WO2000061686A1 - Additive for synthetic resin - Google Patents

Abstract

An additive for synthetic resins which can impart long-lasting antifogging properties to an internal surface layer of an agricultural covering material. The additive comprises a fluorine compound represented by Rf-Q-O-(A-O)¿n?-R (wherein R?f¿ is a C¿1-22? aliphatic polyfluorohydrocarbon group; Q is C1-5 alkylene; n is an integer of 1 to 100; A is C2-4 alkylene, etc.; and R is hydrogen, a C1-18 hydrocarbon group, etc.).

Description

 TECHNICAL FIELD The present invention relates to a synthetic resin additive. More specifically, when added to agricultural coverings made of synthetic resin film, it suppresses the fogging that occurs on the inner surface of the covering and reduces fog generation near the inner surface. It has the ability to suppress (this ability is called anti-fog property), and has the ability to exert an excellent anti-fog effect over a long period of time (this ability is an anti-fog property). (Referred to as cloudiness persistence)

Technical Background In recent years, greenhouse cultivation and tunnel-like greenhouse cultivation have been actively conducted in order to increase the productivity and marketability of useful plants. In this method, useful plants are cultivated, semi-promoted or suppressed under a coating with a covering material such as a synthetic resin film.

 Synthetic resins (for example, vinyl chloride resins), which are currently used as agricultural covering materials, contain an anti-fogging agent, a type of surfactant. This promotes the flow of water droplets on the inner surface of the covering material (the surface facing the inside of the greenhouse; the same applies hereinafter), increasing the amount of sunlight incident. That is.

However, the temperature difference between the inside and outside of the covering material becomes large under the covering of the covering material containing such an antifogging agent. Therefore, fog often occurs near the inner surface of the workpiece. As a technique to improve these disadvantages, a method of blending a fluorine-based surfactant that improves the anti-fog properties (Japanese Patent Publication No. 5-722942) has been proposed. Yes.

 However, according to experiments performed by the present inventors, not all fluorine-based surfactants exhibit anti-fog properties, and they also exhibit anti-fog properties. It has been found that even the compounds described above may adversely affect the antifogging durability of the film.

 The present invention has an ability to suppress the occurrence of fog near the inner surface of a covering material when added to an agricultural covering material (fog resistance), and has an excellent anti-fog property. The purpose is to provide a synthetic resin additive having a long-lasting haze. DISCLOSURE OF THE INVENTION The present invention provides a synthetic resin additive containing a fluorine-containing compound represented by the following formula 1.

R ^f -Q-0-(A —）) _n -R · · 'Equation 1

 However, the symbols in Equation 1 have the following meanings.

 R: a polyfluoroalkyl group having 1 to 22 carbon atoms.

 Q: Alkylene group having 1 to 5 carbon atoms.

 n: 1 to; an integer of L00.

 A: an alkylene group having 2 to 4 carbon atoms, or an aromatic hydrogen group in which at least one hydrogen atom of the alkylene group having 2 to 4 carbon atoms is a monovalent aromatic hydrocarbon group, A group that is substituted with a alkoxy group or a phenoxy group. When n is 2 to 100, A may be the same or different.

Further, the present invention provides an agriculturally disturbed material comprising a synthetic resin film which contains the above-mentioned fluorine-containing compound and does not contain an antifogging agent. BEST MODE FOR CARRYING OUT THE INVENTION The fluorine-containing compound according to the present invention is represented by the following formula 1.

R ^f -Q-O-(A —）) _n -R ·. 'Equation 1

R ^{f in} Formula 1 is a polyfluoroalkyl group (hereinafter, referred to as an R ^f group) having 1 to 22 carbon atoms. The ^Rf group is a group in which two or more hydrogen atoms in an alkyl group have been replaced by fluorine atoms.

