TW201006877A - Anti-fogging surface-treating agent and anti-fogging resin sheet - Google Patents

Abstract

Provided is anti-fogging surface-treating agent, containing anti-fogging property at high temperature, and low temperature and use thereof. Anti-fogging surface-treating agent contain (A) nonionic surfactant (sucrose fatty acid ester and like), (B) water-soluble macromolecule ((B1) vinylpyrrolidone-based polymer and like), and (C) ionic surfactant (sulfonate and like). Further, (B) water-soluble macromolecule could contain (B2) polyoxyalkylene polymer. The ratio of (B2) polyoxyalkylene polymer relative to (B) water-soluble macromolecule is below 50% by weight.

Description

[Technical Field] The present invention relates to a useful antifogging surface treatment agent (antifogging treatment agent) and antifogging for imparting antifogging property to the surface of a resin sheet or the like. A resin sheet, and a method for producing an antifogging resin sheet and a container to which antifogging property is imparted. [Prior Art] The water-repellent synthetic resin sheet of the styrene resin sheet or the like which is used in a packaging container for foods and the like has low antifogging property. Therefore, when a food or the like is stored in a container formed of such a resin sheet, water vapor is adhered to the surface of the container as a minute water droplet due to a change in temperature or temperature, resulting in fogging and a decrease in transparency. Therefore, the visibility of the contents is lowered. Therefore, there has been proposed a method of imparting antifogging property to a resin sheet by using a higher fatty acid ester or the like. For example, JP-A-2002-356572 (Patent Document 1) discloses an antifogging styrene-based transparent resin sheet containing 76 to 99.9% by mass of sucrose fatty acid ester and 0.1 to 24% by mass of Poly®. An antifogging agent of a vinyl pyrrolidone-based (co)polymer (the amount of unreacted vinylpyrrolidone is 1000 ppm or less) is surface-treated. In the styrene resin sheet, 30% by mass or more and 99% by mass or less of sucrose fatty acid ester and 1% by mass or more, 70 are disclosed in Japanese Laid-Open Patent Publication No. 2005-1-2663 (Patent Document 2). An antifogging agent of polyvinyl alcohol (hereinafter abbreviated as PVA) (the total amount of residual methanol and residual methyl acetate is 4% by mass or less) is applied to at least one side of the styrene resin sheet. However, these sheets are insufficient in antifogging property. Further, when rolled into a roll, the antifogging agent comes into contact with the non-anti-fogging surface of the resin sheet to cause an off setting, and the whitening of the sheet 201006877 causes the outer diameter to deteriorate. Further, Japanese Patent Publication No. 3241797 (Patent Document 3) discloses a surface treatment agent containing a sucrose fatty acid ester, a mash emulsion, a polysaccharide, and/or a hydrophilic polymer (excluding polyvinyl alcohol). In this document, since the emulsion is contained, the printability of the sheet can be improved, but the antifogging property or the durability of the film is insufficient. Japanese Patent Publication No. Hei 9-22 1661 (Patent Document 4) discloses an antifogging agent containing a sucrose fatty acid ester and 0.1 to 30% by weight of an anionic interface active agent. However, when the sheet coated with the antifogging agent is wound into a roll shape, the antifogging agent is transferred and the antifogging property is lowered, and the appearance of the sheet is deteriorated due to whitening of the sheet, and the durability of the film is also deteriorated. . Further, Japanese Laid-Open Patent Publication No. 2003-201355 (Patent Document 5) discloses an antifogging resin sheet which is a mixture of a polyol type nonionic surfactant and a polyethylene glycol type nonionic surfactant. It is composed of a coated surface. In this document, a polyol type nonionic surfactant sucrose fatty acid ester and/or a polyglycerin fatty acid ester, and a polyethylene glycol type nonionic surfactant are polyoxypropylene polyoxyethylene blocks. Copolymer. However, since the polyoxypropylene polyoxyethylene block copolymer is used, a part of the coating component is transferred (adhered or deposited) on a roll (metal roll, etc.) in a coating, drying and coiling process, resulting in low antifogging property of the sheet. . [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open No. Hei 9-221661 (Patent Document No. 2) (Patent Document 5) JP-A-2003-2013 No. 55 (Application No. 1) (3) 201006877 [Problem to be Solved by the Invention] Therefore, an object of the present invention is to provide an antifogging surface treatment agent having high antifogging property at a wide temperature and use thereof (antifogging resin sheet) And its preparation method, and a container made of the anti-fog resin sheet). Another object of the present invention is to provide a process for coating, drying, coiling, and thermoforming a resin sheet, which does not cause off setting, and maintains antifogging property and high quality even when the coating amount is small. Appearance © (or anti-whitening) anti-fog surface treatment agent and its use. Still another object of the present invention is to provide an antifogging surface treatment agent capable of maintaining high antifogging property and durability in a process of a resin sheet without contaminating a roll (particularly a metal roll) and use thereof. Another object of the present invention is to provide an antifogging surface treatment agent capable of improving mold release property (or adhesion resistance) while maintaining a high antifogging property in a resin sheet process and use thereof. Still another object of the present invention is to provide an antifogging surface treatment agent capable of preventing transfer while maintaining high antifogging property even if eucalyptus oil is not used, and use thereof. [Means for Solving the Problem] In order to achieve the above-mentioned problems, the inventors of the present invention have found that (A) a nonionic surfactant (such as sucrose fatty acid ester) or (B) a water-soluble polymer (vinyl) When a pyrrolidinone polymer or the like and (C) an anionic surfactant (such as a sulfonate) are combined, high antifogging property can be obtained at a wide temperature, and the process of the resin sheet does not contaminate the roll (especially The present invention has been completed without the transfer of metal rolls. In other words, the antifogging surface treatment agent of the present invention contains (A) a nonionic surfactant, (B) a water-soluble polymer, and (c) an anionic surfactant. (A) The melting point or softening point of the nonionic surfactant may be 5 〇 t: or more. Further, the (A) nonionic surfactant may be at least one selected from the group consisting of sucrose fatty acid esters, polyglycerin fatty acid esters, glycerin fatty acid esters, and polyoxyalkyl ethers. (B) The water-soluble polymer may be (B1) a water-soluble polymer which does not contain an oxyalkylene unit. Further, the (B) water-soluble polymer may be at least one selected from the group consisting of a (B1) vinylpyrrolidone polymer, a vinyl alcohol polymerizable material, a cellulose ether, and alginic acid or a salt thereof. (B) The water-soluble polymer may further contain (B2) a polyoxyalkylene polymer. The ratio of the (B2) polyoxyalkylene polymer to the (B) water-soluble polymer may be 50% by weight or less. By such a ratio, the roller (especially the metal roller) is not contaminated and the durability of the film can be improved. (C) The anionic surfactant may be at least one selected from the group consisting of a carboxylate, a sulfate, a sulfonate, and a phosphate or a phosphate salt. The surface treatment agent is composed of a matrix containing (A) a nonionic surfactant and (B) a water-soluble polymer in a ratio of 100 parts by weight of the former/the latter ❹ =1/99 to 99/1 (weight ratio). The material may be (C) an anionic surfactant containing from 0.1 to 200 parts by weight. The surface treatment agent (A) nonionic surfactant is a sucrose fatty acid ester, (B) the water-soluble polymer contains a vinyl pyrrolidone polymer, and (C) the anionic surfactant is a sulfonate. And the matrix composition containing the ratio of (A) the nonionic surfactant and the (B) water-soluble polymer to 100 parts by weight of the former/the latter = 20/80 to 95/5 (weight ratio) may be It contains about 1 to 150 parts by weight of (C) an anionic surfactant. (B) the water-soluble polymer may further contain (B2) a polyoxyalkylene polymer, and the ratio of the (B2) polyoxyalkylene polymer to the (B) water-soluble polymer of 201006877 is 1 to 40% by weight. about%. The present invention also includes an antifogging resin sheet in which an antifogging layer containing the surface treating agent is formed on at least one side of the resin sheet. An anti-fog layer may be formed on one side of the resin sheet and a release layer may be formed on the other side. The above resin sheet may be a styrene resin sheet. Further, the present invention also relates to a method for producing an antifogging resin sheet which is obtained by applying the surface treatment agent to one surface of a resin sheet. In the above production method, after the surface treatment agent is applied to the resin sheet, it may be wound into a roll. Moreover, the present invention also encompasses a container in which an antifogging layer containing the surface treatment agent is formed on at least a part of a surface of a resin container. Moreover, the present invention also encompasses a container formed of the aforementioned antifogging resin sheet. [Effects of the Invention] In the present invention, by combining (A) a nonionic surfactant, (B) a water-soluble cerium molecule, and (C) an anionic surfactant, high antifogging property can be obtained at a wide temperature. Further, in the process of coating, drying, coiling, and thermoforming of the resin sheet, transfer is not caused, and even when the amount of coating is small, high antifogging property and high quality appearance (or prevention of whitening) can be maintained. Further, in the process of the resin sheet, it is possible to maintain high antifogging property and durability without contaminating the roll (especially the metal roll). Further, in the process of the resin sheet, the mold release property (or the adhesion resistance) can be improved while maintaining high antifogging property. Moreover, even if oyster sauce is not used, it is possible to prevent the transfer while maintaining high anti-fog property. [Embodiment] [Surface Treatment Agent], 201006877 The antifogging surface treatment agent of the present invention contains (A) a nonionic surfactant, (B) a water-soluble polymer, and (C) an anionic surfactant. (A) Nonionic surfactant The nonionic surfactant can be roughly classified into a polyol fatty acid ester and an active hydrogen atom of a hydrophobic compound, and an addition product obtained by adding ethylene oxide. The nonionic surfactant is used in the following to not contain a polyoxyethylene-polyoxypropylene copolymer. Examples of the polyhydric alcohol include C2.12 alkylene glycols such as ethylene glycol, propylene glycol, butanediol, hexanediol, and neopentyl glycol; diethylene glycol, triethylene glycol, and polyethylene glycol; (poly)oxygen C2-4 alkylene glycol with dipropylene glycol, tripropylene glycol, polypropylene glycol, polybutanediol, etc.; glycerin, polyglycerol with a polymerization degree of 2~20 (diglycerol, triglycerin, tetra Glycerin, polyglycerol, etc.), trimethylolethane, trimethylolpropane, neopentyl alcohol, sugars (sucrose, sorbitol, mannitol, xylitol, maltitol, sorbitol) A polyhydroxy compound (polyol) such as an anhydride or an oligosaccharide. These polyols may be used alone or in combination of two or more. The φ fatty acid may, for example, be any one of a monocarboxylic acid or a polyvalent carboxylic acid, and may be either a saturated or unsaturated fatty acid. Further, the fatty acid also contains a component containing a fatty acid, for example, a component containing a fatty acid as a main component (for example, contained in a ratio of 50% by weight or more) (for example, fat or oil such as coconut oil). The fatty acid may be a C6-4 〇 fatty acid, preferably a Cm fatty acid (for example, citric acid, lauric acid, myristic acid, palmitic acid, stearic acid, hydroxystearic acid, arachidic acid, abietic acid, octadecanoic acid, etc. C8_26 saturated fatty acid, oleic acid, sinapic acid, etc., C8_26 unsaturated fatty acid, etc.), more preferably C1G-22 saturated fatty acid (such as C1 ()-2 () fatty acid) is better, with Clc_18 fatty acid (lauric acid, meat, 201006877 Saturated fatty acids such as myristic acid, palmitic acid, and stearic acid are particularly preferable as such a mixture (such as coconut oil or the like) and an unsaturated fatty acid such as oleic acid. Most of the polyhydric alcohol fatty acid esters are selected from the group consisting of sucrose fatty acid esters, polyglycerin fatty acid esters, glycerin fatty acid esters, sorbitan fatty acid esters, and sorbitan fatty acid esters. Examples of the sucrose fatty acid ester include sucrose laurate (such as sucrose mono-laurate), sucrose palmitate (sucrose mono-penta-palmitate, etc.), and sucrose stearate (sucrose mono-pentarate). a sucrose c8_24 saturated or unsaturated fatty acid ester (one to six esters, etc.) such as sucrose sucrose (sucrose-Φ to penta-oleic acid ester), sucrose oleate (sucrose oleate, etc.), In particular, sucrose c8_24 saturated or unsaturated fatty acid esters (mono-tetraesters, etc.), etc.). Examples of the polyglycerin fatty acid esters include esters of polyglycerol and C8-24 saturated or unsaturated fatty acids having a polymerization degree of about 2 to 16, such as decaglyceryl octanoate (decaglyceryl mono-octanoate, etc.), hexaglycerol laurel Acid esters (hexaglycerol mono-laurate, etc.), decaglyceryl laurate (decaglyceryl mono-dodecanoate, etc.), decaglyceryl stearate (decaglyceryl mono-stearate, etc.), decaglycerin oil Acid ester φ (decaglycerine mono to oleic acid ester, etc.), etc.). Examples of the glycerin fatty acid esters include esters of glycerin and C8.24 saturated or unsaturated fatty acids, such as glyceryl octanoate (such as mono- or dicaprylate), glycerin laurate (glycerol mono-dilaurate, etc.). Glyceryl stearate (such as glycerol mono-distearate), glycerol oleate (such as glycerol mono-dioleate), glycerol oleate (such as glycerol mono- or dioleate), etc.). The sorbitol fatty acid ester may, for example, be an ester of sorbitol and a C8_24 saturated or unsaturated fatty acid, such as sorbitol caprylate (sorbitol mono-octanoate, etc.), sorbitol laurate (sorbent pear) Sugar alcohol mono to laurate -10.201006877, etc.), sorbitol palmitate (sorbitol mono-pentapalmitate, etc.), sorbitol stearate (sorbitol mono-pentarate) Etc.), sorbitol oleate (sorbitol monooleate, etc.), etc., sorbitan fatty acid esters such as fatty acid esters. These fatty acid esters may be used alone or in combination of two or more. The preferred polyhydric alcohol fatty acid esters include sucrose fatty acid esters, polyglycerin fatty acid esters, and glycerin fatty acid esters, particularly sucrose fatty acid esters (sucrose C8_24 saturated fatty acid esters such as sucrose fatty acid esters). In the ethylene oxide addition product of the hydrophobic compound, the hydrophobic compound having an active hydrogen atom may, for example, be a higher alcohol (C8_24 alcohol such as lauryl alcohol) or an aromatic hydroxy compound (phenol or alkylphenol). Etc.), a polyol fatty acid ester having a hydroxyl group, a fat having a hydroxyl group (castor oil, hardened castor oil, etc.). The ethylene oxide adduct of the hydrophobic compound contains, for example, an ethylene oxide adduct of a higher alcohol (polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, etc.) Polyoxyethylene c8.26 alkyl ether (preferably polyoxyethylene C1G_2 () alkyl ether), etc.), ethylene oxide adduct of an aromatic hydroxy compound [for example, polyoxyethylene phenyl ether, etc. Oxyethylene aryl ether (preferably polyoxyethylene C6-1G aryl ether, etc.); polyoxyalkylene alkyl aryl ether such as polyoxyethylene nonylphenyl ether (preferably polyoxyethylene c4_26 alkyl C6) .1Q aryl ether, etc.), ethylene oxide adduct of polyol fatty acid ester [polyoxyethylene glyceryl stearate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbose a c8-26 fatty acid ester having a polyoxyethylene chain such as an alcohol stearate (preferably a C1()-2() fatty acid ester having a polyoxyethylene chain, etc.), an ethylene oxide addition of a fat or oil A product (polyoxyethylene castor oil, polyoxyethylene hardened castor oil, polyoxyethylene-11-.201006877, an ethylene oxide adduct of a hydroxyl group-containing fat or the like such as coconut oil, etc.). The above-mentioned polyoxyethylene adduct has a number average molecular weight of, for example, 150 or more (e.g., 150 to 35,000), preferably 200 to 30,000, more preferably 200 to 20,000. In the ethylene oxide adduct of the hydrophobic compound, the average addition molar number of the oxyethylene unit may be, for example, 2 to 100, preferably 2 to 50, more preferably 3 ~30 or so, can also be 2~1 0 or so. © Further, in the polyol fatty acid ester and its ethylene oxide adduct, the fatty acid is not limited to a single fatty acid, and may be a plural fatty acid ester (mixed fatty acid ester). The (A) nonionic surfactant may be used singly or in combination of a plurality of (same or different) surfactants. (A) The nonionic surfactant is at least one selected from the group consisting of sucrose fatty acid esters, polyglycerin fatty acid esters, glycerin fatty acid esters, and polyoxyethylene alkyl ethers (polyoxyethylene C1G-2G alkyl ethers, etc.) It is particularly preferable to contain at least a sucrose fatty acid ester (sucrose C1()_2() fatty acid ring or the like) such as sucrose laurate. (A) The nonionic surfactant is preferably a solid at normal temperature (for example, 20 to 25 ° C). The melting point or softening point of the nonionic surfactant may be 50° C. or higher (for example, about 50 to 100° C.), and preferably 51° C. or higher (for example, 51 to 98° C.) is 52 or more (for example, 53). ~95 ° C) is better. Further, the melting point or softening point of the nonionic surfactant may be a relatively high temperature, and may be 54 to 1 ° C (for example, 60 to 98 ° C) to 65 to 97 ° C (for example, 70 to 96 °). C) is better than 75 to 95 ° C (for example, 80 to 94 ° C), preferably 85 to 93 ° C. Moreover, it can be used at a normal temperature for liquid or low melting point (for example, a melting point of less than 5), without hindering the antifogging property, and causing no transfer from -12 to 201006877 to a roll (especially a metal roll) and adhesion or transfer. 