JPH0819261B2 - Agricultural synthetic resin surface modifier - Google Patents

Description

TECHNICAL FIELD The present invention relates to a surface modifier which imparts excellent antifogging property and antifog property to the surface of an agricultural synthetic resin.

Conventional technology In order to improve productivity and marketability of agricultural products, facility cultivation such as greenhouse cultivation and tunnel cultivation using synthetic resin films has been actively performed.

In this case, an antifogging agent such as sorbitan fatty acid ester or glycerin fatty acid ester is used in order to prevent water drop attached to the surface of the synthetic resin film or the like inside the house or tunnel from flowing down quickly to prevent a decrease in sunlight transmittance. Although it is blended with the synthetic resin, there is a problem that the temperature difference between the inside and outside of the house or tunnel becomes large and fog is generated in the vicinity of the inside surface. That is, the fog generated in this way not only causes the disease occurrence of the agricultural products to be cultivated,
Extra cost to dry wet crops,
Further, the outlook becomes worse, resulting in a decrease in work efficiency.

In order to solve such a problem, a method of using a fluorine-containing compound as an antifog agent in combination with an antifogging agent has been proposed (for example, Japanese Patent Publication No. 59-35573 and Japanese Patent Application Laid-Open No. 61-152).
No. 745), a satisfactory antifogging and antifog effect has not been obtained in practical use.

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention has been made in order to provide a surface modifier which imparts to a surface of an agricultural synthetic resin antifogging and fogproof properties which are sufficiently satisfactory for practical use.

Means for Solving the Problems That is, the present invention has the general formula (I): [Wherein Rf is a perfluoroalkenyl group C ₆ F ₁₁ or C
₉ F ₁₇ and R is an alkyl group having 1 to 18 carbon atoms which may have a branched chain or Wherein R ′ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms which may have a branched chain, and
Represents a number of 1 or 2, and m and n are each independently 0.
Alternatively, the present invention relates to an agricultural synthetic resin surface modifier containing a fluorine-containing aromatic carboxylic acid ester represented by a number of 1 to 30 (provided that m + n ≧ 1)].

In the above general formula (I), the perfluoroalkenyl group C ₆ F ₁₁ or C ₉ F ₁₇ is generally a residue derived from a dimer or trimer of hexafluoropropene, and R has a branched chain. There are also 1 to 1 carbon atoms
18 alkyl groups, preferably methyl, ethyl, dodecyl, octadecyl, etc. or (Wherein R'is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms which may have a branched chain, preferably a hydrogen atom, an octyl group, a nonyl group, etc.), and l is 1 or 2 And m and n each independently represent 0 or a number of 1 to 30, preferably 7 to 20 (provided that m + n
≧ 1).

Further, in the general formula (I), the ethylene oxide group and the propylene oxide group may be bonded in a block form, or both may be bonded randomly.

Among the fluorine-containing aromatic carboxylic acid esters represented by the general formula (I), particularly preferred esters are the following general formula (I
are represented by a) and (I b): (In the formula, Rf, R, m and n have the same meanings as described above) For example, the following compounds may be mentioned.

The method for producing the fluorine-containing aromatic carboxylic acid ester represented by the general formula (I) is not particularly limited, but the following two simple methods are exemplified.

The first method is the general formula (II): (Wherein Rf and l have the same meanings as defined above), for example, perfluoroalkenyloxy aromatic carboxylic acid chloride, such as p- (perfluorononenyloxy) benzoic acid chloride or 5- (perfluorononenyloxy) isophthalic acid. In the presence of a basic compound such as pyridine, triethylamine, dimethylaniline or the like, or an inorganic base such as potassium carbonate or sodium hydroxide or the like, the chloride is converted to the general formula (III): HO (CH ₂ CH ₂ O) nR ( III) (wherein R and n have the same meanings as defined above) and / or the general formula (IV): (Wherein R and m are as defined above).

The second method is the general formula (V): (Wherein Rf and l have the same meanings as defined above), a perfluoroalkenyloxy aromatic carboxylic acid represented by, for example, p- (perfluorononenyloxy) benzoic acid or 5- (perfluorononenyloxy) isophthalic acid is used as an acid catalyst, For example, in the presence of p-toluenesulfonic acid, concentrated sulfuric acid, concentrated hydrochloric acid, a strongly acidic ion exchange resin, etc., a polyethylene glycol monoether represented by the above general formula (III) and / or a polypropylene glycol monomonomer represented by the general formula (IV). It is a method of reacting with ether.

Two or more kinds of the fluorine-containing aromatic carboxylic acid ester represented by the above general formula (I) may be used in combination, if desired.

If desired, the agricultural synthetic resin surface modifier according to the present invention may be appropriately blended with an antifogging agent conventionally used in the art to enhance the antifogging effect.

Examples of such antifogging agents include sorbitan-based surfactants (eg, sorbitan monostearate, sorbitan monopalmitate, sorbitan monobehenate, etc.) and glycerin-based surfactants (eg, glycerin monolaurate, glycerin monopalmitate). , Glycerin monostearate, etc.), polyethylene glycol-based surfactants (eg, polyethylene glycol monostearate,
Examples thereof include polyethylene glycol monopalmitate), trimethylolpropane-based surfactants (eg, trimethylolpropane monostearate), pentaerythritol-based surfactants (eg, pentaerythritol monopalmitate), and the like.

The agricultural synthetic resin surface modifier according to the present invention may optionally further contain conventional additives such as UV absorbers, plasticizers,
Stabilizers, lubricants, antioxidants, colorants and the like may be added appropriately.

The surface modifier according to the present invention comprises a fluorine-containing aromatic carboxylic acid ester represented by the general formula (I) and an optional antifogging agent and other additives in a suitable solvent such as isopropyl alcohol, chloroform, methylene chloride, It may be prepared as a solution or dispersion in which carbon tetrachloride, Freon 113 or the like is dissolved or dispersed, and applied to the surface of the agricultural synthetic resin by spray coating, dip coating, roll coating, brush coating or the like.

In this case, the concentration of the fluorinated aromatic carboxylic acid ester is usually 0.01 to 3.0% by weight, preferably 0.1 to 2.0% by weight, and the concentration of the antifogging agent is usually 0.01 to 2.0% by weight, preferably 0.1 to 1.0%. % By weight.

Alternatively, the surface modifier according to the present invention may be used by kneading it with a base resin and other components and preparing a molding material such as a film or sheet from the kneaded product.

The base resin is exemplified by homopolymers or copolymers of monomers such as vinyl chloride, ethylene, propylene, acrylic acid ester, methacrylic acid ester, etc., but vinyl chloride resin, that is, polyvinyl chloride and vinyl chloride component 50 wt. % Copolymers, such as vinyl chloride, propylene, vinyl ethers, copolymers of one or more selected from the group consisting of acrylates and methacrylates with vinyl chloride, weather resistance, light transmission, strength and cost. Etc. are preferable.

The amount of the fluorine-containing aromatic carboxylic acid ester represented by the general formula (I) is usually 0.01 to 3.0 parts by weight, preferably 0.05 to 1.0 parts by weight, and 0.01 part by weight or less based on 100 parts by weight of the base resin. However, it is difficult to achieve the initial object of the present invention, and if it is blended in a too large amount, cloudiness will occur in the molded film, sheet, etc. and the transparency will be impaired, such being undesirable.

The amount of the above-mentioned antifogging agent is usually 1 to 5 parts by weight, preferably 1.5 to 3.0 parts by weight, based on 100 parts by weight of the base resin.

Furthermore, in addition to the above components, various additives for resins such as plasticizers (for example, phthalic acid derivatives such as di-n-octyl phthalate, di-2-ethylhexyl phthalate and diisodecyl phthalate, and diisooctyl isophthalate) may be added. Isophthalic acid derivative, adipic acid derivative such as di-n-butyl adipate, tricresyl phosphate, epoxidized soybean oil, etc., heat stabilizer (for example, zinc stearate, calcium stearate, barium stearate, phosphite ester, etc.) ), Lubricants (for example, stearic acid, polyethylene wax, etc.), ultraviolet absorbers (for example, benzotriazole, benzoate, benzophenone, cyanoacrylate, phenyl salicylate, etc.), colorants (for example, carbon black, phthalocyanine blue) , Titanium, etc.) and the like may be appropriately blended.

After kneading the above compounding ingredients with a compounding machine or a mixer such as a ribbon blender, a super mixer or a Banbury mixer, a molding method known per se, for example, a melt extrusion method, a calender method, a pressing method or a casting method, etc. It is possible to produce agricultural molding materials such as films and sheets.

In this case, the thickness of the molded film or sheet is not particularly limited, but for example, the thickness of the vinyl chloride resin film is preferably about 20 to 400 μm from the viewpoint of strength, transparency, workability and the like.

 Hereinafter, the present invention will be described with reference to examples.

Examples 1 to 9 Mixtures according to the formulations in Table 1 were heated to 160 ° C. 2
After kneading for 3 minutes using this roll, a film having a thickness of 100 μ was used with a press machine heated to 170 ° C. (Example 1), 2 (Example 2), 3 (Example 3), 4 (Example) Examples 4), 5 (Example 5), 6 (Example 6), 7 (Example 7), 8 (Example 8) and 9 (Example 9).

The anti-fogging property, the anti-fog property and the contact angle with water of these films were examined as follows, and the results are shown in Table-1.

(1) Evaluation of Antifogging Property 150 cc of warm water (50 ° C.) was placed in a beaker (300 cc), the mouth was covered with the above film, and the rubber was sealed with a rubber band. This sealed beaker was allowed to stand in a dryer at 50 ° C. for about 1 hour, then moved to a thermostatic chamber at 5 ° C., and after standing for 60 minutes, the water adhesion state on the inner surface of the film was visually observed.

The evaluation criteria of the antifogging property are as follows: 5: Water adheres in a film form, but no water droplets are observed; 4: Water adheres in a film form, but large water droplets are partially observed. 3: Water adheres in a film form, but large or small water droplets are seen, 2: Large water droplets and small water droplets are seen, 1: Small water droplets are attached to one side and the bottom of the beaker cannot be seen.

(2) Evaluation of fog resistance A frame was made using 1 cm square timbers, the ceiling was tilted at 30 °, the above films were attached to the side and ceiling, and the bottom was immersed in a water tank. After leaving it in a water bath for 2 days and night, it was transferred to a constant temperature chamber at 5 ° C., and 15 minutes later, the generation state of fog near the inner surface of the film was observed.

 The evaluation criteria for fog resistance are as follows: 5: No fog, 4: Slight fog, 3: Fog, 2: Slight fog, 1: Very thick Fog is generated.

(3) Measurement of contact angle with water The film used for the evaluation test of the antifogging property was dried, and this dried film was measured using a goniometer type G-1 type contact angle measuring instrument manufactured by Elma Optical Co., Ltd. The contact angle with water after 1 minute was measured.

In addition, compounds 1 to 9 in Table 1 represent the following compounds: Comparative Examples 1 and 2 According to Examples 1 to 9, films 1 '(Comparative Example 1) and 2' (Comparative Example 2) prepared according to the formulation of Table 1 were used as anti-fog properties, anti-fog properties and water. The contact angle was examined and the results are shown in Table-1.

Effects of the Invention By spreading a synthetic resin film or sheet coated with the surface modifier according to the present invention, or a synthetic resin film or sheet mixed with the surface modifier, in a cultivation facility such as a house or a tunnel On the basis of the excellent anti-fog and anti-fog effect, the above-mentioned conventional problems such as the occurrence of diseases of agricultural products to be cultivated are solved.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Fujito Nemoto 1-1 Oike-cho, Konishi-cho, Koga-gun, Shiga Within Neos Co., Ltd. (56) References Japanese Patent Publication Sho 60-17364 (JP, B2)

Claims (3)

[Claims] 1. General formula (I): [Wherein Rf is a perfluoroalkenyl group C ₆ F ₁₁ or C
₉ F ₁₇ and R is an alkyl group having 1 to 18 carbon atoms which may have a branched chain or Wherein R ′ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms which may have a branched chain, and
Represents a number of 1 or 2, and m and n are each independently 0.
Alternatively, a synthetic resin surface modifier for agriculture containing a fluorine-containing aromatic carboxylic acid ester represented by the formula 1 to 30 (provided that m + n ≧ 1)]. 2. A compound represented by the general formula (I) is represented by the general formula (I a): The agricultural synthetic resin surface modifier according to claim 1, which is a compound represented by the formula (wherein Rf, R, m and n are as defined above). 3. A compound represented by the general formula (I) is represented by the general formula (I b): The agricultural synthetic resin surface modifier according to claim 1, which is a compound represented by: