TWI605098B - Hard coated film, polarizing film using the same, display member, and display device - Google Patents

Hard coated film, polarizing film using the same, display member, and display device Download PDF

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TWI605098B
TWI605098B TW105120257A TW105120257A TWI605098B TW I605098 B TWI605098 B TW I605098B TW 105120257 A TW105120257 A TW 105120257A TW 105120257 A TW105120257 A TW 105120257A TW I605098 B TWI605098 B TW I605098B
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hard coating
film
coating layer
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TW201710420A (en
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Yukio Matsui
Satoshi Kanata
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Toppan Tomoegawa Optical Films Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance 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
    • 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
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/20—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising esters
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • 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
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • 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

Description

硬被覆薄膜、使用它之偏光板、顯示構件、及顯示裝置 Hard coating film, polarizing plate using the same, display member, and display device

本發明係有關於用於顯示構件等的硬被覆薄膜、以及使用它之偏光板、顯示構件及顯示裝置。 The present invention relates to a hard coating film for a display member or the like, and a polarizing plate, a display member, and a display device using the same.

在液晶顯示面板或觸控面板等顯示構件的最表面，為了提升表面硬度與耐擦傷性而使用硬被覆薄膜。硬被覆薄膜係在透明基材的其中一面形成包含樹脂組成物之硬化膜的硬被覆層而成者。隨著近年來顯示裝置的薄型化及輕量化，硬被覆薄膜亦要求薄型化，而謀求用於硬被覆薄膜之透明基材的薄膜化。 On the outermost surface of a display member such as a liquid crystal display panel or a touch panel, a hard coating film is used in order to improve surface hardness and scratch resistance. The hard coating film is formed by forming a hard coating layer containing a cured film of a resin composition on one surface of a transparent substrate. With the reduction in thickness and weight of the display device in recent years, the hard coating film is also required to be thinner, and the thin substrate for the hard coating film is thinned.

惟，透明基材若為40μm以下則硬被覆層的表面硬度會變低，而不易作為硬被覆薄膜應用於顯示構件。又，以卷對卷方式製造硬被覆薄膜時，若透明基材較薄、強度較弱，則會發生硬被覆層的表面與透明基材的背面黏住所引起的黏連不良。換言之，薄層的透明基材不適合以卷對卷方式捲繞成長尺寸，而缺乏硬被覆薄膜的生產性。 However, when the transparent substrate is 40 μm or less, the surface hardness of the hard coating layer becomes low, and it is not easy to apply it as a hard coating film to a display member. Further, when the hard coating film is produced by a roll-to-roll method, if the transparent substrate is thin and the strength is weak, adhesion failure due to adhesion of the surface of the hard coating layer to the back surface of the transparent substrate occurs. In other words, the thin transparent substrate is not suitable for winding up and down in a roll-to-roll manner, and lacks the productivity of the hard coated film.

以往，有人嘗試兼具硬被覆薄膜之表面硬度與抗黏連性。例如，專利文獻1中記載使用包含平均一次粒徑為5nm以上80nm以下的反應性無機微粒子、與平均一次粒徑為100nm以上300nm以下的親水性微粒 子、與對反應性無機微粒子具有交聯反應性的黏著劑成分的樹脂組成物，形成硬度與抗黏連性優良的硬被覆層。 In the past, attempts have been made to combine the surface hardness and blocking resistance of hard coated films. For example, Patent Document 1 describes the use of reactive inorganic fine particles having an average primary particle diameter of 5 nm or more and 80 nm or less, and hydrophilic fine particles having an average primary particle diameter of 100 nm or more and 300 nm or less. A resin composition having an adhesive component having crosslinking reactivity with respect to the reactive inorganic fine particles forms a hard coating layer excellent in hardness and blocking resistance.

又，專利文獻2中記載使用包含1次平均粒徑為10~100nm，且2次平均粒徑為50~300nm的反應性二氧化矽微粒子的樹脂組成物，形成硬度與抗黏連性優良的硬被覆層。 Further, Patent Document 2 describes a resin composition containing reactive cerium oxide microparticles having a primary particle diameter of 10 to 100 nm and a secondary average particle diameter of 50 to 300 nm, and is excellent in hardness and blocking resistance. Hard coating.

先前技術文獻 Prior technical literature 專利文獻 Patent literature

專利文獻1 日本特開2009-132880號公報 Patent Document 1 Japanese Patent Laid-Open Publication No. 2009-132880

專利文獻2 日本特開2010-82864號公報 Patent Document 2 Japanese Patent Laid-Open Publication No. 2010-82864

然而，硬被覆層形成用樹脂組成物中若使用平均粒徑超過80nm的二氧化矽粒子，則容易喪失硬被覆層的透明性，而有導致顯示裝置之視認性降低的問題。 However, when the cerium oxide particles having an average particle diameter of more than 80 nm are used in the resin composition for forming a hard coating layer, the transparency of the hard coating layer is likely to be lost, and the visibility of the display device is lowered.

因此，本發明係以提供一種透明性、表面硬度、抗黏連性優良，且可達薄型化的硬被覆薄膜為目的。又，本發明係以提供使用該硬被覆薄膜之偏光板、顯示構件及顯示裝置為目的。 Therefore, the present invention has an object of providing a hard coating film which is excellent in transparency, surface hardness, and blocking resistance and which can be made thin. Moreover, the present invention has an object of providing a polarizing plate, a display member, and a display device using the hard coating film.

本發明之硬被覆薄膜為在透明基材的單面設置硬被覆層者，硬被覆層係由包含平均粒徑為80nm以下的膠體二氧化矽、與活性能量線硬化性樹脂的硬被覆層形成用組成物所形成，透明基材之運送方向上的彈性 模數為4.5GPa以上7.0GPa以下，透明基材之與運送方向正交之方向上的彈性模數為5.5GPa以上8.0GPa以下，硬被覆薄膜的表面及背面的算術平均高度(Sa)分別為4nm以上10nm以下，硬被覆層形成用組成物的膠體二氧化矽含量為硬被覆層形成用組成物之總固體含量的20質量%以上50質量%以下。 In the hard coating film of the present invention, the hard coating layer is provided on one surface of the transparent substrate, and the hard coating layer is formed of a hard coating layer containing colloidal ceria having an average particle diameter of 80 nm or less and an active energy ray-curable resin. Formed by the composition, the elasticity of the transparent substrate in the direction of transport The modulus is 4.5 GPa or more and 7.0 GPa or less, and the elastic modulus in the direction orthogonal to the transport direction of the transparent substrate is 5.5 GPa or more and 8.0 GPa or less, and the arithmetic mean height (Sa) of the surface and the back surface of the hard coated film are respectively The content of the colloidal cerium oxide of the composition for forming a hard coating layer is 20% by mass or more and 50% by mass or less based on the total solid content of the composition for forming a hard coating layer.