0 ° C) nonionic surfactant. The ratio of the nonionic surfactant at a normal temperature to a liquid or low melting point relative to the (A) nonionic surfactant is less than 50% by weight (for example, about 0 to 45% by weight) to less than 4 It is preferably 0% by weight (e.g., about 0.1 to 5% by weight), more preferably less than 30% by weight (e.g., about 0.5 to 25% by weight). (B) Water-soluble polymer Φ (Β) A water-soluble polymer can use various polymers having a function as a binder, and can be roughly classified into (Β1) oxyalkylene units (extended oxygen) Water-soluble polymer and (Β2) polyoxyalkylene polymer. In the present invention, at least (B1) a water-soluble polymer which does not contain an alkylene oxide unit is used. The water-soluble polymer which does not contain an oxygen-extended alkyl unit in (B1) contains a hydrophilic group or a unit (carboxy group or its salt, a sulfonic acid group or its salt, a hydroxyl group, a mercaptoamine group, a basic nitrogen atom containing group, A polymer such as a vinyl ether unit or the like, a cellulose derivative, a natural polymer polysaccharide (such as glutenic acid such as alginic acid). (B1) The water-soluble polymer not containing an alkylene oxide unit may be any of a water-soluble, water-dispersible, and water-swellable polymer compound. (B1) The water-soluble polymer not containing an alkylene oxide unit may, for example, be a polymer having a carboxyl group or a salt thereof (for example, (meth)acrylic acid, maleic acid, fumaric acid, and itaconic acid) a homo group or copolymer of a monomer having a carboxyl group (including other copolymers such as (meth) acrylate such as alkyl (meth) acrylate, styrene, vinyl carboxylate (vinyl acetate, etc.) Copolymer of a monomer, such as poly(meth)acrylic acid, (meth)acrylic acid-maleic anhydride copolymer, (meth)acrylic acid-vinylsulfonic acid copolymer, (methyl)-13- .201006877 (meth)acrylic polymer such as an acrylic acid-methyl methacrylate copolymer) or a salt thereof (for example, an alkali metal salt such as a sodium salt or a potassium salt, an ammonium salt or an organic amine salt), etc. a polymer of a sulfonic acid group or a salt thereof [such as a homopolymer or a copolymer of a sulfonic acid group-containing monomer such as ethylene sulfonic acid or styrene sulfonic acid (including a copolymer with other copolymerizable monomers described above) or a salt thereof (for example, an alkali metal salt such as a sodium salt or a potassium salt, an ammonium salt, an organic amine salt, etc.) Etc., a hydroxyl group-containing polymer [for example, a hydroxyl group-containing monomer (for example, hydroxyalkyl acrylate such as 2-hydroxyethyl acrylate or 2-hydroxypropyl acrylate, hydroxyalkyl methacrylate, etc., etc., © a homopolymer or a copolymer of polyethylene glycol mono(meth)acrylate (including a copolymer with other copolymerizable monomers described above), a vinyl alcohol polymer, etc.], a mercapto group-containing polymerization a homopolymer or a copolymer of a mercaptoamine-containing monomer such as (meth)acrylamide (including a copolymer with other copolymerizable monomers described above), etc.], a polymerization containing a basic nitrogen atom a homopolymer or a copolymer having a basic nitrogen atom such as N-dimethylaminoethyl acrylate, N-diethylaminoethyl acrylate or a corresponding methacrylate or vinylpyrrolidone ( Also included is a copolymer with other copolymerizable monomers described above), a vinyl oxime ether-based polymer [for example, a vinyl ether monomer (vinyl methyl ether, vinyl ethyl ether, vinyl isopropyl ether) , alkyl vinyl ethers such as vinyl butyl ether, vinyl isobutyl ether, etc. a homopolymer or a copolymer (for example, a copolymer monomer such as polyvinyl methyl ether, polyvinyl ethyl ether, vinyl ether or maleic anhydride copolymer (the aforementioned monomer having a carboxyl group, exemplified above) a copolymer of another copolymerizable monomer or the like), etc., a cellulose derivative [for example, an alkyl cellulose (G-6 alkyl cellulose such as methyl cellulose, ethyl cellulose, or propyl cellulose) ), hydroxyalkyl cellulose (hydroxyethyl cellulose, hydroxypropyl cellulose, etc., hydroxy C2-4 alkyl cellulose, etc.), hydroxyalkyl alkyl cellulose (hydroxyethyl methyl fibrane-14 - 201006877 a hydroxyl group C2_4 alkyl-Ci-6 alkyl cellulose such as hydroxypropyl methylcellulose or the like, or a carboxyl group of carboxyalkyl cellulose (carboxymethyl cellulose, carboxyethyl cellulose, etc.) A cellulose ether such as an alkyl cellulose; a soluble cellulose acetate or the like; a water-soluble polyester, a natural high molecular polysaccharide such as alginic acid or a salt thereof, pectin, starch, hyaluronic acid, cartilage Sodium sulphate, chondroitin heparin, agar, gum arabic, dextrin, etc.] Polymer alone or in combination of two or more. (B1) The melting point or softness point of the water-soluble polymer not containing an alkylene oxide unit is 60 ° C or higher (for example, about 60 to 3 50 ° C), preferably 62 ° C or higher (for example, 65 to 320) °C or so) 'More preferably 65 ° C or more (for example, about 65 to 310 ° C), it can be 100 to 300 ° C (for example, about 130 to 250 ° C) or 150 to 200 ° C or so. Further, the melting point or softening point of the (meth)acrylic polymer having a (meth)acrylic monomer as a main component may be about 60 to 110 ° C (for example, 75 to 105 ° C) to (methyl) The melting point or softening point of the acrylamide-based monomer as a main component may be 100 to 200 ° C (for example, 150 to 190 ° C). The melting point or softening point of the vinyl ether polymer may be ι 〇〇 18 〇Φ °C (for example, I20~l60°c). Further, the glass transition temperature of (B1) a water-soluble polymer not containing an alkylene oxide unit may be 50 to 250. (:, preferably 55 to 230 ° C is better than 60 to 20 (TC is better. Also, the melting point, softening point or glass transition temperature can be analyzed by conventional thermal analysis (thermal analysis using a thermal scanning calorimeter, etc.) (B1) Among the water-soluble polymers not containing an alkylene oxide unit, a vinylpyrrolidone polymer, a vinyl alcohol polymer, a cellulose ether, an alginic acid or a salt thereof is used. Preferably, the base ketone ketone ketone polymer comprises a vinylpyrrolidone or a homopolymer or copolymer of the -15-201006877 derivative, such as polyvinylpyrrolidone, and p-vinylpyrrolidone a copolymer of a copolymerizable copolymerizable monomer [for example, a copolymer of a copolymerizable monomer such as the above (meth)acrylic monomer, vinyl acetate, vinyl quinone, vinyl caprolactam or the like ( For example, vinyl sulphonone-ethyl acetate copolymer, etc.), etc.. The sputum base ketones may be used alone or in combination of two or more kinds. The ratio of the suspicion of the ketones or its derivatives may be, for example, 3 〇 to 100 weights. 'It is more preferably 50 to 95% by weight, and more preferably 60 to 90% by weight. In terms of antifogging property, it is advantageous when the ratio of vinylpyrrolidone or a derivative thereof is 30% by weight or more. The glass transition temperature (Tg) of the vinylpyrrolidone polymer may be, for example, 55 to 25 ° C ' at 60 to 240 ° C (for example, 63 to 23 ° C), preferably 65 to 220 ° C. (For example, about 68 to 20 (TC) is more preferable. Further, the molecular weight of the vinylpyrrolidone-based polymer is not particularly limited, and for example, it may be a weight average molecular weight of 1χ1〇4 to 50〇χ1〇4, to 5xl〇4. 〜30〇χ104 is preferable, and ΙΟχΙΟ4~25〇xl〇4 or so is more preferable. The vinyl alcohol-based polymer may be a saponified product of a fatty acid vinyl ester polymer (the same or a copolymer) such as polyvinyl alcohol. (completely saponified polyvinyl alcohol, partially-formulated polyvinyl alcohol), partially acetalized polyvinyl alcohol, ethylene-ethylene copolymer, ethylene-ethylenesulfonic acid copolymer, vinyl alcohol-maleic acid copolymer, etc. These vinyl alcohol-based polymers may be used alone or in combination of two or more. Among these, polyvinyl alcohol The degree of saponification of the ethylene glycol-based copolymer is not particularly limited, and may be, for example, 6 〇 to 1 〇〇 mol%, preferably 70 to 100 mol% (for example, 80 to 99 mol/») More preferably, it is about 85 to 100 mol%. The melting point of the vinyl alcohol polymer is -16 to 201006877 or the softening point is 130 to 250 ° C, preferably 150 to 240 ° C, and 170 to 230 ° C (for example, 180). More preferably, it is about 220 ° C. The degree of polymerization (or average degree of polymerization) of the vinyl alcohol polymer may be, for example, 100 or more (for example, 1 〇〇 to 5000), 200 to 4,000, and 500 to 3,000. The left and right are better. Among the cellulose ethers, a hydroxyl group c4_4 alkyl cellulose such as methyl-4-cellulose, hydroxyethyl cellulose or hydroxypropyl cellulose, or hydroxyethyl methyl cellulose. a hydroxy C2.4 alkyl-Ci-4 alkyl cellulose such as hydroxypropylmethylcellulose or a carboxyl group C-4 alkyl styrene such as carboxymethylcellulose, etc. The ethers may be used alone