TW201800224A - Liquid-repellent resin sheet and article using same - Google Patents

Abstract

A liquid-repellent resin sheet provided with liquid repellency that is stable in response to pressure from a liquid can be obtained by the use of a resin sheet provided with a convex shape layer (1) having at least one type of fine convex shapes (1a) and containing a thermoplastic resin composition, and a liquid-repellent layer (2) containing hydrophobic inorganic microparticles and a binder resin on the surface having the convex shapes (1a), the liquid-repellent layer (2) having a hydrophobic inorganic microparticle content of over 80 mass% to 95 mass%, and a binder resin content of 5 mass% to less than 20 mass%.

Description

Liquid-repellent resin sheet and article using the same

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

In the past, paper materials and polymer materials were used as packaging materials for foods or daily necessities such as soft drinks, fruit juice drinks, and food and drink. For example, in Patent Document 1, a resin sheet having a liquid-repellent property is proposed in which a concave-convex shape is provided on a resin sheet, and a water-repellent agent is applied to the surface.

However, the liquid-repellent resin sheet described in Special Case Document 1 causes the liquid to adhere to the surface of the liquid-repellent resin sheet due to the pressure given by the liquid, that is, the liquid-repellent property is reduced or lost, and the liquid-repellent property is lost. There is a problem with sexual stability.

[Patent Document 1] International Publication No. 2014/087695

An object of the present invention is to provide a resin sheet having a liquid-repellent property that is stable against pressure from a liquid, and an article using the liquid-repellent resin sheet.

The inventors of this case conducted research on various methods of displaying liquid-repellency, and found that the surface of the sheet imparts a fine convex shape, and a liquid-repellent layer containing hydrophobic inorganic particles and a binder resin is provided at a specific ratio. The liquid repellency that is stable to the pressure from the liquid can be imparted to the surface of the sheet, and the present invention has been completed.

The present invention that solves the above problems is obtained by the following configuration. (1) A liquid-repellent resin sheet comprising: a convex-shaped layer having at least one fine convex shape and containing a thermoplastic resin composition; and hydrophobic inorganic fine particles containing a convex-shaped surface of the convex-shaped layer and Liquid-repellent layer of the binder resin; The content of the hydrophobic inorganic fine particles in the liquid-repellent layer is more than 80% by mass and 95% by mass, and the content of the binder resin is more than 5% by mass and less than 20% by mass. (2) The liquid-repellent resin sheet according to (1), which is liquid-repellent to an aqueous liquid containing sugar. (3) The liquid-repellent resin sheet according to (1) or (2), wherein the melt mass flow rate of the thermoplastic resin composition at 230 ° C. is 5 g / 10 minutes or more. (4) The liquid-repellent resin sheet according to any one of (1) to (3), wherein the thermoplastic resin composition contains a polyolefin-based resin composition. (5) The liquid-repellent resin sheet according to (4), wherein the polyolefin-based resin composition contains 35 to 100% by mass of a polyolefin-based resin. (6) The liquid-repellent resin sheet according to any one of (1) to (5), wherein the hydrophobic inorganic fine particles are hydrophobic silica particles having a trimethylsilyl group on the surface. (7) The liquid-repellent resin sheet according to any one of (1) to (6), wherein the average primary particle diameter of the hydrophobic inorganic fine particles is 5 nm to 1000 nm. (8) The liquid-repellent resin sheet according to any one of (1) to (7), wherein the binder resin contains one or more resins selected from the group consisting of an olefin-based copolymer and a fluorine-based copolymer. (9) The liquid-repellent resin sheet according to any one of (1) to (8), wherein the convex shape is composed of a first convex shape and a second convex shape, a height of the first convex shape, and a second convex shape The heights of the shapes are 20 μm to 150 μm, and the interval between the vertexes of adjacent convex shapes is 20 μm to 100 μm. (10) The liquid-repellent resin sheet according to any one of (1) to (9), wherein the thickness of the convex-shaped 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 when the surface having the liquid-repellent layer side is in contact with a liquid containing sugar is 130 ° or more, and slips The angle is 40 ° or less. (12) The liquid-repellent resin sheet according to any one of (1) to (11), wherein the liquid-repellent property is maintained on the surface of the convex-shaped layer even when a pressure of 866 Pa is applied from the liquid. (13) The liquid-repellent resin sheet according to any one of (1) to (12), wherein one or more substrate layers are laminated on the other side of the convex-shaped layer having the convex-shaped surface, and The base material layer contains one or more resins selected from the group consisting of a styrene resin, an olefin resin, a polyester resin, a nylon resin, an ethylene-vinyl alcohol copolymer resin, and an acrylic resin. (14) The liquid-repellent resin sheet according to (13), wherein a sealant resin layer is formed between the convex layer and the base material layer, and the sealant resin layer contains a material selected from the group consisting of a modified olefin polymer resin and A resin of at least one of thermoplastic elastomers. (15) An article using the liquid-repellent resin sheet according to any one of (1) to (14). (16) The article of (15), wherein the article is a daily necessities, packaging materials or building materials. (17) The article according to (16), wherein the article is a food container, a bag, a raincoat, an umbrella, a wallpaper, or a member of a water place.

According to the present invention, it is possible to provide a liquid-repellent resin sheet having liquid-repellency that is stable against pressure from a liquid, and an article using the liquid-repellent resin sheet.

[First Embodiment] The liquid-repellent resin sheet according to the first embodiment of the present invention has liquid-repellency, as shown in FIG. 1, and includes: a resin having a thermoplastic resin composition having at least one fine convex shape (1a) Convex-shaped layer (1); and a liquid-repellent layer (2) containing hydrophobic inorganic fine particles and a binder resin on a surface having the convex shape (1a); the content of the hydrophobic inorganic fine-particles in the liquid-repellent layer exceeds 80 The mass content is 95% by mass or less, and the content of the binder resin is 5 mass% or more and less than 20 mass%.

<Convex-shaped layer> A convex-shaped layer can be formed using a thermoplastic resin composition. Examples of the thermoplastic resin composition include polyolefin resins, polystyrene resins, polyester resins, and polyvinylidene fluoride resins. For example, when it is used as a food container, it is preferable to use polyolefin resin, and it is preferable to contain 35 mass% or more of polyolefin resin especially. When the polyolefin resin is 35% by mass or more, the transferability of the convex shape can be improved. In addition, the melt mass flow rate of the polyolefin-based resin composition at 230 ° C. is preferably 5 g / 10 minutes or more, and more preferably 15 g / 10 minutes or more. When the melt mass flow rate is 5 g / 10 minutes or more, the transferability of the convex shape can be improved. Here, the melt mass flow rate is calculated in accordance with JIS K 7210 by measuring the outflow mass (g / 10 minutes) at regular intervals. As a standard condition, the melt mass flow rate is measured at a test temperature of 190 ° C to 230 ° C and a load of 2.16 kg to 10.00 kg.

The polyolefin resin refers to a resin mainly containing a polymer containing an α-olefin as a monomer, and particularly preferably a polyethylene resin and a polypropylene resin. Examples of the polyethylene resin include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, linear medium-density polyethylene, and a copolymer or a graft copolymer obtained by using ethylene as a main component. Also includes these mixtures. Examples of the copolymer include ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, ethylene-methacrylate copolymer, and ethylene-vinyl acetate-chlorinated ethylene copolymer. Examples of the above-mentioned graft copolymer include a styrene-ethylene graft copolymer.

Examples of the polypropylene resin include homopolypropylene, random polypropylene, and block polypropylene. When homopolypropylene is used, the structure of the homopolypropylene may be any of the same row, miscellaneous row, and opposite row. When random polypropylene is used, as for the α-olefin copolymerized with propylene, a carbon number of 2 to 20 is preferable, and a carbon number of 4 to 12 is more preferable. For example, ethylene, 1-butene, 1 -Pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and the like. When a block polypropylene is used, a block copolymer (block polypropylene), a block copolymer containing a rubber component, a graft copolymer, etc. are mentioned. These olefin resins may be used alone or in combination with other olefin resins.

The thermoplastic resin composition may contain other additives as long as the effect of the present invention is not impaired. Other additives include stabilizers, surfactants, lubricants, fillers, foaming agents, colorants, and nucleating agents.

(Convex shape) The convex shape layer has one or more fine convex shapes. Although the convex shape may be one of the convex shapes shown in FIG. 1, it is preferable that the convex shape has a first convex shape and a second convex shape having different shapes as shown in FIG. 3. In addition, the convex shape may have three or more convex shapes having different shapes. When the convex shape here has the first convex shape and the second convex shape, the height of the first convex shape is higher than the height of the second convex shape. Although the arrangement of the first convex shape and the second convex shape is not limited, it is preferable that the first convex shape and the second convex shape are arranged alternately in terms of liquid-repellent surface. The configuration of the convex shape is not particularly limited, and there are a checkerboard configuration and a staggered configuration in the vertical and horizontal configurations. To maintain liquid repellency better, staggered configuration is recommended. The method for forming the convex-shaped layer is not particularly limited, and a conventional method can be used. For example, a method of casting the surface of a resin sheet by casting with a transfer roller and a contact roller having an uneven shape formed by a laser engraving method, or heating the sheet with a belt mold and applying pressure How to transfer unevenness.

The height (h) of the convex shape is preferably 20 μm to 150 μm. When the height of the convex shape is 20 μm or more, liquid repellency can be sufficiently ensured, and when the height of the convex shape is 150 μm or less, the size of the convex shape in the mold for providing the convex shape can be stabilized. Among them, the height of the convex shape is a thickness (100 nm to 4000 nm) of a liquid-repellent layer described later. The thickness of the convex-shaped layer is not particularly limited, and the height including the above-mentioned convex shape may be 50 μm to 1000 μm.

The apex interval (t) of adjacent convex shapes should be 20 μm to 100 μm. Among them, the vertex interval refers to the interval between adjacent convex shapes having the shortest distance. Even if the convex shapes are different from each other, as long as they are adjacent, it means the interval between the convex shapes. By setting the interval between the vertices to be 20 μm or more, the convex shape size in the mold for providing a convex shape can be stabilized. Moreover, when it is 100 micrometers or less, the fall of liquid repellency can be prevented.

The height of the convex shape and the apex interval 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 ratio of the height of the second convex shape to the height of the first convex shape is preferably 0.4 or more and 0.8 or less. A more effective liquid repellency can be obtained by setting the ratio of the height to 0.4 or more and 0.8 or less.

The convex shape can be a triangular shape, a quadrangular shape, a hexagonal shape, an octagonal shape, a cone shape, a pyramid shape, a truncated cone shape, and the like. The inventor of this case conducted various studies on the structure of the resin sheet of this embodiment, and knew that The convex shape of the hexagonal cone shape is particularly desirable.

