TW201600331A

TW201600331A - Structure having protrusion formed on surface thereof

Info

Publication number: TW201600331A
Application number: TW104111868A
Authority: TW
Inventors: Keita Wada; Kiyoshi Minoura; Satoko Morioka
Original assignee: Toray Industries
Priority date: 2014-04-15
Filing date: 2015-04-14
Publication date: 2016-01-01
Also published as: WO2015159825A1; JPWO2015159825A1; JP6493206B2

Abstract

The present invention relates to a structure having protrusions formed on the surface thereof, which can be used suitably in technical fields of micro flow paths, cell culture sheets, packaging materials, stain-proof or water-proof sheets, recording materials, screens, separators, ion exchange membranes, battery separator membrane materials, displays, optical materials and the like in which liquid repellency is required for surfaces thereof.

Description

於表面具有突起的構造體 a structure having protrusions on its surface

本發明係關於一種藉由於表面具有微細構造而顯現撥液效果的構造體。 The present invention relates to a structure which exhibits a liquid-repelling effect by having a fine structure on its surface.

以往作為在構造體的表面使撥液效果顯現的手段，多適用塗布氟系聚合物等表面能量低的樹脂的手法。然而，只是塗布撥液性能有限，有時得不到如所期待的撥液性。於是，提出了藉由於表面附加微細構造而得到優於塗布的撥液性的方法(專利文獻1~3)。 Conventionally, as a means for exhibiting a liquid-repelling effect on the surface of a structure, a method of applying a resin having a low surface energy such as a fluorine-based polymer is often applied. However, only the liquid dispensing performance is limited, and sometimes the desired liquid repellency is not obtained. Then, a method of obtaining liquid repellency superior to coating by adding a fine structure to the surface has been proposed (Patent Documents 1 to 3).

此外，作為使撥液效果顯現的微細構造，提出了指向構造體表面垂直的方向以外、具有異向性的突起(專利文獻4)。 In addition, as a fine structure in which the liquid-repellent effect is exhibited, a protrusion having an anisotropy other than the direction perpendicular to the surface of the structure is proposed (Patent Document 4).

先前技術文獻 Prior technical literature 專利文獻 Patent literature

專利文獻1 特開2004-170935號公報 Patent Document 1 JP-A-2004-170935

專利文獻2 特開2009-187025號公報 Patent Document 2, JP-A-2009-187025

專利文獻3 特開2009-42714號公報 Patent Document 3, JP-A-2009-42714

專利文獻4 國際公開第2004/048064號小冊子 Patent Document 4 International Publication No. 2004/048064

然而，在上述專利文獻1~3中所記載的技術中，液體以撥液狀態附著於構造體即薄膜上後，為了使附著的液體移動去除，需要使薄膜傾斜一定角度。薄膜的傾斜小的情況或薄膜放置成水平的情況，液滴大多在附著於構造體即薄膜上的狀態下殘留，有得不到所期待的撥液性效果的問題。 However, in the techniques described in Patent Documents 1 to 3, after the liquid adheres to the film which is a structure in a liquid-repellent state, it is necessary to incline the film at a constant angle in order to remove the adhered liquid. When the inclination of the film is small or the film is placed horizontally, the droplets are often left in a state of being attached to the film which is a structure, and the desired liquid repellency effect is not obtained.

此外，在專利文獻4中所記載的技術中，有得不到穩定的撥液性或撥液性能低的問題。 Further, in the technique described in Patent Document 4, there is a problem that stable liquid repellency or liquid repellency is not obtained.

為了解決上述課題，本發明具有以下構造： In order to solve the above problems, the present invention has the following configuration:

(1)一種構造體，其於表面具有突起，並且(i)前述突起之中，70%以上為從根部的中心畫到前端的中心的直線相對於與構造體的表面垂直的方向傾斜的突起，(ii)前述構造體表面的前述突起的個數在10000μm²中，為10個以上、4×10⁵個以下，(iii)前述突起的平均直徑D為100nm以上、10μm以下，(iv)前述突起的平均高度H與平均直徑D之比(H/D)為1以上、50以下。 (1) A structure having protrusions on a surface, and (i) among the protrusions, 70% or more is a line drawn from a center of the root to a center of the front end with respect to a direction inclined perpendicular to a surface of the structure. (ii) The number of the protrusions on the surface of the structure is 10 or more and 4 × 10 ⁵ or less in 10000 μm ² , and (iii) the average diameter D of the protrusions is 100 nm or more and 10 μm or less, (iv) The ratio (H/D) of the average height H of the protrusions to the average diameter D is 1 or more and 50 or less.

(2)如前述(1)之構造體，其中從前述突起根部的中心畫到前端的中心的直線的方向為不一定。 (2) The structure according to the above (1), wherein the direction of the straight line drawn from the center of the protruding root to the center of the front end is not necessarily.

(3)如前述(1)之構造體，其中從前述突起根部的中心畫到前端的中心的直線的方向為一定。 (3) The structure according to the above (1), wherein a direction of a straight line drawn from the center of the protruding root to the center of the front end is constant.

(4)如前述(1)至(3)中任一項之構造體，其中從前述突起根部的中心畫到前端的中心的直線之中，70%以上相對於與構造體表面垂直的方向，形成25°以上、50°以下的角度。 (4) The structure according to any one of (1) to (3) above, wherein 70% or more of the straight line drawn from the center of the protrusion root to the center of the front end is opposite to the direction perpendicular to the surface of the structure, An angle of 25° or more and 50° or less is formed.

(5)如前述(1)至(4)中任一項之構造體，其中前述突起的高度為不一定。 (5) The structure according to any one of (1) to (4) above, wherein the height of the protrusion is not necessarily.

藉由本發明，可得到下述構造體：利用突起，在液滴附著時，使液滴與突起之間形成空氣層，所以液滴與空氣的接觸面積增加，藉由液滴的表面張力，撥液功能顯著提高。 According to the present invention, it is possible to obtain a structure in which an air layer is formed between the liquid droplet and the protrusion when the liquid droplet is adhered by the protrusion, so that the contact area of the liquid droplet with the air is increased, and the surface tension of the liquid droplet is dialed. The liquid function is significantly improved.

再者，由於突起對於構造體表面的垂直方向傾斜，所以附著於表面的液滴成為被不穩定支持的狀態，液滴容易移動。其結果，可得到下述構造體：即使在使構造體的表面從水平稍微傾斜的狀態或水平的狀態下，都可使液滴容易移動而抑制附著或殘留於構造體的表面，具有更穩定且效果高的撥液性能或防污效果。此外，依據液體或構成突起的材料的種類，按照其表面自由能量或黏度等特性，有時可得到超親水效果。 Further, since the projections are inclined in the vertical direction of the surface of the structure, the droplets adhering to the surface are in an unstable state, and the droplets easily move. As a result, it is possible to obtain a structure in which the droplets are easily moved to suppress adhesion or remain on the surface of the structure, even when the surface of the structure is slightly inclined from the horizontal or horizontal. And the effect is high liquid dispensing performance or antifouling effect. Further, depending on the type of the liquid or the material constituting the protrusion, a superhydrophilic effect may be obtained depending on characteristics such as surface free energy or viscosity.

11‧‧‧構造體 11‧‧‧Structural body

12‧‧‧薄膜的表面 12‧‧‧ Film surface

13‧‧‧突起 13‧‧‧ Protrusion

14‧‧‧突起前端的中心 14‧‧‧Center of the front end of the protrusion

15‧‧‧突起根部的中心 15‧‧‧ Center of the protruding root

16‧‧‧連結突起根部的中心15與突起前端的中心14的直線 16‧‧‧ Straight line connecting the center 15 of the root of the protrusion with the center 14 of the front end of the protrusion

17‧‧‧與薄膜的表面12垂直的方向 17‧‧‧direction perpendicular to the surface 12 of the film

50‧‧‧製造裝置 50‧‧‧Manufacture of equipment

51‧‧‧捲出輥 51‧‧‧Rolling roll

52‧‧‧捲出單元 52‧‧‧Withdraw unit

53‧‧‧模具 53‧‧‧Mold

54‧‧‧加壓單元 54‧‧‧ Pressurizing unit

55‧‧‧剝離手段 55‧‧‧Dissipation means

55A‧‧‧剝離輥 55A‧‧‧ peeling roller

55B‧‧‧剝離輔助輥 55B‧‧‧ peeling auxiliary roller

55H‧‧‧剝離輥55A與模具的離間距離 55H‧‧‧The distance between the peeling roller 55A and the mold

56‧‧‧捲取輥 56‧‧‧Winding roller

57、58‧‧‧加壓板 57, 58‧‧‧ Pressurized plate

59、60‧‧‧緩衝手段 59, 60‧‧‧ buffer means

61‧‧‧捲取單元 61‧‧‧Winding unit

70‧‧‧製造裝置 70‧‧‧ Manufacturing equipment

71‧‧‧突起形成面 71‧‧‧Protrusion forming surface

73‧‧‧捲出輥 73‧‧‧Rolling roll

74‧‧‧積層裝置 74‧‧‧Layered device

75‧‧‧加熱輥 75‧‧‧heating roller

76‧‧‧模具 76‧‧‧Mold

77‧‧‧壓輥 77‧‧‧pressure roller

78‧‧‧冷卻輥 78‧‧‧Cooling roller

79‧‧‧剝離輥 79‧‧‧ peeling roller

79H‧‧‧剝離輥79與模具的離間距離 79H‧‧‧The separation distance between the peeling roller 79 and the mold

80‧‧‧搬送輥 80‧‧‧Transport roller

81‧‧‧捲取輥 81‧‧‧Winding roller

第1圖為本發明之構造體即薄膜的概略剖面圖。 Fig. 1 is a schematic cross-sectional view showing a film which is a structure of the present invention.

第2圖為本發明之構造體即薄膜的概略斜視圖。 Fig. 2 is a schematic perspective view showing a film which is a structure of the present invention.

第3圖為本發明一形態即從突起根部的中心畫到前端的中心的直線的方向為一定的構造體即樹脂薄膜的概略剖面圖。 Fig. 3 is a schematic cross-sectional view showing a resin film which is a structure in which a direction from a center of a projection root to a center of a tip end is constant.

第4圖為本發明一形態即突起的高度為不一定的構造體即樹脂薄膜的概略剖面圖。 Fig. 4 is a schematic cross-sectional view showing a resin film which is a structure in which the height of the projection is not constant, which is one embodiment of the present invention.

第5圖為顯示製造本發明之構造體即薄膜的裝置一例的剖面概略圖。 Fig. 5 is a schematic cross-sectional view showing an example of an apparatus for producing a film which is a structure of the present invention.

第6圖為從薄膜寬度方向看製造本發明之構造體即薄膜的裝置中的剝離手段的概略平面圖。 Fig. 6 is a schematic plan view showing a peeling means in the apparatus for producing a film which is a structure of the present invention as seen from the width direction of the film.

第7圖為顯示製造本發明之構造體即薄膜的裝置一例的剖面概略圖。 Fig. 7 is a schematic cross-sectional view showing an example of an apparatus for producing a film which is a structure of the present invention.

第8圖為將使用於測定突起個數的本發明之構造體的掃描式電子顯微鏡所拍攝的表面照片二值化的圖像的一例。 Fig. 8 is an example of an image obtained by binarizing a surface photograph taken by a scanning electron microscope of the structure of the present invention for measuring the number of protrusions.

