TWI682849B - Transparent conductive film - Google Patents

Abstract

The present invention provides a laminated body for forming a transparent conductive layer and a transparent conductive film using the same. The laminated body for forming a transparent conductive layer has a hard coat with excellent etching resistance and is capable of stably making invisible a pattern shape of the transparent conductive layer, and the obtainable transparent conductive film has excellent anti-blocking properties.

A laminated body for forming a transparent conductive layer formed by laminating a hard coat layer, a substrate film, and an optical adjustment layer in this order, wherein the hard coat is formed by photocuring a composition for forming the hard coat layer containing 100 parts by weight of an energy ray curable resin (A) and 15 to 100 parts by weight of silica microparticles (B).

Description

透明導電性薄膜 Transparent conductive film

本發明係關於透明導電層形成用層合體及透明導電性薄膜。 The present invention relates to a laminate for forming a transparent conductive layer and a transparent conductive film.

尤其是在硬塗層之耐蝕刻性優異，可穩定地不可見化透明導電層之圖型形狀，且在所得之透明導電性薄膜之抗黏著性優異之透明導電層形成用層合體及使用其之透明導電性薄膜。 Especially in the hard coat layer, the etching resistance is excellent, the pattern shape of the transparent conductive layer can be stably not visualized, and the laminated body for forming a transparent conductive layer excellent in the anti-adhesion property of the obtained transparent conductive film and its use Transparent conductive film.

以往，可藉由與圖像顯示部直接接觸輸入信息之觸控面板，係將光透過性之輸入裝置配置在顯示器上而成者。 Conventionally, a touch panel that inputs information by directly contacting an image display unit is configured by disposing a light-transmitting input device on a display.

作為該觸控面板之代表性形式，存在有將2片透明電極基板以個別之透明電極層彼此面對的方式設置間隙並且配置而成之電阻膜式觸控面板、或利用透明電極膜與手指之間所產生之靜電容量的變化之靜電容量式觸控面板。 As a typical form of the touch panel, there is a resistive film type touch panel in which two transparent electrode substrates are arranged with a gap so that individual transparent electrode layers face each other and arranged, or a transparent electrode film and a finger are used Electrostatic capacitance type touch panel that changes the electrostatic capacitance generated between.

其中，於靜電容量式觸控面板，作為用以檢測出手指之接觸位置之感應器，存在大致上區分為透明導 電層層合於玻璃基材上而成之玻璃感應器、與透明導電層層合於透明塑膠薄膜基材上而成之薄膜感應器。 Among them, as an electrostatic capacitance type touch panel, as a sensor for detecting the contact position of a finger, there are roughly divided into transparent guides A glass sensor formed by laminating an electric layer on a glass substrate, and a thin film sensor formed by laminating a transparent conductive layer on a transparent plastic film substrate.

尤其是在薄膜感應器，將具備圖型化成線狀之透明導電層之透明導電性薄膜2片，藉由個別之圖型以彼此交叉的方式進行配置，形成格子狀之圖型為多。 In particular, in a thin film sensor, two transparent conductive films provided with a transparent conductive layer patterned into a linear shape are arranged in such a manner that the individual patterns cross each other to form a grid-like pattern.

然而，如此圖型化透明導電層的情況下，導致圖型部與非圖型部之界線部分變成易於視別，發現靜電容量式觸控面板之外觀惡化的問題。 However, in the case of such a patterned transparent conductive layer, the boundary between the patterned portion and the non-patterned portion becomes easy to distinguish, and the problem of deterioration in the appearance of the capacitive touch panel is found.

因此，揭示有用以解決該問題之技術(例如參照專利文獻1)。 Therefore, a technique useful for solving this problem is disclosed (for example, refer to Patent Document 1).

亦即，專利文獻1中，揭示有一種硬塗基材，其係依透明基材、易接著層、折射率調整層順序包含之硬塗基材，折射率調整層在波長550nm之折射率為1.60~1.90，折射率調整層的厚度為0.3~5μm，易接著層在波長550nm之折射率為1.56~1.70。 That is, Patent Document 1 discloses a hard-coated substrate, which is a hard-coated substrate included in the order of a transparent substrate, an easy adhesion layer, and a refractive index adjustment layer. The refractive index of the refractive index adjustment layer at a wavelength of 550 nm is 1.60~1.90, the thickness of the refractive index adjustment layer is 0.3~5μm, and the refractive index of the easy adhesion layer at a wavelength of 550nm is 1.56~1.70.

又，記載有於與形成在透明基材之折射率調整層之側的相反側，進一步層合具有抗黏著性並包含填料之機能賦予層。 In addition, it is described that a function-imparting layer having an anti-adhesion property and containing a filler is further laminated on the side opposite to the side of the refractive index adjustment layer formed on the transparent substrate.

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

[專利文獻1]日本特開2013-202844號公報(申請專利範圍) [Patent Document 1] Japanese Patent Laid-Open No. 2013-202844 (Patent Application Range)

然而，專利文獻1所揭示之硬塗基材，將透明導電層藉由蝕刻進行圖型化時，發現有包含填料之機能賦予層易藉由蝕刻液進行侵蝕，並藉此穩定地不可見化透明導電層之圖型形狀變困難的問題。 However, when the hard-coated substrate disclosed in Patent Document 1 patterned the transparent conductive layer by etching, it was found that the function-imparting layer containing fillers was easily eroded by the etching solution, and thereby was stably invisible The problem is that the pattern shape of the transparent conductive layer becomes difficult.

更具體而言，近年來伴隨智慧型手機等之生產增加，要求蝕刻處理之迅速化，尤其是蝕刻處理之最終步驟即用以去除殘留之光阻之鹼處理中，例如有使用加溫至40℃之5重量%的氫氧化鈉水溶液的情況。 More specifically, in recent years, with the increase in the production of smartphones, etc., the etching process is required to be accelerated, especially in the final step of the etching process, which is an alkali process for removing residual photoresist, for example, heating to 40 In the case of 5% by weight of sodium hydroxide aqueous solution at ℃.

進行如此嚴格之鹼處理的情況，專利文獻1所揭示之硬塗基材中，在機能賦予層之填料易溶解、或易脫落，其結果，發現有穩定地不可見化透明導電層之圖型形狀變困難的問題。 In the case of such a strict alkali treatment, in the hard-coated base material disclosed in Patent Document 1, the filler of the function-imparting layer is easily dissolved or detached, and as a result, a pattern of the transparent conductive layer that is stably invisible is found The shape becomes difficult.

因此，本發明者等鑑於如以上之事情，進行努力研究時，發現形成透明導電層形成用層合體之最內面之硬塗層時，相對於活性能量線硬化性樹脂，藉由使用將二氧化矽微粒子以特定範圍摻合而成之硬塗層形成用組成物，可解決上述之問題，而完成本發明者。 Therefore, in consideration of the above, the inventors of the present invention have found that when forming the hard coat layer on the innermost surface of the laminate for forming a transparent conductive layer, the active energy ray-curable resin is divided into two The composition for forming a hard coat layer in which silicon oxide fine particles are blended in a specific range can solve the above-mentioned problems and completed the present inventors.

亦即，本發明之目的係提供一種在硬塗層之耐蝕刻性優異，可穩定地不可見化透明導電層之圖型形狀，且在所得之透明導電性薄膜之抗黏著性優異之透明導電層形成用層合體及使用其之透明導電性薄膜。 That is, the object of the present invention is to provide a transparent conductive film having excellent etching resistance in a hard coat layer, a pattern shape of a transparent conductive layer which can be stably invisible, and an excellent adhesion resistance of the resulting transparent conductive film The laminate for layer formation and the transparent conductive film using the same.

根據本發明，提供一種透明導電層形成用層合體，其係依硬塗層、基材薄膜、光學調整層順序層合而成之透明導電層形成用層合體，其特徵為硬塗層係光硬化包含下述(A)~(B)成分之硬塗層形成用組成物而成，可解決上述之問題。 According to the present invention, there is provided a laminate for forming a transparent conductive layer, which is a laminate for forming a transparent conductive layer formed by sequentially laminating a hard coat layer, a base film, and an optical adjustment layer, characterized in that the hard coat layer is optical The above-mentioned problems can be solved by hardening the composition for forming a hard coat layer containing the following components (A) to (B).

亦即，若為本發明之透明導電層形成用層合體，形成其最內面之硬塗層時所使用之硬塗層形成用組成物，相對於活性能量線硬化性樹脂，由於以比較少的範圍包含二氧化矽微粒子，即使進行包含嚴格鹼處理之蝕刻處理的情況，亦可有效果地抑制在硬塗層之二氧化矽微粒子溶解、或是脫落(以下有時將該效果稱為「耐蝕刻性」)。 That is, if it is the laminate for forming a transparent conductive layer of the present invention, the composition for forming a hard coat layer used for forming the hard coat layer on the innermost surface thereof is relatively less than the active energy ray-curable resin. The range includes silicon dioxide fine particles. Even if etching treatment including strict alkali treatment is performed, the silicon dioxide fine particles in the hard coating layer can be effectively suppressed from dissolving or falling off (hereinafter this effect is sometimes referred to as " Etching resistance").

其結果，由於可抑制硬塗層之膜厚及折射率變化，最終可抑制硬塗層之光學特性變化，故可穩定地不可見化透明導電層之圖型形狀。 As a result, changes in the thickness and refractive index of the hard coat layer can be suppressed, and eventually changes in the optical characteristics of the hard coat layer can be suppressed, so that the pattern shape of the transparent conductive layer can be stably invisible.

又，由於可有效果地抑制在硬塗層之二氧化矽微粒子溶解、或是脫落，在硬塗層的表面，有效果地保持起因於二氧化矽微粒子所形成之微細表面凹凸。 Furthermore, since the silica particles in the hard coat layer can be effectively prevented from dissolving or falling off, the fine surface irregularities caused by the silica particles can be effectively maintained on the surface of the hard coat layer.

其結果，將所得之透明導電性薄膜捲繞成輥狀時，可有效果地抑制阻斷直接接觸之薄膜的表內面(以下有時將該效果稱為「抗黏著性」)。 As a result, when the obtained transparent conductive film is wound into a roll shape, the front and back surfaces of the film in direct contact can be effectively prevented from being blocked (hereinafter, this effect may be referred to as "adhesion resistance").

又，在構成本發明之透明導電層形成用層合體，較佳為將作為(B)成分之二氧化矽微粒子的體積平均粒徑(D50)定為10~100nm的範圍內之值。 In addition, in the laminate for forming the transparent conductive layer of the present invention, it is preferable to set the volume average particle diameter (D50) of the silica fine particles as the component (B) to a value in the range of 10 to 100 nm.

藉由如此構成，不會使在硬塗層之透明性降低，而且可得到特定之抗黏著性。 With such a structure, the transparency of the hard coat layer will not be reduced, and a specific anti-sticking property can be obtained.

又，在構成本發明之透明導電層形成用層合體，以作為(B)成分之二氧化矽微粒子為堅實二氧化矽微粒子較佳。 Moreover, in the laminate for forming the transparent conductive layer of the present invention, it is preferable that the silicon dioxide fine particles as the component (B) are solid silicon dioxide fine particles.

藉由如此構成，與中空二氧化矽微粒子進行比較，由於可縮小粒徑，為了得到抗黏著性即便摻合必要的量，亦可有效果地保持硬塗層之透明性。 With such a configuration, compared with the hollow silica fine particles, the particle size can be reduced, and the transparency of the hard coat layer can be effectively maintained even if the necessary amount is blended in order to obtain the anti-adhesion property.

又，在構成本發明之透明導電層形成用層合體，以作為(B)成分之二氧化矽微粒子為反應性二氧化矽微粒子較佳。 In addition, in the laminate for forming the transparent conductive layer of the present invention, it is preferable that the silicon dioxide fine particles as the component (B) are reactive silicon dioxide fine particles.

藉由如此構成，由於對硬塗層可牢牢地固定二氧化矽微粒子，可更有效果地提昇耐蝕刻性。 With such a configuration, since the silicon dioxide fine particles can be firmly fixed to the hard coat layer, the etching resistance can be improved more effectively.

又，在構成本發明之透明導電層形成用層合體，較佳為硬塗層形成用組成物作為(C)成分包含氟系均染劑的同時，相對於作為(A)成分之活性能量線硬化性樹脂100重量份，將該氟系均染劑之摻合量定為0.01~0.2重量份的範圍內之值。 In addition, in forming the laminate for forming a transparent conductive layer of the present invention, it is preferable that the composition for forming a hard coat layer contains a fluorine-based leveling agent as the component (C), and the active energy ray as the component (A) 100 parts by weight of the curable resin, the blending amount of the fluorine-based leveling agent is set to a value in the range of 0.01 to 0.2 parts by weight.

藉由如此構成，由於可更有效果地保護在硬塗層之二氧化矽微粒子，可更有效果地提昇耐蝕刻性。 With this structure, the silicon dioxide particles in the hard coat layer can be more effectively protected, and the etching resistance can be more effectively improved.

又，在構成本發明之透明導電層形成用層合 體，較佳為將硬塗層之膜厚定為0.5~5μm的範圍內之值。 In addition, the laminate for forming the transparent conductive layer of the present invention Preferably, the thickness of the hard coat layer is set to a value in the range of 0.5 to 5 μm.

藉由如此構成，可得到充分之耐蝕刻性，同時實施退火處理時，可有效果地抑制在透明導電層形成用層合體之捲曲的發生。 With such a configuration, sufficient etching resistance can be obtained, and when annealing treatment is performed at the same time, the occurrence of curling in the laminate for forming a transparent conductive layer can be effectively suppressed.

尚，所謂「退火處理」，係意指為了使在透明導電性薄膜之透明導電層的電傳導度提昇，於透明導電層形成用層合體上藉由加熱處理經層合狀態之透明導電層，進行結晶化之處理。 Still, the so-called "annealing treatment" means that in order to improve the electrical conductivity of the transparent conductive layer of the transparent conductive film, the transparent conductive layer in a laminated state is heat-treated on the laminate for forming a transparent conductive layer, Perform crystallization treatment.

又，在構成本發明之透明導電層形成用層合體，較佳為將硬塗層作為第1硬塗層的情況，於基材薄膜、與光學調整層之間具有第2硬塗層。 Furthermore, in the laminate for forming the transparent conductive layer of the present invention, it is preferable that the hard coat layer is used as the first hard coat layer, and a second hard coat layer is provided between the base film and the optical adjustment layer.

藉由如此構成，不僅可有效果地抑制因從基材薄膜滲出之寡聚物成分導致污染光學調整層、或實施退火處理時，可有效果地抑制在透明導電層形成用層合體之捲曲的發生。 With such a configuration, it is possible to effectively suppress not only the contamination of the optical adjustment layer due to the oligomer component exuded from the base film, or the annealing treatment, but also the curling of the laminate for forming a transparent conductive layer occur.

