TWI655252B - Ultraviolet-ray-curable coating composition, hard coat film and method for manufacturing same - Google Patents
Ultraviolet-ray-curable coating composition, hard coat film and method for manufacturing same Download PDFInfo
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Abstract
本發明之課題在於提供一種紫外線硬化性塗佈組成物，該紫外線硬化性塗佈組成物水親和性低且防污性優異，並且可賦予具有高平滑性、高透明性及高硬度之硬化覆膜，對於硬塗層的形成為有用紫外線硬化性塗佈組成物。此外，並提供一種使用該紫外線硬化性塗佈組成物之硬塗薄膜及該硬塗薄膜之製造方法。 An object of the present invention is to provide an ultraviolet curable coating composition which is low in water affinity and excellent in antifouling property, and which can provide hardening coating having high smoothness, high transparency, and high hardness. The film is a useful ultraviolet curable coating composition for the formation of a hard coat layer. Further, a hard coat film using the ultraviolet curable coating composition and a method for producing the hard coat film are provided.
本發明之解決手段係提供一種紫外線硬化性塗佈組成物，含有紫外線硬化性成分、光聚合起始劑及溶劑，該紫外線硬化性成分係分子內含有氟之硬化性化合物與分子內不含氟之硬化性化合物之混合物，並且在將各硬化性化合物1g分別單獨混合分散於丙酮10ml並將水加入所得之分散液時，將至該分散液產生白濁為止之所需水量定義為該硬化性化合物的耐水度，根據所得之各硬化性化合物的耐水度，以下述數學式(1)定義之親和力A係於1至2的範 圍。 The solution of the present invention provides an ultraviolet curable coating composition comprising an ultraviolet curable component, a photopolymerization initiator, and a solvent, wherein the ultraviolet curable component is a curable compound containing fluorine in the molecule and no fluorine in the molecule. a mixture of the curable compounds, and when 1 g of each of the curable compounds is separately mixed and dispersed in acetone 10 ml and water is added to the obtained dispersion, the amount of water required until the dispersion is cloudy is defined as the curable compound. The water resistance is based on the water resistance of each of the obtained curable compounds, and the affinity A defined by the following formula (1) is in the range of 1 to 2. Wai.
親和力A=紫外線硬化性成分中分子內含有氟之硬化性化合物的重量分率×(分子內不含氟之硬化性化合物的耐水度一分子內含有氟之硬化性化合物的耐水度)‧‧‧(1) Affinity A = weight fraction of the curable compound containing fluorine in the ultraviolet curable component × (water resistance of the curable compound containing no fluorine in the molecule; water resistance of the curable compound containing fluorine in one molecule) ‧ ‧ (1)
Description
本發明係關於適合使用在硬塗層的形成之紫外線硬化性塗佈組成物，以及使用該紫外線硬化性塗佈組成物之硬塗薄膜及該硬塗薄膜之製造方法。 The present invention relates to an ultraviolet curable coating composition suitable for use in the formation of a hard coat layer, and a hard coat film using the ultraviolet curable coating composition and a method for producing the hard coat film.
液晶顯示器、電漿顯示面板、映像管(陰極射線管：CRT)顯示器、有機電激發光(EL：Electroluminescence)顯示器等影像顯示裝置，為了防止起因於各種外力之損傷，大多在最表面上設置硬塗層。該硬塗層，從防止外光映入之觀點來看，大多亦施以利用光學多層膜所形成之干涉之抗反射處理，或是於表面形成細微凹凸以使入射光散射而將映入影像模糊化之防眩處理。 Image display devices such as liquid crystal displays, plasma display panels, image tube (CRT) displays, and organic electroluminescence (EL) displays are often hardened on the outer surface in order to prevent damage caused by various external forces. coating. The hard coat layer is often subjected to anti-reflection treatment by interference formed by an optical multilayer film from the viewpoint of preventing external light from being reflected, or fine irregularities are formed on the surface to scatter incident light to be reflected in the image. Fuzzy anti-glare treatment.
一般而言，硬塗層係藉由將含有紫外線硬化性樹脂之塗佈組成物塗佈於基材薄膜上，並於該處照射紫外線使樹脂硬化而製造。該紫外線硬化性樹脂，亦即藉由紫外線進行硬化之化合物，大多採用分子內具有(甲基) 丙烯醯基之單體或低聚物。 In general, a hard coat layer is produced by applying a coating composition containing an ultraviolet curable resin to a base film, and irradiating the ultraviolet rays thereto to cure the resin. The ultraviolet curable resin, that is, a compound which is hardened by ultraviolet rays, is mostly intramolecular (meth) a monomer or oligomer of acrylonitrile.
例如於日本特開2007-262281號公報(專利文獻1)中，揭示一種將紫外線硬化性樹脂組成物塗佈於透明基材上後，對所得之塗膜，於第一照射步驟中，在氧較空氣中之氧含量更少之狀態下，以例如將該塗膜壓抵於模具之狀態，從透明基材側照射紫外線，以使上述紫外線硬化性樹脂組成物硬化，然後於第二照射步驟中，從塗膜側照射紫外線，藉此製造高硬度硬塗薄膜之技術。該紫外線硬化性樹脂組成物含有多官能(甲基)丙烯酸酯、具有羥基之(甲基)丙烯酸酯與六亞甲二異氰酸酯反應所得之多官能胺甲酸乙酯化(甲基)丙烯酸酯，以及光聚合起始劑。 For example, in Japanese Laid-Open Patent Publication No. 2007-262281 (Patent Document 1), after coating an ultraviolet curable resin composition on a transparent substrate, the obtained coating film is subjected to oxygen in the first irradiation step. In a state where the oxygen content in the air is less than that in the air, for example, the coating film is pressed against the mold, ultraviolet rays are irradiated from the transparent substrate side to cure the ultraviolet curable resin composition, and then in the second irradiation step. Among them, a technique of producing a high-hardness hard coat film by irradiating ultraviolet rays from the side of the coating film. The ultraviolet curable resin composition contains a polyfunctional (meth) acrylate, a polyfunctional amine ethyl formate (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylate with hexamethylene diisocyanate, and Photopolymerization initiator.
於日本特開2012-072235號公報(專利文獻2)中，揭示一種將紫外線硬化性樹脂組成物塗佈於可吸收既定波長以下的紫外線之透明基材薄膜上以形成紫外線硬化性層後，在將該紫外線硬化性層妥善壓抵於模具之狀態下，從透明基材薄膜側，照射在該透明基材薄膜吸收之紫外線波長區域外顯示最大發光強度之第1紫外線，接著從紫外線硬化性層側，照射在該透明基材薄膜吸收之紫外線波長區域內顯示最大發光強度之第2紫外線，藉此製造硬塗薄膜之技術。在此，藉由在上述紫外線硬化性樹脂組成物中，使含有在透明基材薄膜吸收之紫外線波長區域外具有極大吸收之第1光聚合起始劑，以及僅在透明基材薄膜吸收之紫外線波長區域內具有極大吸收之第2光聚合起始劑，而形成硬度高且對基材薄膜之密合性優異之硬塗層。 此外，構成紫外線硬化性樹脂組成物之紫外線硬化性樹脂，可列舉多官能(甲基)丙烯酸酯系化合物。 In JP-A-2012-072235 (Patent Document 2), it is disclosed that an ultraviolet curable resin composition is applied onto a transparent base film which can absorb ultraviolet rays having a predetermined wavelength or less to form an ultraviolet curable layer. When the ultraviolet curable layer is properly pressed against the mold, the first ultraviolet ray having the maximum luminescence intensity outside the ultraviolet ray wavelength region absorbed by the transparent substrate film is irradiated from the transparent substrate film side, and then the ultraviolet ray curable layer is applied. On the side, a technique of producing a hard coat film by irradiating the second ultraviolet ray having the maximum luminescence intensity in the ultraviolet ray wavelength region absorbed by the transparent base film is irradiated. Here, in the ultraviolet curable resin composition, the first photopolymerization initiator containing the maximum absorption outside the ultraviolet wavelength region absorbed by the transparent substrate film and the ultraviolet rays absorbed only in the transparent substrate film are contained. A second photopolymerization initiator having a maximum absorption in the wavelength region forms a hard coat layer having high hardness and excellent adhesion to the base film. In addition, examples of the ultraviolet curable resin constituting the ultraviolet curable resin composition include polyfunctional (meth)acrylate compounds.
於日本特開2012-233989號公報(專利文獻3)及日本特開2013-174638號公報(專利文獻4)中，揭示一種在連續運送之基材薄膜上，塗佈含有紫外線硬化性樹脂之塗佈液而形成塗佈層，在將該塗佈層的表面壓抵於模具表面之狀態下，從基材薄膜側照射紫外線使塗佈層硬化，藉此製造光學薄膜之技術。此等文獻中，紫外線硬化性樹脂亦可列舉多官能(甲基)丙烯酸酯化合物。 In Japanese Laid-Open Patent Publication No. 2012-174638 (Patent Document 3), JP-A-2013-174638 (Patent Document 4) discloses the application of a coating containing a UV curable resin on a substrate film which is continuously conveyed. A technique of producing an optical film by forming a coating layer by a liquid coating and pressing the surface of the coating layer against the surface of the mold to irradiate ultraviolet rays from the side of the base film to cure the coating layer. Among these documents, a polyfunctional (meth) acrylate compound is also mentioned as an ultraviolet curable resin.
以上的專利文獻1至4中，亦記載有將平坦化劑調配於紫外線硬化性樹脂組成物(塗佈液)之內容。 In the above-mentioned Patent Documents 1 to 4, the content of the flattening agent in the ultraviolet curable resin composition (coating liquid) is also described.
另一方面，以分子內含有氟之硬化性化合物作為硬化性樹脂亦為人所知。例如於日本國際公開第2007/102370號公報(專利文獻5)中，揭示一種含有：多官能性丙烯酸酯、具有脂肪族不飽和鍵之有機烷氧矽烷、膠體二氧化矽、及具有脂肪族不飽和鍵之氟化合物之紫外線硬化性組成物，亦記載有將該組成物塗佈於基材薄膜上，進行紫外線硬化而形成硬化覆膜(硬塗層)之內容。此外，於日本特表2012-518713號公報(專利文獻6)中，揭示一種含有：含紫外線硬化型官能基之黏合劑樹脂、含氟系紫外線硬化型官能基之化合物、光聚合起始劑、奈米微粒、以及導電性無機粒子之塗佈組成物。 On the other hand, a curable compound containing fluorine in a molecule is also known as a curable resin. For example, Japanese Laid-Open Patent Publication No. 2007/102370 (Patent Document 5) discloses a polyfunctional acrylate, an organic alkoxysilane having an aliphatic unsaturated bond, a colloidal cerium oxide, and an aliphatic The ultraviolet curable composition of the fluorine compound having a saturated bond is also described in which the composition is applied onto a base film and cured by ultraviolet rays to form a cured film (hard coat layer). Japanese Patent Publication No. 2012-518713 (Patent Document 6) discloses a binder resin containing an ultraviolet curable functional group, a fluorine-containing ultraviolet curable functional group compound, a photopolymerization initiator, and A coating composition of nanoparticles and conductive inorganic particles.
[專利文獻1]日本特開2007-262281號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-262281
[專利文獻2]日本特開2012-072235號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2012-072235
[專利文獻3]日本特開2012-233989號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2012-233989
[專利文獻4]日本特開2013-174638號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2013-174638
[專利文獻5]日本國際公開第2007/102370號公報 [Patent Document 5] Japanese International Publication No. 2007/102370
[專利文獻6]日本特表2012-518713號公報 [Patent Document 6] Japanese Patent Publication No. 2012-518713
根據如專利文獻1至4所揭示般在將塗佈層壓抵於模具之狀態下照射紫外線使塗佈層硬化之方法，或是因應必要隨後再從硬化後之塗佈層側再次照射紫外線之方法，能夠以高透明性及高硬度形成平滑鏡面之硬塗層，或是模具的凹凸直接賦形於表面之外觀良好的硬塗層。然而，尤其當採用此方法時，所得硬塗層之水親和性變大，有時難以適應防污性要求特別高之領域。具體而言，當將某塗佈組成物塗佈於基材薄膜上，並在將此與大氣接觸之狀態下硬化時，所得之硬塗層顯示出100°左右的對水接觸角，相對於此，將相同塗佈組成物塗佈於基材薄膜上，並將塗佈層壓抵於模具使硬化時，所得之硬塗層的對水接觸角約為60°左右。 According to the methods disclosed in Patent Documents 1 to 4, the coating layer is cured by irradiating ultraviolet rays in a state where the coating is laminated against the mold, or the ultraviolet rays are again irradiated from the side of the coating layer after hardening as necessary. The method can form a smooth mirror hard coating with high transparency and high hardness, or the concave and convex of the mold can directly form a hard coating with good appearance on the surface. However, especially when this method is employed, the water affinity of the obtained hard coat layer becomes large, and it is sometimes difficult to adapt to a field in which the antifouling property is particularly high. Specifically, when a coating composition is applied onto a base film and hardened in contact with the atmosphere, the obtained hard coat layer exhibits a water contact angle of about 100° with respect to Thus, the same coating composition is applied to the base film, and the coating is laminated against the mold to harden, and the resulting hard coat layer has a water contact angle of about 60°.
其原因可考量如下：當塗佈液含有平坦化劑時，該平坦化劑殘留於硬化後的塗佈層，亦即硬塗層，而往降低水親和性之方向作用時，平坦化劑容易於塗佈層 的表面附近懸浮，在與大氣接觸之狀態下硬化時，該平坦化劑幾乎直接殘留於硬塗層，相對於此，在將塗佈層壓抵於模具之狀態下硬化時，該平坦化劑大多會移往模具的表面。 The reason for this can be considered as follows: When the coating liquid contains a planarizing agent, the planarizing agent remains in the cured coating layer, that is, a hard coat layer, and the planarizing agent is easy to act in the direction of lowering water affinity. Coating layer The flattening agent is suspended in the vicinity of the surface, and the flattening agent remains almost directly on the hard coat layer when it is hardened in contact with the atmosphere. On the other hand, the flattening agent is hardened in a state where the coating is laminated against the mold. Most will move to the surface of the mold.
如專利文獻5及6所揭示般，若使塗佈液內含有於分子內含有氟之硬化性化合物，則可降低所得之硬塗層的水親和性。然而，先前技術中，難以同時實現低水親和性、高平滑性、高透明度以及高硬度等全部特性。尤其在將於分子內含有氟之硬化性化合物，與不含氟之硬化性化合物，例如(甲基)丙烯酸系的硬化性化合物併用時，由於兩者的相溶性不足，亦有使所得之硬塗層的外觀惡化之問題。 As disclosed in Patent Documents 5 and 6, when the coating liquid contains a curable compound containing fluorine in the molecule, the water affinity of the obtained hard coat layer can be lowered. However, in the prior art, it is difficult to simultaneously achieve all characteristics such as low water affinity, high smoothness, high transparency, and high hardness. In particular, when a curable compound containing fluorine in a molecule is used in combination with a curable compound which does not contain fluorine, for example, a (meth)acrylic curable compound, the compatibility between the two is insufficient, and the hardening is also obtained. The problem of deterioration of the appearance of the coating.
因此，本發明之課題在於提供一種水親和性低，因此對水接觸角大而防污性優異，並且可賦予具有高平滑性、高透明性及高硬度且外觀亦良好之硬化覆膜，對於硬塗層的形成極為有用之紫外線硬化性塗佈組成物。本發明之另一課題在於提供一種具有由該紫外線硬化性塗佈組成物所形成，水親和性低，因此對水接觸角大而防污性優異，並且透明性、硬度及外觀亦優異之硬塗層之硬塗薄膜，並且提供其製造方法。 In view of the above, it is an object of the present invention to provide a hardened film having a high water contact angle and excellent antifouling property, and which can provide a smooth film having high smoothness, high transparency, high hardness and good appearance. The formation of a hard coat layer is an extremely useful ultraviolet curable coating composition. Another object of the present invention is to provide a composition which is formed of the ultraviolet curable coating composition and has low water affinity. Therefore, it has a large water contact angle and is excellent in antifouling property, and is excellent in transparency, hardness, and appearance. The coating is hard coated and provides a method of making it.
亦即，根據本發明，提供一種紫外線硬化性塗佈組成物，含有紫外線硬化性成分、光聚合起始劑及溶劑，該紫外線硬化性成分，係於分子內含有氟之硬化性化合物與於分子內不含氟之硬化性化合物之混合物，並且在將各硬化性化合物1g分別單獨混合分散於丙酮10ml並將水加入於所得之分散液時，將至該分散液產生白濁為止之所需水量定義為該硬化性化合物的耐水度，根據所得之各硬化性化合物的耐水度，以下述數學式(1)所定義之親和力A，係於1至2的範圍。 That is, according to the present invention, there is provided an ultraviolet curable coating composition comprising an ultraviolet curable component, a photopolymerization initiator, and a solvent, wherein the ultraviolet curable component is a curable compound containing fluorine in a molecule and a molecule A mixture of hardening compounds which do not contain fluorine, and when 1 g of each curable compound is separately mixed and dispersed in acetone 10 ml and water is added to the obtained dispersion, the amount of water required until the dispersion is white turbid The water resistance of the curable compound is based on the water resistance of each of the curable compounds obtained, and the affinity A defined by the following formula (1) is in the range of 1 to 2.
親和力A=紫外線硬化性成分中分子內含有氟之硬化性化合物的重量分率×(分子內不含氟之硬化性化合物的耐水度一分子內含有氟之硬化性化合物的耐水度)‧‧‧(1) Affinity A = weight fraction of the curable compound containing fluorine in the ultraviolet curable component × (water resistance of the curable compound containing no fluorine in the molecule; water resistance of the curable compound containing fluorine in one molecule) ‧ ‧ (1)
該紫外線硬化性塗佈組成物中，分子內含有氟之上述硬化性化合物，可為分子內具有氟烷基之胺甲酸乙酯化多官能(甲基)丙烯酸酯化合物。 In the ultraviolet curable coating composition, the curable compound containing fluorine in the molecule may be an urethane-based polyfunctional (meth) acrylate compound having a fluoroalkyl group in the molecule.
該胺甲酸乙酯化多官能(甲基)丙烯酸酯化合物的例子，可列舉以下述式(I)所示者。 Examples of the urethane-ethylated polyfunctional (meth) acrylate compound include those represented by the following formula (I).
式中，m表示3至16的整數，n表示1至5的整數，a表示1或2，b表示2至5的整數，X表示O、S或NH，Y表示從二或三異氰酸酯化合物中去除全部的異氰酸基所得之2價或3價的基，Z表示從3價至6價的多元醇中去除全部的羥基所得之3價至6價的基，R表示氫或 甲基。 Wherein m represents an integer of 3 to 16, n represents an integer of 1 to 5, a represents 1 or 2, b represents an integer of 2 to 5, X represents O, S or NH, and Y represents from a di- or triisocyanate compound. A divalent or trivalent group obtained by removing all of the isocyanato groups, and Z represents a trivalent to hexavalent group obtained by removing all of the hydroxyl groups from the trivalent to hexavalent polyol, and R represents hydrogen or methyl.
分子內不含氟之上述硬化性化合物，較佳係分子內具有至少2個(甲基)丙烯醯基。光聚合起始劑，較佳為選自醯基膦氧化物之第一光聚合起始劑，與選自由α-羥烷基苯酮、乙醛酸苯酯、苄基二烷基縮醛、安息香醚及α-胺烷基苯酮所組成之群組之第二光聚合起始劑的混合物。上述溶劑，相對於紫外線硬化性成分的合計量，較佳以0.5至2.5重量倍的比率含有。 The above curable compound which does not contain fluorine in the molecule preferably has at least two (meth) acrylonitrile groups in the molecule. a photopolymerization initiator, preferably a first photopolymerization initiator selected from the group consisting of mercaptophosphine oxides, and selected from the group consisting of α-hydroxyalkylphenones, phenyl glyoxylates, benzyl dialkyl acetals, A mixture of a second photopolymerization initiator of the group consisting of benzoin ether and alpha-aminoalkyl benzophenone. The solvent is preferably contained in a ratio of 0.5 to 2.5 times by weight based on the total amount of the ultraviolet curable components.
本發明之紫外線硬化性塗佈組成物，係以塗佈於基材的表面，將具有鏡面或凹凸面之模具壓抵於所得之塗佈層且使其硬化而形成硬化塗膜之方式中，從提高所得之硬化塗膜的防污性之觀點來看，可特佳地使用。 The ultraviolet curable coating composition of the present invention is applied to a surface of a substrate, and a mold having a mirror surface or a concave-convex surface is pressed against the obtained coating layer and cured to form a cured coating film. From the viewpoint of improving the antifouling property of the obtained cured coating film, it can be particularly preferably used.
此外，根據本發明，亦提供一種硬塗薄膜，具備透明基材薄膜、以及由上述任一項所述之紫外線硬化性塗佈組成物所構成之硬塗層。在此，透明基材薄膜例如可為由三乙酸纖維素、聚甲基丙烯酸甲酯、聚碳酸酯或聚對苯二甲酸乙二酯所構成之樹脂的薄膜。 Further, according to the present invention, there is provided a hard coat film comprising a transparent base film and a hard coat layer comprising the ultraviolet curable coating composition according to any one of the above. Here, the transparent base film may be, for example, a film of a resin composed of cellulose triacetate, polymethyl methacrylate, polycarbonate or polyethylene terephthalate.
再者，根據本發明，亦提供一種硬塗薄膜之製造方法，該方法具備：將上述任一項所述之紫外線硬化性塗佈組成物塗佈於透明基材薄膜的表面而形成塗佈層之塗佈步驟、從所得之塗佈層將溶劑乾燥去除之乾燥步驟、以及將紫外線照射在去除溶劑後之塗佈層而使上述塗佈層硬化之硬化步驟。 Furthermore, according to the present invention, there is provided a method for producing a hard coat film, comprising: applying the ultraviolet curable coating composition according to any one of the above to a surface of a transparent base film to form a coating layer The coating step, a drying step of drying the solvent from the obtained coating layer, and a hardening step of curing the coating layer by irradiating the coating layer with ultraviolet rays on the solvent.
該方法中，硬化步驟可包含：將具有鏡面 或凹凸面之模具壓抵於去除溶劑後之上述塗佈層並照射紫外線之步驟，此時之模具，尤其在連續製造硬塗薄膜時，可為鏡面輥或壓印輥。 In the method, the hardening step may include: having a mirror surface Or the mold of the uneven surface is pressed against the above-mentioned coating layer after removing the solvent and irradiated with ultraviolet rays. At this time, the mold, especially in the continuous production of the hard coat film, may be a mirror roll or an impression roll.
此外，硬化步驟較佳係具備：從上述透明基材薄膜側照射紫外線之第一照射步驟，以及隨後從上述塗佈層側照射紫外線之第二照射步驟。此時之第一照射步驟，可以一邊將鏡面輥或壓印輥壓抵於上述塗佈層、一邊從上述透明基材薄膜側照射紫外線之方式進行。 Further, the hardening step preferably includes a first irradiation step of irradiating ultraviolet rays from the side of the transparent substrate film, and a second irradiation step of subsequently irradiating ultraviolet rays from the side of the coating layer. In this case, the first irradiation step can be performed by irradiating the transparent substrate film side with ultraviolet rays while pressing the mirror roll or the platen roller against the coating layer.
本發明之紫外線硬化性塗佈組成物，即使將其塗佈於基材薄膜上，並在將所得之塗佈層壓抵於模具之狀態下硬化，亦可形成水親和性小，具體而言為對水接觸角大，因此防污性優異，並且具有高平滑性、高透明性、高硬度且具有良好外觀之硬塗層。當然，即使在自由之狀態下，具體而言為接觸於大氣之狀態下使塗佈層表面硬化，亦可形成具有上述優異性能之硬塗層。 The ultraviolet curable coating composition of the present invention can be formed by applying it to a base film and hardening it in a state in which the obtained coating is laminated against a mold, thereby achieving a small water affinity, specifically, It is a hard coat layer which has a large contact angle with water and is excellent in antifouling property, and has high smoothness, high transparency, high hardness, and good appearance. Of course, even in the free state, specifically, the surface of the coating layer is hardened in contact with the atmosphere, a hard coat layer having the above-described excellent properties can be formed.
