JP2009263827A - Flame-retardant chemical agent, flame-retardant fiber and method for producing the fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retardant chemical agent to be used for imparting flame retardancy to textile fiber materials and obtaining high flame retardancy, and also excellent in durability and color fastness such as frictional fastness. <P>SOLUTION: The flame-retardant chemical agent to be used for imparting flame retardancy to textile fiber materials is provided, comprising at least water, a phosphorus compound (A) represented by chemical formula (1) and guanidine sulfamate (B); wherein the guanidine sulfamate (B) content is 1-30 wt.% based on the phosphorus compound (A). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a flame retardant processing agent used for imparting flame retardancy to a fiber material, a flame retardant fiber obtained by treating the fiber material with the flame retardant processing agent, and a method for producing the same.

  Conventionally, a flame retardant in which a halogen compound such as hexabromocyclododecane is dispersed or emulsified in water has been generally used in order to impart flame retardancy to a fiber material. However, although the fiber material treated with such a halogen-based compound has flame retardancy, there is a risk that harmful halogenated gas is generated by combustion, and the movement of dehalogenation is increasing from the environmental aspect. Therefore, it tends to avoid use as much as possible.

  An organophosphorus compound is used as an alternative to the halogen-based compound, but it is difficult to impart sufficient flame retardancy because the phosphorus content in one molecule is small. For this reason, in order to provide sufficient flame retardance, it is necessary to process in large quantities with an organic phosphorus compound. Due to the large amount of treatment, there are problems of causing a decrease in the texture of the fiber and reducing dyeing, friction and light fastness. In order to solve such a problem, it has been proposed to use a phosphorus compound having a large phosphorus content in one molecule as a flame retardant. For example, as in Patent Document 1, a flame retardant composed of a certain phosphorus compound is already known. However, even if such a phosphorus compound is used, it is necessary to apply a large amount of this phosphorus compound in order to have flame retardancy that is excellent in washing resistance and dry cleaning. There was a problem of lowering friction, light fastness.

  Patent Document 2 discloses a flame-retardant processing method for imparting a certain phosphorus compound and phosphoric acid amide to a fiber material as a phosphorus flame retardant. However, the flame retardant mechanism of this phosphorus compound and phosphoric acid amide is the so-called “carbonization type” due to the effect of suppressing the generation of combustion gas by promoting carbonization and the heat insulation effect of the resulting carbonized residue. In this case, there is a problem that the carbonization residue generated by the combustion hinders the flame-retardant effect due to melting and dropping (drip) of the flaming portion, making it difficult to make the flame-retardant.

  Patent Document 3 discloses a flame-retardant processing method for imparting guanidine sulfamate to a cellulosic material. However, when guanidine sulfamate is added, there is a problem that it easily ignites, so it has a flame retardant effect on cellulosic materials that are originally easy to ignite, but fiber materials that are originally difficult to ignite are ignited one after another and burn. It was difficult to spread and impart flame retardancy.

  Patent Document 4 discloses a flame retardant nonwoven fabric in which guanidine sulfamate and ammonium sulfate are added to a nonwoven fabric mainly composed of polyester fibers. However, it is necessary to treat guanidine sulfamate in a large amount, and guanidine sulfamate crystallizes over time, resulting in a problem that the appearance is impaired.

JP-A-60-99167 JP 2004-332187 A Japanese Patent Laid-Open No. 9-20882 JP 2008-13858 A

  The present invention is used for imparting flame retardancy to a fiber material, and provides a flame retardant processing agent that provides good flame retardancy and is excellent in dyeing fastness such as friction fastness and durability. With the goal. Another object of the present invention is to provide a flame retardant fiber that is imparted with good flame retardancy to a fiber material and has excellent dyeing fastness such as friction fastness and durability, and a method for producing the same. .

  As a result of intensive studies to solve the above problems, the present inventors have found that a specific phosphorus compound and sulfamic acid that are flame retardant components in a flame retardant processing chemical used to impart flame retardancy to a fiber material By using guanidine in combination at a specific ratio, the flame retarding mechanism is changed from the so-called “carbonization type” by the conventional effect of suppressing the generation of combustion gas by the promotion of carbonization and the heat insulation effect of the resulting carbonized residue, The so-called “drip type” that suppresses combustion by drip) can be made into a so-called “drip type”, and has better flame retardancy than the case where each is contained alone, particularly V-2 or VTM-2 of UL-94 method, etc. It was found that flame retardancy satisfying the standards can be imparted, and flame retardant performance that is exceptionally excellent in dyeing fastness and durability such as fastness to friction can be imparted, and the present invention has been achieved.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４は同一または異なるアルキル基であり、ｘは０または１を表す。） That is, the present invention is a flame retardant processing agent used for imparting flame retardancy to a fiber material, and includes a phosphorus compound (A) represented by the following chemical formula (1), guanidine sulfamate (B) and It contains at least water and the content of guanidine sulfamate (B) is 1 to 30% by weight with respect to the phosphorus compound (A).

(Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different alkyl groups, and x represents 0 or 1)

  In addition, the flame retardant processing agent of the present invention includes a case where the fiber material includes at least a fiber having a large amount of crystal regions, and may further include a fiber having a large amount of an amorphous region, It is suitable when it contains at least a polymer elastic body. The pH of the flame retardant processing chemical at 25 ° C. is preferably 6-8.

