TWI558777B - A hard coat composition containing an antifouling property - Google Patents
A hard coat composition containing an antifouling property Download PDFInfo
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- TWI558777B TWI558777B TW102112186A TW102112186A TWI558777B TW I558777 B TWI558777 B TW I558777B TW 102112186 A TW102112186 A TW 102112186A TW 102112186 A TW102112186 A TW 102112186A TW I558777 B TWI558777 B TW I558777B
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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
- 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
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
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Description
本發明關於賦予防污性之硬塗層材料,更詳細地,關於添加有在同一分子內具有含氟有機基與烴基和(甲基)丙烯酸基之防污性賦予劑,與在同一分子內具有全氟聚醚基與(甲基)丙烯酸基之防污性賦予劑的賦予防污性之硬塗層組成物。 The present invention relates to a hard coat material which imparts antifouling properties, and more specifically, to an antifouling imparting agent having a fluorine-containing organic group and a hydrocarbon group and a (meth)acrylic group in the same molecule, and in the same molecule A hard coat composition which imparts antifouling properties to an antifouling property imparting agent having a perfluoropolyether group and a (meth)acrylic group.
樹脂材料由於具有與金屬比較下不生銹、輕等之特徵,而廣泛使用於各種電化製品或個人電腦、行動電話等的電子機器之殼體等。又,與玻璃比較下,具有不易破裂等之特徵,丙烯酸樹脂或聚碳酸酯樹脂等之具有高硬度、高透明性等性質的樹脂,係作為單體或硬塗層材料而使用於液晶顯示器或觸控面板等之顯示體。 The resin material is widely used in various electronic products, electronic cases such as personal computers and mobile phones, and the like, because it has characteristics such as no rust and lightness compared with metal. In addition, compared with glass, it has characteristics such as being difficult to be broken, and a resin having high hardness and high transparency such as an acrylic resin or a polycarbonate resin is used as a monomer or a hard coat material for a liquid crystal display or A display body such as a touch panel.
近幾年,尤其在電子機器之殼體等中,從設計面來看,要求高光澤的表面。又,於行動電話或個人電腦用顯示器,具有觸控面板的規格者亦增多,於其最表面上,以防止傷痕等為目的,塗佈丙烯酸樹脂或聚矽氧樹脂等之硬塗 層材料。 In recent years, particularly in the casing of an electronic machine or the like, a high gloss surface is required from the viewpoint of design. In addition, in the case of a mobile phone or a display for a personal computer, there are also a number of specifications including a touch panel. On the outermost surface, a hard coat such as an acrylic resin or a polyoxymethylene resin is applied for the purpose of preventing scratches and the like. Layer material.
此等由於頻繁地與人之手等接觸,皮脂或汗、指紋等的髒污容易附著,當彼等成為痕跡時,多損害外表或視覺辨認性降低。特別地,於靜電容量方式的觸控面板中,必須藉由手指來直接接觸而輸入,無法避免此問題。因此,對於此等的硬塗層材料,強烈要求耐指紋性等之防污性能的提升。 Since such contact with a human hand or the like frequently occurs, sebum, sweat, fingerprints, and the like are easily adhered, and when they become marks, the appearance or the visibility is deteriorated. In particular, in a capacitive touch panel, it is necessary to input by direct contact with a finger, and this problem cannot be avoided. Therefore, for such hard coat materials, an improvement in antifouling properties such as fingerprint resistance is strongly required.
作為此之對策,目前有各種的檢討,大致區分為如以下的2個手法。一個手法為使用聚矽氧系化合物或氟系化合物,在硬塗層表面上形成具有低表面能的撥水.撥油性表面,而指紋等的髒污不易附著,且施予容易去除之處理者。 As a countermeasure against this, there are various reviews at present, which are roughly classified into the following two methods. One method is to use a polyoxymethylene compound or a fluorine compound to form water with low surface energy on the surface of the hard coat layer. The oily surface is oily, and the dirt such as fingerprints is not easily attached, and the processor which is easy to remove is applied.
例如,特開2004-250474號公報:如專利文獻1中所示,以具有全氟聚醚基的矽烷化合物來處理硬塗層的最表面,日本發明專利第3963169號公報:如專利文獻2中所示,藉由將全氟聚醚胺基甲酸丙烯酸酯組成物添加到硬塗層組成物中,使偏向於其表面交聯,而形成撥水.撥油性表面,展現防污性能。 For example, Japanese Laid-Open Patent Publication No. 2004-250474, the entire surface of the hard coat layer is treated with a perfluoropolyether group-containing decane compound, Japanese Patent Laid-Open No. 3963169: Patent Document 2 As shown, by adding a perfluoropolyether urethane acrylate composition to the hard coat composition, the surface is crosslinked to form a water repellent. Oil-repellent surface for anti-fouling performance.
此方法雖然使所附著的髒污變容易被拭去,但因為其高撥水.撥油性,所附著的指紋等係形成微細的液滴,由於將光漫反射而透過性或視覺辨認性降低,由於氟化合物為低折射率,與指紋之成分的皮脂或汗等之折射率差大,即使稍微的附著痕跡也會醒目。 Although this method makes the attached dirt easy to be wiped off, but because of its high water. The oil-repellent property, the attached fingerprint, etc. form fine droplets, and the transmittance or visibility is lowered due to diffuse reflection of light, and the refractive index difference between the sebum or sweat of the component of the fingerprint due to the low refractive index of the fluorine compound Large, even a slight trace of adhesion will be eye-catching.
又,所附著的指紋含有水分或鹽等的無機成分、蛋白 質或油脂等的有機成分等,其組成為複雜,難以完全地防止此等之附著。 In addition, the attached fingerprint contains inorganic components such as water or salt, and proteins. An organic component such as a substance or a fat or oil has a complicated composition, and it is difficult to completely prevent such adhesion.
另一個手法為在硬塗層的最表面上形成對於指紋等的髒污成分有高親和性的親水‧親油表面,藉由與所附著的髒污親密,使薄地潤濕擴展,而變不醒目。 Another method is to form a hydrophilic ‧ lipophilic surface having a high affinity for a dirty component such as a fingerprint on the outermost surface of the hard coat layer, and to make the thin wetting spread by being intimate with the adhered dirt Eye-catching.
例如,特開2001-353808號公報:如專利文獻3中所示,以具有長鏈烷基酯基的矽烷化合物來處理硬塗層的最表面,或國際公開第2009/44912號小冊:如專利文獻4中所示,藉由在丙烯酸聚合物組成物中添加膠態矽石,在表面上形成親水‧親油表面,而使髒污的視覺辨認性降低。 For example, Japanese Laid-Open Patent Publication No. 2001-353808: As shown in Patent Document 3, the outermost surface of a hard coat layer is treated with a decane compound having a long-chain alkyl ester group, or International Publication No. 2009/44912: As shown in Patent Document 4, by adding a colloidal vermiculite to the acrylic polymer composition, a hydrophilic ‧ lipophilic surface is formed on the surface, and the visibility of the stain is lowered.
於此方法中,即使髒污附著硬塗層表面,全體也潤濕擴展而變不易見到。再者,藉由使硬塗層的折射率接近指紋等的髒污成分,可更防止視覺辨認性的降低。然而,由於對髒污成分的親和性高,彼等係徐徐地堆積或難以拭去,故顯示器等的透光性會降低。 In this method, even if the surface of the hard coat layer is contaminated, the whole is wetted and spread and is not easily seen. Further, by making the refractive index of the hard coat layer close to a dirty component such as a fingerprint, it is possible to further prevent a decrease in visibility. However, since the affinity for the soiled components is high, they are slowly deposited or difficult to wipe off, so that the light transmittance of the display or the like is lowered.
又,日本發明專利第4873666號公報:專利文獻5中記載具有全氟聚醚基的丙烯酸酯化合物,當單獨添加該化合物時,指紋拭去性係被非常地改良,但指紋不醒目性不充分。 Japanese Patent No. 4873666: Patent Document 5 describes an acrylate compound having a perfluoropolyether group. When the compound is added alone, the fingerprint wiping off system is greatly improved, but the fingerprint is not conspicuous. .
[專利文獻1]特開2004-250474號公報 [Patent Document 1] JP-A-2004-250474
[專利文獻2]日本發明專利第3963169號公報 [Patent Document 2] Japanese Invention Patent No. 3963169
[專利文獻3]特開2001-353808號公報 [Patent Document 3] JP-A-2001-353808
[專利文獻4]國際公開第2009/44912號小冊 [Patent Document 4] International Publication No. 2009/44912
[專利文獻5]日本發明專利第4873666號公報 [Patent Document 5] Japanese Invention Patent No. 4873666
本發明係鑒於上述情事而完成者,目的在於提供可給予即使附著指紋、皮脂、汗等之人脂、化妝品等也不醒目,或即使附著髒污時拭去性也優異之賦予硬塗層表面防污性之硬塗層組成物。 The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a surface of a hard coat layer which can be imparted to human fats, cosmetics, and the like which adhere to fingerprints, sebum, sweat, and the like, or which is excellent in wiping property even when stains are adhered. Antifouling hard coating composition.
本發明者們為了達成上述目的,重複專心致力的檢討,結果發現於硬塗層材料中,藉由使用添加有下述通式(1)所示之含氟丙烯酸酯化合物、與下述通式(2)所示之具有全氟聚醚基的丙烯酸酯化合物之2種類的防污添加劑之賦予防污性之硬塗層組成物,所得之硬塗層表面係改良指紋不醒目性,指紋拭去性亦良好,而完成本發明。 In order to achieve the above object, the present inventors have repeated the intensive review, and found that a fluorine-containing acrylate compound represented by the following formula (1) is added to the hard coat material, and the following formula is used. (2) A hard coat composition for imparting antifouling properties to two types of antifouling additives of a perfluoropolyether group-containing acrylate compound, the surface of the hard coat layer obtained is improved in fingerprints, and the fingerprint is wiped off. The de-sexability is also good, and the present invention has been completed.
因此,本發明提供下述的賦予防污性之硬塗層組成物。 Accordingly, the present invention provides the following hard coat composition for imparting antifouling properties.
