JPH0756020B2 - Fluorine-based water and oil repellent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an improved water and oil repellent agent,
More specifically, a water-repellent agent containing a polyfluoroalkyl group-containing polymerizable compound, vinyl chloride or vinylidene chloride, and a copolymer obtained by copolymerizing the polyfluoroalkyl group-containing compound with a copolymerizable compound. The present invention relates to a water / oil repellent having a high water / oil repellency and a high storage stability.

[Prior Art] Conventionally, as a water-dispersible fluorine-based water and oil repellent, a polymerizable compound containing a polyfluoroalkyl group can be copolymerized with vinyl chloride or vinylidene chloride and a compound containing the polyfluoroalkyl group. It is known that a copolymer with a compound is very useful as a water and oil repellent. However, when these copolymer compositions are stored for a long period of time, there have been problems such as coloring and gelation due to emulsion disintegration, and changes in the color tone of fabrics and deterioration of performance during treatment have been recognized.

[Problems to be Solved by the Invention] An object of the present invention is to provide a long-term water-dispersible fluorine-based water / oil repellent agent containing a copolymer having vinyl chloride or vinylidene chloride as a copolymerization component, which the prior art has. It aims to solve the deterioration of quality during storage and dramatically improve the storage stability during long-term storage.

[Means for Solving the Problems] The present inventor has copolymerized a polymerizable compound containing a polyfluoroalkyl group with vinyl chloride or vinylidene chloride and a compound copolymerizable with the compound containing a polyfluoroalkyl group. The water-repellent repellency is improved without impairing the excellent performance of the water-dispersible fluorine-based water- and oil-repellent agent containing the obtained copolymer, and further, long-term storage stability is improved to such an extent that it does not cause any problems in actual use. As a result of various studies and studies for the purpose of providing an oil agent, a water-dispersible fluorine-based water / oil repellent agent containing a copolymer containing vinyl chloride or vinylidene chloride as a copolymerization component is subjected to copolymerization. Water- and oil-repellent agents have good storage stability by using an azo-type polymerization initiator that does not contain chloride ion in the form of hydrochloride and is dispersible in water. The present invention has been accomplished by discovering that

That is, the present invention provides a polyfluoroalkyl group-containing polymerizable compound, vinyl chloride or vinylidene chloride, and a copolymer obtained by copolymerizing the polyfluoroalkyl group-containing polymerizable compound with a copolymerizable compound. In a water-dispersible fluorine-based water and oil repellent containing water, use an azo-based polymerization initiator that does not contain chloride ion in the form of hydrochloride and is water-dispersible as a polymerization initiator for copolymerization. According to the present invention, a water / oil repellent agent is provided that reduces the chlorine ion concentration in water, which is a medium of a copolymer composition, exhibits high water / oil repellency, and exhibits good storage stability for a long period of time.

The polymerization initiator used in the present invention is an azo polymerization initiator which does not contain chloride ions in the form of hydrochloride and is water dispersible, and examples thereof include the azo initiators shown below. .

The water- and oil-repellent agent according to the present invention does not contain chloride ion in the form of a hydrochloride salt as exemplified here, and further uses a water-dispersible azo-based polymerization initiator, and contains a polyfluoroalkyl group-containing agent in an aqueous medium. The polymerizable compound is vinyl chloride or vinylidene chloride and a compound copolymerizable with the polyfluoroalkyl group-containing polymerizable compound, a surfactant and optionally a water-soluble organic solvent as a dispersion aid. It can be obtained by carrying out emulsion polymerization. The polymerization temperature can be selected depending on the initiator, but usually 40 ° C to
80 ° C is preferred.

Since the water and oil repellent of the present invention uses a chloride ion-free polymerization initiator, the chloride ion concentration in the water and oil repellent is 0.20 mol / or less, particularly 0.15 mol / or less. be able to.

The polymerizable compound containing a polyfluoroalkyl group, (Here, R ₁ is H or CH ₃ ) and (meth) acrylic acid ester containing a polyfluoroalkyl group can be mentioned as a preferable example. It is also possible to use together more than one species.

The aforementioned Rf is a linear or branched polyfluoroalkyl group having 3 to 21 carbon atoms, preferably 4 to 16 carbon atoms, and usually a terminal one having a perfluoroalkyl group is selected. Those containing a hydrogen atom or a chlorine atom at the terminal portion, or an oxypolyfluoroalkylene-containing group can also be used.

The compound copolymerizable with a polyfluoroalkyl group-containing polymerizable compound such as an acrylic ester or a methacrylic acid ester containing a polyfluoroalkyl group is a compound having a radical-reactive unsaturated bond as described below. in _{and, CH 2 = CR 1 COOR 2} CH 2 = CR 1 COO (CH 2 CH 2 O) p H (P 1 to 12) (Wherein R ₁ is H, or CH ₃ , R ₂ is H, or C _q H _{2q + 1} and q is 1 to 23, and preferably 1 to 6) such as methacrylic acid and acrylic acid or their esters. Or CH ₂ = CR ₁ CONHCH ₂ OH CH ₂ = CR ₁ CONHCH ₂ OC ₄ H ₉ CH ₂ = CHCl CH ₂ = CCl ₂ CH ₂ = CH ₂ OCOCH ₃ CH ₂ = CH ₂ CH ₂ OH CH ₂ = CR ₁ CON (CH ₃ ) ₂ (wherein R ₁ is H or CH ₃ ) a (meth) acrylic acid amide derivative, a halogen-containing vinyl monomer such as vinyl chloride or vinylidene chloride,
Ethylene, vinyl alkyl ether, vinyl acetate, maleic anhydride and maleic acid dialkyl ester, styrene, α-methylstyrene, p-methylstyrene, acrylonitrile, butadiene, isoprene, chloroprene, methyl vinyl ketone and the like are preferable. Of these, vinyl chloride or vinylidene chloride is particularly necessary as an essential component, and it is also possible to use two or more of these copolymerizable compounds in addition to vinyl chloride or vinylidene chloride. By copolymerizing a polymerizable compound containing no polyfluoroalkyl group, in addition to water and oil repellency and stain resistance, dry cleaning resistance, washing resistance, solubility, hardness, touch, etc. Various properties can be improved. The copolymerization ratio of the polyfluoroalkyl group-containing polymerizable compound to 100 parts by weight of the copolymer is 20.
-80 parts by weight is suitable.

Various kinds of surfactants such as nonionic, anionic, cationic and amphoteric surfactants can be adopted as the dispersant for making them water-dispersible, and these may be appropriately used in combination. Specifically, polyoxyethylene monooleyl ether, polyoxyethylene monoalkyl ether, polyoxyethylene mono (alkylphenyl) ether, polyoxyethylene monooleyl acid ester, polyoxyethylene monoalkylcarboxylic acid ester, sorbitan ester, sucrose Nonionic surfactants such as esters and 3
Cationic surfactants such as acetic acid salts of quaternary amines and quaternary ammonium salts, alkyl sulfonic acids and their salts, alkylbenzene sulfonic acids and their salts, alkyl carboxylic acids and their salts, anionic compounds such as sodium alkoxypolyoxyethylene sulfonate An amphoteric surfactant such as a surfactant, a betaine type or a phosphate ester type such as choline or ethanolamine is preferable.

The presence of the water-soluble organic solvent improves the dispersibility of the polymerizable compound containing a polyfluoroalkyl group and improves the copolymerizability with other copolymerizable polymers. The solvent suitable for this purpose can be used without particular limitation as long as it is a water-soluble solvent which is soluble in a polymerizable compound containing a polyfluoroalkyl group, but acetone, methyl ethyl ketone Ketones,
Ethylene glycol derivatives such as ethylene glycol and polyethylene glycol, and alkyl ethers of ethylene glycol derivatives such as polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether and polyethylene glycol monobutyl ether, propylene glycol derivatives such as propylene glycol, dipropylene glycol and polypropylene glycol, Suitable examples include polyethers such as cyclodextrin and dextrin, and esters such as methyl acetate and ethyl acetate. The addition amount of these organic solvents is selected from the range of usually 2 to 300 parts by weight, preferably 5 to 120 parts by weight, per 100 parts by weight of the polymer of the present invention.

The solid content concentration of the copolymer contained in the water-dispersible fluorine-based water and oil repellent of the present invention is not particularly limited, but is usually 2 to 60.
It is adjusted to Wt%, preferably 5 to 50Wt%, and used for processing in a state of being diluted with water to about 0.2 to 16Wt%. And, such a water-dispersed water- and oil-repellent agent has a higher flash point than the organic solvent type,
It has various advantages such as being able to increase the solid content concentration and further minimizing the pollution of the working environment during processing.

The water and oil repellent of the present invention can be applied to an article to be treated by any method depending on the type of the article to be treated. For example,
A known method of coating such as dip coating is applied to the surface of the object to be processed and dried. Also,
If necessary, it may be applied together with a suitable crosslinking agent and cured. Further, it is of course possible to add other water repellents or oil repellents or insect repellents, flame retardants, antistatic agents, dye fixing agents, anti-wrinkle agents, etc. to the water and oil repellents of the present invention and use them together.

The article that can be treated with the water and oil repellent of the present invention is not particularly limited as long as it is a textile product.
For example, cotton, hemp, wool, natural animal and vegetable fibers such as silk, polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, various synthetic fibers such as polypropylene, rayon, semi-synthetic fibers such as acetate, glass fiber, Examples include inorganic fibers such as asbestos fibers, and mixed fibers and woven fabrics thereof.

[Operation] In the present invention, the long-term storage stability of a water-dispersible fluorine-based water / oil repellent agent containing a copolymer containing vinyl chloride or vinylidene chloride as a copolymerization component is It was found that dissolved chlorine ions had an important effect. That is, when an emulsion of a copolymer containing vinyl chloride or vinylidene chloride as a copolymerization component is left to stand for a long period of time, chlorine resulting from the vinyl chloride structure or vinylidene chloride structure causes a desorption reaction, resulting in It degrades the structure and performance of the polymer. This dechlorination reaction depends on the chlorine ion concentration dissolved in the composition, and the higher the dissolved chlorine ion concentration, the more accelerated the dechlorination reaction. However, in the conventional water-dispersible fluorine-based water and oil repellents containing vinyl chloride or vinylidene chloride as a copolymerization component, a polyfluoroalkyl group-containing polymerizable compound and vinyl chloride or vinylidene chloride and this polyfluoroalkyl group-containing As an azo-type hydrochloride is used as a polymerization initiator for copolymerizing the compound of (1) with a compound capable of being copolymerized, chlorine derived from the polymerization initiator is added to water as a medium of the composition after the polymerization. Ions were dissolved in high concentration. Therefore, if this copolymer composition is stored for a long period of time, the dechlorination reaction of the copolymer is promoted by the dissolved chlorine ions, the polymer structure is changed, and the performance is deteriorated during the treatment, as well as coloring and emulsion. It was suggested to cause destruction of. In order to reduce the chlorine ions dissolved in the aqueous medium of the composition, when the source of chlorine ions was examined, it was found that the chlorine ions contained in the polymerization initiator in the form of hydrochloride were generated from the raw materials. It was found that it occupies the majority of the chlorine ions that do. Therefore, by using a polymerization initiator that does not contain chloride ion in the form of hydrochloride and is water dispersible, and reduce the concentration of chloride ion contained in the water medium in the water and oil repellent,
Suppresses the chlorine desorption reaction caused by the vinyl chloride structure or vinylidene chloride structure from the copolymer in a water-dispersed fluorine-based water and oil repellent agent containing vinyl chloride or vinylidene chloride as a copolymer component, and enables long-term storage. It is considered that the stability is improved. Of course, this description does not limit the invention in any way.

[Examples] Next, examples of the present invention will be described more specifically, but it goes without saying that the description does not limit the present invention.

The water repellency and oil repellency shown in the following examples are shown on the following scale. That is, the water repellency is JIS L-109.
It is expressed by the water repellency number by the spray method of 2 (see Table 1 below), and the oil repellency is obtained by placing the test solution shown in Table 2 below on a test cloth in two places (diameter about 4 mm).
It was judged by the permeation state after 0 seconds (AATCC-TM 118-196
6).

In addition, the water-repellent number and the oil-repellent number marked with + indicate that the respective performances were slightly better.

Example 1 In a glass autoclave (internal volume 1) equipped with a thermocouple thermometer and a current stirrer, perfluoroalkylethyl acrylate (hereinafter FA) [C ₈ F ₁₇ CH ₂ CH ₂ OCOCH =
CH ₂ ] 120 g, vinyl chloride 76 g, N-methylol acrylamide 4 g, polyoxyethylene lauryl ether 10
g, stearyl trimethyl ammonium chloride 2 g,
Add 120 g of acetone, 350 g of water, 2 g of azobis (dimethylene isobutyramidine) <Wako chemical product VA-061>,
Perform nitrogen substitution for about 20 minutes while stirring and use 76g vinyl chloride.
Then, the temperature is raised to 60 ° C. to start the polymerization. 60 ° C
After stirring for 15 hours while maintaining the temperature at room temperature, the mixture was cooled to obtain an emulsion having a solid content concentration of 31%. The conversion of the copolymerization reaction by gas chromatography was 99.0 to 99.8% (based on the perfluoroalkyl group-containing polymerizable compound). Also,
The yield of stable emulsion emulsion is
It was 95-99%.

Examples 2 to 6 and Comparative Examples 1 to 4 In the same manner as in Example 1, the monomers and the emulsifier polymerization initiator were changed to carry out emulsion polymerization. The monomers, emulsifiers and polymerization initiators used are shown in Tables 3 and 4.

A water- and oil-repellent performance test was conducted using a latex in which the solid content concentration of the emulsion emulsion obtained by the above method was 12% by weight as a stock solution. The latex stock solution was diluted with water, and the water / oil repellency was measured by setting the ratio of the stock solution to water to 1.5%.

The test was conducted on a nylon taffeta cloth, and the water and oil repellent treatment was performed as follows. That is, the test cloth was dipped in the latex treatment liquid diluted as described above for 30 seconds, and the cloth was squeezed between two rubber rollers to obtain a wet pickup of 30%.
And Then, it was dried at 110 ° C. for 90 seconds and further heat-treated at 170 ° C. for 60 seconds. The results of measuring the water and oil repellency of the treated cloth thus obtained are shown together with the results of the storage stability test.
The results are summarized in Table 5 below.

The storage stability test was carried out by leaving it in a constant temperature bath at 45 ° C for three months.

EFFECTS OF THE INVENTION The present invention provides a water-dispersible fluorinated water- and oil-repellent agent containing a copolymer containing vinyl chloride or vinylidene chloride as a copolymerization component, which is a water-dispersible azo-based polymerization initiator containing no chlorine ion. By polymerizing with an agent, it has become possible to provide an excellent water / oil repellent which has high water / oil repellency and at the same time achieves high storage stability which could not be achieved conventionally.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location C08F 220/58 MNG 222/12 MMH

Claims (4)

[Claims] 1. A copolymer obtained by copolymerizing a polyfluoroalkyl group-containing polymerizable compound, vinyl chloride or vinylidene chloride, and this polyfluoroalkyl group-containing polymerizable compound. In a water-dispersible fluorine-based water and oil repellent containing, the polymerization initiator when performing the copolymerization, characterized in that it is a chloride-free chlorine ion-free water-dispersible azo polymerization initiator A water-dispersible fluorine-based water and oil repellent. 2. The polymerization initiator is The water-dispersible fluorine-based water and oil repellent according to claim 1, which is at least one selected from the group consisting of: 3. The polymerization initiator is 2,2'-azobis [2- (2
-Imidazolin-2-yl) propane].
The water-dispersible fluorine-based water and oil repellent according to. 4. The chlorine ion concentration in the water and oil repellent is 0.20 mol /
The water-dispersible fluorine-based water and oil repellent according to claim 1, which is as follows.