TWI608937B - Hard coating and transparent conductive film - Google Patents

Hard coating and transparent conductive film Download PDF

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Publication number
TWI608937B
TWI608937B TW102141042A TW102141042A TWI608937B TW I608937 B TWI608937 B TW I608937B TW 102141042 A TW102141042 A TW 102141042A TW 102141042 A TW102141042 A TW 102141042A TW I608937 B TWI608937 B TW I608937B
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hard coating
coating layer
layer
film
mass
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TW102141042A
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TW201425035A (en
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Yutaka Toyoshima
Kiyoshige Maeda
Tatsuro Tsuchimoto
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Toray Advanced Film Co Ltd
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    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • 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
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers

Description

硬被覆膜及透明導電性膜 Hard coating and transparent conductive film

本發明係關於一種透明性高且平滑性與抗結塊性良好的硬被覆膜，詳言之，關於一種適合於透明導電性膜的硬被覆膜。 The present invention relates to a hard coating film having high transparency, good smoothness and anti-caking property, and more particularly to a hard coating film suitable for a transparent conductive film.

在基材膜上積層有硬被覆層的硬被覆膜係作為顯示器或觸控面板之表面保護、或是作為觸控面板用電極膜(觸控面板用透明導電性膜)之基材膜使用。使用於該等用途之硬被覆膜要求透明性高、且平滑性與抗結塊性良好。 A hard coating film in which a hard coating layer is laminated on a base film is used as a surface protection of a display or a touch panel, or as a base film of an electrode film for a touch panel (a transparent conductive film for a touch panel) . The hard coating film used for such applications is required to have high transparency and good smoothness and blocking resistance.

為了改良硬被覆膜或聚酯膜之平滑性或抗結塊性，有人提案在表面設置突起(專利文獻1、2)。 In order to improve the smoothness or anti-caking property of the hard coating film or the polyester film, it has been proposed to provide protrusions on the surface (Patent Documents 1 and 2).

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開平7-314628號公報 [Patent Document 1] Japanese Patent Laid-Open No. Hei 7-314628

[專利文獻2]日本特開2000-211082號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2000-211082

然而，在上述專利文獻所揭示的技術中，尚未達到同時使透明性、平滑性與抗結塊性充分符合。 However, in the technique disclosed in the above patent documents, the transparency, smoothness, and anti-caking property are sufficiently matched at the same time.

因而，本發明之目的係有鑒於上述習知技術之問題，在於提供一種透明性高且平滑性與抗結塊性良好的硬被覆膜。本發明之其他目的係在於提供一種適合於透明導電性膜的硬被覆膜。 Accordingly, the object of the present invention is to provide a hard coating film having high transparency, smoothness, and excellent blocking resistance in view of the above-described problems. Another object of the present invention is to provide a hard coating film suitable for a transparent conductive film.

本發明之上述目的係藉由下列之1)至15)中任一項之構成所達成。 The above object of the present invention is achieved by the constitution of any one of the following 1) to 15).

1)一種硬被覆膜，其特徵係在基材膜之至少一側面具備含有粒子之第1硬被覆層，在第1硬被覆層表面，由該粒子構成之突起係以每100μm2存在300至4000個之密度，第1硬被覆層表面的中心線平均粗糙度(Ra1)小於30nm、霧度值小於1.5%。 1) A hard coating film comprising a first hard coating layer containing particles on at least one side surface of a base film, and a protrusion composed of the particles on the surface of the first hard coating layer is 300 per 100 μm 2 At a density of 4,000, the center line average roughness (Ra1) of the surface of the first hard coating layer is less than 30 nm, and the haze value is less than 1.5%.

2)在1)記載之硬被覆膜，其中該粒子之平均粒徑(r)為0.05至0.5μm。 2) The hard coating film according to 1), wherein the particles have an average particle diameter (r) of 0.05 to 0.5 μm.

3)在1)或2)記載之硬被覆膜，其中該粒子之平均粒徑(r)對第1硬被覆層之厚度(d)的比例(r/d)為0.01至0.30。 3) The hard coating film according to 1) or 2), wherein a ratio (r/d) of the average particle diameter (r) of the particles to the thickness (d) of the first hard coating layer is 0.01 to 0.30.

4)在1)至3)中任一項記載之硬被覆膜，其中該突起之平均直徑為0.03至0.3μm，該突起之平均高度為0.03至0.3μm。 4) The hard coating film according to any one of 1) to 3, wherein the protrusion has an average diameter of 0.03 to 0.3 μm, and the protrusion has an average height of 0.03 to 0.3 μm.

5)在1)至4)中任一項記載之硬被覆膜，其中該突起之平均間隔為0.10至0.70μm。 The hard coating film according to any one of 1) to 4, wherein the average interval of the protrusions is 0.10 to 0.70 μm.

6)在1)至5)中任一項記載之硬被覆膜，其中第1硬被覆層之厚度(d)為0.5μm以上小於10μm。 The hard coating film according to any one of 1 to 5, wherein the thickness (d) of the first hard coating layer is 0.5 μm or more and less than 10 μm.

7)在1)至6)中任一項記載之硬被覆膜，其中 在基材膜與第1硬被覆層之間具有樹脂層，該樹脂層係其厚度為0.005至0.3μm，且含有平均粒徑為樹脂層厚度的1.3倍以上之粒子。 7) The hard coating film according to any one of 1) to 6), wherein Between the base film and the first hard coating layer, a resin layer having a thickness of 0.005 to 0.3 μm and containing particles having an average particle diameter of 1.3 times or more the thickness of the resin layer is provided.

8)在1)至7)中任一項記載之硬被覆膜，其中基材膜為聚對苯二甲酸乙二酯，在基材膜與第1硬被覆層之間具有折射率為1.55至1.61之樹脂層。 The hard coating film according to any one of 1), wherein the base film is polyethylene terephthalate, and the refractive index is 1.55 between the base film and the first hard coating layer. To the resin layer of 1.61.

9)在1)至8)中任一項記載之硬被覆膜，其中在基材膜與第1硬被覆層之間具備濕潤張力為52mN/m以下之樹脂層。 The hard coating film according to any one of the above aspects, wherein a resin layer having a wet tension of 52 mN/m or less is provided between the base film and the first hard coating layer.

10)在9)記載之硬被覆膜，其中第1硬被覆層之厚度小於2μm。 10) The hard coating film according to 9), wherein the thickness of the first hard coating layer is less than 2 μm.

11)在1)至10)中任一項記載之硬被覆膜，其中第1硬被覆層中所含之粒子係選自包含已實施用以減少粒子表面自由能之表面處理的無機粒子、及粒子表面已被疏水化處理的無機粒子之群組中的至少一種。 The hard coating film according to any one of 1 to 10, wherein the particles contained in the first hard coating layer are selected from the group consisting of inorganic particles having a surface treatment for reducing the surface free energy of the particles, And at least one of the group of inorganic particles whose surface has been hydrophobized.

12)在11)記載之硬被覆膜，其中為了獲得已實施用以減少該粒子表面自由能之表面處理的無機粒子之表面處理為下列(I)或(II)：(I)使用選自包含由以下列通式(1)所示之具有氟原子之有機矽烷化合物、該有機矽烷化合物之水解物、與該有機矽烷水解物之部分縮合物之群組中的至少一種化合物而表面處理；CnF2n+1-(CH2)m-Si(Q)3…通式(1)(於通式(1)中，n係表示1至10之整數、m係表示1至5之整數。Q係表示碳數1至5之烷氧基或鹵素原子)； (II)以下列通式(2)所示之化合物處理，進一步以下列通式(3)所示之氟化物實施表面處理；B-R4-SiR5 n(OR6)3-n…通式(2) 12) The hard coating film according to 11), wherein the surface treatment for obtaining the inorganic particles which have been subjected to the surface treatment for reducing the surface free energy of the particles is the following (I) or (II): (I) is selected from the group consisting of And comprising at least one compound selected from the group consisting of an organodecane compound having a fluorine atom represented by the following formula (1), a hydrolyzate of the organodecane compound, and a partial condensate of the organodecane hydrolysate; C n F 2n+1 -(CH 2 ) m -Si(Q) 3 Formula (1) (In the formula (1), n represents an integer of 1 to 10, and m represents an integer of 1 to 5 Q is alkoxy or a halogen atom having a carbon number of 1 to 5; (II) is treated with a compound represented by the following formula (2), and further subjected to surface treatment with a fluoride represented by the following formula (3) ;BR 4 -SiR 5 n (OR 6 ) 3-n ...general formula (2)

D-R7-Rf2…通式(3)(於通式(2)與(3)中，B與D係各自獨立地表示反應性部位，R4與R7係各自獨立地表示碳數1至3之伸烷基、或是由該伸烷基所衍生的酯結構，R5與R6係各自獨立地表示氫或碳數1至4之烷基、Rf2係表示氟烷基，n係表示0至2之整數)。 DR 7 -Rf 2 (3) (In the general formulae (2) and (3), B and D each independently represent a reactive moiety, and R 4 and R 7 each independently represent a carbon number of 1 to An alkylene group of 3 or an ester structure derived from the alkylene group, R 5 and R 6 each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms, and Rf 2 represents a fluoroalkyl group, and the n system is Represents an integer from 0 to 2.)

13)在11)記載之硬被覆膜，其中可用於為了獲得經疏水化處理該粒子表面之無機粒子的疏水化處理之疏水性化合物為選自包含具有碳數4以上之氟烷基與反應性部位之氟化物、具有碳數8以上之烴基與反應性部位之長鏈烴化合物、與具有矽氧烷基與反應性部位之聚矽氧化合物之群組中的至少一種化合物。 13) The hard coating film according to 11), wherein the hydrophobic compound which can be used for obtaining the hydrophobization treatment of the inorganic particles on the surface of the particle which is hydrophobized is selected from the group consisting of a fluoroalkyl group having a carbon number of 4 or more and a reaction A fluoride of a substance, a long-chain hydrocarbon compound having a hydrocarbon group having 8 or more carbon atoms and a reactive moiety, and at least one compound selected from the group consisting of a phosphonium alkyl group and a polyoxygen compound having a reactive site.

14)在1)至13)中任一項記載之硬被覆膜，其中第1硬被覆層中所含之粒子為二氧化矽粒子。 (14) The hard coating film according to any one of (1) to (13), wherein the particles contained in the first hard coating layer are cerium oxide particles.

15)在1)至14)中任一項記載之硬被覆膜，其中在與該基材膜設置有第1硬被覆層之面的相反面具備第2硬被覆層，在第2硬被覆層表面實質上不存在由粒子構成的突起，且第2硬被覆層表面之中心線平均粗糙度(Ra2)為25nm以下。 The hard coating film according to any one of the aspects of the present invention, wherein the second hard coating layer is provided on the surface opposite to the surface of the base film on which the first hard coating layer is provided, and the second hard coating layer is provided. The surface of the layer has substantially no protrusions composed of particles, and the center line average roughness (Ra2) of the surface of the second hard coating layer is 25 nm or less.

16)一種透明導電性膜，其係在如1)至15)中任一項記載之硬被覆膜之至少一側面具備透明導電膜。 (16) A transparent conductive film comprising a transparent conductive film on at least one side surface of the hard coating film according to any one of 1) to 15).

若根據本發明，能夠提供一種透明性高且平滑性與抗結塊性良好的硬被覆膜。本發明之硬被覆膜係適合於透明導電性膜的基材膜。 According to the present invention, it is possible to provide a hard coating film having high transparency and excellent smoothness and blocking resistance. The hard coating film of the present invention is suitable for a base film of a transparent conductive film.

1、2、3、4、5、11‧‧‧突起 1, 2, 3, 4, 5, 11‧‧

20‧‧‧橫向之直線 20‧‧‧Horizontal straight line

30‧‧‧縱向之直線 30‧‧‧ vertical line

Lmin‧‧‧突起11之直徑 Lmin‧‧‧diameter of protrusion 11

Lmax‧‧‧突起11之最大直徑 Lmax‧‧‧Maximum diameter of protrusion 11

Lc‧‧‧中心 Lc‧‧ Center

P‧‧‧距離 P‧‧‧ distance

第1圖係使用掃描型電子顯微鏡所觀察到的第1硬被覆層表面觀察圖之一例。 Fig. 1 is an example of a surface observation view of a first hard coating layer observed by a scanning electron microscope.

第2圖係示意表示第1硬被覆層表面之突起的平面形狀之圖形。 Fig. 2 is a view schematically showing a planar shape of a projection on the surface of the first hard coating layer.

第3圖係示意表示第1圖之第1硬被覆層表面之示意圖。 Fig. 3 is a schematic view showing the surface of the first hard coating layer in Fig. 1;

第4圖係省略第3圖一部分之示意圖。 Fig. 4 is a schematic view omitting a part of Fig. 3.

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

關於本發明之一實施形態的硬被覆膜係在基材膜之至少一側面具有第1硬被覆層。該第1硬被覆層係含有粒子，在第1硬被覆層表面，每100μm2具有因粒子所造成的300至4000個突起(以下，簡稱為「突起」)。該第1硬被覆層表面的中心線平均粗糙度(Ra1)小於30nm。如此之本實施形態的硬被覆膜係霧度值小於1.5%。 The hard coating film according to an embodiment of the present invention has a first hard coating layer on at least one side surface of the base film. The first hard coating layer contains particles based, hard surface of the first covering layer, 100μm 2 each having a projection 300 to 4000 caused by particles (hereinafter simply referred to as "projections"). The center line average roughness (Ra1) of the surface of the first hard coating layer is less than 30 nm. The hard coating film of this embodiment has a haze value of less than 1.5%.

藉由在第1硬被覆層表面，每第1硬被覆層表面之單位面積(100μm2)具有300至4000個突起，使平滑性與抗結塊性成為良好。 By having 300 to 4000 protrusions per unit area (100 μm 2 ) of the surface of the first hard coating layer on the surface of the first hard coating layer, smoothness and anti-caking property are improved.

突起的個數密度之範圍係每100μm2較佳為400至3500個之範圍，更佳為500至3000個之範圍，進一 步較佳為600至3000個之範圍，特佳為700至2500個之範圍。 The number density of the protrusions is preferably in the range of 400 to 3500 per 100 μm 2 , more preferably in the range of 500 to 3000, further preferably in the range of 600 to 3000, and particularly preferably in the range of 700 to 2500. range.

若使粒子之個數密度每100μm2成為小於300個時，平滑性或抗結塊性將會降低。另一方面，若使粒子之個數密度每100μm2超過4000個時，第1硬被覆層表面之平滑性將會降低而使霧度值變大，硬被覆膜之透明性將會降低。 When the number density of particles is less than 300 per 100 μm 2 , smoothness or anti-caking property will be lowered. On the other hand, when the number density of particles per 100μm 2 4000 time-over, the surface smoothness of the first hard coating layer will lower the haze value becomes large, the hard coating film of the transparency will be reduced.

本實施形態之硬被覆膜係如上所述，特徵之一係在第1硬被覆層表面具有較多的突起，同時第1硬被覆層表面較為平滑且硬被覆膜之霧度值較小。具體而言，重要的是在本實施形態之第1硬被覆層表面的中心線平均粗糙度(Ra1)小於30nm，且硬被覆膜之霧度值小於1.5%。 As described above, the hard coating film of the present embodiment has a large number of protrusions on the surface of the first hard coating layer, and the surface of the first hard coating layer is smooth and the haze value of the hard coating film is small. . Specifically, it is important that the center line average roughness (Ra1) of the surface of the first hard coating layer of the present embodiment is less than 30 nm, and the haze value of the hard coating film is less than 1.5%.

第1硬被覆層表面的中心線平均粗糙度(Ra1)較佳為25nm以下，更佳為20nm以下，特佳為18nm以下。從確保平滑性與抗結塊性之觀點，下限之中心線平均粗糙度(Ra1)較佳為5nm以上，更佳為7nm以上，特佳為9nm以上。 The center line average roughness (Ra1) of the surface of the first hard coating layer is preferably 25 nm or less, more preferably 20 nm or less, and particularly preferably 18 nm or less. From the viewpoint of ensuring smoothness and anti-caking property, the center line average roughness (Ra1) of the lower limit is preferably 5 nm or more, more preferably 7 nm or more, and particularly preferably 9 nm or more.

若使第1硬被覆層表面的中心線平均粗糙度(Ra11成為30nm以上時，平滑性將會降低，硬被覆膜之透明性將會降低。亦即，使得硬被覆膜之霧度值變大。 When the center line average roughness of the surface of the first hard coating layer is 30 nm or more, the smoothness is lowered, and the transparency of the hard coating film is lowered. That is, the haze value of the hard coating film is made. Become bigger.

從實現高的透明性之觀點，重要的是本實施形態之硬被覆膜的霧度值小於1.5%。本實施形態之硬被覆膜的霧度值進一步較佳為1.1%以下，更佳為1.0%以下。雖然下限之霧度值越小越好，但實際為0.01%左右。 From the viewpoint of achieving high transparency, it is important that the hard coating film of the present embodiment has a haze value of less than 1.5%. The haze value of the hard coating film of the present embodiment is more preferably 1.1% or less, still more preferably 1.0% or less. Although the haze value of the lower limit is as small as possible, it is actually about 0.01%.

在第1硬被覆層表面，針對每100μm2具有300至4000個突起，且將第1硬被覆層表面的中心線平均粗糙度(Ra1)作成小於30nm，並使硬被覆膜之霧度值成為小於1.5%，藉由使其在第1硬被覆層中含有平均粒徑(r)為0.05至0.5μm之粒子，在第1硬被覆層表面附近存在較多的該粒子，較佳為在第1硬被覆層表面形成突起。 The surface of the first hard coating layer has 300 to 4000 protrusions per 100 μm 2 , and the center line average roughness (Ra1) of the surface of the first hard coating layer is made smaller than 30 nm, and the haze value of the hard coating film is made. When the particles having an average particle diameter (r) of 0.05 to 0.5 μm are contained in the first hard coating layer, the particles are less than 1.5%, and a large amount of the particles are present in the vicinity of the surface of the first hard coating layer, preferably A protrusion is formed on the surface of the first hard coating layer.

還有，第1硬被覆層中所含之粒子的平均粒徑(r)(μm)與第1硬被覆層的厚度(d)(μm)之比例(r/d)較佳為0.01至0.30。藉此，使第1硬被覆層表面的中心線平均粗糙度(Ra1)變小，也使硬被覆膜的霧度值變小。 Further, the ratio (r/d) of the average particle diameter (r) (μm) of the particles contained in the first hard coating layer to the thickness (d) (μm) of the first hard coating layer is preferably 0.01 to 0.30. . Thereby, the center line average roughness (Ra1) of the surface of the first hard coating layer is made small, and the haze value of the hard coating film is also reduced.

以下，針對構成硬被覆膜之各構成要件詳加說明。 Hereinafter, each constituent element constituting the hard coating film will be described in detail.

[基材膜] [Substrate film]

針對基材膜，較佳使用塑膠膜。作為構成基材膜之材質，例如，可舉出聚對苯二甲酸乙二酯(PET)、聚萘二甲酸乙二酯(PEN)等之聚酯；聚醯亞胺、聚苯硫醚、芳綸、聚丙烯、聚乙烯、聚乳酸、聚氯乙烯、聚碳酸酯、聚甲基丙烯酸甲酯、脂環式丙烯酸樹脂、環烯烴樹脂、三乙醯基纖維素、及混合及/或共聚合該等樹脂之物。能夠適合將未拉伸該等樹脂或是單軸拉伸或雙軸拉伸該等樹脂形成薄膜而作為基材膜使用。 For the substrate film, a plastic film is preferably used. Examples of the material constituting the base film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyimide and polyphenylene sulfide; Aramid, polypropylene, polyethylene, polylactic acid, polyvinyl chloride, polycarbonate, polymethyl methacrylate, alicyclic acrylic resin, cycloolefin resin, triethyl fluorene cellulose, and mixed and/or The resin is polymerized. It can be suitably used as a base film by forming a film by unstretching these resins, or uniaxially stretching or biaxially stretching these resins.

於上述基材膜之中，聚酯膜係具優越之透明性、尺寸安定性、機械特性、耐熱性、電特性、耐藥品性等，特佳使用聚對苯二甲酸乙二酯膜(PET膜)。 Among the above-mentioned base film, the polyester film has excellent transparency, dimensional stability, mechanical properties, heat resistance, electrical properties, chemical resistance, etc., and polyethylene terephthalate film (PET) is particularly preferably used. membrane).

基材膜之厚度範圍適宜為20至300μm之範圍 ，較佳為30至200μm之範圍，更佳為50至150μm之範圍。 The thickness of the substrate film is suitably in the range of 20 to 300 μm. It is preferably in the range of 30 to 200 μm, more preferably in the range of 50 to 150 μm.

基材膜較佳在至少積層有第1硬被覆層之面上具有如下所示之樹脂層。亦即，在基材膜與第1硬被覆層之間較佳具有下列所示之樹脂層。 The base film preferably has a resin layer as described below on the surface on which at least the first hard coating layer is laminated. That is, it is preferable to have a resin layer shown below between the base film and the first hard coating layer.

[樹脂層] [resin layer]

為了強化基材膜與第1硬被覆層之緊貼性，基材膜較佳在積層有第1硬被覆層之面上設置有樹脂層。 In order to strengthen the adhesion between the base film and the first hard coating layer, the base film preferably has a resin layer provided on the surface on which the first hard coating layer is laminated.

樹脂層係含有將樹脂作為主要成分之層。具體而言，相對於樹脂層之固形物總量100質量%而言，樹脂層係含有50質量%以上為樹脂的層。作為形成樹脂層之樹脂，可舉出聚酯樹脂、丙烯酸樹脂、胺甲酸酯樹脂、聚碳酸酯樹脂、環氧樹脂、醇酸樹脂、尿素樹脂等。該等樹脂能夠單獨使用或是合併複數種使用。 The resin layer contains a layer containing a resin as a main component. Specifically, the resin layer contains 50% by mass or more of a resin-containing layer with respect to 100% by mass of the total solid content of the resin layer. Examples of the resin forming the resin layer include a polyester resin, an acrylic resin, a urethane resin, a polycarbonate resin, an epoxy resin, an alkyd resin, and a urea resin. These resins can be used singly or in combination of plural kinds.

從使樹脂層介於基材膜與第1硬被覆層之中間而使基材膜與第1硬被覆層的緊貼性提高之觀點，樹脂層之樹脂較佳至少含有一種選自包含聚酯樹脂、丙烯酸樹脂及聚胺甲酸酯樹脂之群組中的至少一種。樹脂層之樹脂特佳至少含有聚酯樹脂。 From the viewpoint of improving the adhesion between the base film and the first hard coating layer between the base film and the first hard coating layer, the resin of the resin layer preferably contains at least one selected from the group consisting of polyesters. At least one of the group of a resin, an acrylic resin, and a polyurethane resin. The resin of the resin layer particularly preferably contains at least a polyester resin.

相對於樹脂層之固形物總量100質量%而言，在樹脂層中樹脂的含量較佳為60質量%以上，更佳為70質量%以上，特佳為80質量%以上。關於上限，在樹脂層中樹脂的含量較佳為95質量%以下，更佳為90質量%以下。 The content of the resin in the resin layer is preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more based on 100% by mass of the total solid content of the resin layer. In the upper limit, the content of the resin in the resin layer is preferably 95% by mass or less, and more preferably 90% by mass or less.

又，樹脂層亦可利用2層構造形成。2層構造之情形，較佳從基材膜側起，依序使用以聚酯樹脂作為 主要成分之第1樹脂層與以丙烯酸樹脂作為主要成分之第2樹脂層所構成。針對2層構造，詳細敘述於後。 Further, the resin layer may be formed by a two-layer structure. In the case of a two-layer structure, it is preferred to use a polyester resin as a step from the side of the substrate film. The first resin layer of the main component and the second resin layer containing an acrylic resin as a main component are used. The two-layer structure will be described in detail later.

從確保在硬被覆膜之製造步驟的適度平滑性或捲取性之觀點，樹脂層較佳含有粒子。 The resin layer preferably contains particles from the viewpoint of ensuring moderate smoothness or coilability in the production steps of the hard coating film.

作為樹脂層中所含之粒子，並未被特別限定，可舉出二氧化矽粒子、氧化鈦、氧化鋁、氧化鋯、碳酸鈣、沸石粒子等之無機粒子；或丙烯酸粒子、聚矽氧粒子、聚醯亞胺粒子、Teflon(註冊商標)粒子、交聯聚酯粒子、交聯聚苯乙烯粒子、交聯聚合物粒子、芯殼粒子等之有機粒子。於該等之中，較佳為二氧化矽粒子，特佳為膠體二氧化矽。 The particles contained in the resin layer are not particularly limited, and examples thereof include inorganic particles such as cerium oxide particles, titanium oxide, aluminum oxide, zirconium oxide, calcium carbonate, and zeolite particles; or acrylic particles or polyoxygen oxide particles. Organic particles such as polyimine particles, Teflon (registered trademark) particles, crosslinked polyester particles, crosslinked polystyrene particles, crosslinked polymer particles, and core-shell particles. Among these, cerium oxide particles are preferred, and colloidal cerium oxide is particularly preferred.

樹脂層中所含之粒子係其平均粒徑較佳比樹脂層之厚度為大。具體而言，平均粒徑較佳為樹脂層厚度之1.3倍以上，更佳為1.5倍以上，特佳為2.0倍以上。上限較佳為20倍以下，更佳為15倍以下，特佳為10倍以下。 The particles contained in the resin layer preferably have an average particle diameter larger than the thickness of the resin layer. Specifically, the average particle diameter is preferably 1.3 times or more, more preferably 1.5 times or more, and particularly preferably 2.0 times or more. The upper limit is preferably 20 times or less, more preferably 15 times or less, and particularly preferably 10 times or less.

在如此之平均粒徑含有較樹脂層之厚度為大的粒子之樹脂層中，藉由直接積層第1硬被覆層而進一步提高平滑性與抗結塊性。 In the resin layer in which the average particle diameter contains particles having a larger thickness than the resin layer, the smoothness and the blocking resistance are further improved by directly laminating the first hard coating layer.

