WO2016084895A1

WO2016084895A1 - Anti-fogging resin film and anti-fog coating agent

Info

Publication number: WO2016084895A1
Application number: PCT/JP2015/083226
Authority: WO
Inventors: 近藤　久美子
Original assignee: 丸善薬品産業株式会社
Priority date: 2014-11-27
Filing date: 2015-11-26
Publication date: 2016-06-02
Also published as: JPWO2016084895A1

Abstract

Provided is a technique by which the water resistance of a hydrophilic anti-fog layer can be enhanced, thereby improving the durability thereof. The cohesion of a hydrophobic binder resin employed to improve cohesion of an anti-fog layer 3 and a polyethylene base material 2 of film shape, and hydrophilic inorganic colloidal particles employed to improve the hydrophilic properties of the anti-fog layer 3, can be improved by an ampiphatic thermoplastic resin. Additionally, because the thermoplastic resin for improving cohesion between the binder resin and the inorganic colloidal particles does not dissolve in water drops wetting the anti-fog layer 3 surface, outflow of the hydrophilic inorganic colloidal particles dispersed through the anti-fog layer 3 from the film-shaped base material 2 surface due to water drops wetting the anti-fog layer 3 surface can be minimized by the thermoplastic resin, whereby the water resistance of the hydrophilic anti-fog layer 3 can be enhanced, and the durability of the anti-fog layer can be improved.

Description

Antifogging resin film and antifogging coating agent

The present invention relates to an antifogging resin film and an antifogging coating agent comprising an antifogging layer laminated on at least one main surface of a polyethylene film-like substrate.

Conventionally, in an agricultural house such as a vinyl house, there is a risk that water droplets may adhere mainly to the inner side of the agricultural resin film (vinyl house) due to a rapid temperature change such as dawn. When the water droplets are dripped onto the surface of the agricultural product in the house, the water droplet adhering portion of the agricultural product is whitened, resulting in a decrease in the commercial value of the agricultural product or the occurrence of disease on the buds and leaves. Therefore, by applying an anti-fogging treatment to the inside of the agricultural resin film and imparting hydrophilicity to the resin film, the water droplets evenly wet the inner surface of the agricultural resin film and flow down. Should not be dripped onto crops.

By the way, an anti-fogging agent (also referred to as a droplet agent) is used for the above-described anti-fogging treatment. There are two types of anti-fogging agents: a resin kneading type and a coating type (coating type).

For the resin kneading type, a hydrophilic component (antifogging agent) is kneaded into a film-like substrate (resin film), and the hydrophilic component bleeds out from the resin film and precipitates on the substrate surface. Is applied to the resin film. Examples of the anti-fogging agent of the resin kneading type include surfactants, those mainly composed of inorganic colloid particles such as metal colloids, dicarboxylic acids having 3 to 20 carbon atoms and aliphatic alcohols or aliphatic amines, Proposals include those based on a reaction mixture with a monohydric alcohol or an oxirane ring, and those based on a mixture of a hindered amine compound and a hydrotalcide compound. It is used by being kneaded in advance in a resin film or the like (for example, see Patent Documents 1 to 3).

However, in the resin kneading type, the antifogging agent kneaded into the resin film bleeds out, and the antifogging effect may be significantly reduced in about one year. Therefore, it is difficult to impart antifogging properties to a resin film over a long period of one year or longer with a resin kneading type antifogging agent.

In the coating type, the antifogging property is a resin film by applying an antifogging agent (antifogging coating agent) containing a hydrophilic compound to a film substrate (resin film) to form an antifogging layer. To be granted. As coating type anti-fogging agents, surfactants such as sorbitan acid esters, hydrophilic inorganic compounds such as alumina sol and colloidal silica, and hydrophilic polymers such as polyvinyl alcohol are added as hydrophilic compounds. (For example, refer to Patent Documents 4 and 5). Moreover, in order to improve the durability of the antifogging layer, an antifogging agent in which a polyolefin compound having high adhesion with a resin film (polyethylene) is added together with a hydrophilic compound has been proposed (for example, Patent Document 6). , 7).

Japanese Patent Laid-Open No. 11-151788 Japanese Patent Laid-Open No. 9-31242 Japanese Patent Publication No. 6-99602 Japanese Patent Laid-Open No. 7-53747 JP 2002-88298 A JP 7-52343 A JP-A-9-104773

By the way, the coating type anti-fogging agent is roughly classified into two types: aqueous and solvent type (including solvent / water type).

Compared to solvent-type antifogging agents, water-based antifogging agents are inferior in coating properties and adhesion to resin films, and antifogging agents tend to dissolve into water droplets that evenly wet the antifogging layer surface of resin films. There is a possibility that a problem occurs in the durability of the antifogging layer. On the other hand, the solvent-type antifogging agent improves the coating property on the resin film as compared with the water-based antifogging agent, and the solvent roughens the surface of the resin film. Adhesion to the resin film can be improved. However, since it is difficult to dissolve the hydrophilic compound in the hydrophobic solvent, the antifogging property of the antifogging layer formed by the solvent-type antifogging agent may be insufficient.

In addition, when the antifogging agent contains only the hydrophilic compound, the hydrophilic compound tends to flow into the water droplets that wet the resin film, which may cause a problem in durability of the antifogging layer. Therefore, as described above, in order to improve the adhesion between the hydrophilic compound and the resin film, a binder resin such as a polyolefin compound having adhesion to the resin film may be added to the antifogging agent. However, even in this case, when the hydrophilic compound is a hydrophilic polymer, the antifogging property may gradually deteriorate due to dissolution of the hydrophilic polymer in water droplets that wet the resin film. In addition, when the hydrophilic compound is a hydrophilic inorganic compound such as silica that is hardly soluble in water, the hydrophilic inorganic compound dispersed in the solvent is not likely to be dissolved into water droplets that wet the resin film. May cause serious problems. That is, a hydrophilic inorganic compound added to the antifogging layer to improve hydrophilicity, and a binder resin such as a polyolefin compound added to the antifogging layer to improve adhesion to the resin film substrate; Therefore, the hydrophilic inorganic compound flows out to the water droplets that wet the resin film, and the antifogging property may deteriorate over time.

As described above, the antifogging agent is required to have contradictory properties of hydrophilicity for developing antifogging properties and water resistance for maintaining antifogging properties for a long period of time. .

This invention is made | formed in view of an above-described subject, and it aims at providing the technique which can aim at the improvement of the durability by raising the water resistance of the anti-fogging layer provided with hydrophilicity. .

In order to achieve the above-described object, an antifogging resin film of the present invention comprises a polyethylene film-like substrate and an antifogging layer laminated on at least one main surface of the substrate, The anti-fogging layer has an affinity for the thermoplastic resin, an amphiphilic thermoplastic resin that does not dissolve in a solvent composed only of water, hydrophilic inorganic colloid particles having an affinity for the thermoplastic resin, And a binder resin having adhesiveness to the substrate.

Further, the antifogging coating agent of the present invention is an antifogging coating agent that forms an antifogging layer of an antifogging resin film by being laminated on a polyethylene film-like base material, and alcohol and water are mixed. In the solvent, an amphiphilic thermoplastic resin that does not dissolve in a solvent composed only of water, hydrophilic inorganic colloid particles having an affinity for the thermoplastic resin, and an affinity for the thermoplastic resin, And a binder resin having adhesiveness to the base material.

In the invention thus configured, the antifogging layer is laminated on at least one main surface of the polyethylene film-like base material, and the antifogging layer contains a binder resin having adhesion to the base material. Therefore, the adhesion between the antifogging layer and the film-like substrate can be improved. Moreover, since hydrophilic inorganic colloidal particles are contained in the antifogging layer, the antifogging property can be expressed by imparting hydrophilicity to the antifogging layer.

In addition, the anti-fogging layer contains an amphiphilic thermoplastic resin having affinity for both the binder resin for improving the adhesion to the film-like substrate and the inorganic colloidal particles for improving the hydrophilicity. It is. Therefore, when the thermoplastic resin is interposed between the binder resin and the inorganic colloid particles, the adhesion between the film-like base material, the binder resin having high adhesion, and the hydrophilic inorganic colloid particles is improved. Can do. Moreover, since the said thermoplastic resin contains the hydrophilic group, it can also contribute to the hydrophilic improvement of an anti-fogging layer.

Further, since the thermoplastic resin that improves the adhesion between the binder resin and the inorganic colloidal particles does not dissolve in a solvent composed only of water, there is no possibility that the thermoplastic resin dissolves in water droplets that wet the antifogging layer surface. Therefore, the hydrophilic inorganic colloidal particles dispersed in the antifogging layer flow out of the surface of the film-like substrate by water droplets that wet the antifogging layer surface. Since it can be suppressed by interposing the thermoplastic resin having adhesion to the colloidal particles, the water resistance of the antifogging layer having hydrophilicity can be increased, and the durability of the antifogging layer can be improved. Can do.

The binder resin may be a hydrophobic polyolefin emulsion containing a carboxylic acid group.

The anti-fogging coating agent comprises the binder resin comprising 0.1% by weight to 10% by weight of a hydrophobic polyolefin emulsion containing a carboxylic acid group, and the hydrophilic resin having a weight of 0.1% by weight to 30% by weight. 40 wt% of inorganic colloid particles, 0.1 wt% to 10 wt% of the amphiphilic thermoplastic resin, and alcohol and water mixed in a ratio of alcohol: water = 1: 9 to 9: 1. % To 60% by weight of the solvent.

With such a configuration, since the binder resin is composed of a hydrophobic polyolefin emulsion containing a carboxylic acid group, the adhesion between the antifogging layer and the film-like substrate can be reliably improved. In addition, the affinity between the hydrophobic polyolefin emulsion and the thermoplastic resin containing a hydrophobic group is very high, and the thermoplastic resin is interposed between the binder resin and the inorganic colloidal particles, so that a film-like substrate is obtained. It is possible to reliably improve the adhesion between the polyolefin emulsion having high adhesion and the hydrophilic inorganic colloid particles.

The polyolefin emulsion is a copolymer containing at least one of ethylene and propylene and at least one of a structure represented by the following general formula (1) and a carboxyl group. The structure represented by 1) and / or the carboxyl group may be contained in an amount of 0.1 to 15% by weight.

In this way, it is possible to improve the adhesion between the polyolefin emulsion and the polyethylene film-like substrate.

The copolymer may further contain a vinyl acetate group.

In this way, the adhesion between the polyolefin emulsion and the polyethylene film-like substrate can be further improved.

The inorganic colloidal particles preferably include at least one of silica, alumina, and a layered clay compound, and have a particle size of 3 nm to 200 nm.

In this way, hydrophilicity can be reliably imparted to the antifogging layer by the inorganic colloidal particles.

The thermoplastic resin may be dissolved in a solvent in which alcohol and water are mixed in a ratio of alcohol: water = 1: 9 to 9: 1.

In this case, since the thermoplastic resin does not have a risk of dissolving in the water droplets that wet the surface of the antifogging layer, the antifogging layer having hydrophilicity can be reliably improved.

The thermoplastic resin may contain at least one of a hydroxyl group, ethylene oxide, propylene oxide, ester bond, and urethane bond.

The thermoplastic resin contains a) polyvinyl alcohol having a saponification degree of 20% to 51%, b) 45 mol% to 85 mol% of hydrophilic monomer units, an average degree of polymerization of 1500 to 3500, and an acetalization degree. Is preferably at least one of water-soluble vinyl acetal copolymers having 4 mol% to 20 mol%.

In addition, a compound containing at least two of amide groups, amino groups, hydroxyl groups, and vinyl acetate groups that react with the carboxylic acid groups contained in the polyolefin-based emulsion may be added to the base material. .

In this case, the amide group, amino group, hydroxyl group, or vinyl acetate group contained in the polyethylene film-like substrate reacts with the carboxylic acid group contained in the polyolefin emulsion of the antifogging layer to serve as a crosslinking agent. Since it functions, it is possible to further improve the adhesion between the antifogging layer and the film-like substrate.

Further, a polyolefin-based emulsion containing a carboxylic acid group is added to the base material, the carboxylic acid group contained in the polyolefin-based emulsion contained in the anti-fogging layer and the polyolefin-based emulsion contained in the base material are added to the anti-fogging layer. A compound containing at least two of any one of an amide group, an amino group, a hydroxyl group, and a vinyl acetate group that reacts with the carboxylic acid group contained in may be added.

In this way, the amide group, amino group, hydroxyl group, or vinyl acetate group contained in the antifogging layer is different from the polyolefin emulsion contained in the antifogging layer and the polyolefin emulsion contained in the film-like substrate. Since it reacts with a carboxylic acid group and functions as a crosslinking agent, the adhesion between the antifogging layer and the film-like substrate can be further improved.

