JP2000198896A - Vinyl chloride-based resin composition for agriculture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a vinyl chloride-based resin composition capable of expecting remarkable improvement of heat resistance and weatherability by compounding a vinyl chloride-based resin with polyglycidyl ether of an aliphatic polyhydric alcohol. SOLUTION: This resin composition is obtained by compounding (A) 100 pts.wt. vinyl chloride-based resin with (B) 0.001-10 pts.wt. at least one kind of polyglycidyl ether of an aliphatic polyhydric alcohol having <=250 epoxy equivalent. It is preferable that the composition is combinedly use with (C) 5-100 pts.wt. ester-based plasticizer and (D) 1-20 pts.wt. phosphate-based plasticizer based on 100 pts.wt. component A. Further, it is preferable that the above composition is compounded with (E) 0.001-10 pts.wt. at least one kind of compound selected from compounds of formulas I and II (R1 to R3 are each a 1-30C alkyl; Me is an alkaline earth metal or zinc) based on 100 pts.wt. component A.

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 composition for agricultural use, and more particularly, to a polyvinyl chloride resin for agricultural use which comprises a polyglycidyl ether of an aliphatic polyhydric alcohol and has excellent heat resistance and weather resistance. The present invention relates to a resin composition.

[0002]

2. Description of the Related Art In recent years,
Institutional horticulture has been gradually increasing because profits can be improved by promoting or suppressing cultivation of useful plants.

[0003] Coating materials used for this greenhouse horticulture include polyethylene film, ethylene-vinyl acetate copolymer film, polycarbonate film, methyl methacrylate resin film, acrylic resin film,
Vinyl chloride resin films, glass and the like are used.

[0004] Among the above-mentioned coating materials, a vinyl chloride resin film containing a large amount of a plasticizer is more transparent than other synthetic resin films in terms of light transmittance, heat retention, mechanical strength, durability, workability and economy. It is widely used because of its excellent properties.

However, the vinyl chloride resin film used as a coating material is naturally used outdoors, and is exposed to sunlight, rain and the like.
Changes over time such as burning and tearing caused by light, heat and oxidation occur.

In order to improve these drawbacks, agricultural vinyl chloride resins include, for example, organotin compounds, metal soap stabilizers, organic phosphite compounds, epoxy compounds, phenolic antioxidants, benzophenone-based resins, Various additives for improving the resistance to light, heat, oxidation, etc., such as a benzotriazole-based ultraviolet absorber and a hindered amine-based light stabilizer, are blended.

[0007] Among these additives, epoxy compounds are used not only as a heat stabilizer but also as a plasticizer. Was mainly used. However, in recent years, general-purpose bisphenol-type epoxy resins include:
Since polyphenols such as bisphenol A, which are suspected to be endocrine disruptors, may be contained, their use tends to be avoided, and the development of a heat and weather resistance improving agent that is expected to replace this is expected. I have.

An epoxy compound other than the above epoxy resin,
For example, when using epoxidized vegetable oil, epoxidized fatty acid ester, alicyclic epoxy, etc., the weather resistance is significantly reduced, so even when using these epoxy compounds, the performance is comparable to that when using an epoxy resin. Things were not obtained.

Accordingly, an object of the present invention is to provide a vinyl chloride resin composition for agricultural use which can remarkably improve heat resistance and weather resistance.

[0010]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above object can be achieved by blending a polyglycidyl ether of an aliphatic polyhydric alcohol with a vinyl chloride resin. Was found.

The present invention has been made on the basis of the above findings, and 100 parts by weight of a vinyl chloride resin contains at least one polyglycidyl ether of (a) an aliphatic polyhydric alcohol having an epoxy equivalent of 250 or less. An object of the present invention is to provide a vinyl chloride resin composition for agricultural use in which parts by weight are blended.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The agricultural vinyl chloride resin composition of the present invention will be described in detail below.

Examples of the aliphatic polyhydric alcohol capable of providing the polyglycidyl ether of the aliphatic polyhydric alcohol (a) used in the present invention include ethylene glycol, diethylene glycol, and 1,3-propanediol. , 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,6-hexanediol, 1,5-hexanediol, 3-methyl-1,5 -Pentanediol, 1,8-octanediol, 2-ethyl-1,3-
Hexanediol, 2,2,4-trimethyl-1,3-
Pentanediol, 1,8-octanediol, 1,2
-Octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, cyclohexanedimethanol, 2,2-isopropylenebis (4-hydroxy Cyclohexane) and the like.

