JP4308690B2 - One-component moisture-curable urethane composition that can be easily thermally decomposed - Google Patents
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Description
本発明は、接着剤、シーリング材、塗料、封止材、注型材、発泡体、成形体等の用途において、部材の剥離、解体などにより部材を取除きたい時に加熱処理により容易に加熱分解しうる一液型湿気硬化性ウレタン系組成物、更に詳しくは、オキシム基とイソシアネート基の反応によるウレタン結合を含有する末端イソシアネート基含有ウレタンプレポリマーを成分とする容易に加熱分解しうる一液型湿気硬化性ウレタン系組成物に関し、たとえば自動車窓ガラスの接着に適用する接着剤とした場合、湿気硬化後に所望に応じた加熱処理で容易に軟化、分解し、これによって車体から窓ガラスを容易に剥がすことができる一液型湿気硬化性ウレタン系組成物に関する。 In applications such as adhesives, sealing materials, paints, sealants, casting materials, foams, molded products, etc., the present invention is easily thermally decomposed by heat treatment when it is desired to remove the members by peeling or disassembling the members. One-component moisture-curable urethane composition, more specifically, one-component moisture that can be easily thermally decomposed using a terminal isocyanate group-containing urethane prepolymer containing a urethane bond by reaction of an oxime group and an isocyanate group as a component Regarding curable urethane-based compositions, for example, when used as an adhesive for application to automobile window glass, it is easily softened and decomposed by heat treatment as desired after moisture curing, thereby easily removing the window glass from the vehicle body. The present invention relates to a one-component moisture-curable urethane composition that can be used.
たとえば、現在自動車窓ガラスの接着には、一般にポリオールと過剰量のポリイソシアネート化合物の反応により得られ、ヒドロキシル基とイソシアネート基の反応によるウレタン結合を有する末端イソシアネート基含有ウレタンプレポリマーを主成分とし、これに概して、可塑剤、充填剤、硬化触媒等を配合した一液型湿気硬化性ウレタン系組成物が使用されている。しかして、自動車の窓ガラスの接着剤には自動車の構造上、高強度や高耐久性に優れる接着性が要求されるが、一方、自動車の廃車解体、窓ガラスの交換時解体の必要性が生じた場合には、硬化した接着剤を破断、切断したり、加熱分解による剥離が要せられる。しかしながら、前記接着剤はゴム弾性が強いので、ピアノ線やカッターによる切断が困難である。更に加熱分解をさせる場合には非常に高い高温の加熱処理が必要で、設備負荷や光熱費増加、シアンガスの発生等の恐れを招く。このため、自動車の解体に際し、より低い加熱温度で容易に剥離、解体できることが求められている。 For example, at present, automotive window glass is generally bonded to a terminal isocyanate group-containing urethane prepolymer, which is obtained by a reaction between a polyol and an excess amount of a polyisocyanate compound, and has a urethane bond by a reaction between a hydroxyl group and an isocyanate group. In general, a one-component moisture-curable urethane composition containing a plasticizer, a filler, a curing catalyst, and the like is used. However, automotive window glass adhesives are required to have high strength and high durability due to the structure of the automobile. On the other hand, there is a need to dismantle automobiles and dismantle them when replacing window glass. When it occurs, the cured adhesive must be broken and cut, or peeled off by thermal decomposition. However, since the adhesive has strong rubber elasticity, it is difficult to cut it with a piano wire or a cutter. Further, when heat decomposition is performed, heat treatment at a very high temperature is necessary, which may cause an increase in equipment load, an increase in utility costs, generation of cyan gas, and the like. For this reason, when the automobile is disassembled, it is required that the automobile can be easily peeled and disassembled at a lower heating temperature.
このような状況下で既に、上記主成分の末端イソシアネート基含有ウレタンプレポリマーに、フェノール性のヒドロキシル基とイソシアネート基の反応によるウレタン結合を導入、すなわち、上記ポリオール成分にフェノール性のヒドロキシル基を有する化合物、たとえばハイドロキノン、レゾルシノール、ビスフェノールA、ビスフェノールF、ビスフェノールS、ビス(4−ヒドロキシフェニル)スルフィドなどを加え、これらを過剰量のポリイソシアネート化合物と反応させることによって、該導入前と比べて低い加熱温度で容易に剥離できる技術が提案されている(たとえば特許文献1参照)。 Under such circumstances, a urethane bond by the reaction of a phenolic hydroxyl group and an isocyanate group is already introduced into the terminal isocyanate group-containing urethane prepolymer of the main component, that is, the polyol component has a phenolic hydroxyl group. By adding compounds such as hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, bis (4-hydroxyphenyl) sulfide, etc., and reacting them with an excess amount of polyisocyanate compound, the heating is lower than before the introduction. A technique that can be easily peeled off at a temperature has been proposed (for example, see Patent Document 1).
