JP2007092201A - Flameproofing agent of nylon fiber and flameproofing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a flameproofing agent for flameproofing the fiber surface of nylon textile product of nylon fiber, woven fabric, knitted fabric, nonwoven fabric, etc., and to provide a flameproof method using the same. <P>SOLUTION: The flameproofing method comprises fixing a flame retardant to the surface of nylon fiber constituting a nylon product such as textile, woven fabric, knitted fabric, nonwoven fabric, etc. The nylon product is immersed or brought into contact with an aqueous solution of a flameproofing agent containing at least a phosphorus-based flame retardant, an emulsifying agent and a fixing agent at the liquid temperature higher than or equal to a room temperature and ≤100°C, flameproofed and is after-treated by heat drying at ≥80°C and ≤150°C. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a flame retardant agent and a flame retardant treatment method for nylon fibers constituting nylon products such as fibers, woven fabrics, knitted fabrics and nonwoven fabrics.

  Since halogen-containing flame retardants generate dioxins during combustion, phosphorus-containing flame retardants and other flame retardants have been developed for the purpose of making nylon flame retardant. However, as shown in, for example, a technique (Patent Document 1) in which a nylon resin containing a non-halogen flame retardant is applied to a component such as a connector in the electrical / electronic field, an electrical component in the automotive field, etc. Most flame-retardant nylon products using halogen-based flame retardants are resin molded products.

  In fact, there are few technologies related to flame retardancy of nylon fibers, and the development of technology for flame retarding nylon fibers has become a major issue.

  Conventionally proposed flame retardant methods have not solved practical problems. For example, a method for producing a flame-retardant nylon carpet using nylon fibers obtained by spinning a nylon resin blended with a triazine-based flame retardant has been proposed (Patent Document 2). When about 20% by weight of a flame retardant was contained therein, there was a problem that not only the physical properties of the nylon fiber were impaired, but also the product price was increased.

  As described above, the technology for forming and spinning a flame retardant contained in the conventionally proposed nylon resin cannot open up the prospect of practical application.

Therefore, it is conceivable to make the flame retardant by chemical treatment on the resin and fiber surface, not in the resin, but the technology for making the fiber flame retardant by chemical treatment is flame retardant on the polyester fiber. However, only a method for forming the same is disclosed (Patent Document 3). However, nylon fiber and various woven fabrics, knitted fabrics, and non-woven fabrics using nylon fibers have no excellent technology for imparting flame retardancy by fixing a flame retardant directly to the fiber surface. Because of this, there is a strong desire for the development of technologies that make flame retardants easily and easily made of nylon fibers as interior materials such as clothing, curtain lace and carpets, seat covers for automobiles and railways, and many other industrial materials. It was rare.
JP 2003-292773 A JP 2005-205157 A Japanese Patent No. 3382180

  From the background as described above, the present invention solves the conventional problems and imparts flame retardancy to nylon fibers constituting nylon products such as fibers, woven fabrics, knitted fabrics and nonwoven fabrics by treatment on the surface thereof. The goal is to provide a completely new technical means that can

  In order to solve the above problems, the present inventor has intensively studied from an academic and technical viewpoint for directly fixing a flame retardant to the surface of nylon fibers constituting various nylon products. As a result, the following findings were obtained.

  The present inventor considers that the development of a technology for fixing a nylon fiber, not simply coating (coating) a flame retardant on the fiber surface, is important in solving the problem. Research started from the viewpoint of structure and physical properties.

  That is, first, a phosphorous flame retardant is selected as the non-halogen flame retardant, and a method for fixing the phosphorous flame retardant to the surface of the nylon fiber in an aqueous system (in an aqueous solution) having the best adaptability is examined. I thought it was important. The following findings are emphasized and obtained as a result in the examination process.

  1) Since the amino group at the end of the nylon molecular chain is present on the surface of the nylon fiber, a phosphoric ester compound having an anionic aromatic group or aliphatic group in the molecule as a phosphorus flame retardant. If used, it is considered that the flame retardant can be fixed to the nylon fiber based on a mechanism similar to the well-known method of dyeing nylon with an acid dye.

