JP2003138035A - Polyolefin-based film for agriculture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an agricultural film having good weatherability and anti- fogging properties and excellent in tight adhesion to an anti-fogging coating film even under acidic conditions. SOLUTION: This polyolefin-based film for agriculture consists of multiple layers or a single layer, having at least one layer containing a polyolefin-based resin and at least one hindered amine compound which has at least two piperidine ring structures represented by formula (1) [wherein R1 is a >=1C functional group or compound (including an oligomer and a polymer) containing at least one methylene group] and which has an average molecular weight of 1,000 or higher, and at least one layer containing at least one ultraviolet absorber.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyolefin-based agricultural film excellent in long-term weather resistance, durability, and pesticide resistance, and is used after long-term extension and under acidic conditions such as acid rain and pesticides. The present invention relates to a polyolefin-based agricultural film which has a small decrease in weather resistance and which is excellent in anti-fogging persistence and anti-fogging coating adhesion when an anti-fogging coating is applied.

[Background technology]

In recent years, polyolefin-based resin films for agriculture, which are mainly composed of polyolefin-based resins, are light in weight because they have a density smaller than that of vinyl chloride resin, and generate little toxic gas even when incinerated. Widely-used films that do not require a bonding process to provide such films can be provided at low cost, and are therefore being widely used.

[0003] Agricultural houses are getting larger year by year, and a lot of manpower is required for the film spreading work for covering the houses with a film. On the other hand, the number of farmers is decreasing year by year and the population is aging,
It is not easy to secure manpower for the annual expansion work. In consideration of such a situation, the film to be spread on the house is a film that is easy to spread and has a long service life until it is replaced as much as possible. In other words, it has a long life of 2 years or more and can maintain the initial performance for a long time. Development of high performance agricultural films is required.

[0004] With respect to such requirements, the properties that the film should have include weather resistance and pesticide resistance. Among these performances, the most difficult technique up to now is to impart pesticide resistance, and many studies have been conducted in the past. Conventionally, in agricultural applications, as a method of imparting pesticide resistance to a polyolefin film, a method of combining a hindered amine compound having a general structure with hydrotalcite, a method of using a weathering agent having a special structure, etc. have been proposed. There is.

However, the method of combining with a heat-retaining agent has a low effect of improving pesticide resistance, and when it is actually used for agricultural purposes, when pesticide is sprayed inside the house, the weather resistance is rapidly lowered, and it is practically used. There was a problem. On the other hand, JP-A-11-80569 and JP-A-2001-1398.
The compound as shown in Japanese Patent No. 21 can improve the pesticide resistance by adding it. However, for agricultural films used under harsh conditions,
Further improvement of pesticide resistance has been demanded, and further improvement and a specific combination method of a weather resistance agent and an ultraviolet absorber capable of giving good pesticide resistance have been demanded.

Further, an agricultural film containing an ethylene / cyclic aminovinyl compound copolymer added for the purpose of further sustaining the weather resistance improving effect (for example, JP-A-5-11272).
5 and JP-A-5-124161). This ethylene / cyclic aminovinyl compound copolymer is clearly distinguished from a usual hindered amine weatherproofing agent in terms of its production method and molecular structure (for example, Japanese Patent Nos. 2695971 and 2695975). However, this ethylene-based copolymer has a high compatibility with the resin, and although the weather resistance improving effect by the addition thereof, particularly the weather resistance improving effect in the long term is recognized, it is high cost, so that the addition amount can be increased. There are problems such as difficulties. When the addition amount is low, the proportion of hindered amine groups in the total weight of the compound is low as compared with a normal hindered amine weathering agent, so that the weather resistance improving effect per added weight is low, and it is not always generally used. I couldn't say.

Further, Japanese Patent Laid-Open No. 2001-2842 proposes a resin composition containing a triazine-based ultraviolet absorber and an ethylene-based copolymer having a hindered amine as a side chain. However, even when an agricultural film was produced with the addition amount described in the application, the weather resistance under acidic conditions was still insufficient.

[0008]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that when a hindered amine compound having a specific structure is combined with an ultraviolet absorber, particularly an ultraviolet absorber having a specific structure, It was found that good pesticide resistance can be imparted as compared with the request. In particular, in the method according to the present invention, when the anti-fogging coating is applied, for example, the adhesion of the anti-fogging coating under acidic conditions is good, and it is spread outdoors for a long time, including acid rain and pesticides. It is useful as an agricultural film that is often exposed under acidic conditions. Furthermore, by blending a specific ethylene-cyclic amino vinyl compound to the base film, in addition to the above effects,
The inventors have found that a bleed-out on the resin surface is significantly suppressed, and that a practical agricultural film having excellent anti-fogging durability and long-term weather resistance can be obtained, and completed the present invention.

The present invention has been made based on the above findings, and has a hindered amine having a polyolefin resin and at least two piperidine ring structures represented by the following formula (1) and having an average molecular weight of 1,000 or more. A polyolefin-based agricultural film comprising at least one layer containing at least one compound and at least one layer containing at least one ultraviolet absorber (R1) Has 1 or more carbon atoms,
Functional groups or compounds (including oligomers and polymers) containing at least one or more methylene groups are provided.

[0010]

[Chemical 7] (1)

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The polyolefin resin used in the present invention includes α
-Olefin-based homopolymers, copolymers of α-olefins with different monomers as main components, α-olefins and polyunsaturated compounds such as conjugated dienes or non-conjugated dienes, acrylic acid, methacrylic acid, acetic acid Examples thereof include copolymers with vinyl and the like, for example, high-density, low-density or linear low-density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-4-methyl-1- Examples thereof include a pentene copolymer, an ethylene-vinyl acetate copolymer, an ethylene-acrylic acid copolymer and the like. Among these, low-density polyethylene having a density of 0.910 to 0.935, ethylene-α-olefin copolymer, and ethylene-containing a vinyl acetate content of 30% by weight or less.
A vinyl acetate copolymer is preferable as an agricultural film in terms of transparency, weather resistance and price. Further, in the present invention, an ethylene-α-olefin copolymer resin obtained by copolymerizing with a metallocene catalyst can be used as at least one component of the polyolefin resin.

This is usually called metallocene polyethylene, and ethylene and α such as butene-1, hexene-1, 4-methylpentene-1, octene.
-Copolymer with olefin, for example, JP-A-58-
It can be obtained by various known production methods described in Japanese Patent Application Laid-Open No. 19309 and Japanese Patent Application Laid-Open No. 6-9724.

Preferably, it has the following physical properties. Melt flow rate (MFR) MFR measured by JIS-K7210 is 0.01
It shows a value of -10 g / 10 min, preferably 0.1-5 g / 10 min. When the MFR is larger than this range, the film meanders during molding and is difficult to stabilize. Also, the MF
If R is smaller than this range, the resin pressure at the time of molding increases and a load is applied to the molding machine. Therefore, it is necessary to reduce the production amount and suppress the increase in pressure, which is not practical.

[0014]density The density measured by JIS-K7112 is 0.880.
~ 0.930 g / cm ³  , Preferably 0.880-
0.920 g / cm³  It indicates the value of. The density
If it is larger than this range, the transparency tends to deteriorate. Also,
If the density is lower than this range, the film surface becomes sticky.
As a result, blocking occurs and it becomes impractical.

Molecular weight distribution Gel permeation chromatography (GPC)
The molecular weight distribution (weight average molecular weight / number average molecular weight) determined by 1.5 to 3.5, preferably 1.5 to 3.
It indicates a value of 0. If the molecular weight distribution is larger than this range, the mechanical strength is lowered, which is not preferable. When the molecular weight distribution is smaller than this range, the film meanders during molding and is difficult to stabilize.