or in combination of two or more. The melting point or softening point of the cellulose ether may be about 150 to 350 ° C (e.g., 20 0 to 320 ° C, preferably 220 to 300 ° C). Further, cellulose ethers may be decomposed without exhibiting a melting point. At this time, the decomposition temperature can be used as a melting point. The degree of polymerization (or average degree of polymerization) of the cellulose ethers may be usually 100 or more (e.g., 100 to 2,000), preferably 150 to 1,000, more preferably about 200 to 800. The alginic acid is a linear polymer polysaccharide obtained by extracting brown algae plants such as kelp, wakame, sea φ trumpet, etc., and contains D-mannuronic acid and L- Gluuronic acid is a heteropolymer of constituent units. The salt of alginic acid may, for example, be a salt of alginic acid and an inorganic base, and specific examples thereof include an ammonium salt; an alkali metal salt such as a potassium salt or a sodium salt; an alkaline earth metal salt such as a calcium salt or a magnesium salt; a silver salt and copper. a transition metal salt such as a salt or the like. Among these salts, ammonium salts and other monovalent metal salts (alkali metal salts, etc.) are preferred. These alginic acids may be used alone or in combination of two or more. The melting point or softening point of the natural polymer polysaccharide such as alginic acid may be the same as the "melting point" of the cellulose ether. The degree of polymerization (or average degree of polymerization) of the natural high molecular polysaccharide (alginic acid-17- • 201006877 or its salt, etc.) may be usually 20 or more (for example, 20 to 2000), preferably 50 to 1,500, and 70 to 70. Around 1300 is better. In the above (B) water-soluble polymer, (B2) a polyoxyalkylene polymer may be further used in addition to (B1) a water-soluble polymer which does not contain an alkylene oxide group. (B 2 ) The polyoxyalkylene polymer may, for example, be a polyoxyethylene (or polyethylene glycol) or a polyoxyethylene-polyoxypropylene block copolymer [for example, a polyoxyethylene-polyoxypropylene block copolymer (hereinafter, There is a polymer having an oxidized C2_4 olefin unit (especially an oxygen-extended ethyl unit), etc., which is abbreviated as POE-POP block copolymer. These (B2) polyoxyalkylene polymers may be used alone or in combination of two or more. Among these, a POE-POP block copolymer or the like is preferred. The content of the oxygen-extended ethyl chain in the POE-POP block copolymer may be 10 to 99% by weight, preferably 15 to 95% by weight, more preferably 20 to 95% by weight, even more preferably 30 to 90% by weight. The left and right are especially good. The block structure of the above block copolymer is not particularly limited, and may be a diblock structure, a parablock structure in which an oxygen group is bonded to both ends of a propylene oxide block, and the like. ❷ POE-POP block copolymer contains a copolymer of an exotropy ethyl block-(CH2CH2〇)m- and a propylene oxide block_(CH(CH3)CH20)n-, and the epoxy B in the copolymer The content of the alkyl chain (111/(111 + 11)><100) is 10 to 99 mol%, preferably 15 to 95 mol%, more preferably 20 to 95 mol%, and 30 ~90% of the % is especially good. The block structure of the above block copolymer is not particularly limited, and may be a diblock structure of a block of an oxygen-extended ethyl block and propylene oxide, and an oxygen-extended ethyl block is bonded to both ends of the propylene oxide block. The triblock structure and the like. The copolymer of the triblock structure can be represented by the following formula. -18- 201006877

The content of ethylene oxide chain in the copolymer of HO-(CH2CH2〇)mi-(CH(CH3)CH2〇)n-(CH2CH2〇)m2-H triblock structure [(ml+m2)/( Ml+m2 + n)xl00] can be selected from the same range as the content of the ethylene oxide chain (m/(m + n) X100) in the copolymer. Further, the POE-POP block copolymer may be used singly or in combination of two or more kinds of ethylene oxide chains having different contents, block structures and molecular weights. The melting point or softening point of the (B2) polyoxyalkylene polymer may be usually less than Φ 60 ° C (e.g., 45 to 59 ° C), preferably 48 to 59 ° C, more preferably about 50 to 58 ° C. (B2) The weight average molecular weight of the polyoxyalkylene polymer (POE-POP block copolymer or the like) is not particularly limited and may be 1, 〇〇〇 1,000,000 (for example, 1,000 to 800,000) to 1,500. Preferably, it is preferably about 600,000 (for example, 1,500 to 500,000), and about 2,000 to 400,000 (for example, 2,000 to 300,000). The ratio of the (B 2 ) polyoxyalkylene polymer to the (B) water-soluble polymer may be 50% by weight or more (for example, 1 to 45% by weight), preferably 2 to 40% by weight φ, and 3 to 30%. The weight % is more preferably about 1 to 30% by weight (e.g., 3 to 20% by weight, preferably 5 to 15% by weight). (B1) The ratio (weight ratio) of the water-soluble polymer not containing an alkylene oxide unit to the (B2) polyoxyalkylene polymer may be the former/the latter = 3 0/70 to 100/0 to 35/65 〜 90/10 is preferred, preferably about 40/60 to 80/20 (for example, 45/55 to 70/30) because (B2) polyoxyalkylene polymer (POE-POP block copolymer, etc.) will ( B1) The water-soluble polymer not containing an alkylene oxide unit can be plasticized. If the (B2) polyoxyalkylene polymer is too much, it is applied to the resin sheet and dried, and the film is coated with a -19-201006877 roll (especially a metal). When the roller is in contact, the roller is easily contaminated and the antifogging agent component adheres (or accumulates) on the roller. In the present invention, by using (B2) a polyoxyalkylene polymer in the above ratio, since (B1) a water-soluble polymer not containing an alkylene oxide unit can be appropriately plasticized, it is possible to not contaminate the dyeing roll and also Improve the durability of the film. The matrix composition can be constituted by using (A) a nonionic surfactant and (B) a water-soluble polymer. The ratio (weight ratio) of (A) the nonionic surfactant and (B) the water-soluble polymer is, for example, the former/the latter = 1/99 to 99/1 (for example, 〇5/95 to 99/1), 10/90 to 98/2 (for example, 15/85 to 96/4) is better, with 20/80 to 95/5 (for example, 25/75 to 90/10) as better, to 30/70 to 85. /15 (for example, 40/60 to 80/20) is particularly good. (C) Anionic surfactant for a matrix composition containing (A) a nonionic surfactant and (B) a water-soluble polymer ( (A) the total amount of the nonionic surfactant and (B) the water-soluble polymer), when the (C) anionic surfactant is added, the water-soluble polymer can be plasticized and formed uniformly with the formation. The anti-fog layer or the anti-fog layer containing the surface treatment agent is formed on the resin sheet, and the molded container (especially deep drawing) can ensure high anti-fog property. Further, even if the amount of the surface treatment agent applied is small, high antifogging property can be ensured. (C) The anionic surfactant may be a sulfonate, a sulfate salt, a fatty acid salt, a phosphate or a phosphate salt. The basic substance constituting the salt can be exemplified by an inorganic base [ammonia, an alkali metal (sodium, potassium, etc.), an alumina-based metal (calcium, magnesium, etc.), etc.], an organic base [lower alkylamine (trimethylamine, triethyl) Amine, tributylamine, etc.), alkanolamine (ethanolamine, diethanolamine, dimethylpentylethanolamine, etc.), etc.]. Most of the salt systems are ammonium salts, alkane-20-201006877 base metal salts (sodium, potassium, etc.), alkylamine salts or alkanolamine salts. Examples of the sulfonate include an alkanesulfonate [Cim alkanesulfonate such as lauryl sulfate (such as sodium C1C-18 alkanesulfonate)], and an aromatic hydrocarbonsulfonate (benzenesulfonate, naphthalenesulfonate, etc.). C6_1G aryl sulfonate), alkyl arene sulfonate [octyl benzene sulfonate, undecyl naphthalene sulfonate, dodecyl benzene sulfonate, etc. C4.20 alkyl c6-ie aromatic hydrocarbon Sulfonic acid salt (sodium dodecylbenzenesulfonate, etc.), etc., alkyl sulfosuccinate succinate [di-(2-ethylhexyl) sulfosuccinate di-C6_2G alkyl sulfonate amber An acid salt (such as sodium di-(2-ethylhexyl)sulfonate succinate) or the like, an α β -olefin sulfonate or the like. The sulfate salt may, for example, be an alkylsulfate salt or an alkenyl sulfate salt (higher alcohol sulfate salt) [Clartasulfate salt (sodium lauryl sulfate, etc.), octadecyl sulfate salt, etc., C1 () .2 () alkyl sulfate salt, C10-2G alkenyl sulfate salt of oil sulfonate sulfate salt (sodium oleyl sulfate), etc.], alkyl ether sulfate salt (sodium lauryl ether sulfate) , polyoxyethylene-Ci 0.2 0 alkyl ether sulfate salt, etc.]