JP2018103473A - Liquid repellent resin sheet and article using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin sheet having stable liquid repellency against pressure from a liquid and parts using the same. SOLUTION: A concave layer (1) made of a thermoplastic resin composition having a fine concave shape and a liquid repellent layer (2) made of hydrophobic inorganic fine particles and a binder resin are provided on the surface having the concave shape. The content of the hydrophobic inorganic fine particles in the liquid-repellent layer is preferably 30% by mass to 80% by mass, and the content of the binder resin is preferably 20% by mass to 70% by mass. By using it, a liquid-repellent resin sheet having stable liquid-repellent properties against pressure from a liquid can be obtained. [Selection diagram] Fig. 1

Description

  The present invention relates to a resin sheet having liquid repellency and an article using the same.

  Conventionally, paper materials and polymer materials have been used for foods such as soft drinks, fruit juice beverages, taste foods and drinks, and packaging for household goods.

  However, the sheet provided with the uneven shape described in Patent Documents 1, 2, 3, and 4 has a phenomenon in which the liquid is adapted by applying pressure from the liquid (a phenomenon in which the liquid enters between the uneven shapes), that is, a liquid repellent. As a result, there is a possibility that the stability or liquid repellency may be problematic.

JP 2012-126073 A JP 2014-139017 A Japanese Unexamined Patent Publication No. 2015-02553 Japanese Unexamined Patent Publication No. 2015-02552

  The present invention has been made in view of the above circumstances, and is excellent in liquid repellency and, for example, a resin that has little risk of lowering the liquid repellency due to pressure of contents or the like when used as a food packaging material. An object is to provide a sheet and an article using the resin sheet.

  An object of this invention is to provide the resin sheet provided with the stable liquid repellency with respect to the pressure from a liquid, and the articles | goods using this resin sheet.

  As a result of studying various means for expressing liquid repellency, the present inventor provided a liquid repellent layer that imparts a fine concave shape to the sheet surface and contains hydrophobic inorganic fine particles and a binder resin in a specific ratio. The present inventors have found that a stable liquid repellency against a pressure from a liquid can be imparted to the sheet surface, and have completed the present invention.

The present invention for solving the above-described problems is composed of the following.
(1) A liquid repellent comprising a concave layer composed of a thermoplastic resin composition having a fine concave shape, and a liquid repellent layer composed of hydrophobic inorganic fine particles and a binder resin on the concave surface of the concave layer. Resin sheet.
(2) The liquid repellent resin sheet according to (1), wherein the content of the hydrophobic inorganic particles in the liquid repellent layer is 30 to 80% by mass and the content of the binder resin is 70 to 20% by mass.
(3) The opening diameter of the concave shape is 10 μm to 150 μm, the interval between the deepest portions of the concave shape is 5 μm to 180 μm, the depth of the concave shape is 10 μm to 200 μm, and the aspect ratio (the depth of the concave shape / The liquid repellent resin sheet according to (1) or (2), which has a concave opening diameter of 0.5 to 2.0.
(4) The liquid repellent resin sheet according to any one of (1) to (3), wherein the number of the concave shapes per 1 cm ^{2 on the} resin sheet surface is 2500 to 9500000.
(5) The liquid repellent resin sheet according to any one of (1) to (4), wherein a melt mass flow rate of the thermoplastic resin composition is 5 g / 10 min or more.
(6) The liquid repellent resin sheet according to any one of (1) to (5), wherein the binder resin is an olefin copolymer.
(7) The liquid-repellent resin sheet according to any one of (1) to (6), wherein the hydrophobic inorganic fine particles are hydrophobic silica fine particles whose surface is modified with a trimethylsilyl group or dimethylpolysiloxane.
(8) The liquid repellent resin sheet according to any one of (1) to (7), wherein the hydrophobic inorganic fine particles have an average particle diameter of 5 to 1000 nm.
(9) The liquid repellent resin sheet according to any one of (1) to (8), wherein the thickness of the concave layer is 50 μm to 1000 μm.
(10) A styrene resin, olefin resin, polyester resin, nylon resin, ethylene-vinyl alcohol copolymer resin, acrylic resin, polycarbonate resin is formed on the other surface of the concave layer having the concave shape. The liquid repellent resin sheet according to any one of (1) to (9), wherein one or more base material layers made of one or more kinds of resins selected from thermoplastic elastomers are laminated.
(11) An article using the liquid-repellent resin sheet according to any one of (1) to (10).
(12) The article according to (11), which is a household item, packaging material, or building material member.
(13) The article according to (11), which is a food container, a pouch, a rain gown, an umbrella, wallpaper, or a watering member.

  ADVANTAGE OF THE INVENTION According to this invention, the liquid repellent resin sheet provided with the stable liquid repellency with respect to the pressure from a liquid can be provided.

It is a schematic plan view of a form with the liquid repellent resin sheet which concerns on 1st embodiment of this invention (square pyramid grid arrangement). It is a schematic longitudinal cross-sectional view (C-C ') which shows the liquid repellent resin sheet of FIG. It is a schematic plan view of the other form of the liquid repellent resin sheet which concerns on 1st embodiment of this invention (square pyramid zigzag arrangement). It is a schematic plan view of the other form of the liquid repellent resin sheet which concerns on 1st embodiment of this invention (triangular pyramid staggered arrangement). It is a schematic plan view of the other form of the liquid repellent resin sheet which concerns on 1st embodiment of this invention (conical grid arrangement). It is a schematic plan view of the other form of the liquid repellent resin sheet which concerns on 1st embodiment of this invention (conical zigzag arrangement). It is a schematic plan view of the other form of the liquid repellent resin sheet which concerns on 1st embodiment of this invention (hexagonal pyramid zigzag arrangement). It is a schematic longitudinal cross-sectional view (C-C ') which shows the laminated structure of the liquid repellent resin sheet which concerns on 2nd embodiment of this invention. It is a schematic longitudinal cross-sectional view (C-C ') which shows the laminated structure of the liquid repellent resin sheet which concerns on 3rd embodiment of this invention. It is a schematic longitudinal cross-sectional view (C-C ') which shows the laminated structure of the liquid repellent resin sheet which concerns on 4th embodiment of this invention. This is a vacuum-formed container using a liquid repellent resin sheet.

[First embodiment]
As shown in FIGS. 1 and 2, the liquid repellent resin sheet of the first embodiment according to the present invention comprises a concave layer (1) made of a thermoplastic resin composition having a fine concave shape, and the concave shape. The surface is provided with hydrophobic inorganic fine particles and a liquid repellent layer (2) made of a binder resin. It is preferable that the content of the hydrophobic inorganic fine particles in the liquid repellent layer is 30% by mass to 80% by mass, and the content of the binder resin is 20% by mass to 70% by mass. The liquid repellent resin sheet according to the first embodiment of the present invention has liquid repellency.

<Recessed layer>
(Thermoplastic resin composition)
Examples of the thermoplastic resin composition include a resin composition comprising a thermoplastic resin such as a polyolefin resin, a polystyrene resin, a polyester resin, a fluorine resin, a polycarbonate resin, a nylon resin, a vinyl chloride resin, and a thermoplastic elastomer. It is done. For example, when used as a food container, a polyolefin resin is preferable. The melt mass flow rate at 230 ° C. of the polyolefin-based resin composition is preferably 5 g / 10 minutes or more, and more preferably 15 g / 10 minutes or more. By setting the melt mass flow rate at 230 ° C. of the polyolefin-based resin composition to 5 g / 10 min or more, the concave transferability can be improved. The melt mass flow rate is calculated by measuring the outflow mass (g / 10 minutes) at regular intervals in accordance with JIS K 7210. As standard conditions, measurement is performed at a test temperature of 190 ° C. to 300 ° C. and a load of 2.16 kg to 10.00 kg.

