TW201825615A - Hard Coating Film and Image Display Device Having the Same - Google Patents
Hard Coating Film and Image Display Device Having the Same Download PDFInfo
- Publication number
- TW201825615A TW201825615A TW106127999A TW106127999A TW201825615A TW 201825615 A TW201825615 A TW 201825615A TW 106127999 A TW106127999 A TW 106127999A TW 106127999 A TW106127999 A TW 106127999A TW 201825615 A TW201825615 A TW 201825615A
- Authority
- TW
- Taiwan
- Prior art keywords
- hard coating
- coating composition
- coating film
- coating layer
- hard
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
-
- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/42—Polarizing, birefringent, filtering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Theoretical Computer Science (AREA)
- Optics & Photonics (AREA)
- General Engineering & Computer Science (AREA)
- Human Computer Interaction (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Laminated Bodies (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Paints Or Removers (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polarising Elements (AREA)
- Spectroscopy & Molecular Physics (AREA)
Abstract
Description
本發明是有關於一種硬塗膜及具有其之影像顯示裝置,且特別是有關於一種能夠最小化翹曲發生同時具有優異的抗彎曲性與抗刮擦性的硬塗膜,其具有硬塗膜之影像顯示裝置。The present invention relates to a hard coating film and an image display device having the same, and particularly to a hard coating film capable of minimizing the occurrence of warping and having excellent bending resistance and scratch resistance. Film image display device.
硬塗膜已用於保護各種影像顯示器之表面,該等顯示器包括液晶顯示裝置(LCD)、電致發光(EL)顯示裝置、電漿顯示器(PD)、場發射顯示器(FED)及其類似物。Hard-coated films have been used to protect the surfaces of various video displays, including liquid crystal display (LCD), electroluminescence (EL) display, plasma display (PD), field emission display (FED), and the like .
近年來,可撓式顯示器作為下一代顯示裝置得到越來越多的關注,因為可撓式顯示器應用諸如塑膠之可撓性材料代替一般不具有可撓性之玻璃基板,使得即使像紙一樣將其彎曲,其仍能夠維持顯示器效能。因此,有需要一種硬塗膜,其不但具有高硬度及良好抗刮擦性,且具有適當的可撓性,使得能夠在其製造或使用期間,膜角落處不會出現翹曲而防止裂紋生成。In recent years, flexible displays have received more and more attention as the next-generation display device, because flexible displays use flexible materials such as plastics instead of glass substrates that are not generally flexible, making It is curved, and it can still maintain display performance. Therefore, there is a need for a hard coating film that not only has high hardness and good scratch resistance, but also has appropriate flexibility, so that during its manufacture or use, no warpage occurs at the corners of the film to prevent cracks from forming .
韓國專利申請公開案第10-2016-0057221號揭示了一種高硬度硬塗膜,其使用硬塗佈組成物形成,硬塗佈組成物包括具有重量平均分子量800至30,000之環氧矽氧樹脂、含有具有環氧環己烷結構之化合物的交聯劑、及光聚合起始劑。Korean Patent Application Publication No. 10-2016-0057221 discloses a high-hardness hard coating film formed using a hard coating composition including an epoxy silicone resin having a weight average molecular weight of 800 to 30,000, A crosslinking agent containing a compound having an epoxycyclohexane structure, and a photopolymerization initiator.
然而,在具有此高硬度之硬塗佈組成物的情況下,會有抗彎曲性及/或抗刮擦性不足且翹曲發生的問題。However, in the case of a hard coating composition having such a high hardness, there are problems in that bending resistance and / or scratch resistance are insufficient and warpage occurs.
【技術問題】【technical problem】
本發明之一目的係提供一種硬塗膜,其能夠抑制翹曲發生,同時具有優異的抗彎曲性及抗刮擦性。An object of the present invention is to provide a hard coating film, which can suppress the occurrence of warpage and has excellent bending resistance and scratch resistance.
本發明之另一目的係提供一種具有上述硬塗膜的影像顯示裝置。Another object of the present invention is to provide an image display device having the hard coating film.
【技術手段】[Technical means]
根據本發明之一概念,係提出一種硬塗膜,其中一第一硬塗層與一第二硬塗層係層壓在一基底膜的一側上,其中,當該第一硬塗層與該第二硬塗層的翹曲值分別為A及B時,AB<0。According to a concept of the present invention, a hard coating film is proposed, in which a first hard coating layer and a second hard coating layer are laminated on one side of a base film, and when the first hard coating layer and the When the warpage values of the second hard coat layer are A and B, AB <0.
在本發明的一實施例中,該第一硬塗層可由一第一硬塗佈組成物形成,該第一硬塗佈組成物包括一光可固化丙烯酸系樹脂、一光聚合起始劑及一溶劑,且該第二硬塗層可由一第二硬塗佈組成物形成,該第二硬塗佈組成物包括一光可固化環氧樹脂、一光聚合起始劑及一溶劑。In an embodiment of the present invention, the first hard coating layer may be formed of a first hard coating composition. The first hard coating composition includes a photocurable acrylic resin, a photopolymerization initiator, and A solvent, and the second hard coating layer may be formed of a second hard coating composition. The second hard coating composition includes a photocurable epoxy resin, a photopolymerization initiator, and a solvent.
在本發明的一實施例中,該第一硬塗層可由一第一硬塗佈組成物形成,該第一硬塗佈組成物包括一具有一端(甲基)丙烯酸酯基的樹枝狀化合物、一單官能(甲基)丙烯酸酯、一光聚合起始劑及一溶劑,且該第二硬塗層可由一第二硬塗佈組成物形成,該第二硬塗佈組成物包括一具有環氧基的烷氧基矽烷化合物或聚矽氧樹脂、一光聚合起始劑、及一溶劑。In an embodiment of the present invention, the first hard coating layer may be formed of a first hard coating composition, and the first hard coating composition includes a dendritic compound having a (meth) acrylate group at one end, A monofunctional (meth) acrylate, a photopolymerization initiator, and a solvent, and the second hard coating layer may be formed of a second hard coating composition, the second hard coating composition includes a Alkoxysilane compound or polysiloxane resin, a photopolymerization initiator, and a solvent.
根據本發明之另一概念,係提出一種具有上述硬塗膜的影像顯示裝置。According to another concept of the present invention, an image display device having the hard coating film is provided.
【有利效果】[Beneficial effects]
根據本發明之硬塗膜能最小化翹曲的發生,同時具有優異的抗彎曲性與抗刮擦性,且藉此其能夠有效應用在可撓式顯示裝置的視窗。The hard coating film according to the present invention can minimize the occurrence of warpage, and at the same time has excellent bending resistance and scratch resistance, and thereby it can be effectively applied to a window of a flexible display device.
本發明將於下文詳述。The present invention will be described in detail below.
本發明之一實施例係有關於硬塗膜,其中第一硬塗層與第二硬塗層係層壓在基底膜的一側上,其中,當第一硬塗層與第二硬塗層的翹曲值(curl value)分別為A及B時,AB<0。An embodiment of the present invention relates to a hard coating film, wherein the first hard coating layer and the second hard coating layer are laminated on one side of the base film, wherein when the first hard coating layer and the second hard coating layer are When the curl values are A and B, AB <0.
在本發明的一實施例中,第一硬塗層與第二硬塗層的翹曲值是在第一硬塗層或第二硬塗層各自獨立層壓在基底膜上之後所量測出的值。In an embodiment of the present invention, the warpage value of the first hard coating layer and the second hard coating layer is measured after the first hard coating layer or the second hard coating layer is independently laminated on the base film. Value.
翹曲值可藉由將硬塗膜切斷為10 cm×10 cm之尺寸,留在25℃、48%RH環境下24小時,放置該膜使得其凸形表面係接觸一參考表面,並然後量測從參考表面至四個角落之高度的平均而獲得。正翹曲係以(+)值表示,且相反翹曲係以(-)值表示。The warpage value can be obtained by cutting the hard coating film to a size of 10 cm × 10 cm, leaving it at 25 ° C, 48% RH for 24 hours, and placing the film so that its convex surface contacts a reference surface, and then Measured from the average of the height from the reference surface to the four corners. The positive warpage is represented by a (+) value, and the reverse warp is represented by a (-) value.
當硬塗膜係以基底膜的表面面向參考表面配置時,正翹曲是在硬塗層的表面上具有凹形輪廓的翹曲,凹形輪廓的表面位在基底膜之相反側上,且相反翹曲是硬塗層的表面上具有凸形輪廓的翹曲。When the hard coating film is configured with the surface of the base film facing the reference surface, positive warpage is warping with a concave contour on the surface of the hard coating layer, and the surface of the concave contour is on the opposite side of the base film, and Converse warping is warping with a convex profile on the surface of the hard coating.
因此,AB<0表示第一硬塗層與第二硬塗層之翹曲值的其中之一者為(+)值,且剩餘的一者為(-)值。亦即,第一硬塗層與第二硬塗層任一者具有正翹曲,且剩餘的一者具有相反翹曲。Therefore, AB <0 means that one of the warpage values of the first hard coat layer and the second hard coat layer is a (+) value, and the remaining one is a (-) value. That is, either the first hard coating layer or the second hard coating layer has positive warpage, and the remaining one has opposite warpage.
根據本發明之一實施例的硬塗膜係符合第一硬塗層與第二硬塗層之翹曲值的相乘值為小於0(亦即,AB <0)的條件,藉此抑制翹曲的發生。A hard coating film according to an embodiment of the present invention meets a condition that a multiplication value of warpage values of a first hard coating layer and a second hard coating layer is less than 0 (that is, AB <0), thereby suppressing warping The occurrence of the song.
