JP2009249575A - Antifogging surface treating agent, and antifogging resin sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antifogging treating agent and an antifogging resin sheet of excellent antifogging property. <P>SOLUTION: This antifogging surface treating agent contains (A) an aliphatic amide such as an 8C-30C fatty acid alkanol amide, and (C) 0.1-400 pts.wt. of nonionic surfactant such as a sucrose fatty acid ester, and/or (D) 0.1-200 pts.wt. of anionic surfactant such as an alkane sulfonate, per (B) 100 pts.wt. of base composition constituted of a water-soluble polymer such as a vinyl pyrrolidone polymer. The antifogging resin sheet suitable for a deep-drawing container molding is manufactured by applying the surface treating agent onto at least one face of a styrenic resin sheet. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an antifogging surface treatment agent (antifogging treatment agent) useful for imparting antifogging properties to the surface of a resin sheet or the like, and an antifogging resin sheet obtained by treating a resin sheet with this antifogging treatment agent. And a method for producing the same, and a container having antifogging properties.

  Hydrophobic synthetic resin sheets such as styrene resin sheets that are used in packaging containers for foods have low antifogging properties. When food or the like is stored in a container formed of such a resin sheet, water vapor adheres to the surface of the container as fine water droplets due to changes in temperature and humidity, resulting in cloudiness and reduced transparency. For this reason, the visibility of the contents is lowered.

  Then, the method of providing antifogging property to a resin sheet using fatty acid esters etc. is proposed. For example, in Japanese Patent Publication No. 63-62538 (Patent Document 1), an aqueous solution containing sucrose fatty acid ester, unmodified polyvinyl alcohol having a polymerization degree of 800 or less, and a silicone emulsion in a specific ratio is applied to a styrene resin film. A method is disclosed. In JP-A-10-309785 (Patent Document 2), one surface is coated with a mixture of sucrose fatty acid ester and methylcellulose, and this coating layer is further coated with silicone oil, and the other surface is coated with silicone oil. A styrenic resin sheet coated with is disclosed. In Japanese Patent No. 3241497 (Patent Document 3), a surface treatment agent containing a sucrose fatty acid ester, a silicone emulsion, a polysaccharide and / or a hydrophilic polymer (excluding polyvinyl alcohol) is used. Application to at least one surface is disclosed. JP-A-2003-201355 (Patent Document 4) describes a mixture of a polyhydric alcohol type nonionic surfactant such as sucrose fatty acid ester and polyglycerin fatty acid ester and a polyethylene glycol type nonionic surfactant. An antifogging resin sheet whose surface is coated is disclosed. JP-A-2004-238614 (Patent Document 5) discloses a polyhydric alcohol fatty acid ester, a non-ether hydrophilic polymer excluding polyvinyl alcohol, and an ether-based hydrophilic polymer having at least an oxyethylene unit. An anti-fogging sheet coated with a surface treatment agent composed of silicone oil is disclosed.

  However, these conventional antifogging sheets have insufficient antifogging properties. That is, the anti-fogging sheet has anti-fogging properties (high-temperature anti-fogging property) against water vapor generated from the contents when, for example, high-temperature contents are contained in the container, in particular, the contents containing moisture in the container. When storing (foods etc.) and storing at low temperature, antifogging property (low temperature antifogging property) against water vapor or condensation is low. Further, the antifogging property is greatly reduced by winding the sheet or forming the container. That is, a resin sheet (for example, a styrene resin sheet) used for container molding is, for example, melt-kneaded resin, extruded into a sheet shape, biaxially stretching the formed sheet, and then applying an antifogging agent And dried and wound up into a roll. And in container shaping | molding, the resin sheet is drawn out from the roll and the container is shape | molded by thermoforming. However, with the winding of the resin sheet, the antifogging agent contacts the non-fogging treated surface of the resin sheet and transfers (transfers / transfers) to the back, and the antifogging property is lowered. Appearance deteriorates due to whitening. In particular, since a large pressure acts on the core part of the sheet wound up in a roll shape, the above-mentioned performance reduction is noticeably observed in the sheet of the core part. Furthermore, in the container molding process, the antifogging agent is transferred due to contact with a heating body such as a hot plate, or the antifogging property or blocking resistance of the resin sheet or container is greatly reduced. Is contaminated. In general, when containers are formed by deep drawing, the antifogging property is greatly reduced. For this reason, it is necessary to apply a large amount of the antifogging agent. However, if the application amount of the antifogging agent is increased, the set-up due to the transfer of the antifogging agent described above and contamination of the molding machine occur. Furthermore, in order to improve the releasability of the antifogging sheet, a relatively large amount of silicone oil is required.

JP-A-2001-171052 (Patent Document 6) discloses that an antistatic agent containing a fatty acid amide and a polyoxyethylene-polyoxypropylene block copolymer in a specific ratio is applied on at least one surface in an amount of 2 to 30 mg. A styrenic resin sheet coated at / m ² is disclosed. This document also describes that the antistatic agent further contains silicone oil, and the coating amount of the silicone oil is 1 to 25 mg / m ² . Japanese Patent Application Laid-Open No. 2002-12686 (Patent Document 7) discloses a coating composition composed of a fatty acid amide, a polyoxyethylene-polyoxypropylene block copolymer, a silicone oil, and a water-soluble blue colorant. A resin sheet coated on the surface with a specific quantitative relationship is disclosed, and the fatty acid amide and the polyoxyethylene-polyoxypropylene block copolymer constitute an antistatic composition.

  However, these documents do not describe antifogging properties. Moreover, in the said sheet | seat, although antistatic property is improved to some extent, since there are many ratios of fatty acid amide, transparency falls. Also, a relatively large amount of silicone oil is required in order to improve the releasability of the sheet. Furthermore, when the antistatic agent (or coating agent) is applied to the surface of the resin sheet, dried, and wound up using a roll, a part of the coating component adheres or accumulates and a roll (such as a metal roll) is formed. Contaminated and anti-fogging property is reduced. In addition, deposits or deposits are retransferred to the sheet, and the appearance of the sheet is also impaired.

  JP 2000-178370 A (Patent Document 8) discloses an antifogging agent containing 10 to 90% by weight of an anionic surfactant and 90 to 10% by weight of a hydrophilic polymer. It is disclosed that a styrene transparent resin sheet is surface-treated with an antifogging agent in which 30% by weight or more of the anionic surfactant is a sulfate ester salt to obtain an antifogging sheet. This document exemplifies hydroxyethyl cellulose, polyvinyl pyrrolidone and the like as hydrophilic polymers. In JP-A-2003-26833 (Patent Document 9) and JP-A-2005-356572 (Patent Document 10), the amount of sucrose fatty acid ester of 76 to 99.9% by mass and the amount of unreacted vinylpyrrolidone is 1000 ppm or less. It is disclosed that a rubber-modified styrene resin sheet or a styrene transparent resin sheet is surface-treated with an antifogging agent containing 0.1 to 24% by mass of a polyvinylpyrrolidone (co) polymer to obtain an antifogging sheet. Yes.

However, when a resin sheet coated with these antifogging agents is molded into a container (particularly deep drawing), the antifogging property is greatly reduced. In particular, when the coating amount is reduced, the antifogging property is remarkably lowered by container molding (particularly deep drawing), and it is difficult to achieve high antifogging property.
Japanese Examined Patent Publication No. 63-62538 JP-A-10-309785 Japanese Patent No. 3241797 JP 2003-201335 A (Claim 1 and paragraph number [0005]) JP 2004-238614 A (Claim 1 and paragraph number [0001]) JP 2001-171052 A JP 2002-12686 A JP 2000-178370 A (Claims) JP 2003-26833 A (Claims) Japanese Patent Laying-Open No. 2005-356572 (Claims)

  Accordingly, an object of the present invention is to provide an antifogging surface treatment agent (or antifogging composition) that exhibits high antifogging properties including high temperature antifogging properties and low temperature antifogging properties, and uses thereof (antifogging resins). It is to provide a sheet, a manufacturing method thereof, and a container using the antifogging resin sheet.

  Another object of the present invention is to provide an antifogging surface treatment agent that can provide extremely high antifogging properties even when applied in a small amount and can maintain high antifogging properties even when subjected to container molding (particularly deep drawing). Or an anti-fogging composition) and its use.

  Still another object of the present invention is to provide an anti-fogging surface treatment agent capable of maintaining a high-quality appearance without contaminating a roll (especially a metal roll) even if it is applied to a resin sheet, dried and wound up, and uses thereof. It is to provide.

  Another object of the present invention is to provide an antifogging surface that can be applied to a resin sheet, wound up in a roll shape, and not flipped over in the winding core, maintaining high antifogging properties and high quality appearance. It is in providing a processing agent and its use.

  Still another object of the present invention is to provide an antifogging surface treatment agent capable of maintaining high antifogging properties even when subjected to winding or thermoforming, and having high mold releasability (or anti-blocking properties), and uses thereof. It is to provide.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventor has found that a fatty acid amide, a water-soluble polymer (such as a polyvinylpyrrolidone polymer), a nonionic surfactant (such as a sucrose fatty acid ester) and / or When combined with anionic surfactants (such as sulfonates), extremely high antifogging properties can be obtained even with small coating amounts, and high antifogging properties are maintained even when used for container molding (especially deep drawing). It was found that even if it was applied to a resin sheet, dried and wound up, the roll (especially a metal roll) was not contaminated, and even the core part wound up in the form of a roll was not turned over. completed.

