CN1229026A

CN1229026A - Anti-frost and anti-fog laminated substance

Info

Publication number: CN1229026A
Application number: CN98127129A
Authority: CN
Inventors: 中西美都子; 阪谷泰一; 藤田勉
Original assignee: Sumika Plastech Co Ltd
Current assignee: Santerra Corp.
Priority date: 1997-12-25
Filing date: 1998-12-24
Publication date: 1999-09-22
Anticipated expiration: 2018-12-24
Also published as: JPH11240112A; FR2773100A1; KR19990063384A; KR100740055B1; CN1211202C

Abstract

The invention discloses an anti-fogging laminate, an external A layer of laminate comprising substrate material, resin and very fine particles of an inorganic compound, and a B layer, on the same side of the substrate as the A layer, consisting predominantly of very fine particles of an inorganic compound.

Description

Anti-frost and anti-fog laminated substance

The invention relates to the anti-frost and anti-fog laminated substance of purposes such as being used for horticultural facility and light-passing board.

Past, for example, agricultural film that agricultural greenhouse, tunnel, barrier etc. use and thin slice etc. are owing to use under outdoor environment, when the surface temperature of film reaches the dew point of water vapor when following, produce dewfall, the surface fogs (frost mist), and the transmitance of sunlight can reduce, thereby has delayed growing of farm crop, the water droplet that adheres to is dropped on the farm crop, brings problems such as disease.

Therefore, the various anti-frost mist layered products that anti-frost mist layer is set have been proposed on various substrate materials.Wherein, to improve frost prevention fog effect persistence is purpose, for example in the spy such as opens clear 51-6193,51-81887,53-39347,57-119974,59-15473,60-96682,62-27146,62-283135,63-132989,63-150369 number at communique, proposition utilizes coating method, and the anti-frost mist covered film that contains the mineral compound particulate is set on it is the most surperficial.

Anti-frost mist deterioration etc. was as the motion of purpose when also handlebar prevented covered film damage or prevents high temperature, on the anti-frost mist covered film further on the lamination by hydrophilic resin forms layer.

Yet, in the aforesaid method, in the time of can confirming under hot and humid environment prolonged preservation, the phenomenon that anti-frost mist degenerates can appear also sometimes.

The invention provides a kind of anti-frost and anti-fog laminated substance, even under hot and humid environment, after the prolonged preservation, find in environment for use, also to have good long-term anti-frost mist performance.

Present inventors have carried out big quantity research in order to solve above-mentioned problem, and the result has finished the present invention.

Promptly, the invention provides a kind of anti-frost and anti-fog laminated substance, surfaces A layer of layered product that it is characterized in that comprising substrate material, forms by resin and mineral compound particulate and the B layer that the mineral compound particulate is present in A layer the same side of above-mentioned substrate material as principal constituent.

Among the present invention, said A layer is the layer that is formed by resin and mineral compound particulate, and said B layer is a layer of the mineral compound particulate being made principal constituent.The mineral compound particulate of herein saying be particle diameter at 5 μ m or following particle, preferably in following dispersion medium, can be dispersed into the inorganic compound particle of colloidal.The mineral compound particle dispersion liquid of this mineral compound particulate and colloidal for example can utilize Gypsum﹠amp; The method of record is made among the Lime (No.211, P46 (1987)).

As the particulate of this mineral compound, metal particle, oxide fine particle, hydroxide particulate, carbonate particulate, sulphate particles etc. are arranged.As metal particle, particulates such as gold, palladium, platinum, silver, sulphur are for example arranged, as oxide fine particle, hydroxide particulate, carbonate particulate, sulphate particles, oxide fine particle, hydroxide particulate, carbonate particulate, sulphate particles, clay mineral of metals such as silicon, aluminium, zinc, magnesium, calcium, barium, titanium, zirconium, manganese, iron, cerium, nickel, tin etc. are for example arranged.

In these oxide fine particles, hydroxide particulate, carbonate particulate, the sulphate particles, best is, and oxide fine particle or hydroxide particulate, particularly aluminium or silicon or titanyl compound particulate or hydroxide particulate are better.These mineral compound particulates can 2 kinds or above share.

As the mineral compound particulate of A layer, preferably the titanium oxide microparticle of titanium oxide microparticle, Detitanium-ore-type is better.The median size of titanium oxide microparticle is preferably in 100nm or following usually at 200nm or following.Consider that from the transparency of anti-frost and anti-fog laminated substance it is better at 10nm or following particulate to have a particle diameter.

Median size is 50-5000nm, and more preferably during 80-300nm, the joint performance of anti-frost and anti-fog laminated substance and galvanized sheet etc. reduces significantly, thereby improves.

So-called bondability index E is meant on the frost prevention cloudy surface of water attached to this anti-frost and anti-fog laminated substance, bonding on zine plate, dried stripping strength with polyurethane series baking vanish, measure the test film of wide 20mm with self-registering instrument, on 180 ° of directions, the tensile loading when peeling off with the speed of 50mm/min.So-called galvanized sheet is to have implemented galvanized steel sheet.For example, the zine plate of stipulating among the JIS H8641.Baking vanish is as shown in JISK5980, and after the coating of synthetic resin coatings such as polyurethane series, high temperature heating down makes the hardened method of filming, and is used for the part that indoor and outdoor requires weather resistance mostly.

When bondability index E is excessive,, the strength when peeling off destroys because can producing substrate material, thus bondability index E 500g/20mm or following more fortunately, at 200g/20mm or following better.

At this moment the mineral compound particulate of A layer, with the L value of following formula definition more preferably greater than 1.Particularly consider from stabilising effect, L value more fortunately 1.5 or more than, 2 or above better.And consider that from the transparency of anti-frost and anti-fog laminated substance the L value is preferably in below 4.

L=(N×R)/S

Herein, R is the median size (m) of institute's inorganic-containing compound particulate in the A layer, and S is the surface-area (m of anti-frost and anti-fog laminated substance A layer ²), N is the number of institute's inorganic-containing compound particulate in the A layer of per surface area S, defines with following formula.

N=V/{(4/3)×π×(R/2) ³}

Wherein, V is the volume (cc/m of institute's inorganic-containing compound particulate in the A layer of per surface area S ²).Median size R for example can measure with electron microscope, moving light particles distribution instrument at random, laser refraction method particles distribution instrument at random etc.N is the weight (g/m that removes institute's inorganic-containing compound particulate in the A layer of per surface area with the density (g/cc) of particulate ²), the volume (cc/m of the A layer per unit surface-area that obtains ²), during calculating, suppose with the ball of particle diameter R occupied.

As the mineral compound particulate of B layer,, preferably the oxide fine particle of silicon or the oxide fine particle or the hydroxide particulate of hydroxide particulate and aluminium are used together from coating, film toughness, substrate material adherence, anti-frost mist consideration.

In this blended combination; because the oxide fine particle or the oxyhydroxide grain of silicon; for basoid; the oxide fine particle of aluminium or hydroxide particulate are acidoids; produce firm combination owing to interact; so handy especially, the mineral compound as disperseing to present alkalescence in the water for example preferably uses following various clay minerals.

Its ratio of mixture, when for example using silicon oxide particle and alumina particulate, the weight ratio of alumina/silica is the scope of 90/10-10/90 usually, preferably 80/20-20/80, the more preferably scope of 70/30-30/70.

Among the present invention, the thickness of A layer is considered from the anti-frost mist of gained anti-frost and anti-fog laminated substance and traumatic resistance, in gravimetric thickness, and 0.01g/m more fortunately ²Or more than, 0.02g/m ²Or above better, 0.05g/m ²Or it is above especially good.Consider from the cohesiveness of anti-frost and anti-fog laminated substance, be preferably in 10g/m ²Or below, better at 2g/m ²Or below, at 0.5g/m ²Or it is following especially good.

Among the present invention, the thickness of B layer is considered from the adherence strength of substrate material or A layer and other layer, in gravimetric thickness, and 0.01g/m more fortunately ²Or more than, better at 0.02g/m ²Or more than, at 0.05g/m ²Or it is above especially good.From considerations such as the transparency or outward appearances, be preferably in 10g/m ²Or below, better at 2g/m ²Or below, at 0.5g/m ²Or it is following especially good.

Among the present invention, the ratio (d2/d1) of A layer thickness (d1) and B layer thickness (d2) is considered from the persistence of appearance effect, is preferably 0.01-10.And then, film and during the binding property of galvanized sheet, be preferably 0.01-1 wanting to reduce.

A layer and/or B layer, when strengthening each other the interaction of mineral compound particulate, for example can contain various tensio-active agents, organic system ionogen, various tackiness agents etc., for the dispersion liquid of mineral compound particulate described later is paid thixotropy, also can add and contain various clay minerals etc.

As tensio-active agent, can use over known, for example, anionic property, cationic, nonionic, various tensio-active agents such as both sexes, for example, as the anionic surfactant, Sodium octoate is arranged, potassium octanoate, Sodium decanoic acid, Sodium n-caproate, Sodium tetradecanoate, potassium oleate, the stearic acid tetramethyl-ammonium, sodium stearate, mountain Yu acid potassium etc. has the carboxylic metallic salt or the ammonium salt of 6-24 carbon atom alkyl chain, sodium octyl, sodium laurylsulfonate, dodecane phenyl sodium sulfonate, dodecane phenyl ammonium sulphonate etc. has the metal organic sulfonate or the ammonium salt of 6-24 carbon atom alkyl chain, phosphoric acid ester metal-salt or ammonium salt with 6-24 carbon atom alkyl chain, have hydrocarbon system anionic surfactants such as the metal-salt of boric acid ester of 6-24 carbon atom alkyl chain or ammonium salt, perfluoro decanoate sodium, fluorine series anion surfacants such as perfluoro octyl sulfonic acid sodium, condensation body with polydimethylsiloxane base and epoxide affixture, the silicon series anion surfacants of anionic property bases such as polydimethylsiloxane base and carboxylic metallic salt etc., the carboxy acid alkali's metal-salt that particularly has 6-10 carbon atom alkyl chain is best.

As cationic surfactant, chlorine cetyltrimethyl ammonium, chlorine two-octadecyl Dimethyl Ammonium, bromo-N-octadecyl pyridinium, bromine hexadecyl triethyl phosphine etc. are for example arranged.

As nonionic surfactant, the Sorbitol Powder single-hard ester acid ester is for example arranged, the Sorbitol Powder monopalmitate, Sorbitol Powder fatty acid esters such as Sorbitol Powder list mountain Yu's acid esters are tensio-active agent, glyceryl monolaurate, the glycerine monopalmitate, Zerol, two Stearic diglycerides, glycerol fatty acid esters such as triglycerin monostearate are tensio-active agent, the polyoxyethylene glycol monopalmitate, polyoxyethylene glycol such as polyethylene glycol mono stearate are tensio-active agent, the epoxide affixture of alkylphenol, Sorbitol Powder glycerol condensate and organic acid ester, fluorine such as two glyceryl ester of perfluoro decanoate are nonionic surfactant etc.

In addition, also can use amphoterics.

When using tensio-active agent, its consumption is 0.5 weight part or following for the mineral compound particulate of 100 weight parts, best 0.1 weight part or following.When consumption was very few, the effect that obtains was also too small, therefore, usually 0.001 weight part or more than, be preferably in 0.01 weight part or more than.

As the organic system dielectric medium, right-toluenesulfonic acid sodium salt, benzene sulfonic acid sodium salt, butyl sulfonic acid potassium, phenyl sodium hypophosphite, diethyl sodium phosphate etc. are for example arranged, benzene sulfonic derivative is good especially.When using the organic system dielectric medium, its consumption for 100 weight part mineral compound particulates, usually at 0.1 weight part or following, is preferably in 0.05 weight part or following.When consumption was very few, the effect that obtains was also too small, so, usually 0.0001 weight part or more than, be preferably in 0.001 weight part or more than.

As tackiness agent, thermoplastic resin is for example arranged.As this thermoplastic resin, it is that resin, polyethylene-based resin, vinyl chloride-based resin, vinylidene chloride resin, polyurethane series resin, polycarbonate-based resin, phenylethylene resin series, vinyl acetate between to for plastic are that resin, unsaturated polyester are resin etc. that acrylic resin, ethene-vinyl acetate are arranged, the most handy acrylic resin.These resins preferably carry out crosslinked, also can contain following additive.

In these thermoplastic resins, for example, in media such as water, form and be dispersed into granular emulsion, owing to the tackiness agent that is dissolved in the medium is easy to and the interaction of mineral compound particulate, so can be fit to use.As best adhesive agent emulsion example, the water-based emulsion of acrylic resin and the water-based emulsion of polyurethane series resin are arranged.As best binder solution, poly--2-hydroxyethyl meth acrylate aqueous solution etc. is arranged.

For paying the mineral compound particle dispersion liquid with thixotropy, and the various clay minerals that add, following type is roughly arranged, promptly, on 4 body layers of silicon oxide, have with aluminium and magnesium etc. be central metal 8 body layers the type that forms by 2 layers of structure and will be 8 body layers of central metal with aluminium and magnesium etc., the type that forms from the 3-tier architecture of sandwich.

As former case, kaolin group, antigorite family etc. are arranged.As latter's example, the montmorillonite family that divides by the interlayer cation number, vermiculite family, mica family etc. are arranged.In these clay minerals, say that as following institute be preferably and can bring into play thixotropic inorganic layered compounds to stratiform Peng Run in dispersion medium, particularly aqueous liquid dispersion demonstrates thixotropic montmorillonite family, vermiculite family for well.

From continuing long-term anti-frost mist consideration, the amount of organic compound such as above-mentioned various tensio-active agent, organic system ionogen, tackiness agent, 75 weight % or following more fortunately in A layer and/or B layer, better at 50 weight % or following, at 10 weight % or following good especially, 1 weight % or following especially good.

Among the present invention, as resin used in the A layer, it is that resin, polyethylene-based resin, vinyl chloride-based resin, vinylidene chloride resin, polyurethane series resin, polycarbonate-based resin, phenylethylene resin series, vinyl acetate between to for plastic are that resin, unsaturated polyester are resin etc. that acrylic resin, ethene-vinyl acetate are for example arranged, wherein, best is a following class hydrophilic resin.

So-called hydrophilic resin is to have very strongly hydrophilic polar group person in the molecule, and so-called this polar group is hydrogen bond base and/or ionic base.The ratio of polar group, the weight percent of the hydrogen bond base of per unit weight resin and/or ionic base (have 2 kinds or above these whens base, it amounts to) is about 25～70% usually, preferably is about 30～50%.

So-called hydrogen bond base is meant on the atom except that carbon atom (heteroatoms) to have at least 1 direct base in conjunction with hydrogen.As this hydrogen bond base, hydroxyl, amino, sulfydryl, carboxyl, sulfo group, phosphate etc. are for example arranged.

On the other hand, so-called ionic base is meant and is confined in water, roughly can carry out the base with at least a electric charge in the plus or minus of hydration with the water of water molecules.As this ionic base, carboxylic ester group, azochlorosulfonate acid ion base, phosphate ion base, ammonium, Phosphonium base etc. are arranged.

In hydrogen bond base or ionic base, hydroxyl, amino, carboxyl, sulfonic group, carboxylic ester group, azochlorosulfonate acid ion base, ammonium etc. are best.

The content of these hydrogen bonds or ionic base for example can be measured by nucleus magnetic resonance (NMR) method (1H-NMR, 13C-NMR etc.).

As hydrophilic resin, it is that resin, polyurethane series resin, melamine are resin, phenol resin, polyose and MODIFIED POLYSACCHARIDE class etc. that vinylite, acrylic resin, polyester based resin, epoxy are for example arranged, preferably following.

For example, polyvinyl alcohol or vinyl alcohol branch rate are arranged at polyoses such as 41 moles of % or above ethylene-vinyl alcohol copolymer, Walocel MT 20.000PV, Natvosol, carboxymethyl cellulose, amylose starch, amylopectin, プ Le ラ Application, カ-De ラ Application, morningstar lily, chitin, chitosan, Mierocrystalline cellulose, polyacrylic acid, sodium polyacrylate, polyphenyl sulfonic acid, polyphenyl sodium sulfonate, polymine, polyallylamine, its ammonium salt, polyvinyl mercaptan, polyglycerol ester etc.

In above-mentioned hydrophilic resin, use polyvinyl alcohol and/or polyose (and even its derivative) better.In addition, ideal polyvinyl alcohol [(CH ₂CHOH) _n-] time, be (17/44) * 100=about 39% as the weight percent of the OH base of above-mentioned hydrogen bond base.

So-called polyvinyl alcohol is to have the polymkeric substance of the vinyl alcohol monomeric unit being made main composition, for example, with the acetic ester of vinyl acetate polymer partly add polymkeric substance (accurately saying it is the co-polymer that vinyl alcohol and vinyl acetate between to for plastic form) that water decomposition or transesterify (saponification) obtain or, with the trifluoracetic acid ethene polymers, the formic acid ethene polymers, piperylene acid ethene polymers, uncle-Ding Vinyl Ether polymkeric substance, trimethyl silyl Vinyl Ether polymkeric substance etc. carries out the polymkeric substance that saponification obtains and (about the details of [polyvinyl alcohol], for example can compile with reference to Port パ-Le, [the PVA world], 1992, the meeting of (strain) polymer publication; People such as Nagano, [Port パ-Le],, the meeting of (strain) polymer publication in 1981).

Above-mentioned saponification degree, from the anti-frost mist consideration of layered product initial stage of obtaining, molar percentage more fortunately 50% or more than, better 70% or more than.And preserve anti-frost mist consideration from moisture-proof heat, be preferably in 85% or below.

The mean polymerisation degree of polyvinyl alcohol, from anti-frost mist consideration of initial stage, be preferably in 100 or more than, preserve anti-frost mist and reduce coating fluid viscosity consideration when forming the A layer from moisture-proof heat by coating, more fortunately 10000 or below, better 3000 or following, 500 or following especially good.

Above-mentioned polyvinyl alcohol can use separately, also can 2 kinds or above mixing use.

Also can use the derivative of polyvinyl alcohol, as the functional group beyond the hydroxyl-removal, for example, also can some amino, sulfenyl, carboxyl, sulfo group, phosphate, carboxylic ester group, azochlorosulfonate acid ion base, phosphate ion base, ammonium, Phosphonium base, silyl, siloxanes, alkyl, allyl group, fluoroalkyl, pure oxygen base, carbonyl, halogen radical etc.

As polyose, can replace part or all hydroxyl in its hydroxyl with other substituting group.As other substituting group, pure oxygen base, cyano group, amino, sulfenyl, carboxyl, sulfonic group, phosphate, ammonium, Phosphonium base etc. are for example arranged.Alcohol oxygen base can also contain substituting groups such as hydroxyl, amino, sulfenyl, carboxyl, sulfonic group, phosphate, ammonium, Phosphonium base, and carboxyl, sulfonic group, phosphate, ammonium, Phosphonium base also can be the forms of its ester or salt.

The hydroxyl that polyose has with the ratio that other substituting group replaces, for example can use nucleus magnetic resonance (NMR) method (1H-NMR, 13C-NMR etc.) to measure.

Mierocrystalline cellulose is for example arranged, amylopectin, プ Le ラ Application, カ-De ラ Application, ザ Application Application, chitin, chitosan, cellulose ethers, cellulose esters etc., and then as cellulose ethers, methylcellulose gum is arranged, ethyl cellulose, cyanoethyl cellulose, Natvosol, hydroxypropylcellulose, hydroxyethylmethyl-cellulose, hydroxyethyl ethylcellulose, Vltra tears, carboxymethyl cellulose, carboxymethyl cellulose salt etc., as cellulose esters, nitrocellulose is for example arranged, sulfate cellulose, cellulose acetate, cellulose acetate is saponified, amylose starch etc.It also can be the polyose of putting down in writing during [function セ Le ロ-ス exploitation (distribution in the シ of Co., Ltd.-エ system シ-1985 year)] waits.In these polyoses, preferably water-soluble or water dispersible.In with these polyoses of other substituting group during part or all hydroxyl of hydroxyl, its substitute proportion, for example, with the methoxyl group substitution value be decided to be DS (DS: replace hydroxyl in the cellulosic glucose ring unit by epoch number mean value) with methoxyl group, when hydroxy alkoxy base substitution value is decided to be MS (MS: with the mean value of hydroxyl number in the glucose ring unit of hydroxy alkoxy base substituted cellulose), DS is preferably 1.2-2, or the best 0.1-2.5 of MS.When having the polyose of methoxyl group and two kinds of bases of hydroxy alkoxy base, the best 1.2-2 of DS, the best 0.1-0.4 of MS.

As part or all the specific examples of polyose that replaces with other substituting group in this hydroxyl, be example with the water-soluble cellulose ether, methylcellulose gum, Natvosol, hydroxyethylmethyl-cellulose, Vltra tears are arranged.The viscosity of polyose, usually at 20 ℃, the value of 2% aqueous solution is 2-100000cPs.Exist the correlationship of rule between the viscosity of polyose and the molecular weight of this polyose, viscosity is high more, and molecular weight is big more.When utilizing coating method to form the A layer, considered from applying solution uniformly, the polyose of low viscosity (lower molecular weight) preferably, and consider the preferably polyose of high viscosity (high molecular) from the traumatic resistance and the lasting frost prevention fog effect of gained A layer.Preserve anti-frost mist consideration from following moisture-proof heat, DS is the ether of cellulose of 1.6-2.0, and particularly, methylcellulose gum is better, and 20 ℃, the value of 2% aqueous solution is at 20cps or following, at 5cps or following more handy.

