JP2004051652A - Thermosetting resin composition - Google Patents
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、主として臭閾値が低いアミン、ホルムアルデヒドなどの不快な臭気を軽減して作業環境の悪化を防止ないしは改善できる香料系消臭剤を含んでなる熱硬化性樹脂組成物に関する。
【０００２】
【従来の技術】
従来より、断熱・防音材料（レジンフェルト、樹脂発泡体）、木質系複合材料、成形材料、研磨・摩擦材料、積層材、接着剤などには、硬化剤ないし硬化触媒の存在下又は非存在下で熱硬化性を発現する硬化性樹脂がバインダーないしはマトリックス樹脂として使用されている。
【０００３】
例えば、各種の繊維を強化材として、熱硬化性フェノール樹脂をマトリックス樹脂とした成形材料、例えば、シート・モールディング・コンパウンド、バルク・モールディング・コンパウンド、プルトルージョン（引抜成形法）、レジンインジェクション法（樹脂圧入法）及び樹脂移送成形法（ＲＴＭ）等においては、一般にマトリックス樹脂としてフェノール樹脂が主に用いられている。
【０００４】
【発明が解決しようとする課題】
しかしながら、この種の熱硬化性フェノール樹脂を用いた場合、成形時に樹脂中の未反応分のフェノールや、硬化剤として用いたヘキサメチレンテトラミンに起因した臭閾値が低く不快な臭気を有するアンモニア（０．５９ｐｐｍ）、トリメチルアミン（０．００１４ｐｐｍ）等のアミン及びホルムアルデヒド（１．９ｐｐｍ）などが発生して作業環境を悪化させる問題が生じることから、従来より排気ダクト等の設備対応のほか種々の軽減対策が講じられている。
【０００５】
例えば、ヘキサメチレンテトラミンを使用しないでも熱硬化性を発現するレゾール型フェノール樹脂をバインダーとして用いる方法、又は臭気を軽減できる脱臭剤、例えば特開平９−３８７４８号公報に開示されているようなオレンジオイル、テレビンオイル、シダーウッドオイルを主成分とする脱臭剤を用いる方法などが試みられており、ある程度の臭気軽減効果は得られるが十分であるとは言えずさらなる改善の余地が求められている。
【０００６】
本発明は、上記したように、バインダーないしはマトリックス樹脂として熱硬化性樹脂を用いる際に生じる不快な臭気による作業環境の悪化を防止し、又は改善するためになされたものであり、第１の目的は、特に臭閾値が低いアミン、ホルムアルデヒド等に起因する臭気の軽減に有効な香料系消臭剤を含んでなる熱硬化性樹脂組成物を提供することであり、また第２の目的は、消臭能の持続性に優れた香料系消臭剤を配合してなる熱硬化性樹脂組成物を提供することである。
【０００７】
【課題を解決するための手段】
本発明者等は、上記の課題を消臭剤の観点から鋭意検討を行った結果、特定のエステルを含有する香料系消臭剤を配合してなる熱硬化性樹脂組成物が前記課題達成に有効であることを見出し、本発明を完成するに至った。
【０００８】
すなわち、本発明の熱硬化性樹脂組成物は、（Ａ）熱硬化性樹脂と（Ｂ）３環式炭化水素骨格を有するエステルを含有する香料系消臭剤とを含んでなることを特徴とする。本発明においては、前記香料系消臭剤が、α、β−不飽和ケトン及びα、β−不飽和アルデヒドから選ばれる少なくとも１種を含有することが好ましく、特に炭素数が５〜１６であるα、β−不飽和ケトン、α、β−不飽和アルデヒドであることがより好ましい。
【０００９】
【発明の実施の形態】
本発明において用いられる（Ａ）熱硬化性樹脂は、例えば繊維基材、有機・無機充填材、接着剤、断熱・防音材料等のバインダーないしはマトリックス樹脂として用いられるものであり、硬化剤ないしは硬化触媒、例えばヘキサメチレンテトラミン、ポリイソシアネート、酸性化合物、過酸化物などの存在下又は非存在下で熱硬化して結合機能を有するものである。このような熱硬化性樹脂の例としては、フェノール樹脂、メラミン樹脂、尿素樹脂、キシレン樹脂、エポキシ樹脂、多官能性アクリルアミド系樹脂（特公平７―１０６４２１号公報）、不飽和ポリエステル、ジアリルフタレート樹脂、アルキッド樹脂等が挙げられる。これらは単独で用いてもよいし、２種以上を組合せて用いてもよい。
【００１０】
