JPH0755553B2 - Agricultural synthetic resin coating material - Google Patents

Description

TECHNICAL FIELD The present invention relates to an agricultural synthetic resin coating material. More specifically, the present invention relates to an agricultural synthetic resin coating material capable of preventing adhesion of algae and maintaining high transparency for a long period of time.

[Conventional technology]

Advances in cultivation techniques for agricultural crops have been 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 actively carried out.
This method makes it possible to control the shipping time and cultivate special crops, and greatly contributes to the improvement of 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, antifog agents, stabilizers, etc. are blended in vinyl chloride resin films used as coating materials, but these additives gradually precipitate on the film surface, and dust adheres to them, causing film formation. Of light is reduced.

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

However, even on a film provided with such a polymer coating, deposits 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.

(JP-B-53-19345, JP-A-1-291935, JP-A-1-30172
4, JP-A-1-315432, JP-A-1-316264, JP-A-1-3162
65 etc.) [Problems to be solved by the invention] Various measures are taken to prevent deterioration of long-term weather resistance and light transmission of synthetic resin films for agriculture, but under severe conditions , Obtaining satisfactory results over a long period of use is considered very difficult.

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

[Means for solving problems]

According to the present invention, a synthetic polymer film is formed with a coating of a high molecular polymer containing one or more phenylurea compounds represented by the following general formula (I) on at least one side, and the synthetic resin film A synthetic resin coating material for agriculture, wherein the film or / and the coating film contains an ultraviolet absorber.

General formula: (However, R ₁ is H-, H ₃ C-, H ₃ CO-, Br-, Cl-, 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, -OCH 3, Indicates. ) 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, acryl glycidyl ether, itaconic anhydride, maleic anhydride, acrylamide, methacrylamide, maleamide, N-methyl roll acrylamide, N-methylol methacrylamide, ethylene glycol dimethacrylate, Diethylene glycol dimethacrylate, triethylene glycol dimethacrylate,
Examples thereof include tetraethylene glycol dimethacrylate, tetrahydrofurfuryl methacrylate, tetrahydrofurfuryl acrylate, 1,3-butanediol dimethacrylate, mono (2-methacryloylethyl) acid phosphate, trimethylolpropane trimethacrylate, and the like. Used in 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. These may be used alone or in combination of two or more.

The amount of the phenylurea-based compound added is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the polymer for forming a film,
In particular, the range of 0.5 to 20 parts by weight is more preferable.

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.

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 coating 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. When an aqueous dispersion is used, the drying temperature is not lower than the temperature at which the film is formed, preferably about 100 ° C.

The coating amount of the coating composition is 0.1 to 20 μm after drying.
m, 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 present invention, an ultraviolet absorber is contained in the synthetic resin film or / and the polymer coating film which is the substrate. 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 ultraviolet absorbers.

2-Hydroxy-, which is an enzophenone-based UV absorber
4-methoxybenzophenone, 2,4-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.

2- (2'- which is a benzotriazole type ultraviolet absorber
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, 2-
(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 can be used either individually or in combination of two or more.
It is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, per 0 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 if the amount is 1 to 40 parts by weight, preferably 5 to 30 parts by weight, per 100 parts by weight of the polymer forming the film. Furthermore, the desired effect can be obtained without the inclusion of an ultraviolet absorber.

〔Example〕

 Examples and comparative examples are given below.

Examples 1 to 10 and Comparative Examples 1 to 3 (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 system Stabilizer 2.5 A resin composition consisting of sorbitan monopalmitate 2 was prepared, and the type and amount of the ultraviolet absorber shown in Table 1 were blended. However, in Comparative Example 1, no ultraviolet absorber was added.

Mix each formulation in a Henschel mixer for 10 minutes and then
Kneading was performed at 5 ° C., and then a film having a thickness of 0.1 mm was obtained using an L-type calender device.

(2) Preparation of polyester resin base film Polyethylene terephthalate (having an intrinsic viscosity of 0.65 measured at 25 ° C using o-chlorophenol as a solvent) of 100 parts by weight absorbs ultraviolet rays of the types and amounts shown in Table 1. The agent was blended. However, in Comparative Example 2, no ultraviolet absorber was blended.

After mixing each compound for 10 minutes with a Henschel mixer, melt extrusion is carried out by a conventional method, and the biaxial stretching is carried out at a stretching temperature of 65 ° C in the longitudinal direction and a stretching ratio of 3.5 times, and then in the transverse direction at a stretching temperature of 65 ° C and a stretching ratio of 3.5 times. Then, a biaxially oriented film having a thickness of 0.15 mm was produced. 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 ℃ 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 so that the resin concentration was 20% by weight.
Was prepared.

(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 A urea solution and a pyridine compound of the kind shown in Table 1 were added to the resin solution prepared according to the method described in (3) or (4) above in the ratio (resin It means the ratio to the solid content.).

The above coating composition was applied onto one surface of the base film prepared by the methods (1) and (2) by a roll coater method so that the thickness of the coating became 3 μm, and the coated film was placed in an oven at 100 ° C.
After drying for a minute, a film-forming film was obtained.

(6) Method for measuring algae resistance A house with a frontage of 3 m and a length of 5 m installed in Itoshima-gun, Fukuoka Prefecture was covered so that the surface provided with the coating was outside the house.

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

A: Adhesion of algae is not recognized at all.

○: Adhesion of algae is slightly observed.

Δ: Adhesion of algae is recognized.

X: Adhesion of algae is recognized on the entire surface.

[Effects of the Invention] According to the present invention, it is possible to suppress a decrease in light transmittance of an agricultural synthetic resin coating material that is spread outdoors, so that the efficiency of forcible cultivation or special crop cultivation can be improved. , Has great agricultural utility value.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area C08K 5/21 KBB C08L 33/00 LHX (56) Reference JP-A-1-291935 (JP, A) ) JP-A 1-301724 (JP, A) JP-A 50-125029 (JP, A) JP-A 60-223874 (JP, A) JP-A 59-170162 (JP, A) JP-A 46- 7483 (JP, A) JP-B 46-29757 (JP, B1) JP-B 53-19345 (JP, B2)

Claims (2)

[Claims] 1. A synthetic polymer film, on which at least one surface is coated with a high molecular polymer containing one or more phenylurea compounds represented by the following general formula (I), and A synthetic resin coating material for agriculture, which comprises a synthetic resin film and / or an ultraviolet absorber in the coating. 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, -OCH 3, Or Indicates. ) 2. The agricultural synthetic resin coating material according to claim 1, wherein the high molecular weight polymer is an acrylic resin.