WO2019159792A1 - 樹脂構造体および樹脂構造体の製造方法 - Google Patents

樹脂構造体および樹脂構造体の製造方法 Download PDF

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Publication number
WO2019159792A1
WO2019159792A1 PCT/JP2019/004271 JP2019004271W WO2019159792A1 WO 2019159792 A1 WO2019159792 A1 WO 2019159792A1 JP 2019004271 W JP2019004271 W JP 2019004271W WO 2019159792 A1 WO2019159792 A1 WO 2019159792A1
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WIPO (PCT)
Prior art keywords
base layer
fiber
fibers
layer
resin structure
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2019/004271
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English (en)
French (fr)
Japanese (ja)
Inventor
聡子 森岡
箕浦　潔
惠太 和田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toray Industries Inc
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Toray Industries Inc
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Application filed by Toray Industries Inc filed Critical Toray Industries Inc
Priority to KR1020207018845A priority Critical patent/KR20200123087A/ko
Priority to JP2019508269A priority patent/JP7234917B2/ja
Priority to CN201980012833.0A priority patent/CN111712380B/zh
Publication of WO2019159792A1 publication Critical patent/WO2019159792A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer

Definitions

  • the present invention relates to a resin structure that exhibits a liquid repellent effect by having a fiber layer composed of a large number of fibers on the surface, and a method for producing the resin structure.
  • Patent Documents 2 and 3 As a fine structure that exhibits a liquid repellent effect, a composite shape that is oriented in a direction other than the direction perpendicular to the surface of the structure and has a fiber shape on an anisotropic protrusion or uneven protrusion is proposed. (Patent Documents 2 and 3).
  • Patent Document 4 a method of impregnating a lubricating liquid in a network structure entangled with each other in a three-dimensional direction has been proposed.
  • JP 2004-170935 A International Publication No. 2015/159825 JP 2016-155258 A JP 2016-11375 A
  • Patent Documents 1 to 4 described above have insufficient liquid repellency, and droplets may remain attached to the film as a structure, and the expected liquid repellency effect can be obtained.
  • There is a problem in durability such as a problem that the liquid crystal cannot be formed and the shape of the fine structure collapses due to external force and the liquid repellency decreases.
  • Patent Document 4 has a problem that the type of liquid is limited or the liquid repellency is low because the lubricating liquid needs to be changed depending on the type of liquid.
  • the resin structure of the present invention that solves the above problem is a resin structure including a base layer and a fiber layer composed of a large number of fibers,
  • the fiber layer is on the side close to the base layer and the fiber extends in a substantially vertical state with respect to the surface of the base layer; and the fiber is on the side away from the base layer and the fiber is on the base layer And a substantially parallel portion extending in a substantially parallel state with respect to the surface of All of the fibers constituting the fiber layer are bonded to the surface of the base layer and extend from the surface of the base layer.
  • the resin structure of the present invention that solves the above problem is a resin structure including a base layer and a fiber layer composed of a large number of fibers,
  • the fibers constituting the fiber layer are bonded to the surface of the base layer and extend from the surface of the base layer, and the area of the portion where the fibers are bonded on the surface of the base layer is the fiber layer of the base layer 5 to 40% of the surface area of the surface on which is formed,
  • the ratio of the area occupied by the fibers is 80% or more of the surface area of the base layer.
  • the manufacturing method of this invention which manufactures the resin structure which solves the said subject is a method of manufacturing a resin structure, A step of disposing a resin composition on the surface of the mold having a plurality of minute holes formed on the surface thereof; Pressing the mold and the resin composition while heating, and press-fitting a portion of the resin composition into the hole; A step of cooling the resin composition in a state where a part of the resin composition is in the hole; While stretching the resin composition in the hole, the resin composition is peeled off from the mold to form a large number of fibers stretched by the resin composition.
  • the fiber layer is on the side close to the base layer, and the fiber extends in a state substantially perpendicular to the surface of the base layer; and
  • the resin structure is formed of a substantially parallel portion on the side away from the base layer and in which the fibers extend in a substantially parallel state with respect to the surface of the base layer.
  • the manufacturing method of this invention which manufactures the resin structure which solves the said subject is a method of manufacturing a resin structure, A step of disposing a resin composition on the surface of the mold having a plurality of minute holes formed on the surface thereof; Pressing the mold and the resin composition while heating, and press-fitting a portion of the resin composition into the hole; A step of cooling the resin composition in a state where a part of the resin composition is in the hole; While stretching the resin composition in the hole, the resin composition is peeled off from the mold to form a large number of fibers stretched by the resin composition.
  • the resin structure of the present invention forms a layer of air between the droplet and the base layer when the droplet is adhered, the contact area between the droplet and air is increased by the fiber layer composed of a large number of fibers.
  • the liquid repellent function can be remarkably improved by the surface tension of the droplets.
  • the tip of the fiber extends substantially parallel to the surface of the base layer, the liquid repellency can be maintained even when the shape is deformed by an external force.
  • the infiltration of the liquid can be suppressed and the liquid repellency can be maintained by the air layer formed by the fibers close to the base layer extending substantially vertically.
  • FIG. 1 is a schematic cross-sectional view of a film which is a resin structure of the present invention.
  • FIG. 2 is a schematic perspective view of a film which is a resin structure of the present invention.
  • FIG. 3 is a schematic surface view of a film which is a resin structure of the present invention.
  • FIG. 4 is a schematic diagram showing the structure of the surface of the base layer of the film which is the resin structure of the present invention.
  • FIG. 5 is a schematic cross-sectional view showing an example of an apparatus for producing a film that is a resin structure of the present invention.
  • FIG. 6 is a schematic plan view of the peeling means in the apparatus for producing a film that is the resin structure of the present invention as seen from the film width direction.
  • FIG. 1 is a schematic cross-sectional view of a film which is a resin structure of the present invention.
  • FIG. 2 is a schematic perspective view of a film which is a resin structure of the present invention.
  • FIG. 3 is a schematic surface
  • FIG. 7 is a schematic cross-sectional view showing another example of an apparatus for producing a film that is a resin structure of the present invention.
