JPH0639550B2 - Agricultural polyethylene resin film - Google Patents

Description

TECHNICAL FIELD The present invention relates to an agricultural polyethylene resin film, and particularly to an agricultural polyethylene resin film having excellent weather resistance.

"Conventional technology" Conventionally, as a greenhouse coating material used for greenhouse cultivation of agricultural houses, tunnel houses, etc., polyolefin resin films such as polyvinyl chloride film, polyethylene film, ethylene-vinyl acetate copolymer film etc. are mainly used. ing. Of these, polyvinyl chloride films have been widely used in this field until recent years because they have excellent weather resistance, transparency, toughness, heat retention and the like. However,
The polyvinyl chloride film has the drawback that the plasticizer contained in the film bleeds onto the film surface during use, dust is attached and the light transmittance is impaired, and the temperature rise inside the house is hindered. If this is done, hydrochloric acid gas will be generated, so there is the problem that the disposal process is difficult. Furthermore, there is a problem that it loses flexibility at low temperatures and its impact resistance becomes poor, so that it is difficult to withstand use in cold regions. On the other hand, since the polyolefin resin film does not contain a plasticizer in the film, the light transmittance hardly changes during use, no harmful gas is generated even when incinerated, and it is inexpensive and excellent in processability, This film has the drawback of being inferior in weather resistance to the polyvinyl chloride film. Therefore, it has not been used as a house coating film so far while having the above advantages.

As a coating film having improved weather resistance of a polyolefin resin film, a specific hindered amine light stabilizer and an inorganic fine powder having a specific polarity are added to a polyolefin resin as seen in JP-A-56-41254. And a polyolefin-based film comprising
As disclosed in JP120732, JP-A-60-199039 and JP-A-61-31466, a specific hindered amine light stabilizer and a plurality of specific antioxidants are added to a polyolefin resin. And a polyolefin resin composition comprising
Although a polyolefin-based resin composition obtained by adding a specific organophosphate metal salt compound and a specific hindered phenol-based antioxidant to a polyolefin-based resin as disclosed in Japanese Patent Publication No. Not effective.

"Problems to be solved by the invention" In view of such circumstances, the present inventors intend to obtain a polyethylene film having excellent weather resistance without impairing the soil non-contamination property and the incineration processability of the polyolefin film. As a result of intensive studies, the present invention has been completed.

"Means for Solving Problems" The gist of the present invention is to add 100 parts by weight of a polyethylene resin or an ethylene-vinyl acetate copolymer resin to 1 to 25 parts by weight of a specific hydrotalcite compound and 0.1 to 5 parts by weight. In the polyethylene-based resin film for agriculture, the polyethylene-based resin film for agricultural use is characterized by being blended with at least one compound selected from the organic metal salt of organic phosphates.

Hereinafter, the present invention will be described in more detail.

In the present invention, the polyethylene-based resin means a polyethylene resin or an ethylene-vinyl acetate copolymer resin. Of these, low-density polyethylene having a density of 0.910 to 0.935 and an ethylene-vinyl acetate copolymer having a vinyl acetate content of 30% by weight or less are preferable as an agricultural film in terms of transparency, weather resistance and cost.

Further, among these, ethylene-vinyl acetate copolymers having a vinyl acetate content of 5% by weight or more and 25% by weight or less are particularly preferable in terms of transparency, flexibility, weather resistance and the like.

The hydrotalcite compound represented by the general formula [I] used in the present invention is represented by the general formula M _(1-X) Al _x (OH) ₂ X _{x / n} · mH ₂ O, where M is Indicates alkaline earth metals and Zn.
X represents an n-valent anion.

Then, x and m satisfy the condition of the following equation.

It is a hydrotalcite-type compound represented by 0 <x <0.5 0 ≦ m ≦ 2.

In the above formula, examples of the n-valent anion represented by X include Cl ⁻ , Br ⁻ , I ⁻ , NO ₃ ⁻ , ClO ₄ ⁻ , S.
O ₄ ²⁻ , CO ₃ ²⁻ , SiO ₃ ²⁻ , HPO ₄ ²⁻ , HBO ₃ ³⁻ ,
PO ₄ ³⁻ , Fe (CN) ₆ ⁶⁻ , Fe (CN) ₄ ⁴⁻ , CH ₃ C
OO ⁻ , C ₆ H ₄ (OH) COO ⁻ , Anions such as, for example, can be exemplified.

The compounding amount of these hydrotalcite compounds is selected within the range of 1 to 25 parts by weight with respect to 100 parts by weight of the polyethylene resin. When the amount is less than 1 part by weight, the weather resistance of the polyethylene resin film is not improved even when the organophosphate metal salt compound is used in combination. On the other hand, if the blending amount of the hydrotalcite-based compound is more than 25 parts by weight, an excellent transparent film cannot be obtained, which is not preferable.

Within the above range, 2 to 20 parts by weight is particularly preferable.

The hydrotalcite-based compound is not particularly limited, but has an average secondary particle diameter of 5 μm or less and a BET specific surface area of 30 m ² / g or less in order to particularly improve film processability, physical properties and the like. Those having a refractive index in the range of 1.47 to 1.52 are preferable.

Further, in the present invention, the hydrotalcite compound can be used after being treated with a surface treating agent, further improving the dispersibility or affinity to the polyethylene resin, and imparting a favorable improvement in the processability and physical properties of the film. It is also preferable because it also helps to improve the parallel light transmittance. Examples of such a surface treatment agent include, for example, sodium laurate, potassium laurate, sodium oleate, potassium oleate, sodium stearate,
Alkali metal salts of higher fatty acids such as potassium stearate, sodium palmitate, potassium palmitate, sodium caprate, potassium caprate, sodium myristate, potassium myristate, sodium linoleate, potassium linoleate: Lauric acid, for example. Higher fatty acids such as palmitic acid, oleic acid, stearic acid, capric acid, myristic acid, linoleic acid:
Cups such as isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, vinyl triethoxysilane, gamma methacryloxypropyl trimethoxysilane, gamma glycidoxypropyl trimethoxysilane, etc. Ring agents: etc. can be illustrated.

Surface treatment with these surface treatment agents, for example, in the state of suspending the hydrotalcite compound in warm water,
While stirring, by adding an aqueous solution of an alkali metal salt of a higher fatty acid, or by stirring a hydrotalcite compound powder with a mixer such as a Henschel mixer, a melt of a higher fatty acid or a diluent of a coupling agent is stirred. It can be performed by dropping. The amount of these surface-treating agents imparted by the surface treatment can be appropriately selected and changed, and examples thereof include about 1 to about 10% by weight based on the hydrotalcite compound.

In addition, the general formula [II] or [III] (In the formula, M means zinc, calcium, barium, magnesium, cobalt or strontium. Further, R ¹ , R ² and R ³ are each an alkyl, aryl, arylalkyl, alkylaryl or ether bond. R ¹ of means an alkyl group.) the organic phosphoric acid metal salt compound represented by ^having, R ² and R
Examples of the alkyl group represented by ³ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, sec-butyl, amyl, neopentyl, isoamyl, hexyl, isohexyl, heptyl, octyl,
Isooctyl, 2-ethylhexyl, decyl, isodecyl, lauryl, tridecyl, C ₁₂ -C ₁₃ mixed alkyl,
Examples thereof include stearyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl and 4-methylcyclohexyl groups.

Examples of aryl groups include phenyl and naphthyl groups.

Examples of the arylalkyl group include benzyl, β-phenylethyl, α-phenylpropyl and β-phenylpropyl groups.

Examples of alkylaryl groups include tolyl, xylyl,
Examples thereof include ethylphenyl, butylphenyl, tert-butylphenyl, octylphenyl, isooctylphenyl, tert-octylphenyl, nonylphenyl and 2,4-di-tert-butylphenyl groups.

