JP2862968B2 - Agricultural synthetic resin coating and anti-fog anti-fog agent - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an antifogging / misting agent for agricultural synthetic resin coating materials. More specifically, the present invention relates to a compound which imparts anti-fogging property and anti-frost property alone.

[Related Art] In recent years, crop cultivation in a house or a tunnel has been widely performed for the purpose of forcing cultivation of agricultural and horticultural crops and cultivation outside of the season. Examples of coating materials used in these facilities include plastic films such as polyethylene films and polyvinyl chloride films, and the latter is mainly used because of its excellent light transmittance, heat retention, weather resistance and the like.

However, since the surface of the polyvinyl chloride-based resin film is hydrophobic, water vapor is condensed on the film when the polyvinyl chloride-based resin film is spread, and the film covers the surface and becomes cloudy. This not only reduces the transmittance of sunlight but also causes troubles such as damage to crops caused by falling water droplets.

Conventionally, as a method of solving such a trouble, an antifogging agent (for example, sorbitan fatty acid ester,
Glycerin fatty acid ester) to impart hydrophilicity. As a result, the condensed water droplets are diffused on the film surface and uniformly wet the film and flow down, so that the surface can be maintained in a transparent state.

However, under the coating of a coating material containing such an antifogging agent,
Since the temperature difference between the inside and outside of the coating material increases, a phenomenon that fog is generated near the inner surface of the coating material is often observed. The cause of this fog event, which is common from late autumn to winter, is not clear, but the temperature and humidity inside the house or tunnel, the temperature of the soil inside the house or tunnel, the water content, the amount of solar radiation into the house or tunnel , The degree of hydrophilicity of the inner surface of the coating material is subtly affected, and the decrease in the humidity inside the house or tunnel that adheres to the surface of the coating material due to temperature changes and flows away does not occur smoothly,
It is presumed that some of the moisture becomes mist near the inner surface of the coating material.

In order to suppress such a fog generation phenomenon, Japanese Patent Laid-Open No. 55-91
No. 663, organosiloxane surfactants and JP-A-5
There are proposals such as a method of adding a fluorinated surfactant described in 7-14648 to a film, but none of them is sufficient to suppress the generation of fog, or even if they have an anti-fog effect. There is a drawback that the antifogging effect is not exhibited unless it is used in combination with another antifogging agent.

[Problems to be Solved by the Invention] The present invention has an effect of preventing fog in an agricultural house (fog prevention) and preventing fogging of a vinyl film (fog prevention) by a single compound. It is an object of the present invention to provide an anti-fog anti-fog agent for an agricultural synthetic resin coating material, and an agricultural synthetic resin coating material comprising a synthetic resin material to which the anti-fog anti-fog agent has been added.

Means for Solving the Problems The present inventors provide an agricultural synthetic resin coating material having both anti-fog properties and anti-fog properties by adding a single compound as described above. As a result, the present inventors have found that a special fluorine-containing compound having a structure completely different from those conventionally proposed is extremely effective, and have completed the present invention.

That is, the present invention provides an antifogging and antifog agent for a synthetic resin coating for agricultural use, characterized in that at least one of the fluorine-containing polyhydroxy compounds represented by the following general formula [1] or [2] is used as an active ingredient. And an agricultural synthetic resin coating comprising a synthetic resin material to which the anti-fog and anti-fog agent has been added. By adding at least one of the fluorine-containing polyhydroxy compounds represented by the following general formula [1] or [2], the antifogging property can be added to the agricultural synthetic resin coating material without using a conventional antifogging agent. It has become possible to impart anti-fog properties.

Wherein R ^f is a polyfluoroalkyl group having 3 to 21 carbon atoms, X is a linking group having a hydroxyl group or a linking group having a hydroxyl group and an etheric oxygen atom, and R ¹ and R ² have a hydroxyl group. An alkylene group having 1 to 10 carbon atoms which may be substituted; R ³ and R ^{4 each} represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a hydroxyl group; and R ⁵ has a hydroxyl group. And an alkylene group having 1 to 10 carbon atoms which may be substituted.

Examples of the fluorine-containing polyhydroxy compound represented by the general formula [1] or [2] include the following.

