TWI711541B - Liquid-repellent resin sheet and sheet for building materials and packaging materials for daily life using the sheet - Google Patents

Abstract

The subject of the present invention is to provide a liquid-repellent resin sheet having excellent liquid-repellent properties. Furthermore, the present invention provides a sheet for building materials and a sheet for packaging materials for daily life products that use the liquid-repellent resin sheet with excellent liquid repellency, oxygen barrier properties, and weather resistance.

The solution of the present invention is to provide a concavo-convex shape layer having a fine concavo-convex shape formed of a polyolefin resin composition, having at least one or more convex shapes on one side surface, and having the convex shape A liquid-repellent layer containing hydrophobic oxide particles and a fluorine-based copolymer resin was provided on the surface to obtain a liquid-repellent resin sheet.

Description

Liquid-repellent resin sheet and sheet for building materials and packaging materials for daily life using the sheet

The present invention relates to a resin sheet with liquid repellency, a sheet for building materials and a sheet for packaging materials for daily life products using the resin sheet.

Heretofore, for sheets for building materials such as wallpapers, soft drinks or fruit juices, and sheets for packaging materials for food or daily necessities such as hobby foods and beverages, a sheet coated with a polymer material can be used. For example, Patent Document 1 proposes a sheet in which a fluorine-based copolymer is applied to a nonwoven fabric. In addition, Patent Documents 2 and 3 also propose liquid repellents for paper and cloth.

On the other hand, a film in which an oil repellent is coated on a PET resin in a display member or the like is proposed (Patent Document 4). Furthermore, in automotive parts, a film in which a water repellent is applied to the surface of the uneven shape is also proposed (Patent Document 5).

When using a sheet or film coated with an oil repellent on the above-mentioned paper or PET resin as a packaging material for food or daily use, there is a problem of adhesion of food (oil-based liquid), for example, a sheet for pouch, There is also concern that oil-based or surfactant-based liquids adhere to packaging materials. However, the methods described in Patent Documents 1 to 4 cannot sufficiently solve such problems. Moreover, even with the method described in Patent Document 5, the oil The liquids of the series and the liquids of the surfactant series, etc., cannot sufficiently solve this problem.

Patent Document 1 JP 2010-196196 A

Patent Document 2 JP 2009-256506 A

Patent Document 3 JP 2007-291373 A

Patent Document 4 JP 2009-104054 A

Patent Document 5 JP 2008-122435 A

[Summary of Invention]

The present invention was developed in view of the above circumstances. The main aspect of the present invention is to provide a liquid-repellent resin sheet that reduces oily liquids and interface activity when used as building materials and packaging materials for daily life The agent-based liquid adheres to the surface of the sheet. Furthermore, its object is to provide a sheet for building materials manufactured using this liquid-repellent resin sheet and a sheet for food packaging materials with excellent oxygen barrier properties.

That is, the inventors of the present invention have determined that in order to prevent the adhesion of oil-based liquids and surfactant-based liquids, it is only necessary to impart liquid repellency. As a result of reviewing various liquid repellency performance means, they have found that the surface of the sheet is provided with fine uneven shapes. , And the application of the liquid repellent can impart high liquid repellency to the surface of the sheet to prevent the adhesion of oil-based and surfactant-based liquids, thereby completing the present invention.

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

(1) A liquid-repellent resin sheet having a concavo-convex shape layer composed of a composition containing a polyolefin resin and having fine concavo-convex shapes on one side of the concavo-convex shape layer It has at least one convex shape, and a liquid-repellent layer containing hydrophobic oxide fine particles and a fluorine-based copolymer resin is formed on the surface having the convex shape.

(2) The liquid-repellent resin sheet according to (1), wherein a substrate layer is laminated on the other side of the concavo-convex shape layer, and the substrate layer has at least one layer selected from styrene resins, A layer composed of olefin resin, polyester resin, nylon resin, ethylene-vinyl alcohol copolymer resin, and acrylic resin.

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

(4) The liquid-repellent resin sheet according to any one of (1) to (3), which is formed by forming a sealant resin layer between the concavo-convex shape layer and the substrate layer, and the sealant resin layer is It is composed of at least one resin selected from modified olefin-based polymer resins and hydrogenated styrene-based thermoplastic elastomers.

(5) The liquid-repellent resin sheet according to any one of (1) to (4), wherein the convex shape includes a first convex shape and a second convex shape, the height of the first convex shape and the height of the second convex shape They are 20μm~150μm, and the distance between the apexes of adjacent convex shapes is 20μm~100μm.

(6) The liquid-repellent resin sheet according to (5), wherein the first convex shape and the second convex shape are alternately arranged, and the ratio of the height of the second convex shape to the height of the first convex shape is 0.4 to 0.8.

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

(8) The liquid-repellent resin sheet according to any one of (1) to (7), wherein the hydrophobic oxide particles are hydrophobic silica 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 particles in the liquid-repellent layer is 20% to 70% by mass, and the fluorine-based copolymer The content of the resin is 70% by mass 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 shape layer is 50 μm to 200 μm.

(11) The liquid-repellent resin sheet according to any one of (1) to (10), wherein the contact angle of the surface of the concavo-convex shape layer and the oil-based liquid or the surfactant-based liquid is 130° or more, and The sliding angle is below 40°.

(12) A sheet for building materials using the liquid-repellent resin sheet as described in any one of (1) to (11).

(13) A sheet for packaging materials for daily life products, which uses the liquid-repellent resin sheet as described in any one of (1) to (11).

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

(15) The sheet for packaging materials for household goods as in (13), which is a sheet for water-related components.

(16) The sheet for packaging materials for daily life products as in (13), which is a sheet for cover materials of food containers.

(17) The sheet for packaging materials for daily life products as in (13), which is a sheet for small bags.

In the present invention, it has been found that the concavo-convex shape layer having a fine concavo-convex shape composed of a polyolefin resin composition has at least one or more convex shapes on one side surface, and the aforementioned convex shape A liquid-repellent resin sheet with a liquid-repellent layer containing hydrophobic oxide particles and a fluorine-based copolymer resin formed on the surface can significantly improve the adhesion prevention of oil-based liquids and surfactant-based liquids on the surface of the sheet. In addition, by laminating on the other side of the aforementioned concavo-convex shape layer, there is at least one layer The base layer of a layer composed of a resin selected from styrene resins, olefin resins, polyester resins, nylon resins, ethylene-vinyl alcohol copolymer resins, and acrylic resins, changes in oxygen barrier properties and weather resistance Well. Therefore, the liquid-repellent resin sheet of the present invention can be applied to sheet materials for building materials such as wallpaper members, sheets for kitchen and bathroom members, lid materials for food containers, and sheets for packaging household goods such as small bags.