As the alkyl group having an ether bond, furfuryl, tetrahydrofurfuryl, 5-methylfurfuryl and α-methylfurfuryl groups, or methyl-, ethyl-, isopropyl-, butyl-, isobutyl-, hexyl-, cyclohexyl- , Phenyl cellosolve residue; methyl-, ethyl-, isopropyl-, butyl-, isobutylcarbitol residue; triethylene glycol monomethyl ether, -monoethyl ether, -monobutyl ether residue; glycerin 1,2-dimethyl ether, -1 , 3
-Diethyl ether, -1-ethyl-2-propyl ether residue; nonylphenoxypolyethoxyethyl, lauroxypolyethoxyethyl residue and the like. The organic phosphate metal salt compound having various substituents as described above,
It is possible to mix one kind or two or more kinds in combination.

The compounding amount is selected within the range of 0.1 to 5 parts by weight, preferably within the range of 0.2 to 5 parts by weight, based on 100 parts by weight of the polyethylene resin. If the blending amount is less than 0.1 part by weight, the weather resistance of the polyethylene resin film will not be improved even if a hydrotalcite compound is used in combination. On the other hand, if the amount of the organophosphoric acid metal salt compound is more than 5 parts by weight, the transparency of the film and the transparency are extremely poor, which is not preferable. Within the above range, 0.2 to 2 parts by weight is particularly preferable. Among the types of metals, zinc, calcium and barium are particularly preferable.

Further, the following compounding agents can be used in the film according to the present invention, if necessary.

That is, plasticizer, organic phosphate ester, epoxy compound, heat stabilizer, chelator, lubricant, antifogging agent (surfactant), hindered amine light stabilizer, ultraviolet absorber, infrared absorber, antioxidant, antistatic Agents, fillers, fungicides, algae inhibitors and colorants.

As the plasticizer that can be used in the present invention, those commonly used for plasticizing polyvinyl chloride, olefin-vinyl alcohol copolymers and the like are used. Particularly preferred are low molecular weight polyhydric alcohols having a molecular weight of 250 or less, such as glycerin, ethylene glycol, triethylene glycol and sorbitol. These also exhibit an excellent effect in imparting antifogging property, which is essential as an agricultural film.
Examples of plasticizers other than these alcohol-based ones include dibutyl phthalate, heptyl phthalate, and di-2-phthalate.
Phthalates such as ethylhexyl, butylbenzyl phthalate, butyllauryl phthalate, mixed phthalates of methyloleic acid phthalate, dioctyl adipate, diisodecyl adipate, dioctyl azelate dibasic acid esters And glycol esters such as diethylene glycol benzoate, and fatty acid esters such as butyl oleate and methyl acetylricinoleate.

Organic phosphates that can be used include tricresyl phosphate (TCP) and trixylenyl phosphate (T
XP), dixylenyl monocresyl phosphate, monoxylenyl dicresyl phosphate, and phosphoric acid esters having at least one ethylphenol in the molecule.

Further, the starting material is a mixed alcohol containing xylenol, ethylphenol and cresol as main components, and a phosphoric acid ester produced by using these alcohols in a specific ratio can also be used.

Examples of the epoxy compound include epoxidized soybean oil, epoxidized linseed oil, epoxidized fish oil, epoxidized roll oil fatty acid ester, epoxidized beef tallow oil, epoxidized polybutadiene, methyl epoxystearate, butyl epoxystearate, and epoxystearic acid- 2-ethylhexyl, stearyl epoxystearate, tris (epoxypropyl) isocyanurate, epoxidized castor oil, epoxidized safflower oil, epoxidized linseed oil fatty acid butyl, 3- (2-xenoxy) -1,2-epoxypropane, Examples thereof include bisphenol-A-diglycidyl ether, vinylcyclohexene diepoxide, and a polycondensation product of 2,2-bis (4-hydroxyphenyl) propane and epichlorohydrin.

Examples of the carboxylic acid constituting the metal salt of an organic acid used as a heat stabilizer in the present invention include caproic acid, pelargonic acid, lauric acid, 2-ethylhexylic acid, myristic acid, palmitic acid, undecylenic acid, ricinoleic acid,
Linoleic acid, linoleic acid, neodecanoic acid, oleic acid, stearic acid, isodecanic acid, isostearic acid,
12-hydroxystearic acid, 12-ketostearic acid, chlorostearic acid, phenylstearic acid, arachidic acid, behenic acid, erucic acid, brassic acid and similar acids, and tallow fatty acid, coconut oil fatty acid, tung oil fatty acid, soybean fatty acid and cottonseed oil Naturally occurring mixtures of the above acids such as fatty acids, benzoic acid, chlorobenzoic acid, toluic acid, salicylic acid, p-t-butylbenzoic acid, 5-t-octylsalicylic acid, naphthenic acid, xylic acid, ethylbenzoic acid,
Examples thereof include isopropylbenzoic acid, di-t-butylbenzoic acid, bromobenzoic acid, monobutylmalate, monodecylphthalate and cyclohexanecarboxylic acid.

Phenols are also useful as organic acids. For example, phenol, cresol, ethylphenol, dimethylphenol, isopropylphenol, cyclohexylphenol, t-butylphenol, phenylphenol, nonylphenol, dinonylphenol, methyl-
t-butylphenol, tetramethylphenol, poly (di-penta) isopropylphenol, diisopropyl-m-cresol, butylphenol, isoamylphenol, isooctylphenol, 2-ethylhexylphenol, t-nonylphenol, decylphenol, t-dodecylphenol, t- Examples thereof include octylphenol, octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, methyl-t-octylphenol, di-t-nonylphenol and di-t-dodecylphenol.

The metal component includes zinc and Group Ia metals such as lithium, sodium and potassium, and Group IIa metals such as barium, calcium, magnesium and strontium.

Examples of the organic phosphite compound used in the present invention as a chelator include diphenyldecylphosphite, triphenylphosphite, tris-nonylphenylphosphite, tridecylphosphite, tris (2
-Ethylhexyl) phosphite, tributylphosphite, tris (dinonylphenyl) phosphite, trilauryltrithiophosphite, trilaurylphosphite, bis (neopentylglycol) -1,4-cyclohexanedimethylphosphite, distearylpentaerythrium Stol diphosphite, diisodecyl pentaerythritol phosphite, tris (lauryl-2-thioethyl) phosphite, tetratridecyl-1,1,3-tris (2'-methyl-5'-tert-butyl-4'-oxy phenyl) butane diphosphite, tetra (C ₁₂ -C ₁₅ mixed alkyl (4,4'-isopropylidene diphenyl diphosphite, tris (4-oxy-2,5-di - tert-butyl-phenyl) phosphite, tris (4-oxy-3,5
-Di-tert-butylphenyl) phosphite, 2-ethylhexyldiphenylphosphite, tris (mono, dimixed nonylphenyl) phosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, diphenyl bis [ 4,4'-n-butylidene bis (2-tert-butyl-5-methylphenol)] thiodiethanol diphosphite, bis (octylphenyl) bis [4,4 '
-N-butylidene bis (2-tert-butyl-5-methylphenol)]-1,6-hexanediol diphosphite, phenyl-4,4'-isopropylidene diphenol / pentaerythritol diphosphite, phenyldiisodecyl phosphite , Tetratridecyl-4,4'-n
-Butylidene bis (2-tert-butyl-5-methylphenol) diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, tristearylphosphite, octyldiphenylphosphite, diphenyltridecylphosphite, phenyldi ( Tridecyl) phosphite, tris (2-cyclohexylphenyl) phosphite, ditridecyl-di (2-cyclohexylphenyl) -hydrogenated bisphenol A diphosphite, di (2,
4-di-tert-butylphenyl) cyclohexyl phosphite, 2,4-di-tert-butylphenyl diisodecyl phosphite, tris (butoxyethoxyethyl) phosphite, diphenyl acid phosphite, bis (2-cyclohexylphenyl) acid Phosphite, bis (2,
4-di-t-butylphenyl) acid phosphite, bis (nonylphenyl) acid phosphite, dibenzyl acid phosphite and the like can be mentioned.

Lubricants that can be used include fatty acid lubricants such as stearic acid, palmitic acid and myristic acid; fatty acid amide lubricants such as stearic acid amide, palmitic acid amide, methylene bis stearoamide and ethylene bis stearoamide; butyl stearate. Examples thereof include ester lubricants such as butyl palmitate, polyethylene wax, and liquid paraffin.

As the antifogging agent used in the present invention, nonionic, anionic and cationic surfactants are used, for example, polyoxyalkylene ether, partial ester of polyhydric alcohol, alkylene oxide adduct of polyhydric alcohol. Partial esters, higher alcohol sulfuric acid ester alkali metal salts, alkylaryl sulfonates, quaternary ammonium salts, and aliphatic amine derivatives. Specifically, polyoxyethylene lauryl ether, -stearyl ether, -nonyl phenyl ether, polyethylene glycol monopalmitate, polyethylene glycol monostearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, glycerin Monolaurate, glycerin monopalmitate, glycerin monostearate, glycerin monooleate, pentaerythritol monolaurate, sorbitan monopalmitate, sorbitan monobehenate, sorbitan monostearate, sorbitan distearate, diglycerin monooleate, tri Glycerindiolate, sodium lauryl sulfate, sodium dodecylbenzene sulfonate, butylnaphthalene sulfonate Thorium, cetyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride, dodecylamine hydrochloride, lauric laurylamidoethyl phosphate, triethylcetylammonium iodide, oleylaminodiethylamine hydrochloride, dodecylpyridinium sulfate basic pyridinium salt, etc. To be

The structural formula of the hindered amide compound that can be used in the present invention is as follows.

(1) 2,2,6,6-tetramethylpiperidinyl-4-benzoate (2) Bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate (3) n = 4-6 Average molecular weight-about 3,000 (4) Molecular weight 2,500 or more (5) 1,3,8-triaza, 7,7,9,9-tetramethyl-3-
n-octyl-spiro [4,5] decane-2,4-dione (6) (7) 1,2,3,4-tetra (4-carbonyloxy-2,2,
6,6-Tetramethylpiperidine) -butane (8) (9) Tri- (4-acetoxy-2,2,6,6-tetramethylpiperidine) -amine (10) 4-acetoxy-2,2,6,6-tetramethylpiperidine (11) 4-stearoyloxy-2,2,6,6-tetramethylpiperidine (12) 4-benzyloxy-2,2,6,6-tetramethylpiperidine (13) 4- (phenylcarbamoyloxy) -2,2,6,
6-tetramethylpiperidine (14) 4- (p-toluenesulfonyloxy) -2,2,
6,6-Tetramethylpiperidine (15) Bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate (16) Tris (2,2,6,6-tetramethyl-4-piperidine) phosphite (17) 1,3,8-triaza-7,7,9,9-tetramethyl 2,4
-Dioxo-spiro [4,5] decane (18) (2,2,6,6-tetramethylpiperidine) -4-
Spiro-2 '-(6', 6'-dimethylpiperidi)-
4'-spiro-5 "-hindantoin (19) These hindered amine compounds can be used alone or in combination of two or more.