<Liquid-repellent layer> The liquid-repellent layer substantially maintains the convex shape of the convex-shaped layer originally on the surface of the sheet, and forms a substantially constant thickness on the surface of the convex-shaped layer. The liquid-repellent layer is provided in order to maintain the liquid-repellency even after forming a member, and is formed by using hydrophobic inorganic fine particles and a binder resin. Although the thickness of the liquid-repellent layer is preferably 100 nm to 4000 nm, there is no particular limitation as long as the effect of the present invention can be obtained. Here, "liquid repellency" means liquid repellency to the extent that sugar-based liquids (liquid containing sugars) are prevented from adhering to the resin sheet, and specifically, the contact angle of the liquids of these liquids to the resin sheet The meaning is 130 ° or more and / or the slip angle is 40 ° or less. The contact angle and the slip angle can be measured for a resin sheet using an automatic contact angle meter (for example, DM-501 manufactured by Kyowa Interface Chemical Co., Ltd.). In addition, "maintaining liquid repellency even when a pressure of 866 Pa is applied from a liquid" means the meaning of stable liquid repellency to the pressure from a liquid, and means that the pressure is still applied even if a pressure of 866 Pa is applied to the liquid. The meaning of maintaining liquid repellency.

The liquid-repellent layer is characterized in that the content of the hydrophobic inorganic fine particles exceeds 80% by mass and is 95% by mass or less, and the content of the binder resin is 5% by mass or more and less than 20% by mass. In addition, the content of the hydrophobic inorganic fine particles is 85% to 95% by mass, and the content of the binder resin is preferably 5% to 15% by mass. By having a composition in this range, stable liquid repellency can be obtained even when pressure is applied from a liquid. On the other hand, when the content of the hydrophobic inorganic fine particles is 80% by mass or less, the liquid-repellent property that is sufficiently stable when pressure is applied from a liquid may not be obtained. When the content of the hydrophobic inorganic fine particles exceeds 95% by mass, sometimes The hydrophobic inorganic fine particles may peel off.

For the method of forming a liquid-repellent layer on a convex surface, a dispersion liquid prepared by adding hydrophobic inorganic fine particles in isopropyl alcohol (IPA) in advance is used, and then mixed with an adhesive resin at an arbitrary ratio to the convex shape. A method of coating the surface with a coater or the like.

(Hydrophobic Inorganic Fine Particles) The hydrophobic inorganic fine particles may be those having a hydrophobic group, and may be those having been made hydrophobic by surface treatment. For example, the surface has trimethylsilyl, dimethylsilyl, alkylsilyl, aminoalkylsilyl, methacrylic silyl, dimethylpolysilyl, or dimethylsilyl Hydrophobic silica particles are preferred. In addition, fine particles obtained by subjecting hydrophilic inorganic fine particles to a surface treatment with a silane coupling agent to make the surface state hydrophobic can also be used. The type of the inorganic substance is not limited as long as it is hydrophobic. Among these, at least one of hydrophobic fumed silica, fused silica, alumina, and titanium dioxide can be used. There is no restriction on the shape of these particles as long as they are hydrophobic, and any of spherical and non-spherical (fragmented) shapes can be used. The average primary particle size should be 5nm ~ 1000nm, more preferably 7nm ~ 200nm, and even more preferably 7nm ~ 25nm. By setting the average primary particle diameter to 5 nm to 1000 nm, while achieving the liquid repellency satisfying the conditions of the present invention, the dispersibility with respect to the binder resin can be made good. Among them, the average primary particle size refers to the use of a scanning electron microscope to change the field of view and take multiple images. The image analysis software is used to measure the diameter of 3,000 to 5,000 hydrophobic inorganic particles randomly extracted, and the average value is calculated. And get the value. As specific examples of these, for example, for silicon dioxide, the product names "AEROSIL R972", "AEROSIL R972V", "AEROSIL R972CF", "AEROSIL R974", "AEROSIL RX200", "AEROSIL RY200" (above) (Manufactured by NIPPON AEROSIL CO., LTD.), "AEROSIL R202", "AEROSIL R805", "AEROSIL R812", "AEROSIL R812S", "AEROSIL RY300" (the above are manufactured by EVONIK Degussa Co., Ltd.), etc. As for titanium dioxide, the product name "AEROXIDE TiO2 T805" (manufactured by EVONIK Degussa Co., Ltd.) and the like can be exemplified. For the alumina, for example, the product name "AEROXIDE Alu C" (manufactured by EVONIK Degussa Co., Ltd.) and the like are treated with a silane coupling agent to make the surface of the particles hydrophobic particles.

(Binder resin) The binder resin refers to a dispersion obtained by dispersing any one or more of an olefin-based copolymer and a fluorine-based copolymer in water. In the present specification, the content of the binder resin refers to the content of the solid content in which the resin is the main component in the binder resin used.

The olefin-based copolymer refers to a polymer containing an α-olefin as a monomer, and includes a polyethylene-based polymer or a polypropylene-based polymer. Examples include low-density polyethylene, ultra-low-density polyethylene (copolymer of ethylene and α-olefin), ethylene-vinyl acetate copolymer (EVA), ethylene-alkyl acrylate copolymer, and ethylene-methacrylate. Base ester copolymers, ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, ionic polymers such as low-density polyethylene, propylene-based elastomer materials, and the like. Examples of commercially available products include "CHEMIPEARL S-100" (manufactured by Mitsui Chemicals), "AQUATEX AC-3100", "AQUATEX EC-3500" (manufactured by Japan Coating Resin Corporation), and "Arrows base" SE-1200 "," Arrows base SD-1200 "," Arrows base YA-4010 "(manufactured by UNITIKA LTD.), Etc.