第9圖為將使用於測定突起的平均直徑D的本發明之構造體的掃描式電子顯微鏡所拍攝的表面照片二值化的圖像的一例。 Fig. 9 is an example of an image obtained by binarizing a surface photograph taken by a scanning electron microscope of the structure of the present invention for measuring the average diameter D of the projections.

第10圖為實施例1所記載的藉由本發明而製造的薄膜的掃描式電子顯微鏡所拍攝的表面照片。 Fig. 10 is a surface photograph taken by a scanning electron microscope of the film produced by the present invention described in Example 1.

第11圖為實施例1所記載的藉由本發明而製造的薄膜的掃描式電子顯微鏡所拍攝的剖面照片。 Fig. 11 is a cross-sectional photograph taken by a scanning electron microscope of the film produced by the present invention described in Example 1.

第12圖為實施例2所記載的藉由本發明而製造的薄膜的掃描式電子顯微鏡所拍攝的表面照片。 Fig. 12 is a surface photograph taken by a scanning electron microscope of the film produced by the present invention described in Example 2.

第13圖為實施例2所記載的藉由本發明而製造的薄膜的掃描式電子顯微鏡所拍攝的剖面照片。 Fig. 13 is a cross-sectional photograph taken by a scanning electron microscope of the film produced by the present invention described in Example 2.

第14圖為實施例3所記載的藉由本發明而製造的薄膜的掃描式電子顯微鏡所拍攝的表面照片。 Fig. 14 is a surface photograph taken by a scanning electron microscope of the film produced by the present invention described in Example 3.

第15圖為實施例3所記載的藉由本發明而製造的薄膜的掃描式電子顯微鏡所拍攝的剖面照片。 Fig. 15 is a cross-sectional photograph taken by a scanning electron microscope of the film produced by the present invention described in Example 3.

第16圖為比較例1所記載的製造後的薄膜的掃描式電子顯微鏡所拍攝的表面照片。 Fig. 16 is a surface photograph taken by a scanning electron microscope of the produced film described in Comparative Example 1.

第17圖為比較例1所記載的製造後的薄膜的掃描式電子顯微鏡所拍攝的剖面照片。 Fig. 17 is a cross-sectional photograph taken by a scanning electron microscope of the manufactured film described in Comparative Example 1.

第18圖為比較例2所記載的製造後的薄膜的掃描式電子顯微鏡所拍攝的表面照片。 Fig. 18 is a surface photograph taken by a scanning electron microscope of the manufactured film described in Comparative Example 2.

第19圖為比較例2所記載的製造後的薄膜的掃描式電子顯微鏡所拍攝的剖面照片。 Fig. 19 is a cross-sectional photograph taken by a scanning electron microscope of the manufactured film described in Comparative Example 2.

第20圖為比較例3所記載的製造後的薄膜的掃描式電子顯微鏡所拍攝的表面照片。 Fig. 20 is a surface photograph taken by a scanning electron microscope of the manufactured film described in Comparative Example 3.

第21圖為比較例3所記載的製造後的薄膜的掃描式電子顯微鏡所拍攝的剖面照片。 Fig. 21 is a cross-sectional photograph taken by a scanning electron microscope of the manufactured film described in Comparative Example 3.

本發明為於表面具有突起的構造體，並且最好前述突起之中，70%以上為從根部的中心畫到前端的中心的直線相對於與構造體的表面垂直的方向傾斜的突起，前述構造體表面的前述突起的個數在10000μm²中，為10個以上、4×10⁵個以下，前述突起的平均直徑D為100nm以上、10μm以下，前述突起的平均高度H與平均直徑D之比(H/D)為1以上、50以下。 The present invention is a structure having a projection on the surface, and preferably 70% or more of the protrusions are protrusions which are drawn from the center of the root to the center of the front end, and are inclined with respect to a direction perpendicular to the surface of the structure. The number of the protrusions on the surface of the body is 10 or more and 4 × 10 ⁵ or less in 10000 μm ² , and the average diameter D of the protrusions is 100 nm or more and 10 μm or less, and the ratio of the average height H of the protrusions to the average diameter D (H/D) is 1 or more and 50 or less.

茲使用圖面說明本發明之具有突起的構造體的實施形態。第1圖、第2圖為本發明之構造體即薄膜的概略剖面圖(第1圖)與概略斜視圖(第2圖)。 An embodiment of the structure having projections of the present invention will be described with reference to the drawings. Fig. 1 and Fig. 2 are a schematic cross-sectional view (first drawing) and a schematic oblique view (second drawing) of a film which is a structure of the present invention.

存在於薄膜的表面12的突起13最好獨立且離散地存在。此處，所謂突起，係對於概略剖面圖第1圖所示的構造體即薄膜的表面12，取凸的形狀的部分。突起的形狀可以為任何的形狀，但最好為錘狀的形狀。此外，最好連結突起根部的中心15與突起前端的中心14的直線16從與薄膜的表面12垂直的方向17傾斜。再者，所謂突起根部的中心15，係剖面的突起底部的寬度的中點。此時所謂傾斜，係指直線16和與構造體表面垂直的方向17形成的角度為5°以上。就具體的確認方法而言，係測定以下記載求法的剖面傾斜角度作為直線16和與構造體表面垂直的方向17形成的角度，依此進行判斷。 The protrusions 13 present on the surface 12 of the film are preferably present independently and discretely. Here, the protrusion is a portion having a convex shape on the surface 12 of the film which is a structure shown in Fig. 1 of the schematic cross-sectional view. The shape of the protrusions may be any shape, but is preferably a hammer shape. Further, it is preferable that the straight line 16 connecting the center 15 of the projection root and the center 14 of the projection front end is inclined from the direction 17 perpendicular to the surface 12 of the film. Further, the center 15 of the root portion of the protrusion is the midpoint of the width of the bottom portion of the protrusion of the cross section. The term "tilt" at this time means that the angle formed by the straight line 16 and the direction 17 perpendicular to the surface of the structure is 5 or more. In the specific confirmation method, the inclination angle of the cross section of the method described below is measured as the angle formed by the straight line 16 and the direction 17 perpendicular to the surface of the structure, and the judgment is made accordingly.

(剖面傾斜角度的求法) (method of section inclination angle)

以與構造體(上述的情況下為薄膜)的表面垂直且每隔45°的4個方向的面切斷構造體的4個剖面，分別選擇10個突起，求出此等突起的(a)連結根部的中心與突起前端的中心的線和(b)與構造體表面垂直的方向形成的角度的平均值(以後有時會記載為基準角度)，特別指定基準角度最大的剖面。將該剖面的突起的(a)連結根部的中心與突起前端的中心的線和(b)與構造體表面垂直的方向形成的角度作為剖面傾斜角度。 The four cross sections of the structure are cut in a plane perpendicular to the surface of the structure (the film in the case described above) in four directions of 45°, and ten protrusions are selected to obtain (a) of the protrusions. The average value of the angle between the center of the connecting root and the center of the projection front end and (b) the direction perpendicular to the surface of the structure (hereinafter referred to as the reference angle) is specified, and the section having the largest reference angle is specified. The angle formed by (a) the center of the connecting root portion and the line of the center of the tip end of the protrusion and (b) the direction perpendicular to the surface of the structure are used as the cross-sectional inclination angle.

在構造體的表面為曲面的情況，係以對於突起根部的中心15的接觸面垂直的方向17為基準而判斷有無傾斜。在本發明中，測定上述剖面傾斜角度的剖面的突起之中，70%以上傾斜較好，90%以上傾斜更好，100%傾斜最好。 In the case where the surface of the structure is a curved surface, the presence or absence of inclination is determined based on the direction 17 perpendicular to the contact surface of the center 15 of the root portion of the projection. In the present invention, among the protrusions having a cross section of the cross-sectional inclination angle, 70% or more of the protrusions are preferable, 90% or more of the protrusions are better, and 100% of the protrusions are preferable.

藉由構造體表面的突起傾斜，液滴附著之際，在薄膜表面的液滴被傾斜的突起所支持，所以液滴在構造體表面的保持狀態變得不穩定，液滴容易在構造體的表面移動。液滴本來就會從難以潤濕的地方往容易潤濕的地方移動，所以藉由在液滴周邊形成傾斜的突起，產生使潤濕產生異向性或不均勻性而促進液滴移動的效果。其結果，使薄膜稍微傾斜的情況，或者即使保持水平，構造體表面上的液滴也會移動，從端部落下而被排除，可防止液滴附著或進一步提高防污的效果。 By the inclination of the protrusion on the surface of the structure, when the droplet adheres, the droplet on the surface of the film is supported by the inclined protrusion, so that the state of the droplet on the surface of the structure becomes unstable, and the droplet is easily formed in the structure. The surface moves. The droplets are originally moved from a place that is difficult to wet to a place where they are easily wetted. Therefore, by forming inclined protrusions around the droplets, an effect of promoting anisotropic or unevenness of wetting to promote droplet movement is generated. . As a result, when the film is slightly inclined, or even if it is kept horizontal, the droplets on the surface of the structure move, and are excluded from the end, thereby preventing the droplets from adhering or further improving the antifouling effect.

在本發明之構造體的表面中，若突起的個數在10000μm²中為10個以上、4×10⁵個以下，則容易以突起的頂點支持在構造體表面的液滴，液滴與空氣的接觸面積變大，藉此提高撥液性故較好，為1000個以上、4×10⁵個以下更好。10000μm²中的突起的個數比4×10⁵個多的情況，在液滴附著時，充分的空間不存在於突起之間，與空氣的接觸面積變少，而有撥液效果變得不充分的情況。此外，比10個少的情況，突起的間隔變大，所以液滴進入突起之間，液滴和突起以外的平坦部接觸，而有撥液性降低的情況。再者，若10000μm²中的突起的個數為1000個以上，則突起的間隔大且液滴進入突起之間的情況變少，而有撥液性更加提高的情況。此處，可取得使用掃描式電子顯微鏡的表面的觀察照片，從將該照片進行二值化的圖像讀取突起的個數。將照片進行二值化的方法，首先使用圖像處理濾波器，對取得的表面觀察照片進行平均化處理，去除雜訊後，為了使突起與構造體即薄膜的表面的分界清晰，對進行過平均化處理的表面觀察照片進行二值化處理。二值化係0~256色階之中，以適當的臨限值進行二值化，使突起部清晰。再者，進行二值化的臨限值最好設定在80~140之間。若臨限值小於80，則突起的區域變大，若大於140，則突起的區域變小，而有無法界定突起與構造體的表面的分界的情況。具體而言，首先以80作為進行二值化的臨限值進行二值化，計算白與黑的面積率。其後，將臨限值每隔1即變更該值直到140為止，計算各個臨限值的面積率，以連續5個點的兩端的面積率之差最小的5個點的中央點為臨限值，進行二值化(例如101~105的面積率之差最小的情況，以臨限值為103。)。此外，此處所謂的二值化，係將有濃淡的圖像轉換為白與黑的2個色階的處理，界定某臨限值，若各像素之值超過臨限值，則轉換為白，若低於臨限值，則轉換為黑。 In the surface of the structure of the present invention, if the number of the protrusions is 10 or more and 4 × 10 ⁵ or less in 10000 μm ² , it is easy to support the droplets on the surface of the structure with the apex of the protrusions, the droplets and the air. The contact area is increased, so that the liquid repellency is improved, so that it is preferably 1,000 or more and 4 × 10 ⁵ or less. When the number of the protrusions in 10000 μm ² is more than 4 × 10 ⁵ , when the droplets adhere, a sufficient space does not exist between the protrusions, and the contact area with air is small, and the liquid-repellent effect is not obtained. Full case. Further, in the case where there are fewer than 10, the interval between the projections is increased, so that the liquid droplets enter the projections, and the liquid droplets come into contact with the flat portions other than the projections, and the liquid repellency is lowered. In addition, when the number of the protrusions in 10000 μm ² is 1000 or more, the interval between the protrusions is large and the amount of the droplets entering between the protrusions is small, and the liquid repellency is further improved. Here, an observation photograph using the surface of the scanning electron microscope can be obtained, and the number of projections can be read from the image in which the photograph is binarized. In the method of binarizing a photo, first, an image processing filter is used to average the obtained surface observation photographs, and after the noise is removed, in order to make the boundary between the protrusion and the surface of the structure, that is, the film clear, The averaged surface observation photograph was binarized. Among the 0 to 256 gradations of the binarization system, the binarization is performed with an appropriate threshold to make the protrusions clear. Furthermore, the threshold for binarization is preferably set between 80 and 140. If the threshold value is less than 80, the area of the protrusion becomes large, and if it is larger than 140, the area of the protrusion becomes small, and there is a case where the boundary between the protrusion and the surface of the structure cannot be defined. Specifically, first, 80 is used as a threshold for binarization, and the area ratio of white and black is calculated. Thereafter, the threshold value is changed every one time until the value is changed to 140, and the area ratio of each threshold value is calculated, and the central point of the five points having the smallest difference between the area ratios of the two consecutive points is the threshold. The value is binarized (for example, the difference between the area ratios of 101 to 105 is the smallest, and the threshold value is 103). In addition, the so-called binarization here is a process of converting a dim image into two gradations of white and black, defining a threshold, and converting the white to a white if the value of each pixel exceeds the threshold. If it is below the threshold, it will be converted to black.

本發明之構造體表面的突起的平均直徑D最好為100nm以上、10μm以下。此處，所謂平均直徑D，係取得使用掃描式電子顯微鏡的表面的觀察照片，選擇將該照片二值化的圖像中的突起的等面積圓的直徑(以下記載為相當直徑)為最大的前10個與最小的倒數10個的突起，取該等20個相當直徑的平均。然而，此時測定的突起為完全獨立的突起，2個以上的突起連接的情形在表面的觀察照片的時候即除外。此外，關於倒數10個突起，相當直徑小於50nm的不作為突起處理。將照片進行二值化的方法，係以和上述方法同樣的方法進行二值化。 The average diameter D of the protrusions on the surface of the structure of the present invention is preferably 100 nm or more and 10 μm or less. Here, the average diameter D is obtained by observing a photograph using a surface of a scanning electron microscope, and selecting the diameter of the equilateral circle of the protrusion (hereinafter referred to as a corresponding diameter) of the image in which the photograph is binarized is maximized. The top 10 and the smallest 10 countdown The protrusions take the average of the 20 equivalent diameters. However, the protrusions measured at this time are completely independent protrusions, and the case where two or more protrusions are connected is excluded when the photograph is observed on the surface. Further, regarding the countdown of 10 protrusions, a diameter of less than 50 nm is not treated as a protrusion. The method of binarizing a photograph is binarized in the same manner as the above method.

關於相當直徑的具體測定方法，記載於下。在使用掃描式電子顯微鏡的表面的觀察照片中，觀察到的突起為圓的情況，其直徑為相當直徑，不是圓的情況，替換為等面積的圓時的直徑為相當直徑。平均直徑D小於100nm的情況，要均勻得到此種突起很耗時，有工業上利用極為困難的情況。大於10μm的情況，在液滴附著時，難以使其與突起之間形成空氣層，有得不到撥液效果的情況。 The specific measurement method for the equivalent diameter is described below. In the observation photograph of the surface using the scanning electron microscope, the observed protrusion is a circle, and the diameter thereof is a considerable diameter, which is not a circle, and the diameter when replaced with a circle of an equal area is a considerable diameter. In the case where the average diameter D is less than 100 nm, it is time-consuming to obtain such a protrusion uniformly, and it is extremely difficult to use industrially. In the case of more than 10 μm, it is difficult to form an air layer between the droplets and the protrusions, and a liquid-repelling effect may not be obtained.

以本發明之構造體表面的任意範圍的面積為基底面積S，以突起的底面在該範圍所占的面積的合計為突起總面積A時，最好突起總面積的比例(A/S)為10%以上、30%以下。上述突起總面積的比例大於30%的情況，在液滴附著時，充分的空間不存在於液滴和突起之間，和空氣的接觸面積變少，故有撥液效果變得不充分的情況。此外，小於10%的情況，突起的間隔變大，所以液滴進入突起之間，液滴和突起以外的平坦部接觸，有撥液性降低的情況。 The area of any range of the surface of the structure of the present invention is the base area S, and when the total area of the surface of the protrusion in the range is the total area A of the protrusions, the ratio of the total area of the protrusions (A/S) is preferably 10% or more and 30% or less. When the ratio of the total area of the projections is more than 30%, when the droplets adhere, a sufficient space does not exist between the droplets and the projections, and the contact area with the air is small, so that the liquid-repellent effect is insufficient. . Further, in the case of less than 10%, the interval between the projections is increased, so that the liquid droplets enter the projections, and the liquid droplets come into contact with the flat portions other than the projections, and the liquid repellency may be lowered.

突起總面積的比例(A/S)例如如下求出(以取一邊為100μm的正方形的範圍作為上述任意的範圍的情況為例進行說明)。設定一邊為100μm的正方形的範圍時，基底面積S為10000μm²，取得使用掃描式電子顯微鏡的表面的觀察照片，從將該照片進行二值化的圖像得到此正方形區域的突起總面積A，由此等圖像計算突起總面積的比例(A/S)。將照片進行二值化的方法，係以和上述方法同樣的方法進行。 The ratio (A/S) of the total area of the projections is obtained, for example, as follows (for example, a case where a square having a side of 100 μm is taken as the above-described arbitrary range) will be described as an example. When the range of a square of 100 μm is set, the substrate area S is 10000 μm ² , and an observation photograph of the surface of the scanning electron microscope is obtained, and the total area A of the projections of the square region is obtained from the image obtained by binarizing the photograph. From this image, the ratio of the total area of the protrusions (A/S) is calculated. The method of binarizing a photograph is carried out in the same manner as the above method.

此外，突起傾斜，難以從表面的觀察照片讀取突起所占的面積的情況，可以用液狀矽氧橡膠等取薄膜表面的模子，從該模子的表面圖像讀取突起所占的面積。從硬化的液狀矽氧橡膠剝取薄膜時，液狀矽氧橡膠的表面形成多數個與突起底面對應的孔。取得此表面的掃描式電子顯微鏡照片，將孔所占的面積替換成突起所占的面積。 Further, when the projection is inclined, it is difficult to read the area occupied by the projection from the observation photograph on the surface, and the mold on the surface of the film can be taken by liquid helium oxide rubber or the like, and the area occupied by the projection can be read from the surface image of the mold. When the film is peeled off from the hardened liquid silicone rubber, the surface of the liquid silicone rubber forms a plurality of holes corresponding to the bottom surface of the protrusion. A scanning electron microscope photograph of the surface was taken, and the area occupied by the holes was replaced with the area occupied by the protrusions.

此外，前述突起的平均高度H與平均直徑D之比(H/D)最好為1以上、50以下。平均高度H與平均直徑D之比(H/D)小於1的情況，在水滴附著時，難以使其與突起之間形成空氣層，有得不到撥液效果的情況。另一方面，大於50的情況，有時要很耗時才能得到此種突起。此外，有突起折斷或容易變形等耐久性降低的情況。 Further, the ratio (H/D) of the average height H of the protrusions to the average diameter D is preferably 1 or more and 50 or less. When the ratio (H/D) of the average height H to the average diameter D is less than 1, it is difficult to form an air layer between the water droplets and the protrusions, and the liquid-repellent effect may not be obtained. On the other hand, in the case of more than 50, it is sometimes time consuming to obtain such protrusions. Further, there is a case where the durability such as the protrusion is broken or the deformation is easily deformed.

此處，所謂平均高度H，係從使用掃描式電子顯微鏡的剖面的觀察照片選擇高度最大前10個與高度最小倒數10個的突起，平均該等20個突起高度。此外，所謂高度，為從構造體表面到突起頂部的距離。此處，於選擇高度最小倒數10個之際，係將高度為50nm以上者視為突起，不到該高度者不作為突起處理。 Here, the average height H is a projection having a maximum height of the first 10 and a minimum height of 10 from the observation photograph of the cross section using the scanning electron microscope, and the average of the 20 protrusion heights is averaged. Further, the height is the distance from the surface of the structure to the top of the protrusion. Here, when the minimum height is 10, the height is 50 nm or more, and the protrusion is regarded as a protrusion.

再者，突起的平均高度H最好為500nm~100μm。平均高度H小於500nm的情況，液滴容易接觸到基底，有撥液性降低的情況。此外，大於100μm的情況，往往突起間距離也與高度成比例地擴大，此時液體在突起間潤濕擴大，有撥液性降低的情況。此外，有突起折斷或容易變形等耐久性降低的情況。 Further, the average height H of the protrusions is preferably from 500 nm to 100 μm. When the average height H is less than 500 nm, the droplets are likely to come into contact with the substrate, and the liquid repellency may be lowered. Further, in the case of more than 100 μm, the distance between the protrusions is also enlarged in proportion to the height, and at this time, the liquid is wetted and expanded between the protrusions, and the liquid repellency is lowered. Further, there is a case where the durability such as the protrusion is broken or the deformation is easily deformed.

此外，本發明之構造體不受薄膜限定，只要為可表面熱成形者，可為任何形狀，但從生產性或成本的觀點來考量，薄膜較好。 Further, the structure of the present invention is not limited by the film, and may be any shape as long as it can be surface thermoformed, but the film is preferable from the viewpoint of productivity or cost.

再者，只要為可形成上述突起的材料，可為任何材料，最好使用氟樹脂或矽系樹脂、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚對苯二甲酸丙二酯、聚對苯二甲酸丁二酯等聚酯系樹脂、聚乙烯、聚苯乙烯、聚丙烯、聚異丁烯、聚丁烯、聚甲基戊烯等聚烯烴系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、聚醚系樹脂、聚酯醯胺系樹脂、聚醚酯系樹脂、丙烯酸系樹脂、聚胺基甲酸乙酯系樹脂、聚碳酸酯系樹脂、或聚氯乙烯系樹脂等。特別是最好使用表面能量低的氟系樹脂或矽系樹脂、聚乙烯、聚苯乙烯、聚丙烯、聚異丁烯、聚丁烯、聚甲基戊烯等聚烯烴系樹脂等。就構造體的材料而言，最好含有此等樹脂作為主要的成分。再者，所謂主要的成分，係指以構成構造體的樹脂整體為100質量%時，占50質量%以上的成分。再者，主要的成分為50質量%以上較好，為80質量%以上更好。 Further, as long as it is a material capable of forming the above protrusions, any material may be preferably used, such as fluororesin or lanthanum resin, polyethylene terephthalate, polyethylene naphthalate, or polytrimethylene terephthalate. Polyester resin such as diester or polybutylene terephthalate, polyolefin resin such as polyethylene, polystyrene, polypropylene, polyisobutylene, polybutene, polymethylpentene, or polyamine resin Polyimine resin, polyether resin, polyester amide resin, polyether ester resin, acrylic resin, polyurethane resin, polycarbonate resin, or polyvinyl chloride Resin, etc. In particular, it is preferable to use a fluorine-based resin or a fluorene-based resin having a low surface energy, a polyolefin-based resin such as polyethylene, polystyrene, polypropylene, polyisobutylene, polybutene or polymethylpentene. As for the material of the structure, it is preferable to contain these resins as a main component. In addition, the main component is a component which accounts for 50 mass % or more when the whole resin which comprises a structure is 100 mass %. Further, the main component is preferably 50% by mass or more, more preferably 80% by mass or more.

