JP6131034B2 - Laminated sheet and film for laminating with water repellency - Google Patents

Description

  The present invention relates to a laminated sheet imparted with water repellency and a laminate film that is used after being peeled from the laminated sheet.

  In recent years, with the progress of microfabrication technology, there is an increasing interest in efforts to impart a water-repellent function using the lotus effect by arranging a fine concavo-convex structure on the surface of a molded body. It has been confirmed that a molded article having a fine concavo-convex structure exhibits water repellency (Patent Document 1). And the proposal which improves water repellency further by making formation of a fine concavo-convex structure and coating with a water repellent is also made (patent document 2). Further, in the case of coating with a conventional water repellent, it is considered that the coated water repellent layer is deteriorated and the water repellency is lowered. Therefore, a kneading type water repellent has also been proposed (Patent Document 3).

  In recent years, resin-molded products are often used in watering parts such as washrooms, kitchens, and bathrooms. More specifically, toiletries include soap dishes, washbasins, dust boxes, etc. Kitchen utensils include colander, balls, kitchen pockets, trays, sink corners, cooking bats, tawashirak, washbasins, sink mats, drainers Examples include bath shampoo stands, dust boxes, hot water baths, bath chairs, handbags, and the like. Examples of other resin molded products include washing tubs and dehydration tubs for washing machines, toilets for nursing care, food transport containers, and buckets.

  In view of such a background, if there is a laminating film that can maintain a water-repellent layer without coating a water-repellent agent, it can be used by laminating on various members such as water-circulating parts and wallpaper parts, desirable.

JP-A-7-108552 JP 2000-167955 A JP 2001-335691 A

  The present invention has been made in view of the above circumstances, and a water-repellent laminate sheet in which a laminate film exhibiting significant water repellency even if not coated with a water-repellent agent is releasably laminated, and the laminate sheet is peeled off. It aims at providing the laminate film used.

  Therefore, according to one aspect of the present invention, the concavo-convex shape layer having a fine concavo-convex shape made of a resin composition containing a polyolefin-based resin and a water repellent agent is made of a resin that is incompatible with the resin composition. There is provided a water-repellent laminate sheet that is laminated on one surface of a release resin layer and a base material layer is laminated on the other surface of the release resin layer.

  In the above, in a preferred embodiment, the water repellent is a silicone-based water repellent, more preferably, a resin composition comprising a silicone resin, a higher fatty acid amide, and an olefin resin, and the silicone resin content is And 2 to 20% by mass relative to the total mass of the resin composition of the concavo-convex shape layer.

  Further, in a preferred embodiment, the convex shape of the fine concavo-convex shape is a hexagonal frustum shape having a hexagonal bottom surface and a circular convex vertex, a convex shape height of 50 μm to 90 μm, and a convex shape The bottom diameter (hexagonal diagonal length) is 50 μm to 90 μm, and the aspect ratio (convex height / convex bottom diameter) is 0.6 to 1.0. Moreover, in a preferable embodiment, in the convex shape of the concavo-convex shape, the diameter of the convex vertex portion with respect to the convex bottom surface diameter (diameter of convex vertex portion / convex shape bottom surface diameter) is 0.05 to 0.4. In one embodiment, when the surface of the concavo-convex shape layer is tilted by 60 °, the falling speed at which the liquid rolls is 0.001 m / sec to 0.15 m / sec, and / or the surface of the concavo-convex shape layer. The sliding angle with the liquid is 70 ° or less.

  Furthermore, in a preferred embodiment, the thickness of the uneven shape layer is 60 μm to 100 μm, and / or the thickness of the release resin layer is 10 to 50 μm. In one embodiment, the release resin layer is made of a high impact polystyrene resin or an ethylene-vinyl alcohol copolymer resin. Moreover, in one embodiment, a base material layer contains 10-40 mass% of polystyrene resins and 90-60 mass% of high impact polystyrene resins as a resin component, and also a rubber component is 5 with respect to 100 mass parts of resin components. It is formed from a styrene resin layer containing 0.0 part by mass or more, or is formed from a modified olefin resin.