The ethylene-vinyl acetate copolymer resin used in the present invention has a vinyl acetate content of 10 to 25% by weight, preferably 12 to 20% by weight. If the vinyl acetate content is less than this range, the resulting film becomes hard and wrinkles and slacks are likely to occur when it is spread on the house, and the antifogging property is adversely affected, resulting in poor practicability. Above the range,
Since the melting point of the resin is low, the film sags at a high temperature in the summer when the house is extended, and the film is liable to be fluttered by the wind and is likely to be broken, so that it is not practical.

The agricultural film in the present invention is a layer having at least two piperidine ring structures represented by the following formula (1) and containing at least one hindered amine compound having an average molecular weight of 1,000 or more. A polyolefin-based agricultural film comprising a multi-layered or single-layered base film having at least one layer of the above, and a coating layer of an antifogging paint containing a synthetic resin binder and an inorganic colloid sol as main components. (R1 represents a functional group or compound (including oligomer and polymer) having at least one methylene group having 1 or more carbon atoms)

[Chemical 8] (1)

The method for obtaining the hindered amine compound represented by the above formula (1) is not particularly limited, and a commercially available product can be used. For example, TINUVIN NOR 3
71 (manufactured by Ciba Specialty Chemicals Co., Ltd.),
ADEKA STAB LA-900 (made by Asahi Denka Co., Ltd.) etc. are mentioned. In addition, these compounds are listed in Table 2000-5.
It is obtained in accordance with the method described in Japanese Patent No. 12676 and Japanese Patent Laid-Open No. 2000-336118.

Among the above hindered amine compounds, a hindered amine compound (2,2,6,6-tetramethylpiperidine derivative having a triazine skeleton in the compound and having a molecular weight of 2000 or more (preferably 5000 or less) and a mixture thereof, preferably R1. Is a C1-C20 alkyl group, or a cyclohexyl group or an octyl group.), For example, TINUVIN NOR 371 (manufactured by Ciba Specialty Chemicals Co., Ltd.) is a hindered amine-based weather resistance commonly used for ordinary agricultural films. Because of a similar molecular weight to the agent (Chimasorb 944: a compound having a triazine skeleton and having a hydrogen atom bonded instead of —O—R1 in the above formula (1)),
The acid resistance of the film can be improved by the same addition method. However, since it is colored itself, when it is used for an agricultural film that requires high transparency, it is necessary to devise the amount and method of addition. When a high concentration is added to the film surface layer, the adhesion of the coating film may be hindered due to bleed-out, so in a preferred embodiment, 50% or more of the total amount added to the intermediate layer of the multilayer film is preferred. Is included.

On the other hand, among the above hindered amine compounds, a compound represented by the following general formula (2) has a molecular weight of 300.
Adducts added to the above polymers, such as ADEKA STAB
Since LA-900 (manufactured by Asahi Denka Co., Ltd.) has a high molecular weight, it is difficult to bleed out, but since it is grafted to a polymer, the effect of improving weather resistance per added weight is low. (In the formula, n represents an integer of 1 to 4, and X represents -O-.
Or -NH- is represented, R2 is a hydrogen atom, carbon number 1-20.
Represents an aliphatic acyl group, an aliphatic polyvalent acyl group, an aromatic acyl group or an aromatic polyvalent acyl group. ) As a polymer having a molecular weight of 300 or more, polypropylene,
Examples thereof include polymers having unsaturated bonds such as polyolefins such as high-density polyethylene, low-density polyethylene and linear low-density polyethylene.

[Chemical 9] (2)

The content of the hindered amine compound in the resin composition of the agricultural film of the present invention is less than 10 parts by weight based on 100 parts by weight of the polyolefin resin.
Preferably 0.01 to 5 parts by weight, more preferably 0.1.
~ 4 parts by weight. In the case of the type grafted to a polymer such as ADEKA STAB LA-900, the addition amount can be increased within a range, but in the case of TINUVIN NOR 371 having a molecular weight of 5000 or less, a weathering agent is easily blown to the film surface due to bleeding out, and Concentration addition is difficult. Therefore, if the content is less than the above range, the effect of improving the weather resistance is low, and if it exceeds the above range, bleeding out causes a problem in practical use as an agricultural film.

The molecular weight of the hindered amine compound according to the present invention is 1000 or more, preferably 2000 or more. In order to obtain sufficient bleed-out resistance, it is more preferably 2000 or more, still more preferably 3000 or more.

The hindered amine compound used in the present invention does not necessarily have to be contained in all layers of the multilayer film from the viewpoint of cost, for example, when it is used in a multilayer film, and at least one layer may be contained. Good. For example, in the case of a multi-layer film, the effect on the coating film is not limited to the additives added to the layer in contact with the coating film, but also the additives transferred and transferred from other layers. Layers or inner and outer layers are preferred, but may be inner layers only, intermediate layers only, outer layers only or any combination thereof.

The hindered amine compound can be used in combination with one or more kinds of other commonly used hindered amine weathering agents. Further, for the layer not containing the hindered amine compound, one or more commonly used hindered amine weathering agents can be used. Of course, the hindered amine compound may be contained in all layers, but it may be contained in, for example, the house middle layer, and the other layers may contain a hindered amine-based weathering agent which is usually blended for agriculture. In addition, the hindered amine compound and the hindered amine weatherproofing agent which is usually blended for agriculture can be contained in the same layer. In that case, it is more cost effective than the case where the hindered amine compound is used for all layers.

The hindered amine weatherproofing agents which are usually used in combination for agricultural use have a hindered amine compound having at least two piperidine ring structures represented by the following formula (6) in the molecule and having a molecular weight of 500 or more ( Less than,
It is also referred to as a "piperidine ring-containing hindered amine compound"). Here, when the number of piperidine rings of the piperidine ring-containing hindered amine compound is less than 2, sufficient weather resistance cannot be obtained, and when the molecular weight is less than 500, volatilization tends to occur, and long-term weather resistance cannot be obtained. In addition, the piperidine ring-containing hindered amine compound preferably has 2 to 50 piperidine rings and a molecular weight of 750 or more.

[0026]

[Chemical 10] (6)

Examples of the piperidine ring-containing hindered amine compound that can be used in combination include, for example, bis (1,2,2,2)
6,6-Pentamethyl-4-piperidyl) -2-butyl-2- (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, tetra (2,2,6,6-tetramethyl-4-piperidyl) ) Butane tetracarboxylate,
Tetra (1,2,2,6,6-pentamethyl-4-piperidyl) butane tetracarboxylate, bis (2,2
2,6,6-tetramethyl-4-piperidyl) -di (tridecyl) butane tetracarboxylate, bis (1,
2,2,6,6-pentamethyl-4-piperidyl) .di (tridecyl) butane tetracarboxylate, 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-piperidyloxycarbonyl) (Oxy) 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 and the like.

Examples of commercially available hindered amine compounds that can be used in combination include TINUVIN765 and TINUVI.
N770, TINUVIN780, TINUVIN14
4, TINUVIN 622LD, CHIMASSORB
119FL, CHIMASSORB 944 (above, manufactured by Ciba Geigy), Sanol LS-765 (Sankyo Co., Ltd.)
Manufactured), MARK LA-63, MARK LA-68,
MARK LA-68, MARK LA-62, MAR
K LA-67, MARK LA-57 (above, manufactured by Adeka Argus Co., Ltd.), CYASORB UV-3346,
CYASORB UV-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.

