TWI787182B - Flexible display with repeated bending - Google Patents
Flexible display with repeated bending Download PDFInfo
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Abstract
一種硬塗薄膜1,其具備基材薄膜2、層積在基材薄膜2的至少一主面側之光學調整層3,及層積在光學調整層3之與基材薄膜2側為相反的主面側之硬塗層4,基材薄膜2為聚醯亞胺薄膜,光學調整層3的折射率係聚醯亞胺薄膜的折射率與硬塗層4的折射率之間之值,光學調整層3的厚度為30nm以上、700nm以下。此種硬塗薄膜1係具有經得起重複彎曲之耐彎曲性,同時不容易產生干涉條紋。 A hard coat film 1 comprising a base film 2, an optical adjustment layer 3 laminated on at least one main surface side of the base film 2, and an opposite side to the base film 2 laminated on the optical adjustment layer 3. The hard coating 4 on the main surface side, the base film 2 is a polyimide film, and the refractive index of the optical adjustment layer 3 is the value between the refractive index of the polyimide film and the refractive index of the hard coating 4. The thickness of the adjustment layer 3 is not less than 30 nm and not more than 700 nm. This kind of hard-coated film 1 has the bending resistance to withstand repeated bending, and at the same time, it is not easy to produce interference fringes.
Description
本發明係有關於一種具備基材薄膜及硬塗層之硬塗薄膜,特別是有關於一種能夠適合使用在可撓性顯示器之硬塗薄膜。 The present invention relates to a hard-coated film with a substrate film and a hard-coat layer, in particular to a hard-coated film suitable for use in flexible displays.
在各種電子機器,係廣泛地利用液晶顯示器(LCD)、有機EL顯示器(OELD)、更包括觸控面板等的各種顯示器。在該等各種顯示器的表面,為了防止損傷,多半設置有在基材薄膜設置有硬塗層之硬塗薄膜。 Various displays including liquid crystal displays (LCDs), organic EL displays (OELDs), and touch panels are widely used in various electronic devices. On the surface of these various displays, in order to prevent damage, a hard coat film in which a hard coat layer is provided on a base film is often provided.
近年來,作為如上述的顯示器,係開發能夠彎曲的顯示器亦即所謂的可撓性顯示器。可撓性顯示器係在廣潤的用途被期待,例如使其彎曲而設置在圓柱狀支柱之安置型顯示器用、或折彎或弄圓而能夠搬運之移動式顯示器用。作為可撓性顯示器用硬塗薄膜,在專利文獻1及2係提案揭示一種硬塗薄膜。
In recent years, as the above-mentioned displays, displays capable of bending, that is, so-called flexible displays have been developed. Flexible displays are expected to be widely used, for example, they are used for placement displays that are bent and placed on columnar pillars, or for mobile displays that can be transported by bending or rounding. As a hard coat film for flexible displays,
在此,可撓性顯示器,不是僅進行1次曲面成形,如專利文獻3所記載,亦有使其重複彎曲(折彎)之情況。
Here, the flexible display is not only formed into a curved surface once, but also repeatedly bent (bent) as described in
[專利文獻1]日本特許第5468167號公報 [Patent Document 1] Japanese Patent No. 5468167
[專利文獻2]日本特開2015-69197號公報 [Patent Document 2] Japanese Unexamined Patent Publication No. 2015-69197
[專利文獻3]日本特開2016-2764號公報 [Patent Document 3] Japanese Unexamined Patent Publication No. 2016-2764
但是,將先前的硬塗薄膜使用在如上述用途的可撓性顯示器時,在使其重複彎曲的部分,有產生彎曲痕跡、或白化致使外觀低落,同時作為顯示器之視認性低落之問題。 However, when the conventional hard coat film is used for the above-mentioned flexible display, there is a problem that bending marks or whitening occur in the part repeatedly bent, resulting in poor appearance and low visibility as the display.
另一方面,在硬塗薄膜,有因各種重要原因而產生干涉條紋之情形。在硬塗薄膜產生干涉條紋時,仍然有外觀低落,同時作為顯示器之視認性低落之問題。 On the other hand, in hard-coated films, interference fringes may occur due to various factors. When interference fringes are generated on the hard coat film, there is still a problem of poor appearance and low visibility as a display.
本發明係鑒於此種實際情狀而進行,其目的係提供一種具有經得起重複彎曲之耐彎曲性,同時不容易產生干涉條紋之硬塗薄膜。 The present invention is made in view of such actual situation, and its object is to provide a hard coating film which has the bending resistance to withstand repeated bending and is less likely to generate interference fringes.
為了達成上述目的,本發明第1係提供一種硬塗薄膜,其係具備基材薄膜、層積在前述基材薄膜的至少一主面側之光學調整層,及層積在前述光學調整層之與前述基材薄膜側為相反的主面側之硬塗層之硬塗薄膜,其特徵在於:前述基材薄膜為聚醯亞胺薄膜,前述光學調整層的折射率係前述聚醯亞胺薄膜的折射率與前述硬塗層的折射率之間之值,前述光學調整層的厚度為30nm以上、700nm以下(發明1)。 In order to achieve the above object, the present invention firstly provides a hard coat film comprising a base film, an optical adjustment layer laminated on at least one main surface side of the base film, and an optical adjustment layer laminated on the optical adjustment layer. A hard-coated film with a hard coat layer on the main surface side opposite to the base film side is characterized in that the base film is a polyimide film, and the refractive index of the optical adjustment layer is the same as that of the polyimide film. The value between the refractive index and the refractive index of the hard coat layer, the thickness of the optical adjustment layer is not less than 30nm and not more than 700nm (Invention 1).
上述發明(發明1)之硬塗薄膜,藉由基材薄膜為聚醯亞胺薄膜而具有優異的耐彎曲性。又,該硬塗薄膜係藉由光 學調整層的折射率及厚度為上述範圍,而不容易產生干涉條紋 The hard coat film of the above invention (Invention 1) has excellent bending resistance because the base film is a polyimide film. Also, the hard coat film is The refractive index and thickness of the optical adjustment layer are in the above range, and interference fringes are not easily generated
在上述發明(發明1),較佳是前述光學調整層的折射率為1.45以上、1.75以下(發明2)。 In the above invention (Invention 1), it is preferable that the refractive index of the optical adjustment layer is not less than 1.45 and not more than 1.75 (Invention 2).
在上述發明(發明1、2),較佳是前述硬塗層的折射率為1.40以上、1.70以下(發明3)。
In the above inventions (
在上述發明(發明1~3),較佳是前述聚醯亞胺薄膜的折射率及前述硬塗層的折射率之中央值、與前述光學調整層的折射率之差係絕對值為0.025以下(發明4)。
In the above inventions (
在上述發明(發明1~4),較佳是前述聚醯亞胺薄膜的厚度為5μm以上且300μm以下(發明5)。
In the above inventions (
在上述發明(發明1~5),較佳是前述硬塗層的厚度為0.5μm以上且10μm以下(發明6)。
In the above inventions (
在上述發明(發明1~6),較佳是前述光學調整層為含有金屬氧化物微粒子(發明7)。
In the above inventions (
在上述發明(發明1~7),較佳是前述光學調整層係由使含有活性能量線硬化性成分的組成物硬化而成之材料所形成(發明8)
In the above inventions (
在上述發明(發明1~8)之硬塗薄膜,是作為構成可撓性顯示器之可撓性構件被使用(發明9)
The hard coat film in the above inventions (
在上述發明(發明1~9),較佳是在前述基材薄膜的至少一主面側層積有黏著劑層(發明10)。
In the above inventions (
本發明之硬塗薄膜,係具有經得起重複彎曲之耐彎曲性,同時不容易產生干涉條紋。 The hard-coated film of the present invention has the bending resistance to withstand repeated bending, and is not easy to produce interference fringes.
1、1A、1B‧‧‧硬塗薄膜 1, 1A, 1B‧‧‧hard coating film
2‧‧‧基材薄膜 2‧‧‧Substrate film
3‧‧‧光學調整層 3‧‧‧Optical adjustment layer
4‧‧‧硬塗層 4‧‧‧Hard Coating
5‧‧‧黏著劑層 5‧‧‧Adhesive layer
[第1圖]本發明的一實施形態之硬塗薄膜的剖面圖。 [FIG. 1] A cross-sectional view of a hard coat film according to an embodiment of the present invention.
[第2圖]本發明的其它實施形態之硬塗薄膜的剖面圖。 [FIG. 2] A sectional view of a hard coat film according to another embodiment of the present invention.
[第3圖]本發明之另外的實施形態之硬塗薄膜的剖面圖。 [FIG. 3] A cross-sectional view of a hard coat film according to another embodiment of the present invention.
以下,說明本發明的實施形態。 Embodiments of the present invention will be described below.
第1圖係本發明的一實施形態之硬塗薄膜的剖面圖。本實施形態之硬塗薄膜1係具備基材薄膜2、層積在基材薄膜的一主面側(在第1圖為上側)之光學調整層3,及層積在光學調整層3之與基材薄膜2側為相反的主面側(在第1圖為上側)之硬塗層4而構成。
Fig. 1 is a cross-sectional view of a hard coat film according to an embodiment of the present invention. The
在上述硬塗薄膜1,基材薄膜2為聚醯亞胺薄膜。藉由基材薄膜2為聚醯亞胺薄膜,將該硬塗薄膜1應用在可撓性顯示器且進行重複彎曲時,能夠抑制在基材薄膜2產生彎曲痕跡、或白化且耐彎曲性優異。因而,使用本實施形態之硬塗薄膜1之可撓性顯示器,在預定部分使其重複彎曲時,能夠抑制在該彎曲部分之外觀低落、或視認性低落。
In the
又,光學調整層3的折射率,係聚醯亞胺薄膜的折射率與硬塗層4的折射率之間之值,且光學調整層3的厚度為30nm以上、700nm以下。亦即,在本實施形態之硬塗薄膜1,係存在有光學調整層3且該光學調整層3的折射率為聚醯亞胺薄膜的折射率與硬塗層4的折射率之間之值。藉此,基材
薄膜2的折射率與光學調整層3的折射率之差、及光學調整層3的折射率與硬塗層4的折射率之差為各自變小。藉此,能夠抑制在各界面之光線的反射,不容易與在硬塗層4的表面的反射光產生干渉。又,藉由光學調整層3的折射率為聚醯亞胺薄膜的折射率與硬塗層4的折射率之間之值,基材薄膜2的折射率與光學調整層3的折射率之折射率差、和光學調整層3的折射率與硬塗層4的折射率之折射率差之差為較小,而且光學調整層3的厚度為如上述地較薄。藉此,在基材薄膜2與光學調整層3之界面進行反射之光波,係容易和在光學調整層3與硬塗層4的界面進行反射之光波成為互相抵銷的關係。藉由該等作用,能夠抑制在硬塗薄膜1產生干涉條紋。又,在本說明書之折射率的測定波長係設為589nm,測定溫度係設為25℃。詳細的折射率的測定方法,係如後述之試驗例所揭示。
In addition, the refractive index of the
因為光學調整層3的厚度小於30nm、或大於700nm,均無法得到抑制產生上述干涉條紋之效果,所以光學調整層3的厚度係設定在上述範圍。從抑制產生干涉條紋的觀點而言,光學調整層3的厚度,係以50nm以上為佳,以80nm以上為特佳。又,光學調整層3的厚度係以600nm以下為佳,以500nm以下為特佳。
Since the thickness of the
又,同樣地,從抑制產生干涉條紋的觀點而言,聚醯亞胺薄膜的折射率與硬塗層4的折射率之中央值、和光學調整層3的折射率之差,係絕對值以0.025以下為佳,以0.01以下為特佳,進而以0為佳。藉此,基材薄膜2的折射率與光學調整層3的折射率之差、及光學調整層3的折射率與硬塗層
的折射率之差變為較小且反射光減低。與此同時,在基材薄膜2與光學調整層3的界面進行反射之光線的相位、和在光學調整層3與硬塗層4的界面進行反射之光線的相位為偏移,光波成為互相抵銷的關係,因此,能夠有效地抑制產生干涉條紋。
Again, similarly, from the viewpoint of suppressing interference fringes, the difference between the refractive index of the polyimide film and the median value of the hard coat layer 4 and the refractive index of the
(1)硬塗薄膜的構成構件 (1) Components of hard coat film
(1-1)基材薄膜 (1-1) Substrate film
本實施形態之硬塗薄膜1的基材薄膜2為聚醯亞胺薄膜,顯示器用之情況,係以透明且帶黃色較少的聚醯亞胺薄膜為佳。藉此,能夠得到顯示透明且色再現性較高的影像之顯示器(特別是可撓性顯示器)。
The
具體而言,作為在本實施形態所使用的聚醯亞胺薄膜,從透明性的觀點而言,在波長550nm之透射率係以75%以上為佳,以80%以上為較佳,以85%以上為特佳。在本說明書之透射率的測定方法,係如後述的實施例所揭示。 Specifically, as the polyimide film used in this embodiment, from the viewpoint of transparency, the transmittance at a wavelength of 550 nm is preferably 75% or more, preferably 80% or more, and 85% or more. More than % is especially good. The method for measuring the transmittance in this specification is disclosed in the examples described later.
又,作為在本實施形態所使用的聚醯亞胺薄膜,從減少帶黃色之觀點而言,使用透射測定法之L*a*b*表色系的b*之絕對值,係以10以下為佳,以5以下為較佳,以3以下為特佳。在本說明書之b*的測定方法,係如後述的實施例所揭示。 In addition, as the polyimide film used in this embodiment, the absolute value of b* in the L*a*b* colorimetric system using the transmission measurement method is 10 or less from the viewpoint of reducing yellowing. Preferably, less than 5 is more preferred, and less than 3 is particularly preferred. The measurement method of b* in this specification is as disclosed in the examples described later.
在本說明書之所謂聚醯亞胺薄膜,係指含有較佳是50質量%以上、特佳是80質量%以上、更佳是90質量%以上之聚醯亞胺、亦即在主鏈具有醯亞胺鍵的聚合物之薄膜。又,因為聚(甲基)丙烯醯亞胺不是在主鏈具有醯亞胺鍵,所以不是聚醯亞胺,使此種聚(甲基)丙烯醯亞胺薄膜重複彎曲時, 會產生白化。 The so-called polyimide film in this specification refers to polyimide containing preferably more than 50% by mass, more preferably more than 80% by mass, more preferably more than 90% by mass of polyimide, that is, the main chain has amide Thin films of imine bonded polymers. Also, since poly(meth)acrylimide does not have an imide bond in the main chain, it is not a polyimide, and when such a poly(meth)acrylimide film is bent repeatedly, Whitening will occur.
聚醯亞胺薄膜,係通常能夠使四羧酸酐(較佳為芳香族四羧酸二酐)與二胺(較佳為芳香族二胺)在溶液中聚合而生成聚醯胺酸之後,將該聚醯胺酸成形為薄膜狀,其次,藉由將聚醯胺酸部位進行脫水閉環來得到,但是不被此限定。 The polyimide film is usually able to polymerize tetracarboxylic anhydride (preferably aromatic tetracarboxylic dianhydride) and diamine (preferably aromatic diamine) in solution to generate polyamic acid, and then The polyamic acid is formed into a film, and then obtained by dehydrating and ring-closing the polyamic acid site, but it is not limited thereto.
在聚醯亞胺薄膜之聚醯亞胺亦可被改性。例如,在聚醯亞胺通常所含有的芳香環亦可被脂肪族烴改性,藉此,基材薄膜2係成為與硬塗層4具有優異的密著性者。
The polyimide in the polyimide film can also be modified. For example, the aromatic ring normally contained in polyimide may be modified by aliphatic hydrocarbon, and thereby the
作為聚醯亞胺薄膜的折射率之下限值,通常1.50以上,較佳為1.55以上,更佳為1.60以上。又,作為聚醯亞胺薄膜的折射率之上限值,通常1.85以下,較佳為1.80以下,更佳為1.75以下。 The lower limit of the refractive index of the polyimide film is usually not less than 1.50, preferably not less than 1.55, more preferably not less than 1.60. In addition, the upper limit of the refractive index of the polyimide film is usually 1.85 or less, preferably 1.80 or less, more preferably 1.75 or less.
在上述聚醯亞胺薄膜,為了提升與在其表面所設置的層(硬塗層4、或後述的黏著劑層等)的密著性之目的,能夠依照需要而藉由底漆處理、氧化法、凹凸化法等對一面或兩面施行表面處理。作為氧化法,例如可舉出電暈放電處理、鉻酸處理、火焰處理、熱風處理、臭氧.紫外線處理等,作為凹凸化法,例如可舉出噴砂處理法、溶劑處理法等。 In the above-mentioned polyimide film, in order to improve the adhesion with the layer (hard coat layer 4, or adhesive layer described later, etc.) provided on the surface, it can be treated by primer, oxidation, etc. as necessary. Surface treatment is performed on one or both sides by method, embossing method, etc. As an oxidation method, for example, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone. Ultraviolet treatment etc., as a roughening method, a blasting method, a solvent treatment method, etc. are mentioned, for example.
作為上述聚醯亞胺薄膜的厚度之下限值,係以5μm以上為佳,以7.5μm以上為特佳,進而以10μm以上為佳。藉由聚醯亞胺薄膜的厚度為上述以上,硬塗薄膜1係成為可發揮預定機械強度,即便使其重複彎曲時,亦不容易產生斷裂等。另一方面,作為上述聚醯亞胺薄膜的厚度之上限值,係以300μm以下為佳,以90μm以下為特佳,進而以50μm以
下為佳。因為聚醯亞胺薄膜容易著色,藉由聚醯亞胺薄膜的厚度為上述以下,能夠確保透明性且能夠將上述b*值抑制成為較低,而能夠適合使用作為光學用。又,聚醯亞胺薄膜的厚度為上述以下時,硬塗薄膜1係成為可發揮預定可撓性且容易使其彎曲者。
The lower limit of the thickness of the polyimide film is preferably at least 5 μm , particularly preferably at least 7.5 μm , and more preferably at least 10 μm . When the thickness of the polyimide film is more than the above, the
(1-2)光學調整層 (1-2) Optical adjustment layer
本實施形態之硬塗薄膜1的光學調整層3,係層積在基材薄膜2的一主面側(在第1圖為上側),如前述地發揮抑制產生干涉條紋之作用。
The
光學調整層3的材料,係只要光學調整層3的折射率顯示為基材薄膜2(聚醯亞胺薄膜)的折射率、與硬塗層4的折射率之間之值者,就沒有特別限定。此種光學調整層3,較佳是由含有熱可塑性樹脂之組成物所形成、或由使含有活性能量線硬化性成分之組成物硬化而成之材料所形成,任一種組成物較佳是含有金屬氧化物粒子用以調整折射率。
The material of the
在此,係在光學調整層3上形成硬塗層4,但是在該硬塗層4用塗佈液所含有的溶劑對熱可塑性樹脂為良溶劑時,光學調整層3與硬塗層4的界面變為不清楚,有產生無法抑制產生干涉條紋之不良的情形。從此種觀點而言,光學調整層3,係由使含有活性能量線硬化性成分之組成物硬化而成之材料所形成為佳,特別是以由使含有活性能量線硬化性成分及金屬氧化物粒子之組成物硬化而成之材料所形成為佳。
Here, the hard coat layer 4 is formed on the
(1-2-1)熱可塑性樹脂 (1-2-1) Thermoplastic resin
熱可塑性樹脂,係與基材薄膜2(聚醯亞胺薄膜)的密著性 及與硬塗層4密著性(熔接性)優異,因為其本身亦達成與易接著層同樣的任務,從此種觀點而言,乃是較佳。 Thermoplastic resin, adhesiveness to substrate film 2 (polyimide film) And since it is excellent in adhesion (welding property) with the hard-coat layer 4, since it also achieves the same role as an easy-adhesion layer, it is preferable from this point of view.
作為熱可塑性樹脂,較佳是藉由與金屬氧化物微粒子等的關係而能夠達成前述的折射率者。作為熱可塑性樹脂的具體例,可舉出聚酯樹脂、聚胺酯樹脂、丙烯酸系樹脂、聚烯烴系樹脂、聚氯乙烯、聚苯乙烯、聚乙烯醇、聚偏二氯乙烯(polyvinylidene chloride)等。該等之中,從與聚醯亞胺薄膜的密著性及與硬塗層4的熔接性之觀點而言,以選自聚酯樹脂、聚胺酯樹脂、丙烯酸系樹脂之至少1種為佳,以選自聚酯樹脂及聚胺酯樹脂之至少1種為較佳,以聚酯樹脂為更佳。 The thermoplastic resin is preferably one that can achieve the aforementioned refractive index due to its relationship with metal oxide fine particles or the like. Specific examples of thermoplastic resins include polyester resins, polyurethane resins, acrylic resins, polyolefin resins, polyvinyl chloride, polystyrene, polyvinyl alcohol, polyvinylidene chloride, and the like. Among these, at least one selected from the group consisting of polyester resin, polyurethane resin, and acrylic resin is preferred from the viewpoint of adhesion to the polyimide film and weldability to the hard coat layer 4, At least one selected from polyester resins and polyurethane resins is preferred, and polyester resins are more preferred.
熱可塑性樹脂的數量平均分子量,作為下限值係以1000以上為佳,以5000以上為特佳,進而以1萬以上為佳。又,熱可塑性樹脂的數量平均分子量,作為上限值係以10萬以下為佳,以7.5萬以下為特佳,進而以5萬以下為佳。藉由熱可塑性樹脂的數量平均分子量為此種範圍,有機溶劑引起熱可塑性樹脂溶解的程度變佳,藉此能夠進一步提高熱可塑性樹脂與硬塗層4之熔接性,光學調整層3與硬塗層4之密著性成為更優異者。又,在本說明書之數量平均分子量,係使用凝膠滲透層析法(GPC)法而測定之標準聚苯乙烯換算之值。
The lower limit of the number average molecular weight of the thermoplastic resin is preferably 1,000 or more, particularly preferably 5,000 or more, and further preferably 10,000 or more. Also, the upper limit of the number average molecular weight of the thermoplastic resin is preferably 100,000 or less, particularly preferably 75,000 or less, and further preferably 50,000 or less. When the number average molecular weight of the thermoplastic resin is in this range, the degree of dissolution of the thermoplastic resin by the organic solvent is improved, thereby further improving the fusion property between the thermoplastic resin and the hard coat layer 4, and the
(1-2-2)活性能量線硬化性成分 (1-2-2) Active Energy Ray Curing Ingredients
作為活性能量線硬化性成分,係以藉由照射活性能量線而硬化,而且藉由與金屬氧化物微粒子等之關係而能夠達成前述的折射率差者為佳。 The active energy ray curable component is preferably one that is cured by irradiation with active energy ray and that can achieve the above-mentioned difference in refractive index due to its relationship with metal oxide fine particles and the like.