The polyolefin resin means a resin composed of a polymer containing an α-olefin as a monomer, and particularly preferably includes a polyethylene resin and a polypropylene resin.
Examples of the polyethylene resin include high density polyethylene, low density polyethylene, linear low density polyethylene, and linear medium density polyethylene. The polyethylene resin includes not only polyethylene alone but also a copolymer or graft copolymer having the structure, and a blend thereof. Examples of the latter resin include ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid ester copolymer, ethylene-vinyl acetate-vinyl chloride copolymer. Examples include those obtained by copolymerizing and blending a resin having a polar group in a polyethylene chain, such as a blend or a blend with a ternary copolymer with an acid anhydride.

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

  Examples of polystyrene resins include homopolymers or copolymers of styrene monomers such as styrene, α-methyl styrene, p-methyl styrene, dimethyl styrene, pt-butyl styrene, chlorostyrene, styrene monomers and others. Copolymers with other monomers, such as styrene-acrylonitrile copolymer (AS resin), or other polymers such as styrene monomers and other polymers such as polybutadiene, styrene-butadiene copolymer, polyisoprene, polychloroprene and the like Examples thereof include graft polymers obtained by graft polymerization in the presence of a rubber-based polymer such as high impact polystyrene (HIPS resin) and styrene-acrylonitrile graft polymer (ABS resin).

  Examples of polyester resins include polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, polymethylene terephthalate, and copolymer components such as diol components such as diethylene glycol, neopentyl glycol, polyalkylene glycol, and adipic acid. Polyester resins obtained by copolymerizing dicarboxylic acid components such as sebacic acid, phthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid can be used.

  Fluorine-based resins include vinylidene fluoride homopolymer (PVDF), vinylidene fluoride copolymer based on vinylidene fluoride, tetrafluoroethylene-ethylene copolymer, chlorotrifluoroethylene-ethylene copolymer Is mentioned. For example, PVDF resin is a crystalline resin having various crystal structures such as α-type, β-type, γ-type, and αp-type. Examples of the vinylidene fluoride copolymer include a vinylidene fluoride-hexafluoropropylene copolymer, a vinylidene fluoride-tetrafluoroethylene copolymer, a vinylidene fluoride-chlorotrifluoroethylene copolymer, and a vinylidene fluoride-tri A fluoroethylene copolymer, a vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene terpolymer, a vinylidene fluoride-chlorotrifluoroethylene-hexafluoropropylene terpolymer, and a mixture of two or more thereof. Can be mentioned.

  Examples of the polycarbonate resin include an aromatic polycarbonate resin, an aliphatic polycarbonate resin, and an aromatic-aliphatic polycarbonate resin. Those which are usually classified into engineer plastics, and those obtained by polycondensation of general bisphenol A and phosgene or polycondensation of bisphenol A and carbonate can also be used. When producing by phosgene method or transesterification method using bisphenol, as raw material bisphenol, 2,2-bis- (4-hydroxyphenyl) propane (bisphenol A), 2,4-bis- (4-hydroxyphenyl) ) -Methyl-butane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane and the like. The polycarbonate resin may be a homopolycarbonate resin, a copolycarbonate resin copolymerized with carboxylic acid, or a mixture thereof.

  Examples of nylon resins include lactam polymers such as caprolactam and laurolactam, polymers of aminocarboxylic acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid, hexamethylenediamine, decamethylenediamine, and dodeca. Methylenediamine, aliphatic diamines such as 2,2,4- or 2,4,4-trimethylhexamethylenediamine, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis (p-aminocyclohexylmethane) Alicyclic diamine such as m- or p-xylylenediamine, diamine units such as m- or p-xylylenediamine, aliphatic dicarboxylic acids such as adipic acid, suberic acid and sebacic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid Aromatic dicarboxylic acids such as acid, terephthalic acid, isophthalic acid, etc. Polycondensates of carboxylic acid units, and copolymers thereof, and the like. Specifically, nylon 6, nylon 9, nylon 11, nylon 12, nylon 66, nylon 610, nylon 611, nylon 612, nylon 6T, nylon 6I, nylon MXD6, nylon 6/66, nylon 6/610, nylon 6 / 6T, nylon 6I / 6T, etc. Among them, nylon 6 and nylon MXD6 are preferable.

  As the vinyl chloride resin, a vinyl chloride homopolymer or a copolymer of vinyl chloride and another monomer is used. When polyvinyl chloride is a copolymer, it may be a random copolymer or a graft copolymer. As an example of the graft copolymer, for example, an ethylene-vinyl acetate copolymer or a thermoplastic urethane polymer may be used as a backbone polymer, and vinyl chloride may be graft polymerized thereon. The polyvinyl chloride of the present invention is an extrudable soft polyvinyl chloride and is preferably a composition containing an additive such as a polymer plasticizer. As the polymer plasticizer, known polymer plasticizers can be used. For example, ethylene-vinyl acetate-carbon monoxide copolymer, ethylene- (meth) acrylate-carbon monoxide copolymer, acetic acid A preferred example is an ethylene copolymer polymer plasticizer such as an ethylene-vinyl acetate copolymer having a large vinyl content.

  The thermoplastic elastomer has a structure composed of a soft phase (soft segment) and a hard phase (hard segment). Specifically, an olefin elastomer, a styrene elastomer, a urethane elastomer, a nylon elastomer, and a polyester elastomer. , Selected from vinyl chloride elastomers. These thermoplastic elastomers only need to be available from the market.

  The thermoplastic resin composition may contain other additives as long as the effects of the present invention are not impaired. Other additives include mold release agents such as silicone oil, carbon fibers such as cellulose nanofibers, aramid fibers and carbon nanofibers, fibrous reinforcing agents such as glass fibers, stabilizers, surfactants, lubricants and fillers. And coloring agents such as foaming agents, talc, clay, silica, and carbon black, antistatic agents, ultraviolet absorbers, antibacterial agents, and crystal nucleating agents. Furthermore, the scrap resin generated in the sheet manufacturing process can be mixed and used as long as the physical properties of the sheet are not impaired.

(Concave shape)
The concave shape is a shape in which a concave portion (opening) is formed on the sheet surface as shown in FIG. The shape of the opening in contact with the liquid may be a quadrangle as shown in FIG. 1, but may be a triangle, a hexagon, a circle, or the like. The arrangement form of the concave shape is not particularly limited, and it is sufficient that the opening is in contact with the liquid efficiently, and there are a grid arrangement and a zigzag arrangement arranged vertically and horizontally depending on the shape of the opening. For example, when the shape of the opening is a quadrangle, a grid arrangement may be used, and when the opening is a hexagon, a staggered arrangement may be used. If the liquid repellency is to be maintained, the shape of the opening is preferably a square or a triangle. In addition, the shape of the recess is not limited as long as it exhibits liquid repellency, and may be a cone, a prism, a bell, or the like. The concave shape formed on the sheet surface is not limited to one type, and two or more types of concave shapes having different sizes may be formed. In addition, the formation method of a concave shape is not specifically limited, A well-known method can be used. For example, the surface of a resin sheet is formed by casting with a transfer roll and a touch roll formed with a concavo-convex shape by a laser engraving method or a diamond bite engraving method, or a sheet-like mold is used to heat and press the sheet. And a method of transferring irregularities.

  The concave shape preferably has a depth (h) of 10 μm to 200 μm. If the concave shape depth is less than 10 μm, the liquid repellency may not be sufficiently maintained. If the concave shape depth exceeds 200 μm, the convex shape dimension in the mold for imparting the concave shape becomes unstable. There is. The concave depth is obtained by adding the thickness (100 nm to 4000 nm) of the liquid repellent layer described later. The thickness of the concave layer is not particularly limited, and may be 50 μm to 1000 μm including the concave portion.

  It is preferable that the adjacent deepest space | interval (t1) of concave shape is 5 micrometers-180 micrometers. In addition, the deepest part interval of the concave shape is at the shortest adjacent distance, the deepest part interval of the concave shape including the bank portion between the concave shapes, and if adjacent to each other even if the concave shapes are different, It means the interval of the deepest part of the concave shape. If the interval between the concave shapes is less than 5 μm, the convex shape dimension in the mold for imparting the concave shape may become unstable. On the other hand, if it exceeds 180 μm, the liquid repellency may be lowered.

  The opening diameter of the concave shape is a diagonal line when the shape of the opening is a square or hexagon, a diameter when the opening is circular, and a diameter when it is a triangle, or a perpendicular line connected from the apex to the diagonal side. The opening diameter is preferably 10 μm to 150 μm. If the opening diameter is less than 10 μm, the convex shape dimension in the mold for imparting the concave shape may become unstable. If it exceeds 150 μm, the liquid repellency may not be maintained.

  The aspect ratio of the concave shape (depth of the concave shape / opening diameter of the concave shape) is preferably 0.5 to 2.0. When the aspect ratio exceeds 2.0, the convex shape dimension in the mold for imparting the concave shape may become unstable. On the other hand, if it is less than 0.5, the liquid repellency may be lowered.

The number of concave shapes per unit area (1 cm ² ) on the resin sheet surface is preferably 2500 to 9500000. If the number is less than 2500, the liquid repellency may be lowered. If the number is more than 9500000, the convex shape dimension in the mold for imparting the concave shape may be unstable. In addition, as long as the number of concave shapes is within the above range, there may be two or more types of concave shapes having different geometric dimensions on the surface of the resin sheet.

The concave depth, the concave opening diameter, the concave deepest portion interval, and the concave interval can be measured using a laser microscope (for example, VK-X100 manufactured by Keyence Corporation).
The shape of the concave shape may be a triangular pyramid, a quadrangular pyramid, a hexagonal pyramid, a conical shape, etc. Was found to be preferable.

<Liquid repellent layer>
The liquid repellent layer is formed with a substantially constant thickness on the surface of the concave shaped layer so that the concave shape of the concave shaped layer is maintained almost as it is on the sheet surface, in order to maintain liquid repellency even after molding into a member It is provided and consists of hydrophobic inorganic fine particles and a binder resin. The thickness of the liquid repellent layer is preferably 100 to 4000 nm, but is not particularly limited as long as the effects of the present invention can be obtained. The “liquid repellency” in the present invention means a liquid repellency sufficient to prevent adhesion of a saccharide-based liquid to the resin sheet. Specifically, these liquid resin sheets It means that the contact angle of the liquid with respect to is 130 ° or more and / or the sliding angle is 40 ° or less. In addition, a contact angle and a fall angle | corner can be measured about a resin sheet using an automatic contact angle meter (for example, Kyowa Interface Chemical Co., Ltd. DM-501). Further, “stable liquid repellency with respect to pressure from the liquid” in the present invention means that liquid repellency is maintained even when a pressure such as 3 kPa is applied to the liquid.

  In the liquid repellent layer, the content of the hydrophobic inorganic fine particles is preferably 30% by mass to 80% by mass, and the content of the binder resin is preferably 20% by mass to 70% by mass. More preferably, the content of the hydrophobic inorganic fine particles is 40% by mass to 70% by mass, and the content of the binder resin is 30% by mass to 60% by mass. By setting the composition within this range, stable liquid repellency can be obtained even when pressure is applied from the liquid. On the other hand, if the content of the hydrophobic inorganic fine particles is less than 30% by mass, a sufficiently stable liquid repellency may not be obtained when a pressure is applied from the liquid. If it exceeds 80% by mass, the hydrophobic inorganic fine particles may peel off.

  As a method for forming the liquid repellent layer on the convex surface, a dispersion liquid in which hydrophobic inorganic fine particles are added to isopropyl alcohol (IPA) in advance is prepared, and then mixed with a binder resin at an arbitrary ratio, and the convex shape is formed. A method of coating the surface with a coater or the like is preferable.

(Hydrophobic inorganic fine particles)
The hydrophobic inorganic fine particles may be those having a hydrophobic group, and may be those hydrophobized by surface treatment. For example, hydrophobic silica fine particles whose surface is modified with a functional group such as trimethylsilyl, dimethylsilyl, alkylsilyl, aminoalkylsilyl, methacrylsilyl, or dimethylpolysiloxane are preferred. Further, fine particles in which hydrophilic inorganic fine particles are surface treated with a silane coupling agent or the like to make the surface state hydrophobic can also be used. The kind of inorganic substance is not limited as long as it has hydrophobicity. Among these, at least one of hydrophobic fumed silica, fused silica, alumina, titania and the like can be used. As long as it is hydrophobic, there is no restriction on the shape of these particles, and either spherical or non-spherical (crushed) shape can be used. The primary particles preferably have an average particle size of 5 to 1000 nm, more preferably 7 to 200 nm. By setting the average particle diameter of the primary particles to 5 to 1000 nm, liquid repellency satisfying the conditions of the present invention is obtained, and dispersibility in the binder resin is improved. In addition, the average particle diameter of a primary particle means the value obtained by measuring the diameter of 3000 to 5000 hydrophobic inorganic fine particles using a scanning electron microscope, and calculating an average value. As specific examples of these, for example, as silica, product names “AEROSIL R972”, “AEROSIL R972V”, “AEROSIL R972CF”, “AEROSIL R974”, “AEROSIL RX200”, “AEROSIL RY200”, “AEROSIL R202”, “AEROSIL R805”, “AEROSIL R812”, “AEROSIL R812S”, “AEROSIL RY300” (above, manufactured by Evonik Degussa) and the like. Examples of titania include “AEROXIDE TiO2 T805” (manufactured by Evonik Degussa). Examples of alumina include fine particles in which the product name “AEROXIDE Alu C” (manufactured by Evonik Degussa) is treated with a silane coupling agent to make the particle surface hydrophobic.

(Binder resin)
The binder resin in the present invention represents a dispersion in which an olefin copolymer is dispersed in a solvent such as water or isopropyl alcohol (IPA). In the present specification, the content of the binder resin indicates the content of a solid content mainly composed of the resin in the used binder resin.

  The olefin copolymer in the present invention means a polymer containing an α-olefin as a monomer, and includes a polyethylene polymer and a polypropylene polymer. For example, low density polyethylene, very low density polyethylene (copolymer of ethylene and α-olefin), ethylene-vinyl acetate copolymer (EVA), ethylene-alkyl acrylate copolymer, ethylene-alkyl methacrylate copolymer, Examples include ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, ionomers such as low-density polyethylene, and propylene-based elastomer materials. Commercially available products corresponding to this include “Chemical S-100” (Mitsui Chemicals), “Aquatex AC-3100”, “Aquatex EC-3500” (Japan Coating Resin), “Arrow Base SE-”. 1200 "," Arrow Base SD-1200 "," Arrow Base YA-4010 "(manufactured by Unitika Ltd.) and the like.

<Liquid>
The liquid in the present invention is a liquid having fluidity, and the viscosity of the liquid does not matter. For example, when food liquids are included, specific examples include yogurt, jelly, pudding, fruit sauce, syrup, ketchup, juice, porridge, honey, molasses, liquid sugar and the like.

[Second Embodiment]
As an example of the resin sheet according to the second embodiment of the present invention, as shown in FIG. 8, a concave layer (1) having a liquid repellent layer (2) laminated on the surface and a base material layer (4) A resin sheet having a sealant resin layer (3) formed therebetween. That is, the layer structure of the resin sheet according to the second embodiment includes a liquid repellent layer (2), a concave shaped layer (1), a sealant resin layer (3), and a base material layer (4) from top to bottom. is there. Here, since the liquid repellent layer and the concave shaped layer are the same as those described in the first embodiment, description thereof will be omitted. However, the thickness of the concave layer is preferably 50 to 250 μm. If it is less than 50 μm, the concave transfer may be poor. Moreover, when it exceeds 250 micrometers, production cost may become high.

<Base material layer>
The substrate layer is made of styrene resin (impact polystyrene, polybutadiene-polystyrene-polyacrylonitrile graft polymer, etc.), olefin resin (polyethylene, polypropylene, etc.), polycarbonate, polyester resin (polyethylene terephthalate, polybutylene terephthalate, etc.) It is preferably made of a thermoplastic resin such as a nylon resin (nylon 6, nylon-66, etc.), an ethylene-vinyl alcohol copolymer, an acrylic resin, or a thermoplastic elastomer. In the case of lamination, there are lamination by co-extrusion molding, extrusion lamination molding using an unstretched film, biaxially stretched film, and lamination by dry lamination molding.

  The biaxially stretched film is preferably made of a polyester resin or a nylon resin. For example, as the polyester resin used as the base material layer, polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, polymethylene terephthalate and the like are preferable. Examples of the copolymer component include diol components such as diethylene glycol, neopentyl glycol, and polyalkylene glycol, and dicarboxylic acid components such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid. A copolymerized polyester resin or the like can be used.

  Examples of nylon resins include lactam polymers such as caprolactam and laurolactam, polymers of aminocarboxylic acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid, hexamethylenediamine, decamethylenediamine, and dodeca. Methylenediamine, aliphatic diamines such as 2,2,4- or 2,4,4-trimethylhexamethylenediamine, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis (p-aminocyclohexylmethane) Alicyclic diamine such as m- or p-xylylenediamine, diamine units such as m- or p-xylylenediamine, aliphatic dicarboxylic acids such as adipic acid, suberic acid and sebacic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid Aromatic dicarboxylic acids such as acid, terephthalic acid, isophthalic acid, etc. Polycondensates of carboxylic acid units, and copolymers thereof, and the like.

  Specific examples of nylon resins 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, nylon 6I / 6T, etc., among which nylon 6 and nylon MXD6 are preferred.

  For the base material layer, if necessary, a colorant such as pigment or dye, a release agent such as silicone oil, carbon such as cellulose nanofiber, aramid fiber, or carbon nanofiber, as long as the effects of the present invention are not impaired. Fibrous reinforcing agents such as fibers and glass fibers, colorants such as talc, clay and silica, salt compounds of sulfonic acid and alkali metals, antistatic agents such as polyalkylene glycol, UV absorbers, antibacterial agents and the like Additives can be added. Moreover, the scrap resin generated in the production process of the multilayer resin sheet of the present invention can be mixed and used.

<Sealant resin layer>
A sealant resin layer expresses the adhesiveness of a concave shaped layer and a base material layer. Examples of the resin component include 100% by mass of a modified olefin polymer resin and 100 parts by mass of a thermoplastic elastomer.

  The material for the sealant resin layer is preferably a modified olefin polymer. Examples of the modified olefin polymer resin include olefins having about 2 to 8 carbon atoms such as ethylene, propylene, and butene-1, those olefins, ethylene, propylene, butene-1, 3-methylbutene-1, pentene-1, Copolymers with other olefins having about 2 to 20 carbon atoms such as 4-methylpentene-1, hexene-1, octene-1, decene-1, etc., vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, acrylic Olefin resins such as acid esters, methacrylates, copolymers with vinyl compounds such as styrene, ethylene-propylene copolymers, ethylene-propylene-diene copolymers, ethylene-butene-1 copolymers, propylene -Olefin rubber such as butene-1 copolymer, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid Unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid and tetrahydrophthalic acid, or derivatives thereof such as acid halides, amides, imides, anhydrides and esters, specifically maleyl chloride, maleimide, Typical examples include maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate, and the like modified under graft reaction conditions.

  Among these, an ethylene-propylene-diene copolymer or an ethylene-propylene or ethylene-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, more preferably 40 to 80 μm. If it is less than 20 μm, delamination may occur between the concave shaped layer and the base material layer, and if it exceeds 90 μm, the production cost may increase.

[Third embodiment]
As shown in FIG. 9, the resin sheet according to the third embodiment of the present invention does not use the sealant resin layer (3) shown in the second embodiment, but the concave layer (1) and the base material layer (4). ) Directly laminated. That is, the layer structure of the resin sheet according to the third embodiment is the liquid repellent layer (2), the concave layer (1), and the base material layer (4) from the top to the bottom. The thermoplastic resin sheet has a layer configuration in which the sealant resin layer is removed. Here, the liquid repellent layer and the concave layer are the same as the layers in the first embodiment and the second embodiment, and thus the description thereof is omitted. On the other hand, it is preferable that the base material layer (4) in this embodiment has sufficient adhesiveness with the concave shaped layer.

  Therefore, in the resin sheet which concerns on 3rd embodiment, it is preferable to use the styrene resin which is excellent in adhesiveness with a concave shaped layer as a base material layer. The styrenic resin is preferably 60 to 15% by mass, more preferably 55 to 15% by mass polystyrene resin, preferably 40 to 85% by mass, and more preferably 45 to 85% by mass impact resistant polystyrene resin. A styrene-based substrate layer comprising is preferred. A styrene resin composition to which a hydrogenated styrene thermoplastic elastomer is added can also be used. When a polystyrene resin and a hydrogenated styrene thermoplastic elastomer are used in combination, a styrene resin composition comprising 90 to 95% by mass of a polystyrene resin and 5 to 10% by mass of a hydrogenated styrene thermoplastic elastomer. Is preferred. In this case, if the addition amount of the hydrogenated styrene-based thermoplastic elastomer is less than 5% by mass, the adhesion to the concave layer becomes insufficient, and delamination may occur. May be higher.

[Fourth embodiment]
As shown in FIG. 10, the resin sheet according to the fourth embodiment of the present invention includes a liquid repellent layer (2), a concave shaped layer (1), a first sealant resin layer (3a), an oxygen barrier base material layer ( 5) A resin sheet in which a second sealant resin layer (3b) and a base material layer (4) are laminated in this order. The first sealant resin layer and the second sealant resin layer may have the same composition or different compositions. The thickness of the concave layer is preferably 50 to 250 μm. If it is less than 50 μm, the concave transfer may be poor. Moreover, when it exceeds 250 micrometers, production cost may become high.

