JPH01200957A - Agricultural use laminated film - Google Patents

Abstract

PURPOSE:To improve weatherability and abrasion resistance, by providing a coating layer of an olefinic resin to the single surface or both surfaces composed of an olefin resin containing a hydrotalcite compound and a hindered amino compound. CONSTITUTION:1-25 pts.wt. of a hydrotalcite compound represented by formula I (wherein M is an alkaline earth metal or Zn, X is an n-valent anion, 0<x<0.5 and 0<=m<=2) and 1-5 pts.wt. of a hindered amine compound are mixed per 100 pts.wt. of an olefinic resin in a mixer such as a ribbon blender to prepare a resin composition. This resin composition is formed into a film by T-die processing and a coating layer composed of an olefinic resin is provided to the single surface or both surfaces of the formed film base layer to form an agricultural laminated film.

Description

Detailed Description of the Invention "Field of Industrial Application" The present invention is an agricultural laminated film mainly composed of olefin-based (B fat) which has improved weather resistance, transparency, abrasion resistance, dustproofness and impact resistance. Regarding.

[Conventional technology 1 Conventionally, greenhouse covering materials used for greenhouse cultivation such as agricultural greenhouses and tunnel houses include polyolefins such as polyvinyl chloride film, polyethylene film, and ethylene-hinoacetate conjugate film. Grease film is mainly used.

Among these, polyvinyl chloride film has been widely used in this field until recently because it has excellent heat retention, transparency, toughness, weather resistance, etc. However, during use, polyvinyl chloride film has the disadvantage that the plasticizer contained in the film bleeds onto the film surface, causing dust to adhere to it, severely impairing its light transmittance and preventing the temperature inside the greenhouse from rising. In addition, when incinerated after use, hydrochloric acid gas is generated, making disposal difficult. Furthermore, at low temperatures, it loses its flexibility and its impact resistance becomes poor.
'There is also the problem that it cannot be used in cold regions.

On the other hand, olefin 11 resin film does not contain plasticizers and has a stable chemical structure, so its light transmittance hardly changes even during long-term use, and even when incinerated, it does not produce harmful substances. Although it is superior to polyvinyl chloride film in that it is free of heat, is inexpensive, and easy to process, it is inferior to polyvinyl chloride film in terms of weather resistance. Therefore, although olefin resin films have the above-mentioned advantages, they have not been widely used as house coating films.

As a coating film with improved weather resistance of a polyolefin resin film, as seen in JP-A No. 56-41254, a specific hinged amine light stabilizer and an inorganic fine powder having a specific polarity are added to a polyolefin VT resin. There is a polyolefin film made of polyolefin, but in this case, although the weather resistance is improved to some extent, the transparency and physical strength of the film are severely reduced. For example, JP-A No. 6
As seen in JP-A No. 0-120732, JP-A-60-199039, and JP-A-61-31466, a specific hinged amine light stabilizer and a specific set of antioxidants are added to a polyolefin resin. Polyolefin resin compositions made of
As seen in Publication No. 2, a specific organic phosphate metal salt compound and a specific Hingood 7) are added to polyolefin resin.
There are polyolefin resin compositions made by adding a polyolefin antioxidant, but in these methods, the diffusion rate of the antioxidant in the polyolefin resin is high, and it migrates to the film surface in a short period of time and is exposed to wind and rain. It washes away from the surface and cannot maintain its weather resistance for a long period of time. Furthermore, even if the concentration of antioxidant added to the film is increased for the purpose of maintaining weather resistance for a long period of time, only a large amount will migrate to the film surface, and the amount of antioxidant remaining inside the film will hardly increase, resulting in no increase in weather resistance. Unable to retain sex for long periods of time. Moreover, increasing the concentration of the antioxidant added causes disadvantages in that the surface appearance of the film deteriorates and the transparency decreases.

Particularly during high temperatures in the summer, the amount of sunlight increases, which not only accelerates the photodegradation reaction of the film, but also increases the rate at which antioxidants migrate to the film surface, and the combination of both accelerates the deterioration of the film. Therefore, it was extremely difficult to maintain long-term weather resistance during summer use.

[Problems to be Solved by 1 Ming] The present inventors have solved the above-mentioned olefin resin as an agricultural film! ff title 7? F, remove
As a result of extensive research in order to provide agricultural films with excellent weather resistance, transparency, abrasion resistance, dustproofness, and impact resistance at low prices, we have developed olefinic resins containing specific hydrotalcite compounds and Hingudoamine. By providing a coating layer made of an olefin resin on one or both sides of a film made of a resin composition blended with a polyester compound, weather resistance, transparency, abrasion resistance, dustproofness, and WJ resistance are extremely superior compared to conventional technologies. The inventors discovered that it was possible to obtain a film that has both high impact resistance and completed the present invention.

