JPH0229100B2 - SANFUTSUKAENKAECHIRENJUGOTAIEMARUJON - Google Patents

Description

[Detailed description of the invention]

The present invention relates to trifluorochloroethylene polymer emulsions. More specifically, the present invention relates to an ethylene trifluoride chloride polymer emulsion used in the preparation of a lubricating water- and oil-repellent agent for textiles. In order to add water and oil repellents to raw cotton, raw wool, etc., water and oil repellent treatment is carried out using water and oil repellents, but it is difficult to make yarn from raw cotton or wool that has been treated in this way. There were many cases of yarn breakage due to the heat generated during the process. In order to avoid these drawbacks, it is possible to mix an oil component into the water and oil repellent, but the hydrocarbon oil and silicone oil that are conventionally used therefor have the problem of lowering the water and oil repellency itself. It had a point. The present inventors conducted various studies in search of an additive component that would not cause yarn breakage during the manufacturing process of raw yarn and that would fully demonstrate the performance of the water and oil repellent agent. We have found that coalescent emulsions are highly effective for such purposes. Accordingly, the present invention relates to an ethylene chloride trifluoride polymer emulsion, which is prepared from an ethylene chloride trifluoride polymer, a nonionic surfactant, a hydrophilic organic solvent, and water. or further, by adding a fluorine-containing compound represented by the following general formula to these. R _f Rm (OCHR'CH ₂ ) nX (where, R _f is a perfluoroalkyl group or a perfluoroalkylene glycol group having 4 or more carbon atoms, R is a divalent organic group, and R' is a hydrogen atom. or a methyl group; As the trifluorochloroethylene polymer, polytrifluorochloride ethylene polymer is preferably used, but copolymers of trifluorochloride ethylene and tetrafluoroethylene, hexafluoropropylene, perfluorovinyl ether, etc. Consolidation is also used. These polymers have a viscosity of approximately 0.1 to 10,000 at 2°C from the viewpoint of lubricating performance during spinning.
It is preferable to use centistokes. As the nonionic surfactant, commonly used ones are used. Examples of hydrophilic organic solvents include ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, isopropanol, and n-butanol, cellosolves such as methyl cellosolve and cellosolve acetate, diglyme, triglyme, tetraglyme, dioxane, and tetrahydrofuran. Ethers such as ethers, amides such as dimethylformamide and dimethylacetamide, and sulfur-containing compounds such as sulfolane and dimethylsulfoxide are used. These hydrophilic organic solvents play the role of lowering the interfacial tension and stabilizing the emulsion. The emulsion is prepared by adding about 1 to 80 parts by weight of trifluorochloroethylene polymer and about 1 to 80 parts by weight of nonionic surfactant.
This is carried out by mixing 0.1 to 10 parts by weight, about 1 to 50 parts by weight of a hydrophilic organic solvent, and about 1 to 99 parts by weight of water using a colloid mill or the like. When the fluorine-containing compound represented by the above general formula is added, it is used in an amount of about 0.1 to 10 parts by weight. Addition of a fluorine-containing compound has the effect of further stabilizing the emulsion. As such fluorine-containing compounds, the following compounds are used. C ₆ F ₁₃ C ₂ H ₄ OH C ₈ F ₁₇ C ₂ H ₄ OH C ₈ F ₁₇ C ₃ H ₆ OH C ₈ F ₁₇ C ₄ H ₈ OH C ₉ F ₁₉ C ₂ H ₄ OH C ₁₀ F ₂₁ C ₂ H ₄ OH C ₁₁ F ₂₃ C ₂ H ₄ OH C ₁₂ F ₂₅ C ₂ H ₄ OH C ₇ F ₁₅ COOH (Na) C ₈ F ₁₇ SO ₃ H (Na) C ₈ F ₁₇ C _{2H4COOH (} Na) C ₈ F ₁₇ C ₂ H ₄ (−OCH ₂ CH ₂ )− _o OH The trifluorochloroethylene polymer emulsion according to the present invention can be effectively used by being added to water and oil repellents. Water and oil repellents to which polymer emulsions are added are correspondingly generally preferably aqueous emulsions. The polymer emulsion contains a trifluoroethylene chloride polymer component which is approximately
0.1-500% by weight, preferably about 1-300% by weight,
More preferably, it is used in a proportion of about 5 to 200% by weight. Water and oil repellent treatment using a water and oil repellent containing a trifluorochloroethylene polymer emulsion involves impregnating the washed fibers with the water and oil repellent,
This is done by drying it. The dried fibers are worsted and/or spun. At this time, it is also possible to impregnate the dry fibers with a trifluorochloroethylene polymer emulsion and then carry out carding and/or spinning. By applying water and oil repellent treatment in this way,
Not only is good water and oil repellency with sufficient lubricity obtained, but there is no yarn breakage due to heat generation during the production of raw yarn. Moreover, by treating the yarn during spinning (carding, pre-spinning process), fabrics woven from this yarn, especially thick fabrics, can be treated to be water and oil repellent. It is superior in terms of wear resistance and durability. Next, the present invention will be explained with reference to examples. Example 1 1 part of various nonionic surfactants, 5 parts of acetone, and 82 parts of water were added to 10 parts (weight, same below) of polytrifluorochloroethylene (viscosity 50 centistokes, 25°C), and the mixture was milled in a colloid mill. (0.1 mm intervals) and mixed at 400 rpm for 3 minutes to form a uniform emulsion. In all cases, stable emulsions with no oil layer separation observed even after being left for one week were obtained. [Nonionic surfactant] No. 1 Polyethylene oxide (degree of polymerization 80) No. 2 (degree of polymerization 18) No. 3 Kao soap product Emanon 3199 No. 4 Example of polyethylene oxide monohigher fatty acid ester 2 Polytrifluoride 10 parts of ethylene chloride (viscosity 50 centistokes, 25°C), various fluorine-containing compounds
0.5 part, nonionic surfactant (Kao soap product Emulgen 950, however, No. 5 uses Emulgen 980)
2.5 parts of acetone, 5 parts of acetone, and 82 parts of water were added, and a uniform emulsion was formed using a colloid mill in the same manner as in Example 1. In all cases, stable emulsions with no oil layer separation observed even after being left for one week were obtained. [Fluorine-containing compound] No.1

[Formula] No.2 C ₇ F ₁₅ COONa No.3 C ₈ F ₁₇ SO ₃ Na No.4 C ₈ F ₁₇ CH ₂ OH ₂ COONa No.5 C ₈ F ₁₇ CH ₂ CH ₂ OH No.6

[Formula] No.7 Example 3 In Example 2, 2 parts of _{C8F17CH2CH2 ( -OCH2CH2 ) -10OH} was used as _{the fluorine} -containing compound, and the amount of nonionic surfactant used was 1 part. changed. Similarly, stable emulsions were obtained. Example 4 A fluorine-containing compound was added to 10 parts of polytrifluorochloroethylene having various viscosities (50, 100, 250, 400 or 500 centistokes, 25°C).
C ₈ F ₁₇ CH ₂ CH ₂ OH 2 parts, nonionic surfactant (Emulgen 950) 1 part, acetone 5 parts and water 82
A uniform emulsion was formed using a colloid mill in the same manner as in Example 1. In all cases, stable emulsions with no oil layer separation observed even after being left for one week were obtained. Example 5 In Example 4 using polytrifluorochloroethylene having a viscosity of 50 centistokes (25° C.), acetone was replaced by the same amount of ethanol, diglyme, dioxane, dimethylformamide, or dimethyl sulfoxide, respectively. both,
A stable emulsion was obtained in which no separation of the oil layer was observed even after one week of standing. Example 6 In Example 4 using polytrifluorochloroethylene having a viscosity of 50 centistokes (25° C.), the same amounts of the following fluorine-containing compounds were used. Similarly, stable emulsions were obtained. Example 7, Comparative Example 1 C ₈ F ₁₇ CH ₂ CH ₂ OCOCH=CH ₂ 50 parts Cyclohexyl methacrylate 49 2-hydroxyethyl acrylate 0.5 N-methylolacrylamide 0.5 Acetone 55 Nonionic surfactant (Emulgen 950) 7 Water 338 Emulsion of Example 4 prepared by using polytrifluorochloroethylene having a viscosity of 50 centistokes (25°C) in 100 parts of an emulsion polymer emulsion (solid content concentration 20% by weight) obtained by an emulsion polymerization system. After adding the specified amount of and mixing uniformly, dilute the mixed solution 40 times with water. After immersing various cloths in this diluted solution, they were heat-treated at 80° for 15 hours and then at 170°C for 3 minutes, and water and oil repellency tests were conducted on them. For comparison, a similar water and oil repellency test was conducted using 5 parts of silicone oil emulsion (oil content 30% by weight) instead of polytrifluoride chloride emulsion. The results obtained are shown in the following table.

[Water repellency test]

A drop of water was dropped onto the treated cloth, and the condition was observed after 5 minutes.

[Table] [Oil repellency test] Drop one drop of the test liquid (mixed liquid in the specific proportion shown in the table below) onto the treated cloth and observe the condition after 5 minutes. If the dropped test solution is retained on the cloth, test with a test solution with higher n-heptane content, and conversely, if it is not retained on the cloth, test with a test solution with higher n-heptane content. do. Then, using a test liquid that is at the limit that can be retained on the cloth, the oil repellency is evaluated based on the oil repellency evaluation shown in the table below. In the oil repellency evaluation, the case where 100% Nudyol is retained is 50, and the case where 100% Nudyol is not retained is 0.

【table】

[Table] Example 8 10 kg of pre-spun (0.25 g/m; 65 ^S ) made from Australian Merinofain wool was mixed with the emulsion polymer emulsion of Example 7 and polytrifluorochloroethylene emulsion. The hair was soaked in the solution for 10 minutes and dried. This was carried out using a ring spinning machine (SC type manufactured by Osumi Iron Works), with a spindle rotation speed of 10,000 rpm,
A single yarn was produced under the conditions of a feed rate of 25 m/min and a draft amount of 16. There were no single yarn breakages during manufacturing. Comparative Example 2 In Example 8, only the emulsion polymer emulsion was used without using the polytrifluorochloroethylene emulsion. During the production of single yarn, intense heat generation produced white smoke, and yarn breakage was often observed.

Claims (1)

[Scope of Claims] 1. A trifluoroethylene chloride polymer emulsion prepared from a trifluoroethylene chloride polymer, a nonionic surfactant, a hydrophilic organic solvent, and water. 2 Claim 1 added to water and oil repellent
The trifluorochloroethylene polymer emulsion described in 2. 3. The trifluorochloroethylene polymer emulsion according to claim 2, which is added to a water and oil repellent for textile treatment. 4 Trifluorochloroethylene polymer, the following general formula R _f Rm (OCHR'CH ₂ ) nX (where R _f is a perfluoroalkyl group or a perfluoroalkylene glycol group having 4 or more carbon atoms, and R is It is a divalent organic group, R' is a hydrogen atom or a methyl group, X is a hydroxyl group, carboxyl group, sulfone group and their bases, ammonium group, amino group or aminocarboxyl group, m is 0 to 4, and n is 0 to 50), a nonionic surfactant, a hydrophilic organic solvent, and water. 5 Claim 4 added to water and oil repellent
The trifluorochloroethylene polymer emulsion described in 2. 6. The trifluorochloroethylene polymer emulsion according to claim 5, which is added to a water and oil repellent for textile treatment.