JPH11106585A - Vinyl chloride resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a vinyl chloride resin compsn. for agriculture excellent in resistances to weather, heat, and coloration by compounding a vinyl chloride resin with an organophosphorus compd. having a specified structure, a phosphonic or phosphoric acid compd., and an org. phosphorus-contg. metal salt. SOLUTION: 100 pts.wt. vinyl chloride resin is compounded with 0.01-10.0 pts.wt. at least one organophosphorus compd. represented by formula I (wherein R1 to R4 are each 6-18C alkyl, cycloalkyl, aralkyl, aryl, alkaryl or alkenyl), 0.01-5 pts.wt. at least one phosphonic or phosphoric acid compd. having at least one hydroxyl group directly bonded to phosphorus, and 0.01-5 pts.wt. at least one org. phosphorus-contg. metal salt selected from among salts represented by formulas II and III (wherein R5 and R7 are each 1-30C alkyl, arylalkyl, aryl or alkylaryl; R6 is H or R8 O; R8 is the same as R5 : and M is an alkaline earth metal or zinc).

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 composition. More specifically, it is a vinyl chloride resin composition in which an organic phosphorus compound, a phosphorous acid or phosphoric acid compound and an organic phosphorus-containing metal salt are added to a vinyl chloride resin to improve weather resistance, coloring resistance, and heat resistance. .

[0002]

BACKGROUND ART Vinyl chloride resins are widely used as agricultural films and sheets because they are excellent in transparency, weather resistance, heat retention and strength, are easily processed into films, and are inexpensive.

However, vinyl chloride resins are susceptible to the effects of light and heat, and when exposed to outdoor light or rain for a long period of time, are colored or have reduced transparency, making it difficult to use them as agricultural films or sheets. Therefore, long-term weather resistance is required so that the spreading work can be performed in a small number of times due to a shortage of labor of farmers. On the other hand, vinyl chloride-based resin undergoes the action of heat during molding to cause dehydrochlorination and discoloration, adversely affecting weather resistance and reducing strength, which can reduce the commercial value of the product. Not a little. Especially,
In an agricultural film made of a vinyl chloride-based resin, the weather resistance has been improved by adding a phosphate ester-based plasticizer such as tricresyl phosphate or trixylyl phosphate. However, in the case of vinyl chloride resins to which these phosphate ester plasticizers have been added, it is necessary to add a relatively large amount of these plasticizers in order to improve the weather resistance due to their lack of performance. Bleeds on the film surface and attaches dirt and dust, thereby impairing the transparency of the film. For the purpose of remedying these drawbacks, tricresyl phosphate or trixylyl phosphate is used in combination with a metal salt of organic phosphoric acid or a phosphorus compound having an OH group at the phosphorus atom, but still has heat resistance, weather resistance, etc. Performances were insufficient.

[0004] In addition, inorganic films such as hydrotalcite are often used in agricultural films or sheets made of a vinyl chloride resin composition in order to enhance the heat retention in a house or a tunnel. However, this causes the film or sheet to become colored or less transparent, which adversely affects the crop in the house or tunnel. It has been strongly desired to find a vinyl chloride resin composition having excellent heat resistance and transparency to solve these drawbacks.

The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, by adding an organic phosphorus compound, a phosphorous acid or a phosphoric acid compound and an organic phosphorus-containing metal salt to a vinyl chloride resin, The present inventors have found a vinyl chloride resin composition for agricultural use having improved weather resistance, coloring resistance and heat resistance, and have completed the present invention.

[0006]

That is, the present invention relates to a method for preparing a vinyl chloride resin comprising the steps of: (a) adding a compound represented by the following general formula (I):
At least one kind of an organic phosphorus compound represented by the formula: (b) at least one kind of a phosphorous acid or a phosphoric acid compound having at least one hydroxyl group directly connected to phosphorus, and (c) a general formula of the following chemical formula (4): A vinyl chloride resin composition for agricultural use having excellent weather resistance, heat resistance, and coloring properties, characterized by blending at least one of the organic phosphorus-containing metal salts represented by (II) and (III). To provide.

[0007]

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[0008]

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Hereinafter, the vinyl chloride resin composition of the present invention will be described in more detail.

Some examples of the organophosphorus compounds represented by the general formula (I) of the formula (a) used in the present invention are as follows. No. 1 tetraphenyl / 4,4 '-(2,2-propylene) diphenyl phosphate No. 1 2 Tetraoctyl.4,4 '-(2,2-propylene) diphenyl phosphate No. 2 No. 3 dioctyl ditolyl-4,4 '-(2,2-propylene) diphenyl phosphate No. 3 4 Dioctyl ditridecyl. 4,4 '-(2,2-propylene) diphenyl phosphate No. 5 Tetraoctadecyl-4,4 '-(2,2-propylene) diphenyl phosphate No. 5 No. 6 dibenzyl ditolyl-4,4 ′-(2,2-propylene) difel phosphate No. 6 7 Dibenzyl dinonylphenyl / 4,4 '-(2,2-propylene) difel phosphate No. 7 8 tetraxylyl-4,4 '-(2,2-propylene) differ phosphate No. 8 9 tetraxylyl-4,4 '-(2,2-propylene) differ phosphate No. 9 10 dicyclohexyl ditolyl 4,4 '-(2,2-propylene) diphenyl phosphate No. 10 11 dodecyl octadecyl phenyl xylyl 4,4 '-(2,2-propylene) diphenyl phosphate and the like. The addition amount of the organic phosphorus compound is based on 100 parts by weight of the vinyl chloride resin.
It is 0.01 to 10.0 parts by weight, preferably 0.1 to 5 parts by weight.

As the phosphorous acid or phosphoric acid compound having at least one hydroxyl group directly connected to phosphorus of the component (b) used in the present invention, a compound represented by the following general formula (IV):

[0012]

Embedded image It is a compound represented by these. As a specific example,

[0013]

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[0014]

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[0015]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

Embedded image And so on. The amount of the phosphorous acid or the phosphoric acid compound to be added is 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, per 100 parts by weight of the vinyl chloride resin.

The component (c) used in the present invention [Formula 4]
Specific examples of the organic phosphoric acid constituting the organic phosphorus-containing metal salt represented by the general formulas (II) and (III) include, for example, monooctyl phosphoric acid, didodecyl phosphoric acid, dimethyl phosphoric acid, monoethyl phosphoric acid, monoethyl monooctyl phosphoric acid Dibutyl phosphate, monoisobutyl monooctyl phosphate, monooctyl monostearyl phosphate, diisopropyl phosphate, monotert-butyl phosphate, di-2-ethylhexyl phosphate, didecyl phosphate, monononyl phosphate, monooctadecyl phosphate, monotridecyl phosphate, dihexadecyl phosphate, monomethyl monooctadecyl Phosphoric acid, monoisooctyl monododecyl phosphoric acid, monohexyl monotridecyl phosphoric acid, monooleyl phosphoric acid, monodocosyl phosphoric acid, monooctadecyl monooleyl phosphoric acid, monophenyl phosphoric acid, mono-tert-butylphenyl phosphoric acid, monononylphenyl Acid, mono-2-ethylhexylmonophenylphosphoric acid, monononylphenylmonoamylphosphoric acid, diphenylphosphoric acid, mono (2-tert-butyl-4-methyl-phenyl) monooctylphosphoric acid, dibenzylphosphoric acid, ditolylphosphoric acid, monoisooctylmonoxylyl Phosphoric acid, monononylphenylmono-α-methylbenzylphosphoric acid, monophenylmonoxylylphosphoric acid, dieicosylphosphoric acid, dinaphthylphosphoric acid, monooctylphosphorous acid, monododecylphosphorous acid, monomethylphosphoric acid, monoethylphosphorous acid, monotertiary butylphosphoric acid, Monodecyl phosphite, monononyl phosphite, monooctadecyl phosphite, monotridecyl phosphite, monooleyl phosphite, monodocosyl phosphite, monophenyl phosphite, mono-tert-butylphenyl phosphite, monononylphenyl phosphite, monoxylyl phosphite, monoxylate α Methylbenzyl phosphite, Mononafuchiru phosphite and the like. When synthesizing organic phosphorus-containing metal salts, various organic phosphorus-containing metal salt mixtures comprising reaction products with various organic phosphoric acids synthesized by mixing appropriate amounts of these organic phosphoric acids as reactants are also excellent in the present invention. give. The amount of the organic phosphorus-containing metal salt is 0.01 to 100 parts by weight of the vinyl chloride resin.
To 5 parts by weight, preferably 0.1 to 3 parts by weight.

As the vinyl chloride resin used in the present invention, for example, polyvinyl chloride, polyvinylidene chloride,
Post-chlorinated polyvinyl chloride, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride- Vinyl acetate copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene copolymer, vinyl chloride-acrylate copolymer, vinyl chloride-maleate copolymer, vinyl chloride-methacrylate copolymer Polymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-urethane copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride- Styrene-acrylonitrile terpolymer and the like; And polyethylene, polypropylene, polyisobutylene, polybutene, poly-1-pentene or an ethylene-vinyl acetate copolymer, an olefin copolymer such as an ethylene-propylene copolymer, an acrylonitrile-butadiene-styrene copolymer, methacrylate. Mixtures with butadiene-styrene copolymer, polyurethane and the like can be mentioned.

In general, a vinyl chloride resin composition for agricultural use usually contains a plasticizer, a stabilizer, an antioxidant, and an ultraviolet absorber in addition to the above-mentioned additives in order to enhance the function in processing or use. Various additives such as an agent and an antifogging agent are used in combination.

