JP2014018109A - Agricultural multilayered film - Google Patents

Abstract

The present invention provides an agricultural multi-layer film that has various antifogging properties under acidic conditions such as acid rain and agricultural chemicals and a decrease in the anti-fogging coating film adhesion strength after long-term stretching.
An agricultural polyolefin multilayer film having at least an outer layer, an intermediate layer, and an inner layer, and a coating film layer made of an antifogging agent composition provided on the surface of a base film containing a polyolefin resin. Agricultural use comprising at least one compound having a ring structure and a molecular weight of 1000 or more in an intermediate layer, wherein the antifogging agent composition is mainly composed of a synthetic resin binder and an inorganic colloidal sol. Multilayer film.
[Selection figure] None

Description

  The present invention relates to a multilayer film for agriculture that has little deterioration in antifogging properties under acidic conditions such as acid rain and agricultural chemicals, and adhesion strength of the antifogging coating film after long-term stretching.

  In recent years, semi-forcing or suppressing cultivation of agricultural crops to increase their marketability and productivity, agricultural vinyl chloride film (hereinafter referred to as agricultural bi), polyethylene, ethylene-vinyl acetate copolymer, and polyolefin So-called house cultivation and tunnel cultivation are actively carried out to grow useful plants under the covering with agricultural covering materials such as agricultural polyolefin-based resin films (hereinafter referred to as agricultural poly and agricultural vinegar) mainly composed of resin. Yes. Among them, agricultural polyolefin-based resin film mainly composed of polyolefin-based resin is light because its density is smaller than that of vinyl chloride resin, and generates little toxic gas even when incinerated. Wide films that do not require adhesive processing can be provided at low cost, and are being actively used.

  Such agricultural houses are getting larger year by year, and the film expansion work for covering the house with a film requires a lot of manpower. On the other hand, the number of farmers is declining year by year and aging is progressing, and it is not easy to secure manpower for annual expansion work. In view of such a situation, the film to be spread in the house is a film that is easy to stretch and has a long use period until re-covering as much as possible, in other words, has a long life of 2 years or more and can maintain the initial performance over a long period of time. There is a need to develop high performance agricultural films. In response to such demands, the film has a performance that should be maintained for a long period of time, depending on its application, for example, various performances such as anti-fogging properties, weather resistance, and agrochemical resistance after long-term stretching. Is required. Conventionally, in order to impart these performances to molded articles, resin compositions containing various additives and anti-fogging coatings applied to them have been proposed.

  These agricultural films, especially agricultural polyolefin resin films, have a hydrophobic surface, so that the film surface may become cloudy depending on conditions such as temperature and humidity. When the growth is slowed or the water droplets generated by the collection of cloudy fine water droplets fall on the cultivated plant, the buds are damaged or cause disease.

  In order to eliminate such problems, it is known that anti-fogging properties should be imparted to the surface of agricultural films such as polyolefin resins. Various methods have been proposed for kneading and mixing such hydrophilic substances, or for forming a film and then applying a mixture of, for example, silica or alumina and a surfactant to the surface.

  However, in the former method, the hydrophilic substance kneaded in the resin is blown out and coordinated on the film surface to impart antifogging properties to the film. However, the antifogging property disappears within a short period of time. On the other hand, in the latter method, especially the adhesion between the polyolefin resin film and the above mixture is poor, so the coating film that is formed will fall off over time.

  As another method for imparting antifogging properties, it has also been proposed to provide an antifogging coating mainly composed of an inorganic colloidal sol such as acrylic and colloidal silica after film formation. However, the conventionally proposed combination of an anti-fogging coating and a base film is exposed to the outside air for a long period of time, and agricultural films exposed to acidic conditions such as acid rain and agricultural chemicals are used for ventilation in the house. In addition, the antifogging coating film may be peeled off while the film is wound around the pipe and wound up or down, resulting in a problem that various antifogging performances are lowered. In particular, when exposed to acidic conditions such as acid rain and agricultural chemicals, there is a problem that the surface of the anti-fogging coating film is cracked, the coating film and the base film are easily peeled off, and the anti-fogging durability is also reduced. there were.

  In this way, not only during normal use but also in an environment exposed to acidic conditions such as acid rain and agricultural chemicals, the antifogging coating surface is difficult to crack, and the durability of the antifogging performance and the adhesion of the antifogging coating It was difficult to obtain a film having good properties, durability and pesticide resistance.

  On the other hand, resin compositions containing hindered amine compounds as weathering agents in the base films of these agricultural films are widely used. As such a compound, for example, a hindered amine having two or more piperidine rings (one which is an H-group instead of the R1-O- group in the formula (1) of the present application) in a molecule and having a molecular weight of 500 or more. The system weathering agent can be mentioned. Already, as disclosed in, for example, JP-A-59-86645 and JP-A-2-167350, a hindered amine-based weathering agent can be added to a resin in a small amount to improve the weather resistance of the polyolefin-based resin. It is preferably used because it is remarkably improved, its effect is maintained for a long time, and changes in gloss and color tone of the polyolefin resin film are remarkably suppressed. However, molded articles obtained from such hindered amine-based weathering agent-containing resin compositions are significantly reduced in their effects when used, for example, under conditions exposed to acid rain and pesticides, and are required to have acid resistance and pesticide resistance. However, it could not be used satisfactorily for applications such as agricultural films.

  Various hindered amine compounds have been proposed for the purpose of improving acid resistance. For example, compounds such as those disclosed in JP-A-11-80569 can improve acid resistance by adding them. . However, various properties to be provided as an agricultural film, such as long-term weather resistance and anti-fogging durability except under acidic conditions, or concrete long-term adhesion of an anti-fogging coating film under acidic conditions, etc. It was lacking in description.

  Japanese Patent Application Laid-Open No. 2001-2842 proposes a resin composition to which an ethylene copolymer having a triazine ultraviolet absorber and a hindered amine in the side chain is added. However, even when an agricultural film was prepared with the addition amount described in the present application, the weather resistance under acidic conditions was still insufficient.

JP 59-86645 A JP-A-2-167350 Japanese Patent Laid-Open No. 11-80569 JP 2001-2842 A

  The object of the present invention is to provide excellent antifogging properties and long-term antifogging durability when an antifogging coating is applied to a base film, and under acidic conditions including agricultural chemicals and acid rain. Furthermore, the present invention relates to an agricultural film that exhibits various antifogging properties, long-term antifogging properties, weather resistance, and suppresses the bleeding out of the weathering agent and does not deteriorate long-term weatherability. When it is used for an industrial film, it is intended to provide a film for an agricultural covering material excellent in various antifogging properties, long-term antifogging durability, durability, and pesticide resistance.

  As a result of intensive studies, the present inventor has found an antifogging agent composition having a specific composition on a base film made of a polyolefin resin in which a light stabilizer having a specific structure and a specific ultraviolet absorber are blended. It discovered that the said subject could be solved by apply | coating, and completed this invention.

（Ｒ_１は、官能基または化合物（オリゴマー、ポリマーを含む）を表す。）
前記防曇剤組成物が、合成樹脂バインダーと無機質コロイドゾルを主成分とする、前記農業用多層フィルム、
［２］化合物Ａが、以下の式（２）で表される化合物を平均分子量３００以上の重合体に付加した付加体であることを特徴とする、［１］に記載の農業用ポリオレフィン系多層フィルム

（式中、ｎは１〜４の整数を表し、Ｒ_２及びＲ_３は同一でも異なっていてもよく、それぞれ水素原子又は任意の置換基を表す。）、
［３］化合物Ａが、以下の式（３）で表される化合物を平均分子量３００以上の重合体に付加した付加体であることを特徴とする、［１］又は［２］に記載の農業用ポリオレフィン系多層フィルム

（式中、ｎは１〜４の整数を表し、Ｘは−Ｏ−又は−ＮＨ−を表し、Ｒ_３は水素原子又は任意の置換基を表し、Ｒ_４は水素原子、炭素数１〜２０の脂肪族アシル基、脂肪族多価アシル基、芳香族アシル基又は芳香族多価アシル基を表す。）、
［４］化合物Ａが以下の式（４）で表される、［１］又は［２］に記載の農業用ポリオレフィン系多層フィルム

（式中、Ｒ_５は、水素原子又は任意の置換基を表し、Ｅは、炭素数６０〜１、０００、０００のアルキル基であり、かつ該アルキル基のアルキル鎖はアルキル置換基、芳香族置換基及び置換基としての酸性基を含有すること並びにアルケン単位及びヘテロ原子により中断されることが可能であり、ｎ'は、１〜１０００の整数である）、
［５］アルキル基Ｅが、ロウに由来する、［４］に記載の農業用ポリオレフィン系多層フィルム、
［６］化合物Ａが以下の式（５）で表される、［１］に記載の農業用ポリオレフィン系多層フィルム

（式中、ｍは１ないし１５の範囲で、
Ｒ_１は、Ｃ１〜Ｃ２０のアルキル基、またはシクロアルキル基を示し、
Ｒ_１２は、置換基を有してもよい、炭素原子数１〜１２のアルキレン基、アルケニレン基、シクロアルキレン基、もしくはアリーレン基を示し、
Ｂは、互いに独立して、Ｃｌ，−ＯＲ_１３、−Ｎ（Ｒ_１４）（Ｒ_１５）又は、−Ｙ−に式（１）の基が結合した基を示し、
ここで、
Ｒ_１３、Ｒ_１４、Ｒ_１５は、各々水素原子、置換基を有していてもよい、炭素原子数１〜１８のアルキル基、シクロアルキル基、アルケニル基、アリール基、又はアリールアルキル基を表し、
−Ｙ−は、−Ｏ−又は＞Ｎ−Ｒ_１６を表し、
Ｒ_１１又はＲ_１６は、各々、式（１）で示される基又はＲ_１３に与えられた定義の一つを表す。）、
［７］化合物Ａが、以下の式（６）で表される、［１］に記載の農業用ポリオレフィン系多層フィルム

（式中、Ｒ_６は、Ｃ１〜Ｃ１２のアルキル基を示し、
Ｚは、Ｃ１〜Ｃ４のアルキレン基、またはカルボニル基（Ｃ＝Ｏ）を示す。）、
［８］以下の式（７）で表れる化合物が少なくとも中間層に含まれている、［１］〜［７］のいずれか１に記載の農業用ポリオレフィン系多層フィルム

（式中、Ｒ_７〜Ｒ_１１は、それぞれ独立して、水素原子又は炭素数１〜１０のアルキル基を表す）、
［９］合成樹脂バインダーが、アクリル系樹脂及び／又はウレタン系樹脂であり、無機質コロイドゾルがコロイダルシリカ及び／又はコロイダルアルミナである、［１］〜［８］のいずれか１項に記載の農業用ポリオレフィン系多層フィルム、
［１０］基材フィルムが、エチレン（Ａ）と下記式（８）で表される環状アミノビニル化合物（Ｂ）との共重合体を含有する層を少なくとも１層有する、［１］〜［９］のいずれか１項に記載の農業用ポリオレフィン系多層フィルム

（式中、Ｒ_１２及びＲ_１３は、それぞれ独立して、水素原子又はメチル基を表し、Ｒ_１４は水素原子又は炭素数１〜４のアルキル基を表す。）、及び
［１１］前記基材フィルムがフェノール系酸化防止剤を実質的に含有しない、［１］〜［１０］のいずれか１項に記載の農業用ポリオレフィン系多層フィルムを、提供するものである。 That is, the present invention
[1] An agricultural polyolefin multilayer film having at least an outer layer, an intermediate layer, and an inner layer, and a coating film layer made of an antifogging agent composition provided on the surface of a substrate film containing a polyolefin resin. And
Including at least one compound A having at least one ring structure represented by the following formula (1) and having a molecular weight of 1000 or more in an intermediate layer;

(R ₁ represents a functional group or a compound (including an oligomer and a polymer).)
The anti-fogging agent composition is mainly composed of a synthetic resin binder and an inorganic colloid sol, the agricultural multilayer film,
[2] The agricultural polyolefin-based multilayer according to [1], wherein the compound A is an adduct obtained by adding a compound represented by the following formula (2) to a polymer having an average molecular weight of 300 or more. the film

