KR101319085B1 - Novel nonionic surfactant and fog-preventive agent - Google Patents

Abstract

The present invention is a group represented by formula (I): C ₆ F ₁₃ (CH ₂ ) _n -CH (OH) CH ₂ -at one end of (a) polyethylene glycol (PEG) having an average molecular weight of 250 to 550. (F1 group) or formula (II): A group (F2 group) represented by C ₆ F ₁₃ (CH ₂ ) _n -CH (CH ₂ OH)-(wherein n represents 1 to 10) is added. The molar ratio of the single end adduct, (b) the end end adduct in which the F1 group or the F2 group is added to the end of the PEG, and (c) the unreacted PEG is 50 to 90: 3 to 30: 0 to 30 ( The fluorine-containing polyether composition whose total of (a), (b) and (c) is 100) is provided. The composition exhibits excellent anti-corrosion properties and is used as an anti-foaming agent for agricultural films with a low load on the environment. Moreover, it is excellent in surface tension fall ability and is used also as a nonionic surfactant.

Description

New Nonionic Surfactants and Antifoams {NOVEL NONIONIC SURFACTANT AND FOG-PREVENTIVE AGENT}

FIELD OF THE INVENTION The present invention relates to nonionic compounds based on fluorine-containing epoxides and low surface tensioning agents containing such compounds, in particular agricultural film preventive agents.

Fluorine-containing compounds effective for low surface tension of aqueous solutions and various organic solvents have been used as surfactants, additives to paints, various penetrants, leveling agents, agricultural film spraying agents and the like. An advantage of the fluorine-containing surfactant is that the surface tension of the mother solution is reduced by the addition of an extremely small amount compared to the hydrocarbon-based surfactant.

Conventionally, the polyfluoroalkyl group which is used abundantly in such a fluorine-type surfactant generally contained the C8 or more perfluoroalkyl group (Rf group) (refer Japanese Unexamined-Japanese-Patent No. 57-136534 etc.).

By the way, the compound containing the perfluoroalkyl group (Rf group) of 8 or more carbon atoms obtained by telomerization is abbreviated as perfluoro- octanoic acid (Hereinafter, "PFOA") by decomposing or metabolizing a telomer. EPA (U.S. Environmental Protection Agency) proclaimed that it is likely to produce (see EPA OPPT FACT SHEET April 14, 2003 (http://www.epa.gov/opptintr/pfoa/pfoafacts.pdf)).

In addition, EPA announced a strengthening of the scientific investigation of the PFOA (EPA report "PRELIMINARY RISK ASSESSMENT OF THE DEVELOPMENTAL TOXICITY ASSOCIATED WITH EXPOSURE TO PERFLUOROOCTANOIC ACID AND ITS SALTS" (http://www.epa.gov/opptintr/pfoa/). pfoara.pdf), which poses a concern for the PFOA's environmental load.

Therefore, in recent years, an attempt has been made to use a compound of a short-chain Rf group for the purpose of reducing the load on the environment (see Japanese Patent Laid-Open No. 2006-219586, etc.). It is considered to suppress this.

On the other hand, in order to ensure the humidity indispensable for the growth of cultivated crops, fog is generated because high humidity is maintained in the plastic house. This fog is considered to be closely related to the quality of pests or crops of cultivated crops and to be avoided as much as possible in greenhouse cultivation.

Fog is generated by condensation of water vapor in the greenhouse, and occurs frequently in autumn, winter, morning and evening when the temperature difference between the greenhouse and the greenhouse changes rapidly. As a large use of a nonionic fluorine-containing surfactant, there exists a use (henceforth a "waterproofing agent") which incorporates an agricultural film and suppresses generation | occurrence | production of the fall and winter mist in a plastic house. Here, when adding and mixing surfactant in the raw material resin of a film, after "internal addition", when adding and mixing in film shape, it means adding in resin. Also in the use of this antiseptic agent, the compound containing Rf group of 8 or more carbon atoms has been used conventionally as surfactant (refer Japanese Unexamined-Japanese-Patent No. 59-093739 etc.). Therefore, the problem of PFOA generation also exists in the use of an antifog additive.

Japanese Patent Laid-Open No. 57-136534 Japanese Patent Laid-Open No. 2006-219586 Japanese Patent Laid-Open No. 59-093739

An object of this invention is to provide the composition with the low environmental load which suppressed generation | occurrence | production of PFOA, the provision of the antirust agent of the agricultural film containing the said composition, and the provision of surfactant containing the said composition.

