CN103649408A - Flameproofing agent for fibers, method for producing flame-retardant fiber, and flame-retardant fiber - Google Patents

Abstract

The present invention addresses the problem of providing: a flameproofing agent for fibers, which has excellent color fastness and is capable of providing a fiber material with good flame retardancy even if only a small amount of an organic phosphorus compound is used therefor, thereby reducing pot contamination and load in waste water; a method for producing a flame-retardant fiber using the flameproofing agent; and a flame-retardant fiber which is obtained by the production method. The present invention is a flameproofing agent for fibers, which contains: a tricresyl phosphate (A) that is mainly composed of tri-p-cresyl phosphate; a surfactant; and water. The weight ratio of the tri-p-cresyl phosphate in the total tricresyl phosphate (A) is 90% by weight or more.

Description

Flame-retardant processing agent for fiber, method for producing flame-retardant fiber, and flame-retardant fiber

technical field

The present invention relates to a flame-retardant processing agent for fibers, a method for producing a flame-retardant fiber, and a flame-retardant fiber.

Background technique

Conventionally, in order to impart flame retardancy to a fiber material, a flame retardant obtained by dispersing or emulsifying a halogen compound such as hexabromocyclododecane in water is generally used. However, since the adhesion efficiency of such halogen compounds to fiber materials is low, a large amount of treatment is required, and there is a problem that halogen compounds not attached to fiber materials are discharged into the environment. In addition, although the fiber material treated with a halogen compound has flame retardancy, there is a risk of generating harmful halogenated gas by burning. In this way, dehalogenation tends to be avoided as much as possible, since the trend of dehalogenation is increasing from the viewpoint of the human body and the environment.

Organophosphorus compounds are used as substitutes for halogen-based compounds, but the organophosphorus compounds disclosed in Patent Documents 1 and 2 are liquid at room temperature, so there is a possibility that color fastness such as crocking fastness may decrease due to dye bleedout. question. As such, the use of organic phosphorus compounds that are liquid at normal temperature tends to be avoided.

In recent years, in order to solve the problem of reduction in color fastness due to dye bleed, there has been a tendency to use an organophosphorus compound that is solid at normal temperature. However, since the adhesion efficiency to fiber materials is still low, a large amount of treatment is required, and there is a problem that organic phosphorus compounds not attached to fiber materials are discharged into the environment. In addition, even if the organophosphorus compound is solid at normal temperature, when the melting point or freezing point of the organophosphorus compound disclosed in Patent Documents 3 to 5 is within the dyeing temperature range (80°C to 135°C) of the polyester fiber material , The state of the organophosphorus compound also changes during dyeing, so the emulsification and dispersibility is significantly reduced, and it becomes a problem of contamination (spotting) of the fiber material and contamination of the tank (tank contamination).

In addition, the naphthyl diphenyl phosphate disclosed in Patent Document 6 does not change the state of an organophosphorus compound in the dyeing temperature range, but since its melting point is about 60° C., it is suitable for use in car seats and the like in cars. , In summer and hot areas abroad, the flame retardant will melt and ooze out, resulting in a decrease in color fastness such as rubbing fastness. In addition, the light fastness is obviously poor, and it is not practical.

prior art literature

patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2000-328445

Patent Document 2: Japanese Unexamined Patent Publication No. 2007-70751

Patent Document 3: Japanese Patent Laid-Open No. 2001-254268

Patent Document 4: Japanese Patent Laid-Open No. 2003-193368

Patent Document 5: Japanese Patent Laid-Open No. 2002-275473

Patent Document 6: Japanese Patent Laid-Open No. 2006-70417

Contents of the invention

The problem to be solved by the invention

The object of the present invention is to provide a flame retardant processing agent for fibers that is excellent in color fastness, can impart good flame retardancy even with a small amount of organophosphorus compound treated with respect to the fiber material, and can reduce tank pollution or drainage load, and use A method for producing a flame-retardant fiber using the flame-retardant processing agent, and a flame-retardant fiber obtained by the production method.

solutions to problems

The inventors of the present invention conducted intensive studies to solve the above-mentioned problems, and as a result, found that by using tricresyl phosphate (A) as the organophosphorus compound mainly composed of tricresyl phosphate, even if the treatment amount of the organophosphorus compound was small, Also, good flame retardancy can be imparted, and can body pollution and drainage load can be reduced, thereby realizing the present invention.

That is, the flame-retardant processing agent for fibers of the present invention contains tricresyl phosphate (A) mainly composed of tricresyl phosphate, a surfactant, and water, and tricresyl phosphate is contained in the above-mentioned tricresyl phosphate (A). A) The weight ratio in the whole is 90 weight% or more.

In the flame-retardant processing agent of the present invention, the melting point of the above-mentioned tricresyl phosphate (A) is preferably 65 to 80°C. In addition, the tricresyl phosphate (A) is preferably in a state of being emulsified or dispersed in water.

The flame retardant processing agent of the present invention preferably further contains triphenylphosphine oxide (B).

The weight ratio (A/B) of the tricresyl phosphate (A) to the triphenylphosphine oxide (B) is preferably 95/5 to 5/95.

In addition, it is preferable that the above-mentioned tricresyl phosphate (A) and the above-mentioned triphenylphosphine oxide (B) are in a state of being emulsified or dispersed in water.

The surfactant preferably contains at least one selected from polyoxyalkylene polycyclic aryl ether sulfates and polyoxyalkylene polycyclic aryl ethers.

The method for producing flame-retardant fibers of the present invention includes the step of treating the fiber material with the above-mentioned flame-retardant processing chemical.

In the method for producing flame-retardant fibers of the present invention, in the above-mentioned steps, the treatment amount of tricresyl phosphate (A), or when the above-mentioned flame-retardant processing agent contains triphenylphosphine oxide (B) The total treatment amount of tricresyl phosphate (A) and triphenylphosphine oxide (B) is 0.1 to 5% by weight relative to the fiber material.

The flame-retardant fiber of the present invention is a flame-retardant fiber obtained by the production method of the present invention. For the flame-retardant fiber of the present invention, it is preferable that the amount of tricresyl phosphate (A) attached, or the amount of tricresyl phosphate (A) and The total adhesion amount of triphenylphosphine oxide (B) is 0.1 to 3% by weight based on the flame-retardant fiber.

Invention effect

The flame-retardant processing agent for fibers of the present invention has excellent color fastness, can impart good flame retardancy even with a small amount of organophosphorus compound treated with respect to fiber materials, and can reduce tank pollution and drainage load.

The method for producing a flame-retardant fiber of the present invention uses the above-mentioned flame-retardant processing chemical, so that a fiber having good flame retardancy and excellent color fastness can be obtained even if the amount of organic phosphorus compound treated is small. In addition, tank pollution and drainage load can be reduced. The flame-retardant fiber of the present invention is excellent in flame retardancy and color fastness.

Detailed ways

〔Flame retardant processing agent〕

The flame-retardant processing agent for fibers of the present invention is a composition for imparting flame retardancy to fiber materials, and contains tricresyl phosphate (A) mainly composed of tricresyl phosphate, a surfactant, and water. The details will be described below.

The flame-retardant processing agent for fibers of the present invention selectively uses tricresyl phosphate among tricresyl phosphates. Tricresyl phosphate is obtained through the condensation reaction of phosphorus oxychloride and cresol. Cresol has ortho, meta, and para isomers, and isomer mixtures are usually used. Thus, the obtained tricresyl phosphate is a mixture of ortho, meta and para isomers with a freezing point of about -35°C, and its properties are liquid at normal temperature. When tricresyl phosphate is used as such an isomer mixture, exhaustion and color fastness decrease. The tricresyl phosphate (A) mainly composed of tricresyl phosphate used in the present invention refers to a product obtained by using p-cresol with high purity as a raw material and through the condensation reaction of phosphorus oxychloride and p-cresol Tricresyl phosphate is different from tricresyl phosphate which is a mixture of isomers in that it is solid at normal temperature.

The tricresyl phosphate (A) mainly composed of tricresyl phosphate used in the present invention means that the weight ratio of tricresyl phosphate in the whole tricresyl phosphate (A) is 90% by weight above substances. When the weight ratio is less than 90% by weight, the proportion of tricresyl phosphate other than tricresyl phosphate increases, the melting point of the entire tricresyl phosphate decreases, and the exhaustion and color fastness decrease. The weight ratio is preferably 95% by weight or more, more preferably 96% by weight or more, and still more preferably 97% by weight or more.

In addition, on the basis of the above, tricresyl phosphate (A) with tricresyl phosphate as the main component can also be expressed as "tricresyl phosphate other than tricresyl phosphate" in tricresyl phosphate (A) The weight ratio in the whole is 10 weight% or less. The weight ratio is preferably 5% by weight or less, more preferably 4% by weight or less, and still more preferably 3% by weight or less.