作為具體的活性能量線硬化性成分,可舉出多官 能性(甲基)丙烯酸酯系單體、(甲基)丙烯酸酯系預聚合物、活性能量線硬化性聚合物等,尤其是以多官能性(甲基)丙烯酸酯系單體及/或(甲基)丙烯酸酯系預聚合物為佳,以多官能性(甲基)丙烯酸酯系單體為較佳。多官能性(甲基)丙烯酸酯系單體及(甲基)丙烯酸酯系預聚合物可各自單獨使用,亦可將兩者併用。又,在本說明書,所謂(甲基)丙烯酸酯,係意味著丙烯酸酯及甲基丙烯酸酯之雙方。其它類似用語亦同樣。 Examples of specific active energy ray-curing components include polyfunctional Functional (meth)acrylate monomers, (meth)acrylate prepolymers, active energy ray-curable polymers, etc., especially polyfunctional (meth)acrylate monomers and/or The (meth)acrylate-based prepolymer is preferable, and the polyfunctional (meth)acrylate-based monomer is more preferable. A polyfunctional (meth)acrylate type monomer and a (meth)acrylate type prepolymer may be used individually, respectively, and may use both together. In addition, in this specification, (meth)acrylate means both acrylate and methacrylate. The same applies to other similar expressions.
作為多官能性(甲基)丙烯酸酯系單體,例如可舉出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、羥基三甲基乙酸新戊二醇二(甲基)丙烯酸酯、二(甲基)丙烯酸二環戊酯、己內酯改性二(甲基)丙烯酸二環戊烯酯、環氧乙烷改性磷酸二(甲基)丙烯酸酯、烯丙基化二(甲基)丙烯酸環己酯、三聚異氰酸酯二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、二新戊四醇三(甲基)丙烯酸酯、丙酸改性二新戊四醇三(甲基)丙烯酸酯、新戊四醇三(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、三聚異氰酸參(丙烯醯氧基乙基)酯、丙酸改性二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、環氧乙烷改性二新戊四醇六(甲基)丙烯酸酯、己內酯改性二新戊四醇六(甲基)丙烯酸酯等的多官能性(甲基)丙烯酸酯。該等可單獨使用1種,亦可組合2種以上而使用。 Examples of polyfunctional (meth)acrylate monomers include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl Glycol di(meth)acrylate, Polyethylene glycol di(meth)acrylate, Neopentyl glycol di(meth)acrylate, Dicyclopentyl di(meth)acrylate, Caprolactone modified dicyclopentenyl di(meth)acrylate, Ethylene oxide modified phosphate di(meth)acrylate, Allylated di(meth)acrylate cyclohexyl, Trimeric isocyanate di (meth)acrylate, trimethylolpropane tri(meth)acrylate, diperythritol tri(meth)acrylate, propionic acid-modified dipenteoerythritol tri(meth)acrylate, Neopentylthritol tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, isocyanuric acid ginseng (acryloxyethyl) ester, propionic acid modified Di-Neopentylthritol Penta(Meth)acrylate, Di-Neopentylthritol Hexa(Meth)acrylate, Ethylene Oxide-modified Di-Neopentyl-Ritol Hexa(meth)acrylate, Caprolactone-modified Polyfunctional (meth)acrylates such as diperythritol hexa(meth)acrylate. These may be used individually by 1 type, and may use it in combination of 2 or more types.
上述之中,從薄膜的硬化性之觀點而言,以在1分子中具有3個以上的(甲基)丙烯醯基之多官能性(甲基)丙烯
酸酯系單體為佳,以在1分子中具有4個以上的(甲基)丙烯醯基之多官能性(甲基)丙烯酸酯系單體為特佳。藉由使用此種多官能性(甲基)丙烯酸酯系單體,因為所得到的光學調整層3係充分地硬化,所以隨後形成硬塗層4形成時,不會被稀釋溶劑等侵蝕。因此,能夠防止在光學調整層3與硬塗層4的界面之折射率梯度變為平緩。其結果,能夠更有效地防止因光學調整層3引起光線的干渉作用致使硬塗層4表面產生干涉條紋。又,多官能性(甲基)丙烯酸酯系單體的官能基數的上限係沒有特別限制,從與聚醯亞胺薄膜的密著性之觀點而言,在1分子中以含有20個以下的(甲基)丙烯醯基為佳。
Among the above, polyfunctional (meth)acrylic acid having three or more (meth)acryloyl groups in one molecule is used from the viewpoint of film curability.
The ester-based monomer is preferable, and a polyfunctional (meth)acrylate-based monomer having four or more (meth)acryl groups in one molecule is particularly preferable. By using such a polyfunctional (meth)acrylate monomer, the obtained
又,從容易調整光學調整層3的折射率,不產生著色等之觀點而言,係以使用脂肪族系的多官能性(甲基)丙烯酸酯系單體為特佳。
In addition, from the viewpoint of easy adjustment of the refractive index of the
另一方面,作為(甲基)丙烯酸酯系預聚合物,例如可舉出聚酯丙烯酸酯系、環氧丙烯酸酯系、胺甲酸乙酯丙烯酸酯系、多元醇丙烯酸酯系等的預聚合物。 On the other hand, examples of (meth)acrylate-based prepolymers include prepolymers such as polyester acrylate, epoxy acrylate, urethane acrylate, and polyol acrylate. .
作為聚酯丙烯酸酯系預聚合物,例如能夠將多元羧酸與多元醇藉由縮合而得到之在兩末端具有羥基之聚酯寡聚物的羥基,藉由使用(甲基)丙烯酸進行酯化,或是將環氧烷(alkylene oxide)附加在多元羧酸而得到的寡聚物的末端之羥基,藉由使用(甲基)丙烯酸進行酯化來得到。 As a polyester acrylate prepolymer, for example, the hydroxyl groups of polyester oligomers having hydroxyl groups at both ends obtained by condensation of polycarboxylic acids and polyhydric alcohols can be esterified with (meth)acrylic acid. , or by adding alkylene oxide (alkylene oxide) to the terminal hydroxyl group of the oligomer obtained by adding polycarboxylic acid, and obtaining it by esterifying it with (meth)acrylic acid.
環氧丙烯酸酯系預聚合物,係例如能夠藉由使(甲基)丙烯酸對分子量較低的雙酚型環氧樹脂、或酚醛清漆型環氧樹脂等的環氧乙烷環進行反應而酯化來得到。 Epoxy acrylate-based prepolymers can be esterified, for example, by reacting (meth)acrylic acid with the oxirane rings of bisphenol-type epoxy resins or novolak-type epoxy resins with low molecular weights. to get.
胺甲酸乙酯丙烯酸酯系預聚合物,係例如能夠將聚醚多元醇、或聚酯多元醇等與聚異氰酸酯藉由反應而得到的聚胺酯寡聚物,藉由使用(甲基)丙烯酸進行酯化來得到。 The urethane acrylate prepolymer is, for example, a polyurethane oligomer obtained by reacting polyether polyol or polyester polyol with polyisocyanate, by using (meth)acrylic acid to perform esterification to get.
多元醇丙烯酸酯系預聚合物,係例如能夠將聚醚多元醇的羥基,藉由使用(甲基)丙烯酸進行酯化來得到。 The polyol acrylate prepolymer can be obtained, for example, by esterifying the hydroxyl group of polyether polyol using (meth)acrylic acid.
以上的預聚合物可單獨使用1種,亦可組合2種以上而使用。 The above prepolymers may be used alone or in combination of two or more.
(1-2-3)光聚合起始劑 (1-2-3) Photopolymerization initiator
在光學調整層3係由使含有活性能量線硬化性成分的組成物硬化而成的材料所形成之情況,使用紫外線作為活性能量線時,該組成物係以含有光聚合起始劑為佳。藉由如此地含有光聚合起始劑,能夠使活性能量線硬化性成分效率良好地聚合,而且能夠減少聚合硬化時間及紫外線的照射量。
When the
作為此種光聚合起始劑,例如可舉出苯偶姻、苯偶姻甲醚、苯偶姻***、苯偶姻異丙醚、苯偶姻-正丁醚、苯偶姻異丁醚、苯乙酮、二甲胺基苯乙酮、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-丙烷-1-酮、4-(2-羥基乙氧基)苯基-2-(羥基-2-丙基)酮、二苯基酮、對苯基二苯基酮、4,4’-二乙胺基二苯基酮、二氯二苯基酮、2-甲基蒽醌、2-乙基蒽醌、2-第三丁基蒽醌、2-胺基蒽醌、2-甲基9-氧硫、2-乙基9-氧硫、2-氯9-氧硫、2,4-二甲基9-氧硫、2,4-二乙基9-氧硫、苄基二甲縮酮、苯乙酮二甲縮酮、對二甲胺基苯甲酸酯、寡聚[2-羥基-2- 甲基-1[4-(1-甲基乙烯基)苯基]丙酮]、2,4,6-三甲基苯甲醯基-二苯基-氧化膦等。該等可單獨使用,亦可組合2種以上而使用。 Examples of such photopolymerization initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, Acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy- 2-Methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholine-propane- 1-keto, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylamine Diphenyl ketone, dichlorodiphenyl ketone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methyl 9-oxygen sulfur , 2-Ethyl 9-oxosulfur , 2-chloro 9-oxysulfur , 2,4-Dimethyl 9-oxosulfur , 2,4-Diethyl 9-oxosulfur , benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoate, oligo[2-hydroxy-2-methyl-1[4-(1-methylvinyl) phenyl] acetone], 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, etc. These may be used individually or in combination of 2 or more types.
在組成物中之光聚合起始劑的含量,相對於活性能量線硬化性成分100質量份,下限值係以0.01質量份以上為佳,以0.1質量份以上為特佳,進而以1質量份以上為佳。又,上限值係以20質量份以下為佳,以10質量份以下為特佳,進而以5質量份以下為佳。 The lower limit of the content of the photopolymerization initiator in the composition is preferably 0.01 part by mass or more, particularly preferably 0.1 part by mass or more, and furthermore, 1 part by mass relative to 100 parts by mass of the active energy ray-curing component. More than one serving is better. Moreover, the upper limit is preferably at most 20 parts by mass, particularly preferably at most 10 parts by mass, and further preferably at most 5 parts by mass.
(1-2-4)金屬氧化物微粒子 (1-2-4) Metal oxide fine particles
構成光學調整層3之組成物,係以含有金屬氧化物微粒子為佳。藉此,能夠容易地將光學調整層3的折射率設定為聚醯亞胺薄膜的折射率與硬塗層4的折射率之間之值。
The composition constituting the
作為金屬氧化物微粒子,例如可舉出氧化鈦、氧化鋯、氧化鉭、氧化鋅、氧化銦、氧化鉿、氧化鈰、氧化錫、氧化鈮、錫摻雜氧化銦(ITO)、銻摻雜氧化錫(ATO)等的微粒子,尤其是以氧化鈦、氧化鋯、氧化鉭、氧化鋅、氧化鉿、氧化鈰、氧化鈮等的過渡金屬氧化物微粒子為佳。該等金屬氧化物微粒子可單獨使用1種,亦可組合2種以上而使用。 Examples of metal oxide fine particles include titanium oxide, zirconium oxide, tantalum oxide, zinc oxide, indium oxide, hafnium oxide, cerium oxide, tin oxide, niobium oxide, tin-doped indium oxide (ITO), antimony-doped oxide Fine particles such as tin (ATO), especially transition metal oxide fine particles such as titanium oxide, zirconium oxide, tantalum oxide, zinc oxide, hafnium oxide, cerium oxide, and niobium oxide, are preferable. These metal oxide fine particles may be used alone or in combination of two or more.