(In the formula, n represents an integer of 1 to 4, R ₂ and R ₃ may be the same or different, and each represents a hydrogen atom or an arbitrary substituent).
[3] The agriculture according to [1] or [2], wherein the compound A is an adduct obtained by adding a compound represented by the following formula (3) to a polymer having an average molecular weight of 300 or more. Polyolefin multilayer film

(In the formula, n represents an integer of 1 to 4, X represents —O— or —NH—, R ₃ represents a hydrogen atom or an arbitrary substituent, and R ₄ represents a hydrogen atom, having 1 to 20 carbon atoms. An aliphatic acyl group, an aliphatic polyvalent acyl group, an aromatic acyl group or an aromatic polyvalent acyl group).
[4] The agricultural polyolefin-based multilayer film according to [1] or [2], wherein the compound A is represented by the following formula (4):

(In the formula, R ₅ represents a hydrogen atom or an arbitrary substituent, E is an alkyl group having 60 to 1,000,000 carbon atoms, and the alkyl chain of the alkyl group is an alkyl substituent or an aromatic group. Containing substituents and acidic groups as substituents, and can be interrupted by alkene units and heteroatoms, n ′ is an integer from 1 to 1000),
[5] The polyolefin-based multilayer film for agriculture according to [4], wherein the alkyl group E is derived from wax.
[6] The polyolefin multilayer film for agriculture according to [1], wherein the compound A is represented by the following formula (5):

(Where m is in the range of 1 to 15,
R ₁ represents a C1-C20 alkyl group or a cycloalkyl group;
R ₁₂ represents an optionally substituted alkylene group having 1 to 12 carbon atoms, alkenylene group, cycloalkylene group, or arylene group,
B represents, independently of each other, Cl, —OR ₁₃ , —N (R ₁₄ ) (R ₁₅ ) or a group in which the group of the formula (1) is bonded to —Y—;
here,
R ₁₃ , R ₁₄ , and R ₁₅ each represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an alkenyl group, an aryl group, or an arylalkyl group that may have a substituent. ,
-Y- represents -O- or> N-R ₁₆
R ₁₁ or R ₁₆ each represents a group represented by formula (1) or one of the definitions given for R ₁₃ . ),
[7] The agricultural polyolefin-based multilayer film according to [1], wherein the compound A is represented by the following formula (6):

(Wherein R ₆ represents a C1-C12 alkyl group,
Z represents a C1-C4 alkylene group or a carbonyl group (C = O). ),
[8] The agricultural polyolefin-based multilayer film according to any one of [1] to [7], wherein a compound represented by the following formula (7) is contained in at least the intermediate layer:

(Wherein R _{7 to} R ₁₁ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms),
[9] The agricultural resin according to any one of [1] to [8], wherein the synthetic resin binder is an acrylic resin and / or a urethane resin, and the inorganic colloid sol is colloidal silica and / or colloidal alumina. Polyolefin multilayer film,
[10] The base film has at least one layer containing a copolymer of ethylene (A) and a cyclic aminovinyl compound (B) represented by the following formula (8): [1] to [9 ] The agricultural-use polyolefin-type multilayer film of any one of

(Wherein R ₁₂ and R ₁₃ each independently represent a hydrogen atom or a methyl group, and R ₁₄ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), and [11] the substrate. The polyolefin multilayer film for agricultural use according to any one of [1] to [10], wherein the film does not substantially contain a phenolic antioxidant.

The agricultural multilayer film of the present invention maintains antifogging properties and various properties for a long time, and has good antifogging properties and antifogging coating film adhesion even under acidic conditions such as agricultural chemicals and acid rain. In addition to being excellent in weather resistance, it has a well-balanced performance to be provided as an agricultural film. In particular, when the hindered amine compound, ultraviolet absorber and / or ethylene / cyclic aminovinyl compound copolymer according to the present invention is used, the weather resistance, agricultural chemical resistance and bleed out resistance are excellent, and the effects of the present invention in such applications In addition, when the film is provided with an antifogging coating film, it is preferable because bleeding out is suppressed and adhesiveness with the substrate is not lowered.
The agricultural multilayer film of the present invention may be transparent, satin or semi-satin, and is an agricultural film for house, tunnel, mulching, bag hanging, etc. (so-called farm bi, farm poly, farm sacbi, farm PO, hard It can be suitably used for applications such as film.

Base Film The base film in the present invention has a laminated structure of three or more layers having at least an outer layer, an intermediate layer, and an inner layer. Here, the inner layer refers to a layer that becomes the inside of the house when the agricultural multilayer film of the present invention is spread on the house.

  In the present invention, the base film is preferably composed of a polyolefin resin. Examples of polyolefin resins include α-olefin homopolymers, copolymers of different monomers mainly containing α-olefins, polyunsaturated compounds such as α-olefins and conjugated dienes or nonconjugated dienes, Examples include copolymers with acrylic acid, methacrylic acid, vinyl acetate, and the like, such as high density, low density or linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene. Examples include -4-methyl-1-pentene copolymer, ethylene-vinyl acetate copolymer, and ethylene-acrylic acid copolymer. Among these, low density polyethylene having a density of 0.910 to 0.935, an ethylene-α-olefin copolymer, and an ethylene-vinyl acetate copolymer having a vinyl acetate content of 30% by weight or less have transparency and weather resistance. It is preferable as an agricultural film from the viewpoint of properties and price. In the present invention, an ethylene-α-olefin copolymer resin obtained by copolymerization with a metallocene catalyst can be used as at least one component of the polyolefin resin.

The ethylene-α-olefin copolymer resin obtained by copolymerization with a metallocene catalyst used in the present invention is usually referred to as metallocene polyethylene. Ethylene and 1-butene, 1-pentene, 1-hexene, 4 Examples thereof include copolymers with α-olefins having 4 to 10 carbon atoms, such as -methyl-1-pentene, 1-octene, 1-decene and the like. Among these, a copolymer with an α-olefin having 4 to 8 carbon atoms is more preferable from the viewpoint of resin strength and production cost.
This copolymer is prepared by the method described in (Method I) (Japanese Patent Laid-Open No. 58-19309, Japanese Patent Laid-Open No. 59-95292), that is, a metallocene catalyst, particularly a metallocene / amoxane catalyst, or, for example, International Publication A catalyst comprising a metallocene compound and a compound that reacts with the metallocene compound to form a stable ion as disclosed in the specification of Japanese Patent Publication No. WO92 / 01723 or the like. Using, for example, a catalyst in which a metallocene compound is supported on an inorganic compound as described in No. 5-295022 or the like, a main component ethylene and a sub component C 4-10 α-olefin are obtained. In which the density of the resulting copolymer is 0.900 to 0.930 g / cm ³ , which includes high pressure ion polymerization, Examples thereof include a liquid method, a slurry method, and a gas phase method.

  The melt flow rate (MFR) of the metallocene polyethylene is preferably in the range of 0.1 to 10 g / 10 minutes, more preferably 0.2 to 5 g / 10 minutes as measured by JIS-K6760. When the MFR is larger than this range, the film meanders at the time of inflation molding, and the end of the take-up film becomes uneven, resulting in poor molding stability. Also, if the MFR is smaller than this range, the load on the molding machine increases, so the production speed must be reduced to suppress the increase in pressure, and the productivity is remarkably lowered and the practicality is poor.

The density of the metallocene polyethylene is preferably in the range of 0.900 to 0.930 g / cm ³ , more preferably 0.910 to 0.925 g / cm ³ as measured by JIS-K6760. If the density is larger than this range, the transparency of the film is deteriorated, and wrinkles and slack are likely to occur when the film is stretched to the house. If the density is smaller than this range, blocking occurs due to stickiness and the film is stretched to the house. The practicality is poor because the openability during work and the developability of the film are significantly deteriorated.

  The molecular weight distribution (weight average molecular weight / number average molecular weight) of the metallocene polyethylene is determined by gel permeation chromatography (GPC). In this case, the molecular weight distribution is 1.5 to 3.5, preferably 1.5 to 3.0. When the molecular weight distribution is larger than this range, the mechanical strength is lowered, and the dustproof property is deteriorated by bleeding out of low molecular weight components, which is not preferable. When the molecular weight distribution is smaller than this range, the film meanders during molding and the stability of the bubble is significantly deteriorated.

In a preferred embodiment of the present invention, the outer layer and the inner layer of the base film contain high-pressure radical method low-density polyethylene (HP-LDPE) as a resin component. In the present invention, HP-LDPE having an MFR of 0.1 to 5 g / 10 min and a density in the range of 0.910 to 0.925 g / cm ³ is moldability, transparency, flexibility and price. From the point of view, it is preferable.

  As a preferred embodiment of the present invention, an ethylene-α-olefin copolymer resin obtained by copolymerization with a metallocene catalyst as a resin component of the outer layer of the base film or the outer layer and the inner layer is 45 wt% or more and 100 wt% or less. Preferably, a resin composition containing 55 wt% or more and 95 wt% or less is used, and an ethylene-vinyl acetate copolymer is 45 wt% or more and 100 wt% or less, preferably 55 wt% in the intermediate layer or the intermediate layer and the inner layer. It is preferable to use a resin composition containing 98% by weight or less.

式（１）中、Ｒ_１は、官能基または化合物（オリゴマー、ポリマーを含む）を表す。 Compound A
The polyolefin-based agricultural multilayer film of the present invention has at least one ring structure represented by the following formula (1) and has a molecular weight of 1000 or more (hereinafter also referred to as “light stabilizer”). At least in the intermediate layer.

In formula (1), R ₁ represents a functional group or a compound (including oligomers and polymers).

The compound A represented by the formula (1) is preferably largely classified into two types. One of them is a hindered amine compound having a triazine skeleton in the compound and having a molecular weight of 2000 or more (preferably 5000 or less) (type 1). In this type of compound, the ring structure of the formula (1) is preferably a 2,2,6,6-tetramethylpiperidine derivative and a mixture thereof, preferably, R ₁ is a C1-C20 alkyl group, or A cyclohexyl group or an octyl group.

式（５）において、ｍは１ないし１５の範囲で、Ｒ_１は、Ｃ１〜Ｃ２０のアルキル基、またはシクロアルキル基を示す。Ｒ_１２は、置換基を有してもよい、炭素原子数１〜１２のアルキレン基、アルケニレン基、シクロアルキレン基、もしくはアリーレン基を示す。Ｂは、互いに独立して、Ｃｌ，−ＯＲ_１３、−Ｎ（Ｒ_１４）（Ｒ_１５）又は、−Ｙ−に式（１）の基が結合した基を示し、ここで、Ｒ_１３、Ｒ_１４、Ｒ_１５は、各々水素原子、置換基を有していてもよい、炭素原子数１〜１８のアルキル基、シクロアルキル基、アルケニル基、アリール基、又はアリールアルキル基を表し、−Ｙ−は、−Ｏ−又は＞Ｎ−Ｒ_１６を表す。Ｒ_１１又はＲ_１６は、各々、式（１）で示される基又はＲ_１３に与えられた定義の一つを表す。 Examples of preferred hindered amine compounds having a type 1 triazine skeleton include those represented by the following formula (5).

In the formula (5), m is in the range of 1 to 15, and R ₁ represents a C1-C20 alkyl group or a cycloalkyl group. R ₁₂ represents an alkylene group having 1 to 12 carbon atoms, an alkenylene group, a cycloalkylene group, or an arylene group, which may have a substituent. B, independently of each other, represents Cl, —OR ₁₃ , —N (R ₁₄ ) (R ₁₅ ) or a group in which the group of the formula (1) is bonded to —Y—, wherein R ₁₃ , R ₁₄ and R ₁₅ each represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an alkenyl group, an aryl group, or an arylalkyl group, which may have a substituent, -Y- Represents —O— or> N—R ₁₆ . R ₁₁ or R ₁₆ each represents a group represented by formula (1) or one of the definitions given for R ₁₃ .

