JPH09309996A - Agricultural vinyl chloride resin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an agricultural vinyl chloride resin film excellent in weatherability by compounding a vinyl chloride resin with an epoxidized polybutadiene having a specified epoxy equivalent and if necessary an organophosphorus compd. and a hindered amine light stabilizer. SOLUTION: 100 pts.wt. vinyl chloride resin selected from among polyvinyl chloride, a vinyl chloride-ethylene copolymer, etc., and their mixtures is mixed with 0.1-5.0 pts.wt. epoxidized polybutadiene having an epoxy equivalent of 100-300 and then with 0.01-5.0 pts.wt. organophosphorus compd. represented by formula I and/or formula II (wherein R1 to R7 are each aryl, alkaryl, or aralkyl; and (n) is 1-10), 0.01-0.3 pt.wt. hindered amine light stabilizer having a 2,2,6,6-tetramethylpiperidine unit, a plasticizer, an antiseptic, a fluorine compd., a lubricant, an ultraviolet absorber, etc., kneaded on a mixing roll, etc., and calendered to give 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 a vinyl chloride resin film for agricultural use.

[0002]

2. Description of the Related Art Conventionally, polyvinyl chloride has been used as a covering material for agricultural facilities such as tunnels and houses because of its low cost, good transparency, excellent heat retention and strength, and easy film formation. Agricultural films made of vinyl chloride resin represented by are widely used.

Agricultural film made of this vinyl chloride resin (hereinafter referred to as agricultural vinyl chloride resin film)
Is generally 100 parts by weight of vinyl chloride resin,
A vinyl chloride resin composition prepared by blending a predetermined amount of additives such as a plasticizer such as 2-ethylhexyl phthalate, a stabilizer, a drip-proofing agent, and an antifog agent (fluorine-containing compound) by means such as a calendering method. It is a film. Further, in order to improve the heat resistance and the weather resistance of the film when producing a vinyl chloride resin film for agriculture, an epoxy resin having bisphenol A as a skeleton was added to the above vinyl chloride resin composition. .

[0004]

However, the vinyl chloride resin composition containing the epoxy resin having bisphenol A as the skeleton has excellent heat resistance when formed into a film, but so-called fish eyes are generated. There is a problem that it is easy to occur, and particularly when the film forming work is continuously performed for a long time, the fish eyes tend to be generated more frequently.

The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, by using a specific epoxidized polybutadiene in place of the above-mentioned epoxy resin having bisphenol A as a skeleton, the fish described above can be obtained. It was found that the generation of eyes is suppressed and the dustproof property and weather resistance of the obtained agricultural vinyl chloride resin film are further improved, and the present invention has been completed.

[0006]

The agricultural vinyl chloride resin film of the present invention made to solve the above-mentioned problems is an epoxidized polybutadiene having an epoxy equivalent of 100 to 300 relative to 100 parts by weight of the vinyl chloride resin. To 0.1
It is characterized by being formed into a film from a vinyl chloride-based resin composition added by up to 5.0 parts by weight. In addition, the epoxy equivalent referred to in the present invention is determined by the following equation (1).

[Equation 1]

The vinyl chloride resin in the present invention includes polyvinyl chloride, vinyl chloride and ethylene, propylene, vinyl acetate, vinylidene chloride, acrylic acid, methacrylic acid, acrylic acid, as in the case of conventional agricultural vinyl chloride resin films. A copolymer with ester, methacrylic acid ester, maleic acid, fumaric acid, acrylonitrile, alkyl vinyl ether, or the like, or a mixture of these resins can be used.

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, an inorganic filler and the like. Various additives are added.

Specifically as the above-mentioned plasticizer, 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 , One or more selected from adipic ester plasticizers such as diisodecyl adipate; polyester plasticizers; sebacate ester plasticizers; trimellitic acid ester plasticizers; epoxy plasticizers such as epoxidized soybean oil Wear. The amount of plasticizer added is about 30 to 70 parts by weight based on 100 parts by weight of the vinyl chloride resin.

The above-mentioned drip-proofing agents 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 alkylene oxides such as butylene oxide have been added. 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.
It is about 0.5 to 6.0 parts by weight based on parts by weight.

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. 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], perfluoroalkenyl Group [C _n F _2n-1 group], polyfluoroalkenyl group [H
_m C _n F _2n-1-m group], a perfluoroalkylene group [C _n
F _2n group] and the like (provided that m is an integer of 1 to 3 and n is an integer of 3 to 20). As the alkylene oxide group,
(C ₂ H ₄ O) _n , (C ₃ H ₆ O) _{n and the} like (where n is an integer of 1 to 30).