  • FIG. 8 is a cross-sectional photograph of the resin structure of the present invention, which was used to determine a substantially vertical portion and a substantially parallel portion of the fiber layer, a power spectrum diagram obtained by Fourier transform, and a fiber angle distribution diagram. It is an example.
  • FIG. 9 is a surface photograph of the resin structure (film) of Example 1 using a scanning electron microscope.
  • 10 is a cross-sectional photograph of the resin structure (film) of Example 1 taken with a scanning electron microscope.
  • FIG. 11 is a surface photograph of the resin structure (film) of Example 2 using a scanning electron microscope.
  • FIG. 12 is a cross-sectional photograph of the resin structure (film) of Example 2 taken with a scanning electron microscope.
  • FIG. 13 is a surface photograph of the resin structure (film) of Example 3 taken with a scanning electron microscope.
  • FIG. 14 is a cross-sectional photograph of the resin structure (film) of Example 3 taken with a scanning electron microscope.
  • FIG. 15 is a surface photograph of the resin structure (film) of Comparative Example 1 using a scanning electron microscope.
  • FIG. 16 is a cross-sectional photograph of the resin structure (film) of Comparative Example 1 using a scanning electron microscope.
  • the resin structure of the present invention is a structure including a base layer and a fiber layer composed of a large number of fibers, wherein the fiber layer is on the side close to the base layer and the fibers are on the surface of the base layer.
  • a substantially vertical portion extending in a substantially vertical state, and a substantially parallel portion on a side away from the base layer and the fibers extending in a state substantially parallel to the surface of the base layer; All of the fibers constituting the fiber layer are bonded to the surface of the base layer and extend from the surface of the base layer.
  • the resin structure of the present invention is a resin structure including a base layer and a fiber layer composed of a large number of fibers, and the fibers constituting the fiber layer are bonded to the surface of the base layer.
  • the area of the surface of the base layer extending from the surface of the base layer to which the fibers are bonded is 5 to 40% of the surface area of the surface of the base layer on which the fiber layer is formed.
  • the ratio of the area occupied by the fibers when the resin structure is viewed from the surface on the fiber side is 80% or more of the surface area of the base layer.
  • FIG. 1 is a schematic sectional view of a film which is a resin structure of the present invention
  • FIG. 2 is a schematic perspective view.
  • the resin structure 10 includes a base layer 11 and a fiber layer 14 including a large number of fibers 13.
  • the fibers 13 present on the surface 12 of the base layer 11 are bonded to the surface 12 of the base layer 11 and extend from the surface 12.
  • the fiber 13 is a portion having a convex shape with respect to the surface 12 of the base layer 11 as shown in FIG. 1 which is a schematic cross-sectional view, and the fibers 13 exist independently and discretely. It is preferable to do.
  • the shape of the fiber 13 may be any shape, but is preferably a weight-like shape, and may be swollen at the tip of the fiber 13.
  • the fiber layer 14 composed of a large number of fibers 13 is on the side close to the surface 12 of the base layer 11, and the substantially vertical portion in which the fibers 13 extend in a substantially vertical state with respect to the surface 12 of the base layer 11.
  • 15 and a substantially parallel portion 16 which is on the side away from the surface 12 of the base layer 11 and in which the fibers 13 extend in a state of being substantially parallel to the surface 12 of the base layer 11.
  • the fiber 13 is substantially perpendicular to the surface 12 of the base layer 11 means that the substantially vertical portion 15 extends at an angle of 60 ° to 120 ° with respect to the surface 12 of the base layer 11.
  • the fiber 13 is substantially parallel to the surface 12 of the base layer 11 means that the substantially parallel portion 16 extends at an angle of 0 ° to 30 ° and 150 ° to 180 ° with respect to the surface 12 of the base layer 11.
  • Whether the fiber 13 extends in a substantially vertical state or in a substantially parallel state with respect to the surface 12 of the base layer 11 is determined by image analysis of a cross-sectional photograph of the fiber layer 14 by two-dimensional Fourier transform. Judgment is made using the power spectrum obtained in this way. A detailed determination method will be described in [Measurement method] described later.
  • Reference Documents 1 to 3 and Reference URL 1 The principle of image analysis by two-dimensional Fourier transform is described in detail in, for example, Reference Documents 1 to 3 and Reference URL 1 below.
  • Reference 1 Toshiharu Emae, “Method for analyzing physical properties of paper using image processing”, Paper Pulp Technology Times, 48 (11), 1-5 (2005)
  • Reference 2 Enomae, T., Han, Y.-H. and Isogai, A., "Fiber orientation distribution of paper surface calculated by image analysis," Proceedings of International Papermaking and Environment Conference, Tianjin, PRChina (May 12- 14), Book2, 355-368 (2004)
  • Reference 3 Enomae, T., Han, Y.-H.
  • the fibers 13 are substantially parallel in the substantially parallel portion 16, the interval between the fibers 13 is appropriately narrowed, and the liquid droplets are difficult to enter between the fibers 13, thereby exhibiting liquid repellency. Since the fibers 13 are substantially vertical in the substantially vertical portion 15, an air layer is well formed between the fibers 13, and the liquid repellency is improved. Here, if the fiber 13 is inclined beyond the substantially vertical state in the substantially vertical portion 15, the fiber 13 is inclined at the root, and it becomes difficult to support the fiber 13 on the side away from the base layer 11 independently. As a result, it becomes difficult to form an air layer and liquid repellency may be lowered.
  • the fibers 13 are often relatively sparse in the substantially vertical portion 15 and the fibers 13 are relatively dense in the approximately parallel portion 16.
  • the fibers 13 are relatively sparse in the substantially vertical portion 15
  • an air layer is well formed in the fiber layer 14 and the liquid repellency is improved. Since the fibers 13 are relatively dense at the substantially parallel portion 16, the penetration of the liquid into the fiber layer 14 is prevented and the liquid repellency is improved.
  • FIG. 3 is a schematic surface view of the film which is the resin structure 10 of the present invention as seen from the surface on the fiber side
  • FIG. 4 is a schematic view showing the structure of the base layer surface of the film which is the resin structure 10 of the present invention.
