JP4348407B2 - Flame retardant processing chemical, flame retardant fiber and method for producing the same - Google Patents

Description

  The present invention relates to a flame retardant processing chemical, a flame retardant fiber, 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. Moreover, since the organic phosphorus compound has a low molecular weight, it has poor heat resistance and has a problem of fogging. In order to solve such a problem, it has been proposed to use a diphosphate compound having a large molecular weight as a flame retardant. Patent Documents 1 to 3 disclose, for example, a flame retardant processing method in which resorcinol bis (diphenyl phosphate) is imparted to a fiber material as a phosphorus flame retardant.

  Patent Document 4 discloses a flame retardant processing method in which a solution in which tetra (2,6-dimethylphenyl) -m-phenylene phosphate is dispersed as a phosphorus flame retardant is imparted to a fiber material as a flame retardant. Patent Document 5 discloses a flame retardant processing method in which a solution in which naphthyl diphenyl phosphate is dispersed as a phosphorus flame retardant is imparted to a fiber material as a flame retardant.

Japanese Unexamined Patent Publication No. 2000-328445 Japanese Unexamined Patent Publication No. 2002-88368 Japanese Unexamined Patent Publication No. 2005-15947 Japanese Unexamined Patent Publication No. 2001-254268 Japanese Unexamined Patent Publication No. 2006-70417

  However, since resorcinol bis (diphenyl phosphate) disclosed in Patent Documents 1 to 3 has a phosphorus-oxygen single bond (phosphate ester group) in terms of chemical structure, it is easily hydrolyzed and phosphoric acid generated by hydrolysis Has the problem of causing fiber degradation. Further, since resorcinol bis (diphenyl phosphate) is liquid at room temperature, the dyeing fastness such as friction fastness is lowered. Moreover, the flame retardant processing agent disclosed in Patent Document 3 is slightly improved in hydrolyzability in the flame retardant processing agent by making it a self-emulsifying type of resorcinol bis (diphenyl phosphate). There is a problem of degrading the fiber material over time due to hydrolysis. In general, it is treated in a dye bath to obtain durability and flame resistance for washing and dry cleaning, but resorcinol bis (diphenyl phosphate) has a large molecular weight, so it has poor adhesion to fiber materials and has sufficient durability and flame resistance. Cannot be granted. Although the flame retardant processing agent disclosed in Patent Document 4 has good hydrolysis resistance of tetra (2,6-dimethylphenyl) -m-phenylene phosphate, it has a high molecular weight and is sterically bulky. Adhesion to water is poor and durability and flame resistance are also poor. In addition, since the flame retardant processing agent disclosed in Patent Document 5 has a melting point of naphthyl diphenyl phosphate of about 60 ° C., when used for car seats in vehicles, the flame retardant melts and dyeing fastness such as friction fastness is obtained. Degradation occurs. Moreover, it is remarkably inferior in light resistance and is not practical.

  Thus, all the conventional flame retardants have advantages and disadvantages in performance.

  The subject of the present invention is used to impart flame retardancy to a fiber material, good flame retardancy can be obtained even if the amount used is small, other physical property degradation can be suppressed, and product stability is excellent. A flame-retardant processing agent; a method for producing a flame-retardant fiber including a step of treating with the flame-retardant processing agent; and providing a flame-retardant fiber obtained by the production method.

  As a result of diligent investigations to solve the above problems, the present inventors have used a flame retardant processing agent without reducing flame retardancy by reducing the particle size of a specific phosphorus compound that is a flame retardant component. The inventors have found that the amount can be reduced, other physical properties can be suppressed, and the use of a surfactant in combination improves the product stability and solves the above-mentioned problems, thus reaching the present invention.