樹脂層中所含之粒子的平均粒徑係按照樹脂層之厚度設計而予以適宜選定，具體而言，平均粒徑之範圍較佳為0.02至1μm之範圍，更佳為0.05至0.7μm之範圍，特佳為0.1至0.5μm之範圍。若平均粒徑小於0.02μm時，則有平滑性或抗結塊性將會降低。若平均粒徑超過1μm時，則有粒子將會脫落、或透明性將會降低，或是 外觀將會惡化。 The average particle diameter of the particles contained in the resin layer is appropriately selected in accordance with the thickness of the resin layer. Specifically, the average particle diameter is preferably in the range of 0.02 to 1 μm, more preferably in the range of 0.05 to 0.7 μm. It is particularly preferably in the range of 0.1 to 0.5 μm. If the average particle diameter is less than 0.02 μm, smoothness or anti-caking property will be lowered. If the average particle size exceeds 1 μm, some particles will fall off, or the transparency will decrease, or The appearance will deteriorate.

樹脂層厚度之範圍較佳為0.005至0.3μm之範圍。樹脂層厚度小於0.005μm之情形，基材膜與第1硬被覆層之緊貼性將會降低。又，若使樹脂層之厚度較0.3μm為大時，則有積層第1硬被覆層後之抗結塊性將會降低。樹脂層之厚度進一步較佳為0.01μm以上，更佳為0.015μm以上，特佳為0.02μm以上。關於上限，樹脂層之厚度較佳為0.25μm以下，更佳為0.2μm以下，特佳為0.15μm以下。存在複數樹脂層之情形，合計全部之樹脂層厚度之值較佳符合上述厚度之條件。 The thickness of the resin layer preferably ranges from 0.005 to 0.3 μm. When the thickness of the resin layer is less than 0.005 μm, the adhesion between the base film and the first hard coating layer is lowered. Moreover, when the thickness of the resin layer is made larger than 0.3 μm, the anti-caking property after laminating the first hard coating layer is lowered. The thickness of the resin layer is more preferably 0.01 μm or more, still more preferably 0.015 μm or more, and particularly preferably 0.02 μm or more. The thickness of the resin layer is preferably 0.25 μm or less, more preferably 0.2 μm or less, and particularly preferably 0.15 μm or less. In the case where a plurality of resin layers are present, the total thickness of all the resin layers preferably satisfies the conditions of the above thickness.

相對於樹脂層之固形物總量100質量%而言，在樹脂層中之粒子的含量之範圍較佳為0.05至10質量%之範圍，更佳為0.1至8質量%之範圍，特佳為0.5至5質量%之範圍。若在樹脂層中之粒子的含量小於0.05質量%時，則有得不到良好之平滑性或抗結塊性；若粒子含量超過10質量%時，則有透明性將會降低、第1硬被覆層之塗布性將會惡化、或基材膜與第1硬被覆層之緊貼性將會降低。 The content of the particles in the resin layer is preferably in the range of 0.05 to 10% by mass, more preferably in the range of 0.1 to 8% by mass, particularly preferably 100% by mass based on the total amount of the solid matter of the resin layer. A range of 0.5 to 5% by mass. When the content of the particles in the resin layer is less than 0.05% by mass, good smoothness or blocking resistance is not obtained, and when the content of the particles exceeds 10% by mass, transparency is lowered, and the first hardness is obtained. The coating property of the coating layer is deteriorated, or the adhesion between the base film and the first hard coating layer is lowered.

樹脂層進一步較佳含有交聯劑。樹脂層較佳含有上述樹脂與交聯劑之熱硬化層。藉由將樹脂層作成如此之熱硬化層，能夠進一步提高基材膜與第1硬被覆層之緊貼性。雖然熱硬化樹脂層時之條件(加熱溫度、時間)並未被特別限定，但加熱溫度較佳為70℃以上，更佳為100℃以上，特佳為150℃以上，最佳為200℃以上。關於上限，加熱溫度較佳為300℃以下，加熱時間之範圍，較 佳為5至300秒之範圍，更佳為10至200秒之範圍。 The resin layer further preferably contains a crosslinking agent. The resin layer preferably contains a thermosetting layer of the above resin and a crosslinking agent. By forming the resin layer as such a thermosetting layer, the adhesion between the base film and the first hard coating layer can be further improved. Although the conditions (heating temperature, time) at the time of thermosetting the resin layer are not particularly limited, the heating temperature is preferably 70 ° C or higher, more preferably 100 ° C or higher, particularly preferably 150 ° C or higher, and most preferably 200 ° C or higher. . Regarding the upper limit, the heating temperature is preferably 300 ° C or less, and the heating time range is Preferably, it is in the range of 5 to 300 seconds, more preferably in the range of 10 to 200 seconds.

作為上述交聯劑，例如，可舉出三聚氰胺系交聯劑、唑啉系交聯劑、碳化二醯亞胺系交聯劑、異氰酸酯系交聯劑、吖環丙烷系交聯劑、環氧系交聯劑、羥甲基化或是烷醇化之尿素系交聯劑、丙烯醯胺系交聯劑、聚醯胺系樹脂、醯胺環氧化合物、各種矽烷耦合劑、各種鈦酸鹽系耦合劑等。該等之中，較佳為三聚氰胺系交聯劑、唑啉系交聯劑、碳化二醯亞胺系交聯劑、異氰酸酯系交聯劑、吖環丙烷系交聯劑，特佳為三聚氰胺系交聯劑。 The crosslinking agent may, for example, be a melamine crosslinking agent. An oxazoline crosslinking agent, a carbodiimide crosslinking agent, an isocyanate crosslinking agent, an anthracycline crosslinking agent, an epoxy crosslinking agent, a methylolated or an alkoxylated urea system A crosslinking agent, a acrylamide crosslinking agent, a polyamine resin, a guanamine epoxy compound, various decane coupling agents, various titanate coupling agents, and the like. Among these, a melamine crosslinking agent is preferred. The oxazoline crosslinking agent, the carbodiimide crosslinking agent, the isocyanate crosslinking agent, and the anthracycline crosslinking agent are particularly preferably a melamine crosslinking agent.

作為三聚氰胺系交聯劑，例如，可舉出亞胺基型甲基化三聚氰胺樹脂、羥甲基型三聚氰胺樹脂、羥甲基型甲基化三聚氰胺樹脂、完全烷基型甲基化三聚氰胺樹脂等。該等之中，較佳使用亞胺基型三聚氰胺樹脂、羥甲基化三聚氰胺樹脂。 Examples of the melamine-based crosslinking agent include an imido-type methylated melamine resin, a methylol type melamine resin, a methylol type methylated melamine resin, and a fully alkyl type methylated melamine resin. Among these, an imide type melamine resin or a methylolated melamine resin is preferably used.

相對於樹脂層之固形物總量100質量%而言，在樹脂層中之交聯劑含量之範圍較佳為0.5至40質量%之範圍，更佳為1至30質量%之範圍，特佳為2至20質量%之範圍。 The range of the crosslinking agent content in the resin layer is preferably in the range of 0.5 to 40% by mass, more preferably in the range of 1 to 30% by mass, particularly preferably 100% by mass based on the total amount of the solid matter of the resin layer. It is in the range of 2 to 20% by mass.

在基材膜上，使樹脂層介於中間，積層第1硬被覆層所得之硬被覆膜的反射色較佳為中性無色之色澤。從該觀點，將聚對苯二甲酸乙二酯膜(PET膜)作為基材膜之情形，樹脂層折射率之範圍較佳為1.55至1.61之範圍，更佳為1.56至1.60之範圍，特佳為1.57至1.59之範圍。 In the base film, the resin layer is interposed, and the reflection color of the hard coating film obtained by laminating the first hard coating layer is preferably a neutral colorless color. From this point of view, in the case where a polyethylene terephthalate film (PET film) is used as the substrate film, the refractive index of the resin layer preferably ranges from 1.55 to 1.61, more preferably from 1.56 to 1.60. Good range of 1.57 to 1.59.

聚對苯二甲酸乙二酯膜(PET膜)之折射率一般為1.62至1.70左右，藉由使樹脂層之折射率成為上述之範圍(1.55至1.61)，能夠使硬被覆膜之反射色接近中性無色。亦即，PET膜之折射率(np)與樹脂層之折射率(nr)之差(np-nr)較佳為0.02至0.1之範圍，更佳為0.03至0.09之範圍，特佳為0.04至0.08之範圍。 The refractive index of the polyethylene terephthalate film (PET film) is generally about 1.62 to 1.70, and the reflection color of the hard coating film can be made by making the refractive index of the resin layer into the above range (1.55 to 1.61). Close to neutral colorless. That is, the difference (np-nr) between the refractive index (np) of the PET film and the refractive index (nr) of the resin layer is preferably in the range of 0.02 to 0.1, more preferably in the range of 0.03 to 0.09, and particularly preferably 0.04 to The range of 0.08.

為了使樹脂層之折射率成為1.55至1.61，作為樹脂較佳使用分子中含有萘環之聚酯樹脂。含有萘環之聚酯樹脂，例如藉由將1,4-萘二甲酸、2,6-萘二甲酸等之多元羧酸作為共聚合成分使用而能夠合成。 In order to make the refractive index of the resin layer 1.55 to 1.61, a polyester resin containing a naphthalene ring in the molecule is preferably used as the resin. The polyester resin containing a naphthalene ring can be synthesized, for example, by using a polyvalent carboxylic acid such as 1,4-naphthalene dicarboxylic acid or 2,6-naphthalene dicarboxylic acid as a copolymerization component.

相對於全部樹脂總量100質量%而言，在樹脂層之分子中含有萘環之聚酯樹脂含量之範圍較佳為5至70質量%之範圍，更佳為10至60質量%之範圍。 The content of the polyester resin containing a naphthalene ring in the molecule of the resin layer is preferably in the range of 5 to 70% by mass, and more preferably in the range of 10 to 60% by mass, based on 100% by mass of the total of the total amount of the resin.

樹脂層較佳使用濕式塗布法，在基材膜上進行塗布、熱硬化而予以積層。進一步較佳在基材膜之製造步驟內，使用濕式塗布法而塗布樹脂層，藉由所謂的聯機塗布法而塗布、熱硬化後予以積層。作為濕式塗布法，例如，可舉出逆塗布法、噴霧塗布法、棒塗布法、照相凹版塗布法、模頭塗布法等。 The resin layer is preferably deposited by a wet coating method, coated on a substrate film, and thermally cured. Further preferably, the resin layer is applied by a wet coating method in the production step of the base film, and is applied by a so-called in-line coating method, thermally cured, and then laminated. Examples of the wet coating method include a reverse coating method, a spray coating method, a bar coating method, a gravure coating method, a die coating method, and the like.

如上所述，樹脂層能夠採用2層構造。如此之2層構造的樹脂層較佳為1次塗布一種塗布液，在其乾燥過程中，使自我相分離發生後形成。亦即，較佳採用下列之方法：塗布含有第1樹脂層之主要成分(聚酯樹脂)與第2樹脂層之主要成分(丙烯酸樹脂)的塗布液，在其乾燥過程，利用各自成分的自我相分離而形成第1樹脂層與第 2樹脂層。 As described above, the resin layer can have a two-layer structure. The resin layer of such a two-layer structure is preferably coated with a coating liquid once, and is formed after self-phase separation occurs during the drying process. In other words, it is preferable to apply a coating liquid containing a main component (polyester resin) of the first resin layer and a main component (acrylic resin) of the second resin layer, and to utilize the self of each component in the drying process. Phase separation to form the first resin layer and the first 2 resin layer.

於實施該相分離方法時，較佳擴大第1樹脂層之主要成分(聚酯樹脂)與第2樹脂層之主要成分(丙烯酸樹脂)的表面能量差。亦即，較佳使用表面能量高的聚酯樹脂與表面能量低的丙烯酸樹脂。尤其，為了提高聚酯樹脂之表面能量，較佳使用具有磺酸基之聚酯樹脂。 When the phase separation method is carried out, it is preferred to increase the surface energy difference between the main component (polyester resin) of the first resin layer and the main component (acrylic resin) of the second resin layer. That is, it is preferred to use a polyester resin having a high surface energy and an acrylic resin having a low surface energy. In particular, in order to increase the surface energy of the polyester resin, a polyester resin having a sulfonic acid group is preferably used.

樹脂層為2層構造之情形，從強化基材膜與第1硬被覆層的緊貼性、使硬被覆膜之反射色接近中性無色之觀點，較佳使第1樹脂層之厚度較第2樹脂層之厚度為大。第1樹脂層之厚度較佳為第2樹脂層之厚度的1.5倍以上，更佳為2.0倍以上，特佳為3.0倍以上。 When the resin layer has a two-layer structure, the thickness of the first resin layer is preferably from the viewpoint of the adhesion between the reinforcing base film and the first hard coating layer and the fact that the reflection color of the hard coating film is close to neutral colorless. The thickness of the second resin layer is large. The thickness of the first resin layer is preferably 1.5 times or more, more preferably 2.0 times or more, and particularly preferably 3.0 times or more the thickness of the second resin layer.

具體而言，第1樹脂層厚度之範圍較佳為0.02至0.2μm之範圍，更佳為0.03至0.15μm之範圍，特佳為0.05至0.12μm之範圍。第2樹脂層厚度之範圍較佳為0.005至0.1μm之範圍，更佳為0.01至0.07μm之範圍，特佳為0.01至0.05μm之範圍。 Specifically, the thickness of the first resin layer preferably ranges from 0.02 to 0.2 μm, more preferably from 0.03 to 0.15 μm, and particularly preferably from 0.05 to 0.12 μm. The thickness of the second resin layer preferably ranges from 0.005 to 0.1 μm, more preferably from 0.01 to 0.07 μm, and particularly preferably from 0.01 to 0.05 μm.

在基材膜與第1硬被覆層之間所設置的樹脂層係其表面的濕潤張力較佳為52mN/m以下。亦即，在本發明中，塗布有第1硬被覆層之樹脂層表面的濕潤張力較佳為52mN/m以下。藉由在如此之樹脂層上直接積層第1硬被覆層，而使得因粒子所造成的突起變得容易形成於第1硬被覆層表面，其結果，平滑性與抗結塊性將會進一步提高。於此，濕潤張力係依據JIS K 6768所規定的物性值。 The resin layer provided between the base film and the first hard coating layer preferably has a wet tension on the surface of 52 mN/m or less. That is, in the present invention, the wetting tension of the surface of the resin layer coated with the first hard coating layer is preferably 52 mN/m or less. By directly laminating the first hard coating layer on such a resin layer, protrusions due to particles are easily formed on the surface of the first hard coating layer, and as a result, smoothness and anti-caking property are further improved. . Here, the wet tension is based on the physical property values specified in JIS K 6768.

在上述基材膜與第1硬被覆層之間設置濕潤 張力為52mN/m以下之樹脂層的形態係在第1硬被覆層厚度較小之情形下為有效。若使第1硬被覆層之厚度變小時，也會使第1硬被覆層中所含之粒子的絕對量變小。但是，藉由在濕潤張力為52mN/m以下之樹脂層上積層第1硬被覆層而使第1硬被覆層中所含之粒子於表面附近變得容易不均勻，其結果，便能夠效率佳地形成突起。該形態係有效於第1硬被覆層之厚度小於2μm之情形，還有，在第1硬被覆層之厚度為1.7μm以下之情形下，特別有效。 Wetting is provided between the base film and the first hard coating layer The form of the resin layer having a tension of 52 mN/m or less is effective in the case where the thickness of the first hard coating layer is small. When the thickness of the first hard coating layer is made small, the absolute amount of particles contained in the first hard coating layer is also reduced. However, by laminating the first hard coating layer on the resin layer having a wet tension of 52 mN/m or less, the particles contained in the first hard coating layer are easily uneven in the vicinity of the surface, and as a result, the efficiency can be improved. The ground forms a protrusion. This form is effective when the thickness of the first hard coating layer is less than 2 μm, and is particularly effective when the thickness of the first hard coating layer is 1.7 μm or less.

從上述之觀點，樹脂層表面的濕潤張力進一步較佳為50mN/m以下。另一方面，從確保基材膜與第1硬被覆層的緊貼性之觀點，樹脂層表面的濕潤張力之下限較佳為35mN/m以上，更佳為37mN/m以上，特佳為40mN/m以上。若使樹脂層表面的濕潤張力小於35mN/m時，第1硬被覆層之緊貼性將會降低。 From the above viewpoints, the wetting tension on the surface of the resin layer is more preferably 50 mN/m or less. On the other hand, from the viewpoint of ensuring the adhesion between the base film and the first hard coating layer, the lower limit of the wetting tension on the surface of the resin layer is preferably 35 mN/m or more, more preferably 37 mN/m or more, and particularly preferably 40 mN. /m or more. When the wet tension of the surface of the resin layer is less than 35 mN/m, the adhesion of the first hard coating layer is lowered.

從將樹脂層表面的濕潤張力控制於52mN/m以下、且使基材膜與第1硬被覆層的緊貼性提高之觀點，作為樹脂層中所含之樹脂較佳使用選自包含聚酯樹脂、丙烯酸樹脂及聚胺甲酸酯樹脂之群組中的至少一種。於該等樹脂之中，進一步較佳使用聚酯樹脂及/或丙烯酸樹脂，作為樹脂特佳為至少使用聚酯樹脂。 From the viewpoint of controlling the wet tension of the surface of the resin layer to 52 mN/m or less and improving the adhesion between the base film and the first hard coating layer, the resin contained in the resin layer is preferably selected from the group consisting of polyesters. At least one of the group of a resin, an acrylic resin, and a polyurethane resin. Among these resins, a polyester resin and/or an acrylic resin is further preferably used, and as the resin, at least a polyester resin is preferably used.

又，藉由調整上述交聯劑之種類或含量也能夠控制樹脂層表面之濕潤張力。例如，若使交聯劑之含量變多時，有使樹脂層表面之濕潤張力變小之傾向；相反地，若使交聯劑之含量變少時，有使樹脂層表面之濕 潤張力變大之傾向。 Further, the wetting tension on the surface of the resin layer can be controlled by adjusting the type or content of the above crosslinking agent. For example, when the content of the crosslinking agent is increased, the wetting tension on the surface of the resin layer tends to be small. Conversely, when the content of the crosslinking agent is decreased, the surface of the resin layer is wet. The tendency to moisturize the tension.

[第1硬被覆層] [1st hard coating]

第1硬被覆層係含有粒子，因該粒子所造成的突起係形成第1硬被覆層表面。在第1硬被覆層表面之突起的個數密度係第1硬被覆層表面每單位面積(100μm2)為300至4000個。還有，突起的個數密度之範圍係每100μm2較佳為400至3500個之範圍，更佳為500至3000個之範圍，進一步較佳為600至3000個之範圍，特佳為700至2500個之範圍。 The first hard coating layer contains particles, and the protrusions due to the particles form the surface of the first hard coating layer. The number density of the protrusions on the surface of the first hard coating layer is 300 to 4,000 per unit area (100 μm 2 ) of the surface of the first hard coating layer. Further, the number density of the protrusions is preferably in the range of 400 to 3500 per 100 μm 2 , more preferably in the range of 500 to 3000, further preferably in the range of 600 to 3000, and particularly preferably in the range of 700 to 3,000. 2,500 ranges.

第1硬被覆層中所含之粒子的平均粒徑(r)之範圍較佳為0.05至0.5μm之範圍，更佳為0.06至0.4μm之範圍，特佳為0.07至0.3μm之範圍。 The average particle diameter (r) of the particles contained in the first hard coating layer is preferably in the range of 0.05 to 0.5 μm, more preferably in the range of 0.06 to 0.4 μm, and particularly preferably in the range of 0.07 to 0.3 μm.

若第1硬被覆層中所含之粒子的平均粒徑(r)小於0.05μm時，在第1硬被覆層表面未形成充分大小之突起而有平滑性與抗結塊性未被充分改良。若平均粒徑(r)超過0.5μm時，第1硬被覆層表面之平滑性將會降低，使中心線平均粗糙度(Ra1)成為30nm以上、或使硬被覆膜之霧度值成為1.5%以上而有發生透明性降低等之不當情形。 When the average particle diameter (r) of the particles contained in the first hard coating layer is less than 0.05 μm, protrusions having a sufficient size are not formed on the surface of the first hard coating layer, and smoothness and anti-caking property are not sufficiently improved. When the average particle diameter (r) exceeds 0.5 μm, the smoothness of the surface of the first hard coating layer is lowered, and the center line average roughness (Ra1) is 30 nm or more, or the haze value of the hard coating film is 1.5. More than %, there is an inappropriate situation such as a decrease in transparency.

相對於第1硬被覆層之厚度(d)而言，第1硬被覆層中所含之粒子的平均粒徑(r)較佳為充分的小。亦即，粒子之平均粒徑(r)與第1硬被覆層之厚度(d)的比例(r/d)較佳為0.01至0.30之範圍。較佳使如此之粒子較多存在於第1硬被覆層表面附近，如上所述而使其形成較多的突起。藉此，不會使第1硬被覆層表面層之平滑性降低而 能夠使平滑性與抗結塊性提高。 The average particle diameter (r) of the particles contained in the first hard coating layer is preferably sufficiently small with respect to the thickness (d) of the first hard coating layer. That is, the ratio (r/d) of the average particle diameter (r) of the particles to the thickness (d) of the first hard coating layer is preferably in the range of 0.01 to 0.30. It is preferable that such particles are present in a large amount in the vicinity of the surface of the first hard coating layer, and as described above, a large number of protrusions are formed. Thereby, the smoothness of the surface layer of the first hard coating layer is not lowered. It can improve smoothness and anti-caking property.

第1硬被覆層中所含之粒子的平均粒徑(r)與第1硬被覆層之厚度(d)的比例(r/d)之範圍進一步較佳為0.01至0.20之範圍，更佳為0.01至0.15之範圍，特佳為0.02至0.10之範圍，最佳為0.02至0.08之範圍。 The range of the ratio (r/d) of the average particle diameter (r) of the particles contained in the first hard coating layer to the thickness (d) of the first hard coating layer is more preferably in the range of 0.01 to 0.20, more preferably The range of 0.01 to 0.15 is particularly preferably in the range of 0.02 to 0.10, and most preferably in the range of 0.02 to 0.08.

藉由如上所述之粒子而在第1硬被覆層表面所形成的突起之平均直徑之範圍較佳為0.03至0.3μm之範圍。突起之平均直徑之範圍更佳為0.04至0.25μm之範圍，進一步較佳為0.05至0.2μm之範圍。藉此，不會使透明性降低而能夠使平滑性與抗結塊性提高。 The average diameter of the protrusions formed on the surface of the first hard coating layer by the particles as described above is preferably in the range of 0.03 to 0.3 μm. The range of the average diameter of the protrusions is more preferably in the range of 0.04 to 0.25 μm, still more preferably in the range of 0.05 to 0.2 μm. Thereby, smoothness and anti-caking property can be improved without lowering transparency.

突起之平均高度之範圍較佳為0.03至0.3μm之範圍。突起之平均高度之範圍更佳為0.04至0.25μm之範圍，進一步較佳為0.05至0.2μm之範圍。藉此，不會使透明性降低而能夠使平滑性與抗結塊性提高。 The average height of the protrusions preferably ranges from 0.03 to 0.3 μm. The range of the average height of the protrusions is more preferably in the range of 0.04 to 0.25 μm, still more preferably in the range of 0.05 to 0.2 μm. Thereby, smoothness and anti-caking property can be improved without lowering transparency.

雖然在第1硬被覆層表面所形成的突起之形狀並未被特別限定，但較佳具有圓形或接近於圓形之平面形狀。於此，突起之平面形狀係指使用掃描型電子顯微鏡(SEM)觀察第1硬被覆層表面時之平面形狀。 Although the shape of the protrusion formed on the surface of the first hard coating layer is not particularly limited, it preferably has a circular or close to circular planar shape. Here, the planar shape of the protrusion refers to a planar shape when the surface of the first hard coating layer is observed using a scanning electron microscope (SEM).

第1圖係使用掃描型電子顯微鏡拍攝第1硬被覆層的表面照片之一例。在第1硬被覆層表面上形成有因粒子所造成的突起11。 Fig. 1 is an example of a photograph of a surface of a first hard coating layer taken by a scanning electron microscope. A protrusion 11 due to particles is formed on the surface of the first hard coating layer.

第2圖係示意表示第1硬被覆層表面之突起的平面形狀之圖形。 Fig. 2 is a view schematically showing a planar shape of a projection on the surface of the first hard coating layer.

所謂突起之平面形狀接近圓形係意指在顯示於第2圖之示意圖中，表示以突起11之最大直徑(Lmax) 的線段與中心Lc所正交的突起11之直徑(Lmin)、與突起11之最大直徑(Lmax)的比例(Lmin/Lmax)為0.65以上。 The fact that the planar shape of the protrusion is close to a circular system means that the maximum diameter (Lmax) of the protrusion 11 is shown in the schematic view shown in FIG. The ratio (Lmin/Lmax) of the diameter (Lmin) of the protrusion 11 orthogonal to the center Lc and the maximum diameter (Lmax) of the protrusion 11 is 0.65 or more.

上述之比例(Lmin/Lmax)較佳為0.70以上，更佳為0.80以上，特佳為0.85以上。上限為1.0。 The above ratio (Lmin/Lmax) is preferably 0.70 or more, more preferably 0.80 or more, and particularly preferably 0.85 or more. The upper limit is 1.0.

在第1圖之表面照片的突起平面形狀中任一種皆為圓形或是依照上述定義所說明的「接近圓形」形狀。 Any of the projection plane shapes of the surface photograph of Fig. 1 is circular or a "near circular" shape as explained above.

於本專利說明書中，所謂突起之直徑係意指顯示於第2圖之最大直徑(Lmax)。突起之平均直徑能夠使用掃描型電子顯微鏡而從根據如第1圖所示之第1硬被覆層的表面照片而求得。 In the present specification, the diameter of the protrusion means the maximum diameter (Lmax) shown in Fig. 2. The average diameter of the protrusions can be obtained from a surface photograph of the first hard coating layer as shown in Fig. 1 using a scanning electron microscope.

於本專利說明書中，所謂突起之高度係意指從突起之頂點起直到第1硬被覆層表面為止之長度。突起之平均高度能夠從使用穿透型電子顯微鏡(TEM)拍攝第1硬被覆層的剖面照片而測得。 In the present specification, the height of the protrusion means the length from the apex of the protrusion to the surface of the first hard coating layer. The average height of the protrusions can be measured from a photograph of a cross section of the first hard coating layer using a transmission electron microscope (TEM).

在第1硬被覆層表面之突起的平均間隔之範圍較佳為0.10至0.70μm之範圍，更佳為0.15至0.50μm之範圍，特佳為0.20至0.40μm之範圍。藉此，不會使透明性降低而能夠使平滑性與抗結塊性提高。 The average interval of the protrusions on the surface of the first hard coating layer is preferably in the range of 0.10 to 0.70 μm, more preferably in the range of 0.15 to 0.50 μm, and particularly preferably in the range of 0.20 to 0.40 μm. Thereby, smoothness and anti-caking property can be improved without lowering transparency.

