JPH0121268B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a water- and oil-repellent treatment method, and more specifically, to a novel water- and oil-repellent treatment method comprising simultaneously absorbing a specific polyfluoroalkyl group-containing compound together with a dye into fibers at a relatively high temperature. . Conventionally, polyfluoroalkyl group (hereinafter referred to as PFA
When treating fibers with a water- and oil-repellent finishing agent having a group (hereinafter referred to as "group"), a method is generally adopted in which the surface of the fiber is coated with an aqueous emulsion or an organic solvent solution of an acrylate polymer. . However, such polymeric processing agents are mainly discontinuous phases held on the fiber surface by physical adhesion, so they are susceptible to mechanical action or wear caused by the fibers during the process up to the finished product.
There is a tendency for it to fall off due to friction. In addition, for processing agents copolymerized with N-methylol acrylamide, hydroxyethyl methacrylate, glycidyl methacrylate, etc. for the purpose of increasing adhesion, resins such as methylol melamine are used in the actual processing to form a network and harden on the fibers. Because of this, there is a tendency for the texture to become rough and hard. On the other hand, various means have been proposed to solve the problems of polymer processing agents as described above. for example,
A method has been proposed in which low molecular weight fluorine compounds consisting of ester derivatives such as phthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid are used as processing agents for synthetic fibers. U.S. Patent No. 3,646,153;
See the specifications of the same No. 3870748 and the same No. 4209610. According to the study of the present inventor, in the water and oil repellent treatment of pile-shaped textile products such as raised products or carpets that are difficult to dry, the pad method using a polymer finishing agent may not be able to process them. It's emerging. Also, in terms of performance, a high degree of durability has become required, but no processing means has been found that can satisfy such demands with polymer processing agents. Furthermore, when a fiber dyeing process is required, polymer finishing agents have limitations in their application to products after dyeing is completed, and there are also difficulties in imparting sufficient water and oil repellency with excellent durability. It will be done. The present inventor has conducted various studies on fiber treatment with various fluorine compounds having a PFA group, and as a result, has obtained the following extremely interesting findings. That is, when synthetic fibers are treated at relatively high temperatures with specific low molecular weight fluorine compounds such as urethane compounds and triazine compounds, which will be detailed later, We have discovered that it is possible to achieve performance that cannot be achieved with finishing. In such high temperature treatment, the specific low molecular weight fluorine compound does not simply adhere to the fiber surface, but is well absorbed and fixedly retained within the synthetic resin constituting the fiber. As a result, a high level of water and oil repellency is achieved that can withstand washing, dry cleaning, and mechanical abrasion, and the resulting fibers also have a good texture. Furthermore, surprisingly, high-temperature treatment with a specific