[1]一種賦予防污性之硬塗層組成物,其主成分為:(A)硬塗層材料,(B)下述通式(1)所示之含氟丙烯酸酯化合物,
所示之基,m為2~8之整數,n獨立地為1或2],(C)下述通式(2)所示之具有全氟聚醚基的丙烯酸酯化合物X1-[Z-Rf’-Z-X2]v-Z-Rf’-Z-X1 (2)[式中,Rf’獨立地係2價之分子量500~30,000的全氟聚醚基,亦可含途中分支,X1互相獨立地係下述式(3)
所示之丙烯酸基或含α取代丙烯酸基的基,Q1及Q2互相獨立地係碳數3~20的可含醚鍵、酯鍵、醯胺鍵或胺基甲酸酯鍵之2價連結基,可含途中環狀構造或分支構造,各自可相同或相異]所示之基,X2獨立地係下述式(6)
[2]如[1]之賦予防污性之硬塗層組成物,其中(A)成分之硬塗層材料係紫外線硬化型丙烯酸系硬塗層材料。 [2] The hard coat composition which imparts antifouling property according to [1], wherein the hard coat material of the component (A) is an ultraviolet curable acrylic hard coat material.
[3]如[2]之賦予防污性之硬塗層組成物,其中紫外線硬化型丙烯酸系硬塗層材料係由(甲基)丙烯酸系化合物及光聚合起始劑所構成。 [3] The hard coat composition for imparting antifouling properties according to [2], wherein the ultraviolet curable acrylic hard coat material is composed of a (meth)acrylic compound and a photopolymerization initiator.
藉由本發明的賦予防污性之硬塗層組成物,可給予即使附著指紋、皮脂、汗等之人脂、化妝品等也不醒目,或即使附著髒污時拭去性也優異之硬塗層表面。 By the hard coat composition which imparts antifouling property of the present invention, it is possible to impart a hard coat layer which is excellent in the wiping property even if it adheres to human fat such as fingerprints, sebum, sweat, etc., cosmetics, or the like. surface.
以下,詳細說明本發明。 Hereinafter, the present invention will be described in detail.
本發明的賦予防污性之硬塗層組成物,係將下述的成分作為主成分:(A)硬塗層材料,(B)通式(1)所示之含氟丙烯酸酯化合物,(C)通式(2)所示之具有全氟聚醚基的丙烯酸酯化合物。 The hard coat composition for imparting antifouling property of the present invention contains the following components as a main component: (A) a hard coat material, (B) a fluorine-containing acrylate compound represented by the formula (1), C) An acrylate compound having a perfluoropolyether group represented by the formula (2).
(A)硬塗層材料 (A) hard coating material
作為本發明的(A)成分之硬塗層材料,並沒有特別的限定,但較佳為對於後述的(B)、(C)成分之防污性賦予劑,溶解性與表面溶出性之平衡優異的藉由活性能量線之照射而硬化的樹脂(活性能量線硬化型樹脂組成物),特佳為由(甲基)丙烯酸系化合物及光聚合起始劑所構成之紫外線硬化型丙烯酸系硬塗層材料。 The hard coat material of the component (A) of the present invention is not particularly limited, but is preferably a balance between solubility and surface elution properties of the antifouling agent for the components (B) and (C) to be described later. An excellent resin (active energy ray-curable resin composition) which is cured by irradiation with an active energy ray, and particularly preferably an ultraviolet ray-curable acrylic hardened by a (meth)acrylic compound and a photopolymerization initiator. Coating material.
於紫外線硬化型丙烯酸系硬塗層材料中,作為(甲基)丙烯酸系化合物,例如可使用季戊四醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯、三(甲基)丙烯醯氧基乙基磷酸酯、苯二甲酸氫-(2,2,2-三(甲基)丙烯醯氧基甲基)乙基、甘油三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、雙三羥甲基丙烷四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、山梨糖醇六(甲基)丙烯酸酯 等之2~6官能的(甲基)丙烯酸化合物、此等的(甲基)丙烯酸化合物經環氧乙烷、環氧丙烷、環氧氯丙烷、脂肪酸、烷基、胺基甲酸酯改性品、在環氧樹脂附加丙烯酸而得之環氧丙烯酸酯類、將該(甲基)丙烯酸酯化合物在環氧乙烷、環氧丙烷、環氧氯丙烷、脂肪酸、烷、胺基甲酸乙酯改性產品、環氧樹脂加成丙烯酸所得環氧丙烯酯類、2-羥乙基(甲基)丙烯酯、2-羥基-3-丙烯醯氧基丙基甲基丙烯酸酯及季戊四醇三丙烯酸酯中選出之具有羥基的(甲基)丙烯酸酯、使由六亞甲基二異氰酸酯、異佛爾酮二異氰酸酯、甲苯二異氰酸酯及二苯基甲烷二異氰酸酯中選出之聚異氰酸酯反應之胺基甲酸酯丙烯酸酯類、在丙烯酸酯共聚物之側鏈導入有(甲基)丙烯醯基之共聚物等的多官能(甲基)丙烯酸酯混合物等,於其中摻合苯偶姻、苯偶姻甲基醚、二苯基酮、1-羥基環己基苯基酮等之光聚合起始劑而使用。 In the ultraviolet curable acrylic hard coat material, as the (meth)acrylic compound, for example, pentaerythritol di(meth)acrylate, diethylene glycol di(meth)acrylate, or trimethylolpropane can be used. Tris(meth)acrylate, tetramethylol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate, tris(meth)acryloxyethyl phosphate Ester, hydrogen phthalate-(2,2,2-tris(meth)acryloxymethyl)ethyl, glycerol tri(meth) acrylate, pentaerythritol tetra(meth) acrylate, ditrihydroxy Methylpropane tetra(meth)acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa(meth) acrylate, sorbitol hexa(meth) acrylate 2~6-functional (meth)acrylic compounds, such (meth)acrylic compounds modified with ethylene oxide, propylene oxide, epichlorohydrin, fatty acid, alkyl, urethane Epoxy acrylate obtained by adding acrylic acid to epoxy resin, the (meth) acrylate compound in ethylene oxide, propylene oxide, epichlorohydrin, fatty acid, alkane, ethyl urethane Modified product, epoxy resin obtained by adding acrylic acid to epoxy acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3- propylene methoxy propyl methacrylate and pentaerythritol triacrylate The selected (meth) acrylate having a hydroxyl group, and the amino isocyanate reacted with a polyisocyanate selected from hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate and diphenylmethane diisocyanate a acrylate acrylate or a polyfunctional (meth) acrylate mixture in which a copolymer of (meth) acrylonitrile group is introduced into a side chain of an acrylate copolymer, and a benzoin, benzoin A is blended therein. Ether, diphenyl ketone, 1-hydroxycyclohexyl phenyl ketone The photopolymerization initiator is used.
再者,作為紫外線硬化型丙烯酸系硬塗層材料,可使用市售品,作為(甲基)丙烯酸系化合物,例如可使用EBECRYL 40(4官能丙烯酸酯,DAICEL科學公司製),PETIA(3官能丙烯酸酯,DAICEL科學公司製)、A-TMPT(3官能丙烯酸酯,新中村化學工業製)、A-DPH(6官能丙烯酸酯,新中村化學工業製)、UA-306H(6官能丙烯酸酯,協榮社化學製)、UN-952(15官能丙烯酸酯,根上工業製)等。又,作為光聚合起始劑,例如可使用Irgacure 184、Irgacure 127、Irgacure 651、Darocure 1173(BASF製)等。 Further, as the ultraviolet curable acrylic hard coat material, a commercially available product can be used, and as the (meth)acrylic compound, for example, EBECRYL 40 (4-functional acrylate, manufactured by DAICEL Scientific Co., Ltd.), PETIA (3 functional group) can be used. Acrylate, manufactured by DAICEL Scientific Co., Ltd., A-TMPT (3-functional acrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), A-DPH (6-functional acrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H (6-functional acrylate, Co., Ltd. Chemical Co., Ltd.), UN-952 (15-functional acrylate, manufactured by K.K.). Further, as the photopolymerization initiator, for example, Irgacure 184, Irgacure 127, Irgacure 651, Darocure can be used. 1173 (BASF system) and the like.
此處,光聚合起始劑之使用量,相對於(甲基)丙烯酸系化合物100質量份,較佳為1~10質量份,更佳為1~5質量份。配合量若過少,則硬化性不充分,硬化物有變柔軟之情況,若過多,則在硬化物中不參與交聯的不純物會增加,有物性降低之情況。 Here, the amount of the photopolymerization initiator to be used is preferably 1 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 100 parts by mass of the (meth)acrylic compound. When the amount is too small, the hardenability is insufficient, and the cured product may become soft. If the amount is too large, impurities which do not participate in crosslinking in the cured product may increase, and the physical properties may be lowered.
本發明的(B)成分之含氟丙烯酸酯化合物係以下述通式(1)所示者,具有防污性賦予劑之作用。 The fluorine-containing acrylate compound of the component (B) of the present invention functions as an antifouling agent according to the following formula (1).
通式(1)中,Rf係碳數2~16、較佳碳數2~10、更佳碳數4~8之直鏈狀或分支狀氟伸烷基,用於將撥水.撥油性、防污性、對硬塗層表面的溶出性等特性賦予化合物者。Rf中的碳數超過上述上限值時,損害與硬塗層材料的相溶性,有發生白化或硬化不良等之虞。 In the formula (1), Rf is a linear or branched fluorine alkyl group having 2 to 16 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 4 to 8 carbon atoms, which is used for water withdrawal. The oil-repellent property, the anti-fouling property, and the elution property on the surface of the hard coat layer are imparted to the compound. When the carbon number in Rf exceeds the above upper limit value, the compatibility with the hard coat material is impaired, and whitening or hardening failure occurs.
作為如此的含氟基Rf之例,可例示例如下述所示者。 As an example of such a fluorine-containing group Rf, the following can be illustrated as an example.
