JPS5959778A - Water and oil repellent treatment composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water and oil repellent treatment composition that improves stains left behind when used on textiles, clothing, etc. Fluorine-based water and oil repellents have better water repellency than silicone-based water repellents, are faster-acting, and are effective in small amounts. In addition to its advantages, it also has oil repellency, so it can be expected to have an antifouling effect, so it has recently been widely used as an aerosol type. However, if you spray an aerosol containing a fluorine-based water and oil repellent onto clothing, or apply a solution of the water and oil repellent dissolved in a solvent to clothing, white fleas will appear on the clothing after the solvent evaporates. There is a drawback. Particularly when clothing has dark colors such as black or red, white stains are noticeable and seriously impair the appearance.

Conventionally, organic solvents have been investigated to improve flea residue, and 1,1.2-)lichloro-1,2゜2-trifluoroethane is considered to be preferable as a solvent for fluorine-based water and oil repellents. However, this does not completely resolve the remaining stains. Furthermore, if mineral turpentine, which is a petroleum-based solvent, is used, the remaining stains can be considerably improved, but since mineral turpentine has a high boiling point, it takes a long time to evaporate, which is not good.

As a result of repeated research in order to solve the above-mentioned drawbacks, the present inventors found that stain residue can be significantly improved by blending a specific esterified product with a fluorine-based water and oil repellent and a chlorinated solvent. This has led to the present invention.

That is, the present invention involves adding a di-lower alkyl ester of a dicarboxylic acid having a carbon number of 4 to 1.0 to a mixed stock solution consisting of a fluorine thread water/oil repellent 005-5 by weight and a chlorinated solvent 99.95-95 I. , 1-1) lower alkyl esters of citric acid and lower fatty acid esters of dihydric alcohols having 4 to 10 carbon atoms. This is a water and oil repellent treatment composition.

The fluorine-based water and oil repellent in the present invention is a polymer of a perfluoroalkyl group or a polymerizable monomer having a fluoroalkyl group, or a copolymer of the monomer and other monomers, and is usually commercially available. Fluorine-based water and oil repellents can also be used as they are. Of these, the expression (
Polymers of those represented by 1) or (II) or copolymers of these with those represented by the formula ([ID) are preferred.

RfP, "0COC(R") -CH2...
・・・・・・・・・・・・・・・・・・・・・・・・(
1) RfSO2N (R3) INJ' 0COC (R2
) = Cl-12 (II) (where r
(, f is a perfluoroalkyl group having 3 to 20 carbon atoms, n
,' represents an alkylene group having 1 to 8 carbon atoms, 2 represents hydrogen or a methyl group, and R3 represents hydrogen or an alkyl group having 1 to 3 carbon atoms. ) R'0(X)C(rL') = Cl-I2 ・
・・・・・・・・・・・・・・・・・・・・・・・・
...qII) (in the formula, 1 (? is a carbon number of 3 to 28
The alkyl group represents hydrogen or a methyl group. ) Furthermore, in place of or together with the monomer represented by the general formula (1) or (II) and the monomer represented by the general formula (III), acrylonitrile, methacrylonitrile, ethylene, vinyl acetate, styrene, phthalene, chlorobutene, etc. It is also possible to use one or two copolymerized monomers having no fluoroalkyl group, such as fluoroalkyl group-free monomers. By copolymerizing these monomers that do not have a fluoroalkyl group, it is possible to appropriately improve performance in addition to water and oil repellency and dirt repellency (such as handling, flexibility, and feel). In addition to using one type of polymer as an oil repellent, different content ratios of fluoroalkyl groups2
It is also possible to use a mixture of more than one type of polymer.

For example, a copolymer of general formulas (I) and (g) and a copolymer of general formulas (II) and (IID) may be mixed and used.

The amount of the fluorine-based water and oil repellent is 005 to 5 by weight and 03 to 2 by weight. If the amount is less than 0.05 parts by weight, sufficient water and oil repellency will not be achieved, and if more than 5 parts by weight is added, the solubility in chlorinated solvents will decrease and the texture of the treated object will deteriorate. This is because whitening may occur.

As the chlorinated solvent in the present invention, chlorinated hydrocarbon solvents and Freon solvents are used, and specifically, dichloromethane, 1,2 dichlororecessane, 1°1
．． 1-Trichloroethane, trichlorethylene, perchlorethylene, Freon 112 (S-tetrachlorodifluoroethane), Freon 113 (1,l.

2-trichloro-1,2,2-)lifluoroethane). Of these, dichloromethane, L
LI-trichloroethane, Freon 112, Freon 1
13 is preferred. The amount of chlorinated solvent is 95-99.9
5 parts by weight, preferably 98 to 997 parts by weight.

In the present invention, a diester of a dicarboxylic acid having 4 to 10 carbon atoms and a lower alcohol, a tri-lower alkyl ester of citric acid, and a 4 to 10 carbon atoms At least one esterified product selected from the group of esters of dihydric alcohol and lower fatty acid is blended. The lower alkyl group and lower fatty acid in these esterified products usually have 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms. Furthermore, as the fatty acid ester of dihydric alcohol having 4 to 10 carbon atoms, mono- or diesterified products can be used.

Specifically, these esterified products include dimethylzaku7
dibutyl adipate, diethyl adipate, diethyl adipate, diisobutyl adipate, dimethyl adipate, diethyl adipate, dibutyl adipate, diisobutyl adipate, dibutyl phthalate, dibutyl adipate, dibutyl adipate, diethyl sepa'y-), propyl sebacate, dibutyl seba cate, diisobutyl sebacate, triethyl citrate glycol monoacetate, butylene glycol diacetate, butylene glycol dipropionate, ethylene glycol divalerate, hex/lene glycol diacetate, hexylene glycol dipropionate, and the like. Among these, dicarboxylic acids selected from the group of co-phosphoric acid, adipic acid, speric acid and sebacic acid in terms of odor, methanol, ethanol, propatool,
Diesters with alcohols selected from the group of butanol and isobutanol are preferred.

The blending amount of the esterified product is appropriately selected depending on the amount of the fluorine-based water and oil repellent in the blended stock solution consisting of the fluorine-based water and oil repellent and the chlorinated solvent, but preferably the blended stock solution is 100%
The amount is 0.001 to 5 parts by weight, particularly preferably 0.01 to 1 part by weight. In this way, by adding a specific esterified product to the blended stock solution, it is possible to significantly improve the appearance of stains, and adding ethyl alcohol or ethylene glycol instead of this product does not have an effect comparable to that of the product of the present invention. I can't do it.

The 1-minute water and oil repellent treatment composition of the present invention can be used as a solution by applying it directly to an article to be treated or by dipping a cloth to be treated, but it can also be used as a solution after adjusting the water and oil repellent treatment composition. By adding an agent and filling a container, it can be easily converted into an aerosol and used. The propellant used in this case is LPG, propane, butane, dichlorodifluoromethane (Freon 1
．． 2), fluorotrichloromethane (Freon 1
1), dichlorotetrafluoroethane (Freon 114
), dimethyl ether'IC. 02, N20, etc. can be used.

The blending ratio of the invention product and propellant is 99/1 to 30/70
(% by weight), preferably 97/3 to 50150 (weight %).

The water and oil repellent treatment composition of the present invention can be used on articles to be treated in any manner depending on the convenient form (solution type, aerosol type, etc.) and the type of article to be treated. It is easy to use and is particularly suitable as a usage form of the product of the present invention because it is sufficient to simply spray the product onto the object to be treated.

The water and oil repellent treatment composition of the present invention may further contain small amounts of a silicone water repellent, an insect repellent, an antistatic agent, and a flame retardant.

According to the product of the present invention, natural fibers such as wool, cotton, and silk.

Regenerated fibers such as rayon and cupro, and acetate.

Semi-synthetic fibers such as triacetate, polyester.

polyamide, polyacrylonitrile, polypropylene,
Synthetic fibers such as polyvinyl chloride, mixed fibers thereof, and fabrics, clothing, and glass fibers made from these.

Asbestos fibers, glass, paper, wood, leather, fur.

It leaves no stains on bricks, cement, metals, plastics, and plasters and can impart excellent water and oil repellency. At this time, an antifouling effect is also exhibited as an effect of imparting oil repellency. The product of the present invention has good compatibility with the propellant Freon, so it is particularly suitable for aerosolization.
It has quick drying properties.

Next, the present invention will be explained in detail with reference to Examples. In the following examples, water repellency, oil repellency, and stain retention were evaluated by the following methods.

0 JIS-L- using wool tropical as the water-repellent material
It was evaluated by the spray method of 1,092.

The evaluation base f- is shown in Table 1.

A composition with a mixing ratio of 0 oil repellency + 1-hebutane and Nujol was dropped onto a test cloth (Wool Tropical), and the oil repellency was determined by the liquid composition that could hold the droplets for 3 minutes or more. Base yarns for evaluation of oil repellency are shown in Table 2.

Table 2: 0 stains left Black wool tropical was sprayed with a water and oil repellent treatment composition and hung to air dry, after which the appearance of stains was judged according to the criteria shown in Table 3.

Example 1) Add each additive to 100 parts by weight of the following blended stock solution (Table 4)
Cl-13 C81” 1□5O2N CI-hcI-I20cOc
H= Cl-12 C811□70cOctl = C
Water and oil repellent made of copolymer with l-12
05M quantity 1,, 1. , I-Trichloroethane 995 Chonghui Section (13) Spray agent (Freon 1
2/Freon 11-6/4)i)103)-85/15
An aerosol water and oil repellent treatment composition consisting of (weight ratio) was manufactured and its performance was evaluated. The results are shown in Table 4.

-1.03 parts by weight added.

(Blend piece #,) CB J'17CII2 CI-+20CO (CH3)
C= CHz and C, flz= C)1. C0N)1. C
1,zO (4/1 copolymer with LH9 066 parts by weight,
1. ．． 1-Trichloroethane 25 Weight width Freon 112 22.4% by weight Freon 113 52 Weight width (+3
) Propellant (J, PG) (A)/(+3)=7s/2s (weight ratio) An aerosol water- and oil-repellent treatment composition.

Composition 3 Add 0.2 parts of diethyl sebacate to 100 parts by weight of the stock solution below.
A composition for water and oil repellency treatment to which parts by weight are added.

(Blended stock solution) F2I-IC (CF2)s S 02NH (Cl-1,
2) 3000CH=OH2 and C41190COCI-
i = CI-J, 6/4 copolymer with 2 04 Weight Salary L 1. , 1-1-lichloroethane 49.
8% by weight dichloromethane 498 weight/weight range Applicant Lion Co., Ltd. agent box 1) Atsushi

Claims (1)

[Claims] 1. In a blended stock solution consisting of a fluorine-based water and oil repellent of 0.05 to 5 weight parts and a chlorinated solvent of 99.95 to 95 weight parts, 4
Di-lower argyl esters of dicarboxylic acids having a carbon number of ~10, tri-lower alkyl esters of citric acid and 4
1. A composition for water and oil repellent treatment, characterized in that it contains one or more esterified products selected from the group of lower fatty acid esters of dihydric alcohols having a carbon number of ~1o. 2. The composition according to claim 1, wherein the lower alkyl group and the lower fatty acid in the esterified product have carbon numbers in the range of 1 to 5. 3. A di-lower alkyl ester of a dicarboxylic acid having a carbon number of 4 to 10 is selected from the group of succinic acid, adipic acid, speric acid and sebacic acid and a dicarboxylic acid selected from the group of methanol, ethanol, globanol, butanol and imbutanol. The composition according to claim 1, which is a diesterified product with an alcohol. 4 The content of esterified product is 0.001 parts by weight per 100 parts by weight of the blended stock solution consisting of fluorine-based water and oil repellent and chlorinated solvent.
The water and oil repellent treatment composition according to any one of claims 1 to 3, wherein the amount is within the range of 5 parts by weight.