TW201217408A - Aqueous polyurethane resin dispersion and method for manufacture thereof, and its use - Google Patents

Aqueous polyurethane resin dispersion and method for manufacture thereof, and its use Download PDF

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TW201217408A
TW201217408A TW100130457A TW100130457A TW201217408A TW 201217408 A TW201217408 A TW 201217408A TW 100130457 A TW100130457 A TW 100130457A TW 100130457 A TW100130457 A TW 100130457A TW 201217408 A TW201217408 A TW 201217408A
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Taiwan
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compound
group
polyol
polyurethane resin
aqueous
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TW100130457A
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Chinese (zh)
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Takeshi Yamada
Teruaki Fujii
Masahiro Naiki
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Ube Industries
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

This invention provides an aqueous poly urethane resin dispersion which has excellent storage stability, and whose coating film cured with an active energy ray exhibits excellent adhesion to various plastics (ABS resin, acrylic resin, polycarbonate resin). This invention also provides an aqueous polyurethane resin dispersion which provides a coating film having high hardness. The agueous polyurethane resin dispersion is formed by at least dispersing (A) a polyurethane resin having a polymeric unsaturated bond and (B) a compound having a polymeric unsaturated bond, wherein (A) the polyurethane resin having polymeric unsaturated bond is formed by (a) polycarbonate diol having an alicyclic construction in a main chain, (b) a polyol containing an acidic group, (d) a polyisocyanate, and (e) a compound having, in one molecule, one or more than one group capable of reacting with an isocyanato group and one or more than one polymeric unsaturated bond. This invention also provides a coating composition containing the above aqueous polyurethane resin dispersion, and a method for manufacture of such coating composition.

Description

201217408 六、發明說明： 【發明所屬之技術領域】 本發明係有關一種可經由以紫外線為首之活性能量 線照射而硬化的水性聚氨基曱酸酯樹脂分散體及其製造方 法、以及其用途者。 【先前技術】 聚碳酸酯二醇係成為聚氨基甲酸酯樹脂 (polyurethane，有稱為聚胺基曱酸酯之情形，本案依一般 多數之習慣稱為聚氨基曱酸酯）之原料的有用化合物，藉與 異氰酸酯化合物之反應，可製造使用於硬質發泡、軟質發 泡、塗料、接著劑、合成皮革、印墨黏結劑等之聚氨基曱 酸酯樹脂。又，塗佈以聚碳酸酯多元醇作為原料之水性聚 氨基曱酸酯樹脂分散體所得到的塗膜係已知耐光性、耐熱 性、财水解性、耐油性優異（參照專利文獻1 )。 其中，已知塗佈使用脂肪族聚碳酸酯多元醇 (polycarbonate polyol)之水性氨基曱酸酯樹脂分散體所得 到的塗膜可提高與基材之密著性及防黏性，故可使用來作 為底塗劑（參照專利文獻2)。又，為提昇塗膜之硬度、耐 久性，亦提出一種使用具脂環構造之聚碳酸酯多元醇的水 性聚氨基曱酸酯樹脂分散體（參照專利文獻3、4及5)。 另外，一般所認知的自由基聚合性化合物，即使藉由 加熱以外之方法，硬化性亦為優異，故從生產性、省能源 之觀點，亦具有特長。具有自由基聚合性化合物之活性能 量線硬化性樹脂組成物係按照該特長，可使用來作為金屬 4 323441 201217408 用塗料、各種塑膠薄膜用被覆劑、木I用塗料、印刷印墨 等之各種塗佈或接著料之有效成分。例如，對於水性聚 氨基甲酉夂酉“对月曰分散體，而提案一種使(曱基)丙烯酸酯系 化合物分散之活性能量線硬化型水性樹脂組成物（參照專 利文獻6)。 又，亦提出一種使（曱基）丙烯酸化聚氨基曱酸酯、（曱 基）丙稀酸化合物分散於水系介f中而成之活性能量線硬 化型水性樹脂組成物（參照專利文獻7)。 [先前技術文獻] [專利文獻] [專利文獻1]日本特開平1〇_12〇757號公報 [專利文獻2]曰本特開2〇〇5_281544號公報 [專利文獻3]曰本特開平6-248046號公報 [專利文獻4]世界專利w〇2009/l45242號公報 [專利文獻5]世界專利W02010/004951號公報 [專利文獻6]曰本特開2008-248014號公報 [專利文獻7]曰本特表2009-533504號公報 [發明之揭示] [發明欲解決之課題] 但，在以聚碳酸酯多元醇作為原料之水性聚氨基甲酸 酯樹脂分散體中，若只使用脂肪族聚碳酸酯多元醇作為聚 碳酸酯多元醇時，塗佈水性聚氨基甲酸酯樹脂分散體所得 到之塗膜的密著性、硬度係例如在航空器、汽車等之外板、 住七之外壁面及地板材專之塗料領域或塗佈劑之領域中不 323441 5 201217408 足的問題存在。另外，若使用具有脂環構造之聚碳酸酯多 元醇時，則有水系介質中之分散性變差，使水性聚氨基甲 酸酯樹脂分散體之處理性及安定性出現問題之困擾，又， 可得到滿足密著性、硬度者並未受到認可。 另外’有關能量線硬化型水系樹脂組成物係於前述指 出之專利文獻6中，使用界面活性劑而使（甲基）丙烯酸酯 系化合物對水性聚氨基甲酸酯樹脂分散體分散，界面活性 劑殘存於塗膜中’有降低塗膜性能之問題點。在此組成物 中，若減少界面活性劑之使用量，或不使用，即產生所謂 貯存安定性降低之問題。 又，在專利文獻7中，具體上所揭示之（甲基）丙烯酸 化聚氨基甲酸酯樹脂多元醇與（甲基）丙烯酸化合物之組合 中，從能量線硬化型水系樹脂組成物所得到之塗膜對各種 塑膠（尤其ABS樹脂、丙烯酸樹脂）之密著性有不足的問 題點。 本發明之課題在於得到一種水性聚氨基甲酸酯樹脂 刀政體，其係活性能量線（例如紫外線）硬化型之水性聚 氨基甲酸酯樹脂分散體，具有於良好的水系介質中的分散 性及貯存安定性，且活性能量線（例如紫外線）硬化後之 塗膜對各種歸（ABS樹脂、丙稀酸樹脂、聚碳酸醋樹脂 等）之密著性優異。又，本發明之課題在於得到一種水性 聚氨基曱酸_齡韻，其餘性能量線（例如紫 硬化後之塗膜具有高的硬度者。 [用以解決課題之手段] 323441 6 201217408 本發明人等係為克服前述習知技術之問題點進行各 種研究之結果，發現使具有聚合性不飽和鍵之聚氨基甲酸 醋樹脂與具有聚合性不飽和鍵之化合物分散於水系介質中 而成之水性聚氨基甲酸酯樹脂分散體，係藉由使用具有脂 環構造之聚碳酸酯多元醇作為聚氨基曱酸酯樹脂之原料 者，俾可解決問題點。 本發明（1)係關於一種水性聚氨基甲酸酯樹脂分散 體，其係至少使具有聚合性不飽和鍵之聚氨基曱酸酯樹脂 (A)與具有聚合性不飽和鍵之化合物（B)分散於水系介 質中而成之水性聚氨基曱酸酯樹脂分散體，其特徵係： 具有聚合性不飽和鍵之聚氨基曱酸酯樹脂（A)為至 少使主鏈具有脂環構造之聚碳酸酯二醇(polycarbonatediol) (a )、含有酸性基之多元醇（b )、多元異氰酸酯 (polyisocyanate) (d)、與1分子中具有1個以上可與異氰 酸基反應的基與1個以上聚合性不飽和鍵的化合物（e)反 應所得到的聚氨基曱酸酯樹脂。 本發明（2)係關於本發明（1)之水性聚氨基曱酸酯樹脂 分散體，其中具有聚合性不飽和鍵之化合物（B)包含至 少含有3個（曱基）丙烯醯基之化合物。 本發明（3)係關於本發明（1)或（2)之水性聚氨基曱酸酯 樹脂分散體，其中具有聚合性不飽和鍵之化合物（B)包 含至少含有5個（曱基）丙烯醯基之化合物。 本發明（4)係關於本發明（1)至（3)中任一項之水性聚氨 基曱酸酯樹脂分散體，其中1分子中具有1個以上可與異 7 323441 201217408 氰酸基反應的基與1個以上聚合性不飽和鍵的化合物（e) 包含具有1個可與異氰酸基反應之基與1個以上（曱基）丙 稀醯基的化合物。 本發明（5)係關於本發明（1)至（4)中任一項之水性聚氨 基曱酸酯樹脂分散體，其中1分子中具有1個以上可與異 氰酸基反應的基與1個以上聚合性不飽和鍵的化合物（e) 包含具有1個可與異氰酸基反應之基與3個以上（甲基）丙 烯醯基的化合物。 本發明（6)係關於本發明（1)至（5)中任一項之水性聚氨 基曱酸酯樹脂分散體，其中1分子中具有1個以上可與異 氰酸基反應的基與1個以上聚合性不飽和鍵的化合物（e) 包含具有2個羥基與2個（曱基）丙烯醯基的化合物。 本發明（7)係關於本發明（1)至（6)中任一項之水性聚氨 基曱酸酯樹脂分散體，其中具有聚合性不飽和鍵之聚氨基 曱酸酯樹脂係由使主鏈具有脂環構造之聚碳酸酯二醇 (a)、含有酸性基之多元醇（b)、多元異氰酸酯（d)、與 1分子中具有1個以上可與異氰酸基反應的基與1個以上 聚合性不飽和鍵的化合物（e )、鏈延長劑（C )反應而得 者。 本發明（8)係關於本發明（7)之水性聚氨基曱酸酯樹脂 分散體，其中鏈延長劑（C )為1級多胺化合物。 本發明（9)係關於一種本發明（1)至（6)中任一項之水性 聚氨基甲酸酯樹脂分散體之製造方法，其係包含： 至少使主鏈具有脂環構造之聚碳酸酯二醇（a)、含有 8 323441 201217408 酸性基之多元醇（b)、多元異氰酸酯（d)、與1分子中具 有1個以上可與異氰酸基反應的基與1個以上聚合性不飽 和鍵的化合物（e)反應而得到聚氨基甲酸酯樹脂（A)， 再使聚氨基曱酸酯樹脂（A)及具有聚合性不飽和鍵 之化合物（B)分散於水系介質中。 本發明（10)係關於一種本發明（7)或（8)之水性聚氨基 曱酸酯樹脂分散體之製造方法，其係包含如下步驟： 至少使主鏈具有脂環構造之聚碳酸酯多元醇（a)、含 有酸性基之多元醇（b)、多元異氰酸酯（d)、與具有1個 以上可與異氰酸基反應的基與1個以上聚合性不飽和鍵的 化合物（e)反應而得到聚氨基曱酸酯預聚物（A1)之步 驟（α 1 )、 中和聚氨基曱酸醋預聚物（polyurethane prepolymer) (A1)之酸性基的步驟（/3 )、 使聚氨基曱酸酯預聚物（A1)與具有聚合性不飽和鍵 之化合物（B )分散於水系介質中之步驟（γ )、 使聚氨基曱酸酯預聚物（Α1)、與聚氨基甲酸酯預聚 物（Α1)之異氰酸基具有反應性的鏈延長劑（C)反應而 得到水性聚氨基曱酸酯樹脂的步驟（5 )。 本發明（11)係關於本發明（1)至（8)中任一項之水性聚 氨基曱酸酯樹脂分散體，其中進一步含有光聚合起始劑。 本發明（12)係關於一種塗料組成物，其係含有本發明 (1)至（8)及（11)中任一項之水性聚氨基曱酸酯樹脂分散體 者0 9 323441 201217408 本發明（13)係關於一種塗佈劑組成物，其係含有本發 明（1)至（8)及（11)中任一項之水性聚氨基曱酸酯樹脂分散 體者。 [發明之效果] 若依本發明，即可提供一種於良好的水系介質中具有 分散性及貯存安定性、且活性能量線（例如紫外線）硬化 後之塗膜對各種塑膠（ABS樹脂、丙烯酸樹脂、聚碳酸酯 樹脂等）之密著性優異之水性聚氨基曱酸酯樹脂分散體及 其製造方法。又若依本發明，可提供一種可賦予具有高硬 度之塗膜的水性聚氨基甲酸酯樹脂分散體及其製造方法。 本發明之水性聚氨基曱酸酯樹脂分散體係可作為航空器、 汽車等之外板、汽車的内裝材、行動電話殼體、家電製品 框體、個人電腦框體、加飾薄膜、光學薄膜、地板等之地 板材、外壁等之合成樹脂成形體的塗料（含有底漆）、印墨、 接著劑、塗佈劑、塗料組成物等的原料，可使用於廣泛之 用途。 【實施方式】 [用以實施發明之最佳形態] 本發明之水性聚氨基曱酸酯樹脂分散體，其係至少使 具有聚合性不飽和鍵之聚氨基曱酸酯樹脂（A)與具有聚 合性不飽和鍵之化合物（B)分散於水系介質中而成之水 性聚氨基曱酸酯樹脂分散體，其特徵係： 具有聚合性不飽和鍵之聚氨基曱酸酯樹脂（A)為至 少使於主鏈具有脂環構造之聚碳酸酯二醇（a)、含有酸性 10 323441 201217408 基之多元醇（b)、多元異氰酸酯（d)、與具有1個以上可 與異氰酸基反應的基與1個以上聚合性不飽和鍵的化合物 (e)反應所得到者。 〈具有聚合性不飽和鍵之聚氨基曱酸酯樹脂（A)〉 在本發明中，具有聚合性不飽和鍵之聚氨基曱酸酯樹 脂（A)為至少使於主鏈具有脂環構造之聚碳酸酯二醇 (a)、含有酸性基之多元醇（b)、多元異氰酸酯（d)、與 具有1個以上可與異氰酸基反應的基與1個以上聚合性不 飽和鍵的化合物（e )反應所得到者。 I.於主鏈具有脂環構造之聚碳酸酯多元醇（a) 於本發明使用之聚碳酸酯多元醇從可得到水性聚氨 基甲酸酯樹脂分散體之貯存安定性優異、密著性優異之塗 膜而言，為於主鏈具有脂環構造之聚碳酸酯多元醇（a)(以 下，有時稱為「聚碳酸酯多元醇（a)」）。 聚碳酸酯多元醇（a)係無特別限定，可舉例如，於主 鏈具有脂環構造之多元醇與碳酸酯反應所得到的聚碳酸酯 多元醇、於主鏈具有脂環構造之多元醇與其他之多元醇與 碳酸酯反應所得到的共聚合聚碳酸酯多元醇等。在本說明 書中，於脂環構造中亦包含於環内具有氧原子或氮原子等 之雜原子者。 聚碳酸酯多元醇（a)之較佳的數目平均分子量為400 至3000。若數目平均分子量為此範圍，可容易得到適當的 黏度及良好之處理性。又，容易確保作為軟段鏈之性能， 使用所得到之水性聚氨基曱酸酯樹脂分散體而形成塗膜時 11 323441 201217408 易抑制龜裂的發生’進—步，與多元異氰酸§旨（d)之反應 性充分’可有效率進行氨基甲酸醋聚合物的製造。聚碳酸 酯多元醇（a)之數目平均分子量更宜為4〇〇至15恥，尤 宜為500至1300。 在本發明中’數目平均分子量係依據JISK 1557所測 定之經基價而算出的數目平均分子量。具體上，係測定經 基價’藉末端基定量法，以（561χ1〇〇〇χ價數）/經基價 [mgK〇H/g]算出。在前述式中，價數為ι分子中之經基的 數目，聚碳酸酯多元醇為聚碳酸酯二醇時係價數為2。 於主鏈具有脂環構造之多元醇係無特別限定，可舉例 如1，4·環己烧二甲醇、環己烧二？醇、κ環己二醇、 環戊二醇、认環庚二醇、2,5_雙（經甲基）_M_二噪 【基2)，:: t片燒，、四f夫喃二甲醇、(乙 :元、二％[5.2.l。2,6]癸烧二甲醇為代表之三環癸 ::人:等：!酸二醇(―⑽“。1)之各構造異構體或 八此a物4之主鏈具有脂環構造的 容易性，宜為4-環己燒二甲醇。 從取付 定，m他之多元料，_其他以元_無特別限 疋可舉例如脂環族多元醇、若 _ 聚_多元醇等。 夕购、聚酯多元醇、201217408 SUMMARY OF THE INVENTION [Technical Field] The present invention relates to an aqueous polyaminophthalate resin dispersion which can be cured by irradiation with an active energy ray such as ultraviolet rays, a method for producing the same, and a use thereof. [Prior Art] Polycarbonate diol is useful as a raw material of a polyurethane resin (in the case of a polyamino phthalate, which is called a polyamino phthalate in the conventional practice). The compound can be produced by a reaction with an isocyanate compound to produce a polyaminophthalic acid resin which is used for hard foaming, soft foaming, coatings, adhesives, synthetic leathers, ink binders and the like. In addition, the coating film obtained by applying the aqueous polyurethane phthalate resin dispersion containing a polycarbonate polyol as a raw material is known to have excellent light resistance, heat resistance, chemical hydrolysis property, and oil resistance (see Patent Document 1). Among them, it is known that coating a coating film obtained by coating an aqueous amino phthalate resin dispersion of an aliphatic polycarbonate polyol can improve adhesion to a substrate and adhesion resistance, and thus can be used. As a primer (refer patent document 2). Further, in order to improve the hardness and durability of the coating film, an aqueous polyaminophthalic acid resin dispersion using a polycarbonate polyol having an alicyclic structure has also been proposed (see Patent Documents 3, 4 and 5). In addition, the radically polymerizable compound which is generally known has excellent curability even by heating, and therefore has an advantage in terms of productivity and energy saving. The active energy ray-curable resin composition having a radically polymerizable compound can be used as a coating for metal 4 323441 201217408, a coating material for various plastic films, a coating for wood I, and a printing ink. The active ingredient of the cloth or the subsequent material. For example, in the case of the aqueous polyurethane, the active energy ray-curable aqueous resin composition in which the (fluorenyl) acrylate-based compound is dispersed is disclosed (see Patent Document 6). An active energy ray-curable aqueous resin composition obtained by dispersing a (fluorenyl) acrylated polyamino phthalate or a (mercapto) acrylic acid compound in a water-based medium f has been proposed (see Patent Document 7). [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. [Patent Document 4] World Patent Publication No. WO2009/l45242 [Patent Document 5] World Patent Publication No. WO2010/004951 [Patent Document 6] JP-A-2008-248014 (Patent Document 7) Table 2009-533504 [Disclosure of the Invention] [Problems to be Solved by the Invention] However, in the aqueous polyurethane resin dispersion using polycarbonate polyol as a raw material, if only aliphatic polycarbonate is used, Alcohol as polycarbonate polyol In the case of applying the aqueous polyurethane resin dispersion, the adhesion and hardness of the coating film are, for example, in the field of coatings for aircraft, automobiles, etc. In the field of the agent, there is no problem of 323441 5 201217408. In addition, when a polycarbonate polyol having an alicyclic structure is used, the dispersibility in the aqueous medium is deteriorated, and the aqueous polyurethane resin dispersion is made. In addition, the problem that the handling property and the stability are problematic, and the adhesion and hardness are not recognized. Further, the energy-hardening type water-based resin composition is in the above-mentioned Patent Document 6, and the interface is used. The active agent causes the (meth)acrylate compound to be dispersed in the aqueous polyurethane resin dispersion, and the surfactant remains in the coating film to have a problem of lowering the performance of the coating film. In this composition, if it is reduced The amount of the surfactant used, or not used, causes a problem that the storage stability is lowered. Further, in Patent Document 7, the (meth)acrylic acid specifically disclosed In the combination of a polyurethane resin polyol and a (meth)acrylic compound, the coating film obtained from the energy ray-curable water-based resin composition has insufficient adhesion to various plastics (especially ABS resin and acrylic resin). Problem The object of the present invention is to provide an aqueous polyurethane resin knife body which is an active energy ray (e.g., ultraviolet ray) curing type aqueous polyurethane resin dispersion, which is in a good aqueous medium. The dispersibility and storage stability, and the coating film after curing with an active energy ray (for example, ultraviolet ray) is excellent in adhesion to various sins (ABS resin, acrylic resin, polycarbonate resin, etc.). Further, the present invention The problem is to obtain an aqueous polyamino phthalic acid _ age rhyme, the remaining energy lines (for example, the film after purple hardening has a high hardness. [Means for Solving the Problems] 323441 6 201217408 The inventors of the present invention conducted various studies to overcome the problems of the prior art, and found that the polyurethane resin having a polymerizable unsaturated bond is not polymerizable. The aqueous polyurethane resin dispersion in which the compound of the saturated bond is dispersed in an aqueous medium is prepared by using a polycarbonate polyol having an alicyclic structure as a raw material of the polyaminophthalate resin. Problems. The present invention (1) relates to an aqueous polyurethane resin dispersion which is at least a polyaminophthalate resin (A) having a polymerizable unsaturated bond and a compound (B) having a polymerizable unsaturated bond. An aqueous polyaminophthalate resin dispersion obtained by dispersing in an aqueous medium, characterized in that the polyaminophthalate resin (A) having a polymerizable unsaturated bond is a polycarbonate having at least an alicyclic structure in the main chain. Polycarbonate diol (a), an acid group-containing polyol (b), a polyisocyanate (d), and one or more groups capable of reacting with an isocyanate group in one molecule and one or more A polyaminophthalic acid resin obtained by reacting a compound (e) having a polymerizable unsaturated bond. The invention (2) relates to the aqueous polyaminophthalate resin dispersion of the invention (1), wherein the compound (B) having a polymerizable unsaturated bond contains a compound containing at least three (fluorenyl) acrylonitrile groups. The invention (3) is the aqueous polyaminophthalate resin dispersion according to the invention (1) or (2), wherein the compound (B) having a polymerizable unsaturated bond contains at least 5 (fluorenyl) fluorene oxime Base compound. The present invention (4) is the aqueous polyaminophthalate resin dispersion according to any one of the inventions (1) to (3), wherein one or more of one molecule can react with a different 7 323441 201217408 cyanate group. The compound (e) having one or more polymerizable unsaturated bonds includes a compound having one group reactive with an isocyanate group and one or more (fluorenyl) acrylonitrile groups. The aqueous polyaminophthalate resin dispersion according to any one of the inventions (1) to (4) wherein the one molecule has one or more reactive groups with an isocyanate group and one The compound (e) having one or more polymerizable unsaturated bonds includes a compound having one group reactive with an isocyanate group and three or more (meth)acryl fluorenyl groups. The aqueous polyaminophthalate resin dispersion according to any one of the inventions (1) to (5) wherein the one molecule has one or more reactive groups with an isocyanate group and one The compound (e) having one or more polymerizable unsaturated bonds includes a compound having two hydroxyl groups and two (fluorenyl) acrylonitrile groups. The present invention (7) is the aqueous polyaminophthalate resin dispersion according to any one of the inventions (1) to (6) wherein the polyaminophthalic acid ester resin having a polymerizable unsaturated bond is made of a main chain Polycarbonate diol (a) having an alicyclic structure, polyol (b) containing an acidic group, polyisocyanate (d), and one or more groups capable of reacting with an isocyanate group in one molecule and one The above polymerizable unsaturated bond compound (e) and chain extender (C) are reacted. The invention (8) is the aqueous polyaminophthalate resin dispersion according to the invention (7), wherein the chain extender (C) is a first-order polyamine compound. The invention (9) relates to a method for producing an aqueous polyurethane resin dispersion according to any one of the inventions (1) to (6), which comprises: at least a polycarbonate having an alicyclic structure in a main chain Ester diol (a), polyol (b) containing 8 323441 201217408 acidic group, polyisocyanate (d), and one or more groups capable of reacting with isocyanate groups in one molecule and one or more polymerizable groups The compound (e) having a saturated bond is reacted to obtain a polyurethane resin (A), and the polyaminophthalate resin (A) and the compound (B) having a polymerizable unsaturated bond are dispersed in an aqueous medium. The invention (10) relates to a method for producing an aqueous polyaminophthalate resin dispersion of the invention (7) or (8), which comprises the steps of: at least a polycarbonate having a main chain having an alicyclic structure The alcohol (a), the acidic group-containing polyol (b), the polyvalent isocyanate (d), and the compound (e) having one or more reactive groups capable of reacting with an isocyanate group and one or more polymerizable unsaturated bonds And the step (α1) of obtaining the polyaminophthalate prepolymer (A1), neutralizing the acidic group of the polyurethane prepolymer (A1) (/3), and making the polyamino group a step (γ) in which a phthalate prepolymer (A1) and a compound (B) having a polymerizable unsaturated bond are dispersed in an aqueous medium, a polyaminophthalate prepolymer (Α1), and a polyurethane The step (5) of obtaining an aqueous polyaminophthalic acid resin by reacting an isocyanate group of the ester prepolymer (Α1) with a reactive chain extender (C). The aqueous polyaminophthalate resin dispersion according to any one of the inventions (1) to (8), further comprising a photopolymerization initiator. The present invention (12) relates to a coating composition comprising the aqueous polyaminophthalate resin dispersion of any one of the inventions (1) to (8) and (11). 