TWI791603B - Curable composition for extensible and scratch-resistant coating - Google Patents
Curable composition for extensible and scratch-resistant coating Download PDFInfo
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- TWI791603B TWI791603B TW107130864A TW107130864A TWI791603B TW I791603 B TWI791603 B TW I791603B TW 107130864 A TW107130864 A TW 107130864A TW 107130864 A TW107130864 A TW 107130864A TW I791603 B TWI791603 B TW I791603B
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- poly
- perfluoropolyether
- aforementioned
- meth
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- 239000000203 mixture Substances 0.000 title claims abstract description 58
- 239000006120 scratch resistant coating Substances 0.000 title 1
- -1 poly(oxyalkylene) Polymers 0.000 claims abstract description 60
- 239000010702 perfluoropolyether Substances 0.000 claims abstract description 54
- 238000000576 coating method Methods 0.000 claims abstract description 48
- 239000011248 coating agent Substances 0.000 claims abstract description 43
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 239000011247 coating layer Substances 0.000 claims abstract description 23
- 150000002596 lactones Chemical class 0.000 claims abstract description 18
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 12
- 239000010410 layer Substances 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 19
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- 239000000758 substrate Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000005641 methacryl group Chemical group 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 230000001678 irradiating effect Effects 0.000 claims description 7
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical group O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 5
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- 239000003607 modifier Substances 0.000 claims description 4
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- 238000012986 modification Methods 0.000 claims description 2
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
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- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
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- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
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Classifications
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- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33348—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
- C09D171/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
- C08G2650/48—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen containing fluorine, e.g. perfluropolyethers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
- Manufacturing & Machinery (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Abstract
本發明提供一種具有延伸性及優良耐擦傷性,且呈現透明外觀的硬質塗布層之形成材料。 本發明係關於一種硬質塗布薄膜,其為具備含有(a)活性能量線硬化性內酯變性多官能單體100質量份、(b)於含有聚(氧基全氟伸烷基)基的分子鏈之兩末端上隔著胺基甲酸酯鍵具有活性能量線聚合性基的全氟聚醚(但,除於前述聚(氧基全氟伸烷基)基與前述胺基甲酸酯鍵之間具有聚(氧化伸烷基)基之全氟聚醚以外)0.1~10質量份,及(c)藉由活性能量線產生自由基之聚合起始劑1~20質量份的硬化性組成物,及藉由該組成物所形成的硬質塗布層之硬質塗布薄膜。The present invention provides a material for forming a hard coating layer having elongation, excellent scratch resistance, and a transparent appearance. The present invention relates to a hard coating film comprising (a) 100 parts by mass of an active energy ray-curable lactone denatured polyfunctional monomer, (b) a molecule containing a poly(oxyperfluoroalkylene) group Perfluoropolyether having an active energy ray polymerizable group at both ends of the chain via a urethane bond (except for the aforementioned poly(oxyperfluoroalkylene) group and the aforementioned urethane bond A curable composition consisting of 0.1 to 10 parts by mass of (c) 1 to 20 parts by mass of a polymerization initiator that generates free radicals by active energy rays (except perfluoropolyether having a poly(oxyalkylene) group) and the hard coating film of the hard coating layer formed by the composition.
Description
本發明係關於作為適用於觸控板顯示、液晶顯示等各種顯示元件等表面的硬質塗布層之形成材料為有用的硬化性組成物。詳細而言,具有延伸性及優良耐擦傷性,且可形成呈現透明外觀的硬質塗布層之硬化性組成物。The present invention relates to a curable composition useful as a material for forming a hard coat layer on the surface of various display elements such as touch panel displays and liquid crystal displays. Specifically, it is a curable composition that has elongation and excellent scratch resistance, and can form a hard coating layer with a transparent appearance.
於手機、平板型電腦等攜帶訊息終端機、筆記型電腦、家電製品、汽車內外裝零件等使用大量的樹脂成形品。對於這些樹脂成形品,欲提高該設計性,通常在成形樹脂後,於該表面上藉由印刷等施予裝飾。近年來,作為對於上述樹脂成形品的立體表面之裝飾方法,於薄膜的單面上使用硬質塗布層,另一面上使用各設置印刷層或黏著層的裝飾薄膜,將此等裝飾薄膜隔著黏著層,貼合於樹脂成形品的方法正被檢討著。A large number of resin molded products are used in portable information terminals such as mobile phones and tablet computers, notebook computers, home appliances, and automotive interior and exterior parts. In order to improve the designability of these resin molded products, decoration is usually given to the surface by printing or the like after molding the resin. In recent years, as a decoration method for the three-dimensional surface of the above-mentioned resin molded product, a hard coating layer is used on one side of the film, and a decorative film with a printing layer or an adhesive layer on the other side is used, and these decorative films are adhered through Layers, methods of laminating to resin molded products are being examined.
作為上述裝飾薄膜之要求特性,第1其成形性為必要。換言之,即使被延伸亦無法於硬質塗布層上產生裂紋等,可追隨立體表面的延伸性成為必要。第2其耐擦傷性為必要。上述裝飾薄膜的硬質塗布層在貼合於樹脂成形品的狀態下位置於最表面上,擔任保護該表面的角色。As the required characteristics of the above-mentioned decorative film, the first formability is necessary. In other words, even if stretched, cracks and the like cannot be generated on the hard coat layer, and stretchability that can follow the three-dimensional surface is required. Second, its scratch resistance is necessary. The hard coat layer of the above-mentioned decorative film is located on the outermost surface in a state of being bonded to the resin molded product, and plays a role of protecting the surface.
一般對硬質塗布層賦予耐擦傷性時,例如藉由形成高度交聯結構,即形成分子運動性較低的交聯結構而可使表面硬度提高,賦予對外力的抵抗性之方法被採用。作為這些硬質塗布層形成材料,現在最廣為使用藉由自由基進行3次元交聯的多官能丙烯酸酯系材料。但多官能丙烯酸酯系材料因有較高的交聯密度,故完全無具有延伸性。 另一方面,作為於硬質塗布層賦予延伸性,例如採用使用具有1,000~10,000程度的分子量之丙烯酸酯基密度經調整的多官能丙烯酸酯系寡聚物或多官能胺基甲酸酯丙烯酸酯系寡聚物的方法。這些多官能丙烯酸酯系寡聚物為於分子結構內具有交聯部位與延伸部位,藉由延伸部位的分子運動性,可表現適度延伸性。但交聯密度會降低其耐擦傷性較為差。 如此,硬質塗布層的延伸性與耐擦傷性具有權衡關係,兼具兩者特性為自過去的課題。Generally, when imparting scratch resistance to a hard coating layer, for example, by forming a highly cross-linked structure, that is, forming a cross-linked structure with low molecular mobility, the method of increasing the surface hardness and imparting resistance to external force is adopted. As these hard coat layer forming materials, polyfunctional acrylate-based materials that undergo three-dimensional crosslinking by radicals are most widely used at present. However, multifunctional acrylate materials have no extensibility at all due to their high crosslink density. On the other hand, for imparting extensibility to the hard coat layer, for example, a polyfunctional acrylate oligomer or a polyfunctional urethane acrylate oligomer having a molecular weight of about 1,000 to 10,000 with an adjusted acrylate group density is used. Oligomer method. These polyfunctional acrylate oligomers have crosslinking sites and extension sites in their molecular structures, and can exhibit moderate extensibility through the molecular mobility of the extension sites. However, the crosslinking density will decrease and its scratch resistance will be poor. In this way, the elongation and scratch resistance of the hard coat layer have a trade-off relationship, and it has been a problem since the past to have both characteristics.
然而,對於以手機作為代表的攜帶型訊息終端機而言,人可用手掌握住並以手指進行接觸操作。因此,當手握住時其外殼會附著指紋,會有損害該外觀的問題產生。指紋中含有來自汗水的水分及來自皮脂的油分,欲使這些皆不易附著,對於外殼表面的硬質塗布層賦予撥水性及撥油性成為強烈的期待。 由如此觀點得知,於攜帶訊息終端機的外殼表面上,期待具有對於如指紋等的防污性。但,即使初期的防污性可達到相當高的水準,因人必須每天觸摸,故在使用時亦常降低其功能的情況為多。因此,在使用過程的防污性之耐久性成為課題。However, for a portable information terminal represented by a mobile phone, a person can grasp it with a palm and perform touch operation with fingers. Therefore, there is a problem that fingerprints are attached to the outer casing when it is held by hand, and the appearance is impaired. Fingerprints contain moisture from sweat and oil from sebum, and in order to prevent these from adhering, it is strongly desired to impart water and oil repellency to the hard coating layer on the surface of the case. From such a point of view, antifouling properties such as fingerprints are expected to be provided on the casing surface of the portable information terminal. However, even if the initial antifouling performance can reach a fairly high level, since people have to touch it every day, the function is often reduced during use. Therefore, the durability of the antifouling property during use becomes a problem.
過去,作為對於硬質塗布層表面賦予防污性之方法,有形成硬質塗布層的塗布液中添加少量的氟系表面改質劑之方法被使用。所要添加的氟系化合物為藉由該低表面能量於硬質塗布層的表面上被偏析,而賦予撥水性及撥油性。作為氟系化合物,由撥水性、撥油性的觀點來看,使用稱為具有聚(氧基全氟伸烷基)鏈的全氟聚醚之具有1,000~5,000程度的數平均分子量之寡聚物。然而,全氟聚醚因具較佳氟濃度,通常難溶解於使用在形成硬質塗布層的塗布液之有機溶劑。又,對於所形成的硬質塗布層亦會引起凝集現像。 對於如此全氟聚醚中,欲賦予對於有機溶劑的溶解性及賦予對於硬質塗布層的分散性,使用於全氟聚醚加成有機部位的方法。且欲賦予耐擦傷性,使用鍵結(甲基)丙烯酸酯基為代表的活性能量線硬化性部位之方法。 至今,作為具有耐擦傷性的防污性硬質塗布層,其中對於硬質塗布層表面賦予防污性的成分,已有揭示於聚(氧基全氟伸烷基)鏈的兩末端上,將具有聚(氧化伸烷基)基(Poly (oxyalkylene))及隔著1個胺基甲酸酯鍵之(甲基)丙烯醯基的化合物作為表面改質劑使用的技術(專利文獻1)。 [先前技術文獻] [專利文獻]Conventionally, as a method of imparting antifouling properties to the surface of a hard coat layer, a method of adding a small amount of a fluorine-based surface modifier to a coating solution for forming a hard coat layer has been used. The fluorine-based compound to be added is to impart water repellency and oil repellency by segregating the low surface energy on the surface of the hard coat layer. As the fluorine-based compound, an oligomer having a number average molecular weight of about 1,000 to 5,000 called a perfluoropolyether having a poly(oxyperfluoroalkylene) chain is used from the viewpoint of water repellency and oil repellency. . However, because perfluoropolyether has a better fluorine concentration, it is generally difficult to dissolve in the organic solvent used in the coating solution for forming the hard coating layer. Moreover, the aggregation phenomenon also arises with respect to the formed hard coat layer. In such a perfluoropolyether, in order to impart solubility in an organic solvent and impart dispersibility to a hard coat layer, a method of adding an organic moiety to the perfluoropolyether is used. Furthermore, in order to impart scratch resistance, a method of bonding active energy ray hardening sites represented by (meth)acrylate groups is used. Hitherto, as an antifouling hard coating layer having scratch resistance, a component that imparts antifouling properties to the surface of the hard coating layer has been disclosed on both ends of a poly(oxyperfluoroalkylene) chain, which will have A technique in which a poly(oxyalkylene) group and a (meth)acryl group compound having a urethane bond interposed therebetween are used as a surface modifying agent (Patent Document 1). [Prior Art Literature] [Patent Document]
[專利文獻1]國際公開第2016/163479號[Patent Document 1] International Publication No. 2016/163479
[發明所解決的問題][Problem solved by the invention]
然而,將對表現延伸性的硬質塗布層賦予耐擦傷性作為目的下,即使於多官能丙烯酸酯系寡聚物等添加專利文獻1的表面改質劑,因為這些寡聚物的高分子量及疏水性而使相溶性變差,該硬化物的硬質塗布層有著變白濁之課題產生。 [解決課題的手段]However, for the purpose of imparting scratch resistance to the hard coat layer exhibiting elongation, even if the surface modifying agent of Patent Document 1 is added to a polyfunctional acrylate oligomer, etc., because these oligomers have high molecular weight and hydrophobic The compatibility is deteriorated, and the hard coating layer of the hardened product has the problem of becoming cloudy. [means to solve the problem]
本發明者們,欲達常上述目的而進行重複詳細檢討結果,發現於含有聚(氧基全氟伸烷基)基的分子鏈之兩末端上,未隔著聚(氧化伸烷基)基,而隔著胺基甲酸酯鍵,具有活性能量線聚合性基的全氟聚醚,對於形成含有內酯變性多官能單體之硬質塗布層的塗布液而言具有溶解性及於硬質塗布層中優良分散性,且含有該全氟聚醚與內酯變性多官能單體的硬化性組成物,其具有延伸性及優良耐擦傷性,且可形成呈現透明外觀的硬質塗布層而完成本發明。The present inventors, in order to achieve the above-mentioned purpose, repeated detailed examinations and found that on both ends of the molecular chain containing poly(oxyperfluoroalkylene) groups, there is no poly(oxyalkylene) group interposed therebetween. , and through the urethane bond, the perfluoropolyether having the active energy ray polymerizable group has solubility in the coating solution for forming the hard coating layer containing the lactone-modified polyfunctional monomer and is suitable for hard coating Excellent dispersibility in the layer, and the curable composition containing the perfluoropolyether and the lactone-denatured polyfunctional monomer has elongation and excellent scratch resistance, and can form a hard coating layer showing a transparent appearance to complete the present invention. invention.
