TW201418303A - Ultraviolet curable urethane acrylate composition, thin film molded body, optical film and method for manufacturing thin film molded body - Google Patents

Ultraviolet curable urethane acrylate composition, thin film molded body, optical film and method for manufacturing thin film molded body Download PDF

Info

Publication number
TW201418303A
TW201418303A TW102132522A TW102132522A TW201418303A TW 201418303 A TW201418303 A TW 201418303A TW 102132522 A TW102132522 A TW 102132522A TW 102132522 A TW102132522 A TW 102132522A TW 201418303 A TW201418303 A TW 201418303A
Authority
TW
Taiwan
Prior art keywords
meth
urethane acrylate
film
ultraviolet curable
acrylate
Prior art date
Application number
TW102132522A
Other languages
Chinese (zh)
Other versions
TWI487723B (en
Inventor
Daichi Higuchi
Tamotsu Sakamoto
Yuko Takikawa
Original Assignee
Dainippon Ink & Chemicals
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dainippon Ink & Chemicals filed Critical Dainippon Ink & Chemicals
Publication of TW201418303A publication Critical patent/TW201418303A/en
Application granted granted Critical
Publication of TWI487723B publication Critical patent/TWI487723B/en

Links

Classifications

    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08F299/065—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 from polyurethanes with side or terminal unsaturations
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C08L75/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S525/92—Polyurethane having terminal ethylenic unsaturation

Abstract

The present invention is ultraviolet curable without comprising a photoinitiator and exhibits excellent self-healing property, yellowing resistance, transparency and adequate flexibility. An ultraviolet curable urethane acrylate composition which comprises an urethane acrylate oligomer (E) having a (meth)acryloyl group at the molecular terminals which is obtained by the addition reaction of a (meth)acrylic compound (D) having a hydroxyl group with respect to an urethane prepolymer (C) having an NCO group at the molecular terminals which is obtained by reacting a polyol (A) without an aromatic backbone and a polyisocyanate (B) without an aromatic backbone. This composition further comprises 0.2 to 80 parts by mass of an organic solvent (F) without a specific aromatic backbone and does not comprise a photoinitiator. The (meth)acrylic equivalent of (E) is 450 to 1100 g/equivalent and a tan[delta] peak temperature measured by dynamic viscoelasticity analysis in accordance with JIS K 0129 using a 100 [mu]m thick film produced with the composition is -8 to 45 DEG C.

Description

紫外線硬化性胺基甲酸酯丙烯酸酯組成物、薄膜成形體、光學薄膜、及薄膜成形體之製造方法 Ultraviolet curable urethane acrylate composition, film formed body, optical film, and method for producing film molded body

本發明係關於紫外線硬化性胺基甲酸酯丙烯酸酯組成物、使用它之薄膜成形體、光學薄膜、及薄膜成形體之製造方法。 The present invention relates to an ultraviolet curable urethane acrylate composition, a film molded body using the same, an optical film, and a method for producing a film molded body.

更詳言之，本發明之紫外線硬化性胺基甲酸酯丙烯酸酯組成物係與過去的紫外線硬化性組成物不同，完全不使用光聚合起始劑，且藉由含有特定有機溶劑作為稀釋溶劑，可展現優良的紫外線硬化性。 More specifically, the ultraviolet curable urethane acrylate composition of the present invention is different from the conventional ultraviolet curable composition in that it does not use a photopolymerization initiator at all, and contains a specific organic solvent as a diluent solvent. It exhibits excellent UV curability.

此外，本發明之薄膜成形體(例如薄膜、片材等)可展現一旦受傷即會快速回復之「自我修復性」與耐黃變性、透明性等優良性能。 Further, the film formed body of the present invention (for example, a film, a sheet, or the like) exhibits excellent properties such as "self-healing property", yellowing resistance, and transparency upon rapid recovery.

更進一步，本發明之薄膜成形體與先前技術不同，因完全不含光聚合起始劑，而可得到紫外線照射造成的黃變的程度極小，不會隨時間黃變，也不會有光聚合起始劑的未反應成分與分解物造成的成形物對接觸物之汙染等優良效果，而在例如：光學用構件(例如光學薄膜、光學片材等)、光學用塗布材料、纖維、電子電機材料、食品包裝、化妝品包裝、裝飾膜等，特別是要求耐黃變性、柔軟性、透明性等高度性能之廣泛範圍領域係有用的。 Further, the film formed body of the present invention is different from the prior art in that it is completely free of a photopolymerization initiator, and the degree of yellowing caused by ultraviolet irradiation is extremely small, does not yellow with time, and does not have photopolymerization. Excellent effects such as contamination of the contact product by the unreacted component of the initiator and the decomposition product, for example, optical members (for example, optical films, optical sheets, etc.), optical coating materials, fibers, and electronic motors. Materials, food packaging, cosmetic packaging, decorative films, and the like are particularly useful in a wide range of fields requiring high performance such as yellowing resistance, flexibility, and transparency.

近來，無論是在職場也好、家庭也好，在各種環境中，例如：個人電腦、影印機、行動電話、智慧型手機、平板電腦等高性能/高機能/小型化的多樣化IT機器正急速普及。特別是為了容易謀求操作簡單且高機能，觸控面板方式的利用領域大幅擴展，未來發展也備受期待。 Recently, in the workplace, the family is also good, in various environments, such as: personal computers, photocopiers, mobile phones, smart phones, tablets, and other high-performance / high-performance / miniaturized diverse IT equipment Rapid popularity. In particular, in order to facilitate easy operation and high performance, the field of use of the touch panel method has been greatly expanded, and future development is expected.

一般觸控面板為多層結構，於其最表層上為了防止受傷(提升耐久性)與維持美觀之目的，會設置硬塗層。然而，硬塗層雖然不易受傷，但相反的若一旦受傷則傷痕即無法復元，會有汙垢附著在該傷痕上，以傷痕為起點使汙染擴散之傾向，而成為損害物品美觀的原因。 Generally, the touch panel has a multi-layer structure, and a hard coat layer is provided on the outermost layer for the purpose of preventing injury (improving durability) and maintaining aesthetics. However, although the hard coat layer is not easily damaged, if the wound is damaged, the flaw cannot be recovered, and dirt adheres to the flaw, and the stain tends to spread as a starting point, which is a cause of damage to the appearance of the article.

因此，最近會在例如塑膠構件、金屬構件等物品的表面上加上樹脂塗層。特別是在觸控面板等的透明塑膠製薄膜之表面上，會設置更高硬度的硬塗層，來作為防止進一步受傷之處理。 Therefore, a resin coating is recently added to the surface of an article such as a plastic member or a metal member. In particular, on the surface of a transparent plastic film such as a touch panel, a hard coat having a higher hardness is provided as a treatment for preventing further injury.

然而，上述的高硬度硬塗層由於硬且脆的性質，而有以下等問題：(1)經過長期間使用在表面容易產生龜裂和刮傷；(2)一旦表面受傷即無法復元，而損害物品的美觀；(3)在被塗布之基材為聚碳酸酯等柔軟的材質之情形，無法展現目標水準的高硬度，而無法確保最表層的耐久性。 However, the above-mentioned high-hardness hard coat layer has the following problems due to its hard and brittle nature: (1) cracks and scratches are likely to occur on the surface after a long period of use; (2) once the surface is injured, it cannot be recovered, and (3) When the substrate to be coated is a soft material such as polycarbonate, the high hardness of the target level cannot be exhibited, and the durability of the outermost layer cannot be ensured.

另一方面，提案一種具有表面一旦受傷會自然回復之機能(以下稱為「自我修復性」)之自我修復性 的熱硬化性組成物。此種過去之具有自我修復性之熱硬化性組成物係柔軟且富彈性，因一旦受到如擦傷之凹痕也能在數秒至數分鐘後回復成原本的狀態，而有能跨長期間維持初期的良好之耐擦傷性之優點。 On the other hand, it proposes a self-healing property that has a function of naturally recovering from the surface (hereinafter referred to as "self-repairing"). Thermosetting composition. Such a self-healing thermosetting composition is soft and elastic, and can be restored to its original state after a few seconds to several minutes once it is subjected to a dent, such as a scratch, and can be maintained for a long period of time. The advantage of good scratch resistance.

然而，過去具有自我修復性之熱硬化性組成物有以下等問題：(1)因在加工時為了硬化必須要30分鐘以上的長時間加熱，生產性極差；(2)在基材不耐熱的情形，難以通過加熱來使用。 However, in the past, the self-healing thermosetting composition has the following problems: (1) It is necessary to heat for a long time of 30 minutes or more for hardening during processing, and the productivity is extremely poor; (2) The substrate is not heat resistant. In the case, it is difficult to use by heating.

又，相對於前述熱硬化性組成物，提案一種具有自我修復性之紫外線硬化性(以下也稱為「UV硬化性」)組成物。採用紫外線硬化性組成物有縮短硬化時間與削減能量成本等優點。 Moreover, a composition having a self-healing ultraviolet curability (hereinafter also referred to as "UV curability") is proposed as the thermosetting composition. The use of an ultraviolet curable composition has the advantages of shortening the hardening time and reducing the energy cost.

然而，過去具有自我修復性之紫外線硬化性組成物具有下述等實用上的大問題：(1)在薄薄地塗布在基材上之情形未充分展現自我修復性，無法確保硬化塗膜的最表層之強度；(2)因必須含有光聚合起始劑，初期的黃色度高(在黃色度高之情形，特別是在物品的角落部位，因黃色醒目而使商品價值受損)；(3)耐久性試驗後的耐黃變性比2液硬化型樹脂組成物還差。 However, the ultraviolet curable composition which has been self-healing in the past has such a large practical problem as follows: (1) The case where it is thinly applied to a substrate does not sufficiently exhibit self-healing property, and the most hardened coating film cannot be ensured. The strength of the surface layer; (2) The initial yellowness is high because it must contain a photopolymerization initiator (in the case of high yellowness, especially in the corners of the article, the value of the product is impaired by the yellow color); (3) The yellowing resistance after the durability test is inferior to the two-liquid curing resin composition.

為了改良這些問題，已有各種提案。 In order to improve these problems, various proposals have been made.

例如已知一種具有自我修復性之光硬化性組成物，其相對於100質量份的具有以特定通式表示之(甲基)丙烯醯基的反應性聚合物，係包含0.1~10質量份的光聚合起始劑(例如參照專利文獻1)。 For example, a self-healing photocurable composition containing 0.1 to 10 parts by mass based on 100 parts by mass of a reactive polymer having a (meth)acryl fluorenyl group represented by a specific formula is known. A photopolymerization initiator (for example, refer to Patent Document 1).

記載於專利文獻1之光硬化性組成物，係透過 得自二異氰酸酯化合物之胺基甲酸酯鍵將(甲基)丙烯醯基導入至橡膠成分，藉由將其與光聚合起始劑組合來賦予光硬化性，而可形成賦予不僅是良好的自我修復性，還有加工性與耐彎曲性等優良的塗膜外觀之塗膜。 The photocurable composition described in Patent Document 1 is transmitted through The urethane bond derived from the diisocyanate compound introduces a (meth) acrylonitrile group into the rubber component, and combines it with a photopolymerization initiator to impart photocurability, and the formation of the imparting is not only good. Self-healing, and a coating film with excellent coating film appearance such as processability and bending resistance.

然而，記載於專利文獻1之光硬化性組成物有以下問題：(1)自我修復性尚不充分，如擦傷之凹痕難以在短時間回復為原本的狀態；(2)因必須含有光聚合起始劑，所得到之硬化物的成形初期之黃色度高；(3)在耐熱試驗或耐紫外線試驗後會更明顯的黃變，耐黃變性差。 However, the photocurable composition described in Patent Document 1 has the following problems: (1) self-repairing is not sufficient, and it is difficult for the dent of the scratch to return to the original state in a short time; (2) photopolymerization is necessary because The initial agent, the obtained cured product has a high yellowness at the initial stage of formation; (3) the yellowing is more pronounced after the heat resistance test or the ultraviolet resistance test, and the yellowing resistance is poor.

另外，如專利文獻1般，含有光聚合起始劑之紫外線硬化性胺基甲酸酯丙烯酸酯組成物中，光聚合起始劑的未反應成分與分解物會移動至塗膜或成形體的表面，在將薄膜成形體(例如薄膜、片材等)加以積層之情形，會汙染與該薄膜成形體接觸之物品，或分解之光聚合起始劑會變化為黃色物質，使成形體的黃色度變差。特別是在重視美觀與透明性之食品包裝與化妝品包裝等領域，此種未反應成分與分解物為應除去之雜質，從品質面(衛生面、設計面等)來看也是相當重要的問題。 Further, as in the ultraviolet curable urethane acrylate composition containing a photopolymerization initiator, the unreacted component and the decomposed product of the photopolymerization initiator move to the coating film or the molded body. In the case where a film formed body (for example, a film, a sheet, or the like) is laminated, the article in contact with the film formed body may be contaminated, or the decomposed photopolymerization initiator may be changed to a yellow substance to make the formed body yellow. Degree is worse. In particular, in the fields of food packaging and cosmetic packaging that emphasize beauty and transparency, such unreacted components and decomposed substances are impurities to be removed, and are also an important problem from the viewpoint of quality (sanitary surface, design surface, etc.).

以此種光聚合起始劑誘發的黃變現象，於分解之光聚合起始劑再結合時變化為黃色物質而促進硬化物的黃化，而被認為係讓在使用於要求高等級的透明性之光學用途之光學用構件(例如薄膜、片材、纖維、塗料等)的性能低落的主因。特別是具有芳香族骨架之光聚合起始劑，由於芳香環會吸收光能並有效率的產生自由基，一般被大量使用，但因於再結合時起因於芳香環之醌 型結構，而有形成黃色的發色團之缺點。 The yellowing phenomenon induced by such a photopolymerization initiator changes to a yellow substance upon recombination of the decomposed photopolymerization initiator to promote yellowing of the hardened material, and is considered to be required to be used in a high level of transparency. The main cause of the low performance of optical components (such as films, sheets, fibers, paints, etc.) for optical applications. In particular, a photopolymerization initiator having an aromatic skeleton is generally used in a large amount because the aromatic ring absorbs light energy and efficiently generates radicals, but is caused by an aromatic ring due to recombination. Type structure, but has the disadvantage of forming a yellow chromophore.

如上所述，過去的紫外線硬化性胺基甲酸酯丙烯酸酯組成物有以下尚待解決之問題：(1)自我修復性還不充分；(2)因含有光聚合起始劑，而會造成黃變；(3)光聚合起始劑的未反應成分或分解物會移動，在將薄膜成形體(例如薄膜、片材等)加以積層之情形，會讓與塗膜或成形體接觸之物品被汙染；(4)光聚合起始劑的分解物會變化為黃色物質，使薄膜成形體的色調變差。 As described above, the past ultraviolet curable urethane acrylate composition has the following problems to be solved: (1) self-repairing is not sufficient; (2) due to the inclusion of a photopolymerization initiator, (3) The unreacted component or the decomposition product of the photopolymerization initiator moves, and when the film formed body (for example, a film, a sheet, or the like) is laminated, the article which is in contact with the coating film or the molded body is allowed to be attached. (4) The decomposition product of the photopolymerization initiator changes to a yellow substance to deteriorate the color tone of the film formed body.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開2010-260905號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-260905

本發明之目的係提供一種紫外線硬化性胺基甲酸酯丙烯酸酯組成物、使用它之薄膜成形體、光學薄膜、及薄膜成形體之製造方法，該紫外線硬化性胺基甲酸酯丙烯酸酯組成物與先前技術不同，即使不含光聚合起始劑也可展現優良的紫外線硬化性，且能展現優良的自我修復性、耐黃變性、透明性、及適當的柔軟性。 An object of the present invention is to provide a UV curable urethane acrylate composition, a film formed body using the same, an optical film, and a method for producing a film formed body comprising the ultraviolet curable urethane acrylate composition Unlike the prior art, the material exhibits excellent ultraviolet curability even without a photopolymerization initiator, and exhibits excellent self-healing properties, yellowing resistance, transparency, and appropriate softness.

本案發明人們為了解決上述課題，進行戮力研究的結果，發現：在包含於分子末端具有(甲基)丙烯醯基之胺基甲酸酯丙烯酸酯寡聚物，及作為稀釋溶劑之沒有芳香族骨架之有機溶劑，且不含光聚合起始劑之紫 外線硬化性胺基甲酸酯丙烯酸酯組成物中，藉由讓前述胺基甲酸酯丙烯酸酯寡聚物的(甲基)丙烯酸當量在特定範圍，且讓使用以前述紫外線硬化性胺基甲酸酯丙烯酸酯組成物製作之厚度100μm的薄膜，依據JIS K 0129以動態黏彈性分析所測定之tanδ(損失係數)峰值溫度在特定範圍，可得到能展現優良的自我修復性、耐黃變性、透明性、及適當的柔軟性之紫外線硬化性胺基甲酸酯丙烯酸酯組成物，乃至完成本發明。 In order to solve the above problems, the inventors of the present invention have found that the urethane acrylate oligomer having a (meth) acrylonitrile group at the molecular terminal and the aromatic solvent as a diluent solvent are found. The organic solvent of the skeleton, and does not contain the violet of the photopolymerization initiator In the external curable urethane acrylate composition, the (meth)acrylic equivalent of the urethane acrylate oligomer is in a specific range, and the ultraviolet curable amine base is used. The film having a thickness of 100 μm made of the acid ester acrylate composition has a tan δ (loss coefficient) peak temperature measured by dynamic viscoelastic analysis according to JIS K 0129, and can exhibit excellent self-healing property, yellowing resistance, and The ultraviolet curable urethane acrylate composition having transparency and appropriate flexibility is used to complete the present invention.