本発明者らは、かかる加熱処理温度が比較的低い温度での剥離化の要望を満足すべきため鋭意研究を進めたところ、オキシム基とイソシアネート基の反応によるウレタン結合を含有した末端イソシアネート基含有ウレタンプレポリマーを用いれば上記提案技術に優さるとも劣らない低加熱による分解効果が得られることを見出し、本発明を完成させるに至った。 The inventors of the present invention have made extensive studies to satisfy the demand for exfoliation at a relatively low heat treatment temperature, and have a terminal isocyanate group containing a urethane bond by a reaction between an oxime group and an isocyanate group. The use of a urethane prepolymer has led to the completion of the present invention by finding that a decomposition effect by low heating that is not inferior to the proposed technique can be obtained.
すなわち、本発明は、オキシム基とイソシアネート基(以下、NCOと称す)の反応によるウレタン結合を含有する末端イソシアネート基含有ウレタンプレポリマー[以下、末端NCO含有プレポリマー(A)と称す]を成分とすることを特徴とする容易に加熱分解しうる一液型湿気硬化性ウレタン系組成物を提供するものである。 That is, the present invention comprises a terminal isocyanate group-containing urethane prepolymer [hereinafter referred to as a terminal NCO-containing prepolymer (A)] containing a urethane bond by the reaction of an oxime group and an isocyanate group (hereinafter referred to as NCO) as a component. It is an object of the present invention to provide a one-component moisture-curable urethane composition that can be easily thermally decomposed.
本発明によれば、自動車のフロントおよびリアーの窓ガラスを車体に接着する接着剤に適用する場合において、本来要求される常態接着性に何ら支障なく、加熱処理として低加熱により、接着剤が迅速に軟化し接着界面の破断が生じ、容易に剥離しうることが認められ、このことは、自動車解体時の効率向上並びにガラスの再使用が可能となり、リサイクルすることができ、産業廃棄物の低減にも寄与する。 According to the present invention, when the front and rear window glass of an automobile is applied to an adhesive that adheres to a vehicle body, the normal adhesiveness that is originally required is not affected at all, and the adhesive can be quickly produced by low heating as a heat treatment. It is recognized that the adhesive interface breaks and can be easily peeled off, which can improve the efficiency when dismantling the automobile and reuse the glass, which can be recycled and reduce industrial waste. Also contributes.
本発明において用いる上記末端NCO含有プレポリマー(A)は、オキシム基含有化合物に対して過剰量のイソシアネート基含有ポリイソシアネート化合物(通常、オキシム化合物のOH/ポリイソシアネート化合物のNCO=1/1.5〜1/4.0)を、常法により反応させることによって製造される。 The terminal NCO-containing prepolymer (A) used in the present invention contains an isocyanate group-containing polyisocyanate compound in excess of the oxime group-containing compound (usually OH of the oxime compound / NCO of the polyisocyanate compound = 1 / 1.5). ˜1 / 4.0) is produced by a conventional reaction.
上記オキシム基含有化合物としてジオキシム化合物が望ましく、たとえば、ジメチルグリオキシム、フリルジオキシム、p−ベンゾキノンジオキシム、p,p−ジベンゾイルベンゾキノンジオキシム、式:
HON=CH−R−CH=NOH
(式中、RはC5〜10の脂肪族または脂環式炭化水素基である)
で示されるジオキシム化合物、たとえば1,7−ヘプタンジアールジオキシム、1,8−オクタンジアールジオキシム、2−メチル−1,8−オクタンジアールジオキシム、1,9−ノナンジアールジオキシム、1,10−デカンジアールジオキシム、1,11−ウンデカンジアールジオキシム、1,12−ドデカンジアールジオキシム、3,8−ジメチル−1,10−デカンジアールジオキシム、3,7−ジメチル−1,10−デカンジアールジオキシム、シクロヘキサン−1,3(4)−ジカルバルデヒドジオキシム、ビシクロ[2.2.1]ヘプタン−2(3),5(6)−ジカルバルデヒドジオキシム、ビシクロ[2.2.2]オクタン−2(3),5(6)−ジカルバルデヒドジオキシム、トリシクロ[5.2.1.0]デカン−3(4),8(9)−ジカルバルデヒドジオキシムなどが挙げられる。
The oxime group-containing compound is preferably a dioxime compound, such as dimethylglyoxime, furyl dioxime, p-benzoquinone dioxime, p, p-dibenzoylbenzoquinone dioxime, a formula:
HON = CH-R-CH = NOH
(Wherein R is a C5-10 aliphatic or alicyclic hydrocarbon group)
For example, 1,7-heptane diar dioxime, 1,8-octane diar dioxime, 2-methyl-1,8-octane diar dioxime, 1,9-nonane diar dioxime 1,10-decandial dioxime, 1,11-undecandial dioxime, 1,12-dodecanedial dioxime, 3,8-dimethyl-1,10-decandial dioxime, 3,7 -Dimethyl-1,10-decandial dioxime, cyclohexane-1,3 (4) -dicarbaldehyde dioxime, bicyclo [2.2.1] heptane-2 (3), 5 (6) -dicarba Rudehydrodioxime, bicyclo [2.2.2] octane-2 (3), 5 (6) -dicarbaldehyde dioxime, tricyclo [5.2.1.0] decane-3 (4), 8 (9 -Dikarbar Dehydrodioxime etc. are mentioned.