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

The structural unit (a) is a group obtained by substituting part or all of a hydrogen atom with a fluorine atom for an alkyl group, and having 1 to 6 carbon atoms. The structural unit (a) may be a chain polyfluorocarbon group having an unsaturated bond such as one or more carbon-carbon unsaturated double bonds. The unsaturated group is preferably a (meth) acrylate group.

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

The structural unit (c) is a monomer derived from a monomer having a fluorine atom-free and crosslinkable functional group. As far as the crosslinkable functional group is concerned, it is preferably an isocyanate group, a blocked isocyanate group, an alkoxysilyl group, an amine group, an alkoxymethylamidino group, a silanol group, an ammonium group, an amidino group, and a Oxygen, hydroxyl, An oxazoline group, a carboxyl group, an alkenyl group, a sulfonic group, and the like. In addition, it is more preferably an epoxy group, a hydroxyl group, a blocked isocyanate group, an alkoxysilyl group, an amine group, or a carboxyl group.

As the monomer forming the structural unit (c), a (meth) acrylate, a compound having two or more copolymerizable groups, a vinyl ether, or a vinyl ester is preferable. The structural unit (c) may be a mixture of two or more kinds. The structural unit (c) mainly affects the film-forming property of the liquid-repellent film, the adhesion or adhesion of the liquid-repellent composition to 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 obtained from a homogeneous copolymer solution or dispersion having good film forming properties. As far as the structural unit (d) is concerned, it is particularly preferably derived from vinyl chloride, vinylidene chloride, cyclohexyl methacrylate, polyoxyethylene di (meth) acrylate, polyoxyethylene di (meth) acrylate Alkyl ether, dioctyl maleate. The structural unit (d) can contribute to improvement of the adhesion of the composition to the substrate or improvement of the dispersibility.

For these commercially available products, "AsahiGuard AG-E070", "AsahiGuard AG-E550D" (manufactured by Asahi Glass Co., Ltd.), "UNIDYNE TG-5546", "UNIDYNE TG-5671", "UNIDYNE TG- 6071 "(manufactured by Daikin Industries, Ltd.).

<Water-based liquid> The water-based liquid system in this embodiment uses water as a solvent and has a fluid liquid, regardless of the viscosity of the liquid. In particular, it includes liquids for foods such as sugar-containing liquids. Specifically, it includes yogurt, jelly, pudding, jam, syrup, tomato sauce, fruit 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, there is a convex-shaped layer (1) and a substrate obtained by laminating a liquid-repellent layer (2) on the surface as shown in FIG. A resin sheet having a sealant resin layer (3) formed between the material layers (4). That is, the layer structure of the resin sheet of the second embodiment is a liquid-repellent layer (2), a convex-shaped layer (1), a sealant resin layer (3), and a base material layer (4) from top to bottom. Here, since the liquid-repellent layer and the convex-shaped layer are the same as those described in the first embodiment, description thereof will be omitted. However, the thickness of the convex-shaped layer should be 50 μm to 200 μm. When it is 50 μm or more, the transfer of the convex shape can be prevented from becoming defective. In addition, when the thickness is 200 μm or less, production costs can be prevented from increasing.

<Base material layer> The base material layer is preferably a styrene resin (impact-resistant polystyrene, polybutadiene-polystyrene-polyacrylonitrile graft polymer, etc.), and an olefin resin (polyethylene, polypropylene Etc.), polycarbonate, polyester resins (polyethylene terephthalate, polybutylene terephthalate, etc.), nylon resins (nylon 6, nylon-66, etc.), ethylene-vinyl alcohol copolymerization Materials, thermoplastic resins such as acrylic resins. In addition, when lamination is performed, there are laminations formed by coextrusion, laminations formed by an extruded layer using a non-stretched film, a biaxially stretched film, and a dry layer.

The base material layer is preferably a polyester resin. For example, as the polyester resin used as the base material layer, polyethylene terephthalate, polybutylene terephthalate, polyethylene 2,6-naphthalate, and polydimethyl terephthalate can be used. Esters, and diol components such as diethylene glycol, neopentyl glycol, polyalkylene glycol, or adipic acid, sebacic acid, phthalic acid, isophthalic acid, 2,6-naphthalene A polyester resin obtained by copolymerizing a dicarboxylic acid component such as a dicarboxylic acid as a copolymerization component.

In the base material layer, according to requirements, colorants such as pigments and dyes, release agents such as silicone oil, fiber-like reinforcing agents such as glass fiber, fillers such as talc, clay, and silicon dioxide can be added within a range that does not impair the effects of the present invention. , Salt compounds such as sulfonic acids and alkali metals, antistatic agents such as polyalkylene glycols, ultraviolet absorbers, and antibacterial agents. In addition, waste resin 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 exhibits adhesion between the convex-shaped layer and the substrate layer. The resin component includes 100% by mass of a modified olefin polymer resin and 100% by mass of a thermoplastic elastomer.

The sealant resin layer is preferably a modified olefin-based polymer. Examples of the modified olefin-based polymer resin include olefins having a carbon number of about 2 to 8 such as ethylene, propylene, and 1-butene, and such olefins with ethylene, propylene, 1-butene, and 3- Copolymers of other olefins with 2 to 20 carbons, such as methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, and 1-decene Or olefin resins such as copolymers of such olefins with vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, acrylates, methacrylates, styrene and other ethylene compounds; ethylene-propylene copolymers, ethylene-propylene -Diene copolymers, ethylene-1-butene copolymers, propylene-1-butene copolymers and other olefin-based rubbers, such as acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, Unsaturated carboxylic acids, such as itaconic acid, citraconic acid, and tetrahydrophthalic acid, or their halides, amidines, amines, anhydrides, esters and other derivatives, specifically maleic chloride, Maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, propylene oxide maleate, etc., under the conditions of the graft reaction Those derived modified.