本發明之偏光板、顯示構件及顯示裝置係分別具備上述之硬被覆薄膜者。 The polarizing plate, the display member, and the display device of the present invention each have the hard coating film described above.

根據本發明，可提供一種透明性、表面硬度、抗黏連性優良，且可達薄型化的硬被覆薄膜、以及使用它之偏光板、顯示構件及顯示裝置。 According to the present invention, it is possible to provide a hard coating film which is excellent in transparency, surface hardness, and blocking resistance, and which can be made thinner, and a polarizing plate, a display member, and a display device using the same.

1‧‧‧硬被覆薄膜 1‧‧‧hard coated film

2‧‧‧透明基材 2‧‧‧Transparent substrate

3‧‧‧硬被覆層 3‧‧‧hard coating

第1圖為實施形態之硬被覆薄膜的示意剖面圖。 Fig. 1 is a schematic cross-sectional view showing a hard coating film of an embodiment.

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

第1圖為實施形態之硬被覆薄膜的示意剖面圖。 Fig. 1 is a schematic cross-sectional view showing a hard coating film of an embodiment.

硬被覆薄膜1係在透明基材2的其中一面設置硬被覆層3者。 The hard coating film 1 is one in which the hard coating layer 3 is provided on one surface of the transparent substrate 2.

(透明基材) (transparent substrate)

透明基材2為作為硬被覆薄膜1之基體的薄膜。就透明基材2而言，只要是以透明性及可見光線之穿透性優良的材料形成的薄膜，則不特別限定，可使用 例如三乙酸纖維素薄膜、環烯烴聚合物薄膜、環烯烴共聚物薄膜、丙烯酸薄膜、聚對苯二甲酸乙二酯薄膜、聚醯亞胺薄膜的任一種。 The transparent substrate 2 is a film which is a base of the hard coating film 1. The transparent substrate 2 is not particularly limited as long as it is formed of a material having excellent transparency and visible light transmittance, and can be used. For example, any one of a cellulose triacetate film, a cycloolefin polymer film, a cycloolefin copolymer film, an acrylic film, a polyethylene terephthalate film, and a polyimide film.

透明基材2的厚度較佳為12~40μm。透明基材2的厚度若低於12μm，透明基材2過薄，使硬被覆層3的硬度及硬被覆薄膜1的強度降低。另一方面，透明基材2的厚度若超過40μm，因硬被覆薄膜1增厚，而無助於使用硬被覆薄膜1之顯示構件的薄型化。 The thickness of the transparent substrate 2 is preferably from 12 to 40 μm. When the thickness of the transparent substrate 2 is less than 12 μm, the transparent substrate 2 is too thin, and the hardness of the hard coating layer 3 and the strength of the hard coating film 1 are lowered. On the other hand, when the thickness of the transparent base material 2 exceeds 40 μm, the hard coating film 1 is thickened, and the thickness of the display member using the hard coating film 1 is not reduced.

作為透明基材2，係使用運送方向(MD方向)上的彈性模數為4.5~7.0GPa，且與運送方向正交之方向(TD方向)的彈性模數為5.5~8.0GPa者。使用運送方向及其正交方向的彈性模數滿足此等範圍的薄膜作為透明基材2時，添加作為硬被覆微粒子之膠體二氧化矽的平均粒徑即使為80nm以下，仍可獲得優良的表面硬度。透明基材2之運送方向及其正交方向上的彈性模數若低於上述範圍，硬被覆層3的硬度(鉛筆強度)會降低。透明基材2之運送方向及其正交方向上的彈性模數若超過上述範圍，則透明基材2會脆化而容易裂開，致硬被覆層3的硬度(鉛筆硬度)降低。 As the transparent substrate 2, the elastic modulus in the transport direction (MD direction) is 4.5 to 7.0 GPa, and the elastic modulus in the direction orthogonal to the transport direction (TD direction) is 5.5 to 8.0 GPa. When the film having such a range that the elastic modulus of the transport direction and the orthogonal direction is used as the transparent substrate 2, the average particle diameter of the colloidal ceria to which the hard-coated fine particles are added is 80 nm or less, an excellent surface can be obtained. hardness. When the elastic modulus of the transparent substrate 2 in the transport direction and the orthogonal direction thereof is less than the above range, the hardness (pencil strength) of the hard coating layer 3 is lowered. When the elastic modulus of the transparent substrate 2 in the transport direction and the orthogonal direction thereof exceeds the above range, the transparent substrate 2 is brittle and easily cracked, and the hardness (pencil hardness) of the hard coating layer 3 is lowered.

又，就透明基材2而言，係使用至少其中一面的算術平均高度(Sa、ISO25178)為4~10nm者。透明基材2的兩面當中，只要至少未設有硬被覆層3的面的算術平均高度為此範圍內即可。未設有硬被覆層3的面的算術平均高度(Sa)若低於4nm，由於捲繞硬被覆薄膜1之際會發生黏連，而不適合以卷對卷製造。另一方面， 未設有硬被覆層3的面的算術平均高度(Sa)若超過10nm，則硬被覆薄膜的透明性(霧度)會降低。 Further, in the case of the transparent substrate 2, the arithmetic average height (Sa, ISO 25178) of at least one of the surfaces is 4 to 10 nm. Among the both surfaces of the transparent substrate 2, the arithmetic mean height of at least the surface on which the hard coating layer 3 is not provided may be within this range. If the arithmetic mean height (Sa) of the surface on which the hard coating layer 3 is not provided is less than 4 nm, adhesion occurs when the hard coating film 1 is wound, and it is not suitable for roll-to-roll manufacturing. on the other hand, When the arithmetic mean height (Sa) of the surface on which the hard coating layer 3 is not provided exceeds 10 nm, the transparency (haze) of the hard coating film is lowered.

(硬被覆層) (hard coating)

硬被覆層3係藉由使至少含有膠體二氧化矽、與活性能量線硬化性樹脂的硬被覆層形成用組成物硬化而形成者。硬被覆層3的厚度較佳為4~15μm。硬被覆層3的厚度若低於4μm，則硬被覆層3的硬度不足。另一方面，硬被覆層3的厚度若超過15μm，由於硬被覆薄膜1的厚度增厚，而無助於使用硬被覆薄膜1之顯示構件的薄型化。 The hard coating layer 3 is formed by curing a composition for forming a hard coating layer containing at least colloidal ceria and an active energy ray-curable resin. The thickness of the hard coating layer 3 is preferably 4 to 15 μm. When the thickness of the hard coating layer 3 is less than 4 μm, the hardness of the hard coating layer 3 is insufficient. On the other hand, when the thickness of the hard coating layer 3 exceeds 15 μm, the thickness of the hard coating film 1 is increased, and the thickness of the display member using the hard coating film 1 is not reduced.