又，在構成本發明之透明導電層形成用層合體，較佳為第2硬塗層係與第1硬塗層相同，光硬化硬塗層形成用組成物而成的同時，亦具有與第1硬塗層相同之膜厚。 In addition, in forming the laminate for forming a transparent conductive layer of the present invention, it is preferable that the second hard coat layer is the same as the first hard coat layer, and the composition for forming a photohardenable hard coat layer also has 1 The thickness of the hard coat layer is the same.

藉由如此構成，第1及第2硬塗層的形成變容易的同時，實施退火處理時，可更有效果地抑制在透明導電層形成用層合體之捲曲的發生。 With this configuration, the formation of the first and second hard coat layers is facilitated, and when annealing treatment is performed, the occurrence of curling in the laminate for forming a transparent conductive layer can be more effectively suppressed.

又，本發明之其他態樣，係一種透明導電性 薄膜，其係依硬塗層、基材薄膜、光學調整層、透明導電層順序層合而成之透明導電性薄膜，其特徵為硬塗層係光硬化包含下述(A)~(B)成分之硬塗層形成用組成物而成，

In addition, other aspects of the present invention are a transparent conductive film, which is a transparent conductive film formed by sequentially laminating a hard coat layer, a base film, an optical adjustment layer, and a transparent conductive layer, and is characterized by a hard coat The layer is made of a photohardening composition for forming a hard coat layer containing the following components (A) to (B),

亦即，若為本發明之透明導電性薄膜，由於使用特定之透明導電層形成用層合體，可得到在硬塗層之耐蝕刻性優異，可穩定地不可見化透明導電層之圖型形狀，且優異之抗黏著性。 That is, in the case of the transparent conductive film of the present invention, since the specific transparent conductive layer forming laminate is used, a pattern shape of the transparent conductive layer with excellent etching resistance in the hard coat layer can be stably invisible , And excellent resistance to adhesion.

又，在構成本發明之透明導電性薄膜，較佳為透明導電層係藉由蝕刻而圖型化。 Furthermore, in the transparent conductive film constituting the present invention, it is preferable that the transparent conductive layer is patterned by etching.

即使為如此構成的情況，藉由在硬塗層之耐蝕刻性優異，可穩定地不可見化透明導電層之圖型形狀。 Even in the case of such a configuration, the pattern shape of the transparent conductive layer can be stably invisible due to excellent etching resistance in the hard coat layer.

1‧‧‧透明導電層 1‧‧‧Transparent conductive layer

2‧‧‧光學調整層 2‧‧‧Optical adjustment layer

2a‧‧‧低折射率層 2a‧‧‧Low refractive index layer

2b‧‧‧高折射率層 2b‧‧‧High refractive index layer

3‧‧‧硬塗層 3‧‧‧hard coating

3a‧‧‧第1硬塗層 3a‧‧‧The first hard coating

3b‧‧‧第2硬塗層 3b‧‧‧The second hard coating

4‧‧‧基材薄膜 4‧‧‧ Base film

10‧‧‧透明導電層形成用層合體 10‧‧‧Laminate for transparent conductive layer formation

100‧‧‧透明導電性薄膜 100‧‧‧Transparent conductive film

[圖1]圖1(a)~(b)係供作用以說明本發明之透明導電層形成用層合體的構成之圖。 [FIG. 1] FIG. 1 (a)-(b) are figures for explaining the structure of the laminate for forming a transparent conductive layer of the present invention.

[圖2]圖2係供作用以說明二氧化矽微粒子的摻合量、與在硬塗層之耐蝕刻性及抗黏著性的關係之圖。 [FIG. 2] FIG. 2 is a graph for explaining the relationship between the blending amount of silicon dioxide fine particles, the etching resistance and the adhesion resistance in the hard coat layer.

[圖3]圖3係供作用以說明本發明之透明導電性薄膜的構成之圖。 [FIG. 3] FIG. 3 is a diagram for explaining the structure of the transparent conductive film of the present invention.

[第1實施形態] [First Embodiment]

本發明之第1實施形態係如圖1(a)所示，為一種透明導電層形成用層合體10，其係依硬塗層3a、基材薄膜4、光學調整層2順序層合而成之透明導電層形成用層合體10，其特徵為硬塗層3a係光硬化包含下述(A)~(B)成分之硬塗層形成用組成物而成，

As shown in FIG. 1(a), the first embodiment of the present invention is a laminate 10 for forming a transparent conductive layer, which is formed by sequentially laminating a hard coat layer 3a, a base film 4 and an optical adjustment layer 2 The laminate 10 for forming a transparent conductive layer is characterized in that the hard coat layer 3a is formed by photohardening a composition for forming a hard coat layer containing the following components (A) to (B),

尚，在圖1(a)，於基材薄膜4的兩面雖將具有硬塗層3(3a、3b)之形態的透明導電層形成用層合體10作為一例展示，可省略基材薄膜4、與光學調整層2之間的硬塗層3b。 In addition, in FIG. 1(a), although the laminate 10 for forming a transparent conductive layer having the form of a hard coat layer 3 (3a, 3b) is shown as an example on both sides of the base film 4, the base film 4 may be omitted. The hard coat layer 3b with the optical adjustment layer 2.

又，即使針對光學調整層2，雖將由高折射率層2b及低折射率層2a的2層所構成之態樣作為一例展示，但可為由1層所構成之態樣、或由3層以上所構成之態樣的光學調整層2。 Moreover, even for the optical adjustment layer 2, although the aspect consisting of two layers of the high refractive index layer 2b and the low refractive index layer 2a is shown as an example, it may be a aspect consisting of one layer or three layers The optical adjustment layer 2 as described above.

又，在圖1(a)，各層中之粒子係表示二氧化矽微粒子或金屬氧化物粒子。 In addition, in FIG. 1(a), the particles in each layer represent silica fine particles or metal oxide particles.

以下，將本發明之第1實施形態適當參照圖面具體進行說明。 Hereinafter, the first embodiment of the present invention will be specifically described with reference to the drawings.

1.基材薄膜 1. Substrate film

(1)種類 (1) Type

作為基材薄膜的種類，並非特別限制者，作為光學用基材，可使用周知之基材薄膜。 The type of the base film is not particularly limited, and as the base material for optics, a well-known base film can be used.

例如，較佳可列舉聚苯二甲酸乙二酯(PET)、聚苯二甲酸丁二酯、聚萘二甲酸乙二酯(PEN)等之聚酯薄膜、聚乙烯薄膜、聚丙烯薄膜、玻璃紙(Cellophane)、二乙醯基纖維素薄膜、三乙醯基纖維素薄膜、乙醯基纖維素丁酸酯薄膜、聚氯乙烯薄膜、聚偏二氯乙烯薄膜、聚乙烯醇薄膜、乙烯-乙酸乙烯酯共聚物薄膜、聚苯乙烯薄膜、聚碳酸酯薄膜、聚甲基戊烯薄膜、聚碸薄膜、聚醚醚酮薄膜、聚醚碸薄膜、聚醚醯亞胺薄膜、聚醯亞胺薄膜、氟樹脂薄膜、聚醯胺薄膜、丙烯酸樹脂薄膜、降莰烯系樹脂薄膜、環烯烴樹脂薄膜等之塑膠薄膜。 For example, preferably, polyester films such as polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene naphthalate (PEN), polyethylene films, polypropylene films, cellophane (Cellophane), diacetyl cellulose film, triethyl cellulose film, ethyl cellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-acetic acid Vinyl ester copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyetheretherketone film, polyethersulfone film, polyetherimide film, polyimide film , Fluororesin film, polyamide film, acrylic resin film, norbornene-based resin film, cycloolefin resin film and other plastic films.

又，此等當中，從耐熱性的觀點來看，更佳為聚酯薄膜、聚碳酸酯薄膜、聚醯亞胺薄膜、降莰烯系樹脂薄膜、環烯烴樹脂薄膜。 Among these, from the viewpoint of heat resistance, polyester films, polycarbonate films, polyimide films, norbornene-based resin films, and cycloolefin resin films are more preferred.

又，從透明性及薄膜強度與柔軟性兩立的觀點來看，特佳為PET薄膜。 In addition, from the standpoint of transparency, film strength and flexibility, PET film is particularly preferred.

(2)膜厚 (2) Film thickness

又，較佳為將基材薄膜的膜厚定為20~200μm的範圍內之值。 In addition, it is preferable to set the film thickness of the base film to a value in the range of 20 to 200 μm.

此理由，係因為基材薄膜的膜厚成為未達20μm的 值時，藉由降低基材薄膜的強度，有無法有效果地抑制在光學調整層之透明導電層的存在部分與非存在部分之退火處理時扭曲的發生的情況。另外，係因為基材薄膜的膜厚成為超過200μm的值時，有在基材薄膜之透明性等之光學特性惡化的情況。 This reason is because when the thickness of the base film becomes less than 20 μm , by reducing the strength of the base film, it is not possible to effectively suppress the presence and absence of the transparent conductive layer in the optical adjustment layer Part of the occurrence of distortion during annealing. In addition, when the film thickness of the base film exceeds 200 μm, the optical properties such as the transparency of the base film may deteriorate.

據此，更佳為將基材薄膜的膜厚定為30~180μm的範圍內之值，再更佳為定為50~150μm的範圍內之值。 Accordingly, it is more preferable to set the film thickness of the base material film to a value in the range of 30 to 180 μm, and still more preferably to a value in the range of 50 to 150 μm.

尚，所謂「退火處理」，係意指為了使在透明導電性薄膜之透明導電層的電傳導度提昇，於透明導電層形成用層合體上藉由加熱處理經層合狀態之透明導電層，進行結晶化之處理。 Still, the so-called "annealing treatment" means that in order to improve the electrical conductivity of the transparent conductive layer of the transparent conductive film, the transparent conductive layer in a laminated state is heat-treated on the laminate for forming a transparent conductive layer, Perform crystallization treatment.

2.硬塗層 2. Hard coating

如圖1(a)所示，在構成本發明之透明導電層形成用層合體10，係將至少於與在基材薄膜4之光學調整層2層合之側相反側的面設置硬塗層3a作為特徵。 As shown in FIG. 1(a), the laminate 10 for forming the transparent conductive layer of the present invention is provided with a hard coat layer at least on the side opposite to the side where the optical adjustment layer 2 of the base film 4 is laminated 3a as a feature.

此理由，係因為藉由設置該硬塗層，在透明導電層形成用層合體之製造步驟，除了可對基材薄膜賦予耐擦傷性，防止降低光學特性之外，將基材薄膜捲繞成輥狀的情況，可抑制發生基材薄膜彼此貼合現象(以下，有時將該效果稱為「抗黏著性」)。 The reason for this is that, by providing the hard coat layer, in the manufacturing step of the laminate for forming a transparent conductive layer, in addition to imparting scratch resistance to the base film and preventing degradation of optical properties, the base film is wound into In the case of a roll, it is possible to suppress the phenomenon that the base films are bonded to each other (hereinafter, this effect is sometimes referred to as "anti-adhesion").

又，如圖1(a)所示，較佳為將硬塗層3a作為第1硬塗層的情況，於基材薄膜4、與光學調整層2之間具有第2硬塗層3b。 Further, as shown in FIG. 1( a ), it is preferable that the hard coat layer 3 a is used as the first hard coat layer, and the second hard coat layer 3 b is provided between the base film 4 and the optical adjustment layer 2.

此理由，係因為藉由具有該第2硬塗層，不僅可有效果地抑制因從基材薄膜滲出之寡聚物成分導致污染光學調整層、或可有效果地抑制在透明導電層形成用層合體之捲曲的發生。 This reason is because by having the second hard coat layer, not only can effectively suppress contamination of the optical adjustment layer due to the oligomer component oozing out from the base film, but also can effectively suppress the formation of the transparent conductive layer The occurrence of curling of the laminate.

又，較佳為第2硬塗層係與第1硬塗層相同，光硬化硬塗層形成用組成物而成的同時，亦具有與第1硬塗層相同之膜厚。 In addition, it is preferable that the second hard coat layer is the same as the first hard coat layer, and the composition for forming the photo-hardening hard coat layer also has the same film thickness as the first hard coat layer.

此理由，係因為藉由如此構成第2硬塗層，使得第1及第2硬塗層的形成變容易，同時可更有效果地抑制在實施退火處理的情況在透明導電層形成用層合體之捲曲的發生。 The reason for this is that, by configuring the second hard coat layer in this way, the formation of the first and second hard coat layers is facilitated, and at the same time, it is possible to more effectively suppress the formation of the transparent conductive layer-forming laminate during the annealing process. The occurrence of curly.

據此，以下之說明係第1硬塗層及第2硬塗層兩方所共通之內容。 Accordingly, the following description is common to both the first hard coat layer and the second hard coat layer.

(1)材料物質 (1) Material substance

又，在本發明之硬塗層，其特徵為作為材料物質，係光硬化包含下述(A)~(B)成分之硬塗層形成用組成物而成。 In addition, the hard coat layer of the present invention is characterized in that it is a material substance which is formed by photohardening a composition for forming a hard coat layer containing the following components (A) to (B).

此理由，係因為形成硬塗層時所用之硬塗層形成用組成物，對於活性能量線硬化性樹脂，藉由將二氧化矽微粒子以比較少的範圍包含，即使進行包含嚴格鹼處理之蝕刻 處理的情況，亦可有效果地抑制在硬塗層之二氧化矽微粒子溶解、或是脫落。 This reason is because the composition for forming a hard coat layer used for forming the hard coat layer contains the silicon dioxide fine particles in a relatively small range for the active energy ray-curable resin, even if etching including strict alkali treatment is performed In the case of treatment, the silicon dioxide particles in the hard coat layer can also be effectively suppressed from dissolving or falling off.

更具體而言，如圖1(a)所示，在硬塗層3a之二氧化矽微粒子的摻合量少的情況，由於由樹脂所構成之基質部分的存在比例多，即使進行嚴格鹼處理的情況，二氧化矽微粒子係有效果地保護基質部分，可有效果地抑制溶解、或脫落。 More specifically, as shown in FIG. 1(a), in the case where the amount of silicon dioxide fine particles in the hard coat layer 3a is small, since there is a large proportion of the matrix portion composed of resin, even if strict alkali treatment is performed In the case of silicon dioxide microparticles, the matrix part is effectively protected, and dissolution or shedding can be effectively suppressed.

其結果，可抑制硬塗層的膜厚及折射率變化，最終可抑制硬塗層之光學特性變化。 As a result, changes in the film thickness and refractive index of the hard coat layer can be suppressed, and finally changes in the optical characteristics of the hard coat layer can be suppressed.

另外，如圖1(b)所示，在硬塗層3a’之二氧化矽微粒子的摻合量多的情況，由於由樹脂所構成之基質部分的存在比例少，於進行嚴格鹼處理的情況，二氧化矽微粒子無法藉由基質部分充分保護、變成易溶解、或脫落。 In addition, as shown in FIG. 1(b), in the case where the amount of silicon dioxide fine particles in the hard coat layer 3a' is large, the proportion of the matrix portion composed of the resin is small, so that it is subjected to strict alkali treatment The silicon dioxide particles cannot be fully protected by the matrix part, become soluble, or fall off.