  2) Since most of the phosphoric acid esters are hardly soluble in water, the phosphoric acid ester, which is a flame retardant, can be emulsified in water by using an anionic surfactant having a phosphoric acid ester group as an emulsifier. Furthermore, it is considered that the surfactant itself having the phosphate ester group can also contribute to flame retardancy.

  Furthermore, it is considered that the interaction between the amino group at the end of the nylon molecular chain and the phosphate ester does not have as strong an interaction as the sulfonic acid group of the acid dye. Therefore, it is expected that the effect of fixing the flame retardant to the nylon fiber surface is enhanced by interposing an anionic surfactant having a sulfonic acid group or a sulfate ester group as an emulsifier.

  3) Furthermore, it is conventionally known that acid dyes are more firmly fixed to nylon fibers by tannic acid, that is, polyphenols (“Journal of the Fiber Society”, Vol. 38, T-224 (1982)). Tannic acid diffuses and penetrates to the surface layer of nylon fiber. Furthermore, tannic acid has many aromatic groups in the molecule, so it interacts with phosphate ester flame retardant, that is, is compatible. Since it is thought that it has the effect | action as an emulsifier and a sticking agent, it is guessed that it contributes greatly to sticking of this flame retardant.

  In addition, since the above emulsifier is water-soluble and the flame retardant also has a polar group, the flame retardant and the polar group of the emulsifier are in a non-dissociated state in order to promote fixation to the end of the nylon molecular chain or the nylon fiber surface. It is desirable.

  4) Therefore, the inventor of the present application considered that it is effective to allow the flame retardant and the emulsifier to coexist in the non-dissociated state in the flame retardant.

  5) The present invention has been completed based on such a new idea and knowledge. And the present invention eliminates the problems of the prior art, flame retardant treatment and flame retardant for fixing phosphorus-based flame retardant on the surface of nylon fiber products such as nylon fiber, woven fabric, knitted fabric, non-woven fabric, etc. A processing method is provided.

  That is, the present invention solves the above-mentioned problems. First, a flame retardant is fixed on the surface of nylon fibers constituting nylon products such as fibers, woven fabrics, knitted fabrics and nonwoven fabrics, thereby exhibiting flame retardancy. There is provided a flame retardant treatment agent for nylon fibers characterized in that it comprises at least a phosphorus-based flame retardant, an emulsifier and a fixing agent.

  Second, the flame retardant treatment agent is characterized in that the phosphorus flame retardant is a phosphate ester compound.

  3rdly, the said emulsifier is at least 1 sort (s) chosen from phosphate ester, sulfonate, sulfate ester salt, and polyphenol, The flame retardant treatment agent characterized by the above-mentioned is provided.

  Fourth, the sticking agent is a mixture of at least one selected from the group of at least one polyphenol and an alkaline earth metal salt, trivalent metal salt, and organic acid. Provide a flame retardant.

  Fifth, a nylon fiber characterized by immersing or contacting the nylon product such as the fiber, woven fabric, knitted fabric or nonwoven fabric in an aqueous solution of any one of the first to fourth flame retardants A flame retardant treatment method is provided.

  Sixth, the present invention provides a flame retardant treatment method characterized in that the aqueous solution is immersed or brought into contact at a temperature of room temperature to 100 ° C.

  Seventh, the present invention provides a flame retardant treatment method, wherein the concentration of the phosphorus flame retardant in the aqueous solution is in the range of 0.1 to 20% by weight with respect to water.

  Eighth, the flame retardant treatment method is characterized in that the concentration of the emulsifier in the aqueous solution is in the range of 0.05 to 10% by weight with respect to water.

  Ninth, the flame retardant treatment method is characterized in that the concentration of the fixing agent in the aqueous solution is in the range of 0.01 to 10% by weight with respect to water.

Furthermore, tenthly, after the flame retardant treatment, the nylon product such as the fiber, woven fabric, knitted fabric or nonwoven fabric is dehydrated and post-treated by heat drying at a temperature of 80 ° C. or higher and 150 ° C. or lower. Provide a flame retardant treatment method.