Among these, an ethylene-propylene-diene copolymer, an ethylene-propylene, or a 1-butene copolymer rubber modified by an unsaturated dicarboxylic acid or an anhydride thereof, especially maleic acid or an anhydride thereof is suitable.

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

[Third Embodiment] As shown in FIG. 6, the resin sheet of the third embodiment of the present invention is not used for the sealant resin layer (3) shown in the second embodiment, and the convex-shaped layer (1) and The base material layer (4) is obtained by laminating directly. That is, the resin sheet structure of the third embodiment is a liquid-repellent layer (2), a convex-shaped layer (1), and a substrate layer (4) from the top to the bottom, and has a seal removed from the thermoplastic resin sheet of the second embodiment. Structure of agent resin layer. Here, since the liquid-repellent layer and the convex-shaped layer are the same as those in the first embodiment and the second embodiment, description thereof will be omitted. On the other hand, the substrate layer (4) in this embodiment is preferably one having sufficient adhesion to the convex-shaped layer.

Therefore, in the resin sheet of the third embodiment, it is preferable to use a styrene resin having excellent adhesion to the convex-shaped layer as the base material layer. Contains 60% to 15% by mass of styrene resin, more preferably 55% to 15% by mass of polystyrene resin and 40% to 85% by mass, and more preferably 45% to 85% A styrene-based base material layer made of a mass-% impact-resistant polystyrene resin is preferable. In addition, a styrene-based resin composition obtained by adding a hydrogenated styrene-based thermoplastic elastomer may be used. When a polystyrene resin and a hydrogenated styrene-based thermoplastic elastomer are used together, it is preferably made of a polystyrene-based resin containing 90% to 95% by mass and a hydrogenated styrene-based thermoplastic elastomer of 5% to 10% by mass. A styrene-based resin composition. At this time, if the amount of hydrogenated styrene-based thermoplastic elastomer is less than 5% by mass, the adhesion with the convex-shaped layer may be insufficient, and interlayer peeling may occur. If it exceeds 10% by mass, production costs may change. High situation.

[Fourth Embodiment] As shown in FIG. 7, the resin sheet according to the fourth embodiment of the present invention includes a liquid-repellent layer (2), a convex-shaped layer (1), a first sealant resin layer (3a), and oxygen. A resin sheet obtained by laminating a barrier substrate layer (5), a second sealant resin layer (3b), and a substrate layer (4) in this order. The composition of the first sealant resin layer and the second sealant resin layer may be the same or different. The thickness of the convex-shaped layer is preferably 50 to 250 μm. If it is less than 50 μm, the convex shape may be poorly transferred. Moreover, when it exceeds 200 micrometers, production costs may become high.

<Base material layer> The resin used as a base material layer in the fourth embodiment is preferably a nylon-based resin or a methacrylate-based resin. Examples of nylon resins include lactam polymers such as caprolactam and laurylamine, amine groups such as 6-aminohexanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. Polymers of carboxylic acids, hexamethylene diamine, decanediamine, dodecamethylene diamine, aliphatic diamines such as 2,2,4- or 2,4,4-trimethylhexanediamine, 1,3 -Or alicyclic diamines such as 1,4-bis (aminomethyl) cyclohexane, bis (p-aminocyclohexylmethane), aromatic diamines such as m-xylylenediamine or p-xylylenediamine Diamine unit with aliphatic dicarboxylic acids such as adipic acid, suberic acid, sebacic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, etc. Polycondensates of dicarboxylic acid units such as acids, 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 which nylon 6 and nylon MXD6 are suitable.

The methacrylate resin may be an ethylene polymer based on a methacrylate monomer, and the structure and the like are not particularly limited. Examples of the methacrylate monomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, and hexyl methacrylate. . Among these, methyl methacrylate is particularly suitable. In addition, alkyl groups such as propyl, butyl, pentyl, and hexyl groups in the methacrylate monomer may be linear or branched. In addition, the methacrylate resin blended into the resin composition of this embodiment may be a homopolymer of a methacrylate monomer or a copolymer of a plurality of methacrylate monomers. Alternatively, it may have monomer units derived from ethylene, propylene, butadiene, styrene, α-methylstyrene, acrylonitrile, acrylic acid, and the like, which are conventional ethylene compounds other than methacrylate.

<Oxygen-blocking base material layer> Examples of the oxygen-blocking base material layer include an ethylene-vinyl alcohol copolymer resin and a nylon-based resin. Among these, an ethylene-vinyl alcohol copolymer resin is preferable in terms of processability and formability.

The ethylene-vinyl alcohol copolymer resin is usually obtained by saponifying an ethylene-vinyl acetate copolymer. In order to have oxygen barrier properties, processability, and formability, the ethylene content is 10 mol% to 65 mol%, and is preferably 20 mol% to 50 mol%, and the degree of saponification is more than 90%, preferably more than 95%.

Examples of the nylon-based resin include caprolactam polymers such as caprolactam and laurylamine, 6-aminohexanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. Polymers of aminocarboxylic acids, hexamethylene diamine, decane diamine, dodecamethylene diamine, aliphatic diamines such as 2,2,4- or 2,4,4-trimethylhexanediamine, 1 Aliphatic diamines such as 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis (p-aminocyclohexylmethane), aromatic diamines such as m-xylylenediamine or p-xylylenediamine Diamine units such as amines, and aromatic dicarboxylic acids such as adipic acid, suberic acid, and sebacic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; aromatics such as terephthalic acid and isophthalic acid Polycondensates of dicarboxylic acid units such as dicarboxylic acids, and copolymers thereof.

