JP5523746B2 - One-component moisture-curing urethane adhesive for synthetic resin flooring and floor structure using this one-component moisture-curing urethane adhesive - Google Patents
One-component moisture-curing urethane adhesive for synthetic resin flooring and floor structure using this one-component moisture-curing urethane adhesive Download PDFInfo
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- JP5523746B2 JP5523746B2 JP2009129787A JP2009129787A JP5523746B2 JP 5523746 B2 JP5523746 B2 JP 5523746B2 JP 2009129787 A JP2009129787 A JP 2009129787A JP 2009129787 A JP2009129787 A JP 2009129787A JP 5523746 B2 JP5523746 B2 JP 5523746B2
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- Prior art keywords
- adhesive
- urethane
- synthetic resin
- resin
- flooring
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- 239000000853 adhesive Substances 0.000 title claims description 101
- 230000001070 adhesive effect Effects 0.000 title claims description 99
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- 238000009408 flooring Methods 0.000 title claims description 57
- 229920003002 synthetic resin Polymers 0.000 title claims description 53
- 239000000057 synthetic resin Substances 0.000 title claims description 53
- 238000013008 moisture curing Methods 0.000 title claims description 19
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- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、合成樹脂製床材用一液湿気硬化型ウレタン接着剤及びこの一液湿気硬化型ウレタン接着剤を使用した床構造に関するものである。 The present invention relates to a one-component moisture-curable urethane adhesive for synthetic resin flooring and a floor structure using this one-component moisture-curable urethane adhesive.
従来より、コンクリート、モルタル、耐水合板や、これらの表面を防水層で処理した床下地に、塩化ビニル樹脂の合成樹脂製床材を接着する場合、一液湿気硬化型ウレタン接着剤が汎用されている。
この場合、一液湿気硬化型ウレタン接着剤を、くし目ごてを用いて床下地の表面にくし目状に塗布した後、合成樹脂製床材を接着する工法が一般に採用されている。
一液湿気硬化型ウレタン接着剤は、施工性や接着強度等の点で優れているため、長期に亘って強固に床下地に合成樹脂製床材を接着することができ、使用中に（人が歩行することによって等）合成樹脂製床材が床下地から剥がれたり、下地から床材の一部が遊離して床材表面に膨れが生じる等の不具合を防止できるという優れた特性を有している。
Conventionally, when a synthetic resin floor material made of vinyl chloride resin is bonded to concrete, mortar, water-resistant plywood, or floor bases treated with a waterproof layer, a one-component moisture-curing urethane adhesive has been widely used. Yes.
In this case, a one-component moisture-curing urethane adhesive is generally applied to the surface of the floor base using a comb iron, and then a synthetic resin floor material is bonded.
One-component moisture-curing urethane adhesives are excellent in terms of workability and adhesive strength, and so can be used to firmly bond synthetic resin flooring to the floor base for a long time. It has excellent characteristics that it can prevent problems such as the synthetic resin flooring peeling off from the floor base or part of the flooring being released from the base and causing swelling on the floor surface. ing.
その一方で、近年、汚れたり、古くなった合成樹脂製床材の改修を行う頻度が高まってきた結果、新たな合成樹脂製床材を敷設するために、既設の合成樹脂製床材を床下地から容易に剥離、除去できるようにすることについての要望が強くなってきた。 On the other hand, in recent years, the frequency of repairing dirty or old synthetic resin flooring has increased, and as a result, existing synthetic resin flooring has been installed under the floor to lay new synthetic resin flooring. There has been a growing demand for easy peeling and removal from the ground.
しかしながら、既設の合成樹脂製床材は、前記のように床下地に強固に接着されているため、既設の合成樹脂製床材を床下地から剥離、除去するのに、多大な手数がかかるという問題があった。 However, since the existing synthetic resin flooring is firmly bonded to the floor base as described above, it takes a lot of work to peel and remove the existing synthetic resin flooring from the floor base. There was a problem.
この問題に対処するため、ポリオールとポリイソシアネート化合物とを反応させて得られるイソシアネート基を有するウレタンプレポリマーと中空フィラーを必須成分とする再剥離可能な一液湿気硬化型ウレタン接着剤が提案されている（特許文献１）。 In order to cope with this problem, a releasable one-part moisture curable urethane adhesive comprising an isocyanate group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate compound and a hollow filler as an essential component has been proposed. (Patent Document 1).
しかしながら、特許文献１に記載された接着剤は、接着剤の比重を調整するために特殊な中空フィラーを用いることを必須とするものであるとともに、対象が木質直貼りフローリング材に限られるため、そのまま合成樹脂製床材には適用できなかった。 However, the adhesive described in Patent Document 1 is essential to use a special hollow filler in order to adjust the specific gravity of the adhesive, and because the target is limited to a wood direct-bonded flooring material, It could not be applied to a synthetic resin floor as it is.
本発明は、上記従来の合成樹脂製床材用一液湿気硬化型ウレタン接着剤の有する問題点に鑑み、使用中に合成樹脂製床材が床下地から剥がれたり、膨れたりする等の不具合を生じないようにできるという耐久性及び耐水性に関する基本的な特性を備えながら、改修等に際して、既設の合成樹脂製床材を床下地から容易に剥離、除去できるようにした合成樹脂製床材用一液湿気硬化型ウレタン接着剤及びこの一液湿気硬化型ウレタン接着剤を使用した床構造を提供することを目的とする。 In view of the problems of the conventional one-component moisture-curing urethane adhesive for synthetic resin flooring, the present invention has problems such as the synthetic resin flooring being peeled off or swollen during use. For synthetic resin flooring that can easily remove and remove existing synthetic resin flooring from the floor base during refurbishment, etc. while having the basic characteristics of durability and water resistance that can be prevented from occurring An object of the present invention is to provide a one-component moisture-curable urethane adhesive and a floor structure using the one-component moisture-curable urethane adhesive.
上記目的を達成するため、本発明の合成樹脂製床材用一液湿気硬化型ウレタン接着剤は、合成樹脂製床材を床下地に接着するのに用いられる接着剤であって、ポリオールとポリイソシアネート化合物とを反応させて得られるイソシアネート基を有する下記のウレタンプレポリマー（Ａ）及び（Ｂ）に、難接着性樹脂粉体を配合してなり、硬化後、前記難接着性樹脂粉体が硬化したウレタン樹脂中に均一に分散して存在することになって、当該接着剤によって床下地に接着されている合成樹脂製床材に対して剥離させる力が加えられたとき、ウレタン樹脂と難接着性樹脂粉体との界面に沿って破壊するとともに、該破壊した界面からウレタン樹脂が凝集破壊することによって、合成樹脂製床材が床下地から剥離するものであることを特徴とする。
ウレタンプレポリマー（Ａ）：イソシアネート基と水酸基との比率〔ＮＣＯ〕／〔ＯＨ〕が１．０〜１．５となるようにイソシアネートとポリオールを配合して合成されたウレタンプレポリマー
ウレタンプレポリマー（Ｂ）：イソシアネート基と水酸基との比率〔ＮＣＯ〕／〔ＯＨ〕が１．５より大きくなるようにイソシアネートとポリオールを配合して合成されたウレタンプレポリマー
ここで、「難接着性樹脂」とは、ウレタン接着剤と接着性が無いか、若しくは非常に接着性が乏しい樹脂を意味する。
In order to achieve the above object, the one-component moisture-curing urethane adhesive for synthetic resin flooring of the present invention is an adhesive used for adhering a synthetic resin flooring to a floor base, comprising a polyol and a poly The following urethane prepolymers (A) and (B) having an isocyanate group obtained by reacting with an isocyanate compound are blended with a hardly adhesive resin powder. After curing, the hardly adhesive resin powder is When a force is applied to peel off the synthetic resin floor material that is adhered to the floor base by the adhesive, it is difficult to disperse in the urethane resin. While breaking along the interface with the adhesive resin powder, and the urethane resin cohesively breaks from the broken interface, the synthetic resin floor material is peeled off from the floor base.