Examples of the ultraviolet absorber include 2-hydroxy-4-
Methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-n
-Octadecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-2'carboxybenzophenone, 2-
Hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy-5-chlorobenzophenone, 2,4
-Dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-di-methoxybenzophenone, 2,2'-dihydroxy-4,4'-di-methoxy-5 -Benzophenone-based UV absorbers such as sulfobenzophenone and 2,2 ', 4,4'-tetrahydroxybenzophenone; 2- (2'-hydroxy-5'-methylphenyl) benzotriazole,
2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-
3 ', 5'-dimethylphenyl) benzotriazole,
2- (2'-methyl-4'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-3'-methyl-5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3) ', 5'-di-tert-
Amylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3',
5'-dimethylphenyl) -5-methoxybenzotriazole, 2- (2'-n-octadecyloxy-3 ',
5'-Dimethylphenyl) -5-methylbenzotriazole, 2- (2'-hydroxy-5'-methoxyphenyl) benzotriazole, 2- (2'-hydroxy-
4'-octoxyphenyl) benzotriazole, 2-
(2'-hydroxy-5'-methoxyphenyl) -5-
Methylbenzotriazole, 2- (2'-hydroxy-
5'-methylphenyl) -5,6-dichlorobenzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) -5-chlorobenzotriazole, 2-
(2'-Hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'
-Hydroxy-5'-phenylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-
Dichlorohexylphenyl) benzotriazole, 2-
(2'-hydroxy-3 ', 5'-dichlorophenyl)
Benzotriazole, 2- (2'-hydroxy-4 ',
5'-dichlorophenyl) benzotriazole, 2-
(2'-Didroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'
-Hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-
Hydroxy-3'-methylphenyl) -5-butoxycarbonylbenzotriazole, 2- (2'-hydroxy-4 ', 5'-dimethylphenyl) -5-butoxycarbonylbenzotriazole, 2- (2'-hydroxy)
-5-ethoxycarbonylbenzotriazole, 2-
(2'-acetoxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) -5-ethylsulfone benzotriazole, 2
-(2'-hydroxy-3 ', 5'-dimethylphenyl) -5-ethylsulfone benzotriazole, 2-
Benzotriazole-based UV absorbers such as (2'-hydroxy-5'-phenylphenyl) benzotriazole and 2- (2'-hydroxy-5'-aminophenyl) benzotriazole; phenyl salicylate, p-tert-butylphenyl sali Examples thereof include salicylic acid ester-based ultraviolet absorbers such as citrate, p-methylphenyl salicylate, and p-octylphenyl salicylate.

Examples of phenolic antioxidants include 2,6-di-tert-butyl-p-cresol and stearyl- (3,5-di-
Methyl-4-hydroxybenzyl) thioglycolate,
Stearyl-β- (4-hydroxy-3,5-di-tert-butylphenyl) propionate, distearyl-3,5-
Di-tert-butyl-4-didoxybenzylphosphonate, 2,4,6-tris (3 ', 5'-di-tert-butyl-
4'-hydroxybenzylthio) -1,3,5-triazine, distearyl (4-hydroxy-3-methyl-5-
Tert-Butyl) benzyl malonate, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4 '
-Methylenebis (2,6-di-tert-butylphenol),
2,2'-methylenebis [6- (1-methylcyclohexyl) p-cresol], bis [3,5-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4 ' -Butylidene bis (6-third
Butyl-m-cresol), 2,2'-ethylidene bis (4,6-di-tert-butylphenol), 2,2'-ethylidene bis (4-tert-butyl-6-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-
Tertiary butyl) benzyl isocyanurate, 1,3,5-tris (3,5-di-tertiary butyl-4-hydroxybenzyl)
-2,4,6-Trimethylbenzene, 2,6-diphenyl-4-
Octadecyloxyphenol, tetrakis [methylene-
3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1, 3,5-Tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 2-octylthio-4,6-di (4-hydroxy-3,5-di-second 3butyl) phenoxy-1,3,5-triazine, phenols such as 4,4′-thiobis (6-tert-butyl-m-cresol), and 4,4′-butylidenebis (2-tert-butyl-5- Carbonic acid oligoester of methylphenol (eg degree of polymerization 2,3,4,5,6,7,8,9,10)
Examples include polyhydric phenol carbonic acid oligoesters.

