JPH10120810A - Agricultural vinyl chloride resin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain vinyl chloride resin film improved in dustproofness by forming coating film of a specified acrylic resin composition on one side or both sides of vinyl chloride resin film containing an organophosphoric ester. SOLUTION: Coating film of a composition obtained by blending an acrylic resin (A) comprising a copolymer of 1-30wt.% alkyl (meth)acrylate of formula I (wherein R<1> is H or methyl; and n is 5 to 16), 5-40wt.% hydroxyalkyl (meth) acrylate, 0-20wt.% α,β-unsaturated carboxylic acid compound containing carboxyl groups in the molecule, and other vinyl monomer, and a fluorinated acrylic resin (B) comprising a copolymer of 5-40wt.% perfluoroalkyl (meth)acrylate represented by formula II (wherein m is 0 to 3; a >0; and b is 4 to 16) and 95-60wt.% alkyl (meth)acrylate at a ratio of component A to component B of (1 to 30):1 is formed on one side or both sides of a vinyl chloride resin film containing an organophosphoric ester.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a vinyl chloride resin film for agricultural use. More specifically, the present invention relates to an agricultural vinyl chloride resin film having improved durability against undesired deterioration phenomena such as discoloration, embrittlement, and reduced dust resistance caused by stretching outdoors.

[0002]

2. Description of the Related Art In recent years, farmers who cultivate useful plants,
For the purpose of improving profitability, useful plants are greenhouses,
Alternatively, methods of promoting cultivation and suppression cultivation in tunnels have been widely adopted. As a covering material for this house (greenhouse) or tunnel, polyethylene film,
Ethylene-vinyl acetate copolymer films, polyester films, polycarbonate films, hard and soft vinyl chloride resin films, glass and the like are used. Among them, soft vinyl chloride resin films are widely used because they have the best light transmittance, heat retention, mechanical strength, durability and workability compared to other synthetic resin films. I have.

However, a synthetic resin film used as a covering material for a house or a tunnel, including a vinyl chloride resin, has started to be used as a covering material.
Over the years, it is affected by the sun's rays, especially ultraviolet rays, and changes over time such as deterioration of appearance and decrease in flexibility of the film. In addition, recent improved agricultural techniques,
In particular, agricultural techniques aiming at economic efficiency and labor saving require a covering material to have a property that can withstand even more severe conditions than ever before. Accordingly, a technique of forming a film by adding and blending an organic phosphate with a vinyl chloride resin as a base material for the purpose of improving weather resistance has been widely adopted.

[0004] On the other hand, vinyl chloride resin films used for agriculture have been used for two years after the start of use due to the influence of the area or place where they are used. Dust resistance is significantly reduced,
It cannot be used. As a method for eliminating the above-mentioned disadvantages, there has been proposed a method of coating the surface of a vinyl chloride resin film for agricultural use with the following specific resin or paint. (I) A method of applying an acrylic resin (JP-B-46-2)
9639, JP-B-50-28117, etc.) (ii) A method of applying a fluororesin via an adhesive layer (JP-A-56-86748, JP-A-57-8155, JP-A-57-8155) (Iii) A method of applying a mixture of a fluororesin and an acrylic resin (JP-A-63-21143, JP-A-46-6)
No. 5161, Japanese Patent Publication No. 63-236)

[0005] However, (i) is not enough to prevent the bleed out of the plasticizer or the like of the base material to the surface of the molded article, and (ii) is due to the effect of the plasticizer or the like migrating to the adhesive layer.
The adhesion and integration of the fluororesin and the substrate through the adhesive layer was not practically sufficient. As these improvements (i
ii) has been proposed, but has the drawback that the interfacial adhesion between the base material and the fluororesin mixture is insufficient and that the acrylic resin and the fluororesin are hardly dissolved, so that the coating film becomes opaque.

[0006]

Under such circumstances, the present inventors have significantly improved the undesired deterioration phenomena such as discoloration, embrittlement, and reduced dust resistance caused by stretching outdoors. The present inventors have conducted intensive studies with the aim of providing a vinyl chloride resin film for agricultural use having improved dustproofness, and as a result, have completed the present invention.