上述之中,能夠對光學調整層3賦予較高的折射率,同時不容易使光學調整層3的霧度提升,以第4族元素的氧化物微粒子,具體而言係以氧化鋯微粒子及氧化鈦微粒子為特佳。氧化鈦微粒子的結晶構造係沒有特別限定,以金紅石(rutile)型為佳。藉由金紅石型,能夠抑制因光觸媒活性引起光學調整層3經時劣化。
Among the above, a higher refractive index can be imparted to the
氧化鋯微粒子及氧化鈦微粒子亦可為經表面處理者。例如可被鋁、矽等的氧化物覆蓋,亦可被有機化合物改性。作為有機化合物,例如可舉出多元醇、烷醇胺、硬脂酸、矽烷偶合劑、鈦酸鹽偶合劑。藉由此種表面處理,能夠使分散性等提升且能夠使上述的效果更優異。 Zirconia fine particles and titanium oxide fine particles may be surface-treated. For example, it can be covered with oxides such as aluminum and silicon, and can also be modified by organic compounds. Examples of organic compounds include polyhydric alcohols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. By such a surface treatment, the dispersibility and the like can be improved, and the above-mentioned effects can be made more excellent.
金屬氧化物微粒子的形狀,可為球狀,亦可為非球狀。 The shape of the metal oxide fine particles may be spherical or non-spherical.
作為金屬氧化物微粒子的平均粒徑之下限值,係以1nm以上為佳,以3nm以上為特佳,進而以5nm以上為佳。藉由金屬氧化物微粒子的平均粒徑為1nm以上,分散性提升。又,作為金屬氧化物微粒子的平均粒徑之上限值,係以500nm以下為佳,以200nm以下為特佳,進而以50nm以下為佳。藉由金屬氧化物微粒子的平均粒徑為500nm以下,在所得到的光學調整層3,不容易產生光線散射,光學調整層3的透明性變高。又,金屬氧化物微粒子的平均粒徑,係設為藉由Z電位(Zeta-potential)測定法而測定的一次粒徑。
The lower limit of the average particle diameter of the metal oxide fine particles is preferably at least 1 nm, particularly preferably at least 3 nm, and further preferably at least 5 nm. When the average particle diameter of the metal oxide fine particles is 1 nm or more, the dispersibility is improved. Also, the upper limit of the average particle diameter of the metal oxide fine particles is preferably at most 500 nm, particularly preferably at most 200 nm, and further preferably at most 50 nm. When the average particle diameter of the metal oxide fine particles is 500 nm or less, light scattering is less likely to occur in the obtained
在本實施形態的光學調整層3之金屬氧化物微粒子的含量,在光學調整層3,作為下限值以15質量%以上為佳,以20質量%以上為特佳,進而以25質量%以上為佳。藉由金屬氧化物微粒子的含量為15質量%以上,使光學調整層3的折射率,容易設定為聚醯亞胺薄膜的折射率與硬塗層4的折射率之間之值。另一方面,金屬氧化物微粒子的含量,在光學調整層3,作為上限值以80質量%以下為佳,以70質量%以下為佳,進而以60質量%以下為佳。藉由金屬氧化物微粒子的含量為
80質量%以下,與上述同樣地使光學調整層3的折射率容易設定為聚醯亞胺薄膜的折射率與硬塗層4的折射率之間之值,同時,容易形成使用硬塗層用組成物而成之層。
In the
在此,金屬氧化物微粒子的含量係能夠從調配比率來求取,調配比率不清楚時,係能夠如以下地求取。亦即,將硬塗薄膜1的光學調整層3之一部分從基材薄膜2以斷片等的方式分離,將分離後的光學調整層3之斷片依照JIS 7250-1而燃燒有機成分。接著,能夠從所得到的灰分求取金屬氧化物微粒子的質量%。
Here, the content of the metal oxide fine particles can be obtained from the compounding ratio, and when the compounding ratio is unclear, it can be obtained as follows. That is, a part of the
又,光學調整層3的折射率,亦能夠只藉由活性能量線硬化性成分的折射率來調整,此時,不需要添加金屬氧化物微粒子。作為折射率較高的活性能量線硬化性成分,例如可舉出酚醛清漆型環氧樹脂等。但是,因為折射率之微妙的調整,係能夠藉由添加金屬氧化物微粒子而容易地進行,從此種觀點而言,亦以使用金屬氧化物微粒子為佳。
In addition, the refractive index of the
為了使組成物中之金屬氧化物微粒子的分散性提升,亦可使用分散劑。作為分散劑,從與熱可塑性樹脂或活性能量線硬化性成分的相溶性之觀點而言,係以丙烯酸系樹脂為佳。 In order to improve the dispersibility of the metal oxide fine particles in the composition, a dispersant may also be used. As the dispersant, an acrylic resin is preferable from the viewpoint of compatibility with a thermoplastic resin or an active energy ray-curable component.
(1-2-5)其它成分 (1-2-5) Other ingredients
構成本實施形態的光學調整層3之組成物,係除了前述的成分以外,亦可含有各種添加劑。作為各種添加劑,例如可舉出紫外線吸收劑、抗氧化劑、光安定劑、抗靜電劑、矽烷偶合劑、防止老化劑、熱聚合抑制劑、著色劑、界面活性劑、保存
安定劑、可塑劑、滑劑、消泡劑、有機系填充材、濕潤性改良劑、塗面改良劑等。
The composition constituting the
(1-2-6)物性 (1-2-6) Physical properties
光學調整層3的折射率之下限值,係以1.45以上為佳,以1.47以上為特佳,進而以1.50以上為佳。又,光學調整層3的折射率之上限值,係以1.75以下為佳,以1.72以下為特佳,進而以1.70以下為佳。藉由光學調整層3的折射率為上述範圍,容易成為聚醯亞胺薄膜的折射率與硬塗層4的折射率之間之值。
The lower limit of the refractive index of the
(1-3)硬塗層 (1-3) Hard coating
本實施形態的硬塗薄膜1之硬塗層4,係對硬塗薄膜1賦予較高的表面硬度,成為具有優異的耐擦傷性者。該硬塗層4,係只要光學調整層3的折射率與基材薄膜2(聚醯亞胺薄膜)的折射率滿足前述的關係,具有預定硬度者,就沒有特別限定。此種硬塗層4,係由使含有活性能量線硬化性成分的組成物硬化而成之材料所形成為佳。
The hard-coat layer 4 of the hard-
作為活性能量線硬化性成分,係能夠使用與在光學調整層3所使用的前述活性能量線硬化性成分同樣者。尤其是從耐擦傷性的觀點而言,係以使用3官能以上的多官能(甲基)丙烯酸酯系單體為佳,以使用4官能以上的多官能(甲基)丙烯酸酯系單體為較佳。例如能夠適合舉出二新戊四醇六(甲基)丙烯酸酯等。
As the active energy ray curable component, the same one as the above-mentioned active energy ray curable component used in the
而且,考量使所得到的硬塗薄膜1成為具有更優異的耐彎曲性之觀點時,併用在分子內含有碳數2~4的環氧烷
(alkylene oxide)單元之多官能(甲基)丙烯酸酯系單體(以下,有稱為「含環氧烷鏈的多官能丙烯酸酯」之情形)為佳。
In addition, when considering the viewpoint of making the obtained
使用含環氧烷鏈的多官能丙烯酸酯時,從發揮耐彎曲性改善效果之觀點而言,相對於活性能量線硬化性成分全體,含環氧烷鏈的多官能丙烯酸酯之含量係以10質量%以上為佳,以20質量%以上為較佳,以40質量%以上為特佳。另一方面,從確保耐擦傷性的觀點而言,該含量係以90質量%以下為佳,以80質量%以下為較佳,以70質量%以下為特佳。 When using a polyfunctional acrylate containing an alkylene oxide chain, from the viewpoint of exhibiting the effect of improving bending resistance, the content of the polyfunctional acrylate containing an alkylene oxide chain is 10% relative to the entire active energy ray-curable component. It is preferably at least 20% by mass, more preferably at least 20% by mass, and particularly preferably at least 40% by mass. On the other hand, from the viewpoint of ensuring scratch resistance, the content is preferably at most 90% by mass, more preferably at most 80% by mass, and particularly preferably at most 70% by mass.
又,含環氧烷鏈的多官能丙烯酸酯,係從使耐彎曲性的改善效果發揮之觀點而言,以在分子中含有1莫耳以上的環氧烷單元為佳,以含有5莫耳以上為較佳,以含有9莫耳以上為特佳。另一方面,考慮與併用的其它活性能量線硬化性成分之相溶性時,含環氧烷鏈的多官能丙烯酸酯,係以在分子中含有30莫耳以下的環氧烷單元為佳,以含有20莫耳以下為較佳,以含有15莫耳以下為特佳。作為此種含環氧烷鏈的多官能丙烯酸酯,例如可適合舉出環氧乙烷改性二新戊四醇六(甲基)丙烯酸酯等。 In addition, the polyfunctional acrylate containing an alkylene oxide chain, from the viewpoint of improving the bending resistance, preferably contains more than 1 mole of alkylene oxide units in the molecule, and preferably contains 5 moles of alkylene oxide units. The above is preferred, and it is particularly preferred to contain more than 9 moles. On the other hand, when considering the compatibility with other active energy ray-curing components used in combination, the multifunctional acrylate containing alkylene oxide chains preferably contains 30 moles or less of alkylene oxide units in the molecule. It is preferable to contain 20 moles or less, and it is especially preferable to contain 15 moles or less. As such an alkylene oxide chain-containing polyfunctional acrylate, ethylene oxide-modified dipenteoerythritol hexa(meth)acrylate etc. are suitably mentioned, for example.
為了使活性能量線硬化性成分硬化而使用紫外線作為照射的活性能量線時,上述組成物係以含有光聚合起始劑為佳。作為光聚合起始劑,能夠使用與在光學調整層3所使用的前述光聚合起始劑的同樣物。
When ultraviolet rays are used as active energy rays to be irradiated in order to cure the active energy ray-curable component, it is preferable that the above-mentioned composition contains a photopolymerization initiator. As the photopolymerization initiator, the same thing as the aforementioned photopolymerization initiator used in the
在本實施形態之硬塗層4,亦可含有填料。因此,藉由硬塗層4而能夠賦予較高的表面硬度,能夠成為具有更優異的耐擦傷性者。 The hard coat layer 4 of this embodiment may also contain a filler. Therefore, high surface hardness can be imparted by the hard-coat layer 4, and it can become what has more excellent scratch resistance.
作為填料,係有機系填料、無機系填料的任一者均可,從能夠對硬塗層4賦予較高的表面硬度之觀點而言,係以使用無機系填料為佳,特別是以使用被有機化合物化學改性而成之無機系填料為佳,其中該有機化合物係具有藉由活性能量線照射而聚合之聚合性官能基。又,填料係能夠單獨1種或組合或2種以上而使用。 As the filler, either an organic filler or an inorganic filler may be used. From the viewpoint of being able to impart high surface hardness to the hard coat layer 4, it is preferable to use an inorganic filler. An inorganic filler obtained by chemically modifying an organic compound is preferred, wherein the organic compound has a polymerizable functional group that can be polymerized by irradiation of active energy rays. Moreover, a filler system can be used individually by 1 type, in combination, or 2 or more types.
作為無機填料,例如可舉出由氧化矽、氧化鋁、氧化鋯、氧化鈦、氧化鋅、氧化鍺、氧化銦、氧化錫、銦錫氧化物(ITO)、氧化銻、氧化鈰等的金屬氧化物;氟化鎂、氟化鈉等的金屬氟化物等所形成之填料。上述之中,就對光學特性的影響較少而言,以氧化矽及氧化鋁為佳,以氧化矽為特佳。 Examples of inorganic fillers include metal oxides made of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, and cerium oxide. substances; fillers formed by metal fluorides such as magnesium fluoride and sodium fluoride. Among the above, silicon oxide and aluminum oxide are preferable, and silicon oxide is particularly preferable in terms of less influence on optical properties.
