JPH01291935A - Synthetic resin coating material for agriculture - Google Patents

Abstract

PURPOSE:To prevent waterweed from adhering and keep high transparency for a long time by incorporating a given compound in a dustproof resin film provided on one surface of a synthetic resin film. CONSTITUTION:A dustproof film is proved on one surface of a base synthetic resin film, and an isophthalonitrile group compound represented by the formula is included therein. In the formula, X represents a halogen atom. The dustproof resin film is prepared from acryl resin, fluorine containing resin, urethane resin, polymerizable urethane acrylate resin or the like. As the adding volume of the isophthalonitrile compound, 0.05-10% is preferred to 100pts.wt. of film forming resin. When the adding volume of the compound is less than 0.05%, adhesion of waterweed cannot be prevented. When more than 10%, weathering properties of the film is lowered and the film cannot be used for a long time. Also, dustproof properties are worsesned, which not preferable.

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.

[Conventional technology]

In recent years, in order to increase the marketability and productivity of agricultural crops through forced, semi-forced or suppressed cultivation, so-called greenhouse cultivation and tunnel cultivation have become popular, in which useful plants are grown under agricultural covering materials such as agricultural vinyl film. It is being actively carried out.

The synthetic resin coating materials currently used in greenhouse cultivation and tunnel cultivation, such as vinyl chloride resin films, contain plasticizers, antifogging agents, stabilizers, etc., but these additives degrade over time. As the film surface bleeds, dust tends 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, antifogging 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 dustproof film suppresses the adhesion of dust to the film surface, allowing it to maintain high transparency over a long period of time.In addition, the film contains weather stabilizers, plasticizers, antifogging agents, etc. contained in the base material. Since the loss of water is also suppressed, it is possible to maintain performance such as strength and anti-fogging 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, in terms of film composition, since the digested compound has a step effect, there is a method of mixing the copper compound into the dust-proof resin coating to prevent algae from adhering, but the effect is insufficient.

An object of the present invention is to provide an agricultural synthetic resin coating material that can prevent the adhesion of algae and maintain high transparency over a long period of time.

Means for Solving Section C U] As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a specific compound is contained in the dustproof resin coating provided on at least one side of the synthetic resin film. The present inventors have discovered that this method can prevent the adhesion of algae and maintain high transparency for a long period of time, leading to the completion of the present invention.

That is, the present invention provides an agricultural synthetic resin coating in which vPt& is defined as containing an isophthalonitrile compound represented by the following formula (X: halogen atom) in a dustproof resin coating provided on at least one side of a synthetic resin film. It is a 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 50% or more of vinyl chloride) and ethylene resins (i.e., polyethylene and 50% by weight of ethylene) are used. % or more thereof) are preferred, most preferably polyvinyl chloride.

In the production of the above-mentioned synthetic resin film as a base, resin additives such as plasticizers, heat stabilizers, antioxidants, light stabilizers, antistatic agents, ultraviolet absorbers, far-infrared absorbers, 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 frame of the house) (including work to do)
Normally, 0.03 to 0.5 m + *
, preferably in the order of 0.1 to 0.3.

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

Dust-proof resin coatings include acrylic resin, fluorine-containing resin,
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 and methacrylate. Specific examples of monomers used include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate,
2-Ethylhexyl (meth)acrylate, dodecyl (
meth)acrylate, and vinyl acetate is also used.

The acrylic resin may be copolymerized with an internal crosslinking monomer in addition to the above monomers.

Internal crosslinking monomers include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, allyl alcohol, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate. , vinyl pyridine, tert-butylaminoethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, acrylic glycidyl ether, itaconic anhydride, maleic anhydride, acrylamide, methacrylamide, maleamide, N-methylol acrylamide, N-methylol methacrylamide, ethylene Glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl acrylate,
1゜3-butanediol dimethacrylate, mono (2
-methacryloylethyl) acid phosphate, trimethylolpropane trimethacrylate, etc., which may be used alone or in combination.

Examples of fluorine-containing resins include polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene,
Polytrifluoromonochloroethylene, perfluoropropylene resin, fluoroalkoxyethylene resin, or copolymers thereof, and the above-mentioned fluorine-containing monomers and non-fluorine-containing monomers (e.g., ethylene, propylene, vinyl chloride) It may also be a copolymer with a vinyl compound such as

Examples of urethane resins include polyisocyanates, polyethers, polyesters, polyethers/polyesters, mixtures thereof, mixtures of these and low-molecular polyhydric alcohols, and optionally those having active hydrogen atoms. Polyurethanes obtained by various known methods of isocyanate polymerization addition reaction with chain extenders such as glycols, diamines, amyl alcohols, hydrazine, and hydrogen, or polyurethanes obtained by blending various commonly used additives with polyurethanes. Resin can be given.