1a‧‧‧Convex shape

1b‧‧‧Convex Vertex

1c‧‧‧The vertex of the first convex

1d‧‧‧2nd convex vertex

h‧‧‧Convex shape height

t‧‧‧Vertex interval of convex shape

2‧‧‧Liquid Repellent Layer

3‧‧‧Sealant resin layer

3a‧‧‧The first sealant resin layer

3b‧‧‧Second sealant resin layer

4‧‧‧Substrate layer

5‧‧‧Oxygen barrier substrate layer

6‧‧‧Flange

Figure 1 is a schematic longitudinal sectional side view showing the liquid repellent resin sheet of the first embodiment of the present invention.

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

Figure 3 is a schematic longitudinal sectional side view of another aspect of the liquid-repellent resin sheet of the first embodiment of the present invention.

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

Fig. 5 is a schematic longitudinal sectional side view showing the laminated structure of the liquid-repellent resin sheet of the second embodiment of the present invention.

Fig. 6 is a schematic longitudinal sectional side view showing the laminated structure of the liquid-repellent resin sheet of the third embodiment of the present invention.

Fig. 7 is a schematic longitudinal sectional side view showing the laminated structure of the liquid-repellent resin sheet of the fourth embodiment of the present invention.

Figure 8 is a container made of a single-layer sheet (900μm thick) of impact-resistant polystyrene and vacuum formed.

[Pattern for implementing the invention]

The liquid-repellent resin sheet (hereinafter referred to as "resin sheet") according to the present invention has an uneven shape composed of a resin composition containing polyolefin resin (hereinafter, sometimes referred to as "polyolefin resin") The layer has at least one convex shape on one surface, and the surface having the convex shape is provided with a liquid-repellent layer containing hydrophobic oxide particles and a fluorine-based copolymer resin. In the following, although various embodiments of the resin sheet are described, and then the method of manufacturing the resin sheet is described, the specific description described for one embodiment is applicable to other embodiments, and it is omitted in the other embodiments. Description.

[First implementation aspect]

The resin sheet of the first embodiment of the present invention, as shown in Figs. 1 and 3, includes a concavo-convex shape layer composed of a polyolefin resin composition with fine concavo-convex shapes, the concavo-convex shape layer on one side The surface has at least one convex shape (1a). In addition, a liquid-repellent layer (2) is provided on one side of the convex shape, and the liquid-repellent layer is composed of a fluorine-based copolymer resin containing hydrophobic oxide particles.

<Concave-convex shape layer>

Although the convex shape may be one type of convex shape as shown in Fig. 1, it is preferable to have a first convex shape and a second convex shape having different shapes (heights) as shown in Fig. 3. In addition, three or more types of convex shapes with different shapes may be provided. The height of the first convex shape is set to be higher than the height of the second convex shape. In the case of using the first convex shape and the second convex shape, the arrangement is not limited, but in terms of liquid repellency, the first convex shape and the second convex shape are preferably arranged alternately. The configuration of the convex shape is not particularly limited, but there are checkerboard configurations arranged vertically and horizontally, and staggered configurations. To maintain better water repellency, staggered arrangements are better. Furthermore, as for the method of forming the concave-convex shape layer, a method of die-casting the surface of the resin sheet using a transfer roller and a touch roller in which the concave-convex shape is formed by a laser engraving method, or using a belt-shaped mold, can be mentioned. A method of performing uneven transfer by heating and pressing the sheet.

The convex shape preferably has a height (h) of 20 μm to 150 μm. When the height of the convex shape is less than 20 μm, the liquid repellency may not be sufficiently ensured, and when the height of the convex shape exceeds 150 μm, the size of the concave-convex shape of the mold for providing the concave-convex shape may become unstable. In addition, the height of the convex shape also includes the thickness (100 nm to 4000 nm) of the liquid repellent layer described later.

The distance between the apexes (t) of adjacent convex shapes is preferably 20 μm to 100 μm. Furthermore, the apex interval means the distance between the apexes of the convex shapes at the shortest distance adjacent to each other. Even if the convex shapes are different from each other, as long as they are adjacent, it means the distance between the apexes of the convex shape. When the apex spacing is less than 20 μm, the size of the uneven shape of the mold used to impart the uneven shape may become unstable. Also, if it exceeds 100 μm, the liquid repellency may decrease.

In addition, 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 two types of convex shapes are used, the height ratio of the second convex shape to the first convex shape is preferably 0.4 or more and 0.8 or less. By making the height ratio 0.4 or more and 0.8 or less, liquid repellency can be effectively obtained.

Although the bottom surface of the convex shape can be a pyramidal shape such as a triangular pyramid, a quadrangular pyramid, a hexagonal pyramid, an octagonal pyramid, a cone, etc.; a truncated cone shape; a truncated cone shape, the inventors have conducted various reviews on the composition of the resin sheet of this embodiment As a result, it was found that the convex shape of the hexagonal cone shape is particularly preferable.

In the resin sheet of the present invention, a resin composition containing a polyolefin-based resin can be used for the resin composition forming the concavo-convex shape layer. The content of the polyolefin resin in the resin composition is preferably 35% by mass or more. By being 35% by 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% by mass or less, or 100% by mass or less.

In addition, the melt mass flow rate of the polyolefin resin composition at 230°C is preferably 5 g/10 minutes or more. By making it 5g/10 minutes or more, the transferability of the uneven shape can be improved. Furthermore, the mass flow rate of the melt is the value when measured under the conditions of a test temperature of 230°C and a load of 2.16 kg in accordance with JIS K 7210.

The polyolefin-based resin means a resin composed of a polymer containing α-olefin as a monomer, and particularly preferably contains a polyethylene-based resin and a polypropylene-based resin. As for polyethylene resins, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, linear medium-density polyethylene, etc., are included, and not only monomers, but also those with such structures are included. The copolymer, graft or blend. As for the latter resin (copolymer or blend), for example, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, ethylene-methacrylate copolymer, ethylene -Vinyl acetate-vinyl chloride copolymer, in addition, it can be exemplified by copolymerization and blending with resins having polar groups in the polyethylene chain, such as blending with these copolymers and ternary copolymers of acid anhydrides, etc. Syndicate.

In addition, the polypropylene resins include homopolypropylene, random polypropylene, block polypropylene and the like. In the case of using homopolypropylene, the structure of the homopolypropylene can be any of isotactic, atactic, and syndiotactic. In the case of using random polypropylene, as far as the alpha olefins copolymerized with propylene are concerned, those having preferably 2 to 20 carbon atoms, more preferably 4 to 12 carbon atoms, such as ethylene, 1-butene, 1 -Pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, etc. In the case of using block polypropylene, block copolymers (block polypropylene), block copolymers or graft copolymers containing rubber components, and the like can be cited. In addition to using these olefin resins alone, other olefin resins may also be used in combination.

