JPH066364B2 - Laminated film for agriculture - Google Patents

Description

TECHNICAL FIELD The present invention relates to an agricultural laminated film mainly composed of an olefin resin having improved transparency, durability, abrasion resistance, dust resistance and impact resistance.

"Conventional technology" Conventionally, as greenhouse coating materials used for greenhouse cultivation such as agricultural houses and tunnel houses, polyvinyl chloride films, polyethylene films, polyolefin resin films such as ethylene-vinyl acetate copolymer films are mainly used. It is used. Of these, polyvinyl chloride films have been widely used in this field until recent years because they have excellent heat retention, transparency, toughness, durability and the like. However, the polyvinyl chloride film has a drawback in that the plasticizer contained in the film bleeds to the film surface during use, dust is attached to the film surface and the light transmittance is significantly impaired, and the temperature rise in the house is prevented. When incinerated after use, hydrochloric acid gas is generated and it is difficult to dispose of it. Furthermore, there is a problem that it cannot withstand use in cold regions because it loses flexibility at low temperatures and its impact resistance becomes poor.

On the other hand, since the olefin resin film does not contain a plasticizer in the film and has a stable chemical structure, the light transmittance hardly changes during long-term use, and no harmful gas is generated even when incinerated. Although inexpensive and excellent in processability, this film has the drawback of being less durable than a polyvinyl chloride film. Therefore, it has not been used as a house coating film in the past, while having the above-mentioned advantages.

Further, as a coating film having improved durability of a polyolefin resin film, a specific hindered amine light stabilizer of a polyolefin resin and an inorganic fine powder having a specific polarity are found as disclosed in JP-A-56-41254. There is a polyolefin film added,
In this case, the durability is slightly improved, but the transparency and physical strength of the film are reduced. Furthermore, JP-A-60-12
No. 0732, JP-A-60-199039, JP-A-61-31466, a specific hindered amine light stabilizer of a polyolefin resin and a plurality of specific antioxidants are added. Or a polyolefin resin obtained by adding a specific organophosphoric acid metal salt compound and a specific hindered phenolic antioxidant to the polyolefin resin as seen in JP-A-62-43442. Although resin-based resin compositions and the like are known, in these methods, the diffusion rate of the antioxidant in the polyolefin-based resin is high, migrates to the film surface in a short period of time, is exposed to wind and rain, and is washed away from the surface. Therefore, durability cannot be maintained for a long period of time. Even if the concentration of the antioxidant added to the film is increased for the purpose of maintaining durability for a long period of time, the amount of the antioxidant remaining inside the film does not increase at all, only the amount transferred to the film surface increases. Durability cannot be maintained for a long time. Moreover, when the concentration of the antioxidant added is increased, the surface appearance of the film is deteriorated and the transparency is lowered.

Especially at high temperatures in summer, the amount of solar radiation increases, not only the photodegradation reaction of the film is accelerated, but also the migration rate of the antioxidant to the film surface becomes large, and the deterioration of the film is significantly accelerated due to the combination of both. It is extremely difficult to maintain long-term durability in summer use.

"Problems to be solved by the invention" In view of such actual circumstances, the present inventors have extremely excellent durability, transparency, without impairing the light transmittance of the polyolefin film, the soil non-contamination property, the incineration processability, and the like. As a result of earnest research to provide an agricultural film excellent in dust resistance, abrasion resistance, and impact resistance at low cost, a specific hydrotalcite compound and an organic metal phosphate salt are mixed with an olefin resin. By providing a coating layer made of an olefin resin on one or both sides of a film made of the resin composition, it has extremely excellent durability, transparency, dust resistance, abrasion resistance, and impact resistance as compared with the conventional technology. The present invention has been completed by finding out that a film having a high quality can be obtained.

"Means for Solving Problems" The gist of the present invention is to add 1 to 25 parts by weight of a hydrotalcite compound to 0.1 to 100 parts by weight of a polyolefin resin.
A laminated film for agriculture, characterized in that a coating layer made of an olefin resin is provided on one side or both sides of a base layer made of a composition containing 5 parts by weight of an organophosphate metal salt compound.

The present invention will be described in more detail below.

The olefin resin used for the base layer in the present invention is an α-olefin homopolymer, a copolymer with a different monomer containing α-olefin as a main component, such as polyethylene, polypropylene, ethylene- Propylene copolymer, ethylene-butene copolymer, ethylene-4-
Methyl-1-pentene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer and the like can be mentioned. Among these, low-density polyethylene having a density of 0.910 or more and 0.935 or less, an ethylene-α-olefin copolymer, and an ethylene-vinyl acetate copolymer having a vinyl acetate content of 30% by weight or less have transparency, durability and price. From the viewpoint of, it is preferable as an agricultural film.

Above all, the vinyl acetate content is 5 wt% or more and 25 wt% or more.
Among these, the following ethylene-vinyl acetate copolymers are more preferable in terms of transparency, flexibility, durability and the like.

The olefin-based resin used in the coating layer in the present invention belongs to the same category as the olefin-based resin used in the above-mentioned base layer, but among these, a resin having particularly good abrasion resistance is preferable. For example, in the case of polyethylene, density 0.910 g / cm ³ or more 0.935 g / cm ³ or less melt index of 0.1 g / 10 minutes or more 4g / 10 minutes or less polyethylene or ethylene -α- olefin copolymer.
When the density is 0.910 g / cm ³ or less, heat resistance is not preferable, and when the density is 0.935 g / cm ³ or more, transparency is not preferable. Further, when the melt index is 0.1 g / 10 minutes or less, it is not preferable in terms of workability, and when it is 4 g / 10 minutes or more, it is not preferable in terms of friction characteristics and strength.

In the case of ethylene-vinyl acetate copolymer, the vinyl acetate content is 15% by weight or less, more preferably 10% by weight.
Melt index below 0.1g / 10min or more 4g / 10
Minutes or less, more preferably 0.1 g / 10 minutes or more and 1.5 g / 10 minutes or less. Vinyl acetate content is 15% by weight
The above is not preferable in terms of heat resistance, and a melt index of 0.1 g / 10 minutes or less is not preferable in terms of workability and a melt index of 4 g / 10 minutes or more in terms of friction characteristics and strength.

In the case of ethylene-acrylic acid copolymer, the acrylic acid content is preferably 30% by weight or less, more preferably 25% by weight or less.

The hydrotalcite compound used in the present invention the general formula _{M (1-x) · Al} x · (OH) 2 · X x / n · m H 2 O However Shikichu M is an alkaline earth metal 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.

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

The hydrotalcite compound used in the agricultural laminated film of the present invention is not particularly limited, but in order to improve parallel light transmittance, film processability, physical properties and the like, a refractive index of 1.47 or more and 1.52 or less. Average secondary particle size 5μ
m or less, and the BET specific surface area is preferably 30 m ² / g or less.

Furthermore, in the present invention, the hydrotalcite compound can be used after being treated with a surface treatment agent, which further improves the dispersibility or affinity for an olefin resin,
It is preferable because it gives a favorable improvement in the processability and physical properties of the film and 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, potassium stearate, sodium palmitate,
Alkali metal salts of higher fatty acids such as potassium palmitate, sodium caprate, potassium caprate, sodium myristate, potassium myristate, sodium linoleate, potassium linoleate; for example, lauric acid, palmitic acid, oleic acid, stearic acid ,
Higher fatty acids such as capric acid, myristic acid, linoleic acid, etc .: For example, isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, vinyl triethoxysilane, gamma methacryloxy. Examples thereof include coupling agents such as propyltrimethoxysilane and gammaglycidoxypropyltrimethoxysilane.

The surface treatment with these surface treatment agents is carried out, for example, by adding an aqueous solution of an alkali metal salt of a higher fatty acid to a hydrotalcite powder in a state of being suspended in warm water under stirring, or a hydrotalcite powder. Can be carried out by dropping a melt of a higher fatty acid or a diluting solution of a coupling agent under stirring with a mixer such as a Henschel mixer. The amount of these surface-treating agents can be selected and changed as appropriate, but about 1 to about 10% by weight is suitable with respect to the hydrotalcite compound.

Furthermore, a small amount of impurities such as other metal oxides may be included as long as the gist of the present invention is not impaired.

The mixing ratio of the hydrotalcite compound to the olefin resin as the base layer is generally 1
1 to 25 parts by weight, preferably 2 to 20 parts by weight, relative to 00 parts by weight
More preferably parts by weight. When the compounding amount of the compound is less than 1 part by weight, the effect of improving the heat retaining property of the obtained film is not recognized so much, and when the compounding amount exceeds 25 parts by weight, the strength of the film obtained is unfavorable.

Further, in the base layer, in order to improve the dispersion of the hydrotalcite compound, for example, a sorbitan fatty acid ester such as sorbitan monostearate or a glycerin fatty acid ester such as glycerin monostearate is used as a dispersant for the composition. 0.1 to 3 parts by weight may be added.

The organic phosphate metal salt compound in the present invention has the following general formula (In the formula, M means zinc, calcium, barium, magnesium, cobalt or strontium. Further, R ¹ , R ² and R ³ each have an alkyl, aryl, arylalkyl, alkylaryl or ether bond. Means an alkyl group.). Examples of the alkyl group represented by R ¹ , R ² and R ³ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl,
Tertiary butyl, amyl, neopentyl, isoamyl, hexyl, isohexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, decyl, isodecyl, lauryl, tridecyl, C ₁₂ -C ₁₃ mixed alkyl, stearyl, cyclopentyl, cyclohexyl, cyclooctyl, Examples thereof include dodecyl and 4-methylcyclohexyl group.

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 blending 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 polyolefin resin. If the blending amount is less than 0.1 part by weight, the durability of the polyolefin resin film will not be improved even if a hydrotalcite compound is used in combination. On the other hand, if the amount of the organophosphate metal salt compound is more than 5 parts by weight, the transparency of the film is 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.

If necessary, the following compounding agents may be used in both the base layer and the coating layer of the laminated film according to the present invention.

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, phthalic acid mixed base esters such as methyl oleyl 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), trixylenyl phosphate (TXP), dixylenyl monocresyl phosphate,
Other examples include 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 tall 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 oil fatty acid and Naturally occurring mixtures of the above acids such as cottonseed oil fatty acid, benzoic acid, chlorobenzoic acid, toluic acid, salicylic acid, p-t-butylbenzoic acid, 5-t-octylsalicylic acid, naphthenic acid, xylyl 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-octylphenol, octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, methyl -T-octylphenol, di-t-nonylphene Lumpur, and di -t- dodecyl phenol, and the like.

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, distearylpentaerythritol Diphosphite, diisodecyl bentaerythritol diphosphite, tris (lauryl-2-thioethyl) phosphite, tetratridecyl-1,1,3-
Tris (2'-methyl-5'-tert-4'-oxyphenyl) butane diphosphite, tetra (C ₁₂ -C ₁₅
Mixed alkyl (4,4'-isopropylidene diphenyl diphosphite, tris (4-oxy-2,5-di-tert-butylphenyl) phosphite, tris (4-oxy-3,
5-di-tert-butylphenyl) phosphite, 2-ethylhexyldiphenylphosphite, tris (mono, dimixed nonylphenyl) phosphite, hydrogenated-4,4'-
Isopropylidene diphenyl 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, tetra Tridecyl-4,4'-n-butylidene bis (2-tert-butyl-5-methylphenol) diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, tristearylphosphite, octyldiphenylphosphite , Diphenyl tridecyl phosphite, phenyl di (tridecyl) phosphite,
Tris (2-cyclohexylphenyl) phosphite,
Ditridecyl-di (2-cyclohexylphenyl) -hydrogenated bisphenol A-diphosphite, di (2,4-di-
Tert-butylphenyl) cyclohexylphosphite, 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.