  According to another aspect of the present invention, there is provided a water-repellent laminate film, wherein the water-repellent laminate sheet is composed of a concavo-convex shape layer that is peeled off together with a base material layer. In one embodiment, the water repellent laminate film is a laminate film for water-based members, and in another embodiment, a laminate film for wallpaper members.

  Since the water-repellent laminated sheet according to the present invention is not coated with a water-repellent agent, the water-repellent property is not deteriorated, and the water-repellent laminated film is peeled off and used for various members and applications. Can do.

It is a schematic longitudinal cross-sectional view which shows the laminated structure of the water-repellent laminated sheet which concerns on one Embodiment of this invention. It is a figure which shows the state by which the laminate film is peeled from the water-repellent laminated sheet in the same schematic vertical cross section as FIG. It is a schematic plan view of the water repellent laminated sheet of FIG.

As shown in FIG. 1, the water-repellent laminated sheet according to one embodiment of the present invention includes a concavo-convex shape layer (1) having a fine concavo-convex shape on one surface, and the other surface of the concavo-convex shape layer (in the drawing). , Lower surface) and a base material layer (3) laminated via a release resin layer (2).
In the present invention, “water repellency” of the water-repellent laminated sheet means that the falling angle of the liquid with respect to the laminated sheet is 70 ° or less in consideration of use for a laminating film for water-circulating members and wallpaper members. Shall.

<Uneven shape layer (1)>
The concavo-convex shape layer is provided in order to develop water repellency, and is formed from a thermoplastic resin composition containing a polyolefin resin and a water repellent, and has a fine concavo-convex shape on one surface serving as a sheet surface. It is the resin layer which has.

  Here, the polyolefin resin means a resin made of a polymer containing an α-olefin as a monomer, and particularly includes a polyethylene resin and a polypropylene resin. Examples of the polyethylene resin include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, linear medium-density polyethylene, and the like, as well as copolymers, grafts, and blends having their structure. Things are also included. Examples of the latter resin include ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid ester copolymer, ethylene-vinyl acetate-vinyl chloride copolymer. Examples thereof include those obtained by copolymerizing and blending a resin having a polar group in a polyethylene chain, such as a blend or a ternary copolymer with an acid anhydride. Examples of the polypropylene resin include homopolypropylene, random polypropylene, and block polypropylene. When using homopolypropylene, the structure of the homopolypropylene may be any of isotactic, atactic, and syndiotactic. When using random polypropylene, the α-olefin to be copolymerized with propylene preferably includes those having 2 to 20 carbon atoms, more preferably 4 to 12 carbon atoms, such as ethylene, 1-butene, 1-pentene, 1 Examples include -hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and the like. When block polypropylene is used, a block copolymer (block polypropylene), a block copolymer containing a rubber component, a graft copolymer, or the like can be given. In addition to using these olefin resins alone, other olefin resins can also be used in combination.

  In addition, when giving uneven | corrugated shape to the resin layer surface, the thermal transfer method etc. can be used as mentioned later, but the uneven | corrugated shape shapeability (transferability) in that case, and uneven | corrugated shape depending on the case may be used. From the viewpoint of crosslinkability by electron beam irradiation performed for curing, it may be preferable to use linear low density polyethylene or linear medium density polyethylene. Such linear low density polyethylene and linear medium density polyethylene include those polymerized with a Ziegler type catalyst (t-LLDPE) and those polymerized with a metallocene catalyst (m-LLDPE). , M-LLDPE is a copolymer resin of an olefin having 3 or more carbon atoms as a comonomer, preferably a linear, branched or aromatic nucleus-substituted α-olefin having 3 to 18 carbon atoms and ethylene. Examples of the linear monoolefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, -Octadecene and the like. Examples of the branched monoolefin include 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene and the like. Moreover, styrene etc. are mentioned as a monoolefin substituted by the aromatic nucleus. These comonomers can be copolymerized with ethylene singly or in combination of two or more. In this copolymerization, polyenes such as butadiene, isoprene, 1,4-hexadiene, dicyclopentadiene, and 5-ethylidene-2-norbornene may be copolymerized. The α-olefin content in the copolymer resin is generally 1 to 20 mol%.