As the compound of formula (5), R ₁₂ is preferably a C2-C12 alkylene group, and B is -N (alkyl group) -group of formula (1) or -N (R ₁₄ ) (R ₁₅ ). R ₁₁ is a group of the formula (1), and R ₁ in the formula (1) is a C1-6 alkyl group. Particularly preferably, R ₁₂ is a C6 alkylene group, B is a group of —N (C ₄ H ₉ ) —formula (1) or —N— (C ₄ H ₉ ) ₂ , R ₁₁ is a group of formula (1), And a compound in which R ₁ in formula (1) is a C3 alkyl group.

  Examples of the hindered amine compound having a type 1 triazine skeleton include TINUVINNOR371 (manufactured by Ciba Specialty Chemicals Co., Ltd.). This compound is a hindered amine-based weathering agent (Kimasorb 944: triazine skeleton generally used for ordinary agricultural films, in which a hydrogen atom is bonded instead of —O—R1 in the above formula (1). Since the molecular weight is similar to that of the compound.), The acid resistance of the film can be improved by the same addition method. However, since this compound itself is colored, when it is used for an agricultural film that requires high transparency, it is necessary to devise the amount and method of addition. As a preferable embodiment, the above-mentioned specific hindered amine compound is contained in the intermediate layer of the multilayer film, and another hindered amine compound is contained in the other layer.

式（２）中、ｎは１〜４の整数を表し、Ｒ_２及びＲ_３は同一でも異なっていてもよく、それぞれ水素原子又は任意の置換基を表す。 The other type of compound A represented by formula (1) is an adduct obtained by adding a compound represented by formula (2) below to a polymer having a molecular weight of 300 or more (preferably a molecular weight of 2000 or more) (type). 2).

In formula (2), n represents an integer of 1 to 4, R ₂ and R ₃ may be the same or different, and each represents a hydrogen atom or an arbitrary substituent.

Examples of optional substituents for R ₂ and R ₃ include alkyl groups, vinyl groups, allyl groups, aryl groups, acyl groups, hydroxy groups, alkoxy groups, amino groups, hydroxylamino groups, cycloalkyl groups, cycloalkylcarbonyl groups, Examples thereof include, but are not limited to, a heterocyclic group, an aryloxy group, and a halogen atom. These substituents may further have a substituent. One or more carbon atoms in the cycloalkyl group or cyclocarbonyl group may be substituted with one or more heteroatoms such as oxygen, nitrogen, sulfur, phosphorus or silicon. Further, the optional substituent of R ₂ may be a bond representing carbonyl oxygen or imino group (═NR ′), and in this case, the group of —R ₃ does not exist.

In addition, when n = 2 or more, R ₂ bridges two or more nitroxy groups such as —O—CO— (CH ₂ ) x —CO—O— (x is an integer of 1 or more). It may be a group.

式（３）中、ｎは１〜４の整数を表し、Ｘは−Ｏ−又は−ＮＨ−を表し、Ｒ_３は水素原子又は任意の置換基を表し、Ｒ_４は水素原子、炭素数１〜２０の脂肪族アシル基、脂肪族多価アシル基、芳香族アシル基又は芳香族多価アシル基を表す。 In the present invention, a preferred embodiment of the type 2 compound A is an adduct obtained by adding a compound represented by the following formula (3) to a polymer having an average molecular weight of 300 or more (preferably a molecular weight of 2000 or more).

In formula (3), n represents an integer of 1 to 4, X represents —O— or —NH—, R ₃ represents a hydrogen atom or an arbitrary substituent, R ₄ represents a hydrogen atom, 1 carbon atom. -20 aliphatic acyl groups, aliphatic polyacyl groups, aromatic acyl groups or aromatic polyacyl groups.

Examples of the polymer having a molecular weight of 300 or more include polymers having unsaturated bonds such as polyolefins such as polypropylene, high density polyethylene, low density polyethylene, and linear low density polyethylene when a polyolefin resin is used as a base material. It can be preferably used. In addition to so-called polymers, the polymer in the present invention includes long-chain alkanes such as natural or synthetic waxes. Preferred waxes include polyolefin waxes such as polyethylene wax and polypropylene wax. In the present invention, the long-chain alkane of the polyolefin wax may be linear or branched, and two or more main chains may be crosslinked.
Moreover, the hindered amine compound of Formula (2) or (3) can also be added by forming a carbon-carbon double bond in the polyolefin wax molecule. Further, the hindered amine compound of the formula (2) or (3) is added by forming a carbon / carbon double bond in the polyolefin wax molecule and further converting the double bond into a reactive group. I can do it.

  The addition of the compound represented by the formula (2) or (3) to a polyethylene wax having a molecular weight of 300 or more can be performed by a known method. As the polyethylene wax to be added, any type can be used such as those using a thermal decomposition method, those using a Ziegler catalyst, and those using a metallocene catalyst. Examples of those using metallocene catalysts include polyolefin wax such as EXELEX manufactured by Mitsui Chemicals, Inc., which has features such as low molecular weight, high hardness, and easy introduction of reactive groups. The cost tends to be slightly higher.

  Examples of type 2 compound A include ADK STAB LA-900 (manufactured by Asahi Denka Co., Ltd.).

In the present invention, a compound represented by the following formula (4) can also be used as a modification of the type 2 compound A.

In the formula (4), R ₅ represents a hydrogen atom or an arbitrary substituent, E is an alkyl group having 60 to 1,000,000 carbon atoms, and the alkyl chain of the alkyl group is an alkyl substituent, It can contain aromatic substituents and acidic groups as substituents, and can be interrupted by alkene units and heteroatoms, and n ′ is an integer from 1 to 1000.

  The alkyl group E in formula (4) is preferably derived from wax.

The alkyl group E is a group corresponding to the structure of total synthesis or partial synthesis or natural wax.

Examples of suitable natural waxes include plant waxes such as carnauba wax or candelilla wax, or animal-derived waxes such as shellac. An example of a suitable partially synthetic wax is a salasimmon tallow wax derivative (possibly chemically modified, for example by esterification and / or by partial hydrolysis).
In addition, polar or non-polar fully synthetic waxes (such as polyolefin waxes) can be used. Nonpolar polyolefin waxes can be made by thermal degradation of branched or unbranched polyolefin polymers or by direct polymerization of olefins. Examples of suitable polymerization processes include free radical processes in which olefins, generally ethylene, are reacted under high pressures and temperatures to form waxes with some degree of branching, and also organometallic catalysts (eg Ziegler-Natta or Including processes in which ethylene and / or higher 1-olefins are polymerized into branched or unbranched waxes using a metallocene catalyst).

  Polar polyolefin waxes are grafted by oxidation with air or polar olefin monomers (examples of which are α, β-unsaturated carboxylic acids such as acrylic acid or maleic anhydride and / or their derivatives) Formed by a corresponding modification of a non-polar wax. Still further, polyolefin waxes are produced by copolymerizing ethylene with polar comonomers such as vinyl acetate or acrylic acid or otherwise by oxidative degradation of relatively high molecular weight non-wax-like ethylene homopolymers and copolymers. It is.

  Suitable polyolefin waxes include degraded waxes made by thermal degradation of ethylene or 1-olefin homopolymers and copolymers (eg, polyethylene or polypropylene). Further possibilities are waxes obtained by polymerization in a free radical process or with Ziegler-Natta or metallocene catalysts (examples of which are homopolymers of ethylene or higher 1-olefins or their respective ones). Which is a copolymer of The 1-olefins used are linear or branched olefins having 3 to 18 C atoms, preferably 3 to 6 C atoms, and these olefins are polar functional groups such as ester groups or acid groups. It is also possible to contain groups. Examples thereof are propene, 1-butene, 1-hexene, 1-octene or 1-octadecene, vinyl acetate, acrylic acid and acrylic esters (such as methyl acrylate or ethyl acrylate). Preference is given to homopolymers of ethylene or propene or their respective copolymers. The copolymer is composed of one olefin to the extent of 70-99.9%, preferably 80-99% by weight.

  The polar wax produced by modification of the polyolefin wax mentioned above can also be an alkyl group E. Modification may be by oxidation with an oxygen-containing gas such as air and / or acrylic acid or methacrylic acid, an acrylic ester (such as methyl or ethyl acrylate), maleic anhydride or maleic ester (dimethyl maleate or diethyl maleate) In principle), such as by grafting with α, β-unsaturated acids or their derivatives.

  The alkyl group E is preferably a group corresponding to the structure of a fully synthetic wax (which may be polar or nonpolar or may have undergone polar modification).

  The nonpolar fully synthetic wax is preferably a polyolefin wax or a Fischer-Tropsch paraffin.

Nonpolar fully synthetic waxes are preferably polyolefin waxes made by thermal degradation of branched or unbranched polyolefin polymers or by direct polymerization of olefins, preferably ethylene, propylene and / or other Homopolymers and copolymers of olefins such as copolymers with C ₃ to C ₂₀ alpha olefins.

  Nonpolar fully synthetic waxes are preferably ethylene or propylene homopolymers and copolymers or copolymers of ethylene and propylene made by the Ziegler-Natta process or the metallocene process.

Examples of the optional substituent in R ₅ include an alkyl group, a vinyl group, an allyl group, an aryl group, an acyl group, a hydroxy group, an alkoxy group, an amino group, a hydroxylamino group, a cycloalkyl group, a cycloalkylcarbonyl group, and a heterocyclic group. , An aryloxy group, a halogen atom, and the like, but are not limited thereto. These substituents may further have a substituent. One or more carbon atoms in the cycloalkyl group or cyclocarbonyl group may be substituted with one or more heteroatoms such as oxygen, nitrogen, sulfur, phosphorus or silicon. Further, the optional substituent of R ₅ may be a bond representing carbonyl oxygen or imino group (= NR ′).

  Examples of such a compound represented by the formula (4) include HostavinNOW manufactured by Clariant.

  The compound represented by Formula (4) can impart pesticide resistance by appropriately selecting the addition amount according to the molecular weight of the polymer to be added. Moreover, by using the said compound, the multilayer film for agriculture which does not have a problem of a coloration or an odor without a long-term weather-resistant performance fall can be provided.

Moreover, as another preferred embodiment of the present invention, the compound A contained in at least the intermediate layer of the agricultural multilayer film is represented by the following formula (6).

In Formula (6), R ₆ represents a C1-C12 alkyl group, and Z represents a C1-C4 alkylene group or a carbonyl group (C═O).

  Examples of the compound represented by the formula (6) include LA-81 and NO-Alkyl-1 (manufactured by ADEKA).

  The content of Compound A in the agricultural multilayer film of the present invention is 0.001 to less than 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the polyolefin resin composition in the film intermediate layer. Preferably it is 0.1-4 weight part.

  Content of the said compound A in the agricultural multilayer film of this invention is 0.001-10 weight part with respect to 100 parts of resin in the intermediate | middle layer of a base film, Preferably it is 0.01-5 weight part, More preferably, it is 0.1 to 4 parts by weight.

  In the present invention, compound A is contained in at least the intermediate layer, and may be contained in only the intermediate layer, all layers, the intermediate layer and the inner layer or the outer layer. When a hindered amine compound is added to a layer other than the intermediate layer, it is less than 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, more preferably 0.1 to 100 parts by weight of the resin in each layer. It can be added in an amount of 4 parts by weight.

  In the present invention, Compound A can be used in combination with one or two or more other hindered amine weathering agents that are usually used. Furthermore, the 1 type, or 2 or more types of hindered amine type weathering agent normally used can also be used with respect to the layer which does not contain the said hindered amine compound. For example, the hindered amine compound may be contained in the intermediate layer, and the other layers may contain a hindered amine weathering agent that is usually blended for agricultural use. Moreover, the hindered amine compound and the hindered amine type weathering agent normally mix | blended for agriculture can also be contained in the same layer. In that case, the cost becomes more advantageous than the case where the hindered amine compound is used in all layers.