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, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol monopalmitate, polyethylene glycol monostearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan mono Palmitate, glycerin monolaurate, glycerin monopalmitate, glycerin monostearate, glycerin monooleate,
Pentaerythritol monolaurate, sorbitan monopalmitate, sorbitan monobehenate, sorbitan monostearate, sorbitan distearate, diglycerin monooleate, triglycerin dioleate, sodium lauryl sulphate, sodium dodecylbenzene sulfonate, butylnaphthalene sulfonate Sodium, cetyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride, dodecylamine hydrochloride, lauric acid laurylamidoethyl phosphate, triethylcetylammonium iodide, oleylaminodiethylamine hydrochloride, dodecylpyridinium sulfate basic pyridinium salt, etc. To be

The structural formula of the hindered amine 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) (Four) (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 24-
Dioxose pyro [4,5] decane (18) (2,2,6,6-Tetramethylpiperidine) -4-spiro-2 '-(6', 6'-dimethylpiperidine) -4'-
Spiro-5 "-hydantoin (19) (20) 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'-hydroxy-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- (2'-
Benzotriazole-based UV absorbers such as hydroxy-5'-phenylphenyl) benzotriazole and 2- (2'-hydroxy-5'aminophenyl) benzotriazole; phenyl salicylate, p-tert-butylphenyl salicylate, p-methylphenyl Salicylate-based ultraviolet absorbers such as salicylate and p-octylphenyl salicylate can be mentioned.

Examples of phenolic antioxidants include 2,6-di-tert-butyl-p-cresol, 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-hydroxybenzylphosphonate,
2,4,6-Tris (3 ', 5'-di-tert-butyl-4'-hydroxybenzylthio) -1,3,5-triazine, distearyl (4-hydroxy-3-methyl-5-second 3-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-tertiary]
Butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (6-tert-butyl-m-cresol), 2,2′-ethylidenebis (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-tert-butyl) benzyl isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 2 , 6-Diphenyl-4-octadecyloxyphenol, tetrakis [methylene-3- (3,5-di-tertiary
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-tert-butyl) phenoxy- Phenols such as 1,3,5-triazine, 4,4'-thiobis (6-tert-butyl-m-cresol) and 4,4'-butylidenebis (2-tert-butyl-5)
-Methylphenol) carbonic acid oligoesters (for example, degree of polymerization 2,3,4,5,6,7,8,9,10, etc.) and other 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,
Examples thereof include benzoic acid, cinnamic acid, dibenzoylmethane, stearoylbenzoylmethane and benzoylpentanoylmethane.

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 white, perennant red, quinacridone, and carbon black.

The above various resin additives may be used alone or in combination of several kinds.

The amount of the above various resin additives added is in a range not deteriorating the properties of the film, usually the base olefin-based resin 10
It can be selected within the range of 5 parts by weight or less with respect to 0 parts by weight.

When producing the agricultural laminated film of the present invention, when blending the hydrotalcite-based compound and the organic phosphate metal salt compound in the polyolefin-based resin used for the base layer, and further other resin additives, each is weighed in a necessary amount, 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.

As a method of providing a coating layer made of an olefin resin on one side or both sides of a base layer made of an olefin resin containing such a hydrotalcite compound and an organic phosphate metal salt compound, dry lamination by forming respective films, heat A method of forming a laminated film by a laminating method, a method of extruding and laminating a coating layer made of an olefin-based resin on a base layer of an olefin-based resin film containing a hydrotalcite compound and a metal organic phosphate compound,
Existing techniques such as a method of simultaneously forming a laminated film by a multi-layer co-extrusion method may be used. Particularly, a method of forming by a multi-layer co-extrusion method is easy to form, interlayer adhesion of the resulting film, transparency, cost, etc. In terms of Furthermore, since a wide film is preferred for agricultural applications, a multilayer inflation processing method is desirable. When coating layers are provided on both sides of the base layer, different types of resins may be coated on each side, but considering the cost of the extruder, the same type of resin is sufficient for ordinary purposes.

