JPH06220421A - Sealing material curable by ionizing radiation - Google Patents
Sealing material curable by ionizing radiationInfo
- Publication number
- JPH06220421A JPH06220421A JP995493A JP995493A JPH06220421A JP H06220421 A JPH06220421 A JP H06220421A JP 995493 A JP995493 A JP 995493A JP 995493 A JP995493 A JP 995493A JP H06220421 A JPH06220421 A JP H06220421A
- Authority
- JP
- Japan
- Prior art keywords
- sealing material
- acrylate
- curing
- fine powder
- oligomer
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Sealing Material Composition (AREA)
- Polymerisation Methods In General (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電離放射線硬化型シー
リング材に関する。FIELD OF THE INVENTION The present invention relates to an ionizing radiation-curable sealant.
【０００２】[0002]
【従来の技術】電離放射線硬化型シーリング材は、自動
車、電気及び建材の分野を中心に、近年広く用いられて
きており、必須成分として、不飽和二重結合を有する光
硬化性モノマー及び／又はオリゴマーを、さらに必要に
応じゴム、エラストマー、その他ポリマー、無機充填
剤、光反応開始剤、熱反応開始剤、顔料等を含有する。
上記光硬化性モノマーやオリゴマーとしては、シーリン
グ特性を向上させるために、硬化後に柔軟性を示すもの
が選ばれる。2. Description of the Related Art Ionizing radiation-curable sealing materials have been widely used in recent years, mainly in the fields of automobiles, electricity and building materials, and as an essential component, a photocurable monomer having an unsaturated double bond and / or The oligomer further contains rubber, elastomer, other polymer, inorganic filler, photoreaction initiator, thermal reaction initiator, pigment and the like, if necessary.
As the above-mentioned photo-curable monomer or oligomer, those exhibiting flexibility after curing are selected in order to improve the sealing property.
【０００３】近年、シーリング材の塗布工程が自動化さ
れ、シーリング材を先端の細いノズルから吐出させて塗
布する、いわゆるディスペンサーによる方法が汎用され
ている。この塗布法に用いるシーリング材は、チキソト
ロピー性が要求されるため、ケイ酸マグネシウム、ケイ
酸アルミニウム、ベントナイト、親水性あるいは表面を
メチルグループで覆って疎水化した二酸化ケイ素微粉
末、アスベスト、マイカ粉等の無機充填剤を配合する。In recent years, the sealing material application process has been automated, and a so-called dispenser method has been widely used in which the sealing material is discharged from a nozzle having a thin tip to apply the sealing material. Since the sealing material used in this coating method is required to have thixotropy, magnesium silicate, aluminum silicate, bentonite, silicon dioxide fine powder which is hydrophilic or has its surface covered with methyl groups to be hydrophobic, asbestos, mica powder, etc. Of the inorganic filler.
【０００４】しかしながら、無機充填剤を配合したシー
リング材は、硬化後に内部凝集力が高まるため、シーリ
ング材に要求される柔軟性が損なわれるという欠点があ
る。特に低温下でこの傾向は強く、被着体からシーリン
グ材が剥離したり、内部亀裂が生じやすくなるという欠
点があった。However, the sealing material containing the inorganic filler has a drawback that the flexibility required for the sealing material is impaired because the internal cohesive force increases after curing. This tendency is particularly strong at low temperatures, and there is a drawback that the sealing material tends to peel off from the adherend and internal cracks are likely to occur.
【０００５】また、このような無機充填剤を配合するこ
とにより生ずる悪影響を防止するために、重合後のガラ
ス転移点が低い、ｎ−ブチルアクリレート、２−エチル
ヘキシルアクリレートのような長鎖アルキルアクリレー
トを多量に配合したシーリング材が知られている。しか
しながら、このシーリング材は、硬化前には揮発性に富
み、また皮膚刺激性が強いという欠点があり、さらに硬
化後でも粘着性を有するため、表面にゴミや異物が付着
するという欠点がある。Further, in order to prevent adverse effects caused by blending such an inorganic filler, a long chain alkyl acrylate such as n-butyl acrylate or 2-ethylhexyl acrylate having a low glass transition point after polymerization is used. A sealing material containing a large amount of compound is known. However, this sealing material has drawbacks that it is rich in volatility before curing and has strong skin irritation, and has adhesiveness even after curing, so that dust and foreign matters adhere to the surface.
