JP3821169B2 - Anti-fraying adhesive for glass fiber yarns or woven fabrics - Google Patents
Anti-fraying adhesive for glass fiber yarns or woven fabrics Download PDFInfo
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- JP3821169B2 JP3821169B2 JP11535096A JP11535096A JP3821169B2 JP 3821169 B2 JP3821169 B2 JP 3821169B2 JP 11535096 A JP11535096 A JP 11535096A JP 11535096 A JP11535096 A JP 11535096A JP 3821169 B2 JP3821169 B2 JP 3821169B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、ガラス繊維ヤーンまたは織布（以下、両者を併せて「ガラス繊維織物」ともいう）のほつれ防止固着剤に関し、特に樹脂ワニスを含浸させた形態でプリント基板として用いられるガラス繊維ヤーンまたは織布のほつれ防止固着剤に関する。
【０００２】
【従来の技術】
特開平６−３４１０６５号公報、特公平２−２３６２６号公報等に記載されているように、ガラス繊維織物は、以前は有杼（シャットル）織機により製織されることが殆どであったが、最近は能率性、品質の良好性からエアジェット織機等の無杼織機で織られるものの割合が増大している。このような無杼織機では、緯糸が織物端部で折り返して隣接の緯糸を形成する有杼織機による織物とは異なり、緯糸が一回の緯入れ毎に切断されるため、織物の両耳部に緯糸の切断端部が房状に存在することとなる。ガラス繊維織物の多くはプリント基板に用いられるが、その際、エポキシ樹脂等の熱硬化性樹脂ワニスに含浸した後乾燥してプリプレグとされる。前記のようなエアジェット織機により織られ、前記のような端部を有するガラス繊維織物を樹脂ワニス含浸すると、この端部が多量のワニスを含浸する上、緯糸が折り返されていないため、経糸が容易にほつれ、これが含浸工程のロールに巻き付くなどのトラブルが発生する。端部はカットするので、経済的見地から耳部の長さを短くすると、前記ほつれが一層発生しやすくなる。また有杼織機で織られた織物であっても、二分割や三分割して使用されることがあるが、この場合も、単に機械的切断を施したときには、その切断部から経糸が容易にほつれ出す。
【０００３】
【発明が解決しようとする課題】
このようなほつれを防止するため、織物の端部あるいは地部をレーザー光線でガラス糸を熔融接着しながら切断することが検討されたが、熔融接着力は弱く、強いしごきに対しては容易に接着部分が剥離したり、熔融したガラスが微小な球形物を形成し、樹脂ワニス含浸工程中にワニスバスに落下するなどの欠点を有し、完全な対策とはならない。
また、ホットメルト接着剤を端部や切断部に施してほつれを防止する試みがなされたが、樹脂ワニスに使用される多種の有機溶剤に接着剤が溶出すると、そのワニスの性能に影響を与える恐れがある。特にプリント回路基板などの高度な品質保証が要求される分野に使用されるワニス含浸用ガラス繊維織物では、接着剤が溶出しないことが必須である。しかし、従来使用されてきたエチレン−酢酸ビニル共重合体あるいは重合脂肪酸と脂肪族アミンから得られるポリアミドを主成分とする共重合体等は耐溶剤性が充分ではなく、接着剤として使用不可能である。
また接着剤にエポキシ系樹脂やフェノール系樹脂などの熱硬化性樹脂を用いることも試みられているが、熱硬化性樹脂は耐薬品性が良好であるが、ガラス繊維織物に塗布後硬化するまでに時間を要し、設備面や生産性の面で満足ではない。
さらに熱可塑性樹脂が接着剤として試みられたが、溶融粘度が高く含浸が不十分となり、切断部からガラス糸の毛羽が発生する恐れがあり、塗布部分の織物厚みが他の部分より厚くなり、ガラス繊維織物をロールに巻き取る際に、いわゆる「耳高」などの支障を生じる。
【０００４】
