WO2007032480A1

WO2007032480A1 - Fluorine-containing compounds, process for production thereof, uses of the compounds, method for lowering surface tension, and method for surface modification of resin

Info

Publication number: WO2007032480A1
Application number: PCT/JP2006/318374
Authority: WO
Inventors: Masato Mitsuhashi
Original assignee: Agc Seimi Chemical Co., Ltd.
Priority date: 2005-09-16
Filing date: 2006-09-15
Publication date: 2007-03-22
Also published as: KR20080044280A; JPWO2007032480A1; TW200720321A; CN101263104A; JP5139068B2; CN101263104B; KR101288712B1

Abstract

Fluorine-containing compounds represented by the general formula (I) which are excellent in the ability to lower surface tension and the solubility in water; a process for the production of the same; uses thereof; a method for lowering surface tension; and a method for surface modification of resin: (I) wherein J5 is hydrogen, alkyl having 1 to 10 carbon atoms, or -Z5-O-(AkO)n5-X5-R5; J6 is hydrogen, alkyl having 1 to 10 carbon atoms, or -Z6-O-(AkO)n6-X6-R6; AkO is oxyalkylene; R1 to R6 are each hydrogen or a monovalent organic group, with the proviso that at least one of R1 to R6 is fluorine-containing alkyl having 1 to 12 carbon atoms; m is an integer of 0 to 20; n1 to n6 are each an integer of 0 to 20, with the proviso that the sum of n1 to n6 is larger than 0; X1 to X6 are each a single bond or a divalent connecting group; and Z3 to Z6 are each a single bond or methylene.

Description

Specification

Fluorine-containing compound, production method thereof, use thereof, surface tension reduction method, and resin surface modification method

Technical field

[0001] The present invention relates to a fluorine-containing compound, a method for producing the same, a use of the fluorine-containing compound, a surface tension reducing method using a fluorine-containing compound, and a resin surface modifying method.

This application claims priority to Japanese Patent Application No. 2005-269974 filed on September 16, 2005, the contents of which are incorporated herein by reference.

Background art

[0002] A fluorine-containing compound having a fluorine-containing alkyl group as a hydrophobic group has a high ability to reduce surface tension. Therefore, when it is added as a surfactant to a coating composition, it has excellent permeability and wettability. And exerts effects such as leveling. As the fluorine-containing compound, various structures have been proposed so far.

[0003] Ordinary fluorine-containing compounds have the property of being hardly soluble in water. As fluorine-containing compounds having hydrophilicity, fluorine-containing compounds in which hydrophilic groups are made ionic are known. However, the fluorine-containing compound does not have solubility in an organic solvent.

[0004] As another fluorine-containing compound having hydrophilicity, a fluorine-containing compound having an oxyalkylene group is known (Patent Document 1). Although the fluorine-containing compound is improved in hydrophilicity, the ability to reduce surface tension is poor.

Patent Document 1: Japanese Patent Laid-Open No. 04-145041

Disclosure of the invention

Problems to be solved by the invention

[0005] The present invention provides a fluorine-containing compound having excellent ability to reduce surface tension and solubility in water, a method for producing the same, a use thereof, a method for reducing surface tension, and a method for modifying the surface of a resin. Means for solving the problem

[0006] The fluorine-containing compound of the present invention is a fluorine-containing compound represented by the following formula (I).

[0007] [Chemical 1] … (

[0008] However, J ⁵ is a hydrogen atom, carbon number 1 to: LO alkyl group, or —Z ⁵ —0— (AkO) n5

— X ⁵ — R ⁵ ; J ⁶ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or — Z ⁶ — O— (AkO) — X ⁶ — R ⁶ , AkO represents an oxyalkylene group R'-R ⁶ is a hydrogen atom n6

Or a monovalent organic group! At least one of ^ to is a fluorine-containing alkyl group having 1 to 12 carbon atoms which may have an etheric oxygen atom, m represents an integer of 0 to 20, and nl to n6 represent an integer of 0 to 20 Nl + n2 + n3 + n4 + n5 + n6> 0, Χ Χ ⁶ represents a single bond or a divalent linking group, and ζ ^{3 to} ζ ⁶ represent a single bond or a methylene group.

[0009] The fluorine-containing compound of the present invention is preferably a fluorine-containing compound represented by the following formula (I1).

[0010] [Chemical 2]… (卜 I)

[0011] However, AkO represents an oxyalkylene group, I ^ to R ⁴ represent a hydrogen atom or a monovalent organic group, and at least one of I ^ to R ⁴ has an etheric oxygen atom. A fluorine-containing alkyl group having 1 to 12 carbon atoms, m represents an integer of 0 to 20, nl to n4 represents an integer of 0 to 20, nl + n2 + n3 + n4> 0, and xi X ⁴ represents a single bond or a divalent linking group.

The total of nl to n6 present in the formula (I) or the formula (1-1) is preferably 4 to 50.

In the fluorine-containing compound represented by the formula (1-1), R ¹ — X ¹ —, R ² — X ² —, R ³ — X

³ —, R ⁴ — X ⁴ — is a hydrogen atom or Rf— (CH) p— CH (OH) — CH— Y— (where p

twenty two

Represents an integer of 0 to 16, Rf represents a perfluoroalkyl group having 3 to 12 carbon atoms, Y represents a single bond or a divalent linking group), and R ¹ — X ¹ —, R ² — X ² —, R ³ — X ³ —, at least one of R ⁴ -X ⁴ is Rf— (CH) p— CH (OH) — CH— Y—, and m is 1 to 3 An integer is shown, and nl + n2 + n3 + n4 is preferably 4-50.

[0012] The method for producing a fluorine-containing compound of the present invention comprises an etheric oxygen atom at the terminal hydroxyl group of an alkylene oxide adduct obtained by adding an alkylene oxide to glycerol or polyglycerol. Alternatively, a fluorine-containing compound represented by the above formula (I 1) is obtained by reacting a compound having a fluorine-containing alkyl group having 1 to 12 carbon atoms. In the present specification, “polyglycerin” is represented by “HO— (CH 2 CH (OH) CH 0) n—H”.

twenty two

For glycerin derivatives, it means compounds with n = 2 or more.

In addition, the method for producing a fluorine-containing compound of the present invention includes an alkylene obtained by adding an alkylene oxide to a compound having a fluorine-containing alkyl group having 1 to 12 carbon atoms which may have an etheric oxygen atom. This is a method for obtaining a fluorine-containing compound represented by the above formula (I1) by reacting glycerin or polyglycerin with the terminal hydroxyl group of an oxide adduct.

[0013] The surfactant of the present invention contains the fluorine-containing compound of the present invention.

The leveling agent of the present invention contains the fluorine-containing compound of the present invention. The anti-fogging agent of the present invention contains the fluorine-containing compound of the present invention.

[0014] The surface tension reducing method of the present invention is a method of reducing the surface tension of a liquid by adding the fluorine-containing compound of the present invention to the liquid.

The resin surface modification method of the present invention is a method of modifying the resin surface by adding the fluorine-containing compound of the present invention to the resin.

The invention's effect

[0015] The fluorine-containing compound of the present invention is superior in surface tension reducing ability and water solubility compared to conventional fluorine-containing compounds.

According to the method for producing a fluorine-containing compound of the present invention, a fluorine-containing compound having excellent ability to reduce surface tension and solubility in water can be produced efficiently with few steps.

[0016] The surfactant of the present invention is superior in surface tension reducing ability and water solubility compared to conventional surfactants.

The leveling agent of the present invention easily dissolves in compositions such as coating materials, resists, water glass, cleaning agents, etching solutions, plating solutions, adhesives, antifungal agents, and agricultural chemicals. Leveling performance that is not affected by the presence of objects can be imparted. The anti-fogging agent of the present invention can quickly develop the anti-fogging performance of a film having high surface transferability. In addition, the anti-fogging performance can be exhibited without inhibiting other functions such as anti-fogging performance.

[0017] According to the surface tension lowering method of the present invention, the surface tension of the liquid can be lowered without being limited by the solvent composition of the liquid. Functions such as property, foamability, detergency and emulsification can be imparted.

According to the surface modification method of the present invention, functions such as antistatic properties, antifogging properties, antifogging properties, water repellency and lubricity can be imparted to various types of resins.

BEST MODE FOR CARRYING OUT THE INVENTION

[0018] (Fluorine-containing compound)

The fluorine-containing compound of the present invention is a fluorine-containing compound represented by the following formula (I) (hereinafter referred to as compound (I)).

[0019] [Chemical 3]

[0020] J ⁵ represents a hydrogen atom, carbon number 1 to: LO alkyl group, or —Z ⁵ —0— (AkO) — X ⁵ — R ⁵ n5, J ⁶ represents a hydrogen atom, carbon number 1 to: L0 alkyl group, or — Z ⁶ — O— (AkO)-n6

X ⁶ -R ⁶ is shown.

[0021] AkO represents an oxyalkylene group, and from the viewpoint of ease of synthesis, an oxyethylene group is particularly preferable from the viewpoint of solubility in water, which is preferably an oxyethylene group or an oxypropylene group. The oxyalkylene chain composed of a plurality of AkOs may be composed of one or more AkO forces and may be composed of two or more AkO chains. Each oxyalkylene chain may have the same structure or a different structure.

[0022] R'-R ⁶ represents a hydrogen atom or a monovalent organic group; At least one of ^ ~ is a fluorine-containing alkyl group having 1-12 carbon atoms.

The fluorine-containing alkyl group means a group in which at least one hydrogen atom in the alkyl group is substituted with a fluorine atom. All the carbon atoms in the fluorine-containing alkyl group are single bonds. Connected together. The fluorine-containing alkyl group may have an etheric oxygen atom inserted between carbon atoms.

[0023] The fluorine-containing alkyl group is preferably a linear fluorine-containing alkyl group from the viewpoint of the ability to reduce surface tension.

The fluorine-containing alkyl group is preferably a perfluoroalkyl group from the viewpoint of the ability to reduce the surface tension.

As the fluorine-containing alkyl group, a linear perfluoroalkyl group prepared by a telomerization method is particularly preferred from the viewpoint of ease of synthesis and ability to reduce surface tension.

The number of carbon atoms of the fluorine-containing alkyl group is preferably 3-12, more preferably 4-10, and particularly preferably 4-6, from the viewpoints of solubility in water and ability to reduce surface tension.

[0024] The monovalent organic group is not particularly limited as long as it does not impair the solubility of compound (I) in water.