The present invention also provides a flame retardant fiber obtained by treating a fiber material with the above flame retardant processing agent, wherein the adhesion amount of the phosphorus compound (A) to the entire fiber material is 0.1 to 20% by weight, and sulfamine It is a flame retardant fiber having an adhesion amount of acid guanidine (B) of 0.1 to 6% by weight.
In the flame-retardant fiber of the present invention, the fiber material treated with the flame-retardant processing chemical preferably has a pH of 4 to 8. Here, the pH of the fiber material refers to 5 g of a test piece (fiber), which is obtained by putting 50 mL of distilled water into a 200 mL flask equipped with a glass stopper and boiling gently for 2 minutes, then moving the flask away from the heat source and making 1 cm × 1 cm pieces. Material) is placed in a flask, and the flask is stoppered. Sometimes the stopper is loosened and the flask is left to stand for 30 minutes while shaking, and then the pH measured at 25 ° C.
The manufacturing method of the flame-retardant fiber of this invention includes the process of processing said flame-retardant processing chemical | medical agent.

  The flame retardant processing agent of the present invention imparts good flame retardancy to a fiber material and is excellent in dyeing fastness such as friction fastness and durability. In addition, the flame-retardant fiber and the method for producing the same according to the present invention can impart good flame retardancy to the fiber material, and are excellent in fastness to dyeing such as fastness to friction and durability.

  The present invention is a flame retardant processing agent used for imparting flame retardancy to a fiber material, comprising a phosphorus compound (A) represented by the chemical formula (1), guanidine sulfamate (B) and water. It is a flame retardant processing chemical which is contained at least and the content of guanidine sulfamate (B) is 1 to 30% by weight with respect to the phosphorus compound (A). Moreover, this invention is a manufacturing method of a flame-retardant fiber including the process of processing a flame-retardant processing chemical | medical agent to a fiber material, and the flame-retardant fiber which processed the flame-retardant processing chemical | medical agent to the fiber material. This will be described in detail below.

The fiber material of the present invention is not particularly limited, but a fiber having a large crystal region (for example, aromatic polyester, cationic dyeable polyester, aromatic polyamide, aromatic polyimide, diacetate, triacetate, co-polymerization of monomers thereof) A fiber material containing at least a coalescence or the like is preferable because it is excellent in the adsorptivity of the phosphorus compound (A) contained in the flame retardant processing chemical and the durability and flame retardancy is improved. Among these, a fiber material containing at least an aromatic polyester or a cationic dyeable polyester is more preferable because it is excellent in the adsorption property of the phosphorus compound (A).
Examples of the aromatic polyester and the cationic dyeable polyester include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene terephthalate / isophthalate, polyethylene terephthalate / 5-sodiosulfoisophthalate. Can be mentioned.

  Moreover, as a fiber material, since it is the fiber material which contains a heat-melting type fiber at least, the flame retardance in this invention can be provided effectively, it is preferable. Examples of the hot-melt fiber include aromatic polyester, cationic dyeable polyester, aliphatic polyester, polyamide, nylon, polyurethane, acetate, polyethylene, polypropylene, acrylic, vinylon, polyimide, and polylactic acid. Among them, a fiber material containing at least an aromatic polyester or a cationic dyeable polyester is more preferable because it has high heat meltability and can effectively impart flame retardancy in the present invention.

The fiber material may include a fiber having a large number of crystalline regions and a fiber having a large amount of non-crystalline regions (for example, natural fibers such as cotton, hemp, and wool; nylon).
Here, the crystal region means a region in which the molecular chains constituting the fiber are relatively regularly oriented, for example, formed when a physical treatment such as stretching is performed in the manufacturing process of synthetic fiber or the like. The non-crystalline region is opposite to the above description and means a region in which the molecular chains constituting the fibers are not relatively regular and are randomly oriented.

  The fiber material may contain a polymer elastic body. The polymer elastic body is not particularly limited, and examples thereof include polyurethane elastomers, polyurethane urea elastomers, polyether ester elastomers, polyethylene elastomers, acrylonitrile, butadiene rubber, natural rubber, and polyvinyl chloride. Urea elastomers and polyether ester elastomers are preferred. The form of the polymer elastic body is not particularly limited, and examples thereof include fiber, cotton, yarn, rope, string, resin, film, sheet, membrane, and the like. Alternatively, it may be imparted to fibers other than the polymer elastic body by fusing, bonding or the like.

  The fiber material may be composed of only one type or may be composed of a plurality of types. In the case of including a fiber having a large amount of crystal region and a fiber having a large amount of non-crystalline region, any of mixed spinning, union, union, and union may be used. The form of the fiber material is not limited, and examples thereof include cotton, thread, rope, string, woven fabric, knitted fabric, nonwoven fabric, and artificial leather. Examples of the artificial leather include a woven fabric, a knitted fabric or a non-woven fabric containing ultrafine fibers such as polyester, polyamide, polyacryl, and polyolefin, which are provided by impregnation with a polymer elastic body such as polyurethane elastomer. There are no limitations on the use of the fiber material, such as industrial materials, industrial and household textile products, clothes, clothing, bedding, interiors, sporting goods, daily goods, etc., for example, seat sheets, seat covers, construction Curing sheets, tents, beds, curtains, futons, blankets, mattresses, work clothes, pajamas, ribbons, ropes, wallpaper, ceiling cloths, carpets, sofas, chairs, electrical appliances and the like.

(Flame retardant processing chemicals)
The flame retardant processing chemical of the present invention refers to a liquid material used for imparting flame retardancy to a fiber material. The flame retardant processing chemical of the present invention includes both a processing fluid used when treating a fiber material and a chemical diluted with water or the like to prepare the processing fluid.

  The phosphorus compound (A) used in the present invention is a component that suppresses the flame and burning of the fiber material and improves the flame retardancy by being imparted to the fiber material. However, since the phosphorus compound (A) has a so-called “carbonization type” flame retardant mechanism due to the suppression effect of combustion gas generation by promoting carbonization and the heat insulation effect of the resulting carbonized residue, the phosphorus compound (A) is used alone. Although there is an effect of suppressing the flame and burning of the fiber material, especially in the case of a fiber material containing a heat-melting type fiber, the melted portion carbonizes and burns due to the so-called “candle effect” that plays the role of a candle core. Tend to promote. Therefore, the guanidine sulfamate (B) is used in combination at a specific ratio, so that the hot melted portion of the fiber material melts and drops (drip) before flaming or carbonizing, thereby suppressing the combustion of the fiber material. Type "flame retardant mechanism, and in particular, flame retardancy satisfying standards such as UL-94 V-2 or VTM-2 can be imparted. Furthermore, flame retardancy with excellent dyeing fastness and durability can be imparted.

In the phosphorus compound (A) represented by the chemical formula (1), in the formula, R ¹ , R ² , R ³ , and R ⁴ are the same or different alkyl groups, and even if they are linear, they have a branch. May be. ^{R 1, R 2, R 3} , the carbon number of ^{R 4} is preferably 1-4, more preferably 1 to 3, 1 to 2 is more preferred. Among these, R ¹ , R ² , R ³ , R ⁴ are preferably methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl groups, more preferably R ¹ , R ² , R ⁴ is methyl and R ³ is ethyl. In the formula, x represents 0 or 1. The phosphorus compound (A) may be used alone or in combination of two or more. Examples of such phosphorus compound (A) include bis [(5-ethyl-2-methyl-1,3,2-dioxaphosphorinan-5-yl) methyl] methylphosphonate-P, P′-dioxide, (5-Ethyl-2-methyl-1,3,2-dioxaphosphorinan-5-yl) methyldimethylphosphonate-P-oxide and the like can be mentioned and produced by the method described in JP-A-60-99167. be able to. Moreover, a commercial item can also be used, for example, K-19A (made by Meisei Chemical Industry Co., Ltd.) etc. are mentioned.

  Although there is no limitation in particular about the content rate of the phosphorus compound (A) in the flame-retardant processing chemical | medical agent of this invention, 1 to 90 weight% is preferable with respect to the whole flame-retardant processing chemical | medical agent, and 5 to 80 weight% is more preferable. 5 to 70% by weight is more preferable. When the content of the phosphorus compound (A) is less than 1% by weight, sufficient flame retardancy may not be achieved, and there are too many water and other components, so that the phosphorus compound (A) is gradually changed over time. Hydrolysis can cause problems with storage, stability, and performance of flame retardant chemicals. On the other hand, if the content of the phosphorus compound (A) is more than 90% by weight, it may be difficult to obtain a stable flame retardant processing chemical.

  Further, guanidine sulfamate (B) used in the present invention is a component that promotes drip by imparting to a fiber material, and the flame retardancy is changed from “carbonized type” to “drip type” to improve flame retardancy. It is an ingredient. Specifically, since the phosphorus compound (A) has a so-called “carbonization-type” flame retardant mechanism due to the suppression effect of combustion gas generation by promoting carbonization and the heat insulation effect of the resulting carbonized residue, the phosphorus compound (A) alone When used, there is an effect of suppressing the ignition and combustion of the fiber material, but particularly in the case of a fiber material containing a hot-melt type fiber, the melted portion carbonizes without melting and dropping (drip), and plays the role of a candle core. The so-called “candle effect” tends to promote combustion. Therefore, by using guanidine sulfamate (B) in combination at a specific ratio, it is possible to suppress the combustion of the fiber material by melting and dropping (drip) before the heat melting portion of the fiber material is flamed or carbonized. Furthermore, guanidine sulfamate (B) is a component excellent in dyeing fastness such as friction fastness. Moreover, a commercial item can be used for guanidine sulfamate (B).

  About the content rate of the guanidine sulfamate (B) in the flame-retardant processing chemical | medical agent of this invention, 1-30 weight% is preferable with respect to the phosphorus compound (A) in a flame-retardant processing chemical | medical agent, and 1-20 weight% is more. Preferably, 2 to 15 wt% is more preferable, 5 to 15 wt% is particularly preferable, and 10 to 15 wt% is most preferable. When the content of guanidine sulfamate (B) is less than 1% by weight, the “drip-type” flame retardant effect due to the combined use of the phosphorus compound (A) and guanidine sulfamate (B) is hardly exhibited, and the melted portion carbonizes. In some cases, the so-called “candle effect”, which plays the role of a candle wick, promotes combustion. On the other hand, if the content of guanidine sulfamate (B) exceeds 30% by weight, the fiber material is likely to be flared. Therefore, even if the hot melted portion of the fiber material is melted and dropped (drip), the flammable portion becomes the fiber material. The remaining combustion may continue. In addition, guanidine sulfamate may crystallize over time and whiten to deteriorate the appearance.