さらにまた、前記特公平２−２３６２６号公報にも記載されているように、従来常用されてきたエチレン−酢酸ビニル共重合体等の接着剤は、有機溶剤溶液の形態で適用するとき、オープンタイムが長いという難点がある。すなわち、ガラス繊維織物にエチレン−酢酸ビニル共重合体等の常用される接着剤の溶液を適用した際、この溶液は容易に固化せず、接着剤が長時間粘着性を保持するため、ロール形態に巻き取った際、隣接ガラス繊維織物層が互いに接着するという問題がある。
【０００５】
【課題を解決するための手段】
本発明者は、このようなガラス繊維織物のほつれに関する技術の現状に鑑み、鋭意検討した結果、活性エネルギー線硬化性樹脂組成物を適用することが非常に効果的であることを見い出し、本発明を完成するに至った。
【０００６】
すなわち、第１の発明によれば、芳香族、脂肪族および脂環族から選ばれるジイソシアネートとラクトン変性２−ヒドロキシエチル（メタ）アクリレートとを反応させてなるウレタン（メタ）アクリレートを含む活性エネルギー線硬化性樹脂組成物からなるガラス繊維ヤーンまたは織布のほつれ防止固着剤が提供される。
第２の発明によれば、ウレタン（メタ）アクリレートがトリレンジイソシアネート又はイソホロンジイソシアネートとε−カプロラクトン変性２−ヒドロキシエチル（メタ）アクリレートとを反応させてなるものである前記第１の発明のガラス繊維ヤーンまたは織布のほつれ防止固着剤が提供される。
また、第３の発明によれば、芳香族、脂肪族および脂環族から選ばれるジイソシアネートとラクトン系ポリエステルポリオール及び１分子中に少なくとも１個の水酸基を有する（メタ）アクリレートモノマーとを反応させてなるウレタン（メタ）アクリレートを含む活性エネルギー線硬化性樹脂組成物からなるガラス繊維ヤーンまたは織布のほつれ防止固着剤が提供される。
第４の発明によれば、ウレタン（メタ）アクリレートがトリレンジイソシアネート又はイソホロンジイソシアネートとポリカプロラクトン及び２−ヒドロキシエチル（メタ）アクリレートとを反応させてなるものである前記第３の発明のガラス繊維ヤーンまたは織布のほつれ防止固着剤が提供される。
以下、本発明を詳しく説明する。
【０００７】
【発明の実施の形態】
本発明に用いられるガラス繊維織物としては、織り方、厚み、単位面積当たりのガラス繊維重量、集束剤の有無などには特に限定されない。
【０００８】
本発明に用いられる活性エネルギー線硬化性樹脂組成物としては、活性エネルギー線で硬化するものであれば特に限定されないが以下に述べるものが、例示される。
【０００９】
（活性エネルギー線硬化性樹脂組成物の例）
本発明に使用できる活性エネルギー線硬化性樹脂組成物の例としては、（１）ウレタン（メタ）アクリレート等のオリゴマー類（Ａ）、あるいはこれらと、任意成分であるスチレン、（メタ）アクリルニトリル、（メタ）アクリル酸エステル等のモノマー類（後記希釈モノマー）（Ｂ）との混合物が挙げられる。
【００１０】
（１）ウレタン（メタ）アクリレートとしては、
（１−ａ）有機イソシアネート、および
（１−ｂ）１分子中に少なくとも１個の水酸基を有する（メタ）アクリレートモノマー、を公知の方法によって反応させることにより得られる反応生成物、または（１−ａ）、（１−ｂ）成分に加え、（１−ｃ）１分子中に２個以上の水酸基を有するポリオール、を公知の方法によって反応させることにより得られる反応生成物である。
【００１１】
ここで、有機イソシアネート類としては、トリレンジイソシアネート、４，４−ジフェニルメタンジイソシアネート、１，６−ヘキサメチレンジイソシアネート、キシリレンジイソシアネート、イソホロンジイソシアネート等の芳香族、脂肪族および脂環族ジイソシアネートが挙げられる。
【００１２】
また、前記の１分子中に少なくとも１個の水酸基を有する（メタ）アクリレートモノマーとしては、ラクトン変性２−ヒドロキシエチル（メタ）アクリレートが挙げられる。
【００１３】
さらに、１分子中に２個以上の水酸基を有するポリオールとしては、ポリカプロラクトン、ポリブチロラクトンなどのラクトン系ポリエステルポリオールが挙げられる。
【００１４】
ここでいう公知の方法としてその一例を示すと、常圧において反応温度は６０〜９０℃が好ましく、一般に、反応促進のために触媒の使用が望ましい。触媒の代表例としては、ジブチル錫ジラウレート、ジブチル錫ジエチルヘキソエート、ジブチル錫サルフアイド、ジブチル錫ジブトキサイドなどである。このような水酸基とイソシアネート基の反応に有効な触媒を、好ましくは５０〜５０００ｐｐｍ、特に好ましくは２５０〜１０００ｐｐｍ使用することができる。反応は、通常、残存イソシアネートの濃度が所定濃度以下になるまで行う。
