JP2008050492A - Anti-fogging agent composition and anti-fogging film by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous dispersion-based anti-fogging agent composition capable of maintaining an emulsified state even by diluting with alcohols. <P>SOLUTION: This anti-fogging agent composition is provided by containing each of the components of (A) a film-forming resin composition containing a (meth)acrylic copolymer obtained by the emulsion polymerization of a monomer mixture containing at least a (meth)acrylic acid alkyl ester and (meth)acrylic acid as the monomers in the presence of a reactive nonionic emulsifier, (B) inorganic colloidal sol, (C) a 1 to 10C aliphatic alcohol and (D) water, and having ≥-25 and ≤20°C lowest film-forming temperature. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an antifogging agent composition that imparts antifogging properties to the surface of a film or the like.

  In recent years, various thermoplastic resins have been used, but since many of the molded products produced from these thermoplastic resins have a hydrophobic surface, depending on the usage conditions such as the usage temperature of the molded product, It has the problem of causing fogging on the surface of the molded product. Specifically, in goggles, safety glasses, and the like that use synthetic resin lenses, the visibility may be lost if cloudiness occurs. Moreover, in the film for food packaging, when fogging occurs, the contents become difficult to see. In addition, in agricultural films used in greenhouses, when cloudiness occurs, the transmission of sunlight will worsen, slowing the growth of the plant, or water droplets generated by the collection of cloudy fine water droplets will fall on the cultivated plant. As a result, the young shoots are damaged or cause disease.

  As a method for solving such problems, a method for imparting antifogging properties to the surface of a thermoplastic resin molded product is known. As a method for imparting antifogging properties, a method of kneading a hydrophilic substance such as a surfactant into a thermoplastic resin to form a molded product, or after forming a molded product, on its surface, for example, silica or alumina Various methods for applying a mixture with a surfactant have been proposed.

  However, in the former method, the hydrophilic substance kneaded in the thermoplastic resin is coordinated in a state where it is exposed to the surface of the molded product, and the molded product is imparted with antifogging properties and exhibits antifogging properties. The antifogging properties disappear within a short period of time. On the other hand, since the coating film obtained also in the latter method has poor adhesion to the thermoplastic resin, there is a problem that the formed coating film may fall off with the passage of time.

  In contrast, water-dispersed antifogging agents that have improved adhesion to thermoplastic resins by adding inorganic chlorine compounds or hydrophobic acrylic resins having a predetermined glass transition temperature to silica or alumina are known. (See Patent Document 1).

Japanese Patent Laid-Open No. 09-087615

  However, in general, the antifogging agent is diluted with an alcohol such as isopropanol. At this time, the water-dispersed antifogging agent such as the antifogging agent described in Patent Document 1 is destroyed in an emulsified state, and aggregation and precipitation are likely to occur.

  Accordingly, an object of the present invention is to solve such problems and to provide an anti-fogging agent composition of an aqueous dispersion system that maintains an emulsified state even when diluted with alcohols.

  This invention is obtained by emulsion polymerization of a monomer mixture containing at least (A) (meth) acrylic acid alkyl ester and (meth) acrylic acid as monomers in the presence of a reactive nonionic emulsifier. A film-forming resin composition containing a (meth) acrylic copolymer, (B) an inorganic colloid sol, (C) an aliphatic alcohol having 1 to 10 carbon atoms, and (D) water. The above problems have been solved by using an antifogging agent composition having a minimum film forming temperature of -25 ° C or higher and 20 ° C or lower.

  Since the film-forming resin composition is produced in the presence of the reactive nonionic emulsifier, the nonionic emulsifier component is contained in the antifogging agent composition. Thereby, durability against aggregation by alcohols, that is, alcohol resistance can be improved.

Hereinafter, the present invention will be described in detail.
The antifogging agent composition according to the present invention is a composition containing at least the following components (A), (B), (C), and (D).

(Ingredient (A))
The component (A) is a film-forming resin composition containing a (meth) acrylic copolymer obtained by emulsion polymerization of a monomer mixture containing a predetermined (meth) acrylic monomer. “(Meth) acryl” means “acryl or methacryl”. The same applies hereinafter.

  Examples of the (meth) acrylic monomer contained in the monomer mixture include (meth) acrylic acid alkyl ester and (meth) acrylic acid as essential components. Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, (Meth) acrylic acid pentyl, (meth) acrylic acid isopentyl, (meth) acrylic acid n-hexyl, (meth) acrylic acid 2-methylpenter, (meth) acrylic acid 3-methylpenter, (meth) acrylic acid 4- Methylpentyl, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2,3-dimethylbutyl (meth) acrylate, 2,2-dimethylbutyl (meth) acrylate, 3,3- (meth) acrylic acid Dimethylbutyl, n-heptyl (meth) acrylate, 2-methylhexyl (meth) acrylate, (meth) acryl 3-methylhexyl acid, 4-methylhexyl (meth) acrylate, 5-methylhexyl (meth) acrylate, 2,2-dimethylpentyl (meth) acrylate, 2,3-dimethylpentyl (meth) acrylate, 4,4-dimethylpentyl (meth) acrylate, 3,4-dimethylpentyl (meth) acrylate, n-octyl (meth) acrylate, 2-methylheptyl (meth) acrylate, (meth) acrylic acid 3- Methylheptyl, 4-methylheptyl (meth) acrylate, 5-methylheptyl (meth) acrylate, 3-ethylhexyl (meth) acrylate, 4-ethylhexyl (meth) acrylate, 5-ethylhexyl (meth) acrylate, etc. Can be given.

  In addition to the above-mentioned (meth) acrylic acid alkyl ester and (meth) acrylic acid, the above monomer mixture may contain other copolymerizable monomers. Examples of the other copolymerizable monomers include styrene monomers such as styrene and α-methylstyrene, (meth) acrylonitrile, (meth) acrylamide, maleic acid, maleic anhydride, itaconic acid, vinyl acetate, Among them, vinyl versatate, etc., of which only one type may be used or two or more types may be used.

  Among the monomer mixtures, the composition ratio (weight ratio) between (meth) acrylic acid alkyl ester and (meth) acrylic acid is (meth) acrylic acid alkyl ester / (meth) acrylic acid, and is 95/5 or more. Is preferably 97/3 or more. If it is less than 95/5, the water resistance of the resulting coating film tends to decrease. On the other hand, the upper limit of this composition ratio is preferably 99/1 and preferably 98/2. When it is larger than 99/1, the transparency of the produced coating film tends to be lowered.

  The composition ratio of the monomer mixture is 50 to 99/1 to 5/0 to 49 (weight ratio) as (meth) acrylic acid alkyl ester / (meth) acrylic acid / other copolymerizable monomers. 100 is preferable, and 86 to 98 / 1.5 to 4 / 0.5 to 10 is more preferable. When the amount of the (meth) acrylic acid alkyl ester is less than 50% by weight, the water resistance of the resulting coating film tends to decrease. On the other hand, when it is more than 99% by weight, the transparency of the produced coating film tends to decrease. Moreover, when (meth) acrylic acid is less than 1 weight%, there exists a tendency for the transparency of a produced coating film to fall. On the other hand, when it is more than 5% by weight, the water resistance of the resulting coating film tends to decrease.

  The amount of the other monomer component used may be used depending on the purpose of the copolymerization, but the upper limit of the amount used is preferably 49% by weight in the total monomer components. When this is exceeded, the original property as a (meth) acrylic polymer may be impaired.

  The resin component used as the component (A) is produced by subjecting the monomer mixture to emulsion polymerization in an aqueous medium in the presence of a radical polymerization initiator and an emulsifier.

  The aqueous medium refers to water or a medium containing water as a main component and mixed with a water-soluble organic solvent such as methanol or ethanol as necessary.

  The reaction temperature of the emulsion polymerization is not particularly limited, and may be, for example, about 40 to 80 ° C. Also, the reaction time is not particularly limited, and may be about 4 to 10 hours, for example.

  In the above emulsion polymerization, the charging method is not particularly limited, but a method of reacting while slowly dropping a monomer mixture into an aqueous medium in the presence of a radical polymerization initiator and a surfactant is a reaction heat. It is preferable in that it can be easily removed and a relatively small particle size can be easily obtained.

  As the radical polymerization initiator, those generally used for emulsion polymerization can be used. Examples thereof include initiators composed of persulfates such as ammonium persulfate, potassium persulfate, sodium persulfate, etc., redox initiators in which a reducing agent such as sulfites and thiosulfates is used in combination with the above persulfates, lauroyl peroxide , T-butyl hydroperoxide, organic peroxides such as cumene hydroperoxide, or redox initiators using these in combination with reducing agents such as iron (II) salts, sulfites and thiosulfates, 2,2'-azobis (Isobutyronitrile), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis [2- (2-imidazolin-2-yl) propane] Initiators composed of azo compounds such as dihydrochloride and 2,2'-azobis (2-methylpropionamidine) dihydrochloride are used. It is possible.

  Various emulsifiers can be used as the emulsifier, and in particular, it is necessary to use a reactive nonionic emulsifier. By using the reactive nonionic emulsifier, the nonionic emulsifier component is contained in the film-forming resin and thus contained in the antifogging agent composition. Thereby, durability against aggregation by alcohols, that is, alcohol resistance can be improved.

  Examples of this reactive nonionic emulsifier include α-hydro-ω- (1-alkoxymethyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl)) (Adeka Corporation). Manufactured by: ADEKA rear soap ER-10, ER-20, ER-30, ER-40), polyoxyethylene alkyl propenyl phenyl ether (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Aqualon RN20, RN30, RN50), polyoxyalkylene Examples include alkenyl ethers (manufactured by Kao Corporation: Latemul PD-420, PD-430, PD-450).

  As the emulsifier used, in addition to the reactive nonionic emulsifier, a reactive anionic emulsifier, a nonreactive anionic emulsifier, a nonreactive nonionic emulsifier, and the like can be used as necessary. Examples of this reactive anionic emulsifier include α-sulfo-ω- (1-alkoxymethyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl) ammonium salt (for example, ( ADEKA Co., Ltd .: ADEKA rear soap SR-10, SR-1025, etc.), α-sulfo-ω- (1- (nonylphenoxy) methyl-2- (2-propenyloxy) ethoxy) -poly ( Oxy-1,2-ethanediyl) ammonium salt (for example, ADEKA Co., Ltd .: Adecalia Soap SE-10, SE-1025A, etc.), polyoxyethylene alkylpropenyl phenyl ether sulfate ammonium salt (for example, Daiichi Kogyo Seiyaku Co., Ltd .: Aqualon HS-10, HS-5, BC-10, BC-5, etc. ), Alkyl ether sulfate ammonium salt (for example, Dairon Kogyo Seiyaku Co., Ltd .: Aqualon KH-10, etc.), alkyl allyl sulphate (for example, Sanyo Chemical Industries, Ltd.) : Eleminol JS-20, manufactured by Kao Corporation: Latemulu S-180A, S-180, etc.), polyoxyalkylene alkenyl ether sulfate ammonium salt (for example, manufactured by Kao Corporation: Latemuru PD-104, etc.) Etc.).

  Examples of the non-reactive anionic emulsifier include sodium lauryl sulfate, sodium dodecylbenzenesulfonate, potassium semi-cured fatty acid, potassium alkenyl succinate, dialkyl succinate, sodium lauroyl sarcosine, sodium N-lauroylmethyl taurate, Examples thereof include sodium N-cocoylmethyl taurate, sodium β-naphthalenesulfonate formalin condensate, sodium alkyldiphenyl ether disulfonate, sulfate ester of polyoxyethylene alkyl (or alkylphenyl) ether, sodium polyoxyethylene lauryl ether acetate and the like.

  Examples of the non-reactive nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyoxyethylene fatty acid Examples thereof include esters, polyoxyethylene hydrogenated sterols, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene lanolin, polyoxyethylene lanolin alcohol, polyoxyethylene lanolin alcohol ether, polyoxyethylene lanolin fatty acid esters and the like.

  Among the above, anionic systems such as sodium lauryl sulfate, sodium dodecylbenzenesulfonate, potassium alkenyl oxalate, dialkyl oxalate ester salt, sodium alkyldiphenyl ether disulfonate, polyoxyethylene alkyl ether sulfate ester salt, alkylphenyl ether sulfate ester salt The use of an emulsifier is relatively preferable in that the amount used is small and the emulsion tends to be stable.

  The amount of the reactive nonionic emulsifier added is preferably 1 part by weight or more and more preferably 3 parts by weight or more with respect to 100 parts by weight of the monomer mixture. When the amount is less than 1 part by weight, the miscibility with the component (C) which is an alcohol such as isopropanol tends to deteriorate. On the other hand, the upper limit of the addition amount is preferably 10 parts by weight, and more preferably 7 parts by weight. When the amount is more than 10 parts by weight, the water resistance tends to decrease.

  As said component (A), in addition to the specific (meth) acrylic-type copolymer obtained above, as needed, a film-forming auxiliary is added for the purpose of improving the film-forming property and improving the coating film appearance. By adding, the minimum film forming temperature can be adjusted. Examples of the film forming aid include texanol isobutyrate (TXIB) and butyl cellosolve.

  The amount of the film-forming aid added is preferably 2.5 parts by weight or more and more preferably 5 parts by weight or more with respect to 100 parts by weight of the (meth) acrylic copolymer. When the amount is less than 2.5 parts by weight, the effect of improving the appearance of the coating film tends to be insufficient. On the other hand, the upper limit of the addition amount is preferably 10 parts by weight, and more preferably 7.5 parts by weight. When the amount is more than 10 parts by weight, the drying property of the coating film tends to deteriorate.

(Ingredient (B))
Next, the inorganic colloidal sol that is the component (B) will be described.
This inorganic colloidal sol has a function of imparting hydrophilicity to the surface by coating it on the surface of a molded product such as a hydrophobic film. Examples of this inorganic colloidal sol include silica, alumina, water-insoluble lithium silicate, inorganic aqueous colloidal particles such as iron hydroxide, tin hydroxide, titanium oxide, and barium sulfate in various methods in water or a hydrophilic medium. A dispersed aqueous sol may be mentioned. Of these, silica sol and alumina sol are preferred. These may be used alone or in combination.

  In addition, as the shape of the inorganic colloid sol, there are two types of colloidal sol of spherical silica and colloidal sol of chain silica. In the present invention, only one of the above may be used, and both are used. May be.

  Among the inorganic colloidal sols, the average particle diameter of the spherical silica in the spherical silica colloidal sol is preferably 5 nm or more, and more preferably 10 nm or more. If it is smaller than 5 nm, the stability of the inorganic colloidal sol tends to be lacking. On the other hand, the upper limit of the average particle diameter is preferably 250 nm, and more preferably 100 nm. If it is larger than 250 nm, the coating film tends to be devitrified in white, and the anti-fogging sustainability may be lowered. Within the above range, two or more colloidal sols having different average particle diameters may be used in combination.

  The amount of the component (B) used is preferably 10 parts by weight or more, more preferably 20 parts by weight or more per 100 parts by weight of the component (A). If it is less than 10 parts by weight, the antifogging effect tends to be insufficient. On the other hand, the upper limit of the amount used is preferably 150 parts by weight, and more preferably 100 parts by weight. When the amount is more than 150 parts by weight, the coating film tends to be brittle or the transparency tends to be insufficient.

(Component (C) and Component (D))
Next, the aliphatic alcohol having 1 to 10 carbon atoms as the component (C) and the water as the component (D) will be described.
The said component (C) is a medium used with the water which is a component (D) as a dispersion medium of a component (A) and a component (B). Examples of such alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, t-butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol and the like. Among these, isopropanol is preferable because of miscibility with water.

  In addition, as the usage-amount of the said component (C), it is preferable to set it as 50 weight part or more per 100 weight part of said components (A), and it is more preferable to set it as 100 weight part or more. If it is less than 50 weight part, the drying property of a coating film will deteriorate, or liquid viscosity will become high, and there exists a tendency for workability | operativity to deteriorate. On the other hand, the upper limit of the amount used is preferably 500 parts by weight, and more preferably 300 parts by weight. If it is more than 500 parts by weight, it may be difficult to control the film thickness.

  Further, the weight blending ratio of the component (C) and the component (D) is preferably 0.25 or more and more preferably 0.5 or more in terms of (C) / (D). If it is smaller than 0.25, the drying property after application tends to deteriorate. On the other hand, the upper limit of the weight blending ratio is preferably 5.0, and more preferably 3.0. When it is larger than 5, the viscosity of the composition becomes high and the workability during coating tends to deteriorate.

(Anti-fogging agent composition)
The anti-fogging agent composition concerning this invention is obtained by mixing said component (A)-component (D).

  The minimum film-forming temperature of the resulting antifogging agent composition needs to be −25 ° C. or higher, preferably −10 ° C. or higher, and more preferably −5 ° C. or higher. When it is lower than -25 ° C, the coating film tends to be sticky and tends to block. On the other hand, the upper limit of the minimum film forming temperature is 20 ° C., preferably 10 ° C., and more preferably 5 ° C. When it is higher than 20 ° C, the appearance of the coating film may be deteriorated.

  For the antifogging agent composition, if necessary, conventional additives such as antifoaming agents, plasticizers, film-forming aids, thickeners, pigments, pigment dispersants, weather resistance improvers, heat stabilizers, etc. Can be mixed.

(Anti-fogging film)
The antifogging agent composition described above is applied to the surface of a film-like substrate, and a coating film is formed by volatilizing a liquid dispersion medium by forced drying or natural drying, thereby expressing antifogging properties on the film surface. be able to. As a forced drying method, a hot air drying method, an infrared radiation method, or the like can be employed.

  The heating temperature for forced drying is determined by the applied antifogging agent composition, but is in the range of 50 to 250 ° C, preferably 70 to 200 ° C.

  The film-like substrate means a film, a sheet or the like. Examples of the material for the film-like substrate include synthetic resins and semi-synthetic resins. Among these, examples of particularly great practical value include synthetic resins, particularly thermoplastic resins.

  As a method for coating the antifogging agent composition on the surface of the film-like substrate, any known method such as a roll coating method, a dip coating method, a brush coating method, a spray coating method, a bar coating method, a knife coating method, etc. It may be by a method.

The surface of the above antifogging agent composition of the film-form substrate is coated and dried coating weight of solids after volatilization is preferably ^{0.01~10g / m 2, 0.1~5g / m} 2 Is more preferable. If the adhesion between the film-like substrate surface and the coating film derived from the antifogging agent composition is not sufficient, before applying the antifogging agent composition, the substrate surface is subjected to plasma treatment, Alternatively, the substrate surface may be modified by performing corona discharge treatment or the like.

Hereinafter, the present invention will be described more specifically with reference to examples. First, the evaluation method and the raw materials used will be described.
(Evaluation methods)
[Glass transition temperature (Tg)]
The glass transition temperature (Tg) was calculated according to the following formula (1) (Fox formula).
1 / Tg = Wa / Tga + Wb / Tgb + (1)
In the above formula (1), Tg is the glass transition point (K) of the copolymer, Tga is the glass transition point (K) of the homopolymer of monomer a, and Tgb is the glass transition point of the homopolymer of monomer b (K). ), Wa represents the weight fraction of monomer a, and Wb represents the weight fraction of monomer b.

[Minimum film-forming temperature (MFT)]
The compositions obtained in Examples and Comparative Examples were applied to a thermal gradient tester (manufactured by SHIMADEN Co. LTD) using an applicator so as to be 200 g / m ² . After 24 hours, the minimum temperature of the portion where the continuous film was formed was measured.

[Appearance of coating film]
The compositions obtained in Examples and Comparative Examples were applied to a glass plate degreased with acetone so as to be 5 g / m ² by a bar coating method, and dried at 90 ° C. for 2 minutes (hot air dryer). The transparency of the coating film appearance was visually observed and evaluated according to the following criteria.
◎… Transparency is extremely excellent.
○: Slightly inferior in transparency, but practically no problem
Δ: Inferior in transparency.
X: Transparency is remarkably inferior and cannot be practically used.

[Anti-fogging evaluation]
Install the glass plate on the surface of the aquarium with the coating surface of the glass plate facing the inside of the aquarium. The installation conditions are such that the distance between the coating surface and the water tank surface is 20 cm, the water temperature is 50 ° C., and the outside air temperature is 23 ° C. The antifogging property of the coating film at the initial time (after 30 minutes) and the long time (after 1 week) was observed with the naked eye and evaluated according to the following criteria.
A: Water is attached in a thin film and no water droplets are observed.
○: Water is attached in a thin film, but Otsu water droplets are slightly observed.
Δ: A state in which fine water droplets are partially adhered.
X: A state where fine water droplets are observed to adhere to the entire glass plate.

(raw materials)
<Component (A)>
((Meth) acrylic acid alkyl ester)
-Ethyl acrylate: Mitsubishi Chemical Corporation, hereinafter abbreviated as "EA".
・ Butyl acrylate: manufactured by Mitsubishi Chemical Corporation, hereinafter abbreviated as “BA”.
・ 2-ethylhexyl acrylate: manufactured by Mitsubishi Chemical Corporation, hereinafter abbreviated as “2EHA”.
Methyl methacrylate: Mitsubishi Rayon Co., Ltd .: Acryester MMA (trade name), hereinafter abbreviated as “MMA”.
Allyl methacrylate: manufactured by Mitsubishi Rayon Co., Ltd .: Acryester AMA (trade name), hereinafter abbreviated as “AMA”.

((Meth) acrylic acid)
-Methacrylic acid: Mitsubishi Rayon Co., Ltd., hereinafter abbreviated as "MAA".
Acrylic acid: An aqueous solution with a purity of 80% manufactured by Mitsubishi Chemical Corporation, hereinafter abbreviated as “AA”.

(Other copolymerizable monomers)
Acrylonitrile: manufactured by Dianitricks Co., Ltd., hereinafter abbreviated as “AN”.
-Maleic anhydride: manufactured by Mitsubishi Chemical Corporation, hereinafter abbreviated as “Macid”.
Acrylamide: manufactured by Diaanitrix Co., Ltd., hereinafter abbreviated as “AAm”.
Itaconic acid: manufactured by Iwata Chemical Industry Co., Ltd., hereinafter abbreviated as “IA”.

(Reactive nonionic emulsifier)
.Alpha.-sulfo-.omega .- (1- (alkoxy) methyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl) (10 mol adduct): ADEKA Co., Ltd .: ADEKA Rear soap ER-10, hereinafter abbreviated as “ER10”.
.Alpha.-sulfo-.omega .- (1- (alkoxy) methyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl) (20 mol adduct): ADEKA Co., Ltd .: ADEKA Rear soap ER-20, hereinafter abbreviated as “ER20”.

.Alpha.-sulfo-.omega .- (1- (alkoxy) methyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl) (30 mol adduct): ADEKA Co., Ltd .: ADEKA Rear soap ER-30, hereinafter abbreviated as “ER30”.
.Alpha.-sulfo-.omega .- (1- (alkoxy) methyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl) (40 mol adduct): ADEKA Co., Ltd .: ADEKA Rear soap ER-40, hereinafter abbreviated as “ER40”.

(Non-reactive nonionic emulsifier)
Polyoxyethylene nonylphenyl ether (20 mol adduct): Sanyo Chemical Industries, Ltd. Nonipol 200, hereinafter abbreviated as “N200”.
Polyoxyethylene derivative: manufactured by Kao Corporation: Emulgen A-60, hereinafter abbreviated as “EA60”.
Polyoxyethylene nonylphenyl ether (35 mol adduct): manufactured by Kao Corporation: Emulgen 935, hereinafter abbreviated as “E935”.

(Reactive anionic emulsifier)
.Alpha.-sulfo-.omega .- (1- (alkoxy) methyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl) ammonium salt: ADEKA Co., Ltd .: ADEKA rear soap SR −10, hereinafter abbreviated as “SR10”.
Aqueous solution of polyoxyethylene alkylpropenyl phenyl ether sulfate ammonium salt: manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Aqualon BC-10, hereinafter abbreviated as “BC10”.
Aqueous solution of sodium alkylallylsulfosuccinate: Sanyo Chemical Industries, Ltd .: Eleminol JS-20, hereinafter abbreviated as “JS20”.

(Non-reactive anionic emulsifier)
-Sodium dodecylbenzenesulfonate: manufactured by Kao Corporation: Neoperex G65, hereinafter abbreviated as "G65".
Polyoxyethylene nonyl phenyl ether sulfate ammonium salt: Sanyo Chemical Industries, Ltd .: Eleminol ES-70, hereinafter abbreviated as “ES70”.
Dialkyl succinate ester salt: manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Neocor SWC, hereinafter abbreviated as “SWC”.

(Film forming aid)
2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (Texanol isobutyrate): manufactured by Chisso Corporation: Texanol CS-12, hereinafter abbreviated as “CS12”.

<Component (B)>
(Inorganic colloidal sol)
Colloidal silica: Nissan Chemical Industries, Ltd .: Snowtex CM, chain silica, particle size 20-30 mm, hereinafter abbreviated as “CM”.

