JPH0530859B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an agricultural covering material, and more particularly to an agricultural covering material made of a soft vinyl chloride resin that has anti-fungal properties by incorporating a certain type of specific fluorine-containing compound. Regarding materials. Soft vinyl chloride resin films, especially antifogging soft vinyl chloride resin films, are prone to mold such as black mold and blue mold, which is undesirable because it inhibits light transmission through the film and causes deterioration of the film. To prevent this, conventionally, such vinyl chloride resin films have been prepared with antifungal agents such as 2-(4'-thiazolyl)benzimidazole, N
-(fluorodichloromethylthio)-phthalimide,
It has been proposed to incorporate 10,10'-oxybisphenoxyarsine, etc. (see, for example, Mayumi Inoue, "Mold that Attacks Plastic," published by Rubber Digest, December 12, 1982), but these conventional proposals The anti-mildew agents that have been used have drawbacks such as decreasing the thermal stability of the film, poor compatibility with vinyl chloride resin and being prone to lead-out, and toxicity.Therefore, it is difficult to obtain a film with a satisfactory anti-mildew effect. has not yet been reached. As a result of various studies, the present inventors have found that an ethylene oxide addition compound of a perfluoroalkyl group-containing alkane-1,2-diol has a high durability against agricultural covering materials made of antifogging soft vinyl chloride resin. It has excellent mold-proofing properties without damaging the coating material, i.e., it prevents the growth of various fungi that are conventionally known to cause mold on the coating material, such as gray mold represented by Alternaria fungi and green mold caused by Trichoderma fungi. The present invention was completed based on the discovery that an effective suppressing effect can be imparted. Therefore, according to the present invention, an agricultural product having excellent mold-proofing properties is made of an antifogging soft vinyl chloride resin containing an ethylene oxide addition compound of a perfluoroalkyl group-containing alkane-1,2-diol. A dressing for use is provided. The "ethylene oxide addition compound of perfluoroalkyl group-containing alkane-1,2-diol" used as a fungicide in the present invention has the general formula R _f AlCH (OR ₁ ) CH ₂ O (CH ₂ CH ₂ O) _n R ₂ In the formula, Rf represents a linear, branched or cyclic perfluoroalkyl or perfluoroalkyloxyperfluoroalkyl group having 3 to 21 carbon atoms; A is -CH ₂ -, -SO ₂ ( _CH2 )n, -
_{SO2NR3 ( CH2} )n or -CONR( _CH2 )n, where _R3 is a hydrogen atom or has 1 to 12 carbon atoms.
and n is an integer of 1 to 12; R ₁ represents a hydrogen atom or an alkyl group of 1 to 4 carbon atoms; R ₂ represents a hydrogen atom or an alkyl group of 1 to 12 carbon atoms; Represents an alkyl group or an alkylaryl group containing an alkyl group having 1 to 12 carbon atoms; l is 0 or 1; m is an integer of 1 to 30. Examples include compounds in which A in the above formula is CH ₂ and Rf is linear or branched perfluoroalkyl, that is, perfluoroalkylpropane (or ethane)-1,2-diol compounds. Can be mentioned. More specific examples of the compounds preferably used in the present invention are shown in the following general formulas. C _a F _2a+1 CH ₂ CH(OH)CH ₂ O (CH ₂ CH ₂ O) _b CH ₃ C _a F _2a+1 CH ₂ CH(OH)CH ₂ (CH ₂ CH ₂ O) _b H C _a C _2a+1 SO ₂ CH ₂ CH (OH) CH ₂ O (CH ₂ CH ₂ O) _b
H In the formula, a is an integer of 5 to 12, preferably 6 to 10, and b is an integer of 1 to 30, preferably 2 to 20. Such an ethylene oxide addition compound of a perfluoroalkyl group-containing alkane-1,2-diol can be prepared, for example, by adding polyethylene oxide to a perfluoroalkyl group-containing alkylene epoxide and adding an alkali hydroxide (e.g. KOH, NaOH, LioH).