【００１５】
なお、本発明においては、組成物の粘度調整、ほつれ防止固着剤としての物性を改良するために任意のエチレン性不飽和単量体（以下、希釈モノマーという）を使用することができる。
希釈モノマーの具体例としては、スチレン、（メタ）アクリルニトリル、エチル（メタ）アクリレート、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、イソボニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、２−クロロスチレン、フェノキシエチル（メタ）アクリレート、（メタ）アクリル酸、２−ヒドロキシエチル（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、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等を例示することができる。これらの希釈モノマーは、単独あるいは２種類以上を組み合わせて使用することができる。
【００１６】
さらに本発明で使用する活性エネルギー線硬化性樹脂組成物は、紫外線、電子線などの活性エネルギー線で硬化することが可能であるが、紫外線によって硬化する場合には、光重合開始剤を使用することができ、また必要に応じて光重合開始助剤も併用することが可能である。
【００１７】
光重合開始剤としては、ベンゾイン、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテル、アセトフェノン、２，２−ジメトキシ−２−フェニルアセトフェノン、２，２−ジエトキシ−２−フェニルアセトフェノン、１，１−ジクロロアセトフェノン、１−ヒドロキシシクロヘキシルフェニルケトン、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノ−プロパン−１−オン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、Ｎ，Ｎ−ジメチルアミノアセトフェノン、２−メチルアントラキノン、２−エチルアントラキノン、２−ｔｅｒｔ−ブチルアントラキノン、１−クロロアントラキノン、２−アミルアントラキノン、２−アミノアントラキノン、２，４−ジエチルチオキサントン、２，４−ジイソプロピルチオキサントン、アセトフェノンジメチルケタール、メチルベンゾフェノン、４，４´−ジクロロベンゾフェノン、４，４´−ビスジエチルアミノベンゾフェノン、ミヒラーズケトンなどが挙げられる。これらは、単独あるいは２種類以上を組み合わせて使用することができる。さらに、このような光重合開始剤は、Ｎ，Ｎ−ジメチルアミノ安息香酸エチルエステル、トリエタノールアミン、トリエチルアミンのような公知慣用な光重合開始助剤を単独あるいは２種類以上を組み合わせて使用することができる。光重合開始剤の含有量は前記組成物１００重量部に対して、１〜１０重量部、特には３〜６重量部の範囲であることが好ましい。
【００１８】
以上例示したような活性エネルギー線硬化性組成物は、活性エネルギー線を照射することにより硬化させることができる。
使用できる活性エネルギー線としては、紫外線、電子線が例示される。
紫外線を使用した場合の照射条件は、水銀ランプ、メタルハライドランプ等を用い、硬化エネルギーは２０〜５００ｍＪ／ｃｍ2であることが好ましい。また必要に応じて基材であるガラス繊維織物の両面に紫外線を照射することも可能である。また、電子線を使用した場合の照射条件は、加速電圧１５０〜２５０ｋｅＶで１〜５Ｍｒａｄの照射量であることが好ましい。電子線の照射は、窒素雰囲気下で行う。
【００１９】
【実施例】
以下、実施例により本発明を具体的に説明するが、本発明はこれらに限定されるものではない。
【００２０】
〔合成例１〕
油浴中に浸漬され、攪拌機、温度計、添加ロート及び乾燥空気供給口を備えた反応容器に、２，４−トリレンジイソシアネート（ＴＤＩ）３４８ｇ（２モル）、ジブチル錫ジラウレート（ＤＢＴＤＬ）０．５ｇを仕込み、昇温した。反応容器内が７０℃に達した時点で、添加ロートより、ε−カプロラクトン変性２−ヒドロキシエチルアクリレート（Ｐｌａｃｃｅｌ ＦＡ−２，分子量３４４、ダイセル化学工業(株)製）６８８ｇ（２モル）を添加した。添加終了後、残存ジイソシアネート濃度が０．１重量％以下になるまで熟成しウレタンアクリレート（合成例１）を得た。