The method for producing the polyglycidyl ether of the aliphatic polyhydric alcohol is not particularly limited. For example, the method can be easily carried out by reacting an aliphatic polyhydric alcohol with epichlorohydrin as exemplified above. Can be manufactured.

The polyglycidyl ether of the aliphatic polyhydric alcohol has an epoxy equivalent of 250 or less, preferably 2 or less.
If it is 20 or less and the epoxy equivalent exceeds 250, a sufficient stabilizing effect cannot be obtained.

The amount of the component (a) is 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the vinyl chloride resin, and less than 0.001 part by weight. The effect of use is not obtained, and even if it is used in an amount of more than 10 parts by weight, not only waste but also coloring may occur.

The vinyl chloride resin used in the present invention is not particularly limited to a polymerization method such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization. Examples thereof include polyvinyl chloride, chlorinated polyvinyl chloride, and the like. , Polyvinylidene chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, Vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile terpolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer , Vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, salt Chlorine-containing resins such as vinyl-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-various vinyl ether copolymers, and their mutual blended products or Chlorine-containing resin and another chlorine-free synthetic resin, for example, acrylonitrile-styrene copolymer, acrylonitrile-styrene-
Butadiene terpolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl (meth) acrylate copolymer,
Examples thereof include blends with polyester and the like, block copolymers, graft copolymers, and the like.

In the agricultural vinyl chloride resin composition of the present invention, plasticizers usually used for vinyl chloride resins can be arbitrarily used. In particular, (b) ester plasticizers and (c) It is preferable to use a phosphoric acid ester-based plasticizer in combination, since a material having more excellent heat resistance and weather resistance can be obtained.

Examples of the ester-based plasticizer (b) include phthalates such as dibutyl phthalate, butylhexyl phthalate, diheptyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, and dioctyl terephthalate. Acid plasticizer;
Adipic acid plasticizers such as dioctyl adipate, diisononyl adipate, diisodecyl adipate, di (butyldiglycol) adipate;
Ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,
3-propylene glycol, 1,3-butanediol,
1,4-butanediol, 1,5-hexanediol,
1,6-hexanediol, neopentyl glycol and the like, and dibasic acids such as oxalic acid, malonic acid, succinic acid,
Polyester plasticizer using glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, etc., and, if necessary, a monohydric alcohol or a monocarboxylic acid as a stopper; In addition, tetrahydrophthalic acid plasticizer, azelaic acid plasticizer, sebacic acid plasticizer, stearic acid plasticizer, citric acid plasticizer, trimellitic acid plasticizer,
Examples include a pyromellitic acid-based plasticizer and a biphenylene polycarboxylic acid-based plasticizer.

Examples of the phosphate plasticizer of the component (C) include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, and trioctyl phosphate. , Tri (butoxyethyl) phosphate,
Octyl diphenyl phosphate and the like.

The amount of the ester plasticizer (b) used is preferably 5 to 100 parts by weight, more preferably 1 to 100 parts by weight.
0 to 50 parts by weight, if less than 5 parts by weight, sufficient flexibility may not be obtained. If more than 100 parts by weight, heat resistance and weather resistance may be adversely affected. Therefore, it is not preferable. The amount of the phosphate plasticizer used as the component (c) is preferably 1-2.
0 parts by weight, more preferably 3 to 10 parts by weight. If less than 1 part by weight, a sufficient effect of improving weather resistance may not be obtained. If more than 20 parts by weight, bleeding may occur. It is not preferable because coloring may occur.

The agricultural vinyl chloride resin composition of the present invention includes (d) the following [Chemical Formula 2] (same as the above [Chemical Formula 1]).
It is preferable to use at least one compound selected from the compounds (organic phosphate metal salts) represented by the general formulas (I) and (II) in order to provide more excellent heat resistance and weather resistance.

[0023]

Embedded image

In the above general formulas (I) and (II), R ₁ , R
Examples of the alkyl group having 1 to 30 carbon atoms represented by ₂ and R ₃ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl. Hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henycosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl and the like, particularly preferably an alkyl group having 10 to 25 carbon atoms . Further, it is preferable to use a mixture of a monoester having an alkyl group having 10 to 25 carbon atoms and a diester having an alkyl group having 10 to 25 carbon atoms, since a material having excellent processability can be obtained. When this mixture is used, the weight ratio between the monoester and the diester (the former / the latter) is preferably 1/10 to 10/1, more preferably 1/5 to 5/1.
/ 1. In the above general formulas (I) and (II), M
Examples of the alkaline earth metal represented by e include magnesium, calcium, barium, strontium and the like.

