JP2833447B2 - Agricultural vinyl chloride resin film - Google Patents

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 to a vinyl chloride resin film for agriculture which has less stains when exposed to the outdoors and has good calenderability.

[0002]

2. Description of the Related Art Conventionally, for example, a vinyl house is constructed by connecting a steel or stainless steel pipe bent into a predetermined shape to form a frame, and a skylight or an entrance is provided at a predetermined position.
Its surface is covered with a transparent vinyl chloride resin film.

[0003]

Incidentally, the film covering the conventional vinyl house is usually a film mainly composed of a vinyl chloride resin to which a plasticizer is added. If used for a period, there is a problem that the plasticizer is exposed to sunlight, wind and rain, migrates to the surface of the film due to migration, becomes sticky, and adheres dust and dust outside.

The object of the present invention is to provide a vinyl chloride resin film for agricultural use, which has a small amount of dirt when exposed to the outdoors and has a good calendering processability. I do.

[0005]

SUMMARY OF THE INVENTION The present invention relates to an agricultural vinyl chloride resin film mainly comprising a vinyl chloride resin containing a phosphate ester, wherein the vinyl chloride resin has an ethylene content of 0.1%. 7.0 wt% of an ethylene - vinyl copolymer 5-100 parts by weight chloride and other vinyl chloride polymer is made from 95 to 0 parts by weight, and the total ethylene content in the vinyl chloride resin is 0. 1 to 7.0% by weight, and the phosphate ester is (a) xylenol 5
0 to 75% by weight, (b) 10 to 25% by weight of cresol, and (c) 10 to 25% by weight of ethylphenol (provided that (a) + (b) + (c) = 100% by weight) Raw material, and vinyl chloride resin 1
An object of the present invention is to provide a vinyl chloride resin film for agricultural use, wherein 1 to 7 parts by weight of the phosphate is added to 00 parts by weight.

The ethylene-vinyl chloride copolymer used in the present invention must have an ethylene content of 0.1 to 7.0% by weight, and the ethylene-vinyl chloride copolymer having an ethylene content of less than 0.1% by weight. When a vinyl copolymer is used, the effect of preventing contamination is small. On the other hand, when an ethylene-vinyl chloride copolymer having an ethylene content of more than 7.0% by weight is used, the film is processed by calendering. It tends to stick to rolls during manufacturing. A more preferable range of the ethylene content is 0.5 to 7.0% by weight.

The ethylene-vinyl chloride copolymer may be used alone or as a mixture with another vinyl chloride-based polymer. When mixing and using other vinyl chloride-based polymer during mixing 100 parts by weight of the polymer, 5 parts by weight or more of ethylene - vinyl chloride copolymer, and the total ethylene content of the salt of the vinyl resin is It must be 0.1-7.0% by weight, preferably 0.3-3.0% by weight. If the mixing ratio of the ethylene-vinyl chloride copolymer is less than 5 parts by weight per 100 parts by weight of the mixed polymer, or if the total amount of ethylene in the vinyl chloride resin is less than 0.1% by weight, a sufficient effect of preventing contamination can be expected. Can not.

Other vinyl chloride polymers to be mixed with the ethylene-vinyl chloride copolymer include vinyl chloride homopolymers and copolymers of vinyl chloride and other monomers, which are copolymerizable with vinyl chloride. As other monomers,
For example, propylene, vinyl acetate, vinylidene chloride, acrylic acid, alkyl acrylate, methacrylic acid,
Examples include alkyl methacrylate, maleic acid, fumaric acid, acrylonitrile, and alkyl vinyl ether.

This vinyl chloride resin contains a phosphoric acid ester made from a mixed alcohol consisting of (a) xylenol, (b) cresol and (c) ethylphenol. The mixing ratio of (a) xylenol in the phosphate ester is 50 to 75% by weight, preferably 60 to 75% by weight.
If it is less than 50% by weight, the weather resistance is deteriorated, while if it exceeds 75% by weight, the sticking of the roll at the time of calendering becomes easy. Also, the blending ratio of (b) cresol is 10 to 25% by weight, preferably 12 to 23% by weight. When it is less than 10% by weight, heat resistance is deteriorated, and when it exceeds 25% by weight, dirt tends to adhere. Become. further,
(C) The compounding ratio of ethyl phenol is 10 to 25% by weight, preferably 12 to 23% by weight, and if it is less than 10% by weight, gelation of the vinyl chloride resin composition constituting the film becomes poor, while 25 Exceeding the percentage by weight increases plate-out on a calender roll, which is not preferred.