. The carboxylate can be exemplified by C8.26 fatty acid such as caprylate, laurate, myristate, palmitate or stearate. a salt (for example, a C8-2G fatty acid salt such as C8-2G fatty acid potassium), etc. The phosphate or phosphate salt can be exemplified by a mono- or dialkyl phosphate [octyl phosphate salt (sodium octyl phosphate, etc.), etc., dodecane a c8.20 alkyl phosphate salt such as a phosphatide salt, a polyoxyethylene-alkyl phosphate salt (such as sodium polyoxyethylene-alkyl phosphate), or a polyoxyethylene-alkyl aryl phosphate salt. Or a dialkyl phosphate, etc. These anionic surfactants may be used alone or in combination of two or more. The (C) anionic interface activity Among them, an alkanesulfonate, an alkyl sulfate, particularly a c1D.2Q alkanesulfonate (c1Q.18 sodium alkanesulfonate, etc.) -21 - 201006877, etc. are preferred. (c) Anionic surfactant Among them, it is preferably a solid at room temperature (20 to 25 ° C). The melting point or softening point of the anionic surfactant is 50 ° C or higher (for example, about 50 to 150 ° C), and 55 ° C or higher. Preferably, it is preferably about 60 to 110 ° C (for example, 65 to 100 ° C). When used as an anionic surfactant at room temperature or low melting point, antifogging property It is easy to be low and easy to transfer and adhere to a roll (especially a metal roll) or to cause transfer. (C) The amount of the anionic surfactant can be selected according to the amount of (A) non-ionic surfactant used, etc. The amount of the matrix composition ((A) nonionic surfactant and (B) water-soluble polymer) may be 0.1 to 200 parts by weight (for example, 1 to 150 weight). The portion is preferably 2 to 130 parts by weight (for example, 3 to 125 parts by weight), and more preferably 5 to 120 parts by weight (for example, 7 to 100 parts by weight). Further, the amount of the (C) anionic surfactant may be used in a small amount, for example, may be 1 to 50 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of the matrix composition, preferably 10 It is more preferable that it is about 30 parts by weight. Ο The surface treatment agent may also contain eucalyptus oil. The type of eucalyptus oil is not particularly limited, and examples thereof include dimethyl polyoxy siloxane, diethyl polyoxy siloxane, and trifluoropropyl group. An alkyl polyoxyalkylene such as a polyoxyalkylene; an aryl polyoxyalkylene such as a diphenyl polyoxyalkylene; an alkylaryl polyoxyalkylene such as a methylphenyl polysiloxane or the like. The eucalyptus oil may be a chain polyoxyalkylene or a cyclic polyoxyalkylene. Further, the eucalyptus oil may be, for example, a modified eucalyptus oil, for example, a hydroxyalkyl group (hydroxyc2-4 alkyl group such as hydroxyethyl group, etc.), a polyoxyalkylene group, an amine group, an N-alkylamine group, an epoxypropyl group or An eucalyptus oil such as an epoxy group or a polymerizable group (such as a vinyl group or a (meth) acrylonitrile group). -22- 201006877 Emu oil can be used alone or in combination of two or more. Among the eucalyptus oils, dimethylpolysiloxane having high versatility is usually used. Emu oil can be used in various forms. In general, it is usually used in the form of a mash emulsion (an emulsion obtained by emulsifying and dispersing eucalyptus oil). The viscosity of the eucalyptus oil is not particularly limited. For example, the Auchen viscosity at room temperature (1 5 to 2 5 ° C) is 50 to 5 0000 cSt (0.5 Torr) (Γ5 to 5 00 X 1 〇-4 m2/ s) 'It is better to use 1 00 ~ 30000cSt (1 X 1 0 · 4 ~ 300xl0_4m2 / s), 150 ~ 25000cSt (1.5 χ 1) (1.5 χ 1 (Γ4 ~ © 25〇xl (T4m2 / s) The oil is not necessarily required, and the amount of the eucalyptus oil is selected from the range of 100 parts by weight or less (for example, 0 to 100 parts by weight) with respect to 100 parts by weight of the above-mentioned matrix composition, and can be selected from The ratio of 0 to 50 parts by weight may be 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight, more preferably about 5 to 25 parts by weight. Generally, when the eucalyptus oil is not used, the surface treatment agent can be improved. The anti-fogging property of the resin sheet (anti-fogging resin sheet) is lowered, and the mold release property is lowered, and the transfer is caused. However, in the present invention, even if the eucalyptus oil is not used, the mold release property is excellent and the mold release property is excellent and can be prevented. The surface treatment agent may also contain various additives such as stabilizers (antioxidants, ultraviolet absorbers, etc.) , skimming, coloring agents, antistatic agents, flame retardants, lubricants, waxes, preservatives, viscosity modifiers, tackifiers, leveling agents, defoamers, etc. In addition, surface treatment agents can usually be used as coating liquids. The form of the immersion liquid may be a non-aqueous liquid composition using an organic solvent as a solvent, and is usually used as an aqueous composition. Further, in the aqueous composition, the solvent may be water alone or as a solvent. Water and a hydrophilic solvent (especially a water-miscible solvent) [for example, alcohols (methanol, ethanol, isopropanol, etc.), ketones-23-201006877 (acetone, etc.), ethers (dioxane, tetrahydrofuran, etc.), a mixed solvent of serotypes (methicillin, ethyl siroli, butyl sulphate, etc.), carbitol, etc. The above surface treatment agent can be used by a conventional mixing mixer or a mixing disperser. The eucalyptus oil may be dispersed in accordance with the preparation. The solid content concentration of the surface treatment agent may be, for example, selected from the range of about 0.1 to 10% by weight, for example, 0.1 to 2% by weight, and 0.3 to 1.7 % by weight. Good, to 0.5~ The viscosity of the surface treatment agent is preferably selected in a range that does not impair the coating property, and may be 10 cps (0.01) at a temperature of 20 ° C when measured by a steady flow viscosity measurement method. Pa «s) is preferably 1.1 to 5 cps (for example, 1.2 to 3 cps), and more preferably about 1 to 3 cps. [Antifogging resin sheet and its production method] The antifogging resin sheet of the present invention is made of a resin. The sheet and the antifogging layer (coating layer or coating layer) formed on at least one surface (one surface or both surfaces) of the resin sheet, wherein the antifogging layer contains the surface treatment agent. As the resin sheet, various thermoplastic Φ resins having film or sheet formability can be used, such as polyethylene resin (polyethylene, ethylene-ethyl acrylate copolymer, ionic polymer, etc.), polypropylene resin (polypropylene, An olefin resin such as a propylene-ethylene copolymer or a poly-4-methylpentene-1; a vinyl alcohol resin such as polyvinyl alcohol or an ethylene-vinyl alcohol copolymer; or a vinyl chloride resin such as polyvinyl chloride. a styrene-based resin; a homo- or copolyester resin of an alkyl aryl ester unit such as polyethylene terephthalate or polybutyl phthalate; a nylon or polyamide resin; polypropylene A nitrile resin; a polycarbonate resin; a polyphenylene resin; a poly maple resin; a cellulose derivative or the like. These resins may be used alone or in combination of two or more. Further, the resin sheet may be a single layer sheet, and -24 - 201006877 may be a laminate sheet in which a plurality of resin sheets are laminated. The thickness of the resin sheet can be appropriately selected depending on the use, for example, 10 μm to 5 mm, preferably about 25 μm to 1 mm. When the container is formed, the thickness of the resin sheet may be, for example, 50 μm to 2 mm, preferably 50 μm to 1 μm (e.g., 100 to 1000 μm), more preferably about 120 μm to 500 μm. A preferred resin sheet can use a sheet having a moldability, particularly a hydrophobic synthetic resin sheet, such as an olefin resin (particularly a polypropylene resin) or a polyester resin (particularly polyethylene terephthalate). It is composed of an ester resin and a styrene resin. A resin sheet having high moldability, for example, a styrene resin sheet is particularly preferable. The styrene resin includes a homopolymer, an aromatic vinyl monomer, and a copolymerization property which are contained as a constituent component of an aromatic vinyl monomer (styrene, vinyl toluene, or α-methylstyrene). a copolymer of monomers and mixtures of such. More specifically, the styrene-based resin can be exemplified by a non-rubber-reinforced styrene resin [general polystyrene (GPPS), styrene-methyl methacrylate copolymer (MS resin), acrylonitrile-styrene copolymer ( AS resin), acrylonitrile-styrene-methyl methacrylate copolymer, etc., rubber-containing styrene resin [rubber-reinforced polystyrene (high impact polystyrene: HIPS), styrene-diene embedded Segment copolymer or hydrogen additive thereof (polystyrene-polybutadiene-polystyrene block copolymer, etc.), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile A and styrene S AXS resin obtained by graft-polymerizing rubber component X (acrylic rubber, chlorinated polyethylene, ethylene-propylene rubber (EPDM), ethylene/vinyl acetate copolymer, etc.). These benzene and sulphur resins may be used alone or in combination of two or more. Further, the styrene-based tree--25-201006877 fat sheet may be a styrene-based resin sheet having high transparency (for example, a non-rubber-reinforced styrene-based resin sheet composed of a non-rubber-reinforced styrene-based resin such as GPPS, and benzene). The styrene resin sheet composed of the ethylene resin and the styrene-diene block copolymer or the hydrogen additive thereof may be a rubber-reinforced styrene resin sheet. The resin sheet may also contain various additives such as stabilizers (antioxidants, ultraviolet absorbers, heat stabilizers, etc.), antistatic agents, crystal nucleating agents, hydrocarbon polymers, plasticizers, mineral oils, dips, colorants. The Φ resin sheet can be obtained by a usual film forming method such as a T-die