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, and nylon 6 / 610, nylon 6 / 6T, nylon 6I / 6T, etc., among which nylon 6 and nylon MXD6 are suitable.

<Sealant resin layer> The sealant resin layer is preferably a modified olefin-based polymer. Examples of the modified olefin-based polymer resin include olefins having a carbon number of about 2 to 8 such as ethylene, propylene, and 1-butene, and such olefins with ethylene, propylene, 1-butene, and 3- Copolymers of other olefins with 2 to 20 carbons, such as methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, and 1-decene Or olefin resins such as copolymers of such olefins with vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, acrylates, methacrylates, styrene and other ethylene compounds; ethylene-propylene copolymers, ethylene-propylene -Diene copolymers, ethylene-1-butene copolymers, propylene-1-butene copolymers and other olefin-based rubbers, such as acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, Unsaturated carboxylic acids, such as itaconic acid, citraconic acid, and tetrahydrophthalic acid, or their halides, amidines, amines, anhydrides, esters and other derivatives, specifically maleic chloride, Maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, propylene oxide maleate, etc., under the conditions of the graft reaction Of those obtained.

Among them, vinyl resins, propylene resins, ethylene-propylene or 1-butene copolymer rubbers modified with unsaturated carboxylic acids or anhydrides, especially maleic acid or anhydrides thereof are suitable.

As far as the thickness of the sealant resin layer is concerned, it is preferably from 10 μm to 50 μm, and more preferably from 20 μm to 40 μm on either side. If it is less than 10 μm, sufficient interlayer adhesion strength may not be obtained, and if it is more than 50 μm, production costs may increase.

[Production of liquid-repellent resin sheet] Although the method for producing the resin sheet of the present invention is not limited, it can be any method, and typically includes the following steps: The surface produced on at least one side has one or more convex shapes A single-layer sheet or a laminated resin sheet containing the layer having a convex shape, and finally a liquid-repellent layer is formed on the surface of the convex shape.

First, when producing a single-layer sheet having at least one convex shape on at least one side or a laminated resin sheet including the layer having the convex shape, any resin sheet forming method can be used. For example, in the case of a single layer, a single-shaft extruder is used, and in the case of multiple layers, a plurality of single-shaft extruders are used to melt-extrude each raw resin and obtain a resin sheet by a T-die. In the case of multiple layers, a multi-manifold die can be used. Among them, 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, when the physical properties and the like do not show deterioration, waste raw materials generated in the manufacturing steps of the resin sheet or member of the present invention can be used. It can be added to the base material layer and laminated as an additional layer.

Then, a convex shape is formed on a single-layer or multi-layer resin sheet. This method is not particularly limited, and any method known to those skilled in the art can be used. For example, there are a manufacturing method using an extrusion molding method, a manufacturing method using a photolithography method, a manufacturing method using a hot press method, and a manufacturing method using a pattern roll and a UV curing resin.

Finally, a liquid-repellent layer containing a specific amount of hydrophobic inorganic fine particles and a binder resin is formed on the surface of the convex-shaped layer. The method for forming the liquid-repellent layer is not particularly limited. For example, conventional coating methods such as roll coating, gravure coating, rod coating, doctor blade coating, bristle coating, and powder electrostatic method can be used. In addition, the solvent used for preparing the coating liquid is not particularly limited, and other than water, for example, alcohol (ethanol), cyclohexane, toluene, acetone, IPA, propylene glycol, hexanediol, butyl diethylene glycol, glutaric acid can be appropriately selected. Organic solvents such as alcohol, n-pentane, n-hexane, and hexanol. In this case, a small amount of a dispersant, a colorant, an anti-settling agent, a viscosity adjusting agent, or the like may be used in combination.

[Article] The liquid-repellent resin sheet of the present invention can be applied to articles whose liquid-repellency is necessary as described above. Specifically, it is as follows.

The liquid-repellent resin sheet of the present invention can be suitably used as packaging materials such as food containers, bags, daily necessities such as raincoats, umbrellas, water-side members such as kitchens, bathrooms, toilets, and building materials such as wallpaper.

For example, by using the liquid-repellent resin sheet of the present invention for food containers, bags, etc., the effect of preventing the contents from adhering to the inner walls of the containers, etc. can be achieved, so that the contents can be easily and completely used at the end, or the cleaning can be reduced during waste sorting The effect of container time.

For example, when the liquid-repellent resin sheet of the present invention is used for rain gear such as a raincoat and an umbrella, it is possible to obtain the effect that it is difficult to attach water droplets and it is difficult to attach water droplets to the hand when folded.

For example, by using the liquid-repellent resin sheet of the present invention as a wall panel of a bathroom, it is possible to obtain an effect that it is difficult to attach water droplets.

For example, by using the liquid-repellent resin sheet of the present invention as an interior material or the like, it is possible to obtain an effect that it is difficult to attach dirt or the like. [Example]

Hereinafter, examples and comparative examples of the present invention will be specifically described, but the present invention is not limited in any way by the contents of the examples and the like.