! The portion of ^ ~ that is not a fluorine-containing alkyl group is a hydrogen atom or a carbon atom 1 that is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms in terms of hydrophilicity and ease of synthesis. Particularly preferred is a hydrogen atom, with ~ 4 alkyl groups being more preferred. Of compound (I) and compound (1-1)! In ^ ˜, the number of the moiety that is a fluorine-containing alkyl group is preferably 1 to 3, particularly preferably 1 to 2. In addition, when the compound (I) and the compound (1-1) are a mixture, the average is preferably 1 to 3, and more preferably 1 to 2.5. ,. When the number of the fluorine-containing alkyl group is within the above range, the water solubility is improved, which is preferable.

[0025] m represents an integer of 0 to 20. M is 0 to: LO is preferred 0 to 3 is more preferred 1 to 3 in that compound (I) is easy to handle, exhibits viscosity, and is readily available as a commercial product. Is particularly preferred.

[0026] nl to n6 represent an integer of 0 to 20, and nl + n2 + n3 + n4 + n5 + n6> 0. Nl + n2 + n3 + n 4 + η5 + η6 is 4 to 50 forces, especially 10 to 30 forces, because it has good affinity with the solvent and has a good ability to lower the surface tension. . For the total of nl to n6, existing nl to n6 are targeted. Specifically, η5 and η6 do not exist. Nl + n2 + n3 + n4> 0, and nl + n2 + n3 + n4 is preferably 4-50. Similarly, when n3, n5 and n6 are not present, nl + n2 + n4> 0 and nl + n2 + n4 is preferably 4-50. When the values of nl to n6 are as described above, the water solubility is good, and it is preferable when the surfactant is used as a leveling agent or the like.

[0027] ~ ⁶ represents a single bond or a divalent linking group. ~ ⁶ are single bonds, Tables 1 and 2 show specific examples of — (CH 2) q—, — (CH 2) p—CO—, — (CH 2) p—CH (OH

2 2 2

) -CH One, One (CH) p-CH (CH OH) —CH-, One (CH) p— 0— CH—CH (

2 2 2 2 2 2

OH) — CH—,-(CH) q— O— CO— (CH) r—,-(CH) q— S— (CH) r—,

2 2 2 2 2 One SO—, One SO —N ((CH 2) pH) — (CH 2) q—, One SO—N ((CH 2) pH) — (CH

2 2 2 2 2 2 2

) q—CO—, wherein p represents an integer from 0 to 16, q represents an integer from 1 to 16, and r represents an integer from 1 to 16. (CH) p or (CH) q The alkylene group represented has a branched structure

twenty two

Group), etc. may be mentioned. It is also a fluorine-containing alkyl group! ^ ~ Bound to ~ ⁶ is preferably a linking group other than a single bond in terms of ease of raw material preparation and synthesis-(CH) q-,-(CH) p- CO-,-(CH) p— CH (OH) — CH—,-(CH

2 2 2 2

) p-0-CH -CH (OH) -CH One, one (CH) q— S— (CH) r—, One SO—, One S

2 2 2 2 2 2

O 2 —N ((CH 2) pH) − (CH 2) q— is more preferable. Examples of these are shown in Table 2.

2 2 2

(2-1) to (2-6), (2-9), (2-10), (2-15), (2-20), and (2-23) groups are included. A particularly preferred group is — (CH 2) p—CH (OH) —CH—. ― (CH) p―

2 2 2

In CH (OH) 2 -CH 1, 1 to 3 is preferable as p, and 1 is particularly preferable.

2

Also, ^1-6 is not limited to those shown as specific examples, it may be a ivy structure combination of a plurality of linking groups. Such a structure is-(CH) p- CH (OH)-CH- Y

2 2 1 (Υ is a single bond or a divalent linking group). In this case, examples of the divalent linking group of Υ include linking groups such as amine. ― (CH) p-CH (OH) -CH― Y

2 1 In p, 1 to 3 is preferred as p, and 1 is particularly preferred. In addition, when Y is a single bond, it becomes one (CH 2) p—CH (OH) —CH— described above.

twenty two

[0028] [Table 1]

2]

[0030] Z ³ ~Z ⁶ represents a single bond or a methylene group.

[0031] The compound (I) is preferably a fluorine-containing compound represented by the following formula (I 1) (hereinafter referred to as compound (I 1)). Compound (1-1) is a compound (I) in which hydrogen atoms are selected as J ⁵ and J ⁶ and single bonds are selected as z ³ and z ⁴ .

[0032] [Chemical 4]... (J -i)

[0033] However, AkO represents an oxyalkylene group, I ^ to R ⁴ represent a hydrogen atom or a monovalent organic group, and at least one of I ^ to R ⁴ has an etheric oxygen atom. Good carbon number 1 to 12 fluorine-containing alkyl groups, m represents an integer of 0 to 20, nl to n4 represents an integer of 0 to 20, nl + n2 + n3 + n4> 0, and xi X ⁴ is a single Indicates a bond or a divalent linking group.

[0034] (Method for producing fluorine-containing compound)

As a method for producing the compound (1-1), an alkylene oxide is added to glycerin or polyglycerin to obtain an alkylene oxide adduct, and then an etheric oxygen is added to the terminal hydroxyl group of the alkylene oxide adduct. The method of making the compound which has a C1-C12 fluorine-containing alkyl group which may have an atom react is mentioned.

