JP2003105142A - Polyolefin film for agriculture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyolefin resin composition which is free from a decrease in transparency due to the bleeding of a weatherproofing agent and free from a decrease in long-term weatherability, and which gives an agricultural film excellent in weatherability, durability and resistance to agricultural chemicals and scarcely subject to limitation on the cultivation of crops utilizing e.g. honeybee crossfertilization. SOLUTION: The polyolefin resin composition is characterized in that it contains an ultraviolet absorber comprising a triaryltriazine represented by formula (1), in an amount of less than 0.1 pt.wt. based on 100 pts.wt. polyolefin resin.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to weather resistance, durability,
The present invention relates to an agricultural film which has excellent pesticide resistance and has few restrictions in crop cultivation using bee mating or the like.

[0002]

BACKGROUND ART In recent years, in order to enhance the marketability and productivity of agricultural crops by semi-forcing or suppressing cultivation, agricultural vinyl chloride film (hereinafter referred to as agricultural vinyl), polyethylene, ethylene-vinyl acetate copolymer. Also, so-called greenhouse cultivation and tunnel cultivation are popular, in which useful plants are cultivated under the covering with agricultural coating materials such as agricultural polyolefin resin films (hereinafter referred to as agricultural poly and agricultural vinegar) mainly composed of polyolefin resin. Has been done in.

Among them, the polyolefin resin film for agriculture, which is mainly composed of polyolefin resin, is light in weight because it has a density smaller than that of vinyl chloride resin, has little generation of toxic gas even when incinerated, and is further spliced by the inflation molding method. Wide-width films that do not require adhesive processing for this purpose can be provided at low cost, and are therefore being widely used. Agricultural poly, agricultural vinegar, etc.
Despite its superiority in terms of dust resistance and waste disposal over agricultural products, its transparency, heat retention, water whitening resistance, and house adhesion are inferior, and its improvement is a problem.

[0004] Now, such an agricultural house is getting larger year by year, and a lot of manpower is required for the film spreading work for covering the house with a film. On the other hand, the number of farmers is decreasing year by year and the population is aging, and 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. In order to meet such demands, various performances such as transparency, pesticide resistance, and weather resistance are required as the performance of the film, which should be retained for a long period of time, depending on its use. Heretofore, resin compositions containing various additives have been proposed in order to impart these properties to molded products.

Typical of the additives for the purpose of improving the weather resistance added to these agricultural films are hindered amine weather resistance agents and ultraviolet absorbers.

A resin composition containing a hindered amine compound as a weathering agent in these agricultural films has been widely used. Conventionally, in the above-mentioned agricultural films, a piperidine ring is generally used in an amount of 2 per molecule. Examples thereof include hindered amine weathering agents having three or more and a molecular weight of 500 or more. Already, the hindered amine-based weathering agent is added to the resin in a small amount, as disclosed in, for example, JP-A-59-86645 and JP-A-2-167350, 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 period of time, and changes in gloss and color tone of the polyolefin resin film are significantly suppressed. However, a molded article obtained from such a hindered amine-based weathering agent-containing resin composition has a markedly reduced effect during use, for example, under conditions of exposure to acid rain or pesticides, and is required to have acid resistance and pesticide resistance. It was not satisfactorily used for applications such as agricultural films.

On the other hand, agricultural films (for example, JP-A-5-112725 and JP-A-5-124161) to which an ethylene / cyclic aminovinyl compound copolymer is added for the purpose of sustaining further effects are disclosed. Invented. This ethylene / cyclic aminovinyl compound copolymer is clearly distinguished from ordinary hindered amine weathering agents from the production method and molecular structure (for example, Patent No. 269).
5971 and Japanese Patent No. 2695975). However, this ethylene-based copolymer has a high compatibility with the resin, and although the effect of improving the weather resistance can be recognized by the addition thereof, it is expensive, so that there is a problem that it is difficult to increase the addition amount. When the addition amount is low, the proportion of hindered amine groups in the total weight of the compound is low as compared with ordinary hindered amine weathering agents, so the weather resistance improving effect is low, and it cannot be said that it is generally used. .

When used as an agricultural film, pesticides composed of sulfur-based, phosphoric-acid-based, halogen-based, and other acidic substances are often used, and their action reduces the action and effect of, for example, hindered amine compounds. As a result, the weather resistance decreases. Since the transparency of the film is deteriorated as the resin deteriorates, for the purpose of solving this, for example, Japanese Patent Laid-Open No. 63-175072 discloses:
There has been proposed an agricultural film provided with a pesticide resistance, which is obtained by blending a thermoplastic resin with a hindered amine compound as a light stabilizer and a hydrotalcite compound, and JP-A-8-48822 discloses a sterically hindered amine. A polyolefin (copolymer) film containing a metal oxide or a hydroxide and having weather resistance and pest control agent resistance has been proposed. JP-A-8-224049 discloses a hindered amine compound, hydrotalcite. A polyolefin resin-coated film characterized by being used for institutional horticultural house tunnel cultivation in which soils or plants are treated with an inorganic sulfur agent containing a class compound and an ultraviolet absorber has been proposed, but still satisfactory performance Things have not been obtained.

Further, in JP 2001-2842A, an ethylene copolymer having 0.1 to 1.0 part by weight of a triazine-based UV absorber and 100 parts by weight of a polyolefin resin and a hindered amine as a side chain is disclosed. A resin composition to which is added is proposed. However, it has been found that when a general agricultural film of 100 μm or more for agriculture is prepared with the addition amount described in the publication, there is a limitation in the cultivation of crops inside, particularly in bee mating.

Generally, when a crop is cultivated in a house, the wavelength and intensity of light entering the house influences the activity of honeybees used for generation and mating of the crop. In particular, the amount of transmitted ultraviolet rays is important, and under film coating in which a certain amount of ultraviolet rays is cut, the honey loses its sense of direction, so it cannot return to the nest, and there is a problem in pollination work using honeybees.

Generally, the agricultural outer coating film which is required to have long-term weather resistance has a film thickness of 100 μm or more.
However, the resin composition described in JP 2001-2842A specifically contains 0.5 part by weight or 0.8 part by weight (per 100 parts by weight of resin: 80 μm sheet) of a triazine compound. However, even if this formulation is applied to a film having a thickness suitable for long-term weather resistance, the cultivation of crops is actually limited, and it can hardly be used except for special applications that do not require ultraviolet rays.

Accordingly, it is an object of the present invention to provide a film for agricultural coating material which, when used in an agricultural film, has excellent weather resistance, durability and pesticide resistance and has few restrictions in crop cultivation. .