填料、特別是氧化矽填料表面亦可被化學改性,特別是以被有機化合物化學改性為佳,其中該有機化合物係具有藉由活性能量線照射而聚合之聚合性官能基。化學改性的具體結構係沒有限定,作為一個例子,可舉出透過矽烷偶合劑等而附加有聚合性官能基之結構。此種結構時,藉由活性能量線照射,填料與活性能量線硬化性成分係化學鍵結,而且在該等兩者間不容易產生剝離,硬塗層4的硬度容易成為較高。將如此地被具有聚合性官能基之有機化合物化學改性而成之填料稱為反應性填料,例如只要填料的種類為氧化矽,就能夠稱為反應性氧化矽填料。 The surface of fillers, especially silicon oxide fillers, can also be chemically modified, especially chemically modified by organic compounds, wherein the organic compounds have polymerizable functional groups that can be polymerized by irradiation of active energy rays. The specific structure of the chemical modification is not limited, but one example includes a structure in which a polymerizable functional group is added through a silane coupling agent or the like. In such a structure, the filler and the active energy ray curable component are chemically bonded by irradiation of active energy rays, and peeling between them is less likely to occur, and the hardness of the hard coat layer 4 tends to be higher. A filler chemically modified by an organic compound having a polymerizable functional group in this way is called a reactive filler. For example, as long as the type of the filler is silicon oxide, it can be called a reactive silica filler.
填料的形狀可為球狀,亦可為非球狀。非球狀時,可為不定形,亦可為針狀、鱗片狀之縱橫比較高的形狀。從確保硬塗層4的透明性之觀點而言,填料係以球狀為佳。 The shape of the filler may be spherical or non-spherical. In the case of a non-spherical shape, it may be indeterminate, or may be a needle-like or scaly shape with a high aspect ratio. From the viewpoint of securing the transparency of the hard coat layer 4, the filler is preferably spherical.
填料的平均粒徑之下限值,係以1nm以上為佳,以3nm以上為特佳,進而以5nm以上為佳。藉由填料的平均粒徑為1nm以上,分散性提升。又,填料的平均粒徑之上限值,係以500nm以下為佳、以200nm以下為特佳,進而以50nm以下為佳。藉由填料的平均粒徑為500nm以下,在所得到的硬塗層4光線不容易產生散射,硬塗層4的透明性變高。又,填料的平均粒徑係設為藉由Z電位測定法測定一次粒徑。 The lower limit of the average particle size of the filler is preferably above 1 nm, particularly preferably above 3 nm, and more preferably above 5 nm. When the average particle diameter of the filler is 1 nm or more, the dispersibility is improved. Also, the upper limit of the average particle diameter of the filler is preferably at most 500 nm, particularly preferably at most 200 nm, and further preferably at most 50 nm. When the average particle diameter of the filler is 500 nm or less, it is difficult for light to scatter in the hard coat layer 4 obtained, and the transparency of the hard coat layer 4 becomes high. In addition, the average particle diameter of a filler is set as the primary particle diameter measured by the zeta potential measurement method.
本實施形態的硬塗層4係含有填料時,其含量之下限值,係以10質量%以上為佳,以20質量%以上為特佳,進而以40質量%以上為佳。藉由填料的含量為10質量%以上,能夠有效地提升硬塗層4的硬度。另一方面,在硬塗層4,填料的含量之上限值係以90質量%以下為佳,以80質量%以下為特佳,進而以70質量%以下為佳。藉由填料的含量為90質量%以下,而容易形成層。 When the hard coat layer 4 of this embodiment contains fillers, the lower limit of the content is preferably at least 10% by mass, particularly preferably at least 20% by mass, and more preferably at least 40% by mass. When the content of the filler is 10% by mass or more, the hardness of the hard coat layer 4 can be effectively increased. On the other hand, in the hard coat layer 4, the upper limit of the content of the filler is preferably not more than 90% by mass, particularly preferably not more than 80% by mass, and further preferably not more than 70% by mass. When content of a filler is 90 mass % or less, it becomes easy to form a layer.
本實施形態的硬塗層4,係除了前述的成分以外,亦可含有與在前述的光學調整層3所使用的各種添加劑同樣的各種添加劑。
The hard coat layer 4 of the present embodiment may contain various additives similar to those used in the
硬塗層4的折射率之下限值,係以1.40以上為佳,以1.43以上為特佳,進而以1.45以上為佳。又,硬塗層4的折射率之上限值,係以1.70以下為佳,以1.65以下為佳、進而1.60以下為佳,以1.54以下為最佳。藉由硬塗層4的折射率為上述範圍,能夠減小硬塗層4的折射率與光學調整層3的折射率之差、進而減小光學調整層3的折射率與聚醯亞胺薄膜的折射率之差,而且能夠有效地抑制產生干涉條紋。
The lower limit of the refractive index of the hard coat layer 4 is preferably at least 1.40, particularly preferably at least 1.43, and more preferably at least 1.45. In addition, the upper limit of the refractive index of the hard coat layer 4 is preferably not more than 1.70, more preferably not more than 1.65, more preferably not more than 1.60, most preferably not more than 1.54. With the refractive index of the hard coat layer 4 within the above range, the difference between the refractive index of the hard coat layer 4 and the refractive index of the
硬塗層4的厚度之下限值,係以0.5μm以上為佳,以0.75μm以上為佳,進而以1μm以上為佳。又,硬塗層4的厚度之上限值,係以10μm以下為佳,以8μm以下為特佳,進而以4μm以下為佳。硬塗層4的厚度為0.5μm以上時,硬塗層4的耐擦傷性係成為更優異者。另一方面,硬塗層4的厚度為10μm以下時,硬塗薄膜1係成為容易彎曲者且成為具有更優異的耐彎曲性者。
The lower limit of the thickness of the hard coat layer 4 is preferably at least 0.5 μm , more preferably at least 0.75 μm , and more preferably at least 1 μm . In addition, the upper limit of the thickness of the hard coat layer 4 is preferably not more than 10 μm , more preferably not more than 8 μm , and more preferably not more than 4 μm . When the thickness of the hard coat layer 4 is 0.5 μm or more, the scratch resistance of the hard coat layer 4 becomes more excellent. On the other hand, when the thickness of the hard coat layer 4 is 10 μm or less, the
(2)硬塗薄膜的製造方法 (2) Manufacturing method of hard coat film
本實施形態之硬塗薄膜1,係能夠適合使用以下的方法來製造。又,在本方法,作為一個例子,係設為使用含有活性能量線硬化性成分的組成物來形成硬塗層4。
The
首先,調製含有構成光學調整層3的組成物(光學調整層3用組成物)、以及依照需要的溶劑之光學調整層3用組成物的塗佈液。又,同樣地,調製含有構成硬塗層4的組成物(硬塗層4用組成物)、以及依照需要的溶劑之硬塗層4用組成物的塗佈液。
First, a coating solution of the composition for the
作為溶劑,例如可舉出己烷、庚烷等的脂肪族烴、甲苯、二甲苯等的芳香族烴、二氯甲烷、二氯乙烷等的鹵化烴、甲醇、乙醇、丙醇、丁醇、丙二醇一甲醚等的醇類、丙酮、甲基乙基酮、甲基異丁基酮、2-戊酮、異佛爾酮、環己酮等的酮、乙酸乙酯、乙酸丁酯等的酯、乙基賽路蘇等的賽路蘇系溶劑等。溶劑可以只使用1種類,亦可混合2種類以上而使用。塗佈液的濃度.黏度係能夠塗佈的範圍即可,而沒有特別限制,能夠按照狀況而適當地選定。
Examples of solvents include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride and ethylene dichloride, methanol, ethanol, propanol, and butanol. , alcohols such as propylene glycol monomethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-pentanone, isophorone, cyclohexanone and other ketones, ethyl acetate, butyl acetate, etc. Celuso-based solvents such as esters, ethyl celuso, etc. A solvent may be used only by 1 type, and may mix and
在基材薄膜2的一面,塗佈上述光學調整層3用組成物的塗佈液且使其乾燥。光學調整層3係由含有熱可塑性樹脂之組成物所形成時,係在此時點形成光學調整層3。另一方面,光學調整層3係由含有活性能量線硬化性成分之組成物所形成時,係與含有熱可塑性樹脂的組成物時同樣地進行塗佈且乾燥,而且照射活性能量線。藉由照射活性能量線,光學調整層3用組成物的塗膜硬化,形成光學調整層3。
On one side of the
接著,將上述硬塗層4用組成物的塗佈液塗佈在其光學調整層3上,使其乾燥之後,照射活性能量線。藉由照射活性能量線,硬塗層4用組成物的塗膜硬化,在光學調整層3之與基材薄膜2接觸側為相反側形成硬塗層4。
Next, the above-mentioned coating liquid of the composition for the hard coat layer 4 is applied on the
塗佈液的塗佈,係使用常用方法進行即可,例如使用棒塗佈法、刮刀塗佈法、繞線棒法、輥塗佈法、刮板塗佈法、模塗佈法、凹版塗佈法而進行即可。塗膜的乾燥,係例如能夠藉由在40~180℃加熱30秒~5分鐘左右而進行。 Coating of the coating liquid may be carried out by a common method, for example, bar coating, knife coating, wire wound rod, roll coating, blade coating, die coating, gravure coating, etc. It can be carried out according to the cloth method. Drying of the coating film can be performed, for example, by heating at 40 to 180° C. for about 30 seconds to 5 minutes.
作為活性能量線,係能夠使用紫外線、電子射線等。紫外線照射係能夠使用高壓水銀燈、光固化H燈(Fusion H lamp)、氙燈等而進行,紫外線的照射量,係以照度50~1000mW/cm2、光量50~1000mJ/cm2左右為佳。另一方面,電子射線照射係能夠使用電子射線加速器等而進行,電子射線的照射量係以10~1000krad左右為佳。 As the active energy rays, ultraviolet rays, electron rays, and the like can be used. Ultraviolet irradiation can be carried out using high-pressure mercury lamps, Fusion H lamps, xenon lamps, etc. The irradiation amount of ultraviolet rays is preferably about 50~1000mW/cm 2 illuminance and 50~1000mJ/cm 2 light intensity. On the other hand, electron beam irradiation can be performed using an electron beam accelerator or the like, and the irradiation dose of electron beam is preferably about 10 to 1000 krad.
又,使用紫外線作為活性能量線時,硬塗層4用組成物的塗膜係以在從氧氣隔離的狀態下照射紫外線為佳。藉此,不會遭受氧氣引起的硬化阻礙,而有效地形成表面硬度較 高的硬塗層4。 Also, when ultraviolet rays are used as the active energy rays, it is preferable to irradiate the coating film of the composition for the hard coat layer 4 with ultraviolet rays in a state shielded from oxygen. In this way, it will not be hindered by hardening caused by oxygen, and the surface hardness is effectively formed. High hard coating4.
使上述硬塗層4組成物的塗膜從氧氣隔離,較佳是將覆蓋薄片層積在上述塗膜、或保持在氧氣濃度較低的環境下、例如氮氣環境下。 To isolate the coating film of the composition of the hard coat layer 4 from oxygen, it is preferable to laminate a cover sheet on the coating film or keep it in an environment with a low oxygen concentration, such as a nitrogen atmosphere.
