JP3978830B2 - Adhesive composition - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、接着剤組成物に関するものであり、さらに詳しくは酢酸ビニル系重合体の有機溶剤溶液単独を樹脂分とする接着剤組成物の貼り合わせ可能時間を延長し、貼り合わせ可能時間中の初期接着力に対する環境の影響を低減し、且つ耐久性（特に耐水性）を向上せしめた接着剤組成物に関する。
【０００２】
【従来の技術】
建材用の接着剤、特に床に軟質ポリ塩化ビニル（以下ＰＶＣという）装飾シ−トまたはタイルなどを床下地に施工する際に使用される接着剤として、酢酸ビニル系重合体をメタノ−ルなどの有機溶剤に溶解した溶液に、充填材（炭酸カルシウム、クレ−、タルクなど）や添加剤を加えたペ−スト状の接着剤が使用されている。
【０００３】
しかしながら、この接着剤は溶剤の揮発により初期接着力を発現せしめるため、溶剤の揮発が速い場合には、貼り合わせ可能時間中の初期接着力は優れるものの貼り合わせ可能時間が確保しにくく、溶剤の揮発が遅い場合には、貼り合わせ可能時間が確保出来るものの貼り合わせ可能時間中の初期接着力が弱い、つまり性能が環境に左右されやすいといった欠点を有し、また、施工後の耐久性（特に耐水性）に劣るとの欠点を有していた。
【０００４】
特公昭４９−２３８１２号公報には界面活性剤を添加する方法が提案されているが、貼り合わせ可能時間の延長化効果は認められるものの、貼り合わせ可能時間中における初期接着力及び施工後の耐久性（特に耐水性）が充分では無いといった欠点を有している。
【０００５】
また特開平６−１４５６２１号公報にはポリカプロラクトンを配合する方法が提案されており、貼り合わせ可能時間の延長化効果、貼り合わせ可能時間中における初期接着力向上効果は認められるものの、施工後の耐久性（特に耐水性）は充分ではないといった欠点を有している。
【０００６】
【発明が解決しようとする課題】
本発明は、含有溶剤揮発量の、貼り合わせ可能時間や貼り合わせ可能時間中における初期接着力への影響を少なくし、且つ架橋機構を有するため、施工後の耐久性（特に耐水性）に優れる接着剤組成物を提供することを目的とする。
【０００７】
【課題を解決するための手段】
本発明者等は、上記実状に鑑みて上記課題について鋭意検討したところ、ポリカプロラクトンポリオ−ルをポリオ−ル成分とし、末端にイソシアネ−ト基を有するウレタン樹脂を使用することにより、作業工程に見合った貼り合わせ可能時間を有し、貼り合わせ可能時間中の初期接着力に対する環境の影響を低減し、且つ施工後の耐久性（特に耐水性）に優れる接着剤を供給可能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、本発明は、酢酸ビニル系重合体の有機溶剤溶液（Ａ）と、末端にイソシアネ−ト基を有し、ポリオール成分としてポリカプロラクトンポリオ−ルを含むウレタン樹脂（Ｂ）とを含んでなることを特徴とする接着剤組成物を提供するものであり、好ましくはウレタン樹脂（Ｂ）のイソシアネ−ト基の含有量が、酢酸ビニル系重合体の有機溶剤溶液（Ａ）とウレタン樹脂（Ｂ）の総量１００重量部に対して、固形分換算で２重量部以上であり、好ましくはウレタン樹脂（Ｂ）のポリオ−ル成分が、ポリカプロラクトンポリオ−ルを１０重量％以上含んでなる接着剤組成物を提供するものである。
【０００９】
【発明の実施の形態】
本発明の酢酸ビニル系重合体の有機溶剤溶液（Ａ）中の酢酸ビニル系重合体としては、例えば酢酸ビニルホモポリマ−の他、酢酸ビニルとエチレン、プロピレンなどのオレフィン系、アクリル酸、メタクリル酸などの不飽和酸またはそのアルキルエステル、塩化ビニルなどの酢酸ビニルモノマ−と共重合可能なモノマ−を使用した共重合体が挙げられる。
【００１０】
酢酸ビニル系重合体は、１０,０００〜２００,０００の分子量を有する重合物が一般的に使用される。
有機溶剤としては、酢酸ビニル系重合体を溶解可能であり、イソシアネ−ト基と反応する官能基を有さないものであれば特に限定されないが、例えば酢酸エチル、トルエン、アセトンなどが挙げられる。
【００１１】
酢酸ビニル系重合体と有機溶剤の比率は特に限定されるものでは無いが、一般的には、重量比で酢酸ビニル系重合体：有機溶剤＝２０〜８０：８０〜２０のものが使用される。
【００１２】
本発明で使用する１液反応型ウレタン樹脂（Ｂ）の含有するポリオ−ル成分中のポリカプロラクトンポリオ−ルとしては、ε−カプロラクトンを開環重合したポリカプロラクトンポリオ−ルであればよいが、その中でも、２５℃において液状であり、酢酸ビニル系重合体を溶解している溶剤に溶解するものが、配合物の相溶性が良好であるため好ましい。特に、分子末端に平均２個以上の水酸基を有し、その分子量が１００〜５,０００である液状ポリカプロラクトンポリオ−ルが、末端にイソシアネ−ト基を有する１液反応型ウレタン樹脂と酢酸ビニル系重合体の有機溶剤溶液との相溶性も比較的良好であるためより好ましい。また、ポリカプロラクトンポリオ−ルのポリオ−ル成分中に占める割合としては、固形分配合比において、１０重量％以上であることが好ましい。