Urethane prepolymer (A): Urethane prepolymer synthesized by blending isocyanate and polyol such that the ratio [NCO] / [OH] of isocyanate group to hydroxyl group is 1.0 to 1.5 Urethane prepolymer ( B): Urethane prepolymer synthesized by blending isocyanate and polyol such that the ratio [NCO] / [OH] of isocyanate group to hydroxyl group is greater than 1.5. , Means a resin having no adhesiveness with urethane adhesive or very poor adhesiveness.
この場合において、難接着性樹脂粉体に、ポリオレフィン樹脂粉体を用いることができる。 In this case, polyolefin resin powder can be used as the hardly adhesive resin powder.
また、ウレタンプレポリマーを構成するポリオールの少なくとも一部に、ひまし油系ポリオールを用いることができる。 A castor oil-based polyol can be used for at least a part of the polyol constituting the urethane prepolymer.
また、本発明の一液湿気硬化型ウレタン接着剤を使用した床構造は、上記の合成樹脂製床材用一液湿気硬化型ウレタン接着剤により、床下地に、該床下地側が合成樹脂からなる合成樹脂製床材を接着してなることを特徴とする。 In addition, the floor structure using the one-component moisture-curable urethane adhesive of the present invention is made of the above-described one-component moisture-curable urethane adhesive for synthetic resin flooring, and the floor substrate side is made of synthetic resin. It is characterized in that a synthetic resin floor material is bonded.
本発明の合成樹脂製床材用一液湿気硬化型ウレタン接着剤は、ポリオールとポリイソシアネート化合物とを反応させて得られるイソシアネート基を有するウレタンプレポリマーに、難接着性樹脂粉体を配合してなるものであることから、図１に示すように、硬化後、難接着性樹脂粉体が硬化した接着剤樹脂（ウレタンプレポリマー）中に均一に分散して存在することになる。換言すると、硬化した接着剤樹脂の「海」の中に、難接着性樹脂性粉体の粒子が「島」状に散在する海島構造を構成することになる。
このとき、難接着性樹脂粉体の粒子は、その表面が接着剤樹脂に対して難接着性であるので、接着剤樹脂と強固に接着することなく、実質的に遊離した状態となっている。
そして、このような状態の接着剤樹脂によって床下地に接着されている合成樹脂製床材は、外部から床材に対して剥離させる力が加えられたとき、接着剤樹脂が接着剤樹脂と難接着性樹脂粉体との界面に沿って破壊し（接着剤樹脂と難接着性樹脂粉体との界面で両者は実質的に接着一体化していないため、両者は界面で容易に分離するとともに、分離した界面から派生的に接着剤樹脂中に亀裂が伸長することとなるため、難接着性樹脂粉体を含まない場合に比べ、上記界面が存在する分だけ接着剤樹脂全体の凝集力が小さくなるとともに、接着剤樹脂中に亀裂が生じやすく、小さな力で接着剤樹脂が破壊されやすくなる。）、接着剤が接着剤樹脂単体の系や、接着剤樹脂とこの接着剤樹脂に対して接着性を有する添加物との混合系である場合に比べて、小さな力で合成樹脂製床材を床下地から容易に剥離、除去でき、易剥離性を有するものである。
この現象は、難接着性樹脂粉体が接着剤中に均一に分散しているため、単に難接着性樹脂粉体は接着剤樹脂中に散在するだけではなく、接着剤樹脂の接着界面や端面にも難接着性樹脂粉体の粒子が露出したり浅く埋没していることから、外部から加えられた剥離力が難接着性樹脂粉体の周囲の接着剤樹脂に応力集中し、接着剤樹脂に亀裂が発生しやすくなり、結果として接着剤樹脂が破断しやすくなる。
このように、この合成樹脂製床材用一液湿気硬化型ウレタン接着剤は、難接着性樹脂粉体を含まない場合に比べ、接着剤樹脂全体の凝集力が小さくなるので、合成樹脂製床材の剥離が、接着剤樹脂と床下地又は床材裏面との接着界面で剥離するのではなく、接着剤樹脂自体が凝集破壊することになる。
このように接着剤樹脂自体が凝集破壊することで合成樹脂製床材が剥離することから、床材を剥離するために必要な力を容易に管理でき、ウレタン接着剤に対して極端に接着性（親和性）の悪い床下地や、表面状態が極端に悪い床下地を除き、床下地の性状に関係なく、一定の力で、安定的に床材を剥離することができるとともに、使用中に（人が歩行することによって）合成樹脂製床材が床下地から剥がれたり、膨れたりする等の不具合を生じないようにできるという耐久性及び耐水性に関する基本的な特性を備えるようにできる。
また、接着剤樹脂自体が凝集破壊することで、合成樹脂製床材を剥離する際に、床下地の表層が接着剤樹脂側にとられて床下地を破損することがないので、床下地の補修をすることなく、改修工事を行うことができる。
The one-part moisture-curing urethane adhesive for synthetic resin flooring of the present invention comprises a urethane prepolymer having an isocyanate group obtained by reacting a polyol and a polyisocyanate compound with a hardly adhesive resin powder. Therefore, as shown in FIG. 1, after curing, the hardly-adhesive resin powder is uniformly dispersed in the cured adhesive resin (urethane prepolymer). In other words, a sea-island structure is formed in which the particles of the hardly-adhesive resinous powder are scattered in “islands” in the “sea” of the cured adhesive resin.
At this time, the particles of the hardly-adhesive resin powder are in a substantially free state without strongly adhering to the adhesive resin because the surface thereof is hardly adhesive to the adhesive resin. .
The synthetic resin floor material bonded to the floor base with the adhesive resin in such a state is difficult when the force is applied to the floor material from the outside when the adhesive resin is applied to the adhesive resin. Break along the interface with the adhesive resin powder (Because the two are not substantially bonded and integrated at the interface between the adhesive resin and the hardly adhesive resin powder, both are easily separated at the interface, Since the crack extends in the adhesive resin derivatively from the separated interface, the cohesive force of the adhesive resin as a whole is smaller by the presence of the interface compared to the case where the hardly adhesive resin powder is not included. At the same time, cracks are likely to occur in the adhesive resin, and the adhesive resin is easily destroyed with a small force.) The adhesive is bonded to the adhesive resin itself or to the adhesive resin and the adhesive resin. When it is a mixed system with additive Compared with a small force easily peeled off the synthetic resin floor material from the underfloor it can be removed, and has a easy peelability.
This phenomenon is because the hardly-adhesive resin powder is uniformly dispersed in the adhesive, so that the hardly-adhesive resin powder is not only scattered in the adhesive resin, but also the adhesive interface and end face of the adhesive resin. In addition, since the particles of the hard-to-adhesive resin powder are exposed or shallowly buried, the peeling force applied from the outside concentrates the stress on the adhesive resin around the hard-to-adhesive resin powder, and the adhesive resin Cracks are easily generated, and as a result, the adhesive resin is easily broken.
Thus, this one-component moisture-curing urethane adhesive for flooring made of synthetic resin has a lower cohesive force of the adhesive resin as compared with the case where hard-to-adhere resin powder is not included. The peeling of the material does not peel at the adhesive interface between the adhesive resin and the floor base or the back of the flooring material, but the adhesive resin itself cohesively breaks down.
In this way, the adhesive resin itself cohesively breaks and the synthetic resin flooring peels off, so the force required to peel off the flooring can be easily managed and extremely adhesive to urethane adhesives. Except for floor bases with poor (affinity) and floor bases with extremely poor surface conditions, the flooring can be peeled off with a constant force regardless of the properties of the floor base. It is possible to provide basic characteristics relating to durability and water resistance so that the synthetic resin flooring can be prevented from being peeled off or swollen from the floor base (by a person walking).
