JPH08302132A - Agricultural vinyl chloride resin film - Google Patents

Abstract

PURPOSE: To obtain an agricultural vinyl chloride resin film excellent in weathering resistance and resistant to deterioration at the area being in contact with e.g. a metallic pipe by adding a specified organophosphoric acid compound to a vinyl chloride resin. CONSTITUTION: A vinyl chloride resin composition prepared by adding 0.01-2.5 pts.wt. at least one compound selected from among the organophosphoric acid compounds represented by the formulas (a) to (c) (where R1 to R6 are each an aryl group) is formed into an agricultural film. It is desirable that an organophosphoric acid compound of the formula (wherein at least 30% of R1 to R6 groups are xylyl groups) is used.

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 agriculture, and more particularly, it has excellent weather resistance and is particularly deteriorated in the contact portion between a metal pipe or the like used for a frame of a house and the film. The present invention relates to a vinyl chloride resin film for agriculture, which is less likely to generate.

[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 vinyl chloride resin represented by polyvinyl chloride resin are widely used.

On the other hand, in recent years, due to lack of manpower for farmers and the like, there has been a demand for an agricultural film having excellent weather resistance capable of being spread over a long period of time so that the spreading work can be performed as few times as possible. As such an agricultural film, an agricultural film obtained by filming a vinyl chloride resin composition obtained by adding a specific amount of a phosphate ester plasticizer represented by tricresyl phosphate or trixylyl phosphate to a vinyl chloride resin Is widely used.

[0004]

However, in the agricultural film obtained by film-forming the vinyl chloride resin composition containing the phosphoric acid ester plasticizer in the specified amount, the phosphoric acid ester plasticizer is relatively expensive. Not only there is a problem that the cost is increased by a certain amount, but a relatively large amount of a phosphate ester plasticizer is added in order to impart weather resistance, specifically, 1 part by weight or more per 100 parts by weight of the vinyl chloride resin. Therefore, there is a problem in that the phosphoric acid ester plasticizer blooms and the transparency of the film deteriorates. Moreover, it cannot be said that the essential weather resistance is still sufficient, and the development of an agricultural film having further excellent weather resistance has been earnestly desired.

Further, in order to improve the weather resistance of the vinyl chloride resin film for agriculture, it has been proposed to add the organic phosphoric acid compound shown in Chemical formula 2 to the vinyl chloride resin. Similar to the plasticizers, the weather resistance is still insufficient, and there is a problem that the film is likely to deteriorate particularly at the contact portion between the film and the metal pipe used for the framework of the house.

[0006]

Embedded image (In the formula, R _{1 to} R ₄ represent the same or different alkyl groups, cycloalkyl groups, aralkyl groups, aryl groups, and alkyl-substituted aryl groups.)

The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, by using a vinyl chloride resin composition obtained by adding a specific organic phosphoric acid compound to a vinyl chloride resin, a phosphoric ester Not only can it be provided with excellent weather resistance without the use of plasticizers, but it is better than conventional phosphoric acid ester plasticizers and agricultural films to which organic phosphoric acid compounds that have been used in the past have been added. Further, they have found that an agricultural vinyl chloride resin film having further excellent weather resistance can be obtained, and completed the present invention.

[0008]

The agricultural vinyl chloride resin film of the present invention, which has been made to solve the above-mentioned problems, has a chemical formula of 1 (a) with respect to 100 parts by weight of the vinyl chloride resin.
To (c), a vinyl chloride resin composition obtained by adding 0.01 to 2.5 parts by weight of one or more compounds selected from the organic phosphoric acid compounds shown in FIGS. . Further, the above-mentioned organic phosphoric acid compound is R ₁
A compound in which at least 30% of R ₆ is a xylyl group is particularly preferably used.

[0009]

Embedded image (In the formula, R _{1 to} R ₆ are the same or different,
The aryl group which may have a substituent is shown. )

As the vinyl chloride resin used in the present invention, in addition to polyvinyl chloride, vinyl chloride and other monomers such as ethylene, propylene, vinyl acetate, vinylidene chloride, acrylic acid, acrylic ester, methacrylic acid, Examples thereof include copolymer resins with methacrylic acid esters, maleic acid, fumaric acid, acrylonitrile, alkyl vinyl ethers, etc., and mixtures of these resins.

If necessary, the vinyl chloride resin may contain a plasticizer, a drip-proofing agent, a fluorine-containing compound, a stabilizer, a lubricant or an anti-adhesive agent, an ultraviolet absorber, an antioxidant, a light stabilizer, and an inorganic filler. Various additives such as agents can also be added.

As the above-mentioned plasticizer, specifically, 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 Although one or more selected from epoxy plasticizers and the like can be used, as described above, the phosphoric acid ester plasticizer that has been added for the purpose of improving the weather resistance is a vinyl chloride resin film for agricultural use of the present invention. Then
It is not always necessary to add it, and it is preferable not to add the phosphoric acid ester-based plasticizer from the viewpoints of bloom prevention, cost, and the like. The amount of the plasticizer added is about 30 to 70 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

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 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, / ethylene oxide 2 mol adduct, sorbitan stearate adipate / ethylene oxide 3 mol adduct, sorby Lumpur stearate adipate,
Examples thereof include ethylene oxide 2 mol adduct, diglycerin palmitate sebacate / propylene oxide 3 mol adduct, sorbitol palmitate adipate / ethylene oxide 3 mol adduct, and the like. The drip-proof agent is
One kind or a combination of two or more kinds can be used. Further, the amount of the above-mentioned drip-proof agent added is about 0.5 to 6.0 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.