（式中、Ｒ^１、Ｒ^２、Ｒ^３は同一または異なるものであり、炭素数１〜２４のアルキル基、炭素数２〜２２のアルケニル基、炭素数５〜６の脂環アルキル基、置換基を有しても良いアリール基またはアラルキル基を表す。） That is, the flame retardant processing agent according to the present invention is represented by the following chemical formula (1), a phosphorus compound (A) having a melting point of 130 ° C. or higher, a surfactant comprising an anionic surfactant and a nonionic surfactant ( B) and a flame retardant processing agent containing water and imparting flame retardancy to the fiber material, wherein the median particle size (D ₅₀ ) of the phosphorus compound (A) is 1 μm or less Ah is, the anionic surfactant comprises mandatory aromatic sulfonate formalin condensate salt, said nonionic surfactant is a polyoxyalkylene alkyl aryl ethers, polyoxyalkylene castor oil ethers, polyoxyalkylene hardened castor oil ether And at least one selected from polyoxyalkylene fatty acid esters.

(In the formula, R ¹ , R ² and R ³ are the same or different, and are an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, an alicyclic alkyl group having 5 to 6 carbon atoms, and substitution. Represents an aryl group or an aralkyl group which may have a group.)

In the flame retardant processing chemical of the present invention, it is preferable that it is at least one of the following 1) to 4 ).
1) The anionic surfactant further includes a polyoxyalkylene alkylaryl ether sulfate salt.
2 ) The contents of the phosphorus compound (A) and the surfactant (B) are 20 to 70% by weight and 3 to 20% by weight, respectively, of the total flame retardant processing chemical, and the phosphorus compound (A) is the interface. It is in a state of being dispersed in water by the active agent (B).
3 ) The contents of the phosphorus compound (A) and the surfactant (B) are 30 to 60% by weight and 5 to 15% by weight, respectively, of the total flame retardant processing chemical, and the phosphorus compound (A) is the interface. It is in a state of being dispersed in water by the active agent (B).
4 ) A fiber material in which the fiber material includes at least fibers having a large number of crystal regions and may further include fibers having a large number of non-crystal regions.

The manufacturing method of the flame-retardant fiber concerning this invention includes the process of processing the said flame-retardant processing chemical | medical agent into a fiber material.
In the method for producing a flame-retardant fiber of the present invention, the following A) and / or B) are preferable.
A) A fiber material in which the fiber material includes at least fibers having a large number of crystal regions and may further include fibers having a large number of non-crystal regions.
B) The treatment is performed under the conditions of a treatment temperature of 80 ° C. or more and a treatment time of 2 to 120 minutes by immersing the fiber material in a bath containing the flame retardant processing agent.
The flame-retardant fiber according to the present invention is obtained by the above production method.

  The flame retardant processing agent of the present invention is used for imparting flame retardancy to a fiber material, and can obtain good flame retardancy even if the amount used is small. Other physical property deterioration caused by use can also be suppressed. That is, the flame retardant processing agent of the present invention is less likely to cause deterioration of the fiber material due to the treatment, texture, dyeing fastness, friction fastness, light fastness, etc., and durable flame retardancy for washing and dry cleaning. The load on the environment and the human body is reduced, and the product stability is excellent.

  Since the method for producing a flame retardant fiber of the present invention is processed using the above flame retardant processing chemical, as shown above, good flame retardancy can be obtained, and other physical property degradation caused by the phosphorus compound is reduced. Is also suppressed.

[Flame retardant chemicals]
The flame retardant processing agent of the present invention is a composition used for imparting flame retardancy to a fiber material.
The fiber material 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, copolymer of monomers thereof, etc.) Is preferable because it is excellent in the adsorptivity of triphenylphosphine oxide contained in the flame retardant processing chemical and the durability and flame retardancy is improved. Among them, a fiber material containing at least an aromatic polyester or a cationic dyeable polyester is more preferable because it has excellent adsorbability for the phosphorus compound (A) described later.

  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.

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 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 regions and a fiber having a large amount of non-crystalline regions, it may be either blended or woven. The form of the fiber material is not limited, and examples thereof include yarn, woven fabric, knitted fabric, nonwoven fabric, rope, and string.
The flame retardant processing agent of the present invention contains a phosphorus compound (A), a surfactant (B) composed of an anionic surfactant and / or a nonionic surfactant, and water. These components are components that do not contain halogen and can reduce the load on the environment and the human body.

The phosphorus compound (A) used by this invention is a component which improves a flame retardance by processing to a fiber material. Further, since the phosphorus compound (A) has a molecular structure that is difficult to hydrolyze, it does not cause deterioration of the fiber material seen in the phosphate ester flame retardant as described in the background art, and its melting point is 130 ° C. or higher. Because it is a solid, it is possible to maintain dispersion stability in a flame retardant treatment in a bath at 80 ° C. or higher, and there is no dye pull-out action even when applied to a fiber material. It is a component with excellent fastness.
Further, the molecular weight of the phosphorus compound (A) is not particularly limited, but preferably 250 to 500, more preferably 250 to 400, which has durability and flame retardancy for washing and dry cleaning.

The phosphorus compound (A) is represented by the chemical formula (1). In chemical formula (1), it is preferable that at least one of R ¹ , R ^2, and R ³ is an aryl group or an aralkyl group because adhesion to a fiber material is excellent. More preferably, all of R ¹ , R ² and R ³ are aryl groups or aralkyl groups. Examples of such phosphorus compounds (A) include triphenylphosphine oxide, tris (2-methylphenyl) phosphine oxide, Tris (4-methylphenyl) phosphine oxide, tris (2,6-dimethylphenyl) phosphine oxide, tris (2,6-dimethoxyphenyl) phosphine oxide, tribenzylphosphine oxide, 2- (diphenylphosphinyl) hydroquinone, etc. Can be mentioned.

The median particle size (D ₅₀ ) of the phosphorus compound (A) is 1 μm or less, and is excellent in stability over time, and the effect of the invention is more clearly obtained. More preferably, it is 0.2-0.6 micrometer. When the median particle size of the phosphorus compound (A) is more than 1 μm, the effects of the present invention cannot be obtained, and the stability over time is inferior.
In the present invention, the median particle diameter (D ₅₀ ) means the median value (median value) of the particle diameter based on the volume of the phosphorus compound (A).

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, 20 to 70 weight% is preferable with respect to the whole flame-retardant processing chemical | medical agent, and it is 30 to 60 weight% Further preferred. When the content of the phosphorus compound (A) is less than 20% by weight, there are too many water and other components, which may cause problems in the production, storage, stability, and performance of the flame retardant processing chemical. On the other hand, if the content of the phosphorus compound (A) exceeds 70% by weight, it may be difficult to obtain a stable flame retardant processing chemical.
Surfactant (B) consists of an anionic surfactant and / or a nonionic surfactant, and is a component which improves the dispersibility of a phosphorus compound (A). The phosphorus compound (A) generally has a tendency to agglomerate and is difficult to make into fine particles. However, the surfactant (B) reduces the surface tension between the phosphorus compound (A) and water and wets the phosphorus compound (A). By being in the state, it is a component that can efficiently make the phosphorus compound (A) fine particles. The surfactant (B) is a component that suppresses aggregation of the finely divided phosphorus compound (A) with time and improves the stability of the flame retardant processing chemical. By containing the surfactant (B), the flame retardant processing agent of the present invention can make the phosphorus compound (A) fine particles and dispersed in water.

  The anionic surfactant is not particularly limited, and examples thereof include alkyl sulfate salts, alkyl aryl sulfate salts, polyoxyalkylene alkyl ether sulfate salts, polyoxyalkylene alkyl aryl ether sulfate salts (polyoxyalkylene tristyryl phenyl ether sulfate salts, Polyoxyalkylene distyryl phenyl ether sulfate salt, polyoxyalkylene styryl phenyl ether sulfate salt, polyoxyalkylene nonyl phenyl ether sulfate salt, etc.), polyoxyalkylene alkyl polyhydric alcohol ether sulfate salt, alkyl sulfonate salt, alkyl aryl sulfonate salt ( Xylene sulfonate salt, toluene sulfonate salt, cumene sulfonate salt, etc.), Alkyl aryl disulfonate salts (alkyl diphenyl disulfonate salts, etc.), alkyl sulfosuccinates, alkyl phosphate salts, alkyl aryl phosphate salts, polyoxyalkylene alkyl ether phosphate salts, polyoxyalkylene alkyl aryl ether phosphate salts, polyoxyalkylene alkyl compounds Monohydric alcohol ether phosphate salt, aromatic sulfonic acid formalin condensate salt (naphthalene sulfonate formalin condensate salt, etc.), polyoxyalkylene alkyl ether carboxylate salt, polycarboxylate, funnel oil, lignin sulfonate, etc. It is done. When the anionic surfactant is a salt, it may be an alkali metal salt, alkaline earth metal salt, ammonium salt, organic amine salt, or the like. These anionic surfactants may be used alone or in combination of two or more.

  Among these anionic surfactants, polyoxyalkylene alkylaryl ether sulfate salts, alkylaryl sulfonate salts, alkylaryl disulfonate salts, and aromatic sulfonate formalin condensate salts are preferable in terms of excellent dispersibility. The oxyalkylene alkylaryl ether sulfate salt, alkylaryl sulfonate salt and aromatic sulfonate formalin condensate salt are excellent in dispersibility, and in the case of producing a flame retardant processing chemical, the phosphorus compound (A) is efficiently finely divided. It is more preferable at the point which can be made into. In addition, the aromatic sulfonate formalin condensate salt is more preferable in that it can suppress the aggregation of the finely divided phosphorus compound (A) with time and improve the stability of the flame retardant processing chemical.

  The nonionic surfactant is not particularly limited. For example, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl aryl ether (polyoxyalkylene tristyryl phenyl ether, polyoxyalkylene distyryl phenyl ether, polyoxyalkylene styryl phenyl ether, Polyoxyalkylene nonylphenyl ether, etc.), polyoxyalkylene alkylamine, polyoxyalkylene alkylamide, polyoxyalkylene fatty acid ester, polyoxyalkylene castor oil ether, polyoxyalkylene hydrogenated castor oil ether, polyoxyalkylene polyhydric alcohol ether, etc. Is mentioned. These nonionic surfactants may be used alone or in combination of two or more.

Among these nonionic surfactants, polyoxyalkylene alkyl aryl ethers, polyoxyalkylene castor oil ethers, polyoxyalkylene hydrogenated castor oil ethers, and polyoxyalkylene fatty acid esters are preferable in terms of excellent dispersibility. Castor oil ether, polyoxyalkylene hydrogenated castor oil ether, and polyoxyalkylene fatty acid ester are excellent in dispersibility, and in the production of flame retardant processing chemicals, the phosphorous compound (A) can be made into fine particles efficiently. Further, it is more preferable in that it can be suppressed by agglomeration of the finely divided phosphorus compound (A) with time and the stability of the flame retardant processing chemical can be improved.
In the whole nonionic surfactant contained in the flame retardant processing agent of the present invention, the HLB defined by Griffin's formula is in the range of 11 to 15, and the cloud point of the 1% by weight aqueous solution of the used nonionic surfactant Is preferably 10 ° C. or higher because the dispersibility of the phosphorus compound (A) is excellent.

  Although there is no limitation in particular about the content rate of surfactant (B) in the flame-retardant processing chemical | medical agent of this invention, 3-20 weight% is preferable with respect to the whole flame-retardant processing chemical | medical agent, and is 5-15 weight%. And more preferred. When the content of the surfactant (B) is less than 3% by weight, it may be difficult to obtain a stable flame retardant processing chemical. On the other hand, when the content of the surfactant (B) is more than 20% by weight, the fastness is lowered when a flame retardant processing chemical is used, or the slow dyeing effect is increased when used in combination with dyeing. There is.

The flame retardant processing agent of the present invention is not particularly limited as long as it contains a phosphorus compound (A), a surfactant (B) and water, but other than this within the range not impairing the effect of the present invention. May be included.
Examples of the other components include solvents (methanol, ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, butyl glycol, benzyl alcohol, solfit, butyl carbitol, polyalkylene glycol, etc.), water-soluble polymers (polyvinyl alcohol). -Polyacrylate, 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 maleic anhydride copolymer, soluble starch, cationized starch, carboxymethyl starch, etc.), carrier agent (good Group halogen compounds, N-alkylphthalimides, aromatic carboxylic acid esters, methylnaphthalene, diphenyl, diphenyl esters, naphthol esters, phenol ether, hydroxydiphenyl, etc.), other flame retardants (triphenyl phosphate, tricresyl phosphate, trixylate) Phosphate esters such as nyl phosphate, cresyl phenyl phosphate, xylenyl phenyl phosphate, cresyl xylenyl phosphate, phenyl orthoxenyl phosphate, naphthyl phosphate; resorcinol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), resorcinol Condensed phosphate esters such as bis (dixylenyl phosphate); phosphite esters; hypophosphite esters; Phosphoric ester amide; Chlorine-containing phosphate ester; Chlorine-containing condensed phosphate ester; Phosphorus-containing polyester resin; Phosphazene; Hexabromocyclododecane, decabromodiphenyl ether, ethylene bis (pentabromodiphenyl), ethylene bis (tetrabromophthalimide) ), Tris (tribromophenoxy) triazine and other brominated flame retardants), ultraviolet absorbers (2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, Benzotriazole ultraviolet absorbers such as 2- (2′-hydroxy-5′-methylphenyl) benzotriazole; benzophenones such as 2-hydroxy-4-methoxybenzophenone and 2,2 ′, 4,4′-tetrahydroxybenzophenone UV absorber; 2- (4,6-diphenyl-1 3,5-triazin-2-yl) -5- (hexyloxy) -phenol, 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-octyloxyphenyl) -1, Triazine-based ultraviolet absorbers such as 3,5-triazine; benzoxazinone-based ultraviolet absorbers such as 2,2 ′-(p-phenylene) di-3,1-benzoxazin-4-one; ethyl-2-cyano-3, Cyanoacrylate ultraviolet absorbers such as 3-diphenyl acrylate and (2-ethylhexyl) -2-cyano-3,3-diphenyl acrylate; salicylate ultraviolet absorbers such as pt-butylphenyl salicylate) Can do.

  There is no limitation in particular about the content rate of said other component. By blending a small amount of the solvent, work efficiency, stability at low temperature, and emulsification dispersibility are improved due to a decrease in viscosity. However, if the content increases, problems may occur with respect to production and storage, so 20% by weight or less of the flame retardant processing chemical is preferred.

The flame retardant processing agent of the present invention can be produced by mixing the phosphorus compound (A), the surfactant (B), and water, and there is no particular limitation on the mixing method, mixing order, and the like. As a method for producing the flame retardant processing chemical of the present invention, for example, a phosphorus compound (A) having a median particle size (D ₅₀ ) of 1 μm or less is prepared in advance, and a surfactant (B) and water are mixed ( Method 1): A phosphorus compound (C) having the same physical properties as the phosphorus compound (A) except that the median particle size (D ₅₀ ) exceeds 1 μm, a surfactant (B), and water are mixed to form fine particles. Examples thereof include a method (Method 2) for dispersing and atomizing the phosphorus compound (C) using an apparatus. In Method 2, the median particle size may be further reduced by using the phosphorus compound (A) instead of the phosphorus compound (C).

