WO2015053272A1 - Corps stratifié lipophile, son procédé de production et article - Google Patents

Corps stratifié lipophile, son procédé de production et article Download PDF

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Publication number
WO2015053272A1
WO2015053272A1 PCT/JP2014/076823 JP2014076823W WO2015053272A1 WO 2015053272 A1 WO2015053272 A1 WO 2015053272A1 JP 2014076823 W JP2014076823 W JP 2014076823W WO 2015053272 A1 WO2015053272 A1 WO 2015053272A1
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WIPO (PCT)
Prior art keywords
lipophilic
resin layer
master
mass
laminate
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PCT/JP2014/076823
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English (en)
Japanese (ja)
Inventor
亮介 岩田
水野　幹久
忍 原
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デクセリアルズ株式会社
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Publication of WO2015053272A1 publication Critical patent/WO2015053272A1/fr

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    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/536—Hardness
    • 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
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/208—Touch screens
    • 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
    • B32B2605/00—Vehicles

Definitions

  • the present invention relates to a lipophilic laminate, a method for producing the same, and an article using the lipophilic laminate.
  • the aesthetics of the article will be impaired. For example, if fingerprints adhere to the surfaces of pianos, luxury furniture, home appliances, automobile interior / exterior parts, etc., the aesthetics are impaired and it becomes unsightly.
  • the touch panel of an information display device such as a smartphone or a tablet PC equipped with a touch panel as a user interface (UI) has an advantage that the device can be intuitively operated by directly touching the display screen with a finger.
  • UI user interface
  • an antifouling layer designed so that a fluorine-based compound, a silicone-based compound, or the like appears on the outermost surface as a display surface of a touch panel or the like
  • the proposed technique has an effect of facilitating wiping with a cloth or the like by forming a water- and oil-repellent surface to weaken the adhesion of the oil and fat components constituting the fingerprint.
  • the fingerprint is wiped off with a cloth or the like, the oil and fat component is repelled on the surface of the layer, so that there is a problem that droplets are formed, light is scattered, and the fingerprint becomes conspicuous.
  • the surface of the article is required to have fingerprint resistance that is difficult to see even if fingerprints are attached.
  • a water-repellent lipophilic surface that does not repel oil and fat components has been proposed (see, for example, Patent Document 2).
  • the oil and fat component of the fingerprint adhering to the surface spreads and does not form droplets, making it difficult to see the fingerprint.
  • the laminate attached to the article is required to have excellent surface hardness and flexibility in addition to fingerprint resistance.
  • the present invention provides an oleophilic laminate capable of achieving both excellent surface hardness and excellent flexibility while having fingerprint resistance, a method for producing the same, and an article using the oleophilic laminate. For the purpose.
  • Means for solving the problems are as follows. That is, ⁇ 1> A resin base material and a lipophilic resin layer on the resin base material, The lipophilic resin layer has either a fine convex part or a concave part on the surface, The lipophilic resin layer contains 10% by mass to 55% by mass of inorganic oxide particles; The oleic acid contact angle on the surface of the lipophilic resin layer is 10 ° or less. ⁇ 2> The lipophilic laminate according to ⁇ 1>, wherein the inorganic oxide particles have an average particle diameter of 1 nm to 100 nm.
  • ⁇ 3> The lipophilic laminate according to any one of ⁇ 1> to ⁇ 2>, wherein the lipophilic resin layer contains 10% by mass to 45% by mass of inorganic oxide particles.
  • ⁇ 4> The lipophilic laminate according to any one of ⁇ 1> to ⁇ 3>, wherein the oleic acid contact angle on the surface of the lipophilic resin layer is 5.0 ° or less.
  • any one of the average height of the fine protrusions and the average depth of the fine recesses is 10 nm to 150 nm, and the average distance between the adjacent protrusions and the adjacent recesses
  • the lipophilic laminate according to any one of ⁇ 1> to ⁇ 4>, wherein any one of the average distances is 10 nm to 500 nm.
  • the resin base material is a polyethylene terephthalate (PET) film.
  • ⁇ 7> The method for producing a lipophilic laminate according to any one of ⁇ 1> to ⁇ 6>, An uncured resin layer forming step of forming an uncured resin layer by applying an active energy ray-curable resin composition on a resin substrate; Adhering a transfer master having either a fine convex part or a concave to the uncured resin layer, irradiating the uncured resin layer to which the transfer master is in contact with an active energy ray to cure the uncured resin layer And a lipophilic resin layer forming step of forming a lipophilic resin layer by transferring any one of the fine convex portions and concave portions.
  • ⁇ 8> The parent according to ⁇ 7>, wherein any one of the fine convex portion and the concave portion of the transfer master is formed by etching the surface of the transfer master using a photoresist having a predetermined pattern shape as a protective film. It is a manufacturing method of an oil-based laminated body.
  • ⁇ 9> The lipophilic laminate according to ⁇ 7>, wherein any one of the fine convex portion and the concave portion of the transfer master is formed by irradiating the surface of the transfer master with laser processing of the transfer master. It is a manufacturing method of a body.
  • the conventional problems can be solved, the object can be achieved, and the lipophilic laminate can achieve both excellent surface hardness and excellent flexibility while having fingerprint resistance, And the manufacturing method and the articles
  • FIG. 1A is an atomic force microscope (AFM) image showing an example of the surface of a lipophilic resin layer having convex portions.
  • FIG. 1B is a cross-sectional view taken along line aa in FIG. 1A.
  • FIG. 1C is an AFM image (three-dimensional image) of the lipophilic resin layer in FIG. 1A.
  • FIG. 1D is a scanning electron microscope image (SEM image) of the lipophilic resin layer of FIG. 1A.
  • FIG. 2A is an AFM image showing an example of the surface of a lipophilic resin layer having a recess.
  • FIG. 2B is a cross-sectional view taken along line aa in FIG. 2A.
  • FIG. 3A is a perspective view illustrating an example of a configuration of a roll master that is a transfer master.
  • 3B is an enlarged plan view showing a part of the roll master shown in FIG. 3A.
  • 3C is a cross-sectional view of the track T in FIG. 3B.
  • FIG. 4 is a schematic diagram showing an example of the configuration of a roll master exposure apparatus for producing a roll master.
  • FIG. 5A is a process diagram for explaining an example of a process for producing a roll master.
  • FIG. 5B is a process diagram for explaining an example of a process for producing a roll master.
  • FIG. 5C is a process diagram for explaining an example of a process for producing a roll master.
  • FIG. 5A is a process diagram for explaining an example of a process for producing a roll master.
  • FIG. 5B is a process diagram for explaining an example of a process for producing a roll master.
  • FIG. 5C is a process diagram for explaining an example of a
  • FIG. 5D is a process diagram for explaining an example of a process for producing a roll master.
  • FIG. 5E is a process diagram for explaining an example of a process for producing a roll master.
  • FIG. 6A is a process diagram for explaining an example of a process of transferring fine convex portions or concave portions by a roll master.
  • FIG. 6B is a process diagram for explaining an example of a process of transferring a fine convex portion or a concave portion with a roll master.
  • FIG. 6C is a process diagram for explaining an example of a process of transferring a fine convex portion or a concave portion with a roll master.
  • FIG. 6A is a process diagram for explaining an example of a process of transferring fine convex portions or concave portions by a roll master.
  • FIG. 6B is a process diagram for explaining an example of a process of transferring a fine convex portion or a concave portion with a roll master.
  • FIG. 7A is a plan view illustrating an example of a configuration of a plate-shaped master that is a transfer master.
  • FIG. 7B is a cross-sectional view along the line aa shown in FIG. 7A.
  • FIG. 7C is an enlarged cross-sectional view of a part of FIG. 7B.
  • FIG. 8 is a schematic diagram showing an example of the configuration of a laser processing apparatus for producing a plate-shaped master.
  • FIG. 9A is a process diagram for explaining an example of a process for producing a plate-shaped master.
  • FIG. 9B is a process diagram for explaining an example of a process for producing a plate-shaped master.
  • FIG. 9C is a process diagram for explaining an example of a process for producing a plate-shaped master.
  • FIG. 9A is a process diagram for explaining an example of a process for producing a plate-shaped master.
  • FIG. 9B is a process diagram for explaining an example of a process for producing a plate-shaped master.
  • FIG. 10A is a process diagram for explaining an example of a process of transferring fine convex portions or concave portions with a plate-shaped master.
  • FIG. 10B is a process diagram for explaining an example of a process of transferring fine convex portions or concave portions by a plate-shaped master.
  • FIG. 10C is a process diagram for explaining an example of a process of transferring a fine convex portion or a concave portion with a plate-shaped master.
  • FIG. 11 is a schematic sectional drawing of an example of the lipophilic laminated body manufactured by 4th Embodiment.
  • FIG. 12A is a process diagram for explaining an example of producing the article of the present invention by in-mold molding.
  • FIG. 12A is a process diagram for explaining an example of producing the article of the present invention by in-mold molding.
  • FIG. 12B is a process diagram for explaining an example of producing the article of the present invention by in-mold molding.
  • FIG. 12C is a process diagram for explaining an example of manufacturing the article of the present invention by in-mold molding.
  • FIG. 12D is a process diagram for explaining an example of manufacturing the article of the present invention by in-mold molding.
  • FIG. 12E is a process diagram for explaining an example of manufacturing the article of the present invention by in-mold molding.
  • FIG. 12F is a process diagram for explaining an example of manufacturing the article of the present invention by in-mold molding.
  • 13A is an AFM image of the surface of the lipophilic resin layer of the lipophilic laminate of Example 1.
  • FIG. 13B is a cross-sectional view taken along line aa in FIG. 13A.
  • FIG. 13C is an AFM image (three-dimensional image) of the lipophilic resin layer in FIG. 13A.
  • FIG. 13D is a scanning electron microscope image (SEM image) of the lipophilic resin layer in FIG. 13A.
  • 14A is an AFM image of the surface of the lipophilic resin layer of the lipophilic laminate of Example 2.
  • FIG. 14B is a cross-sectional view taken along line aa in FIG. 14A.
  • FIG. 14C is an AFM image (three-dimensional image) of the lipophilic resin layer in FIG. 14A.