The plasticizer which can be used in combination with the composition of the present invention includes a phthalate ester plasticizer (dimethyl phthalate,
Dibutyl phthalate, diheptyl phthalate, di-2-
Ethylhexyl phthalate, diisooctyl phthalate, di-n-octyl phthalate, diisononyl phthalate, didecyl phthalate, diisodecyl phthalate,
Dilauryl phthalate, dicyclohexyl phthalate,
Butyl benzyl phthalate, dibenzyl phthalate, etc.), ester plasticizers or polyester plasticizers of carboxylic acids other than phthalic acid (di-n-butyl adipate, di-n-octyl adipate, diisononyl adipate, diisodecyl adipate, Polypropylene adipate, polybutylene adipate, diisobutyl azelate, di-2-ethylhexyl azelate, dibutyl sebacate, di-2-ethylhexyl sebacate, polypropylene sebacate, tri-2-ethylhexyl trimellitate, triisodecyl trimellitate , Di-2-ethylhexyl fumarate, tributyl citrate, dibutyl malate, dioctyl malate, methyl acetyl ricinolate, polypropylene sebacate, etc.), phosphate plasticizers (triethyl Phosphates, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri-dimethylphenyl phosphate, diphenyloctyl phosphate, etc., represented by the general formula (I) Epoxidized soybean oil, epoxidized linseed oil, epoxidized tallow oil, epoxidized tallow oil, epoxidized cottonseed oil, epoxidized sunflower oil, epoxidized whale oil, epoxidized tall Oil, epoxidized fish oil, diacet monoglyceride of epoxidized soybean oil, epoxidized diacet monoolefin, epoxidized benzoyl stearate,
Epoxidized butyl stearate, epoxidized cyclohexyl stearate, epoxidized dihydrononyl stearate, epoxidized 2-ethylhexyl stearate, epoxidized isodecyl stearate, epoxidized isooctyl stearate, epoxidized tetrahydrofuryl, epoxidized stearic acid Phenyl, epoxidized acetoxyethyl stearate, butyl epoxidized tall oil, n-octyl, isooctyl and 2-ethylhexyl ester, epoxidized triacetomonoricinoleic acid glyceride, epoxidized stearic acid-ter
9,10-epoxystearic acid ester of t-butylphenyl, 3,4-epoxycyclohexylmethanol, stearyl benzoate epoxidation, 9,10,12,13-epoxycyclohexylmethanol of 3,4-epoxycyclohexylmethanol
Diepoxystearate, 2-ethyl-1,3-hexanediol ester of 3,4-epoxycyclohexylcarboxylic acid, di-n-butyl, epoxidized hexahydrophthalic acid, di-n-hexyl, di-2- Ester such as ethylhexyl, diisooctyl, di-n-decyl, diisodecyl and n-butyldecyl, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, a condensate of epichlorohydrin and bisphenol A, an epoxy resin which is a condensate of epichlorohydrin and a novolak resin, and the like. The amount of the plasticizer to be added is 30 to 70 parts by weight, preferably 40 to 60 parts by weight, per 100 parts by weight of the vinyl chloride resin.

The stabilizers usable in the composition of the present invention include metal salts of carboxylic acids or phenols, organic tin-containing compounds, inorganic metal compounds, and pure organic compound stabilizing aids.

Examples of the carboxylic acids or carboxylic acids of the metal salts of phenols include acetic acid, propionic acid, butanoic acid, 2-methylpropionic acid, pentanoic acid, 3-methylbutanoic acid, hexanoic acid and 2,2-dimethylpropane. Acid, 2-butenoic acid, 2-ethylhexanoic acid, caprylic acid, capric acid, lauric acid, palmic acid, myric acid, stearic acid, isostearic acid, behenic acid, oleic acid, ricinoleic acid, linoleic acid, linoleic acid,
Arachiic acid, erucic acid, 12-hydroxystearic acid, 12-ketostearic acid, phenylstearic acid,
Montanic acid, acetoacetic acid, tallow fatty acid, coconut oil fatty acid,
A mixture of natural fatty acids such as pearl fatty acids, tung oil fatty acids, soybean oil fatty acids, cottonseed oil fatty acids, benzoic acid, P-tert-butyl benzoic acid, dimethyl benzoic acid, ethyl benzoic acid, dimethyl hydroxy benzoic acid, toluic acid, acetoxy benzoic acid, Propylbenzoic acid, 3,5-di-ter
t-butyl-4-hydroxybenzoic acid, salicylic acid, P
-Tert-octylsalicylic acid, thioglycolic acid,
Monovalent carboxylic acids such as mercaptopropionic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, adipic acid, malonic acid, oxalic acid, succinic acid, glutaric acid,
Pimelic acid, sebacic acid, adilineic acid, suberic acid,
Fumaric acid, citraconic acid, metaconic acid, itaconic acid, monoester compounds of divalent carboxylic acids such as oxyphthalic acid, hemi-mellitic acid, diester compounds of trivalent carboxylic acids such as trimellitic acid and pyromellitic acid, melophanic acid, Examples include triester compounds of tetravalent carboxylic acids such as pyromellitic acid, and examples of phenol compounds include phenol, cresol, cyclohexylphenol, nonylphenol, and decylphenol. As the metal bonded to these carboxylic acids or phenol compounds, lithium, sodium, potassium, calcium, barium, strontium, magnesium, aluminum, zinc, cadmium, cesium,
Tin and organic tin.

As the organic tin sulfur-containing compound, mono (or di) methyltin tris (or di) (isooctylthioglycolate), mono (or di) butyl (isooctylthioglycolate), mono (or di) Octyltin tris (or di) (isooctylthioglycolate), mono (or di) methyltin tris (or bis) (2-mercaptoethyl oleate), mono (or di) alkyl ( _C1-12 )
Tin sulfide, mono (or di) (butylcarboxyethyl) tin tris (or bis) (isooctylthioglycolate), mono (or di) alkyl (C _1-12 ) tin oxide, mono (or di) alkyl (C _1-12 ) tin (β-mercaptopropionate), mono (or di) alkyl (C _1-12 ) tin (thioglycolate), mono (or di) alkyl (C _1-12 ) tin tri (or di) ) Mercaptoethanol and the like.

Examples of the inorganic metal compound used as a stabilizer include a zeolite compound having a condensed acid structure of a silicate, a hydrotalcite compound, and a lithium-containing composite hydroxide.

Examples of the zeolite compound include A-type, X-type, and Y-type crystalline hydrous aluminosilicates having a three-dimensional network structure containing an alkali or alkaline earth metal.
Examples include zeolites such as type, faujasite, clinoptilolite, and mordenite, and these zeolite compounds may be either natural products or synthetic products.

As the above hydrotalcite compound,
A double salt compound represented by the following general formula (V) is exemplified.

[0043]

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The lithium-containing composite hydroxide is a composite hydroxide represented by the following general formula (VI).

[0045]

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Examples of the organic phosphite compound include triphenyl phosphite, tri (methylphenyl) phosphite, triisooctyl phosphite, tridecyl phosphite, tri (2-ethylhexyl) phosphite, and tris (nonylphenyl) phosphite. Phyte, tri (octylphenyl) phosphite, tri (cyclohexylphenyl) phosphite, tricyclohexylphosphite, tri (decyl) thiophosphite, triisodecylthiophosphite, phenyl di (2-ethylhexyl) phosphite, phenyl・ Diisodecyl phosphite, phenyl dicyclohexyl phosphite, phenyl diisooctyl phosphite, phenyl di (tridecyl) phosphite, phenyl dicyclohexyl phosphite, diph Nil iso-octyl phosphite,
Diphenyl. 2-ethylhexyl phosphite, diphenyl isodecyl phosphite, diphenyl cyclohexyl phenyl phosphite, diphenyl (tridecyl) thiophosphite, nonylphenyl di (tridecyl) phosphite, phenyl p-tert-butyl
Dodecyl phosphite, tetra (tridecyl) ・ 4
4'-isopropylidene-diphenyl diphosphite,
Tetra (tridecyl) -4,4'-butylidene-bis (2-tert-butyl-5-methylphenyl) diphosphite, tetraisooctyl-4,4'-thiobis (2-tert-butyl-5-methylphenol) diphosphite , Tetra (nonylphenyl) poly (propyleneoxy) isopropyl diphosphite, tetra (tridecyl) propyleneoxypropyl diphosphite,
Tetra (tridecyl) -4,4'-isopropylidene-
Di (cyclohexyl) diphosphite, penta (nonylphenyl) bis [poly (propyleneoxy) isopropyl] triphosphite, hepta (nonylphenyl)
Tetrakis [poly (propyleneoxy) isopropyl]
Pentaphosphite, hepta (nonylphenyl) tetrakis (4,4'-isopropylidene-diphenyl) pentaphosphite, deca (nonylphenyl) heptakis (propyleneoxyisopropyl) octaphosphite, decaphenylhepta (propyleneoxyisopropyl) ) Octaphosphite, di (butoxycarboethyl) · 2,2′-dimethylene-trimethylenedithiophosphite, di (isooctoxycarbomethyl) · 2
2'-dimethylene-trimethylene dithiophosphite,
Tetra (lauryl) · ethylenedithiophosphite, tetra (lauryl) · hexamethylenedithiophosphite, tetra (lauryl) · 2,2′-oxydiethylenedithiophosphite, penta (dodecyl) · di (hexamethylene) trithiophosphite , Tetra (phenyl)
4,4'-isopropylidene-dicyclohexyl diphosphite, tetra (mixed alkyl (C
_12- C ₁₅ )) · 4,4′-isopropylidene-diphenyldiphosphite, 2-tert-butyl-4-
[1- (3-tert-butyl-4-hydroxyphenyl) isopropyl] phenyl di (p-nonylphenyl) phosphite, 4,4'-butylidene-bis (3-
Methyl-6-tert-butylphenyl) -di (tridecyl) diphenyldiphosphite, distearyl 2,2
-Dimethylene-trimethylene diphosphite, tricyclohexylphenyl phosphite, hexa (tridecyl) -4,4 ', 4 "-(1,1,3-butanetriyl) -tris (2-tert-butyl-5-methylphenyl) ) Triphosphite, tri (dodecyl) thiophosphite, decaphenyl hepta (propyleneoxyisopropyl) octaphosphite, dibutylpenta (2,2-dimethylene-trimethylene) diphosphite, dioctylpenta (2,2-dimethylene-trimethylene) ) Diphosphite, didecyl (2,2-dimethylene-trimethylene) diphosphite and the like.