13) A coating composition comprising the aqueous polyaminophthalate resin dispersion of any one of the inventions (1) to (8) and (11). [Effects of the Invention] According to the present invention, it is possible to provide a coating film having a dispersibility and a storage stability in a good aqueous medium and having an active energy ray (for example, ultraviolet ray) hardened to various plastics (ABS resin, acrylic resin). An aqueous polyaminophthalic acid resin dispersion excellent in adhesion to a polycarbonate resin or the like and a method for producing the same. Further, according to the present invention, it is possible to provide an aqueous polyurethane resin dispersion which can impart a coating film having high hardness and a method for producing the same. The aqueous polyaminophthalate resin dispersion system of the present invention can be used as an outer panel of an aircraft or an automobile, an interior material of an automobile, a mobile phone casing, a casing for a home appliance, a personal computer frame, a decorative film, an optical film, A raw material such as a paint (including a primer), an ink, an ink, a coating agent, a coating composition, or the like of a synthetic resin molded body such as a floor or a floor material such as a floor can be used for a wide range of applications. [Embodiment] [Best Mode for Carrying Out the Invention] The aqueous polyaminophthalate resin dispersion of the present invention is at least a polyaminophthalate resin (A) having a polymerizable unsaturated bond and having a polymerization An aqueous polyaminophthalate resin dispersion in which a compound (B) having an unsaturated bond is dispersed in an aqueous medium, characterized in that the polyaminophthalate resin (A) having a polymerizable unsaturated bond is at least a polycarbonate diol (a) having an alicyclic structure in a main chain, a polyol (b) having an acidic 10 323441 201217408 group, a polyvalent isocyanate (d), and a group having one or more reactive groups with an isocyanate group A compound obtained by reacting a compound (e) having one or more polymerizable unsaturated bonds. <Polyaminophthalic acid ester resin (A) having a polymerizable unsaturated bond> In the present invention, the polyaminophthalic acid ester resin (A) having a polymerizable unsaturated bond has at least an alicyclic structure in the main chain. Polycarbonate diol (a), acidic group-containing polyol (b), polyvalent isocyanate (d), and compound having one or more reactive groups capable of reacting with an isocyanate group and one or more polymerizable unsaturated bonds (e) The person obtained by the reaction. I. Polycarbonate polyol having an alicyclic structure in the main chain (a) The polycarbonate polyol used in the present invention is excellent in storage stability and excellent in adhesion from an aqueous polyurethane resin dispersion obtainable The coating film is a polycarbonate polyol (a) having an alicyclic structure in the main chain (hereinafter, referred to as "polycarbonate polyol (a)"). The polycarbonate polyol (a) is not particularly limited, and examples thereof include a polycarbonate polyol obtained by reacting a polyol having an alicyclic structure in a main chain with a carbonate, and a polyol having an alicyclic structure in a main chain. A copolymerized polycarbonate polyol obtained by reacting with other polyols and a carbonate. In the present specification, a hetero atom having an oxygen atom or a nitrogen atom in the ring is also included in the alicyclic structure. The preferred number average molecular weight of the polycarbonate polyol (a) is from 400 to 3,000. If the number average molecular weight is in this range, appropriate viscosity and good rationality can be easily obtained. Moreover, it is easy to ensure the performance of the soft segment chain, and when the coating film is formed using the obtained aqueous polyaminophthalate resin dispersion, 11 323441 201217408 is easy to suppress the occurrence of cracks, and the polyisocyanate (d) Responsiveness is sufficient 'The production of a urethane polymer can be efficiently performed. The number average molecular weight of the polycarbonate polyol (a) is more preferably from 4 to 15 shame, and particularly preferably from 500 to 1300. In the present invention, the number average molecular weight is a number average molecular weight calculated from the base price measured in accordance with JIS K 1557. Specifically, the basis weight is determined by the base value quantitative method, and is calculated as (561χ1〇〇〇χ valence)/base price [mgK〇H/g]. In the above formula, the valence is the number of the radicals in the ι molecule, and the polycarbonate polyol is a polycarbonate diol having a valence of 2. The polyol having an alicyclic structure in the main chain is not particularly limited, and examples thereof include 1,4, cyclohexane, dimethanol, and cyclohexane. Alcohol, κcyclohexanediol, cyclopentanediol, cyclohexanediol, 2,5-bis(methyl)_M_difference [base 2), :: t-tablet, tetraf-f Methanol, (B: Yuan, 2% [5.2.l. 2,6] tert-doped dimethanol represented by tricyclic oxime:: human: et al:! Acid diol (―(10)". 1) The main chain of the body or the arsenal 4 has the susceptibility of the alicyclic structure, and is preferably 4-cyclohexanthrene dimethanol. From the withdrawal, m is a multi-component, _ other is _ no special limitation, for example An alicyclic polyol, a _ poly-polyol, etc., a polyester, a polyester polyol,

之多元醇係無特別限制，可舉例如碳數2至U 丙：族夕元醇等。具體上’可舉❹U-乙二醇、&quot; 丙一醇、M•丁二醇、1&gt;5_ ，· 醇、M-辛二醇、19m_…己-知、1，7·庚二 ，一％荨之直鏈狀脂肪族二醇；2_甲 323441 12 201217408 基-1，3-丙二醇、2-曱基-1,5-戊二醇、3-甲基-1,5-戊二醇、 2-曱基-1,9-壬二醇等之分枝鏈狀脂肪族二醇；1，1，1-三羥曱 基丙烷、新戊四醇等之3官能以上的多元醇等。 芳香族多元醇係無特別限定，可舉例如1,4-苯二曱 醇、1,3-苯二曱醇、1，2-苯二曱醇、4,4’-萘二曱醇、3,4’-萘二曱醇等。 聚酯多元醇係無特別限定、可舉例如6-羥基己酸與己 二醇之聚酯多元醇等的羥基羧酸與二醇之聚酯多元醇、己 二酸與己二醇之聚酯多元醇等之二羧酸與二醇之聚酯多元 醇等。 聚醚多元醇係無特別限定、可舉例如聚乙二醇（例如 二乙二醇、三乙二醇、四乙二醇等）或聚丙二醇或聚伸丁 二醇等之聚烷二醇等。 碳酸酯係無特別限定，可舉例如碳酸二曱酯、碳酸二 乙酯等之脂肪族碳酸酯、碳酸二苯基酯等之芳香族碳酸 酯、碳酸伸乙酯等之環狀碳酸酯等。其他，亦可生成聚碳 酸酯多元醇之光氣等。其中，從聚碳酸酯多元醇之製造容 易性，宜為脂肪族碳酸酯，尤宜為碳酸二曱酯。 從多元醇及碳酸酯製造聚碳酸酯多元醇的方法，可舉 例如於反應器中加入礙酸S旨、對此碳酸S旨之莫耳數為過剩 的莫耳數之多元醇，以溫度160至200°c、壓力50mmHg 左右反應5至6小時後，進一步在數mmHg以下之壓力中 以200至220反應數小時之方法。在前述反應中，宜使副 生成之醇排出至系外並同時反應。其時，碳酸酯藉由與副 13 323441 201217408 生成之醇共沸移出至系外時，亦可加入過剩量之碳酸酯。 又，在前述反應中，亦可使用四丁氧基鈦等之觸媒。 聚碳酸酯多元醇（a)中之脂環構造含有率宜為20至 65重量％。若脂環構造含有率為此範圍，依脂環構造之存 在，易於得到硬度優異之塗膜，塗膜於各種塑膠的密著性 亦充分。其一者，脂環構造之含有率太大，水性聚氨基曱 酸酯樹脂分散體製造時之預聚物的黏度變高，易避免處理 性變困難之事態，可容易得到良好的貯存安定性，脂環構 造含有率更宜為30至55重量％。 此處，脂環構造含有率係謂於聚碳酸酯多元醇（a)中 脂環式基所佔之重量比率。例如依據環己烷殘基等之環烷 殘基（1,4-己烷二曱醇時，係從環己烷除去2個氫原子之 部分）、或四氫呋喃殘基等之不飽和雜環殘基（四氫呋喃二 曱醇時，係從四氫0夫喃除去2個氫原子之部分），所算出之 值。 從水性介質之分散性的觀點，聚碳酸醋多元醇（a )宜 為併用其他之多元醇的共聚合聚碳酸酯多元醇。其他之多 元醇係可使用脂肪族多元醇、芳香族多元醇、聚酯多元醇、 聚醚多元醇，可適用前述之具體例。其中，宜為於主鏈具 有脂環構造之多元醇與脂肪族多元醇之組合，尤其，宜併 用1,4-環己烷二曱醇與1，6-己二醇所得到之共聚合聚碳酸 酉旨多元醇。 聚碳酸酯多元醇（a)係可單獨使用，亦可併用複數種。 II.含有酸性基之多元醇（b) 14 323441 201217408 在本發明中使用之含有酸性基之多元醇（b)係只要 為1分子中含有2個以上羥基與1個以上酸性基者即可， 無特別限定。酸性基可舉例如羧基、磺酸基、磷酸基、酚 性羥基等。尤其，含有酸性基之多元醇（b)宜為包含1 分子中具2個羥基與1個羧基之化合物者。含有酸性基之 多元醇（b)係可單獨使用，亦可併用複數種。 含有酸性基之多元醇（b)具體上可舉例如2,2-二羥甲 基丙酸、2,2-二羥曱基丁酸等以二羥甲基烷酸為首之二烷 醇烷酸；Ν,Ν-雙羥基乙基甘胺酸、Ν,Ν-雙羥基乙基丙胺 酸、3,4-二羥基丁烷磺酸、3,6-二羥基-2-甲苯磺酸、含有酸 性基之聚醚多元醇、含有酸性基之聚酯多元醇等。其中從 取得容易性之觀點，宜為含有2個烷醇基之二烷醇烷酸， 更宜為含有2個羥曱基之碳數4至12的烷酸（二羥曱基烷 酸），二羥甲基烷酸之中，尤宜為2,2-二羥甲基丙酸。 III.其他之多元醇（c) 除聚碳酸酯多元醇（a)及含有酸性基之多元醇以外， 可使用其他之多元醇（c)(以下，有時稱為「其他之多元 醇（c)」）。其他之多元醇（c)可舉例如聚合物多元醇等之 高分子多元醇或低分子多元醇。高分子多元醇可舉例如數 目平均分子量為400至6000者。多元醇係可為二醇，亦可 為3價以上之多元醇。其他之多元醇係可單獨使用，亦可 併用複數種。從塗膜之硬度變高的點，宜為低分子多元醇， 其中宜為低分子二醇。 高分子聚合物多元醇係無特別限定，可適宜使用聚酯 15 323441 201217408 多元醇、聚醚多元醇、 主T有脂環構造之〇聚二稀多元醇、於 聚醋多元醇係無特-曰夕導 多元醇、聚己二酸丁二’可舉例如聚己二酸乙二酽 醋多元醇、聚六”基異耿：/已聚已二酸伸乙基伸丁基曰 酸乙二酯多元醇、聚琥站酸丁：-酸赌多元醇、聚琥拍 酯多元醇、聚癸二酸丁二醋多^多元醇、聚癸二酸乙二 聚（3m，5·伸戊 颂、聚-ε·已〜 體酸之聚縮合物等。已，多元醇、Μ_己二醇與二 内酉旨多元醇 聚驗多元醇係無特別限定 二醇、聚四亞甲基二醇、 牛例如聚乙二醇、聚丙 與環氧丁燒之隨機共聚物或與環氧咕、環氧乙貌 用具有賴無鍵之聚 二、聚物等。進-步亦可使 _ 日夕元醇望 H多元醇麵⑽m定，可與 戊二烯、1，3-戊二烯、氯丁埽 ：例如含丁二烯、異 的聚二烯多元醇等。聚二烯多元=一烯等所衍生之單元 性經基末端液狀聚製「吨…或二官能 經基末端液狀聚異戊二稀（=產杜製「kras〇l」)、 I 士山 冲、出先興產社製「Poly ip」）、羥 基末端液狀㈣烴（出光興產社製「EpGl」）等。 聚丙稀7L醇係無特別限定，可舉例如使用由丙稀 焱基乙酉曰丙稀酸_2·經基丙醋、丙稀酸-I經基丁醋 =具有活性氫的、或甘油之㈣酸單喊甲基 丙婦酸單自旨、絲甲基咕之⑽酸單㈣甲基丙婦酸單 16 323441 201217408 酯之群中選出的單獨或混合物，與由丙烯酸曱酯、丙烯酸 乙酯、丙烯酸異丙酯、丙烯酸正丁酯、丙烯酸-2-乙基己酯 等之丙烯酸酯、甲基丙烯酸-2-羥乙酯、曱基丙烯酸-2-羥丙 酯、曱基丙烯酸-2-羥丁酯、甲基丙烯酸-3-羥丙酯、曱基丙 烯酸-4-羥丁酯等具有活性氫的甲基丙烯酸酯、曱基丙烯酸 甲酯、甲基丙烯酸乙酯、曱基丙烯酸異丙酯、甲基丙烯酸 正丁酯、甲基丙烯酸異丁酯、甲基丙烯酸正己酯、甲基丙 烯酸月桂酯等的曱基丙烯酸酯的群中所選出之單獨或混合 物，在丙烯酸、曱基丙烯酸、馬來酸、衣康酸等之不飽和 羧酸、丙烯醯胺、N-羥曱基丙烯醯胺、二丙酮丙烯醯胺等 之不飽和醯胺、及曱基丙烯酸縮水甘油S旨、苯乙稀、乙烯 基甲苯、醋酸乙烯酯、丙烯腈、富馬酸二丁酯等之其他聚 合性單體的群中所選出之單獨或混合物之存在下或非存在 下，使聚合所得到的聚丙烯酸多元醇。其聚合方法可舉例 如乳化聚合、懸浮聚合、分散聚合、溶液聚合等。乳化聚 合中亦可階段性聚合。 於主鏈不具有脂環構造之聚碳酸酯多元醇係無特別 限定，可舉例如聚碳酸四亞曱酯二醇、聚碳酸酯五亞甲二 醇、聚碳酸六亞曱酯二醇等之脂肪族聚碳酸酯二醇；聚1，4-伸苯二曱基碳酸酯二醇等之芳香族聚碳酸酯二醇；複數種 類的脂肪族二醇與碳酸酯之反應生成物的共聚合聚碳酸酯 二醇；脂肪族二醇與芳香族二醇與碳酸酯之反應生成物的 共聚合聚碳酸酯二醇等之共聚合聚碳酸酯二醇等。 共聚合聚碳酸酯二醇係可舉例如1，3-丙二醇與1,4-丁 17 323441 201217408 二醇與碳酸酯之反應生成物的共聚合聚碳酸酯二醇、L4- 丁二醇與1,5-戊二醇與碳酸酯之反應生成物的共聚合聚碳 酸酯二醇、1，5_戊二醇與ι，6-己二醇與碳酸酯之反應生成 物的共聚合聚碳酸酯二醇、1，4-丁二醇與1，6_己二醇與碳 酸酿之反應生成物的共聚合聚碳酸酯二醇、^^丙二醇與 1，6 -己二醇與碳酸酯之反應生成物的共聚合聚碳酸酯二醇 等。 低为子多元醇係無特別限定，可舉例如數目平均分子 量為60以上未達400者。可舉例如乙二醇、丨，3丙二醇、 2-甲基-1，3-丙二醇、2,2_二甲基.以丙二醇、2 丁基_2-乙 基-1,3-丙二醇、Μ_τ二醇、戊二醇、3甲基戍二 醇、M-己二醇、π壬二醇、2•甲基辛二醇、二乙二 醇、，乙二醇、四乙二醇等之碳數2至9的脂肪族二醇； 1，4-=烷二甲醇、u·環己烷二甲醇、環己烷二醇、 甲=1㈣己院、2,7·降冰片院二醇、四氯咬喃二 甲知2,5-雙（羥甲基）_M_二噁 脂，之二醇;苯二甲醇、u-苯二; 基本等之芳香族二醇等。又旷， -甲基丙烧、新戊四醇、山梨 子量多元醇。 一 g此以上的低分 其他之多元醇（〇)對聚碳_旨 4〇重量％以下。若為此範園 ⑷之比率宜為 性降低，料《氨心塗膜的密著 其他之多元醇⑴的比率更佳為^， 323441 18 201217408 ιν.多元異氰酸酯（d) 本發明可使用之多元異氰酸酯⑷係無特別限定， :舉例如芳㈣多元異氰酸㈣、麟衫元異氰酸醋、脂 環式多元異氰酸酯等。 芳香族多元異氰酸酯具體上係可舉例如L3-苯二異氰 酉文酉曰M-笨一異氰酸酯、2,4_曱苯二異氰酸酯（Tm)、2,6_ 甲苯二異氰酸酯、4,4’-二苯基甲烷二異氰酸酯（MDI)、2,4_ 二苯基甲烷二異氰酸酯、4,4’-二異氰酸基聯苯酯、3,3，_二 甲基-4,4’-二異氰酸聯苯酯、3,3，_二甲基_4,4，_二異氰酸二 本基甲院、1，5-二異氰酸伸萘酯、4,4’，4，，-三苯基曱烧三異 氰酸酯、間-異氰酸基苯基續醯基異氰酸酯、對_異氰酸基 苯基磺醯基異氰酸酯等。 脂肪族多元異氰酸酯具體上係可舉例如二異氰酸伸 乙酯、四亞甲基二異氰酸酯、六亞甲基二異氰酸酯（Hdi )、 十二亞甲基二異氰酸酯、1,6，11-十一碳基三異氰酸酯、 2,2,4-三甲基六亞甲基二異氰酸酯、離胺酸二異氰酸酯、 2,6-二異氰酸基曱基己酸酯、雙（2-異氰酸基乙基）富馬酸 酯、雙（2-異氰酸基乙基）碳酸酯、2-異氰酸基乙基-2,6-二異氰酸基己酸酯等。 脂環式多元異氰酸酯具體上係可舉例如異佛爾酮二 異氰酸酯（1卩〇1)、4,4’-二環己基曱烷二異氰酸酯（氫化 MDI)、伸環己基二異氰酸酯、曱基伸環己基二異氰酸酯（氩 化TDI)、雙（2-異氰酸基乙基）-4-己烯-1，2·二羧酸酯、2,5-降冰片烷基二異氰酸酯、2,6-降冰片烷基二異氰酸酯等。 19 323441 201217408 此等之多元異氰酸酯係可單獨使用，亦可併用複數 種。 多元異氰酸酯之每1分子的異氰酸基一般為2個， 但，在本發明之聚氨基甲酸酯樹脂不進行凝膠化的範圍， 亦可使用如三苯基曱烷三異氰酸酯之具有3個以上異氰酸 基的多元異氰酸S旨。 多元異氰酸酯之中，從反應性的控制、高的硬度、增 加強度等之觀點，宜為4,4’-二伸苯基曱烷二異氰酸酯 (MDI)、異佛爾酮二異氰酸酯（IPDI)、4,4’-二環己基曱 烷二異氰酸酯（氫化MDI)。 V.1分子中具有1個以上可與異氰酸基反應的基與1個以 上聚合性不飽和鍵的化合物（e ) 1分子中具有1個以上可與異氰酸基反應的基與1個 以上聚合性不飽和鍵的化合物（e)(以下，有時稱為「不 飽和化合物（e )」）中之聚合性不飽和鍵係可舉例如包含於 可藉光聚合起始劑所產生的自由基等聚合之不飽和基的 鍵。如此之不飽和基係可為公知者，如含有乙烯性不飽和 鍵之基，從容易取得之點及反應性高，宜為（曱基）丙烯醢 基。在本說明書中，所謂（甲基）丙烯醯基意指丙烯醯基或/ 及甲基丙烯醯基，（甲基）丙烯酸酯意指丙烯酸酯或/及曱基 丙烯酸酯，（曱基）丙烯酸意指丙烯酸或/及甲基丙烯酸。不 飽和化合物（e )係1分子中具有1個以上聚合性不飽和鍵。 可與不飽和化合物（e)中之異氰酸基反應的基，係可 舉例如羥基、胺基、異氰酸基、硫醇基等。其中，從不飽 20 323441 201217408 和化合物（e)之處理容易性之點’宜為羥基。不飽和化合 物（e)係於1分子具有丨個以上可與異氰酸基反應的基。 不飽和化合物（e)從處理容易性之點，宜為具有i 個以上之羥基與1個以上之聚合性不飽和鍵的化合物 (e’）。不飽和化合物（e，）係可舉例如丨分子中具有1個 羥基與1個聚合性不飽和鍵之不飽和化合物（e，」）、【分 子中具有1個經基與2個以上聚合性不飽和鍵之不飽和化 口物（e -2)、1分子中具有2個以上經基與i個聚合性不 飽和鍵之不飽和化合物（e，-3)、i分子中具有2個以上經 基與2個以上聚合性不飽和鍵之不飽和化合物（e，_4)等。 1分子中具有1個羥基與i個聚合性不飽和鍵之不飽 和化合物（e’])係可舉例如基乙基（甲基）丙稀酸醋、 3’基丙基(甲基)丙烯酸酯、4•羥基丁基(甲基)丙烯酸酯 等。 1分子中具有1趣基與2個以上聚合性不飽和鍵之 不飽和化合物（e，-2)係可舉例如甘油二(甲基)丙烯酸醋、 二甘油三（甲基）丙烯酸醋、三經甲基丙燒二β基）丙稀酸 酯、新戊四醇三W基）丙稀酸酯、二新戊四醇五（甲基）丙稀 酸醋、山梨糖醇五（甲基)丙婦酸酯、縮水甘油基（甲基）丙稀 酸酯之（甲基）丙烯酸加成物等。 1分子中具有2細上祕與1 «合性不飽和鍵之 不飽辛，口物（e -3)係、可舉例如甘油單（甲基）丙歸酸醋、 -甘油早基)丙稀酸醋、新戊四醇單⑶基）丙稀酸醋、二 新戊四醇單(甲基)丙稀酸酯、山梨糖醇單_丙烯酸酯 323441 21 201217408 等。 1分子中具有2個以上羥基與2個以上聚合性不飽和 鍵之不飽和化合物（e，-4)係可舉例如二甘油二（曱基）丙烯 酸酯、新戊四醇二（甲基）丙烯酸酯、二新戊四醇二（甲基） 丙烯酸酯、二新戊四醇三（甲基）丙烯酸酯、二新戊四醇四 (曱基）丙烯酸酯、山梨糖醇二（曱基）丙烯酸酯、山梨糖醇三 (曱基）丙烯酸酯、山梨糖醇四（曱基）丙烯酸酯、2分子之（曱 基）丙烯酸與1分子之1，6_己二醇二縮水甘油酯之反應生成 物（例如Nagasechemtex公司製「DA-212」）、2分子之環 氧基（曱基）丙烯酸與1分子之新戊二醇二縮水甘油酯之反 應生成物、2分子之（曱基）丙稀酸與1分子之雙酚a二縮 水甘油Sa之反應生成物（例如Nagase chemtex公司製 「DA-250」）、2分子之（曱基）丙烯酸與雙酚a的環氧丙烷 加成物之二縮水甘油基体之反應生成物、2分子之（曱基) 丙烯酸與1分子之酞酸二縮水甘油酯之反應生成物（例如 Nagase chemtex公司製「Dmi」）、2分子之（曱基）丙烯 酸與1分子之聚乙二醇二縮水甘油酯之反應生成物（例如The polyol is not particularly limited, and examples thereof include a carbon number of 2 to U propylene: a group of ceramyl alcohol. Specifically, 'U-ethylene glycol, &quot; propanol, M•butanediol, 1&gt;5_, · alcohol, M-octanediol, 19m_...hex-known, 1,7·g-2, one % linear linear aliphatic diol; 2_甲323441 12 201217408 base-1,3-propanediol, 2-mercapto-1,5-pentanediol, 3-methyl-1,5-pentanediol a branched chain aliphatic diol such as 2-mercapto-1,9-nonanediol; a trifunctional or higher polyhydric alcohol such as 1,1,1-trihydroxydecylpropane or pentaerythritol; and the like. The aromatic polyol is not particularly limited, and examples thereof include 1,4-benzoic acid alcohol, 1,3-benzoic acid alcohol, 1,2-benzoic acid alcohol, and 4,4'-naphthalene dinonanol. , 4'-naphthalenediol, and the like. The polyester polyol is not particularly limited, and examples thereof include polyester polyols of hydroxycarboxylic acid and diol such as polyester polyol of 6-hydroxycaproic acid and hexanediol, and polyesters of adipic acid and hexanediol. A polyester polyol such as a dicarboxylic acid such as a polyhydric alcohol or a diol. The polyether polyol is not particularly limited, and examples thereof include polyethylene glycol (for example, diethylene glycol, triethylene glycol, tetraethylene glycol, etc.) or polyalkylene glycol such as polypropylene glycol or polybutanediol. . The carbonate is not particularly limited, and examples thereof include aliphatic carbonates such as dinonyl carbonate and diethyl carbonate, aromatic carbonates such as diphenyl carbonate, and cyclic carbonates such as ethyl carbonate. Others may also produce phosgene of a polycarbonate polyol. Among them, from the viewpoint of ease of production of the polycarbonate polyol, it is preferably an aliphatic carbonate, particularly preferably dinonyl carbonate. The method for producing a polycarbonate polyol from a polyhydric alcohol and a carbonate may, for example, be a polyol in which a molar amount of moles of carbonic acid is excessively added to the reactor, and the temperature is 160. After reacting for about 5 to 6 hours at a pressure of about 200 ° C and a pressure of about 50 mmHg, the reaction is further carried out at 200 to 220 for several hours under a pressure of several mmHg or less. In the foregoing reaction, it is preferred that the by-produced alcohol is discharged to the outside of the system and simultaneously reacted. At this time, when the carbonate is azeotropically removed to the outside of the system by the alcohol produced by the sub- 13 323441 201217408, an excess amount of the carbonate may be added. Further, in the above reaction, a catalyst such as titanium tetrabutoxide may also be used. The alicyclic structure content of the polycarbonate polyol (a) is preferably from 20 to 65 % by weight. When the content of the alicyclic structure is in this range, it is easy to obtain a coating film having excellent hardness depending on the structure of the alicyclic structure, and the adhesion of the coating film to various plastics is also sufficient. In one case, the content of the alicyclic structure is too large, and the viscosity of the prepolymer in the production of the aqueous polyaminophthalate resin dispersion becomes high, and it is easy to avoid the trouble that the handling property becomes difficult, and the storage stability can be easily obtained. The alicyclic structure content is more preferably from 30 to 55% by weight. Here, the alicyclic structure content ratio is a weight ratio of the alicyclic group in the polycarbonate polyol (a). For example, an unsaturated heterocyclic residue such as a cyclohexane residue such as a cyclohexane residue (a portion in which two hydrogen atoms are removed from cyclohexane) or a tetrahydrofuran residue is used. The value (the portion obtained by removing two hydrogen atoms from tetrahydrofuran) in the case of tetrahydrofuran decyl alcohol, and the calculated value. From the viewpoint of dispersibility of the aqueous medium, the polycarbonate polyol (a) is preferably a copolymerized polycarbonate polyol in which other polyols are used in combination. As the other polyol, an aliphatic polyol, an aromatic polyol, a polyester polyol, or a polyether polyol can be used, and the above specific examples can be applied. Among them, it is preferred to use a combination of a polyhydric alcohol having an alicyclic structure in the main chain and an aliphatic polyhydric alcohol, and in particular, a copolymerization polymerization obtained by using 1,4-cyclohexanedhenol and 1,6-hexanediol in combination. Barium carbonate is a polyol. The polycarbonate polyol (a) may be used singly or in combination of plural kinds. II. Acid group-containing polyol (b) 14 323441 201217408 The acid group-containing polyol (b) used in the present invention may be one having two or more hydroxyl groups and one or more acidic groups in one molecule. There is no special limit. The acidic group may, for example, be a carboxyl group, a sulfonic acid group, a phosphoric acid group or a phenolic hydroxyl group. In particular, the polyol (b) containing an acidic group is preferably one containing a compound having two hydroxyl groups and one carboxyl group in one molecule. The polyol (b) containing an acidic group may be used singly or in combination of plural kinds. The polyol (b) containing an acidic group may, for example, be a dialkylol alkanoic acid such as 2,2-dimethylolpropionic acid or 2,2-dihydroxymethylbutyric acid, such as dimethylol alkanoic acid. ;Ν,Ν-bishydroxyethylglycine, hydrazine, hydrazine-bishydroxyethylalanine, 3,4-dihydroxybutane sulfonic acid, 3,6-dihydroxy-2-toluenesulfonic acid, acidic A polyether polyol based on a base, a polyester polyol containing an acidic group, and the like. From the viewpoint of easiness of obtaining, it is preferably a dialkyl alkanolic acid containing two alkanol groups, more preferably an alkanoic acid (dihydroxydecyl alkanoic acid) having from 4 to 12 carbon atoms containing two hydroxyl groups. Among the dimethylol alkanoic acids, 2,2-dimethylolpropionic acid is particularly preferred. III. Other Polyols (c) In addition to the polycarbonate polyol (a) and the polyol containing an acidic group, other polyols (c) may be used (hereinafter, sometimes referred to as "other polyols (c) )"). The other polyol (c) may, for example, be a polymer polyol such as a polymer polyol or a low molecular polyol. The polymer polyol may, for example, be a number average molecular weight of from 400 to 6,000. The polyol may be a diol or a polyvalent alcohol having a valence of 3 or more. Other polyols may be used singly or in combination of plural kinds. From the point where the hardness of the coating film becomes high, it is preferably a low molecular polyol, and preferably a low molecular weight diol. The polymer polyol is not particularly limited, and a polyester 15 323441 201217408 polyol, a polyether polyol, a condensed polydiene polyol having a main T alicyclic structure, and a polyester phenol polyol are not particularly suitable.