low-molecular-weight fluorine compound can be smoothly and advantageously applied to the fiber dyeing process, and it has been found that it can be absorbed and fixed within the fiber at the same time as it coexists with the dye. This is what was obtained. As a result, it was completed as an epoch-making method that can simultaneously perform a good dyeing process and a water- and oil-repellent finish using a one-step process that involves adding a specific low-molecular-weight fluorine compound to a dye-containing bath. be. In particular, high-temperature treatments such as steam heat, dry heat, and various dyeing processes performed under high temperature and high pressure can be applied to the absorption and fixation of specific low-molecular-weight fluorine compounds, which is extremely advantageous in terms of energy saving. Thus, the present invention has been completed based on the above findings, and it is possible to apply a polyfluoroalkyl group-containing compound represented by the following general formula () or () and having a molecular weight of 400 to 2000 and a dye onto fibers. To provide a new method for water- and oil-repellent treatment of fibers, which is characterized in that the polyfluoroalkyl group-containing compound and the dye are simultaneously absorbed and fixed in the fiber by maintaining the temperature at 60 to 250°C in a state in which the polyfluoroalkyl group-containing compound and the dye coexist. It is something. Since the present invention can perform water and oil repellent treatment at the thread stage,
It can be easily applied to thick fabrics and pile products that are difficult to process using conventional post-processing methods. That is, it has the advantage of not being affected by the shape of the final product. The PFA group-containing compound used in the present invention is represented by the following general formula. In the above general formula, R _f has 4 carbon atoms.
~16 linear or branched polyfluoroalkyl groups, usually those with a perfluoroalkyl group at the end, but those containing a hydrogen or chlorine atom at the end, or oxy Perfluoroalkylene-containing groups and the like can also be used. A preferred embodiment of R _f is C _p F _2p+1 (where p is 4
(representing an integer of 16 to 16), and those having 6 to 12 carbon atoms are particularly preferred. X is -R-, -CON(R ¹ )-Q-, or -
SO ₂ N(R ¹ )-Q- (where R is an alkylene group, R ¹
is a hydrogen atom or a lower alkyl group, and Q is one of two organic groups), preferably one having 1 to 1 carbon atoms, represented by C _q H _2q (where q is an integer of 1 to 10). Ten alkylene groups are chosen, especially alkylene groups having 2 to 4 carbon atoms. Further, Q is a divalent organic group, and an alkylene group -R- is usually exemplified as a suitable one. A, A ¹ and A ²
are respectively -O-, -S-, or -N(R ² )- (however,
^R2 represents a hydrogen atom or a lower alkyl group), and from the viewpoint of availability, A is -O-, and ^A1 and ^A2 are -O- or -N( ^R2 )- It is preferable that Next, Z is a monovalent organic group containing an alkyl group, an aryl group, or a heteroatom;
Further examples include -X-R _f , but from the viewpoint of water repellency and oil repellency, lower alkyl groups having 1 to 4 carbon atoms are preferably selected. Z ¹ and Z ² are a hydrogen atom or a monovalent organic group, and examples thereof include the same as Z above. For example, −A ¹ −Z ¹ and −A ² −Z ²
are respectively -OR'(R' is an alkyl group), -NH ₂ ,
_-NHCH2OH , _{-NHCH2CH2OH ,}

