JP7568124B2 - Moisture-curable polyurethane resin composition, adhesive, and laminate - Google Patents
Moisture-curable polyurethane resin composition, adhesive, and laminate Download PDFInfo
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- JP7568124B2 JP7568124B2 JP2023548656A JP2023548656A JP7568124B2 JP 7568124 B2 JP7568124 B2 JP 7568124B2 JP 2023548656 A JP2023548656 A JP 2023548656A JP 2023548656 A JP2023548656 A JP 2023548656A JP 7568124 B2 JP7568124 B2 JP 7568124B2
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Description
本発明は、湿気硬化型ポリウレタン樹脂組成物、接着剤、及び、積層体に関する。 The present invention relates to a moisture-curable polyurethane resin composition, an adhesive, and a laminate.
透湿性と防水性とを併せ持つ透湿防水機能性衣料は、透湿性フィルムを接着剤で生地に貼り合わせた構成体であり、前記接着剤としては、透湿性フィルムと生地との双方との密着性が良好な点から、ウレタン系接着剤が一般的に使用されている。また、前記ウレタン系接着剤の中でも、昨今の世界的な溶剤排出規制や残留溶剤規制から、無溶剤型である湿気硬化型ポリウレタン樹脂組成物の使用量が徐々に増加しつつある（例えば、特許文献１を参照。）。 Moisture-permeable, waterproof functional clothing that has both moisture permeability and waterproofness is a structure in which a moisture-permeable film is bonded to a fabric with an adhesive, and urethane-based adhesives are generally used as the adhesive because of their good adhesion to both the moisture-permeable film and the fabric. Furthermore, among the urethane-based adhesives, the amount of use of solvent-free moisture-curing polyurethane resin compositions is gradually increasing due to recent global regulations on solvent emissions and residual solvents (see, for example, Patent Document 1).
一方で、使用される生地は、軽量化・高機能化から細デニール化と撥水度とが向上しており、先撥水処理布と接着剤との接着性が低下する課題があり、現行の湿気硬化型ポリウレタン樹脂組成物では、特に超撥水生地に対する高い密着性を発現するものは見出されていなかった。 On the other hand, the fabrics used are becoming lighter and more functional, with finer denier and improved water repellency, which poses the issue of reduced adhesion between the water-repellent treated fabric and the adhesive. None of the current moisture-curing polyurethane resin compositions have been found to exhibit particularly high adhesion to ultra-water-repellent fabrics.
本発明が解決しようとする課題は、生地（特に、撥水性生地）との接着性、及び、耐洗濯性に優れる湿気硬化型ポリウレタン樹脂組成物を提供することである。 The problem that the present invention aims to solve is to provide a moisture-curable polyurethane resin composition that has excellent adhesion to fabrics (especially water-repellent fabrics) and excellent washability.
本発明は、ポリオール（Ａ）、及び、ポリイソシアネート（Ｂ）の反応物である、イソシアネート基を有するウレタンプレポリマー（ｉ）を含有する湿気硬化型ポリウレタンホットメルト樹脂組成物であって、前記ポリオール（Ａ）が、下記一般式（１）で示される化合物（ａ１）を含有することを特徴とする湿気硬化型ポリウレタンホットメルト樹脂組成物。 The present invention is a moisture-curable polyurethane hot-melt resin composition containing a urethane prepolymer (i) having an isocyanate group, which is a reaction product of a polyol (A) and a polyisocyanate (B), characterized in that the polyol (A) contains a compound (a1) represented by the following general formula (1).
また、本発明は、前記湿気硬化型ポリウレタン樹脂組成物を含有することを特徴とする接着剤を提供するものである。更に、本発明は、少なくとも、生地（ｉ）、及び、前記湿気硬化型ポリウレタン樹脂組成物の硬化物を有することを特徴とする積層体を提供するものである。 The present invention also provides an adhesive that contains the moisture-curable polyurethane resin composition. Furthermore, the present invention also provides a laminate that has at least a substrate (i) and a cured product of the moisture-curable polyurethane resin composition.
本発明の湿気硬化型ポリウレタンホットメルト樹脂組成物は、溶剤を含まないものであり、環境対応型の材料である。また、本発明の湿気硬化型ポリウレタンホットメルト樹脂組成物は、様々な生地に対する接着性に優れるものであり、撥水性生地に対しても優れた接着性を有し、耐洗濯性にも優れるものである。 The moisture-curable polyurethane hot melt resin composition of the present invention does not contain a solvent and is an environmentally friendly material. In addition, the moisture-curable polyurethane hot melt resin composition of the present invention has excellent adhesion to various fabrics, has excellent adhesion to water-repellent fabrics, and is also excellent in washability.
本発明で用いる湿気硬化型ポリウレタンホットメルト樹脂組成物は、特定の化合物を含むポリオール（Ａ）、及び、ポリイソシアネート（Ｂ）の反応物であり、イソシアネート基を有するウレタンプレポリマー（ｉ）を含有するものである。 The moisture-curable polyurethane hot melt resin composition used in the present invention is a reaction product of a polyol (A) containing a specific compound and a polyisocyanate (B), and contains a urethane prepolymer (i) having an isocyanate group.