在根據本發明之實施例的硬塗膜中,第一硬塗層的翹曲值可為(+),且第二硬塗層的翹曲值可為(-)。此時,可最小化翹曲的發生機會。In the hard coating film according to the embodiment of the present invention, the warp value of the first hard coat layer may be (+), and the warp value of the second hard coat layer may be (-). At this time, the occurrence of warpage can be minimized.
根據本發明之實施例的硬塗膜可藉由塗佈硬塗佈組成物於基底膜的一側上,並然後藉由固化從而形成第一硬塗層與第二硬塗層製得。The hard coating film according to the embodiment of the present invention can be obtained by applying a hard coating composition on one side of a base film, and then curing the first hard coating layer and the second hard coating layer.
在根據本發明之一實施例的硬塗膜中,是使用以下所述之第一硬塗佈組成物或第二硬塗佈組成物中的任一者形成第一硬塗層,並使用硬塗佈組成物中剩餘的一者形成第二硬塗層。舉例來說,第一硬塗層可由第一硬塗佈組成物形成,且第二硬塗層可由第二硬塗佈組成物形成。In a hard coating film according to an embodiment of the present invention, a first hard coating layer is formed using any of the first hard coating composition or the second hard coating composition described below, and the hard coating film is used. The remaining one of the coating composition forms a second hard coat layer. For example, the first hard coating layer may be formed from a first hard coating composition, and the second hard coating layer may be formed from a second hard coating composition.
對於基底膜而言,可使用任何具有透明性質的聚合物膜。聚合物膜可藉由根據分子量的膜形成方法或押出方法及膜的製造方法製得,且只要其是商業上可獲得的透明聚合物膜,使用上並沒有限制。其範例包括各種透明的聚合物基底,例如三乙醯纖維素(triacetyl cellulose)、乙醯基丁酸纖維素(acetyl cellulose butyrate)、乙烯-乙酸乙烯酯共聚物(ethylene-vinyl acetate copolymer)、丙醯基纖維素(propionyl cellulose)、丁醯基纖維素(butyryl cellulose)、乙醯丙醯纖維素(acetylpropionyl cellulose)、聚酯(polyester)、聚苯乙烯(polystyrene)、聚醯胺(polyamide)、聚醚醯亞胺(polyether imide)、聚丙烯(polyacryl)、聚亞醯胺(polyimide)、聚醚碸(polyether sulfone),聚碸(polysulfone)、聚乙烯(polyethylene)、聚丙烯(polypropylene)、聚甲基戊烯(polymethyl pentene)、聚氯乙烯(polyvinyl chloride)、聚二氯亞乙烯(polyvinylidene chloride、聚乙烯醇(polyvinylalcohol)、聚乙烯縮醛(polyvinylacetal)、聚醚酮(polyether ketone)、聚醚醚酮(polyether ether ketone)、聚醚碸(polyether sulfone)、聚甲基丙烯酸甲酯(polymethyl methacrylate)、聚乙烯對苯二甲酸酯(polyethylene terephthalate)、聚對苯二甲酸丁二酯(polybutylene terephthalate)、聚萘二甲酸乙二醇酯(polyethylene naphthalate)、聚碳酸酯(polycarbonate)、及其類似物。For the base film, any polymer film having transparent properties can be used. The polymer film can be produced by a film forming method or an extrusion method and a film manufacturing method according to the molecular weight, and there is no limitation in use as long as it is a commercially available transparent polymer film. Examples include various transparent polymer substrates such as triacetyl cellulose, acetyl cellulose butyrate, ethylene-vinyl acetate copolymer, acrylic Propionyl cellulose, butyryl cellulose, acetylpropionyl cellulose, polyester, polystyrene, polyamide, polyether Polyimide (polyether imide), polypropylene (polyacryl), polyimide (polyimide), polyether sulfone, polysulfone, polyethylene (polyethylene), polypropylene (polypropylene), polyethylene Polymethyl pentene, polyvinyl chloride, polyvinylidene chloride, polyvinylcohol, polyvinylacetal, polyether ketone, polyether Polyether ether ketone, polyether sulfone, polymethyl ether Methyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate (Polycarbonate), and the like.
基底膜的厚度並未特別限制,但可為10至1000 ㎛,較佳為20至150 ㎛。當基底膜的厚度小於10 ㎛時,膜的強度下降且因此可加工性質降低。當基底膜的厚度大於1000 ㎛時,透明性質下降或硬塗膜的重量提高。The thickness of the base film is not particularly limited, but may be 10 to 1000 ㎛, and preferably 20 to 150 ㎛. When the thickness of the base film is less than 10 ㎛, the strength of the film decreases and thus the processability decreases. When the thickness of the base film is more than 1000 ㎛, the transparency property decreases or the weight of the hard coating film increases.
第一硬塗層與第二硬塗層可分別具有1至10 ㎛的厚度。當第一硬塗層與第二硬塗層的厚度分別小於1 ㎛時,會難以保證硬度。若厚度大於10 ㎛時,可能會降低抗彎曲性或可能發生嚴重的翹曲。The first hard coating layer and the second hard coating layer may each have a thickness of 1 to 10 ㎛. When the thicknesses of the first hard coating layer and the second hard coating layer are each less than 1 ㎛, it may be difficult to ensure the hardness. If the thickness is more than 10 ㎛, bending resistance may be reduced or severe warpage may occur.
<第一硬塗佈組成物><First Hard Coating Composition>
在本發明的一實施例中,第一硬塗佈組成物可包括光可固化丙烯酸系樹脂、光聚合起始劑及溶劑。In one embodiment of the present invention, the first hard coating composition may include a photocurable acrylic resin, a photopolymerization initiator, and a solvent.
光可固化丙烯酸系樹脂可包括擇自由具有端(甲基)丙烯酸酯基的樹枝狀化合物(dendrimer compound having a terminal (meth)acrylate group)及單官能(甲基)丙烯酸酯(monofunctional (meth)acrylate)所構成之群組其中至少一者 。The photocurable acrylic resin may include a dendrimer compound having a terminal (meth) acrylate group and a monofunctional (meth) acrylate ) At least one of the groups.
在本發明的一實施例中,具有端(甲基)丙烯酸酯基的樹枝狀化合物可使用紫外光藉由以(甲基)丙烯酸酯基取代分支結構的末端而固化,並具有中心完全為脂肪族並由三級酯鍵結構成的結構特性。因此,相較於一般的多官能丙烯酸酯單體,具有端(甲基)丙烯酸酯基的樹枝狀化合物具有隨著生成提高而具有更多相對於分子量之官能基的結構特性。當官能基分佈在末端時,核心部分在其固化期間能幫助提升彎曲性質。藉此,可獲得具有高硬度與提升之翹曲性質及可撓性的硬塗膜。In an embodiment of the present invention, the dendritic compound having a terminal (meth) acrylate group can be cured by using ultraviolet light by replacing the terminal end of the branched structure with a (meth) acrylate group, and having a center completely fat. Group and the structure characteristics of tertiary ester bond structure. Therefore, compared with a general polyfunctional acrylate monomer, a dendritic compound having a terminal (meth) acrylate group has a structural characteristic of having more functional groups relative to molecular weight as the production increases. When the functional groups are distributed at the ends, the core portion can help improve bending properties during its curing. Thereby, a hard coating film having high hardness and improved warpage properties and flexibility can be obtained.
具有端(甲基)丙烯酸酯基的樹枝狀化合物可由以下化學式1表示: [化學式1] [R1 ]4-n -C-[R2 -OR3 ]n 其中, R1 為C1 -C6 烷基, R2 為C1 -C6 伸烷基, R3 為(甲基)丙烯醯基((meth)acryloyl group)或,且至少一個R3 為, R4 為(甲基)丙烯醯基或,且至少一個R4 為, R5 為(甲基)丙烯醯基或R6 為(甲基)丙烯醯基, n為2至4之整數,且 m、x及y為2或3之整數。A dendritic compound having a terminal (meth) acrylate group can be represented by the following Chemical Formula 1: [Chemical Formula 1] [R 1 ] 4-n -C- [R 2 -OR 3 ] n wherein R 1 is C 1 -C 6 alkyl, R 2 is C 1 -C 6 alkyl, R 3 is (meth) acryloyl group or And at least one R 3 is R 4 is (meth) acrylfluorenyl or And at least one R 4 is R 5 is (meth) acrylfluorenyl or R 6 is a (meth) acrylfluorenyl group, n is an integer of 2 to 4, and m, x, and y are integers of 2 or 3.
於此使用的C1 -C6 烷基是指具有1至6個碳原子之線性或分支的單價烴基,且其範例包括甲基、乙基、正丙基(n-propyl)、異丙基(i-propyl)、正丁基、異丁基、叔丁基(t-butyl)、正戊基、正己基,及類似物,但不限於此。The C 1 -C 6 alkyl group used herein refers to a linear or branched monovalent hydrocarbon group having 1 to 6 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, and isopropyl (I-propyl), n-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl, and the like, but not limited thereto.
於此使用的C1 -C6 伸烷基是指具有1至6個碳原子之線性或分支的二價烴基,且其範例包括甲烯基、乙烯基、丙烯基、丁烯基、及類似物,但不限於此。The C 1 -C 6 alkylene group used herein refers to a linear or branched divalent hydrocarbon group having 1 to 6 carbon atoms, and examples thereof include a alkenyl group, a vinyl group, a propenyl group, a butenyl group, and the like Things, but not limited to this.
