JP2500957B2 - Agricultural soft vinyl chloride resin film - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a vinyl chloride resin film for agriculture. More specifically, the present invention relates to a vinyl chloride resin film for agriculture, which prevents contamination due to surface migration of a plasticizer and the like, and is excellent in dust resistance, drip-proofness and durability.

[0002]

2. Description of the Related Art In recent years, for the purpose of improving the profitability of farmers, a method of forcibly or restraining cultivation of useful plants in a house (greenhouse) or a tunnel has been widely adopted. Polyethylene film, ethylene-vinyl acetate copolymer film, polyester film, polycarbonate film, vinyl chloride resin film, glass and the like are used as the covering material for the house or tunnel. Among them, the soft vinyl chloride resin film is the most comprehensive in terms of light transmittance, heat retention, mechanical strength, durability, workability, economy, etc., as compared with other synthetic resin films, so it is widely used. Has been adopted.

The properties required for a house or tunnel covering material are that the outer surface is not soiled over a long period of time and is excellent in dust resistance,
To maintain good light transmittance and promote the growth of cultivated crops. Condensed water adhering to the inner surface of the covering material has excellent "anti-fog property" of flowing down along the inner surface of the film without dropping it on cultivated crops, maintaining an appropriate humidity inside the house or tunnel to prevent illness. Control the occurrence. Etc.

Therefore, as a method for improving the dustproof property,
A method of applying an acrylic resin to the surface of a vinyl chloride resin, a method of applying a fluororesin via an adhesive, and a method of applying a mixture of a fluororesin and an acrylic resin also improve anti-fogging property. As a method, a method of kneading a so-called anti-fogging agent such as a fatty acid ester of glycerin or a fatty acid ester of sorbitan into a base resin, or after forming a film, a method of coating a hydrophilic substance or a water-soluble polymer substance on the surface is performed. ing. Recently, for example, Japanese Patent Laid-Open No. Hei 3
As described in JP-A-51121, there is also proposed a method of forming a dustproof coating derived from a fluororesin on one side of a base film and a coating derived from an antifogging composition on the other side. Further, although fluororesins have excellent stain resistance, non-adhesiveness, weather resistance, etc. as compared with other thermoplastic resins, they are difficult to adhere to other base materials, and the formed coating film is opaque. Therefore, in order to improve this, a method of mixing a vinylidene fluoride copolymer having a specific composition and an acrylic resin (see JP-A-63-21143) and a fluorine-containing copolymer A method of blending an acrylic resin with a polymer (see JP-A-64-65161) has also been proposed. However, in vinyl chloride resin films, it is generally practical to fix and integrate them with fluororesin through these adhesive resins due to migration to the film surface due to compounding agents such as plasticizers in the substrate, and the effect of jetting. However, the transparency of the film has not reached a satisfactory level.

[0005]

Under the circumstances, the inventors of the present invention can easily perform the spreading work, and the unfavorable deterioration such as discoloration, embrittlement, and deterioration of the antifogging property caused by the spreading outdoors. The present invention has been completed as a result of earnest studies for the purpose of providing a vinyl chloride resin film for agriculture in which the phenomenon is significantly improved and the durability is improved.

[0006]

SUMMARY OF THE INVENTION However, the gist of the present invention is that a fluorine-containing acrylic polymer [A] and a fluorine-free acrylic polymer are provided on one side of a soft vinyl chloride resin film. When the main component is the three components of the base polymer [B] and the vinylidene fluoride resin [C], and the mixing ratio of each component is [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 to form a dust-proof coating derived from the composition, and silica sol and / or other surface on one side. A soft vinyl chloride resin film for agriculture, comprising an antifogging film derived from a composition containing alumina sol and a binder as main components.

Hereinafter, the present invention will be described in detail. I. Base Film In the present invention, the vinyl chloride resin means not only polyvinyl chloride but also a copolymer containing vinyl chloride as a main component.
Examples of the monomer compound copolymerizable with vinyl chloride include vinylidene chloride, ethylene, propylene, acrylonitrile, maleic acid, itaconic acid, acrylic acid, methacrylic acid and vinyl acetate. 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 order to impart excellent flexibility and mechanical strength to the vinyl chloride resin as the base, the base resin 10
About 20 to 60 parts by weight of a plasticizer is usually added to 0 parts by weight. As the plasticizer, for example, phthalic acid derivative, isophthalic acid derivative, adipic acid derivative, maleic acid derivative, citric acid derivative, itaconic acid derivative, oleic acid derivative, ricinoleic acid derivative, other tricresyl phosphate, epoxidized soybean oil, Examples thereof include epoxy resin-based plasticizers.