前記ポリオール（Ａ）は、優れた生地（特に、撥水性生地）への接着性、及び耐洗濯性を得る上で、前記した一般式（１）で示される化合物（ａ１）を含むことが必須である。 It is essential that the polyol (A) contains the compound (a1) represented by the general formula (1) described above in order to obtain excellent adhesion to fabrics (especially water-repellent fabrics) and washability.
前記ポリオール（Ａ）として、前記化合物（ａ１）のような、水酸基を両末端に有し、かつシリコーン鎖、および長鎖アルキル基を有する化合物を導入することで、撥水性生地への浸透性（親和性）が向上し、優れた接着性及び耐洗濯性が発現すると考えられる。 By introducing a compound having hydroxyl groups at both ends, a silicone chain, and a long-chain alkyl group, such as compound (a1), into the polyol (A), it is believed that the permeability (affinity) to water-repellent fabrics is improved, and excellent adhesion and washability are achieved.
前記化合物（ａ１）としては、より一層優れた接着性、及び耐洗濯性が得られる点から、Ｒ１が炭素原子数１～２のアルキレン基が好ましく、エチレン基がより好ましい。また、Ｒ２は炭素原子数３～６のアルキレン基が好ましく、プロピレン基がより好ましい。また、ｍはそれぞれ５～２０の整数が好ましく、５～１５の整数がより好ましく、ｎはそれぞれ０～４０の整数が好ましく、０～２０の整数がより好ましい。また、ａは５～３０の整数が好ましく、１０～２０の整数がより好ましい。 In the compound (a1), R 1 is preferably an alkylene group having 1 to 2 carbon atoms, more preferably an ethylene group, from the viewpoint of obtaining even better adhesiveness and wash resistance. R 2 is preferably an alkylene group having 3 to 6 carbon atoms, more preferably a propylene group. m is preferably an integer of 5 to 20, more preferably an integer of 5 to 15, and n is preferably an integer of 0 to 40, more preferably an integer of 0 to 20. a is preferably an integer of 5 to 30, more preferably an integer of 10 to 20.
前記化合物（ａ１）の使用量としては、より一層優れた接着性、及び、耐洗濯性が得られる点から、ポリオール（Ａ）中０．５～３０質量％が好ましく、１．０～１５質量％がより好ましい。 The amount of compound (a1) used is preferably 0.5 to 30% by mass, and more preferably 1.0 to 15% by mass, in polyol (A) in order to obtain even better adhesion and washability.
前記ポリオール（Ａ）としては、前記化合物（ａ１）以外のその他のポリオールを併用してもよい。前記その他のポリオールとしては、例えば、ポリエステルポリオール、ポリエーテルポリオール、ポリカーボネートポリオール、ポリアクリルポリオールなどを用いることができる。これらのポリオールは単独で用いても２種以上を併用してもよい。これらの中でも、より一層優れた機械的強度などが得られる点から、ポリエステルポリオール、及び／又はポリエーテルポリオールが好ましい。 As the polyol (A), other polyols other than the compound (a1) may be used in combination. As the other polyols, for example, polyester polyols, polyether polyols, polycarbonate polyols, polyacrylic polyols, etc. may be used. These polyols may be used alone or in combination of two or more. Among these, polyester polyols and/or polyether polyols are preferred because they provide even better mechanical strength, etc.
前記ポリエステルポリオールとしては、例えば、多塩基酸と水酸基を２個以上有する化合物との反応物を用いることができる。 The polyester polyol can be, for example, a reaction product of a polybasic acid and a compound having two or more hydroxyl groups.
前記多塩基酸としては、例えば、シュウ酸、マロン酸、コハク酸、アジピン酸、セバシン酸、アゼライン酸、ドデカンジカルボン酸、グルタル酸、ピメリン酸、スベリン酸、ダイマー酸、セバシン酸、ウンデカンジカルボン酸、ヘキサヒドロテレフタル酸、フタル酸化合物（フタル酸、無水フタル酸、イソフタル酸、テレフタル酸）等を用いることができる。これらの多塩基酸は単独で用いても２種以上を併用してもよい。これらの中でも、より一層優れた接着性、機械的強度が得られる点から、アジピン酸、及び／又は、フタル酸化合物が好ましい。 Examples of the polybasic acid that can be used include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, glutaric acid, pimelic acid, suberic acid, dimer acid, sebacic acid, undecanedicarboxylic acid, hexahydroterephthalic acid, and phthalic acid compounds (phthalic acid, phthalic anhydride, isophthalic acid, and terephthalic acid). These polybasic acids may be used alone or in combination of two or more. Among these, adipic acid and/or phthalic acid compounds are preferred because they provide even better adhesion and mechanical strength.