According to the present invention, the adhesion between the binder resin that improves the adhesion between the antifogging layer and the polyethylene film-like substrate, and the hydrophilic inorganic colloid particles that improve the hydrophilicity of the antifogging layer, It can be improved by an amphiphilic thermoplastic resin containing a hydrophobic group and a hydrophilic group. Also, since the thermoplastic resin that improves the adhesion between the binder resin and the inorganic colloid particles does not dissolve in the water droplets that wet the antifogging layer surface, the hydrophilic inorganic colloid particles dispersed in the antifogging layer wet the antifogging layer surface. Since the thermoplastic resin having a high affinity with the binder resin can be prevented from flowing out from the surface of the film-like substrate due to water droplets, the water resistance of the antifogging layer having hydrophilicity can be improved, and The durability of the cloud layer can be improved.

It is sectional drawing which shows an anti-fogging resin film provided with the anti-fogging layer concerning one Embodiment of this invention. It is a figure which shows an example of the anti-fogging coating agent of this invention. It is a figure which shows an example of the anti-fogging coating agent of this invention. It is a figure which shows an example of the anti-fogging coating agent of this invention.

An embodiment of the present invention will be described with reference to FIG. FIG. 1 is a cross-sectional view showing an antifogging resin film provided with an antifogging layer according to an embodiment of the present invention.

(Anti-fogging resin film)
As shown in FIG. 1, the antifogging resin film 1 includes a polyethylene film-like substrate 2 and an antifogging layer 3 laminated on at least one main surface of the substrate 2.

(Base material)
The substrate 2 is a general polyethylene-based resin, for example, a low density polyethylene produced by a radical polymerization method, a high density polyethylene produced by an ion polymerization method, or a copolymer of ethylene and an α-olefin. And an ethylene-α-olefin copolymer obtained in the above manner. Examples of the α-olefin include alkenes having 2 to 6 carbon atoms such as propylene, isobutylene, 1-butene, 1-pentene and 1-hexene, and a mixture thereof can also be used. Of these, alkenes having 2 to 4 carbon atoms such as ethylene, propylene, isobutylene and 1-butene are more preferred.

Further, in order to improve the adhesion between the film-like base material 2 and the antifogging layer 3, a polyolefin compound containing a carboxylic acid group (polyolefin emulsion) may be added to the base material 2. In addition, the structure of the polyolefin compound added to the base material 2 is a structure substantially the same as the structure of the polyolefin compound demonstrated by the item of the following "anti-fogging layer".

Specifically, examples of the polyolefin compound containing a carboxylic acid group added to the substrate 2 include a polyethylene resin modified with maleic acid, itaconic acid, fumaric acid or a derivative thereof. Examples of the derivatives include, for example, maleic acid monoester, maleic acid diester, maleic anhydride, itaconic acid monoester, itaconic acid diester, itaconic anhydride, fumaric acid monoester, fumaric acid diester, fumaric anhydride, and the like. And anhydrides. Examples of the polyethylene resin include linear polyethylene, ultra-low density polyethylene, high density polyethylene, ethylene-vinyl acetate (VA) copolymer, ethylene-ethyl acrylate (EA) copolymer, ethylene-methacrylate copolymer. Examples include coalescence. Specific examples of the polyolefin compound containing a carboxylic acid group include Admer AT-1000 (manufactured by Mitsui Chemicals) and Modic L-502 (manufactured by Mitsubishi Chemical Corporation).

(Anti-fog layer)
The anti-fogging layer 3 is formed by in-line coating, for example, by applying an anti-fogging coating agent to one main surface of the unstretched substrate 2 and drying it, followed by stretching together with the substrate 2. . In addition, the anti-fogging layer 3 may be formed in one main surface of the base material 2 by the off-line coating method. Since the in-line coating method and the off-line coating method are well-known techniques, detailed description thereof is omitted.

Further, the antifogging layer 3 contains a hydrophobic polyolefin compound (a binder resin comprising a polyolefin emulsion), hydrophilic inorganic colloid particles, and an amphiphilic thermoplastic resin having a hydrophobic group and a hydrophilic group. ing.

Polyolefin compound The polyolefin compound is a copolymer containing at least one of ethylene and propylene and at least one of a structure represented by the following general formula (1) and a carboxyl group. 2) and (3). The polyolefin compound contains 0.1 to 15% by weight of unsaturated carboxylic acid or maleic anhydride.

Inorganic colloidal particles Inorganic colloidal particles contain at least one of silica, alumina, and layered clay compounds, and have a particle size of 3 nm to 200 nm. Specific examples of the inorganic layered compound include natural clays such as montmorillonite, beidellite and nontrite, and synthetic clays such as saponite, hectorite and stevensite.

-Thermoplastic resin The thermoplastic resin contains, for example, a hydrophobic group having an affinity for a polyolefin compound and a hydrophilic group having an affinity for an inorganic colloidal particle, for example. Further, the thermoplastic resin does not dissolve in a solvent composed only of water. In this embodiment, the alcohol and water are dissolved in a solvent in which alcohol: water = 1: 9 to 9: 1 are mixed. To do. Further, the thermoplastic resin contains at least one of a hydroxyl group, ethylene oxide, propylene oxide, ester bond, and urethane bond. As the alcohol forming the solvent, for example, various alcohols such as methanol, ethanol, n-propanol, isopropanol, and n-butanol are preferable, and isopropanol is particularly preferable.

Next, specific examples of the thermoplastic resin will be described.

a) Polyvinyl alcohol having a saponification degree of 20% to 51% represented by the following general formula (4). In addition,
Degree of polymerization: l + m
Saponification degree: [l / (l + m)] × 100 (mol%)
Defined by

b) a water-soluble vinyl acetal type represented by the following general formula (5), containing 45 mol% to 85 mol% of hydrophilic monomer units, having an average degree of polymerization of 1500 to 3500 and an acetalization degree of 4 mol% to 20 mol% Copolymer.

C) Hydroxypropyl cellulose represented by the following general formula (6), having a hydroxypropoxyl group of 53.4% to 75.5% and a molecular weight of 500,000 to 910,000.

d) Random copolymer of ethylene oxide (EO) and propylene oxide (PO9) represented by the following general formula (7): ethylene oxide / propylene oxide = 20/80 to ethylene oxide / propylene oxide = 0/100 or Copolymer of propylene oxide.

e) A modified polyamide resin, which is a block copolymer of vinylacetamide and sodium acrylate represented by the following general formula (8): vinylacetamide / sodium acrylate = 95/5 to vinylacetamide / sodium acrylate = 85/15 Polymerized polymer.