突起的平均間隔能夠從使用掃描型電子顯微鏡拍攝第1硬被覆層的剖面照片而求得。第3圖係模式化使用掃描型電子顯微鏡拍攝第1硬被覆層的表面照片之圖形。利用第3圖說明突起之平均間隔的測定方法。 The average interval of the projections can be obtained by photographing a cross-sectional photograph of the first hard coating layer using a scanning electron microscope. Fig. 3 is a pattern in which a surface photograph of the first hard coating layer is taken using a scanning electron microscope. A method of measuring the average interval of the protrusions will be described using FIG.

首先，橫向劃出一條直線20，進一步劃出垂直於橫向直線20之縱向直線30。接著，針對沿著橫向直 線20(亦即，接觸於直線20)之全部突起，測定與所鄰接之突起的間隔，對於縱向直線30也進行同樣的操作。進行如此方式而平均所得之全部突起的間隔(距離)。 First, a straight line 20 is drawn laterally, and a longitudinal straight line 30 perpendicular to the transverse straight line 20 is further drawn. Next, for straight along the lateral direction The entire projection of the line 20 (i.e., in contact with the straight line 20) measures the distance from the adjacent projection, and the same operation is performed for the longitudinal straight line 30. The interval (distance) of all the protrusions obtained by averaging in this manner is performed.

針對突起之平均間隔的測定方法，利用第4圖而詳加說明。 The method of measuring the average interval of the protrusions will be described in detail using FIG.

第4圖係僅選擇沿著在第3圖之橫向直線20或縱向直線30的突起所編排者。於第4圖中，沿著橫向直線20之突起係以符號1至5所示之5個。所謂所鄰接之突起的間隔，例如為突起1與鄰接於該突起1之突起2的距離P。同樣地，量測突起2與突起3的間隔、突起3與突起4的間隔、突起4與突起5的間隔，針對沿著橫向直線20之全部粒子而量測所鄰接之突起間的間隔。 Fig. 4 is a selection of only the projections along the transverse straight line 20 or the longitudinal straight line 30 in Fig. 3. In Fig. 4, the projections along the transverse straight line 20 are indicated by five symbols 1 to 5. The interval between the adjacent protrusions is, for example, the distance P between the protrusion 1 and the protrusion 2 adjacent to the protrusion 1. Similarly, the interval between the protrusions 2 and the protrusions 3, the distance between the protrusions 3 and the protrusions 4, and the distance between the protrusions 4 and the protrusions 5 are measured, and the interval between the adjacent protrusions is measured for all the particles along the lateral straight line 20.

同樣地，也針對沿著縱向直線30之全部突起而量測所鄰接之突起間的間隔。 Similarly, the spacing between adjacent protrusions is also measured for all protrusions along the longitudinal line 30.

分別3次變更橫向直線之位置及縱向直線之位置而實施上述之操作，將平均所得之全部的突起間隔設為突起之平均間隔。 The above operation was carried out by changing the position of the horizontal straight line and the position of the longitudinal straight line three times, and the average projection interval obtained by the average was set as the average interval of the projections.

如第1圖所示，在第1硬被覆層表面之各個突起較佳為根據各自的1個粒子所形成。藉此，藉由將第1硬被覆層表面的中心線平均粗糙度(Ra1)調整至小於30nm、與將硬被覆膜之霧度值調整至小於1.5%將會變得容易。若在複數粒子凝聚之狀態下形成突起時，有第1硬被覆層表面的中心線平均粗糙度(Ra1)或硬被覆膜的霧度值變大之傾向，故不佳。 As shown in Fig. 1, each of the protrusions on the surface of the first hard coating layer is preferably formed by one of the respective particles. Thereby, it is easy to adjust the center line average roughness (Ra1) of the surface of the first hard coating layer to less than 30 nm and to adjust the haze value of the hard coating film to less than 1.5%. When the protrusions are formed in a state in which the plurality of particles are aggregated, the center line average roughness (Ra1) of the surface of the first hard coating layer or the haze value of the hard coating film tends to be large, which is not preferable.

相對於第1硬被覆層之固形物總量100質量% 而言，在第1硬被覆層的粒子含量之範圍較佳為2.5至17質量%之範圍，更佳為3至15質量%之範圍，特佳為4至12質量%之範圍。 100% by mass relative to the total solid content of the first hard coating layer The range of the particle content of the first hard coating layer is preferably in the range of 2.5 to 17% by mass, more preferably in the range of 3 to 15% by mass, particularly preferably in the range of 4 to 12% by mass.

如上所述，相對於第1硬被覆層之厚度(d)而言，較佳在第1硬被覆層中含有平均粒徑(r)充分小的粒子，使粒子較多存在於第1硬被覆層表面附近而使較多的突起形成於第1硬被覆層表面。 As described above, the thickness (d) of the first hard coating layer preferably contains particles having a sufficiently small average particle diameter (r) in the first hard coating layer, and the particles are often present in the first hard coating. A large number of protrusions are formed on the surface of the first hard coating layer in the vicinity of the surface of the layer.

為了使粒子存在於第1硬被覆層表面附近，必須在第1硬被覆層之形成過程，使粒子移向(浮上)表面附近。例如，此係使得藉由使用已實施用以縮小粒子表面自由能之表面處理的粒子、或是已實施用以疏水化粒子表面之疏水化處理的粒子將會成為可能。作為已實施該等處理之粒子，較佳為無機粒子，特佳為二氧化矽粒子。 In order to allow the particles to exist in the vicinity of the surface of the first hard coating layer, it is necessary to move the particles toward the vicinity of the (floating) surface during the formation of the first hard coating layer. For example, this is made possible by using particles which have been subjected to surface treatment for reducing the free energy of the surface of the particles, or particles which have been subjected to hydrophobization treatment to hydrophobize the surface of the particles. As the particles subjected to the treatment, inorganic particles are preferred, and cerium oxide particles are particularly preferred.

作為第1硬被覆層中所含之粒子，較佳使用無機粒子。作為無機粒子，可舉出較佳含有選自Si、Na、K、Ca、及Mg之元素的無機粒子。進一步較佳可舉出含有選自二氧化矽粒子(SiO2)、鹼金屬氟化物(NaF、KF等)、及鹼土金屬氟化物(CaF2、MgF2等)之化合物，但從耐久性等之觀點，特佳為二氧化矽粒子。 As the particles contained in the first hard coating layer, inorganic particles are preferably used. The inorganic particles include inorganic particles preferably containing an element selected from the group consisting of Si, Na, K, Ca, and Mg. Further, a compound containing a material selected from the group consisting of cerium oxide particles (SiO 2 ), alkali metal fluoride (such as NaF or KF), and alkaline earth metal fluoride (such as CaF 2 or MgF 2 ) is preferably used, but durability is required. In view of the above, it is particularly preferred to be cerium oxide particles.

作為用以縮小上述粒子之表面自由能的表面處理，可舉出使用以下列通式(1)所示之選自具有氟原子之有機矽烷化合物、該有機矽烷之水解物、及該有機矽烷水解物之部分縮合物的至少一種化合物而表面處理之方法。 As a surface treatment for reducing the surface free energy of the above-mentioned particles, an organodecane compound selected from the group consisting of the following general formula (1), a hydrolyzate of the organodecane, and the hydrolyzate of the organodecane are used. A method of surface treatment of at least one compound of a partial condensate of a substance.

CnF2n+1-(CH2)m-Si(Q)3…通式(1) C n F 2n+1 -(CH 2 ) m -Si(Q) 3 ... Formula (1)

(在通式(1)，n係表示1至10之整數、m係表示1至5之整數。Q係表示碳數1至5之烷氧基或鹵素原子)。 (In the formula (1), n represents an integer of 1 to 10, m represents an integer of 1 to 5. Q represents an alkoxy group having 1 to 5 carbon atoms or a halogen atom).

作為通式(1)之化合物，具體而言，可舉出下列之化合物。 Specific examples of the compound of the formula (1) include the following compounds.

C4F9CH2CH2Si(OCH3)3 C 4 F 9 CH 2 CH 2 Si(OCH 3 ) 3

C6F13CH2CH2Si(OCH3)3 C 6 F 13 CH 2 CH 2 Si(OCH 3 ) 3

C8F17CH2CH2Si(OCH3)3 C 8 F 17 CH 2 CH 2 Si(OCH 3 ) 3

C6F13CH2CH2CH2Si(OCH3)3 C 6 F 13 CH 2 CH 2 CH 2 Si(OCH 3 ) 3

C6F13CH2CH2CH2CH2Si(OCH3)3 C 6 F 13 CH 2 CH 2 CH 2 CH 2 Si(OCH 3 ) 3

C6F13CH2CH2Si(OC2H5)3 C 6 F 13 CH 2 CH 2 Si(OC 2 H 5 ) 3

C8F17CH2CH2CH2Si(OC2H5)3 C 8 F 17 CH 2 CH 2 CH 2 Si(OC 2 H 5 ) 3

C6F13CH2CH2CH2CH2Si(OC2H5)3 C 6 F 13 CH 2 CH 2 CH 2 CH 2 Si(OC 2 H 5 ) 3

C6F13CH2CH2SiCl3 C 6 F 13 CH 2 CH 2 SiCl 3

C6F13CH2CH2SiBr3 C 6 F 13 CH 2 CH 2 SiBr 3

C6F13CH2CH2CH2SiCl3 C 6 F 13 CH 2 CH 2 CH 2 SiCl 3

C6F13CH2CH2Si(OCH3)Cl2 C 6 F 13 CH 2 CH 2 Si(OCH 3 )Cl 2

又，作為用以縮小無機粒子表面自由能之其他的表面處理，可舉出使用以下列通式(2)所示之化合物進行處理，進一步使用以下列通式(3)所示之氟化物進行表面處理之方法。 Further, as another surface treatment for reducing the surface free energy of the inorganic particles, treatment with a compound represented by the following formula (2) can be used, and further, a fluoride represented by the following formula (3) can be used. The method of surface treatment.

B-R4-SiR5 n(OR6)3-n…通式(2) BR 4 -SiR 5 n (OR 6 ) 3-n ... Formula (2)

D-R7-Rf2…通式(3) DR 7 -Rf 2 ... of formula (3)

(在通式(2)與通式(3)，B與D係各自獨立地表示反應性部位，R4與R7係各自獨立地表示碳數1至3之伸 烷基、或是表示從該伸烷基所衍生的酯構造，R5與R6係各自獨立地表示氫或碳數1至4之烷基，Rf2係表示氟烷基，n係表示0至2之整數。) (In the general formula (2) and the general formula (3), B and D each independently represent a reactive moiety, and R 4 and R 7 each independently represent an alkylene group having 1 to 3 carbon atoms, or The ester structure derived from the alkylene group, R 5 and R 6 each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms, Rf 2 represents a fluoroalkyl group, and n represents an integer of 0 to 2.

作為以B與D所表示的反應性部位，例如，可舉出乙烯基、烯丙基、丙烯醯基、甲基丙烯醯基、丙烯醯氧基、甲基丙烯醯氧基、環氧基、羧基、羥基等。 Examples of the reactive sites represented by B and D include a vinyl group, an allyl group, an allyl group, a methacryloyl group, an acryloxy group, a methacryloxy group, and an epoxy group. Carboxyl group, hydroxyl group, and the like.

作為通式(2)的具體例，可舉出丙烯醯氧乙基三甲氧基矽烷、丙烯醯氧丙基三甲氧基矽烷、丙烯醯氧丁基三甲氧基矽烷、丙烯醯氧戊基三甲氧基矽烷、丙烯醯氧己基三甲氧基矽烷、丙烯醯氧庚基三甲氧基矽烷、甲基丙烯醯氧乙基三甲氧基矽烷、甲基丙烯醯氧丙基三甲氧基矽烷、甲基丙烯醯氧丁基三甲氧基矽烷、甲基丙烯醯氧己基三甲氧基矽烷、甲基丙烯醯氧庚基三甲氧基矽烷、甲基丙烯醯氧丙基甲基二甲氧基矽烷、及包含該等化合物中之甲氧基被其他之烷氧基或羥基所取代的化合物等。 Specific examples of the general formula (2) include propylene oxime oxyethyl trimethoxy decane, propylene oxypropyl trimethoxy decane, propylene oxybutyl trimethoxy decane, and propylene oxiranyl trimethoxy hydride. Base alkane, propylene oxyhexyl trimethoxy decane, propylene oxiranyl heptyl trimethoxy decane, methacryl oxiranyl trimethoxy decane, methacryl oxiranyl trimethoxy decane, methacryl oxime Oxybutyl butyl trimethoxy decane, methacryl oxiranyl trimethoxy decane, methacryl oxiranyl trimethoxy decane, methacryl methoxypropyl methyl dimethoxy decane, and the like A compound in which a methoxy group in a compound is substituted with another alkoxy group or a hydroxyl group.

作為通式(3)的具體例，可舉出丙烯酸-2,2,2-三氟乙酯、丙烯酸-2,2,3,3,3-五氟丙酯、丙烯酸-2-過氟丁基乙酯、丙烯酸-3-過氟丁基-2-羥基丙酯、丙烯酸-2-過氟己基乙酯、丙烯酸-3-過氟己基-2-羥基丙酯、丙烯酸過氟辛基甲酯、丙烯酸-2-過氟辛基乙酯、丙烯酸-3-過氟辛基-2-羥基丙酯、丙烯酸-2-過氟癸基乙酯、丙烯酸-2-過氟-3-甲基丁基乙酯、丙烯酸-3-過氟-3-甲氧基丁基-2-羥基丙酯、丙烯酸-2-過氟-5-甲基己基乙酯、丙烯酸-3-過氟-5-甲基己基-2-羥基丙酯、丙烯酸-2-過氟-7-甲基辛基-2-羥基丙酯、丙烯酸四氟丙酯、丙烯酸八氟戊酯、丙 烯酸十二氟庚酯、丙烯酸十六氟壬酯、丙烯酸六氟丁酯；甲基丙烯酸-2,2,2-三氟乙酯、甲基丙烯酸-2,2,3,3,3-五氟丙酯、甲基丙烯酸-2-過氟丁基乙酯、甲基丙烯酸-3-過氟丁基-2-羥基丙酯、甲基丙烯酸過氟辛基甲酯、甲基丙烯酸-2-過氟辛基乙酯、甲基丙烯酸-3-過氟辛基-2-羥基丙酯、甲基丙烯酸-2-過氟癸基乙酯、甲基丙烯酸-2-過氟-3-甲基丁基乙酯、甲基丙烯酸-3-過氟-3-甲基丁基-2-羥基丙酯、甲基丙烯酸-2-過氟-5-甲基己基乙酯、甲基丙烯酸-3-過氟-5-甲基己基-2-羥基丙酯、甲基丙烯酸-2-過氟-7-甲基辛基乙酯、甲基丙烯酸-3-過氟-7-甲基辛基乙酯、甲基丙烯酸四氟丙酯、甲基丙烯酸八氟戊酯、甲基丙烯酸十二氟庚酯、甲基丙烯酸十六氟壬酯、甲基丙烯酸-1-三氟甲基三氟乙酯、甲基丙烯酸六氟丁酯等。 Specific examples of the general formula (3) include 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, and 2-perfluorobutyl acrylate. Ethyl ethyl ester, 3-perfluorobutyl-2-hydroxypropyl acrylate, 2-perfluorohexylethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, perfluorooctyl methacrylate , 2-perfluorooctylethyl acrylate, 3-perfluorooctyl-2-hydroxypropyl acrylate, 2-perfluorodecylethyl acrylate, 2-perfluoro-3-methyl butyl acrylate Ethyl ethyl ester, 3-perfluoro-3-methoxybutyl-2-hydroxypropyl acrylate, 2-perfluoro-5-methylhexylethyl acrylate, 3-perfluoro-5-ethyl acrylate Hexyl-2-hydroxypropyl ester, 2-perfluoro-7-methyloctyl-2-hydroxypropyl acrylate, tetrafluoropropyl acrylate, octafluoropentyl acrylate, C Dodecyl heptanoate, hexadecafluorodecyl acrylate, hexafluorobutyl acrylate; 2,2,2-trifluoroethyl methacrylate, methacrylic acid-2,2,3,3,3- Pentafluoropropyl ester, 2-perfluorobutyl ethyl methacrylate, 3-perfluorobutyl-2-hydroxypropyl methacrylate, perfluorooctyl methyl methacrylate, methacrylic acid-2 -Perfluorooctylethyl ester, 3-perfluorooctyl-2-hydroxypropyl methacrylate, 2-perfluorodecyl methacrylate, 2-perfluoro-3-methyl methacrylate Butyl butyl ethyl ester, 3-perfluoro-3-methylbutyl-2-hydroxypropyl methacrylate, 2-perfluoro-5-methylhexyl methacrylate, methacrylic acid-3 -Perfluoro-5-methylhexyl-2-hydroxypropyl ester, 2-perfluoro-7-methyloctylethyl methacrylate, 3-perfluoro-7-methyloctyl methacrylate Ester, tetrafluoropropyl methacrylate, octafluoropentyl methacrylate, dodecafluoroheptyl methacrylate, hexadecafluorodecyl methacrylate, 1-trifluoromethyltrifluoroethyl methacrylate , hexafluorobutyl methacrylate, and the like.

作為在上述之粒子表面用以實施疏水化處理之疏水性化合物，例如，可舉出在分子中具有疏水基與反應性部位之化合物。疏水性化合物之疏水基，若具有一般疏水性功能的話，並未被特別限定，作為疏水基的具體例，例如，可舉出選自包含碳數4以上之氟烷基、碳數8以上之烴基及矽氧烷基之群組的至少一種官能基。 The hydrophobic compound to be subjected to the hydrophobizing treatment on the surface of the above-mentioned particles may, for example, be a compound having a hydrophobic group and a reactive site in the molecule. The hydrophobic group of the hydrophobic compound is not particularly limited as long as it has a general hydrophobic function. Specific examples of the hydrophobic group include, for example, a fluoroalkyl group having a carbon number of 4 or more and a carbon number of 8 or more. At least one functional group of a group of a hydrocarbyl group and a decyloxy group.

作為上述之反應性部位係藉由接受光或熱等之能量所產生的自由基等而進行化學反應之部位，作為具體例更佳為具有乙烯基、烯丙基、丙烯醯基、甲基丙烯醯基、丙烯醯氧基、甲基丙烯醯氧基、環氧基、羧基、羥基等之接受光或熱等之能量而進行化學反應之部位。 The reactive site is a site where a chemical reaction is carried out by receiving a radical generated by energy such as light or heat, and as a specific example, it is more preferable to have a vinyl group, an allyl group, an acrylonitrile group, or a methacrylic group. A site in which a thiol group, an acryloxy group, a methacryloxy group, an epoxy group, a carboxyl group, a hydroxyl group, or the like is subjected to a chemical reaction by receiving energy such as light or heat.

亦即，作為在粒子表面用以實施疏水化處理之疏水性化合物，較佳使用選自包含具有碳數4以上之氟烷基與反應性部位的化合物(氟化物)、具有碳數8以上之烴基與反應性部位的化合物(長鏈烴化合物)、及具有矽氧烷基與反應性部位的化合物(聚矽氧化合物)之群組的一種。 In other words, as the hydrophobic compound to be subjected to the hydrophobization treatment on the surface of the particles, a compound (fluoride) selected from the group consisting of a fluoroalkyl group having a carbon number of 4 or more and a reactive site, and having a carbon number of 8 or more is preferably used. One of a group of a compound having a hydrocarbon group and a reactive site (long-chain hydrocarbon compound) and a compound having a sulfoxyalkyl group and a reactive site (polyoxyl compound).

長鏈烴化合物係表示分子中具有疏水基的碳數8以上之烴基與反應性部位的化合物。碳數8以上之烴基較佳為碳數8以上30以下。又，不論碳數8以上之烴基是直鏈結構、分枝結構或脂環結構皆能夠選擇。作為長鏈烴化合物，較佳能夠使用碳數10以上22以下之直鏈狀烷醇、烷基環氧化合物、丙烯酸烷酯、甲基丙烯酸烷酯、羧酸烷酯(包含酸酐及酯類)等。 The long-chain hydrocarbon compound is a compound having a hydrocarbon group having 8 or more carbon atoms and a reactive site having a hydrophobic group in the molecule. The hydrocarbon group having 8 or more carbon atoms is preferably a carbon number of 8 or more and 30 or less. Further, the hydrocarbon group having a carbon number of 8 or more can be selected from a linear structure, a branched structure or an alicyclic structure. As the long-chain hydrocarbon compound, a linear alkanol having 10 to 22 or less carbon atoms, an alkyl epoxy compound, an alkyl acrylate, an alkyl methacrylate, or an alkyl carboxylate (including an acid anhydride and an ester) can be preferably used. Wait.

作為長鏈烴化合物的具體例，可舉出辛醇、辛二醇、硬脂醇等之多元醇；丙烯酸辛酯、甲基丙烯酸辛酯、丙烯酸-2-羥基辛酯、甲基丙烯酸-2-羥基辛酯等之丙烯酸酯(甲基丙烯酸酯)；辛基三甲氧基矽烷等之烷基烷氧基矽烷等。 Specific examples of the long-chain hydrocarbon compound include polyhydric alcohols such as octanol, octanediol, and stearyl alcohol; octyl acrylate, octyl methacrylate, 2-hydroxyoctyl acrylate, and methacrylic acid-2. An acrylate (methacrylate) such as hydroxyoctyl ester; an alkyl alkoxy decane such as octyltrimethoxydecane; and the like.

作為聚矽氧化合物，可舉出分子中具有疏水基之矽氧烷基與反應性部位的化合物。聚矽氧化合物之反應性部位較佳使用丙烯醯氧基或甲基丙烯醯氧基。 Examples of the polyoxymethylene compound include a compound having a hydrophobic group and a reactive moiety in the molecule. As the reactive site of the polyoxyxene compound, an acryloxy group or a methacryloxy group is preferably used.

又，作為矽氧烷基較佳使用以下列通式(4)所示之聚矽氧烷基。 Further, as the phosphonyl group, a polydecyloxyalkyl group represented by the following formula (4) is preferably used.

-(Si(R8)(R9)-O)m-…通式(4) -(Si(R 8 )(R 9 )-O) m -...Formula (4)

(在通式(4)，R8與R9係各自獨立地表示碳數1 至6之烷基、苯基、3-丙烯醯氧基-2-羥丙基伸氧丙基、2-丙烯醯氧基-3-羥丙基伸氧丙基、在末端具有丙烯醯氧基或甲基丙烯醯氧基之聚乙二醇丙基醚基、或是在末端具有羥基之聚乙二醇丙基醚基，m係表示10至200之整數。) (In the formula (4), R 8 and R 9 each independently represent an alkyl group having 1 to 6 carbon atoms, a phenyl group, a 3-propenyloxy-2-hydroxypropyloxypropyl group, and a 2-propene fluorene group. Oxy-3-hydroxypropyloxypropyl, polyethylene glycol propyl ether having propylene methoxy or methacryloxy group at the terminal, or polyethylene glycol propyl ether having a hydroxyl group at the terminal Base, m is an integer from 10 to 200.)

作為疏水基係具有以通式(4)所代表的聚矽氧烷基之聚矽氧化合物的具體例，可舉出具有以下列通式(5)所代表的二甲基矽氧烷基、以及反應性部位之化合物。作為具有通式(5)之二甲基矽氧烷基、以及反應性部位之聚矽氧化合物的具體例，可舉出X-22-164B、X-22-164C、X-22-5002、X-22-174D、X-22-167B(以上商品名、信越化學工業股份有限公司製)等。 Specific examples of the polyfluorene oxide compound having a polyoxyalkylene group represented by the general formula (4) as the hydrophobic group include a dimethyl anthracene group represented by the following formula (5). And compounds of the reactive sites. Specific examples of the polyoxonium oxide having a dimethyloxyalkylene group of the formula (5) and a reactive site include X-22-164B, X-22-164C, and X-22-5002. X-22-174D, X-22-167B (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), etc.

(式中，R係表示碳數1以上7以下烷基，k係表示0或1之整數，m係表示10或200之整數。) (wherein R represents an alkyl group having 1 or more and 7 or less carbon atoms, k is an integer of 0 or 1, and m is an integer of 10 or 200.)

又，作為疏水基係具有以通式(4)所代表的聚矽氧烷基與反應性部位之聚矽氧化合物的其他具體例，可舉出以通式(6)所代表的3-丙烯醯氧基-2-羥丙基伸氧丙基與甲基之化合物、以通式(7)所代表的2-丙烯醯氧基-3- 羥丙基伸氧丙基與甲基之化合物。 In addition, as another specific example of the polyoxyalkylene group having a polyoxyalkylene group represented by the formula (4) and a reactive site, as the hydrophobic group, 3-propene represented by the formula (6) a compound of a nonyloxy-2-hydroxypropyloxypropyl group and a methyl group, 2-propenyloxy-3- represented by the formula (7) A compound of hydroxypropyloxypropyl and methyl.

(在通式(6)與(7)，R係表示碳數1以上7以下之烷基，k係表示0或1之整數，m係10至200中任一整數。) (In the general formulae (6) and (7), R represents an alkyl group having 1 or more and 7 or less carbon atoms, k is an integer of 0 or 1, and m is an integer of 10 to 200.)

還有，作為疏水基係具有以通式(4)所代表的聚矽氧烷基與反應性部位之聚矽氧化合物的其他具體例，可舉出以通式(8)所代表的在末端具有丙烯醯氧基或甲基丙烯醯氧基之聚乙二醇丙基醚基與甲基的化合物、以通式(9)所代表的在末端具有羥基之聚乙二醇丙基醚基 與甲基的化合物。 Further, as a specific example of the polyoxyalkyloxy group represented by the general formula (4) and the polyoxyalkylene compound represented by the general formula (4), the terminal represented by the general formula (8) may be mentioned. a compound having a polyethylene glycol propyl ether group of a propylene methoxy group or a methacryloxy group and a methyl group, and a polyethylene glycol propyl ether group having a hydroxyl group at a terminal represented by the formula (9) A compound with a methyl group.