上記ポリイソシアネート化合物としては、たとえばトリレンジイソシアネート(TDI)、4,4'−ジフェニルメタンジイソシアネート(MDI)、キシリレンジイソシアネート(XDI)、ヘキサメチレンジイソシアネート(HDI)、イソホロンジイソシアネート(IPDI)、リジンジイソシアネート、イソプロピリデンビス(4−シクロヘキシルイソシアネート)、水添XDIなどが挙げられる。 Examples of the polyisocyanate compound include tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), lysine diisocyanate, isopropylene. Examples include redenebis (4-cyclohexyl isocyanate) and hydrogenated XDI.
なお、上記末端NCO含有プレポリマー(A)に、通常用いるポリオールに対して過剰量のポリイソシアネート化合物を反応させて製造される末端NCO含有ウレタンプレポリマー[以下、末端NCO含有プレポリマー(B)と称す]を併用してもよい。 The terminal NCO-containing prepolymer (A) and a terminal NCO-containing urethane prepolymer produced by reacting an excess amount of a polyisocyanate compound with a commonly used polyol (hereinafter referred to as a terminal NCO-containing prepolymer (B)) May be used in combination.
上記ポリオールとしては、たとえばポリオキシアルキレンポリオール(PPGと称す)、ポリエーテルポリオール変性体、ポリテトラメチレンエーテルグリコールなどのポリエーテルポリオール;縮合系ポリエステルポリオール、ラクトン系ポリエステルポリオール、ポリカーボネートジオールなどのポリエステルポリオール;アクリルポリオール、ポリブタジエン系ポリオール、ポリオレフィン系ポリオール、ケン化エチレン−酢酸ビニル共重合体などの主鎖がC−C結合よりなるポリオール;その他難燃化用ポリオール、含リンポリオール、含ハロゲンポリオールなどが挙げられる。
Examples of the polyol include polyether polyols such as polyoxyalkylene polyol (referred to as PPG), modified polyether polyol, and polytetramethylene ether glycol; polyester polyols such as condensed polyester polyol, lactone polyester polyol, and polycarbonate diol; A polyol having a main chain composed of a C—C bond, such as an acrylic polyol, a polybutadiene-based polyol, a polyolefin-based polyol, a saponified ethylene-vinyl acetate copolymer; other flame retardant polyols, phosphorus-containing polyols, halogen-containing polyols, etc. It is done.
この場合、末端NCO含有プレポリマー(A)100重量部に対して末端NCO含有プレポリマー(B)を0〜900重量部の割合で選定して用いる。通常末端NCO基含有プレポリマー(A)を湿気硬化させた時、硬い物性の硬化物が得られる傾向にあり、硬い硬化物に設計する接着剤、塗料、注型剤、発泡体、成形体を得たい場合には使用割合を多くする。ゴム弾性が要求されるシーリング材や接着剤の場合には末端NCO基含有プレポリまー(B)を混合して併用するのが望ましい。湿気硬化する所望の物性に応じて末端NCO基含有ウレタンプレポリマー(A)と末端NCO基含有プレポリマー(B)を調製するものである。 In this case, the terminal NCO-containing prepolymer (B) is selected and used at a ratio of 0 to 900 parts by weight with respect to 100 parts by weight of the terminal NCO-containing prepolymer (A). Usually, when the terminal NCO group-containing prepolymer (A) is moisture-cured, a cured product having a hard physical property tends to be obtained. Adhesives, paints, casting agents, foams, and molded products designed to be a hard cured product are used. If you want to get it, increase the usage rate. In the case of a sealing material or adhesive that requires rubber elasticity, it is desirable to mix and use the terminal NCO group-containing prepolymer (B). A terminal NCO group-containing urethane prepolymer (A) and a terminal NCO group-containing prepolymer (B) are prepared according to desired physical properties to be moisture-cured.
上記では、末端NCO基含有プレポリマー(A)と末端NCO基含有プレポリマー(B)を別々に調製してから所望の割合で混合することを説明したが、末端NCO基含有プレポリマー(A)と末端NCO基含有プレポリマー(B)を同時に任意に調製しても良いことは言うまでもない。たとえばオキシム基含有化合物とイソシアネート基含有化合物を反応して末端NCO基含有プレポリマー(A)またはポリオールとイソシアネート基含有化合物を反応して末端NCO基含有プレポリマー(B)を調製するときに、末端NCO基含有ウレタンプレポリマー(B)を調製するときに用いるポリオールとオキシム基含有化合物とを混合したり、順次添加してイソシアネート基含有化合物と反応させても得られる。更に末端NCO基含有ウレタンプレポリマー(A)または(B)の製造において、予めポリオールとイソシアネート基含有化合物と反応させた末端NCO基含有反応生成物を得た後、次いでオキシム基含有化合物を反応させて末端NCO基含有ウレタンプレポリマーを得ることもできるが、逆に予めオキシム基含有化合物とイソシアネート基含有化合物を予め反応させて得られる末端NCO基含有反応生成物にポリオールを反応させて末端NCO基含有プレポリマー(A)または(B)を調製してもよい。このように末端NCO基含有プレポリマー(A)または(B)において、分子中にオキシム基とイソシアネート基と反応したウレタン結合(以下、オキシムウレタン結合と称す)とポリオール基とイソシアネート基と反応したウレタン結合が含まれておればよく、別々の分子中に存在しても良い。 In the above, it has been described that the terminal NCO group-containing prepolymer (A) and the terminal NCO group-containing prepolymer (B) are prepared separately and then mixed in a desired ratio. However, the terminal NCO group-containing prepolymer (A) Needless to say, the terminal NCO group-containing prepolymer (B) may be optionally prepared at the same time. For example, when preparing a terminal NCO group-containing prepolymer (A) by reacting an oxime group-containing compound and an isocyanate group-containing compound to prepare a terminal NCO group-containing prepolymer (B) or a polyol and an isocyanate group-containing compound. It can also be obtained by mixing the polyol used in preparing the NCO group-containing urethane prepolymer (B) and the oxime group-containing compound, or adding them sequentially to react with the isocyanate group-containing compound. Further, in the production of the terminal NCO group-containing urethane prepolymer (A) or (B), a terminal NCO group-containing reaction product obtained by reacting with a polyol and an isocyanate group-containing compound in advance is obtained, and then the oxime group-containing compound is reacted. It is also possible to obtain a terminal NCO group-containing urethane prepolymer, but conversely, a terminal NCO group-containing reaction product obtained by reacting an oxime group-containing compound and an isocyanate group-containing compound in advance is reacted with a polyol to form a terminal NCO group. Containing prepolymer (A) or (B) may be prepared. Thus, in the terminal NCO group-containing prepolymer (A) or (B), the urethane bond (hereinafter referred to as oxime urethane bond) reacted with the oxime group and the isocyanate group in the molecule, and the urethane reacted with the polyol group and the isocyanate group. It only needs to contain a bond and may exist in separate molecules.
上記オキシム基とNCOの反応によるウレタン結合の導入によって、所期目的の低温剥離化が得られるが、さらにより向上せしめるため、熱膨張性バルーンを適量加えてもよい。ここで、熱膨張性バルーンとは、液体ガスまたは低沸点炭化水素などの熱膨張物質を、ポリ塩化ビニリデン、ポリアクリロニトリル、塩化ビニリデン−アクリロニトリル共重合体、アクリロニトリル−メタクリル酸メチル共重合体等の熱可塑性プラスチック殻で内包して成るプラスチック球体を指称する。 By introducing a urethane bond by the reaction of the oxime group and NCO, the intended low-temperature exfoliation can be obtained, but in order to further improve, an appropriate amount of a heat-expandable balloon may be added. Here, the thermally expandable balloon is a thermal expansion material such as liquid gas or low boiling point hydrocarbon such as polyvinylidene chloride, polyacrylonitrile, vinylidene chloride-acrylonitrile copolymer, acrylonitrile-methyl methacrylate copolymer, etc. A plastic sphere encapsulated in a plastic shell is designated.
上記のように末端NCO基含有プレポリマー(A)を成分とした一液型湿気硬化性ウレタン系組成物は、オキシムウレタン結合を加熱処理によって比較的低温の加熱処理条件で軟化、分解させることができる。従って、本願発明の容易に加熱分解しうる一液型湿気硬化性ウレタン系組成物を接着剤、シーリング材、塗料、注型材、封止材、発泡体、成形体等の用途に用いる場合、剥離、解体等の必要時に加熱処理すれば比較的低温の加熱処理条件で容易に軟化分解させることができる。その結果、部材のリサイクルであったり、廃棄物を削減することが可能となり、廃棄する場合にも産業廃棄物が減容化できるので、地球環境を保護、地球環境への負荷を低減できることになる。 As described above, the one-component moisture-curable urethane composition containing the terminal NCO group-containing prepolymer (A) as a component can soften and decompose oxime urethane bonds under heat treatment conditions at a relatively low temperature. it can. Therefore, when the one-component moisture-curable urethane-based composition of the present invention that can be easily thermally decomposed is used for applications such as adhesives, sealing materials, paints, casting materials, sealing materials, foams, molded products, etc., peeling If heat treatment is performed when necessary for dismantling, etc., it can be easily softened and decomposed under relatively low temperature heat treatment conditions. As a result, it is possible to recycle parts and reduce waste, and industrial waste can be reduced in volume when it is discarded, thus protecting the global environment and reducing the burden on the global environment. .
本発明に係る容易に加熱分解しうる一液型湿気硬化性ウレタン系組成物は、上述の末端NCO含有プレポリマー(A)を成分とし(要すれば、これに末端NCO含有プレポリマー(B)や熱膨張性バルーンを加え)、概して可塑剤、充填剤、硬化触媒を配合した系で構成される。ここで、末端NCO含有プレポリマー(A)(主成分)の含有量は通常、組成物全量中20〜60%の範囲で選定すればよい。 The one-component moisture-curable urethane-based composition that can be easily thermally decomposed according to the present invention comprises the above-mentioned terminal NCO-containing prepolymer (A) as a component (if necessary, the terminal NCO-containing prepolymer (B) And a heat-expandable balloon), and generally a system containing a plasticizer, a filler, and a curing catalyst. Here, the content of the terminal NCO-containing prepolymer (A) (main component) may be usually selected in the range of 20 to 60% in the total amount of the composition.
上記可塑剤としては、たとえばジイソノニルフタレート(DINP)、ジオクチルフタレート(DOP)、ジブチルフタレート、ジラウリルフタレート、ブチルベンジルフタレート、ジオクチルアジペート、ジイソデシルアジペート、トリオクチルホスフェート、トリス(クロロエチル)ホスフェート、トリス(ジクロロプロピル)ホスフェート、アジピン酸プロピレングリコールポリエステル、アジピン酸ブチレングリコールポリエステル、エポキシステアリン酸アルキル、アルキルベンゼン、エポキシ化大豆油などが挙げられ、配合量は通常、組成物全量中0〜50%の範囲で選定されてよい。
上記充填剤としては、たとえば炭酸カルシウム、シリカ、カーボンブラック、クレー、タルク、酸化チタン、生石灰、カオリン、ゼオライト、珪藻土などが挙げられ、配合量は通常、組成物全量中0〜50%の範囲で選定されてよい。
Examples of the plasticizer include diisononyl phthalate (DINP), dioctyl phthalate (DOP), dibutyl phthalate, dilauryl phthalate, butyl benzyl phthalate, dioctyl adipate, diisodecyl adipate, trioctyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl). ) Phosphate, propylene glycol adipate polyester, butylene glycol adipate polyester, epoxy alkyl stearate, alkylbenzene, epoxidized soybean oil, etc. are included, and the blending amount is usually selected in the range of 0 to 50% in the total amount of the composition Good.
Examples of the filler include calcium carbonate, silica, carbon black, clay, talc, titanium oxide, quicklime, kaolin, zeolite, diatomaceous earth, and the blending amount is usually in the range of 0 to 50% in the total amount of the composition. May be selected.
上記硬化触媒としては、たとえば有機錫化合物(ジブチル錫ジアセチルアセトネート、ジブチル錫ジラウレート、ジオクチル錫ジラウレート、ジブチル錫マレエート、ジオクチル錫マレエート、オクチル酸錫など);2,2'−ジモルホリノジエチルエーテル、ジ(2,6−ジメチルモルホリノエチル)エーテル;カルボン酸ビスマス(2−エチルヘキサン酸ビスマス、オクチル酸ビスマス、ネオデカン酸ビスマスなど);カルボン酸(安息香酸、フタル酸、2−エチルヘキサン酸、オクチル酸、ステアリン酸、オレイン酸、リノール酸など)が挙げられ、配合量は通常、組成物全量中0.0001〜5%の範囲で選定されてよい。 Examples of the curing catalyst include organic tin compounds (dibutyltin diacetylacetonate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin maleate, dioctyltin maleate, tin octylate, etc.); 2,2′-dimorpholinodiethyl ether, (2,6-dimethylmorpholinoethyl) ether; bismuth carboxylate (bismuth 2-ethylhexanoate, bismuth octylate, bismuth neodecanoate, etc.); carboxylic acid (benzoic acid, phthalic acid, 2-ethylhexanoic acid, octylic acid, Stearic acid, oleic acid, linoleic acid, etc.), and the blending amount may usually be selected in the range of 0.0001 to 5% of the total composition.