  • 3 is a view of the resin structure 10 of FIG. 1 as viewed from the direction A
  • FIG. 4 is a view of the resin structure 10 of FIG. 1 as viewed from the BB cross section.
  • one surface of the resin structure 10 is substantially covered with a fiber layer 14 composed of a large number of fibers 13.
  • the ratio of the area occupied by the fibers 13 is 80% or more of the surface area of the base layer 11.
  • the ratio of the area of the surface 12 of the base layer 11 bonded to the fiber 13 is 5 to 40% of the surface area of the surface of the base layer 11 on which the fiber layer 14 is formed. is there. That is, on the surface of the resin structure 10, the fibers 13 are in a dense state covering almost the whole, and liquid droplets are difficult to enter between the fibers 13, so that liquid repellency is exhibited.
  • the proportion of air is larger than the area of the portion bonded to the fiber 13, the air layer is well formed between the fibers 13 and the liquid repellency is improved.
  • the ratio of the area occupied by the fibers 13 when viewed from the surface of the fiber layer 14 side of the resin structure 10 is obtained by binarizing the observation photograph of the surface of the resin structure 10 using a scanning electron microscope. It can be obtained using an image.
  • the ratio of the area of the surface 12 of the base layer 11 where the fibers 13 are bonded can be determined by the following method (i) or (ii).
  • the fiber layer 14 is cut in parallel with the base layer 11 immediately above the base layer 11 of the resin structure 10, and an observation photograph of the cut surface is obtained using a scanning electron microscope, and the cross-sectional observation photograph is binarized. Obtained using images.
  • observation photographs are obtained using a scanning electron microscope.
  • the value measured by the above method (i) is the ratio of the area of the surface 12 of the base layer 11 where the fibers 13 are bonded.
  • the fibers are very thin such that the fiber diameter is 1 ⁇ m or less, and even if the fiber layer 14 is cut by the method (i) above, the fibers 13 fall down due to the cutting edge of the cutting blade, and the fiber layer 14 is cut.
  • the value measured by the method of (ii) be the ratio of the area of the portion of the surface 12 of the base layer 11 where the fibers 13 are bonded.
  • the fiber diameter is 0.05 ⁇ m or more and 3 ⁇ m or less on the surface of the resin structure 10, it becomes easy to form an air layer in the gap between the fibers, and the contact area between the droplets and the air becomes large. This is preferable because of increased properties.
  • the fiber diameter is more preferably 0.1 ⁇ m or more and 0.5 ⁇ m or less. When the fiber diameter is 0.05 ⁇ m or more, the fiber is not cut or easily deformed, and durability is improved. Furthermore, since the fiber 13 is hard to cut when the resin forming the fiber 13 is stretched, a sufficient fiber layer 14 can be formed.
  • the fiber diameter when the fiber diameter is 0.1 ⁇ m or more, when the resin forming the fiber 13 is stretched, the fiber 13 is unlikely to fall on the surface of the base layer, and a sufficient substantially vertical portion is easily formed.
  • the fiber diameter is 3 ⁇ m or less, an air layer can be sufficiently formed between the fibers, and a liquid repellent effect is exhibited.
  • the fiber diameter when the fiber diameter is 0.5 ⁇ m or less, when the resin is stretched to form the fibers 13, the fibers 13 are easily entangled with each other, so that it is easy to form a sufficient substantially parallel portion on the side away from the base layer. .
  • the fiber diameter refers to an observation photograph of the surface using a scanning electron microscope, selects arbitrary 30 fibers 13 and measures the maximum width of each of the fibers. This is the average of the maximum widths of the middle 20 fibers 13 excluding 5 from the small width.
  • the number of the fibers 13 is 2000 or more and 3 ⁇ 10 6 or less in 10000 ⁇ m 2 of the surface 12 of the base layer 11, the droplets on the surface of the resin structure 10 are easily supported by the fibers 13. It is preferable because the liquid repellency is enhanced by increasing the contact area between the droplet and air.
  • the number of the fibers 13 in 10000 ⁇ m 2 is 3 ⁇ 10 6 or less, a sufficient air layer can exist between the fibers 13 when the droplets adhere, so that the contact area with the air is sufficient, and the liquid repellent effect Is expressed.
  • the number of the fibers 13 in 10000 ⁇ m 2 on the surface 12 of the base layer 11 is 2000 or more, the distance between the fibers 13 is appropriately narrow, and the droplets are difficult to enter between the fibers 13. Contact with the droplet does not occur and liquid repellency is exhibited.
  • the fiber diameter is 0.5 ⁇ m or less
  • the number of fibers 13 in 10,000 ⁇ m 2 on the surface 12 of the base layer 11 is 10,000 or more, the droplets on the surface of the resin structure 10 are fibers 13. It becomes easy to be supported and is more preferable.
  • the number of the fibers 13 is obtained by obtaining an observation photograph using a scanning electron microscope for the cut surface obtained by cutting the resin structure 10 directly above the base layer 11 of the resin structure 10 and parallel to the base layer 11.
  • a surface mold of the resin structure 10 may be taken with liquid silicone rubber and read from a surface image of the mold.
  • the surface of the liquid silicone rubber becomes a surface having a large number of holes corresponding to the bottom surface of the fiber 13 (the surface bonded to the surface 12 of the base layer 11).
  • a scanning electron micrograph of this surface is obtained and the number of fibers 13 is determined.
  • an observation photograph using a scanning electron microscope is obtained for each cross-section obtained by cutting the resin structure 10 in two cross-sections perpendicular to and perpendicular to the surface of the resin structure 10. It is also possible to obtain the number of fibers 13 per 10000 ⁇ m 2 by obtaining the number of fibers 13 per 100 ⁇ m present in the product and taking the product thereof.
  • the thickness of the fiber layer 14 is preferably 5 ⁇ m or more and 50 ⁇ m or less.
  • the thickness of the fiber layer 14 refers to a cross-sectional observation photograph taken using a scanning electron microscope for a cross section obtained by cutting the structure in a cross section perpendicular to the surface of the resin structure 10, and from the surface 12 of the base layer 11. This is a value obtained by measuring 10 points where the distance to the outermost surface is large and averaging the distances of these 10 points.