即，本發明係關於一種紫外線硬化性胺基甲酸酯丙烯酸酯組成物，該紫外線硬化性胺基甲酸酯丙烯酸酯組成物係包含：讓具有羥基之(甲基)丙烯酸類化合物(D)，對沒有芳香族骨架之多元醇(A)與沒有芳香族骨架之聚異氰酸酯(B)進行反應所得到之於分子末端具有異氰酸酯基之胺基甲酸酯預聚物(C)進行加成反應，所得到之於分子末端具有(甲基)丙烯醯基之胺基甲酸酯丙烯酸酯寡聚物(E)，其特徵為：該紫外線硬化性胺基甲酸酯丙烯酸酯組成物係含有0.2~80質量%的從由酮系溶劑、醯胺系溶劑、及鹵化烷系溶劑所構成之群組中所選出的至少一種沒有芳香族骨架之有機溶劑(F)，且不含光聚合起始劑，且前述胺基甲酸酯丙烯酸酯寡聚物(E)的(甲基)丙烯酸當量在450~1100g/當量之範圍，而使用以前述紫外線硬化性胺基甲酸酯丙烯酸酯組成物製作之厚度100μm的薄膜，依據JIS K 0129以動態黏彈性分析測定出的tanδ峰值溫度係在-8~45℃之範圍。 That is, the present invention relates to an ultraviolet curable urethane acrylate composition comprising: a (meth)acrylic compound having a hydroxyl group (D) An addition reaction of a urethane prepolymer (C) having an isocyanate group at a molecular terminal obtained by reacting a polyol (A) having no aromatic skeleton with a polyisocyanate (B) having no aromatic skeleton A urethane acrylate oligomer (E) having a (meth) acrylonitrile group at the molecular end, which is characterized in that the ultraviolet curable urethane acrylate composition contains 0.2 -80% by mass of at least one organic solvent (F) having no aromatic skeleton selected from the group consisting of a ketone solvent, a guanamine solvent, and an alkyl halide solvent, and does not contain a photopolymerization initiation And the (meth)acrylic acid equivalent of the urethane acrylate oligomer (E) is in the range of 450 to 1100 g / equivalent, and is produced by using the ultraviolet curable urethane acrylate composition described above. Film with a thickness of 100 μm according to JIS K 01 The tan δ peak temperature measured by dynamic viscoelastic analysis is in the range of -8 to 45 °C.

本發明係關於一種薄膜成形體，其特徵為： 在基材上具有前述紫外線硬化性胺基甲酸酯丙烯酸酯組成物之硬化塗膜。 The present invention relates to a film formed body characterized by: A cured coating film of the above ultraviolet curable urethane acrylate composition is provided on a substrate.

本發明係關於一種薄膜成形體，其特徵為：其係將前述紫外線硬化性胺基甲酸酯丙烯酸酯組成物塗布在基材上再使其硬化而得，且膜厚係在10~800μm之範圍。 The present invention relates to a film molded body obtained by applying the ultraviolet curable urethane acrylate composition onto a substrate and then hardening it, and the film thickness is 10 to 800 μm. range.

又，本發明係關於一種光學薄膜，該光學薄膜係具有前述紫外線硬化性胺基甲酸酯丙烯酸酯組成物之硬化塗膜，其特徵為：前述硬化塗膜在膜厚50~200μm之依據JIS K7361-1測定之總透光率為92%以上。 Further, the present invention relates to an optical film comprising a cured coating film of the ultraviolet curable urethane acrylate composition, characterized in that the cured coating film has a film thickness of 50 to 200 μm in accordance with JIS. The total light transmittance measured by K7361-1 was 92% or more.

此外，本發明係關於一種薄膜成形體之製造方法，其特徵為：將前述紫外線硬化性胺基甲酸酯丙烯酸酯組成物塗布於基材上，於照射紫外線後，使前述有機溶劑(F)揮發而形成硬化塗膜。 Further, the present invention relates to a method for producing a film molded body, characterized in that the ultraviolet curable urethane acrylate composition is applied onto a substrate, and after the ultraviolet ray is irradiated, the organic solvent (F) is applied. Volatilized to form a hardened coating film.

本發明之紫外線硬化性胺基甲酸酯丙烯酸酯組成物係與過去的紫外線硬化性組成物不同，即使完全不含光聚合起始劑也可展現優良的光硬化性，因可展現優良的自我修復性、耐黃變性、透明性、及適度的柔軟性，而在例如：光學用構件(例如光學薄膜、光學片材等)、光學用塗布材料、纖維、電子電機材料、食品包裝材料、化妝品包裝、裝飾膜等廣泛範圍之用途係有用的。 The ultraviolet curable urethane acrylate composition of the present invention is different from the conventional ultraviolet curable composition, and exhibits excellent photocurability even when it is completely free of a photopolymerization initiator, because it exhibits an excellent self. Repairability, yellowing resistance, transparency, and moderate flexibility, for example, optical components (such as optical films, optical sheets, etc.), optical coating materials, fibers, electronic motor materials, food packaging materials, cosmetics A wide range of uses such as packaging and decorative film are useful.

[實施發明之形態] [Formation of the Invention]

<紫外線硬化性胺基甲酸酯丙烯酸酯組成物> <Ultraviolet curable urethane acrylate composition>

本發明之紫外線硬化性胺基甲酸酯丙烯酸酯組成物與過去的紫外線硬化性組成物不同，完全不含光聚合起始劑。 The ultraviolet curable urethane acrylate composition of the present invention is completely free of a photopolymerization initiator unlike the conventional ultraviolet curable composition.

本發明之紫外線硬化性胺基甲酸酯丙烯酸酯組成物，必須包含：讓具有羥基之(甲基)丙烯酸類化合物(D)，對使沒有芳香族骨架之多元醇(A)與沒有芳香族骨架之聚異氰酸酯(B)進行反應所得到的於分子末端具有異氰酸酯基之胺基甲酸酯預聚物(C)進行加成反應，所得到之於分子末端具有(甲基)丙烯醯基之胺基甲酸酯丙烯酸酯寡聚物(E)，與後述之特定有機溶劑(F)。 The ultraviolet curable urethane acrylate composition of the present invention must contain a (meth)acrylic compound (D) having a hydroxyl group, and a polyhydric alcohol (A) having no aromatic skeleton and no aromatic The urethane prepolymer (C) having an isocyanate group at the molecular terminal obtained by the reaction of the polyisocyanate (B) of the skeleton is subjected to an addition reaction, and the (meth) acrylonitrile group is obtained at the molecular terminal. The urethane acrylate oligomer (E) and a specific organic solvent (F) to be described later.

本發明之紫外線硬化性胺基甲酸酯丙烯酸酯組成物與過去含有光聚合起始劑之紫外線硬化性組成物完全不同，即使完全不含光聚合起始劑，藉由必須包含使用沒有芳香族骨架之反應性原料所得到之於分子末端具有(甲基)丙烯醯基之胺基甲酸酯丙烯酸酯寡聚物(E)，與沒有芳香族骨架之特定有機溶劑(F)，而可正常且迅速地進行紫外線硬化反應。 The ultraviolet curable urethane acrylate composition of the present invention is completely different from the ultraviolet curable composition containing a photopolymerization initiator in the past, and does not contain a photopolymerization initiator, and must contain no aromatics. The urethane acrylate oligomer (E) having a (meth) acrylonitrile group at the molecular end of the skeleton-derived starting material and the specific organic solvent (F) having no aromatic skeleton can be used normally. And the ultraviolet curing reaction proceeds rapidly.

此外，本發明之紫外線硬化性胺基甲酸酯丙烯酸酯組成物係與過去使用光聚合起始劑之紫外線硬化性組成物完全不同，能展現優良的自我修復性以及耐黃變性、透明性、及適度的柔軟性。 Further, the ultraviolet curable urethane acrylate composition of the present invention is completely different from the ultraviolet curable composition using a photopolymerization initiator in the past, and exhibits excellent self-healing properties as well as yellowing resistance, transparency, and And moderate softness.

(A)沒有芳香族骨架之多元醇 (A) Polyol without aromatic skeleton

以下，詳細說明構成本發明之紫外線硬化性胺基甲 酸酯丙烯酸酯組成物的前述(A)~(F)。 Hereinafter, the ultraviolet curable amine base constituting the present invention will be described in detail. The aforementioned (A) to (F) of the acid ester acrylate composition.

本發明所使用之前述沒有芳香族骨架之多元醇(A)，係脂肪族多元醇與脂環族多元醇，可列舉出例如：聚酯多元醇、聚醚多元醇、聚碳酸酯多元醇、低分子量二醇等。 The polyol (A) having no aromatic skeleton used in the present invention is an aliphatic polyol and an alicyclic polyol, and examples thereof include a polyester polyol, a polyether polyol, and a polycarbonate polyol. Low molecular weight diols and the like.

前述聚酯多元醇通常係以二羧酸與二醇為原料來製造。 The polyester polyol is usually produced by using a dicarboxylic acid and a diol as a raw material.

使用於前述聚酯多元醇之製造的二羧酸，係沒有芳香族骨架之二羧酸，可列舉例如：丁二酸、己二酸、壬二酸、癸二酸、十二烷二酸、順丁烯二酸酐、反丁烯二酸、1,3-環戊二羧酸、1,4-環己二羧酸等。這些可以單獨使用，也可2種以上併用。 The dicarboxylic acid used in the production of the polyester polyol described above is a dicarboxylic acid having no aromatic skeleton, and examples thereof include succinic acid, adipic acid, sebacic acid, sebacic acid, and dodecanedioic acid. Maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and the like. These may be used alone or in combination of two or more.

除了前述二羧酸以外，也能使用其衍生物，可列舉出例如：甲基酯等低級烷基酯、酸酐、酸鹵化物等。 In addition to the above-mentioned dicarboxylic acid, a derivative thereof can also be used, and examples thereof include a lower alkyl ester such as a methyl ester, an acid anhydride, and an acid halide.

使用於前述聚酯多元醇之製造的二醇，係沒有芳香族骨架之二醇，可列舉出例如：乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、新戊二醇、1,3-丙二醇、二乙二醇、三乙二醇、四乙二醇、二丙二醇、三丙二醇、3-甲基-1,5-戊二醇、2-丁基-2-乙基-1,3-丙二醇、2-甲基-1,3-丙二醇等脂肪族二醇類，或1,4-環己二醇、1,4-環己二甲醇、氫化雙酚A等脂環族二醇類等。這些可以單獨使用，也可2種以上併用。 The diol used in the production of the polyester polyol described above is a diol having no aromatic skeleton, and examples thereof include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, and 1,3-butylene glycol. , 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,3-propanediol, diethylene glycol, triethylene glycol, tetraethylene glycol , dipropylene glycol, tripropylene glycol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-methyl-1,3-propanediol, etc. An alcohol or an alicyclic diol such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol or hydrogenated bisphenol A. These may be used alone or in combination of two or more.

又，在製造前述聚酯多元醇時，在不妨害本 發明之目的的範圍內，前述二醇也可與例如：丙三醇、三羥甲基乙烷、三羥甲基丙烷、山梨醇、蔗糖、烏頭糖等含有3官能以上羥基之化合物併用。 Moreover, when manufacturing the aforementioned polyester polyol, it does not harm the present. In the range of the object of the invention, the diol may be used in combination with a compound having a trifunctional or higher hydroxyl group such as glycerin, trimethylolethane, trimethylolpropane, sorbitol, sucrose or aconite.

本發明中，除了前述聚酯多元醇以外，也可使用內酯(例如ε-己內酯、γ-丁內酯等)開環加成聚合而成之聚酯多元醇等。 In the present invention, in addition to the polyester polyol described above, a polyester polyol obtained by ring-opening addition polymerization of a lactone (for example, ε-caprolactone or γ-butyrolactone) may be used.

前述聚酯多元醇的數量平均分子量(以下也稱為「Mn」)，期望係考慮在使用於分子末端有異氰酸酯基之胺基甲酸酯預聚物(C)(以下稱為「異氰酸酯基末端之胺基甲酸酯預聚物(C)」)時的目標熔融黏度來設定，較佳係在300~5000之範圍，更佳係在500~3500之範圍。前述聚酯多元醇的Mn若在此範圍，則前述異氰酸酯基末端之胺基甲酸酯預聚物(C)不會有異常的黏度上升，可正常地控制反應，並可得到熔融黏度適當的胺基甲酸酯預聚物。 The number average molecular weight (hereinafter also referred to as "Mn") of the above polyester polyol is desirably considered to be a urethane prepolymer (C) having an isocyanate group at the molecular terminal (hereinafter referred to as "isocyanate group terminal" The target fused viscosity at the time of the urethane prepolymer (C)" is preferably in the range of 300 to 5,000, more preferably in the range of 500 to 3,500. When the Mn of the polyester polyol is in this range, the urethane prepolymer (C) at the terminal end of the isocyanate group does not have an abnormal viscosity increase, the reaction can be normally controlled, and the melt viscosity can be appropriately obtained. A urethane prepolymer.

前述聚酯多元醇，也可列舉出併用上述以外的二羧酸、二醇、二胺等所得到之聚酯二醇、聚醯胺聚酯二醇等。 The polyester polyol obtained by using a dicarboxylic acid, a diol, a diamine or the like other than the above may be used, and a polyamide polyester diol or the like may be used.

又，前述聚醚多元醇可列舉出例如：聚乙二醇(PEG)、聚丙二醇(PPG)、聚(乙二醇-共聚-丙二醇)(PEPG)、聚四亞甲基醚醇(polytetramethyleneglycol，PTMG)，或以丙三醇、三羥甲基丙烷、新戊四醇、山梨醇等至少具有3個以上羥基之化合物作為起始原料，對環氧乙烷、環氧丙烷、環氧丁烷等環氧烷進行加成聚合而得到之聚(氧伸烷基)二醇等。這些之中，較佳為聚四亞 甲基醚醇(Mn為650~2000之PTMG)。前述聚醚多元醇也可具有直鏈、分枝、環狀中任一種結構。 Further, examples of the polyether polyol include polyethylene glycol (PEG), polypropylene glycol (PPG), poly(ethylene glycol-co-propylene glycol) (PEPG), and polytetramethylene glycol (polytetramethylene glycol). PTMG), or a compound having at least three or more hydroxyl groups such as glycerol, trimethylolpropane, neopentyl alcohol, sorbitol, etc. as a starting material for ethylene oxide, propylene oxide, butylene oxide A poly(oxyalkylene) glycol obtained by addition polymerization of an alkylene oxide or the like. Among these, polytetrazol is preferred Methyl ether alcohol (PTMG with Mn of 650-2000). The polyether polyol may have any one of a linear chain, a branched chain, and a cyclic chain.

前述聚醚多元醇之Mn，較佳係在500~3500之範圍，更佳係在600~3000之範圍，再更佳係在650~2000之範圍。前述聚醚多元醇的Mn若在此範圍，則前述異氰酸酯基末端之胺基甲酸酯預聚物不會有異常的黏度上升，可得到熔融黏度適當之胺基甲酸酯預聚物。 The Mn of the polyether polyol is preferably in the range of 500 to 3,500, more preferably in the range of 600 to 3,000, and even more preferably in the range of 650 to 2,000. When the Mn of the polyether polyol is in this range, the urethane prepolymer of the isocyanate group terminal does not have an abnormal viscosity increase, and a urethane prepolymer having a suitable melt viscosity can be obtained.

又，前述聚碳酸酯多元醇也可使用例如讓碳酸與脂肪族多元醇進行酯化反應所得到之多元醇等。具體來說可列舉出如1,3-丙二醇、1,4-丁二醇、1,6-己二醇、二乙二醇、聚乙二醇、聚丙二醇或聚四亞甲基醚醇(PTMG)等二醇，與碳酸二甲酯、光氣等的反應產物等。這些可以單獨使用，也可2種以上併用。 Further, as the polycarbonate polyol, for example, a polyol obtained by subjecting carbonic acid to an aliphatic polyol to carry out an esterification reaction can be used. Specific examples thereof include 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, polyethylene glycol, polypropylene glycol or polytetramethylene ether alcohol ( A diol such as PTMG), a reaction product with dimethyl carbonate, phosgene or the like. These may be used alone or in combination of two or more.

又，前述低分子量二醇可列舉出例如：乙二醇(EG)、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、新戊二醇、二乙二醇、三乙二醇、四乙二醇、二丙二醇、三丙二醇、3-甲基-1,5-戊二醇、2-丁基-2-乙基-1,3-丙二醇、2-甲基-1,3-丙二醇等脂肪族二醇類；或1,4-環己二醇、1,4-環己二甲醇、氫化雙酚A等脂環族二醇類；或丙三醇、三羥甲基丙烷、新戊四醇等3官能以上的含有羥基之化合物等，這些之中，較佳為1,4-丁二醇、三羥甲基丙烷。前述低分子量二醇也可具有直鏈、分枝、環狀中任一種結構。 Further, examples of the low molecular weight diol include ethylene glycol (EG), 1,2-propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, and 1,5. - pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 3-methyl-1,5-pentane An aliphatic diol such as an alcohol, 2-butyl-2-ethyl-1,3-propanediol or 2-methyl-1,3-propanediol; or 1,4-cyclohexanediol, 1,4-ring An alicyclic diol such as hexanediethanol or hydrogenated bisphenol A; or a trifunctional or higher hydroxy group-containing compound such as glycerol, trimethylolpropane or neopentyl alcohol; among these, 1 is preferred. , 4-butanediol, trimethylolpropane. The low molecular weight diol may have any one of a linear chain, a branched chain, and a cyclic chain.