【００１３】
１０重量％に満たないと、酢酸ビニル系重合体有機溶剤溶液との相溶性が損なわれ、配合物が経時において分離する傾向が大きくなる。
また、ポリカプロラクトンポリオール以外の他のポリオ−ル成分としては、ポリオキシアルキレンポリオ−ル、ポリエステルポリオ−ル、ポリブタジエンポリオ−ル、水添ポリブタジエンポリオ−ル若しくはポリアクリルポリオ−ルなどが挙げられる。これらのイソシアネ−ト基と反応する活性水素含有化合物をそれぞれ単独若しくは併用して用いることができる。これらのうち１液反応型ウレタン樹脂の粘度及び耐久性（特に耐水性）の点から、ポリオキシアルキレンポリオ−ル、ポリブタジエンポリオ−ルを併用することが好ましい。
【００１４】
本発明で使用するウレタン樹脂（Ｂ）に使用されるイソシアネ−ト成分としては、例えば２ , ４−トリレンジイソシアネ−ト、２,６−トリレンジイソシアネ−ト、２,４−ジフェニルメタンジイソシアネ−ト、４,４’−ジフェニルメタンジイソシアネ−ト、キシリレンジイソシアネ−ト、ポリメリックジフェニルメタンジイソシアネ−ト、カルボジイミド化ジフェニルメタンジイソシアネ−ト、１,５−ナフタレンジイソシアネ−トなどの芳香族ポリイソシアネ−ト類、エチレンジイソシアネ−ト、エチリデンジイソシアネ−ト、プロピレンジイソシアネ−ト、ブチレンジイソシアネ−ト、ヘキサメチレンジイソシアネ−ト、２,２,４−トリメチルヘキサメチレンジイソシアネ−トなどの脂肪族ポリイソシアネ−ト類、水添ジフェニルメタンジイソシアネ−ト、イソホロンジイソシアネ−ト、水添トリレンジイソシアネ−トなどの脂環式ポリイソシアネ−ト類などが挙げられる。
【００１５】
これらの中、使用されるイソシアネ−トは特に限定されるものでは無いが、反応性の点から芳香族ポリイソシアネ−ト類が好ましい。また、その使用量としては、ＮＣＯ／活性水素基の比率が１以上であれば特に限定されるものではないが、耐久性（特に耐水性）付与の観点より、酢酸ビニル系重合体の有機溶剤溶液（Ａ）と１液反応型ウレタン樹脂（Ｂ）の総量１００重量部に対して、イソシアネ−ト基の含有量が、固形分重量比において、２重量部以上にすることが好ましい。２重量部未満であると、耐久性（特に耐水性）が損なわれる恐れがある。
【００１６】
本発明の接着剤組成物は、例えば以下の様にして調整される。1)ポリカプロラクトンポリオ−ルとその他のポリオ−ルを混合の後、ポリイソシアネ−トを反応せしめる方法、2)ポリカプロラクトンポリオ−ルとポリイソシアネ−トを反応の後その他のポリオ−ルを反応せしめる方法、3)その他のポリオ−ルとポリイソシアネ−トを反応の後ポリカプロラクトンポリオ−ルを反応せしめる方法である。その際、希釈剤としては、イソシアネ−ト基との反応点を有さない有機溶剤、可塑剤などが使用出来、これらの有機溶剤又は可塑剤は単独又は混合して用いられる。
【００１７】
本発明の接着剤は、通常、樹脂単独で貼り合わせ可能時間が長く、貼り合わせ可能時間中における初期接着力に優れ、且つ耐久性（特に耐水性）に優れる１液反応型接着剤として使用することが出来る。
【００１８】
また、上記の成分（Ａ）と（Ｂ）以外にも必要に応じて着色剤、貯蔵安定化剤、充填材、チキソ性付与剤、シランカップリング剤などの接着性付与剤、反応速度を調整するための触媒、作業粘度を調整するための希釈剤（溶剤、可塑剤など）、湿気との反応により活性水素が発生するブロック化活性水素含有化合物及び他の添加剤を混合して接着剤として用いることが出来る。
【００１９】
本発明の接着剤は、無機質からなるボ−ドへの浸透性に優れ、装飾シ−ト、タイル、ボ−ド、フォ−ムなどに対する接着力が良好であり、実使用上問題の無い貼り合わせ可能時間を有し、貼り合わせ可能時間中における初期接着力に優れ、且つ施工後の耐久性（特に耐水性）に優れる。
【００２０】
【実施例】
次に本発明の実施例及び比較例を示す。以下、特に断りが無い限り、部は重量比を、％は重量％を示すものとする。
【００２１】
参考例１ ＜ポリウレタン系プレポリマ−の合成＞
２Ｌ４ツ口フラスコに分子量が２,０００のポリプロピレンジオ−ル３２３部と分子量が約２,０００のポリカプロラクトントリオ−ル３２３部を仕込み脱水を行った後、還流回路をセットし、ジブチル錫ジラウレ−トを５０ｐｐｍを添加し、４０℃にてジフェニルメタンジイソシアネ−ト３５４部を一括添加してＮＣＯ％が一定になるまで約７５℃で反応を行った。粘度が６５,０００ｍＰａ・Ｓ／２５℃であり、イソシアネ−ト含有量が９．１重量％である液状樹脂１を得た。