The agricultural film of the present invention can have good weather resistance by adding an ultraviolet absorber. UV absorbers that are usually blended for agricultural use include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,
2-hydroxy-4-octoxybenzophenone, 5,
2-hydroxybenzophenones such as 5′-methylenebis (2-hydroxy-4-methoxybenzophenone);
2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'
-Di-tert-butylphenyl) benzotriazole, 2-
(2'-Hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl)
-5-chlorobenzotriazole, 2- (2'-hydroxy-5'-tertiaryoctylphenyl) benzotriazole, 2- (2'-hydroxy-3'.5'-dicumylphenyl) benzotriazole, 2,2 2- (2'-hydroxyphenyl) benzotriazoles such as'-methylenebis (4-tertiaryoctyl-6-benzotriazolyl) phenol; phenyl salicylate, resorcinol monobenzoate, 2,4-ditertiary butylphenyl-
3 ', 5'-di-tert-butyl-4'-hydroxybenzoate, 2,4-di-tert-amylphenyl-3', 5'-di-tert-butyl-4'-hydroxybenzoate, hexadecyl-3,5- Benzoates such as ditertiary butyl-4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-
Cyanoacrylates such as β, β-diphenyl acrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; 2- (4,6-diphenyl-1,3,5-triazine-2) -Yl) -5
[(Hexyl) oxy] -phenol, 2- [4,6-
Examples thereof include triazines such as bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol. These ultraviolet absorbers are used alone or in combination of two or more.

As a highly effective ultraviolet absorber, a triaryltriazine type ultraviolet absorber represented by the following formula (3) can be mentioned.

[Chemical 11] (3) (In the formula, R3 to R7 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)

Here, in the formula (3), R3 to R7 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. More preferably, R3 is an alkyl group having 6 to 10 carbon atoms, particularly preferably an alkyl group having 6 to 8 carbon atoms, R4 to R7 are hydrogen atoms or an alkyl group having 1 to 2 carbon atoms, and particularly preferably hydrogen. Atom or a methyl group.

In the above formula (3), if the carbon number of R3 is less than the above range, bleeding out tends to occur, which is not preferable, and if it exceeds the above range, the weather resistance tends to be poor, such being undesirable. If the number of carbon atoms of R2 to R5 is less than the above range, bleeding out tends to occur, which is not preferable, and if it exceeds the above range, the weather resistance is deteriorated, which is not preferable. Particularly, in the ultraviolet absorbent according to the present invention, when R3 in the formula (3) is an octyl group and R4 to R7 are methyl groups, or the ultraviolet absorbent according to the present invention is the R3 in the formula (3). Is a hexyl group and R4 to R7 are hydrogen atoms, an agricultural film having particularly excellent bleed-out resistance and chemical stability can be obtained.

The method for obtaining the triaryltriazine-based UV absorber represented by the above formula (3) is not particularly limited, and a commercially available product can be used. For example UV1164
(Manufactured by Cytec), TINUVIN 1577 FF
(Made by Ciba Specialty Chemicals) and the like.

The content of the triaryltriazine type ultraviolet absorber represented by the above formula (3) in the agricultural film of the present invention is less than 5 parts by weight, preferably 0 parts by weight based on 100 parts by weight of the polyolefin resin. 0.001 to 3 parts by weight, more preferably 0.005 to 1 part by weight. If the content is less than the above range, the effect of improving weather resistance is low, and if the content exceeds the above range, there is a problem such as a decrease in transparency due to bleed-out.

The above-mentioned triaryltriazine type ultraviolet absorber used in the present invention is cost effective.
For example, when it is used for a multilayer film, it does not necessarily have to be contained in all layers of the multilayer film, and it is sufficient that at least one layer is contained. Further, this triaryltriazine type UV absorber can be used in combination with one or more kinds of other UV absorbers which are usually used. Further, for the layer containing no triaryltriazine type ultraviolet absorber, one or two or more types of ultraviolet absorbers usually used can be used. The triaryltriazine type ultraviolet absorber may be contained in all the layers, of course. However, for example, the triaryltriazine type ultraviolet absorber may be contained in the house middle layer, and the other layers may contain the ultraviolet absorber which is usually blended for agriculture. Further, the same layer may contain a triaryltriazine type ultraviolet absorber and an ultraviolet absorber usually blended for agriculture. In that case, it is more cost effective than the case where a triaryltriazine type ultraviolet absorber is used for all layers.

The above-mentioned triaryltriazine type ultraviolet absorber used in the present invention is characterized by having a good bleed-out property, but when it is added to a multilayer film, the bleed-out property can be further improved. I can. As a method of adding good bleed-out resistance,
UV absorber content per unit volume in the intermediate layer X> UV absorber content per unit volume in the inner layer Y, and X
> Agricultural multilayer film having an ultraviolet absorber content rate Z per unit volume in the outer layer, or an agricultural multilayer film in which 80% or more of the ultraviolet absorber addition amount in the entire film is contained in the intermediate layer, and further multilayer There can be mentioned, for example, an agricultural multilayer film obtained by adding an ultraviolet absorber to a layer other than the surface layer of the film (other than the house inner layer and the house outer layer: an intermediate layer).

The present invention further provides, as a light stabilizer, a copolymer of ethylene (A) and a cyclic aminovinyl compound (B) represented by the following formula (5) (hereinafter, "ethylene / cyclic aminovinyl compound copolymer). (Hereinafter referred to as "coalescence"), an agricultural film having excellent long-term weather resistance and bleed-out resistance can be obtained. The ethylene / cyclic aminovinyl compound copolymer exerts an effect as a light stabilizer that markedly improves long-term weather resistance, as compared with a hindered amine-based weather resistance agent used in a general agricultural film.

[0038]

[Chemical 12] (5)

In the above formula (5), R8 and R9 each independently represent a hydrogen atom or a methyl group, and R10 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Preferably, R8 and R9 are each a methyl group, and R10 is a hydrogen atom.

The vinyl compound (B) represented by the formula (5) is known and known in the art, for example, JP-B-47-8539.
No. 48-65180 and the like.

Typical examples of the vinyl compound represented by the formula (5) include 4-acryloyloxy-2,2,6,6-.
Tetramethylpiperidine, 4-acryloyloxy-
1,2,2,6,6-Pentamethylpiperidine, 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-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2
6,6-tetramethylpiperidine, 4-crotonoyloxy-1-propyl-2,2,6,6-tetramethylpiperidine and the like can be mentioned.

The preferred ethylene / cyclic aminovinyl compound copolymer is the (B) relative to the sum of the ethylene (A) and the cyclic aminovinyl compound (B).
Is 0.0005 to 0.85 mol%, more preferably 0.001 to 0.55 mol%. That is, the preferable thing of this copolymer has high photostability although the content of the vinyl monomer (cyclic amino vinyl compound (B)) which has a hindered amine group in the side chain is small. Cyclic amino vinyl compound (B)
When the concentration is 0.0005 mol%, the light-stabilizing effect is sufficiently exerted, while when it exceeds 0.85 mol%, it tends to be substantially uneconomical.

Further, in the ethylene / cyclic aminovinyl compound copolymer, two or more (B) are not continuous in the copolymer, and the ratio of isolated (B) is 8 with respect to the total amount of (B).
It is preferably 3% or more, and more preferably 90% or more.

The presence of the cyclic aminovinyl compound (B) is confirmed as described in JP-A-4-80215, as follows. 13C-NMR (for example, JNM-GSX270 Spectrometer manufactured by JEOL Ltd.) according to a known method (see, for example, Kagaku Dojin's “Machine Analysis Tebiki (1)” pages 53-56 (1985)) Ethyl acrylate (see "Polymer Analysis Handbook", Asakura Shoten, page 969 (1985)) and ethylene-hydroxyethyl acrylate copolymer (Eur. Poly. J.25)
Vol. 4, No. 4, pp. 411-418 (1989)), the peak at 32.9 ppm in the TMS standard is attributed to the methylene group at the α position from the branch point of the isolated vinyl monomer (B). The peak at 35.7 ppm was attributed to a methylene group sandwiched between the branch points of two consecutive vinyl monomers (B). By using these two signals, the ratio of the vinyl monomer (B) existing independently in the copolymer of ethylene (A) and the vinyl monomer (B) can be calculated by the following calculation formula.