  According to the present invention as described above, a flame retardant treatment comprising at least a phosphorus-based flame retardant, an emulsifier, and a fixing agent for achieving flame retardant of fiber products such as nylon fiber, woven fabric, knitted fabric and nonwoven fabric. Furthermore, the flame retardant is fixed to the fiber surface in a state in which the fiber product is immersed in an aqueous solution of the flame retardant, and after dehydration, heat drying (post-treatment) is performed. It is possible to provide a flame retardant treatment method that further increases the adhesion of the flame retardant. This flame retardant treatment and flame retardant treatment method is simple and can be widely used not only for materials such as nylon fibers, woven fabrics, knitted fabrics and nonwoven fabrics, but also for various flame retardants made from them. Is. The excellent effect of flame retardancy of such nylon fibers according to the present invention is completely unexpected from the prior art.

  The invention of this application has the features as described above, and the embodiments thereof will be described in detail below.

  In the present invention, “nylon” is not particularly limited as long as it has an amide bond in the polymer main chain, but nylon 6, nylon 11, nylon 12, nylon 46, nylon 66, nylon 610 Nylon 612, Nylon MXD6, Nylon copolymer, and blends thereof are exemplified as suitable objects.

  Such nylon-based fibers may be undyed yarns or dyed yarns, and the form is not particularly limited. However, fibers, woven fabrics, knitted fabrics, non-woven fabrics, ultrafine fibers, and products made from these materials are suitable. Examples of such products include clothing such as stockings, blouses, skirts, interior materials such as curtain laces, carpets, upholstered furniture, fishing lines, sewing threads, screen doors, fiber membrane materials, filters, etc. Industrial materials such as artificial grass, tire cords, and airbags are exemplified as suitable objects.

  That is, from the above, the “nylon fiber” targeted by the flame retardant treatment of the present invention and the flame retardant treatment method using the same is a fiber, that is, a filament such as a monofilament or a multifilament. In addition, the present invention includes “fibers” constituting woven fabrics, knitted fabrics, non-woven fabrics, and other various nylon products, which are applicable as forms of these products themselves in the flame retardant treatment. The term “product” here includes not only the final product but also the present product, intermediate products, and raw yarn products. These nylon products may coexist with polyester fibers, acrylic fibers, cotton, silk, metal, inorganic fibers, and the like other than nylon as long as flame retardancy is not hindered.

  The phosphoric flame retardant constituting the flame retardant treatment of the present invention for the above-mentioned “nylon fiber” includes a phosphoric ester compound that does not contain a halogen atom and has an aromatic group or an aliphatic group If it is, it will not specifically limit. Tricresyl phosphate (also known as tricresyl phosphate, tolyl phosphate), triphenyl phosphate (also known as triphenyl phosphate), cresyl diphenyl phosphate, xylylene diphenyl phosphate, tributyl phosphate, triethyl phosphate, tris 2-ethylhexyl phosphate ( (Also known as: trioctyl phosphate), octyl diphenyl phosphate, trisisopropylphenyl phosphate, trisbutoxyethyl phosphate, biphenyl phosphate substituted with a methyl group, a t-butyl group, a hydroxyl group and the like, and derivatives thereof One or more of the mixtures are exemplified as suitable.

  In addition, halogen atom-containing phosphate esters such as trisdichloropropyl phosphate and tris β-chloropropyl phosphate are also effective as flame retardants for nylon fibers, but they may generate dioxins even with slight combustion. It is not a suitable target.

  Next, the flame retardant agent of the present invention contains an emulsifier, and this emulsifier may be any one as long as it has a function of emulsifying the phosphorus flame retardant into an aqueous system. May be a function that promotes the action of the fixing agent, or a function that itself functions as a fixing agent. In the case of functioning also as a sticking agent, in the present invention, as the emulsifier and the sticking agent, one kind which is not classified as a substance may be used alone or in combination.

  For example, as an emulsifier for emulsifying a phosphorus-based flame retardant into an aqueous system, surfactants having a phosphate ester group are exemplified, among which polyoxyethylene alkyl ether phosphates, polyoxyethylene phenyl ether phosphates, and these One or more of the mixtures are exemplified as suitable objects.