曰 导 多元 多元 、 、 、 、 、 、 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可 可Polyol, poly-sulphate acid butyl: - acid gambling polyol, poly-succinol ester polyol, polyphthalic acid diced diacetate poly-polyol, polyphthalic acid ethylene dimerization (3m, 5 · pentylene, Poly-ε· ～ 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚 聚. Cattle such as polyethylene glycol, random copolymer of polypropylene and epoxy butyl ketone or polyether, polymer with ruthenium oxime or epoxy ruthenium can be used to make _ _ _ _ _ H polyol surface (10) m, can be combined with pentadiene, 1,3-pentadiene, chloroprene: for example, butadiene, heteropolydiene polyol, etc. Polydiene The unitary liquid-based end-end liquid-like polymerization of "Ten... or difunctional end-group liquid polyisoprene (= "kras〇l"), I Shishan Chong, Yixingxingshe "Poly ip"), hydroxyl-terminated liquid (tetra) hydrocarbon ("EpGl" manufactured by Idemitsu Kosan Co., Ltd.). The polypropylene 7L alcohol is not particularly limited, and for example, it can be used, for example, acrylonitrile acetoacetic acid _2, propyl acetonate, acrylic acid-I butyl vinegar = active hydrogen, or glycerin (IV) Acid mono-methyl acetoacetate single-acting, silk methyl hydrazine (10) acid mono (tetra) methyl acetophenone mono 16 323441 201217408 selected from the group of esters alone or in combination with decyl acrylate, ethyl acrylate, Acrylates such as isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy hydroxy acrylate Oxidized active methacrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, such as butyl ester, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate a single or a mixture of thiol acrylates such as n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, lauryl methacrylate, etc., in acrylic acid, methacrylic acid, horse Unsaturated carboxylic acid, acrylamide, N-hydroxydecyl propylene oxime, such as acid and itaconic acid And other polymerizable monomers such as diacetone acrylamide and other unsaturated decylamine, and methacrylic acid glycidol S, styrene, vinyl toluene, vinyl acetate, acrylonitrile, dibutyl fumarate, etc. The resulting polyacrylic acid polyol is polymerized in the presence or absence of a separate or a mixture selected from the group. The polymerization method can be exemplified by emulsion polymerization, suspension polymerization, dispersion polymerization, solution polymerization, and the like. In the emulsion polymerization, the polymerization can also be carried out in stages. The polycarbonate polyol having no alicyclic structure in the main chain is not particularly limited, and examples thereof include tetradecylene carbonate diol, polycarbonate pentamethylene glycol, and hexamethylene phthalate diol. An aliphatic polycarbonate diol; an aromatic polycarbonate diol such as poly 1,4-terpene dicarbonate diol; a copolymerization polymerization of a reaction product of a plurality of aliphatic diols and a carbonate Carbonate diol; copolymerized of a reaction product of an aliphatic diol and an aromatic diol with a carbonate, a copolymerized polycarbonate diol such as a polycarbonate diol, or the like. The copolymerized polycarbonate diol may, for example, be a copolymerized polycarbonate diol of a reaction product of 1,3-propanediol and 1,4-butyl 17 323441 201217408 diol with a carbonate, L4-butanediol and 1 , a copolymerized polycarbonate of a reaction product of 5-pentanediol and a carbonate, a copolymerized polycarbonate of 1,5-pentanediol and a reaction product of iota,6-hexanediol and a carbonate Copolymerization of diol, 1,4-butanediol and 1,6-hexanediol with a reaction product of carbonic acid, reaction of polycarbonate diol, propylene glycol and 1,6-hexanediol with carbonate The product is a copolymerized polycarbonate diol or the like. The low-sub-polyol group is not particularly limited, and examples thereof include those in which the number average molecular weight is 60 or more and less than 400. For example, ethylene glycol, hydrazine, 3 propylene glycol, 2-methyl-1,3-propanediol, 2,2-dimethyl, propylene glycol, 2 butyl 2 -ethyl-1,3-propanediol, Μ_τ Carbon such as diol, pentanediol, 3-methylnonanediol, M-hexanediol, π-decanediol, 2-methyloctanediol, diethylene glycol, ethylene glycol, tetraethylene glycol, etc. a number of 2 to 9 aliphatic diols; 1,4- = alkane dimethanol, u · cyclohexane dimethanol, cyclohexane diol, methyl = 1 (four) hexa, 2, 7 · norbornene diol, four Chlorhexidine is known as 2,5-bis(hydroxymethyl)_M_dioxin, diol; benzenedimethanol, u-benzene; basic aromatic diol, and the like. Also, - methylpropanol, pentaerythritol, sorbitol polyol. One g or more of the lower part of the other polyol (〇) is less than or equal to 4% by weight. If the ratio of the Fanyuan (4) is to be reduced, it is preferable that the ratio of the adhesive of the ammonia core coating to the other polyol (1) is better, 323441 18 201217408 ιν. Polyisocyanate (d) The isocyanate (4) is not particularly limited, and examples thereof include aryl (tetra) polyisocyanate (tetra), linoleic isocyanuric acid, and alicyclic polyisocyanate. The aromatic polyisocyanate may specifically be, for example, L3-benzene diisocyanide M-p-monoisocyanate, 2,4-nonyl diisocyanate (Tm), 2,6-toluene diisocyanate, 4,4'- Diphenylmethane diisocyanate (MDI), 2,4-diphenylmethane diisocyanate, 4,4'-diisocyanatobiphenyl ester, 3,3,_dimethyl-4,4'-diiso Biphenyl cyanate, 3,3,-dimethyl-4,4,-diisocyanate dibenzamine, 1,5-diisocyanate, 4,4',4, Triphenylsulfonium triisocyanate, m-isocyanatophenyl decyl isocyanate, p-isocyanatophenylsulfonyl isocyanate, and the like. The aliphatic polyisocyanate may specifically be, for example, ethyl diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (Hdi ), dodecamethylene diisocyanate, 1,6,11-ten Mono-carbon triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, ammonium diisocyanate, 2,6-diisocyanatodecyl hexanoate, bis(2-isocyanate) Ethyl ethyl) fumarate, bis(2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, and the like. The alicyclic polyisocyanate may specifically be, for example, isophorone diisocyanate (1卩〇1), 4,4'-dicyclohexyldecane diisocyanate (hydrogenated MDI), cyclohexyl diisocyanate, fluorenyl exocyclic ring. Hexyl diisocyanate (argonized TDI), bis(2-isocyanatoethyl)-4-hexene-1,2.dicarboxylate, 2,5-norbornyl diisocyanate, 2,6- Norbornyl diisocyanate and the like. 19 323441 201217408 These polyisocyanates may be used singly or in combination. The polyisocyanate generally has two isocyanato groups per molecule. However, in the range where the polyurethane resin of the present invention is not gelled, it is also possible to use, for example, triphenyldecane triisocyanate. More than one isocyanate-based polyisocyanate S. Among the polyisocyanates, 4,4'-diphenylene phthalocyanine diisocyanate (MDI), isophorone diisocyanate (IPDI), and the like are preferable from the viewpoints of control of reactivity, high hardness, and strength. 4,4'-Dicyclohexyldecane diisocyanate (hydrogenated MDI). a compound having one or more reactive groups capable of reacting with an isocyanate group and one or more polymerizable unsaturated bonds in the molecule (e) having one or more groups reactive with an isocyanate group in the molecule The polymerizable unsaturated bond in the compound (e) or a polymerizable unsaturated bond (hereinafter referred to as "unsaturated compound (e)") may be, for example, contained in a photopolymerizable initiator. The free radicals such as free radicals are polymerized. Such an unsaturated group may be a known one, such as a group containing an ethylenically unsaturated bond, and is preferably a (fluorenyl) acrylonitrile group from the point of easy availability and high reactivity. In the present specification, the term "(meth)acryl fluorenyl means propylene fluorenyl or / and methacryl fluorenyl, (meth) acrylate means acrylate or / and mercapto acrylate, (mercapto) acrylic acid Means acrylic or/and methacrylic acid. The unsaturated compound (e) has one or more polymerizable unsaturated bonds in one molecule. The group which can react with the isocyanate group in the unsaturated compound (e) can be exemplified by a hydroxyl group, an amine group, an isocyanate group, a thiol group or the like. Among them, the point of easiness of handling from 20 323441 201217408 and compound (e) is preferably a hydroxyl group. The unsaturated compound (e) is a group having one or more molecules reactive with an isocyanate group in one molecule. The unsaturated compound (e) is preferably a compound (e') having one or more hydroxyl groups and one or more polymerizable unsaturated bonds from the viewpoint of easiness of handling. The unsaturated compound (e) may, for example, be an unsaturated compound (e, ") having one hydroxyl group and one polymerizable unsaturated bond in the fluorene molecule, and [one molecule and two or more polymerizable groups in the molecule] An unsaturated bond (e -2) having an unsaturated bond, or two or more unsaturated compounds (e, -3) and i having two or more radicals and one polymerizable unsaturated bond in one molecule An unsaturated compound (e, _4) having two or more polymerizable unsaturated bonds. The unsaturated compound (e']) having one hydroxyl group and one polymerizable unsaturated bond in one molecule may, for example, be a ethyl (meth) acrylate vinegar or a 3 propyl propyl (meth) acrylate. Ester, 4 hydroxybutyl (meth) acrylate, and the like. Examples of the unsaturated compound (e, -2) having 1 molecule and 2 or more polymerizable unsaturated bonds in one molecule include glycerol di(meth)acrylic acid vinegar, diglycerin tris(meth)acrylic acid vinegar, and the like. Methyl propyl bromide bis acrylate, neopentyl alcohol tri W propyl acrylate, dipentaerythritol penta (methyl) acrylate vinegar, sorbitol penta (methyl) A (meth)acrylic acid adduct of propyl malate or glycidyl (meth) acrylate. 1 molecule has 2 fine secrets and 1 «synthesis of unsaturated bonds, oral (e -3), for example, glycerol mono (methyl) a vinegar, - glycerol early base) Dilute vinegar, pentaerythritol mono(3)-based acrylic acid vinegar, dipentaerythritol mono (meth) acrylate, sorbitol mono-acrylate 323441 21 201217408 and the like. Examples of the unsaturated compound (e, -4) having two or more hydroxyl groups and two or more polymerizable unsaturated bonds in one molecule include diglyceryl bis(indenyl) acrylate and neopentyl alcohol di(methyl). Acrylate, dipentaerythritol di(meth) acrylate, dipentaerythritol tri(meth) acrylate, dipentaerythritol tetrakis(meth) acrylate, sorbitol di(decyl) Reaction of acrylate, sorbitol tris(decyl) acrylate, sorbitol tetrakis(meth) acrylate, 2 molecules of (mercapto)acrylic acid with 1 molecule of 1,6-hexanediol diglycidyl ester Product (for example, "DA-212" manufactured by Nagasechemtex Co., Ltd.), reaction product of two molecules of epoxy (fluorenyl) acrylic acid and one molecule of neopentyl glycol diglycidyl ester, and two molecules of (mercapto) a reaction product of dilute acid with one molecule of bisphenol a diglycidyl Sa (for example, "DA-250" manufactured by Nagase Chemex Co., Ltd.), a propylene oxide adduct of two molecules of (mercapto)acrylic acid and bisphenol a Reaction product of diglycidyl base, 2 molecules of (fluorenyl) acrylic acid and 1 molecule Acid diglycidyl esters of the reaction product (e.g., manufactured by Nagase Chemtex Corporation "Dmi") 2 molecules (Yue-yl) acrylic acid with one molecule of polyethylene glycol diglycidyl esters of the reaction product (e.g.

Nagase chemtex 公司製「DM-811」、「DM-832」、 「DM-851」）、2分子之（甲基）丙烯酸與1分子之聚丙二醇 二縮水甘油酯之反應生成物等之（甲基）丙烯酸與多元醇二 縮水甘油酯的反應生成物等。 不飽和化合物（e)亦可使用具有異氰酸基之化合物， 例如，就具有異氰酸基之（曱基）丙烯酸化合物，可舉例如 2_異氰酸基乙基丙烯酸酯（昭和電工製Karenz AOI) 2-異 22 323441 201217408 氰酸基乙基（甲基）丙烯酸酯（昭和電工製Karenz Μ〇ι)、 u-雙（丙烯醯氧甲基）乙基異氰酸酯（KarenzBEi)。不 飽和化合物（e)亦可使用Ν·異丙基（甲基）丙烯醯胺等。 又，以不飽和化合物（e，）為首之不飽和化合物（e) 亦可直接使用市售者。不飽和化合物（e )係可單獨使用， 亦可併用複數種。例如，不飽和化合物（e’q)至（e，_4) 之中’可只使用1種，亦可併用2種以上。 不飽和化合物（e)之添加量係從所得到之塗膜的硬 度、塗膜與基材之密著性的點，使水性聚氨基甲酸醋樹脂 分散體之固形分（包含具有聚合性不飽和鍵之化合物 的全量作為100重量份時，宜為2至5〇重量份，更宜為5 至40重量份。藉由使不飽和化合物（e)之添加量為2重 量份以上，可抑制所得到的塗膜的表面硬度降低。藉由使 不飽和化合物（e)之添加量為5〇重量份以下，可抑制所 得到的塗膜與基材之密著性降低。 不飽和化合物（e)係從聚氨基甲酸酯水分散體之貯存 女疋性&amp;咼的點，在不飽和化合物（e，）之中，宜為具有 1個羥基之化合物，具體上，宜為包含丨分子中具有1個 羥基與1個聚合性不飽和鍵之不飽和化合物（e，〗）、及/ 或1分子中具有1個羥基與2個以上聚合性不飽和鍵之不 飽和化合物（e’-2)。其中，從所得到之塗膜的硬度提昇之 點，更宜包含1分子中具有丨個羥基與2個以上聚合性不 飽和基之不飽和化合物（e，_2)，即使在不飽和化合物（e，_2) 之中’更宜為1分子中具有i個減與3個（甲基）丙稀醯 323441 23 201217408 基之化合物。 不飽和化合物（e’-l)及/或不飽和化合物（e’-2)之 使用量係使水性聚氨基甲酸酯樹脂分散體之固形分（包含 具有聚合性不飽和鍵之化合物（B))的全量作為100重量 份時，宜為2至50重量份，更宜為5至40重量份。 不飽和化合物（e)係從所得到之塗膜的硬度之點.，不 飽和化合物（e’）之中宜為具有2個以上之羥基的化合物， 具體上，宜包含1分子中具有2個以上羥基與1個聚合性 不飽和鍵之不飽和化合物（e’-3)、及/或1分子中具有2 個以上羥基與2個以上聚合性不飽和鍵之不飽和化合物 (e’-4)等。其中，從取得之容易性，更宜為包含1分子 中具有2個以上羥基與2個以上聚合性不飽和基之不飽和 化合物（e’-4)，即使在不飽和化合物（e’-4)之中，更宜 為1分子中具有2個羥基與2個（曱基）丙烯醯基之化合物。 不飽和化合物（e’-3)及/或不飽和化合物（e’-4)之 使用量係使水性聚氨基甲酸酯樹脂分散體之固形分（包含 具聚合性不飽和鍵之化合物（B))的全量作為100重量份 時，宜為2至30重量份，更宜為5至20重量份。 VI.含有多元醇之成分的羥基當量 在本發明中，含有多元醇之成分的經基當量宜為100 至500。羥基當量若為此範圍，則水性聚氨基甲酸酯樹脂 分散體之製造容易，易於得到良好的水性聚氨基曱酸酯樹 脂分散體之貯存安定性及硬度優異之塗膜。從塗膜之硬度 的觀點，宜為120至300，更宜為150至250。此處，含有 24 323441 201217408 多元醇之成分係除了聚碳酸s旨多^醇⑴、含有酸性基之 多元醇⑴、及任意之其他的多元醇（c)之外不飽和化 合物（e)為不飽和化合物（e’_3)及/或（e，_4)時，包含 此等之不飽和化合物（e，_3)及/或（e，_4)。 羥基當量數係可用以下之式⑴及（2)算出。 各多元醇之經基當量數=各多元醇之分子量/各多元醇 之羥基的數目…（1) 多元醇之合計的羥基當量數=M /多元醇之合計莫耳 數…（2) 在式（2)中，Μ係表示[[聚碳酸酯多元醇（a)之羥 基當量數X聚碳酸醋多元醇⑴之莫耳數]+ [含有酸性基 之多元醇（b)之羥基當量數x含有酸性基之多元醇（b)之 莫耳數]+ [其他之多元醇（e)之經基當量數χ其他之多元 醇（〇的莫耳數]+ [ (e’_3)之經基當量數X (e，-3)之 莫耳數]]+ [ (e，-4)之經基當量數χ (eM)之莫耳數]]。 VII.聚氨基甲酸S旨樹脂⑷或聚氨基甲酸_預聚物（ai) 本發明中之聚氨基曱酸酯樹脂（A )係至少使聚碳酸 酯多元醇（a)、含有酸性基之多元醇（b)、多元異氰酸酯 ⑷與不飽和化合物（e)反應所得到之聚氨基甲酸醋樹 脂，或，使聚碳酸酯多元醇（a)、含有酸性基之多元醇（b)、 多元異氰酸g旨⑷、與不飽和化合物（e)反應而得到聚氨 基甲酸S旨預聚物（A1)，再進—步與鏈延長劑（c)反應所 得到之聚氨基甲酸酯樹脂。 在得到聚氨基甲酸酯樹脂（A)時，多元異氰酸酯 25 323441 201217408 之，氰I基的莫耳數對聚碳酸§旨多元醇⑷、含有酸性基 夕元醇（b)、視情形存在之其他的多元醇⑷及不飽和 化合物（e，）之全經基的莫耳數的比宜為Ο %至Μ。大 ;或J於此範Hj日夺，聚氨基甲酸酯樹脂（A)之分子量變 J而有無/占黏性差之情形。多元異氰酸醋（d)之異氰酸 基的莫耳數對前述成分之全經基的莫耳數之比宜為㈣ 至1.05 ’尤宜為〇 95至1 〇1。 聚氨基甲酸酯樹脂⑷及聚氨基甲酸酯預聚物（A1) 係使聚碳酸S旨多元醇（a)、含有酸性基之多元醇（b)、其 他之多元醇（c)、多元異氰酸酯（d)、與不飽和化合物（e) 反應所得到之反應生成物；或為使聚碳酸酯多元醇（a)、含 树性基之多元醇⑴、其他之多元醇⑷、多元異氛酸 酯（d)、與不飽和化合物反應而得到聚氨基甲酸酯預 聚物（A1)，再進一步與鏈延長劑（c)反應所得到之聚氨 基甲酸酯樹脂。 使聚氨基甲酸酯預聚物（A1)與鏈延長劑（c)反應 而得到聚氨基甲酸酯樹脂時，聚氨基甲酸酯預聚物（A1 ) 與鏈延長劑（C)之反應的溫度例如為〇至8〇«&gt;C，宜為〇 至 60°c。 在得到聚氨基甲酸酯預聚物（A1)時’多元異氰酸酯 (d)之異亂酸基的莫耳數對聚碳酸酯多元醇（a)、含有酸 性基之多元醇（b)、視情形存在之其他的多元醇（c)及不 飽和化合物（e，）之全羥基的莫耳數的比宜為1.〇1至2.5。 若為此範圍，因含有前述經基之成分的經基之莫耳數太 323441 26 201217408 多，而於分子末端不具有異氰酸基之聚氨基曱酸酯預聚物 (A1)變多，使不與鏈延長劑（C)反應之分子變多，而 易於避免塗佈水性聚氨基曱酸酯樹脂分散體所得到之塗膜 的強度降低之問題，又，因含有前述羥基之成分的羥基之 莫耳數太少’使未反應之多元異氰酸酯（d)大量地殘存於 反應系内’而與鏈延長劑反應，或與水反應而引起分子伸 長’亦易於避免塗佈水性聚氨基曱酸酯樹脂分散體所得到 之塗膜產生凹凸之問題。多元異氰酸酯（d)之異氰酸基的 莫耳數對前述成分之全羥基的莫耳數的比宜為1,2至 2.2 ’尤宜為1.3至2.0。 在得到聚氨基.曱酸酯樹脂（A )或聚氨基曱酸酯預聚 物（A1 )時，由聚碳酸酯多元醇（a )、含有酸性基之多元 醇（b)視情形之其他之多元醇（c)、及不飽和化合物（e) 所構成的成分、與多元異氰酸酯（d)之反應可使（a)、（b)、 視情形之（c)、（e)以不同順序與（d)反應，亦可混合複 數種而與（d)反應。使前述成分與多元異氰酸酯反 應時’亦可使用觸媒。 觸媒係無特別限定，可舉例如錫系觸媒（三曱基錫月 桂駄酯、二丁基錫二月桂酸酯等）或鉛系觸媒（辛酸鉛等） 等之金屬與有機及無機酸之鹽、以及有機金屬衍生物、胺 系觸媒（三乙胺、N_乙基嗎啉、三乙二胺等）、二氮雜二 裒十碳稀系觸媒等。其中，從反應性之觀點，宜為二丁 基錫—月桂酸g旨。 使前述成分與多元異氰酸酯（d)反應時之反應溫度 27 323441 201217408 係無特別限定，但宜為40至12(rc。若為此範圍，原料之 溶解充分’所得狀聚氨基曱酸㈣m⑷或聚氨基甲 酸醋預聚物（A1)之點度為適當，易於擾拌，X，易於避 免不飽矛化口物（e)中之聚合性不飽和鍵引起聚合反應而 凝膠化，或引起多it異氰酸g|⑷中之異氰酸基的副反應 等的不佳情形。反應溫度更宜為6〇至1〇〇t。 使不飽和化合物（e)與多元異氮酸酿（d)反應時， 為避免不飽和化合物（e)中之聚合性不飽和鍵的不必要消 耗’故宜在氧存在下進行。 本發明中，在得到多元氨基甲酸醋樹脂（A)或聚氨 基甲酸醋預聚物（A1)之步驟中，為避免不飽和化合物⑷ 之聚合性不飽和鍵的不必要消耗，亦可於反應系中預先添 加阻聚劑。 阻聚劑係可舉例如氫醌、氫醌單甲基醚、苯醌、2_第 三丁基氫酿、第三丁基兒茶紛、2,5.雙（u，3,3_ra甲基丁 基）氫酿、2,5-雙（l，i_二甲基丁基）氫職等之酿系阻聚劑； 2,6-雙（1，1-二甲基乙基）_4_曱基酚、2,6•二第三丁基酚、 2,4-一第二丁基酚、2_第三丁基_4,6_二甲基酚、2,6_二第三 丁基-4-甲基酚、2,4,6_三第三丁基紛等之烧基齡系阻聚 劑’酚噻啡等之芳香族胺系阻聚劑；烷基化二苯基胺、N，N，_ 二苯基-對·苯二胺、酚噻哄、4_羥基_2,2,6,6_四甲基六氫吡 啶、4-苯甲醯氧基_2,2,6,6_四甲基六氫吡啶、i，4_二羥基 -2,2,6,6-四甲基六氫吡啶、丨_羥基_4苯甲醯氧基·2,2,6,6四 甲基六氫吡啶、二-對氟苯基胺、2,2,6,6_四甲基六氫吡啶^ — 28 323441 201217408 氧化物（TEMPO)等之胺系阻聚劑；其他2,2_二苯基苦味 基肼（diphenylpicrylhydrazyl) (DppH)、三_對-硝基苯基甲 燒、N- 〇N-氧苯胺基-1,3-二曱基亞丁基）_苯胺氧化物、 氣化笨曱基二曱基銨等之氯化4級銨；二乙基羥基胺、環 狀醯胺、腈化合物、取代尿素、笨並噻唑、雙_( 五甲基-4-六氫口比咬基）癸二酸龜、乳酸、草酸、捧樣酸、 酒石酸、安息香酸等之有機酸；有機磷、亞麟酸鹽等。此 等係可單獨使H亦可併用複數種。尤其藉由併用酿 系阻聚劑減絲纽㈣，料性不飽和鍵之聚合所產 生的消耗可更減少。 阻聚劑之添加量係相對於聚氨基甲酸醋樹脂⑷議 重量份，可為隨至1重量份，更宜為G.G1至〇.5重量 份。 聚石炭酸醋多元醇U)、含有酸性基之多元醇⑴、依 情形之其他之多元醇（ο、及不飽和化合物（e)、與多元 異氰酸醋⑷之反應可在無溶劑下，或加人有機溶劑而進 行。有機溶劑係可舉例如丙酮、曱乙酮、曱基異丁基酮、 四氫吱喃、二姚、二甲基甲酿胺、二甲基亞石風、N_甲基 吡咯烷酮、N-乙基吡咯烷酮、醋酸乙酯等。其中，丙酮、 曱乙酮、醋酸乙酯係聚氨基曱酸酯預聚物於水中之分散及 鏈伸長反應後可藉加熱減壓除去，故佳。又，沁曱基吡咯 燒_、N-乙基吼嘻炫_從所得到之水性聚氨基曱酸醋樹脂 分散體製作塗膜時發揮造膜助劑作用，故佳。有機溶劑之 添加量係相對於聚碳酸酯多元醇（a)、含有酸性基之多元 323441 29 201217408 醇（b)、依情形之其他之多元醇（c)、及不飽和化合物（e) 之全罝，就重量基準，宜為〇至2.0倍，更宜為0.1至0.7 倍。若為此範圍’使得到聚氨基甲酸酯預聚物（A1)時之 黏度為適當的範圍，可得到良好的分散。另外，除去有機 溶劑所需之時間不需太長’於使用水性聚氨基曱酸酯樹脂 为政體所得到之塗膜中殘存有機溶劑，可容易地避免塗膜 物性降低之事態。 在本發明中’聚氨基甲酸酯樹脂（A)或聚氨基甲酸 酉曰預聚物（A1 )之酸價宜為2〇至5〇mgK〇H/y若為此範 圍’易確保於良好的水系介質中的分散性及塗膜之耐水 f生刖述酸饧更宜為25至45mgKOH/g，更宜為30至 40mgKOH/g。 此處，聚氨基甲酸酯樹脂（A)或聚氨基曱酸酯預聚 物（A1)之酸價係謂當製造聚氨基甲酸酯樹脂或聚 氨基甲酸酯預聚物（A1)時為使所使用之溶劑及聚氨基甲 &amp;酉曰預聚物（A1)分散於水系介質巾之巾和劑去除之所謂 的固形分中之酸基的平均含量，從聚碳酸酯多元醇（a)、 含有酸性基之多元醇（b)、依情形之其他之多元醇（c)、 不飽和化合物（e)及多元異氰酸|旨（d)之重量、以及含 有酸性基之多元醇（b)所含有的酸性基求出，可依下述式 (3 )而導出。 [聚氨基甲酸酯樹脂（A)或聚氨基甲酸酯預聚物（A1)之 酸價]=[含有酸性基之多元醇（b)之酸性基的莫耳數]χ 56.11/[聚碳酸酯多元醇（a)、含有酸性基之多元醇（b)、 323441 30 201217408 依情形之其他之多元醇（C)、不飽和化合物（e)及多元異 氰酸酯（d)的合計之重量]…（3) 、 得到聚氨基甲酸醋預聚物（A1)之後，於水系溶劑的 分散與鏈延長劑（C)所得到之鏈延長而得到本發明之水 性聚氨基甲酸醋樹脂分散體時，前述酸價係與聚氨基甲酸 酯預聚物（A1)之酸價同義。 在得到聚氨基甲酸醋樹脂⑷或聚氨基甲酸酉旨預聚 物（A1 )時，使水性聚氨基甲酸酯樹脂分散體之固形分（包 含具有聚合性不飽和鍵之化合物（B))全量為刚重量份 時’聚碳酸醋多元醇（a)宜為2至50重量份，含有酸性 ，之多元醇（b)宜為2至15重量份，其他之多元醇⑷ 宜為〇至30重量份，不飽和化合物（e)宜為5至5〇重量 份。若聚碳酸酯多元醇（a)為前述之範圍，從水性聚氨基 甲酸醋樹脂分散體所得到之塗膜的密著性高，X，聚氨基 曱酸醋樹脂（A)於水系介質之分散性良好，可容^得二 優異之製膜性。聚碳酸酯多元醇（a)宜為3至40重量份， 尤宜為5至30重量份。含有酸性基之多元醇⑴若為前 述之範圍從水性聚氨基mg旨樹脂分散體所得到之塗膜 的耐水性良好，聚氨基甲酸賴脂（a)於水系介質中之 /讀性良好。含有酸性基之多元醇⑴宜為3至10重量 =尤，為4至7重量份。不飽和化合物（e)若為前述之 &amp;，從水性聚氣基甲酸酯樹脂分散體所得到之塗膜的硬 ^密著性良好’可制水性聚氨基甲_旨樹脂分散體之 貯存安定性亦優異者。不飽和化合物（e)更宜為1〇至4〇 323441 31 201217408 重量份。 VIII.鏈延長劑（ς；) ㈣之聚合性不飽和鍵㈣氨基甲酸醋樹脂 乂係稭由使用鏈延長劑(C)而於活性能量線(例如紫 夕卜線）照射前的乾燥塗膜上很少沾黏，成為無沾黏，故宜 使用鏈延長劑（c)所調製者。鏈延長劑⑹可 乙二胺、Μ_四甲基二胺、2-甲基十5-戊二胺、Μ_ 丁二丄 1 一’6 /、亞甲基一胺、Μ六亞甲基二胺、3胺基曱基3,5 5_ ^甲基環己基胺、U，（胺基甲基）環己烧、二甲笨’二 胺/、氫比Π井、2,5-二曱基六氫0比哄、聯胺、己二 二乙三胺、三乙四胺等之胺化： 物、乙一醇、丙二醇、Μ· 丁二醇、1，6·己二醇等之二醇化 ^物、聚乙二醇為代表之聚院二醇類、水等，其中，從所 得到之塗膜的活性能量線（例如紫外線）硬化後之塗膜的 硬度之點，鏈延長劑（C)宜為有機化合物，更宜為多胺 化&amp;物尤且為1級多胺化合物。此等係可單獨使用，亦 可併用複數種。 鍵延長劑（C)之添加量係宜成為聚氨基曱酸醋預聚 物（Α1)中之鏈延長起點的異氰酸基之當量以下，更宜為 異氰酸基之0.7至0.99當量。若為此範圍，使鏈延長之聚 氨基甲酸醋樹脂（Α).的分子量作為適當的範圍，甚至， 塗佈含有此之水性聚氨基甲酸酯樹脂分散體而得到之塗膜 的強度良好。鏈延長劑（c)可於聚氨基曱酸酯預聚物（Α1) 於水中分散後添加，亦可於分散中添加。鏈延長亦可藉水 323441 32 201217408 而進行。此時，作為分散媒之水兼具鏈延長劑。 〈具有聚合性不飽和鍵之化合物（B)〉 本發明中的具有聚合性不飽和鍵之化合物（B )係宜 為光自由基產生劑之共存下，或在熱自由基產生劑的存在 下進行聚合者，但在25°C中宜使用與異氰酸基不反應之化 合物。 具有聚合性不飽和鍵之化合物（B)可舉例如具有乙 烯基或烯丙基等之乙烯性不飽和鍵之化合物，可舉例如具 有（曱基）丙烯醯基之化合物。具有聚合性不飽和鍵之化合 物（B)可為具有1個含（曱基）丙烯醯基等之聚合性不飽和 鍵的基的1官能性之化合物，亦可為具有複數個多官能性 的化合物，亦可適宜使用具有3個以上（曱基）丙烯醯基的 化合物或具有5個以上（曱基）丙烯醯基的化合物。 具有聚合性不飽和鍵之化合物（B)宜為（曱基）丙烯酸 酯化合物。（曱基）丙烯酸酯化合物係可舉例如單體類之（曱 基）丙烯酸酯化合物、或聚氨基曱酸酯（甲基）丙烯酸酯化合 物、聚酯（曱基）丙烯酸酯系化合物、聚（曱基）丙烯酸伸烷酯 系化合物等。 單體類之（曱基）丙烯酸酯化合物係可使用單（曱基）丙 烯酸酯或二（曱基）丙烯酸酯、三（曱基）丙烯酸酯、四（曱基) 丙烯酸酯、五（曱基）丙烯酸酯、六（曱基）丙烯酸酯等之單（甲 基）丙烯酸酯或聚（甲基）丙烯酸酯。 前述單（曱基）丙烯酸酯可舉例如2-乙基己基（曱基）丙 烯酸酯、曱基（甲基）丙烯酸酯、四氫呋喃甲基（曱基）丙烯酸 33 323441 201217408 酯、十二碳基（甲基）丙烯酸酯、環己基（曱基）丙烯酸酯、二 環戊烯基（曱基）丙烯酸酯、2-乙基己基（甲基）丙烯酸酯、二 環戊烯氧基乙基（甲基）丙烯酸酯、苯氧基乙基（曱基）丙烯酸 酯、異冰片基（甲基）丙烯酸酯等。 二（曱基）丙烯酸酯係可舉例如乙二醇二（甲基）丙烯酸 酯、丙二醇二（曱基）丙烯酸酯、新戊二醇二（曱基）丙烯酸 酯、1,4-丁二醇二（曱基）丙烯酸酯、16-己二醇二（曱基）丙 烯酸酯、三環癸烷二曱醇二（甲基）丙烯酸酯、雙酚A二（甲 基）丙烯酸酯等之伸烷二醇二（曱基）丙烯酸酯；聚乙二醇二 (甲基）丙烯酸酯、聚丙二醇二（甲基）丙烯酸酯等之聚醚二 (曱基）丙烯酸酯；雙酚A環氧乙烷改性二（甲基）丙烯酸酯、 雙酚A環氧丙烷改性二（甲基）丙烯酸酯、新戊二醇環氧乙 烧改性二（甲基）丙烯酸酯、新戊二醇環氧丙烷改性二（甲基) 丙稀酸醋等之環氧烷改性二（曱基）丙烯酸酯；1&gt;6_&amp;二醇環 氧基二（曱基）丙烯酸酯、新戊二醇環氧基二（曱基）丙烯酸 酉曰雙紛A %氧基一（甲基）丙浠酸醋、雙紛A環氧丙烧改 性環氧基二（曱基）丙烯酸酯、酞酸環氧基二（曱基）丙烯酸 酯、聚乙二醇環氧基二（曱基）丙烯酸酯、聚丙二醇環氧基 二（甲基）丙烯酸酯等之環氧基二（曱基）丙烯酸酯等。 二（曱基）丙烯酸酯係可舉例如三羥曱基丙烷三（曱基) 丙烯酸酯、環氧乙烷改性三經甲基丙烷三（曱基）丙烯酸 酯、環氧丙烷改性三羥甲基丙烷三（甲基）丙烯酸酯、新戊 四醇二（甲基）丙稀酸g旨等。 四（甲基）丙烯酸酯係可舉例如二新戊四醇四（甲基）丙 34 323441 201217408 烯酸酯、新戊四醇四（曱基）丙烯酸酯、環氧乙烷（4莫耳） 改性新戊四醇四（曱基）丙烯酸醋（Daicel Cytec公司、 Ebecryl40)等之環氧烷改性新戊四醇四（曱基）丙烯酸酯、 二-三羥甲基丙烷四（曱基）丙烯酸酯。 五（曱基）丙烯酸酯係可舉例如二新戊四醇五（曱基）丙 浠酸醋。 六（曱基）丙烯酸酯係可舉例如二新戊四醇六（曱基）丙 烯酸S旨等。 此等之單體類之（甲基）丙烯酸酯化合物中，從硬度之 點，宜為二（曱基）丙烯酸酯、三（曱基）丙烯酸酯、四（曱基) 丙烯酸酯、五（甲基）丙烯酸酯、六（曱基）丙烯酸酯的聚（甲 基）丙烯酸酯。此等係藉由於内子内具有複數之（曱基）丙烯 醯基，較同為單（甲基）丙烯酸酯者更易高分子量化。其中， 從硬度之點，宜為三（甲基）丙烯酸酯、四（曱基）丙烯酸酯、 五（甲基）丙烯酸酯、六（甲基）丙烯酸酯。更佳係五（甲基）丙 烯酸酯、六（曱基）丙烯酸酯。 聚合物類之（甲基）丙烯酸酯係除了具有聚伸烷二醇構 造之（曱基）丙烯酸酯以外，亦可使用聚氨基甲酸酯（曱基) 丙烯酸酯化合物、聚酯（曱基）丙烯酸酯系化合物、聚伸烷 基（曱基）丙烯酸酯系化合物等，例如可使用於分子内具有 聚合性不飽和鍵之丙烯酸系聚合物等，可舉例如於分子片 末端具有聚合性雙鍵之聚丁基丙烯酸酯（綜研化學公司製 「Actflow BGV-100T」）、或於分子兩末端具有聚合性雙鍵 之聚丁基丙烯酸酯（綜研化學公司製「Actflow」）等。 35 323441 201217408 具有聚合性不飽和鍵之化合物⑻亦可使用丙稀醯 基嗎琳、苯乙嫦、N_乙烯基等之基）丙稀酸 醋化合物以外的含有乙烯基或缔丙基的化合物。 具有聚合性不飽和鍵之化合物（Β)可直接使用市售 者。具有聚合性不飽和鍵之化合物⑻係可單獨使用， 亦可併用複數種。 以水性聚氨基甲酸酯樹脂分散體之固形分（包含具有 聚合性不飽和鍵之化合物（Β))的全量作為1〇〇重量f分時， 宜為2至50重量份’更宜為5至40重量份。 具有聚合性不飽和鍵之化合物（B)係以水性聚氨基 曱酸酯樹脂分散體之固形分（含有聚氨基甲酸酯樹脂（A)) 的全量作為100重量份時，宜為1〇至6〇重量份。若為此 範圍，可谷易使從水性聚氰基曱酸酯樹脂分散體所得到之 塗膜的密著性及硬度請，且對於纽聚氨基旨樹脂 分散體可得到良好㈣存安定性。具有聚合性不飽和鍵之 =物⑻更宜為20至50重量份，最宜為3〇至^重 7 聚氨基甲酸酯樹脂分散體〉 X·水系介質 介質:本=二:ΐ基_旨樹脂(A)係分散於水系 混合介質等/舉例*水、或水與親擁有機溶劑之 水係可舉例如自來水 等。其中，若考孴^ 水、蒸餾水、超純水 考I取得料性或_影響錄子變的不安 323441 36 201217408 疋專’宜為離子交換水。 親水性有機溶劑係可舉例 級-元醇;乙二醇、甘油等之多二乙醇、丙醇等之低 尤™ « 疋知，Ν-甲基嗎啉、二甲美 石、-土甲醯胺、ν·甲基％錢 ς 水性有機溶劑等。水系介質中 非買子法的親 0至20重量％。 1質中之親水性有機溶劑的量宜為 XI.水性聚氨基甲酸賴脂分散體之製造方法 其-人水性聚氨基甲酸酯樹脂分散體之製造方 法。 本發明之水性聚氨基甲酸自旨_，其係至少使於主鏈 具有脂環構造之聚碳酸自旨二醇（a)、含有酸性基之多元醇 (b)、多元異氰酸醋⑷、肖i分子中具有】個以上可與 異氰酸基反應的基與i個以上聚合性不飽和鍵的化合物 (e)反應而得到聚氨基甲酸酯樹脂（A)， 使聚氨基甲酸酯樹脂（A)及具有聚合性不飽和鍵之 化合物（B)分散於水系介質中而得。 本發明之水性聚氨基甲酸酯樹脂分散體之製造方 法，其係包含如下步驟： 使聚碳酸醋多元醇（a)、含有酸性基之多元醇、 多元異氰酸醋（d)、與具有i個以上可與異氰酸基反應的 基與1個以上聚合性不飽和鍵的化合物反應而得到聚 氨基甲酸醋預聚物（A1)之步驟（αι)、 中和聚氣基甲酸g旨預聚物（Α1 )之酸性基的步驟 {β)' 37 323441 201217408 使聚氨基甲酸㈣預聚物（A1)與具有聚合性不飽和鍵 之化合物（B)分散於水系介質中之步驟（γ )、 使聚氨基甲酸醋預聚物（Α1)、與聚氨基甲酸醋預聚 物（Α1)之異氰酸基具有反應性的鍵延長劑（c)反應而 得到水性聚氨基甲酸酯樹脂的步驟（$ )。 又，包含如下步驟： 使聚碳酸醋多元醇（a)、含有酸性基之多元醇⑴、 其他之多元醇（c)、多元異氰酸酯⑷、與具有i個以上 可與異氰酸基反應的基與i個以上聚合性不飽和鍵的化合 物（e)反應而得到聚氨基f酸醋預聚物（ai)之步驟 2)、 中和聚氨基甲酸酯預聚物（A1 )之酸性基的步驟 (β)、 使聚氨基甲酸酿預聚物（Α1)與具有聚合性不飽和鍵 之化合物（Β)分散於水系介質中之步驟（γ )、 使聚氨基甲酸酿預聚物（Α1)、與聚氨基甲酸醋預聚 物（Α1)之異氰酸基具有反應性的鍵延長劑（c)反應而 得到水性聚氨基甲酸酯樹脂的步驟（占）。 得到聚氨基曱酸g旨預聚物（Α1)之步驟（α i)及（α 2)係為避免聚合性不飽和鍵之不必要的消耗，宜在氧存在 下進行。又，宜依需要而於反應系内添加阻聚劑。得到聚 氨基曱酸醋預聚物（Α1)之步驟（α ^及（α2)的溫度 係為避免聚合性不飽和鍵之不必要的聚合，可在〇至12〇 C下進行。更宜在〇至100°c下進行。 323441 38 201217408 在中和聚氨基甲酸酯預聚物（A1)之酸性基的步驟 (召）中可使用的酸性基中和劑，係可舉例如三曱胺、三 乙胺、三異丙基胺、三丁胺、三乙醇胺、N—曱基二乙醇胺、 N-苯基二乙醇胺、二曱基乙醇胺、二乙基乙醇胺、N-曱基 嗎琳、°比咬等之有機胺類；氫氧化鈉、氫氧化鉀等之無機 驗類、氨等。其中宜為有機胺類，更佳係3級胺，最佳係 三乙胺。此處，聚氨基曱酸酯預聚物（A1)之酸性基係指 叛酸基、續酸基等。 酸性基中和劑之使用量相對於聚氨基曱酸酯預聚物 (A1)之酸性基，就莫耳數宜成為0.8至1.5之量。若為 此範圍’聚氨基甲酸酯預聚物（A1)於水之分散性充分， 所得到之水性聚氨基曱酸酯樹脂分散體的貯存安定性亦不 致降低’且亦可容易地避免所謂水性聚氨基甲酸酯樹脂分 散體之臭氣變強之事態。 