【００２２】
参考例２ ＜ポリウレタン系プレポリマ−の合成＞
２Ｌ４ツ口フラスコに分子量が２,０００のポリプロピレンジオ−ル６１５部と分子量が２,０００のポリカプロラクトントリオ−ル６９部を仕込み脱水を行った後、還流回路をセットし、ジブチル錫ジラウレ−トを５０ｐｐｍを添加し、４０℃にてジフェニルメタンジイソシアネ−ト３１５部を一括添加してＮＣＯ％が一定になるまで７５℃で反応を行った。粘度が２５,０００ｍＰａ・Ｓ／２５℃であり、イソシアネ−ト含有量が７．６重量％である液状樹脂２を得た。
【００２３】
参考例３ ＜ポリウレタン系プレポリマ−の合成＞
２Ｌ４ツ口フラスコに分子量が２,０００のポリプロピレンジオ−ル６９５部を仕込み脱水を行った後、還流回路をセットし、ジブチル錫ジラウレ−ト５０ｐｐｍを添加し、４０℃にてジフェニルメタンジイソシアネ−ト３０５部を一括添加してイソシアネ−ト含有量が一定になるまで約７５℃で反応を行った。粘度が４,５００ｍＰａ・Ｓ／２５℃であり、ＮＣＯ％が７．３％である液状樹脂３を得た。
【００２４】
実施例１〜４及び比較例１〜２
酢酸ビニル系重合体の有機溶剤溶液としてセビアンＰ−５３８６（ダイセル化学工業社製、Ｎ．Ｖ．＝約６３％、酢酸エチル／トルエン＝５０／５０）を用い、上記参考例１、２、３で得られた樹脂１、樹脂２、樹脂３を表１及び表２に示す配合比にて混合し、下記の試験を行った。
【００２５】
実施例１
酢酸ビニル系重合体の有機溶剤溶液と樹脂１を固形分配合比で、６３：７の比率でブレンドして用いた例。
【００２６】
実施例２
酢酸ビニル系重合体有機溶剤溶液と樹脂１を固形分配合比で、６３：２５の比率でブレンドして用いた例。
【００２７】
実施例３
酢酸ビニル系重合体有機溶剤溶液と樹脂２を固形分配合比で、６３：７の比率でブレンドして用いた例。
【００２８】
実施例４
酢酸ビニル系重合体有機溶剤溶液と樹脂２を固形分配合比で、６３：２５の比率でブレンドして用いた例。
【００２９】
比較例１
酢酸ビニル系重合体有機溶剤溶液単独を用いた例。
比較例２
酢酸ビニル系重合体有機溶剤溶液と樹脂３を固形分配合比で、６３：２５の比率でブレンドして用いた例。
【００３０】
＜試験法及び評価基準＞
（初期接着力及び貼り合わせ可能時間）
実施例、比較例で得られた接着剤をスレ−ト板上にガラス棒を用いて固形分の膜厚が約０．４ｍｍとなる様に塗布し、約５℃×３５％ＲＨ、約２０℃×６５％ＲＨ、約３５℃×９５％ＲＨ条件下での経時における接着力を測定した。
【００３１】
（耐水性）
実施例、比較例で得られた接着剤をガラス板上にガラス棒を用いて固形分の膜厚が約０．４ｍｍとなる様に塗布し、約２０℃×６５％ＲＨ条件下で１日養生後、約２０℃の水中に７日間浸漬した時の接着剤の状態を確認した。
【００３２】
（接着強度）
各試験環境下において、塗布後１０分毎の平面引張強度を測定した。
但し、平面部の素材は面積約１ｃｍ2のＳＵＳとし、圧締強度約１ｋｇ／ｃｍ2、圧締時間約１０秒、圧締,引張速度約２００ｍｍ／ｍｉｎの条件にて測定した。
【００３３】
（貼り合わせ可能時間）
接着強度測定方法において、ＳＵＳへの付着度合において判定した。
（耐水性）
接着剤剤皮膜の溶融の有無を確認した。
【００３４】
これらの結果を実施例１,２,３及び４、比較例１及び２として表１及び表２に示す。但し、配合において接着剤中の溶剤含有量を均一にするため、酢酸エチル及びトルエンを用いて、Ｎ．Ｖ．が約６３％になる様に調整した。
【００３５】
【表１】
表中、樹脂１,２及び３の括弧内の数値は、ＯＨ成分中におけるポリカプロラクトンポリオ−ルの含有率を示す。
表中、接着力の単位はＫｇ／ｃｍ2である。またＡＦとは接着剤がＳＵＳ面に濡れなくなった状態、つまり貼り合わせ可能時間を過ぎた状態を表す。
【００３７】
【表２】
表中、樹脂１,２及び３の括弧内の数値は、ＯＨ成分中におけるポリカプロラクトンポリオ−ルの含有率を示す。
表中、接着力の単位はＫｇ／ｃｍ2である。またＡＦとは接着剤がＳＵＳ面に濡れなくなった状態、つまり貼り合わせ可能時間を過ぎた状態を表す。
ここで、相溶性がある場合には、経時においても著しい分離傾向を生じない。貼り合わせ可能時間は各条件下で３０分以上あれば実使用上問題が無く、貼り合わせ可能時間中の初期接着力は２．０ｋｇ／ｃｍ2以上であれば、実使用に適している。また、耐水性は、フィルムが完全溶融しなければ実使用上問題が無い。従って、実施例１〜４においてその性能は、比較例１,２と比べて、相溶性を有し、貼り合わせ可能時間と貼り合わせ可能時間中の初期接着力のバランスが実用上優れており、また、耐水性にも優れており、大きな性能向上が認められる。
【００３９】
【発明の効果】