_{^{R f CH 2 CH (OH)}} CH 2 N (C 2 H 4 OH) 2) R f CH 2 CH (OH) CH 2 NHCH 2 CH (OH) CH 2 OH R f CH 2 CH (OH) CH 2 N _{(CH 2 CH (OH) CH} 2 OH) 2) R f C 2 H 4 OCH 2 CH (OH) CH 2 N (C 2 H 4 OH) 2 R ^f C ₂ H ₄ OCH ₂ CH (OH) CH ₂ NHC (CH ₂ OH) _{3 The} method for synthesizing the compound represented by the general formula [1] or [2] is not limited at all, but it can be produced as follows. is there.

That is, an epoxy compound having a polyfluoroalkyl group as exemplified in Formula [3], Formula [4] or Formula [5] and a hydroxyamine which is a primary amine or a secondary amine are dissolved in a solvent such as toluene. In the reaction.

Further, by subjecting a fluorine-containing hydroxy compound as a secondary amine and a chlorine-containing hydroquine compound such as ClCH ₂ CH (OH) CH ₂ OH (glycerol-α-monochlorohydrin) to a dehydrochlorination reaction with an alkali catalyst in dioxane. Third
A fluorinated polyhydroxy compound which is a secondary amine can be obtained.

The fluorinated polyhydroxy compound obtained above can exhibit the desired anti-fogging property and anti-fog property even when used alone or in combination of two or more.

The synthetic resin material constituting the agricultural synthetic resin coating material of the present invention generally includes a film-forming thermoplastic synthetic resin. Specifically, homopolymers of monomers such as vinyl chloride, ethylene, propylene, acrylate, and methacrylate or copolymers thereof, or copolymerizable with at least one of these monomers Copolymers with monomers (eg, vinyl acetate, vinylidene chloride, etc.), fluorine-containing resins, polyesters, polyamides, etc., and blends of these polymers can be used. Of these, weather resistance, light transmission, economy,
From the viewpoint of strength, vinyl chloride-based resins and ethylene-based resins are preferred, and polyvinyl chloride is most preferred.

The amount of the fluorinated polyhydroxy compound to be added to the synthetic resin material (hereinafter, also referred to as a base synthetic resin) in the present invention can be changed over a wide range depending on the type of the fluorinated polyhydroxy compound to be mixed, the type of the base synthetic resin, and the like. . Generally, 100 parts by weight of the base synthetic resin (however, excluding compounding agents such as a plasticizer, an anti-fogging agent, and a stabilizer. The same applies hereinafter)
It can be at least 0.01 part by weight, and the upper limit of the blending amount is not strictly limited, but if it is blended in an excessively large amount, bleed out or cloudiness may occur, so it is usually 2.0 parts by weight or less. Is enough. The preferred range of the amount is 0.02 to 1.0 part by weight per 100 parts by weight of the base synthetic resin.

The base synthetic resin constituting the agricultural synthetic resin coating material of the present invention may contain, if necessary, various usual additives such as a plasticizer, a lubricant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, and a dye. And the like can be contained in a usual amount.

For example, regarding the preferred soft vinyl chloride resin in the present invention, polyvinyl chloride having a degree of polymerization of 1,000 to 2,000
The plasticizer can be blended in 30 to 70 parts by weight with respect to 100 parts by weight.

Suitable plasticizers that can be used include phthalic acid derivatives such as di-n-octyl phthalate, bis-2-ethylhexyl phthalate, dibenzyl phthalate, diisodecyl phthalate, didodecyl phthalate and diundecyl phthalate, di-n-butyl adipate, Adipic acid derivatives such as dioctyl adipate, maleic acid derivatives such as di-n-butyl malate, citric acid derivatives such as tri-n-butyl citrate, itaconic acid derivatives such as monobutyl itaconate, oleic acid derivatives such as butyl oleate, Other examples include tricresyl phosphate, epoxidized soybean oil, and epoxy resin plasticizers.

Lubricants that can be included in the synthetic resin substrate, as a heat stabilizer, for example, polyethylene wax, bisamide, stearic acid, zinc stearate, barium stearate,
Examples include calcium stearate and barium ricinoleate. Examples of the ultraviolet absorber include benzotriazole-based, benzoate-based, benzophenone-based, cyanoacrylate-based, and phenyl salicylate-based ultraviolet absorbers. Examples of pigments and dyes include titanium oxide, silica, ultramarine, phthalocyanine blue, and the like.

These resin additives can be contained in a usual content, for example, a small amount of 5 parts by weight or less per 100 parts by weight of the synthetic resin base material.