That is, the antifogging surface treatment agent (antifogging treatment agent) of the present invention comprises (A) a fatty acid amide, (B) a water-soluble polymer, (C) a nonionic surfactant and / or (D). Anionic surfactant. The (A) fatty acid amide includes (A-1) C _8-30 fatty acid amide or a C _2-4 alkylene oxide adduct thereof, and (A-2) C _8-30 fatty acid mono- or dialkanol amide or a C ₂ thereof. _It may be at least one selected from _-4 alkylene oxide adducts. Further, (B) the water-soluble polymer may have a melting point, softening point or glass transition temperature of 60 ° C. or higher. (B) Water-soluble polymers include vinyl pyrrolidone polymers, vinyl alcohol polymers, cellulose ethers, alkylene ether polymers, alginic acid or salts thereof, and at least one of these water-soluble polymers. May be used. (C) The nonionic surfactant may have a melting point, softening point or glass transition temperature of 50 ° C. or higher. (C) The nonionic surfactant may be composed of at least one selected from sucrose fatty acid ester, polyglycerin fatty acid ester, glycerin fatty acid ester and polyoxyethylene alkyl ether. (D) The anionic surfactant may be a sulfonate, a sulfate ester salt, a carboxylate salt, a phosphate salt or a phosphate ester salt, and at least one of these anionic surfactants is used. May be. Further, (D) the anionic surfactant may be composed of at least one selected from alkane sulfonate and alkyl sulfate ester salt.

Further, the surface treatment agent (antifogging agent or antifogging composition) comprises (A-1) C _8-26 fatty acid amide or an ethylene oxide adduct thereof, and (A-2) C _8-26 fatty acid mono- or di- (A) a fatty acid amide composed of at least one selected from alkanolamides or ethylene oxide adducts thereof, (B) a water-soluble polymer composed of a vinylpyrrolidone-based polymer, and (C) a nonionic interface It includes at least (C) a nonionic surfactant among the active agent and (D) anionic surfactant, and (C) the nonionic surfactant may be composed of at least a sucrose fatty acid ester.

  The ratio of each component is, for example, based on 100 parts by weight of the base composition containing (A) fatty acid amide and (B) water-soluble polymer in the ratio of the former / the latter = 1/99 to 99/1 (weight ratio). (C) 0.1 to 400 parts by weight of nonionic surfactant and / or (D) about 0.1 to 200 parts by weight of anionic surfactant may be used.

More specifically, the surface treatment agent (anti-fogging agent or anti-fogging composition) is obtained from (A) a fatty acid amide (A-2) a C _8-20 fatty acid mono- or dialkanol amide or an ethylene oxide adduct thereof. Composed of at least one selected, (B) the water-soluble polymer is composed of at least one selected from vinyl pyrrolidone polymers, vinyl alcohol polymers, cellulose ethers, and a melting point of 62 ° C. or higher, Having a softening point or glass transition temperature, (C) the nonionic surfactant is composed of a sucrose fatty acid ester having a melting point of 53 ° C. or higher, a softening point or a glass transition temperature, and (D) an anionic interface The activator is composed of at least one selected from alkane sulfonate and alkyl sulfate ester salt, and comprises (A) a fatty acid amide and (B) a water-soluble polymer. (C) 1 to 380 parts by weight of nonionic surfactant and / or (D) anionic interface with respect to 100 parts by weight of the base composition containing the latter in a ratio of 10/90 to 90/10 (weight ratio) 1 to 150 parts by weight of activator may be included.

  The surface treatment agent (antifogging agent or antifogging composition) of the present invention forms an antifogging resin sheet in which an antifogging layer composed of the surface treatment agent is formed on at least one surface of the resin sheet. Useful for. In the antifogging resin sheet, the resin sheet may be subjected to corona discharge treatment, and an antifogging layer may be formed on the corona discharge treatment surface. Further, an antifogging layer may be formed on one surface of the resin sheet, and a release layer may be formed on the other surface. Further, the resin sheet may be a styrene resin sheet.

  Such an antifogging resin sheet can be produced by applying the surface treatment agent to at least one surface of the resin sheet. In this manufacturing method, after applying the surface treatment agent to the resin sheet, it may be wound into a roll.

The present invention provides a container in which an antifogging layer composed of the surface treatment agent is formed on at least a part of the surface of a resin container, a container formed of the antifogging resin sheet, and at least one of resin sheets An anti-fogging container in which the surface treatment agent is applied to the surface in an application amount of 5 to 50 mg / m ² and container-molded (for example, deep-draw molding) is also included.

  In the present specification, the “sheet” is used to mean a two-dimensional structure such as a film or a plate. Further, “melting point, softening point or glass transition temperature” is sometimes simply referred to as “melting point”.

  In the present invention, (A) a fatty acid amide, (B) a water-soluble polymer, (C) a nonionic surfactant and / or (D) an anionic surfactant are combined, Anti-fogging properties exhibiting high anti-fogging properties including low-temperature anti-fogging properties can be obtained. In particular, even when the coating amount is small, extremely high antifogging properties can be obtained, and high antifogging properties can be maintained even when subjected to container molding (particularly deep drawing). Furthermore, even if the resin sheet is applied, dried and wound, the roll (particularly metal roll) is not contaminated, and a high-quality appearance can be maintained. Furthermore, even if it is applied to a resin sheet and wound up in a roll shape, it will not be transferred to the winding core portion, and high antifogging properties and high quality appearance can be maintained. Moreover, even if it uses for winding and thermoforming, while being able to maintain high anti-fogging property, high mold release property (or blocking resistance) is obtained.

[Surface treatment agent]
The antifogging surface treatment agent (antifogging agent or antifogging composition) of the present invention comprises (A) a fatty acid amide, (B) a water-soluble polymer, (C) a nonionic surfactant and / or (D ) Anionic surfactant.

(A) Fatty acid amide The fatty acid amide (A) is a compound in which a hydrogen atom of an amine (amine or ammonia) is substituted with an acid group corresponding to a fatty acid (aliphatic carboxylic acid), and is an amide of a fatty acid and an amine. Can be represented. The fatty acid amide (A) also includes an alkylene oxide adduct of a fatty acid amide (for example, a C _2-4 alkylene oxide adduct such as an ethylene oxide adduct or a propylene oxide adduct). Fatty acid amides (including alkylene oxide adducts) can be used alone or in combination of two or more.

The fatty acid constituting the fatty acid amide may be either a monocarboxylic acid or a polycarboxylic acid, but is often a monocarboxylic acid. The fatty acid may be either a saturated or unsaturated fatty acid. The fatty acid is a C _6-40 fatty acid, preferably a C _8-30 fatty acid (eg saturated acids such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, hydroxystearic acid, arachidic acid, behenic acid, montanic acid, etc. , oleic acid, _{C 8-26} fatty acids and unsaturated fatty acids such as erucic acid), more preferably _{C 10-22} fatty acids _{(e.g., C 10-20} fatty acid), especially _{C 10-18} fatty acids (lauric acid, myristic acid , Saturated fatty acids such as palmitic acid and stearic acid, and unsaturated fatty acids such as oleic acid). The fatty acid is not limited to a single fatty acid, and may be a mixture of a plurality of fatty acids (for example, a mixture of capric acid, lauric acid, myristic acid (coconut oil fatty acid, etc.)). That is, the fatty acid amide may be a mixed fatty acid amide.

The amine constituting the fatty acid amide may be ammonia, primary amine (or N-monosubstituted amine) or secondary amine (or N, N-disubstituted amine), monoamine or polyamine, Also good. The primary amine and secondary amine may be alicyclic amines or aromatic amines, but are often aliphatic amines. Examples of the aliphatic primary amine include monoalkylamines such as methylamine, ethylamine, propylamine and butylamine (mono-C _1-6 alkylamines), monoalkanolamines such as ethanolamine, isopropanolamine and butanolamine. (C _1-6 alkanolamines, especially C _2-4 alkanolamines), alkylenediamines such as ethylenediamine, propylenediamine, trimethylenediamine, butylenediamine ( _C2-6 alkylenediamines, etc.) . Examples of the aliphatic secondary amines include dimethylamine, diethylamine, dialkylamines such as dibutylamine (di-C _1-6 alkyl amines, etc.), diethanolamine, dialkanolamines such as diisopropanolamine (di-C _1-6 Alkanolamines, especially diC _2-4 alkanolamines), alkyl alkanolamines such as methylethanolamine, ethylethanolamine (C _1-6 alkyl C _1-6 alkanolamines, especially C _1-4 alkyl C _{2) -4} alkanolamines). The fatty acid amide may be either monoamide or polyamide.

Specific examples of fatty acid amides include saturated or unsaturated fatty acid amides such as alkanecarboxylic acid amides (capric acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, arachidic acid amide, behenic acid amide, C _8-30 alkane carboxylic acid amides such as montanic acid amide and 12-hydroxystearic acid amide), alkene carboxylic acid amides (such as C _8-30 alkene carboxylic acid amides such as oleic acid amide and erucic acid amide), N- Substituted C _8-30 fatty acid amides [N-substituted saturated or unsaturated fatty acid amides, such as N-alkyl-alkanecarboxylic acid amides (eg, N-methyl lauric acid amide, N-methyl palmitic acid amide, N-palmityl palmitic acid) Acid amide, N, N-dimethyl ester _{N-C 1-26} alkyl _{-C 8-30} alkanecarboxylic acid amide, such as phosphoric acid amide (preferably _{N-C 1-20} alkyl _{-C 8-30} alkanecarboxylic acid amide), etc.), N- alkyl - alkene carboxylic Acid amides (for example, N—C _1-26 alkyl-C _8-30 alkene carboxylic acid amides such as N-methyl oleic acid amide (preferably N—C _1-20 alkyl-C _8-30 alkene carboxylic acid amide, etc.) N-alkenyl-alkanecarboxylic acid amides (N-C _2-26 alkenyl-C _8-30 alkanecarboxylic acid amides such as N-oleyl palmitic acid amide (preferably N—C _2-20 alkenyl-C _8-30 alkanes); N-alkenyl-alkene carboxylic acid amide (N-oleyl oleic acid amide) Amides of mono- or di-alkanolamine and alkanecarboxylic acids; any _{N-C 2-26} alkenyl _{-C 8-30} alkene carboxylic acid amide (preferably _{N-C 2-20} alkenyl _{-C 8-30} alkene carboxylic acid amide) (N- (hydroxy C _1-4 alkyl) -C _8-30 such as N-methylol lauric acid amide, capric acid ethanolamide, lauric acid ethanolamide, lauric acid isopropanolamide, myristic acid ethanolamide, coconut oil fatty acid ethanolamide) alkanecarboxylic acid amides (preferably N- (hydroxy _{C 2-3 alkyl) -C 8-30} alkanecarboxylic acid amide; capric acid diethanolamide, lauric acid diethanolamide, myristic acid diethanolamide, coconut oil fatty acid diethanolamine Di C _1-4 amides of alkanolamines (preferably di C _2-3 alkanolamines) and C _8-30 alkanecarboxylic acid) and the like; amides of mono- or di-alkanolamine and an alkene carboxylic acid (oleic acid ethanolamide N- (hydroxy C _1-4 alkyl) -C _8-30 alkene carboxylic acid amides; diC _1-4 alkanolamines (preferably diC _2-3 alkanolamines) such as oleic acid diethanolamide and C _{8- 30} amides of alkene carboxylic acid); N-aminoalkyl - alkanecarboxylic acid amide (N- (aminomethyl) - lauric acid amide, N- (aminoethyl) - N- such lauric acid amide (amino _{C 1-26} Alkyl) -C _8-30 alkanecarboxylic acid amide (preferably N- (amino C _{1 -20} alkyl) -C _8-30 alkanecarboxylic acid amide)); N-aminoalkyl-alkenecarboxylic acid amide (N- (aminoC _1-26 alkyl) _-such as N- (aminoethyl) -oleic acid amide)- C _8-30 alkene carboxylic acid amide (N- (amino C _1-20 alkyl) -C _8-30 alkene carboxylic acid amide and the like), alkylene bisamide [N, N′-methylene bis (lauric acid amide), N, N′-ethylenebis (lauric acid amide), N, N′-ethylenebis (myristic acid amide), N, N′-ethylenebis (stearic acid amide), N, N′-ethylenebis (oleic acid amide), etc. N, N′—C _2-6 alkylene (or alkylidene) bis (C _8-30 alkanecarboxylic acid amide)] and the like.

