WO2014010625A1 - Agricultural multi-layered film - Google Patents

Abstract

[Problems] To provide an agricultural polyolefin-based multi-layered film in which a reduction in the translucency which is caused when dew formation is produced on the surface of the film on the exterior side of a greenhouse immediately after the film is stretched on the greenhouse is inhibited and accordingly a decrease in cultivation due to an insufficient amount of light is prevented from occurring, and a decrease in working performance when processing the film due to static electricity is prevented from occurring. [Solution] An agricultural polyolefin-based multi-layered film which is characterized in that a fluorine-based surfactant component and a fine particulate component having an average particle size of 1.0 µm or greater are at least included in the outer layer of a base film, and an antifogging coating layer comprising as a main component an inorganic colloidal sol or a synthetic resin binder and an inorganic colloidal sol is provided on the surface of the inner layer side of the base film.

Description

Agricultural multilayer film

The present invention suppresses a decrease in translucency due to the formation of condensation on the film surface outside the house immediately after the film is spread on the house to prevent a decrease in cultivatability due to a lack of light quantity, and workability due to static electricity during film processing It is related with the polyolefin-type multilayer film for agriculture which prevents the fall of this.

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

Among the polyolefin films for agriculture, the type of anti-fogging coating on the inner film surface of the house can provide anti-fogging properties for a long period of time, and research is actively underway. As the transition from anti-fogging agent kneading type to anti-fogging agent coating type proceeds, there is a problem of poor translucency due to condensation on the outer surface of the house, which did not occur with conventional anti-fogging agent kneading type films. There was a case. Especially in agricultural polyolefin film with anti-fogging agent coating type, the water repellency of polyolefin resin in the initial stage of expansion causes condensation on the outer surface of the house, resulting in a problem of deterioration of cultivation due to less light entering the house. It was.

The poor translucency due to water repellency on the film surface is alleviated by dirt and dust on the film surface over time, but when it is expanded in the winter, the period from the expansion is short. In some cases, light transmissivity cannot be ensured when light is needed, which causes a practical problem.

Furthermore, due to the transition from such an antifogging agent kneading type to an antifogging agent coating type, there is a problem of workability deterioration due to electrostatic charge during processing that has not been a problem until now. Was desired.

On the other hand, in recent years, it has been pointed out that some of the additives used for agricultural films have or may have bioconcentration properties (environmental persistence) and toxicity. Agricultural film materials are used especially outdoors, so the use of such additives has become a problem. From the viewpoint of applying environmentally friendly agricultural materials, additives with environmental impact The development of products that do not use is required.

Various studies have been made to change the water repellency and antistatic properties of the outer side surface of the polyolefin film for agriculture immediately after such expansion, but it is simply a surfactant component such as a normal antifogging agent or antistatic agent. It was not a practically satisfactory product, for example, that the stickiness between the films would be a problem simply by adding. Due to the above circumstances, further improvements in anti-condensation and antistatic properties of polyolefin films for agriculture are required, and there is a need for a specific combination method of additives that can provide good anti-condensation and antistatic properties. It was.

As a result of intensive studies, the inventor has found that at least the outer layer of the base film contains a fluorosurfactant component and a fine particle component having an average particle size of 1.0 μm or more, and the inner surface of the base film has a synthetic resin. The present invention has been completed by finding that the above-mentioned problems can be solved in an agricultural polyolefin-based multilayer film characterized by providing an anti-fogging coating film layer mainly composed of a binder and / or an inorganic colloid sol.
Furthermore, it has been found that by using a specific type of fluorine-based surfactant component, an agricultural polyolefin-based multilayer film having no environmental impact can be provided.

That is, the present invention
(1) At least an outer layer of a substrate film having at least an outer layer, an intermediate layer, and an inner layer and containing a polyolefin-based resin contains a fluorosurfactant component and a fine particle component having an average particle diameter of 1.0 μm or more, A polyolefin multilayer multilayer film for agricultural use, characterized in that a synthetic resin binder and an inorganic colloid sol, or an antifogging coating layer mainly composed of an inorganic colloid sol is provided on the inner layer side surface of the material film,
(2) The polyolefin-based multilayer film for agriculture according to (1), wherein the fluorosurfactant component comprises a perfluoroalkylethylene oxide adduct or a perfluoroalkylpropylene oxide adduct,
(3) The polyolefin-based multilayer film for agricultural use according to (2), wherein the perfluoroalkylethylene oxide adduct or perfluoroalkylpropylene oxide adduct has a perfluoroalkyl group having 5 to 10 carbon atoms,
(4) The polyolefin multi-layer film for agriculture according to (3), wherein the perfluoroalkylethylene oxide adduct or perfluoroalkylpropylene oxide adduct has a perfluoroalkyl group having 5 to 6 carbon atoms,
(5) The fine particle component contains at least one selected from Si, Mg, Al, Li, and Ca as a constituent element component, according to any one of (1) to (4) Polyolefin multilayer film for agriculture,
(6) The agricultural polyolefin-based multilayer film according to any one of (1) to (5), wherein the fine particle component has an average particle size of 5.0 μm to 20 μm,
(7) The polyolefin multi-layer film for agriculture according to any one of (1) to (6), wherein the synthetic resin binder is an acrylic resin and / or a urethane resin;
(8) The polyolefin multi-layer film for agriculture according to any one of (1) to (7), wherein the inorganic colloidal sol is colloidal silica and / or colloidal alumina,
(9) The polyolefin multi-layer film for agriculture according to any one of (1) to (8), and (10) ethylene (A) and the following formula: Any one of (1) to (9), wherein the copolymer with the cyclic aminovinyl compound (B) represented by 1) is contained in one or more layers of the base film. Agricultural polyolefin multilayer film as described in

(In the formula, R1 and R2 each independently represent a hydrogen atom or a methyl group, and R3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
Is provided.