-CpF2p-,-(CF2)r-CH2-(CF2)s-(式中,p為2~10之整數,較佳為4~8之整數,r為1~8,較佳為2~6之整數,s為1~8,較佳為2~6之整數)。 -C p F 2p -, -(CF 2 ) r -CH 2 -(CF 2 ) s - (wherein p is an integer from 2 to 10, preferably an integer from 4 to 8, and r is from 1 to 8, Preferably, it is an integer of 2 to 6, and s is 1 to 8, preferably an integer of 2 to 6.
於此等之中,可合適地使用下述所示者。 Among these, the following ones can be suitably used.
-CpF2p-(式中,p係與上述相同)。 -C p F 2p - (wherein p is the same as above).
通式(1)中,Q獨立地係單鍵、或碳數1~12、較佳碳數3~8的2價有機基。作為2價有機基,具體地可為亞甲基、伸乙基、伸丙基(三亞甲基、甲基伸乙基)、伸丁基(四亞甲基、甲基伸丙基)、六亞甲基、八亞甲基等之伸烷基、伸苯基等之伸芳基、或可為此等之基的2種以上之組合(伸烷基.伸芳基等),或可為於此等之基中插入由醚鍵、醯胺鍵、酯鍵、二有機矽烯基等中選出的1種或2種以上之構造者,再者於上述以外,可舉出含有包含由氧原子、氮原子、矽原子中選出的1種或2種以上之基的2價烴基。 In the formula (1), Q is independently a single bond or a divalent organic group having 1 to 12 carbon atoms and preferably 3 to 8 carbon atoms. The divalent organic group may specifically be a methylene group, an exoethyl group, a propyl group (trimethylene group, a methyl group ethyl group), a butyl group (tetramethylene group, a methyl group propyl group), and a hexamethyl group. a combination of an alkylene group such as a methylene group or an octamethylene group, an extended aryl group such as a phenyl group, or a combination of two or more groups (such as an alkyl group, an aryl group, etc.), or may be One or two or more kinds of structures selected from the group consisting of an ether bond, a guanamine bond, an ester bond, and a diorganenylalkenyl group are inserted into the base of the above, and in addition to the above, A divalent hydrocarbon group of one or more selected from the group consisting of an atom, a nitrogen atom and a ruthenium atom.
作為如此Q之2價有機基,可舉出下述式所示之基。 Examples of the divalent organic group of Q include a group represented by the following formula.
-CH2-,-CH2CH2-,-CH2CH2CH2-,-CH2-O-(CH2)t-,-CH2CH2-O-(CH2)t-,-OCH2-,-CO-NH-CH2-,-CO-N(Ph)-CH2-,-CO-NH-CH2CH2-,-CO-N(Ph)-CH2CH2CH2-,-CO-N(CH3)-CH2CH2CH2-,-CO-O-CH2-,-CO-N(CH3)-Ph’-,-CO-NR11-Y’-,-CO-NR11-Y’-CH2CH2-(式中,Ph為苯基,Ph’為伸苯基,t為1~10之整數。 -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 -O-(CH 2 ) t -, -CH 2 CH 2 -O-(CH 2 ) t -,- OCH 2 -, -CO-NH-CH 2 -, -CO-N(Ph)-CH 2 -, -CO-NH-CH 2 CH 2 -, -CO-N(Ph)-CH 2 CH 2 CH 2 -, -CO-N(CH 3 )-CH 2 CH 2 CH 2 -, -CO-O-CH 2 -, -CO-N(CH 3 )-Ph'-, -CO-NR 11 -Y'- -CO-NR 11 -Y'-CH 2 CH 2 - (wherein Ph is a phenyl group, Ph' is a phenylene group, and t is an integer of 1 to 10.
Y’係-CH2-或下述式
此處,作為上述R11之非取代或取代的較佳為碳數1~10之1價烴基,例如可舉出甲基、乙基、丙基、異丙基、丁基、異丁基、第三丁基、戊基、新戊基、己基、辛基等之烷基、環己基等之環烷基、乙烯基、烯丙基、丙烯基等之烯基、苯基、甲苯基、二甲苯基、萘基等之芳基、苄基、苯基乙基、苯基丙基等之芳烷基等,或此等基的氫原子之一部分或全部被氟、溴、氯等之鹵素原子、氰基(N≡C-)等所取代者,例如氯甲基、氯丙基、溴乙基、三氟丙基、氰乙基等。 Here, the unsubstituted or substituted R 11 is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. An alkyl group such as a third butyl group, a pentyl group, a neopentyl group, a hexyl group or an octyl group; a cycloalkyl group such as a cyclohexyl group; an alkenyl group such as a vinyl group, an allyl group or a propenyl group; a phenyl group; a tolyl group; An aryl group such as a tolyl group or a naphthyl group, an aralkyl group such as a benzyl group, a phenylethyl group or a phenylpropyl group, or a part or all of the hydrogen atoms of the groups may be a halogen atom such as fluorine, bromine or chlorine. A cyano group (N≡C-) or the like is substituted, for example, a chloromethyl group, a chloropropyl group, a bromoethyl group, a trifluoropropyl group, a cyanoethyl group or the like.
式(1)中,R獨立地係可含氧原子之碳數6~20、較佳碳數8~20的烷基或碳數7~20、較佳碳數8~14的芳烷基,該基具有與髒污或指紋之油成分之親和性,為了使髒污或指紋不醒目而導入。例如,作為烷基,可舉出己基、庚基、辛基、壬基、癸基、十一基、十二基(月桂基)、十四基(肉豆蔻基)、十六基(棕櫚基)、十八基(硬脂基)、二十基等,作為芳烷基,可舉出苄基、苯基乙基、甲苯基乙基等。又,亦可為在此等中插入醚鍵結氧原子(-O-)、羰基鍵(-CO-)、酯鍵(-COO-)等之1種或2種以上者,例如可舉出十一酸乙基、辛基酸乙基、乙氧基戊基等。複數的R可為相同之基或異種之基。 In the formula (1), R is independently an alkyl group having 6 to 20 carbon atoms, preferably 8 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, preferably 8 to 14 carbon atoms. The base has affinity with the oil component of the stain or the fingerprint, and is introduced in order to make the stain or the fingerprint unobtrusive. For example, examples of the alkyl group include a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an undecyl group, a dodecyl group (lauryl group), a tetradecyl group (myristyl group), and a hexadecyl group (palmityl group). And an octadecyl (stearyl), a decyl group, etc., and an aralkyl group, a benzyl group, a phenylethyl group, a tolylethyl group, etc. are mentioned. In addition, one or more types of an oxygen-bonded oxygen atom (-O-), a carbonyl bond (-CO-), and an ester bond (-COO-) may be inserted in the above-mentioned, for example, Ethyl undecanoate, ethyl octylate, ethoxypentyl, and the like. The plural R can be the same base or a heterologous base.
式(1)中,R1互相獨立地係碳數1~6、較佳碳數1~4的烷基、碳數6~10、較佳碳數6~8的芳基、或碳數7~10、較佳碳數7~8的芳烷基,該基係為了在化合物中賦予親油性、對硬塗層材料的相溶性等而導入。例如,可舉出甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、己基、環己基等之烷基、苯基等之芳基、苄基等之芳烷基等。其中,較佳為甲基、正丁基、苯基,特佳為甲基。R1係各自可為相同之基或異種之基。 In the formula (1), R 1 is independently an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, or a carbon number of 7 ~10, preferably an aralkyl group having 7 to 8 carbon atoms, which is introduced in order to impart lipophilicity to a compound, compatibility with a hard coat material, and the like. For example, an alkyl group such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a hexyl group or a cyclohexyl group, an aryl group such as a phenyl group, or a benzyl group may be mentioned. Etc. aralkyl and the like. Among them, a methyl group, a n-butyl group, and a phenyl group are preferred, and a methyl group is particularly preferred. Each of the R 1 systems may be the same or a heterogeneous group.
又,R2係氫原子或甲基。 Further, R 2 is a hydrogen atom or a methyl group.
式(1)中,X係下述通式所示者。 In the formula (1), X is represented by the following formula.
又,式(1)中,n獨立地為1或2,較佳為2;m為2~8之整數,較佳為2~6之整數。 Further, in the formula (1), n is independently 1 or 2, preferably 2; m is an integer of 2 to 8, preferably an integer of 2 to 6.
作為上述通式(1)所示之含氟丙烯酸酯化合物,具體地可例示下述所示者。 Specific examples of the fluorine-containing acrylate compound represented by the above formula (1) include the following.
上述通式(1)所示之含氟丙烯酸酯化合物係可藉由已知的方法來容易地製造。例如,可使下述通式(i)
所示之含有氫矽烷氧基的含氟化合物、與自式(1)的R基中去掉1個氫原子後的殘基所對應之碳數6~20的α-烯烴系化合物與烯醇,較佳在鉑系觸媒之存在下,藉由習知的方法進行氫矽烷化加成反應而成為含氟有機基改性矽氧烷後,使該矽氧烷與含有(甲基)丙烯酸基的異氰酸酯化合物反應而製造。 a fluorine-containing compound containing a hydroquinolyl group, and an α-olefin compound having 6 to 20 carbon atoms and an enol corresponding to a residue obtained by removing one hydrogen atom from the R group of the formula (1). Preferably, in the presence of a platinum-based catalyst, the hydroxylation addition reaction is carried out by a conventional method to form a fluorine-containing organic modified siloxane, and the oxirane and the (meth)acrylic group are contained. The isocyanate compound is produced by reaction.
此處,α-烯烴系化合物係自式(1)的R中去掉1個氫原子後之烯烴,較佳為在一末端具有乙烯基之烯烴。若使用兩末端含有乙烯基的烯烴,則在氫矽烷化加成反應時,在分子間會發生交聯反應,進行高分子化而生成物凝膠化,或對硬塗層材料的溶解性有降低之虞。作為碳數6~ 20的α-烯烴系化合物,具體地可例示1-十六烯、1-十二烯、10-十一烯酸乙酯、乙氧基-1-戊烯等。 Here, the α-olefin compound is an olefin obtained by removing one hydrogen atom from R in the formula (1), and preferably an olefin having a vinyl group at one terminal. When an olefin having a vinyl group at both ends is used, a cross-linking reaction occurs between the molecules during the hydroquinone addition reaction, and the product is gelated, or the solubility of the hard coat material is Reduce the embarrassment. As carbon number 6~ Specific examples of the 20-α-olefin compound include 1-hexadecene, 1-dodecene, 10-undecenoic acid ethyl ester, and ethoxy-1-pentene.
又,作為烯醇,可例示下述式所示者。 Further, examples of the enol include those represented by the following formulas.
HO-R13-CH=CH2(式中,R13係單鍵或碳數1~6的亞甲基、伸乙基、伸丙基、伸丁基等之伸烷基)。 HO-R 13 -CH = CH 2 ( wherein, R 13 based single bond or a methylene group having a carbon number 1 to 6, extending ethyl, propyl stretching, stretching alkylene butyl, etc.).
所謂之含有氫矽烷氧基的含氟化合物與碳數6~20的α-烯烴系化合物,就是以含有氫矽烷氧基的含氟化合物之SiH基係至少1個殘留之方式使反應者,具體地,較佳係以含有氫矽烷氧基的含氟化合物的SiH基與α-烯烴系化合物之末端乙烯基的莫耳比(Vi/SiH比)為0.167~0.833,更佳為0.333~0.667進行反應,而得到具有至少1個、較佳1~3個SiH基之含氟有機基改性矽氧烷。α-烯烴系化合物若比上述過剩,則在添加於硬塗層材料中時,有發生混濁之虞。 The fluorine-containing compound containing a hydroquinolyl group and the α-olefin compound having 6 to 20 carbon atoms are reacted so that at least one of the SiH groups of the fluorine-containing compound containing a hydroquinolyl group remains. Preferably, the molar ratio (Vi/SiH ratio) of the terminal vinyl group of the SiH group containing the hydrofluorenyloxy group-containing fluorine compound and the α-olefin compound is 0.167 to 0.833, more preferably 0.333 to 0.667. The reaction is carried out to obtain a fluorine-containing organic group-modified rhodium oxide having at least one, preferably 1 to 3, SiH groups. When the α-olefin compound is more than the above, when it is added to the hard coat material, turbidity may occur.
接著,使剩餘的SiH基皆與烯醇反應。上述含有氫矽烷氧基的含氟化合物與α-烯烴系化合物反應後之具有至少1個SiH基的含氟有機基改性矽氧烷、與烯醇,較佳係以該含氟有機基改性矽氧烷的SiH基與烯醇的乙烯基之莫耳比(Vi/SiH比)為0.2~1.5,特佳為0.333~1.2,進行反應,而得到不具有SiH基之含氟有機基改性矽氧烷。 Next, the remaining SiH groups are reacted with the enol. The fluorine-containing organic group-modified siloxane having at least one SiH group after the reaction of the fluoroalkoxy group-containing fluorine-containing compound with the α-olefin compound and the enol are preferably modified by the fluorine-containing organic group The molar ratio of the SiH group of the azoxy alkane to the vinyl group of the enol (Vi/SiH ratio) is 0.2 to 1.5, particularly preferably 0.333 to 1.2, and the reaction is carried out to obtain a fluorine-containing organic group having no SiH group. Sexual alkane.
於上述反應中,作為鉑系觸媒,可使用氫矽烷化加成反應時所用之習知的鉑族金屬觸媒。一般由於貴金屬的化合物之高價格,較宜使用比較容易取得之鉑或鉑化合物。 作為如此的鉑化合物,可使用氯鉑酸或氯鉑酸與乙烯等烯烴之錯合物,與醇、乙烯基矽氧烷之錯合物,及擔持在矽石、氧化鋁、碳等上之金屬鉑。作為鉑化合物以外之鉑族金屬觸媒,可使用銠、釕、銥及鈀系化合物,例如可使用RhCl(PPh3)3、RhCl(CO)(PPh3)2、Ru3(CO)12、IrCl(CO)(PPh3)2、Pd(PPh3)4等(式中,Ph為苯基)。 In the above reaction, as the platinum-based catalyst, a conventional platinum group metal catalyst used in the hydroquinone addition reaction can be used. Generally, due to the high price of the noble metal compound, it is preferred to use a platinum or platinum compound which is relatively easy to obtain. As such a platinum compound, a complex of chloroplatinic acid or chloroplatinic acid with an olefin such as ethylene, a complex with an alcohol or a vinyl siloxane, and a ruthenium, alumina, carbon, or the like can be used. Metal platinum. As the platinum group metal catalyst other than the platinum compound, ruthenium, rhodium, iridium, and palladium compounds can be used. For example, RhCl(PPh 3 ) 3 , RhCl(CO)(PPh 3 ) 2 , Ru 3 (CO) 12 , IrCl(CO)(PPh 3 ) 2 , Pd(PPh 3 ) 4 or the like (wherein, Ph is a phenyl group).
鉑系觸媒之使用量係可為催化量,相對於含有氫矽烷氧基的含氟化合物與α-烯烴系化合物或烯醇之合計量100質量份,較佳為0.1~500ppm(鉑質量換算)之量。 The amount of the platinum-based catalyst used may be a catalytic amount, and is preferably 0.1 to 500 ppm, preferably 0.1 to 500 ppm, based on 100 parts by mass of the total of the hydrofluorinated alkoxy group-containing fluorine-containing compound and the α-olefin compound or the enol. The amount.
反應溫度係按照溶劑的量或種類來適宜決定,通常可為室溫~200℃,較佳為40~100℃。反應時間係沒有特別的限制,只要按照個別的反應條件,充分進行反應即可 The reaction temperature is appropriately determined depending on the amount or type of the solvent, and it is usually from room temperature to 200 ° C, preferably from 40 to 100 ° C. The reaction time is not particularly limited as long as the reaction is sufficiently carried out according to individual reaction conditions.
於進行上述各階段的氫矽烷化加成反應時,視需要亦可使用溶劑。溶劑宜為將含有氫矽烷氧基的含氟化合物、α-烯烴系化合物及烯醇的任一者皆溶解者,但即使為僅溶解任一者,只要不阻礙氫矽烷化加成反應,則沒有特別的限制。溶劑之使用量係按照含有氫矽烷氧基的含氟化合物、α-烯烴系化合物及烯醇或生成之含氟有機基改性矽氧烷的黏度或加入量來適宜選定,但相對於含有氫矽烷氧基的含氟化合物、α-烯烴系化合物及烯醇之合計量100質量份,較佳為10~200質量份,特佳為20~100質量份。 When performing the hydrohaloalkylation addition reaction in each of the above stages, a solvent may be used as needed. The solvent is preferably one in which a hydrofluorinated alkoxy group-containing fluorine-containing compound, an α-olefin compound, and an enol are dissolved. However, if only one of them is dissolved, as long as it does not inhibit the hydroquinone addition reaction, There are no special restrictions. The amount of the solvent to be used is appropriately selected according to the viscosity or the amount of the fluorine-containing compound containing a hydrofluorenyloxy group, the α-olefin compound, and the enol or the resulting fluorine-containing organic modified rhodium oxide, but is relative to the hydrogen-containing compound. The total amount of the fluorinated compound of the decyloxy group, the α-olefin compound, and the enol is preferably 10 to 200 parts by mass, particularly preferably 20 to 100 parts by mass.
作為如此的溶劑,可舉出正己烷、正庚烷、異辛烷、異癸烷等之脂肪族烴系化合物,甲苯、二甲苯等之芳香族烴系化合物,三氟甲苯、六氟間二甲苯等之含氟芳香族烴 系化合物,全氟丁基甲基醚、全氟丁基乙基醚、1,1,1,2,2,3,4,5,5,5-十氟-3-甲氧基-4-(三氟甲基)戊烷等之氫氟醚系化合物、Daiproyl(DAIKIN工業製)等之氯氟碳系化合物、六甲基二矽氧烷、八甲基三矽氧烷、十甲基四矽氧烷、十二甲基五矽氧烷、2-(三甲基矽氧烷基)-1,1,1,2,3,3,3-七甲基三矽氧烷等之鏈狀矽氧烷、八甲基環五矽氧烷、十甲基環五矽氧烷等之環狀矽氧烷、Fomblin、Galden(SOLVAY SOLEXIS製)、Demnum(DAIKIN工業製)、Krytox(DuPont製)等之全氟聚醚系化合物等。其中,甲苯、二甲苯、六氟間二甲苯係含有氫矽烷氧基的含氟化合物、α-烯烴系化合物、烯醇及生成的含氟有機基改性矽氧烷之溶解性優異而較合適。 Examples of such a solvent include aliphatic hydrocarbon compounds such as n-hexane, n-heptane, isooctane, and isodecane, and aromatic hydrocarbon compounds such as toluene and xylene, and trifluorotoluene and hexafluoro-di Fluorinated aromatic hydrocarbons such as toluene Compound, perfluorobutyl methyl ether, perfluorobutyl ethyl ether, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(three a hydrofluoroether compound such as fluoromethyl)pentane or a chlorofluorocarbon compound such as Daiproyl (manufactured by DAIKIN Co., Ltd.), hexamethyldioxane, octamethyltrioxane or decamethyltetraoxane Chain-like oxime of alkane, dodecamethylpentaoxane, 2-(trimethylphosphonium oxyalkyl)-1,1,1,2,3,3,3-heptamethyltrioxane a cyclic oxirane such as an alkane, an octamethylcyclopentaoxane or a decamethylcyclopentaoxane, a Fomblin, a Galden (manufactured by SOLVAY SOLEXIS), a Demnum (manufactured by DAIKIN Industries), or a Krytox (manufactured by DuPont). Perfluoropolyether compound or the like. Among them, toluene, xylene, hexafluorom-xylene-based hydrofluoroalkyloxy group-containing fluorine-containing compound, α-olefin compound, enol, and produced fluorine-containing organic modified rhodium oxide are excellent in solubility. .
使所得之含氟有機基改性矽氧烷與含有(甲基)丙烯酸基的異氰酸酯化合物反應。此時,將含氟有機基改性矽氧烷中的醇量予以定量,宜使其量之1.2~3倍莫耳量、較佳1.5~2倍莫耳量之含有(甲基)丙烯酸基的異氰酸酯化合物反應。 The obtained fluorine-containing organic modified azide is reacted with an isocyanate compound containing a (meth)acryl group. In this case, the amount of the alcohol in the fluorine-containing organic modified rhodium oxide is quantified, preferably in an amount of 1.2 to 3 times the molar amount, preferably 1.5 to 2 times the molar amount of the (meth)acrylic group. The isocyanate compound reacts.
此處,作為含有(甲基)丙烯酸基的異氰酸酯化合物,可例示下述式所示者。 Here, the isocyanate compound containing a (meth)acryl group can be exemplified by the following formula.
含氟有機基改性矽氧烷與含有(甲基)丙烯酸基的異氰酸酯化合物之反應,係可藉由在0~120℃、較佳在25 ~80℃之條件下,將兩者混合而進行。 The reaction of the fluorine-containing organic modified alkane with the (meth)acrylic acid-containing isocyanate compound can be carried out at 0 to 120 ° C, preferably 25 Under the condition of ~80 ° C, the two were mixed and carried out.
又,為了增加反應速度,亦可添加適當的觸媒。作為觸媒,例如可例示二乙酸二丁錫、二月桂酸二丁錫、二辛酸二丁錫、二乙酸二辛錫、二月桂酸二辛錫、二辛酸二辛錫、二辛酸亞錫等之烷基錫酯化合物、四異丙氧基鈦、四正丁氧基鈦、四(2-乙基己氧基)鈦、二丙氧基雙(乙醯丙酮)鈦、鈦異丙氧基辛二醇等之鈦酸酯或鈦螯合化合物、鋯四乙醯丙酮化物、鋯三丁氧基單乙醯丙酮化物、鋯單丁氧基乙醯丙酮化物雙(乙基乙醯乙酸酯)、鋯二丁氧基雙(乙基乙醯乙酸酯)、鋯四乙醯丙酮化物、鋯螯合化合物等,但此等係不限定於其1種,也可作為2種或其以上之混合物使用。相對於反應物總質量,藉由以0.01~2質量%、較佳0.05~1質量%來添加此等觸媒,可增加反應速度。 Further, in order to increase the reaction rate, an appropriate catalyst may be added. Examples of the catalyst include dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctoate, stannous dioctoate, and the like. Alkyl tin ester compound, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetrakis(2-ethylhexyloxy), titanium dipropoxy bis(acetonitrile), titanium isopropoxy A titanate or titanium chelate compound such as octanediol, zirconium tetraethoxide acetonide, zirconium tributoxy acetoacetate acetonide, zirconium monobutoxyacetam acetonide bis(ethyl acetamidine acetate) , zirconium dibutoxy bis(ethyl acetamidine acetate), zirconium tetraethyl acetonide, zirconium chelate compound, etc., but these are not limited to one type, and may be two or more types. The mixture is used. The reaction rate can be increased by adding these catalysts in an amount of 0.01 to 2% by mass, preferably 0.05 to 1% by mass, based on the total mass of the reactants.
又,視需要亦可用適當的溶劑來稀釋而進行反應。作為如此的溶劑,只要是不與異氰酸酯及羥基反應之溶劑,則可沒有特別限制而使用,具體地可例示四氫呋喃、二異丙基醚、二丁基醚等之醚類,丙酮、甲基乙基酮、甲基異丁基酮等之酮類,醋酸乙酯、醋酸丁酯等之酯類,甲苯、二甲苯等之芳香族烴系溶劑等。 Further, the reaction may be carried out by diluting with a suitable solvent as needed. The solvent is not particularly limited as long as it is a solvent which does not react with an isocyanate or a hydroxyl group, and specific examples thereof include ethers such as tetrahydrofuran, diisopropyl ether and dibutyl ether, acetone and methyl ethyl. A ketone such as a ketone or a methyl isobutyl ketone; an ester such as ethyl acetate or butyl acetate; an aromatic hydrocarbon solvent such as toluene or xylene; and the like.
本發明的(B)成分係可調製成為在有機溶劑中均勻溶解之溶液。此時,只要是得到均勻溶液之範圍,則溶液中的含氟丙烯酸酯化合物之濃度係沒有特別的限制,通常可為1~50質量%,較佳可為5~30質量%,更佳可為5 ~20質量%左右。 The component (B) of the present invention can be prepared into a solution which is uniformly dissolved in an organic solvent. In this case, the concentration of the fluorine-containing acrylate compound in the solution is not particularly limited as long as the range of the homogeneous solution is obtained, and it is usually 1 to 50% by mass, preferably 5 to 30% by mass, more preferably For 5 ~20% by mass or so.
作為溶解含氟丙烯酸酯化合物之有機溶劑,選擇不與(A)成分的硬塗層材料反應者,例如可舉出己烷、庚烷、異辛烷、異癸烷等之脂肪族烴系溶劑,甲苯、二甲苯等之芳香族烴系溶劑,甲醇、乙醇、異丙醇等之醇系溶劑,丙酮、甲基乙基酮、甲基異丁基酮、環己酮等之酮系溶劑,乙二醇單乙基醚、乙二醇單第三丁基醚、丙二醇單甲基醚等之二醇醚系溶劑,醋酸乙酯、醋酸丁酯、丙二醇單甲基醚醋酸酯等之酯系溶劑等。其中,較宜使用異癸烷、異丙醇、甲基異丁基酮等。 The organic solvent in which the fluorine-containing acrylate compound is dissolved is selected from those which do not react with the hard coat material of the component (A), and examples thereof include aliphatic hydrocarbon solvents such as hexane, heptane, isooctane, and isodecane. An aromatic hydrocarbon solvent such as toluene or xylene; an alcohol solvent such as methanol, ethanol or isopropyl alcohol; a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; A glycol ether solvent such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether or propylene glycol monomethyl ether, or an ester system such as ethyl acetate, butyl acetate or propylene glycol monomethyl ether acetate. Solvents, etc. Among them, isodecane, isopropanol, methyl isobutyl ketone and the like are preferably used.
(B)成分之含氟丙烯酸酯化合物的添加量,相對於(A)成分之硬塗層材料100質量份,若以(上述溶液中的固體成分)0.1~3質量份,更佳以0.2~2質量份之比例來添加,則得到良好的表面特性。未達上述下限值時,對硬塗層表面的溶出係困難,有得不到適宜的特性之虞。又,超過上述上限值時,由於損害對樹脂的親和性,有發生外觀的白化或硬度的降低等之虞。 The amount of the fluorine-containing acrylate compound to be added as the component (B) is 0.1 to 3 parts by mass, more preferably 0.2 to 100 parts by mass of the hard coat material of the component (A). When the ratio of 2 parts by mass is added, good surface characteristics are obtained. When the lower limit is not reached, the elution of the surface of the hard coat layer is difficult, and the appropriate characteristics are not obtained. Moreover, when it exceeds the above-mentioned upper limit, the affinity for the resin may be impaired, and whitening of the appearance or a decrease in hardness may occur.
本發明的(C)成分之具有全氟聚醚基的丙烯酸酯化合物係下述式(2)所示者,具有防污性賦予劑之作用。 The acrylate compound having a perfluoropolyether group of the component (C) of the present invention is an antifouling property imparting agent as shown by the following formula (2).
X1-[Z-Rf’-Z-X2]v-Z-Rf’-Z-X1 (2) X 1 -[Z-Rf'-ZX 2 ] v -Z-Rf'-ZX 1 (2)
式(2)中,Rf’獨立地係2價之分子量500~30,000的全氟聚醚基,亦可含途中分支。 In the formula (2), Rf' is independently a divalent polyfluoropolyether group having a molecular weight of 500 to 30,000, and may also be branched in the middle.
Rf’係含有1~500個通式-CiF2iO-(i係每單位獨立地為1~6之整數)所示的重複單位之2價全氟聚醚殘基,較佳為下述式(7)~(9)所示之全氟聚醚殘基。 Rf' is a divalent perfluoropolyether residue having 1 to 500 repeating units of the formula -C i F 2i O- (i is an integer of from 1 to 6 per unit independently), preferably lower The perfluoropolyether residue represented by the formulas (7) to (9).
式(7)中,Y各自獨立地為F或CF3基,A為2~6之整數,較佳為1~3之整數、B、C各自為0或1~200之整數,較佳為2~100之整數,惟B+C為2~200,較佳為4~100。D為0或1~6之整數,較佳為1~4之整數,各重複單位亦可無規地鍵結。 In the formula (7), Y is each independently F or a CF 3 group, and A is an integer of 2 to 6, preferably an integer of 1 to 3, and B and C are each an integer of 0 or 1 to 200, preferably An integer from 2 to 100, but B+C is 2 to 200, preferably 4 to 100. D is an integer of 0 or 1 to 6, preferably an integer of 1 to 4, and each repeating unit may be randomly bonded.
【化17】-CEF2E(OCF2CF2CF2)GOCEF2E- (8) [Chem. 17]-C E F 2E (OCF 2 CF 2 CF 2 ) G OC E F 2E - (8)
式中,E為1~3之整數,G為1~200之整數,較佳為1~100之整數。 In the formula, E is an integer of 1 to 3, and G is an integer of 1 to 200, preferably an integer of 1 to 100.
式中,Y為F或CF3基,E為1~3之整數,H、J各自為0或1~200之整數,較佳為1~100之整數,惟H+J為2~200,較佳為4~100。各重複單位亦可無規地鍵結。 Wherein Y is an F or CF 3 group, E is an integer from 1 to 3, and H and J are each an integer of 0 or 1 to 200, preferably an integer of 1 to 100, except that H+J is 2 to 200. It is preferably 4 to 100. Each repeating unit can also be randomly bonded.
式(2)中,X1各自獨立地為下述式(3)所示之基。 In the formula (2), X 1 is each independently a group represented by the following formula (3).
式(3)中,a及c各自為0或1~3之整數,b為1~4之整數,較佳為2或3,惟a+b+c為2、3、4的任一者,較佳為3或4,各重複單位的排列亦可為無規。 In the formula (3), a and c are each an integer of 0 or 1 to 3, and b is an integer of 1 to 4, preferably 2 or 3, except that a+b+c is any of 2, 3, and 4. Preferably, it is 3 or 4, and the arrangement of each repeating unit may also be random.