As mentioned above, the compound which has conventionally been used as a fluorine-based surfactant has been used as a fluorine-containing group having a Cf or more Rf group. These Rf groups are usually derived from telomers produced by telomerization of tetrafluoroethylene as in the following formula, and most of them are mixtures of compounds having 8, 10, and 12 carbon atoms in terms of their production advantages and costs.

CF ₃ CF ₂ -I + nCF ₂ = CF ₂ → CF ₃ CF _2- (CF ₂ CF ₂ ) _n -I

In order to avoid the PFOA problem, even in a compound related to a surfactant, it is necessary to develop a surfactant having a low carbon number Rf group as a raw material.

Similarly, it is necessary to develop a spinning agent containing a surfactant having a low carbon number Rf group as a raw material.

That is, in the agricultural film, when the anti-corrosive agent is incorporated into the resin and molded into a film shape, it is necessary to be able to bleed out to the surface over time and modify the surface. Since a fluorine compound is incompatible with water and a general hydrocarbon, and it does not melt | dissolve easily, when a fluorine compound is internally shape | molded by resin and it is shape | molded, it has the property to bleed out on the surface with time. Therefore, when a very small amount is added to the resin, there is a feature that the fluorine compound is exposed to the surface to perform surface modification.

Although surface modification specifically refers to water / oil repellency and antifouling property, it is said that the charging property of a fluorine compound (Rf group) affects an agricultural film. Fog is the gathering of water vapor, and the nuclear material is dust and is positively charged. Since the Rf group of the antifog agent bleeding out on the film is negatively charged, it adsorb | sucks a fog on a film by attracting each other electrically.

On the other hand, an agricultural film is mix | blended with antifog additives (sorbitan fatty acid ester, glycerin fatty acid ester, polyhydric alcohol, nonionic surfactant derived from fatty acid, and alkylene oxide) separately, and these hydrophilize the film surface. Therefore, the mist adsorbed to the film surface by the fluorine-based surfactant flows down the hydrophilized film surface. By the antifog, the mist adsorbed on the film surface does not condense on the film. In the case of dew condensation, the surface of the film becomes cloudy, the transmission of sunlight is insufficient, and a problem arises in the growth of crops. In agricultural and horticultural vinyl houses, fluorine-based surfactants and hydrocarbon-based antifogs are usually used in combination to prevent the generation of fog and to prevent the generation of fog due to condensation.

Therefore, the following items are mentioned as a performance calculated | required by the fluorine-type surfactant as a spinning agent.

(A) Having a negatively charged Rf group and having a large amount of fluorine.

(B) Do not inhibit the hydrophilicity of the film surface, or the thing itself can contribute to hydrophilization.

(C) Solubility in water is small. High solubility in water results in the loss of the bleed-out spinning agent together with the water droplets agglomerated on the film.

(D) It has a certain heat resistance (heat of 150 ° C to 250 ° C is generated during film processing).

In order to develop a waterproofing agent that does not contain the PFOA problem, it is necessary to use an Rf group having 6 or less carbon atoms and satisfy the performance equal to or higher than the existing waterproofing agent. Although Rf groups having 6 or less carbon atoms have been considered to have a low amount of fluorine compared to conventional Rf groups having 8 or more carbon atoms, it is thought that sufficient negative charge amount cannot be secured. However, the present inventors have diligently studied to satisfy particular requirements. In the case of using a waterproofing agent containing an Rf group having 6 or less carbon atoms, it has been found to satisfy the same or better performance as the existing waterproofing agent, and the present invention has been reached.

That is, the present invention relates to a fluorine-containing polyether composition containing a nonionic compound derived from a raw material which does not generate PFOA.

The present invention also relates to an agricultural film anticorrosive containing the fluorine-containing polyether composition.

The present invention also relates to a nonionic surfactant containing the fluorine-containing polyether composition.

More specifically, the present invention is an epoxy compound having an Rf group having 6 carbon atoms (hereinafter sometimes abbreviated as "fluorine-containing C6 epoxide") as a raw material which does not generate PFOA, and a polyethylene having a nonionic hydrophilic group. The problem was solved by reacting glycol (hereinafter sometimes abbreviated as "PEG") to obtain a fluorine-containing nonionic fluorine-containing polyether composition.

That is, the present invention,

(a) at one end of polyethylene glycol having an average molecular weight of 250 to 550,

Formula (I): a group represented by C ₆ F ₁₃ (CH ₂ ) _n -CH (OH) CH _2- (F 1 group) or

Formula (II): group represented by C ₆ F ₁₃ (CH ₂ ) _n -CH (CH ₂ OH)-(F2 group)

(Wherein n represents 1 to 10)

Terminal adjuncts with the addition of

(b) a sock end adduct having F1 or F2 groups added to the sock end of polyethylene glycol, and

(c) Sox-based hydroxyl group polyethylene glycol

The present molar ratio relates to a fluorine-containing polyether composition wherein 30 to 95: 2 to 40: 0 to 40 (the total of (a), (b) and (c) is 100).

Here, the molar ratio of (a) and (b) and (c) is preferably 50 to 90: 3 to 30: 0 to 30 (the sum of (a) and (b) and (c) is 100). It may be.

The present invention also provides the fluorine-containing polyether composition,

Formula (III):

Wherein n is the same as the above, and is a reactant of the fluorine-containing C6 epoxide represented by the sock end hydroxyl group polyethylene glycol,

Single end adduct (a) is a 1: 1 molar ratio adduct of fluorine-containing C6 epoxide and polyethylene glycol,

The sock end adduct (b) is a 2: 1 molar ratio adduct of fluorine-containing C6 epoxide and polyethylene glycol, and

It relates to a fluorine-containing polyether composition wherein the sock end hydroxyl group-type polyethylene glycol (c) is unreacted polyethylene glycol.

The present invention also relates to an agricultural film anticorrosive agent comprising the fluorine-containing polyether composition.

The present invention also relates to an agricultural film containing the antifoaming agent.

The present invention also relates to a low surface tension nonionic surfactant comprising the fluorine-containing polyether composition.

The present invention also relates to a method for producing a fluorine-containing polyether composition by reacting the fluorine-containing C6 epoxide and the sock end hydroxyl group-type polyethylene glycol in a molar ratio of 0.7: 1 to 1.3: 1.

In the fluorine-containing polyether composition of the present invention, the problem of PFOA generation is not latent and the load on the environment is low. Moreover, the fluorine-containing polyether composition of this invention can suppress the generation | occurrence | production of the fog in a plastic house efficiently in autumn and winter by internally attaching (or externally attaching) an agricultural film to the agricultural film. In addition, the fluorine-containing polyether composition of the present invention is excellent in the ability to lower the surface tension, and provides a nonionic surfactant used in a wide range of applications.

Hereinafter, the present invention will be described in detail.

The fluorine-containing polyether composition of the present invention,

Formula (III):

In the formula, n is the same as described above, hereinafter, a mixture of a fluorine-containing C6 epoxide and a nonionic compound that can be produced by reaction with PEG having an average molecular weight of 250 to 550. Hereinafter, there is a case where the notation C6 fluorinated epoxide formula (III) with _{C 6 F 13 (CH 2)} n -CH (O) CH 2.

The reaction can be carried out by a conventional method, for example, using boron trifluoride (BF ₃ -OEt ₂ ) as a catalyst.

The reaction is:

a C ₆ F ₁₃ (CH ₂ ) _n -CH (O) CH ₂ + b HO- (CH ₂ CH ₂ O) _m -X → fluorine-containing polyether composition

(Wherein a is the number of moles of the raw material fluorine-containing C6 epoxide, b is the number of moles of the raw material PEG, X is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (preferably a methyl group), and m represents 1 to 12) Can be represented by Here, X is preferably a hydrogen atom.

In order to obtain "one-terminal adduct (a)" of the present invention, when the terminal X of PEG is a methyl group, for example, when the fluorine-containing C6 epoxide of the raw material disappears at a molar ratio of a: b = 1: 1 When the reaction is carried out until, the compound (called "one end adduct (a)") to which the Rf group was added to the one end of PEG completely can be obtained. In this case, the other end of (a) is a methyl group.

On the other hand, when the terminal X of PEG is a hydrogen atom (so-called hydroxyl group PEG), the fluorine-containing C6 epoxide may react with the hydroxyl group of the PEG terminal, and thus, a: b = 2: 1 in the above reaction formula. By reacting until the fluorine-containing C6 epoxide of a raw material disappears by molar ratio, the compound (referred to as "terminal end adduct (b)") to which the Rf group was added to the sock end of PEG completely can be obtained.

The fluorine-containing polyether composition of the present invention can be produced by mixing (a) and (b) obtained above and the sock end hydroxyl group-type polyethylene glycol (c) in a predetermined molar ratio.

On the other hand, when the terminal X of PEG is a hydrogen atom, the fluorine-containing C6 epoxide and the sock end hydroxyl group PEG are represented by the above reaction in a molar ratio of less than a: b = 2: 1, for example a: b = 1: 1. In the case where the fluorine-containing C6 epoxide of the raw material is reacted until the phosphorus molar ratio disappears, there is a probability that the single-end adduct (a) (the other end in this case is a hydrogen atom), the sock end adduct (b), and A fluorine-containing polyether composition in a predetermined proportion of unreacted PEG (c) is obtained. This embodiment is preferable as the composition of the present invention, and also as a production method, a fluorine-containing polyether composition containing the components (a), (b) and (c) in a predetermined molar ratio is preferably obtained at once.

Specifically, the terminus adduct mentioned here is

C ₆ F ₁₃ (CH ₂ ) _n -CH (OH) CH ₂ -O- (CH ₂ CH ₂ O) _m -X,

C ₆ F ₁₃ (CH ₂ ) _n -CH (CH ₂ OH) -O- (CH ₂ CH ₂ O) _m -X

(n and X are the same as above), and the sock end adduct is specifically,

C ₆ F ₁₃ (CH ₂ ) _n -CH (OH) CH ₂ -O- (CH ₂ CH ₂ O) _m -CH ₂ CH (OH)-(CH ₂ ) _n C ₆ F ₁₃ ,

C ₆ F ₁₃ (CH ₂ ) _n -CH (OH) CH ₂ -O- (CH ₂ CH ₂ O) _m -CH (CH ₂ OH)-(CH ₂ ) _n C ₆ F ₁₃ ,

C ₆ F ₁₃ (CH ₂ ) _n -CH (CH ₂ OH) -O- (CH ₂ CH ₂ O) _m -CH ₂ CH (OH)-(CH ₂ ) _n C ₆ F ₁₃ ,

C ₆ F ₁₃ (CH ₂ ) _n -CH (CH ₂ OH) -O- (CH ₂ CH ₂ O) _m -CH (CH ₂ OH)-(CH ₂ ) _n C ₆ F ₁₃

to be.

Here, in the above formula, it is particularly preferable that n = 1. As a single terminal adduct, the case where X = hydrogen atom is preferable.

In the fluorine-containing polyether composition of the present invention, the molar ratio of single end adduct (a): both end adducts (b): unreacted PEG (c) is 30 to 95: 2 to 40: 0 to 40. (the sum of (a) and (b) and (c) is 100), 50 to 90: 3 to 30: 0 to 30 (the sum of (a) and (b) and (c) is 100), preferably 60 to 80:10 to 20: 0 to 20 (the sum of (a), (b) and (c) is 100). This molar ratio is the range which has the outstanding anti-fog property when using the said fluorine-containing polyether composition as a anti-foaming agent. This molar ratio is also a range in which the fluorine-containing polyether composition exhibits excellent low surface tension. In addition, the presence molar ratio of a fluorine-containing polyether composition can be confirmed by analyzing by LC-MS etc.

In the fluorine-containing polyether composition of the present invention, as described above, a single end adduct and a sock end adduct are prepared respectively, PEG corresponding to the unreacted powder is added, and a mixture of the molar ratios present in the above range It can manufacture by adjusting as much as possible.

Preferably, the fluorine-containing polyether composition of the present invention is reacted with a fluorine-containing C6 epoxide using a sock end hydroxyl group PEG, wherein X is an H atom, and the composition of the fluorine-containing polyether composition is By controlling the reaction as much as possible, the fluorine-containing polyether composition of the present invention can be produced. The molar ratio can be controlled by the molar ratio of the fluorine-containing C6 epoxide to PEG, the amount of the catalyst, the reaction temperature, the reaction time and the like. Among these factors, the main factor that determines the molar ratio present in the fluorine-containing polyether composition is the input molar ratio of fluorine-containing C6 epoxide to PEG. The input molar ratio of fluorine-containing C6 epoxide to PEG is 0.7 to 1.3, preferably 0.8 to 1.1, particularly preferably 1.0.

PEG used by this invention has the role which bears the hydrophilic group of the fluorine-containing polyether composition of this invention. As PEG, as mentioned above, a sock end hydroxyl type is especially preferable.

About PEG, since it is preferable that it is a liquid at normal temperature on handling, the average molecular weight is about 200-1000. When the average molecular weight is 1000 or more, PEG becomes a solid, the mobility in the polymer film is lowered, the bleed-out property is lowered to the surface, and the solubility in water of the reactant with the fluorine-containing C6 epoxide is excessively increased. As a result, it is difficult to use the antifouling agent. When the average molecular weight of PEG becomes 200 or less, since the content of fluorine in a molecule | numerator becomes relatively large and it shows water repellency when added to an agricultural film, it is unpreferable.

More preferably, the average molecular weight of PEG is about 250-550. When the average molecular weight is less than 250, the thermogravimetric decrease in the temperature range (usually 150 ° C to 250 ° C) for molding the resin into a film increases. When the average molecular weight exceeds 550, the solubility in water of the reactants with the fluorine-containing C6 epoxide increases, and the durability decreases. The range with especially preferable average molecular weight of PEG is 300-500.

