CN106715124B

CN106715124B - Liquid-repellent resin sheet, and sheet for building material and sheet for packaging material for living goods each using same

Info

Publication number: CN106715124B
Application number: CN201580048567.9A
Authority: CN
Inventors: 藤原纯平; 大泽知弘; 前田圭史
Original assignee: Denka Co Ltd
Current assignee: Denka Co Ltd
Priority date: 2014-09-12
Filing date: 2015-09-09
Publication date: 2021-11-30
Anticipated expiration: 2035-09-09
Also published as: JP6694388B2; WO2016039379A1; JPWO2016039379A1; CN106715124A; TWI711541B; TW201627140A

Abstract

The invention provides a liquid-repellent resin sheet having excellent liquid repellency. Further, a sheet for building materials and a sheet for packaging living goods, which are excellent in liquid repellency, oxygen barrier property and weather resistance, and which use the liquid-repellent resin sheet. A liquid-repellent resin sheet is obtained by providing a fine uneven-shaped layer made of a polyolefin resin composition, the uneven-shaped layer having at least 1 or more kinds of uneven shapes on one surface, and providing a liquid-repellent layer containing hydrophobic oxide fine particles and a fluorine-based copolymer resin on the surface having the uneven shapes.

Description

Liquid-repellent resin sheet, and sheet for building material and sheet for packaging material for living goods each using same

Technical Field

The present invention relates to a liquid-repellent resin sheet, and a sheet for building materials and a sheet for packaging living goods using the same.

Background

Heretofore, as a sheet for a building material such as wallpaper, a sheet for food such as refreshing drinking water, fruit juice beverage, favorite food and drink, or a sheet for a packaging material for living goods, a sheet obtained by coating a polymer material on a paper material has been used. For example, patent document 1 proposes a sheet in which a fluorine-based copolymer is applied to a nonwoven fabric. Further,

patent documents

2 and 3 also propose a liquid repellent for paper and cloth.

On the other hand, in a display member or the like, a film in which an oil repellent agent is applied to a PET resin has been proposed (patent document 4). Further, in automobile parts, a film in which a water repellent is applied to the surface of an uneven shape has also been proposed (patent document 5).

When a sheet or film obtained by applying an oil repellent agent to the paper material, PET resin, or the like is used as a packaging material for food or living use, there is a problem of adhesion of food (oil-based liquid), and for example, in the case of a sheet for pouch (pouch), there is a concern that an oil-based or surfactant-based liquid adheres to the packaging material. However, the means described in patent documents 1 to 4 cannot sufficiently solve such a problem. In addition, even with the means described in patent document 5, such a problem cannot be sufficiently solved for oil-based liquids, surfactant-based liquids, and the like.

Patent document 1: japanese laid-open patent application No. 2010-196196

Patent document 2: japanese laid-open patent publication No. 2009-256506

Patent document 3: japanese patent laid-open publication No. 2007-291373

Patent document 4: japanese laid-open patent publication No. 2009-104054

Patent document 5: japanese laid-open patent publication No. 2008-122435

Disclosure of Invention

The present invention has been made in view of the above circumstances, and an object of a main aspect of the present invention is to provide a liquid-repellent resin sheet which, when used as a building material or a packaging material for living goods, reduces adhesion of an oil-based liquid and a surfactant-based liquid to a surface of the sheet. Further, it is an object of the present invention to provide a sheet for building materials produced using the liquid-repellent resin sheet and a sheet for food packaging materials having excellent oxygen barrier properties.

That is, the present inventors considered that various liquid repellency developing means were investigated in order to prevent adhesion of an oil-based liquid and a surfactant-based liquid and to impart liquid repellency thereto, and as a result, found that a high liquid repellency capable of preventing adhesion of an oil-based or surfactant-based liquid can be imparted to the surface of a sheet by imparting a fine uneven shape to the surface of the sheet and applying a liquid repellent agent, and completed the present invention.

The present invention for solving the above problems is constituted as follows.

(1) A liquid-repellent resin sheet comprising an uneven-shaped layer which is composed of a composition comprising a polyolefin resin and has a fine uneven shape, wherein at least 1 or more kinds of uneven shapes are formed on one surface of the uneven-shaped layer, and a liquid-repellent layer comprising hydrophobic oxide fine particles and a fluorine-based copolymer resin is formed on the surface having the uneven shape.

(2) The liquid-repellent resin sheet according to (1), wherein a base material layer having at least 1 or more layers made of a resin selected from the group consisting of styrene resins, olefin resins, polyester resins, nylon resins, ethylene-vinyl alcohol copolymer resins and acrylic resins is laminated on the other surface of the uneven-shaped layer.

(3) The liquid-repellent resin sheet according to (1) or (2), wherein the resin composition contains 35 to 100% by mass of a polyolefin-based resin.

(4) The liquid-repellent resin sheet according to any one of (1) to (3), wherein a sealant resin layer composed of at least 1 resin selected from a modified olefin-based polymer resin and a hydrogenated styrene-based thermoplastic elastomer is formed between the uneven shape layer and the base material layer.

(5) The liquid-repellent resin sheet according to any one of (1) to (4), wherein the convex shapes include a 1 st convex shape and a 2 nd convex shape, the height of the 1 st convex shape and the height of the 2 nd convex shape are each 20 μm to 150 μm, and the apex interval of adjacent convex shapes is 20 μm to 100 μm.

(6) The liquid-repellent resin sheet according to (5), wherein the 1 st and 2 nd convex shapes are arranged alternately, and the ratio of the height of the 2 nd convex shape to the height of the 1 st convex shape is 0.4 or more and 0.8 or less.

(7) The liquid-repellent resin sheet according to any one of (1) to (6), wherein the resin composition has a melt mass flow rate at 230 ℃ of 5g/10 minutes or more.

(8) The liquid-repellent resin sheet according to any one of (1) to (7), wherein the hydrophobic oxide fine particles are hydrophobic silica fine particles having trimethylsilyl groups on the surface.

(9) The liquid-repellent resin sheet according to any one of (1) to (8), wherein the content of the hydrophobic oxide fine particles in the liquid-repellent layer is 20 to 70% by mass, and the content of the fluorine-based copolymer resin is 70 to 30% by mass.

(10) The liquid-repellent resin sheet according to any one of (1) to (9), wherein the thickness of the concavo-convex shaped layer is 50 μm to 200 μm.

(11) The liquid-repellent resin sheet according to any one of (1) to (10), wherein a contact angle of the surface of the concavo-convex shape layer when in contact with an oil-based liquid or a surfactant-based liquid is 130 ° or more, and a roll-off angle is 40 ° or less.

(12) A sheet for building materials, which uses the liquid-repellent resin sheet according to any one of (1) to (11).

(13) A sheet for packaging living goods, which uses the liquid-repellent resin sheet according to any one of (1) to (11).

(14) The sheet for a building material according to (12), which is a sheet for a wallpaper member.

(15) The sheet for packaging material of living goods according to (13), which is a sheet for members of a place where water is required in a house.

(16) The sheet for packaging material of living goods according to the item (13), which is a sheet for lid material of food container.