The present invention suppresses a decrease in translucency due to condensation that occurs on the outer surface of the house immediately after spreading, can be used without causing a decrease in cultivatability due to insufficient light quantity in the house, and is excellent in antistatic performance at a processing place A polyolefin-based multilayer film can be provided.
Moreover, by using a specific type of fluorine-based surfactant component, it is possible to provide an agricultural polyolefin-based multilayer film that does not affect the environment.
The agricultural film of the present invention may be transparent, satin or semi-satin, and can be suitably used for agricultural film (so-called agricultural PO) for house, tunnel, mulching, bag hanging, etc. it can.

[Embodiment of the Invention]
Hereinafter, the present invention will be described in detail.
The agricultural polyolefin-based multilayer film (hereinafter also referred to as “the agricultural film of the present invention”) in the present invention is characterized in that a surfactant is contained in the outer layer of the base film. Here, the base film refers to a polyolefin-based multilayer film before an antifogging coating film or the like is formed, and is composed of at least two layers. In the present invention, the base film is preferably composed of three layers of an outer layer, an intermediate layer, and an inner layer, but may include more layers. In the present invention, when the agricultural multilayer film is spread on the house, the layer facing the outside of the house is called an outer layer, and the layer facing the inside of the house is called an inner layer.

In the present invention, the present inventors have found that the effect of suppressing water repellency immediately after stretching is high particularly when a fluorine-based surfactant component is used. Specific examples of the fluorosurfactant include surfactants in which a part or all of them are substituted with F instead of H bonded to C of the hydrophobic group of a normal surfactant. A surfactant containing a fluoroalkenyl group. Such a fluorine-type surfactant can be used individually or in combination of 2 or more types. Examples of the fluorine-containing compound having a perfluoroalkyl group include an anionic fluorine-containing surfactant, a cationic fluorine-containing surfactant, an amphoteric fluorine-containing surfactant, a nonionic fluorine-containing surfactant, and a fluorine-containing oligomer. can give. In the present invention, it is particularly preferable that the fluorosurfactant component contains a perfluoroalkylethylene oxide adduct or a perfluoroalkylpropylene oxide adduct.

In the present invention, the perfluoroalkylethylene oxide adduct or the perfluoroalkylpropylene oxide adduct is preferably a perfluoroalkyl group (C ₅ F ₁₁ − having 5 to 10 carbon atoms, more preferably 5 to 8 carbon atoms). -C ₈ F ₁₇ -group).

On the other hand, PFOA (perfluorooctanoic acid; C ₇ F ₁₅ COOH) remains as a by-product in various fluorine-based products, and PFOA has environmental persistence and is slowly discharged from the living body when ingested by the living body. Therefore, there is a possibility of accumulation. However, perfluoroalkylethylene oxide adducts or perfluoroalkylpropylene oxide adducts having a perfluoroalkyl group having 5 to 6 carbon atoms (C ₅ F ₁₁ — to C ₆ F ₁₃ — group) do not contain PFOA. Therefore, when the perfluoroalkylethylene oxide adduct or perfluoroalkylpropylene oxide adduct is used, the environmental persistence is low, so it does not remain in the soil and is excellent in the environment, and the water repellency is suppressed immediately after spreading. It is particularly preferable because of its high effect.

The content of the fluorosurfactant component is preferably 0.001 to 5.0% by weight, more preferably 0.01 to 3.0% with respect to 100% by weight of the polyolefin resin in the outer layer of the base film. % By weight. If the content of the fluorine-containing surfactant component is less than 0.001% by weight, the water repellency suppressing effect is hardly exhibited, and if it exceeds 5.0% by weight, the effect is saturated, which is not preferable.

The above fluorosurfactant component is effective when contained in the outer layer of the base film. For example, even if the material added to the intermediate layer is bleed out (transferred and precipitated) and contained substantially in the outer layer of the base film, the same effect will be exhibited, so regardless of which layer was added at the time of manufacture. As a result, it is sufficient that the surfactant is contained in the above amount in the outer layer of the film.

Moreover, in this invention, a fluorine-type surfactant component can also be used in combination with another surfactant.
Other surfactants that can be used in combination with the fluorosurfactant component include various known nonionic surfactants, anionic surfactants, cationic surfactants, and other polyvalent surfactants. A polyhydric alcohol partial ester-based compound composed of alcohol and higher fatty acids and a silicone-based surfactant are preferred. Specific examples of such surfactants include, for example, nonionic surfactants such as sorbitan palmitate, alkylene oxide adducts of sorbitan palmitate, sorbitan stearate, alkylene oxide addition of sorbitan stearate. , Polyoxyalkylene sorbitan fatty acid ester, sorbitan alkylene oxide adduct and sorbitan monopalmitate (wherein sorbitan stearate and sorbitan palmitate include monoesters, diesters, triesters, and mixtures thereof) ) Sorbitan surfactants, glycerin monopalmitate, glycerin monostearate, glycerin monolaurate, diglycerin monopalmitate, Glycerin surfactants such as serine dipalmitate, glycerin distearate, diglycerin monopalmitate monostearate, triglycerin monostearate, triglycerin distearate or their alkylene oxide adducts and polyethylene glycol mono Polyethylene glycol surfactants such as stearate, polyethylene glycol monopalmitate, polyethylene glycol alkylphenyl ether, and other trimethylolpropane surfactants such as trimethylolpropane monostearate, pentaerythritol monopalmitate, pentaerythritol monostearate Pentaerythritol surfactants such as acrylate, alkylene oxide adducts of alkylphenols; sorbitan / glycerin Esters of condensate and fatty acid, sorbitan / alkylene glycol condensate and fatty acid; diglycerindiolate sodium lauryl sulfate, sodium dodecylbenzenesulfonate, cetyltrimethylammonium chloride, dodecylamine hydrochloride, lauramidoethyl laurate Examples thereof include phosphates, triethylcetylammonium iodide, oleylaminodiethylamine hydrochloride, dodecylpyridinium salts and the like and isomers thereof.
Among the above, sorbitan palmitate, alkylene oxide adduct of sorbitan palmitate, sorbitan stearate, alkylene oxide adduct of sorbitan stearate, polyoxyalkylene sorbitan fatty acid ester, sorbitan alkylene oxide adduct and sorbitan monopalmitin Sorbitan surfactants such as acid esters are preferred. The alkylene oxide to be added is preferably ethylene oxide or propylene oxide.
In the present invention, among sorbitan antifogging agents, sorbitan palmitate 0.5 mol propylene oxide adduct, polyoxypropylene sorbitan fatty acid ester, sorbitan monostearate 0.5 mol propylene oxide adduct, sorbitan mono Palmitic acid esters are particularly preferred.

