JPH11137097A - Synthetic resin film for agriculture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject film permitting the formation of a coating film having excellent weather resistance and the like and consequently capable of being spread over a long period by mixing an aqueous coating material, colloidal silica having particle diameters in a specific range and a specific emulsion, further adding a silicone surfactant to the mixture, and subsequently coating the obtained coating material on the surface of the film. SOLUTION: This resin film for agriculture is obtained by coating a coating material on at least one surface of a base film comprising a synthetic resin. Therein, the coating material coated on the base film is obtained by mixing an aqueous coating material, colloidal silica having an average particle diameter of 1-200 nm and the emulsion of a hindered amine compound and further adding a silicone surfactant to the mixture. The aqueous coating material is preferably a urethane resin emulsion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an agricultural synthetic resin film used as a covering material for agricultural facilities.

[0002]

2. Description of the Related Art Conventionally, transparent synthetic resin films have been used as covering materials for agricultural houses and tunnels. Examples of the synthetic resin film include vinyl chloride resins such as polyvinyl chloride and ethylene-vinyl chloride copolymer resin, olefin resins such as polyethylene and ethylene-vinyl acetate copolymer resin, polyester resins such as polyethylene terephthalate, and fluorine. A film made of a synthetic resin such as a series resin is generally used, and among them, a single-layer or multi-layer vinyl chloride resin film or an olefin resin film is widely used.

[0003]

However, in recent years, there has been a method which can be spread over the above-mentioned synthetic resin film for agriculture for a long period of time because of the labor shortage of farmers and resource saving. Requested.

In order to be able to spread an agricultural synthetic resin film over a long period of time, the agricultural synthetic resin film must have not only excellent weather resistance but also drip-proof properties. Are required to last for a long time.

As a means for maintaining the drip-proof property for a long period of time, there is known a method of forming a coating film with a coating material to which a hydrophilic substance such as colloidal silica is added. If the weather resistance of the membrane itself is not sufficient,
Its purpose cannot be achieved.

The present invention forms a coating film having excellent weather resistance and drip-proof properties, thereby maintaining various properties required for agricultural synthetic resin films for a long period of time. It is an object of the present invention to provide an agricultural synthetic resin film that can be spread over a period.

[0007]

Means for Solving the Problems The agricultural synthetic resin film of the present invention which has been made to solve the above-mentioned problems, comprises: (A) an aqueous coating material; and (B) an average particle size on at least one surface of a synthetic resin base film. It comprises an emulsion of colloidal silica (C) hindered amine compound having a diameter of 1 to 200 nm, and is coated with a coating material to which a silicon surfactant is added.

The base film of the agricultural synthetic resin film of the present invention is a film conventionally used as an agricultural synthetic resin film, specifically, a vinyl chloride resin, an olefin resin, or a polyester resin. ,
It is a film made of a synthetic resin such as a fluororesin.
Among them, a film made of a vinyl chloride resin or an olefin resin is preferable. Of course, the base film may be a single-layer film or a multilayer film.

Examples of the above-mentioned vinyl chloride resin include polyvinyl chloride, which is a homopolymer of vinyl chloride, and vinyl chloride and other monomers such as vinylidene chloride, acrylonitrile, maleic acid, itaconic acid, acrylic acid, and methacrylic acid. Copolymer resins with acids, vinyl acetate, ethylene, propylene, maleic acid esters, acrylic acid esters, methacrylic acid esters, higher vinyl ethers, and the like, or mixtures thereof can be used.

The above-mentioned olefin resin includes polyethylene such as low-density polyethylene, linear low-density polyethylene, medium-density polyethylene and high-density polyethylene; ethylene-vinyl acetate copolymer resin, ethylene-acrylate copolymer resin, ethylene Olefin-based resins such as ethylene-based copolymer resins such as methacrylic acid ester copolymer resins can be used, and ethylene-vinyl acetate copolymer resins having a vinyl acetate content of 5 to 20% by weight are particularly preferable. , Low-density polyethylene and linear low-density polyethylene. When the base film is a film made of an olefin-based resin, a multilayer film is more preferable than a single-layer film, and in particular,
Two or more layers in which the inner layer when extended to an agricultural facility is a layer composed of the above-mentioned ethylene-vinyl acetate copolymer resin, and the outer layer is a layer composed of low-density polyethylene and / or linear low-density polyethylene. Are preferred.

The synthetic resin constituting the base film may contain, if necessary, a plasticizer, a drip-proof agent, an anti-fog agent, a stabilizer, a lubricant or an anti-adhesive, an ultraviolet absorber, an antioxidant, and a light stabilizer. Various additives conventionally used for agricultural synthetic resin films, such as an agent, a warming agent, and a colorant, are added. The resulting synthetic resin composition is obtained by known methods such as a calendering method, an extrusion method, and an inflation method. Is formed into a film having a desired thickness.

Specific examples of the plasticizer include phthalate plasticizers such as di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisononyl phthalate, butylbenzyl phthalate, diisodecyl phthalate and diundecyl phthalate; tricresyl Phosphate,
Phosphate plasticizers such as trixylyl phosphate, tris (isopropylphenyl) phosphate, tributyl phosphate, triethyl phosphate, triphenyl phosphate, triethylphenyl phosphate; epoxy plastics such as epoxidized soybean oil, epoxidized linseed oil, and epoxy resin Agent: di-2-ethylhexyl adipate, di-2-ethylhexyl sebacate, di-2
Fatty acid ester plasticizers such as ethylhexyl azelate; trimellitic acid ester plasticizers; polyester plasticizers such as polypropylene adipate; chlorinated paraffin; The above plasticizers can be used alone or in combination of two or more. The amount of the plasticizer varies depending on the type of the synthetic resin constituting the base film, but in the case of a vinyl chloride resin, it is 20 to 70 parts per 100 parts by weight of the resin.
It is about parts by weight.

Examples of the anti-drip agent include sorbitan fatty acid ester, sorbitol fatty acid ester, glycerin fatty acid ester, diglycerin fatty acid ester, sorbitan fatty acid / dibasic acid ester, sorbitol fatty acid / dibasic acid ester, glycerin fatty acid / dibasic acid ester, Ester of polyhydric alcohol and fatty acid such as diglycerin fatty acid and dibasic acid ester, ester of polyhydric alcohol and fatty acid and dibasic acid, or alkylene oxide such as ethylene oxide, propylene oxide and butylene oxide added to these Sorbitan palmitate, sorbitan stearate, sorbitan stearate / ethylene oxide 2 mol adduct, sorbitan stearate
Propylene oxide 3 mol adduct, sorbitol stearate, sorbitol stearate / ethylene oxide 3 mol adduct, diglycerin palmitate, diglycerin stearate, glycerin stearate, glycerin palmitate / ethylene oxide 2 mol adduct,
Sorbitan stearate adipate / ethylene oxide 3 mol adduct, sorbitol stearate adipate / ethylene oxide 2 mol adduct, diglycerin palmitate sebacate / propylene oxide 3 mol adduct, sorbitol palmitate adipate / ethylene oxide 3 mol adduct, etc. Is mentioned. These drip-proofing agents can be used alone or in combination of two or more. The amount of the above drip-proofing agent is about 0.5 to 5 parts by weight per 100 parts by weight of the resin.

As the antifog, a fluorine group in one molecule,
A fluorine-containing compound having at least one of a hydroxyl group and an alkylene oxide group can be used. Fluorine groups are perfluoroalkyl groups [C _n F _{2n + 1} -], perfluoroalkoxy group [C _n F _{2n + 1} O-], polyfluoroalkyl group _{[H m C n F 2n + 1} -m - ] , perfluoroalkenyl group [C _n F _2n-1 -], polyfluoroalkenyl group _{[H m C n F 2n-1} -m - ], perfluoroalkylene group [C _n F _2n -] and the like (provided that, m is an integer of 1 to 3 in the formula, n 3-20 integer), also alkylene oxide groups, _{[- (C 2 H 4 O)} n - ], [- (C ₃ H ₆ O)
_n- ] and the like (where n is an integer of 1 to 30).

As the above-mentioned fluorine-containing compound, specifically,
Examples include those represented by the formulas (1) to (13) of Chemical Formula 1, but are not limited thereto.

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The above-mentioned fluorine-containing compounds may be used alone or in combination of two or more. Further, the addition amount of the fluorine-containing compound is 0.0
It is 1 to 1.0 part by weight, preferably 0.05 to 0.5 part by weight.

As the stabilizer, a commonly used stabilizer such as a metal soap, an organic phosphite-based stabilizer, and an organic metal phosphate compound can be used. Metal soaps include zinc stearate, barium stearate, calcium stearate, barium ricinoleate, calcium laurate,
Examples include calcium oleate and zinc octoate. Examples of the organic phosphite-based stabilizer include diphenyldecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, and tris (2-ethylhexyl). Examples include phosphite, tristearyl phosphite, octyl diphenyl phosphite, diphenyl acid phosphite, dioctyl acid phosphite, and the like. As the metal organic phosphate, those represented by the following chemical formula (a) or (b) can be used. Other than the above, dibutyltin dilaurate, dibutyltin maleate, organic tin mercaptide,
Tin-based stabilizers such as organic tin sulfonamides, and lead-based stabilizers such as tribasic lead sulfate, tribasic lead phosphite, and tribasic lead maleate can also be used. The above stabilizers can be used alone or in combination of two or more. In addition, the amount of these stabilizers added is
0.5 to 10 parts by weight, preferably 1 to 10 parts by weight, per 0 parts by weight
5 parts by weight.