さらに必要に応じて、密着剤[分子量1000未満のポリイソシアネート化合物変性体(たとえばヘキサメチレンジイソシアネートのビュレット変性体、イソシアヌレート変性体、トリメチロールプロパン変性体など);前記ポリイソシアネート化合物とアルコキシシリル基含有化合物(メルカプトプロピルトリメトキシシラン、メルカプトプロピルメチルジメトキシシラン、γ−N−フェニルアミノプロピルトリメトキシシラン、γ−イソシアナトプロピルトリメトキシシランなど;さらにアルコキシシリル基含有ポリウレタン系ポリマー、アルコキシシリル基含有ポリエーテル系ポリマー、アルコキシシリル基含有ビニル系ポリマー、アルコキシシリル基含有ポリエステル系ポリマー、アルコキシシリル基含有ジエン系ポリマー、アルコキシシリル基含有ポリアルキレン系ポリマー等)の反応生成物;および該アルコキシシリル基含有化合物から選ばれる1種または2種以上が挙げられ、配合量は通常組成物全量中0.1〜10%の範囲で選定]が配合されてよく、さらに溶剤(キシレン、トルエンなど);その他老化防止剤、酸化防止剤、紫外線吸収剤、吸湿吸水剤、顔料等を適量加えてもよい。 Further, if necessary, an adhesive [modified polyisocyanate compound having a molecular weight of less than 1000 (for example, a hexamethylene diisocyanate modified buret, isocyanurate modified, trimethylolpropane modified, etc.); containing the polyisocyanate compound and an alkoxysilyl group Compound (mercaptopropyltrimethoxysilane, mercaptopropylmethyldimethoxysilane, γ-N-phenylaminopropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane, etc .; further alkoxysilyl group-containing polyurethane polymer, alkoxysilyl group-containing polyether Polymer, alkoxysilyl group-containing vinyl polymer, alkoxysilyl group-containing polyester polymer, alkoxysilyl group-containing diene polymer, alkoxy A reaction product of a silyl group-containing polyalkylene polymer, and the like, and one or more selected from the alkoxysilyl group-containing compound, and the blending amount is usually in the range of 0.1 to 10% in the total amount of the composition. In addition, an appropriate amount of a solvent (xylene, toluene, etc.); an anti-aging agent, an antioxidant, an ultraviolet absorber, a hygroscopic water-absorbing agent, a pigment, etc. may be added.
次に製造例、実施例および比較例を挙げて、本発明をより具体的に説明する。
製造例1:末端NCO含有プレポリマー(A)の製造
ジメチルグリオキシム20gに、水酸基価27.9のポリオキシプロピレンジオール1035gおよび水酸基価33.7のポリオキシプロピレントリオール203gを加え、窒素雰囲気下に90℃で2時間撹拌し、続けて4,4'−ジフェニルメタンジイソシアネート(MDI)258gと、ジイソノニルフタレート(DINP)で1%に希釈したオクチル酸錫0.3gとを加え、窒素雰囲気下80℃で6時間反応させて、全ウレタン結合中のオキシムウレタン結合(35 )モル%、遊離NCO基含有量2.95%および粘度200000mPa・S(20℃)の末端NCO含有プレポリマー(A)を得る。
Next, the present invention will be described more specifically with reference to production examples, examples and comparative examples.
Production Example 1: Production of terminal NCO-containing prepolymer (A) To 20 g of dimethylglyoxime, 1035 g of a polyoxypropylene diol having a hydroxyl value of 27.9 and 203 g of a polyoxypropylene triol having a hydroxyl value of 33.7 were added, and a nitrogen atmosphere was added. Stir at 90 ° C. for 2 hours, then add 258 g of 4,4′-diphenylmethane diisocyanate (MDI) and 0.3 g of tin octylate diluted to 1% with diisononyl phthalate (DINP) at 80 ° C. in a nitrogen atmosphere. The reaction is performed for 6 hours to obtain a terminal NCO-containing prepolymer (A) having an oxime urethane bond (35) mol% in all urethane bonds, a free NCO group content of 2.95%, and a viscosity of 200,000 mPa · S (20 ° C.).