The alkylene oxide adduct of the fatty acid amide only needs to have a polyalkylene oxide unit (such as a poly C _2-4 alkylene oxide unit), and not only a compound in which an alkylene oxide is added to the fatty acid amide but also a fatty acid amide and a polyoxyl. Condensates with alkylenes (polyoxy C _2-4 alkylenes such as polyoxyethylene) are also included. Examples of such alkylene oxide adducts (polyoxyalkylene fatty acid amides) include alkylene oxide adducts of the above fatty acid amides, such as polyoxyethylene capric acid amide, polyoxyethylene lauric acid amide, polyoxypropylene lauric acid amide, Polyoxy C _2-4 alkylene C _8-30 alkane carboxylic acid amide such as polyoxyethylene myristic acid amide, polyoxyethylene oleic acid amide; polyoxyethylene capric acid ethanolamide, polyoxyethylene lauric acid ethanolamide, polyoxypropylene laurin Acid ethanolamide, polyoxyethylene lauric acid isopropanolamide, polyoxyethylene myristic acid ethanolamide, polyoxyethylene coconut oil fatty acid ester Noruamido, polyoxy _{C 2-4} alkylene N- (hydroxy _{C 1-4 alkyl) -C 8-30} alkanecarboxylic acid amides such as polyoxyethylene oleic acid ethanolamide, polyoxyethylene lauric acid diethanolamide, polyoxyethylene coconut oil Examples include C _2-4 alkylene oxide adducts of amides of di C _1-4 alkanolamine and C _8-30 alkanecarboxylic acid, such as fatty acid diethanolamide and polyoxyethylene oleic acid diethanolamide.

  The addition mole number (or average addition mole number) of the alkylene oxide in the alkylene oxide adduct is not particularly limited, and is, for example, 1 to 50 moles, preferably 2 to 30 moles, more preferably 1 mole of the fatty acid amide. 2-20 mol (for example, 2-10 mol) may be sufficient.

Preferred fatty acid amides are amides of C _8-30 fatty acids (for example, C _8-26 fatty acids) or C _2-4 alkylene oxide adducts thereof, for example, (A) fatty acid amides are (A-1) C _8- An amide of ₃₀ fatty acids (eg C _8-26 fatty acids) or a C _2-4 alkylene oxide adduct thereof, (A-2) a mono or dialkanol amide of C _8-30 fatty acids (eg C _8-26 fatty acids) or It is the C _2-4 alkylene oxide adduct. Particularly preferred fatty acid amides are mono- or dialkanol amides of (A-2) C _8-20 fatty acids or their ethylene oxide adducts. Examples of such fatty acid amides include C _8-30 fatty acids (eg, C _8-26 fatty acids) and alkanolamines [eg, C _1-4 alkanolamines such as monoalkanolamine and dialkanolamine (particularly, Mono- or di-C _2-3 alkanolamines etc.)] and the like] [for example, N- (hydroxy C _1-4 alkyl) -C _8-26 fatty acid amide (especially N- (hydroxy C _2-3 alkyl) -C _8-26 fatty acid amides), amides of diC _1-4 alkanolamines and C _8-26 fatty acids (ie, N, N-di ( _{hydroxyC 1-4} alkyl) -C _8-26 fatty acid amides (especially , N, N-di (hydroxy _{C 2-3 alkyl) -C 8-26} fatty acid amide)), etc.], or a _{C 2-4} with alkylene oxide Like body (C _2-3 alkylene oxide adduct such as ethylene oxide adduct, etc.). Among fatty acid amides, in particular, fatty acid amides of C _8-20 saturated fatty acids (C _10-16 saturated fatty acids such as capric acid, lauric acid, myristic acid, coconut oil fatty acid, etc.) and mono- or di-C _1-4 alkanolamines. Or an ethylene oxide adduct thereof.

  The fatty acid amide may be liquid at room temperature (15 to 25 ° C.) or may be solid at room temperature, for example, a “melting point” of about 40 ° C. or less.

  The molar ratio between the fatty acid and the amine (including ammonia) can be appropriately selected according to the number of carboxyl groups of the fatty acid and the number of active hydrogen atoms of the amine. For example, fatty acid / amines = 1 / It may be 5 to 5/1, preferably 1/3 to 3/1, and more preferably about 1/2 to 2/1. For example, for the amide of fatty acid and dialkanolamine (and its alkylene oxide adduct), fatty acid and monoalkanolamine or dialkanolamine were used at a ratio of the former / the latter (molar ratio) = 1/2. 1: 2 type amide (or its alkylene oxide adduct), and 1: 1 type amide (or its alkylene oxide adduct) used at a ratio of the former / the latter (molar ratio) = 1/1, etc. This type of amide can also be used as the fatty acid amide in the present invention.

(B) Water-soluble polymer Water-soluble polymers include hydrophilic groups or units (carboxyl groups or salts thereof, sulfonic acid groups or salts thereof, hydroxyl groups, amide groups, basic nitrogen atom-containing groups, vinyl ether units, oxy Polymer having an ethylene unit), a cellulose derivative, a natural polymer polysaccharide (such as alginic acid), and the like. The water-soluble polymer may be any of water-soluble, water-dispersible and water-swellable polymers.

Examples of the water-soluble polymer include a polymer having a carboxyl group or a salt thereof [for example, a monomer having a carboxyl group such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid or a copolymer thereof. (Including (meth) acrylic acid esters such as (meth) acrylic acid C _1-10 alkyl esters), and copolymers with other copolymerizable monomers such as styrene and carboxylic acid vinyl esters (such as vinyl acetate) For example, poly (meth) acrylic acid, (meth) acrylic acid-maleic anhydride copolymer, (meth) acrylic acid-vinyl sulfonic acid copolymer, (meth) acrylic acid-methyl methacrylate copolymer, etc. (Meth) acrylic acid polymers) or salts thereof (for example, alkali metal salts such as sodium salts and potassium salts, ammonium salts and organic amine salts) ], A polymer having a sulfonic acid group or a salt thereof [for example, a monomer having a sulfonic acid group such as ethylene sulfonic acid or styrene sulfonic acid, or a copolymer (with other copolymerizable monomer) Copolymer) and salts thereof (for example, alkali metal salts such as sodium salt and potassium salt, ammonium salts, organic amine salts and the like)], hydroxyl group-containing polymers [for example, hydroxyl group-containing monomers (for example, , Hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate, hydroxyalkyl methacrylates corresponding to these hydroxyalkyl acrylates, polyethylene glycol mono (meth) acrylates, etc.) or a copolymer (the other copolymerizable monomer) Copolymer), vinyl alcohol polymers, etc.], amino Group-containing polymer [for example, a monomer having an amide group such as (meth) acrylamide or a copolymer (including a copolymer with the other copolymerizable monomer)], basic nitrogen Atom-containing polymer [for example, N-dimethylaminoethyl acrylate, N-diethylaminoethyl acrylate or the corresponding methacrylate, vinyl pyrrolidone, or other monomer having a basic nitrogen atom, or a copolymer (the other copolymer Including a copolymer with a polymerizable monomer)], vinyl ether polymers [eg, alkyls such as vinyl ether monomers (vinyl methyl ether, vinyl ethyl ether, vinyl isopropyl ether, vinyl butyl ether, vinyl isobutyl ether, etc.) Vinyl ethers) or copolymers (eg, polymethyl ether, Copolymerizable monomers such as ethyl vinyl ether and vinyl ether-maleic anhydride copolymer (copolymers with monomers having the carboxyl group, other copolymerizable monomers exemplified above, etc.) ], An alkylene ether polymer, a cellulose derivative [for example, alkyl cellulose (C _1-6 alkyl cellulose such as methyl cellulose, ethyl cellulose, propyl cellulose), hydroxyalkyl cellulose (hydroxy C _2-4 alkyl such as hydroxyethyl cellulose, hydroxypropyl cellulose, etc.) cellulose), hydroxyalkyl alkylcelluloses (hydroxyethyl cellulose, hydroxypropyl _{C 2-4} alkyl _{-C 1-6} alkyl celluloses such as hydroxypropyl methylcellulose), Karubokishia Kill cellulose cellulose ethers such as (carboxymethylcellulose, carboxy C _1-6 alkyl celluloses such as carboxymethyl cellulose); soluble cellulose acetate, etc.], water-soluble polyester, natural polymer polysaccharides [e.g., alginic acid or a salt thereof, pectins, Starch, hyaluronic acid, sodium chondroitin sulfate, chondroitin heparin, agar, gum arabic, dextrin, etc.]. These water-soluble polymers can be used alone or in combination of two or more.

  (B) The “melting point” of the water-soluble polymer is 60 ° C. or higher (for example, about 60 to 350 ° C.), preferably 62 ° C. or higher (for example, about 65 to 320 ° C.), more preferably 65 ° C. or higher (for example, 65 to 310 ° C.), particularly 70 ° C. or higher (for example, about 70 to 300 ° C.), and may be 100 to 300 ° C. (for example, 130 to 250 ° C.) or 150 to 200 ° C. In addition, the “melting point” of the (meth) acrylic polymer containing a (meth) acrylic monomer as a main component may be about 60 to 110 ° C. (for example, 75 to 105 ° C.). The “melting point” of the resin mainly composed of a monomer based monomer may be about 100 to 200 ° C. (for example, 150 to 190 ° C.), and the “melting point” of a vinyl ether polymer may be 100 to 180 ° C. (for example, 120 to 160 ° C.). The melting point, softening point or glass transition temperature can be measured by conventional thermal analysis (thermal analysis using a thermal scanning calorimeter or the like).

  Of the water-soluble polymers, vinylpyrrolidone polymers, vinyl alcohol polymers, cellulose ethers, alkylene ether polymers, and natural polymer polysaccharides [particularly alginic acid or a salt thereof] are preferable. In particular, the water-soluble polymer is preferably composed of at least one selected from vinyl pyrrolidone polymers, vinyl alcohol polymers, and cellulose ethers (in particular, at least vinyl pyrrolidone polymers).

  The vinyl pyrrolidone-based polymer includes vinyl pyrrolidone or a derivative thereof alone or as a copolymer, for example, polyvinyl pyrrolidone, a copolymer of vinyl pyrrolidone and a copolymerizable monomer (for example, the (meth) acrylic monomer) And a copolymer with a copolymerizable monomer such as vinyl acetate, vinyl imidazole, and / or vinyl caprolactam). The vinyl pyrrolidone polymers can be used alone or in combination of two or more. The proportion of vinylpyrrolidone or a derivative thereof in the vinylpyrrolidone polymer may be, for example, 30 to 100% by weight, preferably 50 to 95% by weight, and more preferably about 60 to 90% by weight. When the ratio of vinylpyrrolidone or a derivative thereof is 30% by weight or more, it is advantageous in terms of antifogging property.

The glass transition temperature (Tg) of the vinylpyrrolidone polymer is, for example, 55 to 200 ° C, preferably 60 to 190 ° C (eg 65 to 185 ° C), more preferably 70 to 180 ° C (eg 75 to 170 ° C). ) Degree. The molecular weight of the vinylpyrrolidone polymer is not particularly limited, and is, for example, a weight average molecular weight of 1 × 10 ^{4 to} 500 × 10 ⁴ , preferably 5 × 10 ^{4 to} 300 × 10 ⁴ , more preferably 10 × 10 ⁴ to. It may be about 250 × 10 ⁴ .

  Examples of vinyl alcohol polymers include saponified products of fatty acid vinyl ester polymers (single or copolymer) such as polyvinyl alcohol (fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol), partially acetalized polyvinyl alcohol, and ethylene. -Vinyl alcohol copolymer, vinyl alcohol-ethylene sulfonic acid copolymer, vinyl alcohol-maleic acid copolymer, etc. are mentioned.

  The saponification degree of the vinyl alcohol polymer is not particularly limited, but is, for example, 60 to 100 mol%, preferably 70 to 100 mol% (for example, 80 to 99 mol%), more preferably about 85 to 100 mol%. There may be. The “melting point” of the vinyl alcohol polymer may be about 130 to 250 ° C., preferably 150 to 240 ° C., more preferably about 170 to 230 ° C. (for example, 180 to 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, 100 to 5000), preferably 200 to 4000, and more preferably about 500 to 3000.

Among the cellulose ethers, _{C 1-4} alkyl celluloses, hydroxyethylcellulose, such as methyl cellulose, hydroxyalkyl _{C 2-3} alkyl celluloses such as hydroxypropyl cellulose, hydroxyethyl cellulose, hydroxyethyl _{C 2-3} alkyl -C such as hydroxypropylmethyl cellulose Carboxy C _1-4 alkyl cellulose such as _1-4 alkyl cellulose and carboxymethyl cellulose is preferred.

  The “melting point” of cellulose ethers may be about 150 to 350 ° C. (for example, 200 to 320 ° C., preferably 220 to 300 ° C.). Cellulose ethers may decompose without exhibiting a melting point. In such a case, the decomposition temperature can be the melting point. The degree of polymerization (or average degree of polymerization) of cellulose ethers is usually 100 or more (for example, 100 to 2000), preferably 150 to 1000, more preferably about 200 to 800.

  Examples of the alkylene ether polymers include oxyethylene units such as polyoxyethylene (or polyethylene glycol) and polyoxyethylene-polyoxypropylene block copolymers (hereinafter sometimes simply referred to as POE-POP block copolymers). The polymer which has can be illustrated. The content of the ethylene oxide chain in the POE-POP block copolymer is 10 to 99% by weight, preferably 15 to 95% by weight, more preferably 20 to 95% by weight, particularly about 30 to 90% by weight. Also good. The block structure of the block copolymer is not particularly limited, and may be a diblock structure or a triblock structure in which oxyethylene blocks are bonded to both ends of an oxypropylene block.

  About 60-90 degreeC (for example, 65-85 degreeC) may be sufficient as melting | fusing point of an alkylene ether type polymer. The weight average molecular weight of the alkylene ether polymer (such as POE-POP block copolymer) is not particularly limited, and is 1,000 to 1,000,000 (for example, 1,000 to 800,000), preferably 1, It may be about 500 to 600,000 (for example, 1,500 to 500,000), more preferably about 2,000 to 400,000 (for example, 2,000 to 300,000). The antifogging agent composition containing a POE-POP block copolymer having a low melting point is applied to a resin sheet and dried, and then, when the coated surface comes into contact with a roll (particularly a metal roll), the roll is contaminated, and the antifogging agent Ingredients are likely to adhere to and accumulate on the roll. Therefore, it is advantageous to use polyoxyethylene (or polyethylene glycol) as the alkylene ether polymer.

  Alginic acid is a linear polymer polysaccharide obtained by extraction from brown algae plants such as kombu, wakame and kajime, and is a heteropolymer containing D-mannuronic acid and L-guluronic acid as constituent units. . Examples of the salt of alginic acid include a salt of alginic acid and an inorganic base. Specifically, ammonium salt; alkali metal salt such as potassium salt and sodium salt; alkaline earth metal salt such as calcium salt and magnesium salt; silver Examples thereof include transition metal salts such as salts and copper salts. Of these salts, monovalent metal salts (such as alkali metal salts) are preferable in addition to ammonium salts.

  The “melting point” of natural polymer polysaccharides such as alginic acid may be the same as the “melting point” of cellulose ethers. The degree of polymerization (or average degree of polymerization) of a natural polymer polysaccharide (such as alginic acid or a salt thereof) is usually 20 or more (for example, 20 to 2000), preferably 50 to 1500, and more preferably about 70 to 1300. May be.

  A base composition can be constructed using (A) a fatty acid amide and (B) a water-soluble polymer. The ratio (weight ratio) of (A) fatty acid amide and (B) water-soluble polymer is, for example, the former / the latter = 1/99 to 99/1 (for example, 5/95 to 95/5), preferably 10 / 90 to 90/10 (for example, 15/85 to 85/15), more preferably 20/80 to 80/20 (for example, 25/75 to 75/25), particularly 30/70 to 70/30 (for example, 40/60 to 60/40).

  (A) For a base composition composed of a fatty acid amide and (B) a water-soluble polymer, the surface activity of at least one of (C) a nonionic surfactant and (D) an anionic surfactant When an agent is added, an anti-fogging layer of a surface treatment agent containing a water-soluble polymer (especially a water-soluble polymer having a high “melting point”) is formed on a resin sheet, and water-soluble High anti-fogging property can be ensured because a uniform anti-fogging layer is formed by plasticizing the conductive polymer and following the molding. Moreover, even if there is little application quantity of a surface treating agent, high anti-fogging property is securable.

(C) Nonionic surfactants Nonionic surfactants can be roughly classified into polyhydric alcohol fatty acid esters and adducts obtained by adding ethylene oxide to active hydrogen atoms of hydrophobic compounds having active hydrogen atoms. .

Examples of the polyhydric alcohol include C _2-12 alkylene glycols such as ethylene glycol, propylene glycol, butanediol, hexanediol, and neopentyl glycol; diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, and polypropylene. (Poly) oxy C _2-4 alkylene glycol such as glycol and polytetramethylene glycol; glycerin, polyglycerin having a polymerization degree of about 2 to 20 (diglycerin, triglycerin, tetraglycerin, polyglycerin, etc.), trimethylolethane, triglyceride Methylolpropane, pentaerythritol, saccharides (sucrose, sorbitol, mannitol, xylitol, maltitol, sorbitan, ori Sugar, etc.) polyhydroxy compounds, such as (polyhydric alcohols), and others. These polyhydric alcohols can be used alone or in combination of two or more.

Examples of the fatty acid include the fatty acids described in the section of the fatty acid amide, and usually higher fatty acids such as C _8-30 fatty acids (for example, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, hydroxystearic acid). , C _8-26 fatty acids such as saturated fatty acids such as arachidic acid, behenic acid and montanic acid, unsaturated fatty acids such as oleic acid and erucic acid), preferably C _10-22 fatty acids (eg C _10-20 fatty acids), In particular, C _10-18 fatty acids (saturated fatty acids such as lauric acid, myristic acid, palmitic acid and stearic acid, and unsaturated fatty acids such as oleic acid) are preferred. The fatty acid is often a saturated fatty acid.