本発明の接着剤組成物は、塗布後、実使用上問題の無い貼り合わせ可能時間を有し、貼り合わせ可能時間の接着力の立ち上がり性が良好であり、且つ耐久性（特に耐水性）に優れる。特に、例えば充填材、チキソ性付与剤、可塑剤、触媒などとコンパウンド化することにより、貼り合わせ可能時間中の基材の納まり性に優れ、耐久性に優れる床材用接着剤組成物を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an adhesive composition, and more particularly, extends the bonding time of the adhesive composition having a resin component of an organic solvent solution of a vinyl acetate polymer alone, The present invention relates to an adhesive composition in which the influence of the environment on the initial adhesive force is reduced and the durability (particularly water resistance) is improved.
[0002]
[Prior art]
Adhesives for building materials, especially vinyl acetate polymers as methanol as adhesives used when flooring soft polyvinyl chloride (PVC) decorative sheets or tiles on floors Paste-like adhesives in which fillers (calcium carbonate, clay, talc, etc.) and additives are added to a solution dissolved in the above organic solvent are used.
[0003]
However, since this adhesive exhibits initial adhesive force due to the volatilization of the solvent, when the volatilization of the solvent is fast, the initial adhesive force during the bonding possible time is excellent, but it is difficult to secure the bonding possible time. When the volatilization is slow, the bonding time can be secured, but the initial adhesive force during the bonding time is weak, that is, the performance is easily influenced by the environment, and the durability after construction (especially The water resistance was inferior.
[0004]
Japanese Patent Publication No. SHO 49-23812 proposes a method of adding a surfactant, but although an effect of extending the possible bonding time is recognized, the initial adhesive force during the bonding possible time and the durability after construction. The property (particularly water resistance) is not sufficient.
[0005]
JP-A-6-145621 proposes a method of blending polycaprolactone, and although the effect of extending the bonding possible time and the effect of improving the initial adhesive force during the bonding possible time are recognized, Durability (particularly water resistance) has the drawback of not being sufficient.
[0006]
[Problems to be solved by the invention]
The present invention reduces the influence of the solvent volatilization amount on the initial adhesive force during the bonding possible time and the bonding possible time and has a crosslinking mechanism, so that it is excellent in durability after construction (particularly water resistance). An object is to provide an adhesive composition.
[0007]
[Means for Solving the Problems]
The present inventors diligently studied the above-mentioned problems in view of the above-mentioned situation, and as a result of using a urethane resin having a polycaprolactone polyol as a polyol component and having an isocyanate group at the terminal, It has been found that it has a suitable bonding time, can reduce the influence of the environment on the initial adhesive force during the bonding time, and can supply an adhesive with excellent durability (particularly water resistance) after construction. The present invention has been completed.
[0008]
That is, the present invention comprises an organic solvent solution (A) of a vinyl acetate polymer and a urethane resin (B) having an isocyanate group at the end and containing polycaprolactone polyol as a polyol component. The content of the isocyanate group of the urethane resin (B) is preferably an organic solvent solution (A) of the vinyl acetate polymer and the urethane resin (B). ) In an amount of 2 parts by weight or more in terms of solid content, and preferably the polyurethane component of the urethane resin (B) contains 10% by weight or more of polycaprolactone polyol. A composition is provided.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the vinyl acetate polymer in the organic solvent solution (A) of the vinyl acetate polymer of the present invention include vinyl acetate homopolymer, olefins such as vinyl acetate and ethylene, propylene, acrylic acid, and methacrylic acid. And a copolymer using a monomer copolymerizable with an unsaturated acid such as an alkyl ester or a vinyl acetate monomer such as vinyl chloride.
[0010]
As the vinyl acetate polymer, a polymer having a molecular weight of 10,000 to 200,000 is generally used.
The organic solvent is not particularly limited as long as it can dissolve a vinyl acetate polymer and does not have a functional group that reacts with an isocyanate group, and examples thereof include ethyl acetate, toluene, and acetone.
[0011]
The ratio between the vinyl acetate polymer and the organic solvent is not particularly limited, but generally, a vinyl acetate polymer: organic solvent = 20-80: 80-20 by weight ratio is used. .
[0012]
The polycaprolactone polyol in the polyol component contained in the one-component reactive urethane resin (B) used in the present invention may be a polycaprolactone polyol obtained by ring-opening polymerization of ε-caprolactone. Among these, those which are liquid at 25 ° C. and are dissolved in a solvent in which a vinyl acetate polymer is dissolved are preferred because the compatibility of the blend is good. In particular, a liquid polycaprolactone polyol having an average of two or more hydroxyl groups at the molecular terminals and having a molecular weight of 100 to 5,000 is a one-component reactive urethane resin and vinyl acetate having an isocyanate group at the terminal. The compatibility of the polymer with the organic solvent solution is also preferable because it is relatively good. The proportion of polycaprolactone polyol in the polyol component is preferably 10% by weight or more in the solid content blending ratio.
[0013]
If it is less than 10% by weight, the compatibility with the vinyl acetate polymer organic solvent solution is impaired, and the tendency of the blend to separate over time increases.
Examples of other polyol components other than polycaprolactone polyol include polyoxyalkylene polyol, polyester polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, and polyacryl polyol. These active hydrogen-containing compounds that react with isocyanate groups can be used alone or in combination. Of these, polyoxyalkylene polyol and polybutadiene polyol are preferably used in combination from the viewpoint of viscosity and durability (particularly water resistance) of the one-component reactive urethane resin.
[0014]
Isocyanate used in the urethane resin (B) used in the present invention - The DOO component, e.g. 2, 4 - tolylene diisocyanate - DOO, 2,6-tolylene diisocyanate - DOO, 2,4-diphenylmethane Isocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, polymeric diphenylmethane diisocyanate, carbodiimidized diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate Aromatic polyisocyanates such as ethylene, ethylene diisocyanate, ethylidene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, 2,2, Aliphatic polyisocyanates such as 4-trimethylhexamethylene diisocyanate, hydrogenated diphenylmethane Soshiane - DOO, isophorone diisocyanate - DOO, hydrogenated tolylene diisocyanate - alicyclic polyisocyanates such bets - such as preparative acids and the like.
[0015]
Among these, the isocyanate used is not particularly limited, but aromatic polyisocyanates are preferable from the viewpoint of reactivity. The amount used is not particularly limited as long as the ratio of NCO / active hydrogen groups is 1 or more, but from the viewpoint of imparting durability (particularly water resistance), an organic solvent for a vinyl acetate polymer. It is preferable that the content of the isocyanate group is 2 parts by weight or more in the solid content weight ratio with respect to 100 parts by weight of the total amount of the solution (A) and the one-component reactive urethane resin (B). If it is less than 2 parts by weight, durability (particularly water resistance) may be impaired.
[0016]
The adhesive composition of the present invention is prepared, for example, as follows. 1) Method of reacting polyisocyanate after mixing polycaprolactone polyol and other polyol, 2) Method of reacting polycaprolactone polyol and polyisocyanate and then reacting other polyol 3) A method of reacting other polyols with polyisocyanate and then reacting with polycaprolactone polyol. In that case, as a diluent, an organic solvent, a plasticizer, etc. which do not have a reactive site with an isocyanate group can be used, and these organic solvents or plasticizers are used alone or in combination.