硬被覆層3的表面的算術平均高度(Sa)係調成4~10nm。硬被覆層3的算術平均高度(Sa)若低於4nm，由於捲繞硬被覆薄膜1之際會發生黏連，而不適合以卷對卷製造。另一方面，硬被覆層3的算術平均高度(Sa)若超過10nm，則硬被覆薄膜的透明性(霧度)會降低。 The arithmetic mean height (Sa) of the surface of the hard coating layer 3 is adjusted to 4 to 10 nm. When the arithmetic mean height (Sa) of the hard coating layer 3 is less than 4 nm, adhesion occurs when the hard coating film 1 is wound, and it is not suitable for roll-to-roll manufacturing. On the other hand, when the arithmetic mean height (Sa) of the hard coating layer 3 exceeds 10 nm, the transparency (haze) of the hard coating film is lowered.

膠體二氧化矽為對硬被覆層3賦予硬度的成分。就膠體二氧化矽而言，係使用平均粒徑為80nm以下者。膠體二氧化矽的平均粒徑若超過80nm，則硬被覆薄膜的透明性會降低。膠體二氧化矽的平均粒徑的下限值不特別限定，可適宜使用平均粒徑為5nm以上者。 The colloidal cerium oxide is a component that imparts hardness to the hard coating layer 3. In the case of colloidal cerium oxide, those having an average particle diameter of 80 nm or less are used. When the average particle diameter of the colloidal cerium oxide exceeds 80 nm, the transparency of the hard coating film is lowered. The lower limit of the average particle diameter of the colloidal cerium oxide is not particularly limited, and those having an average particle diameter of 5 nm or more can be suitably used.

膠體二氧化矽的添加量係取硬被覆層形成用組成物中所含之總固體含量的20~50質量%。膠體二氧化矽的添加量若低於樹脂固體含量的20質量%，硬被覆層的硬度不夠充分。另一方面，膠體二氧化矽的添加量 若超過樹脂固體含量的50質量%，由於硬被覆層脆化，結果導致硬度降低。 The amount of the colloidal cerium oxide added is 20 to 50% by mass based on the total solid content contained in the composition for forming a hard coating layer. When the amount of the colloidal cerium oxide added is less than 20% by mass of the resin solid content, the hardness of the hard coating layer is insufficient. On the other hand, the amount of colloidal cerium oxide added If it exceeds 50% by mass of the resin solid content, the hard coating layer is brittle, resulting in a decrease in hardness.

作為膠體二氧化矽，較佳使用以可藉由活性能量線的照射產生反應性之活性能量線反應基經表面修飾的表面修飾膠體二氧化矽。此種表面修飾膠體二氧化矽由於可藉由作為黏著劑使用的活性能量線硬化性樹脂產生交聯，而能夠提升硬被覆層的硬度。 As the colloidal cerium oxide, a surface-modified colloidal cerium oxide which is surface-modified by reactive energy ray reactive groups by irradiation with an active energy ray is preferably used. Such a surface-modified colloidal cerium oxide can increase the hardness of the hard coating layer because it can be crosslinked by the active energy ray-curable resin used as an adhesive.

活性能量線硬化性樹脂為可藉由紫外線、電子束等活性能量線的照射進行聚合而硬化的樹脂，可使用例如單官能、2官能或3官能以上之(甲基)丙烯酸酯單體。此外，於本說明書中，「(甲基)丙烯酸酯」為丙烯酸酯與甲基丙烯酸酯此兩者的總稱，「(甲基)丙烯醯基」為丙烯醯基與甲基丙烯醯基此兩者的總稱。 The active energy ray-curable resin is a resin which can be polymerized by irradiation with an active energy ray such as an ultraviolet ray or an electron beam, and for example, a monofunctional, bifunctional or trifunctional or higher (meth) acrylate monomer can be used. In addition, in the present specification, "(meth) acrylate" is a generic term for both acrylate and methacrylate, and "(meth) acryl oxime" is an acryl fluorenyl group and a methacryl fluorenyl group. The general name of the person.

作為單官能之(甲基)丙烯酸酯化合物的實例，可舉出(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸環氧丙酯、丙烯醯基[口末]啉、N-乙烯吡咯啶酮、丙烯酸四氫糠酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十三酯、(甲基)丙烯酸十六酯、(甲基)丙烯酸十八酯、(甲基)丙烯酸苯甲酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸3-甲氧基丁酯、乙基卡必醇(甲基)丙烯酸酯、磷酸(甲基)丙烯酸酯、氧化乙烯改質磷酸(甲基)丙烯酸酯、(甲基)丙烯酸苯 氧酯、氧化乙烯改質(甲基)丙烯酸苯氧酯、氧化丙烯改質(甲基)丙烯酸苯氧酯、(甲基)丙烯酸壬基苯氧酯、氧化乙烯改質(甲基)丙烯酸壬基苯氧酯、氧化丙烯改質(甲基)丙烯酸壬基苯氧酯、甲氧基二乙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、甲氧基丙二醇(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基乙基-2-羥基丙基鄰苯二甲酸酯、2-羥基-3-苯氧基丙基(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基乙基鄰苯二甲酸氫鹽、2-(甲基)丙烯醯氧基丙基鄰苯二甲酸氫鹽、2-(甲基)丙烯醯氧基丙基六氫鄰苯二甲酸氫鹽、2-(甲基)丙烯醯氧基丙基四氫鄰苯二甲酸氫鹽、(甲基)丙烯酸二甲基胺基乙酯、(甲基)丙烯酸三氟乙酯、(甲基)丙烯酸四氟丙酯、(甲基)丙烯酸六氟丙酯、(甲基)丙烯酸八氟丙酯、具有衍生自2-金剛烷、金剛烷二醇的一價單(甲基)丙烯酸酯之丙烯酸金剛烷酯等的金剛烷衍生物單(甲基)丙烯酸酯等。 Examples of the monofunctional (meth) acrylate compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. N-butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, glycidyl (meth)acrylate, propylene sulfonyl [mouth] porphyrin, N-ethylene Pyrrolidone, tetrahydrofurfuryl acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, isodecyl (meth)acrylate, ( Lauryl methyl methacrylate, tridecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, benzyl (meth) acrylate, 2-(meth) acrylate Ethoxyethyl ester, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth) acrylate, phosphoric acid (meth) acrylate, ethylene oxide modified phosphoric acid (meth) acrylate Benzene (meth)acrylate Oxygen ester, ethylene oxide modified phenoxy (meth) acrylate, propylene oxide modified phenoxy (meth) acrylate, (meth) phenoxy phenoxy ester, ethylene oxide modified bismuth (meth) acrylate Phenoxyphenate, propylene oxide modified (meth) phenoxyphenoxy methacrylate, methoxy diethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy Propylene glycol (meth) acrylate, 2-(methyl) propylene methoxyethyl 2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl (meth) acrylate Ester, 2-(methyl)propenyloxyethylphthalate hydrogenate, 2-(methyl)propenyloxypropylphthalate hydrogenate, 2-(methyl)propenyloxyl Propyl hexahydrophthalate hydrogenate, 2-(methyl)propenyloxypropyltetrahydrophthalate hydrogenate, dimethylaminoethyl (meth)acrylate, (meth)acrylic acid Trifluoroethyl ester, tetrafluoropropyl (meth)acrylate, hexafluoropropyl (meth)acrylate, octafluoropropyl (meth)acrylate, having a monovalent value derived from 2-adamantane, adamantanediol Gold of a single (meth) acrylate such as adamantyl acrylate Derivative mono (meth) acrylate.