Various raw materials used in Examples and the like are as follows. (1) Convex shape layer (A) Random polypropylene "PM921V" (manufactured by SunAllomer Ltd.), melt mass flow rate: 25g / 10min (test temperature: 230 ° C, load: 2.16kg) (2) liquid-repellent layer (B) Hydrophobic inorganic fine particles: Hydrophobic silica "AEROSIL R812S" (manufactured by EVONIK Degussa Co., Ltd.), average primary particle diameter: 7nm, trimethylsilyl modified (C) hydrophobic inorganic fine particles: hydrophobic Silicon dioxide "AEROSIL R8200" (manufactured by EVONIK Degussa Co., Ltd.), average primary particle size: 12nm, trimethylsilyl-modified (D) hydrophobic inorganic fine particles: hydrophobic silica "AEROSIL NAX50" ( NIPPON AEROSIL CO., LTD.), Average primary particle size: 30 nm, trimethylsilyl-modified (E) binder resin: olefin-based copolymer "AQUATEX AC-3100" (manufactured by Japan Coating Resin Corporation), ethylene- Methacrylic copolymer resin (F) binder resin: Fluoro copolymer "AsahiGuard AG-E550D" (manufactured by Asahi Glass Co., Ltd.), (meth) acrylate fluoro copolymer resin

Evaluation methods of various characteristics of the resin sheet produced in Examples and the like are as follows.

(1) Observation of convex shape The convex shape of the sheet was measured using a laser microscope VK-X100 (manufactured by KEYENCE CORPORATION) to measure the convex shape height and the apex interval of the convex shape. In addition, in order to measure the convex shape height and the vertex interval, a convex shape cross-section sample was prepared using a microtome. The height of the convex shape was measured from three arbitrary positions of the resin sheet, and the height of each of the ten pieces of the same shape was measured, and the arithmetic average of the 30 measured values was used. When there are two or more convex shapes, the heights of the first convex shape and the height of the second convex shape can be obtained by the same method. Regarding the vertex interval, the vertex interval of 10 adjacent convex shapes was measured from three arbitrary positions of the resin sheet, and the arithmetic average of the 30 measured values was used. When there are two or more convex shapes, the apex interval between the first convex shape and the second convex shape is measured, and an arithmetic average of 30 measured values is used.

(2) Contact angle and slip angle For a resin sheet, an automatic contact angle meter DM-501 (manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the contact angle and slip angle. In addition, as the test solution, pure honey (manufactured by Nisshin Honey Co., Ltd.) and tomato sauce (manufactured by Kokumei Co., Ltd.) were used. The dropwise addition amount was 8 μL during contact angle measurement and 20 μL during slip angle measurement. If the contact angle is 130 ° or more, it can be judged that the liquid repellency is high, and the adhesion of liquid can be prevented. In addition, if the slip angle is 40 ° or less, it can be determined that the liquid repellency is high, and the adhesion of liquid can be prevented.

(3) Pressure test A 1 g test solution was placed on a resin sheet, and a cylindrical polypropylene case (hereinafter referred to as a cylindrical case) was further placed from the liquid to perform a pressure test. The cylindrical shell is 32mm in diameter and weighs 70g. The pressure applied to the liquid is 866Pa. After the pressurization, as shown in FIG. 8, the residual liquid attached to the resin sheet when the cylindrical case was removed was set to a state of “5” without any adhesion and a state of “1” to be adhered most. Evaluation was performed in five stages. In this 5-step evaluation, if it is "4" or more, it is judged that adhesion is suppressed.

<Example 1 (layer structure of FIG. 1)> A 65-mm uniaxial extruder was used to extrude a resin sheet by a T-die method. This extruded sheet was cast by a transfer engraving method using a laser engraving method to transfer rollers and touch rollers having an uneven shape on the surface to obtain a resin sheet having a convex shape layer provided with a convex shape on the surface.

Then, in order to form a liquid-repellent layer on the surface of the convex-shaped layer, 90% by mass of hydrophobic silica and a binder resin made of hydrophobic silica and 10% by mass of the binder resin were produced in the liquid-repellent layer. A dispersion liquid obtained by mixing the composition ratio of% (the solvent is a mixed liquid of purified water / isopropanol). This mixed dispersion liquid was applied on the surface of the convex-shaped layer using a coating bar, and dried at 90 ° C. to form a liquid-repellent layer.

<Examples 2 to 8, Comparative Examples 1 to 5> The composition of the liquid-repellent layer, the presence or absence of the liquid-repellent layer, and the presence or absence of the convex shape were set as shown in Table 1. Except for this, the method was the same as in Example 1, The resin sheets of Examples 2 to 8 and Comparative Examples 1 to 5 were produced and evaluated. The composition of the liquid-repellent layer is shown in Table 1, and the results are shown in Table 2.

Among them, Comparative Examples 1 to 3 changed the content of the silica particles and the binder resin content in the liquid-repellent layer, Comparative Example 4 did not form the liquid-repellent layer, and Comparative Example 5 did not impart a convex shape.

【Table 1】

【Table 2】

The results shown in Table 2 reveal the following. Regarding the liquid repellency (contact angle, slip angle, and pressure test) of each liquid on the tablet, all of Examples 1 to 8 obtained a contact angle of 130 ° or more, a slip angle of 40 ° or less, and a pressure test of 4 or more. result. In contrast, in Comparative Example 1, the liquid-repellent layer was peeled off during the pressure test, and the formed liquid-repellent layer could not be maintained. In Comparative Example 2, a result of a contact angle of 130 ° or more and a slip angle of 40 ° or less was obtained, but it was 3 or less in the pressure test. In Comparative Example 3, a result of a contact angle of 130 ° or more was obtained, but the slip angle was 40 ° or more, and it was 2 or less in the pressure test. In addition, in Comparative Examples 4 and 5, no effect was obtained with respect to any of the contact angle, the slip angle, and the pressure test.

