JPH0260703B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel antifouling agent containing a specific polyfluoroalkyl group-containing compound as an active ingredient. Conventionally, polyfluoroalkyl group (hereinafter referred to as PFA
In the treatment of textile products such as woven fabrics and carpets with a processing agent having a group of has been adopted. but,
Since such polymer processing agents are discontinuous phases held on the fiber surface mainly by physical adhesion,
There is a tendency for fibers to fall off due to friction due to the mechanical action they receive during the process leading to the finished product or when used as a textile product. Also,
Polymer processing agents having a PFA group have difficulties in imparting antifouling properties such as dry soil resistance, which is particularly important in carpet treatments. 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 derivatives such as phthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid are used as processing agents. See US Pat. No. 3,646,153, US Pat. No. 3,870,748, US Pat. No. 4,209,610, etc. In addition, it is a substance useful as an antifouling agent for carpets, etc.
Various fluorine-containing urethane compounds having a PFA group are described, for example, in U.S. Pat.
It has been proposed in publications such as No. 53-112855 and No. 54-74000. According to the research of the present inventor, a relatively low molecular weight compound obtained by reacting a trifunctional isocyanate compound with a PFA group-containing alcohol etc. can smoothly and advantageously solve the problems of the above-mentioned polymer processing agents, and also It has been found that the friction durability is superior to low molecular weight fluorine compounds such as fluorine-containing urethane compounds. Such a specific compound has a molecular weight of about 800 to 3000, has at least three urethane bonds or urea bonds, and further contains at least one PFA group. and,
Such a specific compound containing a PFA group can be used before the dyeing process, and can also be advantageously used as a processing agent when spinning raw fibers for textile products such as carpets. That is, such a specific processing agent can be used to impart antifouling properties during spinning,
It does not fall off from textile products during dyeing, and has no adverse effect on dyeing. As a result of further studies on antifouling agents made of derivatives from trifunctional isocyanate compounds as described above, the present inventors have come to the following interesting findings. That is, n is added to a trifunctional isocyanate compound together with a PFA group-containing alcohol, etc.
−C ₁₈ H ₃₇ OH, n−C ₁₈ H ₃₇ NH ₂ , or n−
It was discovered that by reacting a combination of C ₁₈ H ₃₇ SH and the like, it is possible to obtain an antifouling agent with particularly excellent water repellency. Such a PFA group and a linear stearyl group (hereinafter referred to as C ₁₈ H ₃₇
A relatively low molecular weight compound containing at least one urethane bond, urea bond, or thiourethane bond and at least three urethane bonds, urea bonds, or thiourethane bonds has a high degree of water and oil repellency and stain resistance. It can be applied and has excellent friction durability. Thus, the present invention relates to the general formula The object of the present invention is to provide a novel antifouling agent containing a polyfluoroalkyl group-containing compound represented by the formula and having a molecular weight of 800 to 3,000 as an active ingredient. In the above general formula, R _f has 1 to 20 carbon atoms,
Preferably, it is a linear or branched polyfluoroalkyl group with 4 to 16 polyfluoroalkyl groups, and those whose terminal end is usually a perfluoroalkyl group are selected, but those containing a hydrogen atom or a chlorine atom at the terminal end. , or an oxyperfluoroalkylene-containing group can also be used. A preferred embodiment of R _f is -C _o
A perfluoroalkyl group represented by F _2o+1 (where n is an integer of 4 to 16), where n is 6 to 12
Particularly preferred are those. X is -R-,-CON
(R ¹ )-Q- or -SO ₂ N(R ¹ )-Q- (wherein, R is a divalent alkylene group, R ¹ is a hydrogen atom or a lower alkyl group, and Q is a divalent organic group) A divalent alkylene group having 1 to 10 carbon atoms, preferably represented by -C _n H _2n - (where m is an integer of 1 to 10), especially a divalent alkylene group having 2 to 4 carbon atoms. A divalent alkylene group is selected. Further, Q is a divalent organic group, and a divalent alkylene group -R- is usually exemplified as a suitable one. A, A ¹ and
A ² is -O-, -S- or -N(Z ³ )- (however,
Z ³ represents a hydrogen atom or a monovalent organic group), and in terms of availability, A is -O-,
A ¹ is -O- and A ² is -O- or -N(Z ³ )-
It is preferable that Z ² is a monovalent organic group, and may be the same as Z ³ above, or may be combined with Z ³ to form a ring. for example,
−A ² −Z ² is −OR′ (R′ is an alkyl group), −
_NHCH2OH , _{-NHCH2CH2OH ,}