[0035] The alkylene oxide adduct of glycerin can be obtained, for example, by blowing ethylene oxide gas into glycerin or polyglycerin in the presence of a base catalyst when the alkylene oxide is ethylene oxide. At that time, the number of added moles of ethylene oxide can be adjusted by the amount of gas blown. In addition, they are commercially available as New Ox G-450, New TG-330 (1000, 2000, 3000, 4000) manufactured by Nippon Oil and Fats Co., Ltd., and can be easily obtained.

Diglycerin alkylene oxide adducts are sold as SC-E450 (750, 1000, 1500, 2000), SC-P400 (750, 1000, 1200, 1600) by Sakamoto Yakuhin Kogyo Co., Ltd. Easy to obtain.

[0036] The compound having a fluorine-containing alkyl group is particularly preferably a compound having the structure (or group) shown in Table 3, which is preferably a compound having a perfluoroalkyl group. Rf group is a perfluoroalkyl group having 3 to 12 carbon atoms, p represents an integer of 0 to 16, q represents an integer of 1 to 16, r represents an integer of 1 to 16, Z Is an atom of chlorine, bromine or iodine. However, the compound is not limited to the following compounds as long as the compound of the formula (I 1) can be synthesized.

[0037] [Table 3] (3-1) Rf (CH2) _p C00H (3-2) RffCHaJqZ

RfiCHs) ^-^

(3-3) Rf (CH ₂ ) _p 0H (3-4)

0

Rf (CH ₂ ) `` 0 ~ ^ \ 1

(3-5) (3-fi) Rf— (CH ₂ ) q-S— (CHz) r— z

0

0 (CH ₂ ) pH

(3-7) (3-8) Rf-SN- (CH ₂ ) q-OH

II

0

1

[0038] As the compound having a fluorine-containing alkyl group, the compounds (3-1) to (3-5) are preferred in view of the availability of raw materials and the synthesizing properties (3-1). In which p is 0, in (3-2) q is 2, in (3-3) p is 1 to 3 in (3-4), and in (3-4) p is 1 in particular.

[0039] The reaction of the alkylene oxide adduct and the compound having a fluorine-containing alkyl group (hereinafter referred to as fluorine-containing alkyl group introduction reaction) may be performed in the absence of a solvent or in the presence of a solvent. You may go on. Examples of the solvent include acetone, ethyl acetate, methanol, ethanol, tetrahydrofuran (THF) and the like as long as the raw material is soluble. Since the production process can be simplified and the volumetric efficiency is excellent, the reaction is preferably carried out in the absence of a solvent.

[0040] The temperature of the fluorine-containing alkyl group introduction reaction is preferably 0 to 150 ° C in terms of ease of control and the like, and a refrigerant medium or a heat medium other than steam is unnecessary and is easy to manufacture. 20-100 ° C is particularly preferred.

The pressure of the fluorine-containing alkyl group introduction reaction is preferably normal pressure because it is simple. The temperature and pressure of the fluorine-containing alkyl group introduction reaction are not limited to the above ranges.

[0041] Examples of the atmosphere of the fluorine-containing alkyl group introduction reaction include air, nitrogen atmosphere, argon atmosphere, helium atmosphere and the like.

In the reaction of introducing a fluorine-containing alkyl group, an acid catalyst or a base catalyst may be used. The raw material charging method in the fluorine-containing alkyl group introduction reaction is not particularly limited.

[0042] The compound (1-1) obtained by the production method may be used after purification or may be used unpurified depending on the application. Examples of the purification means include solvent washing, recrystallization, various chromatography, distillation of residual solvent, use of an adsorbent, and the like.

[0043] The production method of the compound (I 1) is not limited to the above-mentioned method, and may have an etheric oxygen atom and may have a fluorine-containing alkyl group having 1 to 12 carbon atoms. Alternatively, a method may be used in which glycerin or polyglycerin is reacted with a hydroxyl group at the terminal of an alkylene oxide adduct obtained by adding an alkylene oxide to the alkoxide. As an adduct of alkylene oxide, for example, when alkylene oxide is ethylene oxide, it can be obtained by blowing ethylene oxide gas into an alcohol derivative having a fluorine-containing alkyl group in the presence of a base catalyst. . At that time, the number of moles of ethylene oxide added can be adjusted by the amount of gas blown. It can also be obtained by reacting an alcohol derivative having a fluorine-containing alkyl group with polyoxyethylene glycol. Examples of the reaction between the terminal hydroxyl group of the alkylene oxide adduct and glycerin or polyglycerin include a method in which the hydroxyl group at the terminal of the alkylene oxide adduct is halogenated and reacted with glycerin or polyglycerin. Another example is a method in which the terminal hydroxyl group of glycerol or polyglycerol is halogenated and reacted with an alkylene oxide adduct. In the compound (1-1), since the addition number of the fluorine-containing alkyl group can be easily adjusted, a method in which the hydroxyl group at the terminal of the alkylene oxide adduct is nominated is preferred!

[0044] In addition, compound (I) can be produced by replacing glycerin or polyglycerin with trimethylolpropane, pentaerythritol, or dipentaerythritol.