前述低分子量二醇的分子量，較佳係在62~300之範圍，更佳係在62~200之範圍。前述低分子量二 醇的分子量若在此範圍，則在作為沒有芳香族骨架之多元醇(A)併用之情形，因能更容易的控制反應性，且讓成形性(產率、成形不均)更好而為較佳的。 The molecular weight of the aforementioned low molecular weight diol is preferably in the range of 62 to 300, more preferably in the range of 62 to 200. The aforementioned low molecular weight two When the molecular weight of the alcohol is in this range, when the polyol (A) having no aromatic skeleton is used in combination, the reactivity can be more easily controlled, and the formability (yield, molding unevenness) is better. Preferably.

前述沒有芳香族骨架之多元醇(A)也可使用例如：多元醇丙烯酸酯、聚烯烴多元醇、蓖麻油系多元醇等。 As the polyol (A) having no aromatic skeleton, for example, a polyol acrylate, a polyolefin polyol, a castor oil-based polyol or the like can be used.

另外，也可併用多元胺。前述多元胺可使用例如：乙二胺、異佛酮二胺、4,4’-二環己基甲烷二胺、環己二胺、甲基環己二胺、哌、降莰二胺等。 In addition, a polyamine can also be used in combination. As the polyamine, for example, ethylenediamine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, cyclohexanediamine, methylcyclohexanediamine, and piperidine can be used. , lowering diamine and the like.

(B)沒有芳香族骨架之聚異氰酸酯 (B) Polyisocyanate without aromatic skeleton

接下來，以下說明本發明所使用之沒有芳香族骨架之聚異氰酸酯(B)。 Next, the polyisocyanate (B) having no aromatic skeleton used in the present invention will be described below.

又，本發明中所謂「聚異氰酸酯」係指分子中有2個以上異氰酸酯基(以下也稱為「NCO基」)之化合物。 In the present invention, the term "polyisocyanate" means a compound having two or more isocyanate groups (hereinafter also referred to as "NCO groups") in the molecule.

本發明中，前述沒有芳香族骨架之聚異氰酸酯(B)可使用已知的脂肪族聚異氰酸酯、脂環式聚異氰酸酯中的任一種。它們可以單獨使用，也可2種以上併用。 In the present invention, any of the known aliphatic polyisocyanate and alicyclic polyisocyanate can be used as the polyisocyanate (B) having no aromatic skeleton. They may be used singly or in combination of two or more.

前述脂肪族聚異氰酸酯可列舉出例如：伸己二異氰酸酯(HDI)、二聚體酸二異氰酸酯、離胺酸二異氰酸酯等。市售品未特別限定，可列舉出例如：DURANATE TSA-100、TSS-100、TSE-100、TSR-100、THA-100、D101、A201H、TKA-100等，以上均為旭化成工業股份有限公司製。 The aliphatic polyisocyanate may, for example, be hexamethylene diisocyanate (HDI), dimer acid diisocyanate or lysine diisocyanate. Commercially available products are not particularly limited, and examples thereof include: DURANATE TSA-100, TSS-100, TSE-100, TSR-100, THA-100, D101, A201H, TKA-100, etc., all of which are Asahi Kasei Industrial Co., Ltd. system.

前述脂環族聚異氰酸酯可列舉出例如：異佛 酮二異氰酸酯(IPDI)、氫化二苯基甲烷二異氰酸酯(H12MDI)、氫化苯二伸甲基二異氰酸酯、環己二異氰酸酯、1,3-雙(異氰酸基甲基)環己烷、降莰烯二異氰酸酯等。 Examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), hydrogenated diphenylmethane diisocyanate (H 12 MDI), hydrogenated benzene dimethyl methacrylate, cyclohexane diisocyanate, and 1,3. - bis(isocyanatomethyl)cyclohexane, norbornene diisocyanate, and the like.

然而，在如過去之光聚合起始劑的存在下，單就使用二苯基甲烷二異氰酸酯(MDI)或甲苯二異氰酸酯(TDI)、四甲基苯二伸甲基二異氰酸酯等具有芳香族骨架之聚異氰酸酯(B’)(以下也稱為「芳香族聚異氰酸酯」)來製造異氰酸酯基末端之胺基甲酸酯預聚物之情形，前述芳香族聚異氰酸酯所具有之芳香族結構的吸光度會變得過高，不能充分進行藉由照射紫外線所進行之硬化反應，且前述芳香族聚異氰酸酯本身有在紫外線照射中黃變之問題。因此，要得到適用於特別要求高品質的透明性之光學用構件(例如薄膜、片材等)、纖維、塗料、包裝材料等用途之紫外線硬化性胺基甲酸酯丙烯酸酯組成物，係相當困難的。 However, in the presence of a photopolymerization initiator as in the past, an aromatic skeleton such as diphenylmethane diisocyanate (MDI) or toluene diisocyanate (TDI) or tetramethylbenzene dimethyl diisocyanate is used alone. The polyisocyanate (B') (hereinafter also referred to as "aromatic polyisocyanate") is used to produce an isocyanate-terminated urethane prepolymer, and the aromatic polyisocyanate has an aromatic structure absorbance. The curing reaction by ultraviolet irradiation is not sufficiently performed, and the aromatic polyisocyanate itself has a problem of yellowing during ultraviolet irradiation. Therefore, it is necessary to obtain an ultraviolet curable urethane acrylate composition suitable for use in optical members (for example, films, sheets, etc.), fibers, paints, packaging materials, and the like which are particularly required for high-quality transparency. difficult.

本發明不使用芳香族聚異氰酸酯，藉由使用脂肪族聚異氰酸酯或脂環族聚異氰酸酯作為沒有芳香族骨架之聚異氰酸酯(B)，且必須使用沒有芳香族骨架之特定有機溶劑(F)作為稀釋溶劑，而能夠在紫外線照射中沒有黃變，並可不受阻礙地進行紫外線硬化反應，所得到之組成物因具有優良的耐黃變性，而不會在長期間後變色。 The present invention does not use an aromatic polyisocyanate by using an aliphatic polyisocyanate or an alicyclic polyisocyanate as the polyisocyanate (B) having no aromatic skeleton, and it is necessary to use a specific organic solvent (F) having no aromatic skeleton as a dilution. The solvent can be free from yellowing during ultraviolet irradiation, and can be subjected to an ultraviolet curing reaction without hindrance, and the obtained composition has excellent yellowing resistance and does not change color after a long period of time.

(C)於分子末端具有異氰酸酯基之胺基甲酸酯預聚物 (C) a urethane prepolymer having an isocyanate group at the molecular end

接下來，說明本發明所使用之於分子末端具有異氰酸酯基之胺基甲酸酯預聚物(C)(以下稱為「異氰酸酯基末端之胺基甲酸酯預聚物(C)」)。 Next, a urethane prepolymer (C) having an isocyanate group at a molecular terminal used in the present invention (hereinafter referred to as "isocyanate group-terminated urethane prepolymer (C)") will be described.

前述異氰酸酯基末端之胺基甲酸酯預聚物(C)，必須使用前述沒有芳香族骨架之多元醇(A)與前述沒有芳香族骨架之聚異氰酸酯(B)，依照已知方法進行反應而能得到，其反應方法、反應條件未特別限定。 The above-mentioned isocyanate group-terminated urethane prepolymer (C) must be reacted according to a known method using the above-mentioned polyol (A) having no aromatic skeleton and the aforementioned polyisocyanate (B) having no aromatic skeleton. The reaction method and reaction conditions are not particularly limited.

前述異氰酸酯基末端之胺基甲酸酯預聚物(C)，係前述聚異氰酸酯(B)所具有的異氰酸酯基(以下稱為「NCO基」)，對前述多元醇(A)所具有的羥基(以下也稱為「OH基」)，以當量比過剩之添加量，用已知方法進行反應而能得到。 The urethane prepolymer (C) at the terminal of the isocyanate group is an isocyanate group (hereinafter referred to as "NCO group") of the polyisocyanate (B), and the hydroxyl group of the polyol (A). (hereinafter also referred to as "OH group"), it can be obtained by carrying out a reaction by a known method in an excess amount of an equivalent ratio.

於前述異氰酸酯基末端之胺基甲酸酯預聚物(C)之合成中，作為前述聚異氰酸酯(B)的異氰酸酯當量(以下稱為「NCO當量」)與前述多元醇(A)的羥基當量(以下稱為「OH當量」)之比(即[NCO/OH當量比])，考慮目標的物性、製品品質、反應行為等來設定即可，較佳當量比之範圍係在1.5/1.0~10.0/1.0，更佳當量比之範圍係在2.0/1.0~5.0/1.0。 In the synthesis of the urethane prepolymer (C) at the terminal of the isocyanate group, the isocyanate equivalent of the polyisocyanate (B) (hereinafter referred to as "NCO equivalent") and the hydroxyl equivalent of the aforementioned polyol (A) The ratio (hereinafter referred to as "OH equivalent") (that is, [NCO/OH equivalent ratio]) may be set in consideration of physical properties, product quality, reaction behavior, etc., and the preferred equivalent ratio is in the range of 1.5/1.0. The range of 10.0/1.0, better equivalence ratio is between 2.0/1.0 and 5.0/1.0.

前述異氰酸酯基末端之胺基甲酸酯預聚物(C)之合成方法未特別限定，可列舉出例如：[方法1]對已添加入反應容器中之聚異氰酸酯(B)，以滴入、分批、整批等適當手段添加除去水分之多元醇(A)，反應至前述多元醇(A)所具有的羥基實質上變成沒有之方法，或[方法2]對已添加入反應容器中的除去水分之多元醇(A)，以滴 入、分批、整批等適當手段添加聚異氰酸酯(B)，反應至前述多元醇(A)所具有的羥基實質上變成沒有之方法等。 The method for synthesizing the above-mentioned isocyanate group-terminated urethane prepolymer (C) is not particularly limited, and for example, [Method 1] the polyisocyanate (B) which has been added to the reaction container is dripped, The water-removing polyol (A) is added in a batch, a batch, or the like by an appropriate means, and the reaction is carried out until the hydroxyl group of the polyol (A) is substantially not obtained, or [Method 2] has been added to the reaction vessel. Remove the moisture of the polyol (A), drop The polyisocyanate (B) is added by an appropriate means such as a batch, a batch, or a whole batch, and the reaction is carried out until the hydroxyl group of the polyol (A) is substantially not obtained.

為了穩定控制反應中的發熱，同時安全且正常地進行反應，較佳為滴入或分批之添加方法。 In order to stably control the heat generation in the reaction while carrying out the reaction safely and normally, it is preferred to add the method by dropwise or batchwise.

前述異氰酸酯基末端之胺基甲酸酯預聚物(C)之製造，通常係在無溶劑下進行，但也可在溶劑中進行反應來製造。於在溶劑中反應之情形，使用不會妨礙反應之溶劑即可，其種類未特別限定。使用於反應之溶劑，在反應途中或反應結束後，期望以減壓加熱或薄膜餾去等適當方法來除去。 The production of the above-mentioned isocyanate group-terminated urethane prepolymer (C) is usually carried out without a solvent, but it can also be carried out by reacting in a solvent. In the case of reacting in a solvent, a solvent which does not inhibit the reaction may be used, and the kind thereof is not particularly limited. The solvent used in the reaction is desirably removed by a suitable method such as heating under reduced pressure or distillation of the film during or after the completion of the reaction.

前述異氰酸酯基末端之胺基甲酸酯預聚物(C)的反應條件(溫度、時間、壓力等)，設定在能正常地控制反應行為(安全性、穩定性)與製品品質等之範圍即可，未特別限定。通常較佳在反應溫度50~90℃，且反應時間2~24小時之條件下進行。壓力為常壓、加壓、減壓中的任一種均可。 The reaction conditions (temperature, time, pressure, and the like) of the urethane prepolymer (C) at the terminal of the isocyanate group are set to a range in which the reaction behavior (safety, stability), product quality, and the like can be normally controlled. However, it is not particularly limited. It is usually preferably carried out at a reaction temperature of 50 to 90 ° C and a reaction time of 2 to 24 hours. The pressure may be any of normal pressure, pressure, and reduced pressure.

反應方式可選擇例如：批次、半連續、連續等已知的反應方式，未特別限定。 The reaction mode may be, for example, a known reaction mode such as batch, semi-continuous, or continuous, and is not particularly limited.

又，在製造前述異氰酸酯基末端之胺基甲酸酯預聚物(C)時，視需要可使用胺基甲酸酯化觸媒。前述觸媒可在原料添加步驟、反應步驟中的任意階段適當添加。又，觸媒的添加方法係整批、分批、連續等，未特別限定。 Further, in the production of the urethane prepolymer (C) at the terminal of the isocyanate group, a urethane catalyst may be used as needed. The above catalyst can be appropriately added at any stage of the raw material addition step and the reaction step. Further, the method of adding the catalyst is batch, batch, continuous, etc., and is not particularly limited.

前述胺基甲酸酯化觸媒可使用已知之物，可列舉出例如：三乙基胺、三丁基胺、芐基二丁基胺、三 伸乙基二胺、N-甲基啉等含氮化合物；或四丁氧化鈦、氧化二丁錫、二月桂酸二丁錫、2-乙基己酸錫、環烷酸鋅、環烷酸鈷、2-乙基己酸鋅、二醇酸鉬、乙酸鉀、硬脂酸鋅、辛酸錫、二丁錫二月桂酸酯等有機金屬化合物；或氯化鐵、氯化鋅等無機化合物等。 As the aforementioned urethane-catalyzing catalyst, known ones can be used, and examples thereof include triethylamine, tributylamine, benzyldibutylamine, tri-ethylenediamine, and N-methyl. a nitrogen-containing compound such as a porphyrin; or tetrabutyl titanate, dibutyltin oxide, dibutyltin dilaurate, tin 2-ethylhexanoate, zinc naphthenate, cobalt naphthenate, zinc 2-ethylhexanoate, An organometallic compound such as molybdate dibasic acid, potassium acetate, zinc stearate, tin octylate or dibutyltin dilaurate; or an inorganic compound such as ferric chloride or zinc chloride.

通常反應較佳係在氮氣或氬氣等惰性氣體環境下進行，但也可在乾燥空氣環境下或密閉條件下等未混入水分之條件下進行。 The reaction is usually carried out under an inert gas atmosphere such as nitrogen or argon, but it may be carried out under a dry air atmosphere or under a closed condition without mixing water.

前述異氰酸酯基末端之胺基甲酸酯預聚物(C)的異氰酸酯當量(以下也稱為「NCO當量」)較佳係在100~10000之範圍，更佳係在200~1000之範圍。前述(C)的NCO當量若在此範圍，則不會產生異常的黏度上升，可得到加工性優良之胺基甲酸酯預聚物。 The isocyanate equivalent (hereinafter also referred to as "NCO equivalent") of the urethane prepolymer (C) at the terminal of the isocyanate group is preferably in the range of from 100 to 10,000, more preferably in the range of from 200 to 1,000. When the NCO equivalent of the above (C) is within this range, an abnormal viscosity increase does not occur, and a urethane prepolymer excellent in workability can be obtained.

又，本發明中所謂「異氰酸酯當量」(單位：g/eq，即g/當量)係後述之依據JIS K 7301測定之值。 In the present invention, the "isocyanate equivalent" (unit: g/eq, that is, g/equivalent) is a value measured in accordance with JIS K 7301, which will be described later.

(D)具有羥基之(甲基)丙烯酸類化合物 (D) (meth)acrylic compound having a hydroxyl group

下面說明對前述異氰酸酯基末端之胺基甲酸酯預聚物(C)進行加成反應之具有羥基之(甲基)丙烯酸類化合物(D)。 Next, the (meth)acrylic compound (D) having a hydroxyl group in the addition reaction of the above-mentioned isocyanate group-terminated urethane prepolymer (C) will be described.

本發明中，讓一部分或全部量的前述異氰酸酯基末端之胺基甲酸酯預聚物(C)中之異氰酸酯基，與具有羥基之(甲基)丙烯酸類化合物(D)進行加成反應，改性為於分子末端具有(甲基)丙烯醯基之胺基甲酸酯丙烯酸酯寡聚物(E)。 In the present invention, a part or the whole amount of the isocyanate group in the urethane prepolymer (C) of the isocyanate group terminal is subjected to an addition reaction with the (meth)acrylic compound (D) having a hydroxyl group. It is modified to a urethane acrylate oligomer (E) having a (meth) acrylonitrile group at the molecular terminal.

藉由對前述異氰酸酯基末端之胺基甲酸酯預 聚物(C)以前述具有羥基之(甲基)丙烯酸類化合物(D)改性產生之雙鍵的導入，經由照射紫外線在雙鍵部位迅速發生硬化反應，而即使完全不含光聚合起始劑，也可展現優良的紫外線硬化性、塗布至基材後的保型性、機械強度、耐久性、透明性等過去沒有的性能。 By pre-precipitating the aminocyanate at the end of the isocyanate group The introduction of the double bond produced by the modification of the (meth)acrylic compound (D) having a hydroxyl group as described above, and rapid curing reaction at the double bond site by irradiation of ultraviolet rays, even if the photopolymerization initiation is completely absent The agent can also exhibit excellent ultraviolet curability, shape retention after application to a substrate, mechanical strength, durability, transparency, and the like which have not been obtained in the past.

前述具有羥基之(甲基)丙烯酸類化合物(D)可列舉出例如：(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸3-羥丙酯、(甲基)丙烯酸4-羥丁酯、新戊四醇三丙烯酸酯等，這些之中，從例如以照射紫外線產生的快速硬化性優良，且特別以機械強度提升的點來看，較佳為丙烯酸2-羥乙酯(2HEA)、丙烯酸4-羥丁酯(4HBA)。這些可以單獨使用，也可2種以上併用。 Examples of the (meth)acrylic compound (D) having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate. Among the esters, 4-hydroxybutyl (meth)acrylate, neopentyl alcohol triacrylate, etc., among them, for example, it is excellent in rapid hardenability by irradiation of ultraviolet rays, and particularly in terms of mechanical strength improvement, Preferred is 2-hydroxyethyl acrylate (2HEA), 4-hydroxybutyl acrylate (4HBA). These may be used alone or in combination of two or more.

(E)於分子末端具有(甲基)丙烯醯基之胺基甲酸酯丙烯酸酯寡聚物 (E) urethane acrylate oligomer having a (meth) acrylonitrile group at the molecular end

接下來，說明在本發明中使用之於分子末端具有(甲基)丙烯醯基之胺基甲酸酯丙烯酸酯寡聚物(E)(以下稱為「胺基甲酸酯丙烯酸酯寡聚物(E)」)。 Next, a urethane acrylate oligomer (E) having a (meth) acrylonitrile group at the molecular terminal used in the present invention (hereinafter referred to as "amino acrylate acrylate oligomer" will be described. (E)").

前述胺基甲酸酯丙烯酸酯寡聚物(E)，係相對於100質量份的前述異氰酸酯基末端之胺基甲酸酯預聚物(C)，較佳以範圍在0.5~300質量份，更佳以範圍在1.0~100質量份，添加具有羥基之(甲基)丙烯酸類化合物(D)，讓前述具有羥基之(甲基)丙烯酸類化合物(D)與前述異氰酸酯基末端之胺基甲酸酯預聚物(C)中的異氰酸酯基總數的較佳為5~100%，更佳為10~100%進行反應而成之物。 The urethane acrylate oligomer (E) is preferably in a range of from 0.5 to 300 parts by mass per 100 parts by mass of the urethane prepolymer (C) at the terminal isocyanate group. More preferably, the (meth)acrylic compound (D) having a hydroxyl group is added in an amount of from 1.0 to 100 parts by mass, and the above-mentioned (meth)acrylic compound (D) having a hydroxyl group and the above-mentioned aminocyl group at the terminal of the isocyanate group are added. The total number of isocyanate groups in the acid ester prepolymer (C) is preferably from 5 to 100%, more preferably from 10 to 100%.

若讓前述異氰酸酯基末端之胺基甲酸酯預聚物(C)的異氰酸酯基在此範圍內與前述具有羥基之(甲基)丙烯酸類化合物(D)進行反應，則可展現優良的硬化性、塗布到基材後的保型性、機械強度、耐久性、基材密著性等性能。 When the isocyanate group of the above-mentioned isocyanate-terminated urethane prepolymer (C) is reacted in this range with the above-mentioned (meth)acrylic compound (D) having a hydroxyl group, excellent curability can be exhibited. And the properties such as shape retention, mechanical strength, durability, and substrate adhesion after application to the substrate.

前述胺基甲酸酯丙烯酸酯寡聚物(E)的(甲基)丙烯酸當量係在450~1100g/當量(以下省略單位)之範圍，較佳係在500~900之範圍，更佳係在500~750之範圍。前述(E)的(甲基)丙烯酸當量若在此範圍，則可一同顯示優良的自我修復性與良好的紫外線硬化性。 The (meth)acrylic equivalent of the urethane acrylate oligomer (E) is in the range of 450 to 1100 g / equivalent (hereinafter abbreviated units), preferably in the range of 500 to 900, more preferably in the range of 500 to 900. Range of 500~750. When the (meth)acrylic equivalent of the above (E) is in this range, it can exhibit excellent self-healing properties and good ultraviolet curability.

然而，在前述胺基甲酸酯丙烯酸酯寡聚物(E)的(甲基)丙烯酸當量小於450之情形，所得到的薄膜成形體的硬度會變過高，因彈性不足而恐怕不會顯示自我修復性。而在前述(E)的(甲基)丙烯酸當量大於1100之情形，以照射紫外線進行的硬化反應容易變得不充分，恐怕會在薄膜成形體的表面殘存黏性，且不會顯示自我修復性。 However, in the case where the (meth)acrylic equivalent of the aforementioned urethane acrylate oligomer (E) is less than 450, the hardness of the obtained film formed body may become too high, and it may not be displayed due to insufficient elasticity. Self-healing. On the other hand, when the (meth)acrylic acid equivalent of the above (E) is more than 1,100, the hardening reaction by irradiation with ultraviolet rays is likely to be insufficient, and there is a fear that the surface of the film formed body remains sticky and does not exhibit self-healing property. .

而在本發明中，胺基甲酸酯丙烯酸酯寡聚物(E)的(甲基)丙烯酸當量，係每1莫耳(甲基)丙烯醯基的分子量，係以組成物中的(甲基)丙烯醯基濃度(mol/g)之倒數所表示之值。 In the present invention, the (meth)acrylic equivalent of the urethane acrylate oligomer (E) is the molecular weight per 1 mole of (meth)acryl oxime group, The value expressed by the reciprocal of the acrylonitrile concentration (mol/g).

前述胺基甲酸酯丙烯酸酯寡聚物(E)的依據JIS Z 8803測定之在50℃的熔融黏度較佳係在500~200000mPa．s之範圍，更佳係在500~100000之範圍。前述(E)之在50℃的熔融黏度若在此範圍，則加工性與生產 性會提升，且可減少溶劑的使用量，因能對減少環境負擔作出貢獻而係較佳的。 The urethane acrylate oligomer (E) according to JIS Z 8803 has a melt viscosity at 50 ° C preferably in the range of 500 to 200,000 mPa. The range of s is better in the range of 500~100000. If the melt viscosity at 50 ° C of the above (E) is in this range, the processability and production Sex will increase and the amount of solvent used can be reduced, which is better because it can contribute to reducing the environmental burden.

又，本發明中，也可使用未對前述具有羥基之(甲基)丙烯酸類化合物(D)進行加成反應之未反應的於分子末端有異氰酸酯基之胺基甲酸酯預聚物，與加成反應的產物之於分子末端具有(甲基)丙烯醯基之胺基甲酸酯丙烯酸酯寡聚物(E)的混合物。 Further, in the present invention, an unreacted urethane prepolymer having an isocyanate group at the molecular terminal, which is not subjected to an addition reaction of the (meth)acrylic compound (D) having a hydroxyl group, may be used. The product of the addition reaction is a mixture of urethane acrylate oligomer (E) having a (meth) acrylonitrile group at the molecular end.

在讓前述異氰酸酯基末端之胺基甲酸酯預聚物(C)，與具有羥基之(甲基)丙烯酸類化合物(D)進行胺基甲酸酯化反應時，可以是無觸媒，也可以是在胺基甲酸酯化觸媒存在下進行，未特別限定。 When the urethane prepolymer (C) at the terminal end of the isocyanate group is subjected to a urethanization reaction with the (meth)acrylic compound (D) having a hydroxyl group, it may be a catalyst-free, It may be carried out in the presence of a urethane catalyst, and is not particularly limited.

於使用前述胺基甲酸酯化觸媒之情形，可於胺基甲酸酯化反應的初期或途中的任意階段適當添加。 In the case of using the aforementioned urethane-catalyzed catalyst, it may be appropriately added at an initial stage or at any stage in the middle of the urethanization reaction.

前述胺基甲酸酯化觸媒能使用已知者，可列舉出例如：三乙基胺、三伸乙基二胺、N-甲基啉等含氮化合物、或乙酸鉀、硬脂酸鋅、辛酸亞錫等有機金屬鹽、或二月桂酸二辛錫、二月桂酸二丁錫等有機金屬化合物。 The above-mentioned urethane-based catalyst can be used, and examples thereof include triethylamine, tri-ethylidene diamine, and N-methyl group. A nitrogen-containing compound such as a quinone or an organic metal salt such as potassium acetate, zinc stearate or stannous octoate; or an organometallic compound such as dioctyltin dilaurate or dibutyltin dilaurate.

前述胺基甲酸酯化觸媒的使用量，只要不會對反應時的安全性、中間體或製品的穩定性、品質等產生不良影響，即無特別限定。 The amount of the urethane-based catalyst to be used is not particularly limited as long as it does not adversely affect the safety at the time of reaction, the stability or quality of the intermediate or the product, and the like.

前述胺基甲酸酯化反應較佳進行至異氰酸酯當量(單位：g/eq，即g/當量)在實質上達一定量。 The aforementioned urethanization reaction is preferably carried out to an isocyanate equivalent (unit: g/eq, i.e., g/equivalent) in a substantial amount.

又，於反應結束後或反應途中，也可添加已知的觸媒去活化劑，去活化或抑制前述胺基甲酸酯化觸 媒的活性，來謀取反應方面、儲藏方面、品質方面等的安定化。 Further, after the reaction is completed or during the reaction, a known catalyst deactivator may be added to deactivate or inhibit the aforementioned urethane touch. The activity of the medium is to achieve stability in terms of reaction, storage, and quality.

(F)沒有芳香族骨架之有機溶劑 (F) Organic solvent without aromatic skeleton

接下來，對本發明中作為稀釋溶劑所必須使用之沒有芳香族骨架的有機溶劑(F)說明於下。 Next, an organic solvent (F) having no aromatic skeleton which is used as a diluent solvent in the present invention will be described below.

本發明中，由於使用沒有芳香族骨架之有機溶劑(F)，即便完全不使用光聚合起始劑，也可如使用過去的光聚合起始劑之紫外線硬化性胺基甲酸酯丙烯酸酯組成物般，賦予優良的紫外線硬化性，可展現在紫外線照射時無黃變，不易隨時間產生黃變等優良效果。 In the present invention, since an organic solvent (F) having no aromatic skeleton is used, even if a photopolymerization initiator is not used at all, it can be composed of a UV-curable urethane acrylate using a conventional photopolymerization initiator. It imparts excellent ultraviolet curability to the object, and exhibits excellent effects such as no yellowing upon ultraviolet irradiation and yellowing with time.

在完全不使用光聚合起始劑，且不使用前述沒有芳香族骨架之有機溶劑(F)，僅使用具有芳香族骨架之有機溶劑的情形，無法滿足地展現紫外線硬化性、耐黃變性、在塗工面無黏性等性能，無法達成本發明之目的。 In the case where the photopolymerization initiator is not used at all, and the organic solvent (F) having no aromatic skeleton described above is used, and only the organic solvent having an aromatic skeleton is used, the ultraviolet curability and yellowing resistance are unsatisfactory. The coating surface has no properties such as viscosity and cannot achieve the object of the present invention.

本發明中使用之沒有芳香族骨架之有機溶劑(F)，係從由酮系溶劑、醯胺系溶劑、及鹵化烷系溶劑所構成之群組中所選出的至少一種。 The organic solvent (F) having no aromatic skeleton used in the present invention is at least one selected from the group consisting of a ketone solvent, a guanamine solvent, and a halogenated alkyl solvent.

前述酮系溶劑係例如可列舉出甲乙酮、丙酮、甲基異丁基酮、環己酮、二異丁基酮、異佛酮、2,3-己二酮、4-甲基-2,3-戊二酮、5-甲基-2,3-己二酮、2,3-戊二酮、2-己酮、環庚酮、環戊酮、3-癸酮、2-十二酮、4-羥基-4-甲基-2-戊酮(二丙酮醇)、2,3-丁二酮(diacetyl)、2,4-二甲基-3-戊酮、3,4-二甲基-1,2-環戊二酮、3,5-二甲基-1,2-環戊二酮、2-羥基-6-異丙基-3-甲基-2-環己 烯酮、4-庚酮、3-辛酮、3-庚酮、3-乙基-2-羥基-2-環戊烯酮、3-壬酮、3-己酮、1-戊烯-3-酮、2-十七烷酮、2,3-十七烷二酮、3,4-己二酮、6,10,14-三甲基-2-十五烷酮、5-己烯-2-酮、4-己烯-3-酮、1-己烯-3-酮、2-己基環戊酮、1-羥基-2-丁酮、4-羥基-2-丁酮、2-羥基-2-環己烯酮、1-羥基-2-庚酮、3-羥基-2-辛酮、2-羥基-3,4-二甲基-2-環戊烯酮、2-羥基-3-戊酮、1-羥基-4-甲基-2-戊酮、1-羥基-5-甲基-2-己酮、3-羥基-2-戊酮、6-甲基-3-庚酮、2-甲基-3-(2-戊烯基)-2-環戊烯酮、4-異丙基-2-環己烯酮、5-異丙基-3-壬烯-2,8-二酮、5-異丙基-8-甲基-6,8-壬二烯-2-酮、3-甲基-2-(順式-2-戊烯基)-2-環戊烯酮、3-甲基-2-(反式-2-戊烯基)-2-環戊烯酮、對-2-酮、酮、4-甲基-3-戊烯-2-酮、2-庚酮、2-壬酮、2-辛酮、甲基紫羅酮、5-甲基-2-己酮、3-甲基-2-戊酮、2-十一烷酮、2-癸酮、2-戊酮、2-十三烷酮、3-丁烯-2-酮、3-甲基-2-環戊烯酮、6-甲基-2-庚酮、5-甲基-2-庚烯-4-酮、3-甲基-2-己酮、3-甲基-2-戊酮、α-甲基紫羅酮、3-甲基-1,2-環己二酮、3-甲基環己酮、3-甲基環十五烷酮、6-甲基-3,5--庚二烯-2-酮、6-甲基-5-庚烯-2-酮、3-甲基-2,4-壬二酮、4-壬酮、3-壬烯-2-酮、3,5-辛二烯-2-酮、1,5-辛二烯-3-酮、3-辛烯-2-酮、1-辛烯-3-酮、2-辛烯-4-酮、4-側氧基異佛酮、2-十五烷酮、3-戊酮、3-戊烯-2-酮、4-羥基己-3-酮、1-(1-對-6-基)-1-丙酮、2-丙醯基吡咯、覆盆子酮、4-三級丁基環己酮、4-三級戊基環己酮、2-十四烷酮、四甲基乙基環己烯酮、12-十三烷烯-2-酮、3,5,5-三甲基 -1,2-環己二酮、1-(2,4,4-三甲基-2-環己烯基)-反式-2-丁烯-1-酮、2-羥基-2,6,6-三甲基環己酮、2,2,6-三甲基環己酮、3,3,5-三甲基環己酮、2,3-十一烷二酮、6-羥基-5-癸酮、馬鞭烯酮、1,10-十一烯-2-酮、2,2,6-三甲基-1,4-環己二酮、2,3-辛二酮、2,5-己二酮、2-環己烯酮、2-庚烯-4-酮、2-亞己基環戊酮、2-甲基-3-戊酮、3,5,5-三甲基-4-亞甲基-2-環己烯酮、4-(2,3,6-三甲基苯基)-3-丁烯-2-酮、4,5-辛二酮、4,7-二甲基-6-辛烯-3-酮、5,6-癸二酮、5-甲基-5-己烯-2-酮、6-甲基-4,5-庚二烯-2-酮、6-羥基羧酸、7-辛烯-2-酮、8-壬烯-2-酮、3-乙基-2-羥基-4-甲基-2-環戊烯酮、2-己基-2-環戊烯酮、8-羥基-4-對-3-酮、5-壬酮等。這些酮系溶劑之中，由於能展現更優良的紫外線硬化性、耐黃變性等效果，較佳為甲乙酮、丙酮、甲基異丁基酮、環己酮、二異丁基酮、異佛酮。 Examples of the ketone solvent include methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone, isophorone, 2,3-hexanedione, and 4-methyl-2,3. -pentanedione, 5-methyl-2,3-hexanedione, 2,3-pentanedione, 2-hexanone, cycloheptanone, cyclopentanone, 3-fluorenone, 2-dodecanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), 2,3-butanedione (diacetyl), 2,4-dimethyl-3-pentanone, 3,4-dimethyl -1,2-cyclopentadione, 3,5-dimethyl-1,2-cyclopentanedione, 2-hydroxy-6-isopropyl-3-methyl-2-cyclohexenone, 4 -heptanone, 3-octanone, 3-heptanone, 3-ethyl-2-hydroxy-2-cyclopentenone, 3-fluorenone, 3-hexanone, 1-penten-3-one, 2 -heptadecanone, 2,3-heptadecanedione, 3,4-hexanedione, 6,10,14-trimethyl-2-pentadecanone, 5-hexen-2-one, 4-hexen-3-one, 1-hexen-3-one, 2-hexylcyclopentanone, 1-hydroxy-2-butanone, 4-hydroxy-2-butanone, 2-hydroxy-2-cyclo Hexenone, 1-hydroxy-2-heptanone, 3-hydroxy-2-octanone, 2-hydroxy-3,4-dimethyl-2-cyclopentenone, 2-hydroxy-3-pentanone, 1-hydroxy-4-methyl-2-pentanone, 1-hydroxy-5-methyl-2-hexanone, 3-hydroxy-2-pentanone, 6-methyl-3-glycol , 2-methyl-3-(2-pentenyl)-2-cyclopentenone, 4-isopropyl-2-cyclohexenone, 5-isopropyl-3-decene-2,8 -dione, 5-isopropyl-8-methyl-6,8-nonadien-2-one, 3-methyl-2-(cis-2-pentenyl)-2-cyclopentene Ketone, 3-methyl-2-(trans-2-pentenyl)-2-cyclopentenone, pair -2-ketone, Ketone, 4-methyl-3-penten-2-one, 2-heptanone, 2-nonanone, 2-octanone, methyl ionone, 5-methyl-2-hexanone, 3-methyl Ketopentanone, 2-undecyl ketone, 2-nonanone, 2-pentanone, 2-tridecyl ketone, 3-buten-2-one, 3-methyl-2-cyclopentene Ketone, 6-methyl-2-heptanone, 5-methyl-2-hepten-4-one, 3-methyl-2-hexanone, 3-methyl-2-pentanone, α-methyl Ilinone, 3-methyl-1,2-cyclohexanedione, 3-methylcyclohexanone, 3-methylcyclopentadecanone, 6-methyl-3,5-heptadiene- 2-keto, 6-methyl-5-hepten-2-one, 3-methyl-2,4-indanedione, 4-indolone, 3-decen-2-one, 3,5-octyl Dien-2-one, 1,5-octadien-3-one, 3-octen-2-one, 1-octene-3-one, 2-octene-4-one, 4-side oxygen Isofosone, 2-pentadecanone, 3-pentanone, 3-penten-2-one, 4-hydroxyhexan-3-one, 1-(1-pair -6-yl)-1-propanone, 2-propionylpyrrole, raspberry ketone, 4-tributylcyclohexanone, 4-tripentylcyclohexanone, 2-tetradecanone, tetramethyl Ethyl cyclohexenone, 12-tridecen-2-one, 3,5,5-trimethyl-1,2-cyclohexanedione, 1-(2,4,4-trimethyl -2-cyclohexenyl)-trans-2-buten-1-one, 2-hydroxy-2,6,6-trimethylcyclohexanone, 2,2,6-trimethylcyclohexanone , 3,3,5-trimethylcyclohexanone, 2,3-undecanedione, 6-hydroxy-5-fluorenone, whipenone, 1,10-undecen-2-one, 2 , 2,6-trimethyl-1,4-cyclohexanedione, 2,3-octanedione, 2,5-hexanedione, 2-cyclohexenone, 2-hepten-4-one, 2-hexylcyclopentanone, 2-methyl-3-pentanone, 3,5,5-trimethyl-4-methylene-2-cyclohexenone, 4-(2,3,6- Trimethylphenyl)-3-buten-2-one, 4,5-octanedione, 4,7-dimethyl-6-octene-3-one, 5,6-nonanedione, 5 -Methyl-5-hexen-2-one, 6-methyl-4,5-heptadien-2-one, 6-hydroxycarboxylic acid, 7-octene-2-one, 8-decene- 2-ketone, 3-ethyl-2-hydroxy-4-methyl-2-cyclopentenone, 2-hexyl-2-cyclopentenone, 8-hydroxy-4-pair 3-ketone, 5-fluorenone, and the like. Among these ketone solvents, methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone, isophorone are preferred because they exhibit more excellent ultraviolet curability and yellowing resistance. .