再者，可在聚合時或聚合後將各種添加劑加入適用於本發明的材料中。就可添加調配的添加劑的例子而言，可舉例如有機微粒子、無機微粒子、分散劑、染料、螢光增白劑、抗氧化劑、耐候劑、靜電防止劑、脫膜劑、增黏劑、可塑劑、pH調整劑及鹽等。特別是作為脫膜劑，最好進行在聚合時添加少量長鏈羧酸或者長鏈羧酸鹽等低表面張力的羧酸或其衍生物、及長鏈醇或其衍生物、改質矽油等低表面張力的醇化合物等。 Further, various additives may be added to the materials suitable for the present invention at the time of polymerization or after polymerization. Examples of the additive to be added may, for example, be organic fine particles, inorganic fine particles, a dispersant, a dye, a fluorescent whitening agent, an antioxidant, a weathering agent, an antistatic agent, a release agent, a tackifier, or a plasticizer. Agent, pH adjuster and salt. In particular, as a release agent, it is preferred to add a small amount of a long-chain carboxylic acid or a derivative thereof such as a long-chain carboxylic acid or a long-chain carboxylate during polymerization, a long-chain alcohol or a derivative thereof, a modified eucalyptus oil, or the like. Low surface tension alcohol compounds and the like.

此外，構造體可以是積層構造，只在形成突起的表層上使用上述材料。作為表層以外的層，藉由設定強度或耐熱性高於表層的材料，提高成形時的平面性，也可以抑制構造體的變形或皺紋。 Further, the structure may be a laminated structure, and the above materials are used only on the surface layer on which the protrusions are formed. As a layer other than the surface layer, by setting the material having higher strength or heat resistance than the surface layer, the planarity at the time of molding can be improved, and deformation or wrinkles of the structure can be suppressed.

再者，構造體可以是連續體，也可以是薄片體。構造體的厚度並不受特別限制。 Further, the structure may be a continuous body or a sheet. The thickness of the structure is not particularly limited.

作為本發明較佳的形態，可舉從突起根部的中心畫到前端的中心的直線的方向(以後有時簡略記為「突起的方向」)為不一定的形態。此處，所謂突起的方向為不一定，係指各個突起的方向在構造體表面上的空間為隨機的，更具體而言，係指各個突起的方向在(i)與構造體表面平行的面內的突起傾斜的方向、及(ii)對於與構造體表面垂直的方向傾斜的角度的至少一方為隨機的。再者，在前述(i)及(ii)的各個中測定各個突起的方向或角度，關於(i)，除了各個突起的方向為相同的情況之外皆有困難，所以突起的方向為不一定的確認，係不分離上述(i)(ii)而如下進行判斷。即，以與構造體的表面垂直且每隔45°的4個方向的面切斷構造體，觀察剖面時，在剖面的突起的基準角度最大幅傾斜的剖面中，若突起的70%以上相對於基準角度超過±20°，則判斷成突起的方向為不一定。此處，所謂基準角度，係指從剖面的觀察照片選擇10個突起，測定該等突起在剖面的觀察照片上對於與構造體的表面垂直的方向傾斜的角度(以後記載為「剖面傾斜角度」)，進行平均的角度。在此等角度的判斷時，使用掃描式電子顯微鏡即可。由於從根部的中心畫到前端的中心的直線的方向為不一定，在液滴周邊，潤濕產生不均勻性，可促進液滴移動。其結果，使薄膜稍微傾斜的情況，或者即使保持水平，薄膜上的液滴也會被排除，可更加提高防止液滴附著的效果。 In a preferred embodiment of the present invention, a direction from a center of the root of the projection to a straight line at the center of the tip end (hereinafter sometimes referred to simply as "the direction of the protrusion") may be used. Here, the direction of the protrusion is not necessarily, meaning that the direction of each protrusion is random on the surface of the structure, and more specifically, the direction of each protrusion is (i) the plane parallel to the surface of the structure At least one of the direction in which the protrusions are inclined and (ii) the angles inclined with respect to the direction perpendicular to the surface of the structure are random. Furthermore, in each of the above (i) and (ii), the direction or angle of each protrusion is measured, and with respect to (i), it is difficult except for the case where the directions of the respective protrusions are the same, so the direction of the protrusion is not necessarily The confirmation is not determined by separating the above (i) and (ii) as follows. That is, to hang with the surface of the structure In the cross section of the four directions of 45° straight, the structure is cut, and when the cross section is observed, in the cross section in which the reference angle of the projection of the cross section is most inclined, if 70% or more of the projections exceed ±20° with respect to the reference angle, Then, it is judged that the direction of the protrusion is not necessarily. Here, the reference angle means that ten protrusions are selected from the observation photograph of the cross section, and the angle at which the protrusions are inclined in the direction perpendicular to the surface of the structure in the observation photograph of the cross section (hereinafter referred to as "section inclination angle" is measured. ), the average angle is taken. At the judgment of these angles, a scanning electron microscope can be used. Since the direction of the straight line drawn from the center of the root to the center of the front end is not constant, the wetting is uneven around the droplet, and the movement of the droplet can be promoted. As a result, when the film is slightly inclined, or even if it is kept horizontal, the droplets on the film are removed, and the effect of preventing the adhesion of the droplets can be further enhanced.

作為本發明其他較佳的形態，可舉突起的方向為一定的形態。此處，所謂突起的方向為一定，係指各個突起的方向在構造體表面上的空間為大致一方向，更具體而言，係指各個突起的方向在(i)與構造體表面平行的面內的突起傾斜的方向、及(ii)對於與構造體表面垂直的方向傾斜的角度的兩者皆相同。第3圖係突起的方向為一定的本發明之構造體即樹脂薄膜的剖面概略圖，為(i)和與構造體表面平行的面內的突起傾斜的方向平行的剖面。如第3圖所示，可從剖面判斷各個突起係(ii)對於與構造體表面垂直的方向傾斜的角度θ為大致一定。此種突起的方向為一定的確認係如下進行。以與構造體的表面垂直且每隔45°的4個方向的面切斷，觀察剖面時，在剖面的突起的基準角度最大幅傾斜的剖面中，定義為突起的70%以上的突起相對於基準角度，在±20°的範圍全體傾斜。此處，所謂基準角度，係指從剖面的觀察照片選擇10個突起，測定該等突起在剖面的觀察照片上對於與構造體表面垂直的方向傾斜的角度(以後記載為「剖面傾斜角度」)，進行平均的角度。在此等角度的判斷時，使用掃描式電子顯微鏡即可。由於從剖面的突起根部的中心畫到突起前端的中心的直線的方向為一定，在液滴周邊產生潤濕的異向性，可促進液滴往特定的方向移動。其結果，使薄膜稍微向特定的方向傾斜的情況，或者即使保持水平，薄膜上的液滴也會被排除，可提高防止液滴附著的效果。 As another preferable aspect of the present invention, the direction of the protrusions is a constant form. Here, the direction of the protrusion is constant, meaning that the direction of each protrusion on the surface of the structure is substantially one direction, and more specifically, the direction of each protrusion is (i) the plane parallel to the surface of the structure. The direction in which the protrusions are inclined in the same direction and (ii) the angles inclined with respect to the direction perpendicular to the surface of the structure are the same. Fig. 3 is a schematic cross-sectional view showing a resin film which is a structure of the present invention in which the direction of the protrusion is constant, and is a cross section in which (i) is parallel to the direction in which the protrusions in the plane parallel to the surface of the structure are inclined. As shown in Fig. 3, the angle θ at which the respective protrusions (ii) are inclined with respect to the direction perpendicular to the surface of the structure can be determined from the cross section. The confirmation of the direction of such protrusions is as follows. A section perpendicular to the surface of the structure and cut in four directions every 45°, and when the cross section is observed, the section at which the reference angle of the protrusion of the section is inclined is the largest. Among them, 70% or more of the protrusions defined as the protrusions are inclined at a total angle of ±20° with respect to the reference angle. Here, the reference angle means that ten protrusions are selected from the observation photograph of the cross section, and the angle at which the protrusions are inclined in the direction perpendicular to the surface of the structure on the observation photograph of the cross section (hereinafter referred to as "section inclination angle") is measured. , to average the angle. At the judgment of these angles, a scanning electron microscope can be used. Since the direction of the straight line drawn from the center of the protruding root portion of the cross section to the center of the tip end of the projection is constant, wetted anisotropy is generated around the droplet, and the droplet can be moved in a specific direction. As a result, when the film is slightly inclined in a specific direction, or even if it is kept horizontal, the droplets on the film are removed, and the effect of preventing the adhesion of the droplets can be improved.

突起最好從根部的中心畫到前端的中心的直線之中，70%以上相對於與構造體表面垂直的方向，在25°以上、50°以下的範圍內傾斜。此處，所謂在25°以上、50°以下的範圍內傾斜，係指對於薄膜的表面在垂直的方向切斷，觀察剖面時，剖面的突起之中，70%以上的突起在25°以上、50°以下的角度傾斜。70%以上的突起的傾斜小於25°的情況，有不充分顯現液滴周邊的潤濕的不均勻性的情況。因此，液滴難以移動，有殘留於薄膜表面的情況。另一方面，70%以上的突起的傾斜大於50°的情況，突起與液滴的接觸面積變大，有損害撥液性的情況。。 Preferably, the projection is formed from a center of the root portion to a straight line at the center of the front end, and 70% or more is inclined in a range of 25° or more and 50° or less with respect to a direction perpendicular to the surface of the structure. Here, the inclination in the range of 25° or more and 50° or less means that the surface of the film is cut in the vertical direction, and when the cross section is observed, among the protrusions of the cross section, 70% or more of the protrusions are 25° or more. Angled below 50°. When the inclination of 70% or more of the protrusions is less than 25°, the unevenness of the wetting around the droplets may not be sufficiently exhibited. Therefore, the droplets are difficult to move and there is a case where they remain on the surface of the film. On the other hand, when the inclination of 70% or more of the protrusions is larger than 50°, the contact area between the protrusions and the droplets becomes large, and the liquid repellency may be impaired. .

最好前述突起的高度為不一定。此處，所謂突起的高度為不一定，係指以前述突起的平均高度H為100%時，高度不到80%或超過120%的突起的個數為剖面的突起個數的70%以上。第4圖為突起的高度為不一定的本發明之於表面具有突起的構造體即樹脂薄膜的剖面概略圖。由於液滴周邊的突起的高度為不一定，液滴周邊的潤濕成為不均勻的狀態，液滴容易移動。其結果，可抑制液滴在薄膜表面的殘留。使薄膜稍微向特定的方向傾斜的情況，或者即使保持水平，薄膜上的液滴也會被排除，可提高防止液滴附著的效果。 Preferably, the height of the aforementioned protrusions is not necessarily. Here, the height of the protrusion is not necessarily the case, and when the average height H of the protrusion is 100%, the number of protrusions having a height of less than 80% or more than 120% is 70% or more of the number of protrusions in the cross section. Fig. 4 is a schematic cross-sectional view showing a resin film which is a structure having a projection on the surface of the present invention, in which the height of the projection is not constant. Since the height of the protrusion around the droplet is not constant, the wetting around the droplet becomes uneven, and the droplet easily moves. As a result, the residual of the droplet on the surface of the film can be suppressed. When the film is slightly inclined in a specific direction, or even if it is kept horizontal, the droplets on the film are removed, and the effect of preventing the adhesion of the droplets can be improved.