將該塗佈組成物塗佈於透明基材薄膜的表面，並從該處去除溶劑使該塗佈層硬化所得之硬塗薄膜，成為防污性優異，並且具有高平滑性、高透明性及高硬度，且外觀亦良好者。此外，根據本發明之製造方法，能夠有利於製造如此之硬塗薄膜。 Applying the coating composition to the surface of the transparent base film, and removing the solvent from the place to harden the hard coat film obtained by curing the coating layer, is excellent in antifouling property, and has high smoothness and high transparency. High hardness and good appearance. Further, according to the production method of the present invention, it is possible to facilitate the production of such a hard coat film.
10‧‧‧送出輥 10‧‧‧Send rolls
11‧‧‧透明基材薄膜 11‧‧‧Transparent substrate film
12‧‧‧塗佈區 12‧‧‧ Coating area
13‧‧‧紫外線硬化性塗佈組成物(塗佈液) 13‧‧‧UV curable coating composition (coating solution)
14‧‧‧乾燥區 14‧‧‧Drying area
20‧‧‧第一照射區 20‧‧‧First exposure area
21‧‧‧塗膜側輥 21‧‧‧ Coating roll
22‧‧‧第一紫外線光源 22‧‧‧First ultraviolet light source
23、24‧‧‧軋輥 23, 24‧‧‧ Rolls
26‧‧‧第二照射區 26‧‧‧Second irradiation area
27‧‧‧第二紫外線光源 27‧‧‧second ultraviolet light source
30‧‧‧捲取輥 30‧‧‧Winding roller
第1圖係示意顯示從呈輥狀備用之基材薄膜製造硬塗 薄膜時之較佳裝置配置例之流程圖。 Figure 1 is a schematic view showing the production of a hard coat from a substrate film that is in the form of a roll. A flow chart of a preferred device configuration example for a film.
以下詳細說明本發明之實施形態。本發明中，係將於分子內含有氟之硬化性化合物(以下有時稱為「含氟硬化性化合物」)與於分子內不含氟之硬化性化合物(以下有時稱為「不含氟硬化性化合物」)之混合物，設為紫外線硬化性成分，並將光聚合起始劑及溶劑調配於此而構成紫外線硬化性塗佈組成物。 Hereinafter, embodiments of the present invention will be described in detail. In the present invention, a curable compound containing fluorine in the molecule (hereinafter sometimes referred to as "fluorinated curable compound") and a curable compound having no fluorine in the molecule (hereinafter sometimes referred to as "no fluorine" The mixture of the curable compound ") is an ultraviolet curable component, and a photopolymerization initiator and a solvent are blended thereto to form an ultraviolet curable coating composition.
上述紫外線硬化性化合物的混合物，係以使含氟硬化性化合物與不含氟硬化性化合物滿足以下關係之方式混合。亦即，首先將各紫外線硬化性化合物1g分別混合分散於丙酮10ml。然後將水緩慢加入於該分散液，求取至分散液產生白濁為止之所需水量(單位：ml)。此時，將至分散液產生白濁為止之所需水量定義為該紫外線硬化性化合物的耐水度。根據所得之各硬化性化合物的耐水度，將含氟硬化性化合物與不含氟硬化性化合物之混合物的親和力A，定義如前述數學式(1)。然後以使該親和力A位於1至2的範圍之方式，組合含氟硬化性化合物與不含氟硬化性化合物。在此所謂「1至2的範圍」，為包含親和力A為1之情形及2之情形之涵義。測定耐水度時，從求取相對於雜質少之純粹的水之值之觀點來看，一般係使用離子交換水或純水。 The mixture of the ultraviolet curable compounds described above is mixed so that the fluorine-containing curable compound and the fluorine-free curable compound satisfy the following relationship. That is, first, 1 g of each ultraviolet curable compound was mixed and dispersed in 10 ml of acetone. Then, water was slowly added to the dispersion to determine the amount of water (unit: ml) until the dispersion became cloudy. At this time, the amount of water required until the dispersion liquid becomes cloudy is defined as the water resistance of the ultraviolet curable compound. The affinity A of the mixture of the fluorine-containing curable compound and the fluorine-free curable compound is defined by the above formula (1), based on the water resistance of each of the obtained curable compounds. Then, the fluorine-containing curable compound and the fluorine-free curable compound are combined so that the affinity A is in the range of 1 to 2. Here, the "range of 1 to 2" is the meaning of the case where the affinity A is 1 and the case where 2 is included. When the water resistance is measured, ion exchange water or pure water is generally used from the viewpoint of obtaining a pure water value with respect to impurities.
例如，當混合耐水度為2ml之含氟硬化性化合物20重量%與耐水度為9ml之不含氟硬化性化合物80 重量%來構成紫外線硬化性成分時，該紫外線硬化性成分的親和力A，從以下的計算中可得知為1.4。 For example, a non-fluorinated curable compound 80 having a water-resistant degree of 2 ml of a fluorine-containing curable compound of 20% by weight and a water resistance of 9 ml is mixed. When the ultraviolet curable component is composed by weight %, the affinity A of the ultraviolet curable component can be found to be 1.4 from the calculation below.
親和力A=(20/100)×(9-2)=1.4 Affinity A=(20/100)×(9-2)=1.4
使用2種以上的含氟硬化性化合物時，或是使用2種以上的不含氟硬化性化合物時，係根據各重量比率，計算含氟硬化性化合物的耐水度及/或不含氟硬化性化合物的耐水度。例如，當混合耐水度為2ml之含氟硬化性化合物20重量%、耐水度為9ml之不含氟硬化性化合物50重量%、與耐水度為5ml之不含氟硬化性化合物30重量%構成紫外線硬化性成分時，不含氟硬化性化合物(混合物)的耐水度，為(50/80)×9+(30/80)×5=7.5ml，所以該紫外線硬化性成分的親和力A，從以下的計算可得知為1.1。 When two or more types of fluorine-containing curable compounds are used, or when two or more types of fluorine-free curable compounds are used, the water resistance and/or fluorine-free curability of the fluorine-containing curable compound are calculated based on the respective weight ratios. The water resistance of the compound. For example, when blending 20% by weight of a fluorine-containing curable compound having a water resistance of 2 ml, 50% by weight of a fluorine-free curable compound having a water resistance of 9 ml, and 30% by weight of a fluorine-free curable compound having a water resistance of 5 ml, In the case of the curable component, the water resistance of the non-fluorinated curable compound (mixture) is (50/80) × 9 + (30 / 80) × 5 = 7.5 ml, so the affinity A of the ultraviolet curable component is as follows. The calculation can be known as 1.1.
親和力A=(20/100)×(7.5-2)=1.1 Affinity A=(20/100)×(7.5-2)=1.1
上述耐水度，為硬化性化合物相對於水之親和性的指標，該值愈大，水親和性愈高。一般而言，與含氟硬化性化合物相比，不含氟硬化性化合物可賦予較大的耐水度。組合之含氟硬化性化合物與不含氟硬化性化合物的耐水度愈接近，兩者的親和性愈大，其差愈大，兩者的親和性愈小。伴隨於此，以前述數學式(1)定義之親和力A，亦為考量組合含氟硬化性化合物與不含氟硬化性化合物的調配比率之親和力的追加指標。當僅以不含氟硬化性化合物作為硬化性成分時，數學式(1)中之含氟硬化性化合物的重量分率為零，所以就定義上，親和力A為零，此外，當僅以含氟硬化性化合物作為硬化性成分時，數學式(1) 中之含氟硬化性化合物的重量分率為1，所以就定義上，親和力A為負值，但就親和性之方面來看為無意義。惟不論於任一情況中，均不滿足「親和力A位於1至2的範圍」之本發明所規定的要件。含氟硬化性化合物與不含氟硬化性化合物的耐水度及重量比率，只要親和力A位於上述範圍即可，並無特別限制。含氟硬化性化合物的耐水度，例如為0.1至10ml，較佳為0.3至8ml，更佳為0.5至5.4ml。不含氟硬化性化合物的耐水度，例如為2至15ml，較佳為3至12ml，更佳為5.5至10.1ml。此外，含氟硬化性化合物與不含氟硬化性化合物的重量比率，以紫外線硬化性成分的全部重量為基準，例如含氟硬化性化合物為1至99重量%，不含氟硬化性化合物為1至99重量%，較佳為含氟硬化性化合物為5至80重量%，不含氟硬化性化合物為20至95重量%，更佳為含氟硬化性化合物為14至50重量%，不含氟硬化性化合物為50至86重量%。 The above water resistance is an index of the affinity of the curable compound with respect to water, and the larger the value, the higher the water affinity. In general, the fluorine-free curable compound can impart greater water resistance than the fluorine-containing curable compound. The closer the water-resistance of the combined fluorine-containing curable compound to the non-fluorinated curable compound, the greater the affinity between the two, and the greater the difference, the smaller the affinity between the two. Along with this, the affinity A defined by the above formula (1) is also an additional index for considering the affinity of the combination ratio of the fluorine-containing curable compound and the fluorine-free curable compound. When the fluorine-free curable compound is used as the curable component only, the weight fraction of the fluorine-containing curable compound in the formula (1) is zero, so the definition is that the affinity A is zero, and further, when only When a fluorocure compound is used as a curable component, the formula (1) Since the weight fraction of the fluorine-containing curable compound is 1, it is defined that the affinity A is a negative value, but it is meaningless in terms of affinity. However, in either case, the requirements specified in the present invention in which "Affinity A is in the range of 1 to 2" are not satisfied. The water resistance and the weight ratio of the fluorine-containing curable compound and the fluorine-free curable compound are not particularly limited as long as the affinity A is in the above range. The water resistance of the fluorine-containing curable compound is, for example, 0.1 to 10 ml, preferably 0.3 to 8 ml, more preferably 0.5 to 5.4 ml. The water resistance of the non-fluorinated hardening compound is, for example, 2 to 15 ml, preferably 3 to 12 ml, more preferably 5.5 to 10.1 ml. Further, the weight ratio of the fluorine-containing curable compound to the fluorine-free curable compound is, for example, 1 to 99% by weight based on the total weight of the ultraviolet curable component, and the fluorine-free curable compound is 1 Up to 99% by weight, preferably 5 to 80% by weight of the fluorine-containing curable compound, 20 to 95% by weight of the fluorine-free curable compound, more preferably 14 to 50% by weight of the fluorine-containing curable compound, and not containing The fluorosetting compound is 50 to 86% by weight.
即使組合使用含氟硬化性化合物與不含氟硬化性化合物，當如上定義之親和力A低於1時，尤其在將塗佈層壓抵於模具使硬化時之硬塗層表面的對水接觸角變小，無法得到高防污性。對水接觸角，可依據JIS R3257：1999「基板玻璃表面的濡濕性試驗方法」測定，較佳為80°以上。親和力A，較佳為1.1以上，更佳為1.2以上，又更佳為1.3以上。 Even if a fluorine-containing curable compound and a fluorine-free curable compound are used in combination, when the affinity A as defined above is less than 1, the water contact angle of the surface of the hard coat layer when the coating is laminated against the mold to harden It becomes smaller and cannot obtain high antifouling properties. The water contact angle can be measured in accordance with JIS R3257:1999 "Test method for wettability of substrate glass surface", and is preferably 80 or more. The affinity A is preferably 1.1 or more, more preferably 1.2 or more, still more preferably 1.3 or more.