  The flame retardant processing chemical of the present invention contains water as an essential component in addition to the phosphorus compound (A) and guanidine sulfamate (B). The water used in the present invention may be any of tap water, soft water, ion exchange water, distilled water and the like. The flame retardant processing chemical is composed of water except for the phosphorus compound (A) and guanidine sulfamate (B) (except for other components when other components are included).

  The flame retardant processing agent of the present invention is not particularly limited as long as it contains a phosphorus compound (A), guanidine sulfamate (B) and water, but other than this within a range not impairing the effect of the present invention. Ingredients may be included.

  Examples of other components include solvents (methanol, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutanol, t-butanol, ethylene glycol, propylene glycol, methyl glycol, ethyl glycol, butyl glycol, benzyl alcohol, Solfit, butyl carbitol, polyalkylene glycol, etc.), water-soluble polymers (polyvinyl alcohol, polyacrylic acid ester, methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, Xanthan gum, gum arabic, gelatin, polyvinyl pyrrolidone, polyethylene oxide, polyacrylamide, polystyrene sulfonate, polystyrene maleic acid copolymer, methoxyethylene Water maleic acid copolymer, soluble starch, cationized starch, carboxymethyl starch, etc.) Other flame retardants except for phosphorus compound (A) (triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl phenyl phosphate) , Xylenyl phenyl phosphate, cresyl xylenyl phosphate, phenyl orthoxenyl phosphate, naphthyl phosphate, alkyldiphenyl phosphate, etc .; resorcinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), resorcinol bis (dioxy) Phosphonic acid ester; Phosphinic acid ester; Phosphite ester; Hypophosphite ester; Phosphine oxide; Phosphate Phosphonium salt; Phosphate ester amide; Chlorinated phosphate ester; Chlorine-containing condensed phosphate ester; Phosphorus-containing polyester resin; Phosphazene; Ammonium polyphosphate, melamine-coated ammonium polyphosphate, melamine resin-coated ammonium polyphosphate, silicone-coated polyphosphorus Ammonium phosphate, ammonium phosphate phosphate, acid phosphate guanidine salt, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, dimelamine polyphosphate, ethylenediamine phosphate, carbamate phosphate, guanidine phosphate, guanylurea phosphate Phosphate flame retardants such as decabromodiphenyl ether, ethylenebis (pentabromodiphenyl), ethylenebis (tetrabromophthalimide), tris (tribromophenoxy) triazine Brominated flame retardants such as: Nitrogen flame retardants such as melamine, dicyandiamide, tris (2-hydroxyethyl) isocyanurate, melamine cyanurate; ammonium sulfamate; ammonium sulfate; magnesium hydroxide; aluminum hydroxide; pentaerythritol, di Hydroxyl-containing compounds such as pentaerythritol, starch, and sorbitol), surfactants, pH adjusters, crosslinkers, smoothing agents, sewability improvers, anti-slip agents, deodorants, antibacterial agents, thickening agents, softeners , Antistatic agents, water and oil repellents, hard finish agents, binders, coating processing agents, ultraviolet absorbers, antifouling agents, hydrophilizing agents, and the like. These may contain 1 type, or 2 or more types.

  There is no limitation in particular about the content rate of said other component. By blending a small amount of the solvent, the work efficiency and stability at low temperature are improved due to the decrease in viscosity. However, when the content is increased, problems may occur with respect to production and storage, and therefore it is preferably 10% by weight or less, more preferably 5% by weight or less based on the total flame retardant processing chemical.

  The flame retardant processing chemical of the present invention is preferably 6 to 8 at 25 ° C. because it can suppress deterioration of the fiber material over time and suppress the occurrence of metal rust. In particular, when the fiber material includes a polymer elastic body, it is preferable because deterioration of the polymer elastic body and deterioration of the strength of the fiber material including the polymer elastic body can be suppressed. In order to adjust the pH at 25 ° C. of the flame retardant processing agent of the present invention to 6-8, a pH adjuster may be used.

  Although it does not specifically limit as a pH adjuster, What is necessary is just an agent which can adjust the pH in 25 degreeC of a flame-retardant processing chemical | medical agent to 6-8. Examples of the pH adjuster include ammonia, primary amine (alkanolamine, N-alkyl substituted amine, etc.), secondary amine (dialkanolamine, N-alkyl substituted alkanolamine, N, N′-dialkyl substituted amine, etc.). Tertiary amine (trialkanolamine, N-alkyl substituted alkanolamine, N, N-dialkyl substituted alkanolamine, N, N, N-trialkyl substituted alkanolamine, polyoxyalkylene alkylamine, etc.), diamine (N, N , N ′, N′-tetrakis polyoxyalkylene substituted alkyldiamine, etc.), triamine (diethylenetriamine, etc.), alkali metal salts (sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium phosphate) , Potassium phosphate Sodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate, potassium pyrophosphate, potassium tripolyphosphate, potassium metaphosphate, sodium phosphite, sodium hypophosphite, sodium lactate, sodium acetate, sodium carbonate, potassium carbonate, carbonic acid Sodium hydrogen, sodium bicarbonate, sodium nitrite, sodium silicate, sodium tetraborate, sodium sulfite, trisodium EDTA, alkaline earth metal salts (calcium hydroxide, etc.), aluminum hydroxide, ammonium salts (carbonic acid, etc.) Ammonium hydrogen, diammonium hydrogen phosphate, etc.), guanidine salts (guanidine carbonate, guanidine phosphate, etc.), buffer consisting of acid and base (potassium dihydrogen phosphate-disodium hydrogen phosphate buffer, Tris buffer) (Tris (hydroxymethyl) aminomethane-hydrochloric acid buffer), Good buffer (Tris (hydroxymethyl) methylglycine, N-tris (hydroxymethyl) methyl-3-aminopropanesulfonic acid, 2- (cyclohexylamino) ethanesulfone Acid, 3- (cyclohexylamino) propanesulfonic acid) and the like. Among these, as the pH adjuster, those having weak basicity and / or buffering action are preferable. For example, disodium hydrogen phosphate, sodium tripolyphosphate, sodium pyrophosphate, guanidine phosphate, tris (hydroxymethyl) aminomethane Sodium silicate, sodium tetraborate, potassium dihydrogen phosphate-disodium hydrogen phosphate buffer, tris (hydroxymethyl) aminomethane-hydrochloric acid buffer (tris buffer), tris (hydroxymethyl) methylglycine, N -Tris (hydroxymethyl) methyl-3-aminopropanesulfonic acid, 2- (cyclohexylamino) ethanesulfonic acid and the like. These may contain 1 type, or 2 or more types.