【０００６】また、光硬化性オリゴマーとして、ポリエ
ーテルポリオール構造、ポリエステルポリオール構造又
はポリブタジエンポリオール構造のウレタンアクリレー
トを用いたシーリング材や、シリコンゴム、ポリブタジ
エンゴム、イソプレンゴム、ブチルゴム、エチレン酢酸
ビニル共重合体等のポリマー成分を多量に配合したシー
リング材が知られている。しかしながら、これらは常温
で粘稠であるため、作業性が悪いという欠点がある。Further, as a photocurable oligomer, a sealing material using urethane acrylate having a polyether polyol structure, a polyester polyol structure or a polybutadiene polyol structure, a silicone rubber, a polybutadiene rubber, an isoprene rubber, a butyl rubber, an ethylene vinyl acetate copolymer is used. Sealing materials in which a large amount of such polymer components are blended are known. However, since they are viscous at room temperature, they have the drawback of poor workability.
【０００７】また、フタル酸ジ−２−エチルヘキシル、
アジピン酸２−エチルヘキシル、リン酸トリブチル等の
可塑剤を添加したシーリング材も知られているが、この
シーリング材は、塩ビゾル系のシーリング材と同様に、
可塑剤が表面に移行しやすいため、経時に表面が粘着性
をおびるという欠点があった。Further, di-2-ethylhexyl phthalate,
Sealing materials to which plasticizers such as 2-ethylhexyl adipate and tributyl phosphate are added are also known, but this sealing material is similar to the vinyl sol-based sealing material.
Since the plasticizer easily migrates to the surface, there is a drawback that the surface becomes tacky over time.
【０００８】[0008]
【発明が解決しようとする課題】本発明の目的は、硬化
前には適度な粘度とチキソトロピー性を有し、硬化後に
は柔軟性及び適度な硬度を示す電離放射線硬化型シーリ
ング材を提供することにある。SUMMARY OF THE INVENTION It is an object of the present invention to provide an ionizing radiation-curable sealing material which has an appropriate viscosity and thixotropy before curing and shows flexibility and an appropriate hardness after curing. It is in.
【０００９】[0009]
【課題を解決するための手段】本発明は、光硬化性モノ
マー及び／又はオリゴマー、並びにガラス転移点が−１
０℃以下の有機微粉末を含有する電離放射線硬化型シー
リング材である。The present invention provides a photocurable monomer and / or oligomer and a glass transition point of -1.
It is an ionizing radiation-curable sealant containing an organic fine powder at 0 ° C or lower.
【００１０】以下、本発明を詳細に説明する。本発明に
用いる光硬化性モノマーとしては、メチルアクリレー
ト、エチルアクリレート、ｎ−ブチルアクリレート、２
−エチルヘキシルアクリレート、イソデシルアクリレー
ト、ラウリルアクリレート、ステアリルアクリレート、
２−ヒドロキシエチルアクリレート、２−ヒドロキシプ
ロピルアクリレート、トリメチロールプロパントリアク
リレート、メトキシエチルアクリレート、ｎ−ブトキシ
エチルアクリレート、ジメチルアミノエチルアクリレー
ト、エチレングリコールアクリレート、ネオペンチルグ
リコールアクリレート、１，６−ヘキサンジオールジア
クリレート、ジエチレングリコールアクリレート、トリ
エチレンアクリレート、ジプロピレングリコールジアク
リレート、エチルカルビトールアクリレート、１，５−
ペンタンジオールジアクリレート、ペンタエリスリトー
ルアクリレート、テトラヒドロフルフリルアクリレー
ト、グリシジルアクリレート、ベンジルアクリレート、
２−ヒドロキシエチルアクリロイルホスフェート、２−
ヒドロキシ−３−フェノキシプロピルアクリレート、
α，ω−ジアクリロイルビスエチレングリコールフタレ
ート、α，ω−ジアクリロイルビスエチレングリコール
テトラヒドロフタレート等を挙げることができる。光硬
化性モノマーは、後述する光硬化性オリゴマーとして高
粘度のものを用いる場合に、シーリング材の粘度を低下
し、作業性を向上させる。光硬化性モノマーは、粘度、
毒性、硬化性、硬化後の接着性、硬度、強度、破断伸
度、ガラス転移温度等を考慮し、１種又は２種以上を選
択して使用するのが好ましい。また光硬化性モノマー
は、揮発することなく重合時に硬化物の構造の一部とな
るので、硬化後の上記物性がモノマー選択するうえで重
要な要素となる。The present invention will be described in detail below. Examples of the photocurable monomer used in the present invention include methyl acrylate, ethyl acrylate, n-butyl acrylate, and 2