In the resin composition, other resins may be contained within a range that does not inhibit the effects of the present invention. Examples of other resins include styrene resins, vinyl chloride resins, (meth)acrylic resins, and the like. As for styrene resins, general polystyrene, impact-resistant polystyrene, styrene-conjugated diene block copolymer, methyl methacrylate-butadiene-styrene copolymer, Acrylonitrile-butadiene-styrene copolymer, etc. The content of other resins is preferably 50% by mass or less in the concavo-convex shape layer, and more preferably 20% by mass or less.

<Liquid Repellent Layer>

The liquid-repellent layer contains hydrophobic oxide particles and a fluorine-based copolymer resin. The thickness of the liquid repellent layer is preferably 100 nm to 4000 nm, but as long as the effect of the present invention can be obtained, it is not limited to this numerical range. Furthermore, the "liquid repellency" in the present invention means a sufficient level of liquid repellency for preventing the adhesion of oil-based liquids or surfactant-based liquids to the resin sheet. Specifically, it means that these liquids have an effect on the resin. The contact angle of the liquid of the sheet is 130° or more, and the sliding angle of the liquid is 40° or less.

The hydrophobic oxide fine particles may be oxide fine particles having a hydrophobic group, or may be oxide fine particles that are hydrophobized by surface treatment. For example, the hydrophilic oxide particles may be surface-treated with a silane coupling agent or the like to make the surface of the particles hydrophobic. The kind of oxide is not limited as long as it is hydrophobic. Among these, at least one of hydrophobic fumed silica, fused silica, alumina, and titanium dioxide (zirconia) can be used. If it is hydrophobic, there is no restriction on the shape of these particles, and any shape of spherical and non-spherical (broken) can also be used.

Specific examples of these, for example, in terms of silica, include: product names "AEROSIL R972", "AEROSIL R972V", "AEROSIL R972CF", "AEROSIL R974", "AEROSIL RX200", "AEROSIL RY200" (above , Japan AEROSIL Co., Ltd.), "AEROSIL R202", "AEROSIL R805", "AEROSIL R8l2", "AEROSIL R812S", (above, manufactured by Evonik Degussa), etc. For titanium dioxide, the product name "AEROXIDE TiO ₂ T805" (manufactured by Evonik Degussa) and the like can be exemplified. Alumina can be exemplified by treating the product name "AEROXIDE Alu C" (manufactured by Evonik Degussa) with a silane coupling agent to make the particle surface hydrophobic fine particles.

Specifically, in terms of obtaining more excellent water repellency, hydrophobic silica particles having trimethylsilyl groups and dimethylsiloxy groups on the surface are preferred. The commercially available products include the aforementioned "AEROSIL R812", "AEROSIL R812S", "AEROSIL RY300" (manufactured by Evonik Degussa), and the like.

As for the hydrophobic oxide fine particles, the average particle diameter of the primary particles is preferably 5 nm to 1000 nm, and more preferably 7 nm to 200 nm. When the average particle diameter of the primary particles is 5 nm to 1000 nm, the liquid repellency becomes good, and the dispersibility to the fluorine-based copolymer resin becomes good. Furthermore, the average particle diameter of the primary particles means the value obtained by calculating the average value by measuring the diameter of 3000 to 5000 hydrophobic oxide particles using a scanning electron microscope.

The fluorine-based copolymer resin is a copolymer containing fluorine atoms, and preferably contains the following copolymer (1) and copolymer (2). Copolymer (1) and 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 performance of the liquid repellency of the resin sheet, and the copolymer (2) mainly contributes to the durability of the resin sheet.

The constituent unit (a) is an alkyl group in which part or all of the hydrogen atoms are replaced with fluorine atoms, and the number of carbon atoms is 1 to 6. The constituent unit (a) may be a chain polyfluorohydrocarbon group having at least one unsaturated group such as a carbon-carbon unsaturated double bond. As for the unsaturated group, (meth)acrylate is preferred.

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

The constituent unit (c) is a monomer derived from a monomer having no fluorine atom and having a crosslinkable functional group. In terms of crosslinkable functional groups, isocyanate groups, blocked isocyanate groups, alkoxysilyl groups, amines are preferred Group, alkoxymethyl amide group, silanol group, ammonium group, amide group, epoxy group, hydroxyl group, oxazoline group, carboxyl group, alkenyl group, sulfonic acid group, etc. Furthermore, epoxy groups, hydroxyl groups, blocked isocyanate groups, alkoxysilyl groups, amino groups, and carboxyl groups are more preferable.

As for the monomer forming the constituent unit (c), preferably, (meth)acrylates, compounds having two or more copolymerizable groups (for example, (meth)acrylic acid 2-isocyanate Ethyl ester, 3-isocyanatopropyl (meth)acrylate, etc.), vinyl ethers or vinyl esters. The constituent unit (c) may also be derived from a mixture of two or more kinds. The constituent unit (c) mainly affects the film-forming properties of the liquid-repellent film, the adhesiveness and adhesion between the liquid-repellent composition and the substrate, and contributes to the improvement of 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). In addition, it is preferably a monomer that has good film forming properties and can obtain a uniform copolymer solution or dispersion. Regarding the constituent unit (d), particularly preferably those derived from vinyl chloride, vinylidene chloride, cyclohexyl methacrylate, polyoxyethylene di(meth)acrylate, polyoxyethylene di(methyl) ) Alkyl ether of acrylate and dioctyl maleate. The constituent unit (d) can contribute to the improvement of the adhesion to the substrate of the composition or the improvement of the dispersion.

As for the corresponding commercial products, "AG-E070" and "AG-E550D" (manufactured by Asahi Glass Co., Ltd.) can be cited.

In the liquid-repellent layer, the content of the hydrophobic oxide particles is preferably 20% by mass to 70% by mass, and the content of the fluorine-based copolymer resin is preferably 70% by mass to 30% by mass. By setting the composition in this range, the sliding property of liquid can be obtained in the multilayer resin sheet. In contrast, hydrophobic oxide When the content of the fine particles is less than 20% by mass, satisfactory liquid repellency and liquid slippage may not be obtained; if the content of the hydrophobic oxide fine particles exceeds 70% by mass, the hydrophobic oxide fine particles may sometimes peel off.

Regarding the method of forming a liquid-repellent layer on the uneven surface, it is possible to prepare a dispersion liquid in which hydrophobic oxide particles are added to isopropyl alcohol (IPA) in advance, and then combine the aqueous dispersion liquid with the fluorine resin copolymer A method of applying a dispersion liquid adjusted in an arbitrary ratio on the aforementioned uneven surface with a coater or the like.

