JPS6126644A - Mildew-proofing coating material for agricultural use - Google Patents

Abstract

PURPOSE:To provide a coating material having improved mildew-proofing property without lowering the durability of the base resin, and consisting of a flexible vinyl chloride resin containing an ethylene oxide adduct of an alkane-1,2- diol containing perfluoroalkyl group. CONSTITUTION:The objective coating material is composed of an anti-fogging flexible vinyl chloride resin containing an ethylene oxide addition compound of an alkane-1,2-diol containing perfluoroalkyl group. The polymerization degree of the vinyl chloride resin is 800-2,000, preferably 1,000-1,500. The addition compound is an ethylene oxide adduct of perfluoroalkyl propane(or ethane)-1,2-diol, and its amount is 0.01-1pt.wt. per 100pts.wt. of the resin.

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 antifungal properties by incorporating a specific fluorine-containing compound of the following types. Regarding.

Soft vinyl chloride resin films, especially antifogging soft vinyl chloride resin films, are susceptible to the growth of 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, antifungal agents have been added to such vinyl chloride resin films, such as 1-(4'--thiazolyl)benzimidazole, N-(fluorodichloromethylthio)-phthalimide, 10.10'-oxybisphenoxyarsine, etc. (For example, see Mayumi Inoue, Mold that Attacks Plastics, published by Rubber Digest, December 12, 1982). However, these conventionally proposed fungicides do not affect the thermal stability of the film. However, there are drawbacks such as poor compatibility with vinyl chloride resin and toxicity, which tends to bleed out, and it has not been possible to obtain a film with a satisfactory anti-mildew effect.

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.

[Ethylene oxide addition compound of perfluoroalkyl group-containing alkane-1,2-diol] used as a fungicide in the present invention has the general formula %, where Rf is a linear chain having 3 to 21 carbon atoms. represents a perfluoroalkyl or perfluoroalkyloxyperfluoroalkyl group; Δ is -C
Ht-1-8o! (CHi)n, -8O! NR2(
CHRIn or 100NR(CHI)n is shown,
Cocote R3 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and n is an integer of 1 to 12; R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;
R1 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkylaryl group containing an alkyl group having 1 to 12 carbon atoms; 1 is 0 or 1; m is 1 to 30
Preferable specific examples include compounds represented by the following, which is an integer of
Examples include compounds in which A in the above formula is CHi and Rf is linear or branched perfluoroalkyl, that is, perfluoroalkylpropane (or ethane i1,2-diol-based compounds). Preferred in the present invention More specific examples of the compounds to be used are shown in the following general formulas.

C,,Fi,)4t CHt CH(OH)CHz
0(CH20HiO)bCHs In the formula, a is an integer of 5 to 12, preferably 6 to 10, and is 1 to 30. Preferably it is an integer of 2 to 20.

Such perfluoroalkyl group-containing alkane-1,
Examples of ethylene oxide adducts of 2-diol include:
Polyethylene oxide is added to perfluoroalkyl group-containing alkylene epoxide, and alkali hydroxide (e.g. K
OH, NaOH.

LioH, etc.), by heating and/or pressurizing if necessary, and reacting in one step or in multiple steps.

Each of these compounds can be used alone;
Alternatively, two or more types may be used in combination. The amount of the compound added to the soft vinyl chloride resin may vary depending on the type of compound, etc., but generally 100 parts by weight of the vinyl chloride resin (the weight of the resin alone, excluding the weight of plasticizers, etc.) 0.01 to 1 part by weight, preferably 0.05 to 0.
A range of 5 parts by weight is appropriate.

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 used is polyvinyl chloride with a degree of polymerization of about 800 to about 2,000, preferably about 1,000 to about 1,500, or a copolymer mainly composed of vinyl chloride (e.g., ethylene-vinyl chloride copolymer). , acetic acid-vinyl chloride copolymer, vinyl chloride-halogenated olefin copolymer, or other compatible resins based on these polyvinyl chloride or vinyl chloride copolymers (e.g., polyester resin, epoxy resin, acrylic resin) resin, vinyl acetate resin, urethane resin, acrylonitrile-styrene-butadiene copolymer resin, partially saponified polyvinyl alcohol, etc.) When producing a soft vinyl chloride resin, for example, these 3 per 100 parts by weight of vinyl chloride resin
0 to 70 parts by weight of plasticizer, preferably 40 to 60 parts by weight: 0.05 to 7 parts by weight, preferably 1.0 to 5.0 parts by weight of lubricant and/or heat stabilizer 80 to 3.0 parts by weight parts, preferably 0.1 to 0.5 parts by weight of ultraviolet absorber: O to 5.
0 parts by weight, preferably 0.1 to 1.0 parts by weight of an anti-blocking agent, etc. may 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 heptalic acid derivatives such as di-0-octyl phthalate, di-2-ethylhexyl phthalate, and diisodecyl phthalate; isophthalic acid derivatives such as diisooctyl isophthalate; adipic acid derivatives such as dioctyl adipate; Others include tricresyl phosphate, tricylenyl phosphate, epoxidized soybean oil, etc. Among them, dioctyl phthalate, tricresyl phosphate, dioctyl adipate, and epoxidized soybean oil are suitable.

Examples of the lubricant or heat stabilizer 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 layer phosphate, Examples of the ultraviolet absorber include benzo-1-lyazole, benzoate, benzophenone, cyanoacrylate, and phenyl salicylate.

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; metal soaps such as calcium stearate. be done.

Furthermore, examples of antioxidants that can be added as necessary include phenolic antioxidants, such as 2゜6-T-
Butyl-p-cresol, 4,4-monothiobis(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-i-lis(4-°C-butyl-3-hydroxy-2,6-dimethylpencyl)isocyanurate, tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate; thiodipropion Acid esters such as di-n-dodecyl-thiodib O bionate, di-
n-octadecyl-thiodipropionate, aliphatic sulfides and disulfides such as di-n-dodecyl sulfide, di-n-octadecyl sulfide, di-0-octadecyl disulfide: aliphatic, aromatic or aliphatic-aromatic phosphites and thiosphites such as tri-dodecyl-phosphite, tris(n-nonylphenyl) phosphite, tri-dodecyl trithiophosphite, phenyl-di-decyl phosphite, di-
Examples of antistatic agents include quaternary ammonium salts, amines, imidacillins, amine oxidized ethylene adducts, polyethylene glycols, sorbitan esters, etc. . In addition, silica, talc, calcium carbonate, etc. can be used as fillers, and examples of coloring agents include titanium oxide, 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 preactive agents such as sorbitan monostearate, sorbitan monopalmitate, and sorbitan monobehenate; glycerin monolaurate; Glycerin-based surfactants such as diglyrelin monopalmitate and glycerin monostearate; polyethylene glycol-based surfactants such as polyethylene glycol monostearate and polyethylene glycol monopalmitate; trimethylolpropane-based interfaces such as nitrimethylolpropane monostearate Active agent; pentaerythritol surfactant such as pentaerythritol monopalmitate; alkylene oxide adduct of alkylphenol; ester of sorbitan/glycerin condensate and fatty acid, ester of sorbitan/alkylene glycol condensate and fatty acid, 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 agent can be similar to that used for conventional agricultural vinyl films,
Generally, 0.5 parts per 100 parts by weight of vinyl chloride resin
It can be in the range of ~3.0 parts by weight, preferably 0.8 to 2.0 parts by weight, and more preferably 1.3 to 1.8 parts by weight.

Furthermore, in addition to the above-mentioned ethylene oxide addition compound of perfluoroalkyl group-containing alkane-1,2-diol, the agricultural coating material of the present invention may contain known fungicides such as pentachlorophenol, pentachlorophenol, etc. Phenoluna 1-Rium, parachloromethaxinol,
2.2"-methylene-bis-4-chlorophenol, halogen derivative of salicylanilide: 10,10"-oxybisfutuxialsine, α-bromo-〇-chlorobenzalacetone, 2-(4'-thiazolyl〉benz) Imidazole, 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 such as a roll type, Banbury type, or Henschel type, or an extruder, and then applying a calender method, a T-die method, an inflation method, etc. It can be manufactured by molding it into a film according to the usual molding method.

The thickness of the film at that time is generally 30 to 300μ.
, preferably within the range of 50 to 200 microns.

The thus formed film may be subjected to normal surface treatments such as dustproofing, if necessary.

Resins that can be used for such dustproofing include any acrylic resin that has been used for dustproofing soft vinyl chloride resin films in the field of agricultural covering materials, mainly esters of acrylic acid or methacrylic acid. For example, Japanese Patent Publication No. 46-2819
Publication No. 4, Special Publication No. 52-6214, Special Publication No. 57-
15608@ publication, Japanese Patent Application Laid-Open No. 13.92/1980, etc., it can be selected as appropriate.
In particular, it is described in Japanese Patent Publication No. 57-15608,
4-13% by weight of N-methylolacrylamide and 01-CI of acrylic acid or methacrylic acid! A resin mainly composed of acrylic resin obtained by copolymerizing with 87 to 96% by weight of at least one alkyl ester has excellent dustproofness and blocking resistance, as well as flexibility and high frequency weldability. It is suitable because it has

In order to provide a coating layer made of such an acrylic resin on the surface of the vinyl chloride resin film, for example, the acrylic resin as described above is dissolved in an appropriate organic solvent and used for coating. 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, for example, cellulose acetate butyrate, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyurethane,
40 parts by weight or less, preferably 30 parts by weight or less, more preferably 2 parts by weight of other compatible resin such as ethylene-vinyl acetate copolymer, etc. per 100 parts by weight of the acrylic resin.
It may be included in a proportion of 5 parts by weight or less, and if necessary, appropriate amounts of light stabilizers such as ultraviolet absorbers, antistatic agents, colorants, antiblocking agents, plasticizers, etc. may be added. can.

Coating with the above-mentioned coating composition is carried out according to a conventional method, for example, roll coating, knife coating, spray coating, dip coating, curtain 70-
This can be done by a method such as coating, and the thickness of the coating layer is not strictly limited, but is generally 1 to 5.
Advantageously it is in the range of 1 to 3 microns, preferably in the range of 1 to 3 microns.

As is clear from the examples below, the agricultural covering material of the present invention described above has excellent mold-proofing properties, good thermal stability, and there is no concern about toxicity, so it can be used for greenhouses, etc. It can be extended to agricultural and horticultural facilities such as tunnels (including tobacco drying facilities) and used for the cultivation of useful crops. In particular, the present invention is applicable to coating materials that have been made dustproof and weather resistant through surface treatment and can withstand long-term use. is effectively applied and 1q.

Next, the present invention will be further explained by examples.

- and polyvinyl chloride (P = 1300) 100
Parts by weight of dioctyl phthalate l-45.

Tricresyl phosphate 3 nZn-
Ca-based composite stabilizer 3 Epoxy resin
2 I + lithite ester chelator-0,5,Z solhitan monopalmitate
1.5! ! The above ingredients are mixed with various additives in the weight parts shown in Table 1, and the mixture is fed to a calender.
A film with a thickness of 100 microns was created by rolling at 90°C.

Each film thus obtained was tested for mildew resistance and thermal stability using the following methods.

[Mold-proofing test] (1) Test method A pipe house (width 3°6111,
The films of Examples and Comparative Examples were spread on each building from the end of July 1980 to mid-October 1981, and the growth of mold was observed. Observation and evaluation were conducted in mid-October 1958.

(2) Evaluation criteria ◎ No mold growth observed at all.

O There is some mold growth on the ceiling.

△ Mold growth is observed around 115 areas of the ceiling.

× Mold growth is observed on more than 1/3 of the area of the ceiling.

[Thermal stability test] (1) Test method Using a gear set air dryer (with air circulation device)
A heat resistance test was conducted at a concentration of ±2°C.

(2) Evaluation criteria ○ Same as blank.

△ Inferior to blank.

× Considerably inferior to blank.

The results of these tests are summarized in Table 1 below.

=18- (1) Chemical formula: C, F19 CH, 2CH(OH)C
Hi O (CHi CH20) MI CHs (2)
Chemical formula: C9F195O2CH2CH(OH)CHi
O (CHi CH20) + s H (3) O-hydroxydiphenyl (4) Organic nitrogen halogen compound Courtside N manufactured by Narita Pharmaceutical Co., Ltd. (5) 2-(4-thiazolyl)-benzimidazole (
6) Chemical formula: C3F17 C0NH(CH2CHIO
) Button H (7) Chemical formula: C9F19 Sop NH (CHtC
Hi O) w H (8) Alternaria bacteria, Trichoderma bacteria, Penicillium bacteria and unidentified bacteria were isolated and detected.

Claims (1)

[Claims] An agricultural covering material with excellent mildew resistance characterized by being made of an antifogging soft vinyl chloride resin containing an ethylene oxide addition compound of a perfluoroalkyl group-containing alkane-1,2-diol.