  Although there is no limitation in particular about the content rate of the pH adjuster in a flame-retardant processing chemical | medical agent, what is necessary is just to make it contain so that pH in 25 degreeC of a flame-retardant processing chemical | medical agent may be in the range of 6-8. Moreover, it is preferable that it is 3-20 weight% with respect to a phosphorus compound (A), and, as for the content rate of a pH adjuster, it is more preferable that it is 3-15 weight%, and it is 5-15 weight%. Further preferred.

  A method for producing the flame retardant processing chemical is not particularly limited, and a known method can be adopted. For example, a flame retardant processing chemical can be prepared by blending a phosphorus compound (A) and guanidine sulfamate (B) dissolved in water, and optionally further diluting with water. Since the phosphorus compound (A) may hydrolyze with time in the presence of water, the flame retardant processing agent may be prepared immediately before being processed into the fiber material.

(Flame-retardant fiber manufacturing method and flame-retardant fiber)
The manufacturing method of the flame-retardant fiber of this invention includes the process (henceforth a process process) which processes the said flame-retardant processing chemical | medical agent to a fiber material.

  For example, as a treatment process, a fiber material is immersed in a bath containing the above-mentioned flame retardant processing chemical, and a treatment process (hereinafter referred to as process a) performed under conditions of a treatment temperature of 80 ° C. or more and a treatment time of 2 to 120 minutes, After the flame retardant processing agent is attached to the fiber material, heat treatment is performed at a temperature of 90 to 220 ° C., and the phosphorus compound (A) and guanidine sulfamate (B) are exhausted into the fiber material (hereinafter referred to as steps). b)).

  Examples of the method of step a include the following. By immersing the fiber material in a bath containing a flame retardant processing agent or a processing solution diluted with water, the phosphorus compound (A) is imparted to the fiber material, and the fiber material is immersed at 80 ° C. or higher ( When the temperature is 100 ° C. or higher, under heat treatment), heat treatment is performed for 2 to 120 minutes to impart durability. The concentration of the phosphorus compound (A) in the bath when treating the fiber material is preferably 1 to 30% by weight, more preferably 1 to 20% by weight, and even more preferably 2 to 20% by weight. When the treatment temperature in the state where the fiber material is immersed is 80 ° C. or higher, the amorphous region of the fiber material relaxes or swells, and the phosphorus compound (A) and guanidine sulfamate (B) are likely to adhere, and preferably 90 ° C. More preferably, it is -150 degreeC. Step a can be performed using, for example, a liquid dyeing machine, a beam dyeing machine, a cheese dyeing machine, or the like.

  Examples of the process b include the following. Immerse the fiber material in a bath containing a flame retardant processing agent or a processing solution diluted with water (or spray the above flame retardant processing agent or a processing solution diluted with water on the fiber material by spraying etc. ), Phosphorus compound (A) and guanidine sulfamate (B) are applied at room temperature, and then the fiber material taken out of the bath is heat-treated at 90 to 220 ° C. for 10 seconds to 120 minutes and dried. The heat treatment may be either dry heat treatment or wet heat treatment. The density | concentration of the phosphorus compound (A) in the bath at the time of processing to a fiber material is the same as that of the case of the process a. In some cases, in order to impart durability, the fiber material may be further heat treated to exhaust the phosphorus compound (A) and guanidine sulfamate (B) into the fiber material. The temperature at this time is preferably 100 to 220 ° C., more preferably 160 to 200 ° C., because the amorphous region of the fiber material relaxes or expands, and the phosphorus compound (A) easily adheres. When the temperature is lower than 100 ° C., exhaust of the phosphorus compound (A) into the fiber material is insufficient, and the durability and flame retardancy may be inferior. On the other hand, if the temperature is higher than 220 ° C., the fiber material may be thermally deteriorated and the strength may be reduced. The adhesion can be performed by a padding method, a spray method, a coating method, or the like. The heat treatment time is usually 10 seconds to 120 minutes, and either dry heat treatment or wet heat treatment may be used. Step b is, for example, spray-dry method, pad-dry method, spray-cure method, pad-cure method, spray-dry-cure method, pad-dry-steam method, pad-steam method, pad-dry-cure. The method etc. are mentioned.

  In the method for producing a flame-retardant fiber of the present invention, for example, at least any one of the above-described steps a and b may be performed, but the same step may be processed multiple times or the steps a and b may be combined. Higher flame retardancy can be imparted by the treatment. Among these, the phosphorus compound (A) and the guanidine sulfamate (B) can be efficiently exhausted into the fiber material, so that the step b is preferable. Moreover, you may use another process process together using another flame retardant different from the phosphorus compound (A) of this invention.

  Moreover, in the manufacturing method of the flame-retardant fiber of this invention, by performing a process process using the flame-retardant processing chemical | medical agent whose pH in 25 degreeC was adjusted to 6-8, the deterioration of a fiber material with time is suppressed. And the occurrence of metal rust can be suppressed. In particular, when the polymer material contains a polymer elastic body, it is preferable because deterioration of the polymer elastic body and strength of the fiber material containing the polymer elastic body can be suppressed.

  In the method for producing a flame-retardant fiber of the present invention, other components than the phosphorus compound (A) of the present invention and guanidine sulfamate (B) may be added within a range not impairing the effects of the present invention. Examples of other components include other flame retardants except for the phosphorus compound (A) (triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl phenyl phosphate, xylenyl phenyl phosphate, cresyl xylenyl phosphate Phosphate esters such as phenyl orthoxenyl phosphate, naphthyl phosphate, alkyldiphenyl phosphate; condensed phosphate esters such as resorcinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), resorcinol bis (dixylenyl phosphate); Phosphinic acid ester; Phosphite ester; Hypophosphite ester; Phosphine oxide; Phosphine; Phosphonium salt; Phosphate ester amide; Acid ester; chlorine-containing condensed phosphate ester; phosphorus-containing polyester resin; phosphazene; ammonium polyphosphate, melamine-coated ammonium polyphosphate, melamine resin-coated ammonium polyphosphate, silicone-coated ammonium polyphosphate, acidic phosphate ammonium salt, acidic phosphoric acid Phosphate flame retardants such as ester guanidine salts, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, dimelamine polyphosphate, ethylenediamine phosphate, carbamate phosphate, guanidine phosphate, guanylurea phosphate; decabromodiphenyl ether, Brominated flame retardants such as ethylenebis (pentabromodiphenyl), ethylenebis (tetrabromophthalimide), tris (tribromophenoxy) triazine, etc .; melamine, dicyandiamide, (2-hydroxyethyl) isocyanurate, nitrogen-based flame retardants such as melamine cyanurate; ammonium sulfamate; ammonium sulfate; magnesium hydroxide; aluminum hydroxide; hydroxyl-containing compounds such as pentaerythritol, dipentaerythritol, starch, sorbitol) , Dyes (basic dyes, disperse dyes, etc.), carrier agents (aromatic halogen compounds, N-alkylphthalimides, aromatic carboxylic acid esters, methylnaphthalene, diphenyl, diphenyl esters, naphthol esters, phenol ethers, hydroxydiphenyls, etc.), Surfactant, pH adjuster, water-soluble solvent, crosslinking agent, smoothing agent, sewing agent, anti-slip agent, deodorant, antibacterial agent, thickening agent, softener, antistatic agent, water repellent Oil, hard finish, binder, coating Ing processing agents, ultraviolet absorbers, antifouling agents, hydrophilizing agents and the like. You may give these 1 type, or 2 or more types.

The flame-retardant fiber of this invention should just provide the phosphorus compound (A) and the guanidine sulfamate (B) to the fiber material. The amount of the phosphorus compound (A) adhering to the fiber material is not particularly limited because it varies depending on the type and structure of the fiber material, the type of other fiber processing agent adhering to the fiber material, the amount of adhesion, etc. Preferably it is 0.1-20 weight% with respect to the whole, More preferably, it is 0.5-15 weight%, More preferably, it is 1-15 weight%, Especially preferably, it is 5-15 weight% . If the adhesion amount of the phosphorus compound (A) is less than 0.1% by weight, sufficient flame retardancy may not be imparted to the fiber material. On the other hand, if the adhesion amount of the phosphorus compound (A) is more than 20% by weight, the resulting flame-retardant fiber may be unsatisfactory and the flame-retardant effect may be saturated. The amount of guanidine sulfamate (B) attached to the fiber material is not particularly limited, and is preferably 0.1 to 6% by weight, more preferably 0.1 to 3% by weight, based on the entire fiber material. More preferably, it is 0.5 to 3% by weight, and particularly preferably 0.5 to 2% by weight. When the adhesion amount of guanidine sulfamate (B) is less than 0.1% by weight, sufficient flame retardancy may not be imparted to the fiber material. On the other hand, when the adhesion amount of guanidine sulfamate (B) is more than 6% by weight, the resulting flame-retardant fiber is likely to be ignited, and even if the hot melt part of the fiber material is melted and dropped (drip), the ignition part May remain in the fiber material and combustion may continue. In addition, guanidine sulfamate crystallizes over time and may whiten.
Here, the adhesion amount of the phosphorus compound (A) and guanidine sulfamate (B) to the entire fiber material means an amount calculated from the amount of acetone extract or water extract of the flame retardant processed fiber material.