(3)硬塗薄膜的物性 (3) Physical properties of hard coat film
(3-1)最大反射率差 (3-1) Maximum reflectance difference
如前述,在本實施形態之硬塗薄膜1,係能夠抑制產生干涉條紋。該情形係除了藉由目視而進行評價以外,亦能夠藉由最大反射率差之測定值來判定。測定最大反射率差,係首先將薄膜法線方向設為0°,從入射角8°方向照射光線,藉由積分球將該反射後的光線聚光且以反射光的方式檢測。又,光的照射係使波長變化而進行,來檢測對應各自的波長之反射光。
As mentioned above, in the
反射光,係設為將硫酸鋇結晶所產生的反射光作為100之相對值(以下,將其稱為「反射率」),且對應各測定波長而檢測。亦即,能夠得到橫軸為測定波長,縱軸為反射率之圖表。該圖表係通常成為具有複數個極小值及極大值之起伏的形狀。 The reflected light is a relative value (hereinafter referred to as "reflectance") with the reflected light by the barium sulfate crystal as 100, and is detected corresponding to each measurement wavelength. That is, it is possible to obtain a graph in which the horizontal axis represents the measurement wavelength and the vertical axis represents the reflectance. The graph usually has a fluctuating shape with a plurality of minima and maxima.
在此,在測定波長500~600nm之反射率的圖表,隣接極大值與極小值之差之中,測定最大的差作為「最大反射率差」。該最大反射率差係以1.5以下為佳,以1.1以下為特佳。藉由反射率為1.5以下,而能夠抑制產生干涉條紋。 Here, among the differences between the adjacent maximum value and the minimum value in the graph of the reflectance measured at a wavelength of 500 to 600 nm, the largest difference was measured as the "maximum reflectance difference". The maximum reflectance difference is preferably 1.5 or less, particularly preferably 1.1 or less. When the reflectance is 1.5 or less, generation of interference fringes can be suppressed.
(3-2)最小心軸直徑 (3-2) Minimum mandrel diameter
如前述,在本實施形態之硬塗薄膜1,係經得起重複彎曲之耐彎曲性為優異者,針對其彎曲的程度,係能夠依照最小心
軸直徑而判斷。
As mentioned above, in the
本實施形態之硬塗薄膜1,係在依據JIS K5600-5-1之圓筒形心軸法之耐彎曲性試驗,在硬塗層4不產生龜裂和剝落之心軸中,直徑為最小的心軸直徑(最小心軸直徑),係以14mm以下為佳,以6mm以下為特佳,進而以4mm以下為佳。
The
(3-3)影像鮮明度 (3-3) Image sharpness
本實施形態之硬塗薄膜1,其防止干涉條紋,不是添加微小等級的微粒子,而是藉由設置具有預定折射率之光學調整層3來解決。因此,相較於藉由添加微小等級的微粒子來防止干涉條紋之情況,本實施形態之硬塗薄膜1係能夠成為具有更優異的影像鮮明度之薄膜。
In the
將具有優異的影像鮮明度之硬塗薄膜應用在顯示器時,能夠得到顯示具有優異的對比之影像之顯示器。從此種觀點而言,影像鮮明度係以400%以上為佳,以430%以上為較佳,以450%以上為特佳。 When a hard coat film having excellent image clarity is applied to a display, a display displaying an image having excellent contrast can be obtained. From this point of view, the image sharpness is preferably above 400%, preferably above 430%, and particularly preferably above 450%.
又,影像鮮明度係能夠依據JIS K7374,設為在5種類的狹縫(狹縫寬度:0.125mm、0.25mm、0.5mm、1mm及2mm)所測定的各影像鮮明度之合計值而求取。 In addition, the image sharpness can be calculated as the total value of each image sharpness measured in 5 types of slits (slit width: 0.125mm, 0.25mm, 0.5mm, 1mm, and 2mm) according to JIS K7374 .
(3-4)霧度值 (3-4) Haze value
應用在顯示器時,從顯示更鮮明的影像之觀點而言,以將依據JIS K7136而測定的硬塗薄膜1之霧度值設為1%以下為佳,以設為0.8%以下為較佳,以設為0.5%以下為特佳。
When applied to a display, from the viewpoint of displaying a clearer image, the haze value of the
(3-5)60°光澤度 (3-5)60°gloss
應用在顯示器時,從使其顯示更鮮明的影像之觀點而言,
在硬塗薄膜1之硬塗層4,係以將其依據JIS Z8741-1997之60°光澤度(Gloss值)設為100%以上之值為佳,以設為120%以上之值為較佳,以設為140%以上之值為特佳。
When applied to a display, from the viewpoint of making it display a more vivid image,
In the hard coat layer 4 of the
(4)其它實施形態-1 (4) Other Embodiments-1
在上述硬塗薄膜1之基材薄膜2的另一主面側(與層積有上述的光學調整層3及硬塗層4之面為相反側之面側),係如第2圖顯示,亦可與硬塗薄膜1相同地依照順序層積有光學調整層3及硬塗層4(將在第2圖顯示之硬塗薄膜的符號記載為「1A」)。如此,藉由在基材薄膜2的另一主面側亦層積有光學調整層3及硬塗層4,在抑制產生干涉條紋之同時,在基材薄膜2的另一主面側之耐擦傷性提升。又,藉由在基材薄膜2的另一主面側之硬塗層4(及光學調整層3)的硬化收縮,而將在基材薄膜2的一主面側之硬塗層4(及光學調整層3)的硬化收縮相抵銷且能夠抑制硬塗薄膜1A產生卷曲。
On the other main surface side of the
在基材薄膜2的另一主面側之光學調整層3及硬塗層4,可由與在基材薄膜2的一主面側之光學調整層3及硬塗層4同樣的材料或厚度所形成,亦可由不同的材料或厚度所構成。但是基材薄膜2的另一主面側之光學調整層3的折射率,較佳是聚醯亞胺薄膜的折射率與硬塗層4的折射率之間之值,光學調整層3的厚度為30nm以上、700nm以下。
The
本實施形態之硬塗薄膜1A,係基本上能夠與前述硬塗薄膜1同樣地進行而製造。但是,在基材薄膜2的一主面側之硬塗層4(及光學調整層3)的硬化、與在基材薄膜2的另一主面側之硬塗層4(及光學調整層3)的硬化,可同時進行亦可各
別地進行。
The
(5)其它實施形態-2 (5) Other Embodiments-2
在硬塗薄膜1之基材薄膜2的另一主面側(與層積有光學調整層3及硬塗層4之面為相反側的面側),係如第3圖顯示,亦可層積有黏著劑層5(將第3圖顯示之硬塗薄膜的符號記載為「1B」)。藉由層積此種黏著劑層5,能夠將硬塗薄膜1B簡易地貼附在所需要的被黏著物。又,同樣地,在硬塗薄膜1A的一主面側及/或另一主面側之硬塗層4之與光學調整層3側為相反側,亦可層積有黏著劑層。
On the other main surface side of the
作為構成黏著劑層5之黏著劑,係沒有特別限定,能夠使用丙烯酸系黏著劑、橡膠系黏著劑、聚矽氧系黏著劑等習知的黏著劑。黏著劑層5的厚度係沒有特別限定,通常5~100μm,較佳為10~60μm的範圍。
The adhesive constituting the
本實施形態之硬塗薄膜1B,係基本上能夠與前述硬塗薄膜1同樣地進行而製造。黏著劑層5係使用常用的方法形成即可。
The
又,在黏著劑層5的露出面(與基材薄膜2側為相反側的面),亦可層積有剝離薄片。
In addition, a release sheet may be laminated on the exposed surface of the adhesive layer 5 (the surface opposite to the
(6)其它實施形態-3 (6) Other Embodiments-3
本實施形態之硬塗薄膜1亦可層積有其它層、例如黏接著劑層、阻障層、導電層、低反射層、易印刷層、防污層等。
The
(7)硬塗薄膜的用途 (7) Application of hard coating film
以上的實施形態之硬塗薄膜1、1A、1B,係例如能夠適合使用在各種電子機器、特別是可移動式電子機器之可撓性顯示
器,具體而言係液晶顯示器(LCD)、有機EL顯示器(OELD)、電子紙模組(薄膜狀電子紙)等各種可撓性顯示器作為表層(保護薄膜)或中間層的可撓性構件。
The
以上說明的實施形態,係為了容易理解本發明而記載,不是為了限定本發明而記載。因而,在上述實施形態所揭示的各要素,其宗旨亦包含屬於本發明的技術範圍之全部的設計變更和均等物。 The embodiments described above are described in order to facilitate understanding of the present invention, and are not described in order to limit the present invention. Therefore, the meaning of each element disclosed in the above-mentioned embodiments includes all design changes and equivalents belonging to the technical scope of the present invention.
例如,只要不阻礙前述本實施形態的作用效果,硬塗薄膜1、1A、1B之各層之間,亦可存在其他層。
For example, other layers may be present between the layers of the
以下,藉由實施例等而進一步具體地說明本發明,但是本發明的範圍係不被該等實施例等所限定。 Hereinafter, although an Example etc. demonstrate this invention more concretely, the scope of the present invention is not limited by these Examples etc.
[製造例1](基材薄膜的製造1)
[Manufacture Example 1] (
在N,N-二甲基乙醯胺溶劑中,將2,2’-雙(三氟甲基)-4,4’-二胺基聯苯、聯苯基四羧酸二酐、及2,2-雙(3,4-二羧苯基)六氟丙酸二酐在冷卻下進行混合溶解,隨後藉由在常溫攪拌10小時,來得到聚醯胺酸溶液。 In N,N-dimethylacetamide solvent, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, biphenyltetracarboxylic dianhydride, and 2 , 2-bis(3,4-dicarboxyphenyl)hexafluoropropionic dianhydride was mixed and dissolved under cooling, followed by stirring at room temperature for 10 hours to obtain a polyamic acid solution.
在所得到的聚醯胺酸溶液添加乙酸酐及吡啶,充分地攪拌後,塗佈在玻璃板上,慢慢地從常溫升溫至180℃為止。到達180℃後,藉由加熱一定時間,隨後進行抽真空,而將揮發分完全地除去。最後,藉由在真空下冷卻至常溫,來得到膜厚25μm的聚醯亞胺薄膜A。針對該聚醯亞胺薄膜A進行測定時,b*為0.61,折射率為1.62,在波長550nm之透射率為90%。 Acetic anhydride and pyridine were added to the obtained polyamic acid solution, and after stirring well, it applied on the glass plate, and it heated up gradually from normal temperature to 180 degreeC. After reaching 180°C, the volatile matter is completely removed by heating for a certain period of time, followed by vacuuming. Finally, by cooling to room temperature under vacuum, a polyimide film A having a film thickness of 25 μm was obtained. When the polyimide film A was measured, b* was 0.61, the refractive index was 1.62, and the transmittance at a wavelength of 550 nm was 90%.
又,聚醯亞胺薄膜的膜厚,係依據JIS K7130,使用定壓厚度測定器(Teclock公司製、製品名「PG-02」)而測定。 In addition, the film thickness of the polyimide film was measured using a constant pressure thickness measuring device (manufactured by Teclock Corporation, product name "PG-02") in accordance with JIS K7130.
針對上述b*,係依據JIS Z8722,使用同時測定方式分光式色差計(日本電色工業公司製、製品名「SQ-2000」)作為測定裝置,使用C光源2°視野(C/2)作為光源,使用透過測定法而測定L*a*b*表色系的b*。 Regarding b* above, based on JIS Z8722, a simultaneous measurement method spectroscopic colorimeter (manufactured by Nippon Denshoku Industries Co., Ltd., product name "SQ-2000") was used as the measurement device, and a C light source with a 2° field of view (C/2) was used as the measurement device. As for the light source, b* of the L*a*b* colorimetric system was measured using a transmission measurement method.
在上述波長550nm之透射率,係使用紫外線可見近紅外分光透射率計(島津製作所製、製品名「UV3600」)而測定。 The transmittance at the above wavelength of 550 nm was measured using an ultraviolet-visible-near-infrared spectral transmittance meter (manufactured by Shimadzu Corporation, product name "UV3600").