[0045]

[Equation 1] Peak area of 32.9 ppm / 32.9 ppm
Peak area + 35.7 ppm peak area

The MFR of the ethylene / cyclic aminovinyl compound copolymer (JIS-K6760 (190 ° C., 2.
16 kg load) is 0.1 to 2)
00 g / 10 minutes, preferably 0.5 to 20 g / 10 minutes,
It is more preferably 1 to 5 g / 10 minutes. If the MFR is less than the above range, the blending with the polyolefin resin is poor, and when blended, it causes visible defects in film applications such as fish eyes and spots. On the other hand, when the MFR exceeds the above range, bleeding and blooming phenomena due to diffusion loss occur even in a copolymer having a large molecular weight,
When blended with a polyolefin resin, it causes a decrease in strength of the obtained resin composition.

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

The content of the ethylene / cyclic aminovinyl compound copolymer in the polyolefin resin composition of the present invention is 2 to 10 parts by weight, preferably 2 to 6 parts by weight, based on 100 parts by weight of the polyolefin resin. Is.
If this content is less than the above range, the weather resistance will be poor, which is not preferable, and if it exceeds the above range, it is not preferable in terms of economy.

The ethylene / cyclic aminovinyl compound copolymer used in the present invention may of course be contained in all layers. For example, the ethylene / cyclic aminovinyl compound copolymer may be contained in the innermost layer and the outermost layer (outer surface of the house), and the other layers are as described above. In addition, a hindered amine-based light stabilizer which is usually blended for agriculture can be contained. Further, the same layer may contain an ethylene / cyclic aminovinyl compound copolymer and a hindered amine light stabilizer which is usually blended for agriculture. In that case, it is more cost effective than the case where an ethylene / cyclic aminovinyl compound copolymer is used for all layers.

The agricultural film of the present invention can have good heat retention by adding an infrared absorber. Infrared absorber is effective M as a heat retaining agent
Inorganic compounds containing at least one atom of g, Ca, Al, Si and Li (inorganic oxides, inorganic hydroxides, hydrotalcites, etc.) can be used.

In particular, when the hydrotalcite-type infrared absorber represented by the following formula (4) is used, an inexpensive film having good moldability can be obtained.

Embedded image Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ · 3.5H ₂ O (4)

The method for obtaining the infrared absorbent (heat retaining agent) represented by the above formula (4) is not particularly limited, and commercially available ones can be used. For example, DHT4A (Kyowa Chemical Co., Ltd.) can be used.
Manufactured) and the like.

Other infrared absorbers that can be used include
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, lithium-aluminum composite Hydroxide, aluminum-lithium-magnesium complex carbonate compound, aluminum-lithium-magnesium complex silicate compound, magnesium-aluminum Um silicon composite hydroxide, magnesium aluminum silicon composite sulfate compounds, magnesium aluminum silicon composite carbonate compound, a metal complex hydroxide salt containing more anions. These may be dehydrated water of crystallization.

The inorganic fine particles may be natural products,
Further, it may be a synthetic product. Further, the inorganic fine particles,
It can be used without being limited by its crystal structure, crystal grain size and the like.

The surface of the inorganic fine particles is higher fatty acid such as stearic acid, higher fatty acid metal salt such as alkali metal oleate, organic sulfonic acid metal salt such as alkali metal dodecylbenzene sulfonate, higher fatty acid amide. Those coated with higher fatty acid ester or wax can also be used.

The above-mentioned inorganic fine particles can be used alone or in combination of two or more kinds. The average particle size thereof is preferably 0.05 to 15 μm, more preferably 0.1.
It is in the range of 10 μm. When the average particle size of the inorganic fine particles is smaller than the above range, the dispersibility in the resin is poor, and lumps (secondary aggregates of inorganic substances) are generated to deteriorate the film appearance, and powdering during kneading with the resin occurs. Extremely poor handling. On the other hand, when the average particle size of the inorganic fine particles is larger than the above range, the transparency is inferior or the extruder breaker screen portion is clogged, resulting in poor productivity.

In the polyolefin-based agricultural film of the present invention, various additives usually used in synthetic resins can be used in combination. As those additives, for example, 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, sulfur-based, phenol-based and phosphite-based antioxidants, heat stabilizers, lubricants, antistatic agents, colorants, antiblocking agents, antifog agents, Examples include anti-fog agents.

The antifog agent is not particularly limited,
A polyhydric alcohol partial ester type composed of a polyhydric alcohol and higher fatty acids, including various known nonionic surfactants, anionic surfactants, cationic surfactants and the like, is preferable. . Specific examples of such an antifogging agent include, for example, nonionic surfactants such as sorbitan monostearate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monobehenate, condensate of sorbitan and alkylene glycol and fatty acid. Glycerin monopalmitate, glycerin monostearate, glycerin monolaurate, diglycerin monopalmitate, glycerin dipalmitate, glycerin distearate, diglycerin monopalmitate monostea , Triglycerin monostearate, triglycerin distearate or glycerin-based surfactants such as alkylene oxide adducts thereof, polyethylene glycol monostearate, polyethylene glycol Polyethylene glycol-based surfactants such as coal monopalmitate and polyethylene glycol alkyl phenyl ether, and other trimethylolpropane-based surfactants such as trimethylolpropane monostearate, pentaerythritol monopalmitate, pentaerythritol monostearate and other penta Erythritol-based surfactants, alkylene oxide adducts of alkylphenols; esters of sorbitan / glycerin condensates with fatty acids, sorbitan / alkylene glycol condensates with fatty acids; diglycerindiolate sodium lauryl sulfate, dodecylbenzene sulfonic acid Sodium, cetyltrimethylammonium chloride, dodecylamine hydrochloride, lauryl laurylamide ethyl phosphate Can be exemplified triethylammonium cetyl ammonium iodide, oleyl amino diethylamine hydrochloride, and those containing dodecyl pyridinium salts, etc. and their isomers.

Examples of the above-mentioned fog-preventing agent include fluorine-containing surfactants and silicone-containing surfactants, and specific examples of the fluorine-containing surfactants are those bonded to C of the hydrophobic group of ordinary surfactants. Instead of H, part or all of F
And a surfactant containing a perfluoroalkyl group or a perfluoroalkenyl group. The above various additives may be used alone or in combination of two or more. Examples of the fluorine-containing compound having a perfluoroalkyl group include anionic fluorine-containing surfactants, cationic fluorine-containing surfactants, amphoteric fluorine-containing surfactants, nonionic fluorine-containing surfactants and fluorine-containing oligomers. can give.

The amount of the above-mentioned fluorine-containing compound having a perfluoroalkyl group used is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the thermoplastic resin. If the amount of the fluorine-containing compound used is less than 0.001 part by weight, the antifog effect is hardly exhibited, and if it exceeds 10 parts by weight, the effect is saturated, which is not preferable.

As the filler, for example, silica, talc, aluminum hydroxide, in order to suppress stickiness of the film or to further improve heat retention,
Hydrotalcite, calcium sulfate, calcium silicate, calcium hydroxide, magnesium hydroxide, kaolin clay, mica, alumina, magnesium carbonate, sodium aluminate, conductive zinc oxide, lithium phosphate and the like are used. These fillers may be used alone or in combination of two or more.

Examples of the above-mentioned phenolic antioxidants include 2,6-di-tert-butyl-p-cresol and 2,6
-Diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol Bis [(3,5-di-tert-butyl-
4-hydroxyphenyl) propionate], 1,6-
Hexamethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], 4,4'-thiobis (6-tert-butyl-m-cresol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-sec. Tributylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid]
Glycol ester, 4,4'-butylidene bis (6-
Tert-butyl-m-cresol), 2,2'-ethylidene bis (4,6-di-tert-butylphenol), 2,2'-
Ethylidene bis (4-tert-butyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-
Tert-butyl-4-methyl-6- (2-hydroxy-3-
Tert-Butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-)
Hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-)
Hidoxybenzyl) isocyanurate, 1,3,5-
Tris (3,5-di-tert-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-tertiary Butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] 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 sulfur-based antioxidant include, for example,
Examples thereof include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl and distearyl, and β-alkylmercaptopropionate esters of polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate).