製造例2:末端NCO含有プレポリマー(B)の製造
水酸基価27.9のポリオキシプロピレンジオール1035gおよび水酸基価33.7のポリオキシプロピレントリオール203gに、MDI167gと、DINPで1%に希釈したオクチル酸錫0.3gとを加え、窒素雰囲気下に80℃で3時間反応させて、遊離NCO基含有量2.10%および粘度50000mPa・S(20℃)の末端NCO含有プレポリマー(B)を得る。
Production Example 2: Production of terminal NCO-containing prepolymer (B) 1035 g of polyoxypropylene diol having a hydroxyl value of 27.9 and 203 g of polyoxypropylene triol having a hydroxyl value of 33.7, 167 g of MDI, and octyl diluted to 1% with DINP 0.3 g of tin oxide was added and reacted at 80 ° C. for 3 hours under a nitrogen atmosphere to obtain a terminal NCO-containing prepolymer (B) having a free NCO group content of 2.10% and a viscosity of 50000 mPa · S (20 ° C.). obtain.
製造例3:
ジアリールビスフェノールA50gおよびDINP135gに、MDI85.2gを加え、窒素雰囲気下で4時間反応させて、遊離NCO基含有量5.44%のウレタンプレポリマーを得る。
Production Example 3:
85.2 g of MDI is added to 50 g of diarylbisphenol A and 135 g of DINP and reacted for 4 hours under a nitrogen atmosphere to obtain a urethane prepolymer having a free NCO group content of 5.44%.
実施例1
製造例1の末端NCO含有プレポリマー(A)400部(重量部、以下同様)に、DINP200部、乾燥したカーボンブラック200部、炭酸カルシウム150部、熱膨張性バルーン(日本フィライト(株)製「エクスパンセル009DU80」)2部、2,2−ジモルホリノジエチルエーテル1部およびオクチル酸ビスマス0.2部を加え、減圧脱泡下で撹拌混合して、粘度75Pa・sの一液型湿気硬化性ウレタン系組成物を得る。
Example 1
400 parts (parts by weight, the same applies hereinafter) of the terminal NCO-containing prepolymer (A) of Production Example 1 were added to 200 parts of DINP, 200 parts of dried carbon black, 150 parts of calcium carbonate, a thermally expandable balloon (manufactured by Nippon Philite Co., Ltd. EXPANSEL 009DU80 ") 2 parts, 1 part of 2,2-dimorpholinodiethyl ether and 0.2 part of bismuth octylate were added and stirred and mixed under reduced pressure defoaming. One-part moisture curing with a viscosity of 75 Pa · s A functional urethane-based composition is obtained.
比較例1
製造例2の末端NCO含有プレポリマー(B)350部に、DINP200部、乾燥したカーボンブラック200部、炭酸カルシウム200部、2,2−ジモルホリノジエチルエーテル1部およびオクチル酸ビスマス0.2部を加え、減圧脱泡下で撹拌混合して、粘度60Pa・sの一液型湿気硬化性ウレタン系組成物を得る。
Comparative Example 1
To 350 parts of the terminal NCO-containing prepolymer (B) of Production Example 2, 200 parts of DINP, 200 parts of dried carbon black, 200 parts of calcium carbonate, 1 part of 2,2-dimorpholinodiethyl ether and 0.2 part of bismuth octylate are added. In addition, the mixture is stirred and mixed under reduced pressure defoaming to obtain a one-pack type moisture-curable urethane composition having a viscosity of 60 Pa · s.
比較例2
実施例1において、製造例1の末端NCO含有プレポリマー(A)(400部)の代わりに、製造例2の末端NCO含有プレポリマー(B)(375部)および製造例3のウレタンプレポリマー(25部)を用いる以外は、同様にして一液型湿気硬化性ウレタン系組成物を得る。
Comparative Example 2
In Example 1, instead of the terminal NCO-containing prepolymer (A) (400 parts) of Production Example 1, the terminal NCO-containing prepolymer (B) of Production Example 2 (375 parts) and the urethane prepolymer of Production Example 3 ( A one-component moisture-curable urethane composition is obtained in the same manner except that 25 parts) is used.
接着試験
実施例1および比較例1〜2の一液型湿気硬化性ウレタン系組成物について、以下の要領で、剪断試験片を作成し、次いで高周波誘導加熱装置にて加熱した場合の、接着界面が破断するまでの時間と、破断時の温度を測定する。結果を下記表1に示す。
25mm幅のガラス板に、接着前処理としてプライマー(サンスター技研(株)製、#435−41)を塗布し、乾燥する。
一方、自動車用焼付塗料を塗装した25mm幅の塗装鋼板にも、接着前処理してプライマー(サンスター技研(株)製、#435−98)を塗布し、乾燥した後、これに各例の一液型湿気硬化性ウレタン系組成物を接着幅25mm、厚さ5mm、奥行10mmとなるように塗布、修正し、次いで前記の前処理ガラス板を重ね合せて剪断試験片を作成する。
Adhesion interface in the case of preparing a shear test piece in the following manner for the one-component moisture-curable urethane-based composition of Adhesion Test Example 1 and Comparative Examples 1-2, and then heating with a high-frequency induction heating device Measure the time to break and the temperature at break. The results are shown in Table 1 below.
