TWI607231B - Hard coat film - Google Patents

Hard coat film Download PDF

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TWI607231B
TWI607231B TW097124817A TW97124817A TWI607231B TW I607231 B TWI607231 B TW I607231B TW 097124817 A TW097124817 A TW 097124817A TW 97124817 A TW97124817 A TW 97124817A TW I607231 B TWI607231 B TW I607231B
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hard coating
film
coating layer
layer
mass
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TW097124817A
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TW200912365A (en
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泉達矢
小野澤豐
所司悟
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琳得科股份有限公司
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/021—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
    • G02B5/0226—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures having particles on the surface
    • 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
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/02—Diffusing elements; Afocal elements
    • G02B5/0268—Diffusing elements; Afocal elements characterized by the fabrication or manufacturing method
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133502—Antiglare, refractive index matching layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Optical Elements Other Than Lenses (AREA)
  • Laminated Bodies (AREA)

Description

硬被覆膜 Hard coating

本發明係有關於一種硬被覆膜及其製法。更詳言之，本發明係有關於一種硬被覆膜，其具有形成相分離結構且內部霧度值為特定範圍之硬被覆層，該硬被覆膜適合作為特別是液晶顯示裝置等具備彩色濾光片之高精密型影像顯示裝置的防眩性薄膜。The present invention relates to a hard coating film and a process for the preparation thereof. More specifically, the present invention relates to a hard coating film having a hard coating layer which forms a phase separation structure and has an internal haze value of a specific range, and the hard coating film is suitable for coloring as a liquid crystal display device or the like. An anti-glare film for a high-precision image display device of a filter.

在CRT或LCD、PDP等的顯示器，會有光線從外部入射畫面且因該光線反射而難以觀看顯示影像之情形，特別是隨著近年來顯示器的大型化，解決上述問題成為越來越重要的課題。解決該等問題之手段之一可舉出在顯示器表面貼合防眩性(AG)硬被覆膜，而且，在該硬被覆膜賦予防眩性之手法可大致區別為以下3種方法，(1)在用以形成硬被覆層之硬化時藉由物理手法加以粗面化之方法；(2)在硬被覆層形成用的硬被覆劑混入填料之方法；及(3)在硬被覆層形成用的硬被覆劑混入非相溶的2成分，來利用該等的相分離之方法。該等係任一者都是藉由在表面形成微細凹凸來抑制光線的正反射，防止日光燈等外部光線映入。但是，在近年成為主流之高精密型的LCD使用上述方法所製造的防眩性薄膜時，在表面凹凸結構的凸部與彩色濾光片的黑色矩陣重疊位置，因為影像光線散射，該部分的發光會耀眼，亦即顯現所謂耀眼的現象。為了解決該問題，高精密LCD用AG薄膜係檢討設置1層具有內部光擴散性之 層，用以賦予防止耀眼之效果。例如在專利文獻1、專利文獻2等記載在基材薄膜上形成光擴散層及防眩層的2層而成之防眩薄膜，專利文獻3係在薄膜的一側形成防眩層且在另一側的面形成光擴散層。該等手法必須有光擴散性能及防眩層的2層用以防止耀眼。又，專利文獻4、專利文獻5提案揭示一種防眩薄膜，其係藉由使1層中含有折射率不同的透射性微粒子，來同時具有光擴散性及防眩性。任一種方法都是使用微粒子來達成光擴散性，必須考慮被覆劑中之微粒子的凝聚、沈降等問題。In a display such as a CRT or an LCD or a PDP, there is a case where light is incident on the screen from the outside and it is difficult to view the displayed image due to the reflection of the light. In particular, with the increase in size of the display in recent years, it has become increasingly important to solve the above problem. Question. One of the means for solving such problems is to attach an anti-glare (AG) hard coating film to the surface of the display, and the method of imparting anti-glare property to the hard coating film can be roughly distinguished from the following three methods. (1) a method of roughening by physical means for forming a hard coating layer; (2) a method of mixing a hard coating agent for forming a hard coating layer into a filler; and (3) a hard coating layer The hard coating agent for formation is mixed with the two components which are incompatible, and the phase separation method is used. Any of these systems suppresses the regular reflection of light by forming fine irregularities on the surface, and prevents external light such as a fluorescent lamp from being reflected. However, when the anti-glare film manufactured by the above method is used in the high-precision LCD which has become the mainstream in recent years, the convex portion of the surface uneven structure overlaps with the black matrix of the color filter, because the image light is scattered, the portion is The radiance will be dazzling, that is, the phenomenon of so-called dazzling. In order to solve this problem, the AG film for high-precision LCDs is reviewed to provide one layer with internal light diffusibility. Layer to give a dazzling effect. For example, Patent Document 1 and Patent Document 2 describe an antiglare film in which two layers of a light diffusion layer and an antiglare layer are formed on a base film, and Patent Document 3 forms an antiglare layer on one side of the film and is in another The surface on one side forms a light diffusion layer. These methods must have two layers of light diffusing properties and an anti-glare layer to prevent dazzling. Further, Patent Document 4 and Patent Document 5 propose an anti-glare film which has both light diffusibility and anti-glare property by including transmissive fine particles having different refractive indices in one layer. In either method, fine particles are used to achieve light diffusibility, and problems such as aggregation and sedimentation of fine particles in the coating agent must be considered.

[專利文獻1]特開2001-305314號公報[Patent Document 1] JP-A-2001-305314

[專利文獻2]特開2003-302506號公報[Patent Document 2] JP-A-2003-302506

[專利文獻3]特開2004-271666號公報[Patent Document 3] JP-A-2004-271666

[專利文獻4]特許第3507719號公報[Patent Document 4] Patent No. 3507719

[專利文獻5]特許第3515401號公報。[Patent Document 5] Japanese Patent No. 3515401.

鑒於上述情形，本發明的目的係提供一種硬被覆膜，其硬被覆層內部的光擴散性不是藉由先前所使用之存在有凝聚或沈降的問題之微粒子，而是藉由其他手段來達成，該硬被覆膜具有防眩功能，能夠有效地抑制特別是液晶顯示裝置等具備彩色濾光片之高精密型影像顯示裝置的耀眼。In view of the above circumstances, an object of the present invention is to provide a hard coating film in which the light diffusibility inside the hard coating layer is not achieved by the microparticles which have been previously used for the problem of aggregation or sedimentation, but by other means. The hard coating film has an anti-glare function, and can effectively suppress the glare of a high-precision image display device including a color filter such as a liquid crystal display device.

為了達成上述目的，本發明等重複專心研究之結果， 發現使用以特定比例含有活性能量線硬化型化合物及熱塑性樹脂且同時含有具有特定性狀的溶劑混合物之硬被覆層形成材料，在基材薄膜上形成塗膜層，並對其照射活性能量線來使其硬化，上述活性能量線硬化型化合物與熱塑性樹脂形成相分離結構，能夠形成具有需要的光擴散性之硬被覆層，能夠達成該目的。本發明係基於此種見識而完成。 In order to achieve the above object, the present invention repeats the results of intensive research, It has been found that a hard coating layer forming material containing an active energy ray-curable compound and a thermoplastic resin in a specific ratio and containing a solvent mixture having a specific property is formed, a coating layer is formed on the base film, and an active energy ray is irradiated thereto. By hardening, the active energy ray-curable compound and the thermoplastic resin form a phase-separated structure, and a hard coating layer having a desired light diffusibility can be formed, which can achieve the object. The present invention has been completed based on such knowledge.

亦即，本發明係提供[1]一種硬被覆膜，其特徵係在基材薄膜上具有以質量比100：0.3~100：50的比例含有(A)活性能量線硬化型化合物的硬化物、及(B)熱塑性樹脂之硬被覆層，在該硬被覆層中上述(A)成分與(B)成分係形成相分離結構且內部霧度值為3~80%，[2]如[1]項之硬被覆膜，其中該硬被覆層係藉由相分離來形成表面凹凸，[3]如[1]或[2]項之硬被覆膜，其中該硬被覆層更含有(E)透明無機微粒子，且其一部分係露出表面來形成凹凸而構成，[4]如[1]至[3]項中任一項之硬被覆膜，其中在硬被覆層表面，藉由外力物理性地形成凹凸，[5]如[1]至[4]項中任一項之硬被覆膜，其中硬被覆層表面依照JIS B 0601-1994測定之算術平均粗糙度Ra為0.015~0.3微米，[6]如[1]至[5]項中任一項之硬被覆膜，其中在硬被覆層表面，更層積具有表面凹凸之防眩層而構成， [7]如[1]至[6]項中任一項之硬被覆膜，係使用於具備彩色濾光片之影像顯示裝置，及[8]一種如[1]項之硬被覆膜的製法，其特徵係在基材薄膜上，使用硬被覆層形成材料形成塗膜層，接著對該塗膜層照射活性能量線形成硬被覆層，來製造硬被覆膜之方法，其中上述硬被覆層形成材料具有以質量比100：0.3~100：50的比例含有(A’)活性能量線硬化型化合物、及(B)熱塑性樹脂，同時以質量比99：1~10：90的比例含有(C)對前述(A’)成分及(B)成分之良溶劑、及(D)對前述(B)成分之弱溶劑。 That is, the present invention provides [1] a hard coating film characterized in that the base film has a cured product of (A) an active energy ray-curable compound in a mass ratio of 100:0.3 to 100:50. And (B) a hard coating layer of a thermoplastic resin, wherein the (A) component and the (B) component form a phase separation structure in the hard coating layer, and an internal haze value of 3 to 80%, [2] such as [1] The hard coating of the item, wherein the hard coating layer forms surface irregularities by phase separation, [3] the hard coating film of [1] or [2], wherein the hard coating layer further contains (E) The transparent inorganic fine particles, and a part thereof is exposed to the surface to form a concave-convex film, wherein the hard coating film of any one of [1] to [3], wherein the surface of the hard coating layer is externally physics [5] The hard coating film according to any one of [1] to [4], wherein the surface of the hard coating layer has an arithmetic mean roughness Ra of 0.015 to 0.3 μm as measured according to JIS B 0601-1994. [6] The hard coating film according to any one of [1] to [5] wherein, on the surface of the hard coating layer, an antiglare layer having surface irregularities is further laminated, [7] The hard coating film according to any one of [1] to [6], which is used for an image display device having a color filter, and [8] a hard coating film according to [1] The method for producing a hard coating film by using a hard coating layer forming material to form a coating film layer on a base film, and then applying the active energy ray to the coating film layer to form a hard coating film, wherein the hard film is formed The coating layer forming material contains (A') active energy ray-curable compound and (B) thermoplastic resin in a mass ratio of 100:0.3 to 100:50, and is contained in a mass ratio of 99:1 to 10:90. (C) a good solvent for the above (A') component and (B) component, and (D) a weak solvent for the component (B).

依照本發明，能夠提供一種硬被覆膜，其具有硬被覆層，該硬被覆層之活性能量線硬化型化合物的硬化物與熱塑性樹脂係形成相分離結構，能夠賦予需要的光擴散性，較佳是表面形成有凹凸，該硬被覆膜具有防眩功能，能夠有效地抑制特別是液晶顯示裝置等具備彩色濾光片之高精密型影像顯示裝置的耀眼。 According to the present invention, it is possible to provide a hard coating film having a hard coating layer in which a cured product of an active energy ray-curable compound forms a phase-separated structure with a thermoplastic resin, thereby imparting desired light diffusibility. In addition, it is preferable that the hard coating film has an anti-glare function, and it is possible to effectively suppress the glare of a high-precision image display device including a color filter such as a liquid crystal display device.

又，依照本發明，能夠效率良好地製造具有防眩功能之硬被覆膜，能夠有效地抑制上述的耀眼。 Moreover, according to the present invention, it is possible to efficiently produce a hard coating film having an anti-glare function, and it is possible to effectively suppress the above-mentioned dazzling.

[實施本發明之最佳態樣] [The best mode for carrying out the invention]

本發明之硬被覆膜係在基材薄膜具有以質量比100：0.3~100：50的比例含有(A)活性能量線硬化型化合物的硬化物及(B)熱塑性樹脂之硬被覆層，在該硬被覆層中上述(A) 成分與(B)成分係形成相分離結構且內部霧度值為3~80%。The hard coating film of the present invention has a hard coating layer of (A) an active energy ray-curable compound and (B) a hard coating layer of a thermoplastic resin in a base film at a mass ratio of 100:0.3 to 100:50. The above (A) in the hard coating layer The component and the component (B) form a phase-separated structure and have an internal haze value of 3 to 80%.