【００２１】
〔合成例２〕
合成例１中のＴＤＩに代えて、イソホロンジイソシアネート（ＩＰＤＩ）４４４ｇ（２モル）とした他は、合成例１と同様にして、ウレタンアクリレート（合成例２）を得た。
【００２２】
〔合成例３〕
油浴中に浸漬され、攪拌機、温度計、添加ロート及び乾燥空気供給口を備えた反応容器に、２，４−トリレンジイソシアネート（ＴＤＩ）３４８ｇ（２モル）、ジブチル錫ジラウレート（ＤＢＴＤＬ）０．５ｇを仕込み、昇温した。反応容器内が７０℃に達した時点で、添加ロートより、ポリカプロラクトン（Ｐｌａｃｃｅｌ ２０５，分子量５３０のポリカプロラクトンジオール，ダイセル化学工業(株)製）５３０ｇ（１モル）を添加した。添加終了後、残存ジイソシアネート濃度が理論値になるまで反応容器内温度を７０℃に保ち、ポリカプロラクトンウレタンプレポリマーを製造した。その後、２−ヒドロキシエチルアクリレート（ＨＥＡ）２３２ｇ（２モル）の添加後、反応生成物の抜き取りサンプル中のイソシアネート濃度が０．１重量％以下となったことを確認するまで反応容器内を７０℃に保ち熟成を行った。これによりウレタンアクリレートオリゴマー（合成例３）を得た。
【００２３】
〔合成例４〕
合成例３中のＴＤＩをイソホロンジイソシアネート（ＩＰＤＩ）４４４ｇ（２モル）とした他は合成例３と同様にしてウレタンアクリレートオリゴマー（合成例４）を得た。
【００２４】
（実施例１〜４）
表−１に示すような組成（数値は重量部を示す。）からなる活性エネルギー線硬化性樹脂組成物からなるガラス繊維織物のほつれ防止固着剤を調製した。得られたほつれ防止固着剤をローラコーターによりガラス繊維織物（平織り、厚さ２００μｍ）に幅１０ｍｍで経糸方向に沿って塗布し、その後、高圧水銀ランプ（照射条件１２０Ｗ／ｃｍ×５０ｍ／分×１パス）により硬化した。なお、塗布量は１００ｇ／ｍ2であった。
【００２５】
【表１】
【００２６】
上で得られたガラス繊維織物のほつれ防止固着剤の塗布された部分の中央部を経糸に沿って切断し、最端部にある経糸の一本で引張接着強度を測定し、耳ほつれ強度（ｇ）とした。また上で得られたほつれ防止固着剤塗布ガラス繊維織物を各種溶剤に７２時間（２５℃）浸漬し、ほつれ防止固着剤塗布部分の状態観察を行って、耐溶剤性を評価（○：変化せず，△：膨潤する，×：経糸がほつれる）した。さらにガラス繊維織物を屈曲させ、ほつれ防止固着剤の塗布部分の柔軟性を評価（○：柔軟性良好，×：柔軟性不良）した。これらの結果を表−２に示す。
なお、得られたほつれ防止固着剤塗布ガラス繊維織物について、プリプレグを作製し、一定寸法（３０ｃｍ）に切断し、積み重ねた結果、端の部分と中央部分との高さの差は殆ど見られなかった。
【００２７】
【表２】
【００２８】
【発明の効果】
本発明のほつれ防止固着剤は、常温でのポットライフが長く、活性エネルギー線により硬化する時間が短いため、ガラス繊維織物に適用する場合、取扱い性や生産性に優れている。また本発明のほつれ防止固着剤が塗布されたガラス繊維織物は、ほつれ防止固着剤が塗布された部分のほつれ強度が大きく、各種溶剤に対する耐溶剤性にも優れている。また塗布された部分は塗膜が柔軟性を有しているため、取扱い時に割れたり折れたりすることもない。このガラス繊維織物をプリプレグとして多数枚積み重ねても、高さの差は塗布していないものと殆どなく、切断端部も直線状を保っている。[0001]
BACKGROUND OF THE INVENTION
The present invention is a glass fiber yarn or fabric (together both also referred to as "glass fiber fabric") related to raveling-preventing agent, glass fiber yarn used as the printed circuit board in a form is especially impregnating the resin varnish or about the raveling-preventing agent of the woven fabric.