式(3)中,R3獨立地為下述式(4)所示之基。 In the formula (3), R 3 is independently a group represented by the following formula (4).
-(C4H8O)d(C3H6O)e(C2H4O)f(CH2O)gR5 (4) -(C 4 H 8 O) d (C 3 H 6 O) e (C 2 H 4 O) f (CH 2 O) g R 5 (4)
式(4)中,d、e、f及g係在R3的分子量成為45~600、較佳成為60~300之範圍中,各自獨立地為0或1~20之整數,較佳為1~10之整數,d+e+f+g較佳為1~20,更佳為2~15。再者,式(4)中的伸丙基、伸丁基亦可為分支,各重複單位之排列亦可為無規。 Formula (4), d, e, f, and g based on the molecular weight of R 3 is 45 to 600, preferably be in the range of 60 to 300, are each independently an integer of 0 or 1 to 20, preferably 1 An integer of ~10, d+e+f+g is preferably from 1 to 20, more preferably from 2 to 15. Further, the propyl group and the butyl group in the formula (4) may be branched, and the arrangement of each repeating unit may be random.
式(4)中,R5係碳數1~10的飽和或不飽和1價烴基,可舉出甲基、乙基、丙基、異丙基、丁基、戊基、己基、2-乙基己基、環己基等的烷基、苯基等的芳基、苄基等的芳烷基等。特佳為甲基、乙基。 Formula (4), R 5 based saturated carbon atoms of 1 to 10 or an unsaturated monovalent hydrocarbon group include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, 2-B An alkyl group such as a hexyl group or a cyclohexyl group; an aryl group such as a phenyl group; an aralkyl group such as a benzyl group; and the like. Particularly preferred are methyl and ethyl.
作為如此的R3,較佳為下述式所示之基。 As such R 3 , a group represented by the following formula is preferred.
-(C2H4O)f' (C3H6O)e' CH3(式中,f’、e’為0或1~20之整數,f’+e’為1~40,式中的伸丙基亦可為分支,各重複單位亦可無規地鍵結) -(C 2 H 4 O) f ' (C 3 H 6 O) e ' CH 3 (wherein f', e' is 0 or an integer from 1 to 20, and f'+e' is from 1 to 40. The propyl group in the middle can also be a branch, and each repeating unit can also be randomly bonded)
R4係具有下述式(5)所示之至少一個丙烯酸基或α 取代丙烯酸基中的任一者之較佳為碳數1~21的1價有機基。 R 4 is preferably a monovalent organic group having 1 to 21 carbon atoms, which is one of at least one of an acryl group and an α-substituted acryl group represented by the following formula (5).
式(5)中,R6獨立地係氫原子、氟原子、甲基、三氟甲基的任一者,特佳為氫原子、甲基。R7係碳數1~18、較佳為碳數2~10之2價或3價連結基,亦可含醚鍵性氧原子或酯構造,較佳可舉出下述所示者。 In the formula (5), R 6 is independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group. R 7 is a carbon number of 1 to 18, preferably a divalent or trivalent linking group having 2 to 10 carbon atoms, and may have an etheric oxygen atom or an ester structure, and preferably exemplified below.
又,u為1或2。 Also, u is 1 or 2.
作為式(5)所示之基,較佳為下述式所示之基,特佳為含有作為R7的伸乙基之基。 The group represented by the formula (5) is preferably a group represented by the following formula, and particularly preferably a group containing an ethyl group as R 7 .
式(3)中,Q1及Q2互相獨立地係碳數3~20的可含醚鍵、酯鍵、醯胺鍵或胺基甲酸酯鍵之2價連的結基,可含途中環狀構造或分支構造,各自可相同或相異。作為Q1及Q2較佳為以下述式所示之基。 In the formula (3), Q 1 and Q 2 are each independently a two-valent linking group having an ether bond, an ester bond, a guanamine bond or a urethane bond having a carbon number of 3 to 20, which may be included in the middle. The annular structure or the branched structure may each be the same or different. As Q 1 and Q 2 , a group represented by the following formula is preferable.
式(2)中,X2獨立地係下述式(6)所示之2價基。 In the formula (2), X 2 is independently a divalent group represented by the following formula (6).
式(6)中,R3、R4、Q1、Q2係與上述相同,h、k各自為0或1~3之整數,j為1~3之整數,而且h+j+k為1、2、3的任一值,各重複單位之排列亦可為無規。 In the formula (6), R 3 , R 4 , Q 1 , and Q 2 are the same as described above, and h and k are each an integer of 0 or 1 to 3, j is an integer of 1 to 3, and h+j+k is For any value of 1, 2, and 3, the arrangement of each repeating unit may also be random.
式(2)中,Z各自獨立地係可含氧原子、氮原子、二有機矽烯基等的矽原子之2價有機基,而且Z亦可為具有環狀構造、不飽和鍵之基,只要不阻礙丙烯酸基之聚合,則構造係沒有特別的限制。作為Z之例,可舉出下述式所示之基。 In the formula (2), each of Z is independently a divalent organic group which may contain a halogen atom such as an oxygen atom, a nitrogen atom or a diorganenylenyl group, and Z may be a group having a cyclic structure or an unsaturated bond. The structural system is not particularly limited as long as it does not hinder the polymerization of the acrylic group. Examples of Z include a group represented by the following formula.
其中,較佳為以下述式所示之基。 Among them, a group represented by the following formula is preferred.
v為0或1~5之整數,較佳為0、1或2,更佳為0或1。 v is an integer of 0 or 1 to 5, preferably 0, 1 or 2, more preferably 0 or 1.
作為上述通式(2)所示之含有全氟聚醚基的丙烯酸酯化合物,具體地可例示下述所示者。 Specific examples of the fluoroacrylate group-containing acrylate compound represented by the above formula (2) include the following.
本發明之(C)成分係可調製成為在有機溶劑中均勻溶解之溶液。此時,只要是得到均勻溶液之範圍,則溶液中之含有全氟聚醚基的丙烯酸酯化合物之濃度係沒有特別的限制,通常可為1~50質量%,較佳可為5~30質量%,更佳可為5~20質量%左右。 The component (C) of the present invention can be prepared into a solution which is uniformly dissolved in an organic solvent. In this case, the concentration of the perfluoropolyether group-containing acrylate compound in the solution is not particularly limited as long as the range of the homogeneous solution is obtained, and it is usually 1 to 50% by mass, preferably 5 to 30% by mass. %, more preferably about 5 to 20% by mass.
作為溶解含有全氟聚醚基的丙烯酸酯化合物之有機溶劑,選擇不與(A)成分對硬塗層材料反應者,例如可舉出己烷、庚烷、異辛烷、異癸烷等之脂肪族烴系溶劑,甲苯、二甲苯等之芳香族烴系溶劑,甲醇、乙醇、異丙醇等之醇系溶劑,丙酮、甲基乙基酮、甲基異丁基酮、環己酮等之酮系溶劑,乙二醇單乙基醚、乙二醇單第三丁基醚、丙二醇單甲基醚等之二醇醚系溶劑,醋酸乙酯、醋酸丁酯、丙二醇單甲基醚醋酸酯等之酯系溶劑等。其中,較宜使用甲基乙基酮、甲基異丁基酮、異丙醇等。 As the organic solvent for dissolving the perfluoropolyether group-containing acrylate compound, those which do not react with the (A) component for the hard coat material are selected, and examples thereof include hexane, heptane, isooctane, isodecane, and the like. An aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent such as toluene or xylene; an alcohol solvent such as methanol, ethanol or isopropyl alcohol; acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; a ketone solvent, a glycol ether solvent such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether or propylene glycol monomethyl ether, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate An ester solvent such as an ester. Among them, methyl ethyl ketone, methyl isobutyl ketone, isopropyl alcohol and the like are preferably used.
(C)成分之含有全氟聚醚基的丙烯酸酯化合物之添加量,相對於(A)成分之硬塗層材料100質量份,若以(上述溶液中的固體成分)0.1~3質量份,更佳以0.2~2質量份之比例來添加,則可得到良好的表面特性。未達上 述下限值時,對硬塗層表面的溶出係困難,有得不到適宜的特性之虞。又,超過上述上限值時,由於損害對樹脂的親和性,有發生外觀的白化或硬度的降低等之虞。 The amount of the perfluoropolyether group-containing acrylate compound to be added to the component (C) is 0.1 to 3 parts by mass based on 100 parts by mass of the hard coat material of the component (A). More preferably, it is added in a ratio of 0.2 to 2 parts by mass to obtain good surface characteristics. Not up When the lower limit is described, the elution of the surface of the hard coat layer is difficult, and the appropriate characteristics are not obtained. Moreover, when it exceeds the above-mentioned upper limit, the affinity for the resin may be impaired, and whitening of the appearance or a decrease in hardness may occur.
本發明之硬塗層組成物,係為了使各成分均勻地分散,可更用能溶解上述(B)、(C)成分之溶劑所例示之溶劑等來適宜稀釋。又,於不損害本發明的目的之範圍內,亦可摻合均平劑、增黏劑等之添加劑。 The hard coat composition of the present invention is suitably diluted with a solvent exemplified by a solvent capable of dissolving the above components (B) and (C) in order to uniformly disperse the components. Further, an additive such as a leveling agent or a tackifier may be blended insofar as the object of the present invention is not impaired.