在本發明的一實施例中,具有端(甲基)丙烯酸酯基的樹枝狀化合物可典型地具有由以下化學式2表示的結構: [化學式2] In an embodiment of the present invention, the dendritic compound having a terminal (meth) acrylate group may typically have a structure represented by the following Chemical Formula 2: [Chemical Formula 2]
具有端(甲基)丙烯酸酯基的樹枝狀化合物是商業上可獲得的,或可由根據該發明領域已知的方法製備。舉例來說,末端以複數個(甲基)丙烯酸酯基取代之多分支的樹枝狀化合物可由特定多元醇之中心骨幹與二羥甲基丙酸(dimethylol propionic acid)之縮合反應以形成第一生成之樹枝狀結構,作為分支結構的二羥甲基丙酸反覆縮合反應以成長為第二或更高生成之樹枝狀結構,並然後在末端與丙烯酸縮合反應而獲得。Dendrimers having a terminal (meth) acrylate group are commercially available or can be prepared according to methods known in the field of the invention. For example, a multi-branched dendritic compound substituted with a plurality of (meth) acrylate groups at the end may be formed by a condensation reaction between a central backbone of a specific polyol and dimethylol propionic acid to form a first generation The dendritic structure is a branched structure in which dimethylolpropionic acid is repeatedly subjected to condensation reaction to grow into a second or higher generated dendritic structure, and then obtained by condensation reaction with acrylic acid at the terminal.
基於第一硬塗佈組成物之總重量為100%,可含有樹枝狀化合物的量為重量30至60%,較佳為重量35至55%。當樹枝狀化合物的重量含量低於30%時,其會難以表現出彎曲性質,且當樹枝狀化合物的重量含量高於60%時,其會由於立體阻礙所造成之未反應官能基的存在而變得難以對塗層給予硬度特性。The dendritic compound may be contained in an amount of 30 to 60% by weight, preferably 35 to 55% by weight based on the total weight of the first hard coating composition. When the dendritic compound content is less than 30% by weight, it may be difficult to exhibit bending properties, and when the dendritic compound is more than 60% by weight, it may be due to the presence of unreacted functional groups caused by steric hindrance It becomes difficult to impart hardness characteristics to the coating.
在本發明的一實施例中,單官能(甲基)丙烯酸酯可用以紫外光固化,並可增進硬塗膜的彎曲性質、增進可撓性、並最小化翹曲。In one embodiment of the present invention, the monofunctional (meth) acrylate can be cured by ultraviolet light, and can improve the bending properties of the hard coating film, improve flexibility, and minimize warpage.
單官能(甲基)丙烯酸酯的具體範例包括乙烷基(甲基)丙烯酸酯(ethyl (meth)acrylate)、甲烷基(甲基)丙烯酸酯(methyl (meth)acrylate)、2-乙基己基(甲基)丙烯酸酯(2-ethylhexyl (meth)acrylate)、丁基(甲基)丙烯酸酯(butyl (meth)acrylate)、異丁基(甲基)丙烯酸酯(isobutyl (meth)acrylate)、2-乙氧乙基(甲基)丙烯酸酯(2-ethoxyethyl (meth)acrylate)、異癸基(甲基)丙烯酸酯(isodecyl (meth)acrylate)、辛基(甲基)丙烯酸酯(octyl (meth)acrylate)、異辛基(甲基)丙烯酸酯(isooctyl (meth)acrylate)、2-甲氧乙基(甲基)丙烯酸酯(2-methoxyethyl (meth)acrylate)、異莰基(甲基)丙烯酸酯(isobornyl (meth)acrylate)、及類似物。Specific examples of monofunctional (meth) acrylates include ethyl (meth) acrylate, methyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate (2-ethylhexyl (meth) acrylate), butyl (meth) acrylate, isobutyl (meth) acrylate, 2 -2-ethoxyethyl (meth) acrylate, isodecyl (meth) acrylate, octyl (meth ) acrylate), isooctyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, isomethoxytyl (meth) acrylate Acrylate (isobornyl (meth) acrylate), and the like.
基於第一硬塗佈組成物之總重量為100%,可含有單官能(甲基)丙烯酸酯的量為重量5至10%。當單官能(甲基)丙烯酸酯的重量含量少於5%時,其將難以供予可撓性,且當單官能(甲基)丙烯酸酯的重量含量大於10%時,將會降損硬度特性。The amount of the monofunctional (meth) acrylate that can be contained is 5 to 10% by weight based on the total weight of the first hard coating composition. When the monofunctional (meth) acrylate content is less than 5% by weight, it will be difficult to provide flexibility, and when the monofunctional (meth) acrylate content is more than 10% by weight, the hardness will be reduced characteristic.
在本發明的一實施例中,光聚合起始劑是用以光固化第一硬塗佈組成物,且並未特別限制,可使用該技術領域中通常使用的起始劑。In an embodiment of the present invention, the photopolymerization initiator is used for photocuring the first hard coating composition, and is not particularly limited, and an initiator generally used in the technical field may be used.
光聚合起始劑可分類為類型I(Type I)光聚合起始劑與類型II(Type II)(奪氫(hydrogen abstraction)型)光聚合起始劑。類型I光聚合起始劑中自由基藉由化學結構或分子結合能的差異造成分子分解而產生。在類型II(奪氫型)中,三級胺係併作為共起始劑(co-initiator)。類型I光聚合起始劑的具體範例可包括苯乙酮類(acetophenones),例如4-苯氧基二氯苯乙酮(4-phenoxydichloroacetophenone)、4-叔丁基二氯苯乙酮(4-t-butyldichloroacetophenone)、4-叔丁基三氯苯乙酮(4-t-butyltrichloroacetophenone)、二乙氧基苯乙酮(diethoxyacetophenone)、2-羥基-2-甲基-1-苯基丙烷-1-酮(2-hydroxy-2-methyl-1-phenylpropan-1-one)、1-(4-異丙苯基)-2-羥基-2-甲基丙烷-1-酮(1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one)、1-(4-十二烷基苯基)-2-羥基-2-甲基丙烷-1-酮(1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one)、4-(2-羥基乙氧基)- 苯基(2-羥基-2-丙基)酮(4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone)、1-羥基環己基苯基酮(1-hydroxycyclohexyl phenyl ketone)、或類似物;苯偶姻類(benzoins),例如苯偶姻、苯偶姻甲醚(benzoin methyl ether)、苯偶姻***(benzoin ethyl ether)、芐基二甲基縮酮(benzyl dimethyl ketal)、或類似物;醯基膦氧化物(acylphosphine oxides);二茂鈦化合物(titanocene compounds);及類似物。類型II光聚合起始劑的具體範例可包括二苯甲酮類(benzophenones),例如二苯甲酮、苯甲醯苯甲酸(benzoyl benzoic acid)、苯甲醯苯甲酸甲醚(benzoyl benzoic acid methyl ether)、4-苯基二苯甲酮(4-phenylbenzophenone)、羥基二苯甲酮(hydroxybenzophenone)、4-苯甲醯基-4'-甲基二苯基硫醚(4-benzoyl-4'-methyldiphenylsulfide)、3,3'-二甲基-4-甲氧基二苯甲酮(3,3'-dimethyl-4-methoxybenzophenone)、或類似物;及噻噸酮類(thioxanthones),例如噻噸酮(thioxanthone)、2-氯噻噸酮(2-chlorothioxanthone)、2-甲基噻噸酮(2-methylthioxanthone)、2,4-二甲基噻噸酮(2,4-dimethylthioxanthone)、異丙基噻噸酮(isopropylthioxanthone);或類似物。這些光聚合起始劑可單獨或合併二或多個使用。此外,類型I光聚合起始劑與類型II光聚合起始劑可一起使用。Photopolymerization initiators can be classified into type I (Type I) photopolymerization initiators and type II (Type II) (hydrogen abstraction) photopolymerization initiators. Free radicals in type I photopolymerization initiators are generated by molecular decomposition caused by differences in chemical structure or molecular binding energy. In type II (hydrogen abstraction type), tertiary amines are used as co-initiators. Specific examples of the type I photopolymerization initiator may include acetophenones, such as 4-phenoxydichloroacetophenone, 4-tert-butyldichloroacetophenone (4- t-butyldichloroacetophenone), 4-t-butyltrichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1 -Ketone (2-hydroxy-2-methyl-1-phenylpropan-1-one), 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one (1- (4- isopropylphenyl) -2-hydroxy-2-methylpropan-1-one), 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one (1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one), 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) -ketone (4- (2-hydroxyethoxy) -phenyl (2 -hydroxy-2-propyl) ketone), 1-hydroxycyclohexyl phenyl ketone, or the like; benzoins, such as benzoin, benzoin methyl ether), benzoin ethyl ether, benzyl dimethyl Ketals (benzyl dimethyl ketal), or the like; acylphosphine oxides; titanocene compounds; and the like. Specific examples of the type II photopolymerization initiator may include benzophenones, such as benzophenone, benzoyl benzoic acid, benzoyl benzoic acid methyl ether), 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide -methyldiphenylsulfide), 3,3'-dimethyl-4-methoxybenzophenone (3,3'-dimethyl-4-methoxybenzophenone), or the like; and thioxanthones, such as thioxanthones Thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropyl Isopropylthioxanthone; or an analogue. These photopolymerization initiators may be used alone or in combination of two or more. In addition, a type I photopolymerization initiator may be used together with a type II photopolymerization initiator.
基於第一硬塗佈組成物之總重量為100%,可含有光聚合起始劑的量為重量0.1至5%,較佳為重量1至3%。若起始劑的重量含量少於0.1%,固化程度可能會不夠,且因此最終獲得之塗膜的機械性質與黏著力會下降。若起始劑的重量含量高於5%,可能會因為固化收縮而發生黏合失敗、裂紋及翹曲現象。The photopolymerization initiator may be contained in an amount of 0.1 to 5% by weight, preferably 1 to 3% by weight based on the total weight of the first hard coating composition. If the weight content of the initiator is less than 0.1%, the degree of curing may be insufficient, and therefore the mechanical properties and adhesion of the finally obtained coating film may decrease. If the weight content of the initiator is more than 5%, adhesion failure, cracks and warpage may occur due to curing shrinkage.