在使聚氨基甲酸酯預聚物（A1)與具有聚合性不飽和 鍵之化合物（B)分散於水系介質中之步驟（γ )中，係 ==)可分散於水系介質中’其方法及操作順 料，係無特別限定，但例如於（ai)混合（B)而Nagase chemtex "DM-811", "DM-832", "DM-851"), a reaction product of two molecules of (meth)acrylic acid and one molecule of polypropylene glycol diglycidyl ester (methyl) a reaction product of acrylic acid and a polyol diglycidyl ester. The unsaturated compound (e) may also be a compound having an isocyanate group, for example, a (mercapto)acrylic acid compound having an isocyanate group, and, for example, 2-isocyanatoethyl acrylate (manufactured by Showa Denko) Karenz AOI) 2-Iso 22 323441 201217408 Cyanate ethyl (meth) acrylate (Karenz Μ〇ι, manufactured by Showa Denko), u-bis(acryloxymethyl)ethyl isocyanate (KarenzBEi). As the unsaturated compound (e), hydrazine isopropyl (meth) acrylamide or the like can also be used. Further, the unsaturated compound (e) including the unsaturated compound (e,) may be used as it is. The unsaturated compound (e) may be used singly or in combination of plural kinds. For example, one of the unsaturated compounds (e'q) to (e, _4) may be used alone or two or more kinds may be used in combination. The amount of the unsaturated compound (e) added is a solid content (including a polymerizable unsaturated group) of the aqueous polyurethane resin dispersion from the point of the hardness of the obtained coating film and the adhesion between the coating film and the substrate. When the total amount of the compound of the bond is 100 parts by weight, it is preferably 2 to 5 parts by weight, more preferably 5 to 40 parts by weight. By adding the amount of the unsaturated compound (e) to 2 parts by weight or more, the inhibition can be suppressed. The surface hardness of the obtained coating film is lowered. When the amount of the unsaturated compound (e) added is 5 parts by weight or less, the adhesion between the obtained coating film and the substrate can be suppressed from being lowered. Unsaturated compound (e) From the point of storage of the genus &amp; oxime of the polyurethane aqueous dispersion, among the unsaturated compounds (e,), it is preferably a compound having one hydroxy group, and specifically, it is preferably contained in a ruthenium molecule. An unsaturated compound having one hydroxyl group and one polymerizable unsaturated bond (e,), and/or an unsaturated compound having one hydroxyl group and two or more polymerizable unsaturated bonds in one molecule (e'-2) ), from which the hardness of the obtained coating film is increased, An unsaturated compound (e, _2) having one hydroxyl group and two or more polymerizable unsaturated groups in one molecule, even in the unsaturated compound (e, _2), it is more preferable to have i minus one molecule Compound with 3 (meth) propyl oxime 323441 23 201217408. The unsaturated compound (e'-l) and / or unsaturated compound (e'-2) is used to make aqueous polyurethane resin The total amount of the solid content of the dispersion (comprising the compound (B) having a polymerizable unsaturated bond) is preferably from 2 to 50 parts by weight, more preferably from 5 to 40 parts by weight, per 100 parts by weight. Unsaturated compound (e) It is preferable that the unsaturated compound (e') is a compound having two or more hydroxyl groups from the viewpoint of the hardness of the obtained coating film. Specifically, it is preferable to contain two or more hydroxyl groups and one polymerization in one molecule. An unsaturated compound (e'-3) having an unsaturated bond, and/or an unsaturated compound (e'-4) having two or more hydroxyl groups and two or more polymerizable unsaturated bonds in one molecule. It is easier to obtain, and it is more preferable to have two or more hydroxyl groups and two or more polymerizations in one molecule. The unsaturated group unsaturated compound (e'-4), even among the unsaturated compound (e'-4), is more preferably a compound having two hydroxyl groups and two (indenyl) acrylonitrile groups in one molecule. The unsaturated compound (e'-3) and/or the unsaturated compound (e'-4) are used in an amount to form a solid dispersion of the aqueous polyurethane resin dispersion (comprising a compound having a polymerizable unsaturated bond ( The total amount of B)) is preferably from 2 to 30 parts by weight, more preferably from 5 to 20 parts by weight, based on 100 parts by weight. VI. Hydroxyl Equivalent of Component Containing Polyol In the present invention, a component containing a component of a polyol The base equivalent is preferably from 100 to 500. If the hydroxyl equivalent is in this range, the aqueous polyurethane resin dispersion can be easily produced, and the storage stability and hardness of the aqueous polyurethane resin dispersion can be easily obtained. Coating film. From the viewpoint of the hardness of the coating film, it is preferably from 120 to 300, more preferably from 150 to 250. Here, the component containing 24 323441 201217408 polyol is an unsaturated compound (e) other than the polyhydric alcohol s-polyol (1), the acidic group-containing polyol (1), and any other polyol (c). When the compound (e'_3) and/or (e, _4) are saturated, these unsaturated compounds (e, _3) and/or (e, _4) are contained. The number of hydroxyl equivalents can be calculated by the following formulas (1) and (2). The number of base groups of each polyol = the molecular weight of each polyol / the number of hydroxyl groups of each polyol... (1) The total number of hydroxyl groups of the polyol = the total number of moles of M / polyol... (2) In (2), lanthanide indicates [[the number of hydroxyl equivalents of polycarbonate polyol (a) X the number of moles of polycarbonate polyol (1)] + the number of hydroxyl equivalents of polyol (b) containing an acidic group x The number of moles of the polyol (b) containing an acidic group] + the basis number of the other polyol (e), the number of other polyols (the molar number of oxime) + [(e'_3) The number of moles of the number of equivalents X (e, -3)]] + [the number of bases of (e, -4), the number of moles of χ (eM)]]. VII. Polyurethane S resin (4) or poly Carbamate_Prepolymer (ai) The polyaminophthalate resin (A) in the present invention is at least a polycarbonate polyol (a), an acid group-containing polyol (b), a polyvalent isocyanate (4) and an unsaturated group. The polyurethane resin obtained by the reaction of the compound (e), or the polycarbonate polyol (a), the acid group-containing polyol (b), the polyisocyanate g (4), and the unsaturated compound (e) Reaction Polyurethane resin obtained by reacting a polyurethane prepolymer (A1) with a chain extender (c). When a polyurethane resin (A) is obtained, a polyisocyanate is obtained. 25 323441 201217408, the molar number of cyanide I groups for polycarbonate § polyol (4), containing acidic keto alcohol (b), optionally other polyols (4) and unsaturated compounds (e,) The ratio of the molar number of the radical is preferably from Ο% to Μ. Large; or J is in this range of Hj, the molecular weight of the polyurethane resin (A) is changed to J, and there is a case where the viscosity is poor. The molar ratio of the number of moles of the isocyanato group of the cyanic acid vinegar (d) to the molar number of the total mercapto group of the above component is preferably from (4) to 1.05', particularly preferably from 95 to 1 〇 1. Polyurethane resin (4) Polyurethane prepolymer (A1) is a polyhydric alcohol S (polyhydric alcohol) (a), an acidic group-containing polyol (b), another polyhydric alcohol (c), a polyvalent isocyanate (d), and Unsaturated compound (e) The reaction product obtained by the reaction; or the polycarbonate polyol (a), the polybasic group containing the tree group (1), and the like An alcohol (4), a polyisocyanate (d), a polyurethane resin obtained by reacting with an unsaturated compound to obtain a polyurethane prepolymer (A1), and further reacting with a chain extender (c) When the polyurethane prepolymer (A1) is reacted with the chain extender (c) to obtain a polyurethane resin, the polyurethane prepolymer (A1) and the chain extender (C) are used. The temperature of the reaction is, for example, from 〇 to 8 〇 «&gt; C, preferably from 〇 to 60 ° C. When the polyurethane prepolymer (A1) is obtained, the molybdenum group of the polyisocyanate (d) The ratio of the number of moles of the polycarbonate to the polycarbonate polyol (a), the acid group-containing polyol (b), optionally other polyols (c) and the unsaturated compound (e,) It is 1.〇1 to 2.5. If it is in this range, the number of moles of the radical containing the above-mentioned base group is more than 323,441,26,2012,17,408, and the polyaminophthalate prepolymer (A1) which does not have an isocyanate group at the molecular end is more, By increasing the number of molecules which do not react with the chain extender (C), it is easy to avoid the problem of lowering the strength of the coating film obtained by applying the aqueous polyaminophthalate resin dispersion, and also the hydroxyl group of the component containing the aforementioned hydroxyl group. Too little number of moles 'to leave the unreacted polyisocyanate (d) in the reaction system in a large amount 'to react with the chain extender, or to react with water to cause molecular elongation' is also easy to avoid coating aqueous polyaminodecanoic acid The coating film obtained from the ester resin dispersion has a problem of unevenness. The molar ratio of the number of moles of the isocyanato group of the polyisocyanate (d) to the number of moles of the total hydroxyl group of the above component is preferably from 1,2 to 2.2 Å, particularly preferably from 1.3 to 2.0. When the polyamino-phthalic acid ester resin (A) or the polyaminophthalate prepolymer (A1) is obtained, the polycarbonate polyol (a) and the acid group-containing polyol (b) may be other depending on the case. The reaction between the component composed of the polyol (c) and the unsaturated compound (e) and the polyisocyanate (d) allows (a), (b), and (c) and (e) depending on the case. (d) The reaction may be carried out by mixing a plurality of species with (d). When the above components are reacted with the polyisocyanate, a catalyst can also be used. The catalyst is not particularly limited, and examples thereof include a metal such as a tin-based catalyst (trimethyl succinyl lauryl ester, dibutyltin dilaurate, or a lead-based catalyst (lead octanoate), and an organic or inorganic acid. A salt, an organometallic derivative, an amine-based catalyst (triethylamine, N-ethylmorpholine, triethylenediamine, etc.), a diazabifluorene-based carbon-based catalyst, or the like. Among them, from the viewpoint of reactivity, it is preferred to use dibutyltin-lauric acid. The reaction temperature at the time of reacting the above-mentioned component with the polyvalent isocyanate (d) is not particularly limited, but is preferably 40 to 12 (rc. If it is in this range, the dissolution of the raw material is sufficient 'the obtained polyaminodecanoic acid (iv) m (4) or poly The urethane acetal prepolymer (A1) has a suitable degree and is easy to be disturbed. X, it is easy to avoid the polymerization of the unsaturated unsaturated bond in the unsaturated spear (e) to cause polymerization, gelation, or cause more It is not preferable for the side reaction of the isocyanate group in the isocyanate g|(4), etc. The reaction temperature is more preferably 6 Torr to 1 Torr. The unsaturated compound (e) is mixed with the polyismonic acid (d) In the reaction, in order to avoid unnecessary consumption of the polymerizable unsaturated bond in the unsaturated compound (e), it is preferably carried out in the presence of oxygen. In the present invention, a polybasic urethane resin (A) or a polyurethane is obtained. In the step of the vinegar prepolymer (A1), in order to avoid unnecessary consumption of the polymerizable unsaturated bond of the unsaturated compound (4), a polymerization inhibitor may be added in advance to the reaction system. The polymerization inhibitor may, for example, be hydroquinone. Hydroquinone monomethyl ether, benzoquinone, 2_t-butyl hydrogen, third Base tea, 2,5. Double (u, 3, 3_ra methyl butyl) hydrogen brewing, 2,5-bis (l, i-dimethyl butyl) hydrogen grade brewing polymerization inhibitor; 2,6-bis(1,1-dimethylethyl)_4-nonylphenol, 2,6•di-t-butylphenol, 2,4-dibutylphenol, 2_t-butyl _4,6-Dimethylphenol, 2,6-di-t-butyl-4-methylphenol, 2,4,6-tri-tert-butyl, etc. Aromatic amine-based polymerization inhibitors such as morphine; alkylated diphenylamine, N, N, _ diphenyl-p-phenylenediamine, phenothia, 4 hydroxy 2, 2, 6, 6 _ Tetramethylhexahydropyridine, 4-benzylideneoxy-2,2,6,6-tetramethylhexahydropyridine, i,4-dihydroxy-2,2,6,6-tetramethylhexahydro Pyridine, hydrazine-hydroxy-4 benzylideneoxy 2,2,6,6 tetramethylhexahydropyridine, di-p-fluorophenylamine, 2,2,6,6-tetramethylhexahydropyridine^ — 28 323441 201217408 Amine-based polymerization inhibitors such as TEMPO; other 2,2-diphenylpicrylhydrazyl (DppH), tri-p-nitrophenylmethyl, N-〇N -Oxoaniline-1,3-didecylbutylene)-aniline oxide, vaporized albino diammonium ammonium, etc. Diethylhydroxylamine, cyclic guanamine, nitrile compound, substituted urea, stupid thiazole, bis(pentamethyl-4-hexahydropyranyl) phthalic acid turtle, lactic acid, oxalic acid, lactic acid, Organic acids such as tartaric acid and benzoic acid; organic phosphorus, linoleic acid, and the like. These lines can be used alone or in combination with H. In particular, the consumption of the polymerization of the unsaturated unsaturated bond can be further reduced by using the blending inhibitor (S). The amount of the polymerization inhibitor added is from 1 part by weight, more preferably from G.G1 to 5% by weight, based on the weight of the polyurethane resin (4). a polycarbonate vinegar polyol U), an acid group-containing polyol (1), and optionally other polyols (o, and an unsaturated compound (e), and a polyisocyanate vinegar (4) may be reacted without a solvent, or It is carried out by adding an organic solvent, and examples of the organic solvent include acetone, acetophenone, decyl isobutyl ketone, tetrahydrofuran, di Yao, dimethyl ketoamine, dimethyl sapite, N_. Methylpyrrolidone, N-ethylpyrrolidone, ethyl acetate, etc. Among them, acetone, acetophenone, ethyl acetate polyamino phthalate prepolymer can be removed by heat and pressure after dispersion and chain elongation reaction in water. Further, it is good. Further, mercaptopyrrole _, N-ethyl hydrazine _ from the obtained aqueous polyamino phthalic acid vinegar resin dispersion to form a coating film to play the role of a filming aid, so it is good. The amount added is relative to the polycarbonate polyol (a), the acidic group-containing plurality 323441 29 201217408 alcohol (b), and optionally the other polyol (c), and the unsaturated compound (e). On a weight basis, it should be 〇 to 2.0 times, more preferably 0.1 to 0.7 times. 'When the viscosity to the polyurethane prepolymer (A1) is in an appropriate range, a good dispersion can be obtained. In addition, the time required to remove the organic solvent does not need to be too long to use the aqueous polyaminophthalate. The resin is an organic solvent remaining in the coating film obtained by the polity, and the physical properties of the coating film can be easily prevented from being lowered. In the present invention, the 'polyurethane resin (A) or the urethane prepolymer (A1) The acid value is preferably from 2 〇 to 5 〇 mg K 〇 H / y. For this range, it is easy to ensure dispersibility in a good aqueous medium and the water resistance of the coating film is preferably from 25 to 45 mg KOH / g. More preferably, it is 30 to 40 mgKOH/g. Here, the acid value of the polyurethane resin (A) or the polyaminophthalate prepolymer (A1) is when manufacturing a polyurethane resin or a polyamino group. The formate prepolymer (A1) is an acid group in which the solvent to be used and the polyamethylene &amp; ruthenium prepolymer (A1) are dispersed in the so-called solid component of the towel and the agent of the aqueous medium towel. Average content, from polycarbonate polyol (a), polyol containing acid group (b), depending on the situation The alcohol (c), the unsaturated compound (e), and the polyisocyanate, the weight of the (d), and the acidic group contained in the acidic group-containing polyol (b) can be determined according to the following formula (3). And derived. [Polyuric acid value of polyurethane resin (A) or polyurethane prepolymer (A1)] = [molar number of acidic group of polyol (b) containing acid group] χ 56.11 / [Polycarbonate polyol (a), polyol containing acid group (b), 323441 30 201217408 In other cases, the total of other polyol (C), unsaturated compound (e) and polyisocyanate (d) Weight] (3), after obtaining the polyurethane urethane prepolymer (A1), the dispersion of the aqueous solvent and the chain extension agent (C) are extended to obtain the aqueous polyurethane resin dispersion of the present invention. In the meantime, the aforementioned acid value is synonymous with the acid value of the polyurethane prepolymer (A1). When the polyurethane resin (4) or the polyurethane prepolymer (A1) is obtained, the solid content of the aqueous polyurethane resin dispersion (including the compound (B) having a polymerizable unsaturated bond) is completely When it is a part by weight, the polycarbonate polyol (a) is preferably 2 to 50 parts by weight, the acid is contained, and the polyol (b) is preferably 2 to 15 parts by weight, and the other polyol (4) is preferably 〇 to 30 parts by weight. The unsaturated compound (e) is preferably 5 to 5 parts by weight. When the polycarbonate polyol (a) is in the above range, the coating film obtained from the aqueous polyurethane resin dispersion has high adhesion, and X, the polyaminophthalic acid resin (A) is dispersed in the aqueous medium. Good in properties, can accommodate two excellent film forming properties. The polycarbonate polyol (a) is preferably from 3 to 40 parts by weight, particularly preferably from 5 to 30 parts by weight. The acid group-containing polyol (1) is excellent in water resistance of the coating film obtained from the aqueous polyaminoglycol resin dispersion in the above-described range, and the polyurethane lysate (a) has good readability in an aqueous medium. The polyol (1) having an acidic group is preferably from 3 to 10% by weight, particularly preferably from 4 to 7 parts by weight. When the unsaturated compound (e) is the above-mentioned &amp;, the coating film obtained from the aqueous urethane resin dispersion is excellent in the hardness of the 'aqueous base polyurethane resin dispersion' Stability is also excellent. The unsaturated compound (e) is preferably from 1 Torr to 4 〇 323441 31 201217408 parts by weight. VIII. Chain extender (ς;) (4) Polymeric unsaturated bond (IV) Urethane vinegar resin The lyophilized straw is a dry coating film before irradiation with an active energy ray (for example, a purple bud line) using a chain extender (C). It is rarely sticky and becomes non-sticky, so it should be prepared with chain extender (c). Chain extender (6) can be ethylenediamine, hydrazine-tetramethyldiamine, 2-methyldeca-pentanediamine, Μ_丁二丄1-'6, methylene-monoamine, hexamethylenediamine Amine, 3-aminoindenyl 3,5 5_^methylcyclohexylamine, U, (aminomethyl) cyclohexane, dimethyl strepamine, hydrogen ratio, well, 2,5-didecyl Amination of hexahydro 0 to hydrazine, hydrazine, hexanediethylenetriamine, triethylenetetramine, etc.: diolation of ethyl alcohol, propylene glycol, propylene glycol, cesium butanediol, 1,6 hexanediol, etc. a polyethylene glycol or water represented by polyethylene glycol, water, etc., wherein the chain extender (C) is a point of hardness of the coating film after curing of the active energy ray (for example, ultraviolet ray) of the obtained coating film. It is preferably an organic compound, more preferably a polyaminated &amp; These may be used alone or in combination. The amount of the bond extender (C) to be added is preferably less than the equivalent of the isocyanato group of the chain extension starting point in the polyaminophthalic acid vinegar prepolymer (Α1), more preferably 0.7 to 0.99 equivalents of the isocyanate group. In this range, the molecular weight of the chain-extended polyurethane resin is appropriately set, and even the coating film obtained by coating the aqueous polyurethane resin dispersion containing the particles has a good strength. The chain extender (c) may be added after the polyaminophthalate prepolymer (Α1) is dispersed in water, or may be added to the dispersion. Chain extension can also be carried out by water 323441 32 201217408. At this time, the water as a dispersion medium also has a chain extender. <Compound (B) having a polymerizable unsaturated bond> The compound (B) having a polymerizable unsaturated bond in the present invention is preferably in the coexistence of a photoradical generating agent or in the presence of a thermal radical generating agent. The polymerization is carried out, but it is preferred to use a compound which does not react with the isocyanate group at 25 °C. The compound (B) having a polymerizable unsaturated bond may, for example, be a compound having an ethylenically unsaturated bond such as a vinyl group or an allyl group, and examples thereof include a compound having a (fluorenyl) acrylonitrile group. The compound (B) having a polymerizable unsaturated bond may be a monofunctional compound having one group containing a polymerizable unsaturated bond such as a (fluorenyl) acrylonitrile group, or may have a plurality of polyfunctional groups. As the compound, a compound having three or more (fluorenyl) acrylonitrile groups or a compound having five or more (fluorenyl) propylene groups can also be suitably used. The compound (B) having a polymerizable unsaturated bond is preferably a (fluorenyl) acrylate compound. The (fluorenyl) acrylate compound may, for example, be a monomeric (fluorenyl) acrylate compound, a polyaminophthalate (meth) acrylate compound, a polyester (fluorenyl) acrylate compound, or a poly( A mercapto) alkyl acrylate compound or the like. As the monomeric (fluorenyl) acrylate compound, mono(indenyl)acrylate or di(indenyl)acrylate, tris(decyl)acrylate, tetrakis(yl)acrylate, and ruthenium can be used. a mono (meth) acrylate or poly (meth) acrylate such as acrylate or hexakisyl acrylate. The aforementioned mono(indenyl) acrylate may, for example, be 2-ethylhexyl (mercapto) acrylate, decyl (meth) acrylate, tetrahydrofuranmethyl (decyl) acrylate 33 323441 201217408 ester, dodeca ( Methyl) acrylate, cyclohexyl (decyl) acrylate, dicyclopentenyl (mercapto) acrylate, 2-ethylhexyl (meth) acrylate, dicyclopentenyloxyethyl (methyl) Acrylate, phenoxyethyl (fluorenyl) acrylate, isobornyl (meth) acrylate, and the like. Examples of the di(indenyl) acrylate include ethylene glycol di(meth)acrylate, propylene glycol di(decyl)acrylate, neopentyl glycol di(decyl)acrylate, and 1,4-butanediol. Dialkyl (meth) acrylate, 16-hexanediol bis(indenyl) acrylate, tricyclodecane dinonyl di(meth) acrylate, bisphenol A di(meth) acrylate, etc. Diol bis(mercapto) acrylate; polyether bis(indenyl) acrylate such as polyethylene glycol di(meth)acrylate or polypropylene glycol di(meth)acrylate; bisphenol A ethylene oxide Modified di(meth)acrylate, bisphenol A propylene oxide modified di(meth)acrylate, neopentyl glycol epoxy bake modified di(meth)acrylate, neopentyl glycol epoxy An alkylene oxide-modified di(indenyl)acrylate such as propane-modified di(meth)acrylic acid vinegar; 1&gt;6_&amp;diol epoxy bis(indenyl)acrylate, neopentyl glycol epoxy Alkyl bis(indenyl)acrylic acid bismuth A oxy-(meth)propionic acid vinegar, double bismuth A epoxide-modified epoxy bis(indenyl) acrylate Epoxy bis(indenyl) such as decanoic acid bis(indenyl) acrylate, polyethylene glycol epoxy bis(indenyl) acrylate, polypropylene glycol epoxy di(meth) acrylate ) Acrylate and the like. The bis(indenyl) acrylate may, for example, be trihydroxymercaptopropane tris(indenyl) acrylate, ethylene oxide-modified trimethylpropane tris(decyl) acrylate, or propylene oxide-modified trishydroxyl Methylpropane tri(meth)acrylate, neopentyl alcohol di(meth)acrylic acid g, and the like. Examples of the tetra (meth) acrylate include dipentaerythritol tetrakis(methyl)propyl 34 323441 201217408 enoate, pentaerythritol tetrakis(meth) acrylate, ethylene oxide (4 mol). Modified alkylene oxide tetrakis(meth)acrylic acid vinegar (Daicel Cytec, Ebecryl 40), etc., alkylene oxide-modified neopentyl alcohol tetrakis(yl) acrylate, di-trimethylolpropane tetra(fluorenyl) )Acrylate. The penta (indenyl) acrylate is, for example, dipentaerythritol penta(indenyl) propyl citrate. The hexa (indenyl) acrylate type may, for example, be dipentaerythritol hexa(indenyl) acrylate S or the like. Among these monomeric (meth) acrylate compounds, from the point of hardness, it is preferably bis(indenyl) acrylate, tris(decyl) acrylate, tetrakis(yl) acrylate, and five (a) Poly(meth) acrylate of acrylate, hexakis(meth)acrylate. These are due to the fact that there are a plurality of (fluorenyl) propylene fluorenyl groups in the inner phase, which is more easily polymerized than those of the single (meth) acrylate. Among them, from the point of hardness, it is preferably tris(meth)acrylate, tetrakis(meth)acrylate, penta(meth)acrylate, or hexa(meth)acrylate. More preferably, it is a penta (meth) acrylate or a hexa(mercapto) acrylate. The (meth) acrylate of the polymer type may be a urethane (mercapto) acrylate compound or a polyester (mercapto group) in addition to a (mercapto) acrylate having a polyalkylene glycol structure. For example, an acrylate-based compound or a polyalkylene (meth) acrylate-based compound can be used for an acrylic polymer having a polymerizable unsaturated bond in the molecule, and examples thereof include a polymerizable double bond at the end of the molecular sheet. Polybutyl acrylate ("Actflow BGV-100T" manufactured by Soken Chemical Co., Ltd.) or polybutyl acrylate ("Actflow" manufactured by Soken Chemical Co., Ltd.) having a polymerizable double bond at both ends of the molecule. 35 323441 201217408 Compounds having a polymerizable unsaturated bond (8) may also be a compound containing a vinyl group or a propyl group other than an acrylic acid acetonitrile compound, such as acrylonitrile, phenethyl hydrazine or N-vinyl group. . The compound (Β) having a polymerizable unsaturated bond can be used as it is. The compound (8) having a polymerizable unsaturated bond may be used singly or in combination of plural kinds. When the total amount of the solid content of the aqueous polyurethane resin dispersion (comprising a compound having a polymerizable unsaturated bond (Β)) is 1 part by weight, preferably 2 to 50 parts by weight, more preferably 5 Up to 40 parts by weight. The compound (B) having a polymerizable unsaturated bond is preferably 1 Torr to 100 parts by weight of the total amount of the aqueous polyaminophthalate resin dispersion (containing the polyurethane resin (A)). 6 parts by weight. If it is in this range, the adhesion and hardness of the coating film obtained from the aqueous polycyano phthalate resin dispersion can be improved, and the neo-amino resin dispersion can be excellent (4). The polymer (8) having a polymerizable unsaturated bond is more preferably 20 to 50 parts by weight, most preferably 3 to 7 weights. Polyurethane resin dispersion> X·aqueous medium medium: Ben = 2: sulfhydryl group _ The resin (A) is dispersed in a water-based mixed medium or the like, and water such as water or a water-based organic solvent may, for example, be tap water. Among them, if the test water, distilled water, ultrapure water test I get the material or _ affect the recording of the uneasiness of the record 323441 36 201217408 疋 special 'is suitable for ion exchange water. Hydrophilic organic solvent can be exemplified as a grade-alcohol; ethylene glycol, glycerol, etc., such as diethanol, propanol, etc., such as 尤, Ν-methylmorpholine, dimethylformite, and samarium Amine, ν·methyl% ς Aqueous organic solvent, etc. The amount of the non-buy method in the aqueous medium is 0 to 20% by weight. The amount of the hydrophilic organic solvent in the first substance is preferably XI. A method for producing an aqueous polyurethane lysate dispersion - a method for producing a human aqueous polyurethane resin dispersion. The aqueous polyurethane of the present invention is intended to be at least a polycarbonate having a alicyclic structure from the main diol (a), an acid group-containing polyol (b), a polyisocyanate (4), The thiol molecule has one or more groups reactive with an isocyanate group and reacts with the compound (e) having one or more polymerizable unsaturated bonds to obtain a polyurethane resin (A) to give a polyurethane. The resin (A) and the compound (B) having a polymerizable unsaturated bond are dispersed in an aqueous medium. The method for producing an aqueous polyurethane resin dispersion of the present invention comprises the steps of: a polycarbonate polyol (a), an acid group-containing polyol, a polyisocyanate (d), and One or more steps of reacting a group reactive with an isocyanate group with a compound having one or more polymerizable unsaturated bonds to obtain a polyurethane urethane prepolymer (A1) (αι), neutralizing a polyglycolic acid g Step of the acidic group of the prepolymer (Α1) {β)' 37 323441 201217408 Step of dispersing the polyurethane (tetra) prepolymer (A1) and the compound (B) having a polymerizable unsaturated bond in an aqueous medium (γ) A polyurethane polyurethane prepolymer (Α1), a key extender (c) reactive with an isocyanate group of a polyurethane urethane prepolymer (Α1) to obtain an aqueous polyurethane resin Steps ($). Further, the method comprises the steps of: a polycarbonate polyol (a), an acid group-containing polyol (1), another polyol (c), a polyvalent isocyanate (4), and a group having i or more reactive groups with an isocyanate group. Step 2) of reacting the compound (e) having more than one polymerizable unsaturated bond to obtain a polyamino-f-acid prepolymer (ai), and neutralizing the acidic group of the polyurethane prepolymer (A1) Step (β), a step (γ) of dispersing a polyurethane prepolymer (Α1) and a compound having a polymerizable unsaturated bond (Β) in an aqueous medium, and a polyurethane prepolymer (Α1) A step of reacting a key extender (c) reactive with an isocyanate group of a polyurethane urethane prepolymer (Α1) to obtain an aqueous polyurethane resin. The steps (α i) and (α 2) for obtaining the polyamino phthalic acid g prepolymer (?1) are preferably carried out in the presence of oxygen in order to avoid unnecessary consumption of the polymerizable unsaturated bond. Further, it is preferred to add a polymerization inhibitor to the reaction system as needed. The step of obtaining the polyaminophthalic acid vinegar prepolymer (Α1) (the temperature of α ^ and (α2) is to avoid unnecessary polymerization of the polymerizable unsaturated bond, and can be carried out at 〇 to 12 ° C. More preferably It is carried out at 100 ° C. 323441 38 201217408 An acidic base neutralizing agent which can be used in the step of neutralizing the acidic group of the polyurethane prepolymer (A1), for example, tridecylamine , triethylamine, triisopropylamine, tributylamine, triethanolamine, N-decyldiethanolamine, N-phenyldiethanolamine, dimethylethanolamine, diethylethanolamine, N-mercaptoline, ° An organic amine such as a bite; an inorganic test such as sodium hydroxide or potassium hydroxide; ammonia, etc., preferably an organic amine, more preferably a tertiary amine, preferably a triethylamine. Here, a polyamino group The acidic group of the phthalate prepolymer (A1) refers to a tick acid group, a reductive acid group, etc. The acid group neutralizing agent is used in an amount relative to the acidic group of the polyaminophthalate prepolymer (A1). The number of ears is preferably from 0.8 to 1.5. If the range of the 'polyurethane prepolymer (A1) is sufficiently dispersed in water, the obtained aqueous polyaminoguanidine The storage stability of the ester resin dispersion is not lowered, and the odor of the so-called aqueous polyurethane resin dispersion can be easily prevented. In the polyurethane prepolymer (A1) and The compound (B) having a polymerizable unsaturated bond is dispersed in the aqueous medium (γ), and the system can be dispersed in the aqueous medium. The method and operation are not particularly limited, but for example, Ai) mixing (B)

Hit方法、或於(B)混合(A1)而分散於水 系&quot;質中之方法、或使（A1)分散於水系介質中 分散⑻之方法、錢⑻分散於㈣㈣中之後齡 分散（A1)之方法、或使（A1)盘 介質中之後混合的方法等。 ”別刀散於水系 於前述之混合或搜拌、分散中係可使用均混機或均質 323441 39 201217408 機等公知的攪拌裝置。又，於聚氨基甲酸酯預聚物（Al) 或具有聚合性不飽和鍵之化合物（B)中，為了黏度調整 或作業性提昇、分散性提昇，於混合前亦可預先加入親水 性有機溶劑或水等。 混合聚氨基甲酸酯預聚物（A1)與具有聚合性不飽和 鍵之化&amp;物（B )之步驟（r )係為避免聚合性不飽和鍵 之不必要的㈣，宜在氧存在下進行。又，可依需要而添 加阻聚劑。混合聚氨基甲酸酯預聚物（A1)與具有聚合性 不飽和鍵之化合物⑻之時的溫度係為避免聚合性不飽 和鍵之不必要的聚合，可在〇至1〇(rc下進行，更宜在〇 至80t下進行，最宜在〇至7〇t下進行，尤宜在5〇至7〇 °C下進行。 在本發明之製造方法中’中和聚氨基甲酸§旨預聚物 (A◦之酸性基的步驟⑷、與使聚氨基甲㈣預聚物 (A1)與具有聚合性不飽和鍵之化合物 介質中之步驟…，任-者均可先進行，亦可同= 此時，亦可使Ui)與⑻與水系介質與酸性基中和劑 -次混合，亦可使酸性基中和劑預先混合於水系介質或 (B)中’亦可將此等與（A1)混合。 使聚氨基甲酸醋預聚物（A1)與具有聚合性不飽和鍵 之化合物（B)分散於水系介質中之步驟（仆使 甲酸醋預聚物UO與鏈延長劑（c)反應而得到水性^ 氨基甲酸醋樹脂的步驟（(5)亦可同時進行 (A1)、(C)、(B)與水系介質-:欠混合，亦可將(C』 323441 40 201217408 先與水系介質混合，再將此等與（A1)或(B)混合。 中和聚氨基曱酸酯預聚物（A1 )之酸性基的步驟 (万）、使聚氨基曱酸酯預聚物（A1)與具有聚合性不飽 和鍵之化合物（B )分散於水系介質中之步驟（^ )、使聚 氨基甲酸酯預聚物（Α1)與鏈延長劑（C)反應而得到水 性聚氣基曱酸醋樹脂的步驟（（5 )亦可同時進行。此時， 可使（Al )、（ C )、（ B )、酸性基中和劑與水系介質一次混 合’亦可將（C )或酸性基中和劑預先與水系介質或（b)混 合，再將此等與（A1)或(B)混合。 使聚氨基甲酸酯預聚物（A1)與鏈延長劑（C)反應 而得到水性聚氨基曱酸酯樹脂的步驟（（5 )中，反應可在 冷卻下徐緩地進行，又，依情況，亦可在60°C以下之加熱 條件下促進反應。冷卻下之反應時間可為0.5至24小時左 右，在60°C以下之加熱條件下的反應時間可為0.1至6小 時左右。 使水性聚氨基曱酸酯樹脂分散體之固形分（包含具有 聚合性不飽和鍵之化合物（B))的全量作為100重量份時， 聚氨基曱酸酯樹脂(A)宜為5至60重量份，更宜為15至 50重量份，最宜為25至40重量份。聚氨基甲酸酯樹脂(A) 之數目平均分子量宜為1000至1000000。從光硬化前之乾 燥塗膜的無沾黏性之觀點，更宜為10000至1000000。 XII.光聚合起始劑 本發明之水性聚氨基曱酸酯樹脂分散體亦可添加光 聚合起始劑。光聚合起始劑係無特別限定，可使用公知者。 41 323441 201217408 具體上，藉由活性能量線（例如紫外線）照射，容易裂開 而形成2個自由基之光㈣型或去氫型之光聚合起始劑。 亦可併用此等。 如此之光聚合起始劑係可舉例如乙醯苯、2,2_二乙氧 基乙醯本、對二甲基胺基乙酿笨、二苯基酮、氯二苯甲 _、P，P，_雙二乙基胺基二苯基酮、苯偶因乙基鱗、苯偶因 正丙基趟、苯偶因異丙基喊、苯偶因異丁基喊、苯偶因正 丁基醚、苯偶因二甲基縮酮、硫雜蒽酮、對異丙基-α-羥 ，異丁基紛、2,2·二甲氧基_2_笨基乙醯苯、i•經基環己基 苯基酮' 2m [ 4·(甲硫基）苯基]_2·嗎琳基丙烧-卜 酮、2-沒基-2-曱基-1-苯基丙燒]酮、2,4,6_三甲基二苯基 綱4-甲基一苯基酮、2,2_二甲氧基二苯基乙啊等。其 中，宜為羥基環己基苯基酮。 添加光聚合起始劑時，宜在使聚氨基甲酸酯預聚物 (A1)與鏈延長劑（c)反應而得到水性聚氨基甲酸酯樹 月曰（A)之步驟（6)後添加。光聚合起始劑之添加量相對於水 性聚氨基甲酸賴脂分散體之固形分（包含具有聚合性不 飽和鍵之化合物（B))宜為〇 5至5重量份。 ΧΠΙ.添加劑 又，於本發明之水性聚氨基甲酸酯樹脂分散體中依需 要而亦可添加增黏劑、光增敏劑、硬化觸媒、紫外線吸收 劑、光安定劑、消泡劑、塑化劑、表面調整劑、防沉降劑 等之添加劑。添加劑係可單獨使用，亦可併用複數種。本 發明之水性聚氨基甲酸酯樹脂分散體從所得到之塗膜的硬 42 323441 201217408 度、对藥品性而言，實質上，宜不含有保護膠體、乳化劑、 界面活性劑。 〈塗料組成物及塗佈劑組成物〉 本發明亦有關含有前述水性聚氨基甲酸酯樹脂分散 體之塗料組成物及塗佈劑組成物。 本發明之塗料組成物及塗佈劑組成物除了前述水性 t氣基曱酸自旨樹脂分散體以外，亦可添加其他之樹脂。其 他之樹脂，係可舉例如聚酯樹脂、丙烯酸樹脂、聚醚樹脂、 聚碳酸酯樹脂、聚氨基甲酸酯樹脂、環氧樹脂、醇酸樹脂、 聚烯烴樹脂等。此等係可單獨使用，亦可併用複數種。 其他之樹脂宜為具有1個以上之親水性基。親水性基 係可舉例如羥基、羧基、磺酸基、聚乙二醇基等。 其他之樹脂宜為由聚酯樹脂、丙稀酸樹脂、聚婦烴樹 脂所構成之群中選出的至少一種。 聚酯樹脂一般係可藉由酸成分與醇成分之酯化反應 或酯交換反應而製造。酸成分係可使用聚酯樹脂的製造時 一般使用來作為酸成分之化合物。酸成分係可使用例如脂 肪族多元酸、脂環族多元酸、芳香族多元酸等。 聚酯樹脂之羥基宜為10至300mgKOH/g左右，更宜 為50至250mgKOH/g左右，最宜為80至180mgKOH/g左 右。聚酯樹脂之酸價宜為1至200mgKOH/g左右，更宜為 15 至 l〇〇mgKOH/g ’ 最宜為 25 至 60mgKOH/g 左右。 聚酯樹脂之重量平均分子量宜為500至500000,更宜 為 1000 至 300000，最宜為 1500 至 200000。 43 323441 201217408 丙烯酸樹脂宜為含有羥基之丙烯酸樹脂。含有羥基之 丙烯酸樹脂係可使含羥基之聚合性不飽和單體及可與該含 有羥基之聚合性不飽和單體共聚合之其他的聚合性不飽和 單體藉由例如在有機溶劑中之溶液聚合法、在水中之乳液 聚合法等已知的方法而共聚合來製造。 含有羥基之聚合性不飽和單體係1分子中分別具有經 基及聚合性不飽和鍵1個以上之化合物。可舉例如2_經乙 基（曱基）丙烯酸酯、2-羥丙基（甲基）丙烯酸酯、3-羥丙基（甲 基）丙稀酸S旨、4-經丁基（曱基）丙烯酸g旨等之（甲基）丙埽 酸與碳數2至8的二元醇之單酯化物；此等之單酯化物的 ε -己内酯改性體；N-羥甲基（甲基）丙烯醯胺；烯丙基醇； 分子末端為經基之具有聚氧乙稀鏈之（曱基）丙稀酸酯等。 含有羥基之丙烯酸樹脂宜為具有陰離子性官能基。具 有陰離子性官能基之含有羥基之丙稀酸樹脂係可藉由使用 羧酸、磺酸基、磷酸基等具有陰離子性官能基的聚合性不 飽和單體作為聚合性不飽和單體的1種來製造。 含有羥基之丙烯酸樹脂之經基價係從水性聚氨基曱 酸醋樹脂分散體之貯存安定性或所得到之塗膜的耐水性等 之觀點’宜為1至200mg KOH/g左右，更宜為2至i〇〇mg KOH/g左右，最宜為3至60mg KOH/g左右。 含有羥基之丙烯酸樹脂具有羧基等之酸性基時，含有 羥基之丙烯酸樹脂之酸價從所得到之塗膜的耐水性等之觀 點，宜為1至200mg KOH/g左右’更宜為2至150mg KOH/g 左右，最宜為5至100mg KOH/g左右。 323441 44 201217408 含有羥基之丙烯酸樹脂之重量平均分子量宜為1〇〇〇 至200000，更宜為2000至100000，最宜為3000至5〇〇〇〇 的範圍内° 聚醚樹脂係可舉例如具有醚鍵之聚合物或共聚物，可 舉例如聚氧乙烯系聚醚、聚氧丙烯系聚鱒、聚氧丁烯系聚 醚、雙酚A或雙酚F等之芳香族聚羥基化合物所衍生的聚 醚等。 聚碳酸酯樹脂係可舉例如從雙酚化合物所製造之聚 合物，可舉例如雙盼A·聚碳酸酯等。 聚氨基曱酸酯樹脂係可舉例如具有藉由丙烯酸、聚 酉旨、聚鍵、聚碳㈣等之各種多元醇成分與多元異氮酸醋 之反應所付到的聚氣基曱酸@旨鍵之樹脂。 環氧樹脂係可舉例如藉由雙盼化合物與表氣醇之反 應所得到之樹脂等。雙酚可舉例如雙酚A、雙酚F。 醇酸樹脂係可舉例如於敵g楚、對駄酸、號轴酸等之多 元酸與多元醇進-步使油脂、油脂脂騎（大豆油、亞麻 仁油、椰子油、硬脂酸等）、天然樹脂（松香、琥珀等）等 之改性劑反應而得到的醇酸樹脂。 ' 聚烯烴樹脂係可舉例如藉由使烯烴系單體斑適當豆 他之單體依-般的聚合法而聚合或共聚合所得到之聚婦烴 樹脂’使用乳化劑而進行水分散，或藉由使_系單體與 適當其他之單體-起乳化聚合所得到之樹脂。又，視情況， 亦可使用前述㈣烴樹祕氯化之所錢化㈣煙改性樹 脂0 323441 45 201217408 烯烴系單體可舉例如乙烯、丙烯、^丁烯、％曱基-卜 丁稀4_曱基小戊稀、3-曱基-1-戊烯、1-庚稀、己烯、 1-癸烯、；U十二碳烯等之烯烴；丁二烯、亞乙基降冰片 烯、二環戊二烯、丨，5_己二烯、苯乙烯類等之共軛二烯或 非共扼二烯等’此等之單體係可單獨使用，亦可併用複數 種。 ^可與烯烴系單體共聚合之其他的單體，係可舉例如醋 酸乙稀S旨、乙稀醇、馬來酸、檸康酸、衣康酸、馬來酸針、 摔康酸酐、衣康酸肝等，此等之單體係可單獨使用，亦可 併用複數種。 本發明之塗料組成物及塗佈劑組成物中可藉由含有 硬化劑而提昇❹塗料組成物或塗佈劑組成物之塗膜或複 層塗膜、塗佈膜之耐水性等。 一硬化劑係可使用胺基樹脂、多元異氰酸酯、封端化多 元異氰酸酯、三聚氰胺樹脂、碳二亞胺等。硬化劑係可單 獨使用，亦可併用複數種。 1胺基樹脂係可舉例如藉由胺基成分與酸成分之反應 所得到的部分或完全㈣基化絲_。絲成分係可舉 例如三聚氰胺、尿素、苯並脈胺、2,4_二胺基_6_甲基-Us 三哪、固醇胍胺、螺胍胺、二氰二醯胺等。路成分可舉 例如F醛.、多聚甲醛、乙醛、苯甲醛等。 多元異氰酸酯係可舉例如i分子中具有2個以上之異 氰酸基的化合物，可舉例如六亞子基二異氰酸醋、三子基 六亞甲基二異氰酸酯等。 323441 46 201217408 封端化多7G異氰酸g旨係可舉例如於前述之多元異氮 酉文®曰的夕元異氰I基加成封端劑而得到者，封端化劑可舉 例如酚、曱酚等之酚系、甲醇、乙醇等之脂肪族醇系、丙 二酸二曱i旨、乙醯基_等之活性亞甲基系、丁基硫醇、 十-奴基硫醇等之硫醇系、乙醯基苯胺、醋醯胺等之酿胺 系ε己内醯胺、占_戊内醯胺等之内醯胺系、琥拍醢亞 胺、馬來醯亞胺等之隨亞胺系、乙㈣、丙眶、甲基乙 基嗣辟等之㈣、_笨基笨胺、苯胺、次乙亞胺等之胺系 等的封端化劑。 一三聚氰胺樹脂係可舉例如二經甲基三聚氰胺、三經甲 基-聚氰胺等之赵甲基三聚氰胺；此等之經甲基三聚氮胺 的院基醚化物或縮合物；經甲基三聚氰胺祕細化物的 縮合物等。 本發明之塗料組成物及塗佈劑組成物中係可添加著 色顏^或體質顏料、光輝性顏料。 士誃著色顏料可舉例如氧化鈦、鋅白、碳黑、鉬紅、普魯 |鈷藍、偶氮顏料、酞菁顏料、喹吖啶顏料、異吲哚 啉顏料、士林(Threne)顏料、茈顏料等。此等係可單獨使 亦可併用複數種。就著色顏料尤宜使用氧化鈦及/或碳 黑。 體質顧料可舉例如黏土、高嶺土、硫酸鋇、碳酸鋇、 碳酸Μ、、、a /月石、二氧化矽、氧化鋁白等。此等係可單獨使 亦可併用複數種。就體質顏料而言宜使用硫酸鎖及/ 或'月石’更宜使用硫酸鋇。 323441 47 201217408 顏料係可使用·&amp;、銅、鋅、黃鄉 L:雲母'經氣化欽或氧化鐵被覆之氧化銘、經 虱化鈦或氧化鐵被覆之雲母等。 可人料組成物及塗佈劑組成物中係依需要而 :曰’〜、硬化觸媒、紫外線吸收劑、光安定劑、消 加劑。此4係可單獨使用，亦可併用複數種。 本發明之塗料組成物及塗佈劑組成物之製造方法係 無特別限制，但可使用公知的製造方法。—般塗料組成物 及塗佈劑組成物係混合前述水性聚氨基甲酸賴脂分散體 與上述之各種添加劑’添加水系介質，調整成適應塗農方 法之黏度來製造。 塗料組成物之被塗裝材質或塗佈劑組成物之被塗佈 材質可舉例如金屬、塑膠、無機物、木材等。 塗料組成物之塗裝方法或塗佈劑組成物之塗佈方法 可舉例如鐘罩式(bell type)塗装、喷塗塗裝、輥輪塗裝、噴 灑塗裝、浸潰塗裝等。 本發明之水性聚氨基甲酸酯樹脂分散體、水性聚氨基 曱酸酯樹脂分散體組成物、塗料組成物、塗佈劑組成物係 宜於所希望之基材上塗佈或塗裝或塗覆後，在加熱下或非 加熱下’使水性介質的至少一部分蒸發後，照射活性能量 線以硬化。活性能量線係可舉例如電子東、紫外線或r線 之電離性放射線，其中宜為紫外線。 紫外線之光源若為發出紫外線區域之光的光源，即無 48 323441 201217408 特别限疋可使用例如&amp;燈、低壓水銀燈、高壓水銀燈、 超同壓水銀燈、金屬_素燈、碳弧燈、纟I絲燈等。照射時 間係依具有聚合性不飽和鍵之化合物的種類、光聚合起始 劑之種類、覆獏厚度、紫外線料之條件，可適宜變動。 從作業性之點’宜照射U60秒。進—步就完成硬化反應 之目的可在紫外線照射後進行加熱處理。 使本發明之水性聚氨基甲酸酯樹脂分散體、塗料組成 物、塗佈劑组成物等硬化時使用之紫外線的照射量從速硬 化性、作業性之觀點，宜為300至3000mJ/cm2。 為了硬化’除紫外線外，亦可使用電子束等《以電子 束硬化時’可不添加光聚合起始劑，宜為使用具有1〇〇至 500eV之此1的電子束加速裝置。 [實施例] 其次，舉出實施例及比較例而更詳細地說明本發明。 [實施例1 ] 以具備攪拌機及加熱器之反應裝置，使ETERNACOLL (註冊商標）UM 90 (3/1)(宇部興產製；數目平均分子 量916;羥基價i22mgKOH/g;多元醇成分為1,4-環己烷 二甲醇：1，6-己二醇=3 : 1之莫耳比的多元醇混合物與碳 酸酯反應所得到之聚碳酸酯二醇、脂環構造含有率39重量 0/〇、25.9呂）、2,2-二羥曱基丙酸（〇1\«&gt;八、11.1层）與異佛爾 酮二異氰酸酯（IPDI、57.5g)，在N-乙基吡咯烷酮（43.9g) 中，於二月桂酸二丁基錫（〇.lg)存在下，氮環境下，以 80至90°C加熱2.5小時。加入2,6-二第彡丁基-4-曱基酚 49 323441 201217408 (0.2g)與4-甲氧基紛（〇.2g) ’使環境成為空氣。進一步’ 置入2分子之丙烯酸與1分子之丨，6_己二醇二縮水甘油醚 之反應生成物（1，6-HDL-EP-A、i2.6g)、新戊四醇三丙烯 酸酯（PETA、19.7g)，以90〇C加熱6小時。氨基曱酸酯化 反應終止時之NCO基含量為4.01重量。/。。使反應混合物 冷卻至70 C，於此再添加混合二新戊四醇六丙稀酸醋 (DPHA、79.9g)、三乙胺（8.9g)。使反應混合物（226g) 於強烈攪拌下加入水（386g)中。然後，加入35重量％之 2-甲基-1，5-戊二胺水溶液（MPMD、2〇 lg)，得到水性聚 氨基甲酸酯樹脂分散體。 [實施例2] 以具備攪拌機及加熱器之反應裝置，使ETERNAC〇LL (δ主冊商標）UM 9〇 (3/1)(宇部興產製；數目平均分子 篁916，羥基價122 mgK〇H/g ;多元醇成分為込4環己烷 二甲醇：1，6-己二醇=3 : 1之莫耳比的多元醇混合物與碳 酸酯反應所得到之聚碳酸酯二醇、脂環構造含有率39重量 /〇、40.3g)、2,2_二羥曱基丙酸（DMpA、97g)與異佛爾 嗣二異氰酸自旨（IPDI、46.3g)，在N_乙基吡咯烷銅（4〇.5g) 中，於一月桂酸二丁基錫（O.lg)存在下，氮環境下，以 80至90 C加熱2.5小時。加入2,6_二第三丁基-4-曱基酚 (0.2g)與4_甲氧基酚（〇.2g)，使環境成為空氣。進一步， 置入新戊四醇三丙烯酸酯（PETA、16.1g)，以90。(：加熱5 小時。氨基甲酸酯化反應終止時之NC〇基含量為3 51重 量/〇使反應混合物冷卻至70¾，於此再添加混合三羥曱 323441 50 201217408 基丙烧三丙埽酸酯（TMPTA、72.5g)、三乙胺（7.8g)。使 反應混合物（2i〇g)於強烈攪拌下加入水（ 353g)中。然 後，加入35重量％之2-曱基-1，5-戊二胺水溶液（MPMD、 15.8g )’得到水性聚氨基曱酸酯樹脂分散體。 [實施例3] 以具備攪拌機及加熱器之反應裝置，使ETERNACOLL (註冊商標）UM 90 (3/1)(宇部興產製；數目平均分子 量916 ;羥基價122 mgKOH/g ;多元醇成分為1，4-環己烷 二曱醇：丨，6-已二醇=3: 1之莫耳比的多元醇混合物與碳 酸醋反應所得到之聚碳酸酯二醇、脂環構造含有率39重量 %、56‘lg)、2,2_二經甲基丙酸（DMPA、23.5g)與異佛爾 酮二異氰醆酯（IPDI、124g)，在队乙基吡咯烷酮（96.4g) 中，於二月桂酸二丁基錫（〇 2g)存在下，氮環境下，以 80至90〇C加熱3小時。加入2,6-二第三丁基-4-甲基酚 (0.5g)與4-甲氧基酚（〇.5g)’使環境成為空氣。進一步， 置入2分子之丙烯酸與1分子的丨，6·己二醇二縮水甘油醚 之反應生成物（1，6-HDL-EP-A、27.7g)、與新戊四醇三丙 烯酸酯（PETA、42.3g) ’以90°C加熱5小時。氨基曱酸S旨 化反應終止時之NCO基含量為4.05重量％。使反應混合 物冷卻至70 °C，再添加混合二新戎四醇六丙烯酸酯 (DPHA、178g)、三乙胺（19.5g)e使反應混合物（25lg) 於強烈授掉下加入水（423g)中。然後，加入％重量 二乙三胺水溶液（DETA、13.3g)，得到水性聚氨基曱酿酯 樹脂分散體。 51 323441 201217408 [實施例4] 以具備攪拌機及加熱器之反應震置，使ETERNACOLL (s主冊商標）UM 90 (3/1)(宇部興產製；數目平均分子 量916 ;羥基價122 mgKOH/g ;多元醇成分為i，4-環己烷 二甲醇：1，6-己二醇=3 ··丨之莫耳比的多元醇混合物與碳 酸酯反應所得到之聚碳酸酯二醇、脂環構造含有率39重量 %、56.1g)、2,2-二羥甲基丙酸（D]y[pA、23_5g)與異佛爾 酮二異氰酸酯（IPDI、124g)，在乙基吡咯烷酮（96.4g) 中，於二月桂酸二丁基錫（0.2g)存在下，氮環境下，以 80至90 C加熱3小時。加入2,6_二第三丁基_4_曱基酚 (0.5g)與4-甲氧基酚（0.5g)’使環境成為空氣。進一步， 置入2分子之丙烯酸與丨分子的16-己二醇二縮水甘油醚 之反應生成物（1，6-HDL-EP-A、27.7g)、與新戊四醇三丙 婦酸醋（PETA、42.3g)，以9(TC加熱5小時。氨基甲酸酯 化反應終止時之NCO基含量為4 〇5重量％。使反應混合 物冷卻至70°C，於此再添加混合二新戊四醇六丙烯酸酯 (DPHA、178g)、三乙胺（19.5g)。使反應混合物（232g) 於強烈攪拌下加入水（391g)中。然後，加入35重量％之 二乙二胺水溶液（DETA、6.1g)、35重量％之2-曱基-1,5-戊二胺水溶液（MPMD、l〇.4g)，得到水性聚氨基甲酸酯 樹脂分散體。 [實施例5] 以具備攪拌機及加熱器之反應裝置，使ETERNACOLL (註冊商標）UM 90 (3/1)(宇部興產製；數目平均分子 52 323441 201217408 量916 ;羥基價122 mgKOH/g ;多元醇成分為1，4_環己燒 二甲醇；1,6-己二醇=3 : 1之莫耳比的多元醇混合物與碳 酸酯反應所得到之聚碳酸酯二醇、脂環構造含有率39重量 %、25.2g)、2,2-二羥甲基丙酸（DmpA、l〇.6g)與異佛爾 酮二異氰酸酯（IPDI、56·。）’在N-乙基吡咯烷_ (42 9g) 中，於二月桂酸二丁基錫（O.lg)存在下，氮環境下，以 80至90。(：加熱2小時。加入2,6-二第三丁基-4-甲基齡 (0.2g)與4-甲氧基酚（〇.2g)’使環境成為空氣。進—步， 置入2分子之丙烯酸與1分子的1，6-己二醇二縮水甘油喊 之反應生成物（1，6-HDL-EP-A、i2.2g)、與新戊四醇三丙 烯酸酯（PETA、19.9g)，以90°C加熱6小時。氨基甲酸醋 化反應終止時之NCO基含量為3·95重量％。使反應混合 物冷卻至70°C ’於此再添加混合三羥甲基丙烷三丙烯酸酿 (TMPTA、79.1g)、三乙胺（8.6g)。使反應混合物（ 233g) 於強烈擾拌下加入水（401 g )中。然後’加入35重量％之 2-甲基-1，5-戊二胺水溶液（MPMD、19.7g)，得到水性聚 氨基甲酸酯樹脂分散體。 [實施例6] 以具備攪拌機及加熱器之反應裝置，使ETERNACC)LL (註冊商標）UM 90 (3/1)(宇部興產製；數目平均分子 量916 ;羥基價122 mgKOH/g ;多元醇成分為1，4_環己烧 二曱醇；1,6-己二醇=3 : 1之莫耳比的多元醇混合物與碳 酸酯反應所得到之聚碳酸酯二醇、脂環構造含有率39重量 %、1218)、2,2-二羥曱基丙酸（〇]^八、29々）與異佛爾 53 323441 201217408 酮二異氰酸酯（IPDI、139g)，在N-乙基吡咯烷酮（121g) 中，於二月桂酸二丁基錫（0.2g)存在下，氮環境下，以 80至90°C加熱2小時。加入2,6-二第三丁基-4-甲基酚 (0.8g)與4-甲氧基酚（〇.8g)，使環境成為空氣。進一步， 置入新戊四醇三丙稀酸酯（PETA、46.1g)，以90°C加熱6 小時。氨基甲酸酯化反應終止時之NCO基含量為3.83重 量％。使反應混合物冷卻至70°C，於此再添加混合三經曱 基丙烧三丙稀酸醋（TMPTA、22lg)、三乙胺（24· 1 g )。使 反應混合物（201g)於強烈攪拌下加入水（ 332g)中。然 後’加入己二醯肼（AH、8.5g)，得到水性聚氨基甲酸酯 樹脂分散體。 [實施例7] 以具備攪拌機及加熱器之反應裝置，使ETERNACOLL (s主冊商標）um 90 ( 3/1 )(宇部興產製；數目平均分子 置916，羥基價122 mgK〇H/g ;多元醇成分為1&gt;4環己烷 二甲醇；1，6-己二醇=3 :丨之莫耳比的多元醇混合物與碳 酸醋反應所得到之聚礙酸酯二醇、脂環構造含有率39重量 %、121g)、2,2·二羥甲基丙酸（dmpa、29.4g)與異佛爾 酮二異氛酸酯（IPDI、139g)’在队乙基吡咯烷酮（121g) 中’於二月桂酸二丁基錫（〇.2g)存在下，氮環境下，以 80至90 c加熱2小時。.加入2,6-二第三丁基-4-甲基酚 (〇.8g)與4-甲氧基酚（〇.8g)，使環境成為空氣。進一步， 置入新戊四醇三丙烯酸酯（PETA、46.1g)，以90〇C加熱6 小時。氨基曱酸酯化反應終止時之NCO基含量為3.83重 54 323441 201217408 量％。使反應混合物冷卻至70°C，再添加混合三羥曱基丙 烷三丙烯酸酯（TMPTA、221g)、三乙胺（24.1g)。使反應 混合物（199g)於強烈攪拌下加入水（ 337g)中。然後， 加入35重量％之聯胺水溶液（4.8g)，得到水性聚氨基曱 酸酯樹脂分散體。 [實施例8 ] 以具備攪拌機及加熱器之反應裝置，使ETERNACOLL (註冊商標）UM 90 (3/1)(宇部興產製；數目平均分子 量916 ;羥基價122 mgKOH/g ;多元醇成分為1，4-環己烷 二曱醇；1，6-己二醇=3 : 1之莫耳比的多元醇混合物與碳 酸酯反應所得到之聚碳酸酯二醇、脂環構造含有率39重量 %、121§)、2,2-二羥曱基丙酸（〇]^«&gt;八、29.4§)與異佛爾 酮二異氰酸酯（IPDI、139g) ’在N-乙基批咯烷酮（121g) 中，二月桂酸二丁基錫（0.2g)存在下，氮環境下，以80 至90°C加熱2小時。加入2,6-二第三丁基-4-曱基酚（〇.8§) 與4-甲氧基酚（0.8g)，使環境成為空氣。進一步，置入新 戊四醇三丙烯酸酯（PETA、46.1g)，以9〇°C加熱6小時。 氨基曱酸酯化反應終止時之NCO基含量為3.83重量％。 使反應混合物冷卻至70°C，於此再添加品合三經曱基丙院 三丙烯酸酯（TMPTA、221g)、三乙胺（24.1g)。使反應混 合物（253g )於強烈擾拌下加入水（4i〇g )中。然後，加 入13重量％之六氫吡哄水溶液（4.8g)，得到水性聚氨基 甲酸酯樹脂分散體。 [實施例9 ] 55 323441 201217408 以具備攪拌機及加熱器之反應裝置，使ETERNACOLL (註冊商標）UM 90 (3/1)(宇部興產製；數目平均分子 量916 ;羥基價122 mgK〇H/g ;多元醇成分為1,4-環己烷 二曱醇；1，6_己二醇=3: 1之莫耳比的多元醇混合物與碳 酸酯反應所得到之聚碳酸酯二醇、脂環構造含有率39重量 %、100g)、2,2-二羥曱基丙酸（DMPA、36.7g)與異佛爾 酮二異氰酸酯（IPDI、144g) ’在N-乙基吡咯烷酮（114g) 中，於二月桂酸二丁基錫（〇.2g)存在下，氮環境下，以 80至90°C加熱2.5小時。加入2,6-二第三丁基-4-曱基酚 (〇.2g)與4-曱氧基酚（〇.2g)，使環境成為空氣。進一步， 置入新戊四醇三丙烯酸酯（PETA、225g)，以90。(：加熱至 NCO基含量約成為〇重量％為止。使反應混合物冷卻至70 °C ’於此再添加混合三羥甲基丙烷三丙烯酸酯（TMPTA、 219g)、三乙胺（28.4g)。使反應混合物（113g)於強烈攪 拌下加入水（202g)中，得到水性聚氨基甲酸酯樹脂分散 體。 [比較例1 ] 以具備攪拌機及加熱器之反應裝置，使ETERNACOLL (註冊商標）UM 90 (3/1)(宇部興產製；數目平均分子 量916 ;羥基價mgKOH/g ;多元醇成分為M-環己烷 二甲醇；1，6-己二醇=3 : 1之莫耳比的多元醇混合物與碳 酸酯反應所得到之聚碳酸酯二醇、脂環構造含有率39重量 %、40.9g)、2,2-二羥曱基丙酸（DMPA、11.8g)與異佛爾 酮二異氰酸酯（IPDI、52.7g)，在N-乙基吡咯烷酮（44.3g) 56 323441 201217408 中，於二月桂酸二丁基錫（O.lg)存在下，氮環境下’以 80至90°C加熱4小時。氨基曱酸酯化反應終止時之NCO 基含量為0.42重量％。加入2,6-二第三丁基-4-甲基酚 (0.2g)與4-甲氧基酚（〇.2g)，使環境成為空氣。使反應 混合物冷卻至70X：，於此再添加混合三羥甲基丙烷三丙烯 酸酯（TMPTA、101g)、與三乙胺（8.7g)。使反應混合物 (222g)於強烈攪拌下加入水（369g)中。然後，加入35 重量％之2-曱基-1,5-戊二胺水溶液（MPMD、24.8g)，得 到水性聚氨基曱酸酯樹脂分散體。 [比較例2 ] 以具備攪拌機及加熱器之反應裝置，使ETERNACOLL (註冊商標）UH100(宇部興產製；數目平均分子量1〇〇4 ; 羥基價112 mgKOH/g; 1，6-己二醇與碳酸酯反應所得到之 聚碳酸酯二醇、40.8g)、2,2-二羥曱基丙酸（DMPA、7.4g) 與異佛爾酮二異氰酸酯（IPDI、55.5g)，在N-乙基吡咯烷 酮（49.0g)中，於二月桂酸二丁基錫（O.lg)存在下，氮 環境下，以80至90°C加熱2.5小時。加入2,6-二第三丁基 -4-曱基酚（0.2g)與4-曱氧基酚（〇.2g)，使環境成為空氣。 進一步置入2分子之丙烯酸與1分子的1，6-己二醇二縮水 甘油醚之反應生成物（1，6-HDL-EP-A、15.1g )，以90°C加 熱2小時。氨基曱酸酯化反應終止時之NCO基含量為5.47 重量％。使反應混合物冷卻至70°C，於此再添加混合三經 曱基丙烧三丙稀酸醋（TMPTA、78.7g)、與三乙胺（5.6g)。 使反應混合物（241g)於強烈攪拌下加入水（39〇g)中。 57 323441 201217408 然後，加入35重量％之2_甲基·by戊二胺水溶液（mPmd、 29.1g)，得到水性聚氨基甲酸酯樹脂分散體。 [比較例3 ] 以具備授拌機及加熱器之反應裝置，使eTERNAC0LL (註冊商標）UH100(宇部興產製；數目平均分子量ι〇〇4 ; 經基價112 mgKOH/g; 1，6_己二醇與碳酸酯反應所得到之 聚碳酸醋二醇、30.4g)、2,2·二羥曱基丙酸（DMPA、8.6g) 與異佛爾酮二異氰酸酯（IPDI、50.9g)，在N_乙基吡咯烷 _ (43.2g)中，於二月桂酸二丁基錫（〇 lg)存在下，氮 環境下’以80至90。(：加熱2小時。加入2,6-二第三丁基-4-曱基紛（〇.2g)與4-甲氧基酚（〇.2g)，使環境成為空氣。 進一步置入2分子之丙烯酸與1分子的丨，6_己二醇二縮水 甘油醚之反應生成物（1，6_HDL-EP-A、12.5g)、與新戊四 醇三丙烯酸酯（PETA、16.7g)，以90°C加熱6小時。氨基 曱酸酯化反應終止時之NCO基含量為3.59重量％。使反 應混合物冷卻至70。(：，於此再添加混合三羥曱基丙烷三丙 烯酸酯（TMPTA、75.0g)、與三乙胺（6.8g)。使反應混合 物（222g)於強烈攪拌下加入水（ 375g)中。然後，加入 35重量％之2-甲基-1，5-戊二胺水溶液（MPMD、16.5g)， 得到水性聚氨基甲酸酯樹脂分散體。 [比較例4] … _ . 以具備攪拌機及加熱器之反應裝置，使ETERNACOLL (註冊商標）UM 90 (3/1)(宇部興產製；數目平均分子 量916 ;羥基價122 mgKOH/g ;多元醇成分為M-環己烷 58 323441 201217408 一曱醇，1，6己-3.1之莫耳比的多元醇混合物與破 酸醋反應所得到之聚碳咖旨二醇、脂環構造含有率％重量Hit method, or a method in which (B) is mixed (A1) and dispersed in a water system, or a method in which (A1) is dispersed in an aqueous medium (8), and money (8) is dispersed in (4) (4) and dispersed (A1) The method, or the method of mixing after (A1) disk medium, and the like. "Do not disperse the water in the above-mentioned mixing or mixing, dispersing, or use a known mixing device such as a homomixer or a homogeneous 323441 39 201217408 machine. Also, in polyurethane prepolymer (Al) or In the compound (B) having a polymerizable unsaturated bond, a hydrophilic organic solvent or water may be added before mixing for viscosity adjustment, workability improvement, and dispersibility improvement. Mixed polyurethane prepolymer (A1) The step (r) of the compound &amp; substance (B) having a polymerizable unsaturated bond is to avoid unnecessary (four) of the polymerizable unsaturated bond, and is preferably carried out in the presence of oxygen. The polymerization agent is a mixture of the polyurethane prepolymer (A1) and the compound (8) having a polymerizable unsaturated bond at a temperature to avoid unnecessary polymerization of the polymerizable unsaturated bond, and can be adjusted to 1 Torr ( It is carried out under rc, more preferably at 〇 to 80t, and most preferably at 〇 to 7〇t, particularly at 5〇 to 7〇 ° C. In the manufacturing method of the present invention, 'neutralizing urethane § The prepolymer (step (4) of the acidic group of A◦, and the polyaminocarb (IV) The steps in the medium of the polymer (A1) and the compound having a polymerizable unsaturated bond can be carried out first or both. In this case, the Ui) and (8) can be neutralized with the aqueous medium and the acidic group. The agent may be mixed with the acid-based neutralizing agent in the aqueous medium or (B), or may be mixed with (A1). The polyurethane urethane prepolymer (A1) is polymerizable. a step of dispersing the unsaturated bond compound (B) in an aqueous medium (a step of reacting the formic acid acetal prepolymer UO with the chain extender (c) to obtain an aqueous urethane resin ((5) may also be carried out simultaneously (A1), (C), (B) and aqueous medium -: Under-mixed, (C" 323441 40 201217408 may be mixed with the aqueous medium first, and then mixed with (A1) or (B). a step of the acidic group of the polyaminophthalate prepolymer (A1), wherein the polyaminophthalate prepolymer (A1) and the compound (B) having a polymerizable unsaturated bond are dispersed in an aqueous medium. Step (^), a step of reacting a polyurethane prepolymer (Α1) with a chain extender (C) to obtain an aqueous polyglycolic acid vinegar resin ( 5) It can also be carried out at the same time. In this case, (Al), (C), (B), acid-based neutralizer can be mixed with the aqueous medium at one time. (C) or acidic-based neutralizer can also be pre-treated with water system. The medium or (b) is mixed, and then mixed with (A1) or (B). The polyurethane prepolymer (A1) is reacted with a chain extender (C) to obtain an aqueous polyaminophthalate resin. In the step ((5), the reaction can be carried out slowly under cooling, and, depending on the case, the reaction can be promoted under heating conditions of 60 ° C or less. The reaction time under cooling can be about 0.5 to 24 hours. The reaction time under heating conditions of 60 ° C or lower may be about 0.1 to 6 hours. When the total amount of the solid content of the aqueous polyaminophthalate resin dispersion (comprising the compound (B) having a polymerizable unsaturated bond) is 100 parts by weight, the polyaminophthalic acid resin (A) is preferably 5 to 60 parts by weight. It is more preferably 15 to 50 parts by weight, most preferably 25 to 40 parts by weight. The number average molecular weight of the polyurethane resin (A) is preferably from 1,000 to 1,000,000. From the viewpoint of the tackiness of the dried coating film before photohardening, it is more preferably from 10,000 to 1,000,000. XII. Photopolymerization initiator The photopolymerization initiator may also be added to the aqueous polyaminophthalate resin dispersion of the present invention. The photopolymerization initiator is not particularly limited, and a known one can be used. 41 323441 201217408 Specifically, by irradiation with an active energy ray (for example, ultraviolet ray), it is easy to cleave to form a photopolymerization initiator of two radical light (tetra) type or dehydrogenation type. You can also use this together. Such a photopolymerization initiator may, for example, be acetophenone, 2,2-diethoxyacetamidine, p-dimethylaminopropyl, diphenyl ketone, chlorobenzophenone _, P, P, _ bis diethylaminodiphenyl ketone, benzoin ethyl sulphate, benzoin n-propyl fluorene, benzoin isopropyl shunt, benzoin isobutyl shrine, benzoin n-butyl Ether, benzoin dimethyl ketal, thioxanthone, p-isopropyl-α-hydroxy, isobutyl phthalate, 2,2·dimethoxy-2-phenylphenyl benzene, i• Cyclohexyl phenyl ketone ' 2m [ 4 · (methylthio) phenyl] 2 - phenanthrenyl-propanone, 2-diyl-2-mercapto-1-phenylpropanone], 2,4,6-trimethyldiphenyl 4-methyl-phenyl ketone, 2,2-dimethoxydiphenyl ethane, and the like. Among them, hydroxycyclohexyl phenyl ketone is preferred. When the photopolymerization initiator is added, it is preferred to react the polyurethane prepolymer (A1) with the chain extender (c) to obtain the aqueous polyurethane urethane (A) step (6). Add to. The amount of the photopolymerization initiator added is preferably from 5 to 5 parts by weight based on the solid content of the aqueous polyurethane dispersion (comprising compound (B) having a polymerizable unsaturated bond).添加剂.Additives, in addition, in the aqueous polyurethane resin dispersion of the present invention, a tackifier, a photosensitizer, a hardening catalyst, a UV absorber, a light stabilizer, an antifoaming agent, or the like may be added as needed. Additives such as plasticizers, surface conditioners, anti-settling agents, and the like. The additives may be used singly or in combination of plural kinds. The aqueous polyurethane resin dispersion of the present invention contains substantially no protective colloid, emulsifier or surfactant from the hard coating of the obtained coating film. <Coating composition and coating composition> The present invention also relates to a coating composition and a coating composition containing the aqueous polyurethane resin dispersion. The coating composition and the coating composition of the present invention may be added with other resins in addition to the aqueous t-gas phthalic acid-based resin dispersion. Other resins may, for example, be polyester resins, acrylic resins, polyether resins, polycarbonate resins, polyurethane resins, epoxy resins, alkyd resins, polyolefin resins and the like. These may be used alone or in combination. The other resin is preferably one or more hydrophilic groups. The hydrophilic group may, for example, be a hydroxyl group, a carboxyl group, a sulfonic acid group or a polyethylene glycol group. The other resin is preferably at least one selected from the group consisting of polyester resins, acrylic resins, and polysulfate resins. The polyester resin is generally produced by an esterification reaction or a transesterification reaction of an acid component and an alcohol component. As the acid component, a compound which is generally used as an acid component in the production of a polyester resin can be used. As the acid component, for example, an aliphatic polybasic acid, an alicyclic polybasic acid, an aromatic polybasic acid or the like can be used. The hydroxyl group of the polyester resin is preferably from about 10 to 300 mgKOH/g, more preferably from about 50 to 250 mgKOH/g, most preferably from about 80 to 180 mgKOH/g. The acid value of the polyester resin is preferably from about 1 to 200 mgKOH/g, more preferably from 15 to 10 mgKOH/g', most preferably from about 25 to 60 mgKOH/g. The weight average molecular weight of the polyester resin is preferably from 500 to 500,000, more preferably from 1,000 to 300,000, most preferably from 1,500 to 200,000. 43 323441 201217408 The acrylic resin is preferably an acrylic resin containing a hydroxyl group. The hydroxyl group-containing acrylic resin is a solution in which a hydroxyl group-containing polymerizable unsaturated monomer and other polymerizable unsaturated monomer copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer are used, for example, in an organic solvent. It is produced by copolymerization by a known method such as a polymerization method or an emulsion polymerization method in water. Each of the molecules having a hydroxyl group-containing polymerizable unsaturated single system has one or more compounds having a radical and a polymerizable unsaturated bond. For example, 2_ethyl (indenyl) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylic acid S, 4-butyl butyl (fluorenyl) a monoester of a (meth)propionic acid with a carbon number of 2 to 8; an ε-caprolactone modified product of such a monoester; N-hydroxymethyl ( Methyl) acrylamide; allyl alcohol; (mercapto) acrylate having a polyoxyethylene chain at the molecular end. The hydroxyl group-containing acrylic resin preferably has an anionic functional group. The hydroxy group-containing acrylic acid resin having an anionic functional group may be one of polymerizable unsaturated monomers by using a polymerizable unsaturated monomer having an anionic functional group such as a carboxylic acid, a sulfonic acid group or a phosphoric acid group. To manufacture. The base value of the hydroxyl group-containing acrylic resin is preferably from about 1 to 200 mg KOH/g from the viewpoint of storage stability of the aqueous polyaminophthalic acid vinegar resin dispersion or water resistance of the obtained coating film, etc., more preferably 2 to i 〇〇 mg KOH / g, preferably about 3 to 60 mg KOH / g. When the hydroxyl group-containing acrylic resin has an acidic group such as a carboxyl group, the acid value of the hydroxyl group-containing acrylic resin is preferably from about 1 to 200 mg KOH/g from the viewpoint of water resistance of the obtained coating film, etc., more preferably from 2 to 150 mg. It is about KOH/g, and is preferably about 5 to 100 mg KOH/g. 323441 44 201217408 The weight average molecular weight of the hydroxyl group-containing acrylic resin is preferably from 1 to 200,000, more preferably from 2,000 to 100,000, most preferably from 3,000 to 5 Å. The polyether resin may, for example, have The polymer or copolymer of the ether bond may, for example, be derived from an aromatic polyhydroxy compound such as a polyoxyethylene polyether, a polyoxypropylene polyfluorene, a polyoxybutylene polyether, a bisphenol A or a bisphenol F. Polyether and so on. The polycarbonate resin may, for example, be a polymer produced from a bisphenol compound, and examples thereof include a double-prepared A·polycarbonate. The polyaminophthalic acid resin is, for example, a polyglycolic acid which is obtained by a reaction of various polyol components such as acrylic acid, polyfluorene, polycarb, or polycarb (tetra) with polyhydric isocyanate. Key resin. The epoxy resin may, for example, be a resin obtained by a reaction between a double-antibiotic compound and a surface alcohol. The bisphenol may, for example, be bisphenol A or bisphenol F. The alkyd resin may be, for example, a polybasic acid such as an antimony, a phthalic acid or a carboxylic acid, and a polyhydric alcohol, such as a fat or oil, a fat or fat (soybean oil, linseed oil, coconut oil, stearic acid, etc.). An alkyd resin obtained by reacting a modifier such as a natural resin (rosin, amber, etc.). The polyolefin resin may be water-dispersed by using an emulsifier, for example, by using a emulsifier which is obtained by polymerizing or copolymerizing a olefin-based monomer singular monomer-based polymerization method. A resin obtained by emulsion polymerization of a monomer based on a suitable monomer. Further, depending on the case, the above (4) hydrocarbon tree chlorination may be used. (IV) Smoke-modifying resin 0 323441 45 201217408 The olefin-based monomer may, for example, be ethylene, propylene, butene, or decyl-butadiene. 4_ mercapto pentane, 3-mercapto-1-pentene, 1-heptene, hexene, 1-decene, olefins such as U-dodecene; butadiene, ethylidene norbornene A conjugated diene such as an alkene, a dicyclopentadiene, an anthracene, a 5-hexadiene or a styrene, or a non-co-diene diene or the like can be used singly or in combination of plural kinds. ^ Other monomers which can be copolymerized with the olefin-based monomer include, for example, ethyl acetate, ethylene glycol, maleic acid, citraconic acid, itaconic acid, maleic acid needle, squalic anhydride, Yikang sour liver, etc., these single systems can be used alone or in combination. In the coating composition and the coating composition of the present invention, the coating film or the coating film of the coating composition or the coating composition, the water resistance of the coating film, and the like can be improved by containing a curing agent. As the hardener, an amine resin, a polyvalent isocyanate, a blocked polyisocyanate, a melamine resin, a carbodiimide or the like can be used. The hardener may be used singly or in combination. The amine-based resin may, for example, be a partially or completely (tetra)-based filament obtained by the reaction of an amine-based component with an acid component. The silk component may, for example, be melamine, urea, benzoxanthine, 2,4-diamino-6-methyl-Us tris, sterol decylamine, spiramide or dicyanamide. The road component may, for example, be F aldehyde, paraformaldehyde, acetaldehyde or benzaldehyde. The polyisocyanate may, for example, be a compound having two or more isocyanate groups in the i molecule, and examples thereof include hexamethylene diisocyanate and trisyl hexamethylene diisocyanate. 323441 46 201217408 The blocked poly 7G isocyanate g can be obtained, for example, from the above-mentioned polyisoindolizine® oxime Ig-I-based addition-capping agent, and the blocking agent can be, for example, Phenols such as phenol and nonylphenol, aliphatic alcohols such as methanol and ethanol, active methylene groups such as malonate, butyl mercaptan, etc., butyl mercaptan, and decyl mercaptan Such as thiol, acetanilide, acetophenone, etc., such as hexamethyleneamine, decylamine, succinimide, maleimide, etc. A blocking agent such as an amine such as an imide, a B, a propyl ketone or a methyl ethyl oxime, or an amine such as an anthranilamine, an aniline or a thiamine. The melamine resin may, for example, be a methyl melamine such as dimethyl melamine or trimethyl melamine; or a urethral ether or condensate of the methyl melamine; methyl melamine a condensate of the fines, and the like. In the coating composition and the coating composition of the present invention, a coloring matter or an extender pigment or a bright pigment can be added. The gill coloring pigment may, for example, be titanium oxide, zinc white, carbon black, molybdenum red, prolu|cobalt blue, azo pigment, phthalocyanine pigment, quinacridine pigment, isoporphyrin pigment, and threon pigment. , enamel paint, etc. These may be used alone or in combination. It is particularly preferable to use titanium oxide and/or carbon black as the coloring pigment. Examples of the constitution include clay, kaolin, barium sulfate, barium carbonate, barium carbonate, a/moon stone, ceria, alumina white, and the like. These may be used alone or in combination. For the constitutional pigment, it is preferred to use sulphuric acid lock and/or 'moonstone' to use barium sulphate. 323441 47 201217408 The pigment system can be used in &, copper, zinc, and yellow towns. L: mica is oxidized by gasification or iron oxide coating, and mica coated with titanium oxide or iron oxide. The composition of the human material and the composition of the coating agent are as needed: 曰'~, a curing catalyst, an ultraviolet absorber, a light stabilizer, and an additive. These 4 series can be used alone or in combination. The method for producing the coating composition and the coating composition of the present invention is not particularly limited, and a known production method can be used. The general coating composition and the coating agent composition are prepared by mixing the aqueous polyurethane lysate dispersion with the various additives described above and adding an aqueous medium to adjust the viscosity to the agricultural method. The material to be coated or the coating agent composition of the coating composition may be, for example, metal, plastic, inorganic or wood. The coating method of the coating composition or the coating method of the coating composition may, for example, be a bell type coating, a spray coating, a roller coating, a spray coating, a dipping coating or the like. The aqueous polyurethane resin dispersion, the aqueous polyaminophthalate resin dispersion composition, the coating composition, and the coating composition of the present invention are preferably coated or coated or coated on a desired substrate. After coating, at least a portion of the aqueous medium is evaporated under heating or non-heating, and the active energy ray is irradiated to harden. The active energy ray system may, for example, be an ionized radiation of electron east, ultraviolet light or r-line, and preferably ultraviolet light. If the source of ultraviolet light is a light source that emits light in the ultraviolet region, there is no 48 323441 201217408 special limitation. For example, &amp; lamp, low pressure mercury lamp, high pressure mercury lamp, super pressure mercury lamp, metal lamp lamp, carbon arc lamp, 纟I can be used. Silk lamps, etc. The irradiation time can be suitably changed depending on the type of the compound having a polymerizable unsaturated bond, the type of the photopolymerization initiator, the thickness of the coating, and the conditions of the ultraviolet ray. From the point of workability, it should be irradiated for U60 seconds. The purpose of the hardening reaction is to perform the heat treatment after the ultraviolet irradiation. The irradiation amount of the ultraviolet rays used for curing the aqueous polyurethane resin dispersion, the coating composition, the coating composition, and the like of the present invention is preferably from 300 to 3,000 mJ/cm 2 from the viewpoint of rapid hardenability and workability. In order to harden, in addition to ultraviolet rays, an electron beam or the like may be used. When the electron beam is hardened, a photopolymerization initiator may not be added, and an electron beam acceleration device having 1 to 500 eV is preferably used. [Examples] Next, the present invention will be described in more detail by way of examples and comparative examples. [Example 1] A reactor equipped with a stirrer and a heater, ETERNACOLL (registered trademark) UM 90 (3/1) (manufactured by Ube Industries; number average molecular weight 916; hydroxyl value i22 mgKOH/g; polyol component 1 , 4-cyclohexanedimethanol: 1,6-hexanediol = 3: 1 molar ratio of the polyol mixture and the carbonate diol obtained by the reaction of the carbonate, the alicyclic structure content rate 39 weight 0 / 〇, 25.9 L), 2,2-dihydroxymethyl propionic acid (〇1\«&gt; VIII, 11.1 layer) and isophorone diisocyanate (IPDI, 57.5 g) in N-ethylpyrrolidone (43.9 g) is heated at 80 to 90 ° C for 2.5 hours in the presence of dibutyltin dilaurate (〇.lg) under nitrogen. Add 2,6-di-tert-butyl-4-nonylphenol 49 323441 201217408 (0.2g) and 4-methoxyl (〇.2g) to make the environment air. Further 'injecting two molecules of acrylic acid with one molecule of hydrazine, 6-hexanediol diglycidyl ether reaction product (1,6-HDL-EP-A, i2.6g), pentaerythritol triacrylate (PETA, 19.7 g), heated at 90 ° C for 6 hours. The NCO group content at the end of the amino oximation reaction was 4.01 by weight. /. . The reaction mixture was cooled to 70 C, and then dipentaerythritol hexaacetate (DPHA, 79.9 g) and triethylamine (8.9 g) were added. The reaction mixture (226 g) was added to water (386 g) with stirring. Then, a 35 wt% aqueous solution of 2-methyl-1,5-pentanediamine (MPMD, 2 lg) was added to obtain an aqueous polyurethane resin dispersion. [Example 2] ETERNAC〇LL (δ main volume trademark) UM 9〇(3/1) was used as a reaction apparatus equipped with a stirrer and a heater (Ube Industries, Ltd.; number average molecular weight 916, hydroxyl value 122 mgK〇) H/g; polyol component is 聚碳酸酯4 cyclohexane dimethanol: 1,6-hexanediol = 3: 1 molar ratio of polyol mixture and carbonate diol obtained by reaction with carbonate Structure content: 39 wt/〇, 40.3 g), 2,2-dihydromercaptopropionic acid (DMpA, 97 g) and isophora diisocyanate (IPDI, 46.3 g), in N_ethyl The pyrrolidine copper (4 Å. 5 g) was heated at 80 to 90 C for 2.5 hours in the presence of dibutyltin laurate (O.lg) under a nitrogen atmosphere. 2,6-Di-t-butyl-4-nonylphenol (0.2 g) and 4-methoxyphenol (〇2 g) were added to make the environment air. Further, pentaerythritol triacrylate (PETA, 16.1 g) was placed at 90. (: heating for 5 hours. The NC thiol content at the end of the urethanization reaction is 3 51 wt/〇, and the reaction mixture is cooled to 702⁄4, and then the mixed trishydroxy guanidine 323441 50 201217408 propyl propyl tripropionate is added. Ester (TMPTA, 72.5 g), triethylamine (7.8 g). The reaction mixture (2 μg) was added to water (353 g) with vigorous stirring. Then, 35% by weight of 2-mercapto-1,5 was added. Ethyl pentaamine aqueous solution (MPMD, 15.8 g) was obtained to obtain an aqueous polyaminophthalate resin dispersion. [Example 3] A reactor equipped with a stirrer and a heater was used to make ETERNACOLL (registered trademark) UM 90 (3/1) (Ube Hiroshi Production; number average molecular weight 916; hydroxyl value 122 mgKOH / g; polyol component is 1,4-cyclohexanedidecyl alcohol: hydrazine, 6-hexanediol = 3: 1 molar ratio The polycarbonate diol obtained by reacting the polyol mixture with carbonated vinegar, the alicyclic structure content: 39% by weight, 56'lg), 2,2-di-methylpropionic acid (DMPA, 23.5g) and isophor Ketoisoisocyanate (IPDI, 124g) in the presence of dibutyltin dilaurate (〇2g) in a mixture of ethylpyrrolidone (96.4g) under nitrogen It was heated at 80 to 90 ° C for 3 hours, and 2,6-di-tert-butyl-4-methylphenol (0.5 g) and 4-methoxyphenol (〇.5 g) were added to make the environment air. Further, A reaction product of two molecules of acrylic acid with one molecule of hydrazine, 6·hexanediol diglycidyl ether (1,6-HDL-EP-A, 27.7 g), and pentaerythritol triacrylate (PETA) 42.3 g) 'heated at 90 ° C for 5 hours. The NCO group content at the end of the aminoguanidine acid S reaction was 4.05% by weight. The reaction mixture was cooled to 70 ° C, and then mixed with dinonotetraol hexaacrylic acid was added. Ester (DPHA, 178 g), triethylamine (19.5 g) e, the reaction mixture (25 lg) was added to water (423 g) with vigorous addition. Then, a solution of % by weight of diethylenetriamine (DETA, 13.3 g) was added. The water-soluble polyaminoanthracene ester resin dispersion was obtained. 51 323441 201217408 [Example 4] The reaction was carried out with a stirrer and a heater to make ETERNACOLL (s main volume trademark) UM 90 (3/1) The number average molecular weight is 916; the hydroxyl value is 122 mgKOH/g; the polyol component is i,4-cyclohexanedimethanol: 1,6-hexanediol=3 ··丨 molar ratio of polyol mixed The polycarbonate diol obtained by the reaction with the carbonate, the alicyclic structure content: 39% by weight, 56.1 g), 2,2-dimethylolpropionic acid (D]y [pA, 23_5 g) and isophor Keto diisocyanate (IPDI, 124 g) was heated in an ethylpyrrolidone (96.4 g) in the presence of dibutyltin dilaurate (0.2 g) in a nitrogen atmosphere at 80 to 90 C for 3 hours. 2,6-Di-t-butyl-4-indolylphenol (0.5 g) and 4-methoxyphenol (0.5 g) were added to make the environment air. Further, a reaction product of 1 molecule of acrylic acid and a ruthenium molecule of 16-hexanediol diglycidyl ether (1,6-HDL-EP-A, 27.7 g), and pentaerythritol triacetate vinegar were placed. (PETA, 42.3g), heated at 9 (TC for 5 hours. The NCO group content at the end of the urethanization reaction was 4 〇 5% by weight. The reaction mixture was cooled to 70 ° C, and then the mixture was added. Pentaerythritol hexaacrylate (DPHA, 178 g), triethylamine (19.5 g). The reaction mixture (232 g) was added to water (391 g) with vigorous stirring. Then, a 35% by weight aqueous solution of diethylenediamine was added ( DETA, 6.1 g), 35% by weight aqueous solution of 2-mercapto-1,5-pentanediamine (MPMD, 1.0 g) gave an aqueous polyurethane resin dispersion. [Example 5] The reactor of the mixer and the heater is ETERNACOLL (registered trademark) UM 90 (3/1) (manufactured by Ube Industries; number average molecular weight 52 323441 201217408 916; hydroxyl value 122 mgKOH/g; polyol composition is 1,4 _ Cyclohexene dimethanol; 1,6-hexanediol = 3: 1 molar ratio of polyol mixture and carbonate diol obtained by reaction with carbonate Preparation rate: 39% by weight, 25.2g), 2,2-dimethylolpropionic acid (DmpA, l〇.6g) and isophorone diisocyanate (IPDI, 56·.) in N-ethylpyrrole In alkane (42 9g), in the presence of dibutyltin dilaurate (O.lg), under a nitrogen atmosphere, 80 to 90. (: heating for 2 hours. Add 2,6-di-tert-butyl-4- Methyl age (0.2g) and 4-methoxyphenol (〇.2g)' make the environment air. Step by step, put 2 molecules of acrylic acid and 1 molecule of 1,6-hexanediol diglycidide The reaction product (1,6-HDL-EP-A, i2.2g) and neopentyl alcohol triacrylate (PETA, 19.9 g) were heated at 90 ° C for 6 hours. When the carbamate reaction was terminated The NCO group content was 3.95% by weight. The reaction mixture was cooled to 70 ° C. Here, a mixture of trimethylolpropane triacrylate (TMPTA, 79.1 g) and triethylamine (8.6 g) was added. The mixture (233 g) was added to water (401 g) with vigorous scrambling. Then, 35% by weight of 2-methyl-1,5-pentanediamine aqueous solution (MPMD, 19.7 g) was added to obtain an aqueous polyurethane. Ester resin dispersion. [Example 6] With a blender The reactor of the heater is ETERNACC) LL (registered trademark) UM 90 (3/1) (manufactured by Ube Industries; number average molecular weight 916; hydroxyl value 122 mgKOH/g; polyol component is 1,4_cyclohexene a polycarbonate diol obtained by reacting dihydric alcohol; 1,6-hexanediol = 3:1 molar ratio polyol mixture with a carbonate, having an alicyclic structure content of 39% by weight, 1218), 2, 2-Dihydroxymethylpropionic acid (〇)^8, 29々) and isophor 53 323441 201217408 keto diisocyanate (IPDI, 139g) in N-ethylpyrrolidone (121g) in dibutyltin dilaurate In the presence of (0.2 g), it was heated at 80 to 90 ° C for 2 hours under a nitrogen atmosphere. 2,6-Di-t-butyl-4-methylphenol (0.8 g) and 4-methoxyphenol (〇8 g) were added to make the environment air. Further, pentaerythritol triacrylate (PETA, 46.1 g) was placed and heated at 90 ° C for 6 hours. The NCO group content at the termination of the urethanization reaction was 3.83 wt%. The reaction mixture was cooled to 70 ° C, and a mixture of trimethylsulfonium triacetate (TMPTA, 22 lg) and triethylamine (24·1 g) was further added thereto. The reaction mixture (201 g) was added to water (332 g) with vigorous stirring. Then, hexamethylene dioxime (AH, 8.5 g) was added to obtain an aqueous polyurethane resin dispersion. [Example 7] A reaction apparatus equipped with a stirrer and a heater was used to make ETERNACOLL (sibs trademark) um 90 (3/1) (manufactured by Ube Industries; number average molecular weight 916, hydroxyl value 122 mgK〇H/g) The polyol component is 1>4 cyclohexanedimethanol; 1,6-hexanediol=3: the molar mixture of the molar ratio of the molar ratio of the molar ratio of the polyol mixture obtained by reacting with the carbonated vinegar, the alicyclic structure Contents: 39% by weight, 121 g), 2,2·Dimethylolpropionic acid (dmpa, 29.4 g) and isophorone diisocyanate (IPDI, 139 g) in the group of ethylpyrrolidone (121 g) 'In the presence of dibutyltin dilaurate (〇. 2g), it was heated at 80 to 90 c for 2 hours under a nitrogen atmosphere. Add 2,6-di-t-butyl-4-methylphenol (〇.8g) and 4-methoxyphenol (〇.8g) to make the environment air. Further, pentaerythritol triacrylate (PETA, 46.1 g) was placed and heated at 90 ° C for 6 hours. The NCO group content at the end of the amino oximation reaction was 3.83, 54 323,441, 201217,408. The reaction mixture was cooled to 70 ° C, and additional trihydrodecylpropane triacrylate (TMPTA, 221 g) and triethylamine (24.1 g) were added. The reaction mixture (199 g) was added to water (337 g) with vigorous stirring. Then, a 35 wt% aqueous hydrazine solution (4.8 g) was added to obtain an aqueous polyaminophthalate resin dispersion. [Example 8] A reactor equipped with a stirrer and a heater was used to make ETERNACOLL (registered trademark) UM 90 (3/1) (manufactured by Ube Industries; number average molecular weight 916; hydroxyl value: 122 mgKOH/g; polyol component was 1,4-cyclohexanedimethanol; 1,6-hexanediol = 3: 1 molar ratio of the polyol mixture obtained by reacting a carbonate with a carbonate diol, alicyclic structure content: 39 weight %, 121§), 2,2-dihydroxymethylpropionic acid (〇]^«&gt; VIII, 29.4 §) with isophorone diisocyanate (IPDI, 139g) 'in N-ethyl-per In (121 g), in the presence of dibutyltin dilaurate (0.2 g), it was heated at 80 to 90 ° C for 2 hours under a nitrogen atmosphere. 2,6-Di-t-butyl-4-nonylphenol (〇.8§) and 4-methoxyphenol (0.8 g) were added to make the environment air. Further, neopentyl alcohol triacrylate (PETA, 46.1 g) was placed and heated at 9 ° C for 6 hours. The NCO group content at the termination of the aminoguanidine reaction was 3.83 wt%. The reaction mixture was cooled to 70 ° C, and then a mixture of triterpene propylidene triacrylate (TMPTA, 221 g) and triethylamine (24.1 g) was added. The reaction mixture (253 g) was added to water (4i 〇g) with vigorous stirring. Then, a 13% by weight aqueous solution of hexahydropyridinium (4.8 g) was added to obtain an aqueous polyurethane resin dispersion. [Example 9] 55 323441 201217408 A reactor equipped with a stirrer and a heater, ETERNACOLL (registered trademark) UM 90 (3/1) (manufactured by Ube Industries; number average molecular weight 916; hydroxyl value 122 mgK〇H/g a polycarbonate diol or an alicyclic ring obtained by reacting a polyol mixture having a polyol component of 1,4-cyclohexanedonol and 1,6-hexanediol = 3:1 molar ratio of a polyol with a carbonate Structure content: 39% by weight, 100 g), 2,2-dihydroxymethyl propionic acid (DMPA, 36.7 g) and isophorone diisocyanate (IPDI, 144 g) 'in N-ethylpyrrolidone (114 g), It was heated at 80 to 90 ° C for 2.5 hours in the presence of dibutyltin dilaurate (〇. 2 g) under nitrogen. 2,6-Di-t-butyl-4-nonylphenol (〇.2g) and 4-methoxyphenol (〇.2g) were added to make the environment air. Further, pentaerythritol triacrylate (PETA, 225 g) was placed at 90. (: heating until the NCO group content is about 〇% by weight. The reaction mixture is cooled to 70 ° C. Here, trimethylolpropane triacrylate (TMPTA, 219 g) and triethylamine (28.4 g) are further added. The reaction mixture (113 g) was added to water (202 g) under vigorous stirring to obtain an aqueous polyurethane resin dispersion. [Comparative Example 1] A reactor equipped with a stirrer and a heater was used to make ETERNACOLL (registered trademark) UM. 90 (3/1) (Ube Industries; number average molecular weight 916; hydroxyl number mgKOH/g; polyol component M-cyclohexane dimethanol; 1,6-hexanediol = 3: 1 molar ratio The polycarbonate diol obtained by reacting the polyol mixture with the carbonate, the alicyclic structure content: 39% by weight, 40.9 g), 2,2-dihydroxymethyl propionic acid (DMPA, 11.8 g) and isophor Keto diisocyanate (IPDI, 52.7g) in N-ethylpyrrolidone (44.3g) 56 323441 201217408, heated in a nitrogen atmosphere at 80 to 90 ° C in the presence of dibutyltin dilaurate (O.lg) 4 hours. The NCO group content at the end of the amino oximation reaction was 0.42% by weight. Add 2,6-di-t-butyl-4- The phenol (0.2g) and 4-methoxyphenol (〇2g) make the environment air. The reaction mixture is cooled to 70X: and then mixed with trimethylolpropane triacrylate (TMPTA, 101g) And triethylamine (8.7 g). The reaction mixture (222 g) was added to water (369 g) with vigorous stirring. Then, a 35 wt% aqueous solution of 2-mercapto-1,5-pentanediamine (MPMD, 24.8 g), a water-soluble polyaminophthalate resin dispersion was obtained. [Comparative Example 2] A reactor equipped with a stirrer and a heater was used to make ETERNACOLL (registered trademark) UH100 (manufactured by Ube Industries; number average molecular weight: 1〇〇4) ; hydroxyl group 112 mgKOH / g; 1,6-hexanediol and carbonate obtained by reaction of polycarbonate diol, 40.8g), 2,2-dihydroxymethyl propionic acid (DMPA, 7.4g) and Fosone diisocyanate (IPDI, 55.5 g) in N-ethylpyrrolidone (49.0 g) in the presence of dibutyltin dilaurate (O.lg), heated at 80 to 90 ° C under nitrogen atmosphere 2.5 Add 2,6-di-tert-butyl-4-nonylphenol (0.2g) and 4-decyloxyphenol (〇.2g) to make the environment air. Further insert 2 molecules of acrylic acid. The reaction product (1,6-HDL-EP-A, 15.1 g) with 1 molecule of 1,6-hexanediol diglycidyl ether was heated at 90 ° C for 2 hours. When the amino oximation reaction was terminated The NCO group content was 5.47% by weight. The reaction mixture was cooled to 70 ° C, and then a mixture of trimethylsulfonium triacetate (TMPTA, 78.7 g) and triethylamine (5.6 g) was added. The reaction mixture (241 g) was added to water (39 g) with vigorous stirring. 57 323441 201217408 Then, a 35 wt% aqueous solution of 2-methyl-by-pentanediamine (mPmd, 29.1 g) was added to obtain an aqueous polyurethane resin dispersion. [Comparative Example 3] ETERNAC0LL (registered trademark) UH100 (manufactured by Ube Industries, Ltd.; number average molecular weight ι〇〇4; base price 112 mgKOH/g; 1,6_) in a reaction apparatus equipped with a mixer and a heater Polycarbonate diol obtained by reacting hexanediol with carbonate, 30.4 g), 2,2·dihydroxymethyl propionic acid (DMPA, 8.6 g) and isophorone diisocyanate (IPDI, 50.9 g), In N_ethylpyrrolidine _ (43.2 g), in the presence of dibutyltin dilaurate (〇 lg), in the nitrogen environment '80 to 90. (: heating for 2 hours. Add 2,6-di-t-butyl-4-indolyl (〇.2g) and 4-methoxyphenol (〇.2g) to make the environment air. Further insert 2 molecules a reaction product of acrylic acid with 1 molecule of hydrazine, 6-hexanediol diglycidyl ether (1,6_HDL-EP-A, 12.5 g), and pentaerythritol triacrylate (PETA, 16.7 g), Heating at 90 ° C for 6 hours. The NCO group content at the end of the amino oximation reaction was 3.59% by weight. The reaction mixture was cooled to 70. (:, here, a mixture of trihydroxymercaptopropane triacrylate (TMPTA, 75.0 g), and triethylamine (6.8 g). The reaction mixture (222 g) was added to water (375 g) with vigorous stirring. Then, a 3 wt% aqueous solution of 2-methyl-1,5-pentanediamine was added. (MPMD, 16.5 g), an aqueous polyurethane resin dispersion was obtained. [Comparative Example 4] ... _ . ETERNACOLL (registered trademark) UM 90 (3/1) (with a reactor equipped with a stirrer and a heater) Ube Industries; number average molecular weight 916; hydroxyl number 122 mgKOH/g; polyol component M-cyclohexane 58 323441 201217408 monoterpene alcohol, 1,6-3.1 molar ratio The polycarbohydrate diol and the alicyclic structure obtained by reacting the polyol mixture with the acid vinegar contain % by weight

