JP2017002453A - Manufacturing method of flame retardant fiber, flame retardant processing agent and flame retardant processing assistant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a flame retardant fiber capable of reducing stain (spec stain) or tank stain (can body stain) to a fiber material and adding good flame retardancy and washing durability to the fiber material when heat treating the fiber material in a bath containing a flame retardant.SOLUTION: The manufacturing method of a flame retardant fiber including a process of heat treating a fiber material in a bath containing at least one kind of flame retardant (A) selected from a bromine-based flame retardant and a phosphorous-based flame retardant and a compound (B) which is a reaction product of acid anhydride and an organic compound having a hydroxyl group.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a flame retardant fiber, a flame retardant processing agent, and a flame retardant processing aid. In detail, it is related with the manufacturing method of the flame-retardant fiber which provides a flame retardance to fiber material, the flame-retardant processing chemical | medical agent and flame-retardant processing adjuvant which can be used suitably for this manufacturing method.

  Conventionally, a flame retardant in which hexabromocyclododecane (hereinafter HBCD) is dispersed or emulsified in water has been generally used in order to impart flame retardancy to a fiber material. However, HBCD has been designated as a first-class specific chemical substance because it has been found to be hardly decomposable and highly accumulative, and recently there has been an increasing demand for flame retardants for de-HBCD.

  As an alternative to HBCD, bromine-based compounds disclosed in Patent Documents 1 to 4 are used. However, these brominated compounds are inferior in flame retardancy and poor in emulsifying dispersibility as compared with HBCD, and there is a problem of generation of stains (spec stains) and kettle stains (can body contamination) on fiber materials during processing. It has become. In order to solve this problem, tris (2,3-dibromopropyl) isocyanurate is used as a bromine-based compound. In Patent Document 5, flame retardancy and emulsifying dispersibility are improved by using tris (2,3-dibromopropyl) isocyanurate in combination with a specific phosphate ester and a specific surfactant. Moreover, in patent document 6, the flame retardance and emulsification dispersibility are improved by using tris (2,3- dibromopropyl) isocyanurate and a specific surfactant together.

  However, even in these prior arts, the emulsifying dispersibility of the flame retardant is insufficient, and there is a problem inferior in flame retardancy and washing durability. In addition, there is a problem that dirt (spec dirt) on the fiber material during processing increases. In addition, there was a problem that kettle dirt (can body contamination) occurred.

JP 2009-203595 A JP 2009-174109 A JP 2011-37966 A JP 2010-285714 A WO2011 / 96391 Publication JP 2011-195984 A

  The subject of the present invention is that when heat treating a fiber material in a bath containing a flame retardant, stains on the fiber material (spec stains) and kettle stains (can body contamination) can be reduced. It is providing the manufacturing method of the flame-retardant fiber which can provide a flame retardance and washing durability, the flame-retardant processing chemical | medical agent which can be used suitably for this manufacturing method, and a flame-retardant processing adjuvant.

  As a result of intensive studies to solve the above problems, the present inventors have used a specific compound when heat-treating a fiber material in a bath containing a flame retardant, thereby improving the emulsifying dispersibility of the flame retardant. The inventors have found that it is possible to reduce dirt (spec dirt) and pot dirt (can body contamination) on the fiber material due to the reduction, and to impart good flame retardancy and washing durability, and the present invention has been achieved.

  That is, the method for producing a flame-retardant fiber of the present invention is a reaction product of at least one flame retardant (A) selected from a bromine-based flame retardant and a phosphorus-based flame retardant, an acid anhydride and an organic compound having a hydroxyl group. It includes a step of heat-treating the fiber material in a bath containing a certain compound (B).

（ただし、式（１）中、Ｒ及びＲ^２は、それぞれ独立して有機基である。Ａ^１Ｏは炭素数２〜４のオキシアルキレン基である。ｌは０〜５０の数である。ｍは１〜５の数である。Ｍ^１は水素原子又はアルカリ性基である。） The compound (B) is preferably a compound represented by the following general formula (1).

(In the formula (1), R and R ² are each independently an organic group. A ¹ O is an oxyalkylene group having 2 to 4 carbon atoms. L is a number from 0 to 50.) m is a number from 1 to 5. M ¹ is a hydrogen atom or an alkaline group.)

  The ratio of the compound (B) is preferably 1 to 200 parts by weight with respect to 100 parts by weight of the flame retardant (A).

