TW201819956A - Antiglare hard coating film - Google Patents
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- G02F1/133502—Antiglare, refractive index matching layers
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Abstract
Description
本發明是關於一種使用觸控筆的觸控面板用防眩性硬塗薄膜。 The present invention relates to an anti-glare hard-coated film for a touch panel using a stylus.
近年在各種電子設備中,多使用兼具顯示裝置與輸入手段的觸控面板。該觸控面板的表面,通常為了防止損壞而設置具有硬塗層的硬塗薄膜。另外,包括觸控面板在內的各種顯示器,會反射從外部入射的光線,有難以看清顯示圖像的情況,因此有通過將硬塗薄膜的表面粗化,而使用賦予了防眩功能的防眩性硬塗薄膜的情況。 In recent years, in various electronic devices, a touch panel having both a display device and an input means has been used. The surface of the touch panel is usually provided with a hard-coated film having a hard coating layer in order to prevent damage. In addition, various displays, including touch panels, reflect the light incident from the outside, making it difficult to see the displayed image. Therefore, the surface of the hard-coated film is roughened to use anti-glare functions. In the case of anti-glare hard-coated films.
如上所述的觸控面板中,除了用手指輸入以外,還有用觸控筆輸入的觸控面板,由於觸控筆比手指更小,因此可以准確輸入。但是,通常觸控面板的顯示模塊為硬質,附著有上述防眩性硬塗薄膜的觸控面板表面也同樣是硬質。因此,觸控筆的書寫感與用鉛筆或圓珠筆等在紙上書寫時的書寫感不同,難以說是良好。 Among the touch panels described above, in addition to input with a finger, there is also a touch panel with a stylus. Since the stylus is smaller than a finger, it can be accurately input. However, generally, the display module of a touch panel is hard, and the surface of the touch panel to which the anti-glare hard-coated film is attached is also hard. Therefore, the writing feeling of the stylus pen is different from that when writing on paper with a pencil, a ballpoint pen, or the like, and it is difficult to say that it is good.
為瞭解決上述書寫感問題,專利文獻1中,通過在2個基材之間放置具有緩沖性的粘接劑層,使觸控面板具有所定的彈性變形性,來提高觸控筆的書寫感。 In order to solve the above-mentioned problem of writing feeling, in Patent Document 1, a cushioning adhesive layer is placed between two substrates so that the touch panel has a predetermined elastic deformability, thereby improving the writing feeling of the stylus. .
【先前技術文獻】 [Previous Technical Literature]
【專利文獻】 [Patent Literature]
【專利文獻1】專利第2868686號公報 [Patent Document 1] Patent No. 2868686
但是,專利文獻1中有使粘接劑層具有緩沖性的必要。因此,會受到用於該粘接劑層的材料的制約,或需要使該粘接劑層相對較厚。因此,製造過程變得複雜,同時,製造成本增加。 However, in Patent Document 1, it is necessary to make the adhesive layer cushioning. Therefore, it is restricted by the material used for the adhesive layer, or the adhesive layer needs to be relatively thick. Therefore, the manufacturing process becomes complicated, and at the same time, the manufacturing cost increases.
另外,在觸控面板中,即使使用觸控筆輸入方式,也常有手碰到觸控面板的情況,因此在觸控面板的表面,一般會由於手指上的油脂而附有指紋。現有防眩性硬塗薄膜上如果附有指紋,則由於指紋過於明顯而有損外觀,同時,顯示圖像變得難以看清。 In addition, in a touch panel, even if a stylus input method is used, a hand often touches the touch panel. Therefore, fingerprints are generally attached to the surface of the touch panel due to grease on the fingers. If a fingerprint is attached to a conventional anti-glare hard-coated film, the appearance is impaired because the fingerprint is too obvious, and the display image becomes difficult to see.
本發明是鑒於這樣的現狀而進行的,目的在於提供一種用防眩性硬塗薄膜本身即可使觸控筆的書寫感良好,同時不易看出附著的指紋的防眩性硬塗薄膜。 The present invention has been made in view of such a situation, and an object of the present invention is to provide an anti-glare hard-coated film which can improve the writing feel of a stylus pen with an anti-glare hard-coated film itself, and also makes it difficult to see the attached fingerprint.
為了達成上述目的,第一,本發明提供一種防眩性硬塗薄膜,其特徵在於:作為具備基材膜和設置在上述基材膜一側面上的防眩性硬塗層的觸控面板用防眩性硬塗薄膜,對上述防眩性硬塗層表面,將筆尖直徑為0.5mm的硬氈芯觸控筆,在負重150g重量的加壓下,以100mm/分的速度掃描時,筆尖阻力(mN)的初始值(A)以及滑動值(B)滿足以下算式(a)的關係:0≦初始值(A)-滑動值(B)...(a) In order to achieve the above object, first, the present invention provides an anti-glare hard-coated film for use in a touch panel including a base film and an anti-glare hard coating layer provided on one side of the base film. Anti-glare hard coating film. On the surface of the anti-glare hard coating, a stylus with a pen tip diameter of 0.5 mm and a stylus pen with a pen tip diameter of 0.5 mm is scanned at a speed of 100 mm / minute under a pressure of 150 g. The initial value (A) and sliding value (B) of the resistance (mN) satisfy the relationship of the following formula (a): 0 ≦ initial value (A) -sliding value (B) ... (a)
同時,上述防眩性硬塗層表面的油酸接觸角為45°以下(發明1)。 At the same time, the oleic acid contact angle on the surface of the anti-glare hard coat layer is 45 ° or less (Invention 1).
上述發明(發明1)所述防眩性硬塗薄膜,筆尖阻力(mN)的初始值(A)以及滑動值(B)通過滿足上述關係,用防眩性硬塗薄膜本身即可使觸控筆的書寫感變得良好,另外油酸接觸角在45°以下,使附著的指紋不易被看到。 The anti-glare hard-coated film according to the above invention (Invention 1), the initial value (A) and the sliding value (B) of the pen tip resistance (mN) satisfy the above-mentioned relationship, and the touch can be made by the anti-glare hard-coated film itself. The writing feeling of the pen becomes good, and the contact angle of oleic acid is below 45 °, making the attached fingerprints difficult to see.
在上述發明(發明1)中,上述筆尖阻力(mN)的初始值(A)以及滑動值(B),優選為滿足以下算式(b)的關係(發明2)。 In the above invention (Invention 1), the initial value (A) and the slip value (B) of the pen tip resistance (mN) preferably satisfy the relationship of the following formula (b) (Invention 2).
5≦初始值(A)-滑動值(B)≦200...(b) 5 ≦ initial value (A) -sliding value (B) ≦ 200 ... (b)
在上述發明(發明1,發明2)中,上述油酸接觸角優選為25°~45°(發明3)。 In the above invention (Invention 1, Invention 2), the oleic acid contact angle is preferably 25 ° to 45 ° (Invention 3).
在上述發明(發明1~發明3)中,上述防眩性硬塗層,優選為將含有多官能(甲基)丙烯酸酯、平均粒徑為1μm~10μm的微粒子和勻染劑的塗料組合物固化而構成(發明4)。 In the above invention (Invention 1 to Invention 3), the antiglare hard coat layer is preferably a coating composition containing a polyfunctional (meth) acrylate, fine particles having an average particle diameter of 1 to 10 μm, and a leveling agent. It is solidified and comprised (invention 4).
在上述發明(發明1~發明4)中,上述微粒子優選為無定形二氧化矽微粒子(發明5)。 In the above invention (Invention 1 to Invention 4), the fine particles are preferably amorphous silica particles (Invention 5).
本發明所述防眩性硬塗薄膜書寫感良好,同時不易看到附著的指紋。 The anti-glare hard coating film of the present invention has a good writing feeling, and at the same time, it is difficult to see the attached fingerprints.
1‧‧‧防眩性硬塗薄膜 1‧‧‧Anti-glare hard coating film
11‧‧‧基材膜 11‧‧‧ substrate film
12‧‧‧防眩性硬塗層 12‧‧‧Anti-glare hard coating
圖1為本發明一實施形態所有關的防眩性硬塗薄膜的剖面圖。 FIG. 1 is a cross-sectional view of an anti-glare hard coat film according to an embodiment of the present invention.
圖2為顯示筆尖阻力測定結果一例(本實施形態所有關的關於防眩性硬塗薄膜的例)的圖。 FIG. 2 is a diagram showing an example of a measurement result of a pen tip resistance (an example of an anti-glare hard coat film according to the present embodiment).