Among the present invention, the A layer is the layer that is formed by resin and mineral compound particulate, the weight percent of the mineral compound particulate in the A layer, consider from preventing surperficial albefaction or traumatic resistance, the mineral compound particulate be preferably in 1 weight % or more than, preserve anti-frost mist consideration, 99 weight % or following more fortunately from moisture-proof heat, % is better in 20-80 weight, and 40-60 weight % is good especially.

On the other hand, above-mentioned anti-frost and anti-fog laminated substance is for example from preventing that the ammonia ester from being bonding considerations such as baking vanish and zine plate, the mineral compound particulate more fortunately 20 weight % or more than, be preferably in 99 weight % or following, so 40 weight % or more than, better 60 weight % or more than.

The thickness of A layer considers to metal sheet adherent effect that from preventing the gained anti-frost and anti-fog laminated substance in the A layer constituted, preferably the structure of Cai Yonging was mineral compound particulate overlapping 2 or above particulate on thickness direction at this moment, and its gravimetric thickness is 0.05g/m more fortunately ²Or more than, 0.10g/m ²Or above better, 0.25g/m ²Or it is above especially good.Consider from the transparency, more fortunately 10g/m ²Or below, at 5g/m ²Or following better, at 1g/m ²Or it is following especially good.

Do not have particular determination for substrate material used among the present invention, can with resin, paper, cloth, timber, metal, pottery etc. widely material as substrate material.Consider from formability, preferably use resins such as thermosetting resin or thermoplastic resin.But these several be used in combination.

As thermoplastic resin, it is resin that chlorine such as polyolefin-based resins, polyvinyl chloride, vinylchlorid-methyl methacrylate copolymer compound, polyvinylidene chloride are for example arranged, acrylic resins such as polyester based resins such as polyethylene terephthalate, polyethylene naphthalenedicarboxylate acid esters, polymethylmethacrylate, fluorine resin, polycarbonate-based resin etc.

As said polyolefins is resin, be the homopolymerization or the multipolymer of alpha-olefin, alpha-olefin is made the alpha-olefin of principal constituent and the multipolymer of heterobifunctional monomer, for example, polyethylene, polypropylene, ethylene-propylene copolymer, ethene-1-Butylene copolymer, ethene-4 methyl 1 pentene copolymer, ethene-hexene-1 multipolymer, ethylene/alpha-olefin copolymers such as ethylene-octene-1 multipolymer, and then heterobifunctional monomer is the polar ethylene monomer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, the ethylene-methyl methacrylate methyl terpolymer, ethene-vinyl acetate-methylmethacrylate copolymer, ionic resin etc.These thermoplastic resins can also can use with a kind in the several resins fusion.

When anti-frost and anti-fog laminated substance of the present invention is used for agricultural with film, thin slice, as the resin of above-mentioned substrate material thermoplastic resin preferably.

When being used for greenhouse etc. with agricultural ganoine thin film thin slice, acrylic resin, polycarbonate such as polymethylmethacrylate preferably, the resin that the transparency such as vibrin such as polyethylene terephthalate, fluorine resin is good.When seeking intensity, rigidity etc., preferably biaxial stretch-formed film, thin slice are made substrate material.

When being used for agricultural such as greenhouse, tunnel, barrier and using flexible film, better be that particularly available polyolefin-based resins is as substrate material with flexible vinyl chloride or fluorine resin, polyolefin-based resins.

Especially as the polyolefin-based resins that is used for agricultural flexible film substrate material purposes, preferably density is at 0.935g/cm ³Or following new LDPE (film grade) or ethylene/alpha-olefin copolymer or vinyl acetate content be at 30 weight % or following ethylene-vinyl acetate copolymer etc., and it is good to obtain the transparency and flexibility, and the film of cheapness.

Alpha-olefin as ethylene/alpha-olefin copolymer, for example be 3-18 carbon atom, better be 4-12 carbon atom, as specific examples, propylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-ten carbenes, 1-dodecylene, 1-tetrahydrobenzene and cyclohexyl ethene etc. can have been enumerated.Ethylene/alpha-olefin copolymer can be the multipolymer of ethene and a kind of alpha-olefin, also can be ethene and two kinds or above alpha-olefin copolymer.The content of alpha-olefin is generally 2-25 weight %, preferably 4-18 weight %.

For ethylene, consider from anti-frost mist retentivity, preferably form distribution coefficient of variation C by the following formula definition _x0.5 or below.Consider preferably will have C from anti stick and dirt resistance _xBe about 0.1～0.4 ethylene/alpha-olefin copolymer the outside as substrate material.

Cx=σ/SCB?ave????????????????(1)

In the formula, σ represents to utilize setting prop discerning method on the temperature, from the stripping quantity of stripping composition and the ethylene/alpha-olefin copolymer that its degree of branching is tried to achieve are formed the standard deviation that distributes at each temperature.SCB ave represents the mean value of the short chain branches of per 1000 carbon atoms in the ethylene/alpha-olefin copolymer.

σ and SCB ave try to achieve by following respectively.

SCB ave measures with short key ramose such as polyethylene, by usual practice carry out can, try to achieve from the FT-IR spectrum of ethylene/alpha-olefin copolymer.Said herein short key branch is meant the branch's (being typically the branch of 1-4 carbonatoms) with 1-4 carbon atom.σ can utilize on the temperature setting prop to differentiate the method for determining and try to achieve.Promptly, ethylene/alpha-olefin copolymer is dissolved in being heated to the solvent of specified temperature, in the pillar in the column type of packing into the baking oven, the temperature of pillar is in case reduce, then make it to rise to the temperature of regulation, use the FT-IR that is connected with pillar to be determined at the relative concentration and the degree of branching of stripping composition under this temperature.Temperature is raise stage by stage, rise to outlet temperature (for the temperature of the whole strippings of testing of multipolymer).The relative concentration and the degree of branching of each stripping composition of statistical treatment gained are obtained and are formed the standard deviation that distributes.

Above-mentioned ethylene/alpha-olefin polymer can pass through, for example, so-called monosystem catalyzer such as the coordination compound catalyzer of transition metal such as use palladium and nickel or metallocenes series catalysts, solvent or solvent-free following is being arranged, with ethene and carbonatoms is the alpha-olefin of 3-18, carries out the polymeric method with gas phase/solid phase, liquid/solid phases or even liquid phase and makes.Polymerization temperature is generally 30～300 ℃, and polymerization pressure is generally normal atmosphere～3000Kg/cm ²For example, the spy open flat 6-9724, spy open flat 6-136195, spy open flat 6-136196, spy open flat 6-207057, etc. the so-called metallocenes olefin polymerizing that contains the metalloscene catalyst composition put down in writing in the communique with catalyzer in the presence of, carry out polymerization by alpha-olefin, can make ethylene/alpha-olefin polymer ethene and 3-18 carbon atom.

And then, utilize the special method of putting down in writing among the flat 8-276542 of opening, as benchmark, the branches mean value of making than high molecular side subtracts above ethylene/alpha-olefin polymer at the branches mean value of lower molecular weight side with the position at GPC stripping curve peak, and this polymkeric substance can be suitable among the present invention.When using such polymkeric substance, can obtain the good especially multilayer film of resistance to blocking, dirt resistance.

The fusion flow velocity (MFR) of polyolefin-based resins is preferably about 0.1-50g/10 branch, better is about the 0.3-20g/10 branch.This MFR is the standard by ASTM D 1238-65T, under the condition of 190 ℃ of 2.16kg loadings, and the value of measuring.When MFR is too small, the very poor in processability when making multilayer film, when MFR was excessive, the multilayer film intensity that obtains was very poor.Density so that the method for JIS K7112 is measured is preferably 0.91-0.94g/cm ³, 0.92-0.94g/m ³Better, 0.925-0.94g/m ³Especially good.With the molecular weight distribution (Mw/Mn) that Gel Permeation Chromatography (GPC) tries to achieve, consider better to be about 1.5-4 from processibility and intensity, better be about 2-3.5.

Anti-frost and anti-fog laminated substance of the present invention when the agricultural film, the formed film of thermoplastic resin composition that forms by thermoplastic resin and radiation barrier agent of substrate material preferably.

The radiation of herein saying is that the wavelength that is mainly radiated at night by the ground in the facilities such as the warm greenhouse of illumination such as visible light of the sun on daytime etc. is the infrared rays in 2-25 μ m zone, and said radiation barrier agent is to have this radiation of absorption or reflect the material of this radiation character.

As the radiation barrier agent, for example, be example with infrared absorbent or infrared reflection agent etc.So-called infrared reflection agent does not just have particular determination to this so long as can reflect the material of the interior any wavelength of above-mentioned wavelength region, and for example having zinc oxide etc. inorganic is the infrared reflection agent.

As inorganic infrared absorbent, the lithium aluminum complex hydroxide is for example arranged, complex hydroxides such as hydrotalcite-based compound, magnesium oxide, calcium oxide, aluminum oxide, silicon oxide, metal oxides such as titanium oxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, oxyhydroxide such as aluminium hydroxide, magnesiumcarbonate, lime carbonate, carbonate aluminum,basic carbonates such as (for example special alkaline carbonic acid aluminium double salts of putting down in writing in the flat 9-279131 communique of opening), vitriolate of tartar, sal epsom, calcium sulfate, zinc sulfate, Sulfateses such as Tai-Ace S 150, Trilithium phosphate, sodium phosphate, potassiumphosphate, calcium phosphate, zirconium phosphate phosphoric acid salts such as (for example special H type zirconium phosphates of putting down in writing in the flat 8-67774 communique of opening), Magnesium Silicate q-agent, Calucium Silicate powder, pure aluminium silicate, silicates such as titanium silicate, sodium aluminate, potassium aluminate, aluminate class such as calcium aluminate, sodium aluminium silicate, aluminum potassium silicate, aluminum silicates such as calcium aluminosilicate, kaolin, clay, clay minerals such as talcum, composite oxides etc.As organic infrared absorbent, polyacetal, polyvinyl alcohol and its derivative, ethylene/vinyl alcohol co-polymer etc. are arranged.

In these infrared absorbents, consider that from the recirculation efficient of multilayer film density is at about 3g/cm ³Or below, be preferably in about 2g/cm ³Or below, consider that from absorbing the infrared rays performance inorganic is that infrared absorbent is better.

Infrared absorbent is inorganic when being infrared absorbent, considers that from light transmission its specific refractory power will approach the specific refractory power of used resin material, and considers preferably have the absorptive character of broad wavelength region from heat retaining property.From these considerations, preferably hydrotalcite-based compound, lithium aluminum complex hydroxide, aluminum silicate, alkaline carbonic acid aluminium double salts etc.

So-called hydrotalcite-based compound is the compound that following formula I is represented.