前記２個以上有する化合物との反応物としては、例えば、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、１，３－ブタンジオール、１，４－ブタンジオール、ペンタンジオール、２，４－ジエチル－１，５－ペンタンジオール、３－メチル－１，５－ペンタンジオール、ヘキサンジオール、ネオペンチルグリコール、ヘキサメチレングリコール、グリセリン、トリメチロールプロパン、ビスフェノールＡやビスフェノールＦ、及びそのアルキレンオキサイド付加物、２－メチル－１，３－プロパンジオール、２－メチル－１，５－ペンタンジオール、３－メチル－１，５－ペンタンジオール、２，２，４－トリメチル－１，３－ペンタンジオール、１，２－ブタンジオール、１，３－ブタンジオール、２－ブチル－２－エチル－１，３－プロパンジオール、１，２－プロパンジオール、２－メチル－１，３－プロパンジオール、ネオペンチルグリコール、２－イソプロピル－１，４－ブタンジオール、２，４－ジメチル－１，５－ペンタンジオール２，４－ジエチル－１，５－ペンタンジオール、２－エチル－１，３－ヘキサンジオール、２－エチル－１，６－ヘキサンジオール、３，５－ヘプタンジオール、２－メチル－１，８－オクタンジオール、ネオペンチルグリコール、トリメチロールプロパン等を用いることができる。これらの化合物は単独で用いても２種以上を併用してもよい。 Examples of reactants with compounds having two or more of the above groups include ethylene glycol, diethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, pentanediol, 2,4-diethyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, hexanediol, neopentyl glycol, hexamethylene glycol, glycerin, trimethylolpropane, bisphenol A, bisphenol F, and their alkylene oxide adducts, 2-methyl-1,3-propanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,2,4 -Trimethyl-1,3-pentanediol, 1,2-butanediol, 1,3-butanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,2-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-isopropyl-1,4-butanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-ethyl-1,6-hexanediol, 3,5-heptanediol, 2-methyl-1,8-octanediol, neopentyl glycol, trimethylolpropane, etc. can be used. These compounds may be used alone or in combination of two or more.
前記ポリエステルポリオールの数平均分子量としては、より一層優れた接着性、機械的強度が得られる点から、５００～１０，０００が好ましく、７００～５，０００がより好ましい。なお、前記ポリエステルポリオールの数平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により測定した値を示す。 The number average molecular weight of the polyester polyol is preferably 500 to 10,000, and more preferably 700 to 5,000, in order to obtain even better adhesion and mechanical strength. The number average molecular weight of the polyester polyol is a value measured by gel permeation chromatography (GPC).
前記ポリエステルポリオールを用いる場合の使用量としては、より一層優れた機械的強度などが得られる点から、ポリオール（Ａ）中１０～１００質量％が好ましく、３０～１００質量％がより好ましい。 When the polyester polyol is used, the amount used is preferably 10 to 100% by mass, and more preferably 30 to 100% by mass, of the polyol (A) in order to obtain even better mechanical strength, etc.
前記ポリエーテルポリオールとしては、例えば、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコールなどを用いることができる。これらは単独で用いても２種以上を併用してもよい。これらの中でも、より一層より一層優れた接着性、機械的強度が得られる点から、ポリプロピレングリコールが好ましい。 As the polyether polyol, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. can be used. These may be used alone or in combination of two or more. Among these, polypropylene glycol is preferred because it provides even more excellent adhesion and mechanical strength.
前記ポリエーテルポリオールの数平均分子量としては、より一層優れた接着性、機械的強度が得られる点から、５００～１０，０００が好ましく、７００～５，０００がより好ましい。なお、前記ポリエーテルポリオールの数平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により測定した値を示す。 The number average molecular weight of the polyether polyol is preferably 500 to 10,000, more preferably 700 to 5,000, in order to obtain even better adhesion and mechanical strength. The number average molecular weight of the polyether polyol is a value measured by gel permeation chromatography (GPC).
前記ポリエーテルポリオールを用いる場合の使用量としては、より一層優れた機械的強度などが得られる点から、ポリオール（Ａ）中０～９０質量％が好ましく、０～７０質量％がより好ましい。 When the polyether polyol is used, the amount used is preferably 0 to 90% by mass, more preferably 0 to 70% by mass, of the polyol (A) in order to obtain even better mechanical strength, etc.
前記ポリイソシアネート（Ｂ）としては、ポリメチレンポリフェニルポリイソシアネート、ジフェニルメタンジイソシアネート、カルボジイミド変性ジフェニルメタンジイソシアネートイソシアネート、キシリレンジイソシアネート、フェニレンジイソシアネート、トリレンジイソシアネート、ナフタレンジイソシアネート等の芳香族ポリイソシアネート；ヘキサメチレンジイソシアネート、シクロヘキサンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、テトラメチルキシリレンジイソシアネート等の脂肪族又は脂環族ポリイソシアネートなどを用いることができる。これらのポリイソシアネートは単独で用いても２種以上を併用してもよい。これらの中でも、より一層優れた反応性、及び、生地への接着性が得られる点から、芳香族ポリイソシアネートを用いることが好ましく、ジフェニルメタンジイソシアネートがより好ましい。 As the polyisocyanate (B), aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate isocyanate, xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and tetramethylxylylene diisocyanate can be used. These polyisocyanates can be used alone or in combination of two or more. Among these, aromatic polyisocyanates are preferred from the viewpoint of obtaining even better reactivity and adhesion to fabrics, and diphenylmethane diisocyanate is more preferred.
前記ポリイソシアネート（Ｂ）の使用量としては、ウレタンプレポリマー（ｉ）を構成する原料の合計質量中５～４０質量％が好ましく、１０～３０質量％がより好ましい。 The amount of the polyisocyanate (B) used is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, based on the total mass of the raw materials constituting the urethane prepolymer (i).