  Examples of hindered amine weathering agents that are usually blended for use in agriculture include bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-di-). Tert-butyl-4-hydroxybenzyl) malonate, tetra (2,2,6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, tetra (1,2,2,6,6-pentamethyl-4-piperidyl) ) Butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) · di (tridecyl) butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) ) .Di (tridecyl) butanetetracarboxylate, 3,9-bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl-4 Piperidyloxycarbonyloxy) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- {tris (1,2 , 2,6,6-pentamethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,5,8,12-tetrakis [4,6-bis {N- (2,2,6,6-tetramethyl-4-piperidyl) butylamino} -1,3,5-triazin-2-yl] -1,5,8,12- Tetraazadodecane, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / dimethyl succinate condensate, 2-tertiary octylamino-4,6-dichloro -S-triazine / N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine condensate, N, N'-bis (2,2,6,6-tetramethyl) -4-piperidyl) hexamethylenediamine / dibromoethane condensate.

  Examples of commercially available hindered amine compounds that can be used in combination include TINUVIN 765, TINUVIN 770, TINUVIN 780, TINUVIN 144, TINUVIN 622LD, CHIMASSORB119FL, CHIMASSORB944 (above, manufactured by Ciba Geigy), Sanol LS-765 (manufactured by Sankyo R Co., Ltd., 63) , MARK LA-68, MARK LA-68, MARK LA-62, MARK LA-67, MARK LA-57 (manufactured by Adeka Argus), CYASORB UV-3346, CYASORBUV-3529, CYASORB UV-3581, CYASORB UV-3853 etc. are mentioned. These piperidine ring-containing hindered amine compounds are used alone or in combination of two or more.

  In a preferred embodiment of the present invention, a compound represented by the following formula (7) is contained in at least the intermediate layer. The compound represented by the formula (7) is a so-called triaryltriazine-type ultraviolet absorber, and a better effect can be obtained by adding at least one of them.

In Formula (7), R _{7 to} R ₁₁ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. More preferably, R ₇ is an alkyl group having 6 to 10 carbon atoms, particularly preferably an alkyl group having 6 to 8 carbon atoms, and R _{8 to} R ₁₁ are each a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, particularly Preferably they are a hydrogen atom or a methyl group.

In the formula (7), if the number of carbon atoms in R ₇ is less than the above range, bleeding out tends to occur, which is not preferable. Moreover, since it will become easy to bleed out if the carbon number of R < ₈ > -R < ₁₁ > is less than the said range, it is unpreferable since weather resistance is inferior when it exceeds the said range. In particular, in the present invention, when R ₇ in formula (3) is an octyl group and R _{8 to} R ₁₁ are methyl groups, or R ₇ in formula (3) is a hexyl group, R ₈ to When R ₁₁ is a hydrogen atom, an agricultural film having excellent bleed-out resistance and chemical stability can be obtained.

  The method for obtaining the triaryltriazine-based ultraviolet absorber represented by the formula (7) is not particularly limited, and commercially available products can be used. For example, UV1164 (made by Cytec), TINUVIN 1577 FF (made by Ciba Specialty Chemicals), etc. can be mentioned.

  The content of the triaryltriazine type ultraviolet absorber represented by the formula (7) in the agricultural multilayer film of the present invention is less than 5 parts by weight, preferably 0. 001 to 3 parts by weight, more preferably 0.003 to 1 part by weight. If the content is less than the above range, the effect of improving weather resistance is low, and if it exceeds the above range, there are problems such as a decrease in transparency due to bleeding out.

  In the present invention, the triaryltriazine type ultraviolet absorber is contained in at least the intermediate layer, and may be contained in only the intermediate layer, all layers, the intermediate layer and the inner layer or the outer layer. Moreover, this triaryl triazine type | mold ultraviolet absorber can be used in combination with the 1 type, or 2 or more types of other ultraviolet absorber normally used. Further, one or more commonly used ultraviolet absorbers can be used for the layer not containing the triaryltriazine type ultraviolet absorber. For example, the triaryltriazine type ultraviolet absorber may be contained in an intermediate layer, and the other layers may contain an ultraviolet absorber usually blended for agricultural use. Moreover, the triaryltriazine type ultraviolet absorber and the ultraviolet absorber usually blended for agricultural use can be contained in the same layer. In that case, it becomes more advantageous in terms of cost than the case of using a triaryltriazine type ultraviolet absorber in all layers.

  The triaryltriazine type ultraviolet absorber used in the present invention is characterized by good bleeding out properties, but when added to a multilayer film, the bleeding out properties can be further improved. As a method for adding excellent bleed-out resistance, the content of UV absorber X per unit volume in the intermediate layer X> the content Y of UV absorber per unit volume in the inner layer, and X> per unit volume in the outer layer Agricultural multilayer film with UV absorber content Z, agricultural multilayer film in which 80% or more of UV absorber added in all films is contained in the intermediate layer, and other than the surface layer of the multilayer film (house inner layer An agricultural multilayer film obtained by adding a UV absorber to a layer other than the outer layer of the house (intermediate layer).

  Usable ultraviolet absorbers usually used for agriculture are, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5′-methylenebis ( 2-hydroxybenzophenones such as 2-hydroxy-4-methoxybenzophenone); 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-dithane) Tributylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5) '-Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-tertiary octylpheny 2) 2 such as benzotriazole, 2- (2′-hydroxy-3′.5′-dicumylphenyl) benzotriazole, 2,2′-methylenebis (4-tert-octyl-6-benzotriazolyl) phenol -(2'-hydroxyphenyl) benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3 ', 5'-ditert-butyl-4'-hydroxybenzoate, 2,4- Benzoates such as ditertiary amylphenyl-3 ′, 5′-ditertiarybutyl-4′-hydroxybenzoate, hexadecyl-3,5-ditertiarybutyl-4-hydroxybenzoate; 2-ethyl-2′- Substituted oxanilides such as ethoxyoxanilide and 2-ethoxy-4′-dodecyloxanilide; ethyl-α-cyano-β, β Cyanoacrylates such as diphenyl acrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; 2- (4,6-diphenyl-1,3,5-triazin-2-yl)- Triazines such as 5-[(hexyl) oxy] -phenol, 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol And the like. These ultraviolet absorbers are used alone or in combination of two or more.

In a further preferred embodiment of the present invention, the base film has at least one layer containing a copolymer of ethylene (A) and a cyclic aminovinyl compound (B) represented by the following formula (8). .

By using such an ethylene / cyclic aminovinyl compound copolymer, an agricultural film having excellent long-term weather resistance and bleed-out resistance can be obtained. The ethylene / cyclic aminovinyl compound copolymer has an effect as a light stabilizer that significantly improves long-term weather resistance as compared with a hindered amine weathering agent used in general agricultural films. Further, the ethylene / cyclic aminovinyl compound copolymer is also difficult to bleed out, and by using this in combination with the ultraviolet absorber represented by the formula (7), the weather resistance is remarkably high while suppressing the bleed out. Can be obtained.
Moreover, in this invention, since the adhesiveness of an anti-fogging coating film improves by adding an ethylene and a cyclic amino vinyl compound copolymer to any layer of a base film, it is more preferable.

In Formula (8), R ₁₂ and R ₁₃ each independently represent a hydrogen atom or a methyl group, and R ₁₄ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Preferably, R ₁₂ and R ₁₃ are each a methyl group, and R ₁₄ is a hydrogen atom.

  The vinyl compound (B) represented by the formula (8) is known and can be synthesized by a known method, for example, a method described in JP-B-47-8539, JP-A-48-65180, or the like. it can.

  Typical examples of the vinyl compound represented by the formula (8) include 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-1,2,2,6,6-pentamethyl. Piperidine, 4-acryloyloxy-1-ethyl-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-1-propyl-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-1 -Butyl-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine 4-methacryloyloxy-1-ethyl-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-1-butyl-2, , 6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-1-propyl-2,2,6,6-tetramethylpiperidine and the like. Can be mentioned.

  As the preferred ethylene / cyclic aminovinyl compound copolymer, the ratio of (B) to the sum of ethylene (A) and cyclic aminovinyl compound (B) is 0.0005 to 0.85 mol%, More preferably, it is 0.001 to 0.55 mol%. That is, the preferred copolymer is one having a high light stability for a low content of the vinyl monomer having a hindered amine group in the side chain (cyclic aminovinyl compound (B)). When the concentration of the cyclic aminovinyl compound (B) is 0.0005 mol%, a sufficient light stabilizing effect is exhibited. On the other hand, when it exceeds 0.85 mol%, it tends to be substantially uneconomical.

  Further, the ethylene / cyclic aminovinyl compound copolymer is such that (B) is not continuous in two or more in the copolymer, and the ratio of being isolated is 83% or more based on the total amount of (B), Preferably it is 90% or more.

  The MFR (value measured according to JIS-K6760 (190 ° C., 2.16 kg load)) of the ethylene / cyclic aminovinyl compound copolymer is 0.1 to 200 g / 10 min, preferably 0.5 to 20 g / 10 minutes, more preferably 1-5 g / 10 minutes. When the MFR is less than the above range, the compatibility with the polyolefin resin is poor, and when blended, it causes visible defects in film applications such as fish eyes and boots. On the other hand, if the MFR exceeds the above range, even if the copolymer has a large molecular weight, bleeding or blooming due to diffusion loss occurs, or when it is blended with a polyolefin resin, it causes a decrease in strength of the resulting resin composition. It becomes.

  Further, the ethylene / cyclic aminovinyl compound copolymer is expressed by a ratio of the weight average molecular weight to the number average molecular weight determined by preparing a calibration curve with monodisperse polystyrene using GPC. The value is preferably in the range of 3 to 120. A particularly preferred range is 5-20.

The ethylene / cyclic aminovinyl compound copolymer is produced by subjecting required monomers to copolymerization conditions, but can be produced by a high-pressure low-density polyethylene production apparatus. Usually produced by radical polymerization, the catalyst used is a free radical generator, such as dialkyl peroxides, diacyl peroxides, peroxyesters, ketone peroxides, peroxyketals, hydroperoxides, azo Compounds and the like are useful. As the polymerization apparatus, a continuous stirring tank reactor or a continuous tube reactor generally used in the high-pressure radical polymerization method of ethylene can be used. The polymerization pressure is about 1000 to 5000 kg / cm ² , and the polymerization temperature is about 100 to 400 ° C.

  The content of the ethylene / cyclic aminovinyl compound copolymer in the agricultural multilayer film of the present invention is preferably 0.5 to 15 parts by weight with respect to 100 parts by weight of the polyolefin resin in the whole layer of the base film. Particularly preferred is 0.5 to 10 parts by weight. If this content is less than the above range, the weather resistance is inferior because it is inferior, and if it exceeds the above range, it is not preferable in terms of economy.

  Examples of commercially available ethylene / cyclic aminovinyl copolymers that can be used include Novatec LD · XJ100H (manufactured by Nippon Polychem Co., Ltd.).

From the viewpoint of cost, the ethylene / cyclic aminovinyl compound copolymer used in the present invention does not necessarily need to be contained in all layers of the base material film, and may be contained in at least one layer. In the present invention, at least the inner layer preferably contains an ethylene / cyclic aminovinyl compound copolymer. Thereby, the adhesiveness of an anti-fogging coating film can be improved effectively.
Further, the ethylene / cyclic aminovinyl compound copolymer can be used in combination with one or two or more hindered amine weathering agents that are usually used. Further, one or two or more hindered amine weathering agents which are usually used can be used for the layer not containing the ethylene / cyclic aminovinyl compound copolymer. Of course, the ethylene / cyclic aminovinyl compound copolymer may be contained in all layers, for example, it is contained in the innermost layer and the outermost layer (outer surface of the house), and the other layers are usually formulated for agriculture as described above. A hindered amine light stabilizer may also be included. Moreover, the hindered amine light stabilizer normally mix | blended for agricultural use can also be contained in the same layer with an ethylene-cyclic amino vinyl compound copolymer. In this case, the cost becomes more advantageous than the case where an ethylene / cyclic aminovinyl compound copolymer is used for all layers.

  The agricultural multilayer film in the present invention can be provided with good heat retaining properties by adding an infrared absorber. As the infrared absorber, an inorganic compound (inorganic oxide, inorganic hydroxide, hydrotalcite, etc.) containing at least one atom of Mg, Ca, Al, Si and Li that is effective as a heat retaining agent can be used.

Especially, when the hydrotalcite infrared absorber represented by the following formula (9) is used, a film that is inexpensive and has good moldability can be obtained.

  The method for obtaining the infrared absorber (heat retention agent) represented by the formula (9) is not particularly limited, and commercially available products can be used, for example, DHT4A, SYHT-3 (manufactured by Kyowa Chemical Co., Ltd.), etc. Is mentioned.

  The infrared absorbent (heat retention agent) used in the present invention is inorganic fine particles having infrared absorbing ability, and these can be used alone or in combination of two or more. The inorganic fine particles that can be used are not particularly limited, but inorganic compounds containing at least one atom selected from the components: Si, Al, Mg, and Ca can be used. For example, magnesium oxide, calcium oxide, aluminum oxide, silicon oxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, magnesium carbonate, calcium carbonate, calcium sulfate, magnesium sulfate, aluminum sulfate, lithium phosphate, calcium phosphate , Magnesium silicate, calcium silicate, aluminum silicate, calcium aluminate, magnesium aluminate, sodium aluminosilicate, potassium aluminosilicate, calcium aluminosilicate, kaolin, clay, talc, mica, zeolite, hydrotalcite compounds and the like. These may be obtained by dehydrating crystal water.

  The inorganic fine particles may be natural products or synthetic products. The inorganic fine particles can be used without being limited by the crystal structure, crystal particle diameter, and the like.

  Examples of the metal species constituting the organic acid salt, basic organic acid salt and overbased organic acid salt of the metal include Li, Na, K, Ca, Ba, Mg, Sr, Zn, Cd, Sn, Cs, Examples of the organic acid include carboxylic acid, organic phosphoric acid, and phenol.

  In the agricultural multilayer film of the present invention, various additives usually used for synthetic resins can be used in combination within the range not impairing the effects of the present invention. Examples of these additives include metal organic acid salts, basic organic acid salts and overbased organic acid salts, hydrotalcite compounds, epoxy compounds, β-diketone compounds, polyhydric alcohols, halogen oxyacid salts, Examples thereof include sulfur-based, phenol-based and phosphite-based antioxidants, heat stabilizers, lubricants, antistatic agents, coloring agents, antiblocking agents, antifogging agents, and antifogging agents.

  Although there is no restriction | limiting in particular about the said anti-fogging agent, It consists of polyhydric alcohol and higher fatty acids including well-known various nonionic surfactant, anionic surfactant, cationic surfactant, etc. A polyhydric alcohol partial ester type is preferred. Specific examples of such an antifogging agent include, for example, nonionic surfactants such as sorbitan monostearate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monobehenate, sorbitan / alkylene glycol condensate and fatty acid. Sorbitan surfactants such as esters and glycerol monopalmitate, glycerol monostearate, glycerol monolaurate, diglycerol monopalmitate, glycerol dipalmitate, glycerol distearate, diglycerol monopalmitate monostearate Glycerin surfactants such as glycerol, monoglycerate, triglycerin monostearate, triglycerin distearate or alkylene oxide adducts thereof, polyethylene glycol monostearate, polyethylene glycol Polyethylene glycol surfactants such as coal monopalmitate, polyethylene glycol alkyl phenyl ether, and other trimethylolpropane surfactants such as trimethylolpropane monostearate, and pentaerythritol monopalmitate, pentaerythritol monostearate, etc. Erythritol surfactant, alkylene oxide adduct of alkylphenol; sorbitan / glycerin condensate and fatty acid ester, sorbitan / alkylene glycol condensate and fatty acid ester; diglycerin dioleate sodium lauryl sulfate, dodecylbenzenesulfonic acid Sodium, cetyltrimethylammonium chloride, dodecylamine hydrochloride, lauric acid laurylamide ethyl phosphate It can be exemplified triethylammonium cetyl ammonium iodide, oleyl amino diethylamine hydrochloride, and those containing dodecyl pyridinium salts, etc. and their isomers.

  Examples of the anti-fogging agent include a fluorine-based surfactant and a silicone-based surfactant. Specific examples of the fluorine-based surfactant include, instead of H bonded to C of the hydrophobic group of a normal surfactant. In addition, a surfactant having a part or all thereof substituted with F, particularly a surfactant containing a perfluoroalkyl group or a perfluoroalkenyl group. The above various additives can be used alone or in combination of two or more. Examples of the fluorine-containing compound having a perfluoroalkyl group include an anionic fluorine-containing surfactant, a cationic fluorine-containing surfactant, an amphoteric fluorine-containing surfactant, a nonionic fluorine-containing surfactant, and a fluorine-containing oligomer. can give.

  The amount of the fluorine-containing compound having a perfluoroalkyl group used is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts per 100 parts by weight of the polyolefin-based resin in the entire base film. Parts by weight. If the amount of the fluorine-containing compound used is less than 0.001 part by weight, the antifogging effect is hardly exhibited, and if it exceeds 10 parts by weight, the effect is saturated, which is not preferable.

  In addition, as a filler, for example, silica, talc, aluminum hydroxide, hydrotalcite, calcium sulfate, calcium silicate, calcium hydroxide, water, in order to suppress stickiness of the film or to further improve heat retention Magnesium oxide, kaolin clay, mica, alumina, magnesium carbonate, sodium aluminate, conductive zinc oxide, lithium phosphate and the like are used. One type of these fillers may be used, or two or more types may be used in combination.

  Examples of the phenol-based antioxidant include 2,6-ditertiarybutyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditertiarybutyl-4- Hydroxyphenyl) -propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6 -Hexamethylene bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylene bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide] 4,4′-thiobis (6-tert-butyl-m-cresol), 2,2′-methylenebis (4-methyl-6- Tributylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4, 4'-butylidenebis (6-tert-butyl-m-cresol), 2,2'-ethylidenebis (4,6-ditert-butylphenol), 2,2'-ethylidenebis (4-secondarybutyl-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-butylbenzyl) isocyanurate 1,3,5-tris (3,5-ditert-butyl-4-hydroxylbenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) 2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9- Bis [1,1-dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5. ] Undecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], n-octadecyl 3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) ) Propionate, tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane and the like.

  Examples of the phosphite-based antioxidant include trisnonylphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris [2-tert-butyl-4- (3-tert-butyl- 4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, monodecyl diphenyl phosphite, mono (dinonylphenyl) Bis (nonylphenyl) phosphite, di (tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditertiarybutylphenyl) penta Erythritol diphosphie Bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (C 12-15 mixed alkyl) -4,4′-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-) 5-tert-butylphenyl) butanetriphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, 2,2′-methylenebis (4,6-ditert-butylphenyl) (octyl) phosphite , Tetrakis (2,4-di-t-butylphenyl) 4,4′-biphenylene-di Phosphonites, 2,2-methylenebis (4,6-di -t- butyl phenyl) octyl phosphite, and the like.

In the agricultural polyolefin multilayer film of the present invention comprising at least the compound A having at least one ring structure represented by the formula (1) in the intermediate layer, the sulfur-based antioxidant antagonizes the hindered amine-based compound. In order to weaken the effect, it is preferable not to add.
In the agricultural polyolefin-based multilayer film of the present invention, it is preferable that the base film does not substantially contain a phenolic antioxidant. In the present invention, “the substrate film does not substantially contain a phenolic antioxidant” means that no phenolic antioxidant is added as an additive in the blending of the substrate film. Some polyolefin-based resins that are raw materials for the base film contain a phenol-based antioxidant in advance (internally added). In the present invention, however, Even when a polyolefin-based resin is used, if a phenol-based antioxidant is not added as an additive, it is included when “the substrate film does not substantially contain a phenol-based antioxidant”.

  In one preferred embodiment of the present invention, the base film is preferably less than 0.05% by weight of phenolic antioxidant, more preferably 0.03% by weight, based on the weight of polyolefin resin in the entire layer. It is contained at a concentration of not more than%. When the base film contains 0.05 wt% or more of a phenolic antioxidant relative to the weight of the polyolefin resin in the entire layer, the light transmittance at 325 nm tends to decrease when the multilayer film is stored over time. In addition, ultraviolet rays around 325 nm are unfavorable because they are related to the flight and mating of insects such as bees. Moreover, even if the light transmittance at 325 nm once decreases, when the film is exposed to sunlight, the light transmittance usually tends to gradually increase, but the content of the phenolic antioxidant in the base film is small. If it is 0.05% by weight or more, a considerable amount of time is required until recovery, which is not preferable. When the content of the phenolic antioxidant in the entire layer of the base film is less than 0.05% by weight, preferably 0.03% by weight or less, a decrease in light transmittance at 325 nm can be suppressed, Moreover, even if it falls once, when it exposes to sunlight, since recovery | restoration of light transmittance is quick, it is preferable.

  The amount of the above-mentioned phenolic antioxidant added can be quantitatively analyzed from the film by a known method. For example, a film sample can be extracted into an organic solvent by Soxhlet extraction or the like and quantitatively analyzed by GC-MS, gas chromatography, liquid chromatography, or the like. At that time, as a reference, a reference film sample in which the type and amount of the phenolic antioxidant is added can be prepared, and a calibration curve for quantitative analysis can be prepared. The amount of the phenolic antioxidant in the film can be estimated by comparing the quantitative analysis result of the target sample using the calibration curve thus created. In this case, although the extraction efficiency may be a problem, the variation can be reduced by a device such as extraction over time, and a more accurate amount of phenolic antioxidant can be estimated. The phenolic antioxidant used for reference can be a known one such as a hindered type or a semi-hindered type, but a generally available phenolic antioxidant such as BHT, Irganox 1076, Irgonox 1010 should be used. I can do it. In the case of quantitative analysis using GC-MS, there is an advantage of high sensitivity, but since quantitative analysis using fragments is performed, quantitative analysis using converted values is performed. As a conversion target, a known phenol-based antioxidant can be used.

  Examples of the colorant include phthalocyanine blue, phthalocyanine green, hansa yellow, alizarin lake, titanium oxide, zinc white, ultramarine blue, permanent red, quinacridone, and carbon black.

  Examples of the anti-blocking agent include diatomaceous earth, synthetic silica, talc, mica and zeolite. These anti-blocking agents can be used alone or in combination of two or more, and the range of usually 0.01 to 0.5% by weight is preferred.

  The agricultural multilayer film of the present invention contains the above-described components in combination, and can further contain the following optional components that can be used for agricultural films, if necessary. Optional components include other stabilizers, impact resistance improvers, cross-linking agents, fillers, foaming agents, antistatic agents, nucleating agents, plate-out preventing agents, surface treatment agents, flame retardants, fluorescent agents, anti-glare agents Agents, bactericides, metal deactivators, mold release agents, pigments, processing aids and the like.

  In the production of the agricultural multilayer film of the present invention, in order to blend various additives, weigh each necessary amount, blending ribbon blender, Banbury mixer, Henschel mixer, super mixer, single or twin screw extruder, roll, etc. What is necessary is just to use the compounding machine and mixer which were conventionally known for the machine, the kneading machine. 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 and an inflation method), calendar processing, roll processing, extrusion molding processing, Blow molding, inflation molding, melt casting, pressure molding, paste processing, powder molding, and the like can be suitably used.

  Although the base film in the agricultural multilayer film of the present invention has at least three layers of an inner layer, an intermediate layer, and an outer layer, it may be composed of more layers, for example, five layers. The layer ratio constituting the three-layer film is preferably in the range of 1 / 0.5 / 1 to 1/5/1 in terms of moldability, transparency and strength, and 1/2/1 to 1/4/1. The range of is more preferable. Further, the ratio between the outer layer and the inner layer is not particularly specified, but it is preferable that the ratio is approximately the same because of the curl property of the obtained film.

  About the thickness of the base film in this invention, the thing of the range of 0.01-1 mm is preferable at the point of intensity | strength or cost, The thing of 0.05-0.5 mm is more preferable, More preferably, it is 0.05-0. .2 mm. If it is less than this range, there is a problem in strength, and if it exceeds this range, molding is difficult and there is a problem in stretch workability.