In the method 2, examples of the micronizer include a bead mill, a sand grinder, and an attritor. Moreover, in the method 2, you may add additives, such as a non-drying agent, an antifoamer, and a thickener, as needed. As the phosphorus compound (C), a commercially available product may be used as it is, or may be used after coarsely forming fine particles.
The method for producing a flame retardant processing chemical of the present invention may be either method 1 or method 2 described above, but in method 1, the phosphorus compound (A) of 1 μm or less is not dissociated from the aggregated state, and the stability of the dispersed product is not good. Method 2 is preferred because it may be sufficient.

The flame retardant processing chemical of the present invention is used for imparting flame retardancy to a fiber material. Although there is no particular limitation on the form of use, it is usually diluted with water or the like.
[Flame-retardant fiber and method for producing the same]
The manufacturing method of the flame-retardant fiber of this invention includes the process (processing process) which processes the said flame-retardant processing chemical | medical agent to a fiber material.

  The treatment step is a step in which the flame retardant processing agent and the fiber material are brought into contact with each other to adhere the phosphorus compound (A) contained in the flame retardant processing agent to the fiber material. The treatment step is, for example, a treatment step (Step 1) performed by immersing a fiber material in a bath containing a flame retardant processing agent, and a treatment temperature of 80 ° C. or more and a treatment time of 2 to 120 minutes; Examples include a treatment step (step 2) in which a chemical agent is attached to the fiber material and heat treated at a temperature of 100 to 220 ° C. to exhaust the phosphorus compound (A) into the fiber material.

  In the method of Step 1, the step of attaching the phosphorus compound (A) to the fiber material is usually performed by immersing the fiber material in a bath obtained by diluting the flame retardant processing agent with water, thereby adding the phosphorus compound (A) to the fiber material. At the same time, heat treatment is performed at 80 ° C. or higher for 2 to 120 minutes with the fiber material immersed, thereby imparting durability. Although there is no limitation in particular about the dilution rate of a flame-retardant processing chemical | medical agent, it is 10 to 10,000 times normally. 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 expands, and the phosphorus compound (A) is easily attached, and more preferably at 90 ° C. to 150 ° C. is there. Step 1 can be performed using, for example, a liquid dyeing machine, a beam dyeing machine, a cheese dyeing machine, or the like.

  In the method of step 2, the fiber material is immersed in a bath obtained by diluting a flame retardant processing agent with water, the phosphorus compound (A) is attached, and optionally dried, and then the fiber material is heat-treated to obtain a phosphorus compound. (A) is exhausted into the fiber material to provide durability. 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 less 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, when the temperature is higher than 220 ° C., the fiber material may be thermally deteriorated and the strength may be lowered, which is not preferable. The adhesion can be performed by a padding method, a spray method, a coating method, or the like. The heat treatment may be either dry heat treatment or wet heat treatment. For example, a spray-dry-cure method, a pad-dry-steam method, a pad-steam method, a pad-dry-cure method, and the like can be given.

  In the method for producing a flame-retardant fiber of the present invention, for example, at least one of the process steps 1 and 2 may be performed. However, the same process may be performed a plurality of times, or the process 1 and the process 2 may be performed. By processing in combination, higher flame retardancy can be imparted. Moreover, in the manufacturing method of the flame-retardant fiber of this invention, you may use together another process process using another flame retardant different from the flame-retardant processing chemical | medical agent of this invention.

  In the method for producing a flame retardant fiber of the present invention, the fiber material may be treated together with other fiber processing agents and fiber processing aids other than the flame retardant processing agent of the present invention. Other fiber processing agents and fiber processing aids include, for example, other flame retardants except for the phosphorus compound (A), dyes (basic dyes, disperse dyes, etc.), carrier agents (aromatic halogen compounds, N-alkylphthalimides) , Aromatic carboxylic acid ester, methylnaphthalene, diphenyl, diphenyl ester, naphthol ester, phenol ether, hydroxydiphenyl, etc.), deodorant, antibacterial agent, softener, antistatic agent, water / oil repellent, hard finish, ultraviolet light An absorbent, an antifouling agent, a hydrophilizing agent, etc. can be mentioned. These may be used alone or in combination of two or more.