在本發明的一實施例中,溶劑並未特別限制,可使用該技術領域中通常使用的溶劑。In one embodiment of the present invention, the solvent is not particularly limited, and solvents commonly used in the technical field can be used.
溶劑的具體範例可包括醇類溶劑,例如甲醇、乙醇、異丙醇、丁醇、丙烯二醇甲氧基醇(propylene glycol methoxy alcohol)等;酮類溶劑,例如甲基乙基酮(methyl ethyl ketone)、甲基丁基酮(methyl butyl ketone)、甲基異丁基酮(methyl isobutyl ketone)、二乙基酮(diethyl ketone)、二丙基酮(dipropyl ketone)等;醋酸酯溶劑,例如乙酸甲酯(methyl acetate)、乙酸乙酯(ethyl acetate)、乙酸丁酯(butyl acetate)、甲氧基丙二醇乙酸酯(propylene glycol methoxy acetate)等;賽珞蘇(cellosolves)溶劑,例如甲基賽珞蘇(methyl cellosolve)、乙基賽珞蘇(ethyl cellosolve)、丙基賽珞蘇(propyl cellosolve)等;烴類(hydrocarbons)溶劑,例如正己烷(n-hexane)、正庚烷(n-heptane)、苯、甲苯、二甲苯等;及類似物。這些溶劑可單獨或合併二或更多者使用。Specific examples of the solvent may include alcohol-solvent solvents such as methanol, ethanol, isopropanol, butanol, propylene glycol methoxy alcohol, and the like; ketone-solvent solvents such as methyl ethyl ketone (methyl ethyl ketone) ketone), methyl butyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, etc .; acetate solvents such as Methyl acetate, ethyl acetate, butyl acetate, propylene glycol methoxy acetate, etc .; cellosolves solvents, such as methyl Methyl cellosolve, ethyl cellosolve, propyl cellosolve, etc .; hydrocarbon solvents, such as n-hexane, n-heptane (n -heptane), benzene, toluene, xylene, etc .; and the like. These solvents may be used alone or in combination of two or more.
基於硬塗佈組成物之總重量為100%,可含有溶劑的量為重量5至90 %,較佳為重量10至85%。若溶劑的重量含量少於5%,黏度可能增加而使得可加工性質劣化。若溶劑的重量含量高於90%,會難以調變塗膜的厚度,並可能會發生乾燥不勻而造成外觀上的缺陷。The solvent may be contained in an amount of 5 to 90% by weight, preferably 10 to 85% by weight, based on the total weight of the hard coating composition. If the weight content of the solvent is less than 5%, the viscosity may increase to deteriorate the processability. If the weight content of the solvent is higher than 90%, it may be difficult to adjust the thickness of the coating film, and unevenness in drying may occur, causing defects in appearance.
在本發明的一實施例中,第一硬塗佈組成物可更包括無機顆粒,以更進一步提升機械性質。In an embodiment of the present invention, the first hard coating composition may further include inorganic particles to further improve mechanical properties.
無機顆粒可具有平均顆粒粒徑1至100 nm,較佳5至50 nm。這些無機顆粒均勻地形成在塗膜中,並能夠提升機械性質,例如抗磨耗性、抗刮擦性及鉛筆硬度。若顆粒粒徑小於上述範圍,組成物中會發生附聚現象因而無法形成均勻的塗膜且無法達成上述期望的效果。另一方面,若顆粒粒徑超過上述範圍,最後獲得的塗膜不但可能光學性質會退化,且機械性質也可能會減弱。The inorganic particles may have an average particle diameter of 1 to 100 nm, preferably 5 to 50 nm. These inorganic particles are uniformly formed in the coating film and can improve mechanical properties such as abrasion resistance, scratch resistance, and pencil hardness. If the particle diameter is smaller than the above range, an agglomeration phenomenon occurs in the composition, so that a uniform coating film cannot be formed, and the above-mentioned desired effect cannot be achieved. On the other hand, if the particle diameter exceeds the above range, not only the optical properties of the final coating film may be degraded, but also the mechanical properties may be weakened.
無機顆粒可為金屬氧化物,且可使用擇自由Al2 O3 、SiO2 、ZnO、ZrO2 、BaTiO3 、TiO2 、Ta2 O5 、Ti3 O5 、ITO、IZO、ATO、ZnO-Al、Nb2 O3 、SnO及MgO所構成之群組之一者。具體而言,可使用Al2 O3 、SiO2 、ZrO2 及類似物。The inorganic particles may be metal oxides, and Al 2 O 3 , SiO 2 , ZnO, ZrO 2 , BaTiO 3 , TiO 2 , Ta 2 O 5 , Ti 3 O 5 , ITO, IZO, ATO, ZnO- One of the groups consisting of Al, Nb 2 O 3 , SnO and MgO. Specifically, Al 2 O 3 , SiO 2 , ZrO 2 and the like can be used.
無機顆粒可直接製造或從市面上購得。在從市面上購得之產物的情況中,可使用無機顆粒以重量10至80%之濃度分散在有機溶劑中的產物。Inorganic particles can be manufactured directly or commercially available. In the case of a commercially available product, a product in which inorganic particles are dispersed in an organic solvent at a concentration of 10 to 80% by weight can be used.
基於第一硬塗佈組成物之總重量為100%,可含有無機顆粒的量為重量5至50%。當無機顆粒的重量含量少於5%時,機械性質例如抗磨耗性、抗刮擦性及鉛筆硬度可能會不足,且當無機顆粒的重量含量超過50%時,會阻礙可固化性質而造成機械性質的損弱,並造成外觀上的缺陷。The amount of the inorganic particles that can be contained is 5 to 50% by weight based on the total weight of the first hard coating composition. When the content of inorganic particles is less than 5% by weight, mechanical properties such as abrasion resistance, scratch resistance, and pencil hardness may be insufficient, and when the content of inorganic particles exceeds 50% by weight, it may hinder curable properties and cause mechanical problems. Weakness in nature and defects in appearance.
在本發明的一實施例中,第一硬塗佈組成物除了以上所述的成分之外,可更包括所屬技術領域中通常使用的成分,例如調平劑、紫外光穩定劑、熱穩定劑、及類似物。In an embodiment of the present invention, in addition to the components described above, the first hard coating composition may further include components generally used in the technical field, such as a leveling agent, an ultraviolet light stabilizer, and a heat stabilizer. , And the like.
可使用調平劑以提供組成物在塗佈期間的滑順性及塗佈塗膜性質。對於調平劑,可選擇並使用從市面上購得的矽型、氟型、及丙烯酸聚合物型調平劑。舉例來說,可使用BYK-323、BYK-331、BYK-333、BYK-337、BYK-373、BYK-375、BYK-377、BYK-378、BYK-3570(可從BYK Chemie取得)、TEGO Glide 410、TEGO Glide 411、TEGO Glide 415、TEGO Glide 420、TEGO Glide 432、TEGO Glide 435、TEGO Glide 440、TEGO Glide 450、TEGO Glide 455、TEGO Rad 2100、TEGO Rad 2200N、TEGO Rad 2250、TEGO Rad 2300、TEGO Rad 2500 (可從Degussa取得)、FC-4430及FC-4432(可從3M取得),或類似物。基於第一硬塗佈組成物之總重量為100%,可含有調平劑的量為重量0.1至1%。Leveling agents may be used to provide the composition with smoothness during coating and coating film properties. As the leveling agent, commercially available silicon type, fluorine type, and acrylic polymer type leveling agents can be selected and used. For example, BYK-323, BYK-331, BYK-333, BYK-337, BYK-373, BYK-375, BYK-377, BYK-378, BYK-3570 (available from BYK Chemie), TEGO Glide 410, TEGO Glide 411, TEGO Glide 415, TEGO Glide 420, TEGO Glide 432, TEGO Glide 435, TEGO Glide 440, TEGO Glide 450, TEGO Glide 455, TEGO Rad 2100, TEGO Rad 2200N, TEGO Rad 2250, TEGO Rad 2300 , TEGO Rad 2500 (available from Degussa), FC-4430 and FC-4432 (available from 3M), or similar. The leveling agent may be included in an amount of 0.1 to 1% by weight based on the total weight of the first hard coating composition.
由於固化之塗膜的表面會由於連續暴露於紫外線而分解使得變色且碎裂,可添加紫外光穩定劑以遮蔽或吸收此紫外線達到保護塗膜的目的。紫外光穩定劑可依據反應機制分類為吸收劑、消光劑(quencher)、及受阻胺光穩定劑(hindered amine light stabilizer;HALS)。也可依據化學結構分類為水楊酸苯酯(phenyl salicylate)(吸收劑)、二苯甲酮(benzophenone)(吸收劑)、苯並***(Benzotriazole)(吸收劑)、鎳衍生物(消光劑)、自由基捕捉劑(radical scavenger)。在本發明的一實施例中,紫外光穩定劑並未特別限制,只要其能夠不明顯改變塗膜的初始顏色即可。Since the surface of the cured coating film will decompose due to continuous exposure to ultraviolet rays and cause discoloration and chipping, an ultraviolet light stabilizer may be added to shield or absorb the ultraviolet rays to protect the coating film. Ultraviolet light stabilizers can be classified into absorbers, quenchers, and hindered amine light stabilizers (HALS) according to the reaction mechanism. Can also be classified according to chemical structure as phenyl salicylate (absorbent), benzophenone (absorbent), benzotriazole (absorbent), nickel derivatives (matting Agent), radical scavenger. In one embodiment of the present invention, the ultraviolet light stabilizer is not particularly limited as long as it can not significantly change the initial color of the coating film.