[基材薄膜][Substrate film]

該基材薄膜沒有特別限制，能夠從先前作為光學用硬被覆膜的基材薄膜的基材之眾所周知的塑膠薄膜中適當地選擇。此種塑膠薄膜可舉出例如聚對酞酸乙二酯、聚對酞酸丁二酯、聚萘二甲酸乙二酯等的聚酯薄膜、聚乙烯薄膜、聚丙烯薄膜、玻璃紙(cellophane)、二乙酸纖維素薄膜、三乙酸纖維素薄膜、乙酸纖維丁酸酯薄膜、聚氯乙烯薄膜、聚偏二氯乙烯薄膜、聚乙烯醇薄膜、乙烯-乙酸乙烯酯共聚物薄膜、聚苯乙烯薄膜、聚碳酸酯薄膜、聚甲基戊烯薄膜、聚碸薄膜、聚醚醚酮薄膜、聚醚碸薄膜、聚醚醯亞胺薄膜、聚醯亞胺薄膜、氟樹脂薄膜、聚醯胺薄膜、丙烯酸樹脂薄膜、降烯系樹脂薄膜及環烯烴樹脂薄膜等。The base film is not particularly limited, and can be appropriately selected from a well-known plastic film which is a base material of a base film which has been used as an optical hard coating film. Examples of such a plastic film include polyester film of polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, and the like. Cellulose diacetate film, cellulose triacetate film, cellulose acetate butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate film, polystyrene film, Polycarbonate film, polymethylpentene film, polyfluorene film, polyetheretherketone film, polyether enamel film, polyether quinone film, polyimide film, fluororesin film, polyamide film, acrylic Resin film, drop An olefin resin film, a cycloolefin resin film, or the like.

該等基材薄膜可以是透明、半透明之任一者，又，可以是被著色，亦可以是無著色者，可按照用途而適當地選擇。例如使用作為液晶顯示體的保護用時，以無色透明的薄膜為佳。These base film may be either transparent or translucent, or may be colored or uncolored, and may be appropriately selected depending on the use. For example, when it is used for protection of a liquid crystal display, a colorless transparent film is preferred.

該等基材薄膜的厚度沒有特別限制，可按照狀況而適當地選定，通常為15~250微米，以30~200微米為佳。又，為了提升與設置在其表面的層之黏附性，該基材薄膜可以按照需要在一面或兩面藉由氧化法或凹凸化法等施行表面處理。上述氧化法可舉出例如電暈放電處理、電漿處理、鉻酸處理(濕式)、火焰處理、熱風處理、臭氧、紫外線照射處理等，又，凹凸化法可舉出例如噴砂法及溶劑處理法 等。此等表面處理法能夠按基材薄膜的種類而適當地選擇，通常從效果及操作性等方面而言，以使用電暈放電處理為佳。The thickness of the base film is not particularly limited and may be appropriately selected depending on the condition, and is usually 15 to 250 μm, preferably 30 to 200 μm. Further, in order to improve the adhesion to the layer provided on the surface thereof, the base film may be subjected to surface treatment by oxidation or embossing or the like on one or both sides as needed. Examples of the oxidation method include corona discharge treatment, plasma treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone, and ultraviolet irradiation treatment, and examples of the unevenness method include sandblasting and solvent. Treatment Wait. These surface treatment methods can be appropriately selected depending on the type of the base film, and it is usually preferable to use a corona discharge treatment from the viewpoints of effects and workability.

在本發明，可以按照需要，在該基材薄膜之形成有硬被覆層側的表面設置阻障層，在基材薄膜上使用硬被覆層形成用材料形成材形成硬被覆層時，該阻障層係用以保護該基材薄膜，避免受到該硬被覆層形成用材料中的溶劑之影響。In the present invention, if necessary, a barrier layer is provided on the surface of the base film on which the hard coating layer is formed, and when a hard coating layer is formed on the base film using the material for forming a hard coating layer, the barrier is formed. The layer is used to protect the substrate film from the influence of the solvent in the material for forming the hard coating layer.

[硬被覆層][hard coating]

在本發明的硬被覆膜，硬被覆層係使用含有(A)活性能量線硬化型化合物的硬化物及(B)熱塑性樹脂，且該等係形成相分離結構而構成者。In the hard coating film of the present invention, the hard coating layer contains a cured product containing (A) an active energy ray-curable compound and (B) a thermoplastic resin, and these are formed into a phase-separated structure.

(活性能量線硬化型化合物)(active energy ray-hardening compound)

上述形成(A)硬化物之(A')成分之活性能量線硬化型化合物係指在電磁波或荷電粒子射線中具有能量子者，亦即，係指藉由紫外線或電子射線來交聯、硬化之聚合性化合物。The active energy ray-curable compound which forms the (A') component of the (A) cured product refers to an energy source having electromagnetic waves or charged particle rays, that is, crosslinking or hardening by ultraviolet rays or electron rays. A polymeric compound.

此種活性能量線硬化型化合物可舉出例如光聚合性預聚物及/或光聚合性單體。又，亦可使用含聚合性不飽和基有機化合物鍵結而成的二氧化矽微粒子。上述光聚合性預聚物有自由基聚合型及陽離子聚合型，自由基聚合型的光聚合性預聚物可舉出例如聚酯型丙烯酸酯系、環氧丙烯酸酯系、丙烯酸胺基甲酸酯系及多元醇丙烯酸酯系等。在此，聚酯系丙烯酸酯系預聚物例如能夠藉由將多元羧酸與多元 醇縮合所得到在兩末端具有羥基之聚酯低聚物的羥基使用(甲基)丙烯酸加以酯化，或是藉由將在多元羧酸加添環氧烷所得到低聚物末端的羥基使用(甲基)丙烯酸加以酯化來得到。Examples of such an active energy ray-curable compound include a photopolymerizable prepolymer and/or a photopolymerizable monomer. Further, cerium oxide fine particles in which a polymerizable unsaturated organic compound is bonded may be used. The photopolymerizable prepolymer may be a radical polymerization type or a cationic polymerization type, and the radical polymerization type photopolymerizable prepolymer may, for example, be a polyester acrylate type, an epoxy acrylate type or an acrylamide carboxylic acid. Ester type, polyol acrylate type, etc. Here, the polyester acrylate-based prepolymer can be, for example, a polycarboxylic acid and a polybasic The hydroxyl group of the polyester oligomer having a hydroxyl group at both terminals obtained by alcohol condensation is esterified with (meth)acrylic acid, or by using a hydroxyl group at the end of the oligomer obtained by adding an alkylene oxide to the polycarboxylic acid. (Meth)acrylic acid is obtained by esterification.

環氧丙烯酸酯系預聚物係例如能夠藉由在比較低分子量的雙酚型環氧樹脂或酚醛清漆型環氧樹脂的環氧乙烷環，使(甲基)丙烯酸進行反應來加以酯化而得到。丙烯酸胺基甲酸酯系預聚物係例如能夠藉由使用(甲基)丙烯酸將聚醚型多元醇或聚酯型多元醇與聚異氰酸酯反應而得到的聚胺基甲酸酯低聚物加以酯化來得到。而且，多元醇丙烯酸酯系預聚物能夠藉由使用(甲基)丙烯酸將聚醚型多元醇的羥基加以酯化來得到。此等光聚合性預聚物可使用1種，亦可組合使用2種以上。The epoxy acrylate prepolymer can be esterified by reacting (meth)acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or a novolak type epoxy resin, for example. And get it. The urethane-based prepolymer is, for example, a polyurethane oligomer obtained by reacting a polyether polyol or a polyester polyol with a polyisocyanate using (meth)acrylic acid. Esterification is obtained. Further, the polyol acrylate-based prepolymer can be obtained by esterifying a hydroxyl group of a polyether polyol with (meth)acrylic acid. These photopolymerizable prepolymers may be used alone or in combination of two or more.

另一方面，自由基聚合型的光聚合性預聚物通常使用環氧系樹脂。該環氧系樹脂可舉出例如在雙酚樹脂或酚醛清漆樹脂等的多元酚類使用表氯醇等加以環氧化而成的化合物、使用過氧化物將直鏈狀烯烴化合物或環狀烯烴化合物加以氧化而得到的化合物等。On the other hand, an epoxy resin is usually used for the radical polymerization type photopolymerizable prepolymer. Examples of the epoxy resin include a compound obtained by epoxidizing a polyhydric phenol such as a bisphenol resin or a novolak resin with epichlorohydrin or the like, and a linear olefin compound or a cyclic olefin compound using a peroxide. A compound obtained by oxidation or the like.

又，光聚合性單體，可舉出例如1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、新戊二醇己酸二(甲基)丙烯酸酯、羥基三甲基乙酸新戊二醇二(甲基)丙烯酸酯、二(甲基)丙烯酸二環戊酯、己內酯改性二(甲基)丙烯酸二環戊酯、環氧乙烷改性磷酸二(甲基)丙烯酸酯、烯丙 基化二(甲基)丙烯酸環己酯、二(甲基)丙烯酸三聚異氰酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、二新戊四醇三(甲基)丙烯酸酯、丙酸改性二新戊四醇三(甲基)丙烯酸酯、新戊二醇三(甲基)丙烯酸酯、環氧丙烷改性三羥甲基丙烷三(甲基)丙烯酸酯、三聚異氰酸參(丙烯醯氧基乙基)酯、丙酸改性二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯及己內酯改性二新戊四醇六(甲基)丙烯酸酯等的多官能丙烯酸酯。此等光聚合性單體可使用1種，亦可組合使用2種以上，又，亦可並用前述光聚合性預聚物。Further, examples of the photopolymerizable monomer include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and neopentyl glycol di(methyl). Acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol hexanoic acid di(meth) acrylate, hydroxytrimethyl acetic acid neopentyl glycol di(meth) acrylate, di(a) Dicyclopentyl acrylate, caprolactone modified dicyclopentanyl di(meth)acrylate, ethylene oxide modified di(meth) acrylate, allylic Cyclohexyl (meth) acrylate, trimeric isocyanate, trimethylolpropane tri(meth) acrylate, dipentaerythritol tri(meth) acrylate, propionic acid Modified dipentaerythritol tri(meth)acrylate, neopentyl glycol tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, trimeric isocyanate Propylene (propylene oxyethyl) ester, propionic acid modified dine pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and caprolactone modified dicotyl A polyfunctional acrylate such as an alcohol hexa(meth)acrylate. These photopolymerizable monomers may be used singly or in combination of two or more kinds thereof, or the photopolymerizable prepolymer may be used in combination.

而且，含聚合性不飽和基有機化合物鍵結而成的二氧化矽微粒子(以下，有稱為反應性二氧化矽微粒子之情形)能夠藉由在平均粒徑為0.005~1微米左右的二氧化矽微粒子表面的矽烷醇基，使具有能夠與該矽烷醇基反應的官能基之含聚合性不飽和基有機化合物反應來得到。聚合性不飽和基可舉出例如自由基聚合性的丙烯醯基或甲基丙烯醯基等。Further, the cerium oxide microparticles (hereinafter referred to as reactive cerium oxide microparticles) in which the polymerizable unsaturated organic compound is bonded can be oxidized by an average particle diameter of about 0.005 to 1 μm. The stanol group on the surface of the fine particles is obtained by reacting a polymerizable unsaturated organic compound having a functional group reactive with the stanol group. The polymerizable unsaturated group may, for example, be a radically polymerizable acryl oxime group or a methacryl oxime group.

前述具有能夠與該矽烷醇基反應的官能基之含聚合性不飽和基有機化合物以使用例如通式(I) (式中，R1 係氫原子或甲基，R2 係鹵素原子或 所示之基)所示之化合物等為佳。The above polymerizable unsaturated group-containing organic compound having a functional group reactive with the stanol group to use, for example, the general formula (I) (wherein R 1 is a hydrogen atom or a methyl group, and R 2 is a halogen atom or The compound shown in the group shown) is preferred.