M ²⁺ _1-xAl ³⁺ _x(OH ^-) ₂(A ₁ ^n-) _x/n·mH ₂O???????(Ⅰ)

(in the formula, M ²⁺Be divalent metal ion, A ₁ ^N-Satisfy the condition of 0＜x＜0.5 and 0≤m≤2 for n valency negatively charged ion, x and m).As M ²⁺Mg is arranged ²⁺, Ca ²⁺, Zn ²⁺Deng.N valency negatively charged ion does not have particular determination, and Cl is for example arranged ^-, 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 (CN) ₆ ^3-, Fe (CN) ₆ ^4-, CH ₃COO ^-, C ₆H ₄(OH) COO ^-, (COO) ₂ ^2-, negatively charged ion and special poly-silicic acid ion and the polyphosphoric acid ions of putting down in writing among the flat 8-217912 of opening such as terephthalic acid ion, naphthene sulfonic acid ion.Specifically, can use, as natural water talcum or ァ Le カマィザ-DHT-4A (trade(brand)name, consonance chemical industry system) class synthetic hydrotalcite.N in the formula I is preferably 1-4.

Also can be with calcium hydroxide or calcium aluminum complex hydroxide: CaAl _x(OH) _2+3xShare with hydrotalcite-based compound.

As the lithium aluminum complex hydroxide, for example there is the spy to open the compound that disclosed following formula II is represented in the flat 5-179052 communique.

Li ⁺(Al ³⁺) ₂(OH ^-) ₆·(A ₂ ^n-) _1/n·mH ₂O????(Ⅱ)

(in the formula, A ₂ ^N-Be n valency negatively charged ion, m satisfies the condition of 0≤m≤3).N valency negatively charged ion does not have particular determination, for example, have with the formula I compound in A ₁ ^N-Identical negatively charged ion.N in the formula II is preferably 1-4.

As above-mentioned 2 kinds of other complex hydroxides in addition, for example have, contain at least a element and Li and Al, and have the complex hydroxide of hydroxyl from from alkaline-earth metal, transition metal, Zn and Si, selecting.In alkaline-earth metal, preferably magnesium, calcium.Preferably iron, cobalt, nickel, the manganese of divalent or 3 valencys in the transition metal, wherein iron is best.The mol ratio of Al and Li (Al/Li) is generally 1.5/1-2.5/1, is preferably 1.8/1-2.5/1.

The element mol ratio of selecting from alkaline-earth metal, transition metal, Zn and Si (a) for 1 mole of Li element, is generally 0＜a＜1.5, better 0.1≤a≤1.4, more preferably 0.2≤a≤1.2.Anionicsite beyond this complex hydroxide hydroxyl-removal for example has inorganic acid ion, Fe (CN) such as poly-silicic acid ion, carbonic acid ion, halide ions, sulfate ion, sulfurous acid ion, nitrate ion, nitrite ion, phosphate ion, phosphorous acid ion, ortho phosphorous acid ion, polyphosphoric acid ion, aluminic acid ion, silicic acid ion, high chloro acid ion, borate ion such as disilicic acid ion, ring silicic acid ion, different silicic acid ion, page or leaf silicic acid ion, net silicic acid ion ₆ ^3-, Fe (CN) ₆ ^4-Deng organic ions such as anionic property transition metal complex compound, acetic acid ion, M-nitro benzoic acid ion, formic acid ion, terephthaldehyde's acid ion, alkylsulphonic acid ion etc.Wherein, carbonic acid ion, halide ions, sulfate ion, phosphate ion, polyphosphoric acid ion, silicic acid ion, poly-silicic acid ion, high chloro acid ion be for well, and carbonic acid ion, polyphosphoric acid ion, silicic acid ion, to gather the silicic acid ion good especially.Specific examples as this complex hydroxide, be to contain Al, Li, Mg, and the complex hydroxide of the about 2.3/1/0.28 of Al/Li/Mg=(mol ratio) (trade(brand)name LMA, Fuji's chemical industry system) and, contain Al, Li, Si, and the complex hydroxide of Al/Li/Si=about 2/1/1.2 (mol ratio) (trade(brand)name Off ヅレィ Application LS, Fuji's chemical industry system).

For example, the compound that disclosed following formula III is represented in WO97/00828,

[(Li ⁺ _(1-x)M ²⁺ _x)(Al ³⁺) ₂(OH ^-) ₆] ₂(Si _yO _(2y+1) ^2-) _(1+x)·mH ₂O??(Ⅲ)

(M in the formula ²⁺Be the divalent metal ion, m, x and y satisfy the condition of 0≤m＜5,0≤x＜1,2≤y≤4),

With open the compound that disclosed following formula IV is represented in the flat 8-217912 communique the spy,

[(Li ⁺ _(1-x)M ²⁺ _x)(Al ³⁺) ₂(OH ^-) ₆] ₂(A ^n-) _2(1+x)/n·mH ₂O?????????(Ⅳ)

(in the formula, M ²⁺Be divalent metal ion, A ^N-Satisfy the condition of 0≤m＜5 and 0.01≤x＜1 for n valency negatively charged ion, m and x), above-mentioned complex hydroxide is best example.As the M in formula III and the formula IV ²⁺, exemplify and be Mg ²⁺, Ca ²⁺, Zn ²⁺Deng.N in the formula IV is preferably 1-4.

And then, be one of infrared absorbent preferably with the alkaline carbonic acid aluminium double salts of following formula (V) expression,

mAl ₂O ₃·(n/p)M _2/pO·X·kH ₂O??????????????????(Ⅴ)

(in the formula, x is a carbonate, and M is basic metal or alkaline-earth metal, and P is the valence mumber of metal M, m, n and k satisfy the condition of 0.3≤m≤1,0.3≤n≤2,0.5≤k≤4).As the X in the following formula (V), can will contain following anionic double salt and above-mentioned alkaline carbonic acid aluminium double salts share, promptly, organic anions such as the oxygen acid (as perchloric acid) of the oxygen acid (nitric acid, nitrous acid) of the oxygen acid of sulphur (sulfuric acid, sulfurous acid), nitrogen, hydrochloric acid, chlorine, the oxygen acid inorganic anions such as (phosphoric acid, phosphorous acid, tetra-sodiums) of phosphorus and acetic acid, propionic acid, hexanodioic acid, M-nitro benzoic acid, phthalic acid acid, terephthalic acid acid, toxilic acid, fumaric acid, succsinic acid, right-Para Hydroxy Benzoic Acid, salicylic acid, picric acid, toluenesulphonic acids.These double salt can be opened disclosed method manufacturing in the flat 9-279131 communique with the spy.

When using above-mentioned complex hydroxide or alkaline carbonic acid aluminium double salts as infrared absorbent, its median size is usually at 5 μ m or following, more about 0.05-3 μ m, more preferably about 0.1-1 μ m.The specific surface area of utilizing the BET method to measure is 1-30m ²/ g is preferably 2-20m ²/ g.

When anti-frost and anti-fog laminated substance of the present invention is used for the very high purposes of the requirement transparency, the specific refractory power of infrared absorbent better approaches the specific refractory power of used resin material, the specific refractory power of measuring with the method for JIS K0062 record is preferably 1.47-1.55,1.48-1.54 more preferably, 1.49-1.53 is particularly good.These infrared absorbents also can contain crystal water.

In order to improve the dispersiveness of the infrared absorbent in substrate material film and the thin slice, can utilize an alkali metal salt etc. of high fatty acid or high fatty acid that infrared absorbent is implemented surface treatment.

The use level of infrared absorbent, substrate material radiation that film sheet requires sees through index in the time of can be according to 23 ℃, and the layer structure of the kind of used infrared absorbent and substrate material film sheet etc. are with due regard to.For example, as infrared absorbent, when using above-mentioned complex hydroxide, its use level is generally the 0.03-25 weight part with respect to 100 weight part substrate material resins, better is the 1-15 weight part.

This anti-frost and anti-fog laminated substance sees through index at 23 ℃ radiation, be with this film sheet as greenhouse etc. the heat-insulating property yardstick during by multiple material, growing of farm crop produced very big influence, can utilize following measuring method to try to achieve.This value is more little, and the heat-insulating property of film sheet is good more.Among the present invention, film sheet 23 ℃ ray see through index more fortunately 25 or below.When the ray of film sheet sees through index 25 or when following, to compare with the polyvinyl chloride film in past, heat-insulating property is roughly equal or good, when being used to heat the greenhouse, can reduce the greenhouse expense, and can improve economical efficiency.It is zero good more that ray approaches through index, and 20 or following better, 15 or following better.

Ray can be measured with following method through index in the time of 23 ℃.

Use infrared spectrophotometer (パ-キ Application エ Le マ-society's system 1640 type FT-IR), with wave number 4000-400cm ^-1Scope is in 23 ℃ of infrared absorption spectrums (penetrant method) of measuring multilayer film, the value of transmitance T (ν) % that obtains at wave number ν.

On the other hand, according to the formula that obtains by the Planck rule (2), calculate the intensity e (ν) of the blackbody radiation spectrum when 23 ℃ wave number ν.Multiply by blackbody radiation spectrum intensity e (ν) with transmitance T (ν) and obtain ray through intensity f (ν) (formula (3)).Will be at wave number 4000-400cm ^-1Scope is carried out principal value of integral to ray through intensity f (ν) and is decided to be ray through energy F, will be at 4000-400cm ^-1In the scope blackbody radiation spectrum intensity e (ν) being carried out principal value of integral and be decided to be the blackbody radiation ENERGY E, is G=100 * F/E thereby ray sees through index definition.When actual integration, with each wave number interval 2cm ^-1Between dividing regions, pairing approximation is calculated in each interval of trapezoid.The heat retaining property that ray sees through the more little expression film of index is good more.

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(m·K)

T (K) absolute temperature.

λ (cm) wavelength (wave number v is the inverse of wavelength)

(h is a quantum of action, and c is that the light velocity, k are boltzmann constant)

Paste P20

Consider that from cycle efficiency the density of anti-frost and anti-fog laminated substance better is lower than 1.0g/cm according to the method for JIS K7112-1980 23 ℃ of measured values ³Density is 0.99g/cm more fortunately ³Or below, better at 0.98g/cm ³Or below, at 0.97g/cm ³Or it is following especially good.Said cycle efficiency, the meaning are the difference difficulties with the vinyl chloride film that is widely used in agricultural use.

Anti-frost and anti-fog laminated substance of the present invention can contain at least a photostabilizer.Can use nickel complex as photostabilizer is photostabilizer, better be obstructed ammonia based compound, particularly molecular weight 1500 or the above ammonia based compound that is obstructed best.