前記（Ａ）熱硬化性樹脂としてのフェノール樹脂は、酸性触媒及び／又は塩基性触媒の存在下でフェノール類とアルデヒド類を反応させると得られる縮合生成物を主成分とし、上述した硬化剤ないしは硬化触媒の存在下又は非存在下で熱硬化性を発現するフェノール樹脂であり、具体的には、ノボラック型フェノール樹脂、レゾール型フェノール樹脂、アルカリレゾール型フェノール樹脂、含窒素レゾール型フェノール樹脂、ベンジリックエーテル型フェノール樹脂及びこれらの樹脂の製造過程ないしは製造後に任意の化合物、例えばエポキシ樹脂、メラミン樹脂、尿素樹脂、キシレン樹脂、酢酸ビニル樹脂、ポリアミド樹脂、尿素系化合物、メラミン系化合物、エポキシ系化合物、カッシュナット油と混合ないしは反応させて得られる変性フェノール樹脂などが例示される。
【００１１】
本発明において用いられる香料系消臭剤は、必須の成分として（Ｂ）３環式炭化水素骨格を有するエステルを含有する。このようなエステルの例としては、具体的にトリシクロ［５．２．１．０２，６］デカン−２−カルボン酸エチル（フルテート；花王製）、トリシクロ［５．２．１．０２，６］デカン−２−カルボン酸プロピル、トリシクロ［５．２．１．０２，６］デカン−２−カルボン酸ブチル、酢酸セドリル、酢酸カリオフィレン、酢酸トリシクロデセニル、酢酸トリシクロデシルなどが挙げられる。これらのなかでも、消臭効果の安定性の点からトリシクロ［５．２．１．０２，６］デカン−２−カルボン酸エチル（フルテート）が特に好ましい。
【００１２】
また、前記香料系消臭剤としては、例えば硬化剤として用いるヘキサメチレンテトラミン水溶液やアルカリ性の高いフェノール樹脂などのアルカリ性のもとでも消臭効果の持続性を保持するためには、アルカリ域での安定性に優れる（Ｂ）３環式炭化水素骨格を有するエステルのみを用いても良いが、（Ｂ）３環式炭化水素骨格を有するエステルをベースとして用い、それにアミン、ホルムアルデヒドなどに対して化学消臭効果の高いα、β−不飽和ケトン及びα、β−不飽和アルデヒド、特に炭素数が５〜１６のα、β−不飽和ケトン及びα、β−不飽和アルデヒドから選ばれる少なくとも１種を臭気の質に応じて適当量配合するとより好ましい。
【００１３】
前記α、β−不飽和ケトンとしては、具体的にα−又は、β−又は、γ−ダマスコン、α−又は、β−ダマセノン、α−又は、β−又は、γ−ヨノン、α−又は、β−又は、γ−メチルヨノン、アセトフェノン、ｐ−メチルアセトフェノン、メチル−β−ナフチルケトン、テンタローム、α−又は、β−イソメチルヨノン、α−又は、β−又は、γ−イロン、マルトール、エチルマルトール、ｃｉｓ−ジャスモン、ジヒドロジャスモン、ｌ−カルボン、ヌートカトンなどが挙げられる。これらのなかでも、消臭効果の点からα−又は、β−又は、γ−ダマスコン、α−又は、β−ダマセノン、マルトール、エチルマルトールが特に好ましい。
【００１４】
また、α、β−不飽和アルデヒドとしては、具体的にｔ−２−ヘキセナール、２，６−ノナジエナール、シトラール、ベンズアルデヒド、α−ヘキシルシンナミックアルデヒド、α−アミルシンナミックアルデヒド、ヘリオトロピン、アニスアルデヒド、バニリン、エチルバニリン、クミンアルデヒド、シンナミックアルデヒド、ペリラアルデヒドなどが挙げられる。これらのなかでも、消臭効果の点からヘリオトロピン、アニスアルデヒド、バニリン、エチルバニリンが特に好ましい。
【００１５】
前記α、β−不飽和ケトン及びα、β−不飽和アルデヒド（から選ばれる少なくとも１種の成分の配合量は、使途に応じて決定されるが、一般的には質量基準で（Ｂ）成分に該当する成分の合計１００質量部に対して、α、β−不飽和ケトン及び／又はα、β−不飽和アルデヒド各々の成分に該当する成分の合計は０〜１００質量部、好ましくは０．２〜１００質量部である。配合量が１００質量部より多いとアミン、ホルムアルデヒドなどに対する消臭効果の持続性が悪化する傾向にある。
【００１６】
また、熱硬化性樹脂と、香料系消臭剤との配合方法としては、例えば、熱硬化性樹脂に香料系消臭剤を添加ないし溶融混合する方法、水及び／又はアルコール等の溶剤に香料系消臭剤を添加混合した溶液ないし懸濁液、シリカ系微粒子、炭酸カルシウム粉末、ケイ酸カルシウム粉末、熱可塑性樹脂粉末、ヘキサメチレンテトラミン等の無機質・有機質微粉粒体ないしはゼオライト、活性炭等の多孔質粉粒体に香料系消臭剤を担持させたものを熱硬化性樹脂に添加混合する方法又は熱硬化性樹脂配合時若しくは硬化剤に直接添加する方法などが例示されるが、これらに限定されるものではない。本発明に用いられる香料系消臭剤は耐アルカリ性に優れているため、例えばヘキサメチレンテトラミン水溶液に混合して用いることができる。また熱硬化性樹脂への香料系消臭剤の配合量としては、熱硬化性樹脂１００質量部に対して０．０１〜５．０質量部の範囲が好ましく、特に好ましくは０．０２〜２．０質量部である。配合量が０．０１質量部未満では消臭効果が小さい傾向にあり、逆に５．０質量部を超えても消臭効果は変わらず、しかも経済的にも不利となる傾向にある。