[0002]
[Prior art]
As described in JP-A-6-341065, JP-B-2-23626, and the like, glass fiber fabrics were mostly woven by a shuttle loom in the past. The ratio of those woven by a plain loom such as an air jet loom is increasing due to efficiency and good quality. In such a weaving loom, the weft is cut at each weft insertion, unlike the weaving loom, in which the weft is folded at the end of the fabric to form an adjacent weft. In addition, the cut ends of the wefts are present in a tuft shape. Most glass fiber fabrics are used for printed circuit boards. At that time, they are impregnated with a thermosetting resin varnish such as an epoxy resin and then dried to form a prepreg. When a glass fiber fabric woven by an air jet loom as described above and impregnated with a resin varnish as described above is impregnated with a large amount of varnish and the weft is not folded back, Fraying easily causes troubles such as winding around the roll in the impregnation process. Since the end portion is cut, the fraying is more likely to occur if the length of the ear portion is shortened from an economical point of view. In addition, even a woven fabric woven with a knot loom may be used in two or three parts. In this case, too, when the machine is simply mechanically cut, the warp can be easily removed from the cut part. Start fraying.
[0003]
[Problems to be solved by the invention]
In order to prevent such fraying, it has been studied to cut the end or ground of the woven fabric while melting and bonding the glass yarn with a laser beam. However, the melt adhesion is weak and it is easily bonded to strong ironing. There are drawbacks such as peeling off of the part or melting glass forming a fine sphere and falling into the varnish bath during the resin varnish impregnation process, and is not a complete countermeasure.
In addition, attempts have been made to prevent fraying by applying hot melt adhesive to edges and cuts, but if the adhesive dissolves into various organic solvents used in resin varnishes, the performance of the varnish will be affected. There is a fear. In particular, in glass fiber fabrics for impregnating varnish used in fields requiring high quality assurance such as printed circuit boards, it is essential that the adhesive does not elute. However, conventionally used ethylene-vinyl acetate copolymers or copolymers based on polyamides obtained from polymerized fatty acids and aliphatic amines have insufficient solvent resistance and cannot be used as adhesives. is there.
In addition, attempts have been made to use thermosetting resins such as epoxy resins and phenolic resins as adhesives, but thermosetting resins have good chemical resistance, but until they are cured after being applied to glass fiber fabrics. It takes time and is not satisfactory in terms of equipment and productivity.
Furthermore, a thermoplastic resin was tried as an adhesive, but the melt viscosity was high and impregnation was insufficient, and there was a risk of fluffing of glass yarn from the cut part, and the woven fabric thickness of the coated part became thicker than other parts, When the glass fiber fabric is wound on a roll, troubles such as so-called “ear height” occur.
[0004]
Furthermore, as described in the above Japanese Patent Publication No. 23-26626, conventionally used adhesives such as ethylene-vinyl acetate copolymer have an open time when applied in the form of an organic solvent solution. There is a drawback that is long. That is, when a commonly used adhesive solution such as ethylene-vinyl acetate copolymer is applied to a glass fiber fabric, the solution does not easily solidify, and the adhesive retains tack for a long time. There is a problem in that adjacent glass fiber fabric layers adhere to each other when wound on.
[0005]
[Means for Solving the Problems]
As a result of intensive studies in view of the present state of the technology related to the fraying of such glass fiber fabrics, the present inventors have found that it is very effective to apply an active energy ray-curable resin composition, and the present invention. It came to complete.
[0006]
That is, according to 1st invention, the active energy ray containing urethane (meth) acrylate formed by making the diisocyanate chosen from aromatic, aliphatic, and alicyclic and lactone modified | denatured 2-hydroxyethyl (meth) acrylate react. An anti-fraying fixing agent for glass fiber yarns or woven fabrics comprising a curable resin composition is provided.