(在通式(8)與(9)，R係表示碳數1以上7以下之烷基，k係表示0或1之整數，x係1至10之整數，m係10至200之整數。) (In the general formulae (8) and (9), R represents an alkyl group having 1 or more and 7 or less carbon atoms, k is an integer of 0 or 1, x is an integer of 1 to 10, and m is an integer of 10 to 200. )

針對具有碳數4以上之氟烷基與反應性部位的氟化物加以說明。於此，氟烷基可為直鏈結構或分枝結構中任一種。又，作為氟烷基較佳為碳數4以上8以下。作為如此之氟化物，能夠使用氟烷基醇、氟烷基環氧化物、氟烷基鹵化物、丙烯酸氟烷酯、羧酸氟烷酯(含有酸酐及酯類)等。該等之中，較佳為丙烯酸氟烷酯、甲基 丙烯酸氟烷酯，例如，能夠使用從以上述通式(3)所舉出的化合物中具有碳數4以上之氟烷基的化合物。 Fluoride having a fluoroalkyl group having 4 or more carbon atoms and a reactive site will be described. Here, the fluoroalkyl group may be either a linear structure or a branched structure. Further, the fluoroalkyl group is preferably a carbon number of 4 or more and 8 or less. As such a fluoride, a fluoroalkyl alcohol, a fluoroalkyl epoxide, a fluoroalkyl halide, a fluoroalkyl acrylate, a fluoroalkyl carboxylic acid ester (including an acid anhydride and an ester), or the like can be used. Among these, fluoroalkyl acrylate and methyl are preferred. As the fluoroalkyl acrylate, for example, a compound having a fluoroalkyl group having 4 or more carbon atoms from the compound represented by the above formula (3) can be used.

氟化物中之氟烷基數未必為1個，氟化物亦可具有複數之氟烷基。 The number of fluoroalkyl groups in the fluoride is not necessarily one, and the fluoride may have a plurality of fluoroalkyl groups.

第1硬被覆層係用以抑制在硬被覆膜表面發生刮傷，較佳為高硬度，依據JIS K 5600-5-4(1999年)所定義的鉛筆硬度，較佳為H以上。還有，鉛筆硬度之上限為9H左右。 The first hard coating layer is for suppressing scratching on the surface of the hard coating film, and is preferably high in hardness. The pencil hardness is preferably H or more in accordance with JIS K 5600-5-4 (1999). Also, the upper limit of the pencil hardness is about 9H.

第1硬被覆層之作為樹脂較佳含有熱硬化性樹脂或是活性能量線硬化性樹脂，特佳含有活性能量線硬化性樹脂。於此，所謂活性能量線硬化性樹脂係意指藉由紫外線或電子線等之活性能量線所聚合而硬化的樹脂。 The resin of the first hard coating layer preferably contains a thermosetting resin or an active energy ray-curable resin, and particularly preferably an active energy ray-curable resin. Here, the active energy ray-curable resin means a resin which is cured by polymerization of an active energy ray such as ultraviolet rays or electron beams.

作為用以獲得活性能量線硬化性樹脂之聚合性化合物，可舉出具有丙烯醯基、甲基丙烯醯基、丙烯醯氧基、甲基丙烯醯氧基、乙烯基、烯丙基等之聚合性官能基之化合物(單體或寡聚物)。 The polymerizable compound for obtaining an active energy ray-curable resin may, for example, be a polymerization having an acrylonitrile group, a methacryl fluorenyl group, an acryloxy group, a methacryloxy group, a vinyl group, an allyl group or the like. A functional group of compounds (monomers or oligomers).

第1硬被覆層較佳藉由利用濕式塗布法而塗布含有上述聚合性化合物之活性放射線硬化性組成物，於必要時乾燥後，照射活性能量線後硬化所形成之物。 In the first hard coating layer, the active radiation curable composition containing the polymerizable compound is applied by a wet coating method, and if necessary, dried, and then irradiated with an active energy ray to cure the formed material.

以下，舉出聚合性化合物(單體或寡聚物)，但不受該等化合物所限定。還有，於下列之說明中，成為「…(甲基)丙烯酸酯」之表現係包含「…丙烯酸酯」與「…甲基丙烯酸酯」之2種化合物。 Hereinafter, a polymerizable compound (monomer or oligomer) will be mentioned, but it is not limited by these compounds. In addition, in the following description, the expression "...(meth)acrylate" includes two compounds of "...acrylate" and "...methacrylate".

作為單體，例如，可舉出(甲基)丙烯酸甲酯 、(甲基)丙烯酸月桂酯、(甲基)丙烯酸乙氧基二乙二醇酯、(甲基)丙烯酸甲氧基三乙二醇酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸四氫呋喃酯、(甲基)丙烯酸異酯、(甲基)丙烯酸-2-羥乙酯、(甲基)丙烯酸-2-羥丙酯、(甲基)丙烯酸-2-羥基-3-苯氧酯等之單官能丙烯酸酯；二(甲基)丙烯酸新戊二醇酯、二(甲基)丙烯酸-1,6-己二醇酯、三(甲基)丙烯酸三羥甲基丙烷酯、三(甲基)丙烯酸季戊四醇酯、四(甲基)丙烯酸季戊四醇酯、三(甲基)丙烯酸二季戊四醇酯、四(甲基)丙烯酸二季戊四醇酯、五(甲基)丙烯酸二季戊四醇酯、六(甲基)丙烯酸二季戊四醇酯、三(甲基)丙烯酸三季戊四醇酯、六(甲基)三丙烯酸三季戊四醇酯、三羥甲基丙烷(甲基)丙烯酸苯甲酸酯、三羥甲基丙烷苯甲酸酯等之多官能丙烯酸酯；二(甲基)丙烯酸丙三醇酯六亞甲基二異氰酸酯、三(甲基)丙烯酸季戊四醇酯六亞甲基二異氰酸酯等之丙烯酸胺甲酸酯。 Examples of the monomer include methyl (meth)acrylate, lauryl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, and methoxytriethylene (meth)acrylate. Alcohol ester, phenoxyethyl (meth)acrylate, tetrahydrofuran (meth)acrylate, (meth)acrylic acid Monofunctional acrylates such as esters, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxy (meth)acrylate; Neomethyl pentyl methacrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tetra ( Pentaerythritol ethyl methacrylate, dipentaerythritol tris(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tris(A) a polyfunctional acrylate such as tripentaerythritol acrylate, tripentaerythritol hexa(meth) acrylate, benzoate (meth) acrylate, trimethylolpropane benzoate or the like; An urethane urethane such as glycerol (meth) acrylate hexamethylene diisocyanate or pentaerythritol tri(meth) acrylate hexamethylene diisocyanate.

於上述單體之中，較佳使用1分子中具有3個以上聚合性官能基之多官能單體。 Among the above monomers, a polyfunctional monomer having three or more polymerizable functional groups in one molecule is preferably used.

作為寡聚物，例如，可舉出聚(甲基)丙烯酸酯、聚(甲基)丙烯酸胺甲酸酯、(甲基)丙烯酸環氧酯、(甲基)丙烯酸聚醚酯、(甲基)丙烯酸醇酸酯、(甲基)丙烯酸三聚氰胺酯、聚矽氧(甲基)丙烯酸酯等。 Examples of the oligomer include poly(meth)acrylate, poly(meth)acrylic acid urethane, (meth)acrylic acid epoxy ester, (meth)acrylic acid polyether ester, and (methyl). Acrylic acid alkoxide, melamine (meth)acrylate, polyoxymethylene (meth) acrylate, and the like.

於上述寡聚物之中，較佳使用1分子中具有3個以上之聚合性官能基的多官能(甲基)丙烯酸聚胺甲酸酯寡聚物。關聯之多官能的(甲基)丙烯酸聚胺甲酸酯寡聚物能夠使用市售中之物。例如，可舉出共榮社化學( 股)製之丙烯酸聚胺甲酸酯AH系列、丙烯酸聚胺甲酸酯AT系列、丙烯酸聚胺甲酸酯UA系列；根上工業(股)製之UN-3320系列、UN-900系列、新中村化學工業(股)製之NK寡聚物U系列、Daicel UCB公司製之Ebecryl1290系列等。 Among the above oligomers, a polyfunctional (meth)acrylic polyurethane oligomer having three or more polymerizable functional groups in one molecule is preferably used. The associated polyfunctional (meth)acrylic polyurethane oligomer can be used in commercial quantities. For example, Gongrongshe Chemical ( Acrylic Polyurethane AH Series, Acrylic Polyurethane AT Series, Acrylic Polyurethane UA Series; UN-3320 Series, UN-900 Series, Xinzhongcun NK oligomer U series manufactured by Chemical Industry Co., Ltd., Ebecryl 1290 series manufactured by Daicel UCB, etc.

相對於活性能量線硬化性組成物之固形物總量100質量%而言，在活性能量線硬化性組成物之聚合性化的含量較佳為50質量%以上，更佳為55質量%以上，進一步較佳為60質量%以上，特佳為70質量%以上。上限較佳為97質量%以下，更佳為95質量%以下。 The content of the polymerizable property of the active energy ray-curable composition is preferably 50% by mass or more, and more preferably 55% by mass or more, based on 100% by mass of the total solid content of the active energy ray-curable composition. It is more preferably 60% by mass or more, and particularly preferably 70% by mass or more. The upper limit is preferably 97% by mass or less, and more preferably 95% by mass or less.

將紫外線作為活性能量線使用之情形，活性能量線硬化性組成物較佳含有光聚合起始劑。作為關聯之光聚合起始劑的具體例，例如，能夠使用苯乙酮、2,2-二乙氧基苯乙酮、對二甲基苯乙酮、對二甲胺基苯丙酮、二苯甲酮、2-氯二苯甲酮、4,4’-二氯二苯甲酮、4,4’-雙(二乙胺基)二苯甲酮、米其勒酮、苯偶醯、苯偶因、苯偶因甲基醚、苯偶因乙基醚、苯偶因異丙基醚、甲基苯醯基甲酸酯、對異丙基-α-羥基異丁基苯酚、α-羥基異丁基苯酚、2,2-二甲氧基-2-苯基苯乙酮、1-羥基環己基苯基酮等之羰基化合物；一硫化四甲基秋蘭姆、二硫化四甲基秋蘭姆、噻噸酮、2-氯噻噸酮、2-甲基噻噸酮等之硫化物等。該等光聚合起始劑可單獨使用，亦可組合2種以上而使用。 In the case where ultraviolet rays are used as the active energy ray, the active energy ray-curable composition preferably contains a photopolymerization initiator. Specific examples of the photopolymerization initiator to be used include, for example, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, and diphenyl. Ketone, 2-chlorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis(diethylamino)benzophenone, mischrone, benzophenone, benzene Occasion, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, methyl benzoate, p-isopropyl-α-hydroxyisobutyl phenol, α-hydroxyl a carbonyl compound such as isobutylphenol, 2,2-dimethoxy-2-phenylacetophenone or 1-hydroxycyclohexyl phenyl ketone; tetramethylthiuram monosulfide, tetramethylsulfide disulfide a sulfide such as lam, thioxanthone, 2-chlorothioxanthone or 2-methylthioxanthone. These photopolymerization initiators may be used singly or in combination of two or more.

又，光聚合起始劑一般已被市售，能夠使用該等。例如，可舉出Ciba Specialty Chemicals(股)製之 Irgacure(註冊商標)184、Irgacure 907、Irgacure 379、Irgacure 819、Irgacure 127、Irgacure 500、Irgacure 754、Irgacure 250、Irgacure 1800、Irgacure 1870、Irgacure OXE01、DAROCUR TPO、DAROCUR 1173等；日本Siber Hegner(股)製之Speedcure MBB、Speedcure PBZ、Speedcure ITX、Speedcure CTX、Speedcure EDB、Esacure ONE、Esacure KIP150、Esacure KTO46等；日本化藥(股)製之KAYACURE DETX-S、KAYACURE CTX、KAYACURE BMS、KAYACURE DMBI等。 Further, photopolymerization initiators are generally commercially available, and these can be used. For example, it can be made by Ciba Specialty Chemicals. Irgacure (registered trademark) 184, Irgacure 907, Irgacure 379, Irgacure 819, Irgacure 127, Irgacure 500, Irgacure 754, Irgacure 250, Irgacure 1800, Irgacure 1870, Irgacure OXE01, DAROCUR TPO, DAROCUR 1173, etc.; Japan Siber Hegner (share) Speedcure MBB, Speedcure PBZ, Speedcure ITX, Speedcure CTX, Speedcure EDB, Esacure ONE, Esacure KIP150, Esacure KTO46, etc.; KAYACURE DETX-S, KAYACURE CTX, KAYACURE BMS, KAYACURE DMBI, etc. made by Nippon Kayaku Co., Ltd.

相對於活性能量線硬化性組成物之固形物總量100質量%而言，上述光聚合起始劑含量之範圍適宜為0.1至10質量%之範圍，較佳為0.5至8質量%之範圍。 The content of the photopolymerization initiator in the range of preferably from 0.1 to 10% by mass, preferably from 0.5 to 8% by mass, based on 100% by mass of the total solid content of the active energy ray-curable composition.

活性能量線硬化性組成物能夠進一步含有各種添加劑，例如，抗氧化劑、紫外線吸收劑、平坦劑、粒子分散劑、有機系抗靜電劑、潤滑劑、著色劑、顏料等。 The active energy ray-curable composition can further contain various additives such as an antioxidant, an ultraviolet absorber, a flat agent, a particle dispersant, an organic antistatic agent, a lubricant, a colorant, a pigment, and the like.

活性能量線硬化性組成物係含有在第1硬被覆層表面用以形成突起之粒子。作為關聯的粒子較佳使用已實施上述之表面處理或是疏水化處理的粒子。相對於活性能量線硬化性組成物之固形物總量100質量%而言，在活性能量線硬化性組成物含量之範圍較佳為2.5至17質量%之範圍，更佳為3至15質量%之範圍，特佳為4至12質量%之範圍。 The active energy ray-curable composition contains particles for forming protrusions on the surface of the first hard coating layer. As the associated particles, particles which have been subjected to the above surface treatment or hydrophobization treatment are preferably used. The content of the active energy ray-curable composition is preferably in the range of 2.5 to 17% by mass, more preferably 3 to 15% by mass, based on 100% by mass of the total solid content of the active energy ray-curable composition. The range is particularly preferably in the range of 4 to 12% by mass.

第1硬被覆層折射率之範圍較佳為1.48至1.54之範圍，更佳為1.50至1.54之範圍。藉由利用濕式塗 布法而塗布上述之活性能量線硬化性組成物，於必要時乾燥後，照射活性能量線後硬化而形成第1硬被覆層，能夠獲得折射率為1.48至1.54之範圍的第1硬被覆層。 The refractive index of the first hard coating layer preferably ranges from 1.48 to 1.54, more preferably from 1.50 to 1.54. By using wet coating The above-described active energy ray-curable composition is applied by a method of drying, and if necessary, dried, irradiated with an active energy ray, and then cured to form a first hard coating layer, thereby obtaining a first hard coating layer having a refractive index of 1.48 to 1.54. .

第1硬被覆層厚度之，範圍適宜為0.5μm以上小於10μm之範圍，較佳為0.8μm以上7μm以下之範圍，更佳為1μm以上5μm以下之範圍，特佳為1μm以上3μm以下。 The thickness of the first hard coating layer is preferably in the range of 0.5 μm or more and less than 10 μm, preferably in the range of 0.8 μm or more and 7 μm or less, more preferably in the range of 1 μm or more and 5 μm or less, and particularly preferably 1 μm or more and 3 μm or less.

若使第1硬被覆層之厚度成為小於0.5μm時，將使第1硬被覆層之硬度降低而變得容易刮傷。又，若使第1硬被覆層之厚度成為10μm以上時，平滑性或抗結塊性將會降低、使卷縮變大而有發生穿透率將會降低等之不當情形。 When the thickness of the first hard coating layer is less than 0.5 μm, the hardness of the first hard coating layer is lowered to cause scratching. In addition, when the thickness of the first hard coating layer is 10 μm or more, the smoothness or the anti-caking property is lowered, the crimping is increased, and the transmittance is lowered.

[硬被覆膜] [hard coating]

硬被覆膜係在基材膜之至少一側面具有第1硬被覆層。硬被覆膜可僅在基材膜之單面具有第1硬被覆層，亦可在基材膜之雙面具有第1硬被覆層。 The hard coating film has a first hard coating layer on at least one side surface of the base film. The hard coating film may have a first hard coating layer on only one side of the base film, or may have a first hard coating layer on both sides of the base film.

又，作為硬被覆膜之其他較佳的形態，可舉出在基材膜之一側面具有第1硬被覆層，在基材膜之另一側面(亦即，在與已設置基材膜之第1硬被覆層之面相反面上)具有第2硬被覆層的硬被覆膜。 Further, as another preferred embodiment of the hard coating film, the first hard coating layer is provided on one side surface of the base film, and the other side surface of the base film (that is, the base film is provided A hard coating film having a second hard coating layer on the opposite surface of the first hard coating layer.

還有，即使在基材膜另一側面所積層的第2硬被覆層採取與在基材膜之一側面所積層的第1硬被覆層完全相同的構造之情形(亦即，在基材膜之雙面分別積層第1硬被覆層之情形)下，為了與一側面之第1硬被覆層區別，也稱為第2硬被覆層。 Further, even when the second hard coating layer which is laminated on the other side surface of the base film has the same structure as the first hard coating layer which is laminated on one side surface of the base film (that is, in the base film) In the case where the first hard coating layer is laminated on both sides, the second hard coating layer is also referred to as a second hard coating layer in order to distinguish it from the first hard coating layer on one side.

[第2硬被覆層] [2nd hard coating]

以下，針對在基材膜另一側面所設置的第2硬被覆層加以說明。 Hereinafter, the second hard coating layer provided on the other side surface of the base film will be described.

第2硬被覆層係用以抑制在硬被覆膜表面發生刮傷，較佳為高硬度，依據JIS K 5600-5-4(1999年)所定義的鉛筆硬度較佳為H以上，更佳為2H以上。還有，鉛筆硬度之上限為9H左右。 The second hard coating layer is for suppressing scratching on the surface of the hard coating film, and is preferably high in hardness. The pencil hardness defined by JIS K 5600-5-4 (1999) is preferably H or more, more preferably It is 2H or more. Also, the upper limit of the pencil hardness is about 9H.

第2硬被覆層表面較佳為更平滑且透明。例如，第2硬被覆層表面之中心線平均粗糙度(Ra2)較佳為25nm以下，更佳為20nm以下，特佳為15nm以下。下限並未被特別限定，實際上為1nm左右。 The surface of the second hard coating layer is preferably smoother and more transparent. For example, the center line average roughness (Ra2) of the surface of the second hard coating layer is preferably 25 nm or less, more preferably 20 nm or less, and particularly preferably 15 nm or less. The lower limit is not particularly limited, and is actually about 1 nm.

第2硬被覆層係用以使第2硬被覆層表面之中心線平均粗糙度(Ra2)成為25nm以下，第2硬被覆層較佳為實質上並不含有平均粒徑較0.5μm為大的粒子。於此，所謂第2硬被覆層實質上並不含有平均粒徑較0.5μm為大的粒子係意指在用以形成第2硬被覆層之塗布液(例如，活性能量線硬化性組成物)刻意不添加平均粒徑較0.5μm為大的粒子。 The second hard coating layer has a center line average roughness (Ra2) of the surface of the second hard coating layer of 25 nm or less, and the second hard coating layer preferably does not substantially contain an average particle diameter of 0.5 μm. particle. Here, the second hard coating layer does not substantially contain a particle system having an average particle diameter of 0.5 μm or more, and means a coating liquid (for example, an active energy ray-curable composition) for forming a second hard coating layer. Particles having an average particle diameter larger than 0.5 μm were not intentionally added.

第2硬被覆層表面較佳為更平滑且透明。因而，在第2硬被覆層表面上因粒子所造成的突起較佳為實質上並不存在，於此，所謂在第2硬被覆層表面上因粒子所造成的突起實質上並不存在係意指第2硬被覆層表面每單位面積(100μm2)之突起個數為100個以下。第2硬被覆層表面每單位面積(100μm2)之突起個數較佳為50個以下，更佳為30個以下，特佳為0個。 The surface of the second hard coating layer is preferably smoother and more transparent. Therefore, it is preferable that the protrusions due to the particles on the surface of the second hard coating layer do not substantially exist. Here, the protrusions caused by the particles on the surface of the second hard coating layer are substantially not intentional. The number of protrusions per unit area (100 μm 2 ) on the surface of the second hard coating layer is 100 or less. The number of protrusions per unit area (100 μm 2 ) of the surface of the second hard coating layer is preferably 50 or less, more preferably 30 or less, and particularly preferably 0.

第2硬被覆層能夠含有平均粒徑為0.5μm以下 之粒子，從上述之觀點，較佳調整第2硬被覆層中所含之粒子的平均粒徑。 The second hard coating layer can contain an average particle diameter of 0.5 μm or less From the above viewpoints, it is preferred to adjust the average particle diameter of the particles contained in the second hard coating layer.

使第2硬被覆層中含有粒子之情形，粒子之平均粒徑較佳為0.2μm以下，更佳為0.1μm以下。相對於第2硬被覆層之固形物總量100質量%而言，如此粒子含量之範圍適宜為0.1至15質量%之範圍，更佳為0.5至10質量%之範圍，特佳為1至8質量%之範圍。 When the particles are contained in the second hard coating layer, the average particle diameter of the particles is preferably 0.2 μm or less, more preferably 0.1 μm or less. The particle content is suitably in the range of 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, particularly preferably 1 to 8 in terms of 100% by mass of the total solid content of the second hard coating layer. The range of mass %.

作為第2硬被覆層之樹脂較佳含有熱硬化性樹脂或是活性能量線硬化性樹脂。特佳含有活性能量線硬化性樹脂。於此，所謂活性能量線硬化性樹脂係意指藉由紫外線或電子線等之活性能量線所聚合而被硬化之樹脂。 The resin as the second hard coating layer preferably contains a thermosetting resin or an active energy ray-curable resin. It is particularly preferred to contain an active energy ray-curable resin. Here, the active energy ray-curable resin means a resin which is cured by polymerization of an active energy ray such as ultraviolet rays or electron beams.

作為用以獲得活性能量線硬化性樹脂之聚合性化合物，能夠使用與上述第1硬被覆層中所說明之物相同。 The polymerizable compound for obtaining an active energy ray-curable resin can be used in the same manner as described for the first hard coating layer.

第2硬被覆層係相同於第1硬被覆層，較佳藉由利用濕式塗布法而塗布含有聚合性化合物之活性能量線硬化性組成物，於必要時乾燥後，照射活性能量線後硬化所形成者。 The second hard coating layer is the same as the first hard coating layer, and it is preferable to apply an active energy ray-curable composition containing a polymerizable compound by a wet coating method, and if necessary, dry and then irradiate the active energy ray to harden. Formed by.

第2硬被覆層折射率之範圍較佳為1.48至1.54之範圍，更佳為1.50至1.54之範圍。藉由利用濕式塗布法而塗布上述之活性能量線硬化性組成物，於必要時乾燥後，照射活性能量線後硬化而形成第2硬被覆層，能夠獲得折射率為1.48至1.54之範圍的第2硬被覆層。 The refractive index of the second hard coat layer preferably ranges from 1.48 to 1.54, more preferably from 1.50 to 1.54. The active energy ray-curable composition is applied by a wet coating method, dried as necessary, and then irradiated with an active energy ray to be cured to form a second hard coating layer, thereby obtaining a refractive index in the range of 1.48 to 1.54. The second hard coating.

第2硬被覆層厚度之範圍適宜為0.5μm以上小 於10μm之範圍，較佳為0.8μm以上7μm以下之範圍，更佳為1μm以上5μm以下之範圍，特佳為1μm以上3μm以下。 The thickness of the second hard coating layer is preferably 0.5 μm or more. The range of 10 μm is preferably 0.8 μm or more and 7 μm or less, more preferably 1 μm or more and 5 μm or less, and particularly preferably 1 μm or more and 3 μm or less.

若使第2硬被覆層之厚度成為小於0.5μm時，將使第2硬被覆層之硬度降低而變得容易刮傷。又，若使第2硬被覆層之厚度成為10μm以上時，平滑性或抗結塊性將會降低而使卷縮變大、或是有發生穿透率將會降低等之不當情形。 When the thickness of the second hard coating layer is less than 0.5 μm, the hardness of the second hard coating layer is lowered to cause scratching. In addition, when the thickness of the second hard coating layer is 10 μm or more, the smoothness or the anti-caking property is lowered to make the crimping large or the transmittance may be lowered.

為了強化基材膜與第2硬被覆層之緊貼性，較佳使上述樹脂層介於基材膜與第2硬被覆層於中間。 In order to strengthen the adhesion between the base film and the second hard coating layer, it is preferred that the resin layer be interposed between the base film and the second hard coating layer.

[透明導電性膜] [Transparent Conductive Film]

本實施形態之硬被覆膜適合作為透明導電性膜之基材膜。亦即，將本實施形態之硬被覆膜作為基材膜使用的透明導電性膜係在本實施形態之硬被覆膜的至少一側面積層有透明導電膜。 The hard coating film of this embodiment is suitable as a base film of a transparent conductive film. In other words, the transparent conductive film used as the base film of the hard coating film of the present embodiment has a transparent conductive film on at least one side of the hard coating film of the present embodiment.

透明導電膜可僅積層於硬被覆膜中任一側面，亦可積層於兩側面。 The transparent conductive film may be laminated on only one of the hard coating films, or may be laminated on both sides.

以下舉出將本發明之硬被覆膜作為基材膜使用的透明導電性膜之數個構成例，但本發明並不受該等所限定。 Hereinafter, a plurality of structural examples of the transparent conductive film used as the base film of the hard coating film of the present invention will be described below, but the present invention is not limited thereto.

i)第1硬被覆層/樹脂層/基材膜/樹脂層/第1硬被覆層/透明導電膜 i) First hard coating layer/resin layer/base material film/resin layer/first hard coating layer/transparent conductive film

ii)透明導電膜/第1硬被覆層/樹脂層/基材膜/樹脂層/第1硬被覆層/透明導電膜 Ii) transparent conductive film / first hard coating layer / resin layer / base film / resin layer / first hard coating layer / transparent conductive film

iii)第1硬被覆層/樹脂層/基材膜/樹脂層/第2硬被覆層/透明導電膜 Iii) first hard coating layer/resin layer/base material film/resin layer/second hard coating layer/transparent conductive film

iv)透明導電膜/第1硬被覆層/樹脂層/基材膜/樹脂層/第2硬被覆層 Iv) transparent conductive film / first hard coat layer / resin layer / base film / resin layer / second hard coat layer

v)透明導電膜/第1硬被覆層/樹脂層/基材膜/樹脂層/第2硬被覆層/透明導電膜 v) Transparent conductive film / first hard coating layer / resin layer / base film / resin layer / second hard coating layer / transparent conductive film

於上述構造例之中，較佳為i)或iii)。亦即，從確保在透明導電膜的積層步驟或加工步驟之硬被覆膜的平滑性或抗結塊性之觀點，在一側之第1硬被覆層中，透明導電膜較佳為並不積層而是使其露出。 Among the above structural examples, it is preferably i) or iii). In other words, from the viewpoint of ensuring smoothness or blocking resistance of the hard coating film in the lamination step or the processing step of the transparent conductive film, the transparent conductive film is preferably not in the first hard coating layer on one side. Laying is to expose it.