[Means for solving the problem] The gist of the present invention is that 100 parts by weight of olefin resin is
~25 parts by weight of the following general formula % formula % where M represents an alkaline earth metal and Zn, and X represents n
It shows the valence of 7 ions. Also. and C/11 satisfies the conditions of the following formula.

0 〈〈〈0.5 0 ≦ 1 ≦ 2 and a hydrotalcite compound represented by 0.1 to 5
The present invention relates to an agricultural multilayer N film characterized in that a coating layer made of an olefin resin is provided on one or both sides of a base layer made of a composition containing a heavy weight hindered amine compound.

The present invention will be explained in more detail below.

In the present invention, the olefin-based 0 (fat) used in the base layer is a prefectural polymer of α-olefin, a copolymer with a different at-form mainly composed of α-olefin, such as polyethylene, polypropylene, ethylene, etc. -propylene co-1 combination, ethylene-7'?7 co-111 combination,
Examples include ethylene-4-methyl-1-pentene copolymer, ethylene-vinyl acetate copolymer, and ethylene-acrylic acid copolymer. Among these, low-density polyethylene and ethylene-α-olefin copolymers with a density of 0.910 to 0.935 g/c1113 and ethylene-vinyl acetate copolymers with a vinyl acetate content of 30 fold or less are transparent. It is preferable as an agricultural film from the viewpoints of weatherability, weather resistance, and price.

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 preferred in terms of transparency, flexibility, weather resistance, etc.

The olefin resin used for the coating layer in the present invention belongs to the same category as the olefin resin used for the base layer described above, but among these, M resin is preferred because it has particularly good friction resistance. For example, in the case of polyethylene, the density is 0.9 j OFl/cm' or more, 935 g
/ cm' or less, melt index is O, 1g710
Preferably, polyethylene or ethylene-α-olefin copolymer with a molecular weight of 4 g/10 min or more, and a M degree of 0.
If it is less than 910 g/cm", it is unfavorable in terms of heat resistance,
If the density is 0.935 g/cl*3 or more, it is not preferable in terms of transparency. Also, the melt index is 0. Ig/10
If it is less than 4 g/10 minutes, it is unfavorable from the viewpoint of workability, and if it is more than 4 g/10 min, it is unfavorable from the viewpoint of friction characteristics and strength.

Further, in the case of an ethylene-vinyl acetate copolymer, the vinyl acetate content is more preferably 15% by weight or less.

Melt index is 0.1g/less than 10% by weight
4g for 10 minutes or more / 10 minutes or less, preferably 0.1g
/10 minutes or more and 1.5 Fl/10 minutes or less is preferable. If the vinyl acetate content is 15% by weight or more, it is unfavorable in terms of heat resistance, and the melt index is 0.1g/10%.
If it is less than 4 g/10 minutes, it is unfavorable in terms of workability, and if it is more than 4 g/10 minutes, it is unfavorable in terms of friction characteristics and strength.

The hydrotalcite compounds used in the present invention have the general formula %, where M represents an alkaline earth metal and Zn.
X represents an n-valent 7-ion.

7 and gloss satisfy the conditions of the following formula.

Oku Eku 0.5 0≦■≦2 It is a hydrotalcite compound represented by

In the above formula, the n-valent anion represented by X'c is Cl-1Br-1 -1NO, -5Cto 4
-1so,”, CO32-1SiO3'-1HP O,
'-1HB 0.2-1P o, Co, Fe(CN)
, Co, Fe(CN)='-1, and the like can be exemplified.

The hydrotalcite compound used in the agricultural laminated film of the present invention is not particularly limited, but in order to particularly improve parallel light #iI transmittance, film processability, physical properties, etc. Ratio 1.47 to 1.52 Average secondary particle diameter 5μ or less, BET specific surface area 30m
/g or less is preferable.

In the present invention, it is preferable to use the high Y rotary cylindrical compound after treatment with a surface treatment agent. By surface treatment, the dispersibility or affinity for the olefin resin is improved, and the processing suitability, physical properties, and parallel light transmittance of the film are also improved.

Examples of such surface treatment agents include, for example, sodium laurate, potassium uronate, sodium oleate, potassium oleate, sodium stearate, potassium stearate, sodium palmitate, potassium palmitate, and sorghum caprate. Alkali metal salts of higher fatty acids such as , potassium caprate, sodium myristate, potassium myristate, sodium sulfate, potassium sulfate, etc.; lauric acid,
Higher fatty acids such as palmitic acid, oleic acid, stearic acid, capric acid, myristic acid, linoleic acid, etc.;
Isopropyl triisostearoyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, tetraisopropyl bis(dioctyl phosphite) titanate, vinyl triethoxysilane, methacrylic acid dipropyl trimethoxysilane, oxypropyl trimethoxysilane Coupling agents such as; and the like can be exemplified.

Surface treatment with these surface treatment agents can be carried out, for example, by adding an aqueous solution of alkali metal salts of higher fatty acids to a suspension of hydrotalcites in hot water, or by adding hydrotalcite powder to a suspension of hydrotalcites in hot water while stirring. This can be carried out by dropping a melt of a higher fatty acid or a diluted solution of a coupling agent while stirring with a mixer such as a Henschel mixer. The amount of these surface treating agents can be selected and changed as appropriate, but is suitably about 1 to about 10% by weight based on 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.

In addition, the proportion of the hydrotalcite compound in the olefin resin serving as the base layer is generally 1 to 25 parts by weight, preferably 2 to 2 parts by weight, per 100 parts by weight of olefin P and resin.
0 parts by weight is more preferred. If the amount of the blend is less than 1 part by weight, the effect of improving the heat retention of the resulting film will not be very noticeable, and if the amount exceeds 25 parts by weight, the strength of the resulting film will decrease, which is not preferred.

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

Structural formulas of the hinged amine compounds in the present invention include the following.

2.2. G,G-tetramethylpiperidine (11) 4-stearyloxy-2,2,6゜6
-Tetramethylpiperidine (12) 4-benzyloxy-2,2,G,6-
Tetramethylpiperidine (13) 4'-(7, Nylcarbamoyloxy)-
2,2,G,G-tetramethylpiperidine (14) 4-
(p) -2,2,6,(3-
Tetramethylpiperidine (15) Bis(2,2,13
,6-tetramethyl-4-piperidyl)tere7talate (16) ) lis(2,2,6,G-tetramethyl-
4-piperidine) phosphite (17) 1,3,8-triaza-7,7,9.9
-Tetramethyl 2,4-dioxo-spiro c4*sl decane (18) (2,2,G,G-tetramethylpiperidine)
-4-spiro-2"-(6',6"-dimethylpiperidine)-4'-spiro5,"-hinguntoin These hindered amine compounds are blended at 1 mB or in combination of 2 fl or more.

The blending amount shall be selected within the range of 0.1 to 5 parts by weight per 100 parts by weight of the polyolefin resin. If the blending amount is less than 0.1 parts by weight, the weather resistance will not improve even if the hydrotalcium compound is used in combination. On the other hand, if the amount of the hindered amine compound is more than 5 parts by weight, the bloom (spraying out onto the surface of the film) after film formation will be poor, and the effect of improving weather resistance will be small.

Further, in the laminated film according to the present invention, the following compounding agents can be used in both the base layer and the coating layer as necessary.

That is, plasticizers, organic phosphate esters, epoxy compounds, heat stabilizers, chelator-1 lubricants, antifogging agents ('# surfactants), ultraviolet absorbers, antioxidants, stabilization aids, antistatic agents, These include anti-mold agents, anti-algae agents, and coloring agents. Also received F
A hindered amine compound can also be used for the waste.

As the plasticizer that can be used in the present invention, those commonly used for plasticizing such as polyvinyl chloride and olefin-vinyl alcohol combination can be used.

Particularly preferred are molecular compounds such as glycerin, ethylene glycol, triethylene glycol, and sorbitol.
The following low molecular weight polyhydric alcohols. These also exhibit excellent effects in imparting antifogging properties, which are essential for agricultural films. In addition, examples of plasticizers other than these alcohol-based ones include heptatalic acid esters such as diptyl heptalate, heptyl heptalate, di-2-ethylhexyl heptalate, butyl benyl heptalate, butyl lauryl heptatalate, 7-talic acid mixed group esters such as methyl oleyl 7-talate, aliphatic dibasic acid esters such as dioctyl 7-dibate, diisodecyl adipate, dioctyl azelate, glycol esters such as diethylene glycol benzoate, butyl oleate, acetyl Examples include fatty acid esters such as methyl ricinoleate.

Examples of organic phosphoric acid esters that can be used include trifrenyl phosphate (TCPL)
(TXP), dixylenilmo/cresyl phosphate,
In addition to monosilenyl nocresyl phos-7ate, phosphoric acid esters having at least one ethyl 7-ethyl group in the molecule can be mentioned.

Furthermore, it is also possible to use a phosphate ester produced by fM using a mixed alcohol whose raw material is xylenol, ethylphenol, and cresol as main components and using these alcohols in a specific ratio.

