resins, epoxy (meth) acrylates and urethane (meth) acrylates, and photopolymerization starts on epoxy resins. What added the agent is used. In particular, those using urethane (meth) acrylate are prone to be used as a photo-curable sealing agent composition because it is easy to impart flexibility to the cured product (Patent Document 1). The photo-curable sealant composition using urethane (meth) acrylate is excellent in mass productivity, freedom of design, elongation of cured product, etc., and is excellent as a sealing material for the purpose of dust prevention. . On the other hand, the moisture permeability resistance is not sufficiently high, and an excellent moisture-resistant sealing function cannot be realized in the electronic component case.
耐透湿性の高い光硬化性シール剤組成物としては、メタクリロイル変性液状ポリイソプレンおよびアクリル酸エステルモノマーなどを使用した組成物が提案されている（特許文献２）。しかしながらこの光硬化性シール剤組成物は、可撓性付与成分であるブロック共重合体を使用しておらず、またメタクリロイル変性液状ポリイソプレンは末端２官能性でないため、硬化物は熱が加わる環境において硬くなる傾向がある。そのため衝撃や温度サイクルによる部材の動きに追従できなくなり、信頼性の高いシール機能を実現することができなかった。 As a photocurable sealant composition having high moisture resistance, a composition using methacryloyl-modified liquid polyisoprene and an acrylate monomer has been proposed (Patent Document 2). However, this photo-curable sealant composition does not use a block copolymer that is a flexibility-imparting component, and the methacryloyl-modified liquid polyisoprene is not difunctional at the terminal, so that the cured product is an environment where heat is applied. Tend to be stiff. For this reason, it becomes impossible to follow the movement of the member due to the impact or temperature cycle, and a highly reliable sealing function cannot be realized.
また、耐透湿性に優れた光硬化性シール剤組成物として、イソブチレンブロックとそれ以外のブロックの共重合体を主成分とするシール材用組成物（特許文献３）、ガスケット材料（特許文献４）などが提案されている。これらはシール層を形成するために、ロールや押出機、射出成形機などにより成形したのち、適用部材に貼り付けるという工程が必要であり、量産性および設計の自由度の点から問題があった。 Moreover, as a photocurable sealing agent composition excellent in moisture permeation resistance, a composition for a sealing material (Patent Document 3) and a gasket material (Patent Document 4) mainly composed of a copolymer of an isobutylene block and other blocks. ) Etc. have been proposed. In order to form a seal layer, these require a process of being attached to an applicable member after being molded by a roll, an extruder, an injection molding machine, etc., which has problems in terms of mass productivity and design freedom. .
さらに、スチレン−イソブチレン−スチレンブロック共重合体と炭素数１８〜２５の鎖状脂肪族単官能（メタ）アクリレート等を使用した光硬化性シール剤組成物も提案されている（特許文献５）。しかしながら、（メタ）アクリレートが単官能のみで、かつその鎖状脂肪族部分の炭素鎖が斯くのごとく長くなると、硬化したときに緻密なネットワークが形成されにくく、弾性的要素を向上させることができない。その結果、部材上でシール剤組成物を硬化させてシール層を形成するという用途（ＣＩＰＧ）には使用できなかった。
本発明の目的は、前述の課題を解決し、すなわち、耐透湿性が高く、部材上にシール剤組成物を塗布し光照射することによりＣＩＰＧシール層を形成できるため量産性および設計の自由度に優れ、シール層は部材の動きに追従できるため信頼性が高い光硬化性シール剤組成物およびシール層付き部材を提供することである。 The object of the present invention is to solve the above-mentioned problems, that is, high moisture permeability, and a CIPG seal layer can be formed by applying a sealant composition on a member and irradiating it with light. It is excellent in that the seal layer can follow the movement of the member, so that it provides a highly reliable photocurable sealant composition and a member with a seal layer.
本発明者は、前述の課題を解決すべく鋭意検討した結果、以下の組成を持つ光硬化性シール剤組成物およびこの組成物を部材上に塗布、硬化させることによって得た、シール層付き部材によってこれを実現できることを見いだした。すなわち、
（Ａ）主鎖の炭素数が３〜１５であり、分岐鎖を有してもよい脂肪族鎖状炭化水素の両末端に（メタ）アクリロイル基を有する一群の化合物から選ばれる、単独又は複数の２官能（メタ）アクリレート
（Ｂ）分岐鎖を有してもよい炭素数６〜２０の鎖状アルキル骨格の片末端に（メタ）アクリロイル基を有する一群の化合物から選ばれる、単独又は複数の単官能アルキル（メタ）アクリレート
（Ｃ）スチレン−イソブチレン−スチレンブロック共重合体
（Ｄ）光重合開始剤
（Ｅ）シリカ粉
を含む光硬化性シール剤組成物、およびこの組成物を部材上に塗布し光を照射することにより得られるシール層付き部材である。
As a result of intensive studies to solve the above-mentioned problems, the present inventor has obtained a photocurable sealing agent composition having the following composition and a member with a seal layer obtained by applying and curing the composition on the member. I found out that this can be achieved. That is,
(A) The main chain has 3 to 15 carbon atoms, and may be selected from a group of compounds having a (meth) acryloyl group at both ends of an aliphatic chain hydrocarbon which may have a branched chain. The bifunctional (meth) acrylate (B) may have a branched chain, and may be selected from a group of compounds having a (meth) acryloyl group at one end of a chain alkyl skeleton having 6 to 20 carbon atoms. Monofunctional alkyl (meth) acrylate (C) Styrene-isobutylene-styrene block copolymer (D) Photopolymerization initiator (E) Photocurable sealant composition containing silica powder, and coating the composition on a member It is a member with a seal layer obtained by irradiating with shining light.