In addition, since the adhesive resin itself cohesively breaks, when the synthetic resin flooring is peeled off, the surface layer of the floor base is not taken on the adhesive resin side and the floor base is not damaged. Renovation work can be done without repairs.
また、難接着性樹脂粉体に、ポリオレフィン樹脂粉体を用いることにより、ポリオレフィン樹脂の比重（真比重）（通常は、０．８９〜０．９７ｇ／ｃｍ３程度）が、ウレタンプレポリマーの比重（ウレタンプレポリマーと溶媒の混合物（接着剤のうちの液体成分）の比重）（通常は、０．９５〜１．００ｇ／ｃｍ３程度）と近似しているため、接着剤中に難接着性樹脂粉体が均一に分散し、その状態を長期間維持することが可能となる。
このため、接着剤の塗布作業性が向上するとともに、硬化した接着剤樹脂と難接着性樹脂性粉体の粒子の海島構造が均一に構成され、接着力を均一化することができる。
また、接着剤の貯蔵安定性が向上し、長期間、未使用の状態で接着剤を保管しておいてもポリオレフィン樹脂粉体が分離して沈降したり、浮上したりすることがなく、長期保存が可能になり、効率よく接着剤の生産を行うことができる。
Further, by using polyolefin resin powder as the hardly adhesive resin powder, the specific gravity (true specific gravity) of the polyolefin resin (usually about 0.89 to 0.97 g / cm 3 ) can be increased by the specific gravity of the urethane prepolymer. Since it is close to (specific gravity of a mixture of urethane prepolymer and solvent (liquid component of the adhesive)) (usually about 0.95 to 1.00 g / cm 3 ), it is difficult to adhere to the adhesive. The resin powder is uniformly dispersed, and the state can be maintained for a long time.
For this reason, while the workability | operativity of an adhesive agent improves, the sea island structure of the particle | grains of hardened | cured adhesive resin and hard-to-adhere resinous powder is comprised uniformly, and it can equalize | bond adhesive force.
In addition, the storage stability of the adhesive is improved, and even if the adhesive is stored for a long period of time, the polyolefin resin powder does not separate and settle or float, Storage becomes possible, and an adhesive can be efficiently produced.
また、ウレタンプレポリマーを構成するポリオールの少なくとも一部に、ひまし油系ポリオールを用いることにより、硬化後の接着剤樹脂が、脆性を呈するようにすることができる。
このため、使用中は適当な接着強度を発揮する一方、脆い性質が加味されるために、合成樹脂製床材を剥離する際に、接着剤樹脂自体が凝集破壊しやすくなり、一層安定した剥離特性を発揮することができる。そして、この傾向は、後述のとおり、水中浸漬した後でも維持させることが水中浸漬した後の剥離試験でも確認されているので、床材裏面と接着剤層との接着界面若しくは接着剤層と床下地との接着界面に水分が侵入して界面の劣化が進んだ場合でも、接着剤樹脂自体の凝集破壊による安定した剥離特性を発揮することができる。
Further, by using a castor oil-based polyol as at least a part of the polyol constituting the urethane prepolymer, the cured adhesive resin can be made brittle.
For this reason, while exhibiting appropriate adhesive strength during use, the brittle nature is taken into account, so that when the synthetic resin flooring is peeled off, the adhesive resin itself tends to cohesively break down, and more stable peeling. The characteristic can be exhibited. And, as described later, this tendency has been confirmed in the peel test after being immersed in water to be maintained even after being immersed in water, so the adhesive interface between the back surface of the flooring material and the adhesive layer or the adhesive layer and the underfloor Even when moisture enters the adhesive interface with the ground and the interface deteriorates, stable peeling characteristics due to cohesive failure of the adhesive resin itself can be exhibited.
以下、本発明の合成樹脂製床材用一液湿気硬化型ウレタン接着剤及びこの一液湿気硬化型ウレタン接着剤を使用した床構造の実施の形態について説明する。 Hereinafter, an embodiment of a one-component moisture-curing urethane adhesive for a synthetic resin floor material of the present invention and a floor structure using the one-component moisture-curing urethane adhesive will be described.
本発明の合成樹脂製床材用一液湿気硬化型ウレタン接着剤は、合成樹脂製床材を床下地に接着するのに用いられる接着剤であって、ポリオールとポリイソシアネート化合物とを反応させて得られるイソシアネート基を有するウレタンプレポリマーに、難接着性樹脂粉体を配合してなるものである。
この場合、ウレタンプレポリマーには、難接着性樹脂粉体のほか、無機充填剤、揺変剤、希釈溶媒、その他の各種添加剤を配合することができる。
そして、この一液湿気硬化型ウレタン接着剤は、合成樹脂製床材用一液湿気硬化型ウレタン接着剤により、床下地に、少なくとも床下地側が合成樹脂からなる合成樹脂製床材を接着することによって床構造を構築することができる。
The one-component moisture-curing urethane adhesive for synthetic resin flooring of the present invention is an adhesive used for bonding a synthetic resin flooring to a floor base, and reacts a polyol with a polyisocyanate compound. The urethane prepolymer having an isocyanate group is blended with a hardly adhesive resin powder.
In this case, an inorganic filler, a thixotropic agent, a dilution solvent, and other various additives can be blended with the urethane prepolymer in addition to the hardly adhesive resin powder.
And this one-component moisture-curing urethane adhesive is to adhere a synthetic resin floor material, at least the floor substrate side is made of synthetic resin, to the floor substrate with a one-component moisture-curable urethane adhesive for synthetic resin flooring material. A floor structure can be constructed.
［ウレタンプレポリマー］
ウレタンプレポリマーは、単独で用いてもよいことはいうまでもないが、複数種のプレポリマーを組み合わせることが合成樹脂製床材用の接着剤としては効果的である。
すなわち、ベースとなるプレポリマー（Ａ）、下地との密着性を補助するためのプレポリマー（Ｂ）等を適宜組み合わせることが好ましい。
このようにすることで、下地との接着性（密着性）が向上するとともに、接着剤塗布後から床材を貼り付けることができる時間（貼り付け可能時間）を長くすることができ、施工性が向上する。
[Urethane prepolymer]
Needless to say, the urethane prepolymer may be used alone, but combining a plurality of types of prepolymers is effective as an adhesive for synthetic resin flooring.
That is, it is preferable to appropriately combine the prepolymer (A) serving as the base, the prepolymer (B) for assisting adhesion with the base, and the like.
By doing in this way, while improving the adhesiveness (adhesion) with the groundwork, it is possible to lengthen the time during which the flooring can be pasted after applying the adhesive (the pastable time), and the workability Will improve.
プレポリマー（Ａ）は、接着剤としての主要な性能を発揮するプレポリマーであって、その合成に用いるイソシアネート、ポリオールには特に制約はないが、イソシアネート基と水酸基との比率〔ＮＣＯ〕／〔ＯＨ〕が１．０〜１．５となるようにイソシアネートとポリオールを配合して合成したものであることが望ましい。 The prepolymer (A) is a prepolymer that exhibits the main performance as an adhesive, and the isocyanate and polyol used for the synthesis thereof are not particularly limited, but the ratio of isocyanate group to hydroxyl group [NCO] / [ It is desirable to mix and synthesize isocyanate and polyol so that OH] is 1.0 to 1.5.
一方、プレポリマー（Ｂ）は、下地材との密着性を確保したり、貼り付け可能時間を長くするためのプレポリマーであって、〔ＮＣＯ〕／〔ＯＨ〕が１．５より大きくなるようにイソシアネートとポリオールを配合して合成したものであることが望ましい。
この場合、ポリオールの数平均分子量は１０００以下であることが好ましい。
On the other hand, the prepolymer (B) is a prepolymer for ensuring adhesion with the base material or extending the pasting time, so that [NCO] / [OH] is larger than 1.5. It is desirable to be synthesized by blending an isocyanate and a polyol.