[0007]

SUMMARY OF THE INVENTION The gist of the present invention is to provide a vinyl chloride resin film containing an organic phosphate ester on one or both surfaces of an alkyl (I) represented by the general formula (I). 1-30% by weight of a meth) acrylate monomer, 5-40% by weight of a hydroxyalkyl (meth) acrylate monomer, 0-20% by weight of an α, β-unsaturated carboxylic acid compound containing one or more carboxyl groups in a molecule % And an acrylic resin [A] composed of a copolymer with another vinyl monomer copolymerizable therewith, and a perfluoroalkyl (meth) acrylate monomer represented by the general formula (II) in an amount of 5 to 40% by weight. % And an alkyl (meth) acrylate monomer 95
農業 60% by weight of a fluorine-containing acrylic resin [B] consisting of a copolymer.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. 1. Vinyl Chloride Resin In the present invention, the vinyl chloride resin refers to not only polyvinyl chloride but also a copolymer containing vinyl chloride as a main component.
Examples of monomer compounds 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 flexibility to the vinyl chloride resin serving as the base, this resin 1
20 to 60 parts by weight of a plasticizer is added to 00 parts by weight. By setting the blending amount of the plasticizer to the above range,
Excellent flexibility and mechanical properties can be imparted to the desired vinyl chloride resin film.

Examples of the plasticizer include phthalic acid derivatives such as di-n-octyl phthalate, di-2-ethylhexyl phthalate, dibenzyl phthalate, diisodecyl phthalate, didodecyl phthalate and diundecyl phthalate; and isophthalic acids such as dioctyl phthalate Derivatives; adipic acid derivatives such as di-n-butyl adipate and dioctyl adipate; maleic acid derivatives such as di-n-butyl malate; citric acid derivatives such as tri-n-butyl citrate; itaconic acid derivatives such as monobutyl itaconate Oleic acid derivatives such as butyl oleate; ricinoleic acid derivatives such as glycerin monoricinoleate; and other epoxidized soybean oils and epoxy resin plasticizers.

[0010] The agricultural vinyl chloride resin film of the present invention contains an organic phosphate ester in addition to the vinyl chloride resin. Examples of the organic phosphate include triisopropylphenyl phosphate, isodecyldiphenylphosphate, tricresylphosphate, tris (isopropylphenyl) phosphate, tributylphosphate, triethylphosphate, trioctylphosphate, tributoxyethylphosphate, triphenylphosphate, octyldiphenyl Among them, there are phosphate, trixylenyl phosphate and the like. Among them, tricresyl phosphate and trixylenyl phosphate are particularly preferable.

The above organic phosphates can be used alone or in the form of a composite. Specifically, a complex of an organic phosphite and an organic phosphite is mentioned, and the organic phosphite includes, for example, a phosphonate compound such as diphenylphosphonate. The compounding amount of the organic phosphate is in the range of 0.1 to 15 parts by weight, preferably 0.1 to 15 parts by weight, based on 100 parts by weight of the vinyl chloride resin.
It is selected within the range of 2 to 10 parts by weight. If the amount is less than 0.1 part by weight, the weather resistance and the dust resistance of the vinyl chloride resin film are not improved. If the amount is more than 15 parts by weight, the transparency of the film becomes extremely poor, which is not preferable.
It is particularly preferred that the amount be in the range of 0.2 to 8 parts by weight.

The vinyl chloride resin film for agriculture of the present invention is preferably used in combination with an ultraviolet absorber from the viewpoint of coatability and outdoor expandability. The ultraviolet absorber may be any one which is usually blended in an agricultural vinyl chloride film, and includes various ultraviolet absorbers such as benzotriazole, benzophenone, salicylate, hydroquinone, and cyanoacrylate. Particularly, a benzotriazole-based ultraviolet absorber and a benzophenone-based ultraviolet absorber are preferable. Specifically, the following are mentioned.

Benzophenone ultraviolet absorbers: 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-benzoyloxybenzophenone,
2'-dihydroxy-4-methoxybenzophenone, 2
-Hydroxy-4-methoxy-5-sulfonebenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-5-chlorobenzophenone, Bis- (2-methoxy-4-hydroxy-5
-Benzoylphenyl) methane.

Benzotriazole type ultraviolet absorber; 2-
(2′-hydroxyphenyl) benzotriazole, 2
-(2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) -5-carboxylic acid butyl ester benzotriazole, 2- (2'-hydroxy-5 ' -Methylphenyl) -5,6-dichlorobenzotriazole, 2-
(2′-hydroxy-5′-methylphenyl) -5-ethylsulfonebenzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy -5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-aminophenyl) benzotriazole,
2- (2'-hydroxy-3 ', 5'-dimethylphenyl) benzotriazole, 2- (2'-hydroxy-
3 ', 5'-dimethylphenyl) -5-methoxybenzotriazole, 2- (2'-methyl-4'-hydroxyphenyl) benzotriazole, 2- (2'-stearyloxy-3', 5'-dimethylphenyl ) -5-Methylbenzotriazole, 2- (2′-hydroxy-5-
Carboxylic acid phenyl) benzotriazole ethyl ester, 2- (2′-hydroxy-3′-methyl-5′-t
-Butylphenyl) benzotriazole, 2- (2'-
Hydroxy-3 ′, 5′-di-tert-butylphenyl)-
5-chlorobenzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5
Chlorobenzotriazole, 2- (2'-hydroxy-
5'-methoxyphenyl) benzotriazole, 2-
(2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-
Hydroxy-5'-cyclohexylphenyl) benzotriazole, 2- (2'-hydroxy-4 ', 5'-dimethylphenyl) -5-carboxylic acid benzotriazole butyl ester, 2- (2'-hydroxy-3', 5 '
-Dichlorophenyl) benzotriazole, 2- (2 '
-Hydroxy-4 ', 5'-dichlorophenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-
Dimethylphenyl) -5-ethylsulfonebenzotriazole, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, 2- (2′-hydroxy-5′-methoxyphenyl) -5-methylbenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) -5-carboxylic acid ester benzotriazole, 2
-(2'-acetoxy-5'-methylphenyl) benzotriazole.

The amount of the above-mentioned ultraviolet absorber mixed into the base film is based on 100 parts by weight of the base vinyl chloride resin.
A range of 0.02 to 8 parts by weight is preferred. When the amount is less than 0.02 parts by weight, the weather resistance of the agricultural polyvinyl chloride resin film is not sufficiently excellent, which is not preferable. On the other hand, when the amount is more than 8 parts by weight, a problem occurs that the resin is spouted onto the film surface together with other resin additives when the film is used, which is not preferable. Of the above ranges, a range of 0.1 to 3 parts by weight is particularly preferred.

In addition to the above-mentioned plasticizers and organic phosphoric acid esters, if necessary, well-known resin additives usually compounded in a synthetic resin for molding, such as a lubricant, Heat stabilizers, light stabilizers, antioxidants, stabilizing auxiliaries, antistatic agents, antifogging agents, antifog agents, antifungal agents, antialgal agents, inorganic fillers, coloring agents, and the like can be added.
Examples of the lubricant, heat stabilizer, or antioxidant that can be blended in the film according to the present invention include polyethylene wax, bisamide compounds, liquid paraffin, organic phosphite compounds, β-diketone compounds, and the like.

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. As the compound that can be used as an antioxidant, phenolic and sulfuric antioxidants can be used, and specifically, 2,6-di-butyl-4
-Methylphenol-2,2'-methylenebis (6-t
tert-butyl-4-ethylphenol), dilaurylthiodipropionate and the like. These antioxidants can be used alone or in combination of two or more.

Compounds which can be used as a stabilizing aid include triphenyl phosphite, dioctyl phenyl phosphite, tris (nonylphenyl) phosphite, diphenyl indecyl phosphite, trilauryl trithio phosphite, diphenyl acid phosphite and the like. Can be given. These stabilizing aids can be used alone or in combination of two or more. Examples of the antistatic agent include polyoxyethylene alkylamine, polyglycol ether, sodium p-styrenesulfonate and the like.

As the antifogging agent, nonionic surfactants are preferable, and ether-type ones such as polyoxyethylene ether, polyoxyethylene alkylaryl ether and polyoxyethylene polyoxypropylene ether, and polyhydric alcohols And ester type such as polyoxyethylene ether of glycerin ester and polyoxyl ethylene ether of sorbitan ester. Examples of the antimist agent include a fluorine-based surfactant. Specifically, it is a surfactant in which a part or all of a normal surfactant is substituted with F instead of H bonded to C of a hydrophobic group, and particularly contains a perfluoroalkyl group or a perfluoroalkenyl group. It is a surfactant. As the fungicide and the anti-algal agent, various compounds generally used in agricultural vinyl chloride films can be used.
Examples thereof include organic nitrogen compounds, and specific examples thereof include imidazole derivatives, anilide derivatives, urea derivatives, ammonium derivatives, triazine derivatives, and phthalimide derivatives.

In the present invention, an inorganic filler that absorbs in the infrared region can be blended for the purpose of improving heat retention.
Specifically, magnesium carbonate, magnesium silicate (talc), silicon oxide, aluminum oxide, barium sulfate, calcium sulfate, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, metal phosphate, hydrotalcites (hydrous -Or anhydrous-aluminum / magnesium basic carbonate); aluminum / zinc basic carbonate lithilm carbonate-aluminum hydroxide inclusion compound. Examples of usable coloring agents include phthalocyanine blue, phthalocyanine green, Hansa Yellow, Alizarin Lake, titanium oxide, zinc oxide, permanent red, quinacridone, and carbon black.

The above various resin additives can be used alone or in combination of several kinds. The amount of the various resin additives to be added can be selected within a range that does not deteriorate the properties of the film, and usually within a range of 10 parts by weight or less based on 100 parts by weight of the vinyl chloride resin as the substrate. In order to blend the plasticizer, the organic phosphate, and other resin additives with the vinyl chloride resin serving as the base of the film, each of the required amounts is weighed, and a ribbon blender, a Banbury mixer, a super mixer, and other conventional materials are known. What is necessary is just to use the compounding machine and the mixing machine used. The resin composition thus obtained can be formed into a film by 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. I'll do it.

2. Coating component 2-1 Acrylic resin [A] The acrylic resin [A] of the present invention comprises alkyl (meth) acrylate monomers 1 to 3 represented by the general formula (I).
0% by weight, 5 to 40% by weight of a hydroxyalkyl (meth) acrylate monomer, 0 to 20% by weight of an α, β-unsaturated carboxylic acid compound containing one or more carboxyl groups in the molecule, and It is a copolymer obtained by copolymerizing a monomer mixture containing another polymerizable vinyl monomer.

The alkyl (meth) acrylate monomer represented by the above general formula (I) (alkyl ester of acrylic acid or methacrylic acid (hereinafter the same)) includes 2
-Ethylhexyl acrylate, decyl acrylate,
The alkyl group such as lauryl acrylate, myristyl acrylate and palmityl acrylate has 5 to 16 carbon atoms
And alkyl methacrylates having an alkyl group having 5 to 16 carbon atoms, such as 2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, myristyl methacrylate, and palmityl methacrylate. These may be used alone or in combination of two or more. If the proportion of these monomers in the acrylic resin is more than 30% by weight, the adhesion between the formed film and the vinyl chloride resin film is not sufficient.

The hydroxyalkyl (meth) acrylate monomers include hydroxymethyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2
-Hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2-hydroxypentyl acrylate, 2-hydroxypentyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate and the like can give. When the ratio of the hydroxyalkyl (meth) acrylate in the acrylic resin is less than 5% by weight, the solubility in an organic solvent and the adhesion to a vinyl chloride resin film cannot be sufficiently exhibited. If the content is more than 40% by weight, the cost is high, and the effect obtained is not so large as compared with the increase in cost.