According to the second invention, the glass fiber of the first invention, wherein the urethane (meth) acrylate is obtained by reacting tolylene diisocyanate or isophorone diisocyanate with ε-caprolactone-modified 2-hydroxyethyl (meth) acrylate. An anti-fraying adhesive for yarns or woven fabrics is provided.
According to the third invention, a diisocyanate selected from aromatic, aliphatic and alicyclic, a lactone polyester polyol, and a (meth) acrylate monomer having at least one hydroxyl group in one molecule are reacted. An anti-fraying fixing agent for glass fiber yarn or woven fabric comprising an active energy ray-curable resin composition containing urethane (meth) acrylate is provided.
According to the fourth invention, the glass fiber yarn of the third invention, wherein the urethane (meth) acrylate is obtained by reacting tolylene diisocyanate or isophorone diisocyanate with polycaprolactone and 2-hydroxyethyl (meth) acrylate. Or an anti-fraying adhesive for woven fabrics is provided.
The present invention will be described in detail below.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The glass fiber fabric used in the present invention is not particularly limited to the weaving method, thickness, glass fiber weight per unit area, presence or absence of a sizing agent, and the like.
[0008]
The active energy ray-curable resin composition used in the present invention is not particularly limited as long as it is cured with active energy rays, and examples thereof include those described below.
[0009]
(Example of active energy ray-curable resin composition)
Examples of the active energy ray curable resin composition which can be used in the present invention, (1) a urethane (meth) acrylate oligomers such as preparative (A), or with these, styrene is an optional component, (meth) acrylonitrile , (Meth) acrylic acid ester and other monomers (described later dilution monomer) (B).
[0010]
(1) As urethane (meth) acrylate,
(1-a) an organic isocyanate, and (1-b) a reaction product obtained by reacting a (meth) acrylate monomer having at least one hydroxyl group in one molecule by a known method, or (1- In addition to the components a) and (1-b), (1-c) is a reaction product obtained by reacting a polyol having two or more hydroxyl groups in one molecule by a known method.
[0011]
Here, examples of organic isocyanates include aromatic, aliphatic and alicyclic diisocyanates such as tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, xylylene diisocyanate, and isophorone diisocyanate.
[0012]
Examples of the (meth) acrylate monomer having at least one hydroxyl group in one molecule include lactone-modified 2-hydroxyethyl (meth) acrylate.
[0013]
Furthermore, examples of the polyol having two or more hydroxyl groups in one molecule include lactone polyester polyols such as polycaprolactone and polybutyrolactone.
[0014]
As an example of the known method herein, the reaction temperature is preferably 60 to 90 ° C. at normal pressure, and it is generally desirable to use a catalyst for promoting the reaction. Typical examples of the catalyst include dibutyltin dilaurate, dibutyltin diethylhexoate, dibutyltin sulfide, dibutyltin dibutoxide and the like. Such a catalyst effective for the reaction between a hydroxyl group and an isocyanate group is preferably 50 to 5000 ppm, particularly preferably 250 to 1000 ppm. The reaction is usually carried out until the concentration of residual isocyanate is below a predetermined concentration.
[0015]
In the present invention, any ethylenically unsaturated monomer (hereinafter referred to as a dilution monomer) can be used in order to adjust the viscosity of the composition and improve the physical properties as a fraying prevention sticker.
Specific examples of the dilution monomer include styrene, (meth) acrylonitrile, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, 2- Chlorostyrene, phenoxyethyl (meth) acrylate, (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri ( Examples thereof include (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. These dilution monomers can be used alone or in combination of two or more.
[0016]
Furthermore, the active energy ray-curable resin composition used in the present invention can be cured with active energy rays such as ultraviolet rays and electron beams, but when it is cured with ultraviolet rays, a photopolymerization initiator is used. It is also possible to use a photopolymerization initiation aid together if necessary.
[0017]
Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, N, N -Dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone, 2,4-diethylthioxanthone, 2, - diisopropyl thioxanthone, acetophenone dimethyl ketal, methyl benzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone, and the like. These can be used alone or in combination of two or more. Further, as such a photopolymerization initiator, a known and commonly used photopolymerization initiator assistant such as N, N-dimethylaminobenzoic acid ethyl ester, triethanolamine or triethylamine may be used alone or in combination of two or more. Can do. The content of the photopolymerization initiator is preferably in the range of 1 to 10 parts by weight, particularly 3 to 6 parts by weight with respect to 100 parts by weight of the composition.
