JPH10119200A - Agricultural vinyl chloride resin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an agricultural vinyl chloride resin film having excellent dust-proofness, defogging properties and persistence of them. SOLUTION: The agricultural vinyl chloride resin film comprises a film originated from fluororesin and formed on one surface of a base film, and a film originated from defogging composition containing silica sol and/or alumina sol and thermoplastic resin and formed on the other surface. In this case, the base film is blended with surfactant containing 1,5-sorbitan fatty acid ester (A) having 10 to 15 fatty acid carbons and its propylene oxide adduct (B).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin film for agricultural use which has excellent dustproofing and antifogging properties, and which maintains these excellent performances for a long period of time.

[0002]

2. Description of the Related Art In recent years, farmers who cultivate useful plants have widely adopted a method of forcing or suppressing cultivation of useful plants in a house or a tunnel for the purpose of improving profitability. As a coating material for a house or a tunnel, a polyethylene film, an ethylene-vinyl acetate copolymer film, a polyester film, a vinyl chloride resin film, glass and the like are used, and among them, a vinyl chloride resin film has light transmittance, It is widely used because it is the best in terms of heat retention, mechanical strength, durability, etc. The properties required for house or tunnel covering materials are: the outer surface is not stained for a long period of time, has excellent dustproofing, maintains good light transmittance, promotes the growth of cultivated crops, It is required that the water condensed on the surface be allowed to flow down along the film surface without falling onto the cultivated crops, that is, to have excellent so-called "anti-fog properties".

As a method for imparting dust resistance, a method of applying an acrylic resin to the surface of a vinyl chloride resin film, a method of applying a mixture of a fluorine resin and an acrylic resin, and a method of improving the anti-fogging property are provided. A method of kneading a so-called antifogging agent such as glycerin fatty acid ester and sorbitan fatty acid ester into a base film has been widely used. Recently, as described in, for example, JP-A-3-51121, a dustproof coating derived from a fluororesin is formed on one surface of a base film, and a coating derived from an antifogging agent composition is formed on the other surface. Method and Japanese Patent Laid-Open No. 5-24160
As disclosed in Japanese Patent Application Laid-Open Publication No. H11-260, there has been proposed a method in which a dust-proof coating has a composition comprising a fluorine-containing acrylic polymer, an acrylic polymer, and vinylidene fluoride.

[0004]

However, in these methods, in general, in the ventilation work by winding the film, since the winding part is in a wet environment, it is necessary to perform the ventilation work for a long period of time. In addition, the dust-proof coating and the anti-fogging coating are fused, the anti-fogging coating peels off, the anti-fogging property is not exhibited, and the dust-proofing property is not sufficient.

[0005]

Under such a background, the present inventors do not fuse the dust-proof coating and the anti-fog coating even if the film is used for a house coating or the like after a long period of ventilation work. The present inventors have made intensive studies to provide a vinyl chloride resin film for agricultural use which is excellent in dustproofness, antifogging properties and durability thereof, and as a result, the present invention has been completed.

Therefore, the gist of the present invention is as follows.
Composition comprising a fluorine-containing acrylic polymer (a), an acrylic polymer substantially free of fluorine (b), and a vinylidene fluoride resin (c) on one surface of a base film made of a vinyl chloride resin A film derived from an antifogging agent composition containing a silica sol and / or an alumina sol and a thermoplastic resin is formed on another surface of the base film on the other side of the base film. A vinyl chloride-based agricultural material, characterized in that a surfactant comprising a 1,5-sorbitan fatty acid ester having 10 to 15 fatty acid carbon atoms (A) and a propylene oxide adduct thereof (B) is blended in the base film. Exists in resin film.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. I. Base Film The vinyl chloride resin used in the present invention refers to a vinyl chloride homopolymer or a copolymer of vinyl chloride and another monomer copolymerizable therewith. Other monomers copolymerizable with the vinyl chloride monomer include, for example, vinyl esters such as vinyl acetate, vinyl propionate, and vinyl laurate; and acrylic esters such as methyl acrylate, ethyl acrylate, and butyl acrylate. Methacrylates such as methyl methacrylate and ethyl methacrylate, maleic esters such as dibutyl maleate and diethyl maleate, fumaric esters such as dibutyl fumarate and diethyl fumarate, vinyl methyl ether, vinyl butyl ether and vinyl octyl Vinyl ethers such as ether, acrylonitrile, vinyl cyanides such as methacrylonitrile, ethylene, propylene, α-olefins such as styrene, vinylidene chloride,
Vinylidene halide or vinyl halides other than vinyl chloride such as vinyl bromide and the like, and polyfunctional monomers such as diallyl phthalate and ethylene glycol dimethacrylate, and of course, these monomers are those described above. It is not limited. These monomers are used in an amount of usually 30 parts by weight or less, preferably 20 parts by weight, based on the vinyl chloride monomer.
It is used in a proportion of not more than part by weight, but there is no particular limitation. These vinyl chloride resins may be produced by any of conventionally known production methods such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, and a bulk polymerization method.