熱穩定劑可為能從市面上購得的產物,並可獨立或混合使用為主要熱穩定劑的多酚系型熱穩定劑、為次位之熱穩定劑的亞磷酸酯系型熱穩定劑、及內酯系型熱穩定劑。The thermal stabilizer can be a commercially available product, and can be used independently or in combination as a polyphenol-based thermal stabilizer as a main thermal stabilizer, and a phosphite-based thermal stabilizer as a secondary thermal stabilizer. , And lactone-based heat stabilizers.
上述紫外線穩定劑和熱穩定劑能夠在不影響紫外線固化性的水準上以適當的含量使用。The above-mentioned ultraviolet stabilizer and heat stabilizer can be used in an appropriate amount at a level that does not affect ultraviolet curability.
第一硬塗佈組成物可以已知的塗佈製程適當地塗佈至基底膜上,方法例如模塗佈機(die coater)、氣刀(air knife)、逆輥(reverse roll)、噴塗(spray)、刮刀(blade)、澆鑄(casting)、凹版印刷(gravure)、微凹版印刷(micro gravure)、旋塗(spin coating)等。The first hard coating composition can be appropriately applied to the base film by a known coating process, such as a die coater, an air knife, a reverse roll, and a spray coating ( spray), blade, casting, gravure, micro gravure, spin coating, etc.
在將第一硬塗佈組成物塗佈至基底膜上之後,可在30至150℃的環境下執行乾燥製程10秒至1小時,更具體而言30秒至30分鐘,來汽化揮發物質,然後進行UV固化製程。UV固化可執行照射約0.01至10 J/cm2 ,較佳0.1至2 J/cm2 的UV射線。After the first hard coating composition is applied to the base film, a drying process may be performed in an environment of 30 to 150 ° C. for 10 seconds to 1 hour, more specifically 30 seconds to 30 minutes, to vaporize volatile substances, Then a UV curing process is performed. UV curing can be performed by irradiating UV rays of about 0.01 to 10 J / cm 2 , preferably 0.1 to 2 J / cm 2 .
<第二硬塗佈組成物>< Second Hard Coating Composition >
在本發明的一實施例中,第二硬塗佈組成物可包括光可固化環氧樹脂、光聚合起始劑及溶劑。In one embodiment of the present invention, the second hard coating composition may include a photo-curable epoxy resin, a photo-polymerization initiator, and a solvent.
此外,若需要,第二硬塗佈組成物可更包括無機顆粒,並可更括添加劑,例如調平劑、紫外光穩定劑、熱穩定劑、及類似物。In addition, if necessary, the second hard coating composition may further include inorganic particles, and may further include additives such as a leveling agent, an ultraviolet light stabilizer, a heat stabilizer, and the like.
光可固化環氧樹脂可包括具有環氧基的烷氧基矽烷化合物或聚矽氧樹脂。The photocurable epoxy resin may include an alkoxysilane compound or a polysiloxane resin having an epoxy group.
在本發明的一實施例中,具有環氧基的烷氧基矽烷化合物可包括由以下化學式3表示的化合物: [化學式3] R7 n Si(OR8 )4-n 其中,R7 為環氧基,R8 為C1 -C20 烷基,且n為1至3之整數。In an embodiment of the present invention, the alkoxysilane compound having an epoxy group may include a compound represented by the following Chemical Formula 3: [Chemical Formula 3] R 7 n Si (OR 8 ) 4-n wherein R 7 is a ring Oxy, R 8 is C 1 -C 20 alkyl, and n is an integer from 1 to 3.
於此使用的C1 -C20 烷基是指具有1至20個碳原子之線性或分支的烴基,且其範例包括甲基、乙基、正丙基(n-propyl)、異丙基(i-propyl)、正丁基、異丁基、叔丁基(t-butyl)、正戊基、正己基,及類似物,但不限於此。The C 1 -C 20 alkyl group used herein refers to a linear or branched hydrocarbon group having 1 to 20 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, isopropyl ( i-propyl), n-butyl, isobutyl, t-butyl, n-pentyl, n-hexyl, and the like, but not limited thereto.
具有環氧基的烷氧基矽烷化合物由環氧基表現陽離子光聚合反應。陽離子光聚合反應在表面上展現出相當低的收缩且不會引起氧抑制反應。因此,能夠有穩定的固化現象,且固化率優異。此外,由烷氧基矽烷化合物之溶膠-凝膠反應製得的聚矽氧樹脂,由於其存在矽氧網狀物,因此會有陽離子光聚合快速發生且固化率優異的特性。此具有環氧基的烷氧基矽烷化合物與聚矽氧樹脂能對硬塗佈組成物提供優異的硬度,並同時提供優異的可撓性。An alkoxysilane compound having an epoxy group exhibits a cationic photopolymerization reaction from an epoxy group. Cationic photopolymerization exhibits rather low shrinkage on the surface and does not cause oxygen inhibition reactions. Therefore, a stable curing phenomenon can be achieved, and the curing rate is excellent. In addition, the polysiloxane resin prepared by the sol-gel reaction of an alkoxysilane compound has the characteristics of rapid cationic photopolymerization and excellent curing rate due to the presence of a siloxane network. The epoxy-containing alkoxysilane compound and the polysiloxane resin can provide excellent hardness to the hard coating composition, and at the same time provide excellent flexibility.
以化學式3表示之具有環氧基的烷氧基矽烷化合物可擇自由2-(3,4-環氧環己烷)乙基三甲氧基矽烷(2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane)、2-(3,4-環氧環己烷)乙基三乙氧基矽烷(2-(3,4-epoxycyclohexyl)ethyltriethoxysilane)、3-環氧丙氧丙基三甲氧基矽烷(3-glycidoxypropyl trimethoxysilane)、及3-環氧丙氧丙基三乙氧基矽烷(3-glycidoxypropyl triethoxysilane)所構成之群組。The alkoxysilane compound having an epoxy group represented by Chemical Formula 3 may be selected from 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexane) ethyltriethoxysilane (2- (3,4-epoxycyclohexyl) ethyltriethoxysilane), 3-glycidoxypropyl trimethoxysilane ), And 3-glycidoxypropyl triethoxysilane.
具有環氧基的聚矽氧樹脂可由烷氧基矽烷化合物的水解溶膠-凝膠反應製得。The polysiloxane resin having an epoxy group can be prepared by hydrolyzing a sol-gel reaction of an alkoxysilane compound.
具體而言,作為起始材料之烷氧基矽烷的烷氧基與水產生水解反應形成羥基,並與另一烷氧基矽烷化合物的烷氧基或羥基進行縮合反應產生矽氧鍵結而形成聚矽氧。Specifically, the alkoxysilane of the alkoxysilane as a starting material undergoes a hydrolysis reaction with water to form a hydroxyl group, and is subjected to a condensation reaction with an alkoxy group or a hydroxyl group of another alkoxysilane compound to generate a siloxane bond and is formed Polysiloxane.
較佳可引入觸媒以促進水解溶膠-凝膠反應。可使用的觸媒可包括酸觸媒,例如乙酸(acetic acid)、磷酸(phosphoric acid)、硫酸、氫氯酸、硝酸、氯磺酸(chlorosulfonic acid)、對甲基苯甲酸(para-toluic acid)、三氯乙酸(trichloroacetic acid)、聚磷酸(polyphosphoric acid)、焦磷酸(pyrophosphoric acid)、碘酸(iodic acid)、酒石酸(tartaric acid)、過氯酸(perchloric acid);鹼觸媒,例如氨(ammonia)、氫氧化納、正丁胺(n-butylamine)、二正丁胺(di-n-butylamine)、三正丁胺(tri-n-butylamine)、咪唑(imidazole)、過氯酸銨(ammonium perchlorate)、氫氧化鉀(potassium hydroxide)、氫氧化鋇(barium hydroxide);離子樹脂,例如Amberite IPA-400(Cl);及類似物。觸媒的使用量並未特別限制,且基於烷氧基矽烷為100重量份,觸媒加入的量可為0.0001至10重量份。A catalyst may preferably be introduced to promote the hydrolytic sol-gel reaction. Catalysts that can be used can include acid catalysts, such as acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, chlorosulfonic acid, para-toluic acid ), Trichloroacetic acid, polyphosphoric acid, pyrophosphoric acid, iodic acid, tartaric acid, perchloric acid; alkali catalysts, such as Ammonia, sodium hydroxide, n-butylamine, di-n-butylamine, tri-n-butylamine, imidazole, perchloric acid Ammonium perchlorate, potassium hydroxide, barium hydroxide; ionic resins, such as Amberite IPA-400 (Cl); and the like. The use amount of the catalyst is not particularly limited, and based on 100 parts by weight of the alkoxysilane, the amount of the catalyst added may be 0.0001 to 10 parts by weight.
水解溶膠-凝膠反應的執行可在室溫下進行攪拌6至144小時,並也可在60至80°C的環境下進行攪拌12至36小時以加速反應速率,並執行完全的縮合反應。The hydrolysis sol-gel reaction can be performed at room temperature for 6 to 144 hours, and can also be performed at 60 to 80 ° C for 12 to 36 hours to accelerate the reaction rate and perform a complete condensation reaction.
基於第二硬塗佈組成物之總重量為100%,可含有烷氧基矽烷化合物或聚矽氧樹脂的量為重量30至60%,較佳為重量35至55%。當烷氧基矽烷化合物或聚矽氧樹脂的重量含量少於30%時,會變得難以確保硬度。當重量含量大於60%時,塗膜會有裂紋,且會變得難以供予彎曲性質。Based on the total weight of the second hard coating composition being 100%, the amount that may contain an alkoxysilane compound or a polysiloxane resin is 30 to 60% by weight, preferably 35 to 55% by weight. When the content of the alkoxysilane compound or the polysiloxane resin is less than 30% by weight, it becomes difficult to secure hardness. When the weight content is more than 60%, the coating film may be cracked, and it may become difficult to provide bending properties.
