TW201245350A - Active-energy-curable resin composition and coating agent - Google Patents

Active-energy-curable resin composition and coating agent Download PDF

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TW201245350A
TW201245350A TW101107966A TW101107966A TW201245350A TW 201245350 A TW201245350 A TW 201245350A TW 101107966 A TW101107966 A TW 101107966A TW 101107966 A TW101107966 A TW 101107966A TW 201245350 A TW201245350 A TW 201245350A
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compound
polyol
acid
meth
acrylate
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TW101107966A
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Chinese (zh)
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TWI515272B (en
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Atsushi Tsujimoto
Toshiro Noda
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Nippon Synthetic Chem Ind
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    • 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
    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing

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

Abstract

Provided are: an active-energy-curable resin composition which enables the production of a cured coating film having enough restoring performance for practical use and excellent stretching performance; and a coating agent prepared using the active-energy-curable resin composition. This active-energy-curable resin composition contains a urethane (meth)acrylate compound (A) produced by reacting a polyol compound (x), a (meth)acrylate compound (y) containing a hydroxy group and a polyvalent isocyanate compound (z) with one another and having a weight average molecular weight of 10,000 to 800,000, and is characterized in that the polyol compound (x) comprises a polyol compound (x1) containing at least three hydroxy groups.

Description

201245350 六、發明說明： 【發明所屬之技術領域】 [0001] 本發明係關於活性能量射線硬化性樹脂組成物及塗佈劑，更 洋吕之’係關於用以形成對於損傷的復原性或伸縮性優異之硬化 塗膜的活性能量射線硬化性樹脂組成物，及使用該組成物而成的 塗佈劑。 【先前技術】 [0002] 以往’活性能量射線硬化性樹脂組成物係藉由極短時間的放 射線等活性能量射線的照射而完成硬化，所以廣泛使用於當作對 於各種基材的塗佈劑或黏著劑、或黏底塗層(mchor c〇at)劑等。 [0003] 、 / *其中，就塗佈劑而言，希望開發在塑膠基材表面形成硬化被 覆膜，並且就保護基材最表面的塗佈劑而言，希望開發能夠形成 對於損傷具有復原性的硬化塗膜的活性能量射線硬化性樹脂組成 ，，例如有人提出:使用使含聚己内酯之多官能醇與異氰酸酯與含 ^基之（曱基)丙烯酸酯反應而獲得之胺曱酸酯丙烯酸酯募聚物的 紫外線硬化性塗佈組成物(例如:參照專利文獻i)。 先前技彳衧文獻 專利文獻 [0004] 專利文獻1:日本特開2004-35599號公報 【發明内容】 [發明欲解決之課題] [0005] _ 上述專利文獻1之揭示技術，係藉由使用含己内酯之多 - g此醇§作胺曱酸酯（甲基)丙烯酸酯系化合物的構成原料，當製成 201245350 而要車乂冋刀子i且需要類似於高分子橡膠的 貫用上難以獲得充分等級的復原性。 ^發明在如此的背景下，目的在於提供製成硬化塗膜 耐叉貫用性的等級的復原性及伸縮性優 ς、卜二 樹脂組成物，及使用該組成物的塗佈劑。）報㈣射線硬化性 [解決課題之方式] [0007] 多』情事努力研究’結果:藉由在使 夕兀知糸化&物、含經基之（甲基)丙稀酸^ ^^ ^201245350 VI. Description of the Invention: [Technical Field of the Invention] [0001] The present invention relates to an active energy ray-curable resin composition and a coating agent, and more relates to the formation of a recovery or expansion for damage. An active energy ray-curable resin composition of a cured coating film having excellent properties, and a coating agent using the composition. [Prior Art] [0002] Conventionally, an active energy ray-curable resin composition is hardened by irradiation with an active energy ray such as radiation for a very short period of time, and is therefore widely used as a coating agent for various substrates or Adhesive, or mchor c〇at agent. [0003] / / Among them, in the case of a coating agent, it is desired to develop a hard coating film on the surface of a plastic substrate, and in order to protect the coating agent on the outermost surface of the substrate, it is desired to develop a recovery capable of forming damage. The composition of the active energy ray-curable resin of the hardened coating film, for example, it has been proposed to use an amine citric acid obtained by reacting a polycaprolactone-containing polyfunctional alcohol with an isocyanate and a thiol-containing acrylate. An ultraviolet curable coating composition of an ester acrylate copolymer (for example, see Patent Document i). [Patent Document 1] Japanese Laid-Open Patent Publication No. 2004-35599 [Draft of the Invention] [Problems to be Solved by the Invention] [0005] The technique disclosed in the above Patent Document 1 is by using The amount of caprolactone - g of this alcohol is used as a constituent material of the amine phthalate (meth) acrylate compound. When it is made into 201245350, it is difficult to use the kiln knife i and it is difficult to use it similar to polymer rubber. Get a full level of resilience. In view of the above, it is an object of the present invention to provide a resilience and stretchability of a hardened coating film which is resistant to cross-linking properties, a resin composition, and a coating agent using the composition. (4) Radiation hardening [the way to solve the problem] [0007] More erotic efforts to study the results: by knowing the 兀 & & amp amp amp 含 含 含 含 含 含 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^

Sit 物== 具備由於3維網目構造而得的塗膜收縮性，可 獲付具有伸張、收縮性能的橡膠彈性塗膜。所以， 成對於損傷的復雜優異的硬化麵，乃完成林明。〇 y 橋_匕二入Ur 土々夕兀醇系化合物當作胺甲酸酯（曱基)丙 L Ϊ 原料之多猶系化合物，能夠緩解合成時 合物’於硬化塗獅成後可發揮本發明之顯 [0008] ㈣亦明，要旨係關於一種活性能量射線硬化性樹脂組 錄多二;=;含= 201245350 (xl) 又 組 成物而成射線硬化性_ [0009] 1 4儿/、疋使用在取表面的塗佈劑。 [發明之效果] 時對 尤其當作最表面用塗佈劑為有用。I、之效果’ §作塗佈劑’ 【實施方式】 [0010] 以下詳細說明本發明。 美，(又甲其ΙΐΓΛ’ΛΙ基)丙婦酸基係指丙稀酸基或子基丙烯酸 ί在if 基係糾_麵甲絲_基，（甲基)丙烯酸 醋係指丙烯酸酯或甲基丙埽酸酿。 i 巷)内狀 [0011] 本發明之活性能量射線魏性難 (甲基)丙稀酸酯系化合物(A)而成。 U錢r酉夂酉曰 [0012] [胺甲酸酯（甲基)丙烯酸酯系化合物(A)] 本，明使用之胺甲酸醋(甲基〕丙稀酸酉旨系化合物⑷，係使含 其以基的多元醇系化合物(xl)的多元醇系化合物 合物酸酉旨系化合物(y)、及多元異氰酸_ [0013] 仆入L元^系化合物(x) ’只要含有含3個以上的經基的多元醇系 W之多娜化合物㈣」 [0014] 201245350 的經▲的各種多元2 化合物⑽’可舉例如含有3個以上 聚醚系多元醇、具體而言，例如:聚酯系多元醇、 二烯系多元Ϊ、(; 、聚稀煙系多元醇、狀聚丁 分子中不含不飽和基之 又，從糸多元醇、聚石夕氧貌系多元醇等 ^•处U μ Μ Γ Μ之透明性優異的觀點 β此以上的多元醇系化。 [0015] 人物^例如:多元醇與多元敌酸的縮聚物;環狀醋 成的ϋΪΐ /减、乡續較勸旨之3種成分製 應物，4,可舉例如:麵各原料使得含有3個以上的絲者。 j多元醇，例如:乙二醇、二乙二醇、丙二醇、二丙二醇、Sit material == With the shrinkage of the coating film due to the 3-dimensional mesh structure, a rubber elastic coating film having stretch and shrink properties can be obtained. Therefore, Lin Ming is completed as a complex hardened surface for damage. 〇y bridge _ 匕 入 U Ur Ur 々 兀 兀 化合物 当作 当作 当作 当作 当作 当作 U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U U The invention [0008] (4) also clarifies that the main point is that an active energy ray-curable resin group is more than two; =; with = 201245350 (xl) and the composition is ray hardening _ [0009] 1 4 /疋Use a coating agent on the surface. [Effect of the Invention] It is particularly useful as a coating agent for the outermost surface. I. Effect § As a coating agent ‘Embodiment】 [0010] Hereinafter, the present invention will be described in detail. Beauty, (also A ΙΐΓΛ ΛΙ ΛΙ ) 丙 ) ) ) ) ) 系 系 系 if if if if if if if if if if if if if if if if if if if if if if if if if if if if if if if if if Studic acid brewing. i ( Lane) Internal shape [0011] The active energy ray of the present invention is composed of a (meth) acrylate-based compound (A). U 酉夂酉曰 酉夂酉曰 [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ The polyol compound compound (y) and the polyisocyanate of the polyol compound (x1) containing the group-based polyol compound (xl) are exemplified as the L-component compound (x) The polyvalent alcohol compound (4) containing three or more kinds of radicals is a mixture of three or more polyether polyols, for example, including, for example, three or more polyether polyols. : Polyester-based polyols, diene-based polyvalent oximes, (;, poly-smoke-based polyols, polyunsaturated molecules, which do not contain unsaturated groups, and bismuth polyols, polyoxo oxopolyols, etc. ^• U μ Μ Γ 优异 优异 优异 优异 β β β β β β β β β β β β β β β [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ For the three components of the above-mentioned ingredients, 4, for example, the raw materials of the surface may contain three or more wires. j Polyol, for example, ethylene glycol, diethylene glycol , Propylene glycol, dipropylene glycol,

If—醇、M_四亞甲基二醇、四亞甲基二醇、2-甲基-1，3· 基—醇、u_五亞曱基二醇、新戊二醇、l6·六亞曱基二醇、 -甲基-1，5-五亞甲基三醇、2,4_二乙基妙五亞甲基二醇、甲烧三 醇j油、三經甲基丙烷、三羥曱基乙烧、環己二醇類(1，4-環己 —醇等）、雙酚類(雙酚A等）、糖醇類(木糖醇或山梨醇等)等。 [0017] 一上述多元羧酸’例如:丙二酸、馬來酸、富馬酸、琥珀酸、戊 二酸、己二酸、辛二酸、壬二酸、癸二酸、十二烷二酸等脂肪族 二綾酸;1，4-環己烷二羧酸等脂環二羧酸;對苯二甲酸、間苯二曱 酸、鄰苯二曱酸、2,6-萘二羧酸、對伸苯基二羧酸、偏苯三曱酸等 芳香族二羧酸等。 [0018] 上述環狀酯（内酯）’例如:I丁内酯、δ-戊内酯、ε-己内酯等。 [0019] 上述聚醚系多元醇’可舉例如:將成為原料的多元醇進行脱水 縮合使得在分子末端(分子側鏈)含有3個以上的羥基而得的聚醚 糸多元醇。 201245350 該多元醇，只要是含有至少1個3官能 例如：甲烷三醇、甘油、三羥曱基两烧'一^之多凡醇即可， 三醇、季戊四醇等低分子量之 醇巧，:己燒 (alkylene oxide)加成物即聚環氧烷多元醇等。夕7^醇的裱氧烷 [0020] ’ 上述聚碳酸酯系多元醇，例如:為多元 3個h以上，基的多元醇者^環狀碳‘(碳=ΐί [2ίΓ te导之開環聚合物且含有3個以上之 上述多元醇’只要是含有至少i個3官 一 例如：甲烷三醇、甘油、三羥甲基丙烧、二 夕兀醇即可， 醇、季戍四醇等低分子量的多元醇；^土三 (alkylene oxide)加成物即聚環氧烧多元醇等。、夕凡-子的％氧烷 又’聚碳酸衫it醇，只妓分子内具有韻 含有3個以上的經基的化合物即可，也可同時 = (carbonate bond；)與酯鍵(；este]： bcmc〇。 -夂酉曰鍵 [0022] 上，聚烯烴系多元醇’只要是在具有至少丨個分支構 刀子末端(側鍵)合計具有3個以上的經基者即可。 卫 上述虱化^^丁一細糸多元醇，只要是平丁 _膝会取夕_二 構造中所含的乙雕讀和基完全触^ 鏈)具有合計3個以上的羥基即可。 再、I/、刀子末知(側 [0024] 物中乡元醇，p礙在(f細肺旨之聚合 物中或壯合物中含有至少3個以上的經基者即可。該聚 共=之構成早體，可舉例如：（曱基)丙稀酸2_經基乙醋 ===(，稀酸2伽旨、(甲基)丙烯酸:) ΪΓ丙‘、=it6销己酯等(甲基)丙婦_基烧酯、（甲 基)丙㈣”曰、(甲基)丙烯酸乙醋、(甲基)丙烯酸丙醋、(甲基)丙 201245350 2-^m ^ 酸十八酯等㈣)丙稀酸炫H(甲基)丙細酸十二醋、（，丙烯 [0025] 個以在她(主鏈)具妇 [0026] 點，3系,-ί硬，時的柔軟性、耐熱性等機械物性優異之觀 多蝴触。 3官能以上之多元醇系，^ ^ 3〇^50〇mgKOH/g , 40^,75〇4κ〇Η/ί ，絲若過高，合成階段^ 、ίί之而若該_賈過低，活性能量射. 後之錄表面的硬度會有容易降低的傾向。 5亥羥基知係依據JIS K 1557測定之値。 [0028] 3 g月b以上之多元醇系化合物(χ1)之重量平均 5〇；6,00〇10〇.3,50〇 , 能量射線尤其紫外線硬化後之塗膜表面的硬 度曰有谷糾低的傾向，若該重量平均分子量過低，則在合成階 ’ 3維網目構造會變得過於緻密，黏度會急劇上升，製造胺甲酸 酯（曱基)丙烯酸酯系化合物時會有容易凝膠化的傾 [0029] 、 ^又，上述重量平均分子量，係以標準聚苯乙烯分子量換算獲 巧的重里平均为子昼，精由於高速液體層析(曰本遍⑽公司製If-alcohol, M_tetramethylene glycol, tetramethylene glycol, 2-methyl-1,3·yl-alcohol, u-pentamethylene glycol, neopentyl glycol, l6·6 N-mercaptodiol, -methyl-1,5-pentamethylenetriol, 2,4-diethylpentamethylene glycol, metriol J oil, trimethylpropane, three Hydroxymercaptoethane, cyclohexanediol (such as 1,4-cyclohexanol), bisphenols (such as bisphenol A), sugar alcohols (such as xylitol or sorbitol). [0017] one of the above polycarboxylic acids 'for example: malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecane two Aliphatic dicarboxylic acid such as acid; alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid And an aromatic dicarboxylic acid such as phenyldicarboxylic acid or trimellitic acid. [0018] The above cyclic ester (lactone) is, for example, Ibutyrolactone, δ-valerolactone, ε-caprolactone or the like. The polyether polyol may be, for example, a polyether oxime polyol obtained by dehydrating and condensing a polyol as a raw material to have three or more hydroxyl groups at a molecular terminal (molecular side chain). 201245350 The polyol may be a low molecular weight melamine such as triol or pentaerythritol, as long as it contains at least one trifunctional, for example, methane triol, glycerin, or trihydroxyindole. An alkylene oxide adduct is a polyalkylene oxide polyol or the like.裱 ^ 醇 [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ [ The polymer further contains at least three of the above-mentioned polyols as long as it contains at least one of three groups, such as methane triol, glycerin, trimethylolpropane, and tantalyl alcohol, alcohol, tetradecyl alcohol, and the like. Low molecular weight polyol; alkylene oxide adduct is polyepoxy burned polyol, etc., Xifan-zi's % oxane and 'polycarbonate' it alcohol, only 妓 has a rhyme containing 3 More than one trans-based compound may be used, or may be both (carbonate bond) and ester bond (; este): bcmc 〇 - 夂酉曰 bond [0022], the polyolefin-based polyol 'as long as it has At least one branch of the knives (side keys) may have a total of three or more bases. The above-mentioned sputum is a fine sputum, as long as it is a ping _ knee will take the eve _ two structure The inclusion of the B-engraving and the base-complete chain can have a total of three or more hydroxyl groups. Further, I/, the knife is known (the side [0024] in the township alcohol, p (The polymer of the fine-grained polymer or the complex contains at least three or more bases. The aggregate of the aggregates is exemplified by: (mercapto) acrylic acid 2 _ base Ethyl vinegar ===(, dilute acid 2 gamma, (meth)acrylic acid:) ΪΓ ' ', = it 6 pin hexyl ester, etc. (methyl) propyl ketone ester, (meth) propyl (tetra) 曰, (meth)acrylic acid ethyl vinegar, (meth)acrylic acid propyl vinegar, (methyl) propyl 201245350 2-^m ^ acid octadecyl ester, etc. (4)) acrylic acid H (methyl) propionate twelve vinegar, (, propylene [0025] In the (the main chain) with a woman [0026] point, 3 series, - ί hard, when the softness, heat resistance and other mechanical properties are excellent. Alcohol, ^ ^ 3〇^50〇mgKOH/g, 40^, 75〇4κ〇Η/ί, if the silk is too high, the synthesis stage ^, ίί and if the _ Jia too low, active energy shot. The hardness of the surface to be recorded tends to be lowered. 5. The hydroxy group is determined according to JIS K 1557. [0028] The weight of the polyol compound (χ1) of 3 g month b or more averages 5 〇; 6,00 〇 10〇.3,50〇, the hardness of the surface of the coating film after energy ray, especially UV curing, If the weight average molecular weight is too low, the three-dimensional mesh structure in the synthesis stage will become too dense, the viscosity will rise sharply, and the urethane (mercapto) acrylate compound will be easily condensed. The gelation of the [0029], ^, the above weight average molecular weight, based on the standard polystyrene molecular weight conversion of the weight of the average weight of the sub- 昼, fine due to high-speed liquid chromatography (曰本(10) company

Waters 2695(本體)」與「Waters 2414(檢測器）」)，管桂.Sh〇d GPC KF-狐(排除分界分子量;測7、分離範圍侧〜2χ1〇7、理論板 201245350 數:10,000板/根、填充劑材質:苯乙烯_二乙烯基苯共聚物、填充劑 粒徑:1 Ομιη)串聯3根進行測定。 [0030] 又’多兀醇系化合物⑻含有含2個羥基且羥基價小於 4^0mgKOH/g的多元醇系化合物(χ2)(以下有時記載為「2官能多元 醇系化合物(χ2)」）時，可防止3維網目構造變得過於緻密，並可 防止製造胺甲酸酯（曱基)丙烯酸g旨系化合物時發生凝膠&，於能穩 定製造胺價自旨(f基)㈣酸I纽合物 [0031] ^^夕70醇系化合物㈣之經基價必需小於45〇mgK〇H/g， 18〇mgK〇H/g — 财錄制於緻密， 有容易凝膠化的傾向= 外面之硬度會有容易降低=向 編維據咖557測定之値。 多元有2健基的各種 聚碳酸酯系μ醇、聚_系多元、聚_多元醇、 基)丙蝉酸系多元醇、聚石夕氧燒系 g♦丁二稀系多元醇、（甲 具體而言，可依據上述3官能以上〜 明中所例示之各多元醇系化合物 口夕^系化合物(XI)之説 合物使羥基成為2個而得之2官能多元醇、^。疋選擇並組合原料化 厶t 月& ，，以性優異的觀點，2官 [0034] 201245350 2官能多元醇系化合物(x2)之重 階段的3維網目構造會變得過於千^刀於= =醋⑽罐I祕崎有，。製造 3官合物(X)’使用2 _元_化合物㈣時， #；；ΐΓίί；ί^Τ(^ (xlKx^i H 為）:()9〜":1較佳，尤佳為 W，㈣-=8〜50:50，又更佳為(χ1):(χ2)=3:97〜3〇:7〇。 網目二多元醇系化合物(Xl)之锋合比例若過多，3維 = ’分子量變得過高’製造時會有容易凝膠化 均W生優異會有變得困難的傾向。 甲祕及㈣的 [0036] 450m ι<^Λ醇系化合物(Χ) ’宜含有含2個經基且經基價為 夕- ^ gM上之多元醇系化合物(χ3)(以下有時記載為「2官能 物㈣」）較佳，尤其為除了上述記載之3官能多元 私系化合物(xl)、2官能多元醇系化合物(χ2)以外，還更含有含2 ，經基且誠價為45GmgKOH/g以上〇元醇系化合物(χ3)時， =使胺甲酸酯（甲基）丙烯酸酯系化合物之3維網目構造更為舒 緩，且塗膜伸縮性提高之觀點為較理想。 [0037] 丄2官能多元醇系化合物(χ3)之羥基價，需為45〇mgK〇H以上， 較佳為500mgKOH/g以上，尤佳為550mgK〇H/g以上。又，該羥 基價之上限通常為2,000mgKOH/g。 該羥基價係依據JIS K 1557測定之値。 [0038] 201245350 以下ί Hi ΐ多兀醇系化合物(x3)，例如:重量平均分子量約250 二醇化合物，具體而言，可舉例如:乙二醇、二乙 it 2 二醇、三亞甲基二醇、二鮮基丙炫、新戍 丙二醇、2_丁基_2_乙基妙丙二醇、四 五亞f基二醇、π六亞甲基二醇、 ·^甲H，5一 五亞!基：醇、季細醇：「嫩ΐ = 二醇ί 己1醇類辛脂肪族醇類、μ_環己二醇、環己基二甲醇等環 笨:贫又等雙賴、三環癸烧二甲醇、木糖醇或山半醇 雜酵f等，該等可以使用1種或併用2種以上 木知 亥ί之中’《硬化塗膜之黃變性之觀點，宜為不含若夭产·^ ;飽和基之結構的化合物，尤佳為脂肪族醇類，又更佳為 [0039] 〇〜50重量％較佳，户乒盔Λ 1川私糸化5物(χ2)之合計量，為 為.3〜4〇重量％，又更佳為0.5〜25重量。/! 升，^胺°甲==其維網目結構會變得過於緻密，黏度急劇^ :甲W日㈣)丙烯嶋化合物時會有容易凝膠化= [0040] ^ΐ〇5：ί?；^^ —〇> ^ ^ 衡性優困 彈 =構會_大’分得過高，製造時會有容^^ [0041] g返平均絲數’係依以下計算式⑴或叫求得者。 201245350 a平均羥基數=從官能以上之多元醇系化合物(xl)之羥基官 月&基數x3官能以上之多元醇系化合物(χ1)之添加莫耳數)/ {3官能 以上之多元醇系化合物(Xl)之羥基價計算之分子量+從2官能多元 醇系化合物(Χ2)之羥基價計算之分子量}]十從[{2χ2官能多元醇系 化=^勿^2)之添加莫耳數}/{3官能以上之多元醇系化合物(χ1)之羥 基價計异之分子量+從2官能多元醇系化合物(χ2)之羥基價計算之 分子量}] ' [Π] λ平均羥基數=從[Ρ官能以上之多元醇系化合物(xl)之羥基官 月b基數x3官能以上之多元醇系化合物(χ1)之添加莫耳數丨/ {3官能 以十之多元醇系化合物(χ1)之經基價計算之分子量+從2官能多元 醇系化合物(X2)之經基價計算之分子量+從2官能多元醇系化合物 ㈣讀基價計算之分子量}]+從[阳冑能多元醇系化合物㈣之 添力1耳數}/ {3官能以上之多元料化合物(χ1)之經基價計算之 ^子量+從2官能多元醇系化合物㈣之經基價計算之分子量+從2 ，能多觸系化合物㈣之織價計#之分子量}]+從[{2><2官能 夕兀醇系化合物(x3)之添加莫耳數}/ {3官能以上之多元醇系化合 經基價計算之分子量+從2官能多元醇系化合物⑽之經 基仏計鼻之分子量+從2官能多元醇系化合物(χ3)之羥基價計算之 分子量}] 、 ^ [0042] 含羥基之(甲基)丙烯酸g旨系化合物(y)，例如：（甲基)丙稀酸孓 羥基乙醋:（甲基)丙蝉酸2_絲丙醋、（甲基)丙烯酸L經基丁醋、 (甲基)丙烯酸4_經基丁醋、（甲基)丙烯酸卜經基己轉（甲基 η細旨、2_絲乙基丙烯酿基顧_、2_(甲基)丙稀酿氧乙基 =二甲酸s旨、二丙二醇(阳丙触醋、脂肪酸改性 (=)丙烯砂氧丙醋、聚乙二醇單⑶基)丙婦酸醋、聚丙二醇單 =基)丙烯酸酉旨、2_經基各(甲基)丙烯醯氧丙基丙稀酸酯等 =有1個乙烯性不飽和紅含經基之⑼基)丙稀酸醋系化合物;甘 ’由-(?基)丙婦酸醋、2-絲-3—丙烯醮氧丙基▼基丙婦酸醋、季戊 12 201245350 四醇二（甲基)丙稀義、環氧乙烧(ethylene 〇xide)改性季戊四醇三 (曱基)丙稀義、二季戊四醇五(曱基)丙稀酸醋、環氧乙烧改性二 f戊二醇五(曱基)丙烯咖旨等含t 2個以上的乙烯性不飽和基的 ⑽基的（甲基)丙烯酸酯系化合物，該等可使用也可組合使用 2種以上。 口 [0043] 斤八中’含ΐ1個乙稀性不飽和基的經基(甲基)丙烯酸I系 化合物較佳’從反應性及泛祕優異之觀點，（甲基)㈣酸2亭臭 乙酯、（甲基)丙烯酸2-絲丙酯、（甲基)丙烯酸2_經基丁甲 丙烯酸4-羥基丁酯尤佳，（曱基)丙稀酸2_ 土 [0044] Μ主 以下(甲基)丙烯酸酯系化合物(y)使用酸價lmgKOH/g 合物時乂足不易經基之(甲基)丙稀酸醋系化 s曰糸化合物之觀點為雛。纖價小於lmgKQH/g ^ f 合物，具體而言，可舉例如代 乙酉曰、（甲基)丙烯酸2-羥基丙酯、（甲基)丙烯酸2_羥基丁酯 遗基TS旨較佳，尤佳為(甲基)帥酸祕紅§旨。土） 又，含羥基之(甲基)丙烯酸酯系化合物之中，針對己 JriS烯，2_經基乙醋’一般能取得的原料，係己内醋1 ΐ耳改 ^右己内自日改性量增加，其酸價會有增加的傾向， ^旨改性㈣)丙触2_絲乙g旨，會有不紐得本發明之效果的傾 [0046] 多兀異氰酸酯系化合物(z)，例如:甲伸苯基二異氰酸 一 基甲烧二異驗g旨、聚苯基f絲 _旨 ^ 異氛_、亞二甲苯二異氰_、四甲基亞二甲苯二 13 201245350 伸苯基二^氰酸醋、萘二異氰酸酯等芳香族系聚異氰酸酯、六亞 〒基二異氰酸g旨、三甲基六亞p基二異氰酸酯、離胺酸二異氛酸 醋、，胺酸三異級g旨等脂肪⑽、聚異氰酸@旨、氫化二苯基甲烧 一欠g曰、氫化亞二甲苯二異氰酸酯、異佛爾酮二異氰酸酯、 坎稀f f氛酸醋、雙(異氣酸曱基)帛己烧等脂環系聚異氰酸 酉曰或。亥等聚異氰酸酯之3聚體化合物或多聚體化合物、腺甲酸 酯(jlophaiiate)型聚異氰酸酯、縮二脲型聚異氰酸酯、水分散型聚 異氰酸醋(例如：日本聚胺甲酸酯工業(股)製「AQUANATE 1〇〇」、 :A々QUANATE110」、「AqUANATE2〇〇」、「AQUANATE21〇」 等)等。 [0047] 該等之中，較佳為使用甲伸苯基二異氰酸酯、二苯基曱烷二 異氰酸酯、改性二苯基甲烷二異氰酸酯、亞二曱苯二異氰酸酯、 ϋΓ基亞苯二異氰酸§旨、伸苯基二異驗自旨、萘三異氰酸醋 寻，香知系一異氰酸酯;六亞甲基二異氰酸酯、三甲基六亞甲基二 異亂酸目旨〕離胺酸二異紐s旨等脂祕系二異氰義;氫化二苯基 甲烧一異氰酸§旨、氫化亞二甲苯二異氰咖旨、異佛爾酮二異氮酸 ，、降莰烯二異氰酸酯、L3—雙(異氰酸甲基)環己烷等脂環系二異 氮酸醋;等二異氰酸醋系化合物，從硬化塗膜之黃變少或硬化收縮 小的觀點，尤佳為脂環二異氰酸酯化合物，更佳為異佛爾酮二昱 旨、氫化二苯基甲烧二異驗§|、氫化亞二曱苯二異氮酸醋 藉由使含有上述(X)〜(z)之構成原料反應，可獲得胺甲酸酯 基)丙烯酸酯系化合物(A)。 [0049] 胺曱SscSa(甲基)丙細酸|旨糸化合物(A)之製造方法，通常可將 $元醇，化合物(X)、上述含經基之(曱基)丙稀酸醋系化合物(y): 夕元異氰酸醋系化合物(Z)—次添加或分次添加到反應器並使其反 應即可’而使多元醇系化合物(X)與多元異氰酸酷系化合物⑻預先 14 201245350 反應而獲得之反應產物，與含羥基之（甲基)丙烯酸酯系化合物(y) 反應之方法，從反應安定性或減少副產物等觀點為較佳。 [0050] 於使該多元醇系化合物(X)與多元異氰酸酯系化合物(z)預先反 應而獲得之反應產物使含羥基之（甲基)丙烯酸酯系化合物(y)反應 之方法中，上述多元醇系化合物(χ)與多元異氰酸酯系化合物之 反應，可，用公知之反應方法，例如:先以多元異氰酸酯系化合物 (Z)中之異氰酸酯基:多元醇系化合物(χ)中之經基的官能基莫耳比 ，通常約異氰酸酯基mol:(多元醇羥基m〇1，含羥基之丙烯酸酯之 經基111()1)而使其反應，而麟末端含有異氰_旨基之反應產物即 可。 [0051] 使上述多元醇系化合物⑻與多元異氰酸醋系化合物(z)的反應 產物，與含羥基之(甲基)丙烯酸s旨系化合物( ==方法，當反應產物與含經基之(曱基)丙雜旨系化= 的反應莫耳比為例如:反應產物之異旨基有2個、含絲 ί化合彳i(y)之絲有1辦，使反應產物:含經基之 ^(曱基)丙稀_系化合物(y)之有1個時，使 物相基之(曱基)丙湘_化合物(y)以約1:3反應即= 在该反應產物與含羥基之(甲基)丙稀酸醋系化 系之殘存異氰酸絲含有率成為° G,5重量二 合= 獲得本發明之胺他旨(甲基系化 [0053] 又’併用3官能以上之多元醇系化合物 ^物㈣時，3官能以上之多元醇系化合物(^Γ- ' ’、、、免”支、、、。構於胺曱酸酿(曱基)丙稀酸酉旨分 15 201245350 了使分支結構分散於胺甲酸醋（曱基)丙烯酸醋 刀子^ ’宜分成錯段摻合並使其反應較佳。 換人能以上之多元_化合物⑹時，可分割為任意 二例如:以2階段掺合時，從使分支結構以良好 酸醋(曱基)丙稀酸酷/分子中之觀點’宜以重量比第 二。2段，〜90:90〜10之範圍分次添加較佳。 弟 進物(χ)與多元異氰_旨系化合物⑵之反應， ^接於：I ，：’使用觸媒亦為較佳，該觸媒，可舉例如:二 物、錫基氫氧化錫、四正丁基錫等有機金屬化合 屬鹽、三乙夂胺、、=酸酸銘、氣化錫(1)、氯化錫⑼等金 雜擁淨「5 4Π^ ^一 ，氮雜雙環[2,2,2]辛烷、丨，8-二氮 觸媒、石肖_ m魏叙、硫化縛，此外，二 己酸i[丁it二月桂酸二辛基鱗有機叙化合物，或2_乙基 酸㈣、異癸齡鹽、新魏纏、月桂酸叙鹽、 鹽、硬脂_鹽、油_鹽、亞麻油酸㈣、乙酸錢鹽、 、二水揚酸繩、二没食子酸姆等有機_鹽蚤之 -^為理_、i其中，二月桂酸二丁基錫、1,8二氮雜雙環[5,4,0]十 [0055] 至I =夕兀醇系化合物(X)與多元異氰酸酯系化合物(z)之反應， +，：?：目、^應產物與含羥基之(甲基)丙烯酸酯系化合物(y)之反應 有對於異氰酸酯基反應之官能基的有機溶劑，可使用例 田奸s'、乙酸丁自旨等s旨類、f乙酮、甲基異丁細等酮類、 甲本、一甲苯等芳香族類等有機溶劑。 [0056] 有機溶劑也可改為使用不具有對異_®旨基反應之官 此基的（甲基)丙烯酸酉旨單體，該(甲基)丙烯酸醋系單體宜為2官能 16 201245350 (甲基)丙烯酸s旨單體、單官能(曱基)丙稀酸 ： [0057] 酉旨、4乙2-吕醇月匕_7甲$、丙稀，旨單體’例如:乙二醇二(曱基)丙婦酸 乙-ί 巧四乙二醇二(甲基)丙烯酸醋、聚 ，甲:?二二t 曰丙二醇二(甲基)丙烯酸酯、二丙二醇二 烯酸酯、環氧乙細_ a型i甲 甲性㈣A型：(甲基)丙烯酸酯、環己烧 曱酉予一(甲基)丙烯酸酿、乙氧基化環 [0058] 氣笨3官Λ(Ι基w_s_ ’例如:苯乙稀、乙縣甲苯、 細等苯乙烯系單體;（甲基)丙烯酸甲醋、（甲 rZtT，nC^ (甲基)丙稀酸庚酷、(甲基)丙烯酸辛；、(甲i二己二； 丙烯酸癸酯、（甲基)丙烯酸鮮丙=壬知、（甲基） _ 騎怖 i5Sla ^tfA^^l±(n=Z5) (f ^ ^ )丙版四虱槺酉曰、卡必醇(甲基)丙烯_旨、（甲基)丙烯酸丁氧基 17 201245350 乙醋、（甲基)丙烯酸烯丙酯、（甲基)丙烯醯基味啉、聚環氧乙烷二 級烷醚丙烯酸酯等丙烯酸酯系單體;N_羥曱基(甲基)丙烯醯胺、N_ 乙烯基吡咯烷酮、2-乙烯基吡啶、乙酸乙烯酯等。 [0059] 上述多元醇系化合物(X)與多元異氰酸酯系化合物之反應， 再者，其反應產物與含羥基之（曱基)丙烯酸酯系化合物(y)之反應 中，反應溫度通常為30〜loot：，較佳為40〜90〇C，反應時間通常 為2〜10小時’較佳為3〜8小時。 [0060] 本發明使用的胺曱酸酯（曱基)丙烯酸酯系化合物之乙烯性 不飽和基含量（mmol/g)，為〇.01〜10mm〇1/g較佳，尤佳為 0.05〜5mmol/g，又更佳為（U〜，尤佳為〇」〜〇 5mm〇1/g。 該胺甲酸酯（曱基)丙烯酸酯系化合物⑷之乙烯性不飽和基含 量(mmol/g)若過少，則活性能量射線照射時之硬化有不充分的傾 向，若過多則由於活性能量射線而形成交聯的成分會增加，會有 不易獲得目的之硬化塗膜之伸縮性及彈性的傾向。 [0061] 又，胺曱酸酯（甲基)丙烯酸酯系化合物(A)，從活用結構上之 特性即伸縮性、彈性之觀點，較佳為具有10個以下之乙烯性不飽 和基，尤佳為具有6個以下之乙烯性不飽和基，更佳為具有4個 以下之乙烯性不飽和基。又，通常乙烯性不飽和基之下限値 個。 ’ [0062] 本發明使用的胺甲酸酯（甲基)丙烯酸酯系化合物(A)之重量 均分子量，需為1萬〜80萬，尤佳為2萬〜5〇萬，又更佳為 萬。 »亥重里平均分子量若過小，硬化塗膜的伸縮性、彈性會有 低的傾向，若過大，黏度變高，會有不易操作的傾向。曰 [0063] 又，該重量平均分子量係與上述以同樣方法測定。 18Waters 2695 (body) and "Waters 2414 (detector)"), Guan Gui. Sh〇d GPC KF-fox (excluding the boundary molecular weight; measured 7, separation range side ~ 2χ1〇7, theoretical plate 201245350 number: 10,000 plates) / Root, filler material: styrene - divinyl benzene copolymer, filler particle size: 1 Ο μιη) 3 in series for measurement. Further, the 'polynonanol-based compound (8) contains a polyol compound (χ2) having two hydroxyl groups and having a hydroxyl group value of less than 4^0 mgKOH/g (hereinafter referred to as "bifunctional polyol-based compound (χ2)" When the 3D mesh structure is prevented from becoming too dense, and gelation can be prevented when the urethane (mercapto)acrylic acid-based compound is produced, and the amine product can be stably produced. (4) Acid I Conjugate [0031] The base price of the compound of the 70th alcohol compound (4) must be less than 45〇mgK〇H/g, 18〇mgK〇H/g — recorded in dense, easy to gel Tendency = the hardness of the outside will be easily reduced = the measurement is made according to the coffee 557. Various polycarbonate-based oxy alcohols, poly-based polyhydric alcohols, poly-polyols, hydrazino-based polyhydric alcohols, polyoxo-oxygenated g-butadiene-based polyhydric alcohols, Specifically, it is possible to obtain a bifunctional polyol obtained by using a compound of the above-described polyol-based compound (XI) exemplified in the above-mentioned trifunctional or higher functional group to obtain a bifunctional hydroxyl group. In combination with the raw material 厶t月 & ,, in terms of excellentness, the 3D mesh structure of the heavy stage of the 2 official [0034] 201245350 bifunctional polyol compound (x2) will become too much. Vinegar (10) can I Ichizaki has. Made of 3 official compound (X)' when using 2 _ yuan _ compound (four), #;; ΐΓίί; ί^Τ (^ (xlKx^i H is): ()9~&quot ;: 1 is preferable, particularly preferably W, (four) -= 8 to 50:50, and more preferably (χ1): (χ2) = 3:97 to 3〇: 7〇. Mesh diol compound ( If the ratio of the front side of Xl) is too large, the three-dimensional = 'molecular weight becomes too high' tends to be easily gelled at the time of manufacture, and it tends to be difficult to be excellent. The secret of (A) and (4) [45036] 450m ι< ^ sterol compound (Χ) ' should contain 2 base groups Further, the polyol compound (χ3) (hereinafter sometimes referred to as "bifunctional (tetra)")) having a base value of 夕-^gM is preferable, and in particular, in addition to the above-described trifunctional polyvalent compound (xl), In addition to the bifunctional polyol compound (χ2), when the base group is further contained and the price is 45 GmgKOH/g or more, the oxime alcohol compound (χ3) is used to make the urethane (meth) acrylate system. The three-dimensional mesh structure of the compound is more soothing and the film stretchability is preferably improved. [0037] The hydroxyl group of the 丄2-functional polyol compound (χ3) needs to be 45 〇 mg K 〇 H or more, preferably. It is 500 mgKOH/g or more, and more preferably 550 mgK〇H/g or more. Further, the upper limit of the hydroxyl value is usually 2,000 mgKOH/g. The hydroxyl value is determined according to JIS K 1557. [0038] 201245350 or less ί Hi ΐ The polysterol-based compound (x3) is, for example, a weight average molecular weight of about 250 diol compound, and specific examples thereof include ethylene glycol, diethyl 2 diol, trimethylene glycol, and di- succinyl propyl , neoterpene propylene glycol, 2_butyl-2-ethyl propylene glycol, tetrapenta-f-based diol, π hexamethylene glycol, ·^ H,5-5F! Base: alcohol, quarterly alcohol: "Nen ΐ = diol ί 1 alcohol octyl aliphatic alcohol, μ_cyclohexanediol, cyclohexyl dimethanol and other loops stupid: poor and so on Shuanglai, tricyclic smoldering dimethanol, xylitol or saponin, etc., can be used in one type or in combination with two or more kinds of wood cleavage, 'the yellow denaturation of hardened coating film, It is preferably a compound which does not contain a structure of a saturated base, and is preferably an aliphatic alcohol, and more preferably [0039] 〇 50% by weight, preferably a household ping pong Λ 1 Sichuan private 5 5 The total amount of the substance (χ2) is from .3 to 4% by weight, and more preferably from 0.5 to 25 parts by weight. /! Li, ^ amine ° A = = its mesh network structure will become too dense, the viscosity is sharp ^ : A W (4)) propylene 嶋 compound will be easy to gel = [0040] ^ ΐ〇 5: ί? ;^^ —〇> ^ ^ 衡性优困弹==Construction _大' points are too high, there will be capacity when manufacturing ^^ [0041] g return to average number of silks is based on the following formula (1) or request Winner. 201245350 a The average number of hydroxyl groups = the number of hydroxyl groups of the polyol compound (χ1) of the polyol compound (xl) having a functional group or more (xl), and the polyol compound of the polyol compound (χ1) or more. Molecular weight calculated from the hydroxyl value of the compound (Xl) + molecular weight calculated from the hydroxyl value of the bifunctional polyol compound (Χ2)}] Ten added molar number from [{2χ2 functional polyol system=^^^2) }/{Molecular weight of the polyol compound of the above three functional groups (χ1) is different from the molecular weight + molecular weight calculated from the hydroxyl value of the bifunctional polyol compound (χ2)}] ' [Π] λ average hydroxyl number = from [Addition of a molar number of a polyol compound (χ1) having a hydroxyl group of the polyhydric alcohol compound (xl) or more than a functional group of the polyhydric alcohol compound (xl), and a polyhydric alcohol compound (χ1) Molecular weight calculated by base price + molecular weight calculated from the base price of the bifunctional polyol compound (X2) + molecular weight calculated from the reading base price of the bifunctional polyol compound (4)}] + from [yang matens polyol system Addition of compound (4) 1 number of ears} / {Based on the base price of the multi-component compound (χ1) of 3 or more ^ The amount + the molecular weight calculated from the base price of the bifunctional polyol compound (4) + from 2, the molecular weight of the multi-touch compound (4), the molecular weight}] + from [{2><2 functional sterols Mole number of addition of compound (x3)} / molecular weight calculated by base price of polyol having 3 or more functions + molecular weight of rhodium from bifunctional polyol compound (10) + bifunctional polyol system Molecular weight calculated from the hydroxyl value of the compound (χ3)}, ^ [0042] Hydroxy-containing (meth)acrylic acid g-based compound (y), for example: (methyl) acrylate hydroxyethyl vinegar: (methyl Propionate 2_silk vinegar, (meth)acrylic acid L via butyl vinegar, (meth)acrylic acid 4 _ butyl acetonate, (meth) acrylic acid butyl group (methyl η fine purpose, 2 _ Silk ethyl propylene brewing base _, 2_ (methyl) propylene oxyethyl ethyl = dicarboxylic acid s, dipropylene glycol (yang propylene vinegar, fatty acid modified (=) propylene propylene vinegar, polyethylene glycol Mono (3)-based) acetoacetate, polypropylene glycol mono- propyl acrylate, 2 _ yl (meth) propylene oxiran propyl acrylate, etc. = 1 ethylenic unsaturated red containing thiol group (9) base) acrylic vinegar Compound; gan's-(?