For example, (i) the terminal hydroxyl group of an alkylene oxide adduct obtained by adding alkylene oxide to trimethylolpropane, pentaerythritol, or dipentaerythritol has an etheric oxygen atom. A method of reacting a compound having a fluorine-containing alkyl group having 1 to 12 carbon atoms, (ii) having an etheric oxygen atom! / ヽ a fluorine-containing alkyl group having 1 to 12 carbon atoms To the hydroxyl group at the end of the alkylene oxide adduct obtained by adding alkylene oxide to the compound having Compound (I) can be produced by a method of reacting serine or the like.

[0045] Alkylene oxide adducts of trimethylolpropane are commercially available as TMP-30U, TMP-60, TMP-F32 manufactured by Nippon Emulsifier Co., Ltd. it can.

Pentaerythritol with alkylene oxide is a PNT-40 manufactured by Nippon Emulsifier Co., Ltd.

, PNT-60, etc., and are readily available.

In compound (I) and compound (I-1)! In ^ to, the number of parts that are fluorine-containing alkyl groups can be adjusted by the raw material charge ratio. For example, when 2 moles of the fluorinated alkyl group-containing compound is used per 1 mole of glycerin or polyglycerin, compound (I) having an average number of fluorinated alkyl groups of 2 can be obtained.

[0046] (Application)

Compound (I) can be used in various applications because it can exhibit a sufficient surface tension reducing effect even in a small amount. Uses added to liquids such as solvents include penetrants, wettability improvers, leveling agents, paints, emulsifiers, dispersants, fire extinguishing agents, floor waxes, cleaning agents, foaming agents, antifoaming agents, etc. Is mentioned. Applications that are used by adding to cocoa butter include antifogging agents, antifogging agents, foaming agents, antifoaming agents, antistatic agents and the like. It may also be used as a grease diffusion inhibitor by adding to grease. Compound (I) may be used alone or in combination of two or more.

Hereinafter, surfactants, leveling agents, and antifogging agents will be described as uses of compound (I).

[0047] (Surfactant)

The surfactant of the present invention contains compound (I). If necessary, it contains a solvent and other ingredients!

As the solvent, water, water, an organic solvent, and water that is preferably a fluorine-based solvent are particularly preferable. Examples of organic solvents include alcohols such as methanol, ethanol, 1 propanol, 2-propanol, and t-butanol; esters such as ethyl acetate, methyl acetate, and butyl acetate; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Polarities such as N, N dimethylformamide, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone Solvent; Glycol ethers such as diethylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; Daricols such as ethylene glycol and propylene glycol; Ethers such as jetyl ether, tetrahydrofuran and dioxane

And nitrogen-containing solvents such as pyridine and piperazine. As the solvent, one type may be used alone, or two or more types may be used in combination.

[0048] Examples of other components include other surfactants, organic substances having affinity for solvents, and inorganic substances such as various salts. Examples of other surfactants include commercially available surfactants such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants.

By adding the surfactant of the present invention to various liquids, the surface tension of the liquid can be lowered without being limited by the solvent composition of the liquid. Functions such as property, foamability, detergency and emulsification can be imparted.

[0049] (Leveling agent)

The leveling agent of the present invention contains compound (I). If necessary, it contains a solvent and other ingredients!

Examples of the solvent include water, organic solvents, fluorine-based solvents and the like.

Examples of other components include solutes and additives. Examples of solutes include various types of resin. Examples of additives include various surfactants, coupling agents, metal oxides, acid / antioxidant agents, antistatic agents, antifungal agents, antifogging agents, ultraviolet ray preventing agents, and photosensitizers. The leveling agent of the present invention is a coating material such as a printing material, photosensitive material, paint, optical material, floor wax; resist, water glass, cleaning agent, etching solution, plating solution, adhesive, antifungal agent, agricultural chemical. Therefore, leveling performance can be provided without being affected by the presence of other compositions.

[0050] (Anti-fogging agent)

The anti-fogging agent of the present invention contains compound (I). If necessary, other components may be contained.

Examples of other components include plasticizers, antifogging agents, ultraviolet absorbers, heat stabilizers, lubricants, stabilizers, antistatic agents, pigments, and dyes. The anti-fogging agent of the present invention is added to the synthetic resin material constituting the agricultural synthetic resin coating material. Examples of the synthetic resin material include film-forming thermoplastic synthetic resins. Specifically, monomers such as vinyl chloride, ethylene, propylene, acrylic acid ester, methacrylic acid ester alone or their mutual polymers, or at least one of these monomers and other monomers. Examples thereof include a copolymer with a copolymerizable monomer (for example, vinyl acetate, salt vinylidene, etc.), fluorine-containing resin, polyester, polyamide, and a blend thereof.

The anti-fogging agent of the present invention can quickly express the anti-fogging performance of a film having a high transferability to the surface of the resin. Further, by taking a structure having an appropriate number of hydrophilic groups, the fog prevention performance can be exhibited without inhibiting other functions such as the antifogging performance.

[0051] (Surface tension reduction method)

The surface tension reducing method of the present invention is a method for reducing the surface tension of a liquid by adding compound (I) to the liquid.

Examples of the liquid include water and organic solvents, and a liquid containing water is preferable. Examples of the organic solvent include alcohols such as methanol, ethanol, 1 propanol, 2-propanol, and t-butanol; esters such as ethyl acetate, methyl acetate, and butyl acetate; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Polar solvents such as N, N dimethylformamide, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone; glycol ethers such as diethylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; Daricols such as ethylene glycol and propylene glycol; Ethers such as ether, tetrahydrofuran and dioxane

And nitrogen-containing solvents such as pyridine and piperazine. The liquid may be a mixed solvent of two or more.