作為2官能之(甲基)丙烯酸酯化合物的實例，可舉出乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸酯、壬二醇二(甲基)丙烯酸酯、乙氧基化己二醇二(甲基)丙烯酸酯、丙氧基化己二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、乙氧基化新戊二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、羥基三甲基乙酸新戊二醇二(甲基)丙烯酸酯等的二(甲基)丙烯酸酯等。 Examples of the bifunctional (meth) acrylate compound include ethylene glycol di(meth) acrylate, diethylene glycol di (meth) acrylate, and butane diol di(meth) acrylate. , hexanediol di(meth) acrylate, decanediol di(meth) acrylate, ethoxylated hexane diol di(meth) acrylate, propoxylated hexane diol di(methyl) Acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl Alcohol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylic acid A di(meth)acrylate such as an ester.

作為3官能以上之(甲基)丙烯酸酯化合物的實例，可舉出三羥甲基丙烷三(甲基)丙烯酸酯、乙氧基化三羥甲基丙烷三(甲基)丙烯酸酯、丙氧基化三羥甲基丙烷三(甲基)丙烯酸酯、參2-羥基乙基異三聚氰酸三(甲基)丙烯酸酯、甘油三(甲基)丙烯酸酯等的三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、二新戊四醇三(甲基)丙烯酸酯、二三羥甲基丙烷三(甲基)丙烯酸酯等的3官能之(甲基)丙烯酸酯化合物、或新戊四醇四(甲基)丙烯酸酯、二三羥甲基丙烷四(甲基)丙烯酸酯、二新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二三羥甲基丙烷五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、二三羥甲基丙烷六(甲基)丙烯酸酯等的3官能以上之多官能(甲基)丙烯酸酯化合物、或將此等(甲基)丙烯酸酯的一部分以烷基或ε-己內酯取代而成的多官能(甲基)丙烯酸酯化合物等。 Examples of the trifunctional or higher (meth) acrylate compound include trimethylolpropane tri(meth) acrylate, ethoxylated trimethylolpropane tri(meth) acrylate, and propoxy oxygen. Tris(meth)acrylic acid such as trimethylolpropane tri(meth)acrylate, tris(hydroxy)ethyl isocyanurate or tris(meth)acrylate Trifunctional (meth)acrylic acid such as ester, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate Ester compound, or neopentyl alcohol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol five ( 3-functional group of methyl acrylate, ditrimethylolpropane penta (meth) acrylate, dipentaerythritol hexa(meth) acrylate, ditrimethylolpropane hexa(meth) acrylate The above polyfunctional (meth) acrylate compound or a polyfunctional (meth) acrylate of a part of such (meth) acrylate substituted with an alkyl group or ε-caprolactone And the like.

又，作為活性能量線硬化性樹脂，亦可使用胺基甲酸酯(甲基)丙烯酸酯。作為胺基甲酸酯(甲基)丙烯酸酯，可舉出例如使聚酯多元醇與異氰酸酯單體、或者使預聚物反應而得到之生成物與具有羥基的(甲基)丙烯酸酯單體反應而得者。 Further, as the active energy ray-curable resin, a urethane (meth) acrylate can also be used. Examples of the urethane (meth) acrylate include a polyester polyol and an isocyanate monomer, or a product obtained by reacting a prepolymer, and a (meth) acrylate monomer having a hydroxyl group. The reaction comes.

作為胺基甲酸酯(甲基)丙烯酸酯的實例，可舉出新戊四醇三丙烯酸酯六亞甲基二異氰酸酯胺基甲酸酯預聚物、二新戊四醇五丙烯酸酯六亞甲基二異氰酸酯胺基甲酸酯預聚物、新戊四醇三丙烯酸酯甲苯二異氰酸酯胺基甲酸酯預聚物、二新戊四醇五丙烯酸酯甲苯二異 氰酸酯胺基甲酸酯預聚物、新戊四醇三丙烯酸酯異佛爾酮二異氰酸酯胺基甲酸酯預聚物、二新戊四醇五丙烯酸酯異佛爾酮二異氰酸酯胺基甲酸酯預聚物等。 Examples of the urethane (meth) acrylate include neopentyl alcohol triacrylate hexamethylene diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate hexa Methyl diisocyanate urethane prepolymer, neopentyl alcohol triacrylate toluene diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate toluene dimer Cyanate urethane prepolymer, pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer, dipentaerythritol pentaacrylate isophorone diisocyanate amine base Formate prepolymer and the like.

上述之活性能量線硬化性樹脂可使用1種，亦可組合2種以上使用。又，在上述之活性能量線硬化性樹脂、硬被覆層形成用組成物中可為單體，亦可為一部分經聚合的低聚物。 The above-mentioned active energy ray-curable resin may be used alone or in combination of two or more. In addition, the active energy ray-curable resin or the hard coating layer-forming composition may be a monomer or a part of the polymerized oligomer.

活性能量線硬化性樹脂中，較佳以活性能量線硬化性樹脂之固體含量的10~40質量%的比例含有作為黏著劑成分之雙鍵當量為200~600g/mol且重量平均分子量為8000~15000的反應性高分子。藉由摻混該黏著劑成分作為活性能量線硬化性樹脂的一部分，可抑制硬被覆薄膜的捲曲。 In the active energy ray-curable resin, it is preferable that the ratio of the solid content of the active energy ray-curable resin is from 10 to 40% by mass, and the double bond equivalent of the adhesive component is 200 to 600 g/mol and the weight average molecular weight is 8000 〜. 15,000 reactive polymers. By blending the adhesive component as a part of the active energy ray-curable resin, curling of the hard coating film can be suppressed.