據此，如圖1(a)所示，若為在硬塗層3a之二氧化矽微粒子的摻合量少之本發明之透明導電層形成用層合體10，可穩定地不可見化光學調整層2之上所形成之透明導電層的圖型形狀。 Accordingly, as shown in FIG. 1(a), if the amount of silicon dioxide fine particles in the hard coat layer 3a is small, the transparent conductive layer forming laminate 10 of the present invention can be stably invisible optically adjusted The pattern shape of the transparent conductive layer formed on the layer 2.

又，由於有效果地抑制在硬塗層之二氧化矽微粒子溶解、或脫落，在硬塗層的表面，有效果地保持起因於二氧化矽微粒子所形成之微細表面凹凸。 In addition, since the silica particles in the hard coat layer are effectively suppressed from dissolving or falling off, the fine surface irregularities caused by the silica particles are effectively maintained on the surface of the hard coat layer.

據此，將所得之透明導電性薄膜捲繞成輥狀時，可有效果地抑制阻斷直接接觸之薄膜的表內面。 According to this, when the obtained transparent conductive film is wound into a roll shape, the front and back surfaces of the film in direct contact can be effectively prevented from being blocked.

以下，對每個成分進行說明。 Hereinafter, each component will be described.

(1)-1(A)成分：活性能量線硬化性樹脂 (1)-1(A) component: active energy ray curable resin

(A)成分為活性能量線硬化性樹脂。 (A) The component is an active energy ray curable resin.

所謂作為該(A)成分之活性能量線硬化性樹脂，係指於電磁波或荷電粒子線當中具有能量量子者，亦即藉由照射紫外線或電子束等，進行交聯、硬化之聚合性化合物，例如可列舉光聚合性預聚物或光聚合性單體。 The active energy ray-curable resin as the component (A) refers to those having energy quanta in electromagnetic waves or charged particle beams, that is, polymerizable compounds that are cross-linked and hardened by irradiation with ultraviolet rays or electron beams, etc. Examples include photopolymerizable prepolymers and photopolymerizable monomers.

又，上述之光聚合性預聚物中，有自由基聚合型與陽離子聚合型，作為自由基聚合型之光聚合性預聚物，可列舉聚酯丙烯酸酯系、環氧丙烯酸酯系、胺基甲酸乙酯丙烯酸酯系、聚醇丙烯酸酯系等。 In addition, the above-mentioned photopolymerizable prepolymers include radical polymerization type and cation polymerization type, and examples of the radical polymerization type photopolymerizable prepolymers include polyester acrylates, epoxy acrylates, and amines. Ethyl acrylate system, polyol acrylate system, etc.

又，作為聚酯丙烯酸酯系預聚物，例如可列舉藉由於藉由多元羧酸與多元之縮合所得之兩末端具有羥基之聚酯寡聚物的羥基以(甲基)丙烯酸進行酯化、或者藉由於多元羧酸加成環氧烷，將所得之寡聚物末端之羥基以(甲基)丙烯酸進行酯化所得之化合物。 In addition, examples of the polyester acrylate-based prepolymer include esterification of (meth)acrylic acid with hydroxyl groups of polyester oligomers having hydroxyl groups at both ends obtained by condensation of polycarboxylic acids and polyhydric acids. Or a compound obtained by esterifying the hydroxyl group at the end of the obtained oligomer with (meth)acrylic acid by adding polyalkylene oxide to alkylene oxide.

又，作為環氧丙烯酸酯系預聚物，例如可列舉於比較低分子量之雙酚型環氧樹脂或酚荃清漆型環氧樹脂之環氧乙烷(Oxirane)環，藉由以(甲基)丙烯酸進行酯化所得之化合物。 In addition, examples of the epoxy acrylate-based prepolymer include ethylene oxide (Oxirane) rings of relatively low molecular weight bisphenol-type epoxy resins or phenolic varnish-type epoxy resins. ) A compound obtained by esterification of acrylic acid.

又，作為胺基甲酸乙酯丙烯酸酯系預聚物，例如可列舉將藉由聚醚聚醇或聚酯聚醇與聚異氰酸酯的反應所得之聚胺基甲酸乙酯寡聚物藉由以(甲基)丙烯酸進行酯化所得之化合物。 Further, examples of the urethane acrylate prepolymer include, for example, a polyurethane oligomer obtained by the reaction of polyether polyol or polyester polyol with polyisocyanate by ( A compound obtained by esterification of meth)acrylic acid.

進而，作為聚醇丙烯酸酯系預聚物，可列舉將聚醚聚 醇之羥基藉由以(甲基)丙烯酸進行酯化所得之化合物。 Furthermore, examples of the polyol acrylate-based prepolymer include polyether polyether The compound obtained by esterification of (meth)acrylic acid in the hydroxyl group of alcohol.

尚，此等之聚合性預聚物可1種單獨使用，亦可組合2種以上使用。 Still, these polymerizable prepolymers may be used alone or in combination of two or more.

另外，作為陽離子聚合型之光聚合性預聚物，通常使用環氧系樹脂。 In addition, as the cation polymerization type photopolymerizable prepolymer, an epoxy resin is generally used.

作為該環氧樹脂，例如可列舉於雙酚樹脂或酚醛清漆樹脂等之多元酚類以表氯醇等進行環氧化所得之化合物、將直鏈狀烯烴化合物或環狀烯烴化合物以過氧化物等進行氧化所得之化合物等。 Examples of the epoxy resin include compounds obtained by epoxidation of polyphenols such as bisphenol resins and novolac resins with epichlorohydrin, etc., and linear olefin compounds or cyclic olefin compounds with peroxides. Compounds obtained by oxidation.

又，作為光聚合性單體，例如可列舉1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、新戊二醇己二酸酯二(甲基)丙烯酸酯、羥基特戊酸新戊二醇二(甲基)丙烯酸酯、二環戊基二(甲基)丙烯酸酯、己內酯改質二環戊烯基二(甲基)丙烯酸酯、氧化乙烯改質磷酸二(甲基)丙烯酸酯、烯丙基化環己基二(甲基)丙烯酸酯、異氰脲酸酯二(甲基)丙烯酸酯、丙酸改質二季戊四醇三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、氧化丙烯改質三羥甲基丙烷三(甲基)丙烯酸酯、參(丙烯醯氧乙基)異氰脲酸酯、丙酸改質二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、己內酯改質二季戊四醇六(甲基)丙烯酸酯等之多官能丙烯酸酯。 In addition, examples of the photopolymerizable monomer include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and neopentyl glycol di(meth)acrylate. ) Acrylate, polyethylene glycol di(meth)acrylate, neopentyl glycol adipate di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, bicyclic Amyl di(meth)acrylate, caprolactone modified dicyclopentenyl di(meth)acrylate, ethylene oxide modified di(meth)acrylate, allylated cyclohexyl di(meth) Base) acrylate, isocyanurate di(meth)acrylate, propionic acid modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide modified trimethylolpropane Tri(meth)acrylate, ginseng (acryloyloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone modified Multifunctional acrylates such as qualitative dipentaerythritol hexa(meth)acrylate.

尚，此等之光聚合性單體可1種單獨使用，亦可組合2種以上使用。 Still, these photopolymerizable monomers may be used alone or in combination of two or more.

(1)-2(B)成分：二氧化矽微粒子 (1)-2(B) Ingredients: silica fine particles

(B)成分為二氧化矽微粒子。 (B) The component is silicon dioxide fine particles.

作為該二氧化矽微粒子的種類，雖並非被特別限制者，但較佳為使用堅實二氧化矽微粒子。 Although the type of the silica fine particles is not particularly limited, it is preferable to use solid silica fine particles.

此理由，係因為若為堅實二氧化矽微粒子，與體積平均粒徑成為20nm以上之中空二氧化矽微粒子進行比較，由於可縮小粒徑，為了得到抗黏著性即便摻合必要的量，亦可有效果地保持硬塗層之透明性。 This reason is because if it is solid silica fine particles, compared with hollow silica fine particles with a volume average particle diameter of 20 nm or more, the particle size can be reduced, and even if the necessary amount is blended in order to obtain the anti-adhesive property, it can be Effectively maintain the transparency of the hard coating.

又，與高價之中空二氧化矽微粒子進行比較，經濟上亦成為有利。 Moreover, compared with the high-priced hollow silica fine particles, it becomes economically advantageous.

尚，所謂「堅實二氧化矽微粒子」，係意指於粒子之內部不具有空洞之二氧化矽微粒子。 Still, the so-called "solid silica particles" mean silica particles that do not have voids inside the particles.

又，較佳為二氧化矽微粒子為反應性二氧化矽微粒子。 Moreover, it is preferable that the silica fine particles are reactive silica fine particles.

此理由，係因為若為反應性二氧化矽微粒子，由於對硬塗層可牢牢地固定二氧化矽微粒子，可更有效果地提昇耐蝕刻性。 This reason is because if it is a reactive silica fine particle, since the silica fine particle can be firmly fixed to the hard coat layer, the etching resistance can be improved more effectively.

尚，所謂「反應性二氧化矽微粒子」，係結合含有聚合性不飽和基之有機化合物之二氧化矽微粒子，在二氧化矽微粒子表面之矽醇基，可藉由使含有聚合性不飽和基之有機化合物進行反應而得到，該不飽和基係具有可與該矽醇基反應之官能基。 Still, the so-called "reactive silica fine particles" are silica fine particles combined with an organic compound containing a polymerizable unsaturated group. The silanol group on the surface of the silica fine particles can contain a polymerizable unsaturated group. It is obtained by reacting an organic compound. The unsaturated group has a functional group that can react with the silanol group.

又，作為上述之聚合性不飽和基，例如可列舉自由基 聚合性之丙烯醯基或甲基丙烯醯基等。 In addition, examples of the above-mentioned polymerizable unsaturated group include radicals. Polymerizable acryl or methacryl.

又，較佳為將二氧化矽微粒子的體積平均粒徑(D50)定為10~100nm的範圍內之值。 In addition, it is preferable to set the volume average particle diameter (D50) of the silica fine particles to a value in the range of 10 to 100 nm.

此理由，係因為藉由將二氧化矽微粒子的體積平均粒徑(D50)定為該範圍內之值，不會使在硬塗層之透明性降低，而且可得到特定之抗黏著性。 This reason is because by setting the volume average particle diameter (D50) of the silica fine particles to a value within this range, the transparency of the hard coat layer will not be reduced, and a specific anti-adhesion property can be obtained.

亦即，係因為二氧化矽微粒子的體積平均粒徑(D50)成為未達10nm之值時，有在硬塗層表面之表面凹凸過度縮小，難以有效果地表現抗黏著性的情況。另外，係因為二氧化矽微粒子的體積平均粒徑(D50)成為超過100nm之值時，有變成易產生光之散射，易降低在硬塗層之透明性的情況。 That is, when the volume average particle diameter (D50) of the silica fine particles is less than 10 nm, the surface unevenness on the surface of the hard coat layer is excessively reduced, and it is difficult to effectively express the anti-adhesion property. In addition, when the volume average particle diameter (D50) of the silicon dioxide fine particles exceeds 100 nm, light scattering is likely to occur, and the transparency of the hard coat layer may be easily reduced.

據此，更佳為將二氧化矽微粒子的體積平均粒徑(D50)定為12~60nm的範圍內之值，再更佳為定為14~30nm的範圍內之值。 Accordingly, it is more preferable to set the volume average particle diameter (D50) of the silica particles to a value in the range of 12 to 60 nm, and still more preferably to a value in the range of 14 to 30 nm.

尚，二氧化矽微粒子的體積平均粒徑(D50)，例如除了可藉由仄他電位測定法求得之外，亦可使用雷射繞射散射式粒度分布測定裝置求得，進而亦可將SEM圖像為基礎求得。 In addition, the volume average particle diameter (D50) of silica fine particles can be obtained, for example, by a beta potential measurement method, or by a laser diffraction scattering type particle size distribution measuring device, and furthermore Obtained based on SEM images.

又，其特徵為相對於作為(A)成分之活性能量線硬化性樹脂100重量份，將二氧化矽微粒子的摻合量定為15~100重量份的範圍內之值。 In addition, it is characterized in that the blending amount of the silica fine particles is set to a value in the range of 15 to 100 parts by weight with respect to 100 parts by weight of the active energy ray-curable resin as the component (A).

此理由，係因為二氧化矽微粒子的摻合量成為未達15重量份之值時，有硬塗層的硬度變不夠充分、或於硬 塗層的表面難以形成充分之表面凹凸、難以得到對於抗黏著性或黏著劑層等之密著性的情況。另外，係因為二氧化矽微粒子的摻合量成為超過100重量份之值時，於進行包含嚴格鹼處理之蝕刻處理的情況，有亦可有效果地抑制在硬塗層之二氧化矽微粒子溶解、或是脫落的情況。 This reason is because when the blending amount of the silica fine particles is less than 15 parts by weight, the hardness of the hard coating layer becomes insufficient or hard It is difficult to form sufficient surface irregularities on the surface of the coating, and it is difficult to obtain adhesion to the anti-adhesive property or adhesive layer. In addition, when the blending amount of the silicon dioxide fine particles exceeds 100 parts by weight, it is possible to effectively suppress the dissolution of the silicon dioxide fine particles in the hard coat layer when performing an etching treatment including strict alkali treatment , Or fall off.

據此，更佳為相對於作為(A)成分之活性能量線硬化性樹脂100重量份，將二氧化矽微粒子的摻合量定為20~70重量份的範圍內之值，再更佳為定為30~50重量份的範圍內之值。 Accordingly, it is more preferable to set the blending amount of silica fine particles to a value in the range of 20 to 70 parts by weight with respect to 100 parts by weight of the active energy ray-curable resin as the component (A), and even more preferably Set the value within the range of 30-50 parts by weight.

其次，使用圖2，說明二氧化矽微粒子的摻合量、與在硬塗層之耐蝕刻性及抗黏著性的關係。 Next, using FIG. 2, the relationship between the blending amount of silicon dioxide fine particles and the etching resistance and adhesion resistance of the hard coat layer will be described.

亦即，圖2中，顯示於橫軸採取二氧化矽微粒子的摻合量(重量份)，於左縱軸採取在透明導電層形成用層合體之鹼處理前後的反射率變化量(%)之特性曲線A、與於右縱軸採取抗黏著性(相對值)之特性曲線B。 That is, in FIG. 2, the amount of blending of silica fine particles (parts by weight) is shown on the horizontal axis, and the amount of change in reflectance (%) before and after alkali treatment of the laminate for forming a transparent conductive layer is taken on the left vertical axis. The characteristic curve A and the characteristic curve B with the anti-adhesion (relative value) on the right vertical axis.

尚，針對在透明導電層形成用層合體於鹼處理前後之反射率變化量及抗黏著性之具體測定方法，記載在實施例。 Still further, specific methods for measuring the amount of change in reflectance and the anti-adhesion property of the laminate for forming a transparent conductive layer before and after alkali treatment are described in Examples.

又，在透明導電層形成用層合體於鹼處理前後之反射率變化量(%)，係意指藉由藉鹼處理變化硬塗層的膜厚或折射率或者兩方，由於硬塗層之反射率變化，成為硬塗層之耐蝕刻性的指標者，反射率變化量越小，耐蝕刻性越優異，若為0.5%以下之值，可判斷實用上具有優異之耐蝕刻性。 In addition, the amount of change in reflectance (%) of the laminate for forming a transparent conductive layer before and after alkali treatment means that the thickness or refractive index of the hard coat layer or both of them are changed by alkali treatment. When the reflectance changes and becomes an indicator of the etching resistance of the hard coat layer, the smaller the change in reflectance, the better the etching resistance. If the value is 0.5% or less, it can be judged to have excellent etching resistance in practice.

又，抗黏著性之相對值，係如實施例所記載來進行，將評估之抗黏著性沿下述基準成為相對值化之值。 In addition, the relative value of the anti-sticking property was carried out as described in the Examples, and the evaluated anti-sticking property was a relative value along the following criteria.

4：層表面彼此未密著 4: The surface of the layer is not close to each other

1：層表面彼此密著無法動彈 1: The layer surfaces are close to each other and cannot move

首先，從特性曲線A即可理解，反射率變化量伴隨二氧化矽微粒子的摻合量增加，有急速增加之傾向。 First, it can be understood from the characteristic curve A that the amount of change in reflectance tends to increase rapidly with the increase in the amount of silicon dioxide fine particles blended.

更具體而言，理解二氧化矽微粒子的摻合量於100重量份以下的範圍，雖可將反射率變化量穩定地成為0.5%以下之值，但二氧化矽微粒子的摻合量超過100重量份時，急速增加反射率變化量，而超過0.5%。 More specifically, it is understood that the blending amount of silicon dioxide fine particles is within a range of 100 parts by weight or less. Although the amount of change in reflectance can be stably reduced to a value of 0.5% or less, the blending amount of silicon dioxide fine particles exceeds 100 parts by weight. At the time of copying, the amount of change in reflectance is rapidly increased, and exceeds 0.5%.

此急速反射率變化量的增加，推測是因硬塗層之表面或層本身由鹼處理而崩壞者。 The increase in the amount of rapid reflectance change is presumed to be due to the surface of the hard coating layer or the layer itself being destroyed by alkali treatment.

又，從特性曲線B即可理解，抗黏著性之值伴隨二氧化矽微粒子的摻合量增加，有急速增加之傾向。 Furthermore, it can be understood from the characteristic curve B that the value of the anti-adhesion property tends to increase rapidly with the increase of the blending amount of the silica fine particles.

更具體而言，理解二氧化矽微粒子的摻合量於未達15重量份的範圍，雖抗黏著性之值低，但成為15重量份以上時，變成可得到實用上所要求之特定抗黏著性，成為40重量份以上時，變成可穩定得到優異之抗黏著性。 More specifically, it is understood that the blending amount of the silica particles is less than 15 parts by weight. Although the value of the anti-adhesion property is low, when it becomes 15 parts by weight or more, it becomes possible to obtain the specific anti-adhesion that is practically required. When the property becomes 40 parts by weight or more, it becomes stable and excellent anti-sticking property can be obtained.

據此，理解從特性曲線A及B，為了使耐蝕刻性、與抗黏著性兩立，應將二氧化矽微粒子的摻合量定為15~100重量份的範圍內之值。 Based on this, it is understood that from the characteristic curves A and B, in order to make etching resistance and anti-adhesion compatible, the blending amount of silicon dioxide fine particles should be set to a value in the range of 15 to 100 parts by weight.

(1)-3(C)成分：氟系均染劑 (1)-3(C) Ingredient: Fluorine leveling agent

作為(C)成分，較佳為進一步包含氟系均染劑。 As the component (C), it is preferable to further contain a fluorine-based leveling agent.

此理由，係因為藉由包含氟系均染劑，由於可更有效果地保護在硬塗層之二氧化矽微粒子，故可更有效果地提昇耐蝕刻性。 This reason is because by containing a fluorine-based leveling agent, the silicon dioxide fine particles in the hard coat layer can be more effectively protected, so that the etching resistance can be more effectively improved.

更具體而言，係因為藉由氟系均染劑所具有之撥水性，可將在硬塗層之二氧化矽微粒子鹼處理所用之鹼成分有效果地保護。 More specifically, because of the water-repellent property of the fluorine-based leveling agent, the alkali component used for the alkali treatment of the silica fine particles in the hard coat layer can be effectively protected.

尚，作為氟系均染劑之種類，雖可使用以往周知之物，但與直鏈之氟系均染劑進行比較，由於揮發性低且熱穩定性優異，故較佳為包含分支鏈與雙鍵之硬質之分子構造的氟系均染劑，作為如此之氟系均染劑，例如可列舉Neos(股)製、Ftergent 7602A等。 As for the type of fluorine leveling agent, although conventionally known ones can be used, compared with the linear fluorine leveling agent, since it has low volatility and excellent thermal stability, it is preferable to include branched chain and A fluorine-based leveling agent of a double-bonded hard molecular structure. Examples of such a fluorine-based leveling agent include Neos Co., Ltd. and Ftergent 7602A.

又，較佳為相對於作為(A)成分之活性能量線硬化性樹脂100重量份，將氟系均染劑的摻合量定為0.01~0.2重量份的範圍內之值。 In addition, it is preferable to set the blending amount of the fluorine-based leveling agent to a value in the range of 0.01 to 0.2 parts by weight with respect to 100 parts by weight of the active energy ray-curable resin as the component (A).

此理由，係因為氟系均染劑的摻合量成為未達0.01重量份之值時，有可有效果地保護在硬塗層之二氧化矽微粒子變困難，最終使耐蝕刻性提昇變困難的情況。另外，係因為氟系均染劑的摻合量成為超過0.2重量份之值時，有硬塗層之表面自由能量成為過度低之值，得到對於硬塗層所要求之黏著劑層等之特定密著性變困難的情況。 This reason is because when the blending amount of the fluorine-based leveling agent is less than 0.01 parts by weight, it becomes difficult to effectively protect the silicon dioxide fine particles in the hard coat layer, which ultimately makes it difficult to improve the etching resistance. Case. In addition, because the blending amount of the fluorine leveling agent becomes more than 0.2 parts by weight, the surface free energy of the hard coat layer becomes an excessively low value, and the specificity of the adhesive layer required for the hard coat layer is obtained. The case where adhesion becomes difficult.

據此，更佳為相對於作為(A)成分之活性能量線硬化 性樹脂100重量份，將氟系均染劑的摻合量定為0.03~0.18重量份的範圍內之值，再更佳為定為0.05~0.15重量份的範圍內之值。 Accordingly, it is more preferably hardened relative to the active energy ray as the component (A) 100 parts by weight of the sex resin, the blending amount of the fluorine-based leveling agent is set to a value within the range of 0.03 to 0.18 parts by weight, and more preferably to a value within the range of 0.05 to 0.15 parts by weight.

(1)-4(D)成分：光聚合起始劑 (1)-4(D) component: photopolymerization initiator

又，由於將活性能量線硬化性樹脂藉由活性能量線，尤其是紫外線可有效率地硬化，故較佳為藉由所期望併用作為(D)成分之光聚合起始劑。 In addition, since the active energy ray-curable resin can be efficiently cured by the active energy ray, especially ultraviolet rays, it is preferred to use the photopolymerization initiator as the component (D) in combination as desired.

作為該光聚合起始劑，相對於自由基聚合型之光聚合性預聚物或光聚合性單體，例如可列舉安息香、安息香甲基醚、安息香乙基醚、安息香異丙基醚、安息香-n-丁基醚、安息香異丁基醚、苯乙酮、二甲基胺基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、1-羥基環己基苯基酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基-丙烷-1-酮、4-(2-羥基乙氧基)苯基-2(羥基-2-丙基)酮、二苯甲酮、p-苯基二苯甲酮、4,4’-二乙基胺基二苯甲酮、二氯二苯甲酮、2-甲基蒽醌、2-乙基蒽醌、2-第三丁基蒽醌、2-胺基蒽醌、2-甲基噻噸酮、2-乙基噻噸酮、2-氯噻噸酮、2,4-二甲基噻噸酮、2,4-二乙基噻噸酮、苄基二甲基縮酮、苯乙酮二甲基縮酮、p-二甲基胺苯甲酸酯等。 As the photopolymerization initiator, examples of the radical polymerization type photopolymerizable prepolymer or photopolymerizable monomer include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin. -n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy Yl-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methyl Thio)phenyl)-2-morpholinyl-propane-1-one, 4-(2-hydroxyethoxy)phenyl-2(hydroxy-2-propyl)one, benzophenone, p- Phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-third-butylanthracene Quinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethyl Thioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethylamine benzoate, etc.

又，作為對於陽離子聚合型之光聚合性預聚物之光聚合起始劑，例如可列舉芳香族鋶離子、芳香族氧鋶(Oxosulfonium)離子、芳香族碘鎓離子等之鎓、與由四 氟硼酸酯、六氟磷酸酯、六氟銻酸酯、六氟砷酸酯等之陰離子所構成之化合物等。 In addition, examples of the photopolymerization initiator for the photopolymerizable prepolymer of the cation polymerization type include aromatic onium ions, aromatic oxonium ions (Oxosulfonium) ions, aromatic iodonium ions and other onium ions, and four Compounds composed of anions such as fluoroborate, hexafluorophosphate, hexafluoroantimonate, hexafluoroarsenate, etc.

尚，此等可1種單獨使用，亦可組合2種以上使用。 Still, these can be used alone or in combination of two or more.

又，作為光聚合起始劑的摻合量，相對於上述作為(A)成分之活性能量線硬化性樹脂100重量份，以成為0.2~10重量份的範圍內之值較佳，更佳為成為1~5重量份的範圍內之值。 In addition, the blending amount of the photopolymerization initiator is preferably a value in the range of 0.2 to 10 parts by weight relative to 100 parts by weight of the active energy ray-curable resin as the component (A), and more preferably It becomes a value within the range of 1 to 5 parts by weight.

(2)硬塗層形成用組成物 (2) Composition for hard coat layer formation

又，硬塗層較佳為預先調製硬塗層形成用組成物，如後述進行塗佈．乾燥，並藉由硬化而形成。 In addition, the hard coat layer is preferably prepared in advance to form a composition for forming a hard coat layer, which is applied as described later. Dry and form by hardening.

該組成物如有必要，可藉由於適當之溶劑中將活性能量線硬化性樹脂、光聚合起始劑、二氧化矽微粒子、及依所期望而使用之各種添加成分，分別以特定之比例加入，使其溶解或分散來調製。 If necessary, the composition can be added in a specific ratio by adding an active energy ray-curable resin, a photopolymerization initiator, silica fine particles, and various additives used as desired, in an appropriate solvent. , Dissolve or disperse to prepare.

尚，作為各種添加成分，例如可列舉抗氧化劑、紫外線吸收劑、(近)紅外線吸收劑、矽烷系偶合劑、光穩定劑、均染劑、防靜電劑、消泡劑等。 In addition, as various additional components, for example, antioxidants, ultraviolet absorbers, (near) infrared absorbers, silane-based coupling agents, light stabilizers, leveling agents, antistatic agents, defoaming agents and the like can be cited.

又，作為所用之溶劑，例如可列舉己烷、庚烷等之脂肪族烴、甲苯、二甲苯等之芳香族烴、二氯甲烷、二氯乙烷等之鹵化烴、甲醇、乙醇、丙醇、丁醇等之醇、丙酮、甲基乙基酮、2-戊酮、異佛爾酮、環己酮等之酮、乙酸乙酯、乙酸丁酯等之酯、乙基溶纖劑等之溶纖劑系溶劑等。 Examples of the solvent used include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as dichloromethane and dichloroethane, methanol, ethanol, and propanol. , Butanol and other alcohols, acetone, methyl ethyl ketone, 2-pentanone, isophorone, cyclohexanone and other ketones, ethyl acetate, butyl acetate and other esters, ethyl cellosolve, etc. Cellosolve solvents, etc.

作為如此進行所調製之硬塗層形成用組成物的濃度、黏度，若為可塗佈者即可，並未特別限定，可因應狀況適當選定。 The concentration and viscosity of the composition for forming a hard coat layer prepared in this way are not particularly limited as long as they are coatable, and can be appropriately selected according to the situation.

據此，從易將通常所得之硬塗層形成用組成物的膜厚調節在特定的範圍的觀點來看，較佳為以固含量濃度成為0.05~30重量%的方式稀釋，更佳為以成為0.1~25重量%的方式稀釋。 Accordingly, from the viewpoint of easily adjusting the film thickness of the composition for forming a hard coat layer generally obtained in a specific range, it is preferably diluted so that the solid content concentration becomes 0.05 to 30% by weight, and more preferably Dilute by 0.1-25% by weight.

(3)膜厚 (3) Film thickness

又，較佳為將硬塗層的膜厚定為0.5~5μm的範圍內之值。 In addition, it is preferable to set the film thickness of the hard coat layer to a value in the range of 0.5 to 5 μm.

此理由，係因為硬塗層的膜厚成為未達0.5μm之值時，有不僅降低樹脂的硬化性，得到充分之耐蝕刻性變困難，而且藉由退火處理對基材薄膜之熱收縮的保持機能變不夠充分，無法抑制捲曲的發生的情況。另外，係因為硬塗層的膜厚成為超過5μm之值時，有藉由退火處理從硬塗層易發生排氣的情況。 This reason is because when the film thickness of the hard coat layer is less than 0.5 μm, it is not only difficult to reduce the curability of the resin and obtain sufficient etching resistance, but also the heat shrinkage of the substrate film by annealing The retention function becomes insufficient, and the occurrence of curling cannot be suppressed. In addition, when the film thickness of the hard coat layer exceeds 5 μm, exhaust gas may easily occur from the hard coat layer by annealing.

據此，更佳為將硬塗層的膜厚定為0.8~4μm的範圍內之值，再更佳為定為1~3μm的範圍內之值。 Accordingly, the film thickness of the hard coat layer is more preferably set to a value in the range of 0.8 to 4 μm, and even more preferably set to a value in the range of 1 to 3 μm.

3.光學調整層 3. Optical adjustment layer

如圖1(a)所示，光學調整層2，較佳為從基材薄膜4側，依相對性折射率高之高折射率層2b、與相對性折射率低之低折射率層2a順序層合而成。 As shown in FIG. 1(a), the optical adjustment layer 2 is preferably arranged from the base film 4 side in order of a high refractive index layer 2b having a high relative refractive index and a low refractive index layer 2a having a low relative refractive index. Laminated.

此理由，係因為藉由將光學調整層成為如此之層合構造，可有效果地抑制透明導電層之折射率、與起因於和基材薄膜4之折射率的差異，變成易視別透明導電層的圖型形狀。 This reason is because by making the optical adjustment layer into such a laminated structure, the difference between the refractive index of the transparent conductive layer and the refractive index due to the base film 4 can be effectively suppressed, and the transparent conductive can be easily recognized The graphic shape of the layer.

(1)高折射率層 (1) High refractive index layer

(1)-1折射率 (1)-1 refractive index

較佳為高折射率層之折射率定為1.6以上之值。 The refractive index of the high refractive index layer is preferably set to a value of 1.6 or more.

此理由，係因為高折射率層之折射率成為未達1.6之值時，有得不到與低折射率層之顯著折射率差異、或易視別透明導電層之圖型形狀的情況。另外，係因為高折射率層之折射率成為過度大之值時，有高折射率層之膜變脆的情況。 This reason is because when the refractive index of the high refractive index layer is less than 1.6, there may be no significant difference in refractive index from the low refractive index layer, or the pattern shape of the transparent conductive layer may be easily recognized. In addition, when the refractive index of the high refractive index layer becomes an excessively large value, the film of the high refractive index layer may become brittle.

據此，更佳為將高折射率層之折射率定為1.61~2的範圍內之值，再更佳為定為1.63~1.8的範圍內之值。 Accordingly, it is more preferable to set the refractive index of the high refractive index layer to a value in the range of 1.61 to 2, and even more preferably to a value in the range of 1.63 to 1.8.

(1)-2材料物質 (1)-2 Material substance

又，較佳為高折射率層係由包含作為材料物質之金屬氧化物微粒子及活性能量線硬化性樹脂之組成物的硬化物所構成。 In addition, it is preferable that the high refractive index layer is composed of a cured product of a composition containing metal oxide fine particles as a material substance and an active energy ray curable resin.

此理由，係因為藉由包含金屬氧化物微粒子及活性能量線硬化性樹脂，使得在高折射率層之折射率的調整變容易。 This reason is because the inclusion of metal oxide fine particles and active energy ray-curable resin makes it easy to adjust the refractive index of the high refractive index layer.

又，金屬氧化物的種類，較佳可列舉氧化 鉭、氧化鋅、氧化銦、氧化鉿、氧化鈰、氧化錫、氧化鈮、銦錫氧化物(ITO)、銻錫氧化物(ATO)等。 In addition, the type of metal oxide preferably includes oxidation Tantalum, zinc oxide, indium oxide, hafnium oxide, cerium oxide, tin oxide, niobium oxide, indium tin oxide (ITO), antimony tin oxide (ATO), etc.

又，從不降低透明性而實現高折射率化的觀點來看，特佳為選自氧化鈦及氧化鋯中之至少1種。 In addition, from the viewpoint of achieving a high refractive index without lowering the transparency, particularly preferably at least one kind selected from titanium oxide and zirconium oxide.

尚，此等之金屬氧化物可1種單獨使用，亦可併用2種以上。 Still, these metal oxides may be used alone or in combination of two or more.

又，較佳為金屬氧化物微粒子的體積平均粒徑(D50)定為0.005μm~1μm的範圍內之值。 In addition, it is preferable that the volume average particle diameter (D50) of the metal oxide fine particles is set to a value in the range of 0.005 μm to 1 μm.

尚，金屬氧化物微粒子的體積平均粒徑(D50)，例如除了藉由使用仄他電位測定法之測定法求得之外，亦可使用雷射繞射散射式粒度分布測定裝置求得，進而亦可將SEM圖像作為基礎求得。 In addition, the volume average particle diameter (D50) of the metal oxide fine particles can be obtained by using a laser diffraction scattering type particle size distribution measuring device, for example, in addition to the measurement method using the beta potential measurement method, and It can also be obtained based on the SEM image.

又，作為高折射率層所使用之活性能量線硬化性樹脂及光聚合起始劑，可適當使用在硬塗層之說明所列舉者。 In addition, as the active energy ray-curable resin and the photopolymerization initiator used in the high refractive index layer, those listed in the description of the hard coat layer can be suitably used.

又，作為金屬氧化物微粒子的摻合量，相對於活性能量線硬化性樹脂100重量份，較佳為20~2000重量份，更佳為80~1000重量份，再更佳為150~400重量份。 Moreover, as the blending amount of the metal oxide fine particles, it is preferably 20 to 2000 parts by weight, more preferably 80 to 1000 parts by weight, and still more preferably 150 to 400 parts by weight with respect to 100 parts by weight of the active energy ray-curable resin. Copies.

(1)-3高折射率層形成用組成物 (1)-3 Composition for forming high refractive index layer

又，高折射率層較佳為預先調製高折射率層形成用之組成物，如後述進行塗佈．乾燥，並藉由硬化而形成。 In addition, the high refractive index layer is preferably prepared in advance to form a composition for forming a high refractive index layer, coating as described later. Dry and form by hardening.

該組成物如有必要，可藉由於適當之溶劑中將活性能量線硬化性樹脂、光聚合起始劑、二氧化矽微粒子、及依所期望而使用之各種添加成分，分別以特定之比例加入， 使其溶解或分散來調製。 If necessary, the composition can be added in a specific ratio by adding an active energy ray-curable resin, a photopolymerization initiator, silica fine particles, and various additives used as desired, in an appropriate solvent. , It is prepared by dissolving or dispersing.

尚，針對各種添加成分、溶劑、高折射率層形成用之組成物的濃度、黏度等，與在硬塗層之說明的內容相同。 The concentration, viscosity, etc. of various additives, solvents, and high-refractive-index layer forming components are the same as those described in the hard coat layer.

(1)-4膜厚 (1)-4 film thickness

又，較佳為將高折射率層的膜厚定為20~130nm。 In addition, it is preferable to set the film thickness of the high refractive index layer to 20 to 130 nm.

此理由，係因為高折射率層的膜厚成為未達20nm之值時，有高折射率層的膜變脆，無法維持層的形狀的情況。另外，係因為高折射率層的膜厚超過130nm之值時，有透明導電層的圖型形狀變易視別的情況。 This reason is because when the film thickness of the high refractive index layer is less than 20 nm, the film of the high refractive index layer may become brittle and the shape of the layer may not be maintained. In addition, when the film thickness of the high refractive index layer exceeds 130 nm, the pattern shape of the transparent conductive layer may be easily distinguished.

據此，更佳為將高折射率層的膜厚定為23~120nm，再更佳為定為30~110nm。 Accordingly, the film thickness of the high refractive index layer is preferably 23 to 120 nm, and more preferably 30 to 110 nm.

(2)低折射率層 (2) Low refractive index layer

(2)-1折射率 (2)-1 refractive index

較佳為將低折射率層之折射率定為1.45以下之值。 The refractive index of the low refractive index layer is preferably set to a value of 1.45 or less.

此理由，係因為低折射率層之折射率成為超過1.45之值時，有變無法得到與高折射率層之顯著折射率差異，透明導電層之圖型形狀變易視別的情況。另外，係因為低折射率層之折射率成為過度小之值時，有低折射率層之膜變脆的情況。 This reason is because when the refractive index of the low-refractive-index layer exceeds 1.45, a significant difference in refractive index from the high-refractive-index layer may not be obtained, and the pattern shape of the transparent conductive layer may be easily distinguished. In addition, when the refractive index of the low refractive index layer becomes an excessively small value, the film of the low refractive index layer may become brittle.

據此，更佳為將低折射率層之折射率定為1.3~1.44的範圍內之值，再更佳為定為1.35~1.43的範圍內之值。 Accordingly, it is more preferable to set the refractive index of the low refractive index layer to a value in the range of 1.3 to 1.44, and still more preferably to a value in the range of 1.35 to 1.43.

(2)-2材料物質 (2)-2 Material substance

又，在本發明之低折射率層，作為材料物質，較佳為光硬化包含下述(a)~(b)成分之低折射率層形成用組成物而成。 In addition, in the low refractive index layer of the present invention, as the material substance, it is preferable that the composition for forming a low refractive index layer containing the following components (a) to (b) is photocured.

此理由，係因為形成低折射率層時所用之低折射率層形成用組成物，相對於活性能量線硬化性樹脂，藉由以比較少的範圍包含二氧化矽微粒子，即使於進行包含嚴格鹼處理之蝕刻處理的情況，亦可有效果地抑制在低折射率層之二氧化矽微粒子溶解、或是脫落。 This reason is because the composition for forming a low-refractive-index layer used for forming the low-refractive-index layer contains a relatively small range of silicon dioxide fine particles relative to the active energy ray-curable resin, even if it contains a strict alkali In the case of the etching treatment, the silicon dioxide particles in the low refractive index layer can be effectively suppressed from dissolving or falling off.

又，活性能量線硬化性樹脂係藉由硬化構成在低折射率層之基質部分，更有效果地保護在低折射率層之二氧化矽微粒子，可更有效果地提昇耐蝕刻性。 In addition, the active energy ray-curable resin is formed by hardening the matrix portion of the low-refractive-index layer, which effectively protects the silicon dioxide fine particles in the low-refractive-index layer, and can effectively improve the etching resistance.

以下，對每個成分進行說明。 Hereinafter, each component will be described.

(i)(a)成分：活性能量線硬化性樹脂 (i) (a) component: active energy ray curable resin

(a)成分係活性能量線硬化性樹脂。 (a) The component-based active energy ray-curable resin.

作為該作為(a)成分之活性能量線硬化性樹脂，可適當使用在硬塗層之說明所列舉之光聚合性預聚物或光聚合性單體。 As the active energy ray-curable resin as the component (a), a photopolymerizable prepolymer or photopolymerizable monomer listed in the description of the hard coat layer can be suitably used.

又，較佳為活性能量線硬化性樹脂含有撥水性樹脂。 Furthermore, it is preferable that the active energy ray-curable resin contains a water-repellent resin.

此理由，係因為藉由含有撥水性樹脂，由於可更有效果地保護在低折射率層之二氧化矽微粒子，故可更進一層與有效果地使耐蝕刻性提昇。 This reason is because by containing the water-repellent resin, the silicon dioxide fine particles in the low refractive index layer can be more effectively protected, so that the layer can be further layered and the etching resistance can be effectively improved.

又，係因為若為撥水性樹脂，與主要活性能量線硬化樹脂即(甲基)丙烯酸系紫外線硬化性樹脂進行比較，由於折射率低，故可更容易將低折射率層之折射率降低至特定之範圍。 In addition, if it is a water-repellent resin, compared with the (meth)acrylic ultraviolet curable resin which is the main active energy ray curing resin, the refractive index is low, so it is easier to reduce the refractive index of the low refractive index layer to Specific scope.

又，作為該撥水性樹脂，若為具有撥水性之樹脂，則並非特別限制者，可使用以往周知之撥水性樹脂。 In addition, as the water-repellent resin, if it is a resin having water-repellent properties, it is not particularly limited, and a conventionally known water-repellent resin can be used.

更具體而言，若以撥水性樹脂單體形成在樹脂膜之表面自由能量為10~30mN/m的範圍內之值，可適合作為在本發明之撥水性樹脂使用。 More specifically, if the water repellent resin monomer is formed on the surface of the resin film with a free energy in the range of 10 to 30 mN/m, it can be suitably used as the water repellent resin in the present invention.

又，作為撥水性樹脂之具體例，例如可列舉矽氧樹脂、或例如可列舉聚偏二氟乙烯、氟系丙烯酸樹脂及聚氟乙烯等之氟樹脂。 In addition, as specific examples of the water-repellent resin, for example, a silicone resin or, for example, a fluorine resin such as polyvinylidene fluoride, a fluorine-based acrylic resin, and polyvinyl fluoride.

又，其中，較佳為使用氟樹脂，特佳為反應性氟丙烯酸樹脂。 Moreover, among them, it is preferable to use a fluororesin, and particularly preferably a reactive fluoroacrylic resin.

此理由，係因為若為氟樹脂，由於可更有效果地保護在低折射率層之二氧化矽微粒子，故可更有效果地使耐蝕刻性提昇。 This reason is because if it is a fluororesin, since the silicon dioxide fine particles in the low refractive index layer can be protected more effectively, the etching resistance can be improved more effectively.

又，較佳為將(a)成分全體定為100重量%的情況下，將撥水性樹脂的含量定為50~90重量%的範圍內之值。 In addition, it is preferable to set the content of the water-repellent resin to a value in the range of 50 to 90% by weight when the entire component (a) is set to 100% by weight.

此理由，係因為撥水性樹脂的含量成為未達50重量 %之值時，有有效果地保護在低折射率層之二氧化矽微粒子變困難，最終使耐蝕刻性提昇變困難的情況。又，係因為有將低折射率層之折射率定為充分低之值變困難的情況。另外，係因為撥水性樹脂的含量成為超過90重量%之值時，有低折射率層之表面自由能量成為過度低之值，得到對於折射率層所要求之透明導電層等之特定密著性變困難的情況。 This reason is because the content of the water-repellent resin becomes less than 50 weight At a value of %, it becomes difficult to effectively protect the silicon dioxide fine particles in the low refractive index layer, which ultimately makes it difficult to improve the etching resistance. In addition, it may be difficult to set the refractive index of the low refractive index layer to a sufficiently low value. In addition, when the content of the water-repellent resin exceeds 90% by weight, the surface free energy of the low-refractive-index layer becomes an excessively low value, and the specific adhesion of the transparent conductive layer and the like required for the refractive-index layer is obtained. Difficult situation.

據此，更佳為將(a)成分全體定為100重量%的情況下，將撥水性樹脂的含量定為60~85重量%的範圍內之值，再更佳為定為70~80重量%的範圍內之值。 According to this, it is more preferable to set the content of the water-repellent resin to a value within the range of 60 to 85% by weight when the total content of (a) component is set to 100% by weight, and even more preferably to set to 70 to 80% by weight The value in the range of %.

(ii)(b)成分：二氧化矽微粒子 (ii) (b) Ingredients: silica fine particles

(b)成分係二氧化矽微粒子。 (b) The component is silica fine particles.

作為該二氧化矽微粒子的種類，雖並非被特別限制者，但較佳為使用中空二氧化矽微粒子。 Although the type of the silica fine particles is not particularly limited, it is preferable to use hollow silica fine particles.

此理由，係因為若為中空二氧化矽微粒子，由於在內部之中空部分包含空氣，故變成進一步降低作為二氧化矽微粒子全體之折射率，即使為少量之摻合量，亦可更有效率地將低折射率層之折射率調整至特定之折射率。 This reason is because if it is hollow silica particles, since the hollow part inside contains air, the refractive index of the entire silica particles is further reduced, and even a small amount of blending can be more efficient The refractive index of the low refractive index layer is adjusted to a specific refractive index.