  The flame retardant fiber of the present invention may be obtained by adding a phosphorus compound (A) and guanidine sulfamate (B) to the fiber material. If the pH of the fiber material is in the range of 4 to 8, the fiber over time It is preferable because deterioration of the material can be suppressed and generation of metal rust can be suppressed. In particular, when the polymer material contains a polymer elastic body, it is preferable because deterioration of the polymer elastic body and strength of the fiber material containing the polymer elastic body can be suppressed.

  The present invention is described in detail in the following examples and comparative examples, but the present invention is not limited thereto.

〔Evaluation methods〕
(1) Flame retardancy according to JIS L 1091 JIS L 1091 A-1 method for a fiber material that has been flame-retardant processed and a sample that has been subjected to water washing or dry cleaning 5 times under the following conditions: The flame retardancy was measured by both the micro burner method) and the JIS L 1091 D method (coil method).
In the micro burner method, after 1 minute heating and after 3 seconds of flame, “○” indicates that the residual flame is 3 seconds or less, the residual dust is 5 seconds or less, and the carbonized area is 30 cm ² or less. It was set as “x”. In the coil method, the case where the number of times of flame contact was 3 times or more was “◯”, and the case where it was 2 times or less was “x”.

<Water washing>
According to JIS K 3371, 1 g / L of weak alkaline first-class detergent was used, and the fire-retardant processed fiber material was washed with water at 60 ± 2 ° C. for 15 minutes at a bath ratio of 1:40, and then at 40 ± 2 ° C. for 5 minutes. Rinse was performed three times, centrifugal dehydration was performed for 2 minutes, and then a hot-air drying process at 60 ± 5 ° C. was performed once, which was performed a total of 5 times.

<Dry cleaning>
Using 12.6 mL of tetrachloroethylene and 0.265 g of charge soap (nonionic surfactant / anionic surfactant / water = 10/10/1 (weight ratio)) per 1 g of the flame-retardant processed fiber material, 30 ± 2 ° C. The treatment for 15 minutes was made one time, and this was performed 5 times in total.

(2) Flame retardancy by UL-94 VTM (thin material vertical combustion test) For samples after finishing of flame retardant processed fiber materials, it is difficult to comply with the method specified in UL-94 VTM (thin material vertical combustion test). Flammability was evaluated. This is the remaining flame time after three seconds indirect flame the burner flame to the lower end center of the sample held vertically t ^{1 (sec),} the flame of the burner to further lower end of the sample at the time the after flame is extinguished The after-flame time t ² (second) after indirect flame for 3 seconds was used, and t ¹ and t ² were measured 5 times using 5 samples. Also, a total of 5 times t ^1, t ² of the remaining flame time of, determine the remaining flame time meter (s). However, it was set to x when the after-flame to the 125-mm mark line was shown, and it was described as d when the labeling cotton under the sample was ignited by melting and dropping (drip). Based on the measurement results of 5 times, it was classified into VTM-0, 1, 2 However, those that did not meet the flame retardant standards were marked with “x”.

(3) Measurement of pH (a) Flame retardant processing chemical (processing fluid)
The pH of the flame retardant processing chemical at 25 ° C. was measured using a glass electrode pH meter (NavihF-51, manufactured by Horiba, Ltd.).
(B) Fiber material Put 50 mL of distilled water in a 200 mL flask with a glass stopper, boil gently for 2 minutes, move the flask away from the heat source, and put 5 g of test piece (fiber material) into 1 cm x 1 cm pieces into the flask. The flask was stoppered, and the stopper was occasionally loosened and allowed to stand for 30 minutes while shaking the flask. Then, the pH at 25 ° C. was measured using a glass electrode pH meter (manufactured by NavihF-51, Horiba, Ltd.). .

(4) Fastness to friction A fiber material fire-retardant processed in the same dyeing bath using a dye was tested by JIS L 0849 with a friction tester type II and evaluated by a series. The higher the series, the better the frictional fastness.

(5) Rust test A staple core was attached to a flame-retardant processed test piece, and left for 4 weeks in an environment of a temperature of 70 ° C. and a relative humidity of 95% RH, and the occurrence of rust was examined.
(6) Adhering amount About 5 g of a test piece was taken from a finished sample of a fiber material subjected to flame-retardant processing, an absolute dry mass was determined, and then lightly put into a Soxhlet extractor defined in JIS R 3503. Put 100 ml of acetone in the attached flask, heat it for 3 hours to keep the extract weakly boiling on the water bath (heating is about once every 10 minutes, and the solvent is refluxed through the siphon tube), and then accumulate in the sample part. The solution was returned to the flask. After concentrating the contents of the flask to 5 ml or less, the flask was returned to the balance bottle whose absolute dry mass was determined in advance. The flask used for the extraction was washed with acetone at about 40 ° C., the washing solution was put into a balance bottle, the acetone was volatilized, the remaining dry mass was weighed, and the phosphorus compound (A ) Was determined (weight%). Next, the fiber material after having been extracted with acetone was lightly put into a Soxhlet extractor defined in JIS R 3503. Place 100 ml of distilled water in the attached flask and heat for 3 hours to the extent that the extract remains weakly boiling on the oil bath (heating is performed once every 10 minutes and the solvent is refluxed through the siphon tube). The accumulated solution was returned to the flask. After concentrating the contents of the flask to 5 ml or less, the flask was returned to the balance bottle whose absolute dry mass was determined in advance. The flask used for the extraction was washed with distilled water at about 40 ° C., the washing solution was put into a scale bottle, the water was volatilized, the remaining dry mass was weighed, and guanidine sulfamate per fiber material. The adhesion amount (% by weight) of (B) was determined. However, when components other than phosphorus compound (A) or guanidine sulfamate (B) are contained in the residue extracted with acetone or water, they are included in the residue using appropriate equipment such as NMR and liquid chromatography. The amount of phosphorus compound (A) or guanidine sulfamate (B) was determined, and the adhesion amount (% by weight) of phosphorus compound (A) or guanidine sulfamate (B) per fiber material was calculated.

