JPH11240112A - Anti-fogging laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anti-fogging laminate capable of developing excellent anti-fogging properties (moist heat keeping-resistant antifogging properties) in a use environment over a long period of time even after kept under a high temp. and high humidity environment over a long time. SOLUTION: An anti-fogging laminate has a layer (A-layer) comprising a resin and inorg. compd. fine particles and a layer (B-layer) based on inorg. compd. fine particles at least the single surface of a base material and the outermost layer at least on the single surface of the base material is the A-layer. The A-layer is a layer formed by drying a dispersion of a hydrophilic resin and inorg. compd. fine particles and the B-layer may be a layer formed by drying a dispersion of inorg. compd. fine particles. The inorg. compd. fine particles contained in the A-layer and/or the B-layer are metal oxide fine particles and/or metal hydroxide fine particles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anti-fogging laminate for use in greenhouse horticulture or a light-transmitting plate.

[0002]

2. Description of the Related Art Conventionally, agricultural films and sheets used for, for example, agricultural houses, tunnels, curtains, and the like are used in an outdoor environment. Therefore, when the surface temperature of the film falls below the dew point of water vapor. There is a problem that dew condensation occurs, the surface becomes cloudy, the transmittance of sunlight decreases, and the growth of the crop is delayed, and water droplets attached to the crop fall on the crop to cause a disease. For this reason, various antifogging laminates having an antifogging layer provided on various substrates have been proposed. Among them, for the purpose of improving the durability of the anti-fogging effect, for example, JP-A-51-
6193, 51-81877, 53-39347, 57
-11974, 59-15473, 60-9668
2, 62-27146, 62-283135, 63-1
32989, 63-150369 and the like propose that an antifogging film containing fine particles of an inorganic compound be provided on the outermost surface thereof by coating or the like.

It has also been proposed to further laminate a layer made of a hydrophilic resin on the anti-fogging coating for the purpose of preventing the coating from being damaged or preventing the anti-fogging property from deteriorating at high temperatures. ing.

[0004] However, even in the above-mentioned method, when stored in a high-temperature and high-humidity environment for a long time, the anti-fogging property may be deteriorated.

[0005]

According to the present invention, excellent anti-fogging properties (anti-fogging properties after storage under moist heat) are exhibited over a long period of time even after being stored in a high-temperature and high-humidity environment for a long time. The present invention provides an antifogging laminate that can be used.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is, the present invention has a layer (A layer) composed of a resin and inorganic compound fine particles and a layer (B layer) mainly composed of inorganic compound fine particles on at least one side of the substrate, and the outermost layer on the surface side is It is intended to provide an antifogging laminate characterized by being an A layer.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
In the present invention, the layer A is a layer composed of a resin and inorganic compound fine particles, and the layer B is a layer mainly composed of inorganic compound fine particles. Here, the inorganic compound fine particles have a particle diameter of 5 μm.
m or less, and a particulate inorganic compound that can be colloidally dispersed in a dispersion medium as described below is preferable. Such inorganic compound fine particles and colloidal inorganic compound fine particle dispersion are described, for example, in Gypsum & Lime (No. 211, P46 (198
It can be produced by the method described in 7)).

The inorganic compound fine particles include metal fine particles, oxide fine particles, hydroxide fine particles, carbonate fine particles,
Sulfate fine particles. As metal fine particles,
Fine particles of gold, palladium, platinum, silver, sulfur and the like are exemplified, oxide fine particles, hydroxide fine particles, carbonate fine particles,
As the sulfate fine particles, silicon, aluminum,
Zinc, magnesium, calcium, barium, titanium,
Examples include oxide fine particles, hydroxide fine particles, carbonate fine particles, sulfate fine particles, and clay minerals of metals such as zirconium, manganese, iron, cerium, nickel, and tin.

Of these oxide fine particles, hydroxide fine particles, carbonate fine particles, and sulfate fine particles, oxide fine particles or hydroxide fine particles are preferable, and particularly, aluminum, silicon, or titanium oxide fine particles or hydroxide fine particles. Is more preferred. Two or more of these inorganic compound fine particles may be used in combination.

As the inorganic compound fine particles in the layer A, titanium oxide fine particles are preferable, and anatase type titanium oxide fine particles are particularly preferable. The average particle diameter of the titanium oxide fine particles is usually 200 nm or less, preferably 100 nm or less. In particular, from the viewpoint of the transparency of the antifogging laminate, 10
Fine particles having a particle size of not more than nm are more preferred.

The average particle size is 50 to 5000 n.
m, more preferably 80 to 300 nm, because the adhesion between the anti-fogging laminate and the galvanized iron plate can be significantly reduced and improved in some cases.

In the present invention, the adhesion index E refers to the peel strength after water is adhered to the anti-fog surface of the anti-fog laminate, adhered to a galvanized iron plate and dried. Yes, a specimen with a width of 20 mm was moved at a speed of 5 in the 180 ° direction.
0 mm / min. The tensile load at the time of peeling is measured with an autograph. The tin (plate) is a thin steel plate subjected to galvanization, and examples thereof include those specified in JIS H8641. In addition, baking painting is JIS
As described in K5980, this is a method of applying a synthetic resin paint such as a urethane-based resin and then heating it at a high temperature to cure the coating, and is often used indoors and outdoors for parts requiring durability. If the adhesion index E is too large, the substrate may be broken by the force at the time of peeling, so that the adhesion index E is preferably 500 g / 20 mm or less, and 200 g / 20 m or less.
m or less is more preferable.

The inorganic compound fine particles of the layer A at this time are
Is that the value of L defined by the following equation is greater than 1.
preferable. In particular, from the viewpoint of the stability of the effect, L is 1.
It is preferably at least 5, more preferably at least 2.
preferable. Further, from the viewpoint of the transparency of the antifogging laminate, L
Is preferably 4 or less. L = (N × R) / S where R is the average of the inorganic compound fine particles contained in the A layer.
S is the surface of layer A of the antifogging laminate.
Product (m^Two), And N is the amount of N contained in the layer A having the surface area.
The number of organic compound fine particles, which is defined by the following formula. N = V / {(4/3) × π × (R / 2)^Three} Here, V is an inorganic compound contained in the layer A having a unit surface area.
Fine particle volume (cc / m ^Two). The average particle size R is
For example, electron microscope, dynamic light scattering particle size distribution analyzer, laser
It can be measured using a diffraction scattering particle size distribution analyzer.
You. N is a fine particle of the inorganic compound contained in the layer A having a unit surface area.
Particle weight (g / m^Two) Is determined by the density (g / c) of the fine particles.
c) Volume per unit surface area of layer A obtained by dividing by
(Cc / m^Two) Is assumed to be occupied by spheres of particle size R
Is calculated.

Further, as the inorganic compound fine particles of the layer B, silicon oxide fine particles or hydroxide fine particles and aluminum oxide fine particles or hydroxide fine particles are used together to form a coating, film strength and substrate adhesion. It is preferable from the viewpoint of antifogging property. In this combination of mixing, silicon oxide fine particles or hydroxide fine particles are basic colloids, whereas aluminum oxide fine particles or hydroxide fine particles are acidic colloids. It is particularly preferably used because it produces a bond. As the inorganic compound which exhibits basicity when dispersed in water, for example, various clay minerals described below are also preferably used.

For example, when silica fine particles and alumina fine particles are used, the mixing ratio is usually in the range of 90/10 to 10/90 by weight of alumina / silica, and more preferably 80/20 to 20/80. Especially 70/30 to 30/7
A range of 0 is preferred.

In the present invention, the thickness of the layer A is preferably 0.01 g / m ² or more, more preferably 0.02 g / m ² , in terms of weight thickness, from the viewpoint of the anti-fogging property and scratch resistance of the obtained anti-fogging laminate. The above is more preferable, and the amount is particularly preferably 0.05 g / m ² or more. Further, from the viewpoint of the blocking properties of the antifogging laminate,
10 g / m ² or less is preferable, 2 g / m ² or less is more preferable, and 0.5 g / m ² or less is particularly preferable.

In the present invention, the thickness of the B layer is determined by the
In terms of adhesion strength with other layers such as layers,
It is preferably at least 0.01 g / m2, more preferably at least 0.02 g / m2, particularly preferably at least 0.05 g / m2. 10 g / m 2 from the viewpoint of transparency or appearance.
Or less, more preferably 2 g / m 2 or less, and 0.1 g / m 2 or less.
Particularly preferred is 5 g / m 2 or less.

In the present invention, the thickness (d1) of the layer A and the thickness B
The ratio (d2 / d1) of the thickness (d2) of the layer is preferably from 0.01 to 10 from the viewpoint of appearance and sustainability of the effect. In particular, when it is desired to lower the adhesiveness between the coating film and the galvanized iron plate, 0.01 to 1 is preferable.

The layer A and / or the layer B may contain various surfactants, organic electrolytes, various binders, etc. for the purpose of strengthening the interaction between the inorganic compound fine particles. Various clay minerals and the like added for the purpose of imparting thixotropic properties to the dispersion of the compound fine particles may be contained.

As the surfactant, conventionally known various surfactants such as anionic, cationic, nonionic and amphoteric surfactants can be used. Examples of the anionic surfactant include sodium caprylate, Of carboxylic acids having an alkyl chain having 6 to 24 carbon atoms, such as potassium caprylate, sodium decanoate, sodium caproate, sodium myristate, potassium oleate, tetramethylammonium stearate, sodium stearate, and potassium behenate. Metal salts or ammonium salts, metal salts or ammonium salts of sulfonic acids having an alkyl chain having 6 to 24 carbon atoms, such as sodium octyl sulfonate, sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate and ammonium dodecyl benzene sulfonate. Hydrocarbon-based anions such as potassium salts, metal salts or ammonium salts of phosphate esters having an alkyl chain having 6 to 24 carbon atoms, and metal salts or ammonium salts of borate esters having an alkyl chain having 6 to 24 carbon atoms. Surfactants, fluorinated anionic surfactants such as sodium perfluorodecanoate and sodium perfluorooctylsulfonate, condensates of polydimethylsiloxane groups and alkylene oxide adducts, polydimethylsiloxane groups and metal salts of carboxylic acids, etc. Examples include a silicon-based anionic surfactant having an anionic group, and an alkali metal salt of a carboxylic acid having an alkyl chain having 6 to 10 carbon atoms is particularly preferable.