Epoxy compounds include, for example, epoxidized oilseed oil, evoquinated linseed oil, epoxidized fish oil, epoxidized tall oil fatty acid ester, epoxidized raw tallow oil, epoxidized polybutadiene, methyl epoxy stearate, butyl epoxy stearate, and epoxy stearic acid. -2-ethylhexyl, stearyl epoxy stearate, tris(
Epoxyprobyl) isocyanurate, epoxidized castor oil, epoxidized sour 7 laurel oil, epoxidized linseed oil fatty acid butyl, 3-(2-cymo/xy)-1゜2-epoxyprobyl, bisphenol-A-diglycidyl ether , vinylcyclohexene dieboxide, a polycondensate of 2,2-bis(4-hydroxy7enyl)propane and epichlorohydrin, and the like.

Examples of the carboxylic acids 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, and ricinic acid. Ruic acid,
oleic acid, oleic acid, neotecanoic acid, oleic acid, stearic acid, isodecanoic acid, isostearic acid,
12-hydroxystearic acid, 12-ketostearic acid, chlorostearic acid, phenylstearic acid, arachidic acid, behenic acid, erucic acid, brassic acid and similar acids, as well as tallow fatty acids, coconut oil fatty acids, tung oil fatty acids, soybean oil fatty acids and Naturally occurring mixtures of the above acids such as cottonseed oil fatty acids, benzoic acid, chlorobenzoic acid, toluic acid, salicylic acid, pt-butylbenzoic acid, 5-t-octylsalicylic acid, naphthenic acid, doosilylic acid, ethylbenzoic acid. acid, isopropylbenzoic acid, di-t-butylbenzoic acid, bromobenzoic acid, monobutyl maleate, monodecyl heptatarate, cyclohexanecarboxylic acid, and the like.

In addition, phenols are also useful as organic acids.
Phenol, cresol, dimethyl 7 ether, dimethyl 7 ether, isopropylphenol, cyclohexylphenol, t-butyl 7 ether, phenylphenol, nonylphenol, dinonylphenol, methyl-t-butylphenol, tetramethyl 7 ether, poly(nopenta)isopropyl 7 ether, diisopropyl-so-cresol, butylphenol, in7milphenol, inoctylphenol, 2-ethylhexylphenol, nonyl 7ethyl, decyl 7ethyl /
-ol, t-dodecyl 7enol, t-octylphenol, octylphenol, isohexyl 7er/-l, octadecyl 7er/-l, diisobutylphenol, methylpropyl 7enol, methyl-t-octyl 7er/-
Examples thereof include di-t-/nyl-7-el, not-t-dodecyl-7-el, and the like.

Metal components include zinc, Group 1a metals such as lithium, sodium, and potassium, and Group 1a metals such as barium, calcium, magnesium, and strontium.

Organic phosphite compounds used in the present invention as chelators include diphenyldecyl phosphite, triphenyl phosphite, tris-nonyl 7enyl phosphite, tridecyl phosphite, tris(2-
ethylhexyl) phosphite, tributyl phosphite, tris(dinonylphenyl) phosphite, trilauryltrithiophosphite, trilauryl phosphite, bis(neopentyl gelcole)-1,4-cyclohexane dimethyl phosphite, distearylbentaerythritol diphos-7-ite, diisodecylpentaerythritol diphosphite, tris(lauryl-2-
thioethyl) phosphite, tetratridecyl-1,1
,3-)Lis(2゛-methyl-5゛-tert-butyl-4゛
-oxyphenyl)butane diphosphite, tetra(C
32~CIS mixed alkyl) 4'-isopropylidene diphenyl diphosphite, tris(4-oxy-2
,5-cy 3)+luphenyl)phosphite),)I
Js(4-oxy-3,5-cy-tert-butyl-7enyl)
Phosphite, 2-ethylhexyldi7enylphos7ite, tris(mono-, di-mediated nonylphenyl)phosphite, hydrogenated-4,4゛-isopropylidene di7e/-
polyphos 7-ite, diphenyl bis[4,4'-lobylidene bis(2-tert-butyl-5-methyl 7-ite/
-l)] thionoethanol diphosphite, bis(octylphenyl) bis[4,4''-n-butylidenebis(2-tert-butyl-5-methyl7ethyl)]-1,6
-hexanediol diphosphite, phenyl-4,4
゛-isopropylidene diphenol pentaerythritol diphosphite, 7enyl diisodecyl phosphite, tetratridecyl-4,4'-n-butylidene bis(2-tert-butyl-5-methylphenol) diphosphite, tris(2, 4-di-tert-butylphenyl) phosphite, tristearyl phosphite, octyl diphenyl phosphite, nophenyl tridecyl phosphite, phenyl di(tridecyl) phosphite, tris(
2-cyclohexylphenyl) phosphite, ditridecyl di(2-cyclohexylphenyl) hydrogenated bisphenol A diphosphite, di(2,4-di PJS
3-butyl 7enyl) cyclohexyl phosphite, 2,
4-No-31 tylphenyl diisodecyl phosphite, tris(butoxyethoxyethyl) phosphite,
Nophenylacedophosphite, bis(2-cyclohexylphenyl)acidophosphite, bis(2,4-)
-t-butyl7enyl) acid phosphite, bis(nonylphenyl) acid phosphite, dibenzyl acid phosphite, and the like.

