JP2002338764A - Agricultural vinyl chloride resin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an agricultural vinyl chloride resin film excellent in tear strength and transparency. SOLUTION: This agricultural vinyl chloride resin film is prepared by forming a resin composition which is prepared by compounding 100 pts.wt. vinyl chloride resin with 0.1-10 pts.wt. ethylene/unsaturated carboxylic ester/carbon monoxide copolymer, 20-70 pts.wt. plasticizer, and 0.5-5 pts.wt. drip-proofing agent. Thus, a vinyl chloride resin film having an improved tear strength can be obtained without substantial detriment to transparency, and the cost can be kept low in comparison with the case when a vinyl chloride resin having a higher degree of polymerization is used.

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 having excellent tear strength and transparency.

[0002]

2. Description of the Related Art Conventionally, various films have been used as agricultural films, especially as films for covering agricultural houses. Above all, a vinyl chloride resin film is superior in transparency and flexibility as compared with an olefin resin film and a polyester resin film.

[0003]

However, the vinyl chloride resin film has a lower tear strength than the polyolefin resin film and the polyester resin film, and is caught at the joint of pipes when being spread on an agricultural house. There was a problem of breaking. Therefore, by increasing the degree of polymerization of vinyl chloride resin,
Attempts have been made to increase the tear strength. However, when the degree of polymerization of the resin is increased, the cost of the resin is considerably increased, and it has been difficult to produce an inexpensive agricultural vinyl chloride resin film having a high tear strength.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and is intended to solve the above-mentioned problems. Agricultural vinyl chloride resin film obtained by molding a resin composition containing 0.1 to 10 parts by weight of a carbon copolymer, 20 to 70 parts by weight of a plasticizer, and 0.5 to 5 parts by weight of a drip-proof agent. It is.

The vinyl chloride resin used in the present invention includes polyvinyl chloride, a copolymer of a vinyl chloride monomer and another monomer copolymerizable with vinyl chloride, and a copolymer of a vinyl chloride monomer and a higher vinyl ether. Copolymers, etc.
Or a mixture thereof. Examples of monomers copolymerizable with vinyl chloride include olefin monomers such as ethylene, propylene, maleic ester, methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methacrylic acid, acrylic acid, and vinyl acetate. And vinyl monomers.

As plasticizers, dioctyl phthalate (DOP) and diisononyl phthalate (DI
NP), butyl benzyl phthalate (BBP),
General phthalate plasticizers represented by diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), dioctyl adipate (DOA), dioctyl sebacate (D
OS), general fatty acid ester plasticizers such as diazetyl azelate (DOZ), trimellitate plasticizers such as trioctyl trimellitate (TOTM), and polypropylene adipate. Polymeric plasticizers such as polyester plasticizers, other sebacic acid plasticizers, general plasticizers such as chlorinated paraffin, tricresyl phosphate (TCP), trixylyl phosphate (TXP), tris (isopropyl) Phenyl ester-based plasticizers such as phenyl) phosphate, tributyl phosphate, triethyl phosphate, triphenyl phosphate, and triethylphenyl phosphate. These plasticizers can be used alone or in combination of two or more. In the present invention, the plasticizer is added in an amount of 20 to 70 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the added amount of the plasticizer is too small, the resin composition becomes hard and becomes difficult to mold into a film, and if the added amount of the plasticizer is too large, the film becomes too soft,
It becomes difficult to handle.