  • the fiber layer 14 is 5 ⁇ m or more, an air layer can be formed between the fiber 13 and the fiber 13 when the droplet adheres, so that a liquid repellent effect is obtained.
  • the fiber layer is 50 ⁇ m or less, it does not take time to obtain the fibers 13. Further, the durability is sufficient, for example, the fibers 13 are not easily fallen or deformed.
  • the resin structure 10 of the present invention can be suitably used as a film, but is not limited to a film and may have any shape as long as the surface can be thermoformed. From the viewpoint of, a film is preferable.
  • the material of the resin structure 10 may be any material as long as it can form the fibers 13, such as fluororesin, silicone resin, polyethylene terephthalate, polyethylene-2,6-naphthalate, polypropylene terephthalate, and polybutylene terephthalate.
  • Polyester resins, polyethylene resins, polystyrene, polypropylene, polyisobutylene, polybutene, polymethylpentene, and other polyolefin resins, polyamide resins, polyimide resins, polyether resins, polyesteramide resins, polyetherester resins, acrylic resins Resins, polyurethane resins, polycarbonate resins, polyvinyl chloride resins and the like are preferably used.
  • fluororesins and silicone resins having a low surface energy are particularly preferred, and polyolefin resins such as polyethylene, polystyrene, polypropylene, polyisobutylene, polybutene, and polymethylpentene.
  • a material of the resin structure 10 it is preferable to include these resins as main components.
  • a main component means the component which occupies 50 mass% or more when the whole resin which comprises a resin structure is 100 mass%.
  • 50 mass% or more is preferable and, as for the main component, 80 mass% or more is more preferable.
  • additives can be added to the material of the resin structure 10 of the present invention at the time of polymerization or after polymerization.
  • additives that can be added and blended include, for example, organic fine particles, inorganic fine particles, dispersants, dyes, fluorescent brighteners, antioxidants, weathering agents, antistatic agents, mold release agents, thickeners, Examples include plasticizers, pH adjusters, and salts.
  • a releasing agent low surface tension carboxylic acids such as long chain carboxylic acids or long chain carboxylates and derivatives thereof, and low surface tension alcohols such as long chain alcohols and derivatives thereof, and modified silicone oils. It is preferable to add a small amount of a compound or the like during polymerization.
  • the resin structure 10 may have another layer laminated on the side opposite to the side on which the fiber layer 14 of the base layer 11 is laminated.
  • the above material may be used only for the base layer 11 and the fiber layer 14.
  • the resin structure 10 may be a continuous body or a single wafer.
  • the thickness of the resin structure 10 is not particularly limited.
  • the method for producing the resin structure of the present invention comprises a step of arranging a resin composition on a surface of a mold having a plurality of minute holes formed on the surface, the mold and the mold A step of pressing the resin composition while heating and press-fitting a part of the resin composition into the hole (hereinafter referred to as “press-fitting process”), a part of the resin composition being A step of cooling the resin composition in a state (hereinafter referred to as a “cooling step”), and the resin composition is peeled off from the mold while the resin composition in the hole is stretched.
  • a resin structure composed of a fiber layer composed of the fiber and a base layer not containing the fiber by forming a large number of fibers in which the resin composition is stretched (hereinafter referred to as “pulling”).
  • the above steps are performed in this order.
  • the fiber layer is on the side close to the base layer, the fiber extends in a substantially vertical state with respect to the surface of the base layer, and on the side away from the base layer,
  • a resin structure is formed that includes fibers and substantially parallel portions extending in a substantially parallel state to the surface of the base layer.
  • the peeling step pressure is applied to the resin structure from a direction substantially perpendicular to the fiber layer.
  • the fiber layer is on the side close to the base layer, the fiber extends substantially perpendicular to the surface of the base layer, and the fiber layer is on the side away from the base layer.
  • a step of forming the fibers by a substantially parallel portion extending in a state where the fibers are substantially parallel to the surface of the base layer and the fibers are entangled with each other hereinafter referred to as a “pressurizing step”).
  • FIG.5 is a schematic cross-sectional view of manufacturing apparatuses 50 and 70 for manufacturing the resin structure 10 (film) having the fiber layer 14 on the surface 12 of the base layer 11.
  • FIG. 6 is a schematic cross-sectional view showing the operation of peeling the resin structure 10 (film) from the mold in the manufacturing apparatus 50.
  • the material film 10 ′ is pulled out from the unwinding roll 51 in advance, and then, in the press unit 54, a heated mold 53 with fine holes formed on the surface is formed.
  • a fine protrusion structure corresponding to the fine holes of the mold 53 on the surface of the film 10' Form.
  • the molding part is a peeling unit that peels from the mold 53 a press unit 54 that forms a predetermined fine protrusion structure, and a film 10 '' that is attached to the mold 53 by pressurization and has a fine protrusion structure formed on the surface.
  • the peeling means 55 includes a pair of peeling rolls 55 ⁇ / b> A and a peeling auxiliary roll 55 ⁇ / b> B arranged in parallel to hold the peeled film 10 so as to hold it in an S shape.
  • One surface of the film 10 ′ sent intermittently is thermoformed by the mold 53 in the press unit 54 to obtain a film 10 ′′ having a fine protrusion structure formed on the surface. After the thermoforming, as shown in FIG.
  • the peeling means 55 is moved toward the upstream side, whereby the film 10 ′′ attached to the mold 53 is sequentially peeled from the mold 53, and the base layer 11. A film 10 having a fiber layer 14 on the surface 12 is obtained. Thereafter, the film 10 is wound around the winding roll 56.
  • reference numerals 57 and 58 denote pressure plates, and 59 and 60 denote buffer means provided to smoothly perform intermittent conveyance in the mold 53 portion of the film 10 ′.
  • the diameter of the fiber 13 formed by stretching the formed fine protrusion structure The thickness of the fiber layer 14 can be changed.