[0013]

As a result of earnest studies, the present inventor has found that the total film thickness is 100 μm or more,
In an agricultural film containing a polyolefin resin as a main component, a specific ultraviolet absorber represented by the following formula (1) is blended in a polyolefin resin at a certain concentration or less,
Alternatively, by controlling the relationship between the film thickness and the addition amount of the ultraviolet absorber of the formula (1) within a certain range, it is possible to effectively prevent the above problem, that is, the deterioration of the film due to the pesticide that is an acidic substance, and The present invention has been completed by finding that crop cultivability such as pollination using bees can be imparted.

The present invention has been made based on the above findings, and is an agricultural film having a total film thickness of 100 μm or more and containing a polyolefin-based resin as a main component. A polyolefin-based agricultural film comprising a triaryltriazine-type ultraviolet absorber represented by the following formula (1) in an amount of less than 0.1 parts by weight and 0.001 parts by weight or more.

[0015]

[Chemical 4] ... (1)

(In the formula, R1 to R5 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)

Alternatively, the present invention is an agricultural film containing a polyolefin resin as a main component, wherein the total thickness of all films is A μm, and the triaryl represented by the above formula (1) per 100 parts by weight of the polyolefin resin. A × B when the content of the triazine-type ultraviolet absorber is B parts by weight
The value of is in the range of 1 ≦ A × B <15.

Further, the present invention contains 2 to 10 parts by weight of a copolymer of ethylene (A) and a cyclic aminovinyl compound (B) represented by the following formula (2), in addition to the above ultraviolet absorber. The above-mentioned polyolefin-based agricultural film is provided.

[0019]

[Chemical 5] ... (2)

(In the formula, R6 and R7 each independently represent a hydrogen atom or a methyl group, and R8 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

The present invention also relates to R in the above formula (1).
1 is an octyl group, R2 to R5 are methyl groups,
The polyolefin-based agricultural film is provided. The present invention also provides the above-mentioned polyolefin-based agricultural film, wherein R1 in the formula (1) is a hexyl group and R2 to R5 are hydrogen atoms. The present invention also provides the polyolefin-based agricultural film, wherein R6 and R7 in the formula (2) are each a methyl group, and R8 is a hydrogen atom. In addition, in the present invention, by additionally using a specific hindered amine compound as a light stabilizer in addition to the ultraviolet absorber, the weather resistance can be remarkably enhanced while suppressing the bleed-out of the weather resistant agent.

[0022]

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 α of ethylene and butene-1, hexene-1, 4-methylpentene-1, octene and the like is used.
A copolymer with an olefin, for example (A
Method) and (method B). (Method A) A method described in JP-A-58-19309, that is, a metallocene catalyst, particularly a metallocene-alumoxane catalyst, or, for example, International Publication WO92 / 0.
A catalyst comprising a metallocene compound and a compound which reacts with the metallocene compound to form stable ions, as disclosed in Japanese Patent No.
As described in JP-A-295020 and JP-A-5-295022, a catalyst in which a metallocene compound is supported on an inorganic compound is used, and ethylene as a main component and α- having a carbon number of 4 to 20 as a sub-component are used. In this method, an olefin is copolymerized so that the resulting copolymer has a density of 0.880 to 0.930 g / cm ³ . Examples of this polymerization method include a high pressure ionic polymerization method, a solution method, a slurry method, and a gas phase method. Of these, the high pressure ionic polymerization method is preferred.

The high-pressure ionic polymerization method is described in JP-A-56-18607 and JP-A-58-25106, and the pressure is 100 kg / cm ² or more, preferably 300-. It is produced by a high pressure ionic polymerization method under reaction conditions of 1500 kg / cm ² and a temperature of 125 ° C. or higher, preferably 150 to 200 ° C. (Method B) Contains a metallocene catalyst component described in JP-A-6-9724, an organoaluminum oxy compound catalyst component, a fine particle carrier, and, if necessary, an organoaluminum compound catalyst component and an ionized ionic compound catalyst component. In the presence of a catalyst for olefin polymerization, ethylene and α-olefin, specifically 3 to 20 carbon atoms, under various conditions in a gas phase or in a liquid phase of a slurry or a solution.
And the density of the obtained copolymer is 0.
The method of copolymerizing so that it may become 900-0.930 g / cm < ³ >. Without being bound by the above methods (A) and (B) in that good initial transparency and transparency sustainability of the film can be obtained, a polyolefin resin polymerized using a metallocene compound, that is, metallocene polyethylene can be used. Although it can be used, the resin method according to the method (A) is preferable.

Polyethylene resins including these metallocene polyethylenes are subjected to temperature rising elution fractionation (TREF:
Temperature Rising Elutio
nFractionation), MFR, density, molecular weight distribution, and other measurements of various physical properties.

Elution by elevated temperature elution fractionation (TREF)
Measurement of curve Temperature rising elution fractionation (Temperature Ri
sing Elution Fractionatio
n: TREF) is used to measure the elution curve by “Journ
al of Applied Polymer Sci
ence. Vol 126, 4, 217-4, 231
(1981) "," Polymer Discussion Group Proceedings 2P1C09
(1988) ”and the like. Among the peaks specified by the obtained differential elution curve, the metallocene polyethylene having one peak temperature in the range of 20 to 100 ° C, preferably 40 to 80 ° C is used to obtain transparency. It is preferable above. In addition, what elutes at a temperature other than the elution temperature of the peak temperature may substantially exist in the elution curve. If there are two or more peaks within the peak temperature of the elution curve, the transparency tends to deteriorate. If it does not exist, the film becomes sticky.

The ethylene-α-olefin copolymer used as at least one component of the polyolefin resin of the present invention 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 not stable. Also, the MFR
However, if it is less 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.

[0028]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 will deteriorate. Also, the density
Is less than this range, the stickiness of the film surface may
Blocking occurs, resulting in poor practicality.

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 not stable.

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 polyolefin resin composition used as the base material in the present invention is characterized by containing a triazine ultraviolet absorber. The triazine-based UV absorber used in the present invention is a triaryltriazine-type UV absorber represented by the following formula (1).

[0032]

[Chemical 6] ... (1)

In the formula (1), R1 to R5 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Preferably, R1 to R5 each independently represent an alkyl group having 1 to 10 carbon atoms. More preferably R1
Is an alkyl group having 6 to 10 carbon atoms, particularly preferably an octyl group or a hexyl group, and R 2 to R 5 are hydrogen atoms or an alkyl group having 1 to 2 carbon atoms, particularly preferably a methyl group or a hydrogen atom. As a more preferable specific compound, R 1 in the above formula (1) is an octyl group, and R 1
Compounds (2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, wherein 2 to R5 are methyl groups; Made by Cytex: Siasorb UV116
4)) and the like. Alternatively, R1 in the above formula (1)
Is a hexyl group and R2 to R5 are hydrogen atoms (2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol; (TIN manufactured by Ciba Specialty Chemicals
UVIN1577FF)).