As the above phosphite type antioxidant,
For example, trisnonylphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio)] -5-methylphenyl] phosphite, tridecylphosphite, octyldiphenylphosphite, di (decyl) monophenylphosphite, monodecyldiphenylphosphite, mono (dinonylphenyl) bis (nonylphenyl) phosphite, di ( Tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphosphite, bis (2,6) -Di-tert-butyl-4-me Ruphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (C 12-15 mixed alkyl) -4,4′-n-butylidene bis (2-tert-butyl-5-methylphenol)
Diphosphite, hexa (tridecyl) -1,1,3-
Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, tetrakis (2,2
4-di-tert-butylphenyl) biphenylene diphosphonite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) (octyl) phosphite, tetrakis (2,2)
4-di-t-butylphenyl) 4,4'-biphenylene-di-phosphonite, 2,2-methylenebis (4,6-
Examples thereof include di-t-butylphenyl) octyl phosphite.

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

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

The polyolefin-based agricultural film of the present invention contains the above-mentioned components in combination, and may further contain the following optional components, 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, antifungal agents. Agent,
Examples thereof include bactericides, metal deactivators, release agents, pigments, processing aids and the like.

In order to add various additives to the agricultural film of the present invention, the necessary amounts are weighed, ribbon blender,
A Banbury mixer, a Henschel mixer, a super mixer, a single-screw or twin-screw extruder, a roll compounder, a kneader, and other conventionally known compounders and mixers may be used. The resin composition thus obtained is formed into a film by a method known per se, for example, a melt extrusion molding method (including a T die method and an inflation method),
Methods such as calendar processing, roll processing, extrusion molding processing, blow molding, inflation molding, melt casting method, pressure molding processing, paste processing, and powder molding can be preferably used.

Regarding the thickness of the agricultural film of the present invention,
In terms of strength and cost, the range of 0.01 to 1 mm is preferable, the range of 0.05 to 0.5 mm is more preferable,
More preferably, it is 0.05 to 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 workability in spreading.

Further, the polyolefin agricultural film of the present invention may be a single layer or multiple layers. In the case of multiple layers, 3 to 5 layers are easy to balance each layer. The layer ratio of 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 is 1/2
The range of / 1-1 / 4/1 is more preferable. The ratio of the outer layer to the inner layer is not particularly specified,
From the viewpoint of curl of the obtained film, it is preferable that the ratio is approximately the same.

The polyolefin-based agricultural film of the present invention preferably forms an antifogging film in contact with the innermost layer of the polyolefin-based substrate. At this time, if a large amount of the antifogging agent is contained in the film in contact with the antifogging coating, the nonuniform spraying of the antifogging agent on the film surface causes a problem in forming the antifogging coating. There is. However, the object of the present invention is as an anti-adhesive agent at the time of kneading when used as a masterbatch in which various additives are concentrated and mixed in advance with the base resin of each layer, or as a surface modifier when forming an antifogging film. A small amount can be used as long as it does not damage.

Further, the agricultural film of the present invention can form an antifogging coating film and other coating films. For example, the antifogging coating film may be formed on the inner surface of the house and the dustproof coating film may be formed on the outer surface of the house. In that case, the effect of improving the coating film adhesion, which is the effect of the present invention, may be obtained even for the dustproof coating film.

Examples of the antifogging coating film in the present invention include a composition containing an inorganic colloid sol such as silica sol and / or alumina sol and a binder resin such as a thermoplastic resin as main components. Preferably, an anti-fog coating film containing an inorganic colloid substance and a hydrophilic organic compound as main components or an anti-fogging coating film containing an inorganic colloid substance and an acrylic resin as main components can be used.

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

As the inorganic colloidal sol, it is preferable to select an average particle size in the range of 5 to 100 nm, and in this range, two or more kinds of colloidal sols having different average particle sizes may be used in combination. If the average particle size is too large, the coating may become white and devitrified, and
If the average particle size is too small, the stability of the inorganic colloid sol may be insufficient, which is not preferable. It is preferable that the inorganic colloid sol has a blending amount of 0.2 or more and 5 or less, preferably 0.5 or more and 4 or less in terms of solid content weight ratio with respect to the total solid content weight of the binder resin composition. That is, if the blending amount is too small, the sufficient antifogging effect may not be exhibited, while if the blending amount is too large, not only is it difficult to improve the antifogging effect in proportion to the blending amount, but also coating. There is a phenomenon in which the coating film formed later becomes cloudy to reduce the light transmittance of the film, and the coating film may be rough and fragile, which is not preferable.

Examples of the binder resin include acrylic resins, epoxy resins, urethane resins, polyester resins and the like. From the compatibility with the polyolefin base film of the present invention, acrylic resins and / Or, it is preferable to use a urethane resin, more preferably (a) a hydrophilic acrylic polymer, and (c) a hydrophobic acrylic resin, which will be described later.
(E) A hydrophobic acrylic resin and a polyurethane emulsion are preferable because they have respective characteristics.

The acrylic resin includes (a) a hydrophilic acrylic polymer, and (b) a block copolymer containing a hydrophobic molecular chain block and a hydrophilic molecular chain block in one molecule. , (C) those made of a hydrophobic acrylic resin are preferable, and (a) is particularly preferable because it has excellent compatibility with the base film of the present invention in that early anti-fog wetting is fast. ) Is excellent in compatibility with the base film of the present invention and is preferable.

As the hydrophilic acrylic polymer (a), a vinyl monomer component having a hydroxyl group is used as a main component (preferably 60% by weight to 99.9% by weight, more preferably 65% by weight to 95% by weight). ), A copolymer containing 0.1 to 30% by weight of an acid group-containing vinyl monomer component, a partially neutralized product or a completely neutralized product thereof. Examples of the anti-fog coating film containing an inorganic colloid substance and a hydrophilic organic compound as main components that can be used in the present invention include, for example, JP-B-63-45.
No. 432, Japanese Patent Publication No. 63-45717, Japanese Patent Publication No. 64-2
Examples thereof include the compounds shown in Japanese Patent No. 158 and Japanese Patent No. 3094296.

As the hydrophobic acrylic resin (c),
A total of at least 60% by weight of monomers consisting of alkyl esters of acrylic acid or methacrylic acid, or a monomer mixture of alkyl esters of acrylic acid or methacrylic acid and alkenylbenzenes, and 0-40% by weight
A copolymerizable α, β-ethylenically unsaturated monomer of
A water-dispersible polymer or copolymer obtained by emulsion polymerization in an aqueous medium, for example, in the presence of an emulsifier, can be mentioned according to ordinary polymerization conditions.

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 likely to aggregate several times to form a non-uniform dispersion state, and if it is too high,
If it is transparent and uniform, it is difficult to obtain a film.

The hydrophobic acrylic resin used in the present invention is preferably used as an aqueous emulsion. An aqueous emulsion obtained by polymerizing each monomer in an aqueous medium may be used as it is, or it may be diluted by adding a liquid dispersion medium to this, or produced by the above-mentioned polymerization. Alternatively, the polymer may be separately collected and redispersed in a liquid dispersion medium to give an aqueous emulsion.