前記ホットメルトウレタンプレポリマー（ｉ）は、前記ポリオール（Ａ）と前記ポリイソシアネート（Ｂ）とを反応させて得られるものであり、空気中や湿気硬化型ポリウレタンホットメルト樹脂組成物が塗布される基材中に存在する水分と反応して架橋構造を形成しうるイソシアネート基を有するものである。 The hot-melt urethane prepolymer (i) is obtained by reacting the polyol (A) with the polyisocyanate (B), and has an isocyanate group that can react with moisture present in the air or in the substrate to which the moisture-curable polyurethane hot-melt resin composition is applied to form a crosslinked structure.
前記ホットメルトウレタンプレポリマー（ｉ）の製造方法としては、例えば、前記ポリオール（Ａ）の入った反応容器に、前記ポリイソシアネート（Ｂ）を入れ、前記ポリイソシアネート（Ｂ）の有するイソシアネート基が、前記ポリオール（Ａ）の有する水酸基に対して過剰となる条件で反応させることによって製造することができる。 The hot melt urethane prepolymer (i) can be produced, for example, by adding the polyisocyanate (B) to a reaction vessel containing the polyol (A) and reacting them under conditions in which the isocyanate groups of the polyisocyanate (B) are in excess of the hydroxyl groups of the polyol (A).
前記ホットメルトウレタンプレポリマー（ｉ）を製造する際の、前記ポリイソシアネート（Ｂ）が有するイソシアネート基と前記ポリオール（Ａ）が有する水酸基との当量比（イソシアネート基／水酸基）としては、より一層優れた生地への接着性が得られる点から、１．１～５が好ましく、１．５～３．０がより好ましい。 When producing the hot melt urethane prepolymer (i), the equivalent ratio (isocyanate group/hydroxyl group) of the isocyanate group of the polyisocyanate (B) to the hydroxyl group of the polyol (A) is preferably 1.1 to 5, and more preferably 1.5 to 3.0, in order to obtain even better adhesion to fabrics.
以上の方法によって得られたホットメルトウレタンプレポリマー（ｉ）のイソシアネート基含有率（以下、「ＮＣＯ％」と略記する。）としては、より一層優れた接着性が得られる点から、１．７～５の範囲が好ましく、１．８～３．０がより好ましい。なお、前記ホットメルトウレタンプレポリマー（ｉ）のＮＣＯ％は、ＪＩＳ Ｋ１６０３－１：２００７に準拠し、電位差滴定法により測定した値を示す。 The isocyanate group content (hereinafter abbreviated as "NCO%) of the hot melt urethane prepolymer (i) obtained by the above method is preferably in the range of 1.7 to 5, and more preferably 1.8 to 3.0, in order to obtain even better adhesion. The NCO% of the hot melt urethane prepolymer (i) is a value measured by potentiometric titration in accordance with JIS K1603-1:2007.
本発明で用いる湿気硬化型ポリウレタンホットメルト樹脂組成物は、前記ウレタンプレポリマー（ｉ）を必須成分として含有するものであるが、必要に応じて、その他の添加剤を用いてもよい。 The moisture-curable polyurethane hot melt resin composition used in the present invention contains the urethane prepolymer (i) as an essential component, but other additives may be used as necessary.
前記その他の添加剤としては、例えば、耐光安定性、硬化触媒、粘着付与剤、可塑剤、安定剤、充填材、染料、顔料、蛍光増白剤、シランカップリング剤、ワックス、熱可塑性樹脂等を用いることができる。これらの添加剤は単独で用いても２種以上を併用してもよい。 Examples of the other additives that can be used include light resistance stabilizers, curing catalysts, tackifiers, plasticizers, stabilizers, fillers, dyes, pigments, fluorescent brighteners, silane coupling agents, waxes, thermoplastic resins, etc. These additives may be used alone or in combination of two or more.
以上、本発明の湿気硬化型ポリウレタンホットメルト樹脂組成物は、溶剤を含まないものであり、環境対応型の材料である。また、本発明の湿気硬化型ポリウレタンホットメルト樹脂組成物は、様々な生地に対する接着性に優れるものであり、撥水性生地に対しても優れた接着性を有し、かつ耐洗濯性にも優れるものである。 As described above, the moisture-curable polyurethane hot melt resin composition of the present invention does not contain a solvent and is an environmentally friendly material. In addition, the moisture-curable polyurethane hot melt resin composition of the present invention has excellent adhesion to various fabrics, has excellent adhesion to water-repellent fabrics, and also has excellent washability.
次に、本発明の積層体について説明する。 Next, we will explain the laminate of the present invention.
本発明の積層体は、少なくとも、生地（ｉ）、及び、前記湿気硬化型ポリウレタンホットメルト樹脂組成物の硬化物を有するものである。 The laminate of the present invention has at least a substrate (i) and a cured product of the moisture-curable polyurethane hot melt resin composition.
前記生地（ｉ）としては、例えば、ポリエステル繊維、ポリエチレン繊維、ナイロン繊維、アクリル繊維、ポリウレタン繊維、アセテート繊維、レーヨン繊維、ポリ乳酸繊維、綿、麻、絹、羊毛、グラスファイバー、炭素繊維、それらの混紡繊維等による不織布、織布、編み物等の繊維基材；前記不織布にポリウレタン樹脂等の樹脂を含浸させたもの；前記不織布に更に多孔質層を設けたもの；樹脂基材などを用いることができる。 Examples of the fabric (i) that can be used include fiber substrates such as nonwoven fabrics, woven fabrics, knitted fabrics, etc. made of polyester fibers, polyethylene fibers, nylon fibers, acrylic fibers, polyurethane fibers, acetate fibers, rayon fibers, polylactic acid fibers, cotton, hemp, silk, wool, glass fibers, carbon fibers, and blends thereof; nonwoven fabrics impregnated with resins such as polyurethane resin; nonwoven fabrics further provided with a porous layer; and resin substrates.
また、本発明は前記生地（ｉ）として、前記したものに撥水処理を施したもの（以下、「撥水性生地」と略記する。）であっても優れた接着性を示す。なお、本発明において前記撥水性生地の「撥水性」とは、下記計算により得られる表面自由エネルギーが５０ｍＪ／ｍ２以下であるものを示す。 In addition, the present invention also shows excellent adhesiveness even when the above-mentioned fabric (i) is subjected to a water-repellent treatment (hereinafter, abbreviated as "water-repellent fabric"). In the present invention, the "water-repellent" of the water-repellent fabric indicates that the surface free energy obtained by the following calculation is 50 mJ/ m2 or less.
前記生地（ｉ）上での測定用液（水及びジヨードメタン）の接触角を、接触角計（協和界面科学社製「ＤＭ５００」）を使用して測定した。この結果に基づき、下記の式（１）を用いて生地（ｉ）の表面自由エネルギーを算出した。
（１＋ｃｏｓＡ）・γＬ／２＝（γsｄ・γＬｄ）１／２＋（γsｐ・γＬｐ）１／２
The contact angles of the test liquids (water and diiodomethane) on the fabric (i) were measured using a contact angle meter ("DM500" manufactured by Kyowa Interface Science Co., Ltd.) Based on the results, the surface free energy of the fabric (i) was calculated using the following formula (1).
(1+cosA)・γL/2=(γsd・γLd)1/2+(γsp・γLp)1/2
Ａ；生地（ｉ）上の測定用液の接触角
γＬ；測定用液の表面張力
γＬｄ；測定用液の表面自由エネルギーの分散力成分
γＬｐ；測定用液の表面自由エネルギーの極性力成分
γsｄ；生地（ｉ）の表面自由エネルギーの分散力成分
γsｐ；生地（ｉ）の表面自由エネルギーの極性力成分
A; contact angle of the test liquid on the fabric (i); γL; surface tension of the test liquid; γLd; dispersion force component of the surface free energy of the test liquid; γLp; polar force component of the surface free energy of the test liquid; dispersion force component of the surface free energy of the fabric (i); polar force component of the surface free energy of the fabric (i)
前記湿気硬化型ポリウレタンホットメルト樹脂組成物を塗工する方法としては、例えば、ロールコーター、ナイフコーター、スプレーコーター、グラビアロールコーター、コンマコーター、Ｔ－ダイコーター、アプリケーター、ディスペンサー等を使用する方法が挙げられる。 Methods for applying the moisture-curable polyurethane hot melt resin composition include, for example, methods using a roll coater, knife coater, spray coater, gravure roll coater, comma coater, T-die coater, applicator, dispenser, etc.
前記湿気硬化型ポリウレタンホットメルト樹脂組成物を塗工後は、公知の方法により乾燥・養生することができる。 After the moisture-curable polyurethane hot melt resin composition is applied, it can be dried and cured by known methods.
前記湿気硬化型ウレタンホットメルト樹脂組成物の硬化物の厚さとしては、例えば、５～３００μｍの範囲である。 The thickness of the cured product of the moisture-curable urethane hot melt resin composition is, for example, in the range of 5 to 300 μm.
なお、本発明の湿気硬化型ポリウレタンホットメルト樹脂組成物が透湿防水機能性衣料の接着剤として用いられる場合には、前記湿気硬化型ポリウレタンホットメルト樹脂組成物は、グラビアロールコーター、ディスペンサーにより間欠塗布し、生地（ｉ）と公知の透湿フィルムとを貼り合わせることが好ましい。係る場合の前記湿気硬化型ポリウレタンホットメルト樹脂組成物の硬化物の厚さとしては、例えば、５～５０μｍの範囲である。 When the moisture-curable polyurethane hot melt resin composition of the present invention is used as an adhesive for moisture-permeable, waterproof functional clothing, it is preferable to apply the moisture-curable polyurethane hot melt resin composition intermittently using a gravure roll coater or a dispenser, and then bond the fabric (i) to a known moisture-permeable film. In such a case, the thickness of the cured product of the moisture-curable polyurethane hot melt resin composition is, for example, in the range of 5 to 50 μm.
前記透湿フィルムの上には、更に、湿気硬化型ポリウレタンホットメルト樹脂組成物を間欠塗布によりメッシュ生地を貼り合わせてもよい。 A mesh fabric may be attached to the moisture-permeable film by intermittently applying a moisture-curable polyurethane hot melt resin composition.
以下、実施例を用いて本発明をより詳細に説明する。 The present invention will be explained in more detail below using examples.
