JP5009458B2 - Agricultural vinyl chloride resin film - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an agricultural vinyl chloride resin film, and more particularly to an agricultural vinyl chloride resin film having excellent resistance to rubbing at a pipe contact portion.
[0002]
[Prior art]
Conventionally, vinyl chloride resin films have been widely used as covering materials for agricultural tunnels, agricultural houses, etc. because they are inexpensive, have good transparency, and have excellent heat retention and strength. When a covering material made of such is used for tunnels, agricultural houses, etc., there is a problem that rubbing occurs at the contact portion with the pipe, tearing occurs from the rubbing portion, and the crop is greatly adversely affected.
[0003]
In addition, there is a problem that dew condensation occurs inside the covering material of the tunnel or agricultural house, and water drops fall from the covering material to the crop.
In order to solve this problem, the vinyl chloride resin film contains a drip-proofing agent which is a kind of surfactant to increase the hydrophilicity of the film surface so that the surface of the film is uniformly wetted. Water droplets generated on the surface were allowed to flow down quickly.
[0004]
[Problems to be solved by the invention]
However, agricultural vinyl chloride resin films are often used repeatedly, and tears occur, often making them unusable.
[0005]
[Means for Solving the Problems]
The present invention has been made in order to solve the above-described problems. The plasticizer is 20 to 70 parts by weight, the drip-proofing agent is 0.5 to 5 parts by weight, and the chemical formula 1 is 100 parts by weight of the vinyl chloride resin. A vinyl chloride resin film for agriculture, comprising 0.05 to 0.5 parts by weight of the compound (I) represented by the general formula shown.
[0006]
[Chemical 1]
_{R-NHCONH- (CH 2) n} -NHCONH-R '
(N represents an integer of 2 to 12, R and R ′ represent an alkyl group, an alkenyl group, an aryl group, or an alkyl-substituted aryl group)
[0007]
Examples of the vinyl chloride resin used in the present invention include polyvinyl chloride, copolymers of vinyl chloride monomers and other monomers copolymerizable with vinyl chloride, and copolymers of vinyl chloride monomers and higher vinyl ethers. Or a mixture thereof. Examples of monomers copolymerizable with vinyl chloride include olefin monomers such as vinyl acetate, ethylene, propylene, maleate, methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methacrylic acid, and acrylic acid. A vinyl-type monomer is mentioned.
[0008]
Examples of plasticizers include dioctyl phthalate (DOP), diisononyl phthalate (DINP), butyl benzyl phthalate (BBP), diisodecyl phthalate (DIDP), and diundecyl phthalate (DUP). General fatty acid ester plasticizers represented by general phthalate plasticizers, adipic acid dioctyl ester (DOA), sebacic acid dioctyl ester (DOS), azelaic acid dioctyl ester (DOZ), and trimellitic acid trioctyl General sebacic acid plasticizers such as trimellitic acid ester plasticizers typified by esters (TOTM), polyester plasticizers typified by polypropylene adipate, etc., chlorinated paraffin, etc. Plasticizer Phosphate ester plasticizers such as zilphate (TCP), trixylyl phosphate (TXP), tris (isopropylphenyl) phosphate, tributyl phosphate, triethyl phosphate, triphenyl phosphate, triethylphenyl phosphate, epoxidized vegetable oil, epoxy resin Examples of epoxidized vegetable oils include epoxidized soybean oil, epoxidized linseed oil, etc., and epoxy resins include epoxidized polybutadiene, epoxy methyl stearate, epoxy butyl stearate, ethyl hexyl epoxy stearate, tris ( Epoxypropyl) isocyanurate, 3- (2-xenoxy) -1,2-epoxypropane, bisphenol A diglycidyl ether, vinyl dicyclohexene die Kisaido, epoxy plasticizers such as 2,2-bis (4-hydroxyphenyl) polycondensate of propane and epichlorohydrin. These plasticizers can be used alone or in admixture of two or more.
The plasticizer is added in an amount of 20 to 70 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
If the added amount of the plasticizer is too small, the resin composition becomes hard and difficult to be formed into a film. Conversely, if the added amount of the plasticizer is too large, the film becomes sticky and difficult to handle.