圖3為顯示筆尖阻力測定結果另一例(關於一般防眩性硬塗薄膜的例)的圖。 FIG. 3 is a diagram showing another example of the measurement result of the pen tip resistance (an example of a general anti-glare hard coat film).
以下,關於本發明的實施形態進行說明。 Hereinafter, embodiments of the present invention will be described.
如圖1所示,本實施形態所述防眩性硬塗薄膜1,由基材膜11和在基材膜11一側面上形成的防眩性硬塗層12所構成。該防眩性硬塗薄膜1,設置於使用觸控筆的觸控面板的表面。 As shown in FIG. 1, the anti-glare hard coat film 1 according to the present embodiment includes a base film 11 and an anti-glare hard coat layer 12 formed on one side of the base film 11. This anti-glare hard-coated film 1 is provided on the surface of a touch panel using a stylus.
1.物性 Physical property
本實施形態所述防眩性硬塗薄膜1,對防眩性硬塗層12表面(與基材膜11不接觸的一側面),將筆尖直徑為0.5mm的硬氈芯觸控筆,在負重150g重量的加壓下,以100mm/分的速度掃描時筆尖阻力(mN)的初始值(A)以及滑動值(B),滿足以下算式(a)的關係。 In the anti-glare hard coating film 1 according to this embodiment, a hard felt-core stylus with a pen tip diameter of 0.5 mm is placed on the surface of the anti-glare hard coating layer 12 (the side not in contact with the base film 11). The initial value (A) and the sliding value (B) of the pen tip resistance (mN) when scanning at a speed of 100 mm / min under a pressure of 150 g of a load satisfy the relationship of the following formula (a).
0≦初始值(A)-滑動值(B)...(a) 0 ≦ initial value (A) -sliding value (B) ... (a)
這裏的筆尖阻力初始值(A)是指,觸控筆在開始掃描的階段中顯示的筆尖阻力的值,如圖2以及圖3所示,通常檢測為峰值。另一方面,筆尖阻力滑動值(B)是指,初始時的影響消失後在穩定掃描狀態下的筆尖阻力平均值。例如,圖2中掃描長度為10mm~40mm的筆尖阻力的平均值為滑動值(B)。另外,圖3中掃描長度為15mm~40mm的筆尖阻力的平均值為滑動值(B)。 Here, the initial value of the pen tip resistance (A) refers to the value of the pen tip resistance displayed by the stylus at the start of scanning. As shown in FIG. 2 and FIG. 3, it is usually detected as a peak value. On the other hand, the pen tip resistance sliding value (B) refers to the pen tip resistance average value in a stable scanning state after the initial influence disappears. For example, the average value of the pen tip resistance with a scanning length of 10 mm to 40 mm in FIG. 2 is the sliding value (B). In addition, the average value of the pen tip resistance with a scanning length of 15 mm to 40 mm in FIG. 3 is a slip value (B).
如上述算式(a)所示,從初始值(A)中減去滑動值(B)的值(筆尖阻力的差(A-B))為0mN以上,防眩性硬塗薄膜1,特別是無需設置具有緩沖性的粘接劑層等,用防眩性硬塗薄膜本身即可使觸控筆的書寫感變得良好。可以認為這是初始值(A)和滑動值(B)的關係,與用鉛筆在紙上書寫時的關係相近的緣故。從這樣的觀點考慮,從初始值(A)中減去滑動值(B)的值的下限值優選為5mN以上,特別優選為在10mN以上。另外,在表面不具有凹凸的一般硬塗薄膜上,觀察不到表示最高峰值的初始值(A)。另外,在一般防眩性硬塗薄膜中,如圖3所示,雖然可觀察到初始值(A),但其後筆尖阻力增加,滑動值(B)變大,因此上述筆尖阻力的差(A-B),通常顯示為負值。 As shown in the above formula (a), the value of subtracting the sliding value (B) from the initial value (A) (the difference in pen tip resistance (AB)) is 0 mN or more, and the anti-glare hard-coated film 1 does not particularly need to be provided The cushioning adhesive layer and the like can improve the writing feel of the stylus with the anti-glare hard coating film itself. This is considered to be because the relationship between the initial value (A) and the sliding value (B) is similar to the relationship when writing on paper with a pencil. From such a viewpoint, the lower limit value of the value obtained by subtracting the sliding value (B) from the initial value (A) is preferably 5 mN or more, and particularly preferably 10 mN or more. In addition, on a general hard-coated film having no unevenness on the surface, an initial value (A) indicating the highest peak was not observed. In addition, in a general anti-glare hard coating film, although the initial value (A) is observed as shown in FIG. 3, the nib resistance increases and the sliding value (B) increases thereafter, so the difference in the nib resistance ( AB), usually displayed as a negative value.
另外,初始值(A)以及滑動值(B)如果滿足上述關係,則上述硬氈芯的觸控筆,即使在使用材料或筆尖直徑不同的觸控筆(例如,聚縮醛芯觸控筆)的情況時,也可確認到防眩性硬塗薄膜的書寫感提高的效果。 In addition, if the initial value (A) and the sliding value (B) satisfy the above relationship, the stylus with a hard felt core, even when using a stylus with a different material or a different tip diameter (for example, a polyacetal core stylus) In the case of), the effect of improving the writing feeling of the anti-glare hard coating film was also confirmed.
另一方面,從初始值(A)中減去滑動值(B)的值如果過大,則有筆尖容易磨損的問題,可能會有開始部分被卡住的感覺或發出聲音。從這樣的觀點考慮,從初始值(A)中減去滑動值(B)的值的上限值,優選為200mN以下,特別優選為150mN以下,進一步優選為100mN以下。 On the other hand, if the value of subtracting the sliding value (B) from the initial value (A) is too large, there is a problem that the pen tip is prone to wear, and there may be a feeling of getting stuck at the beginning or a sound. From such a viewpoint, the upper limit of the value obtained by subtracting the sliding value (B) from the initial value (A) is preferably 200 mN or less, particularly preferably 150 mN or less, and still more preferably 100 mN or less.
另外,上述初始值(A)優選為200mN~600mN,特別優選為240mN~500mN,進一步優選為280mN~450mN。另一方面,上述滑動值(B)優選為100mN~550mN,特別優選為150mN~490mN,進一步優選為200mN~440mN。 The initial value (A) is preferably 200 mN to 600 mN, particularly preferably 240 mN to 500 mN, and even more preferably 280 mN to 450 mN. On the other hand, the slip value (B) is preferably 100 mN to 550 mN, particularly preferably 150 mN to 490 mN, and still more preferably 200 mN to 440 mN.
另外,本實施形態所述防眩性硬塗薄膜1,其防眩性硬塗層12表面的油酸接觸角為45°以下,優選為25°~45°,特別優選為30°~40°。另外,油酸接觸角是指,在防眩性硬塗層表面,將油酸的液滴在靜置狀態下,在液滴的上述硬塗層表面的接地部分的液滴接線與上述硬塗層表面構成的角度中,包含液滴的一側的角度。 In addition, in the anti-glare hard coat film 1 according to this embodiment, the oleic acid contact angle on the surface of the anti-glare hard coat layer 12 is 45 ° or less, preferably 25 ° to 45 °, and particularly preferably 30 ° to 40 °. . In addition, the contact angle of oleic acid means that the droplets of oleic acid are placed on the surface of the anti-glare hard coating layer in a static state, and the droplets are connected to the ground of the hard coating surface of the droplets and the hard coating. The angle formed by the layer surface includes the angle of one side of the droplet.
防眩性硬塗薄膜1,通過油酸接觸角在45°以下,使附著的指紋不易被看到(指紋非視認性優異)。該油酸接觸角如果超過45°,則附著的指紋容易被看到,觸控面板的外觀變差,同時,顯示圖像變得不易看清。另一方面,油酸接觸角如果未滿25°,有觸控筆的筆尖容易磨損,或防眩性硬塗層12表面的抗劃傷性(鋼絲絨硬度)變差的可能。 The anti-glare hard-coated film 1 has an oleic acid contact angle of 45 ° or less, so that the attached fingerprints are not easily seen (the fingerprints have no visibility). If the oleic acid contact angle exceeds 45 °, the attached fingerprints can be easily seen, the appearance of the touch panel is deteriorated, and at the same time, the display image becomes difficult to see. On the other hand, if the contact angle of oleic acid is less than 25 °, there is a possibility that the pen tip of the stylus is easily worn or the scratch resistance (steel wool hardness) of the surface of the anti-glare hard coat layer 12 is deteriorated.