  • the temperature of the mold 53 at the time of molding is set to be equal to or higher than the melting point of the resin composition that is the material of the film 10
  • the temperature of the mold 53 at the time of peeling is set to be equal to or higher than the glass transition temperature of the resin composition that is the material of the film 10.
  • the stretched fibers 13 themselves are not rigid, the stretched fibers 13 fall in a non-uniform direction when the tips of the fibers 13 are separated from the mold 53, and the fibers 13 are entangled with each other. At this time, since the fiber 13 is finally entangled from the mold 53, that is, from the tip of the fiber 13, the entangled fiber 13 is densely packed in the portion away from the surface 12 of the base layer 11 of the film 10. The substantially parallel part 16 extended in the state substantially parallel with respect to the base layer 11 is formed.
  • the fiber 13 is closer to the surface 12 of the base layer 11 than the substantially parallel portion 16.
  • a substantially vertical portion 15 extending in a substantially vertical state is formed.
  • the stretched fiber 13 has a relatively high rigidity and the fiber 13 has a small entanglement
  • the density of the fiber layer 14 the inclination angle of the fiber 13, the fiber layer
  • the thickness of 14 can be adjusted. For example, if the pressure is increased, the fiber layer 14 becomes thinner, the fibers 13 on the tip side are inclined and become substantially parallel, and the density of the fibers 13 at the substantially parallel portion 16 increases.
  • the film 10 ′ is pulled out from the unwinding roll 73, and is supplied by the heating roll 75 onto the endless belt-shaped mold 76 in which a fine hole structure is formed on the heated surface.
  • the outer surface of the mold 76 is formed with discretely arranged fine holes and heated by the heating roll 75 immediately before coming into contact with the film 10 ′.
  • the continuously supplied film 10 ′ is pressed against the surface of the mold 76 with the fine hole structure processed by the nip roll 77, and a fine protrusion structure corresponding to the fine hole of the mold 76 is formed on the surface of the film 10 ′. It is formed.
  • the temperature at which the film 10 ′ is pressed against the surface on which the microporous structure of the mold 76 has been processed is equal to or higher than the glass transition temperature of the film 10 ′. It is more preferable that the temperature is equal to or higher than the melting temperature of the film 10 ′.
  • the film 10 ′′ having a fine protrusion structure formed on the surface 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 10 ′′ is cooled by heat conduction through the mold 76 by the cooling roll 78, and then peeled off from the mold 76 while the fine protrusion structure formed by the peeling roll 79 is stretched, and the surface of the base layer 11 is peeled off.
  • a film 10 having a fiber layer 14 on 12 is obtained.
  • the film 10 is taken up on a take-up roll 82.
  • the diameter of the fiber 13 and the thickness of the fiber layer 14 formed by stretching the formed fine protrusion structure are changed. can do.
  • the density of the fiber layer 14, the inclination angle of the fiber 13, and the thickness of the fiber layer 14 can be adjusted. For example, if the pressure is increased, the fiber layer 14 becomes thinner, the fibers 13 on the tip side are inclined and become substantially parallel, and the density of the fibers 13 at the substantially parallel portion 16 increases.
  • the area ratio occupied by the minute holes formed on the surfaces of the molds 53 and 76 is that the area ratio is approximately the ratio of the area of the base layer 11 of the film 10 that is bonded to the fiber 13.
  • the area ratio occupied by minute holes formed on the surfaces of the molds 53 and 76 is preferably 5% to 40%.
  • the diameter of the minute holes formed on the surfaces of the molds 53 and 76 is preferably 0.05 ⁇ m to 3 ⁇ m, more preferably 0.1 ⁇ m to 0.5 ⁇ m. When the diameter of the minute holes formed on the surfaces of the molds 53 and 76 is 0.05 ⁇ m or more, a part of the film 10 ′ is easily press-fitted in the press-fitting process.
  • the fiber 13 stretched in the peeling process is not easily collapsed on the surface of the base layer, and a substantially vertical portion is easily formed. Moreover, if it is 0.5 ⁇ m or less, the tip end portion of the fiber 13 stretched in the peeling process is likely to fall, and the fibers 13 are likely to be entangled in the substantially parallel portion 16. In addition, when the thickness is 3 ⁇ m or less, the fiber 13 stretched in the peeling process is easily deformed in the pressing process.
  • the depth of the minute holes formed on the surfaces of the molds 53 and 76 is preferably 2.5 times or more the hole diameter. If the depth of the hole is 2.5 times or more of the hole diameter, the area where the injected resin is in contact with the side surface of the hole of the mold 53, 76 by the press-fitting step is 10 times or more the surface area of the hole part, It is preferable that the resin is easily stretched in the peeling process.
  • the depth of the hole with respect to the hole diameter is more preferably 10 times or more. There is no particular upper limit to the value of the hole depth relative to the hole diameter, but it is preferably about 100 times due to the ease of hole formation.
  • Such a method for producing the dies 53 and 76 having a plurality of fine holes formed on the surface includes a method of directly performing cutting, laser processing and electron beam processing on the metal surface, and a direct coating on the plating film formed on the metal surface. After forming a convex shape reversed with micropores by laser processing or electron beam processing on the metal surface or the plating film formed on the metal surface by cutting, laser processing or electron beam processing, electroforming The method of producing a micropore shape by is mentioned. In addition, after applying the resist on the substrate, the resist is formed with a predetermined patterning by a photolithographic technique, and then the substrate is etched to form a shape. Examples include a method for obtaining a structure.
  • the molds 53 and 76 having a fine pore structure on the surface can also be produced.
  • the materials of the molds 53 and 76 may be silicon wafers, various metal materials, glass, ceramics, plastics, carbon materials, etc., as long as they have strength and workability with required accuracy. Specifically, Si, SiC, SiN, polycrystalline Si, glass, Ni, Cr, Cu, Al, Fe, Ti, C and further one or more of these may be included. Moreover, you may produce by etching the surface of the metal mold
  • the shape of the fiber 13 can be controlled by adjusting the conditions of the press-fitting process, the cooling process, and the peeling process in addition to the shape of the fine holes on the surfaces of the molds 53 and 76. For example, if the hole diameter in the shape of fine holes on the surfaces of the molds 53 and 76 is reduced, the fiber diameter is reduced. By changing the cooling temperature in the cooling process and the stretching speed in the peeling process, the fiber diameter and the fiber are changed. The thickness of the layer 14 can be changed.