又，積層透明導電膜之面的硬被覆層進一步較佳為更平滑且透明。因而，在iii)之構成例中，第2硬被覆層表面之中心線平均粗糙度(Ra2)較佳為25nm以下，更佳為20nm以下，特佳為15nm以下。如上所述，由於積層透明導電膜之面的硬被覆層(例如，第2硬被覆層)之表面較為平滑且透明，因為提高透明導電性膜之透明性，故較佳。 Further, the hard coating layer on the surface of the laminated transparent conductive film is further preferably smoother and more transparent. Therefore, in the configuration example of iii), the center line average roughness (Ra2) of the surface of the second hard coating layer is preferably 25 nm or less, more preferably 20 nm or less, and particularly preferably 15 nm or less. As described above, since the surface of the hard coating layer (for example, the second hard coating layer) on the surface of the laminated transparent conductive film is smooth and transparent, it is preferable because the transparency of the transparent conductive film is improved.

[透明導電膜] [Transparent Conductive Film]

作為形成透明導電性膜之材料，例如，可舉出氧化錫、氧化銦、氧化銻、氧化鋅、ITO(氧化銦錫)、ATO(氧化銻錫)等之金屬氧化物、金屬奈米線(例如銀奈米線)、碳奈米管。該等之中，較佳使用ITO。 Examples of the material for forming the transparent conductive film include metal oxides such as tin oxide, indium oxide, antimony oxide, zinc oxide, ITO (indium tin oxide), and ATO (antimony tin oxide), and metal nanowires ( For example, silver nanowires), carbon nanotubes. Among these, ITO is preferably used.

從確保表面電阻值103Ω/□以下的良好導電性之觀點，透明導電膜之厚度較佳為10nm以上，更佳為15nm以上，特佳為20nm以上。另一方面，若使透明導電膜之厚度變得過大時，因為發生使色調(著色)變強、或透明性將會降低之不當情形，透明導電膜厚度之上限較 佳為60nm以下，更佳為50nm以下，特佳為40nm以下。 The thickness of the transparent conductive film is preferably 10 nm or more, more preferably 15 nm or more, and particularly preferably 20 nm or more from the viewpoint of ensuring good electrical conductivity of the surface resistance value of 10 3 Ω/□ or less. On the other hand, when the thickness of the transparent conductive film is too large, the upper limit of the thickness of the transparent conductive film is preferably 60 nm or less, because the color tone (coloring) is increased or the transparency is lowered. It is 50 nm or less, and particularly preferably 40 nm or less.

作為透明導電膜之形成方法，並未被特別限定，能夠利用習知之方法。具體而言，可舉出真空蒸鍍法、濺鍍法、離子電鍍法等之乾式製膜法(氣相製膜法)、或濕式塗布法 The method for forming the transparent conductive film is not particularly limited, and a conventional method can be used. Specific examples thereof include a dry film forming method (vapor phase forming method) such as a vacuum vapor deposition method, a sputtering method, and an ion plating method, or a wet coating method.

進行如上述所製膜的透明導電膜亦可被圖案化。圖案化係按照透明導電性膜所適用的用途而能夠形成各種圖案。還有，根據透明導電膜之圖案化而形成有圖案部與非圖案部，例如，作為圖案部之形狀可舉出長條狀、格子狀等。 The transparent conductive film which is formed into the film as described above can also be patterned. The patterning can form various patterns in accordance with the application to which the transparent conductive film is applied. In addition, the pattern portion and the non-pattern portion are formed by patterning the transparent conductive film. For example, the shape of the pattern portion may be a long shape or a lattice shape.

一般而言，透明導電膜之圖案化係藉蝕刻所進行。例如，藉由在透明導電膜上，藉光刻法、雷射曝光法、或印刷法形成圖案狀之蝕刻光阻膜後，進行蝕刻處理而使透明導電膜圖案化。透明導電膜被圖案化後，利用鹼性水溶液剝離去除蝕刻光阻膜。 In general, the patterning of the transparent conductive film is performed by etching. For example, a patterned photoresist film is formed on a transparent conductive film by a photolithography method, a laser exposure method, or a printing method, and then an etching treatment is performed to pattern the transparent conductive film. After the transparent conductive film is patterned, the etching resist film is removed by an alkaline aqueous solution.

作為蝕刻液，可使用習知之蝕刻液。例如，氯化氫、溴化氫、硫酸、硝酸、磷酸等之無機酸；醋酸等之有機酸；及該等之混合物、以及該等之水溶液。 As the etching liquid, a conventional etching liquid can be used. For example, inorganic acids such as hydrogen chloride, hydrogen bromide, sulfuric acid, nitric acid, phosphoric acid, etc.; organic acids such as acetic acid; and mixtures thereof, and such aqueous solutions.

作為可用於蝕刻光阻膜之剝離去除的鹼性水溶液，可舉出1至5質量%之氫氧化鈉水溶液或氫氧化鉀水溶液等。 Examples of the alkaline aqueous solution which can be used for the peeling removal of the etching resist film include a 1 to 5 mass% aqueous sodium hydroxide solution or a potassium hydroxide aqueous solution.

[折射率調整層] [refractive index adjustment layer]

在上述透明導電性膜之構成例，透明導電膜可直接積層於第1硬被覆層或是第2硬被覆層之上，較佳使折射率調整層介於透明導電膜與第1硬被覆層或是第2硬被覆 層之間。以下，針對折射率調整層加以說明。 In the configuration example of the transparent conductive film, the transparent conductive film may be directly laminated on the first hard coat layer or the second hard coat layer, and preferably the refractive index adjustment layer is interposed between the transparent conductive film and the first hard coat layer. Or the second hard cover Between the layers. Hereinafter, the refractive index adjustment layer will be described.

折射率調整層可僅以1層構成，亦可為2層以上之積層構造。折射率調整層係具有用以調整其上所積層的透明導電膜之反射色或穿透色的功能、或是用以抑制辨識所圖案化的透明導電膜圖案部之所謂「看得見骨」的功能。 The refractive index adjusting layer may be composed of only one layer, or may have a laminated structure of two or more layers. The refractive index adjusting layer has a function of adjusting a reflection color or a transmission color of a transparent conductive film laminated thereon, or a so-called "visible bone" for suppressing recognition of a patterned transparent conductive film pattern portion. The function.

作為折射率調整層之構造，例如，可舉出折射率(n1)為1.60至1.80之高折射率層的1層構造，折射率(n2)為1.30至1.53之低折射率層的1層構造，或是上述高折射率層與低折射率層的積層構造(低折射率層配置於透明導電膜側)等。 The structure of the refractive index adjusting layer is, for example, a one-layer structure of a low refractive index layer having a refractive index (n1) of 1.60 to 1.80 and a low refractive index layer having a refractive index (n2) of 1.30 to 1.53. Or a laminated structure of the high refractive index layer and the low refractive index layer (the low refractive index layer is disposed on the transparent conductive film side).

上述高折射率層的折射率(n1)之範圍，進一步較佳為1.63至1.78之範圍，更佳為1.65至1.75之範圍。上述低折射率層的折射率(n2)，進一步較佳為1.30至1.50之範圍，更佳為1.30至1.48之範圍，特佳為1.33至1.46之範圍。 The range of the refractive index (n1) of the above high refractive index layer is further preferably in the range of 1.63 to 1.78, more preferably in the range of 1.65 to 1.75. The refractive index (n2) of the above-mentioned low refractive index layer is further preferably in the range of 1.30 to 1.50, more preferably in the range of 1.30 to 1.48, particularly preferably in the range of 1.33 to 1.46.

折射率調整層之厚度(複數層的積層構造之情形係指合計厚度)較佳為200nm以下，更佳為150nm以下，特佳為120nm以下，最佳為100nm以下。下限之厚度較佳為30nm以上，更佳為40nm以上，特佳為50nm以上，最佳為60nm以上。 The thickness of the refractive index adjusting layer (in the case of a laminated structure of a plurality of layers means a total thickness) is preferably 200 nm or less, more preferably 150 nm or less, particularly preferably 120 nm or less, and most preferably 100 nm or less. The thickness of the lower limit is preferably 30 nm or more, more preferably 40 nm or more, particularly preferably 50 nm or more, and most preferably 60 nm or more.

透明導電膜被圖案化之情形，從抑制「看得見骨」之觀點，折射率調整層較佳為高折射率層與低折射率層之積層構造。該情形下，高折射率層之光學厚度與低折射率層之光學厚度的合計(nm)較佳為符合 (1/4)λ(nm)。於此，所謂光學厚度(nm)係折射率與實際之層厚度(nm)的乘積，λ係可見光區域之波長範圍的380至780(nm)。 In the case where the transparent conductive film is patterned, the refractive index adjusting layer is preferably a laminated structure of a high refractive index layer and a low refractive index layer from the viewpoint of suppressing "seeing bone". In this case, the total thickness (nm) of the optical thickness of the high refractive index layer and the optical thickness of the low refractive index layer is preferably in accordance with (1/4) λ (nm). Here, the optical thickness (nm) is a product of a refractive index and an actual layer thickness (nm), and the wavelength range of the λ-based visible light region is 380 to 780 (nm).

於本專利說明書中，所謂高折射率層之光學厚度(nm)與低折射率層之光學厚度(nm)的合計符合(1/4)λ(nm)係指符合下列式1。還有，式中之n1係表示高折射率層之折射率、d1係表示高折射率層之厚度(nm)、n2係表示低折射率層之折射率、d2係表示低折射率層之厚度(nm)。 In the present specification, the sum of the optical thickness (nm) of the high refractive index layer and the optical thickness (nm) of the low refractive index layer corresponds to (1/4) λ (nm), which means that the following formula 1 is satisfied. Further, in the formula, n1 represents the refractive index of the high refractive index layer, d1 represents the thickness (nm) of the high refractive index layer, n2 represents the refractive index of the low refractive index layer, and d2 represents the thickness of the low refractive index layer. (nm).

(380nm/4)≦(n1×d1)+(n2×d2)≦(780nm/4)95nm≦(n1×d1)+(n2×d2)≦195nm…(式1) (380 nm / 4) ≦ (n1 × d1) + (n2 × d2) ≦ (780nm / 4) 95nm ≦ (n1 × d1) + (n2 × d2) ≦ 195nm ... (Formula 1)

亦即，高折射率層之光學厚度(n1×d1)與低折射率層之光學厚度(n2×d2)的合計較佳為95nm以上195nm以下。 That is, the total of the optical thickness (n1 × d1) of the high refractive index layer and the optical thickness (n2 × d2) of the low refractive index layer is preferably 95 nm or more and 195 nm or less.

還有，高折射率層之光學厚度與低折射率層之光學厚度的合計範圍更佳為95至163nm之範圍，特佳為95至150nm之範圍，尤其，最佳為100至140nm之範圍。 Further, the total range of the optical thickness of the high refractive index layer and the optical thickness of the low refractive index layer is more preferably in the range of 95 to 163 nm, particularly preferably in the range of 95 to 150 nm, and particularly preferably in the range of 100 to 140 nm.

例如，高折射率層係藉由利用濕式塗布法而塗布含有折射率1.65以上之金屬氧化物微粒子的活性能量線硬化性組成物，於必要時乾燥後，照射活性能量線後硬化而能夠形成。於此，活性能量線硬化性組成物係含有在上述第1硬被覆層所說明的聚合性化合物與光聚合起始劑之組成物。 For example, the high refractive index layer is coated with an active energy ray-curable composition containing metal oxide fine particles having a refractive index of 1.65 or more by a wet coating method, and dried if necessary, and then cured by irradiation of an active energy ray to form an active energy ray-curable composition. . Here, the active energy ray-curable composition contains a composition of a polymerizable compound and a photopolymerization initiator described in the first hard coating layer.

作為金屬氧化物微粒子，可舉出鈦、鋯、鋅 、錫、銻、鈰、鐵、銦等之金屬氧化物粒子。作為金屬氧化物微粒子的具體例，例如，可舉出氧化鈦、氧化鋯、氧化鋅、氧化錫、氧化銻、氧化鈰、氧化鐵、銻酸鋅、摻雜氧化錫之氧化銦(ITO)、摻雜銻之氧化錫(ATO)、摻雜磷之氧化錫、摻雜鋁之氧化鋅、摻雜鎵之氧化鋅、摻雜氟之氧化錫等，該等金屬氧化物微粒子可單獨使用，亦可合併複數而使用。於上述金屬氧化物微粒子之中，尤其氧化鈦與氧化鋯並不會降低透明性而是能夠提高折射率，故較佳。 Examples of the metal oxide fine particles include titanium, zirconium, and zinc. Metal oxide particles such as tin, antimony, bismuth, iron, and indium. Specific examples of the metal oxide fine particles include titanium oxide, zirconium oxide, zinc oxide, tin oxide, antimony oxide, antimony oxide, iron oxide, zinc antimonate, and tin oxide doped indium oxide (ITO). Tin-doped tin oxide (ATO), phosphorus-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, fluorine-doped tin oxide, etc., such metal oxide fine particles can be used alone, Can be combined with plurals. Among the above metal oxide fine particles, in particular, titanium oxide and zirconium oxide are preferred because they can increase the refractive index without lowering the transparency.

相對於活性能量線硬化性組成物之固形物總量100質量%而言，在活性能量線硬化性組成物之金屬氧化物微粒子的含量較佳為30質量%以上，更佳為40質量%以上，特佳為50質量%以上。上限較佳為70質量%以下，更佳為60質量%以下。 The content of the metal oxide fine particles in the active energy ray-curable composition is preferably 30% by mass or more, and more preferably 40% by mass or more based on 100% by mass of the total solid content of the active energy ray-curable composition. , particularly preferably 50% by mass or more. The upper limit is preferably 70% by mass or less, more preferably 60% by mass or less.

例如，低折射率層係藉由利用濕式塗布法而塗布含有作為低折射率材料之低折射率無機粒子及/或含氟化物的活性能量線硬化性組成物，於必要時乾燥後，照射活性能量線後硬化而能夠形成。於此，活性能量線硬化性組成物係含有在上述第1硬被覆層所說明的聚合性化合物與光聚合起始劑之組成物。 For example, the low refractive index layer is coated with an active energy ray-curable composition containing low refractive index inorganic particles and/or a fluoride as a low refractive index material by a wet coating method, and dried if necessary, and then irradiated. The active energy ray is post-hardened to form. Here, the active energy ray-curable composition contains a composition of a polymerizable compound and a photopolymerization initiator described in the first hard coating layer.

作為低折射率無機粒子，較佳為二氧化矽或氟化鎂等之無機粒子。還有，該等無機粒子較佳為中空狀或多孔質者。相對於活性能量線硬化性組成物之固形物總量100質量%而言，如此之低折射率無機粒子的含量較佳為10質量%以上，更佳為20質量%以上，特佳為30 質量%以上。上限較佳為70質量%以下，更佳為60質量%以下，特佳為50質量%以下。 As the low refractive index inorganic particles, inorganic particles such as cerium oxide or magnesium fluoride are preferable. Further, these inorganic particles are preferably hollow or porous. The content of such low refractive index inorganic particles is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 30%, based on 100% by mass of the total solid content of the active energy ray-curable composition. More than % by mass. The upper limit is preferably 70% by mass or less, more preferably 60% by mass or less, and particularly preferably 50% by mass or less.

作為含氟化物，可舉出含氟單體、含氟寡聚物、含氟高分子化合物。於此，含氟單體或含氟寡聚物係在分子中具有上述聚合性官能基(含有碳-碳雙鍵基之官能基)與氟原子之單體或寡聚物。 Examples of the fluoride-containing compound include a fluorine-containing monomer, a fluorine-containing oligomer, and a fluorine-containing polymer compound. Here, the fluorine-containing monomer or the fluorine-containing oligomer is a monomer or oligomer having a polymerizable functional group (a functional group containing a carbon-carbon double bond group) and a fluorine atom in the molecule.

作為含氟單體、含氟寡聚物，例如，可舉出(甲基)丙烯酸-2,2,2-三氟乙酯、(甲基)丙烯酸-2,2,3,3,3-五氟丙酯、(甲基)丙烯酸-2-(過氟丁基)丙酯、(甲基)丙烯酸-2-(過氟己基)乙酯、(甲基)丙烯酸-2-(過氟辛基)乙酯、(甲基)丙烯酸-2-(過氟癸基)乙酯、(甲基)丙烯酸-β-(過氟辛基)乙酯等之含氟之(甲基)丙烯酸酯類；二(α-氟丙烯酸)-2,2,2-三氟乙基乙二醇酯、二(α-氟丙烯酸)-2,2,3,3,3-五氟丙基乙二醇酯、二(α-氟丙烯酸)-2,2,3,3,4,4,4-七氟丁基乙二醇酯、二(α-氟丙烯酸)-2,2,3,3,4,4,5,5,5-九氟戊基乙二醇酯、二(α-氟丙烯酸)-2,2,3,3,4,4,5,5,6,6,6-十一氟己基乙二醇酯、二(α-氟丙烯酸)-2,2,3,3,4,4,5,5,6,6,7,7,7-十三氟庚基乙二醇酯、二(α-氟丙烯酸)-2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-十五氟辛基乙二醇酯、二(α-氟丙烯酸)-3,3,4,4,5,5,6,6,7,7,8,8,8-十三氟辛基乙二醇酯、二(α-氟丙烯酸)-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-十七氟壬基乙二醇酯等之二(α-氟丙烯酸)氟烷基酯類。 Examples of the fluorine-containing monomer and the fluorine-containing oligomer include (meth)acrylic acid-2,2,2-trifluoroethyl ester and (meth)acrylic acid-2,2,3,3,3-. Pentafluoropropyl ester, 2-(perfluorobutyl)propyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate, 2-(perfluorooctyl) (meth)acrylate Fluorinated (meth) acrylates such as ethyl ester, 2-(perfluorodecyl)ethyl (meth)acrylate, and β-(perfluorooctyl)ethyl (meth)acrylate ; (α-fluoroacrylic acid)-2,2,2-trifluoroethyl glycol ester, bis(α-fluoroacrylic acid)-2,2,3,3,3-pentafluoropropyl glycol ester , bis(α-fluoroacrylic acid)-2,2,3,3,4,4,4-heptafluorobutyl glycol ester, bis(α-fluoroacrylic acid)-2,2,3,3,4, 4,5,5,5-nonafluoropentyl glycol ester, bis(α-fluoroacrylic acid)-2,2,3,3,4,4,5,5,6,6,6-undefluoro Hexyl glycol ester, bis(α-fluoroacrylic acid)-2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl glycol ester, Bis(α-fluoroacrylic acid)-2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl glycol ester, two ( Α-fluoroacrylic acid)-3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl glycol ester, di(α-fluoroacrylic acid)- 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-ten Fluoro-nonyl esters such as ethylene glycol bis (fluoro acrylate alpha]) fluoroalkyl esters.

作為含氟高分子化合物，例如，可舉出以含氟單體與用以賦予交聯性基之單體作為構成單元之含氟共聚物。作為含氟單體單元的具體例，例如，氟烯烴類( 例如，氟乙烯、偏氟乙烯、四氟乙烯、六氟丙烯、過氟-2,2-二甲基-1,3-二唑)、(甲基)丙烯酸之部分或完全氟化烷酯衍生物類(例如Biscoat 6FM(大阪有機化學製)或M-2020(Daikin製)等)、完全或部分氟化乙烯基醚類等。作為用以賦予交聯性基之單鍵，除了如甲基丙烯酸環氧丙酯之分子內預先具有交聯性官能基的(甲基)丙烯酸烷酯單體之外，亦可舉出具有羧基或羥基、胺基、磺酸基等之(甲基)丙烯酸酯單體(例如，(甲基)丙烯酸、(甲基)丙烯酸羥甲酯、(甲基)丙烯酸羥烷酯、丙烯酸烯丙酯等)。 The fluorine-containing polymer compound may, for example, be a fluorine-containing copolymer having a fluorine-containing monomer and a monomer for imparting a crosslinkable group as a constituent unit. Specific examples of the fluorine-containing monomer unit are, for example, fluoroolefins (for example, vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-di Azole, a part of (meth)acrylic acid or a fully fluorinated alkyl ester derivative (for example, Biscoat 6FM (made by Osaka Organic Chemical Co., Ltd.) or M-2020 (made by Daikin)), completely or partially fluorinated vinyl ethers, etc. . Examples of the single bond for imparting a crosslinkable group include a carboxyl group-containing (meth)acrylate monomer having a crosslinkable functional group in the molecule such as glycidyl methacrylate, and a carboxyl group. Or a (meth) acrylate monomer such as a hydroxyl group, an amine group, a sulfonic acid group or the like (for example, (meth)acrylic acid, hydroxymethyl (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate) Wait).

相對於活性能量線硬化性組成物之固形物總量100質量%而言，含氟化物之含量較佳為30質量%以上，更佳為40質量%以上，特佳為50質量%以上。上限較佳為95質量%以下，更佳為90質量%以下，特佳為80質量%以下。 The content of the fluoride is preferably 30% by mass or more, more preferably 40% by mass or more, and particularly preferably 50% by mass or more based on 100% by mass of the total solid content of the active energy ray-curable composition. The upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, and particularly preferably 80% by mass or less.

於含氟化物之中，較佳使用含氟單體、含氟寡聚物。因為含氟單體與含氟寡聚物係在分子中具有聚合性官能基，能夠有助於形成低折射率層之緻密交聯結構，同時也使其低折射率化。 Among the fluorides, a fluorine-containing monomer or a fluorine-containing oligomer is preferably used. Since the fluorine-containing monomer and the fluorine-containing oligomer have a polymerizable functional group in the molecule, it is possible to contribute to the formation of a dense crosslinked structure of the low refractive index layer and also to lower the refractive index.

[觸控面板] [Touch Panel]

將本實施形態之硬被覆膜作成基材膜之透明導電性膜適合作為觸控面板構成構件之一種使用。 The transparent conductive film in which the hard coating film of the present embodiment is used as a base film is suitable for use as one of the touch panel constituent members.

通常，電阻膜式觸控面板係形成使間隔物介於上部電極與下部電極中間所配置的構造，將本實施形態之硬被覆膜作為基材膜之透明導電性膜能夠用於上部 電極與下部電極中任一側或兩側。 In general, the resistive touch panel is formed such that a spacer is interposed between the upper electrode and the lower electrode, and the transparent conductive film having the hard coating film of the present embodiment as a base film can be used for the upper portion. Either or both sides of the electrode and the lower electrode.

又，靜電容量式觸控面板通常利用已圖案化之X電極與Y電極所構成，將本實施形態之硬被覆膜作為基材膜之透明導電性膜能夠用於X電極與Y電極中任一側或兩側。 Further, the capacitance type touch panel is generally composed of a patterned X electrode and a Y electrode, and the transparent conductive film having the hard coating film of the present embodiment as a base film can be used for any of the X electrode and the Y electrode. One side or both sides.

於觸控面板所用之透明導電性膜係要求良好之透明性及加工性(平滑性或抗結塊性)，將本實施形態之硬被覆膜作為基材膜的透明導電性膜能夠充分符合上述特性。 The transparent conductive film used in the touch panel is required to have good transparency and workability (smoothness or anti-caking property), and the transparent conductive film having the hard coating film of the present embodiment as a base film can sufficiently conform to The above characteristics.

[實施例] [Examples]

以下，藉實施例而進一步詳細說明本發明，但本發明並非受該等實施例所限定者。還有，以下顯示在本實施例之測定方法及評估方法。 Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited by the examples. Further, the measurement method and evaluation method of the present embodiment are shown below.

(1)各層折射率之測定 (1) Determination of refractive index of each layer

針對使用旋轉塗布機而將各自的塗布液塗布形成於矽晶圓上之塗膜(乾燥厚度約2μm)，在25℃之溫度條件下，使用相位差測定裝置(Nikon(股)製：NPDM-1000)測定589nm之折射率。 A coating film (dry thickness: about 2 μm) formed by coating each of the coating liquids on a tantalum wafer using a spin coater, and using a phase difference measuring device (manufactured by Nikon Co., Ltd.: NPDM- at a temperature of 25 ° C) 1000) The refractive index at 589 nm was measured.

又，基材膜(PET膜)之折射率係依據JIS K 7105(1981年)，使用Abbe折射率計而測定589nm之折射率。 Further, the refractive index of the base film (PET film) was measured in accordance with JIS K 7105 (1981) using an Abbe refractometer to measure the refractive index at 589 nm.

(2)樹脂層厚度之測定 (2) Determination of thickness of resin layer

將積層有樹脂層之基材膜剖面切成超薄切片，利用藉RuO4染色、OsO4染色、或是兩者之雙重染色所進行的染色超薄切片法，使用TEM(穿透型電子顯微鏡)而以使 剖面構造得以目視之下列條件下觀察，從其剖面照片而測定樹脂層之厚度。還有，測定位置係不存在粒子之部分。另外，測定5處而將其平均值設為樹脂層之厚度。 A cross section of a substrate film in which a resin layer is laminated is cut into ultrathin sections, and a TEM (penetrating electron microscope) is used for dyeing ultrathin sectioning by RuO 4 staining, OsO 4 staining, or double staining of both. The thickness of the resin layer was measured from the cross-sectional photographs under the following conditions in which the cross-sectional structure was visually observed. Also, the measurement position is such that no part of the particles exists. Further, five points were measured, and the average value thereof was defined as the thickness of the resin layer.

‧測定裝置：穿透型電子顯微鏡(日立(股)製H-7100FA型) ‧Measuring device: Penetrating electron microscope (H-7100FA type manufactured by Hitachi Co., Ltd.)