2.防眩性硬塗層 2. Anti-glare hard coating
本實施形態中防眩性硬塗薄膜1的防眩性硬塗層12,只要對筆尖阻力初始值(A)、滑動值(B)以及油酸接觸角能發揮上述物性,則在任何材料形成均可,但優選為將以下說明的塗料組合物C固化而形成。通過塗料組合物C,容易形成滿足上述物性的防眩性硬塗層12。 The anti-glare hard coat layer 12 of the anti-glare hard coat film 1 in this embodiment is formed on any material as long as the initial physical resistance value (A), sliding value (B), and oleic acid contact angle exhibit the physical properties described above. Any of them may be formed by curing the coating composition C described below. With the coating composition C, the anti-glare hard coat layer 12 satisfying the above-mentioned physical properties is easily formed.
本實施形態中的塗料組合物C,含有多官能(甲基)丙烯酸酯和平均粒徑為1μm~10μm的微粒子及勻染劑,優選為進一步含有平均粒徑為1nm~300nm的二氧化矽納米粒子。另外,本說明書中,所說的(甲基)丙烯酸酯,指丙烯酸酯以及甲基丙烯酸酯的兩方。其他的類似用語也同樣。 The coating composition C in this embodiment contains a polyfunctional (meth) acrylate, fine particles having an average particle diameter of 1 to 10 μm, and a leveling agent, and preferably further contains silicon dioxide nanometers having an average particle diameter of 1 to 300 nm. particle. In addition, in this specification, a (meth) acrylate means both an acrylate and a methacrylate. The same applies to other similar terms.
(1)多官能(甲基)丙烯酸酯 (1) Multifunctional (meth) acrylate
塗料組合物C含有多官能(甲基)丙烯酸酯作為固化性主成分。多官能(甲基)丙烯酸酯通過活性能量線的照射而架橋固化。由於將多官能(甲基)丙烯酸酯架橋,架橋密度高,因此通過使用該多官能(甲基)丙烯酸酯,所形成的防眩性硬塗層12,可得到所希望的硬度和抗劃傷性。 The coating composition C contains a polyfunctional (meth) acrylate as a curable main component. The polyfunctional (meth) acrylate is bridge-cured by irradiation with active energy rays. Since the polyfunctional (meth) acrylate is bridged and the bridging density is high, by using the polyfunctional (meth) acrylate, the anti-glare hard coat layer 12 can be formed to obtain the desired hardness and scratch resistance. Sex.
作為多官能(甲基)丙烯酸酯,例如可以舉出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、羥基新戊酸新戊二醇二(甲基)丙烯酸酯、二環戊基二(甲基)丙烯酸酯、己內酯改性二環戊烯基二(甲基)丙烯酸酯、環氧乙烷改性磷酸二(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、三羥甲基丙烷三(甲基)丙烯酸酯、二季戊四醇三(甲基)丙烯酸酯、丙酸改性二季戊四醇三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、環氧丙烷改性三羥甲基丙烷三(甲基)丙烯酸酯、三(丙烯醯氧乙基)異氰脲酸酯、丙酸改性二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、己內酯改性二季戊四醇六(甲基)丙烯酸酯等。這些可以單獨使用一種,也可以組合兩種以上使用。 Examples of the polyfunctional (meth) acrylate include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate. (Meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentyl di (meth) acrylate, caprolactone Dicyclopentenyl di (meth) acrylate, ethylene oxide modified phosphate di (meth) acrylate, allyl cyclohexyl di (meth) acrylate, isocyanurate di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylic acid Ester, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acrylic acid ethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, etc. These may be used alone or in combination of two or more.
從防眩性硬塗層12的抗劃傷性,以及源於與勻染劑親和性的透明性觀點考慮,多官能(甲基)丙烯酸酯的反應官能基數優選為2~10,特別優選為3~8。 From the viewpoint of the scratch resistance of the anti-glare hard coat layer 12 and the transparency derived from the affinity with the leveling agent, the number of reactive functional groups of the polyfunctional (meth) acrylate is preferably 2 to 10, and particularly preferably 3 ~ 8.
(2)微粒子 (2) fine particles
塗料組合物C含有平均粒徑為1μm~10μm的微粒子。通過含有這樣的微粒子,所形成的防眩性硬塗層12,其表面粗 糙,發揮防眩功能。上述微粒子的平均粒徑優選為2μm~8μm,特別優選為3μm~5μm。 The coating composition C contains fine particles having an average particle diameter of 1 to 10 μm. The anti-glare hard coat layer 12 formed by containing such fine particles has a rough surface and exhibits an anti-glare function. The average particle diameter of the fine particles is preferably 2 μm to 8 μm, and particularly preferably 3 μm to 5 μm.
另外,上述微粒子在以下算式中所示的粒徑變動係數(CV值),優選為10%~70%,特別優選為20%~60%。 The particle size variation coefficient (CV value) of the fine particles shown in the following formula is preferably 10% to 70%, and particularly preferably 20% to 60%.
粒徑的變動係數(CV值)=(標准偏差粒徑/平均粒徑)×100 Coefficient of variation of particle size (CV value) = (standard deviation particle size / average particle size) × 100
上述微粒子的CV值在上述範圍,則觸控筆的書寫感變得更加良好。 When the CV value of the fine particles is in the above range, the writing feeling of the stylus pen becomes more favorable.
另外,本說明書中的平均粒徑以及粒徑的變動係數(CV值),為利用鐳射衍射散射式細微性分佈測定裝置,將通過分散劑甲基乙基酮調製的5質量%濃度的分散液作為樣品,使用幾滴而測定的值。 In addition, the average particle diameter and the coefficient of variation (CV value) of the particle diameter in this specification are a dispersion liquid of 5 mass% concentration prepared by a dispersant methyl ethyl ketone using a laser diffraction scattering type fineness distribution measuring device. As a sample, a value measured using a few drops.
上述微粒子,可以為無機微粒子,也可以為有機微粒子,但從所形成的防眩性硬塗層12的硬度觀點考慮,優選為無機微粒子。作為無機微粒子,例如可以列舉由二氧化矽、氧化鋁、氧化鈦、氧化鋯、氧化錫、氧化銦、氧化鎘、氧化銻等所構成的微粒子。其中,優選二氧化矽微粒子。另外,微粒子可以單獨使用一種,也可以組合兩種以上使用。 The fine particles may be inorganic fine particles or organic fine particles, but from the viewpoint of the hardness of the anti-glare hard coat layer 12 formed, inorganic fine particles are preferred. Examples of the inorganic fine particles include fine particles composed of silicon dioxide, aluminum oxide, titanium oxide, zirconia, tin oxide, indium oxide, cadmium oxide, antimony oxide, and the like. Among these, silicon dioxide fine particles are preferred. The fine particles may be used singly or in combination of two or more kinds.
微粒子的形狀,可以為球狀等的固定形狀,但優選為無特定形狀的無定形。無定形的微粒子,比球狀的微粒子,更容易滿足上述筆尖阻力的初始值(A)與滑動值(B)的關係,觸控筆的書寫感變得更加良好。因此,上述微粒子特別優選為無定形二氧化矽微粒子。 The shape of the fine particles may be a fixed shape such as a spherical shape, but is preferably an amorphous shape having no specific shape. Amorphous particles are easier to satisfy the relationship between the initial value (A) and the sliding value (B) of the tip resistance than spherical particles, and the writing feel of the stylus pen becomes better. Therefore, the fine particles are particularly preferably fine particles of amorphous silica.
相對於多官能(甲基)丙烯酸酯(或其固化物)100質量份,上述微粒子的搭配比率,優選為1質量份~50質量份, 特別優選為5質量份~30質量份,進一步優選為10質量份~20質量份。上述微粒子的搭配比率在1質量份以上,則形成的防眩性硬塗層12可被賦予所希望的防眩性。另外,上述微粒子的搭配比率在50質量份以下,則塗料組合物C的塗工性變得良好,可形成膜厚度均勻的防眩性硬塗層12。 The blending ratio of the fine particles is preferably 1 to 50 parts by mass, particularly preferably 5 to 30 parts by mass, and more preferably 100 parts by mass of the polyfunctional (meth) acrylate (or a cured product thereof). 10 parts by mass to 20 parts by mass. When the blending ratio of the fine particles is 1 part by mass or more, the anti-glare hard coat layer 12 can be provided with desired anti-glare properties. In addition, if the blending ratio of the fine particles is 50 parts by mass or less, the coatability of the coating composition C becomes good, and an anti-glare hard coat layer 12 having a uniform film thickness can be formed.