【００１７】
なお、熱硬化性樹脂、硬化剤などへの香料系消臭剤の分散性を高めるためには界面活性剤や溶剤を用いるのが好ましい。界面活性剤としては、カチオン系界面活性剤、アニオン系界面活性剤、ノニオン系界面活性剤、両性界面活性剤などが挙げられる。溶剤としては、ポリアルキレングリコールなどの多価アルコール類や、フタル酸エステル類などが挙げられる。また、本発明の熱硬化性樹脂組成物には、前記必須成分の他、例えばヘキサメチレンテトラミン等の硬化剤、ステアリン酸カルシウム等の離型剤、硬化促進剤などを加えることができる。
【００１８】
【実施例】
次に、本発明を実施例によりさらに詳細に説明するが、本発明はこれらの例によってなんら限定されるものではない。なお、熱硬化性樹脂組成物を用いて製作した検体（レジンフェルト及び積層体）の曲げ強度及び臭気の官能試験については下記の試験法により行なった。
【００１９】
（１）曲げ強度（Ｎ／ｃｍ２）
レジンフェルトはＪＩＳ Ａ ５９０８（焼成条件 １８０℃で１０分間）、積層体はＪＩＳ Ｋ ６９１１に準処して測定した。
【００２０】
（２）臭気の官能試験
温調された金型内（▲１▼レジンフェルトでは２２０℃で６０秒間、▲２▼積層体では１８０℃で３５分間）で成形体を成形して型開きした時の臭気を、下記の評価方法及び評価基準に基づく官能試験で評価した。
【００２１】
（ｉ）評価方法
室温２０℃、相対湿度６０％下で、１５名（内女性５名）の臭気パネラーが官能評価し、得られた官能評価レベルの平均レベルで優劣を評価した。なお、このレベルが高いほど消臭効果が高いことを意味する。
【００２２】
（ｉｉ）評価基準
レベル４：刺激臭はほとんど感じられない。
レベル３：刺激臭はやや感じられるが実用上支障はない。
レベル２：刺激臭はやや強く感じる。
レベル１：刺激臭は非常に強く感じる。
【００２３】
（３）熱硬化性樹脂組成物の有する消臭効果の持続性評価
熱硬化性樹脂組成物を室温下で５週間保管した後に上記（２）臭気の官能試験を行って消臭効果の持続性を評価した。
【００２４】
＜実施例１＞
撹拌機、還流管、温度計を備えたガラス製反応フラスコ内にフェノール１０００ｇ、４７質量％ホルマリン水溶液４８０ｇ、触媒として蓚酸３ｇを入れてからかき混ぜながら還流反応させた後、加熱減圧下で濃縮してノボラック型フェノール樹脂を合成した。次いで、所定温度まで冷却し、該ノボラック型フェノール樹脂１００ｇに対し、表１に示す消臭剤Ｉを０．２ｇの割合で添加混合して熱硬化性樹脂組成物を得た。得られた熱硬化性樹脂組成物は、さらにヘキサメチレンテトラミン（１５質量％／熱硬化性樹脂）と離型剤（１質量％／熱硬化性樹脂）を添加粉砕して粉末とし、熱硬化性樹脂組成物（Ｉ）とした。この熱硬化性樹脂組成物（Ｉ）を次に示す評価例（レジンフェルトの製造）における繊維基材のバインダーとして用いた。
【００２５】
【表１】
評価例（レジンフェルトの製造）
麻繊維５０質量％、綿繊維５０質量％からなる混合繊維基材１００ｇに上記の粉末状の熱硬化性樹脂組成物（Ｉ）を２３．２ｇ入れて十分に混合してフリースを作製した後、これを金型内で熱圧成形（温度２２０℃、圧力１０ｋｇ／ｃｍ２、時間１分間）して厚み３ｍｍの成形フェルト（１）を得た。この成形フェルトについては、上記試験法により曲げ強度を測定し、臭気の官能試験（レジンフェルトの成形時）を行った。その結果を表５に示す。
【００２７】
＜実施例２〜４＞
実施例１において、消臭剤Ｉを、それぞれ表２〜４に示す消臭剤ＩＩ〜ＩＶに変更した以外は、実施例１と同様にして熱硬化性樹脂組成物（ＩＩ）〜（ＩＶ）を用いた３種類の成形フェルト（２）〜（４）を得た。得られた成形フェルトについては、実施例１と同様にしてそれぞれの曲げ強度の測定及び臭気の官能試験を行った。その結果を表５に示す。
【００２８】
【表２】
【表３】
【表４】
＜比較例１〜２＞
実施例１において、消臭剤を使用せず（比較例１）、又は消臭剤Ｉをエアーケム６６２Ｍ（商品名、第一工業製薬株式会社製）に変更（比較例２）した以外は、実施例１と同様にして比較対象用の成形フェルト（５）と（６）を得た。得られた成形フェルトについては、曲げ強度の測定及び臭気の官能試験を行った。その結果を表５に示す。
【００３２】
【表５】
＜実施例５＞