在本發明的一實施例中,光聚合起始劑是用以光固化第二硬塗佈組成物,且起始劑並未特別限制,可使用該技術領域中通常使用的任何起始劑。In one embodiment of the present invention, the photopolymerization initiator is used for photocuring the second hard coating composition, and the initiator is not particularly limited. Any initiator generally used in the technical field may be used.
對於光聚合起始劑,可使用能夠由例如可見光、紫外光、X-光線、電子束之具有活化能量射線的照射產生陽離子物質或路易士酸而起始陽離子光可固化成分之聚合反應的陽離子光聚合起始劑,或類似物。As the photopolymerization initiator, a cation capable of initiating the polymerization reaction of the cationic photo-curable component by generating a cationic substance or Lewis acid from irradiation with active energy rays such as visible light, ultraviolet light, X-rays, and electron beams can be used. Photopolymerization initiator, or the like.
由於陽離子光聚合起始劑是由光線激起觸媒作用,因此即使與陽離子光可固化成分混合,其在儲存穩定性及可加工性質上仍為優異。能由照射活化能量射線產生陽離子物質及路易士酸之化合物的範例包括鎓鹽類(onium salt),例如芳香族重氮鹽類(aromatic diazonium salt)、芳族鋶鹽類(aromatic iodonium salt)、或芳族鋶鹽類(aromatic sulfonium salt);鐵-芳烴錯合物(iron-allene complex),及類似物。這些範例中,以芳族鋶鹽類為較佳,這是因為其即使在約300 nm的波長區域中仍具有紫外光吸收性質,故具有優異的可固化性質並能供予優異的塗膜特性。這些陽離子光聚合起始劑可單獨或合併二或更多者使用。Since the cationic photopolymerization initiator acts as a catalyst by light, it is excellent in storage stability and processability even when mixed with a cationic photocurable component. Examples of compounds capable of generating cationic substances and Lewis acid by irradiating activated energy rays include onium salts, such as aromatic diazonium salts, aromatic iodonium salts, Or aromatic sulfonium salts; iron-allene complexes, and the like. Among these examples, aromatic sulfonium salts are preferred because they have ultraviolet light absorption properties even in a wavelength region of about 300 nm, so they have excellent curable properties and can provide excellent coating film characteristics. . These cationic photopolymerization initiators may be used alone or in combination of two or more.
基於第二硬塗佈組成物之總重量為100%,可含有光聚合起始劑的量為0.1至5%。當光聚合起始劑的重量含量少於0.1%時,固化速率緩慢,且當光聚合起始劑的重量含量大於5%時,可能會由於過度的固化而在硬塗層中發生裂紋。The photopolymerization initiator may be included in an amount of 0.1 to 5% based on 100% of the total weight of the second hard coating composition. When the weight content of the photopolymerization initiator is less than 0.1%, the curing rate is slow, and when the weight content of the photopolymerization initiator is more than 5%, cracks may occur in the hard coating layer due to excessive curing.
第二硬塗佈組成物中含有的其它成分,及其塗佈、乾燥、及固化方法係與那些用以說明第一硬塗佈組成物的部分相同,因此不再重複贅述。The other components contained in the second hard coating composition, and the methods of coating, drying, and curing are the same as those used to describe the first hard coating composition, and will not be repeated here.
本發明之一實施例是有關於具有上述硬塗膜的影像顯示裝置。舉例來說,本發明的硬塗膜可用做影像顯示裝置的視窗,特別是可撓式顯示器的視窗。再者,本發明的硬塗膜可藉由附加至偏光板、感測器、或類似物而被使用。An embodiment of the present invention relates to an image display device having the hard coating film. For example, the hard coating film of the present invention can be used as a window of an image display device, particularly a window of a flexible display. Furthermore, the hard coat film of the present invention can be used by being attached to a polarizing plate, a sensor, or the like.
根據本發明之一實施例的硬塗膜可用於各種操作模式的液晶裝置,包括反射式、穿透式、半反射半穿透式、扭轉向列型(twisted nematic (TN))、 超扭轉向列型(super-twisted nematic (STN))、光學補償彎曲型(optically compensated bend (OCB))、混合排列向列型(hybrid-aligned nematic (HAN))、垂直排列(vertical alignment (VA))型、及平面內切換型(in-plane switching (IPS))液晶裝置。根據本發明之一實施例的硬塗膜也可使用於各種影像顯示裝置,包括電漿顯示器、場發射顯示器、有機電致發光顯示器、無機電致發光顯示器、電子紙、及類似物。The hard coating film according to an embodiment of the present invention can be used for liquid crystal devices of various operation modes, including reflective, transmissive, transflective, twisted nematic (TN), and super twisted Super-twisted nematic (STN), optically compensated bend (OCB), hybrid-aligned nematic (HAN), vertical alignment (VA) , And in-plane switching (IPS) liquid crystal devices. The hard coating film according to one embodiment of the present invention can also be used in various image display devices, including plasma displays, field emission displays, organic electroluminescence displays, inorganic electroluminescence displays, electronic paper, and the like.
以下將參照範例、比較例、與試驗範例更詳細說明本發明。對於所屬技術領域中的通常知識者而言,顯然了解這些範例、比較例、與試驗範例只是為了說明目的,並非用以限制本發明之範圍。Hereinafter, the present invention will be described in more detail with reference to examples, comparative examples, and test examples. For those of ordinary skill in the art, it is obvious that understanding of these examples, comparative examples, and test examples is for illustrative purposes only and is not intended to limit the scope of the invention.
製備範例1:製備第一硬塗佈組成物Preparation Example 1: Preparation of the first hard coating composition
基於第一硬塗佈組成物之總重量為100%,利用攪拌器混合重量40%之具有端(甲基)丙烯酸酯基的樹枝狀化合物(SP-1106,由Miwon Specialty Chemicals製造)、重量5%之單官能丙烯酸酯(丙烯酸丁酯)、重量39%之無機氧化矽(silica)顆粒(顆粒粒徑為10-15 nm)、重量2.5%之光聚合起始劑(1-羥基環己基苯基酮)、重量0.5%之調平劑(BYK-3570,BYK Chemie製造)、及重量13%之溶劑(甲基乙基酮),並接著使用聚丙烯(PP)過濾介質進行過濾以製備出第一硬塗佈組成物。Based on 100% of the total weight of the first hard coating composition, 40% by weight of a dendritic compound (SP-1106, manufactured by Miwon Specialty Chemicals) having a terminal (meth) acrylate group was mixed with a stirrer, and the weight was 5 % Monofunctional acrylate (butyl acrylate), 39% inorganic silica particles (particle size 10-15 nm), 2.5% by weight photopolymerization initiator (1-hydroxycyclohexylbenzene) Ketone), 0.5% by weight leveling agent (BYK-3570, manufactured by BYK Chemie), and 13% by weight solvent (methyl ethyl ketone), followed by filtration using a polypropylene (PP) filter medium to prepare The first hard coating composition.
製備範例2:製備第二硬塗佈組成物Preparation Example 2: Preparation of a second hard coating composition
基於第二硬塗佈組成物之總重量為100%,利用攪拌器混合重量40%之聚矽氧樹脂(SP-3T,由Shin-A T & C製造)、重量5%之無機氧化矽顆粒(顆粒粒徑為10-15 nm)、重量2.5%之光聚合起始劑(雙(4-甲基苯基)碘六氟磷酸鹽(bis(4-methylphenyl)iodonium hexafluorophosphate))、重量0.5%之調平劑(BYK-3570,由BYK Chemie製造)、及重量52%之溶劑(甲基乙基酮),並接著使用聚丙烯過濾介質進行過濾以製備出第二硬塗佈組成物。Based on the total weight of the second hard coating composition is 100%, 40% by weight of a polysilicone resin (SP-3T, manufactured by Shin-A T & C) and 5% by weight of inorganic silica particles are mixed with a stirrer. (Particle size 10-15 nm), 2.5% by weight of photopolymerization initiator (bis (4-methylphenyl) iodonium hexafluorophosphate), 0.5% by weight A leveling agent (BYK-3570, manufactured by BYK Chemie), and a solvent (methyl ethyl ketone) of 52% by weight, followed by filtration using a polypropylene filter medium to prepare a second hard coating composition.
範例1至3及比較例1至2:製備硬塗膜Examples 1 to 3 and Comparative Examples 1 to 2: Preparation of a hard coating film
範例1:Example 1:
製備範例1中製備的第一硬塗佈組成物塗佈在作為基底之光學聚亞醯胺膜(100 ㎛)的一表面上,在80℃之烘箱中乾燥5分鐘,然後在高壓水銀燈中照射0.5 J/cm2 之UV光線以形成第一硬塗層之後,從而具有5 ㎛之厚度。然後,製備範例2中製備的第二硬塗佈組成物塗佈在第一硬塗層上,在80℃之烘箱中乾燥5分鐘,並然後在高壓水銀燈中照射0.5 J/cm2 之UV光線以形成第二硬塗層之後,從而具有5 ㎛之厚度。藉此,製備出硬塗膜。The first hard coating composition prepared in Preparation Example 1 was coated on one surface of an optical polyurethane film (100 F) as a substrate, dried in an oven at 80 ° C. for 5 minutes, and then irradiated in a high-pressure mercury lamp. 0.5 J / cm 2 of UV light to form a first hard coat layer, thereby having a thickness of 5 ㎛. Then, the second hard coating composition prepared in Preparation Example 2 was coated on the first hard coating layer, dried in an oven at 80 ° C. for 5 minutes, and then irradiated with 0.5 J / cm 2 of UV light in a high-pressure mercury lamp. After forming the second hard coat layer, it has a thickness of 5 ㎛. Thereby, a hard coating film was prepared.
範例2:Example 2:
硬塗膜係以範例1中相同的方法製備,除了是將製備範例1中製備的第一硬塗佈組成物塗佈在基底的一表面上,在乾燥之後從而具有7 ㎛之厚度,且是將製備範例2中製備的第二硬塗佈組成物塗佈在第一硬塗層上,在乾燥以形成第二硬塗層之後從而具有3 ㎛之厚度。The hard coating film was prepared in the same manner as in Example 1, except that the first hard coating composition prepared in Preparation Example 1 was coated on one surface of the substrate, and after drying, had a thickness of 7 ㎛, and was The second hard coating composition prepared in Preparation Example 2 was coated on the first hard coating layer, and after drying to form a second hard coating layer, it had a thickness of 3 ㎛.
範例3:Example 3:
硬塗膜係以範例1中相同的方法製備,除了是將製備範例1中製備的第一硬塗佈組成物塗佈在基底的一表面上,在乾燥之後從而具有3 ㎛之厚度,且是將製備範例2中製備的第二硬塗佈組成物塗佈在第一硬塗層上,在乾燥以形成第二硬塗層之後從而具有7 ㎛之厚度。The hard coating film was prepared in the same manner as in Example 1, except that the first hard coating composition prepared in Preparation Example 1 was coated on one surface of the substrate, and after drying, it had a thickness of 3 ㎛, and was The second hard coating composition prepared in Preparation Example 2 was coated on the first hard coating layer, and after drying to form a second hard coating layer, it had a thickness of 7 ㎛.
比較例1:Comparative Example 1:
硬塗膜係以範例1中相同的方法製備,除了是將製備範例1中製備的第一硬塗佈組成物塗佈在基底的一表面上,在乾燥之後從而具有5 ㎛之厚度,且是將製備範例1中製備的第一硬塗佈組成物塗佈在第一硬塗層上,在乾燥以形成第二硬塗層之後從而具有5 ㎛之厚度。The hard coating film was prepared in the same manner as in Example 1, except that the first hard coating composition prepared in Preparation Example 1 was coated on one surface of a substrate, and after drying, had a thickness of 5 ㎛, and was The first hard coating composition prepared in Preparation Example 1 was coated on the first hard coating layer, and after drying to form a second hard coating layer, it had a thickness of 5 ㎛.
比較例2:Comparative Example 2:
硬塗膜係以範例1中相同的方法製備,除了是將製備範例2中製備的第二硬塗佈組成物塗佈在基底的一表面上,在乾燥之後從而具有5 ㎛之厚度,且是將製備範例2中製備的第二硬塗佈組成物塗佈在第一硬塗層上,在乾燥以形成第二硬塗層之後從而具有5 ㎛之厚度。The hard coating film was prepared in the same manner as in Example 1, except that the second hard coating composition prepared in Preparation Example 2 was coated on one surface of the substrate, and after drying, had a thickness of 5 ㎛, and was The second hard coating composition prepared in Preparation Example 2 was coated on the first hard coating layer, and after drying to form a second hard coating layer, it had a thickness of 5 ㎛.
試驗範例1:Test example 1:
試驗範例1-1:Test example 1-1:
製備範例1中製備的第一硬塗佈組成物塗佈在作為基底之光學聚亞醯胺膜(100 ㎛)的一表面上,在80℃之烘箱中乾燥5分鐘,然後在高壓水銀燈中照射0.5 J/cm2 之UV光線以在基底膜上只形成第一硬塗層之後,從而具有3 ㎛之厚度,藉此獲得第一硬塗膜。The first hard coating composition prepared in Preparation Example 1 was coated on one surface of an optical polyurethane film (100 F) as a substrate, dried in an oven at 80 ° C. for 5 minutes, and then irradiated in a high-pressure mercury lamp. 0.5 J / cm 2 of UV light was used to form only the first hard coat layer on the base film, thereby having a thickness of 3 3, thereby obtaining a first hard coat film.
翹曲值是藉由將硬塗膜切斷為10 cm×10 cm之尺寸,留在25℃、48%RH環境下24小時,放置該膜於平坦的玻璃板上,使得其凸形表面係接觸玻璃板,並然後量測從玻璃板(參考表面)至四個角落之高度的平均而獲得。正翹曲係以(+)值表示,且相反翹曲係以(-)值表示。The warpage value is obtained by cutting the hard coating film to a size of 10 cm × 10 cm and leaving it at 25 ° C and 48% RH for 24 hours. The film is placed on a flat glass plate to make its convex surface Touch the glass plate and then measure the average of the height from the glass plate (reference surface) to the four corners. The positive warpage is represented by a (+) value, and the reverse warp is represented by a (-) value.
量測出的翹曲值為3 mm。The measured warpage value was 3 mm.
試驗範例1-2:Test example 1-2:
硬塗膜係以試驗範例1-1中相同的方法製備,除了是塗佈第一硬塗佈組成物,在乾燥之後從而具有5 ㎛之厚度,且量測其翹曲值。The hard coating film was prepared in the same manner as in Test Example 1-1 except that the first hard coating composition was applied, and after drying, it had a thickness of 5 ㎛, and its warpage value was measured.
量測出的翹曲值為5 mm。The measured warpage value was 5 mm.
試驗範例1-3:Test example 1-3:
硬塗膜係以試驗範例1-1中相同的方法製備,除了是塗佈第一硬塗佈組成物,在乾燥之後從而具有7 ㎛之厚度,且量測其翹曲值。The hard coating film was prepared in the same manner as in Test Example 1-1, except that the first hard coating composition was applied, and after drying, it had a thickness of 7 ㎛, and its warpage value was measured.
量測出的翹曲值為7 mm。The measured warpage value was 7 mm.
試驗範例1-4:Test example 1-4:
硬塗膜係以試驗範例1-1中相同的方法製備,除了是使用第二硬塗佈組成物替代第一硬塗佈組成物,並量測其翹曲值。The hard coating film was prepared in the same manner as in Test Example 1-1, except that the second hard coating composition was used instead of the first hard coating composition, and its warpage value was measured.
量測出的翹曲值為-10 mm。The measured warpage value was -10 mm.
試驗範例1-5:Test example 1-5:
硬塗膜係以試驗範例1-2中相同的方法製備,除了是使用第二硬塗佈組成物替代第一硬塗佈組成物,並量測其翹曲值。The hard coating film was prepared in the same manner as in Test Example 1-2, except that the second hard coating composition was used instead of the first hard coating composition, and its warpage value was measured.
量測出的翹曲值為-15 mm。The measured warpage value was -15 mm.
試驗範例1-6:Test example 1-6:
硬塗膜係以試驗範例1-3中相同的方法製備,除了是使用第二硬塗佈組成物替代第一硬塗佈組成物,並量測其翹曲值。The hard coating film was prepared in the same manner as in Test Example 1-3, except that the second hard coating composition was used instead of the first hard coating composition, and its warpage value was measured.
量測出的翹曲值為-20 mm。The measured warpage value was -20 mm.
試驗範例2:Test example 2:
範例與比較例中製備之硬塗膜的物理性質是藉由以下所述的方法量測,且結果顯示在下表1中。The physical properties of the hard coating films prepared in the examples and comparative examples were measured by the methods described below, and the results are shown in Table 1 below.
(1)室溫時抗彎曲性(1) Resistance to bending at room temperature
硬塗膜(寬×長= 10 mm × 100 mm)彎折成一半使得膜面之間的距離為6 mm。然後,當再將膜張開時,用肉眼確認裂紋是否有發生在彎折處,並藉此評價室溫時的抗彎曲性。The hard coating film (width × length = 10 mm × 100 mm) is folded in half so that the distance between the film surfaces is 6 mm. Then, when the film was opened again, it was confirmed with a naked eye whether cracks occurred at the bends, and thereby the bending resistance at room temperature was evaluated.
<評價標準>< Evaluation criteria >
◎:彎折處沒有發生裂紋◎: No crack occurred at the bend
○-A:彎折處有發生裂紋(長度等於或小於5 mm,且數量等於或少於5個)○ -A: Cracks occurred at the bend (length is 5 mm or less, and the number is 5 or less)
○-B:彎折處有發生裂紋(長度等於或小於5 mm,且數量大於5個並等於或少於10個)○ -B: Cracks occur at the bend (length is 5 mm or less, and the number is more than 5 and equal to or less than 10)
○-C:彎折處有發生裂紋(長度等於或小於5 mm,且數量大於10個)○ -C: Cracks occur at the bend (length is 5 mm or less, and the number is greater than 10)
△-A:彎折處有發生裂紋(長度大於5 mm並等於或小於10 mm,且數量等於或少於5個)△ -A: There are cracks at the bend (length is more than 5 mm and equal to or less than 10 mm, and the number is equal to or less than 5)
△-B:彎折處有發生裂紋(長度大於5 mm並等於或小於10 mm,且數量大於5個並等於或少於10個)△ -B: Cracks occur at the bend (length greater than 5 mm and equal to or less than 10 mm, and the number is greater than 5 and equal to or less than 10)
△-C:彎折處有發生裂紋(長度大於5 mm並等於或小於10 mm,且數量大於10個)△ -C: Cracks occur at the bends (length is greater than 5 mm and equal to or less than 10 mm, and the number is greater than 10)
×:彎折處發生破裂×: Rupture at the bend
(2)高溫-高濕度時抗彎曲性(2) High temperature-high humidity resistance to bending
硬塗膜(寬×長= 10 mm × 100 mm)彎折成一半使得膜面之間的距離為6 mm,且然後留在85°C且相對濕度85%的環境下24小時。然後,當再將膜張開時,用肉眼確認裂紋是否有發生在彎折處,並藉此評價抗彎曲性。The hard coating film (width × length = 10 mm × 100 mm) was folded in half so that the distance between the film surfaces was 6 mm, and then left in an environment of 85 ° C and 85% relative humidity for 24 hours. Then, when the film was opened again, it was visually confirmed whether cracks occurred at the bends, and the bending resistance was evaluated therefrom.