[0017]
The adhesive of the present invention is usually used as a one-component reactive adhesive that has a long bonding time with a resin alone, has excellent initial adhesive strength during bonding, and has excellent durability (particularly water resistance). I can do it.
[0018]
In addition to the above components (A) and (B), as necessary, adhesion imparting agents such as colorants, storage stabilizers, fillers, thixotropic agents, silane coupling agents, and reaction rates are adjusted. As an adhesive by mixing a catalyst for controlling the working viscosity, a diluent (solvent, plasticizer, etc.), a blocked active hydrogen-containing compound that generates active hydrogen by reaction with moisture, and other additives Can be used.
[0019]
The adhesive of the present invention has excellent permeability to boards made of inorganic materials, has good adhesion to decorative sheets, tiles, boards, foams, etc., and has no problem in practical use. It has a bonding time, is excellent in initial adhesive strength during the bonding time, and is excellent in durability after construction (particularly water resistance).
[0020]
【Example】
Next, examples and comparative examples of the present invention will be shown. Hereinafter, unless otherwise specified, parts represent weight ratios and% represents weight%.
[0021]
Reference Example 1 <Synthesis of polyurethane prepolymer>
After charging 323 parts of a polypropylene diol having a molecular weight of 2,000 and 323 parts of a polycaprolactone triol having a molecular weight of about 2,000 in a 2L four-necked flask, a reflux circuit was set, and dibutyltin dilaurate was added. Then, 354 parts of diphenylmethane diisocyanate was added all at once at 40 ° C., and the reaction was carried out at about 75 ° C. until the NCO% became constant. A liquid resin 1 having a viscosity of 65,000 mPa · S / 25 ° C. and an isocyanate content of 9.1% by weight was obtained.
[0022]
Reference Example 2 <Synthesis of polyurethane prepolymer>
A 2L 4-necked flask was charged with 615 parts of a polypropylene diol having a molecular weight of 2,000 and 69 parts of a polycaprolactone triol having a molecular weight of 2,000. After dehydration, a reflux circuit was set and dibutyltin dilaurate was added. Was added at once, and 315 parts of diphenylmethane diisocyanate was added all at once at 40 ° C., and the reaction was carried out at 75 ° C. until the NCO% became constant. A liquid resin 2 having a viscosity of 25,000 mPa · S / 25 ° C. and an isocyanate content of 7.6% by weight was obtained.
[0023]
Reference Example 3 <Synthesis of polyurethane prepolymer>
After adding 695 parts of polypropylene diol having a molecular weight of 2,000 to a 2 L four-necked flask and performing dehydration, a reflux circuit was set, 50 ppm of dibutyltin dilaurate was added, and diphenylmethane diisocyanate was added at 40 ° C. A total of 305 parts was added at a time, and the reaction was carried out at about 75 ° C. until the isocyanate content became constant. A liquid resin 3 having a viscosity of 4,500 mPa · S / 25 ° C. and an NCO% of 7.3% was obtained.
[0024]
Examples 1-4 and Comparative Examples 1-2
Ceviane P-5386 (manufactured by Daicel Chemical Industries, NV = approximately 63%, ethyl acetate / toluene = 50/50) was used as the organic solvent solution of the vinyl acetate polymer, and the above Reference Examples 1, 2, 3 were used. The resin 1, the resin 2 and the resin 3 obtained in 1 were mixed at the blending ratios shown in Tables 1 and 2, and the following tests were performed.
[0025]
Example 1
An example in which an organic solvent solution of a vinyl acetate polymer and resin 1 are blended at a solid content ratio of 63: 7.
[0026]
Example 2
An example in which a vinyl acetate polymer organic solvent solution and a resin 1 are blended at a solid content ratio of 63:25.
[0027]
Example 3
An example in which a vinyl acetate polymer organic solvent solution and resin 2 are blended at a solid content ratio of 63: 7.
[0028]
Example 4
An example in which a vinyl acetate polymer organic solvent solution and a resin 2 are blended at a ratio of solid content of 63:25.
[0029]
Comparative Example 1
An example using a vinyl acetate polymer organic solvent solution alone.
Comparative Example 2
An example in which a vinyl acetate polymer organic solvent solution and the resin 3 are blended at a solid content ratio of 63:25.
[0030]
<Test methods and evaluation criteria>
(Initial adhesive strength and possible bonding time)
The adhesives obtained in Examples and Comparative Examples were coated on a slate plate using a glass rod so that the solid film thickness was about 0.4 mm, and about 5 ° C. × 35% RH, about 20 The adhesive strength over time was measured under the conditions of ° C x 65% RH and about 35 ° C x 95% RH.
[0031]
(water resistant)
The adhesives obtained in the Examples and Comparative Examples were applied on a glass plate using a glass rod so that the solid film thickness was about 0.4 mm, and were treated for 1 day under conditions of about 20 ° C. × 65% RH. After curing, the state of the adhesive when immersed in water at about 20 ° C. for 7 days was confirmed.
[0032]
(Adhesive strength)
Under each test environment, the plane tensile strength was measured every 10 minutes after application.
However, the material of the flat portion was SUS having an area of about 1 cm 2 , and the measurement was performed under conditions of a pressing strength of about 1 kg / cm 2 , a pressing time of about 10 seconds, a pressing and a tensile speed of about 200 mm / min.
[0033]
(Pastable time)
In the adhesive strength measurement method, the degree of adhesion to SUS was determined.
(water resistant)
The presence or absence of melting of the adhesive film was confirmed.
[0034]
These results are shown in Tables 1 and 2 as Examples 1, 2, 3 and 4 and Comparative Examples 1 and 2. However, in order to make the solvent content in the adhesive uniform in the blending, N.I. V. Was adjusted to about 63%.
[0035]
[Table 1]
In the table, the numbers in parentheses for resins 1, 2 and 3 indicate the content of polycaprolactone polyol in the OH component.
In the table, the unit of adhesive strength is Kg / cm 2 . AF represents a state in which the adhesive is not wetted with the SUS surface, that is, a state in which the pastable time has passed.
[0037]
[Table 2]
In the table, the numbers in parentheses for resins 1, 2 and 3 indicate the content of polycaprolactone polyol in the OH component.
In the table, the unit of adhesive strength is Kg / cm 2 . AF represents a state in which the adhesive is not wetted with the SUS surface, that is, a state in which the pastable time has passed.
Here, when there is compatibility, no significant separation tendency occurs even with time. If the bonding time is 30 minutes or more under each condition, there is no problem in actual use, and if the initial adhesive force during the bonding time is 2.0 kg / cm 2 or more, it is suitable for actual use. Further, the water resistance has no problem in practical use unless the film is completely melted. Therefore, the performance in Examples 1 to 4 is compatible with that in Comparative Examples 1 and 2, and the balance between the bonding time and the initial adhesive force during the bonding time is practically excellent. Moreover, it is excellent also in water resistance, and a big performance improvement is recognized.
[0039]
【The invention's effect】
The adhesive composition of the present invention has a bonding time that does not cause a problem in actual use after coating, has a good rise in adhesive force during the bonding time, and has durability (particularly water resistance). Excellent. In particular, by providing a compound with a filler, thixotropic agent, plasticizer, catalyst, etc., an adhesive composition for a flooring material that has excellent base material fitability and durability during bonding time is provided. can do.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29698097A JP3978830B2 (en) | 1997-10-29 | 1997-10-29 | Adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29698097A JP3978830B2 (en) | 1997-10-29 | 1997-10-29 | Adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11131046A JPH11131046A (en) | 1999-05-18 |
| JP3978830B2 true JP3978830B2 (en) | 2007-09-19 |
Family
ID=17840701
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29698097A Expired - Fee Related JP3978830B2 (en) | 1997-10-29 | 1997-10-29 | Adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3978830B2 (en) |
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1997
- 1997-10-29 JP JP29698097A patent/JP3978830B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11131046A (en) | 1999-05-18 |
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