撹拌機、還流管、温度計を備えたガラス製反応フラスコにビスフェノールＡ１０００ｇ、４７質量％ホルムアルデヒド水溶液１９６ｇ、９２％パラホルムアルデヒド１００ｇ（ホルムアルデヒド／ビスフェノールＡのモル比＝１．４）および酢酸亜鉛５ｇを入れてからかき混ぜながら徐々に昇温し還流温度で４時間反応させた。次に減圧下で所定温度まで脱水濃縮を行なってから減圧を解除し、ベンジリックエーテル型フェノール樹脂を得た。
【００３４】
続いて、該ベンジリックエーテル型フェノール樹脂１００ｇに対し、表１に示す消臭剤Ｉを０．２ｇの割合で配合させることにより熱硬化性樹脂組成物（Ｖ）とした。得られた熱硬化性樹脂組成物は、次に示す評価例（積層体の製造）において評価した。
【００３５】
評価例（積層体の製造）
２００リットルパルパー（回転数３５００回転／分）内に水１２０リットルと新聞古紙７００ｇを投入し５分間攪拌処理して古紙を粉砕ないし離解状態としたスラリーを得た。次いで、このスラリーを攪拌翼付混合槽（回転数６００回転／分）に全量移送し、前記の粉末状の熱硬化性樹脂組成物（Ｖ）を３００．６ｇ投入して１０分間攪拌混合し、さらにポリアクリルアミド系定着剤を添加後攪拌混合して抄造用スラリーを得た。次いで、この抄造用スラリーを角型バッチ式抄造機（抄造網１５０メッシュ、１０００×１０００ｍｍ）に全量投入し、ろ過し、吸引圧搾脱水を行なってシート状湿潤成形体を８０℃のオーブン内で乾燥させて未硬化状態で秤量９５０ｇ／ｍ２の熱硬化性成形体を得た。引き続き、前述同様の操作を繰り返して同種の熱硬化性成形体を１４枚作製した。次いで、高さ１９ｍｍの金枠内に前記熱硬化性成形体１４枚を積層戴置し、温度１８０℃及び圧力６ｋｇ／ｃｍ２で３５分間加熱加圧して厚み１９ｍｍの積層体（１）を作成した。この積層体については、上記試験法により曲げ強度を測定し、臭気の官能試験（積層体の成形時）を行った。その結果を表６に示す。
【００３６】
＜実施例６〜８＞
実施例５において、消臭剤Ｉを表２〜４に示す消臭剤ＩＩ〜ＩＶに変更した以外は、実施例５と同様にして熱硬化性樹脂組成物（ＶＩ）〜（ＶＩＩＩ）を用いた３種類の積層体（２）〜（４）を得た。得られた積層体については、実施例５と同様にしてそれぞれの曲げ強度の測定及び臭気の官能試験（積層体の成形時）を行った。その結果を表６に示す。
【００３７】
＜比較例３〜４＞
実施例５において、消臭剤を使用せず（比較例３）、又は消臭剤Ｉをエアーケム６６２Ｍ（商品名、第一工業製薬株式会社製）に変更（比較例４）した以外は、実施例５と同様にして比較対象用の積層体（５）及び（６）を得た。得られた積層体については、曲げ強度を測定し、臭気の官能試験を行った。その結果を表６に示す。
【００３８】
【表６】
＜実施例９＞
実施例４で作製した熱硬化性樹脂組成物（ＩＶ）をポリ袋内に詰めた後、上部開放状態で５週間室温で保管して前記試験法により臭気の官能試験（レジンフェルトの製造時）を行った。なお、比較対象として比較例１の熱硬化性樹脂組成物を用いた。その結果、官能臭気レベルは、比較例１の熱硬化性樹脂組成物の臭気レベル１に対し、熱硬化性樹脂組成物（ＩＶ）（実施例４）の臭気レベルは４であり、熱硬化性樹脂組成物作製時点と全く変わらない結果であることから、本発明の熱硬化性樹脂組成物は持続性のある消臭効果を有することが確認された。
【００４０】
【発明の効果】
本発明の香料系消臭剤が配合された熱硬化性樹脂組成物を用いることにより、従来の消臭剤を使用し又は使用しない熱硬化性樹脂組成物よりも、アミン、ホルムアルデヒド等に起因する臭気を大幅に軽減できるため、作業環境の悪化を防止し、又は改善に寄与することができる。本発明の熱硬化性樹脂組成物は、加熱賦形化を要する製品、例えば自動車部品用、土木建築材料用、構造部材用積層板、電気絶縁用積層板、ロックウールボード、ガラス繊維強化板等に利用することができる。
【００４１】
更に、本発明の熱硬化性樹脂組成物は、長期間に亘り消臭効果を保持し、長期保管した製品の使用による作業環境への悪影響を生じる恐れもないため、製造者にとっては、製品の品質管理又は製品保証の面での寄与度は極めて大きく有益である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a thermosetting resin composition containing a fragrance-based deodorant capable of preventing or improving the working environment by reducing unpleasant odors such as amines and formaldehyde having a low odor threshold.