  The agricultural multilayer film of the present invention is characterized by forming an antifogging film in contact with the innermost layer of the base film. At this time, if the film in contact with the antifogging coating contains a large amount of an antifogging agent, it may cause trouble when forming the antifogging coating due to the spraying of the antifogging agent onto the non-uniform film surface. . However, it is an object of the present invention as an anti-adhesive agent during kneading when used as a masterbatch in which various additives are concentrated and blended in advance in each layer of a polyolefin resin, or as a surface modifier when forming an antifogging film. A small amount can be used within a range that does not impair.

  Moreover, in the agricultural multilayer film of this invention, a coating film other than that can be formed. For example, a dust-proof coating film may be formed on the outer surface side of the house. In that case, the effect of improving the adhesion of the coating film, which is the effect of the present invention, may be obtained for the dust-proof coating film.

  Examples of the antifogging agent composition in the present invention include a composition mainly composed of an inorganic colloidal sol such as silica sol and / or alumina sol and a binder resin such as a thermoplastic resin. Preferably, an antifogging agent composition mainly comprising an inorganic colloid substance and a hydrophilic organic compound or an antifogging agent composition mainly comprising an inorganic colloid substance and an acrylic resin can be used.

  The inorganic colloid sol used in the present invention has a function of imparting hydrophilicity to the surface of the film, particularly by applying it to the surface of a hydrophobic polyolefin resin film. As the inorganic colloidal sol, inorganic aqueous colloidal particles such as silica, alumina, water-insoluble lithium silicate, iron hydroxide, tin hydroxide, titanium oxide, barium sulfate were dispersed in water or a hydrophilic medium by various methods. And aqueous sols. Among these, silica sol and alumina sol are preferably used, and these may be used alone or in combination.

  As the inorganic colloid sol, it is preferable to select an average particle size in the range of 5 to 100 nm. In this range, two or more colloid sols having different average particle sizes may be used in combination. If the average particle size is too large, the coating may be devitrified in white, and if the average particle size is too small, the stability of the inorganic colloidal sol may be unfavorable. The amount of the inorganic colloidal sol is preferably 0.2 to 5 and preferably 0.5 to 4 in terms of the weight ratio as the solid content with respect to the total solid weight of the binder resin composition. That is, when the blending amount is too small, a sufficient antifogging effect may not be exhibited. On the other hand, when the blending amount is too large, the antifogging effect is not easily improved in proportion to the blending amount. The film formed later becomes cloudy and causes a phenomenon that the light transmittance of the film is lowered, and the film may be coarse and brittle, which is not preferable.

  Examples of the binder resin include acrylic resins, epoxy resins, urethane resins, polyester resins, and the like, particularly from the viewpoint of compatibility with the polyolefin-based substrate film of the present invention, acrylic resins and / or urethane resins. It is preferable to use a resin, more preferably from (a) a hydrophilic acrylic polymer, (c) a hydrophobic acrylic resin, (e) a hydrophobic acrylic resin, and a polyurethane emulsion. Each has its own attributes and is preferred.

  Examples of the acrylic resin include (a) one made of a hydrophilic acrylic polymer, (b) one made of a block copolymer containing a hydrophobic molecular chain block and a hydrophilic molecular chain block in one molecule, (c ) Which is composed of a hydrophobic acrylic resin, and in particular, (a) is preferable because it is excellent in compatibility with the base film of the present invention in terms of early antifogging wetness, while (c) It is excellent in compatibility with the substrate film of the present invention, and is preferable.

  As the hydrophilic acrylic polymer (a), a hydroxyl group-containing vinyl monomer component is a main component (preferably 60 wt% to 99.9 wt%, more preferably 65 wt% to 95 wt%), acid Examples thereof include a copolymer containing 0.1 to 30% by weight of a group-containing vinyl monomer component, a partially neutralized product thereof, or a completely neutralized product thereof. Examples of the hydroxyl group-containing vinyl monomer component include hydroxyalkyl (meth) acrylates, such as hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- Although hydroxypropyl (meth) acrylate etc. are mentioned, it is not limited to these. These may be homopolymers, or may be copolymers of these hydroxyalkyl (meth) acrylates as main components and other monomers that can be copolymerized therewith.

  Examples of the acid group-containing monomer copolymerizable with these hydroxyalkyl (meth) acrylates include carboxylic acids, sulfonic acids and phosphonic acids, and (meth) acrylic acid belonging to carboxylic acids is particularly preferred.

  Examples of other copolymer components include styrene, vinyl toluene, vinyl chloride, vinylidene chloride, vinyl oxide, (meth) acrylic acid esters, N, N-dimethylaminoethyl (meth) acrylamide, vinyl pyridine, and the like. .

  As the hydrophobic acrylic resin (c), at least a total of 60% by weight of a monomer comprising an alkyl ester of acrylic acid or methacrylic acid, or a single unit of an alkyl ester of acrylic acid or methacrylic acid and an alkenylbenzene. A monomer mixture and 0 to 40% by weight of a copolymerizable α, β-ethylenically unsaturated monomer are obtained by emulsion polymerization in an aqueous medium, for example, in the presence of an emulsifier, under normal polymerization conditions. And water dispersible polymers or copolymers.

  Examples of alkyl esters of acrylic acid or methacrylic acid used in the production of hydrophobic acrylic resins include acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid-n-propyl ester, acrylic acid isopropyl ester, acrylic acid-n- A butyl ester etc. are mentioned, Generally, a C1-C20 acrylic acid alkyl ester and / or a C1-C20 methacrylic acid alkyl ester of an alkyl group are used. Examples of alkenylbenzenes include styrene, α-methylstyrene, vinyltoluene and the like.

  Examples of α, β-ethylenically unsaturated monomers used to obtain hydrophobic acrylic resins include α, β such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, and itaconic acid. -Ethylenically unsaturated carboxylic acids; α, β-ethylenically unsaturated sulfonic acids such as ethylene sulfonic acid; 2-acrylamido-2-methylpropanoic acid; α, β-ethylenically unsaturated phosphonic acids; acrylic acid or methacrylic acid Hydroxyl group-containing vinyl monomers such as hydroxyethyl; acrylonitriles; acrylic amides; glycidyl esters of acrylic acid or methacrylic acid, and the like. These monomers may be used alone or in combination of two or more, and are preferably used in the range of 0 to 40% by weight. If the amount used is too large, the antifogging performance may be lowered, which is not preferable.

  The acrylic resin is a known emulsifier, for example, an anionic surfactant, a cationic surfactant, or a nonionic surfactant, in the presence of one or more kinds in an aqueous medium. It can be obtained by a method of emulsion polymerization, a method of polymerization using a reactive emulsifier, a method of polymerizing based on an oligo soap theory without containing an emulsifier.

  Examples of the polymerization initiator preferably used for the production of the acrylic resin include persulfates such as ammonium persulfate and potassium persulfate. These can be used in the range of 0.1 to 10% by weight based on the total amount of monomers charged.

  It is particularly preferable to use a hydrophobic acrylic resin having a glass transition temperature of 35 to 80 ° C. If the glass transition temperature is too low, the inorganic colloidal particles are agglomerated several times and tend to be in a non-uniform dispersion state. If it is too high, it is difficult to obtain a transparent uniform coating.

  The hydrophobic acrylic resin used in the present invention is preferably used as an aqueous emulsion. An aqueous emulsion obtained by polymerization of each monomer in an aqueous medium may be used as it is, or may be diluted by adding a liquid dispersion medium to this, and also produced by the above polymerization. A polymer may be collected separately and re-dispersed in a liquid dispersion medium to form an aqueous emulsion.

  On the other hand, examples of (d) urethane-based resins include polyether-based, polyester-based, and polycarbonate-based anionic polyurethane aqueous compositions and emulsions. In terms of water resistance and scratch resistance, polycarbonate anionic polyurethane emulsions are preferred, and the water resistance of the further anti-fogging coating film, improvement in scratch resistance, time to develop anti-fogging properties and anti-fogging durability. A polycarbonate anionic polyurethane emulsion containing a silanol group is more preferable. These may be used alone or in combination of two or more.

  A polycarbonate-based anionic polyurethane emulsion containing a silanol group comprises a polyurethane resin containing at least one silanol group in the molecule and a strongly basic tertiary amine as a curing catalyst. Refers to a colloidal dispersion system (emulsion) in which the silanol group-containing polyurethane resin and the strongly basic tertiary amine are dissolved in the aqueous phase, or a colloidal dispersion system in which fine particles are dispersed.

  Furthermore, as a suitable antifogging coating film of the present invention, an embodiment using (e) the above-mentioned (c) hydrophobic acrylic resin and (d) an emulsion obtained by mixing an aqueous polyurethane composition is compatible with the base film. From the standpoints of satisfying both the speed of developing antifogging properties and the sustainability of antifogging in a well-balanced manner and being scratch resistant.

  It is preferable that the amount of the polyurethane aqueous composition is 0.01 or more and 2 or less, more preferably 0.01 or more and 1 or less with respect to the hydrophobic acrylic resin in terms of solid content by weight. When it is less than 0.01, it is difficult to improve the scratch resistance, and it takes a long time until the antifogging property is exhibited, and it is difficult to exhibit a sufficient antifogging effect. In addition, when it is too much, not only the scratch resistance is difficult to improve in proportion to the blending amount, but the coating film formed after coating tends to become cloudy and lower the light transmittance, which is also disadvantageous in terms of cost. It is not preferable.

  When preparing an antifogging agent composition for forming the antifogging coating film of the present invention, an anionic surfactant, a cationic surfactant, a nonionic surfactant, a polymer surfactant, etc. A surfactant can be added. As such a surfactant, those described below can be used.

  Anionic surfactants include fatty acid salts such as sodium oleate and potassium oleate; higher alcohol sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; alkylbenzene sulfones such as sodium dodecylbenzenesulfonate and sodium alkylnaphthalenesulfonate Acid salt and alkyl naphthalene sulfonate salt; naphthalene sulfonic acid formalin condensate; dialkyl sulfosuccinate salt; dialkyl phosphate salt; polyoxyethylene sulfate salt such as sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, etc. Can be mentioned.

  Cationic surfactants include: ethanolamines; laurylamine acetate, triethanolamine monostearate formate; amine salts such as stearamide ethyl diethylamine acetate; lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, dilauryldimethyl And quaternary ammonium salts such as ammonium chloride, distearyldimethylammonium chloride, lauryldimethylbenzylammonium chloride, and the like.

  Nonionic surfactants include polyoxyethylene higher alcohol ethers such as polyoxyethylene lauryl alcohol, polyoxyethylene lauryl ether and polyoxyethylene oleyl ether; polyoxyethylene such as polyoxyethylene octylphenol and polyoxyethylene nonylphenol. Alkylaryl ethers; polyoxyethylene acyl esters such as polyethylene glycol monostearate; polypropylene glycol ethylene oxide adducts; sorbitan fatty acid esters such as sorbitan monostearate, sorbitan monopalmitate, sorbitan monobenzoate; diglycerin monopalmi Diglycerol fatty acid esters such as tate and diglycerol monostearate; glycerol monostearate Glycerin fatty acid esters such as pentaerythritol monostearate, etc .; dipentaerythritol fatty acid esters such as dipentaerythritol monopalmitate; sorbitan monopalmitate half adipate, diglycerin monostearate half Sorbitan such as glutamate and diglycerin fatty acid / dibasic acid esters; or condensates thereof with alkylene oxide such as ethylene oxide and propylene on oxide such as polyoxyethylene sorbitan monolaurate and polyoxypropylene sorbitan monostearate Etc .; Polyoxyethylene stearylamine, polyoxyethylene oleylamine, polyoxyethylene stearamide, etc. Carboxymethyl ethylene alkyl amine fatty acid amides; sugar esters.

  Examples of the polymer surfactant include polyacrylate, polymethacrylate, and cellulose ethers.

  The addition of these surfactants enables the binder resin and the inorganic colloid sol to be easily and rapidly dispersed uniformly, and when used in combination with the inorganic colloid sol, the surface of the hydrophobic polyolefin resin base film is hydrophilic. Fulfills the function of giving The addition amount of the surfactant is preferably selected in the range of 0.1 to 50 parts by weight with respect to 100 parts by weight of the solid content of the resin. If the amount of the surfactant added is too small, it takes time to sufficiently disperse the resin and the inorganic colloid sol, and the antifogging effect in combination with the inorganic colloid sol cannot be sufficiently exhibited. If the amount added is too large, the transparency of the coating will decrease due to the bleed-out phenomenon on the coating surface formed after coating, and if it is noticeable, it may cause deterioration of the blocking resistance of the coating or decrease the water resistance of the coating. .

  When preparing the anti-fogging agent composition for forming the anti-fogging coating film of this invention, a crosslinking agent can be added. The crosslinking agent is particularly effective in crosslinking acrylic resins to improve the water resistance of the coating. Examples of the crosslinking agent include phenol resins, amino resins, amine compounds, aziridine compounds, azo compounds, isocyanate compounds, epoxy compounds, silane compounds, etc., but particularly amine compounds and aziridine compounds. Epoxy compounds can be preferably used.

  A liquid dispersion medium can be mix | blended with the anti-fogging agent composition used for this invention as needed. Such a liquid dispersion medium includes a hydrophilic or water-miscible solvent containing water, water; monohydric alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; polyhydric alcohols such as ethylene glycol, diethylene glycol, and glycerin. Examples: cyclic alcohols such as benzyl alcohol; cellosolve acetates; ketones and the like. These liquid dispersion media may be used alone or in combination.

  The anti-fogging agent composition prepared in the present invention is further mixed with conventional additives such as an antifoaming agent, a plasticizer, a film-forming aid, a thickening agent, a pigment, and a pigment dispersant as necessary. be able to. Further, as a binder component other than the acrylic resin, for example, a polyether-based, polycarbonate-based, or polyester-based water-dispersible urethane resin may be mixed.

  In order to form an antifogging coating film on the surface of a base film, generally a solution or dispersion of an antifogging agent composition is applied to a doctor blade coating method, a roll coating method, a dip coating method, a spray coating method, a rod coating method, A known coating method such as a bar coating method, a knife coating method, or a brush coating method may be employed and dried after coating. As a drying method after coating, either a natural drying method or a forced drying method may be employed. When the forced drying method is employed, the drying method is usually 50 to 250 ° C., preferably 70 to 200 ° C. Good. For heating and drying, an appropriate method such as a hot air drying method, an infrared drying method, a far infrared drying method, and an ultraviolet curing method may be employed, and it is advantageous to adopt the hot air drying method in consideration of the drying speed and stability. is there.

  In the present invention, the thickness of the coating film formed on the surface of the base film may be selected by using 1/10 or less of the base film as a guide, but is not necessarily limited to this range. When the thickness of the coating is greater than 1/10 of the base film, there is a difference in flexibility between the base film and the coating film, so that a phenomenon such as peeling of the coating film from the base film is likely to occur. Moreover, the phenomenon that a crack arises in a coating film and the intensity | strength of a base film falls arises, and is unpreferable.

  Moreover, when the adhesiveness of a base film and an anti-fog coating film is not enough, you may surface-treat to a base film. Examples of the treatment method applied to the surface of the laminated film of the present invention include corona discharge treatment, sputter etching treatment, sodium treatment, and sandblast treatment. In the corona discharge treatment method, discharge is performed between a needle-like or knife-edge electrode and a counter electrode, and a sample is placed between the electrodes, and the film surface contains oxygen such as aldehyde, acid, alcohol peroxide, ketone, ether, etc. This is a process for generating a functional group. In the sputter etching process, a sample is placed between electrodes that are performing low-pressure glow discharge, and a large number of fine protrusions are formed on the film by the impact of positive ions generated by the glow discharge. In the sandblasting process, fine sand is sprayed on the film surface to form a large number of fine irregularities on the surface. Among these surface treatments, corona discharge treatment is preferable from the viewpoints of adhesion to the coating layer, workability, safety, cost, and the like.

  When the agricultural multilayer film of the present invention is actually used, it is preferably stretched so that the side provided with the anti-fogging coating film is inside the house or tunnel.

  The agricultural multilayer film of the present invention maintains antifogging properties and various properties for a long time, and has good antifogging properties and antifogging coating film adhesion even under acidic conditions such as agricultural chemicals and acid rain. In addition to being excellent in weather resistance, it has a well-balanced performance to be provided as an agricultural film. In particular, when a hindered amine compound, an ultraviolet absorber and / or an ethylene / cyclic aminovinyl compound copolymer having the characteristic structure described above is used, the weather resistance, agricultural chemical resistance, and bleed out resistance are excellent. The effect of the present invention is particularly exerted, and when an anti-fogging coating film is provided on the film, bleed out is suppressed and adhesion to the substrate is not lowered, which is preferable. The agricultural multilayer film of the present invention may be transparent, satin or semi-satin, and is an agricultural film for house, tunnel, mulching, bag hanging, etc. (so-called farm bi, farm poly, farm sacbi, farm PO, hard It can be suitably used for applications such as film.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example and a comparative example, this invention is not limited to the following examples, unless the summary is exceeded.

(1) Preparation of laminated film (both antifogging agent kneading type and antifogging coating application type)
As a three-layer inflation molding device, a 100 mmφ (made by Pla Koken Co., Ltd.) was used for a three-layer die. Manufactured by Giken Co., Ltd.) Outer inner layer extruder temperature 180 ° C., intermediate layer extruder temperature 170 ° C., die temperature 180-190 ° C., blow ratio 2.0-3.0, take-off speed 3-7 m / min, thickness 0 A three-layer laminated film composed of the components shown in Tables 1 to 5 at 10 to 0.15 mm was obtained. Since these films are used with the end of the tube cut open when the house is stretched, the tube outer layer during film formation becomes the inner layer (inner surface) of the house when stretched when unfolded.

[Composition] Addition amounts are as described in each table.
Raw material resin HP-LDPE: branched polyethylene produced by a high-pressure radical catalyst (MFR: 1.1 g / 10 min, density 0.920) Novatec LD “YF30” manufactured by Nippon Polychem
Metallocene PE: An ethylene / α-olefin copolymer produced with a metallocene catalyst (MFR: 2 g / 10 min, density 0.907) Kernel “KF270” manufactured by Nippon Polychem
EVA1: Ethylene / vinyl acetate copolymer (vinyl acetate content 5% by weight, MFR 2 g / 10 min)
EVA2: Ethylene / vinyl acetate copolymer (vinyl acetate content 15% by weight, MFR 2 g / 10 min)
Infrared absorber Synthetic hydrotalcite: Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ .3.5H ₂ O
6 parts by weight of 100 parts of polyolefin resin is added to the intermediate layer.

Light Stabilizer Light Stabilizer A: Light Stabilizer “Tinuvin NOR371 FF” manufactured by Ciba Specialty Chemicals Co., Ltd. (2 having a triazine skeleton and having at least two structures described in the general formula (1)) , 2,6,6-tetramethylpiperidine derivative, molecular weight about 3600)
Light Stabilizer B: Light Stabilizer “ADK STAB LA-900” manufactured by Asahi Denka Co., Ltd. (hindered amine compound obtained by graft-adding the compound represented by the general formula (2) to polyethylene having an average molecular weight of about 100,000. (Has at least two structures of formula (1))
Light stabilizer C: Light stabilizer manufactured by Ciba Specialty Chemicals Kimasorb 944 (a hindered amine compound in which a hydrogen atom is bonded to a nitrogen atom of a piperidine ring and does not have the structure described in the general formula (1). Molecular weight) About 2000 to 3000.)
Light stabilizer D: Light stabilizer manufactured by Cytec Co., Ltd. CYASORB UV-3529 (a hindered amine compound of the type in which a methyl group is bonded to the nitrogen atom of the piperidine ring and does not have the structure described in the general formula (1). Average molecular weight 1700.)

Ethylene / Cyclic aminovinyl copolymer: “Novatech LD · XJ100H” manufactured by Nippon Polychem Co., Ltd. (MFR = 3 g / 10 min (190 ° C., JIS-K6760), density = 0.931 g / cm ³ (JIS-K6760) , Cyclic aminovinyl compound content = 5.1% by weight (0.7 mol%), proportion of cyclic aminovinyl compound present in isolation = 90 mol%, melting point = 111 ° C.)

UV absorber Triaryl triazine type UV absorber 1: CYASORB UV 1164 manufactured by Cytec Corporation (in formula (7), R ₇ is an octyl group and R _{8 to} R ₁₁ are methyl groups)
Triaryltriazine type ultraviolet absorber 2: Tinuvin 1577FF manufactured by Ciba Specialty Chemicals (triaryltriazine compound in which R ₇ is a hexyl group and R _{8 to} R ₁₁ are hydrogen atoms in formula (7))

(2) Surface treatment of film (anti-fogging coating application type)
The surface of the outer layer of the obtained tubular film was subjected to corona discharge treatment at a discharge voltage of 120 V, a discharge current of 4.7 A, and a line speed of 10 m / min, and the “wetting index” according to JIS-K6768 was measured and confirmed.

(3) Formation of anti-fogging coating film (anti-fogging coating type)
The main components (silica sol and / or alumina sol) shown below, a thermoplastic resin, a crosslinking agent and a liquid dispersion medium were blended to obtain an antifogging agent composition (antifogging coating type A, B). The antifogging agent composition was blended as follows.

<Anti-fog coating type A>
Inorganic colloidal sol (colloidal silica) 4.0
Thermoplastic resin (Sanmor SW-131: hydrophobic binder resin) 3.0
Cross-linking agent (TAZM) 0.1
Dispersion medium (water / ethanol = 3/1) 93
(Note) The amount of inorganic colloidal sol is indicated by the amount of inorganic particles, and the amount of thermoplastic resin is indicated by the solid content of the polymer.
Colloidal silica: Snowtex 30 manufactured by Nissan Chemical Co., Ltd., average particle size 15 nm, Sunmol SW-131: acrylic emulsion manufactured by Sanyo Kasei Co., Ltd. A. Z. M: Aziridine compound manufactured by Mutual Yakugyo Co., Ltd.

<Anti-fog coating type B>
Alcohol-dispersed colloidal silica (methanol silica) 6
Thermoplastic resin (2-hydroxyethyl acrylate: hydrophilic binder resin) 17
Cross-linking agent (silane derivative) 0.1
Surfactant (polyoxyethylene lauryl ether) 2.5
Dispersion medium (methanol) 74.4
(Note) The amount of inorganic colloidal sol is indicated by the amount of inorganic particles, and the amount of thermoplastic resin is indicated by the solid content of the polymer.
The antifoggant compositions A and B were applied to the surface of the base film surface-treated in (2) using a # 5 bar coater. The applied film was kept in an oven at 80 ° C. for 1 minute to volatilize the liquid dispersion medium to form an antifogging coating film. The thickness of the coating film of each obtained film was about 1 μm.

  Although the following physical properties were measured for each type provided with an anti-fogging coating (film thickness 100 μm), the gist was not changed even with a combination other than the resin and additives used this time, or with a film thickness different from this time. As long as the same effect is obtained. The following tests were conducted for each sample used this time. Each measuring method in an Example and a comparative example is shown below.

Initial film adhesion (film peelability: after itch test)
The stagnation test was carried out with a UF stagnation tester FT-501 manufactured by Ueshima Seisakusho. A film cut to a width of 2 cm and a length of 7 cm was allowed to stand in a thermostatic chamber at 23 ° C. for 60 minutes, and then a sag test was performed 10 times under the conditions of a load of 500 g, a sag width of 2 cm, and a stagnation speed of 120 times / min. Then, the coating film adhesion of the anti-fogging layer in the stagnation width portion was visually evaluated according to the following criteria.

A: peeling area 0 to 10%
○: peeling area 10-20%
Δ: Peeling area 20-50%
×: peeling area> 50%

Coating film adhesion after 800 hours of agricultural chemical resistance test The film was spread in a pipe house constructed in the above-mentioned field in Isshi-gun, Mie Prefecture so as to be in a sealed state. Moreover, the sulfur was fumigated for 8 hours during the day by heating it with a commercially available sulfur fumigator (trade name: Shinkoden) in the pipe house. The film that had been stretched and fumigated for about 4 months from mid-April 2011 to mid-August 2011 was exposed to a weather resistance tester (made by The Q-PANEL COMPANY). The coating film adhesion of these films after the elapse of 800 hours was measured according to the method for measuring the initial coating film adhesion.

Initial anti-fogging property A pipe house in the field of Isshi-gun, Mie Prefecture was spread so that the surface with the anti-fogging coating formed inside the house. The antifogging property on the inner surface of the stretched film was visually evaluated. The evaluation criteria are as follows.

A: Water droplets adhering to the film surface (the one facing the inside of the house, hereinafter the same) are combined to spread in a thin film, and the area of this thin film portion extends over 2/3 of the film surface.
○: Although coalescence of water droplets adhering to the film surface is recognized, the area of this thin film-like portion is less than 2/3 of the film surface and 1/2 or more.
Δ: Coalescence of water droplets adhering to the film surface is observed, but the area of the thin film portion is less than 1/2 of the film surface.
X: A combination of water droplets adhering to the film surface is not recognized.

Antifogging property after 800 hours of pesticide resistance test The film was spread in a sealed state in the pipe house constructed in the above-mentioned field in Isshi-gun, Mie Prefecture. Moreover, the sulfur was fumigated for 8 hours during the day by heating it with a commercially available sulfur fumigator (trade name: Shinkoden) in the pipe house. The film that had been stretched and fumigated for about 4 months from mid-April 2011 to mid-August 2011 was exposed to a weather resistance tester (made by The Q-PANEL COMPANY). The antifogging property after the lapse of 800 hours was measured in accordance with the initial antifogging measuring method (difference: the size of the sample is 15 cm wide and 30 cm long).

Initial physical properties (initial tensile strength)
Based on the measurement method of JIS-K6732, the mechanical strength of each obtained laminated film was measured for the tensile breaking strength in the film flow direction (vertical) at a temperature of 23 ° C., and the numerical value was shown.

Agrochemical weather resistance (tensile strength)
The film was spread on the pipe house constructed in Isshi-gun, Mie Prefecture, in a sealed state. Moreover, the sulfur was fumigated for 8 hours during the day by heating it with a commercially available sulfur fumigator (trade name: Shinkoden) in the pipe house. The film that was stretched and fumigated for about 3 months from mid-April 2011 to mid-July 2011 was exposed to a weather resistance tester (manufactured by The Q-PANEL COMPANY). The strength at break in the machine direction (resin flow direction) of these films at each time was measured by a tensile test (based on JIS-K6732). (Agrochemical resistance evaluation).

After storage for 2 years at 325nm total light transmittance test film after aging storage roll state, spectrophotometer total light transmittance of 325nm (Hitachi, U3500 type) was determined by. Moreover, the total light transmittance of 325 nm of the test film before storage was measured in advance.

[Examples 1-8, Comparative Examples 1-8]
With the above blending, a 100 μm film (antifogging agent kneaded and antifogging coating coating type) was prepared by a processing method. Various tests were carried out under the above conditions using the film obtained here.

Examples 1 and 2 and Comparative Examples 1 and 2
By the above formulation, a three-layer film (anti-fogging coating application type: no UV absorber added) having a film thickness of 100 μm and a layer ratio of 1/3/1 was prepared. Each film was evaluated by measuring the antifogging coating film adhesion after the property test, initial antifogging property, antifogging property after the agricultural chemical resistance test, and physical properties after the agricultural chemical resistance test. The results are shown in Table 1.

[Examples 3 and 4, Comparative Examples 3 and 4]
A three-layer film with a film thickness of 100 μm and a layer ratio of 1/3/1 (anti-fogging coating application type: no UV absorber added, ethylene-cyclic aminovinyl compound copolymer added (inner and outer layers)) was prepared by the above formulation. The initial anti-fogging coating film adhesion, the anti-fogging coating film adhesion after the agricultural chemical resistance test, the initial anti-fogging property, the anti-fogging property after the agricultural chemical resistance test, and the physical properties after the agricultural chemical resistance test are measured by the above methods. Each film was evaluated. The results are shown in Table 2.

[Examples 5 and 6, Comparative Examples 5 and 6]
By the above formulation, a three-layer film (anti-fogging coating application type: UV absorber added (all layers)) having a film thickness of 100 μm and a layer ratio of 1/3/1 is prepared, and the initial anti-fogging coating adhesion by the above method. Each film was evaluated by measuring the antifogging coating film adhesion after the agricultural chemical resistance test, the initial antifogging property, the antifogging property after the agricultural chemical resistance test, and the physical properties after the agricultural chemical resistance test. The results are shown in Table 3.

[Examples 7 and 8, Comparative Examples 7 and 8]
With the above formulation, a three-layer film having a film thickness of 100 μm and a layer ratio of 1/3/1 (anti-fogging coating application type: UV absorber added (intermediate layer), ethylene-cyclic aminovinyl compound copolymer added (inner and outer layers) ), And after the initial anti-fogging coating film adhesion, anti-fog coating adhesion after the agricultural chemical resistance test, initial anti-fogging property, anti-fogging property after the agricultural chemical resistance test, physical properties after the agricultural chemical resistance test Was measured and each film was evaluated. The results are shown in Table 4.

[Examples 9 to 10]
The total light transmittance at 325 nm was measured for a sample in which no phenolic antioxidant was added to the base film and a sample in which the antioxidant was added to the intermediate layer. The results are shown in Table 5. In Examples 9 and 10, 8 parts by weight of ethylene-cyclic aminovinyl copolymer was added to each of the inner and outer layers.

  As is clear from the above results, the surface of the polyolefin-based resin base film according to the present invention contains at least one kind of hindered amine compound having at least one ring structure represented by the formula (1) in the intermediate layer. In addition, the multilayer film for agriculture, which is provided with a coating layer of an antifogging paint mainly composed of a synthetic resin binder and an inorganic colloidal sol, has a coating film adhesion, antifogging property and tensile strength after agrochemical treatment. It is remarkably excellent (Examples 1-8). Furthermore, by combining with a triaryltriazine-type ultraviolet absorber and / or a copolymer of ethylene (A) and the cyclic aminovinyl compound (B) represented by the above formula (8), a coating after a good agricultural chemical treatment is obtained. Film adhesion, antifogging and weather resistance can be imparted (Examples 3 to 8).

  On the other hand, when other than the hindered amine compound according to the present invention is used, sufficient coating film adhesion, antifogging property, and weather resistance after agrochemical treatment cannot be imparted. (Comparative Examples 1-8).

That is, when the resin composition of the present invention is applied to an agricultural film, at least one hindered amine compound having at least one piperidine ring structure having at least one ring structure represented by formula (1) is at least intermediate. The coating film layer of the antifogging paint mainly composed of a synthetic resin binder and an inorganic colloidal sol is included in the polyolefin-based resin base film (R ₁ represents a functional group or a compound (including oligomer and polymer)) contained in the layer. Copolymer of triaryltriazine type ultraviolet absorber and / or ethylene (A) and cyclic aminovinyl compound (B) represented by the above formula (8), which is essential for the agricultural polyolefin-based multilayer film according to the present invention The effect can be further sustained and improved by adding.

  As for the ultraviolet absorber, when the triaryltriazine type ultraviolet absorber described in the present invention is used, since the long-term ultraviolet absorbing ability can be maintained, the effect can be maintained for a long time. On the other hand, unless a UV absorber is added, it is difficult to maintain weather resistance and agricultural chemical resistance at a high level.

  These conditions are indispensable for obtaining the effects of the present invention, and whichever of these conditions is lacking, pesticide resistance, UV-absorbing ability retention, crop cultivatability such as mating using bees, and sustaining these effects. Agricultural films having a good balance of performance such as properties cannot be obtained.

  Furthermore, in the present invention, as shown in Table 5, by setting the concentration of the phenolic antioxidant in the entire layer of the base film to 0.03% by weight or less, the film has a wavelength of about 325 nm after storage over time. The decrease in total light transmittance can be suppressed, and even when the total light transmittance is reduced to less than 40%, the light transmittance near 325 nm is recovered early when exposed to sunlight for a short period. preferable.

Claims (11)

An agricultural polyolefin multilayer film having at least an outer layer, an intermediate layer and an inner layer, and a coating film layer made of an antifogging agent composition provided on the surface of a base film containing a polyolefin resin,
Including at least one compound A having at least one ring structure represented by the following formula (1) and having a molecular weight of 1000 or more in an intermediate layer;

(R ₁ represents a functional group or a compound (including an oligomer and a polymer).)
The multilayer film for agriculture, wherein the antifogging agent composition comprises a synthetic resin binder and an inorganic colloid sol as main components. 2. The agricultural polyolefin-based multilayer film according to claim 1, wherein the compound A is an adduct obtained by adding a compound represented by the following formula (2) to a polymer having an average molecular weight of 300 or more.

(In the formula, n represents an integer of 1 to 4, and R ₂ and R ₃ may be the same or different, and each represents a hydrogen atom or an arbitrary substituent.) 3. The polyolefin-based multilayer film for agriculture according to claim 1 or 2, wherein the compound A is an adduct obtained by adding a compound represented by the following formula (3) to a polymer having an average molecular weight of 300 or more. .

(In the formula, n represents an integer of 1 to 4, X represents —O— or —NH—, R ₃ represents a hydrogen atom or an arbitrary substituent, and R ₄ represents a hydrogen atom, having 1 to 20 carbon atoms. Represents an aliphatic acyl group, an aliphatic polyvalent acyl group, an aromatic acyl group or an aromatic polyvalent acyl group.) The agricultural polyolefin-type multilayer film of Claim 1 or 2 with which the compound A is represented by the following formula | equation (4).

(In the formula, R ₅ represents a hydrogen atom or an arbitrary substituent, E is an alkyl group having 60 to 1,000,000 carbon atoms, and the alkyl chain of the alkyl group is an alkyl substituent or an aromatic group. Can contain substituents and acidic groups as substituents and can be interrupted by alkene units and heteroatoms, n 'is an integer from 1 to 1000)   The agricultural polyolefin multilayer film according to claim 4, wherein the alkyl group E is derived from wax. The agricultural polyolefin-based multilayer film according to claim 1, wherein the compound A is represented by the following formula (5).

(Where m is in the range of 1 to 15,
R ₁ represents a C1-C20 alkyl group or a cycloalkyl group;
R ₁₂ represents an optionally substituted alkylene group having 1 to 12 carbon atoms, alkenylene group, cycloalkylene group, or arylene group,
B represents, independently of each other, Cl, —OR ₁₃ , —N (R ₁₄ ) (R ₁₅ ) or a group in which the group of the formula (1) is bonded to —Y—;
here,
R ₁₃ , R ₁₄ , and R ₁₅ each represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an alkenyl group, an aryl group, or an arylalkyl group that may have a substituent. ,
-Y- represents -O- or> N-R ₁₆
R ₁₁ or R ₁₆ each represents a group represented by formula (1) or one of the definitions given for R ₁₃ . ) The agricultural polyolefin-based multilayer film according to claim 1, wherein the compound A is represented by the following formula (6).

(Wherein R ₆ represents a C1-C12 alkyl group,
Z represents a C1-C4 alkylene group or a carbonyl group (C = O). ) The agricultural polyolefin-type multilayer film of any one of Claims 1-7 in which the compound represented by the following formula | equation (7) is contained in the intermediate | middle layer at least.

(Wherein R _{7 to} R ₁₁ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms)   The agricultural polyolefin multilayer film according to any one of claims 1 to 8, wherein the synthetic resin binder is an acrylic resin and / or a urethane resin, and the inorganic colloid sol is colloidal silica and / or colloidal alumina. The base film has at least one layer containing a copolymer of ethylene (A) and a cyclic aminovinyl compound (B) represented by the following formula (8). The polyolefin multilayer film for agricultural use according to the item.

(In the formula, R ₁₂ and R ₁₃ each independently represent a hydrogen atom or a methyl group, and R ₁₄ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)   The agricultural polyolefin-based multilayer film according to any one of claims 1 to 10, wherein the base film substantially does not contain a phenol-based antioxidant.