另一方面，當如上定義之親和力A高於2時，將該塗佈組成物塗佈於透明基材薄膜上使乾燥時，含 氟硬化性化合物與不含氟硬化性化合物無法充分相溶，於該狀態下使進行紫外線硬化時，所得之硬塗層會白化，或是因各硬化性化合物之硬化收縮不同而在表面形成凹凸，因而觀察到橘皮表面，外觀惡化。此外，伴隨於此，硬塗層的霧度亦增高。霧度，可依據JIS K7136：2000「塑膠-透明材料之霧度求取方法」進行測定，當本發明之塗佈組成物不含用以賦予防眩性之微粒，且壓抵於鏡面的模具使硬化時，可成為1%以下。親和力A，較佳為1.9以下，更佳為1.8以下，又更佳為1.7以下。 On the other hand, when the affinity A as defined above is higher than 2, the coating composition is applied onto a transparent substrate film to be dried, including The fluorine-curable compound and the non-fluorinated curable compound are not sufficiently compatible, and when the ultraviolet curing is performed in this state, the obtained hard coat layer is whitened, or the hardening shrinkage of each curable compound is different to form unevenness on the surface. Thus, the surface of the orange peel was observed and the appearance deteriorated. Further, along with this, the haze of the hard coat layer is also increased. The haze can be measured in accordance with JIS K7136:2000 "Method for Calculating Haze of Plastic-Transparent Material", when the coating composition of the present invention does not contain a microparticle for imparting anti-glare properties and is pressed against the mirror surface. When hardening, it can become 1 % or less. The affinity A is preferably 1.9 or less, more preferably 1.8 or less, still more preferably 1.7 or less.
以下係依序說明構成本發明之紫外線硬化性塗佈組成物之各成分，然後再說明硬塗薄膜及該硬塗薄膜之製造方法。 Hereinafter, the components constituting the ultraviolet curable coating composition of the present invention will be described in order, and then the hard coat film and the method for producing the hard coat film will be described.
構成塗佈組成物之含氟硬化性化合物，只要於分子內具有至少1個聚合硬化性的碳-碳雙鍵，且至少鍵結有1個氟原子者即可，但聚合硬化性的碳-碳雙鍵，較佳於分子內至少有2個。較佳之含氟硬化性化合物的例子，可列舉於分子內具有氟烷基之胺甲酸乙酯化多官能(甲基)丙烯酸酯化合物，較佳者可列舉：由分子內具有氟烷基之醇、硫醇或胺化合物與二或三異氰酸酯化合物以及分子內具有羥基之多官能(甲基)丙烯酸酯化合物反應所得之於分子內具有氟烷基之胺甲酸乙酯化多官能(甲基)丙烯酸酯化合物。如此之具體例可列舉以前述式(I)所示之化合物。 The fluorine-containing curable compound constituting the coating composition may have at least one polymer curable carbon-carbon double bond in the molecule and may have at least one fluorine atom bonded thereto, but the polymer hardenable carbon- The carbon double bond preferably has at least two in the molecule. Examples of preferred fluorination-curable compounds include urethane-based polyfunctional (meth) acrylate compounds having a fluoroalkyl group in the molecule, and preferred examples thereof include alcohols having a fluoroalkyl group in the molecule. a urethane-containing polyfunctional (meth)acrylic acid having a fluoroalkyl group in a molecule obtained by reacting a thiol or an amine compound with a di- or triisocyanate compound and a polyfunctional (meth) acrylate compound having a hydroxyl group in the molecule. Ester compound. Specific examples of such a compound include the compound represented by the above formula (I).
以前述式(I)所示之化合物，例如可藉由以下所示之反應製造。亦即，首先使下述式(II)所示之含氟烷基官能性化合物與下述式(III)所示之二或三異氰酸酯化合物反應，製造式(II)之含氟烷基官能性化合物的官能基-XH加成於二或三異氰酸酯化合物中的1個異氰酸基(-N=C=O)而成之下述式(IV)之化合物。 The compound represented by the above formula (I) can be produced, for example, by the reaction shown below. That is, first, a fluorine-containing alkyl functional compound represented by the following formula (II) is reacted with a di- or triisocyanate compound represented by the following formula (III) to produce a fluorine-containing alkyl functional group of the formula (II). The functional group -XH of the compound is added to one of the isocyanato groups (-N=C=O) in the di- or triisocyanate compound to give a compound of the following formula (IV).
上述式(II)、(III)及(IV)中，m、n、a、X及Y，如先前所定義。 In the above formulae (II), (III) and (IV), m, n, a, X and Y are as defined previously.
接著使下述式(V)所示之含羥基多官能(甲基)丙烯酸酯化合物與所得之上述式(IV)之化合物反應以進行胺甲酸乙酯化，藉此可製造前述式(I)所示之含氟烷基的胺甲酸乙酯化多官能(甲基)丙烯酸酯化合物。 Next, a hydroxyl group-containing polyfunctional (meth) acrylate compound represented by the following formula (V) is reacted with the obtained compound of the above formula (IV) to carry out urethane urelation, whereby the above formula (I) can be produced. A fluoroalkyl-containing urethane-ethylated polyfunctional (meth) acrylate compound is shown.
上述式(V)中，b、z及R如先前所定義。 In the above formula (V), b, z and R are as defined previously.
上述式(II)所示之含氟烷基官能性化合物，為具有相當於CmF2m+1-之氟烷基之醇(X為氧原子O時)、硫醇(X為硫原子S時)或胺(X為亞胺基NH時)。含氟烷基醇 化合物的代表例，有2-(全氟己基)乙醇；將其羥基取代為巰基之化合物，亦即2-(全氟己基)乙烷硫醇，為含氟烷基硫醇化合物的代表例；將其羥基取代為胺基之化合物，亦即2-(全氟己基)乙基胺，為含氟烷基胺化合物的代表例。 The fluorine-containing alkyl functional compound represented by the above formula (II) is an alcohol having a fluoroalkyl group corresponding to C m F 2m+1 - (where X is an oxygen atom O), and a thiol (X is a sulfur atom S) Or amine (when X is an imido NH). Representative examples of the fluorine-containing alkyl alcohol compound are 2-(perfluorohexyl)ethanol; a compound in which a hydroxyl group is substituted with a mercapto group, that is, 2-(perfluorohexyl)ethanethiol, which is a fluorine-containing alkyl mercaptan. A representative example of the compound; a compound in which a hydroxyl group is substituted with an amine group, that is, 2-(perfluorohexyl)ethylamine, is a representative example of a fluorine-containing alkylamine compound.
上述式(III)中，Y係從二或三異氰酸酯化合物中去除全部的異氰酸基(-N=C=O)所得之基，因此，以式(III)所示之化合物，成為二或三異氰酸酯化合物。該二或三異氰酸酯化合物，可為以往被廣泛使用在胺甲酸乙酯化合物的製造中者。列舉二異氰酸酯，亦即2價的異氰酸酯化合物的具體例，係有六亞甲二異氰酸酯、異佛爾酮二異氰酸酯、二環己基甲烷二異氰酸酯、甲苯二異氰酸酯、二甲苯二異氰酸酯、萘二異氰酸酯、二苯基甲烷二異氰酸酯等。三異氰酸酯，亦即3價的異氰酸酯化合物，例如可為上述二異氰酸酯的異三聚氰酸酯三聚物、上述二異氰酸酯的3元醇加成物等。列舉三異氰酸酯的具體例，係有六亞甲二異氰酸酯的異三聚氰酸酯三聚物、甲苯二異氰酸酯的異三聚氰酸酯三聚物、六亞甲二異氰酸酯的三羥甲基丙烷加成物、甲苯二異氰酸酯的三羥甲基丙烷加成物等。 In the above formula (III), Y is a group obtained by removing all of the isocyanato groups (-N=C=O) from the di- or triisocyanate compound, and therefore, the compound represented by the formula (III) becomes di or Triisocyanate compound. The di- or triisocyanate compound can be widely used in the production of an urethane compound. Specific examples of the diisocyanate, that is, the divalent isocyanate compound are hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate, xylene diisocyanate, naphthalene diisocyanate, Diphenylmethane diisocyanate and the like. The triisocyanate, that is, the trivalent isocyanate compound, for example, may be a hetero-isocyanate trimer of the above diisocyanate, a trihydric alcohol adduct of the above-mentioned diisocyanate, or the like. Specific examples of the triisocyanate include an isocyanurate trimer of hexamethylene diisocyanate, an isocyanurate trimer of toluene diisocyanate, and a trimethylolpropane of hexamethylene diisocyanate. An adduct, a trimethylolpropane adduct of toluene diisocyanate, or the like.
此外，上述式(V)中，Z為從3價至6價的多元醇中去除全部的羥基(-OH)所得之3價至6價的基，因此，以式(V)所示之化合物，為具有1個羥基之二、三、四或五(甲基)丙烯酸酯。列舉二(甲基)丙烯酸酯，亦即式(V)中b=2之化合物的具體例，係有二丙烯酸三羥甲基丙烷酯、二丙烯酸三羥甲基乙烷酯、二丙烯酸甘油酯、及對應 於此等之甲基丙烯酸酯等。列舉三(甲基)丙烯酸酯，亦即式(V)中b=3之化合物的具體例，係有三丙烯酸新戊四醇酯、三丙烯酸二-三羥甲基丙烷酯、及對應於此等之甲基丙烯酸酯等。列舉五(甲基)丙烯酸酯，亦即式(V)中b=5之化合物的具體例，係有五丙烯酸二新戊四醇酯、及對應於此等之甲基丙烯酸酯等。 Further, in the above formula (V), Z is a trivalent to hexavalent group obtained by removing all of the hydroxyl groups (-OH) from the trivalent to hexavalent polyol, and therefore, the compound represented by the formula (V) It is a di-, tri-, tetra- or penta (meth) acrylate having one hydroxyl group. Specific examples of the compound of the di(meth)acrylate, that is, b=2 in the formula (V), are trimethylolpropane diacrylate, trimethylolethane diacrylate, and glyceryl diacrylate. And corresponding Such methacrylates and the like. Specific examples of the compound of tri(meth)acrylate, that is, b=3 in the formula (V), are neopentyl triacrylate, di-trimethylolpropane triacrylate, and the like. Methyl acrylate and the like. Specific examples of the compound of the fifth (meth) acrylate, that is, b = 5 in the formula (V) are dipentaerythritol pentaacrylate, methacrylate corresponding thereto, and the like.
可藉由以上說明之反應製造之以前述式(I)所示之含氟硬化性化合物的具體例，如後述合成例所示。含氟硬化性化合物，可僅使用1種，或是在滿足前述數學式(1)所定義之親和力A位於1至2的範圍之前提下，併用2種以上。 A specific example of the fluorine-containing curable compound represented by the above formula (I) which can be produced by the reaction described above is as shown in the synthesis example described later. The fluorinated curable compound may be used alone or in combination of two or more kinds before the affinity A defined by the above formula (1) is in the range of 1 to 2.
構成塗佈組成物之不含氟硬化性化合物，只要於分子內具有至少1個聚合硬化性的碳-碳雙鍵，且未鍵結氟原子之化合物即可，但聚合硬化性的碳-碳雙鍵，較佳係存在為(甲基)丙烯醯基者，尤佳係於分子內具有至少2個(甲基)丙烯醯基者。 The non-fluorinated curable compound constituting the coating composition may be a compound having at least one polymer curable carbon-carbon double bond in the molecule and not having a fluorine atom bonded thereto, but a polymer curable carbon-carbon. The double bond is preferably one having a (meth) acrylonitrile group, and particularly preferably having at least two (meth) acrylonitrile groups in the molecule.
列舉於分子內具有2個(甲基)丙烯醯基之硬化性化合物的具體例，係有二丙烯酸乙二醇酯、二丙烯酸二乙二醇酯、二丙烯酸丙二醇酯、二丙烯酸二丙二醇酯、二丙烯酸聚乙二醇酯、二丙烯酸聚丙二醇酯、及對應於此等之甲基丙烯酸酯等。 Specific examples of the curable compound having two (meth)acryl fluorenyl groups in the molecule include ethylene glycol diacrylate, diethylene glycol diacrylate, propylene glycol diacrylate, and dipropylene glycol diacrylate. Polyethylene glycol diacrylate, polypropylene glycol diacrylate, and methacrylate corresponding thereto.