  The brominated flame retardant is preferably tris (2,3-dibromopropyl) isocyanurate.

The flame retardant processing agent of the present invention is a compound (B) which is a reaction product of at least one flame retardant (A) selected from a brominated flame retardant and a phosphorus flame retardant, an acid anhydride and an organic compound having a hydroxyl group. And water.
The compound (B) is preferably a compound represented by the general formula (1).
The ratio of the compound (B) is preferably 1 to 200 parts by weight with respect to 100 parts by weight of the flame retardant (A).
The brominated flame retardant is preferably tris (2,3-dibromopropyl) isocyanurate.

The flame retardant processing aid of the present invention is used in combination with at least one flame retardant (A) selected from a bromine-based flame retardant and a phosphorus-based flame retardant, and includes an acid anhydride and an organic compound having a hydroxyl group. It contains compound (B) as a reactant.
The compound (B) is preferably a compound represented by the general formula (1).

The method for producing a flame-retardant fiber of the present invention can reduce stains (spec stains) and kettle stains (can body contamination) on fiber materials when heat-treating the fiber materials in a bath containing a flame retardant. Good flame retardancy and washing durability can be imparted to the material.
The flame retardant processing agent and flame retardant processing aid of the present invention can be suitably used in the production method of the present invention, and when these are used, when heat treating a fiber material in a bath containing the flame retardant, Dirt (spec stain) and pot stain (can body contamination) on the fiber material can be reduced, and good flame retardancy and washing durability can be imparted to the fiber material.

[Production method of flame retardant fiber]
The method for producing a flame-retardant fiber according to the present invention is a compound that is a reaction product of at least one flame retardant (A) selected from a brominated flame retardant and a phosphorus flame retardant and an acid anhydride and an organic compound having a hydroxyl group. It includes a step of heat-treating the fiber material in a bath containing (B). According to the production method of the present invention, when heat-treating a fiber material in a bath containing a flame retardant, dirt (hereinafter referred to as spec dirt) or kettle dirt (hereinafter referred to as spec dirt) due to a decrease in the emulsifying dispersibility of the flame retardant. Hereinafter, the can body contamination) can be reduced. Moreover, the obtained flame-retardant fiber is excellent in flame retardancy and is also excellent in washing durability. This will be described in detail below.

<Flame retardant (A)>
The flame retardant (A) is at least one selected from a brominated flame retardant and a phosphorus flame retardant. One type of flame retardant (A) may be used, or two or more types may be used in combination. It is preferable that a flame retardant (A) contains a brominated flame retardant and a phosphorus flame retardant essential.

  Examples of brominated flame retardants include tris (2,3-dibromopropyl) isocyanurate (bromine content: about 66% by weight, melting point: about 115 ° C.), tris (tribromoneopentyl) phosphate (bromine content: about 70% by weight, Melting point 180 ° C.), bis (3,5-dibromo-4-dibromopropyloxyphenyl) sulfone (bromine content about 66% by weight, melting point about 115 ° C.), tetrabromocyclooctane (bromine content about 75% by weight, melting point) About 135 ° C), tetrabromophthalic anhydride (bromine content about 68% by weight, melting point about 280 ° C), decabromodiphenyl ether (bromine content about 83% by weight, melting point 300 ° C or higher), tetrabromobisphenol S (bromine content) About 56 wt%, melting point of about 290 ° C, tetrabromobisphenol A (bromine content of about 58 wt%, melting point of about 180 ° C) Tetrabromobisphenol A bis (2-hydroxyethyl) ether (bromine content about 51 wt%, melting point about 118 ° C.), tetrabromobisphenol A epoxy oligomer (bromine content 50-60 wt%, melting point 100 ° C. or higher), Tetrabromobisphenol A carbonate oligomer (bromine content about 55% by weight, melting point 200 ° C. or higher), tetrabromobisphenol A bis (dibromopropyl ether) (bromine content about 68% by weight, melting point about 117 ° C.), tetrabromobisphenol A Bis (allyl ether) (bromine content about 51% by weight, melting point about 120 ° C.), bis (pentabromophenyl) ethane (bromine content about 82% by weight, melting point about 350 ° C.), 1,2-bis (2, 4,6-tribromophenoxy) ethane (bromine content about 70% by weight, melting point about 24 ° C.), 2,4,6-tris (2,4,6-tribromophenoxy) 1,3,5-triazine (bromine content: about 67% by weight, melting point: about 230 ° C.), ethylenebistetrabromophthalimide ( Bromine content: about 67 wt%, melting point: about 456 ° C), brominated polystyrene (bromine content: about 66 wt%, melting point: about 180 ° C), polybrominated styrene (bromine content: 60 wt% or more, melting point: 100 ° C or more) , Hexabromobenzene (bromine content about 87% by weight, melting point 327 ° C.), pentabromotoluene (bromine content about 82% by weight, melting point about 288 ° C.), hexabromocyclododecane (bromine content about 74% by weight, melting point) About 180 ° C.), brominated cycloalkane (bromine content: 75 to 88% by weight, melting point: 100 ° C. or more), and the like.