[製造例2](基材薄膜的製造2)
[Manufacture Example 2] (
在N,N-二甲基乙醯胺溶劑中,除了變更2,2’-雙(三氟甲基)-4,4’-二胺基聯苯、聯苯基四羧酸二酐、及2,2-雙(3,4-二羧苯基)六氟丙酸二酐的調配比率之同時,調整所得到的聚醯亞胺塗佈液的濃度以外,藉由進行與製造例1同樣的製造方法,來得到膜厚為15μm、b*為2.25、折射率為1.70、在波長550nm的透射率為87%之聚醯亞胺薄膜B(測定方法係如上述)。 In N,N-dimethylacetamide solvent, in addition to changing 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, biphenyltetracarboxylic dianhydride, and While adjusting the compounding ratio of 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropionic dianhydride, the concentration of the obtained polyimide coating liquid was adjusted, and by performing the same procedure as in Production Example 1, According to the production method, polyimide film B (the measurement method is as above) with a thickness of 15 μm, a b* of 2.25, a refractive index of 1.70, and a transmittance of 87% at a wavelength of 550 nm was obtained.
[實施例1] [Example 1]
將作為活性能量線硬化性成分之二新戊四醇六丙烯酸酯100質量份(固體成分換算;以下相同)、作為金屬氧化物微粒子之表面改性氧化鋯微粒子(CIK Nanotec公司製、製品名「ZRMIBK15WT%-F85」、平均粒徑:15nm)85質量份、及作為光聚合起始劑之1-羥基環己基苯基酮5質量份,在以1:1的質量比混合甲基異丁基酮與環己酮而成之混合溶劑中進行攪拌混合,來得到光學調整層用組成物的塗佈液。 100 parts by mass of diperythritol hexaacrylate as an active energy ray-curing component (in terms of solid content; the same applies hereinafter), and surface-modified zirconia fine particles (manufactured by CIK Nanotec Co., Ltd., product name " ZRMIBK15WT%-F85", average particle size: 15nm) 85 parts by mass, and 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator, mixed with methyl isobutyl at a mass ratio of 1:1 The ketone and cyclohexanone were stirred and mixed in a mixed solvent to obtain a coating liquid of a composition for an optical adjustment layer.
又,將作為活性能量線硬化性成分之二新戊四醇 六丙烯酸酯40質量份、作為填料之反應性氧化矽填料(平均粒徑:15nm)60質量份、及作為光聚合起始劑之1-羥基環己基苯基酮10質量份之混合物,在以1:1的質量比混合甲基異丁基酮與環己酮而成之混合溶劑中,進行攪拌混合,來得到硬塗層用組成物的塗佈液。 In addition, diperythritol, which is an active energy ray-curing component, A mixture of 40 parts by mass of hexaacrylate, 60 parts by mass of reactive silica filler (average particle size: 15 nm) as a filler, and 10 parts by mass of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator, in In a mixed solvent in which methyl isobutyl ketone and cyclohexanone were mixed at a mass ratio of 1:1, stirring and mixing were performed to obtain a coating liquid of a composition for a hard coat layer.
其次,在作為基材薄膜之聚醯亞胺薄膜A的一面,使用繞線棒而塗佈上述光學調整層用組成物的塗佈液,使其於50℃加熱乾燥1分鐘。隨後,藉由從上述光學調整層用組成物的塗膜側在以下的條件下照射紫外線,使光學調整層用組成物的塗膜硬化而形成厚度327nm的光學調整層。 Next, on one side of the polyimide film A as the base film, the above-mentioned coating liquid of the optical adjustment layer composition was coated using a wire bar, and heated and dried at 50° C. for 1 minute. Subsequently, the coating film of the composition for optical adjustment layer was cured by irradiating ultraviolet rays from the coating film side of the composition for optical adjustment layer under the following conditions to form an optical adjustment layer with a thickness of 327 nm.
其次,將上述硬塗層用組成物的塗佈液,使用繞線棒塗佈在所形成的光學調整層上,於70℃使其加熱乾燥1分鐘。隨後,在以下的條件下,從上述硬塗層用組成物的塗膜側照射紫外線,使硬塗層用組成物的組成物的塗膜硬化,形成厚度5μm的硬塗層,來得到硬塗薄膜。 Next, the coating liquid of the composition for a hard coat layer was coated on the formed optical adjustment layer using a wire bar, and heated and dried at 70° C. for 1 minute. Subsequently, under the following conditions, ultraviolet rays were irradiated from the coating film side of the composition for the hard coat layer to harden the coating film of the composition for the hard coat layer to form a hard coat layer with a thickness of 5 μm , to obtain Hard coat film.
<紫外線照射條件> <UV irradiation conditions>
.紫外線照射裝置:GS Yuasa Corporation公司製紫外線照射裝置 . Ultraviolet radiation device: UV radiation device manufactured by GS Yuasa Corporation
.光源:高壓水銀燈 . Light source: high pressure mercury lamp
.燈電力:1.4kW . Lamp power: 1.4kW
.照度:100mW/cm2 . Illumination: 100mW/ cm2
.光量:240mJ/cm2 . Light quantity: 240mJ/cm 2
.輸送帶速度:1.2m/min . Conveyor belt speed: 1.2m/min
.在氮氣環境下,紫外線照射(氧濃度1%以下) . Under nitrogen atmosphere, ultraviolet radiation (oxygen concentration below 1%)
[實施例2~7、比較例1~5] [Examples 2~7, Comparative Examples 1~5]
除了將構成光學調整層用組成物及硬塗層用組成物之各成分的種類及調配比率、光學調整層及硬塗層的厚度、以及基材薄膜的種類及厚度如表1所顯示變更以外,係與實施例1同樣地進行而製造硬塗薄膜。但是在實施例3及7之光學調整層的形成時,係不進行紫外線照射。 Except that the types and compounding ratios of the components constituting the composition for the optical adjustment layer and the composition for the hard coat layer, the thicknesses of the optical adjustment layer and the hard coat layer, and the type and thickness of the base film were changed as shown in Table 1 , A hard coat film was produced in the same manner as in Example 1. However, during the formation of the optical adjustment layer in Examples 3 and 7, ultraviolet irradiation was not performed.
又,表1記載的略號等之詳細係如以下。 In addition, the details of the abbreviations and the like described in Table 1 are as follows.
A:二新戊四醇六丙烯酸酯 A: diperythritol hexaacrylate
B:聚酯樹脂(熱可塑性樹脂)(東洋紡公司製、製品名「VYLON 200」、數量平均分子量:17000) B: Polyester resin (thermoplastic resin) (manufactured by Toyobo Co., Ltd., product name "VYLON 200", number average molecular weight: 17000)
C:表面改性氧化鋯微粒子(CIK Nanotec公司製、製品名「ZRMIBK15WT%-F85」、平均粒徑:15nm) C: Surface-modified zirconia fine particles (manufactured by CIK Nanotec, product name "ZRMIBK15WT%-F85", average particle diameter: 15 nm)
D:1-羥基環己基苯基酮 D: 1-Hydroxycyclohexyl phenyl ketone
E:二新戊四醇六丙烯酸酯40質量份、反應性氧化矽填料(平均粒徑:15nm)60質量份及1-羥基環己基苯基酮10質量份的混合物 E: Mixture of 40 parts by mass of dipenteoerythritol hexaacrylate, 60 parts by mass of reactive silica filler (average particle diameter: 15 nm), and 10 parts by mass of 1-hydroxycyclohexyl phenyl ketone
F:環氧乙烷改性二新戊四醇六丙烯酸酯(導入環氧乙烷12莫耳) F: Ethylene oxide modified diperythritol hexaacrylate (imported 12 moles of ethylene oxide)
PI-25:聚醯亞胺薄膜A PI-25: Polyimide film A
PI-15:聚醯亞胺薄膜B PI-15: Polyimide film B
PET:聚對苯二甲酸乙二酯薄膜(三菱樹脂公司製、製品名「Diafoil T-60」、厚度:50μm) PET: Polyethylene terephthalate film (manufactured by Mitsubishi Plastics Corporation, product name "Diafoil T-60", thickness: 50 μm )
[試驗例1](折射率的測定) [Test Example 1] (Measurement of Refractive Index)
(1)基材薄膜的折射率 (1) Refractive index of substrate film
在測定波長589nm、測定溫度25℃的條件下,使用阿貝折射計(ATAGO公司製、製品名「多波長阿貝折射計DR-M2」),依據JIS K7142(2008),測定在實施例及比較例所使用的基材薄膜之折射率。將結果顯示在表2。 Under the conditions of a measurement wavelength of 589 nm and a measurement temperature of 25° C., using an Abbe refractometer (manufactured by ATAGO Corporation, product name “Multi-Wavelength Abbe Refractometer DR-M2”), according to JIS K7142 (2008), measured in Examples and The refractive index of the base film used in the comparative example. The results are shown in Table 2.
(2)光學調整層及硬塗層的折射率 (2) Refractive index of optical adjustment layer and hard coat layer
在一面經易接著處理的聚對苯二甲酸乙二酯薄膜(東洋紡公司製、製品名「COSMOSHINE A4100」、厚度:50μm)之未處理面,與實施例及比較例同樣地進行而形成厚度200nm的光學調整層或硬塗層。其次,使用砂紙(sand paper)摩擦聚對苯二甲酸乙二酯薄膜的易接著處理面,且使用油性筆(ZEBRA公司製、製品名「Mckee黑」)塗滿黑色。 On the untreated side of a polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., product name "COSMOSHINE A4100", thickness: 50 μm ) that has been easily bonded on one side, it is formed in the same manner as in Examples and Comparative Examples. Optical adjustment layer or hard coat layer with a thickness of 200nm. Next, the easily-adhesive surface of the polyethylene terephthalate film was rubbed with sand paper, and filled with black using an oil-based pen (manufactured by ZEBRA, product name "Mckee black").
隨後,在測定波長589nm、測定溫度25℃的條件下,使用分光橢圓偏光計(J.A.WOOLLAM公司製、製品名「M-2000」」),依據JIS K7142(2008)而測定上述硬塗層的折射率。將結果顯示在表2。 Then, under conditions of a measurement wavelength of 589 nm and a measurement temperature of 25° C., the refraction of the above-mentioned hard coat layer was measured in accordance with JIS K7142 (2008) using a spectroscopic ellipsometer (manufactured by J.A. Woollam Co., Ltd., product name "M-2000"). Rate. The results are shown in Table 2.
(3)折射率差的計算 (3) Calculation of refractive index difference
計算在上述所測得之基材薄膜的折射率及硬塗層的折射率之中央值(=(基材薄膜的折射率+硬塗層的折射率)/2),從所得到的中央值減去光學調整層的折射率,來算出折射率差。將結果顯示在表2。 Calculate the median value (=(refractive index of the substrate film+refractive index of the hard coat layer)/2) of the above-mentioned measured refractive index of the base film and the hard coat layer, from the obtained median value The refractive index difference was calculated by subtracting the refractive index of the optical adjustment layer. The results are shown in Table 2.
(試驗例2)(干涉條紋的評價) (Test example 2) (Evaluation of interference fringes)
(1)目視評價 (1) Visual evaluation
將實施例及比較例所製造的硬塗薄膜,透過雙面黏著薄片(LINTEC公司製、製品名「OPTERIA MO-3006C」、厚度:25 μm)而貼附在黑色的壓克力板(三菱Rayon公司製、製品名「Acrylight L502」)。此時,係以硬塗薄膜的基材薄膜為接觸壓克力板之方式貼附。 The hard coat films produced in Examples and Comparative Examples were attached to a black acrylic plate (Mitsubishi manufactured by Rayon Corporation, product name "Acrylight L502"). At this time, it is attached in such a way that the base film of the hard coat film is in contact with the acrylic plate.