(3)勻染劑 (3) Levelling agent
本實施形態所述塗料組合物C含有勻染劑。由此形成的防眩性硬塗層12沒有線紋狀缺陷或斑點等,膜厚度均勻,呈現優異的外觀。 The coating composition C according to this embodiment contains a leveling agent. The anti-glare hard coat layer 12 thus formed has no line-like defects, spots, or the like, has a uniform film thickness, and exhibits an excellent appearance.
作為勻染劑,例如可以舉出矽酮類勻染劑、氟類勻染劑、丙烯酸類勻染劑、乙烯類勻染劑等,其中,從勻染性以及與其他成分的相溶性觀點考慮,優選矽酮類勻染劑以及氟類勻染劑。另外,勻染劑可以單獨使用一種,也可以組合兩種以上使用。 Examples of leveling agents include silicone leveling agents, fluorine leveling agents, acrylic leveling agents, and vinyl leveling agents. Among these, leveling properties and compatibility with other components are considered. Of these, silicone leveling agents and fluorine leveling agents are preferred. The leveling agents may be used singly or in combination of two or more.
矽酮類勻染劑,優選聚二甲基矽氧烷或改性聚二甲基矽氧烷,特別優選為聚二甲基矽氧烷。另外,如果改性聚二甲基矽氧烷的改性率高,為了使發揮勻染性得到的防眩性硬塗層12的外觀變得優異,需增加其添加量。其結果,所形成的防眩性硬塗層12的滑動性變高,無法滿足上述筆尖阻力的初始值(A)與滑動值(B)的關係,有使觸控筆的書寫感下降的情況。 The silicone-based levelling agent is preferably polydimethylsiloxane or modified polydimethylsiloxane, and particularly preferably polydimethylsiloxane. In addition, if the modification rate of the modified polydimethylsiloxane is high, in order to improve the appearance of the anti-glare hard coat layer 12 obtained by exhibiting leveling properties, the amount of addition thereof needs to be increased. As a result, the slip resistance of the formed anti-glare hard coat layer 12 becomes high, and the relationship between the initial value (A) and the slip value (B) of the above-mentioned pen tip resistance cannot be satisfied, and the writing feeling of the stylus pen may be reduced. .
作為氟類勻染劑,可以優選列舉具有全氟烷基或氟化烯基作為主鏈或側鏈的化合物。作為市銷品,可優選列舉BYK日本公司產品BYK-340、NEOS公司產品FTERGENT650A、DIC公司產品MEGAFAC RS-75、大阪有機化學工業公司產品 V-8FM等,但並不限定於此。 As the fluorine-based levelling agent, a compound having a perfluoroalkyl group or a fluorinated alkenyl group as a main chain or a side chain is preferably exemplified. Examples of commercially available products include BYK Japan's product BYK-340, NEOS 'product FTERGENT650A, DIC's product MEGAFAC RS-75, and Osaka Organic Chemical Industry's product V-8FM, but are not limited thereto.
相對於多官能(甲基)丙烯酸酯(或其固化物)100質量份,矽酮類勻染劑的搭配比率,優選為0.001質量份~1.0質量份,特別優選為0.005質量份~0.8質量份,進一步優選為0.01質量份~0.1質量份。另一方面,氟類勻染劑的情況,相對於多官能(甲基)丙烯酸酯(或其固化物)100質量份,優選為0.1質量份~10質量份,特別優選為0.5質量份~5質量份,進一步優選為0.8質量份~3質量份。勻染劑的搭配比率在上述範圍,則可保持觸控筆的書寫感以及指紋非視認性良好,同時可充分獲得勻染效果。 The blending ratio of the silicone leveling agent is preferably 0.001 to 1.0 parts by mass, and particularly preferably 0.005 to 0.8 parts by mass with respect to 100 parts by mass of the polyfunctional (meth) acrylate (or its cured product). , More preferably 0.01 to 0.1 parts by mass. On the other hand, in the case of a fluorine-based levelling agent, it is preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass, with respect to 100 parts by mass of the polyfunctional (meth) acrylate (or its cured product). The mass part is more preferably 0.8 to 3 parts by mass. If the leveling ratio of the leveling agent is within the above range, the writing feeling of the stylus and the non-visibleness of the fingerprint are good, and the leveling effect can be fully obtained.
(4)二氧化矽納米粒子 (4) Silicon dioxide nanoparticles
本實施形態所述塗料組合物C,優選為含有平均粒徑為1nm~300nm的二氧化矽納米粒子。塗料組合物C通過含有這種二氧化矽納米粒子,所形成的防眩性硬塗層12的硬度提高,同時,可抑制眩光。上述二氧化矽納米粒子的平均粒徑,優選為5nm~100nm,特別優選為10nm~50nm。另外,二氧化矽納米粒子的平均粒徑為通過ZETA電位測定法而測定。 The coating composition C according to the present embodiment preferably contains silicon dioxide nanoparticles having an average particle diameter of 1 nm to 300 nm. When the coating composition C contains such silicon dioxide nanoparticles, the hardness of the anti-glare hard coat layer 12 formed is increased, and at the same time, glare can be suppressed. The average particle diameter of the silicon dioxide nanoparticles is preferably 5 nm to 100 nm, and particularly preferably 10 nm to 50 nm. The average particle diameter of the silicon dioxide nanoparticles is measured by a ZETA potential measurement method.
二氧化矽納米粒子,以提高分散性等為目的,也可通過有機物進行修飾。另外,二氧化矽納米粒子還優選為有機溶膠(膠體狀)的形態。通過以有機溶膠的形態,二氧化矽納米粒子的分散性變得良好,所形成的防眩性硬塗層12的均質性以及光透過性提高。 Silicon dioxide nanoparticles can be modified with organic substances for the purpose of improving dispersibility. In addition, the silica particles are also preferably in the form of an organosol (colloid). In the form of an organosol, the dispersibility of the silicon dioxide nanoparticles becomes good, and the homogeneity and light transmittance of the formed anti-glare hard coat layer 12 are improved.
通過有機物進行的修飾,可使用通常的方法實施。例如,可將結構如CH2=C(CH3)COO(CH2)3Si(OCH3)3的矽 烷偶聯劑,添加到二氧化矽納米粒子的有機溶膠中,在50℃左右加溫,通過攪拌幾個小時,修飾二氧化矽粒子的表面。所使用的矽烷偶聯劑的結構以及量,可根據二氧化矽納米粒子的分散性要求程度,適當選擇。 Modification by an organic substance can be performed by a usual method. For example, a silane coupling agent having a structure such as CH 2 = C (CH 3 ) COO (CH 2 ) 3 Si (OCH 3 ) 3 can be added to an organosol of silicon dioxide nanoparticles, and heated at about 50 ° C. The surface of the silica particles was modified by stirring for several hours. The structure and amount of the silane coupling agent used can be appropriately selected according to the required degree of dispersibility of the silicon dioxide nanoparticles.
作為上述有機溶膠的分散溶劑,優選與多官能(甲基)丙烯酸酯和勻染劑的相溶性以及塗層形成時的發揮性優異的甲基乙基酮、甲基異丁基酮等。 As a dispersion solvent of the said organosol, methyl ethyl ketone, methyl isobutyl ketone, etc. which are excellent in compatibility with a polyfunctional (meth) acrylate, a leveling agent, and the performance at the time of coating formation are preferable.
作為上述二氧化矽納米粒子,可使用市面銷售的產品,其中優選為使用日產化學公司產品有機二氧化矽溶膠MEK-ST、MIBK-ST等。 As the silicon dioxide nanoparticles, commercially available products can be used, and among them, organic silicon dioxide sol MEK-ST, MIBK-ST, etc., which are products of Nissan Chemical Co., are preferably used.
相對於多官能(甲基)丙烯酸酯(或其固化物)100質量份,上述二氧化矽納米粒子的搭配比率,優選為1質量份~50質量份,特別優選為2質量份~20質量份,進一步優選為2質量份~10質量份。上述二氧化矽納米粒子的搭配比率在1質量份以上,則可良好地發揮上述效果。另一方面,二氧化矽納米粒子的搭配比率如果在50質量份以下,則會抑制二氧化矽納米粒子的凝集,可良好地保持所形成的防眩性硬塗層12的均質性以及光透過性。 The blending ratio of the silica nanoparticles is preferably 1 to 50 parts by mass, and particularly preferably 2 to 20 parts by mass with respect to 100 parts by mass of the polyfunctional (meth) acrylate (or a cured product thereof). , More preferably 2 to 10 parts by mass. When the blending ratio of the silicon dioxide nanoparticles is 1 part by mass or more, the above-mentioned effect can be exhibited well. On the other hand, if the mixing ratio of the silicon dioxide nanoparticles is 50 parts by mass or less, aggregation of the silicon dioxide nanoparticles is suppressed, and the homogeneity and light transmission of the formed anti-glare hard coat layer 12 can be well maintained. Sex.