Further, the plasticizer is not limited to the above-mentioned plasticizer, and for example, thermoplastic polyurethane resin, polyvinyl acetate resin or the like can be used. Further, the agricultural soft film of the present invention, if necessary, resin additives, such as anti-fog agents, ultraviolet absorbers, light stabilizers, antioxidants, lubricants,
A heat stabilizer, a pigment, a coloring agent such as a dye, an antifog agent, an antistatic agent and the like can be added in usual amounts.

Examples of the antifogging agent include various nonionic, anionic and cationic surface active agents which are usually incorporated in agricultural vinyl chloride films. Of these, nonionic surfactants are preferable. Examples of the ultraviolet absorber include benzotriazole-based, benzoate-based, benzophenone-based, cyanoacrylate-based, and phenyl salicylate-based ultraviolet absorbers. Of these, benzophenone-based UV absorbers and / or benzotriazole-based UV absorbers are preferable.

As the light stabilizer, various compounds commonly used in agricultural vinyl chloride films can be used. Specifically, for example, 4-acetoxy-2,2,
6,6-Tetramethylpiperidine, bis (2,2,6,
6-tetramethyl-4-piperidine) adipate, tris (2,2,6,6-tetramethyl-4-piperidyl)
Examples thereof include hindered amine compounds such as benzene-1,3,5-tricarboxylate.

As the antioxidant, 2,6-di-ter is used.
Examples thereof include t-butyl-4-methylphenol, 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), dilaurylthiodipropionate and the like. Examples of the lubricant or heat stabilizer 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 thereof include metal salts, organic phosphite compounds, phenols, β-diketone compounds and the like.

Examples of the colorant include various pigments and dyes such as phthalocyanine blue, phthalocyanine green, high yellow, alizarin lake, titanium oxide, zinc white, ultramarine blue, permanent red, quinacridone and carbon black. Examples of the antifogging agent include a fluorine-based surfactant, and specifically, a surfactant in which a part or all of F is substituted for H bonded to C of a hydrophobic group of a normal surfactant. In particular, a surfactant containing a perfluoroalkyl group or a perfluoroalkenyl group is preferable.

A soft vinyl chloride resin film (hereinafter referred to as a base film) which is a base of the agricultural film of the present invention.
In, the resin composition containing the required resin additive,
After blending with a blender such as a ribbon blender, a Banbury mixer, and a super mixer, and homogenizing with a kneader, an ordinary film manufacturing method, for example, a calender molding method, an extrusion molding method,
The film is formed by using the inflation method or the like.
The thickness of the film is usually 0.01 to 0.3 mm, preferably 0.04 to 0.25 mm. II. Dustproof coating 1. Fluorine-containing acrylic polymer [A] In the present invention, the fluorine-containing 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 an alkyl ester of acrylic acid or methacrylic acid. Specific examples of the alkyl ester of acrylic acid or methacrylic acid include methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate,
C ₁ -C ₂₂ alkyl esters of acrylic acid such as n-butyl acrylate, iso-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, dodecyl acrylate, tridecyl acrylate, 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, C ₁ -C ₂₂ alkyl esters of methacrylic acid such as stearyl methacrylate: and the like.

Each of the above acrylic monomers is
Alternatively, they can be used as a mixture. Further, these acrylic monomers may be used together with other copolymerizable monomers. Examples of such other monomer include α, β-unsaturated carboxylic acid compounds containing one or more carboxyl groups in the molecule, and acrylic acid, methacrylic acid, itaconic acid, 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
4-hexafluorobutyl acrylate, 2,2,3
3,4,4-hexafluorobutyl methacrylate, 2
-Perfluorooctyl ethyl acrylate, 2-perfluoro octyl methacrylate, 2-perfluoro nonyl ethyl acrylate, 2-perfluoro nonyl ethyl methacrylate, etc. are mentioned. These may be used alone or in combination of two or more.