Here, examples of tricresyl phosphate other than tricresyl phosphate include: tri-o-cresol phosphate derived from o-cresol; tri-m-cresol phosphate derived from m-cresol; Tricresyl phosphate (isomer mixture) of a cresol mixture of 2 to 3 isomers among cresol, m-cresol, and p-cresol, and the like.

In this way, by using tricresyl phosphate (A) as the main component of tricresyl phosphate as an essential component, the color fastness is excellent, and even if the amount of organophosphorus compound processed with respect to the fiber material is small, it can impart Good flame retardancy can reduce tank pollution and drainage load.

In addition, when a fiber material treated with a flame retardant treatment agent (such as a vehicle interior material, etc.) is exposed to high temperature, the flame retardant treatment agent component volatilizes from the fiber surface and adheres to the nearby glass surface, etc. Fog issues with reduced transparency. By using tricresyl phosphate (A) mainly composed of tricresyl phosphate as an essential component, generation of fogging can be suppressed or reduced (excellent fogging property).

The melting point of tricresyl phosphate (A) mainly composed of tricresyl phosphate used in the present invention is preferably 65 to 80°C, more preferably 70 to 80°C, from the viewpoint of remarkably exhibiting the effects of the present application , and more preferably 75 to 78°C. Tris-p-cresyl phosphate has a melting point of about 77°C, tri-o-cresyl phosphate has a melting point of about -25°C, and tri-m-cresyl phosphate has a melting point of about 25°C. The freezing point of tricresyl phosphate of the above-mentioned ortho, meta, and para isomer mixture is about -40°C to -30°C. Therefore, the melting point of tricresyl phosphate (A) being 65 to 80°C means that tricresyl phosphate accounts for a large proportion of the whole tricresyl phosphate (A), and phosphoric acid other than tricresyl phosphate The ratio of tricresyl ester is small.

It should be noted that the melting point mentioned in the present invention refers to the melting point measured by a differential scanning calorimeter, and refers to the endothermic heat that occurs when about 5 mg of a sample is heated up at a heating rate of 10°C/min under a nitrogen atmosphere. peak temperature.

Among the non-volatile components of the flame-retardant processing agent of the present invention, the melting point derived from tricresyl phosphate (A) mainly composed of tricresyl phosphate is preferably 60° C. ~80°C, more preferably 60-75°C, even more preferably 65-75°C. When measuring the melting point of the non-volatile components of the flame-retardant processing chemical, since the non-volatile components also contain other components such as surfactants, the melting point derived from tricresyl phosphate (A) is higher than that of the above-mentioned tricresyl phosphate (A). The melting point is slightly lowered. It should be noted that the non-volatile components (also referred to as solid components) here refer to the following components: spread a certain amount of sample on an aluminum sheet, dry it at 110°C under the irradiation of an infrared lamp, and dry it for 150 seconds. The time at which the fluctuation range of the volatile components in the sample reaches 0.15% by weight is the remaining component at the end of the measurement.

In the flame-retardant processing agent of the present invention, tricresyl phosphate (A) containing tricresyl phosphate as a main component is in a state of being emulsified or dispersed in water. The median diameter (D ₅₀ ) of tricresyl phosphate (A) is not particularly limited, but is preferably 5 μm or less, more preferably 0.2 to 1.0 μm, more preferably 0.2 to 0.8 μm. When the median diameter exceeds 5 μm, stability over time and depletion performance may be poor. In the present invention, the median diameter (D ₅₀ ) refers to the median (median value) of particle diameters based on the volume of the phosphorus compound.

The content of tricresyl phosphate (A) containing tricresyl phosphate as a main component in the flame-retardant processing agent of the present invention is not particularly limited, but is preferably 1 to 50 wt. %, more preferably 10 to 50% by weight. When the content is less than 1% 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, when the content exceeds 50% by weight, it may be difficult to obtain a stable flame-retardant processing chemical.

The flame retardant processing agent of the present invention preferably further contains triphenylphosphine oxide (B). By using tricresyl phosphate (A) with tricresyl phosphate as the main component and triphenylphosphine oxide (B) in combination, tricresyl phosphate with tricresyl phosphate as the main component alone The ester (A) and the triphenylphosphine oxide (B) alone can further improve the exhaustion performance by using a synergistic effect, but the reason for this has not yet been determined. In addition, since the melting point of triphenylphosphine oxide (B) is 135°C or higher, there is no solid-liquid state change in the dyeing temperature range (80°C to 135°C), and the emulsification and dispersibility during dyeing is good. Reduce the occurrence of tank contamination. Furthermore, excellent atomization properties are exhibited by using both in combination.

In the flame-retardant processing chemical containing triphenylphosphine oxide (B), triphenylphosphine oxide (B) is also in a state of being emulsified or dispersed in water like tricresyl phosphate (A).

The median diameter (D ₅₀ ) of triphenylphosphine oxide (B) is not particularly limited, but is preferably 5 μm or less, more preferably 0.2 to 1.0 μm, from the viewpoint of excellent stability over time and further improved exhaustion. μm is more preferably 0.2 to 0.8 μm. When the median diameter of triphenylphosphine oxide (B) exceeds 5 μm, stability over time and depletion performance may be poor.

The content of triphenylphosphine oxide (B) in the flame retardant processing agent of the present invention is not particularly limited, but is preferably 0 to 50% by weight, more preferably 10 to 50% by weight, based on the entire flame retardant processing agent . When the content of triphenylphosphine oxide (B) exceeds 50% by weight, it may be difficult to obtain a stable flame-retardant processing chemical.

The weight ratio (A/B) of tricresyl phosphate (A) and triphenylphosphine oxide (B) containing tricresyl phosphate as a main component in the flame retardant processing agent of the present invention is not particularly limited. It is preferably 95/5 to 5/95 from the viewpoint of improving the exhaustion property by utilizing the synergistic effect, and reducing the pollution of the tank body or the discharge load.

A further preferred range of the weight ratio (A/B) of tricresyl phosphate (A) to triphenylphosphine oxide (B) mainly composed of tricresyl phosphate is based on the ratio of tricresyl phosphate to the fiber material (A) and triphenylphosphine oxide (B) the total amount of treatment changes. That is, depending on the amount of treatment, the range in which an excellent synergistic effect is exhibited changes.

When the total treatment amount of tricresyl phosphate (A) and triphenylphosphine oxide (B) exceeds 5% by weight relative to the fiber material, the weight ratio (A/B) is more preferably 30/70 to 5/95, further Preferably it is 40/60 to 5/95.

When the total treatment amount of tricresyl phosphate (A) and triphenylphosphine oxide (B) is 5% by weight or less relative to the fiber material, the weight ratio (A/B) is more preferably 95/5 to 10/90, More preferably, it is 95/5 to 20/80, and particularly preferably, it is 95/5 to 30/70. When the above-mentioned total treatment amount is 4% by weight or less, it is more preferably 95/5 to 20/80, still more preferably 95/5 to 40/60, particularly preferably 95/5 to 40/60. When the above-mentioned total treatment amount is 3% by weight or less, it is more preferably 95/5 to 30/70, still more preferably 95/5 to 40/60, and particularly preferably 95/5 to 60/40.

The surfactant is a component that improves the dispersibility of tricresyl phosphate (A) and triphenylphosphine oxide (B). The flame retardant processing agent of the present invention can make tricresyl phosphate (A) and triphenylphosphine oxide (B) dispersed in water by containing a surfactant.

Surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and the like, and are preferably anionic surfactants and nonionic surfactants.

The anionic surfactant is not particularly limited, and examples thereof include alkyl sulfates, alkylaryl sulfates, polycyclic aryl sulfates, polyoxyalkylene alkyl ether sulfates, and polyoxyalkylene alkylaryl ethers. Sulfates (polyoxyalkylene nonylphenyl ether sulfate, etc.), polyoxyalkylene polycyclic aryl sulfates (polyoxyalkylene tristyrylphenyl ether sulfate, polyoxyalkylene distyrylphenyl ether sulfate Salt, Polyoxyalkylene Styryl Phenyl Ether Sulfate, Polyoxyalkylene-α-Methyl Styryl Phenyl Ether Sulfate, Polyoxyalkylene Styryl-Methyl-Phenyl Ether Sulfate, Polyoxyalkylene Distyryl-methyl-phenyl ether sulfate, polyoxyalkylene distyryl-cumyl-phenyl ether sulfate, polyoxyalkylene styryl-nonyl-phenyl ether sulfate, etc.) , polyoxyalkylene alkyl polyol ether sulfate, alkyl sulfonate, α-olefin sulfonate, alkylaryl sulfonate, alkylaryl disulfonate (alkyl diphenyl disulfonic acid salt, etc.), alkyl sulfosuccinate, alkyl phosphate, alkyl aryl phosphate, polyoxyalkylene alkyl ether phosphate, polyoxyalkylene alkyl aryl ether phosphate, polycyclic aryl ether phosphate Salt, polyoxyalkylene polycyclic aryl ether phosphate, polyoxyalkylene alkyl polyol ether phosphate, aromatic sulfonate (alkylnaphthalene sulfonate, naphthalene sulfonate, dialkylnaphthalene sulfonate, Creosote sulfonate, melamine sulfonate, bisphenol sulfonate, etc.), aromatic sulfonic acid formaldehyde condensate salt (alkylnaphthalenesulfonic acid formaldehyde condensate salt, naphthalenesulfonic acid formaldehyde condensate salt, dialkyl Naphthalenesulfonic acid formaldehyde condensate salt, creosote sulfonic acid formaldehyde condensate salt, ligninsulfonic acid formaldehyde condensate salt, melaminesulfonic acid formaldehyde condensate salt, bisphenolsulfonic acid formaldehyde condensate salt, etc.), alkyl carboxylic acid Salt, polyoxyalkylene alkyl ether carboxylate, polycarboxylate, sulfonated castor oil (turkey red oil), lignosulfonate, etc.

Examples of the alkyl group constituting these anionic surfactants include methyl, ethyl, propyl, butyl, hexyl, 2-ethylhexyl, decyl, lauryl, isodecyl, tridecyl, cetyl, Wax group, stearyl group, oleyl group, behenyl group, etc. may be any one of primary alkyl group, secondary alkyl group and tertiary alkyl group, and may be straight chain or branched chain.

Similarly, examples of the alkylaryl group include tolyl, xylyl, cumyl, octylphenyl, nonylphenyl, decylphenyl, methylnaphthyl, etc., the position of the alkyl group, The quantity is unlimited.

Similarly, examples of polycyclic aryl groups include styrylphenyl, alkylstyrylphenyl, styryl-methyl-phenyl, distyryl-methyl-phenyl, styryl -cumyl-phenyl, styryl-alkyl-phenyl, tristyrylphenyl, distyrylphenyl, benzylphenyl, dibenzylphenyl, alkyldiphenyl, Diphenyl, etc., the position and number of substituents are not limited.

Similarly, examples of polyhydric alcohols include sorbitol, sorbitol, sorbite, sorbitan, pentaerythritol, trimethylolpropane, glycerin, neopentyl Glycols, xylitol, erythritol, alkanolamines, sugars, etc.

Similarly, polyoxyalkylene groups include polyoxyethylene groups, polyoxypropylene groups, polyoxybutylene groups, etc., and polyoxyethylene groups and polyoxypropylene groups are preferable. When there are two or more types of polyoxyalkylene groups, any of block adducts, alternating adducts, and random adducts may be formed. In addition, the polyoxyalkylene group preferably contains a polyoxyethylene group as an essential component. The proportion of the polyoxyethylene group in the polyoxyalkylene group is preferably 40 mol% or more, more preferably 50 mol% or more, still more preferably 60 mol% or more, particularly preferably 80 mol% or more. The added mole number of oxyalkylene groups is preferably 1-50, more preferably 3-30, and still more preferably 5-20.

When the above-mentioned anionic surfactant is a salt, it may be a hydrogen atom, an alkali metal salt, an alkaline earth metal salt, an ammonium salt, an organic amine salt, a quaternary ammonium salt, or the like. Sodium, potassium, lithium, etc. are mentioned as an alkali metal. Magnesium, calcium, barium, etc. are mentioned as an alkaline earth metal. Examples of organic amines include alkylamines (trimethylamine, triethylamine, monomethylamine, dimethylamine, etc.), alkanolamines (monoethanolamine, diethanolamine, triethanolamine, monoisopropanol amine, diisopropanolamine, triisopropanolamine, dimethylethanolamine, diethylethanolamine, etc.) and the like. As quaternary ammonium, tetramethylammonium, tetraethylammonium, tetramethanolammonium, tetraethanolammonium, etc. are mentioned. These anionic surfactants may be used alone or in combination of two or more.

Among these anionic surfactants, polyoxyalkylene polycyclic aryl ether sulfates and aromatic sulfonic acid formaldehyde condensate salts are preferred because they are excellent in dispersibility and tank contamination, and polyoxyalkylene polycyclic Aryl ether sulfates.

The cationic surfactant is not particularly limited, and examples thereof include quaternary ammonium salts (lauryl dimethyl benzyl ammonium chloride, cetyl trimethyl ammonium chloride, lauryl trimethyl ammonium chloride, stearin trimethylammonium chloride, cetylpyridinium chloride, cetylpyridinium bromide, stearamidomethylpyridinium chloride, etc.) and the like. These cationic surfactants may be used alone or in combination of two or more.

The nonionic surfactant is not particularly limited, and examples thereof include polyalkylene glycols, polyoxyalkylene alkyl ethers, polyoxyalkylene alkylaryl ethers (polyoxyalkylene nonylphenyl ethers, etc.), polyoxyalkylene Polyoxyalkylene polycyclic aryl ethers (polyoxyalkylene tristyrylphenyl ether, polyoxyalkylene distyrylphenyl ether, polyoxyalkylene styrylphenyl ether, polyoxyalkylene-α-methylstyrene phenyl phenyl ether, polyoxyalkylene styryl-methyl-phenyl ether, polyoxyalkylene distyryl-methyl-phenyl ether, polyoxyalkylene distyryl-cumyl-phenyl ether , polyoxyalkylene styryl-nonyl-phenyl ether, etc.), polyoxyalkylene alkylamine, polyoxyalkylene alkylamide, polyoxyalkylene fatty acid ester, polyoxyalkylene castor oil ether, polyoxyalkylene hydrogenated castor Sesame oil ether, polyoxyalkylene polyol ether, etc.

The alkyl group, alkylaryl group, polycyclic aryl group, polyhydric alcohol, and polyoxyalkylene group constituting these nonionic surfactants are the same as those exemplified for anionic surfactants. Examples of the fatty acids constituting these nonionic surfactants include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, montanic acid, oleic acid, linoleic acid, linolenic acid, and citric acid. , ricinoleic acid, erucic acid, etc.

Among these nonionic surfactants, polyoxyalkylene polycyclic aryl ethers are preferable because they are excellent in dispersibility and tank staining properties.

The amphoteric surfactant is not particularly limited, and examples thereof include amino acid-type (laurylaminopropionate, etc.), betaine-type (lauryldimethylammonium betaine, stearyldimethylammonium betaine, lauryldimethylammonium dihydroxyethyl betaine, etc.), etc. These amphoteric surfactants can be used alone or in combination of two or more.

The content of the surfactant in the flame-retardant processing agent of the present invention is not particularly limited, but is preferably 0.1 to 20% by weight, more preferably 1 to 10% by weight, based on the entire flame-retardant processing agent. When the content of the surfactant is less than 0.1% by weight, it may be difficult to obtain a stable flame-retardant processing chemical because the contamination of the can body is lowered. On the other hand, when the content of the surfactant exceeds 10% by weight, when a flame retardant processing chemical is used, the exhaustion property decreases or the fastness decreases, and the flame retardant processing chemical is used together in dyeing. In the case of , it will make the slow dyeing effect larger.

Any of pure water, distilled water, purified water, demineralized water, ion-exchanged water, industrial water, well water, and tap water may be used as water in the flame-retardant processing agent of the present invention.

The flame-retardant processing agent of the present invention may contain the following other components other than the above within the range that does not impair the effect of the present invention.

Examples of other components include solvents (methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methylpropanol, 1,1-dimethylethanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 1,1-dimethylpropanol, 3-methyl- 2-butanol, 1,2-dimethylpropanol, 1-hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethyl Glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, Propylene Glycol Monoethyl Ether, Tripropylene Glycol, Tripropylene Glycol Monomethyl Ether, Polypropylene Glycol, Hexylene Glycol, Benzyl Alcohol, 3-Methyl-3-Methoxy-1-Butanol (Japanese Original: Solfit), Polyalkylene Diol, acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, methyl lactate, lactic acid ethyl ester, amyl lactate, diisopropyl ether, dioxane, tetrahydrofuran, pyridine, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.), pH value Regulators, chelating agents, potential regulators, water-soluble polymers (polyvinyl alcohol, polyacrylate, methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, xanthan gum, Gum Arabic, Gelatin, Polyvinylpyrrolidone, Polyethylene Oxide, Polyacrylamide, Polystyrene Sulfonate, Polystyrene Maleic Copolymer, Methoxyethylene Maleic Anhydride Copolymer, Starch, Alginic Acid, May Melted starch, cationized starch, carboxymethyl starch, polyester resin, etc.), carrier preparation (aromatic halogen compounds (chlorobenzene, dichlorobenzene, trichlorobenzene, etc.), N-alkylphthalimide (N-methylphthalimide, N-ethylphthalimide, N-propylphthalimide, N-butylphthalimide, N-iso Propylphthalimide, N-tert-butylphthalimide, N-sec-butylphthalimide, N-phenylphthalimide, etc.), aromatic carboxylic acids Esters (benzyl benzoate, methyl benzoate, ethyl benzoate, butyl benzoate, etc.), alkylnaphthalene (1-methylnaphthalene, 2-methylnaphthalene, 2,3-dimethylnaphthalene, 1 , 3-dimethylnaphthalene, 1,4-dimethylnaphthalene, 1,5-dimethylnaphthalene, etc.), diphenyl ester, naphthol ester, phenol ether (ethylene glycol monophenyl ether, diethylene di alcohol monophenyl ether, propylene glycol monophenyl ether, dipropylene glycol monophenyl ether, etc.), hydroxydiphenyl (o-phenylphenol, p-phenylphenol, etc.) and the like.

By adding a small amount of solvent, the viscosity is reduced, thereby improving the operation efficiency, stability at low temperature, and emulsification dispersibility. However, when the content rate thereof becomes large, problems may arise in terms of production and storage. Therefore, the content of the solvent in the flame-retardant processing chemical is preferably 20% by weight or less of the flame-retardant processing chemical with respect to the entire flame-retardant processing chemical. It does not specifically limit about content rate of the said other components other than that.

In addition, the flame-retardant processing agent of the present invention may contain other flame retardants other than those described above within the range that does not impair the effects of the present invention. As other flame retardants, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri(butoxyethyl) phosphate, octyldiphenyl phosphate, tributyl phosphate, Phenyl ester, tris(xylyl) phosphate, cresyl diphenyl phosphate, xylenyl phenyl phosphate, cresyl bis(xylyl) phosphate, xylenyl xylyl phosphate Ester, Triisopropylphenyl Phosphate, Diphenyl Biphenyl Phosphate, Phenyl Biphenyl Phosphate, Orthoxenyl Diphenyl Phosphate, Diphenyl Biphenyl Phosphate ester, tri-ortho-biphenyl phosphate, tri-m-biphenyl phosphate, tri-p-biphenyl phosphate, terphenyl phosphate, α-naphthyl diphenyl phosphate, di-α-naphthylphenyl phosphate ester, β-naphthyl diphenyl phosphate, di-β-naphthyl phenyl phosphate, 2-phenoxyethyl diphenyl phosphate, 1,3,2-dioxaphosphorinane ( dioxaphophorinane)-{2-(1,1'-biphenyl-2-yloxy)}-5,5-dimethyl-2-oxide and other phosphates; resorcinol bis(diphenyl phosphate ester), resorcinol bis(xylyl phosphate), resorcinol bis(bis(xylyl) phosphate), hydroquinone bis(diphenyl phosphate), hydroquinone Bis(xylenyl phosphate), hydroquinone bis(bis(xylyl) phosphate), bisphenol A bis(diphenyl phosphate), bisphenol A bis(xylenyl phosphate) , bisphenol A bis (bis (xylyl) phosphate) and other condensed phosphates; dimethyl methanesulfonate, diethyl ethyl sulfonate, dipropyl methanesulfonate, tributyl methanesulfonate Esters, dibutyl butyl sulfonate, diphenyl benzene sulfonate, xylenol benzene sulfonate, bis-xylyl benzene sulfonate, phenyl cresol benzene sulfonate, bis[(5-ethyl- 2-Methyl-1,3,2-dioxaphosphorin-5-yl)methyl]methylphosphonate-P,P'-dioxide, (5-ethyl-2-methyl -1,3,2-dioxaphosphorinan-5-yl)phosphite ester of methyl dimethyl phosphonate-P-oxide; methyl dimethyl phosphinate, diethyl Ethyl phosphinate, propyl dimethyl phosphinate, butyl dimethyl phosphinate, phenyl diphenyl phosphinate, cresol diphenyl phosphinate, diphenyl phosphinate Hypophosphite such as cresyl ester, diethylphosphinic acid metal salt; trimethylphosphine oxide, triethylphosphine oxide, tri-n-propylphosphine oxide, tri-n-butylphosphine oxide, tri-n-hexylphosphine oxide, n-octyl phosphine oxide, tricyclohexyl phosphine oxide, tricresyl phosphine oxide, tris-3-hydroxypropyl phosphine oxide, tris(2-methylphenyl)phosphine oxide, tris(4-methylphenyl) phosphine oxide Phosphine, tris(2,6-dimethylphenyl)phosphine oxide, tris(2,6-dimethoxyphenyl)phosphine oxide, tribenzylphosphine oxide, 2-(diphenylphosphinyl) p- Phosphine oxides such as hydroquinone; 10-benzyl-9,10-dihydro-9-oxo-10λ(5)-phosphaphenanthrene=10-oxide, 10-phenoxy-9,10-dihydro -9-oxo-10λ(5)-phosphaphenanthrene=10-oxide and other phosphaphenanthrene derivatives; diphenyl=(phenylamide) Phosphate, phenyl = phosphoric acid ester amide such as bis(phenylamide) phosphate; chlorine-containing phosphate such as tris(chloropropyl) phosphate and tris(dichloropropyl) phosphate; tris(bromopropyl) phosphate Bromine-containing phosphoric acid esters such as tris(dibromopropyl)phosphate and tris(tribromoneopentyl)phosphate; chlorine-containing condensed phosphoric acid ester; phosphorus-containing polyester resin; hexaphenoxycyclotriphosphazene, hexamethyl Phosphazenes such as oxycyclotriphosphazene and hexapropoxycyclotriphosphazene; decabromodiphenyl ether, ethylene bis (pentabromobenzene), tetrabromobisphenol A, bromoethylene bis (tetra bromophthalimide), tris(tribromophenoxy)triazine, tris(2,3-dibromopropyl)isocyanurate, brominated polystyrene, hexabromocyclododecane , tetrabromocyclooctane, hexabromocycloheptane, hexabromobenzene, brominated cycloalkane, bis(3,5-dibromo-4-dibromopropyloxyphenyl) sulfone and other brominated flame retardants; Antimony trioxide, etc.

In order to improve light resistance, the flame-retardant processing agent of the present invention preferably contains an ultraviolet absorber. Examples of ultraviolet absorbers include 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5 '-Methylphenyl)benzotriazole, 2-{2'-hydroxy-3'-(3", 4", 5", 6"-tetraphthalimidomethyl)-5'- Methylphenyl}benzotriazole, 2-[2'-hydroxy-4'-(2"-hydroxybutoxyphenyl]-5-chlorobenzotriazole, 2-(2',4' -Dihydroxy-5'-benzoylphenyl)-5-chlorobenzotriazole, 2-(2',4'-dihydroxy-3'-benzoylphenyl)-5-chlorobenzotriazole Azole, 2-(3'-benzoyl-2'-hydroxy-5'-methylphenyl)benzotriazole and other benzotriazole UV absorbers; 2-hydroxy-4-methoxydiphenyl Benzophenone-based UV absorbers such as ketone, 2,2', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, etc. ; 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)-phenol, 2,4-bis(2,4-dimethylbenzene Base)-6-(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2'-hydroxy-4'-propoxyphenyl)-4,6 - Triazine-based UV absorbers such as diphenyl-s-triazine; benzoxazinone-based UV absorbers such as 2,2'-(p-phenylene)di-3,1-benzoxazin-4-one; Cyanoacrylate UV absorbers such as ethyl-2-cyano-3,3-diphenylacrylate and (2-ethylhexyl)-2-cyano-3,3-diphenylacrylate; Salicylate-based ultraviolet absorbers such as p-tert-butylphenyl salicylate and the like.

It is preferable that the content rate of the ultraviolet absorber in a flame-retardant processing chemical|chemical is 20 weight% or less with respect to the whole flame-retardant processing chemical|chemical. When the content exceeds 20% by weight, problems may arise in production and storage.

In order to improve the stability of the flame-retardant processing chemical, the flame-retardant processing chemical preferably contains a potential regulator. The potential regulator is not limited as long as it has a charge, and examples thereof include hydrochloric acid, nitrous acid, nitric acid, sulfurous acid, sulfuric acid, persulfuric acid, phosphoric acid, phosphonic acid, phosphinic acid, boric acid, hypochlorous acid, and perchloric acid. etc. Salt etc.

As the salt, a hydrogen atom, an alkali metal salt, an alkaline earth metal salt, an ammonium salt, an organic amine salt, a quaternary ammonium salt, or the like may be used. Sodium, potassium, lithium, etc. are mentioned as an alkali metal. Magnesium, calcium, barium, etc. are mentioned as an alkaline earth metal. Examples of organic amines include alkylamines (trimethylamine, triethylamine, monomethylamine, dimethylamine, etc.), alkanolamines (monoethanolamine, diethanolamine, triethanolamine, monoisopropanol amine, diisopropanolamine, triisopropanolamine, dimethylethanolamine, diethylethanolamine, etc.) and the like. As quaternary ammonium, tetramethylammonium, tetraethylammonium, tetramethanolammonium, tetraethanolammonium, etc. are mentioned. Salts of phosphoric acid, phosphonic acid, and phosphinic acid are preferred, and salts of phosphoric acid are more preferred. Examples of the salt of phosphoric acid include ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, and the like.

By adding a small amount of potential regulator, the stability of the flame retardant processing chemical is improved. However, when the content thereof is increased, the cohesiveness may be increased and the stability of the flame-retardant processing chemical may be lowered. Therefore, the content of the potential adjusting agent in the flame-retardant processing chemical is preferably 5% by weight or less with respect to the entire flame-retardant processing chemical.

The flame retardant processing agent of the present invention can be prepared by mixing tricresyl phosphate (A) mainly composed of tricresyl phosphate, surfactant, water, and if necessary, triphenylphosphine oxide (B), other components, etc. Mix to make. The mixing method, mixing order and the like are not particularly limited. As a method for producing the flame retardant processing agent of the present invention, for example, the method of preparing micronized phosphoric acid in the case of using tricresyl phosphate (A) and triphenylphosphine oxide (B) in combination is mentioned. Tricresyl phosphate (A) and triphenylphosphine oxide (B) as the main component of tricresyl ester are mixed with surfactant and water (method 1); Tricresyl phosphate ester (A), triphenylphosphine oxide (B), surfactant, and water are mixed with ester as the main component, and the micronization device is used to disperse and micronize (method 2); Tricresyl phosphate (A), a surfactant, and water, which are mainly composed of cresyl ester, are mixed, and dispersed and micronized using a micronization device. On the other hand, triphenylphosphine oxide (B), a surfactant, and Mixing with water, dispersion and micronization using a micronization device, and compounding method (method 3), etc.

As a micronization device, a bead mill, a sand mill, an attritor, etc. are mentioned, for example. In addition, solvents, non-drying agents, defoamers (silicone defoamers, mineral oil defoamers, polyether defoamers, fatty acid (salt) defoamers, etc.), thickeners, Additives such as inorganic salts. Tricresyl phosphate (A) and triphenylphosphine oxide (B) may be finely divided into coarse powders, or may be formed into powders by melting solids and solidifying them.

The method for producing the flame-retardant processing agent of the present invention may be any one of the above-mentioned methods 1 to 3. In the case of method 1, tricresol phosphate containing tricresol phosphate as a main component of 1 μm or less may be used. Since ester (A) and triphenylphosphine oxide (B) do not dissociate from the aggregated state, and product stability becomes insufficient, method 2 or 3 is preferable.

The flame-retardant processing agent of the present invention is a flame-retardant processing agent for fibers used to impart flame retardancy to fiber materials. Its usage form is not particularly limited, and it is usually used after being diluted with water or the like.

The fiber material is not particularly limited, and the fiber material is a fiber containing at least many crystalline regions (for example, aliphatic polyester, aromatic polyester, cationic dyeable polyester, aromatic polyamide, aromatic polyimide, bismuth Acetate, triacetate, copolymers of their monomers, etc.), the adsorption properties of tricresyl phosphate (A) containing tricresyl phosphate as the main component contained in the flame retardant processing chemical Excellent and durable flame retardancy is improved, so it is preferable. Among them, among fiber materials containing at least aromatic polyester and cationic dyeable polyester, tricresyl phosphate (A) mainly composed of tricresyl phosphate is more preferable because of its excellent adsorption properties.

Examples of aliphatic polyesters, aromatic polyesters, and cationic dyeable polyesters include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, poly Ethylene naphthalate, Polybutylene naphthalate, Polyethylene terephthalate/Polyethylene isophthalate, Polyethylene terephthalate/Poly 5- Sodium sulfoethylene isophthalate/polyoxybenzoyl ethylene terephthalate, polybutylene terephthalate/polybutylene isophthalate, etc.

The fiber material may contain the above-mentioned fibers with many crystalline regions and fibers with many non-crystalline regions (for example, natural fibers such as kapok, hemp, and wool; nylon, etc.).

Here, the crystalline region means, for example, a region in which the molecular chains constituting the fiber are relatively regularly oriented, which is formed during physical treatment such as stretching in the manufacturing process of synthetic fibers, etc.; On the contrary, the molecular chains used to make up the fibers are relatively irregular and randomly oriented.

A fiber material may consist of only 1 type, and may consist of multiple types. When fibers with many crystalline regions and fibers with many non-crystalline regions are included, either blending or interweaving may be used. The form of the fiber material is not limited, and examples thereof include silk, woven fabric, knitted fabric, nonwoven fabric, rope, and belt.

〔Manufacturing method of flame-retardant fiber〕

The method for producing a flame-retardant fiber of the present invention includes a step of treating a fiber material with the above-mentioned flame-retardant processing chemical (treatment step). According to the production method of the present invention, fibers having good flame retardancy and excellent color fastness can be obtained even if the amount of organic phosphorus compound processed is small. Furthermore, a fiber excellent in atomization property can also be obtained. In addition, tank pollution and drainage load can be reduced.

The treatment step is to contact the flame retardant processing chemical with the fiber material, thereby making tricresyl phosphate (A) mainly composed of tricresyl phosphate contained in the flame retardant processing chemical, triphenylphosphine oxide ( B) (hereinafter sometimes referred to as the organophosphorus compound of the present invention) is a step of adhering to the fiber material. Examples of the treatment step include, for example, a treatment step in which the fiber material is immersed in a bath (treatment bath) containing a flame-retardant processing chemical, and the treatment temperature is 80° C. or higher, and the treatment time is 2 to 120 minutes (step 1). ; a process of attaching the flame retardant processing chemical to the fiber material, performing heat treatment at a temperature of 100 to 220° C., and absorbing the organophosphorus compound of the present invention into the fiber material (step 2), etc.

In the method of step 1, the organophosphorus compound of the present invention is imparted by immersing the fiber material in a bath prepared by diluting the flame retardant processing agent with water, and the fiber material is immersed in a state of 80° C. or higher for 2 to 120 minutes. The heat treatment imparts durability. The dilution rate of the flame retardant processing agent is not particularly limited, but is usually 1 to 10000 times. In order to relax or expand the amorphous region of the fiber material and to facilitate the adhesion of tricresyl phosphate (A) mainly composed of tricresyl phosphate, the treatment temperature in the state of impregnating the fiber material is preferably 80° C. or higher, More preferably, it is 80°C to 140°C. The weight ratio of the fiber material and the treatment bath in the method of step 1 is 1/2 to 1/100, preferably 1/3 to 1/50. Step 1 can be performed using, for example, a jet dyeing machine, a beam dyeing machine, a cheese dyeing machine, or the like.

In the method of step 2, the organophosphorus compound of the present invention is attached by immersing the fiber material in a bath prepared by diluting the flame retardant processing agent with water, and after drying it as the case may be, heat-treating the fiber material to make the fiber material The inventive organophosphorus compound is absorbed into the interior of the fiber material to impart durability. The temperature at this time is preferably 100 to 220°C, more preferably 150 to 200°C. When the temperature is lower than 100°C, tricresyl phosphate (A) and triphenylphosphine oxide (B), which are mainly composed of tricresyl phosphate, sometimes have insufficient exhaustion inside the fiber material, resulting in poor durability and flame retardancy , so it is not preferred. On the other hand, when the temperature exceeds 220° C., the fiber material may be thermally deteriorated to lower the strength, which is not preferable.

Attachment can be performed by a padding method, a spray method, a coating method, or the like. In addition, the heat treatment may be any of dry heat treatment and wet heat treatment. For example, a spraying-drying-curing system, a filling-drying-steaming system, a filling-steaming system, a filling-drying-curing system, etc. are mentioned.

In the method for producing flame-retardant fibers of the present invention, for example, at least one of the above-mentioned step 1 or step 2 may be performed, and the same step may be processed multiple times, or the step 1 and step 2 may be combined. Higher flame retardancy can be imparted. In addition, especially in the method for producing the flame-retardant fiber of the present invention, the method of step 1, the method of step 2, the method of step 2 after step 1, and the method of step 1 after step 2 are preferable, and the method of step 1 is more preferable. , after step 1, step 2 is carried out, and the method of carrying out step 1 is particularly preferred. Other treatment steps using other flame retardants different from the flame retardant processing agent of the present invention may also be used in combination.

In the method for producing flame-retardant fibers of the present invention, in the case of the method of step 1, the treatment amount of tricresyl phosphate (A) mainly composed of tricresyl phosphate (in the case of a flame-retardant processing agent containing three In the case of phenylphosphine oxide (B), it is the total treatment amount of tricresyl phosphate (A) and triphenylphosphine oxide (B) depending on the type or structure of the fiber material and the type of other fiber processing agents attached to the fiber material or the amount of adhesion varies, so it is not particularly limited, but it is usually preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight, even more preferably 0.1 to 4% by weight, and particularly preferably 0.5 to 3% by weight relative to the fiber material. weight%. When the treatment amount is less than 0.1% by weight, sufficient flame retardancy may not be imparted to the fiber material. On the other hand, when the treatment amount exceeds 10% by weight, the resulting flame-retardant fibers may have poor texture and poor adhesion efficiency to fiber materials, which is uneconomical. It should be noted that the treatment amount mentioned in the present invention refers to the weight ratio of the organophosphorus compound contained in the treatment bath relative to the dry weight of the fiber material to be treated.

In addition, in the method for producing the flame-retardant fiber of the present invention, the weight of both when tricresyl phosphate (A) and triphenylphosphine oxide (B) are used in combination The preferred ranges of the ratio and the weight ratio of the two corresponding to the treatment amount are the same as those described in the flame retardant processing agent.

In the method for producing a flame-retardant fiber of the present invention, other components other than the above-mentioned components may be contained in the treatment bath in the treatment step within a range that does not impair the effects of the present invention. Examples of other components include the same components as those exemplified for the flame-retardant processing chemical. For example, other flame retardants, surfactants, solvents, scouring agents, leveling agents, dispersants, bath softeners, chelating agents (polycarboxylic acid, nitrilotriacetic acid (NTA), ethylenediamine Tetraacetic acid (EDTA), hydroxyethane diphosphonic acid, nitrilo trimethylene phosphonic acid, phosphoric acid, glutamic acid diacetic acid and their salts, etc.), dyes, carrier preparations, pH adjusters, pH slip agents , potential regulator, defoamer, deodorant, antibacterial agent, softener, antistatic agent, water and oil repellent, antifouling agent, SR agent, stiff finishing agent, resin (polyester resin, acrylic resin, Polyurethane resin, etc.), UV absorbers, hydrophilic agents, etc. These substances may be used alone or in combination of two or more.

In the method for producing a flame-retardant fiber of the present invention, it is preferable that the treatment bath in the treatment step contains a dye. Examples of dyes include disperse dyes, cationic dyes, acid dyes, acid mordant dyes, metal complex dyes, direct dyes, reactive dyes, vat dyes, etc., preferably disperse dyes and cationic dyes. More preferred are disperse dyes. The disperse dye is not particularly limited, and known dyes can be used. Examples include Sumikaron dyes, Kayalon Polyester dyes, Miketon Polyester dyes, Palanil dyes, Dianix dyes, TD dyes, Kiwalon Polyester dyes, Terasil dyes, Foron dyes, and Serilene dyes.

The content of the dye is preferably 0.01 to 50% by weight, more preferably 0.1 to 20% by weight, and still more preferably 0.2 to 10% by weight, based on the fiber material.

In the method for producing a flame-retardant fiber of the present invention, it is preferable to include an ultraviolet absorber in the treatment bath in the treatment step. Examples of the ultraviolet absorber include the same components as the ultraviolet absorbers exemplified in the flame-retardant processing chemicals. The content of the ultraviolet absorber is preferably 0.01 to 10% by weight, more preferably 0.01 to 3% by weight, particularly preferably 0.05 to 1% by weight, based on the fiber material.

In the method for producing a flame-retardant fiber of the present invention, it is preferable to include a leveling agent in the treatment bath in the treatment step. As a leveling agent, a commercial item can be used.

In the method for producing a flame-retardant fiber of the present invention, it is preferable to include a pH adjuster in the treatment bath in the treatment step. Examples of the pH adjuster include formic acid, sodium formate, acetic acid, sodium acetate, lactic acid, sodium lactate, phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, and trisodium phosphate. The pH value in the treatment step is not limited, but it is preferably acidic, more preferably 3-6, from the viewpoint of high adhesion efficiency to the fiber material and reduction of tank body contamination and drainage load.

〔Flame Retardant Fiber〕

The flame-retardant fiber of the present invention is obtained by the method for producing the flame-retardant fiber of the present invention, and is excellent in flame retardancy and color fastness. Furthermore, it is also excellent in atomization property.

In the flame-retardant fiber of the present invention, the adhesion amount of tricresyl phosphate (A) mainly composed of tricresyl phosphate to the fiber material (when the flame-retardant processing agent contains triphenylphosphine oxide (B) is The total adhesion amount of tricresyl phosphate (A) and triphenylphosphine oxide (B)) varies depending on the type or structure of the fiber material, and the type or amount of other fiber processing agents attached to the fiber material, so there is no Particularly limited, it is preferably 0.1 to 10% by weight, more preferably 0.1 to 3% by weight, and even more preferably 0.5 to 2% by weight based on the flame-retardant fiber (the entire fiber including deposits). When the adhesion amount 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 exceeds 10% by weight, the hand feeling of the obtained flame-retardant fiber may deteriorate, and the flame-retardant effect may become saturated, which is not economical. It should be noted that the adhesion amount mentioned in the present invention refers to: the P element amount of the treated fiber material is measured by ICP analysis and the amount attached to the treated fiber is calculated assuming that the treatment ratio of the organic phosphorus compound is the same as the depletion ratio. The weight ratio of the organophosphorus compound of the material relative to the dry weight of the treated fibrous material.

It should be noted that, in the treatment process of the method for producing flame-retardant fibers of the present invention, it is preferable that the amount of tricresyl phosphate (A) attached to the fiber material or that the above-mentioned flame-retardant processing agent contains triphenyl In the case of phosphine oxide (B), tricresyl phosphate (A) and triphenylphosphine oxide (B) are treated so that the total adhesion amount to the fiber material becomes the above-mentioned adhesion amount.

In the flame-retardant fiber of the present invention, tricresyl phosphate (A) and triphenyl The adhesion weight ratio (A/B) of the phosphine oxide (B) is not particularly limited, but is preferably 95/5 to 5/95.

The preferred range of the attachment weight ratio (A/B) of tricresyl phosphate (A) and triphenylphosphine oxide (B) is based on the total weight of tricresyl phosphate (A) and triphenylphosphine oxide (B) to the fiber material. Changes in the amount of adhesion.

When the total adhesion amount of tricresyl phosphate (A) and triphenylphosphine oxide (B) exceeds 3% by weight relative to the flame-retardant fiber, the adhesion weight ratio (A/B) is more preferably 30/70 to 5/95 , and more preferably 40/60 to 5/95. When the above-mentioned total adhesion amount is 3% by weight or less, it is more preferably 95/5 to 10/90, still more preferably 95/5 to 20/80, and particularly preferably 95/5 to 30/70. When the above-mentioned total adhesion amount is 2.5% by weight or less, it is more preferably 95/5 to 20/80, still more preferably 95/5 to 40/60, and particularly preferably 95/5 to 40/60. When the above-mentioned total adhesion amount is 2% by weight or less, it is more preferably 95/5 to 30/70, still more preferably 95/5 to 40/60, and particularly preferably 95/5 to 60/40.

In the flame-retardant fiber of the present invention, the amount of surfactant attached to the fiber material varies depending on conditions such as the type or texture of the fiber material, and the type or amount of other fiber processing agents attached to the fiber material, so it is not particularly limited. Preferably it is 0 to 10 weight% with respect to a flame-retardant fiber, More preferably, it is 0 to 1 weight%.

In the flame-retardant fiber of the present invention, it is preferable to contain a dye. Examples of dyes include disperse dyes, cationic dyes, acid dyes, acid mordant dyes, metal complex dyes, direct dyes, reactive dyes, vat dyes, etc., preferably disperse dyes and cationic dyes. More preferred are disperse dyes. The amount of dye attached is preferably 0.01 to 50% by weight, more preferably 0.1 to 20% by weight, and still more preferably 0.2 to 10% by weight, based on the flame-retardant fiber.

In the flame-retardant fiber of the present invention, it is preferable to contain an ultraviolet absorber. Examples of the ultraviolet absorber include the same components as the ultraviolet absorbers exemplified in the flame-retardant processing chemicals. The content of the ultraviolet absorber is preferably 0.01 to 10% by weight, more preferably 0.01 to 3% by weight, and still more preferably 0.05 to 1% by weight based on the flame-retardant fiber.

In the flame-retardant fiber of the present invention, other components other than the above-mentioned components may be contained within the range that does not impair the effect of the present invention. Examples of other components include other flame retardants, solvents, scouring agents, leveling agents, dispersants, bath softeners, chelating agents, carrier preparations, pH regulators, pH slip agents, potential regulators, Defoamer, deodorant, antibacterial agent, softener, antistatic agent, water and oil repellent, antifouling agent, SR agent, stiffening agent, resin, hydrophilic agent, etc. These substances may contain 1 type or 2 or more types.

The flame-retardant fiber of the present invention preferably contains a water-soluble flame retardant. Preferred are salts of phosphoric acid, phosphorous acid, hypophosphorous acid, tripolyphosphoric acid, polyphosphoric acid, sulfamic acid, sulfuric acid, etc., for example, ammonium polyphosphate, guanidine phosphate, guanidine sulfamate, ammonium sulfamate, Phosphonate, guanidine dimethyl phosphate, guanidine dimethyl phosphonite, guanidine urea phosphate, hydroxyethane diphosphonate, nitrilo trimethylene phosphonate, etc.

The method of treating the flame-retardant fiber with the above-mentioned dye, ultraviolet absorber, other components, and water-soluble flame retardant is not particularly limited, and known methods can be used. In addition, it may be treated together with the flame-retardant processing chemical of the present invention in the above-mentioned treatment step.

The flame-retardant fiber of the present invention is excellent in flame retardancy and color fastness, and can be used for vehicle interior materials such as automobiles, airplanes, railways, ships, etc.; bedding, mattresses, bed sheets, pillows, quilts, blankets, towel quilts, etc. Supplies; disaster prevention scarves, fireproof clothing and other clothing; curtains, blinds, sofas, chairs, cushions, black curtains, wallpaper, display plywood, fiberboard, curtains, engineering boards, blankets, carpets, tablecloths, cushions , sliding doors, partitions, tents, interior decoration and many other purposes. Examples of automotive interior materials include seat backs, door panels, headliners, seat cushions, armrests, curtains, cushions, sun visors, seat belts, front panels, floor covers, side panels, and the like.

The flame-retardant fiber of the present invention is also excellent in atomization properties, and therefore can be suitably used in vehicle interior materials such as automobiles that require not only flame retardancy and color fastness but also excellent atomization properties.

The flame-retardant fiber of the present invention is preferably used in the UL-94 vertical burning test, the UL-94 light and thin material vertical burning test, and the A method of JIS-L-1091 (micro burner method, Meker burner method) , horizontal method, vertical method), B method (surface combustion test), C method (burning speed test), D method (flame contact test), E method (oxygen index method test), JIS-D-1201, FMVSS-302 Applicable applications in combustion tests such as the Combustion Test of Interior Materials for Automobiles, etc.

Example

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

〔Evaluation method〕

[melting point]

For the non-volatile components of the organophosphorus compound and the prepared flame-retardant processing chemical, using a differential scanning calorimeter DSC220U (manufactured by Seiko Denshi Kogyo Co., Ltd.), the non-volatile components were reduced at a heating rate of 10°C/min under a nitrogen atmosphere. About 5 mg was heated from 0°C to 200°C, and the temperature of the endothermic peak that appeared was measured. In addition, in the case of the non-volatile content of the flame-retardant processing chemical, the endothermic peak derived from the organophosphorus compound was measured (in the case of the non-volatile content of the flame-retardant processing chemical in Examples 9 to 22, the endothermic peak was derived from The temperature of the endothermic peak of tricresyl phosphate mainly composed of tricresyl phosphate). In addition, the non-volatile content of the flame-retardant processing chemical means that a certain amount of sample is spread on an aluminum sheet, dried at 110°C under the irradiation of an infrared lamp, and the fluctuation range of the volatile content reaches 0.15% by weight in 150 seconds. % is the remaining component at the end of the measurement.

〔Exhaustion as much as possible and exhaustion rate〕

For the flame-retardant polyester fiber obtained, the maximum absorption of the P element is measured by ICP analysis, assuming that the treatment ratio of the organic phosphorus compound is the same as the exhaustion ratio, the maximum absorption (attachment amount) and the exhaustion rate of the organic phosphorus compound are calculated ( Adhesion amount/treatment amount×100).

〔Flame Retardancy Evaluation Method〕

The obtained sample for the flame retardancy test was subjected to an automobile interior material combustion test described in FMVSS-302 method (JIS-D-1201), and the average value of 10 measurements was calculated to measure the burning rate. However, when the flame was extinguished within the marked line, the burning speed was recorded as 0; when it was extinguished within 50 mm and within 1 minute, the measurement was performed again.

Under these conditions, when the treated amount of the flame retardant component (organophosphorus compound) is 1.6% by weight relative to the fiber material, the burning rate is preferably 120 mm/min or less, more preferably 100 mm/min or less. When the treated amount of the flame retardant component is 3.2% by weight, the burning rate is preferably 60 mm/min or less, more preferably 40 mm/min or less. When the treated amount of the flame retardant component is 4.8% by weight, the burning rate is preferably 20 mm/min or less, more preferably 10 mm/min or less.

[Evaluation method of anti-staining property and tank fouling property]

Regarding the evaluation of anti-staining property and tank staining property, the prepared flame-retardant processing chemical was put into a MINI COLOR special dyeing tank filled with water to a concentration of 1g/L, and then Kayalon Polyester Black RV-SF300 ( 3% by weight of owf (manufactured by Nippon Kayaku Co., Ltd.) was dissolved in water at 30 to 35° C., put into the dyeing tank, adjusted to pH 4.5 with acetic acid/sodium acetate buffer, and prepared as a dyeing bath. Thereafter, Briand C-1800 (2 g/L, manufactured by Matsumoto Yuyu Pharmaceutical Co., Ltd.) as a knitting oil was put into the bath. The estimated bath ratio at this time was set to 1:20.

Next, only the dyebath is treated with MINI COLOR. As treatment conditions, the temperature was raised to 135° C. at a rate of 2° C. per minute, and 135° C. was maintained for 40 minutes. Then, when it cooled and reached 80 degreeC, the scouring dyeing liquid was filtered using the filter paper. The stain resistance evaluation was performed according to the following reference|standard in the state which made the filter paper dry naturally. In addition, regarding the contamination of the tank, the degree of contamination of the MINICOLOR exclusive dyeing tank is determined according to the following criteria.

・Evaluation criteria for stain resistance

◯: The filter paper is hardly colored.

×: Stains are present on the entire surface of the filter paper, and the filter paper is clearly colored.

Δ: Stains are present on the entire surface of the filter paper, and coloring of the filter paper is observed (intermediate level between ◯ and ×).

·Evaluation criteria for tank contamination

○: Almost no contamination was observed in the MINI COLOR special dyeing tank.

×: Contamination was observed throughout the MINI COLOR dedicated dyeing tank.

△: Contamination was observed in a part of the MINI COLOR exclusive dyeing tank.

〔Exudation evaluation method〕

After treating the flame-retardant processed cloth with the treatment amount of the flame-retardant component at 3.2% by weight relative to the fiber material in an atmosphere of 70°C and 90% Rh for 400 hours, the rubbing fastness test was carried out using a rubbing tester type II according to JIS L 0849 , evaluated in series. The larger the series, the better the exudation.

[Manufacturing example 1]

<Manufacture of tricresyl phosphate (Al) mainly composed of tricresyl phosphate>

716 g of p-cresol (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.70% by weight, containing 0.10% by weight of phenol and 0.20% by weight of o-cresol) and 16 g of aluminum chloride were put into a 2000 mL four-necked flask, and the mixture was heated at 80° C. for 2 hours. Slowly add 335 g of phosphorus oxychloride dropwise to remove the generated hydrogen chloride. After completion of the dropwise addition, aging was performed at 120° C. for 3 hours. The reactant was cooled to 90° C., 500 g of a solution containing 5% by weight of caustic soda was poured in, and stirred at 90° C. for 1 hour. The water phase was removed, the reactant was put into cold water, washed for 1 hour, dehydrated, and washed with water for 1 hour. Dehydration and drying yielded 770 g of tricresyl phosphate (A1) as a white solid with a purity of 99.1% of tricresyl phosphate and a melting point of 77°C.

[Manufacturing example 2]

<Manufacture of tricresyl phosphate (A2) mainly composed of tricresyl phosphate>

Into a 2000 mL four-necked flask, 710 g of p-cresol (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.70% by weight, containing 0.10 weight % of phenol and 0.20 weight % of o-cresol) and m-cresol (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9% by weight) and 16 g of aluminum chloride, 335 g of phosphorus oxychloride was slowly added dropwise at 80° C. over 2 hours to remove generated hydrogen chloride. After completion of the dropwise addition, aging was performed at 120° C. for 3 hours. The reactant was cooled to 90° C., 500 g of a solution containing 5% by weight of caustic soda was poured in, and stirred at 90° C. for 1 hour. The water phase was removed, the reactant was put into cold water, washed for 1 hour, dehydrated, and washed with water for 1 hour. Dehydration and drying gave 773 g of tricresyl phosphate (A2) as a white solid with a purity of 96.5% of tricresyl phosphate and a melting point of 75°C.

[Example 1]

The compounding components shown in Table 1 were put into a DESPA type mixer, and it stirred and dispersed fully at 25 degreeC. Then, using Star Mill ZRS (manufactured by Ashizawa Finetech Ltd.), the obtained slurry was subjected to micronization at 25° C. for 6 hours to prepare flame-retardant processing chemicals, respectively. In addition, POE (13) styrenated phenol sulfate Na salt shown in Table 1 refers to polyoxyethylene styrenated phenol sulfate Na salt, and the average number of repeating numbers of its oxyethylene group is 13. In addition, the degree of styrenation of styrenated phenol is mono:di:tri=15:50:35 by weight ratio. The melting point of the prepared flame-retardant processing chemical was measured. In addition, anti-staining properties and can body staining properties were evaluated using the prepared flame-retardant processing chemicals.

Next, use the prepared flame-retardant processing agent to perform flame-retardant processing (including dyeing and soaping) under the following flame-retardant processing conditions in order to reach the treatment amount of flame-retardant components specified in Table 1, to obtain flame-retardant permanent polyester fiber. The obtained flame-retardant polyester fibers were evaluated for maximum absorption, exhaustion rate, and exudation. It should be noted that the treatment amount of the flame retardant component refers to the treatment amount of the flame retardant component relative to the fiber material.

Next, using the obtained flame-retardant polyester fiber, a sample for a flame-retardant test was produced by the method described later, and the flame retardancy was evaluated.

These results are shown in Table 1.

<Flame Retardant Processing>

Put water and a flame retardant processing chemical composition into the MINI COLOR special dyeing tank of the MINI COLOR dyeing machine (manufactured by Texam Giken Co., Ltd.), and then add Kayalon Polyester Black RV-SF300 (3% by weight owf, Nippon Kayaku Co., Ltd. prepared) was dissolved in water at 30-35° C. and put into the dyeing tank. After that, the pH value was adjusted to 4.5 with acetic acid/sodium acetate buffer to prepare a dyeing bath.

Next, the polyester thin gray fabric is put into the prepared dyeing bath and treated with MINI COLOR. The bath ratio at this time was 1:20. As treatment conditions, the temperature was raised to 135° C. at a rate of 2° C. per minute, and 135° C. was maintained for 40 minutes. Then, when it cooled and reached 70 degreeC, the dyeing bath was discarded, and it washed with water for 5 minutes.

Next, utilize the bath that comprises soaping agent i.e. Mapo Maberin S-1520 (manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.) 1 g/L, dithionite 2 g/L, and caustic soda 2 g/L at a bath ratio of 1: 20. Under the condition of a temperature of 80° C., soaping treatment was carried out for 15 minutes, washed with water, and dried at 160° C. for 1 minute to obtain a flame-retardant polyester fiber.

<Preparation of samples for flame retardancy test>

The flame-retardant processed textiles were dipped in a liquid containing 3% by weight of a silicone-based softening agent, namely Matsumoto Silicone softener N-20 (manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.), and processed with a mangle. ) was squeezed (90% squeeze rate), dried at 110° C. for 3 minutes, and solidified at 160° C. for 1 minute to obtain a sample.

[Examples 2-22, Comparative Examples 1-20]

Except having changed the compounding components shown in Tables 1-5 respectively, it carried out similarly to Example 1, and evaluated. The results are shown in Tables 1-5.

In addition, triphenylphosphine oxide in Tables 2 to 5 represents TPPO (manufactured by K.I CHEMICALINDUSTRY CO., LTD.). In addition, tricresyl phosphate (TCP) of the isomer mixture in Tables 2 and 5 represents the isomer mixture of m-cresol: p-cresol = 50-60: 40-50 (weight ratio) obtained from the isomer mixture of cresol A mixture of isomers of tricresyl phosphate with a freezing point of -35°C. See Table 6 for details of the flame retardant components A to K in Table 2 and the ultraviolet absorbers in Tables 1 to 5.

[Table 1]

[Table 2]

[table 3]

[Table 4]

[table 5]

[Table 6]

In Examples 1 to 22 using tricresyl phosphate (A) mainly composed of tricresyl phosphate, the exhaustion properties, flame retardancy, anti-staining properties, tank staining properties, and exudation properties All items are excellent. On the other hand, in Comparative Examples 1 to 20 using organophosphorus compounds other than tricresyl phosphate (A), the exhaustion property, flame retardancy, anti-staining property, can fouling property, and exudation property were all superior. Either item is poor.

In Examples 9 to 22, in which tricresyl phosphate (A) mainly composed of tricresyl phosphate and triphenylphosphine oxide were used in combination, a synergistic effect was observed on the depletion property. Compared with 1 to 8, the exhaustion rate is improved, and the flame retardancy is also improved. In addition, it is also excellent in stain resistance, can body staining properties, and bleeding properties. In contrast, in Comparative Examples 14 to 20 in which tricresyl phosphate (TCP) and triphenylphosphine oxide were used in combination as a mixture of isomers, no synergistic effect was observed on the depletion property, and flame retardancy, Poor in stain resistance, tank contamination, and exudation.

Using the flame-retardant polyester fibers shown in Examples 1 to 8 and Comparative Examples 1 to 13 (the treated amount of the flame retardant component was 3.2% by weight), the fogging properties were evaluated by the following method. The results are shown in Table 7.

In Examples 1 to 8 in which tricresyl phosphate (A) containing tricresyl phosphate as a main component was used, atomization properties were excellent. On the other hand, in Comparative Examples 2, 11, and 12 using tricresol phosphate, tri-o-cresol phosphate, and tri-m-cresol phosphate of the isomer mixture, the atomization properties were poor.

〔Aerosolization evaluation method〕

10 g of flame-retardant polyester fibers were put into a 1-liter glass container, and covered with a glass plate with a thickness of 5 mm and a size of 5 cm square. The glass container was immersed in an oil bath maintained at 80° C. for 20 hours. Thereafter, the glass plate was taken out, and excess water and the like were evaporated using a commercially available drier. The glass haze (%) (HAZE) of this glass plate was measured. A glass haze of 10% or less was regarded as acceptable.

[Table 7]

Industrial availability

The flame-retardant processing agent for fibers of the present invention can be suitably used when imparting flame retardancy to a fiber material.

Claims (10)

1. A flame-retardant processing agent for fibers, comprising tricresyl phosphate (A) mainly composed of tricresyl phosphate, a surfactant, and water, The weight ratio of tricresyl phosphate in the whole of the tricresyl phosphate (A) is 90% by weight or more. 2. The flame-retardant processing agent according to claim 1, wherein the tricresyl phosphate (A) has a melting point of 65 to 80°C. 3. The flame-retardant processing agent according to claim 1 or 2, wherein the tricresyl phosphate (A) is in a state of being emulsified or dispersed in water. 4. The flame retardant processing agent according to any one of claims 1 to 3, further comprising triphenylphosphine oxide (B). 5. The flame-retardant processing agent according to claim 4, wherein the weight ratio (A/B) of the tricresyl phosphate (A) to the triphenylphosphine oxide (B) is 95/5 to 5 /95. 6. The flame-retardant processing agent according to claim 4 or 5, wherein the tricresyl phosphate (A) and the triphenylphosphine oxide (B) are in a state of being emulsified or dispersed in water. 7. The flame-retardant processing agent according to any one of claims 1 to 6, wherein the surfactant contains polyoxyalkylene polycyclic aryl ether sulfate and polyoxyalkylene polycyclic aryl ether at least 1 species of . 8. A method for producing a flame-retardant fiber, comprising the step of treating a fiber material with the flame-retardant processing agent according to any one of claims 1 to 7. 9. The method for producing flame-retardant fibers according to claim 8, wherein, in the step, the treated amount of tricresyl phosphate (A) or the flame-retardant processing chemical contains triphenylphosphine oxide In the case of (B), the total treatment amount of tricresyl phosphate (A) and triphenylphosphine oxide (B) is 0.1 to 5% by weight based on the fiber material. 10. A kind of flame-retardant fiber, it is the flame-retardant fiber obtained by the manufacturing method described in claim 8 or 9, The amount of tricresyl phosphate (A) attached to the flame-retardant fiber, or when the flame-retardant processing agent contains triphenylphosphine oxide (B), tricresyl phosphate (A) and triphenylphosphine oxide ( The total adhesion amount of B) is 0.1 to 3% by weight relative to the flame-retardant fiber.