method or a blow molding method. The resin sheet may be unstretched, but it is preferably stretched. The stretched film may be a uniaxially stretched film, but it is preferably a biaxially stretched film, and the stretched film may be subjected to heat treatment (heat setting treatment) as necessary. The stretching method may be a conventional stretching method such as roll stretching, calendering stretching, belt stretching, stretcher stretching, tube stretching, or a combination of the stretching methods. The stretching ratio can be appropriately set in accordance with the desired sheet characteristics, for example, 1.2 to 20 times, preferably 1.5 to 15 times, and more preferably 2 to 10 times. A usual surface treatment such as corona discharge treatment, high frequency treatment, or the like can also be applied to the surface of the resin sheet. In particular, it is preferred to subject the resin sheet to a corona discharge treatment and to form an antifogging layer on the corona discharge treated surface. In addition, the surface tension of the resin sheet varies depending on the type of the sheet, and cannot be determined in a single manner. When measured according to JIS K-6 76 8 "Test method for wetness of polyethylene and polypropylene film", it is 30 to 65 dyne/ Dimensions (30χ10·5~65xl (T5N/cm) or so. When the styrene resin sheet is used, the surface tension is 40~62 dynes/cm (4〇xl (T5 ~ 62xl (T5N/cm), with 42~62 It is better to use / centimeters (42) <10_5 to -26- • 201006877 62xl0·5 N/cm), preferably 45 to 60 dyne/cm (4 5xl0_5 to 6〇χ1 (Γ5 N/cm) or so. When the surface tension of the surface of the sheet is too high, the surface of the sheet may be excessively activated to become easily bonded. Therefore, it becomes difficult to unwind the sheet which has been wound into a roll, or the plural will be formed. When the containers are overlapped and perforated, the containers are adhered to each other, and the work efficiency of peeling off the containers and accommodating the contents is easily lowered. The antifogging resin sheet of the present invention is transparent and has a surface appearance (gloss, etc.) © excellent, even if the roll It is also high after being taken into a roll shape or after forming (for example, after deep drawing) The anti-fogging property can also reduce the contamination of the molding machine by the anti-fogging agent. The surface treatment agent can exhibit high anti-fogging property even with a small amount of coating. Therefore, the coating amount of the surface treatment agent (coating amount after drying) For example, it may be selected from a wide range of 2 to 150 mg/m 2 (for example, 3 to 100 mg/m 2 ), usually 5 to 60 mg/m 2 (for example, 7 to 50 mg/cm 2 ). The ruler is preferably φ of about 10 to 40 mg/m 2 . The present invention is a coating amount of 5 to 50 mg/m 2 (for example, 10 to 40 mg/m 2 ) even after drying of the surface treatment agent. In the case of forming the resin sheet into a container (for example, deep drawing), the antifogging property can be maintained. The antifogging resin sheet of the present invention may be treated with at least one surface of the resin sheet using a surface treatment agent, or a surface may be used. Treatment treatment (or coating treatment) - treatment with various treatment agents (such as coating agents containing antistatic agents, antistatic or lubricity antistatic agents or lubricants to improve adhesion resistance) (or coating The other side. In particular, it is also possible to form a coating layer of a surface treatment agent on the side of the resin sheet -27-.201006877 (corona discharge treatment, etc.), and on the other side (may also be a surface treated by corona discharge, etc.) Forming a release layer (or anti-adhesive layer). The release layer (or anti-adhesion layer) may also contain various release agents (or anti-adhesive agents), such as waxes (including mineral waxes, plant waxes, synthetic waxes) Preferably, the release layer contains at least eucalyptus oil. Further, the preferred release layer contains at least an ether-based hydrophilic polymer having an oxygen-extended ethyl group and an eucalyptus oil. Further, the eucalyptus oil can use the same eucalyptus oil (dimethyl methoxide or the like) as described above. Further, an ether-based hydrophilic polymer having a Φ-extended oxygen ethyl unit can use a nonionic surfactant such as a polyoxyethylene-polyoxypropylene block copolymer or a nonionic surfactant having an oxygen-extended ethyl group. Agents, etc. In a preferred embodiment, the eucalyptus oil can be used in the form of an emulsion (aqueous emulsion) in the same manner as described above. Further, the ether-based hydrophilic polymer may contain at least one selected from the group consisting of a polyoxyethylene-polyoxypropylene block copolymer and a nonionic surfactant having an oxygen-extended ethyl unit, and usually has a majority It is at least containing the aforementioned block copolymer. The ratio of the ether-based hydrophilic polymer to the release agent can be selected within a range that does not impair the antifogging property or the anti-adhesive property, and can be selected from the range of 〇 to 1000 parts by weight based on 100 parts by weight of the eucalyptus oil, and usually It is preferably from 1 to 500 parts by weight, preferably from 20 to 200 parts by weight (e.g., from 50 to 150 parts by weight), more preferably from 30 to 100 parts by weight (e.g., from 50 to 100 parts by weight). Further, the treatment agent such as a release agent may contain various additives such as a stabilizer (antioxidant, ultraviolet absorber, etc.), a tanning agent, a coloring agent, an antistatic, a flame retardant, a lubricant, a wax, a preservative, and a viscosity. Adjusting agent, tackifier, leveling agent, defoaming agent, etc. Further, the treating agent is usually in the form of a coating liquid or an immersion liquid of -28 to 201006877, or a non-aqueous liquid composition containing an organic solvent as a solvent, and is usually used as an aqueous composition. Further, in the aqueous composition, the solvent may be water alone or a mixed solvent of water and the above-exemplified hydrophilic solvent (particularly, a water-miscible solvent). The coating amount (the coating amount after drying) of the treatment agent such as a release agent can be selected from a wide range of about 1 to 200 mg/m 2 (for example, 5 to 100 mg/m 2 ) depending on the type of the treatment agent and the like. It is usually 2 to 100 mg / m ^ 2 and is preferably 3 to 50 mg / m ^ 2 (5 to 30 mg / m ^ 2 ). It is preferably about 5 to 25 mg / m ^ 2 . The antifogging resin sheet can be produced by applying the above surface treatment agent (or antifogging agent) to at least one side of the resin sheet. Further, the surface treatment agent (or antifogging agent) may be applied to one surface of the resin sheet, and the treatment agent (for example, a release agent or an anti-adhesive agent) may be applied to the other surface to produce an antifogging resin. sheet. The coating of the aforementioned surface treating agent can be carried out by a usual coating means such as a sprayer, a roll coater, a gravure roll coater, a knife coater, a dip coater or the like. Further, the above-mentioned surface φ surface treating agent may be applied in plural times as necessary. After the surface treatment agent (and treatment agent) is applied to the resin sheet, it is usually dried by a coating layer, and then attached to a roll (for example, a metal roll such as a guide roll), and taken up by a take-up roll. Since the antifogging resin sheet of the present invention is wound on the take-up roll without contaminating the roll, even in the resin sheet of the core portion, the transfer (transfer) of the antifogging component can be greatly suppressed, and not only the high temperature prevention It is also excellent in fogging and low-temperature anti-fog properties, and it can maintain high anti-fog property over a long period of time. Further, whitening can be suppressed without impairing the transparency, gloss, and the like of the resin sheet. Therefore, it can be used for various purposes such as a sheet (or film) for packaging such as a sheet (or film), a food package, or the like. -29- 201006877 The anti-fog resin sheet can be continuously supplied to the post-treatment process, etc., and usually the coiling is a post-rolling process. The resin sheet having high moldability has high secondary moldability and can be suitably molded into a container or the like. [Container and method for producing the same] The container (antifogging container) of the present invention is contained and formed in at least a part of the container. The surface (the surface or the outer surface, at least one of the inner surface or the outer surface of the lid, etc.) may be formed by a coating method (spray or the like) obtained on the surface of the resin container. The container may be obtained by using the antifogging container (the antifogging resin sheet is formed by processing). Since the container is excellent in antifogging property and transparency, a container or the like is used to store the storage containing moisture. The container is a resin exemplified in the resin sheet item constituting the resin container. The container usually has a body for storing food or the like, and