【formula】

[Formula] −OCH ₂ CH ₂ CN, OCH ₂ CH ₂ NO ₂ , −N
( _{CH2CH2OH ) 2} ,

【formula】

[Formula] −NHCON ^- N ⁺ (CH ₃ ) ₂ CH ₂ CH ₂ OH,

[Formula] etc. can be exemplified as suitable ones. Therefore, in the urethane-based compound of the general formula (), Y is a divalent organic group, and a group having 24 or less carbon atoms, especially 6 to 15 carbon atoms, is used to stiffen the urethane molecule and improve performance. From the viewpoint of improving the durability, those containing at least one aromatic ring or aliphatic ring are preferably employed. Further, n is an integer of 1 or more, and is usually an integer of 1 to 10, particularly an integer of 1 to 3. It may be a mixture of a urethane compound (○) corresponding to n=1 and an allophanate compound (○) corresponding to n=2 or more. In the present invention, a specific PFA group-containing compound (hereinafter, specific PFA group-containing compound) of the general formula () or ()
(abbreviated as “compound”) has a molecular weight of about 400 to 2000,
It is important that it is preferably about 700 to 1200. If the molecular weight is too high, it will be difficult to sufficiently absorb and retain the fibers even by the high-temperature treatment of the present invention, and the effect of the water- and oil-repellent treatment, which has excellent durability, will be minimal. The high temperature treatment of the present invention using a specific PFA compound with a relatively low molecular weight is characterized in that it can be smoothly and advantageously applied to the dyeing process. In the present invention, it is possible to use an organic solution or an organic dispersion of a specific PFA compound, but in consideration of application to the dyeing process described below, it is preferable to use an aqueous dispersion. In this case, various types of surfactants such as nonionic, anionic, cationic, and amphoteric surfactants can be used as the dispersant.
These may be used in combination as appropriate. An organic solvent may be used in combination for the purpose of promoting dispersion of the specific PFA compound. In addition, when dispersing a specific PFA compound in a medium mainly composed of water, the general formula R _f -X-A-
It may be dispersed in the presence of a fluorine-containing surfactant such as a hydrophilic group-containing urethane compound represented by CONH-Y-NHCO-W. Here, R _f ,
X, A and Y are as described above, and W is a hydrophilic group. As W, −(CH ₂ CH ₂ O) _l −R ³ (However, l
is an integer from 1 to 50, R ³ is a hydrogen atom or a carbon number of 1 to 50
-(CH ₂ CH ₂ O) _l -SO ₃ M (however, M
represents a hydrogen atom, an alkali metal or an ammonium group), -(CH ₂ CH ₂ O) _l -PO ₃ M, -
Anionic groups such as CH ₂ CH ₂ SO ₃ M, -CH ₂ CH ₂ COOM, and -CH ₂ CH ₂ N R ⁴ R ⁵ R ⁶ X (However, R ⁴ , R ⁵ and R ⁶ are alkyl groups, aryl group, etc., and X represents Cl, Br, I, OCOCH ₃ , etc.)
Examples include various cationic groups such as, but from the viewpoint of compatibility with other processing agents, nonionic groups such as -(CH ₂ CH ₂ O) ₂₂ -CH ₃ can be preferably employed. It is. When coexisting such hydrophilic group-containing urethane compounds, specific PFA
Compound/hydrophilic group-containing urethane compound weight ratio
The coexistence ratio is selected from the range of 99/1 to 25/75, preferably 95/5 to 50/50. Examples of organic solvents used in conjunction with the dispersion of specific PFA compounds in water include 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 monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl Ether, water-soluble glycol ethers such as triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, amides such as formamide, dimethylformamide, acetamide, acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketones,
Examples include ketones such as diacetone alcohol, alcohols such as methanol, ethanol, propanol, and butanol, and esters such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate. The amount of such organic solvent added must be specified.
Normally per 100 parts by weight of PFA compound (total amount with other PFA group-containing compounds when used together)
The amount is selected from the range of 10 to 300 parts by weight, preferably 20 to 150 parts by weight. The specific PFA compound in the present invention can be obtained by various synthetic means. That is, the triazine derivative of the general formula () is, for example, cyanuric trichloride.
It can be synthesized by reacting R _f -X-A-H, Z ¹ -A ¹ -H, and Z ² -A ² -H. Specific examples include the following (a) to (e), and these triazine derivatives are described in "Asahi Glass Research Report" Vol. 31, No. 1 (1981) published on September 25, 1981. Pages 9 to 9 of
It is described on page 15, or in Japanese Patent Publication No. 43-307. Or, the urethane compound of general formula () is
For example, a fluorine-containing compound R _f -X-A-H (e.g. R _f
By adding 1 mol each of CH ₂ CH ₂ OH) and compound Z-A ¹ -H (e.g. methanol),
Urethane compound corresponding to n = 1 R _f -X-A
-CONH-Y-NHCO- ^A1 -Z can be produced. Allophanate compounds (○) corresponding to n=2 or more can be synthesized by an addition reaction between a -CONH- group-containing compound such as the above-mentioned -CONH- group-containing compound and a -N=C=O group-containing compound. Regarding these, please refer to U.S. Patent No. 3398182, Japanese Patent Publication No. 46-348, Japanese Patent Application Laid-open No. 112855-1982, and Japanese Patent Application Laid-open No. 74-74000.
No. 133485, Japanese Patent Application No. 133485, Patent Application No. 1983-
It is described in the specification of No. 49329, etc. As R _f -X-A-H in the above, a fluorine-containing alcohol of the R _f -R-OH type is usually suitably employed. By using a mixture of multiple fluorine-containing alcohols with different carbon numbers or R in R _f as raw materials, a specific PFA compound (
It is also possible to produce () in the form of a mixture. Also, regarding Z-A ¹ -H, as mentioned above,
A lower alcohol in which A ¹ is -O- and Z is a lower alkyl group having 1 to 4 carbon atoms is a particularly preferred embodiment of the present invention. For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t
-Butanol is exemplified, with methanol or ethanol being particularly preferred. Furthermore, Z ¹ −A ¹ −H
Examples of Z ² -A ² -H include, in addition to the lower alcohols, ammonia, water, alkanolamines, amines, diamines, etc. As shown in (b) above, combinations of ammonia and methylolating agents, etc. But it's okay. As for OCN-Y-NCO, as mentioned above, it is preferable that Y is a divalent organic group having 24 or less carbon atoms, particularly 6 to 15 carbon atoms. For example, 2,4
- Aromatic diisocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, tolidine diisocyanate, dianisidine diisocyanate, 2-methyl-cyclohexane-1,4-diisocyanate , isophorone diisocyanate, hydrogenated MDI Examples include alicyclic diisocyanates such as hexamethylene diisocyanate, and aliphatic diisocyanates such as decamethylene diisocyanate. A diisocyanate containing a diisocyanate is preferably employed. Specific examples of the specific PFA compound in the present invention as described above are as follows. That is, as a triazine derivative of general formula (), Examples include. In addition, as a urethane compound of general formula (), Examples include R _f CH ₂ CH ₂ OCONH(CH ₂ ) ₆ NHCOOR ₁ . Here, R _f and R ₁ are as described above, R ₁ , R ₂ and R ₃ are alkyl groups having 1 to 30 carbon atoms, R _f SO ₂ NHCH ₂ CH ₂ −, R _f
CONHCH ₂ CH ₂ − or R _f CH ₂ CH ₂ −, etc. In the present invention, when the specific PFA compound is used in the form of an aqueous dispersion by dispersing it in a medium mainly composed of water, various methods can be employed as the dispersion means. For example, a method in which a mixture of a PFA compound, an emulsifier (surfactant), and an aqueous medium is heated and stirred at high speed, and then cooled to room temperature; dropwise while stirring, or
Possible methods include dropping an aqueous emulsifier solution into an organic solvent solution of a PFA compound while stirring, dropping an organic solvent solution of a PFA compound and emulsifier into water with stirring, or vice versa. It is. The treatment method of the present invention is to heat a specific PFA compound and a dye in a state where they coexist on the fiber, so that both are absorbed and fixed into the fiber at the same time. Such absorption and fixation treatment can be carried out in dyeing machines used for dip dyeing, such as winch, jigger, beam, cheese, cot, cake, and jet dyeing machines, as well as in thermosol dyeing machines, high-temperature steam machines, and high-pressure steam dye machines. It can be carried out in a dyeing machine commonly used for fixing dyes, such as a dyeing machine. In addition to the one-bath one-stage treatment using a bath containing a PFA compound and dye, the present invention also allows one-bath two-stage treatment and two-bath two-stage treatment to treat PFA.