  Furthermore, the emulsifier for emulsifying the flame retardant in an aqueous system and promoting adhesion to the surface of the flame retardant nylon fiber is exemplified by sulfonates and sulfates, which are non-dissociating from the amino group at the end of the nylon chain. Although it will not specifically limit if it forms an ionic bond, Among them, alkylbenzene sulfonates, alkylnaphthalene sulfonates, formalin polycondensate of naphthalene sulfonate, formalin polycondensate of melamine sulfonate, dialkylsulfosuccinate Sulfonates such as salts, alkylsulfoacetates, α-olefin sulfonates, N-acyl-N-methyltaurine salts, dimethyl terephthalate sulfonates, higher alcohol sulfates, secondary higher alcohol sulfates, polyoxy One or two or more of sulfates such as ethylene alkyl sulfates, secondary higher alcohol ethoxy sulfates, polyoxyethylene alkyl phenyl ether sulfates, and mixtures of these sulfonates and sulfates Is exemplified as a suitable target.

  And as a thing which has a function and a property as an emulsifier and a sticking agent, the polyphenols which have a phenolic hydroxyl group and an aromatic group, especially natural tannic acid and synthetic tannic acid are illustrated as a suitable object.

  Furthermore, the flame retardant treatment of the present invention contains a sticking agent, which is preferably a polyphenol as described above, particularly at least one of natural tannic acid and synthetic tannic acid, Mixtures of at least one of alkaline earth metal salts, trivalent metal salts and organic acids are preferably considered. Examples of the latter salts and organic acids include alkaline earth metal salts such as magnesium chloride and calcium chloride, aluminum salts such as potassium aluminum sulfate (alum), silicates such as sodium metasilicate, and trivalent metal salts thereof. A mixture of these and organic acids such as acetic acid are exemplified as suitable subjects.

  The above-described flame retardant treatment for nylon fibers according to the present invention may be prepared by mixing a phosphorus-based flame retardant, an emulsifier and a fixing agent constituting the nylon fiber in advance, partially or as a whole. Each of them may be configured to be mixed when using the crystallization process.

As for the blending ratio of the phosphorus-based flame retardant, the emulsifier and the sticking agent in the flame retardant, the concentration with respect to water in the case of a mixed aqueous solution is also explained below;
Phosphorus flame retardant: 0.1 to 20% by weight
Emulsifier: 0.05 to 10% by weight
Fixing agent: 0.01 to 10% by weight
It is preferably considered to be in the range.

  And in addition to the above essential components, you may further mix | blend various additives with the flame-retarding processing agent of this invention as needed. For example, antifoaming agents, viscosity modifiers, colorants, stabilizers and the like. However, the addition prevents the concentration relative to water from exceeding 0.1% by weight.

  Next, a method for flame retardant treatment of nylon fibers using at least the flame retardant agent comprising the phosphorus flame retardant, the emulsifier and the fixing agent will be described in detail.

  The flame retardant treatment agent is preferably used as a mixed aqueous solution of the above components.

  The concentration of the phosphorus-based flame retardant in the aqueous solution is in the range of 0.1 to 20% by weight, more preferably in the range of 1 to 15% by weight, and further preferably in the range of 2 to 10% by weight with respect to water. The range is exemplified.

  The concentration of the emulsifier in the aqueous solution is in the range of 0.05 to 10% by weight, more preferably 0.1 to 7% by weight, and still more preferably 0.2 to 5% by weight with respect to water. The range is exemplified.

  As the concentration of the fixing agent in the aqueous solution, the concentration of the mixture of the polyphenols and the polyvalent metal salt is 0.01 to 10% by weight, more preferably 0.02 to 7% with respect to water. It is exemplified that the content is in the range of wt%, more preferably in the range of 0.03 to 5 wt%.

  In the fixing agent mixture, the concentration of the polyvalent metal salt or the like is in the range of 0.01 to 3% by weight, more preferably in the range of 0.015 to 1% by weight, and still more preferably in the range of 0.01 to 1% by weight. The range of 02 to 0.7% by weight is exemplified.

  In the mixed aqueous solution of the flame retardant containing each component in the above-mentioned concentration range, the nylon fiber or a product such as a woven fabric, knitted fabric, or non-woven fabric has a liquid temperature of room temperature or higher, that is, changes due to the season or environment. In general, contact or immersion is performed at a temperature range of 10 ° C. or higher and 100 ° C. or lower, more preferably 30 ° C. or higher and 98 ° C. or lower, more preferably 60 ° C. or higher and 95 ° C. or lower. This is an embodiment of the method for flame retardant treatment of nylon fibers.