The synergistic effect with the fluorosurfactant component can be exhibited by containing the other surfactant in the outer layer of the base film. In this case, for example, the material added to the intermediate layer is bleed out (transferred and precipitated), and even if it is substantially contained in the outer layer of the base film, the same effect is exhibited. Regardless of whether or not it exists, it is sufficient that the other surfactant is contained in the outer layer of the film as a result.

The agricultural film of the present invention is characterized in that a fine particle component having an average particle diameter of 1.0 μm or more is contained in at least the outer layer of the base film. Examples of the fine particle component having an average particle diameter of 1.0 μm or more include inorganic fine particles and organic fine particles. As the inorganic fine particles, an inorganic filler containing at least one selected from Si, Mg, Al, Li, and Ca as a constituent element component can be used. Among these, diatomaceous earth, natural silica, synthetic silica, talc, mica, zeolite, and the like that can be usually used as an antiblocking agent can be suitably used. As the organic fine particles, for example, polymer beads mainly composed of a thermoplastic resin can be used. Among them, acrylate, methacrylate, styrene, nylon polymers and / or copolymers thereof can be preferably used. In the present invention, the average particle size of the fine particle component is preferably 1.0 to 30 μm, more preferably 1.0 to 20 μm, and particularly preferably 5.0 to 20 μm. When the average particle size is smaller than 1.0 μm, the opening property is not sufficient, and when it is larger than 30 μm, the translucency of the multilayer film is lowered. In the present invention, the average particle diameter of the fine particle component is suitably measured using a laser diffraction method. These fine particle components can be used alone or in combination of two or more.

In one preferred embodiment of the present invention, the fine particle component is contained in the outer layer and the inner layer of the base film.

The content of the inorganic fine particles is 0.001 to 2.0% by weight, preferably 0.01 to 1.0% by weight, more preferably 0.1% to 100% by weight of the polyolefin resin in the outer layer of the base film. 0.5% by weight. When the amount of the inorganic filler used is less than 0.001% by weight, the films become sticky and practical problems arise. If it exceeds 2% by weight, it is not preferable in terms of decrease in transparency.
The content of the inorganic fine particles in the inner layer of the base film is 0.001 to 4.0% by weight, preferably 0.01 to 2.0% by weight with respect to 100% by weight of the polyolefin resin in the layer. %, More preferably 0.1 to 1.0% by weight.

The agricultural film of the present invention is characterized in that an antifogging coating layer mainly composed of a synthetic resin binder and an inorganic colloid sol or an inorganic colloid sol is formed in contact with the innermost layer of the polyolefin base film. At this time, when a large amount of an antifogging agent is contained in the film in contact with the antifogging coating film, it is difficult to form the antifogging coating film due to the spraying of the antifogging agent onto the non-uniform film surface. There is. However, when used as a master batch in which various additives are concentrated and blended with the base resin of each layer in advance, as an anti-sticking agent during kneading, or as a surface modifier when forming an antifogging coating film A small amount can be used as long as the purpose is not impaired.

Moreover, 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 layer side surface and the dustproof coating film may be formed on the outer layer side surface. In that case, the effect of improving the adhesion of the coating film, which is the effect of the present invention, may be obtained for the dust-proof coating film.

Examples of the antifogging coating film in the present invention include a composition mainly composed of a binder resin such as an inorganic colloidal sol and / or a thermoplastic resin. Preferably, an antifogging coating film mainly comprising an inorganic colloid substance and a hydrophilic organic compound or an antifogging coating film comprising an inorganic colloid substance and an acrylic resin as main components can be used. Further, the binder resin may not be added, and an inorganic material such as colloidal silica or colloidal alumina may be laminated.

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

As the inorganic colloidal sol, it is preferable to select an average particle size in the range of 5 to 100 nm. Within this range, two or more colloidal sols having different average particle sizes may be used in combination. If the average particle size is too large, the coating may be devitrified in white, and if the average particle size is too small, the stability of the inorganic colloidal sol may be unfavorable.

The inorganic colloidal sol is blended in an amount of 0.2 to 5 and preferably 0.5 to 4 in terms of a solid weight ratio with respect to the total solid weight of the binder resin composition. That is, when the blending amount is too small, a sufficient antifogging effect may not be exhibited. On the other hand, when the blending amount is too large, the antifogging effect is not easily improved in proportion to the blending amount. The film formed later becomes cloudy and causes a phenomenon that the light transmittance of the film is lowered, and the film may be coarse and brittle, which is not preferable.