  In one embodiment, the water repellent is a silicone water repellent, and is composed of a composition containing a silicone resin and a higher fatty acid amide in a polyolefin resin as a base, and the silicone resin has a molecular weight of 1,000 to 50,000 in particular. Low molecular weight silicone resin and high molecular weight silicone resin having a molecular weight of 200,000 to 1,000,000. The polyolefin resin here means a resin similar to the polyolefin resin of the base resin of the concavo-convex layer, and examples thereof include low-density polyethylene, high-density polyethylene, and polypropylene. The same or different resin may be used. Examples of the silicone resin include organopolysiloxane, dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and the like. Among them, dimethylpolysiloxane is preferably used. Higher fatty acid amides, in combination with silicone resins, fulfill the function of developing excellent antifouling properties, such as saturated fatty acid amides (such as stearic acid amide and behenic acid amide), unsaturated fatty acid amides (oleic acid). Amide, erucic acid amide, etc.), saturated fatty acid bisamide (ethylene bisstearic acid amide, etc.), unsaturated fatty acid bisamide (ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N, N′-dioleyl sebacic acid amide, etc.) These may be used, and these may be used alone or in combination of two or more. Of these, oleic acid amide which is an unsaturated fatty acid amide is preferable.

  In the silicone-based water repellent, the content of the silicone resin (the total amount of the high molecular weight silicone resin and the low molecular weight silicone resin) is 2 with respect to the total mass of the resin constituting the concavo-convex shape layer including the water repellent itself. ˜20 mass%. By setting the composition within this range, a concavo-convex shape layer that can satisfy all of the concavo-convex shape shapeability (transferability), crosslinkability, and water repellency in a thermal transfer method for imparting concavo-convex shape to the sheet surface can be obtained. However, if it is less than 2% by mass, sufficient water repellency may not be obtained. If it exceeds 20% by mass, poor appearance may occur during sheet production.

  The thickness of the uneven shape layer is preferably 60 to 100 μm. If the thickness is less than 60 μm, thickness unevenness may occur during sheet production. Moreover, when it exceeds 100 micrometers, manufacturing cost will become high.

  The concavo-convex shape is provided for imparting water repellency to the sheet and means a fine undulating concavo-convex shape capable of imparting water repellency to the sheet, but the shape is arbitrary. For example, the convex shape of the concavo-convex portion may be a pyramid shape such as a triangular pyramid, a quadrangular pyramid, a hexagonal pyramid, an octagonal pyramid, a cone, a truncated pyramid shape, or a truncated cone shape, but the present inventor performs various studies on the layer configuration according to the present embodiment. As a result, it was found that a hexagonal pyramidal convex shape is particularly preferable. Further, the convex and concave shape has a height h of 50 μm to 90 μm, a diameter D (bottom diameter, hexagonal diagonal length) of 50 μm to 90 μm, and an aspect ratio (convex height / convex shape bottom). (Diameter) can be 0.6 to 1.0. Even when outside this range, excellent water repellency can be obtained as compared with the case where the concavo-convex shape is not used, but by making the concavo-convex shape within this range, the water repellency to the extent that the liquid rolls can be expressed. On the other hand, if the convex shape height is less than 50 μm, the water repellency to the extent that the liquid rolls may not be exhibited, and if the convex shape height exceeds 90 μm, the concave / convex shape dimension in the mold for imparting the concave / convex shape is small. May become unstable. If the convex bottom surface diameter is less than 50 μm, the concave / convex shape dimension in the mold for imparting the concave / convex shape may become unstable, and if the convex bottom surface diameter exceeds 90 μm, depending on the resin used, the concave / convex surface It may look bad.

  Further, in the convex shape of the concavo-convex shape, the ratio of the diameter d of the convex vertex portion to the convex bottom surface diameter D (the diameter of the convex vertex portion / the convex bottom surface diameter) is preferably 0.05 to 0.40. . By making the concavo-convex shape within this range, water repellency to the extent that the liquid rolls can be expressed. On the other hand, if the ratio is less than 0.05, it may be difficult to produce the concavo-convex mold, and if the ratio is 0.40 or more, water repellency to the extent that the liquid rolls may not be expressed.