  • FIG. 14D is a scanning electron microscope image (SEM image) of the lipophilic resin layer in FIG. 14A.
  • 15A is an AFM image of the surface of the lipophilic resin layer of the lipophilic laminate of Example 3.
  • FIG. 15B is a cross-sectional view taken along line aa in FIG. 15A.
  • FIG. 15C is an AFM image (three-dimensional image) of the lipophilic resin layer in FIG. 15A.
  • FIG. 15D is a scanning electron microscope image (SEM image) of the lipophilic resin layer in FIG. 15A.
  • FIG. 16A is an AFM image of the surface of the lipophilic resin layer of the lipophilic laminate of Example 4.
  • 16B is a cross-sectional view taken along line aa in FIG. 16A.
  • FIG. 16C is an AFM image (three-dimensional image) of the lipophilic resin layer in FIG. 16A.
  • FIG. 16D is a scanning electron microscope image (SEM image) of the lipophilic resin layer of FIG. 16A.
  • FIG. 17A is an AFM image of the surface of the lipophilic resin layer of the lipophilic laminate of Example 9.
  • FIG. 17B is a cross-sectional view taken along the line aa in FIG. 17A.
  • FIG. 17C is an AFM image (three-dimensional image) of the lipophilic resin layer in FIG. 17A.
  • 18A is an AFM image of the surface of the lipophilic resin layer of the lipophilic laminate of Example 10.
  • FIG. 18B is a cross-sectional view taken along the line aa in FIG. 18A.
  • FIG. 18C is an AFM image (three-dimensional image) of the lipophilic resin layer in FIG. 18A.
  • FIG. 19A is an AFM image of the surface of the lipophilic resin layer of the lipophilic laminate of Example 11.
  • FIG. 19B is a cross-sectional view taken along the line aa in FIG. 19A.
  • FIG. 19C is an AFM image (three-dimensional image) of the lipophilic resin layer in FIG. 19A.
  • 20A is an AFM image of the surface of the lipophilic resin layer of the lipophilic laminate of Example 12.
  • FIG. 20B is a cross-sectional view taken along the line aa in FIG. 20A.
  • FIG. 20C is an AFM image (three-dimensional image) of the lipophilic resin layer in FIG. 20A.
  • the lipophilic laminate of the present invention has at least a resin base material and a lipophilic resin layer, and further includes other members as necessary.
  • the said lipophilic resin layer has either a fine convex part and a recessed part on the surface.
  • the lipophilic resin layer contains 10% by mass to 55% by mass of inorganic oxide particles.
  • the oleic acid contact angle on the surface of the lipophilic resin layer is 10 ° or less.
  • the fingerprint resistance in the present invention means a characteristic that is difficult to see even if a fingerprint is attached.
  • a triacetyl cellulose TAC
  • polyester TPE
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PA polyamide
  • PA polyamide
  • PA polyamide
  • PA polyamide
  • PA polyamide
  • PE polyacrylate
  • PE polyether sulfone
  • PP polysulfone
  • PP polypropylene
  • PC polycarbonate
  • PC epoxy resin, urea resin, urethane resin, melamine resin, phenol resin, acrylonitrile-butadiene-styrene copolymer, cycloolefin polymer (COP), cycloolefin copolymer Mer (COC), PC / PMMA laminate, such as rubber
  • the resin base material preferably has transparency.
  • the average thickness of the resin substrate is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 ⁇ m to 1,000 ⁇ m, and preferably 50 ⁇ m to 500 ⁇ m. Is more preferable.
  • the resin substrate is preferably a triacetyl cellulose (TAC) film, a polyethylene terephthalate (PET) film, a polycarbonate (PC) film, a polymethyl methacrylate (PMMA) film, or a PC / PMMA laminate, and polyethylene terephthalate (PET).
  • TAC triacetyl cellulose
  • PET polyethylene terephthalate
  • PC polycarbonate
  • PMMA polymethyl methacrylate
  • PET polyethylene terephthalate
  • a film is more preferable.
  • a character, a pattern, an image, or the like may be printed on the surface of the resin base material.
  • a binder layer may be provided.
  • various adhesives can be used in addition to various binders such as acrylic, urethane, polyester, polyamide, ethylene butyl alcohol, and ethylene vinyl acetate copolymer systems.
  • Two or more binder layers may be provided.
  • the binder to be used one having heat sensitivity and pressure sensitivity suitable for the molding material can be selected.
  • the said lipophilic resin layer has either a fine convex part and a recessed part on the surface.
  • the oleic acid contact angle on the surface of the lipophilic resin layer is 10 ° or less.
  • the lipophilic resin layer is formed on the resin substrate.
  • the lipophilic resin layer contains inorganic oxide particles.
  • the content of the inorganic oxide particles in the lipophilic resin layer is 10% by mass to 55% by mass, preferably 10% by mass to 45% by mass, and more preferably 15% by mass to 35% by mass.
  • the content is less than 10% by mass, the surface hardness becomes insufficient.
  • the content exceeds 55% by mass, the flexibility becomes insufficient.
  • the content is within the more preferable range, it is possible to achieve both excellent surface strength and excellent flexibility.
  • the average particle size of the inorganic oxide particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 nm to 100 nm, and more preferably 5 nm to 90 nm.
  • the average particle diameter is a primary average particle diameter, and can be measured by, for example, ALD-7500 nano (manufactured by Shimadzu Corporation).
  • the inorganic oxide particles are not exposed on the surface of the lipophilic resin layer.
  • the inorganic oxide particles are not particularly limited and may be appropriately selected depending on the purpose.
  • the surface of the inorganic oxide particles is preferably surface-treated with an organic dispersant having a functional group such as a (meth) acryl group, a vinyl group, or an epoxy group at the terminal.
  • an organic dispersant having a functional group such as a (meth) acryl group, a vinyl group, or an epoxy group at the terminal.
  • the silane coupling agent which has the said functional group at the terminal is preferable, for example.
  • the silane coupling agent having an acrylic group at the terminal include KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.
  • Examples of the silane coupling agent having a methacryl group at the terminal include KBM-502, KBM-503, KBE-502, and KBE-503 manufactured by Shin-Etsu Chemical Co., Ltd.
  • silane coupling agent having a vinyl group at the terminal examples include KA-1003, KBM-1003, and KBE-1003 manufactured by Shin-Etsu Chemical Co., Ltd.
  • silane coupling agent having an epoxy group at the terminal examples include KBM-303, KBM-403, KBE-402, and KBE-403 manufactured by Shin-Etsu Chemical Co., Ltd.
  • an organic carboxylic acid may be used.
  • the lipophilic resin layer is not particularly limited and may be appropriately selected depending on the intended purpose, but preferably contains a cured product of an active energy ray-curable resin composition.
  • the said lipophilic resin layer has either a fine convex part and a recessed part on the surface. Either the fine convex part or the concave part is formed on the surface opposite to the resin base material side in the lipophilic resin layer.
  • a fine convex part means that the average distance of an adjacent convex part is 1,000 nm or less in the surface of the said lipophilic resin layer.
  • the fine recess means that the average distance between adjacent recesses is 1,000 nm or less on the surface of the lipophilic resin layer.
  • the shape of the convex portion and the concave portion is not particularly limited and can be appropriately selected depending on the purpose.
  • a partial shape of an ellipsoid for example, a semi-ellipsoidal shape
  • a polygonal shape for example, a sphere, a partial shape of an ellipsoid, and a polygonal shape.
  • These shapes need not be mathematically defined complete shapes, and may have some distortion.
  • the convex portions or the concave portions are two-dimensionally arranged on the surface of the lipophilic resin layer.
  • the arrangement may be a regular arrangement or a random arrangement.
  • the regular arrangement is preferably a close-packed structure from the viewpoint of the filling rate.
  • the average distance between the adjacent convex portions is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 nm to 1,000 nm, more preferably 10 nm to 800 nm, still more preferably 10 nm to 500 nm. 50 nm to 500 nm is particularly preferable.
  • the average distance between the adjacent concave portions is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 nm to 1,000 nm, more preferably 10 nm to 800 nm, still more preferably 10 nm to 500 nm, 50 nm to 500 nm is particularly preferred.
  • the average distance between the adjacent convex portions and the average distance between the adjacent concave portions are within the preferable range, the fingerprint component adhering to the lipophilic resin layer is effectively spread. In addition, the fingerprint wiping property is improved. When the average distance is within the particularly preferable range, the effect of spreading the fingerprint component and the effect of improving the fingerprint wiping property become remarkable.
  • the average height of the protrusions is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 nm to 1,000 nm, more preferably 5 nm to 500 nm, still more preferably 10 nm to 300 nm, and even more preferably 10 nm. Particularly preferred is ⁇ 150 nm.
  • the average depth of the recess is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 nm to 1,000 nm, more preferably 5 nm to 500 nm, still more preferably 10 nm to 300 nm, and more preferably 10 nm to 150 nm is particularly preferred.
  • the fingerprint component attached to the lipophilic resin layer effectively wets and spreads.
  • the fingerprint wiping property is improved.
  • the average height and the average depth are within the particularly preferable range, the effect of spreading the fingerprint component and the effect of improving the fingerprint wiping property become remarkable.
  • the average aspect ratio of the convex part (average height of the convex part / average distance of the adjacent convex part) and the average aspect ratio of the concave part (average depth of the concave part / average distance of the adjacent concave part)
  • it is preferably 0.001 to 1,000, more preferably 0.01 to 50, and particularly preferably 0.04 to 3.0.
  • the average aspect ratio of the convex portions and the average aspect ratio of the concave portions are within the preferable range, the fingerprint component attached to the lipophilic resin layer is effectively spread by wetting. In addition, the fingerprint wiping property is improved.
  • the aspect ratio is within the particularly preferable range, the effect of spreading the fingerprint component and the effect of improving the fingerprint wiping property become remarkable.
  • the average distance (Pm) of the convex part or the concave part, and the average height of the convex part or the average depth (Hm) of the concave part can be measured as follows. First, the surface S of the lipophilic resin layer having a convex portion or a concave portion is observed with an atomic force microscope (AFM), and the pitch of the convex portion or the concave portion and the height of the convex portion are determined from the cross-sectional profile of the AFM. Or the depth of a recessed part is calculated
  • AFM atomic force microscope
  • the pitch of the convex portions is a distance between the vertices of the convex portions.