The α, β-unsaturated carboxylic acid having one or more carboxyl groups in the molecule includes acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, aconitic acid, fumaric acid, Crotonic acid and the like.

The alkyl (meth) acrylate monomer, hydroxyalkyl (meth) acrylate monomer and other vinyl monomers copolymerizable with the α, β-unsaturated carboxylic acid represented by the above general formula (I) include: For example, alkyl acrylates having 1 to 4 carbon atoms such as methyl acrylate, ethyl acrylate, n-propyl acrylate and isopropyl acrylate; carbon numbers of alkyl groups such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate and isopropyl methacrylate Is an alkyl methacrylate having 1 to 4; α, β-ethylenically unsaturated sulfonic acids such as ethylene sulfonic acid; 2-acrylamido-2-methylpropanoic acid; α, β-ethylenically unsaturated phosphonic acids; acrylic acid or methacrylic acid Acid Hydroxyl group-containing vinyl monomers such as Dorokishiechiru; acrylonitriles; is (meth) glycidyl esters of acrylic acid and the; acrylamide compound. These monomers may be used alone or in combination of two or more.

2-2 Fluorinated acrylic resin [B] The fluorinated acrylic resin [B] of the present invention comprises 5 to 40% by weight of a perfluoroalkyl (meth) acrylate monomer represented by the general formula (II), And alkyl (meth)
It is a copolymer obtained by copolymerizing a mixture with 60 to 95% by weight of an acrylate monomer. Examples of the perfluoroalkyl (meth) acrylate monomer represented by the general formula (II) include 1,1,2,2,3,3,4,4-octafluoropentyl acrylate, 1,1,2,2,2
3,3,4,4-octafluoropentyl methacrylate, 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl acrylate, 2,2,3
3,4,4,5,5,6,6,6-undecafluorohexyl methacrylate, 2-perfluorooctylethyl acrylate, 2-perfluorooctylethyl methacrylate, 2-perfluorolauryl acrylate,
Examples thereof include 2-perfluorolauryl methacrylate, 2-perfluoropalmityl acrylate, and 2-perfluoropalmityl methacrylate. These may be used alone or in combination of two or more.

The alkyl (meth) acrylate monomer may be selected from alkyl (meth) acrylates having 1 to 16 carbon atoms in the alkyl group as exemplified in 2-1. If the proportion of the alkyl (meth) acrylate monomer in the resin is less than 60% by weight, the miscibility with the acrylic resin [A] is inferior, the transparency of the formed film is not sufficient, and more than 95% by weight. And the dust resistance of the formed film,
Insufficient effect on weather resistance. The monomer mixture of the present resin may further contain a monomer copolymerizable therewith.

2-3 Polymerization of Resin [A] and Resin [B] The mixture of Resin [A] and Resin [B] is charged together with an organic solvent into a polymerization vessel, and a polymerization initiator and, if necessary, a molecular weight control. It is obtained by adding an agent and performing heat polymerization with stirring. For the polymerization, generally known methods such as a suspension polymerization method and a solution polymerization method are employed. Examples of the organic solvent used for polymerization include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, tert-amyl alcohol, and n
Alcohols such as hexyl alcohol and cyclohexanol; aromatic hydrocarbons such as benzene, toluene and xylene; acetates such as ethyl acetate and butyl acetate; acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isobutyl ketone; Diethyl ketone, 2-
There are ketones such as hexanone, 3-hexanone, di-n-propyl ketone, diisopropyl ketone, di-n-amyl ketone and cyclohexanone; tetrahydrofuran and the like, and these can be used alone or as a mixture of two or more. Examples of the polymerization initiator that can be used include α, α
-Radical formation catalysts such as azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide and the like, and butyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, β-mercaptoethanol and the like as molecular weight regulators Can be

In the above coating composition, in addition to these components,
Auxiliary components such as antioxidants, neutralizers, ultraviolet absorbers, light stabilizers, antistatic agents, pigments, dyes, fungicides, anti-algal agents, foaming agents, lubricants, etc. It can be used after being dispersed and / or dissolved in a solvent. Examples of the organic solvent include heptane and cyclohexane as an aliphatic hydrocarbon; 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. , Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc .; esters, such as methyl acetate, allyl acetate, ethyl stearate, etc .; amines, such as trimethylamine, diphenylamine, hexamethylene diamine; Formamide, dimethylacetamide, dioxane, diethyl ether, diethylenedithioglycol, diacetone alcohol, benzonitrile, dimethyl There are sulfoxides such, which can be used singly or in combination of two or more thereof.