1-3. In the blended polymer [A], the polymerization ratio of the acrylic monomer and the perfluoroalkyl group-containing acrylic monomer is usually preferably in the range of 20 to 99% by weight. If the amount of the acrylic monomer is less than this range, the adhesion of the formed film to the base film is insufficient, and if it is more than this range, the transparency is poor.

Acrylic monomer and perfluoroalkyl group-containing acrylic monomer are blended in a predetermined amount and charged into a polymerization vessel together with an organic solvent. A polymerization initiator and, if necessary, a molecular weight modifier are added and stirred. While heating, polymerize. For the polymerization, generally known methods such as suspension polymerization method and solution polymerization method are adopted. In this case, examples of the polymerization initiator that can be used include radical generating catalysts such as α, α-azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, and butyl mercaptan, n- Dodecyl mercaptan, tert
-Dodecyl mercaptan, β-mercaptoethanol and the like can be mentioned.

The organic solvent used for polymerization is methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-.
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,
Ketones such as 3-hexanone, di-n-propyl ketone, diisopropyl ketone, di-n-amyl ketone, and cyclohexanone; tetrahydrofuran and the like can be used singly or as a mixture of two or more.

2. Acrylic polymer [B] An acrylic polymer [B] substantially free of fluorine is a polymer mainly composed of alkyl esters of acrylic acid or methacrylic acid described in 1-1, It is obtained by a polymerization method.

3. Vinylidene fluoride-based resin [C] The vinylidene fluoride-based resin [C] is a vinylidene fluoride homopolymer or a copolymer of vinylidene fluoride and other fluorine-based unsaturated monomer and / or no fluorine. Copolymers with possible monomers, and polymers obtained by modifying or modifying a part of these polymers are also included. These vinylidene fluoride resins can be used alone or in combination of two or more. Other fluorine-containing resins, such as tetrafluoroethylene, chlorotrifluoroethylene,
It may be used as a mixture with fluoroethylene or the like.

4. Dust-proof coating formation The blending ratio of the fluorine-containing acrylic polymer [A], the fluorine-free acrylic polymer [B], and the vinylidene fluoride resin [C] is A + B + C at 100 parts by weight. In addition, [A] is 3 to 50 parts by weight, [B] is 2 to 40 parts by weight, and [C] is 10 to 95 parts by weight. When the ratio of the polymer [A] to the resin [C] is too small, the transparency of the formed film is insufficient. Further, the polymer [B] with respect to the resin [C]
If the ratio 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, polymer [A] to resin [C] to resin [C]
If the proportion of the polymer [B] is too large, the effect of preventing migration of the plasticizer of the formed film, stain resistance, and water resistance is not sufficient, which is not preferable.

In the above coating composition, in addition to these components,
Auxiliary components, such as antioxidants, neutralizing agents, ultraviolet absorbers, light stabilizers, antistatic agents, pigments, dyes, foaming agents, lubricants, etc., can be added and dispersed and / or dissolved in an organic solvent. Can be used. 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; chloroform as a halogenated hydrocarbon. , Tetrachlorohydrocarbon,
Chlorobenzene, etc .; Ketones, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc .; Esters, methyl acetate, allyl acetate, ethyl stearate, etc .; Amines, trimethylamine, diphenylamine, hexamethylenediamine, etc .; Others dimethylformamide, dimethylacetamide, dioxane ,
There are diethyl ether, diethylenedithioglycol, diacetone alcohol, benzonitrile, dimethyl sulfoxide and the like, and these can be used alone or in combination of two or more kinds.

In order to form a film on the surface of the vinyl chloride resin film with the above film composition, various known methods are applied depending on the shape of the molded product. For example, when forming a film in a solution state, doctor blade coating method, gravure roll coating method, air knife coating method, reverse roll coating method, dip coating method, curtain roll coating method,
A coating method such as a spray coating method or a rod coating method is used. When the coating composition is formed as a single coating without being in a solution state, a coextrusion method, an extrusion coating method, an extrusion laminating method, or a laminating method is used.

As a method for forming a film, as a method for drying a solvent when a coating method is used, there are, for example, a natural drying method, a hot air drying method, an infrared drying method and a far infrared drying method. Considering this, the hot air drying method is advantageous. In this case, the temperature condition is in the range of 50 to 150 ° C., and the time is preferably selected from 10 seconds to 15 minutes. In the present invention,
The thickness of the coating formed on the surface of the base film is preferably 1/10 or less of the thickness of the base film. If the thickness of the coating is more than 1/10 of that of the base film, there is a difference in flexibility between the base film and the base film, and therefore the phenomenon such as peeling of the base film from the base film is likely to occur, and cracks are formed in the base film. Occurs, and the strength of the base film is lowered, which is not preferable.

Before coating the above coating composition, the surface of the soft vinyl chloride resin film is previously washed with alcohol or water, plasma discharge treatment or corona discharge treatment, other paint or primer. May be subjected to a pretreatment such as undercoating.

III. Antifogging Coating The silica sol and / or alumina sol used in the present invention preferably has an average particle size of 5 to 100 mμ. When the average particle size exceeds 100 mμ, the coating film is white and easily devitrifies, and when it is less than 5 mμ, the stability of the antifogging agent composition is insufficient, which is not preferable. These may be used alone or in combination of both. Further, when using both in combination, two or more kinds having different average particle diameters may be used. When both are combined, the weight ratio of silica sol / alumina sol is 95 to 5
The ratio is preferably / 5 to 95 (100 as a whole).

The alumina sol may be either a commercially available product itself or an aqueous sol prepared by dispersing usually commercially available alumina powder in water. Alumina sol shows a so-called thixotropic property that the viscosity of the dispersion rapidly increases when it is dispersed in water at a high concentration, and it is difficult to obtain a homogeneous dispersion, but when a medium shear 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 lowered.

On the other hand, in many cases, the silica sol is negatively charged on the particle surface, but when it is used in combination with an alumina sol, it is not preferable to use a negatively charged one. When silica sol and alumina sol, which are negatively charged, are mixed, the mixed dispersion liquid rapidly agglomerates and gels, resulting in poor dispersion. Therefore, the colloidal silica is preferably positively charged on the particle surface.

As the binder component to be blended with the antifogging composition, known surfactants such as anionic surfactants, cationic surfactants, nonionic surfactants and the like or thermoplastic resins are known and used for public use. Used. It is necessary to change the type of the surfactant used as the binder component depending on the silica sol or the alumina sol. Generally, a negatively charged silica sol and a cationic surfactant, and a positively charged alumina sol and an anionic surfactant. Combinations with active agents should be avoided. These combinations easily cause gelation of the sol and aggregation / separation of the antifogging agent composition, which makes application difficult.

The thermoplastic resin used as the binder component is an acrylic resin, vinyl chloride-vinyl acetate resin, polyethylene resin, vinyl chloride resin, vinylidene chloride resin, polyurethane resin, polycarbonate resin, styrene resin. Examples of the resin include vinyl resins, vinyl acetate resins, unsaturated polyester resins, and acrylic resins are particularly preferable.

The silica sol and / or alumina sol, which is the main component of the antifogging agent composition, is preferably compounded in an amount of 0.5 to 40 times the binder component in terms of solid content weight ratio. When it exceeds 40 times, not only the antifogging effect does not improve in proportion to the compounding amount, but also the coating film formed after coating becomes cloudy to reduce the light transmittance, and the coating film tends to be rough and brittle. Tends to become. On the other hand, when it is less than 0.5 times, it becomes difficult to exert a sufficient antifogging effect.

A crosslinkable compound which crosslinks the binder components may be used in combination with the antifogging composition. By doing so, the water resistance of the anti-fog coating can be improved.
The amount of the crosslinkable compound used is in the range of 0.1 to 30% by weight, particularly 0.5 to 10% by weight, based on the solid content of the binder component.
Is preferred. Further, the antifog composition can be mixed with an antifoaming agent, a lubricant, an antistatic agent, and various other additives, if necessary.

The antifogging composition is usually used in liquid form. The liquid dispersion medium includes an affinity or water-miscible solvent containing water, water: monohydric alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol: polyhydric alcohols such as ethylene glycol, diethylene glycol, glycerin: Cyclic alcohols such as benzyl alcohol: cellosolve acetates: ketones and the like.

These may be used alone or in combination, but the dispersion stability of the antifogging composition used in the present invention, the wettability after coating on the film surface, the difficulty of removing the liquid dispersion medium,
It is preferable to decide in consideration of economic efficiency. Moreover, the the coating of the antifogging agent composition is formed on the surface of the medium film as an adhesion amount of solids, it is generally 0.01 to 10 g / m ^2, particularly from 0.1-5 g / m ² Is preferred.

In order to form an antifogging film on the surface of the base film, generally, a solution or dispersion of each composition may be applied by a known coating method and dried after coating. As a drying method after coating, either natural drying or forced drying may be adopted. When the forced drying method is adopted, it is usually 50 to 2
It may be dried in a temperature range of 50 ° C, preferably 70 to 200 ° C. For heat drying, hot air drying method, infrared drying method,
An appropriate method such as a far infrared ray drying method may be adopted, and it is advantageous to use the hot air drying method in consideration of the drying speed and stability.

When the adhesion between the base film and the antifogging film is not sufficient, the same pretreatment as that for forming the dustproof film may be carried out. The order of forming the two types of coating compositions on the surface of the base film is determined in consideration of heating conditions and the like.

[0039]

The agricultural soft vinyl chloride resin film of the present invention has a dust-proof coating which prevents contamination due to bleed-out of plasticizers, etc. Since it shows haze and durability, it is extremely useful as an agricultural film.

[0040]

EXAMPLES The present invention will be described in detail below based on examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Examples 1-5, Comparative Examples 1-4 Preparation of base film Polyvinyl chloride (Polymerization degree 1400) 100 parts by weight Dioctyl phthalate 50 〃 Tricresyl phosphate 3 〃 Epoxidized soybean oil 3 〃 Barium-zinc compound liquid stabilizer 1.5 〃 Barium stearate 0.2 〃 Zinc stearate 0.4 〃 Sorbitan laurate 1.5 〃 2,4-dihydroxybenzophenone 0.5 〃 After mixing the above ingredients by stirring with a super mixer for 10 minutes, knead them on a mill roll heated to 180 ° C. Then, a substrate film having a thickness of 0.15 mm was prepared.

II. Preparation of fluorinated acrylic polymer [A]
Ltd. thermometer, a stirrer, a reflux condenser and a reactor equipped with a nozzle for raw materials added, 70 parts by weight of methyl ethyl ketone, 30 parts by weight of toluene, of the monomers shown in benzoyl peroxide 1.0 parts by weight Table 1 Charge 100 parts by weight of the mixture,
While stirring in a stream of nitrogen gas, 0.5 parts by weight of benzoyl peroxide was further added at 80 ° C. for 3 hours to carry out the reaction for about 3 hours,
Continuously at the same temperature, resins a and b, which are fluorine-containing acrylic polymers, were obtained.

III. Preparation of Acrylic Polymer [B] In a reactor similar to II, 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 each monomer shown in Table 1 were charged, and benzoyl peroxide was further added at 70 ° C. for 3 hours while stirring in a nitrogen gas stream. The reaction was continued for about 3 hours by adding 0.5 part by weight, and the reaction was continued at the same temperature.
d was obtained.

IV. Formation of Dustproof Coating A fluorine-containing acrylic polymer [A] and an acrylic polymer [B] of the types and amounts shown in Table 2 and a commercially available vinylidene fluoride resin [C] are blended and added to the mixture. 2 solids
Methyl ethyl ketone was added to 0% by weight to obtain a dustproof coating composition.

Each of the dustproof coating compositions was applied to one side of the base film prepared in I using a # 5 bar coater. The applied film was kept in an oven at 130 ° C. for 1 minute to evaporate the solvent. The coating amount of each film obtained was about 3 g / m ² .

V. Formation of anti-fogging coating A main component (silica sol and / or alumina sol) shown in Table 3, a binder component, a cross-linking agent and a liquid dispersion medium were blended to obtain an anti-fogging composition. Each of the antifogging agent compositions was applied to the other surface of the base film having the dustproof coating, using a # 5 bar coater. The coated film is 80 ℃
It was kept in the oven for 1 minute to vaporize the liquid dispersion medium. The coating amount of each film obtained was about 1 g / m ² .

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

[Table 3]

The antifogging composition in Table 2 is as follows. OSCAL-1432 (registered trademark): Catalysis Kasei Kogyo Co., Ltd. solution dispersion type colloidal silica Cataloid SI-30, Cataloid SI-80P (registered trademark): Catalysis Kasei Co., Ltd. water dispersion type colloidal silica Alumina sol-520 : Nissan Chemical Industry Co., Ltd. water dispersion type alumina sol Kayacryl resin H-300 (registered trademark): Nippon Kayaku Co., Ltd. acrylic emulsion DIALNAL BR-101 (registered trademark): Mitsubishi Rayon Co., Ltd. heat Plastic acrylic resin METOLOSE 65SH50: manufactured by Shin-Etsu Chemical Co., Ltd., water-soluble cellulose ether Epicron 860 (registered trademark): manufactured by Dainippon Ink and Chemicals, Inc. bisphenol A type epoxy compound T.I. A. Z. M: Mutual Yakuko Co., Ltd. aziridine compound

VI. Evaluation of Film Each performance of the soft vinyl chloride resin film obtained by the following method was evaluated, and the results are shown in Table 4.

Appearance The appearance of the film was visually observed and evaluated according to the following criteria. ⊚: Film formation appearance is very good ◯: Film formation appearance is good Δ: White turbidity, poor film formation appearance ×: Remarkably white turbidity, film formation appearance is poor.

Dust-proof property 9 kinds of films were installed in a test field in Isshi-gun, Mie prefecture, in a pipe house (frontage: 3 m, depth: 5 m, building height: 1.5 m).
m, roof slope 30 degrees) with a dustproof coating on the outside. The film being spread is collected over time, and the wavelength 55
The light transmittance at 5 millimicrons was measured with a spectrophotometer (Hitachi, EPS-2U type). The display of the measurement result is as follows. A: Light transmittance of 80% or more. Good: Light transmittance in the range of 65 to 79%. Δ: A light transmittance of 45 to 64%. X: Light transmittance of less than 45%.

Antifogging Property With respect to the nine types of films spread in the evaluation of dustproof property, the state of water droplets adhering to the surface on which the antifogging film was formed was visually observed with time. The evaluation criteria are as follows. ◎: Film surface (one facing the inside of the house, the same hereafter)
Water droplets adhering to each other coalesce and spread into a thin film, and the area of this thin film portion covers more than 1/2 of the film surface. ◯: A state in which water droplets adhering to the film surface have coalesced and spread into a thin film is recognized, but the area of this thin film portion is less than 1/2 of the film surface. Δ: The water droplets adhering to the film surface are recognized to be coalesced, but the shape of the thin film portion is not recognized. X: Water droplets adhering to the film surface are not recognized as coalescing.

Durability The stretched film was collected with time, the elongation was measured, and the elongation retention rate was calculated by the following formula.

[0055]

[Equation 1]

The results are displayed as follows. A: Elongation retention rate is 80% or more. Good: The elongation retention rate is in the range of 60 to 79%. Δ: The elongation retention rate is in the range of 40 to 59%. X: The elongation retention rate is less than 40%.

[0057]

[Table 4]

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C08L 27/16 LGG C08L 27/16 LGG C09D 133/16 PGF C09D 133/16 PGF // (C08L 27/16 ( C08L 27/16 33:16 33:16 33:08) 33:08) (56) Reference JP-A-3-51121 (JP, A) JP-A 63-17046 (JP, A) JP-A 62- 169641 (JP, A) JP-A-2-112936 (JP, A)

Claims (1)

(57) [Claims] 1. A soft vinyl chloride resin film having a fluorine-containing acrylic polymer [A], a fluorine-free acrylic polymer [B] and a vinylidene fluoride resin [C] on one side. 3 components as the main component and each component
The compounding ratio is [A] + [B] + [C] as 100 parts by weight.
In the case of [A] 3 to 50 parts by weight, [B] 2 to 40 parts by weight
Part and [C] 10 to 95 parts by weight of the composition, a dust-proof coating derived from the composition is formed, and the other side is coated with a silica sol and / or alumina sol and a composition containing a binder as a main component. A soft vinyl chloride resin film for agriculture, which is characterized by being formed.