Examples of the polyisocyanates include 2.4- and 2.6-dolylene diisocyanate, 4.4'-diphenylmethane diisocyanate, 1.5-naphthylene diisocyanate, triphenylmethane triisocyanate, and polymethylene polyphenylisocyanate. Aromatic polyisocyanate or hexamethylene diisocyanate, xylylene diisocyanate, methylene bis-4,4°-cyclohexyl isocyanate, ω・
Examples include aliphatic polyisocyanates such as ω'-diisocyanate, dimethylcyclohexane, isophorone diisocyanate, and the like. These may be used alone or as a mixture of two or more.

Also polyethers, polyesters, polyethers,
Examples of polyesters include polyhydric alcohols (e.g., ethylene glycol, propylene glycol, butylene glycol, 1,6-hexanediol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, etc.), ethylene oxide,
Addition of alkylene oxide to polyethers and polyhydric phenols (e.g., resorcinol, bisphenol, etc.) having a hydroxyl group at the end obtained by adding one or more alkylene oxides such as propylene oxide, butylene oxide, tetrahydrofuran, and ebihalohydrin. Polymers, polycarboxylic acids (e.g.
alkylene oxide addition polymers of maleic acid, fumaric acid, succinic acid, geltaric acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, pyromellitic acid, etc., and condensation of the above polyhydric alcohols and polycarboxylic acids. The resulting polyesters, condensates of hydroxycarboxylic acids and polyhydric alcohols (for example, reaction products of castor oil fatty acids and ethylene glycol, propylene glycol, etc.), lactone polymers such as caprolactone, and alkylene oxides in addition to the above polyesters. and polyesters/polyethers having hydroxyl groups at the terminals obtained by condensing the above-mentioned polyethers with polycarboxylic acids.

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.

The ethylenically unsaturated compounds mentioned here include compounds containing hydroxy groups (for example, allyl alcohol, 2-hydroxyethyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc.), amino groups, etc. containing compounds (e.g., monomethylaminoethyl (meth)acrylate, monoethylaminoethyl (meth)acrylate, etc.), acrylic acid or methacrylic acid and monoepoxy compounds (e.g., glycidyl (meth)acrylate, n
reaction products of glycidyl acrylate or glycidyl methacrylate with monocarboxylic acid-containing compounds (e.g. acetic acid, butyric acid, benzoic acid, etc.), or secondary monoamine compounds (e.g. dimethylamine, etc.); , diethylamine, piperidine, methylaniline, etc.).

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 divinylbenzene, vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate, phenoxyethyl (meth)acrylate, isodecyl (meth)acrylate, n-hexyl (meth)acrylate Acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, ethoxy (meth)acrylate, methoxyethyl (meth)acrylate, glycidyl (
meth)acrylate, allyl(meth)acrylate, 2
-Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-methoxyethoxyethyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, 2
-Hydroxyethyl (meth)acryloyl phosphate, tetrahydrofurfuryl (meth)acrylate, 1
．． 3-butanediol di(meth)acrylate, 1°4
-Butanediol di(meth)acrylate, 1,6-hexanethiol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate (meth)acrylate, trimethylolpropane di(meth)acrylate, 3-methylbentanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate
(meth)acrylate compounds such as acrylate,
Examples include unsaturated nitrile compounds such as acrylonitrile, acrylamide, diester compounds of unsaturated polycarboxylic acids such as α, β-unsaturated diethyl amidralate, and dibutyl maleate. These may be used alone or in combination of two or more.

In the present invention, an isophthalonitrile compound represented by the following formula is contained in the dustproof resin coating.

Specific examples of isophthalonitrile compounds include Nobucoside N-96, Nobucoside N-96, and Nobucoside N from San Nobuco ■.
-54-D (X=C1') etc. are commercially available.

The amount of the above-mentioned compound to be added is preferably 0.05 to 10 x, more preferably o, iz to 3 x per 100 parts by weight of the film-forming resin.

If the amount of the compound added (i) is less than 0.05χ, adhesion of algae cannot be prevented.

On the other hand, if it exceeds 10χ, the weather resistance of the coating decreases, 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 components, the dust-proof resin coating may contain auxiliary components, such as film-forming aids, surfactants, ultraviolet absorbers, antioxidants, colorants, stabilizers, etc., as necessary. Can be done.

As for the method of forming the film of the dust-proof resin, when forming the film in a solution state, either an aqueous dispersion and/or an organic solvent solution may be used, and it is more preferable that there is little risk of dissolving the synthetic resin film. It is an aqueous dispersion.

The application of the dustproof resin solution to the synthetic resin film does not require any special equipment, and can be carried out using a known coater such as a roll coater, knife coater, rod coater, spray coater, gravure coater, or kiss coater.

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 film forming method when using a polymerizable urethane acrylate 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~
The amount is preferably 20 μm, preferably 0.3 to 10 μm.

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 A vinyl chloride resin composition having the basic composition shown in Table 1 was mixed for 10 minutes in a Henschel mixer, then kneaded at 165°C, and then used in an L-type calender to obtain a film with a thickness of 0.1 mm.

Table 1 Basic formulation reference example 2 Adjustment of acrylic coating liquid Methyl methacrylate 59% by weight, n-butyl methacrylate 33% by weight, hydroxyethyl methacrylate 6
% by weight and 100 parts by weight of a mixture of 12 methacrylic acids and 1.0 parts by weight of polyethylene oxide alkyl phenyl ether derivative dissolved in 125 parts by weight of water at 70°C.
It was added dropwise into the solution of C over 3 hours with stirring, and the mixture was reacted for an additional 3 hours to obtain an aqueous dispersion having a concentration of about 45% by weight. This was adjusted to pH 7 with aqueous ammonia.

Next, to 100 parts by weight of this aqueous dispersion, 1 part by weight of trimethylolpropane polyglycidyl ether, 11 parts of butyl calhitol 5i, and 3 parts by weight of alkylphenylethyl were added, and the resin concentration was adjusted to 20% by weight with water. Adjusted to. This solution is used as a coating liquid.

Examples 1 to 3, Comparative Examples 1 to 2 On one side of the film obtained in Reference Example 1 above, an isophthalonitrile compound was added to the acrylic coating solution prepared in Reference Example 2 in the amount shown in Table 3, and a coating was formed. The film was coated using a rod coater method to a thickness of 5 μI, and dried in an oven at 130° C. for 50 seconds to obtain a dustproof vinyl chloride resin film (hereinafter abbreviated as dustproof vinyl).

Example 4 Methyl methacrylate/butyl acrylate was added as a binder to a compound with the basic composition shown in Table 1 at 2=1.
Using an acrylic copolymer resin copolymerized at a molar ratio of
Three layers were coextruded with a vinylidene fluoride resin and a resin composition in which an isophthalonitrile compound was added to the resin in an amount shown in Table 3, and the thickness of each layer was 95 mm.
A laminated film was obtained by melt casting to have a thickness of μTsuru, 5μm, and 5μAkebono.

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 ms film was obtained.

Example 5 On one side of the film obtained in Reference Example 3, an isophthalonitrile compound was added to the acrylic coating solution prepared in Reference Example 2 in the amount shown in Table 3, and a 5 μm coating was applied in the same manner as in Example 1. A coating was provided.

Table 2 Table 3 shows the results of measuring the anti-algae properties and weather resistance of the dust-proof films obtained using the above basic formulations.

Measurement method (1) Algae resistance Seven houses with a frontage of 3Il and a length of 5+m were constructed in Otaki-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.

○: No adhesion of algae is observed.

Δ: Adhesion of algae is observed.

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

(2) The weather-resistant film was attached to a window frame-shaped exposure test stand (installation location: Nagoyafu) with a 30-degree southward slope, and after a predetermined period (see Table 3) had passed, the appearance of the film was visually judged. .

O: No change.

Δ: Some brown spots are observed.

×: Brown spots are observed.

〔Effect of the invention〕

The agricultural synthetic resin coating material 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 it has a dust-proof resin coating, high transparency can be maintained over a long period of time.

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

Claims (1)

[Claims] 1. The dust-proof resin coating provided on at least one side of the synthetic resin film is an isophthalonitrile compound represented by the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (X: halogen atom) An agricultural synthetic resin covering material characterized by containing.