The ^Rf group has 1 to 22 carbon atoms, but preferably 1 to 16 and particularly preferably 6 to 14 carbon atoms. R ^f number of full Tsu atom in groups, (R ^f off Tsu number atom groups) / (R ^f number of hydrogen atoms in A Le key Le group of the same number of carbon atoms that corresponds to the group) XI 0 When expressed as 0 (%), 60% or more is preferable, and 80% or more is particularly preferable. Further, the ^Rf group may have a straight-chain structure or a branched structure, and a straight-chain structure is particularly preferable. In the case of a branched structure, the branched portion is preferably a short chain having about 1 to 3 carbon atoms, and is preferably present at the terminal of the ^Rf group.

The R ^f group is a perfluoroalkyl group (hereinafter referred to as an “ ^RF group”), and preferably has a linear structure. The ^RF group is a group in which substantially all of the hydrogen atoms in the alkyl group have been replaced by fluorine atoms. That is, the R ^F group is preferably a group represented by F (CF ₂ ) _m — (m is an integer of 1 to 18). m is preferably from 4 to 16 and particularly preferably from 6 to 14.

The ^Rf group having a linear structure can be obtained by adding tetrafluoroethylene to C ₂ F 5 I by a telomerization reaction. The ^Rf group of the branched structure may be a fluorine-containing monomer such as tetrafluoroethylene or hexafluoropropylene, KF or C Catalysts such as s F It can be obtained by ori- gorization.

The fluorine-containing compound may be a mixture of two or more compounds having different numbers of carbon atoms in the ^Rf group. In particular, the carbon number of the R ^f group is 6 to

A mixture mainly containing the fluorine-containing compound of No. 14 and having an average carbon number power of 8 to 10 of the ^Rf group is particularly preferable.

 Q in the fluorine-containing compound is an alkylene group having 1, 2, 3, 4 or 5 carbon atoms. The carbon number of Q is preferably 2, 3, or 4, particularly preferably 3 or 4.

 Fluorine-containing compounds in which Q is an alkylene group having 3 or 4 carbon atoms can be found in various environments, particularly when used as a synthetic resin additive. Even so, it is a compound having excellent chemical stability and heat resistance.

Q represents an ethylene group, a trimethylene group, a tetramethylene group, a propylene group (one CH (CH 3) CH _2- ), a butylene group (- CH (CH 3) CH 2 CH 2 -, - CH 2 CH (CH 3) CH 2 -, one CH (CH 3) CH (CH 3) -) Hitoshigakyo up al is Ru. When Q has an asymmetric structure (for example, a propylene group), R ′ ′ may be bonded to any of the bonds.

 N in the fluorine-containing compound is an integer of 1 to 100, preferably an integer of 2 to 50. Even when the fluorine-containing compound of the present invention is a mixture of two or more compounds having different numbers of n, the average value of n is in the range of 1 to 50. Are preferred, especially those in the range of 2 to 30.

A in the fluorine-containing compound is a monovalent alkylene group having 2 to 4 carbon atoms or one or more hydrogen atoms of the alkylene group having 2 to 4 carbon atoms. This is a group substituted by an aromatic hydrocarbon group, an alkoxy group or a phenoxy group. Preferably, an ethylene group, a tetramethylene group, a propylene group, and one CH (C ₆ H) CH ^{_{One, - CH (CH 2 OR 1}} ) CH 2 - such Dogakyo up al is Ru. When A has an asymmetric structure (for example, a propylene group), its directionality is not limited. However, R ¹ represents an alkyl group having 1 to 10 carbon atoms, and R ¹ is preferably a methyl group, a butyl group, or a 2-ethylhexyl group. .

 If the force is between 2 and 100, then two or more A's may be the same or different. If they are different, they are preferably two or three A-forces, and in particular two. A in the fluorine-containing compound is preferably present in one or two kinds, particularly, in the ethylene group only, the propylene group only, or the ethylene group. Preferably, there are two types of groups, a styrene group and a propylene group.