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

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

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

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

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

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

Examples of alkyl esters of acrylic acid or methacrylic acid used for the production of hydrophobic acrylic resins include acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid-n-propyl ester, acrylic acid isopropyl ester, acrylic acid-n- Examples thereof include butyl esters. Generally, alkyl acrylates having 1 to 20 carbon atoms and / or methacrylic acid alkyl esters having 1 to 20 carbon atoms are used. Examples of alkenylbenzenes include styrene, α-methylstyrene, vinyltoluene and the like.

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

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

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

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

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

On the other hand, examples of (d) urethane-based resins include polyether-based, polyester-based, and polycarbonate-based anionic polyurethane aqueous compositions and emulsions. Polycarbonate anionic polyurethane emulsion is preferred in terms of water resistance, water resistance and scratch resistance, and further increases the water resistance and scratch resistance of anti-fogging coating film, as well as the time until the antifogging property is developed and the antifogging duration. From the viewpoint of properties, 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-based anionic polyurethane emulsion containing a silanol group comprises a polyurethane resin containing at least one silanol group in the molecule and a strongly basic tertiary amine as a curing catalyst. Refers to a colloidal dispersion system (emulsion) in which the silanol group-containing polyurethane resin and the strongly basic tertiary amine are dissolved in the aqueous phase, or a colloidal dispersion system in which fine particles are dispersed.

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

When preparing the antifogging agent composition for forming the antifogging coating film of the present invention, an anionic surfactant, a cationic surfactant, a nonionic surfactant, a polymer surfactant A surfactant such as can be added. The following can be used as such a surfactant.

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

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

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

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

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

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

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

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

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

In the present invention, the thickness of the coating film formed on the inner layer side surface of the film may be selected with 1/10 or less of the base film as a guide, but is not necessarily limited to this range. If the thickness of the coating is larger than 1/10 of the base film, there is a difference in flexibility between the base film and the coating, so that a phenomenon such as peeling of the coating from the base film is likely to occur. The phenomenon that a crack occurs in the coating and the strength of the base film is lowered is not preferable.

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

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

This is usually referred to as metallocene polyethylene, and is a copolymer of ethylene and an α-olefin such as butene-1, hexene-1, 4-methylpentene-1, octene and the like. (Method A) (JP 58-19309, JP 59-95292, JP 60-35005, etc.) and (B) (JP 6-9724, JP 6-136195, No. 6-136196).

A polyolefin resin polymerized by using a metallocene compound, that is, a metallocene polyethylene, is not limited to the above methods (A) and (B) in that good initial transparency and transparency persistence of the film can be obtained. Can be used.

These polyethylene resins including metallocene polyethylene are classified by temperature rise elution fractionation (TREF), MFR, density, molecular weight distribution, and various other physical properties. Measurement of elution curve by temperature rise elution fractionation (Temperature Rising Election Fractionation: TREF) is described in "Journal of Applied Polymer Science. This is carried out based on the principle described in the literature such as “Showa 63”.

The ethylene-α-olefin copolymer used as at least one component of the polyolefin resin of the present invention has an MFR measured by JIS-K7210 of 0.01 to 10 g / 10 min, preferably 0.1 to 5 g / A value of 10 minutes is shown. If the MFR is larger than this range, the film meanders during molding and is not stable. On the other hand, if the MFR is too smaller than this range, the resin pressure at the time of molding increases and a load is applied to the molding machine. Therefore, the increase in pressure must be suppressed by reducing the production amount, which is not practical. Further, the ethylene-α-olefin copolymer used as at least one component of the polyolefin resin of the present invention has a density measured by JIS-K7112 of 0.880 to 0.930 g / cm ³ , preferably 0.8. A value of 880 to 0.920 g / cm ³ is shown. When the density is larger than this range, the transparency is deteriorated. On the other hand, if the density is smaller than this range, blocking occurs due to stickiness of the film surface, resulting in poor practicality. The ethylene-α-olefin copolymer used as at least one component of the polyolefin resin of the present invention has a molecular weight distribution (weight average molecular weight / number average molecular weight) determined by gel permeation chromatography (GPC). The value is 1.5 to 3.5, preferably 1.5 to 3.0. When the molecular weight distribution is larger than this range, the mechanical strength is lowered, which is not preferable. If 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 in the range of 10 to 25% by weight, preferably in the range of 12 to 20% by weight. If the vinyl acetate content is less than this range, the resulting film will be hard and will tend to wrinkle and sag when stretched in a house, which will have a negative effect on anti-fogging properties. If it is larger than the range, the melting point of the resin is low, so that the film loosens at high temperatures in summer during house extension, and is easily broken by wind and flapping with the house structure.

The present invention provides an agricultural film that is excellent in long-term weather resistance and bleed-out resistance by using an ethylene / cyclic aminovinyl compound copolymer, and is less susceptible to a decrease in translucency due to condensation with suppressed surface water repellency. Can be obtained. The ethylene / cyclic aminovinyl compound copolymer has an effect as a light stabilizer that significantly improves long-term weather resistance as compared with a hindered amine weathering agent used in general agricultural films.

The copolymer of ethylene (A) and cyclic aminovinyl compound (B) of the present invention (hereinafter referred to as “ethylene / cyclic aminovinyl compound copolymer”) is composed of ethylene (A) and the compound of formula (1). Copolymers can be used. When the ethylene / cyclic aminovinyl compound copolymer is added in a large amount, the surface properties (water droplet contact angle, etc.) of the polyolefin film of the film can be changed, and can be suitably used for the purpose of the present invention.
Furthermore, when one or more layers of the base film contain an ethylene / cyclic aminovinyl compound copolymer, the coating film adhesion is improved when an antifogging coating film is formed on the base film. Is preferable.

In the above formula (1), R1 and R2 each independently represent a hydrogen atom or a methyl group, and R3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Preferably, R1 and R2 are each a methyl group and R3 is a hydrogen atom.

