JP2001262132A - Agricultural polyolefin-based resin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an agricultural polyolefin-based resin film having a high transparency, hardly melt-adhering on overlapping the films each other and excellent in anti-fogging property (the quickness of development and persistency). SOLUTION: This agricultural polyolefin-based resin film is obtained by forming an acrylic resin membrane having 50-82 deg.C range glass transition temperature on the outer surface of a house on a spreading for setting it up and also forming a membrane consisting of an anti-fogging agent containing three component of (a) an aqueous dispersion of a hydrophobic acrylic resin having 35-80 deg.C range glass transition temperature, (b) a polyurethane aqueous resin composition and (c) an inorganic colloidal sol as indispensable components on another side surface.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin resin film for agricultural use, and more particularly, to a film having high transparency, little fusing when the films are overlapped with each other, and having weather resistance, anti-fogging property, and the like. In particular, the present invention relates to a polyolefin resin film for agricultural use which is excellent in the speed of developing anti-fogging properties and the long-term durability of anti-fogging properties.

[0002]

2. Description of the Related Art In recent years, in order to increase marketability and productivity of agricultural crops by semi-forcing or restraining cultivation, in recent years, agricultural vinyl chloride films, polyethylene, ethylene-vinyl acetate copolymers, and polyolefin resins have been used. BACKGROUND ART So-called house cultivation and tunnel cultivation in which useful plants are cultivated under an agricultural covering material such as a special film as a main component are actively performed.

[0003] Among them, special films mainly composed of polyolefin-based resins have been widely used because they are lightweight, generate little toxic gas even when incinerated, and are inexpensive. . By the way, in such an agricultural house, the film on the side of the house is wound around a metal pipe or the like to open the side of the house in order to prevent the inside of the house from becoming hot when the temperature in the spring to autumn is high. Ventilate. In summer, when the temperature is high, the side film may be left rolled up and left for several months.At this time, the film is exposed to an atmosphere of high temperature and high humidity. The surfaces may fuse together. When the temperature falls in the fall or winter, the film that has been rolled up is rolled down to prevent the inside of the house from becoming cold, but if the film is fused, it cannot be rolled down, and if you forcibly roll it down The film was torn and this was a major problem.

[0004] As a method of solving this problem, the film is subjected to graining or the addition of a large amount of an inorganic compounding agent to roughen the film surface, thereby reducing the contact area of the wound film and fusing. Although a method of preventing this is conceivable, it is not practical because the transparency of the film is greatly impaired by roughening. Also, agricultural polyolefin resin films used in these agricultural houses, because the surface is hydrophobic, depending on the conditions such as temperature and humidity, the film surface fogging, so poor penetration of sunlight, The growth of the plant is slowed down, or water droplets generated by aggregation of cloudy fine water droplets fall on the cultivated plant, thereby damaging the young shoots or causing disease.

[0005] It is known that such problems can be solved by imparting anti-fog properties to the surface of the agricultural polyolefin resin film. In order to impart antifogging properties to the surface of the agricultural polyolefin resin film, a method of kneading a hydrophilic substance such as a surfactant into the polyolefin resin, or after forming the film, on the surface,
For example, various methods have been proposed for applying a mixture of silica or alumina and a surfactant.

However, in the former method, the hydrophilic substance kneaded into the resin blows out onto the film surface and coordinates,
Since the film is provided with anti-fogging property, the time required for the film to exhibit anti-fogging property is short, but it is easily washed away by water, and the anti-fogging property is lost within a short period of time. On the other hand, even in the latter method, since the adhesion to the polyolefin-based resin film is poor, the formed coating film falls off with the passage of time. It was difficult to balance sustainability.

Further, in recent years, there has been a demand for a material which can be spread over agricultural covering materials for a long period of time because of the labor shortage of farmers and resource saving. However, there are problems such as the high price, the rigidity, and the time required for the expansion work.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a rolled-up film which can be fused without impairing the transparency of the film, and which has excellent weather resistance and anti-fog properties and can be spread over a long period of time. It is an object of the present invention to provide an agricultural polyolefin resin film that can be used.

[0009]

The gist of the present invention is a polyolefin resin film for agricultural use, which has a glass transition temperature of 50 to 50 on the outer surface of the house when stretched.
Forming an acrylic resin film in the range of 82 ° C., on the other surface, (a) an aqueous dispersion of a hydrophobic acrylic resin having a glass transition temperature in the range of 35 to 80 ° C., and (b) an aqueous polyurethane resin The composition and (c) an agricultural polyolefin-based resin film formed by forming a coating comprising an anti-fogging agent composition comprising three components of an inorganic colloid sol as essential components, and preferably the blending amount of the component (b) Is 0.01 or more and 1 or less with respect to the component (a) in terms of solid content weight ratio, and the blending amount of the component (c) is 0 with respect to the total of the component (a) and the component (b) in terms of the solid content weight ratio. The present invention relates to an agricultural polyolefin-based resin film having a coating formed of an antifogging agent composition of not less than 5 and not more than 5.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
As the polyolefin resin in the present invention, α-olefin homopolymer, a copolymer with a different monomer having α-olefin as a main component, for example, polyethylene, polypropylene, ethylene-propylene copolymer,
Ethylene-butene copolymer, ethylene-4-methyl-1
-Pentene copolymer, ethylene-vinyl acetate copolymer,
Examples include an ethylene-acrylic acid copolymer. Of these, low-density polyethylene having a density of 0.910 to 0.935, an ethylene-α-olefin copolymer, and an ethylene-vinyl acetate copolymer having a vinyl acetate content of 30% by weight or less are transparent or weather-resistant. It is preferable as an agricultural film in terms 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 one component of the polyolefin resin. This is generally called metallocene polyethylene, and ethylene and α- such as butene-1, hexene-1, 4-methylpentene-1 and octene are used.
A copolymer with an olefin, the copolymer comprising (A)
Method) JP-A-58-19309, JP-A-59-9529
No. 2, JP-A-60-35005, JP-A-60-350
No. 06, JP-A-60-35007, JP-A-60-35
008, JP-A-60-35009, JP-A-61-1
No. 30314, Japanese Unexamined Patent Publication No. Hei 3-163088, European Patent Application Publication No. 420436,
U.S. Pat. No. 5,055,438 and International Publication WO9
1/04247, that is, a metallocene catalyst, particularly a metallocene-alumoxane catalyst, or, for example, WO92 / 01723.
Or a catalyst comprising a metallocene compound and a compound capable of reacting with the metallocene compound to form a stable ion, as disclosed in Japanese Patent Application Laid-open No. Hei.
No. 20, JP-A-5-295022, etc., using a catalyst in which a metallocene compound is supported on an inorganic compound or the like, using ethylene as a main component and α- of a subcomponent having 4 to 20 carbon atoms. In this method, an olefin is copolymerized so that the density of the obtained copolymer is 0.880 to 0.930 g / cm ³ . Examples of the polymerization method include a high-pressure ion polymerization method, a solution method, a slurry method, and a gas phase method. Among these, it is preferable to produce by a high pressure ionic polymerization method.