The amount of compound (I) added is preferably from 0.001 to 20 parts by mass, particularly preferably from 0.005 to 5 parts by mass with respect to 100 parts by mass of the liquid. In this range, the surface tension can be sufficiently reduced without impairing the properties of other additives.

[0052] To the liquid, solutes and additives other than the compound (I) may be added.

Examples of the solute include various resins. Specifically, acrylic resin, epoxy resin, Examples include alkyd resin, urethane resin, polyimide resin, and fluorine-containing resin. Solutes may be used alone or in combination of two or more.

Additives include hydrocarbon surfactants, silicone surfactants, fluorine surfactants, silane coupling agents, titanium coupling agents, metal oxides, antioxidants, antistatic agents, and antifungal agents. Agents, antifogging agents, ultraviolet ray preventing agents, photosensitive agents and the like.

According to the surface tension reducing method of the present invention, since the compound (I) has solubility in various solvents, the surface tension of the liquid can be reduced without being limited by the solvent composition. Functions such as leveling, penetrability, foaming, detergency, and emulsification can be imparted.

[0053] (Resin surface modification method)

The resin surface modification method of the present invention is a method for modifying the resin surface by adding compound (I) to the resin.

Examples of the resin include poly salt resin, polyethylene, polypropylene, polystyrene, polysalt vinylidene, acrylic resin (polymethyl acrylate, etc.), epoxy resin, fluorine resin, polyurethane, polyester, polycarbonate Polyacetal, polyethylene terephthalate, polyamide, polyimide, melamine resin, phenol resin, urea resin, fluorine resin, and the like. The resin may be a natural resin or a synthetic resin. Further, the resin may be a thermoplastic resin or a thermosetting resin. The resin may be a mixture of two or more.

[0054] The addition method may be a method in which compound (I) and rosin are directly kneaded, and compound (I) is added to a small amount of rosin or the like to form a masterbatch, It may be added to the method.

The amount of compound (I) added is preferably 0.001 to: LO parts by mass, particularly preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the resin. Within this range, the surface modification performance is maintained by appropriately bleeding out the compound (I) to the surface of the resin.

[0055] Additives other than the compound (I) and the like may be added to the rosin.

Additives include hydrocarbon surfactants, silicone surfactants, fluorosurfactants; plasticizers such as DOP (dioctyl phthalate) and DMP (dimethyl phthalate); Stabilizers such as tiltin laurate, norlium sarcophagus; Antioxidants such as BHA (Butylhydroxyl-sol); Agents: various antistatic agents, flame retardants, colorants, lubricants, antibacterial agents, and the like.

According to the method for modifying the surface of a resin of the present invention, the compatibility between the compound (I) and the resin can be used for various types of resins, such as antistatic properties, antifogging properties, antifogging properties, water repellency, lubricity, etc. Can be provided. The same function can also be imparted by applying the surfactant solution of the present invention to the surface of the resin.

[0056] The compound (I) of the present invention described above has a structure derived from an alkylene oxide adduct obtained by adding an alkylene oxide to glycerin or polyglycerin, and therefore, compared with a conventional fluorine-containing compound, Excellent solubility in water. Furthermore, since it has a fluorine-containing alkyl group having 1 to 12 carbon atoms, that is, a fluorine-containing group in which all carbon atoms are connected by a single bond, it has an excellent ability to reduce surface tension compared to conventional fluorine-containing compounds. In contrast, the compound described in Patent Document 1 is not saturated with a fluorine-containing group (C F —, C F —) at the terminal.

6 11 9 17 Since it has a hydrating group and is branched, the ability to reduce surface tension is not sufficient.

[0057] (Example)

Hereinafter, the present invention will be described in detail with reference to examples. The present invention is not limited to these examples.

[Example 1]

In a 50 ml three-necked flask, SC-E1000 (ethylene oxide adduct represented by the following formula (1-0), hydroxyl value 210 mgKOHZg, the average molecular weight calculated from the hydroxyl value was 1069, the average molecular weight force calculated nl + The total of n2 + n3 + n4 is 20.5 on average, the total of nl + n2 + n3 + n4 in the catalog is about 20 on average, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) 10. Og, BF -OEt (

3 2 Wako Pure Chemical Industries, Ltd.) 0.08 g, Compound (3-4a) (Daikin Chemicals Sales Co., Ltd.) 7. 59 g was charged and stirred at 60 ° C. for 1 hour. Using a gas chromatograph (hereinafter referred to as G.C), it was confirmed that the conversion rate of compound (3-4a) was 99% or more, the reaction was terminated, and the target compound (I-la) was Obtained. In the compound (I-la), R ^{U to} R ¹⁴ are calculated from the raw material charge ratio, and on average, two are hydrogen atoms and the other two are CF CH CH (OH) CH one. Also, The total of nl + n2 + n3 + n4 is about 20 on average, the same as the raw material. Further, ¹⁹ F-NMR and ¹³ C-NMR were measured for the compound (I-la), and it was confirmed that the compound (I-la) was obtained. The results are shown below.