%、41.lg)、2,2-m_(_PA、n.6g)^M 爾酮二異氰酸醋（IPDI、91.3g)，在N-乙基n比略烧_(69.8g) 中’於二月桂酸二丁基錫（(Ug)存在下，氮環境下，以 80至航加熱2.5小時。加入&amp;二第三丁基冬甲基酴 (〇.2g)與4-曱氧基紛（G.2g)’使環境成為线。進一步 置入2分子之丙烯酸與1分子的W己二醇二縮水甘油醚 之反應生成物（1，6-HDL.EP-A、2i.6g)、與新戊四醇三丙 烯酸酯（PETA、29.3g )，以9(rc加熱6小時。氨基甲酸醋 化反應終止時之NCO基含量為3 %重量％。使反應混合 物冷卻至70°C ’再添加混合三乙胺（143g)。使反應混合 物（241g)於強烈攪拌下加入水（ 334g)中。然後，加入 35重量％之2-曱基-1，5-戊二胺水溶液（MpMD、29 5g)， 得到水性聚氨基甲酸酯樹脂分散體。 [鉛筆硬度與密著性之試料製作] 於實施例1至9、比較例1至4之各水性聚氨基甲酸 酯樹脂分散體中，添加聚合起始劑（IRGACURE 500、Ciba Specialty Chemical公司製）3重量％/固形分，充分攪拌而 得到塗佈劑。將此均一地分別塗佈於ABS樹脂、丙婦酸樹 脂、PC樹脂上使得乾燥後之膜厚成為約20//m。然後，以 60t乾燥30分鐘，得到塗膜（紫外線照射前）。使所得到 之塗膜通過高壓水銀燈之下（照射1次，紫外線照射量1〇00 mJ/cm2)。使所得到之聚氨基曱酸酯樹脂塗膜供予鉛筆硬度 323441 59%, 41.lg), 2,2-m_(_PA, n.6g)^Molone diisocyanate (IPDI, 91.3g), in N-ethyln ratio slightly burned _(69.8g) 'In the presence of dibutyltin dilaurate ((Ug), heated in a nitrogen atmosphere for 80 hours at 80 to voyage. Add &amp; di-tert-butyl-methylene methyl hydrazine (〇.2g) and 4-methoxyl (G.2g) 'The environment is a line. Further, a reaction product of two molecules of acrylic acid and one molecule of W hexanediol diglycidyl ether (1,6-HDL.EP-A, 2i.6g), With neopentyl alcohol triacrylate (PETA, 29.3 g), heated at 9 (rc for 6 hours. The NCO group content at the end of the carbamic acid hydration reaction was 3% by weight. The reaction mixture was cooled to 70 ° C. The mixed triethylamine (143 g) was added. The reaction mixture (241 g) was added to water (334 g) with vigorous stirring. Then, a 3 wt% aqueous solution of 2-mercapto-1,5-pentanediamine (MpMD, 29) was added. 5 g), a water-soluble polyurethane resin dispersion was obtained. [Production of pencil hardness and adhesion test] In each of the aqueous polyurethane resin dispersions of Examples 1 to 9 and Comparative Examples 1 to 4, Add polymerization initiator (IRGACURE 500) 3 wt%/solid content of Ciba Specialty Chemical Co., Ltd., and sufficiently stirred to obtain a coating agent. This was uniformly applied to ABS resin, propylene glycol resin, and PC resin so that the film thickness after drying became about 20/ /m. Then, it was dried at 60 t for 30 minutes to obtain a coating film (before ultraviolet irradiation), and the obtained coating film was passed under a high pressure mercury lamp (illumination once, ultraviolet irradiation amount was 1 〇 m m/cm 2 ). Polyaminophthalate resin coating film for pencil hardness 323441 59

Hnf 201217408 測定、及密著性之評定。 (硬度之評定） 藉由測定聚氨基曱酸酯樹脂塗膜的鉛筆硬度，進行評 定。 [鉛筆硬度之測定] 在前述所得到之丙烯酸樹脂上的聚氨基曱酸酯樹脂 塗膜中’依據JIS K 5600-5-4之方法測定樹脂塗膜的鉛筆 硬度。 (密著性之評定） 在前述所得到之ABS樹脂、丙烯酸樹脂、PC樹脂上 的聚氨基曱酸酯樹脂塗膜中，藉棋盤眼剝離法進行評定。 亦即，於試驗片以切割刀製作4mm2之格眼25個，藉剝離 紙帶研究剝離性。 (貯存安定性之評定） 將實施例1至9、比較例1至4之各水性聚氨基甲酸 酿樹脂分散體之外觀在製造後1週後進行觀察，確認貯存 安定性。評定基準係如下述。 〇：無變化。 x:可看到凝集物 (無沾黏性之評定） 於實施例1至9、比較例1至4之各水性聚氨基甲酸. 酉曰樹脂分散體’添加聚合起始劑（IRGACURE 500、Ciba Specialty Chemical公司製）3重量％/固形分，充分攪拌而 件到塗佈劑。將此均一地分別塗佈於丙烯酸樹脂上使得乾 60 323441 201217408 燥後之膜厚成為約20/zm。然後，以60°C乾燥30分鐘， 得到塗膜（紫外線照射前）。以指觸摸塗膜，評定為無沾黏 性。評定基準係如下述。 〇：無變化 X :指或指紋之痕跡會殘留。 [表1] 組成名稱 化合物 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 多元醇(a) U_(3/1 &gt; 12 21 12 12 12 21 21 UH1 00 異氰酸酯（d) IPDI 26 24 27 26 26 24 24 含酸基之多元醇（C) DMPA 5 5 5 5 5 5 5 鏈延長劑（C) MPMD 4 3 2 4 DETA 2 1 AH 3 肼 3 六氫0秦 (甲基）丙烯酸化合物(e) 1.6-HDL-EP-A 6 6 6 6 PETA 9 8 9 g 9 8 8 (甲基）丙烯酸化合物(B) DPHA 38 39 39 TMPTA 39 39 39 39 硬度 丙烯酸樹脂 2H 〜3H Η〜2H 2Η 2H 2H Η Η 密著性 ABS樹脂 25/25 25/25 25/25 25/25 25/25 25/25 -25/25- 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 丙烯酸樹脂 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 PC樹脂 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 貯存安定性 〇 〇 〇 〇 〇 〇 〇 無沾黏性 〇 —Ω..... 〇 〇 〇 〇 〇 61 323441 龜 201217408 [表2] 組成名稱 實施例8 實施例9 比較例1 比較例2 比較例3 比較命Fi&quot; 多元酵(a) UM90&lt;3/1) 21 14 19 19 — UH100 19 15 異氯酸酯 IPDI 24 20 24 26 25 43 含酸基之多元® dmpa 5 5 5 4 4 8 鏈延長劑（C) MPMD 5 5 3 6 DETA AH 肼 六氫啦嗔 3 (甲基）两烯酸化合物(e) 1.6-HDL-EP-A 7 6 10 PETA 8 31 8 14 (甲基）丙烯蓬化合物(日） DPHA 30 TMPTA 39 47 3Θ 39 硬度 丙烯酸樹脂 Η 2Η 〜3Η Η〜2Η Η—2Η 2Η Η 密著性 ABS樹脂 25/25 25/25 25/25 16/25 16/25 25/25 25/25 25/25 25/25 12/25 15/25 25/25 25/25 25/25 25/25 0/25 1/25 25/25 丙烯後樹脂 25/25 25/25 25/25 15/25 20/25 11/25 25/25 25/25 25/25 2/25 14/25 10/25 25/25 25/25 25/25 2/25 4/25 0/25 PC樹脂 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 貯存安定性 ο 〇 X X 〇 〇 無沾黏性 ο X 〇 〇 Ο 1 Ο 表中之重里伤係表不以樹脂中之全固形分（包含丙稀 酸化合物）作為1〇()重量份時之各化合物的重量份。 表中之錯筆硬度例如「H」表示以Η之鉛筆完全無刮 傷 2Η至3Η」表示以3Η之鉛筆刮傷或無刮傷，以2Η 完全無刮傷。 表中之密著性表示剝離試驗之結果。「25/25」表示試 驗後，25格中，25格密著。 如則述表所示般，實施例之水性聚氨基曱酸酯樹脂分 散體係可形成密著性優異之塗膜，且貯存安定性優異。 於聚氨基甲酸酯樹脂（Α)之調製中，在不使用不飽 和化口物（e)之比較例1中的貯存安定性差。 於聚氨基甲酸酯樹脂（A)之調製中，不使用主鏈具 62 323441 201217408 . 有知％構造之聚碳酸酯二醇（a)的比較例2及3、以及水 性聚氨基甲酸酯樹脂分散體中未摻合具有聚合性不飽和鍵 的化合物(B)之比較例4之任一者的密著性均差。 藉由比較比較例2與比較例3之結果，可知藉由使 用1分子中具有1個羥基之不飽和化合物（e，），即可提高 水性聚氨基甲酸酯樹脂分散體之貯存安定性。 藉由比較實施例5與實施例6之結果，可知藉由使用 1分子中具有2個以上羥基之不飽和化合物（e，），從水性 聚氨基甲酸酯樹脂分散體所得到之塗膜的硬度即可變高。 進一步，藉由比較實施例1與實施例9之結果，可 知藉由使用鏈延長劑，紫外線照射前之乾燥塗膜的無沾黏 性較高。 [產業上之可利用性] 本發明之水性聚氨基曱酸酯樹脂分散體係可廣泛利 用作為塗料或塗佈劑之原料等。 【圖式簡單說明】 無。 【主要元件符號說明】 無。 323441 63Hnf 201217408 Determination, and evaluation of adhesion. (Evaluation of hardness) The evaluation was carried out by measuring the pencil hardness of the polyaminophthalate resin coating film. [Measurement of pencil hardness] The pencil hardness of the resin coating film was measured in accordance with the method of JIS K 5600-5-4 in the polyaminophthalate resin coating film on the acrylic resin obtained above. (Evaluation of Adhesion) The polyaminophthalate resin coating film on the ABS resin, the acrylic resin, and the PC resin obtained above was evaluated by a checkerboard peeling method. That is, 25 pieces of a 4 mm 2 grid were made by a cutting blade on a test piece, and the peeling property was examined by peeling a paper tape. (Evaluation of Storage Stability) The appearance of each of the aqueous polyurethane resin dispersions of Examples 1 to 9 and Comparative Examples 1 to 4 was observed one week after the production, and the storage stability was confirmed. The rating criteria are as follows. 〇: No change. x: Aggregates were observed (no evaluation of adhesion). Each of the aqueous polyurethanes of Examples 1 to 9 and Comparative Examples 1 to 4 was added. The oxime resin dispersion 'addition polymerization initiator (IRGACURE 500, Ciba) Specialty Chemicals Co., Ltd.) 3 wt% / solid content, fully stirred to the coating agent. This was uniformly applied to an acrylic resin so that the film thickness after drying of 60 323441 201217408 became about 20/zm. Then, it was dried at 60 ° C for 30 minutes to obtain a coating film (before ultraviolet irradiation). Touch the coating film to evaluate that it is non-sticky. The rating criteria are as follows. 〇: No change X: Fingers or fingerprints will remain. [Table 1] Composition Name Compound Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Polyol (a) U_(3/1 &gt; 12 21 12 12 12 21 21 UH1 00 Isocyanate (d) IPDI 26 24 27 26 26 24 24 Acid-containing polyol (C) DMPA 5 5 5 5 5 5 5 Chain extender (C) MPMD 4 3 2 4 DETA 2 1 AH 3 肼3 Hexahydrogen 0 Qin (meth)acrylic compound (e) 1.6-HDL-EP-A 6 6 6 6 PETA 9 8 9 g 9 8 8 (meth)acrylic compound (B) DPHA 38 39 39 TMPTA 39 39 39 39 hardness acrylic resin 2H ~3H Η~2H 2Η 2H 2H Η 密 Adhesive ABS resin 25/25 25/25 25/25 25/25 25/25 25/25 -25/25- 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 Acrylic resin 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 PC resin 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/ 25 25/25 25/25 25/25 storage Storage stability 〇〇〇〇〇〇〇 no stickiness 〇—Ω..... 〇〇〇〇〇61 323441 Turtle 201217408 [Table 2] Composition Name Example 8 Example 9 Comparative Example 1 Comparative Example 2 Comparison Example 3 Comparison of Life Fi&quot; Polyester (a) UM90&lt;3/1) 21 14 19 19 — UH100 19 15 Isochlorite IPDI 24 20 24 26 25 43 Acid-containing Poly® Dmpa 5 5 5 4 4 8 Chain Extruder (C) MPMD 5 5 3 6 DETA AH 肼 hexahydropyrene 3 (methyl) enoate compound (e) 1.6-HDL-EP-A 7 6 10 PETA 8 31 8 14 (methyl) propylene Compound (Day) DPHA 30 TMPTA 39 47 3Θ 39 Hardness Acrylic Resin Η 2Η 〜3Η Η~2Η Η—2Η 2Η 密 Adhesive ABS Resin 25/25 25/25 25/25 16/25 16/25 25/25 25 /25 25/25 25/25 12/25 15/25 25/25 25/25 25/25 25/25 0/25 1/25 25/25 Post-propylene resin 25/25 25/25 25/25 15/25 20/25 11/25 25/25 25/25 25/25 2/25 14/25 10/25 25/25 25/25 25/25 2/25 4/25 0/25 PC resin 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 25/25 2 5/25 25/25 25/25 Storage stability ο 〇 XX 〇〇 No stickiness ο X 〇〇Ο 1 Ο The heavy injury in the table is not in the total solids in the resin (including acrylic acid compounds) The parts by weight of each compound in the case of 1 part by weight. The erroneous pen hardness in the table, for example, "H" means that the pencil with Η is completely scratch-free 2 Η to 3 Η" means that it is scratched or scratched with a pencil of 3 inches, and is completely scratch-free with 2 inches. The adhesion in the table indicates the result of the peel test. "25/25" indicates that 25 of the 25 grids are in close contact after the test. As shown in the above table, the aqueous polyaminophthalate resin dispersion system of the examples can form a coating film excellent in adhesion and excellent in storage stability. In the preparation of the polyurethane resin, the storage stability in Comparative Example 1 in which the unsaturated mouth (e) was not used was inferior. In the preparation of the polyurethane resin (A), the main chain is not used 62 323441 201217408. Comparative Examples 2 and 3 of the polycarbonate diol (a) having a % structure, and an aqueous polyurethane In any of Comparative Example 4 in which the compound (B) having a polymerizable unsaturated bond was not blended in the resin dispersion, the adhesion was poor. By comparing the results of Comparative Example 2 with Comparative Example 3, it was found that the storage stability of the aqueous polyurethane resin dispersion can be improved by using the unsaturated compound (e,) having one hydroxyl group in one molecule. By comparing the results of Example 5 and Example 6, it was found that the coating film obtained from the aqueous polyurethane resin dispersion was obtained by using the unsaturated compound (e,) having two or more hydroxyl groups in one molecule. The hardness can be increased. Further, by comparing the results of Example 1 and Example 9, it was found that the dry coating film before ultraviolet irradiation had high tackiness by using a chain extender. [Industrial Applicability] The aqueous polyaminophthalate resin dispersion system of the present invention can be widely used as a raw material of a coating material or a coating agent. [Simple description of the diagram] None. [Main component symbol description] None. 323441 63

Claims (1)

201217408 七、申請專利範圍： 1. 一種水性聚氨基甲酸酯樹脂分散體，其係使至少具有 聚合性不飽和鍵之聚氨基甲酸酯樹脂（A)與具有聚合 性不飽和鍵之化合物（B)分散於水系介質中而成之水 性聚氨基甲酸酯樹脂分散體，其特徵係： 具有聚合性不飽和鍵之聚氨基甲酸酯樹脂（A)為 使至少於主鏈具有脂環構造之聚碳酸酯二醇（a)、含 有酸性基之多元醇（b)、多元異氰酸酯（d)、與工分 子中具有1個以上可與異氰酸基反應的基與丨個以上 來合性不飽和鍵的化合物（e)反應所得到的聚氨基甲 酸酯樹脂。 2. 申請專利範圍第1項所述之水性聚氨基甲酸醋樹脂 刀政體其中具有聚合性不飽和鍵之化合物（B)包含 Ί Am ^ τα — .. 3. 4. 至少含有3個（甲基）丙烯醯基之化合物 ^申凊專利範圍第1或2項所述之水性聚氨基甲酸醋 樹月曰分散體’其巾具有聚合性不鮮鍵之化合物（B) 包含至少含有5個（甲基）㈣喊之化合物。 t申請專利第1至3射任—項所狀水性聚氨 =㈣樹脂分散體，其中1分子中具有以上可 酸基反應的基與1個以上聚合性不飽和鍵的化 2 ^ 〇包含具有1個可與異氰酸基反應之基與1個_ 上（甲基）丙烯醯基的化合物。 如申3青專利範圍第1至 其t 至4項中任一項所述之水性聚氨 樹脂分散體，其中1分子中具有丨個以上可 323441 1 5. 201217408 與異《基反應㈣與丨㈣上聚合性讀和鍵的化 合物（e)包含具有1個可與異氰酸基反應之基與3個 以上（甲基）丙烯醯基的化合物。 6.如申請專利範圍第！至5項中任一項所述之水性聚氛 基甲酸醋樹脂分散體，其中！分子中具有！個以上可 與異氰酸基反應的基與i個以上聚合性不飽和鍵的化 合物（e)包含具有2個經基與2個（甲基）丙稀醯基的 化合物。 7.如申請專利範圍第項中任一項所述之水性聚氨 基甲酸醋樹脂分散體，其中具有聚合性不飽和鍵之聚 風基甲酸醋樹脂係由使至少主鏈具有脂環構造之聚碳 酸酯二醇（a)、含有酸性基之多元醇（b)、多元異氰 酉文酉曰（d)、與1分子中具有丨個以上可與異氰酸基反 應的基與1個以上聚合性不飽和鍵的化合物⑴、鏈 延長劑（C)反應而得。 .如申明專利範圍第7項所述之水性聚氨基甲酸酯樹脂 刀政體，其中鏈延長劑（C)為丨級多胺化合物。 種如申凊專利範圍第1至6項中任一項所述之水性 聚氨基曱酸酯樹脂分散體之製造方法，其係包含： 使至少於主鏈具有脂環構造之聚碳酸酯二醇 (a)、含有酸性基之多元醇多元異氰酸酯（d)、 與1分子中具有1個以上可與異氰酸基反應的基與1 個以上聚合性不飽和鍵的化合物（e)反應而得到聚氨 基甲酸酯樹脂（A)， 2 323441 201217408 鍵之具有聚合性不飽和 H). -種如申請專·_ 7或8項所叙水性聚氨基甲 酸_脂分散體之製造方法，其係包含如下步驟： 使至y於主鏈具有脂環構造之聚碳酸酯多元醇 U)、含有酸性基之多元醇⑴、多元異氰酸醋⑷、 與具有1個以上可與異氰酸基反應的基與1個以上聚 合性不飽和鍵的化合物⑴反應而得㈣氨基甲酸醋 預聚物（A1)之步驟（α丨）、 中和聚4基甲酸自旨預聚物（川之酸性基的步驟 (幻、 使聚氨基甲酸酯預聚物（Α1)與具有聚合性不飽 和鍵之化合物（Β)分散於水系介質中之步驟（γ)、 使聚氨基甲酸酯預聚物（Α1)、與聚氨基甲酸酯預 聚物（Α1)之異氰酸基具有反應性的鏈延長劑（c)反 應而得到水性聚氨基甲酸酯樹脂的步驟（3 )。 U.如申請專利範圍第1至8項中任一項所述之水性聚氨 基甲酸酯樹脂分散體，其中進一步含有光聚合起始劑。 12. —種塗料組成物，其係含有如申請專利範圍第1至8 項及11項中任一項所述之水性聚氨基甲酸酯樹脂分散 體者。 13. —種塗佈劑組成物，其係含有如申請專利範圍第1至$ 項及11項中任一項所述之水性聚氨基甲酸酯樹脂分散 體者。 323441 3 201217408 四、指定代表圖：本案無圖式。 (一) 本案指定代表圖為：無。 (二) 本代表圖之元件符號簡單說明：無。 五、本案若有化學式時，請揭示最能顯示發明特徵的化學式： 本案無代表化學式。 3 323441201217408 VII. Patent Application Range: 1. An aqueous polyurethane resin dispersion which is a polyurethane resin (A) having at least a polymerizable unsaturated bond and a compound having a polymerizable unsaturated bond ( B) an aqueous polyurethane resin dispersion obtained by dispersing in an aqueous medium, characterized in that the polyurethane resin (A) having a polymerizable unsaturated bond has an alicyclic structure at least in the main chain The polycarbonate diol (a), the acidic group-containing polyol (b), the polyvalent isocyanate (d), and one or more groups capable of reacting with an isocyanate group in the industrial molecule are more than one or more. The polyurethane resin obtained by the reaction of the unsaturated bond compound (e). 2. The aqueous polyurethane resin in the first aspect of the patent application, wherein the compound (B) having a polymerizable unsaturated bond contains Ί Am ^ τα — .. 3. 4. at least 3 (methyl The compound of the acryl oxime group according to claim 1 or 2, wherein the compound having a polymerizable non-fresh bond (B) contains at least 5 (A) Base) (4) Compounds called. t Patent application Nos. 1 to 3, the water-based polyurethane = (4) resin dispersion in which the group having the above acid group reaction and the one or more polymerizable unsaturated bonds in one molecule contain 2 ^ 〇 A compound which is reactive with an isocyanate group and a compound of 1 (meth)acryloyl group. The aqueous polyurethane resin dispersion according to any one of claims 1 to 4, wherein the one molecule has more than one of the 323441 1 5. 201217408 and the different "base reaction (four) and 丨(4) The compound (e) having an upper polymerizable read bond and a bond includes a compound having one group reactive with an isocyanate group and three or more (meth)acrylonium groups. 6. If you apply for a patent range! The aqueous dispersion of formic acid vinegar resin according to any one of the five items, wherein! Have in the molecule! The compound (e) having more than one group reactive with an isocyanate group and one or more polymerizable unsaturated bonds contains a compound having two trans groups and two (meth) acrylonitrile groups. 7. The aqueous polyurethane resin dispersion according to any one of the preceding claims, wherein the polyaluminum vinegar resin having a polymerizable unsaturated bond is a polymer having at least a main chain having an alicyclic structure. Carbonate diol (a), polyol (b) containing an acidic group, polyisocyanate (d), and one or more groups capable of reacting with an isocyanate group in one molecule and one or more The polymerizable unsaturated bond compound (1) and the chain extender (C) are obtained by reaction. The aqueous polyurethane resin according to claim 7, wherein the chain extender (C) is a hydrazine polyamine compound. The method for producing an aqueous polyaminophthalic acid resin dispersion according to any one of claims 1 to 6, which comprises: a polycarbonate diol having an alicyclic structure at least in the main chain. (a) a polyol-containing polyvalent isocyanate (d) containing an acidic group, and a compound (e) having one or more reactive groups capable of reacting with an isocyanate group in one molecule and one or more polymerizable unsaturated bonds are obtained. Polyurethane resin (A), 2 323441 201217408 bond with polymerizable unsaturated H). - A method for producing a water-based polyurethane-lipid dispersion as described in Application No. 7 or 8 The method comprises the steps of: a polycarbonate polyol U) having an alicyclic structure in the main chain, a polyol (1) containing an acidic group, a polyisocyanate (4), and having more than one reactable with an isocyanate group The reaction of the compound (1) with one or more polymerizable unsaturated bonds gives the step (4) of the urethane acetal prepolymer (A1) (α丨), and the neutralization of the poly 4-formic acid from the prepolymer (the acidic group of Sichuan) Step (phantom, make polyurethane prepolymer (Α1) with polymerization a step (γ) of dispersing a compound of an unsaturated bond (Β) in an aqueous medium, an isocyanate group of a polyurethane prepolymer (Α1), and a polyurethane prepolymer (Α1) The step (3) of obtaining the aqueous polyurethane resin by reacting the reactive chain extender (c). The aqueous polyurethane of any one of claims 1 to 8. The resin dispersion further comprising a photopolymerization initiator. 12. A coating composition comprising the aqueous polyurethane resin according to any one of claims 1 to 8 and 11 A dispersion agent composition comprising the aqueous polyurethane resin dispersion according to any one of claims 1 to 10 and 11 of the claims. 323441 3 201217408 IV. Designated representative map: There is no schema in this case. (1) The representative representative of the case is: No. (2) The symbol of the symbol of the representative figure is simple: No. 5. If there is a chemical formula in this case, please reveal the best display invention. Chemical formula of the character: This case does not represent a chemical formula. 3 32344 1
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