即,本發明的第1觀點係關於一種硬化性組成物,其含有 (a)活性能量線硬化性內酯變性多官能單體100質量份、 (b)於含有聚(氧基全氟伸烷基)基的分子鏈之兩末端上隔著胺基甲酸酯鍵具有活性能量線聚合性基的全氟聚醚(但,除於前述聚(氧基全氟伸烷基)基與前述胺基甲酸酯鍵之間具有聚(氧化伸烷基)基之全氟聚醚以外)0.1~10質量份,及(c)藉由活性能量線產生自由基之聚合起始劑1~20質量份。 作為第2觀點,前述(b)全氟聚醚係關於於各兩末端上具有至少2個活性能量線聚合性基的第1觀點所記載的硬化性組成物。 作為第3觀點,前述(b)全氟聚醚係關於於各兩末端上具有至少3個活性能量線聚合性基的第2觀點所記載的硬化性組成物。 作為第4觀點,前述聚(氧基全氟伸烷基)基為具有作為重複單位的-[OCF2 ]-及-[OCF2 CF2 ]-的基之第1觀點至第3觀點中任一項所記載的硬化性組成物。 作為第5觀點,前述(b)全氟聚醚係關於具有式[1]所示部分結構之第4觀點所記載的硬化性組成物。 (式中,n為重複單位-[OCF2 CF2 ]-的數與重複單位 -[OCF2 ]-的數之總數,其為5~30的整數) 作為第6觀點,前述(a)多官能單體係關於含有選自由內酯變性多官能(甲基)丙烯酸酯化合物及內酯變性多官能胺基甲酸酯(甲基)丙烯酸酯化合物所成群的至少1個之第1觀點至第5觀點中任一項所記載的硬化性組成物。 作為第7觀點,前述(a)多官能單體為ε-己內酯變性多官能單體,其係關於第1觀點至第6觀點中任一項所記載的硬化性組成物。 作為第8觀點,其係關於進一步含有(d)溶劑之第1觀點至第7觀點中任一項所記載的硬化性組成物。 作為第9觀點,其係關於藉由第1觀點至第8觀點中任一項所記載的硬化性組成物所得之硬化膜。 作為第10觀點,其為於薄膜基材的至少一面上具備硬質塗布層的硬質塗布薄膜,其係關於該硬質塗布層由第9觀點所記載的硬化膜所成的硬質塗布薄膜。 作為第11觀點,其為於薄膜基材的至少一面上具備硬質塗布層的硬質塗布薄膜,其係關於該硬質塗布層為藉由含有將第1觀點至第8觀點中任一項所記載的硬化性組成物塗布於薄膜基材上並形成塗膜的步驟,與於該塗膜照射活性能量線使其硬化的步驟之方法所形成的硬質塗布薄膜。 作為第12觀點,其關於前述硬質塗布層具有1~10μm的膜厚之第10觀點或第11觀點所記載的硬質塗布薄膜。 作為第13觀點,其係關於在含有聚(氧基全氟伸烷基)基的分子鏈之各兩末端上,隔著胺基甲酸酯鍵,具有至少3個活性能量線聚合性基之全氟聚醚化合物(但,除去於前述聚(氧基全氟伸烷基)基與前述胺基甲酸酯鍵之間具有聚(氧化伸烷基)基的全氟聚醚化合物以外)。 作為第14觀點,其係關於前述聚(氧基全氟伸烷基)基具有作為重複單位的-[OCF2 ]-及-[OCF2 CF2 ]-的第13觀點所記載的全氟聚醚化合物。 作為第15觀點,其係關於具有式[1]所示部分結構的第14觀點所記載的全氟聚醚化合物。 (式中,n為重複單位-[OCF2 CF2 ]-的數與重複單位 -[OCF2 ]-的數之總數,其表示5~30的整數)。 作為第16觀點,其係關於由第13觀點至第15觀點中任一項所記載的全氟聚醚化合物所成的表面改質劑。 作為第17觀點,其係關於使用第13觀點至第15觀點中任一項所記載的全氟聚醚化合物在表面改質上的用途。 [發明之效果]That is, the first aspect of the present invention relates to a curable composition comprising (a) 100 parts by mass of an active energy ray-curable lactone-denatured polyfunctional monomer, (b) poly(oxyperfluoroalkylene) A perfluoropolyether (except for the aforementioned poly(oxyperfluoroalkylene) group and the aforementioned amine) having an active energy ray polymerizable group at both ends of the molecular chain of the urethane bond 0.1-10 parts by mass other than perfluoropolyether having poly(oxyalkylene) groups between urethane bonds, and (c) 1-20 parts by mass of a polymerization initiator that generates free radicals by active energy rays share. As a second viewpoint, the aforementioned (b) perfluoropolyether is a curable composition described in the first viewpoint having at least two active energy ray polymerizable groups at both ends. As a third viewpoint, the aforementioned (b) perfluoropolyether is a curable composition described in the second viewpoint having at least three active energy ray polymerizable groups at both ends. As a fourth viewpoint, the aforementioned poly(oxyperfluoroalkylene) group is any one of the first viewpoint to the third viewpoint that has -[OCF 2 ]- and -[OCF 2 CF 2 ]- as repeating units. A hardening composition of record. As a fifth viewpoint, the aforementioned (b) perfluoropolyether is the curable composition described in the fourth viewpoint having a partial structure represented by the formula [1]. (In the formula, n is the sum of the number of repeating units -[OCF 2 CF 2 ]- and the number of repeating units -[OCF 2 ]-, which is an integer of 5 to 30.) As a sixth aspect, the aforementioned (a) is more The functional monosystem contains at least one member selected from the group consisting of lactone-modified polyfunctional (meth)acrylate compounds and lactone-modified polyfunctional urethane (meth)acrylate compounds from the first point of view to The curable composition described in any one of the fifth viewpoints. As a seventh viewpoint, the (a) polyfunctional monomer is an ε-caprolactone-modified polyfunctional monomer, which is the curable composition described in any one of the first viewpoint to the sixth viewpoint. As an eighth viewpoint, it is the curable composition described in any one of the first viewpoint to the seventh viewpoint that further contains (d) a solvent. As a ninth viewpoint, it relates to a cured film obtained from the curable composition described in any one of the first viewpoint to the eighth viewpoint. As a tenth viewpoint, it is a hard coat film provided with a hard coat layer on at least one surface of a film base material, and it is a hard coat film which consists of the cured film as described in a ninth viewpoint about this hard coat layer. As an eleventh viewpoint, it is a hard coat film provided with a hard coat layer on at least one surface of a film substrate, and the hard coat layer is obtained by containing any one of the first viewpoint to the eighth viewpoint. A hard coat film formed by a step of applying a curable composition on a film substrate to form a coating film, and a step of irradiating the coating film with active energy rays to harden it. As a 12th viewpoint, it is about the hard-coat film as described in the 10th viewpoint or the 11th viewpoint that the said hard-coat layer has a film thickness of 1-10 micrometers. As a thirteenth viewpoint, it relates to having at least three active energy ray polymerizable groups at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group via a urethane bond. Perfluoropolyether compounds (except for perfluoropolyether compounds having a poly(oxyalkylene) group between the aforementioned poly(oxyperfluoroalkylene) group and the aforementioned urethane bond). As a 14th viewpoint, it is the perfluoropolyethylene described in the 13th viewpoint that the aforementioned poly(oxyperfluoroalkylene) group has -[OCF 2 ]- and -[OCF 2 CF 2 ]- as repeating units. Ether compounds. As a 15th viewpoint, it relates to the perfluoropolyether compound described in the 14th viewpoint which has a partial structure represented by formula [1]. (In the formula, n is the total number of the repeating unit -[OCF 2 CF 2 ]- and the repeating unit -[OCF 2 ]-, which represents an integer of 5 to 30). As a 16th viewpoint, it relates to the surface modifying agent which consists of the perfluoropolyether compound described in any one of the 13th viewpoint to the 15th viewpoint. As a 17th viewpoint, it relates to the use for surface modification using the perfluoropolyether compound described in any one of the 13th viewpoint to the 15th viewpoint. [Effect of Invention]
依據本發明可提供一種具有在厚度1~10μm程度的薄膜上亦優良的耐擦傷性,外觀亦優良,且具有延伸性的使用於硬化膜及硬質塗布層的形成之硬化性組成物。 又,依據本發明可提供一種藉由前述硬化性組成物所得的硬化膜,或於藉此所形成的硬質塗布層賦予表面之硬質塗布薄膜,其具有耐擦傷性及優良外觀,且具有延伸性的硬質塗布薄膜。According to the present invention, it is possible to provide a curable composition used for forming a cured film and a hard coat layer that has excellent scratch resistance even on a film having a thickness of about 1 to 10 μm, has an excellent appearance, and has elongation. Also, according to the present invention, there can be provided a cured film obtained from the aforementioned curable composition, or a hard coating film provided on the surface of the hard coating layer formed thereby, which has scratch resistance, excellent appearance, and has extensibility hard coating film.
<硬化性組成物> 本發明之硬化性組成物詳細為含有以下(a)~(c)者。 (a)活性能量線硬化性內酯變性多官能單體100質量份、 (b)於含有聚(氧基全氟伸烷基)基的分子鏈之兩末端上隔著胺基甲酸酯鍵具有活性能量線聚合性基的全氟聚醚(但,除於前述聚(氧基全氟伸烷基)基與前述胺基甲酸酯鍵之間具有聚(氧化伸烷基)基之全氟聚醚以外)0.1~10質量份、及 (c)藉由活性能量線產生自由基之聚合起始劑1~20質量份。 以下首先對於上述(a)~(c)的各成分做說明。<Hardening composition> The curable composition of the present invention contains the following (a) to (c) in detail. (a) 100 parts by mass of an active energy ray-curable lactone-denatured polyfunctional monomer, (b) Perfluoropolyethers having active energy ray polymerizable groups at both ends of molecular chains containing poly(oxyperfluoroalkylene) groups via urethane bonds (except for the aforementioned poly 0.1 to 10 parts by mass other than perfluoropolyethers having a poly(oxyalkylene) group between the (oxyperfluoroalkylene) group and the aforementioned urethane linkage), and (c) 1 to 20 parts by mass of a polymerization initiator that generates radicals by active energy rays. First, each component of said (a)-(c) is demonstrated below.
[(a)活性能量線硬化性內酯變性多官能單體] 所謂活性能量線硬化性內酯變性多官能單體係指藉由照射紫外線等活性能量線而進行聚合反應並使其硬化的以內酯進行變性的多官能單體。 作為對於本發明之硬化性組成物的較佳(a)活性能量線硬化性內酯變性多官能單體為選自由內酯變性多官能(甲基)丙烯酸酯化合物及內酯變性多官能胺基甲酸酯(甲基)丙烯酸酯化合物所成群的單體。 且,所謂本發明的(甲基)丙烯酸酯化合物係指丙烯酸酯化合物與甲基丙烯酸酯化合物之雙方。例如(甲基)丙烯酸表示丙烯酸與甲基丙烯酸。[(a) Active energy ray-curing lactone denatured polyfunctional monomer] The active energy ray-curable lactone-denatured polyfunctional monomer system refers to a lactone-denatured polyfunctional monomer that is polymerized and cured by irradiating active energy rays such as ultraviolet rays. Preferred (a) active energy ray-curing lactone-modified polyfunctional monomers for the curable composition of the present invention are selected from lactone-modified polyfunctional (meth)acrylate compounds and lactone-modified polyfunctional amine groups A monomer in which formate (meth)acrylate compounds are grouped. In addition, the (meth)acrylate compound of this invention means both of an acrylate compound and a methacrylate compound. For example (meth)acrylic acid means acrylic acid and methacrylic acid.
作為上述內酯變性多官能(甲基)丙烯酸酯化合物,例如可舉出以γ-丁內酯、δ-戊內酯、ε-己內酯等內酯進行變性(即,將內酯進行開環加成或開環加成聚合)的多元醇或聚硫醇之(甲基)丙烯酸酯化合物。 作為該多元醇,例如可舉出三羥甲基丙烷、二三羥甲基丙烷、季戊四醇、二季戊四醇、甘油、雙酚A、乙氧基化三羥甲基丙烷、乙氧基化季戊四醇、乙氧基化二季戊四醇、乙氧基化甘油、乙氧基化雙酚A、1,3-丙烷二醇、1,3-丁二醇、1,4-丁二醇、1,6-己二醇、2-甲基-1,8-辛烷二醇、1,9-壬二醇、1,10-癸烷二醇、三環[5.2.1.02,6 ]癸烷二甲醇、1,3-金剛烷二醇、1,3-金剛烷二甲醇、乙二醇、二乙二醇、三乙二醇、四乙二醇、聚乙二醇、丙二醇、二丙二醇、聚丙二醇、新戊二醇、二噁烷甘醇、雙(2-羥基乙基)異氰脲酸酯、參(2-羥基乙基)異氰脲酸酯、9,9-雙(4-羥基苯基)芴、9,9-雙[4-(2-羥基乙氧基)苯基]芴等。 又,作為該硫醇,可舉出雙(2-巰基乙基)硫化物、雙(4-巰基苯基)硫化物等。Examples of the above-mentioned lactone-denatured polyfunctional (meth)acrylate compound include denaturation with lactones such as γ-butyrolactone, δ-valerolactone, and ε-caprolactone (that is, the development of lactones). (cycloaddition or ring-opening addition polymerization) polyol or polythiol (meth)acrylate compound. Examples of the polyhydric alcohol include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, glycerin, bisphenol A, ethoxylated trimethylolpropane, ethoxylated pentaerythritol, ethyl Oxylated dipentaerythritol, ethoxylated glycerin, ethoxylated bisphenol A, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol alcohol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, tricyclo[5.2.1.0 2,6 ]decanedimethanol, 1, 3-Adamantanediol, 1,3-Adamantanedimethanol, Ethylene Glycol, Diethylene Glycol, Triethylene Glycol, Tetraethylene Glycol, Polyethylene Glycol, Propylene Glycol, Dipropylene Glycol, Polypropylene Glycol, Neopentyl Glycol Diol, dioxane glycol, bis(2-hydroxyethyl)isocyanurate, ginseng(2-hydroxyethyl)isocyanurate, 9,9-bis(4-hydroxyphenyl)fluorene , 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene, etc. Moreover, examples of the mercaptan include bis(2-mercaptoethyl)sulfide, bis(4-mercaptophenyl)sulfide, and the like.
作為如此內酯變性多官能(甲基)丙烯酸酯化合物,例如可舉出內酯變性三羥甲基丙烷三(甲基)丙烯酸酯、內酯變性雙三羥甲基丙烷四(甲基)丙烯酸酯、內酯變性季戊四醇二(甲基)丙烯酸酯、內酯變性季戊四醇三(甲基)丙烯酸酯、內酯變性季戊四醇四(甲基)丙烯酸酯、內酯變性二季戊四醇五(甲基)丙烯酸酯、內酯變性二季戊四醇六(甲基)丙烯酸酯、內酯變性2-羥基-1,3-二(甲基)丙烯醯氧基丙烷、內酯變性2-羥基-1-丙烯醯氧基-3-甲基丙烯醯氧丙烷、內酯變性甘油三(甲基)丙烯酸酯、內酯變性雙酚A二(甲基)丙烯酸酯、內酯變性乙氧基化三羥甲基丙烷三(甲基)丙烯酸酯、內酯變性乙氧基化季戊四醇四(甲基)丙烯酸酯、內酯變性乙氧基化二季戊四醇六(甲基)丙烯酸酯、內酯變性乙氧基化甘油三(甲基)丙烯酸酯、內酯變性乙氧基化雙酚A二(甲基)丙烯酸酯、內酯變性1,3-丙烷二醇二(甲基)丙烯酸酯、內酯變性1,3-丁二醇二(甲基)丙烯酸酯、內酯變性1,4-丁二醇二(甲基)丙烯酸酯、內酯變性1,6-己二醇二(甲基)丙烯酸酯、內酯變性2-甲基-1,8-辛烷二醇二(甲基)丙烯酸酯、內酯變性1,9-壬二醇二(甲基)丙烯酸酯、內酯變性1,10-癸烷二醇二(甲基)丙烯酸酯、內酯變性三環[5.2.1.02,6 ]癸烷二甲醇二(甲基)丙烯酸酯、內酯變性1,3-金剛烷二醇二(甲基)丙烯酸酯、內酯變性1,3-金剛烷二甲醇二(甲基)丙烯酸酯、內酯變性乙二醇二(甲基)丙烯酸酯、內酯變性二乙二醇二(甲基)丙烯酸酯、內酯變性三乙二醇二(甲基)丙烯酸酯、內酯變性四乙二醇二(甲基)丙烯酸酯、內酯變性聚乙二醇二(甲基)丙烯酸酯、內酯變性丙二醇二(甲基)丙烯酸酯、內酯變性二丙二醇二(甲基)丙烯酸酯、內酯變性聚丙二醇二(甲基)丙烯酸酯、內酯變性新戊二醇二(甲基)丙烯酸酯、內酯變性二噁烷甘醇二(甲基)丙烯酸酯、內酯變性雙(2-羥基乙基)異氰脲酸酯二(甲基)丙烯酸酯、內酯變性參(2-羥基乙基)異氰脲酸酯三(甲基)丙烯酸酯、內酯變性9,9-雙(4-(甲基)丙烯醯氧基苯基)芴、內酯變性9,9-雙[4-(2-(甲基)丙烯醯氧基乙氧基)苯基]芴、內酯變性雙[2-(甲基)丙烯醯基硫代乙基]硫化物、內酯變性雙[4-(甲基)丙烯醯基噻吩基]硫化物等。Examples of such lactone-denatured polyfunctional (meth)acrylate compounds include lactone-denatured trimethylolpropane tri(meth)acrylate, lactone-denatured ditrimethylolpropane tetra(meth)acrylate Esters, lactone-denatured pentaerythritol di(meth)acrylate, lactone-denatured pentaerythritol tri(meth)acrylate, lactone-denatured pentaerythritol tetra(meth)acrylate, lactone-denatured dipentaerythritol penta(meth)acrylate , Lactone-denatured dipentaerythritol hexa(meth)acrylate, lactone-denatured 2-hydroxy-1,3-bis(meth)acryloxypropane, lactone-denatured 2-hydroxy-1-acryloxy- 3-Methacryloxypropane, lactone-denatured glycerol tri(meth)acrylate, lactone-denatured bisphenol A di(meth)acrylate, lactone-denatured ethoxylated trimethylolpropane tri(meth)acrylate base) acrylates, lactone-denatured ethoxylated pentaerythritol tetra(meth)acrylate, lactone-denatured ethoxylated dipentaerythritol hexa(meth)acrylate, lactone-denatured ethoxylated tri(methyl)glycerol ) acrylate, lactone-denatured ethoxylated bisphenol A di(meth)acrylate, lactone-denatured 1,3-propanediol di(meth)acrylate, lactone-denatured 1,3-butanediol Di(meth)acrylate, lactone-denatured 1,4-butanediol di(meth)acrylate, lactone-denatured 1,6-hexanediol di(meth)acrylate, lactone-denatured 2-methacrylate 1,8-octanediol di(meth)acrylate, lactone-denatured 1,9-nonanediol di(meth)acrylate, lactone-denatured 1,10-decanediol di(meth)acrylate base) acrylate, lactone-denatured tricyclo[5.2.1.0 2,6 ]decanedimethanol di(meth)acrylate, lactone-denatured 1,3-adamantanediol di(meth)acrylate, lactone-denatured Ester denatured 1,3-adamantane dimethanol di(meth)acrylate, lactone denatured ethylene glycol di(meth)acrylate, lactone denatured diethylene glycol di(meth)acrylate, lactone denatured Triethylene glycol di(meth)acrylate, lactone-denatured tetraethylene glycol di(meth)acrylate, lactone-denatured polyethylene glycol di(meth)acrylate, lactone-denatured propylene glycol di(meth)acrylate ) acrylate, lactone-denatured dipropylene glycol di(meth)acrylate, lactone-denatured polypropylene glycol di(meth)acrylate, lactone-denatured neopentyl glycol di(meth)acrylate, lactone-denatured dioxin Alkyl glycol di(meth)acrylate, lactone denatured bis(2-hydroxyethyl)isocyanurate di(meth)acrylate, lactone denatured ginseng(2-hydroxyethyl)isocyanurate Ester tri(meth)acrylate, lactone-denatured 9,9-bis(4-(meth)acryloxyphenyl)fluorene, lactone-denatured 9,9-bis[4-(2-(methyl) )acryloxyethoxy)phenyl]fluorene, lactone denatured bis[2-(meth)acrylthioethyl]sulfide, lactone denatured bis[4-(meth)acryl Thienyl] sulfide, etc.
其中作為經變性的內酯以ε-己內酯為佳,例如以上述內酯變性多官能(甲基)丙烯酸酯化合物的內酯為ε-己內酯的化合物為佳。 作為較佳內酯變性多官能(甲基)丙烯酸酯化合物,例如可舉出ε-己內酯變性季戊四醇三(甲基)丙烯酸酯、ε-己內酯變性季戊四醇四(甲基)丙烯酸酯、ε-己內酯變性二季戊四醇五(甲基)丙烯酸酯、ε-己內酯變性二季戊四醇六(甲基)丙烯酸酯等。Among them, ε-caprolactone is preferred as the denatured lactone, for example, the compound in which the lactone of the above-mentioned lactone-denatured polyfunctional (meth)acrylate compound is ε-caprolactone is preferred. Examples of preferable lactone-modified polyfunctional (meth)acrylate compounds include ε-caprolactone-denatured pentaerythritol tri(meth)acrylate, ε-caprolactone-denatured pentaerythritol tetra(meth)acrylate, ε-caprolactone-denatured dipentaerythritol penta(meth)acrylate, ε-caprolactone-denatured dipentaerythritol hexa(meth)acrylate, etc.
上述內酯變性多官能胺基甲酸酯(甲基)丙烯酸酯化合物為於1分子內具有複數個(甲基)丙烯醯基,具有胺基甲酸酯鍵(-NHCOO-)及例如具有γ-丁內酯、δ-戊內酯、ε-己內酯等內酯的開環結構之化合物。 例如作為上述內酯變性多官能胺基甲酸酯(甲基)丙烯酸酯,雖可舉出藉由多官能異氰酸酯與具有以內酯進行變性的羥基之(甲基)丙烯酸酯的反應所得者、藉由多官能異氰酸酯與具有羥基的(甲基)丙烯酸酯與以內酯經變性的多元醇之反應所得者等,在本發明可使用的內酯變性多官能胺基甲酸酯(甲基)丙烯酸酯化合物並未限定於此有關例示。The above-mentioned lactone-modified polyfunctional urethane (meth)acrylate compound has a plurality of (meth)acryl groups in one molecule, has a urethane bond (-NHCOO-), and has, for example, γ - Compounds with ring-opened structures of lactones such as butyrolactone, δ-valerolactone, and ε-caprolactone. For example, as the above-mentioned lactone-denatured polyfunctional urethane (meth)acrylate, those obtained by the reaction of a polyfunctional isocyanate and a (meth)acrylate having a hydroxyl group denatured with a lactone can be mentioned. The lactone-modified polyfunctional urethane (meth)acrylate that can be used in the present invention is obtained by reacting polyfunctional isocyanate, hydroxyl-containing (meth)acrylate, and lactone-denatured polyol, etc. The compound is not limited to this relevant illustration.
且作為上述多官能異氰酸酯,例如可舉出甲苯二異氰酸酯、異佛爾酮二異氰酸酯、亞二甲苯二異氰酸酯、六伸甲基二異氰酸酯等。 又,作為上述具有羥基的(甲基)丙烯酸酯,例如可舉出(甲基)丙烯酸2-羥基乙基、(甲基)丙烯酸2-羥基丙基、季戊四醇三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、三季戊四醇七(甲基)丙烯酸酯等。 而作為上述多元醇,例如可舉出乙二醇、丙二醇、新戊二醇、1,4-丁二醇、1,6-己二醇、二乙二醇、二丙二醇等二醇類;這些二醇類與琥珀酸、馬來酸、己二酸等脂肪族二羧酸類或二羧酸酐類之反應生成物的聚酯多元醇;聚醚多元醇;聚碳酸酯二醇等。In addition, as said polyfunctional isocyanate, for example, tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, etc. are mentioned. Moreover, examples of (meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, di Pentaerythritol penta(meth)acrylate, tripentaerythritol hepta(meth)acrylate, and the like. On the other hand, examples of the aforementioned polyhydric alcohols include glycols such as ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, and dipropylene glycol; these Polyester polyols produced by the reaction of diols with succinic acid, maleic acid, adipic acid and other aliphatic dicarboxylic acids or dicarboxylic anhydrides; polyether polyols; polycarbonate diols, etc.
在本發明中,作為上述(a)活性能量線硬化性內酯變性多官能單體,可使用由上述內酯變性多官能(甲基)丙烯酸酯化合物及上述內酯變性多官能胺基甲酸酯(甲基)丙烯酸酯化合物所成群的單獨一種,或組合二種以上者。In the present invention, as the above-mentioned (a) active energy ray-curable lactone-denatured polyfunctional monomer, the above-mentioned lactone-denatured polyfunctional (meth)acrylate compound and the above-mentioned lactone-denatured polyfunctional carbamic acid can be used. A single type of ester (meth)acrylate compound or a combination of two or more types.
[(b)於含有聚(氧基全氟伸烷基)基的分子鏈之兩末端上隔著胺基甲酸酯鍵具有活性能量線聚合性基的全氟聚醚(但,除於前述聚(氧基全氟伸烷基)基與前述胺基甲酸酯鍵之間具有聚(氧化伸烷基)基之全氟聚醚以外)] 在本發明中,作為(b)成分,使用於含有聚(氧基全氟伸烷基)基的分子鏈之兩末端上,不隔著聚(氧化伸烷基)基而隔著胺基甲酸酯鍵的具有活性能量線聚合性基的全氟聚醚(以下僅有時僅稱為「(b)於兩末端上具有聚合性基的全氟聚醚」)。(b)成分為扮演著作為適用本發明之硬化性組成物的硬質塗布層中之表面改質劑的角色。 又,(b)成分為與(a)成分的相溶性優良,藉此可抑制硬質塗布層的白濁現像,可形成呈現透明外觀的硬質塗布層。 且,所謂上述聚(氧化伸烷基)基表示氧基伸烷基的重複單位數為2以上且於氧基伸烷基中之伸烷基為無取代的伸烷基之基。[(b) Perfluoropolyether (except for the above-mentioned Other than perfluoropolyethers having a poly(oxyperfluoroalkylene) group between the poly(oxyperfluoroalkylene) group and the aforementioned urethane bond)] In the present invention, as the component (b), it is used on both ends of the molecular chain containing a poly(oxyperfluoroalkylene) group, and the aminomethyl group is not interposed between the poly(oxyalkylene) group. A perfluoropolyether having an active energy ray polymerizable group having an ester bond (hereinafter referred to as "(b) a perfluoropolyether having a polymerizable group at both terminals" only sometimes). The component (b) functions as a surface modifier in the hard coat layer of the curable composition to which the present invention is applied. Moreover, (b) component is excellent in compatibility with (a) component, and the cloudiness phenomenon of a hard-coat layer can be suppressed by this, and the hard-coat layer which shows a transparent appearance can be formed. In addition, the poly(oxyalkylene) group means a group in which the number of repeating units of the oxyalkylene group is 2 or more and the alkylene group in the oxyalkylene group is an unsubstituted alkylene group.
於上述聚(氧基全氟伸烷基)基中之伸烷基的碳原子數並無特別限定,以碳原子數1~4者為佳。即,上述聚(氧基全氟伸烷基)基表示具有碳原子數1~4的2價氟化碳基與氧原子以交互連結的結構之基,氧全氟伸烷基表示具有碳原子數1~4的2價氟化碳基與氧原子經連結的結構之基。具體可舉出-[OCF2 ]-(氧全氟伸甲基)、 -[OCF2 CF2 ]-(氧全氟伸乙基)、-[OCF2 CF2 CF2 ]-(氧全氟丙烷-1,3-二基)、-[OCF2 C(CF3 )F]-(氧全氟丙烷-1,2-二基)等基。 上述氧全氟伸烷基可單獨使用一種或組合二種以上使用,視所需複數種的氧全氟伸烷基之鍵結可為嵌合鍵結及無規鍵結中任一種。The number of carbon atoms in the alkylene group in the above poly(oxyperfluoroalkylene) group is not particularly limited, but those with 1 to 4 carbon atoms are preferred. That is, the above-mentioned poly(oxyperfluoroalkylene) group means a group having a structure in which a divalent carbon fluoride group having 1 to 4 carbon atoms and an oxygen atom are alternately linked, and the oxyperfluoroalkylene group means a group having a carbon atom The base of the structure in which the divalent fluorinated carbon group of the number 1 to 4 is connected to an oxygen atom. Specific examples include -[OCF 2 ]-(oxyperfluoromethyl), -[OCF 2 CF 2 ]-(oxyperfluoroethyl), -[OCF 2 CF 2 CF 2 ]-(oxyperfluoro propane-1,3-diyl), -[OCF 2 C(CF 3 )F]-(oxyperfluoropropane-1,2-diyl) and the like. The above-mentioned oxyperfluoroalkylene groups can be used singly or in combination of two or more kinds, and the bonding of plural kinds of oxyperfluoroalkylene groups can be any of chimeric bonding and random bonding depending on the need.
此等中,由可得到可成為耐擦傷性良好的硬化膜之觀點來看,作為聚(氧基全氟伸烷基)基,以使用具有作為重複單位的-[OCF2 ]-(氧全氟伸甲基)與-[OCF2 CF2 ]-(氧全氟伸乙基)的雙方之基為佳。 其中亦作為上述聚(氧基全氟伸烷基)基,以重複單位:-[OCF2 ]-與-[OCF2 CF2 ]-的莫耳比率為[重複單位: -[OCF2 ]-]:[重複單位:-[OCF2 CF2 ]-]=2:1~1:2的比例下含有的基為佳,以約1:1的比例下含有的基為較佳。這些重複單位的鍵結可為嵌合鍵結及無規鍵結中任一種。 上述氧全氟伸烷基的重複單位數中作為該重複單位數的總計而言以5~30的範圍者為佳,以7~21的範圍者為較佳。 又,上述聚(氧基全氟伸烷基)基藉由凝膠滲透層析法以聚苯乙烯換算所測定的重量平均分子量(Mw)為1,000~5,000,以1,500~2,000為佳。Among them, from the viewpoint of obtaining a cured film with good scratch resistance, as the poly(oxyperfluoroalkylene) group, -[OCF 2 ]-(oxyperfluoroalkylene) having as a repeating unit is used. Both groups of fluoromethyl) and -[OCF 2 CF 2 ]-(oxyperfluoroethyl) are preferred. Wherein it is also used as the above-mentioned poly(oxy perfluoroalkylene) group, and the molar ratio of the repeating unit: -[OCF 2 ]- to -[OCF 2 CF 2 ]- is [repeating unit: -[OCF 2 ]- ]: [repeating unit: -[OCF 2 CF 2 ]-]=2:1 to 1:2 are preferred, and about 1:1 is preferred. The linkage of these repeating units may be any of chimeric linkage and random linkage. The total number of repeating units in the above-mentioned oxyperfluoroalkylene group is preferably in the range of 5-30, more preferably in the range of 7-21. Furthermore, the poly(oxyperfluoroalkylene) group has a weight average molecular weight (Mw) of 1,000 to 5,000, preferably 1,500 to 2,000 as measured in terms of polystyrene by gel permeation chromatography.
作為上述隔著胺基甲酸酯鍵進行鍵結的活性能量線聚合性基,可舉出(甲基)丙烯醯基、胺基甲酸酯(甲基)丙烯醯基、乙烯基等。Examples of the active energy ray polymerizable group to be bonded via a urethane bond include a (meth)acryl group, a urethane (meth)acryl group, a vinyl group, and the like.
(b)於兩末端具有聚合性基的全氟聚醚並未限定為於兩末端具有1個(甲基)丙烯醯基等活性能量線聚合性基者,亦可為於兩末端上具有2個以上活性能量線聚合性基者,例如作為含有活性能量線聚合性基的末端結構,可舉出以下所示的A1~A5之結構,及這些結構中之丙烯醯基以甲基丙烯醯基所取代的結構。(b) The perfluoropolyether having a polymerizable group at both ends is not limited to one having an active energy ray polymerizable group such as a (meth)acryl group at both ends, and may have 2 at both ends. For those with more than one active energy ray polymerizable group, for example, as the terminal structure containing the active energy ray polymerizable group, the structures of A1 to A5 shown below, and the acryl group and methacryl group in these structures can be mentioned. The replaced structure.
作為如此(b)於兩末端具有聚合性基的全氟聚醚,例如可舉出以下式[2]所示化合物。 (式中,A表示前述式[A1]~式[A5]所示結構及將這些結構中之丙烯醯基以甲基丙烯醯基所取代的結構中之1者,PFPE表示前述聚(氧基全氟伸烷基)基(但,與L1 直接鍵結的側為氧末端,與氧原子鍵結的側為全氟伸烷基末端。),L1 表示以氟原子1~3個所取代的碳原子數2~3的伸烷基,m各獨立表示1~5的整數,L2 表示自m+1價醇除去OH的m+1價殘基)。Examples of the perfluoropolyether having a polymerizable group at both terminals (b) in this way include compounds represented by the following formula [2]. (In the formula, A represents one of the structures represented by the aforementioned formula [A1] to formula [A5] and a structure in which the acryl group in these structures is replaced by a methacryl group, and PFPE represents the aforementioned poly(oxyl group) Perfluoroalkylene) group (However, the side directly bonded to L1 is an oxygen terminal, and the side bonded to an oxygen atom is a perfluoroalkylene terminal.), L1 means that it is substituted with 1 to 3 fluorine atoms Alkylene groups with 2 to 3 carbon atoms, each of m independently represents an integer of 1 to 5, and L2 represents an m+1-valent residue obtained by removing OH from an m+1-valent alcohol).
作為上述可由1~3個氟原子進行取代的碳原子數2~3之伸烷基,可舉出CH2 CHF、CH2 CF2 、CHFCF2 、CH2 CH2 CHF、CH2 CH2 CF2 、CH2 CHFCF2 等,以CH2 CF2 為佳。Examples of the alkylene group having 2 to 3 carbon atoms which may be substituted by 1 to 3 fluorine atoms include CH2CHF , CH2CF2 , CHFCF2 , CH2CH2CHF , CH2CH2CF2 , CH 2 CHFCF 2 , etc., preferably CH 2 CF 2 .
作為於上述式[2]所示化合物中之部分結構(A-NHC(=O)O)m L2 -,可舉出以下所示的式[B1]~式[B12]所示結構等。 (式中,A表示前述式[A1]~式[A5]所示結構及將於這些結構中之丙烯醯基由甲基丙烯醯基所取代的結構中之一者) 在上述式[B1]~式[B12]所示結構之中,式[B1]及式[B2]相當於m=1之情況,式[B3]~式[B6]相當於m=2之情況,式[B7]~式[B9]相當於m=3之情況,式[B10]~式[B12]相當於m=5之情況。 彼等之中,亦以式[B3]所示結構為佳,特別以式[B3]與式[A3]的組合為佳。Examples of the partial structure (A-NHC(=O)O) m L 2 - in the compound represented by the above formula [2] include structures represented by the following formula [B1] to formula [B12]. (In the formula, A represents one of the structures represented by the above-mentioned formula [A1] to formula [A5] and the structure in which the acryl group in these structures is replaced by a methacryl group) In the above-mentioned formula [B1] ~ Among the structures shown in formula [B12], formula [B1] and formula [B2] correspond to the case of m=1, formula [B3] to formula [B6] correspond to the case of m=2, formula [B7] to Formula [B9] corresponds to the case of m=3, and formula [B10] to formula [B12] correspond to the case of m=5. Among them, the structure represented by the formula [B3] is also preferable, and the combination of the formula [B3] and the formula [A3] is particularly preferable.
作為較佳的(b)於兩末端具有聚合性基的全氟聚醚,可舉出具有式[1]所示部分結構的化合物。 式[1]所示部分結構相當於自式[2]所示化合物除去 A-NHC(=O)的部分。 式[1]中之n表示重複單位-[OCF2 CF2 ]-之數與重複單位-[OCF2 ]-之數的總數,以5~30的範圍之整數為佳,以7~21的範圍之整數為較佳。又,重複單位-[OCF2 CF2 ]-之數與重複單位-[OCF2 ]-之數的比率在2:1~1:2之範圍者為佳,約1:1的範圍者為較佳。這些重複單位之鍵結可為嵌合鍵結及無規鍵結中任一種。As preferable (b) perfluoropolyether which has a polymeric group at both terminals, the compound which has a partial structure represented by a formula [1] is mentioned. The partial structure represented by the formula [1] corresponds to a portion in which A-NHC (=O) is removed from the compound represented by the formula [2]. The n in the formula [1] represents the total number of the repeating unit -[OCF 2 CF 2 ]- and the repeating unit -[OCF 2 ]-, preferably an integer in the range of 5-30, preferably 7-21 Integers in the range are preferred. Also, the ratio of the number of repeating units -[OCF 2 CF 2 ]- to the number of repeating units -[OCF 2 ]- is preferably in the range of 2:1 to 1:2, and the range of about 1:1 is better good. The linkage of these repeating units may be any of chimeric linkage and random linkage.
對於本發明(b)於兩末端具有聚合性基的全氟聚醚的使用比例,對於前述(a)活性能量線硬化性內酯變性多官能單體100質量份時為0.1~10質量份,較佳為0.2~5質量份的比例。The proportion of the perfluoropolyether having a polymerizable group at both ends of the present invention (b) is 0.1 to 10 parts by mass for 100 parts by mass of the active energy ray-curable lactone-denatured polyfunctional monomer of (a), Preferably it is a ratio of 0.2 to 5 parts by mass.
上述(b)於兩末端具有聚合性基的全氟聚醚,例如可藉由對於下式[3] (式中,PFPE、L1 、L2 及m與前述相同意義)所示化合物的兩末端上所存在的羥基,將具有聚合性基的異氰酸酯化合物,即將前述式[A1]~式[A5]所示結構及這些結構中之丙烯醯基以甲基丙烯醯基進行取代的結構中之結合鍵上鍵結異氰酸酯基的化合物(例如,2-(甲基)丙烯醯氧基乙基異氰酸酯、1,1-雙((甲基)丙烯醯氧基甲基)乙基異氰酸酯等)進行反應後形成胺基甲酸酯鍵而得到。The above (b) perfluoropolyether having a polymerizable group at both ends can be obtained by, for example, the following formula [3] (In the formula, PFPE, L 1 , L 2 and m have the same meanings as described above) The hydroxyl groups present at both ends of the compound represented by the polymerizable isocyanate compound, that is, the aforementioned formula [A1] to formula [A5] Compounds in which an isocyanate group is bonded to a bond in the structures shown and those structures in which the acryl group is substituted with a methacryl group (for example, 2-(meth)acryloxyethyl isocyanate, 1 , 1-bis ((meth) acryloxymethyl) ethyl isocyanate, etc.) are reacted to form urethane bonds.
且,於本發明之硬化性組成物中,除含有(b)於含有聚(氧基全氟伸烷基)基的分子鏈之兩末端上隔著胺基甲酸酯鍵具有活性能量線聚合性基的全氟聚醚(但,在前述聚(氧基全氟伸烷基)基與前述胺基甲酸酯鍵之間不具有聚(氧化伸烷基)基)以外,亦可含有於含有聚(氧基全氟伸烷基)基的分子鏈之一端上隔著胺基甲酸酯鍵,具有活性能量線聚合性基,且於該他端上具有羥基之全氟聚醚(但,在前述聚(氧基全氟伸烷基)基與前述胺基甲酸酯鍵之間以及於前述聚(氧基全氟伸烷基)基與前述羥基之間不具有聚(氧化伸烷基)基),或如上述式[3]所示之含有聚(氧基全氟伸烷基)基之於分子鏈的兩端上具有羥基之全氟聚醚(但,在前述聚(氧基全氟伸烷基)基與前述羥基之間不具有聚(氧化伸烷基)基)[不具有活性能量線聚合性基之化合物]。In addition, in the curable composition of the present invention, in addition to containing (b) a poly(oxyperfluoroalkylene) group-containing molecular chain having active energy ray polymerization via a urethane bond at both ends In addition to the perfluoropolyether of the radical (however, there is no poly(oxyalkylene) group between the aforementioned poly(oxyperfluoroalkylene) group and the aforementioned urethane bond), it may also be contained in A perfluoropolyether (but , there is no poly(oxyalkylene) between the aforementioned poly(oxygen perfluoroalkylene) group and the aforementioned urethane bond and between the aforementioned poly(oxygen perfluoroalkylene) group and the aforementioned hydroxyl group base) group), or a perfluoropolyether having hydroxyl groups at both ends of the molecular chain containing a poly(oxy perfluoroalkylene) group as shown in the above formula [3] (however, in the aforementioned poly(oxygen There is no poly(oxyalkylene) group between the perfluoroalkylene) group and the aforementioned hydroxyl group) [a compound without an active energy ray polymerizable group].
本發明且為有關含有聚(氧基全氟伸烷基)基的分子鏈之各兩末端上隔著胺基甲酸酯鍵,具有至少3個活性能量線聚合性基之全氟聚醚化合物(但,除去在前述聚(氧基全氟伸烷基)基與前述胺基甲酸酯鍵之間具有聚(氧化伸烷基)基之全氟聚醚化合物以外)。 作為上述於兩末端具有聚合性基的全氟聚醚化合物,以具有上述式[1]所示部分結構之化合物為佳。 本發明之全氟聚醚化合物如上述,其與(a)成分之相溶性優良,藉此可抑制硬質塗布層的白濁現像,可達成呈現透明外觀的硬質塗布層之形成的優異效果。 本發明又有關由上述全氟聚醚化合物所成的表面改質劑,以及欲使用於該全氟聚醚化合物之表面改質者。The present invention also relates to a perfluoropolyether compound having at least 3 active energy ray polymerizable groups at both ends of a molecular chain containing a poly(oxyperfluoroalkylene) group via a urethane bond. (However, perfluoropolyether compounds having a poly(oxyalkylene) group between the aforementioned poly(oxyperfluoroalkylene) group and the aforementioned urethane bond are excluded). As the perfluoropolyether compound having polymerizable groups at both terminals, a compound having a partial structure represented by the above formula [1] is preferable. As mentioned above, the perfluoropolyether compound of the present invention has excellent compatibility with component (a), thereby suppressing the cloudiness of the hard coat layer and achieving the excellent effect of forming a hard coat layer with a transparent appearance. The present invention also relates to a surface modifying agent made of the above-mentioned perfluoropolyether compound, and a surface modifying agent intended to be used for the perfluoropolyether compound.
[(c)藉由活性能量線產生自由基之聚合起始劑] 本發明之硬化性組成物中較佳的藉由活性能量線產生自由基之聚合起始劑(以下有時僅稱為「(c)聚合起始劑」),例如其為藉由電子線、紫外線、X線等活性能量線,特別為藉由紫外線照射使其產生自由基的聚合起始劑。 作為上述(c)聚合起始劑,例如可舉出安息香類、烷基苯乙酮類、噻噸酮類、偶氮類、疊氮化物類、二氮類、o-醌二疊氮化物類、醯基膦氧化物類、肟酯類、有機過氧化物、二苯甲酮類、雙香豆素類、雙咪唑類、二茂鈦類、硫醇類、鹵化烴類、三氯甲基三嗪類、或者碘鹽、鋶鹽等鎓鹽類等。可使用單獨使用一種,或亦可混合二種以上使用。 其中本發明中,由透明性、表面硬化性、薄膜硬化性之觀點,作為(c)聚合起始劑,以使用烷基苯乙酮類者為佳。藉由使用烷基苯乙酮類,可得到更提高耐擦傷性之硬化膜。[(c) Polymerization initiator that generates free radicals by active energy rays] In the curable composition of the present invention, preferable polymerization initiators that generate radicals by active energy rays (hereinafter sometimes simply referred to as "(c) polymerization initiators") are, for example, those that generate radicals by electron rays, Active energy rays such as ultraviolet rays and X-rays, especially polymerization initiators that generate free radicals by ultraviolet irradiation. Examples of the above (c) polymerization initiator include benzoins, alkylacetophenones, thioxanthones, azos, azides, diazides, and o-quinonediazides. , Acylphosphine oxides, oxime esters, organic peroxides, benzophenones, dicoumarins, biimidazoles, titanocenes, mercaptans, halogenated hydrocarbons, trichloromethyl Triazines, or onium salts such as iodine salts and permeic acid salts, and the like. One type may be used alone, or two or more types may be used in combination. Among them, in the present invention, it is preferable to use alkyl acetophenones as the (c) polymerization initiator from the viewpoint of transparency, surface hardening properties, and film hardening properties. By using alkyl acetophenones, a cured film having improved scratch resistance can be obtained.
作為上述烷基苯乙酮類,例如可舉出1-羥基環己基=苯基=酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、2-羥基-1-(4-(2-羥基乙氧基)苯基)-2-甲基丙烷-1-酮、2-羥基-1-(4-(4-(2-羥基-2-甲基丙醯基)苯甲基)苯基)-2-甲基丙烷-1-酮等α-羥基烷基苯乙酮類;2-甲基-1-(4-(甲基硫基)苯基)-2-嗎啉代丙烷-1-酮、2-苯甲基-2-二甲基胺基-1-(4-嗎啉代苯基)丁烷-1-酮等α-胺基烷基苯乙酮類;2,2-二甲氧基-1,2-二苯基乙烷-1-酮;苯基乙醛酸甲基等。Examples of the above-mentioned alkylacetophenones include 1-hydroxycyclohexyl=phenyl=ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1-( 4-(2-hydroxyethoxy)phenyl)-2-methylpropan-1-one, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzene α-Hydroxyalkylacetophenones such as methyl)phenyl)-2-methylpropan-1-one; 2-methyl-1-(4-(methylthio)phenyl)-2-mol α-aminoalkylacetophenones such as phenopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, etc. ; 2,2-dimethoxy-1,2-diphenylethan-1-one; methyl phenylglyoxylate, etc.
對於本發明,(c)聚合起始劑的使用比例對於前述(a)活性能量線硬化性內酯變性多官能單體100質量份而言為1~20質量份,較佳為2~10質量份。In the present invention, the ratio of the (c) polymerization initiator to be used is 1 to 20 parts by mass, preferably 2 to 10 parts by mass, relative to 100 parts by mass of the aforementioned (a) active energy ray-curable lactone-denatured polyfunctional monomer. share.
[(d)溶劑] 本發明之硬化性組成物可進一步含有(d)溶劑,即亦可作為塗漆(膜形成材料)之形態。 作為上述溶劑,若為溶解前述(a)~(c)成分,又考慮到有關後述硬化膜(硬質塗布層)形成之塗層時的作業性或硬化前後之乾燥性等時,僅適宜地選擇即可,例如可舉出苯、甲苯、二甲苯、乙基苯、四氫萘等芳香族烴類;n-己烷、n-庚烷、礦物油、環己烷等脂肪族或脂環式烴類;氯化甲基、溴化甲基、碘化甲基、二氯甲烷、氯仿、四氯化碳、三氯伸乙基、全氯乙烯、o-二氯苯等鹵素化物類;乙酸乙酯、乙酸丁酯、甲氧基丁基乙酸酯、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、丙二醇單甲基醚乙酸酯等酯類或酯醚類;二乙基醚、四氫呋喃、1,4-二噁烷、甲基溶纖劑、乙基溶纖劑、丁基溶纖劑、丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單-n-丙基醚、丙二醇單異丙基醚、丙二醇單-n-丁基醚等醚類;丙酮、甲基乙基酮、甲基異丁基酮、二-n-丁基酮、環己酮等酮類;甲醇、乙醇、n-丙醇、異丙醇、n-丁醇、異丁基醇、tert-丁基醇、2-乙基己基醇、苯甲基醇、乙二醇等醇類;N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯啶酮等醯胺類;二甲基亞碸等亞碸類,以及這些2種以上之混合溶劑。 這些(d)溶劑之使用量並無特別限定,例如對於本發明之硬化性組成物中的固體成分濃度為1~70質量%,以在5~50質量%的濃度下使用為佳。其中,所謂固體成分濃度(亦稱為不揮發分濃度)表示對於本發明之硬化性組成物的前述(a)~(d)成分(及依據所望的其他添加劑)之總質量(合計質量)的固體成分(自全成分除去溶劑成分者)之含有量。[(d) Solvent] The curable composition of the present invention may further contain (d) a solvent, that is, it may also be in the form of a paint (film forming material). As the above-mentioned solvent, if it is to dissolve the above-mentioned (a) to (c) components, and consider the workability of the coating when the cured film (hard coat layer) is formed later, or the drying properties before and after curing, etc., it can only be selected appropriately. That is, for example, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral oil, and cyclohexane Hydrocarbons; methyl chloride, methyl bromide, methyl iodide, methylene chloride, chloroform, carbon tetrachloride, trichloroethylenyl, perchloroethylene, o-dichlorobenzene and other halogenated compounds; acetic acid Ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate and other esters or ester ethers; Diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl Ether, propylene glycol monoisopropyl ether, propylene glycol mono-n-butyl ether and other ethers; acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone and other ketones ; Methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutyl alcohol, tert-butyl alcohol, 2-ethylhexyl alcohol, benzyl alcohol, ethylene glycol and other alcohols; N , Amides such as N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.; Acids such as dimethylsulfide, and these two kinds The above mixed solvents. The amount of these (d) solvents used is not particularly limited. For example, the solid content concentration in the curable composition of the present invention is 1 to 70% by mass, preferably used at a concentration of 5 to 50% by mass. Here, the so-called solid content concentration (also referred to as non-volatile matter concentration) refers to the total mass (total mass) of the aforementioned (a) to (d) components (and other additives depending on the desired) of the curable composition of the present invention. The content of solid content (the solvent content is removed from the whole content).
[其他添加物] 又,對於本發明之硬化性組成物,不損害本發明之效果下,視必要可適宜地添加一般添加的添加劑,例如可適宜地添加聚合禁止劑、光增感劑、塗平劑、界面活性劑、密著性賦予劑、可塑劑、紫外線吸收劑、抗氧化劑、貯藏安定劑、帶電防止劑、無機填充劑、顏料、染料等。[other additions] Also, for the curable composition of the present invention, without impairing the effect of the present invention, additives generally added can be appropriately added as necessary, such as polymerization inhibitors, photosensitizers, leveling agents, and surface active agents. agent, adhesion imparting agent, plasticizer, ultraviolet absorber, antioxidant, storage stabilizer, antistatic agent, inorganic filler, pigment, dye, etc.
<硬化膜> 本發明之硬化性組成物塗布於基材上而形成塗膜,藉由於該塗膜照射活性能量線使其聚合(硬化),形成硬化膜。該硬化膜亦作為本發明的對象。又,可將於後述硬質塗布薄膜中之硬質塗布層作為由該硬化膜所成者。 作為該情況的前述基材,例如可舉出各種樹脂(聚碳酸酯、聚甲基丙烯酸酯、聚苯乙烯、聚乙烯對苯二甲酸乙二醇酯(PET)或聚乙烯萘二甲酸酯(PEN)等聚酯、聚烯烴、聚醯胺、聚醯亞胺、環氧樹脂、三聚氰胺樹脂、三乙醯纖維素、丙烯腈-丁二烯-苯乙烯共聚物(ABS)、丙烯腈-苯乙烯共聚物(AS)、降冰片烯系樹脂等)、金屬、木材、紙、玻璃、板岩等。這些基材的形狀亦可為板狀、薄膜狀或3次元成形體。<Cured film> The curable composition of the present invention is coated on a substrate to form a coating film, and the coating film is polymerized (cured) by irradiating active energy rays to form a cured film. This cured film is also made into the object of this invention. Moreover, the hard coat layer in the hard coat film mentioned later can be made of this cured film. As the aforementioned base material in this case, various resins (polycarbonate, polymethacrylate, polystyrene, polyethylene terephthalate (PET) or polyethylene naphthalate) can be mentioned, for example. (PEN) and other polyesters, polyolefins, polyamides, polyimides, epoxy resins, melamine resins, triacetyl cellulose, acrylonitrile-butadiene-styrene copolymers (ABS), acrylonitrile- Styrene copolymer (AS), norbornene-based resin, etc.), metal, wood, paper, glass, slate, etc. The shapes of these substrates may be plate-like, film-like, or three-dimensional molded bodies.