  • the pitch of the recesses is the distance between the deepest portions of the recesses.
  • the height of the convex portion is the height of the convex portion based on the lowest point of the valley between the convex portions.
  • the depth of the recess is the depth of the recess based on the highest point of the peak between the recesses.
  • the pitch of the said convex part or a recessed part has in-plane anisotropy
  • the said Pm shall be calculated
  • the height of the convex portion or the depth of the concave portion has in-plane anisotropy
  • the height or depth in the direction in which the height or depth is maximum is used. Is to be sought.
  • the pitch of a short-axis direction is measured as said pitch.
  • the cross-sectional profile is a measurement target so that the convex vertex or concave base of the cross-sectional profile matches the vertex of the solid convex portion or the deepest portion of the concave portion. It cuts out so that it may become a cross section which passes through the top of a convex part of a solid shape, or the deepest part of a concave part of a solid shape.
  • the fine shape formed on the surface of the lipophilic resin layer is a convex portion or a concave portion.
  • the surface S of the lipophilic resin layer having a convex portion or a concave portion is observed with an atomic force microscope (AFM) to obtain a cross section and an AFM image of the surface S.
  • AFM image of the surface is a bright image on the outermost surface side and a dark image on the deep side
  • the bright image is formed in an island shape in the dark image
  • the surface has a convex portion.
  • Shall On the other hand, when a dark image is formed in an island shape in a bright image, the surface thereof has a recess.
  • the surface of the lipophilic resin layer having the AFM image of the surface and cross section shown in FIGS. 1A and 1B has a convex portion.
  • a three-dimensional image of the lipophilic resin layer having the AFM images of the surface and the cross section shown in FIGS. 1A and 1B is as shown in FIG. 1C.
  • the surface shown in FIGS. 2A and 2B and the surface having a cross-sectional AFM image have a recess.
  • the average separation distance is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 1 nm to 999 nm, more preferably 5 nm to 795 nm, still more preferably 10 nm to 490 nm, 100 nm to 190 nm is particularly preferable.
  • the average separation distance is within the preferable range, the fingerprint component adhering to the lipophilic resin layer is effectively wetted and spread. In addition, the fingerprint wiping property is improved.
  • the average separation distance is within the particularly preferable range, the effect of spreading the fingerprint component and the effect of improving the fingerprint wiping property become remarkable.
  • the average separation distance (Dm) of the convex portions or the concave portions that are separated can be measured as follows. First, the surface S of the lipophilic resin layer is observed with a scanning electron microscope (SEM), and the distance between adjacent convex portions or concave portions is determined from the surface SEM image. The separation distance is the shortest distance between the outer edges of adjacent convex portions or concave portions when the surface S is viewed from above. The measurement is repeatedly performed at 10 points randomly selected from the surface of the lipophilic resin layer, and the separation distances D1, D2,. Next, these separation distances D1, D2,..., D10 are simply averaged (arithmetic average) to obtain the average separation distance (Dm) of the convex portions or concave portions.
  • SEM scanning electron microscope
  • FIG. 1D shows an SEM photograph of a lipophilic resin layer having AFM images of the surface and cross section shown in FIGS. 1A and 1B.
  • the pitch (P) of the convex portions is 310 nm
  • the separation distance (D) of the convex portions is 170 nm.
  • the oleic acid contact angle on the surface of the lipophilic resin layer is 10 ° or less, preferably 5.0 ° or less, and more preferably 3.0 ° or less.
  • the oleic acid contact angle can be measured under the following conditions using, for example, PCA-1 (manufactured by Kyowa Interface Chemical Co., Ltd.). Oleic acid is put in a plastic syringe, a Teflon-coated needle is attached to the tip, and the oleic acid is dropped on the evaluation surface.
  • Drip amount of oleic acid 1 ⁇ L Measurement temperature: 25 ° C
  • the contact angle after 100 seconds has elapsed after dropping oleic acid is measured at any 10 locations on the surface of the lipophilic resin layer, and the average value is taken as the oleic acid contact angle.
  • the oleic acid contact angle on the surface of the oleophilic resin layer is preferably reduced with time when the oleic acid contact angle is measured. Between 20 seconds and 100 seconds after dropping oleic acid, 1 More preferably, the angle is smaller than 0.0 °, and particularly preferably smaller than 2.0 °. By doing so, the wiping property of the attached fingerprint by a finger, tissue, cloth or the like is improved.
  • the active energy ray-curable resin composition is not particularly limited and may be appropriately selected depending on the intended purpose as long as the desired oleic acid contact angle can be achieved in the lipophilic resin layer formed after curing.
  • polyfunctional (meth) acrylic monomer examples include 1,3-butylene glycol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, ethoxylated (3) bisphenol A diacrylate, and dipropylene.
  • examples of the polyfunctional (meth) acrylic monomer include bifunctional urethane (meth) acrylate, bifunctional epoxy (meth) acrylate, and bifunctional polyester (meth) acrylate.
  • the bifunctional urethane (meth) acrylate may be a commercially available product.
  • the commercially available products include CN940, CN963, CN963A80, CN963B80, CN963E75, CN963E80, CN982A75, CN982B88, CN983, CN985C, CN901, CN9711, CN97C, CN97C, C97
  • Examples include EBECRYL 284 manufactured by company, AT-600, UF-8001G manufactured by Kyoeisha Chemical Co., Ltd., and the like.
  • the bifunctional epoxy (meth) acrylate may be a commercially available product.
  • the commercially available products include CN104, CN104A80, CN104B80, CN104D80, CN115, CN117, CN120, CN120A75, CN120B60, CN120B80, CN120C60, CN120C80, CN120D80, CN120E50, CN120C50, E1201 UVE150 / 80, CN2100, EBECRYL 600, EBECRYL 605, EBECRYL 3700, EBECRYL 3701, EBECRYL 3702, EBECRYL 3703, Kyoeisha Chemical Co., Ltd. .
  • the bifunctional polyester (meth) acrylate may be a commercially available product.
  • Examples of the commercially available products include CN2203 and CN2272 manufactured by Sartomer.
  • glass transition temperature (Tg) of the said polyfunctional (meth) acryl monomer there is no restriction
  • the Tg is prepared by blending 5 parts by mass of the polymerization initiator with respect to 100 parts by mass of the polyfunctional (meth) acrylic monomer, and using a mercury lamp to irradiate ultraviolet rays with an irradiation amount of 1,000 mJ / cm 2.
  • the cured product obtained as described above can be used as a test piece, and can be obtained by a differential scanning calorimeter or a thermomechanical analyzer.
  • the content of the polyfunctional (meth) acrylic monomer in the active energy ray-curable resin composition is not particularly limited and may be appropriately selected depending on the intended purpose, but it is 15.0% by mass to 99.9%. % By mass is preferable, 50.0% by mass to 99.0% by mass is more preferable, and 75.0% by mass to 98.0% by mass is particularly preferable.
  • photopolymerization initiator examples include a photoradical polymerization initiator, a photoacid generator, a bisazide compound, hexamethoxymethylmelamine, and tetramethoxyglycolyl.
  • the radical photopolymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethoxyphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, bis (2,6-dimethylbenzoyl).
  • the content of the photopolymerization initiator in the active energy ray-curable resin composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1% by mass to 10% by mass, 0.5% by mass to 8% by mass is more preferable, and 1% by mass to 5% by mass is particularly preferable.
  • the active energy ray-curable resin composition can be diluted with an organic solvent when used.
  • organic solvent include aromatic solvents, alcohol solvents, ester solvents, ketone solvents, glycol ether solvents, glycol ether ester solvents, chlorine solvents, ether solvents, N-methylpyrrolidone, dimethyl
  • organic solvent include aromatic solvents, alcohol solvents, ester solvents, ketone solvents, glycol ether solvents, glycol ether ester solvents, chlorine solvents, ether solvents, N-methylpyrrolidone, dimethyl
  • formamide dimethyl sulfoxide, dimethylacetamide, and the like.
  • the active energy ray-curable resin composition is cured when irradiated with active energy rays.
  • active energy ray There is no restriction
  • the Martens hardness of the lipophilic resin layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 220 N / mm 2 to 350 N / mm 2, and is preferably 230 N / mm 2 to 300 N / mm 2. more preferably, 230N / mm 2 ⁇ 280N / mm 2 is particularly preferred.
  • the lipophilic laminate is heated and pressurized at 290 ° C. and 200 MPa. At this time, either the fine convex part or the concave part on the surface of the lipophilic resin layer may be deformed.
  • Examples of the deformation include a decrease in the height of the fine convex portion and a decrease in the depth of the fine concave portion. Although it may be deformed as long as it does not affect the fingerprint resistance, if it is deformed too much, the contact angle of oleic acid is increased and the fingerprint resistance is lowered.
  • the Martens hardness is less than 50 N / mm 2
  • the lipophilic laminate is molded, one of the fine convex portions and concave portions on the surface of the lipophilic resin layer is excessively deformed, and olein The acid contact angle is increased and fingerprint resistance is reduced, and the lipophilic resin layer is subjected to surface cleaning during normal use, such as handling and surface cleaning when manufacturing or molding the lipophilic laminate.
  • the Martens hardness exceeds 300 N / mm 2 , cracks may occur in the lipophilic resin layer or the lipophilic resin layer may be peeled off during molding.
  • the lipophilic laminate can be variously three-dimensionally produced without reducing fingerprint resistance and without causing defects such as scratches, cracks, and peeling. This is advantageous in that it can be easily formed into a shape.
  • the Martens hardness of the lipophilic resin layer may be higher than before the molding process.
  • the Martens hardness can be measured by using, for example, PICODETOR HM500 (trade name; manufactured by Fisher Instruments).
  • the load is 1 mN / 20 s, a diamond cone is used as the needle, and the surface angle is 136 °.
  • the pencil hardness of the lipophilic resin layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3H to 4H.
  • the pencil hardness is less than 3H (softer than 3H)
  • the lipophilic resin layer is applied to the lipophilic resin layer by surface cleaning during normal use, such as handling or surface cleaning when manufacturing or molding the lipophilic laminate. Scratches easily.