F) A polyester compound having an ester structure represented by the following general formula (9).

f-1) PET resin R of the component of the polyester compound represented by the general formula (9) is a terephthalic acid component such as alkali metal sulfoisophthalic acid and / or isophthalic acid, naphthalenedicarboxylic acid, adipic acid, cyclohexane-1, It is derived from acid components such as 4-dicarboxylic acid and p-oxybenzoic acid, and terephthalic acid is particularly preferable.

R ′ of the constituent component of the polyester compound represented by the general formula (9) is derived from a polyol component such as polyoxyalkylene glycol, and is random or block such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide and propylene oxide. A copolymer can be used, but polyethylene glycol is particularly preferred. Also, at least one alkylene glycol selected from alkylene glycols having 2 to 6 carbon atoms such as ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, etc., such as glycerin, trimethylolpropane and pentaerythritol. Polyol, polyvinyl alcohol, polyamide, etc. may be copolymerized.

f-2) Acrylic resin The polyester compound represented by the general formula (9) includes an acidic group-containing vinyl monomer containing an acidic group such as a carboxylic acid group in the structure, or a hydroxyl group-containing vinyl monomer containing a hydroxyl group in the structure, and It may be composed of an acrylic monomer copolymerized with the above monomer. Examples of the acrylic monomer include aromatic vinyl compounds, vinyl cyanide compounds, hydroxyl group-containing vinyl compounds, diene compounds, vinyl carboxylic acid ester compounds, alkyl vinyl ether compounds, other vinyl compounds, and hydrophobic allyl compounds.

G) A urethane compound represented by the following general formula (10).

R ′ as a constituent component of the urethane compound represented by the general formula (10) is derived from an organic diisocyanate. Examples of the organic diisocyanate include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and mixtures thereof ( TDI), diphenylmethane-4,4′-diisocyanate (MDI), naphthalene-1,5-diisocyanate (NDI), 3,3′-dimethyl-4,4′-biphenylene diisocyanate (TODI), polymethylene polyphenyl Aromatic diisocyanates such as diisocyanates, xylylene diisocyanate (XDI), aromatic alicyclic diisocyanates such as phenylene diisocyanate, 4,4'-methylenebiscyclohexyl diisocyanate (hydrogenated MDI), hexamethylene dii Cyanate (HDI), isophorone diisocyanate (IPDI), include aliphatic diisocyanates such as cyclohexane diisocyanate (hydrogenated XDI).

R of the constituent component of the urethane compound represented by the general formula (10) is derived from the above polyoxyalkylene glycol component.

Additive In addition, in order to improve the adhesion between the film-like base material 2 and the antifogging layer 3, the antifogging layer 3 contains the polyolefin compound contained in the antifogging layer 3 and the base material 2. A compound containing at least two of amide groups, amino groups, hydroxyl groups, and vinyl acetate groups that react with carboxylic acid groups contained in each polyolefin compound may be added as an additive.

The compound containing an amide group may be, for example, homopolymerization as shown in the following general formula (11) or may be as shown in the following general formula (12) (for example, polyacrylamide, ethylene · Acrylamide copolymer).

Further, it may be a copolymer with acrylic acid, allylamine, diallylamine, polyester or the like. Specifically, diallyldimethylammonium chloride / acrylamide copolymer PAS-J-81L, PAS-J-81, partially methylcarbonylated poly Allylamine PAA-AC5050A, partially ureated polyallylamine PAA-N5000, PAA-N5050CL (Knitbo Medical Co., Ltd.), diallylammonium chloride / acrylic acid / acrylamide copolymer ZCA100L (Senka Co., Ltd.), polyamide / polyester copolymer Examples thereof include a combined TAPE-617C (T & K Co., Ltd., manufactured by TOKA) and a polyamide polyamine / epichlorohydrin copolymer EPA-SK01 (produced by Yokkaichi Gosei Co., Ltd.).

As the compound containing an amino group, a compound containing two or more amino groups is desirable. For example, a diamine as shown in the following general formula (13) may be used, and as shown in the following general formula (14), (For example, ethylenediamine, polyallylamine).

Specifically, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, hexamethylenediamine, ethylaminoethylamine, N′N-di-tert-butylethylenediamine, 2,2′- Diaminodiethylamine, diethylenetriamine, N, N′-dimethyl-1,3-propanediamine, 3,3′-diaminodipropylamine, N, N′-bis (3-aminopropyl) ethylenediamine, 6,6′-iminodihexyl Amine, N, N′-bis (2-aminoethyl) -1,3-propanediamine, L-arginine, polyethyleneimine (Pure Chemical Co., Ltd.), aminoethylated acrylic polymer NK-200PM (manufactured by Nippon Shokubai Co., Ltd.) , Allylamine polymers PAA-01, PAA-03, allylamine dimethylallyl Amine polymer PAA-1112, diallylamine polymer PAS-21, allylamine maleic acid copolymer PAA-1151, partially uread polyallylamine PAA-N5000, PAA-N5050CL (manufactured by Knitbo Medical Co., Ltd.), polyamide / polyester copolymer Combined TAPE617C (T & K Co., Ltd., manufactured by TOKA) is exemplified.

As the compound containing a hydroxyl group, a polyhydric alcohol having two or more hydroxyl groups is desirable. For example, a compound represented by the following general formula (15) may be used, and a compound represented by the following general formula (16) may be used. It is also possible (for example, ethylene glycol, polyvinyl alcohol).

Specifically, ethylene glycol, propylene glycol, polyethylene glycol, glycerin, polyethylene oxide copolymer Alcox L-11, E160, ethylene oxide / propylene oxide copolymer EP1010N, Alcox EP10, having a sugar structure ( Guar gum: Grinstead Guar 175 (manufactured by Sanki Co., Ltd.), cellulose compound: Cellogen 3H (Daiichi Kogyo Seiyaku Co., Ltd.), Polytail H (manufactured by Mitsubishi Chemical Corporation), Gohsenol KP-08R, Gohsenx Z-100 (Japan Synthetic Chemical Industry Co., Ltd.)).

The compound containing a vinyl acetate group may be, for example, as shown in the following general formula (17) (for example, ethylene-vinyl acetate copolymer).

Specifically, SUMIKAFLEX S-752, S-755, 410HQ (manufactured by Sumitomo Chemtex Co., Ltd.), and RETITECH EL-105 (manufactured by Resitex Corporation) can be mentioned.