etc.), by heating and/or pressurizing if necessary, and reacting in one stage or in multiple stages. These compounds can be used alone or in combination of two or more. The amount of the compound added to the soft vinyl chloride resin may vary depending on the type of compound, etc., but in general, it is 100 parts by weight of the vinyl chloride resin (the weight of the resin alone, not including the weight of plasticizer, etc.) Same) per 0.01 to 1
Parts by weight, preferably within the range of 0.05 to 0.5 parts by weight, are suitable. The soft vinyl chloride resin to which the ethylene oxide addition compound of perfluoroalkyl group-containing alkane-1,2-diol is blended according to the present invention preferably has antifogging properties imparted by blending with an antifogging agent. A soft vinyl chloride resin is used. The vinyl chloride resin that can be used has a polymerization degree of about 800 to about 2000, preferably about 1000.
~1500 polyvinyl chloride or a copolymer mainly composed of vinyl chloride (e.g., ethylene-vinyl chloride copolymer, vinyl acetate-vinyl chloride copolymer, vinyl chloride-halogenated olefin copolymer, or these) Polyvinyl chloride or other compatible resins based on vinyl chloride copolymers (e.g. polyester resins,
Blends with epoxy resins, acrylic resins, vinyl acetate resins, urethane resins, acrylonitrile-styrene-butadiene copolymer resins, partially saponified polyvinyl alcohols, etc.) are included.
When producing soft vinyl chloride resins, for example, per 100 parts by weight of these vinyl chloride resins,
30-70 parts by weight, preferably 40-60 parts by weight of plasticizers; 0.05-7 parts by weight, preferably 1.0-5.0 parts by weight of lubricants and/or heat stabilizers; 0-3.0 parts by weight, preferably 0.1-0.5 parts by weight. Part by weight of ultraviolet absorber: 0-5.0
Parts by weight, preferably 0.1 to 1.0 parts by weight of an anti-blocking agent etc. can be blended. Furthermore, the vinyl chloride resin may contain other conventional resin additives such as antioxidants, antistatic agents, fillers, colorants, etc., if necessary. Examples of plasticizers that can be blended include G-n-
Phthalic acid derivatives such as octyl phthalate, di-2-ethylhexyl phthalate, and diisodecyl phthalate; Isophthalic acid derivatives such as diisooctylisophthalate; Adipic acid derivatives such as dioctyl adipate; Other tricresyl phosphate and tricylenyl phosphate Phate, epoxidized soybean oil and the like are included, among which dioctyl phthalate, tricresyl phosphate, dioctyl adipate and epoxidized soybean oil are suitable. Examples of lubricants or heat stabilizers that can be included in the vinyl chloride resin include polyethylene wax, stearic acid, zinc stearate, barium stearate, calcium stearate, barium ricinoleate, chelators such as organic phosphites, Examples include epoxy resins, and examples of ultraviolet absorbers include benzotriazole,
Included are benzoate-based, benzophenone-based, cyanoacrylate-based, and phenyl salicylate-based ultraviolet absorbers. In addition, anti-blocking agents include, for example, fatty acid amides such as methylene bis stearylamide; higher fatty acids and their derivatives such as butyl stearate; higher alcohols such as stearyl alcohol; and metal soaps such as calcium stearate. Ru. Furthermore, examples of antioxidants that may be added as necessary include phenolic antioxidants, such as 2,6-di-t-butyl-p-cresol, 4,
4'-thiobis-(3-methyl-6-t-butylphenol), 2,2-di(4-hydroxyphenyl)propane, 1,1,3-tris-(2-methyl-4-hydroxy-5 -t-butylphenyl)
Butane, octadecyl-3-(3,5-di-t-
Butyl-4-hydroxyphenyl)propionate, pentaerythritol-tetra-(3.5-di-
t-Butyl-4-hydroxyphenyl)-propionate, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)
Isocyanurate, tris-(3,5-di-t-
butyl-4-hydroxybenzyl) isocyanurate; thiodipropionic acid esters such as di-n-dodecyl-thiodipropionate, di-n
-octadecyl-thiodipropionate, aliphatic sulfides and disulfides such as di-n-