尚，所謂「中空二氧化矽微粒子」，係意指於粒子之內部具有空洞之二氧化矽微粒子。 Still, the so-called "hollow silica particles" means silica particles with holes inside the particles.

又，較佳為二氧化矽微粒子為反應性二氧化矽微粒子。 Moreover, it is preferable that the silica fine particles are reactive silica fine particles.

此理由，係因為若為反應性二氧化矽微粒子，由於可 對低折射率層牢牢地固定二氧化矽微粒子，故可更有效果地提昇耐蝕刻性。 This reason is because if it is a reactive silica particle, it can be The silicon dioxide particles are firmly fixed to the low refractive index layer, so that the etching resistance can be improved more effectively.

尚，所謂「反應性二氧化矽微粒子」，係指結合含有聚合性不飽和基之有機化合物之二氧化矽微粒子，在二氧化矽微粒子表面之矽醇基，可藉由使含有聚合性不飽和基之有機化合物進行反應而得到，該不飽和基係具有可與該矽醇基反應之官能基。 Still, the so-called "reactive silica particles" refers to the combination of silica particles with organic compounds containing polymerizable unsaturated groups, and the silanol groups on the surface of the silica particles can be made by containing polymerizable unsaturated It is obtained by reacting an organic compound of a group, and the unsaturated group has a functional group that can react with the silanol group.

又，作為上述之聚合性不飽和基，例如可列舉自由基聚合性之丙烯醯基或甲基丙烯醯基等。 In addition, examples of the above-mentioned polymerizable unsaturated group include a radically polymerizable acryl group and methacryl group.

又，較佳為將二氧化矽微粒子的體積平均粒徑(D50)定為20~70nm的範圍內之值。 In addition, it is preferable to set the volume average particle diameter (D50) of the silica fine particles to a value in the range of 20 to 70 nm.

此理由，係因為藉由將二氧化矽微粒子的體積平均粒徑(D50)定為該範圍內之值，不會使在低折射率層之透明性降低，而且可得到特定之折射率。 This reason is because by setting the volume average particle diameter (D50) of the silica fine particles to a value within this range, the transparency of the low refractive index layer is not reduced, and a specific refractive index can be obtained.

亦即，係因為二氧化矽微粒子的體積平均粒徑(D50)成為未達20nm之值時，尤其是中空二氧化矽微粒子的情況，有其構造上充分確保粒子內部之空洞部變困難，使低折射率層之折射率降低的效果變不夠充分的情況。另外，係因為二氧化矽微粒子的體積平均粒徑(D50)成為超過70nm之值時，有變成易產生光之散射，易降低在低折射率層之透明性的情況。 That is, when the volume average particle diameter (D50) of the silica particles is less than 20 nm, especially in the case of hollow silica particles, it is difficult to sufficiently ensure the cavity inside the particles by the structure, making When the effect of reducing the refractive index of the low refractive index layer becomes insufficient. In addition, when the volume average particle diameter (D50) of the silicon dioxide fine particles exceeds 70 nm, light scattering is likely to occur, and the transparency of the low refractive index layer may be easily reduced.

據此，更佳為將二氧化矽微粒子的體積平均粒徑(D50)定為30~60nm的範圍內之值，再更佳為定為40~50nm的範圍內之值。 Accordingly, it is more preferable to set the volume average particle diameter (D50) of the silica particles to a value in the range of 30 to 60 nm, and still more preferably to a value in the range of 40 to 50 nm.

尚，二氧化矽微粒子的體積平均粒徑(D50)，例如除了可藉由仄他電位測定法求得之外，亦可使用雷射繞射散射式粒度分布測定裝置求得，進而亦可將SEM圖像為基礎求得。 In addition, the volume average particle diameter (D50) of silica fine particles can be obtained, for example, by a beta potential measurement method, or by a laser diffraction scattering type particle size distribution measuring device, and furthermore Obtained based on SEM images.

又，較佳為相對於含有作為(a)成分之撥水性樹脂之活性能量線硬化性樹脂100重量份，將二氧化矽微粒子的摻合量定為2~120重量份的範圍內之值。 In addition, it is preferable to set the blending amount of the silica fine particles to a value in the range of 2 to 120 parts by weight with respect to 100 parts by weight of the active energy ray-curable resin containing the water-repellent resin as the component (a).

此理由，係因為二氧化矽微粒子的摻合量成為未達2重量份之值時，有使低折射率層之折射率充分降低變困難、或於低折射率層的表面形成充分之表面凹凸變困難、或得到對於透明導電層等之特定密著性變困難的情況。另外，係因為二氧化矽微粒子的摻合量成為超過120重量份之值時，於進行包含嚴格鹼處理之蝕刻處理的情況，有低折射率層之二氧化矽微粒子溶解、或是脫落變容易的情況。 This reason is because when the blending amount of the silica particles is less than 2 parts by weight, it may be difficult to sufficiently reduce the refractive index of the low refractive index layer, or sufficient surface irregularities may be formed on the surface of the low refractive index layer It becomes difficult, or it becomes difficult to obtain specific adhesion to a transparent conductive layer or the like. In addition, when the blending amount of the silicon dioxide fine particles exceeds 120 parts by weight, when the etching treatment including strict alkali treatment is performed, the silicon dioxide fine particles of the low refractive index layer may easily dissolve or fall off Case.

據此，更佳為相對於含有作為(a)成分之撥水性樹脂之活性能量線硬化性樹脂100重量份，將二氧化矽微粒子的摻合量定為30~110重量份的範圍內之值，再更佳為定為50~100重量份的範圍內之值。 Accordingly, it is more preferable to set the blending amount of the silica fine particles to a value in the range of 30 to 110 parts by weight with respect to 100 parts by weight of the active energy ray-curable resin containing the water-repellent resin as the component (a). It is even better to set the value within the range of 50 to 100 parts by weight.

(2)-3低折射率層形成用組成物 (2)-3 Composition for forming low refractive index layer

又，低折射率層為預先調製低折射率層形成用組成物，如後述進行塗佈．乾燥，並藉由硬化而形成。 In addition, the low-refractive-index layer is a composition for forming a low-refractive-index layer prepared in advance, and is coated as described later. Dry and form by hardening.

該組成物如有必要，可藉由於適當之溶劑中將上述之 作為(a)成分之活性能量線硬化性樹脂、及作為(b)成分之二氧化矽微粒子、以及光聚合起始劑其他之各種添加成分，分別以特定之比例加入，使其溶解或分散來調製。 If necessary, the composition can be The active energy ray-curable resin as the component (a), the silica fine particles as the component (b), and various other added components of the photopolymerization initiator are added in specific ratios to dissolve or disperse modulation.

尚，針對各種添加成分、溶劑、低折射率層形成用組成物的濃度、黏度等，與在硬塗層之說明的內容相同。 The concentration, viscosity, etc. of various additives, solvents, and low-refractive-index layer forming compositions are the same as those described in the hard coat layer.

(2)-4膜厚 (2)-4 film thickness

又，較佳為將低折射率層的膜厚定為20~150nm的範圍內之值。 In addition, it is preferable to set the film thickness of the low refractive index layer to a value in the range of 20 to 150 nm.

此理由，係因為藉由將低折射率層的膜厚定為該範圍內之值，可更穩定地不可見化透明導電層之圖型形狀，同時可得到充分之耐蝕刻性。 This reason is because by setting the film thickness of the low refractive index layer to a value within this range, the pattern shape of the transparent conductive layer can be more invisible, and sufficient etching resistance can be obtained.

亦即，低折射率層的膜厚成為未達20nm之值時，有低折射率層的膜變脆，耐蝕刻性變不夠充分的情況。另外，係因為低折射率層的膜厚超過150nm之值時，有透明導電層的圖型形狀變易視別的情況。 That is, when the film thickness of the low refractive index layer is less than 20 nm, the film of the low refractive index layer may become brittle and the etching resistance may become insufficient. In addition, when the film thickness of the low-refractive-index layer exceeds 150 nm, the pattern shape of the transparent conductive layer may be easily distinguished.

據此，更佳為將低折射率層的膜厚定為25~120nm的範圍內之值，再更佳為定為30~100nm的範圍內之值。 Accordingly, the film thickness of the low refractive index layer is more preferably set to a value in the range of 25 to 120 nm, and still more preferably set to a value in the range of 30 to 100 nm.

4.透明導電層形成用層合體之製造方法 4. Manufacturing method of laminated body for forming transparent conductive layer

本發明之透明導電層形成用層合體，例如可藉由包含下述步驟(a)~(b)之製造方法得到。 The laminate for forming a transparent conductive layer of the present invention can be obtained, for example, by a manufacturing method including the following steps (a) to (b).

(a)於基材薄膜之兩面形成硬塗層之步驟 (a) Step of forming hard coating on both sides of the base film

(b)於一側的硬塗層上形成光學調整層之步驟 (b) Step of forming optical adjustment layer on one side of hard coating

以下，省略與目前為止的內容重複之部分，僅詳述不同部分。 In the following, parts that overlap with the contents so far are omitted, and only the different parts are described in detail.

尚，本發明之透明導電層形成用層合體，雖未於基材薄膜之兩面將硬塗層作為必須之構成要件，但在以下之說明，將於基材薄膜之兩面形成硬塗層的情況列舉為例來說明。 Although the laminate for forming a transparent conductive layer of the present invention does not require a hard coat layer on both sides of the base film, the hard coat layer will be formed on both sides of the base film as explained below Take an example to illustrate.

(1)步驟(a)：形成硬塗層之步驟 (1) Step (a): Step of forming hard coating

於基材薄膜之兩面，將上述之硬塗層形成用組成物在以往周知之方法進行塗佈而形成塗膜後，進行乾燥，並藉由於此照射活性能量線使塗膜硬化，來形成硬塗層。 On both sides of the base material film, the above-mentioned composition for forming a hard coat layer is applied in a conventionally well-known method to form a coating film, dried, and the coating film is hardened by irradiation of active energy rays to form a hard layer coating.

又，作為硬塗層形成用組成物之塗佈方法，例如可列舉棒塗佈法、刮刀塗佈法、輥塗法、片塗佈法、模具塗佈．法、凹版塗佈法等。 In addition, as the coating method of the composition for forming a hard coat layer, for example, a bar coating method, a blade coating method, a roll coating method, a sheet coating method, and a die coating method can be cited. Method, gravure coating method, etc.

又，作為乾燥條件，較佳為以60~150℃進行10秒~10分鐘左右。 In addition, as the drying conditions, it is preferably performed at 60 to 150° C. for about 10 seconds to 10 minutes.

進而，作為活性能量線，例如可列舉紫外線或電子束等。 Furthermore, examples of the active energy rays include ultraviolet rays and electron beams.

又，作為紫外線之光源，可列舉高壓水銀燈、無電極燈、金屬鹵素燈、氙氣燈等，其照射量通常以成為100~500mJ/cm²較佳。 In addition, examples of the ultraviolet light source include high-pressure mercury lamps, electrodeless lamps, metal halide lamps, and xenon lamps. The irradiation dose is usually 100 to 500 mJ/cm ² .

另外，作為電子束之光源，可列舉電子束加速器等， 其照射量通常以成為150~350kV較佳。 In addition, as the light source of the electron beam, an electron beam accelerator, etc. may be mentioned. The irradiation dose is usually preferably 150 to 350 kV.

又，照射活性能量線時，更佳為在氮環境下進行。 In addition, when irradiating the active energy ray, it is more preferably performed in a nitrogen environment.

此理由，係因為藉由在氮環境下進行，硬塗層表面之硬化反應有效果地進展，可更有效果地提昇在硬塗層之耐蝕刻性。 This reason is because the hardening reaction on the surface of the hard coat layer progresses effectively by performing under a nitrogen environment, and the etching resistance of the hard coat layer can be more effectively improved.

(2)步驟(b)：形成光學調整層之步驟 (2) Step (b): Step of forming the optical adjustment layer

其次，於所形成之硬塗層上(未形成硬塗層的情況下直接於基材薄膜上)，形成高折射率層。 Secondly, a high refractive index layer is formed on the formed hard coating layer (directly on the substrate film without forming a hard coating layer).

亦即，高折射率層係與於基材薄膜上形成硬塗層同樣進行，可藉由塗佈．乾燥上述之高折射率層形成用組成物，同時照射活性能量線使其硬化來形成。 That is, the high refractive index layer is formed in the same way as the hard coat layer formed on the substrate film, which can be applied by coating. The above composition for forming a high refractive index layer is dried and irradiated with active energy rays to be hardened to form.

其次，於所形成之高折射率層上進一步形成低折射率層。 Secondly, a low refractive index layer is further formed on the formed high refractive index layer.

亦即，低折射率層係與於基材薄膜上形成硬塗層同樣進行，可藉由塗佈．乾燥上述之低折射率層形成用組成物，同時照射活性能量線使其硬化來形成。 That is, the low-refractive-index layer is formed in the same way as the hard coat layer formed on the substrate film, and can be applied by coating. The composition for forming the low-refractive-index layer described above is dried and simultaneously irradiated with active energy rays to be hardened to form.

又，照射活性能量線時，更佳為在氮環境下進行。 In addition, when irradiating the active energy ray, it is more preferably performed in a nitrogen environment.

此理由，係因為藉由在氮環境下進行，光學調整層表面之硬化反應有效果地進展，可更有效果地提昇在光學調整層，尤其是最表面層即低折射率層之耐蝕刻性。 This reason is because the hardening reaction on the surface of the optical adjustment layer progresses effectively under a nitrogen environment, and the etching resistance of the optical adjustment layer, especially the surface layer, that is, the low refractive index layer can be improved more effectively .

[第2實施形態] [Second Embodiment]

本發明之第2實施形態係如圖3所示，一種透明導電 性薄膜，其係依硬塗層、基材薄膜、光學調整層、透明導電層順序層合而成之透明導電性薄膜，其特徵為前述硬塗層係光硬化包含下述(A)~(B)成分之硬塗層形成用組成物而成，

The second embodiment of the present invention is shown in FIG. 3, a transparent conductive film, which is a transparent conductive film formed by sequentially laminating a hard coat layer, a base film, an optical adjustment layer, and a transparent conductive layer, which It is characterized in that the aforementioned hard coat layer is formed by a photohardening composition for forming a hard coat layer containing the following components (A) to (B),

以下，將本發明之第2實施形態省略與目前為止的內容重複之部分，僅詳述不同部分。 In the following, the second embodiment of the present invention omits parts that overlap with the contents so far, and only details the different parts.

1.透明導電層 1. Transparent conductive layer

(1)材料物質 (1) Material substance

在本發明之透明導電性薄膜，作為透明導電層之材料物質，若為一併擁有透明性與導電性者，雖並非被特別限制者，但例如可列舉氧化銦、氧化鋅、氧化錫、銦錫氧化物(ITO)、錫銻氧化物、鋅鋁氧化物、銦鋅氧化物等。 In the transparent conductive film of the present invention, as the material of the transparent conductive layer, if it has both transparency and conductivity, it is not particularly limited, but examples include indium oxide, zinc oxide, tin oxide, and indium. Tin oxide (ITO), tin antimony oxide, zinc aluminum oxide, indium zinc oxide, etc.

又，尤其是作為材料物質，較佳為使用ITO。 Moreover, it is preferable to use ITO especially as a material substance.

此理由，係因為若為ITO，藉由採用適當之造膜條件，可形成透明性及導電性優異之透明導電層。 This reason is because if it is ITO, a transparent conductive layer excellent in transparency and conductivity can be formed by adopting appropriate film forming conditions.

(2)圖型形狀 (2) Pattern shape

又，較佳為透明導電層係藉由蝕刻形成如線狀或格子狀之圖型形狀。 Moreover, it is preferable that the transparent conductive layer is formed into a pattern shape such as a linear shape or a lattice shape by etching.

又，上述之圖型形狀較佳為透明導電層之存在部分的 線寬、與透明導電層未存在部分的線寬略為相等。 In addition, the above-mentioned pattern shape is preferably the part where the transparent conductive layer exists The line width is slightly equal to the line width of the portion where the transparent conductive layer does not exist.

進而，該線寬通常為0.1~10mm，較佳為0.2~5mm，特佳為0.5~2mm。 Furthermore, the line width is usually 0.1 to 10 mm, preferably 0.2 to 5 mm, and particularly preferably 0.5 to 2 mm.

尚，在上述之線狀或格子狀之線寬未限定於一定的情況，例如可自由選擇與靜電容量式之觸控面板所要求之形狀相關連者。 In addition, in the case where the above-mentioned line-shaped or grid-shaped line width is not limited to a certain case, for example, it is possible to freely select a shape related to the shape required by the capacitive touch panel.

具體而言，可列舉菱形部分與線部重複連結之圖型形狀等，如此之圖型形狀亦包含在「線狀」之範疇。 Specifically, a pattern shape in which a rhombic portion and a line portion are repeatedly connected can be cited. Such a pattern shape is also included in the category of “line shape”.

尚，將透明導電層如此形成的情況，藉由實施退火處理，雖然通常透明導電層之圖型形狀變為顯著，但如圖3所示，於基材薄膜兩側設置硬塗層的情況下，若為本發明之透明導電性薄膜，可不可見化透明導電層之圖型形狀。 Still, in the case where the transparent conductive layer is formed in this way, by performing annealing treatment, although the pattern shape of the transparent conductive layer usually becomes significant, as shown in FIG. 3, when a hard coat layer is provided on both sides of the base film If it is the transparent conductive film of the present invention, the pattern shape of the transparent conductive layer may not be visible.

(3)膜厚 (3) Film thickness

又，透明導電層之厚度較佳為5~500nm。 In addition, the thickness of the transparent conductive layer is preferably 5 to 500 nm.

此理由，係因為透明導電層之厚度成為未達5nm之值時，有不僅透明導電層變脆，而且得不到充分之導電性的情況。另外，係因為透明導電層之厚度成為超過500nm之值時，有起因於透明導電層之色味增強，圖型形狀變易認識的情況。 This reason is because when the thickness of the transparent conductive layer is less than 5 nm, the transparent conductive layer may not only become brittle, but sufficient conductivity may not be obtained. In addition, when the thickness of the transparent conductive layer becomes a value exceeding 500 nm, the color taste of the transparent conductive layer is enhanced, and the pattern shape may be easily recognized.

據此，透明導電層之厚度更佳為15~250nm，再更佳為20~100nm。 Accordingly, the thickness of the transparent conductive layer is more preferably 15 to 250 nm, and even more preferably 20 to 100 nm.

2.透明導電性薄膜之製造方法 2. Manufacturing method of transparent conductive film

對於在上述之透明導電層形成用層合體之製造方法之步驟(b)所得之光學調整層，藉由真空蒸鍍法、濺鍍法、CVD法、離子鍍法、噴灑法、溶膠-凝膠法等周知之方法，並藉由形成透明導電層，可得到透明導電性薄膜。 For the optical adjustment layer obtained in step (b) of the method for manufacturing a transparent conductive layer-forming laminate described above, by vacuum evaporation method, sputtering method, CVD method, ion plating method, spray method, sol-gel A well-known method such as a method, and by forming a transparent conductive layer, a transparent conductive film can be obtained.

又，作為濺鍍法，可列舉使用化合物之通常濺鍍法、或者使用金屬靶之反應性濺鍍法等。 In addition, examples of the sputtering method include a general sputtering method using a compound, a reactive sputtering method using a metal target, and the like.

此時，亦佳為導入氧、氮、水蒸氣等作為反應性氣體、或是併用臭氧添加或離子輔助等。 At this time, it is also preferable to introduce oxygen, nitrogen, water vapor, etc. as a reactive gas, or to use ozone addition or ion assist in combination.

又，透明導電層如上述進行來製膜後，藉由光微影法形成特定圖型之抗蝕光罩後，藉由藉周知之方法實施蝕刻處理，可形成線狀之圖型等。 Furthermore, after the transparent conductive layer is formed as described above, after forming a resist mask of a specific pattern by photolithography, an etching process can be performed by a well-known method to form a linear pattern.

尚，作為蝕刻液，較佳可列舉鹽酸、硫酸、硝酸、磷酸等之酸的水溶液等。 In addition, as the etching solution, preferably, an aqueous solution of an acid such as hydrochloric acid, sulfuric acid, nitric acid, or phosphoric acid is used.

又，作為蝕刻處理之最終步驟即用以去除殘留之光阻之鹼處理所使用之溶液，從蝕刻處理之迅速化的觀點來看，較佳為使用液溫10~50℃、濃度1~10重量%、pH13.4~14.4之強鹼水溶液。 In addition, as the final step of the etching process, the solution used in the alkaline process for removing the remaining photoresist, from the viewpoint of rapid etching process, it is preferable to use a liquid temperature of 10 to 50°C and a concentration of 1 to 10 A strong alkaline aqueous solution with a weight% and a pH of 13.4 to 14.4.

又，作為適合之強鹼，可列舉氫氧化鋰、氫氧化鈉、氫氧化鉀、氫氧化銣、氫氧化銫、氫氧化四甲基銨、氫氧化四乙基銨、氫氧化鈣、氫氧化鍶、氫氧化鋇、氫氧化銪(II)、氫氧化鉈(I)、胍等。 Further, suitable strong bases include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, calcium hydroxide, and hydroxide Strontium, barium hydroxide, europium (II) hydroxide, thallium (I) hydroxide, guanidine, etc.

又，為了提高透明導電層之結晶性，降低電阻率，較佳為設置退火步驟進行特定之退火處理。 In addition, in order to improve the crystallinity of the transparent conductive layer and reduce the resistivity, it is preferable to provide an annealing step to perform a specific annealing process.

亦即，較佳為將所得之透明導電性薄膜於130~180 ℃之溫度條件下曝曬0.5~2小時。 That is, it is preferable to obtain the obtained transparent conductive film at 130~180 Exposure at a temperature of ℃ for 0.5~2 hours.

[實施例] [Example]

以下，參照實施例，進一步詳細說明本發明之透明導電層形成用層合體等。 Hereinafter, the laminate for forming a transparent conductive layer of the present invention will be described in further detail with reference to examples.

[實施例1] [Example 1]

1.硬塗層形成用組成物之調製 1. Preparation of the composition for forming the hard coat layer

於容器內，將作為(A)成分之活性能量線硬化性樹脂、與作為(B)成分之二氧化矽微粒子、與作為(C)成分之均染劑、與作為(D)成分之光聚合起始劑收容在下述組成後，加入溶劑混合均勻，以調製固含量濃度22重量%之硬塗層形成用組成物。 In the container, the active energy ray-curable resin as the component (A), the silica fine particles as the (B) component, the leveling agent as the (C) component, and the photopolymerization as the (D) component After the initiator is contained in the following composition, a solvent is added and mixed uniformly to prepare a composition for forming a hard coat layer having a solid content concentration of 22% by weight.

尚，在下述組成及表1所示之組成之摻合量係表示去除稀釋溶劑之純分。 In addition, the blending amount in the following composition and the composition shown in Table 1 shows the pure content except the dilution solvent.

尚，上述之(B)成分的體積平均粒徑(D50)係在雷射繞 射散射式粒度分布測定裝置測定。 Still, the volume average particle diameter (D50) of the above (B) component is It is measured by a jet scattering particle size distribution measuring device.

又，在以下，有時將上述之作為(D)成分之光起始劑稱為「Irgacure 184」。 In the following, the photoinitiator as the component (D) described above may be referred to as "Irgacure 184".

2.高折射率層形成用組成物之調製 2. Modulation of high refractive index layer forming composition

於容器內，收容紫外線硬化性樹脂(大日精化工業(股)製、Seika Beam EXF-01L(NS))100重量份(表示去除稀釋溶劑之純分，以下相同)、與氧化鋯分散液(CIKNANOTEC(股)製、ZRMIBK15WT%-F85)200重量份、與丙烯酸系均染劑(BYK Japan(股)製、BYK-355)0.05重量份、與光聚合起始劑(BASF日本(股)製、Irgacure 907)3重量份後，加入溶劑混合均勻，以調製固含量濃度1重量%之高折射率層形成用組成物。 In a container, contain 100 parts by weight of ultraviolet curable resin (made by Dairi Seiki Co., Ltd., Seika Beam EXF-01L (NS)) (indicating the removal of the diluted solvent, the same below) and zirconia dispersion liquid ( CIKNANOTEC (product), ZRMIBK15WT%-F85) 200 parts by weight, and acrylic leveling agent (BYK Japan (product), BYK-355) 0.05 parts by weight, and photopolymerization initiator (BASF Japan (product) , Irgacure 907) After 3 parts by weight, add a solvent and mix well to prepare a composition for forming a high refractive index layer with a solid content concentration of 1% by weight.

3.低折射率層形成用組成物之調製 3. Modulation of the composition for forming a low refractive index layer

於容器內，將作為(a)成分之含有撥水性樹脂之活性能量線硬化性樹脂、與作為(b)成分之二氧化矽微粒子、與作為(c)成分之均染劑、與作為(d)成分之光聚合起始劑收容在下述組成後，加入溶劑混合均勻，以調製固含量濃度1重量%之低折射率層形成用組成物。 In the container, the active energy ray-curable resin containing the water-repellent resin as component (a), the silica fine particles as component (b), the leveling agent as component (c), and the component (d ) After the photopolymerization initiator of the component is contained in the following composition, a solvent is added and mixed uniformly to prepare a composition for forming a low refractive index layer with a solid content concentration of 1% by weight.

尚，在下述組成所示之組成之摻合量係表示去除稀釋溶劑之純分。 In addition, the blending amount of the composition shown in the following composition means the pure content from which the dilution solvent is removed.

(a)成分：含有氟樹脂之紫外線硬化性丙烯酸樹脂 100重量份

(a) Ingredient: 100 parts by weight of ultraviolet curable acrylic resin containing fluorine resin

尚，上述之(b)成分的體積平均粒徑(D50)係在雷射繞射散射式粒度分布測定裝置測定。 In addition, the volume average particle diameter (D50) of the component (b) described above is measured by a laser diffraction scattering type particle size distribution measuring device.

4.硬塗層之形成 4. Formation of hard coating

作為基材薄膜，係準備膜厚125μm之附易接著層之聚酯薄膜(帝人杜邦(股)製、PET125KEL86W)。 As a base film, a polyester film with an adhesion layer of 125 μm in thickness (made by Teijin DuPont Co., Ltd., PET125KEL86W) was prepared.

其次，於所準備之基材薄膜的表面，將硬塗層形成用組成物塗佈在Wire bar#8。 Next, on the surface of the prepared base film, a composition for forming a hard coat layer is applied to Wire bar#8.

其次，於70℃ 1分鐘使其乾燥後，在氮環境下使用紫外線照射裝置(GS Yuasa Corporation(股)製)，在下述條件照射紫外線，於基材薄膜的表面形成膜厚2μm之硬塗層。 Next, after drying at 70°C for 1 minute, an ultraviolet irradiation device (manufactured by GS Yuasa Corporation) was used under a nitrogen atmosphere, and ultraviolet rays were irradiated under the following conditions to form a hard coating layer with a thickness of 2 μm on the surface of the base film .

又，即使在基材薄膜之相反側的面，亦同樣進行以形成硬塗層。 In addition, even on the surface on the opposite side of the base film, the same process is performed to form a hard coat layer.

光源：高壓水銀燈 Light source: high pressure mercury lamp

照度：150mW/cm² Illumination: 150mW/cm ²

光量：150mJ/cm² Light quantity: 150mJ/cm ²

5.高折射率層之形成 5. Formation of high refractive index layer

其次，於形成一側的硬塗層上，將高折射率形成用組成物塗佈在Wire bar#4。 Next, on the hard coating layer on one side, a composition for forming a high refractive index is applied to Wire bar #4.

其次，於50℃ 1分鐘使其乾燥後，在氮環境下使用紫外線照射裝置(GS Yuasa Corporation(股)製)，在與硬塗層相同條件照射紫外線，於硬塗層上形成膜厚35nm、折射率n_D=1.65之高折射率層。 Next, after drying at 50°C for 1 minute, an ultraviolet irradiation device (manufactured by GS Yuasa Corporation) was used under a nitrogen atmosphere, and ultraviolet rays were irradiated under the same conditions as the hard coating to form a film thickness of 35 nm on the hard coating. High refractive index layer with refractive index n _D = 1.65.

6.低折射率層之形成 6. Formation of low refractive index layer

其次，於形成的高折射率層上，將低折射率形成用之組成物塗佈在Wire bar#4。 Next, on the formed high-refractive index layer, a composition for forming a low-refractive index is coated on Wire bar#4.

其次，於50℃ 1分鐘使其乾燥後，在氮環境下使用紫外線照射裝置(GS Yuasa Corporation(股)製)，在與硬塗層相同條件照射紫外線，於高折射率層上形成膜厚50nm、折射率n_D=1.37之低折射率層，而得到如圖1(a)所示之透明導電層形成用層合體。 Next, after drying at 50°C for 1 minute, an ultraviolet irradiation device (manufactured by GS Yuasa Corporation) was used under a nitrogen atmosphere, and ultraviolet rays were irradiated under the same conditions as the hard coat layer to form a film thickness of 50 nm on the high refractive index layer 1. A low-refractive-index layer with a refractive index n _D =1.37 to obtain a laminate for forming a transparent conductive layer as shown in FIG. 1(a).

7.評估 7. Evaluation

(1)耐蝕刻性的評估 (1) Evaluation of etching resistance

評估在所得之透明導電層形成用層合體之耐蝕刻性。 The etching resistance of the obtained laminate for forming a transparent conductive layer was evaluated.

亦即，將所得之透明導電層形成用層合體之反射率(%)(低折射率層側)使用紫外可見近紅外(UV-vis-NIR)分光光度計(島津製作所(股)製、UV-3600)，反射角度：8°、採樣間隔：1nm、測定模式：在單一條件測定。 That is, the reflectance (%) of the resulting laminate for forming a transparent conductive layer (on the side of the low refractive index layer) uses an ultraviolet-visible-near infrared (UV-vis-NIR) spectrophotometer (manufactured by Shimadzu Corporation, UV -3600), reflection angle: 8°, sampling interval: 1 nm, measurement mode: measurement under a single condition.

其次，使透明導電層形成用層合體浸漬5分鐘在加溫至40℃之5重量%之氫氧化鈉水溶液進行鹼處理後，在與上述之條件相同條件測定反射率(%)。 Next, after immersing the laminate for forming a transparent conductive layer for 5 minutes and performing alkali treatment with a 5 wt% sodium hydroxide aqueous solution heated to 40°C, the reflectance (%) was measured under the same conditions as above.

其次，從鹼處理前之反射率(%)減去鹼處理後之反射率(%)，算出反射率變化量(%)。將所得之結果示於表1。 Next, the amount of reflectance change (%) is calculated by subtracting the reflectance (%) after alkali treatment from the reflectance (%) before alkali treatment. Table 1 shows the obtained results.

尚，反射率變化量若為0.5%以下之值，可判斷實用上具有優異之耐蝕刻性。 Still, if the amount of change in reflectance is 0.5% or less, it can be judged to have excellent etching resistance in practical use.

又，藉由反射率變化量(%)可評估耐蝕刻性的理由，係因為藉由蝕刻處理，使硬塗層的膜厚或折射率或者兩方變化時，亦改變硬塗層的反射率。 In addition, the reason why the etching resistance can be evaluated by the amount of change in reflectance (%) is that the reflectance of the hard coat layer is also changed when the film thickness or refractive index of the hard coat layer or both are changed by the etching process .

(2)圖型可視性的評估 (2) Evaluation of graphic visibility

相對於所得之透明導電層形成用層合體之低折射率層的表面，形成經圖型化之透明導電層，評估其可視性。 A patterned transparent conductive layer was formed on the surface of the low refractive index layer of the obtained transparent conductive layer forming laminate, and its visibility was evaluated.

亦即，將所得之透明導電層形成用層合體切成縱90mm×橫90mm之後，使用ITO靶(氧化錫10重量%、氧化銦90重量%)進行濺鍍，於低折射率層上之中央部形成縱60mm×橫60mm之正方形狀、膜厚30nm之透明導電層。 That is, after cutting the obtained laminate for forming a transparent conductive layer to 90 mm in length×90 mm in width, sputtering was performed using an ITO target (10% by weight of tin oxide and 90% by weight of indium oxide) on the center of the low refractive index layer A transparent conductive layer with a square shape of 60 mm in length and 60 mm in width and a thickness of 30 nm is formed in the portion.

其次，於所得之透明導電層的表面上形成圖型化成格 子狀之光阻膜。 Secondly, a pattern is formed on the surface of the obtained transparent conductive layer Sub-shaped photoresist film.

其次，在室溫下，藉由於10重量%之鹽酸浸漬1分鐘，進行蝕刻處理，而將透明導電層圖型化成格子狀。 Next, at room temperature, the transparent conductive layer was patterned into a lattice by immersing in 10% by weight hydrochloric acid for 1 minute and performing an etching process.

其次，浸漬5分鐘於加溫至40℃之5重量%之氫氧化鈉水溶液，來進行鹼處理，去除透明導電層上之光阻膜，而得到具有經圖型化之透明導電層之透明導電性薄膜。 Next, immerse it for 5 minutes in a 5 wt% aqueous sodium hydroxide solution heated to 40°C to perform alkali treatment to remove the photoresist film on the transparent conductive layer to obtain a transparent conductive layer with a patterned transparent conductive layer Sexual film.

該透明導電性薄膜係具有藉由由線寬2mm之ITO所構成之線部，1邊為2mm之正方形的空隙具有區隔化成格子狀之圖型形狀之30nm透明導電層者。 The transparent conductive film has a line portion made of ITO with a line width of 2 mm, and a square gap of 2 mm on one side has a 30 nm transparent conductive layer partitioned into a lattice pattern.

其次，將所得之透明導電性薄膜設置在從白色螢光燈1m的位置，以映入白色螢光燈在透明導電性薄膜的狀態，藉由從在與設置白色螢光燈相同側之透明導電性薄膜之30cm位置，以目視觀察透明導電層之圖型形狀，依下述基準進行評估。將所得之結果示於表1。 Next, the obtained transparent conductive film is placed at a position 1m from the white fluorescent lamp to reflect the state of the white fluorescent lamp on the transparent conductive film, by the transparent conductive on the same side as the white fluorescent lamp The pattern of the transparent film was visually observed at the 30 cm position of the thin film, and evaluated according to the following criteria. Table 1 shows the obtained results.

○：無法視別透明導電層之圖型形狀 ○: The pattern shape of the transparent conductive layer cannot be distinguished

×：視別透明導電層之圖型形狀 ×: Depending on the shape of the transparent conductive layer

(3)抗黏著性的評估 (3) Evaluation of anti-adhesion

評估在所得之透明導電層形成用層合體之抗黏著性。 The adhesion resistance of the obtained laminate for forming a transparent conductive layer was evaluated.

亦即，於平坦之玻璃板上，不透過黏著劑等，以硬塗層面朝上的方式載置透明導電層形成用層合體。 That is, on a flat glass plate, the transparent conductive layer forming laminate is placed with the hard coat layer facing upward without passing through an adhesive or the like.

其次，於載置之透明導電層形成用層合體之上，重疊放置另一透明導電層形成用層合體後，以手押住，藉由磨擦此等2片透明導電層形成用層合體，進行硬塗層彼此、 及硬塗層與低折射率層的磨擦，依下述基準評估抗黏著性。將所得之結果示於表1。 Next, after placing another laminate for forming a transparent conductive layer on top of the placed laminate for transparent conductive layer formation, hold it by hand, and rub these two laminates for forming a transparent conductive layer, by Hard coat each other, And the friction between the hard coat layer and the low refractive index layer, the blocking resistance was evaluated according to the following criteria. Table 1 shows the obtained results.

○：層表面彼此未密著 ○: The surfaces of the layers are not adhered to each other

×：層表面彼此密著不動搖 ×: The surface of the layer is close to each other without shaking

[實施例2] [Example 2]

於實施例2，調製硬塗層形成用組成物時，除了作為下述組成之外，其他與實施例1同樣進行以製造透明導電層形成用層合體並評估。將所得之結果示於表1。 In Example 2, when preparing the composition for hard-coat layer formation, it carried out similarly to Example 1, except the following composition, and produced and evaluated the laminated body for transparent conductive layer formation. Table 1 shows the obtained results.

尚，在下述組成及表1所示之組成之摻合量係表示去除稀釋溶劑之純分。 In addition, the blending amount in the following composition and the composition shown in Table 1 shows the pure content except the dilution solvent.

尚，上述之(B)成分的體積平均粒徑(D50)係在雷射繞射散射式粒度分布測定裝置測定。 In addition, the volume average particle diameter (D50) of the component (B) described above is measured by a laser diffraction scattering type particle size distribution measuring device.

又，在以下，有時將作為(A2)成分之交聯丙烯酸系共聚物樹脂稱為「Techpolymer XX-27LA」。 In addition, in the following, the crosslinked acrylic copolymer resin as the component (A2) may be referred to as "Techpolymer XX-27LA".

[比較例1] [Comparative Example 1]

於比較例1，調製硬塗層形成用組成物時，除了作為下述組成之外，其他與實施例1同樣進行以製造透明導電層形成用層合體並評估。將所得之結果示於表1。 In Comparative Example 1, when preparing the composition for forming a hard coat layer, the same procedure as in Example 1 was carried out to prepare a laminate for forming a transparent conductive layer and evaluate it except for the following composition. Table 1 shows the obtained results.

尚，在下述組成及表1所示之組成之摻合量係表示去除稀釋溶劑之純分。 In addition, the blending amount in the following composition and the composition shown in Table 1 shows the pure content except the dilution solvent.

尚，上述之(B)成分的體積平均粒徑(D50)係在雷射繞射散射式粒度分布測定裝置測定。 In addition, the volume average particle diameter (D50) of the component (B) described above is measured by a laser diffraction scattering type particle size distribution measuring device.

[比較例2] [Comparative Example 2]

於比較例2，調製硬塗層形成用組成物時，除了作為下述組成之外，其他與實施例1同樣進行以製造透明導電層形成用層合體並評估。將所得之結果示於表1。 In Comparative Example 2, when preparing the composition for forming a hard coat layer, the same procedure as in Example 1 was carried out to produce a laminate for forming a transparent conductive layer and to evaluate it except for the following composition. Table 1 shows the obtained results.

尚，在下述組成及表1所示之組成之摻合量係表示去除稀釋溶劑之純分。 In addition, the blending amount in the following composition and the composition shown in Table 1 shows the pure content except the dilution solvent.

[產業上之可利用性] [Industry availability]

以上，如詳述，根據本發明，變成形成透明導電層形成用層合體之最內面之硬塗層時，相對於活性能量線硬化性樹脂，藉由使用將二氧化矽微粒子以特定範圍摻合而成之硬塗層形成用組成物，可得到在硬塗層之耐蝕刻性優異之透明導電層形成用層合體。 As described above, according to the present invention, according to the present invention, when forming the hard coat layer on the innermost surface of the laminate for forming a transparent conductive layer, the silica particles are mixed in a specific range with respect to the active energy ray-curable resin by using The combined composition for forming a hard coat layer can obtain a laminate for forming a transparent conductive layer having excellent etching resistance in the hard coat layer.

其結果，變成可穩定地不可見化透明導電層之圖型形狀，且可得到在所得之透明導電性薄膜之抗黏著性優異之透明導電層形成用層合體。 As a result, it becomes a pattern shape in which the transparent conductive layer can be stably invisible, and a laminate for forming a transparent conductive layer excellent in the anti-adhesion property of the obtained transparent conductive film can be obtained.

據此，本發明之透明導電層形成用層合體及使用其之透明導電性薄膜，被期待顯著貢獻在觸控面板之高品質化。 Accordingly, the laminate for forming a transparent conductive layer of the present invention and the transparent conductive film using the same are expected to contribute significantly to the improvement of the quality of the touch panel.

2‧‧‧光學調整層 2‧‧‧Optical adjustment layer

2a‧‧‧低折射率層 2a‧‧‧Low refractive index layer

2b‧‧‧高折射率層 2b‧‧‧High refractive index layer

3a‧‧‧第1硬塗層 3a‧‧‧The first hard coating

3a’‧‧‧硬塗層 3a’‧‧‧hard coating

3b‧‧‧第2硬塗層 3b‧‧‧The second hard coating

4‧‧‧基材薄膜 4‧‧‧ Base film

10‧‧‧透明導電層形成用層合體 10‧‧‧Laminate for transparent conductive layer formation

Claims (8)

一種靜電容量式觸控面板用透明導電性薄膜，其係依硬塗層、基材薄膜、光學調整層、透明導電層順序層合而成之靜電容量式觸控面板用透明導電性薄，其特徵為前述硬塗層係光硬化包含下述(A)~(B)成分之硬塗層形成用組成物而成，前述透明導電層係藉由蝕刻而圖型化，(A)活性能量線硬化性樹脂 100重量份(B)二氧化矽微粒子 15~100重量份。 A transparent conductive film for an electrostatic capacitive touch panel, which is a transparent conductive thin film for an electrostatic capacitive touch panel formed by sequentially laminating a hard coat layer, a substrate film, an optical adjustment layer, and a transparent conductive layer, which It is characterized in that the hard coat layer is photo-hardened by a composition for forming a hard coat layer containing the following components (A) to (B), the transparent conductive layer is patterned by etching, (A) active energy line 100 parts by weight of curable resin (B) 15 to 100 parts by weight of silica fine particles. 如請求項1之靜電容量式觸控面板用透明導電性薄膜，其係將前述作為(B)成分之二氧化矽微粒子的體積平均粒徑(D50)定為10~100nm的範圍內之值。 The transparent conductive film for an electrostatic capacitance type touch panel according to claim 1, the volume average particle diameter (D50) of the silicon dioxide fine particles as the component (B) is set to a value in the range of 10 to 100 nm. 如請求項1之靜電容量式觸控面板用透明導電性薄膜，其中，前述作為(B)成分之二氧化矽微粒子為堅實二氧化矽微粒子。 The transparent conductive film for an electrostatic capacitive touch panel according to claim 1, wherein the silicon dioxide fine particles as the component (B) are solid silicon dioxide fine particles. 如請求項1之靜電容量式觸控面板用透明導電性薄膜，其中，前述作為(B)成分之二氧化矽微粒子為反應性二氧化矽微粒子。 The transparent conductive film for a capacitive touch panel according to claim 1, wherein the silicon dioxide fine particles as the component (B) are reactive silicon dioxide fine particles. 如請求項1之靜電容量式觸控面板用透明導電性薄膜，其中，前述硬塗層形成用組成物作為(C)成分包含氟系均染劑的同時，相對於前述作為(A)之活性能量線硬化性樹脂100重量份，將該氟系均染劑之摻合量定為0.01~0.2重量份的範圍內之值。 The transparent conductive film for an electrostatic capacitance type touch panel according to claim 1, wherein the composition for forming a hard coat layer contains the fluorine-based leveling agent as the component (C), and the activity relative to the activity as (A) 100 parts by weight of the energy ray-curable resin, the blending amount of the fluorine-based leveling agent is set to a value in the range of 0.01 to 0.2 parts by weight. 如請求項1之靜電容量式觸控面板用透明導電性薄膜，其係將前述硬塗層的膜厚定為0.5~5μm的範圍內 之值。 The transparent conductive film for an electrostatic capacitance type touch panel according to claim 1, which sets the film thickness of the hard coat layer in the range of 0.5 to 5 μm Value. 如請求項1之靜電容量式觸控面板用透明導電性薄膜，其中，將前述硬塗層作為第1硬塗層的情況下，於前述基材薄膜、與前述光學調整層之間具有第2硬塗層。 The transparent conductive film for an electrostatic capacitance type touch panel according to claim 1, wherein when the hard coat layer is used as the first hard coat layer, there is a second layer between the base film and the optical adjustment layer Hard coating. 如請求項7之靜電容量式觸控面板用透明導電性薄膜，其中，前述第2硬塗層係與前述第1硬塗層相同，光硬化硬塗層形成用組成物而成的同時，亦具有與前述第1硬塗層相同之膜厚。 The transparent conductive film for an electrostatic capacitance type touch panel according to claim 7, wherein the second hard coat layer is the same as the first hard coat layer, and the composition for forming a photohardenable hard coat layer is also It has the same film thickness as the first hard coat layer.

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