[0018]

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Examples of the lubricant or antiadhesive include fatty acid lubricants such as stearic acid, isostearic acid and palmitic acid, fatty acid amide lubricants such as stearic acid amide, methylenebisstearamide and ethylenebisstearamide, butyl palmitate And lubricants such as butyl stearate and the like, ester lubricants such as barium isodecyl phosphate and calcium octadecyl phosphate, polyethylene wax, liquid paraffin and the like. The above lubricants or antiadhesives may be used alone or in combination of two or more.

Examples of the ultraviolet absorber include commonly used ultraviolet absorbers such as benzophenone-based, benzotriazole-based, salicylate-based, and cyanoacrylate-based ultraviolet absorbers. The above ultraviolet absorbers can be used alone or in combination of two or more.

As the light stabilizer, generally used light stabilizers such as hindered amine compounds can be used alone or in combination of two or more.

As the heat insulating agent, a conventionally used fine particle having absorption in the infrared region can be used.
Specifically, it is at least one selected from hydrotalcites, silica, magnesium hydroxide, aluminum hydroxide, talc and the like.

Further, the base film made of a synthetic resin used in the present invention is obtained by adding an organic phosphate compound represented by the general formula as shown in Chemical Formula 3 in order to further improve the weather resistance. There may be.

[0024]

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The coating applied on at least one surface of the base film is a mixture of (A) an aqueous coating, (B) colloidal silica having an average particle diameter of 1 to 200 nm, and (C) an emulsion of a hindered amine compound. However, these mixing ratios are (A)
The ratio of the active ingredient of (B) to the active ingredient of (B) is 10:
It is desirable that the amount of the active ingredient of (C) is from 0.01 to 1 part by weight per 100 parts by weight of the active ingredient of (A). When the mixing ratio of the active ingredients (A) to (C) deviates significantly from the above range, there is a concern that the effects expected in the present invention are not sufficiently exhibited. The term “active ingredient” as used herein refers to a component excluding components removed when a paint such as a dispersion medium is dried and solidified.

The coating film formed by applying the above-mentioned coating material has excellent weather resistance, so that the base film itself has various effects, such as long-lasting effects, and this coating film has a protective effect. It also has the advantage of excellent dropping properties. Therefore, when the above-mentioned paint is applied to only one surface of the base film, it is generally used such that the surface that is inward when the agricultural facility is spread, which is required to be drip-proof, becomes the coated surface. Further, in the above case, an acrylic, urethane, or fluorine-based solvent-based coating or an ultraviolet-curable coating may be applied to the outer surface.

As the aqueous paint contained in the paint used in the present invention, an aqueous paint such as an acrylic paint, a urethane paint, a polyester paint or an epoxy paint can be used, but it is most preferable to achieve the object of the present invention. This is an aqueous paint composed of a urethane resin emulsion. Even when using an aqueous paint other than the aqueous paint composed of a urethane-based resin emulsion, the effects expected in the present invention, such as improvement of the weather resistance of the coating film, are exhibited, but the aqueous paint composed of the urethane-based resin emulsion is used. In some cases, the above effects are most remarkably exhibited.

As the colloidal silica mixed with the water-based paint, those having an average particle size of 1 to 200 nm are used. If the average particle size is larger than the above range, the transparency of the obtained coating film is impaired, and if the average particle size is smaller than the above range, the stability of the coating may be impaired. Also, when this colloidal silica is not added,
When the amount of the colloidal silica added is extremely small, the drip-proof property of the obtained film is significantly impaired.

[0029] A silicone-based surfactant is added to the above paint. This silicon-based surfactant is represented by Chemical Formula 4 (a)
A non-hydrolyzable siloxane-polyoxyalkylene block copolymer type silicone surfactant represented by the following general formula; and a hydrolyzable siloxane-polyoxyalkylene block represented by the following general formula: 4 (b) One or more selected from copolymer type silicon-based surfactants and the like can be used.

[0030]

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The amount of the silicon-based surfactant to be added is preferably 0.01 to 0.3 parts by weight per 100 parts by weight of the paint (including the dispersion medium). If no silicon-based surfactant is added, or if the amount of the silicon-based surfactant is significantly less than the above range, the weather resistance, drip-proof property, and adhesion of the coating film to the base film are reduced.

The coating method of the paint is spray coating,
Known methods such as roll coating, gravure coating, reverse roll coating, dip coating, screen printing, flexographic printing and the like can be adopted, and are not particularly limited.

