TW202006067A - Curing resin composition, film of the curing resin composition, and molded article of the film - Google Patents

Curing resin composition, film of the curing resin composition, and molded article of the film Download PDF

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TW202006067A
TW202006067A TW108119282A TW108119282A TW202006067A TW 202006067 A TW202006067 A TW 202006067A TW 108119282 A TW108119282 A TW 108119282A TW 108119282 A TW108119282 A TW 108119282A TW 202006067 A TW202006067 A TW 202006067A
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resin composition
curable resin
meth
compound
weight
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小野真司
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日商尼歐斯股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The purpose of the present invention is to provide a curable resin composition that is capable of forming a cured coating film which has high chemical resistance, while having an elongation that does not interfere with injection molding. A curable resin composition according to the present invention contains (A) a polyurethane (meth)acrylate compound which has a urethane bond equivalent weight of 210 g/mol or less, (B) a polymerization initiator and (C) an aprotic polar solvent.

Description

硬化性樹脂組合物及使用其之膜、以及使用膜之成形品Curable resin composition, film using the same, and molded product using the film

本發明係關於一種硬化性樹脂組合物。進而，本發明係關於一種使用藉由使硬化性樹脂組合物硬化而獲得之硬化覆膜之成形膜以及成形品。The present invention relates to a curable resin composition. Furthermore, the present invention relates to a molded film and a molded product using a cured coating film obtained by curing a curable resin composition.

汽車內裝、汽車外裝、電化產品等樹脂成形品或塑膠成形品之表面要求具有不會或難以因衝擊而產生損傷之耐擦傷性。因此，以提高該等成形品之表面之耐擦傷性為目的而廣泛地設置耐擦傷性之保護層。先前，藉由射出成形法等而獲得樹脂成形品或塑膠成形品後，進行耐擦傷性成分之塗佈等而設置耐擦傷性保護層。然而，若可藉由射出成形法一次獲得具有耐擦傷性保護層之樹脂成形品或塑膠成形品，則成形加工步驟減少，於經濟上較為有利。因此，嘗試開發可形成兼備能夠耐受射出成形法之較高伸長率及耐擦傷性之保護層之硬化性組合物。The surface of resin molded products or plastic molded products such as automotive interiors, automotive exteriors, electrified products, etc. is required to have scratch resistance that is not or difficult to cause damage due to impact. Therefore, in order to improve the scratch resistance of the surface of these molded products, a scratch-resistant protective layer is widely provided. In the past, after obtaining a resin molded product or a plastic molded product by injection molding or the like, a scratch-resistant component is applied to provide a scratch-resistant protective layer. However, if a resin molded product or a plastic molded product having a scratch-resistant protective layer can be obtained by injection molding at a time, the molding process steps are reduced, which is economically advantageous. Therefore, attempts have been made to develop a curable composition that can form a protective layer that can withstand higher elongation and scratch resistance of the injection molding method.

日本專利第6123428號中揭示一種活性能量線硬化性樹脂組合物，其可形成兼備能夠追隨三維加工時之變形之柔軟性、斷裂強度及機械強度、損傷修復性、耐擦傷性等之硬化膜。該活性能量線硬化性樹脂組合物之特徵在於：包含作為聚異氰酸酯與聚碳酸酯多元醇及(甲基)丙烯酸羥基烷基酯之反應物之胺基甲酸酯(甲基)丙烯酸酯系低聚物，硬化膜之拉伸彈性模數具有特定數值。Japanese Patent No. 6123428 discloses an active energy ray-curable resin composition that can form a cured film that has flexibility, breaking strength and mechanical strength, damage repairability, and scratch resistance that can follow deformation during three-dimensional processing. The active energy ray-curable resin composition is characterized in that it contains a low urethane (meth)acrylate as a reactant of polyisocyanate, polycarbonate polyol and hydroxyalkyl (meth)acrylate. The tensile modulus of elasticity of the polymer and the cured film has a specific value.

[發明所欲解決之問題][Problems to be solved by the invention]

專利文獻1之活性能量線硬化性樹脂組合物如上所述可形成柔軟且具有耐擦傷性之硬化膜，但存在與化學品接觸會變白之問題。因此，本發明之目的在於提供一種硬化性樹脂組合物，其可形成兼備耐受包含嵌入成形法之射出成形法中之變形之較高伸長率、及耐擦傷性，且一併具有耐化學品性之硬化覆膜。 [解決問題之技術手段]The active energy ray-curable resin composition of Patent Document 1 can form a soft and scratch-resistant cured film as described above, but there is a problem that it becomes white when contacted with chemicals. Therefore, an object of the present invention is to provide a curable resin composition that can form a high elongation that is resistant to deformation in the injection molding method including the insert molding method and scratch resistance, and has chemical resistance together Hardening coating. [Technical means to solve the problem]

本發明之實施形態中之硬化性樹脂組合物係包含胺基甲酸酯鍵當量為210克/莫耳以下之聚胺基甲酸酯(甲基)丙烯酸酯化合物(A)、聚合起始劑(B)、及非質子性極性溶劑(C)之硬化性樹脂組合物。此處，聚胺基甲酸酯(甲基)丙烯酸酯化合物(A)之特徵在於：其係使以下之化合物：聚異氰酸酯化合物(a1)與碳數1～6之多元醇化合物(a2)及(甲基)丙烯酸羥基烷基酯化合物(a3)反應而成之化合物。 本發明之其他實施形態係一種成形膜，其具有使硬化性樹脂組合物硬化而成之硬化覆膜、及基材。 本發明之進而其他實施形態係一種使硬化性樹脂組合物硬化而成之硬化覆膜、以及於表面具有使硬化性樹脂組合物硬化而成之硬化覆膜之成形品。 [發明之效果]The curable resin composition in the embodiment of the present invention includes a polyurethane (meth)acrylate compound (A) having a urethane bond equivalent weight of 210 g/mol or less and a polymerization initiator (B), and the curable resin composition of the aprotic polar solvent (C). Here, the polyurethane (meth)acrylate compound (A) is characterized by the following compounds: a polyisocyanate compound (a1) and a C1-C6 polyol compound (a2) and A compound obtained by reacting a hydroxyalkyl (meth)acrylate compound (a3). Another embodiment of the present invention is a formed film having a cured film formed by curing a curable resin composition and a base material. Still another embodiment of the present invention is a molded product having a cured film obtained by curing a curable resin composition and a cured film obtained by curing the curable resin composition on the surface. [Effect of invention]

使用本發明之硬化性樹脂組合物所形成之成形膜於射出成形法等熱成形中具有充分之伸長率。又，將本發明之成形膜用於樹脂成形品或塑膠成形品之表面之加工之成形品於成形品之表面密接有硬化覆膜，從而有效地保護其表面。The formed film formed using the curable resin composition of the present invention has sufficient elongation in thermoforming such as injection molding. In addition, the molded film of the present invention is used for processing the surface of a resin molded product or a plastic molded product. A cured film is closely adhered to the surface of the molded product, thereby effectively protecting the surface.

以下說明本發明之實施形態。本發明之一實施形態係一種硬化性樹脂組合物，其包含胺基甲酸酯鍵當量為210克/莫耳以下之聚胺基甲酸酯(甲基)丙烯酸酯化合物(A)、聚合起始劑(B)、及非質子性極性溶劑(C)。The embodiments of the present invention will be described below. An embodiment of the present invention is a curable resin composition comprising a polyurethane (meth)acrylate compound (A) having an urethane bond equivalent weight of 210 g/mole or less, polymerized Starting agent (B), and aprotic polar solvent (C).

於本實施形態中，硬化性樹脂組合物係指於常溫下存在時為液體狀態，藉由紫外線、紅外線、X射線等活性能量之照射、熱能之施加、化學物質之添加等契機開始硬化反應而可形成硬化物或硬化覆膜之以樹脂或塑膠或該等之原料單體為主成分之混合物。硬化性樹脂組合物用於塗料、止漏(sealing)材料、密封材料、接著劑等廣泛用途，根據其用途而需滿足各種要求性能。本實施形態之硬化性樹脂組合物之硬化物可作為樹脂、塑膠、金屬等成形品之表面之加工用或加飾用膜使用，該硬化覆膜密接於成形品表面上而不易剝離，能夠防止因外部衝擊形成損傷。In the present embodiment, the curable resin composition means that it is in a liquid state when it exists at room temperature, and the curing reaction starts by the opportunity of irradiation of active energy such as ultraviolet rays, infrared rays, X-rays, the application of thermal energy, and the addition of chemical substances. A mixture of resin or plastic or these raw material monomers as the main component that can form a hardened material or hardened film. The curable resin composition is used for a wide range of applications such as paints, sealing materials, sealing materials, and adhesives, and needs to satisfy various required performances according to its use. The cured product of the curable resin composition of this embodiment can be used as a film for processing or decorating the surface of molded products such as resins, plastics, metals, etc. The cured coating is closely attached to the surface of the molded product and is not easily peeled, which can prevent Damage caused by external impact.