(5)其他成分 (5) Other ingredients
本實施形態中的塗料組合物C,除了上述成分以外,還可含有各種添加劑。作為各種添加劑,例如可以舉出光聚合起始劑、紫外線吸收劑、氧化防止劑、光穩定劑、帶電防止劑、矽烷偶聯劑、防老化劑、熱聚合抑制劑、著色劑、表面活性劑、保存穩定劑、增塑劑、潤滑劑、消泡劑、有機填料、潤濕性改 良劑、塗層表面改性劑等。 The coating composition C in this embodiment may contain various additives in addition to the above-mentioned components. Examples of the various additives include a photopolymerization initiator, an ultraviolet absorber, an oxidation inhibitor, a light stabilizer, an antistatic agent, a silane coupling agent, an anti-aging agent, a thermal polymerization inhibitor, a colorant, and a surfactant. , Storage stabilizer, plasticizer, lubricant, defoamer, organic filler, wettability improver, coating surface modifier, etc.
作為光聚合起始劑,例如可以列舉苯偶姻、苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻異丙基醚、苯偶姻正丁基醚、苯偶姻異丁基醚、苯乙酮、二甲氨基苯乙酮、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-(甲基硫代)苯基〕-2-嗎琳-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’-二乙氨基二苯甲酮、二氯二苯甲酮、2-甲基蒽醌、2-乙基蒽醌、2-叔丁基蒽醌、2-氨基蒽醌、2-甲基塞噸酮、2-乙基塞噸酮、2-氯塞噸酮、2,4-二甲基塞噸酮、2,4-二乙基塞噸酮、苄基二甲基縮酮、苯乙酮二甲基縮酮、p-二甲基氨基安息香酸酯等。這些可以單獨使用一種,也可以組合兩種以上使用。 Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, and benzoin isobutyl Ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy 2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholin- Propane-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) one, benzophenone, p-phenylbenzophenone, 4,4'- Diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylxanthone , 2-ethylxanthone, 2-chloroxanthone, 2,4-dimethylxanthone, 2,4-diethylxanthone, benzyldimethylketal, acetophenone Methyl ketal, p-dimethylaminobenzoate and the like. These may be used alone or in combination of two or more.
相對於多官能(甲基)丙烯酸酯(或其固化物)100質量份,上述光聚合起始劑的搭配比率,通常從0.2質量份~10質量份的範圍選擇。 The blending ratio of the photopolymerization initiator is usually selected from a range of 0.2 to 10 parts by mass based on 100 parts by mass of the polyfunctional (meth) acrylate (or a cured product thereof).
通過將以上說明的塗料組合物C在基材膜11上塗布、固化,可形成滿足上述物性的防眩性硬塗層12。 By applying and curing the coating composition C described above on the base film 11, an anti-glare hard coat layer 12 satisfying the above-mentioned physical properties can be formed.
防眩性硬塗層12的厚度,優選為1μm~15μm,特別優選為2μm~10μm。防眩性硬塗層12的厚度在上述範圍,則可有效發揮抗劃傷性以及防眩功能。 The thickness of the anti-glare hard coat layer 12 is preferably 1 μm to 15 μm, and particularly preferably 2 μm to 10 μm. When the thickness of the anti-glare hard coat layer 12 is within the above range, the scratch resistance and anti-glare function can be effectively exhibited.
3.基材膜 3. Substrate film
作為基材膜11,只要從適宜於使用觸控筆的觸控面板用基材膜中適當選擇即可,優選為選擇與防眩性硬塗層12親和 性良好的塑料薄膜。 The base film 11 may be appropriately selected from a base film for a touch panel suitable for use with a stylus, and a plastic film having good affinity with the anti-glare hard coat layer 12 is preferably selected.
作為上述塑膠薄膜,例如可以舉出聚對苯二甲酸乙二醇酯、聚對苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯等的聚酯薄膜;聚乙烯薄膜、聚丙烯薄膜等的聚烯烴薄膜;玻璃紙、二乙醯纖維素薄膜、三乙醯纖維素薄膜、纖維素乙醯基丁酸酯薄膜、聚氯乙烯薄膜、聚偏二氯乙烯薄膜、聚乙烯醇薄膜、乙烯-醋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、聚醚酮薄膜、聚醚碸薄膜、聚醯亞胺薄膜、氟樹脂薄膜、聚醯胺薄膜、丙烯酸樹脂薄膜、聚氨酯樹脂薄膜、降冰片烯聚合物薄膜、環烯烴類聚合物薄膜、環狀共軛二烯聚合物薄膜、乙烯基脂環烴聚合物薄膜等的塑膠薄膜,或者這些的積層薄膜。其中,從機械性強度等方面考慮,優選聚對苯二甲酸乙二醇酯薄膜、聚碳酸酯薄膜、降冰片烯聚合物薄膜等。 Examples of the plastic film include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyethylene films and polypropylene films And other polyolefin films; cellophane, diethyl cellulose film, triethyl cellulose film, cellulose ethyl butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene -Vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polyfluorene film, polyetherketone film, polyetherfluorene film, polyfluorine film, fluororesin film, poly Amine film, acrylic resin film, polyurethane resin film, norbornene polymer film, cyclic olefin polymer film, cyclic conjugated diene polymer film, vinyl alicyclic polymer film, etc., or plastic film, or These laminated films. Among them, polyethylene terephthalate film, polycarbonate film, norbornene polymer film, and the like are preferred from the viewpoint of mechanical strength and the like.
另外,上述基材膜11中,以提高與形成於其表面的層(防眩性硬塗層12、後述粘接劑層等)的密合性為目的,可根據需要,在一面或兩面進行底漆處理,根據氧化法、凹凸化法等進行表面處理。作為氧化法,例如可以列舉出電暈放電處理、鉻酸鹽處理、火焰處理、熱空氣處理、臭氧‧紫外線處理等;作為凹凸化法,例如可以列舉出噴砂法、溶劑處理法等。這些表面處理法,可根據基材膜11的種類適當選擇,但一般利用在效果和操作性等方面優異的電暈放電處理法。 In addition, the substrate film 11 may be formed on one surface or both surfaces for the purpose of improving adhesion to a layer (anti-glare hard coat layer 12, adhesive layer, etc.) to be formed on the surface thereof. The primer is subjected to a surface treatment according to an oxidation method, a bumping method, or the like. Examples of the oxidation method include corona discharge treatment, chromate treatment, flame treatment, hot air treatment, ozone · ultraviolet treatment, and the like. Examples of the bumping method include a sandblasting method and a solvent treatment method. These surface treatment methods can be appropriately selected depending on the type of the base film 11, but a corona discharge treatment method which is excellent in terms of effects and operability is generally used.
基材膜11的厚度,通常為15μm~300μm左右,優選為30μm~200μm左右。 The thickness of the base film 11 is usually about 15 μm to 300 μm, and preferably about 30 μm to 200 μm.
4.防眩性硬塗薄膜的製造方法 4. Manufacturing method of anti-glare hard coating film
本實施形態所述防眩性硬塗薄膜1,可以通過將防眩性硬塗層12用的塗料組合物,特別是優選塗料組合物C與根據需要含有溶劑的塗工液在基材膜11上塗布、固化,形成防眩性硬塗層12來製造。 The anti-glare hard coat film 1 according to the present embodiment can be prepared by using the coating composition for the anti-glare hard coat layer 12, particularly, the coating composition C and a coating solution containing a solvent as needed in the base film 11. It is manufactured by coating and curing to form an anti-glare hard coat layer 12.
溶劑可為了塗工性的改良、粘度調整、固體成分濃度的調整等而使用,如果是溶解多官能(甲基)丙烯酸酯以及勻染劑等,尤其可以無任何限制地使用。 The solvent can be used for the purpose of improving the workability, adjusting the viscosity, adjusting the solid content concentration, and the like. If the solvent is a polyfunctional (meth) acrylate, a leveling agent, etc., it can be used without any limitation.