【formula】

【formula】

【formula】

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

【formula】

【formula】

[Formula] -N (R') ₂ , -NH (R'), -N N (CH ₃ )
_{CH2CH2OH ,}

This can be exemplified as a suitable example such as [Formula]. It is important that Z ¹ is a linear stearyl group. In the case of branched or lower alkyl groups, the effect of the present invention, especially the effect of improving water repellency, is reduced, and the specific effect of such a linear stearyl group is surprising. be. In the PFA group-containing compound of the general formula, W is a trivalent organic group, a is an integer of 1 to 2, and b is an integer of 1 to 2. It is important that such a PFA group-containing compound has a molecular weight of about 800 to 3,000, preferably about 1,000 to 2,000. If the molecular weight is too high, the effect of antifouling treatment, which has excellent durability, will be slight, resulting in difficulties in use before the dyeing process or during spinning of raw yarn. In addition, compared to derivatives from bifunctional isocyanate compounds such as relatively low molecular weight fluorine-containing urethane compounds,
The trifunctional isocyanate compound derivative of the present invention has excellent durability. In the present invention, a PFA group-containing compound in which a+b is 3 is also suitable, but from the viewpoint of further improving durability through sufficient adhesion to the synthetic fiber surface, a+b is 2, and at least Those containing one -NHCO- ^A2 - ^Z2 group are preferred. And usually trifunctional isocyanate compounds

[Formula] is a fluorine-containing compound R _f -X-A-H and a stearyl group-containing compound
A PFA group-containing compound suitable for the _present invention can be synthesized by reacting _C18H37 - ^A1 -H with compound ^Z2 - ^A2 -H. The specific PFA group-containing compound of the present invention includes:
The following specific examples may be given. In the present invention, it is also possible to use an organic solution or an organic dispersion of a specific PFA group-containing compound, but in consideration of application to a dyeing process, etc., it is particularly suitable 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 a specific PFA group-containing compound. In addition, when dispersing a specific PFA group-containing compound in a medium mainly composed of water, the general formula R _f -X-A-CONH-Y-
It may be dispersed in the presence of a fluorine-based surfactant such as a urethane compound containing a hydrophilic group represented by NHCO-T. Here, R _f , X and A are as described above, Y is a divalent organic group, and T is a hydrophilic group. T is represented by -(CH ₂ CH ₂ O) _l -R ³ (where l is an integer from 1 to 50, and R ³ represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms). nonionic group, -(CH ₂ CH ₂ O) _l -SO ₃ M (where M represents one of 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 , R ⁶ are alkyl groups, aryl (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 such hydrophilic group-containing urethane compounds coexist, certain
Weight ratio of PFA group-containing compound/hydrophilic group-containing urethane compound is 99/1 to 25/75, preferably 95/5 to 50/50
The coexistence ratio is selected from the range. Examples of organic solvents used in combination when dispersing a specific PFA group-containing compound in water include dioxane, tetrahydrofuran, water-soluble ethers such as ethylpropyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monomethyl ether, and 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, triethylene glycol monoethyl Water-soluble glycol ethers such as ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, amides such as formamide, dimethylformamide, acetamide, acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diacetone alcohol, etc. Ketones, alcohols such as methanol, ethanol, propanol, butanol, methyl acetate, ethyl acetate,
Examples include esters such as propyl acetate and butyl acetate. The amount of such organic solvent added is usually 10 to 300 parts by weight, preferably 20 to 300 parts by weight, per 100 parts by weight of the specific PFA group-containing compound (if other PFA group-containing compounds are used together, the total amount with these). Selected from a range of 150 parts by weight. As is clear from the above specific examples, W is not particularly limited as long as it is a trivalent organic group. That is, W
(NCO) ₃ is an example of a trifunctional isocyanate compound, W can be exemplified over a wide range, such as. The trifunctional isocyanate compound W(NCO) ₃ is selected in consideration of availability, molecular weight as a specific PFA group-containing compound, etc. Moreover, as R _f -X-A-H in the above,
Usually, R _f -R-OH type fluorine-containing alcohol is preferably employed. It is also possible to produce a specific PFA group-containing compound in the form of a mixture by using a mixture of a plurality of fluorine-containing alcohols having different numbers of carbon atoms in R _f or R, etc. as a raw material. Furthermore, when Z ² -A ² -H is used, alcohols in which A ² is -O- or amines in which A ² is -N(Z ³ )- are particularly preferred in the present invention. It is a mode. As Z ² -A ² -H, from the viewpoint of imparting affinity with the surface of synthetic fibers, etc.