<評價標準>< Evaluation criteria >
◎:彎折處沒有發生裂紋◎: No crack occurred at the bend
○-A:彎折處有發生裂紋(長度等於或小於5 mm,且數量等於或少於5個)○ -A: Cracks occurred at the bend (length is 5 mm or less, and the number is 5 or less)
○-B:彎折處有發生裂紋(長度等於或小於5 mm,且數量大於5個並等於或少於10個)○ -B: Cracks occur at the bend (length is 5 mm or less, and the number is more than 5 and equal to or less than 10)
○-C:彎折處有發生裂紋(長度等於或小於5 mm,且數量大於10個)○ -C: Cracks occur at the bend (length is 5 mm or less, and the number is greater than 10)
△-A:彎折處有發生裂紋(長度大於5 mm並等於或小於10 mm,且數量等於或少於5個)△ -A: There are cracks at the bend (length is more than 5 mm and equal to or less than 10 mm, and the number is equal to or less than 5)
△-B:彎折處有發生裂紋(長度大於5 mm並等於或小於10 mm,且數量大於5個並等於或少於10個)△ -B: Cracks occur at the bend (length greater than 5 mm and equal to or less than 10 mm, and the number is greater than 5 and equal to or less than 10)
△-C:彎折處有發生裂紋(長度大於5 mm並等於或小於10 mm,且數量大於10個)△ -C: Cracks occur at the bends (length is greater than 5 mm and equal to or less than 10 mm, and the number is greater than 10)
×:彎折處發生破裂×: Rupture at the bend
(3)鉛筆硬度(3) Pencil hardness
鉛筆硬度是使用鉛筆硬度測試機(PHT,韓國Sukbo Science公司製造)施加500 g的荷重量測。鉛筆使用三菱公司(Mitsubishi Corporation)製品,且各鉛筆硬度進行5次量測。當發現二或更多個劃痕時,判定其為有缺陷的,並記錄判定為OK的最大硬度。The pencil hardness is measured using a pencil hardness tester (PHT, manufactured by Sukbo Science, Korea) with a load of 500 g. A pencil made by Mitsubishi Corporation was used, and the hardness of each pencil was measured 5 times. When two or more scratches are found, they are judged to be defective, and the maximum hardness judged as OK is recorded.
(4)翹曲(4) Warping
將範例與比較例中製備的硬塗膜切斷為10 cm×10 cm之尺寸,留在25℃、48%RH環境下24小時,並然後放置在一平玻璃板上,使得其凸形表面係與玻璃板接觸。接著,量測從玻璃板之底部(參考表面)到四個角落之高度的平均以獲得翹曲值。結果係基於以下評價標準紀錄。The hard coating films prepared in the examples and comparative examples were cut to a size of 10 cm × 10 cm, left in an environment of 25 ° C. and 48% RH for 24 hours, and then placed on a flat glass plate so that the convex surface was Contact with glass plate. Next, the average of the height from the bottom (reference surface) of the glass plate to the four corners was measured to obtain the warpage value. Results are recorded based on the following evaluation criteria.
<評價標準>< Evaluation criteria >
◎:四個角落的平均高度等於或小於20 mm◎: The average height of the four corners is equal to or less than 20 mm
◯:四個角落的平均高度大於20 mm且等於或小於50 mm◯: The average height of the four corners is greater than 20 mm and equal to or less than 50 mm
Δ:四個角落的平均高度大於50 mmΔ: The average height of the four corners is greater than 50 mm
×:四個角落完全地浮起,且膜翹曲成圓筒狀×: The four corners completely floated, and the film warped into a cylindrical shape
(5)抗刮擦性(5) Scratch resistance
抗刮擦性是使用鋼絲棉測試機(WT-LCM100,韓國Protec公司製造),在1 kg/(2 cm×2 cm)之荷重下使其往復運動10次進行測試。鋼絲棉使用編號0000款(#0000)。Scratch resistance was tested using a steel wool tester (WT-LCM100, manufactured by Korean Protec Corporation) under a load of 1 kg / (2 cm × 2 cm) for 10 times. Steel wool uses the number 0000 (# 0000).
<評價標準>< Evaluation criteria >
S:0個劃痕S: 0 scratches
A:1至10個劃痕A: 1 to 10 scratches
B:11至20個劃痕B: 11 to 20 scratches
C:21至30個劃痕C: 21 to 30 scratches
D:等於或大於31個劃痕 【表1】
如表1所示,根據本發明之範例1至3的硬塗膜不但具有優異的抗彎曲性與抗刮擦性,並抑制翹曲現象發生。另一方面,能發現比較例1與2之硬塗膜的抗彎曲性質、抗刮擦性及翹曲特性差。As shown in Table 1, the hard coating films according to Examples 1 to 3 of the present invention not only have excellent bending resistance and scratch resistance, but also suppress the occurrence of warping. On the other hand, it was found that the hard coating films of Comparative Examples 1 and 2 had poor bending resistance, scratch resistance, and warpage characteristics.
綜上所述,雖然本發明已以實施例揭露如上,然其並非用以限定本發明。本發明所屬技術領域中具有通常知識者,在不脫離本發明之精神和範圍內,當可作各種之更動與潤飾。因此,本發明之保護範圍當視後附之申請專利範圍所界定者為準。In summary, although the present invention has been disclosed as above with the embodiments, it is not intended to limit the present invention. Those with ordinary knowledge in the technical field to which the present invention pertains can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention shall be determined by the scope of the attached patent application.
無no
無no
Claims (10)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR20160113948 | 2016-09-05 | ||
??10-2016-0113948 | 2016-09-05 | ||
??10-2017-0029333 | 2017-03-08 | ||
KR1020170029333A KR20180027317A (en) | 2016-09-05 | 2017-03-08 | Hard Coating Film and Image Display Device Having the Same |
Publications (1)
Publication Number | Publication Date |
---|---|
TW201825615A true TW201825615A (en) | 2018-07-16 |
Family
ID=61660245
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW106127999A TW201825615A (en) | 2016-09-05 | 2017-08-17 | Hard Coating Film and Image Display Device Having the Same |
Country Status (3)
Country | Link |
---|---|
JP (1) | JP2018047691A (en) |
KR (1) | KR20180027317A (en) |
TW (1) | TW201825615A (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112055874A (en) * | 2018-05-07 | 2020-12-08 | 东洋纺株式会社 | Folding display and mobile terminal device |
WO2020067165A1 (en) * | 2018-09-27 | 2020-04-02 | グンゼ株式会社 | Cover film |
WO2022108053A1 (en) * | 2020-11-19 | 2022-05-27 | 주식회사 엘지화학 | Cover window for flexible display device, and flexible display device |
US20230407026A1 (en) * | 2021-01-15 | 2023-12-21 | Lg Chem, Ltd. | Protecting film for cover window of flexible display device, cover window and flexible display device comprising the same |
KR20240003276A (en) * | 2022-06-30 | 2024-01-08 | 동우 화인켐 주식회사 | A hardcoat film, window and image display device using the same |
-
2017
- 2017-03-08 KR KR1020170029333A patent/KR20180027317A/en unknown
- 2017-08-17 TW TW106127999A patent/TW201825615A/en unknown
- 2017-08-31 JP JP2017166771A patent/JP2018047691A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
JP2018047691A (en) | 2018-03-29 |
KR20180027317A (en) | 2018-03-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10370558B2 (en) | Hard coating composition and hard coating film using the same | |
TW201825615A (en) | Hard Coating Film and Image Display Device Having the Same | |
TWI640568B (en) | Curable composition containing siloxane oligomer and inorganic fine particle | |
US8492450B2 (en) | Siloxane resin composition and protective film for touch panel using the same | |
TWI717529B (en) | Hard coating film and image display device using the same | |
US20180066152A1 (en) | Hard coating film and image display device having the same | |
KR101402105B1 (en) | Silsesquioxane Compound And The Fabrciation Method Of The Same, And A Hard coating Panel Using Silsesquioxane Compound And The Fabrciation Method Of The Same. | |
US20170335114A1 (en) | Hard coating composition and hard coating film using the same | |
US10519342B2 (en) | Hard coating composition and hard coating film using the same | |
JP4412705B2 (en) | Photosensitive resin composition and film having cured film thereof | |
US10351726B2 (en) | Hard coating composition and hard coating film using the same | |
JP2006212987A (en) | Transfer material | |
KR20170075343A (en) | Hard Coating Composition and Hard Coating Film Using the Same | |
KR20160088000A (en) | Multi-functional (meta)acryl alkoxy silane oligomer, method for preparing thereof and composition for optical film comprising the same and its use | |
KR102436845B1 (en) | Hard Coating Composition and Hard Coating Film Using the Same | |
TW201807109A (en) | Hard coating composition, and hard coating film, window film and display device comprising the same | |
KR20170100808A (en) | Hard Coating Film and Flexible Display Having the Same | |
TWI726152B (en) | Hard coating composition and hard coating film using the same | |
KR20180036269A (en) | Hard Coating Composition and Hard Coating Film Using the Same | |
KR20170088062A (en) | Hard Coating Composition and Hard Coating Film Using the Same | |
KR102320488B1 (en) | Hard Coating Composition and Hard Coating Film Using the Same | |
KR20200082886A (en) | Hard-coating composition, hard-coating film and method for preparating the hard-coating film | |
KR20170075342A (en) | Hard Coating Composition and Hard Coating Film Using the Same | |
JP4640762B2 (en) | Hard coat film | |
TW201809160A (en) | Hard coating composition and hard coating film using the same |