JP2003292989A - Fluorine-based surfactant composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorine-based surfactant composition which has high surface-active effects such as high permeating and wetting properties and a high leveling property and has good solubility. <P>SOLUTION: This fluorine-based surfactant comprising two or more fluorine- based compounds having partially fluorinated alkyl groups represented by formula: F(CF<SB>2</SB>)<SB>2n</SB>CH<SB>2</SB>CH<SB>2</SB>- [(n) is an integer of 1 to 10] and having purities of ≥85 wt.%, respectively, such as fluorine-based compounds represented by the following general formula (1): F(CF<SB>2</SB>)<SB>2n</SB>CH<SB>2</SB>CH<SB>2</SB>XY (1) [(n) is an integer of 1 to 10; X is a direct bond or a divalent connecting bond; Y is an amphiphilic group], is characterized in that the two or more fluorine-based compounds are those having partially fluorinated alkyl groups having different (n) values, respectively. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to various coating materials such as printing materials, photosensitive materials, photographic materials, paints, adhesives, surface functional protective film forming materials, cleaning agents, optical materials, release agents, and automobiles. , Ships, vehicles, aircraft, building materials, home appliances, OA
Applied to compositions such as equipment, electrical / electronic equipment, communication equipment, optical members, electric wires / wiring materials, molding materials for various industrial parts, grease, various sealing materials, etc., penetration / wettability, leveling property, surface The present invention relates to a fluorosurfactant composition suitable for enhancing functionality.

[0002]

2. Description of the Related Art Fluorine-based surfactants are superior to hydrocarbon-based or silicon-based surfactants in that they are added to compositions for coating, molding, etc. based on their high surface tension reducing ability. It is a material that realizes excellent penetration / wetting properties, leveling properties, etc., and various fluorochemical surfactants have been proposed so far. Perfluoroalkyl (R that is the source that realizes the surface-active effect of the fluorine-based surfactant
Examples of the method for producing the group f) include an electrolytic fluorination method, a telomerization method, and an oligomerization method, and any method can produce a surfactant having a different Rf group chain length. Is.

Among these, recently, among the fluorine-based surfactants produced by the electrolytic fluorination method, those having an Rf group chain length of 8 have low toxicity but high bioaccumulation, and therefore can be used as various industrial materials. It has become shunned. Also, Rf
Surfactants composed of only those having a base chain length of 7 or less,
The low surface-active effect has unavoidably limited its applications.

On the other hand, the Rf group of the fluorosurfactant produced by the telomerization method is usually produced by the addition reaction of tetrafluoroethylene, so that the Rf group chain length usually has a distribution. That is, when trying to obtain a useful Rf group chain length as a surfactant, a shorter chain and a longer chain are inevitably produced. If the length of the chain or the distribution of the chain length is shorter than the desired one, the surfactant effect decreases, and if the length of the long chain occurs, the solubility in the composition to be added decreases, resulting in processing work. It was not uncommon to reduce sex.

Further, in order to improve these problems,
Fluorine-based surfactants having an Rf group consisting of a single chain length are also commercially available and are used in some applications.
Depending on the purpose, sufficient ones satisfying the surface active effects such as penetrability / wettability and leveling property and the solubility in the composition to be added have not been obtained.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a fluorosurfactant composition having a high surfactant effect and good solubility.

[0007]

Means for Solving the Problems The inventors of the present invention have made extensive studies to solve the above problems, and found that Rf
By containing two or more kinds of fluorine compounds having a narrow distribution width of the base chain length, that is, fluorine compounds having a purity of a certain level or more in a combination having different Rf base chain lengths, the surfactant effect is high and the solubility is high. The inventors have found that a good fluorine-based surfactant composition can be obtained, and have completed the present invention.

That is, according to the present invention, F is used as a surfactant.
(CF ₂ ) _2n CH ₂ CH ₂ — (n represents an integer of 1 to 10) A fluorine-based compound containing two or more fluorine-containing compounds having a partially fluorinated alkyl group and a purity of 85% by weight or more. A surfactant composition, wherein the two or more kinds of fluorine compounds are fluorine compounds having partially fluorinated alkyl groups in which n is different from each other. Is.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
To do. Usually, in the telomerization method,
Add tetrafluoroethylene to chill iodide
The Rf base chain length. Then add ethylene
Perfluoroethyl iodide, which is the starting material
Of various fluorine-containing compounds for surfactants
It can be synthesized. Therefore, by the telomerization method
Most of the manufactured fluorine-based compounds for surfactants are F
(CF₂)_2nCH₂CH ₂Partially fluorinated ar represented by-
Will have a kill group.

According to the knowledge of the present inventors, in order to combine the surface-active effects such as penetrability / wettability and leveling property with the solubility of the resin, solvent and various additives in the composition to be added. In particular, _{n in the} partially fluorinated alkyl group represented by F (CF ₂ ) _2n CH ₂ CH ₂ — varies depending on the intended composition, the level of these performances, the processing steps, and the like.

Therefore, depending on the desired composition, performance, processing step, etc., a partially fluorinated alkyl group of different n [F
(CF ₂ ) _2n CH ₂ CH ₂ — (n is an integer of 1 to 10)] having a purity of 85% by weight or more and containing two or more fluorine-containing compounds have a surfactant effect and a composition. It has been found that it is extremely effective to combine the solubility in substances. Here, the purity of the fluorine-based compound is usually measured by a gas chromatography (GC) method.
When the compound cannot be detected by the GC method,
After chemically modifying the moiety other than the partially fluorinated alkyl group, for example, the divalent linking group X and / or the hydrophilic group Y in the fluorine-based compound represented by the general formula (1) described below, G
The method C is used. Alternatively, the measurement may be performed by using various other chromatographic methods such as high performance liquid chromatography and capillary electrophoresis, and mass spectrometry.
The purity of the fluorine-based compound is preferably 95% by weight or more, more preferably 98% by weight or more.