In addition to alcohols such as those represented by the formula, alkanolamines, diamines, or a combination of ammonia and a methylolating agent may also be used. And as C ₁₈ H ₃₇ −A ¹ −H,
C ₁₈ H ₃₇ OH, C ₁₈ H ₃₇ NH ₂ , C ₁₈ H ₃₇ SH, or
An example is C ₁₈ H ₃₇ NHZ ³ . In the present invention, when a specific PFA group-containing compound is dispersed in a medium mainly composed of water and used in the form of an aqueous dispersion, various methods can be employed as the dispersion means. For example, a method in which a mixture of a PFA group-containing compound, an emulsifier (surfactant), and an aqueous medium is stirred at high speed while heating and then cooled to room temperature;
A method in which an organic solvent solution of a PFA group-containing compound (with an emulsifier added in some cases) is dropped into an aqueous emulsifier solution while stirring, or an aqueous solution of an emulsifier is dropped into an organic solvent solution of a PFA group-containing compound while stirring. Possible methods include dropping an organic solvent solution of a PFA group-containing compound and an emulsifier into water with stirring, or dropping water dropwise. When the antifouling agent of the present invention is made into an aqueous dispersion, the solid content concentration is not particularly limited, but is usually 5.
It is adjusted to 60% by weight, preferably 15 to 50% by weight, and used in processing after being diluted with water to about 0.1 to 4% by weight. and,
Such aqueous dispersion type antifouling agents have advantages over organic solvent type agents, such as a higher flash point of the stock solution and the ability to increase the solid content concentration.
Furthermore, it has various advantages such as being able to minimize pollution of the working environment during processing. The antifouling agent of the present invention can be applied to various articles made of polyamide, polyester, leather, wood, etc.
For example, it can be advantageously applied not only to interior products such as carpets, reception sets, curtains, wallpaper, and vehicle interior items, but also to outdoor tents. 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. For example, known coating methods such as dipping, spraying, and coating may It can be applied by methods such as attaching it to the surface of the object to be treated or drying it by absorbing it. In addition, during construction, antistatic agents, insect repellents, flame retardants, dye stabilizers,
It is also possible to use various treatment agents such as anti-wrinkle agents, additives, etc. The antifouling agent of the present invention as described above has the following advantages. It has excellent water repellency, can impart high performance to fibers for processing during spinning, has good stain resistance, and has high friction durability. Furthermore, it has high compatibility with spinning oil, making it highly stable especially in the case of an aqueous dispersion type, and the processing agent does not fall off during dyeing.
Satisfactory dyeing is possible. 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 in weight percent or parts by weight, unless otherwise specified. In addition, in the following examples and comparative examples, oil repellency and oil repellency were measured as follows. That is,
Water repellency is expressed by placing a few drops of an isopropanol aqueous solution with the composition shown in Table 1 below on the sample cloth, and is expressed as the highest concentration point at which the solution is retained without penetrating into the cloth, and oil repellency is expressed by the following. Place several drops (approximately 4 mm in diameter) of the test solution shown in Table 2 on two places on the sample cloth, and judge by the state of penetration after 30 seconds (AATCC
−TM118−1966).

【table】

[Table] Stain resistance was determined by cutting the sample cloth into 5 x 7 cm pieces and applying the dry stains shown in Table 3 below (twice the weight of the sample).
and the sample in a container, and mix and stir vigorously for 3 minutes to contaminate. After contamination, excess dirt was removed using a vacuum cleaner, and the reflectance was measured to determine and evaluate the degree of contamination. The degree of contamination is calculated using the following formula. Degree of contamination (%) = R ₀ - R / R ₀ × 100 (R ₀ : Reflectance of uncontaminated cloth R: Reflectance of contaminated cloth)

