JPH0768510B2 - Water and oil repellent - Google Patents

Description

The present invention relates to a water and oil repellent agent, and more particularly to an aerosol type water and oil repellent agent. In recent years, with the improvement of the standard of living of consumers and the modernization of their lives, water repellency and oil repellency are imparted to textiles and the like to prevent the penetration of liquid or to prevent oil stains.
There is a growing demand for a treatment that can be easily washed off with ordinary laundry. In response, various water and oil repellents are sold on the market, especially from the viewpoint of ease of use, but they are all satisfactory in terms of water and oil repellent performance, whitening phenomenon, safety, odor, and economical efficiency. What is done is not yet developed.

That is, although mineral oil or silicone was initially used as the water / oil repellent component, the water / oil repellency was insufficient, and the action mechanism that the effect was obtained by coating the fiber etc. And the durability (persistence of water / oil repellency) or wash resistance cannot be expected.

The subsequently developed fluororesin-based water and oil repellent component has the effect of substituting the fluorine compound for the treated surface of the fiber etc. to reduce the surface energy of the treated surface, and impair the breathability of the water and oil repellent performance. However, since the fluororesin component was deposited on the treated surface after the treatment, the whitening phenomenon was noticeable especially in black clothing and leather products.
This occurs because the solvent evaporates before the fluororesin component penetrates into the inside of the treated surface such as the fiber, and the component remaining on the surface easily deviates due to abrasion, resulting in lack of durability.

Therefore, for the purpose of increasing the solubility of the fluororesin component and infiltrating the inside of the fiber etc., for example, a method of using a chlorine-based solvent such as 1,1,1-trichloroethane (chlorocene) has been adopted, It cannot be used in large quantities indoors because it does not provide sufficient bleaching suppression effect and gives the odor and anesthesia characteristic of solvents.

On the other hand, low boiling point alcohols such as ethyl alcohol and vegetable oils can be considered as safer and less peculiar odors, but the bleaching phenomenon becomes rather severe, and when these solvents are flammable, a large amount of flames etc. There is a risk, which is not desirable.

In view of the above situation, the inventors of the present application have focused on a solvent that plays a particularly important role in performance and use pipe among water / oil repellent compositions as means for solving the problems, and have conducted various studies and studies. As a result, we came to the following interesting facts.

That is, as a solvent for the fluororesin-based water / oil repellent component, a paraffinic solvent containing 80% or more of normal or isoparaffin having 7 to 12 carbon atoms is used in an aerosol undiluted solution in an amount of 2 to 15% by weight. Not only does it show performance and durability, it also significantly reduces the whitening phenomenon, and when mixed with chlorocene, it reduces the concentration of chlorocene to 1 /
It was discovered that it can be reduced to 2 or less, and it also contributes significantly to the improvement of odor and safety.

Thus, the present invention has been completed based on the novel findings as described above, and the obtained water and oil repellent agent does not impair the air permeability and texture of fibers and the like, and is independent of the type of materials such as fibers. It provides excellent water and oil repellency and a feeling of use.

The content composition of the fluororesin-based water- and oil-repellent component used in the present invention is not particularly limited, and the amount is 0.1 to 1.0% by weight as an effective solid content.

If it is less than 0.1% by weight, the effect is inferior, and if it exceeds 1.0% by weight, not only is it uneconomical, but the texture of fibers and the like is impaired.

The present invention has a particular feature in the selection of a solvent that dissolves a fluororesin-based water- and oil-repellent component. Among the paraffin-based solvents that make up 2 to 15% by weight in the aerosol stock solution,
It is essential that 80% or more is contained in the normal or isoparaffin fraction having 7 to 12 carbon atoms shown below.

n-heptane bp 98 ° C isoheptane n-octane bp 125 ° C isooctane n-nonane bp 150 ° C isononane n-decane bp 174 ° C isodecane n-undecane bp 195 ° C isoundecane n-dodecane bp 216 ° C isododecane Generally as a mixed solvent of these. It is often obtained, for example, a petroleum fraction such as ligroin, which contains heptane or octane as a main component, and Isobar C, E, G, H, L manufactured by Exxon Chemical Co., Ltd. or Idemitsu Petrochemical Co., Ltd. Of course, it is also possible to use isoparaffinic hydrocarbons such as Ivy Solvent 1620.

A paraffinic solvent having 7 to 12 carbon atoms has a water- and oil-repellent component that is more soluble than the treated surface because of the solubility of the fluororesin-based water- and oil-repellent component and suitable drying properties and mild chemical properties for the treated surface. By penetrating inside, it helps the components to be distributed evenly throughout the treated area, and as a result, it prevents whitening and provides excellent water and oil repellency and durability. On the other hand, when the carbon number is 6 or less, the boiling point is too low and the solvent is immediately dried on the treated surface, and the water / oil repellent component remains on the surface to cause a whitening phenomenon. When it is 13 or more, the boiling point is too high and the drying property is extremely deteriorated, and the feeling of use is impaired. Even if the carbon number is 7 to 12, it is unsaturated, or if other elements are included, it has a peculiar odor or reaction. It is difficult to process because of its ability and dissolving power. Further, the content of the paraffinic solvent is preferably 2 to 15% by weight, and when it is used in the aerosol undiluted solution in excess of 15% by weight, the solubility of the water / oil repellent component,
It has become clear that problems occur in the dryness after aerosol injection.

Further, other types of solvents used in combination with the above-mentioned paraffinic solvent include, but are not limited to, fluorocarbon type, halogenated hydrocarbon, aromatic type solvent, etc., but fluorocarbon type is preferable, and F113 (trichlorotrifluoroethane) is particularly preferable. ) Or a mixed solvent of F113 and chlorocene is preferably used.

Trichlorotrifluoroethane is not only non-flammable, but also has little solvent odor and does not damage the fabric.

Since the boiling point is relatively low, the drying property is high at the time of use, and the blending amount is appropriately determined in consideration of the compatibility with the paraffinic solvent.

A propellant gas may be added to the thus-prepared aerosol stock solution by a conventional method and filled in an appropriate aerosol container to obtain an aerosol-type water and oil repellent agent.

The propellant gas is preferably liquefied petroleum gas, particularly preferably propane. CFC gas, dimethyl ether, etc. can be used if necessary, but only 20 to 30% can be mixed in the injection gas. It is desirable that the compounding amount is as small as possible, but if it is less than 5.0% by weight, it is difficult to form an aerosol, and if it exceeds 15% by weight, the water / oil repellency effect becomes low.

The water and oil repellent of the present invention can be applied to an article to be treated by any method. For example, it can be dried immediately by simply spraying it on the part to be treated and it can exhibit sufficient water and oil repellency.
You may process with an iron etc. after drying. Furthermore, it is also possible to add other active ingredients such as insect repellent, anti-twisting agent, antistatic agent, dye adhesive, anti-wrinkle agent to the water / oil repellent composition of the present invention to apply it as a multipurpose composition. Needless to say, fragrances can be added according to taste.

The article which can be treated with the water and oil repellent of the present invention includes various examples without limitation. For example, textile fabric, glass, paper, wood, leather, fur, asbestos, brick, cement,
Metals, ceramic products, plastics, painted surfaces and plasters.

As the fiber woven fabric, natural animal and vegetable fibers such as cotton, hemp, wool and silk, various synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile and polypropylene, semi-synthetic fibers such as rayon and acetate, and glass. Examples thereof include fibers and mixed fibers thereof.

Next, examples of the present invention will be specifically described, but it goes without saying that the present invention is not limited thereto.

Example 1 (parts by weight) Asabi Card AG-650 (solid content 15%) 3.0 (as solid content) (0.45) trichlorotrifluoroethane 77.0 Ivy solvent 1620 10.0 propane 10.0 total 100.0 Asahi Glass Co., Ltd. AG-650 3.0 weight Dissolve 7 parts by weight of trichlorotrifluoroethane and 10.0 parts by weight of Idemitsu Solvent 1620 Idemitsu Petrochemical Co., Ltd. to prepare a stock solution.
90 parts by weight of this stock solution is filled in a tin pressure resistant container, an aerosol valve is attached, and 10.0 parts by weight of propane is press-fitted and a button is attached to obtain a product. This aerosol product suppressed the whitening phenomenon well, had a very high water and oil repellency effect, and was extremely durable, and was excellent in usability.

Example 2 (parts by weight) Asahi Guard AG-650 4.0 (as solid content) (0.6) Trichlorotrifluoroethane 70.0 Chlorosene 10.0 Ligroin 7.9 Perfume (Oshika Co., Ltd.) CH-650 0.1 Propane 8.0 Total 100.0 Asahi Glass Co., Ltd. AG-650 (4.0 parts by weight) is dissolved in trichlorotrifluoroethane (70.0 parts by weight) and chlorocene (10.0 parts by weight), and ligroin (7.9 parts by weight) and perfume (0.1 parts by weight) are added to prepare a stock solution. 92.0 parts by weight of this stock solution is filled in a tin pressure resistant container, and 8.0 parts by weight of propane is further press-fitted and an aerosol valve is attached. An aerosol button was attached to this to make the product. This aerosol product not only has excellent water and oil repellency and durability, but also has excellent usability because it does not cause a whitening phenomenon and can suppress the odor of chlorothane.

Examples 3 to 8 and Comparatives 1 to 14 were commercialized in the same manner as in Example 1 according to the compositions shown in the table. The results are shown in the table below.

Black cotton fabric is used as the treated sample, and water repellency is JIS L10
It was judged according to 92.

100: No adhesion and wetting on the surface 90: Slight adhesion and wetting on the surface 80: Water droplet-like wetting on the surface 70: Significant partial wetting on the surface 50: Wetting on the entire surface Item 0: The surface shows complete wetting The oil repellency was judged according to AATCC Test Method 118.

0: No effect 1: Nujol does not penetrate 2: Nujol / n-hexadecane = 65/35 (vol) does not penetrate 3: n-hexadecane does not penetrate 4: n-tetradecane does not penetrate 5: n-dodecane penetrates None 6: n-Decane does not penetrate 7: n-Octane does not penetrate 8: n-Heptane does not penetrate Texture, whitening, stains, and odor were judged by sensory tests.

◯: No problem Δ: Slightly difficult ×: Not usable Flammability was measured with a Cleveland open type tester.

○: No flash point ×: Inflammability Safety investigated by literature ○: Almost no problem △: Slight problem ×: Some problem Pressure was judged by the value at 25 ° C ○: 2.0-4.5kg / cm ² G △: 4.6 kg / cm ² G or more ×: less than 2.0 kg / cm ² G (cannot be sufficiently jetted) Based on the above results, it was determined whether the aerosol type water / oil repellent is suitable or not.

○: Appropriate △: Somewhat unsuitable ×: Inappropriate As a result of the test, the water and oil repellent of the present invention not only exhibits good water repellency, oil repellency and durability, but also has no problems such as whitening phenomenon and flammability, and is particularly suitable for general household use. Can be said to be a product.

Claims (1)

[Claims] 1. A fluororesin-based water / oil repellent component and a carbon number of 7 to 12
2 to 15% by weight of a paraffinic solvent containing 80% or more of normal or isoparaffin of 1.