[0002]
[Prior art]
Conventionally, heat-insulating and sound-insulating materials (resin felt, resin foam), wood-based composite materials, molding materials, abrasive / friction materials, laminates, adhesives, etc., in the presence or absence of a curing agent or curing catalyst Curable resins that exhibit thermosetting properties are used as binders or matrix resins.
[0003]
For example, molding materials using various fibers as a reinforcing material and a thermosetting phenolic resin as a matrix resin, such as sheet molding compound, bulk molding compound, pultrusion (pultruding method), resin injection method (resin In the press-in method and the resin transfer molding method (RTM), a phenol resin is generally mainly used as a matrix resin.
[0004]
[Problems to be solved by the invention]
However, when this type of thermosetting phenol resin is used, the unreacted phenol in the resin at the time of molding and ammonia (0) having an unpleasant odor having a low odor threshold due to hexamethylenetetramine used as a curing agent are low. .59 ppm), amines such as trimethylamine (0.0014 ppm), and formaldehyde (1.9 ppm) are generated, which causes a problem of deteriorating the work environment. Has been taken.
[0005]
For example, a method using a resole-type phenol resin that exhibits thermosetting properties without using hexamethylenetetramine as a binder, or a deodorant capable of reducing odor, for example, an orange oil disclosed in JP-A-9-38748 Attempts have been made to use a deodorant containing turpentine oil and cedarwood oil as a main component, and the effect of reducing odor can be obtained to some extent, but it cannot be said that it is sufficient, and there is a need for room for further improvement.
[0006]
As described above, the present invention has been made to prevent or improve the working environment from being deteriorated due to an unpleasant odor generated when a thermosetting resin is used as a binder or a matrix resin. The object of the present invention is to provide a thermosetting resin composition containing a fragrance-based deodorant which is particularly effective in reducing odors caused by amines, formaldehyde and the like having a low odor threshold. An object of the present invention is to provide a thermosetting resin composition containing a fragrance-based deodorant excellent in persistence of odor ability.
[0007]
[Means for Solving the Problems]
The present inventors have conducted intensive studies on the above problems from the viewpoint of a deodorant, and as a result, a thermosetting resin composition containing a fragrance-based deodorant containing a specific ester has been found to achieve the above objects. They have found that they are effective, and have completed the present invention.
[0008]
That is, the thermosetting resin composition of the present invention is characterized by comprising (A) a thermosetting resin and (B) a fragrance-based deodorant containing an ester having a tricyclic hydrocarbon skeleton. I do. In the present invention, the fragrance-based deodorant preferably contains at least one selected from α, β-unsaturated ketones and α, β-unsaturated aldehydes, and particularly has 5 to 16 carbon atoms. More preferably, they are α, β-unsaturated ketones and α, β-unsaturated aldehydes.
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
The (A) thermosetting resin used in the present invention is used as a binder or a matrix resin such as a fiber base material, an organic / inorganic filler, an adhesive, a heat insulating / soundproofing material, etc., and is used as a curing agent or a curing catalyst. For example, those having a bonding function by thermosetting in the presence or absence of hexamethylenetetramine, polyisocyanate, acidic compound, peroxide and the like. Examples of such a thermosetting resin include a phenol resin, a melamine resin, a urea resin, a xylene resin, an epoxy resin, a polyfunctional acrylamide resin (Japanese Patent Publication No. 7-106421), an unsaturated polyester, and a diallyl phthalate resin. And alkyd resins. These may be used alone or in combination of two or more.
