JPH0147594B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a water- and oil-repellent treatment method for fibers, and more specifically, a novel method that involves absorbing and fixing a relatively low molecular weight compound containing a polyfluoroalkyl group onto fibers through a specific dry heat treatment. This invention relates to a water and oil repellent treatment method. 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 inventor's study, 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. In other words, 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 explained in detail later, performance that cannot be achieved with finishing using conventional polymer finishing agents can be achieved. We have found that it is possible to achieve this. 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 low molecular weight compounds containing PFA groups is possible by employing dry heat treatment in the fiber dyeing process, and specific PFA compounds can be absorbed into fibers even when coexisting with dyes. We found that it is fixed. the result,
It was completed as an epoch-making method that can efficiently carry out dyeing and water- and oil-repellent finishing.
Furthermore, since the dry heat treatment in the dyeing process can be applied to absorb and fix PFA group-containing low molecular weight compounds, it is extremely advantageous in terms of energy saving. Thus, the present invention was completed based on the above findings, and it is possible to prepare a polyfluoroalkyl group-containing compound having a molecular weight of 40 to 2000 at a temperature of 180 to 220°C.
The present invention provides a new method for treating fibers with water and oil, which is characterized by absorbing and fixing fibers through dry heat treatment. According to the method of the present invention, (1) a PFA compound is absorbed and fixed on the fiber at the same time as the dye, (2) after dyeing is completed,
Add a PFA compound to the same bath or another bath and let it absorb and stick to the fibers under the same conditions as dyeing, (3)
Various embodiments are possible, such as dyeing after absorbing and fixing the PFA compound onto the fibers. Even products that are pile-like and difficult to dry, such as brushed products or carpets, can be treated with a high degree of water and oil repellency, and retain good durability against washing, dry cleaning, and mechanical abrasion. , without impairing the texture of the resulting textile products. In the present invention, a wide variety of relatively low-molecular-weight PFA group-containing compounds can be employed, but a compound represented by the following general formula is exemplified as a preferred representative example. 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 a divalent organic group), 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, R ²
represents a hydrogen atom or a lower alkyl group), and in terms of availability, A is -O-,
Preferably, A ¹ and A ² are -O- or -N(R ² )-. Next, Z is a monovalent organic group, and examples include those containing an alkyl group, an aryl group, a hetero atom, and -X-R _f , but the number of carbon atoms is limited from the viewpoint of water repellency and oil repellency. 1 to 4 lower alkyl groups 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 -OR'(R' is an alkyl group), -NH ₂ , -
NHCH ₂ OH, −NHCH ₂ CH ₂ OH, −NHCH ₂ − −OCH ₂ CH ₂ CN, −OCH ₂ CH ₂ NO ₂ , −N
( _{CH2CH2OH ) 2} , etc. can be exemplified as suitable examples. Therefore, in the urethane compound of general formula (), Y is a divalent organic group, and usually has 24 carbon atoms.
or less, especially 6 to 15, and preferably contains at least one aromatic or aliphatic ring from the viewpoint of making the urethane molecule rigid and improving durability of performance. Also, n
is an integer of 1 or more, usually an integer of 1 to 10, particularly an integer of 1 to 3. It may also be a mixture of urethane compound (○) corresponding to n=1 and urethane 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 dry heat treatment of the present invention, and the effect of the highly durable water and oil repellent treatment will be minimal. The dry heat 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, and 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-
It may be dispersed in the presence of a fluorine-based surfactant such as a hydrophilic group-containing urethane compound represented by A-CONH-Y-NHCO-W. Here,
R _f , X, A, and Y are as described above, and W is a hydrophilic group. For W, −(CH ₂ CH ₂ O) _l −R ³
(However, 1 is an integer from 1 to 50, and R ³ is a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms.) A nonionic group represented by -(CH ₂ CH ₂ O) _l -SO _3M
(However, M represents one of a hydrogen atom, an alkali metal, or an ammonium group), -(CH ₂ CH ₂ O) _l -
Anionic groups such as PO ₃ M, −CH ₂ CH ₂ SO ₃ M, −CH ₂ CH ₂ COOM, and even −CH ₂ CH ₂ N
R ⁴ R ₅ R ⁶ X (However, R ⁴ , R ⁵ , R ⁶ are alkyl groups,
Indicates an aryl group, etc., and X is Cl, Br, I,
_Various examples include cationic groups such as
(CH ₂ CH ₂ O) ₂₂ −CH ₃ and the like can be preferably employed. When such a hydrophilic group-containing urethane compound is allowed to coexist, the weight ratio of the specific PFA compound/hydrophilic group-containing urethane compound is from 99/1 to 25/75, preferably from 95/5 to 50/50. A percentage is selected. Water-soluble organic solvents are suitable as the organic solvent used in combination when dispersing the specific PFA compound in water, including water-soluble ethers such as dioxane, tetrahydrofuran, and ethylpropyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and ethylene. Glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether,
Water-soluble glycol ethers such as diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, formamide, dimethyl Amides such as formamide and acetamide, acetone, methyl ethyl ketone, methyl isopropyl ketone,
Examples include ketones such as methyl isobutyl ketone and 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 water-soluble organic solvent added is usually 10 to 300 parts by weight per 100 parts by weight of the specific PFA compound (if other PFA group-containing compounds are used together, the total amount with these),
It is preferably selected from a range of 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 and Z ¹ -A ¹ -H, Z ² -A ² -H. Specific examples include the following a) to e). It is described on pages 9 to 15, or in Japanese Patent Publication No. 307-1973. Further, the urethane compound of the general formula () is, for example, a diisocyanate (OCN-Y-NCO) and a fluorine-containing compound R _f -X-A-H (for example, 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. The urethane compound ○B corresponding to n=2 or more can be synthesized by the addition reaction of a -CONH- group-containing compound such as ○A above 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. 112855-1980, Japanese Patent Application Laid-open No. 74000-1989,
It is described in Japanese Patent Application Laid-Open No. 54-133485, Japanese Patent Application No. 56-49329, 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. 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 ammonia, water, alkanolamines, amines, diamines, etc. in addition to the above-mentioned lower alcohols, and b)
A combination of ammonia and a methylolating agent may also be used as shown in FIG. 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, 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. 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; A method of dropping it into an aqueous solution of while stirring,
Alternatively, a method in which an aqueous solution of an emulsifier is dropped into a water-soluble organic solvent solution of a PFA compound while stirring, PFA
Possible methods include dropping a solution of a compound and an emulsifier in a water-soluble organic solvent into water while stirring, or dropping water dropwise. In the treatment method of the present invention, a specific PFA compound is subjected to dry heat treatment in a state where it is present on the fibers, so that the specific PFA compounds are absorbed and fixed within the fibers. Such absorption fixing treatment can be carried out in a dyeing machine used for dry heat treatment in the dyeing process. In addition to the one-bath one-stage treatment using a bath containing a PFA compound and dye, the present invention can also be carried out by one-bath two-stage treatment or two-bath two-stage treatment. 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, dye bath and PFA
A two-bath two-stage process with separate compound-containing baths is also possible. This treatment allows the PFA compound and the dye to coexist on the fiber, and the treatment in this state allows both to be absorbed and fixed within the fiber. In the present invention, the fibers are treated with the PFA compound present on the fibers as described above. A relatively high heating temperature of 180 to 220° C. is adopted, but it is desirable to select a suitable temperature range depending on the type of fiber and the type of processing means. The method of the present invention is mainly applied to polyester fibers,
A temperature of 180 to 220°C, preferably about 200 to 220°C is employed. The heating temperature can be selected from the same range as the preferred range generally used for absorbing and fixing dyes into fibers. The amount of PFA compound absorbed and fixed into the fiber is 0.05 to 100 parts by weight of fiber.
5 parts by weight, preferably about 0.1 to 1.0 parts by weight. In the case of the dry heat treatment of the present invention, similarly to the thermosol dyeing method, the fibers are padded in a bath, then dried and then heated in a thermosol dyeing machine or the like. For polyester fibers, at temperatures of 180-220℃
Hold for 60 seconds to 120 seconds to allow it to be absorbed into the fibers. The absorption fixation method described above not only uses a PFA compound in combination with dyes for dyeing synthetic fibers, such as disperse dyes, acid dyes, cationic dyes, etc.
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 uses dry heat treatment, for example, 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. 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】

[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 using a household electric washing machine, using 55g of detergent (Blue Diamond: brand name), bath volume 20, 40℃,
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】

[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 (Holonrubin S-2GL: Sandoz Co., Ltd.)
Disperse dye) 1% owf Dyeing aid (Disper GS-57: Anionic emulsifier manufactured by Meisei Chemical Industry Co., Ltd.) 0.5g / Acetic acid (90%) 0.25cc / Bath ratio (1:20) Adjust the above dye liquor and make polyester The processed yarn knit was padded at a squeezing rate of 80% and then dried at 100°C for 3 minutes. This dyed material is dyed at 200℃ using a thermosol dyeing machine.
Processed for 60 seconds. After washing the dyed item with water, soaping it in a bath of 2g/Latsucol ST at 80℃ for 10 minutes,
It was washed with water, dried, and heat set at 180°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 2 to 5 and Comparative Example 1 The processing agent was prepared and the polyester 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. Further, 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 the third section below.
Shown in the table.

【table】

[Table] Comparative Example 2 In Example 1, when the treatment temperature was set to 150°C, both the initial water repellency and oil repellency of the resulting polyester fiber cloth were 0. Example 6

[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 polyester processed 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 7

[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 polyester processed yarn knit in the same manner as in Example 1. As a result, the water repellency was 90 and the oil repellency was 7, and the water repellency after washing 10 times was 80 and the oil repellency was 6.

Claims (1)

[Claims] 1. A polyfluoroalkyl group-containing triazine compound or urethane compound having a molecular weight of 400 to 2000 is absorbed and fixed to fibers by dry heat treatment at a temperature of 180 to 220°C. A method for making fibers water and oil repellent. 2 The polyfluoroalkyl group-containing triazine compound or urethane compound has the following general formula ()
The method according to claim 1, wherein the compound is a compound represented by (). 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, and Z ¹ and Z ² are a hydrogen atom or a monovalent organic group , Y is a divalent organic group, and n is an integer of 1 or more. 3 R _f is a perfluoroalkyl group represented by C _p F _2P+1 (where p is an integer of 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 No. 2. 4. The method according to claim 1, wherein the amount of the polyfluoroalkyl group-containing triazine compound or urethane compound absorbed and fixed into the fiber is 0.05 to 5 parts by weight per 100 parts by weight of the fiber.