(Examples 1-9)
Prepare flame retardant processing chemicals (working fluids) for each example and perform flame retardant processing under the conditions shown below. For the resulting fiber materials, pH, adhesion, flame retardancy, friction fastness, rust The test was measured.
<Flame retardant processing>
A dyeing bath containing a polyester 80% / polyurethane 20% knit (textile material) using a mini-color dyeing machine (made by Tecsum Giken) and 2% owf of disperse dye Kayalon Polyester Black AL 167 (made by Nippon Kayaku Co., Ltd.) Then, the mixture was treated for 30 minutes under the conditions of a bath ratio of 1:15, pH 4.5, and a temperature of 120 ° C. Next, a bath containing 1 g / L of Marvelin S-1520 (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), hydrosulfite 2 g / L, and soda ash 2 g / L as a soaping agent, with a bath ratio of 1:15 and a temperature of 80 ° C. Then, it was soaped for 20 minutes, washed with water, and dried at a temperature of 90 ° C. for 60 minutes to obtain a dyed fabric.
Next, each component of the compounding amount (parts by weight) shown in Tables 1 and 2 was mixed to obtain a flame retardant processing chemical (processing liquid). Table 1 shows the pH at 25 ° C. of the flame retardant processing chemical (processing fluid) of each Example. Immerse this dyed cloth in the working fluid, squeeze with mangle (squeezing rate 90%), dry at 110 ° C. for 3 minutes, cure at 180 ° C. for 1 minute, flame retardant polyester 80% / polyurethane 20% fiber Got. About the obtained fiber material, pH, adhesion amount, flame retardance, friction fastness, and a rust test were measured. The results are shown in Tables 1 and 2.

(Comparative Examples 1-7)
Flame retardant processing was performed in the same manner as in Examples 1 to 9, except that a flame retardant processing chemical (processing fluid) obtained by mixing the components shown in Tables 3 and 4 was used. About the obtained fiber material, pH, adhesion amount, flame retardance, friction fastness, and a rust test were measured. The results are shown in Tables 3 and 4.
In addition, in the flame-retardant processing chemical | medical agent (processing liquid) of the comparative example 5, the anilino diphenyl phosphate dispersion liquid was prepared as follows.

(Preparation of anilinodiphenyl phosphate dispersion)
40 parts by weight of anilinodiphenyl phosphate and 3.5 parts by weight of sodium dioctylsulfosuccinate were mixed with 25 parts by weight of water. This mixture was charged into a mill filled with glass beads having a diameter of 0.3 mm, pulverized until the average particle diameter of the anilinodiphenyl phosphate became 0.37 μm, and then non-volatile when dried at a temperature of 105 ° C. for 30 minutes. An anilinodiphenyl phosphate dispersion was prepared by adjusting the partial concentration to 40% by weight.

  In Examples 1 to 9, after processing (UL-94 method), the afterflame time is small, the flame retardancy satisfying the standard of VTM-2 is exhibited, and the friction fastness is also excellent. In Examples 1 to 5 and Examples 7 to 9, processing is completed, and after 5 times of water washing and after 5 times of dry cleaning, both show extremely durable flame retardancy. On the other hand, Comparative Examples 1 to 7 generally have poor flame retardancy and / or friction fastness.

Claims (8)

A flame retardant processing agent used for imparting flame retardancy to a fiber material, comprising at least a phosphorus compound (A) represented by the following chemical formula (1), guanidine sulfamate (B) and water, The flame retardant processing chemical | medical agent whose content rate of guanidine sulfamate (B) is 1 to 30 weight% with respect to a phosphorus compound (A).

(Wherein R ¹ , R ² , R ³ and R ⁴ are the same or different alkyl groups, and x represents 0 or 1)   The flame retardant processing agent according to claim 1, wherein the fiber material is a fiber material that includes at least fibers having a large amount of crystalline regions and may further include fibers having a large amount of non-crystalline regions.   The flame-retardant processing agent according to claim 1 or 2, wherein the fiber material is a fiber material containing at least a hot-melt fiber.   The flame retardant processing agent according to any one of claims 1 to 3, wherein the flame retardant processing agent has a pH of 6 to 8 at 25 ° C.   The flame-retardant processing chemical according to any one of claims 1 to 4, wherein the fiber material is a fiber material containing at least a polymer elastic body.   A flame retardant fiber obtained by treating the fiber material with the flame retardant processing agent according to any one of claims 1 to 5, wherein an adhesion amount of the phosphorus compound (A) to the entire fiber material is 0.1 to 20 wt. %, And the amount of guanidine sulfamate (B) attached is 0.1 to 6% by weight.   The flame-retardant fiber according to claim 6, wherein the fiber material treated with the flame-retardant processing chemical has a pH of 4 to 8. The manufacturing method of a flame-retardant fiber including the process of processing the flame-retardant processing chemical | medical agent in any one of Claims 1-5 to a fiber material.