[0010]
The phenolic resin (A) as a thermosetting resin contains, as a main component, a condensation product obtained by reacting a phenol with an aldehyde in the presence of an acidic catalyst and / or a basic catalyst. A phenolic resin that exhibits thermosetting properties in the presence or absence of a curing catalyst, specifically, a novolak-type phenolic resin, a resole-type phenolic resin, an alkali resole-type phenolic resin, a nitrogen-containing resole-type phenolic resin, benzene Rick ether type phenolic resin and any compound after or after the production of these resins, for example, epoxy resin, melamine resin, urea resin, xylene resin, vinyl acetate resin, polyamide resin, urea compound, melamine compound, epoxy compound , Modified by mixing or reacting with ash nut oil Such as phenol resin.
[0011]
The fragrance-based deodorant used in the present invention contains (B) an ester having a tricyclic hydrocarbon skeleton as an essential component. Specific examples of such an ester include ethyl tricyclo [5.2.1.0 2,6 ] decane-2-carboxylate (furtate; manufactured by Kao), tricyclo [5.2.1.0 2, 6 ] propyl decane-2-carboxylate, tricyclo [5.2.1.0 2,6 ] butyl decane-2-carboxylate, ceryl acetate, caryophyllene acetate, tricyclodecenyl acetate, tricyclodecyl acetate, etc. No. Among these, ethyl tricyclo [5.2.1.0 2,6 ] decane-2-carboxylate (flutate) is particularly preferred from the viewpoint of the stability of the deodorizing effect.
[0012]
Further, as the fragrance-based deodorant, for example, in order to maintain the persistence of the deodorant effect even under alkaline conditions such as a hexamethylenetetramine aqueous solution used as a curing agent or a highly alkaline phenol resin, in the alkali region Only the (B) ester having a tricyclic hydrocarbon skeleton which is excellent in stability may be used. However, the ester having the (B) tricyclic hydrocarbon skeleton is used as a base, and it is chemically reacted with amine, formaldehyde and the like. Α, β-unsaturated ketones and α, β-unsaturated aldehydes having high deodorizing effect, especially at least one selected from α, β-unsaturated ketones having 5 to 16 carbon atoms and α, β-unsaturated aldehydes Is more preferably added in an appropriate amount according to the quality of the odor.
[0013]
As the α, β-unsaturated ketone, specifically, α- or β- or γ-damascon, α- or β-damasenone, α- or β- or γ-yonone, α- or β- or γ-methylyonone, acetophenone, p-methylacetophenone, methyl-β-naphthylketone, tentarome, α- or β-isomethylyonone, α- or β- or γ-iron, maltol, ethylmaltol, cis -Jasmon, dihydrojasmon, l-carvone, nootkatone and the like. Among these, α- or β- or γ-damascon, α- or β-damasenone, maltol, and ethyl maltol are particularly preferred from the viewpoint of the deodorizing effect.
[0014]
Examples of the α, β-unsaturated aldehyde include t-2-hexenal, 2,6-nonadienal, citral, benzaldehyde, α-hexylcinnamic aldehyde, α-amyl cinnamic aldehyde, heliotropin, and anisaldehyde. , Vanillin, ethyl vanillin, cuminaldehyde, cinnamaldehyde, perilaldehyde and the like. Among these, heliotropin, anisaldehyde, vanillin, and ethylvanillin are particularly preferred from the viewpoint of the deodorizing effect.
[0015]
The blending amount of at least one component selected from the above α, β-unsaturated ketone and α, β-unsaturated aldehyde is determined according to the use, but generally, the component (B) is based on mass. Is 100 to 100 parts by mass, preferably 0 to 100 parts by mass, preferably 0.1 to 100 parts by mass, based on 100 parts by mass of the components corresponding to .alpha., .Beta.-unsaturated ketone and / or .alpha., .Beta.-unsaturated aldehyde. If the amount is more than 100 parts by mass, the sustainability of the deodorizing effect on amines, formaldehyde and the like tends to be deteriorated.
[0016]
Examples of the method of blending the thermosetting resin with the fragrance-based deodorant include a method of adding or melting and mixing a fragrance-based deodorant to the thermosetting resin, and a method of adding a fragrance to a solvent such as water and / or alcohol. Solution or suspension containing a mixed deodorant, silica-based fine particles, calcium carbonate powder, calcium silicate powder, thermoplastic resin powder, inorganic or organic fine powder such as hexamethylenetetramine, or porous material such as zeolite or activated carbon Examples of the method include a method in which a fragrance-based deodorant is carried on a porous powder and added to a thermosetting resin, or a method in which a thermosetting resin is blended or directly added to a curing agent. It is not done. Since the fragrance-based deodorant used in the present invention has excellent alkali resistance, it can be used by being mixed with, for example, an aqueous solution of hexamethylenetetramine. The amount of the fragrance-based deodorant added to the thermosetting resin is preferably in the range of 0.01 to 5.0 parts by mass, particularly preferably 0.02 to 2 parts by mass, per 100 parts by mass of the thermosetting resin. 0.0 parts by mass. If the amount is less than 0.01 part by mass, the deodorizing effect tends to be small. Conversely, if the amount exceeds 5.0 parts by mass, the deodorizing effect does not change and tends to be economically disadvantageous.