此種化合物能夠使用例如丙烯酸、丙烯醯氯、丙烯酸2-異氰酸乙酯、丙烯酸環氧丙酯、丙烯酸2,3-亞胺基丙酯、丙烯酸2-羥基乙酯、丙烯醯氧基丙基三甲氧基矽烷等及對應該等的丙烯酸衍生物之甲基丙烯酸衍生物。該等丙烯酸衍生物或甲基丙烯酸衍生物可單獨使用，亦可組合2種以上而使用。Such a compound can be used, for example, acrylic acid, acrylonitrile chloride, ethyl 2-isocyanatoacrylate, glycidyl acrylate, 2,3-iminopropyl acrylate, 2-hydroxyethyl acrylate, propylene methoxy propyl acrylate. A methacrylic acid derivative such as a methoxymethoxy decane or the like and an acrylic acid derivative corresponding thereto. These acrylic acid derivatives or methacrylic acid derivatives may be used singly or in combination of two or more.

如此進行所得到含聚合性不飽和基有機化合物鍵結而成的二氧化矽微粒子，其活性能量線硬化成分係藉由照射活性能量線來交聯、硬化。The cerium oxide microparticles obtained by bonding the obtained polymerizable unsaturated group-containing organic compound in this manner are subjected to crosslinking and hardening of the active energy ray-hardening component by irradiation of an active energy ray.

該反應性二氧化矽微粒子具有提升所得到硬被覆膜的耐擦傷性之效果。該反應性二氧化矽微粒子的調配量以在形成的硬被覆層中含有10~90質量%的比率之方式選定為佳。The reactive cerium oxide microparticles have an effect of improving the scratch resistance of the obtained hard coating film. The amount of the reactive cerium oxide fine particles to be blended is preferably selected so as to be contained in a ratio of 10 to 90% by mass in the hard coating layer to be formed.

含有在此種二氧化矽微粒子使具有聚合性不飽和基的有機化合物鍵結而構成的化合物之紫外線(UV)硬化型硬被覆劑例如有JSR(股)製、商品名「OPSTAR-Z7530」、「OPSTAR-Z7524」、「OPSTAR-TU4086」等上市。An ultraviolet (UV) hardening type hard coating agent containing a compound in which such an organic compound having a polymerizable unsaturated group is bonded to such a cerium oxide fine particle is, for example, a product of the product "OPSTAR-Z7530" manufactured by JSR Corporation. "OPSTAR-Z7524" and "OPSTAR-TU4086" are listed.

該等聚合性化合物能夠按照需要並用光聚合引發劑。 對於自由基聚合型的光聚合性預聚物或光聚合性單體，該光聚合引發劑可舉出例如苯偶姻、苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻丙基醚、苯偶姻正丁基醚、苯偶姻異丁基醚、乙醯苯、二甲胺基乙醯苯、2,2-二甲氧基-2-苯基乙醯苯、2,2-二乙氧基-2-苯基乙醯苯、2-羥基-2-甲基-1-苯基丙烷-1-酮、1-羥基環己基苯基酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉-丙烷-1-酮、4-(2-羥基乙氧基)苯基-2(羥基-2-丙基)酮、二苯基酮、對苯基二苯基酮、4,4'-二乙胺基二苯基酮、二氯二苯基酮、2-甲基蒽醌、2-乙基蒽醌、2-第三丁基蒽醌、2-胺基蒽醌、2-甲基噻噸酮、2-乙基噻噸酮、2-氯噻噸酮、2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、苄基二甲基縮酮、乙醯苯二甲基縮酮及對二甲胺基苯甲酸酯等。又，對於陽離子聚合型的光聚合性預聚物之光聚合引發劑可舉出例如由芳香族鋶離子、芳香族氧鋶離子及芳香族碘鎓離子等的鎓與四氟合硼酸鹽、六氟合硼酸鹽、六氟合銻酸鹽及六氟合砷酸鹽等的陰離子所構成的化合物。此等可使用1種，亦可組合使用2種以上，又，相對於前述光聚合性預聚物及/或光聚合性單體100質量份，其調配量通常可在0.2~10質量份的範圍選擇。These polymerizable compounds can be used in combination with a photopolymerization initiator as needed. The photopolymerization initiator may be, for example, a benzoin, a benzoin methyl ether, a benzoin ethyl ether or a benzoin C. The photopolymerization initiator may be, for example, a benzoin, a benzoin methyl ether or a benzoin. Ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoethyl benzene, 2,2-dimethoxy-2-phenyl acetophenone, 2, 2-diethoxy-2-phenylethyl benzene, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4-(Methylthio)phenyl]-2-morpholine-propan-1-one, 4-(2-hydroxyethoxy)phenyl-2(hydroxy-2-propyl)one, diphenyl Ketone, p-phenyldiphenyl ketone, 4,4'-diethylaminodiphenyl ketone, dichlorodiphenyl ketone, 2-methyl hydrazine, 2-ethyl hydrazine, 2-third butyl Base, 2-aminoindole, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-di Ethyl thioxanthone, benzyl dimethyl ketal, acetophenone ketal, and p-dimethylamino benzoate. In addition, examples of the photopolymerization initiator of the cationic polymerization type photopolymerizable prepolymer include ruthenium and tetrafluoroborate such as aromatic ruthenium ion, aromatic oxonium ion, and aromatic iodonium ion, and A compound composed of an anion such as a fluoroborate, a hexafluoroantimonate or a hexafluoroarsenate. These may be used in combination of two or more kinds, and may be used in an amount of usually 0.2 to 10 parts by mass based on 100 parts by mass of the photopolymerizable prepolymer and/or the photopolymerizable monomer. Range selection.

在本發明，關於前述活性能量線硬化型化合物的硬化，在後述之本發明的硬被覆膜的製法詳述。In the present invention, the hardening of the active energy ray-curable compound is described in detail in the method for producing a hard coating film of the present invention to be described later.

((B)熱塑性樹脂)((B) thermoplastic resin)

與前述(A)成分之活性能量線硬化型化合物的硬化物一同構成硬被覆層的主要成分之(B)成分的熱塑性樹脂沒 有特別限制，能夠使用各式各樣的樹脂，就與前述活性能量線硬化型化合物之相分離性、或所形成硬被覆層的防眩性能等而言，以聚酯系樹脂、聚酯型胺基甲酸酯系樹脂、丙烯酸系樹脂等為佳，該等可單獨使用1種，亦可組合使用2種以上。The thermoplastic resin of the component (B) which constitutes the main component of the hard coating layer together with the cured product of the active energy ray-curable compound of the above component (A) There is a particular limitation that a wide variety of resins can be used, and the phase separation property of the active energy ray-curable compound or the antiglare property of the hard coating layer to be formed is, for example, a polyester resin or a polyester resin. A urethane-based resin, an acryl-based resin, or the like is preferable, and these may be used alone or in combination of two or more.

在此，聚酯系樹脂可舉出例如使選自乙二醇、丙二醇、1,3-丙二醇、1,4-丙二醇、二甘醇、三甘醇、1,5-戊二醇、1,6-己二醇、新戊二醇、環己烷-1,4-二甲醇、氫化雙酚A、雙酚A的環氧乙烷或環氧丙烷加成物等的醇成分中之至少1種、與選自對酞酸、異酞酸、萘二羧酸、環己烷-1,4-二羧酸、己二酸、壬二酸、順丁烯二酸、反丁烯二酸、伊康酸及其酸酐等的羧酸成分中至少1種進行縮聚而得到的聚合物等。Here, the polyester resin may, for example, be selected from the group consisting of ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-propanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, and 1, At least 1 of an alcohol component such as 6-hexanediol, neopentyl glycol, cyclohexane-1,4-dimethanol, hydrogenated bisphenol A, bisphenol A ethylene oxide or propylene oxide adduct And selected from the group consisting of citric acid, isophthalic acid, naphthalene dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, adipic acid, sebacic acid, maleic acid, fumaric acid, A polymer obtained by polycondensation of at least one of carboxylic acid components such as itaconic acid and its acid anhydride.

又，聚酯型胺基甲酸酯系樹脂可舉出例如使前述的醇成分與羧酸成分縮聚而得到之在末端具有羥基的聚酯型多元醇，使各種的聚異氰酸酯化合物反應而得到的聚合物等。In addition, the polyester urethane-based resin is obtained by, for example, a polyester-type polyol obtained by polycondensing the above-described alcohol component and a carboxylic acid component and having a hydroxyl group at the terminal, and reacting various polyisocyanate compounds. Polymers, etc.

而且，丙烯酸系樹脂可舉出例如選自烷基的碳數為1~20的(甲基)丙烯酸烷基酯中之至少1種單體的聚合物、或前述的(甲基)丙烯酸烷基酯與其他能夠共聚合的單體之共聚物等。Further, the acrylic resin may, for example, be a polymer of at least one monomer selected from the group consisting of alkyl (meth)acrylic acid alkyl esters having 1 to 20 carbon atoms, or the aforementioned (meth)acrylic acid alkyl group. a copolymer of an ester and another monomer capable of copolymerization, and the like.

該等之中，以聚酯系樹脂及/或聚酯型胺基甲酸酯系樹脂為特佳。Among these, polyester-based resins and/or polyester-based urethane-based resins are particularly preferred.

在該硬被覆層之前述(A)成分的活性能量線硬化型化合物的硬化物與前述(B)成分的熱塑性樹脂的含有比率，是 以質量基準在100:0.3~100:50的範圍選定。相對於(A)成分100質量份，(B)成分的含量為0.3質量份以上時，能夠在硬被覆層的內部賦予需要的光擴散性，又，在表面容易形成微細的凹凸結構，小於50質量份時，該硬被覆層成為具有良好的硬度(耐擦傷性)者。前述含有比率[(A):(B)]以質量基準為100:0.5~100:50較佳，以100:1~100:45為更佳。The content ratio of the cured product of the active energy ray-curable compound of the component (A) to the thermoplastic resin of the component (B) in the hard coating layer is It is selected in the range of 100:0.3 to 100:50 on a mass basis. When the content of the component (B) is 0.3 parts by mass or more based on 100 parts by mass of the component (A), it is possible to impart a desired light diffusibility to the inside of the hard coating layer, and it is easy to form a fine uneven structure on the surface, and less than 50. In the case of a part by mass, the hard coating layer has a good hardness (scratch resistance). The content ratio [(A): (B)] is preferably 100:0.5 to 100:50 on a mass basis, and more preferably 100:1 to 100:45.

(相分離結構)(phase separation structure)

在該硬被覆層，前述(A)成分之活性能量線硬化型化合物與前述(B)成分之熱塑性樹脂係形成相分離結構。In the hard coating layer, the active energy ray-curable compound of the component (A) forms a phase-separated structure with the thermoplastic resin of the component (B).

在該相分離結構，使用顯微鏡能夠觀察到之表面的相分離結構係以(1)均勻的海/島結構，該島的大小為直徑為0.1微米～20微米的範圍；(2)具有不均勻大小的島之海/島結構，該島的最大直徑為0.1微米～50微米的範圍；及(3)形成連續(調制)結構之任一者為佳。In the phase separation structure, the phase separation structure of the surface which can be observed using a microscope is (1) a uniform sea/island structure having a size ranging from 0.1 μm to 20 μm in diameter; (2) having unevenness The size of the sea/island structure of the island, the maximum diameter of the island is in the range of 0.1 micrometer to 50 micrometers; and (3) it is preferred to form either a continuous (modulated) structure.

(1)的結構時，島的直徑小於0.1微米時無法發揮充分的防眩性，相反地，大於20微米時會產生鮮明度降低、耀眼之問題。(2)的結構時，最大島的直徑小於0.1微米時無法發揮充分的防眩性，相反地，大於50微米時會產生鮮明度降低、耀眼之問題。關於(3)的結構，若是塗布溶解在溶劑中的被覆劑來形成硬被覆層並乾燥後，採用活性能量線照射之方法時，能夠顯示良好的光學物性。In the case of the structure of (1), when the diameter of the island is less than 0.1 μm, sufficient anti-glare property cannot be exhibited. Conversely, when it is larger than 20 μm, the problem of sharpness reduction and dazzling is caused. In the case of the structure (2), when the diameter of the largest island is less than 0.1 μm, sufficient anti-glare property cannot be exhibited, and conversely, when it is larger than 50 μm, the problem of sharpness reduction and dazzling is caused. The structure of (3) can exhibit good optical properties when the coating layer dissolved in a solvent is applied to form a hard coating layer and dried, and then subjected to an active energy ray irradiation method.