Examples of the cationic surfactant include:
Cetyltrimethylammonium chloride, dioctadecyldimethylammonium chloride, -N-octadecylpyridinium bromide, cetyltriethylphosphonium bromide and the like can be mentioned.

Examples of the nonionic surfactant include, for example,
Sorbitan monostearate, sorbitan monopalmitate, sorbitan fatty acid ester surfactants such as sorbitan monobehenate, glycerin monolaurate,
Glycerin fatty acid ester surfactants such as glycerin monopalmitate, glycerin monostearate, diglycerin distearate, and triglycerin monostearate; polyethylene glycol surfactants such as polyethylene glycol monopalmitate and polyethylene glycol monostearate And fluorinated nonionic surfactants such as alkylene oxide adducts of alkylphenols, esters of sorbitan / glycerin condensates with organic acids, and diglycerin esters of perfluorodecanoic acid.

In addition, amphoteric surfactants can be used. When a surfactant is used, the amount used is 0.5 part by weight or less, preferably 0.1 part by weight or less, based on 100 parts by weight of the inorganic compound fine particles. Also, if the amount used is too small, the desired effect may be too small,
Usually, it is 0.001 part by weight or more, and preferably 0.01 part by weight or more.

Examples of the organic electrolyte include sodium p-toluenesulfonate, sodium benzenesulfonate, potassium butylsulfonate, sodium phenylphosphinate and sodium diethylphosphate. Particularly, a benzenesulfonic acid derivative is preferable. . When an organic electrolyte is used, the amount of use is usually 0.1 part by weight or less, preferably 0.05 part by weight or less, based on 100 parts by weight of the inorganic compound fine particles. Also, if the amount is too small, the desired effect may be too small,
Usually, it is 0.0001 parts by weight or more, preferably 0.001 parts by weight or more.

Examples of the binder include a thermoplastic resin. As such a thermoplastic resin,
Acrylic resin, ethylene-vinyl acetate resin, polyethylene resin, vinyl chloride resin, vinylidene chloride resin, polyurethane resin, polycarbonate resin, styrene resin, vinyl acetate resin, unsaturated polyester resin, etc. And an acrylic resin is particularly preferable. These resins may be crosslinked, and may contain additives as described below.

In these thermoplastic resins, a binder which forms an emulsion dispersed in a medium such as water or the like or which dissolves in the medium easily interacts with the fine particles of the inorganic compound. it can. Preferred examples of the binder emulsion include an aqueous emulsion of an acrylic resin and an aqueous emulsion of a polyurethane resin. Preferred examples of the binder solution include an aqueous solution of poly-2-hydroxyethyl methacrylate.

Various clay minerals added for the purpose of imparting thixotropic properties to the dispersion of inorganic compound fine particles include:
On top of a tetrahedral layer of silica, a two-layer structure having an octahedral layer made of aluminum or magnesium as a central metal, and a three-layer structure sandwiching an octahedral layer made of aluminum or magnesium as a central metal from both sides It is classified into types consisting of structures.

Examples of the former include kaolinites and antigolites, and examples of the latter include smectites, vermiculites and micas depending on the number of interlayer cations. Among such clay minerals, an inorganic layered compound that swells in a layered manner in a dispersion medium and exhibits thixotropy, as described later, is preferred, and particularly, an aqueous dispersion is preferably a smectite group and a vermiculite group showing thixotropy. .

From the viewpoint of long-lasting antifogging performance, the amount of the above-mentioned organic compounds such as various surfactants, organic electrolytes, and binders is preferably 75% by weight or less in the A layer and / or B layer, and 50% by weight. % Or less, more preferably 10% by weight or less, and most preferably 1% by weight or less.

In the present invention, examples of the resin used for the layer A include acrylic resin, ethylene-vinyl acetate resin, polyethylene resin, vinyl chloride resin, vinylidene chloride resin, polyurethane resin, polycarbonate resin, Examples thereof include a styrene-based resin, a vinyl acetate-based resin, and an unsaturated polyester-based resin. Among them, the following hydrophilic resins are preferable.

The hydrophilic resin has a highly hydrophilic polar group in the molecule, and the polar group is a hydrogen bonding group and / or an ionic group. The proportion of polar groups is
The weight percentage of the hydrogen bonding group and / or the ionic group (in the case of having two or more of these groups, the total thereof) per unit weight of the resin is usually about 25 to 70%,
Preferably, it is about 30 to 50%.

The term "hydrogen-bonding group" means a group having at least one hydrogen directly bonded to an atom other than carbon (hetero atom). As the hydrogen bonding group, for example, a hydroxyl group,
Amino group, thiol group, carboxyl group, sulfone group,
And a phosphate group.

On the other hand, the ionic group refers to a group having at least one of positive and negative charges localized to such an extent that water molecules can be hydrated in water. Examples of such an ionic group include a carboxylate group, a sulfonate ion group, a phosphate ion group, an ammonium group, and a phosphonium group.

Among the hydrogen bonding groups or ionic groups, a hydroxyl group, an amino group, a carboxyl group, a sulfonic acid group, a carboxylate group, a sulfonic acid ion group, an ammonium group and the like are more preferable. The content of these hydrogen bonding groups or ionic groups can be determined, for example, by nuclear magnetic resonance (NM).
R) (1H-NMR, 13C-NMR, etc.) can be suitably measured.

Examples of the hydrophilic resin include vinyl resins, acrylic resins, polyester resins, epoxy resins, urethane resins, melamine resins, phenol resins, polysaccharides and modified polysaccharides. The following are particularly preferred.

For example, polyvinyl alcohol or an ethylene-vinyl alcohol copolymer having a vinyl alcohol fraction of at least 41 mol%, hydroxymethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, amylose, amylopectin, pullulan, curdlan, xanthan, chitin, chitosan, Examples thereof include polysaccharides such as cellulose, polyacrylic acid, sodium polyacrylate, polybenzenesulfonic acid, sodium polybenzenesulfonate, polyethyleneimine, polyallylamine, ammonium salts thereof, polyvinyl thiol, and polyglycerin.

Among the above-mentioned hydrophilic resins, polyvinyl alcohol and / or polysaccharide (or a derivative thereof)
It is more preferred to use In the case of ideal polyvinyl alcohol [-(CH2 CHOH) n-],
The weight percentage of the OH group as the hydrogen bonding group is (1
7/44) × 100 = about 39%.

The polyvinyl alcohol is a polymer having a monomer unit of vinyl alcohol as a main component. For example, a polymer obtained by hydrolyzing or transesterifying (saponifying) an acetic ester portion of a vinyl acetate polymer (exactly). Is a copolymer of vinyl alcohol and vinyl acetate), vinyl trifluoroacetate polymer, vinyl formate polymer, vinyl pivalate polymer, t
Polymers obtained by saponifying -butyl vinyl ether polymer, trimethylsilyl vinyl ether polymer and the like (for details of "polyvinyl alcohol", see, for example, Povarkai, "PVA World", 199
2 years, Polymer Publishing Association; Nagano et al., "Poval", 1
981 (Polymer Publishing Association) can be referred to).

The degree of saponification is preferably 50% or more, more preferably 70% or more in terms of mole percentage from the viewpoint of the initial antifogging property of the obtained laminate. Also,
From the viewpoint of moisture storage resistance and antifogging property, the content is preferably 85% or less.

The average degree of polymerization of polyvinyl alcohol is preferably 100 or more from the viewpoint of the initial antifogging property. Further, from the viewpoint of the anti-fogging property during storage under moist heat and the viscosity of the coating liquid when the layer A is formed by coating, 10
000 or less is preferable, 3000 or less is more preferable,
Particularly preferred is 500 or less.

The above polyvinyl alcohols may be used alone or in combination of two or more. Further, a polyvinyl alcohol derivative can also be used, and as a functional group other than a hydroxyl group, for example, an amino group, a thiol group, a carboxyl group, a sulfone group, a phosphate group, a carboxylate group, a sulfonate ion group, a phosphate ion group, an ammonium group, a phosphonium group , A silyl group, a siloxane group, an alkyl group,
It may have partly an allyl group, a fluoroalkyl group, an alkoxy group, a carbonyl group, a halogen group, and the like.

The polysaccharide may have some or all of its hydroxyl groups replaced by other substituents. Other substituents include an alkoxy group, a cyano group, an amino group, a thiol group, a carboxyl group, a sulfonic acid group, a phosphate group,
Examples thereof include an ammonium group and a phosphonium group. The alkoxy group may further have a substituent such as a hydroxyl group, an amino group, a thiol group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an ammonium group, a phosphonium group, and the like. The group, ammonium group, phosphonium group may be in the form of its ester or salt. The rate at which the hydroxyl group of the polysaccharide is replaced by these other substituents can be suitably measured, for example, by a nuclear magnetic resonance (NMR) technique (such as 1 H-NMR and 13 C-NMR).

For example, cellulose, amylopectin, pullulan, curdlan, xanthan, chitin, chitosan, cellulose ethers, cellulose esters and the like can be exemplified. Further, as cellulose ethers, methyl cellulose, ethyl cellulose, cyanoethyl cellulose,
Hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxyethylethylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, carboxymethylcellulose salts and the like, as cellulose esters, cellulose nitrate, cellulose sulfate, cellulose acetate, cellulose acetate saponified, amylose and the like Can be illustrated. Further, polysaccharides described in "Development of Functional Cellulose (CMC Co., Ltd., 1985)" and the like can also be exemplified. Among these polysaccharides, water-soluble or water-dispersible ones are preferred. When some or all of the hydroxyl groups of these polysaccharides are substituted with other substituents, the substitution ratio, for example, the degree of methoxy group substitution is determined by DS (DS: hydroxyl group in glucose unit of cellulose is methoxy group). When the hydroxyalkoxyl group substitution degree is MS (MS: average value of the number of hydroxyl groups substituted by hydroxyalkoxyl groups in the glucose ring unit of cellulose), the DS is 1.2 to 2.0. 0.1 for 2 or MS
~ 2.5 is preferred. In the case of a polysaccharide having both a methoxy group and a hydroxyalkoxyl group, a DS of 1.2 to
2, MS of 0.1 to 0.4 is preferable.