dodecyl sulfide, di-n-octadecyl sulfide, di-n-octadecyl disulfide; aliphatic, aromatic or aliphatic-aromatic phosphites and thiosphites, such as tri-n-dodecyl-phosphite, tris(n- Examples of the antistatic agent include quaternary ammonium Examples include salts, amines, imidazolines, amine oxidized ethylene adducts, polyethylene glycols, sorbitan esters, and the like. In addition, silica, talc, calcium carbonate, etc. can be used as a filler, and as a coloring agent, for example, titanium oxide,
Examples include ultramarine blue, phthalocyanine blue, and quinacridone red. If necessary, an antifogging agent is added to the soft vinyl chloride resin having the composition described above to provide antifogging properties. Antifogging agents that can be used include mainly nonionic surfactants, such as sorbitan surfactants such as sorbitan monostearate, sorbitan monopalmitate, and sorbitan monobehenate; glycerin monolaurate, diglycerin monopalmitate; Glycerin surfactants such as tate and glycerin monostearate; polyethylene glycol surfactants such as polyethylene glycol monostearate and polyethylene glycol monopalmitate; trimethylolpropane surfactants such as trimethylolpropane monostearate; Includes pentaerythritol surfactants such as pentaerythritol monopalmitate; alkylene oxide adducts of alkylphenols; esters of sorbitan/glycerin condensates and fatty acids, esters of sorbitan/alkylene glycol condensates and fatty acids, etc. These can be used alone or in combination of two or more. Antifogging agents that can be used particularly advantageously in the present invention include diglycerol monostearate and sorbitan monopalmitate. The amount of such antifogging agents can be the same as that used for conventional agricultural vinyl films, and generally, vinyl chloride resins are used.
0.5 to 3.0 parts by weight per 100 parts by weight, preferably 0.8 to 2.0 parts by weight
Parts by weight, more preferably in the range of 1.3 to 1.8 parts by weight. Furthermore, the agricultural coating material of the present invention may optionally contain the above-mentioned perfluoroalkyl group-containing alkane.
In addition to the ethylene oxide addition compound of 1,2-diol, known fungicides such as pentachlorophenol, sodium pentachlorophenol, parachloromethaxinol, 2,2'-methylene-bis-4-chlorophenol, Halogen derivatives of salicylanilide; 10,10'-oxybisphenoxyarsine, α-bromo-p-chlorobenzalacetone, 2-(4'-thiazolyl)benzimidazole, N-(fluorodichloromethylthio)
-phthalimide, N,N-dimethyl-N'-phenyl-(fluorodichloromethylthio)sulfamide, etc. may be blended. The agricultural covering material of the present invention is produced by thoroughly mixing or kneading the above-mentioned components using a mixer or extruder such as a roll type, Banbury type, Henschel type, etc., and then using a calendar method, a T-die method, or an inflation method. It can be manufactured by molding into a film according to a conventional molding method such as a method such as a method. The appropriate thickness of the film in this case is generally in the range of 30 to 300 microns, preferably 50 to 200 microns. The film thus formed may be subjected to ordinary surface treatments such as dustproofing, if necessary. As the resin that can be used for such dustproofing, any acrylic resin that has been conventionally used for dustproofing soft vinyl chloride resin films in the field of agricultural covering materials, mainly esters of acrylic acid or methacrylic acid, can be used. For example, Japanese Patent Publication No. 46-28194, Japanese Patent Publication No. 52
-6214 Publication, Japanese Patent Publication No. 57-15608, Japanese Patent Publication No. 15608
You can choose as appropriate from those disclosed in Publication No. 54-1392, etc., but especially Japanese Patent Publication No. 57-15608.
4 to 13% by weight of N-methylol acrylamide and at least one C ₁ to C ₁₂ alkyl ester of acrylic acid or methacrylic acid, as described in the above publication.
The material, which is mainly composed of acrylic resin obtained by copolymerizing with 87 to 96% by weight of seeds, has excellent dustproofing and blocking resistance, as well as flexibility and high frequency weldability. suitable. In order to provide a coating layer made of such an acrylic resin on the surface of the above-mentioned vinyl chloride resin film, the acrylic resin as described above is dissolved in a suitable organic solvent and used for coating, for example, in the same manner as in the usual dustproofing method. A composition is prepared and coated on the surface of a vinyl chloride resin film. In addition to the acrylic resin, the coating composition may optionally contain other materials such as cellulose acetate butyrate, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyurethane, ethylene-vinyl acetate copolymer, etc. A compatible resin may be included in an amount of 40 parts by weight or less, preferably 30 parts by weight or less, more preferably 25 parts by weight or less per 100 parts by weight of the acrylic resin, and if necessary, Appropriate amounts of light stabilizers such as ultraviolet absorbers, antistatic agents, colorants, anti-blocking agents, plasticizers, etc. can also be blended. Coating with the above-mentioned coating composition can be carried out according to conventional methods, such as roll coating, knife coating, spray coating, dip coating, curtain flow coating, etc., and the thickness of the coating layer is strictly limited. Generally 1 to 5 microns, although not a
Advantageously, it is preferably within the range of 1 to 3 microns. The agricultural covering material of the present invention described above has excellent mildew resistance, as is clear from the examples below.
Moreover, it has good thermal stability and there are no concerns about toxicity, so it can be deployed in agricultural and horticultural facilities such as greenhouses and tunnels (including leaf tobacco drying facilities), and used for cultivating useful crops. can. In particular, the present invention has the advantage that there is no reduction in light transmission or strength due to the growth of mold on coating materials that have been made dustproof through surface treatment and have improved weather resistance to withstand long-term use. can be effectively applied. Next, the present invention will be further explained by examples. Examples and Comparative Examples Polyvinyl chloride (=1300) 100 parts by weight Dioctyl phthalate 45 Tricresyl phosphate 3 Zn-Ca composite stabilizer 3 Epoxy resin 2 Phosphite chelator 0.5 Sorbitan monopalmi Tate 1.5〃 Mix various additives in parts by weight shown in Table 1 with each of the above ingredients, feed the mixture to a calendar,
A film with a thickness of 100 microns was created by rolling at 190°C. Each film thus obtained was tested for mildew resistance and thermal stability using the following methods. [Mold resistance test] (1) Test method A pipe house (width 3.6
20 m in depth, 2 m in height), and from the end of July 1980 to mid-October 1988, the films of Examples and Comparative Examples were spread out in each building and mold growth was observed. Observational evaluation was conducted in mid-October 1958. (2) Evaluation criteria ◎No mold growth is observed. 〇Some mold growth is observed on the ceiling. △Mold growth is observed on about 1/5 of the ceiling area. ×Mold growth is observed on more than 1/3 of the ceiling area. [Thermal Stability Test] (1) Test Method A heat resistance test was conducted at a temperature of 180±2°C using a gear air dryer (equipped with an air circulation device). (2) Evaluation criteria 〇Equivalent to blank. △Inferior to blank. ×Significantly inferior to blank. The results of these tests are summarized in Table 1 below. 【table】

Claims (1)

[Claims] 1 General formula R _f A _l CH (OR ₁ ) CH ₂ O (CH ₂ CH ₂ O) _n R ₂ In the formula, R _f is a linear or branched chain having 3 to 21 carbon atoms. represents a perfluoroalkyl or perfluoroalkyloxyperfluoroalkyl group; A is -CH ₂ -, -SO ₂ (CH ₂ ) - _o , -
SO ₂ NR ₃ (CH) - _o or -CONR (CH ₂ ) - _o , where R ₃ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and n is an integer of 1 to 12 R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
represents an alkylaryl group containing ~12 alkyl groups or an alkyl group having 1 to 12 carbon atoms;
1 is 0 or 1; m is an integer of 1 to 30. A fungicide for agricultural covering materials made from soft vinyl chloride resin.