The high-pressure ionic polymerization method is described in JP-A-56-18607 and JP-A-58-25106, and the pressure is at least 100 kg / cm ² , preferably at least 300 kg / cm ^2. It is produced by high-pressure ion polymerization under the reaction conditions of 1500 kg / cm ² and a temperature of 125 ° C. or more, preferably 150 to 200 ° C.
On the other hand, ethylene-α called metallocene polyethylene
-As a method for producing an olefin copolymer, for example, (B
Method) JP-A-6-9724, JP-A-6-136195
JP-A-6-136196, JP-A-6-20705
An olefin polymerization catalyst comprising a metallocene catalyst component, 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 described in each of the publications of No. 7 In the presence of, ethylene and α-olefin, specifically α-olefin having 3 to 20 carbon atoms, under various conditions in a gas phase, or a liquid phase in a slurry or a solution, to obtain a copolymer obtained Of 0.900 to 0.9
It can also be prepared by copolymerization to give 30 g / cm 3, but the production of metallocene polyethylene by the above-mentioned method (A) is more preferred in that good initial transparency and transparency persistence of the film can be obtained.

The metallocene polyethylene obtained by the method (A) is fractionated by elution at elevated temperature (TREF: Temperatutu).
re Rising Elution Fraction
nation) is determined by a differential elution curve obtained by the measurement according to the present invention. That is, there is one peak of the elution curve obtained by the temperature-rise elution fractionation, and the peak temperature is in the range of 20 to 100 ° C, preferably 40 to 80 ° C. In addition, the substance eluted 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 becomes poor.
If not present, the film will be sticky.

Measurement of elution curve by temperature rise elution fractionation (TREF) The above temperature rise elution fractionation (Temperature Ri)
sing Elution Fractionation
n: TREF) is described in “Journ
al of Applied Polymer Sci
ence. Vol 126, 4, 217-4, 231
(1981) "," Polymer Symposium Proceedings 2P1C09 "
(1988) ”and the like. That is, the target polyethylene is first completely dissolved in a solvent. Then cool down,
Generate a thin polymer layer on the surface of the inert carrier. Such a polymer layer is formed such that an easily crystallizable material is formed on the inner side (a side close to the surface of the inert carrier), and a hardly crystallizable material is formed on the outer side. Next, by elevating the temperature continuously or stepwise, first, at a low temperature, it elutes from an amorphous portion in the target polymer, that is, from a polymer having a large degree of short-chain branching of the polymer. As the elution temperature rises, the one with a low degree of branching gradually elutes, and finally the linear portion without branching elutes, ending the measurement. The concentration of the eluting component at each temperature is continuously detected, and the composition distribution of the polymer can be measured by the peak of a graph (elution curve) drawn by the elution amount and the elution temperature.

The ethylene-α-olefin copolymer used as one component of the polyolefin resin of the present invention is:
It shows the following physical properties. Melt flow rate (MFR) MFR measured by JIS-K7210 is 0.01
It shows a value of from 10 to 10 g / 10 min, preferably from 0.1 to 5 g / 10 min. If the MFR is larger than this range, the film will meander during molding and will not be stable. In addition, the MFR
If the pressure 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.

[0016]density The density measured by JIS-K7112 is 0.880
~ 0.930 g / cm ^Three, Preferably 0.880-0.
920 g / cm^ThreeIt shows the value of. This density is
If it is larger than the range, transparency deteriorates. Also, the density
If it is smaller than the range, the film surface will become sticky due to stickiness.
Locking occurs and the utility becomes poor.

Molecular weight distribution gel permeation chromatography (GPC)
Molecular weight distribution (weight average molecular weight / number average molecular weight) determined by (1) is 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 decreases, which is not preferable. If the molecular weight distribution is smaller than this range, the film will meander during molding and will not be stable.

The agricultural polyolefin resin film of the present invention may further comprise a plasticizer, an anti-fogging agent, an ultraviolet absorber, a light-stable material, if necessary, as long as the adhesion of the dust-proof coating film and the anti-fog coating film is not impaired. Agents, antioxidants, lubricants, heat stabilizers, coloring agents such as pigments and dyes, anti-fog agents, antistatic agents, inorganic fine particles and the like can be added. As the plasticizer, for example,
Phthalic acid derivatives, isophthalic acid derivatives, adipic acid derivatives, maleic acid derivatives, citric acid derivatives, itaconic acid derivatives, oleic acid derivatives, ricinoleic acid derivatives, other tricresyl phosphates, epoxidized soybean oil, epoxy resin plasticizers, etc. No.