The thickness of the coating film formed by applying the coating material is not particularly limited, but is usually 0.5 to 5.0.
The range is about 0 μm.

In order to improve the adhesion between the coating film and the base film, it is desirable to add 3 to 10 mol of nonylphenyl ether of polyoxyethylene to the base film. This polyoxyethylene 3 ~
The addition amount of the 10 mol-added nonylphenyl ether is 0.1 to 100 parts by weight of the synthetic resin constituting the base film.
It is desirable that the amount be from 0.01 to 0.7 parts by weight.

[0035]

EXAMPLES Specific examples will be given below, but the present invention is not limited to the following examples.

[Examples 1 to 6, Comparative Examples 1 to 5] One of the base films A to C having the composition shown in Table 1 was coated on one surface of any one of the paints a to h shown in Table 2. These paints were applied in the combinations shown in Table 3 using a gravure roll of 200 mesh,
After drying for a minute, an agricultural polyvinyl chloride film was obtained.
The obtained agricultural polyvinyl chloride film was evaluated for adhesion, drip resistance and weather resistance of the coating film by the following methods. Table 3 shows the results.

[Evaluation Method] (1) Adhesion of Coating Film A commercially available pressure-sensitive adhesive tape was stuck on the coating surface (coating surface) and rubbed strongly 10 times. The state was visually observed. In addition, in the evaluation,
The evaluation was performed on a five-point scale based on the following criteria. 5: No part where the coating film was peeled was found at all. 4: The coating film is very slightly peeled off (where the peeling is 5
%Less than). 3: Less than 50% (5% or more) of the part where the coating film has peeled off. 2: 50% or more (less than 95%) of the part where the coating film has peeled off. 1: The coating film was almost peeled off (less than 5% remained). (2) Drip-proof property The obtained polyvinyl chloride film for agriculture was treated with a frontage of 2 m,
After 12 months had passed since the tunnel house having a height of 1 m and a length of 10 m was stretched so that the coating surface was on the inside, the state of the inside surface of the house was visually observed. The evaluation was performed on a five-point scale using the following criteria as a guide. 5: Adhesion of water droplets was hardly observed, and water was flowing in a film form. 4: Adhesion of water droplets is slightly observed, but water flows in a film form. 3: Adhesion of water droplets was observed, and water was flowing in a streak shape. 2: Adhesion of water droplets is remarkable, and water flows in a streak shape. 1: Adhesion of water droplets was remarkable and hardly flowed. (3) Weather resistance of coating film The state of the coating film after 18 months has passed since the obtained agricultural polyvinyl chloride film was spread as described above was visually observed, and evaluated on a 5-point scale using the following criteria as a guide. did. 5: No crack and discoloration are observed. 4: Cracks are slightly observed, but no discoloration is observed. 3: Cracks are observed and some discoloration is observed. 2: Cracks are remarkable (some areas are peeled off) and discoloration is observed. 1: Discoloration is remarkable, and there are many places where the coating film is peeled off.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

[Table 3]

[0041]

As described in detail above, the agricultural synthetic resin film of the present invention is formed with a coating film having excellent weather resistance and drip-proof properties. Is maintained over Therefore, the agricultural synthetic resin film of the present invention can be spread over a long period of time, and is extremely useful from the viewpoint of labor saving and resource saving of agricultural work.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // B05D 7/24 303 B05D 7/24 303B

Claims (5)

[Claims] An agricultural synthetic resin film obtained by applying a paint on at least one surface of a base film made of a synthetic resin, wherein the paint applied to the base film is an aqueous paint, and has an average particle diameter of 1 to 200 nm. A synthetic resin film for agricultural use, which is a coating obtained by mixing an emulsion of a colloidal silica and a hindered amine compound described above, and to which a silicone surfactant is added. 2. The agricultural synthetic resin film according to claim 1, wherein the aqueous paint is a paint comprising a urethane resin emulsion. 3. The weight ratio of the active ingredient of the aqueous paint to the active ingredient of the colloidal silica contained in the paint is 1:10.
The agricultural synthetic resin film according to claim 1 or 2, wherein the active ingredient of the hindered amine compound emulsion is 0.01 to 3 parts by weight per 100 parts by weight of the active ingredient of the aqueous paint. 4. The amount of the silicone-based surfactant added to the paint is 0.01 to 0.3 per 100 parts by weight of the paint.
The agricultural synthetic resin film according to any one of claims 1 to 3, which is part by weight. 5. The synthetic resin composition according to claim 1, wherein the base film is composed of 0.01 to 0.7 parts by weight of nonylphenyl ether added with 3 to 10 mol of polyoxyethylene per 100 parts by weight of the synthetic resin. The agricultural synthetic resin film according to claim 1.