本發明之於表面具有突起的構造體即薄膜可利用經由例如如第5圖、第6圖、第7圖所示的裝置的步驟製造。 The film of the present invention having a structure having protrusions on its surface can be produced by a step of, for example, a device as shown in Figs. 5, 6, and 7.

第5圖、第7圖顯示用於製造於薄膜的表面具有突起的薄膜的製造裝置50、70的剖面概略圖。此外，第6圖為顯示在製造裝置50中，從模具剝離薄膜的動作的剖面概略圖。 Fig. 5 and Fig. 7 are schematic cross-sectional views showing the manufacturing apparatuses 50 and 70 for producing a film having projections on the surface of the film. In addition, FIG. 6 is a schematic cross-sectional view showing an operation of peeling a film from a mold in the manufacturing apparatus 50.

在第5圖所示之例中，在捲出單元52中，預先從捲出輥51拉出薄膜，其次在加壓單元54中，將於表面形成有突起構造並經加熱的模具53按壓於間歇送來的薄膜上，進行加壓，其後，藉由在保持接觸狀態下進行冷卻，於薄膜的表面形成預定的突起。 In the example shown in Fig. 5, in the unwinding unit 52, the film is pulled out from the take-up roll 51 in advance, and secondly, in the pressurizing unit 54, a protruding structure is formed on the surface and pressed by the heated mold 53. Pressurization is performed on the intermittently fed film, and thereafter, predetermined protrusions are formed on the surface of the film by cooling while maintaining the contact state.

成形部包含形成預定的突起的加壓單元54、及將利用加壓貼附於模具53上的薄膜從模具53上剝離的剝離手段55。剝離手段55係由對薄膜以緊抱成S型的方式進行夾持的一對配置成平行的剝離輥55A及剝離輔助輥55B所構成。間歇送來的薄膜的一面在加壓單元54內為模具53所熱成形，熱成形後，如第6圖所示，藉由使上述剝離手段55向上游側移動，就可從模具53上依次剝離貼附於模具53上的薄膜。其後，為捲取輥56所捲取。 The molding portion includes a pressurizing unit 54 that forms a predetermined projection, and a peeling means 55 that peels the film attached to the mold 53 by pressure from the mold 53. The peeling means 55 is composed of a pair of parallel peeling rolls 55A and peeling auxiliary rolls 55B which are sandwiched so that the film is held in an S-shape. One side of the intermittently fed film is thermoformed in the press unit 54 for the mold 53, and after thermoforming, as shown in Fig. 6, By moving the peeling means 55 to the upstream side, the film attached to the mold 53 can be sequentially peeled off from the mold 53. Thereafter, it is taken up by the take-up roll 56.

再者，在第5圖中，57、58顯示加壓板，59、60顯示為了使薄膜在模具53部分的間歇搬送順利地進行而設置的緩衝手段。 Further, in Fig. 5, 57 and 58 show pressure plates, and 59 and 60 show buffer means for providing intermittent transfer of the film in the mold 53 portion.

藉由調整剝離輥55A與模具的離間距離55H或剝離時的模具53的溫度，可使所成形的突起的方向變得不一定或一定。 By adjusting the distance 55H between the peeling roller 55A and the mold or the temperature of the mold 53 at the time of peeling, the direction of the formed protrusion can be made unnecessary or constant.

此外，例如將剝離輥55A與模具的離間距離55H確保一定距離，比構成薄膜成形面的樹脂的玻璃轉移溫度更低地設定剝離時的模具的溫度的情況，可形成傾斜方向為一定的突起。剝離時，向從與模具表面垂直的方向傾斜的方向施加張力至薄膜，可形成變形成向一定方向傾斜的突起。再者，剝離後的薄膜受到充分冷卻，所以即使受到和剝離輔助輥55B的接觸壓力，傾斜狀態也不易變化。 In addition, for example, when the separation distance 55H between the peeling roller 55A and the mold is fixed to a certain distance, the temperature of the mold at the time of peeling is set lower than the glass transition temperature of the resin constituting the film forming surface, and a projection having a constant inclination direction can be formed. At the time of peeling, tension is applied to the film in a direction inclined from the direction perpendicular to the surface of the mold, and a protrusion which is inclined in a certain direction can be formed. Further, since the peeled film is sufficiently cooled, even if it is subjected to the contact pressure with the peeling auxiliary roller 55B, the inclined state does not easily change.

此外，例如盡量縮小離間距離55H，將剝離時的模具的溫度設定於構成薄膜成形面的樹脂的玻璃轉移溫度附近的情況，可形成傾斜方向不一定的突起。這是因為在剝離時，由於向對於模具表面大致垂直的方向施加張力而剝離薄膜，所以一旦形成對於薄膜的表面垂直的突起後，藉由以一定的壓力被剝離輔助輥55B所按壓，尚未充分冷卻完的突起變形，而偏向於隨機的方向。 Further, for example, when the distance between the separations is minimized to 55H and the temperature of the mold at the time of peeling is set to the vicinity of the glass transition temperature of the resin constituting the film forming surface, protrusions having a constant inclination direction can be formed. This is because, at the time of peeling, since the film is peeled off by applying tension to a direction substantially perpendicular to the surface of the mold, once the protrusion perpendicular to the surface of the film is formed, it is not sufficiently pressed by the peeling auxiliary roller 55B at a constant pressure. The cooled protrusions deform and are biased in a random direction.

在第7圖所示之例中，從捲出輥73拉出薄膜，供應給被加熱輥75所加熱的表面上形成有突起構造的環帶狀的模具76上。 In the example shown in Fig. 7, the film is pulled out from the take-up roll 73, and supplied to an endless belt-shaped mold 76 having a projection structure formed on the surface heated by the heated roll 75.

在模具76的外表面上形成有獨立且離散地配置的微細凹坑，在即將和薄膜接觸之前，被加熱輥75所加熱。被連續供應的薄膜被壓輥77按壓於模具76中加工了凹坑構造的表面上，在薄膜的表面上形成突起。 On the outer surface of the mold 76, fine pits which are independently and discretely arranged are formed, which are heated by the heating roller 75 immediately before coming into contact with the film. The continuously supplied film is pressed against the surface of the mold 76 in which the pit structure is formed by the press roller 77, and a projection is formed on the surface of the film.

其後，薄膜在和模具76的表面密合的狀態下，被搬送到冷卻輥78的外表面位置。薄膜利用冷卻輥78經由模具76由於導熱的緣故受到冷卻後，利用剝離輥79從模具76剝離，捲取於捲取輥81。藉由此種步驟，可將形成有突起的薄膜連續地以高生產性逐漸熱成形。 Thereafter, the film is conveyed to the outer surface position of the cooling roll 78 in a state of being in close contact with the surface of the mold 76. The film is cooled by the cooling roll 78 through the die 76 by heat transfer, and then peeled off from the die 76 by the peeling roller 79, and taken up by the take-up roll 81. By such a step, the film on which the protrusions are formed can be continuously thermoformed with high productivity.

藉由調整剝離輥79與模具的離間距離79H或冷卻輥78的溫度，可使所成形的突起的方向變得不一定或一定。 By adjusting the separation distance 79H of the peeling roller 79 from the mold or the temperature of the cooling roller 78, the direction of the formed projection can be made unnecessary or constant.

例如增大剝離輥79與冷卻輥78的離間距離79H，比構成薄膜成形面的樹脂的玻璃轉移溫度更低地設定剝離時的模具的溫度的情況，可形成突起的方向為一定的構造體。 For example, when the separation distance 79H between the peeling roller 79 and the cooling roller 78 is increased, the temperature of the mold at the time of peeling is set lower than the glass transition temperature of the resin constituting the film forming surface, and a structure in which the direction of the protrusion is constant can be formed.

此外，例如盡量縮小離間距離79H，將剝離時的模具的溫度設定於構成薄膜成形面的樹脂的玻璃轉移溫度附近的情況，可形成突起的方向為不一定的構造體。這是因為在剝離時，由於向對於模具表面大致垂直的方向施加張力而剝離薄膜，所以一旦形成對於薄膜的表面垂直的突起後，在其後搬送輥80與成形面接觸時，被以一定的壓力按壓，尚未充分冷卻完的突起變形，而偏向於隨機的方向。 Further, for example, when the distance between the separations is minimized and the temperature of the mold at the time of peeling is set to the vicinity of the glass transition temperature of the resin constituting the film forming surface, the direction in which the protrusions are formed can be formed. This is because, at the time of peeling, since the film is peeled off by applying tension to a direction substantially perpendicular to the surface of the mold, once the protrusion perpendicular to the surface of the film is formed, the transfer roller 80 is brought into contact with the forming surface thereafter. At this time, the protrusion is pressed with a certain pressure, and the protrusion which has not been sufficiently cooled is deformed, and is biased in a random direction.

於表面具有凹坑構造的各模具的製作方法，可舉對金屬表面直接施以切削、雷射加工或電子射線加工的方法；對形成於金屬表面上的鍍敷皮膜直接施以切削、雷射加工或電子射線加工的方法；製作此等反轉的突起形狀後，利用電鑄製作凹坑形狀的方法。此外，可舉將抗蝕劑塗布於基板上後，利用光微影手法以預定的圖案形成抗蝕劑後，蝕刻處理基板，形成突起，去除抗蝕劑後，以電鑄利用其反轉圖案得到凹坑構造的方法等。 The method for manufacturing each mold having a concave structure on the surface may be a method of directly applying cutting, laser processing or electron beam processing to a metal surface; directly applying a cutting or laser to a plating film formed on a metal surface. A method of processing or electron beam processing; a method of producing a pit shape by electroforming after forming the inverted protrusion shape. Further, after the resist is applied onto the substrate, the resist is formed in a predetermined pattern by photolithography, and then the substrate is etched to form a protrusion, and after the resist is removed, the reverse pattern is electroformed. A method of obtaining a pit structure or the like.

此外，也可以藉由對模具表面施以蝕刻，製作於表面具有凹坑構造的模具。就模具的材料而言，只要是矽晶圓、各種金屬材料、玻璃、陶瓷、塑膠、碳材料等具有強度與所要求的精度的加工性的材料即可，具體而言，為Si、SiC、SiN、多晶Si、玻璃、Ni、Cr、Cu、Al、Fe、Ti、C、進一步含一種以上此等元素的材料即可。此外，可以藉由對於表面具有以此等元素為主要成分的非晶構造的模具表面，利用硝酸等強酸性的液體進行蝕刻而製作。 Alternatively, a mold having a pit structure on the surface may be formed by etching the surface of the mold. As far as the material of the mold is concerned, as long as it is a material having a strength and a required precision, such as a silicon wafer, various metal materials, glass, ceramics, plastic, or carbon material, specifically, Si, SiC, SiN, polycrystalline Si, glass, Ni, Cr, Cu, Al, Fe, Ti, C, and materials further containing one or more of these elements may be used. Further, it can be produced by etching a surface of a mold having an amorphous structure having such an element as a main component on the surface, using a highly acidic liquid such as nitric acid.