(17) The sheet for packaging living goods according to (13), which is a sheet for a pouch.

In the present invention, it has been found that the liquid-repellent resin sheet having a liquid-repellent layer containing hydrophobic oxide fine particles and a fluorine-based copolymer resin on a surface having at least 1 or more kinds of projections on one surface of a fine-textured-shaped layer formed of a polyolefin-based resin composition has significantly improved adhesion prevention properties with respect to an oil-based liquid and a surfactant-based liquid on the surface of the sheet. Further, by laminating a base material layer having at least 1 or more layers of a resin selected from the group consisting of styrene resins, olefin resins, polyester resins, nylon resins, ethylene-vinyl alcohol copolymer resins, and acrylic resins on the other surface of the uneven layer, the oxygen barrier property and weather resistance are improved. Therefore, the liquid-repellent resin sheet of the present invention can be suitably used as a building material sheet such as a wallpaper member, a member of a place requiring water in a house, a lid material for a food container, a living product packaging sheet for a pouch, and the like.

Drawings

Fig. 1 is a longitudinal cross-sectional side view schematically showing a liquid-repellent resin sheet according to a first embodiment of the present invention.

Fig. 2 is a schematic plan view of the liquid-repellent resin sheet of fig. 1.

Fig. 3 is a longitudinal cross-sectional schematic view of another embodiment of the liquid-repellent resin sheet according to the first embodiment of the present invention.

Fig. 4 is a schematic plan view of the liquid-repellent resin sheet of fig. 3.

Fig. 5 is a longitudinal cross-sectional side view schematically showing a laminated structure of liquid-repellent resin sheets according to a second embodiment of the present invention.

Fig. 6 is a longitudinal cross-sectional side view schematically showing a laminated structure of liquid-repellent resin sheets according to a third embodiment of the present invention.

Fig. 7 is a longitudinal cross-sectional side view schematically showing a laminated structure of liquid-repellent resin sheets according to a fourth embodiment of the present invention.

FIG. 8 shows a vacuum-formed container using a single-layer sheet (900 μm thick) of impact-resistant polystyrene.

Detailed Description

The liquid-repellent resin sheet (hereinafter, simply referred to as "resin sheet") according to the present invention has at least 1 or more kinds of projections on one surface of a corrugated layer formed of a resin composition containing a polyolefin resin (hereinafter, sometimes referred to as "polyolefin resin"), and has a liquid-repellent layer containing hydrophobic oxide fine particles and a fluorine-based copolymer resin on the surface having the projections. Various embodiments of the resin sheet will be described below, and a method for producing the resin sheet will be described next, but when a specific description given for one embodiment is applied to another embodiment, the description thereof will be omitted in the other embodiment.

[ first embodiment ]

As shown in fig. 1 and 3, the resin sheet according to the first embodiment of the present invention includes an uneven layer made of a polyolefin resin composition having a fine uneven shape, and the uneven layer has at least 1 or more kinds of uneven shapes (1a) on one surface. The convex surface is provided with a liquid-repellent layer (2) which is composed of a fluorine-based copolymer resin containing hydrophobic oxide fine particles.

< layer of irregular shape >

The convex shape may be 1 kind of convex shape as shown in fig. 1, but preferably has a 1 st convex shape and a 2 nd convex shape which are different in shape (height) as shown in fig. 3. In addition, 3 or more kinds of convex shapes having different shapes may be provided. Wherein the height of the 1 st convex shape is set higher than the height of the 2 nd convex shape. When the 1 st projection and the 2 nd projection are used, the arrangement is not limited, but in terms of liquid repellency, the 1 st projection and the 2 nd projection are preferably arranged alternately. The convex shape is not particularly limited in arrangement form, and may be arranged in a checkerboard manner or in a staggered manner. If the water repellency is further maintained, the staggered arrangement is preferable. Further, as a method for forming the uneven shape layer, there is a method in which a transfer roller and a contact roller having uneven shapes formed by a laser engraving method are used to cast a resin sheet surface; and a method of transferring the unevenness of the sheet by heating and pressing with a belt-shaped mold.

The height (h) of the convex shape is preferably 20 to 150. mu.m. If the height of the convex shape is less than 20 μm, sufficient liquid repellency may not be secured, and if the height of the convex shape is greater than 150 μm, the size of the concave-convex shape in the mold for imparting the concave-convex shape may become unstable. The height of the projections also includes the thickness (100nm to 4000nm) of a liquid repellent layer described later.

The distance (t) between the apexes of the adjacent convex shapes is preferably 20 to 100 μm. The vertex spacing is the spacing between the vertices of the convex shapes that are positioned at the shortest distance from each other, and even if the convex shapes are different from each other, the vertex spacing means the spacing between the vertices of the convex shapes as long as they are adjacent to each other. When the apex interval is less than 20 μm, the uneven shape size in the die for imparting the uneven shape may become unstable. If it exceeds 100. mu.m, the liquid repellency may be lowered.

The height of the convex shape and the distance between the apexes of the convex shape can be measured using a laser microscope (for example, VK-X100 manufactured by Keyence Corporation).

When 2 kinds of convex shapes are used, the ratio of the height of the 2 nd convex shape to the height of the 1 st convex shape is preferably 0.4 or more and 0.8 or less. By setting the height ratio to 0.4 or more and 0.8 or less, the liquid repellency can be more effectively obtained.

The bottom surface of the convex shape can be triangular pyramid, rectangular pyramid, hexagonal pyramid, octagonal pyramid, cone, etc.; a pyramid shape; the present inventors have made various studies on the structure of the resin sheet according to the present embodiment, and as a result, have found that a convex shape having a hexagonal pyramid shape is particularly preferable.

In the resin sheet of the present invention, a resin composition containing a polyolefin resin is used as the resin composition for forming the uneven shape layer. The content of the polyolefin resin in the resin composition is preferably 35% by mass or more. By making the content of the inorganic particles to 35 mass% or more, the transferability of the uneven shape can be improved. The upper limit is not particularly limited, and may be, for example, 80 mass% or less or 100 mass% or less.

The polyolefin resin composition preferably has a melt mass flow rate at 230 ℃ of 5g/10 min or more. By setting the ratio to 5g/10 min or more, the transferability of the uneven shape can be improved. The melt mass flow rate was measured in accordance with JIS K7210 under the conditions of a test temperature of 230 ℃ and a load of 2.16 kg.

The polyolefin-based resin means a resin composed of a polymer containing an α -olefin as a monomer, and particularly preferably contains a polyethylene-based resin and a polypropylene-based resin. Examples of the polyethylene resin include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and linear medium-density polyethylene, and copolymers, grafts, and blends having these structures in addition to monomers are also included. Examples of the latter resin (copolymer, blend) include an ethylene-vinyl acetate copolymer, an ethylene-acrylic acid copolymer, an ethylene-acrylic ester copolymer, an ethylene-methacrylic ester copolymer, and an ethylene-vinyl acetate-vinyl chloride copolymer, and further include those obtained by copolymerizing and blending a resin having a polar group in a polyethylene chain, such as those obtained by blending these copolymers with a 3-membered copolymer of an acid anhydride, and the like.