作為溶劑的具體例子,可以舉出甲醇、乙醇、異丙醇、丁醇、辛醇等的醇類;丙酮、甲基乙基酮、甲基異丁基酮、環己酮等的酮類;乙酸乙酯、乙酸丁酯、乳酸乙酯、γ-丁內酯等的酯類;乙二醇單甲醚(甲基溶纖劑)、乙二醇單乙醚(乙基溶纖劑)、二甘醇單丁醚(丁基溶纖劑)、丙二醇單甲醚等的醚類;苯,甲苯,二甲苯等的芳香烴;二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯烷酮等的醯胺類等。 Specific examples of the solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, etc .; ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), two Glycol monobutyl ether (butyl cellosolve), propylene glycol monomethyl ether, and other ethers; aromatic hydrocarbons such as benzene, toluene, and xylene; dimethylformamide, dimethylacetamide, and N-methylpyrrolidone And so on.
塗料組合物塗工液的塗布,可用通常的方法進行,例如可以利用棒塗布法、刮刀塗布法、輥塗布法、板塗布法、模具塗布法、凹板塗布法進行。如果將塗料組合物的塗工液塗布,優選為將塗膜在40℃~120℃進行30秒~5分鐘左右的乾燥。 The coating composition coating liquid can be applied by a common method. For example, it can be performed by a bar coating method, a blade coating method, a roll coating method, a plate coating method, a die coating method, or a gravure coating method. When the coating liquid of the coating composition is applied, the coating film is preferably dried at 40 ° C. to 120 ° C. for about 30 seconds to 5 minutes.
在此,像塗料組合物C一樣,塗料組合物含有勻染劑的情況,塗布該塗料組合物的塗膜,沒有線紋狀缺陷或斑點等,因此,可形成膜厚度均勻,外觀優異的防眩性硬塗層12。 Here, like the coating composition C, when the coating composition contains a leveling agent, the coating film coated with the coating composition has no line-like defects or spots, and therefore, it is possible to form a uniform film thickness and excellent appearance. Glare Hard Coating 12.
像塗料組合物C一樣,塗料組合物為活性能量線 固化性的情況時,塗料組合物的固化,可通過在氮氣氣氛下,在塗料組合物的塗膜上照射紫外線、電子束等的活性能量線來進行。紫外線的照射可通過高壓水銀燈、Fusion H燈、氙氣燈等進行,紫外線的照射量優選照度為50mW/cm2~1000mW/cm2、光量為50mJ/cm2~1000mJ/cm2左右。另一方面,電子束的照射可通過電子束加速器等進行,電子束的照射量優選為10krad~1000krad左右。 Like coating composition C, when the coating composition is active energy ray curable, curing of the coating composition can be achieved by irradiating the coating film of the coating composition with active energy such as ultraviolet rays and electron beams under a nitrogen atmosphere. Line to proceed. The irradiation of ultraviolet rays can be performed by a high-pressure mercury lamp, a Fusion H lamp, a xenon lamp, and the like. The irradiation amount of ultraviolet rays is preferably 50 mW / cm 2 to 1000 mW / cm 2 and the light amount is about 50 mJ / cm 2 to 1000 mJ / cm 2 . On the other hand, the irradiation of the electron beam can be performed by an electron beam accelerator or the like, and the irradiation amount of the electron beam is preferably about 10 krad to 1,000 krad.
5.其他 5. Other
本實施形態所述防眩性硬塗薄膜1中,防眩性硬塗層12為最外表面,優選為具有基材膜11和防眩性硬塗層12,在防眩性硬塗層12與基材膜11之間,或與基材膜11的防眩性硬塗層12不接觸的一側的面上,具有其他層也可。例如,在與基材膜11的防眩性硬塗層12不接觸的一側的面上,可以形成粘接劑層,另外,也可以在粘接劑層上積層剝離片。 In the anti-glare hard coat film 1 according to this embodiment, the anti-glare hard coat layer 12 is the outermost surface, and preferably has a base film 11 and an anti-glare hard coat layer 12, and the anti-glare hard coat layer 12 There may be another layer on the surface that is not in contact with the base film 11 or the anti-glare hard coat layer 12 of the base film 11. For example, an adhesive layer may be formed on the surface of the side which is not in contact with the anti-glare hard coat layer 12 of the base film 11, and a release sheet may be laminated on the adhesive layer.
作為構成粘接劑層的粘接劑,沒有特別的限制,可使用丙烯酸類粘接劑、橡膠類粘接劑、矽酮類粘接劑等已知的粘接劑。另外,該粘接劑層,無需具有如專利文獻1中所述的緩沖性。 The adhesive constituting the adhesive layer is not particularly limited, and known adhesives such as an acrylic adhesive, a rubber adhesive, and a silicone adhesive can be used. The adhesive layer need not have cushioning properties as described in Patent Document 1.
本實施形態所述防眩性硬塗薄膜1的防眩性硬塗層12的算術平均表面粗糙度(Ra),優選為0.01μm~10μm,特別優選為0.1μm~1μm,進一步優選為0.15μm~0.5μm。算術平均表面粗糙度(Ra)在上述範圍,則防眩性硬塗層12可發揮優異的防眩性。另外,本說明書中的算術平均表面粗糙度(Ra)為基於JIS B0601-1994,從使用接觸型粗糙度計(試驗例中使用 了三豐公司產品SV3000S4)測定的粗糙度曲線中求得。 The arithmetic average surface roughness (Ra) of the anti-glare hard coat layer 12 of the anti-glare hard coat film 1 according to this embodiment is preferably 0.01 μm to 10 μm, particularly preferably 0.1 μm to 1 μm, and more preferably 0.15 μm. ~ 0.5μm. When the arithmetic average surface roughness (Ra) is within the above range, the anti-glare hard coat layer 12 can exhibit excellent anti-glare properties. In addition, the arithmetic average surface roughness (Ra) in the present specification is obtained from a roughness curve measured using a contact-type roughness meter (Mitutoyo Corporation product SV3000S4 is used in the test example) based on JIS B0601-1994.
本實施形態所述防眩性硬塗薄膜1的防眩性硬塗層12,優選為利用# 0000的鋼絲絨,在250g/cm2的負重下,將防眩性硬塗層12在10cm來回摩擦10次不產生刮痕。通過具有這種由鋼絲絨硬度評價的抗劃傷性,將防眩性硬塗薄膜1用於觸控面板的表面時,可抑制防眩性硬塗層12上出現刮痕。 The anti-glare hard coat layer 12 of the anti-glare hard coat film 1 according to this embodiment is preferably made of steel wool of # 0000, and the anti-glare hard coat layer 12 is moved back and forth at 10 cm under a load of 250 g / cm 2 . No scratches after rubbing 10 times. By having such scratch resistance evaluated from the hardness of steel wool, when the anti-glare hard coating film 1 is used on the surface of a touch panel, the occurrence of scratches on the anti-glare hard coating layer 12 can be suppressed.
另外,本實施形態所述防眩性硬塗薄膜1的霧度值,優選為30%以下,特別優選為20%以下,進一步優選為15%以下。霧度值如果在30%以下,則可進行高清化,適宜作為觸控面板用。另外,從發揮防眩性的觀點考慮,霧度值優選為0.5%以上,特別優選為2%以上,進一步優選為6%以上。另外,霧度值為基於JIS K7136-2000所測定的值。 The haze value of the anti-glare hard coat film 1 according to this embodiment is preferably 30% or less, particularly preferably 20% or less, and still more preferably 15% or less. If the haze value is less than 30%, it can be high-definition, which is suitable for use as a touch panel. From the viewpoint of exhibiting anti-glare properties, the haze value is preferably 0.5% or more, particularly preferably 2% or more, and still more preferably 6% or more. The haze value is a value measured based on JIS K7136-2000.
以上說明的實施形態,是為了易於對本發明的理解而記述的,並不是對本發明進行限定而進行的記述。因此,上述實施形態中所公開的各要素,也包括屬於本發明的技術範圍的所有設計變更以及均等物。 The embodiments described above are described for easy understanding of the present invention, and are not described to limit the present invention. Therefore, each element disclosed in the above embodiment includes all design changes and equivalents belonging to the technical scope of the present invention.
例如,防眩性硬塗薄膜1中,基材膜11與防眩性硬塗層12之間也可介入其他的層。 For example, in the anti-glare hard coat film 1, another layer may be interposed between the base film 11 and the anti-glare hard coat layer 12.
【實施例】 [Example]
以下,通過實施例等進一步對本發明進行具體說明,但是本發明的範圍並不受這些實施例等的限定。 Hereinafter, the present invention will be described in more detail through examples and the like, but the scope of the present invention is not limited by these examples and the like.
〔實施例1〕 [Example 1]
作為多官能(甲基)丙烯酸酯,將二季戊四醇六丙烯酸酯(新中村化學公司製,NK酯A-DPH)100質量份(表示固體成分換算 值。以下,對於其他成分也同樣。);作為光聚合起始劑,將1-羥基環己基苯基酮(巴斯夫公司製,IRUGACURE 184)4.3質量份;二氧化矽微粒子(富士矽化學公司製,SYLOPHOBIC 702;平均粒徑:4.1μm,CV值48%,無定形)11質量份;作為勻染劑,將聚二甲基矽氧烷(東麗˙道康寧公司製,SH28)0.01質量份與二氧化矽納米粒子(日產化學工業公司製,MIBK-ST,平均粒徑:10nm)8.3質量份,進行混合,得到塗料組合物。將該塗料組合物用丙二醇單甲醚進行稀釋,調製固體成分濃度為30%的塗工液。 As a polyfunctional (meth) acrylate, 100 parts by mass of dipentaerythritol hexaacrylate (manufactured by Shin Nakamura Chemical Co., Ltd., NK ester A-DPH) (representing a solid content conversion value. Hereinafter, the same applies to other components.); As a photopolymerization initiator, 4.3 parts by mass of 1-hydroxycyclohexylphenyl ketone (IRUGACURE 184, manufactured by BASF Corporation); silica fine particles (SYLOPHOBIC 702, manufactured by Fuji Silicon Chemical Co., Ltd.); average particle diameter: 4.1 μm, CV value 48%, amorphous) 11 parts by mass; As a levelling agent, 0.01 parts by mass of polydimethylsiloxane (manufactured by Toray Dow Corning Corporation, SH28) and silicon dioxide nanoparticles (manufactured by Nissan Chemical Industries, Ltd., MIBK) -ST, average particle diameter: 10 nm) 8.3 parts by mass, and mixed to obtain a coating composition. This coating composition was diluted with propylene glycol monomethyl ether to prepare a coating liquid having a solid content concentration of 30%.
在作為基材膜,附有易粘接層的聚酯薄膜(東洋紡公司製,COSMO SHINE A4300,厚度:125μm)的易粘接層一側的面上,將上述所得到的塗工液用Wire Bar # 10塗布,在70℃下進行1分鐘乾燥。接著,在氮氣氣氛下,使用紫外線照射裝置(EYE GRAPHIC公司製,EYE GRANTAGEECS-401GX型),在如下條件下照射紫外線,形成厚度為3μm的防眩性硬塗層,得到防眩性硬塗薄膜。 On the side of the easily-adhesive layer of the polyester film (COSMO SHINE A4300, thickness: 125 μm) with an easily-adhesive layer as the base film, the coating solution obtained above was coated with Wire. Bar # 10 was applied and dried at 70 ° C. for 1 minute. Next, an ultraviolet irradiation device (EYE GRANTAGEECS-401GX, manufactured by EYE GRAPHIC, Inc.) was used in a nitrogen atmosphere to irradiate ultraviolet rays under the following conditions to form an anti-glare hard coat layer having a thickness of 3 μm to obtain an anti-glare hard coat film. .
〔紫外線照射條件〕 [UV irradiation conditions]
‧光源:高壓水銀燈 ‧Light source: high pressure mercury lamp
‧燈泡功率:2kW ‧Bulb power: 2kW
‧輸送帶速度:4.23m/min ‧Conveyor speed: 4.23m / min
‧照度:240mW/cm2 ‧Illumination: 240mW / cm 2
‧光量:307mJ/cm2 ‧Light quantity: 307mJ / cm 2
〔實施例2〕 [Example 2]
除了將勻染劑的搭配量變更為0.14質量份,形成防眩性 硬塗層外,與實施例1同樣地進行操作,製造防眩性硬塗薄膜。 An anti-glare hard-coated film was produced in the same manner as in Example 1 except that the blending amount of the leveling agent was changed to 0.14 parts by mass to form an anti-glare hard-coat layer.
〔實施例3〕 [Example 3]
除了將勻染劑的搭配量變更為0.70質量份,形成防眩性硬塗層外,與實施例1同樣地進行操作,製造防眩性硬塗薄膜。 An anti-glare hard coat film was produced in the same manner as in Example 1 except that the blending amount of the leveling agent was changed to 0.70 parts by mass to form an anti-glare hard coat layer.
〔實施例4〕 [Example 4]
除了將紫外線反應型氟低聚物(NEOS公司製,FTERGENT650A)作為勻染劑使用,將其搭配量變更為1.4質量份,形成防眩性硬塗層外,與實施例1同樣地進行操作,製造防眩性硬塗薄膜。 An ultraviolet-reactive fluorine oligomer (FTERGENT650A, manufactured by NEOS Corporation) was used as a leveling agent, and the blending amount was changed to 1.4 parts by mass to form an anti-glare hard coat layer. Manufacture of anti-glare hard coating film.
〔比較例1〕 [Comparative Example 1]
除了將具有丙烯醯基的聚醚改性聚二甲基矽氧烷(BYK公司製,BYK-UV3500)作為勻染劑使用,將其搭配量變更為1.4質量份,形成防眩性硬塗層外,與實施例1同樣地進行操作,製造防眩性硬塗薄膜。 In addition to using a polyether-modified polydimethylsiloxane (BYK-UV3500, manufactured by BYK) as a levelling agent, the blending amount was changed to 1.4 parts by mass to form an anti-glare hard coat layer. In addition, it carried out similarly to Example 1, and produced the anti-glare hard-coat film.
〔比較例2〕 [Comparative Example 2]
除了將勻染劑的搭配量變更為1.4質量份,形成防眩性硬塗層外,與實施例1同樣地進行操作,製造防眩性硬塗薄膜。 An anti-glare hard coat film was produced in the same manner as in Example 1 except that the blending amount of the leveling agent was changed to 1.4 parts by mass to form an anti-glare hard coat layer.
〔比較例3〕 [Comparative Example 3]
除了將實施例1的二氧化矽微粒子變更為二氧化矽微粒子(綜研化學工程公司製,MX-300;平均粒徑:3.0μm,CV值15%,球形),將其搭配量變更為10質量份,並將塗工液塗布時的Wire Bar從#10變為#14,將防眩性硬塗層的膜厚度變更為5μm外,與實施例1同樣地進行操作,製造防眩性硬塗薄膜。 In addition to changing the silicon dioxide fine particles of Example 1 to silicon dioxide fine particles (MX-300 manufactured by Soken Research Chemical Engineering Co., Ltd .; average particle diameter: 3.0 μm, CV value 15%, spherical shape), the blending amount was changed to 10 mass The coating was changed from # 10 to # 14 when the coating liquid was applied, and the film thickness of the anti-glare hard coat layer was changed to 5 μm. The same operation as in Example 1 was performed to produce an anti-glare hard coat. film.
〔試驗例1〕(筆尖阻力的測定) [Test Example 1] (Measurement of Pen Tip Resistance)
對於實施例以及比較例中製造的防眩性硬塗薄膜的防眩性硬塗層表面,使用萬能試驗機(ORIENTEC公司製,TENSILON)以及觸控筆,在負重150g重量下,用觸控筆的筆尖接觸薄膜表面,以100mm/min的速度進行掃描的條件下進行試驗。然後,在得到的試驗圖表中,求出筆尖阻力的初始值(A)以及滑動值(B)。另外,計算從筆尖阻力的初始值(A)中減去滑動值(B)的值。另外,作為觸控筆,使用了筆尖為硬氈芯的觸控筆(WACOM公司製,ACK-2003,筆尖直徑:0.5mm)。將結果示於表1。 For the anti-glare hard-coated surface of the anti-glare hard-coated film produced in the examples and comparative examples, a universal tester (tensilon manufactured by ORIENTEC) and a stylus pen were used under a weight of 150 g. The test was performed under the condition that the pen tip touched the film surface and scanned at a speed of 100 mm / min. Then, in the obtained test chart, the initial value (A) and the sliding value (B) of the pen tip resistance were obtained. In addition, a value obtained by subtracting the sliding value (B) from the initial value (A) of the pen resistance is calculated. In addition, as the stylus, a stylus with a hard felt tip (wacom, ACK-2003, nib diameter: 0.5 mm) was used. The results are shown in Table 1.