本實施形態之硬化性樹脂組合物包含胺基甲酸酯鍵當量為210克/莫耳以下之聚胺基甲酸酯(甲基)丙烯酸酯化合物(A)。聚胺基甲酸酯(甲基)丙烯酸酯化合物係指於分子內具有胺基甲酸酯鍵、且具有選自丙烯醯基(acryl)或甲基丙烯醯基(metaacryl)之聚合基之聚合物，即聚合體或低聚物。於聚胺基甲酸酯(甲基)丙烯酸酯化合物(A)中包含藉由照射活性能量線或賦予熱、或添加聚合起始劑而裂解開始自由基聚合之丙烯醯基(acryl)或甲基丙烯醯基(metaacryl)。聚胺基甲酸酯(甲基)丙烯酸酯化合物(A)之胺基甲酸酯鍵當量為210克/莫耳以下。此處，胺基甲酸酯鍵當量係指聚胺基甲酸酯(甲基)丙烯酸酯化合物(A)之重量平均分子量(即1莫耳之聚胺基甲酸酯(甲基)丙烯酸酯化合物(A)之重量)與聚胺基甲酸酯(甲基)丙烯酸酯化合物(A)中所存在之胺基甲酸酯鍵數量之比，單位為克/莫耳。胺基甲酸酯鍵當量之值較小意味著聚胺基甲酸酯(甲基)丙烯酸酯化合物(A)之分子中存在較多胺基甲酸酯鍵。The curable resin composition of this embodiment contains a polyurethane (meth)acrylate compound (A) having a urethane bond equivalent weight of 210 g/mole or less. Polyurethane (meth)acrylate compound refers to a polymerization having a urethane bond in the molecule and having a polymer group selected from acryl or metaacryl Substances, that is, polymers or oligomers. The polyurethane (meth)acrylate compound (A) contains an acrylic group (acryl) or methyl group that starts to undergo free radical polymerization by irradiating active energy rays, applying heat, or adding a polymerization initiator. Methacrylic acid (metaacryl). The urethane bond equivalent of the polyurethane (meth)acrylate compound (A) is 210 g/mole or less. Here, the urethane bond equivalent refers to the weight average molecular weight of the polyurethane (meth)acrylate compound (A) (that is, 1 mole of polyurethane (meth)acrylate The ratio of the weight of compound (A)) to the number of urethane bonds present in the polyurethane (meth)acrylate compound (A), the unit is g/mol. The smaller value of the urethane bond equivalent means that there are more urethane bonds in the molecule of the polyurethane (meth)acrylate compound (A).

若使用胺基甲酸酯鍵當量之值較小之聚胺基甲酸酯(甲基)丙烯酸酯化合物作為(A)，則於使硬化性樹脂組合物硬化而成之硬化覆膜聚合物中存在較多胺基甲酸酯鍵。若聚胺基甲酸酯(甲基)丙烯酸酯化合物(A)之胺基甲酸酯鍵當量為210克/莫耳以下，則可確保足以賦予硬化覆膜耐化學品性之胺基甲酸酯鍵數。If a polyurethane (meth)acrylate compound having a smaller value of urethane bond equivalent is used as (A), in the cured film polymer obtained by curing the curable resin composition There are more urethane bonds. If the urethane bond equivalent of the polyurethane (meth)acrylate compound (A) is 210 g/mole or less, sufficient amino acid can be ensured to impart chemical resistance to the cured film Number of ester bonds.

於實施形態中，作為(A)成分之聚胺基甲酸酯(甲基)丙烯酸酯化合物較佳為使聚異氰酸酯化合物(a1)與碳數1～6之多元醇化合物(a2)及(甲基)丙烯酸羥基烷基酯化合物(a3)反應而成之化合物。聚異氰酸酯化合物(a1)係指於1分子中具有2個以上之異氰酸基(-N=C=O)之化合物。作為聚異氰酸酯化合物(a1)，特佳為使用於分子內具有2個異氰酸基之二異氰酸酯化合物。此處，作為二異氰酸酯化合物，可列舉：雙(異氰酸基甲基)環己烷、環己烷二異氰酸酯、二苯基甲烷二異氰酸酯(MDI)、六亞甲基二異氰酸酯(HDI)、甲苯二異氰酸酯(Toluene/Tolylene diisocyanate、TDI)、苯二甲基二異氰酸酯(XDI)、異佛爾酮二異氰酸酯(IPDI)、環己基二異氰酸酯、二環己基甲烷4,4'-二異氰酸酯等，可使用該等之中1種以上。In the embodiment, the polyurethane (meth)acrylate compound as the component (A) is preferably a polyisocyanate compound (a1), a C1-C6 polyol compound (a2) and (a Group) hydroxyalkyl acrylate compound (a3) reacted compound. The polyisocyanate compound (a1) refers to a compound having two or more isocyanate groups (-N=C=O) in one molecule. The polyisocyanate compound (a1) is particularly preferably a diisocyanate compound having two isocyanate groups in the molecule. Here, examples of the diisocyanate compound include bis(isocyanatomethyl)cyclohexane, cyclohexane diisocyanate, diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), Toluene/Tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), cyclohexyl diisocyanate, dicyclohexylmethane 4,4'-diisocyanate, etc., One or more of these can be used.

多元醇化合物(a2)係指於1分子中具有2個以上之羥基(-OH)之化合物。於實施形態中，多元醇化合物(a2)較佳為碳數1～6。藉由使用分子量相對較低之多元醇化合物作為(a2)，可使聚胺基甲酸酯(甲基)丙烯酸酯化合物(A)中之胺基甲酸酯鍵數較多。即，可藉由調整多元醇化合物(a2)之碳數，而調整聚胺基甲酸酯(甲基)丙烯酸酯化合物(A)之胺基甲酸酯鍵當量。作為此種多元醇化合物，例如可列舉：甲二醇、乙二醇、正丙二醇、異丙二醇、正丁二醇、異丁二醇、第三丁二醇、正戊二醇、正己二醇、二羥基環己烷等脂肪族或脂環族二醇化合物；1,2,4-丁三醇等脂肪族或脂環族三醇化合物；鄰苯二酚、間苯二酚、對苯二酚等芳香族二醇化合物；及偏苯三酚、間苯三酚、鄰苯三酚等芳香族三醇化合物。可使用該等之中1種以上。The polyol compound (a2) refers to a compound having two or more hydroxyl groups (-OH) in one molecule. In the embodiment, the polyol compound (a2) preferably has 1 to 6 carbon atoms. By using a polyol compound with a relatively low molecular weight as (a2), the number of urethane bonds in the polyurethane (meth)acrylate compound (A) can be increased. That is, the urethane bond equivalent of the polyurethane (meth)acrylate compound (A) can be adjusted by adjusting the carbon number of the polyol compound (a2). Examples of such polyol compounds include methylene glycol, ethylene glycol, n-propylene glycol, isopropylene glycol, n-butanediol, isobutanediol, third butanediol, n-pentanediol, and n-hexanediol. Aliphatic or cycloaliphatic diol compounds such as dihydroxycyclohexane; aliphatic or cycloaliphatic triol compounds such as 1,2,4-butanetriol; catechol, resorcinol, hydroquinone Etc. aromatic diol compounds; and aromatic triol compounds such as pyrogallol, phloroglucinol, pyrogallol, etc. One or more of these can be used.

(甲基)丙烯酸羥基烷基酯化合物(a3)係指於1分子中具有羥基烷基(具有羥基之烷基)、及丙烯醯基(acryl)或甲基丙烯醯基(metaacryl)之化合物。作為(甲基)丙烯酸羥基烷基酯化合物，可列舉：丙烯酸羥基甲酯、甲基丙烯酸羥基甲酯、丙烯酸羥基乙酯、甲基丙烯酸羥基乙酯、季戊四醇二丙烯酸酯、季戊四醇二甲基丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇三甲基丙烯酸酯等，可使用該等之中1種以上。The hydroxyalkyl (meth)acrylate compound (a3) refers to a compound having a hydroxyalkyl group (alkyl group having a hydroxy group), and acryl or methacryl group in one molecule. Examples of hydroxyalkyl (meth)acrylate compounds include hydroxymethyl acrylate, hydroxymethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, pentaerythritol diacrylate, and pentaerythritol dimethacrylate. , Pentaerythritol triacrylate, pentaerythritol trimethacrylate, etc., one or more of them can be used.

可藉由使上述(a1)中存在之異氰酸基與(a2)中存在之羥基及(a3)中存在之羥基反應而形成胺基甲酸酯鍵，從而生成聚胺基甲酸酯(甲基)丙烯酸酯化合物(A)。較佳為首先使(a1)成分與(a2)成分反應，繼而追加(a3)成分，藉此生成聚胺基甲酸酯(甲基)丙烯酸酯化合物(A)。於聚胺基甲酸酯(甲基)丙烯酸酯化合物(A)中存在來自(a3)之自由基聚合性基(丙烯醯基(acryl)或甲基丙烯醯基(metaacryl))。該自由基聚合性基之反應有助於實施形態之硬化性樹脂組合物之硬化。Polyurethanes can be formed by reacting the isocyanate groups present in (a1) above with the hydroxyl groups present in (a2) and the hydroxyl groups present in (a3) to form a carbamate bond ( Methacrylate compound (A). Preferably, the component (a1) and the component (a2) are reacted first, and then the component (a3) is added, thereby generating the polyurethane (meth)acrylate compound (A). In the polyurethane (meth)acrylate compound (A), there is a radical polymerizable group (acryl or metaacryl) derived from (a3). The reaction of the radical polymerizable group contributes to the curing of the curable resin composition of the embodiment.

實施形態之硬化性樹脂組合物除了聚胺基甲酸酯(甲基)丙烯酸酯化合物(A)以外亦包含聚合起始劑(B)。聚合起始劑係響應光照射、熱賦予等刺激而引發單體之聚合反應之化合物。於實施形態之硬化性樹脂組合物中，較佳為使用藉由包括紫外線、電子束、可見光在內之光之照射而引發聚合之光聚合起始劑。作為光聚合起始劑，可使用：藉由光之照射而產生自由基活性種之光自由基聚合起始劑(例如乙醯苯、二甲氧基苯偶醯、二苯甲醯、苯偶姻、二苯甲酮、苯甲醯苯甲酸、雙(二甲胺基)二苯甲酮、雙(二乙胺基)二苯甲酮、氯9-氧硫

Figure 108119282-A0304-12-01
、乙基蒽醌)、產生陽離子活性種之光陽離子聚合起始劑(例如六氟磷酸雙(4-第三丁基苯基)錪、三氟甲磺酸雙(4-氟苯基)錪、六氟磷酸二苯基錪、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三𠯤、4-硝基苯重氮鎓四氟硼酸鹽)、產生陰離子活性種之光陰離子聚合起始劑(苯乙酮-O-苯甲醯肟、環己基胺基甲酸1,2-雙(4-甲氧基苯基)-2-側氧乙酯、硝苯地平)。作為光聚合起始劑，可使用Irgacure(BASF)等市售品。可使用Irgacure184(1-羥基環己基苯基酮)、Irgacure907(2-甲基-1-(4-(甲硫基)苯基)-2-嗎啉基丙烷-1-酮)、Lucirin TPO(2,4,6-三甲基苯甲醯基二苯基氧化膦)等。又，該等可單獨使用或混合2種以上使用。The curable resin composition of the embodiment includes a polymerization initiator (B) in addition to the polyurethane (meth)acrylate compound (A). The polymerization initiator is a compound that initiates the polymerization reaction of the monomer in response to stimuli such as light irradiation and heat application. In the curable resin composition of the embodiment, it is preferable to use a photopolymerization initiator that initiates polymerization by irradiation of light including ultraviolet rays, electron beams, and visible light. As a photopolymerization initiator, a photoradical polymerization initiator that generates free radical active species by irradiation of light (for example, acetophenone, dimethoxybenzyl, dibenzoyl, benzoyl) Marriage, benzophenone, benzoyl benzoic acid, bis(dimethylamino) benzophenone, bis(diethylamino) benzophenone, chloro 9-oxythio
Figure 108119282-A0304-12-01
, Ethylanthraquinone), photocationic polymerization initiators that generate cationic active species (such as bis(4-third butylphenyl) hexafluorophosphate, bis(4-fluorophenyl) chlorotrifluoromethanesulfonate , Diphenylphosphonium hexafluorophosphate, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-tris, 4-nitro Phenyldiazonium tetrafluoroborate), photoanionic polymerization initiator that produces anionic active species (acetophenone-O-benzoyl oxime, cyclohexylaminocarbamic acid 1,2-bis(4-methoxybenzene) Radical)-2-oxoethyl ester, nifedipine). As the photopolymerization initiator, commercially available products such as Irgacure (BASF) can be used. Irgacure 184 (1-hydroxycyclohexyl phenyl ketone), Irgacure 907 (2-methyl-1-(4-(methylthio) phenyl)-2-morpholinylpropane-1-one), Lucirin TPO ( 2,4,6-trimethylbenzyl diphenylphosphine oxide), etc. Moreover, these can be used individually or in mixture of 2 or more types.

實施形態之硬化性樹脂組合物包含非質子性極性溶劑(C)。非質子性極性溶劑係指於分子中不具有供質子性基之極性溶劑。作為非質子性極性溶劑，可列舉：二***、四氫呋喃等醚類；丙酮、甲基乙基酮等酮類；乙酸甲酯、乙酸乙酯等酯類；及二甲基亞碸、N,N-二甲基甲醯胺、六甲基磷酸三胺等。非質子性極性溶劑(C)可使用該等之中1種或混合使用2種以上，就介電常數之觀點而言，較佳為包含N,N-二甲基甲醯胺及二甲基亞碸中之至少一者。藉由使硬化性樹脂組合物中包含非質子性極性溶劑(C)，可抑制硬化性樹脂組合物中所含之聚胺基甲酸酯(甲基)丙烯酸酯化合物(A)之分子間相互作用。因此，聚胺基甲酸酯(甲基)丙烯酸酯化合物(A)均勻分佈於硬化性樹脂組合物中。若使此種硬化性樹脂組合物硬化，則可形成均勻之硬化覆膜。再者，於硬化性樹脂組合物硬化時，非質子性極性溶劑(C)揮發。使用將如上所述具有特定之胺基甲酸酯鍵當量之值之聚胺基甲酸酯(甲基)丙烯酸酯化合物(A)與非質子性極性溶劑(C)加以組合之本實施形態之硬化性樹脂組合物，可形成更加強固之硬化覆膜。The curable resin composition of the embodiment includes an aprotic polar solvent (C). Aprotic polar solvents refer to polar solvents that do not have proton donating groups in the molecule. Examples of aprotic polar solvents include ethers such as diethyl ether and tetrahydrofuran; ketones such as acetone and methyl ethyl ketone; esters such as methyl acetate and ethyl acetate; and dimethyl sulfoxide, N, N -Dimethylformamide, triamine hexamethylphosphate, etc. As the aprotic polar solvent (C), one of these or two or more of them may be used in combination. From the viewpoint of dielectric constant, it is preferably composed of N,N-dimethylformamide and dimethyl At least one of arrogance. By including the aprotic polar solvent (C) in the curable resin composition, the interaction between the molecules of the polyurethane (meth)acrylate compound (A) contained in the curable resin composition can be suppressed effect. Therefore, the polyurethane (meth)acrylate compound (A) is uniformly distributed in the curable resin composition. If such a curable resin composition is cured, a uniform cured film can be formed. Furthermore, when the curable resin composition is cured, the aprotic polar solvent (C) volatilizes. This embodiment of the present embodiment uses a combination of a polyurethane (meth)acrylate compound (A) having a specific value of a urethane bond equivalent as described above and an aprotic polar solvent (C) The hardenable resin composition can form a hardened and hardened coating.