前述醯胺系溶劑可列舉出例如：二甲基甲醯胺、N,N-二甲基乙醯胺、烷氧基-N-異丙基-丙醯胺、羥基烷基醯胺等脂肪族醯胺系溶劑、或N-甲基-2-吡咯啶酮、N-乙基-吡咯啶酮等脂環族醯胺系溶劑。這些醯胺系溶劑之中，由於能展現更優良的紫外線硬化性、耐黃變性等效果，較佳為二甲基甲醯胺。 Examples of the amide-based solvent include aliphatic groups such as dimethylformamide, N,N-dimethylacetamide, alkoxy-N-isopropyl-propionamide, and hydroxyalkylguanamine. A guanamine-based solvent or an alicyclic amide-based solvent such as N-methyl-2-pyrrolidone or N-ethyl-pyrrolidone. Among these amide-based solvents, dimethylformamide is preferred because it exhibits more excellent effects such as ultraviolet curability and yellowing resistance.

前述鹵化烷系溶劑係氟系、氯系、溴系、碘系等有機溶劑，這些之中，由於能展現更優良的紫外線硬化性、耐黃變性等效果，較佳為氯系有機溶劑。 The halogenated alkane-based solvent is an organic solvent such as a fluorine-based, chlorine-based, bromine-based or iodine-based organic solvent. Among them, a chlorine-based organic solvent is preferred because it exhibits more excellent effects such as ultraviolet curability and yellowing resistance.

前述氯系有機溶劑可列舉出例如：二氯甲烷、氯仿、三氯乙烯、四氯乙烯、四氯化碳、1,2-二氯乙 烷、1,1,1-三氯乙烷等，較佳係二氯甲烷、氯仿。 Examples of the chlorine-based organic solvent include dichloromethane, chloroform, trichloroethylene, tetrachloroethylene, carbon tetrachloride, and 1,2-dichloroethane. An alkane, 1,1,1-trichloroethane or the like is preferably dichloromethane or chloroform.

前述有機溶劑(F)之中，酮系溶劑因對於紫外線硬化性、耐黃變性之提升可更有效地作用，而為較佳。 Among the above organic solvents (F), a ketone solvent is preferred because it can act more effectively on ultraviolet curability and yellowing resistance.

本發明之紫外線硬化性胺基甲酸酯丙烯酸酯組成物係將前述胺基甲酸酯丙烯酸酯寡聚物(E)與前述沒有芳香族骨架之有機溶劑(F)混合而得，前述有機溶劑(F)的含有率係在0.2~80質量%之範圍。 The ultraviolet curable urethane acrylate composition of the present invention is obtained by mixing the urethane acrylate oligomer (E) with the organic solvent (F) having no aromatic skeleton, and the organic solvent. The content of (F) is in the range of 0.2 to 80% by mass.

本發明之紫外線硬化性胺基甲酸酯丙烯酸酯組成物中的前述有機溶劑(F)之含有率若在此範圍，則在照射紫外線時可有效率且正常地使紫外線硬化性胺基甲酸酯丙烯酸酯組成物進行硬化反應，能夠不產生硬化不均地平坦且漂亮地塗布。 When the content ratio of the organic solvent (F) in the ultraviolet curable urethane acrylate composition of the present invention is within this range, the ultraviolet curable urethane can be efficiently and normally irradiated when irradiated with ultraviolet rays. The ester acrylate composition is subjected to a curing reaction, and can be applied in a flat and beautiful manner without causing unevenness in hardening.

前述沒有芳香族骨架之有機溶劑(F)的混合係採用已知方法即可，未特別限定。 The mixing system of the organic solvent (F) having no aromatic skeleton described above may be a known method, and is not particularly limited.

一般所使用之具有芳香族結構的光聚合起始劑(例如1-羥基環己基苯基酮等)，已知藉由芳香族結構的光吸收而分解產生自由基，分解之光聚合起始劑會再結合，此時，會成為黃色度高的醌型結構。 A photopolymerization initiator having an aromatic structure (for example, 1-hydroxycyclohexyl phenyl ketone or the like) which is generally used, and is known to be decomposed by light absorption of an aromatic structure to generate a radical, and a photopolymerization initiator which decomposes. Will be combined again, at this time, it will become a yellow structure with a high degree of yellowness.

本發明被認為，藉由完全不使用光聚合起始劑，並使用沒有芳香族骨架之有機溶劑(F)，進行與使用光聚合起始劑之情形相同的紫外線硬化反應，但此時，因與使用光聚合起始劑的情形不同，不會生成醌型結構，不會使硬化物黃變，推測能得到無黃變且透明性優良之成形體與塗膜等。 In the present invention, it is considered that the same ultraviolet curing reaction as in the case of using a photopolymerization initiator is carried out by using no photopolymerization initiator at all and using an organic solvent (F) having no aromatic skeleton, but at this time, Unlike the case of using a photopolymerization initiator, a ruthenium-based structure is not formed, and the cured product is not yellowed, and it is presumed that a molded article, a coating film, and the like which are free from yellowing and have excellent transparency can be obtained.

本發明之紫外線硬化性胺基甲酸酯丙烯酸酯組成物，在係未與前述具有羥基之(甲基)丙烯酸類化合物(D)進行加成反應之未反應的於分子末端具有異氰酸酯基之胺基甲酸酯預聚物，與加成反應的產物之於分子末端具有(甲基)丙烯醯基之胺基甲酸酯丙烯酸酯寡聚物(E)的混合物之情形，在製造步驟的任一階段，可調配具沒有芳香族骨架的官能基之反應性化合物作為硬化劑。 The ultraviolet curable urethane acrylate composition of the present invention is an unreacted amine having an isocyanate group at a molecular terminal in an addition reaction which is not subjected to an addition reaction with the above-mentioned (meth)acrylic compound (D) having a hydroxyl group. a urethane prepolymer, a mixture of a product of an addition reaction and a urethane acrylate oligomer (E) having a (meth) acrylonitrile group at the molecular terminal, in the manufacturing step In one stage, a reactive compound having a functional group having no aromatic skeleton can be used as a hardener.

前述硬化劑可列舉出例如：脂肪族多元醇、脂環族多元醇、脂肪族多元胺、脂環族多元胺等。 Examples of the curing agent include aliphatic polyhydric alcohols, alicyclic polyhydric alcohols, aliphatic polyamines, and alicyclic polyamines.

使用作為硬化劑之多元醇的羥基，與紫外線硬化性胺基甲酸酯丙烯酸酯組成物中的異氰酸酯基之當量比，即[NCO/OH當量比]，較佳係在0.7~20之範圍，更佳係在0.7~10之範圍，再更佳係在0.9~5.0之範圍，最佳係在0.9~1.1。前述[NCO/OH當量比]若在此範圍，則能有效率且良好地進行硬化反應。 The equivalent ratio of the hydroxyl group of the polyol as the curing agent to the isocyanate group in the ultraviolet curable urethane acrylate composition, that is, the [NCO/OH equivalent ratio] is preferably in the range of 0.7 to 20, More preferably in the range of 0.7 to 10, and even better in the range of 0.9 to 5.0, and the best is in the range of 0.9 to 1.1. When the above [NCO/OH equivalent ratio] is within this range, the curing reaction can be carried out efficiently and satisfactorily.

本發明之紫外線硬化性胺基甲酸酯丙烯酸酯組成物中，除了前述胺基甲酸酯丙烯酸酯寡聚物(E)以外，在不超出本發明之目的的範圍內，可使用沒有芳香族骨架之丙烯酸類單體。前述丙烯酸類單體可列舉出例如：(甲基)丙烯酸；(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸二級丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯等C1-24的( 甲基)丙烯酸烷酯；(甲基)丙烯酸環己酯、(甲基)丙烯酸環戊酯等(甲基)丙烯酸環烷酯；(甲基)丙烯酸三環[5.2.1.02,6]癸-8-酯(dicyclopentanyl(meta)acrylate)、(甲基)丙烯酸三環[5.2.1.02,6]癸烯-8-酯(dicyclopentenyl(meta)acrylate)、(甲基)丙烯酸三環[5.2.1.02,6]癸烯-8-氧基乙酯(dicyclopentenyloxyethylene(meta)acrylate)、(甲基)丙烯酸酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸三環癸酯等橋接環式(甲基)丙烯酸酯；(甲基)丙烯酸羥乙酯、(甲基)丙烯酸羥丙酯、(甲基)丙烯酸羥丁酯等(甲基)丙烯酸羥基C2-10烷酯或C2-10烷烴二醇單(甲基)丙烯酸酯；(甲基)丙烯酸三氟乙酯、(甲基)丙烯酸四氟丙酯、(甲基)丙烯酸六氟異丙酯等(甲基)丙烯酸氟化C1-10烷酯；(甲基)丙烯酸甲氧基乙酯等(甲基)丙烯酸烷氧基烷酯；聚乙二醇單(甲基)丙烯酸酯等聚伸烷二醇單(甲基)丙烯酸酯；丙三醇單(甲基)丙烯酸酯等烷烴多元醇單(甲基)丙烯酸酯；(甲基)丙烯酸2-二甲胺乙酯、(甲基)丙烯酸2-二乙胺乙酯、(甲基)丙烯酸2-三級丁胺乙酯等具有胺基之(甲基)丙烯酸酯；(甲基)丙烯酸環氧丙酯、(甲基)丙烯酸烯丙酯；乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、1,3-丙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯等烷烴二醇二(甲基)丙烯酸酯；丙三醇二(甲基)丙烯酸酯等烷烴多元醇二(甲基)丙烯酸酯；二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、二伸丙二醇二(甲基)丙烯酸酯、 聚丙二醇二(甲基)丙烯酸酯等聚伸烷二醇二(甲基)丙烯酸酯；脂肪酸改性新戊四醇等酸改性烷烴多元醇的二(甲基)丙烯酸酯；三環癸烷二甲醇二(甲基)丙烯酸酯(tricyclodecanedimethanoldi(meta)acrylate)等橋接環式二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、丙三醇三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、四羥甲基甲烷四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯等烷烴多元醇(甲基)丙烯酸酯；三羥甲基丙烷、丙三醇等烷烴多元醇的C2-4環氧烷加成物之三(甲基)丙烯酸酯；參(2-羥乙基)三聚異氰酸三(甲基)丙烯酸酯等有三環之三(甲基)丙烯酸酯等。這些可以單獨使用，也可以組合2種以上使用。 In addition to the aforementioned urethane acrylate oligomer (E), the ultraviolet curable urethane acrylate composition of the present invention may be used without aromatics insofar as the object of the present invention is not exceeded. Skeleton acrylic monomer. Examples of the acrylic monomer include (meth)acrylic acid; methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate; Isobutyl acrylate, butyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate Ethyl ester of C1-24 such as ester, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate or stearyl (meth)acrylate (cyclo) (meth) acrylate, cycloalkyl (meth) acrylate such as cyclopentyl (meth) acrylate; tricyclo [5.2.1.0 2,6 ] 癸-8-ester (dicyclopentanyl) (meta)acrylate), (meth)acrylic acid tricyclo [5.2.1.0 2,6 ] dicyclopentenyl (meta) acrylate, (meth)acrylic tricyclo [5.2.1.0 2,6 ] Dicyclopentenyloxyethylene (meta) acrylate, (meth)acrylic acid Bridged cyclic (meth) acrylate such as ester, isodecyl (meth) acrylate or tricyclodecyl (meth) acrylate; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, ( Methyl) hydroxybutyl acrylate such as hydroxy C2-10 alkyl (meth) acrylate or C2-10 alkane diol mono (meth) acrylate; trifluoroethyl (meth) acrylate, (meth) acrylate a fluorinated C1-10 alkyl (meth) acrylate such as fluoropropyl acrylate or hexafluoroisopropyl (meth) acrylate; or an alkoxyalkyl (meth) acrylate such as methoxyethyl (meth)acrylate; a polyalkylene glycol mono(meth)acrylate such as polyethylene glycol mono(meth)acrylate; an alkane polyol mono(meth)acrylate such as glycerol mono(meth)acrylate; a (meth) acrylate having an amine group such as 2-dimethylamine ethyl acrylate, 2-diethylamine ethyl (meth)acrylate, 2-tert-butylamine ethyl (meth)acrylate; Glycidyl acrylate, allyl (meth) acrylate; ethylene glycol di(meth) acrylate, propylene glycol di(meth) acrylate, 1,3-propanediol di(meth) acrylate, 1,4-butanediol di(meth)acrylate, neopentyl Alkane diol di(meth) acrylate such as alcohol di(meth) acrylate or 1,6-hexane diol di(meth) acrylate; alkane polyol 2 such as glycerol di(meth) acrylate (meth) acrylate; diethylene glycol di(meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di(methyl) a poly(alkylene glycol) di(meth)acrylate such as an acrylate or a polypropylene glycol di(meth)acrylate; or a di(meth)acrylate of an acid-modified alkane polyol such as a fatty acid-modified neopentyl alcohol; Bridged cyclic di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerol tris, etc. such as tricyclodecanedimethanoldi(meta)acrylate Methyl) acrylate, neopentyl alcohol tri(meth) acrylate, neopentyl alcohol tetra (meth) acrylate, tetramethylol methane tetra (meth) acrylate, dipentaerythritol five ( Alkane polyol (meth) acrylate such as methyl acrylate, dipentaerythritol hexa(meth) acrylate; C2- of alkane polyol such as trimethylolpropane or glycerol 4 alkylene oxide adducts of tri (meth) acrylate; ginseng (2-hydroxyethyl) tripolyisocyanate tri(meth) acrylate, etc. Ring tris (meth) acrylate and the like. These may be used alone or in combination of two or more.

本發明之紫外線硬化性胺基甲酸酯丙烯酸酯組成物中，除了上述原料以外，在不超出本發明之目的的範圍內，也可在製造步驟的任何階段使用各種添加劑。 In the ultraviolet curable urethane acrylate composition of the present invention, various additives may be used at any stage of the production step, in addition to the above-mentioned raw materials, within the range not exceeding the object of the present invention.