在本發明中，希望更加增大和水的接觸角，使撥液性更加提高的情況，在如上述所得到的突起的表面被覆表面能量低的官能基，特別是氟基較理想。 In the present invention, it is desirable to further increase the contact angle with water and to improve the liquid repellency. It is preferable to coat the surface of the protrusion obtained as described above with a functional group having a low surface energy, particularly a fluorine group.

就此種被覆處理方法而言，只要不是以被覆材料埋填掉突起的構造的方法，則不受特別限定，可舉例如朗繆爾一布洛吉特(Langmuir-Blodgett)法(LB法)、物理氣相沉積法(PVD法)、化學氣相沉積法(CVD法)、自組織法、濺鍍法、塗布以溶劑稀釋單分子的材料的方法等。 The coating treatment method is not particularly limited as long as it is not a method of embedding the projections with the coating material. Examples include Langmuir-Blodgett (LB method), physical vapor deposition (PVD), chemical vapor deposition (CVD), self-organization, sputtering, coating A method of diluting a single molecule material with a solvent or the like.

再者，也可以對形成突起的平板施以如上述材料的任意厚度的撥液處理後，利用上述的方法形成突起。 Further, after the liquid-repellent treatment of any thickness of the above-described material is applied to the flat plate on which the projections are formed, the projections may be formed by the above-described method.

本發明之構造體可發揮其表面特性，適用於例如細胞培養片或生物晶片等生物裝置、光學薄膜或異向性薄膜等光學裝置、撥液片、防污片等建築材料。 The structure of the present invention can exhibit surface characteristics and can be applied to, for example, a biological device such as a cell culture sheet or a biochip, an optical device such as an optical film or an anisotropic film, a building material such as a liquid-repellent sheet or an anti-fouling sheet.

實施例Example 〔測定方法〕〔test methods〕 (突起的個數的測定) (Measurement of the number of protrusions)

將薄膜切成10mm×10mm，利用掃描式電子顯微鏡((股)KEYENCE VE-7800)，用倍率5000倍以反射電子像觀察表面。此時的圖像尺寸為13.3μm×13.3μm，像素數為375像素×375像素，1個像素的大小為35nm×35nm。對此圖像進行平均化處理，去除雜訊。其後，進行二值化處理，使突起與薄膜的表面的分界清晰。 The film was cut into 10 mm × 10 mm, and the surface was observed with a reflection electron microscope by a scanning electron microscope (KEYENCE VE-7800) at a magnification of 5000 times. The image size at this time was 13.3 μm × 13.3 μm, the number of pixels was 375 pixels × 375 pixels, and the size of one pixel was 35 nm × 35 nm. This image is averaged to remove noise. Thereafter, binarization is performed to make the boundary between the protrusion and the surface of the film clear.

將照片進行二值化的方法係如下進行。首先，使用圖像處理濾波器，對取得的表面觀察照片進行平均化處理，去除雜訊。其後，為了使突起與構造體的表面的分界清晰，對進行過平均化處理的表面觀察照片進行二值化處理。二值化係0~256色階之中，以適當的臨限值進行二值化，使突起部與薄膜的表面的分界清晰。在這次取得的表面圖像中，進行二值化的臨限值首先以125進行，但不能順利得到二值化圖像的情況，在80~140之間調整臨限值。第8圖中顯示進行平均化處理後進行二值化的照片。 The method of binarizing a photograph is performed as follows. First, an image processing filter is used to average the acquired surface observation photographs to remove noise. Thereafter, in order to make the boundary between the protrusion and the surface of the structure clear, the surface observation photograph subjected to the averaging treatment is binarized. In the binarization system, among the 0~256 color steps, the binarization is performed with an appropriate threshold, so that the boundary between the protrusion and the surface of the film is clear. Clear. In the surface image obtained this time, the threshold value for binarization is first performed at 125, but the binarized image cannot be obtained smoothly, and the threshold value is adjusted between 80 and 140. Fig. 8 shows a photograph of binarization after averaging processing.

在測定突起的個數時，使用Snipping Tool(剪切工具)，一面對突起附上記號一面進行測定。將以此方法得到的突起個數換算成10000μm²中的突起個數。 When measuring the number of protrusions, a Snipping Tool was used, and the measurement was performed while attaching a mark to the protrusion. The number of protrusions obtained by this method was converted into the number of protrusions in 10000 μm ² .

(突起的平均直徑D的測定) (Measurement of average diameter D of protrusions)

將薄膜切成10mm×10mm，利用掃描式電子顯微鏡((股)KEYENCE VE-7800)，用倍率10000倍以反射電子像觀察表面。此時的圖像尺寸為12.1μm×9.1μm。再者，像素數為1280像素×960像素，1個像素的大小為9.4nm×9.5nm。對此圖像進行平均化處理，去除雜訊。其後，進行二值化處理，使突起與薄膜的表面的分界清晰。將照片進行二值化的方法係和(測定突起個數)之際同樣地進行。第9圖中顯示進行平均化處理後進行二值化的照片。 The film was cut into 10 mm × 10 mm, and the surface was observed with a reflection electron microscope by a scanning electron microscope (KEYENCE VE-7800) at a magnification of 10,000 times. The image size at this time was 12.1 μm × 9.1 μm. Furthermore, the number of pixels is 1280 pixels × 960 pixels, and the size of one pixel is 9.4 nm × 9.5 nm. This image is averaged to remove noise. Thereafter, binarization is performed to make the boundary between the protrusion and the surface of the film clear. The method of binarizing a photograph is performed in the same manner as in the case of measuring the number of protrusions. Fig. 9 shows a photograph of binarization after averaging processing.

從觀察照片選擇突起的相當直徑為最大的前10個與最小的倒數10個的突起，取該等20個的相當直徑的平均，作為平均直徑D。再者，在觀察照片中，觀察到的突起為圓的情況，將其直徑作為相當直徑，不是圓的情況，將替換為等面積的圓時的直徑作為相當直徑。 From the observation photograph, the protrusions were selected to have the largest diameter of the first 10 and the smallest 10 of the projections, and the average of the 20 equivalent diameters was taken as the average diameter D. Further, in the observation photograph, the observed protrusion is a circle, and the diameter is regarded as a relatively large diameter. When it is not a circle, the diameter when replacing the circle of the same area is regarded as a corresponding diameter.

(突起的平均高度H的測定) (Measurement of the average height H of the protrusions)

在對於薄膜的表面垂直的方向切斷薄膜，利用掃描式電子顯微鏡((股)KEYENCE VE-7800)，用倍率5000倍觀察其剖面。此時的圖像尺寸為24.3μm×18.2μm。再者，像素數為1280像素×960像素，1個像素的大小為19.0nm×19.0nm。從觀察照片選擇高度最大前10個與高度最小倒數10個的突起，將使該等20個的突起高度平均化者作為平均高度H。此外，所謂高度，為從薄膜表面到突起頂部的距離。 The film was cut in a direction perpendicular to the surface of the film, and the cross section was observed by a scanning electron microscope (KEYENCE VE-7800) at a magnification of 5000 times. The image size at this time was 24.3 μm × 18.2 μm. Furthermore, the number of pixels is 1280 pixels × 960 pixels, and the size of one pixel is 19.0 nm × 19.0 nm. From the observation photograph, the protrusions of the top 10 and the lowest height 10 are selected, and the height of the 20 protrusions is averaged as the average height H. Further, the so-called height is the distance from the surface of the film to the top of the protrusion.

(突起的剖面傾斜角度的測定) (Measurement of the inclination angle of the profile of the protrusion)

以與薄膜的表面垂直且每隔45°的4個方向的面切斷薄膜，就各個薄膜，利用掃描式電子顯微鏡((股)KEYENCE VE-7800)，用倍率5000倍觀察其剖面。觀察對象範圍為24.3μm×18.2μm，像素數為1280像素×960像素，1個像素的大小為19.0nm×19.0nm。就4張觀察照片，分別選擇10個突起，測定此等突起的(a)連結根部的中心與突起前端的中心的線和(b)和與構造體表面垂直的方向形成的角度，並且計算平均值，作為基準角度。將如此得到的剖面的突起的基準角度最大幅傾斜的剖面作為評估對象，將其剖面的10個突起的(a)連結根部的中心與突起前端的中心的線和(b)和與構造體表面垂直的方向形成的角度的個別值作為剖面傾斜角度，進行突起狀況(有無傾斜、突起的方向)的判定。再者，在各實施例、比較例中顯示的剖面的照片為突起的基準角度最大幅傾斜的剖面的照片。 The film was cut in a plane perpendicular to the surface of the film and in four directions every 45°, and the cross section of each film was observed by a scanning electron microscope (KEYENCE VE-7800) at a magnification of 5000 times. The observation target range was 24.3 μm × 18.2 μm, the number of pixels was 1280 pixels × 960 pixels, and the size of one pixel was 19.0 nm × 19.0 nm. For each of the four observation photographs, ten protrusions were selected, and the angles of (a) the center of the joint root and the center of the front end of the protrusion and (b) and the direction perpendicular to the surface of the structure were measured, and the average was calculated. The value is used as the reference angle. The cross section in which the reference angle of the projection of the cross section thus obtained is inclined to the maximum is used as the evaluation target, and the (10) of the 10 protrusions of the cross section and the line connecting the center of the root and the center of the protrusion front end and (b) and the surface of the structure are used. The individual value of the angle formed in the vertical direction is determined as the inclination angle of the section, and the state of the protrusion (the presence or absence of the inclination or the direction of the protrusion) is determined. In addition, the photograph of the cross section displayed in each Example and the comparative example is a photograph of the cross section which the inclination of the protrusion of the protrusion is the largest.

(實施例1) (Example 1) (1)薄膜 (1) film

使用含以聚丙烯為主體的聚合物(熔點144℃)的厚度100μm的薄膜。 A film having a thickness of 100 μm containing a polymer mainly composed of polypropylene (melting point 144 ° C) was used.

(2)模具 (2) mold

在不銹鋼板的表面被覆厚度100μm左右以Ni為主體的材料。其後，製作模具，該模具係對於模具表面，以雷射加工全面形成有直徑300nm至800nm左右的凹坑構造。形成有凹坑的區域相對於表面為20%。 The surface of the stainless steel plate was coated with a material mainly composed of Ni having a thickness of about 100 μm. Thereafter, a mold for forming a pit structure having a diameter of about 300 nm to 800 nm was formed on the surface of the mold by laser processing. The area in which the pits are formed is 20% with respect to the surface.

(3)成形裝置及條件 (3) Forming equipment and conditions

裝置適用如第5圖所示的裝置。加壓單元為以油壓泵加壓的機構，於內部上下安裝兩片加壓板，分別與加熱裝置、冷卻裝置連結。模具設置於下側加壓板的上面。此外，在加壓單元內設有用於剝離貼在模具上的薄膜的剝離手段。 The device is adapted to the device shown in Figure 5. The pressurizing unit is a mechanism that pressurizes the hydraulic pump, and two pressurizing plates are vertically mounted inside and connected to the heating device and the cooling device. The mold is placed on the lower side of the lower pressure plate. Further, a peeling means for peeling off the film attached to the mold is provided in the pressurizing unit.