In the present invention, the fatty acid has 10 to 1 carbon atoms.
5, a surfactant comprising 1,5-sorbitan fatty acid ester (A) and its propylene oxide adduct (B) is blended in a base film. As the component (B), those represented by the following structural formula are preferable. N in the structural formula is 10 to
It is an integer of 15.

Embedded image

The surfactant comprising the component (A) and the component (B) may be used alone or in combination of two or more.
Component (A) and component (B) in the surfactant are present in an amount of 0.2 to 0.8 mol, preferably 0.4 to 0.8 mol per mol of component (A).
A proportion of 0.6 mol is preferred. If it is less than 0.2, the adhesion between the anti-fogging coating and the base film is poor, and if it is more than 0.8, the transparency is poor and it is easy to blow out. The preferred range of the compounding amount is 0.1 to 5.0 parts by weight, particularly 0.5 to 3.0 parts by weight, per 100 parts by weight of the vinyl chloride resin.
Parts by weight. If the amount is less than 0.1 part by weight, the adhesion between the antifogging film and the base film is not sufficient, and the antifogging effect and the dustproof effect cannot be sufficiently obtained. On the other hand, if the blending amount is more than 5 parts by weight, the transparency of the film is extremely deteriorated, which is not preferable.

The vinyl chloride resin film for agricultural use according to the present invention contains a plasticizer, usually about 20 to 60 parts by weight, per 100 parts by weight of the base resin in order to impart excellent flexibility and mechanical strength. I do. As the plasticizer, for example,
Phthalic acid derivatives, isophthalic acid derivatives, adipic acid derivatives, maleic acid derivatives, citric acid derivatives, itaconic acid derivatives, oleic acid derivatives, ricinoleic acid derivatives, other tricresyl phosphates, epoxidized soybean oil, epoxy resin plasticizers, etc. can give. Further, in order to impart flexibility to the resin film, the resin film is not limited to the above-described plasticizer, and for example, a thermoplastic polyurethane resin, polyvinyl acetate, or the like can be used.

In the agricultural film of the present invention, if necessary, additives for resins, such as antifoggants, ultraviolet absorbers, light stabilizers, antifog agents, antioxidants, lubricants, heat stabilizers, pigments, A coloring agent such as a dye, an inorganic substance, an antistatic agent and the like can be added in usual amounts. As the ultraviolet absorber, for example, benzotriazole, benzoate, benzophenone,
Ultraviolet absorbers such as cyanoacrylate type and phenyl salicylate type are exemplified. Among them, a benzophenone-based ultraviolet absorber and / or a benzotriazole-based ultraviolet absorber are particularly preferred.

As the light stabilizer, there can be used various compounds usually compounded in agricultural vinyl chloride films. Specifically, for example, 4-acetoxy-2, 2, 6,
6-tetramethylpiperidine, bis (2,2,6,6-
Hindered amine compounds such as tetramethyl-4-piperidyl) adipate and tris (2,2,6,6-tetramethyl-4-piperidyl) benzene-1,3,5-tricarboxylate.

Examples of the antifog include fluorine-based surfactants. More specifically, some or all of the surfactants are replaced with F instead of H bonded to C of the hydrophobic group of ordinary surfactants. Surfactants, especially surfactants containing perfluoroalkyl or perfluoroalkenyl groups.

As the antioxidant, 2,6-di-ter
t-butyl-4-methylphenol, 2,2′-methylenebis (6-tert-butyl-4-ethylphenol), dilaurylthiodipropionate, and the like. Examples of lubricants or heat stabilizers include polyethylene wax, liquid paraffin, bisamide, stearic acid, zinc stearate, aliphatic alcohol, calcium stearate, barium stearate, barium ricinoleate, dibutyltin dilaurate, dibutyltin dimaleate, and organic phosphoric acid Examples include metal salts, organic phosphite compounds, phenols, β-diketone compounds, and the like.

Examples of the colorant include phthalocyanine blue, phthalocyanine green, Hansa Yellow, Alizarin Lake, titanium oxide, zinc white, ultramarine, permanent red, quinacridone, carbon black and the like. Examples of the inorganic substance include oxides, hydroxides, carbonates, silicates and the like of calcium, magnesium, aluminum and the like, and composites thereof. These resin additives have a normal content, for example, the synthetic resin base material 1
It can be blended in an amount of 10 parts by weight or less per 100 parts by weight.

In order to mix the resin additives with the vinyl chloride resin, the respective required amounts are weighed, and a ribbon blender, a Banbury mixer, a super mixer and other conventionally known compounding machines and mixers may be used. In order to form the resin composition thus obtained into a film, a method known per se, for example, a melt extrusion molding method (including a T-die method and an inflation method), a calendar molding method, a solution casting method, and the like. May be used according to the conventionally known method. The thickness of the film is preferably in the range of 0.01 to 0.3 mm, preferably in the range of 0.04 to 0.25 mm.

II. Dustproof coating 1. Fluorinated acrylic polymer (a) In the present invention, the fluorinated acrylic copolymer (a) is a copolymer of an acrylic monomer and a perfluoroalkyl group-containing acrylic monomer. 1-1. Acrylic monomer The acrylic monomer refers to alkyl esters of acrylic acid or methacrylic acid. Specific examples of the alkyl esters of acrylic acid or methacrylic acid include methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate,
n- butyl acrylate, iso- butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, dodecyl acrylate, tridecyl acrylate, alkyl esters of C ₁ -C ₂₂ acrylic acids such as stearyl acrylate, methyl methacrylate, Ethyl methacrylate,
n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, cyclohexyl methacrylate, 2-
Ethylhexyl methacrylate, decyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, alkyl esters of C ₁ -C ₂₂ methacrylic acid such as stearyl methacrylate, and the like.

The above acrylic monomers are each independently
Alternatively, they can be used as a mixture. Further, these acrylic monomers may be used together with other copolymerizable monomers. Such other monomers include, for example, α, β-unsaturated carboxylic acid compounds containing one or more carboxyl groups in the molecule, such as acrylic acid, methacrylic acid, itaconic acid, and maleic acid. , Aconitic acid, crotonic acid and the like. Further, for example, styrene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, acrylamide, methacrylamide, n-butoxyacrylamide, n-butoxymethacrylamide and the like can also be used.

1-2. Perfluoroalkyl group-containing acrylic monomer The perfluoroalkyl group-containing acrylic monomer is an ester of acrylic acid or methacrylic acid having a perfluoroalkyl group.
2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl acrylate, 2,2,3,3-
Tetrafluoropropyl methacrylate, 2,2,3
3,3-pentafluoropropyl acrylate, 2,
2,3,3,3-pentafluoropropyl methacrylate, 1-trifluoromethyl-2,2,2-trifluoroethyl acrylate, 1-trifluoromethyl-2,
2,2-trifluoroethyl methacrylate, 2,2
3,3,4,4,5,5-octafluoropentyl acrylate, 2,2,3,3,4,4,5,5-octafluoropentyl methacrylate, 2,2,3,3,4
4-hexafluorobutyl acrylate, 2,2,3
3,4,4-hexafluorobutyl methacrylate, 2
-Perfluorooctylethyl acrylate, 2-perfluorooctyl methacrylate, 2-perfluorononylethyl acrylate, 2-perfluorononylethyl methacrylate and the like. These may be used alone or in combination of two or more.

1-3. In the compounding polymer (a), the polymerization ratio of the acrylic monomer and the perfluoroalkyl group-containing acrylic monomer is preferably 20 to 99% by weight in the former case. If the amount of the acrylic monomer is less than this range, the adhesion of the formed coating to the base film is not sufficient, and if it is more than this range, the transparency is poor. A prescribed amount of an acrylic monomer and a perfluoroalkyl group-containing acrylic monomer are blended and charged together with an organic solvent into a polymerization vessel, and a polymerization initiator and, if necessary, a molecular weight regulator are added, and the mixture is heated with stirring. Polymerizes. Polymerization is generally known methods, for example, suspension polymerization method,
A solution polymerization method or the like is employed. In this case, examples of the polymerization initiator that can be used include a radical generation catalyst such as α, α-azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, and the like. As the molecular weight regulator, butyl mercaptan, n- Dodecyl mercaptan, tert-dodecyl mercaptan, β-mercaptoethanol and the like.

The organic solvent used for the polymerization includes methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol.
Alcohols such as butanol, n-amyl alcohol, isoamyl alcohol, tert-amyl alcohol, n-hexyl alcohol, and cyclohexanol; aromatic hydrocarbons such as benzene, toluene and xylene; and acetates such as ethyl acetate and butyl acetate. , Acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isobutyl ketone, diethyl ketone, 2-hexanone,
There are ketones such as 3-hexanone, di-n-propyl ketone, diisopropyl ketone, di-n-amyl ketone and cyclohexanone, and tetrahydrofuran, and these can be used alone or in combination of two or more.

2. Acrylic polymer (b) The acrylic polymer (b) substantially containing no fluorine is a polymer mainly containing alkyl esters of acrylic acid or methacrylic acid described in 1-1, Obtained by a polymerization method.

3. Vinylidene fluoride resin (c) Vinylidene fluoride resin (c) is a homopolymer of vinylidene fluoride or a copolymer containing no vinylidene fluoride and other fluorine-containing unsaturated monomers and / or fluorine. Copolymers with possible monomers, as well as polymers in which some of these polymers have been modified or modified, are also included. One or more of these vinylidene fluoride resins can be used. In addition, other fluorine-containing resins, for example, tetrafluoroethylene, chlorotrifluoroethylene,
It may be used by mixing with fluoroethylene or the like.

4. Formation of Dustproof Coating The mixing ratio of the fluorine-containing acrylic polymer (a), the acrylic polymer (b) containing substantially no fluorine, and the vinylidene fluoride resin (c) is when a + b + c is 100 parts by weight. (A) 3 to 50 parts by weight, (b) 2 to 40 parts by weight, and (c) 10 to 95 parts by weight. If the ratio of the polymer (a) to the resin (c) is too small, the transparency of the formed film is not sufficient. Further, the polymer (b) with respect to the resin (c)
Is too small, the adhesion of the formed coating to the surface of the base film is poor, and the coating is easily peeled off, which is not preferable. On the other hand, the polymer (a) or the resin (c) for the resin (c)
If the proportion of the polymer (b) is too large, the effect on the migration inhibitor such as a plasticizer and the stain resistance of the formed film is insufficient, which is not preferable. In the coating composition, in addition to these components, auxiliary components such as antioxidants, neutralizers, ultraviolet absorbers, light stabilizers, antistatic agents, pigments, dyes, foaming agents,
It can be blended with a lubricant or the like, and can be used after being dispersed and / or dissolved in an organic solvent.

Examples of the organic solvent include heptane and cyclohexane as aliphatic hydrocarbons, benzene, toluene, xylene and the like as aromatic hydrocarbons, methanol, ethanol, isopropyl alcohol, polyoxyethylene glycol and the like as alcohols. Hydrogen such as chloroform, tetrachloride hydrocarbon, and chlorobenzene; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; esters such as methyl acetate, allyl acetate and ethyl stearate; amines such as trimethylamine, diphenylamine and hexamethylene diamine , Other dimethylformamide, dimethylacetamide, dioxane, diethyl ether, diethylenedithioglycol, diacetone alcohol, benzonit Le, there are dimethyl sulfoxide and the like, which can be used singly or in combination of two or more thereof.

In order to form a coating on the surface of the vinyl chloride resin film with the above coating composition, various known methods are applied depending on the shape of the molded article. For example, when forming a film in a solution state, such as doctor blade coating, gravure roll coating, air knife coating, reverse roll coating, dip coating, curtain roll coating, spray coating, rod coating, etc. An application method is used. When the coating composition is formed as a single coating without being in a solution state, coextrusion, extrusion coating, extrusion lamination, and lamination are used. As a method of forming a film, as a method of drying a solvent when using a coating method, for example, there are an air drying method, a hot air drying method, an infrared drying method, a far infrared drying method, and the like. Hot air drying is advantageous. The temperature condition in this case is in the range of 50 to 150 ° C., and the time is 1
It is better to choose between 0 seconds and 15 minutes.

In the present invention, the thickness of the film formed on the surface of the base film is 1/10 of the thickness of the base film.
It is preferred that: If the thickness of the coating is more than 1/10 of the thickness of the base film, there is a difference in flexibility between the base film and the coating, so that the coating is liable to peel off from the base film and the like. Occurs, and a phenomenon that the strength of the base film is reduced occurs, which is not preferable. Before applying the coating composition, the surface of the soft vinyl chloride-based resin film is previously washed with alcohol or water, plasma discharge treatment, or corona discharge treatment, or undercoated with another paint or primer. May be performed beforehand.

III. Antifogging Coating On the other side of the base film, a coating derived from an antifogging composition containing silica sol and / or alumina sol and a thermoplastic resin is formed. The average particle size of the silica sol and / or the alumina sol is preferably in the range of 5 to 100 mμ. When the average particle diameter exceeds 100 μm, the coating film is white and easily devitrified, and when the average particle diameter is less than 5 μm, the stability of the anti-fogging composition is unfavorably lacking. These may be used alone or in combination. When used alone or in combination of two or more, two or more kinds having different average particle diameters may be used in combination. When both are combined, it is preferable that the weight ratio of silica sol / alumina sol is 95-5 / 5-95 (100 as a whole).

The alumina sol may be a commercially available product itself or an aqueous sol obtained by dispersing a commercially available alumina powder in water. Alumina sol exhibits a so-called thixotropic property in which the viscosity of the dispersion rapidly increases when water is to be dispersed in water at a high concentration, and it is difficult to obtain a homogeneous dispersion, but when a medium shearing internal stirrer such as a colloid mill is used. , A homogeneous dispersion can be obtained. Further, when silica sol is mixed with this dispersion, the viscosity of the dispersion can be reduced. In many cases, the silica sol has a negatively charged particle surface, but when used in combination with alumina sol, it is not preferable to use a negatively charged one. This is because when the silica sol and the alumina sol are mixed, the mixed dispersion rapidly agglomerates, gels, and causes poor dispersion. Therefore, it is preferable that the colloidal silica has a positively charged particle surface.

The thermoplastic resin used as a binder component includes acrylic resin, vinyl chloride-vinyl acetate resin, polyethylene resin, vinyl chloride resin, vinylidene chloride resin, polyurethane resin, polycarbonate resin, styrene resin. Resins, vinyl acetate resins, unsaturated polyester resins, cellulose ethers and the like can be mentioned, and hydrophobic acrylic resins are preferred in view of the water resistance of the antifogging film and the durability of the antifogging film. These may be used alone or in combination of two or more.

Examples of the hydrophobic acrylic resin include at least 70% by weight of acrylic acid or methacrylic acid alkyl esters (hereinafter referred to as (meth) acrylic acid alkyl esters) or (meth) acrylic acid. A mixture of monomers of alkyl esters and alkenylbenzenes and 0 to 30% by weight of copolymerizable α,
A polymer or copolymer obtained by polymerizing a β-ethylenically unsaturated monomer with ordinary polymerization conditions, for example, in the presence of a surfactant, is preferred.

As the polymerization method, one or two kinds of conventionally known emulsifiers such as anionic surfactants, cationic surfactants and nonionic surfactants can be used. In the presence of the above, it can be obtained by a method of emulsion polymerization in an aqueous medium, a method of polymerization using a reactive emulsifier, a method of polymerization based on the oligosoap theory without containing an emulsifier, and the like. In the case of a polymerization method in the presence of an emulsifier, these emulsifiers are used in a range of 0.1 to 10% by weight based on the total amount of charged monomers. Outside this range, it is difficult to control the polymerization rate, and the dispersion stability of the synthesized resin is poor.

The silica sol contained in the antifogging agent composition and / or
Alternatively, the amount of the alumina sol is preferably in the range of 0.5 to 40 times that of the thermoplastic resin in terms of solid content weight ratio. If it exceeds 40 times, not only does the anti-fogging effect not increase in proportion to the blending amount, but also a phenomenon occurs in which the coating film formed after application becomes cloudy and the light transmittance decreases. Further, the coating film tends to be rough and brittle. on the other hand,
When it is less than 0.5 times, it is difficult to exhibit a sufficient anti-fog effect.

The anti-fogging agent composition may be used in combination with a crosslinkable compound for crosslinking a thermoplastic resin. By doing so, the water resistance of the anti-fog coating can be improved. The amount of the crosslinkable compound used is 0.1% based on the solid content of the thermoplastic resin.
The range is preferably from 30 to 30% by weight, particularly preferably from 0.5 to 10% by weight. Further, the antifog composition may be mixed with an antifoaming agent, a lubricant, an antistatic agent, and other various additives as required. Thus, the antifogging agent composition is usually used in a liquid form. The liquid dispersion medium includes an affinity or water-miscible solvent containing water, and water: monohydric alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol: ethylene glycol, diethylene glycol,
Polyhydric alcohols such as glycerin; cyclic alcohols such as benzyl alcohol; cellosolve acetates: ketones; These may be used alone or in combination, but are determined in consideration of the dispersion stability of the anti-fogging agent composition to be used, the wettability after being applied to the film surface, the difficulty of removing the liquid dispersion medium, and the economic efficiency. Is preferred.

Further, the film of the antifogging agent composition formed on the surface of the base film, as a coating weight of solids, generally 0.01 to 10 g / m ^2, particularly from 0.1-5 g / m ² It is preferred that In order to form a film of the antifogging agent composition on the surface of the substrate film, a solution or dispersion of each composition is generally coated with a doctor blade coating method, a roll coating method, a dip coating method, a spray coating method, a rod coating method, a bar coating method. A coating method known per se, such as a coating method, a knife coating method, and a brush coating method, may be employed, and drying may be performed after the coating. The drying method after the application may be any of natural drying and forced drying, and when the forced drying method is adopted, it is usually dried in a temperature range of 50 to 250 ° C, preferably 70 to 200 ° C. Good. Any appropriate method such as a hot-air drying method, an infrared drying method, or a far-infrared drying method may be used for the heat drying, and the hot-air drying method is advantageous in consideration of the drying speed and stability.

When the adhesiveness between the base film and the coating derived from the coating composition is not sufficient, the surface of the base film is washed with alcohol or water in advance, or subjected to plasma discharge treatment or corona discharge treatment. Alternatively, a pretreatment such as undercoating with another paint or primer may be performed. When actually using the agricultural polyvinyl chloride-based resin film according to the present invention, it is preferable that the side provided with the anti-fogging film is stretched so as to be inside a house or a tunnel.

[0037]

According to the agricultural vinyl chloride resin film of the present invention, a specific sorbitan ester surfactant is blended in the base resin, and the dust-proof coating and the anti-fog provided on the base material surface. Since the dust-proofing property, the anti-fogging property, and the sustainability thereof are remarkably improved by the synergistic effect of the water-soluble coating, the utility value as the agricultural coating material is extremely high.

[0038]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. Examples 1 to 7, Comparative Examples 1 to 5 (1) Preparation of base film Polyvinyl chloride (degree of polymerization = 1300) 100 parts by weight dioctyl phthalate 50 tricresyl phosphite 3 epoxy resin 3 Ba-Zn liquid Stabilizer 2 Ba-Zn powder stabilizer 1 Barium stearate 0.2 Zinc stearate 0.4 Benzophenone ultraviolet absorber 0.5 The surfactant was blended and mixed with a super mixer. The mixture is supplied to a calender molding machine heated to 180 ° C.
It was formed into a film by a conventional method to produce a film having a thickness of 0.15 mm.

[0039]

[Table 1]

(2) Preparation of Dustproof Coating Preparation of Fluorine-Containing Acrylic Copolymer (a) In a reactor equipped with a thermometer, a stirrer, a reflux condenser and a nozzle for adding raw materials, 70 parts by weight of methyl ethyl ketone, 30 parts by weight of toluene, 1.0 part by weight of benzoyl peroxide and 100 parts by weight of a mixture of the respective monomers shown in Table 1 were charged, and the mixture was stirred at 80 ° C. for 3 hours at 80 ° C. for 0.5 hour while stirring in a nitrogen gas stream. About 3 parts by weight
Continuously at the same temperature for a period of time, resins 1 and 2, which are fluorine-containing acrylic polymers shown in Table 2, were obtained.

In the same reactor as in the preparation of the acrylic polymer (b), 70 parts by weight of methyl ethyl ketone,
30 parts by weight of toluene, 1.0 part by weight of benzoyl peroxide and 100 parts by weight of a mixture of the respective monomers shown in Table 1 were charged, and the mixture was further peroxide-treated at 70 ° C. for 3 hours while stirring in a nitrogen gas stream. After adding 0.5 parts by weight of benzoyl, the reaction was
Continuously at the same temperature for a time, resins 3 and 4 as acrylic polymers shown in Table 2 were obtained.

[0042]

[Table 2]

Formation of Dust-Proof Coating Fluorine-containing acrylic polymer (a) and acrylic polymer (b) of the kind and weight ratio (effective component ratio) shown in Table 3 and commercially available vinylidene fluoride-based The resin (c) was blended, and methyl ethyl ketone was added thereto so that the solid content became 20% by weight, to obtain a dustproof composition. On one surface of the base film prepared in (1), apply each dustproof coating composition to # 5
Each was applied using a bar coater. The applied film was kept in an oven at 130 ° C. for 1 minute to evaporate the solvent. The amount of the coating on each of the obtained films was about 3 g /
m ² . The components (c), Kainer ADS, Kainer 7201 and Neoflon VP-850 are as follows. Kainer ADS: Vinylidene fluoride / 4-tetrafluoroethylene / 6-fluoropropylene copolymer manufactured by Penwold Corporation USA Kynar 7201: Vinylidene fluoride / 4-tetrafluoroethylene copolymer manufactured by Penwald Corporation USA NEOFLON VP-850: Daikin Industries Vinylidene fluoride resin

[0044]

[Table 3]

(3) Anti-fogging coating A silica anti-fogging composition was obtained by blending silica sol and / or alumina sol of the type and amount shown in Table 4, a thermoplastic resin, a crosslinking agent and a liquid dispersion medium. On one surface of the substrate film on which the dustproof coating was formed in (2), the above antifogging agent composition was # 5
Each anti-fog coating was applied using a bar coater. The applied film was kept in an oven at 80 ° C. for 1 minute to evaporate the liquid dispersion medium. The amount of the coating on each of the obtained films was about 1 g / m ² .

[0046]

[Table 4]

The trade names in Table 4 are as follows. Cataloid SI-30, Cataloid SI-80P (registered trademark): water dispersion type colloidal silica manufactured by Catalyst Chemical Industry Co., Ltd. OSCAL-1432 (registered trademark): solution dispersion type colloidal silica manufactured by Catalyst Chemical Industry Co., Ltd. Alumina sol 520: Nissan Water-dispersible alumina sol, Kayacryl Resin H-300 (registered trademark), manufactured by Nippon Kayaku Kogyo Co., Ltd. Acrylic emulsion Dianal BR-101 (registered trademark), manufactured by Mitsubishi Rayon Co., Ltd., thermoplastic acrylic Resin Metroose 65SH50: Water-soluble cellulose ether manufactured by Shin-Etsu Chemical Co., Ltd. A. Z. M: Aziridine compound manufactured by Mutual Pharmaceutical Co., Ltd. Epicron 860 (registered trademark): Bisphenol A type epoxy compound manufactured by Dainippon Ink and Chemicals, Inc.

(4) Evaluation of Film The performance of the vinyl chloride resin film for agriculture was evaluated by the following methods, and the results are shown in Tables 5 and 6. Transparency The parallel light transmittance of each of the obtained films at a wavelength of 555 mm was measured using a spectrophotometer (330, manufactured by Hitachi, Ltd.).
(Type) and indicated the value. Dustproof 5.4m frontage, 3m high, 1 depth
Each film obtained in each 5-meter pipe house was coated so that the surface on which the antifogging film was formed was located inside the house. After winding the film side part during the day and sealing the evening film, the film of the ceiling part and the winding part of the film being stretched are collected with time, and the light transmittance at a wavelength of 555 mm is measured with a spectrophotometer. (Hitachi, 330
(Type). The measurement criteria are as follows. ：: Light transmittance of 80% or more ：: Light transmittance of 65 to 79% △: Light transmittance of 45 to 64% ×: Light transmittance of less than 45%

After the film stretched with the anti-fog property is wound on the film side during the day and the evening film is sealed, the state of water droplets adhering to the ceiling portion of the film being stretched and the inner surface of each of the rolled portions is measured over time. And visually observed. The evaluation criteria are as follows. ◎: Film surface (facing the inside of the house, the same applies hereinafter)
Water droplets adhering to each other are united and spread in a thin film shape, and the area of the thin film portion extends over 2/3 or more of the film surface. ：: coalescence of water droplets adhering to the film surface is observed, but the area of the thin film portion is less than 2/3 of the film surface,
1/2 or more. Ｘx: Cohesion of water droplets adhering to the film surface is observed, but the area of the thin film portion is less than 1/2 of the film surface. Δ: Coalescence of water droplets adhering to the film surface is recognized, but the shape of the thin film portion is not recognized. ×: No coalescence of water droplets adhering to the film surface is observed.

Accelerated anti-fogging test 300 cc of water (50 ° C.) was placed in a 500 cc beaker, and the beaker was coated with a sample film so that the surface on which the anti-fogging film was formed was located inside the beaker. The beaker was inclined at 10 ° from the ground surface at (50 ° C.) and immersed in water up to 2/3 from the bottom. After standing in a constant temperature room at 25 ° C. for a predetermined time, the state of the film surface was visually observed. The state of flow of water droplets on the film surface was evaluated according to the same criteria as in the anti-fog test.

Using a film after the accelerated antifogging test (after 160 days) performed in the adhesion test, a cellophane tape was adhered to the surface on which the antifogging film was formed. The state of peeling was visually observed. The evaluation criteria are as follows. ：: Completely remained without peeling of the coating film. Ｘ: one part (less than 1/3) of the coating film was peeled off Δ: one third or more and less than 2/3 of the coating film was peeled off. X: 2/3 of the coating film was peeled off.

[0052]

[Table 5]

[0053]

[Table 6]

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI B32B 27/00 B32B 27/00 Z C08J 7/04 CEV C08J 7/04 CEVS (72) Inventor Shunichi Onishi Nakamura-ku, Nagoya-shi, Aichi Prefecture 2 Oike, Iwazuka-cho Nagoya Office, Mitsubishi Chemical MKV Corporation

Claims (5)

[Claims] 1. A fluorine-containing acrylic polymer (a), an acrylic polymer (b) substantially containing no fluorine, and a vinylidene fluoride resin (c) on one surface of a base film made of a vinyl chloride resin. A film derived from a composition containing is formed, and silica sol and / or
Or, in an agricultural vinyl chloride resin film having a coating derived from an anti-fogging agent composition containing an alumina sol and a thermoplastic resin, a 1,5-sorbitan fatty acid ester having 10 to 15 fatty acid carbon atoms is formed on the base film. (A)
A vinyl chloride resin film for agricultural use, comprising a surfactant comprising the propylene oxide adduct (B). 2. Component (A) and component (B) in the surfactant are present in an amount of 0.2 to 0.8 component (B) per mole of component (A).
The vinyl chloride resin film for agricultural use according to claim 1, which is in a molar ratio. 3. The method according to claim 1, wherein the surfactant is a vinyl chloride resin.
The agricultural polyvinyl chloride resin film according to claim 1 or 2, which is blended in an amount of 0.1 to 5.0 parts by weight per part by weight. 4. A composition comprising a fluorinated acrylic polymer (a), an acrylic polymer (b) substantially containing no fluorine, and a vinylidene fluoride resin (c), wherein (a) +
When (b) + (c) is 100 parts by weight, (a) 3
To 50 parts by weight, (b) 2 to 40 parts by weight, and (c) 10 to 10 parts by weight.
4. The composition according to claim 1, which is blended in a proportion of 95 parts by weight.
A vinyl chloride resin film for agricultural use according to any one of the above items. 5. The silica sol and / or the alumina sol,
The agricultural polyvinyl chloride resin film according to any one of claims 1 to 4, which is contained in an amount of 0.5 to 40 times the thermoplastic resin in terms of solid content weight ratio.