列舉於分子內具有3個(甲基)丙烯醯基之硬 化性化合物的具體例，係有三丙烯酸三羥甲基丙烷酯、三丙烯酸甘油酯、環氧化三丙烯酸甘油酯、環氧化異三聚氰酸三丙烯酸酯、三丙烯酸新戊四醇酯、及對應於此等之甲基丙烯酸酯等。 Listed as hard in the molecule with 3 (meth) acrylonitrile groups Specific examples of the compound are trimethylolpropane triacrylate, glyceryl triacrylate, epoxidized glycerol triacrylate, epoxidized isocyanuric acid triacrylate, neopentyl glycol triacrylate, and corresponding Such methacrylates and the like.
列舉於分子內具有4個以上的(甲基)丙烯醯基之硬化性化合物的具體例，係有四丙烯酸新戊四醇酯、四丙烯酸二-三羥甲基丙烷酯、環氧化四丙烯酸新戊四醇酯、四丙烯酸二新戊四醇酯、五丙烯酸二新戊四醇酯、六丙烯酸二新戊四醇酯、及對應於此等之甲基丙烯酸酯等。 Specific examples of the curable compound having four or more (meth)acryl fluorenyl groups in the molecule include neopentyl tetraacrylate, di-trimethylolpropane tetraacrylate, and epoxidized tetraacrylic acid. Pentaerythritol ester, dineopentaerythritol tetraacrylate, di pentaerythritol pentaacrylate, dineopentaerythritol hexaacrylate, and methacrylate corresponding thereto.
此外，亦可將稱為(甲基)丙烯酸胺甲酸乙酯之低聚物形式的(甲基)丙烯酸酯作為不含氟硬化性化合物使用。(甲基)丙烯酸胺甲酸乙酯，例如可藉由於分子內具有羥基之(甲基)丙烯酸酯與先前例示作為式(III)所示化合物之二或三異氰酸酯化合物之胺甲酸乙酯化反應而製造。具體而言，例如可列舉三丙烯酸新戊四醇酯與六亞甲二異氰酸酯之反應生成物。 Further, a (meth) acrylate in the form of an oligomer called ethyl (meth) acrylate may be used as the non-fluorinated curable compound. Ethyl methacrylate (meth) acrylate, for example, by a urethane reaction of a (meth) acrylate having a hydroxyl group in the molecule with a di or triisocyanate compound previously exemplified as a compound of the formula (III) Manufacturing. Specifically, for example, a reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate can be mentioned.
不含氟硬化性化合物，可僅使用1種，亦可在滿足前述數學式(1)定義之親和力A位於1至2的範圍之前提下，併用2種以上。此外，在滿足前述數學式(1)定義之親和力A位於1至2的範圍之前提下，可將於分子內僅具有1個(甲基)丙烯醯基之單官能(甲基)丙烯酸酯，以及於分子內僅具有1個(甲基)丙烯醯基以外的聚合性碳-碳雙鍵且未鍵結氟原子之單官能硬化性化合物，使用作為不含氟硬化性化合物的一部分。 The fluorine-free curable compound may be used alone or in combination of two or more kinds, and the affinity A as defined in the above formula (1) may be in the range of 1 to 2. Further, a monofunctional (meth) acrylate having only one (meth)acryl fluorenyl group in the molecule, which is provided before the affinity A defined in the above formula (1) is satisfied, is taken up in the range of 1 to 2. Further, a monofunctional curable compound having only one polymerizable carbon-carbon double bond other than a (meth)acryl fluorenyl group in the molecule and not having a fluorine atom bonded thereto is used as a part of the non-fluorinated curable compound.
塗佈組成物，除了以上說明之含氟硬化性化合物及不含氟硬化性化合物之外，另含有用以使此等硬化性成分開始聚合之光聚合起始劑。光聚合起始劑，只要是可作用於(甲基)丙烯醯基的雙鍵使開始自由基聚合者即可。該自由基聚合起始劑，例如可列舉醯基膦氧化物、α-羥烷基苯酮、乙醛酸苯酯、苄基二烷基縮醛、安息香醚、α-胺烷基苯酮等。 The coating composition contains, in addition to the fluorine-containing curable compound and the fluorine-free curable compound described above, a photopolymerization initiator for starting polymerization of the curable components. The photopolymerization initiator may be any one which can act on a (meth)acryl fluorenyl group to initiate radical polymerization. Examples of the radical polymerization initiator include mercaptophosphine oxide, α-hydroxyalkylphenone, phenyl glyoxylate, benzyl dialkyl acetal, benzoin ether, α-aminoalkylphenone, and the like. .
醯基膦氧化物，典型者如下述式(VI)所示，式中的Q1、Q2及Q3分別獨立表示有機基，但此等當中的至少一個為醯基，亦即酸殘基，Q1、Q2及Q3通常具有苯環。 The mercaptophosphine oxide is typically represented by the following formula (VI): wherein Q 1 , Q 2 and Q 3 each independently represent an organic group, but at least one of these is a mercapto group, that is, an acid residue. , Q 1 , Q 2 and Q 3 usually have a benzene ring.
列舉醯基膦氧化物的具體例，係有2,4,6-三甲基苯甲醯基二苯基膦氧化物、及雙(2,4,6-三甲基苯甲醯基)苯基膦氧化物，前者由BASF公司以"Lucirin TPO"或"Irgacure TPO"的商品名稱販售，後者同樣由BASF公司以"Irgacure 819"的商品名稱販售。 Specific examples of the mercaptophosphine oxides are 2,4,6-trimethylbenzimidyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzylidene)benzene. The base phosphine oxide, the former is sold under the trade name "Lucirin TPO" or "Irgacure TPO" by BASF, and the latter is also sold under the trade name "Irgacure 819" by BASF.
α-羥烷基苯酮，典型者如下述式(VII)所示，式中的R1表示氫原子或低級烷基，R2表示低級烷基，R1及R2可一同與彼等所鍵結之碳原子形成環，此外，構成 苯甲醯基(C6H5-CO-)之苯環的氫原子可被其他有機基取代。 The α-hydroxyalkylphenone is typically represented by the following formula (VII): wherein R 1 represents a hydrogen atom or a lower alkyl group, R 2 represents a lower alkyl group, and R 1 and R 2 may together with them. The bonded carbon atoms form a ring, and further, the hydrogen atom of the benzene ring constituting the benzamidine group (C 6 H 5 -CO-) may be substituted with another organic group.
列舉α-羥烷基苯酮的具體例，係有2-羥基-2-甲基-1-苯基-丙烷-1-酮、及(1-羥基環己基)苯基酮，前者由BASF公司以"Darocur 1173"的商品名稱販售，後者同樣由BASF公司以"Irgacure 184"的商品名稱販售。 Specific examples of the α-hydroxyalkylphenone include 2-hydroxy-2-methyl-1-phenyl-propan-1-one and (1-hydroxycyclohexyl)phenyl ketone, the former being by BASF Corporation. It is sold under the trade name "Darocur 1173", which is also sold under the trade name "Irgacure 184" by BASF.
乙醛酸苯酯，為苯基乙醛酸的酯類，典型者如下述式(VIII)所示，式中的R3表示低級烷基，此外，構成苯甲醯基之苯環的氫原子可被其他有機基取代。 Phenyl glyoxylate is an ester of phenylglyoxylic acid, and is typically represented by the following formula (VIII): R 3 in the formula represents a lower alkyl group, and further, a hydrogen atom constituting a benzene ring of a benzamidine group Can be substituted by other organic groups.
列舉乙醛酸苯酯的具體例，係有乙醛酸甲基苯酯，此係由BASF公司以"Darocur MBF"的商品名稱販售。 A specific example of phenyl glyoxylate is exemplified by methyl phenyl glyoxylate, which is sold under the trade name "Darocur MBF" by BASF Corporation.
苄基二烷基縮醛，典型者如下述式(IX)所示，式中的R4及R5分別獨立表示低級烷基，此外，構成苯甲醯基之苯環的氫原子可被其他有機基取代。 The benzyl dialkyl acetal is typically represented by the following formula (IX), wherein R 4 and R 5 each independently represent a lower alkyl group, and further, the hydrogen atom of the benzene ring constituting the benzamidine group may be other Replacement with an organic group.
列舉苄基二烷基縮醛的具體例，係有苄基二甲基縮醛，別名為2,2-二甲氧基-1,2-二苯基乙烷-1-酮，此係由BASF公司以"Irgacure 651"的商品名稱販售。 Specific examples of the benzyldialkyl acetal are benzyl dimethyl acetal, and the name is 2,2-dimethoxy-1,2-diphenylethane-1-one. BASF is sold under the trade name "Irgacure 651".
安息香醚，典型者如下述式(X)所示，式中的R6表示低級烷基，此外，構成苯甲醯基之苯環的氫原子可被其他有機基取代。 The benzoin ether is typically represented by the following formula (X): R 6 in the formula represents a lower alkyl group, and further, the hydrogen atom of the benzene ring constituting the benzamidine group may be substituted with another organic group.
列舉安息香醚的具體例，係有安息香甲醚、安息香***、安息香異丙醚、安息香異丁醚等。 Specific examples of the benzoin ether include benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and the like.
α-胺烷基苯酮，典型者如下述式(XI)所示，式中的R7及R8分別獨立表示低級烷基或苯基低級烷基，R9及R10分別獨立表示氫原子或低級烷基，但R9及R10可一同與彼等所鍵結之氮原子形成環，且該環更可讓氧等異質原子成為環原子，此外，構成苯甲醯基之苯環的氫原子可被其他有機基取代。 The α-aminoalkylphenone is typically represented by the following formula (XI): wherein R 7 and R 8 each independently represent a lower alkyl group or a phenyl lower alkyl group, and R 9 and R 10 each independently represent a hydrogen atom. Or a lower alkyl group, but R 9 and R 10 may form a ring together with the nitrogen atom to which they are bonded, and the ring may allow a hetero atom such as oxygen to form a ring atom, and further, a benzene ring constituting the benzamidine group; The hydrogen atom may be substituted by other organic groups.
列舉α-胺烷基苯酮的具體例，係有2-甲基-1-(4-甲基硫苯基)-2-嗎啉丙烷-1-酮、及2-苄基-2-二甲基胺基-1-(4-嗎啉苯基)丁酮-1，前者由BASF公司以"Irgacure 907"的商品名稱販售，後者同樣由BASF公司以"Irgacure 369"的商品名稱販售。 Specific examples of the α-aminoalkyl benzophenone include 2-methyl-1-(4-methylthiophenyl)-2-morpholinepropan-1-one, and 2-benzyl-2-di Methylamino-1-(4-morpholinyl)butanone-1, the former sold by BASF under the trade name "Irgacure 907", which is also sold under the trade name "Irgacure 369" by BASF .
聚合起始劑，只要調配至少1種即可，但組合使用分解波長不同的至少2種亦為有效。於後者時，較佳係併用：於波長較長的紫外線或近紫外線區域，例如超過370nm且未達450nm的波長區域顯示至少一個極大吸收之聚合起始劑；以及僅於波長較短的區域，例如於370nm以下的波長區域顯示極大吸收之聚合起始劑。上述例示者中，由於醯基膦氧化物較多係於波長較長的紫外線或近紫外線區域顯示極大吸收，所以將選自由醯基膦氧化物所組成之群組之聚合起始劑構作為第一聚合起始劑，此外，α-羥烷基苯酮、乙醛酸苯酯、苄基二烷基縮醛、安息香醚及α-胺烷基苯酮，較多係僅於波長較短的波長區域顯示極大吸收，所以將選自由此等所組成之群組之聚合起始劑構作為第二光聚合起始劑，較佳係組合此等第一聚合起始劑及第二聚合起始劑。 The polymerization initiator may be formulated in at least one type, and it is also effective to use at least two types having different decomposition wavelengths in combination. In the latter case, it is preferred to use at least one wavelength-infrared ultraviolet or near-ultraviolet region, for example, a wavelength region exceeding 370 nm and less than 450 nm to exhibit at least one polymerization initiator having a maximum absorption; and only in a region having a shorter wavelength, For example, a polymerization initiator which exhibits a maximum absorption in a wavelength region of 370 nm or less. In the above-mentioned examples, since the mercaptophosphine oxide is mostly absorbed in the ultraviolet light or the near ultraviolet region having a long wavelength, the polymerization initiator selected from the group consisting of mercaptophosphine oxides is used as the first a polymerization initiator, in addition, α-hydroxyalkylphenone, phenyl glyoxylate, benzyl dialkyl acetal, benzoin ether and α-aminoalkyl benzophenone, more only in the shorter wavelength The wavelength region shows a great absorption, so a polymerization initiator selected from the group consisting of such a composition is used as the second photopolymerization initiator, preferably combining the first polymerization initiator and the second polymerization initiator. Agent.