As the ammonia based compound that is obstructed, for example have the spy to open the compound of the structural formula of putting down in writing in the flat 8-73667 communique, specific examples has trade(brand)name チヌピ Application 622 LD, キマソ-Block 944LD, チヌ PVC Application 123 (above チバスペシヤリティケミカ Le ズ society system), ホス PVC Application N30, VP Sanduvor PR-31 (above Network ラリァ Application ト society system) サィヤソ-Block UV 3526 (サィテ Star Network society system) etc.As the stablizer that contains the ammonia based compound that is obstructed, the composition (trade(brand)name チヌピ Application 492, チヌピ Application 494, (the チバスペシヤ Le ティケミカ Le ズ) that have the spy to open to put down in writing in the clear 63-286448 communique.

When using photostabilizer, its consumption is considered from the balance of improving weathering resistance effect and inhibition albefaction, is generally about 0.02-5 weight % in multilayer film, is preferably about 0.1-2 weight %, more preferably about 0.5-2 weight %.Consider that from improving the weathering resistance effect photostabilizer and following UV light absorber are share better.

Anti-frost and anti-fog laminated substance of the present invention can contain at least a UV light absorber.UV light absorber can be an organic compound, also can be mineral compound.It is that UV light absorber, benzoate fibre are that UV light absorber, cyanoacrylate are UV light absorber etc. that spendable organic system UV light absorber example has benzophenone series UV light absorber, benzotriazole.Inorganic is that UV light absorber can contain metal oxides such as cerium oxide or titanium oxide, for example, can use the UV light absorber of commercially available Japanese inorganic chemistry industry system trade(brand)name セリガ-De.

When using UV light absorber, its consumption is considered from the balance of improving effect of weather and inhibition albefaction, in multilayer film integral body, is generally about 0.01-3 weight %, better is about 0.05-1 weight %.

The substrate material of anti-frost and anti-fog laminated substance of the present invention prevents that for reaching the good initial stage purpose of frost mist also can contain anti-frost mist agent.Substrate material contains when preventing the frost mist agent, and its consumption in substrate material is overall, is generally about 0.1-4 weight %, is preferably about 0.5-3 weight %, more preferably about 1.5-3 weight %, and about 2.2-2.8 weight % is especially good.

This anti-frost mist agent at normal temperature (23 ℃), can be a solid, also can be liquid.As the anti-frost mist agent of solid, nonionic surfactant is arranged, and (for example, Sorbitol Powder fatty acid esters such as Sorbitol Powder monostearate, Sorbitol Powder monopalmitate, Sorbitol Powder list mountain Yu's acid esters, Sorbitol Powder list montanate are tensio-active agent; Glycerol fatty acid esters such as glyceryl monolaurate, glycerine monopalmitate, Zerol, two Stearic diglycerides, triglycerin monostearate, triglycerin list montanate are tensio-active agent; Polyoxyethylene glycol such as polyoxyethylene glycol monopalmitate, polyethylene glycol mono stearate are tensio-active agent; The alkylene oxide affixture of alkane phenol; Sorbitol Powder/glycerol condensate and organic acid ester; Polyoxyethylene (2 moles) stearylamide, polyoxyethylene (2 moles) lauryl amine, polyoxyethylene alkyl amine compounds such as polyoxyethylene (4 moles) Stearyl Amine, polyoxyethylene (2 moles) Stearyl Amine monostearate, polyoxyethylene (2 moles) Stearyl Amine SUNSOFT Q-182S, polyoxyethylene (4 moles) Stearyl Amine monostearate, polyoxyethylene (4 moles) Stearyl Amine distearyl acid fat, polyoxyethylene (8 moles) Stearyl Amine monostearate, polyoxyethylene (2 moles) Stearyl Amine list mountain Yu's acid esters, the fatty acid ester of polyoxyethylene alkyl amine compounds such as polyoxyethylene (2 moles) lauric acid amine stearate, the amine such as fatty acid amide of the polyoxyethylene alkyl amine compound of polyoxyethylene (2 moles) stearic amide etc. are tensio-active agent etc.).

As the anti-frost mist agent of liquid, it is fatty acid ester (glyceryl monooleate, two glyceryl monooleates, two glycerine sesquioleate, four glyceryl monooleates, six glyceryl monooleates, four trioleins, six glycerine, five oleic acid esters, four glyceryl monolaurates, six glyceryl monolaurates etc. are for example arranged) and Sorbitol Powder fatty acid ester (for example have sorbitol monooleate, Sorbitol Powder dioleate, sorbityl monododecanoate etc.) that glycerine is arranged.

When cooperating aqueous frost prevention mist agent, its consumption is generally about 0.2-3 weight % in substrate material, be preferably the scope of about 0.5-2 weight %.Containing in substrate material under the normal temperature is the anti-frost and anti-fog laminated substance that liquid is prevented the frost mist agent, can be suppressed at the loss of light perviousness when preserving and sprawling.

Anti-frost and anti-fog laminated substance of the present invention can contain antifogging agent in the substrate material.As spendable antifogging agent, for example have and contain perfluor footpath base, ω-fluorine cpd such as hydrogen fluorocarbon based (particularly fluorine is a tensio-active agent), contain the silicon based compound (particularly silicon is tensio-active agent) of alkylsiloxane base etc.When containing antifogging agent, its consumption is generally about 0.01-3 weight % in substrate material, is preferably about 0.02-1 weight % scope.

Anti-frost and anti-fog laminated substance of the present invention can contain the near infrared ray barrier agent.The anti-frost and anti-fog laminated substance that will contain the near infrared ray barrier agent is during as the multiple material of the quilt in greenhouse, can suppress daytime hot summer weather phase greenhouse temperature inside and reduce.There is the spy (for example to open in the flat 10-193522 communique disclosed organic compound as the near infrared ray barrier agent, nitroso compound and its metal-complexing salt, flower cyanines based compound, the Squarrium based compound, the salt based compound is closed in the coordination of mercapto nickel, the phthalocyanine based compound, three allyl methane series compounds, the imines based compound, the Sanya amine compound, the naphthoquinones based compound, the anthraquinone based compound, aminocompound, the ammonium salt based compound) and mineral compound (for example, carbon black, weisspiessglanz, the stannic oxide of doped indium oxide, belong to periodictable 4A, the metal oxide of 5A or 6A family or carbide, boride), on the outer side of anti-frost and anti-fog laminated substance of the present invention, can form the covered film that contains the near infrared ray barrier agent, as the method that forms covered film, for example there is the coating liquid that to contain near infrared ray barrier agent and water soluble resin tackiness agent to be coated on the anti-frost and anti-fog laminated substance outer side, and carries out the exsiccant method.

Can also in this substrate material film, add the additive such as various stablizers (for example, photostabilizer, oxidation inhibitor etc. such as nickel compound), antistatic agent, lubrication prescription, pigment, fire retardant of the general use except that above-mentioned as required.(with reference to ([Port リマ-additive separates, the other volume of analytical technology ぉょび] (Tanaka ら, Japanese scientific information (strain) are published 1987), [プラスチ Star Network ぉょび go system with the practical brief guide of additive] (back rattan ら, the publication of (strain) chemical industry, 1970)).Each additive can use separately, also can 2 kinds or above share.

Substrate material can be an individual layer, also can be 2 layers for or more than, 2 layers or when above, at least 1 layer is that the resin matrix material of said polyolefins resin is for well.

This resin matrix material by 3 layers or more than when constituting, constitute the total thickness of substrate material two sides outside layer, the 10-90% of total thickness normally, better 20-80%, better 30-70%.When in the resin matrix material interior layer, containing a large amount of above-mentioned rung ray barrier agent, be preferably 10-40%, 15-30% more preferably, on two faces of substrate material, the thickness that constitutes these outside layers can be different.

Resin matrix material is film like or laminar preferably, and for example, common manufacturing process has film blow-moulding process, T die head moulding method etc.In order to obtain the multiwalled substrate material, can use various combination forming methods according to different purposes.For example, when use forms multiwalled film blow-moulding machine and T die head by mold structure,, can obtain different types of multilayer substrate material by making different resins by squeezing out in each mold layer.To the thin slice that makes with the die head moulding method, by tackiness agent or melting resin, will with the film blow-moulding process make film adhered on, obtain the multilayer substrate material.

Anti-frost and anti-fog laminated substance of the present invention requires to have by resin and mineral compound particulate to form, this layered product have top layer A layer with, contain the mineral compound particulate and make principal constituent, with respect to the B layer of substrate material and A layer homonymy.Between the A layer and B layer with respect to the substrate material homonymy, and between B layer and the substrate material, other layer such as tackifier coating or bonding coat can be arranged.Two outermost layers of this layered product can be both the A layer.At this moment, the composition of these two A layers can be identical, also can be different.Between A layer and substrate material, a B layer can be arranged, two or above B layer also can be arranged.When 2 or above B layer were arranged between A layer and substrate material, the composition of these B layers each other can be identical, also can be different.Consider that from the persistence of initial stage frost prevention fog effect and frost prevention fog effect for well, and B layer contact laminating (can carry out surface treatments such as corona treatment, flame treating) for well to the A layer contact laminating on top layer on substrate material on the B layer.

The thickness of anti-frost and anti-fog laminated substance can suitably be selected with different purposes such as the transparency, flexibilities according to mechanical strength.For example, when being used for agricultural installations such as greenhouse, be generally 10-400 μ m, be preferably 30-300 μ m.

Layer structure for it does not have particular restriction, for example, can be by 3 kinds 3 layers, 3 kinds 5 layers, layers such as 4 kinds 5 layers and 5 kinds 5 layers constitute.When anti-frost and anti-fog laminated substance of the present invention is used for agricultural horticultural facility, when on agricultural installations such as greenhouse, being launched into tent usually, cry outerly towards the layer in the facility outside, be internal layer, layer cry middle layer (have sometimes 2 layers or more than) between skin and the internal layer towards the layer of inboard, greenhouse.

The substrate material of anti-frost and anti-fog laminated substance of the present invention considers that from the transparency, flexibility and economy better being at least 1 layer is at 0.935g/cm by above-mentioned density ³Or following new LDPE (film grade), ethylene/alpha-olefin polymer or vinyl acetate content are at the layer of 30 weight % or following ethene-vinyl acetate polymer formation.

At this moment, the thickness of this layer better be the substrate material total thickness 5% or more than, more preferably 10% or more than.

The resin of other resin layer can be different with the cooperation of additive, also can implement dustproof handle, prevent frost mist processing, antifog processing respectively.In addition, consider that from dirt resistance with to the intensity of frictions such as greenhouse band preferably one deck uses above-mentioned fusion flow velocity at least, C _xOr high molecular side branches mean value is lower molecular weight side branches mean value or above ethylene/alpha-olefin polymer, is preferably used on the side relative with the A layer.

The manufacture method of anti-frost and anti-fog laminated substance of the present invention, can be that each is pressed in method on the substrate material layer by layer, for example, the lay-up method of Shi Yonging in the past, methods such as coating (reference: [コ-ティ Application グ mode] former rugged brave work,, the distribution of Maki bookstore in 1979).