［実施例１］
温度計、撹拌機、不活性ガス導入口および還流冷却器を備えた四口フラスコに、ポリエステルポリオール１（アジピン酸、及び、２－メチル－１，３－プロパンジオールを反応させたもの、数平均分子量；２，０００）４９５質量部、ポリエステルポリオール２（無水フタル酸、ジエチレングリコール、及び、ネオペンチルグリコールを反応させたもの、数平均分子量；１，０００）４９５質量部、式（１）において、Ｒ１がエチレン基、ｍが２０、ｎが０、ａが１５を示す化合物（以下「ａ１－１」と略記する。）を１０質量部を仕込み、１１０℃にて減圧乾燥して、水分量が０．０５質量％以下となるまで脱水した 次いで、６０℃に冷却後、ジフェニルメタンジイソシアネート（以下、「ＭＤＩ」と略記する。）３３１質量部加え、１１０℃まで昇温し、イソシアネート基含有量が一定となるまで２時間反応することで、ウレタンプレポリマー（１）を得て、湿気硬化型ポリウレタンホットメルト樹脂組成物（１）とした。
[Example 1]
A four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser was charged with 495 parts by mass of polyester polyol 1 (a reaction product of adipic acid and 2-methyl-1,3-propanediol, number average molecular weight: 2,000), 495 parts by mass of polyester polyol 2 (a reaction product of phthalic anhydride, diethylene glycol, and neopentyl glycol, number average molecular weight: 1,000), and 10 parts by mass of a compound represented by formula (1) in which R 1 is an ethylene group, m is 20, n is 0, and a is 15 (hereinafter abbreviated as "a1-1"). The mixture was then dried under reduced pressure at 110°C to dehydrate the mixture until the water content was 0.05% by mass or less. Next, after cooling to 60°C, 331 parts by mass of diphenylmethane diisocyanate (hereinafter abbreviated as "MDI") was added, the temperature was raised to 110°C, and the mixture was reacted for 2 hours until the isocyanate group content became constant, thereby obtaining a urethane prepolymer (1), which was used as a moisture-curable polyurethane hot-melt resin composition (1).
［実施例２］
温度計、撹拌機、不活性ガス導入口および還流冷却器を備えた四口フラスコに、ポリエステルポリオール３（１，６－ヘキサンジオール及び無水フタル酸を反応させたもの、数平均分子量；２，０００）１５０質量部、ポリエステルポリオール４（無水フタル酸、アジピン酸、テレフタル酸、及びエチレングリコールを反応させたもの、数平均分子量；３，５００）７００質量部、式（１）において、Ｒ１がエチレン基、ｍが１５、ｎが５、ａが１５を示す化合物（以下「ａ１－２」と略記する。）を３０質量部を仕込み、１１０℃にて減圧乾燥して、水分量が０．０５質量％以下となるまで脱水した 次いで、６０℃に冷却後、ＭＤＩ２００質量部加え、１１０℃まで昇温し、イソシアネート基含有量が一定となるまで２時間反応することで、ウレタンプレポリマー（２）を得、湿気硬化型ポリウレタンホットメルト樹脂組成物（２）とした。
[Example 2]
A four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser was charged with 150 parts by mass of polyester polyol 3 (1,6-hexanediol and phthalic anhydride reacted, number average molecular weight: 2,000), 700 parts by mass of polyester polyol 4 (phthalic anhydride, adipic acid, terephthalic acid, and ethylene glycol reacted, number average molecular weight: 3,500), and 30 parts by mass of a compound in which R 1 is an ethylene group, m is 15, n is 5, and a is 15 (hereinafter abbreviated as "a1-2"). The mixture was dried under reduced pressure at 110 ° C. and dehydrated until the water content was 0.05% by mass or less. Next, after cooling to 60 ° C., 200 parts by mass of MDI was added, the temperature was raised to 110 ° C., and the mixture was reacted for 2 hours until the isocyanate group content became constant, to obtain a urethane prepolymer (2), which was a moisture-curable polyurethane hot melt resin composition (2).
［実施例３］
温度計、撹拌機、不活性ガス導入口および還流冷却器を備えた四口フラスコに、ポリポロピレングリコール１（数平均分子量；４００）２９５質量部、ポリプロピレングリコール２（数平均分子量；１，０００）２９５質量部、式（１）において、Ｒ１がエチレン基、ｍが１０、ｎが１０、ａが１５を示す化合物（以下「ａ１－３」と略記する。）を３０質量部を仕込み、１１０℃にて減圧乾燥して、水分量が０．０５質量％以下となるまで脱水した 次いで、６０℃に冷却後、ＭＤＩを４５９質量部加え、１１０℃まで昇温し、イソシアネート基含有量が一定となるまで２時間反応することで、ウレタンプレポリマー（３）を得、湿気硬化型ポリウレタンホットメルト樹脂組成物（３）とした。
[Example 3]
A four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser was charged with 295 parts by mass of polypropylene glycol 1 (number average molecular weight; 400), 295 parts by mass of polypropylene glycol 2 (number average molecular weight; 1,000), and 30 parts by mass of a compound in which R 1 is an ethylene group, m is 10, n is 10, and a is 15 in the formula (1) (hereinafter abbreviated as "a1-3"). The mixture was dried under reduced pressure at 110 ° C. and dehydrated until the water content was 0.05% by mass or less. Next, after cooling to 60 ° C., 459 parts by mass of MDI was added, the temperature was raised to 110 ° C., and the mixture was reacted for 2 hours until the isocyanate group content became constant, thereby obtaining a urethane prepolymer (3), which was a moisture-curable polyurethane hot melt resin composition (3).
［比較例１］
温度計、撹拌機、不活性ガス導入口および還流冷却器を備えた四口フラスコに、ポリエステルポリオール１（アジピン酸、及び、２－メチル－１，３－プロパンジオールを反応させたもの、数平均分子量；２，０００）４９５質量部、ポリエステルポリオール２（無水フタル酸、ジエチレングリコール、及び、ネオペンチルグリコールを反応させたもの、数平均分子量；１，０００）４９５質量部、１１０℃にて減圧乾燥して、水分量が０．０５質量％以下となるまで脱水した 次いで、６０℃に冷却後、ジフェニルメタンジイソシアネート（以下、「ＭＤＩ」と略記する。）３３１質量部加え、１１０℃まで昇温し、イソシアネート基含有量が一定となるまで２時間反応することで、ウレタンプレポリマー（Ｒ１）を得て、湿気硬化型ポリウレタンホットメルト樹脂組成物（Ｒ１）とした。
[Comparative Example 1]
A four-neck flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser was charged with 495 parts by mass of polyester polyol 1 (adipic acid and 2-methyl-1,3-propanediol reacted, number average molecular weight: 2,000), 495 parts by mass of polyester polyol 2 (phthalic anhydride, diethylene glycol, and neopentyl glycol reacted, number average molecular weight: 1,000), and dried under reduced pressure at 110 ° C. to dehydrate the water content to 0.05% by mass or less. Next, after cooling to 60 ° C., 331 parts by mass of diphenylmethane diisocyanate (hereinafter abbreviated as "MDI") was added, the temperature was raised to 110 ° C., and the mixture was reacted for 2 hours until the isocyanate group content became constant, to obtain a urethane prepolymer (R1), which was used as a moisture-curing polyurethane hot melt resin composition (R1).
［数平均分子量の測定方法］
実施例及び比較例で用いたポリオールの数平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により、下記の条件で測定した値を示す。
[Method for measuring number average molecular weight]
The number average molecular weights of the polyols used in the examples and comparative examples are values measured by gel permeation chromatography (GPC) under the following conditions.
測定装置：高速ＧＰＣ装置（東ソー株式会社製「ＨＬＣ－８２２０ＧＰＣ」）
カラム：東ソー株式会社製の下記のカラムを直列に接続して使用した。
「ＴＳＫｇｅｌ Ｇ５０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ４０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ３０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
「ＴＳＫｇｅｌ Ｇ２０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
検出器：ＲＩ（示差屈折計）
カラム温度：４０℃
溶離液：テトラヒドロフラン（ＴＨＦ）
流速：１．０ｍＬ／分
注入量：１００μＬ（試料濃度０．４質量％のテトラヒドロフラン溶液）
標準試料：下記の標準ポリスチレンを用いて検量線を作成した。
Measurement device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were used, connected in series.
"TSKgel G5000" (7.8mm I.D. x 30cm) x 1 "TSKgel G4000" (7.8mm I.D. x 30cm) x 1 "TSKgel G3000" (7.8mm I.D. x 30cm) x 1 "TSKgel G2000" (7.8mm I.D. x 30cm) x 1 Detector: RI (differential refractometer)
Column temperature: 40°C
Eluent: tetrahydrofuran (THF)
Flow rate: 1.0 mL/min Injection volume: 100 μL (sample concentration 0.4% by mass in tetrahydrofuran solution)
Standard sample: A calibration curve was prepared using the following standard polystyrene.
（標準ポリスチレン）
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－５００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－１０００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－２５００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ａ－５０００」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－１」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－２」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－４」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－１０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－２０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－４０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－８０」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－１２８」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－２８８」
東ソー株式会社製「ＴＳＫｇｅｌ 標準ポリスチレン Ｆ－５５０」
(Standard polystyrene)
"TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation
［積層体の作製方法］
まず、溶剤型ポリウレタン樹脂「クリスボンＳ－５２５（ＤＩＣ株式会社製）」と、メチルエチルケトンと、ジメチルホルムアミドとを混合したものを、ナイフコーターを用いて離型紙上に塗布量が１００ｇ／ｍ2（ｗｅｔ）になるように均一に塗布した後、７０℃で１分間、次いで１２０℃で２分間乾燥することで、厚さ１５μｍの透湿性ポリウレタンフィルムを作製した。
次いで、１２０℃で加熱溶融した前記湿気硬化型ポリウレタン樹脂組成物（１）～（３）および（Ｒ１）を、それぞれ１２０℃に加熱した格子状のグラビアロールを用いて、上記透湿性ポリウレタンフィルム１上に２０ｇ／ｍ２で間欠塗布した後、繊維質基材である４０デニールの撥水処理ナイロンタフタと貼り合わせ、温度２３℃・相対湿度６５％の環境下で３日間放置することにより積層体を作製した。
[Method of producing laminate]
First, a mixture of solvent-based polyurethane resin "CRISBON S-525 (DIC Corporation)", methyl ethyl ketone, and dimethylformamide was uniformly applied onto release paper using a knife coater so that the application amount was 100 g/m2 (wet), and then dried at 70°C for 1 minute and then at 120°C for 2 minutes to produce a moisture-permeable polyurethane film with a thickness of 15 μm.
Next, the moisture-curable polyurethane resin compositions (1) to (3) and (R1) were each heated and melted at 120°C, and then intermittently coated on the moisture-permeable polyurethane film 1 at 20 g/ m2 using a lattice-shaped gravure roll heated to 120°C. The film was then laminated with a 40 denier water-repellent nylon taffeta, which is a fibrous substrate, and allowed to stand for 3 days in an environment of 23°C and 65% relative humidity to produce a laminate.
［生地との接着性の評価方法］
得られた積層体を構成する透湿性ポリウレタンフィルム側に、１インチ幅のホットメルト布テープを１３０℃で５秒間かけて接着した後、ＪＩＳＫ６８５４－２に準拠して、株式会社島津製作所製「オートグラフＡＧ－１」（ヘッドスピード；２００ｍｍ／分）を使用して、温度２３℃及び相対湿度５０％の状態での常態接着強度を測定し、６．０Ｎ／ｉｎｃｈ以上であるものは優れた撥水性生地との接着性を有すると判断した。
[Method for evaluating adhesion to fabric]
A 1-inch-wide hot melt cloth tape was adhered to the moisture-permeable polyurethane film side of the obtained laminate at 130°C for 5 seconds, and then the normal adhesive strength was measured at a temperature of 23°C and a relative humidity of 50% using an Autograph AG-1 (head speed: 200 mm/min) manufactured by Shimadzu Corporation in accordance with JIS K6854-2. A normal adhesive strength of 6.0 N/inch or more was determined to have excellent adhesion to water-repellent fabric.
［耐洗濯性の評価方法］
得られた積層体を、ＪＩＳ Ｌ １０８９－１９７０に準拠して、水洗濯を５０回行い、洗濯後の外観を評価した。なお外観は下記の基準にしたがって目視で評価した。
「〇」；外観上、全く剥離していなかった。
「×」；外観上、接着面積の半分以上が剥離していた。
[Method for evaluating washing resistance]
The obtained laminate was washed 50 times in water in accordance with JIS L 1089-1970, and the appearance after washing was evaluated. The appearance was evaluated visually according to the following criteria.
"Good": No peeling was observed at all.
"X": More than half of the adhesive area was peeled off.
本発明の湿気硬化型ポリウレタンホットメルト樹脂組成物は、撥水性生地との接着性、及び、耐洗濯性に優れることが分かった。 It was found that the moisture-curable polyurethane hot melt resin composition of the present invention has excellent adhesion to water-repellent fabrics and excellent washability.
一方、比較例１は、化合物（ａ１）を用いない態様であるが、撥水生地に対する接着性、及び、耐洗濯性が不良であった。 On the other hand, Comparative Example 1, which does not use compound (a1), had poor adhesion to water-repellent fabric and poor washability.
Claims (6)
前記ポリオール（Ａ）が、下記一般式（１）で示される化合物（ａ１）と、ポリエステルポリオール、ポリエーテルポリオール、ポリカーボネートポリオール、ポリアクリルポリオールから選択される１種又は２種以上のポリオールと、を含有し、
前記ポリオール（Ａ）中における前記化合物（ａ１）の使用量が、０．５～３０質量％の範囲であることを特徴とする湿気硬化型ポリウレタンホットメルト樹脂組成物。
The polyol (A) contains a compound (a1) represented by the following general formula (1) and one or more polyols selected from a polyester polyol, a polyether polyol, a polycarbonate polyol, and a polyacrylic polyol ,
The amount of the compound (a1) used in the polyol (A) is in the range of 0.5 to 30 mass% .
前記ポリエーテルポリオールが、ポリプロピレングリコールである請求項１記載の湿気硬化型ポリウレタンホットメルト樹脂組成物。 The polyol (A) contains the polyether polyol,
2. The moisture-curable polyurethane hot-melt resin composition according to claim 1 , wherein the polyether polyol is polypropylene glycol.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008174749A (en) | 2007-01-17 | 2008-07-31 | Bayer Material Science Llc | Polyether-polysiloxane polyol |
| JP2013528667A (en) | 2010-03-29 | 2013-07-11 | モメンティブ パフォーマンス マテリアルズ インコーポレイテッド | Mixture of polydiorganosiloxane-containing silylated polyurethane and silylated polyurethane, and substrate containing the same, and process for producing the substrate |
| WO2018122940A1 (en) | 2016-12-26 | 2018-07-05 | サンスター技研株式会社 | Curable composition |
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| JP3837735B2 (en) * | 2001-05-29 | 2006-10-25 | 日本ポリウレタン工業株式会社 | Polyisocyanate composition for rigid polyurethane foam and method for producing rigid polyurethane foam using the same |
| CN109836554A (en) * | 2017-11-26 | 2019-06-04 | 沈阳益泰科信息咨询有限公司 | A kind of preparation method of polysiloxane modified polyurethane sealant performed polymer |
| CN108410412A (en) * | 2018-03-28 | 2018-08-17 | 陈太师 | A kind of rapid curing polyurethane water-proof fluid sealant and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008174749A (en) | 2007-01-17 | 2008-07-31 | Bayer Material Science Llc | Polyether-polysiloxane polyol |
| JP2013528667A (en) | 2010-03-29 | 2013-07-11 | モメンティブ パフォーマンス マテリアルズ インコーポレイテッド | Mixture of polydiorganosiloxane-containing silylated polyurethane and silylated polyurethane, and substrate containing the same, and process for producing the substrate |
| WO2018122940A1 (en) | 2016-12-26 | 2018-07-05 | サンスター技研株式会社 | Curable composition |
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