  The brominated flame retardant preferably has a melting point of 40 to 150 ° C. When the melting point of the brominated flame retardant is within this range, the state change from solid to liquid or from liquid to solid occurs when heat-treated in a bath and cooled, and the emulsifying dispersibility of the flame retardant by using the compound (B) The effect of suppressing the decrease is increased. As a result, the effect of reducing spec stains and can body contamination is increased. The melting point of the brominated flame retardant is more preferably 50 to 150 ° C, and further preferably 100 to 140 ° C. The melting point referred to in the present invention is a melting point measured using a differential scanning calorimeter, and represents the temperature of an endothermic peak that appears when about 5 mg of a sample is heated at a heating rate of 10 ° C./min in a nitrogen atmosphere. Say.

  Examples of the brominated flame retardant having a melting point of 40 to 150 ° C. include tris (2,3-dibromopropyl) isocyanurate, bis (3,5-dibromo-4-dibromopropyloxyphenyl) sulfone, and tetrabromocyclooctane. Tetrabromobisphenol A bis (2-hydroxyethyl) ether, tetrabromobisphenol A bis (dibromopropyl ether), tetrabromobisphenol A bis (allyl ether), brominated cycloalkane, and the like.

  As a brominated flame retardant, tris (2,3-dibromopropyl) isocyanurate, tris (tribromoneopentyl) phosphate, bis (3,5-dibromo-) are high in exhaustibility and excellent in flame retardancy. 4-Dibromopropyloxyphenyl) sulfone, tetrabromocyclooctane, ethylenebistetrabromophthalimide, hexabromobenzene, and brominated cycloalkane are preferred.

  The brominated flame retardant is particularly tris (2,3-dibromopropyl) isocyanurate because it is highly effective in reducing dirt and kettle dirt on the fiber material, has high exhaustibility, and is excellent in flame retardancy. preferable.

