JPH01193336A - Antifogging agent, antifogging synthetic resin film and method for suppressing fog using said agent or film - Google Patents

Abstract

PURPOSE:To provide the above antifogging agent containing a fluorine- containing ester compound having polyoxyethylene group, polyfluoroalkyl group and ester bond, having excellent antifogging property and compatibility to resins and useful for the treatment of agricultural house, etc. CONSTITUTION:The objective antifogging agent contains a fluorine-containing ester compound having polyoxyethylene group, polyfluoroalkyl group and ester bond. Preferably, the ester compound has >=2 polyoxyethylene groups wherein the terminal of at least one of said ethylene groups forms an ester hand with a monocarboxylic acid having polyfluoroalkyl group. Furthermore, the compound is preferably composed of (A) an ethylene oxide adduct of a 3-6-valent alcohol and/or an ethylene oxide adduct of an esterified product of said alcohol with a fatty acid and (B) a monocarboxylic acid having polyfluoroalkyl group and forming an ester bond with the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to a fog-proofing agent, a fog-proof synthetic resin film, and a fog-suppressing method using the same.

(Prior art) Vinyl chloride resins and I-lyolefin resins are relatively inexpensive and have excellent transparency, weather resistance, mechanical strength, etc., so they can be used to promote, semi-stimulate or suppress agricultural crops such as vegetables and fruit trees. It is used as a film for greenhouse cultivation.

The films used in these agricultural greenhouses tend to become cloudy when fog generated inside the greenhouse condenses on the inner surface of the film, that is, water droplets adhere to the inner surface of the film. This results in a decrease in sunlight transmittance, which adversely affects the growth of agricultural crops. In order to prevent this dew condensation, a surfactant (for example, sorbitan fatty acid ester, glycerin fatty acid ester, etc.), which is generally called an antifogging agent, is blended into the film base material.

However, although it is effective in preventing dew condensation on agricultural screens spread with synthetic resin films containing such antifogging agents, in the mornings and evenings from autumn to winter, when the temperature difference between the inside and outside of the film becomes large, the film is A large amount of fog is generated near the inner surface of the building, and countermeasures have become a problem.

This phenomenon of fog formation not only reduces the transmittance of sunlight and deteriorates the working environment for agricultural work, but also causes the occurrence of various diseases by wetting the crops grown in greenhouses, which has become a serious problem.

In order to prevent the occurrence of such fog,
No. 573 and Japanese Patent Application Laid-open No. 57-192445,
Cal with a fluoroalkyl group? Anionic fluorinated surfactants such as phosphoric acid and sulfonic acid, cationic fluorinated surfactants such as salts of amines having a fluoroalkyl group, alcohols having a fluoroalkyl group, and their ethylene oxide adducts. Nonionic fluorosurfactants or amphoteric fluorosurfactants such as betaine compounds having a fluoroalkyl group, sorbitan, norhytol, glycerin or their ethylene oxide, propylene oxide adducts, polyoxyethylene monoalkyl ethers, Agricultural antifogging agent containing a mixture of oxyethylene alkylarylru-thyl and a fluorine-free nonionic surfactant is kneaded into a film of vinyl chloride or polyolefin resin. Covering materials have been proposed.

(Problems to be Solved by the Invention) However, these antifogging agents have insufficient antifogging properties and poor compatibility with synthetic resins as described above, and as a result, transparent synthetic resins such as vinyl chloride resin Films to which they are added have the disadvantage that their transparency decreases when they are laminated.

Therefore, it is expected to develop a fog-proofing agent that has superior fog-proofing properties compared to conventional fog-proofing agents and also has excellent compatibility with synthetic resins.

[Structure of the invention]

(Means for Solving the Problems) In view of the above circumstances, the present inventors have conducted extensive research on fog-proofing agents that are highly compatible with synthetic resins and have excellent fog-proofing properties, and have found that polyoxyethylene Base? The present inventors have discovered that a fog preventer containing a fluorine-containing ester compound having a fluoroalkyl group-to-ester bond is effective in the above-mentioned respects, and have completed the present invention.

