JPH08302133A - Agricultural vinyl chloride resin film - Google Patents

Abstract

PURPOSE: To obtain an agricultural film resistant to deterioration at the area being in contact with a metal by adding a specified hindered amine compound to a vinyl chloride resin containing an ethylene/vinyl chloride copolymer resin having a specified ethylene content. CONSTITUTION: This resin composition prepared by adding 0.01-0.2 pt.wt. hindered amine compound having at least one structural unit represented by the formula (wherein R1 to R5 are each H or a 1-4C alkyl group) in the molecule to 100 pts.wt. vinyl chloride resin comprising 5-100 pts.wt. ethylene/vinyl chloride copolymer resin having an ethylene content of 0.1-7.0wt.% and 95-0 pt.wt. other vinyl chloride resins and having a total ethylene content of 0.1-7.0wt.% is formed into an agricultural vinyl chloride resin film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an agricultural vinyl chloride resin film, and more particularly to an agricultural vinyl chloride resin film which suppresses deterioration of a portion such as a metal pipe forming a house frame of a film in contact with a metal. Regarding a resin film.

[0002]

2. Description of the Related Art Conventionally, as a covering material for agricultural tunnels, simple greenhouses, etc., it is inexpensive, has good transparency, excellent heat retention and strength, and is easy to process into a film. Agricultural films made of polyvinyl chloride resin, which is a vinyl chloride homopolymer, are widely used. Further, as an agricultural film which positively uses a vinyl chloride resin other than polyvinyl chloride, there is disclosed in Japanese Patent Application Laid-Open No. 2-24341.
There is known one using an ethylene-vinyl chloride copolymer resin containing a specific amount of ethylene proposed in Japanese Patent Laid-Open Publication No. This proposal aims at improving the drip-proof persistence or the fog-proof persistence of a vinyl chloride-based resin film for agriculture, and therefore the ethylene content in the ethylene-vinyl chloride copolymer resin is set to a relatively wide range. However, it is an essential requirement to add a drip-proofing agent.

[0003]

These agricultural films are to be spread on a house or the like having a skeleton made of a metal pipe or the like by appropriately using fasteners or the like. There has been a problem that the film is apt to deteriorate at a portion where the metal part such as the pipe and the agricultural film come into contact with each other. In particular, this tendency was more remarkable when rust was generated in the metal portion in contact with the film.

The present inventors further proceed with research based on a vinyl chloride resin film for agriculture using the ethylene-vinyl chloride copolymer resin containing the above specified amount of ethylene, which has been previously proposed. As a result, surprisingly, a vinyl chloride resin containing an ethylene-vinyl chloride copolymer resin containing ethylene in a specific range more than the above proposal is used, and the total amount of ethylene in the vinyl chloride resin is specified. At the same time, it was found that an agricultural film capable of solving the above-mentioned problems can be obtained by containing a specific amount of a hindered amine compound having a specific structural formula, and completed the present invention.

[0005]

The agricultural vinyl chloride resin film of the present invention has an ethylene content of 0.1 to 7.0.
5 to 100 parts by weight of ethylene-vinyl chloride copolymer resin and 95 to 0 parts by weight of another vinyl chloride resin,
A hindered amine compound having 100 or more parts by weight of a vinyl chloride resin having a total ethylene content of 0.1 to 7.0% by weight has at least one structural unit represented by the general formula shown in Chemical formula 1 in the molecule. It is characterized in that a vinyl chloride resin composition obtained by adding 0.01 to 0.2 parts by weight is formed into a film.

Embedded image (In the formula, R _{1 to} R ₅ each represent the same or different hydrogen or an alkyl group having 1 to 4 carbon atoms)

In the present invention, 5% by weight in total vinyl chloride resin
The ethylene-vinyl chloride copolymer resin contained above has an ethylene content in the range of 0.1 to 7.0% by weight. Even if an ethylene-vinyl chloride copolymer resin having an ethylene content of less than 0.1% by weight is used, the effect of suppressing the deterioration in the metal contact portion expected by the present invention is not improved, and the ethylene content is also reduced. Is more than 7.0% by weight, it becomes difficult to process it into a film, and it is impossible to obtain a vinyl chloride resin film for agriculture which has a smooth surface and is excellent in transparency.