<Base material layer>
As the material of the base material layer of the fourth embodiment, the same material as that of the base material layer of the second embodiment can be used. For example, a styrene resin, a polyester resin, a nylon resin, an acrylic resin, etc. It is preferable to have sufficient adhesiveness with the sealant resin layer. The acrylic resin is particularly preferably used, and the structure thereof is not particularly limited as long as it is a vinyl polymer based on a methacrylic acid ester monomer. Examples of the methacrylic acid ester monomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate and hexyl methacrylate. Of these, methyl methacrylate is particularly preferred. Further, alkyl groups such as propyl group, butyl group, pentyl group and hexyl group in the methacrylic acid ester monomer may be linear or branched. Further, the methacrylic ester resin blended in the resin composition of the present embodiment may be a homopolymer of a methacrylic ester monomer or a copolymer of a plurality of methacrylic ester monomers. Or you may have a monomer unit derived from ethylene, propylene, butadiene, styrene, (alpha) -methylstyrene, acrylonitrile, acrylic acid etc. which are well-known vinyl compounds other than methacrylic acid ester.

  For the base material layer, if necessary, a colorant such as pigment or dye, a release agent such as silicone oil, carbon such as cellulose nanofiber, aramid fiber, or carbon nanofiber, as long as the effects of the present invention are not impaired. Fibrous reinforcing agents such as fibers and glass fibers, colorants such as talc, clay and silica, salt compounds of sulfonic acid and alkali metals, antistatic agents such as polyalkylene glycol, UV absorbers, antibacterial agents and the like Additives can be added. Moreover, the scrap resin generated in the production process of the multilayer resin sheet of the present invention can be mixed and used.

<Oxygen barrier substrate layer>
Examples of the material for the oxygen barrier base material layer include ethylene-vinyl alcohol copolymer resins and nylon resins. Among these, ethylene-vinyl alcohol copolymer resin is preferable in terms of processability and moldability.

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

  Examples of nylon resins include lactam polymers such as caprolactam and laurolactam, polymers of aminocarboxylic acids such as 6-aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, hexamethylenediamine, and decamethylenediamine. , Dodecamethylenediamine, aliphatic diamine such as 2,2,4- or 2,4,4-trimethylhexamethylenediamine, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis (p-aminocyclohexyl) Methane) and other alicyclic diamines, m- or p-xylylenediamine and other aromatic diamines and other diamine units, adipic acid, suberic acid, sebacic acid and other aliphatic dicarboxylic acids, cyclohexanedicarboxylic acid and other alicyclic rings Aromatic dicarboxylic such as dicarboxylic acid, terephthalic acid, isophthalic acid Polycondensates of a dicarboxylic acid unit and the like, and copolymers thereof, and the like.

  Specific examples of nylon resins 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, nylon 6I / 6T, etc., among which nylon 6 and nylon MXD6 are preferred.

<Sealant resin layer>
The material for the sealant resin layer is preferably a modified olefin polymer. Examples of the modified olefin polymer resin include olefins having about 2 to 8 carbon atoms such as ethylene, propylene, and butene-1, those olefins, ethylene, propylene, butene-1, 3-methylbutene-1, pentene-1, Copolymers with other olefins having about 2 to 20 carbon atoms such as 4-methylpentene-1, hexene-1, octene-1, decene-1, etc., vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, acrylic Olefin resins such as acid esters, methacrylates, copolymers with vinyl compounds such as styrene, ethylene-propylene copolymers, ethylene-propylene-diene copolymers, ethylene-butene-1 copolymers, propylene -Olefin rubber such as butene-1 copolymer, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid Unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid and tetrahydrophthalic acid, or derivatives thereof such as acid halides, amides, imides, anhydrides and esters, specifically maleyl chloride, maleimide, Typical examples include maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate, and the like modified under graft reaction conditions.

  Among these, an ethylene-based resin, a propylene-based resin, or an ethylene-propylene or ethylene-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 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 it exceeds 50 μm, the production cost may increase.

[Manufacture of liquid-repellent resin sheet]
The method for producing the resin sheet according to the present invention is not limited and may be any method, but typically, a single-layer sheet having a concave shape on one surface or a laminated resin sheet including a layer having the concave shape It is preferable to include a step of finally forming a liquid repellent layer on the concave surface.

  First, when producing a single layer sheet having a concave shape on one surface or a laminated resin sheet including a layer having the concave shape, any resin sheet forming method can be used. For example, in the case of a single layer, a single-screw extruder is used, and in the case of a multilayer, a plurality of single-screw extruders are used to melt-extrude each raw resin and obtain a resin sheet by a T die. It is done. In the case of multiple layers, a multi-manifold die may be used. The layer structure of each embodiment of the resin sheet of the present invention is basically the same as described above. In addition, for example, scrap raw materials generated in the manufacturing process of the resin sheet or member of the present invention, physical properties, etc. As long as no deterioration is observed, it may be added to the base material layer or may be laminated as a further layer.

  Next, although the concave shape is formed in the single layer or multilayer resin sheet, this method is not particularly limited, and any method known to those skilled in the art can be used. For example, a method of manufacturing using an extrusion molding method, a method of manufacturing using a photolithography method, a method of manufacturing using a hot press method, a method of manufacturing using a pattern roll and a UV curable resin, a roll-to-roll method And the like.

  Finally, a liquid repellent layer comprising a specific content of hydrophobic inorganic fine particles and a binder resin is formed on the surface of the concave shaped layer. The method for forming the liquid repellent layer is not particularly limited, and for example, a known coating method such as roll coating, gravure coating, bar coating, doctor blade coating, brush coating, or electrostatic powder method can be employed. In addition, the solvent for preparing the coating liquid is not particularly limited, and other than water, for example, alcohol (ethanol), cyclohexane, toluene, acetone, IPA, propylene glycol, hexylene glycol, butyl diglycol, pentamethylene glycol, An organic solvent such as normal pentane, normal hexane, and hexyl alcohol can be appropriately selected. At this time, a very small amount of a dispersant, a colorant, an anti-settling agent, a viscosity modifier and the like can be used in combination.

[Goods]
The liquid repellent resin sheet according to the present invention can be applied to the above-described articles that require liquid repellency. Specific description will be given below.

  The liquid-repellent resin sheet of the present invention can be applied as packaging materials such as food containers and pouches, household items such as rain feathers and umbrellas, water-related members used in kitchens, bathrooms, toilets, and wallpaper.

  For example, the liquid-repellent resin sheet of the present invention can be applied to food containers, pouches, etc. to prevent the contents from adhering to the inner wall of the containers, etc. The effect of reducing the trouble of washing the container at the time of separation can be obtained.

  For example, when the liquid-repellent resin sheet of the present invention is applied to rain feathers, umbrellas, etc., it is difficult for water droplets to adhere to the liquid repellent resin sheet.

  For example, when the liquid repellent resin sheet of the present invention is applied to a wall panel in a bathroom, it is possible to obtain an effect that water droplets and the like are hardly attached.

  For example, when the liquid repellent resin sheet of the present invention is applied to an interior material or the like, an effect that dirt or the like hardly adheres can be obtained.