Examples of the polypropylene resin include homopolypropylene, atactic polypropylene, and block polypropylene. In the case of using homopolypropylene, the structure of the homopolypropylene may be any of isotactic, atactic and syndiotactic. When random polypropylene is used, the alpha-olefin copolymerized with propylene is preferably an alpha-olefin having 2 to 20 carbon atoms, more preferably 4 to 12 carbon atoms, and examples thereof include ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, and 1-decene. When the block polypropylene is used, a block copolymer (block polypropylene), a block copolymer containing a rubber component, a graft copolymer, or the like can be exemplified. Other olefin resins may be used in combination with these olefin resins alone.

The resin composition may contain other resins within a range not to impair the effects of the present invention. Examples of the other resins include styrene resins, vinyl chloride resins, and (meth) acrylic resins. Examples of the styrene resin include general-purpose polystyrene, impact-resistant polystyrene, a styrene-conjugated diene block copolymer, a methyl methacrylate-butadiene-styrene copolymer, and an acrylonitrile-butadiene-styrene copolymer. The content of the other resin is preferably 50% by mass or less, more preferably 20% by mass or less, in the uneven layer.

< liquid repellent layer >

The liquid-repellent layer contains hydrophobic oxide fine particles and a fluorine-based copolymer resin. The thickness of the liquid repellent layer is preferably 100nm to 4000nm, but the thickness is not limited to this numerical range as long as the effects of the present invention are obtained. The term "liquid repellency" as used herein means a liquid repellency to a sufficient degree to prevent adhesion of an oil-based liquid or a surfactant-based liquid to a resin sheet, and specifically means that the contact angle of these liquids with respect to the liquid on the resin sheet is 130 ° or more and the roll-off angle of the liquids is 40 ° or less.

The hydrophobic oxide fine particles may be oxide fine particles having a hydrophobic group, or may be oxide fine particles hydrophobized by surface treatment. For example, hydrophilic oxide fine particles may be surface-treated with a silane coupling agent or the like to make the surface hydrophobic. The kind of the oxide is not limited as long as it is hydrophobic. Of these, at least 1 kind of hydrophobic fumed silica, fused silica, alumina, titania, and the like can be used. The hydrophobic particles are not limited in shape, and may be spherical or non-spherical (crushed).

Specific examples of these include, for example, silica, which includes: the product names "AEROSIL R972", "AEROSIL R972V", "AEROSIL R972 CF", "AEROSIL R974", "AEROSIL RX 200", "AEROSIL RY 200" (manufactured by Nippon AEROSIL Co. Ltd., "AEROSIL R202", "AEROSIL R805", "AEROSIL R812", and "AEROSIL R812S" (manufactured by Evonik Degussa Corporation). The titanium dioxide may be named "AEROXIDE TiO2T 805" (manufactured by Evonik Degussa Corporation), for example. Examples of the alumina include: fine particles having a hydrophobic particle surface are obtained by treating a product name "Aeroxide Alu C" (manufactured by Evonik Degussa Corporation) or the like with a silane coupling agent.

Specifically, hydrophobic silica fine particles having a trimethylsilyl group or a dimethylsiloxane group on the surface are preferable in obtaining more excellent water repellency. Examples of commercially available products include: the above-mentioned "AEROSIL R812", "AEROSIL R812S", and "AEROSIL RY 300" (manufactured by Evonik Degussa Corporation), and the like.

The hydrophobic oxide fine particles preferably have an average primary particle diameter of 5nm to 1000nm, more preferably 7nm to 200 nm. When the average particle diameter of the primary particles is 5nm to 1000nm, the liquid repellency is improved and the dispersibility in the fluorine-based copolymer resin is improved. The average particle diameter of the primary particles is a value obtained by measuring the diameters of 3000 to 5000 hydrophobic oxide fine particles using a scanning electron microscope and calculating the average value.

The fluorine-based copolymer resin is a copolymer containing a fluorine atom, and preferably contains the copolymer (1) and the copolymer (2) described below. The copolymer (1) and the copolymer (2) may contain the following structural units (a) to (d). However, the copolymer (1) contains the structural unit (a) and the structural unit (b), and the copolymer (2) contains the structural unit (a) and the structural unit (c). The copolymer (1) mainly contributes to the development of liquid repellency of the resin sheet, and the copolymer (2) mainly contributes to the durability of the resin sheet.

The structural unit (a) is an alkyl group in which a part or all of hydrogen atoms are substituted with fluorine atoms, and the number of carbon atoms is 1 to 6. The structural unit (a) may be a chain polyfluoroalkyl group having 1 or more unsaturated groups such as carbon-carbon unsaturated double bonds. As the unsaturated group, (meth) acrylate is preferable.

The structural unit (b) is preferably a monomer having a saturated hydrocarbon group having 16 to 40 carbon atoms, more preferably a (meth) acrylate containing an alkyl group having 16 to 40 carbon atoms, and still more preferably stearyl (meth) acrylate or behenyl (meth) acrylate.

The structural unit (c) is a monomer derived from a monomer having a crosslinkable functional group and not containing a fluorine atom. As the crosslinkable functional group, an isocyanate group, a blocked isocyanate group, an alkoxysilyl group, an amino group, an alkoxymethylamide group, a silanol group, an ammonium group, an amide group, an epoxy group, a hydroxyl group, an oxazoline group, a carboxyl group, an alkenyl group, a sulfonic group, and the like are preferable. Further, epoxy group, hydroxyl group, blocked isocyanate group, alkoxysilyl group, amino group, and carboxyl group are more preferable.

The monomer forming the structural unit (c) is preferably a (meth) acrylate, a compound having 2 or more copolymerizable groups (for example, 2-isocyanatoethyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate, etc.), a vinyl ether or a vinyl ester. The structural unit (c) may also be derived from a mixture of 2 or more species. The structural unit (c) mainly affects the film-forming property of the liquid-repellent film, the adhesiveness and the close adhesion of the liquid-repellent composition to the substrate, and contributes to the improvement of the durability.

The structural unit (d) is a structural unit derived from a monomer having a polymerizable group other than the structural units (a), (b) and (c). Further, a monomer which is excellent in film-forming property and can give a uniform copolymer solution or dispersion is preferable. As the structural unit (d), vinyl chloride, vinylidene chloride, cyclohexyl methacrylate, polyoxyethylene di (meth) acrylate, alkyl ether of polyoxyethylene di (meth) acrylate, and dioctyl maleate are particularly preferable. The structural unit (d) can contribute to improvement in adhesion of the composition to a substrate and improvement in dispersibility.

Commercially available products corresponding to these include "AG-E070" and "AG-E550D" (manufactured by Asahi glass Co., Ltd.).

The liquid-repellent layer preferably contains the hydrophobic oxide fine particles in an amount of 20 to 70% by mass and the fluorine-based copolymer resin in an amount of 70 to 30% by mass. With the composition in this range, the multilayer resin sheet can have good rolling properties. On the other hand, when the content of the hydrophobic oxide fine particles is less than 20% by mass, the liquid repellency and the liquid falling property that can be satisfied may not be obtained; if the content of the hydrophobic oxide fine particles exceeds 70 mass%, the hydrophobic oxide fine particles may peel off.