The dripproofing agents usable in the present invention include conventionally known sorbitan fatty acid esters, sorbitol fatty acid esters, glycerin fatty acid esters, diglycerin fatty acid esters, sorbitan fatty acid / dibasic acid esters, glycerin fatty acid / dibasic acid esters. Acid esters, esters of polyhydric alcohols such as diglycerin fatty acids and dibasic acid esters with fatty acids, esters of polyhydric alcohols with fatty acids and dibasic acids, or alkylene oxides such as ethylene oxide and propylene oxide added thereto Sorbitan palmitate, sorbitan stearate, sorbitan stearate / ethylene oxide 1 mol adduct, sorbitan stearate / ethylene oxide 2 mol adduct, sorbitan Areto-propylene oxide 3
Mol adduct, sorbitan stearate / ethylene oxide 3 mol adduct, diglycerin palmitate, diglycerin stearate, glycerin palmitate, glycerin stearate, glycerin palmitate / ethylene oxide 2 mol adduct, sorbitan stearate adipate / ethylene A 3 mol adduct of oxide, a 2 mol adduct of sorbitol stearate adipate / ethylene oxide, a 3 mol adduct of diglycerin palmitate sebacate / propylene oxide, a 3 mol adduct of sorbitol palmitate adipate / ethylene oxide, and the like can be used. Preferred are sorbitan dripproofing agents such as sorbitan palmitate. These drip proof agents are
They may be used alone or in combination of two or more. In the present invention, the addition amount of the above-mentioned drip-proofing agent is 0.5 parts per 100 parts by weight of the vinyl chloride resin.
Add up to 5 parts by weight. If the addition amount of the drip-proof agent is too small,
If the drip-proof effect is not sufficient and the amount of the drip-proof agent is too large, not only does the cost increase, but also bleeding occurs,
The film surface may be whitened.

The ethylene-unsaturated carboxylic acid ester-carbon monoxide copolymer used in the present invention is a copolymer of ethylene, unsaturated carboxylic acid ester and carbon monoxide, and is used for producing high-pressure polyethylene. Similarly,
It can be obtained by radical copolymerization of each polymerization component under high temperature and high pressure.

The unsaturated carboxylic acid ester is, for example, an ester of an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, and more specifically, methyl acrylate, acrylic acid Ethyl acrylate, isopropyl acrylate, isobutyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate,
Examples thereof include dimethyl maleate and diethyl maleate.

[0010] The ethylene-unsaturated carboxylic acid ester-carbon monoxide copolymer has an ethylene content of 50%.
~ 80 wt%, unsaturated carboxylic acid ester is 10 ~ 45
It is preferable that carbon monoxide is copolymerized at 1 to 20% by weight.

The agricultural vinyl chloride resin film of the present invention may contain, if necessary, an antifogging agent, a heat stabilizer, a light stabilizer, a lubricant or an anti-adhesive, an ultraviolet absorber, an antioxidant, a filler, and the like. Can be added.

[0012] As an antifog, fluorine is contained in one molecule.
Group and at least a hydroxyl group or an alkylene oxide group
A fluorine-containing compound having at least one fluorine-containing compound;
As a perfluoroalkyl group (C_nH_{2n + 1}Group),
Perfluoroalkoxy group (C _nF_{2n + 1}O group), polyflu
Oroalkyl group (H_mC_nF_{2n + 1-m}Group), perfluoroa
Lucenyl group (C_nF_2n-1Group), polyfluoroalkenyl group
(H_mC_nF_2n-1-m(Wherein m is an integer of 1 to 3)
Number, n is an integer of 3 to 20), an alkylene oxide group and
Then, (C_TwoH_FourO)_n, (C_ThreeH₆O)_n Etc.
(Where n is an integer of 1 to 30). These fluorine compounds
The amount of the additive is 0.0
1 to 1 part by weight, preferably 0.05 to 0.5 part by weight
You. Specific examples of the fluorine compound are shown in Chemical formula 1.
Such compounds are mentioned.

[0013]

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Examples of the heat stabilizer include zinc stearate, barium stearate, calcium stearate, barium ricinoleate, calcium laurate, calcium oleate and other metal soaps, epoxy compounds such as epoxidized soybean oil, diphenyl decyl phosphite, triphenyl Phenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, tristearyl phosphite,
Organic phosphite-based stabilizers such as octyl diphenyl phosphite, and tin-based stabilizers such as dibutyl tin laurate, dibutyl tin malate, organic tin mercaptide, and organic tin sulfonamide can be used. These stabilizers can be used alone or in combination of two or more. The amount of the heat stabilizer to be added 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 resin.