  • the pressure applied can be appropriately changed depending on the form of the fiber 13, and the inclination angle, the degree of density, and the thickness of the fiber layer 14 can be changed by the pressure.
  • the surface of the fiber 13 obtained as described above has a functional group having a low surface energy, It is particularly desirable to coat a fluorine group.
  • Such a coating treatment method is not particularly limited as long as the structure of the fiber 13 is not filled with a coating material.
  • LB method Langmuir Blodget method
  • PVD method physical vapor deposition method
  • CVD method Chemical vapor deposition method
  • self-organization method self-organization method
  • sputtering method and a method in which a single molecule diluted with a solvent is applied. It is also possible to form the fiber 13 by the above-mentioned method after performing a liquid repellent treatment with an arbitrary thickness on the film 10 ′ forming the fiber 13 with the above-described material.
  • the resin structure of the present invention can be used for building materials such as biodevices such as cell culture sheets and biochips, optical devices such as optical films and anisotropic films, liquid repellent sheets, and antifouling sheets, taking advantage of its surface characteristics. It can be used suitably. Moreover, since the resin structure of this invention contains not only liquid repellency but the air layer in the base layer vicinity of the resin structure, it can be used also for other uses, such as a heat insulation sheet.
  • the presence or absence of 16 is determined by the following procedure. (1) A 10 mm ⁇ 10 mm sample is cut out from an arbitrary location of the resin structure 10. One cut surface is arbitrarily selected from the four cut surfaces of the sample. About the selected cut surface, the observation object is the right end portion viewed with the fiber layer 14 on the upper side and the base layer 11 on the lower side.
  • the elliptical approximate inclination angle distribution of the fiber 13 is such that the average value of the average amplitude of 60 degrees or more and 120 degrees or less is compared with the average value of the average amplitude of 0 degrees or more and less than 60 degrees and greater than 120 degrees and 180 degrees or less.
  • it is large it is determined that the fibers 13 in this cross-sectional photograph are in a substantially vertical state.
  • the right end portion viewed from the fiber layer 14 on the upper side and the base layer 11 on the lower side is an observation object, and items (2) to (5) Do the same work. Further, the sample is cut through the center of the 10 mm ⁇ 10 mm sample in parallel with the cut surface selected in the item (1), and the left and right central portions of the cut surface are set as observation objects, and the items (2) to (5) Do the same work.
  • the one-third portion farthest from any base layer 11 of the three observation objects is in a state in which the fibers 13 are substantially parallel, the one-third farthest from the base layer 11 of the fiber layer 14 The part is determined to be a substantially parallel part. If the one-third portion closest to any of the base layers 11 of the three observation targets is the fiber 13 in a substantially vertical state, the one-third portion closest to the base layer 11 of the fiber layer 14 is a substantially vertical portion. It is determined that
  • FIG. 8A shows a cross-sectional photograph used for image analysis by two-dimensional Fourier transform
  • FIG. 8B shows a power spectrum obtained by image analysis
  • FIG. FIG. 8 shows an example in which the fiber 13 extends in a state substantially parallel to the surface 12 of the base layer 11.
  • the Fiber Orientation Analysis Ver. 8.03 was used in order to Fourier transform the basal plane dislocation image. This Fourier transform software extracts the luminance information of each point from the image data, performs a Fourier transform process, and calculates the power spectrum and average amplitude Aave. Processing for obtaining ( ⁇ ) is performed. Detailed procedures are described in Reference Documents 1 to 3 and Reference URL 1 described above.
  • the image is converted into a bitmap in advance in order to extract numerical information on luminance. Further, in order to perform fast Fourier transform, adjustment is made in advance so that the number of pixels on one side of the image is an integer multiple of four.
  • Fourier transform processing is performed on an image having an aspect ratio of 3 or more, the original image is pasted in the direction in which the aspect ratio of the image to be Fourier transformed is reduced, and the Fourier transform processing is performed as one image. Do.
  • the film 10 molded in Examples and the like was cut out to 10 mm ⁇ 10 mm, and the surface was observed with a secondary electron image at a magnification of 10,000 times with a scanning electron microscope (Keyence VE-7800, Inc.).
  • the image size at this time was 12.1 ⁇ m ⁇ 9.1 ⁇ m.
  • the number of pixels was 1280 pixels ⁇ 960 pixels, and the size of one pixel was 9.4 nm ⁇ 9.5 nm.
  • the observation photograph was binarized into black and white, and the area of the bright portion of the image (hereinafter referred to as “white portion”) in the entire image was defined as the ratio of the area occupied by the fibers 13 viewed from the surface on the fiber layer 14 side.
  • the threshold for binarization is an intermediate light amount value between two light amount peaks indicating a white portion and a dark portion (hereinafter referred to as “black portion”), and binarization before and after the light amount value is performed.
  • the light quantity value with the smallest change in the ratio of the white part and the black part was set.
  • the number of pixels was 1280 pixels ⁇ 960 pixels, and the size of one pixel was 9.4 nm ⁇ 9.5 nm.
  • the observation photograph was binarized into black and white, and the area of the bright portion of the image (hereinafter referred to as “white portion”) in the entire image was defined as the area of the surface 12 of the base layer 11 where the fibers 13 were bonded.
  • the threshold value for binarization is an intermediate light amount value between two light amount peaks indicating a white portion and a dark portion (hereinafter referred to as “black portion”), and in binarization before and after the light amount value.
  • black portion dark portion
  • the film 10 is cut in two directions perpendicular to and perpendicular to the surface of the film 10, and each cross section is magnified 5000 times using a scanning electron microscope (Keyence Corporation VE-7800). And observed.
  • the image size at this time was 24.3 ⁇ m ⁇ 18.2 ⁇ m.
  • the number of pixels was 1280 pixels ⁇ 960 pixels, and the size of one pixel was 19.0 nm ⁇ 19.0 nm.