3 Coating 3-1 Mixing of Coating The mixing ratio of the resin [A] and the resin [B] is preferably such that the ratio A / B is 1 to 30 in terms of the solid content weight ratio, and especially 2 to 20.
Is preferred. If it exceeds 30, the dust resistance of the molded film,
If the weather resistance cannot be sufficiently improved, and if it is less than 1, on the other hand, the permeability of the molded film is not sufficient, and the cost is high.

3-2 Formation of Coating In order to form a coating on the surface of the vinyl chloride resin film,
Various known methods are applied. 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 described in 3-1 is formed as a single coating without being in a solution state, a co-extrusion method,
Extrusion coating, extrusion lamination, and lamination are 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, a far infrared drying method and the like. 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 film 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 greater than 1/10 of the substrate firno,
Since there is a difference in flexibility between the base film and the coating, phenomena such as peeling of the coating from the base film are likely to occur,
In addition, a phenomenon occurs in which a crack is generated in the coating and the strength of the base film is reduced, which is not preferable.

Before applying the coating composition, the surface of the vinyl chloride-based resin film is previously washed with alcohol or water, subjected to plasma discharge treatment or corona discharge treatment, or coated with another paint or primer. A pretreatment such as undercoating may be performed. In actually using the agricultural polyvinyl chloride resin film according to the present invention for agricultural purposes, when the coating is formed on only one side, the side provided with the coating is outside the house or tunnel. Use it as

[0035]

The vinyl chloride resin film for agricultural use according to the present invention is provided with a base film and a coating derived from a specific acrylic resin coating composition formed on the surface thereof. The value of application as agricultural coating materials is extremely high.

[0036]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below with reference to embodiments, but the present invention is not limited to the following examples unless it exceeds the gist. Examples 1 to 5, Comparative Examples 1 to 7 Preparation of base film Polyvinyl chloride (average degree of polymerization = 1400) 100 parts by weight dioctyl phthalate 50 〃 epoxidized soybean oil 3 〃 barium-zinc composite liquid stabilizer 1.5 バ barium stearate 0.2 亜 鉛 zinc stearate 0 A resin composition consisting of 1.5% sorbitan laurate was prepared, and the types and amounts of organic phosphates and ultraviolet absorbers shown in Table 2 were blended. Each of the blends was stirred and mixed with a super mixer for 10 minutes, and then kneaded on a mill roll heated to 180 ° C. to prepare a substrate film having a thickness of 0.15 mm.

II. Preparation of Acrylic Resin [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 and 1.0 part by weight of benzoyl peroxide were added. And 100 parts by weight of a mixture of each monomer shown in Table 1, and stirred at 70 ° C. for 3 hours while further adding 0.5 part by weight of benzoyl peroxide while stirring in a nitrogen gas stream to carry out a reaction. About 3
Time, at the same temperature, the resin a to be an acrylic resin
d was obtained.

III. Preparation of Fluorinated Acrylic Resin [B] In the same reactor as in Preparation II, 70 parts by weight of methyl ethyl ketone was added.
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 further stirred at 80 ° C. for 3 hours while stirring in a nitrogen gas stream. After adding 0.5 parts by weight of benzoyl, the reaction was
For a period of time and at the same temperature, resins e to h, which are fluorine-containing acrylic resins, were obtained.