As a method for forming the liquid repellent layer on the uneven surface, a method of preparing a dispersion in which hydrophobic oxide fine particles are added to isopropyl alcohol (IPA) in advance and then applying a dispersion adjusted at an arbitrary ratio with an aqueous dispersion of a fluorine-based resin copolymer to the uneven surface by an applicator or the like can be employed.

[ second embodiment ]

As shown in fig. 5, an example of the resin sheet according to the second embodiment of the present invention is a resin sheet in which a sealant resin layer (3) is formed between a textured layer (1) having a liquid repellent layer (2) laminated on the surface thereof and a base material layer (4). Specifically, the layers of the resin sheet according to the second embodiment form, from top to bottom, a liquid repellent layer (2), a textured layer (1), a sealant resin layer (3), and a base material layer (4). Note that the liquid repellent layer and the uneven layer are the same as those described in the first embodiment, and therefore, the description thereof is omitted. However, the thickness of the uneven layer is preferably 50 μm to 200 μm. If the thickness is less than 50 μm, transfer of the uneven shape may be defective. In addition, if it exceeds 200. mu.m, the production cost may be increased.

< substrate layer >

The substrate layer is preferably a thermoplastic resin such as a styrene resin (e.g., impact-resistant polystyrene, polybutadiene-polystyrene-polyacrylonitrile graft polymer), an olefin resin (e.g., polyethylene or polypropylene), a polycarbonate, a polyester resin (e.g., polyethylene terephthalate or polybutylene terephthalate), a nylon resin (e.g., nylon 6 or nylon-66), an ethylene-vinyl alcohol copolymer, or an acrylic resin. In the case of lamination, there are lamination by coextrusion, and lamination by extrusion lamination or dry lamination using an unstretched film or a biaxially stretched film.

As the base layer, a polyester resin is preferable. For example, as the polyester resin to be the base layer, polyethylene terephthalate, polybutylene terephthalate, polyethylene-2, 6-naphthalate, polypropylene terephthalate, and polyester resins obtained by copolymerizing a diol component such as diethylene glycol, neopentyl glycol, or polyalkylene glycol, and a dicarboxylic acid component such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, or 2, 6-naphthalenedicarboxylic acid, for example, as a copolymerization component can be used.

In the base material layer, a coloring agent such as a pigment or a dye may be added as necessary within a range not to impair the effect of the present invention; releasing agents such as silicone oil; fibrous reinforcing agents such as glass fibers; colorants such as talc, clay and silica; salt compounds of sulfonic acid and alkali metals, antistatic agents such as polyalkylene glycol, and ultraviolet absorbers; an antimicrobial agent. Further, the resin scrap generated in the production process of the multilayer resin sheet of the present invention may be mixed and used.

< sealing agent resin layer >

The sealant resin layer is a layer that exhibits adhesion between the uneven layer and the base material layer. The resin components include 100 mass% of a modified olefin polymer resin and 100 parts by mass of a hydrogenated styrene thermoplastic elastomer.

The sealant resin layer is preferably a modified olefin polymer. As the modified olefin-based polymer resin, the following are exemplified: olefin-based resins such as copolymers of olefins having 2 to 8 carbon atoms such as ethylene, propylene and butene-1, copolymers of these olefins with other olefins having 2 to 20 carbon atoms such as ethylene, propylene, butene-1, 3-methylbutene-1, 1-pentene, 4-methylpentene-1, hexene-1, octene-1 and decene-1, and copolymers with vinyl compounds such as vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, acrylic ester, methacrylic ester and styrene, olefin-based rubbers such as ethylene-propylene copolymers, ethylene-propylene-diene copolymers, ethylene-butene-1 copolymers and propylene-butene-1 copolymers, and the like are treated with acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, maleic acid, and maleic acid, Unsaturated carboxylic acids such as itaconic acid, citraconic acid and tetrahydrophthalic acid, and derivatives thereof such as acid halides, amides, imides, acid anhydrides and esters, specifically, maleic acid chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate, and the like, are modified under grafting reaction conditions.

Among them, ethylene-propylene-diene copolymer or ethylene-propylene or butene-1 copolymer rubber modified with an unsaturated dicarboxylic acid or its anhydride, particularly maleic acid or its anhydride, is preferable.

The thickness of the sealant resin layer is preferably 20 to 90 μm, and more preferably 40 to 80 μm. If the thickness is less than 20 μm, interlayer peeling may occur between the uneven surface layer and the substrate layer, and if the thickness exceeds 90 μm, the production cost may be increased.

[ third embodiment ]

As shown in fig. 6, the resin sheet according to the third embodiment of the present invention is a resin sheet in which the uneven shape layer (1) and the base material layer (4) are directly laminated without using the sealant resin layer (3) shown in the second embodiment. Specifically, the resin sheet according to the third embodiment has a layer structure in which the liquid repellent layer (2), the uneven shape layer (1), and the base material layer (4) are formed from top to bottom, and the sealant resin layer is removed from the thermoplastic resin sheet according to the second embodiment. Note that the liquid repellent layer and the uneven shape layer are the same as those in the first and second embodiments, and therefore, description thereof is omitted. On the other hand, the base material layer (4) in the present embodiment is preferably designed to have sufficient adhesiveness to the uneven shape layer.

Therefore, in the resin sheet according to the third embodiment, a styrene resin having excellent adhesion to the uneven layer is preferably used as the base layer. The styrene resin is preferably a styrene base layer comprising preferably 60 to 15 mass%, more preferably 55 to 15 mass%, of a polystyrene resin and preferably 40 to 85 mass%, more preferably 45 to 85 mass%, of an impact-resistant polystyrene resin. Further, a styrene-based resin composition to which a hydrogenated styrene-based thermoplastic elastomer is added can also be used. When a polystyrene resin and a hydrogenated styrene-based thermoplastic elastomer are used in combination, a styrene-based resin composition containing 90 to 95 mass% of a polystyrene-based resin and 5 to 10 mass% of a hydrogenated styrene-based thermoplastic elastomer is preferable. In this case, when the amount of the hydrogenated styrene-based thermoplastic elastomer added is less than 5% by mass, the adhesiveness to the uneven layer may become insufficient, and delamination may occur, and when it exceeds 10% by mass, the production cost may become high.

[ fourth embodiment ]

As shown in fig. 7, the resin sheet according to the fourth embodiment of the present invention is a resin sheet in which a liquid repellent layer (2), a textured layer (1), a 1 st sealant resin layer (3a), an oxygen barrier base layer (5), a 2 nd sealant resin layer (3b), and a base layer (4) are sequentially stacked. The compositions of the 1 st and 2 nd sealant resin layers may be the same or different. The thickness of the textured layer is preferably 50 to 250 μm. If the thickness is less than 50 μm, transfer of the uneven shape may be defective. In addition, if it exceeds 200. mu.m, the production cost may become high.