成形時的模具溫度設定為150℃，就加壓力而言，全面施加5MPa的壓力。加壓時間為30秒。此外，剝離時的模具溫度為110℃。 The mold temperature at the time of molding was set to 150 ° C, and a pressure of 5 MPa was applied in total for the pressure application. The pressurization time is 30 seconds. Further, the mold temperature at the time of peeling was 110 °C.

剝離輥與薄膜的離間距離為0.1mm。將剝離的薄膜送到下游側的捲取裝置側捲取。 The distance between the peeling roller and the film was 0.1 mm. The peeled film is taken up to the side of the winding device on the downstream side for winding.

(4)成形結果 (4) Forming results

第10圖中顯示成形的薄膜的突起形成面的掃描式電子顯微鏡((股)KEYENCE VE-7800)所拍攝的照片。在本實施例中，於表面全面形成有平均直徑D為300nm、平均高度H為1.0μm、突起的平均高度H與平均直徑D 之比(H/D)為3.3的突起。此時，形成於10000μm²的突起的個數為21595個。突起傾斜的方向為不一定。再者，在對於薄膜的表面垂直的方向切斷薄膜時，剖面的突起之中，70%以上相對於與薄膜的表面垂直的方向傾斜5°以上。此外，第11圖為以掃描式電子顯微鏡拍攝本發明之於表面具有突起的構造體即樹脂薄膜的剖面的照片，突起的方向為不一定。 Fig. 10 is a photograph taken by a scanning electron microscope (KEYENCE VE-7800) showing the protrusion forming surface of the formed film. In the present embodiment, protrusions having an average diameter D of 300 nm, an average height H of 1.0 μm, and a ratio (H/D) of the average height H of the protrusions to the average diameter D of 3.3 were formed on the entire surface. At this time, the number of protrusions formed at 10000 μm ² was 21,595. The direction in which the protrusions are inclined is not necessarily. Further, when the film is cut in a direction perpendicular to the surface of the film, 70% or more of the protrusions in the cross section are inclined by 5 or more with respect to the direction perpendicular to the surface of the film. In addition, Fig. 11 is a photograph of a cross section of a resin film which is a structure having a projection on the surface of the present invention taken by a scanning electron microscope, and the direction of the protrusion is not necessarily required.

(5)撥液性、液滴移動性效果 (5) Liquid repellency and droplet mobility effect

將1.41μL的水滴下到撥液性物品的表面，使用接觸角計(協和界面科學社製造，CA-D型)，測定水滴的接觸角。一滴下水滴，水滴就在薄膜的表面滾動，無法停留在一處，所以不能測定接觸角。 1.41 μL of water was dropped on the surface of the liquid-repellent article, and the contact angle of the water drop was measured using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., CA-D type). A drop of water droplets, the water droplets rolling on the surface of the film, can not stay in one place, so the contact angle cannot be measured.

(實施例2) (Example 2) (1)薄膜 (1) film

(2)模具 (2) mold

在不銹鋼板的表面被覆厚度100μm左右以Ni為主體的材料。其後，製作模具，該模具係對於模具表面，以雷射加工全面形成有直徑300nm至1.0μm的凹坑構造。形成有凹坑的區域對於表面，為21%。 The surface of the stainless steel plate was coated with a material mainly composed of Ni having a thickness of about 100 μm. Thereafter, a mold was prepared which was formed into a pit structure having a diameter of 300 nm to 1.0 μm by laser processing on the surface of the mold. The area where the pits were formed was 21% for the surface.

(3)成形裝置及條件 (3) Forming equipment and conditions

裝置適用如第5圖所示的裝置。加壓單元為以油壓泵加壓的機構，於內部上下安裝兩片加壓板，分別與加熱裝置、冷卻裝置連結。模具設置於下側加壓板的上面。此外，在加壓單元內設有用於剝離貼在模具上的薄膜的剝離手段。成形時的模具溫度設定為150℃，就加壓力而言，全面施加5MPa的壓力。加壓時間為30秒。此外，剝離時的模具溫度為80℃。剝離輥與薄膜的離間距離為0.3mm。將剝離的薄膜送到下游側的捲取裝置側捲取。 The device is adapted to the device shown in Figure 5. The pressurizing unit is a mechanism that pressurizes the hydraulic pump, and two pressurizing plates are vertically mounted inside and connected to the heating device and the cooling device. The mold is placed on the lower side of the lower pressure plate. Further, a peeling means for peeling off the film attached to the mold is provided in the pressurizing unit. The mold temperature at the time of molding was set to 150 ° C, and a pressure of 5 MPa was applied in total for the pressure application. The pressurization time is 30 seconds. Further, the mold temperature at the time of peeling was 80 °C. The distance between the peeling roller and the film was 0.3 mm. The peeled film is taken up to the side of the winding device on the downstream side for winding.

(4)成形結果 (4) Forming results

第12圖中顯示成形的薄膜的突起形成面的掃描式電子顯微鏡((股)KEYENCE VE-7800)所拍攝的照片。於表面全面形成有平均直徑D為350nm、平均高度H為1.2μm、突起的平均高度H與平均直徑D之比(H/D)為3.4的突起。此時，形成於10000μm²的突起的個數為14345個。此外，在與薄膜的表面垂直的方向切斷薄膜的剖面的突起的傾斜角度的範圍，剖面的突起的70%以上相對於與薄膜的表面垂直的方向，為20°~45°的範圍。第13圖為以掃描式電子顯微鏡拍攝本發明之於表面具有突起的構造體即樹脂薄膜的剖面的照片，突起的方向為一定。 Fig. 12 is a photograph taken by a scanning electron microscope (KEYENCE VE-7800) showing the protrusion forming surface of the formed film. A protrusion having an average diameter D of 350 nm, an average height H of 1.2 μm, and a ratio (H/D) of an average height H of the protrusions to an average diameter D of 3.4 was formed on the surface. At this time, the number of protrusions formed at 10000 μm ² was 14,345. Further, in the range perpendicular to the surface of the film, the range of the inclination angle of the protrusion of the cross section of the film is cut, and 70% or more of the protrusion of the cross section is in the range of 20 to 45 with respect to the direction perpendicular to the surface of the film. Fig. 13 is a photograph showing a cross section of a resin film which is a structure having a projection on the surface of the present invention taken by a scanning electron microscope, and the direction of the projection is constant.

將1.41μL的水滴下到撥液性物品的表面，使用接觸角計(協和界面科學社製造，CA-D型)，測定水滴的接觸角。一滴下水滴，水滴就在薄膜的表面滾動，無法停留在一處，所以不能測定接觸角。此時，水滴滾動的方向有優先性，向相同的方向滾動。 1.41 μL of water was dropped on the surface of the liquid-repellent article, and the contact angle of the water drop was measured using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., CA-D type). A drop of water droplets, the water droplets rolling on the surface of the film, can not stay in one place, so the contact angle cannot be measured. At this time, the direction in which the water droplets roll has priority and rolls in the same direction.

(實施例3) (Example 3) (1)薄膜 (1) film

(2)模具 (2) mold

在不銹鋼板的表面被覆厚度100μm左右以Ni為主體的材料。其後，製作模具，該模具係對於模具表面，以雷射加工全面形成有直徑350nm至500nm的凹坑構造。形成有凹坑的區域相對於表面為6%。 The surface of the stainless steel plate was coated with a material mainly composed of Ni having a thickness of about 100 μm. Thereafter, a mold was prepared which was formed into a pit structure having a diameter of 350 nm to 500 nm by laser processing on the surface of the mold. The area in which the pits were formed was 6% with respect to the surface.

(3)成形裝置及條件 (3) Forming equipment and conditions

裝置適用如第5圖所示的裝置。加壓單元為以油壓泵加壓的機構，於內部上下安裝兩片加壓板，分別與加熱裝置、冷卻裝置連結。模具設置於下側加壓板的上面。此外，在加壓單元內設有用於剝離貼在模具上的薄膜的剝離手段。成形時的模具溫度設定為150℃，就加壓力而言，全面施加7MPa的壓力。加壓時間為30秒。此外，剝離時的模具溫度為80℃。剝離輥與薄膜的離間距離為0.3mm。將剝離的薄膜送到下游側的捲取裝置側捲取。 The device is adapted to the device shown in Figure 5. The pressurizing unit is a mechanism that pressurizes the hydraulic pump, and two pressurizing plates are vertically mounted inside and connected to the heating device and the cooling device. The mold is placed on the lower side of the lower pressure plate. Further, a peeling means for peeling off the film attached to the mold is provided in the pressurizing unit. The mold temperature at the time of molding was set to 150 ° C, and the pressure of 7 MPa was applied in full in terms of the pressing force. The pressurization time is 30 seconds. Further, the mold temperature at the time of peeling was 80 °C. The distance between the peeling roller and the film was 0.3 mm. The peeled film is taken up to the side of the winding device on the downstream side for winding.

(4)成形結果 (4) Forming results

第14圖中顯示成形的薄膜的突起形成面的掃描式電子顯微鏡((股)KEYENCE VE-7800)所拍攝的照片。於表面全面形成有平均直徑D為410nm、平均高度H為700nm、突起的平均高度H與平均直徑D之比(H/D)為1.7的突起。此時，形成於10000μm²的突起的個數為3200個。此外，在與薄膜的表面垂直的方向切斷薄膜的剖面的突起的傾斜角度的範圍，剖面的突起的70%以上相對於與薄膜的表面垂直的方向，為20°~45°的範圍。第15 圖為以掃描式電子顯微鏡拍攝本發明之於表面具有突起的構造體即樹脂薄膜的剖面的照片，突起的方向為一定。 Fig. 14 is a photograph taken by a scanning electron microscope (KEYENCE VE-7800) showing the protrusion forming surface of the formed film. A protrusion having an average diameter D of 410 nm, an average height H of 700 nm, and a ratio (H/D) of an average height H of the protrusions to an average diameter D of 1.7 was formed on the entire surface. At this time, the number of protrusions formed at 10000 μm ² was 3,200. Further, in the range perpendicular to the surface of the film, the range of the inclination angle of the protrusion of the cross section of the film is cut, and 70% or more of the protrusion of the cross section is in the range of 20 to 45 with respect to the direction perpendicular to the surface of the film. Fig. 15 is a photograph showing a cross section of a resin film which is a structure having a projection on the surface of the present invention taken by a scanning electron microscope, and the direction of the projection is constant.

(比較例1) (Comparative Example 1) (1)薄膜 (1) film

(2)模具 (2) mold

在不銹鋼板的表面被覆厚度100μm左右以Ni為主體的材料。其後，製作模具，該模具係對於模具表面，以雷射加工全面形成有直徑1.0μm至4.0μm的凹坑構造。形成有凹坑的區域相對於表面為35%。 The surface of the stainless steel plate was coated with a material mainly composed of Ni having a thickness of about 100 μm. Thereafter, a mold was prepared which was formed into a pit structure having a diameter of 1.0 μm to 4.0 μm by laser processing on the surface of the mold. The area in which the pits were formed was 35% with respect to the surface.

