JPH01301724A - Synthetic resin-covering material for agriculture - Google Patents

Abstract

PURPOSE:To obtain the subject covering material capable of preventing algae from sticking and maintaining high transparency over a long period, consisting of a synthetic resin film with a dust-proof resinous coating film containing a specified compound on one side of the film at least. CONSTITUTION:An imidazole-based compound expressed by the formula (R is alkyl) is mixed into a dust-proof resinous coating film formed at least on one side of a synthetic resin film (polyvinyl chloride with 0.1-0.3mm thickness is most suitable) preferably in an amount of 0.1-3wt.%, thus obtaining the objective covering film.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an agricultural coating material, and particularly to an agricultural synthetic resin coating material that can prevent algae from adhering and can maintain high transparency for a long period of time.

[Prior Art] In recent years, in order to test the marketability and productivity of agricultural crops by forced, semi-forced or suppressed cultivation, so-called cultivation of useful plants under agricultural covering materials such as agricultural vinyl film has been introduced. Greenhouse cultivation and tunnel cultivation are widely practiced.

The synthetic resin coating materials currently used in greenhouse cultivation and single-cell cultivation, such as vinyl chloride resin films, contain plasticizers, antifogging agents, stabilizers, etc. The agent tends to adhere to the film surface over time, making it easy for dust to adhere to it, and the light transmittance decreases significantly over a period of -2 years.

In order to prevent dust from adhering to the bleed plasticizer, antifog agent, etc., recently, acrylic resins, fluorine-containing resins,
Dustproof films coated with dustproof resins such as urethane resins and polymerizable urethane acrylate resins are often used.

This dust-proof film suppresses the adhesion of dust to the film surface, allowing it to maintain high transparency over a long period of time. Since the loss of fogging agents and the like is also suppressed, it is possible to maintain performance such as strength and antifogging properties over a long period of time.

[Problem to be solved by the invention]

However, even a film provided with such a dustproof resin coating may not be able to exhibit its dustproof performance depending on the environment in which it is used.

For example, if the film is used in an environment surrounded by thickets of cedar, pine, etc., green substances (algae) will form on the surface of the film over time, significantly reducing the light transmittance.

This algae has a strong adhesion to the film, so it does not wash away due to rain or wind, and the only way to remove it is to wipe it off with a cloth during rain or while running water, and you have to wipe it all over the entire surface of the house. This makes the work difficult.

Mechanical methods can also be considered, but they require large-scale equipment, which can lead to enormous costs and put pressure on management.

On the other hand, from the viewpoint of the film composition, since copper compounds have a bactericidal effect, there is a method of mixing the copper compounds into the dust-proof resin coating to prevent the adhesion of algae, but the effect is insufficient.

An object of the present invention is to provide an agricultural synthetic resin covering material that can prevent algae from adhering to the material and maintain high transparency for a long period of time.

[Means for Solving the Problems] As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that by incorporating a specific compound into a dust-proof resin coating provided on at least one side of a synthetic resin film. They discovered that it is possible to prevent the adhesion of algae and maintain high transparency for a long period of time, and have completed the present invention.

That is, the uninvented agricultural synthesis is characterized in that a dustproof resin coating provided on at least one side of a synthetic resin film contains an imidazole compound represented by the following formula (1) (R: alkyl group). It is a resin coating material.

The synthetic resin film in the present invention generally includes thermoplastic synthetic resins having film-forming properties, such as monomers such as vinyl chloride, ethylene, propylene, acrylic esters, methacrylic esters, vinyl acetate, and vinylidene chloride. homopolymers, copolymers of at least one of these monomers with other copolymerizable monomers, polyesters, polyamides, etc., or blends of these polymers. From the viewpoints of properties, light transmittance, strength, economic efficiency, etc., vinyl chloride resins (i.e., polyvinyl chloride and its copolymers containing vinyl chloride of 50 weight or more - 1) and ethylene resins (i.e., polyethylene and ethylene) are used. A copolymer thereof containing 50% by weight or more) is preferred;
Most preferred is polyvinyl chloride.

In the production of the above synthetic resin film, which is the base material, resin additives such as plasticizers, heat stabilizers, antioxidants, light stabilizers, antistatic agents, ultraviolet absorbers, and far-infrared absorbers are added as necessary. , antifogging agents, lubricants, pigments, etc. can be added.

The base synthetic resin film according to the present invention is produced from the above composition by a known film forming technique. Known film-forming techniques include calendar molding, T-die extrusion, inflation molding, and melt casting.

If the thickness of this film is too thin, the strength will be insufficient, so it is undesirable.On the other hand, if it is too thick, it will be difficult to make the film into a film, and other handling (cutting the film and joining it into a house shape, spreading it on the framework of the house) will be undesirable. (including work to do)
Normally, 0.03 to 0.5 mm,
Preferably, 0.1 to 0.3 mm is appropriate.

The agricultural synthetic resin coating material of the present invention has a dustproof resin coating on at least one side of the small synthetic resin film produced by the above production method, and further contains an imidazole compound represented by the above formula. It is.

Dust-proof resin coatings include acrylic resins, fluorine-containing resins,
It is obtained from urethane resin, polymerizable urethane acrylate resin, etc.

The acrylic resin referred to herein is a polymer obtained by polymerizing mainly acrylate-1 to tsutacrylate.

Specific examples of the tsuma used include methyl (meth) acrylate, ethyl (meth) acrylate [. I., dodecyl (meth)acrylate, and vinyl acetate are also used.

In addition to the above-mentioned materials, acrylic resins can also be used for internal crosslinking.
may be copolymerized.

Examples of internal crosslinking agents include acrylic acid, methacrylic acid, chlorinated acid, iconic acid, maleic acid, allyl alcohol, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 2-hydroquinepropyl acrylate-1.・, dimethylaminoethyltuacrylate, diethylaminoconityl methacrylate, vinylpyridine, tert-butylaminoethyl methacrylate, glycidyl acrylate, glycidyl methacrylate,
Acrylic glycidyl ether, itaconic anhydride, maleic anhydride, acrylamide, acrylamide, maleamyl 11, N-methylolacrylamide, 11-
Notyrol notacrylamide, ethylene glycol somemethacrylate, soethylene glycol dinotacrylate
1~, l-lyethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate-1, tetrahy[-rofurfuryl methacrylate, tetrahydrofurfuryl acrylate I, 1゜3-butanediol di Examples include methacrylate, mono(2-tacrylic Dylethyl)acin 1'bosphae I., trimedylolpropane trimethacrylate, etc., which can be used alone or in combination.

Examples of the 7-component synthetic resin include polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, polytrifluoromonochloroethylene, perfluoropropylene resin, fluoroalkoxyethylene resin, or copolymers thereof. Furthermore, it may be a copolymer of the above-mentioned fluorine-containing monomer and a fluorine-free monomer (for example, a vinyl compound such as ethylene, propylene, vinyl chloride, etc.).

As the urethane resin, for example, polyisocyanun-1.
and polyethers, polyesters, polyether/polyesters, or mixtures thereof, and mixtures of these and low-molecular polyhydric alcohols, and if necessary, chain extenders having active hydrogen atoms, such as glycols, diamines, Examples include polyurethane obtained by various known methods of isocyanate polymerization of amyl alcohol, hydrazine, and hydrogen, and polyurethane resins obtained by blending polyurethane with one commonly used additive. .

Examples of the above-mentioned polyisocyanates include 2°4- and 2.6-) lylene diisocyanate-1, 4.4'
- Aromatic polyisocyanates such as diphenylmethane diisoso-1-1-11,5-naphthylene diisocyanate, triphenylmethane 1-lysosoate, polymethylene polyphenylisocyanate, or hekylinothylene diisocyanate, Examples include aliphatic polyisonanates such as polyisocyanate, methylene bis-4,4'-cyclohexyl isocyanate, methylene bis-4,4'-cyclohexyl isocyanate, ω·ω'-diisocyanato dinotylcyclohexane isophorone diisonanate, and the like. These may be used alone or as a mixture of two or more.

Also polyethers, polyesters, polyether
Examples of polyesters include polyhydric alcohols (e.g., ethylene glycol, propylene glycol, butylene glycol, 1,6-hexaneol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, etc.) and ethylene oxychloride. Zaid,
Polyethers with hydroxyl groups at the terminals obtained by adding one or more alkylene oxides such as brobylene oxite, butylene oxide, tetrahydrofuran, and ebihalohydrin, polyhydric phenols (e.g., resorcinol, hisphenol, etc.) ) alkylene oxylide addition polymers, polycarboxylic acids (e.g., maleic acid, fumaric acid, succinic acid, geltaric acid,
Adipic acid, azelaic acid, sebacic acid, phthalic acid,
pyromellitic acid, etc.), polyesters obtained by condensing the above-mentioned polyhydric alcohols and polycarboxylic acids, condensates of hydroxycarboxylic acids and polyhydric alcohols (e.g., castor oil BFj
(reaction products of acid and ethylene glycol, propylene glycol, etc.), lactone polymers such as caprolactone, addition polymerization of alkylene oxide to the above polyesters, and the above polyethers and polycarboxylic acids. Examples include polyesters and polyethers having hydroxyl groups at the ends obtained by condensation.

The polymerizable urethane acrylate resin can be obtained by using an ethylenically unsaturated compound as a compound having an active hydrogen atom used in the polymerization reaction of the urethane resin.

Examples of ethylenically unsaturated compounds include compounds containing a 10-oxy group (for example, allyl alcohol, 2-hydroxyethyl (meth)acrylate-I, polyethylene glycol mono(tsuku)acrylate-I, polypropylene glycol mono (acrylate, etc.), amino group-containing compounds (e.g., mononotylaminoethyl (tsuku) acrylate-1, monoconichi J rareminoethyl (tsuku))
acrylate, etc.), reaction products of acrylic acid or methacrylic acid with monoepoxy compounds (e.g., glycidyl acrylate, n-butyl glycidyl ether, allyl glycidyl ether, etc.), glycidyl acrylate-1 or glycidyl acrylate, monocarboxylic acid-containing compounds (e.g. acetic acid, butyric acid, benzoic acid, etc.),
Alternatively, reaction products of secondary monoamine compounds (eg, dimethylamine, dimethylamine, piperazine, medylaniline, etc.) can be mentioned.

Monomers that can be polymerized with the polymerizable urethane acrylate resin include styrene, vinyltoluene, t-butylstyrene, monochlorostyrene, α-methylstyrene, p-
- Styrene compounds such as methylstyrene and divinylhenzen, vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl henschede, phenoxyethyl (meth)acryle-I, isodecyl (meth)acrylate, n -Hexyl (meth)acrylate, stearyl (meth)acrylate-1~, lauryl (meth)acrylate [・, ethoxy (meth)acrylate, methoxyethyl (meth)acrylate, glycidyl (tsuku)acrylate, allyl (meth)acrylate, 2 -Hydroxyethyl (meth)acrylate, 2-
Hydroxypropyl(tsuku)acrylate, 2-methoxyethoxyethyl(meth)acrylate, Hensyl(tsuku)acryle-I, cyclohexyl(meth)acrylate, 2-human [coxoethyl(meth)acryloylphosphny 1, tetrahydrofurfuryl( meth)acrylate-1-11,3-butanedioredi(meth)acrylate, 1゜4-butanedioredi(meth)acrylate, 1,6-hexanethiol di(tsuku)acrylate, diethylene glyco-lredi(meth)acrylate, Bentyl glycol di(meth)acrylate, triconylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, l-IJ methylolpropane(meth)acrylate-l-33-methylbentanediol(meth)acrylate (meth)acrylate compounds such as , trimethylolprobantosu(meth)acrylate, pentaerythritol tri(meth)acrylate, unsaturated nitrile compounds such as acrylonitrile, acrylamide, α,β-unsaturated amides, diethyl fumarate and diester compounds of unsaturated polycarboxylic acids such as dibutyl maleate. These may be used alone or in combination of two or more.

In the present invention, the imidazur compound represented by the formula (1) is contained in the dustproof resin coating.

As a specific example of the imidazur compound, Fine Nyl:'CP-10 is commercially available from Tokyo Fine Gemical Flie.

The amount of the l-coupling compound added is preferably 0.05x to 10x, more preferably 0.1x to 3x, per 100 parts by weight of the film-forming resin.

If the amount of the above-mentioned compound added is less than 0.05, adhesion of algae cannot be prevented.

On the other hand, if it exceeds 10χ, the weather resistance of the coating will decrease, making it impossible to use it for a long period of time. Further, the dust resistance is also deteriorated, which is not preferable.

In addition to these ingredients, the bird-proofing resin coating may contain auxiliary ingredients, such as film-forming aids, surfactants, ultraviolet absorbers, antioxidants, colorants, stabilizers, etc., as necessary. be able to.

The method for forming a film using the above-mentioned dustproof resin is υ. When forming a film in a solution state, use an aqueous dispersion and/or an organic dispersion.
Of the medium? Any dispersion may be used; more preferred is an aqueous dispersion that is unlikely to dissolve the synthetic resin film.

” Part 2: Dust-proof resin? Coating of the 8 liquid onto a synthetic resin film does not require any special equipment, and can be carried out using a known coater such as a roll coater-1 knife coater, a Rono I coater, a spray coke, a gravure coke, or a giscoco.

There are various types of drying equipment, such as a flash drying method, an electric heating drying method, and an infrared heating method, and the one suitable for the solvent used is selected. In addition, when using a solution using an organic solvent,
It is necessary to take various measures against organic solvents. The drying temperature is determined as appropriate depending on the dustproof resin composition, the solvent used, the coating thickness, etc. When an aqueous dispersion is used,
The temperature is at least the temperature at which the film is formed, preferably about 100°C.

In addition, as a method for forming a film when using a polymerizable urethane acrylate-I type resin, curing by ultraviolet irradiation is appropriate. As a light source for causing this curing reaction, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a xenon lamp, an arc lamp, etc. are used.

The amount of dustproof resin liquid to be applied is such that the thickness of the film after drying is 0.1~
A plastic having a diameter of 20 μm, preferably 0.3-10 μm is preferred.

In addition, when forming the above-mentioned dustproof resin as an independent coating without forming it in a solution state, coextrusion method, extrusion coating method,
Extrusion lamination method and lamination method are used.

[Example] The present invention will be explained below with reference to Examples.

Reference Example 1 After mixing the vinyl chloride resin & II composition with the basic composition shown in Table 1 in a Henschel mixer for 10 minutes, the mixture was heated to 165°C.
and then kneaded with an L-type calender to a thickness of 0.1 mm.
I got the film.

Reference Example 2 Preparation of acrylic coating liquid Methyl methacrylate 59% by weight, n-butyl methacrylate 33% by weight, hydroxyethyl methacrylate-1.
70 parts by weight of a mixture of 6% by weight and 2% by weight of methacrylic acid and 1.0 parts by weight of polyethylene oxide alkyl phenyl ether derivative dissolved in 125 parts by weight of water.
Dropwise into the solution at °C over 3 hours with stirring,
The reaction was further continued for 3 hours to obtain an aqueous dispersion having a resin flow rate of about 45% by weight. This was adjusted to pH 76 with aqueous ammonia. Next, 1.
1 part by weight of limethylolpropane polyglycyl ether, 5 parts by weight of butylcarhydrol and 3 parts by weight of argylphenyl ether were added, and the resin concentration was adjusted to 20% by weight with water. This solution is used as a coating liquid.

Table 1 Dead wood combination Examples 1 to 3, Comparative Examples 1 to 2 On one side of the film obtained in Reference Example 1 above, an imidazole compound was added to the acrylic coating solution prepared in Reference Example 2 in the amounts and proportions shown in Table 3. Then, it was coated using a rod coater method so that the thickness of the coating became 57 mm, and it was dried in an oven at 130°C for 50 seconds to form a dust-proof vinyl chloride resin film (
A dust-proof layer (hereinafter abbreviated as vinyl) was obtained.

Example 4 Methyl methacrylate/butyl acrylate 1 and 2 were added as a binder to the compound with the basic composition shown in Table 1.
・Using an acrylic copolymer resin copolymerized at a molar ratio of 1, three layers are coextruded with a vinylidene difluoride resin and a resin composition in which an imidazole compound is added to the resin in an amount shown in Table 3. The thickness of each layer is 95μ in turn.
Melt-cast laminated films were obtained so that the thicknesses were 5 μm, 5 μm, and 5 μm.

Reference Example 3 The ethylene-vinyl acetate copolymer composition shown in Table 2 was
-Feed to die extruder and melt extrude to 0 thickness
．． A 1 mm film was obtained.

Table 2 Basic compounding ability Example 5 On one side of the film obtained in Reference Example 3, the acrylic coating solution prepared in Reference Example 2 was blended with the imidazole compound in the amount shown in Table 3, and the same as in Example J was applied. A coating of 5 μm was provided.

Table 3 shows the results of measuring the anti-algae properties and weather resistance of the infantile film obtained above.

Measurement method (1) Algae resistance Seven greenhouses with a frontage of 3 m and a length of 5 m were constructed in Nosakae-cho, Chiba Prefecture, and the films obtained in Examples and Comparative Examples were coated with the dust-proof resin coating on the outside.

The state of adhesion of algae to each sample was visually determined.

○; Adhesion of algae is not observed.

△: Adhesion of algae is observed.

×: Adhesion of algae is observed on the entire surface.

(2) Attach the 1lli 4-weather film to a window frame-shaped exposure test stand (installation location: Ni Nagoya City) with a 30-degree slope facing south, and visually evaluate the appearance of the film after a specified period of time (see Table 3) has elapsed. did.

○: No change.

Δ: Some brown spots are observed.

×: Brown spots are observed.

〔Effect of the invention〕

The agricultural synthetic resin coating phase according to the present invention has the following effects and greatly contributes to greenhouse horticulture.

■Since it prevents algae from attaching, it can be used for a long period of time even under special environments.

■Since a dust-proof resin coating is provided, high transparency can be maintained over a length of 1υl.

■ House management is extremely easy as stains caused by algae can be prevented.

Claims (1)

[Claims] 1. The dustproof resin coating provided on at least one side of the synthetic resin film has the following formula (1) ▲ mathematical formula, chemical formula, table, etc. ▼ (1) (R: alkyl An agricultural synthetic resin coating material comprising an imidazole compound represented by the following formula.