(A-O) _tl is an _oxyalkylene group or a polyoxyalkylene group obtained by subjecting a cyclic ether to a ring-opening addition reaction. is there .

 As the cyclic ether, a compound containing a 3- to 5-membered cyclic ether group having one oxygen atom in the ring is suitable, and has one 3-membered cyclic ether group. Compounds (monoepoxides) are more preferred. Particularly preferred are alkylenoxysides having 2, 3 or 4 carbon atoms.

Cyclic ethers include ethylenoxide, propylene oxide, 1,2—butylene oxide, 2,3—butylene oxide, Isobutylene Oxide, Oxetane, Methyloxenate, Phenyl Dali Syl ether, Tetrahydrofuran, Styrene Oxide And the Alkyl Glycidile Ether. Alkyl glycol ethers include methyl glycidyl ether, butyl dexidyl ether, and 2-ethyl hexyl ether ether. Etc. are listed. Preferred cyclic ethers are ethylenoxide, propylenoxide or tetrahydrofuran. A formed by ring opening of tetrahydrofuran is a tetramethylene group.

 Preferably, one or more cyclic ethers are used. When two or more cyclic ethers are used, a mixture of two or more cyclic ethers may be used for the reaction, or two or more cyclic ethers may be sequentially used for the reaction. Okay.

 R in the fluorine-containing compound represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an acyl group having 1 to 18 carbon atoms.

 When R is an alkyl group having 1 to 18 carbon atoms, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group are preferred. . When R is an acyl group having 1 to 18 carbon atoms, an acyl group having 1 to 10 carbon atoms is preferable, and an acyl group having 1 to 6 carbon atoms is particularly preferable. Yes. In addition, the acyl group may have a functional group such as a carboxyl group. As R, a hydrogen atom or a methyl group is preferable, and particularly, a hydrogen atom is preferable.

Specific examples of the fluorine-containing compound (however, examples of the compound having an ^Rf group of C ₈ F i ₇ —) include, but are not limited to, the following compounds. No. It's was, and had us to the following formula compounds, the part you the contact with the R ^F group is rather good even if even if Tsu Oh straight structure Tsu Oh branched structure, a linear structure is not the good or. In addition, when there is a polyalkylene chain containing two or more kinds of oxyalkylene groups, their linkage is represented by a block. It can be random or random. The (C ₃ H ₆ 〇) portion indicates an oxypropylene group and is [CH (CH 3) CH ₂₀ ] or [CH ₂ CH (CH 3) 〇]. And. Also, the (C ₄ H ₈ O) portion indicates that it is a ring-opened product of tetrahydrofuran (CH., CH ₂ CH., CH ₉₀ ). Γ

rrj »τ5 * T1 ^l ~ i" 3

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O o o o o o o o

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 m r

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 CD CD o o o o CD o o o o

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 Γ n LHix

X r ~ i ιχ ^γ v-

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H 0 C H Ϊ r

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^ ¾Factory T C ₁₀ F _{2 l} C ₃ H ₆₀ (C ₄ H ₈₀ ) ₃ (C ₂ H ₄₀ ),. H,

C 10 ^ 21 C ₄ H ₈ 0 (CJH ₆ 0), ₀ H,

C _{l 0} F ₂ , C ₄ H _s 0 (C ₃ H _fi 0) ₄ (C ₂ H ₄ 0) ₈ H,

_{C, 0 FC 4 H s 0} (C 2 H 4 0) l 3 Ho

This onset Ming containing full Tsu fluorinated compound is obtained, et al is Ru with a child Ru cyclic er Te le by ring-opening addition reaction R ^f QOH.

There are the following methods for synthesizing R ^f Q 〇 H (if R ^f = R ^F ).