In this case, the number average molecular weight of the polyol is preferably 1000 or less.
（イソシアネート）
イソシアネートとしては、通常の一液湿気硬化型ウレタン組成物に用いられるポリイソシアネートであればいずれのものも使用することができる。例えば、以下のものを挙げることができる。
２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、ｐ−フェニ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、２，４−ジフェニルメタンジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート、１，５−ナフタレンジイソシアネート、トリジンジイソシアネート等の芳香族ジイソシアネート類、ポリフェニルメタンポリイソシアネート等の芳香族ポリイソシアネート類、
エチレンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、リジンジイソシアネート等の脂肪族ジイソシアネート類、
イソホロンジイソシアネート、シクロヘキシルジイソシアネート、ジシクロヘキシルメタンジイソシアネート、水添キシレンジイソシアネート、ノルボルネンジイソシアネート等の脂環族ジイソシアネート類、
前記イソシアネートのビウレット体、ダイマー体、トリマー体、ダイマー・トリマー体、ウレトンイミン変性体。
(Isocyanate)
As the isocyanate, any polyisocyanate can be used as long as it is a polyisocyanate used in a normal one-component moisture-curable urethane composition. For example, the following can be mentioned.
2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-phenylene diisocyanate, 4,4-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 1,5-naphthalene Aromatic diisocyanates such as diisocyanate and tolidine diisocyanate, aromatic polyisocyanates such as polyphenylmethane polyisocyanate,
Aliphatic diisocyanates such as ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate,
Alicyclic diisocyanates such as isophorone diisocyanate, cyclohexyl diisocyanate, dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate,
Biuret body, dimer body, trimer body, dimer / trimer body and uretonimine modified body of the isocyanate.
（ポリオール）
ポリオールとしては、以下のポリエーテルポリオール類、ポリエステルポリオール類、低分子量多価アルコール類、その他ポリオール類を単独又は２種以上混合したものを用いることができる。例えば、以下のものを挙げることができる。
ポリエーテルポリオール類：
エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、グリセリン、トリメチロールプロパン、１，２，５−ヘキサントリオール、１，３−ブタンジオール、１，４−ブタンジオール、ビスフェノールＡ、４，４−ジヒドロキシフェニルメタン、ペンタエリスリトール等の多価アルコールの１種又は２種以上にプロピレンオキサイド、エチレンオキサイド、ブチレンオキサイド等の１種又は２種以上を付加して得られるポリエーテルポリオールで、具体的には、例えば、ポリオキシエチレンジオール、ポリオキシプロピレンジオール、ポリオキシブチレンジオール、ポリオキシエチレントリオール、ポリオキシプロピレントリオール、また、テトラヒドロフランの開環重合によって得られるポリテトラメチレングリコール。
ポリエステルポリオール類：
エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、１，４−ブタンジオール、１，３−ブタンジオール、ネオペンチルグリコール、１，５−ペンタンジオール、ネオペンチググリコール、３−メチル−１，５−ペンタンジオール、１，６−ヘキサンジオール、２，２−ジエチル−１，３−プロパンジオール、１，８−オクタンジオール、２−エチル−１，３−ヘキサンジオール、２−ｎ−ブチル−２−エチル−１，３−プロパンジオール、２，４−ジエチル−１，５−ペンタンジオール、デカメチレングリコール、シクロヘキサンジメタノール、ビスフェノールＡのエチレンオキサイド又はプロピレンオキサイド付加物、トリメチロールプロパン、グリセリン、ペンタエリスリトール等の多価アルコールの１種又は２種以上と、コハク酸、グルタル酸、アジピン酸、アゼライン酸、セバシン酸、ドデカン二酸、ダイマー酸、水添ダイマー酸、テレフタル酸、イソフタル酸等の低分子量多価カルボン酸の１種又は２種以上との縮合重合体、及びプロピオンラクトン、バレロラクトン、カプロラクトン等の開環重合体。
低分子量多価アルコール類：
エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、１，４−ブタンジオール、１，３−ブタンジオール、ネオペンチルグリコール、１，５−ペンタンジオール、ネオペンチググリコール、３−メチル−１，５−ペンタンジオール、１，６−ヘキサンジオール、２，２−ジエチル−１，３−プロパンジオール、１，８−オクタンジオール、２−エチル−１，３−ヘキサンジオール、２−ｎ−ブチル−２−エチル−１，３−プロパンジオール、２，４−ジエチル−１，５−ペンタンジオール、デカメチレングリコール、シクロヘキサンジメタノール、ビスフェノールＡのエチレンオキサイド又はプロピレンオキサイド付加物、トリメチロールプロパン、グリセリン、ペンタエリスリトール等。
その他ポリオール類：
ポリカーボネートポリオール、ポリブタジエンポリオールとその水素添加物、ポリイソプレンポリオールとその水素添加物、アクリルポリオール、ひまし油系ポリオール等。
この中でも、ひまし油は後述する接着力（特に、耐水接着力）の評価で、接着剤の凝集破壊の比率が５０％を超えることから、非常に好ましい。接着剤の凝集破壊の比率が５０％を超えると、接着界面での剥離に比べて接着剤自体の凝集剥離の比率が大きいため、床材の剥離強度が安定し、床材の改修時には易剥離性を奏するとともに、床材使用時では必要な接着強度を確保することができる。
なお、ひまし油（蓖麻子油、Ｃａｓｔｏｒ ｏｉｌ）は植物油の一種で、不飽和脂肪酸（リシノール酸、オレイン酸、リノール酸等）と少量の飽和脂肪酸（パルミチン酸、ステアリン酸等）のグリセリドである。ひまし油系ポリオールとしては、１分子鎖当りに水酸基が２以上含まれるもの、特に、精製ひまし油を用いることが好ましい。
(Polyol)
As the polyol, the following polyether polyols, polyester polyols, low molecular weight polyhydric alcohols, and other polyols may be used alone or in combination of two or more. For example, the following can be mentioned.
Polyether polyols:
Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, 1,2,5-hexanetriol, 1,3-butanediol, 1,4-butanediol, bisphenol A, 4,4-dihydroxyphenyl A polyether polyol obtained by adding one or two or more of propylene oxide, ethylene oxide, butylene oxide or the like to one or more of polyhydric alcohols such as methane and pentaerythritol. Specifically, for example, , Polyoxyethylene diol, polyoxypropylene diol, polyoxybutylene diol, polyoxyethylene triol, polyoxypropylene triol, and polytetraethylene obtained by ring-opening polymerization of tetrahydrofuran Methylene glycol.
Polyester polyols:
Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, 1,5-pentanediol, neopentig glycol, 3-methyl-1,5- Pentanediol, 1,6-hexanediol, 2,2-diethyl-1,3-propanediol, 1,8-octanediol, 2-ethyl-1,3-hexanediol, 2-n-butyl-2-ethyl -1,3-propanediol, 2,4-diethyl-1,5-pentanediol, decamethylene glycol, cyclohexanedimethanol, ethylene oxide or propylene oxide adduct of bisphenol A, trimethylolpropane, glycerin, pentaerythritol, etc. Multivalent Low molecular weight polyvalent carboxylic acids such as succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid, hydrogenated dimer acid, terephthalic acid, isophthalic acid, etc. Or a ring-opening polymer such as propionlactone, valerolactone, caprolactone, and the like.
Low molecular weight polyhydric alcohols:
Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, 1,5-pentanediol, neopentig glycol, 3-methyl-1,5- Pentanediol, 1,6-hexanediol, 2,2-diethyl-1,3-propanediol, 1,8-octanediol, 2-ethyl-1,3-hexanediol, 2-n-butyl-2-ethyl -1,3-propanediol, 2,4-diethyl-1,5-pentanediol, decamethylene glycol, cyclohexanedimethanol, ethylene oxide or propylene oxide adduct of bisphenol A, trimethylolpropane, glycerin, pentaerythritol and the like.