A primer (Sunstar Giken Co., Ltd., # 435-41) is applied as a pretreatment for adhesion to a 25 mm wide glass plate and dried.
On the other hand, a primer (Sunstar Giken Co., Ltd., # 435-98) was applied to a 25 mm wide coated steel sheet coated with an automotive baking paint, dried, and then dried. A one-component moisture-curable urethane-based composition is applied and corrected so as to have an adhesion width of 25 mm, a thickness of 5 mm, and a depth of 10 mm, and then the pretreated glass plate is overlaid to prepare a shear test piece.
かかる剪断試験片を20℃、65%RHにて168時間放置せしめ、この時点で、常態引張強度(MPa)を測定する(引張強度50mm/分)。
また、同様に作成した剪断試験片の解体性を確認する。すなわち、高周波誘導加熱装置(アキレス(株)製、オールオーバー接着装置)の照射面から塗装鋼板側が4mmの距離となるように、剪断試験片の塗装鋼板部を固定し、照射開始から塗装鋼板と接着剤界面が自然に破断するまでの時間と、その破断時の接着剤付近の塗装鋼板の温度を測定する。
Such a shear test piece is allowed to stand at 20 ° C. and 65% RH for 168 hours, and at this point, the normal tensile strength (MPa) is measured (tensile strength 50 mm / min).
Moreover, the dismantling property of the shear test piece produced similarly is confirmed. That is, the coated steel plate part of the shear test piece is fixed so that the coated steel plate side is at a distance of 4 mm from the irradiated surface of the high frequency induction heating device (Achilles Co., Ltd., all-over bonding device). The time until the adhesive interface naturally breaks and the temperature of the coated steel sheet near the adhesive at the time of the breakage are measured.
本発明の容易に加熱分解しうる一液型湿気硬化性ウレタン系組成物は、特に自動車窓ガラスの接着に用いる接着剤に有用であるが、他の接着剤、シーリング材、塗料、注型材、封止材、発泡体、成形体等においても部材の修理交換、リサイクル、廃棄処理するときなど、部材を取除くときに加熱処理して容易に分解する用途に適用できることは云うまでもない。
本発明の好ましい態様は、以下を包含する。
[1] オキシム基とイソシアネート基の反応によるウレタン結合を含有する末端イソシアネート基含有ウレタンプレポリマーを成分とすることを特徴とする容易に加熱分解しうる一液型湿気硬化性ウレタン系組成物。
[2] 該オキシム基含有化合物がジオキシム化合物であり、かつ該イソシアネート基含有化合物がポリイソシアネート化合物である[1]に記載の容易に加熱分解しうる一液型湿気硬化性ウレタン系組成物。
[3] 加熱処理により容易に軟化、解体させる必要のある接着剤、シーリング材、塗料、注型材、封止材、発泡体の用途に用いる[1]または[2]に記載の容易に加熱分解しうる一液型湿気硬化性ウレタン系組成物。
[4] 自動車窓ガラスの接着に用いる接着剤である[1]乃至[3]のいずれか1つに記載の容易に加熱分解しうる一液型湿気硬化性ウレタン系組成物。
The one-component moisture-curable urethane-based composition that can be easily thermally decomposed according to the present invention is particularly useful as an adhesive used for bonding automobile window glass, but other adhesives, sealing materials, paints, casting materials, Needless to say, the present invention can also be applied to a sealing material, a foam, a molded body, etc. that can be easily decomposed by heat treatment when removing the member, such as when repairing, recycling, or discarding the member.
Preferred embodiments of the present invention include the following.
[1] A readily heat-decomposable one-component moisture-curable urethane-based composition comprising, as a component, a terminal isocyanate group-containing urethane prepolymer containing a urethane bond by a reaction between an oxime group and an isocyanate group.
[2] The easily heat-decomposable one-component moisture-curable urethane composition according to [1], wherein the oxime group-containing compound is a dioxime compound and the isocyanate group-containing compound is a polyisocyanate compound.
[3] Easy thermal decomposition as described in [1] or [2] used for adhesives, sealing materials, paints, casting materials, sealing materials, foams that need to be easily softened and disassembled by heat treatment One-pack type moisture curable urethane composition that can be used.
[4] The one-component moisture-curable urethane-based composition that can be easily thermally decomposed according to any one of [1] to [3], which is an adhesive used for bonding an automobile window glass.
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