[Second Implementation Aspect]

As for the example of the resin sheet of the second embodiment of the present invention, as shown in Fig. 5, the surface area layer has a liquid-repellent layer (2) of the uneven shape layer (1) and the base layer (4) In between, a resin sheet with a sealant resin layer (3) is formed. That is, the layer composition of the resin sheet of the second embodiment is, from top to bottom, the liquid-repellent layer (2), the uneven shape layer (1), the sealant resin layer (3), and the base layer (4). Among them, the liquid-repellent layer and the concavo-convex shape layer are the same as those described in the first embodiment, so their description is omitted. However, the thickness of the concavo-convex shape layer is preferably 50 μm to 200 μm. If it is less than 50 μm, the transfer of the uneven shape may become poor. In addition, if it exceeds 200 μm, the production cost may increase.

<Substrate layer>

The base layer is preferably styrene resin (impact resistant polystyrene, polybutadiene-polystyrene-polyacrylonitrile graft polymer, etc.), olefin resin (polyethylene, polypropylene, etc.), poly Carbonate, polyester resin (polyethylene terephthalate, polybutylene terephthalate, etc.), nylon resin (nylon 6, nylon-66, etc.), ethylene-vinyl alcohol copolymer, acrylic resin, etc. Thermoplastic 性resin. In addition, in the case of lamination, it is a lamination formed by co-extrusion; or extruded lamination forming using a non-stretched film or biaxially stretched film; or a lamination formed by dry lamination.

The base material layer is preferably a polyester resin. For example, as the polyester resin of the base layer, polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, and polyethylene terephthalate can be used. , And as far as copolymerization components are concerned, glycol components such as diethylene glycol, neopentyl glycol, polyalkylene glycol, etc. can be used together with adipic acid, sebacic acid, phthalic acid, isophthalic acid , 2,6-naphthalenedicarboxylic acid and other dicarboxylic acid components copolymerized polyester resin, etc.

In the substrate layer, if necessary, additives such as coloring agents such as pigments and dyes; release agents such as polysiloxane oil; fibrous reinforcing agents such as glass fibers; talcum powder may be added as needed within the range that does not hinder the effects of the present invention. , Clay, silica, etc. coloring agent; sulfonic acid and alkali metal chloride or polyalkylene glycol, etc. antistatic agent and ultraviolet absorber; antibacterial agent. In addition, the resin scraps generated in the manufacturing process of the multilayer resin sheet of the present invention may be mixed and used.

<Sealant resin layer>

The sealant resin layer is one that allows the concavo-convex shape layer and the substrate layer to express adhesion. In terms of resin components, there are 100% by mass of modified olefin polymer resin and 100 parts by mass of hydrogenated styrene-based thermoplastic elastomer.

The sealant resin layer is preferably a modified olefin-based polymer. Regarding modified olefin polymer resins, the following can be cited as representatives: ethylene, propylene, butene-1 and other olefins with a carbon number of about 2-8; these olefins and ethylene, propylene, butene-1 , 3-methylbutene-1, pentene-1, Copolymers of other olefins such as 4-methylpentene-1, hexene-1, octene-1, and decene-1 with a carbon number of about 2-20, or with vinyl acetate, vinyl chloride, acrylic acid, methyl Olefin resins such as copolymers of vinyl compounds such as acrylic acid, acrylate, methacrylate, styrene, etc.; or ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-butene-1 copolymer Acrylic, methacrylic, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid Such as unsaturated carboxylic acids, or their acid halides, amides, imines, anhydrides, esters, etc. (specifically, maleic chloride, maleic imine, maleic anhydride, citraconic anhydride , Monomethyl maleate, dimethyl maleate, glycidyl maleate, etc.), modified under grafting reaction conditions.

Among them, ethylene-propylene-diene copolymer or ethylene-propylene or butene-1 copolymer rubber modified by unsaturated dicarboxylic acid or its anhydride, especially maleic acid or its anhydride, is particularly preferred.

The thickness of the sealant resin layer is preferably 20 μm to 90 μm, more preferably 40 μm to 80 μm. If it is less than 20 μm, interlayer peeling may occur between the uneven-shaped layer and the base layer, and if it exceeds 90 μm, the production cost may increase.

[Third Implementation Aspect]

The resin sheet of the third embodiment of the present invention, as shown in Fig. 6, does not use the sealant resin layer (3) shown in the second embodiment, but combines the concave-convex shape layer (1) and the base layer (4) Direct layering. That is, the layer structure of the resin sheet of the third embodiment, from top to bottom, is the liquid repellent layer (2), the concave-convex shape layer (1), and the base material layer (4). Thermoplastic Tree The grease sheet removes the layer composition of the sealant resin layer. Among them, the liquid-repellent layer and the concavo-convex shape layer are the same as the layers in the first embodiment and the second embodiment, so their description is omitted. On the other hand, the base material layer (4) in this embodiment is preferably designed to have sufficient adhesion with the uneven shape layer.

Therefore, in the resin sheet of the third embodiment, it is preferable to use a styrene-based resin having excellent adhesion to the concave-convex shape layer for the base layer. As far as the styrene resin is concerned, it is preferably a polystyrene resin containing 60% to 15% by mass, more preferably 55% to 15% by mass; and 40% to 85% by mass, more preferably 45% by mass A styrene-based substrate layer made of impact-resistant polystyrene resin of %-85% by mass is preferable. In addition, a styrene-based resin composition to which a hydrogenated styrene-based thermoplastic elastomer is added can also be used. When polystyrene resin and hydrogenated styrene-based thermoplastic elastomer are used in combination, it is preferable to include 90% to 95% by mass of polystyrene-based resin and 5% to 10% by mass of hydrogenated styrene-based thermoplastic elastomer The styrene-based resin composition formed by the body. In this case, when the addition amount of the hydrogenated styrene-based thermoplastic elastomer is less than 5% by mass, the adhesion to the concavo-convex shape layer becomes insufficient, and interlayer peeling may occur. If it exceeds 10% by mass, the production cost is Increased situation.

[Fourth Implementation Aspect]

The resin sheet of the fourth embodiment of the present invention, as shown in Figure 7, is a liquid-repellent layer (2), an uneven shape layer (1), a first sealant resin layer (3a), and an oxygen barrier substrate layer ( 5) A resin sheet in which the second sealant resin layer (3b) and the base material layer (4) are sequentially laminated. The first sealant resin layer and the second sealant resin The composition of the layers can be the same or different. The thickness of the concavo-convex shape layer is preferably 50 μm to 250 μm. If it is less than 50 μm, the transfer of the uneven shape may become poor. In addition, if it exceeds 200 μm, the production cost may increase.

<Substrate layer>

As for the resin used as the substrate layer in the fourth embodiment, nylon-based resin or methacrylate-based resin is preferred. As for nylon resins, examples include: caprolactam, dodecanolide and other internal amide polymers, 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid Alkanoic acid and other amino carboxylic acid polymers, hexamethylene diamine, decamethylene diamine, dodecamethylene diamine, 2,2,4- or 2,4,4-trimethyl Aliphatic diamines such as hexamethylene diamine, alicyclic diamines such as 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis(p-aminocyclohexylmethane), etc. Or diamine units such as aromatic diamines such as p-xylylenediamine; and aliphatic dicarboxylic acids such as adipic acid, suberic acid, sebacic acid, cyclohexane dicarboxylic acid, etc. Polycondensates of dicarboxylic acid units such as aromatic dicarboxylic acids 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, and nylon 6. /6T, nylon 6I/6T, etc. Among them, nylon 6 and nylon MXD6 are preferred.

The methacrylate-based resin may be a vinyl polymer based on a methacrylate monomer, and its structure and the like are not particularly limited. As for the methacrylate monomer, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate and hexyl methacrylate can be mentioned. Wait. Among these, In particular, methyl methacrylate is particularly preferred. In addition, the alkyl groups such as propyl, butyl, pentyl and hexyl in the methacrylate monomer may be straight chain or branched. In addition, the methacrylate resin blended in the resin composition of this embodiment may be a single polymer of methacrylate monomers or a copolymer of multiple methacrylate monomers. Alternatively, it may have monomer units derived from well-known vinyl compounds other than methacrylate, that is, ethylene, propylene, butadiene, styrene, α-methylstyrene, acrylonitrile, and acrylic acid.

<Oxygen barrier substrate layer>

Examples of the oxygen barrier substrate layer include ethylene-vinyl alcohol copolymer resin and nylon-based resin. Among them, ethylene-vinyl alcohol copolymer resins are preferred in terms of processability and moldability.

Ethylene-vinyl alcohol copolymer resin is usually obtained by saponification of ethylene-vinyl acetate copolymer. In order to have oxygen barrier properties, processability, and moldability, it is preferable to have an ethylene content of 10 mol% to 65 mol% %, preferably 20 mol%-50 mol%, and the saponification degree is above 90%, preferably above 95%.

In addition, as for nylon resins, random polymers such as caprolactam and dodecanolide, 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, etc. Alkanoic acid and other amino carboxylic acid polymers, hexamethylene diamine, decamethylene diamine, dodecamethylene diamine, 2,2,4- or 2,4,4-trimethyl Aliphatic diamines such as hexamethylene diamine, alicyclic diamines such as 1,3- or 1,4-bis(aminomethyl)cyclohexane and bis(p-aminocyclohexylmethane), Diamine units such as aromatic diamines such as meta or p-xylylenediamine; and aliphatic dicarboxylic acids such as adipic acid, suberic acid and sebacic acid, ring Polycondensates of dicarboxylic acid units such as alicyclic dicarboxylic acids such as hexanedicarboxylic acid, aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, and copolymers thereof.

As nylon-based resins, 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, and nylon 6. /610, nylon 6/6T, nylon 6I/6T, etc. Among them, nylon 6 and nylon MXD6 are preferred.

<Sealant resin layer>

As for the sealant resin layer, a modified olefin-based polymer is preferred. Regarding modified olefin polymer resins, the following can be cited as representatives: ethylene, propylene, butene-1 and other olefins with a carbon number of about 2-8; these olefins and ethylene, propylene, butene-1 , 3-methylbutene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1, decene-1 and other olefins with a carbon number of about 2-20 Copolymers, or olefin resins such as copolymers with vinyl compounds such as vinyl acetate, vinyl chloride, acrylic, methacrylic, acrylic, methacrylate, styrene, etc.; or ethylene-propylene copolymers, ethylene -Propylene-diene copolymer, ethylene-butene-1 copolymer, propylene-butene-1 copolymer and other olefinic gums, using acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, rich Unsaturated carboxylic acids such as maleic acid, itaconic acid, citraconic acid, and tetrahydrophthalic acid, or derivatives of acid halides, amides, imines, anhydrides, esters, etc., specifically, maleic acid Chlorine, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate, etc., modified under grafting reaction conditions .

Among them, unsaturated dicarboxylic acid or its anhydride, especially ethylene resin, propylene resin, or ethylene-propylene or butene-1 copolymer rubber modified with maleic acid or its anhydride is preferred.

Regarding the thickness of the sealant resin layer, any side is preferably 10 μm to 50 μm, and more preferably 20 μm to 40 μm. If it is less than 10 μm, it may become impossible to obtain sufficient layer adhesion strength, and if it exceeds 50 μm, the production cost may increase.

<Manufacturing of Liquid Repellent Resin Sheet>

The method of manufacturing the resin sheet of the present invention is not limited, and any method may be used. However, it typically includes the following steps: making a single-layer sheet having at least one convex shape on one side or including the The single-layer sheet is used as a laminated resin sheet with a concave-convex shape layer, and finally a liquid-repellent layer is formed on the surface of the concave-convex shape.

First, when producing a single-layer sheet having at least one or more convex shapes on one surface or a laminated resin sheet including the single-layer sheet as a layer of concavo-convex shapes, any resin sheet molding method can be used. For example, one single-axis extruder is used in the case of a single layer, and multiple single-axis extruders are used in the case of multiple layers to melt and extrude various raw resins to obtain a resin sheet with a T die. In the case of multiple layers, a multi-manifold die can also be used. Furthermore, the layer structure of each embodiment of the resin sheet of the present invention is basically the same as described above. However, for example, the raw material of the scraps generated in the manufacturing step of the resin sheet or the molded container of the present invention may be separately used. It can be added to the base material layer within the range of deterioration of physical properties, or it can be laminated on the base material layer by adding another layer.

Then, the concavo-convex 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 having ordinary knowledge in the field of the present invention can be used. For example, the method of manufacturing using extrusion molding method, the method of manufacturing using photolithography method, the method of manufacturing using hot press method, the method of manufacturing using pattern roller and UV curing resin, etc.

Finally, a liquid-repellent layer is formed on the surface of the uneven shape layer. The method of forming the liquid-repellent layer is not particularly limited, and well-known coating methods such as roll coating, gravure coating, bar coating, blade coating, brush coating, and powder electrostatic method can be used. In addition, the solvent for preparing the coating solution is not particularly limited. In addition to water, for example, alcohol (ethanol), cyclohexane, toluene, acetone IPA, propylene glycol, 2-methyl-2,4-pentanediol ( Organic solvents such as hexylene glycol), butanediol, pentamethylene glycol, n-pentane, n-hexane, and hexanol. At this time, a small amount of dispersant, colorant, sedimentation inhibitor, viscosity regulator, etc. can also be used in combination.

The resin sheet of the present invention has a liquid-repellent layer on the convex portion of the concavo-convex shape layer, and the fine concavo-convex shape and the liquid-repellent property produced by the liquid-repellent layer complement each other and exhibit excellent liquid repellency. That is, the resin sheet of the present invention, as described above, has a liquid contact angle of 130° or more, has sufficient liquid repellency, and the liquid rolls on the resin sheet. When the contact angle is less than 130°, the slipping property of the liquid may not be obtained on the resin sheet, and it cannot be said to have liquid repellency. In addition, in the resin sheet of the present invention, the sliding angle of the liquid is preferably 40° or less. If the sliding angle exceeds 40°, the sliding property of the liquid may not be obtained on the resin sheet, and it cannot be said to have liquid repellency. In addition, the contact angle and the slip angle can be measured with an automatic contact angle meter (for example, DM-501 manufactured by Kyowa Interface Science Co., Ltd.) for the resin sheet.