[0017]
In order to enhance the dispersibility of the fragrance-based deodorant in a thermosetting resin, a curing agent, or the like, it is preferable to use a surfactant or a solvent. Examples of the surfactant include a cationic surfactant, an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant. Examples of the solvent include polyhydric alcohols such as polyalkylene glycol and phthalic acid esters. The thermosetting resin composition of the present invention may further contain, in addition to the essential components, a curing agent such as hexamethylenetetramine, a release agent such as calcium stearate, and a curing accelerator.
[0018]
【Example】
Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, the sensory test of the bending strength and the odor of the sample (resin felt and laminated body) manufactured using the thermosetting resin composition was performed by the following test methods.
[0019]
(1) Flexural strength (N / cm 2 )
Resin felt was measured according to JIS A 5908 (calcining conditions at 180 ° C. for 10 minutes), and the laminate was measured according to JIS K 6911.
[0020]
(2) Odor sensory test When a molded article is molded and opened in a temperature-controlled mold (1) at 220 ° C for 60 seconds for resin felt, and 2) at 180 ° C for 35 minutes for a laminated body. Was evaluated by a sensory test based on the following evaluation methods and evaluation criteria.
[0021]
(I) Evaluation method Fifteen odor panelists (five women) performed sensory evaluation at room temperature of 20 ° C. and relative humidity of 60%, and evaluated the average level of the obtained sensory evaluation levels. The higher the level, the higher the deodorizing effect.
[0022]
(Ii) Evaluation reference level 4: Almost no irritating odor is felt.
Level 3: Irritating odor is slightly felt, but there is no practical problem.
Level 2: The irritating odor is somewhat strong.
Level 1: The irritating odor is very strong.
[0023]
(3) Evaluation of the persistence of the deodorizing effect of the thermosetting resin composition After storing the thermosetting resin composition at room temperature for 5 weeks, the above-mentioned (2) Sensory test of odor was conducted to maintain the deodorizing effect. Was evaluated.
[0024]
<Example 1>
In a glass reaction flask equipped with a stirrer, a reflux tube, and a thermometer, 1000 g of phenol, 480 g of a 47% by mass formalin aqueous solution, and 3 g of oxalic acid as a catalyst were mixed, and the mixture was refluxed with stirring, and then concentrated under heating and reduced pressure. A novolak type phenol resin was synthesized. Next, the mixture was cooled to a predetermined temperature, and the deodorant I shown in Table 1 was added and mixed at a ratio of 0.2 g to 100 g of the novolak-type phenol resin to obtain a thermosetting resin composition. The obtained thermosetting resin composition is further pulverized by adding hexamethylenetetramine (15% by mass / thermosetting resin) and a release agent (1% by mass / thermosetting resin) to form a powder, Resin composition (I) was obtained. This thermosetting resin composition (I) was used as a binder for a fiber base in the following evaluation examples (production of resin felt).
[0025]
[Table 1]
Evaluation example (manufacture of resin felt)
After 23.2 g of the above powdery thermosetting resin composition (I) was added to 100 g of a mixed fiber base material composed of 50% by mass of hemp fiber and 50% by mass of cotton fiber and mixed well to prepare a fleece, This was hot-pressed in a mold (temperature: 220 ° C., pressure: 10 kg / cm 2 , time: 1 minute) to obtain a molded felt (1) having a thickness of 3 mm. For this molded felt, the bending strength was measured by the above test method, and an odor sensory test (at the time of molding the resin felt) was performed. Table 5 shows the results.
[0027]
<Examples 2 to 4>
In Example 1, the thermosetting resin compositions (II) to (IV) were the same as in Example 1 except that the deodorant I was changed to deodorants II to IV shown in Tables 2 to 4, respectively. To obtain three types of molded felts (2) to (4). About the obtained molded felt, measurement of each bending strength and odor sensory test were performed in the same manner as in Example 1. Table 5 shows the results.
[0028]
[Table 2]
[Table 3]
[Table 4]
<Comparative Examples 1-2>
Example 1 was carried out in the same manner as in Example 1 except that the deodorant was not used (Comparative Example 1) or the deodorant I was changed to Airchem 662M (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) (Comparative Example 2). In the same manner as in Example 1, molded felts (5) and (6) for comparison were obtained. About the obtained molded felt, the bending strength was measured and the odor sensory test was performed. Table 5 shows the results.
[0032]
[Table 5]
<Example 5>
A glass reaction flask equipped with a stirrer, a reflux tube, and a thermometer was charged with 1000 g of bisphenol A, 196 g of a 47% by mass aqueous formaldehyde solution, 100 g of 92% paraformaldehyde (molar ratio of formaldehyde / bisphenol A = 1.4) and 5 g of zinc acetate. The temperature was gradually raised while stirring, and the reaction was carried out at reflux temperature for 4 hours. Next, after dehydrating and concentrating to a predetermined temperature under reduced pressure, the reduced pressure was released to obtain a benzylic ether type phenol resin.
[0034]
Subsequently, 0.2 g of the deodorant I shown in Table 1 was added to 100 g of the benzylic ether-type phenol resin to obtain a thermosetting resin composition (V). The obtained thermosetting resin composition was evaluated in the following evaluation examples (production of a laminate).
[0035]
Evaluation example (production of laminate)
120 liters of water and 700 g of used newspaper were put into a 200 liter pulper (rotation speed: 3500 rpm) and stirred for 5 minutes to obtain a slurry in which the used paper was pulverized or disintegrated. Next, the whole amount of the slurry was transferred to a mixing tank equipped with stirring blades (rotation speed: 600 rpm), and 300.6 g of the powdery thermosetting resin composition (V) was charged and stirred and mixed for 10 minutes. Further, a polyacrylamide-based fixing agent was added and stirred and mixed to obtain a papermaking slurry. Next, the whole amount of the slurry for papermaking is put into a square batch-type papermaking machine (papermaking net 150 mesh, 1000 × 1000 mm), filtered, suction-pressed and dewatered, and the sheet-like wet molded body is dried in an oven at 80 ° C. In this way, a thermosetting molded body weighing 950 g / m 2 in an uncured state was obtained. Subsequently, the same operation as described above was repeated to produce 14 thermosetting molded articles of the same type. Next, 14 thermosetting moldings are stacked and placed in a 19 mm high metal frame, and heated and pressed at a temperature of 180 ° C. and a pressure of 6 kg / cm 2 for 35 minutes to form a 19 mm thick laminated body (1). did. With respect to this laminate, the bending strength was measured by the above-described test method, and an odor sensory test (at the time of molding the laminate) was performed. Table 6 shows the results.
[0036]
<Examples 6 to 8>
In Example 5, the thermosetting resin compositions (VI) to (VIII) were used in the same manner as in Example 5, except that the deodorant I was changed to deodorants II to IV shown in Tables 2 to 4. Thus, three types of laminates (2) to (4) were obtained. About the obtained laminated body, the bending strength measurement and the odor sensory test (at the time of forming the laminated body) were performed in the same manner as in Example 5. Table 6 shows the results.
[0037]
<Comparative Examples 3 and 4>
Example 5 was carried out in the same manner as in Example 5 except that the deodorant was not used (Comparative Example 3) or the deodorant I was changed to Airchem 662M (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) (Comparative Example 4). In the same manner as in Example 5, laminates (5) and (6) for comparison were obtained. About the obtained laminated body, the bending strength was measured and the sensory test of the odor was performed. Table 6 shows the results.
[0038]
[Table 6]
<Example 9>
After the thermosetting resin composition (IV) prepared in Example 4 was packed in a plastic bag, it was stored at room temperature for 5 weeks with the top open, and the sensory test for odor was conducted according to the test method (at the time of manufacturing resin felt). Was done. The thermosetting resin composition of Comparative Example 1 was used as a comparative object. As a result, the odor level of the thermosetting resin composition (IV) (Example 4) was 4 with respect to the odor level 1 of the thermosetting resin composition of Comparative Example 1, and the functional odor level was 4. Since the results were not different from those at the time of preparing the resin composition, it was confirmed that the thermosetting resin composition of the present invention had a persistent deodorizing effect.
[0040]
【The invention's effect】
By using a thermosetting resin composition in which the fragrance-based deodorant of the present invention is blended, the use of a conventional deodorant or a thermosetting resin composition not using a deodorant causes amine, formaldehyde, and the like. Since the odor can be significantly reduced, deterioration of the working environment can be prevented or contributed to improvement. The thermosetting resin composition of the present invention is a product requiring heat shaping, such as a laminate for an automobile part, a civil engineering building material, a laminate for a structural member, a laminate for electrical insulation, a rock wool board, a glass fiber reinforced plate, and the like. Can be used for
[0041]
Furthermore, the thermosetting resin composition of the present invention retains the deodorizing effect over a long period of time, and there is no possibility that the use of a product stored for a long time will adversely affect the working environment. The contribution in terms of quality control or product assurance is extremely large and beneficial.
Claims (3)
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| CN106700000A (en) * | 2016-12-13 | 2017-05-24 | 沈阳化工大学 | Heat-resistant phenolic resin containing 4-dimethyl amino cinnamyl aldehyde and preparation method thereof |
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