Although the present invention has been described using various embodiments, the technical scope of the present invention is not limited to the scope described in the above embodiments. It is clear that those skilled in the art can make various changes or improvements to the above embodiments. In addition, it is clear from the description of the scope of patent application that the forms obtained by applying such changes or improvements are intended to be included in the technical scope of the present invention.

1a‧‧‧ convex shape
1b‧‧‧ convex vertex
1c‧‧‧Vertex of 1st convex shape
1d‧‧‧ 2nd convex vertex
h‧‧‧ convex shape height
t‧‧‧ interval between convex vertices
2‧‧‧Liquid layer
3‧‧‧ Sealant resin layer
3a‧‧‧The first sealant resin layer
3b‧‧‧Second sealant resin layer
4‧‧‧ substrate layer
5‧‧‧ oxygen barrier substrate layer

[Fig. 1] A schematic longitudinal cross-sectional view showing a liquid-repellent resin sheet according to a first embodiment of the present invention. [Fig. 2] A schematic plan view of the liquid-repellent resin sheet of Fig. 1. [Fig. [Fig. 3] A schematic vertical cross-sectional view of another embodiment of the liquid-repellent resin sheet according to the first embodiment of the present invention. [Fig. 4] A schematic plan view of the liquid-repellent resin sheet of Fig. 3. [Fig. [Fig. 5] A schematic longitudinal cross-sectional view showing a laminated structure of a liquid-repellent resin sheet according to a second embodiment of the present invention. [Fig. 6] A schematic longitudinal cross-sectional view showing a laminated structure of a liquid-repellent resin sheet according to a third embodiment of the present invention. [Fig. 7] A schematic longitudinal sectional view showing a laminated structure of a liquid-repellent resin sheet according to a fourth embodiment of the present invention. [Fig. 8] A diagram showing evaluation criteria of a pressure test of the present invention.

t‧‧‧ interval between convex vertices

h‧‧‧ convex shape height

2‧‧‧Liquid layer

1a‧‧‧ convex shape

Claims (17)

A liquid-repellent resin sheet comprising: a convex-shaped layer having at least one fine convex shape and containing a thermoplastic resin composition; and a hydrophobic inorganic fine particle and a binder resin on a convex-shaped surface of the convex-shaped layer The content of the hydrophobic inorganic fine particles in the liquid-repellent layer is more than 80% by mass and less than 95% by mass, and the content of the binder resin is more than 5% by mass and less than 20% by mass. For example, the liquid-repellent resin sheet of the scope of application for patent No. 1 is liquid-repellent to an aqueous liquid containing sugar. For example, the liquid-repellent resin sheet according to item 1 or 2 of the patent application scope, wherein the melt mass flow rate of the thermoplastic resin composition at 230 ° C. is 5 g / 10 minutes or more. For example, the liquid-repellent resin sheet according to item 1 or 2 of the patent application scope, wherein the thermoplastic resin composition contains a polyolefin-based resin composition. For example, the liquid-repellent resin sheet according to item 4 of the patent application, wherein the polyolefin-based resin composition contains 35% to 100% by mass of the polyolefin-based resin. For example, the liquid-repellent resin sheet according to item 1 or 2 of the patent application scope, wherein the hydrophobic inorganic fine particles are hydrophobic silica particles having trimethylsilyl groups on the surface. For example, the liquid-repellent resin sheet according to item 1 or 2 of the patent application scope, wherein the average primary particle diameter of the hydrophobic inorganic fine particles is 5 nm to 1000 nm. For example, the liquid-repellent resin sheet according to item 1 or 2 of the patent application scope, wherein the binder resin includes one or more resins selected from the group consisting of olefin-based copolymers and fluorine-based copolymers. For example, the liquid-repellent resin sheet of item 1 or 2 of the patent application scope, wherein the convex shape is composed of the first convex shape and the second convex shape, and the height of the first convex shape and the height of the second convex shape are respectively 20μm ~ 150μm, the interval between the apexes of adjacent convex shapes is 20μm ~ 100μm. For example, the liquid-repellent resin sheet according to item 1 or 2 of the patent application scope, wherein the thickness of the convex-shaped layer is 50 μm to 200 μm. For example, the liquid-repellent resin sheet according to item 1 or 2 of the patent application scope, wherein the contact angle when the surface having the liquid-repellent layer side is in contact with a liquid containing sugar is 130 ° or more and the slip angle is 40 ° or less. For example, the liquid-repellent resin sheet according to item 1 or 2 of the patent application scope, wherein the surface of the convex-shaped layer maintains liquid-repellency even when a pressure of 866Pa is applied from the liquid. For example, the liquid-repellent resin sheet according to item 1 or 2 of the patent application scope, wherein one or more substrate layers are laminated on the other side of the convex-shaped layer of the convex-shaped surface, and the substrate layer includes One or more resins among styrene resin, olefin resin, polyester resin, nylon resin, ethylene-vinyl alcohol copolymer resin, and acrylic resin. For example, a liquid-repellent resin sheet according to item 13 of the patent application, wherein a sealant resin layer is formed between the convex layer and the base material layer, and the sealant resin layer contains a polymer selected from a modified olefin-based polymer resin. And at least one of thermoplastic elastomers. An article using a liquid-repellent resin sheet according to any one of claims 1 to 14 of the scope of patent application. For example, the item in the scope of application for patent No. 15 wherein the item is daily necessities, packaging materials or building materials. For example, the item in the scope of application for patent No. 16 wherein the item is a food container, a bag, a raincoat, an umbrella, a wallpaper, or a component in a water place.