  • any one of the fine protrusions and recesses on the surface of the lipophilic resin layer is deformed too much, resulting in a high oleic acid contact angle and a decrease in fingerprint resistance.
  • 3H softer than 3H
  • the lipophilic laminate can be variously three-dimensionally produced without reducing fingerprint resistance and without causing defects such as scratches, cracks, and peeling. This is advantageous in that it can be easily formed into a shape.
  • high temperature and high pressure are applied to the lipophilic resin layer in the injection molding process, so that the pencil hardness of the lipophilic resin layer may be higher than before the molding process.
  • the pencil hardness is measured according to JIS K 5600-5-4.
  • the average thickness of the lipophilic resin layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 ⁇ m to 100 ⁇ m, more preferably 1 ⁇ m to 50 ⁇ m, and particularly preferably 1 ⁇ m to 30 ⁇ m.
  • the anchor layer is a layer provided between the resin base material and the lipophilic resin layer.
  • the refractive index of the anchor layer is preferably close to the refractive index of the lipophilic resin layer in order to prevent interference unevenness. Therefore, the refractive index of the anchor layer is preferably within ⁇ 0.10 of the refractive index of the lipophilic resin layer, and more preferably within ⁇ 0.05. Or it is preferable that the refractive index of the said anchor layer is between the refractive index of the said lipophilic resin layer and the refractive index of the said resin-made base materials.
  • the anchor layer can be formed, for example, by applying an active energy ray-curable resin composition.
  • an active energy ray-curable resin composition for example, an active energy ray-curable resin composition containing at least urethane (meth) acrylate and a photopolymerization initiator, and further containing other components as necessary.
  • the active energy ray-curable resin composition for example, an active energy ray-curable resin composition containing at least urethane (meth) acrylate and a photopolymerization initiator, and further containing other components as necessary.
  • the urethane (meth) acrylate and the photopolymerization initiator include the bifunctional urethane (meth) acrylate and the photopolymerization initiator exemplified in the description of the lipophilic resin layer.
  • coating method there is no restriction
  • coating method For example, wire bar coating, blade coating, spin coating, reverse roll coating, die coating, spray coating, roll coating, gravure coating , Micro gravure coating, lip coating, air knife coating, curtain coating, comma coating method, dipping method and the like.
  • the average thickness of the anchor layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.01 ⁇ m to 10 ⁇ m, more preferably 0.1 ⁇ m to 5 ⁇ m, and particularly preferably 0.3 ⁇ m to 3 ⁇ m. preferable.
  • the anchor layer may be provided with a function of reducing reflectivity or preventing charging.
  • the protective layer is not particularly limited as long as it is a layer that prevents the lipophilic resin layer from being damaged when the lipophilic laminate is formed or processed on the lipophilic resin layer. It can be appropriately selected depending on the purpose.
  • the protective layer is peeled off when the lipophilic laminate is used.
  • the pressure-sensitive adhesive layer and the adhesive layer are not particularly limited as long as they are layers formed on the resin base material and adhere the lipophilic laminate to a workpiece, an adherend, and the like. It can be appropriately selected depending on the case.
  • the elongation percentage of the lipophilic laminate is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10% or more, more preferably 10% to 200%, and particularly preferably 40% to 150%. preferable. If the elongation is less than 10%, molding may be difficult. When the elongation percentage is within the particularly preferable range, it is advantageous in that the moldability is excellent.
  • the said elongation rate can be calculated
  • the lipophilic laminate is formed into a strip shape having a length of 10.5 cm and a width of 2.5 cm to obtain a measurement sample.
  • the lipophilic laminate preferably has a smaller difference in heat shrinkage between the X direction and the Y direction in the plane of the lipophilic laminate.
  • the X direction and the Y direction of the lipophilic laminate correspond to, for example, the longitudinal direction and the width direction of the roll when the lipophilic laminate has a roll shape.
  • the difference between the heat shrinkage rate in the X direction and the heat shrinkage rate in the Y direction in the lipophilic laminate is preferably within 5% at the heating temperature used in the heating step during molding. Outside this range, during the molding process, the lipophilic resin layer may be peeled or cracked, or the characters, patterns, images, etc. printed on the surface of the resin base material may be deformed or misaligned. This may cause the molding process to be difficult.
  • the lipophilic laminate is particularly suitable for in-mold molding films, insert molding films, and overlay molding films.
  • the second method is a method for producing an oleophilic resin body in which the oleophilic resin layer and the resin base material are integrated, and the present invention thus provides the oleophilic resin.
  • the layer and the resin base material may be integrated. That is, the lipophilic resin body has either a fine convex portion or a concave portion on the surface, and the oleic acid contact angle on the surface is 10 ° or less.
  • a resin base material having either a fine convex portion or a concave portion on the surface is prepared, and the surface having either the fine convex portion or the concave portion of the resin base material is formed on the surface.
  • This is a method of forming an oleophilic resin layer that follows either a fine convex portion or a concave portion.
  • a melt extrusion method, a transfer method, or the like can be used.
  • the melt extrusion method for example, immediately after the thermoplastic resin composition is discharged from a die into a film or the like, a resin base material that is a thermoplastic resin composition having a roll surface niped by two rolls.
  • the method of transferring to is mentioned.
  • the transfer method for example, the molding surface of the master is pressed by pressing the molding surface of the master having any one of the fine protrusions and recesses against the resin base material and heating it near or above its glass transition point.
  • a thermal transfer method in which the shape is transferred to the surface of the resin base material.
  • the said active energy ray curable resin composition for forming the lipophilic resin layer on the surface of the resin-made base materials which has either a fine convex part and a recessed part on the surface, the said active energy
  • an oleophilic resin layer that follows the shape of either the fine convex portion or the concave portion is formed.
  • the second method is a method for producing a lipophilic resin body in which the lipophilic resin layer and the resin base material are integrated.
  • a resin base material itself having a fine convex portion or a concave portion on the surface and produced by using the melt extrusion method, the transfer method or the like in the first method is used.
  • the method of using an oil-based resin body is mentioned.
  • the method for producing a lipophilic laminate of the present invention includes at least an uncured resin layer forming step and a lipophilic resin layer forming step, and further includes other steps as necessary.
  • the method for producing the lipophilic laminate is a method for producing the lipophilic laminate of the present invention.
  • the uncured resin layer forming step is not particularly limited as long as it is a step of forming an uncured resin layer by applying an active energy ray-curable resin composition on a resin substrate, and is appropriately performed depending on the purpose. You can choose.
  • the active energy ray-curable resin composition is not particularly limited and may be appropriately selected depending on the purpose.
  • the active energy ray-curable resin composition is exemplified in the description of the lipophilic resin layer of the lipophilic laminate of the present invention.
  • An active energy ray-curable resin composition is exemplified.
  • the uncured resin layer is formed by applying the active energy ray-curable resin composition on the resin substrate and drying it as necessary.
  • the uncured resin layer may be a solid film or a film having fluidity due to a low molecular weight curable component contained in the active energy ray curable resin composition.
  • coating method there is no restriction
  • coating method For example, wire bar coating, blade coating, spin coating, reverse roll coating, die coating, spray coating, roll coating, gravure coating , Micro gravure coating, lip coating, air knife coating, curtain coating, comma coating method, dipping method and the like.
  • the uncured resin layer is not cured because it is not irradiated with active energy rays.
  • the active energy ray-curable resin composition may be applied on the anchor layer of the resin base material on which the anchor layer is formed to form the uncured resin layer.
  • the anchor layer There is no restriction
  • a transfer master having either a fine convex portion or a concave portion is brought into close contact with the uncured resin layer, and active energy rays are irradiated to the uncured resin layer to which the transfer master is in close contact.
  • active energy rays are irradiated to the uncured resin layer to which the transfer master is in close contact.
  • the transfer master has either a fine convex part or a concave part.
  • the method for forming any of the fine convex portions and concave portions of the transfer master and it can be selected as appropriate according to the purpose.
  • the transfer using a photoresist having a predetermined pattern shape as a protective film is possible. It is preferably formed by etching the surface of the master. Further, it is preferable to form the transfer master by irradiating the surface of the transfer master with a laser.
  • the active energy ray is not particularly limited as long as it is an active energy ray that cures the uncured resin layer, and can be appropriately selected according to the purpose. For example, description of the lipophilic laminate of the present invention And the active energy rays exemplified in 1.
  • the oleophilic resin is formed by using a transfer master in which either a fine convex portion or a concave portion is formed by etching the surface of the transfer master using a photoresist having a predetermined pattern shape as a protective film. It is an example of a layer formation process.
  • FIG. 3A is a perspective view illustrating an example of a configuration of a roll master that is a transfer master.
  • 3B is an enlarged plan view showing a part of the roll master shown in FIG. 3A.
  • 3C is a cross-sectional view of the track T in FIG. 3B.
  • the roll master 231 is a transfer master for producing the lipophilic laminate having the above-described configuration, more specifically, a master for forming a plurality of convex portions or concave portions on the surface of the lipophilic resin layer. .
  • the roll master 231 has, for example, a columnar or cylindrical shape, and the columnar surface or cylindrical surface is a molding surface for molding a plurality of convex portions or concave portions on the surface of the lipophilic resin layer.
  • a plurality of structures 232 are two-dimensionally arranged on the molding surface.
  • the structure 232 has a concave shape with respect to the molding surface.
  • glass can be used, but it is not particularly limited to this material.
  • the plurality of structures 232 disposed on the molding surface of the roll master 231 and the plurality of protrusions or recesses disposed on the surface of the lipophilic resin layer have an inverted uneven relationship. That is, the arrangement, size, shape, arrangement pitch, height or depth, aspect ratio, and the like of the structures 232 of the roll master 231 are the same as the convex portions or concave portions of the lipophilic resin layer.
  • FIG. 4 is a schematic diagram showing an example of the configuration of a roll master exposure apparatus for producing a roll master. This roll master exposure apparatus is configured based on an optical disk recording apparatus.
  • the laser beam 234 emitted from the laser light source 241 travels straight as a parallel beam and enters an electro-optic element (EOM: Electro Optical Modulator) 242.
  • EOM Electro Optical Modulator
  • the mirror 243 is composed of a polarization beam splitter and has a function of reflecting one polarization component and transmitting the other polarization component.