根據此形態，例如在將組合有此等2種聚合起始劑之塗佈液塗佈於基材薄膜上形成塗佈層，並從該塗佈層中將溶劑乾燥去除，然後將紫外線照射在去除溶劑後之塗佈層使塗佈層硬化以製造硬塗薄膜之方法中，可區分成：從上述透明基材薄膜側照射紫外線之第一照射、與隨 後從上述塗佈層側進行之第二照射，第一照射中，係照射包含較多使上述第一聚合起始劑分解之波長較長區域之紫外線，第二照射中，照射包含較多使上述第二聚合起始劑分解之波長較短區域之紫外線，如此可在第一照射中使硬化性成分高分子量化後，在第二照射中使充分進行交聯，而達到能夠提升硬塗層表面硬度之效果。 According to this aspect, for example, a coating liquid in which two kinds of polymerization initiators are combined is applied onto a substrate film to form a coating layer, and the solvent is dried and removed from the coating layer, and then ultraviolet rays are irradiated thereon. The method of curing the coating layer after removing the solvent to harden the coating layer to produce a hard coating film can be distinguished by: first irradiation of ultraviolet rays from the side of the transparent substrate film, and Then, the second irradiation is performed from the side of the coating layer, and in the first irradiation, ultraviolet rays containing a large wavelength region in which the first polymerization initiator is decomposed are irradiated, and in the second irradiation, the irradiation is included in a large amount. The ultraviolet ray having a shorter wavelength in the second polymerization initiator is decomposed, so that the curable component can be highly polymerized in the first irradiation, and then sufficiently crosslinked in the second irradiation to achieve a hard coat resistance. The effect of surface hardness.
聚合起始劑的調配量，只要是可使紫外線硬化性成分聚合之充足的量即可，例如，相對於包含不含氟硬化性化合物及含氟硬化性化合物之紫外線硬化性成分的全體100重量份，因應紫外線硬化性成分的種類或調配比率、以及聚合起始劑的種類等，從約0.2至20重量份的範圍適當選擇即可。聚合起始劑的調配量，相對於紫外線硬化性成分的全體100重量份，可設為約0.2至10重量份的範圍，或是約0.2至5重量份的範圍。當併用2種以上的聚合起始劑時，彼等的合計量可設為以上範圍。 The amount of the polymerization initiator to be added may be sufficient to polymerize the ultraviolet curable component, for example, 100 weights per 100 parts of the ultraviolet curable component containing the fluorine-free curable compound and the fluorine-containing curable compound. In the range of from about 0.2 to 20 parts by weight, the type of the ultraviolet curable component, the blending ratio, and the type of the polymerization initiator may be appropriately selected. The amount of the polymerization initiator to be added may be in the range of about 0.2 to 10 parts by weight, or about 0.2 to 5 parts by weight, based on 100 parts by weight of the entire ultraviolet curable component. When two or more types of polymerization initiators are used in combination, the total amount of these may be set to the above range.
構成塗佈組成物之溶劑，只要是可溶解以上說明之紫外線硬化性成分及聚合起始劑形成溶液之有機溶劑即可。例如可從己烷及辛烷般之脂肪族烴類；甲苯及二甲苯般之芳香族烴類；乙醇、1-丙醇、異丙醇及1-丁醇般之醇類；甲乙酮及甲基異丁酮般之酮類；乙酸乙酯、乙酸丁酯及乙酸異丁酯般之酯類；乙二醇單甲醚、乙二醇單***、二乙二醇單***、丙二醇單甲醚及丙二醇單***般之二醇醚 類；乙二醇單甲醚乙酸酯及丙二醇單甲醚乙酸酯般之酯化二醇醚類等適當選擇使用。此等有機溶劑可單獨使用，當然亦可因應必要混合2種以上使用。 The solvent constituting the coating composition may be any organic solvent which can dissolve the ultraviolet curable component and the polymerization initiator forming solution described above. For example, aliphatic hydrocarbons such as hexane and octane; aromatic hydrocarbons such as toluene and xylene; alcohols such as ethanol, 1-propanol, isopropanol and 1-butanol; methyl ethyl ketone and methyl Isobutyl ketone-like ketones; esters of ethyl acetate, butyl acetate and isobutyl acetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether and Propylene glycol monoethyl ether glycol ether Ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate esterified glycol ethers, etc. are suitably selected and used. These organic solvents may be used singly or in combination of two or more kinds as necessary.
溶劑，由於在塗佈後被乾燥去除，所以其量較佳係在可溶解上述紫外線硬化性成分及聚合起始劑之範圍內不宜過多，例如，相對於包含不含氟硬化性化合物及含氟硬化性化合物之紫外線硬化性成分的合計量100重量份，較佳以0.5至2.5重量倍的比率含有。 Since the solvent is dried and removed after coating, the amount thereof is preferably not too large insofar as it dissolves the ultraviolet curable component and the polymerization initiator, for example, with respect to the fluorine-containing hardening compound and fluorine-containing compound. 100 parts by weight of the total amount of the ultraviolet curable components of the curable compound is preferably contained in a ratio of 0.5 to 2.5 times by weight.
塗佈組成物，係必須含有以上說明之紫外線硬化性成分、光聚合起始劑及溶劑，除此之外，可適當含有：用以提升硬化層(硬塗層)表面的平滑性之平坦化劑、用以使硬化層(硬塗層)表現抗帶電性之抗帶電劑、用以將防眩性賦予至硬化層(硬塗層)之有機或無機微粒等該領域慣用之添加劑。防眩性，亦可藉由將由該塗佈組成物所得之塗佈層壓抵於具有凹凸面之模具使硬化之方法，亦即所謂的UV壓印法賦予。 The coating composition must contain the ultraviolet curable component, the photopolymerization initiator, and the solvent described above, and may contain a flattening for improving the smoothness of the surface of the hardened layer (hard coat layer). The agent, an antistatic agent for causing a hardened layer (hard coat layer) to exhibit antistatic property, an organic or inorganic fine particle for imparting antiglare property to a hardened layer (hard coat layer), and the like which are conventionally used in the field. The anti-glare property can also be imparted by a method of hardening a coating obtained by coating the coating composition against a mold having an uneven surface, that is, a so-called UV imprint method.
本發明之塗佈組成物，可使用在塗佈於基材的表面使乾燥後，將紫外線照射在所得之塗佈層而形成硬化層之用途，尤其可較佳使用在將具有鏡面或凹凸面之模具壓抵於 上述所得之塗佈層使硬化之方式。如此形成之塗佈層的代表例，係有形成於透明基材薄膜的表面之硬塗層。因此，該塗佈組成物可妥適使用在硬塗層的形成。具體而言，將以上說明之塗佈組成物塗佈於透明基材薄膜的表面上，從所得之塗佈層將溶劑去除後，將紫外線照射在該塗佈層使硬化，藉此形成具備透明基材薄膜與由上述塗佈組成物構成之硬塗層之硬塗薄膜。 The coating composition of the present invention can be used for forming a hardened layer by applying ultraviolet rays to the obtained coating layer after drying on the surface of the substrate, and particularly preferably having a mirror surface or a concave-convex surface. The mold is pressed against The coating layer obtained above is hardened. A representative example of the coating layer thus formed is a hard coat layer formed on the surface of the transparent base film. Therefore, the coating composition can be suitably used in the formation of a hard coat layer. Specifically, the coating composition described above is applied onto the surface of the transparent base film, and after the solvent is removed from the obtained coating layer, ultraviolet rays are irradiated onto the coating layer to be cured, thereby forming transparent A hard coat film of a base film and a hard coat layer composed of the above coating composition.
使硬塗層形成於表面之透明基材薄膜，一般由透明樹脂構成，例如可列舉由三乙酸纖維素、二乙酸纖維素及纖維素乙酸丙酸酯般之纖維素樹脂；聚碳酸酯系樹脂；以聚甲基丙烯酸甲酯為代表例之(甲基)丙烯酸系樹脂；聚對苯二甲酸乙二酯及聚萘二甲酸乙二酯般之聚酯系樹脂；聚乙烯及聚丙烯般之鏈狀聚烯烴系樹脂；環狀聚烯烴系樹脂；苯乙烯系樹脂；聚碸；聚醚碸等構成之樹脂薄膜。此等當中，從透明性、機械強度、熱穩定性、低濕度穿透性、等向性等之觀點來看，較佳可使用三乙酸纖維素、聚甲基丙烯酸甲酯、聚碳酸酯及聚對苯二甲酸乙二酯。 The transparent base film on which the hard coat layer is formed on the surface is generally composed of a transparent resin, and examples thereof include cellulose resins such as cellulose triacetate, cellulose diacetate, and cellulose acetate propionate; and polycarbonate resins. a (meth)acrylic resin represented by polymethyl methacrylate; a polyester resin such as polyethylene terephthalate or polyethylene naphthalate; polyethylene and polypropylene A chain polyolefin resin; a cyclic polyolefin resin; a styrene resin; a polyfluorene; a resin film composed of a polyether oxime or the like. Among these, from the viewpoints of transparency, mechanical strength, thermal stability, low-humidity permeability, isotropic property, etc., it is preferred to use cellulose triacetate, polymethyl methacrylate, polycarbonate, and Polyethylene terephthalate.
如此於透明基材薄膜的表面形成硬塗層以製造硬塗薄膜之方法，係具備：將先前說明之紫外線硬化性塗佈組成物塗佈於透明基材薄膜的表面形成塗佈層之塗佈步驟、從所得之塗佈層將溶劑乾燥去除之乾燥步驟、以及將紫外線照射在去除溶劑後之塗佈層使塗佈層硬化之硬化步驟。 The method of forming a hard coat layer on the surface of a transparent base film to produce a hard coat film, comprising: applying the ultraviolet curable coating composition described above to the surface of the transparent base film to form a coating layer. And a drying step of drying the solvent from the obtained coating layer, and a hardening step of irradiating the coating layer after removing the solvent with ultraviolet rays to harden the coating layer.
硬化步驟，可採用：將具有鏡面或凹凸面 之模具壓抵於去除溶劑後之塗佈層，照射紫外線使塗佈層硬化之方法。尤其當一邊運送呈輥狀備用之長條的基材薄膜，一邊將塗佈層連續形成於其表面使硬化，而以輥狀連續製造硬塗薄膜時，上述模具較佳為輥，因此，此時的模具為鏡面輥或壓印輥(具有凹凸面之輥)。使用壓印輥進行賦形時，可將防眩性賦予至硬塗層，而得到具有細微凹凸表面之防眩薄膜。 Hardening step, can be: will have a mirror or concave surface The mold is pressed against the coating layer after the solvent is removed, and the coating layer is cured by irradiation with ultraviolet rays. In particular, when the base film which is in the form of a roll is used, the coating layer is continuously formed on the surface thereof to be hardened, and when the hard coat film is continuously formed in a roll shape, the mold is preferably a roll. The mold at the time is a mirror roll or an embossing roll (roller having a concave-convex surface). When the embossing roll is used for shaping, the anti-glare property can be imparted to the hard coat layer, and an anti-glare film having a fine uneven surface can be obtained.
