JPS6137386B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a water- and oil-repellent fiber and a method for producing the same. More specifically, the present invention relates to a fiber with significantly improved durability and water and oil repellency, and a method for producing the same. Recently, there has been a demand for water-repellent fibers and textile products in the sports and leisure fields, and in the carpet field, in order to prevent stains, in addition to water repellency, oil repellency and stain prevention properties are required. The demand for certain things is becoming higher. Silicon-based compounds and fluorine-based compounds have conventionally been known as water- and oil-repellent finishing agents for fibers, and among them, fluorine-based compounds exhibit excellent effects in both water and oil repellency. However, this water and oil repellency is easily lost by washing, and the current situation is that a sufficient effect cannot be sustained over the period of use of the textile product. Additionally, recently there has been a demand for water and oil repellency that is even more advanced than before, and even though fluorine-based compounds are highly effective, they cannot fully meet the demands of all fields. It's not a thing. In view of the above-mentioned current situation, the present inventors aimed to make the water and oil repellency by a fluorine-based compound permanent to a practically sufficient degree, and to provide a higher level of water and oil repellency. The present invention was completed as a result of intensive research. That is, the gist of the present invention is as follows. Water- and oil-repellent fibers formed by attaching higher fatty acid amides and fluorine-based compounds to cross-linked polyalkylene polyamines, and reactions in which compounds obtained by dehydration condensation of polyalkylene polyamines and higher fatty acids are polymerized using a cross-linking agent. A method for producing water- and oil-repellent fibers, which comprises treating the fibers with a product, then treating them with a fluorine-based compound, drying them, and further heat-treating them at 70 to 200°C. The present invention relates to a reaction product (hereinafter simply referred to as compound A) obtained by polymerizing a compound obtained by dehydration condensation of a polyalkylene polyamine and a higher fatty acid using a crosslinking agent.
This is a durable fiber characterized by having a fluorine-based compound attached to the fiber, and also has a high degree of water and oil repellency, and a method for producing the same. According to the present invention, the adhesion of the fluorine-based compound to the fibers is extremely strong and can sufficiently withstand normal washing or dry cleaning. Therefore, it is possible to impart practically sufficient durable water and oil repellency to the fibers. The present invention will be explained in detail below. Compound A used in the present invention is a compound obtained by dehydrating and condensing a polyalkylene polyamine and a higher fatty acid and polymerizing it using a crosslinking agent. By using this compound in combination with a fluorine-based compound to adhere to fibers, the adhesion of the fluorine-based compound to the fibers can be made much stronger compared to when the fluorine-based compound is used alone. . What is even more surprising is that by using the above compound A, water and oil repellency is superior to when a fluorine-based compound is attached alone to the fibers. Although it is not yet clear why the above-mentioned unique effect is produced by using Compound A, it is believed that the interaction between Compound A and the fluorine-based compound causes both compounds to firmly adhere to the fibers. at the same time,
It is presumed that this is because there are few adhesion spots and the adhesion is uniform. In the present invention, the above-mentioned fibers refer to natural, semi-synthetic or synthetic fibers, including raw cotton, spun yarn, fabrics, knitted fabrics, non-woven fabrics, and fibers for various clothing, industrial products, etc. made from these fibers. It means a product. Specific examples of these fibers include natural fibers such as cotton, linen, and wool, semi-synthetic fibers such as rayon, acetate, and Bemberg, polyester, nylon,
Acrylic, vinyl chloride, vinylidene chloride,
Examples include polyolefin-based and polyvinyl alcohol-based synthetic fibers. In the present invention, the polyalkylene polyamine constituting the compound A, which exhibits specific effects when used in combination with a fluorine-based compound, has the general formula H ₂ N [-(CH ₂ )- _o NH]- _n H ( n is an integer of 1 to 3, m is an integer of 2 to 9), and specific examples include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine,
Nonaethylenedecamine, 1,3-bis(2'-aminoethylamino)propane, triethylene-bis(trimethylene)hexamine, bis-3(aminoethyl)amine, 1,3-bis(3'-aminopropylamino) ) Propane, etc. These polyalkylene polyamines may be used alone or in combination. Next, the higher fatty acids constituting Compound A include saturated fatty acids or lower unsaturated fatty acids having 16 or more carbon atoms, and specific examples of these compounds include palmitic acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid. , cetylonic acid, montanic acid, melisic acid, zomaric acid, oleic acid, linoleic acid, cadoic acid, and cetrenic acid. Among these higher fatty acids, compounds with 18 to 22 carbon atoms have excellent durability due to the synergistic effect of Compound A and fluorine-based compounds, and also exhibit a high degree of water and oil repellency. This is a particularly preferred compound for providing Compound A. These fatty acids can be reacted alone or in a mixture with the polyalkylene polyamine. When the compound A of the present invention is obtained by dehydration condensation of a polyalkylene polyamine and a higher fatty acid, when the polyalkylene polyamine is a compound represented by the above general formula, the higher fatty acid is m- 2 to m mol (m
is 3 or more) or 0.5 to 2 mol (when m is 2). In the case of other polyalkylene polyamines, it is also preferable to carry out the reaction under conditions in which 1 to 3 amino groups and imino groups remain in the compound obtained by dehydration condensation of a polyalkylene polyamine and a higher fatty acid. When the number of reactive moles of the higher fatty acid is less than m-2 or 0.5, the water and oil repellency of the obtained compound A when used in combination with a fluorine-based compound is not significantly improved, nor is its permanence improved.