Examples of the sulfur-based antioxidant include dilauryl-, dimyristyl-, dialkylthiodipropionates such as distearyl- and butyl-, octyl-, lauryl-, stearyl-, and other polyhydric alcohols of alkylthiopropionic acids (such as glycerin, Trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate) ester (for example, pentaerythritol tetralauryl thiopropionate) can be mentioned.

Examples of the stabilizing aid used in the present invention include 2,6
-Di-t-butyl-p-cresol, dilaurylthiodipropionate, diphenylthiourea, phenylindole, thiodiglycolbis (aminocrotonate),
Pentaerythritol, tris (hydroxyethyl) isocyanurate, sorbitol, mannitol, anilinodithiotriazine, melamine, dipentaerythritol adipate, p-t-butylbenzoic acid, dehydroacetic acid, zinc dehydroacetate, nonylphenoxypolyethoxyphosphoric acid, benzoic acid , Cinnamic acid, dibenzoylmethane, stearoylbenzoylmethane, benzoylpentanoylmethane and the like.

Examples of the antistatic agent include polyoxyethylene alkylamine, polyglycol ether, sodium p-styrenesulfonate, and the like.

Compounds that can be used as fungicides and algae preventative agents are 2,
4,5,6-Tetrachloroisophthalonitrile, 10,10'-oxybisphenoxyarsine, 2- (4-thiazolyl)
-Benzimidazole, N (fluorodichloromethylthio) phthalimide, N-dimethyl-N'-phenyl-
(N'-florodichloromethylthio) sulfamide, paraoxybenzoic acid ester, 5-bromo-5-nitro-
Examples thereof include 1,3-dioxane, 2,3,5,6-tetrachloro-4-methylsulfonylpyridine, 3-methyl-4-chlorophenol, N (tetrachloroethylthio) phthalimide, and tributyltin laurate.

Examples of usable colorants include phthalocyanine blue, phthalocyanine green, Hansa yellow, alizarin lake, titanium oxide, zinc oxide, permanent red, quinacridone, carbon black and the like.

The above various resin additives can be used alone or in combination of two kinds.

The above-mentioned various resin additives are added in such a range that the properties of the film are not deteriorated.
It can be selected within the range of 5 parts by weight or less with respect to parts by weight.

In order to mix the above-mentioned hydrotalcite compounds and organic phosphate metal salt compounds into the base polyethylene resin, and further other resin additives, each is weighed in a necessary amount, a ribbon blender,
A Banbury mixer, super mixer, or other conventionally known compounding machine or mixing machine may be used. In order to form the resin composition thus obtained into a film, a method known per se, for example, a melt extrusion molding method (including a T-die method, an inflation method), a calender molding method, etc., has been conventionally known. You can follow the method.

The film according to the present invention may be transparent, satin-finished, or semi-finished, and can be used for covering agricultural houses (greenhouses), tunnels, etc., as well as mulching, bags, etc.

The film thickness is 0.03 in terms of strength and cost.
.About.0.3 mm is preferable, and in particular, 0.05 to 0.2 mm is particularly preferable.

"Action" As described above, the present invention in which a specific amount of a specific hydrotalcite compound and a specific organic metal phosphate compound is blended is to provide an agricultural polyethylene resin film having particularly excellent weather resistance. Can be done.

"Examples" Hereinafter, the present invention will be described in detail based on Examples,
The present invention is not limited to the following examples as long as the gist thereof is not exceeded.

Example 100 parts by weight of ethylene-vinyl acetate copolymer (vinyl acetate content = 15% by weight melt index = 1.5 g / 10 minutes) 0.1 parts by weight of ethylene bis stealoid (lubricant) 1.0 part by weight of sorbitan monostearate (anti-fog Agent) 2-hydroxy-4-octoxybenzophenone (ultraviolet absorber) 0.1 part by weight is used as a basic composition, and the hydrotalcite compounds and organic phosphate metal salt compounds shown in Table 1 are shown in Table 1 as well. After mixing in a ratio, the resin temperature is 130 to 1 in the test Banbury.
After kneading at 50 ° C for 5 minutes, granulated pellets were produced by an extruder.