In this way, the various functional groups contained in the antifogging layer 3 react with the polyolefin compound contained in the antifogging layer 3 and the polyolefin compound contained in the film-like substrate 2 to function as a crosslinking agent. The adhesion between the antifogging layer 3 and the film-like base material 2 can be further improved.

(Anti-fogging coating agent)
The anti-fogging coating agent forms the anti-fogging layer 3 of the anti-fogging resin film by being laminated on at least one main surface of the polyethylene film-like substrate 2 as described above. The anti-fogging coating agent is adjusted as follows, for example.

That is, the anti-fogging coating agent is composed of IPA and water.
IPA: water = 1: 9 to 9: 1
0.1 wt% to 10 wt% of the above-described polyolefin compound (a binder resin comprising a polyolefin emulsion), and 0.1 wt% to 30 wt% in a solvent of 40 wt% to 60 wt% mixed in a ratio of % Of the inorganic colloid particles described above and 0.1 to 15% by weight of the thermoplastic resin described above are mixed. A polyolefin emulsion may be mixed as the polyolefin compound. If it does in this way, the particle dispersibility in an anti-fogging coating agent will be stabilized easily, and handling will be easy. Further, since the polyolefin compound, the inorganic colloid particles, and the thermoplastic resin are substantially the same as the above-described configuration, detailed description of the configuration is omitted.

(Other)
In order to improve the adhesion of the base material 2 to the anti-fogging layer 3, an amide group, an amino group, a hydroxyl group, a vinyl acetate group reacting with the carboxylic acid group contained in the polyolefin compound of the anti-fogging layer 3 on the base material 2. A compound containing at least two of any of the above may be added. In this way, when the antifogging coating agent applied to one main surface of the substrate 2 is dried by heating to form the antifogging layer 3, the amide group, amino group, hydroxyl group or vinyl acetate group described above is formed. Can be made to react with the carboxylic acid group contained in the polyolefin compound of the antifogging layer 3 to improve the adhesion of the base material 2 to the antifogging layer 3.

The compound containing an amide group may be, for example, homopolymerization as shown in the following general formula (18) or may be as shown in the following general formula (19) (for example, polyacrylamide, ethylene-acrylamide copolymer) Coalescing). Further, it may be a copolymer with acrylic acid, allylamine, diallylamine, polyester or the like. Specifically, polyamide polyester copolymer TXM-80, TAPEH151, TAPE2371P-11A (manufactured by T & K TOKA Co., Ltd.), N-vinyl. Examples thereof include sodium acetamide acrylate copolymer GE167-000 (manufactured by Showa Denko KK).

As the compound containing an amino group, for example, a diamine as represented by the following general formula (20) may be used, or a compound represented by the following general formula (21) (for example, ethylenediamine, polyallylamine). Specifically, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, hexamethylenediamine, ethylaminoethylamine, N′N-di-tert-butylethylenediamine, 2,2′-diamino Diethylamine, diethylenetriamine, N, N′-dimethyl-1,3-propanediamine, 3,3′-diaminodipropylamine N, N′-bis (3-aminopropyl) ethylenediamine, 6,6′-iminodihexylamine, N, N′-bis (2-aminoethyl) -1,3-propanediamine, L-arginine, polyethyleneimine (manufactured by Junsei Chemical Co., Ltd.), aminoethylated acrylic polymer NK-200PM (manufactured by Nippon Shokubai Co., Ltd.), Allylamine polymers PAA-01, PAA-03, allylamine dimethyl ali Amine polymer PAA-1112, diallylamine polymer PAS-21, allylamine maleic acid copolymer PAA-1151, partially uread polyallylamine PAA-N5000, PAA-N5050CL (manufactured by Knitbo Medical Co., Ltd.), polyamide polyester copolymer TAPE617C (T & K Co., Ltd., manufactured by TOKA) can be mentioned.

Examples of the compound containing a hydroxyl group are those represented by the following general formula (22) and those represented by the following general formula (23) (for example, ethylene glycol and polyvinyl alcohol). Specifically, ethylene glycol, propylene glycol, polyethylene glycol, glycerin, polyethylene oxide copolymer Alcox L-11, E160, ethylene oxide / propylene oxide copolymer EP101ON, Alcox EP10, having a sugar structure ( Guar gum: Grinstead Guar 175 (Sanki Co., Ltd.), Cellulose compound: Serogen 3H (Daiichi Kogyo Seiyaku Co., Ltd.), Polyhydroxy polyolefin oligomer Polytail H (Mitsubishi Chemical Co., Ltd.), Polyvinyl alcohol Poval LM-25 (stock) Kuraray Co., Ltd.), Gohsenol KP-08R, Gohsenx Z-100 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), polyamide polyester copolymer TAPE617 (manufactured by T & K TOKA Corporation) And the like.

As the compound containing a vinyl acetate group, for example, a compound represented by the following general formula (24) may be used (for example, ethylene vinyl acetate copolymer).

As described above, in this embodiment, the antifogging layer 3 is laminated on at least one main surface of the polyethylene film-like substrate 2, but the hydrophobic polyolefin compound containing a carboxylic acid group is used as the antifogging layer 3. Therefore, the adhesion between the antifogging layer 3 and the film-like substrate 2 can be improved. Further, since hydrophilic inorganic colloidal particles are contained in the antifogging layer 3, the antifogging property can be expressed by imparting hydrophilicity to the antifogging layer 3.

Further, the antifogging layer 3 contains an amphiphilic thermoplastic resin containing a hydrophobic group having affinity for the polyolefin compound and a hydrophilic group having affinity for the inorganic colloidal particles. Therefore, by interposing the thermoplastic resin, the adhesion between the film-like substrate 2 and the polyolefin compound having high adhesion and the hydrophilic inorganic colloid particles can be improved. Further, since the thermoplastic resin contains a hydrophilic group, it can contribute to the improvement of the hydrophilicity of the antifogging layer 3.

In addition, since the thermoplastic resin that improves the adhesion between the polyolefin compound and the inorganic colloidal particles does not dissolve in a solvent composed only of water, there is no possibility that the thermoplastic resin dissolves in water droplets that wet the antifogging layer 3 surface. . Therefore, the hydrophilic inorganic colloid particles dispersed in the antifogging layer 3 can be prevented from flowing out from the surface of the film-like base material 2 by water droplets that wet the surface of the antifogging layer 3. The water resistance of the anti-fogging layer 3 having the properties can be increased, and the durability of the anti-fogging layer 3 can be improved.

In addition, as described above, by forming the antifogging layer 3 using the antifogging coating agent for the polyethylene film-like substrate 2, hydrophilicity is imparted to the surface of the film-like substrate 2, and the droplets are dropped. An effect can be obtained. Therefore, for example, by applying the above-described antifogging coating agent to the inside of an agricultural house or forming an agricultural house using the antifogging resin film 1 so that the antifogging layer 3 is on the inside, the house It is possible to prevent water droplets adhering to the inner surface from dropping on the crop. Further, when the antifogging layer 3 is formed on the outside of the house, the dirt flows down together with the water droplets that wet the film-like substrate 2, so that the antifogging resin film having an antifouling effect and excellent in durability is provided. 1 can be obtained.

In the above-described embodiment, the binder resin is composed of a hydrophobic polyolefin compound (polyolefin emulsion) containing a carboxylic acid group, but the type of the binder resin is not limited to the polyolefin compound. That is, any resin can be used as long as it has an affinity for the thermoplastic resin for improving the adhesion between the binder resin and the inorganic colloidal particles and has an adhesion to the polyethylene film-like substrate. The binder resin may be constituted, and the binder resin may be constituted by a resin such as a polyester resin, a urethane resin, an acrylic resin, or an epoxy resin.

Specifically, for example, when the binder resin is composed of a urethane resin, a polycarbonate anionic urethane emulsion, an ester anionic urethane emulsion, a polyether anionic urethane emulsion, etc. The binder resin may be constituted by In particular, from the viewpoint of adhesion to a polyolefin-based substrate film and water resistance of the anti-fogging coating film, the binder resin is preferably composed of a urethane-based resin mainly composed of an anionic urethane compound containing a silanol group. Moreover, you may comprise binder resin combining these 1 type, or 2 or more types of resin. In this case, a water-soluble vinyl acetal copolymer may be used as the thermoplastic resin. At this time, the antifogging coating agent may be constituted using the above-mentioned mixed solution of water and alcohol as a solvent, and since the alcohol is added to the antifogging coating agent, the coating property can be improved.

For example, when the binder resin is composed of an acrylic resin, the binder resin may be composed of an acrylic polymer containing at least one of acidic groups such as carboxylic acid groups, esters thereof, and hydroxyl groups in the structure. In particular, from the viewpoint of adhesion to the base film and water resistance of the antifogging coating film, the binder resin is preferably composed of a hydrophobic acrylic emulsion such as an acidic group-containing vinyl ester polymer. In this case, a water-soluble vinyl acetal copolymer or the like may be used as the thermoplastic resin. What is necessary is just to comprise an anti-fogging coating agent by using the above-mentioned mixed solution of water and alcohol as a solvent, and since alcohol is added to the anti-fogging coating agent, the coatability can be improved.

Specific examples and comparative examples will be described with reference to FIGS. 2 to 4 are diagrams showing examples of the antifogging coating agent of the present invention. In addition, this invention is not limited to the Example mentioned later.

Examples 1 to 6 of the anti-fogging coating agent will be described with reference to FIG.

(Examples 1 to 6)
a) Binder resin Examples 1 to 4: Arrow base SB1200 (polyolefin emulsion (polyolefin compound): manufactured by Unitika Ltd.): mass in 100 parts by mass of anti-fogging coating agent is 0.3% by weight
Example 5: Polymeron 351T (polyolefin emulsion (polyolefin compound): Arakawa Chemical Industries): 0.3% by weight in 100 parts by weight of anti-fogging coating agent
Example 6: Takelac W-5030 (urethane emulsion (urethane compound): Mitsui Chemicals, Inc.): 0.5% by weight in 100 parts by weight of anti-fogging coating agent
b) Inorganic colloidal particles (alumina, colloidal silica)
Examples 1, 2, 4, 5: Snowtech YL (Colloidal silica: manufactured by Nissan Chemical Industries, Ltd.): 1.0% by weight in 100 parts by weight of anti-fogging coating agent
Example 3: Alumina sol 200 (alumina: manufactured by Nissan Chemical Industries, Ltd.): The mass in 100 parts by weight of the antifogging coating agent is 1.0% by weight.
Example 6: Snow Tech YL (Colloidal Silica: manufactured by Nissan Chemical Industries, Ltd.): The mass in 100 parts by weight of the antifogging coating agent is 0.6% by weight
c) Amphiphilic thermoplastic resin-Example 1: TAPE617 (polyamide polyester copolymer: manufactured by T & K TOKA Corporation): 0.4% by mass in 100 parts by mass of the antifogging coating agent
Example 2: Gohsenx LL-940 (polyvinyl alcohol: manufactured by Nippon Synthetic Chemical Industry Co., Ltd.): 0.4% by mass in 100 parts by mass of the antifogging coating agent
Examples 3 to 6: ESREC KX-5 (vinyl acetal copolymer: manufactured by Sekisui Chemical Co., Ltd.): 0.3% by weight in 100 parts by weight of the antifogging coating agent
d) Solvent ion-exchanged water: isopropyl alcohol (IPA) = 6: 4 solvent: mass in 100 parts by mass of anti-fogging coating agent is 98% by weight
Examples 1 to 6 of the anti-fogging coating agent were prepared by dispersing or dissolving each material in a solvent at the above-described ratio.

(Comparative Examples 1 to 4)
Comparative Examples 1 to 4 of the anti-fogging coating agent were prepared by mixing each material in the solvent in the ratio shown in FIG. In Comparative Example 4, as a comparison target of the amphiphilic thermoplastic resin, Pitzcol K-30 (polyvinylpyrrolidone resin: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), which is a water-soluble resin, was added to 100 mass of the antifogging coating agent. It mixes so that the mass in a part may be 0.4 weight%.