[0018]
The active energy ray-curable composition as exemplified above can be cured by irradiation with active energy rays.
Examples of active energy rays that can be used include ultraviolet rays and electron beams.
The irradiation conditions when ultraviolet rays are used are preferably a mercury lamp, a metal halide lamp, etc., and the curing energy is preferably 20 to 500 mJ / cm 2 . Moreover, it is also possible to irradiate ultraviolet rays to both surfaces of the glass fiber fabric which is a base material as needed. Moreover, it is preferable that the irradiation conditions at the time of using an electron beam are the irradiation amount of 1-5 Mrad with the acceleration voltage 150-250 keV. The electron beam irradiation is performed in a nitrogen atmosphere.
[0019]
【Example】
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
[0020]
[Synthesis Example 1]
In a reaction vessel immersed in an oil bath and equipped with a stirrer, thermometer, addition funnel and dry air supply port, 348 g (2 mol) of 2,4-tolylene diisocyanate (TDI), dibutyltin dilaurate (DBTDL) 0. 5 g was charged and the temperature was raised. When the inside of the reaction vessel reached 70 ° C., 688 g (2 mol) of ε-caprolactone-modified 2-hydroxyethyl acrylate (Placcel FA-2, molecular weight 344, manufactured by Daicel Chemical Industries, Ltd.) was added from the addition funnel. . After completion of the addition, the mixture was aged until the residual diisocyanate concentration was 0.1% by weight or less to obtain urethane acrylate (Synthesis Example 1).
[0021]
[Synthesis Example 2]
A urethane acrylate (Synthesis Example 2) was obtained in the same manner as in Synthesis Example 1, except that 444 g (2 mol) of isophorone diisocyanate (IPDI) was used instead of TDI in Synthesis Example 1.
[0022]
[Synthesis Example 3]
In a reaction vessel immersed in an oil bath and equipped with a stirrer, thermometer, addition funnel and dry air supply port, 348 g (2 mol) of 2,4-tolylene diisocyanate (TDI), dibutyltin dilaurate (DBTDL) 0. 5 g was charged and the temperature was raised. When the inside of the reaction vessel reached 70 ° C., 530 g (1 mol) of polycaprolactone (Placcel 205, polycaprolactone diol having a molecular weight of 530, manufactured by Daicel Chemical Industries, Ltd.) was added from the addition funnel. After completion of the addition, the temperature in the reaction vessel was kept at 70 ° C. until the residual diisocyanate concentration reached the theoretical value to produce a polycaprolactone urethane prepolymer. Thereafter, after the addition of 232 g (2 mol) of 2-hydroxyethyl acrylate (HEA), the reaction vessel was kept at 70 ° C. until it was confirmed that the isocyanate concentration in the sample withdrawn from the reaction product was 0.1% by weight or less. The aging was carried out. As a result, a urethane acrylate oligomer (Synthesis Example 3) was obtained.
[0023]
[Synthesis Example 4]
A urethane acrylate oligomer (Synthesis Example 4) was obtained in the same manner as in Synthesis Example 3 except that TDI in Synthesis Example 3 was changed to 444 g (2 mol) of isophorone diisocyanate (IPDI).
[0024]
(Examples 1-4)
An anti-fraying fixing agent for a glass fiber fabric comprising an active energy ray-curable resin composition having a composition as shown in Table 1 (numerical values represent parts by weight) was prepared. The obtained anti-fraying adhesive was applied to a glass fiber fabric (plain weave, thickness 200 μm) by a roller coater along the warp direction with a width of 10 mm, and then a high-pressure mercury lamp (irradiation conditions 120 W / cm × 50 m / min × 1). Cured by pass). The application amount was 100 g / m 2 .