[Example]

Hereinafter, examples and comparative examples are given to explain the present invention more specifically, but the present invention is not limited at all by the contents of the examples and the like.

The various raw materials used in the examples are as follows.

(1) Concave-convex shape layer

. (A-1) Random polypropylene "PM921V" (manufactured by Sun Allomer)

. (A-2) Block polypropylene "PM854X" (manufactured by Sun Allomer)

. (B-1) Linear medium density polyethylene resin (C4) "Neo-Zex 45200" (manufactured by Prime Polymer)

. (B-2) Linear low-density polyethylene resin (C6) "Ult-Zex 20200J" (manufactured by Prime Polymer)

. (C) Styrene-conjugated diene block copolymer resin "730L" (manufactured by Denki Kagaku Kogyo Co., Ltd.) (diene content 25% by mass)

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

(2) Liquid repellent layer

. (E) Hydrophobic oxide particles: Hydrophobic silica "AEROSIL R812S" (manufactured by Evonik Degussa)

. (F-1) Fluorine-based copolymer resin: "AG-E070" (manufactured by Asahi Glass)

. (F-2) Fluorine-based copolymer resin: "AG-E550D" (manufactured by Asahi Glass)

(3) Sealant resin layer

. (G) Hydrogenated styrene-based thermoplastic elastomer "Tuftec P2000" (manufactured by Asahi Kasei Corporation)

. (H) Hydrogenated styrene-based thermoplastic elastomer "Tuftec M1943" (manufactured by Asahi Kasei Corporation)

. (I) Modified olefin-based polymer resin "Modic F502" (manufactured by Mitsubishi Chemical Corporation)

. (J) Modified olefin-based polymer resin "Admer SE810" (manufactured by Mitsui Chemicals)

(4) Substrate layer

. (G) Hydrogenated styrene-based thermoplastic elastomer "Tuftec P2000" (manufactured by Asahi Kasei Corporation)

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

. (L)GPPS resin "HRM23" (manufactured by Toyo Styrene)

. (M) PET resin (film) "Ester film E5102: 16μm" (manufactured by Toyobo Co., Ltd.)

. (N) Nylon 6 resin (film) "Harden film N1100: 15μm" (manufactured by Toyobo Co., Ltd.)

. (O) Ethylene-vinyl alcohol copolymer "Eval J-171B" (manufactured by Kuraray)

. (P) Acrylic resin "HBS000" (manufactured by Mitsubishi Chemical Corporation)

The methods for evaluating various characteristics of the resin sheets produced in the examples and the like are as follows.

(1) Convex shape observation

The convex shape of the sheet was measured using a laser microscope VK-X100 (manufactured by Keyence) to measure the height of the convex shape and the distance between the apexes of the convex shape. In addition, in order to measure the height of the convex shape and the distance between the vertices, a slicer was used to prepare a cross-sectional sample of the concave and convex shape. Regarding the height of the convex shape, measure the height of 10 pieces of the same shape at any 3 positions of the resin sheet, and use the 30 pieces to measure The arithmetic mean of the fixed value. When there are two or more types of convex shapes, the heights of the first convex shape and the second convex shape are respectively obtained by the same method. Regarding the distance between the apexes, the distance between the apexes of 10 adjacent convex shapes was measured at any 3 places on the resin sheet, and the arithmetic average of the 30 measured values was used. When there are two or more convex shapes, the distance between the apexes of the first convex shape and the second convex shape is measured, and the arithmetic average of the 30 measured values is used.

(2) Contact angle and sliding angle

The contact angle and the sliding angle were measured for the resin sheet using an automatic contact angle meter DM-501 (manufactured by Kyowa Interface Science Co., Ltd.). In addition, the test liquid used salad oil (Nisshin Oillio Group), hand soap "Kirei Kirei" (manufactured by LION), emulsion "Yukigokochi" (manufactured by ROHTO Pharmaceutical Co., Ltd.), and paint "black" (manufactured by Pentel). The amount is 8 μL when measuring the contact angle and 20 μL when measuring the sliding angle. If 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. In addition, if the sliding angle is 40° or less, the liquid repellency is high, and it can be judged that the adhesion of the liquid can be prevented.

(3) Tightness evaluation

Using a single-layer sheet (900 μm thick) of impact-resistant polystyrene, cut out the flange portion (refer to Figure 8) of the vacuum-formed container, and heat-sealed it using a heat-sealing tester (manufactured by Sagawa Manufacturing Co., Ltd.). The width of the sealing iron of the heat sealing tester is 1.0mm, and the resin sheet is used as the cover material. The sealing temperature is 210°C and the sealing pressure is 0.36MPa. In addition, the peel strength was measured by using Strograph VE1D (manufactured by Toyo Seiki Co., Ltd.), and the cover material (resin sheet) was pinched by the chuck on one side of the Strograph, and the flange of the container was pinched by the chuck on the other side. The peeling speed is 200mm/min. If the peel strength is 2.8N or more, it is judged that the sealing property is good.

In addition, the above-mentioned heat seal tester (manufactured by Sagawa Manufacturing Co., Ltd.) was used to produce a pouch so that the uneven shape layer of the produced sheet was on the inner surface side. The sealing temperature is 210°C, the sealing pressure is 0.36MPa, and the width of the sealing iron is 5mm. The peeling strength was measured using Strograph VE1D (manufactured by Toyo Seiki Co., Ltd.), and the resin sheet was pinched in the grip of the Strograph. The peeling speed is 200mm/min. If the peel strength is 8.5N or more, it can be judged that the sealability is good.

(4) Measurement of melt mass flow rate

According to JIS K 7210, it is measured under the conditions of test temperature: 230°C and load: 2.16Kg. The test machine used was Melt Indexer F-F01, manufactured by Toyo Seiki Seisakusho Co., Ltd.

(5) Oxygen transmission rate

The oxygen transmission rate of the resin sheet was measured using an OX-TRAN oxygen transmission rate measuring device (manufactured by Mocon), based on the JIS K7126-B method, at a temperature of 25°C and a relative humidity of 65%. If the oxygen transmission rate is less than 3.0ml/m ² . day. Atm, it can be judged that the oxygen barrier is good.

<Example 1 (Layer structure in Figure 1)>

Using a 65mm single-axis extrusion machine, the resin sheet is extruded by the T-die method. This extruded sheet is die-casted with a transfer roller and a touch roller whose surface is provided with uneven shapes by a laser engraving method, to obtain a resin sheet composed of a layer with uneven shapes on the surface.