As light stabilizers, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,2
6,6-pentamethyl-4-piperidyl stearate,
2,2,6,6-tetramethyl-4-piperidylbenzoate, N- (2,2,6,6-tetramethyl-4-piperidyl) dodecylsuccinimide, 1-[(3,5-
Di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] -2,2,6,6-tetramethyl-4-piperidyl (3,5-di-tert-butyl-
4-hydroxyphenyl) propionate, bis (2,
2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6,-
(Pentamethyl-4-piperidyl) -2-butyl-2-
(3,5-di-tert-butyl-4-hydroxybenzyl) malonate, N, N′-bis (2,2,6,6-
Tetramethyl-4-piperidyl) hexamethylenediamine, tetra (2,2,6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, bis (2
2,6,6-tetramethyl-4-piperidyl) di (tridecyl) butanetetracarboxylate, bis (1,
2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) butanetetracarboxylate, 3,9
-Bis {1,1-dimethyl-2- [tris (2,2,
6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy] ethyl} -2,
4,8,10-tetraoxysaspiro [5,5] undecane, 3,9-bis {1,1-dimethyl-2- [tris (1,2,2,6,6-pentamethyl-4-piperidyloxy) Carbonyloxy) butylcarbonyloxy] ethyl {-2,4,8,10-tetraoxaspiro [5
5] Undecane, 1,5,8,12-tetrakis @ 4
6-bis [N- (2,2,6,6-tetramethyl-4-
Biperidyl) butylamino] -1,3,5-triazin-2-yl {-1,5,8,12-tetraazadodecane, 1- (2-hydroxyethyl) -2,2,6,6-
Tetramethyl-4-piperidinol / dimethyl succinate condensate, 2-tert-octylamino-4,6-dichloro-s-triazine / N, N'-bis (2,2,6,
6-tetramethyl-4-piperidyl) hexamethylenediamine condensate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine /
Hindered amine light stabilizers such as dibromoethane condensate and the like are included.

Examples of the lubricant include metal soaps such as zinc stearate, barium stearate, and calcium stearate; hydrocarbons such as liquid paraffin, polyethylene waxes and chlorinated hydrocarbons; stearic acid, stearamide, and palmitamide And fatty acid amides such as methylene bis-stearamide and ethylene bis-stearamide; and lubricants such as fatty acid esters such as butyl stearate, cetyl palmitate and monoglyceride stearate. These lubricants may be used alone or in combination of two or more.

Examples of the ultraviolet absorber include salicylic acid ester, benzotriazole, hydroxybenzophenone,
And acrylonitrile-substituted products. These ultraviolet absorbers can be used alone or in combination of two or more. Specifically, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-ethoxybenzophenone,
-Hydroxy-4-octoxybenzophenone, 5,
2-hydroxybenzophenones such as 5'-methylenebis (2-hydroxy-4-methoxybenzophenone);
2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'
-Di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-ter
t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-te
rt-octylphenyl) benzotriazole, 2-
(2′-hydroxy-3 ′, 5′-dicumylphenyl)
Benzotriazole, 2,2′-methylenebis (4-t
2- (2'-hydroxyphenyl) benzotriazoles such as tert-octyl-6-benzotriazole) phenol; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3 ', 5'-Di-tert-butyl-4'-hydroxybenzoate, hexadecyl-3,5-di-tert
Benzoates such as -butyl-4-hydroxybenzoate; oxanilides such as 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-β, β-diphenylacrylate, methyl-2-cyano-3-methyl −
And cyanoacrylates such as 3- (p-methoxyphenyl) acrylate. These ultraviolet absorbers may be used alone or in combination of two or more.

Examples of the antioxidant include alkylphenol, alkylenebisphenol, alkylphenol thioether, β, β'-thiopropionate, organic phosphite, aromatic amine, and phenol / nickel complex. These antioxidants can be used alone or in combination of two or more.

As the filler, calcium carbonate, titanium oxide, aluminum hydroxide, talc, feldspar, silica, hydrotalcite and the like can be used.

The vinyl chloride-based resin composition obtained by adding the above-mentioned plasticizer, stabilizer and various additives to be added to the vinyl chloride-based resin can be prepared by an appropriate method such as a calendering method, an extrusion method and an inflation method. By means, it is formed into a film of a desired thickness. For the thickness of the film, see
It is preferably about 0.05 to 0.2 mm.

The film made of the vinyl chloride resin obtained as described above may be formed on one or both sides thereof with a coating film of an appropriate paint. For example, when used as a covering material for agricultural facilities, a dust-proof coating of a solvent-based, water-based, or UV-curable paint is formed on the surface that becomes the outer surface when spread, or the inner surface when the material is spread. On the surface to be formed, a drip-proof coating film can be formed using a paint obtained by adding a hydrophilic substance such as colloidal silica to a solvent-based, water-based, or ultraviolet-curable paint.

As the solvent-based paint, for example, an acrylic resin-based, vinyl chloride resin-based, cellulose resin-based, fluorine resin-based, polyamide-based, urethane resin-based, epoxy resin-based, or silicone resin-based paint can be used. As the water-based paint, for example, acrylic resin, polyester,
Paints such as urethane resin and epoxy resin can be used. As the UV-curable paint, for example, an acrylic resin-based, acrylic-modified urethane resin-based, acrylic-modified epoxy resin-based, mercapto derivative-based, epoxy resin-based paint, or the like can be used.

[0023]

EXAMPLES Examples 1 to 5 and Comparative Examples 1 to 4 As examples and comparative examples, from the formulations shown in Tables 1 and 2,
A film having a thickness of 0.1 mm was produced by a calender method. In addition, the tear strength of the produced film was measured according to JIS K
It measured by the method based on 6732, and evaluated the blooming property of the film visually. Frontage 3
m, height 2m, length 10m pipe house
The degree of tearing after one and a half years was visually evaluated. The evaluation criteria for transparency and tear are as follows.

[0024]

[Table 1] * 1 Epikote 828 (manufactured by Ciel Chemical) * 2 Bisamide (manufactured by Nippon Kasei) * 3 Slipax E (manufactured by Nippon Kasei) * 4 Elvaloy HP553 (manufactured by Mitsui DuPont) (ethylene 60% by weight, n-butyl acrylate) 30% by weight,
* 5 Elvaloy 741 (manufactured by Mitsui DuPont) (ethylene 66% by weight, vinyl acetate 24% by weight, carbon monoxide 10)
* 6 DS-403 (manufactured by Daikin) * 7 Chima Soap 944LD (manufactured by Ciba Geigy) * 8 ｛(C ₁₈ H ₃₇ O) ₃ COO｝ ₂ Zn * 9 Almost no blooming △ Some blooming × Intense bloom * 10 Almost no tears □ Some small tears are noticeable △ Many tears × Torn and cut

[0025]

[Table 2] * 1 to 10 are the same as Table 1

[0026]

According to the present invention, the tear strength of the vinyl chloride resin film can be improved by adopting the above-mentioned structure without significantly impairing the transparency. Also,
The cost can be reduced as compared with the case where the degree of polymerization of the vinyl chloride resin is increased.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 73:00) F-term (Reference) 2B024 DB01 2B029 EB02 EC04 EC09 EC20 4F071 AA15X AA24 AA31X AA36X AA79 AC10 AC15 AE04 AE22 4J002 BB072 BB082 BB243 BD041 BD051 BD061 BD071 BD081 BD091 CF033 EH047 EH096 EH146 EW046 FD023 FD026 FD207

Claims (1)

[Claims] [Claim 1] 100 parts by weight of a vinyl chloride resin,
Molding a resin composition containing 0.1 to 10 parts by weight of an ethylene-unsaturated carboxylic acid ester-carbon monoxide copolymer, 20 to 70 parts by weight of a plasticizer, and 0.5 to 5 parts by weight of a drip-proof agent. Agricultural vinyl chloride resin film.