JP2001031776A - Agricultural vinyl chloride-based resin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an agricultural vinyl chloride-based resin film which is excellent in heat resistance during processing and weather resistance and can be spread for a long term by compounding a vinyl chloride-based resin with specified amounts of an epoxy compound polymer and/or a copolymer of an epoxy compound with another monomer and an aromatic Zn compound. SOLUTION: A vinyl chloride-based resin in an amount of 100 pts.wt. is compounded with 0.1-1.5 pts.wt. polymer of an epoxy compound represented by the formula and/or copolymer of an epoxy compound of the formula and another monomer and 0.1-1.5 pts.wt. aromatic Zn compound. Zn salts and Zn complexes of aromatic carboxylic acids are preferable as the aromatic Zn compound. Zn benzoate, Zn m-tert-butyl benzoate, Zn p-methylbenzoate, etc., are given as the Zn salts, Zn p-methylbenzoate being especially preferable among them.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a vinyl chloride resin film for agricultural use which is excellent in heat resistance during processing and weather resistance.

[0002]

2. Description of the Related Art A vinyl chloride resin film for agriculture is stretched outdoors and is often exposed to the sun, wind and rain, so that it is necessary to change the film periodically. However, the replacement of the agricultural film is difficult, and there is a demand for a film that can be extended for a long time.

[0003]

In order to develop a film which can be stretched for a long time, it is necessary to have a higher weather resistance than ever.

[0004]

Means for Solving the Problems The invention according to claim 1 for solving the above-mentioned problems is to provide an epoxy compound represented by a chemical formula shown in Chemical formula 1 with respect to 100 parts by weight of a vinyl chloride resin. The polymer obtained by polymerizing the polymer obtained by the polymerization reaction and / or the epoxy compound represented by the chemical formula shown in Chemical Formula 1 with another monomer is 0.1 to 0.1%.
An agricultural vinyl chloride resin film containing 7 parts by weight and 0.01 to 1.5 parts by weight of an aromatic-Zn compound. [Formula 1] The invention according to claim 2 is an agricultural vinyl chloride resin film characterized in that the aromatic-Zn compound is zinc p-tert-butylbenzoate in addition to the constitution of the invention according to claim 1. is there.

[0005] The vinyl chloride resin in the present invention includes polyvinyl chloride, vinyl chloride, ethylene, propylene, vinyl acetate, vinylidene chloride, acrylic acid, methacrylic acid, and the like, similarly to conventional vinyl chloride resin films for agricultural use. Acrylic acid esters, methacrylic acid esters,
A copolymer with maleic acid, fumaric acid, acrylonitrile, alkyl vinyl ether, or the like, or a mixture of these resins can be used.

[0006] The above-mentioned vinyl chloride resin may contain a plasticizer, a drip-proofing agent, a fluorine-containing compound, a stabilizer, a lubricant or an anti-adhesive, an ultraviolet absorber, an antioxidant, an inorganic filler, Various additives such as stabilizers are added.

[0007] A polymer of the epoxy compound represented by the chemical formula shown in Chemical Formula 1 and / or another epoxy compound represented by the chemical formula shown in Chemical Formula 1 mixed with the vinyl chloride resin film for agricultural use of the present invention. The amount of the copolymer with the monomer is as follows, based on 100 parts by weight of the vinyl chloride resin.
It is particularly preferred that the amount be 0.5 to 3.0 parts by weight. Agricultural vinyl chloride resin film obtained when the amount of the polymer of the epoxy compound represented by the chemical formula shown in Chemical Formula 1 and / or the copolymer of the epoxy compound represented by the chemical formula shown in Chemical Formula 1 is too large. Tends to have poor dust resistance, and if the addition amount is too small, the obtained polyvinyl chloride resin film for agriculture tends to have insufficient weather resistance.