The polyhydric alcohol fatty acid ester is often selected from glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, sorbitol fatty acid ester, and sorbitan fatty acid ester. Examples of such polyhydric alcohol fatty acid esters include sucrose fatty acid esters (for example, sucrose laurate (such as sucrose mono to penta laurate)), sucrose palmitate (such as sucrose mono to penta palmitate). Ester), sucrose stearate (sucrose mono to pentastearate, etc.), sucrose behenate (sucrose mono to pentabehenate, etc.), sucrose oleate (sucrose mono to pentaoleate) Sucrose C _8-24 saturated or unsaturated fatty acid esters (mono to hexaesters, etc.), especially sucrose C _8-24 saturated or unsaturated fatty acid esters (mono to tetraesters etc.)); Polyglycerin fatty acid ester (degree of polymerization 2-16 Esters of every polyglycerol with C _8-24 saturated or unsaturated fatty acids, for example, (such as decaglycerol mono- to Dekakapuriru ester) decaglycerol caprylate ester, hexaglycerin laurate (hexaglycerin mono- to Pentaraurin acid Ester, etc.), decaglycerin lauric acid ester (decaglycerin mono to decalauric acid ester, etc.), decaglycerin stearic acid ester (such as decaglycerin mono to decastearic acid ester), decaglycerin oleic acid ester (decaglycerin mono to dekaoleic acid ester) etc.), etc.); glycerin fatty acid ester (ester of glycerin and C _8-24 saturated or unsaturated fatty acids, for example, glycerin caprylate esters (glycerol mono- to deer Glyceryl laurate (eg glycerol mono to dilaurate), glycerol stearate (eg glycerol mono to distearate), glycerol behenate (eg glycerol mono to dibehenate), glycerol olein Acid esters (such as glycerin mono to dioleic acid esters); sorbitol fatty acid esters (esters of sorbitol and C _8-24 saturated or unsaturated fatty acids, such as sorbitol caprylic acid esters (such as sorbitol mono to pentacaprylic acid esters)) Sorbitol laurate (such as sorbitol mono to pentalaurate), sorbitol palmitate (such as sorbitol mono to pentapalmiti) Acid esters, etc.), sorbitol stearates (such as sorbitol mono to pentastearate), sorbitol oleates (such as sorbitol mono to pentaoleates), sorbitan fatty acid esters corresponding to these fatty acid esters, etc. It is done. These fatty acid esters can be used alone or in combination of two or more.

  Preferred polyhydric alcohol fatty acid esters are sucrose fatty acid esters, polyglycerin fatty acid esters, glycerin fatty acid esters, especially at least sucrose fatty acid esters.

  In the ethylene oxide adduct, examples of the hydrophobic compound having an active hydrogen atom include higher alcohols (such as lauryl alcohol), aromatic hydroxy compounds (such as phenols and alkylphenols), polyhydric alcohol fatty acid esters having a hydroxyl group, Examples include fats and oils having a hydroxyl group (such as castor oil and hardened castor oil).

Examples of the ethylene oxide adduct include an ethylene oxide adduct of a higher alcohol (polyoxyethylene C _8-26 alkyl ether such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene octadecyl ether (preferably C _{10 -20} alkyl ethers), ethylene oxide adducts of aromatic hydroxy compounds [for example, polyoxyethylene aryl ethers such as polyoxyethylene phenyl ether (preferably polyoxyethylene C _6-10 aryl ethers); Polyoxyalkylene alkyl aryl ethers such as nonyl phenyl ether (preferably polyoxyethylene C 4 _-26 alkyl phenyl ether etc.) Ethylene oxide adduct of _cole fatty acid ester [C _8-26 fatty acid ester having polyoxyethylene chain such as polyoxyethylene glyceryl stearate ester, polyoxyethylene sorbitan stearate ester, polyoxyethylene sorbitol stearate ester (preferably poly C _10-20 fatty acid ester having an oxyethylene chain, etc.]], ethylene oxide adducts of fats and oils (polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene coconut oil and other hydroxyl group-containing fats and ethylene oxides) Etc.). Even an ethylene oxide adduct of a fatty acid amide may be used as the (C) nonionic surfactant as long as it is an ethylene oxide adduct different from the (A) fatty acid amide. The number average molecular weight of the polyoxyethylene adduct is, for example, 150 or more (for example, 150 to 35,000), preferably 200 to 30,000, and more preferably about 200 to 20,000.

  In the ethylene oxide adduct, the average addition mole number of oxyethylene units may be, for example, 2 to 100, preferably 2 to 50, more preferably about 3 to 30, and about 2 to 10 mol. Also good.

  In the polyhydric alcohol fatty acid ester and its ethylene oxide adduct, the fatty acid is not limited to a single fatty acid but may be a plurality of fatty acid esters (mixed fatty acid esters).

Said (C) nonionic surfactant may be comprised independently, and may be comprised combining multiple (same kind or different kind) surfactant. (C) The nonionic surfactant is at least one component selected from sucrose fatty acid ester, polyglycerin fatty acid ester, glycerin fatty acid ester and polyoxyethylene alkyl ether (such as _C10-20 alkyl ether), particularly at least It is preferably composed of sucrose fatty acid ester (such as sucrose _C10-20 fatty acid ester such as sucrose laurate).

  (C) It is preferable that a nonionic surfactant is solid at normal temperature (20-25 degreeC). The “melting point” of the nonionic surfactant is 50 ° C. or more (for example, about 50 to 120 ° C.), preferably 53 ° C. or more (for example, 53 to 115 ° C.), more preferably 55 to 110 ° C. (for example, 60 ˜105 ° C.), particularly about 65 to 100 ° C. (for example, 70 to 95 ° C.). When a nonionic surfactant having a liquid or low melting point at room temperature is used, the antifogging property tends to be lowered, and transfer / attachment to a roll (especially a metal roll) and set-off are likely to occur.

  (C) The amount of the nonionic surfactant used can be selected according to whether or not (D) the anionic surfactant is used and the amount used, and when (C) the nonionic surfactant is used, 0.1 to 400 parts by weight (for example, 1 to 380 parts by weight), preferably 5 to 360 parts by weight with respect to 100 parts by weight of the base composition (total amount of (A) fatty acid amide and (B) water-soluble polymer) Parts (for example, 10 to 350 parts by weight), more preferably about 25 to 250 parts by weight (for example, 50 to 200 parts by weight), and usually about 30 to 170 parts by weight (for example, 50 to 150 parts by weight). is there.

(D) Anionic surfactant (D) The anionic surfactant may be a sulfonate, sulfate ester salt, carboxylate salt, phosphate salt or phosphate ester salt.

Examples of the sulfonate include alkane sulfonate (C _10-20 alkane sulfonate such as lauryl sulfate) and arene sulfonate (C _6-10 arene sulfonate such as benzene sulfonate and naphthalene sulfonate). ), Alkylarene sulfonates (C _4-20 alkyl C _6-10 arene sulfonates such as octylbenzene sulfonate, undecyl naphthalene sulfonate, dodecyl benzene sulfonate), alkyl sulfosuccinates (di- Examples thereof include di-C _6-20 alkylsulfosuccinates such as (2-ethylhexyl) sulfosuccinate) and α-olefin sulfonates.

Examples of the sulfate ester salt include alkyl sulfate ester salt or alkenyl sulfate ester salt (higher alcohol sulfate ester salt) [ _C10-20 alkyl sulfate ester salt such as lauryl sulfate ester salt, octadecyl sulfate ester salt, and oleyl sulfate ester salt. _10-20 alkenyl sulfate ester salt], alkyl ether sulfate ester salt [polyoxyethylene · C _10-20 alkyl ether sulfate ester salt, etc.] and the like.

Examples of the carboxylate include C _8-26 fatty acid salts (for example, C _8-20 fatty acid salts) such as laurate, myristate, palmitate and stearate.

As phosphates or phosphate esters, mono- or dialkyl phosphates (C _8-20 alkyl phosphates such as octyl phosphates, dodecyl phosphates), polyoxyethylene alkyl phosphates Examples thereof include mono- or dialkyl phosphates such as salts and polyoxyethylene / alkylaryl phosphate esters.

  Basic substances constituting the salt include inorganic bases [ammonia, alkali metals (sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.)], organic bases [lower alkylamines (trimethylamine, triethylamine, tributylamine). Etc.), alkanolamines (ethanolamine, diethanolamine, dimethylaminoethanol, etc.)] and the like. The salt is often an ammonium salt, an alkali metal salt (sodium, potassium, etc.), an alkylamine salt or an alkanolamine salt.

  These anionic surfactants can be used alone or in combination of two or more. Of these (D) anionic surfactants, sulfonates (such as alkane sulfonates) and sulfates (such as alkyl sulfates) are preferred.

  (D) The anionic surfactant is preferably solid at room temperature (20 to 25 ° C.). The “melting point” of the anionic surfactant is 50 ° C. or higher (for example, about 50 to 150 ° C.), preferably 55 ° C. or higher (for example 55 to 130 ° C.), more preferably 60 to 110 ° C. (for example 65 to 150 ° C.). 100 ° C). When an anionic surfactant having a liquid or low melting point at room temperature is used, the antifogging property is lowered, and transfer / attachment to a roll (especially a metal roll) and set-off are likely to occur.

  (D) The amount of the anionic surfactant used can be selected according to whether or not (C) the nonionic surfactant is used and the amount used, and when (D) the anionic surfactant is used, 0.1 to 200 parts by weight (for example, 1 to 150 parts by weight), preferably 2 to 130 parts by weight (for example, 3 to 125 parts by weight), and more preferably 5 to 120 parts by weight with respect to 100 parts by weight of the composition. Part (for example, 7 to 120 parts by weight), usually about 10 to 100 parts by weight.

  In addition, although the surface treating agent should just contain at least one component among (C) nonionic surfactant and (D) anionic surfactant, it provides higher antifogging property to a resin sheet. For this purpose, it is preferable to include at least components of (C) a nonionic surfactant, particularly (C) a nonionic surfactant and (D) an anionic surfactant.

(E) Silicone oil The surface treatment agent may contain silicone oil. When silicone oil is used, the antiblocking property or release property of the resin sheet (antifogging resin sheet) to which the surface treatment agent is applied can be improved. The type of silicone oil is not particularly limited. For example, alkylpolysiloxanes such as dimethylpolysiloxane, diethylpolysiloxane, and trifluoropropylpolysiloxane; arylpolysiloxanes such as diphenylpolysiloxane; alkylarylpolysiloxanes such as methylphenylpolysiloxane Etc. The silicone oil may be a chain polysiloxane or a cyclic polysiloxane.