-) propyl acetoacetate, 2-sil-3-propenyl propyloxy-methoxyglycolic acid vinegar, penta 12 201245350 tetraol di(methyl) propyl, epoxy Ethylene (ethylene 〇xide) modified pentaerythritol tris(fluorenyl) propylene, dipentaerythritol penta (indenyl) acrylic acid vinegar, epoxy ethylene bromide modified di-f-pentyl diol five (mercapto) propylene (10)-based (meth) acrylate-based compound containing two or more ethylenically unsaturated groups, and these may be used in combination of two or more kinds. Mouth [0043] 斤八中'-containing one ethylenically unsaturated group-based (meth)acrylic acid I-based compound is preferred 'from the viewpoint of excellent reactivity and general secret, (methyl) (tetra) acid 2 Ethyl ester, 2-methyl propyl (meth) acrylate, 2-hydroxybutyl 2-(butyl) hydroxybutyl methacrylate, especially (indenyl) acrylate 2 _ [0044] The methyl acrylate-based compound (y) is based on the viewpoint that the acidity of 1 mg KOH/g of the compound is difficult to pass through the (meth) acrylate vinegar-based s 曰糸 compound. The fiber content is less than 1 mg KQH/g ^ f compound, and specific examples thereof include acetamidine, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate. You Jia is the (methyl) handsome sour red § purpose. In addition, among the hydroxyl group-containing (meth) acrylate compounds, for the JriS olefin, the raw material that can be obtained by the 2 _ ke vine vinegar is the vinegar in the vinegar. When the amount of sex increases, the acid value tends to increase, and it is intended to modify (4)) C-touch 2 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ For example, methyl phenyl diisocyanate-based ketone two-dimensional test g, polyphenyl f wire _ _ ^ heterochromic _, xylene diisocyanide _, tetramethyl xylene xylene 23 201245350 An aromatic polyisocyanate such as phenyl phthalic acid or naphthalene diisocyanate, hexamethylene diisocyanate g, trimethylhexa-p-diisocyanate or lysine diiso-acid vinegar, Amino acid tri-equivalent g is equivalent to fat (10), polyisocyanate@, hydrogenated diphenyl-methyl-anhydrous, hydrogenated xylene diisocyanate, isophorone diisocyanate, candied vine vinegar, An alicyclic polyisocyanate or a bis(isohalo acid sulfhydryl) oxime. a trimeric or multimeric compound of a polyisocyanate such as hai, a jlophaiiate type polyisocyanate, a biuret type polyisocyanate, a water-dispersible polyisocyanate (for example, a Japanese polyurethane) Industrial (stock) system "AQUANATE 1〇〇", :A々QUANATE110", "AqUANATE2〇〇", "AQUANATE21〇", etc.). [0047] Among these, it is preferred to use methylphenyl diisocyanate, diphenyldecane diisocyanate, modified diphenylmethane diisocyanate, dianylene diisocyanate, mercapto phenyl diisocyanate. Acid §, phenyl diene test, naphthalene triisocyanate vinegar, fragrant isocyanate; hexamethylene diisocyanate, trimethyl hexamethylene diisolog acid Acid diiso-Nuss is equivalent to the diester isocyanide; hydrogenated diphenyl-methyl-isocyanate §, hydrogenated xylene diisocyanate, isophorone diisoxamic acid, halo Alicyclic diisocyanate, alicyclic diisocyanine vinegar such as L3-bis(isocyanatomethyl)cyclohexane; diisocyanate-based compound, such as less yellowing or hardening shrinkage from the hardened coating film More preferably, it is an alicyclic diisocyanate compound, more preferably isophorone dihydrazide, hydrogenated diphenylcarbamate dimer test §|, hydrogenated quinone diisophthalic acid vinegar by containing the above (X The constituents of ~(z) are reacted to obtain a urethane-based acrylate-based compound (A). Aminoguanidine SscSa(methyl)propionic acid|The method for producing the compound (A), usually, may be a dollar alcohol, a compound (X), and the above-mentioned mercapto-containing (mercapto) acrylic acid vinegar system. Compound (y): octadecyl isocyanate compound (Z) - sub-addition or fractional addition to the reactor and reaction to make 'polyol-based compound (X) and polyisocyanate-based compound (8) The method of reacting the reaction product obtained by the reaction of 14 201245350 with the hydroxyl group-containing (meth) acrylate compound (y) is preferred from the viewpoints of reaction stability or reduction of by-products. [0050] In the method of reacting a hydroxyl group-containing (meth) acrylate compound (y) with a reaction product obtained by previously reacting the polyol compound (X) with a polyvalent isocyanate compound (z), the above plural The reaction of the alcohol compound (χ) with the polyvalent isocyanate compound may be carried out by a known reaction method, for example, by using an isocyanate group in a polyvalent isocyanate compound (Z): a transbasic group in a polyhydric alcohol compound (χ) The functional group molar ratio, usually about isocyanate group mol: (polyol hydroxy m〇1, hydroxyl group-containing acrylate group 111()1), and the reaction product of the isocyanide group Just fine. The reaction product of the above polyol-based compound (8) and the polyisocyanate-based compound (z), and the hydroxyl group-containing (meth)acrylic acid s-based compound (== method, when the reaction product and the warp-containing group) The reaction molar ratio of the reaction product is, for example, two of the reaction products, and one of the wires containing the silk, and the reaction product: When there is one of the thiol-based compounds (y), the phase of the (mercapto)propylamine-compound (y) is reacted at about 1:3, ie, in the reaction product The content of residual isocyanate in the hydroxyl group-containing (meth)acrylic acid vinegar-based system is ° G, 5 weights in combination = obtaining the amine of the present invention (methylation [0053] and 'using 3 When the polyhydric alcohol-based compound (4) is a functional group or more, a trifunctional or higher polyhydric alcohol compound (^Γ-' ', ,,,,,,,,,,,,,,,,,,,,,,,, Purpose 15 201245350 Disperse the branch structure in the urethane acetate (mercapto) vinegar vinegar knife ^ 'It should be divided into the wrong section to mix and make the reaction better. When the substitution can be divided into the above _ compound (6), can be divided into arbitrary For example, when blending in two stages, from the viewpoint of making the branched structure in a good acid vinegar (mercapto) acrylic acid/molecule, it is preferable to use a weight ratio of the second. 2 segments, ~90: 90 to 10 The second addition is preferred. The reaction between the parent material (χ) and the polyisocyanate compound (2) is carried out, and is preferably: I, : 'the catalyst is also preferably used, and the catalyst may be, for example, two materials, tin. Organometallic compound salt such as tin hydroxide or tetra-n-butyltin, triacetamide, = acid acid, gasification tin (1), tin chloride (9), etc. "5 4 Π ^ ^ one, nitrogen Heterobicyclo[2,2,2]octane, anthracene, 8-diazo catalyst, Shi Xiao _ m Wei Xu, sulphide, in addition, dihexanoic acid i [butit dilaurate dioctyl scale organic compound , or 2_ethyl acid (4), isobarium salt, new Wei wrap, lauric acid salt, salt, stearic acid salt, oil salt, linoleic acid (four), acetic acid money salt, dihydrate acid acid rope, Two gallic acid and other organic _ salt 蚤 - - ^ 为 _, i which, dibutyl tin dilaurate, 1,8 diazabicyclo [5,4,0] ten [0055] to I = oxime alcohol Reaction of compound (X) with polyisocyanate compound (z), +,:? An organic solvent which reacts with a hydroxyl group-containing (meth) acrylate-based compound (y) and which has a functional group reactive with an isocyanate group, and can be used as an example of a genus An organic solvent such as a ketone such as f-ethyl ketone or methyl isobutyl ketone, or an aromatic compound such as methyl or mono-toluene. [0056] The organic solvent may also be used instead of a reaction having no reaction to the same. The (meth)acrylic acid oxime monomer, the (meth)acrylic acid vinegar monomer is preferably a bifunctional 16 201245350 (meth)acrylic acid s monomer, monofunctional (fluorenyl) acrylic acid: [0057]酉, 4,2-Ethyl alcohol, 匕7, propylene, propylene, monomer, for example: ethylene glycol bis(indenyl) acetophenric acid, ethyl phthalate, diethylene glycol di(meth) acrylate Vinegar, poly, A: 222 曰 propylene glycol di(meth) acrylate, dipropylene glycol dicarboxylate, epoxy _ a type i methyl (4) type A: (meth) acrylate, cyclohexyl Burning 曱酉 to a (meth)acrylic brewing, ethoxylated ring [0058] gas stupid 3 official Λ (Ι基 w_s_ 'such as: styrene, ethyl toluene, fine styrene monomer; Base) acrylic vinegar, ( rZtT, nC^ (methyl) acrylic acid, hexyl (meth) acrylate; (i, dihexamethylene; decyl acrylate, fresh propyl acrylate = 壬, (methyl) _ riding i i5Sla ^tfA^^l±(n=Z5) (f ^ ^ ) propyl plate tetramine, carbitol (meth) propylene _, (meth) acrylate butoxy 17 201245350 vinegar, Acrylate monomer such as allyl (meth) acrylate, (meth) propylene sulfhydryl porphyrin, polyethylene oxide secondary alkyl ether acrylate; N-hydroxyindole (meth) acrylamide N_vinylpyrrolidone, 2-vinylpyridine, vinyl acetate, and the like. [0059] The reaction of the above polyol compound (X) with a polyvalent isocyanate compound, and in the reaction of the reaction product with a hydroxyl group-containing (fluorenyl) acrylate compound (y), the reaction temperature is usually 30~ Loot: preferably 40 to 90 〇C, and the reaction time is usually 2 to 10 hours', preferably 3 to 8 hours. The content of the ethylenically unsaturated group (mmol/g) of the amine phthalate acrylate compound used in the present invention is preferably 0.01 to 10 mm 〇 1 /g, more preferably 0.05 〜 5 mmol/g, more preferably (U~, especially preferably 〇)~〇5 mm〇1/g. The ethylenically unsaturated group content of the urethane (mercapto) acrylate compound (4) (mmol/g) When the amount is too small, the curing at the time of irradiation with an active energy ray tends to be insufficient. When the amount is too large, the component which forms a crosslink due to the active energy ray increases, and the tendency of the cured film to be stretched and the elasticity tends to be difficult to obtain. Further, the amine phthalate (meth) acrylate compound (A) preferably has 10 or less ethylenically unsaturated groups from the viewpoint of utilizing structural properties, that is, stretchability and elasticity. More preferably, it has 6 or less ethylenically unsaturated groups, more preferably 4 or less ethylenically unsaturated groups. Further, usually, the lower limit of the ethylenically unsaturated group is one. [0062] The amine used in the present invention The weight average molecular weight of the formate (meth) acrylate compound (A) needs to be 10,000 to 80 , especially for 20,000 to 50,000, and more preferably 10,000. If the average molecular weight of Haiheli is too small, the stretchability and elasticity of the hardened coating film will have a low tendency. If it is too large, the viscosity will become high and it will be difficult to operate. The tendency is 曰 [0063] Further, the weight average molecular weight is measured in the same manner as described above.