  • the number of fibers 13 present in the cross section and the average cross-sectional width of the fibers 13 were determined, and the ratio of the fibers 13 bonded per unit length of the base layer 11 in each cross section was determined from the product. Further, the product of the proportions of fibers 13 in each cross section was determined, and the value was defined as the ratio of the area of the surface 12 of the base layer 11 where the fibers 13 were bonded.
  • the film 10 molded in Examples and the like was cut out to 10 mm ⁇ 10 mm, and the surface was observed with a secondary electron image at a magnification of 10,000 times with a scanning electron microscope (Keyence VE-7800, Inc.).
  • the image size at this time was 12.1 ⁇ m ⁇ 9.1 ⁇ m.
  • the number of pixels was 1280 pixels ⁇ 960 pixels, and the size of one pixel was 9.4 nm ⁇ 9.5 nm. From the observation photograph, arbitrary 30 fibers 13 were selected, and the average of the widths of the middle 20 fibers 13 obtained by removing 5 from the wide width and 5 from the small width was the fiber.
  • the diameter The diameter.
  • the film 10 molded in Examples and the like was cut out to 10 mm ⁇ 10 mm, and the surface was observed with a secondary electron image at a magnification of 10,000 times with a scanning electron microscope (Keyence VE-7800, Inc.).
  • the image size at this time was 12.1 ⁇ m ⁇ 9.1 ⁇ m.
  • the number of pixels was 1280 pixels ⁇ 960 pixels, and the size of one pixel was 9.4 nm ⁇ 9.5 nm.
  • the number of fibers 13 is read from this image. At the time of measuring the number of the fibers 13, the measurement was performed while marking the fibers 13 using the Snipping Tool.
  • the number of fibers obtained by this method was converted to the number of fibers in 10,000 ⁇ m 2 .
  • the surface of the film 10 may be taken with liquid silicone rubber or the like and read from the surface image of the mold.
  • the film 10 is peeled off from the cured liquid silicone rubber, the surface of the liquid silicone rubber becomes a surface in which many holes corresponding to the bottom surface of the fiber 13 are opened. A scanning electron micrograph of this surface is obtained to determine the number of fibers 13.
  • the film 10 formed in Examples and the like was cut in a direction perpendicular to the surface of the film 10, and the cross section thereof was observed with a scanning electron microscope (Keyence VE-7800) at a magnification of 5000 times.
  • the image size at this time was 24.3 ⁇ m ⁇ 18.2 ⁇ m.
  • the number of pixels was 1280 pixels ⁇ 960 pixels, and the size of one pixel was 19.0 nm ⁇ 19.0 nm.
  • a cured resin Cutting or polishing can be performed after the film 10 is hardened together with the fiber layer 14 so that the structure of the fiber layer 14 is not destroyed by ice or ice.
  • the cured resin is made hydrophilic after lyophilic treatment (corona discharge treatment or plasma treatment) within a range that does not destroy the surface structure of the film 10. It can be hardened with ice or ice and cut.
  • the film 10 formed in Examples and the like was cut into 10 mm ⁇ 30 mm, and the contact angle of water droplets was measured using a contact angle meter (Kyowa Interface Science Co., Ltd., CA-D type). Pure water was used as the measurement liquid, and 1.41 ⁇ L of pure water was dropped onto the film surface. The measurement was performed at 10 points in the film, and the average value of the 10 points was defined as the contact angle.
  • Non-adhesion test The film 10 molded in Examples and the like was cut into 10 mm ⁇ 30 mm, and fixed to a fixing jig so that the measurement surface was on top. Thereafter, with the fixing jig tilted at 45 °, 0.3 ml of yogurt (Morinaga biplane plain yogurt sweetened type) was dropped, and the time until the droplet moved 20 mm after dropping was measured. Moreover, the adhesion residue of yogurt was observed visually. The case where there was no adhesion residue was marked with ⁇ , and the others were marked with ⁇ .
  • Example 1 Film A 100 ⁇ m thick film containing a polymer mainly composed of polypropylene (melting point: 144 ° C., glass transition temperature: ⁇ 20 ° C.) was used. (2) Mold On the surface of the stainless steel plate, a material mainly composed of Ni was coated with a thickness of about 100 ⁇ m. Thereafter, a mold was produced in which a fine pore structure having a diameter of about 0.3 ⁇ m to 0.6 ⁇ m and a depth of about 7 ⁇ m to 10 ⁇ m was formed on the entire surface of the mold surface by laser processing. The area where the fine holes were formed was 20% with respect to the surface where the fine holes were formed.
  • the press unit 54 is a mechanism that is pressurized by a hydraulic pump.
  • Two pressurizing plates 57 and 58 are attached inside the press unit 54 and are connected to a heating device and a cooling device, respectively.
  • the mold 53 is installed on the upper surface of the lower pressure plate 57.
  • a peeling means 55 for peeling the film 10 ′′ attached to the mold 53 is installed in the press unit 54.
  • the mold temperature at the time of molding was set to 160 ° C., and a pressure of 10 MPa was applied over the entire surface.
  • the pressurizing time was 60 seconds.
  • the mold temperature at the time of peeling was 50 ° C.
  • the separation distance between the peeling roll and the film was 0.3 mm.
  • the peeled film was pressed with a nip roll 62 at 0.6 MPa, then sent to the downstream winding unit 61 side and wound up.
  • FIG. 9 is a surface photograph of the fiber-formed surface of the film 10 molded in Example 1 using a scanning electron microscope (Keyence VE-7800).
  • FIG. 2 is a cross-sectional photograph of the molded film 10 taken with a scanning electron microscope (Keyence VE-7800).
  • the formed film 10 was composed of a base layer 11 and a fiber layer 14 in which a large number of fibers 13 were formed.
  • the fiber layer 14 includes a substantially vertical portion 15 made of fibers 13 that are substantially perpendicular to the surface 12 of the base layer 11 on the side close to the base layer 11, and a surface that is substantially away from the surface 12 of the base layer 11 on the side away from the base layer 11.