-Ethylhexyl acrylate, isodecyl acrylate, lauryl acrylate, stearyl acrylate,
2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, trimethylolpropane triacrylate, methoxyethyl acrylate, n-butoxyethyl acrylate, dimethylaminoethyl acrylate, ethylene glycol acrylate, neopentyl glycol acrylate, 1,6-hexanediol diacrylate , Diethylene glycol acrylate, triethylene acrylate, dipropylene glycol diacrylate, ethyl carbitol acrylate, 1,5-
Pentanediol diacrylate, pentaerythritol acrylate, tetrahydrofurfuryl acrylate, glycidyl acrylate, benzyl acrylate,
2-hydroxyethyl acryloyl phosphate, 2-
Hydroxy-3-phenoxypropyl acrylate,
Examples thereof include α, ω-diacryloylbisethylene glycol phthalate and α, ω-diacryloylbisethylene glycol tetrahydrophthalate. The photocurable monomer lowers the viscosity of the sealing material and improves workability when a highly curable photocurable oligomer described below is used. The photocurable monomer has a viscosity,
Considering toxicity, curability, adhesiveness after curing, hardness, strength, elongation at break, glass transition temperature, etc., it is preferable to select and use one kind or two or more kinds. Further, since the photocurable monomer does not volatilize and becomes a part of the structure of the cured product at the time of polymerization, the above physical properties after curing are important factors in selecting the monomer.
【００１１】本発明に用いる光硬化性オリゴマーとして
は、エポキシアクリレート樹脂、ウレタンアクリレート
樹脂、ポリエステルアクリレート樹脂等を挙げることが
でき、中でも、ウレタンアクリレート樹脂は、硬化後の
シーリング材に柔軟性及び弾性を付与するので好まし
い。光硬化性オリゴマーは硬化物の特性を決定づけるベ
ースレジンである。光硬化性モノマー及び／又はオリゴ
マーの配合量は、２０〜９５重量％、好ましくは３０〜
９０重量％である。Examples of the photo-curable oligomer used in the present invention include epoxy acrylate resin, urethane acrylate resin, polyester acrylate resin, and the like. Among them, the urethane acrylate resin provides the sealing material after curing with flexibility and elasticity. It is preferable because it is added. The photocurable oligomer is a base resin that determines the properties of the cured product. The content of the photocurable monomer and / or oligomer is 20 to 95% by weight, preferably 30 to
90% by weight.
【００１２】本発明に用いる有機微粉末のガラス転移温
度は、−１０℃以下、好ましくは、−３０〜−１３０℃
である。ガラス転移温度が−１０℃を超えるときには、
硬化後のシーリング材の可撓性が０℃以下で不十分にな
る。このような有機微粉末としては、ＣＨ2 ＝ＣＨＣＯ
ＯＲ（式中、Ｒは炭素数４〜１４のアルキル基を表す）
で示されるアルキルアクリレートを、公知の方法、例え
ば米国特許第３６９１１４０号明細書に記載された方法
で懸濁重合させて得られる粘着性微粉末、ウレタン微粉
末、アクリルウレタン微粉末、天然ゴム微粉末、合成ゴ
ム微粉末、ポリエチレン微粉末、エチレン酢酸ビニル共
重合体微粉末等を挙げることができる。有機微粉末は、
混合する他の各種モノマーに溶解も膨潤もしないか、又
は膨潤はするが溶解はしない性質を持つ必要がある。The glass transition temperature of the organic fine powder used in the present invention is -10 ° C or lower, preferably -30 to -130 ° C.
Is. When the glass transition temperature exceeds −10 ° C.,
The flexibility of the sealing material after curing becomes insufficient at 0 ° C or lower. As such an organic fine powder, CH 2 ═CHCO
OR (in the formula, R represents an alkyl group having 4 to 14 carbon atoms)
The adhesive fine powder, urethane fine powder, acrylic urethane fine powder, natural rubber fine powder obtained by suspension polymerization of the alkyl acrylate represented by the above-mentioned by a known method, for example, the method described in US Pat. No. 3,691,140. , Synthetic rubber fine powder, polyethylene fine powder, ethylene vinyl acetate copolymer fine powder, and the like. Organic fine powder,
It must not dissolve or swell in other various monomers to be mixed, or it must swell but not dissolve.
【００１３】有機微粉末の粒子径は、０．１〜５０μm
が好ましい。粒子径が上記下限値未満のときには、シー
リング材の製造時に微粒子が飛散して取り扱いが悪くな
り、上限値を超えるときには、シーリング材を硬化させ
た後の表面のきめが粗くなり、平滑面が得られない場合
がある。有機微粉末の配合量は、５〜８０重量％、好ま
しくは１０〜７０重量％である。The particle size of the organic fine powder is 0.1 to 50 μm.
Is preferred. When the particle size is less than the above lower limit value, fine particles are scattered during the production of the sealing material, resulting in poor handling.When the particle size exceeds the upper limit value, the surface texture after curing the sealing material becomes rough and a smooth surface is obtained. It may not be possible. The compounding amount of the organic fine powder is 5 to 80% by weight, preferably 10 to 70% by weight.
【００１４】本発明のシーリング材には、上記光硬化性
モノマー及び／又はオリゴマー、並びに有機微粉末の
外、ゴム、エラストマー、その他のポリマーを配合する
ことができ、具体例としては、天然ゴム、ポリイソプレ
ンゴム、ポリイソブチレンゴム、ポリブタジエンゴム、
ブチルゴム、ニトリルブチルゴム、ポリクロロプレンゴ
ム、スチレンブタジエンゴム、スチレンイソプレンゴ
ム、アクリルゴム、ポリブチレン、ポリブテン、ポリフ
ェニレンオキシド、ポリカーボネート、ポリ酢酸ビニ
ル、メタクリル樹脂、ポリアクリロニトリル、熱可塑性
ポリエステル類、ポリアミド類、ポリビニルブチラー
ル、熱可塑性エポキシ樹脂、エチレン酢酸ビニル共重合
体等を挙げることができる。これらはモノマーやオリゴ
マーに溶解するか、あるいは均一に分散させて用いる。
配合量は、硬化前の粘度や硬化後の物性等を考慮し、適
宜に調節することができる。In the sealing material of the present invention, in addition to the above-mentioned photo-curable monomer and / or oligomer and organic fine powder, rubber, elastomer and other polymers can be blended. Specific examples include natural rubber, Polyisoprene rubber, polyisobutylene rubber, polybutadiene rubber,
Butyl rubber, nitrile butyl rubber, polychloroprene rubber, styrene butadiene rubber, styrene isoprene rubber, acrylic rubber, polybutylene, polybutene, polyphenylene oxide, polycarbonate, polyvinyl acetate, methacrylic resin, polyacrylonitrile, thermoplastic polyesters, polyamides, polyvinyl butyral, Examples thereof include thermoplastic epoxy resins and ethylene vinyl acetate copolymers. These are dissolved in the monomer or oligomer, or are dispersed evenly before use.
The compounding amount can be appropriately adjusted in consideration of the viscosity before curing and the physical properties after curing.