Examples of lubricants that can be used include fatty acid lubricants such as stearic acid, valmitic acid, and myristic acid; stearamide, palmitic acid amide, methylene bisstearamide,
Fatty acid amide lubricants such as ethylene bisstearamide;
Examples include ester lubricants such as butyl stearate and butyl palmitate, polyethylene wax, and liquid paraffin.

As the antifogging agent used in the present invention, nonionic, anionic, and cationic surfactants are used, such as polyol dialkylene ether, partial ester of polyhydric alcohol, and fullylene oxide of polyhydric alcohol. Examples include partial esters of adducts, alkali metal salts of higher alcohol sulfates, alkylaryl sulfonates, quaternary ammonium salts, and aliphatic amine derivatives. Specifically, polyoxyethylene lauryl ether, polyoxystearyl ether, polyoxy/nylphenyl 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,
Sorbitannostearate, diglycerin monooleate, triglycerin diolate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium butylnaphthalene sulfonate, cetyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride, dodecylamine hydrochloride, lauryl laurate Examples include basic pyridinium salts of amidoethyl phosphate, triethylcetylammonium ioguide, oleylamitsunoethylamine hydrochloride, and dodecylpyridinium sulfate.

As an ultraviolet absorber, for example, 2-hydroxy-4-
Methoxybenzo7ene/2-hydroxy-4-n-octyloxybenzo7ene, 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-methoxybenzobenzophenone, 2.2
Benzophenone ultraviolet absorbers such as '-nohydroxy-4゜4゛-di-methoxy-5-sulfobenzo7ene, 2.2', 4.4'-tetrahydroxybenzo7ene: 2-(2'-Hydroxy-5'-methylphenyl)benzotriazole,2-(2'-hydroxy-5
'Lert -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'-jjert7milphenyl)benzotriazole, 2-(2'-hydroxy-3'
゛.

5'-not-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',S'-dimethylphenyl)-5-methoxybenzotriazole, 2-(
2'-n-octadecyloxy-3',5''-tsumethylphenyl)-5-methylbenztriazole, 2-(2
'-Hydroxy-5'-methoxy7enyl)benzotriazole, 2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-methoxy7enyl)- 5-methylbenzotriazole, 2-(2'-hydroxy-5'-methylphenyl)-5,6-dichlorobenzotriazole, 2-(
2'-hydroxy-5' tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3').

5'-not-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'-not-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'
tert-butyl-5'-methylphenyl)-5-
Chlorobenztriazole, 2-(2'-hydroxy-3'-methylphenyl)-5-butoxycarbonylbenzotriazole, 2-(2'-hydroxy-4'', 5'
-5-methylphenyl)-5-butoxycarbonylbenzotriazole, 2-(2'-hydroxy)-5-ethoxycarbonylbenzotriazole, 2-(2'-7cetoxy5'-methyl7enyl)benzotriazole, 2
-(2'-hydroxy-5'-methyl7enyl)-5-
Ethylsulfonebenzotriazole, 2-(2'-hydroxy-3',5'-dimethyl7enyl)-5-ethylsulfonebenztriazole2-(2'-hydroxy-51-phenylphenyl)benzotriazole, 2
Benzotriazole UV absorbers such as -(2'-hydroxy-5'-7minophenyl)benzotriazole; 7enyl salicylate, p-tert-butyl 7enyl salicylate, p-methylphenyl salicylate,
Examples include salicylic acid ester ultraviolet absorbers such as p-octylphenyl salicylate.

Examples of the 7ヱ/-ol antioxidant include 2.

6-C-tert-butyl-p-cresol, stearyl-(
3.5-cymethyl-4-hydroxylebenzyl)thioglyflate, stearyl-β-(4-hydroxy-3,
5-di-tert-butylphenyl)propionate, distearyl-3,5-cyf53butyl-4-hydroxybennorphosphonate, 2.

4,6-)ris(3',5'-G-tpJ3 butyl-4
゛-Hydroxybennorthio)-1.3.5-) riazine, distearyl (4-hydroxy-3-methyl-5-
43butyl) benzyl malonate, 2,2-methylenebis(4-methyl-〇-tert-butyl 7-ethyl), 4,
4'-methylenebis(2,6-c-tert-butylphenol), 2,2'-methylenebis[6-(1-methylcyclohexyl) p-cresol], bis[3,5-bis(
4-Hydroxy-3-PIS3butylphenyl)butyric acid 1 glycol ester, 4,4°-butylidenebis(6-tert-butyl-transcresol), 2,2°
-ethylidene bis(4゜6-no-tert-butyl-7 ethyl), 2,2゛-ethylidene bis(4-tert-butyl-6-
f:IIJ3butyl7ethyl), 1.1.3-)lis(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-)lis(
2゜6-nomethyl-3-hydroxy-4-31styl)
Benzyl isocyanurate, 1,3.5-)lis(3°5-no-tert-butyl-4-hydroxybenzyl)-2,
4,6-)limethylbenzene, 2,6-7enyl4
-octadecyloxyphenol, tetrakis[methylene-3-(3,5-cy-tert-butyl-4-hydroxyphenyl)propionate]methane, 1.3.5-)lis(
3,5-tert-butyl-4-hydroxybennol)incyanuride), 1,3°5-tris[(3,5-]-
]@3butyl-4-human axyphenylphyllobionyloxyethyl]in cyanurate, 2-octylthio-
7 such as 4,6-(4-hydroxy-3,5-nor-tert-butyl) 717
Carbonic acid oligoester of 2/-ols and 4,4'-butylidene bis(2-tert-butyl-5-methylphenol) (
For example, polyhydric phenol carbonate oligoesters having a polymerization degree of 2, 3, 4, 5, 6, 7, 8, 9.10, etc.) can be mentioned.

Examples of sulfur-based antioxidants include dialkylthionopropionates such as dilauryl, similystyl, and distearyl, and polyhydric alcohols of alkylthiopropionic acids such as butyl, octyl, lauryl, and stearyl (e.g., glycerin). , trimethylolethane, trimethylolpropane, pentaerythritol, trishydroxyethyl isocyanurate) (for example, pentaerythritol-lutetralaurylthiopropionate).

Examples of the stabilizing aid used in the present invention include 2,
6-di-7-butyl-p-cresol, dilauryl thiodipropionate, diphenylthiourea, 7-ethyl indole, 1,000 osyglycol bis(aminocrotonate)
, pentaerythritol, tris(hydroxyethyl)
Isocyanurate, sorbitol, mannitol, anilinodithiotriazine, melamine, nopentaerythritol adibate, pt-butylbenzoic acid, dehydroacetic acid, zinc dehydroacetate, nonylphenoxypolyethoxyphosphoric acid, benzoic acid, cinnamic acid, dibenzoylmethane , stearoylbenzoylmethane, benzoylpenta/ylmethane, etc.

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

Compounds that can be used as fungicides and algaecides include 2.
,4,5.6-titrachloroiso7talonitrile, 10
．． 10'-oxybis7e/xialsine, 2-(4-
thiazolyl)-benzimiguzole, N(fluorodichloromethylthio)7talimide, N-dimethyl-N'-
Phenyl-(Nゝ-70 rhodichloromethylthio)sulfamide, paraoxy rest! acid ester, 5-bromo-
Examples include 5-nitro-1,3-dioxane, 2.3.5.6-tetrachloro-4-methylsulfonylpyridine, 3-methyl-4-chlorophenol, N(tetrachloroethylthio)7talimide, tributyltin laurate, etc. be able to.

Examples of the coloring agent that can be used include 7-talocyanine blue, 7-talocyanine green, Hansa yellow, alizarin lake, titanium oxide, zinc white, permanent red, quinacridone, and carbon black.

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

The amount of the various resin additives mentioned above should be within a range that does not deteriorate the properties of the film, usually 10% of the base polyolefin resin.
It can be selected within a range of 5 parts by weight or less relative to 0 parts by weight.

When producing the agricultural film of the present invention, the olefin Ml used for the base layer (if the hydrotalcite compounds and hindered amine compounds and other resin additives are added to the fat, the necessary amounts of each are weighed, Any conventional compounding machine or mixer such as a ribbon blender, Banbury mixer, super mixer, extruder, etc. may be used.

The resin composition thus obtained may be formed into a film by a method known per se, for example, a conventional molding method such as in-7 resin processing, calendar processing, T-shaped processing, etc.

A method of providing a coating layer made of olefin Mflf resin on one or both sides of a base layer made of an olefin resin containing a hydrotalcite compound and a hindered amine compound is to form respective films and dry lamination or heat lamination. A method of forming a laminated film, a method of extruding and laminating a coating layer made of an olefin resin on a base layer of an olefin resin film containing a hydrotalcite compound and a hindered amine compound, a method of simultaneously forming a laminated film using a multilayer coextrusion method, etc. Existing technology can be used (in particular, multilayer coextrusion is preferred in terms of ease of molding, interlayer adhesion, transparency, and cost of the resulting film.Furthermore, for agricultural applications, wide film is preferred, so the multi-layer in-7 resin processing method is desirable.In addition, when providing a coating layer on both sides of the base layer, one side may be coated with a different type of resin, but considering the use of extruder helmets, etc. The same type of resin is sufficient for this purpose.

In addition, the thickness of both the base layer and the coating layer is determined depending on the end use and purpose, so it is not specified in part, but the base layer depends on the required level of heat retention and the proportion of hydrotalcite compounds in the resin. It depends, but usually 20μ-~200μ
The coating layer may have a thickness that reduces the external haze of the base layer and exhibits abrasion resistance, and is usually 5 μl to 5 μl.
A thickness of about 0 μm is sufficient.

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

Regarding the thickness of the laminated film, 30 μm to 300 μl of ll[I is preferable from the viewpoint of strength and cost, and 50 μm to 200 μl is particularly preferable.

In addition, each physical property test in Examples and Comparative Examples was conducted as follows.

Weather resistance test: Each film was exposed for 24 months starting in September 1960 on a window frame-shaped airtight test stand facing south and tilted at 45 degrees to the ground (location: Nagoya City, Aichi Prefecture). A part of the film was removed from the exposure test stand, and the appearance and 1 elongation (JIS
K-6783> was evaluated. The evaluation criteria were as follows. ,○...There is no change in appearance and the remaining elongation rate is 80% or more.

○X: No change in appearance, remaining elongation rate is 79-60%
Those within the range of.

Δ: Appearance changes such as cracks and tears are partially observed, and the residual elongation rate is in the range of 79 to 60%.

ΔX: Significant changes in appearance such as cracks and tears are observed.
The remaining elongation rate is in the range of 59 to 40%.

×: V cracks are observed over the entire surface or the remaining elongation is less than 40%.

Note that the residual elongation rate was calculated using the following formula.

Dust-proofing test: The test film was installed in a test field in Shigun, Mie Prefecture, in a pipe house (FI1 mouth 311 depth 5mm, ridge height 1.5-1
Roof slope 30 degrees) was covered from September 1985 to 1986.
A 24-month extended exam was conducted until September 2015.

The film after the stretching test was collected, and the light transmittance at a wavelength of 555 millimicrons was measured using a spectrophotometer (manufactured by Hitachi, Ltd., 330
(type). The measurement results were displayed as follows.

◎...Light transmittance is 80% or more.

○... Light transmittance is in the range of 65 to 79%.

Δ... Light transmittance is in the range of 45 to 64%.

×...Light transmittance is less than 45%.

Transparency test: The parallel light transmittance of the film obtained in the present invention at a wavelength of 555 millimicrons was measured using a spectrophotometer (manufactured by Hitachi, Ltd., 330
(type), and the values are shown.

Abrasion resistance test: Using the U-F abrasion resistance test, attach the film test piece to the fixed side to avoid wrinkles by attaching paper #400 to the corresponding side (the side that moves left and right). The film was brought into contact with a fixed film surface and the number of times the film was rubbed until it broke was evaluated.

Note that the greater the number of tears, the better the abrasion resistance.

The values of the obtained film are shown in the table.

Impact resistance test: A sample piece with a thickness of 76 μm, a medium diameter of 10 cm, and a length of 10 cm was left in an atmosphere of -5°C for over 1 hour, and then its impact strength was measured using a non-etched film impact tester. , a 1772-inch spherical surface was used.

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

Example-1 Chemical composition Mfio consisting of an ethylene-vinyl acetate copolymer with a vinyl acetate content of 15% by weight (melt index 1.5 g/10 min, refractive index 1.495) and surface treatment with sodium stearate in advance , yAl. ,.

(OH)2(CO, ). , 3.・Average secondary particle size 0.3μ with 0.55820, BET specific surface area 12m”
/H hydrotalcite compound (R refractive index 1.50)
10 parts by weight, 5ANOL LS-770 (molecular weight 480°, 7 melting point 80''-90'CN, 0 parts by weight, manufactured by Sanjo Co., Ltd.) as an amine compound, glycerin monostearate as an antifogging agent and a dispersant. 0.5 parts by weight, 1.0 parts by weight of polyglycerin stearate, and 0.5 parts by weight of 2-hydroxy-4-octoxybenzophenone as a weathering aid.
After adding 2 parts by weight, the mixture was kneaded in a Banbury mixer for 5 minutes at a resin temperature of 130°C to 150°C, and then transferred to an extruder to produce granulated pellets.

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

By using a two-type three-layer in-seven resin molding method, the base layer is supplied with the above-mentioned filler mixed resin, and the coating layer is a high-pressure low-density polyethylene resin composition (density 0.924 g/cIm).
3. 100 parts by weight of polyethylene with a melt index of 1.3 g/10 minutes and 0.5 parts by weight of glycerin monostearate as an antifog agent b1 Polyglycerin stearate 1.
0 parts by weight, and 2-hydroxy-4- as a weathering aid
A transparent film having a three-layer sandwich structure in which each layer had a thickness of 50 μm for the base layer and 13 μm for each coating layer was obtained.

The results of measuring the transparency, abrasion resistance, weather resistance, dustproofness, and impact resistance of the obtained film are summarized in Table 2.

Example-2 The Hingodamine compound used for the base layer in Example-1 was manufactured by 7Deca-A, Inc. under the trade name MARK LA-
Example-1 except that it was replaced with 57 (melting point 60-140°C)
This process was repeated to obtain a transparent film.

Example 3 The Hingodamine compound used for the base layer in Example 1 was manufactured by Ciba Iggy under the trade name CHIMASSORB.
A transparent film was obtained by repeating Example 1, except that 944-molecular weight (molecular weight: 2,500 to 4,000) was used.

Example-4 Instead of the high-pressure low-density polyethylene resin used for the coating layer in Example-1, an ethylene-vinyl acetate copolymer with a vinyl acetate content of 5% by weight, a density of 0, and a density of 92 g/am was used.
Example 1 was repeated except that the melt index was changed to 2 g/10 min) to obtain a transparent film.

Example-5 In Example-1, high-pressure low-density polyethylene (density 0.924 g/cm
Example 1 was repeated except that the melt index was changed to 1.3 g/10 min) to obtain a transparent film.

Example-6 The base layer hydrotalcite compound used in Example-1 had a chemical composition of Mgo, ssA 10.34 (OH).
Example 1 was repeated, except that hydrotalcites of 0.52820 (average secondary particle size 0.4μ, BET specific surface area 1511”/g) were used to prepare a transparent film. I got it.

Comparative Example 1 A chemical 11f4. rlt
MRll, TA 10.3(OH)t(COi)o,
Is ・0, 55H20 (average secondary particle size 0.3 μm
, BETJjS surface area 12 m27 g, refractive index 1.5
10 parts by weight of the hydrotalcite compound of 0), 0.5 parts by weight of glycerin monostearate and 1.0 parts by weight of polyglycerin stearate as an antifogging agent and dispersant, and 2-hydroxy-4-oct as a weathering aid. A film was obtained by repeating Example 1, except that only 0.2 parts by weight of dibenzophenone was added. The resulting film had slightly poor transparency.

Comparative Example 2 A single layer film having a thickness of 76 μm was obtained using the filler mixed resin used for the base layer in Example 1 by a single layer in 7 resin 1 in molding method. The resulting film had slightly poor transparency.

"Effects of the Invention" As is clear from the above Examples and Comparative Examples, the film according to the present invention, that is, the olefin-based maw containing a specific hydrotalcite compound and a hinged amine compound, is coated with another olefin-based resin layer. The laminated film has exceptional weather resistance, and has excellent transparency (parallel light transmittance), abrasion resistance, dustproofness, and impact resistance, making it extremely suitable as an agricultural film. I understand.

Note that a film formed by laminating an olefin resin layer containing only a specific hydrotalcite compound with another olefin resin layer can achieve abrasion resistance, but weather resistance and
Transparency is insufficient, and dust resistance and impact resistance are also poor. Moreover, a single layer film of an olefin resin containing a specific hydrotalcite compound and a hinged amine compound has insufficient transparency and is inferior in other physical properties.

Claims (1)

[Claims] 1) 1 to 25 parts by weight of the following general formula M_(_1_-_x_)・Alx・(OH)_2・Xx to 100 parts by weight of the olefin resin.
_/_n·mH_2O In the formula, M represents an alkaline earth metal and Zn, and X represents an n-valent anion. Moreover, and m satisfy the conditions of the following formula. A hydrotalcite compound represented by 0<x<0.5 0≦m≦2 and 0.1 to 5
1. A laminated film for agricultural use, characterized in that a coating layer made of an olefin resin is provided on one or both sides of a base layer made of a composition blended with a hindered amine compound in an amount by weight. 2) The agricultural laminate according to claim 1, wherein the olefin resin is an ethylene-vinyl acetate copolymer, a low-density polyethylene having a density of 0.935 g/cm^3 or less, or an ethylene-α-olefin copolymer. film. 3) The refractive index of the hydrotalcite compound is 1.47~
BE in the range of 1.52 and the average secondary particle size is 5 μm or less
The laminated agricultural film according to claim 1, having a T specific surface area of 30 m^2/g or less. 4) The density of the olefin resin used for the coating layer is 0.9
Polyethylene or ethylene-α-olefin copolymer with a melt index of 15 g/cm^3 or more and 0.935 g/cm^3 or less and a melt index of 0.1 g/10 minutes or more and 4 g/10 minutes or less, or a melt index of 0.1 g/10
The agricultural laminated film according to claim 1, which is an ethylene-vinyl acetate copolymer having a vinyl acetate content of 15% by weight or less at a rate of 4 g/10 min or more.