When using thermoplastic resin to make substrate material, general because the surface tension great majority of thermoplastic resin are very low, so, for example,, surface treatment is carried out on the surface of substrate material improved surface tension in advance for well on the B course substrate material during lamination.By carrying out following coating during lamination B layer, the wettability that is coated with face from the bag of mineral compound particle dispersion liquid and substrate material will be got well, do not produce defective because of not being stained with, and all high consideration of dry back each layer bond strength, on the lamination substrate material surface tension of B layer be preferably in 36 dyne (dyne)/cm or more than.The capillary upper limit does not have particular restriction, is generally about 60 dyne/cm, is preferably 40-50 (dyne)/cm.

As surface treatment method, methods such as corona treatment, Cement Composite Treated by Plasma, the processing of flame ion body, UV processing, EB (electron beam irradiation) processing are so long as the method for carrying out is all passable usually.Can reach at the surface-tension energy after the processing and implement under the condition of prescribed value to handle.Because the surface-treated effect generally can reduce after after a while, so preferably carry out lamination with methods such as coatings as far as possible apace after surface treatment.Therefore, the most handy machine on-line continuous that connects for the treatment of part and for example coating part is carried out.

Improve the capillary method except carrying out surface treatment, consider, also can on the substrate material surface, with after the coating of tackify paint, use B layer on the coating process lamination more in advance from improving wettability.

So-called above-mentioned coating is after the solution that will be dispersed with the dispersion liquid of mineral compound particulate in the dispersion medium or dissolved hydrophilic resin in solvent applies as coating liquid, to carry out drying again, removes dispersion medium or solvent, cambial method.

For coating, application pattern such as recessed roller mode, dip-coating mode, spraying method are for example arranged.For example, when on blown film, applying, consider, preferably use the tubular film substrate material to carry out coating, can select the whole bag of tricks according to the shape of substrate material from making efficient.

Also can be according to mineral compound particulate and resin, dispersion medium or the solvent of selecting dispersion liquid or solution to use arbitrarily.

Dispersion medium as the mineral compound particle dispersion liquid is used for example has water, methyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, ethylene glycol, dimethylbenzene etc., and their mixed solution.Water, alcohol etc. are polar solvents preferably, consider that with regard to environmental problem and equipment water is good especially.

For example, as hydrophilic resin, have, when for example polyvinyl alcohol, polyose and its derivative etc. being made the dissolved solvent, water, methyl alcohol, Virahol, propyl carbinol, isopropylcarbinol etc. are for example arranged, and their mixed solution, consider that with regard to aspects such as environment, equipment water is good especially.

When forming the B layer with coating, by regulating the mineral compound particulate loading in the mineral compound particle dispersion liquid, reach the amount of per unit area coating dispersion liquid, after the drying, the gravimetric thickness that can obtain stipulating, for example, 0.01-10g/m ²Deng, can suitably set the amount of dispersion liquid according to the area that applies, must be the amount that can evenly apply at least.

For the mineral compound particle dispersion liquid, owing to improve not being stained with property and the ununiformity of screening characteristics with the elimination dispersion liquid, or pay thixotropic purpose to dispersion liquid, also can add above-mentioned various tensio-active agents, organic system ionogen, various clay mineral.When adding clay mineral, its addition is generally the 0.005-3 weight part for 100 weight part dispersion medium, better 0.01-0.5 weight part, more preferably 0.01-0.2 weight part.

When forming the A layer by coating, in the dispersion liquid except that containing resin and mineral compound particulate, also can be the same with the coating of B layer.And can directly the A layer be coated on the B layer with coating method.

After the coating, preferably the formation of each layer is quickened in rapid drying.If not having under the state of complete drying,,, when using anti-frost and anti-fog laminated substance, can cause that A layer and B layer peel off, so bad with overlapping the rolling of anti-frost and anti-fog laminated substance of making by ways such as coilings.

Anti-frost and anti-fog laminated substance of the present invention from consideration easy to use, is preferably made film like or laminar.Its manufacture method can illustration has coating process and obtains the method for laminated film or laminated foil usually, perhaps these methods is used in combination.

When anti-frost and anti-fog laminated substance of the present invention is used for agricultural use, preferably with film or the laminar greenhouse that is used for horticultural facility, tunnel, curtain wall etc.Consider that from the viewpoint that solar ray energy is entered in the facility effectively the transparency such as film is high for well certainly.As the yardstick of the transparency, total transmitance of the light of general using film or thin slice and smog value (diffusion light rate) are weighed, the total transmitance height of light, and the smog value is hanged down the person, film transparent good.

When anti-frost and anti-fog laminated substance of the present invention is used for agricultural use, use the total transmitance of light be 80% or more than, be preferably 85% or more than, 90% or above good especially, and the smog value 40% or below, be preferably in 25% or following person.From the night insulation consideration, preferably above-mentioned ray sees through index 25% or following, from the consideration of growing of agriculture thing, be more preferably 20% or following, 15% or following person especially good.

Anti-frost and anti-fog laminated substance of the present invention except agricultural use, just prevents purpose considerations such as car noise, can also be used as the road light-passing board.When being used for this purposes,, consider, preferably use acrylic resin and polycarbonate-based resins such as polymethylmethacrylate from the transparency, rigidity as substrate material.

Anti-frost and anti-fog laminated substance of the present invention can be used for other various purposes, for example can be used for road sign, the multiple film of quilt that the multiple film of the quilt that automobile exterior panel, dwelling house, buildings outer walls such as electronics Decorative Cover, Marking film, automobile lampshade such as billboard are used, window are used, the thin slice that pastes window, the roof in the anti-frost mist thin slice of anti-frost mist packaging film, bathroom mirror, eye-protection glasses, Glasses used in water, lid shape court, garden etc., the particularly purposes under the high humidity environment in the open air.

Anti-frost and anti-fog laminated substance of the present invention even after prolonged preservation under the hot and humid degree environment, finds also to have long-term good anti-frost mist (the anti-frost mist after the damp and hot preservation) in environment for use.Particularly during by multiple material, brought into play extraordinary anti-frost mist performance as agricultural out of doors.

Anti-frost and anti-fog laminated substance of the present invention, owing to be difficult to damage anti-frost mist layer, so, be difficult to produce bad outward appearance and then keeping rerum natura such as anti-frost mist chronically, and effective especially aspect the purposes of life-time service.

Anti-frost and anti-fog laminated substance of the present invention also can be easy to peel even engage with galvanized sheet that is used for the agricultural greenhouse parts etc., and not injure upper layer and substrate material.

And then, containing on the thermoplastic resin matrix material of ray barrier agent, the layer that contains the anatase-type titanium oxide particulate on the lamination, when being used for the horticultural facility greenhouse, demonstrate good especially anti-frost mist, can improve the transit dose to the effective sunlight of photosynthesis daytime, and then can suppress the radiation cooling from ground night, can improve growing of farm crop effectively.

Embodiments of the invention below are shown, but the present invention is not limited in these embodiment.Test method among the embodiment is as follows.

The adhesion test of filming

With pulling cylinder adhesive tape (glass paper tape) is fitted on the applicator surface of substrate material, make the short lattice-shaped of wide 1.8cm, use the speed of self-registering instrument (Tianjin, island AGS 100, ロ-De セ Le 5kg) again with 300mm/min, on 90 degree directions, peel off adhesive tape, obtain the wide intensity of every 1cm this moment from substrate material.

Anti-frost mist test (1)

With two sides band film is attached on the frame of the vinylformic acid system that 34cm is long, 5cm is wide, test is faced down, in being arranged on the testing laboratory of steady temperature, above the Water Tank with Temp.-controlled, with respect to the horizontal plane be obliquely installed with 15 degree.The condition of testing laboratory's envrionment temperature/Water Tank with Temp.-controlled temperature of this moment is taken as 23 ℃/40 ℃.Observe the water droplet situation on the pellicular front after 2 weeks, judge by following benchmark.But, even △, * evaluation be also included within the viewing duration once state.

Zero: pellicular front is roughly evenly moistening.

△: in the subregion, have water droplet to adhere to.

*: adhere to water droplet on whole, form vaporific in vain.

Anti-frost mist test (2)

With film in 60 ℃, the permanent groove of the constant temperature of 90%RH, carry out 10 days burin-in process after, according to above-mentioned anti-frost mist test method, observe after 1 day～film surface water droplet situation after 2 weeks, press following benchmark evaluation.

Zero: roughly evenly moistening on the sake.

△: adhere to water droplet in the subregion.

*: adhere to water droplet on whole, form vaporific in vain.

Radiation sees through index

Calculate the ray of obtaining 23 ℃ with the method for previous narration and see through index.

The galvanized sheet bond test

Galvanized sheet (article number: APC0.35, CGCCR, F-1041 ヤネ in blue look (urethane) baking; NKK system) on, adhere to water, make it to be bonded on the film A aspect of wide 20mm, at 60 ℃ of stove inner dryings after 3 hours, with self-registering instrument (Tianjin, island AGS 100, ロ-De ヤ Le 5kg), measure the intensity of on 180 ℃ of directions, peeling off with 50mm/min speed.

Each layer of anti-frost mist film cooperates example, and manufacture method is as follows.

A layer material

Resin/mineral compound particle dispersion liquid (1)

The polyvinyl alcohol (polymerization degree 300 with 1 weight %, 80 moles of % of saponification deg, Network ラレ system) aqueous solution is with 96.7 weight % and titanium oxide colloid aqueous dispersions (trade(brand)name STS-01 TiO 2 sol (Detitanium-ore-type) titanium oxide content 30 weight %, particle diameter 7nm, the former テ Network of liquid PH ≈ 1.7 stones ノ system) mixes with 3.3 weight %, obtain resin/mineral compound particulate aqueous dispersions (1).

Resin/mineral compound particle dispersion liquid (2)

With 1 weight % polyvinyl alcohol (polymerization degree 300,80 moles of % of saponification deg; Network ラ Le system) aqueous solution and titanium oxide colloid aqueous dispersions (trade(brand)name: STS-21 TiO 2 sol; Take off the titanium ore type, titanium oxide content 40 weight %, particle diameter 20nm, liquid PH ≈ 8.5, the former テ Network of stone ノ system) mix with 97.5 weight % and 2.5 weight %, obtain resin/mineral compound particulate aqueous dispersions (2).

Resin/mineral compound particle dispersion liquid (3)

1 weight % polyvinyl alcohol (polymerization degree 300, saponification deg: 80 moles of % with 94 weight %; Network ラレ system) aqueous solution and 6 weight % colloidal silicon-dioxide (the density: (trade(brand)name: スノ-テ Star Network ス ZL of aqueous dispersions 2.2g/cc); Solids component 40 weight %; Particle diameter 100nm; Daily output chemical industry system) mixes, obtain resin/mineral compound particulate aqueous dispersions (3).

Resin/mineral compound particle dispersion liquid (4)

1 weight % polyvinyl alcohol water solution (polymerization degree 300,80 moles of % of saponification deg, Network ラレ system) is made resin/mineral compound micropartical aqueous dispersions (4).

B layer material

Mineral compound particle dispersion liquid (1)

For water, add the colloidal aluminum oxide aqueous dispersions (trade(brand)name: alumina sol 520 of 9 weight %; Solids component 20 weight %, particle diameter 20nm; Daily output chemical industry system), colloidal silica aqueous dispersion (the trade(brand)name スノ-テ Star Network ス 20 of 2.4 weight %, solids component 20 weight %, particle diameter 20nm, daily output chemical industry system), the clay mineral of 0.09 weight % (the synthetic スメ Network ィトケニミネ industry of trade(brand)name スメ Network ト Application SA system), be the Sodium octoate of 0.014 weight % as the anionic surfactant, 0.002 the paratoluenesulfonic acid sodium salt of weight % is made the mineral compound particle dispersion liquid (1) of 100 weight %.

Mineral compound particle dispersion liquid (2)

For water, add the colloidal aluminum oxide aqueous dispersions (trade(brand)name: alumina sol 520 of 9 weight %; Solids component 20 weight %, particle diameter 20nm, daily output chemical industry system), the colloidal silica aqueous dispersion (trade(brand)name: スノ-テ Star Network ス 20 of 2.4 weight %, solids component 20 weight %, particle footpath 20nm, daily output chemical industry system), the clay mineral (trade(brand)name: スメ Network ト Application SA of 0.09 weight %; Synthetic スメ Network ィト; ケニミネ industry system), be the Sodium octoate of 0.014 weight % as the anionic surfactant, the paratoluenesulfonic acid sodium salt of 0.002 weight % adds the titanium oxide colloid aqueous dispersions (trade(brand)name: STS-01 of 3.3 weight % again; TiO 2 sol; Detitanium-ore-type; Titanium oxide content 30 weight %, particle diameter 7nm, liquid PH ≈ 1.7; The former テ Network of stone ノ system), make the mineral compound particle dispersion liquid (2) of 100 weight %.

The preparation of substrate material

To ethene-vinyl acetate co-polymer (trade(brand)name: エバテ-ト H2031; vinyl acetate content 19 weight %; the MFR1.5g/10 branch; Sumitomo Chemical system) in; add mineral compound (the trade(brand)name ミズカラ Star Network lithium aluminum complex hydroxide of 12 weight %; water gauge chemical industry system); 0.6 the photostabilizer hindered amine based compound A of weight part (trade(brand)name チヌ PVC Application 622-LD チバスペシヤリティ-ケミカ Le ズ system); 0.2 the hindered amine based compound B of weight part (trade(brand)name キマソ-プ 944-LD チバスペシヤリティ-ケミカ Le ズ system); 0.2 the oxidation inhibitor c of weight % (trade(brand)name ィ Le ガノ Star Network ス 1010; チバスペシヤリティ-ケミカ Le ズ system); make the mixture of 100 weight %; descend mixing after 5 minutes with Banbury at 130 ℃; use the tablets press granulation again; obtain particulate composition, 1. it be decided to be resin combination

Then, in ethene-vinyl acetate co-polymer (trade(brand)name: エバテ-ト D2011, vinyl acetate content 5 weight %, the MFR0.5g/10 branch, Sumitomo Chemical system) in, adds 1. same operation of the oxidation inhibitor C of hindered amine based compound, 0.06 weight % of 0.6 weight % and resin combination, obtain particle, 2. it be decided to be resin combination.

Again in new LDPE (film grade) (trade(brand)name: スミカセ Application F 208, density 0.923g/cm ³, MFR1.5g/10 branch, Sumitomo Chemical system) in, add the hindered amine based compound of 0.6 weight %, the oxidation inhibitor of 0.06 weight %, the UV light absorber D (trade(brand)name: スミソ-Block 130 of 0.28 weight %; Sumitomo Chemical system), the lubrication prescription amine hydroxybenzene of 0.05 weight %, 1. the same with resin combination, obtain particle, 3. it be decided to be resin combination.

Make the thick blown film of 100 μ m (the about 65 μ m in middle layer with 3 layers of blown film forming mill, the about 17.5 μ m of ectonexine), 1. resin combination is done the middle layer, 2. resin combination is made the skin of blowing, 3. resin combination is made the internal layer of blowing, this blown film is cut out to cut make substrate material 1..

The making of anti-frost mist layered product

Corona treatment

Utilize corona treatment, to each substrate material surface handle, make surface energy reach 45 dyne (dyne)/cm or more than.

Coating

With the smart mechanism test of Kang Jing coating machine.Carry out corona treatment with miniature intaglio mode (using miniature gravure roller, oblique line 120 orders), on the substrate material after the processing, coating mineral compound particle dispersion liquid carries out drying, forms the B layer, coating resin and mineral compound particle dispersion liquid carry out drying again, form the A layer.Coating can be carried out on the outside of any blown film pipe (skin).Linear velocity is 5m/min, and dryer temperature is 80 ℃.

Embodiment 1

On the skin of substrate material (1), according to above-mentioned [anti-frost and anti-fog laminated substance making method], form the B layer by mineral compound particle dispersion liquid (1), form the A layer, obtain anti-frost and anti-fog laminated substance by resin/mineral compound particulate aqueous dispersions (1) again.Various tests the results are shown in table 1.Any all very good.

Embodiment 2

Except being formed the A layer by resin/mineral compound particulate aqueous dispersions (2), other is the same with embodiment 1, obtains anti-frost and anti-fog laminated substance.Various test-results are shown in table 1.Any all very good.

Embodiment 3

Except being formed the B layer by mineral compound particle dispersion liquid (2), being formed the A layer by resin/mineral compound particulate aqueous dispersions (3), other is identical with embodiment 1, obtains anti-frost and anti-fog laminated substance.Various test-results are shown in table 1, and are any all very good.The galvanized sheet bond test the results are shown in table 2, the separability result is very good.

Embodiment 4

Except being formed the A layer by resin/mineral compound particulate aqueous dispersions (2), other is the same with embodiment 3, obtains anti-frost and anti-fog laminated substance.Various test-results are shown in table 1.Any all very good.

Comparative example 1

Except being formed the A layer by resin/mineral compound particulate aqueous dispersions (4), other is the same with embodiment 1, obtains anti-frost and anti-fog laminated substance.Various test-results are shown in table 1, and after the damp and hot preservation, anti-frost mist obviously reduces.

Reference example 1

Except using commercially available polyolefin-based resins agricultural film to do the substrate material [Network リ Application テ-ト DX: firmly change plastics system, thick 75 μ m], other is the same with embodiment 1, obtains being applicable to that agricultural is by the anti-good anti-frost and anti-fog laminated substance of frost mist of multiple material.

Reference example 2

Do the sill [エ Off Network リ Application 15: エ Off Network リ-Application システ system dealer shell system, thick 100 μ m] except using commercially available fluorine resin agricultural film, other is the same with embodiment 1, make and be applicable to the agricultural material of being answered, dirt resistance, the anti-good anti-frost and anti-fog laminated substance of frost mist.

Reference example 3

Do the substrate material [シ Network スラィト Network リ-Application: the MKV of Mitsubishi Chemical system, thick 150 μ m] except using commercially available polyester based resin agricultural film, other is identical with embodiment 1, make be applicable to agricultural by multiple material, intensity and the good anti-frost and anti-fog laminated substance of anti-frost mist.

Reference example 4

In the substrate material (1),, adopt commercially available ethene/1-hexene polymkeric substance (trade(brand)name: スミカセ Application E FV 401 density: 0.902g/cm made from metalloscene catalyst as resin combination resin 1. ³, melt index: the 4g/10 branch), as resin material 2. and resin 3., commercially available ethene/1-hexene polymkeric substance (trade(brand)name: スミカセ Application EFV202, density: 0.925g/cm of making in order to metalloscene catalyst ³, melt index: the 1.5g/10 branch), in addition, other is the same, makes substrate material (2).Except using substrate material (2), other is the same with embodiment 1, makes to be applicable to and agriculturally to be answered material, intensity and the good anti-frost and anti-fog laminated substance of anti-frost mist.

Reference example 5

Use the stripper plate of commercially available plexiglass to do to spray with embodiment 1 the same solution outside the substrate material (trade(brand)name: スミペ Star Network ス E, thick 10mm Sumitomo Chemical system), make the anti-frost and anti-fog laminated substance that is suitable for light-passing board.

Table 1

	The adhesion test (g/cm) of filming	Anti-frost mist test	Damp and hot keeping rear defence frost mist test (60 ℃, 90%RH, 10 days keeping backs)				Radiation sees through index (%)
								After 2 days	After 7 days	After 10 days	After 14 days
			Embodiment 1	320	○	○		After 2 days	After 7 days	After 10 days	After 14 days	○	○	○	15
Embodiment 2	320	○	Embodiment 1	320	○	○	○	○	○	○	15	○	○	○	15
Embodiment 2	320	○	Embodiment 3	320	○	○	○	○	○	○	15	○	○	○	15
Embodiment 4	320	○	Embodiment 3	320	○	○	○	○	○	○	15	○	○	○	15
Embodiment 4	320	○	Comparative example 1	310	○	○	○	○	○	○	15	△	×	×	15

Table 2

	The L value	A layer thickness (g/m ²)	B layer thickness (g/m ²)	Mineral compound fraction of particle (weight %) in the layer	Stripping strength (g/20mm)
	The L value	A layer thickness (g/m ²)	B layer thickness (g/m ²)		Stripping strength (g/20mm)	Embodiment 3	2	0.34	0.20	70	26

Claims

1, a kind of anti-frost and anti-fog laminated substance, the top layer A layer of the layered product that it is characterized in that comprising substrate material, forms by resin and mineral compound particulate and with the mineral compound particulate as main component and be positioned at the B layer of above-mentioned A layer the same side.

2, according to the anti-frost and anti-fog laminated substance of record in the claim 1, it is characterized in that resin contained in the A layer is a hydrophilic resin.

3, according to the anti-frost and anti-fog laminated substance of record in the claim 2, it is characterized in that the A layer be dispersion liquid by hydrophilic resin and mineral compound particulate carry out dry forms layer.

4,, it is characterized in that the B layer is to carry out the dry layer that forms by the mineral compound particle dispersion liquid according to the anti-frost and anti-fog laminated substance of record in the claim 1.

5, according to the anti-frost and anti-fog laminated substance of record in the claim 1, it is characterized in that mineral compound particulate contained in the A layer is oxide fine particle and/or hydroxide particulate.

6, according to the anti-frost and anti-fog laminated substance of record in the claim 1, it is characterized in that mineral compound particulate contained in the B layer is oxide fine particle and/or hydroxide particulate.

7, according to the anti-frost and anti-fog laminated substance of record in the claim 1, it is characterized in that mineral compound particulate contained in A layer and/or the B layer is the oxide fine particle and/or the hydroxide particulate of metal.

8, according to the anti-frost and anti-fog laminated substance of record in the claim 7, it is characterized in that metal is at least a kind that selects by in silicon, aluminium, zinc, magnesium, calcium, barium, titanium, zirconium, manganese, iron, cerium, nickel and the tin.

9, the middle according to Claim 8 anti-frost and anti-fog laminated substance of putting down in writing is characterized in that metal is by selecting at least a kind of metal in silicon, aluminium and the titanium.

10, according to the anti-frost and anti-fog laminated substance of record in the claim 1, it is characterized in that mineral compound particulate contained in the B layer is the oxide fine particle of silicon or the oxide fine particle or the hydroxide particulate of hydroxide particulate and aluminium.

11, according to the anti-frost and anti-fog laminated substance of record in the claim 1, it is characterized in that mineral compound particulate contained in A layer and/or the B layer is the anatase-type titanium oxide particulate.

12, according to the anti-frost and anti-fog laminated substance of record in the claim 11, the median size that it is characterized in that the anatase-type titanium oxide particulate is at 10nm or following.

13,, it is characterized in that grain meets sex index E at 500g/20mm or following according to the anti-frost and anti-fog laminated substance of record in the claim 1.

14, according to the anti-frost and anti-fog laminated substance of record in claim 1 or 13, the median size that it is characterized in that mineral compound particulate contained in the A layer is 50～5000nm.

15, according to the anti-frost and anti-fog laminated substance of record in claim 13 or 14, the L value that it is characterized in that following formula definition is greater than 1,

L=(N×R)/S

Wherein R is the median size (m) of institute's inorganic-containing compound particulate in the A layer, and S is the A surface layer (m of anti-frost and anti-fog laminated substance ²), N is the number of institute's inorganic-containing compound particulate in the A layer of per surface area S, is defined as follows formula,

N=V/{(4/3)×π×(R/2) ³}

Wherein, V is mineral compound particulate volume (cc/m in the A layer of per surface area S ²).

16, according to the anti-frost and anti-fog laminated substance of record in the claim 11, it is characterized in that institute's inorganic-containing compound particulate is anatase-type titanium oxide particulate and hydroxide particulate and/or other oxide fine particle except that the anatase-type titanium oxide particulate in the B layer.

17, according to the anti-frost and anti-fog laminated substance of record in the claim 11, it is characterized in that institute's inorganic-containing compound particulate is at least a kind the particulate of selecting by in anatase-type titanium oxide particulate and silicon oxide particle, alumina particulate, zinc oxide fine particles, cerium oxide particulate, zirconium white particulate, silicon hydroxide particulate, aluminum hydroxide particle, zinc hydroxide particulate, cerous hydroxide particulate, zirconium hydroxide particulate and the clay mineral in the B layer.

18, according to the anti-frost and anti-fog laminated substance of record in the claim 11, it is characterized in that mineral compound particulate contained in the B layer is anatase-type titanium oxide particulate and alumina particulate and/or aluminum hydroxide particle and silicon oxide particle and/or silicon hydroxide particulate.

19, according to the anti-frost and anti-fog laminated substance of record in the claim 1, the gravimetric thickness that it is characterized in that the A layer is 0.01-10g/m ²

20, according to the anti-frost and anti-fog laminated substance of record in the claim 1, the gravimetric thickness that it is characterized in that the B layer is 0.01-10g/m ²

21, according to the anti-frost and anti-fog laminated substance of record in the claim 2, it is characterized in that hydrophilic resin is at least a kind that selects by in polyvinyl alcohol, polyose and its derivative.

22,, it is characterized in that the ratio (d2/d1) of the thickness (d2) of the thickness (d1) of A layer and B layer is 0.01-10 according to the anti-frost and anti-fog laminated substance of record in the claim 1.

23,, it is characterized in that the ratio (d2/d1) of the thickness (d2) of the thickness (d1) of A layer and B layer is 0.01-1 according to the anti-frost and anti-fog laminated substance of record in the claim 13.

24, according to the anti-frost and anti-fog laminated substance of record in the claim 1, it is characterized in that substrate material is to be formed by thermoplastic resin.

25, according to the anti-frost and anti-fog laminated substance of record in the claim 24, it is characterized in that thermoplastic resin is at least a kind that selects by in polyolefin-based resins, acrylic resin, polycarbonate-based resin, fluorine resin and the polyester based resin.

26,, it is characterized in that polyolefin-based resins is at least a kind that is selected in 30 weight % or following ethylene/vinyl acetate co-polymer by new LDPE (film grade), ethylene/alpha-olefin co-polymer, vinyl acetate content according to the anti-frost and anti-fog laminated substance of record in the claim 25.

27, according to the anti-frost and anti-fog laminated substance of record in the claim 1, the surface tension that it is characterized in that substrate material 36 dyne/cm or more than.

28,, it is characterized in that substrate material is that the thermoplastic resin composition who contains the radiation barrier agent by 100 parts by weight of thermoplastic resin and 0.03-25 weight part is formed according to the anti-frost and anti-fog laminated substance of record in the claim 24.

29, according to the anti-frost and anti-fog laminated substance of record in the claim 28, it is characterized in that the radiation barrier agent is an infrared absorbent.

30, according to the anti-frost and anti-fog laminated substance of record in the claim 29, it is characterized in that infrared absorbent is the mineral compound that contains by at least a element of selecting among Li, Al, Si, Mg, Ca, the Zn.

31, according to the anti-frost and anti-fog laminated substance of record in the claim 30, it is characterized in that infrared absorbent is at least a mineral compound of selecting from the mineral compound of formula I～(V) expression down,

Paste P38 (I)

(in the formula, M ²⁺Expression divalent metal ion, A ^N-Expression n valency negatively charged ion, x and m satisfy the condition of 0＜x＜0.5 and 0≤m≤2)

Paste P38 (II)

(in the formula, A ^N-The negatively charged ion of expression n valency, m satisfies the condition of 0≤m≤3).

Paste P39 (III)

(in the formula, M ²⁺Metal ion, m, x and the y of expression divalent satisfy the condition of 0≤m＜5,0≤x＜1,2≤y≤4),

Paste P39 (IV)

(in the formula, M ²⁺Expression divalent metal ion, A ^N-Negatively charged ion, m and the x of expression n valency satisfy the condition of 0≤m＜5 and 0.01≤x＜1),

Paste P39 (V)

(in the formula, x is a carbonate, and M is basic metal or alkaline-earth metal ions, and P is the valence mumber of metal ions M, m, n and k satisfy the condition of 0.3≤m≤1,0.3≤n≤2,0.5≤k≤4).

32, according to the anti-frost and anti-fog laminated substance of record in the claim 30, it is characterized in that infrared absorbent is silicon oxide and/or pure aluminium silicate.

33,, it is characterized in that the thermoplastic resin composition also contains at least a kind in photostabilizer, UV light absorber, antifogging agent and the anti-frost mist agent according to the anti-frost and anti-fog laminated substance of record in the claim 28.

34,, it is characterized in that the thermoplastic resin composition forms by 100 parts by weight of thermoplastic resin with by the reagent place that selects a kind in 0.02-5 weight part photostabilizer, 0.01-3 weight part UV light absorber, 0.01-3 weight part antifogging agent, the anti-frost mist agent of 0.1-4 weight part at least according to the anti-frost and anti-fog laminated substance of record in the claim 33.

35,, it is characterized in that substrate material is formed by 2 layers or above layer according to the anti-frost and anti-fog laminated substance of record in claim 1 or 24.

36,, it is characterized in that substrate material contains the layer that one deck is formed by polyolefin-based resins at least according to the anti-frost and anti-fog laminated substance of record in the claim 35.

37, according to the anti-frost and anti-fog laminated substance of record in the claim 36, it is characterized in that polyolefin-based resins is that new LDPE (film grade), ethylene/alpha-olefin co-polymer or vinyl acetate content are at 30 weight % or following ethene-vinyl acetate co-polymer.

38,, it is characterized in that layered product is laminar or film like according to the anti-frost and anti-fog laminated substance of each record among the claim 1-37.

39, among the claim 1-38 anti-frost and anti-fog laminated substance of each record as the purposes of agricultural film.

40, the purposes of the agricultural film that the anti-frost and anti-fog laminated substance of record is used as horticultural facility in the claim 38.

41, among the claim 1-38 anti-frost and anti-fog laminated substance of each record as the purposes of light-passing board.

42, in the claim 1,24 and 38 the anti-frost mist of each record press layer by layer body be used for electricity decorations with cover, sign film, automobile exterior panel, dwelling house, buildings outer wall with by multiple film, window with any purposes of being pasted thin slice, anti-frost mist packaging film, the anti-frost mist sheet of mirror by multiple film, window.

43, a kind of anti-frost and anti-fog laminated substance, it is characterized in that above-mentioned mineral compound particulate is that anatase-type titanium oxide particulate, substrate material are that the thermoplastic resin composition that the ray barrier agent by 100 parts by weight of thermoplastic resin and 0.03-25 weight part forms is formed by being formed with the layer and the substrate material of mineral compound particulate by main component.

44, according to the anti-frost and anti-fog laminated substance of record in the claim 43, it is characterized in that other mineral compound particulate except that the anatase-type titanium oxide particulate is hydroxide particulate and/or oxide fine particle.

45, according to the anti-frost and anti-fog laminated substance of record in the claim 43, it is characterized in that other mineral compound particulate except that the anatase-type titanium oxide particulate is at least a kind of particulate selecting by in alumina particulate, zinc oxide fine particles, cerium oxide particulate, zirconium white particulate, aluminum hydroxide particle, zinc hydroxide particulate, cerous hydroxide particulate, zirconium hydroxide particulate and the clay mineral.

46, according to the anti-frost and anti-fog laminated substance of record in the claim 43, it is characterized in that the mineral compound particulate except that the anatase-type titanium oxide particulate is the oxide fine particle and/or the hydroxide particulate of silicon.

47, according to the anti-frost and anti-fog laminated substance of record in the claim 43, it is characterized in that the mineral compound particulate except that the anatase-type titanium oxide particulate is the oxide fine particle of aluminium and/or the oxide fine particle and/or the hydroxide particulate of hydroxide particulate and silicon.

48,, it is characterized in that the thermoplastic resin composition also contains at least a kind in photostabilizer, UV light absorber, antifogging agent, the anti-frost mist agent according to the anti-frost and anti-fog laminated substance of each record among the claim 43-47.

49, according to the anti-frost and anti-fog laminated substance of each record among the claim 43-48, it is characterized in that substrate material be by two layers or above contain at least one deck by polyolefin-based resins form the layer.

50, among the claim 44-49 anti-frost and anti-fog laminated substance of each record as the purposes of agricultural film.