JPS5974181A - Organic solvent soluble fluorine-containing repellant for water and oil - Google Patents

Abstract

PURPOSE:To provide the titled water and oil repellant exhibiting improved penetration and diffusion into/on the surface of material to be processed, prepared by adding a specified surfactant to a fluorine-contg. repellant for water and oil. CONSTITUTION:A fluorine-contg. repellant for water and oil is prepared by dissolving in a solvent such as acetone or methyl ethyl ketone a copolymer of an unsaturated ester such as (meth)acrylate having 4-20C perfluoroalkyl group and at least one compd. having no perfluoroalkyl group selected from ethylene, styrene, acrylamide, chloroprene, etc. Then a sorbitan nonionic surfactant having an HLB value of 8 or lower (e.g. sorbitan sesquioleate) is added to the repellant in an amount of 5-30wt% based on the solid content of the repellant.

Description

DETAILED DESCRIPTION OF THE INVENTION Misfire 1] jJ &:i, relates to an organic solvent-soluble fluorine-based water and oil repellent that has completely improved permeability and diffusivity to the surface of a treated object.

Due to the manufacturing method, there are latex type and organic solvent-soluble type of so-called fluorine fiber water repellent which gives excellent water and oil repellent treatment to woven fabrics, paper, leather products, etc. something is known.

Most of the commonly known organic solvent types are made by depositing a water- and oil-repellent polymer liquid on the optical surface of the object by coating or dipping.
Does drying make the treated object water and oil repellent? give. In the case of this mold, a curing process is not necessarily required unlike the latex mold, and simple water and oil repellent treatment is possible.

Is this solution type suitable for adding propellers? Enclosing it in one container and making it into an aerosol allows for even simpler processing.

I was fully aware that if the above-mentioned bath liquid type was made into an aerosol and applied to the surface of the object to be treated, preferably a fabric, a white ring stain could be produced on the surface of the object.

After investigating the cause, it was found that the lower the boiling point of the organic solvent, the more remarkable the phenomenon.

Also, a certain part of the surface to be treated can be removed by aerosol etc.
c) li! I found it easy to use. Therefore, we thought that the cause of this problem was that the solvent evaporated before the water and oil repellent components in the solution could sufficiently penetrate and diffuse into the surface of the object to be treated, and we investigated countermeasures. As a result, it was found that by cooling the surfactant in a certain glaze, such white ring staining phenomenon could be completely prevented. That is, the present invention provides a novel organic solvent-soluble fluorine-based water and oil repellent, which is characterized in that it contains a surfactant gold having an rjHLB value of 8 or less.

The surfactant effective in the present invention is a surfactant having a so-called HLB value of 8 or less, which shows a balance between lipophilicity and hydrophilicity. Particularly suitable is one that promotes permeation and diffusion of the water and oil repellent components in the solution and at the same time does not inhibit the original water and oil repellency at all. This surfactant is preferably a nonionic surfactant. Among those with cationic groups, those whose oxidation value falls within the above range, and those with anionic or amphoteric groups, are well soluble in organic solvents and have a moisture content (1.
A cylindrical, permeable material is preferred.

Specific examples of nonionic surfactants include ether types such as polyoxyethylene alkyl ether and alkyl allyl ether/l/, amide types such as fatty acid ethanolamide, and esters such as higher fatty acid sorbitan ester and polyoxyethylene sorbitan fatty acid ester. Types of surfactants or fluorine-based surfactants can be mentioned. Particularly suitable are oleic acid monoglyceride, sorbitan sesquiolate, polyoxyethylene sorbitol tetate, laolate, polyoxyethylene pentaolate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, Solpic/triolate, etc. It is.

The amount of surfactant added is selected from the range of 5 to 30% by weight, preferably 10% by weight, based on the solid content of the fluorine-based water and oil repellent.
There are ~20 cracks. If the amount added is too small, a white ring stain'fJ1. The anti-bleaching ability (anti-whitening ability) is not sufficient, and too much water and oil repellency is undesirable because it completely inhibits water and oil repellency. Note that the preferable range of the amount added varies somewhat depending on the material of the object to be treated. With a solution type water and oil repellent, it is sufficient to apply, dip or spray the object to be treated and then dry it naturally, but it is advantageous to use a solvent with a low boiling point because it dries more quickly. However, as mentioned above, low-boiling point solvation, penetration and diffusion of the water and oil repellent components were not sufficiently achieved, and there was a risk of whitening, or in other words, that uniform water and oil repellency could not be achieved. Therefore, the types of solvents used are naturally limited. According to the present invention, this point has been improved and a wide range of solvents can be used. For example, acetone, methyl ethyl ketone, diethyl ether, dioxane, methyl chloroform, trichloroethylene, detrachloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroecne, etc. are suitable. These can be used as a mixture of two or more types (support).
You can also use 'C'. Furthermore, by adding a propellant such as dichlorodifluoromethane, 7-fluorometrotrichloroethane, dichlorotetoxyfluoroethane, CO□, LPG, DME, etc. to these solvents, it becomes possible to produce an air-fuel mixture.

The fluorine-based water and oil repellent for organic solvent bath molds used in the present invention is not limited in any way, but the following are common. In other words, unsaturated esters such as acrylates and methacrylates containing a fluoroalkyl group having 4 to 20 carbon atoms, and ethylene or vinyl acetate.

Vinyl chloride, vinyl chloride, vinylidene chloride,
Styrene, α-menal styrene, 'P-1 tylstyrene, alkyl esters of acrylic acid, methacrylic acid and its alkyl esters acrylamide, methacrylamide, diacetone acrylamide, methylolated diacetone acrylamide, N-methylol acrylamide vinyl alkyl ether, norogen alkyl vinyl ether, vinyl alkyl keto/, phytadiene, isopreno, cyclosidyl acrylate, benzyl methacrylate, benzyl acrylate, cyclohexyl acrylate),! water maleinoic acid, dioctyl maleate.

It is a copolymerization of one or more polymerizable compounds that do not contain a perfluoroalkyl group, such as aziridinyl methacrylate and aziridinyl acrylate.

The articles treated with the water and oil repellent of the present invention are those that require a beautiful surface, especially textiles, but are not limited to these, such as glass, paper, wood, and leather. 9 fur 2 asbestos, brick.

These include cement, metals and their oxides, ceramic products, plastics, painted surfaces, and plasters.

Examples of textiles include animal and plant natural fibers such as cotton, hemp, wool, and silk, polyamide, polyester, polyvinyl alcohol, and polyacrylonitrile.

List various synthetic fibers such as polyvinyl chloride and polypropylene, semi-synthetic fibers such as rayon and acetate, inorganic fibers such as glass fibers, asbestos fibers, and fibers, or woven fabrics of mixed fibers. Can be done.

Next, the application of the present invention will be explained in more detail, but it goes without saying that the present invention is not limited to this explanation in any way. Regarding the water repellency shown in the following examples, water repellency J
f6, and oil repellency is AATCC-
According to TM-118-1966, 8 points n-hebutane (2
0('yrl sif n kara 1 point nujol (32,1"'
ne/crn) surface tension on the casing or different oil droplets (approximately 4/
1uH) f Observe the condition after 30 seconds have elapsed, and check whether the surface tension on the carpet does not vh? The content of anti-whitening properties is shown in Table 1. In addition, those marked with 10's on the water repellent plate indicate slightly better performance, and those marked with - indicate slightly inferior performance.

On the other hand, the water and oil repellent used for performance evaluation is a copolymer consisting of -fluoroalkyl acrylate, pen/zylmec acrylate, dioctyl maleate, and aziridinyl methacrylate, and the solvent is 1.1 .2-) Lichloro 1.2.2-trifluoroethane//Methylchlorontorum 75/25 mixed solvent is used to form an aerosol with dichlorodifluoromec/. The second coating shows the effects of various surfactants and their derivatives on whitening prevention and water and oil repellency. Furthermore, the third light shows the effect that 1 cup of sorbitan monooleate added to the solid content of the water and oil repellent has on the water and oil repellency.

Table 1 Table 2

Claims (1)

[Scope of Claims] 1) An organic solvent-soluble fluorine-based water-repellent agent characterized in that it contains a surfactant with an HLB value of 8 or less. 2) A fluorine-based water-repellent agent with an HLB value of 8 or less. The water and oil repellent according to item 1 of the scope of the invention, characterized in that it is a sorbitan-based nonionic surfactant. 3) Fluorine thread water and oil repellent 5-30' based on solid content! h
2. The water and oil repellent according to item 1, characterized in that it comprises a UIii active agent in an amount of bFc%.