  • the polarization component transmitted through the mirror 243 is received by the photodiode 244, and the electro-optic element 242 is controlled based on the received light signal to perform phase modulation of the laser beam 234.
  • the laser beam 234 is condensed by an condenser lens 246 onto an acousto-optic module (AOM) 247 made of glass (SiO 2 ) or the like.
  • AOM acousto-optic module
  • the laser beam 234 is intensity-modulated by the acousto-optic element 247 and diverges, and then converted into a parallel beam by the lens 248.
  • the laser beam 234 emitted from the modulation optical system 245 is reflected by the mirror 251 and guided horizontally and parallel on the moving optical table 252.
  • the moving optical table 252 includes a beam expander 253 and an objective lens 254.
  • the laser beam 234 guided to the moving optical table 252 is shaped into a desired beam shape by the beam expander 253 and then irradiated to the resist layer on the roll master 231 through the objective lens 254.
  • the roll master 231 is placed on a turntable 256 connected to a spindle motor 255. Then, while rotating the roll master 231 and moving the laser beam 234 in the height direction of the roll master 231, the laser light 234 is intermittently applied to the resist layer formed on the peripheral side surface of the roll master 231. Then, a resist layer exposure step is performed.
  • the formed latent image has a substantially elliptical shape having a major axis in the circumferential direction.
  • the laser beam 234 is moved by moving the moving optical table 252 in the arrow R direction.
  • the exposure apparatus includes a control mechanism 257 for forming a latent image corresponding to the two-dimensional pattern of the plurality of convex portions or concave portions described above on the resist layer.
  • the control mechanism 257 includes a formatter 249 and a driver 250.
  • the formatter 249 includes a polarity reversal unit, and this polarity reversal unit controls the irradiation timing of the laser beam 234 on the resist layer.
  • the driver 250 receives the output from the polarity inversion unit and controls the acoustooptic device 247.
  • a signal is generated by synchronizing the polarity inversion formatter signal and the rotation controller for each track so that the two-dimensional pattern is spatially linked, and the intensity is modulated by the acoustooptic device 247.
  • a two-dimensional pattern such as a hexagonal lattice pattern can be recorded by patterning with a constant angular velocity (CAV) and an appropriate rotational speed, an appropriate modulation frequency, and an appropriate feed pitch.
  • CAV constant angular velocity
  • a columnar or cylindrical roll master 231 is prepared.
  • the roll master 231 is, for example, a glass master.
  • a resist layer (for example, a photoresist) 233 is formed on the surface of the roll master 231.
  • the material for the resist layer 233 include organic resists and inorganic resists.
  • the organic resist include novolak resist and chemically amplified resist.
  • the inorganic resist include metal compounds.
  • the resist layer 233 formed on the surface of the roll master 231 is irradiated with laser light (exposure beam) 234.
  • the roll master 231 is placed on the turntable 256 of the roll master exposure apparatus shown in FIG. 4, the roll master 231 is rotated, and the resist layer 233 is irradiated with a laser beam (exposure beam) 234.
  • the laser beam 234 is intermittently irradiated while moving the laser beam 234 in the height direction of the roll master 231 (a direction parallel to the central axis of the columnar or cylindrical roll master 231).
  • Layer 233 is exposed over the entire surface.
  • a latent image 235 corresponding to the locus of the laser beam 234 is formed over the entire surface of the resist layer 233.
  • the latent image 235 is, for example, arranged so as to form a plurality of rows of tracks T on the surface of the roll master and is formed with a regular periodic pattern of a predetermined unit cell Uc.
  • the latent image 235 has, for example, a circular shape or an elliptical shape.
  • the elliptical shape preferably has a major axis direction in the extending direction of the track T.
  • the surface of the roll master 231 is etched using the pattern (resist pattern) of the resist layer 233 formed on the roll master 231 as a mask.
  • the structure (recessed part) 232 which has a cone shape can be obtained.
  • the cone shape is preferably, for example, an elliptical cone shape or an elliptical truncated cone shape having a major axis direction in the extending direction of the track T.
  • the etching for example, dry etching or wet etching can be used.
  • a pattern of the cone-shaped structure 232 can be formed.
  • the intended roll master 231 is obtained.
  • a resin base material 211 on which an uncured resin layer 236 as shown in the sectional view of FIG. 6A is formed is prepared.
  • the roll master 231 and the uncured resin layer 236 formed on the resin base material 211 are brought into close contact with each other, and the active energy ray 237 is irradiated to the uncured resin layer 236.
  • the uncured resin layer 236 is cured to transfer any of the fine convex portions and concave portions, thereby obtaining the lipophilic resin layer 212 in which any one of the fine convex portions and concave portions 212a is formed.
  • the obtained lipophilic resin layer 212 is peeled from the roll master 231 to obtain a lipophilic laminate (FIG. 6C).
  • the resin base material 211 is made of a material that does not transmit active energy rays such as ultraviolet rays
  • the roll master 231 is made of a material that can transmit active energy rays (for example, quartz). You may make it irradiate an active energy ray with respect to the uncured resin layer 236 from the inside of H.231.
  • the transfer master is not limited to the roll master 231 described above, and a flat master may be used. However, from the viewpoint of improving mass productivity, it is preferable to use the roll master 231 described above as the transfer master.
  • the lipophilic resin layer formation is performed using a transfer master in which either a fine convex portion or a concave portion is formed by irradiating the surface of the transfer master with a laser to laser-process the transfer master. It is an example of a process.
  • FIG. 7A is a plan view showing an example of the configuration of a plate-shaped master.
  • FIG. 7B is a cross-sectional view along the line aa shown in FIG. 7A.
  • FIG. 7C is an enlarged cross-sectional view of a part of FIG. 7B.
  • the plate-shaped master 331 is a master for producing the lipophilic laminate having the above-described configuration, more specifically, a master for molding a plurality of convex portions or concave portions on the surface of the lipophilic resin layer. is there.
  • the plate-shaped master 331 has, for example, a surface provided with a fine concavo-convex structure, and the surface is a molding surface for molding a plurality of convex portions or concave portions on the surface of the lipophilic resin layer.
  • a plurality of structures 332 are provided on the molding surface.
  • the structure 332 illustrated in FIG. 7C has a concave shape with respect to the molding surface.
  • a material of the plate-shaped master 331 for example, a metal material can be used.
  • the metal material for example, Ni, NiP, Cr, Cu, Al, Fe, and alloys thereof can be used.
  • the alloy is preferably stainless steel (SUS). Examples of the stainless steel (SUS) include, but are not limited to, SUS304, SUS420J2, and the like.
  • the plurality of structures 332 provided on the molding surface of the plate-shaped master 331 and the plurality of protrusions or recesses provided on the surface of the lipophilic resin layer have an inverted uneven relationship. That is, the arrangement, size, shape, arrangement pitch, height, depth, and the like of the structures 332 of the plate-like master 331 are the same as those of the protrusions or recesses of the lipophilic resin layer.
  • FIG. 8 is a schematic diagram showing an example of the configuration of a laser processing apparatus for producing a plate-shaped master.
  • the laser body 340 is, for example, IFRIT (trade name) manufactured by Cyber Laser Corporation.
  • the wavelength of the laser used for laser processing is, for example, 800 nm. However, the wavelength of the laser used for laser processing may be 400 nm or 266 nm.
  • the repetition frequency is preferably larger in consideration of the processing time and the narrow pitch of the concave portions or convex portions to be formed, and is preferably 1,000 Hz or more.
  • the pulse width of the laser is preferably shorter, and is preferably about 200 femtoseconds (10 ⁇ 15 seconds) to 1 picosecond (10 ⁇ 12 seconds).
  • the laser body 340 emits laser light linearly polarized in the vertical direction. Therefore, in this apparatus, linear polarization or circular polarization in a desired direction is obtained by rotating the polarization direction using a wave plate 341 (for example, a ⁇ / 2 wave plate). Further, in this apparatus, a part of the laser light is extracted using an aperture 342 having a square opening. This is because the intensity distribution of the laser beam is a Gaussian distribution, so that only the center vicinity is used to obtain a laser beam having a uniform in-plane intensity distribution. Further, in this apparatus, the laser beam is focused using two orthogonal cylindrical lenses 343 so that a desired beam size is obtained. When processing the plate-shaped master 331, the linear stage 344 is moved at a constant speed.
  • a wave plate 341 for example, a ⁇ / 2 wave plate.
  • the beam spot of the laser irradiated on the plate-shaped master 331 is preferably a square shape.
  • the beam spot can be shaped by using, for example, an aperture or a cylindrical lens.
  • the intensity distribution of the beam spot is preferably as uniform as possible. This is because it is preferable to make the in-plane distribution such as the depth of the unevenness formed in the mold as uniform as possible.
  • the size of the beam spot is smaller than the area to be processed, it is necessary to give an uneven shape to all the areas to be processed by scanning the beam.
  • the master (mold) used to form the surface of the lipophilic resin layer is, for example, a substrate such as a metal such as SUS, NiP, Cu, Al, or Fe, and a pulse width of 1 picosecond (10 ⁇ 12 seconds) or less. It is formed by drawing a pattern using an ultrashort pulse laser, so-called femtosecond laser.
  • the polarization of the laser light may be linearly polarized light, circularly polarized light, or elliptically polarized light.
  • a pattern having desired irregularities can be formed by appropriately setting the laser wavelength, repetition frequency, pulse width, beam spot shape, polarization, laser intensity applied to the sample, laser scanning speed, and the like.
  • the parameters that can be changed to obtain the desired shape include the following.
  • the fluence is an energy density (J / cm 2 ) per pulse, and is obtained by the following equation.
  • F P / (fREPT ⁇ S)
  • S Lx ⁇ Ly
  • F fluence
  • P laser power
  • fREPT laser repetition frequency
  • S area at the laser irradiation position
  • Lx ⁇ Ly beam size
  • N fREPT ⁇ Ly / v Ly: Beam size in laser scanning direction
  • v Laser scanning speed
  • the material of the plate-shaped master 331 may be changed in order to obtain a desired shape.
  • the shape of laser processing varies depending on the material of the plate-shaped master 331.
  • the surface of the master may be coated with a semiconductor material such as DLC (diamond-like carbon).