The thickness of both the base layer and the coating layer is not specified because it is determined depending on the end use and purpose, but it is usually 2 depending on the mixing ratio of the hydrotalcite-type compound shown in the figure.
The thickness of 0 μm to 200 μm is sufficient, and the coating layer may have a thickness that reduces the external haze of the base layer and exhibits abrasion resistance, and normally 5 μm to 50 μm is sufficient.

The laminated film according to the present invention, whether transparent or satin,
Semi-pear cloth may also be used, and its application can be used for covering agricultural houses (greenhouses), tunnels, etc., as well as mulching, bag hanging, etc.

Further, the film thickness when laminated is preferably in the range of 30 μm to 300 μm in view of strength and cost, and particularly preferably 50 μm to 200 μm.

"Operation" and "Effect" The agricultural laminated film of the present invention has the following operations and effects.

The agricultural laminated film of the present invention contains hydrotalcite and an organic phosphate metal salt compound as an inorganic filler in the base layer. Since the hydrotalcite has a refractive index almost similar to that of the olefin resin, the olefin resin / The internal haze is not reduced without causing light scattering at the filler interface. Furthermore, by providing a resin layer containing no filler on at least one surface of the base layer, the surface unevenness due to the filler generated during film processing is significantly improved and the external haze is also significantly reduced as a result, so that the parallel light transmittance is very excellent. A transparent film is obtained. In addition, the heat retention, which has been a drawback of conventional polyolefin films, is greatly improved and is increased to a level comparable to that of polyvinyl chloride films.

Further, the agricultural laminated film of the present invention, by providing a resin layer containing no filler excellent in abrasion resistance on the coated surface, the abrasion resistance of the obtained film is significantly improved, and it has toughness. Further, the surface irregularities generated during film processing are remarkably improved, and as a result, the accumulation of dust and contaminants on the film surface is remarkably suppressed, so that heat storage deterioration and the like due to these are remarkably improved, and durability is greatly improved.

Next, since the agricultural laminated film of the present invention gradually bleeds out a surfactant such as an antifogging agent once adsorbed during processing due to the adsorption performance of the hydrotalcite-type compound, the antifogging sustainability of the film can be maintained for a long time. Have sex.

Incidentally, the hydrotalcite compound having a preferable refractive index in the present invention is produced by a known production method, and addition to the olefin resin is a general additive used when producing a conventional agricultural film. Since it can be added together, it is possible to use the conventional manufacturing process as it is, and it is generally easy to form a film.As a result, the present invention provides an extremely excellent olefin-based agricultural laminated film. .

Furthermore, since the agricultural laminated film of the present invention is mainly composed of an olefin resin, it is essentially easy to incinerate, and there is no problem that a particularly harmful substance is generated during incineration.

"Examples" Next, the present invention will be described with reference to examples, but these examples are merely illustrative, and the invention is not limited thereto.

Example 1 Ethylene-vinyl acetate copolymer having a vinyl acetate content of 15% by weight (melt index 1.5 g / 10 min, refractive index 1.495) and chemical composition Mg _0.7 Al surface-treated with sodium stearate in advance. _0.3 (OH) ₂ (CO ₃ ) _0.15 / 0.55H
Average secondary particle diameter of 0.3 μm with ₂ O, BET specific surface area 1
2m ² / g hydrotalcite compound (refractive index 1.50)
10 parts by weight and 1.0 part by weight of zinc stearyl phosphate as an organic metal phosphate compound, 0.5 part by weight of glycerin monostearate as an antifogging agent and a dispersant, 1.0 part by weight of polyglycerin stearate, and 2-hydroxy as a weathering aid. -4-octoxybenzophenone 0.2 part by weight was added,
Resin temperature 130 ° C ~ 150 ° C with 2L Banbury mixer
After kneading for 5 minutes, granulated pellets were produced by an extruder.