IV. Formation of Coating Acrylic resin [A] and fluorine-containing acrylic resin [B] of the types and amounts shown in Table 2 were blended, and methyl ethyl ketone was added thereto so that the solid content was 20% by weight. Was added to obtain a coating composition. The above coating composition was applied to one surface of the substrate film obtained 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 amount of the coating on each of the obtained films was about 3 g / m ² .

V. Evaluation of Film The performance of the film was evaluated by the following methods, and the results are shown in Table-3. Initial appearance The appearance of the film was visually observed. The evaluation criteria are as follows. A: Colorless and excellent in transparency. ：: Somewhat white, but transparent. Δ: White and translucent. X: Cloudy and devitrified.

Film Flexibility Each film was cut into a width of 5 cm and a length of 15 cm, and was alternately folded at 2 cm intervals in a direction perpendicular to the length direction. In this state, a load of 2 kg was applied from the top and 15
It was left for 24 hours in a thermostat kept at ℃. Then, the load was removed, the fold of the film was extended, and the appearance of the coating was visually observed. The evaluation criteria are as follows. A: No change in the film at the fold was observed. Δ: Cracks are observed in the film at the fold. ×: Cracks are remarkably observed in the film at the fold.

Outdoor Extension Test Each film was covered on a roof-type house (width 3 m, depth 5 m, ridge height 1.5 m, roof slope 30 °) with the surface provided with the coating outside the house, April 1994. From 1996 to 3
An expansion test was performed in a test field in the ash fall area for two years until January. For the stretched film, the appearance test of the film and the elongation retention of the film were measured by the following methods, and the dust resistance of the film during the stretching test was evaluated.

I) Appearance of film: appearance observed with naked eyes. The evaluation criteria are as follows. ◎: No change in appearance such as discoloration is observed. ：: Some change in appearance such as slight discoloration is observed. Δ: Appearance change such as discoloration is considerably observed. ×: Discoloration is observed on the entire surface. ii) Elongation retention rate of the film means a value calculated by the following equation. (Elongation of film after stretching) / (Elongation of film before stretching) x 100

Iii) Dust-proofing property The value calculated by the following equation was judged according to the following evaluation criteria. (Light transmittance of the film collected over time after stretching)
(Light transmittance before expansion *) x 100 * Direct light transmittance at wavelength of 555 mμ (using EPS-2U type manufactured by Hitachi, Ltd.) A: 90% or more. ：: 70 to 89%. Δ: 50 to 69%. X: Less than 50%.

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3]

[Procedure amendment]

[Submission date] December 2, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0045

[Correction method] Change

[Correction contents]

[0045]

[Table 1]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI B32B 27/30 B32B 27/30 D 101 101 (72) Inventor Shunichi Onishi 2 Oike, Iwatsukacho, Nakamura-ku, Nagoya-shi, Aichi Mitsubishi MKV Nagoya Office Co., Ltd.

Claims (3)

[Claims] An alkyl (meth) acrylate monomer represented by the general formula (I) on one or both sides of a vinyl chloride resin film containing an organic phosphate.
0% by weight, 5 to 40% by weight of a hydroxyalkyl (meth) acrylate monomer, 0 to 20% by weight of an α, β-unsaturated carboxylic acid compound containing one or more carboxyl groups in the molecule, and An acrylic resin [A] comprising a copolymer with another polymerizable vinyl monomer, 5 to 40% by weight of a perfluoroalkyl (meth) acrylate monomer represented by the general formula (II),
Fluorinated acrylic resin [B] consisting of a copolymer with an alkyl (meth) acrylate monomer 95 to 60% by weight
A vinyl chloride resin film for agricultural use, comprising a coating of a composition comprising: Embedded image (Wherein, R ¹ is hydrogen or a methyl group, n is an integer of 5 to 16, m is an integer of 0 to 3, a is an integer of 0 or more, b
Represents an integer of 4 to 16, respectively. ) 2. The agricultural polyvinyl chloride resin film according to claim 1, wherein the mixing ratio of the resin [A] and the resin [B] is 1 to 30 in the ratio A / B. 3. The agricultural vinyl chloride resin film according to claim 1, wherein the vinyl chloride resin film contains an ultraviolet absorber.