對於前述基材上的塗布方法可適宜地選擇鑄塗膜法、旋轉塗布法、刮刀塗布法、浸塗法、輥塗布法、噴霧塗布法、棒塗布法、模塗法、噴墨法、印刷法(凸版、凹版、平版、絲網印刷等)等,其中可利用卷對卷(roll-to-roll)法,又由薄膜塗布性之觀點來看,可望使用凸版印刷法,特別使用凹版塗布法。且,於事前使用孔徑0.2μm程度的濾器等,過濾硬化性組成物後,提供於塗布者為佳。且塗布時,視必要於該硬化性組成物添加溶劑亦可作為塗漆之形態。作為該此狀況之溶劑,可舉出在前述[(d)溶劑]所舉出的種種溶劑。 於基材上塗布硬化性組成物形成塗膜後,視必要藉由加熱板或烤箱等將塗膜進行預備乾燥而除去溶劑(溶劑除去步驟)。作為此時的加熱乾燥之條件,例如在40~120℃進行30秒~10分鐘程度者為佳。 乾燥後,照射紫外線等活性能量線,使塗膜硬化。作為活性能量線,可舉出紫外線、電子線、X線等,特別以紫外線為佳。作為使用於紫外線照射的光源,可使用太陽光線、化學燈、低壓水銀燈、高壓水銀燈、金屬鹵素燈、氙氣燈、UV-LED等。 且其後,藉由進行後烘烤,具體為使用加熱板、烤箱等進行加熱而使聚合完成。 且,所形成的硬化膜之厚度對於乾燥、硬化後而言,通常為0.01~50μm,較佳為0.05~20μm。For the coating method on the aforementioned substrate, cast coating method, spin coating method, knife coating method, dip coating method, roll coating method, spray coating method, rod coating method, die coating method, inkjet method, printing method, etc. method (letterpress, gravure, lithography, screen printing, etc.), among which roll-to-roll (roll-to-roll) method can be used, and from the viewpoint of film coatability, it is expected to use letterpress printing method, especially gravure printing method coating method. Furthermore, it is preferable to provide the applicator after filtering the curable composition in advance using a filter with a pore size of about 0.2 μm or the like. In addition, when coating, adding a solvent to the curable composition as necessary can also be used as a form of painting. As a solvent in this case, various solvents mentioned in said [(d) solvent] are mentioned. After coating the curable composition on the substrate to form a coating film, the coating film is pre-dried with a hot plate or an oven if necessary to remove the solvent (solvent removal step). As the conditions of heat drying at this time, it is preferable to perform, for example, at 40 to 120°C for about 30 seconds to 10 minutes. After drying, the coating is cured by irradiating active energy rays such as ultraviolet rays. Examples of active energy rays include ultraviolet rays, electron rays, X-rays, and the like, and ultraviolet rays are particularly preferred. As a light source used for ultraviolet irradiation, sunlight, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, xenon lamps, UV-LEDs, and the like can be used. And thereafter, polymerization is completed by performing post-baking, specifically, heating using a hot plate, an oven, or the like. In addition, the thickness of the formed cured film is usually 0.01 to 50 μm after drying and curing, preferably 0.05 to 20 μm.
<硬質塗布薄膜> 使用本發明之硬化性組成物,可製造出於薄膜基材的至少一面(表面)具備硬質塗布層的硬質塗布薄膜。該硬質塗布薄膜亦為本發明之對象,該硬質塗布薄膜可適用於保護例如觸控板或液晶顯示等各種顯示元件等表面。<Hard Coating Film> Using the curable composition of the present invention, a hard coat film having a hard coat layer on at least one side (surface) of a film substrate can be produced. The hard coating film is also the object of the present invention, and the hard coating film is suitable for protecting the surfaces of various display elements such as touch panels or liquid crystal displays.
於本發明之硬質塗布薄膜中之硬質塗布層可藉由含有將前述本發明之硬化性組成物塗布於薄膜基材上形成塗膜之步驟、於該塗膜照射紫外線等活性能量線使該塗膜硬化的步驟之方法而形成。The hard coat layer in the hard coat film of the present invention can be formed by applying the curable composition of the present invention to a film substrate to form a coating film, irradiating the coating film with active energy rays such as ultraviolet rays to make the coating layer Formed by the method of film hardening step.
作為前述薄膜基材,可舉出在前述<硬化膜>所舉出的基材中,可使用於光學用途之各種透明樹脂製薄膜。較佳例如可舉出選自聚乙烯對苯二甲酸乙二醇酯(PET)、聚丁烯對苯二甲酸乙二醇酯(PBT)、聚乙烯萘二甲酸酯(PEN)等之聚酯、聚碳酸酯、聚甲基丙烯酸酯、聚苯乙烯、聚烯烴、聚醯胺、聚醯亞胺、三乙醯纖維素等樹脂製薄膜。 又,對於前述薄膜基材上的硬化性組成物之塗布方法(塗膜形成步驟)及對於塗膜的活性能量線照射方法(硬化步驟)可使用在前述<硬化膜>所舉出的方法。又,於本發明之硬化性組成物含有溶劑(塗漆形態之)的情況,在塗膜形成步驟後,視必要可含有乾燥該塗膜使溶劑除去的步驟。此時,可使用在前述<硬化膜>所舉出的塗膜之乾燥方法(溶劑除去步驟)。 如此所得之硬質塗布層的膜厚,以1~20μm為佳,較佳為1~10μm。 [實施例]Examples of the film base material include various transparent resin films that can be used for optical applications among the base materials listed in the aforementioned <cured film>. Preferred examples include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN) and the like. Polyester, polycarbonate, polymethacrylate, polystyrene, polyolefin, polyamide, polyimide, triacetyl cellulose and other resin films. Also, the methods mentioned above in <cured film> can be used for the method of coating the curable composition on the film substrate (coating film forming step) and the method of irradiating the coating film with active energy rays (curing step). Also, when the curable composition of the present invention contains a solvent (in the form of a paint), after the coating film forming step, a step of drying the coating film to remove the solvent may be included if necessary. At this time, the drying method (solvent removal step) of the coating film mentioned above in <cured film> can be used. The film thickness of the hard coat layer thus obtained is preferably 1 to 20 μm, more preferably 1 to 10 μm. [Example]
以下可舉出實施例,可更具體說明本發明,但本發明並未限定於此下述實施例。 且,對於實施例,使用於試料的調製及物性分析之裝置及條件如以下所示。Examples are given below, and the present invention can be described more specifically, but the present invention is not limited to the following examples. In addition, in Examples, the apparatus and conditions used for preparation of samples and analysis of physical properties are as follows.
(1)棒塗布塗布 裝置:(股)SMT製 PM-9050MC 棒:OSG System Products(股)製 A-Bar OSP-22,最大濕膜厚22μm(線錠#9相當) 塗布速度:4m/分鐘 (2)烤箱 裝置:Advantech Oriental(股)製之無塵乾燥器 DRC433FA (3)UV硬化 裝置:Heraeus(股)製 CV-110QC-G 燈光:Heraeus(股)製 高壓水銀燈H-bulb (4)凝膠滲透層析法(GPC) 裝置:Tosoh公司(股)製 HLC-8220GPC 管柱:昭和電工(股)製 Shodex(註冊商標)GPC K-804L、GPC K-805L 管柱溫度:40℃ 溶離液:四氫呋喃 檢測器:RI (5)擦傷試驗 裝置:新東科學(股)製 往返摩耗試驗機 TRIBOGEAR TYPE:30S 掃描速度:3,000mm/分鐘 掃描距離:50mm (6)全光線透過率、霧度 裝置:日本電色工業(股)製 霧度測試器 NDH5000 (7)接觸角 裝置:協和界面科學(股)製 DropMaster DM-501 測定溫度:20℃ (8)拉伸試驗 裝置:(股)島津製作所製 卓上形精密萬能試驗機Autograph AGS - 10 kNX 夾抓具:1kN手動扭轉式平面形夾抓具 抓牙:高強度塗膠抓牙 拉伸速度:20mm/分鐘 測定溫度:20℃(1) Bar coating Device: PM-9050MC made by SMT Rod: A-Bar OSP-22 manufactured by OSG System Products Co., Ltd., with a maximum wet film thickness of 22 μm (equivalent to wire spindle #9) Coating speed: 4m/min (2) Oven Device: Dust-free dryer DRC433FA manufactured by Advantech Oriental Co., Ltd. (3) UV hardening Device: CV-110QC-G manufactured by Heraeus Co., Ltd. Lighting: Heraeus Co., Ltd. high-pressure mercury lamp H-bulb (4) Gel Permeation Chromatography (GPC) Device: HLC-8220GPC manufactured by Tosoh Co., Ltd. String: Shodex (registered trademark) GPC K-804L, GPC K-805L manufactured by Showa Denko Co., Ltd. Column temperature: 40°C Eluent: Tetrahydrofuran Detector: RI (5) Scratch test Device: Shinto Science Co., Ltd. reciprocating abrasion tester TRIBOGEAR TYPE: 30S Scanning speed: 3,000mm/min Scanning distance: 50mm (6) Total light transmittance, haze Device: Nippon Denshoku Industry Co., Ltd. haze tester NDH5000 (7) Contact angle Device: DropMaster DM-501 manufactured by Kyowa Interface Science Co., Ltd. Measuring temperature: 20°C (8) Tensile test Device: Takumi Precision Universal Testing Machine Autograph AGS - 10 kNX manufactured by Shimadzu Corporation Gripper: 1kN manual torsion flat gripper Teeth gripping: high-strength rubberized gripping teeth Tensile speed: 20mm/min Measuring temperature: 20°C
又,簡稱號碼表示以下意思。 PFPE1:各兩末端不隔著聚(氧化伸烷基)基具有2個羥基之全氟聚醚[Solvay Specialty Polymers, Inc.製 Fomblin(註冊商標)T4] PFPE2:於兩末端隔著聚(氧化伸烷基)基(重複單位數8~9)具有羥基的全氟聚醚[Solvay Specialty Polymers, Inc.製 Fluorolink 5147X] SM2:於各兩末端隔著胺基甲酸酯鍵具有2個甲基丙烯醯基之全氟聚醚[Solvay Specialty Polymers, Inc.製 Fomblin(註冊商標)MT70、80質量%MEK溶液] BEI:1,1-雙(丙烯醯氧基甲基)乙基異氰酸酯[昭和電工(股)製 Karenz(註冊商標)BEI] DOTDD:二新癸烷酸二辛基錫[日東化成(股)製 Neostan(註冊商標)U-830] DPCL:己內酯變性二季戊四醇六丙烯酸酯[日本化藥(股)製 KAYARAD DPCA-60] DPHA:二季戊四醇五丙烯酸酯/二季戊四醇六丙烯酸酯混合物[日本化藥(股)製 KAYARAD DPHA] PETA:季戊四醇三丙烯酸酯/季戊四醇四丙烯酸酯混合物[新中村化學工業(股)製 NK酯 A-TMM-3LM-N] I2959:2-羥基-1-(4-(2-羥基乙氧基)苯基)-2-甲基丙烷-1-酮[BASF日本(股)製 IRGACURE(註冊商標)2959] MEK:甲基乙基酮 PGME:丙二醇單甲基醚Also, the abbreviated numbers indicate the following meanings. PFPE1: perfluoropolyether [Fomblin (registered trademark) T4 manufactured by Solvay Specialty Polymers, Inc.] having two hydroxyl groups without a poly(oxyalkylene) group interposed between both ends PFPE2: Perfluoropolyether having a hydroxyl group via a poly(oxyalkylene) group (number of repeating units: 8 to 9) at both ends [Solvay Specialty Polymers, Inc. Fluorolink 5147X] SM2: Perfluoropolyether having two methacryl groups at both ends via a urethane bond [Solvay Specialty Polymers, Inc. Fomblin (registered trademark) MT70, 80% by mass MEK solution] BEI: 1,1-bis(acryloxymethyl)ethyl isocyanate [Karenz (registered trademark) BEI manufactured by Showa Denko Co., Ltd.] DOTDD: Dioctyltin dineodecanoate [Neostan (registered trademark) U-830 manufactured by Nitto Kasei Co., Ltd.] DPCL: Caprolactone-denatured dipentaerythritol hexaacrylate [KAYARAD DPCA-60 manufactured by Nippon Kayaku Co., Ltd.] DPHA: dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate mixture [KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.] PETA: Pentaerythritol triacrylate/pentaerythritol tetraacrylate mixture [NK Ester A-TMM-3LM-N manufactured by Shin-Nakamura Chemical Co., Ltd.] I2959: 2-Hydroxy-1-(4-(2-hydroxyethoxy)phenyl)-2-methylpropan-1-one [IRGACURE (registered trademark) 2959 manufactured by BASF Japan Co., Ltd.] MEK: methyl ethyl ketone PGME: Propylene Glycol Monomethyl Ether
[實施例1]於各兩末端隔著胺基甲酸酯鍵具有4個丙烯醯基之全氟聚醚(SM1)的製造 於螺絲管裝入PFPE1 1.19g(0.5mmol)、BEI 0.52g(2.0mmol)、DOTDD 0.017g(PFPE1及BEI之合計質量的0.01倍量)及MEK 1.67g。將該混合物使用攪拌器片在室溫(約23℃)下攪拌24小時,得到目的化合物之SM1的50質量%MEK溶液。 藉由所得之SM1的GPC以聚苯乙烯換算所測定的重量平均分子量:Mw為3,000,分散度:Mw(重量平均分子量)/Mn(數平均分子量)為1.2。[Example 1] Production of perfluoropolyether (SM1) having 4 acryl groups via urethane bonds at both ends 1.19g (0.5mmol) of PFPE1, 0.52g (2.0mmol) of BEI, 0.017g of DOTDD (0.01 times the total mass of PFPE1 and BEI) and 1.67g of MEK were placed in the screw tube. This mixture was stirred at room temperature (about 23° C.) for 24 hours using a stirrer blade to obtain a 50% by mass MEK solution of SM1 of the target compound. The weight average molecular weight measured by GPC of the obtained SM1 in terms of polystyrene: Mw was 3,000, and the degree of dispersion: Mw (weight average molecular weight)/Mn (number average molecular weight) was 1.2.
[製造例1]SM2之50質量%MEK溶液的調製 於螺絲管中裝入SM2 2.5g及MEK 1.5g。將該混合物使用攪拌器片在室溫(約23℃)下進行24小時攪拌,得到SM2的50質量%MEK溶液。[Manufacturing example 1] Preparation of 50% by mass MEK solution of SM2 Put SM2 2.5g and MEK 1.5g into the screw tube. This mixture was stirred at room temperature (about 23° C.) for 24 hours using a stirrer blade to obtain a 50% by mass MEK solution of SM2.
[比較製造例1]於各兩末端隔著聚(氧化伸烷基)基及1個胺基甲酸酯鍵且具有2個丙烯醯基之全氟聚醚(SM3)的製造 於螺絲管中裝入PFPE2 1.05g(0.5mmol)、BEI 0.26g(1.0mmol)、DOTDD 0.013g(PFPE2及BEI之合計質量的0.01倍量)及MEK 1.30g。將該混合物使用攪拌器片在室溫(約23℃)下進行24小時攪拌,得到目的化合物之SM3的50質量%MEK溶液。 藉由所得之SM3的GPC以聚苯乙烯換算所測定的重量平均分子量:Mw為3,100,分散度:Mw/Mn為1.1。[Comparative Production Example 1] Production of perfluoropolyether (SM3) having two acryl groups via poly(oxyalkylene) groups and one urethane bond at both ends PFPE2 1.05g (0.5mmol), BEI 0.26g (1.0mmol), DOTDD 0.013g (0.01 times the total mass of PFPE2 and BEI) and MEK 1.30g were placed in the screw tube. This mixture was stirred using a stirrer blade at room temperature (about 23° C.) for 24 hours to obtain a 50% by mass MEK solution of SM3 of the target compound. The weight average molecular weight measured by GPC of the obtained SM3 in terms of polystyrene: Mw was 3,100, and the degree of dispersion: Mw/Mn was 1.1.
[實施例2、3、比較例1~3] 依據表1的記載,混合以下各成分,調製出表1所記載的固體成分濃度之硬化性組成物。且,其中所謂固體成分係指溶劑以外的成分。又,表中[份]表示[質量份]。 (1)多官能單體:表1所記載的多官能單體 100質量份 (2)表面改質劑:將表1所記載的表面改質劑以表1所記載的量(固體成分換算)表示 (3)聚合起始劑:I2959 5質量份 (4)溶劑:PGME 158質量份 將該硬化性組成物使用棒塗布而塗布於A4尺寸的兩面易接著處理PET薄膜[Toray(股)製 Lumirror(商標登録)U403、厚度100μm]上,得到塗膜。將該塗膜在120℃的烤箱進行3分鐘乾燥而除去溶劑。將所得的膜在氮環境下,照射曝光量300mJ/cm2 之UV光使其曝光後,製造出具有約5μm膜厚的硬質塗布層(硬化膜)之硬質塗布薄膜。[Examples 2, 3, Comparative Examples 1-3] Based on the description in Table 1, the following components were mixed to prepare curable compositions with solid content concentrations described in Table 1. In addition, the term "solid content" here refers to components other than the solvent. In addition, [parts] in the table represent [parts by mass]. (1) Multifunctional monomer: 100 parts by mass of the multifunctional monomer listed in Table 1 (2) Surface modifying agent: The surface modifying agent listed in Table 1 is expressed in the amount listed in Table 1 (in terms of solid content) Indicates (3) Polymerization initiator: I2959 5 parts by mass (4) Solvent: 158 parts by mass of PGME This curable composition is coated on both sides of an A4 size easy-to-adhesive PET film [Toray Co., Ltd. Lumirror by bar coating] (trademark registration) U403, thickness 100 μm] to obtain a coating film. The coating film was dried in a 120° C. oven for 3 minutes to remove the solvent. The obtained film was exposed to UV light at an exposure dose of 300 mJ/cm 2 in a nitrogen atmosphere, and then a hard coat film having a hard coat layer (cured film) with a film thickness of about 5 μm was produced.
評估各硬化性組成物之均質性以及所得之硬質塗布薄膜的外觀、耐擦傷性、延伸性、全光線透過率、霧度及水的接觸角。組成物均質性、外觀、耐擦傷性、延伸性、及接觸角的評估程序如以下所示。結果合併表示於表2。 [組成物均質性] 將調製2小時後的硬化性組成物之外觀以目視確認,依據以下基準進行評估。 A:透明溶液 C:白濁 [外觀] 將硬質塗布薄膜的外觀以目視進行確認,依據以下基準進行評估。 A:於通過硬質塗布層全面為透明且無斑點 C:硬質塗布層全面有斑狀且白濁而使斑點醒目 [耐擦傷性] 將硬質塗布層表面以附有往返摩耗試驗機之不銹鋼毛紡[Bonther販賣(股)製 Bonther(註冊商標)#0000(超極細)]施予250g/cm2 的負荷進行2,000往返擦拭,將造成傷痕程度以目視進行確認,依據以下基準進行評估。且,作為硬質塗布層假設實際使用時,至少可求得B,以A為佳。 A:未有傷痕 B:稍有傷痕 C:全面傷痕 [延伸性] 將硬質塗布薄膜取出長度80mm,寬度10mm的矩形,製作出試驗片。自試驗片的縱方向之兩端,將各20mm以萬能試驗機之夾抓具抓住取出,使延伸率(=(夾抓具間距離之增加量)÷(夾抓具間距離)×100)成為5%、10%、15%、20%下進行拉伸試驗。於試驗片的硬質塗布層上未產生裂紋的最大延伸率評估為延伸性。 [接觸角] 將水1μL附著於硬質塗布層表面,測定該5秒後的接觸角θ之5點,將該平均值作為接觸角值。The homogeneity of each curable composition and the appearance, scratch resistance, elongation, total light transmittance, haze and water contact angle of the obtained hard coating film were evaluated. Evaluation procedures for composition homogeneity, appearance, scratch resistance, elongation, and contact angle are as follows. The results are combined and shown in Table 2. [Composition Homogeneity] The appearance of the curable composition after 2 hours of preparation was visually confirmed and evaluated based on the following criteria. A: Transparent solution C: Cloudy [Appearance] The appearance of the hard coat film was visually confirmed and evaluated based on the following criteria. A: The hard coating layer is completely transparent and has no spots. C: The hard coating layer is spotty and white and makes the spots eye-catching. [Scratch resistance] The surface of the hard coating layer is made of stainless steel wool with a reciprocating abrasion tester [Bonther Bonther (registered trademark) #0000 (ultra-fine)] manufactured by Sales Co., Ltd. was rubbed 2,000 times with a load of 250 g/cm 2 , and the degree of damage was visually confirmed and evaluated according to the following criteria. And, assuming actual use as a hard coating layer, at least B can be obtained, and A is preferable. A: No scratches B: Slight scratches C: Full-scale scratches [Extensibility] The hard coating film was taken out into a rectangle with a length of 80 mm and a width of 10 mm to prepare a test piece. From the two ends of the longitudinal direction of the test piece, take out each 20mm with the gripper of the universal testing machine, so that the elongation (= (the increase in the distance between the grippers) ÷ (the distance between the grippers) × 100 ) becomes 5%, 10%, 15%, and 20% to carry out the tensile test. The maximum elongation at which cracks did not occur on the hard coat layer of the test piece was evaluated as elongation. [Contact Angle] 1 μL of water was attached to the surface of the hard coat layer, and the contact angle θ was measured at 5 points after 5 seconds, and the average value was taken as the contact angle value.
【表1】
【表2】
如表1所示,於硬質塗布層中,各使用作為多官能單體將內酯變性丙烯酸酯,作為表面改質劑於各兩末端隔著胺基甲酸酯鍵具有4個丙烯醯基之全氟聚醚SM1(實施例2),或於各兩末端隔著胺基甲酸酯鍵具有2個甲基丙烯醯基之全氟聚醚SM2(實施例3)之硬化性組成物呈現透明溶液,又使用該硬化性組成物所製作的硬質塗布薄膜其具有優良耐擦傷性之同時亦具有適度延伸性,可得到透明且無斑點之外觀。As shown in Table 1, in the hard coat layer, lactone-modified acrylate is used as a multifunctional monomer, and as a surface modifier, acrylates having 4 acryl groups at both ends via urethane bonds are used. The curable composition of perfluoropolyether SM1 (Example 2) or perfluoropolyether SM2 (Example 3) having two methacryl groups via urethane bonds at each end is transparent solution, and the hard coating film produced by using the curable composition has excellent scratch resistance and moderate extensibility, and can obtain a transparent and spot-free appearance.
另一方面,作為表面改質劑使用於各兩末端隔著聚(氧化伸烷基)基及1個胺基甲酸酯鍵之具有2個丙烯醯基的全氟聚醚SM3的比較例2,該組成物為白濁且均質性較差,且由該組成物所得之硬質塗布層與實施例相比較,霧度惡化且外觀為白濁狀態。 又,各使用作為多官能單體未經內酯變性的丙烯酸酯作為表面改質劑的上述SM1之比較例1,結果為皆未具有延伸性。On the other hand, comparative example 2 in which perfluoropolyether SM3 having two acryl groups having two acryl groups interposed between poly(oxyalkylene) groups and one urethane bond at both ends was used as a surface modifying agent , the composition was cloudy and poor in homogeneity, and the hard coating layer obtained from the composition had worse haze and a cloudy appearance than those in Examples. In addition, as a result of Comparative Example 1 using the above-mentioned SM1 as a surface modifying agent, acrylate which is a polyfunctional monomer and which has not been denatured by lactone, none of them had elongation.
以上如實施例之結果所示,組合經內酯變性的多官能單體,及特定全氟聚醚的硬化性組成物,第一次可得到耐擦傷性、延伸性及外觀皆令人滿足的硬質塗布薄膜。As shown in the results of the above examples, combining the polyfunctional monomer modified by lactone and the curable composition of specific perfluoropolyether can obtain a scratch resistance, elongation and appearance satisfactory for the first time. Hard coated film.
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