< substrate layer >

As the resin used as the base layer in the fourth embodiment, a nylon-based resin or a methacrylate-based resin is preferable. Examples of the nylon-based resin include: lactam polymers such as caprolactam and laurolactam, polymers of aminocarboxylic acids such as 6-aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, aliphatic diamines such as hexamethylenediamine, decamethylenediamine, dodecamethylenediamine and 2,2, 4-or 2,4, 4-trimethylhexamethylenediamine, alicyclic diamines such as 1, 3-or 1, 4-bis (aminomethyl) cyclohexane and bis (p-aminocyclohexylmethane), polycondensates of diamine units such as aromatic diamines such as m-or p-xylylenediamine with aliphatic dicarboxylic acids such as adipic acid, suberic acid and sebacic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, dicarboxylic acid units such as terephthalic acid and isophthalic acid, and copolymers thereof. Specifically, there are 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 and the like, and among them, nylon 6 and nylon MXD6 are preferable.

The methacrylate-based resin is not particularly limited in structure, as long as it is a vinyl polymer based on a methacrylate monomer. Examples of the methacrylate ester monomer include: methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, and the like. Among them, methyl methacrylate is particularly preferable. In the methacrylate monomer, an alkyl group such as a propyl group, a butyl group, a pentyl group, or a hexyl group may be linear or branched. The methacrylate ester resin to be blended in the resin composition of the present embodiment may be a homopolymer of a methacrylate ester monomer or a copolymer of a plurality of methacrylate ester monomers. Alternatively, the monomer unit may be derived from a known vinyl compound other than methacrylate, i.e., ethylene, propylene, butadiene, styrene, α -methylstyrene, acrylonitrile, acrylic acid, or the like.

< oxygen barrier substrate layer >

Examples of the oxygen barrier base layer include: ethylene-vinyl alcohol copolymer resin, nylon resin. Among them, an ethylene-vinyl alcohol copolymer resin is preferable in view of processability and moldability.

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

Examples of the nylon-based resin include lactam polymers such as caprolactam and laurolactam, polymers of aminocarboxylic acids such as 6-aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, aliphatic diamines such as hexamethylenediamine, decamethylenediamine, dodecamethylenediamine and 2,2, 4-or 2,4, 4-trimethylhexamethylenediamine, 1, 3-or 1, 4-bis (aminomethyl) cyclohexane, polycondensates of diamine units such as alicyclic diamines such as bis (p-aminocyclohexylmethane) or aromatic diamines such as m-or p-xylylenediamine with dicarboxylic acid units such as aliphatic dicarboxylic acids such as adipic acid, suberic acid and sebacic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, and copolymers thereof.

Specific examples of the nylon-based resin include 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, and nylon 6I/6T, and nylon 6 and nylon MXD6 are preferable.

< sealing agent resin layer >

The sealant resin layer is preferably a modified olefin polymer. As the modified olefin-based polymer resin, the following are exemplified: olefin-based resins such as copolymers of olefins having 2 to 8 carbon atoms such as ethylene, propylene and butene-1, copolymers of these olefins with other olefins having 2 to 20 carbon atoms such as ethylene, propylene, butene-1, 3-methylbutene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1 and decene-1, and copolymers with vinyl compounds such as vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, acrylic ester, methacrylic ester and styrene, olefin-based rubbers such as ethylene-propylene copolymers, ethylene-propylene-diene copolymers, ethylene-butene-1 copolymers and propylene-butene-1 copolymers, and the like are treated with acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, maleic acid, and maleic acid, Unsaturated carboxylic acids such as itaconic acid, citraconic acid and tetrahydrophthalic acid, and derivatives thereof such as acid halides, amides, imides, acid anhydrides and esters, specifically, maleic acid chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate, and the like, which have been modified under the grafting reaction conditions.

Among them, ethylene-based resins, propylene-based resins, or ethylene-propylene or butene-1 copolymer rubbers modified with an unsaturated dicarboxylic acid or an anhydride thereof, particularly maleic acid or an anhydride thereof, are preferable.

The thickness of the sealant resin layer is preferably 10 to 50 μm, more preferably 20 to 40 μm, on either side. If the thickness is less than 10 μm, sufficient interlayer adhesion strength may not be obtained, and if the thickness exceeds 50 μm, the production cost may be increased.

< production of liquid-repellent resin sheet >

The method for producing the resin sheet according to the present invention is not limited, and any method can be used, and typically, the method includes the following steps: a single-layer sheet having at least 1 or more kinds of convex shapes on one surface thereof or a laminated resin sheet including the single-layer sheet as a concavo-convex shape layer is produced, and finally a liquid repellent layer is formed on the surface of the concavo-convex shape.

First, when a single-layer sheet having at least 1 or more kinds of convex shapes on one surface or a laminated resin sheet including the single-layer sheet as a concave-convex shape layer is produced, any resin sheet molding method can be used. For example, there is a method of obtaining a resin sheet by melt-extruding various raw material resins through a T-die using 1 single-screw extruder in the case of a single layer and a plurality of single-screw extruders in the case of a multilayer. In the case of multiple layers, a multi-manifold die may also be used. The layer structure of each embodiment of the resin sheet of the present invention is basically as described above, and for example, as long as deterioration of physical properties or the like does not occur, the resin sheet of the present invention and the scrap material generated in the production process of the molded container may be added to the base layer, or may be laminated as a further layer.

Next, the uneven shape is formed on the single-layer or multi-layer resin sheet, but the method is not particularly limited, and any method known to those skilled in the art may be used. For example, the method of manufacturing by an extrusion molding method, the method of manufacturing by a photolithography method, the method of manufacturing by a hot press method, the method of manufacturing by a pattern roll and a UV curable resin, and the like are mentioned.

Finally, a liquid repellent layer is formed on the surface of the uneven layer. The method for forming the liquid repellent layer is not particularly limited, and a known coating method such as roll coating, gravure coating, bar coating, blade coating, brush coating, powder electrostatic method, or the like can be used. The solvent used in the preparation of the coating liquid is not particularly limited, and, in addition to water, an organic solvent such as alcohol (ethanol), cyclohexane, toluene, acetone, IPA, propylene glycol, hexylene glycol, butylene glycol, pentamethylene glycol, n-pentane, n-hexane, or hexanol can be suitably selected. In this case, a small amount of a dispersant, a coloring agent, an anti-settling agent, a viscosity modifier, or the like may be used in combination.

The resin sheet according to the present invention has a liquid repellent layer on the convex portion of the uneven layer, and exhibits excellent liquid repellency by supplementing the fine uneven shape with the liquid repellency caused by the liquid repellent layer. That is, the resin sheet of the present invention has a contact angle of liquid of 130 ° or more as described above, and has sufficient liquid repellency, and the liquid falls down on the resin sheet. When the contact angle is less than 130 °, the resin sheet may not have a liquid-rolling property, and the resin sheet may not have liquid repellency. In the resin sheet according to the present invention, the roll-off angle of the liquid is preferably 40 ° or less. If the roll off angle exceeds 40 °, the resin sheet may not have roll off properties of the liquid, and the liquid repellency cannot be said to be provided. The contact angle and the roll off angle of the resin sheet can be measured by using an automatic contact angle meter (for example, DM-501, manufactured by Kyowa Kagaku Co., Ltd.).