Specific examples of such polysaccharides in which some or all of the hydroxyl groups are substituted with other substituents include, for example, water-soluble cellulose ethers, such as methylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose, and hydroxypropyl. Methyl cellulose is mentioned. The viscosity of the polysaccharide is usually 2 to 100,000 cPs as a value of a 2% aqueous solution at 20 ° C. There is a regular correlation between the viscosity of the polysaccharide and the molecular weight of the polysaccharide,
The higher the viscosity, the higher the molecular weight. When the layer A is formed by coating, a low-viscosity (low molecular weight) polysaccharide is preferred from the viewpoint of obtaining a uniform coating solution, and from the viewpoint of the durability of the obtained layer A for scratch resistance and anti-fogging effect. And high viscosity (high molecular weight) polysaccharides are preferred.
From the viewpoint of the moisture / heat storage / fogging resistance described below, DS is 1.6.
Cellulose ethers of from 2.0 to 2.0, particularly methylcellulose, are preferred, and 20 cPs or less, particularly 5 cPs or less in a 2% aqueous solution at 20 ° C. are preferably used.

In the present invention, the layer A is a layer composed of a resin and fine particles of an inorganic compound, and the weight fraction of the fine particles of the inorganic compound in the layer A is determined from the viewpoint of preventing whitening of the surface or scratch resistance.
The content of the inorganic compound fine particles is preferably 1% by weight or more, and from the viewpoint of resistance to moist heat storage and fogging, 99% by weight or less, more preferably 20 to 80% by weight, and particularly preferably 40 to 60% by weight.

On the other hand, from the viewpoint of preventing the aforementioned antifogging laminate from adhering to, for example, a urethane-based baking-coated galvanized iron plate, the content of the inorganic compound fine particles is preferably 20% by weight or more, and 99% by weight or less. Preferably, more preferably 40% by weight
More preferably, it is at least 60% by weight.

In this case, from the viewpoint of the effect of preventing the resulting anti-fogging laminate from adhering to the metal plate, the thickness of the layer A is two or more in the thickness direction of the inorganic compound fine particles in the layer A. preferably it has taken the overlapped structure, 0.05 g / m ² or more preferably in a weight thickness, 0.10 g / m ² or more preferably, 0.25 g / m ² or more is particularly preferable. From the viewpoint of transparency, preferably 10 g / m ² or less, more preferably 5 g / m ² or less, 1 g / m ² or less is particularly preferred.

The substrate used in the present invention is not particularly limited, and a wide range of materials such as resin, paper, cloth, wood, metal and ceramics may be used. From the viewpoint of moldability, a resin such as a thermosetting resin or a thermoplastic resin is preferably used. These may be used in combination.

Examples of the thermoplastic resin include polyolefin resins, polyvinyl chloride, vinyl chloride-methyl methacrylate copolymer, and chlorine resins such as polyvinylidene chloride.
Examples include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acrylic resins such as polymethyl methacrylate, fluorine resins, and polycarbonate resins.

As the polyolefin resin, α-
An olefin homo- or copolymer, a copolymer of an α-olefin having α-olefin as a main component and a different monomer, for example, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene-1 Copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-hexene-1 copolymer, ethylene-octene-
Ethylene / α-olefin copolymer such as 1 copolymer,
Further, the different monomer is a polar vinyl monomer, such as ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-vinyl acetate-methyl methacrylate copolymer, and ionomer resin. Can be given. These thermoplastic resins may be used alone or as a blend of several resins.

The antifogging laminate of the present invention is applied to an agricultural film
When used for a sheet, a thermoplastic resin is preferable as the resin of the base material. When used for agricultural hard films and sheets used in houses, etc., acrylic resins such as polymethyl methacrylate, polycarbonate,
Polyester resin such as polyethylene terephthalate,
A resin excellent in transparency, such as a fluororesin, is preferable. When strength, rigidity and the like are required, a biaxially stretched film or sheet is preferable as the substrate.

When used for soft agricultural films used for houses, curtains, tunnels, etc., soft vinyl chloride, fluorine resins and polyolefin resins are preferred, and polyolefin resins are particularly preferably used as the base material.

In particular, a polyolefin resin used as a base material for an agricultural soft film has a density of 0.935 g.
/ Cm ³ or less, low density polyethylene or ethylene / α-
Olefin copolymers and ethylene-vinyl acetate copolymers having a vinyl acetate content of 30% by weight or less are preferred in that they are excellent in transparency and flexibility and can be obtained at low cost.

The ethylene / α-olefin copolymer α-olefin
Examples of the olefin include those having 3 to 18 carbon atoms, preferably those having 4 to 12 carbon atoms. Specific examples include propylene, 1-butene, 1-pentene,
Examples thereof include 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-cyclohexene and cyclohexylethylene. The ethylene / α-olefin copolymer may be a copolymer of ethylene and one type of α-olefin, or a copolymer of ethylene and two or more types of α-olefin. The content of α-olefin is usually 2 to 25% by weight,
Preferably it is 4 to 18% by weight.

The ethylene / α-olefin copolymer preferably has a composition distribution variation coefficient Cx defined by the following general formula of about 0.5 or less from the viewpoint of antifogging property retention. Particularly, from the viewpoint of anti-blocking property and dustproof property, Cx
It is preferred to use an ethylene / α-olefin copolymer having from about 0.1 to about 0.4 as the outside of the substrate. Cx = σ / SCBave. (1) In the formula, σ represents the composition distribution of the ethylene / α-olefin copolymer obtained from the elution amount of the eluting component at each temperature and the degree of branching at each temperature by the temperature rising column fractionation method. Represents the standard deviation. SCBave. Represents the average value of the number of short-chain branches per 1000 carbon atoms in the ethylene / α-olefin copolymer. σ and SCBave. are respectively obtained as follows. SCBave., As is commonly performed in the measurement of short-chain branching of polyethylene, etc.,
It can be determined from the FT-IR spectrum of the α-olefin copolymer. Here, the short-chain branch is generally a branch having about 1 to 4 carbon atoms (typically, a branch having 1 to 4 carbon atoms).
~ 4 branches). Further, σ is obtained by a standard method of the temperature rise column fractionation method. That is, the ethylene / α-olefin copolymer is dissolved in a solvent heated to a predetermined temperature, put into a column in a column oven, and
The temperature of the oven is lowered, then raised to a predetermined temperature, and the relative concentration and branching degree of the components eluted at that temperature are measured by FT-IR connected to the column. Subsequently, the temperature is increased stepwise to the final temperature (the temperature at which all the copolymers subjected to the test elute). Statistical processing is performed on the obtained relative concentration and branching degree of each eluted component, and the standard deviation σ of the composition distribution is obtained.

The ethylene / α-olefin copolymer can be obtained, for example, by converting ethylene and an α-olefin having 3 to 18 carbon atoms into a so-called single catalyst such as a complex catalyst of a transition metal such as palladium or nickel or a metallocene catalyst. Using a site catalyst, in the presence or absence of a solvent,
It can be produced by a method of polymerizing in a gas phase / solid phase, liquid phase / solid phase or homogeneous liquid phase. The polymerization temperature is usually about 30 ° C. to about 300 ° C., the polymerization pressure is usually at or near atmospheric to about 3000 kg / cm ^2. For example, JP-A-6-9724, JP-A-6-136195,
JP-A-6-136196, JP-A-6-20705
No. 7 and the like, by copolymerizing ethylene with an α-olefin having 3 to 18 carbon atoms in the presence of a so-called metallocene-based olefin polymerization catalyst containing a metallocene catalyst component. A copolymer can be produced. Further, Japanese Unexamined Patent Application Publication No.
According to the method described in No. 76542, the ethylene / α-olefin copolymer is such that the average value of the number of branches on the high molecular weight side is equal to or more than the average value of the number of branches on the low molecular weight side based on the peak position of the GPC elution curve. Coalescence can be produced and can be suitably used in the present invention.
When such a copolymer is used, a multilayer film having particularly excellent antiblocking properties and dustproof properties can be obtained.

The melt flow rate (MFR) of the polyolefin resin is preferably from about 0.1 to about 50 g / 10 minutes, more preferably from about 0.3 to about 20 g / 10 minutes. The M
FR conforms to ASTM D 1238-65T and is 1
It is a value measured under the conditions of 90 ° C. and a load of 2.16 kg. If the MFR is too low, the processability during the production of the multilayer film may be poor. If the MFR is too high, the strength of the obtained multilayer film may be poor. Also, JIS
The density measured by the method of K7112 is 0.91 to 0.9.
4 g / cm ³ is preferable, and 0.92 to 0.94 g / cm ³
Is more preferably 0.925 to 0.94 g / cm ³ . Gel PermeationChrom
molecular weight distribution (M) determined by atomography (GPC)
w / Mn) is from about 1.5 to about 4 from the viewpoint of processability and strength.
Is preferred, and about 2 to about 3.5 is more preferred.

When the antifogging laminate of the present invention is used as an agricultural film, the substrate is preferably made of a thermoplastic resin composition comprising a thermoplastic resin and a radiation blocking agent. Here, the radiation is radiated from the ground or the like in a facility such as a house warmed mainly by the visible light of the sun or the like in the daytime as infrared light in the wavelength range of 2 to 25 μm at night. The line blocking agent has a property of absorbing or reflecting this radiation.

Examples of the radiation blocking agent include an infrared absorbing agent and an infrared reflecting agent. The infrared reflector is not particularly limited as long as it reflects at least one of the wavelengths in the above wavelength range, and examples thereof include inorganic infrared reflectors such as zinc oxide.

Examples of the inorganic infrared absorber include lithium aluminum composite hydroxide, composite hydroxides such as hydrotalcite compounds, and oxides of metals such as magnesium oxide, calcium oxide, aluminum oxide, silicon oxide, and titanium oxide. Hydroxides such as lithium hydroxide, magnesium hydroxide, calcium hydroxide, and aluminum hydroxide;
Carbonates such as magnesium carbonate, calcium carbonate, basic aluminum carbonate (for example, a basic aluminum carbonate double salt described in JP-A-9-279131), potassium sulfate, magnesium sulfate, calcium sulfate, zinc sulfate, and aluminum sulfate; Sulfates, lithium phosphate,
Phosphates such as sodium phosphate, potassium phosphate, calcium phosphate, zirconium phosphate (for example, H-type zirconium phosphate described in JP-A-8-67774), silicates such as magnesium silicate, calcium silicate, aluminum silicate, titanium silicate, and aluminate Sodium, potassium aluminate, aluminates such as calcium aluminate, sodium aluminosilicate, potassium aluminosilicate,
Aluminosilicates such as calcium aluminosilicate; clay minerals such as kaolin, clay and talc; and composite oxides. Examples of the organic infrared absorber include polyacetal, polyvinyl alcohol and derivatives thereof, and ethylene / vinyl alcohol copolymer. Among these infrared absorbers, those having a density of about 3 g / cm ³ or less, particularly about 2.4 g / cm ³ or less are preferable from the viewpoint of the recycling efficiency of the multilayer film. Absorbers are more preferred. When the infrared absorbent is an inorganic infrared absorbent, its refractive index is closer to the refractive index of the resin material used from the viewpoint of light transmittance, and from the viewpoint of heat retention, it can be applied to a wide wavelength range. It is preferable to have absorption performance. From these viewpoints, hydrotalcite compounds, lithium aluminum composite hydroxides, aluminosilicates, basic aluminum carbonate double salts, and the like are preferable.

The hydrotalcite compound is represented by the following formula (I): M 2 ⁺ _{1 -x} Al ³⁺ _x (OH ⁻ ) ₂ (A ₁ ^{n −} ) _{x / n} · mH ₂ O (I) In the ^formula , M ²⁺ is a divalent metal ion, A ₁ ⁿ⁻ is an n-valent anion, and x and m are 0 <x <0.5, 0 ≦
The condition of m ≦ 2 is satisfied. ). Examples of M ²⁺ include Mg ²⁺ , Ca ²⁺ , Zn ^{2+ and the} like. The n-valent anion is not particularly limited.
^{l -, Br -, I -} , NO 3 -, ClO 4 -, SO 4 2-, CO 3 2-,
_{^{SiO 3 2-, HPO 4 3-,}} HBO 4 3-, PO 4 3-, Fe (C
^{_{N) 6 3-, Fe (CN}} ) 6 4-, CH 3 COO -, C 6 H 4 (O
H) Anions such as COO ⁻ , (COO) ₂ ²⁻ , terephthalate ion and naphthalene sulfonate ion;
And polyphosphoric acid ions and polyphosphate ions described in JP-A-217912, and n is preferably 1 ≦ n ≦ 3.
Specifically, for example, natural hydrotalcite or synthetic hydrotalcite such as Alkamizer DHT-4A (trade name, manufactured by Kyowa Chemical Industry Co., Ltd.) can be used.
Further, calcium hydroxide or a calcium-aluminum composite hydroxide (CaAl _x (OH) _{2 + 3x} ) may be used in combination with the hydrotalcite compound.

[0062] The lithium aluminum complex hydroxide, for example, the following formula disclosed in ^{JP-A-5-179052 (II): Li + (} Al 3+) 2 (OH -) 6 · (A 2 n- _{1 / n} · mH ₂ O (II) (wherein, A ₂ ⁿ⁻ is an n-valent anion, and m is 0 ≦ m ≦
3 is satisfied). Although the n-valent anion is not particularly limited, for example,
Examples include the same anions as A ₁ ^n- in the compound of the formula (I), and n is preferably 1 ≦ n ≦ 3.

Other than the above two types of composite hydroxides,
For example, alkaline earth metals, transition metals, Zn and Si
At least one element selected from the group consisting of
A composite hydroxide containing Li and Al and having a hydroxyl group is exemplified. Of the alkaline earth metals, magnesium and calcium are preferred. Further, among the transition metals, divalent or trivalent iron, cobalt, nickel, and manganese are preferable, and among them, iron is particularly preferable. The molar ratio of Al to Li (Al / Li) is usually 1.5 / 1 to 2.5 / 1.
And preferably from 1.8 / 1 to 2.5 / 1.

Further, alkaline earth metals, transition metals, Zn
The molar ratio (a) of an element selected from the group consisting of Si and Si is usually 0 <a <1.
5, preferably 0.1 ≦ a ≦ 1.4, more preferably 0.2 ≦ a ≦ 1.2. The anion portion other than the hydroxyl group of the composite hydroxide is, for example, pyrosilicate ion, cyclosilicate ion, isosilicate ion, phyllosilicate ion, polysilicate ion such as tectosilicate ion, carbonate ion, halide ion, sulfate ion, Inorganic acid ions such as sulfite ion, nitrate ion, nitrite ion, phosphate ion, phosphite ion, hypophosphite ion, polyphosphate ion, aluminate ion, silicate ion, perchlorate ion and borate ion , Fe (C
^{_{N) 6 3-, Fe (CN}} ) 6 4- , etc. anionic transition metal complexes of, acetate ion, benzoate ion, formate ion, terephthalate ion and organic acid ions such as an alkyl sulfonate ion. Among these, carbonate ions,
Preference is given to halide ions, sulfate ions, phosphate ions, polyphosphate ions, silicate ions, polysilicate ions and perchlorate ions, and particularly preferred are carbonate ions, polyphosphate ions, silicate ions and polysilicate ions.
Specific examples of such a composite hydroxide include Al, L
i, containing Mg, and Al / Li / Mg = about 2.3
/1/0.28 (molar ratio) complex hydroxide (trade name)
LMA, manufactured by Fuji Chemical Co., Ltd., or a composite hydroxide containing Al, Li, and Si and having Al / Li / Si = approximately 2/1 / 1.2 (molar ratio) (trade names: Fujirain LS, Fuji Chemical Industry).

The following formula (III) disclosed in WO 97/00828: [(Li ⁺ _(1-x) M ²⁺ _x ) (Al ³⁺ ) ₂ (OH ⁻ ) ₆ ] ₂ (Si _y O _{(2y + 1)} ^2- ) _{(1 + x)} · mH ₂ O (III) (wherein, M ²⁺ is a divalent metal ion, and m, x, and y are 0 ≦ m <5, 0 ≦ x < 1, 2 ≦ y ≦ 4) and JP-A-8-21
No. 7912, the following formula (IV): [(Li ⁺ _(1-x) M ²⁺ _x ) (Al ³⁺ ) ₂ (OH ⁻ ) ₆ ] ₂ (A ⁿ⁻ ) _{2 (1 + x ) / n} · mH ₂ O (IV) (where M ²⁺ is a divalent metal ion, A ⁿ⁻ is an n-valent anion, and m, x and n are 0 ≦ m <5) , 0.
A compound represented by the following formula (01 ≦ x <1, 1 ≦ n ≦ 3) is also a preferable example of the composite hydroxide. Examples of M ²⁺ in formulas (III) and (IV) include Mg ²⁺ , Ca ²⁺ , and Zn ²⁺ . Furthermore,
Formula (V): mAl ₂ O ₃ · (n / p) M _{2 / p} O · X · kH ₂ O (V) (where X is a carbonate group, and M is an alkali metal or an alkaline earth metal. , P is the valence of the metal M, and m, n and k are 0.3 ≦ m ≦ 1, 0.3 ≦ n ≦ 2, 0.5 ≦ k
(Satisfies the condition of ≦ 4) is also one of the preferred infrared absorbers. In the above formula (V), X represents sulfur oxyacid (sulfuric acid, sulfurous acid), nitrogen oxyacid (nitric acid, nitrous acid), hydrochloric acid,
Inorganic anions such as oxyacids of chlorine (eg, perchloric acid), oxyacids of phosphorus (phosphoric acid, phosphorous acid, metaphosphoric acid), acetic acid, propionic acid, adipic acid, benzoic acid, phthalic acid, terephthalic acid, A double salt containing an organic anion such as maleic acid, fumaric acid, succinic acid, p-oxybenzoic acid, salicylic acid, picric acid, and toluenesulfonic acid may be used in combination with the basic aluminum carbonate double salt. These double salts can be produced by the method disclosed in JP-A-9-279131.

When the above-mentioned composite hydroxide or basic aluminum carbonate double salt is used as an infrared absorbent, its average particle size is usually about 5 μm or less, preferably about 0.02 μm or less.
It is 5 to about 3 μm, more preferably about 0.1 to about 1 μm. The specific surface area measured by the BET method is 1 to 30.
m ² / g, preferably from about 2 to about 20 m ² / g. When the antifogging laminate of the present invention is used for applications requiring a high degree of transparency, the refractive index of the infrared absorber is preferably close to the refractive index of the resin material used, and JIS K00
The refractive index measured by the method described in 62 is 1.47 to 1.55.
Is preferable, 1.48 to 1.54 is more preferable, and 1.49 to 1.53 is particularly preferable. Note that these infrared absorbers may contain water of crystallization.

In order to improve the dispersibility of the infrared absorber in the base film / sheet, the infrared absorber may be subjected to a surface treatment with a higher fatty acid or an alkali metal salt of a higher fatty acid. The compounding amount of the infrared absorber is appropriately set in consideration of a desired radiation transmission index of the base film / sheet at 23 ° C., the type of the infrared absorber used, the layer structure of the base film / sheet, and the like. For example, when the above-mentioned composite hydroxide is used as an infrared absorbing agent, the compounding amount is usually 0.03 to 100 parts by weight of the base resin.
To 25 parts by weight, preferably 1 to 15 parts by weight.

The radiation transmission index at 23 ° C. of the anti-fogging laminate is a measure of the heat retention when the film / sheet is used as a covering material for a green house or the like, and has an influence on the growth of the crop. And is determined by a measurement method described later. The smaller the value, the better the heat retention of the film / sheet. In the present invention, the radiation transmission index at 23 ° C. of the film / sheet is preferably 25 or less. When the film / sheet has a radiation transmission index of 25 or less, the heat retention is equal to or better than that of the conventional polyvinyl chloride film, and when used in a heated house, the heating cost can be reduced and the cost can be reduced. Contributes to improved efficiency. The radiation transmission index is preferably as close to zero as possible, more preferably 20 or less, and even more preferably 15 or less.