19

[0059] F—NMR (300 MHz, solvent: CD OD, standard: CFC1): — 74.3 (3F, S) ゝ

3 3

-113.8 (2F, S), -122.3 (2F, S), -123.4 (2F, S), -124.1 (2F, S), -126.2 (2F, S).

¹³ C—NMR (NOE complete removal decoupling method) (300 MHz, solvent: CD OD, standard

Three

Material: Hexamethyldisiloxane): 35.5 (2C, T), 62.2 (2C, S), 64.5 (2C, S), 71.6 (46C, with multiple shoulders), 73.7 (2C, S), 75.9 (2C) , S), 79, 6 (2C, S), 116-124 (multiple split peaks).

[0060] [Chemical 5]

0- (C ₂ H ₄ 0) _n4 ~ H

H- (OC ₂ H ₄ ) _n `` 0— CH HCH ₂ — 0_CH ₂ CHCH ₂ — 0— (C ₂ H ₄ 0> n2— H (1-0)

0— (C ₂ H ₄ 0) f H

[0061] [6]

^C 6 ^F 13 ^CH 2 \ ... (3- _4a )

0

[0062] [Chemical 7] ■■ '(卜 la)

[0063] Compound (3-4a) by changing to other compounds of the formula (3-4), at least one of R ⁿ to R ¹⁴ in the compounds (1 la), I匕合prepared by using A compound with a structure corresponding to (3-4) is obtained.

Rf (CH ₂ ) _p ^ _r7

0

(3-4) (However, Rf is a perfluoroalkyl group having 3 to 12 carbon atoms, and p represents an integer of 0 to 16)

The following will be exemplified at least one has the structure of R ⁿ to R ^14.

[Table 4]

Compound (3-4a) by changing to other compounds of the formula (3-5), at least one of R ⁿ to R ¹⁴ in the compound (1 one la), I匕合prepared by using (3 — A compound with a structure corresponding to 5) is obtained.

(3-5)

[Table 5]

By changing the compound (3-4a) to another compound represented by the formula (3-1), at least one of R ⁿ R ¹⁴ in the compound (1 1 la) is converted into the used compound (3-1). A compound with the corresponding structure is obtained.

Rf (CH _z ) p— COOH

(3-1)

Examples of the structure possessed by at least one of R ⁿ R ¹⁴ are shown below.

[¾6]

C ₃ F 7— C〇1 C ₃ F ₇ -CH ₂ -CO-

C ₄ F ₉ — CO— C ₄ F ₉ — CH ₂ — CO—

CsFu— CO— C ₅ Fu-CH ₂ -C〇一

C ₆ F ₁₃ — CO— C ₆ F ₁₃ — CH ₂ — CO—

C ₇ F ₁₅ — CO— C ₇ F ₁₅ -CH _2- CO-

C ₈ F ₁₇ — CO— ₈ F ₁₇ — h _ <> — O—

C ₉ F ₁₉ — C〇— C ₉ F ₁₉ — CH ₂ — CO—

10F21― CO— C ₁₀ F ₂₁ — CH ₂ — CO—

CiiFgg— CO— CiiF ₂₃ — CH ₂ — CO—

^ 1 2-^ 25― CO— C ₁₂ F ₂₅ — CH ₂ — C〇ichi

[Comparative Example 1]

PEG-1000 (polyethylene glycol, manufactured by Nippon Oil & Fats Co., Ltd.) 20g, 0.15g of BF-OEt (manufactured by Wako Pure Chemical Industries, Ltd.), compound (3-4a) (Daikin Chemicals Sales)

3 2

150.4 g) was added, and the mixture was heated and stirred at 60 ° C for 1 hour. It was confirmed by G.C that the conversion rate of compound (3-4a) was 99% or more, and the reaction was terminated to obtain the desired compound (II). In the compound (Π), k is 22 on average.

[0067] [Chemical 8]

C ₆ F ₁₃ C CHCH ₂ — 0— (C ₂ H ₄ 0> _k — CH ₂ HCH ₂ C _s F ₁₃ ... (n)

OH OH

[Comparative Example 2]

In the same manner as in Comparative Example 1, compound (III) was synthesized. Compound (III) is a compound obtained by changing CF in compound (II) to CF.

6 13 3 17

[Comparative Example 3]

SC-E1000 (Sakamoto Yakuhin Kogyo Co., Ltd.) 10g, anhydrous carbonic acid carbonate (Nihon Soda Co., Ltd.) 1.38g, acetonitrile 31.3g Xafluoropropene trimer (Amax Co.) 9. Og And stirred at room temperature for 7 hours. At G.C, it was confirmed that the conversion rate of hexafluoropropene trimer was 99% or more, and stirring was stopped. Then, filtration and solvent distillation were performed to obtain the target compound (IV). R ²¹ R ²⁴ in compound (IV) is On average, two are hydrogen atoms and the other two are CF. In addition, for compound (IV), "C

9 17

— NMR was measured. The results are shown below.

1 ³ C—NMR (NOE complete removal decoupling method) (300 MHz, solvent: CD OD, standard

3 substances: hexamethyldisiloxane): 62.1 (2C, S), 69.3 (2C, m), 71.4 (42C, with multiple shoulders), 73.6 (2C, S), 79 4 (2C, S) 116-124 (many split peaks).

[0070] [Chemical 9] · ■-(I)

[0071] The compounds of Examples and Comparative Examples were dissolved in water to prepare aqueous solutions having a predetermined concentration. Thereafter, static surface tension was measured by the Wilhelmi method using an automatic surface tension meter CBVP-A3 type (manufactured by Kyowa Interface Chemical Co., Ltd.). The results are shown in Table 4.

[0072] [Table 7]

[0073] From the results in Table 4, it was found that the compound (I la) of the present invention has a good ability to lower the surface tension even at a low concentration.

Industrial applicability

[0074] The fluorine-containing compound of the present invention is characterized by being superior in solubility in each solvent and also having excellent surface tension reducing ability as compared with conventional fluorine-containing compounds, and exhibits a sufficient effect even in a small amount. Can be used for a wide range of purposes.

Claims

Claims [1] A fluorine-containing compound represented by the following formula (I):

[Chemical 1]

... (|)

However, J ⁵ is a hydrogen atom, carbon number 1 to: LO alkyl group, or —Z ⁵ — O— (AkO) n5

[2] The fluorine-containing compound according to claim 1, represented by the following formula (I1):

[Chemical 2]

RLX ¹ — i0Ak) _n “0 + 10 CH ₂ CHCH ₂ — 0”) ”CH ₂ CHCH ₂ — 0— (Ak0) _n2 — X ² _R ² .. · (\-])

, / Rn j

R and X ³ — (0Ak) _n3 — 0 0 ~ (Ak0) _n4 — X ⁴ — R ⁴ where AkO represents an oxyalkylene group, R′-R ⁴ represents a hydrogen atom or a monovalent organic group , I ^ to R ^{4 is} a fluorine-containing alkyl group having 1 to 12 carbon atoms which may have an etheric oxygen atom, m represents an integer of 0 to 20, and nl to n4 represent 0 represents an integer of 20, a nl + n2 + n3 + n4> 0, 1 ~: ^ 4 is a single bond or a divalent linking group.

[3] The fluorine-containing compound according to claim 1 or 2, wherein the total force of nl to n6 existing in formula (I) or formula (1-1) is 50.

[4] R ¹ — X ¹ —, R ² — X ² —, R ³ — X ³ —, R ⁴ — X ⁴ — is a hydrogen atom or Rf— (CH) p— CH

2

(OH) — CH— Y— (where p is an integer from 0 to 16, and Rf is a perfume having 3 to 12 carbon atoms. R ¹ — X ¹ —, R ² — X ² —, R ³ — X ³ —, R ⁴ — X ⁴ at least 1 Rf— (CH) p— CH (OH) — C

2

H—Y—, m represents an integer of 1 to 3, and nl + n2 + n3 + n4 is 4 to 50.

2

2. The fluorine-containing compound according to 2.

[5] A fluorine-containing alkyl having 1 to 12 carbon atoms, which has an etheric oxygen atom at the terminal hydroxyl group of an alkylene oxide adduct obtained by adding alkylene oxide to glycerin or polyglycerin. A method for producing a fluorine-containing compound, wherein a fluorine-containing compound represented by the following formula (I 1) is obtained by reacting a compound having a group.

[Chemical 3]

R ¹ — X ¹ — (OAk) _n1 -0 + CH ₂ CHCH ₂ -o -CH ₂ CHCH ₂ — 0— (AkO) _n2 -X ² — R ² … (卜 1)

^{^{R 3 -X 3 ™ {0Ak)}} n3 - OO- (AkO) rv4 ~ -X --R 4 However, AKO represents a Okishiarukiren group, an R'-R ⁴ is a hydrogen atom or a monovalent organic group At least one of I ^ to R ⁴ is a fluorine-containing alkyl group having 1 to 12 carbon atoms which may have an etheric oxygen atom, m represents an integer of 0 to 20, and nl to n4 are It represents an integer of 0 to 20, nl + n2 + n3 + n4> 0, and ¹ to ^ ⁴ represents a single bond or a divalent linking group.

[6] A terminal hydroxyl group of an alkylene oxide adduct obtained by adding an alkylene oxide to a compound having an etheric oxygen atom and optionally having a fluorine-containing alkyl group having 1 to 12 carbon atoms. , A method for producing a fluorine-containing compound obtained by reacting glycerin or polyglycerol to obtain a fluorine-containing compound represented by the following formula (1-1).

[Chemical 4]

R ¹ — X ¹ ... (t ι)

However, AkO represents an oxyalkylene group, R′-R ⁴ represents a hydrogen atom or a monovalent organic group, and at least one of I ^ to R ⁴ may have an etheric oxygen atom. A fluorine-containing alkyl group of 1 to 12, m represents an integer of 0 to 20, nl to n4 represents 0 to 20 Nl + n2 + n3 + n4> 0, ¹ to: ^ ⁴ represents a single bond or a divalent linking group.

[7] A surfactant containing the fluorine-containing compound according to claim 1 or 2.

[8] A leveling agent comprising the fluorine-containing compound according to claim 1 or 2.

[9] An antifogging agent comprising the fluorine-containing compound according to claim 1 or 2.

[10] A method for reducing surface tension, wherein the fluorine-containing compound according to claim 1 or 2 is added to a liquid to reduce the surface tension of the liquid.

[11] A method for modifying a resin surface, wherein the fluorine-containing compound according to claim 1 or 2 is added to the resin to modify the surface of the resin.