針對所得到的積層體,在3波長螢光燈下,從硬塗層側藉由目視而確認干涉條紋且依照以下的基準進行評價。將結果顯示在表2。 With regard to the obtained laminate, under a three-wavelength fluorescent lamp, interference fringes were visually confirmed from the hard-coat layer side, and evaluation was performed according to the following criteria. The results are shown in Table 2.
良好(◎):幾乎無法看到干涉條紋 Good (◎): Almost no interference fringes can be seen
大致良好(○):不容易看到干涉條紋 Generally good (○): Interference fringes are not easily seen
稍微不良(△):能夠看到干涉條紋 Slightly bad (△): Interference fringes can be seen
不良(×):能夠清楚地看到干涉條紋 Bad (×): Interference fringes can be seen clearly
(2)最大反射率差的測定 (2) Determination of maximum reflectance difference
針對(1)所得到的積層體,在以下的條件下,使用分光光度計測定在反射率光譜的波長500~600nm間之最大反射率差。將結果顯示在表2。 With respect to the laminate obtained in (1), under the following conditions, the maximum reflectance difference between the wavelengths of 500 to 600 nm in the reflectance spectrum was measured using a spectrophotometer. The results are shown in Table 2.
<測定條件> <Measurement conditions>
.分光光度計:島津製作所公司製,製品名「紫外可見近紅外分光光度計UV-3600」 . Spectrophotometer: manufactured by Shimadzu Corporation, product name "ultraviolet visible near infrared spectrophotometer UV-3600"
.試料保持器:島津製作所公司製、製品名「大型試料室MPC-3100」 . Sample holder: manufactured by Shimadzu Corporation, product name "large sample chamber MPC-3100"
.積分球:島津製作所公司製、製品名「積分球附屬裝置ISR-3100」 . Integrating sphere: Made by Shimadzu Corporation, product name "Integrating sphere attachment ISR-3100"
.入射角:8° . Angle of incidence: 8°
[試驗例3](耐擦傷性的評價) [Test Example 3] (Evaluation of Scratch Resistance)
針對在實施例及比較例所製造的硬塗薄膜之硬塗層表 面,使用#0000的鋼絲絨,在125g重/cm2的荷重進行往復摩擦10次,將長度100mm、寬度20mm的範圍設為試驗範圍。在3波長螢光燈下藉由目視確認在該試驗範圍之傷痕條數且依照以下的基準進行評價耐擦傷性。將結果顯示在表2。 For the hard coat surface of the hard coat film manufactured in the examples and comparative examples, use #0000 steel wool to rub back and forth 10 times at a load of 125 g/cm 2 , and set the range of length 100 mm and width 20 mm to be test range. Scratch resistance was evaluated by visually confirming the number of scratches in the test range under a 3-wavelength fluorescent lamp in accordance with the following criteria. The results are shown in Table 2.
○:傷痕條數為小於20條。 ◯: The number of scratches is less than 20.
×:傷痕條數為20條以上。 ×: The number of scars is 20 or more.
[試驗例4](心軸試驗) [Test example 4] (mandrel test)
針對在實施例及比較例所製造的硬塗薄膜,使用圓筒型心軸彎曲試驗機(CORTEC公司製),實施依據JIS K5600-5-1之心軸試驗。該心軸試驗係使硬塗薄膜的硬塗層成為外側而進行。求取在硬塗層及光學調整層不產生龜裂、剝落等的不良之心軸之中,直徑為最小的心軸之直徑(最小心軸直徑)。將結果顯示在表2。 About the hard coat film manufactured in the Example and the comparative example, the mandrel test based on JISK5600-5-1 was implemented using the cylindrical mandrel bending tester (made by CORTEC). This mandrel test was performed with the hard coat layer of the hard coat film on the outside. The diameter of the mandrel with the smallest diameter (minimum mandrel diameter) among the mandrels with no defects such as cracking and peeling of the hard coat layer and the optical adjustment layer was obtained. The results are shown in Table 2.
[試驗例5](耐彎曲性試驗) [Test Example 5] (bending resistance test)
針對實施例及比較例所製造的硬塗薄膜,使用耐久試驗機(YUASA SYSTEM機器公司製、製品名「面狀體無負荷U字伸縮試驗機DLDMLH-FS」)且使硬塗層成為外側,在試驗速度60mm/s且將試驗次數(往復數)及彎曲徑進行各種變更而使其重複彎曲。接著,確認有無產生硬塗層及光學調整層的龜裂.剝落、硬塗薄膜的白化.彎曲痕跡等的不良,依照以下的基準進行評價耐彎曲性。將結果顯示在表2。 For the hard-coated films produced in Examples and Comparative Examples, a durability tester (manufactured by YUASA SYSTEM Instruments Co., Ltd., product name "planar body no-load U-shaped stretch tester DLDMLH-FS") was used, and the hard-coated layer was turned to the outside. The test speed was 60 mm/s, and the number of tests (number of reciprocations) and the bending diameter were changed in various ways, and the bending was repeated. Next, it was checked whether there were any cracks in the hard coat layer and the optical adjustment layer. Peeling, whitening of hard coat film. Defects such as bending marks were evaluated for bending resistance according to the following criteria. The results are shown in Table 2.
◎:彎曲直徑5mm以下,且即便試驗次數2萬次以上亦不產生不良。 ⊚: The bending diameter is 5 mm or less, and no defect occurs even if the number of tests is 20,000 or more.
○:彎曲直徑10mm以下,且即便試驗次數2萬次以上亦 不產生不良。 ○: Bend diameter 10mm or less, and even if the number of tests is more than 20,000 times No defect occurs.
×:未達到○的基準之水準。 ×: The standard level of ○ was not reached.
[試驗例6](影像鮮明度的評價) [Test Example 6] (Evaluation of Image Sharpness)
針對實施例及比較例所製造的硬塗薄膜,使用影像鮮明性測定器(SUGA試驗機公司製、製品名「ICM-10P」),依據JIS K7374且以影像鮮明度(%)的方式測定5種類的狹縫(狹縫幅:0.125mm、0.25mm、0.5mm、1mm及2mm)之合計值。基於該結果,將影像鮮明度小於400%評定為×,將400%以上且小於450%評定為○,將450%以上評定為◎。將結果顯示在表2。 For the hard coat films manufactured in Examples and Comparative Examples, using an image clarity measuring device (manufactured by SUGA Testing Instrument Co., Ltd., product name "ICM-10P"), according to JIS K7374, the image clarity (%) was measured. The total value of the type of slit (slit width: 0.125mm, 0.25mm, 0.5mm, 1mm and 2mm). Based on the results, the image sharpness of less than 400% was rated as ×, 400% or more and less than 450% was rated as ◯, and 450% or more was rated as ⊚. The results are shown in Table 2.
[試驗例7](霧度值的評價) [Test Example 7] (Evaluation of haze value)
針對實施例及比較例所製造的硬塗薄膜,使用霧度計量器(日本電色工業公司製、製品名「NDH5000」),依據JIS K7136而測定霧度值(%)。基於該結果,將霧度值大於1%評定為×,將1%以下且大於0.5%評定為○,將0.5%以下評定為◎。將結果顯示在表2。 The haze value (%) was measured based on JISK7136 about the hard-coat film manufactured in the Example and the comparative example using the haze meter (made by Nippon Denshoku Kogyo Co., Ltd., product name "NDH5000"). Based on this result, the haze value was rated as × greater than 1%, ○ as 1% or less and greater than 0.5%, and ◎ as 0.5% or less. The results are shown in Table 2.
[試驗例8](60°光澤度的評價) [Test Example 8] (Evaluation of 60° Glossiness)
針對實施例及比較例所製造的硬塗薄膜,使用光澤度計(日本電色工業公司製),依據JIS Z8741-1997而測定60°光澤度(Gloss值)。基於該結果,將60°光澤度小於100%評定為×,將100%以上且小於140%評定為○,將140%以上評定為◎。將結果顯示在表2。 About the hard-coat film manufactured in the Example and the comparative example, 60 degree glossiness (gloss value) was measured based on JISZ8741-1997 using the gloss meter (made by Nippon Denshoku Kogyo Co., Ltd.). Based on the results, the 60° glossiness was rated as ×, 100% or more and less than 140% as ◯, and 140% or more as ⊚. The results are shown in Table 2.
從表2能夠清楚明白,實施例所得到的硬塗薄膜,係具有優異的耐擦傷性及光學特性,同時具有優異的耐彎曲性,進而不容易產生干涉條紋者。 It can be clearly seen from Table 2 that the hard-coated films obtained in Examples have excellent scratch resistance and optical properties, as well as excellent bending resistance, and are less prone to interference fringes.
本發明的硬塗薄膜,係能夠適合作為構成被重複彎曲的可撓性顯示器之可撓性構件,特別是位於表層之保護薄膜。 The hard-coated film of the present invention can be suitably used as a flexible member constituting a repeatedly bent flexible display, especially as a protective film on the surface layer.
1‧‧‧硬塗薄膜 1‧‧‧Hard Coating Film
2‧‧‧基材薄膜 2‧‧‧Substrate film
3‧‧‧光學調整層 3‧‧‧Optical adjustment layer
4‧‧‧硬塗層 4‧‧‧Hard Coating
Claims (9)
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WOPCT/JP2016/074568 | 2016-08-23 | ||
??PCT/JP2016/074568 | 2016-08-23 | ||
PCT/JP2016/074568 WO2018037490A1 (en) | 2016-08-23 | 2016-08-23 | Hard coat film |
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Publication Number | Publication Date |
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TW201807435A TW201807435A (en) | 2018-03-01 |
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KR (1) | KR102610371B1 (en) |
CN (1) | CN109073788B (en) |
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JP7000701B2 (en) * | 2017-04-13 | 2022-01-19 | 大日本印刷株式会社 | Optical film and image display device |
KR20230171478A (en) | 2017-10-27 | 2023-12-20 | 어플라이드 머티어리얼스, 인코포레이티드 | Flexible cover lens films |
KR20200142594A (en) | 2018-05-10 | 2020-12-22 | 어플라이드 머티어리얼스, 인코포레이티드 | Interchangeable cover lenses for flexible displays |
JP2021536030A (en) | 2018-08-14 | 2021-12-23 | アプライド マテリアルズ インコーポレイテッドApplied Materials, Incorporated | Multi-layer wet and dry hard coat for flexible cover lenses |
KR20200040137A (en) | 2018-10-08 | 2020-04-17 | 삼성전자주식회사 | Laminated film, and display device including same |
KR20230173232A (en) | 2019-06-26 | 2023-12-26 | 어플라이드 머티어리얼스, 인코포레이티드 | Flexible multi-layered cover lens stacks for foldable displays |
KR20220032572A (en) * | 2019-07-12 | 2022-03-15 | 도요보 가부시키가이샤 | Hard coat film for folding display and its use |
CN111086307A (en) * | 2020-01-03 | 2020-05-01 | 湖南中天碧水膜科技有限公司 | Shadow eliminating film and method for attaching protective film to shadow eliminating film |
WO2021194312A1 (en) * | 2020-03-26 | 2021-09-30 | 코오롱인더스트리 주식회사 | Optical film having excellent restoring force after folding and display device including same |
KR102458462B1 (en) * | 2020-06-23 | 2022-10-24 | 코오롱인더스트리 주식회사 | A multi-layered film with improving interference fringe and display apparatus comprising the same |
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KR20190039465A (en) | 2019-04-12 |
WO2018037490A1 (en) | 2018-03-01 |
CN109073788B (en) | 2023-09-01 |
CN109073788A (en) | 2018-12-21 |
KR102610371B1 (en) | 2023-12-05 |
TW201807435A (en) | 2018-03-01 |
JPWO2018037490A1 (en) | 2018-11-22 |
JP6307205B1 (en) | 2018-04-04 |
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