The amount of the component (d) is preferably 0.001 to 10 parts by weight per 100 parts by weight of the vinyl chloride resin.
Parts by weight, more preferably 0.01 to 5 parts by weight,
If the amount is less than 0.001 part by weight, the effect of use may not be obtained. If the amount is more than 10 parts by weight, not only wasteful but also coloring may be caused, which is not preferable.

In the composition of the present invention, a carboxylic acid or a phenolic metal (Li, Na, K, Ca, Mg,
A normal salt, an acidic salt, a basic salt or an overbased salt of Ba, Sr, Zn, Al, Sn) can be used in combination.

Examples of the carboxylic acids include caproic acid, caprylic acid, pelargonic acid, 2-ethylhexylic acid, capric acid, neodecanoic acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid,
Isostearic acid, 12-hydroxystearic acid, chlorostearic acid, 12-ketostearic acid, phenylstearic acid, ricinoleic acid, linoleic acid, linoleic acid, oleic acid, arachinic acid, behenic acid, erucic acid, brassic acid and similar acids and Tallow fatty acids, coconut oil fatty acids, tung oil fatty acids, soybean oil fatty acids, cottonseed oil fatty acids, and other naturally occurring mixtures of the above acids, benzoic acid, p-tert-butylbenzoic acid, ethylbenzoic acid, isopropylbenzoic acid,
Toluic acid, xylic acid, salicylic acid, 5-tert-octylsalicylic acid, naphthenic acid, cyclohexanecarboxylic acid, adipic acid, maleic acid, acrylic acid, methacrylic acid and the like, and the phenols include, for example, phenol, Cresol, ethylphenol, cyclohexylphenol, nonylphenol, dodecylphenol and the like can be mentioned.

The composition of the present invention may further contain various additives usually used as additives for vinyl chloride resins, for example, antifoggants, antifog agents, liquid polybutadiene,
Hydrotalcite compounds, β-diketone compounds, perchlorates, zeolite compounds, organic phosphite compounds, phenolic or sulfuric antioxidants, epoxy compounds, polyols, ultraviolet absorbers, hindered amine light stabilizers, and others An inorganic metal compound or the like can also be blended.

Examples of the anti-fogging agent include polyoxyethylene lauryl ether, -stearyl ether,-
Nonylphenyl ether, polyethylene glycol monopalmitate, -monostearate, polyoxyethylene sorbitan monolaurate, -monopalmitate, glycerin monolaurate, -monopalmitate, -monostearate, -monooleate, pentaerythritol monolau Rate, sorbitan monopalmitate, -monobehenate, -distearate, diglycerindiolate sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium butylnaphthalenesulfonate, cetyltrimethylammonium chloride,
Dodecylamine hydrochloride, lauric lauramide ethyl phosphate, triethylcetyl ammonium iodide, oleylaminodiethylamine hydrochloride, dodecylpyridinium salt and the like can be mentioned.

Examples of the above antifoggant include an anionic fluorinated surfactant, a cationic fluorinated surfactant,
Examples include amphoteric fluorinated surfactants, nonionic fluorinated surfactants, and fluorinated compounds such as fluorinated oligomers.

Examples of the liquid polybutadiene include 1,2-atactic polybutadiene, 1,2-syndiotactic polybutadiene, 1,2-isotactic polybutadiene, and 1,2-atactic polybutadiene obtained by homopolymerization of 1,3-butadiene. 4-cis polybutadiene, 1,
4-transpolybutadiene or block polymers, graft polymers and mixtures thereof, further partially epoxidized, those having terminal hydroxyl and / or carboxyl groups or partially maleated, halogenated, boiled, hydrogenated, acrylic-modified And urethane-modified and ester-modified products. Among these liquid polybutadienes, epoxy-modified ones are particularly preferred since they have the effect of improving weather resistance. The average molecular weight of these liquid polybutadienes is preferably 250
２５25000, more preferably 500〜１０10000.