In order to include the fluorine-containing polyhydroxy compound and various resin additives as necessary in the base synthetic resin, usual compounding techniques and mixing techniques such as a ribbon blender, a Banbury mixer, a super mixer, and other compounding machines and mixers And then forming a film. In order to form a synthetic resin into a film, a method known per se, for example, a melt extrusion method, a solution casting method, a calendar method, or the like may be employed.

When the thickness of the agricultural synthetic resin coating material of the present invention is too thin, the strength is insufficient and it is not preferable. Conversely, when it is too thick, it is formed into a film, and the subsequent handling (work of cutting the film and joining it into a house shape, (Including work to spread the house, etc.), it is preferable to set the range of 0.01 to 0.5 mm.

EXAMPLES <Production Example _{1: C 8 F 17 CH 2} CH (OH) CH 2 N (C 2 H 4 OH) 2 Synthesis> reflux condenser, a 300ml with suitable funnel, a stirrer 4
23.8 g (0.05 mol) of an epoxy compound represented by the formula [3] wherein R ^f is C ₈ F ₁₇ and 100 g of toluene were placed in a necked flask and dissolved by stirring at room temperature. After dropping 5.5 g (0.053 mol) of diethanolamine over 30 minutes, the temperature was raised to the reflux temperature of toluene, and the reaction was continued for 8 hours. After confirming that the conversion of the raw material epoxy compound was 98% or more, 110 ° C, 1mmHg
Then, toluene, residual diethanolamine and epoxy compound were distilled off. The weight of the obtained yellow solid is 27.6
g (94% yield).

<Production Example _{2: C 8 F 17 C 2} H 4 OCH 2 CH (OH) CH 2 NHC (CH 2 OH) Synthesis of _3> reflux condenser, suitable funnel, a 500ml equipped with a stirrer 4
23.8 g (0.05 mol) of the epoxy compound represented by the formula [5] wherein R ^f is C ₈ F ₁₇ and H ₂ NC (CH ₂ OH) ₃ (2
-Amino-2-hydroxymethyl-1,3-propanediol) (6.4 g, 0.053 mol) and methanol (250 g) were added, and the mixture was dissolved under stirring, followed by reaction under reflux of methanol for 8 hours. After confirming that the conversion of the epoxy compound was 98% or more, methanol and the remaining epoxy compound were distilled off at 110 ° C. and 1 mmHg. Excess H ₂ NC (CH ₂ OH) ₃ remaining in the white solid after distillation was removed by washing with water. The white solid obtained by filtration and drying was 30.4 g (95% yield).

<Production Example ^{_{3: R f C 2 H 4}} OCH 2 CH (OH) CH 2 N (CH 2 CHOH) CH 2 O
H) Synthesis of ₂ > 500 ml of 4 equipped with a reflux condenser, a funnel and a stirrer
An epoxy compound of the formula [5] (average molecular weight: 543) (27.2 g, 0.05 mol) and toluene (200 g) were put into a necked flask and dissolved by stirring. 4.8 g (0.053 mol) of H ₂ NCH ₂ CH (OH) CH ₂ OH (3-amino-1,2-propanediol) was added dropwise over 30 minutes, then the temperature was raised to the reflux temperature of toluene, and the reaction was continued for 8 hours. Was. After confirming that the conversion of the starting epoxy compound was 98% or more, toluene and the remaining epoxy compound were distilled off at 110 ° C. and 1 mmHg.

16.6 g (0.15 mol) of the reaction product after distillation and ClCH ₂ CH (OH) CH ₂ OH (glycerol-α-monochlorohydrin)
Dissolved in 200 g of 1,4-dioxane and 10% NaOH aqueous solution
After dropping 0 g (0.1 mol), the temperature was raised to 80 ° C and the reaction was carried out for 8 hours. After standing overnight, the lower layer was dissolved in ethyl acetate, washed with a separating funnel, and the ethyl acetate layer was dried over sodium sulfate. Ethyl acetate was distilled off to give a pale yellow solid 30 (yield
80%).

<Example> A synthetic resin film was prepared by converting an anti-fog anti-fog agent synthesized according to each of the production methods shown in Production Examples 1 to 3 and an anti-fog anti-fog agent synthesized in the same manner as in Production Examples 1 to 3. Was evaluated as a test film. Table 1 shows the results.

Film composition Polyvinyl chloride (degree of polymerization 1300) 100 parts by weight Dioctyl phthalate 45 parts by weight Tricresyl phosphate 3 parts by weight Ba-Zn liquid stabilizer 2 parts by weight Ba-Zn powdery stabilizer 1 part by weight Anti-fog Atomizer 0.5 parts by weight A mixture of the above composition is kneaded at 160-170 ° C., and
A thick film was produced.

評 価 Evaluation of anti-fogging property 150 ml of hot water at 75 ° C. is placed in a 300 ml beaker in a room at 25 ° C., and the opening of the beaker is sealed with the above-mentioned test film. After 5 minutes, the surface condition of the inner surface of the film is observed.
The evaluation criteria were the following five levels.

1. Water adheres to the film surface in the form of a film.

2. There are large water drops in a part.

3. There are large and small water droplets, but there are also film-like parts.

4. There are large and small water droplets and no film-like part.

5. Small water droplets adhere to one side and the bottom of the beaker is not visible.

霧 Evaluation of anti-fog properties A wooden board on all sides, a water surface in a water tank on the bottom, a fog observation box with a ceiling inclined and a test film stretched, were left in a water tank with a water temperature of 40 ° C at room temperature of 25 ° C for 48 hours. I do. While maintaining the water temperature at 40 ° C., the room temperature was lowered to 5 ° C., and after 1 hour, the state of fog generation near the surface of the test film on the water tank side was visually observed.
The evaluation criteria were the following four levels.

A. No fog is observed.

B. An extremely small amount of fog is observed.

C. Generation of fog is observed.

D. An extremely large amount of fog is observed.

Compounds 1 to 3 in Table 1 have the following structures. Here, is a compound produced in Production Example 1, is a compound produced in Production Example 3, and is a compound produced in Production Example 2, respectively.

C ₈ H ₁₇ CH (OH) CH ₂ N (C ₂ H ₄ OH) ₂ C ₁₀ F ₂₁ CH (OH) CH ₂ NHCH ₂ CH (OH) CH ₂ OH C ₆ F ₁₃ CH (OH) CH ₂ − − _{N (CH 2 CH (OH)} CH 2 OH) 2 C 8 F 17 C 2 H 4 OCH 2 CH (OH) CH 2 N (C 2 H 4 OH) 2 C 8 F 17 C 2 H 4 OCH 2 CH ( _{OH) CH 2 - -NHCH 2 CH} (OH) CH 2 OH R f C 2 H 4 OCH 2 CH (OH) CH 2 - -N (CH 2 CH (OH) CH 2 OH) 2 C 8 F 17 C 2 H ₄ OCH ₂ CH (OH) CH ₂ NHC (CH ₂ OH) ₃ [Effect of the Invention] The agricultural synthetic resin coating material containing the antifogging and antifog agent according to the present invention exhibits the following remarkable effects. However, its industrial utility value is extremely large.

The present invention has performance that conventional additives could not do. That is, the addition of a single compound (without the addition of a general-purpose antifogging agent) can impart excellent antifogging properties and antifogging properties to agricultural synthetic resin coatings.

────────────────────────────────────────────────── ⁶ Continuation of the front page (51) Int.Cl. ⁶ identification symbol FI C09K 3/18 103 C09K 3/18 103 (56) References JP-A-62-164764 (JP, A) JP-A-63-162760 (JP, a) JP Akira 64-14263 (JP, a) JP flat 2-69538 (JP, a) JP flat 3-215562 (JP, a) (58 ) investigated the field (Int.Cl. ⁶ , DB name) C08K 5/00-13/08 B01F 17/00-17/56 C09K 3/18 A01G 9 / 14,13 / 00-13/02

Claims (2)

(57) [Claims] 1. An antifogging and antifog agent for a synthetic resin coating material for agricultural use, comprising as an active ingredient at least one fluorine-containing polyhydroxy compound represented by the following general formula [1] or [2]. . R ^f —X—NH—CR ³ R ⁴ —R ⁵ OH [2] where R ^f is a polyfluoroalkyl group having 3 to 21 carbon atoms, X is a linking group having a hydroxyl group, or a hydroxyl group and an etheric group. A linking group having an oxygen atom, R ¹ , R ² is an alkylene group having 1 to 10 carbon atoms which may have a hydroxyl group, R ³ , R ⁴ has a hydrogen atom, or has a hydroxyl group; R ⁵ is an alkylene group having 1 to 10 carbon atoms which may have a hydroxyl group. 2. An agricultural synthetic resin coating material comprising a synthetic resin to which the antifogging and antifog agent for an agricultural synthetic resin coating material according to claim 1 is added.