On the other hand, as the urethane resin (d), there may be mentioned an aqueous composition of a polyether type, polyester type, polycarbonate type anionic polyurethane, or an emulsion, which is adhered to the base polyolefin type resin film of the anti-fog coating. From the viewpoint of water resistance, water resistance, and scratch resistance, a polycarbonate-based anionic polyurethane emulsion is preferable, and the time until the water resistance, scratch resistance, and anti-fog property of the anti-fog coating are further improved and the anti-fog durability is improved. In this respect, a polycarbonate-based anionic polyurethane emulsion containing a silanol group is more preferable. These may be used alone or in combination of two or more.

A polycarbonate type 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. Specifically, it refers to the one in which the silanol group-containing polyurethane resin and the strongly basic tertiary amine are dissolved in the aqueous phase, or the one in the colloidal dispersion system (emulsion) dispersed in the form of fine particles.

Further, as a suitable anti-fogging film of the present invention,
(E) A mode in which an emulsion obtained by mixing the above-mentioned (c) hydrophobic acrylic resin and (d) polyurethane aqueous composition is used, because of compatibility with the substrate, the development speed of antifogging property and antifogging sustaining property are improved. Both are preferable and preferable in terms of scratch resistance.

When preparing the antifogging composition for forming the antifogging film of the present invention, various highland anionic surfactants, cationic surfactants, nonionic surfactants, A surfactant such as a polymer surfactant, a cross-linking agent, and, if necessary, a liquid dispersion medium can be added. Further, if necessary, an antifoaming agent, a plasticizer, a film-forming aid, a thickener, a pigment,
Conventional additives such as pigment dispersants can be mixed.
Further, as the binder component other than the acrylic resin, for example, a polyether-based, polycarbonate-based, polyester-based water-dispersible urethane resin or the like may be mixed.

In order to form an antifogging film on the surface of a substrate film, generally, a solution or dispersion of the antifogging composition is subjected to doctor blade coating, roll coating, dip coating, spray coating, rod coating. A coating method known per se such as a coating method, a bar coating method, a knife coating method, and a brush coating method may be adopted, and the coating may be dried after coating. As a drying method after coating, either natural drying or forced drying may be adopted, and when the forced drying method is adopted, it is usually 5
It may be dried in a temperature range of 0 to 250 ° C, preferably 70 to 200 ° C. For heating and drying, a hot air drying method, an infrared drying method, a far infrared ray drying method, an ultraviolet curing method, or the like may be appropriately used. Considering the drying speed and stability, it is advantageous to use the hot air drying method. is there.

In the present invention, the thickness of the coating film formed on the surface of the base film may be selected to be 1/10 or less of the base film, but is not necessarily limited to this range. The film thickness is 1/10 of the base film
If it is larger, 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, and cracks are generated in the coating film to lower the strength of the base film. A phenomenon occurs, which is not preferable.

When the adhesion between the base film and the coating derived from the coating composition is not sufficient, the base film may be surface-treated. As the method of treatment applied to the surface of the laminated film of the present invention, corona discharge treatment,
Examples of the method include sputter etching treatment, sodium treatment, and sandblast treatment. Among these surface treatments, the corona discharge treatment is preferable in terms of adhesion to the coating layer, workability, safety, cost and the like.

When the agricultural thermoplastic resin film according to the present invention is actually used, it is preferable to stretch the film so that the side provided with the anti-fog coating is the inside of the house or tunnel.

[0090]

The present invention will be described in more detail based on the following examples and comparative examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

(1) Preparation of laminated film (both anti-fogging agent kneading type and anti-fogging coating coating type) As a three-layer inflation molding apparatus, a 100 mmφ (manufactured by Pla Koken Co., Ltd.) was used for a three-layer die and an extruder. Is the outer and inner layer of the tube 30mm
φ (manufactured by Pla Giken Co., Ltd.) 2 units, intermediate layer 40 mmφ
(Made by Pla Giken Co., Ltd.), the outer and inner layer extruder temperature 18
0 ℃, middle layer extruder temperature 170 ℃, die temperature 18
0-190 ℃, blow ratio 2.0-3.0, take-off speed 3
-7 m / min, thickness 0.10 to 0.15 mm Table-2 ~
A three-layer laminated film composed of the components shown in Table-7 was obtained. Since these films are used by cutting open the ends of the tubes during the expansion of the house, the outer layer of the tube during film formation when expanded becomes the inner layer (inner surface) of the house during expansion.

[Blending] The addition amount is as described in each table. HP-LDPE: Branched polyethylene produced by a high pressure radical method catalyst (MFR: 1.1 g / 10 min, density 0.9
20) Nippon Polychem Novatec LD “YF30” Metallocene PE: Ethylene produced with a metallocene catalyst.
α-olefin copolymer (MFR: 2 g / 10 min, density 0.907) Kernel “KF270” manufactured by Nippon Polychem EVA: Ethylene / vinyl acetate copolymer (vinyl acetate content 5% by weight, MFR 2 g / 10 min) EVA: Ethylene / vinyl acetate copolymer (vinyl acetate content 15% by weight, MFR 2g / 10 minutes) Light stabilizer A: Light stabilizer "Tinuvin NOR371 FF" manufactured by Ciba Specialty Chemicals Co., Ltd. Triazine skeleton and the general formula (1) 2,2,6,6 having the described structure
-Tetramethylpiperidine derivative, molecular weight about 3600 Light stabilizer B: Light stabilizer "Adeka Stab LA-900" manufactured by Asahi Denka Co., Ltd. Hindered amine-based compound obtained by graft-adding the compound represented by the general formula (2) to polyethylene. . It has the structure of the general formula (1). Light stabilizer C: Light stabilizer manufactured by Ciba Specialty Chemicals Co., Ltd. Chimassorb 944 A hindered amine compound of the type in which a hydrogen atom is bonded to the nitrogen atom of the piperidine ring, and does not have the structure described in the above general formula (1). Molecular weight about 2000-3000. Light stabilizer D: Light stabilizer CYASORB manufactured by Cytec
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 about 1700. Ethylene / Cyclic Amino Vinyl Copolymer: "Novatech LD / XJ100H" manufactured by Nippon Polychem Co., Ltd. MFR = 3
g / 10 minutes (190 ° C., JIS-K6760) Density =
0.931 g / cm3 (JIS-K6760) Cyclic aminovinyl compound content = 5.1% by weight (0.7 mol%) Proportion of cyclic aminovinyl compound present independently = 90 mol% Melting point = 111 ° C. Triaryltriazine Type ultraviolet absorber: triaryltriazine compound in which R1 is an octyl group and R2 to R5 are methyl groups Triaryltriazine type ultraviolet absorber: triaryltriazine in which R1 is a hexyl group and R2 to R5 are hydrogen atoms Compound

(2) Surface treatment of film (anti-fogging coating type) The outer surface of the obtained tubular film was subjected to discharge voltage 1
20V, discharge current 4.7A, line speed 10m / m
The corona discharge treatment was carried out in in and the "wetting index" according to JIS-K6768 was measured and confirmed.

(3) Formation of anti-fog coating film (anti-fog coating film coating type) The following main components (silica sol and / or alumina sol), a thermoplastic resin, a crosslinking agent and a liquid dispersion medium are blended. An antifogging composition was obtained. The formulation of the antifogging agent composition was as follows. Inorganic colloidal sol (colloidal silica) 4.0 Thermoplastic resin (Samol SW-131: hydrophobic binder resin) 3.0 Crosslinking agent (TAZM) 0.1 Dispersion medium (water / ethanol = 3 / 1) 93 (Note) The compounding amount of the inorganic colloid sol is indicated by the amount of inorganic particles, and the compounding amount of the thermoplastic resin is indicated by the polymer solid content. Colloidal silica: Snowtex 30, manufactured by Nissan Chemical Co., Ltd.
Average particle size 15 nm Sunmor SW-131: Acrylic emulsion T.M. manufactured by Sanyo Chemical Co., Ltd. A. Z. M: Mutual Pharmaceutical Co., Ltd. aziridine compound

On the surface of the base film surface-treated in (2), the above antifogging agent compositions A and B were respectively applied using a # 5 bar coater. The coated 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 is about 1
was μm.