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

Various raw materials used in Examples and the like are as follows.
(1) Concave 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) “Neozex 45200” (manufactured by Prime Polymer Co., Ltd.)
(B-2) Linear low density polyethylene resin (C6) “Ultzex 20200J” (manufactured by Prime Polymer)
(C) Styrene-conjugated diene block copolymer resin “730L” (manufactured by Denka) (diene content: 25% by mass)
(D) GPPS resin “G100C” (manufactured by Toyo Styrene Co., Ltd.)
(E) PET resin “TRN-8580FC” (manufactured by Teijin Limited)
(F) Vinyl chloride resin “CG60EB” (Mitsubishi Chemical Corporation)
(G) Nylon 6 resin “1022B” (manufactured by Ube Industries)
(H) Polyvinylidene fluoride resin “Kyner 720” (manufactured by Arkema)
(I) Polycarbonate resin “L-1225L” (manufactured by Teijin Limited)
(2) Liquid repellent layer (J) Hydrophobic inorganic fine particles: Hydrophobic silica “AEROSIL R812S” (manufactured by Evonik Deguza), surface-modified with a trimethylsilyl group, average primary particle size: 7 nm
(K) Hydrophobic inorganic fine particles: Hydrophobic silica “AEROSIL RY200” (manufactured by Evonik Degussa) surface-modified with dimethylpolysiloxane, average primary particle size: 12 nm
(L) Binder resin: Olefin-based copolymer resin “Aquatex AC-3100” (manufactured by Japan Coating Resin Co., Ltd.)
(3) Sealant resin layer (M) Hydrogenated styrene thermoplastic elastomer “Tuftec P2000” (manufactured by Asahi Kasei Corporation)
(N) Hydrogenated styrene thermoplastic elastomer “Tuftec M1943” (manufactured by Asahi Kasei Corporation)
(O) Modified olefin resin “Modic F502” (Mitsubishi Chemical Corporation)
(P) Modified olefin resin “Admer SE810” (Mitsui Chemicals)
(4) Base material layer (M) Hydrogenated styrene thermoplastic elastomer “Tuftec P2000” (manufactured by Asahi Kasei Corporation)
(Q) HIPS resin “Toyostyrene H850N” (manufactured by Toyo Styrene Co., Ltd., butadiene content: 9.0% by mass)
(R) GPPS resin “HRM23” (manufactured by Toyo Styrene Co., Ltd.)
(S) PET resin (film) “Ester film E5102: 16 μm” (manufactured by Toyobo Co., Ltd.)
(T) Nylon 6 resin (film) “Harden film N1100: 15 μm” (manufactured by Toyobo Co., Ltd.)
(U) Ethylene-vinyl alcohol copolymer “Eval J-171B” (manufactured by Kuraray Co., Ltd.)
(V) Acrylic resin “HBS000” (Mitsubishi Chemical Corporation)

  The evaluation method of various characteristics about the resin sheet produced in the example etc. is as follows.

(1) Observation of concave shape The concave shape of the sheet was measured by using a laser microscope VK-X100 (manufactured by Keyence Corporation). The depth of the concave shape, the depth of the concave shape, the interval of the concave shape, and the opening diameter of the concave shape were measured. Moreover, in order to measure the concave shape depth and the deepest interval between the concave shapes, a concave cross-section sample was prepared using a microtome. For the depth of the concave shape, 10 depths having the same shape were measured from arbitrary three locations on the resin sheet, and the arithmetic average value of the 30 measured values was used. About the deepest part space | interval, the adjacent deepest part space | interval of ten concave shapes was measured from arbitrary three places of the resin sheet, and the arithmetic mean value of the 30 measured values was used.

(2) Contact angle and tumbling angle The contact angle and tumbling angle were determined by using a vacuum / pressure forming machine (manufactured by Asano Laboratories) for the resin sheet and resin sheet, and the draw ratio (= The tray container molded so that (sheet thickness / container bottom thickness) was 1.6 times was measured using an automatic contact angle meter DM-501 (manufactured by Kyowa Interface Science Co., Ltd.). The test solution was a syrup solution (manufactured by Melodian Co., Ltd.), and the dropping amount was 8 μL when measuring the contact angle and 20 μL when measuring the falling angle. In the case of a sheet, it can be determined that if the contact angle is 130 ° or more, the liquid repellency is high and liquid adhesion can be prevented. Further, when the falling angle is 40 ° or less, the liquid repellency is high, and it can be determined that the adhesion of the liquid can be prevented.
In the case of a tray container, it can be determined that if the contact angle is 120 ° or more, the liquid repellency is high and liquid adhesion can be prevented. Further, when the falling angle is 70 ° or less, the liquid repellency is high, and it can be determined that the adhesion of the liquid can be prevented.

(3) Hydraulic pressure test The pressure test was performed by attaching a 10 mm square resin sheet to the bottom of a cylindrical polypropylene case (hereinafter, cylindrical case: 14 mm diameter, 50 mm height), and applying a hydraulic pressure of 3 kPa. Fill the cylindrical case with syrup (Melodyne), remove the syrup after 1 hour, take out the liquid repellent sheet attached to the bottom of the cylindrical case with tweezers, and attach the syrup on the resin sheet. As shown in 2, 4, and 6, the state where there was no adhesion at all was “5”, and the state where there was the most adhesion was “1”. In this five-step evaluation, it was determined that adhesion was suppressed if it was “4” or more.

(4) Measurement of melt mass flow rate In accordance with JIS K 7210 and ASTM D 1238, olefin resin and vinyl chloride resin have a test temperature of 190 ° C., load: 2.16 Kg, and PS resin has a test temperature of 200 ° C., load. : 5.00 Kg, test temperature: 230 ° C. for fluororesin, load: 5.0 Kg, PET resin for test temperature: 280 ° C., load: 1.2 Kg, PC resin for test temperature: 300 ° C., load: 1 Measured under the condition of 2 kg. The test equipment used was a melt indexer F-F01 (manufactured by Toyo Seiki Seisakusho Co., Ltd.).

(5) Oxygen permeability The oxygen permeability of the resin sheet was measured at a temperature of 25 ° C. and a relative humidity of 65% using an OX-TRAN oxygen permeability measuring device (manufactured by Mocon) according to JIS K7126-B method. Measured under conditions. It can be determined that the oxygen barrier property is good when the oxygen permeability is less than 3.0 ml / m ² · day · atm.

(6) Sealability evaluation (container)
Using a single layer sheet (900 μm thick) of impact-resistant polystyrene, the flange portion (see FIG. 11) of the vacuum-formed container was cut out, and heat sealing was performed using a heat seal tester (manufactured by Sagawa Seisakusho). The seal iron width of the heat seal tester was 1.0 mm, and the produced resin sheet was used as a lid. The sealing temperature is 210 ° C. and the sealing pressure is 0.36 MPa. Peel strength is measured using a strograph VE1D (manufactured by Toyo Seiki Co., Ltd.) with a lid (resin sheet) sandwiched between one chuck portion of the strograph and a flange portion of the container sandwiched between the other chuck portion. did. The peeling speed is 200 mm / min. It can be determined that the sealing property is good when the peel strength is 2.8 N or more.

(7) Sealability evaluation (pouch)
A pouch was produced using the heat seal tester (Sagawa Seisakusho) with the concave layer of the produced sheet facing the inner surface. The seal temperature is 210 ° C., the seal pressure is 0.36 MPa, and the seal iron width is 5 mm. The peel strength was measured using a strograph VE1D (manufactured by Toyo Seiki Co., Ltd.) with a resin sheet sandwiched between the chuck parts of the strograph. The peeling speed is 200 mm / min. It can be determined that the sealing property is good when the peel strength is 8.5 N or more.

(8) Number of concave shapes (unit area: per 1 cm ² )
Using the laser microscope VK-X100 (manufactured by Keyence Corporation), the number of concave shapes per 10,000 μm ² is counted on the surface of the concave layer of the produced sheet, and the concave shape per unit area (1 cm ² ) is based on the count number. The number of was calculated.

<Example 1 (concave shape of FIG. 1, layer structure of FIG. 2)>
Using the (A-1) random polypropylene as a material for the concave layer, a single 65 mm single-screw extruder was used, and a single-layer resin sheet was extruded by the T-die method. The extruded sheet was cast with a transfer roll and a touch roll having a convex shape on the surface by a diamond bite engraving method, and a concave shape was imparted to one surface.

  Next, in order to form a liquid repellent layer on the surface of the concave layer having the concave shape, the hydrophobic silica in the liquid repellent layer is mixed with the (J) hydrophobic silica and the (L) binder resin in a solid content ratio. A dispersion (mixture of purified water / isopropyl alcohol) was prepared by mixing so that the composition ratio would be 49% by mass of the active silica and 51% by mass of the binder resin. The mixed dispersion was coated on the surface having a concave shape using a bar coater and dried at 90 ° C. to form a liquid repellent layer. The thickness of each layer of the resin sheet on which the liquid repellent layer is formed is shown in Table 1 (the numerical value in parentheses of the liquid repellent layer indicates the thickness of the liquid repellent layer after drying). Various characteristics of the liquid repellent resin sheet produced as described above were evaluated by the above-described methods. The results are shown in Table 2.

<Examples 2-12, Comparative Examples 1-6>
Except that the material composition and thickness of each layer were set as shown in Table 1, it was the same as Example 1, and the concave shape was changed to the concave shape shown in FIGS. Liquid repellent resin sheets according to Examples 2 to 12 and Comparative Examples 1 to 6 were produced. Further, the obtained liquid repellent resin sheet was subjected to the same evaluation test as in Example 1, and the results are shown in Table 2.

  In Comparative Example 1, no liquid repellent layer is formed, and in Comparative Example 2, a concave shape is not provided. Comparative Example 3 did not contain hydrophobic silica, and Comparative Example 4 provided a bell-shaped convex shape. In Comparative Example 5, the composition does not contain a binder resin in the liquid repellent layer, and in Comparative Example 6, the composition uses silica that has not been subjected to hydrophobic surface treatment.

From the results shown in Table 2, the following became clear.
Although a slight performance decrease in the liquid repellency of Example 6 can be seen, in all of the other Examples 1 to 5 and 7 to 12, the liquid repellency (contact angle, falling angle, hydraulic pressure) with respect to each liquid in the sheet. With respect to the test), a contact angle of 130 ° or more, a sliding angle of 40 ° or less, and a pressure test of 4 or more were obtained. On the other hand, in Comparative Example 1, the result was 3 or less in the hydraulic pressure test, and in Comparative Example 2, the contact angle was 130 ° or more and the sliding angle was 40 ° or less, but the result was 3 or less in the hydraulic test. . In Comparative Example 3, although a result that the contact angle was 130 ° or more was obtained, the falling angle was 40 ° or more and 3 or less in the pressure test. Further, in Comparative Example 4, the hydraulic pressure test was 3 or less, and in Comparative Example 5, the effect was obtained with respect to any of the contact angle, the falling angle, and the hydraulic pressure test, but the coated hydrophobic silica was detached. It was seen. In Comparative Example 6, no effect was obtained with respect to any of the contact angle, the falling angle, and the hydraulic pressure test.

<Example 13 (concave shape of FIG. 1, layer structure of FIG. 8)>
Using the (A-1) random polypropylene as the material for the concave layer and the (P) modified olefin resin as the material for the sealant resin layer, feed using two 40 mm single screw extruders and a T die After the concave layer and the sealant resin layer are laminated by the block method, the laminate is extruded on the (S) PET resin (film) to be the base material layer, and is composed of the concave shape layer / sealant resin layer / base material layer 3 A layered resin sheet was obtained. At that time, casting was performed with a transfer roll and a touch roll having a convex shape on the surface by a diamond bite engraving method, and a concave shape was imparted to the surface on the concave layer side.

  Subsequently, a liquid repellent layer was formed on the surface of the concave layer provided with the concave shape in the same manner as in Example 1. The thickness of each layer of the resin sheet on which the liquid repellent layer is formed is shown in Table 3 (the numerical value in parentheses of the liquid repellent layer indicates the thickness of the liquid repellent layer after drying). Various characteristics of the liquid repellent resin sheet produced as described above were evaluated by the above-described methods. The results are shown in Table 4.

<Examples 14 to 24, Comparative Examples 7 to 12>
About Example 14, 19, 22-24, and Comparative Example 12, it carried out similarly to Example 13 except having set the material composition and thickness of each layer as shown in Table 3, and Example 15-18, 20, 21 and For Comparative Examples 7 to 11, a three-layer resin sheet comprising a concave layer / sealant resin layer / base material layer was obtained by a feed block method using three 40 mm single-screw extruders and a T-die, Except that the material composition and thickness of each layer were set as shown in Table 3, it was the same as in Example 13, and the concave shape was changed to the concave shape shown in FIGS. To 24 and Comparative Examples 7 to 12 were prepared. Further, the obtained liquid repellent resin sheet was subjected to the same evaluation test as in Example 13, and the results are shown in Table 4.

  In Comparative Example 7, no liquid repellent layer is formed, and in Comparative Example 8, a concave shape is not provided. Comparative Example 9 gives a bell-shaped convex shape, and Comparative Example 10 does not contain hydrophobic silica. In Comparative Example 11, the liquid repellent layer does not contain a binder resin, and in Comparative Example 12, the composition uses silica that has not been subjected to hydrophobic surface treatment.

From the results shown in Table 4, the following became clear.
Although a slight performance decrease in the liquid repellency of Example 18 is observed, in all of Examples 13 to 17 and 19 to 24, the liquid repellency for each liquid in the sheet (contact angle, sliding angle, hydraulic pressure test). The results were that the contact angle was 130 ° or more, the falling angle was 40 ° or less, and the pressure test was 4 or more. On the other hand, in Comparative Example 7, the result was 3 or less in the hydraulic pressure test. In Comparative Example 8, the contact angle was 130 ° or more and the sliding angle was 40 ° or less. . In Comparative Example 9, although a result that the contact angle was 130 ° or more was obtained, the falling angle was 40 ° or more and 3 or less in the pressure test. Further, in Comparative Example 10, the hydraulic pressure test was 3 or less, and in Comparative Example 11, the effect was obtained with respect to any of the contact angle, the falling angle, and the hydraulic pressure test, but the coated hydrophobic silica was detached. It was seen. In Comparative Example 12, no effect was obtained with respect to any of the contact angle, the falling angle, and the hydraulic pressure test.

<Example 25 (concave shape of FIG. 5, layer structure of FIG. 9)>
A mixture of (A-1) 50% by mass of random polypropylene and (C) 50% by mass of styrene-conjugated diene block copolymer resin as the material for the concave layer, and (M) as a material for the base material layer. Using a mixture of 5% by mass of a hydrogenated styrene-based thermoplastic elastomer and 95% by mass of the (Q) HIPS resin, a concave layer and a substrate are formed by a feed block method using two 40 mm single screw extruders and a T die. A two-layer resin sheet consisting of layers was extruded. This extruded sheet was cast with a transfer roll and a touch roll having a convex shape on the surface by a diamond bite engraving method to give the concave shape to the surface on the concave layer side.

  Next, the (J) hydrophobic silica and the (L) binder resin are mixed so that the composition ratio is such that the hydrophobic silica in the liquid-repellent layer is 66 mass% and the binder resin is 34 mass% in solid content ratio. A liquid repellent layer was formed on the surface of the concave layer provided with the concave shape in the same manner as in Example 1 except that the prepared dispersion liquid (both solvents were a mixture of purified water / isopropyl alcohol) was prepared. The thickness of each layer of the resin sheet on which the liquid repellent layer is formed is shown in Table 3 (the numerical value in parentheses of the liquid repellent layer indicates the thickness of the liquid repellent layer after drying). Various characteristics of the liquid repellent resin sheet produced as described above were evaluated by the above-described methods. The results are shown in Table 4.