  The arrangement of the convex shape is not particularly limited, and there are a grid arrangement and a zigzag arrangement arranged vertically and horizontally. If it is desired to maintain water repellency after thermoforming, a staggered arrangement is preferred.

<Peeling resin layer (2)>
In the embodiment according to the present invention, the release resin layer is a thermoplastic resin composition that is incompatible with the thermoplastic resin composition constituting the concavo-convex shape layer and is non-adhesive, preferably a polyolefin resin. It is a resin that does not adhere. Examples of such resins include styrene resins, ethylene-vinyl alcohol copolymer resins, polyamide resins, and the like.

  Styrene resins constituting the release resin layer include styrene monomers such as styrene, α-methyl styrene, p-methyl styrene, dimethyl styrene, p-t-butyl styrene, chlorostyrene, or copolymers thereof. Copolymers of monomers and other monomers, such as styrene-acrylonitrile copolymer (AS resin), or other polymers such as styrene monomers, such as polybutadiene, styrene-butadiene copolymer, polyisoprene, poly Examples thereof include graft polymers obtained by graft polymerization in the presence of a diene rubber polymer such as chloroprene, such as high impact polystyrene (HIPS resin), styrene-acrylonitrile graft polymer (ABS resin), and the like. Among these, polystyrene (GPPS resin) and high impact polystyrene (HIPS resin) are preferable from the viewpoint of sheet formability. The styrene resin layer preferably contains 5.0 to 8.6% by mass of a butadiene rubber component. The butadiene rubber component content is a simple method to adjust by blending GPPS resin and HIPS resin, but it may be adjusted at the manufacturing stage of HIPS resin. If the butadiene rubber component is less than 5.0% by mass, the sheet may be cracked during film formation, and if it exceeds 8.6% by mass, the concavo-convex layer may not be partially peeled off.

  The ethylene-vinyl alcohol copolymer resin is usually obtained by saponifying an ethylene-vinyl acetate copolymer, and has an ethylene content of 10 to 10 in order to have oxygen barrier properties, workability, and moldability. It is preferably 65 mol%, preferably 20 to 50 mol%, and a saponification degree of 90% or more, preferably 95% or more.

  Polyamide resins include lactam polymers such as caprolactam and laurolactam, polymers of aminocarboxylic acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid, hexamethylenediamine, decamethylenediamine, and dodecamethylenediamine. Aliphatic diamines such as 2,2,4- or 2,4,4-trimethylhexamethylenediamine, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis (p-aminocyclohexylmethane), etc. Diamine units such as alicyclic diamines, aromatic diamines such as m- or p-xylylenediamine, aliphatic dicarboxylic acids such as adipic acid, suberic acid and sebacic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, Dicals of aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid Polycondensates of phosphate units, and copolymers thereof, and the like. Specifically, nylon 6, nylon 9, nylon 11, nylon 12, nylon 66, nylon 610, nylon 611, nylon 612, nylon 6T, nylon 6I, nylon MXD6, nylon 6/66, nylon 6/610, nylon 6 / 6T, nylon 6I / 6T, etc., among which nylon 6 and nylon MXD6 are preferred.

  The thickness of the release resin layer is preferably 10 to 50 μm, more preferably 20 to 40 μm. If it is less than 10 μm, it may be peeled off during sheet production, and if it exceeds 50 μm, the production cost may increase depending on the resin used.