the opening of the container body may be a packaging container. It is composed of a container body and a lid that passes through the opening of the hinge body. Further, the inner surface of the lid body can also be treated with the surface treatment agent. The container formed of the resin sheet, the antifogging resin sheet described above can be formed by a conventional hot forming method (or secondary forming process) by, for example, a blow molding method or a pressure forming method (hot plate heating type pressure forming method). And the I process (the shape of the container formed into a shape, and the coated resin sheet to be processed is processed. The resin container, such as the inner surface of the container body) is an anti-fog layer (including may be formed by coating the surface treatment agent resin sheet) It is useful for food packaging, and the fat can be used to cover at least the container film of the front material. When it is covered with the molded product of the container body, it is treated*. Container, hot forming method, vacuum forming radiant heating type -30-201006877, heating and pressure forming method such as forming method, vacuum pressure forming method, plug assist forming method, mold forming method, etc. When a resin sheet is stretched, it is usually a hot plate heating type vacuum forming method. In the present invention, even when such hot forming (secondary forming) is supplied, high antifogging can be maintained. In addition, the anti-fog resin sheet is subjected to deep drawing molding, which is excellent in anti-fogging property and low-temperature anti-fogging property, and can maintain high anti-fog property. (The ratio of the height of the container / the inner diameter of the opening) may be 0.4 to 1.5, preferably about 0.5 to 1.2 (for example, 0.6 to 1). [Industrial Applicability] Because of the antifogging resin of the present invention The sheet is excellent in antifogging property, and can prevent transfer, and is applied to a resin sheet by coating or the like to obtain an antifogging resin sheet. Further, since the antifogging surface treatment agent has little adhesion to a metal roll or the like. In the case of the anti-fogging resin sheet, the anti-fog resin sheet is highly transparent and glossy. The anti-fog resin sheet can be kept high even when it is supplied to secondary molding (for example, thermoforming). Anti-fog. A container having an antifogging layer formed of an antifogging surface treatment agent on the surface of the crucible has excellent antifogging property and high visibility of the stored product (or the contents). Therefore, the container of the present invention is suitable for storing various storage items (contents), in particular, a storage item (food or the like) containing moisture, and a container for use in an environment where fogging is likely to occur (for example, for storage in a container) It is also useful for containers such as fresh foods or prepared foods that are kept at a low temperature and other heat-conditioned foods. [Examples] Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the examples. Further, in the examples and comparative examples, the following components (A) to (D) ° (A) nonionic surfactant (A1) sucrose fatty acid ester (manufactured by RITAMAL A, RIKEMAL A, melting point) were used. 90 ° C ) (A2) polyoxyethylene lauryl ether (first industrial pharmaceutical (stock), DKS, NL-600 'melting point 54 ° C) (A3) glycerol mono oleate (Lita VITAMIN (shares) System, RIKEMAL U B-100, melting point of 75 ~ 82..). (B) Water-soluble polymer (Bl-i) polyvinylpyrrolidone (manufactured by BASF Corporation, LUVITEC K-90, glass transition temperature of 180 ° C, weight average molecular weight of 9〇xl04 〜1 5〇χ 1 04 (Bl-ii) vinylpyrrolidone/vinyl acetate copolymer (manufactured by BASF Corporation, LUVITEC VA 64, glass transition temperature: 70 °C) (Bl-iii) polyvinyl alcohol (KURARAY, POVAL) PVA117, ❹ melting point of 180 ° C, saponification degree of 98~99 mol%) (Bl-iv) methyl cellulose (manufactured by Shin-Etsu Chemical Co., Ltd., METOLOSE SM100 > melting point 300 °C) (Bl- v) Carboxymethyl cellulose (manufactured by DAICEL Chemical Industry Co., Ltd., CMC DAICEL 1 260, melting point 230 ° C) (B2) Polyoxyethylene-polyoxypropylene block copolymer (first industrial pharmaceutical company) , EPAN U108, melting point 57 ° C), weight average molecular weight 18000, ethylene oxide content rate 80%) (C) anionic surfactant -32- 201006877 (Cl) sodium alkane sulfonate (Kao (share) system, LATEMUL PS, sodium alkane sulfonate of about 15 carbon atoms) (C2) sodium lauryl sulfate (made by Kao), EMAL 2FG (D) oyster sauce (D1) 矽 emulsion (TORAY-DOWCORNING, SM7025, solid content concentration: 33% by weight) Examples 1 to 18 and Comparative Examples 1 to 6 were prepared so that the solid content ratio of each component (weight ratio after drying of each component) φ was expressed as a ratio (parts by weight) shown in the table. Aqueous surface treatment agent (anti-fog treatment agent). Further, the concentration of the treating agent differs depending on the evaluation item, and the concentration of the treating agent indicates the concentration (% by weight) of the solid component. Furthermore, the aqueous surface treatment agent (antifogging treatment agent) is applied to the corona discharge treatment surface of the biaxially stretched polystyrene film having a sheet thickness of 0.25 mm in a predetermined amount by the following evaluation characteristics. The anti-fog layer was formed by drying at 80 ° C for 2 minutes using a hot air dryer. The characteristics (initial characteristics) of the antifogging resin sheet obtained by the following evaluation were evaluated, and the characteristics (post-pressurization characteristics) of the sheet after the antifogging resin sheet was laminated and pressurized were evaluated. (1) Initial characteristics of antifogging resin sheet (Ι-i) Transferability to metal A biaxially stretched polystyrene sheet having a sheet thickness of 0.25 mm at 54 dynes/cm or more (54 x 10 _ 5 N/cm) Corona discharge treatment was carried out, and an anti-fogging treatment agent (concentration: 1.0% by weight) was applied to the corona discharge treatment using a No. 5 Mayer's bar at a coating amount of 30 mg/m 2 after drying. The surface was dried by a hot air dryer at 80 °C for 2 minutes to form an anti-fog-33-201006877 layer. The obtained antifogging resin sheet was cut into a predetermined size (5 cm X 5 cm), and laminated on the anti-fog side with aluminum sheets of the same size, and sandwiched with a stainless steel plate (thickness: 5 mm, 3 cm x 5 cm) . It was placed horizontally in a 60 ° 恒温 thermostat, and then a 15 kg weight was placed and left for 1 hour. After standing, after taking out from the constant temperature bath and cooling to normal temperature, the surface where the anti-fog surface is in contact with the aluminum sheet was observed, and the ratio of the anti-fog surface to the aluminum sheet with respect to the contact area was determined. Five sheets were evaluated and their average was determined. (1-Π) High-temperature anti-fog property A biaxially stretched polystyrene sheet having a sheet thickness of 0.25 mm is subjected to corona discharge treatment at 54 dynes/cm or more (54 x 10 _ 5 N/cm), and an anti-fogging treatment agent ( The concentration of 0.7% by weight) was coated on the corona discharge treated surface with a No. 5 Mayer's bar at a coating amount of 20 mg/m 2 after drying, and dried by a hot air dryer at 80 ° C for 2 minutes. To form an anti-fog layer. The obtained antifogging resin sheet was cut into a predetermined size (120 mm X 120 mm) and stretched by 70 mm using a table type biaxial stretching machine (manufactured by Iwamoto Seisakusho Co., Ltd.). The sheet was placed in the opening of the container in which hot water was placed at 60 ° C, and placed on the antifogging layer of the sheet, and left in a normal temperature environment for 2 minutes. Then, the vapor-contacting portion of the sheet was placed on the "anti-fogging property" of a character group of different font sizes printed on the paper, and visually evaluated in accordance with the following criteria, and the degree of haze of the five sheet sheets was evaluated. 5: The "anti-fog" text with a font size of 5 can clearly read 4: The "anti-fog" text with a font size of 10 can clearly read 3: "The size of the font is 14" The "fog" text can be clearly read 2: The "anti-fog" text with a font size of 18 can be clearly read 1: the text is indistinguishable. -34- r 201006877 (1-iii) Low-temperature anti-fog property at a temperature of 23 °C in the surrounding water, in a container filled with water (23 °C), will be obtained in the evaluation of (2) high-temperature anti-fog property The antifogging resin sheet which was stretched was placed with the antifogging layer facing the opening of the container, and placed in a 5 t thermostatic bath in this state and left for 10 minutes. Then, similarly to the evaluation of (2) high-temperature antifogging property of the initial characteristics of the anti-fogging resin sheet, the degree of haze of the sheet just taken out was evaluated, and the average enthalpy of the results of evaluation of the five sheets was calculated. (Ι-iv) Durability ^ 20 g of an antifogging aqueous solution having a solid concentration of 1% by weight was poured into a cup made of aluminum foil, and placed in an oven at 80 ° C to evaporate water (drying time was 2 hours). The film was obtained. After cooling to room temperature, the film was peeled off from the aluminum cup, and the film was repeatedly bent at an angle of 90 degrees and once every 2 seconds by hand, and then returned to observe the bent portion. 5: No change in 20 bends 4: When it is bent 20 times, whitening or a little crack is observed. 3: 11~19 bends occur when cracking occurs.> 2: 6~10 bends occur when cracking 1: 5 times The following bending occurs when cracking occurs. (2) Characteristics of the sheet after pressurization A biaxially stretched polystyrene sheet having a sheet thickness of 0.25 mm is subjected to corona discharge treatment at 54 dynes/cm or more (54 x 10 _ 5 N/cm), and An antifogging treatment agent (concentration: 0.7% by weight) was applied to the corona discharge treated surface with a No. 5 Mayer's bar at a coating amount of 20 mg/m 2 after drying, and dried to form an antifogging layer. . The obtained anti-fog resin sheet was cut into a predetermined size (30 cm χ 30 cm) and 10 sheets were superposed, and after pressurizing for 1 hour at a temperature of 40 - 35 - 201006877 ° C and a load of 10 kgf / cm 2 (with 98 N / cm 2 ), The pressure was released, and each sheet was separated, and the sheet transfer and the high-temperature antifogging property were evaluated in accordance with the following, as an index of the sheet characteristics when the sheet was wound into a roll. (2-i) Whitening The haze (%) before and after the pressurization of the antifogging resin sheet was measured, and the difference was determined. (2-ii) High-temperature anti-fogging property The sheet separated after the pressurization is operated in the same manner as the evaluation of the high-temperature antifogging property (Ι-ii) of the initial characteristics of the anti-fogging resin sheet, and The evaluation of the high-temperature anti-fogging property (Ι-ii) was similarly evaluated, and the average enthalpy of the five sheets was calculated. The results are shown in Tables 1 to 3. -36- 201006877

[1 5

Embodiment 9 〇〇»n inch 实施 Example 8 rn 〇〇 〇〇 » » » 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 对 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施Example 3 jn 〇〇ο inch Example 2 s 〇〇»n ο Example 1 JQ IT) (S 〇〇»n tJ· ο inch nonionic surfactant A1 (parts by weight) Ionic surfactant 8.2 (parts by weight) Nonionic surfactant 8.3 (parts by weight) Aqueous solution of polymer Bl-i®) Aqueous solution of polymer Bl-ii (parts by weight) Aqueous solution of high liver Bl-iii ( Parts by weight) aqueous solution high liver Bl-iv (parts by weight) aqueous solution high liver Bl-v (parts by weight) 1 aqueous solution polymer B2 (parts by weight) anionic surfactant C1 (parts by weight) anionic surfactant C2 (weight Parts) Metal transfer li (%) High temperature anti-fog l-ii Low temperature anti-fog l-iii Durability l-iv Transitive 2-i High temperature anti-fog property 2-ii < U — Li_ 201006877

Example 18 g 〇〇in m 实施 Example 17 § 〇 〇 〇 〇 〇 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施Example 12 g 〇〇 Vi inch 实施 Example 11 实施 inch inch 实施 Example 10 § 〇〇 inch inch non-ionic surfactant A1 (parts by weight) Nonionic surfactant A2 (parts by weight) Nonionic surfactant A3 (parts by weight) aqueous solution polymer Bl-i (parts by weight) aqueous solution high liver Bl-ii (parts by weight) aqueous solution polymer Bl-iii (parts by weight) aqueous solution polymer Bl-iv (parts by weight) Aqueous solution polymer Bl-v (parts by weight) aqueous solution polymer Β 2 (parts by weight) anionic surfactant C1 (parts by weight) anionic surfactant C2 (parts by weight) metal transfer 1-TO high temperature antifogging L-ii Lion anti-fog l-iii Durability l-iv Transitive 2-i High temperature anti-fog property 2-ii PQ U

Oo CO 201006877 ο❹ [ε谳]

Comparative Example 6 g • 〇 inch inch <NO) Comparative Example 5 § 〇 (N CS cn un cs cn Comparative Example 4 〇 2 〇 CN inch < N (N Comparative Example 3 § 〇 (N m CN CS Comparative Example 2 § 〇cn inch CN <N CN Comparative Example 1 § 〇 (N CN (N 〇in oi nonionic surfactant A1 (parts by weight) Nonionic surfactant A2 (parts by weight) Nonionic surfactant A3 (parts by weight) aqueous solution polymer Bl-i (parts by weight) aqueous solution polymer Bl-ii (parts by weight) aqueous solution polymer Bl-ii swollen part) aqueous solution polymer Bl-iv (parts by weight) aqueous solution polymer Bl- v (parts by weight) aqueous solution polymer B2 (parts by weight) anionic surfactant C1 (parts by weight) anionic surfactant C2 (parts by weight) eucalyptus oil D1 metal transferability li (%) high temperature antifogging property 1-ii Low temperature antifogging property l_iii Durability l-iv Printing property 2-i High temperature antifogging property 2-ii <3 PQ UQ -67 201006877 It is clear from the above table that the antifogging property of the example is compared with the comparative example. Resin sheet can be displayed even if the coating amount is small High anti-fogging property (high-temperature and low-temperature anti-fogging property) can maintain high anti-fog property even in supply molding (especially deep drawing, etc.), and the anti-fog resin sheet is wound up in a roll shape. Low printability and low adhesion to metal, and low transferability. [Simplified illustration] Μ 〇 [Main component symbol description] No.

-40-

Claims (1)

201006877 VII. Patent Application Range: 1. An anti-fogging surface treatment agent comprising (A) a nonionic surfactant, (B) a water-soluble polymer, and (C) an anionic surfactant. 2. The surface treatment agent of claim 1, wherein the (A) nonionic surfactant has a melting point or softening point of 50 ° C or more. 3. The surface treatment agent according to claim 1 or 2, wherein the (A) nonionic surfactant is selected from the group consisting of sucrose fatty acid esters, polyglycerin fatty acid esters, glycerin fatty acid esters, and polyoxyethylene alkyl groups. At least one of ethers. The surface treatment agent according to any one of claims 1 to 3, wherein the (B) water-soluble polymer does not contain (B1) a water-soluble polymer of an oxyalkylene unit. 5. The surface treatment agent according to any one of claims 1 to 4, wherein (B) the water-soluble polymer is selected from the group consisting of (B1) vinylpyrrolidone polymer, vinyl alcohol polymer, At least one of cellulose ethers and alginic acid or a salt thereof. 6. The surface treatment agent of claim 4 or 5, wherein the (B) water-soluble polymer further contains (B2) a polyoxyalkylene polymer. 7. The antifogging surface treatment agent according to the sixth aspect of the invention, wherein the ratio of the (B2) polyoxyalkylene polymer is 50% by weight or less based on the total of the (B) water-soluble polymer. The surface treatment agent according to any one of claims 1 to 7, wherein the (C) anionic surfactant is selected from the group consisting of a carboxylate, a sulfate, a sulfonate, and a phosphate or a phosphate salt. At least one of them. The surface treatment agent according to any one of claims 1 to 8, which comprises (A) a nonionic surfactant and (B) water-41 - , 201006877 , a soluble polymer with respect to 100 parts by weight. The ratio of the former/the latter = 1/99 to 99/1 (by weight) of the matrix composition contains 0.1 to 200 parts by weight of the (C) anionic surfactant. 10. The surface treatment agent according to any one of claims 1 to 9, wherein (A) the nonionic surfactant is a sucrose fatty acid ester, and (B) the water soluble polymer contains a vinyl pyrrolidone a polymer, (C) an anionic surfactant sulfonate; and a ratio of (A) a nonionic surfactant to (B) a water-soluble polymer relative to 1 part by weight of the former/the latter φ The matrix composition of =20/80 to 95/5 (by weight) contains 1 to 150 parts by weight of (C) an anionic surfactant. 11. The surface treatment agent according to claim 10, wherein the (B) water-soluble polymer further contains (B2) a polyoxyalkylene polymer, and (B) a water-soluble polymer, (B2) The ratio of the polyoxyalkylene polymer is from 1 to 40% by weight. 12. An antifogging resin sheet comprising an antifogging layer comprising a surface treating agent as described in any one of claims 1 to 11 on at least one side of the resin sheet. The antifogging resin sheet according to Item 12 of the patent application, wherein an antifogging layer is formed on one surface of the resin sheet and a release layer is formed on the other surface. 14. The antifogging resin sheet according to claim 12, wherein the resin sheet is a styrene resin sheet. A method of producing an antifogging resin sheet, which is a surface treatment agent according to any one of claims 1 to 11, which is applied to one side of a resin sheet. 16. The method for preparing an anti-fog resin sheet according to claim 15 of the patent application, which is obtained by coating a surface treatment agent on a resin sheet, and winding it into a roll, which is a resin. The surface of at least a portion of the container is formed with an antifogging layer containing the surface treating agent according to any one of claims 1 to 11. A container formed of an antifogging resin sheet according to any one of claims 12 to 14. -43- 201006877 * ‘ IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: