JPH0848802A - Vinyl chloride-based resin film for agriculture - Google Patents

Abstract

PURPOSE:To obtain the subject film having an improved life and slight selectiv ity of crops by coating the surface of a film consisting essentially of a vinyl chloride-based resin with a specific acrylic resin-based coating compound. CONSTITUTION:This film is obtained by coating (A) at least one side of a film consisting essentially of a vinyl chloride-based resin with (B) an acrylic resin-based coating compound prepared by copolymerizing a monomer having ultraviolet light absorption ability [e.g. 2-(2'-hydroxy-5'-methacryloxy ethylphenyl)-2H-benzotriazole] of the formula. The thickness of the coating film of the component B is 0.1-5mum, especially 0.5-2mm as dried film thickness.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an agricultural vinyl chloride resin film, and more specifically to an agricultural vinyl chloride resin film having a long useful life without using a large amount of an ultraviolet absorber and having a small crop selectivity. Regarding a resin film.

[0002]

2. Description of the Related Art Conventionally, for example, a vinyl house is made by connecting iron or stainless steel pipes bent into a predetermined shape to form a skeleton, and a skylight or a doorway is provided at a predetermined position, and its surface is made of a transparent vinyl chloride resin. Covered by film. In recent years, films covering vinyl houses tend to have improved service life.

[0003]

By the way, as mentioned above, there is a film for a vinyl house which has an improved service life. However, a vinyl chloride resin film originally has a solid surface due to the addition of a plasticizer. There is a problem in that dust cannot be used because the dust is apt to adhere and the dirt becomes severe, and the years of use are shortened. Therefore, for a long period of time, there has been a strong demand for development of a vinyl chloride resin film for agriculture having a dustproof property. In addition, a conventional vinyl chloride resin film used a copolymer containing methyl methacrylate as a main component as a coating material for surface coating, but this coating material deteriorates the film base. It was necessary to add a large amount to block ultraviolet rays. However, since an ultraviolet absorber is mixed in the film for use, the influence of ultraviolet rays on the film base is unavoidable, and it was insufficient to protect the film base from ultraviolet rays.

The present invention has been made against the background of the problems of the prior art as described above, and is excellent in dustproof property and can be improved in service life without using a large amount of ultraviolet absorber.
Moreover, it is an object of the present invention to provide an agricultural vinyl chloride resin film having a low crop selectivity.

[0005]

The present invention is characterized in that an acrylic resin-based paint in which a monomer having an ultraviolet absorbing ability is copolymerized is applied to at least one surface of a film containing a vinyl chloride-based resin as a main component. A vinyl chloride resin film for agriculture is provided.

As the vinyl chloride resin used in the present invention, in addition to polyvinyl chloride, vinyl chloride and other vinyl monomers such as ethylene, propylene, vinyl acetate, vinylidene chloride, acrylic acid, alkyl acrylate, methacryl Examples thereof include copolymers with acid, methacrylic acid alkyl ester, maleic acid, fumaric acid, acrylonitrile, alkyl vinyl ether and the like, or blends thereof.

The agricultural vinyl chloride resin film of the present invention may further contain a plasticizer, a stabilizer, a lubricant or an anti-adhesive agent, an ultraviolet absorber, an antioxidant, a light stabilizer, an inorganic filler, etc., if necessary. Can be added. As the plasticizer added to the vinyl chloride resin, a general plasticizer, a phosphate ester plasticizer, or an epoxy plasticizer can be used.

Examples of the general plasticizer include di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, dibutyl phthalate, butylbenzyl phthalate, dilauryl phthalate, didecyl phthalate, diundecyl phthalate and ditridecyl phthalate. In addition to adipic acid ester plasticizers such as phthalic acid ester plasticizers, dioctyl adipate, ditrinonyl adipate, and diisodecyl adipate, polyester plasticizers, sebacic acid ester plasticizers, trimellitic acid ester plasticizers, etc. can also be used. .

As the phosphoric acid ester type plasticizer, tricresyl phosphate, trixylyl phosphate, tris (isopropylphenyl) phosphate, tributylphosphate, triethylphosphate, triphenylphosphate, triethylphenylphosphate and the like can be used.

As the epoxy-based plasticizer, epoxidized vegetable oil and epoxy resin can be used. Epoxidized soybean oil, epoxidized linseed oil and the like can be used as the epoxidized vegetable oil.