  Phosphorus flame retardants include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, octyl diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, tri-p-cresyl phosphate, trixylenyl phosphate , Cresyl diphenyl phosphate, dicresyl phenyl phosphate, cresyl dixylenyl phosphate, dicresyl xylenyl phosphate, triisopropyl phenyl phosphate, diphenyl xenyl phosphate, phenyl dixenyl phosphate, diphenyl orthoxenyl phosphate, phenyl diorxose Nyl phosphate, triorxenyl phosphate, trimetaxenyl phosphate Triparaxenyl phosphate, trixenyl phosphate, α-naphthyl diphenyl phosphate, di-α-naphthyl phenyl phosphate, β-naphthyl diphenyl phosphate, di-β-naphthyl phenyl phosphate, 2-phenoxyethyl diphenyl phosphate, 5,5-dimethyl -2- (4′-phenylphenoxy) -1,3,2-dioxaphosphorinane-2-oxide, 1,3,2-dioxaphosphorinane- {2- (1,1′-biphenyl-2-) Yloxy)}-5,5-dimethyl-2-oxide, phosphate esters such as 5,5-dimethyl-2- (2′-phenylphenoxy) -1,3,2-dioxaphosphorinane-2-oxide; Resorcinol bis (diphenyl phosphate), resorcinol bis (dicresyl phosphate) ), Resorcinol bis (dixylenyl phosphate), hydroquinone bis (diphenyl phosphate), hydroquinone bis (dicresyl phosphate), hydroquinone bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate), bisphenol A bis (dicresyl) Phosphate), condensed phosphate esters such as bisphenol A bis (dixylenyl phosphate); dimethyl methylphosphonate, diethyl ethylphosphonate, dipropyl methylphosphonate, dibutyl methylphosphonate, dibutyl butylphosphonate, diphenyl phenylphosphonate, dicresyl phenylphosphonate , Dixylyl phenylphosphonate, phenylcresyl phenylphosphonate, bis [(5-ethyl-2-methyl-1,3,2-di Oxaphosphorinan-5-yl) methyl] methylphosphonate-P, P′-dioxide, (5-ethyl-2-methyl-1,3,2-dioxaphosphorinan-5-yl) methyldimethylphosphonate-P -Phosphorous acid ester of oxide; such as methyl dimethylphosphinate, ethyl diethylphosphinate, propyl dimethylphosphinate, butyl ditylphosphinate, phenyl diphenylphosphinate, cresyl diphenylphosphinate, xylyldiphenylphosphinate, metal salt of diethylphosphinate, etc. Hypophosphite; trimethylphosphine oxide, triethylphosphine oxide, tri-n-propylphosphine oxide, tri-n-butylphosphine oxide, tri-n-hexylphosphine oxide, tri-n-o Tylphosphine oxide, tricyclohexylphosphine oxide, tolylphosphine oxide, tris-3-hydroxypropylphosphine oxide, tris (2-methylphenyl) phosphine oxide, tris (4-methylphenyl) phosphine oxide, tris (2,6-dimethyl) Phenyl) phosphine oxide, tris (2,6-dimethoxyphenyl) phosphine oxide, tribenzylphosphine oxide, 2- (diphenylphosphinyl) hydroquinone, phosphine oxide such as triphenylphosphine oxide; 10-benzyl-9,10-dihydro -9-oxo-10λ (5) -phosphaphenanthrene = 10-oxide, 10-phenoxy-9,10-dihydro-9-oxo-10λ (5) Phosphaphenanthrene derivatives such as phosphaphenanthrene = 10-oxide; Phosphate ester amides such as diphenyl = (phenylamido) phosphate, phenyl = bis (phenylamido) phosphate; Tris (1,3-dichloro-2-propyl) phosphate , Phosphorous esters such as tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate; chlorine-containing condensed phosphate ester; phosphorus-containing polyester resin; hexaphenoxycyclotriphosphazene, hexamethoxycyclotriphosphazene, hexapropoxycyclotri And phosphazenes such as phosphazenes.

  The phosphorus-based flame retardant preferably has a melting point of 40 to 150 ° C. When the melting point of the phosphorus-based flame retardant is within this range, the state change from solid to liquid or from liquid to solid occurs when heat-treated in a bath and cooled, and the emulsifying dispersibility of the flame retardant by using the compound (B) The effect of suppressing the decrease is increased. As a result, the effect of reducing spec stains and can body contamination is increased. The melting point of the phosphorus-based flame retardant is more preferably 50 to 150 ° C, and further preferably 70 to 140 ° C.

  Examples of the phosphorus-based flame retardant having a melting point of 40 to 150 ° C. include triphenyl phosphate (melting point: about 50 ° C.), tri-p-cresyl phosphate (melting point: about 80 ° C.), p-xenyl diphenyl phosphate (melting point: about 62 ° C.), triorxenyl phosphate (melting point about 114 ° C.), α-naphthyl diphenyl phosphate (melting point about 52 ° C.), di (β-naphthyl) phenyl phosphate (melting point about 60 ° C.), di (β-naphthyl) phenyl Phosphate (melting point approximately 63 ° C.), tri (β-naphthyl) phosphate (melting point approximately 111 ° C.), 5,5-dimethyl-2- (2′-phenylphenoxy) -1,3,2-dioxaphosphorinane-2 Oxide (melting point: about 128 ° C.), resorcinol bis (dixylenyl phosphate) (melting point: about 92 ° C.), triphenylphosphine Xide (melting point: about 150 ° C.), 10-benzyl-9,10-dihydro-9-oxo-10λ (5) -phosphaphenanthrene = 10-oxide (melting point: about 110 ° C.), 10-phenoxy-9,10-dihydro -9-oxo-10λ (5) -phosphaphenanthrene = 10-oxide (melting point: about 110 ° C.), diphenyl = (phenylamide) phosphate (melting point: about 130 ° C.), hexaphenoxycyclotriphosphazene (melting point: about 110 ° C.), etc. Is mentioned.

  From the viewpoint of excellent flame retardancy, the weight ratio of brominated flame retardant to phosphorus flame retardant in the bath (brominated flame retardant / phosphorous flame retardant) is preferably 100/0 to 1/99, 95/5 to 5/95 is more preferable, 95/5 to 50/50 is more preferable, and 95/5 to 70/30 is particularly preferable.

The median particle size (D ₅₀ ) of the flame retardant (A) in the bath is not particularly limited, but is preferably 5 μm or less in view of excellent stability over time and further exerting the effects of the present invention. 2-2.0 micrometers is more preferable and 0.2-1.0 micrometer is still more preferable. When the median particle size exceeds 5 μm, stability over time and exhaustion may be inferior. In the present invention, the median particle diameter (D ₅₀ ) means a median value (median value) of particle diameters based on volume.

<Compound (B)>
The compound (B) is a reaction product of an acid anhydride (b1) and an organic compound (b2) having a hydroxyl group (a compound obtained by reacting an acid anhydride and an organic compound having a hydroxyl group). By using the flame retardant (A) and such a compound (B), the emulsifying dispersibility of the flame retardant (A) melted by the heat treatment can be improved, and spec stains and can contamination can be reduced. Compound (B) may be used alone or in combination of two or more.

  The acid anhydride (b1) as used herein refers to a compound having one or more structures in which two molecules of carboxylic acid are dehydrated and condensed in the molecule. The structure in which two molecules of carboxylic acid in the molecule are dehydrated and condensed may be one, or may be two or more like an acid dianhydride.

  Examples of the acid anhydride include maleic acid anhydride, succinic acid anhydride, alkenyl succinic acid anhydride, phthalic acid anhydride, cyclopentane-1,2-dicarboxylic acid anhydride, hexahydrophthalic acid anhydride, 1, 2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 4-phenylethynylphthalic anhydride Product, trimellitic acid anhydride, cyclohexa-1,2,4-tricarboxylic acid-1,2-anhydride, nadic acid anhydride, methyl nadic acid anhydride, bicyclo [2,2,1] heptane-2, 3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride, 2,3-na Phthalenedicarboxylic anhydride, 1,8-naphthalenedicarboxylic anhydride, 2,3-anthracenedicarboxylic anhydride, styrene-maleic anhydride copolymer, olefin-maleic anhydride copolymer, methyl And vinyl ether-maleic anhydride copolymer. Examples of the acid dianhydride include ethylenetetracarboxylic dianhydride, pyromellitic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic acid. Acid dianhydride, 4,4'-oxydiphthalic anhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, ethylene glycol bistrimellitic dianhydride, glycerin bistrimellitic dianhydride monoacetate, p-phenylenebis (trimellitate anhydride), 5 -(2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2carboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-cycl Lohexene-1,2 carboxylic dianhydride, bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic anhydride, 1,2,3,4-cyclobutanetetracarboxylic And acid dianhydrides, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, and the like.

  Among these, phthalic anhydride, cyclopentane-1,2-dicarboxylic anhydride, hexahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6- Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 4-phenylethynylphthalic anhydride, trimellitic anhydride, cyclohexa-4-1,2,4-tricarboxylic acid 1,2-anhydride, 2,3-naphthalenedicarboxylic acid anhydride, 1,8-naphthalenedicarboxylic acid anhydride, 2,3-anthracenedicarboxylic acid anhydride, pyromellitic acid anhydride, 1,2,3,4 -Butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid Anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, ethylene glycol bistrimellitic dianhydride, glycerin bistrimellitic dianhydride monoacetate, p-phenylenebis (trimellitate anhydride), 2,3,6,7-naphthalenetetracarboxylic dianhydride is preferred, 1,4,5,8-naphthalenetetracarboxylic dianhydride, phthalic anhydride, trimellitic anhydride, cyclohexa-1, 2,4-tricarboxylic acid-1,2-anhydride, pyromellitic anhydride, 4,4'-oxydiphthalic anhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3, More preferred are 3 ′, 4,4′-biphenyltetracarboxylic dianhydride and ethylene glycol bistrimellitate dianhydride.

  The organic compound (b2) having a hydroxyl group refers to a compound having one or more hydroxyl groups in the molecule, and examples thereof include alcohols and phenols. Examples of the organic compound having a hydroxyl group include monohydric alcohols, polyhydric alcohols, monohydric phenols, polyhydric phenols, these alkylene oxide adducts, and derivatives thereof. Moreover, alkylene oxide adducts of alkanolamines and alkylamines are also included.

Examples of the organic compound (b2) having a hydroxyl group include methanol, ethanol, propanol, isopropyl alcohol, butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexyl alcohol, decyl alcohol, dodecyl alcohol, lauryl alcohol, myristyl alcohol, Cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, allyl alcohol, crotyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, ethylene glycol, propanediol, glycerin, trimethylolpropane, sorbitan, sorbitol, pentaerythritol, xylitol, polyethylene Glycol, polyalkylene glycol, polyoxya Xylene alkyl ether, polyoxyalkylene alkyl aryl ether (polyoxyalkylene nonyl phenyl ether, etc.), polyoxyalkylene polycyclic aryl ether (polyoxyalkylene tristyryl phenyl ether, polyoxyalkylene distyryl phenyl ether, polyoxyalkylene styryl phenyl ether) Polyoxyalkylene tristyryl methyl phenyl ether, polyoxyalkylene distyryl methyl phenyl ether, polyoxyalkylene benzyl phenyl ether, polyoxyalkylene cumyl phenyl ether, polyoxyalkylene dicumyl phenyl ether, polyoxyalkylene naphthyl ether, etc.), Polyoxyalkylene castor oil ether, polyoxyalkylene hydrogenated castor oil Ether, polyoxyalkylene polyhydric alcohol ether, monoethanolamine, diethanolamine, triethanolamine, polyoxyalkylene alkyl amino ethers. In addition, various substituents may be bonded to these compounds.
Among these, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl aryl ether (polyoxyalkylene nonyl phenyl ether, etc.), polyoxyalkylene polycyclic aryl ether (Polyoxyalkylene tristyryl phenyl ether, polyoxyalkylene distyryl phenyl ether, polyoxyalkylene styryl phenyl ether, polyoxyalkylene tristyryl methyl phenyl ether, polyoxyalkylene distyryl methyl phenyl ether, polyoxyalkylene benzyl phenyl ether, poly Oxyalkylene cumyl phenyl ether, polyoxy Lucylene dicumyl phenyl ether, polyoxyalkylene naphthyl ether, etc.), polyoxyalkylene castor oil ether, polyoxyalkylene hydrogenated castor oil ether, polyoxyalkylene polyhydric alcohol ether, diethanolamine, triethanolamine, polyoxyalkylene alkylamino ether Cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, polyoxyalkylene polycyclic aryl ether (polyoxyalkylene tristyryl phenyl ether, polyoxyalkylene distyryl phenyl ether, polyoxyalkylene styryl phenyl ether, polyoxyalkylene tristyryl Methyl phenyl ether, polyoxyalkylene distyryl methyl phenyl ester Ether, polyoxyalkylene benzyl phenyl ether, polyoxyalkylene cumyl phenyl ether, polyoxyalkylene cumyl phenyl ether, polyoxyalkylene naphthyl ether and the like), polyoxyalkylene alkyl amino ethers is more preferred.

  The molar ratio when the acid anhydride (b1) is reacted with the organic compound (b2) having a hydroxyl group is preferably 1: 0.1 to 2, more preferably 1: 0.3 to 2, and 1: 0. 5 to 2 is more preferable.

  The method for reacting the acid anhydride (b1) with the organic compound (b2) having a hydroxyl group is not particularly limited, and a known method can be employed. For example, in a nitrogen atmosphere, the acid anhydride (b1) and the organic compound (b2) having a hydroxyl group are mixed and heated, and stirred at 100 to 150 ° C. for 1 to 6 hours to obtain the compound (B). be able to.

It is preferable that a compound (B) is a compound represented by the said General formula (1) from the point which exhibits the effect of this invention more.
In formula (1), R is an organic group. R- [A ¹ O] ₁ -is a residue obtained by removing a hydrogen atom from the hydroxyl group of the organic compound (b2) having a hydroxyl group.

  R is preferably a functional group represented by the following general formula (A) or a functional group represented by the following general formula (B).

（ただし、式（Ａ）中、Ｒ^１ａは水素原子、炭素数１〜３０の炭化水素基又は下記一般式（１ａ）で表される官能基である。）

(In the formula (A), R ^1a is a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a functional group represented by the following general formula (1a).)

（ただし、式（Ｂ）中、Ｒ^１ｂは水素原子、炭素数１〜３０の炭化水素基又は炭素数１〜３０のアルカノイル基である。Ａ^１Ｏは炭素数２〜４のオキシアルキレン基である。ｌ’及びｌ”はそれぞれ独立して０〜５０の数である。Ｍ^３は水素原子又は下記式（１ｂ）で表される官能基である。）

(In the formula (B), R ^1b is a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or an alkanoyl group having 1 to 30 carbon atoms. A ¹ O is an oxyalkylene group having 2 to 4 carbon atoms. L ′ and l ″ are each independently a number from 0 to 50. M ³ is a hydrogen atom or a functional group represented by the following formula (1b).)

（ただし、式（１ａ）中、Ｒ^３は水素原子又は炭素数１〜２４の炭化水素基である。Ｄ^１は炭素数７〜１６のアラルキル基である。ｎは１〜４の整数である。）

(Wherein (1a), ^{R 3} is .D ¹ is a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms is an aralkyl group having 7 to 16 carbon atoms .n is an integer of from 1 to 4 .)

（ただし、式（１ｂ）中、Ｒ^２は有機基である。ｍは１〜５の数である。Ｍ^１は水素原子又はアルカリ性基である。）

(In the formula (1b), R ² is an organic group. M is a number from 1 to 5. M ¹ is a hydrogen atom or an alkaline group.)

The hydrocarbon groups of R ^1a and R ^1b may be linear or have a branched structure. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkadienyl group, and an alkatrienyl group. The number of carbon atoms of the hydrocarbon group is preferably 12 to 30, more preferably 14 to 24, because the flame retardant has excellent emulsifying properties, suppresses foaming, and can further reduce spec stains and can contamination. preferable. From the same point, the hydrocarbon group is preferably an alkyl group, an alkenyl group, or an alkadienyl group, and more preferably an alkenyl group or an alkadienyl group.

  As the alkyl group, methyl group, ethyl group, isopropyl group, propyl group, butyl group, t-butyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, isodecyl group, lauryl group, tridecyl group, cetyl group , An isocetyl group, a stearyl group, a behenyl group, and the like, which may be primary, secondary, or tertiary, and may be linear or have a branched structure. Moreover, there is no restriction | limiting in particular with respect to the number of branches of an alkyl group, and a position.

  Examples of the alkenyl group, alkadienyl group, and alkatrienyl group include a vinyl group, an allyl group, an oleyl group, etc., which may be primary, secondary, or tertiary, and have a straight chain or branched structure. May be. There are no particular restrictions on the isomers such as the number of branches of carbon atoms constituting the alkenyl group, alkadienyl group, alkatrienyl group, the position of the unsaturated bond, trans, cis and the like.

The alkanoyl group of R ^1b may have a straight chain or a branched structure. The number of carbon atoms of the alkanoyl group is preferably 8 to 30, and more preferably 10 to 24, because the flame retardant is excellent in emulsifying properties, suppresses foaming properties, and can further reduce spec stains and can body contamination. .

R ³ is a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms. The hydrocarbon group may be linear or branched, and may be one or more. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkadienyl group, and an alkatrienyl group. 1-18 are preferable and, as for carbon number of a hydrocarbon group, 1-9 are more preferable. The alkyl group, alkenyl group, alkadienyl group, and alkatrienyl group are the same as those having 1 to 24 carbon atoms in the examples described for R.
R ³ is preferably a hydrogen atom or an alkyl group having 1 to 9 carbon atoms from the viewpoint of excellent emulsifiability of the flame retardant, suppressing foaming, and further reducing spec stains and can body contamination. An atom and a methyl group are more preferable, and a methyl group is particularly preferable. The position of R ³ may be any position, but the meta position and para position are preferred.

D ¹ is an aralkyl group having 7 to 16 carbon atoms. Examples of the aralkyl group include a benzyl group, a cumyl group, a styryl group, a distyryl group, a phenethyl group, a methylstyryl group, and an α-methylbenzyl group. An α-methylbenzyl group, a styryl group, a distyryl group, and a phenethyl group are preferable, and an α-methylbenzyl group, a styryl group, and a phenethyl group are more preferable.

  n is a number from 1 to 4. Among these, n is preferably 1 to 3 because the flame retardant is excellent in emulsifying properties, suppresses foaming, and can reduce spec stains and can body contamination.