Examples

The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the contents of the examples.

The various starting materials used in the examples and the like are shown below.

(1) Layer of concavo-convex shape

(A-1) random Polypropylene "PM 921V" (manufactured by Sun Allomer Corporation)

(A-2) Block Polypropylene "PM 854X" (manufactured by Sun Allomer Corporation)

(B-1) straight-chain Medium-Density polyethylene resin (C4) "Neo-Zex 45200" (manufactured by Prime Polymer Corporation)

(B-2) Linear Low-Density polyethylene resin (C6) 'Ult-Zex 20200J' (manufactured by Prime Polymer Corporation)

(C) styrene-conjugated diene Block copolymer resin "730L" (manufactured by electrochemical engineering Co., Ltd.) (diene content 25% by mass)

(D) GPPS resin "G100C" (manufactured by Toyo Styrene Corporation)

(2) Liquid repellent layer

Hydrophobic oxide microparticles (E): hydrophobic silica "AEROSIL R812S" (manufactured by Evonik Degussa Corporation)

(F-1) fluorine-based copolymer resin: "AG-E070" (manufactured by Asahi glass Co., Ltd.)

(F-2) fluorine-based copolymer resin: "AG-E550D" (manufactured by Asahi glass Co., Ltd.)

(3) Sealant resin layer

(G) hydrogenated styrene-based thermoplastic elastomer "Tuftec P2000" (manufactured by Asahi Kasei Co., Ltd.)

(H) hydrogenated styrene-based thermoplastic elastomer "Tuftec M1943" (manufactured by Asahi Kasei Co., Ltd.)

(I) modified olefin Polymer resin "Modic F502" (manufactured by Mitsubishi chemical Co., Ltd.)

(J) modified olefin Polymer resin "Admer SE 810" (manufactured by Mitsui chemical Co., Ltd.)

(4) Substrate layer

(K) HIPS resin "Toyo Styrene H850N" (manufactured by Toyo Styrene Corporation, butadiene content 9.0 mass%)

(L) GPPS resin "HRM 23" (manufactured by Toyo Styrene Corporation)

(M) PET resin (Film) "Ester Film E5102: 16 μm "(manufactured by Toyo textile Co., Ltd.)

(N) nylon 6 resin (Film) "Harden Film N1100: 15 μm "(manufactured by Toyo textile Co., Ltd.)

(O) ethylene-vinyl alcohol copolymer "Eval J-171B" (manufactured by Kuraray Corporation)

(P) acrylic resin "HBS 000" (manufactured by Mitsubishi chemical Co., Ltd.)

Evaluation methods of various properties of the resin sheets produced in examples and the like are as follows.

(1) Observation of convex shape

The height of the convex shape and the distance between the apexes of the convex shape were measured by using a laser microscope VK-X100 (manufactured by Keyence Corporation). In addition, in order to measure the height of the convex shape and the distance between the apexes, a sample of a concave-convex shaped cross section was produced using a microtome. The height of the convex shape was measured at 10 points of the resin sheet, which had the same shape, at 3 points, and the arithmetic average of the 30 measured values was used. When the number of the convex shapes is 2 or more, the heights of the 1 st convex shape and the 2 nd convex shape are determined in the same manner. The vertex interval was measured from any 3 points of the resin sheet for 10 adjacent convex shapes, and the arithmetic average of the 30 measured values was used. When the number of the convex shapes is 2 or more, the distance between the 1 st convex shape and the 2 nd convex shape is measured, and the arithmetic average of the 30 measured values is used.

(2) Contact angle and roll off angle

The contact angle and the roll off angle were measured with respect to the resin sheet by using an automatic contact angle meter DM-501 (manufactured by Kyowa Kagaku Co., Ltd.). Further, as the test solution, salad oil (Nisshin Oillio group Corporation), hand cleanser "Kirei Kirei" (manufactured by LION CORPORATION), emulsion "Yukikochi" (manufactured by Ledun pharmaceutical Co., Ltd.), drawing tool "Black" (manufactured by Pentel Corporation) were used in an amount of 8. mu.L in contact angle measurement and 20. mu.L in roll-off angle measurement. When the contact angle is 130 ° or more, the liquid repellency is high, and it can be judged that the adhesion of the liquid can be prevented. Further, when the roll-off angle is 40 ° or less, the liquid repellency is high, and it is judged that the adhesion of the liquid can be prevented.

(3) Evaluation of sealing Properties

A single-layer sheet (900 μm thick) of impact-resistant polystyrene was used, and a flange portion (see fig. 8) of a vacuum-molded container was cut out and heat-sealed using a heat-sealing tester (manufactured by wakawa corporation). The sealing iron width of the heat seal tester was 1.0mm, and the resin sheet thus produced was used as a lid material. The sealing temperature is 210 ℃ and the sealing pressure is 0.36 MPa. The peel strength was measured by using a Strograph VE1D (manufactured by tokyo seiki corporation), in which a lid material (resin sheet) was held between one jig part of the Strograph and a flange part of the container was held between the other jig part. The peeling speed was 200 mm/min. When the peel strength is 2.8N or more, the sealing property is judged to be good.

Further, a pouch was produced using the heat seal tester (manufactured by zuoka corporation) described above so that the uneven layer of the produced sheet became the inner surface side. The sealing temperature is 210 ℃, the sealing pressure is 0.36MPa, and the width of the sealing iron is 5 mm. The peel strength was measured by using a stragraph VE1D (manufactured by toyoyo seiki co., ltd.) with a resin sheet sandwiched between clamps of the stragraph. The peeling speed was 200 mm/min. When the peel strength is 8.5N or more, the sealing property is judged to be good.

(4) Determination of melt mass flow Rate

According to JIS K7210, at test temperature: 230 ℃, load: the measurement was carried out under the condition of 2.16 Kg. The test equipment used was Melt Indexer F-F01 (manufactured by Toyo Seiki Seisaku-sho Co., Ltd.).

(5) Oxygen transmission rate

As for the oxygen permeability of the resin sheet, the oxygen permeability was measured under the measurement conditions of a temperature of 25 ℃ and a relative humidity of 65% according to JIS K7126-B method using an OX-TRAN oxygen permeability measuring apparatus (manufactured by Mocon Corporation). If the oxygen transmission rate is less than 3.0ml/m²Day atm is good in oxygen barrier property.

< example 1 (layer formation in FIG. 1) >

The resin sheet was extruded by a T-die method using a 1-station 65mm single-screw extruder. The extruded sheet was cast by a transfer roller and a contact roller having a surface provided with irregularities by a laser engraving method, to obtain a resin sheet including an irregular layer having irregularities provided on the surface.