‧測定條件：加速電壓100kV ‧Measurement conditions: Acceleration voltage 100kV

‧試料調整：冷凍超薄切片法 ‧ Sample adjustment: frozen ultra-thin sectioning

‧倍率：30萬倍 ‧ Magnification: 300,000 times

(3)第1及第2硬被覆層、高折射率層、低折射率層厚度之測定 (3) Measurement of the thickness of the first and second hard coating layers, the high refractive index layer, and the low refractive index layer

將硬被覆膜之剖面切成超薄切片，使用TEM(穿透型電子顯微鏡)，以加速電壓100kV觀察(以1至30萬倍之倍率觀察)，從其剖面照片而測定厚度。還有，如第1硬被覆層，對於在表面具有突起之層係於不存在突起之部分的厚度。厚度之測定係在5處進行，將其平均值設為厚度。 The cross section of the hard coating film was cut into ultrathin sections, and observed by an TEM (transmission electron microscope) at an acceleration voltage of 100 kV (observed at a magnification of 10,000 to 300,000 times), and the thickness was measured from the cross-sectional photograph. Further, as for the first hard coating layer, the layer having the protrusion on the surface is attached to the thickness of the portion where the protrusion is not present. The thickness was measured at 5 places, and the average value was set to the thickness.

(4)第1硬被覆層中所含之粒子的平均粒徑之測定 (4) Measurement of average particle diameter of particles contained in the first hard coating layer

使用TEM(穿透型電子顯微鏡)觀察第1硬被覆層之剖面(約1萬至10萬倍)，從其剖面照片而量測任意所選出的30個粒子之各自的最大長度，將平均該等之值設為平均粒徑。 Observing the cross section of the first hard coating layer (about 10,000 to 100,000 times) using a TEM (transmission electron microscope), and measuring the maximum length of each of the selected 30 particles from the cross-sectional photograph, and averaging the The value of the equal value is set to the average particle diameter.

(5)樹脂層中所含之粒子的平均粒徑之測定 (5) Determination of the average particle diameter of particles contained in the resin layer

使用SEM(掃描型電子顯微鏡)，以倍率1萬倍觀察在基材膜所積層的樹脂層表面，將粒子之影像(因粒子所形 成的光之濃淡)連結影像分析器(例如，Cambridge Instrument製QTM900)，改變觀察位置而擷取數據，於合計粒子數成為5000個以上時，進行下列之數值處理，將藉此所求出的數量平均直徑d設為平均粒徑(直徑)。 Using SEM (Scanning Electron Microscope), the surface of the resin layer deposited on the substrate film was observed at a magnification of 10,000 times, and the image of the particles was formed. The image analyzer (for example, QTM900 manufactured by Cambridge Instrument) is connected to the observation position and the data is extracted. When the total number of particles is 5,000 or more, the following numerical processing is performed, and the obtained numerical value is obtained. The number average diameter d is set to an average particle diameter (diameter).

d=Σdi/N d=Σdi/N

於此，di係粒子的等值圓直徑(具有與粒子之剖面積相等面積的圓之直徑)、N係個數。 Here, the iso-circle diameter of the di-type particles (the diameter of a circle having an area equal to the cross-sectional area of the particles) and the number of N-systems.

(6)第1及第2硬被覆層表面之中心線平均粗糙度(Ra1、Ra2)之測定 (6) Determination of the center line average roughness (Ra1, Ra2) of the surface of the first and second hard coating layers

依據JIS B 0601(1982年)，使用探針式表面粗糙度測定器SE-3400(小坂研究所(股)製)而測定。 According to JIS B 0601 (1982), it was measured using a probe type surface roughness measuring device SE-3400 (manufactured by Otaru Laboratory Co., Ltd.).

<測定條件> <Measurement conditions>

傳送速度：0.5mm/秒 Transmission speed: 0.5mm / sec

評估長度：8mm Evaluation length: 8mm

截止值λc：0.08mm Cutoff value λc: 0.08mm

(7)在第1硬被覆層表面之突起個數之量測 (7) Measurement of the number of protrusions on the surface of the first hard coating layer

準備硬被覆膜之切割試料(20cm×15cm)，使用SEM(掃描型電子顯微鏡)拍攝5處該切割試料之第1硬被覆層表面(約1萬至10萬倍)，製作5張影像(表面照片)。接著，針對5張各自的影像，量測存在於影像之1μm正方形(面積1μm2)或是2μm正方形(面積4μm2)之範圍的突起個數，換算成每面積100μm2之個數並加以平均。還有，量測突起個數之面積係按照拍攝倍率而適當變更。 A cut sample (20 cm × 15 cm) of a hard coating film was prepared, and the surface of the first hard coating layer (about 10,000 to 100,000 times) of the cut sample was photographed by SEM (scanning electron microscope) to prepare five images ( Surface photo). Next, the number of protrusions in the range of 1 μm square (area 1 μm 2 ) or 2 μm square (area 4 μm 2 ) of the image is measured for each of the five images, and is converted into an average of 100 μm 2 per area and averaged. . Further, the area in which the number of projections is measured is appropriately changed in accordance with the imaging magnification.

(8)在第1硬被覆層表面之突起的平均直徑之測定 (8) Determination of the average diameter of the protrusion on the surface of the first hard coating layer

使用SEM(掃描型電子顯微鏡)拍攝硬被覆膜之第1硬被覆層表面(約1萬至10萬倍)而作成影像(表面照片)。接著，測定並平均從該影像之中隨意所選出的30個突起之直徑(最大長度)。 The surface of the first hard coating layer (about 10,000 to 100,000 times) of the hard coating film was imaged by SEM (scanning electron microscope) to prepare an image (surface photograph). Next, the diameter (maximum length) of the 30 protrusions randomly selected from the images was measured and averaged.

(9)在第1硬被覆層表面的突起平均高度之測定 (9) Determination of the average height of the protrusion on the surface of the first hard coating layer

準備硬被覆膜之切割試料(20cm×15cm)，使用SEM(掃描型電子顯微鏡)拍攝5處該切割試料之第1硬被覆層剖面(約1萬至10萬倍)，製作5張剖面照片。接著，測定並平均存在於5張剖面照片之全部突起高度。 A cut sample (20 cm × 15 cm) of a hard coating film was prepared, and a cross section of the first hard coating layer (about 10,000 to 100,000 times) of the cut sample was photographed by SEM (scanning electron microscope) to prepare five cross-sectional photographs. . Next, the total protrusion heights of the five cross-sectional photographs were measured and averaged.

(10)突起之平均間隔 (10) Average interval of protrusions

使用SEM(掃描型電子顯微鏡)拍攝硬被覆膜之第1硬被覆層表面(約1萬至10萬倍)，製作影像(表面照片)。在該影像上，劃出橫向與縱向相垂直的各自1條直線。接著，針對沿著橫向之1條直線上(接觸於直線)之突起全部而測定與相鄰接之突起的間隔。針對縱向之1條直線也進行同樣的操作。各自3次變更橫向直線之位置與縱向直線之位置而實施該操作，平均所得之全部的突起間隔。 The surface of the first hard coating layer (about 10,000 to 100,000 times) of the hard coating film was imaged by SEM (scanning electron microscope) to prepare an image (surface photograph). On the image, a straight line perpendicular to the longitudinal direction is drawn. Next, the distance from the adjacent protrusions was measured for all the protrusions on one straight line (contacting the straight line) in the lateral direction. The same operation is performed for one straight line in the vertical direction. This operation was performed by changing the position of the horizontal straight line and the position of the longitudinal straight line three times, and the average projection interval was averaged.

(11)硬被覆膜之測定 (11) Determination of hard coating

依據JIS K 7136(2000年)，使用日本電色工業(股)製之濁度計「NDH-2000」而測定。於測定時，使光射入硬被覆膜之第1硬被覆層的相反面(亦即，設置有第2硬被覆層表面)之表面的方式來配置。 According to JIS K 7136 (2000), it was measured using a turbidity meter "NDH-2000" manufactured by Nippon Denshoku Industries Co., Ltd. At the time of measurement, light is incident on the surface of the opposite surface of the first hard coating layer of the hard coating film (that is, the surface of the second hard coating layer is provided).

(12)硬被覆膜之全光線穿透率 (12) Total light transmittance of hard coating

依據JIS K 7361(1997年)，使用濁度計NDH2000(日 本電色工業(股)製)而測定。 According to JIS K 7361 (1997), use turbidity meter NDH2000 (day This electrochromic industry (stock) system was measured.

(13)硬被覆膜之反射色的目視評估 (13) Visual assessment of the reflection color of the hard coating

將黑色黏著膠帶(日東電工製“乙烯膠No.21 Tokuhaba黑”)貼附於硬被覆膜之第2硬被覆層表面，在暗室三波長螢光燈下，以目視觀察第1硬被覆層表面之反射色，以下列之基準進行。 A black adhesive tape ("ethylene rubber No. 21 Tokuhaba black" manufactured by Nitto Denko Corporation) was attached to the surface of the second hard coating layer of the hard coating film, and the first hard coating layer was visually observed under a dark room three-wavelength fluorescent lamp. The reflected color of the surface was measured on the basis of the following.

同樣地，將黑色黏著膠帶(日東電工製“乙烯膠帶No.21 Tokuhaba黑”)貼附於硬被覆膜之第1硬被覆層表面，在暗室三波長螢光燈下，以目視觀察第2硬被覆層表面之反射色，以下列之基準進行。 In the same manner, a black adhesive tape ("ethylene tape No. 21 Tokuhaba black" manufactured by Nitto Denko Corporation) was attached to the surface of the first hard coating layer of the hard coating film, and the second observation was carried out under a dark room three-wavelength fluorescent lamp. The reflection color of the surface of the hard coating layer was carried out on the basis of the following.

A：反射色為中性且幾乎為無色。 A: The reflected color is neutral and almost colorless.

C：反射色呈現著色。 C: The reflected color is colored.

(14)平滑性之評估 (14) Evaluation of smoothness

切斷硬被覆膜而製作2片薄片(20cm×15cm)。使2片薄片之第1硬被覆層表面與第2硬被覆層表面相向的方式來些微地偏移2片薄片而重疊後放置於平滑之台上，用手指而將下方之薄片固定於台上，利用以手來使上方之薄片滑動的方法而進行平滑性良否之判定。測定環境係23℃、55%RH。 The hard coating film was cut to prepare two sheets (20 cm × 15 cm). The surface of the first hard coating layer of the two sheets is slightly offset from the surface of the second hard coating layer, and the two sheets are slightly overlapped, placed on a smooth table, and the lower sheet is fixed to the table with a finger. The smoothness is determined by a method of sliding the upper sheet by hand. The measurement environment was 23 ° C and 55% RH.

A：上方之薄片的平滑性良好。 A: The smoothness of the upper sheet is good.

B：雖然上方之薄片的平滑性變差，但仍為良好。 B: Although the smoothness of the upper sheet deteriorated, it was still good.

C：上方之薄片不平滑。 C: The sheet above is not smooth.

(15)抗結塊性之評估 (15) Evaluation of anti-caking properties

切斷硬被覆膜而製作2片薄片(20cm×15cm)。使該2片薄片之第1硬被覆層面與第2硬被覆層面相向的方式來 重疊。接著，以玻璃板夾入重疊2片薄片的試料，放置約3kg之載重，在50℃、90%(RH)之環境中放置48小時。接著，藉目視觀察重疊面而確認牛頓環之發生狀況後，剝離兩者，依照下列之基準而評估。 The hard coating film was cut to prepare two sheets (20 cm × 15 cm). The first hard cover layer of the two sheets is opposed to the second hard cover layer. overlapping. Next, a sample in which two sheets were stacked was sandwiched between glass plates, and a load of about 3 kg was placed, and placed in an environment of 50 ° C and 90% (RH) for 48 hours. Next, after confirming the occurrence of the Newton's ring by visually observing the overlapping surface, both were peeled off and evaluated according to the following criteria.

A：剝離前未發生牛頓環，於剝離時未發出剝離聲音，輕易地被剝離。 A: No Newton's ring occurred before peeling, and no peeling sound was emitted at the time of peeling, and it was easily peeled off.

B：剝離前發生一部分發生牛頓環，於剝離時一面發出小的剝離聲音，一面輕易地被剝離。 B: A part of the Newton's ring occurred before peeling, and a small peeling sound was emitted while peeling, and it was easily peeled off.

C：剝離前整面發生牛頓環，於剝離時發出大的剝離聲音而被剝離。 C: A Newton's ring occurred on the entire surface before peeling, and a large peeling sound was emitted at the time of peeling and peeled off.

(16)第1及第2硬被覆層之鉛筆硬度 (16) Pencil hardness of the first and second hard coating layers

針對硬被覆膜之第1硬被覆層表面與第2硬被覆層表面，分別依據JIS K 5600-5-4(1999年)而測定。載重為750g、速度為30mm/分鐘。測定裝置係使用新東科學(股)製之表面性硬度計(HEIDON；型式14DR)。測定時之環境係23℃±2℃、相對濕度為55%±5%。 The surface of the first hard coating layer and the surface of the second hard coating layer of the hard coating film were measured in accordance with JIS K 5600-5-4 (1999). The load is 750 g and the speed is 30 mm/min. The measuring apparatus was a surface hardness tester (HEIDON; type 14DR) manufactured by Shinto Scientific Co., Ltd. The environment at the time of measurement was 23 ° C ± 2 ° C, and the relative humidity was 55% ± 5%.

(17)透明導電膜圖案之辨識性 (17) Identification of transparent conductive film patterns

將試料放置於黑色板上，藉目視而以下列基準來評估是否能夠辨識透明導電膜之圖案部。 The sample was placed on a black plate, and it was evaluated by visual observation whether the pattern portion of the transparent conductive film could be recognized.

A：無法辨識圖案部。 A: The pattern portion cannot be recognized.

C：能夠辨識圖案部。 C: The pattern portion can be recognized.

(18)樹脂層之濕潤張力之測定 (18) Determination of wet tension of resin layer

在常態(23℃、相對濕度50%)之環境中，6小時季化(seasoning)已積層樹脂層之基材膜，在相同環境中，依據JIS K-6768(1999年)而測定。 In a normal state (23 ° C, relative humidity: 50%), a base film of a resin layer having a layered resin layer was seasoned for 6 hours, and it was measured in accordance with JIS K-6768 (1999) in the same environment.

<樹脂層形成用塗布液> <Coating liquid for forming a resin layer>

(樹脂層形成用塗布液a) (coating liquid a for forming a resin layer)

以固形物質量比，混合26質量%之Tg(玻璃轉移溫度)為120℃之聚酯樹脂a、54質量%之Tg為80℃之聚酯樹脂b、18質量%之三聚氰胺系交聯劑、2質量%之粒子而調製水分散塗布液。 In a solid mass ratio, 26% by mass of a polyester resin a having a Tg (glass transition temperature) of 120 ° C, 54% by mass of a polyester resin b having a Tg of 80 ° C, and 18 mass % of a melamine-based crosslinking agent, The water-dispersed coating liquid was prepared by using 2% by mass of particles.

‧聚酯樹脂a：共聚合2,6-萘二甲酸43莫耳%、間苯二甲酸-5-磺酸鈉7莫耳%、含有乙二醇之二醇成分50莫耳%所得之聚酯樹脂。 ‧Polyester resin a: agglomeration of 43 mol% of 2,6-naphthalenedicarboxylic acid, 7 mol% of sodium isophthalate-5-sulfonate, and 50 mol% of glycol component of ethylene glycol Ester resin.

‧聚酯樹脂b：共聚合對苯二甲酸38莫耳%、偏苯三甲酸12莫耳%、含有乙二醇之二醇成分50莫耳%所得之聚酯樹脂。 ‧ Polyester resin b: a polyester resin obtained by copolymerizing 38 mol% of terephthalic acid, 12 mol% of trimellitic acid, and 50 mol% of a glycol component of ethylene glycol.

‧三聚氰胺系交聯劑：三和Chemical(股)製之「NIKALAC MW12LF」。 ‧ Melamine cross-linking agent: "NIKALAC MW12LF" manufactured by Sanhe Chemical Co., Ltd.

‧粒子：平均粒徑0.19μm之膠體二氧化矽。 ‧ Particles: Colloidal ceria having an average particle diameter of 0.19 μm.

(樹脂層形成用塗布液b) (coating liquid b for forming a resin layer)

以固形物質量比，混合下列80質量%之丙烯酸樹脂、18質量%之三聚氰胺系交聯劑、2質量%之粒子而調製水分散塗布液。 The water-dispersed coating liquid was prepared by mixing the following 80% by mass of the acrylic resin, 18% by mass of the melamine-based crosslinking agent, and 2% by mass of the particles in a solid mass ratio.

‧丙烯酸樹脂(包含下列共聚合組成的丙烯酸樹脂) ‧Acrylic resin (including the following copolymerized acrylic resin)

甲基丙烯酸甲酯 63重量% Methyl methacrylate 63% by weight

丙烯酸乙酯 35重量% Ethyl acrylate 35 wt%

丙烯酸 1重量% Acrylic acid 1% by weight

N-羥甲基丙烯醯胺 1重量% N-methylol acrylamide 1% by weight

‧三聚氰胺系交聯劑：三和Chemical(股)製之「NIKALAC MW12LF」。 ‧ Melamine cross-linking agent: "NIKALAC MW12LF" manufactured by Sanhe Chemical Co., Ltd.

‧粒子：平均粒徑0.19μm之膠體二氧化矽。 ‧ Particles: Colloidal ceria having an average particle diameter of 0.19 μm.

<表面處理二氧化矽粒子分散液> <Surface treatment of cerium oxide particle dispersion>

(表面處理二氧化矽粒子分散液A) (Surface treatment of cerium oxide particle dispersion A)

在膠體二氧化矽(日產化學工業股份有限公司製之「有機二氧化矽溶膠IPA-ST-ZL」)150質量份中，混合甲基丙烯醯氧丙基三甲氧基矽烷13.7質量份與10質量%甲酸水溶液1.7質量份，在70℃攪拌1小時。接著，添加氟化物(H2C=CH-COO-CH2-(CF2)8F)13.8質量份及2,2-偶氮二異丁腈0.57質量份後，在90℃加熱攪拌60分鐘而獲得分散液。 In a 150 parts by mass of colloidal cerium oxide ("organic cerium oxide sol IPA-ST-ZL" manufactured by Nissan Chemical Industries, Ltd.), 13.7 parts by mass and 10 masses of methacrylic methoxypropyltrimethoxy decane were mixed. 1.7 parts by mass of a % formic acid aqueous solution was stirred at 70 ° C for 1 hour. Next, 13.8 parts by mass of a fluoride (H 2 C=CH-COO-CH 2 -(CF 2 ) 8 F) and 0.57 parts by mass of 2,2-azobisisobutyronitrile were added, followed by heating and stirring at 90 ° C for 60 minutes. The dispersion was obtained.

(表面處理二氧化矽粒子分散液B) (Surface treatment of cerium oxide particle dispersion B)

在膠體二氧化矽(日產化學工業股份有限公司製之「有機二氧化矽溶膠IPA-ST-ZL」)150質量份中，混合甲基丙烯醯氧丙基三甲氧基矽烷13.7質量份與10質量%甲酸水溶液1.7質量份，在70℃攪拌1小時。接著，添加作為疏水性化合物之氟化物(H2C=CH-COO-CH2-(CF2)8F)9質量份與聚矽氧化合物(大日本Ink化學工業股份有限公司製之「PC-4131」)4.8質量份及2,2-偶氮二異丁腈0.57質量份後，在90℃加熱攪拌60分鐘而獲得分散液。 In a 150 parts by mass of colloidal cerium oxide ("organic cerium oxide sol IPA-ST-ZL" manufactured by Nissan Chemical Industries, Ltd.), 13.7 parts by mass and 10 masses of methacrylic methoxypropyltrimethoxy decane were mixed. 1.7 parts by mass of a % formic acid aqueous solution was stirred at 70 ° C for 1 hour. Next, 9 parts by mass of a fluoride (H 2 C=CH-COO-CH 2 -(CF 2 ) 8 F) as a hydrophobic compound and a polyfluorene oxide compound ("PC manufactured by Dainipa Ink Chemical Industry Co., Ltd.") were added. -4131") 4.8 parts by mass and 0.57 parts by mass of 2,2-azobisisobutyronitrile, and the mixture was heated and stirred at 90 ° C for 60 minutes to obtain a dispersion.

(表面處理二氧化矽粒子分散液C) (Surface treatment of cerium oxide particle dispersion C)

在膠體二氧化矽(日產化學工業股份有限公司製之「有機二氧化矽溶膠IPA-ST-ZL」)330質量份中，於添加混合甲基丙烯醯氧丙基三甲氧基矽烷(信越化學工業( 股)製)8質量份、十三氟辛基三甲氧基矽烷(GE東芝Silicone(股)製)2質量份、及二異丙氧基鋁乙基乙酸酯1.5質量份後，添加離子交換水9質量份。於60℃反應8小時後，冷卻直到室溫，添加乙醯丙酮1.8質量份。接著，一面將環己酮添加於該分散液中，一面在壓力20kPa下藉減壓蒸餾進行溶劑置換而獲得分散液。 In 330 parts by mass of colloidal cerium oxide ("organic cerium oxide sol IPA-ST-ZL" manufactured by Nissan Chemical Industries Co., Ltd.), mixed methacrylic methoxypropyltrimethoxy decane (Shin-Etsu Chemical Industry) ( Addition of ion exchange after 8 parts by mass of trifluorooctyltrimethoxydecane (manufactured by GE Toshiba Silicone Co., Ltd.) and 1.5 parts by mass of diisopropoxy aluminum ethyl acetate 9 parts by mass of water. After reacting at 60 ° C for 8 hours, it was cooled to room temperature, and 1.8 parts by mass of acetamidine acetone was added. Next, cyclohexanone was added to the dispersion, and the solvent was replaced by distillation under reduced pressure at a pressure of 20 kPa to obtain a dispersion.

(表面處理二氧化矽粒子分散液D) (Surface treatment of cerium oxide particle dispersion D)

在膠體二氧化矽(日產化學工業股份有限公司製之「有機二氧化矽溶膠MEK-ST-2040」)150質量份中，混合甲基丙烯醯氧丙基三甲氧基矽烷13.7質量份與10質量%甲酸水溶液1.7質量份，在70℃攪拌1小時。接著，添加氟化物(H2C=CH-COO-CH2-(CF2)8F)13.8質量份及2,2-偶氮二異丁腈0.57質量份後，在90℃加熱攪拌60分鐘而獲得分散液。 In a 150 parts by mass of colloidal cerium oxide ("organic cerium oxide sol MEK-ST-2040" manufactured by Nissan Chemical Industries, Ltd.), 13.7 parts by mass and 10 masses of methacrylic methoxypropyltrimethoxy decane were mixed. 1.7 parts by mass of a % formic acid aqueous solution was stirred at 70 ° C for 1 hour. Next, 13.8 parts by mass of a fluoride (H 2 C=CH-COO-CH 2 -(CF 2 ) 8 F) and 0.57 parts by mass of 2,2-azobisisobutyronitrile were added, followed by heating and stirring at 90 ° C for 60 minutes. The dispersion was obtained.

(表面處理二氧化矽粒子分散液E) (Surface treatment of cerium oxide particle dispersion E)

在膠體二氧化矽(日產化學工業股份有限公司製之「有機二氧化矽溶膠MEK-ST-L」)150質量份中，混合甲基丙烯醯氧丙基三甲氧基矽烷13.7質量份與10質量%甲酸水溶液1.7質量份，在70℃攪拌1小時。接著，添加氟化物(H2C=CH-COO-CH2-(CF2)8F)13.8質量份及2,2-偶氮二異丁腈0.57質量份後，在90℃加熱攪拌60分鐘而獲得分散液。 In a 150 parts by mass of colloidal cerium oxide ("organic cerium oxide sol MEK-ST-L" manufactured by Nissan Chemical Industries Co., Ltd.), 13.7 parts by mass and 10 masses of methacrylic methoxypropyltrimethoxy decane were mixed. 1.7 parts by mass of a % formic acid aqueous solution was stirred at 70 ° C for 1 hour. Next, 13.8 parts by mass of a fluoride (H 2 C=CH-COO-CH 2 -(CF 2 ) 8 F) and 0.57 parts by mass of 2,2-azobisisobutyronitrile were added, followed by heating and stirring at 90 ° C for 60 minutes. The dispersion was obtained.

[實施例1] [Example 1]

依照下列要領而製作硬被覆膜。 Make a hard coating according to the following guidelines.

<樹脂層積層PET膜之製作> <Production of Resin Layered PET Film>

在折射率1.65且厚度100μm之聚對苯二甲酸乙二酯膜(PET膜)之雙面，在PET膜之製造步驟內聯機塗布各自的樹脂層。亦即，利用棒塗布法而將各自的樹脂層形成用塗布液a塗布於長邊方向所單軸拉伸的PET膜之雙面，在100℃乾燥後，接著，於寬度方向進行雙軸拉伸，在230℃實施20秒加熱處理，使其熱硬化，製作在雙面積層有樹脂層之PET膜。在PET膜之雙面所積層的樹脂層折射率分別為1.59、厚度分別為0.09μm。 On both sides of a polyethylene terephthalate film (PET film) having a refractive index of 1.65 and a thickness of 100 μm, the respective resin layers were applied in-line in the production process of the PET film. In other words, each of the coating liquids for forming a resin layer is applied to both sides of a PET film which is uniaxially stretched in the longitudinal direction by a bar coating method, and dried at 100° C., followed by biaxial stretching in the width direction. The film was heat-treated at 230 ° C for 20 seconds to be thermally cured, and a PET film having a resin layer in a double-area layer was produced. The refractive index of the resin layer laminated on both sides of the PET film was 1.59 and the thickness was 0.09 μm, respectively.

<第1及第2硬被覆層之積層> <Layer of the first and second hard coating layers>

在雙面積層有樹脂層的PET膜之一側面的樹脂層上，利用照相凹版塗布法塗布下列之活性放射線硬化性組成物a，在90℃乾燥後，照射紫外線400mJ/cm2使其硬化而形成第1硬被覆層。該第1硬被覆層係厚度為2.6μm、折射率為1.51。 The following active radiation curable composition a was applied onto the resin layer on one side of the PET film having the resin layer of the double-layer layer by a gravure coating method, dried at 90 ° C, and then cured by irradiation with ultraviolet rays of 400 mJ/cm 2 . A first hard coating layer is formed. The first hard coating layer had a thickness of 2.6 μm and a refractive index of 1.51.

接著，在PET膜之另一側面(與積層有第1硬被覆層之面的相反面)的樹脂層上，也使用活性能量線硬化性組成物a，進行與上述同樣的方式而形成第2硬被覆層，製作硬被覆膜。該第2硬被覆層係厚度為2.6μm、折射率為1.51。 Then, the active energy ray-curable composition a is also used on the resin layer of the other side of the PET film (opposite to the surface on which the first hard coating layer is laminated), and the second embodiment is formed in the same manner as described above. Hard coating to make a hard coating. The second hard coat layer had a thickness of 2.6 μm and a refractive index of 1.51.

<活性能量線硬化性組成物a> <Active energy ray-curable composition a>

將六丙烯酸二季戊四醇酯50質量份、丙烯酸酯化合物(東亞合成股份有限公司之「Aronix M111」)37質量份、以固形物換算表面處理二氧化矽粒子分散液A為8質量份、光聚合起始劑(Ciba Specialty Chemicals(股)製「Irgacure 184」)5質量份混入有機溶劑(甲基乙基酮)中而 調製。 50 parts by mass of dipentaerythritol hexaacrylate, 37 parts by mass of an acrylate compound ("Aronix M111" from Toagosei Co., Ltd.), and 8 parts by mass of surface-treated cerium oxide particle dispersion A in terms of solid content, photopolymerization 5 parts by mass of a starting agent ("Irgacure 184" manufactured by Ciba Specialty Chemicals Co., Ltd.) was mixed in an organic solvent (methyl ethyl ketone). modulation.

[實施例2] [Embodiment 2]

除了將第2硬被覆層變更為下列活性能量線硬化性組成物b之外，亦進行相同於實施例1的方式來製作硬被覆膜。該第2硬被覆層之厚度為2.6μm、折射率為1.52。 A hard coating film was produced in the same manner as in Example 1 except that the second hard coating layer was changed to the following active energy ray-curable composition b. The second hard coating layer had a thickness of 2.6 μm and a refractive index of 1.52.

<活性能量線硬化性組成物b> <Active energy ray-curable composition b>

將六丙烯酸二季戊四醇酯48質量份、丙烯酸胺甲酸酯寡聚物(根上工業(股)之「UN-901T」；分子中含有9個聚合性官能基)47質量份、光聚合起始劑(Ciba Specialty Chemicals(股)製「Irgacure 184」)5質量份分散‧溶解於有機溶劑(甲基乙基酮)中而調製。 48 parts by mass of dipentaerythritol hexaacrylate, urethane acrylate oligomer ("UN-901T" of Kosei Industrial Co., Ltd.; 9 polymerizable functional groups in the molecule), 47 parts by mass, photopolymerization initiator (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) 5 parts by mass of dispersion was dissolved in an organic solvent (methyl ethyl ketone) to prepare.

[實施例3] [Example 3]

除了將用以形成第1及第2硬被覆層的活性能量線硬化性組成物變更為下列活性能量線硬化性組成物c之外，亦進行相同於實施例1的方式來製作硬被覆膜。第1及第2硬被覆層的厚度分別為2.6μm、折射率分別為1.51。 A hard coating film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first and second hard coating layers was changed to the following active energy ray-curable composition c. . The thickness of each of the first and second hard coating layers was 2.6 μm and the refractive index was 1.51.

<活性能量線硬化性組成物c> <Active energy ray hardening composition c>

將六丙烯酸二季戊四醇酯87質量份、以固形物換算表面處理二氧化矽粒子分散液B為8質量份、光聚合起始劑(Ciba Specialty Chemicals(股)製「Irgacure 184」)5質量份混入於有機溶劑(甲基乙基酮)中而調製。 87 parts by mass of dipentaerythritol hexaacrylate, 8 parts by mass of surface-treated cerium oxide particle dispersion B in terms of solid content, and 5 parts by mass of a photopolymerization initiator ("Irgacure 184" manufactured by Ciba Specialty Chemicals Co., Ltd.) It is prepared in an organic solvent (methyl ethyl ketone).

[實施例4] [Example 4]

除了將第2硬被覆層變更為上述活性能量線硬化性組成物b之外，亦進行相同於實施例3的方式來製作硬被覆膜。該第2硬被覆層的厚度為2.6μm、折射率為1.52。 A hard coating film was produced in the same manner as in Example 3 except that the second hard coating layer was changed to the active energy ray-curable composition b. The second hard coating layer had a thickness of 2.6 μm and a refractive index of 1.52.

[實施例5] [Example 5]

除了將用以形成第1及第2硬被覆層的活性能量線硬化性組成物變更為下列活性能量線硬化性組成物d之外，亦進行相同於實施例1的方式來製作硬被覆膜。第1及第2硬被覆層的厚度分別為2.6μm、折射率分別為1.51。 A hard coating film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first and second hard coating layers was changed to the following active energy ray-curable composition d. . The thickness of each of the first and second hard coating layers was 2.6 μm and the refractive index was 1.51.

<活性能量線硬化性組成物d> <Active energy ray hardening composition d>

將六丙烯酸二季戊四醇酯87質量份、以固形物換算表面處理二氧化矽粒子分散液C為8質量份、光聚合起始劑(Ciba Specialty Chemicals(股)製「Irgacure 184」)5質量份分散‧溶解於有機溶劑(甲基乙基酮與環己酮之質量比為8：2之混合溶劑)中而調製。 87 parts by mass of dipentaerythritol hexaacrylate, 8 parts by mass of surface-treated cerium oxide particle dispersion C in terms of solid content, and 5 parts by mass of a photopolymerization initiator ("Irgacure 184" manufactured by Ciba Specialty Chemicals Co., Ltd.) ‧ It is prepared by dissolving in an organic solvent (a mixed solvent of methyl ethyl ketone and cyclohexanone in a mass ratio of 8:2).

[實施例6] [Embodiment 6]

除了將第2硬被覆層變更為上述活性能量線硬化性組成物b之外，亦進行相同於實施例5的方式來製作硬被覆膜。該第2硬被覆層的厚度為2.6μm、折射率為1.52。 A hard coating film was produced in the same manner as in Example 5 except that the second hard coating layer was changed to the active energy ray-curable composition b. The second hard coating layer had a thickness of 2.6 μm and a refractive index of 1.52.

[實施例7] [Embodiment 7]

除了將用以形成第1及第2硬被覆層的活性能量線硬化性組成物變更為下列活性能量線硬化性組成物e之外，亦進行相同於實施例1的方式來製作硬被覆膜。第1及第2硬被覆層的厚度分別為2.6μm、折射率分別為1.51。 A hard coating film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first and second hard coating layers was changed to the following active energy ray-curable composition e. . The thickness of each of the first and second hard coating layers was 2.6 μm and the refractive index was 1.51.

<活性能量線硬化性組成物e> <Active energy ray hardening composition e>

將六丙烯酸二季戊四醇酯50質量份、丙烯酸酯化合物(東亞合成股份有限公司之「Aronix M111」)37質量份、以固形物換算表面處理二氧化矽粒子分散液D為8質量份、光聚合起始劑(Ciba Specialty Chemicals(股)製「 Irgacure 184」)5質量份混入有機溶劑(甲基乙基酮)中而調製。 50 parts by mass of dipentaerythritol hexaacrylate, 37 parts by mass of an acrylate compound ("Aronix M111" from Toagosei Co., Ltd.), and 8 parts by mass of a surface-treated cerium oxide particle dispersion D in terms of solid content, photopolymerization Starting agent (Ciba Specialty Chemicals) Irgacure 184") 5 parts by mass was mixed in an organic solvent (methyl ethyl ketone) to prepare.

[實施例8] [Embodiment 8]

除了將第2硬被覆層變更為上述活性能量線硬化性組成物b之外，亦進行相同於實施例7的方式來製作硬被覆膜。該第2硬被覆層的厚度為2.6μm、折射率為1.52。 A hard coating film was produced in the same manner as in Example 7 except that the second hard coating layer was changed to the active energy ray-curable composition b. The second hard coating layer had a thickness of 2.6 μm and a refractive index of 1.52.

[實施例9] [Embodiment 9]

除了將用以形成第1及第2硬被覆層的活性能量線硬化性組成物變更為下列活性能量線硬化性組成物f之外，亦進行相同於實施例1的方式來製作硬被覆膜。第1及第2硬被覆層的厚度分別為2.6μm、折射率分別為1.51。 A hard coating film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first and second hard coating layers was changed to the following active energy ray-curable composition f. . The thickness of each of the first and second hard coating layers was 2.6 μm and the refractive index was 1.51.

<活性能量線硬化性組成物f> <Active energy ray hardening composition f>

將六丙烯酸二季戊四醇酯50質量份、丙烯酸酯化合物(東亞合成股份有限公司之「Aronix M111」)37質量份、以固形物換算表面處理二氧化矽粒子分散液E為8質量份、光聚合起始劑(Ciba Specialty Chemicals(股)製「Irgacure 184」)5質量份混入有機溶劑(甲基乙基酮)中而調製。 50 parts by mass of dipentaerythritol hexaacrylate, 37 parts by mass of an acrylate compound ("Aronix M111" from Toagosei Co., Ltd.), and 8 parts by mass of surface-treated cerium oxide particle dispersion E in terms of solid content, photopolymerization 5 parts by mass of a starting agent ("Irgacure 184" manufactured by Ciba Specialty Chemicals Co., Ltd.) was added to an organic solvent (methyl ethyl ketone) to prepare a mixture.

[實施例10] [Embodiment 10]

除了將第2硬被覆層變更為上述活性能量線硬化性組成物b之外，亦進行相同於實施例9的方式來製作硬被覆膜。該第2硬被覆層的厚度為2.6μm、折射率為1.52。 A hard coating film was produced in the same manner as in Example 9 except that the second hard coating layer was changed to the active energy ray-curable composition b. The second hard coating layer had a thickness of 2.6 μm and a refractive index of 1.52.

[比較例1] [Comparative Example 1]

除了將用以形成第1及第2硬被覆層的活性能量線硬化性組成物變更為下列活性能量線硬化性組成物g之外 ，亦進行相同於實施例1的方式來製作硬被覆膜。第1及第2硬被覆層的厚度分別為2.6μm、折射率分別為1.51。 In addition to changing the active energy ray-curable composition for forming the first and second hard coating layers to the following active energy ray-curable composition g A hard coating film was also produced in the same manner as in Example 1. The thickness of each of the first and second hard coating layers was 2.6 μm and the refractive index was 1.51.

<活性能量線硬化性組成物g> <Active energy ray curable composition g>

將六丙烯酸二季戊四醇酯87質量份、以固形物換算二氧化矽粒子(日產化學工業股份有限公司製之「有機二氧化矽溶膠IPA-ST-ZL」)為8質量份、光聚合起始劑(Ciba Specialty Chemicals(股)製「Irgacure 184」)5質量份分散‧溶解於有機溶劑(甲基乙基酮與環己酮之質量比為8：2之混合溶劑)中而調製。 87 parts by mass of dipentaerythritol hexaacrylate and 8 parts by mass of a photopolymerization initiator based on solid content conversion of cerium oxide particles ("organic cerium oxide sol IPA-ST-ZL" manufactured by Nissan Chemical Industries, Ltd.) (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) 5 parts by mass of the dispersion was dissolved in an organic solvent (a mixed solvent of a methyl ethyl ketone and a cyclohexanone having a mass ratio of 8:2) to prepare.

[比較例2] [Comparative Example 2]

除了將第2硬被覆層變更為上述活性能量線硬化性組成物b之外，亦進行相同於比較例1的方式來製作硬被覆膜。該第2硬被覆層的厚度為2.6μm、折射率為1.52。 A hard coating film was produced in the same manner as in Comparative Example 1 except that the second hard coating layer was changed to the active energy ray-curable composition b. The second hard coating layer had a thickness of 2.6 μm and a refractive index of 1.52.

[比較例3] [Comparative Example 3]

除了將用以形成第1及第2硬被覆層的活性能量線硬化性組成物變更為下列活性能量線硬化性組成物h之外，亦進行相同於實施例1的方式來製作硬被覆膜。第1及第2硬被覆層的厚度分別為2.6μm、折射率分別為1.52。 A hard coating film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first and second hard coating layers was changed to the following active energy ray-curable composition h. . The thickness of each of the first and second hard coating layers was 2.6 μm and the refractive index was 1.52.

<活性能量線硬化性組成物h> <Active energy ray hardening composition h>

將六丙烯酸二季戊四醇酯87質量份、以固形物換算聚甲基丙烯酸甲酯粒子(綜研化學(股)製之「MX-150H」)為8質量份、光聚合起始劑(Ciba Specialty Chemicals(股)製「Irgacure 184」)5質量份分散.溶解於有機溶劑(甲基乙基酮與環己酮之質量比為8：2之混合溶劑)中而調製。 87 parts by mass of dipentaerythritol hexaacrylate and 8 parts by mass of a polymethyl methacrylate particle ("MX-150H" manufactured by Soken Chemical Co., Ltd.) in terms of solid content, and a photopolymerization initiator (Ciba Specialty Chemicals ( 5 parts by mass of "Irgacure 184") was dispersed and dissolved in an organic solvent (mixed solvent of a molar ratio of methyl ethyl ketone to cyclohexanone of 8:2).

[比較例4] [Comparative Example 4]

除了將第2硬被覆層變更為上述活性能量線硬化性組成物b之外，亦進行相同於比較例3的方式來製作硬被覆膜。該第2硬被覆層的厚度為2.6μm、折射率為1.52。 A hard coating film was produced in the same manner as in Comparative Example 3 except that the second hard coating layer was changed to the active energy ray-curable composition b. The second hard coating layer had a thickness of 2.6 μm and a refractive index of 1.52.

[實施例11] [Example 11]

除了將用以形成第1及第2硬被覆層的活性能量線硬化性組成物變更為下列活性能量線硬化性組成物i之外，亦進行相同於實施例1的方式來製作硬被覆膜。第1及第2硬被覆層的厚度分別為2.6μm、折射率分別為1.51。 A hard coating film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first and second hard coating layers was changed to the following active energy ray-curable composition i. . The thickness of each of the first and second hard coating layers was 2.6 μm and the refractive index was 1.51.

<活性能量線硬化性組成物i> <Active energy ray hardening composition i>

將六丙烯酸二季戊四醇酯54質量份、丙烯酸酯化合物(東亞合成股份有限公司之「Aronix M111」)37質量份、以固形物換算表面處理二氧化矽粒子分散液A為4質量份、光聚合起始劑(Ciba Specialty Chemicals(股)製「Irgacure 184」)5質量份混入有機溶劑(甲基乙基酮)中而調製。 54 parts by mass of dipentaerythritol hexaacrylate, 37 parts by mass of an acrylate compound ("Aronix M111" from Toagosei Co., Ltd.), and 4 parts by mass of surface-treated cerium oxide particle dispersion A in terms of solid content, photopolymerization 5 parts by mass of a starting agent ("Irgacure 184" manufactured by Ciba Specialty Chemicals Co., Ltd.) was added to an organic solvent (methyl ethyl ketone) to prepare a mixture.

[實施例12] [Embodiment 12]

除了將用以形成第1及第2硬被覆層的活性能量線硬化性組成物變更為下列活性能量線硬化性組成物j之外，亦進行相同於實施例1的方式來製作硬被覆膜。第1及第2硬被覆層的厚度分別為2.6μm、折射率分別為1.51。 A hard coating film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first and second hard coating layers was changed to the following active energy ray-curable composition j. . The thickness of each of the first and second hard coating layers was 2.6 μm and the refractive index was 1.51.

<活性能量線硬化性組成物j> <Active energy ray hardening composition j>

將六丙烯酸二季戊四醇酯52質量份、丙烯酸酯化合物(東亞合成股份有限公司之「Aronix M111」)37質量份、以固形物換算表面處理二氧化矽粒子分散液A為6質量份、光聚合起始劑(Ciba Specialty Chemicals(股)製「 Irgacure 184」)5質量份混入有機溶劑(甲基乙基酮)中而調製。 52 parts by mass of dipentaerythritol hexaacrylate, 37 parts by mass of an acrylate compound ("Aronix M111" of Toagosei Co., Ltd.), and 6 parts by mass of surface-treated cerium oxide particle dispersion A in terms of solid content, photopolymerization Starting agent (Ciba Specialty Chemicals) Irgacure 184") 5 parts by mass was mixed in an organic solvent (methyl ethyl ketone) to prepare.

[實施例13] [Example 13]

除了將用以形成第1及第2硬被覆層的活性能量線硬化性組成物變更為下列活性能量線硬化性組成物k之外，亦進行相同於實施例1的方式來製作硬被覆膜。第1及第2硬被覆層的厚度分別為2.6μm、折射率分別為1.51。 A hard coating film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first and second hard coating layers was changed to the following active energy ray-curable composition k. . The thickness of each of the first and second hard coating layers was 2.6 μm and the refractive index was 1.51.

<活性能量線硬化性組成物k> <Active energy ray-curable composition k>

將六丙烯酸二季戊四醇酯50質量份、丙烯酸酯化合物(東亞合成股份有限公司之「Aronix M111」)35質量份、以固形物換算表面處理二氧化矽粒子分散液A為10質量份、光聚合起始劑(Ciba Specialty Chemicals(股)製「Irgacure 184」)5質量份混入有機溶劑(甲基乙基酮)中而調製。 50 parts by mass of dipentaerythritol hexaacrylate, 35 parts by mass of an acrylate compound ("Aronix M111" from Toagosei Co., Ltd.), and surface-treated cerium oxide particle dispersion A in terms of solid content, 10 parts by mass, photopolymerization 5 parts by mass of a starting agent ("Irgacure 184" manufactured by Ciba Specialty Chemicals Co., Ltd.) was added to an organic solvent (methyl ethyl ketone) to prepare a mixture.

[實施例14] [Embodiment 14]

除了將用以形成第1及第2硬被覆層的活性能量線硬化性組成物變更為下列活性能量線硬化性組成物1之外，亦進行相同於實施例1的方式來製作硬被覆膜。第1及第2硬被覆層的厚度分別為2.6μm、折射率分別為1.51。 A hard coating film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first and second hard coating layers was changed to the following active energy ray-curable composition 1. . The thickness of each of the first and second hard coating layers was 2.6 μm and the refractive index was 1.51.

<活性能量線硬化性組成物1> <Active energy ray hardening composition 1>

將六丙烯酸二季戊四醇酯50質量份、丙烯酸酯化合物(東亞合成股份有限公司之「Aronix M111」)33質量份、以固形物換算表面處理二氧化矽粒子分散液A為12質量份、光聚合起始劑(Ciba Specialty Chemicals(股)製「Irgacure 184」)5質量份混入有機溶劑(甲基乙基酮)中而 調製。 50 parts by mass of dipentaerythritol hexaacrylate, 33 parts by mass of an acrylate compound ("Aronix M111" of Toagosei Co., Ltd.), and 12 parts by mass of surface-treated cerium oxide particle dispersion A in terms of solid content, photopolymerization 5 parts by mass of a starting agent ("Irgacure 184" manufactured by Ciba Specialty Chemicals Co., Ltd.) was mixed in an organic solvent (methyl ethyl ketone). modulation.

[比較例5] [Comparative Example 5]

除了將用以形成第1及第2硬被覆層的活性能量線硬化性組成物變更為下列活性能量線硬化性組成物m之外，亦進行相同於實施例1的方式來製作硬被覆膜。第1及第2硬被覆層的厚度分別為2.6μm、折射率分別為1.51。 A hard coating film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first and second hard coating layers was changed to the following active energy ray-curable composition m. . The thickness of each of the first and second hard coating layers was 2.6 μm and the refractive index was 1.51.

<活性能量線硬化性組成物m> <Active energy ray hardening composition m>

將六丙烯酸二季戊四醇酯56質量份、丙烯酸酯化合物(東亞合成股份有限公司之「Aronix M111」)37質量份、以固形物換算表面處理二氧化矽粒子分散液A為2質量份、光聚合起始劑(Ciba Specialty Chemicals(股)製「Irgacure 184」)5質量份混入有機溶劑(甲基乙基酮)中而調製。 56 parts by mass of dipentaerythritol hexaacrylate, 37 parts by mass of an acrylate compound ("Aronix M111" of Toagosei Co., Ltd.), and 2 parts by mass of surface-treated cerium oxide particle dispersion A in terms of solid content, photopolymerization 5 parts by mass of a starting agent ("Irgacure 184" manufactured by Ciba Specialty Chemicals Co., Ltd.) was added to an organic solvent (methyl ethyl ketone) to prepare a mixture.

[比較例6] [Comparative Example 6]

除了將用以形成第1及第2硬被覆層的活性能量線硬化性組成物變更為下列活性能量線硬化性組成物n之外，亦進行相同於實施例1的方式來製作硬被覆膜。第1及第2硬被覆層的厚度分別為2.6μm、折射率分別為1.51。 A hard coating film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first and second hard coating layers was changed to the following active energy ray-curable composition n. . The thickness of each of the first and second hard coating layers was 2.6 μm and the refractive index was 1.51.

<活性能量線硬化性組成物n> <Active energy ray hardening composition n>

將六丙烯酸二季戊四醇酯45質量份、丙烯酸酯化合物(東亞合成股份有限公司之「Aronix M111」)30質量份、以固形物換算表面處理二氧化矽粒子分散液A為20質量份、光聚合起始劑(Ciba Specialty Chemicals(股)製「Irgacure 184」)5質量份混入有機溶劑(甲基乙基酮)中而調製。 45 parts by mass of dipentaerythritol hexaacrylate, 30 parts by mass of an acrylate compound ("Aronix M111" of Toagosei Co., Ltd.), 20 parts by mass of surface-treated cerium oxide particle dispersion A in terms of solid content, and photopolymerization 5 parts by mass of a starting agent ("Irgacure 184" manufactured by Ciba Specialty Chemicals Co., Ltd.) was added to an organic solvent (methyl ethyl ketone) to prepare a mixture.

[比較例7] [Comparative Example 7]

於實施例1之樹脂層積層PET膜之製作中，除了將樹脂層形成用塗布液變更為樹脂層形成用塗布液b之外，亦進行相同於實施例1的方式來製作在雙面積層有樹脂層的PET膜。在PET膜雙面所積層的樹脂層之折射率分別為1.52、厚度分別為0.09μm。 In the production of the resin layered PET film of the first embodiment, the coating liquid for forming a resin layer was changed to the coating liquid b for forming a resin layer, and the same was produced in the same manner as in the first embodiment. A PET film of a resin layer. The resin layers laminated on both sides of the PET film had a refractive index of 1.52 and a thickness of 0.09 μm, respectively.

<第1及第2硬被覆層之積層> <Layer of the first and second hard coating layers>

在上述之樹脂層積層PET膜上，進行相同於比較例5而積層第1及第2硬被覆層，製作硬被覆膜。第1及第2硬被覆層的厚度分別為2.6μm、折射率分別為1.51。 On the above-mentioned resin laminated PET film, the first and second hard coating layers were laminated in the same manner as in Comparative Example 5 to prepare a hard coating film. The thickness of each of the first and second hard coating layers was 2.6 μm and the refractive index was 1.51.

[硬被覆膜之評估] [Evaluation of hard coating]

針對上述所得之實施例與比較例之硬被覆膜，將第1及第2硬被覆層之構造顯示於表1，將該等硬被覆膜的評估結果顯示於表2。 With respect to the hard coating films of the examples and the comparative examples obtained above, the structures of the first and second hard coating layers are shown in Table 1, and the evaluation results of the hard coating films are shown in Table 2.

又，針對上述實施例與比較例中之代表性試料，測定在第1硬被覆層表面之突起的平均直徑、平均高度及平均間隔。將其結果顯示於表3。 Further, with respect to the representative samples in the above examples and comparative examples, the average diameter, the average height, and the average interval of the projections on the surface of the first hard coating layer were measured. The results are shown in Table 3.

從上述結果，在實施例1至14，因為在第1硬被覆層表面每單位面積(100μm2)形成300至10000個突起，稱得上平滑性與抗結塊性為良好。又，因為第1及第2硬被覆層之中心線平均粗糙度(Ra1、Ra2)小於30nm，使硬被覆膜之霧度值成為小於1.5%，透明性為良好，稱得上全光線穿透率高。 From the above results, in Examples 1 to 14, since 300 to 10,000 protrusions per unit area (100 μm 2 ) were formed on the surface of the first hard coating layer, it was found that the smoothness and the blocking resistance were good. In addition, since the center line average roughness (Ra1, Ra2) of the first and second hard coating layers is less than 30 nm, the haze value of the hard coating film is less than 1.5%, and the transparency is good, and it is called total light wear. High penetration rate.

[實施例15至24] [Examples 15 to 24]

在實施例1至10之硬被覆膜的第2硬被覆層表面，使得作為透明導電膜之ITO膜成為25nm的方式來利用濺鍍法積層，製作透明導電性膜。相對於該等透明導電膜，評估平滑性與抗結塊性。將其結果顯示於表4。 On the surface of the second hard coating layer of the hard coating film of Examples 1 to 10, a transparent conductive film was produced by lamination by a sputtering method so that the ITO film as the transparent conductive film was 25 nm. Smoothness and anti-caking property were evaluated with respect to the transparent conductive films. The results are shown in Table 4.

還有，透明導電性膜之平滑性與抗結塊性之評估係在上述之「(14)平滑性之評估」及「(15)抗結塊性之評估」中，除了使第1硬被覆層表面與透明導電膜表面相向的方式來重疊而變更之外，亦進行同樣的方式來評估。 In addition, the evaluation of the smoothness and anti-caking property of the transparent conductive film is in the above-mentioned "(14) Evaluation of smoothness" and "(15) Evaluation of anti-caking property", except that the first hard cover is made. The surface of the layer was overlapped and changed in such a manner as to face the surface of the transparent conductive film, and was evaluated in the same manner.

實施例15至24之透明導電性膜中任一種，不論平滑性與抗結塊性皆為良好。 Any of the transparent conductive films of Examples 15 to 24 was excellent in both smoothness and blocking resistance.

[實施例25至29] [Examples 25 to 29]

在實施例2、4、6、8與10之硬被覆膜的第2硬被覆層表面，依照下列之高折射率層與低折射率層之順序來積層，接著在低折射率層之上形成下列之透明導電膜，製作靜電容量式觸控面板用之透明導電性膜。 The surfaces of the second hard coating layer of the hard coating films of Examples 2, 4, 6, 8, and 10 were laminated in the order of the following high refractive index layer and low refractive index layer, and then on the low refractive index layer. The following transparent conductive film was formed to produce a transparent conductive film for a capacitive touch panel.

<高折射率層之積層> <Lamination of high refractive index layer>

利用照相凹版法塗布下列之高折射率層形成用之活性能量線硬化性組成物，在90℃下乾燥後，照射紫外線400mJ/cm2來使其硬化而形成厚度50nm之高折射率層。該高折射率層之折射率為1.68。 The active energy ray-curable composition for forming the following high refractive index layer was applied by a gravure method, dried at 90 ° C, and then cured by irradiation with ultraviolet rays of 400 mJ/cm 2 to form a high refractive index layer having a thickness of 50 nm. The high refractive index layer has a refractive index of 1.68.

(高折射率層形成用之活性放射線硬化性組成物) (Active radiation curable composition for forming a high refractive index layer)

將六丙烯酸二季戊四醇酯21質量份、丙烯酸胺甲酸酯寡聚物(根上工業(股)之「UN-901T」；分子中含有9個聚合性官能基)21質量份、氧化鋯55質量份、及光聚合起始劑(Ciba Specialty Chemicals(股)製「Irgacure 184」)3質量份分散或是溶解於有機溶劑(丙二醇單甲基乙醇)中而調製。 21 parts by mass of dipentaerythritol hexaacrylate, 21 parts by mass of urethane acrylate oligomer ("UN-901T" of Kosei Industrial Co., Ltd.; 9 polymerizable functional groups in the molecule), and 55 parts by mass of zirconia And 3 parts by mass of a photopolymerization initiator ("Irgacure 184" manufactured by Ciba Specialty Chemicals Co., Ltd.) was dispersed or dissolved in an organic solvent (propylene glycol monomethylethanol) to prepare.

<低折射率層之積層> <Layer of low refractive index layer>

利用照相凹版法塗布下列之低折射率層形成用之活性能量線硬化性組成物，在90℃下乾燥後，照射紫外線400mJ/cm2來使其硬化而形成厚度40nm之低折射率層。該低折射率層之折射率為1.40。 The following active energy ray-curable composition for forming a low refractive index layer was applied by a gravure method, dried at 90 ° C, and then cured by irradiation with ultraviolet rays of 400 mJ/cm 2 to form a low refractive index layer having a thickness of 40 nm. The low refractive index layer has a refractive index of 1.40.

(低折射率層形成用之活性放射線硬化性組成物) (Active radiation curable composition for forming a low refractive index layer)

將二(α-氟丙烯酸)-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-十七氟壬基乙二醇酯87質量份、六丙烯酸二季戊四醇酯10質量份、及光聚合起始劑(Ciba Specialty Chemicals(股)製「Irgacure 184」)3質量份分散或是溶解於有機溶劑(甲基乙基酮)中而調製。 Bis(α-fluoroacrylic acid)-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluoroindenyl 87 parts by mass of an alcohol ester, 10 parts by mass of dipentaerythritol hexaacrylate, and 3 parts by mass of a photopolymerization initiator ("Irgacure 184" manufactured by Ciba Specialty Chemicals Co., Ltd.) are dispersed or dissolved in an organic solvent (methyl ethyl ketone) Modulation in the middle.

<透明導電膜之積層> <Lamination of Transparent Conductive Film>

使厚度成為25nm的方式來利用濺鍍法積層ITO膜，圖案加工(蝕刻處理)成格子狀圖案而形成透明導電膜。 The ITO film was deposited by a sputtering method so that the thickness was 25 nm, and the pattern processing (etching treatment) was carried out in a lattice pattern to form a transparent conductive film.

[評估] [assessment]

針對實施例25至29之透明導電性膜，評估平滑性、 抗結塊性與透明導電膜圖案之辨識性。將其結果顯示於表5。 For the transparent conductive films of Examples 25 to 29, the smoothness was evaluated, Anti-caking property and visibility of transparent conductive film patterns. The results are shown in Table 5.

還有，透明導電性膜之平滑性與抗結塊性之評估係在上述之「(14)平滑性之評估」及「(15)抗結塊性之評估」中，除了使第1硬被覆層表面與透明導電膜表面相向的方式來重疊而變更之外，亦進行同樣的方式來評估。 In addition, the evaluation of the smoothness and anti-caking property of the transparent conductive film is in the above-mentioned "(14) Evaluation of smoothness" and "(15) Evaluation of anti-caking property", except that the first hard cover is made. The surface of the layer was overlapped and changed in such a manner as to face the surface of the transparent conductive film, and was evaluated in the same manner.

實施例25至29之透明導電性膜中任一種皆顯示良好之平滑性、抗結塊性與透明導電膜圖案之辨識性。 Any of the transparent conductive films of Examples 25 to 29 exhibited good smoothness, blocking resistance, and visibility of the transparent conductive film pattern.

[實施例31至40] [Examples 31 to 40]

如下所示，準備濕潤張力不同的5種樹脂層形成用塗布液。 Five kinds of coating liquids for forming a resin layer having different wet tensions were prepared as follows.

(樹脂層形成用塗布液c；濕潤張力42mN/m) (coating liquid c for forming a resin layer; wetting tension 42 mN/m)

以固形物質量比，混合下列27質量%之聚酯樹脂c、54質量%之聚酯樹脂d、18質量%之三聚氰胺系交聯劑、1質量%之粒子而調製分散塗布液。 The polyester resin d of the following 27 mass%, the polyester resin d of the 54 mass%, the melamine-type crosslinking agent of 18 mass%, and the particle|grains of 1 mass% were mixed in the solid mass ratio, and the dispersion coating liquid was prepared.

‧聚酯樹脂c：由2,6-萘二甲酸43莫耳%/間苯二甲酸-5-磺酸鈉7莫耳%/乙二醇45莫耳%/二乙二醇5莫耳%所構成的聚酯樹脂。 ‧ Polyester resin c: 43 mol % from 2,6-naphthalenedicarboxylic acid / 7 mol % sodium isophthalate-5-sulfonate / ethylene glycol 45 mol % / diethylene glycol 5 mol % The polyester resin is composed.

‧聚酯樹脂d：對苯二甲酸38莫耳%/偏苯三甲酸12莫耳%/乙二醇45莫耳%/二乙二醇5莫耳%所構成的聚酯樹脂。 ‧ Polyester resin d: 38 mol% of terephthalic acid / 12 mol% of trimellitic acid / ethylene glycol 45 mol % / diethylene glycol 5 mol %.

‧三聚氰胺系交聯劑：三和Chemical(股)製之「NIKALAC MW12LF」。 ‧ Melamine cross-linking agent: "NIKALAC MW12LF" manufactured by Sanhe Chemical Co., Ltd.

‧粒子：平均粒徑0.19μm之膠體二氧化矽。 ‧ Particles: Colloidal ceria having an average particle diameter of 0.19 μm.

(樹脂層形成用塗布液d；濕潤張力44mN/m) (coating liquid d for forming a resin layer; wetting tension 44 mN/m)

以固形物質量比，混合下列42質量%之聚酯樹脂e、42質量%之丙烯酸樹脂a、6質量%之環氧系交聯劑、9質量%之界面活性劑、1質量%之粒子而調製分散塗布液。 The following 42% by mass of the polyester resin e, 42% by mass of the acrylic resin a, 6% by mass of the epoxy-based crosslinking agent, 9% by mass of the surfactant, and 1% by mass of the particles were mixed at a solid mass ratio. The dispersion coating liquid was prepared.

‧聚酯樹脂e：對苯二甲酸35莫耳%/間苯二甲酸11莫耳%/間苯二甲酸-5-磺酸鈉4莫耳%/乙二醇45莫耳%/二乙二醇4莫耳%/聚乙二醇(重複單元數n=23)1莫耳%所構成的聚酯樹脂。 ‧ Polyester resin e: 35 mol% of terephthalic acid / 11 mol% of isophthalic acid / sodium isophthalate-5-sulfonate 4 mol% / ethylene glycol 45 mol% / two ethylene A polyester resin composed of 4 mol% of alcohol/polyethylene glycol (number of repeating units n=23) and 1 mol%.

‧丙烯酸樹脂a：甲基丙烯酸甲酯75莫耳%/甲基丙烯酸乙酯18莫耳%/N-羥甲基丙烯醯胺4莫耳%/甲氧基聚乙二醇(重複單元數n=10)甲基丙烯酸酯3莫耳%所構成的丙烯酸樹脂。 ‧Acrylic resin a: methyl methacrylate 75 mol % / ethyl methacrylate 18 mol % / N-methylol acrylamide 4 mol % / methoxy polyethylene glycol (repeating unit number n = 10) Acrylic resin composed of 3 mol% of methacrylate.

‧環氧系交聯劑：1,3-雙(N,N-二環氧丙基胺)環己烷。 ‧ Epoxy crosslinking agent: 1,3-bis(N,N-diepoxypropylamine) cyclohexane.

‧界面活性劑：聚氧化乙烯月桂基醚。 ‧ Surfactant: Polyoxyethylene lauryl ether.

‧粒子：平均粒徑0.19μm之膠體二氧化矽。 ‧ Particles: Colloidal ceria having an average particle diameter of 0.19 μm.

(樹脂層形成用塗布液e；濕潤張力48mN/m) (coating liquid e for forming a resin layer; wetting tension 48 mN/m)

以固形物質量比，混合下列40質量%之聚酯樹脂f、40質量%之丙烯酸樹脂b、10質量%之三聚氰胺系交聯劑、9質量%之界面活性劑、1質量%之粒子而調製分散塗布液。 The mixture is prepared by mixing 40% by mass of the polyester resin f, 40% by mass of the acrylic resin b, 10% by mass of the melamine-based crosslinking agent, 9% by mass of the surfactant, and 1% by mass of the particles in the solid mass ratio. Disperse the coating solution.

‧聚酯樹脂f：對苯二甲酸30莫耳%/間苯二甲酸15莫耳%/間苯二甲酸-5-磺酸鈉5莫耳%/乙二醇30莫耳%/1,4-丁二醇20莫耳%所構成的聚酯樹脂。 ‧ Polyester resin f: 30 mol% of terephthalic acid / 15 mol% of isophthalic acid / sodium isophthalate-5-sulfonate 5 mol% / ethylene glycol 30 mol% / 1,4 a polyester resin composed of 20% by mole of butanediol.

‧丙烯酸樹脂b：甲基丙烯酸甲酯75莫耳%/甲基丙烯酸乙酯22莫耳%/丙烯酸1莫耳%/N-羥甲基丙烯醯胺2莫耳%所構成的丙烯酸樹脂。 ‧Acrylic resin b: an acrylic resin composed of methyl methacrylate 75 mol % / ethyl methacrylate 22 mol % / acrylic acid 1 mol % / N-methylol acrylamide 2 mol %.

‧三聚氰胺系交聯劑：三和Chemical(股)製之「NIKALAC MW12LF」。 ‧ Melamine cross-linking agent: "NIKALAC MW12LF" manufactured by Sanhe Chemical Co., Ltd.

‧界面活性劑：聚氧化乙烯月桂基醚。 ‧ Surfactant: Polyoxyethylene lauryl ether.

‧粒子：平均粒徑0.19μm之膠體二氧化矽。 ‧ Particles: Colloidal ceria having an average particle diameter of 0.19 μm.

(樹脂層形成用塗布液f；濕潤張力51mN/m) (coating liquid f for forming a resin layer; wetting tension 51 mN/m)

以固形物質量比，混合下列45質量%之聚酯樹脂g、45質量%之丙烯酸樹脂c、5質量%之三聚氰胺系交聯劑、4質量%之界面活性劑、1質量%之粒子而調製分散塗布液。 The mixture is prepared by mixing 45 mass% of the polyester resin g, 45 mass% of the acrylic resin c, 5% by mass of the melamine-based crosslinking agent, 4% by mass of the surfactant, and 1% by mass of the particles in the solid mass ratio. Disperse the coating solution.

‧聚酯共聚物g：對苯二甲酸32莫耳%/間苯二甲酸12莫耳%/間苯二甲酸-5-磺酸鈉6莫耳%/乙二醇46莫耳%/二乙二醇4莫耳%所構成的聚酯共聚物。 ‧ polyester copolymer g: terephthalic acid 32 mol% / isophthalic acid 12 mol % / isophthalic acid sodium - sodium sulfonate 6 mol % / ethylene glycol 46 mol % / two A polyester copolymer composed of 4% by mole of diol.

‧丙烯酸樹脂c：甲基丙烯酸甲酯70莫耳%/甲基丙烯酸乙酯22莫耳%/N-羥甲基丙烯醯胺4莫耳%/N,N-二甲基丙烯醯胺4莫耳%所構成的丙烯酸樹脂。 ‧Acrylic resin c: methyl methacrylate 70 mol % / ethyl methacrylate 22 mol % / N-methylol acrylamide 4 mol % / N, N-dimethyl decylamine 4 Mo Acrylic resin composed of % of ear.

‧三聚氰胺系交聯劑：三和Chemical(股)製之「NIKALAC MW12LF」。 ‧ Melamine cross-linking agent: "NIKALAC MW12LF" manufactured by Sanhe Chemical Co., Ltd.

‧界面活性劑：聚氧化乙烯月桂基醚。 ‧ Surfactant: Polyoxyethylene lauryl ether.

‧粒子：平均粒徑0.19μm之膠體二氧化矽。 ‧ Particles: Colloidal ceria having an average particle diameter of 0.19 μm.

(樹脂層形成用塗布液g；濕潤張力53mN/m) (coating liquid g for forming a resin layer; wetting tension 53 mN/m)

以固形物質量比，85質量%之胺甲酸酯樹脂、5質量%之環氧系交聯劑、9質量%之界面活性劑、1質量%之粒子而調製分散塗布液。 The dispersion coating liquid was prepared in a mass ratio of solid content, 85 mass% of a urethane resin, 5 mass% of an epoxy type crosslinking agent, 9% by mass of a surfactant, and 1% by mass of particles.

‧胺甲酸酯樹脂：大日本Ink化學工業(股)製之「HYDRAN AP-20」。 ‧ Urethane resin: "HYDRAN AP-20" manufactured by Dainipa Ink Chemical Industry Co., Ltd.

‧環氧系交聯劑：三乙二醇二環氧丙基醚。 ‧ Epoxy crosslinking agent: triethylene glycol diepoxypropyl ether.

‧界面活性劑：聚氧化乙烯月桂基醚。 ‧ Surfactant: Polyoxyethylene lauryl ether.

‧粒子：平均粒徑0.19μm之膠體二氧化矽。 ‧ Particles: Colloidal ceria having an average particle diameter of 0.19 μm.

[實施例31] [Example 31]

依照下列之要領而製作硬被覆膜。 Make a hard coating according to the following guidelines.

<樹脂層積層PET膜之製作> <Production of Resin Layered PET Film>

在折射率1.65且厚度100μm之聚對苯二甲酸乙二酯膜(PET膜)之雙面，在PET膜之製造步驟內聯機塗布各自的樹脂層。亦即，利用棒塗布法，將各自的樹脂層形成用塗布液c塗布於長邊方向所單軸拉伸的PET膜之雙面，在100℃下乾燥後，接著在寬邊方向進行雙軸拉伸，在230℃下實施20秒加熱處理而使其熱硬化，製作在雙面積層有樹脂層之PET膜。在PET膜雙面所積層的樹脂層之厚度分別為0.08μm。 On both sides of a polyethylene terephthalate film (PET film) having a refractive index of 1.65 and a thickness of 100 μm, the respective resin layers were applied in-line in the production process of the PET film. In other words, the coating liquid c for forming a resin layer is applied to both sides of the uniaxially stretched PET film in the longitudinal direction by a bar coating method, and dried at 100 ° C, followed by biaxial stretching in the width direction. The film was stretched and heat-treated at 230 ° C for 20 seconds to be thermally cured to prepare a PET film having a resin layer in a double-area layer. The thickness of the resin layer laminated on both sides of the PET film was 0.08 μm, respectively.

<第1及第2硬被覆層之積層> <Layer of the first and second hard coating layers>

在雙面積層有樹脂層之PET膜一側面的樹脂層上，利用照相凹版塗布法塗布在實施例1所用之活性能量線硬化性組成物a，在90℃下乾燥後，照射紫外線400mJ/cm2而使其硬化，形成第1硬被覆層。該第1硬被覆層之厚度 為1.6μm。 The active energy ray-curable composition a used in Example 1 was applied onto the resin layer on one side of the PET film having the resin layer of the double-layer layer by a gravure coating method, and dried at 90 ° C, and then irradiated with ultraviolet rays of 400 mJ/cm. 2 , it hardens and forms a 1st hard coating layer. The thickness of the first hard coating layer was 1.6 μm.

接著，在PET膜另一側面(與積層有第1硬被覆層之面的相反面)的樹脂層上，與上述同樣地塗布在實施例2所用之活性能量線硬化性組成物b，形成第2硬被覆層而製作硬被覆膜。該第2硬被覆層之厚度為1.6μm。 Then, the active energy ray-curable composition b used in Example 2 was applied to the resin layer on the other side of the PET film (opposite to the surface on which the first hard coating layer was laminated) to form the first 2 Hard coating layer to make a hard coating film. The thickness of the second hard coating layer was 1.6 μm.

[實施例32至35] [Examples 32 to 35]

除了如表6的方式來變更樹脂層形成用塗布液之外，亦進行與實施例31同樣的方式來製作硬被覆膜。 A hard coating film was produced in the same manner as in Example 31 except that the coating liquid for forming a resin layer was changed as shown in Table 6.

[實施例36至40] [Examples 36 to 40]

除了將第1硬被覆層之厚度變更成2.6μm、及將第2硬被覆層之厚度變更成2.6μm之外，亦進行與實施例31至35同樣的方式來製作硬被覆膜。 A hard coating film was produced in the same manner as in Examples 31 to 35 except that the thickness of the first hard coating layer was changed to 2.6 μm and the thickness of the second hard coating layer was changed to 2.6 μm.

[硬被覆膜之評估] [Evaluation of hard coating]

針對上述所得之實施例31至40之硬被覆膜，將第1及第2硬被覆層之構造顯示於表6、將該等硬被覆膜的評估結果顯示於表7。 With respect to the hard coating films of Examples 31 to 40 obtained above, the structures of the first and second hard coating layers are shown in Table 6, and the evaluation results of the hard coating films are shown in Table 7.

從上述結果，得知藉由在濕潤張力為52mN/m以下的樹脂層上直接積層第1硬被覆層，在第1硬被覆層表面上容易形成因粒子所造成的突起(得知每單位面積之突起個數變多)。而且，得知樹脂層表面之濕潤張力的影響係在第1硬被覆層厚度小於2μm之情形下，變得明顯。亦即，在濕潤張力為52mN/m以下的樹脂層上直接積層第1硬被覆層之形態係在第1硬被覆層厚度小於2μm之情形下，第1硬被覆層中所含之粒子容易在表面附近不均勻，其結果，有效地形成因粒子所造成的突起。又，由於將第1硬被覆層厚度作成小於2μm，使霧度值變小而提高透明性。 From the above results, it is found that by directly laminating the first hard coating layer on the resin layer having a wet tension of 52 mN/m or less, protrusions due to particles are easily formed on the surface of the first hard coating layer (known per unit area) The number of protrusions has increased.) Further, it was found that the influence of the wetting tension on the surface of the resin layer became apparent when the thickness of the first hard coating layer was less than 2 μm. In other words, when the thickness of the first hard coating layer is directly deposited on the resin layer having a wet tension of 52 mN/m or less, when the thickness of the first hard coating layer is less than 2 μm, the particles contained in the first hard coating layer are likely to be present. The vicinity of the surface is uneven, and as a result, protrusions due to particles are effectively formed. Moreover, since the thickness of the first hard coating layer is made smaller than 2 μm, the haze value is made small, and transparency is improved.

11‧‧‧突起 11‧‧‧ Protrusion

Claims (17)

一種硬被覆膜，其特徵係在基材膜之至少一側面具備含有粒子之第1硬被覆層，在第1硬被覆層表面，由該粒子構成之突起係以每100μm2為300至4000個之密度存在，第1硬被覆層表面的中心線平均粗糙度(Ra1)小於30nm、霧度值小於1.5%。 A hard coating film comprising a first hard coating layer containing particles on at least one side surface of a base film, and a protrusion composed of the particles on the surface of the first hard coating layer is 300 to 4000 per 100 μm 2 The density of the first hard coating layer has a center line average roughness (Ra1) of less than 30 nm and a haze value of less than 1.5%. 如請求項1之硬被覆膜，其中該粒子之平均粒徑(r)為0.05至0.5μm。 The hard coating film of claim 1, wherein the particles have an average particle diameter (r) of 0.05 to 0.5 μm. 如請求項1之硬被覆膜，其中該粒子之平均粒徑(r)對第1硬被覆層之厚度(d)的比例(r/d)為0.01至0.30。 The hard coating film of claim 1, wherein the ratio (r/d) of the average particle diameter (r) of the particles to the thickness (d) of the first hard coating layer is 0.01 to 0.30. 如請求項1之硬被覆膜，其中該突起之平均直徑為0.03至0.3μm，該突起之平均高度為0.03至0.3μm。 The hard coating film of claim 1, wherein the protrusions have an average diameter of 0.03 to 0.3 μm, and the protrusions have an average height of 0.03 to 0.3 μm. 如請求項1之硬被覆膜，其中該突起之平均間隔為0.10至0.70μm。 The hard coating of claim 1, wherein the average spacing of the protrusions is from 0.10 to 0.70 μm. 如請求項1之硬被覆膜，其中第1硬被覆層之厚度(d)為0.5μm以上小於10μm。 The hard coating film of claim 1, wherein the thickness (d) of the first hard coating layer is 0.5 μm or more and less than 10 μm. 如請求項1之硬被覆膜，其中在該基材膜與第1硬被覆層之間具備厚度為0.005至0.3μm之樹脂層，該樹脂層含有具有厚度的1.3倍以上之平均粒徑的粒子。 The hard coating film of claim 1, wherein a resin layer having a thickness of 0.005 to 0.3 μm is provided between the base film and the first hard coating layer, and the resin layer contains an average particle diameter of 1.3 times or more of a thickness. particle. 如請求項1之硬被覆膜，其中該基材膜為由聚對苯二甲酸乙二酯構成，在該基材膜與第1硬被覆層之間具備折射率為1.55至1.61之樹脂層。 The hard coating film of claim 1, wherein the base film is made of polyethylene terephthalate, and a resin layer having a refractive index of 1.55 to 1.61 is provided between the base film and the first hard coating layer. . 如請求項1之硬被覆膜，其中在該基材膜與第1硬被覆層之間具備濕潤張力為52mN/m以下之樹脂層。 The hard coating film of claim 1, wherein a resin layer having a wet tension of 52 mN/m or less is provided between the base film and the first hard coating layer. 如請求項9之硬被覆膜，其中第1硬被覆層之厚度小於 2μm。 The hard coating film of claim 9, wherein the thickness of the first hard coating layer is less than 2 μm. 如請求項1之硬被覆膜，其中第1硬被覆層中所含之該粒子係由無機物構成，對於該粒子表面，實施用以減少表面自由能之處理或疏水化處理。 The hard coating film of claim 1, wherein the particles contained in the first hard coating layer are made of an inorganic material, and a treatment for reducing surface free energy or a hydrophobic treatment is performed on the surface of the particles. 如請求項11之硬被覆膜，其中對於第1硬被覆層中所含之該粒子表面，使用以通式1(CnF2n+1-(CH2)m-Si(Q)3)所示之有機矽烷化合物、該有機矽烷化合物之水解物、或該水解物之部分縮合物而實施用以減少表面自由能之處理；但是，於通式1中，n係表示1至10之整數、m係表示1至5之整數、Q係表示碳數1至5之烷氧基或鹵素原子。 The hard coating film of claim 11, wherein for the surface of the particle contained in the first hard coating layer, the formula 1 (C n F 2n+1 -(CH 2 ) m -Si(Q) 3 ) is used. The organic decane compound, the hydrolyzate of the organodecane compound, or the partial condensate of the hydrolyzate is subjected to a treatment for reducing the surface free energy; however, in the formula 1, n represents an integer of 1 to 10. m is an integer of 1 to 5, and Q is an alkoxy group having 1 to 5 carbon atoms or a halogen atom. 如請求項11之硬被覆膜，其中第1硬被覆層中所含之該粒子表面係藉由於使用以通式2(B-R4-SiR5 n(OR6)3-n)所示之化合物予以處理後，使用以通式3(D-R7-Rf2)所示之氟化物予以處理而被疏水化；但是，於通式2與3中，B與D係各自獨立地表示反應性部位，R4與R7係各自獨立地表示碳數1至3之伸烷基、或是由該伸烷基所衍生的酯結構，R5與R6係各自獨立地表示氫或碳數1至4之烷基、Rf2係表示氟烷基，n係表示0至2之整數。 The hard coating film of claim 11, wherein the surface of the particle contained in the first hard coating layer is a compound represented by the formula 2 (BR 4 -SiR 5 n (OR 6 ) 3-n ) After being treated, it is hydrophobized by treatment with a fluoride represented by Formula 3 (DR 7 - Rf 2 ); however, in Formulas 2 and 3, B and D each independently represent a reactive site, R 4 and R 7 each independently represent an alkylene group having 1 to 3 carbon atoms or an ester structure derived from the alkylene group, and R 5 and R 6 each independently represent hydrogen or a carbon number of 1 to 4. the alkyl group, Rf 2 represents a fluoroalkyl-based group, n is an integer of 0-2 are diagrams of. 如請求項11之硬被覆膜，其中第1硬被覆層中所含之該粒子表面係藉由使用具有碳數4以上之氟烷基與反應性部位之氟化物、具有碳數8以上之烴基與反應性部位之長鏈烴化合物、或是具有矽氧烷基與反應性部位之 聚矽氧化合物予以處理而被疏水化。 The hard coating film of claim 11, wherein the surface of the particle contained in the first hard coating layer is a fluoride having a carbon number of 4 or more and a fluoride of a reactive portion, and has a carbon number of 8 or more. a long-chain hydrocarbon compound having a hydrocarbon group and a reactive moiety, or having a decyloxy group and a reactive moiety The polyoxyxides are treated to be hydrophobized. 如請求項1之硬被覆膜，其中第1硬被覆層中所含之該粒子為二氧化矽粒子。 The hard coating film of claim 1, wherein the particles contained in the first hard coating layer are cerium oxide particles. 如請求項1之硬被覆膜，其中在與該基材膜設置有第1硬被覆層之面的相反面具備第2硬被覆層，在第2硬被覆層表面實質上不存在由粒子構成的突起，且第2硬被覆層表面之中心線平均粗糙度(Ra2)為25nm以下。 The hard coating film of claim 1, wherein the second hard coating layer is provided on a surface opposite to a surface on which the base film is provided with the first hard coating layer, and substantially no surface is formed on the surface of the second hard coating layer. The protrusion has a center line average roughness (Ra2) of the surface of the second hard coating layer of 25 nm or less. 一種透明導電性膜，其係在如請求項1至16中任一項之硬被覆膜之至少一側面具備透明導電膜。 A transparent conductive film comprising a transparent conductive film on at least one side surface of the hard coating film according to any one of claims 1 to 16.
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