Furthermore, the silicone oil is a modified silicone oil such as a hydroxyalkyl group (such as a hydroxy _C2-4 alkyl group such as a hydroxyethyl group), a polyoxyalkylene group, an amino group, an N-alkylamino group, a glycidyl group or an epoxy group. Or a silicone oil having a polymerizable group (such as a vinyl group or a (meth) acryloyl group).

  Silicone oils can be used alone or in combination of two or more. Of silicone oils, dimethylpolysiloxane having high versatility is usually used. Silicone oil can be used in various forms, but is usually used in the form of a silicone emulsion (emulsion in which silicone oil is emulsified and dispersed).

The viscosity of the silicone oil is not particularly limited. For example, Ostwald viscosity at room temperature (15 to 25 ° C.) 50 to 50000 cSt (centistokes) (0.5 × 10 ^{−4 to} 500 × 10 ⁻⁴ m ² / s), Preferably it is about 100 to 30000 cSt (1 × 10 ^{−4 to} 300 × 10 ⁻⁴ m ² / s), more preferably about 150 to 25000 cSt (1.5 × 10 ⁻⁴ to 250 × 10 ⁻⁴ m ² / s). There may be.

  Silicone oil is not necessarily required, and the amount of silicone oil used can be selected, for example, from a range of about 0 to 50 parts by weight, preferably 0.1 to 40 parts by weight, preferably 100 parts by weight of the base composition. It may be about 1 to 30 parts by weight, more preferably about 5 to 25 parts by weight.

  Surface treatment agents include various additives such as stabilizers (antioxidants, UV absorbers, etc.), fillers, colorants, antistatic agents, flame retardants, lubricants, waxes, preservatives, viscosity modifiers, increase agents. It may contain a sticking agent, leveling agent, antifoaming agent and the like. Further, the surface treatment agent can be usually used in the form of a coating solution or an impregnation solution, and may be a non-aqueous liquid composition using an organic solvent as a solvent, but is usually used as an aqueous composition. In the aqueous composition, the solvent may be water alone, water and a hydrophilic solvent (especially a water miscible solvent) [for example, alcohols (methanol, ethanol, isopropanol, etc.), ketones (acetone, etc.), A mixed solvent with ethers (dioxane, tetrahydrofuran, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, butyl cellosolve, etc.), carbitols, etc.] may be used.

  The surface treatment agent can be prepared by using a conventional mixing stirrer or mixing / dispersing machine, and the silicone oil may be dispersed along with the preparation. The solid content concentration of the surface treatment agent can be selected from a range of, for example, about 0.1 to 10% by weight, for example, 0.1 to 2% by weight, preferably 0.3 to 1.8% by weight, more preferably It is about 0.5 to 1.5% by weight. The viscosity of the surface treatment agent can be appropriately selected within a range that does not impair the coating property. When measured by a steady flow viscosity measurement method, for example, at a temperature of 20 ° C., 10 cps (= 0.01 Pa · s) or less, preferably It may be about 1.1 to 5 cps (for example, 1.2 to 3 cps), more preferably about 1.3 to 2 cps.

[Anti-fogging resin sheet and manufacturing method thereof]
The antifogging resin sheet of the present invention comprises a resin sheet and an antifogging layer (a coating layer or a coating layer) formed on at least one surface (one surface or both surfaces) of the resin sheet. The cloud layer is composed of the surface treatment agent.

  The resin sheet may be various thermoplastic resins having film or sheet moldability, such as polyethylene resin (polyethylene, ethylene-ethyl acrylate copolymer, ionomer, etc.), polypropylene resin (polypropylene, propylene-ethylene copolymer). ), Olefin resins such as poly-4-methylpentene-1; vinyl alcohol resins such as polyvinyl alcohol and ethylene-vinyl alcohol copolymer; vinyl chloride resins such as polyvinyl chloride; styrene resins; polyethylene terephthalate Homo or copolyester resins having an alkylene arylate unit such as polybutylene terephthalate; nylon or polyamide resins; polyacrylonitrile resins; polycarbonate resins; polyphenylene oxide resins; Risuruhon resins; can be formed by cellulose derivatives and the like. These resins can be used alone or in combination of two or more. The resin sheet may be a single layer sheet or a laminated sheet in which a plurality of resin layers are laminated. The thickness of the resin sheet can be appropriately selected depending on the application, and is, for example, about 10 μm to 5 mm, preferably about 25 μm to 1 mm. When used for container molding, the thickness of the resin sheet may be, for example, 50 μm to 2 mm, preferably 50 to 1000 μm (for example, 100 to 1000 μm), and more preferably about 120 to 500 μm.

  A preferable resin sheet can be composed of a sheet having molding processability, particularly a hydrophobic synthetic resin sheet, such as an olefin resin (particularly polypropylene resin), a polyester resin (particularly polyethylene terephthalate resin), or a styrene resin. In particular, a resin sheet having high moldability, for example, a styrene resin sheet is preferable.

  Styrenic resins include homopolymers containing aromatic vinyl monomers (such as styrene, vinyltoluene, and α-methylstyrene) as constituents, and copolymerization of aromatic vinyl monomers and copolymerizable monomers. Combinations and mixtures thereof are included. More specifically, as the styrene resin, for example, non-rubber reinforced styrene resin [polystyrene (GPPS) for general use, 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 block copolymer or hydrogenated product thereof (polystyrene-polybutadiene-polystyrene). Block copolymer, etc.), acrylonitrile-butadiene-styrene copolymer (ABS resin), rubber component X (acrylic rubber, chlorinated polyethylene, ethylene-propylene rubber (EPDM), ethylene-vinyl acetate copolymer, etc.) A and the styrene S and AXS resin obtained by graft polymerization] are exemplified. These styrenic resins can be used alone or in admixture of two or more. The styrene resin sheet is a highly transparent styrene resin sheet (for example, a non-rubber reinforced styrene resin sheet composed of a non-rubber reinforced styrene resin such as GPPS, a styrene resin and a styrene-diene block copolymer). A styrene resin sheet composed of a coalescence or a hydrogenated product thereof, or a rubber-reinforced styrene resin sheet.

  Resin sheets are made of various additives such as stabilizers (antioxidants, UV absorbers, heat stabilizers, etc.), antistatic agents, crystal nucleating agents, hydrocarbon polymers, plasticizers, mineral oil, filling An agent, a coloring agent, etc. may be included.

  The resin sheet can be obtained by a conventional method, for example, a conventional film forming method such as a T-die method or an inflation method. The resin sheet may be unstretched, but is preferably stretched. The stretched film may be a uniaxially stretched film, but is preferably a biaxially stretched film. Moreover, you may heat-process (heat-setting process) a stretched film as needed. Examples of the stretching method include conventional stretching methods such as roll stretching, roll stretching, belt stretching, tenter stretching, tube stretching, and stretching methods combining these. The draw ratio can be appropriately set according to the desired sheet properties, and may be, for example, 1.2 to 20 times, preferably 1.5 to 15 times, and more preferably about 2 to 10 times.

The surface of the resin sheet may be subjected to a conventional surface treatment such as corona discharge treatment or high frequency treatment. In particular, the resin sheet is preferably subjected to corona discharge treatment to form an antifogging layer on the corona discharge treatment surface. The surface tension of the resin sheet varies depending on the type of the sheet and cannot be determined unconditionally. However, when measured in accordance with JIS K-6768 “wetting test method for polyethylene and polypropylene films”, the surface tension is 30 to 65 dyn / cm (30 × 10 ^{−5 to} 65 × 10 ⁻⁵ N / cm). In the case of a styrene resin sheet, the surface tension is 40 to 62 dyn / cm (40 × 10 ^{−5 to} 62 × 10 ⁻⁵ N / cm), preferably 42 to 62 dyn / cm (42 × 10 ^{−5 to} 62 × 10 ^{− 5} N / cm), more preferably about 45 to 60 dyn / cm (45 × 10 ^{−5 to} 60 × 10 ⁻⁵ N / cm).

  If the surface tension of the sheet surface is too high, the sheet surface is activated too much, or blocking is likely to occur. Therefore, it becomes difficult to rewind a sheet wound in a roll shape, or when a plurality of molded containers are stacked and punched out, the containers are brought into close contact with each other, and the work efficiency of separating the containers and storing the contents decreases. easy.

  The antifogging resin sheet of the present invention is excellent in transparency and surface appearance (such as gloss), and has high antifogging properties even after being wound into a roll or after forming (for example, after deep drawing). Furthermore, the contamination of the molding machine by the antifogging agent can be reduced.

The surface treatment agent exhibits high antifogging properties even when the amount of coating is small. Therefore, the coating amount of the surface treatment agent (coating amount after drying) can be selected from a wide range of, for example, about ^{2 to} 150 mg / m ² (for example, 3 to 100 mg / m ² ), and is usually 5 to 60 mg / m. ² (for example, 7 to 50 mg / m ² ), preferably about 10 to 40 mg / m ² . In the present invention, the coating amount after drying of the surface treatment agent is 5 to 50 mg / ^{m 2} (e.g., 10 to 40 mg / ^{m 2)} be about, a resin sheet container forming (e.g., deep-drawn) to High antifogging property is maintained.

  In the antifogging resin sheet of the present invention, at least one surface of the resin sheet may be treated with a surface treatment agent, one surface is treated (or applied) with the surface treatment agent, and the other surface is treated with various kinds of materials. You may process (or application | coating treatment) with a processing agent (For example, the anti-blocking agent for improving blocking resistance, the antistatic agent for improving antistatic property and slipperiness, the coating agent containing a lubricant, etc.). In particular, a coating layer of a surface treatment agent is formed on one surface (such as a corona discharge treatment surface) of a resin sheet, and a release layer (or anti-blocking layer) is formed on the other surface (such as a surface that may be subjected to corona discharge treatment). ) May be formed.

  The release layer (or anti-blocking layer) may be composed of various release agents (or anti-blocking agents) such as wax (including mineral wax, plant wax, synthetic wax, etc.) It is preferable to use at least silicone oil. Furthermore, a preferable release layer can be composed of at least an ether-based hydrophilic polymer having an oxyethylene unit and silicone oil. In addition, as a silicone oil, the same silicone oil (dimethyl polysiloxane etc.) as the above can be used. Further, as the ether-based hydrophilic polymer having an oxyethylene unit, a nonionic surfactant such as a polyoxyethylene-polyoxypropylene block copolymer, a nonionic surfactant having an oxyethylene unit, or the like can be used. .

  In a preferred embodiment, the silicone oil can be used in the form of an emulsion (aqueous emulsion) as described above. The ether-based hydrophilic polymer may be composed of at least one selected from a polyoxyethylene-polyoxypropylene block copolymer and a nonionic surfactant having an oxyethylene unit. Often composed of block copolymers.

  In the release agent, the proportion of the ether-based hydrophilic polymer can be selected within a range that does not impair the antifogging property and blocking resistance, and can be selected from a range of about 0 to 1000 parts by weight with respect to 100 parts by weight of the silicone oil. Usually, it may be about 10 to 500 parts by weight, preferably 20 to 200 parts by weight (for example, 50 to 150 parts by weight), more preferably about 30 to 100 parts by weight (for example, 50 to 100 parts by weight).

  The processing agent such as a release agent is various additives such as stabilizers (antioxidants, ultraviolet absorbers, etc.), fillers, colorants, antistatic agents, flame retardants, lubricants, waxes, preservatives. Further, it may contain a viscosity modifier, a thickener, a leveling agent, an antifoaming agent and the like. The treatment agent can be usually used in the form of a coating solution or an impregnation solution, and may be a non-aqueous liquid composition using an organic solvent as a solvent, but is usually used as an aqueous composition. In the aqueous composition, the solvent may be water alone or a mixed solvent of water and the above-mentioned hydrophilic solvent (especially water-miscible solvent).

The coating amount of the processing agent such as a release agent (the coating amount after drying) 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 processing agent. Usually, it may be ^{2 to} 100 mg / m ² , preferably 3 to 50 mg / m ² (for example, 5 to 30 mg / m ² ), and more preferably about 5 to 25 mg / m ² .

  The antifogging resin sheet can be produced by applying the surface treatment agent (or antifogging agent) to at least one surface of the resin sheet. Further, an antifogging resin sheet is produced by applying the surface treatment agent on one surface of the resin sheet and applying the treatment agent (for example, a mold release agent or an antiblocking agent) on the other surface. May be. For the application of the surface treatment agent (or treatment agent), conventional application means such as spray, roll coater, gravure roll coater, knife coater, dip coater and the like can be used. If necessary, the surface treatment agent (or treatment agent) may be applied a plurality of times. After the surface treatment agent (and treatment agent) is applied to the resin sheet, the antifogging layer and the treatment layer (such as a release layer) can be usually formed by drying the coating layer.

  The antifogging resin sheet may be continuously provided in a post-treatment process (such as a container molding process), but is usually wound in a roll and is often provided in a post-treatment process. In the take-up roll wound up with a resin sheet, the resin sheet in the winding core part can greatly suppress the antifogging component transfer (back-off) and not only has excellent anti-fogging properties but also high-temperature anti-fogging properties. High anti-fogging property can be maintained over a long period of time. Moreover, whitening can be suppressed and the transparency and gloss of the resin sheet are not impaired. Therefore, it can be used for various uses, for example, a cover sheet (or film), a packaging sheet (or film) such as food packaging. A coated resin sheet using a resin sheet having high moldability has high secondary moldability and is suitable for molding processing of containers and the like.

[Container and its manufacturing method]
The container (anti-fogging container) of the present invention is formed on a resin container and at least a part of the surface of the container (for example, at least one surface such as the inner surface or outer surface of the container body or the inner surface or outer surface of the lid). The anti-fogging layer (anti-fogging layer composed of the surface treatment agent) may be used, and obtained by applying the surface treatment agent to the surface of the resin container by the application method (spraying, etc.). The container formed by the said anti-fogging resin sheet (The container obtained by shape | molding an anti-fogging resin sheet, etc.) etc. may be sufficient. Since such a container is excellent in anti-fogging property and transparency, it is useful as a container for storing a contained material containing moisture such as a food packaging container. In the former container, as the resin constituting the resin container, the resin exemplified in the section of the resin sheet can be used.

  The container usually has at least a container main body for containing a container such as food, and the opening of the container main body may be covered with a wrapping film. Moreover, you may comprise a container with a container main body and the cover body which covers the opening part of the said container main body through a hinge part. In addition, in the molded article which has a cover body, you may process the inner surface of a cover body with the said surface treating agent.

  In many cases, a container formed of an antifogging resin sheet is formed from the antifogging resin sheet by a conventional thermoforming method. Examples of the thermoforming method (or secondary forming process) include a blow molding method, a vacuum forming method, a pressure forming method (a heating / pressure forming method such as a hot plate heating type pressure forming method, a radiation heating type pressure forming method), a vacuum, and the like. A pressure forming method, a plug assist forming method, a matched mold forming method and the like can be used. When using a stretched resin sheet, a hot plate heating type pressure forming method is usually used in many cases.

  In this invention, even if it uses for such thermoforming (secondary shaping | molding), high anti-fogging property and transparency can be maintained. In particular, even when the antifogging resin sheet is deep-drawn, it is excellent not only in high temperature antifogging properties but also in low temperature antifogging properties and can maintain high antifogging properties. In deep drawing container molding, the drawing ratio (ratio of container height / inner diameter of opening) is about 0.4 to 1.5, preferably about 0.5 to 1.2 (for example, 0.6 to 1). There may be.

  Since the antifogging surface treatment agent of the present invention is excellent in antifogging property and can prevent set-off, it is useful for obtaining an antifogging resin sheet by applying it to a resin sheet by coating or the like. Further, the antifogging surface treatment agent has low adhesion to a metal roller or the like, and does not contaminate the metal roller. Therefore, the antifogging resin sheet often has high transparency and gloss. Furthermore, even if the antifogging resin sheet is subjected to secondary molding (for example, thermoforming), high antifogging properties can be maintained. A container having an anti-fogging layer formed with an anti-fogging surface treatment agent on the surface is excellent in anti-fogging properties, and the visibility of the contents (or contents) is also high. For this reason, the container of the present invention is suitable for accommodating various contents (contents), particularly, contents containing moisture (such as food), and is used in an environment where condensation is likely to occur (for example, at a low temperature). It is also useful as a container for storing cooked foods as well as fresh foods and cooked foods to be stored.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

  In Examples and Comparative Examples, the following components (A) to (D) were used.

(A) Fatty acid amide
(A1) Coconut oil fatty acid diethanolamide (manufactured by Sanyo Chemical Industries, Prophan Extra 128, Coconut oil fatty acid: diethanolamide = 1 type)
(A2) Lauric acid diethanolamide (manufactured by Sanyo Chemical Industries, Prophan AA-62EX, lauric acid: diethanolamide = 1 type)
(A3) Coconut oil fatty acid monoethanolamide (manufactured by Sanyo Chemical Industries, Prophan AB-20, Coconut oil fatty acid: monoethanolamide = 1 type)
(A4) Polyoxyethylene coconut oil fatty acid monoethanolamide (manufactured by Sanyo Chemical Industries, Profan ME-20, coconut oil fatty acid: monoethanolamide = 1 type)
(A5) Lauric acid monoisopropanolamide (manufactured by Sanyo Chemical Industries, Prophan AD-31, lauric acid: monoisopropanolamide = 1 type)
(A6) Coconut oil fatty acid diethanolamide (manufactured by Sanyo Chemical Industries, Profan 2012E, coconut oil fatty acid: diethanolamide = 1: 2 type).

(B) Water-soluble polymer
(B1) Polyvinylpyrrolidone (manufactured by BASF, Rubytec K-90, glass transition temperature 180 ° C., weight average molecular weight 90 × 10 ^{4 to} 150 × 10 ⁴ )
(B2) Vinylpyrrolidone / vinyl acetate copolymer (BASF, Rubytec VA64, glass transition temperature 70 ° C.)
(B3) Polyvinyl alcohol (manufactured by Kuraray Co., Ltd., Poval PVA117, melting point 180 ° C., saponification degree 98 to 99 mol%)
(B4) Methylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd., Metrows SM100, melting point 300 ° C.)
(B5) Carboxymethylcellulose (Daicel Chemical Industries, CMC Daicel 1260, melting point 230 ° C.)
(B6) Polyoxyethylene (manufactured by Meisei Chemical Industry Co., Ltd., Alcox L-11, melting point 70 ° C., weight average molecular weight 11 × 10 ⁴ ).

(C) Nonionic surfactant
(C1) Sucrose laurate (manufactured by Riken Vitamin Co., Ltd., Riquemar A, melting point 90 ° C., aqueous solution with a solid content of 41% by weight)
(C2) Polyoxylauryl ether (Daiichi Kogyo Seiyaku Co., Ltd., DKS NL-600, melting point 54 ° C.)
(C3) Glycerol monobehenate (Riken Vitamin Co., Ltd., Riquemar B-100, melting point 75-82 ° C.).

(D) Anionic surfactant
(D1) Sodium alkane sulfonate (manufactured by Kao Corporation, Latemuru PS, sodium alkane sulfonate having about 15 carbon atoms, melting point 70 ° C., aqueous solution having a solid content of 40% by weight)
(D2) Sodium lauryl sulfate (manufactured by Kao Corporation, Emar 2FG, melting point 104 ° C.).

Examples 1-26 and Comparative Examples 1-7
An aqueous surface treatment agent (antifogging treatment agent) was prepared so that the solid content ratio of each component (weight ratio after drying of each component) was the ratio (parts by weight) shown in the table. In addition, although the density | concentration of a processing agent changes with evaluation items, the density | concentration of a processing agent shows the density | concentration (weight%) of solid content. Then, a predetermined amount of an aqueous surface treatment agent (antifogging treatment agent) is applied to the corona discharge treatment surface of the biaxially stretched polystyrene sheet having a sheet thickness of 0.25 mm according to the following evaluation characteristic items, and a hot air dryer is used. Then, an antifogging layer was formed by drying at 80 ° C. for 2 minutes.

  The properties (initial properties) of the obtained antifogging resin sheet and the properties of the sheets after the antifogging resin sheets were laminated and pressed (characteristics after pressing) were evaluated as follows.

(1) Initial characteristics of anti-fogging resin sheet
(1-i) High temperature anti-fogging property A biaxially stretched polystyrene sheet having a sheet thickness of 0.25 mm is subjected to corona discharge treatment at 54 dyn / cm or more (54 × 10 ⁻⁵ N / cm or more), and dried on this corona discharge treatment surface. The coating amount of 20 mg / m ² was applied to the anti-fogging treatment agent (concentration 0.7% by weight) No. An anti-fogging layer was formed by applying with a 5 Mayer bar and drying. The obtained antifogging resin sheet was cut into a predetermined size (120 mm × 120 mm) and stretched by 70 mm with a desktop biaxial stretching machine (manufactured by Iwamoto Seisakusho Co., Ltd.). The sheet was placed with the antifogging layer of the sheet facing the opening of a container containing hot water at 60 ° C., and left for 2 minutes in a room temperature environment. Next, the steam contact portion of the sheet is placed on a character group “antifogging” having a different font size printed on paper, and the degree of fogging of the sheet is visually evaluated according to the following criteria, and about five sheets The average value of the evaluated results was calculated.

5: “Anti-fogging” character with font size 5 can be clearly read 4: “Anti-fogging” character with font size 10 can be read clearly 3: “Anti-fogging” character with font size 14 can be read clearly Readable 2: Font size 18 “anti-fogging” characters can be clearly read 1: Characters cannot be identified.

(1-ii) Low-temperature anti-fogging property A stretched anti-fogging resin obtained by evaluating high-temperature anti-fogging property (1-i) in a container containing water (23 ° C.) at an ambient temperature of 23 ° C. The sheet was placed with the antifogging layer of the sheet facing the opening of the container, and in this state, the sheet was placed in a thermostatic bath at 5 ° C. and left for 10 minutes. Next, the degree of fogging of the sheet immediately after taking out was evaluated in the same manner as the evaluation of the high temperature antifogging property (1-i) in the initial characteristics of the antifogging resin sheet, and the average of the results of evaluation for five sheets The value was calculated.

(1-iii) Transferability to metal A biaxially stretched polystyrene sheet having a sheet thickness of 0.25 mm is subjected to corona discharge treatment at 54 dyn / cm or more (54 × 10 ⁻⁵ N / cm or more), and dried on this corona discharge treatment surface. The coating amount of 30 mg / m ² of No. ¹ was added to the anti-fogging treatment agent (concentration: 1.0% by weight). An anti-fogging layer was formed by applying with a 5 Mayer bar and drying. The obtained antifogging resin sheet was cut into a predetermined size (5 cm × 5 cm), the aluminum sheet of the same size and the antifogging surface side were combined, and sandwiched between stainless plates (thickness 5 mm, 3 cm × 5 cm). This was placed horizontally in a constant temperature bath at 60 ° C., and a 15 kg weight was placed thereon and left for 1 hour. After leaving, it was taken out from the thermostat and cooled to room temperature, and then the surface where the antifogging surface and the aluminum sheet were in contact was observed, and the ratio of the antifogging surface transferred to the aluminum sheet was determined relative to the contact area. Evaluation was made with 5 sheets, and the average was obtained.

(2) Sheet characteristics after pressing A biaxially stretched polystyrene sheet having a sheet thickness of 0.25 mm was subjected to corona discharge treatment to 54 dyn / cm or more (54 × 10 ⁻⁵ N / cm or more), and this corona discharge treatment surface was dried. With an application amount of 20 mg / m ² , an antifogging treatment agent (concentration: 0.7% by weight) was No. An anti-fogging layer was formed by applying with a 5 Mayer bar and drying. After the antifogging resin sheet is cut into a predetermined size (30 cm × 30 cm), 10 sheets are stacked, and pressed at a temperature of 40 ° C. and a load of 10 kgf / cm ² (≈98 N / cm ² ) for 1 hour, the pressure is changed. The sheet was opened and separated one by one, and the back-off property and high-temperature anti-fogging property of the sheet were evaluated according to the following, and used as an index of sheet characteristics when the sheet was rolled up.

(2-i) Whitening The haze value (%) before and after pressurization of the antifogging resin sheet was measured to determine the difference.

(2-ii) High-temperature antifogging property About the separated sheet after pressing, the same operation as in the evaluation of the high-temperature antifogging property (1-i) in the initial characteristics of the antifogging resin sheet was performed, and the high-temperature antifogging property ( Evaluation was performed in the same manner as in 1-i), and the average value of five sheets was calculated.

  The results obtained in the examples and comparative examples are shown in Tables 1 to 3.

  As is clear from the table, the antifogging resin sheets of the examples show extremely high antifogging properties (high temperature and low temperature antifogging properties) even when the application amount is small, and container molding (especially deep drawing) High anti-fogging properties could be maintained even when subjected to molding. In addition, the antifogging surface treatment agent of the example had a low set-off property even when the sheet was wound into a roll shape, and also had a low adhesion to metal and transferability.

Claims (20)

  An antifogging surface treatment agent comprising (A) a fatty acid amide, (B) a water-soluble polymer, (C) a nonionic surfactant and / or (D) an anionic surfactant. (A) Fatty acid amide is (A-1) C _8-30 fatty acid amide or C _2-4 alkylene oxide adduct thereof, (A-2) C _8-30 fatty acid mono- or dialkanol amide or C _2-4 thereof The surface treating agent according to claim 1, which is at least one selected from alkylene oxide adducts.   (B) The surface treatment agent according to claim 1 or 2, wherein the water-soluble polymer has a melting point, softening point or glass transition temperature of 60 ° C or higher.   (B) The water-soluble polymer is at least one selected from vinylpyrrolidone polymers, vinyl alcohol polymers, cellulose ethers, alkylene ether polymers and alginic acid or salts thereof. The surface treating agent according to crab.   (C) The surface treatment agent according to any one of claims 1 to 4, wherein the nonionic surfactant has a melting point, a softening point or a glass transition temperature of 50 ° C or higher.   (C) The nonionic surfactant is comprised by at least 1 type selected from sucrose fatty acid ester, polyglycerol fatty acid ester, glycerol fatty acid ester, and polyoxyethylene alkyl ether in any one of Claims 1-5. The surface treating agent as described.   (D) The anionic surfactant is at least one selected from a sulfonate, a sulfate ester salt, a carboxylate salt, and a phosphate salt or a phosphate ester salt. Surface treatment agent.   (D) The surface treatment agent according to any one of claims 1 to 7, wherein the anionic surfactant is composed of at least one selected from alkane sulfonate and alkyl sulfate ester salt. (A-1) C _8-26 fatty acid amide or ethylene oxide adduct thereof, and (A-2) C _8-26 fatty acid mono- or dialkanol amide or ethylene oxide adduct thereof. (A) a fatty acid amide, a vinyl pyrrolidone-based polymer (B) a water-soluble polymer, (C) a nonionic surfactant and (D) an anionic surfactant at least (C The surface treatment agent according to any one of claims 1 to 8, wherein the surface treatment agent comprises a nonionic surfactant, and (C) the nonionic surfactant comprises at least a sucrose fatty acid ester.   (C) Nonionic with respect to 100 parts by weight of a base composition containing a fatty acid amide and (B) a water-soluble polymer in a ratio of the former / the latter = 1/99 to 99/1 (weight ratio). The surface treating agent according to any one of claims 1 to 9, comprising 0.1 to 400 parts by weight of a surfactant and / or (D) 0.1 to 200 parts by weight of an anionic surfactant. (A) The fatty acid amide is composed of at least one selected from (A-2) mono- or dialkanolamides of C _8-20 fatty acids or their ethylene oxide adducts, and (B) the water-soluble polymer is a vinylpyrrolidone series (C) a nonionic surfactant comprising at least one selected from polymers, vinyl alcohol polymers, and cellulose ethers, and having a melting point, softening point or glass transition temperature of 62 ° C. or higher. Is composed of a sucrose fatty acid ester having a melting point of 53 ° C. or higher, a softening point, or a glass transition temperature, and (D) the anionic surfactant is composed of at least one selected from alkane sulfonate and alkyl sulfate ester salt A base containing (A) a fatty acid amide and (B) a water-soluble polymer in a ratio of the former / the latter = 10/90 to 90/10 (weight ratio). The composition according to any one of claims 1 to 10, comprising (C) 1 to 380 parts by weight of a nonionic surfactant and / or (D) 1 to 150 parts by weight of an anionic surfactant with respect to 100 parts by weight of the composition. The surface treating agent as described in.   The anti-fogging resin sheet in which the anti-fogging layer comprised with the surface treating agent in any one of Claims 1-11 is formed in the at least one surface of the resin sheet.   The antifogging resin sheet according to claim 12, wherein the resin sheet is subjected to corona discharge treatment, and an antifogging layer is formed on the corona discharge treatment surface.   The antifogging resin sheet according to claim 12 or 13, wherein an antifogging layer is formed on one surface of the resin sheet, and a release layer is formed on the other surface.   The antifogging resin sheet according to any one of claims 12 to 14, wherein the resin sheet is a styrene resin sheet.   The manufacturing method of the anti-fogging resin sheet which apply | coats the surface treating agent in any one of Claims 1-11 to the at least one surface of a resin sheet.   The manufacturing method of Claim 16 which winds up in roll shape after apply | coating a surface treating agent to a resin sheet.   A container in which an antifogging layer composed of the surface treatment agent according to any one of claims 1 to 11 is formed on at least a part of a surface of a resin container.   A container formed of the antifogging resin sheet according to any one of claims 12 to 15. The anti-fogging container by which the surface treating agent in any one of Claims 1-11 was apply | coated with the application amount of 5-50 mg / m < ² > on the at least one surface of the resin sheet, and the container was shape | molded.