(Evaluation methods)
The obtained anti-fogging coating agent was applied to a polyolefin film subjected to corona discharge treatment so that the WET film thickness was 10 μm, and dried at about 90 ° C. for about 2 minutes to form an anti-fogging resin film. And about the obtained anti-fogging resin film, tests, such as wettability, adhesiveness, durability, and liquid stability, were done.
(1) Antifogging Whether or not a film of water is formed on the surface of the film after flowing water for 30 seconds while flowing the flowing water on the antifogging layer surface of the antifogging resin film formed by applying the antifogging coating agent. The presence or absence of a hydrophilic effect was determined.
A: A water film is formed on the entire film, and the film thickness is remarkably thick. O: A water film is formed on the entire film. Δ: A water film is not formed on the edge of the film, and the central part. Water film is formed on X: Almost no water film is formed

(2) Water resistance Further, flowing water was kept flowing over the antifogging layer surface of the antifogging resin film for 5 minutes, and the presence or absence of the hydrophilic effect was determined by whether or not a water film was formed on the film surface after flowing water.
A: A water film is formed on the entire film, and the film thickness is remarkably thick. O: A water film is formed on the entire film. Δ: A water film is not formed on the edge of the film, and the central part. Water film is formed on X: Almost no water film is formed

(3) Adhesion A cellophane tape is applied to the surface of the anti-fogging layer, and the cellophane tape is peeled off. Then, running water is allowed to flow on the peeled surface for 30 seconds, and whether or not a water film is formed on the film surface after running water. The presence or absence of was determined.
A: A water film is formed on the entire film, and the film thickness is remarkably thick. O: A water film is formed on the entire film. Δ: A water film is not formed on the edge of the film, and the central part. A film of water is formed on the surface. ×: A film of water is hardly formed. (4) Liquid stability Judgment was made based on the presence or absence of precipitation one week after the preparation.

(Evaluation)
As shown in FIG. 2, compared with Comparative Examples 1 to 4, Examples 1 to 5 have excellent antifogging properties, adhesion properties, and water resistance antistatic properties, respectively.

Referring to FIG. 3, Examples 7 to 9 of the antifogging coating agent will be described.

(Examples 7 to 9)
a) Binder resin Examples 7 to 9: VE1217 (polyolefin emulsion (polyolefin compound): manufactured by Seiko PMC Co., Ltd.): 0.3 wt% in 100 parts by mass of the antifogging coating agent
b) Inorganic colloidal particles (colloidal silica)
Examples 7 to 9: Snow Tech YL (Colloidal Silica: manufactured by Nissan Chemical Industries, Ltd.): The mass in an antifogging coating agent 100 parts by weight is 1.0% by weight.
c) Amphiphilic thermoplastic resin Examples 7 to 9: Eslek KX-5 (vinyl acetal copolymer: manufactured by Sekisui Chemical Co., Ltd.): The mass in 100 parts by mass of the antifogging coating agent is 0.3. weight%
d) Solvent Ion-exchanged water: Isopropyl alcohol (IPA) = 6: 4 Solvent: The mass in 100 parts by mass of the antifogging coating agent is 98.4% by weight.
Each material was dispersed or dissolved in the solvent at the above-mentioned ratios to prepare Examples 7 to 9 of the anti-fogging coating agent.

(Comparative Example 5)
Comparative Example 5 is an anti-fogging coating agent having the same structure as in Examples 7 to 9. In Examples 7 to 9, various additives shown in FIG.

(Evaluation methods)
For each of Examples 7 to 9, a polyolefin film in which an additive was mixed as follows was prepared.
Example 7: TAPE-617C (amide group: manufactured by T & K TOKA Co., Ltd.): mass in 100% by mass of film is 5.0% by weight
Example 8: Polytail H (hydroxyl group: manufactured by Mitsubishi Chemical Corporation): mass in 100% by mass of film is 5.0% by weight
Example 9: NUC-3224 (vinyl acetate group: manufactured by Nihon Unicar Co., Ltd.): mass in 100% by mass of film is 5.0% by weight

Subsequently, each of the polyolefin films prepared for each of Examples 7 to 9 was subjected to corona discharge treatment, and the obtained antifogging coating agent was applied to the polyolefin film subjected to corona discharge treatment so that the WET film thickness was 10 μm. The antifogging resin film was formed by applying and drying at about 90 ° C. for about 2 minutes. And about the obtained anti-fogging resin film, tests, such as wettability, adhesiveness, durability, and liquid stability, were done.

(Evaluation)
As shown in FIG. 3, compared with Comparative Example 5, Examples 7 to 9 each have improved adhesion.

Examples 10 to 13 of the antifogging coating agent will be described with reference to FIG.

(Examples 10 to 13)
a) Binder resin Examples 10 to 13: VE1217 (polyolefin emulsion (polyolefin compound): manufactured by Seiko PMC Co., Ltd.): 0.3% by weight in 100 parts by weight of the antifogging coating agent
b) Inorganic colloidal particles (colloidal silica)
Examples 10 to 13: Snowtech YL (Colloidal silica: manufactured by Nissan Chemical Industries, Ltd.): 1.0% by weight in 100 parts by weight of antifogging coating agent
c) Amphiphilic thermoplastic resin Examples 10 to 13: Eslek KX-5 (vinyl acetal copolymer: manufactured by Sekisui Chemical Co., Ltd.): The mass in 100 parts by mass of the antifogging coating agent is 0.3. weight%
d) Additives Example 10: TAPE-617C (amide group: manufactured by T & K TOKA Co., Ltd.): 0.1% by weight in 100 parts by weight of anti-fogging coating agent
Example 11: Ethylenediamine (amino group: manufactured by Kishida Chemical Co., Ltd.): The mass in 100 parts by mass of the antifogging coating agent is 0.001% by weight.
Example 12: Alcox EP1010N (hydroxyl group: manufactured by Nasei Chemical Industry Co., Ltd.): the mass in 100 parts by mass of the antifogging coating agent is 0.1% by weight
Example 13: Sumikaflex S-755 (vinyl acetate group: manufactured by Sumitomo Chemtex Co., Ltd.): The mass in 100 parts by mass of the antifogging coating agent is 0.1% by weight.
f) Solvent Ion-exchanged water: Isopropyl alcohol (IPA) = 6: 4 Solvent: The mass in 100 parts by mass of the anti-fogging coating agent is 98.4% by weight.
Each of the materials was dispersed or dissolved in the solvent at the above-mentioned ratio to prepare Examples 10 to 13 of the anti-fogging coating agent.

(Comparative Example 6)
Comparative Example 6 is an anti-fogging coating agent in which the various additives of Examples 10 to 13 are not added, and the configuration excluding the additives is adjusted in the same manner as in Examples 10 to 13.

(Evaluation methods)
A polyolefin film in which Admer AT1000 (polyolefin compound containing a carboxylic acid group: manufactured by Mitsui Chemicals, Inc.) was added so that the mass at 100% by mass of the film was 5.0% by weight was prepared.

Subsequently, each polyolefin film to which the additive was added was subjected to corona discharge treatment, and the obtained antifogging coating agent was applied to the polyolefin film subjected to corona discharge treatment so that the WET film thickness was 10 μm, and about An antifogging resin film was formed by drying at 90 ° C. for about 2 minutes. And about the obtained anti-fogging resin film, tests, such as wettability, adhesiveness, durability, and liquid stability, were done.