  • DLC diamond-like carbon
  • the method for coating the surface of the master with the semiconductor material include plasma CVD and sputtering.
  • DLC diamond-like carbon
  • the semiconductor material to be coated in addition to DLC, for example, DLC mixed with fluorine (F), titanium nitride, chromium nitride, or the like can be used.
  • the average thickness of the coating obtained by coating may be about 1 ⁇ m, for example.
  • a plate-shaped master 331 is prepared.
  • a surface 331A that is a surface to be processed of the plate-like master 331 is in a mirror state, for example.
  • the surface 331A may not be in a mirror state.
  • the surface 331A may have irregularities finer than the transfer pattern, or may be equivalent to the transfer pattern. Rougher irregularities may be formed.
  • the surface 331A of the plate-shaped master 331 is laser-processed as follows using the laser processing apparatus shown in FIG. First, a pattern is drawn on the surface 331A of the plate-shaped master 331 using an ultrashort pulse laser having a pulse width of 1 picosecond (10 ⁇ 12 seconds) or less, so-called femtosecond laser. For example, as shown in FIG. 9B, the surface 331A of the plate-shaped master 331 is irradiated with femtosecond laser light Lf, and the irradiation spot is scanned with respect to the surface 331A.
  • the laser wavelength, the repetition frequency, the pulse width, the beam spot shape, the polarization, the intensity of the laser applied to the surface 331A, the laser scanning speed, etc. are appropriately set, as shown in FIG. A plurality of structures 332 having the structure is formed.
  • a resin base material 311 having an uncured resin layer 333 as shown in the sectional view of FIG. 10A is prepared.
  • the plate-shaped master 331 and the uncured resin layer 333 formed on the resin base material 311 are brought into close contact with each other, and the active energy ray 334 is applied to the uncured resin layer 333.
  • the active energy ray 334 is applied to cure the uncured resin layer 333.
  • transfer any of the fine convex portions and concave portions of the plate-shaped master 331, and form the lipophilic resin layer 312 formed with either of the fine convex portions or concave portions. obtain.
  • the obtained lipophilic resin layer 312 is peeled from the plate-shaped master 331 to obtain a lipophilic laminate (FIG. 10C).
  • the resin base material 311 is made of a material that does not transmit active energy rays such as ultraviolet rays
  • the plate-shaped master 331 is made of a material that can transmit active energy rays (for example, quartz)
  • 3rd Embodiment is an example of the said lipophilic resin layer formation process performed using the transfer original disc formed by forming a porous alumina layer in an aluminum base material.
  • Examples of the aluminum base material processed into the transfer master include, for example, an aluminum film formed on a bulk aluminum, a glass base material, or a plastic base material through an underlayer or the like.
  • the shape of the aluminum substrate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a plate shape, a cylindrical shape, and a columnar shape.
  • the porous alumina layer is formed by, for example, anodic oxidation or wet etching.
  • the porous alumina layer has fine concave portions.
  • the arrangement of the fine recesses may or may not have periodicity.
  • a method for forming the porous alumina layer specifically, as disclosed in, for example, Japanese Patent Application Laid-Open No. 2005-156695, an aluminum base material is immersed in an acidic electrolytic solution or an alkaline electrolytic solution. Examples include a method of forming a porous alumina layer having a plurality of fine recesses by applying a voltage as the anode. This anodizing treatment and a hole diameter enlargement treatment by etching treatment may be appropriately combined.
  • Examples of the lipophilic resin layer forming step performed using the produced transfer master include the same methods as in the first embodiment and the second embodiment.
  • the lipophilicity is carried out using a transfer master having a macro uneven structure formed on the surface of an aluminum substrate and subsequently forming a fine recess (micro structure) in the macro uneven structure. It is an example of a resin layer formation process. Examples of the method for producing the transfer master include the method described in JP-T-2001-517319.
  • the anti-glare layer is formed on the lipophilic laminate obtained by using the transfer master by forming the macro uneven structure and the fine recesses (micro structure) on the transfer master. Functions can be added.
  • the macro uneven structure for imparting the antiglare function can be imparted to the surface of the aluminum substrate by, for example, blasting (sand blasting or bead blasting), etching using acid, or a combination thereof.
  • the fine recesses (microstructure) can be formed by anodic oxidation, wet etching, or the like.
  • Examples of the lipophilic resin layer forming step performed using the manufactured transfer master include the same methods as in the first embodiment and the second embodiment.
  • An example of the lipophilic laminate obtained using this transfer master is shown in FIG.
  • the lipophilic laminate shown in FIG. 11 has a resin base material 401 and a lipophilic resin layer 402 on the resin base material 401.
  • the article of the present invention has the lipophilic laminate of the present invention on the surface, and further includes other members as necessary.
  • the article is not particularly limited and can be appropriately selected according to the purpose.
  • a touch panel a smartphone, a tablet PC, a cosmetic container, accessories, a glass window, a refrigerated / frozen showcase, a car window, etc.
  • Examples include window materials, mirrors in bathrooms, mirrors such as car side mirrors, pianos, and building materials.
  • the article includes glasses, goggles, a helmet, a lens, a micro lens array, a headlight cover of an automobile, a front panel, a side panel, a rear panel, a door trim, an instrument panel, a center cluster / center console panel, a shift knob, a shift knob, It may be a steering emblem.
  • These are preferably formed by in-mold molding, insert molding, or overlay molding.
  • the lipophilic laminate may be formed on a part of the surface of the article or may be formed on the entire surface.
  • the method for manufacturing the article is not particularly limited and may be appropriately selected depending on the intended purpose. However, the method for manufacturing the article of the present invention described later is preferable.
  • the method for producing an article according to the present invention includes at least a heating step, a lipophilic laminate molding step, and an injection molding step, and further includes other steps as necessary.
  • the manufacturing method of the article is the manufacturing method of the article of the present invention.
  • the heating step is not particularly limited as long as it is a step of heating the lipophilic laminate, and can be appropriately selected according to the purpose.
  • the lipophilic laminate is the lipophilic laminate of the present invention.
  • heating there is no restriction
  • limiting in particular as the temperature of the said heating Although it can select suitably according to the objective, It is preferable that it is the glass transition temperature vicinity of the said resin-made base materials, or more than a glass transition temperature.
  • time of the said heating According to the objective, it can select suitably.
  • the lipophilic laminate molding step is not particularly limited as long as it is a step of molding the heated lipophilic laminate into a desired shape, and can be appropriately selected according to the purpose.
  • mold into a desired shape with an air pressure are mentioned.
  • the injection molding process is not particularly limited as long as it is a process for injecting a molding material onto the resin base material side of the lipophilic laminate molded into a desired shape and molding the molding material. It can be appropriately selected depending on the case.
  • Examples of the molding material include resin.
  • Examples of the resin include olefin resins, styrene resins, ABS resins (acrylonitrile-butadiene-styrene copolymers), AS resins (acrylonitrile-styrene copolymers), acrylic resins, urethane resins, unsaturated polyesters. Resin, epoxy resin, polyphenylene oxide / polystyrene resin, polycarbonate, polycarbonate modified polyphenylene ether, polyethylene terephthalate, polysulfone, polyphenylene sulfide, polyphenylene oxide, polyether imide, polyimide, liquid crystal polyester, polyallyl heat resistant resin, various composite resins, various modified resins Resin etc. are mentioned.
  • the injection method is not particularly limited and can be appropriately selected depending on the purpose.
  • the molten mold is formed on the resin base material side of the lipophilic laminate adhered to a predetermined mold.
  • the method of pouring material is mentioned.
  • the manufacturing method of the article is preferably performed using an in-mold molding apparatus, an insert molding apparatus, and an overlay molding apparatus.
  • This manufacturing method is a manufacturing method using an in-mold molding apparatus.
  • the lipophilic laminate 500 is heated. Heating is preferably infrared heating.
  • the heated lipophilic laminate 500 is disposed at a predetermined position between the first mold 501 and the second mold 502.
  • the resin base material of the lipophilic laminate 500 is arranged so that the first mold 501 faces and the lipophilic resin layer faces the second mold 502.
  • the first mold 501 is a fixed mold
  • the second mold 502 is a movable mold.
  • the lipophilic laminate 500 is disposed between the first mold 501 and the second mold 502, the first mold 501 and the second mold 502 are clamped. Subsequently, the lipophilic laminate 500 is sucked through the suction holes 504 opened in the cavity surface of the second mold 502, and the lipophilic laminate 500 is mounted on the cavity surface of the second mold 502. By doing so, the cavity surface is shaped with the lipophilic laminate 500. At this time, the outer periphery of the lipophilic laminate 500 may be fixed and positioned by a film pressing mechanism (not shown). Thereafter, unnecessary portions of the lipophilic laminate 500 are trimmed (FIG. 12B).
  • the pressure hole of the first mold 501 can be connected to the lipophilic laminate 500.
  • the lipophilic laminate 500 is attached to the cavity surface of the second mold 502.
  • the molten molding material 506 is injected from the gate 505 of the first mold 501 toward the resin base material of the lipophilic laminate 500, and the first mold 501 and the second mold 502 are clamped. Then, it is injected into the cavity formed (FIG. 12C). Thereby, the molten molding material 506 is filled in the cavity (FIG. 12D). Further, after the filling of the molten molding material 506 is completed, the molten molding material 506 is cooled to a predetermined temperature and solidified.
  • the second mold 502 is moved to open the first mold 501 and the second mold 502 (FIG. 12E). By doing so, an article 507 in which the lipophilic laminate 500 is formed on the surface of the molding material 506 and in-mold molded into a desired shape is obtained. Finally, the protruding pin 508 is pushed out from the first mold 501 and the obtained article 507 is taken out.
  • the average distance of the convex portions, the average distance of the concave portions, the average height of the convex portions, the average depth of the concave portions, and the average aspect ratio were determined as follows. First, the surface of the lipophilic resin layer having a convex portion or a concave portion is observed with an atomic force microscope (AFM), and the pitch of the convex portion or the concave portion, the height of the convex portion or the concave portion from the cross-sectional profile of the AFM. Sought the depth of.
  • AFM atomic force microscope
  • the pitch of the convex portions is a distance between the vertices of the convex portions.
  • the pitch of the recesses is the distance between the deepest portions of the recesses.