The radiation transmission index at 23 ° C. is measured by the following method. Using an infrared spectrophotometer (Perkin Elmer 1640 type FT-IR), a wave number of 40
An infrared absorption spectrum (transmission method) of the multilayer film is measured at a temperature of 23 ° C. in the range of 00 to 400 cm ⁻¹ to obtain a value of transmittance T (ν)% at a wave number ν. On the other hand, according to the equation (2) obtained from Planck's law, the blackbody radiation spectrum intensity e (ν) at the wave number ν at 23 ° C. is calculated. Here, a value obtained by multiplying the blackbody radiation spectrum intensity e (ν) by the transmittance T (ν) becomes a radiation transmission intensity f (ν) (formula (3)). Radiation transmission intensity f (ν) integrated over a wave number range of 4000 to 400 cm ⁻¹ , radiation transmission energy F, black body radiation spectrum intensity e (ν) integrated over a wave number range of 4000 to 400 cm ^−1. Is defined as black body radiation energy E, and a radiation transmission index G = 100 × F / E is defined. In the actual integration, the interval is divided into intervals of 2 cm ^-1 at the wave number interval, and each interval is calculated and integrated by trapezoidal approximation. The smaller the radiation transmission index, the better the heat retention of the film. e (ν) = (A / λ ⁵ ) / {exp (B / (λ × T)) − 1} (2) A = 2πhC ² = 3.74 × 10 ⁻¹⁶ (W · m ² ) B = hC /K=0.01439 (mK) T (K) is an absolute temperature. λ (cm) is the wavelength. (The wave number ν is the reciprocal of the wavelength.) (H is Planck's constant, C is the speed of light, k is Boltzmann's constant.) F (ν) = e (ν) × T (ν) / 100 (3)

The density of the antifogging laminate is preferably less than 1.0 g / cm ³ at a temperature of 23 ° C. according to the method of JIS K7112-1980 from the viewpoint of recycling efficiency. Density is preferably 0.99 g / cm ³ or less, more preferably 0.98 g / cm ³ or less, 0.97
g / cm ³ or less is particularly preferred. What is recycling efficiency?
It means easy separation from vinyl chloride film widely used for agricultural applications.

The anti-fogging laminate of the present invention can contain at least one kind of light stabilizer. As the light stabilizer, a nickel complex light stabilizer can be used, but a hindered amine compound is preferable, and in particular, a molecular weight of about 1500
The above hindered amine compounds are preferred. Examples of the hindered amine compound include, for example, JP-A-8-7366.
No. 7 having the structural formula described in,
Specific examples include Tinuvin 622-LD, Chimasorb 944-LD, Tinuvin 123 (all manufactured by Ciba Specialty Chemicals), Hostabin N30, VP S
and PR-31 (from Clariant), Syasorb UV3526 (from Sytec) and the like. Examples of the hindered amine compound-containing stabilizer include compositions described in JP-A-63-286448 (trade names: Tinuvin 492, Tinuvin 49).
4, (Ciba Specialty Chemicals).

When a light stabilizer is used, its amount is determined from the viewpoint of the balance between the effect of improving weather resistance and the suppression of blooming.
Usually about 0.02 to about 5% by weight, preferably about 0.1 to about 2% by weight, more preferably about 0.5% by weight in the multilayer film.
To about 2% by weight. From the viewpoint of the weather resistance improving effect, the light stabilizer is more preferably used in combination with the following ultraviolet absorber.

The antifogging laminate of the present invention can contain at least one kind of ultraviolet absorber. The ultraviolet absorber may be an organic compound or an inorganic compound.
Examples of organic UV absorbers that can be used include benzophenone UV absorbers, benzotriazole UV absorbers,
Benzoate UV absorbers, cyanoacrylate UV absorbers, and the like. The inorganic ultraviolet absorber may contain a metal oxide such as cerium oxide or titanium oxide. For example, an ultraviolet absorber commercially available from Nippon Inorganic Chemical Industry Co., Ltd. under the trade name: Serigard can be used. . When an ultraviolet absorber is used, the amount thereof is usually about 0.01 to about 3% by weight, preferably about 0.05 to about 3% by weight in the whole multilayer film, from the viewpoint of the balance between the effect of improving weather resistance and suppressing blooming. It is in the range of about 1% by weight.

The substrate of the antifogging laminate of the present invention may contain an antifogging agent for the purpose of achieving excellent initial antifogging properties. When the substrate contains an antifogging agent, the amount is usually about 0.1 to about 4% by weight, preferably about 0.5 to about 3% by weight of the whole substrate.
%, More preferably from about 1.5 to about 3% by weight, particularly preferably from about 2.2 to about 2.8% by weight.

The antifogging agent may be solid or liquid at normal temperature (23 ° C.). As a solid anti-fog agent,
Nonionic surfactants (for example, sorbitan monostearate, sorbitan monopalmitate, sorbitan monobehenate, sorbitan fatty acid ester-based surfactants such as sorbitan monomontanate; glycerin monolaurate, glycerin monopalmitate, glycerin monoester) Glycerin fatty acid ester surfactants such as stearate, diglycerin distearate, triglycerin monostearate, and triglycerin monomontanate; polyethylene glycol surfactants such as polyethylene glycol monopalmitate and polyethylene glycol monostearate; Alkylene oxide adduct of alkylphenol; ester of sorbitan / glycerin condensate with organic acid; polyoxyethylene (2 mol) stearylamine, polio Polyoxyethylene alkylamine compounds such as polyethylene (2 mol) laurylamine and polyoxyethylene (4 mol) stearylamine, polyoxyethylene (2 mol) stearylamine monostearate, polyoxyethylene (2 mol) stearylamine distear , Polyoxyethylene (4 mol) stearylamine monostearate, polyoxyethylene (4 mol) stearylamine distearate, polyoxyethylene (8 mol) stearylamine monostearate, polyoxyethylene (2 mol) stearylamine Fatty acid esters of polyoxyethylene alkylamine compounds such as monobehenate, polyoxyethylene (2 mol) laurylamine stearate, polyoxyethylene (2 mol)
Amine-based surfactants such as fatty acid amides of polyoxyethylene alkylamine compounds such as stearic acid amide; Examples of the liquid antifogging agent include glycerin fatty acid esters (for example, glycerin monooleate, diglycerin monooleate, diglycerin sesquioleate, tetraglycerin monooleate,
Hexaglycerin monooleate, tetraglycerin trioleate, hexaglycerin pentaoleate, tetraglycerin monolaurate, hexaglycerin monolaurate, etc., and sorbitan fatty acid esters (for example, sorbitan monooleate, sorbitan dioleate, sorbitan monolau) Rates, etc.).

When a liquid antifogging agent is incorporated, its amount is usually about 0.2 to about 3% by weight in the base material, preferably about 0.2 to about 3% by weight.
It ranges from 5 to about 2% by weight. An antifogging laminate containing a liquid antifogging agent in a substrate at room temperature can suppress loss of light transmittance during storage and expansion.

The antifogging laminate of the present invention can contain an antifog in the substrate. Antifog agents that can be used include:
Examples include a fluorine compound having a perfluoroalkyl group or an ω-hydrofluoroalkyl group (particularly, a fluorine-based surfactant), and a silicon-based compound having an alkylsiloxane group (particularly, a silicon-based surfactant). When containing an antifog, the amount is usually about 0.01 to
It is in the range of about 3% by weight, preferably about 0.02 to about 1% by weight.

The anti-fogging laminate of the present invention can contain a near-infrared ray blocking agent. When using an antifogging laminate containing a near-infrared blocking agent as a coating material for a green house,
It is possible to suppress a decrease in the temperature inside the house during a hot day. As a near-infrared ray blocking agent, for example,
Organic compounds disclosed in JP-A-193522 (for example, nitroso compounds and metal complex salts thereof, cyanine compounds, squarrium compounds, thiol nickel complex salt compounds, phthalocyanine compounds, triallylmethane compounds, immonium (Imonium)
-Based compounds, diimonium (Diimonium) -based compounds, naphthoquinone-based compounds, anthraquinone-based compounds, amino compounds, aminium (Aminium) salt-based compounds) and inorganic compounds (for example, carbon black, antimony oxide, indium oxide-doped tin oxide, 4A, 5 in the periodic table
Oxides or carbides of metals belonging to Group A or 6A,
Boron compound). A coating containing a near-infrared ray blocking agent may be formed on the outer surface of the antifogging laminate of the present invention. Examples of the method for forming the coating include a method in which a coating liquid containing a near-infrared ray blocking agent and a water-soluble resin binder is applied to the outer surface of the anti-fogging laminate and dried.

The base film may further contain, if necessary, various commonly used stabilizers other than those described above (eg, light stabilizers such as nickel compounds, antioxidants, etc.), antistatic agents, lubricants, pigments, and the like. And additives such as flame retardants (see “Separation and Analysis Techniques for Polymer Additives and Separate Volume” (Tanaka et al., Published by Nippon Scientific Information, 1987)
Year), "Practical Handbook of Additives for Plastics and Rubber"
(See Goto et al., Chemical Industry Publishing Co., 1970).
Further, each additive may be used alone, or two or more kinds may be used in combination.

The substrate may be a single layer or two or more layers. In the case of two or more layers, it is preferable that at least one layer is the above-mentioned resin substrate which is the polyolefin resin layer. When the resin substrate has a configuration of three or more layers, the total thickness of the layers constituting the outer surfaces of both sides of the substrate is usually 10 to 90% of the total thickness of the substrate, preferably 20 to 80%,
30-70% is more preferred. When a large amount of the above-mentioned radiation blocking agent is contained in the inner layer of the resin substrate, the content is preferably 10 to 40%, more preferably 15 to 30%. Note that the thicknesses of the layers constituting the outer sides may not be the same on both surfaces of the base material.

The resin substrate is preferably in the form of a film or a sheet.
An ordinary molding method such as a die molding method may be used. In order to obtain a multi-layer substrate, it can be used in various combinations according to the purpose. For example, in the case of using an inflation molding machine or a T-die having a multi-layered die configuration, different types of substrates can be obtained by extruding different resins from the respective die layers. Also, T
A multilayer substrate can also be obtained by laminating a film obtained by inflation molding to a sheet obtained by die molding with an adhesive or a molten resin.