In the above formula (1), when the carbon number of R1 is less than the above range, bleeding out tends to occur, which is not preferable, and when it exceeds the above range, the weather resistance is deteriorated, which is not preferable. When the carbon number of R2 to R5 exceeds the above range, the weather resistance is deteriorated, which is not preferable.

The method for obtaining the triaryltriazine-based UV absorber represented by the above formula (1) is not particularly limited, and a commercially available product can be used.

The content of the triaryltriazine type ultraviolet absorber represented by the above formula (1) in the polyolefin-based agricultural film of the present invention is 10% by weight.
The amount is less than 0.1 parts by weight and 0.001 parts by weight or more, preferably 0.001 to 0.09 parts by weight, and more preferably 0.01 to 0.07 parts by weight, relative to 0 parts by weight. When the content is less than the above range, the effect of improving weather resistance is low, and when the content exceeds the above range, it is applied to a general agricultural film of 100 μm or more, particularly 120 μm or more, and further 140 μm or more, by using bees. Crop cultivability such as pollination tends to be restricted, so it is difficult to use except for special purposes. Incidentally, the above content, the entire film of the agricultural film (means a film made of a polyolefin resin,
It means the relationship between the content of the triazine-type ultraviolet absorber in the entire film as in the case of the polyolefin resin in the coating antifogging layer and the like).

Alternatively, in the present invention, the total thickness of the agricultural film is A μm, and the content of the triaryltriazine-type ultraviolet absorber represented by the above formula (1) is 100 parts by weight of the polyolefin resin, B parts by weight. Where 1 ≦ A × B <15, preferably 2 ≦ A × B ≦ 1
3, and more preferably, 3 ≦ A × B ≦ 10. If it exceeds this range, the crop cultivability such as pollination due to the use of bees will be restricted, so that it cannot be used for any purpose other than the special purpose. If it is less than this range, it becomes difficult to maintain the weather resistance of the film, which is the object of the present application. Also in this case, the amount of the polyolefin resin and the amount of the triazine-type ultraviolet absorber mean the amount in the entire film.

The above-mentioned triaryltriazine type ultraviolet absorber used in the present invention is, from the viewpoint of cost,
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. In this case, the amount of triaryltriazine relative to the polyolefin resin in the one layer does not have to be within the above range. For example, when the triazine-type UV absorber is added to only one layer in an amount larger than the above range and not added to the other layers, the polyolefin resin and the triazine-type UV absorber of the entire film are in the above weight ratio. The embodiment within the range of (5) belongs to the scope of the present invention and is a preferable embodiment.

The 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 UV absorbers which are usually used in combination for agriculture include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone,
2-Hydroxybenzophenones such as 5,5′-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'-tertiary octylphenyl) benzotriazole,
2- (2'-hydroxy-3'.5'-dicumylphenyl)
2- (2′-hydroxyphenyl) benzotriazoles such as benzotriazole, 2,2′-methylenebis (4-tertiaryoctyl-6-benzotriazolyl) phenol; phenyl salicylate, resorcinol monobenzoate, 2,4- Di-tert-butylphenyl-3 ', 5'-di-tert-butyl-4'-hydroxybenzoate, 2,4-
Ditertiary amylphenyl-3 ', 5'-ditertiary butyl-4'
-Benzoates such as hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2-ethyl-2'-ethoxyoxanilide, 2
Substituted oxanilides such as -ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3-
Examples thereof include cyanoacrylates such as (p-methoxyphenyl) acrylate. These UV absorbers
Used in one kind or two or more kinds.

In addition to the triaryltriazine type UV absorber represented by the above formula (1), the polyolefin resin composition of the present invention further comprises ethylene (A) and the following formula (2) as a light stabilizer. A copolymer with the represented cyclic aminovinyl compound (B) (hereinafter, referred to as “ethylene / cyclic aminovinyl compound copolymer”) can be contained. The ethylene / cyclic aminovinyl compound copolymer is also unlikely to bleed out, and by using this together with the ultraviolet absorber represented by the formula (1), remarkably high weather resistance is obtained while suppressing bleeding out. be able to.

[0042]

[Chemical 7] ... (2)

In the above formula (2), R6 and R7 each independently represent a hydrogen atom or a methyl group, and R8 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Preferably, R6 and R7 are each a methyl group, and R8 is a hydrogen atom.

The vinyl compound (B) represented by the formula (2) 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 (2) 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 ethylene (A) and the cyclic aminovinyl compound (B) relative to the sum (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 in the following manner, as described in JP-A-4-80215. In 13 C-NMR (for example, JNM-GSX270 Spectrometer manufactured by JEOL Ltd.), according to a known method (for example, refer to Kagaku Dojin's "Machine Analysis Tebiki (1)" pages 53 to 56 (1985)), and described in the literature. Polyethyl 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.

[0049]

[Equation 1]

The proportion of vinyl monomers having a hindered amine group in the side chain, which are estimated in the above, is not continuous and exists in an isolated manner, and the proportion thereof is 83% or more based on the total amount of vinyl monomers (B) in the copolymer. Is preferred. When two or more vinyl monomers having a hindered amine group in the side chain are not continuous and the proportion of isolated vinyl monomers is less than 83%, the content of the vinyl monomer having a hindered amine group in the side chain is small, but the light stability is high. There is a case where the feature of having is not exhibited.

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 Mw / expressed by the ratio of the weight average molecular weight and the number average molecular weight, which is determined by making a calibration curve with monodisperse polystyrene using GPC. The Mn (Q 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 the required monomers to copolymerization conditions, and can be produced by a high-pressure low-density polyethylene production apparatus. Usually, the catalyst produced by radical polymerization is a free radical generating initiator such as dialkyl peroxide, diacyl peroxides, peroxyesters, ketone peroxides, peroxyketals, hydroperoxides and 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. Polymerization pressure is 1
000-5000 kg / cm 2, polymerization temperature is 10
It is about 0 to 400 ° C.