Then, in order to form a liquid-repellent layer on the surface of the concave-convex shape layer, a hydrophobic silica and a fluorine-based copolymer resin were prepared to make the liquid-repellent layer The hydrophobic silica is 66% by mass, and the fluorine-based copolymer resin is 34% by mass (the solvent is a mixture of purified water and isopropanol). Use a bar coater to coat the mixed dispersion on the surface of the corona-treated concavo-convex shape layer, and dry it at 90°C to 150°C to form a liquid repellent layer. Table 1 shows the composition of the resin sheet in which the liquid-repellent layer is formed on the surface of the uneven shape layer.

In addition, the various characteristics of the resin sheet produced as described above were evaluated by the aforementioned methods. The results are shown in Table 2.

<Examples 2 to 12, Comparative Examples 1 to 6>

Except that the composition, thickness, and MFR of the concave-convex shape layer and the liquid-repellent layer are set as shown in Table 1, the resin sheets of Examples 2 to 12 and Comparative Examples 1 to 6 were produced in the same manner as in Example 1, and Make an evaluation. The results are shown in Table 2.

In addition, in Comparative Example 1, the liquid-repellent layer was not formed, and in Comparative Example 2, the uneven shape was not provided. In Comparative Example 3, hydrophobic silica is not included, and Comparative Example 4 is a composition in which no fluorine-based copolymer resin is used in the liquid repellent layer. Comparative Example 5 is a composition using silica that has not been subjected to a hydrophobic surface treatment on the liquid-repellent layer. In Comparative Example 6, the convex shape is formed into a bell-shaped sheet by thermal transfer of only the HIPS resin.

From the results shown in Table 2, the following matters are understood. In all of Examples 1 to 12, it is possible to obtain results that fully satisfy the evaluation criteria for the liquid repellency (contact angle, sliding angle) of the resin sheet for each liquid. In contrast, in Comparative Examples 1 to 4 and 6, no liquid other than purified water slipped off on the resin sheet. In Comparative Example 5, none of the liquid slipped off.

<Example 13 (Layer Structure in Figure 5)>

Using two 40mm single-axis extruders, by the feedblock method, a layer with an uneven shape layer of 80μm, a sealant resin layer of 40μm, and a substrate layer (PET resin) of 16μm are sequentially laminated and the thickness is 136μm The multilayer resin sheet is extruded by the T-die method. Furthermore, the PET base material layer is laminated by the extrusion lamination method when the uneven shape layer and the sealant layer are extruded.

<Example 15>

Using three 40mm single-axis extruders, by the feed head method, a layer with a concave and convex shape of 90μm, a sealant resin layer of 50μm, and a base The material layer (HIPS/GPPS=80/20) consists of a layer of 310μm and a multilayer resin sheet with a thickness of 450μm is extruded by the T-die method.

The extruded sheet obtained above is die-casted using a transfer roller and a touch roller to which surface irregularities are given by a laser engraving method, to obtain a multilayer resin sheet having irregularities on the surface of the sheet. The sheet thickness is 0.12mm.

Next, in order to form a liquid-repellent layer on the surface of the concavo-convex shape layer, a hydrophobic silica and a fluorine-based copolymer resin are prepared so that the hydrophobic silica becomes 66% by mass and the fluorine-based copolymer resin becomes 34% by mass. The dispersion (the solvent is a mixture of purified water/isopropanol). Using a bar coater, apply the mixed dispersion on the corona-treated surface of the concave-convex shape layer and dry it at 90°C~150°C to form a liquid repellent layer. Table 3 shows the composition and layer structure of each layer of the resin sheet in which the liquid-repellent layer is formed on the surface of the uneven shape layer.

In addition, the various characteristics of the resin sheet produced in the above-mentioned manner were evaluated by the aforementioned methods. The results are shown in Table 4.

<Examples 14-24, Comparative Example 7, Comparative Examples 9-12>

Except that the composition, thickness, and MFR of each layer of the concavo-convex shape layer, liquid repellent layer, and other multilayer resin sheets were set as shown in Table 3, the same manner as in Example 13 or Example 15 was used to produce Examples 14 and 16 The results are shown in Table 4 for the resin sheets of ~24, Comparative Example 7, and Comparative Examples 9-12. In addition, in Examples 13, 14, 19, 22 to 24 and Comparative Examples 11 and 12, the sealing properties were evaluated.

Furthermore, in Comparative Example 7, no liquid repellent layer was formed. In Comparative Example 9, since polyethylene with an MFR of 1.1 g/10 min was used for the uneven shape layer, the transferability was poor. Comparative Example 10 was not used in the liquid repellent layer. Composition of hydrophobic silica. Comparative Example 11 is a composition that does not use a fluorine-based copolymer resin in the liquid-repellent layer, and Comparative Example 12 is a composition that uses silica without a hydrophobic surface treatment in the liquid-repellent layer.

From the results shown in Table 4, the following matters can be understood. In all of Examples 13 to 24, the liquid repellency (contact angle, sliding angle) and airtightness (Examples 13, 14, 19, 22, 23, 24) of the relevant resin sheet for each liquid can be obtained. The results of the evaluation criteria. In contrast, in Comparative Example 7 and Comparative Examples 9 to 11, it was a result that liquids other than purified water did not slip off. In Comparative Example 12, none of the liquid slipped off.

<Example 25 (Layer Structure in Figure 6)>

Using two 40mm single-axis extruders, by the feed head method, a multilayer resin sheet with a thickness of 700μm and a layer with a concave-convex shape layer of 90μm and a styrene-based base layer of 610μm laminated in sequence, with a T die Extruded. In addition, for the styrene-based base material layer, a mixture of HIPS resin and hydrogenated thermoplastic elastomer at a mass ratio of 95/5 (HIPS/hydrogenated styrene-based thermoplastic elastomer) was used. With respect to the extruded sheet obtained above, the resin sheet of Example 25 was formed in the same manner as in Example 13. About the formed resin sheet, the same evaluation test as Example 13 was performed. The results are shown in Table 4.

<Example 26, Comparative Example 8>

Except that the composition, thickness, and MFR of the concavo-convex shape layer, the liquid repellent layer, and the styrene-based base layer were set as shown in Table 3, in the same manner as in Example 25, Examples 26 and Comparative Example 8 were produced Table 4 shows the evaluation results of the characteristics of the resin sheet. In addition, in Comparative Example 8, the composition was not provided with an uneven shape.

From the results shown in Table 4, the following matters can be understood. In Examples 25 to 26, it was possible to obtain results that fully satisfied the evaluation criteria for the liquid repellency (contact angle, sliding angle) of the resin sheet for each liquid. In contrast, in Comparative Example 8, the result was that liquids other than purified water did not slip off.