該硬被覆層係如前述，(A)成分與(B)成分係形成相分離結構，而且，內部霧度值通常為3~80%，以5~70%為佳， 以16~50%為更佳。通常，因為光學用薄膜基材的內部霧度值係大致為0%，所以藉由使硬被覆層的內部霧度值為3~80%，能使硬被覆膜的內部霧度值為3~80%。內部霧度值小於3%時，會有無法得到防止耀眼的效果之情形。又，該內部霧度值大於80%時會有對光線的透射性造成不良影響之情形。而且，在本發明，硬被覆膜的內部霧度值係指在構成該硬被覆膜的霧度值之光線的散射主要原因之中，將起因於與基材薄膜相反側的薄膜表面散射因素之霧度除外後，只有薄膜內部的散射因素所引起之霧度值，係如以下進行來測定。亦即，準備已知總霧度值之透明黏著薄膜，並以與欲測定內部霧度值之硬被覆膜的基材薄膜係相反側的表面係接觸前述透明黏著薄膜的黏著層之方式黏貼，依照JIS K 7136測定黏貼有透明黏著薄膜之薄膜整體的霧度值。將所得到的值減去透明黏著薄膜的總霧度值後之值作為內部霧度值。又，所使用的透明黏著薄膜若是透明且能夠測定霧度值的程度時，可以使用任何的黏著薄膜，以總霧度值係非常小的值為佳。In the hard coating layer, as described above, the component (A) and the component (B) form a phase separation structure, and the internal haze value is usually 3 to 80%, preferably 5 to 70%. It is better to use 16~50%. In general, since the internal haze value of the optical film substrate is approximately 0%, the internal haze value of the hard coating film can be set to 3 by setting the internal haze value of the hard coating layer to 3 to 80%. ~80%. When the internal haze value is less than 3%, there is a case where the effect of preventing dazzling cannot be obtained. Further, when the internal haze value is more than 80%, there is a case where the light transmittance is adversely affected. Further, in the present invention, the internal haze value of the hard coating film refers to scattering of the surface of the film on the opposite side to the substrate film among the scattering factors of the light constituting the haze value of the hard coating film. After the haze of the factor is excluded, only the haze value caused by the scattering factor inside the film is measured as follows. That is, a transparent adhesive film having a known total haze value is prepared, and the surface of the opposite side of the base film of the hard coating film to be measured for the internal haze value is attached to the adhesive layer of the transparent adhesive film. The haze value of the entire film to which the transparent adhesive film was adhered was measured in accordance with JIS K 7136. The value obtained by subtracting the total haze value of the transparent adhesive film from the obtained value was taken as the internal haze value. Further, if the transparent adhesive film to be used is transparent and can measure the haze value, any adhesive film can be used, and the total haze value is very small.

從提高防眩性能的觀點，在該硬被覆層以具有表面凹凸形狀為佳。該表面凹凸的形成方法沒有特別限制，能夠採用(1)利用前述(A)、(B)成分的相分離來形成凹凸之方法；(2)使用透明微粒子並使其一部分露出表面來形成凹凸之方法；及(3)使用具有凹凸形狀之夾具等，藉由外力來物理性地形成凹凸之方法等。該等方法可單獨使用1種，亦可並用2種以上。From the viewpoint of improving the antiglare performance, it is preferred that the hard coating layer has a surface uneven shape. The method for forming the surface unevenness is not particularly limited, and (1) a method of forming irregularities by phase separation of the components (A) and (B), and (2) using transparent fine particles and partially exposing the surface to form irregularities. And (3) a method of physically forming irregularities by an external force using a jig having a concavo-convex shape or the like. These methods may be used alone or in combination of two or more.

從防眩性的觀點，在該硬被覆層之表面的算術平均粗糙度Ra以在0.015~0.3微米之間為佳。表面粗糙度Ra小於0.015微米時，難以顯現防眩性，又，表面粗糙度Ra大於0.3微米時，透過鮮明度下降，會產生耀眼、發白等問題。From the viewpoint of antiglare property, the arithmetic mean roughness Ra of the surface of the hard coating layer is preferably between 0.015 and 0.3 μm. When the surface roughness Ra is less than 0.015 μm, it is difficult to exhibit anti-glare properties, and when the surface roughness Ra is more than 0.3 μm, the transparency of the transmission is lowered, which causes problems such as dazzling and blushing.

又，前述算術平均粗糙度Ra係依照JIS B 0601-1994所測定的值。在此，為了防止耀眼之目的時，不需要防眩性，此時，表面粗糙度Ra亦可以小於0.015微米，例如表面粗糙度Ra為0.01微米以下的透明硬被覆層亦可。Further, the arithmetic mean roughness Ra is a value measured in accordance with JIS B 0601-1994. Here, in order to prevent the glare, the anti-glare property is not required. In this case, the surface roughness Ra may be less than 0.015 μm, and for example, the transparent hard coating layer having a surface roughness Ra of 0.01 μm or less may be used.

該硬被覆層的厚度以0.5~20微米的範圍為佳。該厚度小於0.5微米時硬被覆膜的耐擦傷性會有無法充分發揮之可能性，又，大於20微米時，會有在硬被覆膜產生卷曲之可能性。就耐擦傷性及60度鏡面光澤度的平衡等而言，該硬被覆層的厚度以1~15微米的範圍為更佳，以2~10微米的範圍為特佳。The thickness of the hard coating layer is preferably in the range of 0.5 to 20 μm. When the thickness is less than 0.5 μm, the scratch resistance of the hard coating film may not be sufficiently exhibited, and when it is more than 20 μm, the hard coating film may be curled. The thickness of the hard coating layer is preferably in the range of 1 to 15 μm, and particularly preferably in the range of 2 to 10 μm in terms of scratch resistance and balance of 60-degree specular gloss.

在該硬被覆層，亦可進而層積具有表面凹凸之防眩層。防眩層以由活性能量線硬化型材料的硬化物所構成為佳，表面凹凸能夠與在前述硬被覆層形成凹凸形狀時同樣地進行來形成。防眩層的厚度以1~20微米左右為佳，防眩層的表面粗糙度以0.015~0.3微米為佳。In the hard coating layer, an antiglare layer having surface irregularities may be further laminated. The antiglare layer is preferably formed of a cured product of an active energy ray-curable material, and the surface unevenness can be formed in the same manner as when the hard coating layer has an uneven shape. The thickness of the anti-glare layer is preferably about 1 to 20 μm, and the surface roughness of the anti-glare layer is preferably 0.015 to 0.3 μm.

接著，說明本發明的硬被覆膜之製法。Next, a method of producing the hard coating film of the present invention will be described.

[硬被覆膜之製法][Method of making hard coating]

本發明的硬被覆膜之製法其特徵係在基材薄膜上，使用硬被覆層形成材料形成塗膜層，接著對該塗飾膜照射活 性能量線而形成硬被覆層，來製造硬被覆膜之方法，其中上述硬被覆層形成材料(以下，有簡稱為硬被覆層用被覆劑之情形)具有以質量比100:0.3~100:50的比例含有(A')活性能量線硬化型化合物、及(B)熱塑性樹脂，同時以質量比99:1~10:90的比例含有(C)對前述(A')成分及(B)成分之良溶劑、及(D)對前述(B)成分之弱溶劑。The method for producing a hard coating film of the present invention is characterized in that a coating layer is formed on a base film by using a hard coating layer forming material, and then the coating film is irradiated. A method of producing a hard coating film by forming a hard coating layer by a performance amount line, wherein the hard coating layer forming material (hereinafter, simply referred to as a coating material for a hard coating layer) has a mass ratio of 100:0.3 to 100: The ratio of 50 contains (A') active energy ray-curable compound and (B) thermoplastic resin, and contains (C) the above-mentioned (A') component and (B) at a mass ratio of 99:1 to 10:90. a good solvent for the component and (D) a weak solvent for the component (B).

在上述硬被覆層用被覆劑，相對於(A')成分100質量份，若(B)成分的含量為0.3質量份以上時，能夠對所形成的硬被覆層的內部賦予需要的光擴散性，又，容易在表面形成微細的凹凸結構，50質量份以下時，該硬被覆層成為具有良好的硬度(耐擦傷性)者。前述含有比率[(A'):(B)]以質量基準較佳為100:0.5~100:50，以100:1~100:45為更佳。When the content of the component (B) is 0.3 parts by mass or more based on 100 parts by mass of the (A') component, the coating material for the hard coating layer can impart desired light diffusibility to the inside of the hard coating layer to be formed. Further, it is easy to form a fine uneven structure on the surface, and when it is 50 parts by mass or less, the hard coating layer has good hardness (scratch resistance). The content ratio [(A'): (B)] is preferably 100:0.5 to 100:50 on a mass basis, and more preferably 100:1 to 100:45.

(溶劑)(solvent)

在該硬被覆層用被覆劑，溶劑係使用(C)成分亦即對前述(A')成分及(B)成分之良溶劑、及(D)成分亦即對(B)成分之弱溶劑所構成之混合溶劑。在此，良溶劑及弱溶劑係指具有依照以下所示的方法測定得到的溶解性。In the coating material for a hard coating layer, the solvent (C) component, that is, the good solvent for the components (A') and (B), and the weak solvent of the component (B), that is, the component (B), are used as the solvent. A mixed solvent constituting. Here, the good solvent and the weak solvent mean the solubility measured by the method shown below.

對相當對象試料的固體成分3克，以總量為20克之方式添加欲測定溶解性的溶劑，並在溫度25℃攪拌時，若能夠得到均勻且具有透明性之溶液時，該溶劑對於該試料係良溶劑，另一方面，若認定為混濁、分離者，該溶劑對於該試料係弱溶劑。3 g of the solid component of the corresponding sample, the solvent to be measured is added in a total amount of 20 g, and when a solution having uniformity and transparency is obtained at a temperature of 25 ° C, the solvent is for the sample. A good solvent is used. On the other hand, if it is determined to be turbid or separated, the solvent is a weak solvent for the sample.

(B)成分的熱塑性樹脂係例如聚酯系樹脂或聚酯型胺 基甲酸酯系樹脂時，對前述樹脂之良溶劑可例示環己酮、丙酮、乙酸乙酯、四氫呋喃及甲基乙基酮等。另一方面，弱溶劑可例示甲苯、二甲苯、甲基異丁基酮、乙基賽路蘇、丙二醇一甲基醚、異丁醇、異丙醇、乙醇、甲醇、己烷及精製水等。The thermoplastic resin of the component (B) is, for example, a polyester resin or a polyester amine. In the case of a carboxylic acid ester-based resin, examples of the solvent of the resin include cyclohexanone, acetone, ethyl acetate, tetrahydrofuran, and methyl ethyl ketone. On the other hand, the weak solvent may, for example, be toluene, xylene, methyl isobutyl ketone, ethyl celecoxib, propylene glycol monomethyl ether, isobutanol, isopropanol, ethanol, methanol, hexane, purified water, or the like. .

又，(B)成分的熱塑性樹脂係丙烯酸系樹脂時，良溶劑可例示環己酮、丙酮、乙酸乙酯、四氫呋喃、二甲苯、甲苯、甲基乙基酮、甲基異丁基酮、乙基賽路蘇及丙二醇一甲基醚等。另一方面，弱溶劑可例示異丁醇、異丙醇、乙醇、甲醇、己烷及精製水等。Further, when the thermoplastic resin of the component (B) is an acrylic resin, examples of the good solvent include cyclohexanone, acetone, ethyl acetate, tetrahydrofuran, xylene, toluene, methyl ethyl ketone, methyl isobutyl ketone, and B. Kesailusu and propylene glycol monomethyl ether. On the other hand, examples of the weak solvent include isobutanol, isopropanol, ethanol, methanol, hexane, purified water, and the like.

又，前述的良溶劑及除了精製水以外之弱溶劑，任一者對於通常使用的活性能量線硬化型化合物都是良溶劑。Further, any of the above-mentioned good solvent and weak solvent other than purified water is a good solvent for the active energy ray-curable compound which is generally used.

在本發明，前述(C)成分的溶劑可單獨使用1種，亦可混合使用2種以上，前述(D)成分的溶劑可單獨使用1種，亦可混合使用2種以上。In the present invention, the solvent of the component (C) may be used singly or in combination of two or more. The solvent of the component (D) may be used singly or in combination of two or more.

在該硬被覆層用被覆劑之前述(C)成分的溶劑與前述(D)成分的溶劑之含有比率[(C):(D)]，是以質量基準為99:1~10:90的範圍選定。該含有比率在上述範圍時，在形成硬被覆層時，能夠產生良好的相分離，能夠對所得到的硬被覆層內部賦予需要的光擴散性，又，容易在表面形成微細的凹凸結構。該含有比率係質量基準時為97:3~15:85，以95:5~40:60為更佳。The content ratio of the solvent of the component (C) of the coating material for the hard coating layer to the solvent of the component (D) [(C): (D)] is based on a mass ratio of 99:1 to 10:90. The range is selected. When the content ratio is in the above range, when the hard coating layer is formed, good phase separation can be produced, and the required light diffusibility can be imparted to the inside of the obtained hard coating layer, and a fine uneven structure can be easily formed on the surface. The content ratio is 97:3 to 15:85, preferably 95:5 to 40:60.

((E)透明無機微粒子)((E) transparent inorganic fine particles)

在該硬被覆層用被覆劑藉由以各自前述比例含有前述 (A')與(B)、(C)與(D)的成分，並藉由硬被覆層形成時之相分離，能夠對所得到的硬被覆層的內部賦予需要的光擴散性，又，容易在表面形成微細的凹凸結構，能夠賦予高精密的防眩性。如此，雖然在硬被覆層用被覆劑不必如先前調配用以賦予防眩性之無機系微粒子或有機系微粒子，但是在不損害本發明的效果之範圍，能夠按照需要調配透明無機微粒子作為(E)成分。The coating composition for a hard coating layer contains the aforementioned in each of the above ratios (A') and (B), (C) and (D), and the phase separation at the time of formation of the hard coating layer, can impart desired light diffusibility to the inside of the obtained hard coating layer, and It is easy to form a fine uneven structure on the surface, and it is possible to impart high-precision anti-glare properties. In this way, it is not necessary to mix the inorganic fine particles or the organic fine particles for imparting anti-glare properties to the coating material for the hard coating layer. However, the transparent inorganic fine particles can be blended as needed (E in the range which does not impair the effects of the present invention). )ingredient.

前述透明無機微粒子沒有特別限制，能夠從先前用以對硬被覆層賦予防眩性所使用的各種透明性無機微粒子之中，適當地選擇使用。特別適合舉出的透明無機微粒子係平均粒徑為10~100奈米左右膠體二氧化矽微粒子。The transparent inorganic fine particles are not particularly limited, and can be appropriately selected from among various transparent inorganic fine particles used for imparting anti-glare properties to the hard coating layer. Particularly suitable for the transparent inorganic fine particle system is an average particle diameter of about 10 to 100 nm of colloidal cerium oxide microparticles.

在本發明，(E)透明無機微粒子可單獨使用1種，亦可組合使用2種以上。其含量可以遠低於先前技術，相對於前述(A')成分及(B)成分的合計量，通常為0.1~10質量份左右。該微粒子的含量為上述範圍時，所形成的層能夠得到安定的光學特性，同時能夠賦予更良好的防眩性。該微粒子的含量以1~8質量份，以1.5~5質量份為更佳。In the present invention, the (E) transparent inorganic fine particles may be used singly or in combination of two or more. The content thereof is much lower than that of the prior art, and is usually about 0.1 to 10 parts by mass based on the total amount of the components (A') and (B). When the content of the fine particles is in the above range, the formed layer can obtain stable optical characteristics and can impart more excellent anti-glare properties. The content of the fine particles is preferably from 1 to 8 parts by mass, more preferably from 1.5 to 5 parts by mass.

在本發明，能夠按照需要與上述透明無機微粒子一同適當地調配透明有機微粒子。In the present invention, the transparent organic fine particles can be appropriately blended together with the above transparent inorganic fine particles as needed.

(硬被覆層的形成)(formation of hard coating)

在該硬被覆層用被覆劑之溶劑的含量沒有特別限制，可適當地選定該含量來得到適合塗布的黏度之被覆劑，以50~95質量%為佳。The content of the solvent of the coating material for the hard coating layer is not particularly limited, and the coating material can be appropriately selected to obtain a coating material suitable for coating, preferably 50 to 95% by mass.

在該硬被覆層用被覆劑，除了前述(A')~(E)成分以外， 亦可在不損害本發明效果的範圍，含有各種添加劑、例如光聚合引發劑、防靜電劑、抗氧化劑、紫外線吸收劑、光安定劑、調平劑及消泡劑等。又，光聚合引發劑能夠使用與前述硬被覆層的說明所記載者同樣之物。In addition to the components (A') to (E) described above, the coating agent for a hard coating layer Further, various additives such as a photopolymerization initiator, an antistatic agent, an antioxidant, an ultraviolet absorber, a photostabilizer, a leveling agent, an antifoaming agent, and the like may be contained in a range not impairing the effects of the present invention. Further, the photopolymerization initiator can be the same as those described in the description of the hard coating layer.

在本發明，能夠藉由在基材薄膜上或在其表面上按照需要所設置的阻障層上，使用先前眾所周知的方法、例如棒塗布法、刮刀塗布法、輥塗布法、刮板塗布法、模頭塗布法及凹版塗布法等塗布如前述進行所調製的硬被覆層用被覆劑形成塗膜，乾燥後並對其照射活性能量線使該塗膜硬化，能夠形成硬被覆層。在本發明，在阻障層上塗布硬被覆層用被覆劑時，基材薄膜不會受到該被覆劑中的溶劑之損傷。In the present invention, a previously known method such as a bar coating method, a knife coating method, a roll coating method, or a blade coating method can be used on the barrier layer provided on the substrate film or on the surface thereof as needed. Coating, such as a die coating method and a gravure coating method, a coating film for a hard coating layer prepared as described above is formed, dried, and then irradiated with an active energy ray to cure the coating film, whereby a hard coating layer can be formed. In the present invention, when the coating material for a hard coating layer is applied onto the barrier layer, the substrate film is not damaged by the solvent in the coating material.

活性能量線可舉出例如紫外線或電子射線等。上述紫外線能夠使用高壓水銀燈、熔融H燈、氙燈等而得到，照射量通常為100~500mJ/cm2 ，另一方面，電子射線能夠藉由電子射線加速器等而得到，照射量通常為150~350kV。該活性能量線之中，以紫外線為特佳。又，使用電子射線時，不必添加聚合引發劑亦能夠得到硬化膜。Examples of the active energy ray include ultraviolet rays, electron beams, and the like. The ultraviolet light can be obtained by using a high-pressure mercury lamp, a molten H lamp, a xenon lamp, or the like, and the irradiation amount is usually 100 to 500 mJ/cm 2 . On the other hand, the electron beam can be obtained by an electron beam accelerator or the like, and the irradiation amount is usually 150 to 350 kV. . Among the active energy rays, ultraviolet rays are particularly preferred. Further, when an electron beam is used, a cured film can be obtained without adding a polymerization initiator.

(藉由外力形成凹凸)(formation of irregularities by external force)

按照需要進行之藉由外力在硬被覆層表面，物理性形成凹凸之方法，可舉出例如轉印凹凸之方法。具體上，可舉出在將硬被覆層用被覆劑塗布在基材薄膜並乾燥溶劑而得到的塗膜上，貼合具有凹凸面之薄膜(凹凸薄膜)的凹凸面，並在該狀態照射活性能量線後，剝離除去凹凸薄膜之 方法。除去凹凸薄膜後，亦可進而照射能量線。能量線的照射條件能夠與形成前述的硬被覆層時相同條件進行。凹凸薄膜以使活性能量線之紫外線透射者為佳，可舉出例如具有塗布能量線硬化型樹脂與二氧化矽等的填料之混合物並硬化而成的層之聚對酞酸乙二酯或在表面藉由壓紋加工等形成凹凸而成的聚乙烯薄膜等。凹凸面的表面粗糙度Ra以0.015~0.5微米為佳。凹凸薄膜的表面粗糙度在該範圍時，所得到的硬被覆膜的防眩性良好。A method of physically forming irregularities on the surface of the hard coating layer by an external force as needed, for example, a method of transferring irregularities. Specifically, the coating film obtained by applying the coating material for a hard coating layer to the base film and drying the solvent is attached to the coating film having the uneven surface (concave-convex film), and the active surface is irradiated in this state. After the energy line, peeling off the uneven film method. After the uneven film is removed, the energy ray can be further irradiated. The irradiation conditions of the energy ray can be performed under the same conditions as in the case of forming the hard coating layer described above. The uneven film is preferably one having a layer of a polyethylene terephthalate having a layer obtained by coating a mixture of an energy ray-curable resin and a filler such as cerium oxide, or the like. A polyethylene film or the like formed by forming irregularities on the surface by embossing or the like. The surface roughness Ra of the uneven surface is preferably 0.015 to 0.5 μm. When the surface roughness of the uneven film is within this range, the obtained hard coating film is excellent in antiglare property.

(防眩層的形成)(formation of anti-glare layer)

按照需要層積於硬被覆層之防眩層的形成方法可舉出例如(1)與本發明的硬被覆膜同樣地，將含有活性能量線硬化型化合物、熱塑性樹脂及溶劑之防眩層用被覆劑塗布在硬被覆層並乾燥，藉由相分離形成凹凸且照射活性能量線之方法；(2)將在活性能量線硬化型化合物調配無機系微粒子或有機系微粒子而成的防眩層用被覆劑塗布在硬被覆層上，並照射活性能量線之方法；及(3)將含有活性能量線硬化型化合物之防眩層用被覆劑塗布在硬被覆層後，藉由外力形成凹凸，且照射活性能量線之方法等。該等方法所使用的活性能量線硬化型化合物、熱塑性樹脂、溶劑、無機系微粒子及有機系微粒子、藉由外力之凹凸形成方式係各自能夠使用與在本發明的硬被覆膜的說明所記載者相同之物。For example, (1) an antiglare layer containing an active energy ray-curable compound, a thermoplastic resin, and a solvent, in the same manner as the hard coating film of the present invention, as a method of forming the antiglare layer to be laminated on the hard coating layer. a method in which a coating layer is applied to a hard coating layer and dried to form irregularities by phase separation, and an active energy ray is irradiated; and (2) an anti-glare layer in which an active energy ray-curable compound is blended with inorganic fine particles or organic fine particles a method in which a coating agent is applied to a hard coating layer and irradiated with an active energy ray; and (3) a coating agent for an antiglare layer containing an active energy ray-curable compound is applied to the hard coating layer, and irregularities are formed by an external force. And a method of irradiating an active energy ray or the like. The active energy ray-curable compound, the thermoplastic resin, the solvent, the inorganic fine particles, and the organic fine particles used in the methods can be used as described in the description of the hard coating film of the present invention. The same thing.

[硬被覆膜][hard coating]

如此進行所形成之本發明的硬被覆膜之內部霧度值必 須為3~80%。內部霧度值小於3%時抑制耀眼之性能不充分，大於80%時視認性降低。較佳之內部霧度值為5~70%，以為16~50%為更佳。能夠具有更良好的內部霧度值，同時具有以下所示的光學特性，乃是較佳。The internal haze value of the hard coating film of the present invention thus formed must be Must be 3~80%. When the internal haze value is less than 3%, the performance of suppressing glare is insufficient, and when it is more than 80%, the visibility is lowered. A preferred internal haze value is 5 to 70%, preferably 16 to 50%. It is preferred to have a better internal haze value while having the optical characteristics shown below.

在本發明的硬被覆膜，總霧度值及60度鏡面光澤度係防眩性的指標，總霧度值以3%以上為佳，又60度鏡面光澤度以200以下為佳。總霧度值小於3%時，難以發揮充分的防眩性，又60度鏡面光澤度大於200時表面光澤度大(光的反射大)、會成為對防眩性造成不良影響之原因。但是，總霧度值太高時光透射性變差，乃是不佳。又影像鮮明度的合計值以30以上為佳。該影像鮮明度的合計值係顯示畫質、亦即視認性的指標，該值小於30時無法得到良好的顯示畫質(視認性)。而且，總光線透射率以88%以上為佳，小於88%時會有透明性不充分的可能性。又，內部霧度值係如前述之說明。In the hard coating film of the present invention, the total haze value and the 60-degree specular glossiness are indicators of the anti-glare property, and the total haze value is preferably 3% or more, and the 60-degree specular gloss is preferably 200 or less. When the total haze value is less than 3%, it is difficult to exhibit sufficient anti-glare property, and when the 60-degree specular gloss is more than 200, the surface glossiness is large (reflection of light is large), which may cause an adverse effect on the anti-glare property. However, when the total haze value is too high, the light transmittance is deteriorated, which is not preferable. Further, the total value of the image sharpness is preferably 30 or more. The total value of the vividness of the image is an index indicating the image quality, that is, the visibility, and when the value is less than 30, good display quality (visibility) cannot be obtained. Further, the total light transmittance is preferably 88% or more, and when it is less than 88%, the transparency may be insufficient. Further, the internal haze value is as described above.

從防眩性、顯示畫質(視認性)、光透射性、透明性等的平衡面而言，總霧度值以10~80%為佳，影像鮮明度的合計值以35以上為更佳，總光線透射率係以90%以上為更佳。From the balance surface of anti-glare property, display image quality (visibility), light transmittance, transparency, etc., the total haze value is preferably 10 to 80%, and the total value of image sharpness is preferably 35 or more. The total light transmittance is preferably 90% or more.

而且，在本發明，總霧度值係指起因於硬被覆膜的內部之霧度值(內部霧度值)與起因於表面的凹凸之霧度值(內部霧度值)之合計值，係將霧度計放置在該硬被覆膜上，依照JIS K 7136來測定。又60度鏡面光澤度係依照JIS K 7105使用光澤計來測定。Further, in the present invention, the total haze value refers to a total value of a haze value (internal haze value) due to the inside of the hard coating film and a haze value (internal haze value) due to the unevenness of the surface. A haze meter was placed on the hard coating film and measured in accordance with JIS K 7136. The 60-degree specular gloss was measured in accordance with JIS K 7105 using a gloss meter.

又，影像鮮明度的合計值係依照JIS K 7105來求取5 種類的狹縫(狹縫寬度：0.125毫米、0.25毫米、0.5毫米、1毫米及2毫米)的影像鮮明度，並將所得到5個值的合計定義為影像鮮明度的合計值。Moreover, the total value of the vividness of the image is obtained in accordance with JIS K 7105. The image sharpness of the type of slit (slit width: 0.125 mm, 0.25 mm, 0.5 mm, 1 mm, and 2 mm), and the total of the obtained five values was defined as the total value of the image sharpness.

又，前述光學特性的測定方法係在以後說明。Moreover, the method of measuring the optical characteristics will be described later.

在本發明的硬被覆膜，為了賦予防止反射性等之目的，能夠按照必要在最上層設置防止反射層、例如矽氧烷系被膜、氟系被膜等。此時，該防止反射層的厚度以0.05~1微米左右為佳。藉由設置該防止反射層，能夠消除來自太陽光、日光燈等反射所產生的映入畫面，又，藉由抑制表面的反射率，總光線透射率提升、透明性提高。又，依照阼止反射層的種類，能夠謀求提升防靜電性。In the hard coating film of the present invention, an antireflection layer such as a siloxane-based coating film, a fluorine-based coating film, or the like can be provided in the uppermost layer as needed for the purpose of imparting antireflection properties and the like. At this time, the thickness of the antireflection layer is preferably about 0.05 to 1 μm. By providing the anti-reflection layer, it is possible to eliminate the reflection screen generated by reflections such as sunlight and fluorescent lamps, and to suppress the reflectance of the surface, the total light transmittance is improved, and the transparency is improved. Further, according to the type of the antireflection layer, it is possible to improve the antistatic property.

在本發明的硬被覆膜，可以在與基材薄膜的硬被覆層相反側形成黏著劑層，用以黏貼液晶顯示體等的被黏物。該構成黏著劑層之黏著劑，以使用適合光學用途之例如丙烯酸系黏著劑、胺基甲酸酯系黏著劑、矽系黏著劑為佳。該黏著劑層的厚度通常為5~100微米，以10~60微米的範圍為佳。In the hard coating film of the present invention, an adhesive layer may be formed on the side opposite to the hard coating layer of the base film to adhere the adherend such as a liquid crystal display. The adhesive constituting the adhesive layer is preferably an acrylic adhesive, an urethane-based adhesive or an oxime-based adhesive suitable for optical use. The thickness of the adhesive layer is usually from 5 to 100 μm, preferably from 10 to 60 μm.

而且，可按照必要在該黏著劑層上設置剝離薄膜。該剝離薄膜可舉出在例如聚對酞酸乙二酯、聚丙烯等的各種塑膠薄膜上塗布矽樹脂等的剝離劑而成者等。該剝離薄膜的厚度沒有特別限制，通常為20~150微米左右。Further, a release film may be provided on the adhesive layer as necessary. The release film may be a release agent such as a ruthenium resin coated on various plastic films such as polyethylene terephthalate or polypropylene. The thickness of the release film is not particularly limited and is usually about 20 to 150 μm.

本發明的硬被覆膜之活性能量線硬化型化合物的硬化物與熱塑性樹脂係形成相分離結構，來賦予需要的光擴散性，較佳是具有在表面形成凹凸的硬被覆層，能夠使用作 為防眩性薄膜，適合作為特別是能夠有效地抑制特別是液晶顯示裝置等具備彩色濾光片之高精密型影像顯示裝置的耀眼之防眩性薄膜。The cured product of the active energy ray-curable compound of the hard coating film of the present invention forms a phase-separated structure with a thermoplastic resin to impart desired light diffusibility, and preferably has a hard coating layer having irregularities formed on the surface, and can be used as a coating layer. The anti-glare film is particularly suitable as a dazzling anti-glare film which can effectively suppress a high-precision image display device including a color filter, such as a liquid crystal display device.

[實施例][Examples]

接著，藉由實施例來更詳細地說明本發明，但是本發明絲毫未限定於此等例子。Next, the present invention will be described in more detail by way of examples, but the invention is not limited thereto.

又，硬被覆膜的性能係依照下述的方法來評價。Moreover, the performance of the hard coating film was evaluated by the following method.

(1)總光線透射率及總霧度值(1) Total light transmittance and total haze value

使用日本電色工業(股)製霧度計「NDH2000」，並依照JIS K 7136測定。A haze meter "NDH2000" manufactured by Nippon Denshoku Industries Co., Ltd. was used and measured in accordance with JIS K 7136.

(2)60度鏡面光澤度(2) 60 degree specular gloss

使用日本電色工業(股)製透明測定計「VG2000」，並依照JIS K 7105測定。A transparent measuring instrument "VG2000" manufactured by Nippon Denshoku Industries Co., Ltd. was used and measured in accordance with JIS K 7105.

(3)影像鮮明度的合計值(3) Total value of image sharpness

使用SUGA試驗機(股)製影像鮮明性測定器「ICM-10」，並依照JIS K 7105測定。以5種類的狹縫(狹縫寬度：0.125毫米、0.25毫米、0.5毫米、1毫米及2毫米)的合計值作為影像鮮明度的合計值。The image sharpness tester "ICM-10" manufactured by the SUGA tester (unit) was used and measured in accordance with JIS K 7105. The total value of the five types of slits (slit width: 0.125 mm, 0.25 mm, 0.5 mm, 1 mm, and 2 mm) was used as the total value of the image sharpness.

(4)耐擦傷性(4) Scratch resistance

目視觀察使用鋼絲絨(#0000)擦拭被覆層表面後之受傷的情形。○係表示未受傷。The condition of the wound after wiping the surface of the coating layer with steel wool (#0000) was visually observed. ○ indicates that it is not injured.

(5)表面的算術平均粗糙度Ra(5) Arithmetic mean roughness Ra of the surface

使用MITUTOYO(股)製表面粗糙度測定機「SV30000S4」，並依照JIS B 0601-1994測定硬被覆膜的 最表層(硬被覆層、防眩層或防止反射層)。The surface roughness measuring machine "SV30000S4" manufactured by MITUTOYO Co., Ltd. was used, and the hard coating film was measured in accordance with JIS B 0601-1994. The outermost layer (hard coating, anti-glare layer or anti-reflection layer).

(6)內部霧度值(6) Internal haze value

在100質量丙烯酸系黏著劑[日本CARBIDE公司製、商品名「PE-121」]，添加2質量份異氰酸酯交聯劑[東洋油墨公司製、商品名「BHS-8515」]及100質量份甲苯，來製造黏著劑溶液。在厚度50微米的聚對酞酸乙二酯[東洋紡績公司製、商品名「A4300」]薄膜，以乾燥後的厚度為20微米的方式塗布黏著劑溶液，並在100℃乾燥3分鐘來製造透明黏著薄膜。將所製造的透明黏著薄膜貼在硬被覆膜的硬被覆層、防眩層或防止反射層而作為內部霧度測定用試料。測定該透明黏著薄膜及內部霧度測定用試料的霧度值，將從內部霧度測定用試料的霧度值減去另外測定之透明黏著薄膜的霧度值後之值作為硬被覆膜的內部霧度值。又，同樣地進行測定在實施例及比較例所使用的基材薄膜(三乙酸纖維素薄膜)的內部霧度值時，為小於0.01%係可忽視的值。又，霧度值的測定係使用日本電色工業(股)製霧度計「NDH2000」，並依照JIS K 7136進行測定。2 parts by mass of an isocyanate crosslinking agent (manufactured by Toyo Ink Co., Ltd., trade name "BHS-8515") and 100 parts by mass of toluene were added to a 100-mass acrylic adhesive [manufactured by Japan CARBIDE Co., Ltd., trade name "PE-121"). To make an adhesive solution. A film of polyethylene terephthalate (manufactured by Toyobo Co., Ltd., trade name "A4300") having a thickness of 50 μm was applied with an adhesive solution having a thickness of 20 μm after drying, and dried at 100 ° C for 3 minutes. Transparent adhesive film. The produced transparent adhesive film was attached to the hard coating layer of the hard coating film, the antiglare layer, or the antireflection layer, and used as a sample for internal haze measurement. The haze value of the transparent adhesive film and the internal haze measurement sample was measured, and the haze value of the internal haze measurement sample was subtracted from the haze value of the separately measured transparent adhesive film as a hard coating film. Internal haze value. In the same manner, when the internal haze value of the base film (triacetate film) used in the examples and the comparative examples was measured, the value was negligible to be less than 0.01%. In addition, the haze value was measured by using a haze meter "NDH2000" manufactured by Nippon Denshoku Industries Co., Ltd., and measured in accordance with JIS K 7136.

(7)耀眼(7) dazzling

在將SHARP公司製液晶顯示器「AQUOS LC-20AX5」之表面的偏光板後的表面，設置使用在實施例及比較例所得到的硬被覆膜所製造的偏光板，並目視觀察亮度的閃爍。又，偏光板係在使拉伸聚乙烯醇吸附碘而成之偏光鏡的一面貼合硬被覆膜，並在另外一面貼合三乙酸纖維素(以下稱為「TAC」)薄膜[KONICA MINOLTA OPTO(股)製、商 品名「KC8UX2M」來製造。A polarizing plate produced by using the hard coating film obtained in the examples and the comparative examples was placed on the surface of the surface of the polarizing plate on the surface of the liquid crystal display "AQUOS LC-20AX5" manufactured by the SHARP company, and the flicker of the brightness was visually observed. In addition, the polarizing plate is bonded to the hard coating film on one side of the polarizer in which the polyvinyl alcohol is adsorbed by the stretching of the polyvinyl alcohol, and the cellulose triacetate (hereinafter referred to as "TAC") film is bonded to the other surface [KONICA MINOLTA] OPTO (share) system, business The product name is "KC8UX2M".

(8)相分離狀態(8) Phase separation state

使用KEYENCE公司製數位顯微鏡「VHX-100」，簡易地確認表面的相分離狀態，並使用比例尺測定海/島結構的大小，且測定觀察區域中央部的任意10個島的直徑。實施例5係在形成防眩性硬被覆層之前，對透明硬被覆層進行測定。因為實施例6之防止反射層為較薄之0.1微米，所以能夠觀察硬被覆層的相分離。Using a digital microscope "VHX-100" manufactured by KEYENCE Co., Ltd., the phase separation state of the surface was easily confirmed, and the size of the sea/island structure was measured using a scale, and the diameter of any 10 islands in the central portion of the observation region was measured. In Example 5, the transparent hard coating layer was measured before the formation of the antiglare hard coating layer. Since the antireflection layer of Example 6 was 0.1 μm thinner, phase separation of the hard coating layer could be observed.