  In the method for producing a flame-retardant fiber of the present invention, the adhesion amount of the phosphorus compound (A), which is a flame retardant, to the fiber material is the type and structure of the fiber material, the type of other fiber processing agent attached to the fiber material, Although there is no particular limitation since it varies depending on conditions such as the amount of adhesion, it is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight with respect to the fiber material. When 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 30% by weight, the resulting flame-retardant fiber may be unsatisfactory and the flame-retardant effect may become saturated and not economical.

  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) Median particle diameter (D ₅₀ ) and volume average diameter Sampling the flame retardant processing agent obtained by microparticulation, using a laser diffraction / scattering particle size distribution measuring device LA-910 (manufactured by Horiba), The median particle diameter and volume average diameter based on volume were measured.

(2) Product stability The appearance of the flame retardant chemicals left for 1 month at 40 ° C. was visually evaluated. Precipitates and those where no separation was observed were marked with “◯”, and those where precipitation or separation was observed were marked with “x”.

(3) Flame retardancy JIS L 1091 A-1 for a fabric that has been flame-retarded with a flame retardant processing chemical and a sample that has been processed and washed five times under the following conditions with water washing or dry cleaning. Flame retardancy was measured by both the method (microburner method) and the JIS L 1091 D method (coil method).
In the micro burner method, after 1 minute of heating and after 3 seconds of flaming, “○” indicates that the after 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 weakly alkaline first-class detergent was used, and the fire retardant processed fabric 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. Rinsing was performed 3 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 30 g of flame-retardant processed fabric at 30 ± 2 ° C. The treatment for 15 minutes was performed once, and this was performed 5 times in total.

(4) Friction fastness A fabric subjected to flame-retardant processing in a dyeing bath using a dye was tested by a friction tester type II according to JIS L 0849 and evaluated by a series. The higher the series, the better the frictional fastness.

(5) Light fastness According to JIS-L-0842, the obtained polyester dyed cloth was irradiated with carbon arc fluorescence for 100 hours, and evaluated by a series. The higher the series, the better the light fastness.

[Examples 1 to 3, Reference Example 4 ]
The compounding components shown in Table 1 were added to a stirrer and sufficiently stirred and dispersed. Then, using Starmill ZRS (manufactured by Ashizawa Finetech Co., Ltd.), the obtained slurry was made into fine particles for 4 hours to prepare flame retardant processing chemicals. The POE (20) tristyrenated phenol sulfate Na salt shown in Table 1 is a polyoxyethylene tristyrenated phenol sulfate Na salt, which means that the number of repeating oxyethylene groups is 20. .
About the obtained flame-retardant processing chemical | medical agent, the median particle diameter and the volume average diameter were measured, and product stability was evaluated visually. In addition, using the obtained flame retardant processing chemicals, flame retardant processing (including dyeing and soaping) is performed under the following conditions, and the resulting fiber materials are flame retardant, fast against friction and fast against light. Was measured.
<Flame retardant processing>
Polyester tropical 100% undyed cloth is used with a mini-color dyeing machine (manufactured by Teksam Giken), disperse dye Kayalon Polyester Black AL 167 (manufactured by Nippon Kayaku Co., Ltd.) is 6% owf and flame retardant processing shown in Table 1 The treatment was performed for 30 minutes in a dyeing bath containing a drug (the amount of treatment is shown in Table 1) under conditions of a bath ratio of 1:15, pH 4.5, and a temperature of 130 ° C. Next, a soap containing a soaping agent (Matsumoto Yushi Seiyaku Co., Ltd.) 1 g / L, hydrosulfite 2 g / L, caustic soda 2 g / L, and a soaping treatment for 20 minutes under conditions of a bath ratio of 1:15 and a temperature of 80 ° C. And washed with water and dried at 170 ° C. for 1 minute to obtain flame-retardant polyester fiber.

[Comparative Examples 1-6]
Comparative flame-retardant processing chemicals were prepared in the same manner as in Examples 1 to 4 except that the blending components shown in Table 2 were used. Subsequently, using the obtained comparative flame retardant processing chemical, flame retardant processing (including dyeing and soaping) was performed in the same manner as in Examples 1 to 4, respectively. About the obtained fiber material, flame retardance, friction fastness, and light fastness were also measured.

  In Examples 1 to 4, after finishing processing, after 5 times of water washing and after 5 times of dry cleaning, both show extremely durable flame retardancy and are excellent in friction fastness and product stability. On the other hand, in Comparative Examples 1-6, product stability was bad and isolation | separation was seen. In addition, as in Comparative Example 3, the flame retardancy is improved by increasing the amount of treatment, which is about the same as in Examples 1 to 4, but the wet friction fastness and light fastness are reduced. In Comparative Examples 4 and 5, the flame retardancy and the fastness to friction are generally poor. In Comparative Example 6, the light fastness is inferior.

Industrial application fields

The flame retardant processing agent of the present invention is suitable for imparting flame retardancy to a fiber material. The flame retardant processing agent of the present invention is less likely to cause deterioration of the fiber material, texture, dyeing fastness, friction fastness, light fastness, etc. due to the treatment, and obtains durable flame retardancy for washing and dry cleaning. The load on the environment and the human body is reduced, and the product stability is excellent.

Claims (9)

A fiber material containing a phosphorus compound (A) represented by the following chemical formula (1) and having a melting point of 130 ° C. or more, a surfactant (B) composed of an anionic surfactant and a nonionic surfactant , and water. It is a flame retardant processing agent used for imparting flame retardancy to the phosphorous compound (A), wherein the phosphorus compound (A) has a median particle size (D ₅₀ ) of 1 μm or less, and the anionic surfactant is an aromatic sulfonic acid A salt of formalin condensate, and the nonionic surfactant is at least one selected from polyoxyalkylene alkylaryl ether, polyoxyalkylene castor oil ether, polyoxyalkylene hydrogenated castor oil ether, and polyoxyalkylene fatty acid ester. Including flame retardant processing chemicals.

(In the formula, R ¹ , R ² and R ³ are the same or different, and are an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, an alicyclic alkyl group having 5 to 6 carbon atoms, and substitution. Represents an aryl group or an aralkyl group which may have a group.) The anionic surface active agent comprises a polyoxyalkylene alkyl aryl ether sulfate salts further, flame retarding agent according to claim 1. The contents of the phosphorus compound (A) and the surfactant (B) are 20 to 70% by weight and 3 to 20% by weight, respectively, of the whole flame retardant processing chemical, and the phosphorus compound (A) is the surfactant. The flame-retarding chemical | medical agent of Claim 1 or 2 which exists in the state disperse | distributed in water by (B). The contents of the phosphorus compound (A) and the surfactant (B) are 30 to 60% by weight and 5 to 15% by weight of the total flame retardant processing chemical, respectively, and the phosphorus compound (A) is the surfactant. The flame-retarding chemical | medical agent in any one of Claims 1-3 which exists in the state disperse | distributed in water by (B). The flame-retardant processing agent according to any one of claims 1 to 4 , wherein the fiber material is a fiber material that includes at least fibers having a large number of crystal regions and may further include fibers having a large number of non-crystal regions. 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 into a fiber material. The method for producing flame retardant fibers according to claim 6 , wherein the fiber material is a fiber material that includes at least fibers having a large number of crystal regions and may further include fibers having a large number of amorphous regions. The flame retardant according to claim 6 or 7 , wherein the treatment is performed under conditions of a treatment temperature of 80 ° C or more and a treatment time of 2 to 120 minutes by immersing a fiber material in a bath containing the flame retardant processing agent. A method for producing fibers. To any one of claims 6-8 obtained by the production method of the flame-retardant fiber according, flame retardant fiber.