本發明之硬塗層組成物係藉由在硬塗層材料中摻合上述2種類的防污性賦予劑((B)、(C)成分),而可對硬塗層表面賦予防污性、耐指紋性等。藉此,可賦予即使附著指紋、皮脂、汗等之人脂、化妝品等也不醒目,或即使附著髒污時拭去性也優異之硬塗層表面。因此,本發明之硬塗層組成物係可施予在因人體接觸而有被人脂、化妝品等污染之可能性的物品表面,可使用於形成塗裝膜或保護膜,有用作為硬化性組成物。作為如此的物品,例如可舉出以光磁碟、CD‧LD‧DVD‧藍光光碟等之光碟、全像記錄等為代表之光記錄媒體;眼鏡片、稜鏡、透鏡片、皮膜、偏光板、光學濾片、雙凸透鏡、菲涅透鏡、防反射膜、光纖或光耦合器等之光學零件‧光學裝置;CRT、液品顯示器、電漿顯示器、電致發光顯示器、背面投影型顯示器、螢光顯示管(VFD)、場致發光顯示器、碳粉系顯示器等之各種畫面顯示機器,尤其PC、行動電話、攜帶式資訊終端、遊戲機、數位相機、數位攝影機、自動現金取出存入裝置、自動提款機、自動販售機、汽車用等之 導航裝置、保全系統終端等之影像顯示裝置、及該操作亦進行之觸控面板(觸控感測器、觸控螢幕)式影像顯示輸入裝置;行動電話、攜帶式資訊終端、攜帶式音樂播放器、攜帶式遊戲機、遙控器、控制器、鍵盤等、車載裝置用面板開關等之輸入裝置;行動電話、攜帶式資訊終端、照相機、攜帶式音樂播放器、攜帶式遊戲機等之殼體表面;汽車之外裝、鋼琴、高級家具、大理石等之塗裝及表面;美術品展示用保護玻璃、陳列窗、陳列箱、廣告用蓋、相片座用蓋、手錶、汽車用前玻璃、列車、航空飛機等之窗玻璃、汽車頭燈、尾燈等之透明玻璃製或透明塑膠製(壓克力、聚碳酸酯等)構件、各種鏡面構件等。 The hard coat composition of the present invention can impart antifouling properties to the surface of the hard coat layer by blending the above two types of antifouling imparting agents (components (B) and (C)) into the hard coat material. , fingerprint resistance, etc. Thereby, it is possible to impart a surface of the hard coat layer which is excellent in the wiping property even when the human fat, the cosmetics, and the like which adhere to fingerprints, sebum, sweat, and the like are not conspicuous, or even if the stain is adhered. Therefore, the hard coat composition of the present invention can be applied to the surface of an article which is likely to be contaminated by human fat, cosmetics or the like due to human contact, and can be used for forming a coating film or a protective film, and is useful as a hardening component. Things. Examples of such an article include optical recording media such as optical disks, CDs, CDs, DVDs, Blu-ray disks, and the like, and holograms, lenses, lenses, films, and polarizers. Optical components such as optical filters, lenticular lenses, Fresnel lenses, anti-reflection films, optical fibers or optical couplers, optical devices, CRTs, liquid displays, plasma displays, electroluminescent displays, rear projection displays, and fluorescent devices. Various display devices such as light display tubes (VFDs), electroluminescent displays, and toner-based displays, especially PCs, mobile phones, portable information terminals, game consoles, digital cameras, digital cameras, automatic cash withdrawal devices, Automatic teller machines, vending machines, automobiles, etc. Video display device for navigation device, security system terminal, etc., and touch panel (touch sensor, touch screen) image display input device for the operation; mobile phone, portable information terminal, portable music player Input device such as a portable game machine, a remote controller, a controller, a keyboard, a panel switch for an in-vehicle device, a mobile phone, a portable information terminal, a camera, a portable music player, a portable game machine, and the like Surface; exterior and exterior of automobile, piano, high-grade furniture, marble, etc.; protective glass for art display, display window, display box, advertising cover, photo cover, watch, front glass for cars, train Transparent glass or transparent plastic (acrylic, polycarbonate, etc.) components such as window glass, automobile headlights, and taillights, and various mirror members.
藉由將本發明之硬塗層組成物塗佈在上述物品之外面,進行紫外線硬化,而形成硬塗層塗膜(硬化膜)。 The hard coat layer (cured film) is formed by applying the hard coat composition of the present invention to the outer surface of the article and ultraviolet curing.
作為塗布方法,可例示旋塗、浸塗、刷毛塗佈等。 As a coating method, spin coating, dip coating, brush coating, etc. are illustrated.
再者,作為紫外線硬化條件,可藉由以照射量200~2,000mJ/cm2,較佳400~1,600mJ/cm2左右,照射波長100~400nm、較佳200~400nm左右之紫外線而使硬化。 Further, as the ultraviolet curing condition, the ultraviolet light can be hardened by irradiation with an ultraviolet ray having a wavelength of 100 to 400 nm, preferably about 200 to 400 nm, with an irradiation amount of 200 to 2,000 mJ/cm 2 , preferably about 400 to 1,600 mJ/cm 2 . .
再者,硬塗層硬化膜之厚度通常可為0.1~30μm,較佳可為1~10μm左右。 Further, the thickness of the hard coat cured film may be usually from 0.1 to 30 μm, preferably from about 1 to 10 μm.
以下,藉由實施例及比較例來具體說明本發明,惟本發明係不受以下之實施例所限定。 Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited by the following examples.
於10ml玻璃製樣品瓶中,秤量下述防污添加劑(B)、(C)成分中的任一者2.0g與甲基異丁基酮(MIBK)8.0g,進行密栓,振盪30分鐘。確認該防污添加劑已完全溶解,用孔徑0.45μm之PTFE(聚四氟乙烯)製薄膜過濾器來過濾,分別調製含有20質量%的(B)成分或(C)成分作為防污性賦予成分之防污性賦予劑。 In a 10 ml glass sample vial, 2.0 g of any of the following antifouling additives (B) and (C) and 8.0 g of methyl isobutyl ketone (MIBK) were weighed and sealed, and shaken for 30 minutes. It was confirmed that the antifouling additive was completely dissolved, and it was filtered with a membrane filter made of PTFE (polytetrafluoroethylene) having a pore size of 0.45 μm to prepare 20% by mass of the component (B) or the component (C) as an antifouling imparting component. Antifouling imparting agent.
Rf’:-CF2(OCF2CF2)G1(OCF2)H1OCF2-(G1/H1=0.9、G1+H1≒45) Rf': -CF 2 (OCF 2 CF 2 ) G1 (OCF 2 ) H1 OCF 2 - (G1/H1=0.9, G1+H1≒45)
Rf’:-CF2(OCF2CF2)G1(OCF2)H1OCF2-(G1/H1=0.9、G1+H1≒45) Rf': -CF 2 (OCF 2 CF 2 ) G1 (OCF 2 ) H1 OCF 2 - (G1/H1=0.9, G1+H1≒45)
以如下述表1所示之配合來調製硬塗層組成物。 The hard coat composition was prepared by blending as shown in Table 1 below.
EBECRYL 40:4官能丙烯酸酯,DAICEL科學公司製 EBECRYL 40: 4-functional acrylate, manufactured by DAICEL Scientific
Irgacure 184:1-羥基環己基苯基酮,CIBA日本公司製 Irgacure 184: 1-hydroxycyclohexyl phenyl ketone, manufactured by CIBA Japan
將摻合有防污性賦予劑的各溶液(硬塗層組成物)旋塗在黑色的聚甲基丙烯酸甲酯板(5×5×0.2cm)上,用輸送型紫外線照射裝置(PANASONIC電工公司製),在氮氣環境中,照射1.6J/cm2之紫外線以形成硬化膜。硬化後的硬塗層膜之膜厚為7μm。將塗佈有此硬塗層膜的材料當作試件,供以下之試驗。 Each solution (hard coat composition) blended with the antifouling agent was spin-coated on a black polymethyl methacrylate plate (5 × 5 × 0.2 cm), and a transport type ultraviolet irradiation device (PANASONIC electrician) As a company, ultraviolet rays of 1.6 J/cm 2 were irradiated in a nitrogen atmosphere to form a cured film. The film thickness of the hardened coating film after hardening was 7 μm. The material coated with this hard coat film was used as a test piece for the following test.
目視評價硬塗層膜之外觀(色調.透明性、平滑性)。表2中記載結果。 The appearance (hue, transparency, smoothness) of the hard coat film was visually evaluated. The results are shown in Table 2.
使用接觸角計(協和界面科學公司製)來測定硬塗層膜表面對水及油酸之接觸角。表2中記載結果。 A contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the contact angle of the surface of the hard coat film with water and oleic acid. The results are shown in Table 2.
用以下之方法進行耐指紋性試驗(指紋視覺辨認性、指紋拭去性)。試驗係藉由5名的小組成員來進行。評價結果係將5名的評價值中最多的評價值當作評價結果。當2個以上的評價值為同數,由5名之協議來決定評價值。表2中記載結果。 The fingerprint resistance test (fingerprint visibility, fingerprint wiping property) was carried out by the following method. The trial was conducted by five panelists. As a result of the evaluation, the most evaluation value among the five evaluation values was taken as the evaluation result. When two or more evaluation values are the same, the evaluation value is determined by a protocol of five. The results are shown in Table 2.
用食指按壓硬塗層膜表面,保持3秒後,安靜地使手指離開。在波長發光形螢光燈下,從塗膜之正上方來目視觀察所附著的指紋之視覺辨認性,用以下4個等級來評價。 The surface of the hard coating film was pressed with the index finger, and after holding for 3 seconds, the finger was quietly left. Under the wavelength-emitting fluorescent lamp, the visibility of the attached fingerprint was visually observed from directly above the coating film, and evaluated by the following four grades.
◎…無法看到指紋。 ◎... I can't see the fingerprint.
○…幾乎無法看到指紋。 ○...I can hardly see the fingerprint.
△…可看到若干指紋。 △...You can see several fingerprints.
×…可清晰地看到指紋。 ×...The fingerprint can be clearly seen.
用不織布(Bemcot M-3II[旭化成纖維公司製])單向來回拭去在硬塗層膜表面所附著的指紋。於三波長發光形螢光燈下,自塗膜的傾斜45°上方,目視觀察拭去後之狀 態,用以下的3個等級來評價直到無法目視看到指紋為止的來回次數。 The non-woven fabric (Bemcot M-3II [made by Asahi Kasei Fiber Co., Ltd.]) was used to wipe back the fingerprint attached to the surface of the hard coat film. Under the three-wavelength luminescent fluorescent lamp, the angle of the self-coated film is inclined above 45°, and the shape after wiping is visually observed. State, the following three levels are used to evaluate the number of round trips until the fingerprint is not visible.
◎…未達3次來回而可拭去指紋。 ◎... The fingerprint can be wiped off after 3 round trips.