上述硬化步驟，可具備：從透明基材薄膜側照射紫外線之第一照射步驟；以及隨後從塗佈層側照射紫外線之第二照射步驟。此時，如先前第一聚合起始劑與第二聚合起始劑的組合中所說明般，第一照射步驟係照射：在使第一聚合起始劑分解之較長波長的區域中，例如超過370nm的波長區域中具有最大發光強度之紫外線；於第二照射步驟則照射：在使第二聚合起始劑分解之較短波長區域中，例如370nm以下的波長區域中具有最大發光強度之紫外線，如此，可使乾燥後的塗佈層充分硬化，得到高硬度的硬塗薄膜。當連續製造長條的硬塗薄膜時，第一照射步驟，較佳係一邊將鏡面輥或壓印輥壓抵於塗佈層，一邊從基材薄膜側照射紫外線來進行。 The hardening step may include a first irradiation step of irradiating ultraviolet rays from the transparent substrate film side, and a second irradiation step of subsequently irradiating ultraviolet rays from the coating layer side. At this time, as explained in the combination of the first first polymerization initiator and the second polymerization initiator, the first irradiation step is irradiation: in a region of a longer wavelength at which the first polymerization initiator is decomposed, for example, Ultraviolet light having a maximum luminous intensity in a wavelength region exceeding 370 nm; and irradiation in a second irradiation step: ultraviolet rays having a maximum luminous intensity in a shorter wavelength region in which the second polymerization initiator is decomposed, for example, a wavelength region below 370 nm Thus, the dried coating layer can be sufficiently cured to obtain a hard coating film having a high hardness. When the long hard coating film is continuously produced, the first irradiation step is preferably carried out by irradiating the substrate film side with ultraviolet rays while pressing the mirror roll or the platen roller against the coating layer.
硬化步驟所使用之紫外線光源，以及第一照射步驟與第二照射步驟分別進行時各步驟使用之紫外線光源，可從發射出必要的紫外線者當中適當選擇使用。此等步驟中之紫外線照射量或積算光量等照射條件，係以可使最終所得之硬塗層充分硬化之方式適當設定條件。 The ultraviolet light source used in the hardening step and the ultraviolet light source used in each step of the first irradiation step and the second irradiation step can be appropriately selected from those in which necessary ultraviolet rays are emitted. The irradiation conditions such as the amount of ultraviolet irradiation or the amount of integrated light in these steps are appropriately set so that the hard coat layer finally obtained can be sufficiently cured.
第1圖係示意顯示從呈輥狀備用之基材薄膜製造硬塗薄膜時之較佳裝置配置例之流程圖。參照該圖說明硬塗薄膜之妥適製造方法。 Fig. 1 is a flow chart showing an example of a preferred apparatus arrangement for producing a hard coat film from a substrate film which is in the form of a roll. A suitable manufacturing method of the hard coat film will be described with reference to the figure.
參照第1圖，於塗佈區12，將紫外線硬化性塗佈組成物(塗佈液)13塗佈於從送出輥10送出之透明基材薄膜11，如此形成塗佈層之透明基材薄膜，於乾燥區14進行乾燥後，被導入至第一照射區20。於第一照射區20中，配置有塗膜側輥21與第一紫外線光源22，以及用以將附塗佈層之透明基材薄膜的塗佈層壓抵於塗膜側輥21之入口側軋輥23及出口側軋輥24。然後藉由入口側軋輥23將塗佈層壓抵於塗膜側輥21，於該狀態下，使來自第一紫外線光源22的紫外線通過透明基材薄膜11進行照射，使塗佈層硬化。隨後通過出口側軋輥24，從塗膜側輥21中剝離，並被導入至第二照射區26。於第二照射區26中，配置有第二紫外線光源27，其紫外線係從透明基材薄膜11上形成之塗佈層側進行照射，如此施以至少2次紫外線照射後製成之硬塗薄膜被捲取於捲取輥30。該圖中，係顯示於第二照射區僅配置1個紫外線光源之例子，但在此進行2次紫外線照射者亦為有效。圖中，直線的箭頭表示薄膜的行進方向，曲線的箭頭表示輥的旋轉方向。 Referring to Fig. 1, an ultraviolet curable coating composition (coating liquid) 13 is applied to the transparent base film 11 fed from the delivery roller 10 in the coating zone 12, thereby forming a transparent base film of the coating layer. After drying in the drying zone 14, it is introduced into the first irradiation zone 20. In the first irradiation zone 20, the coating film side roller 21 and the first ultraviolet light source 22 are disposed, and the coating of the transparent substrate film with the coating layer is applied to the inlet side of the coating film side roller 21. Roller 23 and outlet side roll 24. Then, the coating is applied to the coating film side roller 21 by the inlet side roll 23, and in this state, the ultraviolet ray from the first ultraviolet light source 22 is irradiated through the transparent base film 11, and the coating layer is cured. Subsequently, it is peeled off from the coating film side roll 21 by the outlet side roll 24, and introduced into the second irradiation zone 26. In the second irradiation zone 26, a second ultraviolet light source 27 is disposed, and the ultraviolet light is irradiated from the side of the coating layer formed on the transparent base film 11, and thus the hard coat film is formed by applying at least two times of ultraviolet irradiation. It is taken up by the take-up roll 30. In the figure, an example in which only one ultraviolet light source is disposed in the second irradiation region is shown, but it is also effective to perform ultraviolet irradiation twice. In the figure, a straight arrow indicates the traveling direction of the film, and a curved arrow indicates the direction of rotation of the roller.
第1圖所示之方式中，若使用表面平滑者作為塗膜側輥21，則可製造表面平滑之硬塗薄膜。另一方面，若使用表面具有細微凹凸之壓印模具作為該塗膜側輥21，則可製造表面形成細微凹凸之防眩性硬塗薄膜。 In the embodiment shown in Fig. 1, when a smooth surface is used as the coating film side roller 21, a hard coating film having a smooth surface can be produced. On the other hand, when an imprint mold having fine irregularities on its surface is used as the coating film side roll 21, an antiglare hard coat film having fine irregularities on its surface can be produced.
使用本發明之紫外線硬化性塗佈組成物製造之硬塗薄膜，不會產生橘皮表面或白化，為外觀良好者，此外，即使採用將塗佈層壓抵於模具使硬化之方法，亦可得到對水接觸角大且防污性優異之薄膜。因此，該薄膜為透明性亦優異、總透光率亦高者。總透光率，可依據JIS K7361-1：1997「塑膠-透明材料之總透光率的試驗方法-第1部：單光束法」進行測定，由本發明之塗佈組成物製造之硬塗薄膜，可使總透光率大致成為90%以上。 The hard coat film produced by using the ultraviolet curable coating composition of the present invention does not cause surface or whitening of the orange peel, and has a good appearance, and can be cured by applying the laminate to the mold. A film having a large water contact angle and excellent antifouling property is obtained. Therefore, the film is also excellent in transparency and high in total light transmittance. The total light transmittance can be measured according to JIS K7361-1:1997 "Testing method for total light transmittance of plastic-transparent materials - Part 1: Single beam method", and hard coating film produced from the coating composition of the present invention. The total light transmittance can be made approximately 90% or more.
以下係顯示實施例更具體說明本發明，但本發明並不限定於此等例子。例中，表示使用量之份，在無特別記載時為重量基準。首先顯示製造數種含氟胺甲酸乙酯化多官能丙烯酸酯化合物作為含氟硬化性化合物之合成例。 The present invention will be more specifically described by the following examples, but the invention is not limited thereto. In the examples, the parts used are indicated, and unless otherwise specified, they are based on weight. First, a synthesis example in which a plurality of fluorine-containing urethane-based polyfunctional acrylate compounds are produced as a fluorine-containing curable compound is shown.
將1,6-六亞甲二異氰酸酯[由Asahi Kasei Chemicals股份有限公司販售之"DURANATE 50M-HDI"]84.0g、2-(全氟己基)乙醇[由Du Pont公司販售之"CAPSTONE 62-AL"]36.4g以及二月桂酸二丁基錫[由ARKEMA公司販售之"FASCAT 4202"]0.3g，裝入具備攪拌機、溫度調節器、溫度計及冷凝器之內容量1公升的三頸燒瓶，以使內溫成為60至70℃之方式藉由油浴加熱，並進行3小時的反應。另外，將使氫醌單甲醚[EASTMAN CHEMICAL公司販售之"Eastman HQMME"]0.2g均勻混合溶解於三丙烯酸新戊四醇酯[新中村化學工業股份有限公司販售之"NK Ester A-TMM-3L"]620g後之液體，裝入預先保溫50℃之附側管之滴液漏斗內。將滴液漏斗內之液體，於氮氣環境下，於攪拌下滴入混合於溫度保持在60至70℃之上述三頸燒瓶內的內容物中，並於同一溫度下攪拌4小時。藉此得到常溫(25℃)下為黏稠液狀的反應生成物。 1,6-hexamethylene diisocyanate ["DURANATE 50M-HDI" sold by Asahi Kasei Chemicals Co., Ltd.] 84.0 g, 2-(perfluorohexyl)ethanol [CAPSTONE 62 sold by Du Pont) -AL"]36.4g and dibutyltin dilaurate [FASCAT 4202"] sold by ARKEMA, 0.3g, and filled into a three-necked flask containing a stirrer, a temperature regulator, a thermometer and a condenser. The reaction was carried out for 3 hours by heating in an oil bath so that the internal temperature became 60 to 70 °C. In addition, hydroquinone monomethyl ether will be made [Eastman sold by Eastman Chemical Company" HQMME"] 0.2g uniformly mixed with a liquid dissolved in neodymetic acid triacrylate ("NK Ester A-TMM-3L"] sold by Xinzhongcun Chemical Industry Co., Ltd., and filled with a pre-insulation of 50 °C In the dropping funnel of the side tube, the liquid in the dropping funnel is dropped into the contents of the above three-necked flask maintained at a temperature of 60 to 70 ° C under stirring under a nitrogen atmosphere at the same temperature. The mixture was stirred for 4 hours, whereby a reaction product in a viscous liquid at normal temperature (25 ° C) was obtained.
合成例1中，將1,6-六亞甲二異氰酸酯變更為異佛爾酮二異氰酸酯[由EVONIK公司販售之"VESTANAT IPDI"]111.0g，其他進行與合成例1相同之操作，得到黏稠液狀的反應生成物。 In Synthesis Example 1, 1,6-hexamethylene diisocyanate was changed to 111.0 g of isophorone diisocyanate [VESTANAT IPDI" sold by EVONIK, and the same operation as in Synthesis Example 1 was carried out to obtain a thick one. A liquid reaction product.
合成例1中，將1,6-六亞甲二異氰酸酯變更為1,6-六亞甲二異氰酸酯的異三聚氰酸酯三聚物[由Asahi Kasei Chemicals股份有限公司販售之"DURANATE TKA-100"]182g，其他進行與合成例1相同之操作，得到黏稠液狀的反應生成物。 In Synthesis Example 1, a 1,3 - hexamethylene diisocyanate was changed to an isomeric isocyanate trimer of 1,6-hexamethylene diisocyanate [DURANATE TKA sold by Asahi Kasei Chemicals Co., Ltd. -100"]182g, and the same operation as in Synthesis Example 1 was carried out to obtain a reaction product in a viscous liquid state.
合成例1中，將1,6-六亞甲二異氰酸酯變更為二環己基甲烷-4,4'-二異氰酸酯[由BAYER MATERIALSCIENCE公 司販售之"DESMODUR W"]134.0g，其他進行與合成例1相同之操作，得到黏稠液狀的反應生成物。 In Synthesis Example 1, 1,6-hexamethylene diisocyanate was changed to dicyclohexylmethane-4,4'-diisocyanate [by BAYER MATERIALSCIENCE 134.0 g of "DESMODUR W" sold by the company was subjected to the same operation as in Synthesis Example 1 to obtain a reaction product in a viscous liquid state.
以上合成例1至4所得之含氟胺甲酸乙酯化多官能丙烯酸酯化合物的結構式，表示如下。 The structural formula of the fluorinated urethane-formated polyfunctional acrylate compound obtained in the above Synthesis Examples 1 to 4 is shown below.