此種添加劑可使用例如：整泡劑、抗氧化劑、消泡劑、磨粒、填充劑、顏料、染料、著色劑、增黏劑、界面活性劑、阻燃劑、可塑劑、滑劑、抗靜電劑、耐熱穩定劑、賦黏劑、硬化觸媒、穩定劑、矽烷偶合劑、蠟等已知之物。此外，視需要，在不妨礙本發明之目的的範圍內，可適當選擇過去已知的熱塑性樹脂、熱硬化性樹脂等作為摻合用樹脂。此外，前述添加劑係僅屬一範例，只要不妨礙本發明之目的，其種類及使用量不 特別限定。 Such additives can be used, for example, foam stabilizers, antioxidants, defoamers, abrasive particles, fillers, pigments, dyes, colorants, tackifiers, surfactants, flame retardants, plasticizers, lubricants, anti-wear agents Known materials such as an electrostatic agent, a heat-resistant stabilizer, an adhesive, a curing catalyst, a stabilizer, a decane coupling agent, and a wax. In addition, a thermoplastic resin, a thermosetting resin, and the like which have been known in the past can be appropriately selected as a blending resin, as long as the object of the present invention is not impaired. In addition, the foregoing additives are merely examples, and as long as they do not hinder the purpose of the present invention, the types and usage amounts thereof are not Specially limited.

前述賦黏劑可使用例如：松香系樹脂、松香酯系樹脂、氫化松香酯系樹脂、萜烯系樹脂、萜烯酚系樹脂、氫化萜烯系樹脂、與作為石油樹脂之C5系的脂肪族樹脂、C9系的芳香族樹脂、及C5系和C9系的共聚樹脂等。 For the tackifier, for example, a rosin-based resin, a rosin ester-based resin, a hydrogenated rosin-based resin, a terpene-based resin, a terpene-based resin, a hydrogenated terpene-based resin, and a C 5 -based fat as a petroleum resin can be used. A family resin, a C 9 -based aromatic resin, and a C 5 -based or C 9 -based copolymer resin.

前述可塑劑可使用例如：鄰苯二甲酸二丁酯、鄰苯二甲酸二辛酯、鄰苯二甲酸二環己酯、鄰苯二甲酸二異辛酯、鄰苯二甲酸二異癸酯、鄰苯二甲酸二苄酯、鄰苯二甲酸丁酯苄酯、磷酸三辛酯、環氧系可塑劑、甲苯磺醯胺、氯化石蠟、己二酸酯、蓖麻油等。還可舉出甲基酸磷酸酯(AP-1)、丙烯酸系表面調整劑(BYK-361N)等。 As the aforementioned plasticizer, for example, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, diisooctyl phthalate, diisononyl phthalate, Dibenzyl phthalate, butyl benzyl phthalate, trioctyl phosphate, epoxy plasticizer, toluene sulfonamide, chlorinated paraffin, adipate, castor oil, and the like. Further, methyl acid phosphate (AP-1), an acrylic surface conditioner (BYK-361N), or the like can be given.

前述穩定劑可使用例如：受阻酚系化合物、苯并***系化合物、受阻胺系化合物等。 As the stabilizer, for example, a hindered phenol compound, a benzotriazole compound, a hindered amine compound or the like can be used.

前述填充材料可使用例如：矽酸衍生物、滑石、金屬粉、碳酸鈣、黏土、碳黑等。 As the aforementioned filler, for example, a citric acid derivative, talc, metal powder, calcium carbonate, clay, carbon black or the like can be used.

本發明之紫外線硬化性胺基甲酸酯丙烯酸酯組成物完全不使用光聚合起始劑，且藉由含有特定有機溶劑作為稀釋溶劑，可展現優良的紫外線硬化性。 The ultraviolet curable urethane acrylate composition of the present invention does not use a photopolymerization initiator at all, and exhibits excellent ultraviolet curability by containing a specific organic solvent as a diluent solvent.

在以紫外線照射本發明之紫外線硬化性胺基甲酸酯丙烯酸酯組成物使其硬化之情形，可使用例如：汞燈(低壓、高壓、超高壓等)、氫燈、氘燈、鹵素燈、氙氣燈、碳弧燈、螢光燈、He-Cd雷射等各種光源，這些之中，較佳為高壓汞燈。 When the ultraviolet curable urethane acrylate composition of the present invention is irradiated with ultraviolet rays to be cured, for example, a mercury lamp (low pressure, high pressure, ultra high pressure, etc.), a hydrogen lamp, a xenon lamp, a halogen lamp, or the like can be used. Various light sources such as xenon lamps, carbon arc lamps, fluorescent lamps, He-Cd lasers, and the like, preferably high pressure mercury lamps.

使用本發明之紫外線硬化性胺基甲酸酯丙烯酸酯組成物，使用依據後述方法製作的薄膜，依據JIS K 0129以動態黏彈性分析所測得的tanδ峰值溫度(損失係數峰值溫度)係在-8~45℃之範圍，較佳係在-5~40℃之範圍，更佳係在0~35℃之範圍。前述薄膜的tanδ峰值溫度若在此範圍，則一旦受傷可展現快速回復自然回到原本的狀態之機能，即優良的自我修復性。 Using the ultraviolet curable urethane acrylate composition of the present invention, the tan δ peak temperature (loss coefficient peak temperature) measured by dynamic viscoelastic analysis according to JIS K 0129 is used in a film produced by the method described later. The range of 8 to 45 ° C is preferably in the range of -5 to 40 ° C, more preferably in the range of 0 to 35 ° C. If the tan δ peak temperature of the film is within this range, once it is injured, it exhibits a function of quickly returning to the original state, that is, excellent self-healing property.

然而，在前述薄膜的tanδ峰值溫度大於45℃之情形，薄膜成形體缺乏彈性，傷痕的回復需要長時間，或一旦受傷恐怕不會充分地回復。另一方面，在前述薄膜的tanδ峰值溫度小於-8℃之情形，因硬化物的強度不足，自我修復性變的不充分，或在薄膜成形體的表面容易產生黏著性，與物品的表面接觸而恐怕無法使用。 However, in the case where the tan δ peak temperature of the above film is more than 45 ° C, the film formed body lacks elasticity, the recovery of the scar takes a long time, or may not be sufficiently recovered once it is injured. On the other hand, in the case where the tan δ peak temperature of the film is less than -8 ° C, the self-healing property is insufficient due to insufficient strength of the cured product, or adhesion is likely to occur on the surface of the film formed body, and the surface of the article is in contact with the surface of the article. I am afraid I can't use it.

<薄膜成形體及光學薄膜> <Film formed body and optical film>

本發明之薄膜成形體係在基材上具有前述紫外線硬化性胺基甲酸酯丙烯酸酯組成物之硬化塗膜。 The film forming system of the present invention has a cured coating film of the above ultraviolet curable urethane acrylate composition on a substrate.

本發明之薄膜成形體可將前述紫外線硬化性胺基甲酸酯丙烯酸酯組成物塗布於基材上，形成具有自我修復性之最表層，接下來將前述最表層加以紫外線硬化來得到。前述最表層可展現優良的自我修復性、透明性、耐黃變性、黏彈性等性能。 In the film formed article of the present invention, the ultraviolet curable urethane acrylate composition can be applied onto a substrate to form a self-healing outermost layer, and then the outermost layer is obtained by ultraviolet curing. The aforementioned outermost layer can exhibit excellent self-healing properties, transparency, yellowing resistance, viscoelasticity and the like.

前述紫外線硬化性胺基甲酸酯丙烯酸酯組成物，儘管完全不含光聚合起始劑，但因經由照射紫外線可展現優良的紫外線硬化性，且所得到之塗膜與硬化物不會隨時間而黃變，對接觸物也沒有汙染，並具有塗布 性、成形性、透明性等優良性能，而在例如：除了在光學用構件(例如薄膜、片材)以外，於纖維、塗布材料、電子電機材料、食品包裝、化妝品包裝、裝飾膜等廣泛範圍用途係有用的。 The ultraviolet curable urethane acrylate composition, although completely free of a photopolymerization initiator, exhibits excellent ultraviolet curability by irradiation of ultraviolet rays, and the obtained coating film and cured product do not with time. Yellowing, no pollution to the contact, and coating Good properties such as properties, formability, transparency, etc., and in addition to optical components (such as films and sheets), in a wide range of fibers, coating materials, electronic motor materials, food packaging, cosmetic packaging, decorative films, etc. Use is useful.

又，本發明之薄膜成形體中，前述硬化塗膜的膜厚較佳係在10~800μm之範圍。 Further, in the film formed article of the present invention, the film thickness of the cured coating film is preferably in the range of 10 to 800 μm.

此外，本發明中，依據日本國內一般稱呼的基準，將厚度為200μm以下的構件定義為「薄膜」，將厚度大於200μm的構件定義為「片材」。 In the present invention, a member having a thickness of 200 μm or less is defined as a "film", and a member having a thickness of more than 200 μm is defined as a "sheet".

前述薄膜成形體可列舉出例如：自己修復薄膜、自己修復塗料、導光薄膜(導光膜)、光學薄膜、表面保護薄膜、導光片材、導光纖維等。 Examples of the film formed body include a self-healing film, a self-healing paint, a light-guiding film (light-guiding film), an optical film, a surface protective film, a light guiding sheet, and a light guiding fiber.

本發明之光學薄膜係具有前述紫外線硬化性胺基甲酸酯丙烯酸酯組成物的硬化塗膜之薄膜，前述硬化塗膜的膜厚較佳係在10~200μm之範圍，更佳係在50~200μm之範圍，且依據JIS K7361-1所測定之總透光率為92.0%以上。薄膜的膜厚與總透光率若在此範圍，則可展現優良的透光性，可適用於例如：導光薄膜(導光膜)、平面顯示面板用光學薄膜、抗反射薄膜(防眩膜、抗眩膜)、配向薄膜、偏光薄膜、偏光層保護薄膜、相位差薄膜(光學補償薄膜)、視角提升薄膜(廣角薄膜)、輝度提升薄膜、電磁波屏蔽薄膜、遮光薄膜、特定頻率選擇性遮蔽薄膜(透明電波遮蔽薄膜、紅外線遮蔽薄膜、紫外線遮蔽薄膜)、光學低通濾波器(OLPF)薄膜、鏡頭濾光片等光學用材料。 The optical film of the present invention has a film of a cured coating film of the ultraviolet curable urethane acrylate composition, and the film thickness of the cured film is preferably in the range of 10 to 200 μm, more preferably 50 to 50. The range of 200 μm and the total light transmittance measured according to JIS K7361-1 was 92.0% or more. When the film thickness and total light transmittance of the film are in this range, excellent light transmittance can be exhibited, and it can be suitably applied to, for example, a light guiding film (light guiding film), an optical film for a flat display panel, and an antireflection film (anti-glare). Film, anti-glare film, alignment film, polarizing film, polarizing layer protective film, retardation film (optical compensation film), viewing angle lifting film (wide-angle film), brightness enhancement film, electromagnetic wave shielding film, light shielding film, specific frequency selectivity Optical materials such as shielding films (transparent radio wave shielding film, infrared shielding film, ultraviolet shielding film), optical low-pass filter (OLPF) film, and lens filter.

<薄膜成形體之製造方法> <Method for Producing Film Formed Body>

本發明之薄膜成形體之製造方法，可舉出例如：將本發明之紫外線硬化性胺基甲酸酯丙烯酸酯組成物塗布於離型基材上，照射紫外線硬化後，將前述沒有芳香族骨架之有機溶劑(F)加以揮發，形成硬化塗膜，來得到較佳在10~1000μm之範圍，更佳在10~800μm之範圍，再更佳在50~800μm之範圍，最佳在10~200μm之薄厚度的薄膜成形體(例如、薄膜、片材等)之方法等。 In the method for producing a film formed article of the present invention, for example, the ultraviolet curable urethane acrylate composition of the present invention is applied onto a release substrate, and after curing by ultraviolet light, the aforementioned aromatic skeleton is not provided. The organic solvent (F) is volatilized to form a hardened coating film, preferably in the range of 10 to 1000 μm, more preferably in the range of 10 to 800 μm, still more preferably in the range of 50 to 800 μm, and most preferably in the range of 10 to 200 μm. A method of forming a thin film formed body (for example, a film, a sheet, or the like).

前述基材可列舉出例如：金屬(板、箔等)、塑膠(板、片材、薄膜等)、紙(離型紙等)、玻璃、陶器、木板(化妝板等)、陶瓷、布等，不特別限定。 Examples of the substrate include metal (plate, foil, etc.), plastic (plate, sheet, film, etc.), paper (release paper, etc.), glass, ceramics, wood (made of a cosmetic board, etc.), ceramics, cloth, and the like. Not particularly limited.

本發明之紫外線硬化性胺基甲酸酯丙烯酸酯組成物，在前述異氰酸酯基末端之胺基甲酸酯預聚物(C)與具有(甲基)丙烯醯基之胺基甲酸酯丙烯酸酯寡聚物(E)的混合物之情形，可預先調配作為硬化劑的具沒有芳香族骨架的官能基之反應性化合物，在例如80~140℃之範圍加熱加以硬化，並將前述有機溶劑(F)揮發。 The ultraviolet curable urethane acrylate composition of the present invention, the urethane prepolymer (C) at the terminal isocyanate group and the urethane acrylate having a (meth) acrylonitrile group In the case of a mixture of the oligomers (E), a reactive compound having a functional group having no aromatic skeleton as a curing agent may be previously prepared, and hardened by heating, for example, in the range of 80 to 140 ° C, and the aforementioned organic solvent (F) ) Volatile.

若要展示本發明之薄膜成形體之製造方法的一例，可舉出如下述所示之包括[步驟1]~[步驟2]的一連串步驟之製造方法。 An example of a method for producing a film formed article of the present invention is a method for producing a series of steps including [Step 1] to [Step 2] as described below.

[步驟1]紫外線硬化性胺基甲酸酯丙烯酸酯組成物之調整 [Step 1] Adjustment of ultraviolet curable urethane acrylate composition

將熔融狀態的沒有芳香族骨架之多元醇(A)添加至反應容器，並開始攪拌。接下來，一邊注意發熱，一邊添加既定量的沒有芳香族骨架之聚異氰酸酯(B)，將內溫 上升至既定溫度後，於該溫度攪拌既定時間，得到異氰酸酯基末端之胺基甲酸酯預聚物(C)。 The polyol (A) having no aromatic skeleton in a molten state was added to the reaction vessel, and stirring was started. Next, while paying attention to heat, add a certain amount of polyisocyanate (B) without an aromatic skeleton, and set the internal temperature. After rising to a predetermined temperature, the mixture is stirred at the temperature for a predetermined period of time to obtain an isocyanate-terminated urethane prepolymer (C).

接下來，添加既定量的聚合抑制劑與具有羥基之(甲基)丙烯酸類化合物(D)，繼續反應既定時間後，得到目標之胺基甲酸酯丙烯酸酯寡聚物(E)。 Next, a predetermined amount of the polymerization inhibitor and the (meth)acrylic compound (D) having a hydroxyl group are added, and the reaction is continued for a predetermined period of time to obtain the desired urethane acrylate oligomer (E).

然後，添加作為稀釋溶劑的沒有芳香族骨架之有機溶劑(F)來調整熔融黏度，得到本發明之紫外線硬化性胺基甲酸酯丙烯酸酯組成物。 Then, an organic solvent (F) having no aromatic skeleton as a diluent solvent is added to adjust the melt viscosity, and the ultraviolet curable urethane acrylate composition of the present invention is obtained.

[步驟2]薄膜成形體之製造 [Step 2] Fabrication of a film formed body

將前述[步驟1]所得到之紫外線硬化性胺基甲酸酯丙烯酸酯組成物，以刮刀塗布機在經過施以離型處理之聚對苯二甲酸乙二酯(PET)薄膜上，在目標的薄膜成形體為薄膜之情形係塗布成200μm以下之厚度，或在薄膜成形體為片材之情形係塗布成大於200μm之厚度。接下來，一邊進行氮氣迫淨，一邊以紫外線照射裝置(例如高壓汞燈)照射紫外線加以硬化。 The ultraviolet curable urethane acrylate composition obtained in the above [Step 1] is applied to a polyethylene terephthalate (PET) film subjected to release treatment by a knife coater at a target When the film formed body is a film, it is applied to a thickness of 200 μm or less, or when the film formed body is a sheet, it is applied to a thickness of more than 200 μm. Next, while purging the nitrogen gas, it is hardened by irradiating ultraviolet rays with an ultraviolet irradiation device (for example, a high-pressure mercury lamp).

接下來，以通常的60℃加熱熟成既定時間，將前述有機溶劑(F)揮發，可得到本發明之薄膜成形體之薄膜。 Next, the organic solvent (F) is volatilized by heating at a usual temperature of 60 ° C for a predetermined period of time to obtain a film of the film formed article of the present invention.

[實施例] [Examples]

以下，以實施例更進一步具體的說明本發明，但本發明之範圍並非僅限定於這些實施例。 Hereinafter, the present invention will be further specifically described by examples, but the scope of the invention is not limited to the examples.

又，本發明中，除非有特別說明，否則「%」係表示「質量%」。 Further, in the present invention, "%" means "% by mass" unless otherwise specified.

此外，本發明所使用之測定方法及評價方法，係如下述。 Further, the measurement method and evaluation method used in the present invention are as follows.

[異氰酸酯基末端之胺基甲酸酯預聚物(C)的異氰酸酯當量之測定方法] [Method for Measuring Isocyanate Equivalent of Isocyanate-terminated Urethane Prepolymer (C)]

本發明所使用之異氰酸酯基末端之胺基甲酸酯預聚物(C)的異氰酸酯當量(單位：g/eq，即g/當量)，係依據JIS K 7301所測得之值。 The isocyanate equivalent (unit: g/eq, i.e., g/equivalent) of the isocyanate-terminated urethane prepolymer (C) used in the present invention is a value measured in accordance with JIS K 7301.