The mixing ratio of the phosphate ester is 1 to 7 parts by weight, preferably 2 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the amount exceeds the weight part, the weather resistance becomes poor.

Incidentally, 0.5 to 6 parts by weight of a drip-proofing agent can be added per 100 parts by weight of the vinyl chloride resin. When the amount is less than 0.5 part by weight, the drip-proof property is poor.

Examples of the anti-drip 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 Esters, esters of polyhydric alcohols such as glycerin fatty acid and dibasic acid esters, and esters of fatty acids and polyhydric alcohols with fatty acids and dibasic acids, or alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide added to these And the like, 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, diglycerin stearate Glycerin stearate, glycerin palmitate / ethylene oxide 2 mol adduct, sorbitan stearate adipate / ethylene oxide 3 mol adduct, sorbitol stearate adipate / ethylene oxide 2 mol adduct, diglycerin palmitate sebacate propylene oxide 3 A molar adduct, a sorbitol palmitate adipate / ethylene oxide 3 mol adduct, and the like. These drip-proofing agents can be used alone or in combination of two or more.

The agricultural vinyl chloride resin film of the present invention, together with the anti-drip agent, is used in an amount of 0.01 to 1.0 part by weight, preferably 0.0 to 1.0 part by weight, per 100 parts by weight of the vinyl chloride resin.
5 to 0.5 parts by weight of a fluorine-containing compound can be added.

The fluorinated compound is a fluorinated compound having a fluorinated group and at least one of a hydroxyl group and an alkylene oxide group in one molecule. The fluorinated group is a 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), perfluoroalkylene group (C _n F _2n group)
Where m = 1 to 3 and n = 3 to 20. Examples of the alkylene oxide group include (C ₂ H ₄ O) _n ,
(C ₃ H ₄ O) _n , where n = 1 to 30.

Specific examples of the fluorine-containing compound include C ₈ F
₁₇ C ₂ H ₄ O (C ₂ H ₄ O) ₈ CH ₃ , C ₈ F ₁₇ CH ₂ CH ₂ OHCH ₂ O (C ₂ H ₄ O) ₁₀ CH
₃ , C ₁₄ F ₂₁ CH ₂ CH (OCH ₃ ) CH ₂ O (C ₂ H ₄ O) ₁₀ CH ₃ , C ₁₄ F ₂₁ CH ₂ C
H (OH) CH ₂ O (C ₂ H ₆ O) ₁₀ H, C ₈ F ₁₇ CH ₂ CH (OCOH ₃ ) CH ₂ O (C ₃ H ₆ O)
₈ CH ₃ , C ₈ F ₁₇ SO ₂ N (C ₂ H ₅ ) (C ₂ H ₄ O) ₁₂ , C ₆ F ₁₃ CON (C ₂ H ₅ ) (C ₂ H
₄ O) ₈ H, C ₈ F ₁₇ SO ₂ N [CH ₂ CH (OH) CH ₂ CH] ₂ , HCF ₂ C ₅ F ₁₀ CH ₂ O
(C ₂ H ₄ O) ₁₀ H, C ₃ F ₇ OC ₃ F ₆ CH ₂ CH ₂ SCH (COOH) CH ₂ COO (C ₂ H ₄ O)
₁₀ H, C ₃ F ₇ OC ₃ F ₁₀ CH ₂ CH ₂ SCH (CH ₂ COOH) CH ₂ COO (C ₂ H ₄ O)
₁₅ H, And the like, but are not limited thereto.

The vinyl chloride resin film for agriculture of the present invention may further comprise, if necessary, a plasticizer other than the phosphate ester, a stabilizer, a lubricant or an anti-adhesive, an ultraviolet absorber,
Antioxidants, light stabilizers, inorganic fillers and the like can be added. As the plasticizer added to the vinyl chloride resin, a general plasticizer and an epoxy plasticizer can be used.

Examples of general plasticizers include di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, dibutyl phthalate, butyl benzyl phthalate, dilauryl phthalate, didecyl phthalate, diunadecyl phthalate, and ditridecyl phthalate. Phthalate plasticizer, dioctyl adipate, ditrinonyl adipate, diisodecyl adipate, etc., as well as polyester plasticizer, sebacate ester plasticizer, trimellitate plasticizer, etc. it can.