[0025]
[Table 1]
[0026]
Cut the central part of the glass fiber fabric obtained above with the anti-fraying adhesive applied along the warp, measure the tensile bond strength with one warp at the end, g). Also, the glass fiber woven fabric coated with anti-fraying agent obtained above is immersed in various solvents for 72 hours (25 ° C), and the state of the anti-fraying agent-coated portion is observed to evaluate the solvent resistance (O: change) △: Swelled, ×: Warp frayed). Further, the glass fiber fabric was bent, and the flexibility of the application part of the anti-fraying adhesive was evaluated (◯: good flexibility, x: poor flexibility). These results are shown in Table-2.
In addition, about the obtained fraying prevention fixing agent application | coating glass fiber fabric, a prepreg was produced, it cut | disconnected to a fixed dimension (30 cm), and as a result of stacking, the difference in the height of an edge part and a center part was hardly seen. It was.
[0027]
[Table 2]
[0028]
【The invention's effect】
The fray-preventing fixing agent of the present invention has a long pot life at normal temperature and a short time for curing with active energy rays, and therefore has excellent handleability and productivity when applied to glass fiber fabrics. Further, the glass fiber woven fabric coated with the anti-fraying fixing agent of the present invention has a high fraying strength at the portion where the anti-fraying fixing agent is applied, and is excellent in solvent resistance against various solvents. Moreover, since the coating film has a softness | flexibility in the applied part, it is not cracked or broken at the time of handling. Even when a large number of glass fiber fabrics are stacked as a prepreg, there is almost no difference in height, and the cut ends are kept straight.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11535096A JP3821169B2 (en) | 1996-04-12 | 1996-04-12 | Anti-fraying adhesive for glass fiber yarns or woven fabrics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11535096A JP3821169B2 (en) | 1996-04-12 | 1996-04-12 | Anti-fraying adhesive for glass fiber yarns or woven fabrics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09279481A JPH09279481A (en) | 1997-10-28 |
| JP3821169B2 true JP3821169B2 (en) | 2006-09-13 |
Family
ID=14660355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11535096A Expired - Lifetime JP3821169B2 (en) | 1996-04-12 | 1996-04-12 | Anti-fraying adhesive for glass fiber yarns or woven fabrics |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3821169B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108929426A (en) * | 2017-05-27 | 2018-12-04 | 科思创德国股份有限公司 | A kind of polyurethane prepreg and the preparation method and application thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5659646A (en) * | 1979-10-19 | 1981-05-23 | Shin Etsu Chem Co Ltd | Treatment of glass fiber product |
| JPS60194182A (en) * | 1984-03-12 | 1985-10-02 | ユニチカユ−エムグラス株式会社 | Treatment of glass cloth |
| JPS63196791A (en) * | 1987-02-10 | 1988-08-15 | 大和紡績株式会社 | Industrial belt like fabric reinforced in selvage part |
| JPH0633572B2 (en) * | 1989-02-21 | 1994-05-02 | 信越化学工業株式会社 | Treatment agent for glass fiber fabric and glass fiber fabric treated with the treatment agent |
| JP3058897B2 (en) * | 1990-08-29 | 2000-07-04 | 宇部日東化成株式会社 | Method for producing fiber-reinforced curable resin fine filaments |
| JP2846516B2 (en) * | 1992-01-17 | 1999-01-13 | サンノプコ株式会社 | Ear reinforcement for dryer canvas and dryer canvas with reinforced ear |
| FR2691171B1 (en) * | 1992-05-15 | 1994-12-23 | Vetrotex France Sa | Process for manufacturing a continuous wire by mechanical drawing and products resulting therefrom. |
| JPH0813343A (en) * | 1994-06-30 | 1996-01-16 | Nitto Boseki Co Ltd | Antifray fixing agent for glass cloth, glass fiber fabric using the same and their production |
| JPH08260340A (en) * | 1995-03-28 | 1996-10-08 | Unitika U M Glass Kk | Method for preventing raveling of selvage part of woven glass fiber fabric |
-
1996
- 1996-04-12 JP JP11535096A patent/JP3821169B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108929426A (en) * | 2017-05-27 | 2018-12-04 | 科思创德国股份有限公司 | A kind of polyurethane prepreg and the preparation method and application thereof |
| WO2018219756A1 (en) * | 2017-05-27 | 2018-12-06 | Covestro Deutschland Ag | A polyurethane prepreg and preparation method and applications thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09279481A (en) | 1997-10-28 |
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