The antifogging laminate of the present invention has a layer (layer A) comprising a resin and inorganic compound fine particles on at least one side of the substrate.
And a layer (B layer) containing inorganic compound fine particles as a main component, and the outermost layer on the surface side may be an A layer, and between the A layer and the B layer on the same side with respect to the substrate, Further, another layer such as an anchor coat layer or an adhesive layer may be provided between the layer B and the substrate. The outermost layers on both sides of the laminate are A
It may be a layer, but in this case, the layer B may be on both sides or one side of the substrate. Further, the compositions of the A layers in the outermost layers may be the same or different from each other. There may be one B layer or two or more B layers between the A layer and the substrate. When there are two or more B layers between the A layer and the base material, the compositions of the B layers may be the same or different from each other. From the viewpoint of the initial anti-fogging effect and the durability of the anti-fogging effect, it is preferable that the outermost layer A is directly laminated on the layer B, and the layer B is formed directly on the substrate (corona treatment, frame treatment, etc.). (May be treated).

The thickness of the anti-fogging laminate can be appropriately selected depending on the purpose, such as mechanical strength, transparency and flexibility. For example, when the laminate is used in an agricultural facility such as a house, it is usually 10 to 4 times.
It is 00 μm, preferably 30 to 300 μm.

Further, there is no particular limitation on the layer constitution, and for example, a layer constitution of three kinds, three layers, three kinds, five layers, four kinds, five layers, five kinds, five layers and the like can be exemplified. When the antifogging laminate of the present invention is used for horticulture and the like for agricultural use, usually, when the book is exhibited at an agricultural facility such as a house, the layer facing the outside of the facility is the outer layer, and the layer facing the inside of the house is facing the inside. A layer between the outer layer and the inner layer may be referred to as an inner layer, and a layer between the outer layer and the inner layer may be referred to as an intermediate layer (there may be two or more layers).

The substrate of the antifogging laminate of the present invention has transparency,
From the viewpoint of flexibility and economy, at least one layer has a density of 0.935 g / cm 3 or less as described above, a low-density polyethylene, an ethylene / α-olefin copolymer or a vinyl acetate content of 30% by weight or less. It is preferably a layer composed of an ethylene-vinyl acetate copolymer.

In this case, the thickness of the layer is preferably at least 5% of the total thickness of the substrate, more preferably at least 10%.

The resins and additives in the other resin layers may be different in composition, and may be subjected to dustproofing, antifogging, and fogproofing. In addition, from the viewpoint of the dust resistance and the strength against friction of a house band or the like, the average value of the above-mentioned melt flow rate, Cx or the number of branches on the high molecular weight side is not less than the average value of the number of branches on the low molecular weight side.
It is preferable to use at least one layer of the olefin copolymer, and it is more preferable to use the olefin copolymer on the side opposite to the layer A.

The method for producing the antifogging laminate of the present invention is not particularly limited as long as each layer can be laminated on a substrate, and examples thereof include conventionally used laminating methods and coating methods. (Reference: “Coating method”, written by Yuji Harasaki, 1979, published by Maki Shoten)

When a thermoplastic resin substrate is used as the substrate, the surface tension of the thermoplastic resin is generally low in many cases. For example, when the B layer is laminated on the substrate, the surface of the substrate is subjected to a surface treatment. Preferably, the surface tension is increased.
When the layer B is laminated by coating described below, the viewpoint that the wettability between the inorganic compound fine particle dispersion and the coating surface of the substrate is improved to eliminate defects due to repelling, and that the adhesive strength of each layer after drying is also increased. Therefore, it is preferable that the surface tension of the substrate on which the layer B is laminated is 36 dyne / cm or more. Although the upper limit of the surface tension is not particularly limited, it is usually about 60 dyne / cm, preferably 40 to 50 dy.
ne / cm.

As the surface treatment method, corona treatment, plasma treatment, flame plasma treatment, UV treatment,
Any method generally used, such as EB (electron beam irradiation) treatment, may be used, and the treatment may be performed under the condition that the surface tension after the treatment becomes a desired value. In general, the effect of the surface treatment decreases with time, so that it is desirable to laminate by coating or the like as soon as possible after the surface treatment. Therefore, it is preferable that the processing section and, for example, the coating section are continuous in-line.

In addition to the method of increasing the surface tension by performing a surface treatment, the surface of the base material is coated in advance with various anchor coating agents for the purpose of improving the wettability, and then the layer B is laminated by coating or the like. Is also good.

The above-mentioned coating means, for example, a dispersion in which fine particles of an inorganic compound are dispersed in a dispersion medium or a solution in which a hydrophilic resin is dissolved in a solvent is applied as a coating liquid and then dried to remove the dispersion medium or the solvent. And a method of forming a layer. The coating includes, for example, a coating method such as a gravure method, a dipping method, and a spray method. For example, when coating an inflation film, from the viewpoint of production efficiency, it is preferable to use a tubular film substrate and coat it, but various methods can be selected depending on the shape of the substrate.

The dispersion medium or solvent for preparing the dispersion or solution can be freely selected according to the inorganic compound fine particles and the resin. Examples of the dispersion medium used in the dispersion liquid of the inorganic compound fine particles include water, methyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, ethylene glycol, xylene, and the like, and a mixture thereof. A polar solvent is preferred, and water is particularly preferred in terms of environmental problems and equipment.

For example, as a solvent for dissolving polyvinyl alcohol, polysaccharide and derivatives thereof as a hydrophilic resin, for example, water, methyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol and the like and a mixture thereof are used. Water is particularly preferred from the viewpoints of environmental problems and facilities.

When the layer B is formed by coating, the weight and thickness after drying can be reduced by adjusting the concentration of the inorganic compound fine particles in the inorganic compound fine particle dispersion and the amount per unit area of the applied dispersion. , For example, 0.01
It can be made to have a desired thickness such as 10 g / m 2. The amount of the dispersion is appropriately set according to the area to be coated, but at least an amount capable of uniformly coating is required.

The above-mentioned various surfactants may be added to the inorganic compound fine particle dispersion for the purpose of improving coating properties and eliminating repellency and unevenness of the dispersion, and for imparting thixotropic properties to the dispersion. Organic electrolytes and various clay minerals can be added. When the clay mineral is added, the amount of the clay mineral is usually 0.005 to 3 parts by weight, preferably 0.01 to 0.5 part by weight, preferably 0.01 to 0.2 part by weight, per 100 parts by weight of the dispersion medium. Parts by weight are more preferred.

When the layer A is formed by coating, except that the dispersion contains a resin and fine particles of an inorganic compound,
This can be done in the same way as the coating of the layers. A method of directly coating the A layer on the B layer is also preferably used.

After coating, it is preferable to dry quickly to promote the formation of each layer. If the antifogging laminates produced by winding or the like are not sufficiently dried, the layer A or the layer B is undesirably peeled off when the antifogging laminate is used.

The antifogging laminate of the present invention is preferably in the form of a film or a sheet from the viewpoint of ease of use. Examples of the production method include the above-described coating method, a method for obtaining a usual laminated film or laminated sheet, or a combination thereof.

When the antifogging laminate of the present invention is used for agricultural purposes, it is preferably used in the form of a film or a sheet for facilities such as houses, curtains, tunnels and the like used for facility horticulture. From the viewpoint of efficiently taking in light into the facility, it is preferable that the film or the like has good transparency. As a measure of the transparency, generally, the total light transmittance and the haze value (diffuse light rate) of the film or sheet are used, and the higher the total light transmittance and the smaller the haze value, the better the transparency of the film.

When the antifogging laminate of the present invention is used as an agricultural film, the total light transmittance is 80% or more, preferably 85% or more, particularly 90% or more, and the haze value was 40% or less. It is preferable to use those having a content of 25% or less. In addition, from the viewpoint of heat retention at night, those having a radiation transmission index of 25% or less are preferable from the viewpoint of crop viability, more preferably 20% or less, and particularly preferably 15% or less.

The anti-fogging laminate of the present invention is preferably used as a light-transmitting plate used on roads for the purpose of preventing noise from automobiles, in addition to the agricultural use. When used for this purpose, an acrylic resin such as polymethyl methacrylate or a polycarbonate resin is preferably used as a substrate from the viewpoint of transparency and rigidity.

The anti-fogging laminate of the present invention can be used in various other applications, for example, covers for illuminations such as road signs and signboards, automobile films such as marking films and automobile lamp covers, houses and buildings. Used in outdoor, especially in high humidity environments, such as exterior wall coating films, window coating films, window sticking sheets, anti-fog wrapping films, anti-fog sheets for bathroom mirrors, goggles, underwater glasses, and dome-type stadium roofs It can be more preferably used for such applications.

[0104]

The anti-fogging laminate of the present invention has excellent anti-fogging properties (anti-fogging properties after storage under wet heat) for a long period of time even after being stored in a high-temperature and high-humidity environment for a long time. It can be expressed. In particular, when used as an agricultural covering material outdoors, it exhibits excellent anti-fog properties.
In addition, the anti-fogging laminate of the present invention is less likely to scratch the anti-fogging layer, is less likely to have poor appearance, and retains properties such as anti-fogging property for a long time, and is particularly effective for long-term use. is there. Further, the antifogging laminate of the present invention can be easily peeled off even when it is adhered to a galvanized sheet used for an agricultural house member, and does not damage the surface layer or the base material. Furthermore, a layer obtained by laminating a layer containing anatase-type titanium oxide fine particles on a thermoplastic resin base material containing a radiation-shielding agent shows particularly excellent anti-fog properties, such as when used for a house for facility horticulture, during the daytime. The amount of sunlight that is effective in photosynthesis can be improved, and radiation cooling from the ground can be suppressed at night, so that the effect of increasing crop viability can be obtained.

[0105]

The present invention will now be described by way of examples, which should not be construed as limiting the invention. In addition, the test method in an Example is as follows.

[Coating film adhesion test]: A cellophane tape was adhered to the coated surface of the substrate with a hand roller.
Autograph (Shimadzu AGS10)
The cellophane tape was peeled off from the substrate at a speed of 300 mm / min. At a speed of 300 mm / min. By using a load cell (5 kg) to determine the strength per 1 cm width at that time.

[Anti-fogging test]: A film was stuck on an acrylic frame measuring 34 cm in length and 5 cm in width by a double-sided tape, and the test surface was placed on a constant temperature water bath placed in a constant temperature environmental test chamber. It was installed at an angle of 15 degrees with respect to the horizontal plane. At this time, the temperature condition of the environmental test chamber / constant temperature water tank was 2
3 ° C / 40 ° C. Then, the state of water droplets on the film surface was observed up to two weeks later, and the evaluation was made according to the following criteria. However, the evaluations of △ and × include the case where the state was at least once during the observation period. ：: The film surface is almost uniformly wet. Δ: Water droplets are partially adhered. ×: Water droplets adhered to the entire surface and are cloudy white.

[Anti-fogging test]: The film was heated at 60 ° C. for 9 hours.
After aging for 10 days in a thermo-hygrostat at 0% RH, the state of water droplets on the film surface from one day to two weeks after was observed according to the method of the above-mentioned anti-fogging test, and evaluated according to the following criteria. ：: The film surface is almost uniformly wet. Δ: Water droplets are partially adhered. ×: Water droplets adhered to the entire surface and are cloudy white.

[Radiation Transmission Index] The radiation transmission index at 23 ° C. was calculated by the method described above.

[Adhesion test method of galvanized iron plate] A galvanized iron plate (product number: APC0.35, CGC)
CR, F-1041 Yane; made by Nippon Kokan), width 2
Water is attached to the A layer surface of the 0 mm film and adhered.
After drying in an oven at 0 ° C. for 3 hours, using an autograph (Shimadzu AGS100, load cell 5 kg), a speed of 50 mm / min. At 180 ° to measure the strength.

Examples of the composition of each layer of the antifogging film and examples of the production method are as follows.

[Layer A] Resin / inorganic compound fine particle dispersion (1) 96.7% by weight of a 1% by weight aqueous solution of polyvinyl alcohol (polymerization degree: 300, saponification degree: 80 mol%, manufactured by Kuraray)
Titanium oxide colloid aqueous dispersion (trade name: STS-01)
Titania sol (anatase type) titanium oxide content 30% by weight Particle size 7nm pH of the liquid = about 1.7 manufactured by Ishihara techno) is mixed to 3.3% by weight, and a resin / inorganic compound fine particle aqueous dispersion (1) I got

Resin / inorganic compound fine particle dispersion (2) polyvinyl alcohol (degree of polymerization: 300; degree of saponification:
97.5% by weight of a 1% aqueous solution of 80 mol%;
% By weight and an aqueous dispersion of titanium oxide colloid (trade name: ST
S-21 titania sol; anatase type; titanium oxide content: 40% by weight; particle diameter: 20 nm pH of liquid: about 8.
5; manufactured by Ishihara Techno Co., Ltd.) to obtain a resin / inorganic compound fine particle aqueous dispersion liquid (1).

Resin / inorganic compound fine particle dispersion (3) polyvinyl alcohol (degree of polymerization: 300; degree of saponification: 8)
94% by weight of a 1% by weight aqueous solution of 0 mol%;
And an aqueous dispersion of colloidal silica (density: 2.2 g / cc) (trade name: Snowtex ZL; solid content: 40% by weight; particle diameter: 100 nm; manufactured by Nissan Chemical Industries) to be mixed so as to be 6% by weight. Thus, a resin / inorganic compound fine particle aqueous dispersion (3) was obtained.

Resin / inorganic compound fine particle dispersion (4) polyvinyl alcohol (degree of polymerization: 300; degree of saponification: 8)
A 1% by weight aqueous solution (0 mol%; manufactured by Kuraray Co., Ltd.) was used as a resin / inorganic compound fine particle aqueous dispersion (4).

[Layer B] Inorganic Compound Fine Particle Dispersion (1) Aqueous aqueous colloidal alumina dispersion (trade name: alumina sol 520, solid content: 20% by weight, particle size: 20 nm)
9% by weight of Nissan Chemical Industries, Ltd., aqueous dispersion of colloidal silica (trade name: Snowtex 20, solid content: 20% by weight)
Particle size 20 nm 2.4% by weight (manufactured by Nissan Chemical Industry), clay mineral (trade name: Smecton SA, synthetic smectite manufactured by Kunimine Industries) 0.09% by weight, sodium caprylate 0.014% by weight as an anionic surfactant, paratoluene Add 0.002% by weight of sodium sulfonate and add 1
Inorganic compound fine particle dispersion (1% by weight)
And

Inorganic Compound Fine Particle Dispersion (2) Colloidal aqueous alumina dispersion (trade name: Aluminasol 520, solid content 20% by weight, particle size 20 nm, based on water)
9% by weight of Nissan Chemical Industries, Ltd., aqueous dispersion of colloidal silica (trade name: Snowtex 20, solid content: 20% by weight)
Particle size 20 nm 2.4% by weight (manufactured by Nissan Chemical Industry), clay mineral (trade name: Smecton SA, synthetic smectite manufactured by Kunimine Industries) 0.09% by weight, sodium caprylate 0.014% by weight as an anionic surfactant, paratoluene 0.002% by weight of sodium sulfonate,
Further, an aqueous dispersion of titanium oxide colloid (trade name: STS)
-01 titania sol; anatase type; titanium oxide content: 30% by weight; particle diameter: 7 nm;
7; manufactured by Ishihara Techno Co., Ltd. so as to be 3.3% by weight, and 100% by weight is defined as an inorganic compound fine particle dispersion liquid (2).

[Substrate] Substrate (1) Ethylene-vinyl acetate copolymer (trade name: Evatate)
H2031, vinyl acetate content 19% by weight, MFR 1.5
g / 10 min Sumitomo Chemical Co., Ltd.) and an inorganic compound (Mizukarak lithium aluminum composite hydroxide)
12% by weight of Mizusawa Chemical Industry, hindered amine compound A (trade name Tinuvin 622-LD) as a light stabilizer
0.6 parts by weight, manufactured by Ciba Specialty Chemicals)
Hindered amine compound B (trade name Chimasorb 94)
4-LD Ciba Specialty Chemicals) 0.2
Parts by weight, antioxidant C (trade name Irganox 101)
0.2% by weight) and kneaded at 130 ° C. for 5 minutes using a Banbury mixer, and then granulated by a granulator to obtain composition pellets. . This is referred to as a resin composition. Next, an ethylene-vinyl acetate copolymer (trade name: Evatate D2011, vinyl acetate content 5% by weight)
MFR 0.5 g / 10 min Sumitomo Chemical Co., Ltd.), hindered amine compound A 0.6% by weight, antioxidant C
0.06% by weight was added, and pellets were obtained in the same manner as in the resin composition. This is referred to as a resin composition. Further, 0.6% by weight of a hindered amine compound A, 0.06% by weight of antioxidant C, UV absorber D
(Product name Sumisorb 130 manufactured by Sumitomo Chemical Co., Ltd.)
28% by weight and 0.05% by weight of oleic acid amide as a lubricant were added to obtain pellets in the same manner as in the resin composition. This is referred to as a resin composition. Using a three-layer blown film molding machine, the resin composition is used as an intermediate layer, the resin composition is used as an outer layer of inflation, and the resin composition is used as an inner layer of inflation.
μm, about 17.5 μm of the inner and outer layers). This was cut to obtain a substrate (1).

[Method of Preparing Antifogging Laminate] Corona treatment method: The surface of each base material was corona treated with a corona treatment machine to have a surface tension of 45 dyne / cm or more. -Coating method: Microgravure method (microgravure roll diagonal line 1) using a test coater manufactured by Yasui Seiki
On a substrate after corona treatment using a 20 mesh), an inorganic compound fine particle dispersion is applied and dried to form a B layer. Further, a resin and an inorganic compound fine particle dispersion are applied and dried.
A layer was formed. The coating was performed on the outside (outer layer) of the blown film tube. Line speed is 5m
/ Min. And the temperature of the dryer was 80 ° C.

Example 1 A layer B was formed on the outer layer of the base material (1) from the inorganic compound fine particle dispersion liquid (1) according to the above-mentioned [Method for preparing an antifogging laminate]. Layer A was formed from the aqueous fine particle dispersion (1) to obtain an antifogging laminate. Table 1 shows the results of various tests. All were excellent.

Example 2 An antifogging laminate was obtained in the same manner as in Example 1 except that the layer A was formed from the aqueous resin / inorganic compound fine particle dispersion (2). Table 1 shows the results of various tests. All were excellent.

Example 3 The procedure of Example 1 was repeated, except that a layer B was formed from the inorganic compound fine particle dispersion (2) and a layer A was formed from the resin / inorganic compound fine particle aqueous dispersion (3). An antifogging laminate was obtained. Table 1 shows the results of various tests. All were excellent. Table 2 shows the results of the galvanized sheet adhesion test. The result was good peelability.

Example 4 An antifogging laminate was obtained in the same manner as in Example 3 except that the layer A was formed from the aqueous resin / inorganic compound fine particle dispersion (2). Table 1 shows the results of various tests. All were excellent.

Comparative Example 1 An antifogging laminate was obtained in the same manner as in Example 1 except that the layer A was formed from the aqueous resin / inorganic compound fine particle dispersion (4). Table 1 shows the results of various tests. The antifogging property after storage under moist heat was extremely poor.

Reference Example 1 Example 1 was repeated except that a commercially available polyolefin resin agricultural film “Clintate DX: manufactured by Sumika Plustech Co., Ltd., thickness 75 μm” was used as the base material.
In the same manner as described above, an antifogging laminate excellent in antifogging properties and suitable for agricultural covering materials can be obtained.

[Reference Example 2] A dust-proof and anti-fogging property was obtained in the same manner as in Example 1 except that a commercially available fluorine-based resin agricultural film “Efculin 15: manufactured by F-Clean System, thickness 100 μm” was used as a base material. An excellent antifogging laminate suitable for agricultural covering materials can be obtained.

Reference Example 3 The same procedure as in Example 1 was carried out except that a commercially available polyester resin agricultural film “Sixlight Clean: manufactured by Mitsubishi Chemical MKV, thickness 150 μm” was used as the base material, and was excellent in strength and antifogging property. An antifogging laminate suitable for agricultural covering materials can be obtained.

REFERENCE EXAMPLE 4 A commercially available ethylene / 1-hexene copolymer (trade name: Sumikacene E FV401, density: 0.902 g / cm ³ , melt index 4 g / 10 min), and the resin with the resin composition is commercially available ethylene /
1-hexene copolymer (trade name: Sumikacene E FV2
02, except that the density was 0.925 g / cm 3 and the melt index was 1.5 g / 10 min) to obtain the base material (2). Except for using the base material (2), an antifogging laminate excellent in strength and antifogging property suitable for agricultural coating materials can be obtained in the same manner as in Example 1.

[Reference Example 5] A commercially available extruded plate of polymethyl methacrylate resin (trade name: SUMIPEX E)
By spray-coating the same liquid as in Example 1 with a thickness of 10 mm (manufactured by Sumitomo Chemical Co., Ltd.), an antifogging laminate suitable for a light-transmitting plate can be obtained.

[0130]

[Table 1]

[0131]

[Table 2]

Claims (42)

[Claims] 1. A substrate comprising a layer (A layer) composed of resin and fine particles of an inorganic compound and a layer (B layer) mainly composed of fine particles of an inorganic compound on at least one side of a substrate, and the outermost layer on the side of the surface is An anti-fogging laminate comprising an A layer. 2. The antifogging laminate according to claim 1, wherein the resin contained in the layer A is a hydrophilic resin. 3. The antifogging laminate according to claim 2, wherein the layer A is a layer obtained by drying a dispersion of a hydrophilic resin and inorganic compound fine particles. 4. The antifogging laminate according to claim 1, wherein the layer B is a layer obtained by drying a dispersion of inorganic compound fine particles. 5. The inorganic compound fine particles contained in the layer A are oxide fine particles and / or hydroxide fine particles.
3. The antifogging laminate according to item 1. 6. An inorganic compound fine particle contained in the layer B is an oxide fine particle and / or a hydroxide fine particle.
3. The antifogging laminate according to item 1. 7. The antifogging laminate according to claim 1, wherein the inorganic compound fine particles contained in the layer A and / or the layer B are metal oxide fine particles and / or hydroxide fine particles. 8. The antifogging property according to claim 7, wherein the metal is at least one selected from silicon, aluminum, zinc, magnesium, calcium, barium, titanium, zirconium, manganese, iron, cerium, nickel and tin. Laminate. 9. The antifogging laminate according to claim 8, wherein the metal is at least one metal selected from the group consisting of silicon, aluminum and titanium. 10. The inorganic compound fine particles contained in the layer B are silicon oxide fine particles or hydroxide fine particles and aluminum oxide fine particles or hydroxide fine particles.
3. The antifogging laminate according to item 1. 11. The antifogging laminate according to claim 1, wherein the fine particles of the inorganic compound contained in the layer A and / or the layer B are fine particles of anatase type titanium oxide. 12. The antifogging laminate according to claim 11, wherein the anatase type titanium oxide fine particles have an average particle size of 10 nm or less. 13. The antifogging laminate according to claim 1, wherein the adhesiveness index E is 500 g / 20 mm or less. 14. The antifogging laminate according to claim 1, wherein the average particle diameter of the fine particles of the inorganic compound contained in the layer A is 50 nm to 5000 nm. 15. The antifogging laminate according to claim 13, wherein the value of L defined by the following formula is larger than 1. L = (N × R) / S (where R is the average particle diameter (m) of the fine particles of the inorganic compound contained in the A layer, and S is the surface area (m ² ) of the A layer of the antifogging laminate. ), And N is the number of inorganic compound fine particles contained in the layer A per surface area S, and is defined by the following formula: N = V / {(4/3) × π × (R / 2) ) ^3} where, V is a volume of the inorganic compound fine particles of the layer a per unit surface area (cc / m ^2).) 16. The antifogging property according to claim 11, wherein the inorganic compound fine particles contained in the layer B are fine particles of anatase-type titanium oxide, fine particles of hydroxide and / or fine particles of oxide other than fine particles of anatase-type titanium oxide. Laminate. 17. The inorganic compound fine particles contained in the layer B are silicon oxide fine particles, aluminum oxide fine particles, zinc oxide fine particles, cerium oxide fine particles, zirconium oxide fine particles, silicon hydroxide fine particles, aluminum hydroxide fine particles, zinc hydroxide fine particles, The antifogging laminate according to claim 1, which is at least one kind of fine particles selected from the group consisting of cerium hydroxide fine particles, zirconium hydroxide fine particles, and clay minerals, and anatase-type titanium oxide fine particles. 18. The inorganic compound fine particles contained in the layer B are aluminum oxide fine particles and / or aluminum hydroxide fine particles, silicon oxide fine particles and / or silicon hydroxide fine particles, and anatase type titanium oxide fine particles. 3. The antifogging laminate according to item 1. 19. The layer A has a weight thickness of 0.01 to 10 g /
^2. The antifogging laminate according to claim 1, wherein m2 is m2. 20. The layer B has a weight thickness of 0.01 to 10 g / m.
^2. The antifogging laminate according to claim 1, which is ² . 21. The hydrophilic resin is a polyvinyl alcohol,
The antifogging laminate according to claim 2, which is at least one selected from polysaccharides and derivatives thereof. 22. The thickness (d1) of the layer A and the thickness (d2) of the layer B
The antifogging laminate according to claim 1, wherein the ratio (d2 / d1) is from 0.01 to 10. 23. The thickness (d1) of the layer A and the thickness (d) of the layer B
The antifogging laminate according to claim 13, wherein the ratio (d2 / d1) of 2) is 0.01 to 1. 24. The antifogging laminate according to claim 1, wherein the substrate is made of a thermoplastic resin. 25. The antifogging laminate according to claim 24, wherein the thermoplastic resin is at least one selected from the group consisting of a polyolefin resin, an acrylic resin, a polycarbonate resin, a fluorine resin and a polyester resin. body. 26. The polyolefin resin according to claim 25, wherein the polyolefin resin is at least one of a low density polyethylene, an ethylene / α-olefin copolymer, and an ethylene / vinyl acetate copolymer having a vinyl acetate content of 30% by weight or less. Antifogging laminate. 27. The antifogging laminate according to claim 1, wherein the surface tension of the substrate is 36 dyne / cm or more. 28. The method according to claim 24, wherein the base material comprises a thermoplastic resin composition containing 100 parts by weight of a thermoplastic resin and 0.03 to 25 parts by weight of a radiation blocking agent.
3. The antifogging laminate according to item 1. 29. The antifogging laminate according to claim 28, wherein the radiation blocking agent is an infrared absorbing agent. 30. An infrared absorbent comprising Li, Al, Si, M
The anti-fogging laminate according to claim 29, which is an inorganic compound containing at least one element selected from g, Ca, and Zn. 31. An infrared absorbent according to the following formulas (I) to (V):
At least one selected from inorganic compounds represented by
31. The antifogging laminate according to claim 30, which is an inorganic compound. M²⁺ _(1-x)Al³⁺ _x(OH^-)_Two・ (A^n-)_{x / n}・ MH_TwoO (I) (where M²⁺Contains magnesium, calcium and
Indicates a divalent metal ion selected from the group consisting of lead,
x and m are 0 <x <0.5, 0 ≦ m ≦ 2, A^n-Is n-valent
Li)⁺(Al³⁺)_Two(OH^-)₆・ (A^n-)_{1 / n}・ MH_TwoO (II) (wherein A^n-Represents an n-valent anion, and m represents 0 ≦ m
≤ 3) [(Li⁺ _(1-x)・ M²⁺ _x) (Al³⁺)_Two(OH^-)₆]_Two(Si_yO_{(2y + 1)} ^2-)_{(1 + x)} ・ MH_TwoO (III) (wherein, M²⁺Represents a divalent metal ion, m, x and
And y satisfy the conditions of 0 ≦ m <5, 0 ≦ x <1, 2 ≦ y ≦ 4.
Satisfy) [(Li⁺ _(1-x)・ M²⁺ _x) (Al³⁺)_Two(OH^-)₆]_Two(A^n-)_{2 (1 + x) / n} ・ MH _Two O (IV) (where M²⁺Is a divalent metal ion, A^n-Is n-valent
Represents an anion, and m and x are 0 ≦ m <5, 0.01 ≦
x <1) mAl_TwoO_Three・ (N / p) M_{2 / p}O ・ X ・ kH_TwoO (V) (where X is a carbonate group and M is an alkali metal or
An alkaline earth metal ion, p is the valence of the metal ion M
M, n and k are 0.3 ≦ m ≦ 1, 0.3 ≦
(satisfies the conditions of n ≦ 2, 0.5 ≦ k ≦ 4) 32. The antifogging laminate according to claim 30, wherein the infrared absorber is silicon oxide and / or aluminum silicate. 33. The antifogging laminate according to claim 28, wherein the thermoplastic resin composition further contains at least one selected from a light stabilizer, an ultraviolet absorber, an antifog and an antifogging agent. 34. A thermoplastic resin composition comprising 0.02 to 5 parts by weight of a light stabilizer per 100 parts by weight of a thermoplastic resin,
0.01 to 3 parts by weight of ultraviolet absorber, 0.01 to 3 antifog agent
The anti-fogging laminate according to claim 33, comprising at least one part by weight and 0.1 to 4 parts by weight of an anti-fog agent. 35. The antifogging laminate according to claim 1, wherein the base material comprises two or more layers. 36. The antifogging laminate according to claim 35, wherein the substrate has at least one layer made of a polyolefin resin. 37. The anti-fog according to claim 36, wherein the polyolefin resin is a low density polyethylene, an ethylene / α-olefin copolymer or an ethylene-vinyl acetate copolymer having a vinyl acetate content of 30% by weight or less. Laminate. 38. The antifogging laminate according to claim 1, wherein the laminate is in the form of a sheet or a film. 39. The antifogging laminate according to claim 1, which is used as an agricultural film. 40. The antifogging laminate according to claim 38, which is used as an agricultural film for greenhouse horticulture. 41. A light-transmitting plate.
The antifogging laminate according to any one of the above. 42. Any one of an illumination cover, a marking film, an automobile outer panel, a housing / building outer wall covering film, a window covering film, a window sticking sheet, an antifogging packaging film, and a mirror fogging preventing sheet. Claims 1 and 2 used for applications
39. The antifogging laminate according to any one of 4 and 38.