I 201245350 [0064] 又，本發明中， 當〉谷 脸田®fc at，m 甘、t- ._x .I 201245350 [0064] Further, in the present invention, when > 谷面田®fc at, m 甘, t-._x.

潍能量射線硬倾樹齡成物巾，視需要可添加 ⑻、胺甲_旨(甲基)_酸縣化合物⑷以外的乙 如不飽和單體(〇、丙稀酸樹脂、表面調整劑 等。 [0067] ^女疋劑、補強劑、消光劑、研削劑、有機微粒、無機粒子 —上述光聚合起始劑(Β)，例如:二乙氧基苯乙酮、2_羥基_2_甲基 -1苯基丙烧-1-酮、节基二甲基縮嗣、4_(2_經基乙氧基)苯基(2_經基 -2-丙基)酮、1_羥基環己基苯基酮、孓甲基_2_味琳代(心硫曱基苯基) 丙-1 -酮、2_节基_2_二曱胺基小(4_味啉代苯基)丁酮、2_經基_2_曱1 -1-[4_(1二曱基乙烯基)苯基]丙酮寡聚物等苯乙酮類;笨偶因、苯偶^ :醚、苯偶因***、苯偶因異丙醚、苯偶因異丁醚等苯偶因類;二 本基酮、钟本曱酿基苯曱酸甲醋、4_苯基二苯基酮、4_苯甲酸基_4，_ :基-二苯基硫醚、3,3，，4,4，-四（第三丁氧基羰基)二苯基酮、^'，4,6_ ，甲基二苯基酮、4-苯曱醯基-Ν，Ν-二曱基-N-[2-(l-側氧基_2_丙烯 氧基)乙基]苯溴化甲胺、（4-苯曱醯基苄基)三曱基氯化銨等二苯基 酮類;2-異丙基噻吨酮、和異丙基噻吨酮、2,4_二乙基噻吨酮、2,4_ 二氯噻吨酮、1-氯-4-丙氧基噻吨酮、2-(3-二曱胺基-2-羥基)_3,4-二 19 201245350 甲基-9H-嗟吨酮-9-酮内消旋(meso)氣化物等噻吨酮類;2,4,6_三甲 基苯甲^基-二苯基氧化膦、雙(2,6_二曱氧基苯甲醯基)_2,4,4-三曱 ，:戊，氧化膦、雙(2,4,6-三甲基苯甲醯基)_苯基氧化膦等醯基氧化 膦類;等。又，該等光聚合起始劑(B)可以僅使用1種，也可併用2 種以上。 [0068] ^又，’就该等的助劑而言，也可併用例如:三乙醇胺、三異丙醇 月ί ""一甲胺基二笨基酮(米音酮）、4,4’_二乙胺基二苯基酮、2- 二曱〒基乙基苯甲酸、4_二甲胺基苯價乙g旨、4_二甲胺基苯曱酸 (正氧基)乙酯、4-二甲胺基苯甲酸異戊酯、4_二甲胺基苯罕酸2_ 酯、2,4_二乙基噻吨酮、2,4_二異丙基噻吨酮等。 德Ϊίt中’較佳騎基二甲基、_、1_經基環己基苯基嗣、苯 甲其? ^、4_(2為基乙氧基)苯基-(2-羥基丙基)酮、2_經基-L τ 术基丙烧小酉同。 [0070] 化人ίϋίΐ·1(β)之含量，相對於胺曱酸醋（曱基)丙烯酸醋系 重：4八 ^里份，宜為0.1〜2〇重量份較佳，尤佳為0.5〜10 重里份，更佳為1〜10重量份。 傾向光始！Ι(Γί含量若過少，硬化不良，會有難形成膜的 色的問題的^ /成為硬化塗膜黃變的原因，會有容易發生著 [0071] [0072] 早g此早體、2官能單體、3官能以上之單體。 基苯^如:苯乙烯、乙烯基甲苯、氯苯乙烯、α-曱 ;==2體甲(:其基)丙請酷、⑽繼乙醋、 (甲基)丙烯酸、闕稱酸2德乙醋、 二土 -曰、（甲基)丙烯酸2-經基丁酯、（甲基)丙烯 20 201245350 基)丙烯酸酯、（甲基)丙嫌ϋ稀吼_2-經基丙醋、甘油單(甲 甲基(甲基)丙烯酸醋、環己烧螺ane>4_基> 曱基(曱基}丙烯酸醋、3_乙先二錯(二：喊_10X0laneM-基> 丁内醋(甲基)丙烯酸酉旨、（甲不元土 ^基(甲基)丙烯酸醋、γ-(甲基)丙烯酸庚醋、（甲基)丙^酸=甲^丙烯酸己醋、 丙稀酸癸酉旨、（甲基)兩烯酸異癸 壬酉匕旨、（甲基） 丙烯酸正硬脂酯、（甲芙)兩梳於—jO四烯-欠十—酯、（甲基） 基)丙烯醯基味琳、聚環氧乙院二 ^ 醋系單體、2-經基乙基丙稀_ 基)丙城 =爾酮、2.乙雜喊、基)抛胺、N_ 其、jit能單體，例如:乙二醇二(甲基)丙稀酸醋、二乙二醇二(曱 二砂，欠日、四乙二醇二（甲基)丙烯酸酯、聚乙二醇二（尹其)兩梳 酸醋、丙二醇二(甲基)丙婦酉变醋、二丙 二(/基)丙席 (丙甲^1甲,基)丙烯酸醋、丁二醇二(甲基)丙稀二ίΓ-1醇聚 (甲基)丙炸酸醋、環氧乙烧改性雙紛二f甲其、祕^戊一知一 、ί ,、田乙 1 氧基化己烧二甲醇二(甲基)兩烯酸酯、二㈣λ!严；i 烷-(甲基)丙烯酸酯、三環癸烷二甲醇 土了义 二醇二(《)丙稀義、甘油二㈣丙婦酸醋、=^ 201245350 丙棘醋、乙二醇二環氧丙鱗二（甲 丙醚二（曱基)内稀酸酷、鄰苯 曰乙一酉予—每乳 氧乙烧改性二兩烯酸酉旨等。 （甲基)丙細酉夂酉曰、異麟酸環 [0074]潍Energy ray hard-aged ageing tissue towel, if necessary, (e), an ethylenically unsaturated monomer (anthracene, acrylic acid resin, surface conditioner, etc.) other than the (meth)-acid acid compound (4). [0067] ^N. licking agent, reinforcing agent, matting agent, grinding agent, organic fine particles, inorganic particles - the above photopolymerization initiator (Β), for example: diethoxyacetophenone, 2-hydroxy-2-a Phenyl-1 phenylpropan-1-one, benzyl dimethyl hydrazide, 4-(2-cyanoethoxy)phenyl (2-cyano-2-propyl) ketone, 1-hydroxycyclohexyl Phenyl ketone, hydrazine methyl 2 _ _ _ _ _ _ _ _ _ _ _ ke ke ke ke ke ke ke ke ke ke ke ke ke ke ke ke ke ke ke ke ke ke ke ke ke ke Benzene ketones such as 2_ thiol_2_曱1 -1-[4_(1 dimethylphenyl)phenyl]acetone oligomer; styrene, benzophenone: ether, benzoin ether , benzoin isopropyl ether, benzoin isobutyl ether and other benzoin; bis- ketone, clock broth benzoic acid methyl vinegar, 4 phenyl diphenyl ketone, 4 benzoic acid _4,_: yl-diphenyl sulfide, 3,3,,4,4,-tetrakis(t-butoxycarbonyl)diphenyl ketone, ^', 4,6_, methyldiphenyl ketone , 4-phenylhydrazinyl-fluorene, hydrazine- Diphenyl such as fluorenyl-N-[2-(l-sideoxy-2-propenyloxy)ethyl]benzene bromide and (4-phenylhydrazinobenzyl)trimethylammonium chloride Ketones; 2-isopropylthioxanthone, and isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythiophene Toxanone, 2-(3-dioxanyl-2-hydroxy)_3,4-di 19 201245350 methyl-9H-xanthone-9-one meso ketones such as meso vapors; 2,4,6-trimethylbenzylidene-diphenylphosphine oxide, bis(2,6-dimethoxybenzylphenanthryl)-2,4,4-triazole, pentane, phosphine oxide, a fluorenylphosphine oxide such as bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide; etc. Further, the photopolymerization initiator (B) may be used alone or in combination. Further, two or more types may be used. [0068] Further, in the case of such adjuvants, for example, triethanolamine, triisopropanol, and monomethylaminobisphenyl ketone may be used in combination. Ketone), 4,4'-diethylaminodiphenyl ketone, 2-dimercaptoethyl benzoic acid, 4-dimethylamino benzene valence, 4-dimethylaminobenzoic acid ( N-oxy)ethyl ester, 4-dimethylaminobenzoic acid isoamyl ester, 4-dimethylaminobenzonic acid 2-ester, 2,4_Diethylthioxanthone, 2,4-diisopropylthioxanthone, etc. DeΪίt中's preferred riding dimethyl, _, 1_ylcyclohexylphenyl fluorene, benzoic acid ^, 4_(2 is ethoxylated) phenyl-(2-hydroxypropyl) ketone, 2_ thiol-L τ 基 丙 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The content is relative to the weight of the amine phthalic acid vinegar (meth) vinegar vinegar: 4 8%, preferably 0.1 to 2 〇 by weight, more preferably 0.5 to 10 parts by weight, more preferably 1 to 10 parts. Parts by weight. Tend to light! Ι (Γ 含量 含量 含量 含量 含量 含量 含量 含量 含量 含量 含量 含量 含量 含量 含量 含量 含量 含量 含量 含量 含量 含量 / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / Monomer, trifunctional or higher monomer. Benzobenzene such as: styrene, vinyl toluene, chlorostyrene, α-曱; == 2 body armor (: its base) C, please cool, (10) followed by vinegar, (A Acrylic acid, nickname acid 2 ethane vinegar, bismuth-bismuth, (meth)acrylic acid 2-butyl butyl acrylate, (meth) propylene 20 201245350 acrylate), (meth) propylene sputum _2-P-propyl vinegar, glycerol mono (methyl (meth) acrylate, cyclohexane snail > 4 _ base 曱 曱 (曱 } acrylate vinegar, 3 _ first two wrong (two: Shout _10X0laneM-base> Ding vinegar (meth) acrylate 、, (A gluten-free (meth) acrylate vinegar, γ-(meth) acrylate vinegar, (methyl) propyl acid = Acetic acid hexaacetic acid, acrylic acid, methic acid (meth) bisenoic acid, (methyl) acrylate, stearyl ester, (meth) two combs - jO tetraene - owed Dec-ester, (meth) group) propylene oxime-based, poly epoxy epoxide 2 Vinegar monomer, 2-ylethyl propyl propyl group, propyl ketone, ketone ketone, ketone, sulfonate, N-, jit-energy, for example, ethylene glycol di(methyl) Acetate vinegar, diethylene glycol bis(bismuth sulphate, owe day, tetraethylene glycol di(meth) acrylate, polyethylene glycol bis (Yin Qi) two comb vinegar, propylene glycol di(methyl) ) 丙 酉 酉 vinegar, dipropyl bis ( / base) propyl s (propyl propyl ketone) acrylic acid vinegar, butane diol di (methyl) propylene di Γ 醇 醇 醇 醇 醇 醇Sour vinegar, epoxy Ethylene sulphate modified double singular two f 甲 甲, secret ^ 戊一知一, ί, 田乙1 oxylated hexanes dimethanol di(methyl) enoate, two (four) λ! Yan I-alkyl-(meth)acrylate, tricyclodecane dimethanol tert-diol diol (") propyl, glycerol di(tetra)-propyl vinegar, =^ 201245350 albino vinegar, ethylene glycol bicyclic Oxyfluoride bismuth (methylene ether bis(indenyl) dilute acid cool, o-benzoquinone 酉 酉 — 每 每 每 每 每 每 每 每 每 每 每 每 每 每 每 每 每 每 每 。 。 , isolinic acid ring [0074]