實施形態之硬化性樹脂組合物可進而包含於分子內具有1個以上之自由基性聚合性基之乙烯性不飽和化合物(D)。此處，乙烯性不飽和化合物係指至少具有1個乙烯性不飽和基(-C=C-)之化合物。乙烯性不飽和化合物(D)較佳為於分子內具有1個以上之自由基聚合性基。自由基聚合性基係如上所述以乙烯基、丙烯醯基(acryl)、甲基丙烯醯基(metaacryl)、丙烯醯基、甲基丙烯醯基、烯丙基等為代表之藉由照射活性能量線或賦予熱、或添加聚合起始劑而裂解開始自由基聚合之雙鍵或三鍵。作為此種乙烯性不飽和化合物(D)，例如可列舉：乙氧基化甘油三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、二羥甲基丙烷四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯為代表之多官能(甲基)丙烯酸酯化合物；(甲基)丙烯酸羥基丁酯、(甲基)丙烯酸羥基丙酯、(甲基)丙烯酸羥基乙酯為代表之(甲基)丙烯酸系單體；及(甲基)丙烯醯胺、二甲基(甲基)丙烯醯胺為代表之(甲基)丙烯醯胺類。又，只要不對實施形態造成影響，可使用至少具有1個乙烯性不飽和基之聚合物作為乙烯性不飽和化合物(D)。藉由將乙烯性不飽和化合物(D)作各種變更，可改變硬化覆膜之伸長率、硬度、對基材之密接性等。因此，根據應用硬化覆膜之基材之種類、成形方法、完成成形品之用途等，可使用或不使用乙烯性不飽和化合物(D)。The curable resin composition of the embodiment may further contain an ethylenically unsaturated compound (D) having one or more radical polymerizable groups in the molecule. Here, the ethylenically unsaturated compound refers to a compound having at least one ethylenically unsaturated group (-C=C-). The ethylenically unsaturated compound (D) preferably has one or more radical polymerizable groups in the molecule. The radical polymerizable group is represented by vinyl, acryl, methacryl, metaacryl, acryl, methacryl, allyl, etc. as described above. The energy ray either imparts heat or adds a polymerization initiator to cleave the double bond or triple bond that initiates free radical polymerization. Examples of such ethylenically unsaturated compound (D) include ethoxylated glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and trimethylol. Propylene tri (meth) acrylate, dimethylol propane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate is represented by multifunctional (meth) acrylate compounds; (meth) acrylic acid (Meth)acrylic monomers represented by hydroxybutyl ester, hydroxypropyl (meth)acrylate, and hydroxyethyl (meth)acrylate; and (meth)acrylamide, dimethyl (meth)acrylic acid Acetamide is the representative (meth)acrylamide. As long as it does not affect the embodiment, a polymer having at least one ethylenically unsaturated group can be used as the ethylenically unsaturated compound (D). By making various changes to the ethylenically unsaturated compound (D), the elongation, hardness, adhesion to the substrate, etc. of the cured film can be changed. Therefore, the ethylenically unsaturated compound (D) may or may not be used depending on the type of base material to which the cured coating is applied, the molding method, and the use of the finished molded product.

實施形態之硬化性樹脂組合物除了上述成分以外，亦可調配以硬化性樹脂組合物中通常所含之添加劑(例如染料、顏料、塑化劑、分散劑、防腐劑、消光劑、抗靜電劑、阻燃劑、紫外線吸收劑、光穩定劑、防污劑、抗黏連劑、抗菌劑、無機粒子)。In addition to the above-mentioned components, the curable resin composition of the embodiment can also be formulated with additives (such as dyes, pigments, plasticizers, dispersants, preservatives, matting agents, and antistatic agents) generally contained in the curable resin composition. , Flame retardants, ultraviolet absorbers, light stabilizers, antifouling agents, anti-blocking agents, antibacterial agents, inorganic particles).

實施形態之硬化性樹脂組合物可根據用途調配以質子性極性溶劑進行稀釋。作為質子性極性溶劑，可使用甲醇、乙醇、1-丙醇、異丙醇、乙二醇甲醚、丙二醇單甲醚等醇類中之1種或混合使用2種以上。再者，於本說明書中，藉由質子性極性溶劑稀釋實施形態之硬化性樹脂組合物所得者有時亦稱為「硬化性樹脂組合物」。The curable resin composition of the embodiment can be prepared by using a protic polar solvent for dilution according to the application. As the protic polar solvent, one kind of alcohols such as methanol, ethanol, 1-propanol, isopropanol, ethylene glycol methyl ether, propylene glycol monomethyl ether, or two or more kinds can be used in combination. In addition, in the present specification, those obtained by diluting the curable resin composition of the embodiment with a protic polar solvent are sometimes referred to as "curable resin composition".

較佳之硬化性樹脂組合物可藉由如下方式製造，即，準備聚胺基甲酸酯(甲基)丙烯酸酯化合物(A)，與聚合起始劑(B)、根據硬化性樹脂組合物之用途而定之適當量之非質子性極性溶劑(C)、及視情形之乙烯性不飽和化合物(D)加以混合，進而視情形藉由質子性極性溶劑進行稀釋。The preferred curable resin composition can be produced by preparing a polyurethane (meth)acrylate compound (A), and a polymerization initiator (B), according to the curable resin composition An appropriate amount of an aprotic polar solvent (C) and an ethylenically unsaturated compound (D) as appropriate depending on the purpose are mixed, and then diluted with a protic polar solvent as appropriate.

此處，聚胺基甲酸酯(甲基)丙烯酸酯化合物(A)(非揮發分)之含量以硬化性樹脂組合物之重量(即，成分(A)、成分(B)、成分(C)、成分(D)之合計重量)為基準係15～50%，較佳為20～45%。 又，聚合起始劑(B)之含量以硬化性樹脂組合物之重量為基準係0.5～5%，較佳為1～3%。 非質子性極性溶劑(C)之含量以硬化性樹脂組合物之重量為基準係40%～80%，較佳為45%～75%。 乙烯性不飽和化合物(D)之含量以硬化性樹脂組合物之重量為基準係5～20%，較佳為10～20%。 而且，實施形態之硬化性樹脂組合物可根據用途調配質子性極性溶劑進行稀釋。於該情形時，可藉由質子性極性溶劑以成為1.1倍～5倍之量，較佳為1.3倍～3倍之量之方式稀釋包含成分(A)、成分(B)、成分(C)、成分(D)之硬化性樹脂組合物。即，聚胺基甲酸酯(甲基)丙烯酸酯化合物(A)(非揮發分)之含量可以包含溶劑之硬化性樹脂組合物之總重量(即成分(A)、成分(B)、成分(C)、成分(D)、稀釋溶劑之合計重量)為基準設為5～30%，較佳為10～25%。 聚合起始劑(B)之含量以包含溶劑之硬化性樹脂組合物之總重量為基準係0.1～3%，較佳為0.5～2%。 非質子性極性溶劑(C)之含量以包含溶劑之硬化性樹脂組合物之總重量為基準係20%～60%，較佳為25%～60%。 乙烯性不飽和化合物(D)之含量以包含溶劑之硬化性樹脂組合物之總重量為基準係3～15%，較佳為5～10%。Here, the content of the polyurethane (meth)acrylate compound (A) (non-volatile matter) is based on the weight of the curable resin composition (ie, component (A), component (B), component (C ), the total weight of component (D) is 15 to 50% based on the standard, preferably 20 to 45%. In addition, the content of the polymerization initiator (B) is 0.5 to 5%, preferably 1 to 3%, based on the weight of the curable resin composition. The content of the aprotic polar solvent (C) is 40% to 80% based on the weight of the curable resin composition, preferably 45% to 75%. The content of the ethylenically unsaturated compound (D) is 5 to 20% based on the weight of the curable resin composition, preferably 10 to 20%. Furthermore, the curable resin composition of the embodiment can be prepared by diluting a protic polar solvent according to the application. In this case, the component (A), component (B), and component (C) can be diluted by a protic polar solvent in an amount of 1.1 times to 5 times, preferably 1.3 times to 3 times 1. The curable resin composition of component (D). That is, the content of the polyurethane (meth)acrylate compound (A) (non-volatile matter) may include the total weight of the curable resin composition of the solvent (ie, component (A), component (B), component (C), the total weight of the component (D) and the diluted solvent) is set to 5 to 30% based on the standard, preferably 10 to 25%. The content of the polymerization initiator (B) is 0.1 to 3% based on the total weight of the curable resin composition containing a solvent, preferably 0.5 to 2%. The content of the aprotic polar solvent (C) is 20% to 60% based on the total weight of the curable resin composition containing the solvent, preferably 25% to 60%. The content of the ethylenically unsaturated compound (D) is 3 to 15%, preferably 5 to 10%, based on the total weight of the curable resin composition containing the solvent.

實施形態之硬化性樹脂組合物可塗佈於適當之基材表面，於其上進行硬化而形成硬化覆膜。硬化覆膜之厚度可根據用途而變更，一般而言為1～20 μm，較佳為1～10 μm。作為使硬化性樹脂組合物硬化時之基材，可列舉：玻璃、塑膠、金屬等，實施形態之硬化性樹脂組合物可特別適合於塑膠上進行硬化而形成硬化覆膜。作為基材，例如可使用丙烯酸樹脂、或最表層被丙烯酸樹脂覆蓋之聚碳酸酯樹脂。對基材表面之硬化性樹脂組合物之塗佈可藉由先前之塗佈方法而適當地進行。可加熱所塗佈之硬化性樹脂組合物而形成硬化覆膜。關於硬化性樹脂組合物之加熱，只要加熱至藉由硬化性樹脂組合物中之聚合起始劑(B)之作用而引發聚胺基甲酸酯(甲基)丙烯酸酯化合物(A)、及視情形之乙烯性不飽和化合物(D)之聚合或共聚合反應所需之充分之溫度即可。加熱溫度根據使用之(A)及(D)及聚合起始劑(B)之種類而異，通常藉由加熱至80～150℃、較佳為100～150℃左右可引發共聚合反應。可藉由燃燒器或烘箱等加熱裝置對硬化性樹脂組合物塗佈物進行加熱，另外亦可藉由乾燥機等利用熱風之加熱方法進行加熱。The curable resin composition of the embodiment can be applied to the surface of a suitable substrate and cured on it to form a cured film. The thickness of the cured coating can be changed according to the application, but it is generally 1 to 20 μm, preferably 1 to 10 μm. Examples of the substrate for curing the curable resin composition include glass, plastic, and metal. The curable resin composition of the embodiment can be particularly suitable for curing on plastic to form a cured film. As the base material, for example, acrylic resin or polycarbonate resin whose outermost layer is covered with acrylic resin can be used. The coating of the curable resin composition on the surface of the base material can be appropriately performed by the previous coating method. The applied curable resin composition can be heated to form a cured film. Regarding the heating of the curable resin composition, as long as it is heated to initiate the polyurethane (meth)acrylate compound (A) by the action of the polymerization initiator (B) in the curable resin composition, and A sufficient temperature required for the polymerization or copolymerization of the ethylenically unsaturated compound (D) according to circumstances. The heating temperature varies according to the types of (A) and (D) and the polymerization initiator (B) used, and usually the copolymerization reaction can be initiated by heating to about 80 to 150°C, preferably about 100 to 150°C. The coating material of the curable resin composition may be heated by a heating device such as a burner or an oven, or may be heated by a heating method such as a dryer using hot air.

此外，亦可將實施形態之硬化性樹脂組合物塗佈於基材表面，對塗佈表面照射活性能量線而引發聚胺基甲酸酯(甲基)丙烯酸酯化合物(A)與視情形之乙烯性不飽和化合物(D)之聚合或共聚合反應。作為照射之活性能量線，可列舉：可見光、紫外線光、紅外線光、α射線、β射線、γ射線、X射線等。In addition, the curable resin composition of the embodiment may be applied to the surface of the base material, and the coated surface is irradiated with active energy rays to initiate the polyurethane (meth)acrylate compound (A) and optionally Polymerization or copolymerization of ethylenically unsaturated compound (D). Examples of the active energy rays to be irradiated include visible light, ultraviolet light, infrared light, α-rays, β-rays, γ-rays, and X-rays.

如此可使實施形態之硬化性樹脂組合物於塑膠基材上硬化而形成硬化覆膜，從而形成成形膜。實施形態之成形膜可作為用於加工塑膠等成形品之表面之膜使用。實施形態之成形膜可具有花紋、花樣、圖案、色彩等，亦可為透明。具有花紋等之成形膜稱為加飾膜，較佳地用於對成形品之表面施加花紋等。可將實施形態之成形膜裝填至射出成形模具內，於射出成形之同時將硬化覆膜貼附於成形品(嵌入成形法)。又，可將實施形態之成形膜貼附於成形品之表面，剝離基材而轉印施有花紋或花樣之硬化覆膜(轉印法)。使實施形態之硬化性樹脂組合物硬化而獲得之硬化覆膜可形成具有針對射出成形法之耐熱性、及可追隨成形品表面之充分之伸長性、且密接於成形品表面之強固之覆膜。 [實施例]In this way, the curable resin composition of the embodiment can be cured on a plastic substrate to form a cured film, thereby forming a molded film. The formed film of the embodiment can be used as a film for processing the surface of molded products such as plastic. The formed film of the embodiment may have patterns, patterns, patterns, colors, etc., or may be transparent. A formed film having a pattern or the like is called a decorative film, and is preferably used to apply a pattern or the like to the surface of a molded product. The molded film of the embodiment can be filled into an injection molding die, and the cured film can be attached to the molded product at the same time as the injection molding (embedded molding method). In addition, the formed film of the embodiment can be attached to the surface of the formed product, the base material can be peeled off, and a hardened film with a pattern or pattern applied can be transferred (transfer method). The cured film obtained by curing the curable resin composition of the embodiment can form a strong film having heat resistance for the injection molding method and sufficient elongation that can follow the surface of the molded product and is closely adhered to the surface of the molded product . [Example]

(1)硬化性樹脂組合物之製作 (1-1)聚胺基甲酸酯(甲基)丙烯酸酯化合物(A-1)之合成 於300 mL之茄型燒瓶中加入作為(a1)成分之二環己基甲烷-4,4'-二異氰酸酯30.0重量份、作為(a2)成分之乙二醇6.9重量份、作為(C)成分之N,N-二甲基甲醯胺98.7重量份、及作為觸媒之二月桂酸二辛基錫0.024重量份，一面攪拌一面於70℃下反應6小時。反應結束後，加入作為(a3)成分之季戊四醇三丙烯酸酯(東亞合成股份有限公司製造，商品名：ARONIX M-306)5.4重量份，於60℃下反應6小時，從而獲得具有自由基聚合性基之聚胺基甲酸酯丙烯酸酯(A-1)。 重量平均分子量＝12100、非揮發分＝30%、胺基甲酸酯鍵當量＝170克/莫耳(1) Preparation of curable resin composition (1-1) Synthesis of Polyurethane (Meth)acrylate Compound (A-1) In a 300 mL eggplant flask, add 30.0 parts by weight of dicyclohexylmethane-4,4'-diisocyanate as (a1) component, 6.9 parts by weight of ethylene glycol as (a2) component, and (C) component 98.7 parts by weight of N,N-dimethylformamide and 0.024 parts by weight of dioctyltin dilaurate as a catalyst were reacted at 70°C for 6 hours while stirring. After completion of the reaction, 5.4 parts by weight of pentaerythritol triacrylate (manufactured by East Asia Synthesizing Co., Ltd., trade name: ARONIX M-306) as a component (a3) was added, and reacted at 60°C for 6 hours to obtain radical polymerizability Based polyurethane acrylate (A-1). Weight-average molecular weight = 12100, non-volatile matter = 30%, urethane bond equivalent = 170 g/mole

再者，以下進行說明之實施例及比較例所合成之聚胺基甲酸酯(甲基)丙烯酸酯化合物係指聚胺基甲酸酯(甲基)丙烯酸酯化合物與作為反應溶劑之非質子性極性溶劑之混合物。「非揮發分」表示藉由反應所獲得之混合物中所含之聚胺基甲酸酯(甲基)丙烯酸酯化合物之實質比率。例如，於上述聚胺基甲酸酯丙烯酸酯(A-1)中，「非揮發分＝30%」意味著獲得聚胺基甲酸酯丙烯酸酯(A-1)30%與作為反應溶劑之N,N-二甲基甲醯胺70%之混合物，使用其作為(A-1)成分。關於以下之聚胺基甲酸酯(甲基)丙烯酸酯化合物之合成，全部相同地進行記載。In addition, the polyurethane (meth)acrylate compound synthesized in the examples and comparative examples described below refers to the polyurethane (meth)acrylate compound and the aprotic as the reaction solvent Mixture of polar solvents. "Nonvolatile" means the substantial ratio of the polyurethane (meth)acrylate compound contained in the mixture obtained by the reaction. For example, in the above-mentioned polyurethane acrylate (A-1), "nonvolatile content = 30%" means that 30% of the polyurethane acrylate (A-1) and the reaction solvent are obtained A mixture of 70% N,N-dimethylformamide, which is used as component (A-1). The synthesis of the following polyurethane (meth)acrylate compounds will be described in the same way.

(1-2)聚胺基甲酸酯(甲基)丙烯酸酯化合物(A-2)之合成 於300 mL之茄型燒瓶中加入作為(a1)成分之二環己基甲烷-4,4'-二異氰酸酯30.0重量份、作為(a2)成分之乙二醇6.6重量份、作為(C)成分之N,N-二甲基甲醯胺110.0重量份、及作為觸媒之二月桂酸二辛基錫0.024重量份，一面攪拌一面於70℃下反應6小時。反應結束後，加入作為(a3)成分之季戊四醇三丙烯酸酯(東亞合成股份有限公司製造，商品名：ARONIX M-306)11.2重量份，於60℃下反應6小時，從而獲得具有自由基聚合性基之聚胺基甲酸酯丙烯酸酯(A-2)。 重量平均分子量＝5600、非揮發分＝30%、胺基甲酸酯鍵當量＝179克/莫耳(1-2) Synthesis of Polyurethane (Meth)acrylate Compound (A-2) In a 300 mL eggplant-shaped flask, add 30.0 parts by weight of dicyclohexylmethane-4,4'-diisocyanate as (a1) component, 6.6 parts by weight of ethylene glycol as (a2) component, and (C) component 110.0 parts by weight of N,N-dimethylformamide and 0.024 parts by weight of dioctyltin dilaurate as a catalyst were reacted at 70°C for 6 hours while stirring. After completion of the reaction, 11.2 parts by weight of pentaerythritol triacrylate (manufactured by East Asia Synthesizing Co., Ltd., trade name: ARONIX M-306) as a component (a3) was added, and reacted at 60°C for 6 hours to obtain radically polymerizable Based polyurethane acrylate (A-2). Weight-average molecular weight = 5600, non-volatile matter = 30%, urethane bond equivalent = 179 g/mole

(1-3)聚胺基甲酸酯(甲基)丙烯酸酯化合物(A-3)之合成 於300 mL之茄型燒瓶中加入作為(a1)成分之二環己基甲烷-4,4'-二異氰酸酯30.0重量份、作為(a2)成分之乙二醇6.6重量份、作為(C)成分之N,N-二甲基甲醯胺110.0重量份、及作為觸媒之二月桂酸二辛基錫0.024重量份，一面攪拌一面於70℃下反應6小時。反應結束後，加入作為(a3)成分之季戊四醇三丙烯酸酯(東亞合成股份有限公司製造，商品名：ARONIX M-306)37.6重量份，於60℃下反應6小時，從而獲得具有自由基聚合性基之聚胺基甲酸酯丙烯酸酯(A-3)。 重量平均分子量＝5000、非揮發分＝40%、胺基甲酸酯鍵當量＝181克/莫耳(1-3) Synthesis of Polyurethane (Meth)acrylate Compound (A-3) In a 300 mL eggplant-shaped flask, add 30.0 parts by weight of dicyclohexylmethane-4,4'-diisocyanate as (a1) component, 6.6 parts by weight of ethylene glycol as (a2) component, and (C) component 110.0 parts by weight of N,N-dimethylformamide and 0.024 parts by weight of dioctyltin dilaurate as a catalyst were reacted at 70°C for 6 hours while stirring. After completion of the reaction, 37.6 parts by weight of pentaerythritol triacrylate (manufactured by East Asia Synthetic Co., Ltd., trade name: ARONIX M-306) as a component (a3) was added, and reacted at 60°C for 6 hours to obtain radical polymerizability Based polyurethane acrylate (A-3). Weight average molecular weight = 5000, non-volatile matter = 40%, urethane bond equivalent = 181 g/mole

(1-4)聚胺基甲酸酯(甲基)丙烯酸酯化合物(A-4)之合成 於300 mL之茄型燒瓶中加入作為(a1)成分之二環己基甲烷-4,4'-二異氰酸酯30.0重量份、作為(a2)成分之1,4-丁二醇9.6重量份、作為(C)成分之N,N-二甲基甲醯胺118.6重量份、及作為觸媒之二月桂酸二辛基錫0.024重量份，一面攪拌一面於70℃下反應6小時。反應結束後，加入作為(a3)成分之季戊四醇三丙烯酸酯(東亞合成股份有限公司製造，商品名：ARONIX M-306)11.2重量份，於60℃下反應6小時，從而獲得具有自由基聚合性基之聚胺基甲酸酯丙烯酸酯(A-4)。 重量平均分子量＝5600、非揮發分＝30%、胺基甲酸酯鍵當量＝194克/莫耳(1-4) Synthesis of Polyurethane (Meth)acrylate Compound (A-4) In a 300 mL eggplant flask, add 30.0 parts by weight of dicyclohexylmethane-4,4'-diisocyanate as (a1) component and 9.6 parts by weight of 1,4-butanediol as (a2) component as ( C) 118.6 parts by weight of N,N-dimethylformamide as a component and 0.024 parts by weight of dioctyltin dilaurate as a catalyst were reacted at 70°C for 6 hours while stirring. After completion of the reaction, 11.2 parts by weight of pentaerythritol triacrylate (manufactured by East Asia Synthesizing Co., Ltd., trade name: ARONIX M-306) as a component (a3) was added, and reacted at 60°C for 6 hours to obtain radically polymerizable Based polyurethane acrylate (A-4). Weight-average molecular weight = 5600, non-volatile matter = 30%, urethane bond equivalent = 194 g/mole

(1-5)聚胺基甲酸酯(甲基)丙烯酸酯化合物(A-5)之合成 於300 mL之茄型燒瓶中加入作為(a1)成分之二環己基甲烷-4,4'-二異氰酸酯30.0重量份、作為(a2)成分之1,6-己二醇12.5重量份、作為(C)成分之N,N-二甲基甲醯胺125.3重量份、及作為觸媒之二月桂酸二辛基錫0.024重量份，一面攪拌一面於70℃下反應6小時。反應結束後，加入作為(a3)成分之季戊四醇三丙烯酸酯(東亞合成股份有限公司製造，商品名：ARONIX M-306)11.2重量份，於60℃下反應6小時，從而獲得聚胺基甲酸酯丙烯酸酯化合物(A-5)。 重量平均分子量＝5600、非揮發分＝30%、胺基甲酸酯鍵當量＝208克/莫耳(1-5) Synthesis of Polyurethane (Meth)acrylate Compound (A-5) In a 300 mL eggplant-shaped flask, add 30.0 parts by weight of dicyclohexylmethane-4,4'-diisocyanate as (a1) component and 12.5 parts by weight of 1,6-hexanediol as (a2) component as ( C) 125.3 parts by weight of N,N-dimethylformamide and 0.024 parts by weight of dioctyltin dilaurate as a catalyst were reacted at 70°C for 6 hours while stirring. After completion of the reaction, 11.2 parts by weight of pentaerythritol triacrylate (manufactured by East Asia Synthetic Co., Ltd., trade name: ARONIX M-306) as a component (a3) was added, and reacted at 60°C for 6 hours to obtain polyaminocarboxylic acid Ester acrylate compound (A-5). Weight average molecular weight = 5600, non-volatile matter = 30%, urethane bond equivalent = 208 g/mole

(1-6)聚胺基甲酸酯(甲基)丙烯酸酯化合物(A'-1)之合成 合成胺基甲酸酯鍵當量之值較大之聚胺基甲酸酯(甲基)丙烯酸酯化合物。於500 mL之茄型燒瓶中加入異佛爾酮二異氰酸酯30.0重量份、聚碳酸酯二醇(旭化成股份有限公司製造，商品名：DURANOL T4691)57.2重量份、1,4-丁二醇4.3重量份、作為反應溶劑之甲基乙基酮(MEK)150.0重量份、及作為觸媒之二月桂酸二辛基錫0.005重量份，一面攪拌一面於80℃下反應9小時。反應結束後冷卻至60℃後，加入二月桂酸二辛基錫0.03重量份、甲基對苯二酚0.05重量份、甲基乙基酮10.6重量份，並滴加甲基丙烯酸2-羥基乙酯8.1重量份，於70℃下反應10小時，從而獲得聚胺基甲酸酯甲基丙烯酸酯化合物(A'-1)。 重量平均分子量＝4250、非揮發分＝40%、胺基甲酸酯鍵當量＝371克/莫耳(1-6) Synthesis of Polyurethane (Meth) Acrylate Compound (A'-1) Synthesize a polyurethane (meth)acrylate compound with a large value of urethane bond equivalent. In a 500 mL eggplant-shaped flask, 30.0 parts by weight of isophorone diisocyanate, polycarbonate diol (manufactured by Asahi Kasei Corporation, trade name: DURANOL T4691), 57.2 parts by weight, and 1,4-butanediol 4.3 parts by weight Parts, 150.0 parts by weight of methyl ethyl ketone (MEK) as a reaction solvent, and 0.005 parts by weight of dioctyl tin dilaurate as a catalyst, and reacted at 80° C. for 9 hours while stirring. After the reaction, after cooling to 60°C, 0.03 parts by weight of dioctyltin dilaurate, 0.05 parts by weight of methylhydroquinone, and 10.6 parts by weight of methyl ethyl ketone were added, and 2-hydroxyethyl methacrylate was added dropwise 8.1 parts by weight of the ester was reacted at 70°C for 10 hours to obtain a polyurethane methacrylate compound (A'-1). Weight-average molecular weight = 4250, non-volatile matter = 40%, urethane bond equivalent = 371 g/mole

(1-7)聚胺基甲酸酯(甲基)丙烯酸酯化合物(A'-2)之合成 合成胺基甲酸酯鍵當量之值較大之聚胺基甲酸酯(甲基)丙烯酸酯化合物。於500 mL之茄型燒瓶中加入二環己基甲烷-4,4'-二異氰酸酯77.7重量份、甘油單甲基丙烯酸酯(日油股份有限公司製造，商品名：Blemmer GLM)45.1重量份、作為反應溶劑之乙酸乙酯(EA)204.8重量份、及作為觸媒之二月桂酸二辛基錫0.004重量份，一面攪拌一面於60℃下反應6小時。反應結束後，加入季戊四醇三丙烯酸酯(東亞合成股份有限公司製造，商品名：ARONIX M-306)14.6重量份，於60℃下反應6小時，從而獲得聚胺基甲酸酯丙烯酸酯化合物(A'-2)。 重量平均分子量＝9200、非揮發分＝40%、胺基甲酸酯鍵當量＝222克/莫耳(1-7) Synthesis of Polyurethane (Meth)acrylate Compound (A'-2) Synthesize a polyurethane (meth)acrylate compound with a large value of urethane bond equivalent. In a 500 mL eggplant-shaped flask, 77.7 parts by weight of dicyclohexylmethane-4,4'-diisocyanate and 45.1 parts by weight of glycerol monomethacrylate (manufactured by NOF Corporation, trade name: Blemmer GLM) were added as 204.8 parts by weight of ethyl acetate (EA) as the reaction solvent and 0.004 parts by weight of dioctyltin dilaurate as the catalyst were reacted at 60°C for 6 hours with stirring. After the reaction was completed, 14.6 parts by weight of pentaerythritol triacrylate (manufactured by East Asia Synthetic Co., Ltd., trade name: ARONIX M-306) was added, and reacted at 60°C for 6 hours to obtain a polyurethane acrylate compound (A '-2). Weight average molecular weight = 9200, non-volatile matter = 40%, urethane bond equivalent = 222 g/mole

將上述(A-1)～(A-5)以及(A'-1)及(A'-2)、作為聚合起始劑(B)之Irgacure907(BASF)、作為視情形之乙烯性不飽和化合物(D)之季戊四醇三丙烯酸酯(東亞合成化學股份有限公司製造，ARONIX M-306)、及作為溶劑之丙二醇單甲醚(PGM)或甲基乙基酮(MEK)以表1所記載之重量比率進行調配，從而製作本發明之實施例1～6之硬化性樹脂組合物以及比較例1～4之硬化性樹脂組合物。再者，如上所述，上述(A-1)～(A-5)以及(A'-1)及(A'-2)係聚胺基甲酸酯(甲基)丙烯酸酯化合物與作為反應溶劑之非質子性極性溶劑(C)之混合物。表1及表2中之(A-1)～(A-5)以及(A'-1)及(A'-2)之數值係該等成分整體(即包含非質子性極性溶劑(C)者)之重量比。而且，括弧內之數值係僅非揮發分(即聚胺基甲酸酯(甲基)丙烯酸酯)之重量比。The above (A-1) to (A-5) and (A'-1) and (A'-2), Irgacure907 (BASF) as the polymerization initiator (B), as the ethylenic unsaturation as the case may be Pentaerythritol triacrylate (ARONIX M-306 manufactured by East Asia Synthetic Chemical Co., Ltd.) of compound (D), and propylene glycol monomethyl ether (PGM) or methyl ethyl ketone (MEK) as solvents are listed in Table 1. The weight ratio is adjusted to produce the curable resin compositions of Examples 1 to 6 of the present invention and the curable resin compositions of Comparative Examples 1 to 4. Furthermore, as described above, the above-mentioned (A-1) to (A-5) and (A'-1) and (A'-2)-based polyurethane (meth)acrylate compounds react as A mixture of solvent aprotic polar solvents (C). The values of (A-1) to (A-5) and (A'-1) and (A'-2) in Table 1 and Table 2 are the whole of these components (that is, including the aprotic polar solvent (C) The weight ratio. Moreover, the value in parentheses is the weight ratio of only non-volatile matter (ie, polyurethane (meth)acrylate).

(2)硬化性樹脂組合物之硬化覆膜之製作 作為形成硬化性樹脂組合物之硬化覆膜之基材，使用最表層被丙烯酸樹脂覆蓋之聚碳酸酯膜。以硬化後之膜厚成為4 μm之方式藉由棒式塗佈法將上述各硬化性樹脂組合物塗佈於基材。然後，將塗佈有硬化性樹脂組合物之基材於100℃之烘箱中乾燥1分鐘，繼而，藉由照射作為活性能量線之紫外線而使硬化性樹脂組合物硬化。藉此，獲得具有硬化覆膜之成形膜。(2) Preparation of cured film of curable resin composition As the base material for forming the cured film of the curable resin composition, a polycarbonate film whose outermost layer is covered with acrylic resin is used. The above curable resin compositions were applied to the substrate by a bar coating method so that the film thickness after curing became 4 μm. Then, the substrate coated with the curable resin composition was dried in an oven at 100° C. for 1 minute, and then the curable resin composition was cured by irradiating ultraviolet rays as active energy rays. By this, a formed film having a cured film is obtained.

(3)成形膜之性能評價 (3-1)外觀評價 對於各實施例之成形膜，使用JIS K 7136規定之霧度計測定霧度值。霧度值越大表示越不透明，越小表示越透明。(3) Performance evaluation of formed film (3-1) Appearance evaluation For the formed film of each example, the haze value was measured using the haze meter specified in JIS K 7136. A larger haze value means more opaque, and a smaller value means more transparent.

(3-2)密接性評價 依據JIS K 5600-5-6，藉由目測成形膜中硬化覆膜有無剝離而如下所示進行評價。 合格：沒有看到剝離 不合格：一部分或全部剝離(3-2) Evaluation of adhesion According to JIS K 5600-5-6, evaluation was performed as follows by visually inspecting the cured film for peeling of the cured film. Pass: No peeling is seen Unqualified: part or all stripped

(3-3)加熱後之密接性評價 進而，將各成形膜於沸水中浸漬30分鐘，依據JIS K 5600-5-6，藉由目測成形膜中硬化覆膜有無剝離而如下所示進行評價。 合格：沒有看到剝離 不合格：一部分或全部剝離(3-3) Evaluation of adhesion after heating Furthermore, each molded film was immersed in boiling water for 30 minutes, and evaluated according to JIS K 5600-5-6 by visually inspecting the molded film for peeling of the cured film, and evaluated as follows. Pass: No peeling is seen Unqualified: part or all stripped

(3-4)耐擦傷性之評價 對於所獲得之各成形膜，於鋼絲絨＃0000上施加250 g/cm2 之負載並往復10次，使用霧度計測定霧度值。求出耐擦傷性試驗前後之霧度值之差。該值越小意味著耐擦傷性越高。(3-4) Evaluation of scratch resistance For each formed film obtained, a load of 250 g/cm 2 was applied to steel wool #0000 and reciprocated 10 times, and the haze value was measured using a haze meter. The difference between the haze values before and after the scratch resistance test was determined. The smaller the value, the higher the scratch resistance.