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 used in the present invention
From the viewpoint of cost, the cyclic amino vinyl compound copolymer does not necessarily need to be contained in all layers of the multilayer film, and may be contained in at least one layer. Also,
This ethylene / cyclic aminovinyl compound copolymer can be used in combination with one or more commonly used hindered amine weathering agents. Further, for the layer not containing the ethylene / cyclic aminovinyl compound copolymer, one or more commonly used hindered amine weatherproofing agents can be used. The ethylene / cyclic aminovinyl compound copolymer may be contained in all layers, of course, but for example, it is contained in the innermost layer and the outermost layer (outer surface of the house), and the other layers are hindered amine-based compounds usually blended for agriculture. A light stabilizer can also be included. 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 hindered amine-based weatherproofing agents which are usually used for agricultural use in combination are hindered amine compounds having at least two piperidine ring structures represented by the following formula (3) in the molecule and having a molecular weight of 500 or more. (Hereinafter, also referred to as “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.
Further, the piperidine ring-containing hindered amine compound preferably has 2 to 50 piperidine rings,
The molecular weight is preferably 750 or more.

[0057]

[Chemical 8] ... (3)

Examples of the piperidine ring-containing hindered amine compound 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 (2,2,2
6,6-Tetramethyl-4-piperidyl) -di (tridecyl) butanetetracarboxylate, bis (1,2,2)
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-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 and the like. In addition, a hindered amine in which an OR group is bonded to the N group of the piperidine ring (R is 1 carbon atom
Functional groups or oligomers containing the above methylene groups are also included. Examples of commercially available hindered amine compounds that can be used include TINUVIN770 and TINUVIN.
780, TINUVIN 144, TINUVIN 622
LD, CHIMASSORB119FL, CHIMAS
SORB944 (above, manufactured by Ciba Geigy), Sanol LS-765 (manufactured by Sankyo Co., Ltd.), MARK LA-6
3, MARK LA-68, MARK LA-68, M
ARK LA-62, MARK LA-67, MARK
LA-57 (above made by ADEKA ARGUS), TIN
UVIN NOR371 (made by Ciba Specialty Chemicals), ADEKA STAB LA-900 (made by Asahi Denka Co., Ltd.), etc. are mentioned. These piperidine ring-containing hindered amine compounds are used alone or in combination of two or more.
The content of the piperidine ring-containing hindered amine compound is 0.001 to 100 parts by weight of the thermoplastic resin.
20 parts by weight, preferably 0.01 to 10 parts by weight.
If the content is less than 0.001 part by weight, a sufficient effect cannot be obtained, and if it exceeds 20 parts by weight, not only the effect is not improved but also the physical properties of the film are deteriorated.

In the thermoplastic resin film of the present invention, various additives usually used in synthetic resins can be used together. Examples of such additives include organic acid salts of infrared absorbent (heat retaining agent) metal, basic organic acid salts and overbased organic acid salts, hydrotalcite compounds, epoxy compounds, β-diketone compounds, polyvalent compounds. Examples include alcohols, halogen oxyacid salts, sulfur-based, phenol-based and phosphite-based antioxidants, heat stabilizers, lubricants, antistatic agents, colorants, anti-blocking agents, anti-fog agents, anti-fog agents, etc. .

The above infrared absorber (heat retaining agent) is an inorganic fine particle having an 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 the components: Li,
An inorganic compound containing at least one atom selected from 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, lithium-aluminum composite Hydroxide carbonate compound, Aluminum-lithium-magnesium composite hydroxide carbonate compound, Aluminum-lithium-magnesium composite hydroxide silicate Compound, magnesium aluminum 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 metal complex hydroxide salt may be used alone or in combination with 2.
It can be used in combination of two or more species. The average particle diameter is preferably in the range of 0.05 to 15 μm, more preferably 0.1 to 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.

As the metal species composing the above-mentioned metal organic acid salt, basic organic acid salt and overbased organic acid salt, L is
i, Na, K, Ca, Ba, Mg, Sr, Zn, Cd,
Examples thereof include Sn, Cs, Al and organic Sn. Examples of the organic acid include carboxylic acid, organic phosphoric acid and phenols. Examples of the carboxylic acid include acetic acid, propionic acid, butyric acid, valeric acid and caproic acid. , Enanthic acid, caprylic acid, neodecanoic acid, 2-ethylhexylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid , Montanic acid, elaidic acid, oleic acid, linoleic acid, linolenic acid, thioglycolic acid, mercaptopropionic acid, octylmercaptopropionic acid, benzoic acid, monochlorobenzoic acid, p-tert-butylbenzoic acid,
Dimethylhydroxybenzoic acid, 3,5-di-tert-butyl-
4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cumic acid, n-propylbenzoic acid, acetoxybenzoic acid, salicylic acid, p-tertiary octylsalicylic acid, and other monocarboxylic acids, oxalic acid, malonic acid , Succinic acid, glutaric acid, adipic acid, pimelic acid,
Suberic acid, azelaic acid, sebacic acid, maleic acid,
Fumaric acid, citraconic acid, metaconic acid, itaconic acid,
Divalent carboxylic acids such as aconitic acid, thiodipropionic acid, phthalic acid, isophthalic acid, terephthalic acid, oxyphthalic acid, and chlorophthalic acid, or their monoesters or monoamide compounds, butanetricarboxylic acid, butanetetracarboxylic acid, hemimellitic acid , Di- or triester compounds of trivalent or tetravalent carboxylic acids such as trimellitic acid, melophanoic acid and pyromellitic acid.
Examples of the organic phosphoric acids include mono- or dioctyl phosphoric acid, mono- or didodecyl phosphoric acid, mono- or di-octadecyl phosphoric acid, mono- or di- (nonylphenyl) phosphoric acid, phosphonic acid nonylphenyl ester, phosphonic acid stearyl ester and the like. Examples of the phenols include phenol, cresol, xylenol, methylpropylphenol, methyl tert-octylphenol, ethylphenol, isopropylphenol, tert-butylphenol, n-butylphenol, diisobutylphenol, isoamylphenol, diamylphenol and iso. Hexylphenol, octylphenol, isooctylphenol, 2-ethylhexylphenol, tertiary octylphenol, nonylphenol, dinonylphenol , Third nonylphenol, decylphenol, dodecylphenol, octadecyl phenol, cyclohexyl phenol, phenylphenol phenol, cresol, ethylphenol, cyclohexylphenol, nonylphenol and dodecyl phenol.

The antifogging 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 antifogging agent include fluorine-based surfactants and silicone-based surfactants, and specific examples of the fluorine-based 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 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 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-
Examples include di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane.

Examples of the above sulfur-based antioxidant include
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) butanetriphosphite, tetrakis (2,2 Four
-Di-tert-butylphenyl) biphenylenediphosphonite, 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 thermoplastic resin film of the present invention comprises the above-mentioned components in combination and, if necessary, further contains the following optional components which can be contained in the thermoplastic resin film of the present invention. be able to. 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. Examples include agents, bactericides, metal deactivators, release agents, pigments, processing aids and the like.

To mix various additives, the thermoplastic resin film of the present invention is weighed in a necessary amount, and a ribbon blender, a Banbury mixer, a Henschel mixer, a super mixer, a single-screw or twin-screw extruder, a roll, etc. A compounding machine, a kneader, and other conventionally known compounding machines and mixers may be used. To form a film of the resin composition thus obtained, a method known per se, for example,
Methods such as melt extrusion molding method (including T-die method and inflation method), calendar processing, roll processing, extrusion molding processing, blow molding, inflation molding, melt casting method, pressure molding processing, paste processing, powder molding, etc. Can be preferably used.

The thickness of the thermoplastic resin film of the present invention is preferably 0.1 to 1 mm, more preferably 0.1 to 0.5 mm in terms of strength and cost. If it is less than this range, there is a problem in strength, and if it exceeds this range, molding becomes difficult.

When a polyolefin resin is used for the base material layer in the present invention, an antifogging film can be formed in contact with the innermost layer of the polyolefin base material. As the anti-fog coating film in the present invention, an anti-fog coating film that can be used for a known agricultural film can be applied. Preferably an inorganic colloid substance and a hydrophilic organic compound as an anti-fog coating film or an inorganic colloid substance and an acrylic resin,
An antifogging coating film containing a urethane resin as a main component can be used.

Examples of the anti-fog coating film containing an inorganic colloidal substance and a hydrophilic organic compound as main components which can be used in the present invention include, for example, JP-B-63-45432 and JP-B-6.
No. 3-45717, Japanese Patent Publication No. 64-2158, and Patent No. 3
A combination of a compound shown in 094296, for example, colloidal silica or alumina, and a surfactant can be mentioned.

In the present invention, an antifogging coating mainly composed of an acrylic resin or urethane resin and an inorganic colloid sol can also be preferably used. Examples of acrylic resins include hydrophilic acrylic polymers and hydrophobic acrylic resins. As the hydrophilic acrylic resin, a hydroxyl group-containing vinyl monomer component is a main component (preferably 60% by weight to
99.9% by weight. More preferably 65 wt% to 95 wt%), 0.1 to 30 wt% acid group-containing vinyl monomer
The copolymer to be contained, a partially neutralized product thereof or a completely neutralized product thereof can be mentioned. The hydrophobic acrylic resin is, for example, at least 60% by weight in total (preferably 80% by weight or more).
Monomer of acrylic acid or methacrylic acid alkyl ester, or monomer mixture of acrylic acid or methacrylic acid alkyl ester and alkenylbenzenes, and 0 to 40% by weight of copolymerizable α, β An ethylenically unsaturated monomer, according to the usual polymerization conditions,
For example, a hydrophobic acrylic resin which is a water-dispersible polymer or copolymer obtained by emulsion polymerization in an aqueous medium in the presence of an emulsifier can be mentioned. Examples of the urethane-based resin include an aqueous composition of a polyether-based, polyester-based, and polycarbonate-based anionic polyurethane, and an emulsion. These may be used alone or in combination of two or more.

Examples of the alkyl esters of acrylic acid or methacrylic acid used in the production of acrylic resin include acrylic acid methyl ester, acrylic acid ethyl ester,
Acrylic acid-n-propyl ester, acrylic acid isopropyl ester, acrylic acid-n-butyl ester, acrylic acid-2-ethylhexyl ester, acrylic acid decyl ester, methacrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid-n-propyl ester Esters, methacrylic acid isopropyl ester, methacrylic acid-n-butyl ester, methacrylic acid-2-ethylhexyl ester, methacrylic acid decyl ester and the like can be mentioned. Generally, an acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms. And / or a methacrylic acid alkyl ester having 1 to 20 carbon atoms in the alkyl group is used.

Examples of the alkenylbenzenes include styrene, α-methylstyrene, vinyltoluene and the like.

Α and β used for obtaining an acrylic resin
Examples of the ethylenically unsaturated monomer include α, β-ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid and itaconic acid; ethylene sulfonic acid and the like. α, β-ethylenically unsaturated sulfonic acids; 2-acrylamido-2-methylpropanoic acid; α, β-ethylenically unsaturated phosphonic acids; hydroxyl group-containing vinyl monomers such as hydroxyethyl of acrylic acid or methacrylic acid; acrylonitrile Examples: 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, but in order to obtain a hydrophobic acrylic resin, the amount is in the range of 0 to 40% by weight, preferably 0 to 20% by weight. Preference is given to using. If the amount used is too large, the antifogging performance may be deteriorated, which is not preferable.

The acrylic resin is an aqueous medium in the presence of a known emulsifier, for example, one or more selected from anionic surfactants, cationic surfactants and nonionic surfactants. Among them, it can be obtained by emulsion polymerization, polymerization using a reactive emulsifier, polymerization based on oligosoap theory without containing an emulsifier. In the case of the polymerization method in the presence of an emulsifier, these emulsifiers are added in an amount of 0.1 to 1 with respect to the total amount of the charged monomers.
It is preferably used in the range of 0% by weight from the viewpoint of adjusting the polymerization rate and dispersion stability of the resin to be synthesized.

Examples of the polymerization initiator preferably used for producing the acrylic resin include persulfates such as ammonium persulfate and potassium persulfate; organic peroxides such as acetyl peroxide and benzoyl peroxide. These are 0.1 to 10% by weight based on the total amount of charged monomers.
It can be used in a range of. As the hydrophobic acrylic resin, it is particularly preferable to use one 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, it tends to be difficult to obtain a transparent and uniform coating film.

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, inorganic aqueous colloidal particles such as silica, alumina, water-insoluble lithium silicate, iron hydroxide, tin hydroxide, titanium oxide and barium sulfate can be prepared by various methods in water or a hydrophilic medium. An aqueous sol that has been dispersed can be used. Of these, silica sol and alumina sol are preferably used, and these 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 be 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. The content of the inorganic colloid sol is preferably 50 to 400% by weight as a solid content with respect to the solid content of the binder resin. That is, if the blending amount is too small,
In some cases, a sufficient antifogging effect may not be exhibited. On the other hand, if the blending amount is too large, not only the antifogging effect does not improve in proportion to the blending amount, but also the coating formed after coating becomes cloudy and the film The phenomenon of lowering the light transmittance may appear, and the coating may be rough and brittle, which is not preferable.

When preparing the antifogging composition for forming the antifogging film of the present invention, an anionic surfactant, a cationic surfactant, a nonionic surfactant, a polymer surfactant Surfactants such as agents can be added.