The ethylene-vinyl chloride copolymer resin can be used alone, and the amount of the ethylene-vinyl chloride copolymer resin in the total vinyl chloride resin is not less than 5% by weight, and the total vinyl chloride resin is not used. Total ethylene content is 0.1
It may be used by mixing with other vinyl chloride resin as long as it is in the range of up to 7.0% by weight.

The vinyl chloride resin used in the present invention, which comprises the ethylene-vinyl chloride copolymer resin alone or a mixture of the ethylene-vinyl chloride copolymer resin and another vinyl chloride resin, is a vinyl chloride resin. The total ethylene content of 0.1 to 7.0% by weight, preferably 0.3 to 3.0% by weight. Ethylene content is 0.1
Even if an ethylene-vinyl chloride copolymer resin of up to 7.0% by weight is used, if the total amount of ethylene in the vinyl chloride resin is less than 0.1% by weight, the metal contact portion is greatly deteriorated.
When it is in the range of more than 0% by weight, the calendering property of the film is deteriorated.

Vinyl chloride resins which can be mixed with ethylene-vinyl chloride copolymer resins having an ethylene content of 0.1 to 7.0% by weight include polyvinyl chloride (vinyl chloride homopolymer resin) and vinyl chloride. And a copolymer resin of another monomer. Examples of monomers other than ethylene that are copolymerizable with vinyl chloride include propylene, vinyl acetate,
Examples thereof include vinylidene chloride, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, maleic acid, fumaric acid, acrylonitrile and alkyl vinyl ether. Further, if the total ethylene content in the total vinyl chloride resin is within the range of 0.1 to 7.0% by weight, the vinyl chloride resin mixed with the above ethylene-vinyl chloride copolymer resin The ethylene content is 0.
Less than 1% by weight or more than 7.0 parts by weight of ethylene-
A vinyl chloride copolymer resin can also be used.

A vinyl chloride resin (hereinafter, simply referred to as "vinyl chloride") used in the present invention, which comprises the above-mentioned ethylene-vinyl chloride copolymer resin alone or a mixture of the ethylene-vinyl chloride copolymer resin and another vinyl chloride resin. System resin "), if necessary, a plasticizer, a drip-proofing agent, a fluorine-containing compound, a stabilizer, a lubricant or an anti-adhesive agent, an ultraviolet absorber,
Various additives such as antioxidants and inorganic fillers can also be added.

Specific examples of the above plasticizer include di-n-
Phthalates such as octyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, dibutyl phthalate, butylbenzyl phthalate, dilauryl phthalate, didecyl phthalate, diundecyl phthalate, ditridecyl phthalate; dioctyl adipate, ditrinonyl adipate Adipic acid ester plasticizers such as diisodecyl adipate; phosphoryl ester plasticizers such as trixylyl phosphate, tricresyl phosphate, tris (isopropylphenyl) phosphate, tributyl phosphate, triethyl phosphate, triphenyl phosphate, triethylphenyl phosphate; Polyester plasticizer; Sebacate ester plasticizer; Trimellitic ester plasticizer; Epoxidized soybean One or more selected from epoxy-based plasticizers, etc. and the like. Further, the addition amount of the above plasticizer is 30 to 70 with respect to 100 parts by weight of the vinyl chloride resin.
It is about parts by weight.

Specific examples of the drip-proof 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 ester.
Ester of polyhydric alcohol and fatty acid such as dibasic acid ester, diglycerin fatty acid and dibasic acid ester, ester of polyhydric alcohol and fatty acid and dibasic acid, or ethylene oxide, propylene oxide, butylene oxide, etc. Examples thereof include compounds to which alkylene oxide is added. Specific examples include 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, diglycerin stearate, glycerin stearate, glycerin palmitate / ethylene oxide 2 mol adduct, Rubitan 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. The above-mentioned drip-proof agents can be used alone or in combination of two or more. The amount of the drip-proofing agent added is 0.5 to 100 parts by weight of the vinyl chloride resin.
It is about 6.0 parts by weight.