〔試驗例2〕(書寫感評價) [Test Example 2] (Evaluation of Writing Feeling)
從實施例以及比較例中製造的防眩性硬塗薄膜,將防眩性硬塗層一側朝上,載置於玻璃基板上。對該防眩性硬塗薄膜的防眩性硬塗層表面,用與試驗例1相同的觸控筆以及聚縮醛芯的觸控筆(筆尖直徑:0.4mm),分別評價書寫感。評價中,將與在5張重疊的紙(國譽科技公司製,CAMPUS NOTE A鉛線NO-201A)上,用鉛筆(三菱鉛筆公司製,MITSUBISHI PENCIL UNI B),以筆壓約150g重量書寫時的書寫感相近的作為良好,將與該書寫感差距大的作為不良。另外,評價由3人的專門小組成員進行,3人全部感覺良好時作為良好,只要有1人感覺不良時作為不良。將結果示於表1。 The anti-glare hard-coated films produced in the examples and comparative examples were placed on a glass substrate with the anti-glare hard-coat side facing up. On the surface of the anti-glare hard coat layer of the anti-glare hard coat film, the same stylus as in Test Example 1 and a polyacetal-core stylus (pen tip diameter: 0.4 mm) were used to evaluate the writing feeling. In the evaluation, a sheet of paper (manufactured by KOKUYO Technology Co., Ltd., CAMPUS NOTE A lead wire NO-201A) was written with a pencil (MITSUBISHI PENCIL UNI B, manufactured by Mitsubishi Pencil Co., Ltd.) with a pen pressure of about 150 g. Those with a similar writing feeling at the time were good, and those with a large gap from the writing feeling were bad. In addition, the evaluation was performed by three panelists. When all three felt good, it was considered good, and when only one felt bad, it was considered bad. The results are shown in Table 1.
〔試驗例3〕(油酸接觸角的測定) [Test Example 3] (Measurement of oleic acid contact angle)
實施例以及比較例中製造的防眩性硬塗薄膜的防眩性硬塗層表面的油酸接觸角,以使用全自動式接觸角測定儀(協和介面科學公司製,DM-701),在以下條件下測定。另外,油酸 使用了東京化成工業公司製造的油酸。將結果示於表1。 The oleic acid contact angle on the surface of the anti-glare hard coat layer of the anti-glare hard coat film produced in the examples and comparative examples was measured using a fully automatic contact angle tester (produced by Kyowa Interface Science Co., Ltd., DM-701) Measured under the following conditions. As the oleic acid, oleic acid manufactured by Tokyo Chemical Industry Co., Ltd. was used. The results are shown in Table 1.
‧油酸的液滴量:2μl ‧ Droplet volume of oleic acid: 2μl
‧測定時間:滴下3秒後 ‧Measurement time: 3 seconds after dropping
‧圖像分析法:θ/2法 ‧Image analysis method: θ / 2 method
〔試驗例4〕(指紋非視認性評價) [Test Example 4] (Evaluation of non-visible fingerprints)
將手指接觸於在實施例以及比較例中製造的防眩性硬塗薄膜的防眩性硬塗層表面,將手指使勁按壓前後的防眩性硬塗薄膜的霧度值(%),使用霧度測量計(日本電色工業公司製,NDH2000),基於JIS K7136-2000進行測定。然後,求出從手指使勁按壓後的薄膜霧度值中,減去手指使勁按壓前的薄膜霧度值的值(霧度值差),按照以下基準進行評價。另外,評價對象的霧度值,為將3人各用手指使勁按壓1次的樣品,分別測定時的平均值。將結果示於表1。另外,將用手指使勁按壓前防眩性硬塗薄膜的霧度值全部示於表1。 The haze value (%) of the anti-glare hard-coated film before and after pressing the finger firmly on the anti-glare hard-coated surface of the anti-glare hard-coated film produced in the examples and comparative examples, using a mist A degree meter (NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.) was measured based on JIS K7136-2000. Then, the value of the film haze value before the finger is strongly pressed (the difference in the haze value) is subtracted from the film haze value after the finger is strongly pressed, and evaluated according to the following criteria. In addition, the haze value of the evaluation target is an average value at the time of measurement in a sample in which each of three persons was strongly pressed with their fingers once. The results are shown in Table 1. In addition, all haze values of the anti-glare hard-coated film before strongly pressing with a finger are shown in Table 1.
◎:霧度值差未滿0.5 ◎: Haze value difference is less than 0.5
○:霧度值差為0.5以上1.0以下 ○: Haze value difference is 0.5 or more and 1.0 or less
×:霧度值差超過1.0 ×: Haze value difference exceeds 1.0
〔試驗例5〕(外觀評價) [Test Example 5] (Appearance Evaluation)
對實施例以及比較例中製造的防眩性硬塗薄膜,使用3波長熒光燈,用肉眼對反射時以及透過時的外觀進行評價。評價中,將線紋狀缺陷或斑點少的作為良好,將線紋狀缺陷或斑點多的作為不良。將結果示於表1。 The anti-glare hard-coated films produced in the examples and comparative examples were evaluated with naked eyes for external appearances during reflection and transmission using a 3-wavelength fluorescent lamp. In the evaluation, those with few line-like defects or spots were regarded as good, and those with many line-like defects or spots were regarded as bad. The results are shown in Table 1.
〔試驗例6〕(表面粗糙度的測定) [Test Example 6] (Measurement of Surface Roughness)
將從實施例以及比較例中製造的防眩性硬塗薄膜的防眩 性硬塗層表面的算術平均表面粗糙度(Ra;單位μm),基於JIS B0601-1994,以使用接觸型粗糙度計(三豐公司製,SV3000S4)所測定的粗糙度曲線求得。將結果示於表1。 The arithmetic average surface roughness (Ra; unit μm) of the anti-glare hard coat surface of the anti-glare hard coat film manufactured from the examples and comparative examples is based on JIS B0601-1994, using a contact-type roughness meter (SV3000S4, manufactured by Mitutoyo Corporation). The results are shown in Table 1.
〔試驗例7〕(抗劃傷性評價:鋼絲絨硬度) [Test Example 7] (Scratch Resistance Evaluation: Steel Wool Hardness)
對實施例以及比較例中製造的防眩性硬塗薄膜的防眩性硬塗層表面,使用# 0000的鋼絲絨,在250g/cm2的負重下,在10cm來回摩擦10次,將該防眩性硬塗層的表面用以下基準進行評價。 The anti-glare hard coating surface of the anti-glare hard coating film manufactured in the examples and comparative examples was made of steel wool of # 0000 and rubbed back and forth at 10 cm under a load of 250 g / cm 2 for 10 times. The surface of the glare hard coat layer was evaluated by the following criteria.
◎:外觀與試驗前完全沒有變化。 :: There was no change in appearance from before the test.
○:雖然沒看到刮痕,但由於粒子的脫落,防眩性降低。 ○: Although no scratches were observed, the anti-glare property was reduced due to the falling of the particles.
×:看到線狀的刮痕。 ×: Linear scratches were seen.
由表1可知,在實施例中製造的防眩性硬塗薄膜,書寫感良好,同時附著的指紋不易被看到,外觀以及防眩性也良好。 As can be seen from Table 1, the anti-glare hard-coated film produced in the examples has a good writing feeling, while the attached fingerprints are not easily seen, and the appearance and anti-glare properties are also good.
【產業上可利用性】 [Industrial availability]
本發明的防眩性硬塗薄膜,適宜作為使用觸控筆的觸控面板的表層而使用。 The anti-glare hard coat film of the present invention is suitable for use as a surface layer of a touch panel using a stylus.
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TWI678552B (en) * | 2013-05-30 | 2019-12-01 | 日商琳得科股份有限公司 | Anti-glare hard coating film |
TWI700187B (en) * | 2019-04-19 | 2020-08-01 | 日商大賽璐股份有限公司 | Surface material for pen input device |
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JP7004498B2 (en) * | 2016-12-14 | 2022-01-21 | リンテック株式会社 | Writing quality improvement film |
JP6325637B1 (en) * | 2016-11-16 | 2018-05-16 | リンテック株式会社 | Writing quality improvement film |
JP6871756B2 (en) * | 2017-02-20 | 2021-05-12 | リンテック株式会社 | Image display device with position detection function |
JP2018173906A (en) * | 2017-03-31 | 2018-11-08 | リンテック株式会社 | Writing feel improvement sheet |
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TWI700187B (en) * | 2019-04-19 | 2020-08-01 | 日商大賽璐股份有限公司 | Surface material for pen input device |
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