[Table] Synthesis Example 1 Polyisocyanate was placed in a four-neck flask with an internal volume of 500 c.c., equipped with a dropping funnel with a uniform tube, a thermometer, a cooling tube, and a vacuum stirrer, and set on an oil bath. 95.6 g (0.2 mol) of dibutyltin dilaurate (C ₄ H ₁₀ ) ₂ Sn (OCOC ₁₂ H ₂₅ ) ₂ , dioxane
Pour in 100g and start stirring. After replacing the air in the system with dry nitrogen, raise the liquid temperature to 80°C and maintain it. By continuously feeding a small amount of dry nitrogen gas into the system from the top of the dropping funnel through the pressure equalization pipe, C _o F _2o+1 is maintained while maintaining a nitrogen atmosphere inside the system.
205.6 g (0.4 mol) of CH ₂ CH ₂ OH (n is a mixture of 6, 8, 10, and 12 with an average value of 9.0) was added dropwise from the dropping funnel over 2 hours. After the addition was completed, stirring was continued for 30 minutes, and then the reaction temperature was lowered to 60° C., and 54.0 g (0.2 mol) of stearyl alcohol n-C ₁₈ H ₃₇ OH was poured from the dropping funnel and stirring was continued for 1 hour. The reaction rate is
It was 100%. The above reaction mixture can be used as it is in the next emulsification step. The solvent dioxane was distilled off under reduced pressure from this reaction mixture. 350 g of yellow solid was obtained. From the infrared absorption spectrum and C ₁₃ NMR analysis, the main product was It was hot. Synthesis Example 2 R _f compound of Synthesis Example 1 10 parts Butyl acetate 15 parts PBC-44 (nonionic emulsifier manufactured by Nikko Chemical Co., Ltd.) 2 parts ween80 (nonionic emulsifier manufactured by Kao Atlas Co., Ltd.) 2 parts Furmin DMC (manufactured by Kao Soap Co., Ltd.) Cationic emulsifier) 1 part Water (deionized water) 70 parts The above mixture was pre-emulsified by stirring at 80°C for 30 minutes at 1000 rpm, then using a homogenizer.
Emulsification was carried out at 60°C for 30 minutes to prepare a processing agent consisting of an aqueous latex. Example 1 After diluting the aqueous latex of Synthesis Example 2 with deionized water to a solid content of 0.5% by weight, a nylon knit cloth was immersed in the emulsion for 2 seconds, and then placed between two rubber rollers. I squeezed the cloth to get a wet pick up of 90%. 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 4 below. Next, the following dye solution was poured into 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. 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 dispersant manufactured by Meisei Chemical Co., Ltd.) 1% owf 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 4 below. Examples 2 to 7 The R _f compounds shown in Table 4 below, which were synthesized in the same manner as in Synthesis Example 1, were made into aqueous dispersions in the same manner as in Synthesis Example 2. The measurement results of water and oil repellency and antifouling performance are shown in Table 4 below. Comparative Examples 1-2 Regarding R _f compounds derived from the bifunctional isocyanate compounds shown in Table 4 below, Examples 1-2
The performance was measured in the same manner as in Example 7, and the results are shown in Table 4 below.

【table】

【table】

[Table] In Table 4, R _f indicates C _o F _2o+1 (where n is a mixture of 6, 8, 10, and 12, with an average value of 9.0). Table 5 shows the appearance and melting point (° C.) of the R _f compounds of Examples 1 to 7 shown in Table 4.

【table】

【table】

Claims (1)

[Claims] 1. General formula An antifouling agent containing a polyfluoroalkyl group-containing compound represented by the formula and having a molecular weight of 800 to 3,000 as an active ingredient. However, in the above general formula, R _f has 1 to 1 carbon atoms.
20 polyfluoroalkyl groups, and X is -
C _n H _2n - (where m is an integer from 1 to 10), and A, A ¹ and A ² are each -O-, -S- or -N
(Z ³ ) - (However, Z ³ represents a hydrogen atom or an alkyl group)
Z ¹ is a linear stearyl group,
Z ² is an alkyl group or a lower substituted alkyl group,
W is three - from a trifunctional isocyanate compound
It is a trivalent organic residue from which the NCO group has been removed, a is an integer of 1 to 2, and b is an integer of 1 to 2. 2 R _f is a perfluoroalkyl group represented by C _o F _2o+1 (where n is an integer of 4 to 16), and X is
C _n H _2n , A is -O-, A' is -O- or -S-,
A ² is one of -O- or -N(Z ³ )- (where Z ³ represents a hydrogen atom or an alkyl group), Z ² is an alkyl group or a lower substituted alkyl group, and W is a trifunctional isocyanate Claim 1 is a trivalent organic residue obtained by removing three -NCO groups from a compound, a is an integer of 1 to 2, and b is an integer of 1 to 2.
Antifouling agent as described in section. 3 a is 1, b is 1, -A ² -Z ² is [Formula] -OR' (however, R' is an alkyl group), -OCH ₂ CH ₂ CN, -OCH ₂ CH ₂ NO ₂ , -
OCH ₂ CH ₂ OH, −NHCH ₂ OH, −
NHCH ₂ CH ₂ OH, [Formula] -NHR' (however, R' is the same as above), -NR'R' (however, R' is the same as above), -N(CH ₂ CH ₂ OH) ₂ or The antifouling agent according to claim 2, which is the formula: