JPH068041B2 - Agricultural synthetic resin film - Google Patents

Description

The present invention relates to an agricultural synthetic resin film. More specifically, it relates to an agricultural synthetic resin film capable of preventing adhesion of algae and maintaining high transparency for a long period of time.

[Conventional technology]

Advances in cultivation technology for agricultural crops are remarkable, and as part of this, greenhouse cultivation and tunnel cultivation, in which plants are cultivated inside covered with a vinyl chloride resin film, are being actively carried out.
This method makes it possible to control the shipping time and cultivate special crops, and greatly contributes to the improvement of the productivity and market value of agricultural products.

Weather resistance and light transmittance are important for the coating material used for the greenhouse cultivation and tunnel cultivation. Therefore, plasticizers, antifogging agents, stabilizers, etc. are blended in the vinyl chloride resin film, etc. used as a covering material, but these additives gradually precipitate on the surface of the film and dust adheres to it, causing the film to grow. Of light is reduced.

As a countermeasure against this, recently, a polymer film such as acrylic resin, fluorine-containing resin, urethane resin, and polymerizable urethane acrylate resin is formed on the surface of vinyl chloride resin film to prevent the exposure of precipitates. The reduction of the light transmittance due to the adhesion of dust is alleviated.

However, even in a film provided with such a polymer coating, an adhered substance may be formed on the film surface over time depending on the use environment, and the light transmittance of the film may be significantly impaired. This is thought to be caused by molds or some algae.

As a countermeasure against this, it has been proposed to incorporate various bactericides into the high molecular weight polymer which is a material for forming a film on the film surface.

(Japanese Patent Publication No. 53-19345, JP-A-1-291935,
JP-A-1-301724, JP-A-1-315432, JP-A-1-316264, JP-A-1-316265, etc. [Problems to be Solved by the Invention] Long-term weather resistance and light transmittance of a synthetic resin film for agriculture. Although various measures have been taken to prevent the decrease, it is considered very difficult to obtain satisfactory results over a long period of use under severe conditions.

The present inventors have conducted various studies, in particular, on a technique for preventing a decrease in light transmittance due to algae settlement.

[Means for solving problems]

The present inventors have found that certain phenylurea compounds and 2,3,3
It was arrived at as a result of research after knowing that algae did not grow on the surface containing a certain concentration of 5,6-tetrachloro-4-methylsulfonylpyridine for a long period of time.

That is, the present invention provides one of the phenylurea compounds represented by the following general formula (I) on at least one side of a synthetic resin film.
Species or two or more species and 2,3,5,6-tetrachloro-
A synthetic resin film for agriculture, characterized in that a film of a high-molecular polymer containing 4-methylsulfonylpyridine is formed.

General formula: (However, R ₁ is H-, H ₃ C-, H ₃ CO-, Br-,
Cl-, Or R ₂ is H-, C-, F ₃ C-, or R ₃ and _{R 4} is -H, or _-CH 3, _{R 5} is _{-H, -CH 3, - (CH} 2) 3 CH 3, -OC
H ₃ , Or Indicates. ) Another is, on at least one side of a synthetic resin film, 1 of the phenylurea-based compound represented by the general formula (I).
Species or two or more species and 2,3,5,6-tetrachloro-
A synthetic resin film for agricultural use, wherein a polymer film containing 4-methylsulfonylpyridine is formed, and the synthetic resin film or / and an ultraviolet absorber is contained in the film. Is.

Next, the present invention will be described in more detail.

Examples of the synthetic resin forming the synthetic resin film in the present invention include vinyl chloride polymers (hard and soft), acrylic polymers, polyesters (thermoplastic and thermosetting resins), polyolefins (polyethylene, polyvinyl acetate, etc.). ) And other thermoplastic and thermosetting resins.

In the above-mentioned synthetic resin which is the base, if necessary, a resin additive such as a plasticizer, a heat stabilizer, an antioxidant, a light stabilizer,
Antistatic agents, far-infrared ray absorbing agents, non-dripping agents, lubricants, inorganic fillers, pigments and the like can be added.

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

If the thickness of the base film is too thin, the strength becomes insufficient, which is not preferable. Conversely, if the thickness is too thick, it causes inconvenience to the film forming work, so 0.03 to 0.5 mm, preferably 0.1 to 0.3 mm is suitable. is there.

The synthetic resin film according to the present invention has a film of a high molecular polymer containing a specific phenylurea compound, which will be described in detail later, formed on at least one surface thereof.

Examples of the high molecular weight polymer that forms a film include acrylic resins, amino resins (alkyd resins, melamine alkyd resins), organosiloxane resins, fluororesins,
Examples thereof include polyester resins, alkylphenol resins, epoxy resins and the like. Of these, acrylic resins are particularly preferable.

The acrylic resin here is a polymer obtained by polymerizing mainly acrylate and methacrylate. Specific examples of the monomer to be used include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-.
Examples thereof include ethylhexyl (meth) acrylate and 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.

As the internal crosslinking monomer, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, allyl alcohol, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, dimethylaminoethyl 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,
Examples thereof include mono (2-methacryloylethyl) acid phosphate and trimethylolpropane trimethacrylate, which may be used alone or in combination.

The above polymer may be used alone or in combination of two or more.

Specific examples of the specific phenylurea compound to be contained in the coating film of the present invention include, for example, chlorophenoxyphenyldimethylurea. Fluoromethylphenyl dimethyl urea Bromophenyl methoxymethyl urea Methoxyphenoxyphenyl dimethyl urea Chlorophenyl dimethyl urea Methyl cyclohexyl phenyl urea Dichlorophenyldimethylurea Dichlorophenyl methyl butyl urea Phenyldimethylurea Chlorophenyl methoxymethyl urea Dichlorophenyl methoxymethyl urea Dimethylbenzyl p-tolylurea Dimethylbenzyl methyl phenyl urea Dimethyl ureido phenyl carbamate Chlorophenylmethylpropynyl urea And the like, and these are used alone or in combination of two or more.

The amount of the phenylurea compound added is preferably 0.1 to 30 parts by weight, and more preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the polymer for forming a film.

If the addition amount of the above compound is less than the lower limit amount, the object is not achieved, and if it is more than the upper limit amount, there is a problem that the transparency of the coating film formed on the film decreases.

Other herbicides, fungicides, fungicides, insecticides, pest repellents and the like can be used in combination with the above composition for the purpose of enhancing efficacy or expanding application.

If necessary, auxiliary components such as film-forming aids, surfactants, antioxidants, colorants, stabilizers, thickeners, defoamers and the like can be added.

The amount of 2,3,5,6-tetrachloro-4-methylsulfonylpyridine used is in the range of 0.01 to 10 times the weight of the phenylurea compound used in combination, particularly preferably 0.1 to 2
It is double. If the amount used is below the lower limit, there is no effect, and if it is above the upper limit, the effect saturates, and the weather resistance and transparency of the film deteriorate.

2,3,5,6-Tetrachloro-4-methylsulfonylpyridine is used in combination with the above-mentioned phenylurea compound in the polymer coating. Although 2,3,5,6-tetrachloro-4-methylsulfonylpyridine alone has almost no algal colonization inhibitory effect, when used in combination with a phenylurea compound, it exerts an extremely strong antialgal effect for a long period of time. The reason for this and the physiological effects on plants have not been clarified, but it is considered that the two synergistically exert synergistic toxic effects.

As the method for forming the film of the above-mentioned composition for a film, when the film is formed in a solution state, either an aqueous dispersion and / or a solution of an organic solvent may be used.

Application of the coating composition solution to the synthetic resin film,
It can be performed by a known method such as a doctor blade method, a roll coating method, a dip coating method, a spray coating method, a rod coating method, a bar code method, a knife coating method or a brush coating method.

There are various drying devices such as a gas stream drying system, an electric drying system, and an infrared heating system, and the one suitable for the solvent used is selected. When using a solution containing an organic solvent,
It is necessary to take various measures against organic solvents. The drying temperature is appropriately determined depending on the conditions such as the polymer, the solvent used and the coating thickness, and when an aqueous dispersion is used, it is at least the temperature at which the film is formed, preferably about 100 ° C.

The coating amount of the coating composition is such that the thickness of the coating after drying is 0.1 to 20.
The amount is preferably μm, preferably 0.3 to 10 μm.

When the coating composition is formed as a single film without being in a solution state, a coextrusion method, an extrusion coating method,
An extrusion laminating method and a laminating method are used.

In the invention described in claim (2) of the present application, the ultraviolet absorbent is contained in the synthetic resin film or / and the polymer coating film as the substrate.

Of course, the ultraviolet absorber is effective in preventing the photodegradation of the synthetic resin film and the polymer film, maintaining the film strength and reducing the decrease in the light transmittance due to the dustproof effect, but in the present invention, The ultraviolet absorber prevents the photo-deterioration of the phenylurea compound and 2,3,5,6-tetrachloro-4-methylsulfonylpyridine contained in the polymer coating and extends the effective period, It is recognized that it has an effect of activating and enhancing the antialgal effect.

Examples of the ultraviolet absorber used here include the following.

2-Ethylhexyl-2-cyano-3,3'-diphenyl acrylate and ethyl-2-cyano-3,3'-diphenyl acrylate, which are cyanoacrylate-based ultraviolet absorbers.

2-Hydroxy-, which is a benzophenone-based UV absorber
4-methoxybezophenone, 4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2,2'-dihydroxy- 4,
4'-dimethoxybenzophenone, 2-hydroxy-4
-Benzoyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonebenzophenone, 2,
2 ', 4,4'-tetrahydroxybenzophenone,
2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-5-chlorobenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl) methane.

Bezotriazole-based UV absorber 2- (2'-hydroxyphenyl) benzotriazole, 2- (2'-
Hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5-methylphenyl)-
5-carboxylic acid butyl ester benzotriazole, 2
-(2'-hydroxy-5'-methylphenyl) -5,
6-dichlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) -5-ethylsulfone benzotriazole, 2- (2'-hydroxy-5'-t
-Butylphenyl) -5-chlorobenzotriazole,
2- (2'-hydroxy-5'-t-butylphenyl)
Benzotriazole, 2- (2'-hydroxy-5'-
Aminophenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-dimethylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-dimethylphenyl) -5-methoxybenzotriazole, Two
-(2'-methyl-4'-hydroxyphenyl) benzotriazole, 2- (2'-stearyloxy-3 ',
5'-Dimethylphenyl) -5-methylbenzotriazole, 2- (2'-hydroxy-5-carboxylic acid phenyl) benzotriazole ethyl ester, 2- (2'-
Hydroxy-3'-methyl-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-t
-Butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-methoxyphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t -Butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-
5'-cyclohexylphenyl) benzotriazole,
2- (2'-hydroxy-4 ', 5'-dimethylphenyl) -5-carboxylic acid benzotriazole butyl ester, 2- (2'-hydroxy-3', 5'-dichlorophenyl) benzotriazole, 2- (2'-hydroxy-4 ', 5'-dichlorophenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-dimethylphenyl) -5-ethylsulfone benzotriazole, 2
-(2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-methoxyphenyl) -5-methylbenzotriazole, 2
-(2'-hydroxy-5'-methylphenyl) -5-
Carboxylic acid ester benzotriazole, 2- (2'-
Acetoxy-5'-methylphenyl) benzotriazole.

The above-mentioned ultraviolet absorbers can be mentioned, but among them, it is preferable to use a benzophenone-based ultraviolet absorber or a benzotriazole-based ultraviolet absorber.

These ultraviolet absorbers may be used either individually or in combination of two or more. The amount used is the synthetic resin 1 which is the substrate.
It is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, per 00 parts by weight. If the amount used is too small, the desired effect of improving anti-algae persistence cannot be obtained, and conversely, if the amount is too large, the effect of improving anti-algae sustainability is not recognized for the amount used, and an ultraviolet absorber. Undesirably bleeds on the film surface and reduces the transparency of the film.

When the ultraviolet absorber is contained in the film, the amount used is in the above range when the amount is 1 to 40 parts by weight, preferably 5 to 30 parts by weight, per 100 parts by weight of the high molecular weight polymer forming the film. Furthermore, the desired effect can be obtained without the inclusion of an ultraviolet absorber.

〔Example〕

The present invention will be described in detail below with reference to test examples and examples.

Test Example-1 An acrylic resin was dissolved in toluene to prepare a 25% solution. Each drug shown in Table 1 was added to this solution at a predetermined ratio, mixed and prepared.

After applying a predetermined amount of this solution to Toyo filter paper NO5C, 100
It was dried at ℃ for 5 minutes. This was cut into 10 × 10 mm to obtain a test piece. After injecting 20 ml of synthetic medium for green algae into a plastic dish having a diameter of 9 cm and solidifying, 0.2 ml of a test solution of algae that had been cultured in advance was inoculated into the surface layer portion with corn sludge, and each of the above test pieces was brought into contact with this medium for coating. Affixing and culturing at 28 ° C. for 3 months under light irradiation, the algae control effect was visually determined.

The results are shown in Table 1. According to the table, tetrachloromethylsulfonyl pyridine alone has almost no algal protection,
When it is used in combination with dichlorophenyldimethylurea or other phenylurea compounds, the efficacy is synergistically increased as compared with the case where it is not used together, and the efficacy is obviously superior to various fungicidal compounds.

Examples-1 to 16 and Comparative Examples-1 to 5 (1) Preparation of vinyl chloride resin base film Polyvinyl chloride resin (: 1300) 100 parts by weight Dioctyl phthalate 45 Tricresyl phosphate 5 Epoxy resin 2.5 Ca-Ba- Zn-based stabilizer 2.5 A resin composition comprising sorbitan monopalmitate 2 was prepared, part of which was mixed with the type and amount of UV absorbers shown in Tables 2 and 3, and part of which was mixed. Nakatsuta.

After mixing each formulation with a Henschel mixer for 10 minutes,
Knead at 165 ° C, then use an L-type calender to reduce the thickness to 0.
A 1 mm film was obtained.

(2) Preparation of polyester resin base film For 100 parts by weight of polyethylene terephthalate (having an intrinsic viscosity of 0.65 measured at 25 ° C. using o-chlorophenol as a solvent), the types and the types shown in Tables 2 and 3 The amount of UV absorber was compounded. Moreover, the ultraviolet absorber was not mixed in a part.

After mixing each formulation with a Henschel mixer for 10 minutes,
Melt extrusion by a conventional method, stretching temperature 65 ° C in the longitudinal direction, stretching ratio 3.5 times, then stretching temperature 65 ° C in the transverse direction, stretching ratio
Sequential biaxial stretching was performed at 3.5 times to produce a 0.15 mm thick biaxially oriented film. The density of this film was 1.36 g / cm ³ .

(3) Preparation of acrylic resin solution Methyl methacrylate 50 parts by weight Butyl methacrylate 30 〃 2-hydroxyethyl methacrylate 18 〃 Methacrylic acid 2 〃 Isopropyl alcohol 100 〃 Benzoyl peroxide 1 〃 While stirring at 70 ° C for 3 hours. After the reaction, 0.5 part by weight of benzoyl peroxide was added, and the reaction was continued for another 3 hours at the same temperature. Isopropyl alcohol was added to the obtained polymer solution to prepare a resin concentration of 20% by weight.

(4) Preparation of Fluorine Resin Solution 17 parts by weight of polyvinylidene fluoride resin, 3 parts by weight of polymethylmethacrylate resin and 80 parts by weight of methyl ethyl ketone were mixed to prepare a solution having a resin concentration of 20% by weight.

(5) Formation of coating film The resin solution obtained by the methods (3) and (4) above was added to the phenylurea compounds, bactericidal compounds and 2,3,3 shown in Tables 2 and 3.
5,6-Tetrachloro-4-methylsulfonylpyridine (TCSP) was added in the proportions shown in the table (representing the proportion to the resin solid content) to obtain a coating composition.

On one side of the substrate film prepared by the above method (1), (2),
This composition was applied by a roll coater method so that the thickness of the coating would be 3 μm, and dried in an oven at 100 ° C. for 1 minute to obtain a coating-forming film.

(6) Measurement of algae control efficacy A house with a frontage of 3 m and a length of 5 m installed in Itoshima-gun, Fukuoka Prefecture was coated with each of the above-mentioned test films so that the surface on which the coating was formed was the outside of the house. The adhered state of the adherents on each test film was visually determined.

The results are shown in Tables 2 and 3.

According to Table 2, the combined use of dichlorophenyldimethylurea (DCMU) and TCSP in the coating is significantly more effective than that of DCMU alone.

UV absorber is added to the base film and DCMU is applied to the film.
The one to which TCSP and TCSP are added together maintains the algae control effect for a longer period of time.

According to Table 3, each phenylurea compound of the present invention and T
The sample film to which CSP was added together with the coating did not have algae settlement for about 24 months or longer.

UV absorber is added to the base film and DCMU is applied to the film.
With the addition of TCSP and TCSP, algae did not settle for about 30 months or longer.

〔The invention's effect〕

The agricultural synthetic resin film of the present invention suppresses a decrease in light transmittance for a long period of time even when stretched outdoors under severe conditions,
Useful for institutional gardening.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08L 33/00 LHX 7921-4J LHY 7921-4J

Claims (3)

[Claims] 1. A synthetic resin film having, on at least one side thereof, one or more phenylurea compounds represented by the following general formula (I) and 2,3,5,6-tetrachloro-4-methyl. A synthetic resin film for agriculture, wherein a film of a high-molecular polymer containing sulfonylpyridine is formed. General formula: (However, R ₁ is H-, H ₃ C-, H ₃ CO-, Br-,
Cl-, Or R ₂ is H-, Cl-, F ₃ C-, or R ₃ and _{R 4} is -H, or _-CH 3, _{R 5} is _{-H, -CH 3, - (CH} 2) 3 CH 3, -OC
H ₃ , Or Indicates. ) 2. The synthetic resin film for agriculture according to claim 1, wherein the synthetic resin film and / or the coating contains an ultraviolet absorber. 3. The synthetic resin film for agriculture according to claim 1, wherein the high molecular polymer is an acrylic resin.