<Example 26 (concave shape of FIG. 1, layer structure of FIG. 9)>
Except that the material composition and thickness of each layer were set as shown in Table 3, the same procedure as in Example 25 was performed, and the concave shape shown in FIG. A functional resin sheet was prepared. The obtained liquid repellent resin sheet was subjected to the same evaluation test as in Example 25, and the results are shown in Table 4.

  From the results shown in Table 4, the following became clear. That is, in Examples 25 and 26, the results satisfying all the evaluation criteria regarding the liquid repellency (contact angle, falling angle, hydraulic pressure test) for each liquid in the sheet were obtained.

<Example 27 (concave shape in FIG. 1, layer structure in FIG. 10)>
The (A-1) random polypropylene as the material for the concave layer, the (O) modified olefin resin as the material for the first sealant resin layer, and the (U) as the material for the oxygen barrier substrate layer. ) By using the ethylene-vinyl alcohol copolymer as the material for the second sealant resin, the (P) modified olefin resin, and the feed block method using four 40 mm single-screw extruders and a T-die. After laminating in the order of the shape layer / first sealant resin layer / oxygen barrier substrate layer / second sealant resin layer, extrusion lamination is performed on the (S) PET resin (film) to be the substrate layer, and the concave A five-layer resin sheet comprising a shape layer / first sealant resin layer / oxygen barrier substrate layer / second sealant resin layer / substrate layer was obtained. At that time, casting was performed with a transfer roll and a touch roll having a convex shape on the surface by a diamond bite engraving method, and a concave shape was imparted to the surface on the concave layer side.

  Subsequently, a liquid repellent layer was formed on the surface of the concave layer provided with the concave shape in the same manner as in Example 1. The thickness of each layer of the resin sheet on which the liquid repellent layer is formed is shown in Table 5 (the numerical value in parentheses of the liquid repellent layer indicates the thickness of the liquid repellent layer after drying). Various characteristics of the liquid repellent resin sheet produced as described above were evaluated by the above-described methods. The results are shown in Table 6.

<Examples 28 to 39, Comparative Examples 13 to 18>
For Examples 28, 29, 33, 36 to 39, and Comparative Examples 13 and 16, except that the material composition and thickness of each layer were set as shown in Table 5, Examples 30 to 32, 34, 35, and Comparative Examples 14, 15, 17 and 18 were obtained by a feed block method using five 40 mm single-screw extruders and a T-die to form a concave layer / first sealant resin layer / oxygen barrier group. A five-layer resin sheet consisting of a material layer / second sealant resin layer / base material layer was obtained, and the material composition and thickness of each layer were set as shown in Table 5. About the shape, the concave shape shown in FIGS. 1 and 3 to 7 was given by changing the transfer roll, and liquid repellent resin sheets according to Examples 28 to 39 and Comparative Examples 13 to 18 were produced. The obtained liquid repellent resin sheet was subjected to the same evaluation test as in Example 27, and the results are shown in Table 6.

  In Comparative Example 13, a liquid repellent layer is not formed, and in Comparative Example 14, a concave shape is not provided. Comparative Example 15 gives a bell-shaped convex shape, and Comparative Example 16 does not contain hydrophobic silica. In Comparative Example 17, the liquid repellent layer does not contain a binder resin, and in Comparative Example 18, the composition uses silica that has not been subjected to hydrophobic surface treatment.

From the results shown in Table 6, the following became clear.
Although there is a slight performance decrease in the liquid repellency of Example 32, in all of Examples 27 to 31, 33 to 39, the liquid repellency of each liquid on the sheet (contact angle, falling angle, hydraulic pressure test). The results were that the contact angle was 130 ° or more, the falling angle was 40 ° or less, and the pressure test was 4 or more. On the other hand, in Comparative Example 13, the result was 3 or less in the hydraulic pressure test. In Comparative Example 14, the contact angle was 130 ° or more and the falling angle was 40 ° or less. . In Comparative Example 15, the result that the contact angle was 130 ° or more was obtained, but the rolling angle was 40 ° or more and 3 or less in the pressure test. Further, in Comparative Example 16, the hydraulic pressure test was 3 or less, and in Comparative Example 17, the effects were obtained with respect to any of the contact angle, the falling angle, and the hydraulic pressure test, but the coated hydrophobic silica was detached. It was seen. In Comparative Example 18, no effect was obtained with respect to any of the contact angle, the falling angle, and the hydraulic pressure test.

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

DESCRIPTION OF SYMBOLS 1 Concave-shaped layer 1a Concave-shaped 1b Concave-shaped deepest part h Concave-shaped depth t1 Concave-shaped deepest part space | interval d Concave-shaped opening diameter 2 Liquid repellent layer 3 Sealant resin layer 3a 1st sealant resin layer 3b 2nd sealant resin layer 4 Base material layer 5 Oxygen barrier base material layer 6 Container flange 7 Container bottom surface

Claims (13)

  A liquid repellent resin sheet comprising a concave layer made of a thermoplastic resin composition having a fine concave shape, and a liquid repellent layer made of hydrophobic inorganic fine particles and a binder resin on the concave shape surface of the concave layer. .   The liquid repellent resin sheet according to claim 1, wherein the content of the hydrophobic inorganic particles in the liquid repellent layer is 30 to 80% by mass, and the content of the binder resin is 70 to 20% by mass.   The opening diameter of the concave shape is 10 μm to 150 μm, the interval between the deepest concave portions is 5 μm to 180 μm, the depth of the concave shape is 10 μm to 200 μm, and the aspect ratio (the depth of the concave shape / the concave shape) The liquid repellent resin sheet according to claim 1 or 2, which has an opening diameter of 0.5 to 2.0. 4. The liquid-repellent resin sheet according to claim 1, wherein the number of the concave shapes per 1 cm ^{2 on the} surface of the resin sheet is 2500 to 9500000. 5.   The liquid-repellent resin sheet according to any one of claims 1 to 4, wherein a melt mass flow rate of the thermoplastic resin composition is 5 g / 10 min or more.   The liquid repellent resin sheet according to any one of claims 1 to 5, wherein the binder resin is an olefin copolymer.   The liquid-repellent resin sheet according to any one of claims 1 to 6, wherein the hydrophobic inorganic fine particles are hydrophobic silica fine particles whose surface is modified with a trimethylsilyl group or dimethylpolysiloxane.   The liquid repellent resin sheet according to any one of claims 1 to 7, wherein the hydrophobic inorganic fine particles have an average particle diameter of 5 to 1000 nm.   The liquid-repellent resin sheet according to any one of claims 1 to 8, wherein the concave layer has a thickness of 50 µm to 1000 µm.   A styrene resin, olefin resin, polyester resin, nylon resin, ethylene-vinyl alcohol copolymer resin, acrylic resin, polycarbonate resin, and heat The liquid-repellent resin sheet according to any one of claims 1 to 9, wherein one or more base material layers made of one or more kinds of resins selected from plastic elastomers are laminated.   An article using the liquid repellent resin sheet according to any one of claims 1 to 10.   The article according to claim 11, wherein the article is a household item, a packaging material, or a building material member.   The article according to claim 11, which is a food container, a pouch, a rain gown, an umbrella, a wallpaper, or a watering member.