JPS6127517B2 - - 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. In addition, water and oil repellency has recently become required to be more advanced than ever. In view of the above-mentioned current situation, the inventors of the present invention aimed to make the water and oil repellency by a silicone-based water repellent agent 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. A water- and oil-repellent fiber made by attaching a higher fatty acid amide and a silicone-based water repellent to a crosslinked polyalkylene polyamine, and a compound obtained by dehydration condensation of a polyalkylene polyamine and a higher fatty acid are polymerized using a cross-linking agent. A method for producing water- and oil-repellent fibers, which comprises treating the fibers with a reaction product, followed by treatment with a silicone-based water repellent, drying, and further heat-treating 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 with a high degree of water and oil repellency, characterized by having a silicone water repellent attached to the fiber, and a method for producing the same. According to the present invention, the adhesion of the silicone water repellent 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 silicone-based water repellent to adhere to the fibers, the adhesion of the silicone-based water repellent to the fibers becomes much stronger than when the silicone-based water repellent is used alone. be able to. What is even more surprising is that the use of Compound A provides superior water and oil repellency compared to when a silicone-based water repellent is applied alone to the fibers. The reason why the above-mentioned unique effect is produced by using Compound A is not clear, but the interaction between Compound A and the silicone-based water repellent causes both compounds to firmly adhere to the fibers. It is presumed that this is because there are few spots of adhesion and the adhesion is uniform. In the present invention, the above-mentioned fiber means natural, semi-synthetic or synthetic fiber, and also includes raw cotton, spun yarn, fabric, knitted fabric, non-woven fabric, and various clothing, industrial goods, etc. made of these. It means textile products. 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, and vinylidene chloride. , polyolefin-based, and polyvinyl alcohol-based synthetic fibers. In the present invention, the polyalkylene polyamine constituting Compound A, which exhibits specific effects when used in combination with a silicone water repellent, has the general formula H ₂ N [-(CH ₂ )- _o NH]- _n H (n is 1 to 3
m is an integer of 2 to 9), specific examples include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, nonaethylenedecamine, 1,3- Bis (2′−
aminoethylamino)propane, triethylene-
Examples include bis(trimethylene)hexamine, bis-3(aminoethyl)amine, and 1,3-bis(3'-aminopropylamino)propane. These polyalkylene polyamines may be used alone or in combination. Next, compound A
The higher fatty acids that make up include saturated fatty acids with 16 or more carbon atoms or slow unsaturated fatty acids,
Specific compounds include palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melisic acid,
These include zomarinic acid, oleic acid, linoleic acid, gadolenic acid, and cetolenic acid. Among these higher fatty acids, compounds with 18 to 22 carbon atoms have excellent long-lasting and highly water- and oil-repellent effects due to the synergistic effect of Compound A and silicone water repellent. This is a particularly preferred compound for providing compound A that expresses 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 repellent effect of the obtained compound A when used in combination with a silicone water repellent is not significantly improved, nor is its permanence improved. In addition, 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, resulting in the obtained compound A.
The water and oil repellency effect and its durability are not 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 2 to 3
) (2) R ₂ (−COOH) _k (R ₂ is an organic residue, k is an integer from 2 to
(3) R ₃ (-COOl) _j (R ₃ is an organic residue, j is 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 diisocyanate, 1-methylbenzole 2,4,6-triisocyanate, biphenyl 2,4,6-triisocyanate, 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 the general formula 3 is a compound obtained by chlorinating the carboxyl group of the compound represented by the above general formula (2). 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 the aromatic ring 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 the silicone water repellent in combination with the silicone water repellent, which is the object of the present invention, and to make it permanent, the 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 silicone-based water repellent that imparts water and oil repellency to fibers is a well-known compound that has been conventionally known as a water and oil repellent. Alternatively, these are amino-modified polysiloxanes and epoxy-modified polysiloxanes in which amino groups, epoxy groups, etc. are introduced into these compounds. These silicone-based water repellents have conventionally been known as substances that can impart water and oil repellency to fibers either alone or in combination with other compounds. Compound A
By using this together with this silicone water repellent,
It is possible to further improve the action and effect, and at the same time, to further improve the durability of the action and effect, and it is possible to obtain a fiber that has sufficient durability for practical use. The mode of adhesion of Compound A and the silicone water repellent to the fibers is not particularly limited, but
A mode in which Compound A is attached to the fiber and then a silicone water repellent is attached, a mode in which a mixture of Compound A and a silicone water repellent is attached, or a mode in which a silicone water repellent is attached to the fiber and then Any mode may be used, such as a mode in which Compound A is attached to the surface of the substrate. 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 have been attached into products, an embodiment in which Compound A is attached and then a silicone-based water repellent is attached. is preferred. The amount of Compound A attached and the amount of silicone water repellent 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, below). similar), preferably
0.1 to 3%, silicone water repellent 0.01 to 20%, preferably 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 silicone water repellent are attached to fibers, either one of the compounds can be attached first and then the other compound can be attached, or these compounds can be attached at the same time. . 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 silicone water repellent 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 silicone-based water repellent is applied to the fibers to which Compound A has been applied. Water and oil repellents made of silicone-based water repellents are not particularly limited, and as mentioned above, conventionally known compounds can be used, such as DICSILICONE CONC V (Dainippon Ink Silicone water repellent manufactured by Kagaku Kogyo Co., Ltd. (product name),
POLON NWS (silicon water repellent manufactured by Shin-Etsu Chemical Co., Ltd.: product name), POLON MR (same as above, product name),
NR-100 (silicon water repellent manufactured by Takamatsu Yushi Co., Ltd.: trade name), MY-Silicone A-30 (silicon water repellent manufactured by Yoshimura Yukagaku Co., Ltd. trade name), FZ-350, FZ-
343 and LE-9300 (silicon water repellent manufactured by Nippon Unicar Co., Ltd.: trade name). These silicone-based water repellents are applied by spraying onto the fibers as an aqueous dispersion or a solution dissolved in an organic solvent, or by immersing the fibers in the solution. The amount of silicone water repellent applied is usually 0.01 to 20% of the fibers, and the concentration of the silicone water repellent in the dispersion or solution and the amount of the liquid impregnated on the fibers are adjusted to fall within this range. Prepare. Next, the fibers coated with the silicone water repellent are dried and further heat treated. Drying is performed at room temperature to 180°C, preferably with hot air at 60 to 130°C, heated rollers, etc., and heat treatment is performed at 70 to 200°C, preferably 90 to 140°C.