(Evaluation)
As shown in FIG. 4, compared to Comparative Example 6, Examples 10 to 13 each have improved adhesion. In Examples 11 and 12, antifogging properties are improved.

In addition, this invention is not limited to each above-mentioned embodiment, Unless it deviates from the meaning, it is possible to perform a various change other than above-mentioned, for example, the film-form base material 2 The anti-fogging layer 3 may be formed on both surfaces.

Further, in order to improve the adhesion between the inorganic colloid particles and the polyolefin compound, in addition to the above-described thermoplastic resin, other cross-linking agents, silane coupling agents, and the like are further added to the substrate 2 and the antifogging layer 3 (antifogging coating agent). ) May be contained. Moreover, at least a part of the carboxylic acid groups contained in the polyolefin compound contained in the antifogging coating agent may be contained in the polyolefin compound in a salt state. Moreover, when the antifogging coating agent is applied to a film-like substrate to form an antifogging layer, some carboxylic acid groups may remain in the salt state in the antifogging layer.

Further, the mixing ratio of alcohol such as IPA and water constituting the solvent of the anti-fogging coating agent is not limited to the above-described example, and depends on the type of the amphiphilic thermoplastic resin of the present invention. As long as the thermoplastic resin can be dissolved in the solvent, the alcohol and water should be appropriately mixed at a mixing ratio of alcohol: water = 1: 9 to 9: 1. Thus, by mixing alcohol in a solvent, the anti-fogging coating agent of this invention in which the amphiphilic thermoplastic resin was melt | dissolved can be comprised. Moreover, the applicability | paintability of an anti-fogging coating agent can be improved with alcohol.

Moreover, in the antifogging layer and the antifogging coating agent in the present invention, in addition to those described above, a surfactant, a crosslinking agent, an antifoaming agent, if necessary, as long as the purpose of the present invention is not impaired. Various additives such as a lubricant, a film-forming aid, a thickener, a pigment, a pigment dispersant, and an antistatic agent can be contained. Furthermore, in order to improve the weather resistance of the coating film, an ultraviolet absorber or a binderd amine type light stabilizer may be mixed.

The present invention can be widely applied to an antifogging resin film having an antifogging layer laminated on at least one main surface of a polyethylene film-like substrate and an antifogging coating agent.

1 Antifogging resin film 2 Base material 3 Antifogging layer

Claims

A polyethylene film-like substrate;
An antifogging layer laminated on at least one main surface of the base material,
The anti-fogging layer is
An amphiphilic thermoplastic resin that does not dissolve in a solvent consisting only of water;
Hydrophilic inorganic colloid particles having affinity for the thermoplastic resin;
An antifogging resin film comprising: a binder resin having affinity for the thermoplastic resin and having adhesion to the substrate.
The anti-fogging resin film according to claim 1, wherein the binder resin is a hydrophobic polyolefin emulsion containing a carboxylic acid group.
The polyolefin emulsion is a copolymer containing at least one of ethylene and propylene and at least one of a structure represented by the general formula (1) and a carboxyl group, and represented by the general formula (1). The antifogging resin film according to claim 2, wherein the structure and / or carboxyl group is contained in an amount of 0.1 to 15% by weight.
General formula (1):
The anti-fogging resin film according to claim 3, wherein the copolymer further contains a vinyl acetate group.
The antifogging resin film according to any one of claims 2 to 4, wherein the inorganic colloidal particles include at least one of silica, alumina, and a layered clay compound, and have a particle size of 3 nm to 200 nm.
The thermoplastic resin is alcohol and water,
Alcohol: water = 1: 9-9: 1
The antifogging resin film according to claim 2, wherein the antifogging resin film is dissolved in a solvent mixed at a ratio of
The antifogging resin film according to any one of claims 2 to 6, wherein the thermoplastic resin contains at least one of hydroxyl group, ethylene oxide, propylene oxide, ester bond, and urethane bond.
The thermoplastic resin includes a) polyvinyl alcohol having a saponification degree of 20% to 51%, b) 45 mol% to 85 mol% of hydrophilic monomer units, an average polymerization degree of 1500 to 3500, and an acetalization degree of 4 mol. The antifogging resin film according to any one of claims 2 to 7, which is at least one of water-soluble vinyl acetal copolymers in an amount of from 20 to 20 mol%.
A compound containing at least two of any one of an amide group, an amino group, a hydroxyl group, and a vinyl acetate group that reacts with the carboxylic acid group contained in the polyolefin-based emulsion is added to the base material. The antifogging resin film according to any one of claims 2 to 8.
A polyolefin emulsion containing a carboxylic acid group is added to the base material, and the antifogging layer contains a carboxylic acid group contained in the polyolefin emulsion contained in the antifogging layer and a polyolefin emulsion contained in the base material. 9. A compound containing at least two of any one of an amide group, an amino group, a hydroxyl group and a vinyl acetate group, which reacts with a carboxylic acid group, is added. Anti-fogging resin film.
In the antifogging coating agent that forms an antifogging layer of an antifogging resin film by being laminated on a polyethylene film-like substrate,
In a solvent in which alcohol and water are mixed,
An amphiphilic thermoplastic resin that does not dissolve in a solvent consisting only of water;
Hydrophilic inorganic colloid particles having affinity for the thermoplastic resin;
An anti-fogging coating agent comprising: a binder resin having affinity for the thermoplastic resin and having adhesion to the substrate.
The binder resin comprising 0.1% to 10% by weight of a hydrophobic polyolefin emulsion containing carboxylic acid groups;
0.1% to 30% by weight of the hydrophilic inorganic colloid particles,
0.1 wt% to 10 wt% of the amphiphilic thermoplastic resin,
12. The anti-fogging coat according to claim 11, wherein the alcohol and water contain 40 wt% to 60 wt% of the solvent mixed in a ratio of alcohol: water = 1: 9 to 9: 1. Agent.
The anti-fogging coating agent according to claim 12, wherein the thermoplastic resin contains at least one of hydroxyl group, ethylene oxide, propylene oxide, ester bond, and urethane bond.
The thermoplastic resin includes a) a polyvinyl alcohol having a saponification degree of 20 to 51%, b) 45 to 85 mol% of hydrophilic monomer units, an average polymerization degree of 1500 to 3500, and an acetalization degree of 4 mol% to The anti-fogging coating agent according to claim 12 or 13, which is at least one of 20 mol% of a water-soluble vinyl acetal copolymer.