<Base material layer (3)>
The base material layer may be any material as long as it has been conventionally used as a base material for thermoplastic resin sheets, and is formed from a styrene resin, a modified olefin polymer resin, or the like.
Styrenic resins include styrene monomers such as styrene, α-methyl styrene, p-methyl styrene, dimethyl styrene, pt-butyl styrene, chlorostyrene, or copolymers, styrene monomers and other monomers. Copolymer, such as styrene-acrylonitrile copolymer (AS resin), or diene rubber such as styrene monomer and other polymer such as polybutadiene, styrene-butadiene copolymer, polyisoprene, polychloroprene, etc. Examples include graft polymers obtained by graft polymerization in the presence of a porous polymer, such as high impact polystyrene (HIPS resin) and styrene-acrylonitrile graft polymer (ABS resin). Among these, polystyrene (GPPS resin) and high impact polystyrene (HIPS resin) are preferable from the viewpoint of sheet formability. Moreover, it is preferable that a styrene resin layer contains 5.0 mass% or more of butadiene rubber components. The butadiene rubber component content is a simple method to adjust by blending GPPS resin and HIPS resin, but it may be adjusted at the manufacturing stage of HIPS resin. If the butadiene rubber component is less than 5.0% by mass, it may be cracked during film formation.

  Examples of the modified olefin polymer include homopolymers of olefins having about 2 to 8 carbon atoms such as ethylene, propylene and butene-1, and these olefins and ethylene, propylene, butene-1, 3-methylbutene-1, pentene- Other olefins having about 2 to 20 carbon atoms such as 1,4-methylpentene-1, hexene-1, octene-1 and decene-1, vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, acrylic ester, methacrylic acid Olefin resins such as acid esters and copolymers with vinyl compounds such as styrene, ethylene-propylene copolymers, ethylene-propylene-diene copolymers, ethylene-butene-1 copolymers, propylene-butene-1 Copolymers and other olefin rubbers such as acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic Unsaturated carboxylic acids such as acid, fumaric acid, itaconic acid, citraconic acid and tetrahydrophthalic acid, or derivatives thereof such as acid halides, amides, imides, anhydrides and esters, specifically maleenyl chloride, maleimide, maleic anhydride Typical examples include acids, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like modified under the graft reaction conditions. Among them, an ethylene-based resin, a propylene-based resin, or an ethylene-propylene or butene-1 copolymer rubber modified with an unsaturated dicarboxylic acid or an anhydride thereof, particularly maleic acid or an anhydride thereof is preferable.

<Water-repellent laminated sheet>
The layer structure of the water-repellent laminated sheet according to the present invention is, in a typical embodiment, concavo-convex shape layer / release resin layer / base material layer.
The thickness of the water repellent laminated sheet is preferably 500 to 1200 μm, more preferably 700 to 1000 μm. When the thickness is less than 500 μm, uneven shape transfer may be insufficient, and when it exceeds 1200 μm, the production cost may increase.

  The method for laminating the water-repellent laminated sheet is not particularly limited, and a general method can be used. For example, each raw material resin is melt extruded using three single-screw extruders, and a multilayer resin sheet is obtained using a feed block and a T die, and a multilayer resin sheet is obtained using a multi-manifold die. . Moreover, there is no restriction | limiting in particular in the formation method of the uneven | corrugated shape in this invention, The method manufactured using an extrusion molding system, The method manufactured using a photolithography system, The method manufactured using a hot press system, A pattern roll and Various methods such as a method of manufacturing using a UV curable resin can be used.

<Water-repellent laminate film>
The water-repellent laminate film according to the present invention is obtained by peeling the release resin layer together with the base material layer from the water-repellent laminated sheet. That is, it is a sheet made of an uneven shape layer. Since the release resin layer is made of a resin that is incompatible with the resin of the concavo-convex shape layer, the laminate film can be easily peeled from the release resin layer.
Since the laminate film thus obtained has excellent water repellency, it can be suitably used for various applications requiring water repellency. For example, it is used for bathroom doors, windows, and building materials that do not require transparency used in bathrooms, etc., and is laminated to various water-related parts such as gutters, laminates on the exterior of cars, baths, etc. Thus, it can be used for imparting water repellency, and it can also be used for laminating wallpaper members used around the water in kitchens, bathrooms and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the content of these Examples etc. at all.

