JP2003061486A - Agricultural vinyl chloride-based resin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an agricultural film solving the problem that when a conventional agricultural film flaps and chafes at parts thereof butting on MAIKASEN (R) (plastic tape for fixing plastic film for greenhouse) or the like, it may break, therefore has been unusable for a long period. SOLUTION: This agricultural film is obtained by making a vinyl chloride- based resin composition into film; wherein the composition comprises 100 pts.wt. of a vinyl chloride-based resin, 0.1-10 pt(s).wt. of a homopolymer or copolymer of glycidyl acrylate and/or glycidyl methacrylate or copolymer of glycidyl acrylate or glycidyl methacrylate and at least one kind of monomer selected from methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate and butyl acrylate, 0.01-1 pt.wt. of an alkylbenzoic acid metal salt, and 0.1-10 pt(s).wt. of an ethylene-vinyl acetate copolymer 20-70 wt.% in vinyl acetate content.

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an agricultural vinyl chloride resin film. Conventionally, vinyl chloride resin films have been widely used as coating materials for agricultural tunnels, agricultural houses, etc. because of their low cost, good transparency, excellent heat retention and strength. I have. [0003] The conventional agricultural film has a problem that the film is broken if it flutters and rubs in a portion in contact with a mica wire or the like, and cannot be used for a long time. . DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and the invention according to claim 1 provides glycidyl acrylate and glycidyl acrylate based on 100 parts by weight of a vinyl chloride resin. / Or glycidyl methacrylate homopolymer or copolymer, or glycidyl acrylate or glycidyl methacrylate, methyl methacrylate,
A copolymer with at least one monomer selected from ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, and butyl acrylate is used in 0.1%.
1 to 10 parts by weight, metal alkyl benzoate 0.01 to
Agricultural vinyl chloride resin film obtained by filming a vinyl chloride resin composition containing 1 part by weight and 0.1 to 10 parts by weight of ethylene-vinyl acetate having a vinyl acetate content of 20 to 70% by weight. And The vinyl chloride resin used in the present invention includes polyvinyl chloride, a copolymer of a vinyl chloride monomer and another monomer copolymerizable with vinyl chloride, and a copolymer of a vinyl chloride monomer and a higher vinyl ether. Such as copolymers,
Or a mixture thereof. Examples of monomers copolymerizable with vinyl chloride include olefin monomers such as ethylene, propylene, maleic ester, methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methacrylic acid, acrylic acid, and vinyl acetate. And vinyl monomers. The homopolymer or copolymer of glycidyl acrylate or glycidyl methacrylate used in the present invention, or glycidyl acrylate or glycidyl methacrylate, and methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, or butyl acrylate. The copolymer with one or more monomers is a vinyl chloride resin 10
0.1 to 10 parts by weight is added to 0 parts by weight. If the addition amount is small, the weather resistance is not improved, and if the addition amount is large, the weather resistance is not much improved although the cost is increased. As the metal alkyl benzoate used in the present invention, for example, those represented by the general formula shown in Chemical formula 1 can be used. Embedded image (R represents a straight-chain or branched-chain alkyl group having 2 to 5 carbon atoms, and M represents a metal.) As the substituent R of the above-mentioned metal alkyl benzoate, for example, an ethyl group, a propyl group Groups, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, amyl group, isoamyl group and the like. R is preferably a branched alkyl group having 3 to 5 carbon atoms. Particularly preferably, tert-
It is a butyl group. Metals which can form salts with alkylbenzoic acids include magnesium, calcium, barium,
Zinc can be exemplified. Particularly preferred are barium and zinc. [0010] The metal alkyl benzoate used in the present invention is used in an amount of 0.01 to 100 parts by weight of the vinyl chloride resin.