<Ingredient (C)>
(Aliphatic alcohol)
Isopropanol: manufactured by Nippon Alcohol Co., Ltd .: Toxo IPA, hereinafter abbreviated as “IPA”.

<Others>
-Bisphenol A type liquid epoxy resin: manufactured by Japan Epoxy Resins Co., Ltd .: JER828XA, hereinafter abbreviated as “828XA”.
Trisdimethylaminomethylphenol: manufactured by Japan Epoxy Resins Co., Ltd .: JER Cure 3010, hereinafter abbreviated as “E3010”.
-Sorbitol polyglycine ether: manufactured by Nagase ChemteX Corporation: Denacol EX-614B, hereinafter abbreviated as "EX614B".

(Production of component (A))
A four-necked flask was charged with 80 parts by weight of water and heated to 60 ° C. under a nitrogen gas stream, and 0.3 parts by weight of ammonium persulfate was added thereto. Subsequently, the monomer mixture which mixed each monomer shown in Table 1, the emulsifier, etc. in the quantity shown in Table 1 was dripped over 3 hours. The reaction temperature at this time was maintained in the range of 60 to 70 ° C., but after the completion of the dropwise addition, the reaction temperature was maintained in the same temperature range for 2 hours and then cooled to produce an aqueous dispersion of component (A).

(Examples 1-11, Comparative Examples 1-5)
(Manufacture of anti-fogging agent composition)
As shown in Table 2, a film-forming auxiliary is added to the component (A) as necessary, and this and components (B) to (D) are mixed in the amounts shown in Table 2 to form an antifogging agent composition. The thing was manufactured. Said evaluation was performed using the obtained anti-fogging agent composition. The results are shown in Table 2. In Table 2, since the component (A) and the component (B) are hydrated substances, the amount of dry is shown in both columns, and the amount of water is listed in the component (D). Therefore, the amount of the component (D) indicates the total amount of moisture in the components (A) and (B) and, if necessary, the amount of moisture newly added.

Claims (11)

An antifogging agent composition containing at least the following components (A), (B), (C), and (D) and having a minimum film-forming temperature of −25 ° C. or higher and 20 ° C. or lower.
(A) A (meth) acrylic copolymer obtained by emulsion polymerization of a monomer mixture containing (meth) acrylic acid alkyl ester and (meth) acrylic acid as monomers in the presence of a reactive nonionic emulsifier. A film-forming resin composition containing a polymer.
(B) Inorganic colloidal sol.
(C) An aliphatic alcohol having 1 to 10 carbon atoms.
(D) Water.   The antifogging agent composition according to claim 1, wherein the monomer mixture contains another copolymerizable monomer in addition to the (meth) acrylic acid alkyl ester and (meth) acrylic acid.   The composition ratio of the monomer mixture is (meth) acrylic acid alkyl ester / (meth) acrylic acid / other copolymerizable monomer = 50 to 99/1 to 5/0 to 49 (whole ratio). The antifogging agent composition according to claim 1 or 2, wherein   The antifogging agent composition according to any one of claims 1 to 3, wherein the emulsion polymerization is performed in the presence of an anionic emulsifier in addition to the reactive nonionic emulsifier.   5. The antifogging agent composition according to any one of 1 to 4, wherein the inorganic colloid sol as the component (B) is one or both selected from a spherical silica colloid sol and a chain silica colloid sol.   6. The antifogging composition according to claim 5, wherein the spherical silica in the spherical silica colloid sol has an average particle diameter of 5 to 250 nm.   The antifogging composition according to any one of claims 1 to 6, wherein the aliphatic alcohol having 1 to 10 carbon atoms, which is the component (C), is isopropanol.   The blending ratio of the component (B) per 100 parts by weight of the component (A) is 10 to 150 parts by weight, and the blending ratio of the component (C) is 50 to 500 parts by weight. The anti-fogging agent composition in any one.   The antifogging agent composition according to any one of claims 1 to 8, wherein a weight blending ratio of the component (C) and the component (D) is (C) / (D) = 0.25 to 5.0. .   The antifogging composition according to any one of claims 1 to 9, wherein the minimum film-forming temperature is -10 ° C or higher and 10 ° C or lower. An antifogging film obtained by applying the antifogging agent composition according to any one of claims 1 to 10 to a film-like substrate and drying.