The purity of the fluorine-based compound in the present invention refers only to the difference due to the distribution of n in the partially fluorinated alkyl group represented by F (CF ₂ ) _2n CH ₂ CH _2- , and it depends on the production method. Other compounds that are by-products are not included in this calculation of purity. For example, in Synthesis Example 1 described later, a fluorine-based compound having a purity of 98.6% by weight and having an n = 8 partially fluorinated alkyl group is synthesized. The specific composition is as follows. n) is 4 to 1
A mixture of two and their weight ratio is (n =
4) / (n = 6) / (n = 8) / (n = 10) / (n =
12) = 0 / 0.2 / 0.5 / 98.6 / 0.6 / 0.
1 (GC analysis value).

The fluorine-based compound used in the present invention is
F (CF ₂ ) _2n CH ₂ CH ₂ — (n is an integer of 1 to 10) represented by F (CF ₂ ) _2n CH ₂ CH ₂ — (n is an integer of 1 to 10) may be a fluorine-based compound having a purity of 85% by weight or more. It may have two or more fluorinated alkyl groups. Therefore, the fluorosurfactant composition of the present invention contains 1 partly fluorinated alkyl group in addition to 2 or more kinds containing only 1 partly fluorinated alkyl group having a purity of 85% by weight or more. Containing a fluorine-based compound having a purity of 85% by weight or more and a fluorine-containing compound having a purity of 85% by weight or more having two or more partially fluorinated alkyl groups, or having a purity of 85% having two or more partially fluorinated alkyl groups %, Or two or more kinds of only fluorine compounds may be contained. However, in any case, it is essential that a combination of fluorine-based compounds having partially fluorinated alkyl groups with different n is used.

In the present invention, the method for obtaining a fluorine-based compound having a purity of 85% by weight or more is not particularly limited. That is,
Purification may be carried out at the stage of perfluoroiodide or perfluoroethyl iodide, which are the raw materials, or may be carried out at any step of producing the target fluorine-based compound from these compounds. In addition, there is no limitation on the method of purification, for example, distillation using various equipment, extraction using various solvents, column or batch treatment using various adsorbents such as silica, alumina, activated carbon and ion exchange resins, and washing. Known publicly known operations such as processing can be used.

According to the knowledge of the present inventors, in order to combine the surface-active effect such as penetration / wetting property and leveling property with the solubility in the composition to be added such as resin, solvent and various additives. It is necessary to contain two or more kinds of the above-mentioned 85% by weight pure fluorine-containing compounds having the optimum n depending on the purpose, application and processing step. Where 2
When containing more than one kind of fluorine-based compound, they may be mixed by any method.

According to the knowledge of the present inventors, the composition to be added in the fluorine-containing surfactant composition of the present invention containing two or more kinds of fluorine-containing compounds having partially fluorinated alkyl groups different in n. In addition to its solubility in water, in applications where foaming suppression, rapid defoaming properties are required, and in processing steps, the fluorine-containing compound having a n ≦ 5 partially fluorinated alkyl group in the all-fluorine-containing compound is used. The content is preferably 5% by weight or less, particularly preferably 3% by weight or less, most preferably 1% by weight or less. Thus, n ≧ 5
By positively removing the fluorine-containing compound having a partially fluorinated alkyl group from the fluorine-containing surfactant composition, the solubility in the target composition is increased and the allowable range of the addition amount is expanded. it can. Also, suppression of foamability,
It is also expected that the defoaming property will be improved, the process conditions can be simplified in many processing steps, and the process time can be shortened.

Further, in order to efficiently obtain the surface-active effect with a lower addition amount, the fluorine-containing surfactant composition of the present invention contains a fluorine-containing compound having a partially fluorinated alkyl group of n = 1. The ratio is preferably 5% by weight or less, and 3
It is particularly preferably not more than 1% by weight, most preferably not more than 1% by weight. Depending on the target composition, if the fluorine compound having a partially fluorinated alkyl group of n = 1 is contained in an amount of more than 5% by weight, not only the target surfactant effect cannot be obtained, but also a high addition amount is required. There is a case where the necessity is imposed and, as a result, the original performance of the composition to be added is impaired. From such a viewpoint, the present inventors further selected the chain length of the partially fluorinated alkyl group and the ratio thereof more strictly with respect to the intended composition, and thereby more efficiently than the conventionally known compound. It has been found that a surface-active effect can be obtained, and as a result, the permissible range of processing conditions can be widened depending on the purpose and application.

Specifically, permeation into a fine base material and area
Wetness, when a high addition amount is required to obtain a high leveling property in thin film coating of 10 to 3000 nm, or when it is desired to suppress foamability due to restrictions such as line speed and coating equipment, it is added. It is preferable that the composition has a high solubility in the composition to be formed, the foaming property is suppressed, and the defoaming property is improved. That is, the content of the fluorine-containing compound having a partially fluorinated alkyl group of n = 2 in the fluorine-containing surfactant composition of the present invention is preferably 25% by weight or more,
Above all, it is more preferably 40% by weight or more.

On the other hand, when it is not desired to impair the original performance of the composition to be added, it is desirable from the economical point of view that the addition amount of the fluorosurfactant composition is kept to a minimum. In such a case, the content of the fluorine-containing compound having a partially fluorinated alkyl group of n = 4 in the fluorine-containing surfactant composition is, in order to effectively obtain the surface-active ability even when added in a small amount, It is preferably 25% by weight or more, more preferably 40% by weight or more.
It is particularly preferably at least 0% by weight.