Specific examples of the fluorine-containing compound include compounds 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.
The amount is 1.0 part by weight, more preferably about 0.05 to 0.5 part by weight.

[0013]

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As the stabilizer, a commonly used stabilizer such as a metal soap and an organic phosphite stabilizer can be used. Examples of the metal soap include zinc stearate, barium stearate, calcium stearate, barium ricinoleate, calcium laurate, calcium oleate, and zinc octoate. 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 the stabilizer is 0.5 to 100 parts by weight of the vinyl chloride resin.
The amount is 10 parts by weight, more preferably about 1 to 5 parts by weight.

Examples of the lubricant or anti-adhesive 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 UV absorber include benzophenone-based, benzotriazole-based, salicylate-based, and cyanoacrylate-based UV absorbers that are generally used. The above 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.

The agricultural vinyl chloride resin film of the present invention uses epoxidized polybutadiene in place of the conventionally used epoxy resin having bisphenol A as a skeleton. As the epoxidized polybutadiene, those having an epoxy equivalent of 100 to 300 can be used. If the epoxy equivalent of the epoxidized polybutadiene is too high or too low, the resulting vinyl chloride resin film for agriculture does not sufficiently improve the dust resistance and the weather resistance, especially the weather resistance.

The amount of the epoxidized polybutadiene added is 0.1 to 100 parts by weight of the vinyl chloride resin.
The amount is 5.0 parts by weight, preferably 0.5 to 3.0 parts by weight. If the addition amount of the epoxidized polybutadiene is too large, the dustproof property of the obtained vinyl chloride resin film for agriculture will be impaired, and if the addition amount is too small, the weather resistance of the obtained vinyl chloride resin film for agriculture will not be sufficiently improved.

In the agricultural vinyl chloride resin film of the present invention, epoxidized polybutadiene is used in place of the epoxy resin having bisphenol A as a skeleton to suppress the generation of fish eyes and to obtain an agricultural product. It further improves the weather resistance and dust resistance of the vinyl chloride resin film for use, but if it does not impair this effect, it is also possible to use an epoxy resin having a skeleton of bisphenol A that has been conventionally used in combination. It is possible.

In the vinyl chloride resin film for agriculture of the present invention, it is desirable to add an organic phosphorus compound represented by the general formula shown in Chemical formula 4 or Chemical formula 5 in addition to the epoxidized polybutadiene.

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As the above-mentioned organic phosphorus compound, one or more compounds represented by the general formula shown in Chemical formula 4, one or more compounds represented by the general formula shown in Chemical formula 5, or the general formula shown in Chemical formula 4 It may be a mixture of one or more compounds represented and one or more compounds represented by the general formula shown in Chemical formula 5. By adding this organic phosphorus compound in combination, the weather resistance and dust resistance of the obtained agricultural vinyl chloride resin film are further improved.

The amount of the above organic phosphorus compound added is 0.01 to 5.0 parts by weight, preferably 0.1 to 4.0 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the addition amount of the organophosphorus compound is too small, the weather resistance and dust resistance are not sufficiently improved, and if the addition amount is too large, not only the cost increases, but also due to the bloom of the added organophosphorus compound, etc. The transparency of the obtained agricultural vinyl chloride resin film may be impaired.

Further, in the vinyl chloride resin film for agriculture of the present invention, in order to further improve weather resistance,
It is desirable to add a hindered amine light stabilizer having a 2,2,6,6-tetramethylpiperidine unit.
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 added is 0.01 to 0.3 parts by weight based on 100 parts by weight of the vinyl chloride resin.
If the addition amount of the hindered amine light stabilizer is too small, the weather resistance is not sufficiently improved, and if the addition amount is too large, not only the cost increases, but also the agricultural vinyl chloride resin film obtained by blooming or the like. May impair transparency.

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 agricultural vinyl chloride resin film.

The agricultural vinyl chloride resin film of the present invention, like the conventional agricultural vinyl chloride resin film,
A dust-proof coating made of a solvent-based, water-based or UV-curable coating material may be formed on the surface that becomes the outer side when spread. 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 a water-based paint,
For example, acrylic resin type, polyester resin type, urethane resin type, epoxy resin type and the like can be mentioned. Examples of the ultraviolet curable coating material include acrylic resin-based, acrylic modified urethane resin-based, acrylic modified epoxy resin-based, mercapto derivative-based, and epoxy resin-based coatings.

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 A coating film obtained by adding colloidal silica or the like to an ultraviolet curable coating material may be formed.

[0028]

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 9] Vinyl chloride resin compositions having the compositions shown in Table 1 were kneaded at 175 ° C for 20 minutes with 8-inch test rolls, respectively, and then the thickness was adjusted to 0.
A 1 mm film was dispensed. With respect to the obtained film, the degree of generation of fish eyes, dust resistance, and weather resistance were evaluated by the following methods. Table 1 shows the results.

(1) Degree of Fish Eye Generation The obtained film was visually observed, and the degree of fish eye generation was evaluated on a scale of 5 according to the following criteria. [Evaluation Criteria] 5: No fish eyes were generated. 4: Fisheye is hardly generated. 3: Fish eyes are slightly generated. 2... Fish eyes are slightly generated. 1: Very many fish eyes are generated. (2) Evaluation of dustproofness The film was placed on the exposure table in the shape of a window frame facing the south side with an inclination angle of 45 °, and the dirt condition after 6 months was visually observed, and the following criteria were used as a guide. It was evaluated in five levels. [Evaluation Criteria] 5 ... Almost no stain is observed. 4: Slightly adhered. 3: Adhesion of dirt is observed. 2 ... Adhesion of dirt is remarkably observed. 1: Very large amount of dirt adhered. (3) Weather resistance The obtained film was spread on a pipe house having a frontage of 1.5 m and a height of 1 m, and the state of the film after 12 months was visually observed, and evaluated on a scale of 5 according to the following criteria. [Evaluation criteria] 5: Almost the same as before expansion. 4: No tearing, but slightly browning. 3: Slight tearing occurs and browning is observed. 2 ... Browning is remarkable and tears are often observed. 1... Browning occurs over the entire surface, and breakage is extremely large.

[0031]

[Table 1]

Comparative Examples 1 to 11 Films were obtained from the vinyl chloride resin compositions having the formulations shown in Table 2 in the same manner as in Examples. The obtained film was evaluated for the degree of generation of fish eyes, dust resistance, and weather resistance in the same manner as in the examples. Table 2 shows the results.

[0033]

[Table 2]

From the above results, the agricultural vinyl chloride resin film of the present invention has a better fish-eye appearance than the conventionally used agricultural vinyl chloride resin film to which the epoxy resin having bisphenol A as a skeleton is added. It can be seen that the degree of occurrence, dust resistance, and weather resistance are all excellent. Further, by adding the organic phosphorus compound and the hindered amine light stabilizer together, the dust resistance and weather resistance are further improved.

[0035]

As described in detail above, the vinyl chloride resin film for agriculture of the present invention is extremely low in the generation of fish eyes when formed into a film, and is superior to conventional vinyl chloride resin films for agriculture. However, it is also excellent in dust resistance and weather resistance. As described above, the agricultural vinyl chloride resin film of the present invention has a low frequency of occurrence of defects during production, and can be spread over a long period of time.
It significantly contributes to reducing the burden on farmers and saving resources.

Further, by using the organic phosphorus compound and the hindered amine light stabilizer in combination, the dustproof property and the weather resistance are further improved, and the vinyl chloride resin for agricultural use which can be spread for a longer period of time. A film is obtained.

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Claims (3)

[Claims] [Claim 1] 100 parts by weight of a vinyl chloride resin,
A vinyl chloride resin film for agriculture, which is formed by filming a vinyl chloride resin composition containing 0.1 to 5.0 parts by weight of epoxidized polybutadiene having an epoxy equivalent of 100 to 300. 2. The organic phosphorus compound represented by the general formula shown in Chemical formula 1 and / or the organic phosphorus compound shown by the general formula shown in Chemical formula 2 is added in an amount of 0.01 to 100 parts by weight of a vinyl chloride resin. The vinyl chloride resin film for agriculture according to claim 1, which is added by about 5.0 parts by weight. Embedded image Embedded image 3. A hindered amine light stabilizer having a 2,2,6,6-tetramethylpiperidine unit is added in an amount of 0.01 to 0.3 parts by weight based on 100 parts by weight of the vinyl chloride resin. The vinyl chloride resin film for agriculture according to 1 or 2.