(3)成形裝置及條件 (3) Forming equipment and conditions

(4)成形結果 (4) Forming results

第16圖中顯示成形的薄膜的突起形成面的掃描式電子顯微鏡((股)KEYENCE VE-7800)所拍攝的照片。於表面全面形成有平均直徑為3.0μm、平均高度為2.5μm、突起的平均高度H與平均直徑D之比(H/D)為0.8的突起。此時，形成於10000μm²的突起的個數為720個。此外，未觀察到突起的傾斜。第17圖為以掃描式電子顯微鏡拍攝於表面具有突起的構造體即樹脂薄膜的剖面的照片。 Fig. 16 is a photograph taken by a scanning electron microscope (KEYENCE VE-7800) showing the protrusion forming surface of the formed film. A protrusion having an average diameter of 3.0 μm, an average height of 2.5 μm, and a ratio (H/D) of an average height H of the protrusions to an average diameter D of 0.8 was formed on the surface. At this time, the number of protrusions formed at 10000 μm ² was 720. In addition, the inclination of the protrusion was not observed. Fig. 17 is a photograph showing a cross section of a resin film which is a structure having a projection on its surface, which is taken by a scanning electron microscope.

將1.41μL的水滴下到撥液性物品的表面，使用接觸角計(協和界面科學社製造、CA-D型)，測定水滴的接觸角。此時的接觸角為105°，相較於成形前的薄膜，10°接觸角變高。再者，成形前的接觸角為95°。此外，此時如實施例1或2，未觀察到水滴滾動的舉動。 1.41 μL of water was dropped on the surface of the liquid-repellent article, and the contact angle of the water drop was measured using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., CA-D type). The contact angle at this time was 105°, and the 10° contact angle became higher than that of the film before molding. Further, the contact angle before molding was 95°. Further, at this time, as in Example 1 or 2, no behavior of water droplet rolling was observed.

(比較例2) (Comparative Example 2) (1)薄膜 (1) film

(2)模具 (2) mold

在不銹鋼板的表面被覆厚度100μm左右以Ni為主體的材料。其後，製作模具，該模具係對於模具表面，以雷射加工全面形成有直徑400nm至700nm的凹坑構造。形成有凹坑的區域相對於表面為10.7%。 The surface of the stainless steel plate was coated with a material mainly composed of Ni having a thickness of about 100 μm. Thereafter, a mold was prepared which was formed into a pit structure having a diameter of 400 nm to 700 nm by laser processing on the surface of the mold. The area in which the pits were formed was 10.7% with respect to the surface.

(3)成形裝置及條件 (3) Forming equipment and conditions

裝置適用如第5圖所示的裝置。加壓單元為以油壓泵加壓的機構，於內部上下安裝兩片加壓板，分別與加熱裝置、冷卻裝置連結。模具設置於下側加壓板的上面。此外，在加壓單元內設有用於剝離貼在模具上的薄膜的剝離手段。成形時的模具溫度設定為150℃，就加壓力而言，全面施加10MPa的壓力。加壓時間為30秒。此外，剝離時的模具溫度為80℃。剝離輥與薄膜的離間距離為0.3mm。將剝離的薄膜送到下游側的捲取裝置側捲取。 The device is adapted to the device shown in Figure 5. The pressurizing unit is a mechanism that pressurizes the hydraulic pump, and two pressurizing plates are vertically mounted inside and connected to the heating device and the cooling device. The mold is placed on the lower side of the lower pressure plate. Further, a peeling means for peeling off the film attached to the mold is provided in the pressurizing unit. The mold temperature at the time of molding was set to 150 ° C, and a pressure of 10 MPa was applied in total in terms of pressure. The pressurization time is 30 seconds. Further, the mold temperature at the time of peeling was 80 °C. The distance between the peeling roller and the film was 0.3 mm. The peeled film is taken up to the side of the winding device on the downstream side for winding.

(4)成形結果 (4) Forming results

第18圖中顯示成形的薄膜的突起形成面的掃描式電子顯微鏡((股)KEYENCE VE-780))所拍攝的照片。於表面全面形成有平均直徑D為550nm、平均高度H為500nm、突起的平均高度H與平均直徑D之比(H/D)為0.91的突起。此時，形成於10000μm²的突起的個數為4500個，突起對於基底面積的總面積率為7.8%。此外，在與薄膜的表面垂直的方向切斷薄膜的剖面的突起的傾斜角度的範圍，剖面的突起的70%以上相對於與薄膜的表面垂直的方向，為20°~45°的範圍。第19圖為以掃描式電子顯微鏡拍攝本發明之於表面具有突起的構造體即樹脂薄膜的剖面的照片，突起的方向為一定。 Fig. 18 is a photograph taken by a scanning electron microscope (KEYENCE VE-780) showing the protrusion forming surface of the formed film. A protrusion having an average diameter D of 550 nm, an average height H of 500 nm, and a ratio (H/D) of an average height H of the protrusions to an average diameter D of 0.91 was formed on the surface. At this time, the number of protrusions formed at 10000 μm ² was 4,500, and the total area ratio of the protrusions to the substrate area was 7.8%. Further, in the range perpendicular to the surface of the film, the range of the inclination angle of the protrusion of the cross section of the film is cut, and 70% or more of the protrusion of the cross section is in the range of 20 to 45 with respect to the direction perpendicular to the surface of the film. Fig. 19 is a photograph showing a cross section of a resin film of a structure having protrusions on the surface of the present invention taken by a scanning electron microscope, and the direction of the protrusions is constant.

將1.41μL的水滴下到撥液性物品的表面，使用接觸角計(協和界面科學社製造，CA-D型)，測定水滴的接觸角。此時的接觸角為131°，相較於成形前的薄膜，接觸角變高36°。再者，成形前的接觸角為95°。此外，此時如實施例1或2，未觀察到水滴滾動的舉動。 1.41 μL of water was dropped on the surface of the liquid-repellent article, and the contact angle of the water drop was measured using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., CA-D type). The contact angle at this time is 131°, which is in contact with the film before forming. The angle becomes 36° higher. Further, the contact angle before molding was 95°. Further, at this time, as in Example 1 or 2, no behavior of water droplet rolling was observed.

(比較例3) (Comparative Example 3) (1)薄膜 (1) film

(2)模具 (2) mold

在不銹鋼板的表面被覆厚度100μm左右以Ni為主體的材料。其後，製作模具，該模具係對於模具表面，以雷射加工全面形成有直徑300nm至500nm的凹坑構造。形成有凹坑的區域相對於表面為15%。 The surface of the stainless steel plate was coated with a material mainly composed of Ni having a thickness of about 100 μm. Thereafter, a mold was prepared which was formed into a pit structure having a diameter of 300 nm to 500 nm by laser processing on the surface of the mold. The area in which the pits are formed is 15% with respect to the surface.

(3)成形裝置及條件 (3) Forming equipment and conditions

成形時的模具溫度設定為150℃，就加壓力而言，全面施加5MPa的壓力。加壓時間為30秒。此外，剝離時的模具溫度為70℃。 The mold temperature at the time of molding was set to 150 ° C, and a pressure of 5 MPa was applied in total for the pressure application. The pressurization time is 30 seconds. Further, the mold temperature at the time of peeling was 70 °C.

(4)成形結果 (4) Forming results

第20圖中顯示成形的薄膜的突起形成面的掃描式電子顯微鏡((股)KEYENCE VE-7800)所拍攝的照片。於表面全面形成有平均直徑為350nm、平均高度為1.2μm、突起的平均高度H與平均直徑D之比(H/D)為3.3的突起。此時，形成於10000μm²的突起的個數為14900個。此外，未觀察到突起的傾斜。第21圖為以掃描式電子顯微鏡拍攝於表面具有突起的構造體即樹脂薄膜的剖面的照片。 Fig. 20 is a photograph taken by a scanning electron microscope (KEYENCE VE-7800) showing the protrusion forming surface of the formed film. A protrusion having an average diameter of 350 nm, an average height of 1.2 μm, and a ratio (H/D) of an average height H of the protrusions to an average diameter D of 3.3 was formed on the surface. At this time, the number of protrusions formed at 10000 μm ² was 14,900. In addition, the inclination of the protrusion was not observed. Fig. 21 is a photograph showing a cross section of a resin film which is a structure having a projection on its surface, which is taken by a scanning electron microscope.

將1.41μL的水滴下到撥液性物品的表面，使用接觸角計(協和界面科學社製造，CA-D型)，測定水滴的接觸角。此時的接觸角為158°，相較於成形前的薄膜，接觸角變高63°。再者，成形前的接觸角為95°。此外，此時如實施例1或2，未觀察到水滴滾動的舉動，但使薄膜傾斜10°時，水滴向使其傾斜的方向滾動。 1.41 μL of water was dropped on the surface of the liquid-repellent article, and the contact angle of the water drop was measured using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., CA-D type). The contact angle at this time was 158°, and the contact angle became 63° higher than that of the film before forming. Further, the contact angle before molding was 95°. Further, at this time, as in Example 1 or 2, the behavior of water droplet rolling was not observed, but when the film was inclined by 10°, the water droplets rolled in the direction in which they were inclined.

產業上之利用可能性Industrial use possibility

本發明之於表面具有突起的構造體適用於微流路、細胞培養片、包裝材料、防污或防水片、記錄材料、螢幕、分隔板、離子交換膜、電池隔膜材料、顯示器、光學材料等在表面需要撥液性的製品或構件。 The structure of the present invention having protrusions on the surface is suitable for micro flow paths, cell culture sheets, packaging materials, antifouling or waterproof sheets, recording materials, screens, partition plates, ion exchange membranes, battery separator materials, displays, optical materials. Wait for products or components that require liquid repellency on the surface.

11‧‧‧構造體 11‧‧‧Structural body

12‧‧‧薄膜的表面 12‧‧‧ Film surface

13‧‧‧突起 13‧‧‧ Protrusion

15‧‧‧突起根部的中心 15‧‧‧ Center of the protruding root

Claims

一種構造體，其於表面具有突起，並且(1)前述突起之中，70%以上為從根部的中心畫到前端的中心的直線相對於與構造體的表面垂直的方向傾斜的突起，(2)前述構造體表面的前述突起的個數在10000μm²中，為10個以上、4×10⁵個以下，(3)前述突起的平均直徑D為100nm以上、10μm以下，(4)前述突起的平均高度H與平均直徑D之比(H/D)為1以上、50以下。 A structure having protrusions on a surface, and (1) 70% or more of the protrusions are protrusions drawn from a center of the root to a center of the front end with respect to a direction perpendicular to a surface of the structure, (2) The number of the protrusions on the surface of the structure is 10 or more and 4 × 10 ⁵ or less in 10000 μm ² , and (3) the average diameter D of the protrusions is 100 nm or more and 10 μm or less, and (4) the protrusions The ratio (H/D) of the average height H to the average diameter D is 1 or more and 50 or less.

如請求項1之構造體，其中從前述突起根部的中心畫到前端的中心的直線的方向為不一定。 The structure of claim 1, wherein the direction of the straight line drawn from the center of the protruding root to the center of the front end is not necessarily.

如請求項1之構造體，其中從前述突起根部的中心畫到前端的中心的直線的方向為一定。 The structure of claim 1, wherein a direction of a straight line drawn from a center of the protruding root to a center of the front end is constant.

如請求項1至3中任一項之構造體，其中從前述突起根部的中心畫到前端的中心的直線之中，70%以上相對於與構造體的表面垂直的方向，形成25°以上、50°以下的角度。 The structure according to any one of claims 1 to 3, wherein 70% or more of the straight line drawn from the center of the protruding root to the center of the front end is formed at 25° or more with respect to a direction perpendicular to the surface of the structural body, Angles below 50°.

如請求項1至4中任一項之構造體，其中前述突起的高度為不一定。 The structure of any one of claims 1 to 4, wherein the height of the aforementioned protrusion is not necessarily.