Other polyols:
Polycarbonate polyol, polybutadiene polyol and its hydrogenated product, polyisoprene polyol and its hydrogenated product, acrylic polyol, castor oil-based polyol and the like.
Among these, castor oil is very preferable because the ratio of cohesive failure of the adhesive exceeds 50% in the evaluation of adhesive strength (particularly water-resistant adhesive strength) described later. If the ratio of cohesive failure of the adhesive exceeds 50%, the ratio of cohesive peeling of the adhesive itself is larger than that of peeling at the adhesive interface, so the peel strength of the flooring material is stable and easy peeling when the flooring material is repaired. As well as exhibiting the properties, it is possible to ensure the necessary adhesive strength when using the flooring.
Castor oil (castor oil) is a kind of vegetable oil, and is a glyceride of unsaturated fatty acid (such as ricinoleic acid, oleic acid, linoleic acid) and a small amount of saturated fatty acid (such as palmitic acid, stearic acid). As the castor oil-based polyol, one having two or more hydroxyl groups per molecular chain, particularly purified castor oil is preferably used.
プレポリマー（Ａ）とプレポリマー（Ｂ）と比率は、プレポリマー全体の質量を１００としたとき、プレポリマー（Ａ）が５０〜１００質量部となるように配合することが好ましい。
プレポリマー（Ａ）が５０質量部を下回ると、オープンタイムを短くして床材を貼り付けた場合、適切な初期接着強さが得られず、床材の巻き癖を抑えることができずに床材が下地から浮いてしまったり、施工中に床材がズレやすい。そのため長くオープンタイムをとる必要が生じ、結果として施工性が悪くなる。
プレポリマー（Ａ）とプレポリマー（Ｂ）との配合比率〔プレポリマー（Ａ）〕／〔プレポリマー（Ｂ）〕は、６０〜９０／１０〜４０とするとさらに好ましい。このようにすると、初期接着強さ発現速度、貼り付け可能時間、下地との密着性、床材への接着性のバランスが良好にできる。
The ratio of the prepolymer (A) to the prepolymer (B) is preferably blended so that the prepolymer (A) is 50 to 100 parts by mass when the total mass of the prepolymer is 100.
When the prepolymer (A) is less than 50 parts by mass, when the flooring is pasted with a short open time, an appropriate initial adhesive strength cannot be obtained, and curling of the flooring cannot be suppressed. The flooring floats off the ground, and the flooring is easily misaligned during construction. Therefore, it is necessary to take a long open time, resulting in poor workability.
The blending ratio [prepolymer (A)] / [prepolymer (B)] of the prepolymer (A) and the prepolymer (B) is more preferably 60 to 90/10 to 40. If it does in this way, initial balance strength expression speed, pasting time, adhesion with a groundwork, and the balance of adhesiveness to a flooring can be made favorable.
［難接着性樹脂粉体］
難接着性樹脂とは、ウレタン接着剤との接着性が無いか、若しくは非常に接着性が乏しい樹脂をいい、具体的には、ポリオレフィン、弗素樹脂等を挙げることができる。
そして、難接着性樹脂粉体には、難接着性樹脂を微粉砕した粉体（微粒子）を用いることができる。ただし、微小な粒状で重合した粉体の適用を妨げるものではない。
難接着性樹脂の中でも、接着剤の接着樹脂成分と比重の近いポリオレフィンが貯蔵中の分離現象を防止できるため、特に好ましく用いられる。その中でも、ポリエチレンが好ましい。ポリエチレンであれば、低密度ポリエチレン、直鎖状ポリエチレン、高密度ポリエチレン、ポリプロピレンとのブレンド体や共重合体等、ウレタン樹脂との接着性が乏しい限り、限定されるものではない。
弗素樹脂としては、ポリテトラフロオロエチレン、ポリクロロトリフルオロエチレン、ポリビニリデンフルオライド、ポリビニルフルオライド等が用いられるが、入手のしやすさの点でポリテトラフロオロエチレンが好ましい。
これらの粉体は、例えば、必要とされる床材の接着力や床材を剥離するために必要な力に応じて任意の量を添加することができるが、後述の実施例等から、ウレタンプレポリマー（複数のウレタンプレポリマーを用いる場合はそれらの合計）の容積を１００とした場合、粉体の容積が４０〜１６０、好ましくは、６０〜１３０となるように添加することが望ましい。
粉体の容積比が６０未満であると接着力が大きく、易剥離性が小さくなり、４０未満であるとその傾向が一層強まるが、大きい床材の接着力が必要とされる場合には、４０未満とすることも可能である。
また、容積比が１３０を超えると接着力が小さく、剥離性が大きくなり、１６０を超えるとその傾向が一層強まるが、大きい床材の接着力が必要とされない場合には、１６０を超えるようにすることも可能である。
難接着性樹脂粉体は、難接着性樹脂を微粉砕等によって粉体としたものだけではなく、接着性樹脂の粉体や無機物粉体の表面を難接着性の樹脂で被覆したもの、例えば、表面をシリコン処理したガラスビーズ等を用いることもできる。つまり、粉体表面にウレタン接着剤と接着性が無いか、若しくは非常に接着性が乏しい樹脂の層が形成されていても、同様の効果を奏することができる。
粒子のサイズ（粒径）は１ｍｍ以下とすることが望ましい。
１ｍｍよりも大きいサイズのものを用いると、難接着性樹脂が接着剤内で充分に分散した状態にならず、また、接着剤を塗布する際、くし目ごてのくし目に引っかかりやすくなって作業を阻害することになる。
好ましい粒子サイズは、１００μｍ以下であり、レーザー回折散乱法で測定したときの平均粒径が１０〜５０μｍ程度、より好ましくは、２０〜３０μｍ程度であることが、分散作業の容易さと奏する易剥離性のバランスをとる上で特に好ましい。
また、後述する実施例では、サイズが８〜６０μｍのフレーク状の粒子（平均粒径が２５μｍ程度）からなる粉体を用いている。
このように、難接着性樹脂粉体の粒子に、フレーク状の粒子を用いることによって、粒子の表面には大小の凹凸が存在するため、粒子の周囲で接着剤樹脂に対する破壊応力が凹凸部に集中しやすく、亀裂を伸長させることができる。
[Hard adhesive resin powder]
The hardly adhesive resin refers to a resin that does not have adhesiveness with a urethane adhesive or has very poor adhesiveness. Specific examples thereof include polyolefins and fluorine resins.
As the hardly adhesive resin powder, powder (fine particles) obtained by finely pulverizing the hardly adhesive resin can be used. However, this does not hinder the application of finely polymerized powder.
Among difficult-to-adhere resins, polyolefin having a specific gravity close to that of the adhesive resin component of the adhesive can be particularly preferably used because it can prevent a separation phenomenon during storage. Among these, polyethylene is preferable. If it is polyethylene, it will not be limited as long as adhesiveness with urethane resin, such as a low density polyethylene, a linear polyethylene, a high density polyethylene, a blend with a polypropylene, and a copolymer, is scarce.
As the fluororesin, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, or the like is used, and polytetrafluoroethylene is preferable from the viewpoint of availability.
These powders can be added in any amount depending on, for example, the required adhesive strength of the flooring material or the force necessary to peel off the flooring material. When the volume of the prepolymer (the total when a plurality of urethane prepolymers are used) is 100, it is desirable to add so that the volume of the powder is 40 to 160, preferably 60 to 130.
If the volume ratio of the powder is less than 60, the adhesive force is large and the easy peelability is reduced, and if it is less than 40, the tendency is further strengthened, but when the adhesive force of a large flooring is required, It is also possible to make it less than 40.
In addition, when the volume ratio exceeds 130, the adhesive strength is small and the peelability increases, and when it exceeds 160, the tendency is further increased. It is also possible to do.