Hereinafter, the mixture will be referred to as a filler mixed resin.

The above filler-mixed resin was supplied to the base layer by the two-kind three-layer inflation molding method, and the high-pressure method low-density polyethylene resin composition (density 0.924 g / cm ³ , melt index 2 g / 10 min polyethylene 100 parts by weight) was used for the coating layer. 0.5 parts by weight of glycerin monostearate as an antifogging agent, 1.0 part by weight of polyglycerin stearate, and 0.2 parts by weight of 2-hydroxy-4-octoxybenzophenone as a weather resistance auxiliary agent are added to each layer, and each layer is supplied. A transparent film having a three-layer sandwich structure having a base layer of 50 μm and each coating layer of 13 μm was obtained.

The results of measuring the transparency, abrasion resistance, durability, dust resistance and impact resistance of the obtained film are shown in the table together.

Example-2 A transparent film was obtained by repeating Example-1, except that the organophosphoric acid metal salt compound used in the base layer in Example-1 was replaced with barium stearylphosphate.

Example-3 A transparent film was obtained by repeating Example-1 except that the organophosphoric acid metal salt compound used for the base layer in Example-1 was replaced with calcium stearylphosphate.

Example-4 Instead of the high-pressure low-density polyethylene resin used in the coating layer in Example-1, an ethylene-vinyl acetate copolymer (vinyl acetate content 5% by weight, density 0.92 g / cm ³ , melt index 2 g / Example 1 was repeated except that the transparent film was changed to 10 minutes).

Example-5 In place of the ethylene-vinyl acetate copolymer used as the base of the filler mixed resin used for the base layer in Example-1, high-pressure low density polyethylene (density 0.924 g / cm ³ , melt index 1.3 g / 10 Example 1 was repeated, except that the transparent film was obtained.

Example -6 Example chemical composition Mg _0.66 Al _0.34 a hydrotalcite compound of the base layer used in the _{-1 (OH) 2 (SiO 3} ) 0.17
· 0.52H ₂ O (average secondary particle diameter 0.4 .mu.m, BET specific surface area of 15 m ² / g) was replaced by hydrotalcite in got repeatedly transparent film in Example 1.

Example-7 In Example-1, the filler mixed resin used for the base layer was further a hindered amine compound SA manufactured by Sankyo Co., Ltd.
NOL LS-770 (Molecular weight 480.7 Melting point 80-90 °
Example 1 was repeated except that 1.0 part by weight of C) was added to obtain a transparent film.

Comparative Example-1 Example-1 except that the stearylphosphate zinc salt of the organophosphoric acid metal salt compound used for the base layer was removed in Example-1.
1 was repeated to obtain a film. The obtained film had a slightly poor transparency.

Comparative Example-2 A single layer film having a thickness of 76 μm was obtained by a single layer inflation molding method using the filler mixed resin used for the base layer in Example-1. The obtained film had a slightly poor transparency.

Each physical property test was conducted as follows. The values are shown in the table.

Transparency test: The parallel light transmittance of the film obtained by the present invention at a wavelength of 555 mm is measured by a spectrophotometer (330 manufactured by Hitachi Ltd.).
Type) and the values are shown in the table.

Rubbing resistance test: Using a U-F rubbing resistance tester, attach the film test piece to the fixed side so that wrinkles do not occur and attach the paper file # 400 to the corresponding side (the side that operates to the left and right) to fix it. The number of times of rubbing until the film was broken was evaluated.

The greater the number of tears, the better the abrasion resistance. The values of the obtained film are shown in the table.

Durability test: Each film was exposed for 24 months from September 1960 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). Part of the film was removed from the exposure test stand, and the appearance and elongation (JIS
Evaluation of K-6783). The evaluation criteria are as follows.

⊚: No change in appearance and 90% or more residual elongation.

○: There is no change in appearance and residual elongation is 89% to 80%
In the range of.

○ _{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.

Dustproofness test: Hype house (frontage 3m, depth 5m, ridge height 1.5m) with test film installed in a test field in Isshi-gun, Mie prefecture 30
The test was conducted for 24 months from September 1985 to September 1987.

The film after the spreading test is collected, and the light transmittance at a wavelength of 555 mm is measured by a spectrophotometer (manufactured by Hitachi Ltd., 330
Type). The display of measurement results is as follows.

A: Light transmittance of 80% or more.

◯: Light transmittance of 65 to 79%.

Δ: A light transmittance of 45 to 64%.

X: Light transmittance of less than 45%.

Impact strength test: A film test piece having a thickness of 76 μm, a width of 10 cm and a length of 10 cm is left in an atmosphere of −5 ° C. for 1 hour or more, and then a puncture film impact tester is used.
The impact strength was measured using an inch spherical surface, and the values are shown in the table.

"Effects of the Invention" As is apparent from the examples and the comparative examples above, the film according to the present invention, that is, the olefin resin containing the specific hydrotalcite compound and the organophosphate metal salt compound is added to another olefin resin. A film made by laminating resins has extremely excellent durability, and also has excellent transparency (parallel light transmittance), abrasion resistance, dust resistance, and impact resistance, and is extremely suitable as an agricultural film. I understand.

A olefin resin single layer film containing a specific hydrotalcite compound can achieve heat retention and transparency, but is inferior in abrasion resistance, durability, dust resistance, and impact resistance. A film obtained by laminating another olefin resin on an olefin resin containing only a specific hydrotalcite compound can achieve abrasion resistance, but has insufficient transparency, durability, dust resistance, and It is clear from the above description that the impact strength is also inferior and needless to say by showing concrete examples.

Further, when a hydrotalcite compound and a metal salt of an organic phosphoric acid compound are further used in combination with a hindered amine compound, durability and initial strength are further improved.

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Claims (4)

[Claims] 1. To 100 parts by weight of olefin resin, 1 to 2 parts
5 parts by weight of the following general formula M _(1-x) · Al _x · (OH) ₂ · X _{x / n} · _m H ₂ O where M is an alkaline earth metal and Zn is an n-valent anion. Show. Further, x and m satisfy the condition of the following formula. 0 <x <0.5 0 ≦ m ≦ 2 Hydrotalcite compound and 0.1 to 5 parts by weight of the following general formula (In the formula, M means zinc, calcium, barium, magnesium or strontium. Further, R ₁ , R ₂ and R ₃ each represent an alkyl group having an alkyl bond, aryl, arylalkyl, alkylaryl or ether bond. The coating layer made of an olefin resin is provided on one side or both sides of a base layer made of a composition in which one or more compounds selected from the specific organophosphate metal salt compounds represented by Characteristic laminated film for agriculture. 2. The agricultural use according to claim 1, wherein the olefin resin is an ethylene-vinyl acetate copolymer or a low-density polyethylene having a density of 0.935 g / cm ³ or less or an ethylene-α-olefin copolymer. Laminated film. 3. The refractive index of the hydrotalcite compound is 1.
BE in the range of 47 to 1.52 with an average secondary particle size of 5 μm or less
Claim 1 having a T specific surface area of 30 m ² / g or less.
The agricultural laminated film according to the item. 4. Polyethylene or ethylene-α in which the density of the olefin resin used in the coating layer is 0.915 g / cm ³ or more and 0.935 g / cm ³ or less, and the melt index is 0.1 g / 10 min or more and 4 g / 10 min or less. The agriculture according to claim 1, which is an olefin copolymer or an ethylene-vinyl acetate copolymer having a melt index of 0.1 g / 10 minutes or more and 4 g / 10 minutes or less and a vinyl acetate content of 15% by weight or less. Laminated film for.