○…3次來回以上且未達5次來回而可拭去指紋。 ○... 3 times back and forth and less than 5 round trips can be wiped off.
×…即使5次來回以上擦拭也無法拭去指紋。 ×... Even if you wipe it back and forth 5 times, you cannot wipe the fingerprint.
與前述實施例1同樣,以下述表3之配合來調製硬塗層組成物。 The hard coat composition was prepared in the same manner as in the above Example 1 by the combination of the following Table 3.
與前述實施例1同樣,調製硬塗層塗佈材料,同樣地測定特性,為下述表4之結果。 The hard coat coating material was prepared in the same manner as in the above Example 1, and the properties were measured in the same manner, and the results are shown in Table 4 below.
以下顯示B-1~B-3成分之合成例。 The synthesis examples of the components B-1 to B-3 are shown below.
於安裝有回流冷卻管與溫度計之燒瓶中,加入下述式(I)
其次,於安裝有回流冷卻管與溫度計之燒瓶中,加入上述所得之含氟矽氧烷(II)44.8g(0.030莫耳)與丙烯醯氧基乙基異氰酸酯8.9g(0.063莫耳)及甲基異丁基酮53.7g。將內溫加熱至50℃為止後,添加二月桂酸二丁錫 0.02g,在50~60℃反應2小時。反應後,添加乙醇0.90g,藉由IR光譜之測定確認NCO的吸收已消失後,在25℃餾去溶劑,結果得到49.9g透明的糊狀生成物。 Next, in the flask equipped with the reflux cooling tube and the thermometer, 44.8 g (0.030 mol) of the fluorine-containing fluorinated alkane (II) obtained above and 8.9 g (0.063 mol) of acryloxyethyl isocyanate and A were added. Isobutyl ketone 53.7 g. After heating the internal temperature to 50 ° C, dibutyltin dilaurate was added. 0.02 g, reacted at 50 to 60 ° C for 2 hours. After the reaction, 0.90 g of ethanol was added, and it was confirmed by IR spectrum measurement that the absorption of NCO had disappeared, and the solvent was distilled off at 25 ° C to obtain 49.9 g of a transparent paste product.
藉由1H-NMR及IR光譜之測定來分析上述所得之生成物,結果為下述式所示之含氟丙烯酸酯化合物。 The product obtained above was analyzed by measurement of 1 H-NMR and IR spectrum, and found to be a fluorine-containing acrylate compound represented by the following formula.
於安裝有回流冷卻管與溫度計之燒瓶中,加入上述式(I)所示之含氟氫矽氧烷43.1g(0.050莫耳)、甲苯18.8g、鉑/乙烯基矽氧烷錯合物甲苯溶液0.04g(含有0.2mg的鉑)。將內溫加熱至60℃為止後,自滴液漏斗,以內溫不成為70℃以上之方式,調整滴下速率,滴下1-十二烯33.6g(0.20莫耳)。在60~70℃加熱1小時後,以內溫不成為70℃以上之方式,調整滴下速率,滴下4-戊烯醇17.2g(0.20莫耳)。藉由IR光譜之測定,確認來自含氟氫矽氧烷(I)之SiH基的吸收已消失後,於減壓下餾去六氟間二甲苯與過剩的環四矽氧烷,得到下述式(III)所示之含氟矽氧烷80.4g。 To the flask equipped with the reflux cooling tube and the thermometer, 43.1 g (0.050 mol) of fluorine-containing hydrooxane represented by the above formula (I), 18.8 g of toluene, and platinum/vinyl azide complex toluene were added. The solution was 0.04 g (containing 0.2 mg of platinum). After the internal temperature was heated to 60 ° C, the dropping rate was adjusted so that the internal temperature did not become 70 ° C or more, and 33.6 g (0.20 mol) of 1-dodecene was dropped. After heating at 60 to 70 ° C for 1 hour, the dropping rate was adjusted so that the internal temperature did not become 70 ° C or higher, and 17.2 g (0.20 mol) of 4-pentenol was dropped. After confirming the disappearance of the absorption of the SiH group derived from the fluorine-containing hydroquinone (I) by the measurement of the IR spectrum, the hexafluorom-xylene and the excess cyclotetraoxane were distilled off under reduced pressure to obtain the following. 80.4 g of a fluorine-containing oxirane represented by the formula (III).
其次,於安裝有回流冷卻管與溫度計之燒瓶中,加入上述所得之含氟矽氧烷(III)31.4g(0.030莫耳)與丙烯醯氧基乙基異氰酸酯8.9g(0.063莫耳)及甲基異丁基酮40.3g。將內溫加熱至50℃為止後,添加二月桂酸二丁錫0.02g,在50~60℃反應2小時。反應後,添加乙醇1.55g,藉由IR光譜之測定確認NCO的吸收已消失後,在25℃餾去溶劑,結果得到36.4g透明的糊狀生成物。 Next, in the flask equipped with the reflux cooling tube and the thermometer, 31.4 g (0.030 mol) of the fluorine-containing fluorinated alkane (III) obtained above and 8.9 g (0.063 mol) of acryloxyethyl isocyanate and a Isobutyl ketone 40.3 g. After heating the internal temperature to 50 ° C, 0.02 g of dibutyltin dilaurate was added, and the reaction was carried out at 50 to 60 ° C for 2 hours. After the reaction, 1.55 g of ethanol was added, and it was confirmed by IR spectrum measurement that the absorption of NCO had disappeared, and the solvent was distilled off at 25 ° C to obtain 36.4 g of a transparent paste product.
藉由1H-NMR及IR光譜之測定來分析上述所得之生成物,結果為下述式所示之含氟丙烯酸酯化合物。 The product obtained above was analyzed by measurement of 1 H-NMR and IR spectrum, and found to be a fluorine-containing acrylate compound represented by the following formula.
於安裝有回流冷卻管與溫度計之燒瓶中,加入上述式(I)所示之含氟氫矽氧烷43.1g(0.050莫耳)、甲苯20.6g、鉑/乙烯基矽氧烷錯合物甲苯溶液0.04g(含有 0.2mg的鉑)。將內溫加熱至60℃為止後,自滴液漏斗,以內溫不成為70℃以上之方式,調整滴下速率,滴下10-十一烯酸乙酯42.5g(0.20莫耳)。在60~70℃加熱1小時後,以內溫不成為70℃以上之方式,調整滴下速率,滴下4-戊烯醇17.2g(0.20莫耳)。藉由IR光譜之測定,確認來自含氟氫矽氧烷(I)之SiH基的吸收已消失後,於減壓下餾去六氟間二甲苯與過剩的環四矽氧烷,得到述式(IV)所示之含氟矽氧烷93.4g。 To the flask equipped with the reflux cooling tube and the thermometer, 43.1 g (0.050 mol) of the fluorine-containing hydrooxane represented by the above formula (I), 20.6 g of toluene, and platinum/vinyl azide complex toluene were added. Solution 0.04g (containing 0.2 mg of platinum). After the internal temperature was heated to 60 ° C, the dropping rate was adjusted so that the internal temperature did not become 70 ° C or higher, and 42.5 g (0.20 mol) of ethyl 10-undecenoate was added dropwise. After heating at 60 to 70 ° C for 1 hour, the dropping rate was adjusted so that the internal temperature did not become 70 ° C or higher, and 17.2 g (0.20 mol) of 4-pentenol was dropped. After confirming the disappearance of the absorption of the SiH group derived from the fluorine-containing hydroquinone (I) by the measurement of the IR spectrum, the hexafluorom-xylene and the excess cyclotetraoxane were distilled off under reduced pressure to obtain a formula. 93.4 g of fluorine-containing oxane as shown in (IV).
其次,於安裝有回流冷卻管與溫度計之燒瓶中,加入上述所得之含氟矽氧烷(IV)30.9g(0.030莫耳)與丙烯醯氧基乙基異氰酸酯8.9g(0.063莫耳)及甲基異丁基酮39.8g。將內溫加熱至50℃為止後,添加二月桂酸二丁錫0.02g,在50~60℃反應2小時。反應後,添加乙醇1.58g,藉由IR光譜之測定確認NCO的吸收已消失後,在25℃餾去溶劑,結果得到34.2g透明的糊狀生成物。 Next, in the flask equipped with the reflux cooling tube and the thermometer, 30.9 g (0.030 mol) of the fluorine-containing fluorinated alkane (IV) obtained above and 8.9 g (0.063 mol) of acryloxyethyl isocyanate and A were added. Isobutyl ketone 39.8 g. After heating the internal temperature to 50 ° C, 0.02 g of dibutyltin dilaurate was added, and the reaction was carried out at 50 to 60 ° C for 2 hours. After the reaction, 1.58 g of ethanol was added, and it was confirmed by IR spectrum measurement that the absorption of NCO had disappeared, and the solvent was distilled off at 25 ° C to obtain 34.2 g of a transparent paste product.
藉由1H-NMR及IR光譜之測定來分析上述所得之生成物,結果為下述式所示之含氟丙烯酸酯化合物。 The product obtained above was analyzed by measurement of 1 H-NMR and IR spectrum, and found to be a fluorine-containing acrylate compound represented by the following formula.
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JPWO2016143565A1 (en) * | 2015-03-12 | 2018-02-01 | 旭硝子株式会社 | LAMINATE MANUFACTURING METHOD, LAMINATE, AND PHOTOCURABLE COMPOSITION |
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JP7021856B2 (en) * | 2016-03-14 | 2022-02-17 | 中国塗料株式会社 | A photocurable resin composition, a cured film, a coated base material and a method for producing the same, and an anti-fog treatment method for the base material. |
JP6497350B2 (en) * | 2016-04-15 | 2019-04-10 | 信越化学工業株式会社 | Fluorine-containing acrylic composition and method for producing the same, fluorine-containing active energy ray-curable composition and article |
JP6658449B2 (en) * | 2016-10-25 | 2020-03-04 | 信越化学工業株式会社 | Fluorine-containing acrylic compound, method for producing the same, and curable composition and article |
KR102659594B1 (en) * | 2017-10-04 | 2024-04-19 | 닛토 가세이 가부시끼 가이샤 | Antifouling paint composition, a painted object having an antifouling coating film formed using this composition on the surface |
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