The vinyl compound (B) represented by the formula (1) can be synthesized by a known method, for example, the method described in JP-B-47-8539, JP-A-48-65180, or the like.

Representative examples of the vinyl compound (B) represented by the formula (1) 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-acryloyl Oxy-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-buty -2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-1-propyl-2,2,6,6-tetra A methyl piperidine etc. can be mentioned.

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

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

The presence of the cyclic aminovinyl compound (B) is confirmed as follows, as described in JP-A-4-80215. ^{In 13} C-NMR (for example, JNM-GSX270 Spectrometer manufactured by JEOL Ltd.), in accordance with a known method (for example, see “Equipment of Analyzes (1)”, pages 53 to 56 (1985)) Polyethyl acrylate (see "Polymer Analysis Handbook", page 969 (1985), published by Asakura Shoten) and ethylene-hydroxyethyl acrylate copolymer (Eur. Poly. J. 25, 4, 411-418 (1989) ))), The 32.9 ppm peak in the TMS standard is attributed to the methylene group in the α position from the branch point of the isolated vinyl monomer (B), and the 35.7 ppm peak It was attributed to the methylene group sandwiched between the branch points of the vinyl monomer (B). Using these two signals, the ratio of the vinyl monomer (B) present in isolation in the copolymer of ethylene (A) and vinyl monomer (B) can be calculated by the following formula.

The proportion of the hindered amine group-containing vinyl monomers having two or more hindered amine groups that are estimated as described above is not continuous but is present in an isolated state of 83% or more based on the total amount of vinyl monomers (B) in the copolymer. Is preferred. If the proportion of vinyl monomers having hindered amine groups in the side chain is less than 83% without two or more vinyl monomers having hindered amine groups in the side chain, the light stability is relatively high In some cases, the feature of having

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

Further, the ethylene / cyclic aminovinyl compound copolymer was determined by creating a calibration curve with monodisperse polystyrene using GPC. The Mw / Mn (Q value) expressed as the ratio of the weight average molecular weight to the number average molecular weight 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 agricultural polyolefin-based multilayer film of the present invention is preferably 0.5 to 15 parts by weight with respect to 100 parts by weight of the polyolefin-based resin in all layers. The amount is preferably 0.5 to 10 parts by weight. If this content is less than the above range, the weather resistance is inferior because it is inferior, and if it exceeds the above range, it is not preferable in terms of economy.

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

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

In addition, various additives usually used for agricultural films can be used in combination in the agricultural polyolefin-based multilayer film of the present invention. These additives include, for example, ultraviolet absorbers, weathering agents, hindered amine compounds, infrared absorbers, heat retention agents, fillers, metal organic acid salts, basic organic acid salts and overbased organic acid salts, hydrotalc. Site compounds, epoxy compounds, β-diketone compounds, polyhydric alcohols, halogen oxyacid salts, sulfur-based, phenol-based and phosphite-based antioxidants, thermal stabilizers, lubricants, antistatic agents, colorants, antiblocking Agents, etc.

Examples of hindered amine compounds that can be used include bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl). Malonate, tetra (2,2,6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, tetra (1,2,2,6,6-pentamethyl-4-piperidyl) butanetetracarboxylate, bis (2 , 2,6,6-tetramethyl-4-piperidyl) .di (tridecyl) butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) .di (tridecyl) butanetetracarboxylate 3,9-bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyl] Oxy) 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-tert-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 / And dibromoethane condensate.

Examples of commercially available hindered amine compounds that can be used include TINUVIN 770, TINUVIN 780, TINUVIN 144, TINUVIN 622LD, TINUVIN NOR 371, CHIMASSORB 119FL, CHIMASSORB 944 (above, manufactured by Ciba Geigy), Sanol LS-765 (Sankyo LS-765) -63, MARK LA-68, MARK LA-62, MARK LA-67, MARK LA-57, LA-900, LA-81, NO-Alkyl-1 (above, manufactured by ADEKA), UV-3346, UV- 3529, UV-3581, UV-3853 (from Cytec), Hostabin N20, Hostabin N24, Hostabin N30, Hostabin 845, Hostabin NOW, Sande Bore PR-31, Nairosutabbu S-EED (or more, manufactured by Clariant Japan KK), UVINUL5050H (or more, BASF Japan Co., Ltd.), and the like. These piperidine ring-containing hindered amine compounds are used alone or in combination of two or more.

The content of the hindered amine compound is 0.001 to 5% by weight, preferably 0.01 to 1% by weight, based on 100% by weight of the polyolefin resin in all layers. When the content is less than 0.001% by weight, a sufficient effect cannot be obtained, and when the content is more than 5% by weight, the effect is not improved, and the physical properties of the film are deteriorated.

In the present invention. A hindered amine light stabilizer can be contained in any one or more layers of the base film. Normally, when an additive such as a hindered amine compound is added to each layer, a master batch of the additive is prepared and kneaded with a base resin, but when a fluorosurfactant is added, the master batch is added. There is a tendency to color. However, when a hindered amine compound is added, there is also an advantage that coloring of the masterbatch by the fluorosurfactant is suppressed.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chloro Benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy) such as-(2'-hydroxy-3'.5'-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tert-octyl-6-benzotriazolyl) phenol Phenyl) benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3 ′, 5′-di-tert-butyl-4′-hydroxybenzoate, 2,4-di-tert-amylphenyl- Benzoates such as 3 ′, 5′-ditert-butyl-4′-hydroxybenzoate, hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; 2-ethyl-2′-ethoxyoxanilide, 2 -Substituted oxanilides such as ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-β, β-diphenylacrylate Cyanoacrylates such as methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- Triazines such as [(hexyl) oxy] -phenol, 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol Can be given. These ultraviolet absorbers are used alone or in combination of two or more.

The content of the ultraviolet absorber is preferably more than 0.001% by weight and less than 2% by weight, more preferably 0.01 to 1% by weight, based on 100% by weight of the polyolefin resin. If the content is less than the above range, the effect of improving weather resistance is low, and if it exceeds the above range, there are problems such as a decrease in transparency due to bleeding out.

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

Especially, when the hydrotalcite infrared absorber represented by the following formula (2) is used, a film that is inexpensive and has good moldability can be obtained.
_{Mg 4.5 Al 2 (OH) 13} CO 3 · 3.5H 2 O (2)

In particular, when an infrared absorber represented by the following formula (3) is used, a film that is inexpensive and has good moldability can be obtained.
[Al ₂ (Li _(1-x) · M _{(x + y)} ) (OH) _{6 + y} ] ₂ (An ⁻ ) _{2 (1 + x) / n} · mH ₂ O (3) (wherein M is Mg and / or Zn A is an n-valent anion, m is 0 or a positive number, and x and y are in the range of 0 ≦ x <1, 0 ≦ y ≦ 0.5.)

The method for obtaining the infrared absorber (heat retention agent) represented by the above formula (3) is not particularly limited, and commercially available products can be used, for example, DHT4A, SYHT-3 (manufactured by Kyowa Chemical Co., Ltd.) HT-P (manufactured by Sakai Chemical Co., Ltd.), Optima (manufactured by Toda Kogyo Co., Ltd.), Mizukarak (manufactured by Mizusawa Chemical Co., Ltd.), and the like.

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

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

The content of the inorganic fine particles is preferably more than 0.1% by weight and less than 15% by weight, more preferably 1 to 12% by weight with respect to 100% by weight of the polyolefin-based resin in all layers. If the content is less than the above range, the effect of improving heat retention is low, and if it exceeds the above range, there are problems such as a decrease in transparency.

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

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

Examples of the phenolic antioxidant include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4- Hydroxyphenyl) -propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], 1,6 -Hexamethylene bis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate] and the like.

Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl, and distearyl, and β-alkyl mercapto of polyols such as pentaerythritol tetra (β-dodecyl mercaptopropionate). And propionic acid esters.

Examples of the phosphite antioxidant include trisnonylphenyl phosphite, tris (2,4-ditert-butylphenyl) phosphite, tris [2-tert-butyl-4- (3-tert-butyl- 4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite.

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

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

The base film of the present invention is weighed in a necessary amount for blending various additives, and blender such as a ribbon blender, a Banbury mixer, a Henschel mixer, a super mixer, a single or twin screw extruder, a roll, or a kneading machine. Any other known blending machine or mixing machine may be used. In order to form the resin composition thus obtained into a film, a method known per se, for example, a melt extrusion molding method (including a T-die method and an inflation method), calendar processing, roll processing, extrusion molding processing, Blow molding, inflation molding, melt casting, pressure molding, paste processing, powder molding, and the like can be suitably used.

The thickness of the base film of the present invention is preferably in the range of 0.01 to 1 mm in terms of strength and cost, more preferably 0.05 to 0.5 mm, and still more preferably 0.05 to 0.00 mm. 2 mm. If it is less than this range, there is a problem in strength, and if it exceeds this range, molding is difficult and there is a problem in stretch workability.

Also, in the agricultural polyolefin-based multilayer film of the present invention, 3 to 5 layers are easy to balance each layer. The layer ratio constituting the three-layer film is preferably in the range of 1 / 0.5 / 1 to 1/5/1 from the viewpoint of moldability, transparency and strength, and 1/2/1 to 1/4/1. The range of is more preferable. Further, the ratio between the outer layer and the inner layer is not particularly specified, but it is preferable that the ratio is approximately the same because of the curl property of the obtained film.

In actually using the polyolefin-based multilayer film for agriculture according to the present invention, it is preferable that the side provided with the anti-fogging coating film is spread inside the house or tunnel.

The agricultural polyolefin-based multilayer film of the present invention is an agricultural film in which a decrease in translucency due to condensation immediately after spreading is suppressed, and can be suitably used even in an area where condensation is likely to occur.
Furthermore, it is very easy to handle because it does not cause a decrease in openability that normally occurs when a surfactant component is added to the layer facing the outside of the house, and it is very easy to handle, and is provided as an agricultural film. It has a good balance of performance. The agricultural film of the present invention may be transparent, pear or semi-pear, and is suitable for use in agricultural films (so-called agricultural poly, agricultural sacbi, agricultural PO, etc.) for house, tunnel, mulching, bag hanging, etc. Can be used for

Hereinafter, the present invention will be described in more detail based on examples and comparative examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

(1) Adjustment of laminated film 100 mmφ (made by Pla Koken Co., Ltd.) is used for a three-layer die as a three-layer inflation molding device, and the extruder has an outer tube inner layer of 30 mmφ (made by Pla Giken Co., Ltd.), two intermediate layers Is 40 mmφ (manufactured by Pla Giken Co., Ltd.), the outer layer extruder temperature is 180 ° C., the intermediate layer extruder temperature is 170 ° C., the die temperature is 180 to 190 ° C., the blow ratio is 2.0 to 3.0, the take-off speed is 3 to A three-layer laminated film comprising the components shown in Tables 1 to 3 was obtained at 7 m / min and a thickness of 0.15 mm. Since these films are used with the end of the tube cut open when the house is stretched, the tube outer layer during film formation becomes the inner layer (inner surface) of the house when stretched when unfolded.

[Composition] Addition amounts are as described in each table.
HP-LDPE: Branched polyethylene produced with a high-pressure radical catalyst (MFR: 1.1 g / 10 min, density 0.920) Novatec LD “YF30” manufactured by Nippon Polychem
Metallocene PE: An ethylene / α-olefin copolymer produced with a metallocene catalyst (MFR: 2 g / 10 min, density 0.907) Kernel “KF270” manufactured by Nippon Polychem
EVA1: Ethylene / vinyl acetate copolymer (vinyl acetate content 5% by weight, MFR 2 g / 10 min)
EVA2: Ethylene / vinyl acetate copolymer (vinyl acetate content 15% by weight, MFR 2 g / 10 min)

Fluorosurfactant A: Perfluoroalkylethylene oxide adduct DS-405 (perfluoroalkyl group having 8 carbon atoms) (Daikin Chemicals Sales Co., Ltd.)
Fluorosurfactant B: Perfluoroalkylethylene oxide adduct DSN-403N (carbon number of perfluoroalkyl group is 6) (Daikin Chemicals Sales Co., Ltd.)
Surfactant A: Nonionic surfactant “Electro Stripper TS-EA” manufactured by Kao Corporation
Surfactant B: Polyoxyethylene sorbitan monooleate Surfactant C: Sorbitan palmitate 0.5 mol propylene oxide adduct UV absorber A: Cyaryl triaryl triazine UV absorber “UV1164”
Synthetic hydrotalcite A: “DHT4A” manufactured by Kyowa Chemical Co., Ltd.

Light Stabilizer A: Light Stabilizer “Tinuvin NOR 371 FF” manufactured by Ciba Specialty Chemicals
Ethylene / Cyclic aminovinyl copolymer: “Novatech LD / XJ100H” manufactured by Nippon Polyethylene Co., Ltd. MFR = 3 g / 10 min (190 ° C., JIS-K6760) Density = 0.931 g / cm ³ (JIS-K6760) Cyclic amino Vinyl compound content = 5.1% by weight (0.7 mol%) Percentage of cyclic aminovinyl compound present in isolation = 90 mol% Melting point = 111 ° C.

Inorganic fine particle A: added as a master batch “MF20KG” made by Nippon Polyethylene Co., Ltd. containing natural silica.
Inorganic fine particle B: “F-30” manufactured by Fuji Chemical Industry Co., Ltd.
The average particle size of the above-mentioned fine particle component is the value of D50 by a laser diffraction method using a “Microtrack particle size distribution measuring device” manufactured by Nikkiso Co., Ltd. (particle size (μm )) Was used.

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

(3) Formation of antifogging coating film The main component (silica sol and / or alumina sol) shown below, a thermoplastic resin, a crosslinking agent and a liquid dispersion medium were blended to obtain an antifogging agent composition.

The antifogging agent composition was blended as follows.
Inorganic colloidal sol (colloidal silica) 4.0
Thermoplastic resin (Sanmor SW-131: hydrophobic binder resin) 3.0
Cross-linking agent (TAZM) 0.1
Dispersion medium (water / ethanol = 3/1) 93
(Note) The amount of inorganic colloidal sol is indicated by the amount of inorganic particles, and the amount of thermoplastic resin is indicated by the solid content of the polymer.

Colloidal silica: Snowtex 30 manufactured by Nissan Chemical Industries, average particle size of 15 nm
Sunmole SW-131: acrylic emulsion T.M. manufactured by Sanyo Kasei Co., Ltd. A. Z. M: Aziridine compound manufactured by Mutual Yakugyo Co., Ltd.

The above antifogging agent composition was applied to the surface of the base film surface-treated in (2) using a # 5 bar coater. The applied film was kept in an oven at 80 ° C. for 1 minute to volatilize the liquid dispersion medium to form an antifogging coating film. The thickness of the coating film of each obtained film was about 1 μm.

The following physical properties were measured for each type provided with an antifogging coating (film thickness: 100 μm), but the resin, additives, combinations other than the coating used this time, As long as the gist is not changed, the same effect can be obtained. The following tests were conducted for each sample used this time. Each measuring method in an Example and a comparative example is shown below.

(1) Water drop contact angle measurement The water drop contact angle of each sample was measured with a water drop contact angle measuring device (manufactured by Elma), and the results were evaluated according to the following criteria.
○: Water droplet contact angle is smaller than 60 °.
Δ: Water droplet contact angle is 60 ° or more and less than 90.
X: Water droplet contact angle is larger than 90 °.

(2) Water drop adhesion test at the initial stage of expansion A film was spread on October 28, 2011 in a pipe house constructed in a field in Matsusaka City, Mie Prefecture. On the morning of November 2, five days after being deployed in the house, the state of water droplets adhering to the outside surface of the house was visually observed from inside the pipe house.
Percentage of water droplet (drop-shaped portion) adhesion area due to condensation on the outside of the house ○: 70% or less Δ: 70-90%
×: 90 to 100%

(3) Charge voltage measurement The charge voltage of each sample was measured with a static Honestator (manufactured by SHISHIDO.Co), and the ratio of the charge voltage after 5 minutes to the initial charge voltage (%) was evaluated according to the following criteria. It was shown to.
○: The ratio (%) of the charged voltage after 5 minutes to the initial charged voltage is lower than 20%.
Δ: The ratio (%) of the charged voltage after 5 minutes to the initial charged voltage is in the range of 20 to 80%.
X: The ratio (%) of the charged voltage after 5 minutes to the initial charged voltage is higher than 80%.

(4) Openability test results The openability of each sample was evaluated with the film just prepared by the inflation molding apparatus.

Mouth openness evaluation:
Method = Cut the four corners of the tube-shaped film with scissors and visually evaluate the state when the two films are lifted by holding one of them. ◎: The films are completely separated from each other before being lifted. The film can be peeled off naturally without adding X: The film is difficult to peel off, and cannot be separated without applying artificial force

(5) Presence / absence of PFOA (perfluorooctanoic acid) content When the fluorosurfactant component used contains PFOA (perfluorooctanoic acid), it is described as “Yes”. It was written as “nothing”.

[Example 1, Comparative Examples 1 to 3]
By the above formulation, a three-layer film (anti-fogging coating application type) with a film thickness of 150 μm and a layer ratio of 1/3/1 is prepared, and the water droplet contact angle measurement, water droplet adhesion evaluation immediately after stretching, and charged voltage measurement by the above methods. The mouth openability was evaluated. The results are shown in Table 1.

[Examples 1 and 2, Comparative Example 4]
By the above formulation, a three-layer film (anti-fogging coating application type) with a film thickness of 150 μm and a layer ratio of 1/3/1 is prepared, and the water droplet contact angle measurement, water droplet adhesion evaluation immediately after stretching, and charged voltage measurement by the above methods. The mouth opening property was evaluated. The results are shown in Table 2.

[Examples 1, 3 and 4, Comparative Examples 5 to 6]
By the above formulation, a three-layer film (anti-fogging coating application type) with a film thickness of 150 μm and a layer ratio of 1/3/1 is prepared, and the water droplet contact angle measurement, water droplet adhesion evaluation immediately after stretching, and charged voltage measurement by the above methods. The mouth opening property was evaluated. The results are shown in Table 3.

[Examples 1 and 5]
By the above formulation, a three-layer film (anti-fogging coating application type) with a film thickness of 150 μm and a layer ratio of 1/3/1 is prepared, and the water droplet contact angle measurement, water droplet adhesion evaluation immediately after stretching, and charged voltage measurement by the above methods. Table 4 shows the results of mouth opening evaluation and the presence or absence of PFOA.

As is clear from the above results, the fluorosurfactant component according to the present invention and the fine particle component having an average particle size of 1.0 μm or more are contained in at least the outer layer of the base film, and synthesized on the inner layer side surface of the base film. Polyolefin agricultural multilayer film characterized by providing a resin binder and / or an anti-fogging coating film layer mainly composed of an inorganic colloidal sol is a reduction in translucency due to dew condensation immediately after stretching, The mouth opening is remarkably excellent (Examples 1 to 4).

On the other hand, when the fluorine-based surfactant component according to the present invention is lacking, it is not possible to sufficiently suppress the decrease in translucency due to condensation (Comparative Example 1). Further, when a surfactant other than the fluorosurfactant is used, there is an effect of suppressing a decrease in translucency due to condensation, but when comparing Examples 1 and 2 with Comparative Examples 2 to 4, the fluorosurfactant It can be seen that there is a remarkable suppression effect when the agent is used.
Further, when the fine particle component according to the present invention is not added to the outer layer, the openability is inferior and there is a problem in use (Comparative Example 5). Further, when the particle size range of the fine particle component according to the present invention is below, the openability is inferior as in the case where the fine particle component is absent (Comparative Example 6). That is, when the constituent elements according to the present invention are lacking, it cannot be said that the performance to be provided as an agricultural film is provided in a balanced manner.

Further, when a fluorosurfactant having a C 6 perfluoroalkyl group is used, there is no environmental impact, and in addition, the reduction in translucency due to condensation immediately after stretching, the voltage resistance, and the mouth opening property Table 4 shows that a significantly superior agricultural multilayer film can be provided (Example 5).

Claims (10)

1. At least the outer layer of the substrate film having at least an outer layer, an intermediate layer and an inner layer and containing a polyolefin-based resin contains a fluorosurfactant component and a fine particle component having an average particle size of 1.0 μm or more, A polyolefin multilayer film for agriculture, comprising an anti-fogging coating layer mainly composed of a synthetic resin binder and an inorganic colloid sol or an inorganic colloid sol on the inner layer side surface.
2. The polyolefin-based multilayer film for agriculture according to claim 1, wherein the fluorine-based surfactant component contains a perfluoroalkylethylene oxide adduct or a perfluoroalkylpropylene oxide adduct.
3. The agricultural polyolefin-based multilayer film according to claim 2, wherein the perfluoroalkylethylene oxide adduct or perfluoroalkylpropylene oxide adduct has a perfluoroalkyl group having 5 to 10 carbon atoms.
4. The agricultural polyolefin-based multilayer film according to claim 3, wherein the perfluoroalkylethylene oxide adduct or perfluoroalkylpropylene oxide adduct has a perfluoroalkyl group having 5 to 6 carbon atoms.
5. The agricultural polyolefin system according to any one of claims 1 to 4, wherein the fine particle component contains at least one selected from Si, Mg, Al, Li, and Ca as a constituent element component. Multilayer film.
6. The polyolefin multilayer film for agricultural use according to any one of claims 1 to 5, wherein an average particle size of the fine particle component is 5.0 µm to 20 µm.
7. The agricultural polyolefin multilayer film according to any one of claims 1 to 6, wherein the synthetic resin binder is an acrylic resin and / or a urethane resin.
8. The agricultural polyolefin-based multilayer film according to any one of claims 1 to 7, wherein the inorganic colloidal sol is colloidal silica and / or colloidal alumina.
9. The agricultural polyolefin-based multilayer film according to any one of claims 1 to 8, comprising the fine particle component in an outer layer and an inner layer of a base film.
10. 2. A copolymer of ethylene (A) and a cyclic aminovinyl compound (B) represented by the following formula (1) is contained in one or more layers of a base film. The agricultural polyolefin-based multilayer film according to any one of 1 to 9.
    

    

    (In the formula, R1 and R2 each independently represent a hydrogen atom or a methyl group, and R3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)