JPS59157166A - Water-dispersed stain-proofing liquid agent - Google Patents

Abstract

PURPOSE:To provide the titled stain-proofing agent which is a stable aqueous dispersion free of the danger of ignition, having slight odor, and capable of minimizing the pollution of the working environment, by using a urethane compound containing a polyfluoroalkyl group in combination with a dibasic acid diester as a water-insoluble organic solvent. CONSTITUTION:The objective stain-proofing agent can be prepared by combining a urethane compound containing polyfluoroalkyl group [preferably a reaction product of a compound having a perfluoroalkyl group of formula CnF2n+1 (n is 4-16) with a polyvalent isocyanate] with a dibasic acid diester (e.g. diethyl succinate) as a water-insoluble organic solvent. The organic solvent solution of the compound containing perfluoroalkyl group is preferably converted to an aqueous dispersion by adding the solution to an aqueous solution of an emulsifier dropwise under agitation. USE:Suitable for the treatment of carpet, arm chair, outdoor tent, etc., and especially useful as a stain-proofing agent for synthetic fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aqueous dispersion type antifouling agent containing a polyfluoroalkyl group-containing compound as an active ingredient and using a dibasic acid diester as a water-insoluble organic solvent.

A compound obtained by reacting a polyfunctional incyanate compound with an alcohol containing a polyfluoroalkyl group (hereinafter abbreviated as PVA group) can be used to impart antifouling properties during spinning and sales. It is known to have excellent properties, such as not falling off from textile products during reeding or dyeing, and having no negative effect on dyeing. These compounds can be used as organic solutions, organic dispersions, or aqueous dispersions, but it is most desirable to use them as aqueous dispersions in order to prevent fires and contaminate the working environment. However, the aqueous molecular fluids of these compounds have low stability, and organic solvents are generally used to promote dispersion. 6) The present inventors have found that a stable aqueous liquid can be obtained by using a low-volatility, low-odor dibasic acid diester as an organic solvent. Furthermore, they have discovered that there is no fear of ignition and that pollution of the working environment can be minimized, thus arriving at the present invention.

That is, the present invention provides an aqueous dispersion type antifouling agent characterized in that a dibasic acid diester is used as a water-insoluble organic solvent in an antifouling agent containing a polyfluoroalkyl group-containing urethane compound as an active ingredient. This is related to drugs.

The P, FA group-containing urethane compound mentioned here is, for example, CH3, etc. In the above general formula, Rf is a linear or branched polyfluorocarbon having 1 to 20 carbon atoms, preferably 4 to 16 carbon atoms. An alkyl group, usually a perfluoroalkyl group at the end, is selected, but a group containing a hydrogen or chlorine atom at the end, or an oxyperfluoroalkylene-containing group can also be used. A preferred embodiment of Rf is -〇n 1! It is a perfluoroalkyl group represented by '2n+1' (where n is an integer from 4 to 16), and those in which n is 6 to 12 are particularly preferred. A is 10-, -8- or -N-(Z')- (however,
2' represents a hydrogen atom or a -valent organic group; 2 is an example of an organic group; -A-2 is -OR
'(R' is an alkyl group), -NHC! H20
H.

-NTTOH,0H20H2-NH(J12'0H20
0H20H-OH2゜\1 -ocH2ca2cu, -ocH,aH2No2
; -00H20H20H.

U CH20H20H, -NN(CH3)20H20HOH
3 and the like can be exemplified as suitable H.

Dibasic acid diesters in the present invention include, for example, dimethyl succinate, diethyl conophosphate, dipropyl succinate, diptyl succinate, dimethyl adipate, diethyl adipate, dipropyl adipate, diptyl adipate, dimethyl glutarate, and glutaric acid. dipropyl acid, diptyl glutarate, dimethyl oxalate, diethyl oxalate,
Dipropyl oxalate, dibutyl oxalate.

These include dimethyl phthalate, diethyl phthalate, dipropyl phthalate, and diptyl phthalate. A water-miscible organic solvent may be used in combination with this, for example, dioxane, tetrahydrofuran, water-soluble ethers such as ethylpropyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Ethylene glycol monopropyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol motsubutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether ) Water-soluble glycol ethers such as IJ ethylene glycol motuptyl ether, formamide, dimethylformamide.

Amides such as acetamide, water-soluble ketones such as acetone and diacetone alcohol, and alcohols such as methanol, ethanol, propatool, and phthanol can be used, but it is best to use them to the extent that they do not lower the flash point. desirable.

In the present invention, when dispersing a PFA group-containing compound in a medium mainly consisting of water to form an aqueous dispersion, for example, a solution of the PFA group-containing compound in an organic solvent (with an emulsifier added as the case may be) is mixed with an aqueous solution of an emulsifier. A method of dropping an aqueous solution of an emulsifier into a solution of a PFA group-containing compound in an organic solvent while stirring, or a method of dropping an organic solvent solution of a PFA group-containing compound and an emulsifier into water while stirring. Or, conversely, a method of dropping water may be adopted.

In this case, various types of dispersants and surfactants such as nonionic, anionic, cationic, and amphoteric surfactants can be used, and these may be used as appropriate. Also, the general formula 'Rf-X A-CONH, -Y-NHC! It may be dispersed in the coexistence of a fluorosurfactant such as a hydrophilic group-containing urethane compound represented by OT. Here, Rf and AB in the above-mentioned 6. D, or -R-
, -coIJ(R LeeQ, or -8O2N(R1)-Q
- (where R is a divalent alkylene group, R1 is a hydrogen atom or lower alkyl group, and Q is a divalent organic group), Y is a divalent organic group, and T is a hydrophilic group. be. T is a nonionic compound represented by -(C!H20H20), -R:l (where l is an integer of 1 to 50, R3 represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms), etc. group, -(ca2'aH2o)1so3M (where M represents one of a hydrogen atom, an alkali metal, or an ammonium group)
(However, R4,, R5, H6 represent a narkyl group, an aryl group, etc., and X is 01.Br,
C! Examples include cationic groups such as I (indicating 3, etc.).

Although the solid content concentration of the antifouling agent of the present invention is not particularly limited, it is usually adjusted to 5 to 60% by weight, preferably 15 to 50% by weight, and during processing, it is adjusted to 0.5% by weight with water. 1
It is used diluted to about 4% by weight. and,
KARIKI Lambda water-based dispersion-type antifouling agents have a higher flash point and a lower solid content concentration than organic solvent-based or aqueous dispersion-based agents that use highly volatile organic solvents. It is possible to make it higher. It has the advantage of being easy to machine, and also has other advantages such as being able to minimize contamination of the IJ surface during processing.

The antifouling agent of the present invention can be applied to various articles made of polyamide, polyester, leather, wood, etc., such as carpets, reception sets, curtains, wallpaper, and interior products such as car width interior products. , it can also be advantageously applied to outdoor tents and the like. In particular, it is useful as an antifouling agent for synthetic fibers, and has the characteristic that it can be applied before the dyeing process or during spinning of raw yarn.

The method of applying the antifouling agent of the present invention is not particularly limited, and various well-known methods can be employed, such as dipping and spraying.

It is possible to apply the coating by applying it to the surface of the object to be treated, or by absorbing it and drying it, using known coating methods such as coating. When constructing a trench, use antistatic agents, insect repellents, and a retardant.

It is also possible to use various processing agents such as dye stabilizers and anti-wrinkle agents, and additives.

The antifouling agent of the present invention as described above has the following advantages. It can impart high performance to the fiber during processing during spinning, has good stain resistance, and has high friction durability. Furthermore, it has high compatibility with spinning oil and can produce highly stable products, and the processing agent can be ignored during dyeing, making it possible to achieve satisfactory dyeing.

Next, examples of the present invention will be described in more detail, but it goes without saying that the present invention is not limited to the following description. Unless otherwise specified, the proportions are N amount % or parts by weight.

Na. In the following Examples and Comparative Examples, water repellency and oil repellency were measured as follows. That is, water repellency is expressed by placing a few drops of a mixed solution consisting of 20 parts by volume of isopropanol and 80 parts by volume of water on two places on a sample cloth, and measuring the time it takes for the solution to penetrate. For oiliness, apply a few drops of the test solution shown in Table 1 below on two places on the sample cloth (
Approximately 4 cm in diameter) and judge the penetration state after 30 seconds (
, AATO'C! -TM 11s -u66').

Table 1 (AATC!OTM 118-1966) Antifouling properties are as follows:
Cut the sample cloth into 5 x 7 cfn pieces, put the dry stains shown in Table 2 below (twice the weight of the sample) and the sample into a container,
Mix and agitate vigorously for 3 minutes to contaminate. After contamination, excess dirt was removed using a vacuum cleaner, and the degree of contamination was determined and evaluated by measuring reflectance. The degree of contamination is calculated using the following formula.

Degree of contamination (chi)=Ha2Δx, oO O Table 2 Synthesis Example 1 100 tons of dioxane was charged into a 500-meter internal volume four-tube flask equipped with a Starcy 2 dropping funnel, a thermometer, and a condenser tube. Temperature n is 6”, '8, 1D
', 12 mixtures with an average value of 9.0) were added dropwise over 2 hours. Next, the reaction temperature was increased to 60° C. and the reaction was carried out for 1 hour. The reaction rate was 100.

Synthesis Example 2 The above mixture was pre-emulsified by stirring at 11,000 rpm for 30 minutes at 80°C, and then emulsified using a homogenizer at 60°C.
The mixture was emulsified at ℃ for 30 minutes to prepare a processing agent consisting of an aqueous latex. The flash point of this aqueous latex was 100°C or higher.

Example 1 The aqueous latex of Synthesis Example 2 had a solid content of 0.5 weight JFt.
%, a nylon knit cloth was immersed in the emulsion for 2 seconds, and the cloth was squeezed between two rubber rollers to give a wet pickup of 90 inches. Then, it was dried at 100°C for 3 minutes. The initial water- and oil-repellent performance and antifouling performance of the thus obtained treated fabric were measured. The results are shown in Table 3 below. ,next,
The following dye solution was placed in a pot of Colorpet (manufactured by Nippon Senzo Kikai Co., Ltd.), the treated fabric was placed in a holder, the temperature was raised to 100°C, and dyeing was carried out for 60 minutes.

Bath ratio (1:20) After washing the dyed object with water for 10 minutes, it was dried at 85° C. for 10 minutes. The water- and oil-repellent performance and antifouling performance of the obtained dyed fabric were measured. The results are also shown in Table 3 below.

Examples 2 to 9 Rf shown in Table 3 below synthesized in the same manner as Synthesis Example 1
The compounds used in Example 2.5 were the same as in Synthesis Example 2, and in Example 4.5, diethyl conophosphate in Synthesis Example 2 was replaced with dimethyl adipate. The procedure was the same as in Synthesis Example 2, except that in Example 6.7, diethyl succinate in Synthesis Example 2 was replaced with diethyl glutarate, and in Example 8.9, diethyl oxalate was used. The water- and oil-repellent performance and stain-proofing performance of the nylon knit cloth which was prepared into an aqueous dispersion and further treated in the same manner as in Example 1 are shown in Table 3 below.

Comparative Examples 1 to 2 The Rf compound used in Example 1.2 was converted to the compound of Synthesis Example 2.
The performance was measured in the same manner as in Examples 1 to 9 in the same manner as in Synthesis Example 2 except that diethyl phosphate was changed to butyl acetate in Comparative Example 1 and methylinobutyl ketone in Comparative Example 2. It is shown in Table 3 below.

Claims (1)

[Claims] 1. An aqueous dispersion type antifouling agent containing a polyfluoroalkyl group-containing urethane compound as an active ingredient, characterized in that a dibasic acid diester is used as a water-insoluble organic solvent. Antifouling agent. 2. Polyfluoroalkyl group-containing urethane compound is C
n'2n-1-4 (where n represents an integer from 4 to 16)
The antifouling agent according to claim 1, which is a reaction product of a compound containing perfluoroalkyl 4 represented by the following formula and a polyvalent isocyanate.