季戍甲例三經甲基丙烧三(曱基)丙烯酸I 丙烯酿氧/乙減^曰季戊四醇六（甲基)丙烯酸醋、三(甲基） Ξ(曱三丙烯_旨、己内醋改性二季 =ί 五（曱基)丙稀酸醋、己内醋改性二季 =四酉子 内酉旨改性季戊四醇三(甲基)丙烯_旨戊己==)丙^酸醋、己 基)丙烯酸酯、環氧乙烧改性二季戊 曰^戍四醇四（甲 乙烧改性二季戊四醇met匕％五（甲基)丙_醋、環氧 r甲編(甲基)丙烯酸s|、環氧乙烧改性季戊四醇： (曱基)丙喊s旨、環氧乙纽性季戊 ^四％·- 基化甘油三丙騎醋等。手戊叫四（甲基)丙埽酸醋、乙氧 [0075]戍 例 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三 三Modified two seasons = ί five (mercapto) acrylic acid vinegar, caprolactone modified two seasons = four scorpions, modified pentaerythritol tris(methyl) propylene _ _ _ _ _ _ _ _ vine vinegar, hexyl Acrylate, Ethylene Ethylene Modified Dipentazone, Tetrakiol Tetrahydrate (Ethyl Ethyl Acetate Modified Dipentaerythritol Mexi%, Five (Methyl) Propylene, Vinegar, Epoxy Resin (M) Acrylic Acid s|, Epoxy Ethylene-modified Pentaerythritol: (曱基), 丙, s, Ethylene, Ethyl, Ethyl, Ethyl, Ethyl, Ethyl, Ethyl, Ethyl, Acetate, etc. Ethoxygen [0075]