As the antifogging agent, a nonionic surfactant,
Examples include anionic surfactants and cationic surfactants. Examples of the ultraviolet absorber include benzotriazole-based, benzoate-based, benzophenone-based, cyanoacrylate-based, phenyl salicylate-based, and triazine-based ultraviolet absorbers. Among them, a benzophenone-based ultraviolet absorber and / or a benzotriazole-based ultraviolet absorber are particularly preferable.

As the light stabilizer, various compounds usually used for agricultural purposes can be used. In particular,
JP-B-62-59745, column 5, line 37 to column 16, line 18; JP-A-2-30529, page 20, 15
Hindered amine compound described in the third to third lines of page 38. Examples of commercially available hindered amine compounds that can be used in the present invention include TINUVIN 770,
TINUVIN 780, TINUVIN 144, TIN
UVIN622LD, CHIMASSORB119F
L, CHIMASSORB 944 (above, manufactured by Ciba-Geigy), Sanol LS-765 (manufactured by Sankyo), MA
RKLA-63, MARK LA-68, MARK L
A-68, MARK LA-62, MARK LA-6
7, MARK LA-57 (all manufactured by Adeka Argus) and the like.

As the antioxidant, 2,6-di-ter
Examples thereof include t-butyl-4-methylphenol, 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), and dilaurylthiodipropionate. Examples of lubricants or heat stabilizers include polyethylene wax, liquid paraffin, bisamide, stearic acid, zinc stearate, aliphatic alcohol, calcium stearate, barium stearate, barium ricinoleate, dibutyltin dilaurate, dibutyltin dimaleate, and organic phosphoric acid Examples include metal salts, organic phosphite compounds, phenols, β-diketone compounds, and the like.

Examples of the coloring agent include phthalocyanine blue, phthalocyanine green, Hansa Yellow, Alizarin Lake, titanium oxide, zinc white, ultramarine, permanent red, quinacridone, carbon black and the like. Examples of the antifog include fluorine-based surfactants. Specifically, the C-type of the hydrophobic group of a normal surfactant is used.
Surfactants in which part or all of H is bonded to F instead of H, particularly surfactants containing perfluoroalkyl or perfluoroalkenyl groups. These various additives can be used alone or in combination of two or more. The amounts of the various additives can be selected within a range that does not deteriorate the performance of the film, particularly the adhesion of the dustproof coating and the antifogging coating.

The inorganic fine particles include inorganic oxides, inorganic hydroxides and hydrotalcites containing at least one atom of Mg, Ca, Al, Si and Li effective as a heat insulator. Specifically, SiO ₂ , Al ₂ O
₃ , inorganic oxides such as MgO and CaO; Al (OH) ₃ ,
Inorganic hydroxides such as Mg (OH) ₂ and Ca (OH) ₂ ; formula M 2 ⁺ _{1 -X} Al _X (OH) ₂ (A ⁿ⁻ ) _{X / n} · mH ₂ O [wherein M ²⁺ is, Mg, a divalent metal ion of Ca or Zn, a ^{n-is Cl -, Br -, I-,} NO 3 2-, ClO 4-,
SO ₄ ²⁻ , CO ₂ ²⁻ , SiO ₃ ²⁻ , HPO ₄ ²⁻ , HB
Anion such as O ₃ ²⁻ and PO ₄ ²⁻ , wherein x is 0 <x <
Is a numerical value satisfying the condition of 0.5, and m is 0 ≦ m ≦ 2
And a hydrotalcite such as a fired product thereof.

These inorganic fine particles can be used alone or in combination of two or more. The amount of the above various additives is within a range that does not deteriorate the performance of the film, and is usually 1 to 100 parts by weight of the base olefin resin.
It can be selected in a range of 2 parts by weight or less. In order to mix various additives with the base polyolefin-based resin, a necessary amount of each additive is weighed, and a ribbon blender, a Banbury mixer, a super mixer and other conventionally known compounding machines and mixers may be used. In order to form the resin composition thus obtained into a film, conventionally known methods such as a melt extrusion molding method (including a T-die method and an inflation method) and a calender molding method are known. According to the method.

Such a film may be a single layer, but may be a laminated film in terms of dustproofness, flexibility and strength, and for example, a three-layer laminated film is preferable. For example, 3
Of the layers, the layer that is outside when the house is stretched is a layer made of metallocene polyethylene as a main resin, and the intermediate layer is a layer made of an ethylene-vinyl acetate copolymer having a vinyl acetate content of 10 to 20% by weight as a main resin. A mode in which the inner layer is formed as a layer having an ethylene-vinyl acetate copolymer having a vinyl acetate content of 3 to 12% by weight as a main resin, the inner and outer layers are layers having a metallocene polyethylene as a main resin, and the intermediate layer is ethylene-acetic acid. An embodiment in which a layer containing a vinyl copolymer as a main resin is formed is preferably exemplified.

The film according to the present invention may be transparent, satin-finished or semi-matted, and can be used for covering agricultural houses (greenhouses), tunnels, etc., as well as for mulching and bagging. Can be used. The thickness of the film is preferably in the range of 0.03 to 0.3 mm in terms of strength and cost, and more preferably 0.05 to 0.2 mm.

In the present invention, an acrylic resin film having a glass transition temperature in the range of 50 to 82 ° C., preferably 55 to 80 ° C. is formed on the outer surface of the house at the time of stretching of the base polyolefin resin film. It is characterized by. If the glass transition temperature of the acrylic resin coating is too low, fusion between the coating and the base film is likely to occur,
Also, if it is too high, the film is insufficient in flexibility, so that the film cannot follow the film deformation due to winding up or the flapping deformation due to the wind during stretching, and peeling and cracking occur and the film transparency is impaired. And the utility is poor.