As a secondary effect of using the fluorosurfactant composition of the present invention, after a desired processing step such as coating or molding, a film or paste formed by the composition is formed. It is also possible to functionalize the surface of the molded body or the like. Such surface properties that can be expected after processing include water and oil repellency, slipperiness, non-stickiness, water resistance,
Antifouling property and the like can be mentioned, but in order to effectively realize these, the content of the fluorine-containing surfactant having a partially fluorinated alkyl group of n = 4 in the fluorine-containing surfactant composition is It is preferably 50% by weight or more, and more preferably 70% by weight or more.

According to the knowledge of the present inventors, a surfactant composition having a more balanced balance of the surfactant effect, the solubility in the compound to be added, the suppression of the foaming property and the improvement of the defoaming property. In order to achieve the following, a fluorine-based compound having a partial fluorinated alkyl group of n = 2 and a purity of 85% or more,
= 2 or more fluorine-based compounds selected from the group consisting of fluorine-based compounds having a partially fluorinated alkyl group of = 3 and a purity of 85% or more and fluorine-containing compounds having a partially fluorinated alkyl group of n = 4 and a purity of 85% or more It is preferable that the compound contains a fluorine-based compound having a partial fluorinated alkyl group of n = 2 and a purity of 85% or more, a fluorine-based compound having a partially fluorinated alkyl group of n = 3 and a purity of 85% or more, and It is more preferable to use together all fluorine-based compounds having a partially fluorinated alkyl group of n = 4. In this case, the mixing ratio of these fluorine-containing compounds of n = 2, 3 and 4 is [(n = 2) / (n = 3) /
(N = 4)] is (5-50) / (5-85) / (10
90) is preferable, and (10-40) / (20-70) /
(25-80) is more preferable.

By the way, in order to make the fluorine-containing compound containing a partially fluorinated alkyl group function as a surfactant, a resin, a solvent, etc. are added in the same molecule as shown in the following general formula (1). It is preferable that a hydrophilic group that enhances solubility in the composition is bound. F (CF ₂ ) _2n CH ₂ CH ₂ XY (1) (wherein, n represents an integer of 1 to 10, X represents a direct bond or a divalent linking group, Y Indicates a hydrophilic group.)

Here, when X is a direct bond, the hydrophilic group Y is directly bonded to the partially fluorinated alkyl group. However, in the production method in which Y is introduced, the desired fluorosurfactant composition is obtained. Considering the compatibility with the composition to which the product is added, there are many cases where a divalent linking group is used. The divalent linking group X is designed according to the target Y and the composition to be added, and is not particularly limited, but examples thereof include the following compounds. -SO ₂ NR- (R is a hydrogen, the number phenyl group or a C 1
To 18 alkyl _{group) -O- -O (CH 2) k} - (k is an integer of 1 to _{8) - (CH 2) k -} (k is an integer of 1 to 8) -CH (OH) (CH ₂ ) _K (k is an integer of 1 to 8) -CONR- (R is hydrogen, a phenyl group or 1 to 8 carbon atoms)
18 _{alkyl) - (OC p H 2P +} 1) q (CH 2) k - (p is an integer of from 2 to 6, q is 1 to 100 integer, k is an integer of 1 to 8) -NR (CH _{2) k} - (R is hydrogen, phenyl or alkyl group having 1 to 18 carbon atoms, k is an integer of 1 to _{8) -SO 2 NR (CH 2)} k - (R is hydrogen, the number phenyl group or a C 1 to 18 alkyl group, k is an integer of 1 to _{8) -SO 2 N (CH 2 CH} 2 OH) (CH 2) k - (k is an integer of 1 to _{8) -SO 2 NR 1 (CH 2} ) k1 _{CONR 2 (CH 2) k2 -} (R 1, R
₂ are both hydrogen, a phenyl group or an alkyl group having 1 to 18 carbon atoms, k1, k2 are both an integer of 1 to _{8) -S (CH 2) k -} (k is an integer of 1 to 8) -S (CH _{2 ) k1 CONR (CH 2) k2} - (R is hydrogen, phenyl or alkyl group having 1 to 18 carbon atoms, k1, k2 are both an integer of 1 to 8) --OCO is (CH _{2) k} - _(k is 1 8 integer)

Of these, in consideration of versatility as a surfactant, production method, etc., the divalent linking group X is a direct bond, --SO ₂ NR-- (R is hydrogen or alkyl having 1 to 18 carbon atoms). _{group), - SO 2 NR (CH} 2) k - (R is hydrogen or an alkyl group having 1 to 18 carbon atoms, k is an integer of 1 to 8),
_{-S (CH 2) k - (} k is an integer of 1 to 8) are preferred. When the divalent linking group X is introduced, depending on the composition to be added, both X and Y contribute to the role of a hydrophilic group, that is, to improve the solubility in the solvent, resin, etc. in the composition to be added. .

Next, the hydrophilic group Y will be described. The amphiphilic group Y referred to here is for enhancing the solubility by making the target fluorine-based compound function as a surfactant and making it compatible with the composition of various additives such as solvents, resins, pigments and fillers. And a functional group or segment that imparts hydrophilicity and / or lipophilicity to a partially fluorinated alkyl group that exhibits hydrophobicity / oleophobicity. The selection of Y is the desired composition,
Depending on the application, compatibility with the system, ionicity, functionality, etc. are taken into consideration. For example, -SO ₃ H, -COOH, PO
Acid groups such as (OH) ₃ and its Li, Na, K, Ca, M
g, metal salts such as Al, ammonia, diethylamine, triethylamine, n-propylamine, iso-propylamine, n-butylamine, tert-butylamine, di (n-butyl) amine, ethylenediamine, diethylenediamine, monoethanolamine, diethanolamine , Organic amine salts such as propanolamine, toluidine, pyridine, etc., ester groups such as sulfuric acid ester group, carboxylic acid ester group, phosphoric acid ester group, nitric acid ester group, hydroxyl group, methoxyl obtained by reaction of these acid groups with various alcohols, etc. Group, alkoxyl group such as ethoxyl group, amino group, sulfonylamido group, carbonylamido group, mercapto group, epoxy group, polymerization degree of 1 to 10
0 polyethylene oxide, polypropylene oxide,
A polyalkylene oxide group such as polybutylene oxide,
An allyl group, an acryloyl group, a vinyl group such as a methacryloyl group, a quaternary amine salt residue represented by the following general formula _{^{(2), -N + R 3}} R 4 R 5 · Z - ········ (2) (In the formula, R ₃ , R ₄ , and R ₅ are phenyl groups or 1 to 1 carbon atoms.
8 is an alkyl group, Z ⁻ is halogen, CH ₃ (C
₆ H ₄ ) SO ₃ ^{− and} other anions. ) The following general formula (3)
An amine and an acid salt residue represented by: -NR ₁ R ₂ · A (3) (wherein R ₁ and R ₂ are both hydrogen, a phenyl group or a carbon number of 1 to 1). 18 is an alkyl group, A is an acid such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, etc.) and the like. Among these, an acid group and a metal or amine salt thereof, a polyalkylene oxide group, or a quaternized amine salt residue is preferable from the viewpoint of versatility in a publicly known composition.

Specific examples of the above-mentioned fluorine-containing surfactant having a partially fluorinated alkyl group and a hydrophilic group in the same molecule include (1) C ₈ F ₁₇ CH ₂ CH ₂ SO ₃ K (2) C ₆ F ₁₃ CH ₂ CH ₂ SO ₃ K (3) C ₄ F ₉ CH ₂ CH ₂ SO ₃ K (4) C ₈ F ₁₇ CH ₂ CH ₂ SO ₃ H (5) C ₆ F ₁₃ CH ₂ CH ₂ SO ₃ H (6) C ₄ F ₉ CH ₂ CH ₂ SO ₃ H (7) C ₈ F ₁₇ CH ₂ CH ₂ SO ₃ Li (8) C ₈ F ₁₇ CH ₂ CH ₂ SCH ₂ COOLi (9 ) C ₈ F ₁₇ CH ₂ CH ₂ SCH ₂ CH ₂ COOLi (10) C ₆ F ₁₃ CH ₂ CH ₂ SCH ₂ CH ₂ COOLi (11) C ₄ F ₉ CH ₂ CH ₂ SCH ₂ CH ₂ COOLi (12) C ₈ F ₁₇ CH ₂ CH ₂ SCH ₂ CH ₂ COOK (13) C ₈ F ₁₇ CH ₂ CH ₂ SCH ₂ CH ₂ COONa (14) C ₈ F ₁₇ CH ₂ CH ₂ SO ₂ NHCH ₂ COOK (15) C ₆ F ₁₃ CH ₂ CH ₂ SO ₂ NHCH ₂ COOK (16) C ₆ F ₁₃ CH ₂ CH ₂ SO ₂ N ( C ₃ H ₇ ) CH ₂ CO
OK (17) C ₆ F ₁₃ CH ₂ CH ₂ SO ₂ N (C ₂ H ₅ OH) CH ₂
COOK (18) C ₆ F ₁₃ CH ₂ CH ₂ SO ₂ N (C ₆ H ₅ ) CH ₂ CO
OK (19) C ₁₄ F ₂₉ CH ₂ CH ₂ O (CH ₂ CH ₂ O) _n H
(N is an integer of 2 to 10) (20) C ₁₂ F ₂₅ CH ₂ CH ₂ O (CH ₂ CH ₂ O) _n H
(N is an integer of 2 to 10) (21) C ₁₀ F ₂₁ CH ₂ CH ₂ O (CH ₂ CH ₂ O) _n H
(N is an integer of 2 to 10) (22) C ₈ F ₁₇ CH ₂ CH ₂ O (CH ₂ CH ₂ O) _n H
(N is an integer of 2 to 10) (23) C ₆ F ₁₃ CH ₂ CH ₂ O (CH ₂ CH ₂ O) _n H
(N is an integer of 2 to 10) (24) C ₄ F ₉ CH ₂ CH ₂ O (CH ₂ CH ₂ O) _n H
(N is an integer of 2 to 10) (25) C ₂ F ₅ CH ₂ CH ₂ O (CH ₂ CH ₂ O) _n H
(N is an integer of 2 to 10) (26) C ₈ F ₁₇ CH ₂ CH ₂ O (CH ₂ CH ₂ O) _n (CH ₂ ) ₄
SO ₃ Na (n is 2 to 10 _{integer) (27) C 6 F 13} CH 2 CH 2 O (CH 2 CH 2 O) n CH
₃ (n is an integer of 2 to 10) (28) C ₆ F ₁₃ CH ₂ CH ₂ O (CH ₂ CH (CH ₃ ) O)
_{m (CH 2 CH 2 O)} n H (m, n are both 2 to 10 _{integer) (29) C 8 F 17} CH 2 CH 2 OPO (OH) 2 (30) C 6 F 13 CH 2 CH 2 OPO (OH) ₂ (31) C ₈ F ₁₇ CH ₂ CH ₂ OSO ₂ N (C ₃ H ₇ ) CH ₂ C
H ₂ OPO (OH) ₂ (32) C ₈ F ₁₇ CH ₂ CH ₂ OH (33) C ₈ F ₁₇ CH ₂ CH ₂ SH (34) C ₈ F ₁₇ CH ₂ CH ₂ OCOCH = CH ₂ (35) C ₈ F ₁₇ CH ₂ CH ₂ SO ₂ NH ₂ (36) C ₆ F ₁₃ CH ₂ CH ₂ SO ₂ NH ₂ (37) C ₄ F ₉ CH ₂ CH ₂ SO ₂ NH ₂ (38) C ₈ F ₁₇ CH ₂ CH ₂ SO ₂ NH (CH ₂ ) ₃ N ⁺ (CH
^{_{3) 3 I - (39)}} C 8 F 17 CH 2 CH 2 SO 2 NH (CH 2) 3 N + (CH
^{_{3) 3 Br - (40)}} C 8 F 17 CH 2 CH 2 SO 2 NH (CH 2) 3 N + (CH
^{_{3) 3 Cl - (41)}} C 8 F 17 CH 2 CH 2 SO 2 NH (CH 2) 3 N + (CH 3) 3 CH 3 C 6 H 4 SO 3 - (42) C 8 F 17 CH 2 CH ₂ SO ₂ NH (CH ₂ ) ₃ N (C
_{H 3) 2 HCl (43)} C 6 F 13 CH 2 CH 2 SCH 2 CH 2 CON (CH 2)
Compounds such as ₃ SO ₃ Na may be mentioned.