可f用丙烯酸之加成物或2_丙烯醯氧美乙A 編烯酸二聚物、丙烯酸三聚物成酸二聚物、 四聚物1基丙烯酸四聚物等。甲基丙版二聚物、丙烯酸 酸，ΐ:丄丙⑦J具有特定取代基的幾 基琥猶單醋、2-丙烯醯氧^單2:甲七 氣乙基鄰苯二〒酸單醋、2-丙刺氧基乙甲基丙烯醯 ^甲基丙烯酿氧乙基六氫鄰苯酸=旨、 暴酯丙烯酸酯。 平曰夺再者，也可列舉其他 [0076] 22 201245350 時之造膜性的作用。 私鲛树知具有賦予塗佈 [0077] 用予作 =顧_旨 '纽性齡、絲^樹ί ，可使用 對^述S抑制劑，例如:對苯酿、萘艇、甲苯驅、2 5--装其 對本S比、虱醌、2,5-二第三丁基氮酿、甲其 卜:5 —本基- 第三丁基聽、對第三丁基兒甲基贱、麟單甲鱗、單 [0079] ίίίίΐΐ，宜使於稀釋之有機溶劑較佳。該有 ^甲Ιΐ _'㈣、丙醇、正丁醇、異丁醇等醇類、 甲1、丁酮、曱乙酮、環己轉峨、乙基赛路蘇等謇这 =甲苯:二甲苯等芳香族類、丙二醇單甲 乙酸乙醋、乙酸丁®旨等乙酸酯類、二丙酮醇等。該等上 处有機溶劑可以單獨使用，也可併用2種以上。 、 [0080] 2用十述2種以上時’組合選用二醇醚類、酮類、醇類之中 的2種以上，從塗膜外觀之觀點為較佳。 [0081] 又，製造本發明之活性能量射線硬化性樹脂組成物時，扁於 ^甲酸自旨(Τ基)丙烯酸1¾化合物⑷及其他成分之混合.方法，不 特別限定’可利用各種方法混合。 [0082] 本發明之活性能量射線硬化性樹脂組成物，可有效地當作對 於各種基材之面塗劑或黏底塗層劑等、塗膜形成用之硬化性樹脂 組成物，當將活性能量射線硬化性樹脂組成物塗佈於基材後(塗佈 23 201245350 溶劑稀釋之組成物時，係進—步乾 置射線而使硬化。 月匕 [0083] 論為上述本發明之活性能量射線硬化性樹脂組成物對象的 树月旨丙烯腈丁二稀苯乙婦共聚物(规)、$苯乙婦系樹脂 成型品(膜、片、杯等)等塑朦基材、該等之複合基材、 璃纖維或無杨而得之前 二 等辞、鎂、該等之合金等)，或在玻= [0084] 塗、:能ίΪ線^性樹脂組成物之塗佈方法，例如:喷塗、淋 疋主、網版印刷等濕式塗佈法，通常於常严之 條件塗佈於基材即可。 1広m吊y吊/皿之 [0085] 有機二ίίΓΐ=ίϊ射線硬化性樹脂組成物，宜使用上述 成分濃料財Wi為Μ [0086] 40〜&amp;機=(^稀_之乾_件，溫度通常為 為2〜10分^為50〜100c，乾燥時間通常為㈣分鐘，較佳 [0087] 用；2ί ί=:ϊ=硬=脂，· 中性子束等，從硬化速度、子束、質子束、 利用紫外線照射進行硬化為有#f置又取^料度、價格等觀點， 不用光聚合起始劑(B)也能硬化。 仃電子束照射時，即使 [0088] 24 201245350 一利用紫外線照射使硬化時，使用發出波長區15〇〜45〇nm之光 的高壓水銀燈、超高壓水銀燈、碳弧燈、金屬_化物燈、氣燈、 化學燈、無電極放電燈、LED等，通常照射3〇〜3〇〇〇mJ/cm2 為100〜1500mJ/cm2)之紫外線即可。 紫外線照射後，視需要也可進行加熱而達成完全硬化。 [0089] 塗佈膜厚(硬化後之膜厚），係與推想當作損傷復原性的損傷深 度相關、’要是定為損傷深度不超驗賴厚的任意 可，通常’紫外線硬化型之塗膜考慮到光聚合起始劑⑻為了 反應之光線穿透，定為3〜麵_即可，較佳為5_，尤佳 為 10〜200μπι。 土 [0090] 本發明之活性能量射線硬化性樹脂組成物，特徵在於 甲酸醋(甲基)丙稀酸g旨化合物(Α)，該胺甲酸醋（甲基)丙稀酸酿化入 物㈧係使含有含3個以上的絲的多元醇系化合物㈣之多元^ 糸化合物(X)、含羥基之(甲基)丙烯酸酯系化合物(y)、及多元显 ，醋系化合物⑻反應而成，當該活性能量射線硬化性樹脂^ ^成硬化塗膜時，由於維持胺甲酸親構特有的麵伸張性= N·具備由於3維網目結構而得之塗膜收縮性，所以可獲 ° 收縮性能的諸，所以，能形賴於娜的復雜时用性甲張、 =塗膜，當作塗料、印墨、塗佈劑，尤其最表關塗佈劑特= 實施例 [0091] 以下舉實施例更f體說明本發明，但本發明在不超過 的摩i圍’不限於以下貫施例。又，例中「十、、「0/ /、曰 指重量基準。 伤」、、」’係意 [0092] 照表1) 製備以下物質當作胺甲酸醋（甲基)丙烯酸酯系化合物(a)(參 25 201245350 [0093] &lt;製造例1:胺曱酸酯（甲基)丙烯酸酯系化合物(A-i)&gt; 於具備溫度計、授拌機、水冷冷凝器、氮氣吹入口的4 口燒 瓶中，添加甲苯66.7g、氫化亞二甲苯二異氰酸酯莫 耳）、新戊二醇(X3)(羥基價 l〇78mgKOH/g)2.80g(0.027 莫耳）、3 官 能之聚酯多元醇(xl)(羥基價264mgK〇H/g)7.30g(〇.〇ll莫耳）、2官 能之聚酯多元醇(x2)(羥基價62.8mgKOH/g)42.6g(0.024莫耳）、當 作聚合抑制劑的氫醌曱醚〇.〇2g、當作反應觸媒的二月桂酸二丁^ 錫0.02g ’於6(Tt使反應2小時，添加3官能之聚酯多元醇(xl)(^ 基價264mgKOH/g)2.20g(0_0040莫耳)、2官能之聚酯多元醇(x2)(^ 基^ 63mgKOH/g)21.3g(0,012莫耳），於6(TC使反應2小時，添加 丙烯酸2-羥基乙酯(y)4.〇〇g(〇‘〇34莫耳），於60〇C使反應3小時， 於殘存異氰酸酯基成為0.3%的時點結束反應，獲得胺曱酸酯（曱基) 丙烯酸酯系化合物(A-1)(重量平均分子量(Mw);85,000)之曱苯溶液 (樹脂成分6Q%；)。 [0094] &lt;製造例2:胺曱酸酯（曱基)丙烯酸酯系化合物(A_2)&gt; 於具備溫度計、擾拌機、水冷冷凝器、氮氣吹入口的4 口燒 瓶中，添加甲苯66.7g、氫化亞二甲苯二異氰酸酯⑻19.0g(0 〇98 耳）、新戊二醇(X3)(羥基價 i〇78mgK〇H/g)3.40g(〇.〇33 莫耳）、3 官 能之聚酯多元醇(xl)(羥基價264mgKOH/g)7.30g(0.011莫耳）、以 1，5-戊二醇與丨，6_己二醇當作原料的2官能之聚碳酸酯多元醇 (x2)(經基價55mgKOH/g)66.5g(〇.〇33莫耳）、當作聚合抑制劑的氫 酿曱喊0.02g、當作反應觸媒的二月桂酸二丁基錫〇 〇2g，於6〇&lt;3c 反，3小時’添加2-羥基乙基丙烯酸酯(y)3.8〇g(〇.〇33莫耳），於 60=反應3小時，於殘存異氰酸酯基成為〇·3%的時點結束反應， 獲得胺曱酸酯（甲基）丙烯酸酯系化合物(Α-2)(重量平均分子量 (Mw);57,000)之甲苯溶液(樹脂成分6〇0/(〇。 [0095] 〈衣is·例3.如曱酸§旨（曱基)丙稀酸g旨系化合物(a__3)&gt; 26 201245350 ,於具備溫度計、攪伴機、水冷冷凝器、氮氣吹入口的4 口燒 瓶中，添加曱苯66.7g '氫化亞二甲苯二異氰酸醋⑻】8 4g(〇 〇95莫 f、新戊二醇(x3)(經基價 i〇78mgK〇H/g)2.50g(0.〇24 莫耳）、3 官 旎之聚酯多元醇(xl)(羥基價264mgKOH/g)l〇.lg(〇.〇16莫耳）、以 1，6-己二醇當作原料的2官能的聚碳酸酯多元醇(χ2)(羥基價 60mgKOH/g)65.lg(0.035莫耳）、當做聚合抑制劑的氫醌曱醚 〇.〇2g g作反應觸媒的—月桂酸二丁基錫〇.〇2g，於60。〇反應3 小1，添加丙烯酸2-羥基乙酯(y)3.9〇g(〇 033莫耳），於6〇。〇反應3 小時，於殘存異氰酸酯基成為0.3%的時點結束反應，獲得胺曱酸 酉曰（曱基)丙烯酸酯系化合物(A-3)(重量平均分子量(Mw);78,000)之 甲本浴液(樹脂成分60%)。 [0096] 〈製造例4:胺曱酸酯（曱基)丙烯酸酯系化合物(A_4)&gt; ,於具備溫度計、擾拌機、水冷冷凝器、氮氣吹入口的4 口燒 瓶中，添加曱苯66.7g、氫化亞二甲苯二異氰酸酯(z)29.6g(〇.15莫 耳）、新戊二醇(X3)(經基價 1078mgKOH/g)5.00g(0.048 莫耳）、3 官 能之聚酯多元醇(Xl)(羥基價264mgKOH/g)17.8g(0.028莫耳）、以 2二曱基-1，3_丙二醇與i，4-丁二醇當作原料的2官能的聚碳酸酯多元 ，(x2)(經基價i3〇mgKOH7g)41.7g(a〇48莫耳)、當作聚合抑制劑的 氫酿曱醚0.0¾、當作反應觸媒的二月桂酸二丁基錫0.02g，於6〇。〇 反應3小時，添加丙烯酸2-羥基乙酯(y)5.9〇g(〇.〇51莫耳），於6〇。〇 反應3小時，於殘存異氰酸酯基成為0.3°/。的時點結束反應，獲得 胺曱酸酯（甲基）丙烯酸酯系化合物(A_4)(重量平均分^量 (Mw);135,000)之曱苯溶液(樹脂成分60%)。 [0097] 〈製造例5:胺曱酸酯（甲基)丙烯酸酯系化合物(a_5)&gt; 於具備溫度計、攪拌機、水冷冷凝器、氮氣吹入口的4 口燒 瓶中’添加曱苯66.7g、氫化亞二甲苯二異氰酸酯(z)29.5g(〇.l5莫 耳）、新戊—醇(x3)(經基價 1078mgKOH/g)3.70g(0.035 莫耳）、3 士 能之聚酯多元醇(xl)(羥基價264mgKOH/g)9.70g(0.015莫耳）、以 27 201245350 與1,6·己二鮮當作原料之2官能之聚碳酸®旨多元醇 ㈣(羥鐘ISOmgKOHygN^o.o^莫耳）、當作聚合抑 ^ 酷情0.02g、當作反應觸媒的二月桂酸二丁基錫〇 〇2g，於^ 反應3小時’添加丙烯酸2_羥基乙酯(y)6 〇〇g(〇 〇52莫耳 反應3小時，於殘存異氰酸酷基成為〇 3 ' 胺甲酸酉旨（甲基）丙稀酸I系化合物(A_5)(重量平均應= (Mw);119,000)之甲苯溶液(樹脂成分6〇 于里 [0098] &lt;製造例6:胺曱酸酯（曱基)丙烯酸酯系化合物(A_6)&gt; ,於具備溫度計、麟機、水冷冷凝器、氮氣吹人口之4 瓶中丄^加T苯66.7g、氫化亞二甲苯二異氰酸蝴19.5g(〇.l〇 ί* 魏二甲醇㈣(經基價 572mgKOH/g)5.2_.026 莫耳 3丄，之聚酯多元醇(xl)(羥基價264mgK〇H/g)7 s〇g(〇 〇14莫 ^官能之聚酯多元醇(X2)(羥基價63mgK〇H/g)62 lg(〇 〇35莫 =作聚合抑制劑的鱗曱_.Q2g、當作反應觸媒的二月桂酸二丁 土錫0.02g，於60C反應3小時，添加丙烯酸2_經基乙gt 莫耳），於6G&lt;t反應3小時，於殘存異氰酸絲成^ μ 時點結束反應，獲得胺甲酸酯（甲基）丙烯酸酯系化合物 00¾重量平均分子量(Mw);51，000)之甲苯溶液(樹脂成分60%)。 〈製造例7:胺甲酸酯（甲基)丙烯酸酯系化合物(AJ)〉 ,於具備溫度計、攪綷機、水冷冷凝器、氮氣吹入口之4 口燒 ，中丄^加甲苯66.7g、異佛爾酮二異氰酸酯(z)22.2g(〇.10莫耳）、 二醇(x3)(羥基價 1078mgKOH/g)2.80g(0.027 莫耳）、3 官能之 ，，多元醇(Xl)(羥基價 264mgKOH/g)9.20g(0.014 莫耳）、2 官^之 ，酯多元醇(X2)(羥基價63.4mgKOH/g)61.9g(0.035莫耳）、當作聚 5抑制劑的子醌甲醚0.02g、當作反應觸媒的二月桂酸二^基錫 ^〇2g ’於60 C反應3小時，添加丙烯酸2-經基乙g旨(y)3 9〇g(〇.〇34 、耳）’於6〇t反應3小時，於殘存異氰酸酯基成為〇3%的時點 28 201245350 結束反應，獲得胺曱酸酯（甲基)丙烯酸酯系化合物(A_7)(重量平均 分子量(Mw);29,000)之甲苯溶液(樹脂成分6〇%)。 〈製造例8:胺甲酸酯（甲基)丙烯酸酯系化合物(A_8)&gt; 於具備/m度计、攪拌機、水冷冷凝器、氮氣吹入口的4 口燒 瓶中加甲苯66.7g、六亞甲基二異氰酸酯⑵178g(〇 u莫耳）、 新戊二醇(X3)(羥基價1078mgK〇H/g)2 9〇g(〇 〇28莫耳）、3官能之An acrylic acid adduct or a 2-acrylic oxime A styrene dimer, an acrylic trimer acid dimer, a tetramer 1-based acryl tetramer, or the like may be used. Methyl propyl plate dimer, acryl acid, hydrazine: hydrazine propylene 7J has a specific substituent of a few groups of succinyl vinegar, 2-propene oxime ^ 2: a seven-n-ethyl ethyl phthalic acid monoacetic acid, 2-propenyloxyethyl methacrylate 甲基 methacrylic acid oxyethylhexahydrophthalic acid = propyl ester acrylate. In addition, the role of membrance in other [0076] 22 201245350 can also be listed. The private tree is known to have a coating effect [0077] for the use of _ _ _ _ 'new age, silk ^ tree ί, can be used to describe S inhibitors, such as: benzene, naphthalene, toluene, 2 5--Packed with this S ratio, 虱醌, 2,5-di-tert-butyl nitrogen, kiwi: 5-n-butyl-tert-butyl, p-tert-butyl benzyl hydrazine, lin Single scale, single [0079] ίίίί, preferably suitable for diluting organic solvents. There are alcohols such as Ιΐ _ ' (4), propanol, n-butanol, isobutanol, methyl 1, methyl ethyl ketone, acetophenone, cyclohexyl hydrazine, ethyl celecoxib, etc. An aromatic type such as toluene, an acetate such as propylene glycol monoacetic acid ethyl acetate or butyl acetate, or diacetone alcohol. These organic solvents may be used singly or in combination of two or more. When two or more kinds are used in combination, two or more kinds of glycol ethers, ketones, and alcohols are used in combination, and it is preferable from the viewpoint of the appearance of the coating film. Further, when the active energy ray-curable resin composition of the present invention is produced, it is a method in which the compound (4) and other components are mixed with a carboxylic acid, and the method is not particularly limited, and can be mixed by various methods. . The active energy ray-curable resin composition of the present invention can be effectively used as a curable resin composition for forming a coating film or a primer coating agent for various substrates, and when it is active. After the energy ray curable resin composition is applied to the substrate (when the composition of the solvent dilution of 23 201245350 is applied, the radiation is hardened by the step of drying. [0093] The active energy ray of the present invention described above The composition of the curable resin composition is a composite of a acrylonitrile butadiene benzophenone copolymer (regular), a styrene-based resin molded article (film, sheet, cup, etc.), and the like. a substrate, a glass fiber or a second grade without a yang, a magnesium, an alloy of the same, or the like, or a coating method of a glass resin composition, for example, a spray. Wet coating methods such as coating, dripping, and screen printing are usually applied to a substrate under normal conditions. 1広m hanging y hanging / dish [0085] organic two ίίΓΐ = ϊ ϊ 硬化 硬化 硬化 硬化 ϊ ϊ 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 00 The temperature is usually 2 to 10 minutes ^ 50 to 100 c, the drying time is usually (four) minutes, preferably [0087]; 2 ί ί =: ϊ = hard = fat, · neutral beam, etc., from hardening speed, sub Beams, proton beams, hardening by ultraviolet irradiation, etc., can be hardened without photopolymerization initiator (B). When electron beam irradiation is used, even [0088] 24 201245350 A high-pressure mercury lamp, an ultra-high pressure mercury lamp, a carbon arc lamp, a metal-chemical lamp, a gas lamp, a chemical lamp, an electrodeless discharge lamp, an LED, etc., which emit light having a wavelength region of 15 〇 to 45 〇 nm when hardened by ultraviolet irradiation. It is usually irradiated with ultraviolet rays of 3 〇 to 3 〇〇〇 mJ/cm 2 and 100 to 1500 mJ/cm 2 ). After the ultraviolet irradiation, heating may be performed as needed to achieve complete hardening. [0089] The thickness of the coating film (the thickness of the film after hardening) is related to the depth of damage that is expected to be the damage recovery property, and it is usually determined that the depth of damage is not excessively thick. The film is considered to be a photopolymerization initiator (8) for the light penetration of the reaction, and is preferably 3 to _, preferably 5 Å, and more preferably 10 to 200 μm. Soil [0090] The active energy ray-curable resin composition of the present invention is characterized by a formic acid (meth) acrylic acid gram compound (Α), the urethane carboxylic acid (meth) acrylic acid emulsifiable product (eight) The reaction is carried out by reacting a polyvalent alcohol compound (X) containing a polyhydric alcohol compound (4) containing three or more kinds of wires, a hydroxyl group-containing (meth)acrylate compound (y), and a polybasic compound, and a vinegar compound (8). When the active energy ray-curable resin is formed into a hardened coating film, since the surface stretch property peculiar to maintaining the amine formate structure is satisfied = N·the shrinkage of the coating film obtained by the 3-dimensional mesh structure is obtained, so that the shrinkage is obtained. The performance of the various, so, can be based on Na's complex time-use sheet, = coating film, as a coating, ink, coating agent, especially the most representative coating agent = Example [0091] The present invention will be described in more detail, but the present invention is not limited to the following examples. In addition, in the example, "10, "0/ /, 曰 refers to the weight basis. Injury", ""system [0092] according to Table 1) The following materials were prepared as urethane (meth) acrylate-based compounds ( a) (Ref. 25 201245350) [Production Example 1: Amine phthalate (meth) acrylate compound (Ai)&gt; 4 ports equipped with a thermometer, a mixer, a water-cooled condenser, and a nitrogen gas inlet To the flask, 66.7 g of toluene, hydrogenated xylene diisocyanate molybdenum, neopentyl glycol (X3) (hydroxyl valence of 78 mg KOH/g), 2.80 g (0.027 mol), and a trifunctional polyester polyol ( Xl) (hydroxyl 264 mg K 〇 H / g) 7.30 g (〇. 〇 mol), bifunctional polyester polyol (x2) (hydroxyl price 62.8 mg KOH / g) 42.6 g (0.024 m), as The polymerization inhibitor of hydroquinone ether 〇. 〇 2g, dibutyltin dilaurate as a reaction catalyst 0.02g ' at 6 (Tt to react for 2 hours, adding a trifunctional polyester polyol (xl) ( ^ base price 264 mg KOH / g) 2.20 g (0_0040 mol), bifunctional polyester polyol (x2) (^ base ^ 63 mg KOH / g) 21.3 g (0,012 mol), at 6 (TC for 2 hours, Add 2-hydroxyethyl acrylate (y) 4. 〇〇g (〇'〇34莫The reaction was allowed to proceed at 60 ° C for 3 hours, and the reaction was terminated when the residual isocyanate group became 0.3% to obtain an amine phthalate acrylate compound (A-1) (weight average molecular weight (Mw); 85,000) a benzene solution (resin component 6Q%;). [Production Example 2: Amine phthalate acrylate compound (A_2)&gt; A thermometer, a scrambler, and a water-cooled condenser are provided. To a four-necked flask equipped with a nitrogen gas inlet, 66.7 g of toluene, hydrogenated xylene diisocyanate (8), 19.0 g (0 〇 98 Å), and neopentyl glycol (X3) (hydroxy valence i 〇 78 mg K 〇 H/g) 3.40 were added. g(〇.〇33 Moer), 3-functional polyester polyol (xl) (hydroxyl price 264mgKOH/g) 7.30g (0.011 mole), 1,5-pentanediol and hydrazine, 6-hexane A bifunctional polycarbonate polyol (x2) having an alcohol as a raw material (base price: 55 mgKOH/g) 66.5 g (〇.〇33 mol), hydrogen as a polymerization inhibitor, 0.02 g, 2 g of dibutyltin dilaurate of the reaction catalyst, at 6 〇 &lt;3c, 3 hours 'addition of 2-hydroxyethyl acrylate (y) 3.8 〇g (〇.〇33 mol), at 60= Reaction for 3 hours, in the residual isocyanate group The reaction was terminated at a time of 3%, and a toluene solution of an amine phthalate (meth) acrylate compound (Α-2) (weight average molecular weight (Mw); 57,000) was obtained (resin component 6 〇 0 / (〇) . [Apparently, Example 3. For example, 曱 旨 曱 曱 丙 丙 丙 丙 丙 丙 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 26 具备In a 4-neck flask, 66.7 g of hydrogenated xylene dihydrocyanate (8) was added to the flask (8) (〇〇95 莫f, neopentyl glycol (x3) (base price i〇78 mgK〇H/g) 2.50g (0. 〇24 Moer), 3 bureaucratic polyester polyol (xl) (hydroxyl price 264mgKOH/g) l〇.lg (〇.〇16mol), with 1,6-hexanediol As a raw material, a bifunctional polycarbonate polyol (χ2) (hydroxyl price 60 mgKOH/g) 65. lg (0.035 mol), as a polymerization inhibitor, hydroquinone ether 〇 2 g g as a reaction catalyst - Dibutyltin laurate. 〇 2g, at 60. 〇 Reaction 3 small 1, add 2-hydroxyethyl acrylate (y) 3.9 〇 g (〇 033 Mo), at 6 〇. 〇 reaction for 3 hours, in the residual When the isocyanate group became 0.3%, the reaction was terminated, and a bismuth sulfonate (A-3) hydride (weight average molecular weight (Mw); 78,000) was obtained as a bath (resin component 60%). <Production Example 4: Amine phthalate acrylate compound (A_4)&gt;, in a four-necked flask equipped with a thermometer, a scrambler, a water-cooled condenser, and a nitrogen gas inlet, 66.7 g of toluene and 29.6 g of hydrogenated xylene diisocyanate (z) (〇.15 mol) were added. ), neopentyl glycol (X3) (base price 1078 mg KOH / g) 5.00 g (0.048 mol), 3-functional polyester polyol (Xl) (hydroxyl price 264 mg KOH / g) 17.8 g (0.028 mol), a bifunctional polycarbonate having 2,2,3,3-propanediol and i,4-butanediol as raw materials, (x2) (base price i3〇mgKOH7g) 41.7g (a〇48m ), hydrogen ruthenium ether 0.03⁄4 as a polymerization inhibitor, 0.02 g of dibutyltin dilaurate as a reaction catalyst, at 6 Torr. The reaction was carried out for 3 hours, and 2-hydroxyethyl acrylate (y) 5.9 添加 was added. g (〇.〇51 mol), at 6 〇. The reaction was carried out for 3 hours, and the reaction was terminated at the time when the residual isocyanate group became 0.3° / to obtain an amine phthalate (meth) acrylate compound (A_4) ( A weight average amount (Mw); 135,000) of a benzene solution (resin component: 60%). [Production Example 5: Amine phthalate (meth) acrylate compound (a-5)&gt; Mixer, water-cooled condenser In a 4-neck flask with a nitrogen purge inlet, '66.7 g of toluene, 29.5 g of hydrogenated xylene diisocyanate (z), 新.l5 mole, and neopentyl alcohol (x3) (base price 1078 mgKOH/g) 3.70 g (0.035 mol), 3 polyester polyester (xl) (hydroxyl 264 mg KOH / g) 9.70 g (0.015 mol), 27 201245350 and 1,6 · hexa fresh as a raw material Polycarbonate® is a polyol (4) (oxygen clock ISOmgKOHygN^oo^mole), as a polymerization inhibitor 0.02g, as a reaction catalyst, dibutyltin dilaurate 2g, reacted for 3 hours Adding 2-hydroxyethyl acrylate (y) 6 〇〇g (〇〇52 molar reaction for 3 hours, and remaining isocyanate to 〇3' urethane carboxylic acid (methyl) acrylate I compound ( A_5) (toluene average = (Mw); 119,000) toluene solution (resin component 6 in [0098] &lt;Production Example 6: Amine phthalate acrylate compound (A_6)&gt; In a bottle with a thermometer, a lining machine, a water-cooled condenser, and a nitrogen-blowing population, 66.7 g of T benzene and 19.5 g of hydrogenated xylene diisocyanate (〇.l〇ί* Wei dimethanol (4) Base price 572mgKOH/g) 5.2_.026 Mo 3丄, polyester polyol (xl) (hydroxyl 264mgK〇H/g) 7 s〇g (〇〇14 Mo functional polyester polyol (X2) (hydroxyl price 63mgK〇H/g) 62 lg (〇〇35Mo = squamous 曱.. Q2g as a polymerization inhibitor, 0.02 g of dibutyltin dilaurate as a reaction catalyst, reacted at 60 C for 3 hours, and added with acrylic acid 2_glycol gt Mo) After reacting at 6G&lt;t for 3 hours, the reaction was terminated when the residual isocyanate was formed to obtain a urethane (meth)acrylate compound 003⁄4 weight average molecular weight (Mw); 51,000) toluene solution (Resin component 60%). <Production Example 7: a urethane (meth) acrylate compound (AJ)>, which was equipped with a thermometer, a masher, a water-cooled condenser, and a nitrogen gas inlet, and was burned with 66.7 g of toluene. Isophorone diisocyanate (z) 22.2 g (〇.10 mol), diol (x3) (hydroxyl price 1078 mg KOH/g) 2.80 g (0.027 mol), trifunctional, polyol (Xl) ( Hydroxyl valence 264 mgKOH/g) 9.20 g (0.014 mol), 2 s., ester polyol (X2) (hydroxyl price 63.4 mg KOH/g) 61.9 g (0.035 mol), as a sub-inhibitor of poly 5 inhibitor 0.02 g of methyl ether and dilauric acid dilaurate 2 g of the reaction catalyst were reacted at 60 C for 3 hours, and 2-acrylic acid was added to the base (y) 3 9 〇g (〇.〇34) , the ear) was reacted at 6 〇t for 3 hours, and the reaction was terminated when the residual isocyanate group became 〇3% at 28 201245350 to obtain an amine phthalate (meth) acrylate compound (A_7) (weight average molecular weight (Mw) ;29,000) toluene solution (resin component 6%). <Production Example 8: urethane (meth) acrylate type compound (A_8)> To a four-necked flask equipped with a meter, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 66.7 g of toluene was added to Liu Ya. Methyl diisocyanate (2) 178g (〇u Mo), neopentyl glycol (X3) (hydroxyl price 1078mgK〇H/g) 2 9〇g (〇〇28mol), 3-functional