Resin raw materials used in Examples and the like are as follows.
(1) Concavity and convexity layer ・ Linear low density polyethylene resin: “UF240” (manufactured by Nippon Polyethylene)
・ Polypropylene resin: “PM822V” (manufactured by Sun Allomer)
Water repellent A (resin composition comprising silicone resin and olefin resin): Silicone resin content 30% by mass “Crimbell 30PE” (Fuji Chemical Co., Ltd.)
Water repellent B (resin composition comprising a silicone resin and an olefin resin): 50% by mass of a silicone resin “Crimbell 50PP” (manufactured by Fuji Chemical Co., Ltd.)
(2) Release resin layer • HIPS resin: “Toyostyrene H850” (manufactured by Toyo Styrene Co., Ltd., butadiene content: 9.0% by mass)
GPPS resin: “HRM23” (manufactured by Toyo Styrene Co., Ltd.)
-Ethylene-vinyl alcohol copolymer: "EVAL J-102B" (Kuraray Co., Ltd., ethylene content 32 mol%, saponification degree 99% or more)
(3) Base material layer-Modified olefin polymer: "Modic F502" (Mitsubishi Chemical Corporation)
Styrenic resin: Resin composition comprising HIPS resin and GPPS resin HIPS resin: “Toyostyrene H850” (Toyo Styrene Co., Ltd., butadiene content: 9.0% by mass)
GPPS resin: “HRM23” (manufactured by Toyo Styrene Co., Ltd.)

<Example 1>
Three 40 mm single screw extruders were used to extrude a 900 μm thick multilayer resin sheet having a layer configuration of uneven layer 75 μm / release resin layer 20 μm / base material layer 805 μm by a feed block method. The extruded sheet was cast with a transfer roll having a concavo-convex shape on the surface and a touch roll by a laser engraving method to obtain a water-repellent laminated sheet having a concavo-convex shape. The temperature control of the uneven shape transfer roll and the touch roll was 85 ° C., and the touch pressure was 9 MPa.

  Various evaluations of the obtained water-repellent laminated sheet were performed by the following methods. The results are shown in Table 2.

(1) Irregular shape observation The irregular shape of the sheet is observed using a laser microscope VK-X100 (manufactured by Keyence Corporation), and the height of the convex shape, the convex bottom surface diameter, the convex vertex interval, and the convex vertex portion diameter are measured. And recorded together with the aspect ratio (convex shape height / convex shape bottom surface diameter). Moreover, the sample for observing the concavo-convex shape cross section was produced using a microtome.
(2) Falling speed The falling speed was measured using an automatic contact angle meter DM-501 (manufactured by Kyowa Interface Science Co., Ltd.). With the sheet tilted by 60 °, the speed at which the liquid falls on the surface of the uneven layer was measured. The test solution was purified water, noodle soup, and honey, and the dropping amount was 20 μL.
(3) Slipping angle The sliding angle was measured using an automatic contact angle meter DM-501 (manufactured by Kyowa Interface Science Co., Ltd.). The test solution was purified water, noodle soup, and honey, and the dropping amount was 20 μL.
If the sliding angle is 70 ° or less, it can be determined that the water repellency is high.
(4) Interlaminar peelability The produced sheet was peeled off manually, and the peelability was evaluated. The evaluation criteria were as follows.
・ Peels without tearing: Good ・ Does not peel off, is partially bonded: Defective

<Examples 2 to 10 and Comparative Examples 1 to 6>
The water-repellent laminates according to Examples 2 to 10 and Comparative Examples 1 to 9 are the same as Example 1 except that the uneven shape layer, release resin layer, and base layer composition and thickness are set as shown in Table 1. A sheet was produced. About the produced sheet | seat, it carried out similarly to the case in Example 1, and evaluated various characteristics. The results are shown in Table 2.
In Comparative Example 1, no water repellent material was added, and in Comparative Example 2, the uneven shape was not imparted. In Comparative Example 3, the release resin layer was SEBS resin, and in Comparative Example 4, the release resin layer was HIPS resin. In Comparative Example 5, the release resin layer itself was not provided, and in Comparative Example 6, the uneven shape layer itself was not provided.

From the results shown in Table 2, the following became clear.
In all of Examples 1 to 10, satisfactory water repellency was obtained for any of the falling speed and falling angle for purified water, noodle soup and honey, and the delamination property was also excellent. On the other hand, in Comparative Example 1, Comparative Example 2 and Comparative Example 6, sufficient water repellency was not obtained. In Comparative Example 3, the delamination property was poor, and in Comparative Example 4, the delamination property was poor, and in the case of honey, the water repellency was not sufficient. Furthermore, in Comparative Example 5, delamination occurred between the concavo-convex shape layer and the base material layer during production.

  As mentioned above, although this invention was demonstrated using embodiment, it cannot be overemphasized that the technical scope of this invention is not limited to the range as described in the said embodiment. It will be apparent to those skilled in the art that various modifications or improvements can be added to the above embodiment. Further, it is apparent from the scope of the claims that the embodiments added with such changes or improvements can be included in the technical scope of the present invention.

DESCRIPTION OF SYMBOLS 1 Concave-shaped layer 2 Peeling resin layer 3 Base material layer h Convex-shaped height D Bottom face diameter (diagonal length of hexagon)
d Diameter of convex shape apex

Claims (15)

  A concavo-convex shape layer provided with a fine concavo-convex shape made of a resin composition containing a polyolefin-based resin and a water repellent is laminated on one surface of a release resin layer made of a resin incompatible with the resin composition, A water-repellent laminate sheet comprising a base material layer laminated on the other surface of the release resin layer.   The water repellent laminated sheet according to claim 1, wherein the water repellent is a silicone water repellent.   3. The silicone water repellent comprises a resin composition comprising a silicone resin, a higher fatty acid amide, and an olefin resin, and the content of the silicone resin in the water repellent is 2 to 20% by mass. The water-repellent laminated sheet described in 1.   The convex and concave bottom surface of the fine concavo-convex shape is hexagonal, the convex vertex is a hexagonal truncated pyramid, the convex height is 50 μm to 90 μm, and the convex bottom surface diameter is 50 μm to 90 μm. The water repellent laminated sheet according to any one of claims 1 to 3, wherein the aspect ratio (convex shape height / convex shape bottom surface diameter) is 0.6 to 1.0.   5. The convex shape of the concavo-convex shape, wherein the diameter of the convex vertex portion with respect to the convex bottom surface diameter (diameter of the convex vertex portion / convex shape bottom surface diameter) is 0.05 to 0.4. The water-repellent laminated sheet according to one item. The water repellency according to any one of claims 1 to 5, wherein when the surface of the concavo-convex shape layer is inclined by 60 °, the falling speed at which purified water rolls is 0.001 m / sec to 0.15 m / sec. Laminated sheet. The water-repellent laminated sheet according to any one of claims 1 to 6, wherein a tumbling angle with purified water on the surface of the uneven shape layer is 70 ° or less.   The water-repellent laminated sheet according to any one of claims 1 to 7, wherein the thickness of the concavo-convex shape layer is 60 µm to 100 µm.   The water-repellent laminated sheet according to any one of claims 1 to 8, wherein the release resin layer has a thickness of 10 to 50 µm.   The water repellent laminated sheet according to any one of claims 1 to 9, wherein the release resin layer is made of a high impact polystyrene resin or an ethylene-vinyl alcohol copolymer resin.   A base material layer contains 10-40 mass% of polystyrene resins and 90-60 mass% of high impact polystyrene resins as resin components, and further contains 5.0 mass parts or more of rubber components with respect to 100 mass parts of resin components. The water-repellent laminated sheet according to any one of claims 1 to 10, wherein the water-repellent laminated sheet is formed from a styrenic resin layer.   The water-repellent laminated sheet according to any one of claims 1 to 10, wherein the base material layer is formed from a modified olefin resin.   The water-repellent laminate film which consists of an uneven | corrugated shaped layer of the water-repellent laminated sheet as described in any one of Claims 1-12.   The water-repellent laminate film according to claim 13, which is a laminate film for water-circulating members.   The water-repellent laminate film according to claim 13, which is a laminate film for a wallpaper member.

Images