接著使用以上製造之含氟胺甲酸乙酯化多官能丙烯酸酯化合物調製紫外線硬化性塗佈組成物，並顯示由該塗佈組成物製作硬塗薄膜之實施例及比較例。在此，不含氟硬化性化合物係使用以下所示者。於後表中，以下述前頭所顯示之編號表示。 Next, the ultraviolet curable coating composition was prepared by using the above-mentioned fluorine-containing urethane-based polyfunctional acrylate compound, and an example and a comparative example in which a hard coat film was produced from the coating composition were shown. Here, the fluorine-free curable compound is used as follows. In the following table, the numbers indicated by the headings below are indicated.
M-305：三丙烯酸新戊四醇酯[由東亞合成股份有限公 司販售之"Aronix M-305"]，A-TMPT：三丙烯酸三羥甲基丙烷酯[由新中村化學工業股份有限公司販售之"NK Ester A-TMPT"]，DPEA-12：經EO(環氧乙烷)改質之六丙烯酸二新戊四醇酯[由日本化藥股份有限公司販售之"KAYARAD DPEA-12"]，M4004：經EO(環氧乙烷)改質之四丙烯酸新戊四醇酯[由MIWON公司販售之"MIRAMER M4004"]，A-400：聚二丙烯酸乙二醇酯[由新中村化學工業股份有限公司販售之"NK Ester A-400"]，對於以上所示之不含氟硬化性化合物及先前合成例製造之含氟硬化性化合物，分別藉由以下方法求取耐水度，其結果如表1所示。 M-305: pentaerythritol triacrylate [from East Asia Synthetic Co., Ltd. "Aronix M-305" sold by the company, A-TMPT: Trimethylolpropane triacrylate [NK Ester A-TMPT" sold by Shin-Nakamura Chemical Industry Co., Ltd., DPEA-12: EO (ethylene oxide) modified dipentaerythritol hexaacrylate [KAYARAD DPEA-12" sold by Nippon Kayaku Co., Ltd., M4004: modified by EO (ethylene oxide) Neopentyl tetraacrylate [MIRAMER M4004" sold by MIWON], A-400: Polyethylene glycol diacrylate ["NK Ester A-400" sold by Shin-Nakamura Chemical Industry Co., Ltd." The water resistance was determined by the following method for each of the fluorine-free curable compound and the fluorine-containing curable compound produced in the previous synthesis example. The results are shown in Table 1.
分別將各硬化性化合物1g與丙酮10ml投入於容量100ml的燒杯使混合分散。使用滴定管將離子交換水緩慢加入於該分散液，求取至分散液產生白濁為止之所需離子交換水量(單位：ml)，作為該硬化性化合物的耐水度。 1 g of each curable compound and 10 ml of acetone were placed in a beaker having a capacity of 100 ml to be mixed and dispersed. Ion-exchanged water was slowly added to the dispersion liquid using a burette, and the amount of ion-exchanged water (unit: ml) required until the dispersion liquid became cloudy was determined as the water resistance of the curable compound.
此外，以下的例子中，光聚合起始劑係使用以下商品名稱者。以後僅顯示下列所示以""包圍之商品名稱。 Further, in the following examples, the photopolymerization initiator is the one having the following trade names. Only the product names surrounded by "" shown below will be displayed in the future.
"Irgacure 184"：化學名稱為(1-羥基環己基)苯基酮，由BASF公司販售，"Lucirin TPO"：化學名稱為2,4,6-三甲基苯甲醯基二苯基膦氧化物，由BASF公司販售。 "Irgacure 184": chemical name (1-hydroxycyclohexyl) phenyl ketone, sold by BASF, "Lucirin TPO": chemical name 2,4,6-trimethylbenzhydryldiphenylphosphine Oxide, sold by BASF Corporation.
〈硬塗薄膜的製作〉 <Production of Hard Coating Film>
以表2所示之重量比率(合計設為100份之值)混合含氟硬化性化合物及不含氟硬化性化合物。惟於比較例12及13中，僅使用不含氟硬化性化合物。表2中，由先前數 學式(1)計算之親和力A之值亦一同顯示。將作為光聚合起始劑之"Irgacure 184"2份及"Lucirin TPO"1份、以及作為溶劑之乙酸乙酯40份及乙酸丁酯20份添加於此等硬化性化合物合計37份中混合後，使用棒塗佈機，以使乾燥後的膜厚成為5μm之方式塗佈於三乙酸纖維素薄膜上。接著進行乾燥以去除溶劑，將鎳製的平板貼合於該塗佈層側。於該狀態下，以Fusion公司製的"V Bulb"燈(最大發光波長420nm)作為光源，以積算光量700mJ/cm2從該三乙酸纖維素薄膜側照射紫外線(第一照射步驟)。然後從鎳平板剝離硬化塗膜，以Fusion公司製的"H Bulb"燈(最大發光波長360nm)作為光源，以積算光量300mJ/cm2從該硬化塗膜側照射紫外線(第二照射步驟)。如此製成於三乙酸纖維素薄膜的表面形成硬塗層之薄膜(硬塗薄膜)。 The fluorine-containing curable compound and the fluorine-free curable compound were mixed at a weight ratio shown in Table 2 (total value of 100 parts). However, in Comparative Examples 12 and 13, only the fluorine-free curable compound was used. In Table 2, the value of the affinity A calculated by the previous mathematical formula (1) is also shown together. 2 parts of "Irgacure 184" and 1 part of "Lucirin TPO" as a photopolymerization initiator, and 40 parts of ethyl acetate as a solvent and 20 parts of butyl acetate were added to 37 parts of the total of the curable compounds. The film was applied to a cellulose triacetate film by using a bar coater so that the film thickness after drying became 5 μm. Subsequently, drying was performed to remove the solvent, and a nickel plate was attached to the coating layer side. In this state, a "V Bulb" lamp (maximum emission wavelength of 420 nm) manufactured by Fusion Co., Ltd. was used as a light source, and ultraviolet rays were irradiated from the cellulose triacetate film side at a total amount of light of 700 mJ/cm 2 (first irradiation step). Then, the hardened coating film was peeled off from the nickel plate, and a "H Bulb" lamp (maximum emission wavelength: 360 nm) manufactured by Fusion Co., Ltd. was used as a light source, and ultraviolet rays were irradiated from the hardened coating film side at a total amount of light of 300 mJ/cm 2 (second irradiation step). The film (hard coat film) formed into a hard coat layer on the surface of the cellulose triacetate film was thus formed.
〈硬塗薄膜的評估〉 <Evaluation of hard coat film>
所得之硬塗薄膜以下列方法進行評估，結果彙總於表3。 The obtained hard coat film was evaluated in the following manner, and the results are summarized in Table 3.
1)塗膜的外觀評估 1) Appearance evaluation of the film
以目視觀察硬塗薄膜的外觀，以下列基準進行評估。 The appearance of the hard coat film was visually observed and evaluated on the following basis.
○：無凝聚物的產生、橘皮表面或白化。 ○: No generation of aggregates, surface of orange peel or whitening.
×：觀察到凝聚物的產生、橘皮表面或白化。 ×: The generation of aggregates, the surface of orange peel or whitening was observed.
2)霧度值及總透光率的測定 2) Determination of haze value and total light transmittance
依據先前揭示之JIS K7136：2000及JIS K7361-1：1997，藉由村上色彩技術研究所製造的霧度儀"HM-150"測定霧度值及總透光率。 According to the previously disclosed JIS K7136:2000 and JIS K7361-1:1997, the haze value and the total light transmittance were measured by a haze meter "HM-150" manufactured by Murakami Color Research Institute.
3)密合性試驗 3) Adhesion test
依據JIS K5600-5-6：1999「塗料一般試驗方法-第5部：塗膜的機械性質-第6節：附著性(橫切法)」規定之棋盤目膠帶法，以裁切刀於硬塗層切割1mm間隔之棋盤目狀切痕形成100個方格，然後將由Nichiban股份有限公司販售之玻璃紙膠帶貼合於附有該棋盤目狀切痕之硬塗層表面，一口氣將其剝離後，計算未剝離之殘留硬塗層的方格數，並以殘留方格數相對於原先方格數100之比率來表示。100/100意指無剝離，0/100意指完全剝離。 According to JIS K5600-5-6:1999 "General Test Methods for Coatings - Part 5: Mechanical Properties of Coatings - Section 6: Adhesion (Cross-cutting Method)", the chessboard tape method is used to cut the knife hard. The coating cuts a 1 mm-interval checkerboard shape to form 100 squares, and then attaches the cellophane tape sold by Nichiban Co., Ltd. to the surface of the hard coat layer with the checker-shaped cut of the checkerboard, and peels it off in one breath. Thereafter, the number of squares of the unpeeled residual hard coat layer was calculated, and the ratio of the number of remaining squares to the original square number of 100 was expressed. 100/100 means no peeling, and 0/100 means complete peeling.
4)對水接觸角的測定 4) Determination of water contact angle
依據先前揭示之JIS R3257：1999，藉由協和界面科學股份有限公司製造的接觸角計(CA-X型)測定對水接觸角。若對水接觸角為80°以上，則可判斷防污性大致良好。 The water contact angle was measured by a contact angle meter (CA-X type) manufactured by Concord Interface Science Co., Ltd. according to JIS R3257:1999 previously disclosed. When the water contact angle is 80 or more, it can be judged that the antifouling property is substantially good.
如表3所示，使用親和力A位於1至2的範圍之硬化性化合物的混合物之實施例1至15，對硬塗膜的外觀及對水接觸角均可賦予良好的結果。相對於此，使用親和力A小於1之硬化性化合物的混合物之比較例5、6及8至11，雖然硬塗膜的外觀良好，但由於接觸角小而容易污染。未使用含氟硬化性化合物之比較例12及13亦相同。另一方面，使用親和力A大於2之硬化性化合物的混合物之比較例1至4及7，接觸角為100°以上，所以防污性良好，但於在硬塗膜容易產生凝聚物或是形成橘皮表面或白化，故外觀不良，霧度亦增高。 As shown in Table 3, Examples 1 to 15 using a mixture of curable compounds having an affinity A in the range of 1 to 2 gave good results to both the appearance of the hard coat film and the water contact angle. On the other hand, in Comparative Examples 5, 6, and 8 to 11 in which a mixture of curable compounds having an affinity A of less than 1 was used, although the appearance of the hard coat film was good, it was easily contaminated due to a small contact angle. Comparative Examples 12 and 13 in which the fluorine-containing curable compound was not used were also the same. On the other hand, in Comparative Examples 1 to 4 and 7 in which a mixture of curable compounds having an affinity A of more than 2 was used, since the contact angle was 100 or more, the antifouling property was good, but cohesive or formation was likely to occur in the hard coat film. The surface of the orange peel is white or white, so the appearance is poor and the haze is also increased.
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- 2015-09-18 TW TW104130912A patent/TWI655252B/en active
- 2015-09-23 CN CN201510612452.XA patent/CN105462476B/en active Active
- 2015-09-23 KR KR1020150134745A patent/KR102303672B1/en active IP Right Grant
- 2015-09-24 JP JP2015186418A patent/JP6613758B2/en active Active
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| TW201041985A (en) * | 2009-02-27 | 2010-12-01 | Lg Chemical Ltd | Coating composition and coating film having enhanced abrasion resistance and contamination resistance |
| JP2012072235A (en) * | 2010-09-28 | 2012-04-12 | Sumitomo Chemical Co Ltd | Method for producing hard coat film, polarizing plate, and image display device |
| US20140186542A1 (en) * | 2012-12-27 | 2014-07-03 | Lg Display Co., Ltd. | Anti-Finger Printed Hard Coating Resin Composition and Method of Fabricating Anti-Finger Printed Hard Coating Film Using the Same |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201623485A (en) | 2016-07-01 |
| JP6613758B2 (en) | 2019-12-04 |
| CN105462476A (en) | 2016-04-06 |
| KR102303672B1 (en) | 2021-09-16 |
| JP2016069649A (en) | 2016-05-09 |
| KR20160037097A (en) | 2016-04-05 |
| CN105462476B (en) | 2019-06-28 |
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