The addition of these surfactants allows the hydrophobic acrylic resin and the inorganic colloid sol to be easily and quickly dispersed uniformly, and when used in combination with the inorganic colloid sol, the hydrophobic polyolefin resin film It has the function of imparting hydrophilicity to the surface. 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 acrylic resin. If the amount of the surfactant added is too small, it takes time for the acrylic resin and the inorganic colloid sol to sufficiently disperse, and the antifogging effect in combination with the inorganic colloid sol cannot be sufficiently exhibited. If the amount of the activator added is too large, the transparency of the coating will decrease due to the bleed-out phenomenon formed on the surface of the coating after application, and if remarkable, the blocking resistance of the coating will deteriorate and the water resistance of the coating will decrease. There is.

A cross-linking agent can be added when preparing the antifogging composition for forming the antifogging film of the present invention. The cross-linking agent has the effect of cross-linking the acrylic resins with each other and improving the water resistance of the coating. Examples of the cross-linking agent include phenol resins, amino resins, amine compounds, aziridine compounds, azo compounds, isocyanate compounds, epoxy compounds, silane compounds and the like, but particularly amine compounds and aziridine compounds. , And epoxy compounds can be preferably used. The addition amount of these crosslinking agents is 0.1 to 30 relative to the acrylic resin solid content.
It can be used in the range of% by weight.

If necessary, a liquid dispersion medium may be added to the antifogging agent composition used in the present invention. The 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 thereof include cyclic alcohols such as benzyl alcohol; cellosolve acetates; ketones. These liquid dispersion media may be used alone or in combination. The antifogging agent composition is generally prepared at a concentration of 0.5 to 50% by weight as the solid content of the acrylic resin and the inorganic colloid, and it is often diluted and used.

The antifog composition prepared in the present invention may further contain, if necessary, an antifoaming agent, a plasticizer, a film-forming aid, a thickener,
Conventional additives such as pigments and pigment dispersants can be mixed. 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 an amount range less than the content of the acrylic resin.

The glass transition temperature of the acrylic resin coating referred to in the present invention was calculated by the following equation.

1 / Tg = W1 / Tg1 + W2 / Tg2 +
... + Wn / Tgn where Tg is the glass transition temperature (absolute temperature) of the acrylic resin, Tg1, Tg2, ..., Tgn are the components 1 and 2,
..., the glass transition temperature (absolute temperature) of the homopolymer of n,
, Wn represent the weight fractions of the components 1, 2, ..., N, respectively.

In order to form an antifogging film on the surface of the base film, the acrylic resin solution and the antifogging composition obtained by the above-mentioned polymerization are respectively subjected to a doctor blade coating method,
Roll coating method, dip coating method, spray coating method, rod coating method, bar coating method, knife coating method,
A coating method known per se, such as a brush coating method, may be employed and dried after coating. As a drying method after coating, either natural drying or forced drying may be adopted. When the forced drying method is adopted, it is usually 50 to 250 ° C., preferably 70.
It may be dried in a temperature range of up to 200 ° C. Any appropriate method such as a hot air drying method, an infrared drying method, or a far infrared drying method may be adopted for the heat drying, and the hot air drying method is advantageous in view of the drying speed and stability.

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 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.

If 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.

The polyolefin-based agricultural film of the present invention is excellent in long-term weather resistance because the weather resistance stabilizer does not easily bleed out on the resin surface, and the transparency is not impaired.
The surface appearance is also excellent. In particular, an agricultural film is excellent not only in weather resistance and pesticide resistance but also in crop cultivability such as pollination using bees, and the effects of the present invention are particularly exerted in such applications. Further, when an anti-fog coating film is provided on the film, bleed-out is suppressed and the adhesiveness to the substrate is not deteriorated, which is preferable. The film using the polyolefin-based resin composition of the present invention may be transparent, satin, or semi-pear, and is an agricultural film for house, tunnel, mulching, bagging, etc. (so-called agricultural plastic, agricultural poly, agricultural sacrifice). , Agricultural PO, hard film, etc.).

[0100]

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 was used. 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
Table-1 at -7 m / min and thickness 0.10-0.15 mm
A three-layer laminated film composed of the components shown in Table 6 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 shown 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” made 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 2 g / 10 min) CHIMASORB 944: light stabilizer manufactured by Ciba Specialty Chemicals (described in JP-A-10-219044) Ethylene / cyclic aminovinyl copolymer Polymer: “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 in isolation = 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 compound in which R1 is a hexyl group and R2 to R5 are hydrogen atoms

(2) Surface treatment of film (anti-fog coating film coating type) The outer surface of the obtained tubular film was exposed to a discharge voltage of 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) A main component (silica sol and / or alumina sol) shown below, a thermoplastic resin, a crosslinking agent and a liquid dispersion medium are blended. An antifogging composition was obtained.

The formulation of the antifogging composition was as follows. Inorganic colloid sol (colloidal silica) 4.0 Thermoplastic resin (Sammol SW-131) 3.0 Crosslinking agent (TAZM) 0.1 Dispersion medium (water / ethanol = 3/1) 93 (Note The compounding amount of the inorganic colloid sol is shown by the amount of the inorganic particles, and the compounding amount of the thermoplastic resin is shown by the polymer solid content. Colloidal silica: Snowtex 30, manufactured by Nissan Chemical Co., Ltd.
Average particle size 15 mμ Sunmor SW-131: acrylic emulsion T.M. manufactured by Sanyo Kasei Co., Ltd. A. Z. M: Mutual Pharmaceutical Co., Ltd. aziridine compound

The above antifogging composition was applied to the surface of the substrate film surface-treated in (2) by 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 was about 1 μm.

A type in which an antifog agent is kneaded and mixed (film thickness 1
00 μm), type with anti-fog coating (film thickness 1
50 μm) The following physical properties were measured for each.
In addition, even if the resin used this time, a combination other than additives, or a film thickness different from this time, unless the gist is changed,
The same effect can be obtained. The respective measuring methods in Examples and Comparative Examples are shown below.

Evaluation of Bee Activity The film was spread in a pipe house constructed in the field of Isshi-gun, Mie Prefecture, in a sealed state. 2001 March
From mid-March to late March 2001 for 1 week (Examples 1 to 4, Comparative Examples 1 to 9) or from late March 2001 to April 2001
For the first week of the month (Examples 5-7, Comparative Examples 10-13), a honeycomb box (3000 / box) is placed in the pipe house.
And honey plate. In order to obtain an average value, the position of the honey plate was moved to the positions of 30 cm, 1 m, and 3 m from the birdhouse every two days. Since there may be individual differences between birdhouses,
Considering the effect of the birdhouse, the results obtained on average during the period were classified as follows. (Bee bee activity evaluation) Observation result: Shown in the attached table. However, the activity classification of bees was judged according to the following criteria. ◎ Honeybees are active in the house. ○ The house is partially active and gathers at the honey source. △ There are about 10 and about 5 flying honey sources. × Two or three are flying without being in the honey source. ×× No bees have appeared.

Transparency [0109] A pipe house constructed in a field in Kaifu-gun, Aichi prefecture, has a laminated film obtained by three-layer inflation molding. Was formed (after coating) and expanded so as to be in a sealed state. The straight light transmittance at a wavelength of 555 nm and the total light transmittance at a wavelength of 325 nm were measured by a spectrophotometer (U3500 type, manufactured by Hitachi, Ltd.), and the values are shown.

Haze Value (Haze) In a laminated film obtained by three-layer inflation molding (in the case of the 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), Haze value (haze value) is a haze meter (Tokyo Denshoku: TC-H3DP)
Was measured and the value was shown.

Transparency (NAS: Characteristic value of narrow-angle transmitted light) In the case of the laminated film obtained by three-layer inflation molding (in the case of the type in which an anti-fog coating film is applied, an anti-fog coating film is formed on the inner surface of the house After (coating), the NAS value (narrow-angle transmitted light characteristic value) was measured by a visual transparency tester (manufactured by Toyo Seiki), and the value was shown.

Initial Physical Properties 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 and tensile breaking elongation in the film flow direction (vertical direction) at a temperature of 23 ° C. were measured, and the numerical values were shown.

Agrochemical resistance test (white turbidity) A film was spread in a pipe house constructed in the above-mentioned field of Isshi-gun, Mie prefecture so as to be hermetically sealed. In addition, 5 g of sulfur in the above pipe house is a commercially available sulfur fumigator (trade name:
It was fumigated for 8 hours during the day by heating with fresh kodenen. Early November 2000 to early January 2001 (Examples 1 to 4 and Comparative Examples 1 to 9) or early April 2001 to early June 2001 (Examples 5 to 7 and Comparative Example 10) ~
The film that has been subjected to the fumigation treatment for about 2 months of 13) was subjected to a weather resistance tester (The Q-PANEL COMP
Exposed to ANY) for 400 hours. Of these films,
The straight-line light transmittance at a wavelength of 555 nm was measured by a spectrophotometer (U3500 manufactured by Hitachi Ltd.), and the value was shown. (Pesticide resistance evaluation).

Pesticide weather resistance (tensile elongation) The film was stretched in a sealed state in a pipe house constructed in the field of Isshi-gun, Mie Prefecture as described above. In addition, 5 g of sulfur in the above pipe house is a commercially available sulfur fumigator (trade name:
It was fumigated for 8 hours during the day by heating with fresh kodenen. Early November 2000 to early January 2001 or early April 2001 to early June 2001 (Example 5
.About.7, Comparative Examples 10 to 13), the film that has been spread and fumigated for about 2 months is subjected to a weather resistance tester (The Q-PA).
NEL COMPANY). At each time, the breaking strength / elongation of these films in the longitudinal direction (resin flow direction) was measured by a tensile test (according to JIS-K6732), and the retention ratio for the breaking strength / elongation at the origin was calculated. (Pesticide resistance evaluation).

Insulation (Far Infrared Part Average Transmittance) The far infrared part average transmittance is measured by using a black body radiant energy spectrum at 15 ° C. as the incident energy and using a separate infrared spectroscope for wavelengths of 4 μm to 25 μm. The transmission energy spectrum obtained by multiplying the transmission energy spectrum obtained by multiplying the transmission spectrum of the film measured in the range was integrated to obtain the transmission energy, which was divided by the incident energy to obtain the transmittance. The smaller the value of transmittance, the better the heat retention. UV transmittance change with time Laminated film obtained by three-layer inflation molding on a pipe house constructed in a field in Kaifu-gun, Aichi prefecture. (For the type that applies anti-fog and film, an anti-fog coating film on the inner layer side of the house After formation (coating), it was spread so as to be in a sealed state. From the end of August 1999 to the end of July 2001, a part of the film being spread in the pipe house was sampled, and its ultraviolet absorption capacity (total light transmittance at a wavelength of 325 nm) was measured by a spectrophotometer (Hitachi Ltd.). Made, U35
00 type), and the value is shown.

[Examples 1 to 7 and Comparative Examples 1 to 13] A 100 µm film (anti-fogging agent kneading type) and a 150 µm film (anti-fogging coating coating type) were prepared by the above-mentioned composition and processing method. Various tests were performed under the above conditions using the film obtained here.

[Example 1, Comparative Examples 1 to 3] A three-layer film having a film thickness of 100 μm and a layer ratio of ⅓ / 1 (anti-fogging agent kneading type) was prepared by the above formulation, and the bee activity was performed by the above method. Each film was evaluated by measuring properties, initial transparency, transparency after pesticide resistance test, initial haze value, initial transparency, heat retention, initial physical properties, physical properties after pesticide resistance test, and the like.
The results are shown in [Table-1].

[0118]

[Table 1]

[Examples 2, 3 and 4] A three-layer film (anti-fogging coating type) having a film thickness of 150 µm and a layer ratio of 1/3/1 was prepared by the above-mentioned composition, and the bee activity, Each film was evaluated by measuring the initial transparency, the transparency after the pesticide resistance test, the initial haze value, the initial transparency, the heat retention property, the initial physical properties, the physical properties after the pesticide resistance test, and the like. The results are shown in [Table-2].

[0120]

[Table 2]

Comparative Examples 4 to 6 Honeybee activity, initial transparency, transparency after pesticide resistance test, initial cloudiness, initial transparency, heat retention, initial physical properties, physical properties after pesticide resistance test, etc. Was measured and each film was evaluated. The results are shown in [Table-3].

[0122]

[Table 3]

[Comparative Examples 7 to 9] Bee activity, initial transparency, transparency after pesticide resistance test, initial haze value, initial transparency, heat retention, initial physical properties, physical properties after pesticide resistance test, etc. Was measured and each film was evaluated. The results are shown in [Table-4].

[0124]

[Table 4]

[Examples 5 and 6, Comparative Examples 10 and 11] A three-layer film (anti-fog coating film coating type) having a film thickness of 150 µm and a layer ratio of 1/3/1 was prepared by the above-mentioned composition and prepared by the above method. Each film was evaluated by measuring the bee activity, the initial transparency and its change after the two-year extension, the initial ultraviolet transmittance and the change after the two-year extension. The results are shown in [Table-
5].

[0126]

[Table 5]

[Example 7, Comparative Examples 12 to 13] A three-layer film having a film thickness of 100 µm and a layer ratio of ⅓ / 1 (anti-fogging agent kneading type) was prepared by the above formulation, and the bee activity was performed by the above method. The properties of the films were evaluated by measuring properties, ultraviolet ray shielding properties, initial physical properties, physical properties after the pesticide resistance test, and the like. The results are shown in [Table-6].

[0128]

[Table 6]

As is clear from the above results, less than 0.1 part by weight of the triaryltriazine type ultraviolet absorber represented by the following formula (1) and 0.001 part by weight or more based on 100 parts by weight of the polyolefin resin. Agricultural film using a polyolefin resin composition, which is characterized by containing, is remarkably excellent in various properties such as cultivating properties such as bee mating, transparency, heat retention, and pesticide resistance. (See Examples).

On the other hand, when the resin composition described in JP 2001-2842 A was used (Comparative Examples 1, 3, 7).
~ 9,12) has good weather resistance and pesticide resistance, but since the bees do not work in the house, the breeding of the bees cannot be done and the crop cultivability is limited, so it is generally used as an agricultural film. I can not use it. On the other hand, when the triaryltriazine type ultraviolet absorber according to the present invention is not contained (Comparative Examples 2, 4 to 6 and 13), the physical properties (tensile elongation) after exposure to a pesticide and the decrease in light transmittance after exposure to a pesticide are observed. Insufficient suppression. Moreover, when other ultraviolet absorbers are contained (Comparative Example 1
0, 11) is problematic in that the change in ultraviolet transmittance after long-term expansion is large.

That is, when the resin composition of the present invention is applied to an agricultural film, it is preferable that the constitutional requirement is less than 0.1 part by weight of the triaryltriazine type ultraviolet absorber. Property, pesticide resistance cannot be maintained, and if it exceeds this range, 100 μm or more, especially 14
When the film thickness is 0 μm or more, crop cultivability such as mating using bees is impaired. Alternatively, the relationship A × B between the total film thickness (A) and the content of the triaryltriazine-type ultraviolet absorber (per 100 parts by weight of resin) (B)
If it is outside the specified range, it will interfere with crop cultivability such as mating using bees. These conditions are indispensable in order to obtain the effects of the present invention, and lack of these conditions, crop cultivability such as mating using bees, transparency, heat retention,
It is not possible to obtain an agricultural film having a well-balanced performance such as pesticide resistance (strength, transparency), prevention of deterioration of see-through property, and persistence of those effects.

[0132]

INDUSTRIAL APPLICABILITY The polyolefin-based agricultural film of the present invention is excellent in long-term weather resistance because the weather resistance stabilizer is unlikely to bleed out on the resin surface, the transparency is not impaired, and the surface appearance is also excellent. Furthermore, not only is the weather resistance and pesticide resistance excellent, but the crop cultivability such as pollination using bees is also good, and the effects of the present invention are particularly exerted. Further, when an anti-fog coating film is provided on the film, bleed-out is suppressed and the adhesiveness to the substrate is not deteriorated, which is preferable.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08J 5/18 CES C08J 5/18 CES C08K 5/3435 C08K 5/3435 5/3492 5/3492 (72) Inventor Shunichi Onishi 2 Oike, Iwazuka-cho, Nakamura-ku, Aichi Prefecture Nagoya, Mitsubishi Chemical MKV Co., Ltd. (72) Inventor Takashi Takazawa 2 Oike, Iwazuka-cho, Nakamura-ku, Nagoya City, Aichi F, Mitsubishi Chemical MKV Co., Ltd. term (reference) 2B024 DA05 DB01 DB07 2B029 EB03 EC02 EC09 EC14 4F071 AA14 AA15 AA20 AC12 AE05 AE09 AE17 AF02 AF03 AF13 AH01 BB02 BB04 BB06 BC01 4F100 AA20 AH07B AK03B AK04A AK06 AK61B AK62 AK62B AK66B AK68 AL01 AL01A BA02 BA03 BA04 BA05 BA15 BA16 CA02 CA07B CA10 EH20 EH46 GB01 JB01 JD09 JD14 JJ02 JL00 JL09 JN01 4J002 BB001 BB031 BB121 BB151 EU077 EU186 FD01 FD076 FD077 FD09 FD31 GA01 GF00

Claims (10)

[Claims] 1. A triaryltriazine represented by the following formula (1) with respect to 100 parts by weight of a polyolefin resin, which is an agricultural film having a total film thickness of 100 μm or more and containing a polyolefin resin as a main component. A polyolefin-based agricultural film comprising less than 0.1 parts by weight of 0.001 parts by weight or more and 0.001 parts by weight or more. [Chemical 1] ... (1) (In formula, R1-R5 respectively independently represents a hydrogen atom or a C1-C10 alkyl group.) 2. A film for agriculture comprising a polyolefin resin as a main component, wherein the total thickness of all films is A μm, and the above formula (1) is based on 100 parts by weight of the polyolefin resin.
When the content of the triaryltriazine type ultraviolet absorber represented by the formula is B parts by weight, the value of A × B is 1 ≦ A × B
<15. A polyolefin-based agricultural film characterized by having a range of <15. 3. Further, 2 to 10 parts by weight of a copolymer of ethylene (A) and a cyclic aminovinyl compound (B) represented by the following formula (2) is contained per 100 parts by weight of a polyolefin resin. The polyolefin-based agricultural film according to claim 1 or 2, wherein [Chemical 2] (2) (In the formula, R6 and R7 each independently represent a hydrogen atom or a methyl group, and R8 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) 4. The polyolefin-based agricultural film according to claim 1, wherein R 1 to R 5 in the formula (1) each independently represent an alkyl group having 1 to 10 carbon atoms. 5. The R 1 in the formula (1) is an octyl group, and R 2 to R 5 are methyl groups.
The polyolefin-based agricultural film described. 6. The polyolefin-based agricultural film according to claim 1, wherein R 1 in the formula (1) is a hexyl group, and R 2 to R 5 are hydrogen atoms. 7. The polyolefin-based agricultural film according to claim 1, wherein R6 and R7 in the formula (2) are each a methyl group, and R8 is a hydrogen atom. 8. A multi-layered agricultural film, comprising an ethylene-based copolymer having a hindered amine in a side chain, which is obtained by copolymerizing ethylene represented by the above formula (2) and a cyclic aminovinyl compound. At least one layer containing
2. At least one layer and at least one layer containing an ultraviolet absorber component, which is a triazine-based compound represented by the above formula (1), in a part and / or all of the components. 7. The polyolefin-based agricultural film according to 7. 9. Further, it has at least two piperidine ring structures represented by the following formula (3) and has a molecular weight of 500.
The agricultural film according to claim 8, which has at least one layer containing at least one of the above hindered amine compounds. [Chemical 3] ... (3) 10. The agricultural film according to claim 1, further comprising at least one layer containing at least one infrared absorber.