作為雙鍵當量為200~600g/mol且重量平均分子量為8000~15000的反應性高分子，可使用主鏈上鍵結有複數個(甲基)丙烯基((metha)acryl)或(甲基)丙醯烯基((metha)acryloyl)的高分子化合物。作為該高分子化合物的實例，可舉出BEAMSET 371、BEAMSET 371MLV、BEAMSET DK1、BEAMSET DK2、BEAMSET DK3(以上為荒川化學工業股份有限公司)、SMP220A、SMP-250A、SMP-360A、SMP-550A(以上為共榮社化學股份有限公司)。 As a reactive polymer having a double bond equivalent of 200 to 600 g/mol and a weight average molecular weight of 8,000 to 15,000, a plurality of (meth)acryl (meth) acryl or (methyl) may be bonded to the main chain. a polymer compound of (metha) acryloyl. Examples of the polymer compound include BEAMSET 371, BEAMSET 371MLV, BEAMSET DK1, BEAMSET DK2, BEAMSET DK3 (above, Arakawa Chemical Industries Co., Ltd.), SMP220A, SMP-250A, SMP-360A, and SMP-550A ( The above is Gongrongshe Chemical Co., Ltd.).

硬被覆層形成用組成物中也可添加光聚合起始劑。作為光聚合起始劑的實例，可舉出2,2-乙氧基苯乙酮、1-羥基環己基苯基酮、聯苯甲醯、安息香、安息 香甲醚、安息香***、對氯二苯甲酮、對甲氧基二苯甲酮、米勒酮、苯乙酮、2-氯噻噸酮等。可將此等單獨、或者組合2種以上使用。 A photopolymerization initiator may be added to the composition for forming a hard coating layer. Examples of the photopolymerization initiator include 2,2-ethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, benzamidine, benzoin, and rest. Anthracyl ether, benzoin ethyl ether, p-chlorobenzophenone, p-methoxybenzophenone, meloketone, acetophenone, 2-chlorothioxanthone, and the like. These may be used alone or in combination of two or more.

又，硬被覆層形成用組成物中，亦可適宜添加溶劑。作為溶劑的實例，可舉出二丁醚、二甲氧基甲烷、二甲氧基乙烷、二乙氧基乙烷、氧化丙烯、1,4-二烷、1,3-二氧戊烷、1,3,5-三烷、四氫呋喃、苯甲醚及苯***(phenetole)等的醚類；丙酮、甲基乙基酮、二乙基酮、二丙基酮、二異丁基酮、甲基異丁基酮、環戊酮、環己酮、及甲基環己酮等的酮類；還有甲酸乙酯、甲酸丙酯、甲酸正戊酯、乙酸甲酯、乙酸乙酯、丙酸甲酯、丙酸乙酯、乙酸正戊酯、及γ-丁內酯等的酯類，甚而甲基賽路蘇、賽路蘇、丁基賽路蘇、賽路蘇乙酸酯等的賽路蘇類。可將此等單獨、或者組合2種以上使用。 Further, in the composition for forming a hard coating layer, a solvent may be appropriately added. Examples of the solvent include dibutyl ether, dimethoxymethane, dimethoxyethane, diethoxyethane, propylene oxide, and 1,4-diene. Alkane, 1,3-dioxolane, 1,3,5-three An ether such as an alkane, tetrahydrofuran, anisole or phenetole; acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, methyl isobutyl ketone, ring Ketones such as pentanone, cyclohexanone, and methylcyclohexanone; and ethyl formate, propyl formate, n-amyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate , esters such as n-amyl acetate, and γ-butyrolactone, and even celecoxibs such as methyl sirolius, serotonin, butyl seduce, and sedum acetate. These may be used alone or in combination of two or more.

又，作為其它的添加劑，亦可對硬被覆層形成用組成物添加防汙劑、表面調整劑、整平劑、折射率調整劑、光敏化劑、導電材料。 Further, as another additive, an antifouling agent, a surface conditioner, a leveling agent, a refractive index adjuster, a photosensitizer, and a conductive material may be added to the composition for forming a hard coating layer.

本實施形態之硬被覆薄膜可透過以卷對卷，對透明基材的至少其中一面，藉由濕塗布法塗布上述之硬被覆層形成用組成物的塗液，再對塗膜照射電子束或紫外線等的活性能量線，使活性能量線硬化性樹脂硬化而形成。作為濕塗布法，可採用流動塗布法、噴射塗布法、輥塗布法、凹版輥塗布法、空氣刮刀塗布法、刀片塗布法、線刮刀塗布法、刀塗布法、反向塗布法、轉送輥塗布法、微凹版塗布法、觸壓塗布法、流延塗布法、 狹縫模孔塗布法、壓光塗布法、模塗布法等周知之方法。又，在藉由紫外線照射使塗膜硬化的情況下，若採紫外線照射時，可使用高壓水銀燈、鹵素燈、氙燈、無電極燈(fusion lamp)等。紫外線照射量通常為100~800mJ/cm2左右。 The hard coating film of the present embodiment can be applied to a coating liquid for forming a composition for forming a hard coating layer by wet coating on at least one side of a transparent substrate by roll-to-roll, and then irradiating the coating film with an electron beam or The active energy ray such as ultraviolet rays is formed by curing the active energy ray-curable resin. As the wet coating method, a flow coating method, a spray coating method, a roll coating method, a gravure roll coating method, an air knife coating method, a blade coating method, a wire blade coating method, a knife coating method, a reverse coating method, a transfer roll coating method, or the like can be employed. Well-known methods such as a method, a micro gravure coating method, a touch coating method, a cast coating method, a slit die coating method, a calender coating method, and a die coating method. Further, when the coating film is cured by ultraviolet irradiation, a high-pressure mercury lamp, a halogen lamp, a xenon lamp, a fusion lamp or the like can be used when irradiated with ultraviolet rays. The amount of ultraviolet irradiation is usually about 100 to 800 mJ/cm 2 .

就本實施形態之硬被覆薄膜，作為透明基材，透過使用運送方向(MD方向)上的彈性模數為4.5~7.0GPa，且與運送方向正交之方向(TD方向)的彈性模數為5.5~8.0GPa者，可使用平均粒徑為80nm以下的膠體二氧化矽來提升硬被覆層的表面硬度。由於對硬被覆層賦予硬度之膠體二氧化矽的平均粒徑為80nm以下，亦可確保硬被覆薄膜的透明性。又，透過將硬被覆層的表面的算術平均高度、與透明基材的背面的算術平均高度均調成4~10nm，可抑制捲繞時的黏連，因此，本實施形態之硬被覆薄膜薄膜能以卷對卷有效地製造。 In the hard coating film of the present embodiment, as the transparent substrate, the elastic modulus in the transport direction (MD direction) is 4.5 to 7.0 GPa, and the elastic modulus in the direction orthogonal to the transport direction (TD direction) is For 5.5 to 8.0 GPa, colloidal ceria having an average particle diameter of 80 nm or less can be used to increase the surface hardness of the hard coating layer. Since the average particle diameter of the colloidal cerium oxide which imparts hardness to the hard coating layer is 80 nm or less, the transparency of the hard coating film can be ensured. Moreover, by adjusting the arithmetic mean height of the surface of the hard coating layer and the arithmetic mean height of the back surface of the transparent substrate to 4 to 10 nm, the adhesion at the time of winding can be suppressed, and therefore, the hard coating film of the present embodiment is obtained. It can be manufactured efficiently in roll-to-roll.

(其它的變形例) (Other variants)

此外，亦可使用本實施形態之硬被覆薄膜構成偏光板(偏光薄膜)。具體而言，可藉由在第1圖所示之硬被覆薄膜1之透明基材2的另一面(未設有硬被覆層3的面)，以周知之方法設置偏光層，而構成偏光板。偏光層可例如藉由使碘或染料吸附於聚乙烯醇使其配向而形成。 Further, a polarizing plate (polarizing film) may be formed using the hard coating film of the present embodiment. Specifically, the polarizing layer can be formed by a known method by providing a polarizing layer on the other surface of the transparent substrate 2 of the hard coating film 1 shown in FIG. 1 (the surface on which the hard coating layer 3 is not provided). . The polarizing layer can be formed, for example, by absorbing iodine or a dye to polyvinyl alcohol to align it.

又，本實施形態之硬被覆薄膜可利用於構成影像顯示裝置所使用的抗反射薄膜等的顯示構件。抗反射薄膜可藉由在第1圖所示之硬被覆層3上設置積層折 射率不同之複數層而成的抗反射層而構成。作為抗反射薄膜的構成例，可舉出在透明基材2上，依序積層硬被覆層3、高折射率層、折射率低於高折射率層之低折射率層者。也可在硬被覆層3與高折射率層之間，進一步設置折射率低於高折射率層，且折射率高於低折射率層的中折射率層。 Further, the hard coating film of the present embodiment can be used for a display member which constitutes an antireflection film or the like used in an image display device. The antireflection film can be provided with a laminate fold on the hard coating layer 3 shown in FIG. It is composed of an antireflection layer composed of a plurality of layers having different incident rates. As a configuration example of the antireflection film, a hard coating layer 3, a high refractive index layer, and a low refractive index layer having a refractive index lower than that of the high refractive index layer are sequentially laminated on the transparent substrate 2. A medium refractive index layer having a refractive index lower than that of the high refractive index layer and having a higher refractive index than the low refractive index layer may be further disposed between the hard coating layer 3 and the high refractive index layer.

再者，本實施形態之硬被覆薄膜可利用於與液晶面板等組合而構成顯示裝置。作為顯示裝置的構成例，可舉出由觀察側起依序積層使用本實施形態之硬被覆薄膜的抗反射薄膜、偏光板、液晶面板、偏光板與背光單元者。又，亦可進一步積層觸控感測器，而構成附有觸控感測器之顯示裝置。 Further, the hard coating film of the present embodiment can be used in combination with a liquid crystal panel or the like to constitute a display device. Examples of the configuration of the display device include an antireflection film, a polarizing plate, a liquid crystal panel, a polarizing plate, and a backlight unit in which the hard coating film of the present embodiment is laminated in this order from the observation side. Moreover, the touch sensor can be further laminated to form a display device with a touch sensor.

另外，本實施形態之硬被覆薄膜可利用作為智慧型手機或平板電腦、筆記型電腦等的顯示裝置或附有觸控感測器之顯示裝置(觸控面板)所使用的光學機能薄膜。作為光學機能薄膜，除硬被覆薄膜外，還可舉出上述之偏光薄膜或抗反射薄膜、防眩薄膜等。具體而言，本實施形態之硬被覆薄膜可利用於作為設於液晶顯示裝置等的顯示面板之最表面的薄膜、或者作為設於觸控面板之最表面的薄膜、或在以直接接合方式或氣隙方式組裝而成的觸控面板中，作為設於觸控感測器與顯示面板之間的中間薄膜。 Further, the hard coating film of the present embodiment can be used as an optical functional film used for a display device such as a smart phone, a tablet computer, a notebook computer, or a display device (touch panel) with a touch sensor. Examples of the optical functional film include a polarizing film, an antireflection film, and an antiglare film described above in addition to the hard coating film. Specifically, the hard coating film of the present embodiment can be used as a film provided on the outermost surface of a display panel such as a liquid crystal display device, or as a film provided on the outermost surface of the touch panel, or in a direct bonding manner or The touch panel assembled by the air gap method serves as an intermediate film provided between the touch sensor and the display panel.

又，既已就本實施形態之硬被覆薄膜，說明在透明基材的其中一面設置硬被覆層的實例，惟亦可構成在透明基材的兩面設置硬被覆層的硬被覆薄膜。 In the hard coating film of the present embodiment, an example in which a hard coating layer is provided on one surface of the transparent substrate will be described, but a hard coating film in which a hard coating layer is provided on both surfaces of the transparent substrate may be used.

[實施例] [Examples]

以下，對具體地實施本發明之實施例加以說明。 Hereinafter, embodiments of the present invention will be specifically described.

就實施例1~7及比較例1~8，作為透明基材，係使用厚度為25μm的三乙酸纖維素薄膜。 In Examples 1 to 7 and Comparative Examples 1 to 8, a cellulose triacetate film having a thickness of 25 μm was used as the transparent substrate.

對透明基材的其中一面，藉由棒塗布法塗布以下之組成的硬被覆層形成用組成物並使其乾燥後，使用金屬鹵化物燈以照射線量200mJ/m2照射紫外線使塗膜硬化，而得到硬被覆薄膜。此外，硬被覆層形成用組成物的塗布量係調節成使硬化膜的厚度成為6μm。 On one side of the transparent substrate, a hard coating layer-forming composition having the following composition was applied and dried by a bar coating method, and then the coating film was cured by irradiating ultraviolet rays with a metal wire halide lamp at an irradiation dose of 200 mJ/m 2 . A hard coated film is obtained. Further, the coating amount of the composition for forming a hard coating layer was adjusted so that the thickness of the cured film was 6 μm.