[0009]
As the drip-proofing agent that can be used in the present invention, conventionally known sorbitan fatty acid ester, sorbitol fatty acid ester, glycerin fatty acid ester, diglycerin fatty acid ester, sorbitan fatty acid / dibasic acid ester, glycerin fatty acid / dibasic acid ester, Diglycerin fatty acid / dibasic acid ester and other polyhydric alcohols and fatty acid esters, polyhydric alcohol fatty acid and dibasic acid esters, or compounds in which alkylene oxides such as ethylene oxide and propylene oxide are added Specifically, sorbitan palmitate, sorbitan stearate, sorbitan stearate / ethylene oxide 1 mol adduct, sorbitan stearate / ethylene oxide 2 mol adduct, sorbitan stearate / Lopylene oxide 3 mol adduct, sorbitan stearate / ethylene oxide 3 mol adduct, diglycerol palmitate, diglycerol stearate, glycerol palmitate, glycerol stearate, glycerol 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, etc. can be used However, sorbitan drip-proofing agents such as sorbitan palmitate are particularly preferable. These drip-proofing agents may be used alone or in combination of two or more.
As addition amount of said dripproofing agent, 0.5-5 weight part is added with respect to 100 weight part of vinyl chloride resin.
If the amount of drip-proofing agent added is too small, the drip-proofing effect will not be sufficient. Conversely, if the amount of drip-proofing agent added is too large, not only will the cost increase, but bleeding will occur and the film surface will be whitened. There is.
[0010]
To the agricultural vinyl chloride resin film of the present invention, 0.05 to 0.5 parts by weight of the compound (I) represented by the general formula 1 is added with respect to 100 parts by weight of the resin.
If the amount of the compound represented by the general formula of Chemical Formula 1 is too small, the rub resistance cannot be sufficiently improved, and if it is too large, bloom occurs and the transparency is lowered.
[0011]
In the agricultural vinyl chloride resin film of the present invention, additives such as an antifogging agent, a heat stabilizer, a light stabilizer, a lubricant or an anti-adhesive agent, an ultraviolet absorber, an antioxidant, and a filler are added as necessary. Can be added.
[0012]
Examples of the anti-fogging agent include a fluorine-based compound having at least one of a fluorine-containing group and a hydroxyl group or an alkylene oxide group in one molecule. The fluorine-containing group includes a perfluoroalkyl group (C _n F _{2n + 1} group), 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) And a polyfluoroalkenyl group (H _m C _n F _2n-1-m group) and the like (wherein m is an integer of 1 to 3, n is an integer of 3 to 20), and an alkylene oxide group is (C ₂ H ₄ O) _n , (C ₃ H ₆ O) _{n and the} like (in the formula, n is an integer of 1 to 30). The amount of these fluorine compounds added is 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, based on 100 parts by weight of the resin. Moreover, as a specific example of a fluorine-type compound, a compound as shown to Chemical formula 2 is mentioned.
[0013]
[Chemical formula 2]
[0014]
Examples of heat stabilizers include zinc stearate, barium stearate, calcium stearate, barium ricinoleate, calcium laurate and calcium oleate, epoxy compounds such as epoxidized soybean oil, diphenyldecyl phosphite, and triphenyl phosphite. Organic phosphite stabilizers such as tris (nonylphenyl) phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, tristearyl phosphite, octyl diphenyl phosphite, dibutyltin laurate, dibutyltin malate, organic Tin-based stabilizers such as tin mercaptide and organic tin sulfonamide can be used.
Moreover, these stabilizers can be used individually or in mixture of 2 or more types.
The addition amount of the heat stabilizer is 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight with respect to 100 parts by weight of the resin.
[0015]
Examples of the light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetra Methyl-4-piperidylbenzoate, N- (2,2,6,6-tetramethyl-4-piperidyl) dodecylsuccinimide, 1-[(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl Oxyethyl] -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-piperidyloxycarbonyloxy) butylcarbonyloxy] ethyl} -2,4,8,10-tetra Oxaspiro [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 condensation 2-tert-octylamino-4,6-dichloro-s-triazine / N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine condensate, N, N '-Bis ( And hindered amine light stabilizers such as 2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine / dibromoethane condensate.
[0016]
Lubricants include metal soaps such as zinc stearate, barium stearate, calcium stearate; hydrocarbons such as liquid paraffin, polyethylene waxes, chlorinated hydrocarbons; stearic acid, stearamide, palmitate, methylenebis Lubricants such as fatty acids and fatty acid amides such as stearoamide and ethylenebisstearamide; fatty acid esters such as butyl stearate, cetyl palmitate and monoglyceride stearate can be used.
These lubricants may be used alone or in combination of two or more.
[0017]
Examples of ultraviolet absorbers include salicylic acid esters, benzotriazoles, hydroxybenzophenones, acrylonitrile substitution products, and the like. These ultraviolet absorbers can be used alone or in admixture of two or more. Specifically, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-ethoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5′-methylenebis (2-hydroxy 2-hydroxybenzophenones such as -4-methoxybenzophenone); 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl) Phenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-tert-) Octylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) 2- (2′-hydroxyphenyl) benzotriazoles such as nzotriazole and 2,2′-methylenebis (4-tert-octyl-6-benzotriazole) phenol; phenyl salicylate, resorcinol monobenzoate, 2,4 Benzoates such as di-tert-butylphenyl-3 ′, 5′-di-tert-butyl-4′-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2-ethoxy Oxanilides such as -4'-dodecyl oxanilide; cyanoacrylates such as ethyl-α-cyano-β, β-diphenylacrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate Is mentioned.