A type provided with an antifogging coating (film thickness 1
00 μm) The following physical properties were measured for each, but the combinations other than the resins, additives and coatings used this time,
Alternatively, even if the film thickness is different from this time, the same effect can be obtained unless the gist thereof is changed. The following tests were performed on each sample used this time. The respective measuring methods in Examples and Comparative Examples are shown below.

Initial coating adhesion (coating releasability: after rubbing test) A rubbing test was performed with a UF rubbing resistance tester FT-501 manufactured by Kamijima Seisakusho. After the film cut into a width of 2 cm and a length of 7 cm was placed in a constant temperature chamber at 23 ° C. for 60 minutes, a load of 5 was applied.
A rubbing test was carried out 10 times under the conditions of 00 g, a rubbing width of 2 cm, and a rubbing speed of 120 times / min. After that, of the rubbing width part,
The coating adhesion of the antifogging layer was visually evaluated according to the following criteria.

[0098] A: Peeling area 0 to 10% ◯: Peeling area 10 to 20% Δ: Peeling area 20 to 50% ×: Peeling area> 50%

Pesticide resistance test Adhesion of coating film after 1000 hours The above film was spread in a sealed state in a pipe house constructed in the field of Isshi-gun, Mie Prefecture. Further, the sulfur was fumigated for 8 hours in the day by heating the sulfur in a commercially available sulfur fumigator (trade name: Shinkodenen) in the pipe house. The film subjected to spreading and fumigation for about 4 months from mid-April 2001 to mid-August 2001 was exposed to a weather resistance tester (made by The Q-PANEL COMPANY). The coating adhesion of these films after 1000 hours was measured according to the method for measuring the initial coating adhesion.

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

⊚ ... Water droplets adhering to the film surface (the one facing the inside of the house, the same applies hereinafter) coalesces and spreads in a thin film form, and the area of this thin film part is 2 / of the film surface.
Three or more. ○: Water droplets adhering to the film surface are seen to coalesce, but the area of this thin film-like part is 2 / of the film surface.
Less than 3 and 1/2 or more. △: coalescence of water droplets adhering to the film surface is recognized, but the area of this thin film-like portion is 1 / of the film surface.
Less than 2. X: Water droplets adhering to the film surface were not recognized as coalescing.

Anti-fogging property after 1000 hours of pesticide resistance test The film was spread in a sealed state in a pipe house constructed in the field of Isshi-gun, Mie Prefecture as described above. Further, the sulfur was fumigated for 8 hours in the day by heating the sulfur in a commercially available sulfur fumigator (trade name: Shinkodenen) in the pipe house. The film subjected to spreading and fumigation for about 4 months from mid-April 2001 to mid-August 2001 was exposed to a weather resistance tester (made by The Q-PANEL COMPANY). The antifogging property after 1000 hours was measured according to the method for measuring the initial antifogging property (difference: sample size is width 15 cm, length 30 cm).

Initial transparency: A laminated film obtained by three-layer inflation molding (in the case of a type in which an anti-fog coating film is applied, after forming (coating) the anti-fog coating film on the surface of the house inner layer side), wavelength 555 nm Straight-line light transmittance in a spectrophotometer (Hitachi, U
3500 type) and the value was shown.

Initial UV-shielding property A laminated film obtained by three-layer inflation molding (in the case of a type in which an anti-fog coating film is applied, after forming (coating) the anti-fog coating film on the inner layer side surface of the house), wavelength The total light transmittance at 325 nm is measured by a spectrophotometer (U3 manufactured by Hitachi, Ltd.).
500 type) and the value is shown.

Initial Physical Properties (Initial Tensile Strength) The mechanical strength of each laminated film obtained was measured according to JIS-K67.
According to the measurement method of No. 32, the tensile breaking strength in the film flow direction (vertical) at a temperature of 23 ° C. was measured, and the numerical value was shown.

Agrochemical resistance (tensile strength) The film was spread in a pipe house constructed in the above-mentioned field of Isshi-gun, Mie prefecture so as to be hermetically sealed. Further, the sulfur was fumigated for 8 hours in the day by heating the sulfur in a commercially available sulfur fumigator (trade name: Shinkodenen) in the pipe house. The film subjected to the spreading and fumigation treatment for about 3 months from the middle of April 2001 to the middle of July 2001 was exposed to a weather resistance tester (made by The Q-PANEL COMPANY). At each time, the breaking strength of these films in the machine direction (resin flow direction) was tested by a tensile test (JIS-K673).
2). (Pesticide resistance evaluation).

[Examples 1 to 4 and Comparative Examples 1 to 8] With the above blending, 100 μm films (types in which an antifogging agent was kneaded and an antifogging coating was applied) were prepared by a processing method. Various tests were performed under the above conditions using the film obtained here.

[Examples 1 and 2, Comparative Examples 1 and 2] With the above blending, a three-layer film having a film thickness of 100 μm and a layer ratio of 1/3/1 (anti-fogging coating type: ultraviolet absorber added) was prepared. Then, the initial antifogging coating adhesion by the above method, the antifogging coating adhesion after the pesticide resistance test, the initial antifogging property, the antifogging property after the pesticide resistance test, the initial transparency, the initial ultraviolet shielding property, The initial tensile strength and physical properties after the pesticide resistance test were measured, and each film was evaluated. The results are shown in [Table 1].

[Table 1]

[Examples 3 and 4, Comparative Examples 3 and 4] With the above composition, a three-layer film having a film thickness of 100 μm and a layer ratio of 1/3/1 (anti-fogging coating type: addition of an ultraviolet absorber, ethylene- Cyclic amino vinyl compound copolymer addition (inner and outer layers) was prepared, and the initial anti-fogging coating adhesion by the above method,
Measurement of adhesion of anti-fog coating film after pesticide resistance test, initial anti-fog property, anti-fog property after pesticide resistance test, initial transparency, initial UV shielding property, initial tensile strength, physical properties after pesticide resistance test, etc. Then, each film was evaluated. The results are shown in [Table 2].

[Table 2]

[Comparative Examples 5 to 8] A three-layer film having a film thickness of 100 μm and a layer ratio of 1/3/1 (anti-fogging coating type: no ultraviolet absorber added) was prepared by the above-mentioned formulation, and the above-mentioned method was used. Initial anti-fog coating adhesion, anti-fog coating adhesion after pesticide resistance test, initial anti-fog property, anti-fogging property after pesticide resistance test, initial transparency, initial UV shielding property, initial tensile strength, resistance The physical properties after the pesticide test were measured and each film was evaluated. The results are shown in [Table 3].

[Table 3]

As is clear from the above results, the hindered amine according to the present invention which has at least two polyolefin resins and at least two piperidine ring structures represented by the above formula (1) and has an average molecular weight of 1,000 or more. It has at least one layer containing at least one compound, and at least one layer containing an ultraviolet absorber, particularly at least one ultraviolet absorber having a specific structure according to the present invention. , A multi-layered or single-layered polyolefin-based agricultural film (R1 represents a functional group or compound (including oligomer and polymer) having 1 or more carbon atoms and containing at least one methylene group) is a coating after a pesticide treatment. It is remarkably excellent in film adhesion, antifogging property and tensile strength (Examples 1 and 2). Further, by combining with a copolymer of ethylene (A) and the cyclic amino vinyl compound (B) represented by the above formula (5), good adhesion of coating film after pesticide treatment, antifogging property, and weather resistance can be obtained. A property can be imparted (Examples 3 to 4).

On the other hand, when a compound other than the hindered amine compound according to the present invention is used, it is impossible to impart sufficient coating film adhesion, antifogging property and weather resistance after the pesticide treatment. (Comparative Examples 1 to 4). Moreover, when the ultraviolet absorber according to the present invention is not used, sufficient weather resistance cannot be imparted.

That is, when the resin composition of the present invention is applied to an agricultural film, it has at least two piperidine ring structures represented by the above-mentioned formula (1), which is a constitutional requirement, and has an average molecular weight of 1,000 or more. At least one of a hindered amine compound (R1 represents a functional group or a compound (including an oligomer and a polymer) having 1 or more carbon atoms and containing at least one methylene group), and at least one kind of an ultraviolet absorber, particularly The ultraviolet absorber having a specific structure according to the present invention is essential for the polyolefin-based agricultural film according to the present invention, and further, ethylene (A)
The effect can be further sustained and improved by adding a copolymer of the cyclic aminovinyl compound (B) represented by the above formula (5).

As for the ultraviolet absorber, when the triaryltriazine type ultraviolet absorber described in the present invention is used, the ultraviolet absorbing ability can be maintained particularly for a long period of time, so that the effect can be maintained for a long period of time. On the other hand, if the ultraviolet absorber is not added, the weather resistance and pesticide resistance cannot be maintained at a high level.

These conditions are indispensable for obtaining the effects of the present invention, and even if either of them is lacking, the pesticide resistance, the antifogging coating adhesion, the ultraviolet absorbing ability retention, and the sustainability of those effects are maintained. Agricultural film having a good balance of properties such as properties cannot be obtained.

The agricultural film of the present invention has pesticide resistance,
Maintains weather resistance, anti-fog property and its various properties, and has excellent weather resistance, anti-fog property, anti-fog coating adhesion and weather resistance even under acidic conditions such as pesticides and acid rain. In addition, it has well-balanced performance that should be provided as an agricultural film. Further, when an ethylene / cyclic aminovinyl compound copolymer is used, the weather resistance, the pesticide resistance and the bleed-out resistance are excellent, and the effect of the present invention is particularly exerted in such applications, and the film is an antifogging coating film. It is preferable to provide since the bleed-out is suppressed and the adhesiveness to the substrate is not lowered. The agricultural film of the present invention may be transparent, satin-finished, or semi-pear-finished, and is an agricultural film for soot, tunnel, mulching, bagging, etc. (so-called agricultural plastic, agricultural poly, agricultural sachet, agricultural PO, hard film). Etc.) can be suitably used.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission Date] November 11, 2002 (2002.11.
11)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 4

[Correction method] Change

[Correction content]

[Chemical 3] (3) (In the formula, R3 to R7 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 6

[Correction method] Change

[Correction content]

[Chemical 5] (5) (In the formula, R8 and R9 each independently represent a hydrogen atom or a methyl group, and R10 represents a hydrogen atom or a carbon number of 1 to 4)
Represents an alkyl group. )

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0030

[Correction method] Change

[Correction content]

As a highly effective ultraviolet absorber, a triaryltriazine type ultraviolet absorber represented by the following formula (3) can be mentioned.

[Chemical 11] (3) (In the formula, R3 to R7 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0032

[Correction method] Change

[Correction content]

In the above formula (3), if the carbon number of R3 is less than the above range, bleeding out tends to occur, which is not preferable, and if it exceeds the above range, the weather resistance tends to be poor, such being undesirable. If the carbon number of R 4 to R 7 is less than the above range, bleeding out tends to occur, which is not preferable, and if it exceeds the above range, the weather resistance tends to be poor, such being undesirable. Particularly, in the ultraviolet absorbent according to the present invention, when R3 in the formula (3) is an octyl group and R4 to R7 are methyl groups, or the ultraviolet absorbent according to the present invention is the R3 in the formula (3). Is a hexyl group and R4 to R7 are hydrogen atoms, an agricultural film having particularly excellent bleed-out resistance and chemical stability can be obtained.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction content]

[0038]

[Chemical 12] (5)

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 5/3435 C08K 5/3435 C08L 23/00 C08L 23/00 (72) Inventor Takashi Takazawa Nagoya City, Aichi Prefecture 2 Oike, Iwazuka-machi, Nakamura-ku, Nagoya, Mitsubishi Kagaku MKV Co., Ltd. (72) Inventor Shunichi Onishi 2 Oike, Iwazuka-cho, Nakamura-ku, Aichi, Nagoya Mitsubishi Kagaku MKV Co., Ltd. 2B024 DA03 DA05 DB01 DB07 2B029 EB03 EC02 EC14 EC16 EC19 EC20 4F071 AA14 AA15 AC07 AC11 AC12 AE05 BA01 BB04 BB06 BC01 4F100 AH03A AK03A AK03B BA02 BA07 BA57 BA0BA07 BA0BA16 BA25 CA07B GB01 JA07A JB01 EU0177 BB0 JL1 4J009

Claims (8)

[Claims] 1. A polyolefin resin and at least two piperidine ring structures represented by the following formula (1):
And a multilayer or single layer having at least one layer containing at least one hindered amine compound having an average molecular weight of 1000 or more, and at least one layer containing at least one ultraviolet absorber. Polyolefin-based agricultural film consisting of. (R1 has 1 carbon
The above represents a functional group or compound (including oligomer and polymer) containing at least one methylene group) ・ ・ ・ ・ ・ ・ (1) 2. The hindered amine compound according to claim 1, wherein the hindered amine compound has an average molecular weight of 2000 or more, and has at least 2 of the triazine skeleton and the piperidine ring structure represented by the above formula (1).
A polyolefin-based agricultural film having at least one piece. 3. The hindered amine compound according to claim 1, wherein the compound represented by the following general formula (2) has an average molecular weight of 2
A polyolefin-based agricultural film, which is an adduct added to 000 or more polymers. (In the formula, n represents an integer of 1 to 4, X represents -O- or -NH-,
R2 represents a hydrogen atom, an aliphatic acyl group having 1 to 20 carbon atoms, an aliphatic polyvalent acyl group, an aromatic acyl group or an aromatic polyvalent acyl group. ) [Chemical 2] ・ ・ ・ ・ ・ ・ (2) 4. The polyolefin agricultural film according to claim 1, wherein the ultraviolet absorber according to claim 1 is a triaryltriazine type ultraviolet absorber according to the following general formula (3). [Chemical 3] (3) (In the formula, R3 to R7 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.) 5. The polyolefin agricultural film according to any one of claims 1 to 4, wherein the base film contains an infrared absorbing agent which is an inorganic compound represented by the chemical formula (4) below. Embedded image Mg _4.5 Al ₂ (OH) ₁₃ CO ₃ · 3.5H ₂ O (4) 6. A base film having at least one layer containing a copolymer of ethylene (A) and a cyclic aminovinyl compound (B) represented by the following formula (5): The polyolefin-based agricultural film according to claim 1. [Chemical 5] (5) (In the formula, R8 and R9 each independently represent a hydrogen atom or a methyl group, and R10 represents a hydrogen atom or a carbon number of 1 to 4)
Represents an alkyl group. ) 7. At least one layer containing an ethylene copolymer having a hindered amine as a side chain, which is obtained by copolymerizing ethylene according to claim 7 and a cyclic aminovinyl compound, and one of the components. Part / or all have at least one layer containing the ultraviolet absorber component which is the triazine-based compound according to claim 4, represented by the above formula (3) with respect to 100 parts by weight of the polyolefin-based resin in all the films. A polyolefin-based agricultural multilayer film comprising less than 2 parts by weight of the triaryltriazine type ultraviolet absorber described above. 8. Further, it has at least two piperidine ring structures represented by the following formula (6) and has an average molecular weight of 5:
The polyolefin agricultural film according to claim 1, which has at least one layer containing at least one kind of a hindered amine compound of 00 or more. [Chemical 6] (6)