  • the height of the convex portion is the height of the convex portion based on the lowest point of the valley between the convex portions.
  • the depth of the recess is the depth of the recess based on the highest point of the peak between the recesses.
  • pitches P1, P2,..., P10 and the heights or depths H1, H2,..., H10 are simply averaged (arithmetic average), and the average distance between the convex portions or the concave portions is calculated.
  • Pm the average height of the convex portions or the average depth (Hm) of the concave portions were determined.
  • An average aspect ratio (Hm / Pm) was determined from the Pm and the Hm.
  • ⁇ Oleic acid contact angle> The oleic acid contact angle was measured using PCA-1 (manufactured by Kyowa Interface Chemical Co., Ltd.) under the following conditions. Oleic acid was placed in a plastic syringe, a Teflon-coated needle was attached to the tip, and the oleic acid was dropped onto the evaluation surface. Drip amount of oleic acid: 1 ⁇ L Measurement temperature: 25 ° C The contact angle after 100 seconds after dropping oleic acid was measured at any 10 locations on the surface of the lipophilic resin layer, and the average value was defined as the oleic acid contact angle.
  • Double-sided pressure-sensitive adhesive sheet manufactured by Nitto Denko Corporation, product
  • a black acrylic plate Mitsubishi Rayon Co., Ltd., trade name: Acrylite
  • the evaluation surface lipophilic resin layer surface facing up.
  • LUCIACS CS9621T LUCIACS CS9621T
  • ⁇ Tissue wipeability Fingerprints are attached to the surface of the oleophilic resin layer with the index finger 20 times, and after wiping the tissue 10 times with a tissue (Daiou Paper Co., Ltd., Erière) in a circle, the fluorescent light is reflected and the surface is visually observed. And evaluated according to the following criteria. ⁇ Evaluation criteria ⁇ A: Fingerprint stains were gone. ⁇ : Fingerprint stains remained slightly. X: Fingerprint stains remained clearly.
  • ⁇ Pencil hardness> The pencil hardness of the oleophilic resin layer was measured in accordance with JIS K 5600-5-4.
  • the Martens hardness of the lipophilic resin layer was measured using PICODERTOR HM500 (trade name; manufactured by Fisher Instruments).
  • the load was 1 mN / 20 s, a diamond cone was used as the needle, and the surface angle was 136 °.
  • Example 1 Preparation of transfer master (glass roll master) having either fine convex part or concave part>
  • a glass roll master having an outer diameter of 126 mm was prepared, and a resist layer was formed on the surface of the glass roll master as follows. That is, the photoresist was diluted to 1/10 by weight with a thinner, and this diluted resist was applied to the average thickness of about 70 nm on the cylindrical surface of the glass roll master by dipping, thereby forming a resist layer.
  • the glass roll master is transported to the roll master exposure apparatus shown in FIG. 4, and the resist layer is exposed to form a hexagonal lattice pattern between three adjacent tracks while being continuous in one spiral.
  • the latent image was patterned on the resist layer. Specifically, a hexagonal lattice-shaped exposure pattern was formed by irradiating a region where a hexagonal lattice-shaped exposure pattern was to be formed with 0.50 mW / m of laser light.
  • the resist layer on the glass roll master was subjected to development treatment, and the exposed resist layer was dissolved and developed.
  • an undeveloped glass roll master is placed on a turntable of a developing machine (not shown), and a developer is dropped on the surface of the glass roll master while rotating the entire turntable to develop the resist layer on the surface. did. Thereby, a resist glass master having a resist layer opened in a hexagonal lattice pattern was obtained.
  • an oleophilic laminate was produced by UV imprinting using the roll master obtained as described above. Specifically, it was performed as follows. U40 (average thickness 100 ⁇ m, polyethylene terephthalate (PET) film) manufactured by Toray Industries, Inc. was used as the resin substrate.
  • PET polyethylene terephthalate
  • the ultraviolet curable resin composition for a lipophilic resin layer having the following composition was applied onto the resin substrate so that the average thickness of the resulting lipophilic resin layer was 2.5 ⁇ m.
  • the base material coated with the ultraviolet curable resin composition for the lipophilic resin layer is brought into close contact with the roll master obtained as described above, and a dose of 1, from the resin base material side using a metal halide lamp.
  • the lipophilic resin layer was cured by irradiating with ultraviolet rays at 000 mJ / cm 2 . Thereafter, the lipophilic resin layer and the roll master were peeled off.
  • -UV curable resin composition for lipophilic resin layer- -CN9006 hexafunctional aliphatic urethane acrylate, manufactured by Sartomer
  • 31 parts by mass-C150 (produced by Evonik Degussa) 64 parts by mass (50 mass% silica nanoparticle trimethylolpropane triacrylate dispersion)
  • Lucirin TPO manufactured by BASF 5 parts by mass
  • FIG. 13A shows an AFM image of the surface of the lipophilic resin layer of the obtained lipophilic laminate.
  • FIG. 13B A cross-sectional view taken along line aa in FIG. 13A is shown in FIG. 13B.
  • FIG. 13C shows a three-dimensional AFM image.
  • FIG. 13D shows an SEM image.
  • the average distance (or average distance of a recessed part) (Pm), the average height (or average depth of a recessed part) (Hm), average aspect of a convex part The ratio (Hm / Pm), the oleic acid contact angle, the conspicuousness of the attached fingerprint, the tissue wiping property, the pencil hardness, the Martens hardness, and the flexibility were evaluated. The results are shown in Table 2.
  • Example 2 In Example 1, a lipophilic laminate was produced in the same manner as in Example 1, except that the exposure pattern of the resist layer when producing the glass roll master was changed.
  • FIG. 14A shows an AFM image of the surface of the lipophilic resin layer of the obtained lipophilic laminate.
  • FIG. 14B A cross-sectional view taken along line aa in FIG. 14A is shown in FIG. 14B.
  • FIG. 14C shows a three-dimensional AFM image.
  • FIG. 14D shows an SEM image. About the produced lipophilic laminated body, evaluation similar to Example 1 was performed. The results are shown in Table 2.
  • Example 3 In Example 1, a lipophilic laminate was produced in the same manner as in Example 1 except that the exposure pattern of the resist layer when the glass roll master was produced was changed.
  • FIG. 15A shows an AFM image of the surface of the lipophilic resin layer of the obtained lipophilic laminate.
  • FIG. 15B A cross-sectional view taken along line aa in FIG. 15A is shown in FIG. 15B.
  • FIG. 15C shows a three-dimensional AFM image.
  • FIG. 15D shows an SEM image. About the produced lipophilic laminated body, evaluation similar to Example 1 was performed. The results are shown in Table 2.
  • Example 4 In Example 1, a lipophilic laminate was produced in the same manner as in Example 1 except that the exposure pattern of the resist layer when the glass roll master was produced was changed.
  • An AFM image of the surface of the lipophilic resin layer of the obtained lipophilic laminate is shown in FIG. 16A.
  • a cross-sectional view taken along line aa of FIG. 16A is shown in FIG. 16B.
  • FIG. 16C shows a three-dimensional AFM image.
  • FIG. 16D shows an SEM image. About the produced lipophilic laminated body, evaluation similar to Example 1 was performed. The results are shown in Table 2.
  • Examples 5 to 8 lipophilic laminates were produced in the same manner as in Examples 1 to 4, respectively, except that the ultraviolet curable resin composition for the lipophilic resin layer was changed to the composition shown below.
  • -UV curable resin composition for lipophilic resin layer- -CN9006 hexafunctional aliphatic urethane acrylate, manufactured by Sartomer
  • 58 parts by mass-C150 produced by Evonik Degussa
  • 37 parts by mass (50% by mass silica nanoparticle trimethylolpropane triacrylate dispersion)
  • Lucirin TPO manufactured by BASF
  • Example 2 The same evaluation as Example 1 was performed about the produced lipophilic laminated body. The results are shown in Table 2.
  • Example 9 ⁇ Preparation of transfer master (plate-like master) having either fine convex part or concave part>
  • the apparatus shown in FIG. 8 was used.
  • the laser body 340 As the laser body 340, IFRIT (trade name) manufactured by Cyber Laser Co., Ltd. was used. The laser wavelength was 800 nm, the repetition frequency was 1,000 Hz, and the pulse width was 220 fs.
  • a master was prepared by coating DLC (diamond-like carbon) on the surface of a plate-like substrate (SUS) by a sputtering method.
  • fine concave portions were formed on the surface of the DLC film of the master using the laser processing apparatus.
  • laser processing was performed under the laser processing conditions shown in Table 1.
  • a plate-shaped master for shape transfer was obtained. Note that the size of the master was a rectangular shape of 2 cm ⁇ 2 cm.
  • FIG. 17A shows an AFM image of the surface of the lipophilic resin layer of the obtained lipophilic laminate.
  • FIG. 17B A cross-sectional view taken along line aa in FIG. 17A is shown in FIG. 17B.
  • FIG. 17C shows a three-dimensional AFM image.
  • evaluation similar to Example 1 was performed. The results are shown in Table 2.
  • Example 9 a lipophilic laminate was produced in the same manner as in Example 9 except that the conditions for producing the plate-shaped master were changed to the conditions shown in Table 1.
  • An AFM image of the surface of the lipophilic resin layer of the obtained lipophilic laminate of Example 10 is shown in FIG. 18A.
  • a cross-sectional view taken along line aa in FIG. 18A is shown in FIG. 18B.
  • FIG. 18C shows a three-dimensional AFM image.
  • FIG. 19A shows an AFM image of the surface of the lipophilic resin layer of the obtained lipophilic laminate of Example 11.
  • FIG. 19B A cross-sectional view taken along line aa in FIG. 19A is shown in FIG. 19B.
  • FIG. 19C shows a three-dimensional AFM image.
  • FIG. 20A An AFM image of the surface of the lipophilic resin layer of the obtained lipophilic laminate of Example 12 is shown in FIG. 20A.
  • FIG. 20B A cross-sectional view taken along line aa in FIG. 20A is shown in FIG. 20B.
  • FIG. 20C shows a three-dimensional AFM image.
  • Evaluation similar to Example 1 was performed. The results are shown in Table 2.