(3-5)耐化學品性之評價 對於所獲得之各成形膜，將市售之防曬霜(Ultra Sheer Dry - Touch Sunscreen SPF45，Neutrogena公司製造)0.2克塗佈於1 cm2 之面積，於80℃下靜置1小時。其後藉由大量水洗淨所塗佈之防曬霜，藉由目測觀察硬化覆膜外觀之變化。 高：外觀沒有看到任何變化 中：外觀之一部分看到變白等變化 低：外觀看到變白等變化(3-5) Evaluation of chemical resistance For each formed film obtained, 0.2 g of a commercially available sunscreen (Ultra Sheer Dry-Touch Sunscreen SPF45, manufactured by Neutrogena) was applied to an area of 1 cm 2 . Let stand at 80°C for 1 hour. Afterwards, the applied sunscreen was washed with a large amount of water, and the change of the appearance of the hardened film was observed by visual observation. High: No changes are seen in the appearance: Part of the appearance sees changes such as whitening Low: Changes in the appearance sees changes such as whitening

(3-6)延伸性之評價 對於所獲得之各成形膜，於高溫下(150℃)進行拉伸試驗(樣品尺寸：200 mm×10 mm、夾頭間距離：110 mm、拉伸速度：50 mm/min)，將目測到硬化覆膜產生裂痕之時間點設為斷裂點伸長率，由其結果評價成形膜之延伸性。(3-6) Evaluation of extensibility For each formed film obtained, a tensile test was carried out at a high temperature (150°C) (sample size: 200 mm×10 mm, distance between chucks: 110 mm, and tensile speed: 50 mm/min). The time at which the cured film cracked was defined as the elongation at break point, and the stretchability of the formed film was evaluated from the results.

[表1]

Figure 108119282-A0304-0001
[Table 1]
Figure 108119282-A0304-0001

[表2]

Figure 108119282-A0304-0002
[Table 2]
Figure 108119282-A0304-0002

再者，表1中之括號內之數值係非揮發分之成分量。例如，表1實施例1之A-1欄中記載之數值「46.1」意味著A-1之聚胺基甲酸酯丙烯酸酯與作為反應溶劑(即非質子性極性溶劑(C))之DMF之合計量為46.1重量份，其中聚胺基甲酸酯丙烯酸酯A-1之量為13.8重量份。為了方便製造，作為(A)成分之聚胺基甲酸酯(甲基)丙烯酸酯係以聚胺基甲酸酯(甲基)丙烯酸酯與非質子性極性溶劑(C)之混合物之形式使用，故而於表中如上述說明般記載。實施例1之硬化性樹脂組合物係將溶解於非質子性極性溶劑(C)之A-1 46.1重量份、聚合起始劑(B)0.9重量份、乙烯性不飽和單體(D)7.7重量份、及稀釋溶劑45.3重量份加以混合而製作所得者。同樣地，表2中之括號內之數值係非揮發分之成分量。例如，表2比較例1之A'-1欄中記載之數值「53.9」意味著A'-1之聚胺基甲酸酯丙烯酸酯與作為反應溶劑(即非質子性極性溶劑(C))之MEK之合計量為53.9重量份，其中聚胺基甲酸酯甲基丙烯酸酯A'-1之量為21.6重量份。比較例1之硬化性樹脂組合物係將溶解於非質子性極性溶劑(C)之A'-1 53.9重量份、聚合起始劑(B)1.2重量份、進而MEK44.9重量份加以混合而製作所得者。In addition, the value in parentheses in Table 1 is the amount of non-volatile components. For example, the value "46.1" in the column A-1 of Example 1 of Table 1 means that the polyurethane acrylate of A-1 and DMF as the reaction solvent (ie, aprotic polar solvent (C)) The total amount is 46.1 parts by weight, and the amount of polyurethane acrylate A-1 is 13.8 parts by weight. For convenience of manufacturing, the polyurethane (meth)acrylate as the component (A) is used in the form of a mixture of the polyurethane (meth)acrylate and the aprotic polar solvent (C) Therefore, it is described in the table as described above. The curable resin composition of Example 1 is composed of 46.1 parts by weight of A-1 dissolved in an aprotic polar solvent (C), 0.9 parts by weight of a polymerization initiator (B), and 7.7 ethylenically unsaturated monomers (D) 45.3 parts by weight of the diluent and the diluent are mixed to prepare the obtained product. Similarly, the values in parentheses in Table 2 are the non-volatile content. For example, the value "53.9" described in column A'-1 of Comparative Example 1 in Table 2 means that the polyurethane acrylate of A'-1 is used as a reaction solvent (that is, an aprotic polar solvent (C)) The total amount of MEK is 53.9 parts by weight, and the amount of polyurethane methacrylate A'-1 is 21.6 parts by weight. The curable resin composition of Comparative Example 1 was prepared by mixing 53.9 parts by weight of A′-1 dissolved in an aprotic polar solvent (C), 1.2 parts by weight of a polymerization initiator (B), and 44.9 parts by weight of MEK. Producer.

再者，表中之縮寫之含義如下所示： Irgacure907：2-甲基-1-(4-甲硫基苯基)-2-嗎啉基丙烷-1-酮(BASF) M-306：季戊四醇三丙烯酸酯(東亞合成) PGM：丙二醇單甲醚 MEK：甲基乙基酮 DMF：N,N-二甲基甲醯胺 EA：乙酸乙酯Furthermore, the meaning of the abbreviations in the table is as follows: Irgacure907: 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one (BASF) M-306: Pentaerythritol triacrylate (East Asia Synthesis) PGM: propylene glycol monomethyl ether MEK: methyl ethyl ketone DMF: N,N-dimethylformamide EA: ethyl acetate

本發明之實施例之硬化覆膜均密接性優異，加熱後亦保持密接性。本發明之實施例之硬化性樹脂組合物可形成耐擦傷性以及耐化學品性優異之硬化覆膜。使用本發明之實施例之硬化性樹脂組合物之成形膜具有較高之斷裂點伸長率、即延伸性，提示具有可耐受嵌入成形法等之充分之伸長率。與此相對，使用比較例之硬化性樹脂組合物之成形膜於密接性、耐擦傷性、耐化學品性及延伸性之任一性能方面均不充分，比較例之硬化性樹脂組合物中使用之聚胺基甲酸酯(甲基)丙烯酸酯(A)之胺基甲酸酯鍵當量不滿足本發明之規定。The cured films of the embodiments of the present invention are excellent in adhesion, and maintain the adhesion even after heating. The curable resin composition of the embodiment of the present invention can form a cured coating film excellent in scratch resistance and chemical resistance. The formed film using the curable resin composition of the embodiment of the present invention has a high elongation at break point, that is, extensibility, suggesting a sufficient elongation that can withstand the insert molding method and the like. On the other hand, the formed film using the curable resin composition of the comparative example is insufficient in any of the properties of adhesion, scratch resistance, chemical resistance, and elongation, and is used in the curable resin composition of the comparative example. The equivalent of the urethane bond of the polyurethane (meth)acrylate (A) does not satisfy the requirements of the present invention.

Claims (7)

一種硬化性樹脂組合物，其包含胺基甲酸酯鍵當量為210克/莫耳以下之聚胺基甲酸酯(甲基)丙烯酸酯化合物(A)、聚合起始劑(B)、及非質子性極性溶劑(C)。A curable resin composition comprising a polyurethane (meth)acrylate compound (A) having a urethane bond equivalent weight of 210 g/mol or less, a polymerization initiator (B), and Aprotic polar solvent (C). 如請求項1之硬化性樹脂組合物，其中該聚胺基甲酸酯(甲基)丙烯酸酯化合物(A)係使聚異氰酸酯化合物(a1)與碳數1～6之多元醇化合物(a2)及(甲基)丙烯酸羥基烷基酯化合物(a3)反應而成之化合物。The curable resin composition according to claim 1, wherein the polyurethane (meth)acrylate compound (A) is a polyisocyanate compound (a1) and a polyol compound having 1 to 6 carbon atoms (a2) A compound formed by reacting with (meth)acrylic acid hydroxyalkyl ester compound (a3). 如請求項1或2之硬化性樹脂組合物，其進而包含於分子內具有1個以上之自由基性聚合性基之乙烯性不飽和化合物(D)。The curable resin composition according to claim 1 or 2, which further contains an ethylenically unsaturated compound (D) having one or more radical polymerizable groups in the molecule. 如請求項1或2之硬化性樹脂組合物，其進而包含質子性極性溶劑。The curable resin composition according to claim 1 or 2, which further contains a protic polar solvent. 如請求項3之硬化性樹脂組合物，其進而包含質子性極性溶劑。The curable resin composition according to claim 3, which further contains a protic polar solvent. 一種成形膜，其具有使如請求項1至5中任一項之硬化性樹脂組合物硬化而成之硬化覆膜、及基材。A formed film having a cured film obtained by curing the curable resin composition according to any one of claims 1 to 5 and a base material. 一種成形品，其於表面具有使如請求項1至5中任一項之硬化性樹脂組合物硬化而成之硬化覆膜。A molded product having a hardened film obtained by hardening the curable resin composition according to any one of claims 1 to 5 on the surface.
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