<硬被覆層形成用組成物> <Composition for forming a hard coating layer> ‧樹脂材料 ‧Resin material

PE-3A(新戊四醇三丙烯酸酯)，共榮社化學股份有限公司 9質量份 PE-3A (neopentitol triacrylate), Gongrongshe Chemical Co., Ltd. 9 parts by mass

UA-306H(新戊四醇三丙烯酸酯六亞甲基二異氰酸酯胺基甲酸酯預聚物)，共榮社化學股份有限公司 13質量份 UA-306H (neopentitol triacrylate hexamethylene diisocyanate urethane prepolymer), Gongrongshe Chemical Co., Ltd. 13 parts by mass

BEAMSET 371，荒川化學工業股份有限公司 7質量份 BEAMSET 371, Arakawa Chemical Industry Co., Ltd. 7 parts by mass

‧膠體二氧化矽：MEK-ST或MEK-ST-ZL，日產化學工業股份有限公司 47質量份 ‧ Colloidal cerium oxide: MEK-ST or MEK-ST-ZL, Nissan Chemical Industry Co., Ltd. 47 parts by mass

‧聚合起始劑：IRGACURE 184，BASF 2質量份 ‧ Polymerization initiator: IRGACURE 184, BASF 2 parts by mass

‧溶劑：甲基乙基酮 22質量份 ‧ Solvent: methyl ethyl ketone 22 parts by mass

將實施例1~7及比較例1~8中所使用之硬被覆層形成用組成物的組成示於表1。 The composition of the composition for forming a hard coating layer used in Examples 1 to 7 and Comparative Examples 1 to 8 is shown in Table 1.

表2示出實施例1~7及比較例1~8中所使用之透明基材的彈性模數、所得硬被覆薄膜的算術平均高度、鉛筆硬度、霧度、黏連面積。 Table 2 shows the elastic modulus of the transparent substrate used in Examples 1 to 7 and Comparative Examples 1 to 8, the arithmetic mean height of the obtained hard coating film, the pencil hardness, the haze, and the adhesion area.

表2所示之彈性模數、算術平均高度、鉛筆硬度、霧度、黏連面積的測定方法如下。 The measurement methods of the elastic modulus, the arithmetic mean height, the pencil hardness, the haze, and the adhesion area shown in Table 2 are as follows.

<彈性模數> <Elastic Modulus>

基於JIS Z2241，製作朝測定對象方向為100mm、朝寬度方向(與測定對象方向正交的方向)為15mm的帶狀試片，使用小型桌上試驗器(LSC02-30，島津製作所股份有限公司)量測彈性模數。 A strip-shaped test piece having a width of 100 mm in the direction of the measurement and a direction perpendicular to the direction of the measurement target of 15 mm was produced in accordance with JIS Z2241, and a small table tester (LSC02-30, Shimadzu Corporation) was used. Measure the modulus of elasticity.

<算術平均高度> <Arithmetic average height>

基於ISO25178，使用掃描型探針顯微鏡(AFM5400L，Hitachi High-Tech Science股份有限公司)量測100μm×100μm之範圍的算術平均高度(Sa)。 The arithmetic mean height (Sa) in the range of 100 μm × 100 μm was measured using a scanning probe microscope (AFM 5400L, Hitachi High-Tech Science Co., Ltd.) based on ISO25178.

<鉛筆硬度> <pencil hardness>

基於JIS K5600(4.9N荷重)，使用鉛筆擦劃試驗機(HA-301，TESTER SANGYO股份有限公司)量測硬被覆層表面的鉛筆硬度。當測得之鉛筆硬度為3H以上時係判定為表面硬度充足，小於3H時則判定為表面硬度不足。 The pencil hardness of the surface of the hard coating layer was measured using a pencil scratch tester (HA-301, TESTER SANGYO Co., Ltd.) based on JIS K5600 (4.9 N load). When the measured pencil hardness was 3H or more, it was judged that the surface hardness was sufficient, and when it was less than 3H, it was judged that the surface hardness was insufficient.

<霧度> <Haze>

基於JIS K7105，使用霧度計(NDH-2000，日本電色工業股份有限公司)量測霧度。 The haze was measured using a haze meter (NDH-2000, Nippon Denshoku Industries Co., Ltd.) based on JIS K7105.

<黏連面積> <adhesion area>

將裁切成100mm×100mm之正方形的硬被覆薄膜，以硬被覆層與透明基材成交互的方式在玻璃板上疊合5片，並將四角以膠帶固定於玻璃板。將四角以膠帶固定，是為了抑制試樣具有之捲曲對於黏連的影響。 將固定於玻璃板上之硬被覆薄膜的積層體於90℃加熱30分鐘，其後，於120℃進一步加熱120分鐘。發生黏連的部分，由於上下之硬被覆薄膜彼此密接，因此，與無黏連的部分相比看起來較黑。根據目視觀察評定發生黏連之部位(因發生黏連而看起來較黑的部分)的比例。 A hard coated film of a square shape of 100 mm × 100 mm was cut, and five sheets were laminated on the glass plate in such a manner that the hard coating layer and the transparent substrate were interposed, and the four corners were tape-fixed to the glass plate. The four corners are taped to suppress the effect of the curl of the sample on the adhesion. The laminate of the hard coating film fixed on the glass plate was heated at 90 ° C for 30 minutes, and then further heated at 120 ° C for 120 minutes. The portion where the adhesion occurs is because the upper and lower hard coating films are in close contact with each other, and therefore appear darker than the non-adhered portion. The proportion of the site where adhesion occurred (the portion that appears dark due to adhesion) was visually observed.

如表2所示，實施例1~7之硬被覆薄膜係將透明基材的厚度減薄為25μm，但藉由使透明基材之運送方向的彈性模數為4.5~7.0GPa，且使與運送方向正交之方向的彈性模數為5.5~8.0GPa，使用平均粒徑為80nm以下的膠體二氧化矽，可獲得鉛筆硬度為3H以上的硬被覆層。又，在實施例1~7中，透過膠體二氧化矽的平均粒徑採用80nm以下，霧度的值亦壓低至0.20%以下，硬被覆薄膜的透明性極充分。再者，實施例1~7之硬被覆薄膜的黏連面積係小於10%，確認適合以卷對卷製造。 As shown in Table 2, the hard-coated films of Examples 1 to 7 reduced the thickness of the transparent substrate to 25 μm, but the elastic modulus of the transparent substrate was 4.5 to 7.0 GPa, and The elastic modulus in the direction orthogonal to the transport direction is 5.5 to 8.0 GPa, and a hard coat layer having a pencil hardness of 3H or more can be obtained by using colloidal ceria having an average particle diameter of 80 nm or less. Further, in Examples 1 to 7, the average particle diameter of the colloidal ceria was 80 nm or less, and the haze value was also lowered to 0.20% or less, and the transparency of the hard coating film was extremely excellent. Further, the adhesion areas of the hard coating films of Examples 1 to 7 were less than 10%, and it was confirmed that it was suitable for roll-to-roll production.

相對於此，就比較例1及2，由於透明基材的彈性模數落在上述範圍外，硬被覆層的鉛筆強度不足。又，就比較例3及5，由於透明基材或硬被覆層任一者的算術平均高度的值均過小，而顯著發生黏連。就比較例4及6，由於透明基材或硬被覆層任一者之算術平均高度的值均過大而使得霧度降低。就比較例7及8，由於膠體二氧化矽的添加量落在上述範圍外，以致硬被覆層的鉛筆強度降低。 On the other hand, in Comparative Examples 1 and 2, since the elastic modulus of the transparent substrate fell within the above range, the pencil strength of the hard coating layer was insufficient. Further, in Comparative Examples 3 and 5, since the values of the arithmetic mean heights of either the transparent substrate or the hard coating layer were too small, adhesion occurred remarkably. In Comparative Examples 4 and 6, since the values of the arithmetic mean heights of either the transparent substrate or the hard coating layer were too large, the haze was lowered. In Comparative Examples 7 and 8, since the amount of the colloidal cerium oxide added fell outside the above range, the pencil strength of the hard coating layer was lowered.

如此，根據本發明，經確認可提供一種透明性、表面硬度、抗黏連性優良，且可達薄型化的硬被覆薄膜。 Thus, according to the present invention, it has been confirmed that a hard coating film which is excellent in transparency, surface hardness, and blocking resistance and which can be made thinner can be provided.

[產業上可利用性] [Industrial availability]

本發明之硬被覆薄膜係可利用於影像顯示裝置等。 The hard coating film of the present invention can be used for an image display device or the like.

1‧‧‧硬被覆薄膜 1‧‧‧hard coated film

2‧‧‧透明基材 2‧‧‧Transparent substrate

3‧‧‧硬被覆層 3‧‧‧hard coating

Claims (9)

一種硬被覆薄膜，其為在透明基材的單面設置硬被覆層的硬被覆薄膜，其特徵為：該硬被覆層係由包含平均粒徑為80nm以下的膠體二氧化矽、與活性能量線硬化性樹脂的硬被覆層形成用組成物所形成，該透明基材之運送方向上的彈性模數為4.5GPa以上7.0GPa以下，該透明基材之與該運送方向正交之方向上的彈性模數為5.5GPa以上8.0GPa以下，該硬被覆薄膜的表面及背面的算術平均高度(Sa)分別為4nm以上10nm以下，該硬被覆層形成用組成物的膠體二氧化矽含量為該硬被覆層形成用組成物之總固體含量的20質量%以上50質量%以下；該透明基材為三乙酸纖維素薄膜、環烯烴聚合物薄膜、環烯烴共聚物薄膜、丙烯酸薄膜、聚對苯二甲酸乙二酯薄膜、聚醯亞胺薄膜的任一種。 A hard coating film comprising a hard coating layer provided with a hard coating layer on one side of a transparent substrate, characterized in that the hard coating layer comprises colloidal cerium oxide having an average particle diameter of 80 nm or less, and an active energy ray. The hard coating layer is formed of a hard coating layer forming composition, and the elastic modulus of the transparent substrate in the transport direction is 4.5 GPa or more and 7.0 GPa or less, and the elastic substrate is elastic in a direction orthogonal to the transport direction. The modulus is 5.5 GPa or more and 8.0 GPa or less, and the arithmetic mean height (Sa) of the surface and the back surface of the hard coating film is 4 nm or more and 10 nm or less, respectively, and the colloidal ceria content of the hard coating layer forming composition is the hard coating. 20% by mass or more and 50% by mass or less of the total solid content of the composition for layer formation; the transparent substrate is a cellulose triacetate film, a cycloolefin polymer film, a cycloolefin copolymer film, an acrylic film, polyterephthalic acid Any one of an ethylene glycol film and a polyimide film. 如請求項1之硬被覆薄膜，其中在將裁成100mm×100mm之正方形的該硬被覆薄膜，以該硬被覆層與該透明基材交互積層的方式貼合5片，於90℃加熱30分鐘，且進一步於120℃加熱120分鐘之際，該硬被覆層與該透明基材貼附之部分的面積率為10%以下。 The hard coating film according to claim 1, wherein the hard coating film which is cut into a square of 100 mm × 100 mm is laminated with 5 pieces of the hard coating layer and the transparent substrate, and heated at 90 ° C for 30 minutes. And further heated at 120 ° C for 120 minutes, the area ratio of the portion of the hard coating layer to the transparent substrate is 10% or less. 如請求項1之硬被覆薄膜，其中該膠體二氧化矽為表面具有活性能量線反應基的表面處理膠體二氧化矽。 The hard coated film of claim 1, wherein the colloidal ceria is a surface treated colloidal ceria having an active energy ray reactive group on its surface. 如請求項1之硬被覆薄膜，其中該硬被覆層形成用組成物係含有該活性能量線硬化性樹脂之固體含量質量的10質量%以上40質量%以下之雙鍵當量為200g/mol以上600g/mol以下且重量平均分子量為8000以上15000以下的反應性高分子物質。 The hard coating film according to claim 1, wherein the hard coating layer forming composition contains 10% by mass or more and 40% by mass or less of the solid content mass of the active energy ray-curable resin, and the double bond equivalent is 200 g/mol or more and 600 g. a reactive polymer material having a weight average molecular weight of 8,000 or more and 15,000 or less. 如請求項1之硬被覆薄膜，其中該透明基材的厚度為12μm以上40μm以下。 The hard coating film of claim 1, wherein the transparent substrate has a thickness of from 12 μm to 40 μm. 如請求項1之硬被覆薄膜，其中該硬被覆層的厚度為4μm以上15μm以下。 The hard coating film of claim 1, wherein the hard coating layer has a thickness of 4 μm or more and 15 μm or less. 一種偏光板，其係具有如請求項1至6中任一項之硬被覆薄膜。 A polarizing plate having the hard coating film according to any one of claims 1 to 6. 一種顯示構件，其係具有如請求項1至6中任一項之硬被覆薄膜。 A display member having the hard coated film according to any one of claims 1 to 6. 一種顯示裝置，其係具有如請求項1至6中任一項之硬被覆薄膜。 A display device having the hard coating film according to any one of claims 1 to 6.
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