The above-mentioned fluorine-containing compound is a compound having at least one of a fluorine-containing group and a hydroxyl group or an alkylene oxide group in one molecule. As the fluorine-containing group,
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), a perfluoroalkenyl Group (C _n F _2n-1 group), polyfluoroalkenyl group (H
_m C _n F _2n-1-m group), perfluoroalkylene group (C _n
F _2n group) and the like (in the formula, m is 1 to 3 and n is 3 to 20).
Is an integer of (C ₂ H
₄ O) _n , (C ₃ H ₆ O) _{n, and the} like (wherein n
Is an integer of 1 to 30).

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

[0015]

Embedded image

As the stabilizer, commonly used stabilizers such as metal soaps and organic phosphite stabilizers can be used. Examples of the metal soap include zinc stearate, barium stearate, calcium stearate, barium ricinoleate, calcium laurate, calcium oleate, zinc octoinate and the like. Examples of the organic phosphite stabilizer include diphenyldecylphosphite, triphenylphosphite, tris (nonylphenyl) phosphite, tridecylphosphite, tris (2-ethylhexyl) phosphite, tristearylphosphite, octyldiphenylphosphite. Etc. The above stabilizers can be used alone or in combination of two or more. The amount of stabilizer added is
0.5 to 10 with respect to 100 parts by weight of vinyl chloride resin
Parts by weight, preferably about 1 to 5 parts by weight.

As the lubricant or anti-sticking agent, fatty acid type lubricants such as stearic acid, isostearic acid and palmitic acid; fatty acid amide type lubricants such as stearic acid amide, methylene bis stearoamide, ethylene bis stearoamide; butyl palmitate. , Ester lubricants such as butyl stearate; metal organophosphate lubricants such as barium isodecyl phosphate and calcium octadecyl phosphate; polyethylene wax; liquid paraffin and the like. The above lubricants or antiblocking agents can be used alone or in combination of two or more.

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

As the inorganic filler, at least one of magnesium carbonate, magnesium silicate, silicon oxide, aluminum oxide, aluminum hydroxide, magnesium hydroxide and hydrotalcites can be used. The above-mentioned inorganic filler preferably has a particle size of 20 μm or less.

The agricultural vinyl chloride resin film of the present invention comprises a hindered amine compound having at least one structural unit represented by the general formula shown in Chemical Formula 1 in the molecule, based on 100 parts by weight of the vinyl chloride resin. It is formed by forming a vinyl chloride resin composition containing 01 to 0.2 part by weight, preferably 0.02 to 0.15 part by weight, into a film. When the amount of the hindered amine compound added is less than 0.01 parts by weight with respect to 100 parts by weight of the vinyl chloride resin,
The effect of preventing the deterioration of the film at the metal contact portion expected by the present invention is not sufficiently exerted, and conversely, even if the addition amount exceeds 0.2 parts by weight with respect to 100 parts by weight of the vinyl chloride resin, Not only the above effect is not improved but the cost is increased, but also the added hindered amine compound may bloom to impair the transparency of the film. In the hindered amine-based compound used in the present invention, a hindered amine-based compound in which R ₅ in the following general formula is a methyl group is particularly preferable in order to prevent deterioration of a metal contact portion.

[0021]

Embedded image (In the formula, R _{1 to} R ₅ each represent the same or different hydrogen or an alkyl group having 1 to 4 carbon atoms)

The above vinyl chloride resin composition is formed into a film by a known means such as a calendering method, an extrusion method or an inflation method to obtain the agricultural vinyl chloride resin film of the present invention. Processing conditions such as temperature when forming a film may be the same as those in the case of the conventional polyvinyl chloride film.

The agricultural vinyl chloride resin film of the present invention is, like the conventional agricultural polyvinyl chloride film, for the purpose of imparting dustproofness to the outer surface when expanded.
You may form the coating film by a solvent type, a water type, or an ultraviolet curable coating material. Examples of the solvent type paint include acrylic resin type, vinyl chloride resin type, cellulose resin type, fluororesin type, polyamide resin type, urethane resin type, epoxy resin type and silicone resin type. As the water-based paint, for example, acrylic resin-based, polyester resin-based, urethane resin-based, epoxy resin-based, etc. can be used. As the ultraviolet curable coating material, an acrylic resin system, an acrylic modified urethane resin system, an acrylic modified epoxy resin system, a mercapto derivative system, an epoxy resin system, etc. can be used. In addition, the agricultural vinyl chloride resin film of the present invention is a coating intended to impart drip-proof property to the inner surface when spread, for example, the above solvent type, water type, or ultraviolet curing type. A coating film obtained by adding colloidal silica or the like to the coating material may be formed.

[0024]

[Function] The agricultural vinyl chloride resin film of the present invention is
It comprises 5 to 100 parts by weight of an ethylene-vinyl chloride copolymer resin having an ethylene content of 0.1 to 7.0% by weight and 95 to 0 parts by weight of another vinyl chloride resin, and has a total ethylene content of 0.1. ~ 7.0 wt% vinyl chloride resin 100
Since a vinyl chloride resin composition obtained by adding 0.01 to 0.2 part by weight of a hindered amine compound having one or more specific structural units in the molecule to a part by weight is formed into a film, conventional polyvinyl chloride is used. As compared with an agricultural film using a resin, an agricultural film that is less likely to deteriorate in the metal contact portion of the film can be obtained.

[0025]

【Example】

[Examples 1 to 9 and Comparative Examples 1 to 4] The formulations shown in Table 1 were placed in a Henschel mixer, and after stirring and mixing for 10 minutes,
A vinyl chloride resin film for agriculture was obtained by heating and melting at 175 ° C., kneading with a roll, and then forming into a film having a thickness of 0.1 mm by a calender device. With respect to the obtained agricultural vinyl chloride resin film, the degree of deterioration in the metal contact portion and the calendering workability were evaluated by the following methods. The results are shown in Table 1.

<Degree of Deterioration in Metal Contact Area> [Test Method] After 18 months have passed since the obtained agricultural vinyl chloride resin film was spread on a house using a uniformly rusted pipe as a frame material, the metal of the film was used. The contact portion was visually observed and evaluated according to the following evaluation criteria. [Evaluation Criteria] A: Almost no discoloration is observed. ○: Yellowed part is seen. △: Yellowed in most parts and partially browned. X: The film turned brown in most places, and the film was torn.

<Calendar Workability> [Test Method] The appearance during calendering and the surface condition of the obtained film were visually observed and evaluated according to the following criteria. [Evaluation Criteria] ◎ ・ ・ ・ Processing is possible without problems as with polyvinyl chloride ○ ・ ・ ・ Slightly sticky, but good processing △ ・ ・ ・ Strong adhesiveness, processing is possible but surface smoothness is poor × ... Strong adhesion, difficult or impossible to process

[0028]

[Table 1] * 1 Compound shown in Chemical formula 3 * 2 Compound shown in Chemical formula 4 * 3 Compound shown in Chemical formula 5

[0029]

Embedded image

[0030]

[Chemical 4]

[0031]

Embedded image

[0032]

As described in detail above, the agricultural vinyl chloride resin film of the present invention is less likely to deteriorate in the metal contact portion than the conventional agricultural film using polyvinyl chloride, and therefore It can be extended over a long period of time. Therefore, it is possible to significantly reduce the number of times of reworking of the agricultural film spread on the house,
This will contribute to reducing the burden on farmers and saving resources.

Claims (1)

[Claims] 1. The ethylene content is 0.1 to 7.0% by weight.
Vinyl chloride resin 100 comprising 5 to 100 parts by weight of ethylene-vinyl chloride copolymer resin and 95 to 0 parts by weight of another vinyl chloride resin, and having a total ethylene content of 0.1 to 7.0% by weight. A vinyl chloride resin composition obtained by adding 0.01 to 0.2 parts by weight of a hindered amine compound having at least one structural unit represented by the general formula shown in Chemical Formula 1 in a molecule is formed into a film. A vinyl chloride resin film for agriculture. Embedded image (In the formula, R _{1 to} R ₅ each represent the same or different hydrogen or an alkyl group having 1 to 4 carbon atoms)