<Example 27 (Layer Structure in Figure 7)>

Using 5 40mm uniaxial extruders, by the feed head method, the first sealant resin layer consisting of 80μm concave and convex shape layer, 10μm of modified olefin polymer, and ethylene vinyl alcohol copolymer The formed oxygen barrier base layer 15μm, the second sealant resin layer composed of modified olefin-based polymer 10μm, and the polyester base layer 16μm of the fourth embodiment of the multilayer resin sheet with a thickness of 131μm T die head is extruded. In addition, regarding PET resin and nylon 6 resin, when the second sealant resin layer is extruded from the concavo-convex shape layer, the layers are laminated by an extrusion lamination method.

Using 5 sets of 40mm uniaxial extruders, by the feed head method, the first sealant resin layer composed of 90μm concave and convex shape layer, 20μm of modified olefin polymer, and ethylene-vinyl alcohol copolymer are sequentially included. The thickness of the formed oxygen barrier substrate layer 30μm, the second sealant resin layer composed of modified olefin polymer 20μm, and the substrate layer (HIPS/GPPS=80/20) 540μm in the fourth embodiment 700μm multi-layer resin sheet, extruded by T die.

By die-casting the obtained extruded sheet with a transfer roller and a touch roll with uneven shapes on the surface by a laser engraving method, a multilayer resin sheet with uneven shapes on the sheet surface is obtained.

Then, in order to form a liquid-repellent layer on the surface of the uneven shape layer, a hydrophobic silica and an olefin copolymer resin are produced, and the hydrophobic silica becomes 66% by mass and the fluorine copolymer resin becomes 34% by mass. The dispersion (the solvent is a mixture of purified water/isopropanol). Use a bar coater to coat this mixed dispersion on the surface of the corona-treated concavo-convex shape layer and dry it at 90°C to 150°C to form a liquid repellent layer. Table 5 shows the composition and layer structure of each layer of the resin sheet with the liquid-repellent layer formed on the surface of the uneven layer.

In addition, the various characteristics of the resin sheet produced in the above-mentioned manner were evaluated by the aforementioned methods. The results are shown in Table 6.

<Examples 28-29, 31-39, Comparative Examples 13-18>

Except that the composition, thickness, and MFR of each layer of the concavo-convex shape layer, liquid repellent layer, and other multilayer resin sheets are set as shown in Table 5, in the same manner as in Example 27 or Example 30, Examples 28 to 29 were produced. , 31~39 and comparative examples 13-18 resin sheets. In addition, in Examples 27 to 29, 33, 36 to 39, and Comparative Example 13, the sealing properties were evaluated.

In addition, in Comparative Example 13, the liquid-repellent layer was not formed, and in Comparative Example 14, the uneven shape was not provided. In Comparative Example 15, because polyethylene with an MFR of 1.1 g/10 min was used in the uneven shape layer, the transferability was poor. Comparative Example 16 had a composition in which no hydrophobic silica was used in the liquid repellent layer. Comparative Example 17 is a composition in which a fluorine-based copolymer is not used in the liquid-repellent layer. In Comparative Example 18, silica without a hydrophobic surface treatment is used for the liquid-repellent layer.

From the results shown in Table 6, the following matters can be understood. In all of Examples 27 to 39, it was possible to obtain results that fully satisfied the evaluation criteria of the liquid repellency (contact angle, sliding angle), sealing property, and oxygen barrier property of the resin sheet for each liquid. On the other hand, in Comparative Examples 13 to 17, the result that liquids other than purified water did not slip off was obtained. In Comparative Example 18, none of the liquid slipped off.

In the foregoing, although various embodiments have been used to describe the present invention, it goes without saying that the technical scope of the present invention is not limited to the scope described in the above embodiments. Those with ordinary knowledge in the field of the present invention should understand that various changes or improvements can be added to the above-mentioned embodiments. In addition, the addition of these various changes or improvements is also included in the technical scope of the present invention, which is clear from the description of the scope of the patent application.

1a‧‧‧Convex shape

2‧‧‧Liquid Repellent Layer

t‧‧‧Vertex interval of convex shape

h‧‧‧Convex shape height

Claims (15)

A liquid-repellent resin sheet having a concavo-convex shape layer composed of a resin composition containing a polyolefin resin and having a fine concavo-convex shape, and at least one surface of the concavo-convex shape layer One or more convex shapes, a liquid repellent layer containing hydrophobic oxide particles and a fluorine-based copolymer resin is formed on the surface having the convex shape, and the surface of the concave-convex shape layer is mixed with an oil-based liquid or a surfactant-based liquid The contact angle during contact is 130° or more, and the sliding angle is 40° or less, the content of the hydrophobic oxide 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. The liquid-repellent resin sheet of claim 1, wherein a substrate layer is laminated on the other side of the concavo-convex shape layer, and the substrate layer has at least one layer selected from the group consisting of styrene resin and olefin A layer composed of resin, polyester resin, nylon resin, ethylene-vinyl alcohol copolymer resin, and acrylic resin. The liquid-repellent resin sheet of claim 1 or 2, wherein the resin composition contains 35 mass% to 100 mass% of polyolefin resin. The liquid-repellent resin sheet of claim 2, wherein a sealant resin layer is formed between the concavo-convex shape layer and the substrate layer, and the sealant resin layer is selected from modified olefin polymer resins and hydrogenated benzene It is composed of at least one type of resin among ethylene-based thermoplastic elastomers. Such as the liquid-repellent resin sheet of claim 1 or 2, wherein the convex shape includes a first convex shape and a second convex shape, and the height of the first convex shape and the height of the second convex shape are respectively 20μm~150μm, and adjacent convex shapes Top of shape The dot interval is 20μm~100μm. The liquid-repellent resin sheet according to claim 5, wherein the first convex shape and the second convex shape are alternately arranged, and the ratio of the height of the second convex shape to the height of the first convex shape is 0.4 to 0.8. The liquid-repellent resin sheet of claim 1 or 2, wherein the melt mass flow rate of the resin composition at 230° C. is 5 g/10 minutes or more. According to claim 1 or 2, the liquid repellent resin sheet, wherein the hydrophobic oxide particles are hydrophobic silica particles having trimethylsilyl groups on the surface. The liquid-repellent resin sheet of claim 1 or 2, wherein the thickness of the concave-convex shape layer is 50 μm to 200 μm. A sheet for building materials, which uses the liquid-repellent resin sheet according to any one of claims 1 to 9. For example, the building material sheet of claim 10 is a sheet for wallpaper components. A sheet for packaging materials for daily life products, which uses the liquid-repellent resin sheet according to any one of claims 1 to 9. For example, the sheet for packaging materials for living goods in claim 12 is a sheet for water-related components. For example, the sheet for packaging materials for daily life products in claim 12 is a sheet for cover materials of food containers. For example, the sheet for packaging materials for living goods of claim 12 is a sheet for pouch.

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