As the pure organic compound stabilizing aid, 4
-Cyclopentene-1,3-dione, 4-methylcyclohexane-1,3-dione, 2-phenylcyclohexane-1,3-dione, 2,2-dimethylcyclohexane-1,3,5-trione, 2-benzylcyclohexane -1,3-dione, 2-acetylcyclohexanone, 2
-Benzoylcyclohexanone, 2-acetylcyclohexane-1,3-dione, 1,4-bis (2,6-dioxocyclohexyl) -2-butene, bis (4-butylbenzoyl) methane, benzoyl. Acetylmethane, 4
-Methoxybenzoyl hexanoyl methane, benzoyl acetyl octyl methane, tribenzoyl methane, dehydroacetic acid, dehydropropionyl acetic acid, 2-
(2-cyclohexen-1-yl) cyclohexane-
1,3-dione, caproyl acetylmethane, benzoyl diacetylmethane, cyclohexylcarbonyl
Acetylmethane, cyclohexylcarbonyl-benzoylmethane, benzoyltetralone, acetyltetralone, bis (cyclohexylcarbonyl) methane, dibenzoylmethane, acetylacetone, butanoylacetone, stearoylacetone, lauroylacetone, benzoylphenylacetylmethane, benzoylformylmethane, Β-diketone compounds such as benzoyl palmitoylmethane, hexadecanoylformylmethane, isovaleryl cyclohexylcarbonylmethane, cyclohexylcarbonylacetylacetylmethane, and these β-diketone compounds and lithium, sodium, potassium, magnesium, calcium, strontium, Metal salts with barium, aluminum, zinc, tin, organotin, etc., trimethylol pro Bread, pentaerythritol,
Examples thereof include polyhydric alcohols such as dipentaerythritol, mannitol, sorbitol, trehalol, and tris (2-hydroxyethyl) isocyanurate.

The above-mentioned various stabilizers can be mixed and formulated in a wide variety of manners in order to appropriately set conditions for appropriately processing and molding the agricultural vinyl chloride resin composition or physical properties and performance as a product thereof. And the amount of each of them is 10% with respect to the vinyl chloride resin.
0 to 5 parts by weight per 0 parts by weight.