本発明の光硬化性シール剤組成物は、ハードディスクドライブをはじめとする電子回路素子や電子部品を内在した電子部品ケース等のシールにおいて、部材上でシール剤組成物を硬化させてシール層を形成するという封止方法をとることにより量産性および設計の自由度が高く、また優れた弾性的要素を有することから部材の動きに対する追従性が良好で、特にＣＩＰＧ用途に適しており、そのため発生するアウトガスの問題も解決することができ、さらに耐透湿性に優れたシール層を形成することが可能である。 The photocurable sealant composition of the present invention forms a seal layer by curing a sealant composition on a member in a seal of an electronic circuit element including a hard disk drive or an electronic component case containing an electronic component. By adopting the sealing method, the mass productivity and the degree of freedom of design are high, and since it has an excellent elastic element, the followability to the movement of the member is good, and it is particularly suitable for CIPG use, and thus occurs. The problem of outgas can be solved, and a seal layer having excellent moisture resistance can be formed.
以下、本発明の光硬化性シール剤組成物を詳細に説明する。本発明の光硬化性シール剤組成物は、（Ａ）２官能（メタ）アクリレート及び（Ｂ）単官能アルキル（メタ）アクリレートが、光と反応しラジカルを発生する（Ｄ）光重合開始剤により重合する反応を基本とする。 Hereinafter, the photocurable sealing agent composition of the present invention will be described in detail. The photo-curable sealant composition of the present invention comprises (A) a bifunctional (meth) acrylate and (B) a monofunctional alkyl (meth) acrylate that reacts with light to generate radicals. Based on the polymerization reaction.
本発明（Ａ）成分の２官能（メタ）アクリレートは、光硬化性シール剤組成物の接着強度および耐熱性を高める目的で使用される。なお、２官能とは反応に寄与する（メタ）アクリロイル基を分子中に２個有する化合物のことである。 The bifunctional (meth) acrylate of the component (A) of the present invention is used for the purpose of increasing the adhesive strength and heat resistance of the photocurable sealing agent composition. Bifunctional is a compound having two (meth) acryloyl groups contributing to the reaction in the molecule.
ここで本発明の（Ａ）成分について説明する。（Ａ）成分の２官能（メタ）アクリレートは、主鎖の炭素数が３〜１５の脂肪族鎖状炭化水素であれば特に限定されず、分岐鎖を有してもよい骨格を持つ２官能（メタ）アクリレートである。ここで、２官能（メタ）アクリレートを（メタ）アクリル酸と２価アルコールのエステル化物と考えたとき、その２価アルコールは主鎖骨格が炭素数が３〜１５である直鎖状の飽和あるいは不飽和な脂肪族炭化水素であり、その炭化水素鎖中に分岐鎖を有していてもよく、かつその炭化水素鎖の両末端に水酸基を有するものである。具体的な上述の（Ａ）２官能（メタ）アクリレートとして、１，３−ブタンジオールジ（メタ）アクリレート、２−エチル−２−ブチルプロパンジオ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、ネオペンチルグリコールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、３−メチル−１，５−ペンタンジオールジ（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、２，４−ジエチル−１，５−ペンタンジオールジ（メタ）アクリレート、２−メチル−１，８−オクタンジオールジ（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、２−エチル−２−ブチルプロパンジオールジ（メタ）アクリレート等が挙げられ、これらから単独又は複数種類を選び使用することができる。これらの２官能（メタ）アクリレートは、硬化物の接着強度及び耐熱性を損なわないためには、主鎖炭化水素の炭素数は３〜１５である必要がある。また、その添加量は０．ｌ〜２０重量％であることが好ましく、さらには０．５〜１０重量％が好ましい。 Here, the component (A) of the present invention will be described. The bifunctional (meth) acrylate as the component (A) is not particularly limited as long as it is an aliphatic chain hydrocarbon having 3 to 15 carbon atoms in the main chain, and is bifunctional having a skeleton that may have a branched chain. (Meth) acrylate. Here, when the bifunctional (meth) acrylate is considered to be an esterified product of (meth) acrylic acid and a dihydric alcohol, the dihydric alcohol is a linear saturated or main chain skeleton having 3 to 15 carbon atoms. It is an unsaturated aliphatic hydrocarbon, which may have a branched chain in the hydrocarbon chain, and has hydroxyl groups at both ends of the hydrocarbon chain. Specific examples of the above-mentioned (A) bifunctional (meth) acrylate include 1,3-butanediol di (meth) acrylate, 2-ethyl-2-butylpropanediol diacrylate, and 1,4-butanediol di (meth). Acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate 2,4-diethyl-1,5-pentanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2-ethyl -2-butylpropanediol di (meth) acrylate, etc., and from these alone or It is possible to select and use several types. In order for these bifunctional (meth) acrylates not to impair the adhesive strength and heat resistance of the cured product, the main chain hydrocarbons must have 3 to 15 carbon atoms. Moreover, the addition amount is 0. It is preferably 1 to 20% by weight, more preferably 0.5 to 10% by weight.
本発明の（Ｂ）単官能アルキル（メタ）アクリレートは、光硬化性シール剤組成物の柔軟性及び硬化性を高める目的で使用される。具体的には、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、イソアミル（メタ）アクリレート、イソオクチル（メタ）アクリレート、イソノニル（メタ）アクリレート、イソデシル（メタ）アクリレート、トリデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、イソミリスチル（メタ）アクリレート、セチル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレートなどが挙げられる。これらは、硬化物の柔軟性が目的に合うよう、１種類又は複数種類を合わせて使用することができる。 The (B) monofunctional alkyl (meth) acrylate of the present invention is used for the purpose of enhancing the flexibility and curability of the photocurable sealant composition. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isoamyl (meth) acrylate , Isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, Examples include isostearyl (meth) acrylate. These can be used singly or in combination, so that the flexibility of the cured product meets the purpose.