The monomers copolymerizable with the epoxy compound represented by the chemical formula shown in Chemical Formula 1 include vinyl chloride,
Examples include styrene, vinylidene chloride, methacrylamide, methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, N, N-dimethylacrylamide, acrylonitrile, vinyl acetate, glycidyl methacrylate, β-methyl glycidyl methacrylate, and allyl glycidyl methacrylate.

The vinyl chloride resin film of the present invention includes:
Although 0.01 to 3 parts by weight of the aromatic-Zn compound is blended,
As the aromatic-Zn compound, a zinc salt of an aromatic carboxylic acid or a complex compound of an aromatic carboxylic acid and zinc is preferable.

As the aromatic-Zn compound, zinc benzoate, zinc m-tert-butyl benzoate, zinc m-methyl benzoate, zinc p-tert-butyl benzoate, p-
Zinc methyl benzoate and the like. Among them, p-te
Particularly preferred is rt-butyl zinc benzoate.

Specific examples of the plasticizer include di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, dibutyl phthalate, butyl benzyl phthalate, dilauryl phthalate, didecyl phthalate, diundecyl phthalate, and ditridecyl phthalate. Phthalate plasticizers such as dioctyl adipate, ditrinonyl adipate, diisodecyl adipate, etc .; polyester plasticizers; sebacate ester plasticizers; trimellitate plasticizers; One or more selected from epoxy plasticizers such as soybean oil can be used. The amount of the plasticizer added is 100 parts by weight of the vinyl chloride resin.
30 to 70 parts by weight are preferred.

Examples of the above drip-proofing 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 ester Esters of polyhydric alcohols and fatty acids such as acid esters, esters of polyhydric alcohols and fatty acids and dibasic acids, or ethylene oxide, propylene oxide,
Examples thereof include compounds to which an alkylene oxide such as butylene oxide is added, and 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 / ethylene oxide 2 mol adduct, sorbitan stearate adipate / ethylene oxide 3 mol adduct, sorbitol stearate adipate / ethylene oxide 2 mol adduct And diglycerin palmitate sebacate / propylene oxide 3 mol adduct, sorbitol palmitate adipate / ethylene oxide 3 mol adduct and the like. The above drip-proofing agents can be used alone or in combination of two or more. Further, the amount of the above drip-proofing agent is 100 vinyl chloride resin.
0.5 to 6.0 parts by weight based on parts by weight is preferred.

The above-mentioned fluorine-containing compound is a compound having a fluorine-containing group and at least one of a hydroxyl group and an alkylene oxide group in one molecule. Examples of the fluorinated group include a perfluoroalkyl group [C _n F _{2n + 1} group], a perfluoroalkoxyl group [C _n F _{2n + 1} O group], a polyfluoroalkyl group [H _m C _n F _{2n + 1-m} Group), a perfluoroalkenyl group [C _n F _2n-1 group], a polyfluoroalkenyl group [H _m C _n F _2n-1-m group], a perfluoroalkenyl group [C _n F _2n group] and the like. (However, m in the formula is 1 to
3, n is an integer of 3 to 20), and examples of the alkylene oxide group include (C ₂ H ₄ O) _n and (C ₃ H ₆ O) _n (where n in the formula is 1 to 30). integer).

Specific examples of the fluorine-containing compound include those shown in Chemical formulas (1) to (13), but are not limited thereto. The amount of the fluorine-containing compound is 0.01 to 100 parts by weight of the vinyl chloride resin.
1.0 parts by weight is preferred, and more preferably 0.05 to
0.5 parts by weight.

[0015]

Embedded image

As the stabilizer, a commonly used stabilizer such as a metal soap, an organic phosphite-based stabilizer and a β-diketone compound can be used. As metal soap,
Examples include zinc stearate, barium stearate, calcium stearate, barium ricinoleate, calcium laurate, calcium oleate, and zinc octoate. Examples of the organic phosphite-based stabilizer include diphenyldecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, tristearyl phosphite, and octyl diphenyl phosphite. And the like. Examples of the β-diketone compound include dibenzoylmethane. The above stabilizers can be used alone or in combination of two or more. The amount of the stabilizer is preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin.

Examples of the lubricant or anti-tackiness agent include fatty acid lubricants such as stearic acid, isostearic acid and palmitic acid; fatty acid amide lubricants such as stearic acid amide, methylenebisstearamide and ethylenebisstearamide; butyl palmitate Butyl stearate and the like; lubricants such as metal salts of organic phosphates such as barium isodecyl phosphate and calcium octadecyl phosphate; polyethylene wax; and liquid paraffin. The above lubricants or antiadhesives can be used alone or in combination of two or more.

Examples of the ultraviolet absorber include commonly used ultraviolet absorbers such as benzophenone-based, benzotriazole-based, salicylate-based and cyanoacrylate-based ones. The above-mentioned ultraviolet absorbers can be used alone or in combination of two or more.

Examples of the inorganic filler include magnesium carbonate, magnesium silicate, silicon oxide, aluminum oxide, aluminum hydroxide, magnesium hydroxide, hydrotalcites and the like. The above-mentioned inorganic filler preferably has a particle size of 20 μm or less.

In the vinyl chloride resin film for agricultural use of the present invention, a polymer of an epoxy compound represented by the chemical formula shown in Chemical Formula 1 and / or a copolymer of an epoxy compound represented by the chemical formula shown in Chemical Formula 1 In addition to the above, it is desirable to add one of the organic phosphorus compounds represented by the general formulas shown in Chemical formulas 3 and 4. Furthermore, in addition to a polymer of an epoxy compound represented by the chemical formula shown in Chemical Formula 1 and / or a copolymer of an epoxy compound represented by the chemical formula shown in Chemical Formula 1, It is particularly preferred to add both of the organic phosphorus compounds represented.

Embedded image R _{1 to} R ₃ represent the same or different aryl groups, alkyl-substituted aryl groups, and aryl-substituted alkyl groups.

Embedded image R _{4 to} R ₇ represent the same or different aryl groups, alkyl-substituted aryl groups, and aryl-substituted alkyl groups, and n represents an integer of 1 to 10.

As the above-mentioned organic phosphorus compound, one or more compounds represented by the general formula shown in Chemical formula 3, one or more compounds represented by the general formula shown in Chemical formula 4, or the compound represented by the general formula shown in Chemical formula 3 Any of a mixture of one or more compounds represented by the general formula shown in Chemical Formula 4 and one or more compounds represented by the chemical formula 4 may be used. By adding these organic phosphorus compounds in combination, the weather resistance and dust resistance of the obtained agricultural vinyl chloride resin film are further improved.

The amount of the organic phosphorus compound to be added is preferably 0.01 to 5.0 parts by weight, more preferably 0.1 to 4.0 parts by weight, based on 100 parts by weight of the vinyl chloride resin. .

Further, in the agricultural vinyl chloride resin film of the present invention, in order to further improve the weather resistance,
It is desirable to add a hindered amine light stabilizer having a 2,2,6,6-tetramethylpiperidine skeleton.
The hindered amine light stabilizer has a molecular weight of 8
Those having about 00 to 2000 are preferable. The amount of the hindered amine light stabilizer is preferably 0.01 to 0.5 part by weight based on 100 parts by weight of the vinyl chloride resin.

The above-mentioned vinyl chloride resin composition is formed into a film by known means such as a calendering method, an extrusion method and an inflation method, and the agricultural vinyl chloride resin film of the present invention is obtained. The processing conditions such as the temperature at which the film is formed into a film may be the same as in the case of a conventional agricultural vinyl chloride resin film.