It is possible if heat absorption fixation can be carried out in a state where the compound and dye coexist. For example, the fibers are treated in a dyeing bath and then a PFA compound is added to the same dyeing bath to treat the fibers, or the fibers are treated in a bath containing a PFA compound and a dye is added to the same bath for dyeing. Two-stage bath treatment is possible. Also,
A two-bath, two-step process in which the dyeing bath and the PFA compound-containing bath are separate is also possible. By such processing
The PFA compound and the dye are made to coexist on the fiber, and heated in this state so that both are simultaneously absorbed and fixed within the fiber. In the present invention, as described above, the fiber is heated in a state where the PFA compound and the dye coexist on the fiber. A relatively high heating temperature of 60 to 250° C. is employed, but it is desirable to select a suitable temperature range depending on the type of fiber and the type of processing means. For example, for polyester fiber, 60 to 250℃,
Preferably 70-220℃, 60-130℃ for polyamide fibers and polyacrylic fibers, preferably 70-110℃
degree is adopted. Such heating temperature can be selected from the same range as the preferred range generally used when absorbing and fixing dyes into fibers. PFA
The amount of the compound absorbed and fixed into the fibers is about 0.05 to 5 parts by weight, preferably about 0.10 to 1.0 parts by weight per 100 parts by weight of the fibers. The simultaneous absorption and fixation means of the present invention will be explained in more detail below. That is, examples of such processing means include those similar to the methods, equipment, and conditions employed in dyeing synthetic fibers, as described above.
For example, in the case of drying treatment, the fibers are padded in a bath, dried, and then heated in a thermosol dyeing machine or the like, similar to the thermosol dyeing method.
Polyester fibers are held at a temperature of 180 to 220°C for 60 to 120 seconds to be absorbed into the fibers. In addition, in the case of steaming, high-pressure steaming or high-temperature steaming may be used, and usually the fibers are padded or
After printing with printing paste containing PFA compound, drying
Steam treatment. For polyester fibers, high-pressure steaming at 70-130℃ for 10-60 minutes, high-temperature steaming
By holding it at 70-180°C for 10-60 minutes, it is absorbed into the fibers. Polyamide fibers and polyacrylic fibers are steam-treated at 70-100°C for 10-60 minutes. Furthermore, in the case of high-temperature and high-pressure treatment, ordinary dyeing methods can be used, and when using a carrier component for dyeing with polyester fibers, it is possible to
For ~60 minutes, high-pressure staining requires holding at 70~140°C for 10~60 minutes. Polyamide fibers and polyacrylic fibers can be subjected to high temperature and high pressure treatment by holding them at 70 to 100°C for 10 to 60 minutes. The above-mentioned absorption fixation method not only uses dyes for dyeing synthetic fibers, such as disperse dyes, acid dyes, cationic dyes, etc., in combination with PFA compounds, but also
After treatment with a PFA compound, dyeing with these dyes may be performed simultaneously with absorption and fixation by heating. In addition to the advantage of being able to perform water and oil repellency treatment and dyeing treatment at the same time, the present invention employs steam heat treatment to provide good water and oil repellency and dyeing to brushed or piled items such as blankets and carpets. It is something that can be granted. In the case of dyeing polyester fibers, ortho-phenylphenol,
A carrier method in which a carrier such as methylnaphthalene or chlorobenzene is added may also be used. In the thermosol method, a glue agent such as sodium alginate may be used in combination for the purpose of preventing migration during the drying process. Furthermore, it is also possible to use a leveling agent, a slowing agent, a dispersing agent, etc. as a dyeing aid. Next, embodiments of the present invention will be described in more detail, but it goes without saying that the present invention is not limited by such explanations. Percentages are percentages or parts by weight unless otherwise specified. In addition, in the following examples and comparative examples, water repellency and oil repellency were measured as follows. That is,
Water repellency is determined by JIS L-1005 spray method.
No. (see Table 1 below), and oil repellency is determined by placing a few drops (approximately 4 mm in diameter) of the test solution shown in Table 2 below on the sample cloth in two places, and penetration after 30 seconds. Judgment is based on the condition (AATCC-TM118-1966).

【table】

[Table] Regarding durability, JIS L-0217-103
The samples were washed according to the method and evaluated by measuring the degree of decrease in water and oil repellency. That is, after washing for 10 minutes at 40℃ using a household electric washing machine with 55g of detergent (Blue Diamond: brand name), bath volume 20,
The process of rinsing for 10 minutes and then drying is performed once, and the water and oil repellency is measured after a predetermined number of times. Example 1

[Table] The above mixture was pre-emulsified by stirring at 1000 rpm for 30 minutes at 80°C, then 60°C using a homogenizer.
Emulsification was carried out at ℃ for 30 minutes to prepare a processing agent A consisting of an aqueous latex. Processing agent A 0.5% owf Dye (Suminol Leveling Sky Blue R: Acid dye manufactured by Sumitomo Chemical Co., Ltd.) 1% owf (NH ₄ ) ₂ SO ₄ 3% owf Dyeing aid (Disper SV: Anionic dispersion manufactured by Meisei Chemical Co., Ltd.) 1% owr Bath ratio (1:20) Add the above dye solution to Colorpet (manufactured by Nippon Senzo Kikai Co., Ltd.)
A nylon processed yarn knit was placed in a holder, heated to 100°C, and dyed for 30 minutes. After washing the dyed item with water, apply Ratcor ST2.
After soaping for 10 minutes at 80°C in a bath of 100g/g/g/g/g/g/g/g/g/g of bath, the sample was washed with water, dried, and heat set at 180°C for 1 minute. The resulting nylon cloth has a water repellency of 90 and an oil repellency of 7.
After washing 10 times, the water repellency was 80 and the oil repellency was 6. Example 2 Processing agent A 0.5% owf Dye (Holonrubin S-2GL: disperse dye manufactured by Sandoz Co., Ltd.) 1% owf Dyeing aid (Disper GS-50: anionic emulsifier manufactured by Meisei Chemical Industry Co., Ltd.) 0.5 g/Acetic acid (90%) ) 0.25cc/bath ratio (1:20) Pour the above dye solution into the pot of Colorpet, put the polyester processed yarn knit into the holder, and
After raising the temperature to ℃, staining was carried out for 30 minutes. Wash the dyed item with water,
It was subjected to reduction cleaning and heat set at 180°C for 1 minute. The water repellency was 90 and the oil repellency was 7. After washing 10 times, the water repellency was 80 and the oil repellency was 6. Example 3 Processing agent A 0.5% owf Dye (Sumya Acrylic Blue N-3RL: cationic dye manufactured by Sumitomo Chemical Co., Ltd.) 1% owf Acetic acid (90%) 1% owf Sodium acetate 0.5% owf Dyeing aid (Dylevelin AN: (Cationic emulsifier manufactured by Meisei Kagaku Kogyo Co., Ltd.) 1% owf Bath ratio (1:20) The above dyeing liquid was placed in a pot of Colorpet, and a cashmilon fabric was placed in the holder and the temperature was raised to 100°C, followed by dyeing for 30 minutes. After washing the dyed object with water, it was soaped in a bath containing 2 g of Latcol PSK at 80°C for 10 minutes, and after washing and drying, it was heat set at 130°C for 1 minute. The water repellency was 80 and the oil repellency was 6. After washing 10 times, the water repellency was 70 and the oil repellency was 5. Examples 4 to 7 and Comparative Example 1 The processing agent was prepared and the nylon processed yarn was prepared in the same manner as in Example 1, except that the R _f group-containing compound in the processing agent A of Example 1 was replaced as shown in Table 3 below. Treatment was carried out using a knit dyeing bath. Also,
A similar experiment was conducted as Comparative Example 1 using a polymer containing an R _f group and having a molecular weight of 20,000 instead of the R _f group-containing compound. The results are shown in Table 3 below.

[Table] Comparative Example 2 In Example 1, when the treatment temperature was set to 50°C, both the initial water repellency and oil repellency of the resulting nylon cloth were 0. Comparative Example 3 In Example 2, when the treatment temperature was set to 50° C., both the initial water repellency and oil repellency of the resulting polyester fiber cloth were 0. Comparative Example 4 In Example 3, when the treatment temperature was set to 50°C, both the initial water repellency and oil repellency of the resulting polyacrylic fiber cloth were 0. Examples 8-9 Processing agent A 0.5% owf Holonrubin S-2GL (disperse dye manufactured by Sandoz)
2% owf Disper GS-57 (Anionic emulsifier manufactured by Meisei Chemical Industry Co., Ltd.) 0.5g / Acetic acid (90%) 0.25ml / After preparing the above dye liquor and padding a polyester fiber fabric with a squeezing rate of 80%, it was heated to 100℃. and dried for 3 minutes. Next, a piece of the treated fabric was treated in a thermosol dyeing machine at 200°C for 260 seconds (Example 8),
Another piece was treated in a high-pressure steamer at 130°C for 30 minutes (Example 9). After washing the two pieces of fabric thus obtained,
Reduction cleaning was performed at 85°C for 10 minutes with an aqueous solution containing 0.2% Laccol ST, 0.2% hydrosulfide, and 0.2% NaOH, and heat set at 180°C for 60 seconds.
As a result, all the fabrics had a water repellency of 70 and an oil repellency of 5, and could be dyed in good hues. Example 10

[Table] The above mixture was placed in an autoclave equipped with a thermometer and a stirrer, heated while performing high shear stirring, held at 100°C for 30 minutes, and then cooled to room temperature to obtain an aqueous latex. The latex was processed into nylon textured yarn knit in the same manner as in Example 1. As a result, the water repellency was 100 and the oil repellency was 7, and the water repellency after 10 washes was 90 and the oil repellency was 6. Example 11

【table】

[Table] The above mixture was pre-emulsified by stirring at 1000 rpm for 30 minutes at 80°C, then 60°C using a homogenizer.
Emulsification was carried out at ℃ for 30 minutes to obtain an aqueous latex. The latex was processed into nylon textured yarn knit in the same manner as in Example 1. As a result, the water repellency was 90 and the oil repellency was 7. After 10 washes, the water repellency was 80 and the oil repellency was 6.
It was hot.

Claims (1)

[Claims] 1. A polyfluoroalkyl group-containing compound represented by the following general formula () or () and having a molecular weight of 400 to 2000 and a dye coexist on the fiber at a temperature of 60 to 250°C. 1. A method for water- and oil-repellent treatment of fibers, which comprises simultaneously absorbing and fixing the polyfluoroalkyl group-containing compound and the dye into the fibers. However, in the above general formula, R _f has 4 to 4 carbon atoms.
16 polyfluoroalkyl groups, X is -R
−, −CON(R ¹ )−Q− or −SO ₂ N(R ¹ )−Q−
(However, R is an alkylene group, R ¹ is a hydrogen atom or a lower alkyl group, and Q is a divalent organic group), and A, A ¹ and A ² are -O-, -S- or -N
(R ² )- (where R ² represents a hydrogen atom or a lower alkyl group), Z is a monovalent organic group, Y is a divalent organic group, and n is 1 or more. is an integer. 2 R _f is a perfluoroalkyl group represented by C _p F _2p+1 (where p is an integer from 4 to 16), and X is
An alkylene group represented by C _q H _2q (where q is an integer of 1 to 10), A is -O-, A ¹ and A ² are -O- or -N(R ² )- (however, R ² represents a hydrogen atom or a lower alkyl group), Y is a divalent organic group having at least one aromatic ring or aliphatic ring, and n is an integer of 1 to 3. The method described in Scope 1. 3. The method according to claim 1, in which the polyfluoroalkyl group-containing compound and the dye are simultaneously brought into contact with the fibers using a dye-containing liquid to which the polyfluoroalkyl group-containing compound is added, so that the polyfluoroalkyl group-containing compound and the dye coexist on the fibers. . 4 A polyfluoroalkyl group-containing compound and a dye are allowed to coexist on the fiber, and heated to a temperature of 70 to 70°C under steaming conditions.
The method according to claim 1 or 3, wherein the temperature is maintained at 180°C for 5 minutes to 2 hours. 5 A polyfluoroalkyl group-containing compound and a dye are made to coexist on the fiber, and heated to a temperature of 160°C under dry heat conditions.
Claim 1: Holding at ~250°C for 5 to 300 seconds
or the method described in paragraph 3. 6. The method according to claim 1, in which a polyfluoroalkyl group-containing compound and a dye are allowed to coexist on the fiber and held at a temperature of 70 to 140°C for 5 minutes to 2 hours under a high pressure state of 1.5 atmospheres or more. . 7 The amount of the polyfluoroalkyl group-containing compound absorbed and fixed into the fiber is 0.05 to 5 per 100 parts by weight of the fiber.
2. The method of claim 1, wherein parts by weight.