for at least 1 minute, preferably 5 to 15 minutes. The thus obtained fibers to which Compound A and the silicone water repellent are attached are better than those to which only the silicone water repellent is attached, or when they are combined with a known auxiliary agent for improving durability. The durability has also been further improved. 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. DICSILICONE CONC V (silicon water repellent manufactured by Dainippon Ink Chemical Co., Ltd.: trade name) 3 is applied to this fiber.
% emulsion aqueous solution and dried in hot air at 95°C to obtain fibers with 3% silicone water repellent attached, and then further treated in hot air at 115°C for 15 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 80. 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 L0217-103. Example 2 1 mol of pentaethylenehexamine, behenic acid
The product obtained by reacting 4.5 mol and 1 mol of hexamethylene diisocyanate in the same manner as in Example 1.
100 parts by weight was emulsified by adding 3.5 parts by weight of acetic acid to obtain an emulsion containing 1.5% of Compound A. This emulsion is attached to acrylic fibers (undried yarn manufactured by wet spinning method using nitric acid as a solvent, using a copolymer consisting of 91% acrylonitrile, 8.5% methyl acrylate, and 0.5% sodium methallylsulfonate). Compound A was dried in hot air at 95°C.
A fiber with 0.45% adhesion was obtained. This fiber was treated in hot air at 125℃ for 30 minutes, and then POLON MWS
(Silicone-based water repellent manufactured by Shin-Etsu Chemical Co., Ltd.: Product name)
, then dried in hot air at 98℃, and then
Heat treatment was performed in hot air at 110°C. 4% silicone water repellent was attached to the obtained fibers. The initial water repellency of a knitted fabric made of this fiber was 100, and the water repellency after 10 washes was 80. For comparison, fibers obtained in exactly the same manner except that Compound A was not attached were also 90 and 50 or less. Example 3 The acrylic fiber to which Compound A was attached, produced in Examples 1 and 2, was processed into a knitted fabric, treated with NR-100 (silicon-based water repellent manufactured by Takamatsu Yushi Co., Ltd.: trade name), After drying, it was treated in hot air at 115°C for 30 minutes. The resulting fibers were coated with 5% silicone water repellent. 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, make this polo shirt MY-Silicone A-30
(Product name of silicone water repellent manufactured by Yoshimura Yukagaku Co., Ltd.) to adhere 5% silicone water repellent and 95℃
It was dried in hot air at 125°C and further treated in hot air at 125°C for 50 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 80, 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, the knitted fabric of the present invention showed almost no oil stains after washing, but the comparative fabric showed almost no oil stains after washing.
Oil stains remained as stains.

Claims (1)

[Claims] 1. A water- and oil-repellent fiber made of a cross-linked polyalkylene polyamine to which a higher fatty acid amide and a silicone-based water repellent are attached. 2 Polyalkylene polyamine is a compound represented by 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), carbon number of higher fatty acid is 16 or more, and the crosslinking agent is as follows.
The water- and oil-repellent fiber according to claim 1, which is one or more compounds selected from (1) to (4). (1) R ₁ (−NCO) − _e (R ₁ is an organic residue, e is an integer of 2 or 3) (2) R ₂ (−COOH) − _k (R ₂ is an organic residue, k is 2 or (3) R ₃ (−COOl) − _j (R ₃ is an organic residue, j is an integer of 2 or 3) (4) [Formula] (R ₄ is an organic residue, i is 2 or 3) (an integer of 3) The fibers are treated with a reaction product obtained by polymerizing a compound obtained by dehydration condensation of a polyalkylene polyamine and a higher fatty acid using a crosslinking agent, then treated with a silicone water repellent, dried, 70 more
A method for producing water- and oil-repellent fibers that is characterized by heat treatment at 200℃.