The hard-adhesive resin powder is not only a powder obtained by pulverizing the hard-adhesive resin, but also a powder of an adhesive resin or a surface of an inorganic powder coated with a hard-adhesive resin, for example, Alternatively, glass beads whose surfaces are siliconized can be used. That is, even if a resin layer having no adhesiveness with the urethane adhesive or having a very poor adhesiveness is formed on the powder surface, the same effect can be obtained.
The size (particle size) of the particles is desirably 1 mm or less.
If a size larger than 1 mm is used, the hard-to-adhere resin is not sufficiently dispersed in the adhesive, and when applying the adhesive, it becomes easy to get caught in the comb of the comb eye. This will hinder your work.
The preferred particle size is 100 μm or less, and the average particle size as measured by the laser diffraction scattering method is about 10 to 50 μm, more preferably about 20 to 30 μm. It is particularly preferable in order to balance the above.
Moreover, in the Example mentioned later, the powder which consists of flaky particle | grains (average particle diameter is about 25 micrometers) with a size of 8-60 micrometers is used.
Thus, by using flaky particles as the particles of the hardly adhesive resin powder, there are large and small irregularities on the surface of the particles, so that the fracture stress on the adhesive resin around the particles is in the irregularities. It is easy to concentrate and cracks can be extended.
［無機充填剤］
本発明の接着剤には、硬化後の肉やせ防止のための増量剤として無機充填剤を添加することが好ましい。
無機充填剤としては公知の無機粉体が用いられるが、それらの具体例として以下のものを挙げることができる。
シリカ類、クレー類、タルク類、炭酸塩類（炭酸マグネシウム類や炭酸カルシウム類等）、ケイソウ土、硫酸バリウム、マイカ、セピオライト、ウォラストナイト、軽石粉、火山灰、硅砂、ガラス粉、ガラス繊維等の１種又は２種以上。
より具体的には、以下のものを挙げることができる。
シリカ類：無水微粉ケイ酸、及びそのジメチルシリコーンオイル、トリメチルシリル基、オクチルシラン、ジメチルジクロロシラン等で表面処理した疎水性のもの、含水微粉ケイ酸等。
クレー類：カオリン質クレー、パイロフィライト質クレー、セリサイト質クレー、焼成クレー等。
炭酸カルシウム類：重質炭酸カルシウム、軽質炭酸カルシウム、及びそれらの脂肪酸、樹脂酸、脂肪酸エステル、高級アルコール付加イソシアネート、カチオン、シランカップリング剤等により表面処理されたもの。
これらの中でも、シリカ類、クレー類、炭酸カルシウム類は、揺変剤としても機能するので、好ましく用いられる。
無機充填剤はプレポリマーの合計容積を１００とした場合、無機充填剤の容積が０〜３０となるように添加するのがよい。
[Inorganic filler]
In the adhesive of the present invention, it is preferable to add an inorganic filler as a bulking agent for preventing flesh thinning after curing.
Known inorganic powders are used as the inorganic filler, and specific examples thereof include the following.
Silicas, clays, talcs, carbonates (magnesium carbonates, calcium carbonates, etc.), diatomaceous earth, barium sulfate, mica, sepiolite, wollastonite, pumice powder, volcanic ash, cinnabar sand, glass powder, glass fiber, etc. 1 type or 2 types or more.
More specifically, the following can be mentioned.
Silicas: Anhydrous finely divided silicic acid and its hydrophobic materials treated with dimethylsilicone oil, trimethylsilyl group, octylsilane, dimethyldichlorosilane, hydrous finely divided silicic acid and the like.
Clays: kaolin clay, pyrophyllite clay, sericite clay, calcined clay, etc.
Calcium carbonates: those subjected to surface treatment with heavy calcium carbonate, light calcium carbonate, and their fatty acids, resin acids, fatty acid esters, higher alcohol addition isocyanates, cations, silane coupling agents, and the like.
Among these, silicas, clays, and calcium carbonates are preferably used because they function as thixotropic agents.
The inorganic filler is preferably added so that the volume of the inorganic filler is 0 to 30 when the total volume of the prepolymer is 100.
［揺変剤］
くし目こてで接着剤を下地に塗布する際の、接着剤の山立ちを保持させる目的で公知の揺変剤を添加することができる。
揺変剤を添加すると、不陸のある下地であっても、接着剤の塗布厚（山立ち）が高ければ床材となじませやすいので、施工性の点で好ましい。
揺変剤としては、シリカ、表面処理炭酸カルシウム、マイカ、セピオライトの無機物粉体や、有機ベントナイト、水添ひまし油等が用いられる。
[Thixotropic agent]
A known thixotropic agent can be added for the purpose of maintaining the ridges of the adhesive when the adhesive is applied to the base with a comb iron.
Addition of a thixotropic agent is preferable in terms of workability, because even if it is a ground surface with unevenness, if the application thickness (mountain standing) of the adhesive is high, it can be easily blended with the flooring material.
As the thixotropic agent, silica, surface treated calcium carbonate, mica, sepiolite inorganic powder, organic bentonite, hydrogenated castor oil and the like are used.
［希釈溶媒］
希釈溶媒は、接着剤の粘度を調整し、塗布性を確保するために用いられるが、それらの具体例として以下のものを挙げることができる。
ヘキサン、ヘプタン、イソパラフィン等の脂肪族炭化水素、シクロペンタン、シクロヘキサン、メチルシクロペンタン、メチルシクロヘキサン等の脂環族炭化水素、トルエン、キシレン等の芳香族炭化水素、酢酸エチル、酢酸ブチル、炭酸ジメチル等のエステル系溶剤、アセトン、メチルエチルケトン等のケトン系溶剤、ジプロピルエーテル、テトラヒドロフラン等のエーテル系溶剤、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチルピロリドン等の含窒素溶剤。
これらの希釈溶媒は、硬化後の肉やせ防止や接着強さを確保するために、溶媒は接着剤全体として５０％以下となるように配合することが好ましい。
[Diluted solvent]
The diluent solvent is used to adjust the viscosity of the adhesive and ensure applicability. Specific examples thereof include the following.
Aliphatic hydrocarbons such as hexane, heptane, and isoparaffin, alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane, aromatic hydrocarbons such as toluene and xylene, ethyl acetate, butyl acetate, dimethyl carbonate, etc. Ester solvents, ketone solvents such as acetone and methyl ethyl ketone, ether solvents such as dipropyl ether and tetrahydrofuran, nitrogen-containing solvents such as N, N-dimethylformamide and N-methylpyrrolidone.
These diluting solvents are preferably blended so that the total amount of the adhesive is 50% or less in order to prevent the skin from being thinned and to secure the adhesive strength after curing.
上記の充填剤や、希釈溶媒は、接着剤が床材用として適用可能なように、粘度が５〜５０Ｐａ・ｓ／２５℃（ＢＨ型粘度計 スピンドルＮｏ.６、２０ｒｐｍ）で、チクソトロピックインデックスが３〜８（ＢＨ型粘度計 スピンドルＮｏ.６、２ｒｐｍ／２０ｒｐｍ）となるように、配合することが好ましい。 The above filler and dilution solvent have a viscosity of 5 to 50 Pa · s / 25 ° C. (BH viscometer spindle No. 6, 20 rpm) and a thixotropic index so that the adhesive can be applied for flooring. Is preferably 3 to 8 (BH viscometer spindle No. 6, 2 rpm / 20 rpm).
さらに、この一液湿気硬化型ウレタン接着剤には、必須成分であるウレタンプレポリマー及び難接着性樹脂粉体、さらに、無機充填剤、揺変剤、希釈溶媒のほかに、本発明の課題解決を阻害しない範囲で、必要に応じて、粘着性付与樹脂、硬化促進触媒、脱水剤、安定剤、可塑剤、軟化剤、粘度調整剤、カップリング剤、老化防止剤、発泡防止剤、着色剤等の各種添加剤の１種又は２種以上を添加することもできる。 Furthermore, this one-component moisture-curing urethane adhesive includes the essential components of urethane prepolymer and hard-to-adhere resin powder, as well as inorganic fillers, thixotropic agents, and diluting solvents. If necessary, tackifying resin, curing accelerator, dehydrating agent, stabilizer, plasticizer, softener, viscosity modifier, coupling agent, anti-aging agent, antifoaming agent, coloring agent 1 type, or 2 or more types of various additives, such as these, can also be added.
［床材］
少なくとも裏面層（上記一液湿気硬化型ウレタン接着剤によって下地と接着される層）が軟質塩化ビニル樹脂やポリオレフィン等の合成樹脂製である床材、特に、軟質塩化ビニル製の床材が好ましく適用できる。
長尺シート状、タイル形状等、床材の形態は問わず、断面が略逆Ｌ字状の階段用床材にも適用できる。
[Floor materials]
Floor materials in which at least the back layer (the layer to be bonded to the base by the one-component moisture-curing urethane adhesive) is made of a synthetic resin such as soft vinyl chloride resin or polyolefin, particularly floor materials made of soft vinyl chloride are preferably applied. it can.
Regardless of the form of the floor material, such as a long sheet shape or a tile shape, the present invention can be applied to a stair floor material having a substantially inverted L-shaped cross section.
以下、本願発明のより具体的な実施例について説明する。 Hereinafter, more specific examples of the present invention will be described.
［ウレタンプレポリマーの合成］
（プレポリマー（Ａ１）（プレポリマー（Ａ））の合成）
ポリオキシプロピレンジオール（数平均分子量２０００）７５ｇと、ポリブチレンアジペートジオール（数平均分子量２０００）７５ｇと、ひまし油（官能基数２．７、水酸基価１５５〜１６５）９４．７ｇと、３−メチル−１，５−ペンタンジオール４４．６ｇとを仕込んで混合し、そこに２，４−トリレンジイソシアネート／２，６−トリレンジイソシアネート＝８０／２０の混合物を１３９．１ｇ（ＮＣＯ／ＯＨ＝１．３６）加えて、窒素雰囲気下で攪拌しながら樹脂温度９０℃にて６時間反応させてプレポリマー（Ａ１）を得た。その後、酢酸エチル２８５．６ｇを加えて希釈し、反応容器から取り出した。
[Synthesis of urethane prepolymer]
(Synthesis of prepolymer (A1) (prepolymer (A)))
75 g of polyoxypropylene diol (number average molecular weight 2000), 75 g of polybutylene adipate diol (number average molecular weight 2000), castor oil (number of functional groups 2.7, hydroxyl value 155 to 165) 94.7 g, 3-methyl-1 , 5-pentanediol 44.6 g was charged and mixed therewith, and 139.1 g (NCO / OH = 1.36) of a mixture of 2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate = 80/20. In addition, the mixture was reacted at a resin temperature of 90 ° C. for 6 hours with stirring in a nitrogen atmosphere to obtain a prepolymer (A1). Thereafter, 285.6 g of ethyl acetate was added for dilution, and the mixture was taken out from the reaction vessel.
（プレポリマー（Ａ２）（プレポリマー（Ａ））の合成）
ポリオキシプロピレンジオール（数平均分子量２０００）１５０ｇと、ポリブチレンアジペートジオール（数平均分子量２０００）７５ｇと、３−メチル−１，５−ペンタンジオール５３．１ｇとを仕込んで混合し、そこに２，４−トリレンジイソシアネート／２，６−トリレンジイソシアネート＝８０／２０の混合物を１１７．５ｇ（ＮＣＯ／ＯＨ＝１．２）加えて、窒素雰囲気下で攪拌しながら樹脂温度９０℃にて６時間反応させてプレポリマー（Ａ２）を得た。その後、酢酸エチル２６３．７ｇを加えて希釈し、反応容器から取り出した。
(Prepolymer (A2) (Prepolymer (A)) Synthesis)
150 g of polyoxypropylene diol (number average molecular weight 2000), 75 g of polybutylene adipate diol (number average molecular weight 2000), and 53.1 g of 3-methyl-1,5-pentanediol were charged and mixed. 117.5 g (NCO / OH = 1.2) of a mixture of 4-tolylene diisocyanate / 2,6-tolylene diisocyanate = 80/20 was added, and the mixture was stirred under a nitrogen atmosphere at a resin temperature of 90 ° C. for 6 hours. It was made to react and the prepolymer (A2) was obtained. Thereafter, 263.7 g of ethyl acetate was added for dilution, and the mixture was taken out from the reaction vessel.
（プレポリマー（Ｂ）の合成）
ポリオキシプロピレンジオール（数平均分子量４００）２００ｇに２，４−トリレンジイソシアネート／２，６−トリレンジイソシアネート＝８０／２０の混合物１７４ｇ（ＮＣＯ／ＯＨ＝２．０）を加えて、窒素雰囲気下で攪拌しながら樹脂温度８０℃にて５時間反応させることによりプレポリマー（Ｂ）を得た。
(Synthesis of prepolymer (B))
To 200 g of polyoxypropylene diol (number average molecular weight 400), 174 g of a mixture of 2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate = 80/20 (NCO / OH = 2.0) was added, and under nitrogen atmosphere The prepolymer (B) was obtained by reacting at a resin temperature of 80 ° C. for 5 hours with stirring.
［一液湿気硬化型ウレタン接着剤の混合・調整］
プレポリマー（Ａ）及びプレポリマー（Ｂ）を混合し、続いて難接着性樹脂粉体と無機充填剤（乾燥させたクレーと疎水性シリカ）を加え、難接着性樹脂粉並びに無機充填剤が充分に細かくウレタン樹脂液と均一に混ざるまで混練する。その後、希釈溶剤で粘度調整を行い、接着剤組成物を得た。
これらの混合には、ディスパー又は卓上攪拌機を用いた。
[Mixing and adjustment of one-component moisture-curing urethane adhesive]
The prepolymer (A) and the prepolymer (B) are mixed, and then the hardly adhesive resin powder and the inorganic filler (dried clay and hydrophobic silica) are added, and the hardly adhesive resin powder and the inorganic filler are added. Knead until sufficiently finely mixed with urethane resin liquid. Thereafter, the viscosity was adjusted with a diluting solvent to obtain an adhesive composition.
A disper or a table stirrer was used for the mixing.
各実施例及び比較例におけるプレポリマー（Ａ）及びプレポリマー（Ｂ）、難接着性樹脂粉体の配合比率を、表１に示す。
なお、Ａ系ウレタンプレポリマーの配合部数は、プレポリマー自体の配合比率を表したもので、酢酸エチルの質量は含まない。
Table 1 shows the blending ratios of the prepolymer (A), the prepolymer (B), and the hardly adhesive resin powder in each Example and Comparative Example.
In addition, the compounding part number of A-type urethane prepolymer represents the compounding ratio of prepolymer itself, and does not include the mass of ethyl acetate.
［評価方法］
（常態接着力と耐水接着力試験）
表１に示す評価方法における常態接着力と耐水接着力は、それぞれＪＩＳ Ａ ５５３６に規定された「剥離接着強さ」の「常態」、「水中浸せき」によって測定した。「常態」においては、下地材（モルタル板）への接着剤の塗布は、ＪＩＳ Ａ ５５３６に規定の「くし目ごて」を用いて行い、塗布後２０分を経過後、タキロン株式会社製の軟質塩化ビニル製ビニル床シートを、下地材に接着して温度２３±２℃、湿度５０±１０％で４８時間養生して試験体とした。「水中浸せき」においては、「常態」の試験体を、さらに２３±２℃の水中に１６８時間浸漬したものを試験体とした。これら試験体は、浮動ローラ法を用いて「剥離接着強さ」を測定した。
表中の剥離状態に示した数値は、剥離した試験体における破断位置を面積比で表したもので、「Ａ」は破断位置が「接着剤」（接着剤の凝集破壊）、「ＧＡ」は「下地材と接着剤の界面」（下地との接着界面での剥離）、「Ｆ」は「床材」、「ＡＦ」は「接着剤と床材の界面」であることを示している。
[Evaluation method]
(Normal adhesive strength and water resistant adhesive strength test)
The normal adhesive strength and water-resistant adhesive strength in the evaluation methods shown in Table 1 were measured by “normal” and “immersion in water” of “peeling adhesive strength” defined in JIS A 5536, respectively. In the “normal state”, the adhesive is applied to the base material (mortar board) using the “comb iron” defined in JIS A 5536. After 20 minutes from the application, the product manufactured by Takiron Co., Ltd. is used. A soft vinyl chloride vinyl floor sheet was bonded to the base material and cured at a temperature of 23 ± 2 ° C. and a humidity of 50 ± 10% for 48 hours to obtain a test specimen. In “immersion in water”, a “normal state” test specimen was further immersed in water at 23 ± 2 ° C. for 168 hours as a test specimen. These specimens were measured for “peel adhesion strength” using a floating roller method.
The numerical values shown in the peeled state in the table are the broken positions in the peeled specimens expressed as area ratios. “A” is the broken position is “adhesive” (cohesive failure of adhesive), “GA” is “Interface between the base material and adhesive” (peeling at the adhesive interface between the base), “F” indicates “floor material”, and “AF” indicates “interface between adhesive and floor material”.
（貯蔵安定性試験）
０．５リットル入りの金属缶に接着剤を０．４〜０．４５リットル分入れ、樹脂製中蓋と金属製上蓋とで密封した状態で、温度２３±２℃、湿度５０±１０％の環境下に保管し、１ヶ月毎に接着剤の状態を目視確認して評価した。
(Storage stability test)
In a state where a 0.4 to 0.45 liter adhesive is put into a 0.5 liter metal can and sealed with a resin inner lid and a metal top lid, the temperature is 23 ± 2 ° C. and the humidity is 50 ± 10%. It was stored in the environment, and the state of the adhesive was visually confirmed and evaluated every month.
以上、本発明の合成樹脂製床材用一液湿気硬化型ウレタン接着剤及びこの一液湿気硬化型ウレタン接着剤を使用した床構造について、その実施例に基づいて説明したが、本発明は上記実施例に記載した構成に限定されるものではなく、その趣旨を逸脱しない範囲において適宜その構成を変更することができるものである。 As described above, the one-component moisture-curable urethane adhesive for synthetic resin flooring of the present invention and the floor structure using this one-component moisture-curable urethane adhesive have been described based on the examples. It is not limited to the structure described in the Example, The structure can be changed suitably in the range which does not deviate from the meaning.
本発明の合成樹脂製床材用一液湿気硬化型ウレタン接着剤及びこの一液湿気硬化型ウレタン接着剤を使用した床構造は、使用中に合成樹脂製床材が床下地から剥がれたり、膨れたりする等の不具合を生じないようにできるという耐久性及び耐水性に関する基本的な特性を備えながら、改修等に際して、既設の合成樹脂製床材を床下地から容易に剥離、除去できる特性を有していることから、改修を行う頻度が高い合成樹脂製床材の敷設の用途に好適に用いることができるほか、それ以外の用途にも広く用いることができる。 The one-component moisture-curable urethane adhesive for synthetic resin flooring of the present invention and the floor structure using this one-component moisture-curable urethane adhesive peel off or swell the synthetic resin flooring from the floor base during use. In addition to having the basic characteristics of durability and water resistance that can prevent problems such as Therefore, it can be suitably used for laying a synthetic resin floor material that is frequently repaired, and can also be widely used for other purposes.
Claims (4)
ウレタンプレポリマー（Ａ）：イソシアネート基と水酸基との比率〔ＮＣＯ〕／〔ＯＨ〕が１．０〜１．５となるようにイソシアネートとポリオールを配合して合成されたウレタンプレポリマー
ウレタンプレポリマー（Ｂ）：イソシアネート基と水酸基との比率〔ＮＣＯ〕／〔ＯＨ〕が１．５より大きくなるようにイソシアネートとポリオールを配合して合成されたウレタンプレポリマー The following urethane prepolymers (A) and (B) having an isocyanate group obtained by reacting a polyol and a polyisocyanate compound, which is an adhesive used for bonding a synthetic resin floor material to a floor base The hard-to-adhesive resin powder is blended, and after curing, the hard-to-adhesive resin powder is uniformly dispersed in the cured urethane resin and bonded to the floor base by the adhesive. When a peeling force is applied to the synthetic resin floor material, the urethane resin breaks along the interface between the urethane resin and the hardly adhesive resin powder, and the urethane resin coheses and breaks from the broken interface. A one-component moisture-curing urethane adhesive for synthetic resin flooring, wherein the synthetic resin flooring is peeled off from the floor base.
Urethane prepolymer (A): Urethane prepolymer synthesized by blending isocyanate and polyol such that the ratio [NCO] / [OH] of isocyanate group to hydroxyl group is 1.0 to 1.5 Urethane prepolymer ( B): Urethane prepolymer synthesized by blending isocyanate and polyol so that the ratio [NCO] / [OH] of isocyanate group to hydroxyl group is greater than 1.5
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009129787A JP5523746B2 (en) | 2009-05-29 | 2009-05-29 | One-component moisture-curing urethane adhesive for synthetic resin flooring and floor structure using this one-component moisture-curing urethane adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009129787A JP5523746B2 (en) | 2009-05-29 | 2009-05-29 | One-component moisture-curing urethane adhesive for synthetic resin flooring and floor structure using this one-component moisture-curing urethane adhesive |
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| JP5523746B2 true JP5523746B2 (en) | 2014-06-18 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP4112668A1 (en) * | 2021-06-28 | 2023-01-04 | Sika Technology AG | Reactive hot-melt adhesive having good adhesion to both polar and non-polar substrates |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US10017674B2 (en) * | 2009-12-31 | 2018-07-10 | Bostik, Inc. | Moisture curable adhesive compositions |
| JP5610537B2 (en) * | 2011-03-25 | 2014-10-22 | 大日精化工業株式会社 | One-pack type adhesive composition and composition using the same as an adhesive layer |
| KR102271145B1 (en) * | 2019-07-30 | 2021-07-01 | 주식회사 삼양사 | Isocyanate prepolymer, moisture-curing polyurethane and eco-friendly adhesive composition comprising the same |
| KR102351307B1 (en) * | 2019-07-30 | 2022-01-14 | 주식회사 삼양사 | Isocyanate prepolymer, moisture-curing polyurethane and eco-friendly adhesive composition comprising the same |
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| JP2001279220A (en) * | 2000-03-31 | 2001-10-10 | Nippon Nsc Ltd | Cold-seal adhesive and information carrier produced by using the adhesive |
| JP2001335615A (en) * | 2000-05-26 | 2001-12-04 | Yokohama Rubber Co Ltd:The | One-package polyurethane composition |
| JP2004051878A (en) * | 2002-07-23 | 2004-02-19 | Dainippon Ink & Chem Inc | Heat sensitive adhesive resin composition and recording medium therewith |
| JP4756310B2 (en) * | 2004-10-15 | 2011-08-24 | Ｄｉｃ株式会社 | One-component reactive polyurethane resin adhesive |
| JP5719495B2 (en) * | 2007-04-04 | 2015-05-20 | オート化学工業株式会社 | Two-component urethane-based curable composition, flooring adhesive and repair agent using the same, and flooring construction method and repairing method |
| JP2008285616A (en) * | 2007-05-21 | 2008-11-27 | Seikoh Chem Co Ltd | One-package type moisture-curable polyurethane resin-based adhesive |
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| EP4112668A1 (en) * | 2021-06-28 | 2023-01-04 | Sika Technology AG | Reactive hot-melt adhesive having good adhesion to both polar and non-polar substrates |
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