Add ~ 1 part by weight. If the addition amount is small, the weather resistance is not improved, and if the addition amount is large, the weather resistance is not improved although the cost is increased. [0011] The ethylene-vinyl acetate copolymer used in the present invention has a vinyl acetate content of 20 to 70% by weight, which sufficiently satisfies the effects of the present invention. It is particularly preferably 30 to 50% by weight, and the effect of the present invention tends to be further improved. The ethylene-vinyl acetate copolymer used in the present invention is added in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the vinyl acetate content or ethylene-vinyl acetate copolymer is low, the tear strength tends not to improve.If the vinyl acetate content or ethylene-vinyl acetate copolymer is high, the tear strength tends to increase. Tend not to improve much. [0012] In addition to the ethylene-vinyl acetate copolymer, polyethylene, polypropylene, polybutene, ethylene-α-olefin copolymer may be used as long as the weather resistance, tear strength and rubbing resistance of the film are not impaired. ,
Olefin resins such as propylene-α olefin copolymer, ethylene-acrylate copolymer, ethylene-methacrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer are compounded. Is also good. The homopolymer or copolymer of glycidyl acrylate or glycidyl methacrylate used in the present invention, or glycidyl acrylate or glycidyl methacrylate, and methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, or butyl acrylate. The addition amount of the copolymer with one or more kinds of monomers is related to the weather resistance of the film. Glycidyl acrylate or glycidyl methacrylate homopolymer or copolymer, or glycidyl acrylate or glycidyl methacrylate, and methyl methacrylate, ethyl methacrylate, Methacrylate, methyl acrylate, ethyl acrylate, copolymers and ethylene with one or more monomers selected from butyl acrylate -
Vinyl acetate content of vinyl acetate copolymer and ethylene-
By the amount of vinyl acetate copolymer added to the desired value,
The rub resistance of the film can be improved. If the addition amount of either one is small, the rub resistance of the film cannot be improved. The lubricant used in the present invention is added in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the vinyl chloride resin. If the addition amount is small, the effect of the present invention cannot be obtained, and if the addition amount is large, the effect of the present invention does not change while the cost increases. The lubricant used in the present invention includes metal soaps such as zinc stearate, barium stearate and calcium stearate; hydrocarbons such as liquid paraffin, polyethylene waxes and chlorinated hydrocarbons; stearic acid, stearin Fatty acids and fatty acid amides such as acid amide, palmitic acid amide, methylene bisstearamide, ethylene bisstearamide; and lubricants such as fatty acid esters such as butyl stearate, cetyl palmitate, and monoglyceride stearate can be used. These lubricants
They may be used alone or in combination of two or more. Preferred is 0.01-1 and particularly preferred is 0.05-0.5. The vinyl chloride resin film for agriculture of the present invention may further contain a plasticizer, a drip-proof agent, an anti-fog agent, an anti-fog agent, a heat stabilizer, a light stabilizer, Additives such as an anti-adhesion agent, an ultraviolet absorber, an antioxidant, and a filler can be added. The drip-proofing agents usable in the present invention include conventionally known sorbitan fatty acid esters, sorbitol fatty acid esters, glycerin fatty acid esters, diglycerin fatty acid esters, sorbitan fatty acid / dibasic acid esters, glycerin fatty acid / dibasic acid esters. Acid esters, esters of polyhydric alcohols such as diglycerin fatty acids and dibasic acid esters with fatty acids, esters of polyhydric alcohols with fatty acids and dibasic acids, or alkylene oxides such as ethylene oxide and propylene oxide added thereto Sorbitan palmitate, sorbitan stearate, sorbitan stearate / ethylene oxide 1 mol adduct, sorbitan stearate / ethylene oxide 2 mol adduct, sorbitan stearate Rate propylene oxide 3
Mol adduct, sorbitan stearate / ethylene oxide 3 mol adduct, diglycerin palmitate, diglycerin cetearate, glycerin palmitate, 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 mol adduct, sorbitol palmitate adipate / ethylene oxide 3 mol adduct, and the like can be used, and particularly, Preferred are sorbitan dripproofing agents such as sorbitan palmitate. These drip proof agents are
They may be used alone or in combination of two or more. It is preferable to add 0.5 to 5 parts by weight of the above drip-proofing agent to 100 parts by weight of the vinyl chloride resin. If the addition amount of the drip-proof agent is too small, the drip-proof effect is not sufficient, and if the addition amount of the drip-proof agent is too large, not only does the cost increase but also bleeding occurs,
The film surface may be whitened. Examples of the antifog include fluorine-containing compounds having a fluorine-containing group and at least one of a hydroxyl group and an alkylene oxide group in one molecule. As the fluorine-containing group, a perfluoroalkyl group (C _n F _{2n + 1} ),
Perfluoroalkoxy group (C _n F _{2n + 1} O group), polyfluoroalkyl group _{(H m C n F 2n +} 1-m group), perfluoro alkenyl group (C _n F _2n-1 group), polyfluoroalkenyl Base
_{(H m C n F 2n-} 1-m group), and the like (wherein m is an integer of 1 to 3, n represents 3 to 20 integer), the alkylene oxide group, (C ₂ H ₄ O) _n , (C ₃ H ₆ O) _{n and the} like (where n is an integer of 1 to 30). The addition amount of these fluorine compounds is 0.01 to 1 part by weight, preferably 0.05 to 0.1 part by weight, per 100 parts by weight of the vinyl chloride resin.
5 parts by weight. Further, specific examples of the fluorine-based compound include compounds as shown in Chemical formula 2. Embedded image Examples of the heat stabilizer include metal soaps such as zinc stearate, barium stearate, calcium stearate, barium ricinoleate, calcium laurate and calcium oleate; epoxy compounds such as epoxidized soybean oil; diphenyldecyl phosphite; Phenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, tristearyl phosphite,
Organic phosphite-based stabilizers such as octyl diphenyl phosphite, and tin-based stabilizers such as dibutyltin laurate, dibutyltin malate, organic tin mercaptide, and organic tin sulfonamide can be used. These stabilizers can be used alone or in combination of two or more. The amount of the heat stabilizer to be added is as follows.
0.5 to 10 parts by weight, preferably 1 to 10 parts by weight, based on 0 parts by weight
5 parts by weight are preferred. As the light stabilizer, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,2
6,6-pentamethyl-4-piperidyl stearate,
2,2,6,6-tetramethyl-4-piperidylbenzoate, N- (2,2,6,6-tetramethyl-4-piperidyl) dodecylsuccinimide, 1-[(3,5-
Di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] -2,2,6,6-tetramethyl-4-piperidyl (3,5-di-tert-butyl-
4-hydroxyphenyl) propionate, bis (2,
2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6,-
(Pentamethyl-4-piperidyl) -2-butyl-2-
(3,5-di-tert-butyl-4-hydroxybenzyl) malonate, N, N′-bis (2,2,6,6-
Tetramethyl-4-piperidyl) hexamethylenediamine, tetra (2,2,6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, bis (2
2,6,6-tetramethyl-4-piperidyl) di (tridecyl) butanetetracarboxylate, bis (1,
2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) butanetetracarboxylate, 3,9
-Bis {1,1-dimethyl-2- [tris (2,2,
6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy] ethyl} -2,
4,8,10-tetraoxysaspiro [5,5] undecane, 3,9-bis {1,1-dimethyl-2- [tris (1,2,2,6,6-pentamethyl-4-piperidyloxy) Carbonyloxy) butylcarbonyloxy] ethyl {-2,4,8,10-tetraoxaspiro [5,
5] Undecane, 1,5,8,12-tetrakis @ 4
6-bis [N- (2,2,6,6-tetramethyl-4-
Biperidyl) butylamino] -1,3,5-triazin-2-yl {-1,5,8,12-tetraazadodecane, 1- (2-hydroxyethyl) -2,2,6,6-
Tetramethyl-4-piperidinol / dimethyl succinate condensate, 2-tert-octylamino-4,6-dichloro-s-triazine / N, N'-bis (2,2,6,
6-tetramethyl-4-piperidyl) hexamethylenediamine condensate, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine /
Hindered amine light stabilizers such as dibromoethane condensate and the like are included. Examples of the ultraviolet absorber include salicylic acid ester, benzotriazole, hydroxybenzophenone,
And acrylonitrile-substituted products. These ultraviolet absorbers can be used alone or in combination of two or more. Specifically, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-ethoxybenzophenone,
-Hydroxy-4-octoxybenzophenone, 5,
2-hydroxybenzophenones such as 5'-methylenebis (2-hydroxy-4-methoxybenzophenone);
2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'
-Di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-ter
t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-te
rt-octylphenyl) benzotriazole, 2-
(2'-hydroxy-3 ', 5'-dicumylphenyl)
Benzotriazole, 2,2′-methylenebis (4-t
2- (2'-hydroxyphenyl) benzotriazoles such as tert-octyl-6-benzotriazole) phenol; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3 ', 5'-Di-tert-butyl-4'-hydroxybenzoate, hexadecyl-3,5-di-tert
Benzoates such as -butyl-4-hydroxybenzoate; oxanilides such as 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-β, β-diphenylacrylate, methyl-2-cyano-3-methyl −
Examples include cyanoacrylates such as 3- (p-methoxyphenyl) acrylate. These ultraviolet absorbers may be used alone or in combination of two or more. Examples of the antioxidant include alkylphenol, alkylenebisphenol, alkylphenol thioether, β, β'-thiopropionate, organic phosphite, aromatic amine, phenol / nickel complex and the like. These antioxidants can be used alone or in combination of two or more. As the filler, calcium carbonate, titanium oxide, aluminum hydroxide, talc, feldspar, silica, hydrotalcite and the like can be used. As the plasticizer, dioctyl phthalate (DOP) and diisononyl phthalate (DI
NP), butyl benzyl phthalate (BBP),
General phthalate plasticizers represented by diisodecyl phthalate (DIDP) and diundecyl phthalate (DUP), dioctyl adipate (DOA), dioctyl sebacate (D
OS), general fatty acid ester plasticizers represented by dioctyl azelate (DOZ), trimellitate plasticizers represented by trioctyl trimellitate (TOTM), polypropylene adipate and the like. Polymeric plasticizers such as polyester plasticizers, other sebacic acid-based plasticizers, general plasticizers such as chlorinated paraffin, tricresyl phosphate (TCP), trixylyl phosphate (TXP), tris (isopropyl) Phenyl) phosphate, tributyl phosphate, triethyl phosphate, triphenyl phosphate, phosphate plasticizers such as triethylphenyl phosphate, epoxidized vegetable oils, epoxy resins can be used. As epoxidized vegetable oils,
Epoxidized soybean oil Epoxidized linseed oil and the like are listed. Epoxy resins include epoxidized polybutadiene, methyl epoxystearate, butyl epoxystearate, ethylhexyl epoxystearate, tris (epoxypropyl) isocyanurate, and 3- (2- Xenoxy) -1,2-epoxypropane, bisphenol A
Epoxy plasticizers such as diglycidyl ether, vinyl dicyclohexene diepoxide, and a polycondensate of 2,2-bis (4-hydroxyphenyl) propane and epichlorohydrin. These plasticizers can be used alone or in combination of two or more. The amount of the plasticizer to be added is preferably 20 to 70 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the added amount of the plasticizer is small, the film becomes too hard and tends to be difficult to handle as an agricultural film, while if the added amount of the plasticizer is large, the film becomes too soft and tends to be difficult to handle. . The vinyl chloride resin composition obtained by adding the above-mentioned plasticizer, stabilizer and various additives to be added to the vinyl chloride resin can be prepared by a suitable method such as a calendering method, an extrusion method and an inflation method. By means, it is formed into a film of a desired thickness. Regarding the thickness of the film, a value of 0.