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 shown in 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.

[0016]

[Chemical 4]

As the stabilizer, a commonly used stabilizer such as metal soap and organic phosphite stabilizer 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-based lubricants such as stearic acid, isostearic acid and palmitic acid; fatty acid amide-based lubricants such as stearic acid amide, methylene bis stearamide and ethylene bis stearamide; 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 ultraviolet absorber include benzophenone-based, benzotriazole-based, salicylate-based, and cyanoacrylate-based ultraviolet absorbers that are commonly used. The above ultraviolet absorbers can be used alone or in combination of two or more.

As the light stabilizer, a generally used light stabilizer such as a hindered amine compound can be used. The light stabilizers can be used alone or in combination of two or more.

As the inorganic filler, at least one selected from 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.

To the above vinyl chloride resin composition used in the present invention, one or more compounds selected from the organic phosphoric acid compounds represented by the general formulas (a) to (c) are added. ing.

[0023]

Embedded image (In the formula, R _{1 to} R ₆ are the same or different,
The aryl group which may have a substituent is shown. )

The amount of the above-mentioned organic phosphoric acid compound added is 0.01 to 2.5 parts by weight, preferably 0.01 to 1.5 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the addition amount of the organic phosphoric acid compound is too small, the weather resistance is not sufficiently improved, and if the addition amount of the organic phosphoric acid compound is too large, the weather resistance is not proportionally improved and not only the cost is increased. The transparency of the vinyl chloride resin film for agriculture may be impaired due to bloom of the added organic phosphoric acid compound. In addition, phosphate ester plasticizers such as tricresyl phosphate and trixylyl phosphate may be used in combination as long as bloom is not generated, and the organic phosphoric acid compound shown in Chemical formula 2 may be used in combination. it can.

The above-mentioned organic phosphoric acid compound is preferably an organic phosphoric acid compound in which 30% or more, and more preferably 45% or more of R _{1 to} R ₆ in the organic phosphoric acid compound are xylyl groups. By using such an organic phosphoric acid compound, the effect expected by the present invention, in particular, the effect of preventing deterioration in the contact portion between the metal pipe and the film, which is a framework of an agricultural house or the like, is improved.

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.

[0028]

[Function] The agricultural vinyl chloride resin film of the present invention is
Since a vinyl chloride resin composition obtained by adding a specific amount of a specific organic phosphoric acid compound is used, a phosphoric acid ester plasticizer or an organic phosphoric acid compound that has been added for the purpose of improving weather resistance from the past can be used. It has weather resistance higher than that of the added one, and in particular, it is hard to cause deterioration in the contact portion with the metal.

[0029]

EXAMPLES 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 and Comparative Examples 1 to 5] Vinyl chloride resin compositions having the formulations shown in Table 1 were placed in a Henschel mixer and mixed with stirring for 10 minutes, and then at 175 ° C.
Was melted by heating, kneaded with a roll, and then formed into a film having a thickness of 0.1 mm by a calender device to obtain a vinyl chloride resin film for agriculture.

[Test Method] After a lapse of 18 months from spreading the obtained agricultural vinyl chloride resin film on a house using a uniformly rusted pipe as a frame material, visually observing the metal contact part of the film Then, the following evaluation criteria were evaluated. [Evaluation Criteria] A: Almost no discoloration is observed. ○: A part where yellowing is observed is seen △: Yellowing occurs at most of the parts and partly turns brown. X: The film turned brown in most places, and the film was torn.

[0032]

[Table 1] * 1 Compound shown in Chemical formula 3 * 2 Compound shown in Chemical formula 4 * 3 Compound shown in Chemical formula 5 * 4 Compound shown in Chemical formula 6 * Compound shown in Chemical formula 7

[0033]

Embedded image

[0034]

[Chemical 4]

[0035]

Embedded image

[0036]

[Chemical 6]

[0037]

[Chemical 7]

[0038]

As described in detail above, the agricultural vinyl chloride resin film of the present invention is excellent in weather resistance, and is particularly resistant to deterioration of the metal contact portion. Therefore, it can be extended for a long period of time, which significantly contributes to reducing the burden on farmers and saving resources.

Claims (2)

[Claims] 1. To 100 parts by weight of vinyl chloride resin,
0.01 to 2. One or more compounds selected from the organic phosphoric acid compounds represented by the general formulas (1) to (c).
An agricultural vinyl chloride resin film obtained by film-forming a vinyl chloride resin composition obtained by adding 5 parts by weight. Embedded image (In the formula, R _{1 to} R ₆ are the same or different,
The aryl group which may have a substituent is shown. ) 2. R _{1 to} R in one or more compounds selected from the organic phosphoric acid compounds represented by the general formulas shown in Chemical Formulas 1 (a) to (c), which are added to the vinyl chloride resin composition. The agricultural vinyl chloride resin film according to claim 1, wherein at least 30% of ₆ is a xylyl group.