Epoxy resins include epoxidized polybutadiene, methyl epoxystearate, butyl epoxystearate, ethylhexyl epoxystearate, tris (epoxypropyl) isocyanurate, and 3
-(2-xenoxy) -1,2-epoxypropane, bisphenol A, diglycidyl ether, vinyldicyclohexene diepoxy side, and polycondensation product of 2,2-bis (4-hydroxyphenyl) propane and epichlorohydrin are mentioned. The above-mentioned plasticizers may be used alone or in combination of two or more, and the preferable addition amount is 30 to 70 parts by weight of phthalate ester-based plasticizer and phosphoric acid ester-based plasticizer per 100 parts by weight of vinyl chloride resin. 1 to 7 parts by weight and 0.5 to 7 parts by weight of epoxy plasticizer.

As the stabilizer, commonly used stabilizers such as metal soap and organic phosphite stabilizers can be used. Examples of the metal soap include zinc stearate, barium stearate, calcium stearate, barium ricinoleate, calcium laurate, calcium oleate, zinc octoinate and the like.

Examples of the organic phosphite stabilizer include diphenyldecylphosphite, triphenylphosphite, tris (nonylphenyl) phosphite, tridecylphosphite, tris (2-ethylhexyl) phosphite, tristearylphosphite, octyl. Examples include diphenyl phosphite. These stabilizers may be used either individually or in combination of two or more.

Examples of the lubricant or anti-tacking agent include fatty acid-based lubricants such as stearic acid, isostearic acid and palmitic acid, fatty acid amide-based lubricants such as stearic acid amide, methylene bis stearamide and ethylene bis stearamide, and butyl palmitate. , Ester lubricants such as butyl stearate, organophosphate metal salt lubricants such as barium isodecyl phosphate, calcium octadecyl phosphate, polyethylene wax, liquid paraffin, etc., and one or more of them may be used. it can.

Examples of the ultraviolet absorber include commonly used benzophenone-based, benzotriazole-based, salicylate-based, cyanoacrylate-based ultraviolet absorbers, and one or more of these can be used. . The ultraviolet absorber is usually used in an amount of about 0.04 to 1.0 part by weight per 100 parts by weight of the vinyl chloride resin.

As the antioxidant, one kind or two or more kinds of antioxidants such as phenol type, thiodipropionate type and aliphatic sulfide type can be used.
As the light stabilizer, one or more commonly used light stabilizers such as hindered amines can be used.

The inorganic fine powder can be used for the purpose of preventing stickiness of the film surface and improving heat retention. As such an inorganic fine powder, at least one kind of magnesium carbonate, magnesium silicate, silicon oxide, aluminum oxide, aluminum hydroxide, magnesium hydroxide and hydrotalcites can be used. The diameter is preferably 20 μm or less.

0.5 to 6 parts by weight of the dripproofing agent may be added to 100 parts by weight of the vinyl chloride resin. If it is less than 0.5 part by weight, the drip-proof property is poor, while if it exceeds 6 parts by weight, it is not preferable because the amount of blistering on the film surface increases.

Examples of the antidrip agent include sorbitan fatty acid ester, sorbitol fatty acid ester, glycerin fatty acid ester, diglycerin fatty acid ester, sorbitan fatty acid / dibasic acid ester, sorbitol fatty acid / dibasic acid ester, diglycerin fatty acid / dibasic acid. Esters, esters of polyhydric alcohols and fatty acids such as glycerin fatty acid and dibasic acid esters, esters of polyhydric alcohols and fatty acids and dibasic acids, or alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide added to these And the like, specifically, sorbitan palmitate,
Sorbitan stearate, sorbitan stearate / ethylene oxide 2 mol adduct, sorbitan stearate / propylene oxide 3 mol adduct, sorbitol stearate, sorbitol stearate / ethylene oxide 3 mol adduct, diglycerin palmitate, diglycerin stearate , Glycerin stearate, glycerin palmitate / ethylene oxide 2 mol adduct, sorbitan stearate adipate / ethylene oxide 3 mol adduct, sorbitol stearate adipate / ethylene oxide 2 mol adduct, diglycerin palmitate sebacate / propylene oxide 3 And a sorbitol palmitate adipate / ethylene oxide 3 mol adduct. These drip-proof agents can be used alone or in combination of two or more kinds.

The agricultural vinyl chloride resin film of the present invention, together with this drip-proofing agent, is 0.01 to 1.0 part by weight, preferably 0.0 per 100 parts by weight of the vinyl chloride resin.
5 to 0.5 parts by weight of a fluorine-containing compound can be added.

The fluorinated compound is a fluorinated compound having at least one of a fluorinated group and a hydroxyl group or an alkylene oxide group in one molecule, and the fluorinated group is a perfluoroalkyl group (C _n F
_{2n + 1} group), perfluoroalkoxy group (C _n F _{2n + 1} O
Group), a polyfluoroalkyl group (H _m C _n F
_{2n + 1-m} group), perfluoroalkenyl group (C _n F
_2n-1 group), polyfluoroalkenyl group (H _m C _n F
_2n-1-m group), perfluoroalkylene group (C _n F _2n group)
Etc., and in the formula, m = 1 to 3 and n = 3 to 20 are integers. As the alkylene oxide group, (C ₂ H ₄ O) _n ,
(C ₃ H ₄ O) _{n and the} like, where n = 1 to 30.

Specific examples of the fluorine-containing compound include C ₈ F
₁₇ C ₂ H ₄ O (C ₂ H ₄ O) ₈ CH ₃ , C ₈ F ₁₇ CH ₂ CH ₂ OHCH ₂ O (C ₂ H ₄ O) ₁₀ CH
₃ , C ₁₄ F ₂₁ CH ₂ CH (OCH ₃ ) CH ₂ O (C ₂ H ₄ O) ₁₀ CH ₃ , C ₁₄ F ₂₁ CH ₂ C
H (OH) CH ₂ O (C ₂ H ₆ O) ₁₀ H, C ₈ F ₁₇ CH ₂ CH (OCOH ₃ ) CH ₂ O (C ₃ H ₆ O)
₈ CH ₃ , C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) (C ₂ H ₄ O) ₁₂ , C ₆ F ₁₃ CON (C ₂ H ₅ ) (C ₂ H
₄ O) ₈ H, C ₈ F ₁₇ SO ₂ N [CH ₂ CH (OH) CH ₂ CH] ₂ , HCF ₂ C ₅ F ₁₀ CH ₂ O
(C ₂ H ₄ O) ₁₀ H, C ₃ F ₇ OC ₃ F ₆ CH ₂ CH ₂ SCH (COOH) CH ₂ COO (C ₂ H ₄ O)
₁₀ H, C ₃ F ₇ OC ₃ F ₁₀ CH ₂ CH ₂ SCH (CH ₂ COOH) CH ₂ COO (C ₂ H ₄ O)
₁₅ H, However, the present invention is not limited to these.

The paint applied to at least one side of the agricultural vinyl chloride resin film of the present invention is an acrylic resin paint obtained by copolymerizing a monomer having an ultraviolet absorbing ability as described above.

Examples of the UV absorbing monomer include 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole represented by the following structural formula (I), and the following structural formulas (II) to Examples thereof include compounds represented by (IV), but the compounds are not limited to these as long as they are monomers capable of absorbing ultraviolet light and copolymerizable with alkyl acrylates and / or alkyl methacrylates.

[0025]

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[0026]

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[0027]

[Chemical 3]

[0028]

[Chemical 4]

Further, the acrylic resin-based coating material contains, as a main component, an acrylic acid alkyl ester and / or a methacrylic acid alkyl ester, and another copolymerizable monomer.

Examples of alkyl acrylates include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, and the like.

Examples of the alkyl methacrylates include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate and the like.

Other copolymerizable monomers include styrene and maleic acid. In addition, as the other copolymerizable monomer, acrylic acid, methacrylic acid, hydroxymethacrylate, glycidylmethacrylate, hydroxyacrylate, glycidylacrylate, or the like having a functional group at the terminal group can be used. When the contained monomer is used, it can be crosslinked with an isocyanate compound, an epoxy compound, a melamine compound, or the like.

The acrylic resin paint of the present invention can be easily manufactured by the same method as the conventional polymerization method. Further, the acrylic resin-based paint of the present invention may be of a solvent solution type or an emulsion type.

As a method for applying the acrylic resin-based coating material to the agricultural vinyl chloride-based resin film, for example, a coating method such as roll coater, dipping, brush coating, gravure coating, knife coating or reverse coating can be adopted. The polymer layer may be formed not only on one side of the film but also on both sides of the film. The film thickness of the acrylic resin-based coating layer is a dry film thickness of usually 0.1 to 5 μm, preferably 0.5 to 2 μm. If it is less than 0.1 μm, the weather resistance is improved and deterioration due to light or heat is caused. The effect of reducing is not sufficiently obtained, while 5 μm
If it exceeds, the flexibility of the film may be impaired or the coating film may be easily cracked due to bending or the like, which may cause stains.

In the use of the agricultural vinyl chloride resin film of the present invention, the acrylic resin paint surface is attached so as to cover the frame of the vinyl house (not shown) from the outside. For example, when the sunlight in the summer is strong and the acrylic resin-based paint layer side is covered on the outside to cover the frame of the vinyl house, the acrylic resin-based paint formed on at least one side of the film can extend the life of the film. . Moreover, by coating the base film with an acrylic resin-based coating material obtained by copolymerizing this UV-absorbing monomer, it is possible to control the amount of UV light transmitted through the film, so that the necessary amount of UV light can be stored inside the vinyl house. Since it is irradiated to, even in the case of crops such as eggplant, strawberry, tomato that use insects such as bumblebee for pollination,
There is no problem that insects do not fly and pollination is not performed well.

[0036]

EXAMPLES The present invention will be described in more detail with reference to examples. Examples 1 and 2, Comparative Example 1 A vinyl chloride resin composition having a formulation shown in Table 1 was charged in a Henschel mixer, and the mixture was stirred and mixed for 10 minutes, and then 1
It was heated and melted at 75 ° C., kneaded by a roll, and then a calender device was used to form a film having a thickness of 0.1 mm.

[0037]

[Table 1]

Acrylic resin-based paints having the formulation shown in Table 2 were synthesized on these films, and the film obtained from the composition (A) was coated with the paint (I) by a gravure roll to about 1%.
Apply it to 0 g / m ² and apply about 1μ on the film surface.
m coating layer was formed (the test body of Comparative Example 1). Similarly, the film obtained from the composition (B) is coated with the paint (II).
Was applied (the test body of Example 1), and the coating (III) was applied to the film obtained from the composition (B) (the test body of the Example 2) to obtain a film of each test body.

[0039]

[Table 2]

* 1) As an ultraviolet absorber monomer, 2-
(2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole is used * 2) As a solvent, a mixed solvent of isopropyl alcohol / ethyl acetate / toluene (weight ratio) = 100/15/10 is used. The spectral light transmittance of the above film at 280 nm to 600 nm is as shown in FIG. 1, and it is understood that the absorption curves of Examples 1 and 2 have better light transmittance than Comparative Example 1.

Next, these films were spread in a test house (experimental building owned by the applicant of the present application) in the beach area of Chiba prefecture for about two years from April 1992 to April 1994,
The stain and residual elongation were evaluated. The results are shown in Table 3. The stain was evaluated by the transmittance of 555 nm, and the residual elongation was calculated by the following formula. Residual elongation (%) = (elongation after exposure / elongation before exposure) x 1
00

[0042]

[Table 3]

In Examples 1 and 2, the residual elongation of about 80% remains, which is practically within the safe use range. However, in Comparative Example 1, the residual elongation is 50%, and there is a risk of breaking in a strong wind.

[0044]

INDUSTRIAL APPLICABILITY In the vinyl chloride resin film for agricultural use of the present invention, an acrylic resin coating material obtained by copolymerizing a monomer having an ultraviolet absorbing ability is coated on at least one surface of the film containing the vinyl chloride resin as a main component. Due to
It is possible to provide a vinyl chloride resin film for agriculture, which has improved service life and low crop selectivity.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between wavelength and transmittance of an agricultural vinyl chloride resin film of the present invention and a conventional film.

Claims (1)

[Claims] 1. A vinyl chloride resin film for agriculture, characterized in that an acrylic resin paint which is copolymerized with a monomer having an ultraviolet absorbing ability is applied to at least one surface of a film containing a vinyl chloride resin as a main component.