JPS6366953B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to an oil composition for imparting level dyeing properties and water and oil repellency to polyamide fibers. (Prior Art) Conventionally, a so-called post-processing method has been commonly used in which fabric products such as carpets are treated with a fluorine compound having a perfluoroalkyl group by spraying or dipping to make them antifouling. When applying by spraying, it is not possible to uniformly apply the treatment agent to the fibers, and when using dipping, the treatment agent does not require substantially stain-proofing properties such as within the carpet base fabric or the bottom of the pile. There was a problem that the carpet adhered to certain areas and deteriorated the texture of the entire carpet. In addition, the above-mentioned processing agents generally have weak adhesion to fibers, so they cannot be used for long periods of time.
Another problem was that the performance of processed products deteriorated due to washing. In order to solve the above problems, in the spinning process such as spinning, drawing, and crimping of synthetic fibers,
A so-called spin finishing method has been proposed to provide a water- and oil-repellent oil agent mainly composed of a fluorine compound having a perfluoroalkyl group. for example,
A method of applying a treatment agent to undrawn polyamide yarn, which is a mixture of a specific polyurethane compound having a perfluoroalkoxy group and an oil agent containing a smoothing agent, a surfactant, etc. (see JP-A-57-171760) ), or by applying a water-free spinning oil to an undrawn polyamide yarn, followed by applying a treatment agent mainly consisting of a perfluoroalkyl group-containing polyurethane compound, and then drawing and heat-treating this yarn to achieve water and oil repellency. , a method for producing polyamide fibers having antifouling properties (see Japanese Unexamined Patent Publication No. 59-204921), and other spin finishing methods have been proposed. (Problems to be Solved by the Invention) The treatment agents proposed above all use fluorine compounds having perfluoro groups, so they have excellent water and oil repellency, but ,
It is not intended to prevent the occurrence of dyeing differences due to unevenness such as filament unevenness due to denier difference, curling difference, etc., physical structural unevenness due to fine structure difference, etc., that is, to improve level dyeing property. In addition, the above-mentioned Japanese Patent Application Publication No. 1983
JP-A-171760 discloses the use of ethylene oxide adducts of higher alcohols and ethylene oxide adducts of aliphatic sulfates as combined oil agents, but these are not selected as leveling agent components. In particular, the latter, the ethylene oxide adduct of aliphatic sulfate, can be expected to have some effect as a leveling agent with affinity for fibers when dyeing acidic dyes, but it can be expected to be effective to some extent as a leveling agent with affinity for fibers. The leveling effect is not necessarily sufficient in practical dyeing where there is a lot of dyeing. (Means for Solving the Problems) This invention provides a fluorine compound (A) having a perfluoro group and represented by the following formula (), and (a) R-O
(X-O) _n H, (b)

[Formula] (c) R-SO ₃ M and (d)

[Formula] (In the above formula, R is a C ₁₀ to C ₂₅ alkal group, X is an ethylene group or a propylene group, M is H or Na,
It consists of a mixed component (B) of metals such as K and Ca (m is 5 to 20), a liquid oil agent (C), and an ester smoothing agent (D), and the above (A) component 100 A level-dying, water- and oil-repellent oil agent for polyamide fibers containing 50 to 400 parts by weight of component (B), 50 to 200 parts by weight of component (C), and 50 to 200 parts by weight of component (D), based on parts by weight. It is a composition. [However, in the formula (), R ₁ is hydrogen or a methyl group,
i is 3 to 10, x is 0 or an integer of 6 or more, p: q
= 3 to 20:1] In the formula () representing the fluorine compound (A) having a perfluoro group, if i is less than 3, the water repellency and oil repellency effects are insufficient; If it exceeds 10, the surface energy lowering effect becomes small, resulting in a decrease in water and oil repellency. In addition, x in formula () is 0 or an integer of 6 or more, preferably 6
~20, and when x is 1 to 5, the recontamination prevention effect decreases. Further, in the formula (), p:q=3 to 20:1, and when q/p is larger than 1/3, the recontamination prevention effect improves, but the water repellency and oil repellency decrease. When q/p is smaller than 1/20, water repellency and oil repellency are improved, but the recontamination prevention effect is reduced. As a specific example of the fluorine compound (A), R in the formula is a methyl group, i=8, x=9, p:q=4:
1 is preferred. In addition, this fluorine compound (A) contains a polyurethane compound in an amount of 5 to 30% relative to the fluorine compound.
The polyurethane compound may be a mixture of % by weight, and specifically preferred is one represented by the following formula (). (In the above formula, R is a C ₁ to C ₅ alkyl group) The fluorine compound (A) of the above formula includes two types of nonionic compounds represented by the following formulas (a) and (b), and ( Mixed component (B) of two types of anionic compounds shown in c) and (d) is blended. (a) R-O-(X-O) _n H (b)

[Formula] (c) R-SO ₃ M (d)

[Formula] In the above formulas (a) to (d), R=C ₁₀ to C ₂₅ alkyl group,
X is an ethylene group or a propylene group, M is H or a metal such as Na, K, Ca, etc., m is 5 to 20,
Preferably it is 5-10. The blending ratio in the above mixed component (B) is (b), (c), (
D)
Preferably 0.5 to 2 parts by weight of each compound. Liquid oils (C) include lubricity, antistatic properties, focusing properties, and heat resistance that can withstand thermal decomposition on heaters in order to maintain productivity and performance in spinning, stretching, crimping, and other post-processes. The required characteristics such as gender must be satisfied. Specifically, high viscosity mineral oil, silicone oil, etc. are preferred. Examples of the ester smoothing agent (D) include monobasic acid esters, dibasic acid esters, polybasic acid esters, glycol esters, polyhydric alcohol esters, etc. Esters are preferred, such as dipropyl sebacate, dilauryl sebacate, dilauryl adipate, sorbitan monooleate, and the like. Note that the above-mentioned ester-based smoothing agent also functions as a swelling agent for polyamide. The blending ratio of the above fluorine compound (A), mixed component (B), mineral oil (C) and ester leveling agent (D) is 50 parts by weight of component (B) per 100 parts by weight of the fluorine compound (A). ~400 parts by weight, preferably 50 to 200 parts by weight, component (C) 50 to 200 parts by weight, preferably 50 to 100 parts by weight, component (D) 50 to 200 parts by weight
parts by weight, preferably 50 to 100 parts by weight. If component (B) is less than 50 parts by weight, the leveling effect will not be sufficient, and if it exceeds 400 parts by weight, water and oil repellency will decrease. If component (C) and component (D) are each less than 50 parts by weight, the spinning properties will be reduced, thread breakage will occur, and
If it exceeds 200 parts by weight, guide pins, guide plates, etc. during spinning become more likely to become dirty, and water repellency and oil repellency may decrease slightly. Furthermore, the above
The blending ratio of component (C) and component (D) is preferably 85 to 20 parts by weight to 15 to 80 parts by weight. The above oil composition may optionally contain a fluorescent dye,
Blue-tinged dyes, spinning agents, ultraviolet absorbers, etc. can be added. It is possible to use a cationic compound that has an affinity for dyes in order to improve the level dyeing properties of polyamide fibers, but it is possible to use cationic compounds that have an affinity for dyes, but the compatibility with other liquid oils, ester leveling agents, etc. It is unsuitable because there are problems such as formation of complexes with other materials and discoloration. The oil composition of the present invention can be applied to short polyamide fibers or filament yarns, particularly undrawn fibers, by a known method such as roller coating, dipping, or spraying, and used as a spinning oil during drawing. suitable. Polyamide fibers include synthetic fibers such as nylon 6, nylon 66, nylon 11, nylon 12, and aromatic nylon, as well as protein-acrylonitrile copolymer fibers and natural polyamide fibers such as wool and silk. . (Function) Mixed component (B) blended into the oil composition of this invention
It was discovered that the specific nonionic compounds (a) and (b) and the specific anionic compounds (c) and (d) among these exhibit a leveling effect on both acid dyes and metal-containing dyes. It was. At this time, nonionic compound (a),
(B) mainly exhibits a level dyeing effect due to improved wettability and a barrier-like slow dyeing effect, and anionic compounds (C),
In addition to the above-mentioned effects, (d) is thought to exhibit a level dyeing effect with affinity for fibers. By using the above nonionic compounds (a) and (b) together with anionic compounds (c) and (d), there is a synergistic improvement in level dyeing.
Particularly good level dyeing properties are expected to be obtained in practical dyeing in which acidic dyes and metal-containing dyes are used in combination. Examples Three types of undrawn yarns with different shades of dyeability obtained by melt-spinning three types of nylon 6 with different amounts of amino end groups as raw resins in the usual manner are shown in Table 1 below. A nylon bulky filament yarn (800 d, 164 single yarns) was produced by applying 4% by weight of the indicated treatment agent and then drawing and crimping. The three types of yarns obtained were fed to a tufting machine so as to be adjacent to each other and tufted onto a base fabric to obtain a loop pile carpet.
The carpet was then win dyed with an acidic dye or a metal-containing dye, and then backed with a backing material in a conventional manner. The resulting loop pile carpet was evaluated for level dyeing, water and oil repellency, and stain resistance, and the results are shown in Table 1 below. The dyeability of the above-mentioned undrawn yarn is determined by dyeing the yarn in a dye bath consisting of 5 g of Suminol Milling Cyanine 5R (blue acid dye, manufactured by Sumitomo Chemical Co., Ltd.) and 30 g of ammonium sulfate. Dyeing was carried out at a ratio of 1:100 at boiling for 60 minutes, and with the dyeing rate of intermediate colors as the standard, the dyeing rate was +1% for dark colors and -1% for light colors.

[Table] The fluorine compound A ₁ in Table 1 above is R=CH ₃ in the formula (), i=8, x=9, p:q=4:1, and the fluorine compound A ₂ is , the above fluorine compound A ₁
10 parts by weight of a compound of the following formula are mixed with 90 parts by weight of . In addition, (A) in the mixed component (B) is R=C ₁₂ H ₂₅ , m=
5 nonionic compound, (b) is R=C ₁₂ H ₂₅ , m=
5 nonionic compound, (c) is R=C ₁₈ H ₃₇ , M=
Anionic compound of Na, (d) is R=C ₁₂ H ₂₅ , M=
It is an anionic compound of Na. Further, the ester smoothing agent D ₁ is dilauryl sebacate, and the ester leveling agent D ₂ is sorbitan monooleate.
Acidic 1 in the dyeing test used a dye bath containing the following acid dye (manufactured by Bayer AG). Teron Yellow K-FGL 0.2%owf Teron Red BLL 0.2%owf Teron Blue K-GGLL 0.2%owf Acetic acid 0.5cc/ Sodium acetate 2.5g/ Leveling agent Nonionic compound (a) 0.2%owf Leveling agent Anionic compound (d) 0.2% owf The dyeing conditions were a bath ratio of 1:50 and a temperature of 70°C from 30°C to 98°C.
Raise the temperature in minutes, hold at 90℃ for 60 minutes, then wash with hot water.
I washed it with water. In addition, dyeing method (1) in the above table is when a leveling agent is not mixed, dyeing method (2) is when a leveling agent is mixed, and dyeing method (1) without a leveling agent is: The time to raise the temperature from 30°C to 98°C was 30 minutes. Acidity 2 in the dyeing test is the following acid dye (manufactured by Sumitomo Chemical Industries, Ltd.) in the above acidity 1 dye bath.
It was used. Suminol Milling Yellow 0.15%owf Suminol Milling Scarlet G
0.2% owf Suminol Leveling Blue AGG 0.1% owf Regarding the metal content in the dyeing test, the following metal-containing dye (manufactured by Sumitomo Chemical Industries, Ltd.) was used in the acidic 1 dye bath. Ranil Yellow G 0.1% owf Ranil Blue G 0.5% owf The dyeing methods (1) and (2) and dyeing conditions for acidic 2 and metal containing are all the same as acidic 1. The level dyeing properties of the above various dyes are determined by
The degree of occurrence of irritation and streaks was visually determined, and those with excellent level dyeing were rated ◎, and those with poor level dyeing were rated ○, △, and × in order. The water repellency in Table 1 above was determined by mixing isopropanol and water in different volume ratios, placing small droplets of this mixture on a carpet surface, and determining the wetting state as shown in Table 2 below.

[Table] Oil repellency was evaluated according to AATCC118-1975. Practical stain resistance was determined by dropping a liquid such as juice, coffee, soy sauce, or salad oil onto a carpet from a height of 10 cm, leaving it for 5 minutes, wiping it off with tissue paper, and visually determining whether it stained. . (Effects of the Invention) As shown in Table 1 above, the oil composition of the present invention has improved level dyeing properties on nylon fibers and is excellent in water repellency and oil repellency.

Claims (1)

[Scope of Claims] 1. A fluorine compound (A) having a perfluoro group and represented by the following formula (), (a) R-O(X-O) _n H,
(b) [Formula] (c) R-SO ₃ M and (d) [Formula] (in the above formula, R is a C ₁₀ to _{C 25} alkyl group, X is an ethylene group or a propylene group, and M is H or It consists of a mixed component (B) of metals such as Na, K, Ca, etc. (m is 5 to 20), a liquid oil agent (C), and an ester smoothing agent (D), and the above (A) 50 parts of component (B) per 100 parts by weight of component
~400 parts by weight, component (C) 50 to 200 parts by weight, component (D) 50 to
200 parts by weight of a level-dying, water- and oil-repellent oil composition for polyamide fibers. [However, in the formula (), R ₁ is hydrogen or a methyl group,
i is 3 to 10, x is 0 or an integer of 6 or more, p: q
= 3 to 20:1] 2. Mixed component (B) is a patent claim in which each of compounds (b), (c), and (d) is 0.5 to 2 parts by weight per 1 part by weight of chemical formula (a). The level dyeing, water- and oil-repellent oil composition for polyamide fibers according to item 1.