具體來說，將所得到之胺基甲酸酯預聚物的試料放在三角燒瓶中精秤，再以乾燥甲苯加以溶解，於添加10ml的二正丁胺溶液後，使其均勻後靜置，使用溴甲酚綠作為指示劑，以0.5當量鹽酸的標準溶液作中和滴定來定量。 Specifically, the obtained sample of the urethane prepolymer was placed in a conical flask, and then dissolved in dry toluene. After adding 10 ml of di-n-butylamine solution, it was allowed to stand evenly and then allowed to stand. Using bromocresol green as an indicator, it was quantified by neutralization titration with a standard solution of 0.5 equivalent of hydrochloric acid.

[於分子末端具有(甲基)丙烯醯基之胺基甲酸酯丙烯酸酯寡聚物(E)的(甲基)丙烯酸當量之計算方法] [Method for calculating (meth)acrylic equivalent of urethane acrylate oligomer (E) having (meth) acrylonitrile group at the molecular end]

本發明中記載之(甲基)丙烯酸當量，係由原料的質量平衡來計算，含有1莫耳的(甲基)丙烯醯基之胺基甲酸酯丙烯酸酯寡聚物(E)的分子量(g/eq)，於實施例及比較例得到的組成物中，係以(甲基)丙烯醯基濃度(mol/g)的倒數所表示之值。 The (meth)acrylic equivalent described in the present invention is calculated from the mass balance of the raw material, and has a molecular weight of 1 mol of the (meth)acrylonitrile-based urethane acrylate oligomer (E) ( g/eq), the compositions obtained in the examples and the comparative examples are values represented by the reciprocal of the (meth) acrylonitrile group concentration (mol/g).

[紫外線硬化性(無黏性)之評價方法與判定基準] [Evaluation method and criterion for UV curability (non-stickiness)]

以刮刀塗布機將實施例及比較例所得到之紫外線硬化性胺基甲酸酯丙烯酸酯組成物塗布在施加過離型處理之聚對苯二甲酸乙二酯(PET)薄膜上形成塗膜，以具有1盞120w/cm的高壓汞燈，及氮氣迫淨裝置之紫外線照射裝置「N2迫淨式附輸送帶之UV照射裝置」(GS YUASA股份有限公司製)，在照射光量0.8J/cm2、氮氣環境下(氧氣濃 度1%)之條件下照射紫外線，將前述塗膜加以硬化。 The ultraviolet curable urethane acrylate composition obtained in the examples and the comparative examples was applied onto a polyethylene terephthalate (PET) film subjected to a release treatment by a knife coater to form a coating film. The high-pressure mercury lamp having a temperature of 1盏120w/cm and the ultraviolet irradiation device of the N 2 forced-cleaning conveyor belt (manufactured by GS YUASA Co., Ltd.) are used for the amount of light to be irradiated. The coating film was cured by irradiating ultraviolet rays under conditions of cm 2 and nitrogen atmosphere (oxygen concentration: 1%).

然後，進一步在溫度60±5℃加熱10分鐘，將使用的有機溶劑揮發掉，得到在基材上具有硬化塗膜之薄膜成形體的薄膜(厚度100μm之物)。 Then, the film was further heated at a temperature of 60 ± 5 ° C for 10 minutes, and the organic solvent to be used was volatilized to obtain a film (thickness of 100 μm) having a film formed body having a cured coating film on a substrate.

以手指觸摸來確認前述薄膜的表面(最表層)有無黏性，依據下述基準評價。 The surface of the film (the outermost layer) was confirmed to have viscosity by finger touch, and was evaluated according to the following criteria.

紫外線硬化性(無黏性)之判定基準 Benchmark of UV curability (non-stickiness)

○：無黏性，手指沒有附著液狀物之情形，紫外線硬化性優良。 ○: It has no stickiness, and the liquid does not adhere to the finger, and the ultraviolet curability is excellent.

×：有黏性，手指有附著著液狀物之情形，紫外線硬化性差。 ×: It is sticky, and the liquid adheres to the finger, and the ultraviolet curability is poor.

[薄膜的表面硬度之測定方法] [Method for Measuring Surface Hardness of Film]

使用實施例及比較例所製成之薄膜，在調整至內溫23℃、相對濕度50%之恆溫恆濕室中，以鉛筆硬度計(負重750g)加以劃傷，以目視確認劃傷後20秒的薄膜之表面狀態，取無法確認損傷之界限的鉛筆硬度為表面硬度。 The film prepared in the examples and the comparative examples was scratched with a pencil hardness meter (load weight: 750 g) in a constant temperature and humidity chamber adjusted to an internal temperature of 23 ° C and a relative humidity of 50% to visually confirm the scratch after 20 In the surface state of the film of the second, the pencil hardness which is the limit of the damage cannot be confirmed as the surface hardness.

[薄膜的黏彈性之評價方法與判定基準] [Evaluation method and criterion of viscoelasticity of film]

依據下述順序，使用實施例及比較例所製成之薄膜，依據JIS K 0129以動態黏彈性分析測定tanδ峰值溫度(損失係數峰值溫度)，評價黏彈性。 The tan δ peak temperature (loss coefficient peak temperature) was measured by dynamic viscoelasticity analysis according to JIS K 0129 using the film prepared in the examples and the comparative examples in accordance with the following procedure to evaluate the viscoelasticity.

以刮刀塗布機將前述實施例及比較例得到的組成物塗布在離型聚對苯二甲酸乙二酯板或聚碳酸酯板上形成塗膜。接下來，使用紫外線照射機，在氮氣環境下對塗膜照射紫外線，將前述塗膜加以硬化。 The composition obtained in the above Examples and Comparative Examples was coated on a release polyethylene terephthalate sheet or a polycarbonate plate by a knife coater to form a coating film. Next, the coating film was irradiated with ultraviolet rays in a nitrogen atmosphere using an ultraviolet ray irradiator to cure the coating film.

然後，進一步以60±5℃之溫度加熱10分鐘，將使用 的有機溶劑揮發掉，得到在基材上有硬化塗膜的薄膜成形體之薄膜(厚度100μm之物)。 Then, further heated at 60 ± 5 ° C for 10 minutes, will be used The organic solvent was evaporated to obtain a film (thickness of 100 μm) of a film formed body having a cured coating film on a substrate.

使用黏彈性頻譜儀(型式：DMS6100，SII NanoTechnology股份有限公司製)，在升溫速度5℃/分鐘、頻率1Hz之條件下，以拉伸模式測定使用前述組成物製成之薄膜的儲存彈性模數(E’)及損失彈性模數(E”)。取E’/E”為tanδ，取tanδ達最大值之溫度為「tanδ峰值溫度(℃)」，依據下述基準評價黏彈性。 Using a viscoelastic spectrum analyzer (type: DMS6100, manufactured by SII NanoTechnology Co., Ltd.), the storage elastic modulus of the film prepared using the above composition was measured in a tensile mode at a temperature rising rate of 5 ° C/min and a frequency of 1 Hz. (E') and the loss elastic modulus (E"). Take E'/E" as tan δ, and take the temperature at which tan δ reaches the maximum value as "tan δ peak temperature (°C)", and evaluate the viscoelasticity according to the following criteria.

薄膜的黏彈性之判斷基準 Judgement criteria for film viscoelasticity

○：tanδ峰值溫度為0~35℃之情形。 ○: The case where the tan δ peak temperature is 0 to 35 °C.

×：tanδ峰值溫度小於0℃，或大於35℃之情形。 ×: The case where the tan δ peak temperature is less than 0 ° C or greater than 35 ° C.

[薄膜的自我修復性之評價方法與判定基準] [Evaluation method and criteria for self-healing of film]

本發明中所謂「自我修復性」，係在薄膜成形體(例如薄膜、片材等)的表面(最表層)產生的損傷可隨時間復元之特性，以下述方法評價並判定。 In the present invention, the "self-healing property" is evaluated by the following method in the case where the damage generated on the surface (the outermost layer) of the film formed body (for example, a film or a sheet) can be recovered over time.

於調整至溫度23℃、相對濕度50%之恆溫恆濕室中，測定從以加重至500g之黃銅刷(線直徑0.1mm)劃傷所得到的薄膜之表面(最表層)的當下起，到以目視無法確認傷痕為止之回復時間(秒)，依據下述基準判定自我修復性。 In the constant temperature and humidity chamber adjusted to a temperature of 23 ° C and a relative humidity of 50%, the surface (the outermost layer) of the film obtained by scratching a brass brush (wire diameter of 0.1 mm) weighted to 500 g was measured. The recovery time (seconds) until the flaw can be confirmed by visual inspection is determined based on the following criteria.

自我修復性之判斷基準 Self-repairing benchmark

○：回復時間為20秒以內之情形，自我修復性優良。 ○: The recovery time is within 20 seconds, and the self-healing property is excellent.

×：回復時間大於20秒之情形，自我修復性差。 ×: When the reply time is longer than 20 seconds, the self-healing property is poor.

××：未回復之情形，沒有自我修復性。 ××: In the case of non-response, there is no self-healing.

[薄膜的初期黃色度(YI0)之評價方法與判定基準] [Evaluation method and criterion for initial yellowness (YI 0 ) of film]

依據JIS Z8722以多光源分光測色計(SUGA試驗機股份有限公司製)測定實施例及比較例所製成之薄膜的厚度方向之黃色指數(YI0)，依據下述基準評價。 The yellowness index (YI 0 ) in the thickness direction of the film produced in the examples and the comparative examples was measured by a multi-source spectrophotometer (manufactured by SUGA Testing Machine Co., Ltd.) in accordance with JIS Z8722, and evaluated according to the following criteria.

初期黃色度之判定基準 Initial yellowness criterion

○：在厚度方向的YI0為0.5以下之情形，初期黃色度優良。 ○: When the YI 0 in the thickness direction is 0.5 or less, the initial yellowness is excellent.

×：在厚度方向的YI0大於0.5之情形，初期黃色度差。 ×: In the case where YI 0 in the thickness direction is more than 0.5, the initial yellowness is poor.

[薄膜的耐黃變性之評價方法與判定基準] [Evaluation method and criterion for yellowing resistance of film]

使用在前述初期黃色度之評價所用的薄膜，在乾燥機中暴露120℃×72小時暴露，依據JIS Z8722以多光源分光測色計(SUGA試驗機股份有限公司製)測定暴露後的黃色度(黃色指數：YI1)，依據下述基準評價。 The film used for the evaluation of the initial yellowness was exposed to 120 ° C for 72 hours in a dryer, and the yellowness after exposure was measured by a multi-source spectrophotometer (manufactured by SUGA Testing Co., Ltd.) in accordance with JIS Z8722 ( Yellow index: YI 1 ), evaluated according to the following criteria.

耐黃變性之判定基準 Benchmark of yellowing resistance

○：在厚度方向的YI1為0.7以下之情形，耐黃變性優良。 ○: When the YI 1 in the thickness direction is 0.7 or less, the yellowing resistance is excellent.

×：在厚度方向的YI1大於0.7之情形，耐黃變性差。 ×: In the case where YI 1 in the thickness direction is more than 0.7, the yellowing resistance is poor.

[薄膜的透明性之評價方法與判定基準] [Evaluation method and criteria for transparency of film]

使用日本電色工業股份有限公司製NDH-2000，依據JIS K7361-1測定實施例及比較例所製成之薄膜的總透光率(%)，依據下述基準評價。 The total light transmittance (%) of the film produced in the examples and the comparative examples was measured in accordance with JIS K7361-1 using NDH-2000 manufactured by Nippon Denshoku Industries Co., Ltd., and evaluated according to the following criteria.

透明性之判定基準 Benchmark of transparency

○：在總透光率為92.0%以上之情形，透明性優良。 ○: When the total light transmittance is 92.0% or more, the transparency is excellent.

×：在總透光率小於92.0%之情形，透明性差。 ×: In the case where the total light transmittance is less than 92.0%, the transparency is poor.

[合成例1] [Synthesis Example 1]

≪於分子末端具有(甲基)丙烯醯基之胺基甲酸酯丙烯酸酯寡聚物(E1)之合成≫ Synthesis of urethane acrylate oligomer (E1) having a (meth) acrylonitrile group at the molecular end

將50質量份作為沒有芳香族骨架之多元醇(A)之50℃的熔融狀態之聚四亞甲基醚醇(商品名：PTMG-1000，三菱化學股份有限公司製，Mn=1000)添加進反應容器，開始攪拌。 50 parts by mass of polytetramethylene ether alcohol (trade name: PTMG-1000, manufactured by Mitsubishi Chemical Corporation, Mn = 1000) in a molten state of 50 ° C as a polyol (A) having no aromatic skeleton The reaction vessel was started to stir.

接下來，添加100質量份作為沒有芳香族骨架之聚異氰酸酯(B)之伸己二異氰酸酯(以下簡稱「HDI」)的異氰酸酯改性物(異氰酸酯當量=204g/eq)，一邊注意發熱一邊將內溫上升至85℃後，一邊保持著溫度，一邊攪拌3小時，得到於分子末端具有異氰酸酯基之胺基甲酸酯預聚物(C1)。 Next, 100 parts by mass of an isocyanate modified product (isocyanate equivalent = 204 g/eq) which is a hexamethylene diisocyanate (hereinafter referred to as "HDI") which is a polyisocyanate (B) having no aromatic skeleton, is added, and attention is given to heat generation. After the temperature was raised to 85 ° C, the mixture was stirred for 3 hours while maintaining the temperature to obtain a urethane prepolymer (C1) having an isocyanate group at the molecular terminal.

接下來，一邊注意加熱，一邊慢慢添加57質量份作為具有羥基之(甲基)丙烯酸類化合物(D)之丙烯酸4-羥丁酯(以下簡稱「4HBA」)，於85℃攪拌2小時，得到胺基甲酸酯丙烯酸酯寡聚物(E1)。 Next, while paying attention to heating, 57 parts by mass of 4-hydroxybutyl acrylate (hereinafter referred to as "4HBA") as a (meth)acrylic compound (D) having a hydroxyl group was gradually added, and the mixture was stirred at 85 ° C for 2 hours. A urethane acrylate oligomer (E1) was obtained.

[合成例2~9] [Synthesis Examples 2 to 9]

除了將使用之多元醇(A)、聚異氰酸酯(B)、及具有羥基之(甲基)丙烯酸類化合物(D)的種類及添加量，如表1所示般變更以外，以與合成例1相同之反應條件得到胺基甲酸酯丙烯酸酯寡聚物(E2)~(E9)。 The type and amount of the polyol (A), the polyisocyanate (B), and the (meth)acrylic compound (D) having a hydroxyl group to be used were changed as shown in Table 1, and Synthesis Example 1 was used. The same reaction conditions gave the urethane acrylate oligomers (E2) to (E9).

其中，表1中的縮寫，係意指下述名稱。 The abbreviations in Table 1 mean the following names.

PTMG-1000：聚四亞甲基醚醇(商標：三菱化學股份有限公司製、數量平均分子量1000) PTMG-1000: polytetramethylene ether alcohol (trademark: manufactured by Mitsubishi Chemical Corporation, number average molecular weight 1000)

PCL：聚己內酯多元醇(數量平均分子量520) PCL: polycaprolactone polyol (quantitative average molecular weight 520)

2HEA：丙烯酸2-羥乙酯 2HEA: 2-hydroxyethyl acrylate

4HBA：丙烯酸4-羥丁酯 4HBA: 4-hydroxybutyl acrylate

HDI：1,6-伸己二異氰酸酯 HDI: 1,6-extended diisocyanate

H12MDI：4,4’-二環己基甲烷二異氰酸酯 H12MDI: 4,4'-dicyclohexylmethane diisocyanate

IPDI：異佛酮二異氰酸酯 IPDI: Isophorone diisocyanate

MDI：4,4’-二苯基甲烷二異氰酸酯 MDI: 4,4'-diphenylmethane diisocyanate

[實施例1] [Example 1]

將100質量份的合成例1所得到之前述胺基甲酸酯丙烯酸酯寡聚物(E1)，與20質量份的作為沒有芳香族骨架的有機溶劑(F)之甲乙酮(以下稱為「MEK」)，於容器中秤量，於室溫混合至均勻，調製為本發明之紫外線硬化性胺基甲酸酯丙烯酸酯組成物(X1)。 100 parts by mass of the urethane acrylate oligomer (E1) obtained in Synthesis Example 1 and 20 parts by mass of methyl ethyl ketone (hereinafter referred to as "MEK" as an organic solvent (F) having no aromatic skeleton The mixture was weighed in a container and mixed at room temperature to obtain a composition (X1) of the ultraviolet curable urethane acrylate composition of the present invention.

以刮刀塗布機將上述所調製之紫外線硬化性胺基甲酸酯丙烯酸酯組成物(X1)塗布於聚對苯二甲酸乙二酯(PET)製剝離薄膜上，於最表層形成塗膜。 The ultraviolet curable urethane acrylate composition (X1) prepared above was applied onto a release film made of polyethylene terephthalate (PET) by a knife coater to form a coating film on the outermost layer.

於塗工後即以具有1盞120w/cm的高壓汞燈，及氮氣迫淨裝置之紫外線照射裝置，以照射光量0.8J/cm2、在氮氣環境下(氧氣濃度1%以下)照射紫外線，使前述塗膜硬化。再進一步於烤箱中以60℃加熱10分鐘，將有機溶劑揮發掉，製作成薄膜成形體之薄膜(P1)(厚度100μm之物)。 After the coating, a high-pressure mercury lamp having a temperature of 1 盏 120 w/cm and an ultraviolet ray irradiation device of a nitrogen gas squeezing device are used to irradiate ultraviolet rays with a light amount of 0.8 J/cm 2 and a nitrogen atmosphere (oxygen concentration of 1% or less). The aforementioned coating film is cured. Further, the mixture was heated at 60 ° C for 10 minutes in an oven to evaporate the organic solvent to prepare a film (P1) of a film formed body (thickness of 100 μm).

[實施例2~9、及比較例1~10] [Examples 2 to 9 and Comparative Examples 1 to 10]

除了將使用之預聚物、有機溶劑的種類、使用量變更成如表2及表3所示以外，與實施例1同樣地進行，分別調整紫外線硬化性胺基甲酸酯丙烯酸酯組成物(X2)~(X19)，製作成厚度100μm之薄膜(P2)~(P19)。 The ultraviolet curable urethane acrylate composition was adjusted in the same manner as in Example 1 except that the type of the prepolymer and the organic solvent to be used and the amount of use were changed as shown in Table 2 and Table 3 ( X2)~(X19), a film (P2)~(P19) having a thickness of 100 μm is produced.

其中，表2及表3中的縮寫，係意指下述名稱。 Among them, the abbreviations in Table 2 and Table 3 mean the following names.

PTMG-1000：聚四亞甲基醚醇(商標：三菱化學股份有限公司製，數量平均分子量1000) PTMG-1000: polytetramethylene ether alcohol (trademark: manufactured by Mitsubishi Chemical Corporation, number average molecular weight 1000)

PCL：聚己內酯多元醇(數量平均分子量520) PCL: polycaprolactone polyol (quantitative average molecular weight 520)

1,4PBD：1,4-聚丁二烯二醇(數量平均分子量1200) 1,4PBD: 1,4-polybutadiene diol (number average molecular weight 1200)

2HEA：丙烯酸2-羥乙酯 2HEA: 2-hydroxyethyl acrylate

4HBA：丙烯酸4-羥丁酯 4HBA: 4-hydroxybutyl acrylate

HDI：1,6-伸己二異氰酸酯 HDI: 1,6-extended diisocyanate

H12MDI：4,4’-二環己基甲烷二異氰酸酯 H 12 MDI: 4,4'-dicyclohexylmethane diisocyanate

IPDI：異佛酮二異氰酸酯 IPDI: Isophorone diisocyanate

MDI：4,4’-二苯基甲烷二異氰酸酯 MDI: 4,4'-diphenylmethane diisocyanate

MEK：甲乙酮 MEK: methyl ethyl ketone

MIBK：甲基異丁基酮 MIBK: methyl isobutyl ketone

Irgacure 184：Irgacure 184(商標：長瀨產業股份有限公司製，自由基系光聚合起始劑，化學名：1-羥基環己基苯基酮) Irgacure 184: Irgacure 184 (trademark: Changchun Industry Co., Ltd., free radical photopolymerization initiator, chemical name: 1-hydroxycyclohexyl phenyl ketone)

[產業上之可利用性] [Industrial availability]

本發明之紫外線硬化性胺基甲酸酯丙烯酸酯組成物與過去的紫外線硬化性組成物不同，即使完全不含光聚合起始劑也可展現優良的紫外線硬化性，且所得到之薄膜成形體因具有自我修復性、耐黃變性、透明性、及適度的柔軟性等優良的性能，而在例如：光學用構件(例如光學薄膜、光學片材等)、光學用塗布材料、纖維、電子電機材料、食品包裝、化妝品包裝、裝飾膜等廣泛範圍領域係有用的。 The ultraviolet curable urethane acrylate composition of the present invention is different from the conventional ultraviolet curable composition, and exhibits excellent ultraviolet curability even when the photopolymerization initiator is completely contained, and the obtained film formed body It has excellent properties such as self-healing property, yellowing resistance, transparency, and moderate flexibility, and is, for example, optical members (for example, optical films, optical sheets, etc.), optical coating materials, fibers, and electronic motors. A wide range of fields such as materials, food packaging, cosmetic packaging, and decorative films are useful.

Claims (7)

一種紫外線硬化性胺基甲酸酯丙烯酸酯組成物，該紫外線硬化性胺基甲酸酯丙烯酸酯組成物係包含於分子末端具有(甲基)丙烯醯基之胺基甲酸酯丙烯酸酯寡聚物(E)，該於分子末端具有(甲基)丙烯醯基之胺基甲酸酯丙烯酸酯寡聚物(E)係讓具有羥基之(甲基)丙烯酸類化合物(D)，對使沒有芳香族骨架之多元醇(A)與沒有芳香族骨架之聚異氰酸酯(B)進行反應所得到之於分子末端有異氰酸酯基之胺基甲酸酯預聚物(C)進行加成反應而得，其特徵為：該紫外線硬化性胺基甲酸酯丙烯酸酯組成物係含有0.2~80質量%的從由酮系溶劑、醯胺系溶劑、及鹵化烷系溶劑所構成之群組中所選出的至少一種沒有芳香族骨架之有機溶劑(F)，且不含光聚合起始劑，且前述胺基甲酸酯丙烯酸酯寡聚物(E)的(甲基)丙烯酸當量在450~1100g/當量之範圍，而使用以前述紫外線硬化性胺基甲酸酯丙烯酸酯組成物製作之厚度100μm的薄膜，依據JIS K 0129以動態黏彈性分析測定出的tanδ峰值溫度係在-8~45℃之範圍。 An ultraviolet curable urethane acrylate composition comprising an urethane acrylate oligomer having a (meth) acrylonitrile group at a molecular terminal (E), the urethane acrylate oligomer (E) having a (meth) acrylonitrile group at the terminal of the molecule is a (meth)acrylic compound (D) having a hydroxyl group, The aromatic skeleton polyol (A) is obtained by an addition reaction of a urethane prepolymer (C) having an isocyanate group at a molecular terminal obtained by reacting a polyisocyanate (B) having no aromatic skeleton. The ultraviolet curable urethane acrylate composition is selected from the group consisting of a ketone solvent, a guanamine solvent, and a halogenated alkane solvent in an amount of 0.2 to 80% by mass. At least one organic solvent (F) having no aromatic skeleton, and containing no photopolymerization initiator, and the (meth)acrylic equivalent of the aforementioned urethane acrylate oligomer (E) is 450 to 1100 g / equivalent Scope of the use of the aforementioned ultraviolet curable urethane acrylate The film having a thickness of 100 μm made of the composition had a tan δ peak temperature measured by dynamic viscoelastic analysis in the range of -8 to 45 ° C according to JIS K 0129. 如請求項1之紫外線硬化性胺基甲酸酯丙烯酸酯組成物，其中前述具有羥基之(甲基)丙烯酸類化合物(D)係從由(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸3-羥丙酯、(甲基)丙烯酸4-羥丁酯、及新戊四醇三丙烯酸酯所構成之群組中所選出的至少一種。 The ultraviolet curable urethane acrylate composition of claim 1, wherein the (meth)acrylic compound (D) having a hydroxyl group is derived from 2-hydroxyethyl (meth)acrylate, (methyl) At least one selected from the group consisting of 2-hydroxypropyl acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and pentaerythritol triacrylate. 如請求項1之紫外線硬化性胺基甲酸酯丙烯酸酯組成 物，其中前述胺基甲酸酯丙烯酸酯寡聚物(E)的依據JIS Z 8803測定之在50℃的熔融黏度係在500~100000mPa．s之範圍。 The ultraviolet curable urethane acrylate composition of claim 1 The melting viscosity at 50 ° C of the aforementioned urethane acrylate oligomer (E) according to JIS Z 8803 is 500~100000 mPa. The range of s. 如請求項1之紫外線硬化性胺基甲酸酯丙烯酸酯組成物，其中前述有機溶劑(F)係從由甲乙酮、丙酮、甲基異丁基酮、環己酮、二異丁基酮、異佛酮、二甲基甲醯胺、二氯甲烷、及氯仿所構成之群組中所選出的至少一種。 The ultraviolet curable urethane acrylate composition according to claim 1, wherein the organic solvent (F) is derived from methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone, and the like. At least one selected from the group consisting of phorbolone, dimethylformamide, dichloromethane, and chloroform. 一種薄膜成形體，其特徵為：其係在基材上具有如請求項1至4中任一項之紫外線硬化性胺基甲酸酯丙烯酸酯組成物的硬化塗膜。 A film formed body having a cured coating film having the ultraviolet curable urethane acrylate composition according to any one of claims 1 to 4 on a substrate. 一種光學薄膜，其係具有如請求項1至4中任一項之紫外線硬化性胺基甲酸酯丙烯酸酯組成物的硬化塗膜之光學薄膜，其特徵為：前述硬化塗膜在膜厚50~200μm之依據JIS K7361-1測定之總透光率為92%以上。 An optical film comprising a cured film of a UV curable urethane acrylate composition according to any one of claims 1 to 4, characterized in that the cured film is 50 in film thickness The total light transmittance of ~200 μm measured according to JIS K7361-1 was 92% or more. 一種薄膜成形體之製造方法，其特徵為：將如請求項1至4中任一項之紫外線硬化性胺基甲酸酯丙烯酸酯組成物塗布於基材上，於照射紫外線後，使前述有機溶劑(F)揮發而形成硬化塗膜。 A method for producing a film molded body, comprising: applying the ultraviolet curable urethane acrylate composition according to any one of claims 1 to 4 to a substrate, and irradiating the ultraviolet ray to cause the organic The solvent (F) volatilizes to form a hardened coating film.
TW102132522A 2012-09-20 2013-09-10 A method for producing an ultraviolet-curable urethane acrylate composition, a film-formed product, an optical film, and a film-forming body TWI487723B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2012207000 2012-09-20

Publications (2)

Publication Number Publication Date
TW201418303A true TW201418303A (en) 2014-05-16
TWI487723B TWI487723B (en) 2015-06-11

Family

ID=50341106

Family Applications (1)

Application Number Title Priority Date Filing Date
TW102132522A TWI487723B (en) 2012-09-20 2013-09-10 A method for producing an ultraviolet-curable urethane acrylate composition, a film-formed product, an optical film, and a film-forming body

Country Status (5)

Country Link
JP (1) JP5633768B2 (en)
KR (1) KR101508706B1 (en)
CN (1) CN104619735B (en)
TW (1) TWI487723B (en)
WO (1) WO2014045782A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI752030B (en) * 2016-06-28 2022-01-11 日商迪愛生股份有限公司 Polyurethane foam sheet, method for producing the same, and method for producing a laminate

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104977633B (en) * 2014-04-08 2018-07-17 株式会社巴川制纸所 Protective film, film laminate and polarizer
JP2015203770A (en) * 2014-04-14 2015-11-16 リンテック株式会社 Hard coat film, coating liquid for forming hard coat layer, and method of manufacturing the hard coat film
WO2016126103A1 (en) * 2015-02-03 2016-08-11 주식회사 엘지화학 Composition for forming coating layer having self-healing characteristics, coating layer, and coating film
KR101807207B1 (en) 2015-02-03 2017-12-08 주식회사 엘지화학 Coating composition, coating layer and coating film having self-healing property
JP6558000B2 (en) * 2015-03-12 2019-08-14 東ソー株式会社 Active energy ray-curable resin composition
JP6596852B2 (en) * 2015-03-16 2019-10-30 日油株式会社 Curable resin composition and laminated structure
CN107709615B (en) * 2015-06-26 2019-10-11 Dic株式会社 Surface of steel plate inorganic agent and steel plate with its film
CN106700024A (en) * 2015-11-15 2017-05-24 惠州市长润发涂料有限公司 Preparation method of UV-curable polyurethane acrylate self-repair resin
JP2019520608A (en) * 2016-06-09 2019-07-18 スリーエム イノベイティブ プロパティズ カンパニー Polyurethane Acrylate Protective Display Film
US10962688B2 (en) * 2016-07-01 2021-03-30 3M Innovative Properties Company Low Tg polyurethane protective display film
JP2019151815A (en) * 2018-02-28 2019-09-12 東レ株式会社 Laminate and resin film
KR20210048440A (en) * 2018-08-23 2021-05-03 도레이 카부시키가이샤 Resin film, laminate, and manufacturing method of laminate
CN109705382B (en) * 2018-12-14 2021-08-10 张家港康得新光电材料有限公司 Self-repairing resin, coating, film preparation method and application
KR102124853B1 (en) 2018-12-14 2020-06-19 건국대학교 산학협력단 UV-curable urethane acrylate polymer using mixture of polyester polyols and process for the preparation thereof
CN113667054B (en) * 2021-06-18 2022-09-06 广东邦固化学科技有限公司 Self-repairing resin, preparation method and application thereof, and preparation method of self-repairing optical film
CN113980638B (en) * 2021-11-11 2023-01-10 上海昀通电子科技有限公司 UV pressure-sensitive delayed curing adhesive and preparation method and application thereof
US11939418B2 (en) * 2021-12-15 2024-03-26 Stratasys, Inc. Photo-curable compositions
CN115340817B (en) * 2022-09-15 2023-10-20 中国科学技术大学 Hardening coating with wide temperature range and high damping performance and preparation method thereof

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2837233B2 (en) * 1990-04-27 1998-12-14 三井化学株式会社 Radiation-curable resin and coating composition thereof
JP2003084102A (en) * 2001-06-25 2003-03-19 Asahi Glass Co Ltd Optical film and method for manufacturing the same
JP4142330B2 (en) * 2002-04-12 2008-09-03 ナトコ株式会社 Lens sheet
JP2004217809A (en) * 2003-01-16 2004-08-05 Mitsubishi Chemicals Corp Active energy beam-cured resin sheet
JP4812069B2 (en) * 2004-06-30 2011-11-09 日本化薬株式会社 Resin composition, lens resin composition and cured product thereof
JP2011074266A (en) * 2009-09-30 2011-04-14 Nippon Shokubai Co Ltd Curable resin composition for optical disk, cured product thereof, and optical disk
JP5617312B2 (en) * 2010-03-30 2014-11-05 大日本印刷株式会社 Electron beam curable resin composition and laminate comprising the same
JP5558257B2 (en) 2010-08-06 2014-07-23 株式会社昭和インク工業所 Curable composition
EP2468782A1 (en) * 2010-12-27 2012-06-27 Cytec Surface Specialties, S.A. Radiation curable compositions
JP5589911B2 (en) * 2011-03-15 2014-09-17 東亞合成株式会社 Electron beam curable composition for optical film or sheet formation, optical film or sheet, polarizer protective film and polarizing plate
JP5950107B2 (en) * 2011-07-29 2016-07-13 Jsr株式会社 Method for producing self-healing material, and method for producing composition for producing self-healing material
JP5803661B2 (en) * 2011-12-26 2015-11-04 東亞合成株式会社 Electron beam curable composition for optical film or optical sheet formation
WO2013146193A1 (en) * 2012-03-30 2013-10-03 Dic株式会社 Ultraviolet light curing urethane acrylate composition, thin-film formed body, optical film, and method for manufacturing thin-film formed body
JP5880304B2 (en) * 2012-06-18 2016-03-09 東亞合成株式会社 Method for producing optical film or sheet
JP2014024880A (en) * 2012-07-24 2014-02-06 Dic Corp Uv-curable urethane acrylate resin composition, thin film molded article, optical film, and production method of thin film molded article
JP2014048453A (en) * 2012-08-31 2014-03-17 Toagosei Co Ltd Production method of low retardation optical film or sheet by heat treatment

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI752030B (en) * 2016-06-28 2022-01-11 日商迪愛生股份有限公司 Polyurethane foam sheet, method for producing the same, and method for producing a laminate

Also Published As

Publication number Publication date
WO2014045782A1 (en) 2014-03-27
TWI487723B (en) 2015-06-11
JP5633768B2 (en) 2014-12-03
CN104619735B (en) 2016-08-17
KR20150009605A (en) 2015-01-26
KR101508706B1 (en) 2015-04-07
JPWO2014045782A1 (en) 2016-08-18
CN104619735A (en) 2015-05-13

Similar Documents

Publication Publication Date Title
TWI487723B (en) A method for producing an ultraviolet-curable urethane acrylate composition, a film-formed product, an optical film, and a film-forming body
TWI472547B (en) Method for manufacturing cured coating film, optical film and method for manufacturing thin-film formed body
US9018319B2 (en) Radical-curable hot-melt urethane resin composition and optical molded body
JP5859926B2 (en) Active energy ray curable composition for interlayer filling
JP5564949B2 (en) Curable composition
JP2014024880A (en) Uv-curable urethane acrylate resin composition, thin film molded article, optical film, and production method of thin film molded article
TWI545138B (en) Activation-energy-ray-curable resin composition
JP2016027073A (en) Polycarbonate diol, and polyurethane and urethane (meth)acrylate using the same
JP2014080585A (en) Active energy ray-curable resin composition, coating agent composition using the same and cured coating film
JP6899225B2 (en) Active energy ray-curable composition
JP2020084093A (en) Highly safe urethane acrylate and method for producing the same
CN110446736A (en) Polyurethane (methyl) acrylate polymer
JP2015063616A (en) Active energy ray-curable composition, cured coating film of the same, and article having the cured film
JP2014231591A (en) Urethane (meth)acrylate oligomer, curable resin composition, cured product and laminate
JP2003137964A (en) Urethane (meth)acrylate containing ultraviolet- absorbing functional group, and composition thereof
TWI667312B (en) Hardened resin composition for interlayer filling
JP2019157093A (en) Active energy ray-curable resin composition, and coating agent and sheet using the same
JP7257815B2 (en) Urethane (meth)acrylate, active energy ray-curable composition containing the same, and cured product thereof
JP6705165B2 (en) Urethane (meth)acrylate oligomer