  • Liquid repellency / droplet transfer effect 1.41 ⁇ L of water is dropped on the surface of the fiber layer 14 of the molded film 10 and a contact angle meter (Kyowa Interface Science Co., Ltd., CA-D type) is used. Used to measure the contact angle of water droplets. When a water droplet is dropped, the water droplet rolls on the surface of the film 10 and cannot be kept in one place, so that the contact angle cannot be measured. In addition, 0.3 ml of yogurt was dropped on the surface of the film 10 inclined at 45 °, and the time from the dropping to the movement of 20 mm was 0.2 s, and there was no adhesion residue.
  • Example 2 (1) Film The same film as in Example 1 was used. (2) Mold The same mold as in Example 1 was used. (3) Molding apparatus and conditions The same molding apparatus 50 as in Example 1 was used, and a film was molded under the same conditions as in Example 1 except that the mold temperature at the time of molding was 150 ° C.
  • FIG. 11 is a surface photograph of the fiber-formed surface of the film 10 molded in Example 2 by a scanning electron microscope (Keyence VE-7800).
  • FIG. 2 is a cross-sectional photograph of the molded film 10 taken with a scanning electron microscope (Keyence VE-7800).
  • the formed film 10 was composed of a base layer 11 and a fiber layer 14 in which a large number of fibers 13 were formed.
  • the fiber layer 14 includes a substantially vertical portion 15 made of fibers 13 that are substantially perpendicular to the surface 12 of the base layer 11 on the side close to the base layer 11, and a surface that is substantially away from the surface 12 of the base layer 11 on the side away from the base layer 11.
  • the fibers 13 which became parallel, and was comprised with the substantially horizontal part 16 extended in the state in which the fibers were entangled. In the substantially vertical portion 15, the fibers 13 are relatively sparse, and in the approximately parallel portion 16, the fibers 13 are relatively dense.
  • the fiber diameter was 0.6 ⁇ m, and the fiber layer thickness was 5.0 ⁇ m.
  • the number of fibers 13 formed at 10,000 ⁇ m 2 was 10300.
  • the area of the part where the fibers 13 are bonded on the surface 12 of the base layer 11 was measured by the method (i). The measured values of the obtained fiber 13 are shown in Table 1.
  • Example 3 (1) Film The same film as in Example 1 was used. (2) Mold The same mold as in Example 1 was used. (3) Molding apparatus and conditions The same molding apparatus 50 as in Example 1 was used, and a film was molded under the same conditions as in Example 1 except that the mold temperature at the time of peeling was 80 ° C.
  • FIG. 13 is a surface photograph of the fiber-formed surface of the film 10 molded in Example 3 by a scanning electron microscope (Keyence VE-7800), and FIG. 2 is a cross-sectional photograph of the molded film 10 taken with a scanning electron microscope (Keyence VE-7800).
  • the formed film 10 was composed of a base layer 11 and a fiber layer 14 in which a large number of fibers 13 were formed.
  • the fiber layer 14 includes a substantially vertical portion 15 made of fibers 13 that are substantially perpendicular to the surface of the base layer on the side close to the base layer 11, and a fiber 13 that is substantially parallel to the surface of the base layer on the side away from the base layer 11.
  • the substantially parallel part 16 extended in the state which consists of fibers and was entangled.
  • the fibers 13 are relatively sparse, and in the approximately parallel portion 16, the fibers 13 are relatively dense.
  • the fiber diameter was 0.45 ⁇ m, and the thickness of the fiber layer 14 was 6.0 ⁇ m.
  • the number of fibers 13 formed at 10,000 ⁇ m 2 was 12700.
  • the area of the part where the fibers 13 are bonded on the surface 12 of the base layer 11 was measured by the method (ii). The measured values of the obtained fiber 13 are shown in Table 1.
  • the press unit 54 is a mechanism that is pressurized by a hydraulic pump. Two pressurizing plates 57 and 58 are attached inside the press unit 54 and are connected to a heating device and a cooling device, respectively.
  • the mold 53 is installed on the upper surface of the lower pressure plate 57. Further, a peeling means 55 for peeling the film 10 ′′ attached to the mold 53 is installed in the press unit 54.
  • the mold temperature at the time of molding was set to 165 ° C., and the pressure was 5 MPa over the entire surface.
  • the pressurization time was 30 seconds.
  • the mold temperature at the time of peeling was 80 ° C.
  • the separation distance between the peeling roll 55A and the mold 53 was 0.3 mm.
  • the peeled film 10 was sent out to the downstream winding unit 61 side and wound up.
  • FIG. 15 is a surface photograph of the molding surface of the film molded in Comparative Example 1 using a scanning electron microscope (Keyence VE-7800), and FIG. 16 is molded in Comparative Example 1.
  • 2 is a cross-sectional photograph of the film taken with a scanning electron microscope (Keyence VE-7800).
  • the formed film was composed of a base layer and a large number of fibers formed on the entire surface of the base layer.
  • the average diameter of the fiber was 0.35 ⁇ m, the average height was 1.2 ⁇ m, and the fiber was not stretched.
  • the number of fibers formed at 10,000 ⁇ m 2 was 14300.
  • the range of the fiber inclination angle in the cross section obtained by cutting the film in a direction perpendicular to the surface of the base layer is 20 ° to more than 70% of the protrusions in the cross section perpendicular to the surface of the base layer.
  • the range was 45 °.
  • the drawing direction of the fiber was constant, there was no rough portion, and the fiber was not composed of a substantially parallel part and a substantially vertical part.
  • the area of the part where the fibers are bonded on the surface of the base layer was measured by the method (ii). The measured values of the obtained fibers are shown in Table 1.
  • the resin structure of the present invention is liquid repellent on the surface of microchannels, cell culture sheets, packaging materials, antifouling or waterproof sheets, recording materials, screens, separators, ion exchange membranes, battery membrane materials, displays, optical materials, etc. It is suitably used for products and parts that require high performance.

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PCT/JP2019/004271 2018-02-16 2019-02-06 樹脂構造体および樹脂構造体の製造方法 Ceased WO2019159792A1 (ja)

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JPH09155972A (ja) * 1995-12-12 1997-06-17 Ykk Corp 撥水性フィルムとその製造方法
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