【００１５】紫外線硬化用のシーリング材には、光反応
開始剤を、シーリング材１００重量部に対し１〜７重量
部、好ましくは２〜５重量部を配合することができる。
光反応開始剤としては、ベンゾインメチルエーテル、ベ
ンゾインエチルエーテル、α−メチルベンゾイン、ベン
ゾフェノン、ベンジル、アセトフェノン、アントラキノ
ン、フェナントラキノン、ベンジルスルフィド、２−ク
ロロチオキサントン、２−メチルチオキサントン等を挙
げることができる。また、本発明のシーリング材には、
必要に応じて熱反応開始剤、顔料、重合禁止剤等を配合
することができる。本発明のシーリング材は、上記成分
を混合して得ることができ、自動ディスペンサー、チュ
ーブ、シーラーガン等で適用箇所に塗布した後、電離放
射線を照射して硬化し施工する。The ultraviolet curing sealant may contain a photoreaction initiator in an amount of 1 to 7 parts by weight, preferably 2 to 5 parts by weight, based on 100 parts by weight of the sealing material.
Examples of the photoreaction initiator include benzoin methyl ether, benzoin ethyl ether, α-methylbenzoin, benzophenone, benzyl, acetophenone, anthraquinone, phenanthraquinone, benzyl sulfide, 2-chlorothioxanthone, and 2-methylthioxanthone. it can. Further, the sealing material of the present invention,
If necessary, a thermal reaction initiator, a pigment, a polymerization inhibitor and the like can be added. The sealing material of the present invention can be obtained by mixing the above-mentioned components, and is applied to an application site with an automatic dispenser, a tube, a sealer gun or the like, and then is irradiated with ionizing radiation to be cured and applied.
【００１６】[0016]
実施例１〜３及び比較例１〜３ 表１に示す成分の所定量（重量部）を、高速撹拌機で混
合し、６種類の紫外線硬化型シーリング材を調製した。
得られたシーリング材について、下記に示す引張り試
験、硬度試験、粘度試験、筆さばき性、剪断力試験、及
び耐寒折曲げ性試験を行った。結果を表１に示す。Examples 1 to 3 and Comparative Examples 1 to 3 Predetermined amounts (parts by weight) of the components shown in Table 1 were mixed with a high-speed stirrer to prepare 6 types of UV-curable sealing materials.
The following tensile test, hardness test, viscosity test, brush release property, shearing force test, and cold bending resistance test were performed on the obtained sealing material. The results are shown in Table 1.
【００１７】引張り試験 シーリング材を、へら及び治具を用いて、幅１０mm、厚
さ２±０．２mmに成型し、紫外線を照射して完全に硬化
させ、フィルム状の試料を得、これをテンシロン型試験
機にて幅４０mmでつかみ、速度２００mm／分にて引張り
試験を行った。なお、試験は２３℃及び−５℃雰囲気下
で行った。 Tensile test Sealing material was molded into a width of 10 mm and a thickness of 2 ± 0.2 mm using a spatula and a jig, and was completely cured by irradiation with ultraviolet rays to obtain a film-like sample. A tensile test was performed at a speed of 200 mm / min by gripping with a Tensilon type tester with a width of 40 mm. The test was conducted in an atmosphere of 23 ° C and -5 ° C.
【００１８】硬度試験 引張り試験で用いたものと同様の試料を３枚重ねにし、
これを硬質の台上に置き、ＪＩＳＡ型スプリング式硬さ
試験機で押しつけたときの値を、５カ所平均で求め、測
定値とした。 Hardness test Three samples similar to those used in the tensile test were stacked,
This was placed on a hard table and pressed by a JISA type spring hardness tester, and the value was calculated as an average value at 5 points and used as the measured value.
【００１９】粘度試験 スパイラル二重円筒管式粘度計（ＰＣ−１ＴＬ、マルコ
ム（株）製）を用い、２３℃における硬化前のシーリン
グ材の粘度を測定した。 Viscosity Test The viscosity of the sealing material before curing at 23 ° C. was measured using a spiral double cylindrical tube viscometer (PC-1TL, manufactured by Malcolm Co., Ltd.).
【００２０】筆さばき性 ５mm径のガラス棒を深さ５０mmまで垂直に差し込んだ
後、素早く抜き取り、ガラス棒に付着したシーリング材
がたれ落ちる状態を観察した。A glass rod having a diameter of 5 mm for brushing was vertically inserted to a depth of 50 mm, and then quickly withdrawn, and a state in which the sealing material attached to the glass rod fell down was observed.