Moreover, if the higher fatty acid is larger than mmol or 2 moles, the reaction between the obtained compound and the crosslinking agent described below will not proceed sufficiently, and the water and oil repellency effect and the durability of the obtained compound A will not be sufficiently improved. The above-mentioned dehydrated condensate of polyalkylene polyamine and higher fatty acid is further polymerized using a crosslinking agent described below to become Compound A which exhibits the above-mentioned specific effects. This crosslinking agent is a compound included in each group of the following general formulas (1) to (4). That is, the crosslinking agent of the present invention has the following properties: (1) R ₁ (-NCO)- _e (R ₁ is an organic residue, e is an integer of 2 to 3) (2) R ₂ (-COOH) _k (R ₂ is an organic residue, k is an integer from 2 to 3) (3) R ₈ (-COCl) _j (R ₈ is an organic residue, j is an integer from 2 to 3) (4)

It is a compound represented by the formula: (R ₄ is an organic residue, i is an integer of 2 to 3). Examples of the crosslinking agent represented by general formula (1) include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate,
Hexamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, 1,3-phenylene diisocyanate,
1,4-phenylene diisocyanate, toluylene diisocyanate, naphthalene diisocyanate, 4,4'-diphenylmethane isocyanate,
These are 1-methylbenzole 2,4,6-triisocyanate, biphenyl 2,4,6-triisocyanate, and biphenyl 2,4,4'-triisocyanate. Examples of the crosslinking agent represented by the general formula (2) include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, and terephthalic acid. be able to. The crosslinking agent also represented by general formula (3) is a compound obtained by chlorinating the carboxyl group of the compound represented by general formula (2) above. Next, the compounds represented by the general formula (4) include butadiene oxide, diglycide ether, glycerin bisglycide ether, butanediol bisglycide ether, (R ₄ ′ is

[Formula] or aromatic acid of divalent phenol). As these crosslinking agents, polyisocyanate compounds represented by the general formula (1) are preferred because of crosslinking reaction and easy availability. In order to further improve the water and oil repellency effect by using it in combination with a fluorine-based compound, which is the object of the present invention, and to make it permanent, the above-mentioned crosslinking agent is added in a range of 0.5 to 1.5 mol. , it is preferable to react with a dehydrated condensate of the polyalkylene polyamine and higher fatty acid. If the number of moles of the crosslinking agent reacted with respect to 1 mole of the dehydrated condensate of polyalkylene polyamine and higher fatty acid is less than 0.5, the effects of the present invention will not be sufficiently obtained, and if it is greater than 1.5 moles, Compound A will be highly This is undesirable because it becomes three-dimensional and interferes with adhesion to fibers. Next, the fluorine-based compounds that impart water and oil repellency to fibers are known compounds conventionally known as water and oil repellents, such as compounds having fluorinated fatty acids in their side chains, fluorinated vinyl , vinylidene fluoride alone or as a copolymer, and is also a commonly known commercially available water and oil repellent. These fluorine-based compounds have conventionally been known as substances that can impart water and oil repellency to fibers either alone or in combination with other compounds, but according to the present invention, the above-mentioned specific By using Compound A in combination with this fluorine-based compound, it is possible to further improve the effect and durability of the effect, and it is possible to improve the durability of the effect, which is sufficient for practical use. It is possible to obtain fibers having the following properties. The manner in which Compound A and the fluorine-based compound are attached to the fibers is not particularly limited; Any of the embodiments may be used, such as an embodiment in which a mixture of the fluorine-based compounds is attached to the fibers, or an embodiment in which the fluorine-based compounds are attached to the fibers, and then the compound A is attached to the fibers. However, when considering the difficulty of processing in the process of attaching these compounds and the process of finishing the fibers to which these compounds are attached, it is difficult to apply a method in which compound A is attached and then a fluorine-based compound is attached. preferable. The amount of Compound A attached and the amount of fluorine-based compound attached to the fibers vary depending on the desired degree of water and oil repellency and its durability, but usually Compound A
is 0.01 to 10% (by weight, the same applies below), preferably 0.1
~3%, and fluorine compounds from 0.01 to 20%, preferably from 0.1 to 5%. If the amount of adhesion is small, water and oil repellency will not be sufficient and durability will also be lacking. On the other hand, although it is possible to deposit these in an amount exceeding the above-mentioned upper limit, the water and oil repellency is not improved in proportion to the amount of deposition, and on the contrary, unpleasant sensations such as stickiness occur. Next, the method for producing the fiber of the present invention will be described. In the present invention, when compound A and a fluorine-based compound are attached to fibers, either one of the compounds is attached first, and then the other compound is attached, or
Alternatively, these compounds can be deposited simultaneously. The attachment method can be appropriately determined depending on the form of the fibers and the difficulty of the attachment process, but a method of attaching the fluorine-based compound after attaching the compound A is preferred because the process is easy. Compound A is attached to the fibers by spraying a solution or dispersion of compound A or by immersing the fibers in the solution. A solution or dispersion of Compound A using water as a medium is easy to handle. In this case, when Compound A is poorly soluble, it is preferable to use it as an aqueous dispersion using an emulsifying dispersant or an organic or inorganic acid such as acetic acid, lactic acid, hydrochloric acid, sulfuric acid, phosphoric acid, etc. The concentration of compound A is 0.05-5
%, and the amount of auxiliary agents such as emulsifiers is usually 1 to 20% based on Compound A. After adjusting the amount of Compound A attached to the fibers to be 0.01 to 10%, the fibers are dried, and then, if necessary, further heat treated at 80 to 180°C. Next, a water and oil repellent made of a fluorine-based compound is applied to the fibers to which Compound A has been applied.
In this case, a silicone-based water repellent may also be used. The water and oil repellent agent made of a fluorine-based compound is not particularly limited, and as mentioned above, conventionally known compounds can be used, such as Ribasol, which is commercially available.
KF311A (fluorine-based water and oil repellent manufactured by Tokai Oil Industries Co., Ltd.: product name), TS Card T317 (product name), Asahi Guard AG-710, 730, 800 (manufactured by Meisei Chemical Industry Co., Ltd.) Fluorine-based water and oil repellent: Product name), Geranex F-2 (Matsumoto Yushi Pharmaceutical Co., Ltd. Fluorine-based water and oil repellent: Product name) NK Guard FP-100 (Nicca Chemical Industry Co., Ltd.)
One example is Fluorinated water and oil repellent (trade name) manufactured by Co., Ltd. As the silicone water repellent, known compounds can be used, such as organopolysiloxane, amino-modified siloxane, and epoxy-modified siloxane. These fluorine-based compounds are attached by spraying onto the fibers as an aqueous dispersion or a solvent dissolved in an organic solvent, or by immersing the fibers in the solution. The amount of the fluorine-based compound attached is usually 0.01 to 20% based on the fiber, and the concentration of the fluorine-based compound in the dispersion or solution and the amount of impregnation of the liquid into the fiber are adjusted to fall within this range. do. Next, the fibers to which the fluorine-based compound has been attached are dried and further subjected to heat treatment. Drying is performed at room temperature to 180°C, preferably 60 to 130°C using hot air, heated rollers, etc., and heat treatment is performed at 80 to 180°C, preferably 90 to 140°C.
C. for 1 minute or more, preferably 5 minutes to 15 minutes. The thus obtained fibers to which Compound A and the fluorine-based compound are attached are more durable than when the fluorine-based compound is attached alone, or when they are combined with known auxiliary agents for improving durability. The quality will be improved to the next level. The present invention will be explained below with reference to Examples. Example 1 103 g (1 mol) of diethylene triamine and 512 g (2 mol) of palmitic acid were reacted at 150°C under a nitrogen atmosphere, and 134 g (0.8 mol) of hexamethylene diisocyanate was gradually added to the reaction product at 60°C, and then The reaction was carried out at 120°C for 2 hours. 4 parts by weight of acetic acid was added to 100 parts by weight of the obtained reaction product (compound A) to emulsify it to produce an emulsion containing 1% of compound A. Acrylic fibers (copolymer fibers consisting of 95% acrylonitrile, 4.6% methyl acrylate, and 0.4% sodium allylsulfonate) are immersed in this dispersion, squeezed between rollers, and dried in hot air at 95°C. A fiber to which 0.6% of Compound A was attached was obtained. Next, this fiber was heat treated in hot air at 130°C for 30 minutes. This fiber was impregnated with an emulsion aqueous solution containing 0.5% Asahi Guard AG-730 (fluorine compound manufactured by Meisei Chemical Co., Ltd.: trade name) and dried in hot air at 95°C to obtain fibers with 3% fluorine compound attached. , and then further treated in hot air at 110°C for 10 minutes. The fibers obtained in this way are processed into knitted fabrics,
I checked the water repellency. The initial water repellency was 100, and the water repellency after 10 washes was 90. On the other hand, fibers treated in the same manner as above except that Compound A was not attached had an initial water repellency of 90 and a water repellency of 50 or less after 10 washes. The water repellency was measured by the spray method in accordance with JIS L1092, and the washing method was carried out by the tumble drying method in accordance with JIS L217-103. Example 2 1 mole of pentaethylenehexamine, pehenic acid
The product obtained by reacting 4.5 mol and 1 mol of hexamethylene diisocyanate in the same manner as in Example 1.
3.5 parts by weight of acetic acid was added to 100 parts by weight and emulsified to obtain an emulsion containing 1.5% of compound A. This emulsion is mixed into acrylic fiber (undried yarn produced by a wet spinning method using a copolymer of 91% acrylonitrile, 8.5% methyl acrylate, and 0.5% sodium methallylsulfonate using nitric acid as a solvent).
Compound A is attached to the surface and dried in hot air at 95℃, and
A fiber with 0.45% adhesion was obtained. The fibers were treated in hot air at 125°C for 30 minutes, then Ribasol KF
-311A (fluorinated water and oil repellent manufactured by Tokai Seishin Kogyo Co., Ltd.: trade name), then dried in hot air at 98°C, and further heat-treated in hot air at 108°C. The resulting fibers had 4.5% fluorine resin attached to them. The initial water repellency of the knitted fabric made of this fiber is 100,
The water repellency after 10 washes was 90. For comparison,
Fibers obtained in exactly the same manner except that Compound A was not attached had a weight of 100 and 50 or less. Example 3 The acrylic fibers to which Compound A was attached, produced in Examples 1 and 2, were processed into a knitted fabric, and TS Guard
K317 (fluorine-based water and oil repellent manufactured by Tokai Seishin Kogyo Co., Ltd.):
(trade name), dried, and then treated in hot air at 110°C for 30 minutes. The resulting fibers had 5% fluorine resin attached to them. Sports shirts were manufactured using these knitted fabrics and a wear test was conducted. The wear test was carried out by washing the fabric normally at home after wearing it for one week, repeating this process 10 times, and comparing the degree of water repellency with the knitted fabric according to Example 1. As a result, no difference was observed in both the initial water repellency and the water repellency after being worn 10 times compared to Example 1. Example 4 The emulsion of Compound A produced in Example 2 was applied to a polo shirt made of 65% polyester and 35% cotton, dried to adhere 0.55% of Compound A, and then heated in hot air at 135°C. Treated for 30 minutes. Next, this polo shirt is Rivasol KF-311A
(Tokai Seishin Kogyo Co., Ltd. fluorine-based water and oil repellent: trade name) to adhere 5.5% fluorine-based resin.
Dry in hot air at 95℃, then dry in hot air at 115℃ for 50 minutes.
Processed for minutes. Example 3 The polo shirt obtained by this treatment was
When the same wearing test was conducted, the water repellency at the initial stage and after wearing was both 100 and 90, indicating excellent durability. Example 5 0.5 cc of edible oil (salad oil) was applied to the knitted fabric produced in Example 2, and after 30 minutes, it was washed at home and dried. This test was repeated 10 times. For comparison, the same test as above was conducted on the knitted fabric of the comparative example of Example 2. As a result, no oil stains were observed on the knitted fabric of the present invention after washing, but oil stains remained as stains on the comparative fabric.

Claims (1)

[Scope of Claims] 1. A water- and oil-repellent fiber made of a cross-linked polyalkylene polyamine to which a higher fatty acid amide and a fluorine-based compound are attached. 2 The polyalkylene polyamine has the general formula H ₂ N [-(CH ₂ )- _o NH]- _n H (n is an integer from 1 to 3,
m is an integer of 2 to 9), the higher fatty acid has 16 or more carbon atoms, and the crosslinking agent is one of the following (1) to
(4) The water- and oil-repellent fiber according to claim 1, which is at least one compound selected from (1) R ₁ (-NCO) _-e (R ₁ is an organic residue, e is 2 or (integer of 3) (2) R ₁ (−COOH) _k (R ₂ is an organic residue, k is an integer of 2 or 3) (3) R ₃ (−COCl) _j (R ₃ is an organic residue, j is an integer of 2 or 3) (Integer of 2 or 3) (4) [Formula] (R ₄ is an organic residue, i is an integer of 2 or 3) 3 A compound obtained by dehydration condensation of a polyalkylene polyamine and a higher fatty acid is highly The fibers are treated with the molecularized reaction product, then treated with a fluorine-based compound, dried, and further
A method for producing water- and oil-repellent fibers characterized by heat treatment at °C.