The reaction of the fluorine-containing C6 epoxide with the sock end hydroxyl group PEG is carried out using a catalyst and, optionally, a solvent, under heating to a temperature range of 30 ° C to 150 ° C, preferably 50 ° C to 120 ° C, Is carried out. Suitable catalysts include metal halides of periodic groups Groups 12-15 and 8, such as ZnCl ₂ , AlCl ₃ , SnCl ₄ , SbCl ₅ , FeCl ₃ , BF ₃ (complex with ether or alcohol), sulfuric acid, NaHSO ₄ Acid catalysts such as these may be used. Particularly preferably used catalyst is BF ₃ (complex with ether or alcohol) in view of high reaction rate and few by-products. The amount of the catalyst used is usually 0.01 to 2% by weight, preferably 0.5 to 1.0% by weight based on the weight of the fluorine-containing C6 epoxide. The reaction solution is analyzed by gas chromatography, thin layer chromatography, liquid chromatography, or the like, and the reaction is carried out at the point of time when the fluorine-containing C6 epoxide of the raw material disappears. Although reaction time in particular is not restrict | limited, It is the range of 1 hour-24 hours normally, Preferably it is 3 hours-12 hours in view of reaction rate, removal of reaction heat, etc.

Next, the antistatic agent of this invention is demonstrated.

The antistatic agent of this invention contains the said fluorine-containing polyether composition of this invention. In the fluorine-containing polyether composition, the molar ratio of single end adduct: end end adduct: unreacted PEG is 50 to 90: 3 to 30: 0 to 30 (total 100), as described above. Is 60 to 80:10 to 20: 0 to 20 (total 100), and the molar ratio is in a range having excellent anti-fogging properties when the fluorine-containing polyether composition is used as the anti-corrosive agent.

The said anti-corrosive agent is used internally in an agricultural film. That is, after adding, mixing, and melting the said anti-rust agent to agricultural film base resins, such as polyvinyl chloride resin mentioned later, it can process into a film by a conventional method and can be made into an agricultural film.

0.05-2 weight part is preferable with respect to 100 weight part of agricultural film base resins, and, as for the addition amount of the antistatic agent of this invention, 0.1-0.5 weight part is more preferable. If it is less than 0.05 part by weight, a sufficient anti-corrosion effect may not be exhibited. If it is more than 2 parts by weight, the film becomes cloudy or the surface becomes sticky due to bleed-out, and dust and dirt easily adhere to it.

It is preferable to use together the antifogging agent of this invention with an antifogging agent. As the antifogging agent to be used in the present invention, any antifogging agent generally used may be used. Examples thereof include sorbitan fatty acid esters, glycerin fatty acid esters, polyhydric alcohols and nonionic surfactants derived from fatty acids and alkylene oxides. Can be. For example, as esters of sorbitan and higher fatty acids having 12 to 22 carbon atoms, esters of glycerin and higher fatty acids having 12 to 22 carbon atoms, or alkylene oxide adducts thereof, for example, sorbitan monolaurate and sorbitan mono Sorbitan compounds such as palmitate, sorbitan monostearate, sorbitan monooleate or their polyethylene oxide adducts, glycerin monolaurate, glycerin monopalmitate, glycerin monostearate, glycerin monooleate or their poly Glycerin type compounds, such as an oxyethylene adduct, are mentioned. 0.3-3 weight part is preferable with respect to 100 weight part of agricultural film base resins, and, as for the addition amount of these antifog additives, More preferably, it is 0.5-2 weight part.

As an agricultural film material which can be used for this invention, since it has the film formation ability which can be melt-molded at about 150-250 degreeC generally, it can use whatever it is generally used for agricultural coating materials. For example, vinyl chloride resins, such as vinyl chloride resin, ethylene resins, such as polyethylene and an ethylene-vinyl acetate copolymer, propylene resin, etc. are mentioned as a typical thing, Preferable things are vinyl chloride resin and ethylene resin, Particularly preferred is vinyl chloride resin. However, the synthetic resin in the present invention is not limited to these resins.

Moreover, the agricultural film of this invention has various resin additives normally used as needed, for example, a lubricating agent, an antistatic agent, a weather resistance improving agent (ultraviolet absorber, a hindered amine light stabilizer, etc.), a plasticizer, antioxidant (heat stabilizer). And dyes and pigments can be blended in an additive amount of the degree normally used. Thereby, the effect of this invention is not impaired and neither the function of each of the various resin additives is impaired.