The antioxidants are 2,6-di-tert-butylphenol, 2,6
-Di-tert-butyl-4-methylphenol, 2,
6-di-tert-butyl-4-ethylphenol, 2
-Tert-butyl-4,6-dimethylphenol,
2,4,6-tri-tert-butylphenol, 2-
tert-butyl-4-methoxyphenol, 3-methyl-4-isopropylphenol, 2.6-di-ter
t-butyl-4-hydroxymethylphenol, 2,2
-Bis (4-hydroxyphenyl) propane, bis (5
-Tert-butyl-4-hydroxy-2-methylphenyl) sulfide, 2.5-di-tert-amylhydroquinone, 2,5-di-tert-butylhydroquinone, 1,1-bis (3-tert-butyl- 4-hydroxy-5-methylphenyl) butane, bis (3-ter
t-butyl-2-hydroxy-5-methylphenyl) methane, 2,6-bis (2-hydroxy-3-tert-
Butyl-5-methylbenzyl) -4-methylphenol, bis (3-tert-butyl-4-hydroxy-5)
-Methylbenzyl) sulfide, bis (3-tert-
Butyl-5-ethyl-2-hydroxyphenyl) methane, bis (3,5-di-tert-butyl-4-hydroxyphenyl) methane, bis (3-tert-butyl-
2-hydroxy-5-methylphenyl) sulfide,
1,1-bis (4-hydroxyphenyl) cyclohexane, bis [3,3-bis (3-tert-butyl-4-)
Hydroxyphenyl) butanoic acid] glycol ester,
Bis [2- (2-hydroxy-3-tert-butyl-
5-methylbenzyl) -4-methyl-6-tert-butylphenyl] terephthalate, 1,1-bis (2-hydroxy-3,5-di-methylphenyl) -2-methylpropane, 4-methoxyphenol, cyclohexyl 1. Phenol, p-phenylphenol, catechol, hydroquinone, 4-tert-butylcallechol, ethyl gallate, propyl gallate, octyl gallate, lauryl gallate, cetyl gallate, β-naphthol,
4,5-trihydroxybutyrophenone, tris (3,
5-di-tert-butyl-4-hydroxyphenyl)
Isocyanate, 1,3,5-trimethyl-2,4.
6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1.6-bis [2- (3.
5-di-tert-butyl-4-hydroxyphenyl)
Propionyloxy] hexane, tetrakis [3-
(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane, bis (3-
Cyclohexyl-2-hydroxy-5-methylphenyl) methane, bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] sulfide, n-octadecyl-3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate, bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionylamino] hexane, 2,6-bis (3-tert-butyl- 2-hydroxy-5-methylphenyl) -4-methylphenol, bis (S- (4-tert-butyl-3-hydroxy-2,6-di-methylbenzyl) thioterephthalate, tris [3- (3,5 -Di-tert-butyl-4
-Hydroxyphenyl) propionyloxyethyl] isocyanurate, 1,1,3-tris (3-tert-
Butyl-4-hydroxy-6-methylphenyl) butane, bis (dodecyloxycarbonylethyl) sulfide, bis (tridecyloxycarbonylethyl) sulfide, bis (tetradecyloxycarbonylethyl) sulfide, bis (dodecyloxycarbonylethyl) sulfide as sulfur-based antioxidants (Hexadecyloxycarbonylethyl) sulfide, bis (2-hexadecyloxycarbonyl-1-methyl-ethyl) sulfide, dodecyloxycarbonylethyl hexadecyloxycarbonylethyl sulfide, 3,3'-thiodipropionic acid, pentaerythritol Tetra (3-
Dodecylthiopropionate) and 4-stearoyloxy-2,2,2 as hindered amine antioxidants.
6,6-tetramethylpiperidine, 4-stearoyloxy-1,2.2.6.6-pentamethylpiperidine,
4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-dodecylsuccinimide-2,2
6,6-tetramethylpiperidine, 1- (3,5-di-
tert-butyl-4-hydroxyphenyl) propionyloxyethyl-4- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy-
2,2,6,6-tetramethylpiperidine, 4,4'-
Ce6yldioxy-bis (2,2,6,6-tetramethylpiperidine), 4,4'-sebacoildioxy-bis (1,2,2,6,6-pentamethylpiperidine),
4,4 '-(3,5-di-tert-butyl-4-hydroxybenzyl) -butylmalonyldioxy-bis (1,2,2,6,6-pentamethylpiperidine),
4,4'-hexamethylenediimino-bis (2,2,
6,6-tetramethylpiperidine), 4,4 ', 4 ",
4 '"-1,2,3,4-butanetetracarbonyltetraoxy-tetra (2,2,6,6-tetramethylpiperidine), 4,4', 4", 4 ""-1,2 , 3,
4-butanetetracarbonyltetraoxy-tetra (1,2,2.6,6-pentamethylpiperidine),
4,4 '-(ditridecyloxycarbonylbutanedicarbonyldioxy) -bis (2,2,6,6-tetramethylpiperidine), tris [2-hydroxy-3-
(2,2,6,6-tetramethyl-4-piperidylamino) propyl] isocyanurate, poly [ethylene-
(2,2,6,6-tetramethyl-4-piperidyl) imino-hexamethylene- (2,2,6,6-tetramethyl-4-piperidyl) imino], poly [1-ethylene-
2,2,6,6-tetramethyl-4-piperidyl-malonyloxy], poly {(4-morpholino-1,3,5-
Triazine-2,6-diyl) [(2,2,6,6-tetramethyl-4-piperidyl) imino-hexamethylene-bis (2,2,6,6-tetramethyl-4-piperidyl) imino]} , 1,5.8,12-tetrakis [2,
4-bis (butyl (2,2,6,6-tetramethyl-4
-Piperidyl) amino) -6-1,3,5-triazinyl] -1,5,8.12-tetraazadodecane, 4,
4 ', 4 "-Nitrilotri (methylenecarbonyloxy) -tris (2,2,6,6-tetramethyl-4-piperidine), poly {[4- (1,1,3,3-tetramethylbutyl) imino -1,3,5-triazine-2,6
-Diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino-hexamethylene- (2,2,6,6
-Tetramethyl-4-piperidyl) imino]} and the like. The amount of the antioxidant to be added is from 0 to 3 parts per 100 parts by weight of the vinyl chloride resin.
0 parts by weight, preferably 0.01 to 1.0 parts by weight.

As the ultraviolet absorber, benzophenones (2-hydroxy-4-methoxybenzophenone,
2-hydroxy-4-n-octylbenzophenone, 2
-Hydroxy-4-dodecyloxybenzophenone, 2
-Hydroxy-4-stearyloxybenzophenone,
2-hydroxy-4-benzyloxybenzophenone,
2-hydroxy-4-methoxy-4'-chlorobenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxy-2 '
-Carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2,4-
Dihydroxy-benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-n-octylbenzophenone, 2.2'-dihydroxy-4,4'-dimethoxybenzophenone,
2,4,5-trihydroxybenzophenone, etc.), benzotriazoles (2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzo) Triazole, 2- (2'-hydroxy-5'-tert-
Octylphenyl) benzotriazole, 2- (2'-
Hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-tert-amylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chloro-benzotriazole, 2- (2- Hydroxy-3'-tert
-Butyl-5'-methylphenyl) -5-chloro-benzotriazole, 2- (2'-hydroxy-3'-te
tert-butyl-5'-methacryloxyethylphenyl) -5-chloro-benzotriazole, etc.) and salicylates (phenyl salicylate, 4-tert-butylphenyl salicylate, 4-tert-octylphenyl salicylate, bisphenol A disalicylate,
2-isopropyl-methyl-cyclohexyl salicylate, 1,7,7-trimethylbicyclo [2,21] -2
Heptyl salicylate, monoglycol salicylate, etc.). The amount of the ultraviolet absorber to be added is 0 to 2.0 parts by weight, preferably 0.05 to 0.5 parts by weight, per 100 parts by weight of the vinyl chloride resin.

Since the surface of the synthetic resin itself is hydrophobic, when the molded product is used, depending on conditions such as temperature and humidity, the adsorbed or collected water forms fine water droplets to cover the surface. Various inconveniences have occurred due to fogging. For example, when a synthetic resin film is used for an agricultural house or tunnel cultivation, the water or water that has evaporated or sprinkled from the soil or crops in the house or tunnel causes water droplets formed on the film surface. The cloudiness caused by the water droplets impairs the penetration of the sun's rays, slows the growth of crops and causes crop diseases. In order to eliminate these drawbacks, when molding a synthetic resin product, an antifogging agent is blended and kneaded or applied to the surface of the molded product. Examples of the antifogging agent used in these methods include glycerin fatty acid esters, sorbitan fatty acid esters, ethylene oxide adducts thereof, and polyglycerin fatty acid esters.

Examples of the glycerin fatty acid ester include glycerin monopalmitate, glycerin monostearate, glycerin monooleate, glycerin monolith, glycerin monobehenate and glycerin mono 12-.
Monoglycerides such as hydroxystearate, glycerin monocaprylate, glycerin monolaurate,
Glycerin mono-dipalminate, glycerin mono-distearate, glycerin di-tristearate, glycerin mono-diolate, glycerin di-triolate, glycerin mono-dilinoleate, glycerin mono-
Mono-diglycerides such as dibehenate, glycerin mono-diricinolate, glycerin mono-di-12-hydroxystearate, glycerin mono-diolate stearate glycerin mono-di-cocoate, glycerin tri-2-ethylhexoate, glycerin tricaprylate Triglycerides such as glycerin trifatty acid (C _7-11 ) ester, glycerin diacet monolaurate, glycerin diacet monostearate, glycerin diacet mono monolate, glycerin diacet monolinoleate, glycerin diacet mono 12-hydroxystearate, glycerin dia Cetmonomyristate, glycerin diacetomonopalmitate, glycerin diacetomonolaurate, glycerin monoacetomonostearate, glycerin Noacetomonomyristate, glycerin monoacetomonopalminate, glycerin monoacetomonoricinoleate, glycerin monoacetomono 12-hydroxystearate, glycerin monoacetomonobehenate, glycerin monoacetomonooleate, glycerin monoacetomonolaurate, glycerin Acetylated glycerides such as monoacetodiolate, glycerin monoacetodiricinolate, glycerin monoacetodicaprylate, glycerin monoacetodilaurate, glycerin monoacetodistearate, succinic acid saturated fatty acid monoglyceride, citrate saturated fatty acid monoglyceride,
Organic acid monoglycerides such as citrate unsaturated fatty acid monoglyceride, diacetyltartaric acid saturated fatty acid monoglyceride, diacetyltartaric acid unsaturated fatty acid monoglyceride, and lactic acid saturated fatty acid monoglyceride.

The sorbitan fatty acid esters and their ethylene oxide adducts include sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan tristearate, sorbitan oleate, sorbitan triolate, sorbitan behenate, sorbitan behenate Sorbitan monolaurate, sorbitan dilaurate, sorbitan distearate, sorbitan dipalminate, sorbitan monoerucinate, sorbitan monoricinoleate, sorbitan palm fatty acid ester, sorbitan palm fatty acid ester, sorbitan bovine fatty acid ester, etc. , Polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene ( 0) sorbitan monostearate,
Polyoxyethylene 20) sorbitan tristearate, polyoxyethylene (20) sorbitan triolate, polyoxyethylene (30) sorbitan monomyristate, polyoxyethylene (20) sorbitan tetraolate, polyoxyethylene (40) sorbitan dipearl Fatty acid esters, polyoxyethylene (60) sorbitan tetraoleate, polyoxyethylene (60) sorbitan tricoco fatty acid esters and the like can be mentioned.

As the polyglycerin fatty acid ester,
Diglycerin laurate, diglycerin stearate,
Diglycerin fatty acid esters such as diglycerin oleate, diglycerin caprylate, diglycerin behenate, diglycerin myristate, diglycerin palm fatty acid ester, diglycerin palm fatty acid ester, diglycerin bovine fatty acid ester, tetraglycerin stearate, Examples thereof include polyglycerin fatty acid esters such as tetraglycerin oleate, hexaglycerin laurate, decaglycerin laurate, decaglycerin oleate, and polyglycerin polyricinoleate. The addition amount of these antifogging agents is 100
0-5.0 parts by weight, preferably 1.0-4.
0 parts by weight.

In addition, if necessary, a fluorescent agent, a deterrent agent,
Plate-out preventing agents, processing aids, cross-linking agents, surfactants, reinforcing agents, release agents, dyes, pigments, clay-lowering agents, lubricants, etc. may be included in the polyvinyl chloride resin composition of the present invention. it can.

The above-mentioned vinyl chloride resin composition is formed into a film by a known processing method such as a calendering method, an inflation method and an extrusion method.

[0057]

The stabilizing effect of the polyvinyl chloride resin composition according to the present invention will be described in detail with reference to the following examples. However, the present invention is, of course, not limited to the following examples. In the following examples, the evaluation values of the initial colorability, transparency and weather resistance are in accordance with the following criteria, and the thermal stability is the time until the sheet piece turns black.

Example 1 In order to examine the stabilizing effect of the polyvinyl chloride resin composition obtained in the present invention, the following compound was formed into a sheet having a thickness of 0.5 mm with two rolls at 180 ° C. Using this sheet, a thermal stability test was performed in a gear oven at 190 ° C. Further, using this sheet, 175 ° C., 100 kg
/ Cm ² , a press sheet was prepared, and the initial coloring property and transparency were compared. Table 1 shows the results. Compounding parts by weight Polyvinyl chloride resin (average degree of polymerization: 1000) 100 Dioctyl phthalate 45 Epoxidized soybean oil 2.0 Zinc octoate 0.5 Barium nonylphenate 0.2 Barium stearate 0.3 Organic phosphorus compounds Table 1 Organic phosphorous acid or phosphoric acid analogues Table 1 Organic phosphorus metal salts Table 1

[0059]

[Table 1]

[0060]

[Table 2]

Example 2 A sheet was prepared with the following composition in the same manner as in Example 1, and a similar test was conducted. Further, a film having a thickness of 0.1 mm was prepared and subjected to a one-year outdoor exposure test. Table 2 shows the results of these tests. Blended parts by weight Polyvinyl chloride resin (average degree of polymerization: 1000) 100 Dioctyl phthalate 45 Epoxy resin 1.5 Zinc octoate 0.1 Zinc stearate 0.5 Alkamizer 1 ¹⁾ 0.2 Calcium stearate 0.5 Tetra Tridecyl-4,4 '-(2,2-propylene) 0.5 diphenylphosphite methylene bisamide 0.4 sorbitan monopalmitate 2.0 2-hydroxy-4-n-octoxybenzophenone 0.1 organic phosphorus compound Table 2 Organic phosphorous acid or phosphoric acid analog Table 2 Organic phosphorus metal salts Table 2 ¹⁾ Kyowa Chemical Industry Co., Ltd.

[0062]

[Table 3]

[0063]

[Table 4]

[0064]

As described above, the vinyl chloride resin composition of the present invention is excellent in heat stability, transparency and weather resistance and can be used for a long time in the agricultural field.

Claims (1)

[Claims] (A) at least one kind of an organic phosphorus compound represented by the following general formula (I); and (b) phosphorous acid or phosphoric acid having at least one hydroxyl group directly connected to phosphorus. A vinyl chloride resin composition comprising at least one compound and (c) at least one organic phosphorus-containing metal salt represented by the following general formulas (II) and (III). Embedded image Embedded image