ここで、単官能アルキル（メタ）アクリレートとは、（メタ）アクリル酸と直鎖アルキル骨格を持った１価のアルコールとのエステル化物であり、その１価アルコールは直鎖アルキル骨格中に分岐鎖を有していてもよい構造である。 Here, the monofunctional alkyl (meth) acrylate is an esterified product of (meth) acrylic acid and a monohydric alcohol having a linear alkyl skeleton, and the monohydric alcohol is branched in the linear alkyl skeleton. It is the structure which may have.
なお、（Ｂ）成分の上記アルキル基の炭素数が小さくなりすぎると、硬化物の柔軟性が低下したり、表面の粘着性が増加するなどしてシール剤としての使用が困難となり、炭素数が大きくなりすぎると硬化性が悪くなり生産性が低下する。硬化物に適度な柔軟性および硬化性を与えるために、炭素数６〜２０のアルキル基を持つ単官能（メタ）アクリレートが好ましく、さらに炭素数８〜１８のものがより好ましい。また、その添加量は４０〜８０重量％であることが好ましく、さらには５０〜７０重量％が好ましい。添加量が４０重量％以下であると硬化物が硬くなり過ぎ、８０重量％以上であると高温環境下での使用時に軟らかくなり過ぎ、シール性が低下してしまう。 In addition, when carbon number of the said alkyl group of (B) component becomes small too much, the softness | flexibility of hardened | cured material will fall or the adhesiveness of a surface will increase and it will become difficult to use as a sealing agent, and carbon number If the value is too large, the curability is deteriorated and the productivity is lowered. In order to give the cured product appropriate flexibility and curability, monofunctional (meth) acrylates having an alkyl group having 6 to 20 carbon atoms are preferable, and those having 8 to 18 carbon atoms are more preferable. Moreover, it is preferable that the addition amount is 40 to 80 weight%, Furthermore, 50 to 70 weight% is preferable. When the addition amount is 40% by weight or less, the cured product becomes too hard, and when it is 80% by weight or more, the cured product becomes too soft when used in a high temperature environment, and the sealing performance is deteriorated.
本発明の（Ｃ）スチレン−イソブチレンブロック共重合体は、光硬化性シール剤組成物に耐透湿性と可撓性を与える目的で使用される。（Ｃ）成分はスチレン単量体からなるポリスチレンブロックとイソブチレン単量体からなるポリイソブチレンブロックをもったブロック共重合体であればよいが、トリブロック構造のスチレン−イソブチレン−スチレントリブロック共重合体がより好ましい。本発明においては、該重合体のスチレンブロック含量が１０〜４０重量％であるものが好ましいが、より好ましくは１５〜３５重量％のものである。（Ｃ）成分の添加量は１０〜５０重量％であることが好ましく、さらには２０〜４０重量％が好ましい。添加量が１０重量％未満であると、組成物に十分な耐透湿性を付与することができず、５０重量％を超えると、（Ａ）及び（Ｂ）成分中に十分に相溶あるいは分散させることができない。なおトリブロック共重合体の市販品としては、ＳＩＢＳＴＡＲ０７２Ｔ、ＳＩＢＳＴＡＲ１０２Ｔ（株式会社カネカ製）などがある。 The (C) styrene-isobutylene block copolymer of the present invention is used for the purpose of imparting moisture resistance and flexibility to the photocurable sealant composition. The component (C) may be a block copolymer having a polystyrene block composed of a styrene monomer and a polyisobutylene block composed of an isobutylene monomer, but a styrene-isobutylene-styrene triblock copolymer having a triblock structure. Is more preferable. In the present invention, the polymer preferably has a styrene block content of 10 to 40% by weight, more preferably 15 to 35% by weight. The amount of component (C) added is preferably 10 to 50% by weight, and more preferably 20 to 40% by weight. If the addition amount is less than 10% by weight, sufficient moisture permeation resistance cannot be imparted to the composition, and if it exceeds 50% by weight, it is sufficiently compatible or dispersed in the components (A) and (B). I can't let you. Examples of commercially available triblock copolymers include SIBSTAR072T and SIBSTAR102T (manufactured by Kaneka Corporation).
上述の（Ａ）２官能（メタ）アクリレート、（Ｂ）単官能アルキル（メタ）アクリレート及び（Ｃ）スチレン−イソブチレンブロック共重合体を組み合わせることにより、光硬化性シール剤組成物の硬化物は優れた弾性的要素を有することができ、これによりＣＩＰＧ用途における高いシール性を発現させられる。なお、それぞれの配合量は上記に記載した量から大きく外れると、必要とされる弾性的要素を得ることができない。 By combining the above-mentioned (A) bifunctional (meth) acrylate, (B) monofunctional alkyl (meth) acrylate, and (C) styrene-isobutylene block copolymer, the cured product of the photocurable sealant composition is excellent. It is possible to have a high elastic property in CIPG applications. In addition, when each compounding quantity remove | deviates greatly from the quantity described above, the required elastic element cannot be obtained.
本発明の（Ｄ）光重合開始剤は、光硬化性シール剤組成物を硬化させる目的で使用される。（Ｄ）成分は光照射によってラジカルを発生させる開始剤であれば特に限定されず、公知のものを使用することができる。例えば、ジメトキシアセトフェノン、１−ヒドロキシシクロヘキシルフェニルケトン、ジエトキシアセトフェノン、アセトフェノン、プロピオフェノン、ベンゾフェノン、キサントール、フルオレイン、ベンズアルデヒド、アンスラキノン、トリフェニルアミン、２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン、カルバゾール、２−ヒドロキシ−２−メチルフェニルプロパン−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、２−ヒドロキシ−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、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−１−ブタノン、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−［４−（１−メチルビニル）フェニル］プロパノンオリゴマー、３−メチルアセトフェノン、４−メチルアセトフェノン、３−ペンチルアセトフェノン、４−メトキシアセトフェノン、３−ブロモアセトフェノン、ｐ−ジアセチルベンゼン、３−メトキシベンゾフェノン、４−アリルアセトフェノン、４−メチルベンゾフェノン、４−クロロ−４−ベンジルベンゾフェノン、３−クロロキサントーン、３，９−ジクロロキサントーン、３−クロロ−８−ノニルキサントーン、ベンゾイル、ベンゾインメチルエーテル、ベンゾインブチルエーテル、ビス（４−ジメチルアミノフェニル）ケトン、ベンジルメトキシケタール、２−クロロチオキサトーンなどが挙げられる。なお、添加量は０．１〜１０重量％の範囲が好ましいが、０．１〜５重量％の範囲とすることがより好ましい。 The (D) photopolymerization initiator of the present invention is used for the purpose of curing the photocurable sealing agent composition. (D) A component will not be specifically limited if it is an initiator which generates a radical by light irradiation, A well-known thing can be used. For example, dimethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, diethoxyacetophenone, acetophenone, propiophenone, benzophenone, xanthol, fluorin, benzaldehyde, anthraquinone, triphenylamine, 2,2-dimethoxy-1,2-diphenylethane -1-one, carbazole, 2-hydroxy-2-methylphenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -1-butanone Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] Propanone oligomer, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-allylacetophenone, 4-methylbenzophenone, 4 -Chloro-4-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoyl, benzoin methyl ether, benzoin butyl ether, bis 4-dimethylaminophenyl) ketone, benzyl methoxy ketal, 2-chlorothiazol-oxa tone like. The addition amount is preferably in the range of 0.1 to 10% by weight, but more preferably in the range of 0.1 to 5% by weight.
本発明の（Ｅ）シリカ粉は、硬化前の液状組成物に揺変性を与えるために使用される。部材上で光硬化性シール剤組成物を硬化させてシール層を形成するためには、一定以上の高さで塗布し硬化するまで形状を維持する必要があるため、組成物に揺変性を付与する目的でシリカ粉を添加しこれを実現する。このシリカ粉としては、平均一次粒子径が１〜１００ｎｍ、好ましくは５〜５０ｎｍの微粉末シリカで、表面処理を施されたもの、表面処理を施されていないものどちらでも使用が可能である。表面処理が施されたものとして具体的には、四塩化硅素を酸水素焔中で加水分解させる際に、塩化チタニウム、塩化アルミニウム、塩化鉄等の塩化物を併存させたアルミナ含有シリカ、酸化チタン含有シリカ、酸化鉄含有シリカ等の微粉末シリカを挙げることができるが、特に親水性微粉末シリカの表面を疎水処理したものが好ましい。疎水性微粉末シリカは、通常の親水性微粉末シリカの表面をｎ−オクチルトリアルコキシシラン等疎水基を有するアルキル、アリール、アラルキル系シランカップリング剤、ジメチルジクロロシラン、ヘキサメチルジシラザン等のシリル化剤、末端に水酸基を有するポリジメチルシロキサン等、或いはステアリルアルコールのような高級アルコール、ステアリン酸のような高級脂肪酸で処理して得られるものである。この微粉末シリカは１種単独で或いは２種以上を混合して用いても構わない。なお、添加量は０．ｌ〜３０重量％であることが好ましく、さらには１．０〜１５重量％が好ましい。 The (E) silica powder of the present invention is used to give thixotropic properties to the liquid composition before curing. In order to cure the photo-curable sealant composition on a member to form a seal layer, it is necessary to maintain the shape until it is applied and cured at a certain height or higher. For this purpose, silica powder is added to achieve this. As the silica powder, fine powder silica having an average primary particle diameter of 1 to 100 nm, preferably 5 to 50 nm, which has been subjected to surface treatment and which has not been subjected to surface treatment, can be used. Specifically, the surface-treated alumina-containing silica, titanium oxide containing titanium chloride, aluminum chloride, iron chloride and other chlorides coexisting when hydrolyzing silicon tetrachloride in hydrogen peroxide. Examples thereof include fine powdered silica such as silica containing iron and silica containing iron oxide, and those obtained by subjecting the surface of hydrophilic fine powdered silica to hydrophobic treatment are particularly preferable. Hydrophobic fine-powder silica is a surface of normal hydrophilic fine-powder silica, such as n-octyltrialkoxysilane and other alkyl, aryl, aralkyl silane coupling agents, dimethyldichlorosilane, hexamethyldisilazane and other silyl groups. It can be obtained by treatment with an agent, polydimethylsiloxane having a hydroxyl group at the end, higher alcohol such as stearyl alcohol, and higher fatty acid such as stearic acid. The fine powder silica may be used alone or in combination of two or more. The amount added was 0. It is preferably 1 to 30% by weight, and more preferably 1.0 to 15% by weight.
シリカ粉の他の無機充填剤、例えば炭酸カルシウムやカーボンブラックでは、本発明における（Ａ）及び（Ｂ）成分とのなじみが悪く、（Ａ）及び（Ｂ）成分中に十分に分散しないため揺変性を発現することができない。なお、本発明の硬化性組成物は光照射によって硬化を実現するため、シリカ粉の使用に当たっては極度に隠蔽性の高いものを選ぶと硬化性に支障を及ぼす可能性がある。 Other inorganic fillers such as calcium carbonate and carbon black do not fit well with the components (A) and (B) in the present invention and do not sufficiently disperse in the components (A) and (B). Unable to express denaturation. In addition, since the curable composition of the present invention achieves curing by irradiation with light, if a silica powder having extremely high concealing properties is selected, the curability may be hindered.
本発明光硬化性シール剤組成物には、（Ａ）から（Ｅ）成分の他に、必要に応じて別の成分を添加することができる。添加する成分を例示すると、安定剤、着色剤、熱重合開始剤、密着付与剤、老化防止剤、分散助剤などを挙げることができる。 In addition to the components (A) to (E), other components can be added to the photocurable sealant composition of the present invention as necessary. Examples of the component to be added include a stabilizer, a colorant, a thermal polymerization initiator, an adhesion imparting agent, an antiaging agent, and a dispersion aid.
本発明光硬化性シール剤組成物の接着性を向上させるため、特に密着助剤を添加することが好ましい。密着助剤としては、シランカップリング剤、チタンカップリング剤等が適用できるが、組成物の保存安定性、相溶性等からシランカップリング剤が好ましい。具体的には、分子中にエポキシ基、（メタ）アクリル基、ビニル基、カルバメート基から選ばれる少なくとも１個の官能基と、ケイ素原子結合ヒドロキシル基を有するシランカップリング剤が好ましい。 In order to improve the adhesiveness of the photocurable sealant composition of the present invention, it is particularly preferable to add an adhesion assistant. As the adhesion assistant, a silane coupling agent, a titanium coupling agent, and the like can be applied, but a silane coupling agent is preferable from the viewpoint of storage stability and compatibility of the composition. Specifically, a silane coupling agent having at least one functional group selected from an epoxy group, a (meth) acryl group, a vinyl group, and a carbamate group in the molecule and a silicon atom-bonded hydroxyl group is preferable.
本発明の光硬化性シール剤付き部材およびシール剤付きハードディスクドライブ筐体用部材は、前記シール剤組成物を部材上に塗布した後、光照射することによって硬化させて形成される。塗布は任意の方法で行うことができ、光源には、高圧水銀ランプ、超高圧水銀ランプ、メタルハライドランプ、水銀キセノンランプ、キセノンランプ、ＬＥＤなどを使用することができる。なお、照射雰囲気温度は通常１０〜２００℃の範囲で、照射光の波長は（Ｄ）光重合開始剤の吸収波長帯である。 The photocurable sealant-attached member and sealant-attached hard disk drive housing member of the present invention are formed by applying the sealant composition onto the member and then curing it by light irradiation. The application can be performed by any method, and as a light source, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a mercury xenon lamp, a xenon lamp, an LED, or the like can be used. In addition, irradiation atmosphere temperature is the range of 10-200 degreeC normally, and the wavelength of irradiation light is an absorption wavelength band of (D) photoinitiator.
以下、本発明を実施例によって具体的に説明するが、本発明はこれらの例により限定されるものではない。なお、シール剤組成物の評価内容は硬化物の耐透湿性として水蒸気透過係数及び弾性的要素として伸び率の２項目である。水蒸気透過係数の数値は小さいほど耐透湿性に優れており、０〜２０ｇ／ｍ２・２４ｈ・ａｔｍの範囲にあることが好ましい。伸び率の数値は大きいほどシール時の追従性に優れており、９０重量％以上であることが好ましい。なお、伸び率及び水蒸気透過係数は以下の方法により測定した。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The evaluation contents of the sealant composition are two items, that is, moisture permeability of the cured product, water vapor transmission coefficient and elongation factor as an elastic element. The smaller the value of the water vapor transmission coefficient, the better the moisture permeability, and it is preferably in the range of 0 to 20 g / m 2 · 24 h · atm. The larger the numerical value of the elongation, the better the followability at the time of sealing, and it is preferably 90% by weight or more. The elongation rate and the water vapor transmission coefficient were measured by the following methods.
［伸び率］
硬化させる前の本発明光硬化性シール剤組成物を厚さ１ｍｍの均質な膜状に形成し、これに高圧水銀ランプを使用して３０００ｍＪ／ｃｍ２の光を片面ずつそれぞれ両面に照射することにより硬化させ、シート状硬化物を得た。これをＪＩＳ Ｋ ６２５１に規定された３号形ダンベルにより打ち抜き、ダンベル形状の引張試験用試験片を作成した。この試験片を用い、万能引張試験機によりＪＩＳ Ｋ ６２５１号に規定された引張試験を実施することで本発明シール剤組成物の硬化物の切断時伸び（伸び率）について測定した。なお、万能引張試験機の引張速度は毎分５００ｍｍとし、伸びた部位の測定にはＪＩＳ Ｂ ７５０３により規定されたノギス、又は同等以上の性能のノギスにより測定した。なお、伸び率の値は試験を３回実施したときの中央値を採用した。
[Growth rate]
Before curing, the photocurable sealant composition of the present invention is formed into a uniform film having a thickness of 1 mm, and a high-pressure mercury lamp is used to irradiate each side with 3000 mJ / cm 2 of light. To obtain a sheet-like cured product. This was punched out with a No. 3 type dumbbell defined in JIS K 6251 to prepare a dumbbell-shaped tensile test specimen. Using this test piece, the elongation at break (elongation) of the cured product of the sealant composition of the present invention was measured by carrying out a tensile test specified in JIS K 6251 with a universal tensile tester. The tensile speed of the universal tensile testing machine was 500 mm per minute, and the stretched part was measured with a vernier caliper defined by JIS B 7503 or a caliper with equivalent or better performance. In addition, the median value when the test was carried out three times was adopted as the elongation value.
［水蒸気透過係数］
硬化させる前の本発明光硬化性シール剤組成物を厚さ０．５ｍｍの均質な膜状に形成し、これに高圧水銀ランプを使用して３０００ｍＪ／ｃｍ２の光を片面ずつそれぞれ両面に照射することにより硬化させ、シート状硬化物を得た。このシートを１５．２ｃｍ２の円形になるよう切り抜き試験片とし、差圧式蒸気透過率測定装置（ＧＴＲ−３０ＸＡ３Ｂ、ＧＴＲテック社製）にて水蒸気透過係数の測定を実施した。
[Water vapor transmission coefficient]
Before curing, the photocurable sealant composition of the present invention is formed into a uniform film having a thickness of 0.5 mm, and a high-pressure mercury lamp is used to irradiate each side with 3000 mJ / cm 2 light. By curing, a sheet-like cured product was obtained. This sheet was cut into a 15.2 cm 2 circular cut test piece, and the water vapor transmission coefficient was measured with a differential pressure vapor transmission rate measuring device (GTR-30XA3B, manufactured by GTR Tech).
［実施例１］
（Ａ）成分として２−エチル−２−ブチルプロパンジオールジアクリレート、（Ｂ）成分としてイソノニルアクリレート、（Ｃ）成分としてトリブロック構造のスチレン−イソブチレン−スチレン共重合体（スチレン含量２３重量％：商品名ＳＩＢＳＴＡＲ ０７２Ｔ 株式会社カネカ製）、（Ｄ）成分として２−ヒドロキシ−２−メチル−１−〔４−（１−メチルビニル）フェニル〕プロパンのオリゴマー（商品名 ＥＳＡＣＵＲＥ ＫＩＰ １５０ Ｌａｍｂｅｒｔｉ社製）、（Ｅ）成分として表面無処理ヒュームドシリカ（商品名アエロジル２００ 日本アエロジル株式会社製）を用いた。（Ａ）（Ｂ）（Ｃ）（Ｄ）成分を６０℃に加温しながら撹拌して均一な液体を得た後、プラネタリーミキサーで（Ｅ）成分を混合して、シール剤組成物を得た。それぞれの配合量は表１に重量部により示した。高圧水銀ランプを用いて３０００ｍＪ／ｃｍ２の光を片面ずつそれぞれ照射して硬化物を作成し、水蒸気透過係数および伸び率を測定したところ、表１に示すようにいずれも良好な結果を得た。
[Example 1]
2-ethyl-2-butylpropanediol diacrylate as component (A), isononyl acrylate as component (B), styrene-isobutylene-styrene copolymer having a triblock structure as component (C) (styrene content 23 wt%: (Trade name SIBSTAR 072T manufactured by Kaneka Corporation), (D) component 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane oligomer (trade name: ESACURE KIP 150 Lamberti), As the component (E), surface-untreated fumed silica (trade name: Aerosil 200 manufactured by Nippon Aerosil Co., Ltd.) was used. The components (A), (B), (C), and (D) are stirred while heating to 60 ° C. to obtain a uniform liquid, and then the component (E) is mixed with a planetary mixer to obtain a sealant composition. Obtained. The amount of each compound is shown in Table 1 in parts by weight. A cured product was prepared by irradiating each side with 3000 mJ / cm 2 light using a high-pressure mercury lamp, and the water vapor transmission coefficient and the elongation were measured. As shown in Table 1, all obtained good results.
［実施例２］
（Ａ）成分として主鎖骨格の炭素数が５で側鎖を持つ２官能アクリレート（２，４−ジエチル−１，５−ペンタンジオールジアクリレート）を用いた他は、実施例１と同様の手順でシール剤組成物を得た。実施例１と同様に硬化物を作成し測定したところ、表１に示すように水蒸気透過係数および伸び率いずれも良好な結果を得た。
[Example 2]
The same procedure as in Example 1 except that a bifunctional acrylate (2,4-diethyl-1,5-pentanediol diacrylate) having a side chain of 5 carbon atoms in the main chain skeleton was used as the component (A). A sealant composition was obtained. A cured product was prepared and measured in the same manner as in Example 1. As shown in Table 1, both the water vapor transmission coefficient and the elongation were good.
［実施例３］
（Ａ）成分として主鎖骨格の炭素数が１２の２官能アクリレート（１，１２−ドデカンジオールジアクリレート）を用いた他は、実施例１と同様の手順でシール剤組成物を得た。実施例１と同様に硬化物を作成し測定したところ、表１に示すように水蒸気透過係数および伸び率いずれも良好な結果を得た。
[Example 3]
A sealant composition was obtained in the same procedure as in Example 1 except that a bifunctional acrylate having a main chain skeleton having 12 carbon atoms (1,12-dodecanediol diacrylate) was used as the component (A). A cured product was prepared and measured in the same manner as in Example 1. As shown in Table 1, both the water vapor transmission coefficient and the elongation were good.
［実施例４］
（Ｂ）成分としてイソオクチルアクリレートとイソステアリルアクリレートの混合物を用いた他は、実施例１と同様の手順でシール剤組成物を得た。実施例１と同様に硬化物を作成し測定したところ、表１に示すように水蒸気透過係数および伸び率いずれも良好な結果を得た。
[Example 4]
A sealant composition was obtained in the same procedure as in Example 1 except that a mixture of isooctyl acrylate and isostearyl acrylate was used as the component (B). A cured product was prepared and measured in the same manner as in Example 1. As shown in Table 1, both the water vapor transmission coefficient and the elongation were good.
［実施例５］
（Ｃ）成分としてトリブロック構造のスチレン−イソブチレン−スチレンブロック共重合体（スチレン含量１５重量％：ＳＩＢＳＴＡＲ １０２Ｔ 株式会社カネカ製）を用いた他は、実施例１と同様の手順でシール剤組成物を得た。実施例１と同様に硬化物を作成し測定したところ、表１に示すように水蒸気透過係数および伸び率いずれも良好な結果を得た。
[Example 5]
(C) A sealing agent composition in the same procedure as in Example 1 except that a styrene-isobutylene-styrene block copolymer having a triblock structure (styrene content 15% by weight: manufactured by SIBSTAR 102T, Kaneka Corporation) was used as the component (C). Got. A cured product was prepared and measured in the same manner as in Example 1. As shown in Table 1, both the water vapor transmission coefficient and the elongation were good.
［実施例６］
（Ｃ）成分としてジブロック構造のスチレン−イソブチレンブロック共重合体（スチレン含量２０重量％、数平均分子量約３０，０００）を用いた他は、実施例１と同様の手順でシール剤組成物を得た。実施例１と同様に硬化物を作成し測定したところ、表１に示すように水蒸気透過係数および伸び率いずれも良好な結果を得た。
[Example 6]
The sealing agent composition was prepared in the same procedure as in Example 1 except that a styrene-isobutylene block copolymer having a diblock structure (styrene content 20 wt%, number average molecular weight about 30,000) was used as component (C). Obtained. A cured product was prepared and measured in the same manner as in Example 1. As shown in Table 1, both the water vapor transmission coefficient and the elongation were good.
［比較例１］
（Ａ）成分を使用しない他は、実施例１と同様の手順でシール剤組成物を得た。実施例１と同様に硬化物を作成しようとしたが、硬化性が不十分であり硬化膜を形成することができなかったため測定できなかった。
[Comparative Example 1]
(A) The sealing agent composition was obtained in the same procedure as Example 1 except not using a component. An attempt was made to make a cured product in the same manner as in Example 1, but the measurement was not possible because the curability was insufficient and a cured film could not be formed.
［比較例２］
（Ａ）成分に代えてトリメチロールプロパントリアクリレートを用いた他は、実施例１と同様の手順でシール剤組成物を得た。実施例１と同様に硬化物を作成し測定したところ、伸び率及び水蒸気透過係数ともに満足のいくものではなかった。
[Comparative Example 2]
A sealant composition was obtained in the same procedure as in Example 1 except that trimethylolpropane triacrylate was used instead of the component (A). When a cured product was prepared and measured in the same manner as in Example 1, neither the elongation rate nor the water vapor transmission coefficient was satisfactory.
［比較例３］
（Ａ）成分に代えて１，２１‐ヘニコサンジオールジアクリレートを用いた他は、実施例１と同様の手順でシール剤組成物を得た。実施例１と同様に硬化物を作成し測定したところ、伸び率及び水蒸気透過係数ともに満足のいくものではなかった。
[Comparative Example 3]
A sealant composition was obtained in the same procedure as in Example 1 except that 1,21-henicosandiol diacrylate was used in place of the component (A). When a cured product was prepared and measured in the same manner as in Example 1, neither the elongation rate nor the water vapor transmission coefficient was satisfactory.
［比較例４］
（Ａ）成分に代えてＰＯ変性ビスフェノールＡジアクリレートを用いた他は、実施例１と同様の手順でシール剤組成物を得た。実施例１と同様に硬化物を作成し測定したところ、伸び率及び水蒸気透過係数ともに満足のいくものではなかった。
[Comparative Example 4]
A sealant composition was obtained in the same procedure as in Example 1 except that PO-modified bisphenol A diacrylate was used instead of the component (A). When a cured product was prepared and measured in the same manner as in Example 1, neither the elongation rate nor the water vapor transmission coefficient was satisfactory.
［比較例５］
（Ｂ）成分に代えてパラクミルフェノキシエチレングリコールアクリレートを用いた他は、実施例１と同様の手順でシール剤組成物を調整したところ、組成物は均一な液体とならず、シール剤を得ることができなかった。
[Comparative Example 5]
(B) A sealant composition was prepared in the same procedure as in Example 1 except that paracumylphenoxyethylene glycol acrylate was used in place of the component. As a result, the composition did not become a uniform liquid and a sealant was obtained. I couldn't.
［比較例６］
（Ｂ）成分に代えてイソボルニルアクリレートを用いた他は、実施例１と同様の手順でシール剤組成物を得た。実施例１と同様に硬化物を作成し測定したところ、硬化物が非常に硬くなってしまい、試験片を作成することができず測定できなかった。
[Comparative Example 6]
A sealant composition was obtained in the same procedure as in Example 1 except that isobornyl acrylate was used instead of the component (B). When a cured product was prepared and measured in the same manner as in Example 1, the cured product became very hard, and a test piece could not be prepared and could not be measured.
［比較例７］
（Ｂ）成分に代えてエイコサニルアクリレートを用いた他は、実施例１と同様の手順でシール剤組成物を得た。実施例１と同様に硬化物を作成し測定したところ、伸び率及び水蒸気透過係数ともに満足のいくものではなかった。
[Comparative Example 7]
A sealant composition was obtained in the same procedure as in Example 1 except that eicosanyl acrylate was used instead of the component (B). When a cured product was prepared and measured in the same manner as in Example 1, neither the elongation rate nor the water vapor transmission coefficient was satisfactory.
［比較例８］
（Ｃ）成分に代えてメタクリロイル化液状ポリイソプレン（ＵＣ−２０３ 株式会社クラレ製）を用いた他は、実施例１と同様の手順でシール剤組成物を得た。実施例１と同様に硬化物を作成し測定したところ、表１に示すように水蒸気透過係数については良好な結果を得たものの伸び率は小さく、ＣＩＰＧシール剤として使用できるものではなかった。
[Comparative Example 8]
A sealant composition was obtained in the same procedure as in Example 1 except that methacryloylated liquid polyisoprene (UC-203, manufactured by Kuraray Co., Ltd.) was used instead of the component (C). When a cured product was prepared and measured in the same manner as in Example 1, as shown in Table 1, although a good result was obtained for the water vapor transmission coefficient, the elongation was small and it was not usable as a CIPG sealant.
［比較例９］
（Ｃ）成分に代えてスチレン−エチレン／ブチレン−スチレンブロック共重合体（クレイトンＧ１７２６ クレイトンポリマー社製）を用いた他は、実施例１と同様の手順でシール剤組成物を得た。実施例１と同様に硬化物を作成し測定したところ、表１に示すように伸び率については良好な結果を得たものの、水蒸気透過係数については満足するものではなかった。
[Comparative Example 9]
A sealant composition was obtained in the same procedure as in Example 1 except that a styrene-ethylene / butylene-styrene block copolymer (Clayton G1726, manufactured by Kraton Polymer Co., Ltd.) was used instead of the component (C). When a cured product was prepared and measured in the same manner as in Example 1, good results were obtained for the elongation as shown in Table 1, but the water vapor transmission coefficient was not satisfactory.
［比較例１０］
（Ｃ）成分に代えてスチレン−エチレン／プロピレン−スチレンブロック共重合体（セプトン２０６３ 株式会社クラレ製）を用いた他は、実施例１と同様の手順でシール剤組成物を得た。実施例１と同様に硬化物を作成し測定したところ、表１に示すように伸び率については良好な結果を得たものの、水蒸気透過係数については満足するものではなかった。
[Comparative Example 10]
A sealant composition was obtained in the same procedure as in Example 1 except that a styrene-ethylene / propylene-styrene block copolymer (Septon 2063, manufactured by Kuraray Co., Ltd.) was used instead of the component (C). When a cured product was prepared and measured in the same manner as in Example 1, good results were obtained for the elongation as shown in Table 1, but the water vapor transmission coefficient was not satisfactory.
［比較例１１］
（Ｃ）成分に代えてポリウレタンアクリレート（紫光ＵＶ−３７００Ｂ 日本合成化学工業株式会社製）を用いた他は、実施例１と同様の手順でシール剤組成物を得た。実施例１と同様に硬化物を作成し測定したところ、表１に示すように、伸び率及び水蒸気透過係数ともに満足するものではなかった。
[Comparative Example 11]
(C) A sealing agent composition was obtained in the same procedure as in Example 1 except that polyurethane acrylate (purple UV-3700B manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was used instead of the component (C). When a cured product was prepared and measured in the same manner as in Example 1, as shown in Table 1, neither the elongation rate nor the water vapor transmission coefficient was satisfied.
本発明から得られた光硬化性シール剤組成物及び該シール剤付き部材は、その優れた耐透湿性及び弾性的要素から、ハードディスクなどの電子回路素子や電子部品を内在した電子部品ケースのシールをはじめとして、その他の耐透湿性を必要とする部材おいて耐透湿シール剤として有用である。 The photocurable sealant composition and the member with the sealant obtained from the present invention are sealed in an electronic component case containing an electronic circuit element such as a hard disk or an electronic component because of its excellent moisture permeability resistance and elastic element. In addition to the above, it is useful as a moisture permeable sealant in other members that require moisture resistance.
Claims (4)
（Ｂ）分岐鎖を有してもよい炭素数６〜２０の鎖状アルキル骨格の片末端に（メタ）アクリロイル基を有する一群の化合物から選ばれる、単独又は複数の単官能アルキル（メタ）アクリレート
（Ｃ）スチレン−イソブチレンブロック共重合体
（Ｄ）光重合開始剤
（Ｅ）シリカ粉
上記（Ａ）〜（Ｅ）成分を含むことを特徴とする光硬化性シール剤組成物。 (A) The main chain has 3 to 15 carbon atoms, and may be selected from a group of compounds having a (meth) acryloyl group at both ends of an aliphatic chain hydrocarbon which may have a branched chain. The bifunctional (meth) acrylate (B) may have a branched chain, and may be selected from a group of compounds having a (meth) acryloyl group at one end of a chain alkyl skeleton having 6 to 20 carbon atoms. Monofunctional alkyl (meth) acrylate (C) Styrene-isobutylene block copolymer (D) Photopolymerization initiator (E) Silica powder Photocurable sealant comprising the above components (A) to (E) Composition.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2006250723A JP2008069302A (en) | 2006-09-15 | 2006-09-15 | Photocurable sealant composition and component with sealing layer |
| TW096133752A TW200831650A (en) | 2006-09-15 | 2007-09-10 | Photocurable sealant composition and article having sealed layer |
| PCT/JP2007/068021 WO2008032851A1 (en) | 2006-09-15 | 2007-09-11 | Photocurable sealing agent composition and member with sealing layer |
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| JP2006250723A JP2008069302A (en) | 2006-09-15 | 2006-09-15 | Photocurable sealant composition and component with sealing layer |
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| JP2008069302A true JP2008069302A (en) | 2008-03-27 |
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| JP (1) | JP2008069302A (en) |
| TW (1) | TW200831650A (en) |
| WO (1) | WO2008032851A1 (en) |
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-
2006
- 2006-09-15 JP JP2006250723A patent/JP2008069302A/en active Pending
-
2007
- 2007-09-10 TW TW096133752A patent/TW200831650A/en unknown
- 2007-09-11 WO PCT/JP2007/068021 patent/WO2008032851A1/en active Application Filing
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010138290A (en) * | 2008-12-11 | 2010-06-24 | Nichiban Co Ltd | Photocurable composition, use thereof as sealing material for dye-sensitized solar cell, and dye-sensitized solar cell |
| JP2014532769A (en) * | 2011-10-21 | 2014-12-08 | テーザ・ソシエタス・ヨーロピア | Adhesives especially for the encapsulation of electronic devices |
| WO2013108731A1 (en) * | 2012-01-16 | 2013-07-25 | 味の素株式会社 | Resin composition for sealing |
| US9676978B2 (en) | 2012-01-16 | 2017-06-13 | Ajinomoto Co., Ltd. | Resin composition for sealing |
| CN104968690A (en) * | 2013-02-04 | 2015-10-07 | 株式会社普利司通 | Photocurable elastomer composition, seal material, gasket for hard disk drive, hard disk drive and device |
| JP2016135860A (en) * | 2015-01-15 | 2016-07-28 | 三菱化学株式会社 | Curable composition and encapsulating agent using the same |
| JP2018104646A (en) * | 2016-12-28 | 2018-07-05 | 日立化成株式会社 | Resin composition for forming elastic resin layer |
| US11912857B2 (en) | 2020-02-28 | 2024-02-27 | Nidec Corporation | Photocurable gasket resin composition for hard disk drive and hard disk drive |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200831650A (en) | 2008-08-01 |
| WO2008032851A1 (en) | 2008-03-20 |
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