Epoxy plasticizers include epoxidized vegetable oils and epoxy resins. Epoxidized vegetable oils include epoxidized soybean oil and epoxidized linseed oil.

Epoxy resins include epoxidized polybutadiene, methyl epoxy stearate, butyl epoxy stearate, ethylhexyl epoxy stearate, tris (epoxypropyl) isocyanurate,
-(2-xenoxy) -1,2-epoxypropane, bisphenol A, diglycidyl ether, vinyl dicyclohexene diepoxide, polycondensate of 2,2-bis (4-hydroxyphenyl) propane and epichlorohydrin. The plasticizers may be used alone or as a mixture of two or more. The preferred amounts are 30 to 70 parts by weight of a phthalate ester plasticizer and 100 parts by weight of an epoxy plasticizer per 100 parts by weight of a vinyl chloride resin. 5 to 7 parts by weight.

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-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. One or more of these stabilizers can be used.

Examples of the lubricant or antiadhesive 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; ester lubricants such as barium isodecyl phosphate and calcium octadecyl phosphate; lubricants such as polyethylene wax and liquid paraffin; and one or more of these may be used. it can.

Examples of the ultraviolet absorber include commonly used ultraviolet absorbers such as benzophenone-based, benzotriazole-based, salicylate-based, and cyanoacrylate-based ones, and one or more of these can be used. .

As the antioxidant, one or more antioxidants such as phenol-based, thiodipropionate-based and aliphatic sulfide-based antioxidants can be used.
As the light stabilizer, one or more commonly used light stabilizers such as hindered amines can be used.

The inorganic fine powder can be used for the purpose of preventing stickiness on the film surface and improving the heat retaining property. As such inorganic fine powder, at least one or more of magnesium carbonate, magnesium silicate, silicon oxide, aluminum oxide, aluminum hydroxide, magnesium hydroxide and hydrotalcites can be used. The diameter is preferably 20 μm or less.

[0026]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. Examples 1 to 5 and Comparative Examples 1 to 8 A vinyl chloride resin shown in Table 1 and a phosphate ester shown in Table 2 were charged into a Henschel mixer according to the formulation shown in Table 3 and mixed by stirring for 10 minutes. The mixture was heated and melted and kneaded in a roll, and then a film having a thickness of 0.1 mm was formed by a calender. This film was used in a test laboratory for approximately 6 years from winter to summer.
The film was exposed outdoors for months, and the parallel light transmittance of the film was measured. In addition, calendering properties during film production [roll adhesion, plate-out, heat discoloration (heat resistance, gelling properties)] were also checked. Table 3 shows the results.

[0027]

[Table 1]

[0028]

[Table 2]

[0029]

[Table 3]

*) Judgment of calendering processability 〇: Roll adhesion is small, and good processing can be performed. X: Roll adhesion is strong and processing is difficult. As is evident from Table 3, films within the scope of the present invention have little stain on outdoor exposure and have no problem in calenderability.

[0031]

The agricultural vinyl chloride resin film of the present invention contains an ethylene-vinyl chloride copolymer having an ethylene content of 0.1 to 7.0% by weight, and the total ethylene content in the vinyl chloride resin. (A) 50-75% by weight of xylenol, and (b)
Cresol 10-25% by weight and (c) ethylphenol 10-25% by weight [however, (a) + (b) +
(C) = 100% by weight], so that the plasticizer hardly emerges on the surface of the film even after long-term use. Stickiness is suppressed, and film stains during outdoor exposure can be reduced. In addition, since the ethylene content is also kept within the range of 0.1 to 7.0% by weight, even when a film is produced by calendering, the film can be favorably produced without sticking the resin to the roll.

Claims (1)

(57) [Claims] 1. An agricultural vinyl chloride resin film mainly comprising a vinyl chloride resin containing a phosphate ester, wherein the vinyl chloride resin has an ethylene content of 0.1%.
~ 7.0 wt% ethylene-vinyl chloride copolymer 5-1
00 parts by weight and 95 to 0 parts by weight of another vinyl chloride- based polymer, and the total ethylene content in the vinyl chloride-based resin is 0.1 to 7.0% by weight, and the phosphate ester is (A) 50 to 75% by weight of xylenol, (b) 10 to 25% by weight of cresol, and (c) 10 to 25% by weight of ethylphenol [where (a) + (b) + (c) =
100% by weight], and 1 to 7 parts by weight of the phosphoric ester is added to 100 parts by weight of the vinyl chloride resin.