That is, the present invention provides a fog repellent characterized by containing a fluorine-containing ester compound having a polyoxyethylene group, a polyfluoroalkyl group, and an ester bond, and a fog preventive agent having a polyoxyethylene group, a monofluoroalkyl group, and an ester bond. Provided are a synthetic resin film containing a fluorine-containing ester compound, and a method for suppressing fog using a synthetic resin film containing a fluorine-containing ester compound having a preoxyethylene group, a polyfluoroalkyl group, and an ester bond. It is something.

The fluorine-containing ester compound used in the present invention may be any fluorine-containing ester compound having a polyoxyethylene group, a polyfluoroalkyl group, and an ester bond, but the number of preoxyethylene groups is 2 or more, A fluorine-containing ester compound having a structure in which at least one terminal thereof has an ester bond with a monocarboxylic acid having a polyfluoroalkyl group is preferable because it has excellent fog prevention properties.

Among them, compounds containing a structure in which an ethylene oxide adduct of a 13- to hexa-valent alcohol and/or an ethylene oxide adduct of a fatty acid partial ester of the alcohol and a monocarboxylic acid having a -lifluoroalkyl group are ester bonded. Fluorine ester compounds, especially those having 3 to 6 polyoxyethylene groups and having 8 to 22 carbon atoms
Particularly preferred are those having a fatty acid group of

Further, the method for producing the fluorine-containing ester compound used in the present invention is not particularly limited, and any method can be employed as long as it can obtain a compound having the structure described above.

Specifically, for example, an ethylene oxide adduct of an alcohol and/or an ethylene oxide adduct of a fatty acid ester of the alcohol (hereinafter collectively referred to as a -lyoxyethylene alcohol compound) and a polyfluoroalkyl group. Cal? A method of dehydrating and condensing fluorine-containing acid (hereinafter abbreviated as fluorine-containing cargonic acid) can be mentioned.
For this esterification, for example, the following fluorine-containing carboxylic acids (4) to (I) can be used. These fluorine-containing carboxylic acids may be used alone or as a mixture of two or more.

C.H.

(B) C3F1. CH2C00H (C') C6F1. CH2C0OH (6)C,F, ,CH2CH20CCH2CH2CO
OH(F5 C, F2n+1CH2CH20CCH2
A mixture of CH2COOHn=6.8.10 ()OC! 1F2n+, CM2CM2OCCH2CH2
Mixture of C0OHn=10.12.14 (■) CnF2n+, CH2CH20CCH2CH2C
00Hn=12.14.16 On the other hand, examples of polyoxyethylene alcohol compounds include those usually used as drip-proofing agents for synthetic resin films, such as the following compounds (1) to (a): can be used.

These polyoxyethylene alcohol compounds may be used alone or as a mixture of two or more.

(1) Polyoxyethylene (20 mol) Sorbitan (2) Polyoxyethylene (15 mol) Glycerin (3) Polyoxyethylene (6 mol) Sorbitan monolaurate (4) Polyoxyethylene (20 mol) Sorbitan monolaurate (5) f') Oxyethylene (6 mol) Solpitan monopalmi f-) (6)
Polyoxyethylene (20 mol) sorbitan mono/4
lumitate (7) /IJ oxyethylene (6 mol)
Sorbitan monostearate (8) Polyoxyethylene (20 mol) Sorbitan monostearate (9)
Polyoxyethylene (6 moles) Sorbitan monooleate α (J polyoxyethylene (20 moles) Sorbitan monooleate α1) Polyoxyethylene (30 moles)
Sorbitol tetraoleate (2) Polyoxyethylene (60 mol) Sorbitol tetraoleate (to) Polyoxyethylene (5 mol) Glycerin monooleate α4 Polyoxyethylene (15 mol) Glycerin monostearate (2) / IJ Oxy Ethylene (30 moles)
Sorbitan Monolaurate C1 → Polyoxyethylene (60 mol) Sorbitan Monostearate (Incorporated) Polyoxyethylene (20 mol) Sorbitol (To) 417 Oxyethylene (5 mol) Lauryl Ether (2) Polyoxyethylene (20 mol) Lauryl ether (a) Polyoxyethylene (5 mol) Nonylphenyl ether Cucafolioxyethylene (20 mol) Nonylphenyl ether (a) Polyoxyethylene (5 mol) Monostearate Polyoxyethylene (20 mol) Monostearate (c) Polyoxyethylene (5 mol) Monono J? Lumitate (c) Polyoxyethylene (15 mol) monooleate Among these polyoxyethylene alcohol compounds, ethylene oxide adducts of trivalent to hexavalent alcohols such as (1) to (b) and/or fatty acid moieties of the alcohols I dioxyethylene polyhydric alcohol compounds such as esterified ethylene oxide adducts are preferred.

Molar ratio during esterification of fluorine-containing caldicic acid and 4-lioxy-engineered tyrene alcohol compound (cal xyl group moles:
The appropriate molar ratio of hydroxyl groups is 1:4 to 1:1. Esterification is carried out by dehydrating and condensing a fluorine-containing caldic acid and a 4-lioxy-engineered tyrene alcohol compound using an esterification catalyst such as sulfuric acid in a toluene solvent using, for example, a Dean-Stark apparatus (decanter). Just go.

The fluorine-containing ester compound has a fluorine content of 10 to 3
Even if the fluorine content is within the range of 0% by weight, it is possible to obtain superior fogproofing properties compared to conventional fogging agents, but if the fluorine content is reduced to 3% by weight,
By setting the amount to 0 to 50 M%, it is possible to surprisingly improve the fog resistance without impairing the compatibility with the synthetic resin (that is, without impairing the transparency of the synthetic resin film).

The fluorine-containing ester compounds used in the present invention may be used alone or in combination of two or more. Further, the fluorine-containing ester compound may or may not contain unreacted raw materials, and may be used in combination with other antifogging agents.

The amount added is usually 0.0, O1 per 100 parts by weight of synthetic resin.
- 2 parts by weight, preferably 0.05 to 0.5 parts by weight.

As the base material for the synthetic resin film of the present invention, polyolefin resins such as vinyl chloride resins, polyethylene, and ethylene-vinyl acetate copolymer resins are generally used, and commonly used drip-proofing agents, plasticizers, and stabilizers are also used. , a lubricant, an antistatic agent, etc. may be added as appropriate.

The synthetic resin base material can be prepared by a known method, such as a T-die extrusion method,
It is formed into a film by the inflation method, calendar method, etc., and the film thickness is 0.05 to 0.3 m.
be made into

Next, the present invention will be explained in more detail based on reference examples and examples, but it goes without saying that these examples do not limit the present invention in any way.

In the following, all parts and parts are based on weight unless otherwise specified.

・Synthesis of fluorine-containing ester compounds (Reference Examples 1 to 24) Reference Example 1 The following raw materials were charged into a four-loaf flask equipped with a Dean Stark device (decanter), a cooling condenser, a thermometer, and a stirrer, and the toluene was refluxed. (approximately 110℃), 2
A time-dehydrated cotton mixture reaction was performed.

After the reaction, it was cooled to 60°C, and the calcium hydroxide was reduced to 15.9°C.
and stirred at 60° C. for 1 hour. After that, 200.9 g of toluene was added, and after stirring for 10 minutes, vacuum filtration was performed using a diatomaceous earth filter aid, and the F solution was desolventized with air blow at 80°C in a rotary evaporator. A fluorine-containing ester compound (1) was synthesized.

Hereinafter, a fluorine-containing ester compound (ID-(Peng) is used as reference example 1.
It was synthesized in the same way. The amounts of the fluorine-containing calgenic acid and polyoxyethylene polyhydric alcohol compound used in the synthesis of the fluorine-containing ester compounds of Reference Examples 2 to 24 are shown in Table 1.

The t used for toluene and 97% sulfuric acid are both 150 I and 2.51, respectively.

7/ 7/ / Examples 1 to 24 and Comparative Examples 1 to 7 The following film formulations were carried out as Examples 1 to 24.

- Film compound I vinyl chloride (lower = 1300) 100
dioctyl phthalate) (DOP)
45 parts tricresyl phosphate) (TCP)
3IISCa-Zn composite stabilizer
2 parts 4 xy resin
Part 2 phosphite chelator
0.5 parts fulvitan mono/4 lumitate
2 parts fluorine-containing ester compound
A 0.1 part thick film was prepared from 0.3 parts of the above blend using a calendar roll at 190°C. In addition,
As the fluorine-containing ester compounds, (1) to (XXIV) synthesized in Reference Examples 1 to 24 were used.

- Fog resistance test The film was subjected to a fog generation test under normal conditions and a fog generation test under severe conditions using the following methods.

Spread the film on the wooden frame with the sloping ceiling, except for the bottom.
Place it on a water bath at about 40℃ at room temperature, leave it for a specified time, then lower the room temperature to 10℃ (normal conditions) or 0℃ (severe conditions), drain the water from the water bath, and after a certain period of time, near the inner surface of the film. observed the fog that appeared.

〔Evaluation criteria〕

Degree of fog generation (near the inner surface of the film) 5... Very much 4... Much 3... Slightly much 2... Little 1... Very little 0... Hardly occurs Film transparency In addition, 10 films having a thickness of 0.1 am prepared in order to examine the compatibility with vinyl chloride resin were stacked to examine the transparency of the films.

[Transparency evaluation criteria]

0... Good transparency Δ... Slightly opaque ×... Opaque The results of the fog proofing and transparency tests are shown in Table 2 as Examples 1 to 24.

As Comparative Examples 1 to 7, in the case of a film having the same film formulation as Examples 1 to 24 but without adding a fluorine-containing ester compound (Comparative Example 1), the following [Note] was used instead of the fluorine-containing ester compound used in the present invention. l] In the case of films to which ordinary nonionic fluorosurfactants (a) to (・) shown in K were added (Comparative Examples 2 to 6), and unreacted mixtures [Note 2
1(f) (Comparative Example 7) was tested in the same manner, and the results are also shown in Table 2.

[Note 1] 2H5 0■ (@) C, F,, Cl2CH20 (CH2CH20
) 26H [Note 2] / /'' / / , 7/ /' , / 2, / / As is clear from Table 2, the films of Examples 1 to 12 using fluorine-containing ester compounds with low fluorine content had the same properties. Example using a fluorine-containing ester compound with a high fluorine content, which has excellent transparency and fog-proofing properties compared to the films of Comparative Examples 2 to 6, which used a nonionic fluorine-based surfactant with an equivalent or higher fluorine content. It is recognized that the films of Nos. 13 to 24 have extremely excellent anti-fog properties even under severe conditions without any loss in transparency as compared to the films of Examples 1 to 12.

Furthermore, in Comparative Example 7, the fog-proofing effect of (f) shown in [Note 2] was exemplified. Example 1 of the present invention uses the reactant of [Note 2''] (f), and even when compared with Comparative Example 7, it is recognized that the anti-fog properties are significantly superior.

From the above comparative experiments, it is understood that the structural characteristics of the fluorine-containing ester compound have a significant influence on the fog prevention properties.

The reason for this is not clear, but the fluorine-containing ester compound used in the present invention is structurally similar to fatty acid monoester of sorbitan or its ethylene oxide adduct, which is commonly used as a drip-proof agent. This is thought to be due to the fact that when kneaded into vinyl chloride resin, etc., it efficiently coordinates with the drip-proofing agent on the film surface.

〔Effect of the invention〕

The specific fluorine-containing ester compound used in the present invention is
It has surprising performance in that it has excellent fog prevention properties and good compatibility with resins compared to conventionally used nonionic fluorosurfactants.

The greenhouse, tunnel, etc. in which the synthetic resin film containing the fluorine-containing ester compound used in the present invention is spread effectively suppresses the generation of fog near the inner surface of the film, and almost completely eliminates the fog. Occurrence can be prevented. Therefore, the synthetic resin film of the present invention exhibits an extremely excellent effect on reducing the transmittance of sunlight caused by the formation of fog and the occurrence of disease in agricultural crops, and can greatly contribute to increasing the yield of agricultural facilities. can.

/

Claims (1)

[Scope of Claims] 1. An antifog agent characterized by containing a fluorine-containing ester compound having a polyoxyethylene group, a polyfluoroalkyl group, and an ester bond. 2. It is characterized by containing a fluorine-containing ester compound having two or more polyoxyethylene groups, in which the terminal of at least one polyoxyethylene group is ester bonded to a monocarboxylic acid having a polyfluoroalkyl group. Anti-fog agent. A fluorine-containing ester compound in which an ethylene oxide adduct of a trivalent to hexavalent alcohol and/or an ethylene oxide adduct of a fatty acid partial ester of the alcohol and a monocarboxylic acid having a polyfluoroalkyl group are ester bonded. An antifog agent characterized by containing. 4. The antifogging agent according to claim 3, wherein the number of polyoxyethylene groups in the fluorine-containing ester compound is 3 to 6. 5. The antifogging agent according to claim 3 or 4, wherein the fatty acid group in the fluorine-containing ester compound is a fatty acid group having 8 to 22 carbon atoms. 6. The fluorine atom content in the fluorine-containing ester compound is 1
The antifogging agent according to claim 3, 4 or 5, which is 0 to 50 weight percent. 7. A synthetic resin film containing a fluorine-containing ester compound having a polyoxyethylene group, a polyfluoroalkyl group, and an ester bond. 8. The fluorine-containing ester compound has two or more polyoxyethylene groups, and the terminal of at least one polyoxyethylene group is ester-bonded with a monocarboxylic acid having a polyfluoroalkyl group. 8. The film according to claim 7. 9. The fluorine-containing ester compound is formed by forming an ester bond between an ethylene oxide adduct of a trivalent to hexavalent alcohol and/or an ethylene oxide adduct of a fatty acid partial ester of the alcohol and a monocarboxylic acid having a polyfluoroalkyl group. The film according to claim 8, which is a fluorine-containing ester compound. 10. The film according to claim 8 or 9, wherein the number of polyoxyethylene groups in the fluorine-containing ester compound is 3 to 6. 11. Claim 8, 9 or 10, wherein the fatty acid group in the fluorine-containing ester compound is a fatty acid group having 8 to 22 carbon atoms.
The film mentioned. 12. The fluorine atom content in the fluorine-containing ester compound is
12. The film of claim 8, 9, 10 or 11, wherein the amount is 10 to 50 weight percent. 13. The content of the fluorine-containing ester compound is higher than that of the synthetic resin 1
Claim 8: 0.01 to 2 parts by weight per 00 parts by weight
, 9, 10, 11 or 12. 14. The film according to claim 8, 9, 10, 11, 12, or 13, wherein the synthetic resin is one selected from polyethylene, ethylene-vinyl acetate copolymer resin, and vinyl chloride resin. 15. A fog suppression method characterized by using a synthetic resin film containing a fluorine-containing ester compound having a polyoxyethylene group, a polyfluoroalkyl group, and an ester bond. 16. The fluorine-containing ester compound has two or more polyoxyethylene groups, and the terminal of at least one polyoxyethylene group is ester bonded to a monocarboxylic acid having a polyfluoroalkyl group. 16. The method of claim 15. 17. The fluorine-containing ester compound is formed by forming an ester bond between an ethylene oxide adduct of a trivalent to hexavalent alcohol and/or an ethylene oxide adduct of a fatty acid partial ester of the alcohol and a monocarboxylic acid having a polyfluoroalkyl group. 17. The method according to claim 16, wherein the fluorine-containing ester compound is a fluorine-containing ester compound. 18. The method according to claim 17, wherein the number of polyoxyethylene groups in the fluorine-containing ester compound is 13 to 6. 19. The method according to claim 17 or 18, wherein the fatty acid group in the fluorine-containing ester compound is a fatty acid group having 8 to 22 carbon atoms. 20. The fluorine atom content in the fluorine-containing ester compound is
20. A method according to claim 17, 18 or 19, wherein the amount is 10 to 50 weight percent. 21. The content of the fluorine-containing ester compound is
Claim 1: 0.01 to 2 parts by weight per 00 parts by weight
7, 18, 19 or 20. 22. The method according to claim 17, 18, 19, 20 or 21, wherein the synthetic resin is one selected from polyethylene, ethylene-vinyl acetate copolymer resin and vinyl chloride resin.