The agricultural polyvinyl chloride resin film of the present invention is similar to the conventional agricultural vinyl chloride resin film,
A dust-proof coating made of a solvent-type, water-type, or UV-curable paint may be formed on the surface that becomes the outside when the sheet is spread. Examples of the solvent-type paint include solvent-type paints such as acrylic resin, vinyl chloride resin, cellulose resin, fluorine resin, polyamide resin, urethane resin, epoxy resin, and silicone resin. Examples of the water-based paint include water-based paints such as acrylic resin, polyester resin, urethane resin, and epoxy resin. Examples of the UV-curable paint include UV-curable paints such as acrylic resin, acrylic-modified urethane resin, acrylic-modified epoxy resin, mercapto derivative, and epoxy resin.

Further, the vinyl chloride resin film for agriculture of the present invention is a film for imparting drip-proof property to a surface which becomes inside when stretched, for example, the above-mentioned solvent type, aqueous type, or A coating film or the like obtained by adding colloidal silica or the like to a UV-curable paint may be formed.

[0027]

Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the examples shown below.

Examples 1 to 4 A vinyl chloride resin composition having the composition shown in Table 1 was kneaded for 20 minutes at 175.degree.
A 1 mm film was dispensed. The obtained film was evaluated for heat resistance during processing and weather resistance by the following methods. Table 1 shows the results.

(1) Evaluation of heat resistance during processing Kneading was carried out at 175 ° C. for 40 minutes using an 8-inch test roll, and the color of the compound and the adhesiveness to the roll were evaluated. [Evaluation Criteria] 5: slight discoloration is seen but not sticking at all 4 ... slight discoloration is seen and slight adhesion is seen 3 ... discoloration is seen and slight adhesion is seen 2 ... Discoloration is severe and strong adhesion is observed 1 ... Discoloration to brown and sticking and not peeling off (2) Weather resistance The film obtained in a pipe house with a frontage of 1.5 m and a height of 1 m is used. After stretching, the state of the film after 24 months was visually observed and evaluated based on the following criteria. [Evaluation Criteria] 5: Almost the same as before expansion 4 ... No tearing, but slightly browning 3 ... Slight tearing, browning observed 2 ... There is remarkable browning, and many occurrences of tearing are observed. 1 ... Browning occurs over the entire surface and occurrence of tearing is extremely large.

[0030]

[Table 1] * 1 Di-2-ethylhexyl phthalate * 2 MERK LA-63 (manufactured by Asahi Denka Kogyo) * 3 Biosoap 130 (manufactured by Kyodo Yakuhin) * 4 Methylene bisstearamide * 5 Sorbitan monostearate * 6 Unidyne DS- 401 (manufactured by Daikin Industries, Ltd.) * 7 Falpack 50M (manufactured by NOF Corporation) * 8 Bisphenol A type epoxy compound * 9 Novolac type epoxy compound

Comparative Examples 1 to 6 Films were obtained from the vinyl chloride resin compositions having the formulations shown in Table 2 in the same manner as in the examples. About the obtained film, heat resistance during processing and weather resistance were evaluated like Example. Table 2 shows the results
Shown in

[0032]

[Table 2]

[0033]

From the above results, the vinyl chloride resin film for agricultural use of the present invention is represented by the polymer of the epoxy compound represented by the chemical formula shown in Chemical formula 1 and / or the chemical formula shown in Chemical formula 1. Epoxy compound copolymer and aromatic-Z
By blending with the n compound, heat resistance and weather resistance during processing are improved.

As described in detail above, the agricultural vinyl chloride resin film of the present invention is excellent in heat resistance and weather resistance during processing, and is an agricultural film that can be spread over a long period of time.

Claims (2)

[Claims] 1. A polymer obtained by polymerizing an epoxy compound represented by the chemical formula shown in Chemical Formula 1 with respect to 100 parts by weight of a vinyl chloride resin, and / or an epoxy compound represented by the chemical formula shown in Chemical Formula 1. 0.1 to 7 parts by weight of a copolymer obtained by a polymerization reaction of
A vinyl chloride resin film for agricultural use, comprising 0.01 to 1.5 parts by weight of a Zn compound. Embedded image 2. The agricultural vinyl chloride resin film according to claim 1, wherein the aromatic-Zn compound is zinc p-tert-butylbenzoate.