Next, in order to form a liquid-repellent layer on the surface of the uneven-shaped layer, a dispersion (a mixed solution of purified water and isopropyl alcohol as a solvent) was prepared in which hydrophobic silica and a fluorine-based copolymer resin were mixed so that the hydrophobic silica in the liquid-repellent layer was 66 mass% and the fluorine-based copolymer resin was 34 mass%. The mixed dispersion was applied to the surface of the corona-treated uneven surface using a bar coater, and dried at 90 to 150 ℃. The composition of the resin sheet having the liquid repellent layer formed on the surface of the uneven layer is shown in table 1.

The resin sheet produced as described above was evaluated for various properties by the above-described methods. The results are shown in Table 2.

TABLE 1

TABLE 2

< examples 2 to 12, comparative examples 1 to 6 >

Resin sheets according to examples 2 to 12 and comparative examples 1 to 6 were produced and evaluated in the same manner as in example 1, except that the composition, thickness and MFR of the uneven layer and the liquid repellent layer were set as shown in table 1. The results are shown in table 2.

In comparative example 1, no liquid repellent layer was formed, and in comparative example 2, no uneven shape was provided. In comparative example 3, the hydrophobic silica was not contained, and in comparative example 4, the fluorine-based copolymer resin was not used in the liquid repellent layer. Comparative example 5 is a composition in which silica having not been subjected to hydrophobic surface treatment is used in the liquid repellent layer, and comparative example 6 is a convex shape formed into a bell-shaped sheet by hot pressing using only HIPS resin.

The following matters are apparent from the results shown in table 2. In all of examples 1 to 12, the results were obtained that completely satisfied the evaluation criteria regarding the liquid repellency (contact angle, roll off angle) of the sheet material with respect to each liquid. On the other hand, in comparative examples 1 to 4 and 6, the liquid other than purified water did not fall off the sheet. In comparative example 5, all the liquid did not roll off.

< example 13 (layer constitution of FIG. 5) >

A multilayer resin sheet having a thickness of 136 μm and comprising layers in which an uneven layer of 80 μm, a sealant resin layer of 40 μm and a base layer of 16 μm (PET resin) were sequentially laminated by a feedblock (feedblock) method was extruded by a T-die method using a 2-station 40mm single screw extruder. When the uneven surface layer and the sealant layer are extruded, the PET base layer is laminated by an extrusion lamination method.

< example 15 >

A multilayer resin sheet having a thickness of 450 μm and comprising a layer in which an uneven shape layer of 90 μm, a sealant resin layer of 50 μm, and a base material layer (HIPS/GPPS: 80/20) of 310 μm were sequentially laminated by a feedblock method was extruded by a T-die method using a 3-station 40mm single screw extruder.

The extruded sheet obtained above was cast using a transfer roller and a contact roller, the surfaces of which were provided with irregularities by a laser engraving method, to obtain a multilayer resin sheet having irregularities on the sheet surface. The sheet thickness was 0.12 mm.

Next, in order to form a liquid repellent layer on the surface of the uneven layer, a dispersion (a mixed solution of purified water and isopropyl alcohol as a solvent) was prepared in which hydrophobic silica and a fluorine-based copolymer resin were mixed so that the hydrophobic silica became 66 mass% and the fluorine-based copolymer resin became 34 mass%. The mixed dispersion was applied to the surface of the corona-treated uneven surface using a bar coater, and dried at 90 to 150 ℃. The composition and layer structure of each layer of the resin sheet having the liquid-repellent layer formed on the surface of the uneven layer are shown in table 3.

TABLE 3

The resin sheet produced as described above was evaluated for various properties by the above-described methods. The results are shown in table 4.

TABLE 4

< examples 14 to 24, comparative example 7, and comparative examples 9 to 12 >

Resin sheets according to examples 14 and 16 to 24, comparative examples 7 and comparative examples 9 to 12 were produced in the same manner as in example 13 or example 15, except that the composition, thickness and MFR of the uneven layer, the liquid repellent layer and each layer of the multilayer resin sheet were set as shown in table 3, and the results are shown in table 4. In examples 13, 14, 19, 22 to 24 and comparative examples 11 and 12, the sealing property was evaluated.

Further, in comparative example 7, no liquid repellent layer was formed, and in comparative example 9, polyethylene having an MFR of 1.1g/10 min was used for the uneven layer, so that the transferability was poor, and in comparative example 10, hydrophobic silica was not used for the liquid repellent layer. Comparative example 11 is a composition in which a fluorine-based copolymer resin is not used in the liquid-repellent layer, and comparative example 12 is a composition in which silica that has not been subjected to hydrophobic surface treatment is used in the liquid-repellent layer.

The following matters are apparent from the results shown in table 4. In all of examples 13 to 24, the results were obtained that completely satisfied the evaluation criteria regarding the liquid repellency (contact angle, roll off angle) and sealing property (examples 13, 14, 19, 22, 23, and 24) of the sheet material with respect to each liquid. On the other hand, in comparative examples 7 and 9 to 11, the result was that the liquids other than purified water did not fall off. In comparative example 12, all the liquid did not roll off.

< example 25 (layer formation in FIG. 6) >

A multilayer resin sheet having a thickness of 700 μm and comprising layers in which a concavo-convex shape layer of 90 μm and a styrene base material layer of 610 μm were sequentially laminated was extruded through a T-die by a plug feed method using a 2-stage 40mm single screw extruder. As the styrene-based substrate layer, a substrate layer obtained by mixing a HIPS resin and a hydrogenated thermoplastic elastomer at a mass ratio of 95/5 (HIPS/hydrogenated styrene-based thermoplastic elastomer) was used. The resin sheet according to example 25 was formed on the extruded sheet obtained as described above in the same manner as in example 13. The resin sheet thus formed was subjected to the same evaluation test as in example 13. The results are shown in Table 4.

< example 26, comparative example 8 >

Resin sheets according to example 26 and comparative example 8 were produced in the same manner as in example 25, except that the composition, thickness, and MFR of the uneven layer, liquid repellent layer, and styrene-based base layer were set as shown in table 3, and the evaluation results of the properties thereof are shown in table 4. Further, comparative example 8 had a composition to which no uneven shape was applied.

The following matters are apparent from the results shown in table 4. In examples 25 to 26, the results that completely satisfied the evaluation criteria regarding the liquid repellency (contact angle, roll off angle) of the sheet material with respect to each liquid were obtained. On the other hand, in comparative example 8, the result was that the liquid other than purified water did not fall off.

< example 27 (layer constitution of FIG. 7) >

A multilayer resin sheet having a thickness of 131 μm according to the fourth embodiment, which comprises, in order, a concavo-convex shaped layer of 80 μm, a 1 st sealant resin layer of 10 μm made of a modified olefin polymer, an oxygen barrier substrate layer of 15 μm made of an ethylene-vinyl alcohol copolymer, a 2 nd sealant resin layer of 10 μm made of a modified olefin polymer, and a polyester substrate layer of 16 μm, was extruded from a T die by a block feeding method using a 5-station 40mm single screw extruder. Further, the PET resin and the nylon 6 resin were laminated by an extrusion lamination method when the 2 nd sealant resin layer was extruded from the uneven shape layer.

A multilayer resin sheet having a thickness of 700 μm according to the fourth embodiment, which was composed of a concavo-convex shape layer of 90 μm, a 1 st sealant resin layer of 20 μm made of a modified olefin polymer, an oxygen barrier substrate layer of 30 μm made of an ethylene-vinyl alcohol copolymer, a 2 nd sealant resin layer of 20 μm made of a modified olefin polymer, and a substrate layer (HIPS/GPPS: 80/20) of 540 μm in this order, was extruded from a T-die by a block feeding method using a 5-station 40mm single screw extruder.

The extruded sheet obtained above was cast using a transfer roller and a contact roller, each having an uneven surface formed by a laser engraving method, to obtain a multilayer resin sheet having an uneven surface formed on the sheet surface.

Next, in order to form a liquid repellent layer on the surface of the uneven layer, a dispersion (a mixed solution of purified water and isopropyl alcohol as a solvent) was prepared in which hydrophobic silica and an olefin-based copolymer resin were mixed so that the hydrophobic silica was 66 mass% and the fluorine-based copolymer resin was 34 mass%. The mixed dispersion was applied to the surface of the corona-treated uneven surface using a bar coater, and dried at 90 to 150 ℃. The composition and layer structure of each layer of the resin sheet having the liquid-repellent layer formed on the surface of the uneven layer are shown in table 5.

TABLE 5

The resin sheets produced as described above were evaluated for various properties by the methods described above. The results are shown in Table 6.

TABLE 6

< examples 28 to 29, 31 to 39 and comparative examples 13 to 18 >

Resin sheets according to examples 28 to 29, 31 to 39 and comparative examples 13 to 18 were produced in the same manner as in example 27 or example 30, except that the composition, thickness and MFR of the uneven layer, the liquid repellent layer and each of the other multilayer resin sheets were set as shown in Table 5. In examples 27 to 29, 33, 36 to 39 and comparative example 13, the sealing property was evaluated.

In comparative example 13, no liquid repellent layer was formed, and in comparative example 14, no uneven shape was provided. In comparative example 15, since polyethylene having MFR of 1.1g/10 min was used for the uneven layer, transferability was poor, and in comparative example 16, hydrophobic silica was not used for the liquid repellent layer. Comparative example 17 is a composition in which a fluorine-based copolymer is not used in the liquid repellent layer, and comparative example 18 is a composition in which silica having not been subjected to a hydrophobic surface treatment is used in the liquid repellent layer.

The following matters are apparent from the results shown in table 6. All of examples 27 to 39 completely satisfied the evaluation criteria of the sheet for liquid repellency (contact angle, roll off angle), sealing property, and oxygen barrier property with respect to each liquid. On the other hand, in comparative examples 13 to 17, the result was that the liquids other than purified water did not fall off. In comparative example 18, all the liquid did not roll off.

The present invention has been described above using various embodiments, but the technical scope of the present invention is not limited to the scope described in the above embodiments. It will be apparent to those skilled in the art that various modifications or improvements may be added to the above embodiments. Further, the technical scope of the present invention may include modifications and improvements as described in the patent claims.

Description of the reference numerals

1a convex shape

1b convex apex

1c 1 st convex apex

1d 2 nd convex apex

height of h-convex shape

t convex shape vertex spacing

2 liquid repellent layer

3 sealant resin layer

3a 1 st sealant resin layer

3b 2 nd sealant resin layer

4 base material layer

5 oxygen barrier substrate layer

6 Flange part

Claims

1. A liquid-repellent resin sheet comprising a layer having an uneven configuration which is composed of a resin composition comprising a polyolefin resin and has a fine uneven configuration, wherein at least 1 or more kinds of uneven configurations are formed on one surface of the uneven configuration layer, and a liquid-repellent layer comprising hydrophobic oxide fine particles and a fluorine-based copolymer resin is formed on the surface having the uneven configurations, wherein the contact angle of the surface of the uneven configuration layer when in contact with a surfactant-based liquid is 130 DEG or more and the roll-off angle is 40 DEG or less,

the fluorine-containing copolymer resin comprises a copolymer 1 and a copolymer 2,

the copolymer 1 contains a structural unit a and a structural unit b,

the copolymer 2 contains a structural unit a and a structural unit c,

the structural unit a is an alkyl group in which a part or all of hydrogen atoms are substituted with fluorine atoms, the number of carbon atoms is 1 to 6,

the structural unit b is a monomer having a saturated hydrocarbon group with 16-40 carbon atoms,

the structural unit c is a monomer derived from a monomer containing no fluorine atom and having a crosslinkable functional group.

2. The liquid-repellent resin sheet according to claim 1, wherein a base material layer having at least 1 or more layers of a resin selected from the group consisting of styrene resins, olefin resins, polyester resins, nylon resins, ethylene-vinyl alcohol copolymer resins, and acrylic resins is laminated on the other surface of the uneven-shaped layer.

3. The liquid-repellent resin sheet according to claim 1 or 2, wherein the resin composition contains 35 to 100 mass% of a polyolefin-based resin.

4. The liquid-repellent resin sheet according to claim 2, wherein a sealant resin layer composed of at least 1 resin selected from a modified olefin-based polymer resin and a hydrogenated styrene-based thermoplastic elastomer is formed between the textured layer and the base layer.

5. The liquid-repellent resin sheet according to claim 1 or 2, wherein the convex shapes include a 1 st convex shape and a 2 nd convex shape, the height of the 1 st convex shape and the height of the 2 nd convex shape are each 20 μm to 150 μm, and the apex interval of adjacent convex shapes is 20 μm to 100 μm.

6. The liquid-repellent resin sheet according to claim 5, wherein the 1 st convex shapes and the 2 nd convex shapes are arranged alternately, and the ratio of the height of the 2 nd convex shapes to the height of the 1 st convex shapes is 0.4 or more and 0.8 or less.

7. The liquid repellent resin sheet according to claim 1 or 2, wherein the resin composition has a melt mass flow rate at 230 ℃ of 5g/10 min or more.

8. The liquid-repellent resin sheet according to claim 1 or 2, wherein the hydrophobic oxide fine particles are hydrophobic silica fine particles having trimethylsilyl groups on the surface.

9. The liquid-repellent resin sheet according to claim 1 or 2, wherein the content of the hydrophobic oxide fine particles in the liquid-repellent layer is 20 to 70 mass%, and the content of the fluorine-based copolymer resin is 70 to 30 mass%.

10. The liquid-repellent resin sheet according to claim 1 or 2, wherein the thickness of the concavo-convex shape layer is 50 μm to 200 μm.

11. A sheet for building materials, which uses the liquid-repellent resin sheet according to any one of claims 1 to 10.

12. A sheet for consumer packaging material, which uses the liquid-repellent resin sheet according to any one of claims 1 to 10.

13. The sheet for building materials according to claim 11, which is a sheet for wallpaper members.

14. The sheet for packaging material of living goods according to claim 12, which is a sheet for members of a portion of a house where water is required.

15. The sheet for packaging material of living goods according to claim 12, which is a sheet for lid material of food container.

16. The sheet for packaging living goods according to claim 12, which is a sheet for a pouch.