The hydrotalcite compound is a complex salt compound comprising magnesium and / or an alkali metal and aluminum or zinc, magnesium and aluminum as represented by the following general formula (III), and is obtained by dehydrating water of crystallization. It may be.

Ia _X1 Mg _X2 Zn _X3 Al _y (OH) _{X1 + 2 (X2 + X3) + 3y-2} (CO ₃ ) _{1-Z / 2} (ClO ₄ ) mH ₂ O (III) (wherein Ia Represents an alkali metal atom, x1, x
2, x3, y, and z each represent a number that satisfies the condition represented by the following equation, and m represents a real number. 0 ≦ x1 ≦ 10,0 ≦
x2 ≦ 10, 0 ≦ x3 ≦ 10, 0 ≦ y ≦ 10, 0 ≦ z ≦
10. However, x1 and x2 are never 0 at the same time. )

The hydrotalcite compound may be a natural product or a synthetic product. The method for synthesizing the synthetic product is described in JP-B-46-2280, JP-B-50-30039, and JP-B-51-29129.
Gazette, Japanese Patent Publication No. 3-36839, JP-A-61-174
Known methods described in, for example, Japanese Patent Application Laid-Open No. 270, JP-A-5-17952 and the like can be exemplified. Further, the above hydrotalcite compound can be used without being limited by its crystal structure, crystal particle system and the like.

The above-mentioned hydrotalcite compound has a surface whose surface is composed of a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal oleate, an organic sulfonic acid metal salt such as an alkali metal dodecylbenzenesulfonate, or a higher salt thereof. It may be one coated with a fatty acid amide, a higher fatty acid ester or a wax.

Examples of the β-diketone compound include dibenzoylmethane, benzoylacetone, stearoylbenzoylmethane, caproylbenzoylmethane, dehydroacetic acid, tribenzoylmethane, 1,3-bis (benzoylacetyl) benzene, and the like. Metal salts (lithium, sodium, potassium, calcium, magnesium, barium, zinc, etc.) and the like.

The above perchlorates include lithium perchlorate, sodium perchlorate, potassium perchlorate, strontium perchlorate, barium perchlorate, zinc perchlorate,
Aluminum perchlorate, lead perchlorate, ammonium perchlorate and the like, and these perchlorates may be anhydrous or hydrated salts, and butyl diglycol, alcohols such as butyl diglycol adipate and the like. It may be one dissolved in an ester-based solvent or a dehydrated product thereof.

The zeolite compound is an alkali or alkaline earth metal aluminosilicate having a unique three-dimensional zeolite crystal structure.
Type, X type, Y type, and P type zeolite, monodenite,
Analsite, sodalite group aluminosilicate, clinbutyrolite, erionite, chabazite and the like can be mentioned, and the hydrate or crystallization water containing crystal water of these zeolite compounds (so-called zeolite water) is removed. Any of anhydrides may be used.

Examples of the organic phosphite compound include triphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, Tris (mono- and di-mixed nonylphenyl) phosphite, bis (2-tert-butyl-4,6-dimethylphenyl) .ethyl phosphite, diphenyl acid phosphite, 2,2'-methylenebis (4,6-di Tributylphenyl) octyl phosphite, diphenyldecyl phosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, dibutyl acid phosphite,
Dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentyl glycol)
1,4-cyclohexanedimethyldiphosphite, bis (2,4-ditertbutylphenyl) pentaerythritol diphosphite, bis (2,6-ditertbutyl-4-)
Methylphenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, phenyl-4,4'-isopropylidenediphenol pentaerythritol diphosphite, tetra (C
12-15 mixed alkyl) -4,4'-isopropylidenediphenyl phosphite, bis [2,2'-methylenebis (4,6-diamylphenyl)] isopropylidene diphenyl phosphite, hydrogenated-4,4 ' -Isopropylidene diphenol polyphosphite, bis (octylphenyl) bis [4,4'-n-butylidenebis (
2-tert-butyl-5-methylphenol)] • 1,6-hexanediol • diphosphite, tetratridecyl •
4,4'-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl)
-1,1,3-tris (2-methyl-5-tert-butyl-
4-hydroxyphenyl) butane triphosphonite,
Examples thereof include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-butyl-2-ethylpropanediol, 2,4,6-tritert-butylphenol monophosphite, and the like.

Examples of the phenolic antioxidants include 2,6-di-tert-butyl-p-cresol and 2,6-di-tert-butyl-p-cresol.
Diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, tridecyl-3,3 5-di-tert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-m -Cresol), 2-octylthio-4,6-di (3,5-ditert-butyl-4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-tert-butylphenol) , Bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid]
Glycol ester, 4,4'-butylidenebis (4,
6-di-tert-butylphenol), 2,2′-ethylidenebis (4,6-di-tert-butylphenol), 1,1,3
-Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) Phenyl] terephthalate, 1,3,5-
Tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl)
Isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-di-tert. Tributyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl- 6- (2-Acroyloxy-3-tert-butyl-
5-methylbenzyl) phenol, 3,9-bis [2-
(3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl]-
2,4,8,10-tetraoxaspiro [5.5] undecane] and triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate].

Examples of the above sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl and distearyl esters of thiodipropionic acid, and pentaerythritol tetra (β-dodecylmercaptopropionate). And β-alkyl mercaptopropionates of polyols.

Examples of the epoxy compound include epoxidized animal and vegetable oils such as epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized tallow oil, epoxidized castor oil, epoxidized safflower oil, and the like. Epoxidized methyl stearate, -butyl, -2-
Ethylhexyl, -stearyl ester, epoxidized polybutadiene, tris (epoxypropyl) isocyanurate, epoxidized tall oil fatty acid ester, epoxidized linseed oil fatty acid ester, vinylcyclohexene diepoxide, dicyclohexene carboxylate, 3,
4-epoxycyclohexenemethylepoxycyclohexanecarboxylate and the like.

Examples of the polyols include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, polypentaerythritol, pentaerythritol or dipentaerythritol half-ester stearic acid, bis (dipentaerythritol) adipate, Glycerin,
Tris (2-hydroxyethyl) isocyanurate, sorbitol, mannitol, trehalose and the like can be mentioned.

As the above-mentioned ultraviolet absorber, for example,
4-dihydroxybenzophenone, 2-hydroxy-4
-Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-tert-butyl-4 '-(2-methacryloyloxyethoxyethoxy) benzophenone, 5,5'-methylenebis (2-hydroxy-4 2-hydroxybenzophenones such as -methoxybenzophenone); 2- (2-hydroxy-5-
Methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-ditert-butylphenyl) -5-chlorobenzotriazole, 2- ( 2-hydroxy-3-tert-butyl-5-methylphenyl) -5
-Chlorobenzotriazole, 2- (2-hydroxy-
3-dodecyl-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3-tert-butyl-5-C7
~ 9 mixed alkoxycarbonylethylphenyl) triazole, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tert-octyl-6-benzotriazolylphenol), 2- (2-hydroxyphenyl) benzotriazoles such as polyethylene glycol ester of 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole; 2- (2-hydroxy-4
-Hexyloxyphenyl) -4,6-diphenyl-1,
3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6 -Bis (2,4-dimethylphenyl)-
2- (2-hydroxyphenyl) -1,3,5-triazines such as 1,3,5-triazine; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert. Tributyl-4-hydroxybenzoate, 2,4-ditert-amylphenyl-
3,5-di-tert-butyl-4-hydroxybenzoate,
Benzoates such as hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; 2-ethyl-2'-
Substituted oxanilides such as ethoxy oxanilide and 2-ethoxy-4'-dodecyl oxanilide; ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-
And cyanoacrylates such as cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, , 2,6,6-tetramethyl-4-piperidylbenzoate, bis (2,
2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-
Tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2
2,6,6-pentamethyl-4-piperidyl) -1,
2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl).
Bis (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) .bis (tridecyl) -1,
2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-di-tert-butyl-4-
Hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6- Tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino- s
Triazine polycondensate, 1,6-bis (2,2,6,6
-Tetramethyl-4-piperidylamino) hexane /
2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,
4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazine-
6-yl] -1,5,8,12-tetraazadodecane,
1,5,8,12-Tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-
Piperidyl) amino) -s-triazin-6-yl]-
1,5,8,12-tetraazadodecane, 1,6,11
-Tris [2,4-bis (N-butyl-N- (2,2,
6,6-tetramethyl-4-piperidyl) amino-s-
Triazin-6-ylamino] undecane, 1,6,1
1-tris [2,4-bis (N-butyl-N- (1,
2,2,6,6-pentamethyl-4-piperidyl) amino-s-triazin-6-ylamino] undecane.

The above-mentioned other inorganic metal compounds include
Examples include calcium silicate, calcium phosphate, calcium oxide, calcium hydroxide, magnesium silicate, magnesium phosphate, magnesium oxide, magnesium hydroxide and the like.

The composition of the present invention may further contain other stabilizing aids usually used for vinyl chloride resins. Examples of such a stabilizing aid include diphenylthiourea, diphenylurea, anilinodithiotriazine, melamine, benzoic acid, cinnamic acid, p-tert-butylbenzoic acid, and the like.

In addition, the composition of the present invention may contain, if necessary, additives usually used for vinyl chloride resins, for example,
Fillers, colorants, cross-linking agents, antistatic agents, plate-out inhibitors, surface treatment agents, lubricants, flame retardants, fluorescent agents, fungicides,
A bactericide, a metal deactivator, a release agent, a pigment, a processing aid, an antioxidant, a light stabilizer, a foaming agent, and the like can be added.

The composition of the present invention can be used irrespective of the method for processing a vinyl chloride resin.
For example, it can be suitably used for calendering, rolling, extrusion molding, melt rolling, pressure molding, powder molding, and the like.

The composition of the present invention can be suitably used as agricultural materials such as agricultural houses and tunnels.

[0051]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited by the following examples.

Example 1 The following formulation was calendered at 190 ° C.
A 0.4 mm sheet and a 0.1 mm sheet were prepared.
A 0.4 mm sheet was laminated and pressed at 190 ° C. to prepare a 1 mm sheet, which was placed in a gear oven at 190 ° C., and the blackening time (thermal stability) was measured.

Further, a 0.1 mm film is oriented 45
It was set on an exposure table with different degrees, and the state of deterioration (weather resistance) over time was observed. The evaluation of the weather resistance was visually evaluated on a 10-point scale, and the evaluation criteria were shown below. The evaluation results are shown in Table 1.

(Weather Resistance Evaluation Criteria) 1: No change in appearance. 2-3: A brown portion is observed. 4-7: Black-brown spots are observed. 8-9: Large black-brown spots are observed, and there are tears. 10: The entire surface is broken. (Note) Larger values indicate greater deterioration.

(Blending) Parts by weight Vinyl chloride resin (degree of polymerization 1300) 100 Dioctyl phthalate 47 Tricresyl phosphate 5 Sorbitan monopalmitate 2 Ethylene bisamide 0.5 Tetra (C12-15 mixed alkyl) -4,4'- Isopro 0.8 pyridene diphenyl phosphite zinc stearate 0.6 mono / di mixed zinc stearyl phosphate (weight ratio 1/1) 0.3 barium stearate 0.9 1,5,8,12-tetrakis [2 , 4-Bis (N-butyl 0.1-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8, 12-tetraazadodecane 5,5'-methylenebis (2-hydroxy-4-methoxy 0.1 benzophenone) epoxy compound (described in Table 1) 2.0

[0056]

[Table 1]

The details of each epoxy compound in Table 1 are as follows (the same applies to Tables 2 to 4 below). Further, in Example 1-2 shown in Table 1 above, zinc stearate was used in place of the mono / di mixed zinc stearyl phosphate (Examples 2-2 and 3- shown in Tables 2 and 3 below).
2). Epoxy resin: Adeka resin EP-13 (made by Asahi Denka Kogyo Co., Ltd .;
Hexphenol A-type epoxy resin, ethoxy equivalent 190) HEP-1: octanol monoglycidyl ether, ethoxy equivalent 187 EP-1: adecalezin ED-505 (same as above; pentaerythritol polylactic acid, ethoxy equivalent 150) EP-2: adecalezin -507 (same as above; glycerin-polyglycidyl ether, ethoxy equivalent 145) EP-3: ADEKARESIN ED-503T (same as above; hexanediol-polylactic acid, ethoxy equivalent 145) EP-4: ADEKARESIN ED-523T (same as above, 2, 2-dimethyl
-1,3-Fluorocarbon-polycarboxylic ether, ethoxy equivalent 140) EP-5: Adekaresin EP-4080S (same as above; hydrogenated bisphenol)
A-polycarboxylic ether, ethoxy equivalent 210) EP-6: ADEKARESIN EP-4085S (same as above; cyclohexane dimethyl methanol-polycarboxylic ether, ethoxy equivalent 138)

Example 2 The same test as in Example 1 was conducted with the following composition. Table 2 shows the results.

(Blending) Parts by weight Vinyl chloride resin (degree of polymerization 1300) 100 Dioctyl phthalate 47 Tricresyl phosphate 5 Sorbitan monopalmitate 2 Ethylene bisamide 0.5 Dioctyl diphenyl phosphite 0.8 Barium stearate 0.5 BF -1000 1 (manufactured by Nippon Soda Co., Ltd .; liquid polybutadiene) mono / di mixed zinc stearyl phosphate (weight ratio 1/1) 0.3 Surflon S-145 (manufactured by Asahi Glass; fluorinated anti-fogging agent) 0.1 epoxy Compound (described in Table 2) 2.0

[0060]

[Table 2]

Example 3 The same test as in Example 1 was conducted with the following composition. Table 3 shows the results.

(Blending) Parts by weight Vinyl chloride resin (degree of polymerization 1300) 100 Dioctyl phthalate 47 Tricresyl phosphate 5 Sorbitan monopalmitate 2 Ethylene bisamide 0.5 Trisnonylphenyl phosphite 0.8 Stearyl acid phosphate 0 0.05 Stearyl benzoylmethane 0.02 Mono / di mixed zinc stearyl phosphate (weight ratio 1/1) 0.3 Surflon S-115 (manufactured by Asahi Glass; fluorine-based anti-fog agent) 0.1 Epoxy compound (described in Table 3) ) 2.0

[0063]

[Table 3]

Example 4 The same test as in Example 1 was conducted with the following composition. Table 4 shows the results.

(Blending) Parts by weight Vinyl chloride resin (degree of polymerization: 1300) 100 Dioctyl phthalate 47 Tricresyl phosphate 5 Sorbitan monopalmitate 2 Ethylene bisamide 0.5 Trisnonylphenyl phosphite 0.8 Barium stearate 0.5 Stearyl acid phosphate ester 0.05 Stearyl benzoylmethane 0.02 Mono / di mixed zinc stearyl phosphate (weight ratio 1/1) 0.4 Surflon S-115 (manufactured by Asahi Glass; fluorine-based anti-fog agent) 0.1 Epoxy Compound (described in Table 4) 2.0

[0066]

[Table 4]

As is clear from the above examples, when the glycidyl ether of an aliphatic monoalcohol was used (Comparative Examples 1-3, 2-3, 3-3 and 4-3), an epoxy resin was used. Case (Comparative Examples 1-2, 2-2, 3-2,
Heat resistance and weather resistance are also significantly reduced as compared to 4-2).

On the other hand, when the polyglycidyl ether of the aliphatic polyhydric alcohol of the component (A) according to the present invention is used (each Example), both the heat resistance and the weather resistance are comparable to those of the epoxy resin. Demonstrate the performance you need. Furthermore, by using a metal salt of an organic phosphate together with this, the weather resistance is also remarkably improved.

[0069]

The agricultural vinyl chloride resin composition of the present invention is excellent in heat resistance and weather resistance without using an epoxy resin having mutagenic properties. It can be used as agricultural materials such as agricultural houses and tunnels.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) C08K 5/1515 C08K 5/15 B 5/521 5/521 5/527 5/527 (72) Inventor Honda Tomoki 5-2-13-1 Shirahata, Urawa-shi, Saitama F-term (reference) in Asahi Denka Kogyo Co., Ltd. EW047 EW048 FD026 FD027 GA01

Claims (3)

[Claims] 1. 100 parts by weight of a vinyl chloride resin,
(A) at least one polyglycidyl ether of an aliphatic polyhydric alcohol having an epoxy equivalent of 250 or less 0.001
A vinyl chloride resin composition for agricultural use, comprising 10 to 10 parts by weight. 2. 100 parts by weight of a vinyl chloride resin,
2. A vinyl chloride resin composition for agricultural use according to claim 1, which comprises 5 to 100 parts by weight of (b) at least one kind of ester plasticizer and (1) 1 to 20 parts by weight of (c) at least one kind of phosphate plasticizer. object. 3. 100 parts by weight of a vinyl chloride resin,
(D) An agricultural chloride according to claim 1 or 2, wherein at least one 0.001 to 10 parts by weight of at least one compound selected from the compounds represented by the following formulas (I) and (II) is compounded. Vinyl-based resin composition. Embedded image