The agricultural film of the present invention can also be produced by a known method, for example, extrusion method (T die extrusion, inflation molding method, etc.), calender roll molding method, etc., wherein the film thickness is 20 to 1000 micrometers, preferably Is adjusted to 50 to 300 micrometers.

Next, the nonionic surfactant of this invention is demonstrated. The nonionic surfactant of this invention contains the said fluorine-containing polyether composition of this invention, and is excellent in the fall ability of surface tension. Therefore, it can be used also for the use of additives, such as a foaming agent, paint, etc., various penetrants, and a leveling agent, for example.

EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to this.

[Example]

The physical property evaluation in a following example and a comparative example was performed by the method shown below.

Solubility Test

In a transparent glass container, the fluorine-containing polyether composition, which is an addition product of fluorine-containing C6 epoxide and PEG, was dissolved in distilled water or an organic solvent at a predetermined concentration (10 wt% and 0.1 wt%), and the state was visually observed.

<Surface tension measurement>

The surface tension of the solution in water or an organic solvent was measured at 25 ° C. by the Wilhelmi method.

<Thermal weight loss test>

Using the heat balance, the weight loss value at 200 ° C. was measured when the temperature was raised at a rate of 10 ° C./min in an air atmosphere.

<Fog Evaluation>

Agricultural films were loaded in tunnel-shaped greenhouses 8m wide, 4m high and 110m deep, and the fog was observed at the morning when the temperature difference between inside and outside the greenhouse increased, and the following criteria were evaluated:

-1: no fog at all

+1: slightly cloudy

+2: some fog

+3: very foggy

Reference Example 1 <Synthesis of Single Terminal Additives>

In a 200 ml four-necked flask equipped with a thermometer, a cooler, and a stirring device, 37.6 g (0.1 mol) of fluorine-containing C6 epoxide represented by C ₆ F ₁₃ -CH ₂ CH (O) CH ₂ , with an average molecular weight of 400 40 g (0.1 mol) of polyethylene glycol (Me-PEG) terminally sealed with methyl group (epoxide: PEG molar ratio = 1: 1) and 0.2 g (0.0013 mol) of BF ₃ ether complex as a catalyst were added, and with stirring, 70 The reaction was carried out at 占 폚 for 3 hours. The completion of the reaction was confirmed by performing gas chromatography analysis of the reaction solution and disappearing the peak of the epoxide. After the reaction was completed, a fluorine-containing polyether composition which was a viscous liquid was obtained. This composition is a single terminal adduct in which an Rf group is added to the single terminal of PEG.

As a result of visually observing the water solubility of the obtained fluorine-containing polyether composition, 10 wt% and 0.1 wt% were completely dissolved, and it became a uniform solution. The surface tension of the aqueous solution was a low value of 18.1 mN / m. The thermogravimetric decrease at 200 ° C. was slightly greater, 17%.

These results are shown in Table 1.

Reference Example 2 <Synthesis of Both End Additives>

In a 200 ml four-necked flask equipped with a thermometer, cooler and stirring device, 75.2 g (0.2 mol) of fluorine-containing C6 epoxide represented by C ₆ F ₁₃ -CH ₂ CH (O) CH ₂ , an average molecular weight of 400 However, 40 g (0.1 mol) of polyethylene glycol (H-PEG) having a hydroxyl group (epoxide: PEG molar ratio = 2: 1) and 0.4 g (0.0025 mol) of BF ₃ ether complex as a catalyst were added and stirred at 4 ° C. at 70 ° C. Time reaction was performed. The completion | finish of reaction was confirmed by gas chromatographic analysis of the reaction liquid, and the peak of the epoxide disappeared. After completion of the reaction, a viscous liquid-containing polyether composition was obtained. This composition is a sock end adduct having an Rf group added to the sock end of PEG.

As a result of visually observing the water solubility of the obtained fluorine-containing polyether composition, it was cloudy at 10 wt% and separated into two layers at 0.1 wt%. Therefore, the surface tension of the aqueous solution could not be measured. The thermogravimetric decrease at 200 ° C. was small at 8%. These results are shown in Table 1.

Example 1 <Synthesis of Mixed Fluorine-Containing Polyether Compositions of Single-Ended Adduct, Socks-Ended Adduct, and Unreacted PEG>

In a 200 ml four-necked flask equipped with a thermometer, a cooler, and a stirring device, 37.6 g (0.1 mol) of fluorine-containing C6 epoxide represented by C ₆ F ₁₃ -CH ₂ CH (O) CH ₂ , and an average molecular weight of 400 However, 40 g (0.1 mole) of epoxy glycol (H-PEG) which is a hydroxyl group (epoxide: PEG molar ratio = 1: 1) and 0.2 g (0.0013 mole) of BF ₃ ether complex as a catalyst were added and stirred at 70 ° C. The reaction was carried out for 3 hours. The completion | finish of reaction was confirmed by gas chromatographic analysis of the reaction liquid, and the peak of the epoxide disappeared. After completion of the reaction, a viscous liquid-containing polyether composition was obtained. This composition is a mixed fluorine-containing polyether composition comprising a single end adduct having an Rf group added to one end of a PEG, a sock end adduct having an Rf group added to a sock end, and unreacted PEG. In the fluorine-containing polyether composition, the molar ratio of single end adduct: end end adduct: unreacted PEG was 64:12:12 when measured by LC-MS.