  Furthermore, in order to enhance the adhesion of the phosphorus flame retardant to the surface of the nylon fiber, after the flame retardant treatment, the nylon fiber or the woven fabric, knitted fabric, nonwoven fabric, etc. from the aqueous solution of the flame retardant treatment agent After the dehydration, the post-treatment by heating and drying is effective. The post-treatment temperature is a temperature range of 80 ° C. or higher and 150 ° C. or lower, more preferably a temperature range of 90 ° C. or higher and 140 ° C., and still more preferably a temperature range of 100 ° C. or higher and 130 ° C. or lower. A time of 10 minutes or more and 2 hours or less, more preferably a time of 20 minutes or more and 1 hour or less, and more preferably a time of 30 minutes or more and 50 minutes or less, such as nylon fiber, woven fabric, knitted fabric, nonwoven fabric, etc. It is set as the more preferable embodiment of the flame-retardant processing method.

  Examples will be shown below and described in more detail. Of course, the invention is not limited by the following examples, and it goes without saying that there are various modes for details.

  In the flame retardant treatment, nylon satin (nylon undyed curtain lace fabric) was used as a nylon fiber sample. The nylon satin has 30 denier nylon 6 fibers as warps and 110 denier nylon 6 fibers as wefts, and the finishing density is 260 warps / inch and 75 wefts / inch. The nylon satin used in the flame retardant treatment test described later is 10 g, and the size is about 140 mm in width (warp direction) and about 800 mm in length (weft direction).

  First, the nylon satin was washed by stirring for 30 minutes at 60 ° C. in a 3% by weight aqueous solution of Hypol 400 (a composite nonionic surfactant mainly composed of polyoxyethylene alkyl ether) manufactured by Shoei Riken, After pre-washing with water, drying was performed to perform pre-treatment for flame-retardant treatment.

  In a stainless steel pot usually used for dyeing tests, Wako Pure Chemical's tricresyl phosphate (TCP) with a concentration of 6% by weight as a flame retardant and polyoxyethylene alkyl ether phosphate with a concentration of 0.6% by weight as an emulsifier (Asahi) PS-440E) made by Denka, 150 mL of a mixed aqueous solution containing 3% Wako Pure Chemicals Tannic Acid (CAS No. 1401-55-4) and 0.5% by weight Wako Pure Chemicals calcium chloride as fixing agents Then, 10 g of the nylon satin loaded in a holder usually used for a dyeing test cloth was placed, immersed in the aqueous solution, and then the stainless steel pot was sealed with a lid. Subsequently, using a dye test machine manufactured by Texam Giken, flame retardancy treatment was performed at 95 ° C. for 40 minutes while rotating the stainless steel pot. Thereafter, a nylon satin sample was taken out from the pot, dehydrated, and kept in an electric dryer at 130 ° C. for 20 minutes to sufficiently dry the nylon satin sample for post-treatment.

This way, the flame retardancy evaluation nylon satin sample subjected to flame retardant treatment, flammability test method JIS L1091 D Method textile according (coil method), Suga combustion tester FL-45M (45 ⁰ Combustion The number of flame contact of the flame-retardant-treated sample was measured using a property tester). In addition, the case where the frequency | count of flame contact was 3 or more was evaluated as a flame retardance. As a result, as shown in Table 1, it was recognized that the flame-retarded nylon satin sample had excellent flame retardancy of 5, 4, and 4.

  Further, the fire-treated sample was subjected to a water washing treatment five times in accordance with the Fire and Disaster Management Agency Notification No. 1 on February 21, 1986, and then subjected to a combustion test in the same manner. As a result, as shown in Table 1, it was recognized that the flame retardant frequency was 4, 4, 4 and excellent flame retardancy was maintained even after water washing.

  A flame retardant treatment of nylon satin was performed in the same manner as in Example 1 except that the calcium chloride concentration was 0.05% by weight. As a result, as shown in Table 1, it was revealed that the number of flame contact was excellent in flame retardancy of 4, 4, and 4.

  Further, as a result of performing a combustion test on the flame-retardant treated sample after washing with water 5 times in the same manner as in Example 1, as shown in Table 1, the number of flame contact was 4, 3, and 4 with water washing. It was later confirmed that it has sufficient flame retardancy.

  The flame retardant treatment of nylon satin was performed in the same manner as in Example 1 except that the TCP concentration was 3 wt%, the tannic acid concentration was 1.5 wt%, and the calcium chloride concentration was 0.1 wt%. As a result, as shown in Table 1, it was revealed that the number of times of flame contact has excellent flame retardancy of 4, 4, and 4.

  Further, as a result of performing a combustion test on the flame-retardant treated sample after washing with water 5 times in the same manner as in Example 1, as shown in Table 1, the number of flame contact was 4, 3, and 4 with water washing. It was later confirmed that it has sufficient flame retardancy.

The flame retardant treatment of nylon satin was carried out in the same manner as in Example 3 except that 0.3% by weight of sodium metasilicate 9 hydrate (Na ₂ SiO ₃ .9H ₂ O) was used instead of calcium chloride. As a result, as shown in Table 1, the number of times of flame contact was 4, 3, and 3, and in this case also, it became clear that the flame retardance was sufficient.

  Further, as a result of performing a combustion test on the flame-retardant treated sample after washing with water 5 times in the same manner as in Example 1, as shown in Table 1, the number of flame contact was 4, 3, and 3 with water washing. It was later confirmed that it has sufficient flame retardancy.

  The concentration of TCP is 3% by weight, and as an emulsifier component, polyoxyethylene alkylphenyl ether sulfate (NES-60N manufactured by Asahi Denka) having a concentration of 0.6% by weight is used instead of polyoxyethylene alkyl ether phosphate (PS-440E). Except for the above, the flame retardant treatment of nylon satin was performed in the same manner as in Example 1. As a result, as shown in Table 1, the number of times of flame contact was 5, 4, and 4, and even when the emulsifier component was replaced with a phosphate ester as a sulfate ester, it was effective for fixing the flame retardant to the nylon fiber. Proven to be.

  Further, as a result of performing a combustion test on the flame-retardant treated sample after washing with water 5 times in the same manner as in Example 1, as shown in Table 1, the number of flame contact was 4, 4, and 4 with water washing. It was later confirmed that it has sufficient flame retardancy.

  Nylon is the same as in Example 1 except that the polyoxyethylene alkyl ether phosphate (PS-440E) is excluded from the flame retardant component (concentration: 0% by weight) and the calcium chloride concentration is set to 0.3% by weight. Satin flame retardant treatment was performed. As a result, as shown in Table 1, the number of times of flame contact was 4, 4, and 4, and it was recognized that the synergistic effect of tannic acid and calcium chloride as the fixing agent effectively acts on the fixing of the flame retardant. It was. This result also proves that polyphenols having a hydroxyl group and an aromatic group have both an effect as an emulsifier and a fixing agent of the flame retardant.

  Further, as a result of performing a combustion test on the flame-retardant treated sample after washing with water 5 times in the same manner as in Example 1, as shown in Table 1, the number of flame contact was 4, 3, and 3 with water washing. It was later confirmed that it has sufficient flame retardancy.

  Next, in order to examine the influence of the flame retardant treatment temperature and the treatment time, after the flame retardant treatment at a temperature of 60 ° C. for 10 minutes, the treated sample is quickly dehydrated and then heated at 130 ° C. for 20 minutes. A flame retardant treatment was performed in the same manner as in Example 5 except that the post-treatment was performed by drying. As a result, compared with Example 5, although the processing temperature was low and the processing time was short, the flame contact number was 4, 3, and 4, and sufficient flame retardancy was recognized. Furthermore, after performing the flame retardancy test, the number of flame contact after water washing 5 times was 3, 3, 3 and the flame retardancy decreased slightly, but the flame retardancy treatment at 60 ° C was also possible. It was found to be effective. This indicates that the flame retardant treatment technology of the present invention also has an energy saving effect.

  Furthermore, Example 7 was carried out except that after the flame retardant treatment at a flame retardant treatment temperature of 30 ° C. for 1 minute, the treated sample was quickly dehydrated and then post-treated by heat drying at 130 ° C. for 20 minutes. In the same manner as above, flame retardant treatment was performed. As a result, the number of flame contact after the flame retardant treatment was 3, 3, and 3, although inferior to the value of Example 7, and flame retardancy was recognized. As described above, the fact that the flame retardancy was exhibited even at a temperature as low as 30 ° C. even after the treatment for a short time of 1 minute is that the technique of the present invention is a simple and inexpensive method, and energy saving. It has proven to be an excellent and effective one.

  In addition, after the water-washing of the sample after the flame retardant treatment, the number of flame contact becomes 3, 3, 2 and the flame retardant adheres to the nylon fiber although it is not sufficiently flame retardant. Suggests that

  The nylon satin used in Examples 1 to 8 was an unstained sample. However, in order to examine whether the technique of the present invention is effective for a stained sample, the nylon satin was subjected to the method described below. The sample dyed with was prepared and the flame retardant treatment test was conducted. This dyeing method is a general technique widely used for dyeing nylon fibers.

  First, a stainless steel pot for dyeing described in Example 1 was added to a 0.1 wt% Cayanol Yellow N3R, a 0.1 wt% Cayanol Red NBR, and a 0.1 wt% Cayanol Blue NR ( 150 ml of an aqueous solution of a mixture of 0.6% by weight polyoxyethylene alkyl ether phosphate (PS-440E manufactured by Asahi Denka) is added to each dye, and then Example 1 is added to this dyeing solution. After putting the unstained nylon satin loaded in the holder described in 1), the stainless steel pot was sealed with a lid. Subsequently, dyeing was performed at 95 ° C. for 40 minutes while rotating the stainless steel pot using a dyeing tester manufactured by Texam Giken. The nylon satin thus dyed was sufficiently washed with water and then dried by heating at a temperature of 130 ° C. for 20 minutes.

  The obtained dyed nylon satin was subjected to a flame retardant treatment in the same manner as in Example 5 except that the TCP concentration as the phosphorus flame retardant was changed to 6% by weight. A flame test of the dyed nylon satin after the flame retardant treatment was conducted, and as shown in Table 1, the number of times of flame contact was 4, 4, and 4, which was sufficient even for the dyed nylon satin. Flammability was observed.

  Furthermore, as a result of performing a combustion test after 5 times of water washing for the flame retardant treated nylon satin, the number of flame contact was 4, 3, and 3, and sufficient flame retardancy was maintained even after water washing. It was recognized that Thus, it can be said that the technique of the present invention can be widely applied to flame retardant nylon fibers regardless of whether they are undyed fibers or dyed fibers.

  The nylon satin was dyed in the same manner as in Example 9 except that 4% by weight of isolan black 2S-LD (chromium complex type azo dye manufactured by Dystar Japan) was used as the dye.

The obtained dyed nylon satin was subjected to a flame retardant treatment and a combustion test in the same manner as in Example 9. As shown in Table 1, the number of flame contact was 5, 4, and 4, and the dyed nylon was dyed. Excellent flame retardancy was also observed for satin, and the number of flame contact was 4, 4, 3 even after 5 times of water washing, and the flame retardancy was retained after water washing Was confirmed.
<Comparative Example 1>

In order to investigate the effect of the sticking agent on the flame retardancy of nylon fiber, TCP containing 6% by weight of TCP as a phosphorus flame retardant and 0.6% by weight of polyoxyethylene as an emulsifier does not contain tannic acid and calcium chloride. The flame retardant treatment was performed in the same manner as in Example 1 except that only alkyl ether phosphate was used as a component of the aqueous solution of the flame retardant. Next, as shown in Table 1, as a result of performing a combustion test of the sample after the flame retardant treatment as in Example 1, the number of times of flame contact was 2, 1, and 1, and the phosphorus-based flame retardant It was difficult to make the nylon fiber and its product flame-retardant only with the emulsifier alone, and it was proved that the synergistic effect of tannic acid and salts was effective in making the nylon fiber flame-retardant.
<Comparative example 2>

The flame retardant treatment of nylon satin was performed in the same manner as in Example 1 except that the tannic acid concentration was 0.15 wt% and the calcium chloride concentration was 0 wt%, that is, calcium chloride was excluded. Next, as in Example 1, as a result of performing a combustion test on the sample after the flame retardant treatment, as shown in Table 1, the number of times of flame contact was 3, 2, and 2, compared with Comparative Example 1. Although some improvement in flame retardancy was observed, sufficient flame retardancy was not observed. When considered together with the result of Comparative Example 1, this result shows that tannic acid tends to have an effect on the expression of flame retardancy, but the salt (for example, calcium chloride) having the effect of further enhancing the fixation is obtained. When it does not exist, it indicates that flame retardancy is insufficient.
<Comparative Example 3>

In order to investigate whether tannic acid itself, which is one of the emulsifier components of the present invention, is effective for flame retardancy of nylon fibers and products thereof, an aqueous solution having a tannic acid concentration of 3% by weight is used as a flame retardant treatment. In the same manner as in Example 1, the flame retardant treatment of nylon satin was performed. Next, as in Example 1, as a result of performing a combustion test of the sample after the flame retardant treatment, the number of flame contact was 3, 2, 2 as shown in Table 1, and sufficient flame retardancy was obtained. I was not able to admit. This result shows that flame retardant properties cannot be imparted to nylon fibers simply by adsorbing or fixing tannic acid to the fiber surface.
<Comparative example 4>

  Next, in order to investigate the effect of the salts among the binder components that enhance the adhesion of tannic acid to the nylon fiber surface, nylon was added in the same manner as in Comparative Example 3 except that 0.3% by weight of calcium chloride was added. Flame retardant treatment and post-treatment (heat drying) of satin were performed. As a result of performing a combustion test of the obtained sample, as shown in Table 1, the number of times of flame contact was 3, 2, and 2, and the flame retardance was improved only by increasing the adhesion of tannic acid to the nylon fiber. It became clear that not.

  From these results, the flame retardant treatment method for nylon fiber products such as nylon fiber, woven fabric, knitted fabric and nonwoven fabric of the present invention is a novel technology that has not been available in the past, and the fiber surface is simple, inexpensive and energy-saving. It can be said that this is an excellent technology that can make a nylon fiber flame retardant without impairing the physical properties of the fiber.

Claims (10)

A flame retardant treatment for fixing a flame retardant to the surface of nylon fiber constituting a nylon product such as fiber, woven fabric, knitted fabric, nonwoven fabric, etc.
A flame retardant treatment for nylon fibers, comprising at least a phosphorus-based flame retardant, an emulsifier and a fixing agent. The flame retardant agent according to claim 1, wherein the phosphorus flame retardant is a phosphate ester compound. The flame retardant agent according to claim 1, wherein the emulsifier is at least one selected from phosphate esters, sulfonates, sulfate esters and polyphenols. The said fixing agent is at least 1 sort (s) selected from the group of at least 1 sort (s) of polyphenols, an alkaline-earth metal salt, a trivalent metal salt, and an organic acid, The Claim 1 characterized by the above-mentioned. Flame retardant treatment. A method for flame retardant treatment of nylon fibers, comprising immersing or contacting nylon products such as fibers, woven fabrics, knitted fabrics and nonwoven fabrics with the aqueous solution of the flame retardant treatment agent according to claim 1. 6. The flame retardant treatment method according to claim 5, wherein the aqueous solution is immersed or brought into contact at a temperature of room temperature to 100 ° C. The flame retardant treatment method according to claim 5, wherein the concentration of the phosphorus flame retardant in the aqueous solution is in the range of 0.1 to 20% by weight with respect to water. The flame retardant treatment method according to claim 5, wherein the concentration of the emulsifier in the aqueous solution is in the range of 0.05 to 10% by weight with respect to water. The flame retardant treatment method according to claim 5, wherein the concentration of the fixing agent in the aqueous solution is in the range of 0.01 to 10% by weight with respect to water. After the flame retardant treatment according to claim 5, the nylon product such as the fiber, woven fabric, knitted fabric, and nonwoven fabric is dehydrated and post-treated by heat drying at a temperature of 80 ° C. or higher and 150 ° C. or lower. Combustion treatment method.