There are no particular restrictions on the method for producing the fluorine-containing compound used as the fluorine-containing surfactant in the present invention with respect to either the partially fluorinated alkyl group or the hydrophilic group Y, and known publicly known organic compounds can be used depending on the purpose. It is possible to carry out the chemical reaction using the known equipment. The telomerization method is industrially useful as the method for introducing the partially fluorinated alkyl group, but it is also possible to introduce it by using a fluorinated alkylating agent or the like after producing a non-fluorine equivalent compound in advance. Is. Further, the obtained fluorine-based compound may be purified by a known method, or may be used as it is as a composition containing a compound by-produced during production depending on the use and purpose.

The addition amount of the fluorosurfactant composition of the present invention to the intended composition is not particularly limited, but the application,
Appropriately selected in consideration of desired performance, economy, processing steps, etc., and usually 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, relative to 100 parts by weight of the desired composition. It is preferably 0.1 to 2 parts by weight. If necessary, a silicone-based surfactant, a hydrocarbon-based surfactant, and a fluorine-based surfactant other than the fluorine-based compound having a partially fluorinated alkyl group used in the present invention and having a purity of 85% by weight or more may be used in combination. Is also possible. By mixing such different kinds of surfactants, there are cases where the surface active effects such as penetrating / wetting properties and leveling properties which cannot be obtained by themselves are obtained.

The composition to which the fluorine-containing surfactant composition of the present invention is added is not particularly limited, and it can be added to a publicly known composition. Examples of the compound used in the composition include the followings.

First, water and the following organic solvents. Examples of organic solvents include methanol, ethanol,
Isopropyl alcohol, n-butanol, iso-butanol, tert-butanol and other alcohols, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone and other ketones, methyl acetate, ethyl acetate , Esters such as butyl acetate, methyl lactate, ethyl lactate, butyl lactate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, butyl 2-oxypropionate, 2
-Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2
-Monocarboxylic acid esters such as butyl methoxypropionate, polar solvents such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, ethers such as methyl cellosolve, cellosolve, butyl cellosolve, butyl carbitol, ethyl cellosolve acetate,
Propylene glycols such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, and esters thereof, Halogen-based solvents such as 1,1,1-trichloroethane and chloroform, ethers such as tetrahydrofuran and dioxane, aromatics such as benzene, toluene and xylene, and perfluorooctane and perfluorotri-n-butylamine. Examples thereof include fluorinated inner liquids. These solvents may be a single system or a mixed solvent system of two or more kinds. It should be noted that the solvent referred to herein is also a solvent that acts as a dispersion medium in the system.

Next, the resin. Examples of the resin include acrylic resin, urethane resin, phenol resin, polyester resin, alkyd resin, epoxy resin, olefin resin such as polyethylene and polypropylene, vinyl resin such as polyvinyl chloride and polystyrene, fluorine resin, polycarbonate resin, polyimide resin. , Engineering resins such as polyamide resin and polyparaphenylene sulfide, thermoplastic and thermosetting resins such as ABS resin, SBR, NBR, EPM, EPDM, nitrile rubber, urethane rubber, norbornene rubber, acrylic rubber,
Examples thereof include rubbers such as chloroprene rubber, epichlorohydrin rubber, silicone rubber and fluororubber. These resins may be used alone or in combination of two or more. Further, when two or more kinds of resins are used in combination with the surfactant of the present invention, one of the surfactant effects can be expected to act as a compatibilizing agent for resins having different compositions or molecular weights.

Finally, there are additives other than the surfactant.
Examples of the additives include silane-based, titanium-based, zirco-aluminate-based coupling agents, and fluorine-containing alkoxysilane compounds, fluorine-containing titanium acylate compounds, fluorine-containing alkoxyzirconium compounds and other fluorine-based coupling agents. Coupling agents, organic / inorganic pigments, dyes, colorants such as carbon, silica, titanium oxide, zinc oxide, aluminum oxide, tin oxide, zirconium oxide, calcium oxide, calcium carbonate, inorganic powder such as glass filler, filling Material, higher fatty acid, poly (vinylidene fluoride), poly (tetrafluoroethylene), polyethylene,
Organic fine powder such as acrylic beads, further photosensitizer, sensitizer, light resistance improver, weather resistance improver, heat resistance improver, conductive agent, antioxidant, rust preventive, rheology control agent,
Examples include various fillers such as thickeners, anti-settling agents, defoamers and deodorants. The additive may be used alone or in combination of two or more.

The composition to which the fluorine-containing surfactant composition of the present invention is added can obtain excellent penetrability / wetting property and leveling property by applying a publicly known processing method. Examples of the processing method include a gravure coater, a knife coater, a roll coater, a comma coater, a spin coater, a bar coater, a brush coating, a dipping coating, a spray coating, an electrostatic coating, a coating method and an apparatus such as screen printing, an inkjet method, an injection. Various molding methods such as extrusion, hollowing, compression, reaction, vacuum, FRP, heat, roll sheet, calendar, biaxially stretched film, lamination and rotation, various molds, and injection molding using a stamper are used.

The composition containing the fluorine-containing surfactant composition of the present invention can be used without any limitation. Utilizing excellent paintability / penetration and leveling properties,
For example, printing materials such as PS plate, LCD, LSI, organic E
L, photosensitive materials such as various photoresists for plasma display manufacturing, anti-reflection film agent for LSI manufacturing, LCD, L
SI, organic EL, cleaning agent for plasma display manufacturing,
Photographic materials such as etching agents, release agents, developing solutions, emulsions, paints for automobiles, aircraft, ships, building materials, home appliances, etc., dyes, adhesives for industrial and household use, scratch resistance, slipperiness, non-adhesion , Water- and oil-repellent property, hydrophilic property, lipophilic property, gas barrier property, heat resistance, light resistance, weather resistance, physiological activity, water resistance, moisture resistance, stain resistance, etc. surface functional protective film forming material, cleaning agent, Floor polish, foam extinguishing agent, plating bath mist preventive agent, lens sheet, optical material such as optical fiber, clothing, furniture, shoes, textiles such as sundries, artificial leather, synthetic leather non-woven fabric, etc.
Various coating agents for paper, films, cards, etc., automobiles, building materials, home appliances, medical materials, OA equipment, electric / electronic equipment, optical members, electric wires / wiring materials, molding materials for various industrial parts, grease, wax, etc. Sealing material, release agent,
To be applied to compositions such as rust preventives, anti-fog agents, anti-fog agents, anti-blocking agents, and dispersion media for polymer production or organic chemical reaction, to enhance penetration / wetting properties, leveling properties or various surface functionalities. It is useful as an additive.

[0035]

EXAMPLES Next, reference examples, examples and comparative examples are given in order to explain the present invention in more detail. "Parts" in the text are by weight unless otherwise specified.

Synthesis Example 1: Nonionic Fluorine Compound (S
-1) C ₈ F ₁₇ CH ₂ CH ₂ OH (FAl-8) in an autoclave equipped with a synthetic thermometer, heating, cooling, stirring, and a decompressor [however, the weight determined by gas chromatography (GC)] Ratio: C ₂ F ₅ CH ₂ CH ₂ OH / C ₄ F ₉ CH ₂ CH ₂ OH
/ C ₆ F ₁₃ CH ₂ CH ₂ OH / C ₈ F ₁₇ CH ₂ CH ₂ OH / C
₁₀ F ₂₁ CH ₂ CH ₂ OH / C ₁₂ F ₂₅ CH ₂ CH ₂ OH = 0 /
0.1 / 0.4 / 98.5 / 0.7 / 0.3] 233 g
(0.5 mol), sodium borohydride 0.76 g
(0.02 mol) and 1.5 g (0.006 mol) of iodine were charged and heated to 100 ° C. Then, 132 g (3.0 mol) of ethylene oxide (EO) was introduced,
The temperature was raised to 130 ° C. and held for 5 hours. Then, the mixture was cooled to room temperature and unreacted EO was removed under reduced pressure to obtain a target compound, a fluorine-based compound (S-1). The chain length of the partially fluorinated alkyl group of this compound is (n = 4) / (n = 6) /
(N = 8) / (n = 10) / (n = 12) = 0 / 0.2
/0.5/98.6/0.6/0.1 (GC analysis value), and the average addition mole number q of EO was 5.3.

Synthetic Examples 2 to 6: Synthesis of Nonionic Fluorine Compounds (S-2) to (S-6) The same reaction as in Synthetic Example 1 was carried out by using fluorine having n = 2 to 12 partially fluorinated alkyl groups. Fluorinated alcohols containing fluorinated alcohols in the weight distribution shown in Table 1 (FA1-
8), (FA1-6), (FA1-4), (FA1-M
1), (FA1-M2) and (FA1-M3) were applied to obtain fluorine compounds (S-2) to (S-6). Table 2 shows the fluorine compounds (S-2) to (S-
6) and the fluorine-based compound (S-
The weight distribution of the fluorine-based compound having a partially fluorinated alkyl group of n = 2 to 12 in 1) and the average number of moles of ethylene oxide added are collectively shown.

[0038]

[Table 1]

[0039]

[Table 2]

Synthesis Example 7: Anionic fluorinated compound (S
-7) In a 4-necked flask equipped with a thermometer, a stirrer, and a cooling device, perfluorooctylethyl iodide (C ₈ F ₁₇ CH ₂ CH ₂ I) having a single chain length of a partially fluorinated alkyl group was added. 14
4 g (0.25 mol) and thiourea 19 g (0.25 mol) were added to 125 ml of dimethylformamide (DMF).
Stir in the solution at 80 ° C for 3 hours to obtain thiuronium salt (C
A DMF solution of ₈ F ₁₇ CH ₂ CH ₂ SC (NH ₂ ) = NH ₂ ⁺ I ⁻ ) was prepared.

Then, ethyl acetate 226 was placed in a four-necked flask equipped with a stirrer, a gas introduction tube, a dropping funnel, and a cooling device.
g and ion-exchanged water 226 g, and the prepared DMF solution of thiuronium salt was added dropwise to chlorine gas 16800 m.
1 was blown in at 20 ° C. for 1 hour, and the mixture was further stirred for 30 minutes. Then, saturated sodium hydrogen sulfite aqueous solution was added to decompose chlorine blown in excessively. Then 30
0 ml of ion-exchanged water was added, and the resulting precipitate was filtered, washed with a saturated aqueous solution of sodium hydrogen sulfite and ion-exchanged water, dried at room temperature under reduced pressure, and dried with perfluoroethylsulfonyl chloride (C ₈ F ₁₇ CH ₂ CH ₂ SO ₂ Cl) was obtained.

Next, 4 equipped with a thermometer, stirring and cooling device
Glycine ethyl ester hydrochloride 42 in a two-necked flask
g (0.3 mol) and sodium hydrogen carbonate 28 g (0.3
(3 mol), 100 ml of ethyl acetate and 100 ml of water were charged, the mixture was stirred at 30 ° C. for 3 hours, 51 g (0.1 mole) of perfluoroethylsulfonyl chloride was added, and the mixture was further stirred for 4 hours. The organic layer was extracted from the obtained reaction solution with ethyl acetate and dried under reduced pressure to obtain C ₈ F ₁₇ C.
To obtain a _{H 2 CH 2 SO 2 NHCH 2} COOC 2 H 5.

Next, 4 equipped with a thermometer, stirring and cooling device
In a _two- necked flask, C ₈ F ₁₇ CH ₂ CH ₂ SO ₂ NHCH ₂
COOC ₂ H ₅ 47 g (0.08 mol), potassium hydroxide 4.5 g (0.08 mol), ion-exchanged water 150 ml
Was charged and stirred at 85 ° C. for 4 hours. Next, 150 ml of isopropyl alcohol was added, the solvent was distilled off under reduced pressure, and the residue was dried to give a fluorosurfactant (S-7).
(C ₈ F ₁₇ CH ₂ CH ₂ SO ₂ NHCH ₂ COOK) was obtained. In this reaction, a partially fluorinated alkyl group having a single chain length of perfluorooctylethyl iodide is used as a raw material, and the partially fluorinated alkyl group does not directly participate in the reaction in any step. The purity related to the present invention of the surfactant (S-7) can be regarded as 100%.

Synthesis Examples 8 to 10: Synthesis of Anionic Fluorine Compounds (S-8) to (S-10) As in Synthesis Example 7, a perfluorinated starting material is a perfluorinated alkyl group having a single chain length. Hexylethyl iodide (C ₆ F ₁₃ CH ₂ CH ₂ I), perfluorobutyl ethyl iodide (C ₄ F ₉ CH ₂ CH ₂ I) or perfluorodecanylethyl iodide (C ₁₀ F ₂₁ CH ₂ CH ₂ CH _2).
By using I) respectively, corresponding fluorinated surfactant _{(S-8) (C 6} F 13 CH 2 CH 2 SO 2 NHCH 2
COOK), (S-9) (C 6 F 13 CH 2 CH 2 SO 2 NHC
_{H 2 COOK), (S-} 10) (C 1 0 F 21 CH 2 CH 2 SO
₂ NHCH ₂ COOK) was obtained. In addition, since a raw material having a single chain length of a partially fluorinated alkyl group is used and the partially fluorinated alkyl group does not directly participate in the reaction in any step, the fluorine-based surfactants (S-8) to (S-8) The purity related to the present invention of -10) can be regarded as 100%.

Synthesis Example 11: Synthesis of cationic fluorine compound (S-11) In a four-necked flask equipped with a thermometer, stirring and cooling device,
36.8 g of N, N-dimethylpropanediamine (0.3
6 mol) and charged with ethyl acetate 50 ml, perfluorooctyl sulfonyl chloride was synthesized in the same manner as in Reference Example _{7 (C 8 F 1 7 CH} 2 CH 2 SO 2 Cl) 92.4g
A solution of (0.18 mol) in 250 ml of ethyl acetate was added dropwise at room temperature with stirring for 30 minutes. afterwards,
After stirring for 4 hours, 300 ml of ion-exchanged water was added, the organic layer was taken out, washed with ion-exchanged water and dried under reduced pressure, and then dried under reduced pressure. C ₈ F ₁₇ CH ₂ CH ₂ SO ₂ NH (CH ₂ ) ₃ N (C
Were obtained H _{3) 2.}

Next, 4 equipped with a thermometer, stirring and cooling device
During necked flask, C ₈ resulting _{F 1 7 CH 2 CH 2 SO} 2 N
41 g (0.07 mol) of H (CH ₂ ) ₃ N (CH ₃ ) ₂ and 300 ml of ethyl acetate were charged and dissolved with stirring, and then 11 g (0.077 mol) of methyl iodide was gradually added thereto, and the mixture was allowed to stand at room temperature. Stir for 3 hours, then concentrate and dry under reduced pressure to C ₈ F ₁₇ CH _{2.
CH 2 SO 2 NH (CH 2} ) 3 N + (CH 3) 3 I - was obtained. A partially fluorinated alkyl group having a single chain length is used, and
Since the partially fluorinated alkyl group does not directly participate in the reaction in any step, the fluorosurfactant (S-11)
The purity related to the present invention can be regarded as 100%.

Synthesis Examples 12 to 14: Synthesis of Cationic Fluorine Compounds (S-12) to (S-14) As in Synthesis Example 11, a perfluorinated alkyl group having a single chain length is used as a starting material. hexyl ethyl iodide _{(C 6 F 13 CH 2 CH} 2 I), perfluoro butyl ethyl iodide _{(C 4 F 9 CH 2 CH} 2 I) or perfluoro decanyl ethyl iodide (C ₁₀ F ₂₁ CH ₂
CH ₂ I) is used to obtain a corresponding fluorine-based surfactant (S-12) (C ₆ F ₁₃ CH ₂ CH ₂ SO _{2
^{NH (CH 2) 3 N +}} (CH 3) 3 I -), (S-13) (C 4 F 9
_{CH 2 CH 2 SO 2 NH (} CH 2) 3 N + (CH 3) 3 I -), (S
_{-14) (C 10 F 21 CH} 2 CH 2 SO 2 NH (CH 2) 3 N
⁺ (CH ₃ ) ₃ I ⁻ ) was obtained. In addition, since a partially fluorinated alkyl group has a single chain length and the partially fluorinated alkyl group does not directly participate in the reaction in any step, the fluorosurfactants (S-12) to (S-12). The purity relating to the present invention of -14) can be regarded as 100%.

Examples 1 to 11 and Comparative Examples 1 to 5 The obtained fluorine compounds (S-1) to (S-14) are
Table 3 for each type of surfactant with different ionicity,
The ingredients were blended in the proportions shown in Tables 4 and 5. The solvent has a third
Nonionic and anionic fluorochemical surfactants shown in Tables and 4 are ion-exchanged water, and cationic fluorochemical surfactants shown in Table 5 are ion-exchanged water / isopropyl alcohol = 1/1 (weight ratio). All of the concentrations were set to 0.1% by weight using the aqueous solution of). As the evaluation of the surfactant solution, the solubility at room temperature is shown in Tables 3, 4, and 5 together with the value of the surface tension which is the basis of the surfactant effect.

The surface tension is measured by an automatic surface tension meter CBPV-Z.
(Manufactured by Kyowa Interface Science Co., Ltd.) was measured by the Wilhelmy platinum plate method at 20 ° C.

The solubility in water at room temperature was visually evaluated,
The following criteria are entered in the table. 5: Clear solution 4: No precipitation but slightly cloudy solution 3: No precipitation but cloudy solution 2: Slight precipitation 1: Large amount of precipitation

[0051]

[Table 3] * The surface tension was not measured for the precipitates because they do not function as a surfactant at this concentration. It is shown as-in the table.

[0052]

[Table 4]

[0053]

[Table 5]

As is apparent from Tables 3, 4, and 5, the surfactant composition of the present invention has good solubility in a solvent and excellent surface tension lowering ability.

[0055]

EFFECTS OF THE INVENTION The use of the fluorosurfactant composition of the present invention allows a wide range of solubility in the composition to be added, so that not only can the optimum addition amount be selected, but effective penetration / It is possible to improve surface activity such as wettability and leveling property.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Koji Kinoshita             3-11-3-306 Matsunami, Chuo-ku, Chiba-shi, Chiba Prefecture F-term (reference) 4H003 AA02 FA04                 4H006 AA03 AB68 GP01 GP10 GP20

Claims (10)

[Claims] 1. F (CF ₂ ) _2n CH ₂ CH as a surfactant
A fluorine-containing surfactant composition containing two or more kinds of fluorine-containing compounds having a partially fluorinated alkyl group represented by _2- (n is an integer of 1 to 10) and having a purity of 85% by weight or more. A fluorine-containing surfactant composition, wherein the two or more fluorine-containing compounds are fluorine-containing compounds having n-different partially fluorinated alkyl groups. 2. The fluorosurfactant composition according to claim 1, wherein each of the two or more types of fluorochemical compounds is a fluorochemical compound represented by the following general formula (1). _{F (CF 2) 2n CH 2} CH 2 XY (1) ( wherein, n represents an integer of 1 to 10, X represents a direct bond or a divalent linking group, Y represents a Shin'nakadachimoto.) 3. X in the general formula (1) is a direct bond, --SO
₂NR- (R is hydrogen, phenyl group or 1 to 18 carbon atoms
Is an alkyl group. ), -SO₂NR (CH ₂)_k-(R
Is hydrogen, a phenyl group or an alkyl group having 1 to 18 carbon atoms
Is shown and k shows the integer of 1-8. ) Or -S (C
H₂)_k-(K represents an integer of 1 to 8).
The fluorinated surfactant composition described. 4. Y in the general formula (1) is an acid group, a metal thereof,
The fluorosurfactant composition according to claim 3, which is an amine salt, a polyalkylene oxide group or a quaternized amine salt residue. 5. F (CF ₂ ) _2n CH ₂ CH ₂ — (n is 1 to 1)
Indicates an integer of 0. 2) a fluorine-containing compound having a partially fluorinated alkyl group and having a purity of 95% by weight or more.
The fluorosurfactant composition according to claim 4, containing at least one species. 6. The total content of fluorine compounds having a partially fluorinated alkyl group of n ≧ 5 in the total fluorine compound is 5% by weight or less.
Item 5. A fluorosurfactant composition according to item. 7. The fluorosurfactant composition according to claim 6, wherein the content of the fluorochemical compound having a partially fluorinated alkyl group of n = 1 in the total fluorochemical compound is 5% by weight or less. 8. The fluorine-containing surfactant composition according to claim 7, wherein the content of at least one of the fluorine-containing compounds having a partially fluorinated alkyl group of n = 2 or n = 4 is 25% by weight or more. . 9. A fluorine-containing compound containing n = 2 partially fluorinated alkyl groups and having a purity of 85% by weight or more, a fluorine-containing compound containing n = 3 partially fluorinated alkyl groups and having a purity of 85% by weight or more, and n. 8. The fluorosurfactant composition according to claim 7, which is a mixture of two or more fluorochemical compounds selected from the group consisting of fluorochemical compounds containing a partially fluorinated alkyl group of 4 and having a purity of 85% by weight or more. 10. A fluorine-based compound containing a partially fluorinated alkyl group of n = 2 and having a purity of 85% by weight or more, a fluorine-containing compound containing a partially fluorinated alkyl group of n = 3, having a purity of 85% by weight or more, and n. Containing a partially fluorinated alkyl group having a purity of 85% by weight or more and a weight ratio thereof ([n = 2) / (n = 3) / (n =
4)] is (5-50) / (5-85) / (10-90)
The fluorosurfactant composition according to claim 7, which is