It is preferably from 0.3 to 0.3, and particularly preferably from 0.05 to 0.2 mm. The vinyl chloride resin film obtained as described above may be formed on one or both sides with a coating film of an appropriate paint. For example, when used as a covering material for agricultural facilities, a dust-proof coating of a solvent-based, water-based, or UV-curable paint is formed on the outer surface when spread, or the inner surface when spread. On the surface to be formed, a drip-proof coating film of a coating obtained by adding a hydrophilizing substance such as colloidal silica to a solvent-based, water-based or ultraviolet-curable coating can be formed. As the solvent-based coating, for example, acrylic resin-based, vinyl chloride resin-based, cellulose resin-based, fluorine resin-based, polyamide-based, urethane resin-based, epoxy resin-based, and silicone resin-based paints can be used. As the water-based paint, for example, acrylic resin-based, polyester-based,
Paints such as urethane resin and epoxy resin can be used. As the UV-curable paint, for example, an acrylic resin paint, an acrylic-modified urethane resin paint, an acrylic-modified epoxy resin paint, a mercapto derivative paint, an epoxy resin paint, or the like can be used. As means for applying the above coating material to a film, ordinary coating means such as a doctor knife coater, a comma doctor coater, a roll coater, a gravure coater, a spray coater and the like are employed. A gravure coater is preferable in consideration of the properties such as the viscosity and the amount of coating. As a method for mixing the composition of the present invention, there is a method such as melt kneading. Specific examples of the melt-kneading apparatus include a mixing roll, a Banbury mixer, a kneader, a single-screw extruder, a twin-screw extruder, and a tandem-type extruder. As a method for producing a film, T
Die method, inflation method, calendar method and the like can be mentioned. EXAMPLES Examples 1 to 11 and Comparative Examples 1 to 6 Films having a thickness of 0.1 mm were prepared according to the formulations shown in Tables 1 and 2 using a calender at a roll temperature of 180 ° C. Created. The obtained film was 4 m wide, 3 m high, and 10 m long.
m, and the film was evaluated for weather resistance, tear strength, and rub resistance by the following methods. The results are shown in Tables 1 and 2. (1) The maximum elongation of the film after 18 months from the weathering expansion,
From the maximum elongation of the film immediately after production, the remaining elongation was determined by the following formula, and evaluated according to the following criteria. (Equation 1) <Standard>: Residual elongation is 80% or more ○: Residual elongation is 50% or more and less than 80% Δ: Residual elongation is 20% or more and less than 50% X: Residual elongation is less than 20% (2) Make a 10 cm vertical cut in the film before tear strength expansion,
Eighteen months after the spreading, the state of the tear was visually observed and evaluated according to the following criteria. ：: Almost no cracks spread ○: Slightly cracks spread X: Large tears from the cuts (3) Scratch resistance 18 months after expansion, the film was torn at the part where it came into contact with the mica wire or pipe. It was visually observed and evaluated according to the following criteria. <Criterion> ◎: Not broken at all ：: Partially broken but not problematic for practical use △: Slight tears are noticeable and need repair X: Many tears and need to be replaced [Table 1] ] * 1: Sorbitan monostearate * 2: Bisamide (Nippon Kasei) * 3: VS-130 (Kyodo Yakuhin) * 4: LA-63 (Asahi Denka) * 5: DS-403 (Daikin) * 6: Glycidyl methacrylate and methyl methacrylate * 7: Homopolymer of glycidyl methacrylate * 8: Bisphenol A diglycidyl ether * 9: Vinyl acetate content = 15% * 10: Vinyl acetate content = 41% * 11: Vinyl acetate content = 60% * 1 to 11 are the same as those in the examples. [Effects of the present invention] As described in detail above, the vinyl chloride resin film for agriculture of the present invention has excellent weather resistance, tear strength and rub resistance. It is excellent. Furthermore, since it is possible to reduce the breakage even at the portion in contact with the mica wire or the like even if it flaps, it can be used for a long time.

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Claims (1)

Claims: 1. A glycidyl acrylate and / or glycidyl methacrylate homopolymer or copolymer, or glycidyl acrylate or glycidyl methacrylate, and methyl methacrylate or ethyl methacrylate, based on 100 parts by weight of a vinyl chloride resin. Butyl methacrylate, methyl acrylate, ethyl acrylate, 0.1 to 10 parts by weight of a copolymer with one or more monomers selected from butyl acrylate, metal benzoate 0.01 to 1 part by weight, vinyl acetate Agricultural vinyl chloride resin film obtained by filming a vinyl chloride resin composition containing 0.1 to 10 parts by weight of ethylene-vinyl acetate having a content of 20 to 70% by weight