In addition, in Example 12, the following CHIMASSORB 944, which is a hindered amine-based light stabilizer, was used in addition to the above compounds.
LD was added at 0.2 parts by weight.

-CHIMASSOR B 944 LD: manufactured by Ciba Geigy, molecular weight 2,500 or less, melting point 100-135 ° C. The pellets thus obtained were subjected to T-die melt extrusion (2
21 kinds of films having a thickness of 0.1 mm were manufactured at 00 ° C.).

The obtained films were evaluated according to the following methods. The results are also shown in Table 1.

Weather resistance test We exposed each film for 15 months from September 1985 on a window frame-shaped closed test stand facing the south side and installed at an angle of 45 degrees to the ground (installation location: Nagoya City, Aichi Prefecture). Then, a part of the film was periodically removed from the exposure test stand, and the appearance and stretch were evaluated, and the evaluation criteria were as follows.

Good: Appearance does not change and residual elongation is 80% or more.

○ _{x: No} change in appearance and residual elongation rate of 79 to 60%
In the range of.

B: Some of the appearance changes such as cracks and tears are recognized, and the residual elongation is in the range of 79 to 60%.

△ _x : Appearance changes such as cracks and tears were observed,
The residual elongation is in the range of 59 to 40%.

C: Cracks are observed over the entire surface or the residual elongation is less than 40%.

The residual elongation rate was calculated by the following formula.

Transparency test Each film was pressed under a temperature condition of 180 ° C to prepare a sheet having a thickness of 2 m / m. The transparency of this sheet was visually evaluated as follows.

◎ ・ ・ ・ Transparency is good ○ ・ ・ ・ Slight turbidity is felt △ ・ ・ ・ Slight white turbidity is felt × ・ ・ ・ Transparency is inferior (quite white turbidity is felt) Spoutability test Sample film in the room for 3 months After leaving it to stand, the surface was lightly rubbed with a finger, and the spouting state was visually evaluated as follows according to the degree of marks.

◎ ・ ・ ・ No squirt (no trace) ○ ・ ・ ・ Most squirt (slightly finger marks) △ ・ ・ ・ Spitting but little stickiness × ・ ・ ・ Stickingly sticky Is remarkable "Effects of the Invention" As is apparent from the examples and comparative examples above, the film according to the present invention, that is, a specific hydrotalcite compound, and a polyethylene-based compound containing a specific amount of the essential components of the organophosphate metal salt compound A film made of a resin composition has remarkably excellent weather resistance even when used outdoors for a long period of time.
It also has good transparency and little spouting.

Further, from Example 12, it can be seen that the effect of improving the weather resistance is further enhanced by further using the hindered amine compound in combination.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C08L 31/04 LDF 6904-4J // (C08K 13/02 3:26 5: 527 5: 521) (56) References JP-A 61-218646 (JP, A) JP-A 60-219246 (JP, A) JP-A 60-104141 (JP, A)

Claims (1)

[Claims] 1. A hydrotalcite compound represented by the following general formula [I] in an amount of 1 to 25 parts by weight per 100 parts by weight of a polyethylene resin or an ethylene-vinyl acetate copolymer resin, and 0.1 to 5 parts by weight of the following general compounds. A polyethylene-based resin film for agricultural use M _(wherein each is blended with at least one compound selected from the specific organophosphate metal salt compounds represented by the formulas [II] and / or [III] _1-X) Al _x (OH) ₂ X _{x / n} · mH ₂ O [I] However, in the formula, M represents an alkaline earth metal and Zn.
X represents an n-valent anion. Then, x and m satisfy the condition of the following equation. 0 <x <0.5 0 ≦ m ≦ 2 (In the formula, M means zinc, calcium, barium, magnesium, cobalt, or strontium. Further, R ¹ , R ² , and R ³ are each an alkyl, aryl, arylalkyl, alkylaryl or ether bond. Means an alkyl group having