調製例1兼具有內部霧度、表面凹凸形狀雙方之防眩性硬被覆層用被覆劑(A)之調製Preparation Example 1 Modulation of the anti-glare hard coating layer coating agent (A) having both internal haze and surface unevenness

將100質量份(A)活性能量線硬化型化合物之紫外線(UV)硬化型硬被覆劑[JSR(股)製、商品名「OPSTAR TU4086」、58質量%含有反應性二氧化矽微粒子及多官能丙烯酸酯之活性能量線硬化型化合物、2質量%防靜電劑、35質量%甲基異丁基酮、5質量%甲基乙基酮]、23質量份(B)熱塑性樹脂之聚酯樹脂[東洋紡績(股)製、商品名「VYLON20SS」、30質量%聚酯樹脂、56質量%甲苯、14質量%甲基乙基酮]、2.4質量份光聚合引發劑之1-羥基環己基苯基酮[CIBA SPECIALTY CHEMICALS(股)製、商品名「IRGACURE184」、固體成分100%]及稀釋溶劑之35質量份乙基賽路蘇、85質量份環己酮均勻地混合，來調製固體成分28質量%兼具有內部霧度、表面凹凸形狀雙方之防眩性硬被覆層用被覆劑(A)。又，上述的溶劑之中，只有乙基賽路蘇係(B)成分的弱溶劑(D)，此外係(A)成分、(B)成分的 良溶劑(C)。(C):(D)的比例為80.1:19.9。Ultraviolet (UV) hardening type hard coating agent of 100 parts by mass of (A) active energy ray-curable compound [JSR (manufactured by JSR), trade name "OPSTAR TU4086", 58% by mass containing reactive cerium oxide microparticles and polyfunctional Acrylate active energy ray-curable compound, 2% by mass antistatic agent, 35 mass% methyl isobutyl ketone, 5% by mass methyl ethyl ketone], 23 parts by mass (B) thermoplastic resin of polyester resin [ Toyo Textiles Co., Ltd., trade name "VYLON20SS", 30% by mass of polyester resin, 56% by mass of toluene, 14% by mass of methyl ethyl ketone), and 2.4 parts by mass of 1-hydroxycyclohexylphenyl group of photopolymerization initiator A ketone [manufactured by CIBA SPECIALTY CHEMICALS (trade name), trade name "IRGACURE 184", solid content 100%] and 35 parts by mass of a diluted solvent, ethyl sirolimus, and 85 parts by mass of cyclohexanone are uniformly mixed to prepare a solid component 28 mass. % The coating agent (A) for an antiglare hard coating layer having both internal haze and surface unevenness. Further, among the above solvents, only the weak solvent (D) of the ethyl sirolimus-based (B) component, and the components (A) and (B) are contained. Good solvent (C). (C): The ratio of (D) is 80.1:19.9.

調製例2具有內部霧度但是表面凹凸少之硬被覆層用被覆劑(B)之調製Modification Example 2 Modulation of hard coating layer coating agent (B) having internal haze but having few surface irregularities

將100質量份(A)活性能量線硬化型化合物之紫外線(UV)硬化型硬被覆劑[JSR(股)製、商品名「OPSTAR TU4086」、58質量%含有反應性二氧化矽微粒子及多官能丙烯酸酯之活性能量線硬化型化合物、2質量%防靜電劑、35質量%甲基異丁基酮、5質量%甲基乙基酮]、23質量份(B)熱塑性樹脂之聚酯樹脂[東洋紡績(股)製、商品名「VYLON20SS」、30質量%聚酯樹脂、56質量%甲苯、14質量%甲基乙基酮]、2.4質量份光聚合引發劑之1-羥基環己基苯基酮[CIBA SPECIALTY CHEMICALS(股)製、商品名「IRGACURE184」、固體成分100%]及稀釋溶劑之60質量份甲基乙基酮、60質量份環己酮均勻地混合，來調製固體成分為28質量%之具有內部霧度但是表面凹凸少之硬被覆層用被覆劑(B)。Ultraviolet (UV) hardening type hard coating agent of 100 parts by mass of (A) active energy ray-curable compound [JSR (manufactured by JSR), trade name "OPSTAR TU4086", 58% by mass containing reactive cerium oxide microparticles and polyfunctional Acrylate active energy ray-curable compound, 2% by mass antistatic agent, 35 mass% methyl isobutyl ketone, 5% by mass methyl ethyl ketone], 23 parts by mass (B) thermoplastic resin of polyester resin [ Toyo Textiles Co., Ltd., trade name "VYLON20SS", 30% by mass of polyester resin, 56% by mass of toluene, 14% by mass of methyl ethyl ketone), and 2.4 parts by mass of 1-hydroxycyclohexylphenyl group of photopolymerization initiator Ketone [manufactured by CIBA SPECIALTY CHEMICALS (trade name), trade name "IRGACURE 184", solid content: 100%] and 60 parts by mass of methyl ethyl ketone and 60 parts by mass of cyclohexanone in a diluent solvent were uniformly mixed to prepare a solid content of 28 The coating agent (B) for a hard coating layer having an internal haze of a mass % but having a small surface unevenness.

調製例3在調製例2的被覆劑添加二氧化矽微粒子之防眩性硬被覆層用被覆劑(C)的調製Preparation Example 3 Modification of Anti-glare Hard Coating Layer Coating Agent (C) by Adding Cerium Oxide Fine Particles to the Coating Agent of Preparation Example 2

將100質量份(A)活性能量線硬化型化合物之紫外線(UV)硬化型硬被覆劑[JSR(股)製、商品名「OPSTAR TU4086」、58質量%含有反應性二氧化矽微粒子及多官能丙烯酸酯之活性能量線硬化型化合物、2質量%防靜電劑、35質量%甲基異丁基酮、5質量%甲基乙基酮]、23質量份(B)熱塑性樹脂之聚酯樹脂[東洋紡績(股)製、商品名 「VYLON20SS」、30質量%聚酯樹脂、56質量%甲苯、14質量%甲基乙基酮]、2.4質量份光聚合引發劑之1-羥基環己基苯基酮[CIBA SPECIALTY CHEMICALS(股)製、商品名「IRGACURE184」、固體成分100%]、1.0質量份二氧化矽微粒子[富士SILISIA化學(股)製、商品名「SAIROHOBIK 702」、固體成分100%]及稀釋溶劑之60質量份甲基乙基酮、60質量份環己酮均勻地混合，來調製固體成分為28質量%之在調製例2的被覆劑添加二氧化矽微粒子之防眩性硬被覆層用被覆劑(C)，亦即調製兼具有內部霧度、表面凹凸形狀雙方之防眩性硬被覆層用被覆劑(C)。Ultraviolet (UV) hardening type hard coating agent of 100 parts by mass of (A) active energy ray-curable compound [JSR (manufactured by JSR), trade name "OPSTAR TU4086", 58% by mass containing reactive cerium oxide microparticles and polyfunctional Acrylate active energy ray-curable compound, 2% by mass antistatic agent, 35 mass% methyl isobutyl ketone, 5% by mass methyl ethyl ketone], 23 parts by mass (B) thermoplastic resin of polyester resin [ Toyo Textile Co., Ltd., product name "VYLON20SS", 30% by mass of polyester resin, 56% by mass of toluene, 14% by mass of methyl ethyl ketone), and 2.4 parts by mass of 1-hydroxycyclohexyl phenyl ketone of photopolymerization initiator [manufactured by CIBA SPECIALTY CHEMICALS Co., Ltd. , product name "IRGACURE 184", solid content 100%], 1.0 part by mass of cerium oxide microparticles [Fuji SILISIA Chemical Co., Ltd., trade name "SAIROHOBIK 702", solid content 100%] and 60 parts by mass of methyl ester diluent solvent Ethyl ketone and 60 parts by mass of cyclohexanone were uniformly mixed to prepare a coating agent (C) for an antiglare hard coating layer in which a solid content of 28% by mass of the coating agent of Preparation Example 2 was added with cerium oxide fine particles. In other words, the coating agent (C) for an antiglare hard coating layer having both internal haze and surface unevenness is prepared.

調製例4未具有內部霧度但是具有表面凹凸之防眩層用被覆劑(D)的調製Modification Example 4 Modulation of the anti-glare layer coating agent (D) having no internal haze but having surface irregularities

將84質量份活性能量線硬化型化合物之紫外線(UV)硬化型硬被覆劑[大日精化製、商品名「SEIKABEAM EXF-01L(NS)」、95質量%含有多官能丙烯酸酯之活性能量線硬化型化合物、5質量%光引發劑]、5質量份紫外線(UV)硬化型硬被覆劑[大日精化製、商品名「SEIKABEAM EXF-01L(NE2)」、85質量%含有多官能丙烯酸酯之活性能量線硬化型化合物、10質量%平均粒徑為7微米的二氧化矽填料、5質量%光引發劑]、及稀釋溶劑之130質量份乙基賽路蘇均勻地混合，來調製未具有內部霧度但是具有表面凹凸之防眩層用被覆劑(D)。又，塗布該被覆劑(D)並乾燥硬化所得到的層係具有硬被覆性者。An ultraviolet (UV) hardening type hard coating agent of 84 parts by mass of an active energy ray-curable compound [manufactured by Daisei Seiki Co., Ltd., trade name "SEIKABEAM EXF-01L (NS)", and 95% by mass of active energy ray containing polyfunctional acrylate) Hardening type compound, 5% by mass of photoinitiator], and 5 parts by mass of ultraviolet (UV) hardening type hard coating agent [manufactured by Daisei Seiki Co., Ltd., trade name "SEIKABEAM EXF-01L (NE2)"), and 85 mass% of polyfunctional acrylate The active energy ray-curable compound, 10% by mass of a cerium oxide filler having an average particle diameter of 7 μm, a 5% by mass photoinitiator, and 130 parts by mass of a diluted solvent of ethyl sirolius are uniformly mixed to prepare A coating agent (D) for an antiglare layer having internal haze but having surface irregularities. Further, the layer obtained by applying the coating agent (D) and drying and hardening has a hard coating property.

調製例5防止反射層形成用被覆劑(E)的調製Modification Example 5 Preparation of Coating (E) for Preventing Reflection Layer Formation

將100質量份活性能量線硬化型化合物之紫外線(UV)硬化型硬被覆劑[荒川化學工業(股)製、商品名「BEAMSET 575CB」、固體成分100%]、80質量份多孔性二氧化矽粒子的甲基異丁基酮(MIBK)分散體[觸媒化成工業(股)製、商品名「ELCOM RT-1002SIV」、固體成分21質量%、多孔性二氧化矽粒子：比重1.8、折射率1.30、平均粒徑60奈米]混合後，以總體的固體成分濃度為2質量%的方式使用MIBK稀釋，來調製防止反射層形成用被覆劑(E)。Ultraviolet (UV) hardening type hard coating agent of 100 parts by mass of active energy ray-curable compound [manufactured by Arakawa Chemical Industry Co., Ltd., trade name "BEAMSET 575CB", solid content: 100%], 80 parts by mass of porous cerium oxide Methyl isobutyl ketone (MIBK) dispersion of particles [manufactured by Catalyst Chemical Co., Ltd., trade name "ELCOM RT-1002SIV", solid content 21% by mass, porous cerium oxide particles: specific gravity 1.8, refractive index 1.30. The average particle diameter is 60 nm. After mixing, the coating agent (E) for preventing reflection layer formation is prepared by diluting with MIBK so that the total solid content concentration is 2% by mass.

實施例1Example 1

在厚度80微米的TAC薄膜[KONICA MINOLTA(股)製、商品名「KC8UX2M」的表面，以硬化膜厚度為約3.5微米的方式使用繞線棒塗布調製劑1所得到的被覆劑(A)。使用70℃的烘箱乾燥1分鐘後使用高壓水銀燈照射300 mJ/cm2 的紫外線，形成兼具有內部霧度、表面凹凸形狀雙方之防眩性硬被覆層，來製造硬被覆膜。The coating agent (A) obtained by coating the preparation 1 with a wire bar so that the thickness of the cured film was about 3.5 μm on the surface of a TAC film (KONICA MINOLTA Co., Ltd., trade name "KC8UX2M") having a thickness of 80 μm was used. After drying in an oven at 70 ° C for 1 minute, ultraviolet rays of 300 mJ/cm 2 were irradiated with a high-pressure mercury lamp to form an anti-glare hard coating layer having both internal haze and surface unevenness, thereby producing a hard coating film.

該硬被覆膜的性能係如表1所示。The properties of the hard coating are shown in Table 1.

實施例2Example 2

在厚度80微米的TAC薄膜[KONICA MINOLTA(股)製、商品名「KC8UX2M」的表面，以硬化膜厚度為約3.5微米的方式使用繞線棒塗布調製劑2所得到的被覆劑(B)。使用70℃的烘箱乾燥1分鐘後使用高壓水銀燈照射300 mJ/cm2 的紫外線，形成硬被覆層(透明硬被覆層)，來製造具有內部霧度之硬被覆層。The coating agent (B) obtained by coating the preparation 2 with a wire bar so that the thickness of the cured film was about 3.5 μm on the surface of a TAC film (KONICA MINOLTA Co., Ltd., trade name "KC8UX2M") having a thickness of 80 μm was used. After drying in an oven at 70 ° C for 1 minute, ultraviolet rays of 300 mJ/cm 2 were irradiated with a high-pressure mercury lamp to form a hard coating layer (transparent hard coating layer) to produce a hard coating layer having internal haze.

該硬被覆膜的性能係如表1所示。The properties of the hard coating are shown in Table 1.

實施例3Example 3

在厚度80微米的TAC薄膜[KONICA MINOLTA(股)製、商品名「KC8UX2M」的表面，以硬化膜厚度為約3.5微米的方式使用繞線棒塗布調製劑3所得到的被覆劑(C)。使用70℃的烘箱乾燥1分鐘後使用高壓水銀燈照射300 mJ/cm2 的紫外線，形成兼具有內部霧度、表面凹凸形狀雙方之防眩性硬被覆層，來得到硬被覆膜。The coating agent (C) obtained by coating the preparation 3 with a wire bar so that the thickness of the cured film was about 3.5 μm on the surface of a TAC film (KONICA MINOLTA Co., Ltd., trade name "KC8UX2M") having a thickness of 80 μm was used. After drying in an oven at 70 ° C for 1 minute, ultraviolet rays of 300 mJ/cm 2 were irradiated with a high-pressure mercury lamp to form an anti-glare hard coating layer having both internal haze and surface unevenness, to obtain a hard coating film.

該硬被覆膜的性能係如表1所示。The properties of the hard coating are shown in Table 1.

實施例4Example 4

在實施例2所得到具有內部霧度之透明的硬被覆層以硬化膜厚度為約3.5微米的方式使用繞線棒塗布調製劑1所得到的被覆劑(A)。使用70℃的烘箱乾燥1分鐘後使用高壓水銀燈照射300 mJ/cm2 的紫外線，形成兼具有內部霧度、表面凹凸形狀雙方之防眩性硬被覆層，來得到硬被覆膜。The hard coating layer having the internal haze obtained in Example 2 was coated with the coating agent 1 obtained by using the wire bar coating so that the thickness of the cured film was about 3.5 μm. After drying in an oven at 70 ° C for 1 minute, ultraviolet rays of 300 mJ/cm 2 were irradiated with a high-pressure mercury lamp to form an anti-glare hard coating layer having both internal haze and surface unevenness, to obtain a hard coating film.

該硬被覆膜的性能係如表1所示。The properties of the hard coating are shown in Table 1.

實施例5Example 5

在實施例2所得到具有內部霧度之透明的硬被覆層以硬化膜厚度為約3.5微米的方式使用繞線棒塗布調製劑4所得到的防眩層用被覆劑(D)。使用70℃的烘箱乾燥1分鐘後使用高壓水銀燈照射300 mJ/cm2 的紫外線，形成兼具有內部霧度、表面凹凸形狀雙方之防眩性硬被覆層，來得到硬被覆膜。In the hard coating layer having a transparent haze obtained in Example 2, the coating agent (D) for an antiglare layer obtained by coating the preparation agent 4 with a wire bar was used so that the thickness of the cured film was about 3.5 μm. After drying in an oven at 70 ° C for 1 minute, ultraviolet rays of 300 mJ/cm 2 were irradiated with a high-pressure mercury lamp to form an anti-glare hard coating layer having both internal haze and surface unevenness, to obtain a hard coating film.

該硬被覆膜的性能係如表1所示。The properties of the hard coating are shown in Table 1.

實施例6Example 6

在實施例1所得到具有內部霧度之透明的硬被覆層以硬化膜厚度為約0.1微米的方式使用繞線棒塗布調製劑5所得到的防止反射層形成用被覆劑(E)。使用70℃的烘箱乾燥1分鐘後使用高壓水銀燈照射300 mJ/cm2 的紫外線，形成兼具有內部霧度、表面凹凸形狀雙方之防眩性硬被覆層，來得到硬被覆膜。In the hard coating layer having the internal haze obtained in Example 1, the coating material for forming an antireflection layer (E) obtained by coating the preparation agent 5 with a wire bar having a cured film thickness of about 0.1 μm was used. After drying in an oven at 70 ° C for 1 minute, ultraviolet rays of 300 mJ/cm 2 were irradiated with a high-pressure mercury lamp to form an anti-glare hard coating layer having both internal haze and surface unevenness, to obtain a hard coating film.

該硬被覆膜的性能係如表1所示。The properties of the hard coating are shown in Table 1.

實施例7Example 7

在厚度80微米的TAC薄膜[KONICA MINOLTA(股)製、商品名「KC8UX2M」的表面，以硬化膜厚度為約3.5微米的方式使用繞線棒塗布調製劑2所得到的被覆劑(B)。使用70℃的烘箱乾燥1分鐘後，對其貼合表面粗糙度Ra=0.3微米的凹凸薄膜，並在該狀態使用高壓水銀燈照射150 mJ/cm2 的紫外線，將凹凸薄膜剝離後並以300 mJ/cm2 的紫外線照射，形成兼具有內部霧度、表面凹凸形狀雙方之防眩性硬被覆層，來得到硬被覆膜。The coating agent (B) obtained by coating the preparation 2 with a wire bar so that the thickness of the cured film was about 3.5 μm on the surface of a TAC film (KONICA MINOLTA Co., Ltd., trade name "KC8UX2M") having a thickness of 80 μm was used. After drying in an oven at 70 ° C for 1 minute, an uneven film having a surface roughness Ra of 0.3 μm was attached thereto, and in this state, ultraviolet rays of 150 mJ/cm 2 were irradiated with a high-pressure mercury lamp, and the uneven film was peeled off and 300 mJ. Ultraviolet irradiation of /cm 2 forms an anti-glare hard coating layer having both internal haze and surface unevenness to obtain a hard coating film.

該硬被覆膜的性能係如表1所示。The properties of the hard coating are shown in Table 1.

又，凹凸薄膜係使用在厚度50微米的聚對酞酸乙二酯，設置由100質量份紫外線硬化型樹脂「SEIKABEAM EXF-01L(NS)」、10質量份二氧化矽填料(平均粒徑2微米)的混合物所構成之厚度為2微米的硬化層而成者。Further, the uneven film was made of polyethylene terephthalate having a thickness of 50 μm, and 100 parts by mass of an ultraviolet curable resin "SEIKABEAM EXF-01L (NS)" and 10 parts by mass of a cerium oxide filler (average particle diameter 2) were used. The mixture of micron) is composed of a hardened layer having a thickness of 2 μm.

比較例1Comparative example 1

在厚度80微米的TAC薄膜[KONICA MINOLTA(股) 製、商品名「KC8UX2M」的表面，以硬化膜厚度為約3.5微米的方式使用繞線棒塗布調製劑4所得到的防眩層用被覆劑(D)。使用70℃的烘箱乾燥1分鐘後，使用高壓水銀燈照射300 mJ/cm2 的紫外線，形成未具有內部霧度但是表面具有凹凸形狀之硬被覆膜。The coating agent for an anti-glare layer obtained by coating the preparation agent 4 with a wire rod having a thickness of a hardened film of about 3.5 μm on a surface of a TAC film (KONICA MINOLTA Co., Ltd., trade name "KC8UX2M") having a thickness of 80 μm (D). After drying in an oven at 70 ° C for 1 minute, ultraviolet rays of 300 mJ/cm 2 were irradiated with a high-pressure mercury lamp to form a hard coating film having no internal haze but having a concave-convex shape on the surface.

該硬被覆膜的性能係如表1所示。The properties of the hard coating are shown in Table 1.

在相分離狀態()內的數值係表示島的大小(單位微米)。 The values in the phase separation state () indicate the size of the island (in micrometers).

[註]實施例1：形成具有兼具有內部霧度、表面凹凸形狀雙方的相分離結構之防眩性硬被覆層之硬被覆膜。[Note] Example 1: A hard coating film having an anti-glare hard coating layer having a phase separation structure of both internal haze and surface unevenness was formed.

實施例2：形成具有內部霧度但是表面凹凸少的相分離結構之透明硬被覆層之硬被覆膜。Example 2: A hard coating film of a transparent hard coating layer having a phase separation structure having an internal haze but a small surface unevenness was formed.

實施例3：在實施例2的被覆劑添加填料而成之具有內部霧度、表面凹凸形狀的相分離結構之防眩性硬被覆層之硬被覆膜。Example 3: A hard coating film of an antiglare hard coating layer having a phase separation structure of internal haze and surface unevenness, which was obtained by adding a filler to the coating material of Example 2.

實施例4：在實施例2的透明硬被覆層上層積具有內部霧度、表面凹凸形狀的相分離結構之防眩層而成之硬被覆膜。Example 4: A hard coating film having an anti-glare layer having a phase separation structure of internal haze and surface unevenness was laminated on the transparent hard coating layer of Example 2.

實施例5：在實施例2的透明硬被覆層上，層積無內部霧度但是藉由添加填料而具有表面凹凸形狀的防眩層而成之硬被覆膜。Example 5: On the transparent hard coating layer of Example 2, a hard coating film having an internal haze but having an antiglare layer having a surface uneven shape by adding a filler was laminated.

實施例6：在實施例1的防眩性硬被覆層上，層積防止反射層而成之硬被覆膜。Example 6: A hard coating film in which an antireflection layer was formed was laminated on the antiglare hard coating layer of Example 1.

實施例7：在實施例2的透明硬被覆層上，形成表面凹凸形狀而成之硬被覆膜。Example 7: A hard coating film having a surface uneven shape was formed on the transparent hard coating layer of Example 2.

比較例1：具有含填料的防眩性硬被覆層之硬被覆膜。幾乎無內部霧度。Comparative Example 1: A hard coating film having an antiglare hard coating layer containing a filler. There is almost no internal haze.

[產業上之利用可能性][Industry use possibility]

本發明的硬被覆膜能夠賦予需要的光擴散性，較佳是具有在表面形成有凹凸之硬被覆層，能夠使用作為防眩性薄膜，作為能夠有效地抑制特別是液晶顯示裝置等具備彩色濾光片之高精密型影像顯示裝置的耀眼之防眩性薄膜係適合的。The hard coating film of the present invention can impart a desired light diffusing property, and preferably has a hard coating layer having irregularities formed on the surface thereof, and can be used as an anti-glare film, and can effectively suppress the color of a liquid crystal display device or the like. A dazzling anti-glare film of a high-precision image display device of a filter is suitable.

Claims (3)

一種硬被覆膜，其特徵係在基材薄膜上具有以質量比100：0.3~100：50的比例含有(A)活性能量線硬化型化合物的硬化物、及(B)熱塑性樹脂之硬被覆層，在該硬被覆層中，該(A)成分與(B)成分係形成相分離結構，該相分離結構係(1)均勻的海/島結構，其島的大小為直徑為0.1微米~20微米的海/島結構，且該硬被覆層之內部霧度值為3~80%，該硬被覆層係該硬被覆層表面之依照JIS B 0601-1994測定之算術平均粗糙度Ra為0.01微米以下的透明硬被覆層。 A hard coating film comprising a cured product of (A) an active energy ray-curable compound and (B) a hard coating of a thermoplastic resin in a mass ratio of 100:0.3 to 100:50 on a base film. In the hard coating layer, the (A) component and the (B) component form a phase separation structure (1) a uniform sea/island structure, and the island has a diameter of 0.1 μm. a 20 μm sea/island structure, and the internal haze value of the hard coating layer is 3 to 80%, and the hard coating layer has an arithmetic mean roughness Ra of 0.01 on the surface of the hard coating layer in accordance with JIS B 0601-1994. A transparent hard coating layer below micrometers. 如申請專利範圍第1項之硬被覆膜，其內部霧度值為5~80%。 For example, the hard coating film of the first application of the patent scope has an internal haze value of 5 to 80%. 如申請專利範圍第1或2項之硬被覆膜，係使用於具備彩色濾光片之影像顯示裝置。The hard coating film of claim 1 or 2 is used for an image display device having a color filter.
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