【００２１】剪断力試験 幅２０mm、厚さ３mm、長さ１２０mmのアクリル板２枚で
シーリング材を厚さ２mmで幅２０mm四方に挟み込み、は
み出し分は除去した後、直接あるいはアクリル板越しに
紫外線を照射し、全体を完全に硬化させて、テンシロン
型試験機で、アクリル板の両端をつかみ、引張り速度５
０mm／分で引張り、剪断力を測定した。 Shearing force test A sealing material was sandwiched between two acrylic plates having a width of 20 mm, a thickness of 3 mm and a length of 120 mm and having a thickness of 2 mm and a width of 20 mm. After removing the protruding portion, ultraviolet rays were directly or through the acrylic plate. Irradiate, completely cure the whole, grasp the both ends of the acrylic plate with the Tensilon type tester, pulling speed 5
It was pulled at 0 mm / min and the shear force was measured.
【００２２】耐寒折曲げ性試験 シーリング材を、厚さ０．８mm、幅７０mm、長さ１５０
mmの電着塗装板のテストピース上に長手方向に塗布し、
へらと治具にて厚さ１mm、幅３mm、長さ１５０mmに成形
した後、塗布表面に紫外線を照射して完全に硬化させ試
料とした。このシーリング塗布テストピースを−３０℃
で３時間放置後、同雰囲気内で塗布面を外側とし、幅方
向に径３０mmのマンドレルをあてがい、これに１〜２秒
以内に１８０度に巻きつけて低温下での柔軟性を評価し
た。A cold-rolling bending resistance test sealing material was used, with a thickness of 0.8 mm, a width of 70 mm, and a length of 150.
Apply it longitudinally on the test piece of the electrodeposition coating plate of mm,
After molding with a spatula and a jig to a thickness of 1 mm, a width of 3 mm and a length of 150 mm, the coated surface was irradiated with ultraviolet rays to be completely cured to obtain a sample. Apply this sealing test piece to -30 ℃
After being left for 3 hours, the coated surface was set to the outside in the same atmosphere, a mandrel having a diameter of 30 mm was applied in the width direction, and the mandrel was wound at 180 degrees within 1 to 2 seconds to evaluate the flexibility at low temperature.
【００２３】なお、上記一連の試験において、シーリン
グ材の硬化は、１００Ｗ高圧水銀ランプ（２００〜２５
０Ｗ／cm2 ）の照射強度で数十秒間照射することにより
行なった。また、測定は耐寒折曲げ性試験以外は作製試
料を２３℃、６５％ＲＨの雰囲気中に３時間以上放置
後、同雰囲気内で行った。In the above series of tests, the curing of the sealing material was performed by using a 100 W high pressure mercury lamp (200 to 25
The irradiation was performed for several tens of seconds at an irradiation intensity of 0 W / cm 2 ). In addition, the measurement was performed in the same atmosphere after leaving the manufactured sample for 3 hours or more in an atmosphere of 23 ° C. and 65% RH, except for the cold bending resistance test.
【００２４】[0024]
【表１】 [Table 1]
【００２５】表１に示す試験結果から明らかなように、
実施例１〜３のシーリング材は、粘度、チキソトロピー
性、伸び、耐寒折曲げ性等が優れ、作業性、自動機械適
合性が良く、低温下でも良好な可撓性を示す。これに対
し、比較例１の無機充填剤を用いたシーリング材では、
耐寒折曲げ性試験で硬化物の縦方向に亀裂が入り、電着
塗装板テストピースからシーリング材が剥離した。ま
た、比較例２のエチレン・酢酸ビニル共重合体（ポリマ
ー成分）を多量に配合し、有機微粉末を含まないシーリ
ング材では、耐寒折曲げ性等は良好であるが、粘度がき
わめて高く、筆さばき性試験では糸引を生じた。また比
較例３のポリカプロラクトンジオール変性ウレタンアク
リレートオリゴマーを多量に配合し、有機微粉末を含ま
ないシーリング材は、粘度が高く、耐寒折曲げ性試験で
は亀裂が入り、可撓性が不十分であった。As is clear from the test results shown in Table 1,
The sealing materials of Examples 1 to 3 are excellent in viscosity, thixotropy, elongation, cold bending resistance, etc., have good workability and automatic machine compatibility, and exhibit good flexibility even at low temperatures. On the other hand, in the sealing material using the inorganic filler of Comparative Example 1,
In the cold bending resistance test, a crack was formed in the longitudinal direction of the cured product, and the sealing material was peeled from the electrodeposition coated plate test piece. In addition, a sealing material containing a large amount of the ethylene / vinyl acetate copolymer (polymer component) of Comparative Example 2 and containing no organic fine powder has good cold bending resistance, but has a very high viscosity. Stringing occurred in the handling test. Further, the sealing material containing a large amount of the polycaprolactone diol-modified urethane acrylate oligomer of Comparative Example 3 and containing no organic fine powder had a high viscosity and cracked in the cold bending resistance test, resulting in insufficient flexibility. It was
【００２６】[0026]
【発明の効果】本発明の電離放射線硬化型シーリング材
は、硬化前には作業性、自動機械適合性に優れ、硬化後
には、常温及び低温下においても、柔軟性に富む。EFFECT OF THE INVENTION The ionizing radiation-curable sealing material of the present invention is excellent in workability and automatic mechanical compatibility before curing, and is highly flexible after curing even at room temperature and low temperature.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｊ 4/00 ＪＢＧ 7921−4Ｊ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location C09J 4/00 JBG 7921-4J
Claims (1)
ー、並びにガラス転移点が−１０℃以下の有機微粉末を
含有する電離放射線硬化型シーリング材。1. An ionizing radiation-curable sealant containing a photocurable monomer and / or oligomer, and an organic fine powder having a glass transition point of -10 ° C. or lower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP995493A JPH06220421A (en) | 1993-01-25 | 1993-01-25 | Sealing material curable by ionizing radiation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP995493A JPH06220421A (en) | 1993-01-25 | 1993-01-25 | Sealing material curable by ionizing radiation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06220421A true JPH06220421A (en) | 1994-08-09 |
Family
ID=11734356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP995493A Pending JPH06220421A (en) | 1993-01-25 | 1993-01-25 | Sealing material curable by ionizing radiation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06220421A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002044299A1 (en) * | 2000-12-01 | 2002-06-06 | Nichiban Company Limited | Energy-curable sealing material composition |
| JP2002226509A (en) * | 2001-02-05 | 2002-08-14 | Nichiban Co Ltd | Photo-setting composition adhesive to oily face |
| WO2003083001A1 (en) * | 2002-03-28 | 2003-10-09 | Toppan Forms Co., Ltd. | Radiation hardenable adhesive composition containing dispersed natural rubber fine particles |
| WO2012013028A1 (en) * | 2010-07-30 | 2012-02-02 | 东莞市派乐玛新材料技术开发有限公司 | Radiation curable sealant used for encapsulating glasses nameplates or decorations |
-
1993
- 1993-01-25 JP JP995493A patent/JPH06220421A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002044299A1 (en) * | 2000-12-01 | 2002-06-06 | Nichiban Company Limited | Energy-curable sealing material composition |
| WO2002044298A1 (en) * | 2000-12-01 | 2002-06-06 | Nichiban Company Limited | Photocurable sealing material composition |
| US6818256B2 (en) | 2000-12-01 | 2004-11-16 | Nichiban Company Limited | Energy curable sealant composition |
| JP2002226509A (en) * | 2001-02-05 | 2002-08-14 | Nichiban Co Ltd | Photo-setting composition adhesive to oily face |
| WO2003083001A1 (en) * | 2002-03-28 | 2003-10-09 | Toppan Forms Co., Ltd. | Radiation hardenable adhesive composition containing dispersed natural rubber fine particles |
| US7232857B2 (en) | 2002-03-28 | 2007-06-19 | Toppan Forms Co., Ltd. | Radiation hardenable adhesive composition containing dispersed natural rubber fine particles |
| CN100336879C (en) * | 2002-03-28 | 2007-09-12 | 凸版资讯股份有限公司 | Radiation hardenable adhesive composition containing displersed natural rubber fine particles |
| WO2012013028A1 (en) * | 2010-07-30 | 2012-02-02 | 东莞市派乐玛新材料技术开发有限公司 | Radiation curable sealant used for encapsulating glasses nameplates or decorations |
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