In the present invention, one example of the acrylic resin preferably used as the acrylic resin for the coating formed on the outer surface of the house at the time of stretching is 5 to 40% by weight of hydroxylalkyl (meth) acrylate, and one or two hydroxylalkyl (meth) acrylates in the molecule. Α, β-unsaturated carboxylic acid containing a carboxyl group as described above
Copolymers obtained by copolymerizing a monomer component consisting of another vinyl compound which can be copolymerized with these compounds in an amount of up to 20% by weight and the remainder can be mentioned.

The hydroxyalkyl (meth) acrylate monomers include hydroxymethyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2
-Hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2-hydroxypentyl acrylate, 2-hydroxypentyl methacrylate, 6-hydroxyhexyl acrylate,
6-hydroxyhexyl methacrylate and the like.

The α, β-unsaturated carboxylic acid having one or more carboxyl groups in the molecule includes acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, aconitic acid, fumaric acid, Crotonic acid and the like can be mentioned, and it is preferable to use it at 20% by weight or less. Other vinyl compounds copolymerizable with the compound include alkyl acrylates having an alkyl group of 1 to 5 such as methyl acrylate, ethyl acrylate, n-propyl acrylate, and isopropyl acrylate; methyl methacrylate, ethyl methacrylate, n Alkyl methacrylates having an alkyl group of 1 to 5 such as -propyl methacrylate and isopropyl methacrylate; α, β-ethylenically unsaturated phosphonic acids such as ethylene sulfonic acid; containing hydroxyl groups such as hydroxyethyl of acrylic acid or methacrylic acid Vinyl monomers: acrylonitriles; acrylamides; glycidyl esters of (meth) acrylic acid, and the like. These monomers may be used alone or in combination of two or more.

In the polymerization of the acrylic resin, a predetermined amount of a monomer is mixed, charged into a polymerization vessel together with an organic solvent, a polymerization initiator and, if necessary, a molecular weight regulator are added, and the mixture is heated with stirring and heated. I do. For the polymerization, generally known methods such as a suspension polymerization method and a solution polymerization method are employed. In this case, examples of the polymerization initiator that can be used include a radical generation catalyst such as α, α-azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, and the like. As the molecular weight regulator, butyl mercaptan, n -Dodecyl mercaptan, tert-dodecyl mercaptan, β-
And mercaptoethanol. Examples of the organic solvent used for the polymerization include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-
Alcohols such as butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, tert-amyl alcohol, n-hexyl alcohol, and cyclohexanol; aromatic hydrocarbons such as benzene, toluene and xylene; ethyl acetate, butyl acetate and the like Acetates; acetone, methyl ethyl ketone, methyl-n-
Ketones such as propyl ketone, 2-hexanone, 3-hexanone, di-n-propyl ketone, di-n-amyl ketone cyclohexanone; and tetrahydrofuran.
These can be used alone or in combination of two or more.

Further, in the present invention, another example which is preferably used as an acrylic resin for a film formed on the outer surface of the house at the time of spreading includes a method in which a methacrylic acid alkyl ester monomer is added in the presence of a crosslinked acrylate-based elastic material. body,
Or a graft copolymer obtained by polymerizing a mixture of a methacrylic acid alkyl ester as a main component and a vinyl compound monomer copolymerizable therewith, wherein the crosslinked acrylate-based elastic material is from 5 to 80%. % By weight.

As the alkyl acrylate, those having 1 to 8 carbon atoms in the alkyl group are preferably used.
It may be linear or branched. Specific examples include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, and the like, and these can be used in combination.

The vinyl compound monomers copolymerizable with these alkyl acrylates include methacrylic acid, alkyl esters of methacrylic acid, dialkyl esters of itaconic acid, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, styrene, Nuclear alkyl-substituted styrene, α-methylstyrene and the like can be mentioned.

As the crosslinkable monomer, those usually used as polyfunctional compounds may be used. Specifically, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, propylene glycol dimethacrylate, Methylolpropane trimethacrylate, tetramethylolmethanetetramethacrylate,
Examples include dipropylene glycol dimethacrylate, divinylbenzene, divinyl adipate, diallyl phthalate, diallyl maleate, allyl acrylate, allyl methacrylate, triallyl cyanurate, and the like, and two or more of these may be used in combination.

The crosslinked acrylate-based elastic material is preferably produced by an emulsion polymerization method. The polymerization initiator that can be used at this time is a usual free radical generation initiator. Specifically, inorganic persulfides such as potassium persulfate and ammonium persulfate; organic hydroperoxides such as cumene hydroperoxide, p-menthane hydroperoxide and ditertiary butyl hydroperoxide; benzoyl peroxide and lauroyl peroxide And organic peroxides such as cumene peroxide and azo-based initiators such as azobisisobutyronitrile. Further, ordinary redox initiators obtained by combining these with reducing agents such as sodium sulfite, sodium acid sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, glucose, polyamine and hydroxyacetone ascorbate can also be used.

Examples of the emulsifier that can be used include ordinary surfactants for emulsion polymerization. For example, anionic surfactants such as sodium, potassium and ammonium salts of alkyl sulfates having 8 to 20 carbon atoms and sodium and potassium salts of aliphatic carboxylic acids such as lauric acid, stearic acid and palmitic acid, and alkylphenols And non-ionic surfactants such as aliphatic alcohols and reaction products of polypropylene oxides and ethylene oxide. In some cases, two or more of these surfactants can be used in combination. Further, a surfactant such as a naphthalene formaldehyde condensed sulfonate may be added. Still further, a cationic surfactant such as an alkylamine hydrochloride can be used.

In order to produce a crosslinked acrylate-based elastic material by an emulsion polymerization method, for example, an alkyl acrylate monomer or a mixture of an alkyl acrylate and a vinyl compound monomer copolymerizable therewith is used. It may be prepared by adding a small amount of a crosslinkable monomer and by an emulsion polymerization method. An alkyl acrylate monomer or a mixture of an alkyl acrylate and a vinyl compound monomer copolymerizable therewith can be added to the polymer emulsion obtained by this method, and the emulsion can be produced by an emulsion polymerization method.

The average particle diameter of the crosslinked elastomer emulsion particles can be adjusted by adjusting the amount of the surfactant and the amount of the aqueous medium used in the crosslinked acrylate elastic body. The monomer to be grafted to the crosslinked acrylic ester-based elastic material may be an alkyl methacrylate or a mixture of an alkyl methacrylate and a vinyl compound monomer copolymerizable therewith. The methacrylic acid ester as a component to be grafted can be selected from the above-mentioned ones used in the production of an elastic body, and a vinyl compound monomer copolymerizable therewith is also used in the production of an elastic body. Then, you can select from those exemplified.

The graft polymerization reaction is preferably carried out by an emulsion polymerization method, but may be carried out by a solution polymerization method.
When the emulsion polymerization method is used, for example, a monomer to be grafted is added to an emulsion of a crosslinked acrylate-based elastic material, and if necessary, an emulsifier, a polymerization initiator, a molecular weight regulator, water, etc. are added, and ordinary emulsification is performed. The polymerization can be carried out under selected conditions.

The graft polymer can be used as an acrylic resin for forming a film, as it is, or by blending a transparent thermoplastic resin compatible with the graft polymer. In the present invention, (a) an aqueous dispersion of a hydrophobic acrylic resin having a glass transition temperature in the range of 35 to 80 ° C., and (b) an aqueous polyurethane resin composition are provided on the inner surface of the house when the base polyolefin resin film is stretched. And (c) an antifogging coating containing three components of an inorganic colloid sol as essential components. The acrylic resin is preferably hydrophobic, and when the glass transition temperature of the hydrophobic acrylic resin is too low, the inorganic colloid particles are likely to take a non-uniform dispersion state by aggregation of several orders, and the inorganic colloid particles Insufficient fixation to the coating substrate may cause the inorganic colloid particles to fall off and flow off the substrate surface over time, impairing the anti-fog performance.If too high, a transparent and uniform coating may be formed. It is difficult to obtain and poor in practicality.

In the present invention, one example preferably used as the hydrophobic acrylic resin of the film to be formed is at least a total of 60% by weight of a monomer composed of an alkyl ester of acrylic acid or methacrylic acid, or acrylic monomer. A monomer mixture of an alkyl ester of an acid or methacrylic acid and an alkenylbenzene;
A water-dispersible polymer obtained by emulsion-polymerizing a copolymerizable α, β-ethylenically unsaturated monomer by weight in an aqueous medium in the presence of an emulsifier, for example, under ordinary polymerization conditions. Or a copolymer can be mentioned.

The alkyl esters of acrylic acid or methacrylic acid used in the production of the hydrophobic acrylic resin include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, isopropyl acrylate and the like. n-butyl ester, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, methacrylic acid Acid-2-ethylhexyl ester, decyl methacrylate, and the like. Generally, the alkyl group has 1 to 20 carbon atoms.
Acrylates and / or alkyl methacrylates having 1 to 20 carbon atoms in the alkyl group are used. Examples of alkenylbenzenes include styrene, α-methylstyrene, vinyltoluene, and the like.

The hydrophobic acrylic resin used in the present invention comprises:
It is preferable to contain at least a total of 60% by weight of the above-mentioned alkyl ester of acrylic acid or methacrylic acid, or a monomer mixture of an alkyl ester of acrylic acid or methacrylic acid and an alkenylbenzene. When the amount is less than 60% by weight, the water resistance of the formed coating film is not sufficient, so that the antifogging sustaining performance may not be exhibited, which is not preferable.

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

The hydrophobic acrylic resin is a known emulsifier,
For example, anionic surfactants, cationic surfactants,
One or two selected from nonionic surfactants
In the presence of more than one species, in an aqueous medium, a method of emulsion polymerization,
It can be obtained by a method of polymerizing using a reactive emulsifier, a method of polymerizing based on oligosoap theory without containing an emulsifier, and the like. In the case of a polymerization method in the presence of an emulsifier, these emulsifiers are added in an amount of 0.1 to the total amount of charged monomers.
The polymerization initiator preferably used in the range of 1 to 10% by weight is preferably used in the production of the hydrophobic acrylic resin of the present invention, which is preferable from the viewpoint of adjusting the polymerization rate and the dispersion stability of the synthesized resin. Persulfates such as ammonium persulfate and potassium persulfate; organic peroxides such as acetyl peroxide and benzoyl peroxide; They are,
It can be used in the range of 0.1 to 10% by weight based on the total amount of charged monomers.

As the aqueous emulsion of the hydrophobic acrylic resin used in the present invention, an aqueous emulsion obtained by polymerizing each monomer in an aqueous medium may be used as it is, and a liquid dispersion medium may be further added thereto. In addition, it may be a diluted one, or a polymer produced by the above-described polymerization may be separately collected and redispersed in a liquid dispersion medium to form an aqueous emulsion.

As the aqueous polyurethane composition used in the present invention, a polyether-based, polyester-based, or polycarbonate-based anionic polyurethane emulsion is used, and the adhesion of the anti-fog coating to the base polyolefin-based resin film, the water resistance, and the like. A polycarbonate-based anionic polyurethane emulsion is preferable from the viewpoint of scratch resistance, and a silanol group is used in view of the water resistance of a further anti-fog coating, the improvement of scratch resistance, and the time until the anti-fogging property is exhibited and the anti-fogging durability. Polycarbonate-based anionic polyurethane emulsions are more preferred. These may be used alone or in combination of two or more.

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

The aqueous polyurethane composition is added in an amount of 0.01 to 0.01 wt.
As mentioned above, it is preferable to set it as 2 or less, more preferably 0.01 or more and 1 or less. When it is less than 0.01, the improvement of the scratch resistance is hard to be seen, and the time until the anti-fogging property is developed is long, so that it is difficult to exert a sufficient anti-fogging effect. When the amount is too large, not only is the scratch resistance difficult to improve in proportion to the compounding amount, but also the coating film formed after application becomes turbid and the light transmittance is easily reduced, and the cost is disadvantageous. Not preferred.

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

The inorganic colloid sol preferably has an average particle diameter in the range of 5 to 100 μm, and within this range, two or more kinds of colloid sols having different average particle diameters may be used in combination. If the average particle diameter is too large, the coating may be white and devitrified. On the other hand, if the average particle diameter is too small, the stability of the inorganic colloid sol may be insufficient, which is not preferable.

The amount of the inorganic colloid sol to be added is 0.5 to 5 in terms of the weight ratio of the solid content to the total weight of the solid content of (a) the hydrophobic acrylic resin and (b) the aqueous polyurethane resin composition. It is preferable to set the following. That is, if the amount is too small, a sufficient anti-fogging effect may not be exhibited.On the other hand, if the amount is too large, the anti-fog effect is not easily improved in proportion to the amount, and the A phenomenon that a film formed later becomes cloudy and lowers the light transmittance of the film appears, and the film may be coarse 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 A surfactant such as an agent can be added. Examples of the anionic surfactant include fatty acid salts such as sodium oleate and potassium oleate; higher alcohol sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; sodium dodecylbenzene sulfonate;
Alkyl benzene sulfonates and alkyl naphthalene sulfonates such as sodium alkyl naphthalene sulfonate; naphthalene sulfonic acid formalin condensate; dialkyl sulfosuccinate; dialkyl phosphate salt; sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate And the like.

Examples of the cationic surfactant include ethanolamines; laurylamine acetate, triethanolamine monostearate formate; amine salts such as stearamide ethyl diethylamine acetate; lauryltrimethylammonium chloride, stearyltrimethylammonium chloride; And quaternary ammonium salts such as dilauryl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, and lauryl dimethyl benzyl ammonium chloride.

Examples of the nonionic surfactant include polyoxyethylene higher alcohol ethers such as polyoxyethylene lauryl alcohol, polyoxyethylene lauryl ether and polyoxyethylene oleyl ether; and polyoxyethylene octyl phenol and polyoxyethylene nonyl phenol. Polyoxyethylene alkyl aryl 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 fatty acid esters such as glycerin monopalmitate and diglycerin monostearate; Glycerol fatty acid esters such as stearate; pentaerythritol fatty acid esters such as pentaerythritol monostearate; dipentaerythritol fatty acid esters such as dipentaerythritol monopalmitate; sorbitan monopalmitate,
Sorbitan such as half adipate, diglycerin monostearate and half glutamate and diglycerin fatty acid dibasic acid esters; or condensates thereof with alkylene oxides such as ethylene oxide and propylene onoxide such as polyoxyethylene sorbitan monoester Laurate, polyoxypropylene sorbitan monostearate, etc .; polyoxyethylene stearylamine, polyoxyethylene oleylamine,
Polyoxyethylene alkylamines and fatty acid amides such as polyoxyethylene stearamide; sugar esters;

Examples of the polymer surfactant include polyacrylate, polymethacrylate, cellulose ethers and the like. The addition of these surfactants makes it possible to easily and quickly disperse the hydrophobic acrylic resin and the inorganic colloid sol uniformly. Also, by using the surfactant together with the inorganic colloid sol, the surface of the hydrophobic polyolefin resin film becomes hydrophilic. Performs the function of imparting properties. The addition amount of the surfactant is preferably selected in the range of 0.1 to 50 parts by weight based on 100 parts by weight of the solid content of the hydrophobic acrylic resin. If the addition amount of the surfactant is too small, it takes time for the hydrophobic acrylic resin and the inorganic colloid sol to be sufficiently dispersed, and the anti-fogging effect cannot be sufficiently exhibited in combination with the inorganic colloid sol. On the other hand, if the added amount of the surfactant is too large, the transparency of the film is reduced due to a bleed-out phenomenon to the surface of the film formed after coating, and if it is remarkable, the blocking resistance of the film is deteriorated and the water resistance of the film is reduced. May cause.

When preparing the antifogging agent composition for forming the antifogging film of the present invention, a crosslinking agent can be added. The crosslinking agent has the effect of crosslinking the acrylic resins and improving the water resistance of the coating. Examples of the cross-linking agent include phenolic resins, amino resins, amine compounds, aziridine compounds, azo compounds, isocyanate compounds, epoxy compounds, silane compounds, and the like. Particularly, amine compounds, aziridine compounds And epoxy compounds can be preferably used.

Examples of the amine compounds include aliphatic polyamines such as diethylenetriamine, triethylenepentamine, and hexamethylenediamine; 3,3′-dimethyl-4,
Alicyclic amines such as 4'-diaminodicyclohexylmethane and isophoronediamine; and aromatic amines such as 4-4'-diaminodiphenylmethane and m-phenylenediamine are used. Aziridine compounds include Tris-2,
4,6- (1-aziridinyl) -1,3,5-triazine, trimethylolpropane-tri-β-aziridinylpropionate, tris [1- (2-methyl) -aziridinyl] phosphine oxide, hexa [ 1- (2-methyl) -aziridinyl] triphosphatriazine and the like are used. Epoxy compounds include bisphenol A
Or an epoxidized novolak resin produced by a reaction between bisphenol F and epichlorohydrin, a resin reaction product of phenol (or substituted phenol) with formaldehyde and epichlorohydrin, epichlorohydrin and an aliphatic polyhydric alcohol such as glycerol, Resinous reaction products formed from 4-butanediol, poly (oxypropylene) glycol or similar polyhydric alcohol components, resins obtained by epoxidation using peracetic acid, and the like are used. In epoxy compounds, tertiary amines and quaternary ammonium salts can be used in combination as a catalyst. These crosslinking agents can be used in an amount of 0.1 to 30% by weight based on the solid content of the acrylic resin. A liquid dispersion medium can be added to the antifogging agent composition used in the present invention, if necessary. Such a liquid dispersion medium includes a hydrophilic or water-miscible solvent containing water, and water; monohydric alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; polyhydric alcohols such as ethylene glycol, diethylene glycol, and glycerin. Kind;
Cyclic alcohols such as benzyl alcohol; cellosolve acetates; ketones and the like. These liquid dispersion media may be used alone or in combination.

The antifogging agent composition comprises a hydrophobic acrylic resin,
Generally, the solid content of the aqueous polyurethane composition and the inorganic colloid is prepared at a concentration of 0.5 to 50% by weight, and this is often used after dilution. The antifogging agent composition prepared in the present invention is further mixed, if necessary, with conventional additives such as an antifoaming agent, a plasticizer, a film forming aid, a thickening agent, a pigment and a pigment dispersant. be able to.

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

[0062]

1 / Tg = W1 / Tg1 + W2 / Tg2 +... +
Wn / Tgn, where Tg is the glass transition temperature (absolute temperature) of the acrylic resin, and Tg1, Tg2,.
..., glass transition temperature (absolute temperature) of n homopolymer,
, Wn indicate the weight fraction of each component 1, 2, ..., n, respectively.

In order to form an acrylic resin film and an anti-fogging film on the surface of the base film, respectively, the acrylic resin solution and the anti-fogging agent composition obtained by the above-mentioned polymerization are each subjected to a doctor blade coating method, A coating method known per se, such as a coating method, a dip coating method, a spray coating method, a rod coating method, a bar coating method, a knife coating method, a brush coating method, may be employed, and the coating may be dried after application. As the drying method after the application, any of natural drying and forced drying may be adopted.
Drying may be performed at a temperature in the range of 0 to 250 ° C, preferably 70 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 used for the heat drying, and the hot-air drying method is advantageous in consideration of the drying speed and stability.

In the present invention, the thickness of the film formed on the surface of the base film is preferably selected to be 1/10 or less of the base film, but is not necessarily limited to this range. The thickness of the coating is 1/10 of the base film
If it is larger, there is a difference in the 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, and that the coating is cracked 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 surface of the base film may be washed in advance with alcohol or water, or subjected to a plasma discharge treatment or a corona discharge treatment. You may keep it. When the agricultural polyolefin-based resin film according to the present invention is actually used, the side provided with the acrylic resin coating is outside the house or tunnel, and the side provided with the anti-fog coating is used as the house or tunnel. It is good to extend it inside.

[0066]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below with reference to embodiments, but the present invention is not limited to the following examples unless it exceeds the gist. (1) Preparation of a polyolefin-based substrate film
mmφ (Pura Koken Co., Ltd.), the extruder used was 30 mmφ outer and inner layers (Pura Giken Co., Ltd.), and the middle layer was 40 m.
As mφ (manufactured by Pla Giken Co., Ltd.), at a molding temperature of 160 ° C., a blow ratio of 2.0, and a take-up speed of 5 m / min, polyolefin-based base films (AC) shown in Table 1 were obtained.

(2) Formation of Acrylic Resin Coating on House Exterior Surface An acrylic resin having the monomer composition shown in Table 2 was dissolved in MEK, and the solid content was adjusted to 20%. A coating solution for a dustproof coating film was obtained. The obtained coating solution is coated on the surface of the base film by the gravure coating method, and then the coating material is retained in a hot-air drying oven controlled at 150 ° C. for 2 minutes to disperse the solvent and remove the dust-proof coating. Was formed. The thickness of each coating was 2 μm.

(3) Formation of antifogging film on inner surface of house A water dispersion of an acrylic resin having the monomer composition shown in Table 3 was prepared.
The aqueous polyurethane composition, inorganic colloid sol, and other components described in 4 were blended to prepare various antifogging compositions. The obtained antifogging agent composition was applied by gravure coating to a surface different from the surface of the substrate film on which the acrylic resin film was formed on the outer surface of the house, and then heated in a hot air drying oven controlled at 80 ° C. For 2 minutes, and the liquid dispersion medium was scattered to form a film. In addition, the thickness of all the coatings was 0.5 μm.

(4) Evaluation of Film Each of the obtained films was subjected to the following evaluation tests, and the results are shown in Table-5. a) Fusing property test A film cut into a width of 30 cm and a length of 150 cm was immersed in tap water of Nagoya City for 2 days, and this was immersed in a 2 cm diameter, 3 cm width.
Wrap around a 5 cm galvanized iron pipe, 6
It was left in an oven at 5 ° C. for one week and dried. The ratio of the area where the fusion occurred at the film contact portion when the film was unwound from the iron pipe to the area of the entire film is shown.

B) Film Transparency Test The parallel light transmittance of the obtained film at a wavelength of 555 nm was measured using a spectrophotometer (Model 330, manufactured by Hitachi, Ltd.), and the value was shown. c) Film transparency after the fir test A kneading test was carried out using a UF-kneading tester FT-501 manufactured by Kamishima Seisakusho Co., Ltd. After leaving the film cut to a width of 2 cm and a length of 7 cm in a constant temperature chamber at 23 ° C. for 60 minutes, a load of 500 g, a fir width of 2 cm,
The kneading test was performed 10 times under the condition of the fir speed of 120 times / min. After that, the parallel light transmittance at the wavelength of 555 nm of the pad portion was measured with a U-2000 type Hitachi double beam spectrophotometer.

D) Scratch resistance test for antifogging coating film A scotch bright (3M) cut into a square of 10 cm was placed on the surface on which the antifogging coating film was formed, and at a pulling rate of 2 cm / sec under a load of 1 kg. The film was pulled and visually observed for damage on the coating surface. The evaluation criteria are as follows. : No damage is observed on the surface of the coating film. ×: Some damage is observed on the surface of the coating film.: Some damage is observed on the surface of the coating film. E) Anti-fogging test 1) Condition 1 The anti-fog coating surface of the film was placed on the top of the water tank with water facing the water tank, and the outside air temperature was 20 ° C. The temperature in the aquarium is 50 ℃
, And at a point in time after a predetermined period of time had elapsed since the film was placed on the upper portion of the water tank, the speed of developing antifogging properties was visually observed. The evaluation criteria are as follows.

◎: Water adhered in a thin film form and no water droplets were observed. ：: Water adhered in a thin film state, but slightly large water droplets were observed. ×: Water adhered in a thin film state. Despite that, large droplets are partially adhered. △: Fine droplets are partially adhered. ×: Fine droplets are adhered to the entire film surface. 2) Condition 2 Condition For each film that has passed one month at 1, the outside air temperature 1
The temperature was maintained at 0 ° C. and the temperature in the water tank at 20 ° C., and the speed of developing antifogging property after a predetermined period of time was visually observed. This evaluation criterion is the same as the condition 1 described above.

3) Condition 3 The film was placed on a single-roof type house (frontage 2 m, depth 20 m, ridge height 2 m, roof slope 30)
Degree), coat the anti-fog coating surface so as to be inside the house,
An 18 month extension test was performed. The antifogging property of each film was visually observed with time during the stretching test. This evaluation criterion is the same as the condition 1 described above.

[0074]

[Table 1]

[0075]

[Table 2]

[0076]

[Table 3]

[0077]

[Table 4]

[0078]

[Table 5]

[0079]

According to the present invention, agriculture having high transparency, little fusion even when films overlap each other, and excellent in anti-fogging properties (speed of development, sustainability). A polyolefin-based resin film can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B32B 27/40 B32B 27/40 4J038 C08J 7/04 C08J 7/04 S CES CESL C09D 133/08 C09D 133 / 08 133/10 133/10 151/00 151/00 175/04 175/04 // C08L 23:02 C08L 23:02 (72) Inventor Emi Yoshimura 2nd Oike, Iwatsuka-cho, Nakamura-ku, Nagoya City, Aichi Prefecture Nagoya Office Co., Ltd. F-term (reference) 2B024 DB01 2B029 EB03 EB16 EC02 EC06 EC09 EC17 EC19 RA03 4F006 AA12 AB24 AB37 AB74 AB76 BA02 BA10 CA06 DA04 4F100 AA00C AA19C AA19H AA20C AA20H AK03A05AK25 AK03AK51BAK25BAKB BA07 BA10B BA10C GB01 JA05B JA05C JB20C JL00 JM01C JM01H JN01 YY00B YY00C 4H020 AA01 AA04 AA06 AB02 4J038 CC021 CC022 CC071 CC072 CD021 CD022 CD081 CD082 CG031 CG032 CG141 CG161 CG162 CG171 CG172 CH031 CH041 CH042 CH121 CH171 CH172 CL001 CL002 CP071 CP072 DB221 DB222 GA01 GA03 GA06 GA09 GA10 GA12 GA13 GA14 HA216 HA034 KA08 MA02

Claims (8)

[Claims] 1. An agricultural polyolefin resin film having a glass transition temperature of 50 to 8 on the outer surface of a house when stretched.
Forming an acrylic resin film in the range of 2 ° C., on the other surface, (a) an aqueous dispersion of a hydrophobic acrylic resin having a glass transition temperature in the range of 35 to 80 ° C., and (b) an aqueous polyurethane resin 3 of the composition and (c) the inorganic colloid sol
An agricultural polyolefin-based resin film formed by forming a coating made of an anti-fogging agent composition containing an essential component. 2. The amount of component (b) in the antifogging agent composition is from 0.01 to 1 in terms of solids weight ratio with respect to component (a). 2. The polyolefin resin film for agricultural use according to claim 1, wherein the compounding amount is 0.5 or more and 5 or less with respect to the total of the component (a) and the component (b) in terms of a solid content weight ratio. 3. An acrylic resin for forming a coating on the outer surface of a house of a film, wherein the acrylic resin contains 5 to 40% by weight of a hydroxyalkyl (meth) acrylate and contains one or more carboxyl groups in the molecule. Saturated carboxylic acid 0-2
3. A copolymer obtained by copolymerizing 0% by weight and a balance of a monomer component composed of another vinyl compound copolymerizable with these compounds.
The polyolefin resin film for agriculture according to the above. 4. An acrylic resin for forming a coating on the outer surface of a house of a film, wherein the acrylic resin comprises, as a main component, an alkyl methacrylate monomer or an alkyl methacrylate in the presence of a crosslinked acrylate-based elastic material. 3. A graft copolymer obtained by polymerizing a mixture of a vinyl compound copolymerizable with a rubber compound, wherein the graft copolymer contains 5 to 80% by weight of the crosslinked acrylate-based elastic material. The polyolefin resin film for agriculture according to the above. 5. An ethylene-α-olefin copolymer resin obtained by copolymerization with a metallocene catalyst is used as one component of the polyolefin resin.
5. The agricultural polyolefin-based resin film according to any one of items 1 to 4. 6. The component (b) in the antifogging agent composition comprises a polyurethane resin containing at least one silanol group in a molecule and a strongly basic tertiary amine as a curing catalyst. The agricultural polyolefin resin film according to any one of claims 1 to 5, which is an aqueous polyurethane composition. 7. The agricultural polyolefin resin film according to claim 1, wherein the component (b) in the antifogging agent composition is a polycarbonate-based anionic polyurethane aqueous composition. 8. The component (c) in the antifogging agent composition is silica and / or alumina sol.
The agricultural resin film according to any one of the above.