When Q of R ^F CH ₂ 0 H number force 1 carbon of the terrorist main pel full obtained in Li Ze one sheet yo emission O B A Le key Le iodine (R ^F I), E Ji Le emissions the addition was then § relay mosquito Li processing Ru obtain the path over full O b a Ruki Le E Ji les emissions _{^{(R F CH = CH 2)}} . This is to give the oxidized path over full O b A Le mosquitoes down mosquitoes Rubo phosphate (R ^F C O O H), and etc. The method of the Re this that obtained by reduction with etc. N a BH ₄ There is.

The method of synthesizing ^{_{Q R F (CH 2) 2}} OH with carbon number force 2 is above R ^F I Chi was inserted the ethylene les down, etc. The terminal iodine way that obtained by replacing the hydroxyl Oh .

The method of synthesizing ^{_{Q R F (CH 2) 3}} OH with carbon number force 3 of the Chi was added to § Li relay A Le co Lumpur to the R ^F I, by substituting the hydrogen iodide with a reducing agent There are ways to get it.

The method of synthesizing R ^F (CH _{2) 4} OH having a carbon number of 4 Q is in the R ^F I 3 - butene emissions - 1 - Chi was added an O-Le, the hydrogen Motozai changing the iodine There is a method that can be obtained by substitution.

In addition, the method for synthesizing R ^F CH ₂ CH and CH (OH) CH ₃ , which are isomers of the above compound having 4 carbon atoms, uses the above R ^F CH 2 CH ₂ with a large amount of ethanol. A method such as a method in which a predetermined radical initiator is added in a solvent and heated, and the mixture is heated and stirred, and then ethanol is added in response to the radical addition reaction to add ethanol. is there . R ^F (CH _{2) 5} OH synthesis methods Q having a carbon number of 5 to the R ^F I 4 - substituted hydrogen Chi was added to pen te down one 1 one-ol, iodine with a reducing agent There is a way to get it.

 When two or more cyclic ethers are subjected to a ring-opening addition reaction, they may be mixed and reacted, or may be reacted sequentially. When only one kind of cyclic ether is used, two or more kinds of cyclic ethers may be used in the reaction system at the same time or may be gradually added to the reaction system. .

Including full Tsu-containing compound is usually a cyclic ether and R ^f Q 〇 H

/ It is formed by reacting a dilute in the presence of a catalyst. Also, the reaction can be carried out by gradually adding a cyclic ether to the reaction system. In general, alkaline catalysts such as KOH, NaOH, and Cs〇H can be used. R ^f QOH BF _3, etc. Acid catalysts For, double engagement metal sheets § Roh of compound complexes, etc. of the metal complex catalyst is not to good or.

In the case of R ^f Q 〇 H, a mild reaction such as a ternary catalyst of Na BHN a II ₇ may result in a side reaction of HF removal under strong alkaline conditions. It is preferable to use a calcite catalyst or the above-mentioned acid catalyst or metal complex catalyst. In the case of an acid catalyst, if the acidity of the catalyst is too strong, a hydrogen atom bonded to a carbon atom adjacent to the carbon atom to which the fluorine atom in the ^Rf group is bonded Since there is a possibility that HF is desorbed, a diluting solvent may be used as needed to suppress the HF reaction. Examples of the diluting solvent include ether-based solvents such as glyme, nglyme, triglyme, methyl 1-t-butyl ether, and the like.

The reaction temperature at which the ether is added is preferably from 120 to 180 ° C, particularly preferably 0: to 130 ° C. When using a low-boiling diluent, take into account the rise in internal pressure. The reaction is preferably performed at a temperature lower than the boiling point of the medium + 20).

 The terminal hydroxyl group of the thus obtained polyoxyalkylene chain is

In addition, various properties as a fluorine-containing compound can be adjusted by terminal modification such as esterification and alkylation.

 Acetic acid, propionic acid, butanoic acid, 2-ethylhexanoic acid (octylic acid) is used as the organic carboxylic acid for esterification.

Monovalent carboxylic acids such as, 3,5,5-trimethylethylhexanoic acid (isononanoic acid), oleic acid, and stearic acid; Esters and acid anhydrides of these carboxylic acids and low-boiling alcohols are used. In addition, divalent carboxylic acids such as oxalic acid, succinic acid, maleic acid, fumaric acid, and fluoric acid, and carboxylic acid esters, and other Acid anhydrides can also be used.

 Esterification involves adding these carboxylic acids, carboxylic esters or anhydrides to the hydroxyl-terminated fluorine-containing polyalkylene compounds. No catalyst or presence of trace acid catalysts such as paratoluenesulfonic acid or sulfuric acid, or catalysts such as sodium hydroxide or sodium hydroxide Stir while heating underneath. This is followed by dehydration, deacoll, or by distilling off unreacted acid.

 Alkylation includes a method of reacting with monohaloalkyl under strong alkaline conditions and a method of using alkylsulfuric acid. In order to suppress the elimination reaction of fluorine, a reaction using an alkylating agent such as alkylsulfuric acid is preferred.

The fluorine-containing compound thus obtained may be subjected to an acid treatment using sulfuric acid, phosphoric acid, or the like, a synthetic magnesium, an activated clay, an activated carbon, if necessary. It is preferable to purify by adsorption treatment etc. The amount of Ah Ru R ^f Q 0 H with initiator charged to the reactor, Ru different in Tsu by the addition of the cyclic E Ichite Le compounds you added. Considering the stirring conditions of the reactor, it is preferable to charge at least 1/10 of the internal volume of the reactor. Considering the volumetric efficiency, it is preferable that the volume ratio after the addition of the cyclic ether is 80 to 95%, and the present invention is not particularly limited to this.

 The amount of the fluorine-containing compound to be mixed with the synthetic resin is appropriately determined according to the type of the fluorine-containing compound to be compounded. The compounding amount of the fluorine-containing compound is preferably 500 to 100 parts by mass per 100 parts by mass of the synthetic resin, and particularly preferably 70 to 99 parts by mass.

 The agricultural covering material of the present invention is a synthetic resin film cap that contains the above-mentioned fluorine-containing compound and does not contain an anti-fogging agent.

 When the fluorine-containing compound of the present invention is added to synthetic resin, which is a material for agricultural covering materials, 100 parts by mass of synthetic resin (however, plasticizer is not included in the calculation) The same shall apply hereinafter.) 0.01 or more by mass is preferable. The upper limit is not strictly limited, but if the amount is too large, bleeding or clouding may occur, so that the upper limit is usually 2.0 mass. Parts or less is sufficient. The compounding amount of the fluorine-containing compound is from 0.02 to 1 per 100 parts by mass of the synthetic resin.

.0 parts by weight are particularly preferred.

The synthetic resin, which is the material of the synthetic resin and the agricultural covering material, is not only a thermosetting resin or a thermoplastic resin for mold molding, but also a film-forming thermoplastic synthetic resin. Resin is listed. Specifically, monomers such as vinyl chloride, ethylene, propylene, acrylate ester, and methyl acrylate ester alone may be used. Or copolymers of each other, or one or more of these monomers and another copolymerizable monomer (for example, vinyl acetate, vinyl chloride). Copolymers with styrene, etc.), fluorine-containing resins, polyesters, and polyamides. And those obtained by mixing these polymers.

 Among them, from the viewpoints of weather resistance, light transmission, economy, and strength, vinyl chloride resin (that is, polyvinyl chloride) is used for film. Polymers containing 50% by mass or more of vinyl chloride polymerized units) and ethylene resins (ie, polyethylene and ethylene polymerized units of 50% by mass) % By mass) is preferred, and polyvinyl chloride is particularly preferred.

 The synthetic resin of the present invention may contain ordinary various additives, for example, a plasticizer, a lubricant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment dye, a warming improver, and the like. Mix in quantity.

 The plasticizers include, for example, dioctyl phthalate, bis-2-ethyl hexyl acrylate, dibenzyl phthalate, and diphenyl phthalate. Sodesirirata rate, Jidodesiryu evening rate, Jin

Phthalic acid derivatives such as 7 "silyl phthalate, etc., isophthalic acid derivatives such as dioctyl isocyanate, dibutyl radical, octyl phthalate, etc. Adipic acid derivatives such as dibutyl, maleic acid derivatives such as dibutyl maleate, etc., citric acid derivatives such as tributyl citrate, monobutyl itaco Itaconic acid derivatives such as neat, o-an forms such as butylolate, etc., and other triglyceryl phosphates and triglyceryl phosphates And plasticized soybean oil, epoxy resin-based plasticizer and the like.

 Examples of the above lubricants or heat stabilizers include poly (ethylene oxide), bis (amide), stearic acid, zinc stearate, and stainless steel. Examples include barium phosphate, calcium stearate, and ricinoleate.

Examples of the ultraviolet absorber include benzotriazole, benzolate, benzophenone, cyanoacrylate, and the like. UV absorbers such as UV-based and phenolic silicate-based UV absorbers .

 Examples of the above-mentioned pigments or dyes include titanium oxide, silica, ultramarine, fluoric acid and the like.

 Examples of the above-mentioned warming improver include a hydrorotal site. In order to improve the performance of the resin coating material for agricultural use, it is preferable to include a Hide □ Talsite.

 These additives are contained in a usual content, for example, 5 parts by mass or less per 100 parts of the synthetic resin.

 Synthetic resin used as material In order to mix the fluorinated compound of the present invention and, if necessary, various additives, ordinary compounding and mixing techniques can be used. For example, it can be mixed with a Ribbon Blender, Ban Remixer, Super Mixer, and other compounding machines. It is then filmed.

 In order to form a resin from a resin, a known method, for example, a melt extrusion method, a solution casting method, a calendar method, or the like may be used.

 The thickness of the synthetic resin fisolem, which is a coating material, is preferably from 0.01 to 0.5 mm, particularly preferably from 0.020.2 mm. If it is too thin, the strength will be insufficient, and if it is too thick, it will be used for filming and handling afterwards. Inconveniences, including the work and the work of spreading it in eight us).

When the synthetic resin additive of the present invention is added to an agricultural coating material, the synthetic resin additive is excellent not only in the effect of suppressing fog generation but also in antifogging properties and antifogging durability. Therefore, the agricultural covering material containing the synthetic resin additive [] agent is useful for institutional cultivation of plants. Examples The following are synthesis examples (Example 16), examples (Example 7 12), and comparisons. The present invention will be described in detail with reference to examples (Examples 13 to 18).

 [Example 1: Synthesis of fluorine-containing compound D]

500 g of F (CF ₂ ) ₈ (CH ₂ ) ₃ OH was added as powder in a stainless steel pressure-resistant auto wrap, and the zinc hexanocono was added. 0.25 g of relitate complex was added. Heat up to 55 ° C, dissolve with stirring, heat up to 80, and maintain the temperature at 80 ° C. 4 was introduced continuously over 3 hours.

 After completion of the reaction, unreacted P 2 O was distilled off under reduced pressure to obtain a crude product. After adding the chelating reagent and excluding the heavy metals of the catalyst, the adsorbents KW—100 and KW—600 (both manufactured by Kyowa Chemicals, trade names) The inorganic compound was adsorbed by sequentially adding 1 part by mass to 100 parts by mass of the crude product. Dehydration, filtration, and drying were performed to obtain a fluorine-containing compound D.

The hydroxyl value of the fluorine-containing compound D was 57.4 mg KOH / g. The NMR spectrum of the product—NMR, ¹⁹ F-NMR, and ¹³ C—NMR) showed that F (CF ₂ ) ₈ (CH ₂ ) 30 [CH ₂ CH (CH 3 ) 0] n H (however, the average value of n is 8.6).

 [Example 2: Synthesis of fluorine-containing compound E]

 The reaction was performed in the same manner as in Example 1, except that a mixture of PO / ethylene oxide (hereinafter referred to as EO) = 40/60 (mass ratio) was used instead of PO. As a result, a fluorine-containing compound E was obtained.

 The hydroxyl value of the fluorine-containing compound E was 56.8 mg K〇HZg. Due to the NMR spectrum of the product, F (CF),

(CH,), 0 [CH., CH (CH _Ί ) Ο] (C Η, C Η., Ο

) _C1 H (However, the connection between PO and EO is random. The average value of p + Q is 10 and p: q = 4: 6.) Generation was confirmed.

 [Example 3: Synthesis of fluorine-containing compound F]

 During the stainless steel pressure-resistant autoclave, 500 g of F (

CF _? ) (CH _? ) Ο Ο Η 粉末 粉末 粉末 粉末 粉末 粉末 粉末 粉末 粉末 粉末 粉末 粉末 粉末 粉末 粉末 粉末 粉末 粉末 粉末 粉末 粉末 粉末 粉末 CH CH CH CH CH CH CH CH CH CH CH CH CH CH CH . Dissolve with stirring, raise the temperature to 30 ° C, and maintain the temperature at 30 ° C with a force of tetrahydrofuran (hereinafter referred to as THF) ZEO = 60/4 546 g of the 0 mixture was introduced continuously over 3 hours.

 After further aging reaction for 5 hours, unreacted THF and a solvent gram were distilled off under reduced pressure to obtain a crude product. After neutralizing the acid content by adding a 10% aqueous sodium hydroxide solution, the adsorbents KW-1000 and KW-600 (same as above) were added, respectively. The inorganic compound was adsorbed by sequentially adding 1 part by mass to 100 parts by mass of the crude product. Dehydration, filtration, and drying

As a result, a fluorine-containing compound F was obtained.

The hydroxyl value of the fluorine-containing compound F was 59.2 mg KOHZ g. Ri by the NMR scan Bae click preparative Le _{product, F (CF 2) 8 (} CH,) 3 O (CH 2 CH 2 CH 2 CH 2 _{〇) p (CH 2 CH 2 O} ) to I _q H (other The connection between THF and E〇 is random. The average value of p + q is 7.7, and p: Q = 6: 4.) .

 [Example 4: Synthesis of fluorine-containing compound G]

The reaction was carried out in the same manner as in Example 3, except that 577.3 g of PO was used instead of THFZEO, to obtain a fluorine-containing compound G. The hydroxyl value of the fluorinated compound G was 56.5 mg K〇HZ g. According to the NMR spectrum of the product, F (CF ₂ ) _s (CH,) 3 [CH ₂ CH (CH 3) 〇] „H (where n is the average value of n) Is 8.9. ) Generation was confirmed.

 [Example 5: Synthesis of fluorine-containing compound H]

The reaction was carried out in the same manner as in Example 3 except that 546 g of EO was used instead of THFZEO, to obtain a fluorine-containing compound H. The hydroxyl value of the fluorine-containing compound H was 56.3 mg KOHZ g. According to the NMR spectrum of the product, F (CF ₂ ) ₈ (CH ₂ ) 3 O (CH ₂ CH ₂ O) _n H (where the average value of n was 11.8). Generation) was confirmed.

 [Example 6: Synthesis of fluorine-containing compound I]

 Use F (C F,) (C H,) Η instead of F

_{(CF,) R CH 2 CH} 2 C Η (C Η 3) 〇 This and except that had use of Eta is had row the reaction as in Example 3, was obtained containing full Tsu containing compound I. The hydroxyl value of the fluorine-containing compound I was 56.3 mg KOHZ g. According to the NMR spectrum of the product, F (CF) CHCH ₂ CH (CH 3) O (CH, CH ₂₀ ) H (where n is an average of 11.5). )) Was confirmed to be generated. The surface tension of a fluorine-containing compound I in a 0.01% aqueous solution was found to be 17.6 dyn cm.

 [Example 7 to Example 2 2]

100 parts by mass of poly (vinyl chloride) (average degree of polymerization = 1300), 50 parts by mass of octyl phthalate, and 2 parts of Ba-Zn liquid stabilizer Parts by mass: 1 part by mass of Ba-Zn powder stabilizer as the basic composition, and the anti-fogging agents of the types and amounts (unit: mass parts) shown in Tables 1 and 2 And fluorinated compounds were mixed. The mixture is supplied to a calendar molding machine heated to 180 ° C, and formed into a film having a thickness of 0.075 mm by a conventional method. 15 species (except for example 22) were created. Table 3 shows the fluorine-containing compounds J, K, and L. The above 15 films and a commercially available 0.075 mm thick anti-fog agricultural polyvinyl chloride film containing no fluorine-containing compound. A total of 16 species (Example 22) were evaluated.

 The experimental greenhouse was assembled on an outdoor temperature-controllable water tank. It was made by stretching a frame with a height of 0.5 m, a width of 0.8 m, and a depth of 0.4 m. The antifogging property and fog generation were evaluated by the following methods. The results are shown in Tables 1 and 2.

 [Evaluation of anti-fog property]

 The test was started in September, and the inside of the film stretched in the experimental greenhouse was observed for 8 months. The antifogging property was evaluated according to the following criteria.

 ◎: No adhesion of water droplets was observed.

 〇: Slightly adhering water droplets,

 △: Adhesion of water droplets is observed,

 X: Significant water droplets are observed.

 XX: Water droplets are observed over the entire surface.

 [Evaluation of fog generation status]

 In the morning and evening when the temperature drops, the temperature of the water tank is raised to 45 ° C, and the fog inside the film stretched over the experimental greenhouse for about 2 hours. The occurrence was observed. These observations were made twice a month in September and four times a month from October to April. The fog occurrence was evaluated based on the following criteria.

 ◎: No fog is observed.

 〇: The generation of fog is slightly observed.

 △: fog generation is observed,

X: The occurrence of fog is remarkably recognized. table 1

 Table 3

Fluorine-containing compound J: c ₈ F ₁₇ CH ₂ CH (OH) CH, 0- (CH ₂ CH ₂ 0) ₁₀ [CH ₂ CH (CH ₃ ) 0] CH ₃ fluorinated compound K: C ₉ F ₁₉ CON (CH ₃ ) (CH ₂ CH ₂₀ ) 12 H Fluorine-containing compound L: C ₈ F ₁₇ S0 ₂ N (CH ₃ ) (CH ₂ CH ₂₀ ) lo H

Claims

The scope of the claims 1. A synthetic resin additive containing a fluorine-containing compound represented by the following formula 1.  R f — Q — 〇 — (A-0) „-R ·.. Equation 1  However, the symbols in the formula 1 have the following meanings.  R ': a polyfluoroalkyl group having 1 to 22 carbon atoms.  Q: Alkylene group having 1 to 5 carbon atoms.  n: An integer from 1 to 100.  A: an alkylene group having 2 to 4 carbon atoms, or at least one hydrogen atom of an alkylene group having 2 to 4 carbon atoms, a monovalent aromatic hydrocarbon group, A group substituted by a alkoxy group or a phenoxy group. When n is 2 to 100, A may be the same or different.  R: a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an acyl group having 1 to 18 carbon atoms. 2. The synthetic resin additive according to claim 1, wherein R is a hydrogen atom. 3. The method according to claim 1, wherein A is at least one group selected from an ethylene group, a propylene group, and a tetramethylene group. Synthetic resin additives. 4. The synthetic resin additive according to claim 1, wherein the carbon number of Q is 3 or 4. 5. An agricultural material comprising the synthetic resin film, which contains the fluorine-containing compound according to claim 1, 2, 3, or 4, and does not contain an anti-fogging agent. Industrial coating materials