聚酯多元醇(xl)(羥基價264mgKOH/g)9.70g(0.015莫耳）、2官能之 聚酯多元醇(x2)(羥基價63mgK〇H/g)65.4g(0.037莫耳）、當作聚合 抑制劑的氫，曱醚〇.〇2g、當作反應觸媒的二月桂酸二丁基錫 〇.〇2g，於601反應3小時，添加丙烯酸2_經基乙醋(y)4 1〇g(〇 〇35 莫耳），於60°C反應3小時，於殘存異氰酸醋基成為〇3%的時點 結束反應，獲得胺曱酸酯（曱基)丙烯酸酯系化合物(A_8)(重量平均 〈製造例9:胺甲酸酯（甲基)丙烯酸酯系化合物(A_9)&gt; 於具備溫度計、麟機、水冷冷凝器、氮氣吹人口的4 口燒 1添加甲.笨1〇〇g、氮化亞二甲苯二異氰酸醋(z)23.8g(〇.12莫 耳）、新戊二醇(X3)(經基價1078mgK⑽g)3 4〇g(〇 〇33莫耳）、3官 Ϊ之聚喊多元醇(xl)⑽基價77mgK⑽g)4ai_18莫耳）、2官 $^轉多兀醇(X2勝基價168mgK⑽幻28輕_2莫耳》當作 =抑制劑的賊甲醚_g、t作反應觸媒的二月桂酸二丁基錫 苔g ’於60〒反應3小時’添加丙稀酸2-經基乙醋(y)4.70g(0.040 W 6QC反應3小時’於殘存異氰酸絲成為G.3%的時點 a ’獲得胺曱酸醋(曱基)丙烯酸酷系化合物(A-9)(重量平均 ίiLfMW);5〇,〇〇〇)之曱苯溶液(樹脂成分5〇%)。 於具備溫度計、擾拌機、水冷 瓶中添加丙稀酸四氫糠酯66.7g &lt;製造例ίο:胺曱義(曱基)丙烯酸酉旨系化合物(A_1〇)&gt; 水冷冷凝器、氮氣吹入口的4 口燒 )6//g、氫化亞二曱苯二異氰酸酯 29 201245350 (z)19.8g(0.10莫耳）、新戊二醇（x3)(經基價 1078mgKOH/g)2.80g(0.027莫耳)、3官能之聚醋多元醇(χι)(經基價 264mgKOH/g)7.30g(0.011莫耳）' 2官能之聚酯多元醇(χ2)(經基價 63mgKOH/g)42.6g(0,024莫耳）、當作聚合抑制劑的氫醌曱喊 0.02g、當作反應觸媒的二月桂基二丁基錫〇.〇2g，於60〇c反應2 小時，添加3官能之聚酯多元醇（xi)(羥基價 264mgKOH/g)2.20g(0.0〇4〇莫耳)、2官能之聚酯多元醇(χ2)(羥基價 63mgKOH/g)21.3g(0.012莫耳）’於6〇°C反應2小時，添加丙浠酸 2-輕基乙酉曰(y)4.00g(0.034莫耳），於6〇。〇反應3小時，於殘存異氰 酸酯基成為0.3%的時點結束反應，獲得胺曱酸酯（曱基)丙稀酸醋 系化合物(A-10)(重量平均分子量(MW);52,〇〇〇)之丙烯酸四氫糠酯 溶液。 [0103] 〈製造例11:胺甲酸酯（甲基)丙烯酸酯系化合物(AM)&gt; 於具備溫度計、攪拌機、水冷冷凝器、氮氣吹入口的4 口燒 瓶中，添加異佛爾酮二異氰酸酯(z)12.9g(〇.〇58莫耳）、2官能之聚 酯多元醇(x2)(羥基價54mgKOH/g)82.6g(0.040莫耳）、當作反應觸 媒的二月桂基二丁基錫〇.G2g，於6Gt反應2小時，添加丙烯酸 2-經基乙S曰(y)4.40g(0.038莫耳）、當作聚合抑制劑的氫醌曱醚 〇.(Mg，於6〇t：反應3小時’於殘存異氰酸酯基成為〇撕的時點結 束反應，獲得胺曱酸酯（甲基)丙烯酸酯系化合物(Aq)(重 子量(Mw);17,000)。 [0104] &lt;製造例12:胺曱酸酯（曱基)丙烯酸酯系化合物(A，_ 於具備溫度計、麟機、水冷冷凝器、氮氣吹人口的4 口燒 升瓦中，添加異佛爾酮二異氰酸酯⑻26.5g(〇 12莫耳 多元醇(xl)(經基價264mgKOH/g)9,40g(〇,〇l5莫耳）、2官&quot;雙醚 ί元離防莫耳）、當作ί應觸媒 ί、 §，於6叱反應3小時，添加丙烯酸2~ 綠乙S日〇〇16離14莫耳）、當作聚合抑·的魏曱醚， 30 201245350 於60°C反應3小時’於殘存異氰酸酯基成為03%的時點結束反 應，獲得胺曱酸酯丙烯酸酯化合物(A’-2)(重量平均分子量 (Mw);4,000)。 [0105] 〈製造例13:胺曱酸酯（甲基)丙烯酸酯系化合物(a，^)〉 於具備溫度計、攪拌機、水冷冷凝器、氮氣吹入口的4 口燒 瓶中，添加曱苯42.9g、氫化亞二曱苯二異氰酸酯⑻32 3g(〇.17莫 耳）、新戊二醇(w)11.6g(0.11莫耳）、2官能之聚酯多元醇(χ2)(經基 價63mgKOH/g)49.6g(0.028莫耳）、當做聚合抑制劑的氫醌^醚 0.02g、^作反應角萄媒的一月桂基二丁基錫〇.〇2g，於6〇。〇反應2 小時，添加丙烯酸2-羥基乙酯(y)6.5〇g(〇.〇56莫耳），於㈨它反^ 3 小時’於殘存異氰酸醋基成為0.3%的時點結束反應，獲得胺甲〜酸 [酉0旨ίο甲6]基)丙稀酸醋系化合物(A、3)(重量平均*子量(MW);13,〇〇〇)。 準備以下物質當作光聚合起始劑(B)。 羥基環己基笨基酮(BASF JAPAN (股 「Irgacure 184」） ）J 衣 [0107] [實施例1〜9]Polyester polyol (xl) (hydroxyl price 264 mgKOH/g) 9.70 g (0.015 mol), bifunctional polyester polyol (x2) (hydroxyl price 63 mg K〇H/g) 65.4 g (0.037 mol), when As a polymerization inhibitor, hydrogen, oxime ether 〇. 〇 2g, dibutyltin dilaurate ruthenium ruthenium ruthenium 2g, used as a reaction catalyst, reacted at 601 for 3 hours, and added with acrylic acid 2 _ ethyl vinegar (y) 4 1 〇 g (〇〇35 mol), reacted at 60 ° C for 3 hours, and the reaction was terminated when the residual isocyanate group became 3%, to obtain an amine phthalate ester compound (A_8) ( Weight average <Production Example 9: urethane (meth) acrylate compound (A_9)&gt; In a thermometer, a lining machine, a water-cooled condenser, and a nitrogen-blowing population, four burners were added. g, xylene xylene diisocyanate (z) 23.8g (〇.12 mole), neopentyl glycol (X3) (base price 1078mgK (10)g) 3 4〇g (〇〇33 mol), 3 bureaucratic poly-polyol (xl) (10) base price 77mgK (10) g) 4ai_18 Moer), 2 official $ ^ to more sterols (X2 wins the base price 168mgK (10) illusion 28 light _2 Moer" as a = inhibitor of the thief Ether _g, t as a reaction catalyst for dibutyl tin dilaurate g g '60 The reaction was carried out for 3 hours 'addition of acrylic acid 2- via base ethyl vinegar (y) 4.70 g (0.040 W 6QC for 3 hours' to obtain an amine phthalic acid vinegar when the residual isocyanate was changed to G.3%. Acrylic cool compound (A-9) (weight average ίiLfMW); 5 〇, 〇〇〇) 曱 benzene solution (resin component 5 〇%). Adding acrylic acid to a thermometer, scrambler, water-cooled bottle Tetrahydrofurfuryl ester 66.7 g &lt;Production Example ίο: Amine 曱 曱 曱 曱 化合物 & & 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水Benzene diisocyanate 29 201245350 (z) 19.8 g (0.10 mol), neopentyl glycol (x3) (base price 1078 mg KOH / g) 2.80 g (0.027 mol), trifunctional polyglycol polyol (χι) (base price 264 mgKOH/g) 7.30 g (0.011 mol) '2-functional polyester polyol (χ2) (base price 63 mgKOH/g) 42.6 g (0,024 mol), hydroquinone as polymerization inhibitor 0.02 g of dilauryltin ruthenium ruthenium ruthenium 2 g, which is used as a reaction catalyst, was reacted at 60 ° C for 2 hours, and a trifunctional polyester polyol (xi) (hydroxyl price 264 mg KOH/g) was added at 2.20 g ( 0.0〇4〇莫耳), 2-functional polyester polyol (χ2) (hydroxyl group) 63mgKOH / g) 21.3g (0.012 mole) 'in response to 6〇 ° C 2 hours, propionic acid 2 Hay yiyou said light group (y) 4.00g (0.034 mole), in 6〇. The reaction was completed for 3 hours, and the reaction was terminated when the residual isocyanate group became 0.3% to obtain an amine phthalate (mercapto) acrylic acid vinegar compound (A-10) (weight average molecular weight (MW); 52, 〇〇〇 a solution of tetrahydrofurfuryl acrylate. <Production Example 11: urethane (meth) acrylate type compound (AM)> In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, isophorone II was added. Isocyanate (z) 12.9 g (〇. 58 mol), bifunctional polyester polyol (x2) (hydroxyl price 54 mg KOH / g) 82.6 g (0.040 mol), as a reaction catalyst, dilauryl di Butyltin oxime. G2g was reacted at 6 Gt for 2 hours, and 2-ethyl acrylate (y) 4.40 g (0.038 mol) was added as a polymerization inhibitor of hydroquinone ether. (Mg, 6 〇t The reaction was terminated at the time when the residual isocyanate group became a tear, and an amine phthalate (meth) acrylate type compound (Aq) (the amount of baryon (Mw); 17,000) was obtained. [0104] 12: Amine phthalate acrylate compound (A, _ added isophorone diisocyanate (8) 26.5g in a 4-burner tile equipped with a thermometer, a lining machine, a water-cooled condenser, and a nitrogen blowing population. (〇12 molar polyol (xl) (base price 264mgKOH / g) 9,40g (〇, 〇l5 moer), 2 official &quot; double ether ί元离防莫耳), as ί should be catalyst ί, § After reacting at 6 3 for 3 hours, adding 2% of green acrylic acid S, 〇〇16 to 14 moles, and as a polymerization inhibitor, 30 201245350 was reacted at 60 ° C for 3 hours', and the residual isocyanate group became 03%. The reaction was terminated to obtain an amine phthalate acrylate compound (A'-2) (weight average molecular weight (Mw); 4,000). [Production Example 13: Amine phthalate (meth) acrylate compound ( a,^)〉 42.9 g of toluene, hydrogenated bis-p-phenylene diisocyanate (8) 32 3 g (〇.17 mol), and neopentazone were placed in a 4-neck flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet. Alcohol (w) 11.6 g (0.11 mol), bifunctional polyester polyol (χ2) (base price 63 mg KOH/g) 49.6 g (0.028 mol), hydroquinone ether as a polymerization inhibitor 0.02 g, ^ As a reaction medium, a lauryl dibutyltin 〇. 〇 2g, at 6 〇. 〇 reaction for 2 hours, adding 2-hydroxyethyl acrylate (y) 6.5 〇 g (〇. 〇 56 Moer), in (9) It is reversed for 3 hours' at the time when the residual isocyanate group becomes 0.3%, and the reaction is terminated to obtain an amine acetal-acid compound (A, 3). * The average molecular weight (MW); 13, 〇〇〇). The following were prepared as photopolymerization initiator (B). Hydroxycyclohexyl phenyl ketone (BASF JAPAN (share "Irgacure 184")) J clothing [0107] [Examples 1 to 9]

丙~酸酯系化合物 、曱笨’使固體成分濃 [實施例10]The propionate-ester compound and the oxime compound make the solid component thick [Example 10]

[0109] (比較例1) T丞)内烯酸酯系化合物 ’獲得活性能量射線硬化 31 201245350 將實施例1中^胺曱酸酯（甲基)丙烯酸酯系化合物(A-1)改成 使用上述製造例11獲得之胺甲酸酯（曱基)丙烯酸酯(AM)，並將光 聚合起始劑(B-1)之使用1改為4份，除此以外與實施例丨同樣進 行，獲得活性能量射線硬化性樹脂組成物。 、 [0110] [比較例2] 將實施例1中之胺曱酸酯（甲基)丙烯酸酯系化合物(Α_υ改為 使用上述製造例12獲得之胺甲酸酯（甲基)丙烯酸酯(Α，_2)，並將光 t合起始劑(Β-1)之使用量改為4份’除此以外與實施例1同樣進 行，獲得活性能量射線硬化性樹脂組成物。 [0111] [比較例3] 將實施例1中之胺甲酸酯（甲基)丙烯酸酯系化合物(A_i)改為 使用上述製造例13獲得之胺曱酸酯（甲基)丙烯酸酯(A，_3)，除此以 外與貫施例1同樣進行’獲得活性能量射線硬化性樹脂組成物。 [0112] ’ 針對上述實施例1〜10、比較例1〜3獲得之活性能量射線硬化 性樹脂組成物，評價透明性。 [0113] &lt;透明性&gt; 與APHA((Hazen單位色數)標準液進行比色，測定活性能量 綿硬化性樹脂組成物之APHA値，並以下列評價基準評價。結果 如下表1。 (評價基準） Q:APHA値小於30 x:APHA値為30以上。 [0114] 又，使用獲得之活性能量射線硬化性樹脂組成物，進行復原 性、伸縮性的評價。 ” [0115] 32 201245350 &lt;復原性&gt; 、將上述獲得之活性能量射線硬化性樹脂組成物以塗佈器塗佈 於黑色聚碳酸酯基材（日本Testpanel(股)公司製，2x70x150mm)使 硬化塗膜成為膜厚40μηι厚，於90。(：使乾燥ό分鐘後，使用高壓 欠銀4燈80W、1燈，從18cm的向度以3.4m/min的傳送帶速度 進行3次脈衝的紫外線照射(累積照射量1〇〇〇mJ/cm2)，獲得硬化 ^臈二又，實施例10獲得之活性能量射線硬化性樹脂組成物由於 為無溶劑之組成物，故上述硬化塗膜形成步驟省略乾燥 得硬化塗膜。 Λ —使用上述硬化塗膜，於23 C、50%Rh的條件，使用黃銅製2 =毛刷’以500g負荷來回5次使塗膜損傷，測定直到以目視能確 涊有損傷為止的時間，以下列評價基準進行評價。其結 (評價基準） 〇:損傷在3分鐘以内復原 △.損傷在超過3分鐘、1〇分鐘以内復原 X:在施以損傷1〇分鐘後確認損傷未復原 [0116] &lt;伸縮性&gt; 將上述獲得之活性能量射線硬化性樹脂組成物利用塗佈哭塗 2在玻璃基材(日本Testpanel (股)公司製，2χ70χ150 ς j成為厚度40μιη ’於9(TC錢6分鐘後，使用高壓水銀燈燈 、1燈，從18cm的高度以3.4m/min的傳送帶速度進行3次^ ，紫外線照射(歸照射量議邊m2)，軸 ： 剝離塗膜，獲得硬化塗膜。 ^土犋後，僅 益溶ΐ之舌性能量射線硬化性樹脂組成物由於為 …'奋J之、，且成物，故上述硬化塗腹形成步驟省略乾 硬化塗膜。 /冲馒侍 將上述硬化塗膜裁切為寬丨〇mmx長度3〇mm，將声 二坑、纖h的條件π娜方向拉伸，於維 _的狀4(I.5倍的*度），固定秒，之後脫_定，測 33 201245350 膜的伸長度成為與伸張前為相同大小的時間，並以下列評價基準 評價。其結果如下表1所示。 (評價基準） 〇:1分鐘以内回到原來的大小 △:於超過1分鐘、3分鐘以内回到原來的大小 X:超過3分鐘仍未回到原來的大小 [0117] [表1] 胺甲酸酯(甲基)丙烯酸酯系化合物(Α) 光聚合 起始劑 (B) 透明性 復原性 伸縮性 種類 摻合 m(重 a份） 平均 羥基 數 (mol) 乙烯性不 飽和基含 (mmol/g) 重s平 均分子 S (B-I)(重 量份） APHA 値 評 價 時間 評 價 時間 評 偾 施 例1 Α-1 100 2.29 0.35 85,000 2.4 11 0 瞬間 〇 5秒 0 施 例2 Α-2 100 2,26 0.33 57,000 2.4 12 〇 瞬間 〇 5秒 0 實 施 例3 Α-3 100 2.31 0.33 78,000 2.4 10 〇 瞬間 〇 5秒 0 實 施 例4 Α-4 100 2.37 0.51 135,000 2.4 13 0 3分 鐘 〇 5秒 0 施 例5 Α-5 100 2.18 0.52 119,000 2.4 11 〇 3分 鐘 〇 5秒 0 實 施 例6 Α-6 100 2.29 0.34 51,000 2.4 13 0 瞬間 〇 5秒 0 ίΓΤϊϊ 5Λ 施 例7 Α-7 100 2.29 0.34 29,000 2.4 12 0 10 秒 〇 5秒 0 實 施 例8 Α-8 100 2.29 0.36 158,000 2.4 10 0 瞬間 〇 5秒 0 施 例9 Α-9 100 2.31 0.41 50,000 2.4 12 〇 瞬間 〇 5秒 0 施 例 10 Α-10 100 2.29 0.34 52,000 4 16 〇 瞬間 〇 5秒 0 比 較 例1 Α’·] 100 2.00 0.38 17,000 4 12 〇 X 5秒 0 34 201245350 比 較 例2 Α’-2 100 比 較 例3 Α，-3 100 2.35 2.00(Comparative Example 1) T丞) lactone-based compound 'obtained active energy ray hardening 31 201245350 The amine phthalate (meth) acrylate compound (A-1) in Example 1 was changed to The same procedure as in Example 丨 was carried out except that the urethane (mercapto) acrylate (AM) obtained in the above Production Example 11 was used, and the use 1 of the photopolymerization initiator (B-1) was changed to 4 parts. An active energy ray curable resin composition was obtained. [Comparative Example 2] The amine phthalate (meth) acrylate compound of Example 1 (Α_υ was changed to the urethane (meth) acrylate obtained by the above Production Example 12 (Α In the same manner as in Example 1 except that the amount of the photo-initiating agent (Β-1) was changed to 4 parts, an active energy ray-curable resin composition was obtained. [0111] [Comparative Example 3] The urethane (meth) acrylate type compound (A_i) in Example 1 was changed to the amine phthalate (meth) acrylate (A, _3) obtained by the above Production Example 13, except In the same manner as in Example 1, the active energy ray-curable resin composition was obtained. [0112] The active energy ray-curable resin compositions obtained in the above Examples 1 to 10 and Comparative Examples 1 to 3 were evaluated for transparency. &lt;Transparency&gt; The color of the APHA (the (Hazen unit color) standard solution was measured, and the APHA of the active energy sclerosing resin composition was measured and evaluated according to the following evaluation criteria. The results are shown in Table 1 below. (Evaluation criteria) Q: APHA 値 is less than 30 x: APHA 値 is 30 or more. [0114] The performance amount of the radiation-curable resin composition was evaluated for the restorability and the stretchability. [0115] 32 201245350 &lt;Recoverability&gt; The active energy ray-curable resin composition obtained above was applied by an applicator. The black polycarbonate substrate (manufactured by Japan Testpanel Co., Ltd., 2x70x150mm) has a thickness of 40 μm thick at 90°. (:: After drying for a minute, use a high-pressure under-silver 4 lamp 80W, 1 lamp, from Three-pulse ultraviolet irradiation (accumulated irradiation amount: 1 〇〇〇 mJ/cm 2 ) at a conveyor speed of 3.4 m/min to obtain a hardening effect, and an active energy ray-curable resin obtained in Example 10 Since the composition is a solvent-free composition, the hardened coating film forming step is omitted, and the dried hardened coating film is omitted. Λ The above-mentioned hardened coating film is used, and in the condition of 23 C and 50% Rh, a brass 2 = brush is used. The coating film was damaged by a load of 500 g five times, and the time until the damage was visually confirmed was evaluated by the following evaluation criteria. The knot (evaluation standard) 〇: The damage was restored within 3 minutes Δ. The damage exceeded 3 points The clock is restored within 1 minute. X: After the damage is applied for 1 minute, the damage is not restored. [0116] &lt;Flexibility&gt; The active energy ray-curable resin composition obtained above is coated with a coating of 2 in the glass. The substrate (manufactured by Japan Testpanel Co., Ltd., 2χ70χ150 ς j becomes the thickness 40μιη ' at 9 (after 6 minutes of TC money, using a high-pressure mercury lamp, 1 lamp, 3 times from a height of 18cm at a conveyor speed of 3.4m/min) ^, ultraviolet irradiation (return to the side of the irradiation m2), shaft: peeling off the coating film to obtain a hardened coating film. After the soil is cured, the composition of the tongue-forming energy ray-curable resin is only a hardened coating film, and the hardening coating film is omitted. / 馒 馒 馒 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 上述 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化 硬化), fixed seconds, then de-determined, measured 33 201245350 The elongation of the film became the same time as before stretching, and was evaluated on the following evaluation criteria. The results are shown in Table 1 below. (Evaluation criteria) 〇: Return to the original size within 1 minute △: Return to the original size within 1 minute and 3 minutes. X: It has not returned to the original size for more than 3 minutes [0117] [Table 1] Amine Acid ester (meth) acrylate compound (Α) Photopolymerization initiator (B) Transparency resilience type blending m (weight a part) Average number of hydroxyl groups (mol) Ethylene unsaturated group containing (mmol /g) Weight s average molecular S (BI) (parts by weight) APHA 値 Evaluation time evaluation time evaluation Example 1 Α-1 100 2.29 0.35 85,000 2.4 11 0 Instant 〇 5 seconds 0 Example 2 Α-2 100 2, 26 0.33 57,000 2.4 12 〇 instantaneous 〇 5 seconds 0 Example 3 Α-3 100 2.31 0.33 78,000 2.4 10 〇 instantaneous 〇 5 seconds 0 Example 4 Α-4 100 2.37 0.51 135,000 2.4 13 0 3 minutes 〇 5 seconds 0 5 Α-5 100 2.18 0.52 119,000 2.4 11 〇3 minutes 〇5 seconds 0 Example 6 Α-6 100 2.29 0.34 51,000 2.4 13 0 Instant 〇 5 seconds 0 ΓΤϊϊ 5 Λ Example 7 Α-7 100 2.29 0.34 29,000 2.4 12 0 10 seconds 〇 5 seconds 0 Example 8 Α-8 100 2.29 0.36 158,000 2.4 10 0 Instant 〇 5 seconds 0 Example 9 Α-9 100 2.31 0.41 50,000 2.4 12 〇 Instant 〇 5 seconds 0 Example 10 Α-10 100 2.29 0.34 52,000 4 16 〇 Instant 〇 5 seconds 0 Comparative Example 1 Α'·] 100 2.00 0.38 17,000 4 12 〇X 5 seconds 0 34 201245350 Comparative Example 2 Α'-2 100 Comparative Example 3 Α, -3 100 2.35 2.00

1.43 0.56 4,000 4 25 ο ※l X X ------ ~·_ 一 13,000 2.4 8 ο ※l X ※3 X ※l··於經過10分鐘的時點未復原 ※之:塗膜未伸長到規定的長度，無法測定 ※3於經過3分鐘的時點未回到原來的長度 [0118] 醇 .80 季化價、ΐί;Γ°:使用含有含3個以上的經基的多元 f二Γ=勿而獲得之二 [0119] 官』官能之多元醇系化合物，並使用不含3 胺甲酸酷(甲基)丙稀酸醋系化合物 而獲付之比較例1及3之硬化塗膜，復 之硬化塗關伸雛亦差。 幻《比#乂例3 八工^’使用雖含有3官能以上之多元醇系化合物但是重量平均 系化合物而獲得之比較例2 之硬化塗膜，復原性、伸縮性均差。 [0120] 與施i:二係針對本發明之具體形態揭示’但上述 11的各種變形，係在本發明之範圍内。 [0121] 本發明之活性能量概硬化性樹脂 時，能維持胺甲酸酯結構特有之涂膣 田衣成吏土、 am 饮伸張性且具備由於3維網目 構而付的她收祕，所以可獲得具有伸張 、收縮性能的彈性 35 201245350 塗膜，因此，能形成就對於損傷之復原性而言為高實用性的硬化 塗膜，當作塗料、印墨、塗佈劑，尤其最表面用塗佈劑為有用。 【圖式簡單說明】 〇 【主要元件符號說明】 無。 361.43 0.56 4,000 4 25 ο *l XX ------ ~·_ 13,000 2.4 8 ο *l X *3 X *l··There is no recovery after 10 minutes. ※The coating film is not stretched to the prescribed level. The length cannot be measured. *3 does not return to the original length after 3 minutes [0118] Alcohol. 80 Quaternary price, ΐί; Γ °: Use a multi-element containing more than 3 meridians. And the obtained poly-alcohol-based compound of the [0119] official function, and the cured coating film of Comparative Examples 1 and 3 obtained by using the 3-aminocarbamic acid cool (meth)acrylic acid vinegar-based compound, Hardening and coating are also poor. The hardened coating film of Comparative Example 2 obtained by using a polyvalent alcohol-based compound having a trifunctional or higher functional group but having a weight average compound was inferior in both the restorability and the stretchability. [0120] It is to be noted that the second embodiment is disclosed in the specific form of the present invention, but various modifications of the above 11 are within the scope of the present invention. In the active energy-hardening resin of the present invention, it is possible to maintain the urethane structure, which is unique to the urethane structure, and to obtain the abundance of the 膣 、 、 am am am am am am 且 且 且 且 且 且 且 且 am am am am am am am am am am am am am am Elastic 35 201245350 coating film with stretch and shrink properties, therefore, it can form a hardened coating film which is highly practical for the recovery of damage, and is used as a coating, ink, coating agent, especially for the most surface coating. The agent is useful. [Simple description of the diagram] 〇 [Description of main component symbols] None. 36

Claims (1)

201245350 七、申請專利範圍： 1. 一種活性能量射線硬化性樹脂組成物，係含有使多元醇 合物(X)、含羥基之（甲基)丙烯酸酯系化合物(y)、及多元異^酸酽 系化合物(Z)反應而成的重量平均分子量為i萬〜80萬之胺曱^酉: 入物fif元醇系化合物(X)包含含有3個以上之羥基的多元醇系化 ^如申請專職圍第丨項之活性能量射線硬化性樹赌 物、中，該含有3個以上之經基的多元醇系化合物(χ1)，係 於聚酯系多元醇及聚醚系多元醇中之至少i種。 ’、、 私!ΐ中請專利範圍第1或2項之活性能量射線硬化性樹脂虹成 上鄕说繼合綱之重量平 樹脂範項中任—項之活性能量射線硬化性 痴其西 /、中以夕元醇系化合物⑻係包含含有2個羥基且 里土 小於450mgKOH/g之多元醇系化合物(χ2)。 編匕31^利範圍11至4項中任—項之活性能量射線硬化性 秘月曰組成物，其中’該多元醇系化人物ω白八人古？袖〜甘， 45〇mgKOHyg W sir 任一含有如申請專糧圍第1至7項中 Λ由^置5化性樹脂組成物而成。 使用。38項之塗佈劑’其係作為最表面用塗佈劑 37201245350 VII. Patent application scope: 1. An active energy ray-curable resin composition containing a polyol compound (X), a hydroxyl group-containing (meth) acrylate compound (y), and a polyisophthalic acid The weight average molecular weight of the reaction of the lanthanoid compound (Z) is from 10,000 to 800,000 amines. The fluorinated alcohol compound (X) contains a polyol containing three or more hydroxyl groups. The active energy ray-curable tree gambling material of the second aspect of the present invention, wherein the polyol compound (χ1) containing three or more kinds of radicals is at least one of a polyester polyol and a polyether polyol. i kind. ',, Private! In the middle of the patent range, the active energy ray-curable resin of the first or second patent range, Hong Cheng, said that the active energy ray-curable stagnation of the syllabus The middle oxime alcohol compound (8) is a polyol-based compound (χ2) containing two hydroxyl groups and having a soil of less than 450 mgKOH/g. Compiled 31% of the active energy ray-curable secret moon 曰 composition of the range of items 11 to 4, where the 'polyol-based character ω white eight ancient? Sleeve ~ Gan, 45 〇 mgKOHyg W sir Any one of the items 1 to 7 of the application for special grain is composed of a compound of 5 resin. use. The coating agent of item 38 is used as the coating agent for the outermost surface 37
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