  • Example 13 In Example 2, a lipophilic laminate was produced in the same manner as in Example 2, except that the ultraviolet curable resin composition for the lipophilic resin layer was changed to the composition shown below. About the produced lipophilic laminated body, evaluation similar to Example 1 was performed. The results are shown in Table 2.
  • -UV curable resin composition for lipophilic resin layer- -CN9006 hexafunctional aliphatic urethane acrylate, manufactured by Sartomer
  • 80 parts by mass-C150 (produced by Evonik Degussa) 20 parts by mass (50 mass% silica nanoparticle trimethylolpropane triacrylate dispersion)
  • Lucirin TPO manufactured by BASF 5 parts by mass
  • Example 14 In Example 2, a lipophilic laminate was produced in the same manner as in Example 2, except that the ultraviolet curable resin composition for the lipophilic resin layer was changed to the composition shown below. About the produced lipophilic laminated body, evaluation similar to Example 1 was performed. The results are shown in Table 2.
  • -UV curable resin composition for lipophilic resin layer- CN9006 (hexafunctional aliphatic urethane acrylate, manufactured by Sartomer) 19 parts by mass C150 (produced by Evonik Degussa) 76 parts by mass (50% by mass silica nanoparticle trimethylolpropane triacrylate dispersion) ⁇ Lucirin TPO (manufactured by BASF) 5 parts by mass
  • Example 15 In Example 2, a lipophilic laminate was produced in the same manner as in Example 2, except that the ultraviolet curable resin composition for the lipophilic resin layer was changed to the composition shown below. About the produced lipophilic laminated body, evaluation similar to Example 1 was performed. The results are shown in Table 2.
  • -UV curable resin composition for lipophilic resin layer- CN9006 (hexafunctional aliphatic urethane acrylate, manufactured by Sartomer) 9 parts by mass C150 (produced by Evonik Degussa) 86 parts by mass (50% by mass silica nanoparticle trimethylolpropane triacrylate dispersion) ⁇ Lucirin TPO (manufactured by BASF) 5 parts by mass
  • Example 16 In Example 2, a lipophilic laminate was produced in the same manner as in Example 2, except that the ultraviolet curable resin composition for the lipophilic resin layer was changed to the composition shown below. About the produced lipophilic laminated body, evaluation similar to Example 1 was performed. The results are shown in Table 2.
  • -UV curable resin composition for lipophilic resin layer- -CN9006 hexafunctional aliphatic urethane acrylate, manufactured by Sartomer
  • 31 parts by mass-C150 (produced by Evonik Degussa) 64 parts by mass (50 mass% silica nanoparticle trimethylolpropane triacrylate dispersion)
  • Lucirin TPO manufactured by BASF 5 parts by mass
  • Example 17 In Example 2, a lipophilic laminate was produced in the same manner as in Example 2, except that the ultraviolet curable resin composition for the lipophilic resin layer was changed to the composition shown below. About the produced lipophilic laminated body, evaluation similar to Example 1 was performed. The results are shown in Table 2.
  • -UV curable resin composition for lipophilic resin layer- -CN9006 (hexafunctional aliphatic urethane acrylate, manufactured by Sartomer) 31 parts by mass-nanobyk-3601 (produced by Big Chemie Japan) 64 parts by mass (30 mass% alumina nanoparticle TPGDA dispersion) ⁇ Lucirin TPO (manufactured by BASF) 5 parts by mass
  • Example 18 In Example 2, a lipophilic laminate was produced in the same manner as in Example 2, except that the ultraviolet curable resin composition for the lipophilic resin layer was changed to the composition shown below. About the produced lipophilic laminated body, evaluation similar to Example 1 was performed. The results are shown in Table 2.
  • -UV curable resin composition for lipophilic resin layer- CN9006 (hexafunctional aliphatic urethane acrylate, manufactured by Sartomer) 31 parts by mass Titania dispersion 1 64 parts by mass (50% mass titania nanoparticle trimethylolpropane triacrylate dispersion) ⁇ Lucirin TPO (manufactured by BASF) 5 parts by mass
  • titanium oxide ST-01 manufactured by Ishihara Sangyo Co., Ltd. was used as titania.
  • TMPTA trimethylolpropane triacrylate
  • Example 19 In Example 2, a lipophilic laminate was produced in the same manner as in Example 2, except that the ultraviolet curable resin composition for the lipophilic resin layer was changed to the composition shown below. About the produced lipophilic laminated body, evaluation similar to Example 1 was performed. The results are shown in Table 2.
  • -UV curable resin composition for lipophilic resin layer- CN9006 (hexafunctional aliphatic urethane acrylate, manufactured by Sartomer) 31 parts by mass Titania dispersion 2 64 parts by mass (50% mass titania nanoparticle trimethylolpropane triacrylate dispersion) -Lucirin TPO (manufactured by BASF) 5 parts by mass Titanium used was Titanium Oxide F-1 manufactured by Showa Denko KK This was mixed with trimethylolpropane triacrylate (TMPTA) at a ratio of 1: 1 (mass ratio), and the beads were dispersed for 9 hours using zirconia beads having a diameter of 0.65 mm in a paint shaker to prepare titania dispersion 2. .
  • TMPTA trimethylolpropane triacrylate
  • Example 20 A lipophilic laminate was prepared in the same manner as in Example 2, except that the ultraviolet curable resin composition for the lipophilic resin layer was changed to the composition shown below. About the produced lipophilic laminated body, evaluation similar to Example 1 was performed. The results are shown in Table 2.
  • -UV curable resin composition for lipophilic resin layer- -CN9006 (hexafunctional aliphatic urethane acrylate, manufactured by Sartomer) 48 parts by mass-Trimethylolpropane triacrylate (manufactured by Nihon Gosei Co., Ltd.) 47 parts by mass-Lucirin TPO (manufactured by BASF) 5 parts by mass
  • -UV curable resin composition for lipophilic resin layer- -CN9006 (hexafunctional aliphatic urethane acrylate, manufactured by Sartomer) 48 parts by mass-Trimethylolpropane triacrylate (manufactured by Nihon Gosei Co., Ltd.) 47 parts by mass-Lucirin TPO (manufactured by BASF) 5 parts by mass
  • Example 2 the lipophilic laminated body was obtained like Example 2 except having changed the ultraviolet curable resin composition for lipophilic resin layers into the composition shown below. About the produced lipophilic laminated body, evaluation similar to Example 1 was performed. The results are shown in Table 2.
  • -CN9006 hexafunctional aliphatic urethane acrylate, manufactured by Sartomer 85 parts by mass-C150 (produced by Evonik Degussa) 10 parts by mass (50 mass% silica nanoparticle trimethylolpropane triacrylate dispersion)
  • Lucirin TPO manufactured by BASF 5 parts by mass
  • Example 10 (Comparative Example 10)
  • the lipophilic laminated body was obtained like Example 2 except having changed the ultraviolet curable resin composition for lipophilic resin layers into the composition shown below.
  • evaluation similar to Example 1 was performed. The results are shown in Table 2.
  • Example 11 In Example 2, the lipophilic laminated body was obtained like Example 2 except having changed the ultraviolet curable resin composition for lipophilic resin layers into the composition shown below. About the produced lipophilic laminated body, evaluation similar to Example 1 was performed. The results are shown in Table 2.
  • Trimethylolpropane triacrylate (manufactured by Nihon Gosei Co., Ltd.) 35 parts by mass ⁇ 90 G (manufactured by Evonik Degussa) 60 parts by mass (silica nanoparticle powder) -Lucirin TPO (manufactured by BASF) 5 parts by mass
  • the beads are dispersed in a paint shaker for 9 hours using zirconia beads having a diameter of 0.65 mm, and an ultraviolet curable resin composition for a lipophilic resin layer.
  • the additive particle size in Table 2 is the average particle size of the inorganic oxide particles contained in the lipophilic resin layer.
  • the average particle diameter is a primary average particle diameter.
  • Examples 1 to 20 have fingerprint resistance, pencil hardness of 3H or higher, Martens hardness of 220 N / mm 2 or higher, and excellent flexibility test.
  • the oil-based laminate had both excellent surface hardness and excellent flexibility while having fingerprint resistance.
  • the content of the inorganic oxide particles in the lipophilic resin layer is 10% by mass to 45% by mass, the balance between surface hardness and flexibility is very excellent, and 15% by mass to 35% by mass. In this case, the balance between surface hardness and flexibility was extremely excellent (for example, see Examples 1, 5, 13, 14, 15, and 20).
  • Comparative Examples 1 to 8 since the lipophilic resin layer did not contain inorganic oxide particles, the surface strength was insufficient. In Comparative Examples 9 to 10, the lipophilic resin layer contained inorganic oxide particles, but the surface strength was insufficient due to the small content. In Comparative Example 11, since the lipophilic resin layer contained inorganic oxide particles, the surface strength was sufficient, but because the content was too large, the flexibility was insufficient.
  • the lipophilic laminate of the present invention can be used by bonding to a touch panel, a smartphone, a smartphone cover, a tablet PC, a home appliance, a cosmetic container, accessories, and the like.
  • the lipophilic laminate of the present invention uses in-mold molding, insert molding, and overlay molding to provide automotive interior parts such as door trims, instrument panels, center cluster / center console panels, shift knobs, shift knobs, and steering emblems. It can be used on the surface of automobile exterior parts such as surfaces and door handles.

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Abstract

L'invention concerne un corps stratifié lipophile composé d'un matériau de base en résine et d'une couche de résine lipophile disposée sur le matériau de base en résine. La couche de résine lipophile présente, sur une surface de celle-ci, soit de minuscules saillies soit de minuscules évidements. La couche de résine lipophile comprend 10 à 55 % en masse de particules d'oxydes inorganiques. L'angle de contact avec l'acide oléique de la surface de la couche de résine lipophile est inférieur ou égal à 10°.
PCT/JP2014/076823 2013-10-08 2014-10-07 Corps stratifié lipophile, son procédé de production et article WO2015053272A1 (fr)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
WO2015170546A1 (fr) * 2014-05-09 2015-11-12 デクセリアルズ株式会社 Stratifié lipophile, son procédé de fabrication et article
EP4108445A4 (fr) * 2020-02-17 2024-03-20 Mitsubishi Chemical Corporation Stratifié et procédé de fabrication de stratifié

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