These ultraviolet absorbers may be used alone or in combination of two or more.
[0018]
Examples of the antioxidant include alkylphenols, alkylene bisphenols, alkylphenol thioethers, β, β′-thiopropionic acid esters, organic phosphites, aromatic amines, phenol / nickel composites, and the like. These antioxidants can be used alone or in admixture of two or more.
[0019]
As the filler, calcium carbonate, titanium oxide, aluminum hydroxide, talc, feldspar, silica, hydrotalcite and the like can be used.
[0020]
The vinyl chloride resin composition obtained by adding the above-described plasticizer, stabilizer and various additives added as necessary to the vinyl chloride resin is obtained by appropriate means such as a calendar method, an extrusion method, an inflation method, etc. A film having a desired thickness is formed.
About the thickness of a film, about 0.05-0.2 mm is preferable.
[0021]
The vinyl chloride resin film obtained as described above can also form a coating film with an appropriate paint on one side or both sides.
For example, if it is used as a covering for agricultural facilities, a dust-proof coating film with solvent-based, water-based or UV-curing paint is formed on the outer surface when expanded, or the inner surface when expanded. On the surface, a drip-proof coating film can be formed by using a paint obtained by adding a hydrophilic substance such as colloidal silica in a solvent-based, water-based or ultraviolet curable paint.
[0022]
Examples of the solvent-based paint that can be used include acrylic resin-based, vinyl chloride resin-based, cellulose resin-based, fluororesin-based, polyamide-based, urethane resin-based, epoxy resin-based, and silicone resin-based paints.
Examples of water-based paints that can be used include acrylic resin-based, polyester-based, urethane resin-based, and epoxy resin-based paints.
As the ultraviolet curable coating material, for example, acrylic resin-based, acrylic-modified urethane resin-based, acrylic-modified epoxy resin-based, mercapto derivative-based, epoxy resin-based coatings and the like can be used.
[0023]
【Example】
As an example, the composition shown in Table 1 was stirred and mixed for 10 minutes with a Henschel mixer, kneaded with a Banbury mixer, and then a film having a thickness of 0.1 mm and a width of 300 cm was prepared by a calendar method.
The resulting agricultural vinyl chloride resin film is inscribed, and the inscribed part is displaced from the pipe at the top of the agricultural house, opening 4m, height 2.5m, length 30m. Each was expanded and checked for rubbing and tearing of the pipe part every four months. The expansion period is from October 1, 1998 to September 31, 1999. In addition, the bloom was evaluated after being left indoors for 1 month after film formation.
[0024]
[Table 1]
* 1 Epicoat 6828 (manufactured by Ciel Chemical Co., Ltd.)
* 2 Bisacid (manufactured by Nippon Kasei Co., Ltd.)
* 3 SLIPAX E (Nippon Kasei Co., Ltd.)
* 4 Hexamethylenebisstearyl urea Haclean SH (Nippon Kasei Co., Ltd.)
* 5 DS-403 (Daikin)
* 6 Kima Soap 944LD (Ciba Geigy)
* 7 {(C ₁₈ H ₃₇ O) ₃ POO} ₂ Zn
* 8 Number of places where tears occur at the intersection of the pipe at the top of the house and the mica line (50 places in total) * 9 ○ Less bloom △ Some bloom is seen × Bloom is bad and poorly transparent [0025]
As a comparative example, a film was produced from the formulation shown in Table 2 by the same method as in the example and evaluated in the same manner as in the example.
[0026]
[Table 2]
* 1 to 9 are the same as Table 1. [0027]
【Effect of the invention】
By adopting the above-described configuration, the present invention reduces the frequency of tearing after being spread on a house in an agricultural film, and can suppress the effects on crops in the house. It also saves the trouble of repairing the film, which is a great advantage for farmers.

Claims (1)

20-70 parts by weight of a plasticizer, 0.5-5 parts by weight of a drip-proofing agent, and 0.05-0.5 of the compound (I) represented by the general formula shown in Chemical formula 1 with respect to 100 parts by weight of a vinyl chloride resin. Agricultural vinyl chloride resin film with parts by weight added.
[Chemical 1]
_{R-NHCONH- (CH 2) n} -NHCONH-R '
(N represents an integer of 2 to 12, R and R ′ represent an alkyl group, an alkenyl group, an aryl group, or an alkyl-substituted aryl group)