As a result of visually observing the water solubility of the obtained fluorine-containing polyether composition, it was cloudy at 10 wt%, and uniform cloudy at 0.1 wt%. The surface tension was as low as 17.9 mN / m. The thermogravimetric decrease in 200 degreeC was also 11%. These results are shown in Table 1.

Comparative Example 1 <Synthesis of Single Terminal Additives>

Instead of the fluorine-containing C6 epoxide in Reference Example 1, 57.6 g (0.1 mol) of a fluorine-containing epoxide containing an Rf group having an average carbon number of 10 represented by C ₁₀ F ₂₁ -CH ₂ CH (O) CH ₂ . The reaction and post-treatment were performed similarly to the reference example 1 except having used, and the single terminal type adduct was obtained. The 10 wt% aqueous solution of the obtained adduct was cloudy, and the 0.1 wt% aqueous solution was cloudy uniformly. The surface tension was 21.5 mN / m. Compared with Example 1, the surface tension was a high value. These results are shown in Table 1.

Comparative Example 2 <Synthesis of Mixed Fluorine-Containing Polyether Composition of Single-Ended Adduct, Socks-Ended Adduct, and Unreacted PEG>

Instead of the fluorine-containing C6 epoxide in Example 1, 57.6 g (0.1) of a fluorine-containing epoxide containing an Rf group having an average carbon number of 10 represented by C ₁₀ F ₂₁ -CH ₂ CH (O) CH ₂ . Mole) The reaction and post-treatment were performed like Example 1 except having used, and the mixed addition reaction product was obtained. The 10 wt% aqueous solution of the obtained reaction mixture was cloudy, and the 0.1 wt% aqueous solution was cloudy uniformly. The surface tension was 23.5 mN / m. Compared with Example 1, the surface tension was a high value. These results are shown in Table 1.

As a result, it was found that the reactant using the fluorine-containing C6 epoxide had lower surface tension than the reactant using the fluorine-containing C10 epoxide evaluated for comparison (used as an existing spinning agent). This result suggests that the fluorine-containing polyether composition of the present invention has excellent performance as a antifoaming agent, and shows that the fluorine-containing polyether composition has an excellent ability to lower surface tension even as a nonionic surfactant.

In addition, the characteristics required as the anti-corrosive agent include "the point that the solubility in water should not be large (because it flows down with water droplets after incorporation into an agricultural film and the durability is lost)" and the point that does not impair hydrophilicity. There is. From the results in Table 1, when the fluorine-containing C6 epoxide was reacted with PEG as a raw material, the single end adduct was excessively dissolved in water, while the end end adduct was not familiar with water, thereby impairing antifogging property. It turns out that all are not preferable at the point which makes it let.

Therefore, as a preferable compound as an agricultural film anticorrosive agent, it becomes a mixture of the fluorocarbon C6 epoxide and the sock end hydroxyl group PEG stoichiometrically, the terminal end adduct, and the unreacted PEG.

In fact, the compound of Example 1 was analyzed by liquid chromatography, and the mixed molar ratio with the single-end adduct, the sock end adduct, and the unreacted PEG was 64:12:12.

Examples 2 to 4

The reaction and post-treatment were carried out in the same manner as in Example 1 except that instead of the sock end hydroxyl group PEG having an average molecular weight of 400 in Example 1, a sock end hydroxyl group PEG having an average molecular weight of 200, 300, and 600 was used. It was. The result of having measured the physical property of the obtained fluorine-containing polyether composition was shown in Table 2 with the result of Example 1.

Comparative Example 3

In Comparative Example 2, the reaction and post-treatment were carried out in the same manner as in Comparative Example 2, except that a socks-edge hydroxyl-type PEG having an average molecular weight of 300 was used instead of the socks-edge hydroxyl-type PEG having an average molecular weight of 400. The result of having measured the physical property of the obtained reaction composition is shown in Table 2 with the result of the comparative example 2.

From Table 2, it can be seen that when the average molecular weight of PEG is small, the thermal weight loss is large, and when the average molecular weight is large, the solubility in water increases.

Therefore, as an agricultural film anticorrosion agent, it turned out that the average molecular weight of PEG exceeds 200 and is less than 600, Preferably it is the range of 250-550, More preferably, it is the range of 300-500.

Example 5 <Results in Practical Full Length Films>

The fluorine-containing polyether composition obtained in Example 1 was embedded in EVA resin which is a base material, and the agricultural film was manufactured as described below. As an antifog additive, the chemical preparation agent (HP-IV) was used together. Table 3 shows the anti-corrosion properties of the obtained agricultural film.

<Film manufacturing method>

The master batch for film production used a kneader, single and double extrusion pelletizer. The film had a three-layer structure (film thickness of 1: 1: 1), and the fluorine-containing polyether composition was added only to the innermost layer, or the innermost layer and the intermediate layer. The film forming machine formed the film at 150 degreeC-205 degreeC using SJ-90 / 30, and the film was 0.1 mm thick.

Note 1) Addition amount is parts by weight based on 100 parts by weight of each film layer.

Note 2) Evaluation of work

-1: no fog at all

+1: slightly fogged

+2: slightly cloudy

+3: very heavy fog

The fluorine-containing polyether composition of the present invention does not have a problem of PFOA generation and can be used internally as an antifogging agent for agricultural films with a low load on the environment. In addition, the fluorine-containing polyether composition of the present invention is a nonionic surfactant excellent in the ability to lower the surface tension, and can be used for applications such as an additive to a saturating agent, a paint, various penetrants and leveling agents.

Claims (13)

(a) at one end of polyethylene glycol having an average molecular weight of 250 to 550,
Formula (I): a group represented by C ₆ F ₁₃ (CH ₂ ) _n -CH (OH) CH _2- (F 1 group) or
Formula (II): group represented by C ₆ F ₁₃ (CH ₂ ) _n -CH (CH ₂ OH)-(F2 group)
(Wherein n represents 1 to 10)
Terminal adjuncts with the addition of
(b) a sock end adduct having F1 or F2 groups added to the sock end of polyethylene glycol, and
(c) Sox-based hydroxyl group polyethylene glycol
The fluorine-containing polyether composition whose molar ratio of is 30-95: 2-40: 0-40 (the sum total of (a) and (b) and (c) is 100). The composition of claim 1 wherein the composition is formula (III):

Wherein n is the same as the above, and is a reactant of the fluorine-containing C6 epoxide represented by the sock end hydroxyl group polyethylene glycol,
Single-ended adduct (a) is a 1: 1 molar ratio adduct of fluorine-containing C6 epoxide and polyethylene glycol,
The sock end adduct (b) is a 2: 1 molar ratio adduct of fluorine-containing C6 epoxide and polyethylene glycol,
A fluorine-containing polyether composition wherein the sock end hydroxyl group-type polyethylene glycol (c) is unreacted polyethylene glycol. The fluorine-containing polyether composition according to claim 2, which is obtained by reacting a fluorine-containing C6 epoxide and a sock end hydroxyl group polyethylene glycol in a molar ratio of 0.7: 1 to 1.3: 1. The fluorine-containing polyether composition according to claim 2, which is obtained by reacting a fluorine-containing C6 epoxide and a sock end hydroxyl group-type polyethylene glycol in a molar ratio of 1: 1. The molar ratio of the single terminal adduct (a), the distal end adduct (b), and the polyethylene glycol (c) is 60 to 80:10 to 20: 0. A fluorine-containing polyether composition, wherein the sum of (a), (b), and (c) is from 20 to 100; The fluorine-containing polyether composition according to claim 1, wherein the polyethylene glycol has an average molecular weight of 300 to 500. The film-proofing film for agricultural films containing the fluorine-containing polyether composition in any one of Claims 1-4. The anti-fog agent for agricultural films of Claim 7 which further contains a anti-fog agent. An agricultural film comprising the anti-rust agent according to claim 7. Nonionic surfactant containing the fluorine-containing polyether composition in any one of Claims 1-4. The method for producing the fluorine-containing polyether composition according to claim 1 or 2, wherein the fluorine-containing C6 epoxide and the sock end hydroxyl group-type polyethylene glycol are reacted at a molar ratio of 0.7: 1 to 1.3: 1. The method according to claim 11, wherein the fluorine-containing C6 epoxide and the sock end hydroxyl group polyethylene glycol are reacted in a molar ratio of 1: 1. The method according to claim 11, wherein the reaction between the fluorine-containing C6 epoxide and the sock end hydroxyl group polyethylene glycol is performed in the presence of a BF ₃ complex catalyst.