A ¹ O is an oxyalkylene group having 2 to 4 carbon atoms, and may be one type or two or more types. In the case of two or more types, any of a block adduct, an alternating adduct, or a random adduct may be configured. Among these, it is preferable to contain an oxyethylene group and an oxypropylene group from the viewpoint that the flame retardant is excellent in emulsifying properties, suppresses foaming properties, and can reduce spec stains and can body contamination. More preferably, it contains a group.

  l, l ′ and l ″ are each independently a number of 0 to 50. Above all, the flame retardant is excellent in emulsifying properties, suppresses foaming, and can reduce spec stains and can contamination. In view of this, l and l ′ are preferably 1 to 30, more preferably 2 to 25, and particularly preferably 2 to 20. l ″ is preferably 0 to 30.

  m is a number from 1 to 5. Among these, from the viewpoint of emulsifying dispersibility, m is preferably 1 to 4, and more preferably 1 to 3.

R ² is an organic group. R ² is a residue obtained by removing the structure obtained by dehydration condensation of two molecules of carboxylic acid from the acid anhydride (b1).

M ¹ and M ³ are each independently a hydrogen atom or an alkaline group. Examples of the alkaline group include an alkali metal, an alkaline earth metal, or ^a group represented by NR ^a R ^b R ^c R ^d . R ^a , R ^b , R ^c and R ^d are each independently a hydrogen atom, an alkyl group, an alkanol group or a polyoxyalkylene group.
Examples of the alkali metal include lithium, sodium, and potassium. Examples of the alkaline earth metal include magnesium, calcium, barium and the like.

R ^a , R ^b , R ^c and R ^d are each independently a hydrogen atom, an alkyl group, an alkanol group or a polyoxyalkylene group. 1-30 are preferable and, as for carbon number of an alkyl group, 1-10 are more preferable. Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. 1-30 are preferable and, as for carbon number of an alkanol group, 1-10 are more preferable. Examples of such alkanol groups include a methanol group, an ethanol group, an n-propanol group, and an isopropanol group. As for carbon number of a polyoxyalkylene group, 2-4 are preferable. Examples of such a polyoxyalkylene group include a polyoxyethylene group and a polyoxypropylene group.
Among these, M ¹ and M ³ are preferably an alkali metal or ^a group represented by NR ^a R ^b R ^c R ^d .

<Fiber material>
The fiber material is not particularly limited, but a fiber having a large crystal region (for example, aliphatic polyester fiber, aromatic polyester fiber, cationic dyeable polyester fiber, aromatic polyamide fiber, aromatic polyimide fiber, diacetate fiber, triacetate). A fiber material including at least a fiber and a fiber of a monomer copolymer thereof is preferable because the flame retardant (A) is excellent in exhaustion and durability and flame retardancy is improved. Among these, a fiber material containing at least an aromatic polyester or a cationic dyeable polyester is more preferable.

  Examples of the aliphatic polyester fiber, aromatic polyester fiber, and cationic dyeable polyester fiber include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyethylene terephthalate / isophthalate, polyethylene terephthalate / 5- Examples thereof include fibers such as sodiosulfoisophthalate polyethylene / polyoxybenzoyl terephthalate and polybutylene terephthalate / isophthalate.

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 crystalline region and a fiber having a large amount of non-crystalline region, 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.

<Process of heat-treating fiber material in bath>
The method for producing a flame-retardant fiber of the present invention may be a step of heat-treating a fiber material in a bath containing the flame retardant (A) and the compound (B) (hereinafter simply referred to as a flame-retardant treatment step). ). By immersing the fiber material in such a bath, the flame retardant (A) can be imparted, and heat treatment can be performed while the fiber material is immersed, thereby imparting washing durability.

  The heat treatment temperature is preferably 80 ° C. or higher, more preferably 100 to 150 ° C. The heat treatment time is preferably 2 to 120 minutes, more preferably 10 to 60 minutes. The weight of the flame retardant (A) in the bath is preferably 0.1 to 50% by weight, more preferably 0.1 to 30% by weight, still more preferably 0.5 to 20% by weight, based on the fiber material. ˜15% by weight is particularly preferred. If 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, if the treatment amount is more than 50% by weight, the resulting flame-retardant fiber has a poor texture, and the adhesion efficiency to the fiber material is poor, which may not be economical.

The weight ratio of the fiber material to the bath is preferably 1/2 to 1/100, more preferably 1/3 to 1/50.
The proportion of the compound (B) in the bath is preferably 1 to 200 parts by weight, more preferably 1 to 100 parts by weight, and still more preferably 2 to 50 parts by weight with respect to 100 parts by weight of the flame retardant (A). When the ratio is less than 1 part by weight, the spec stain and can contamination may not be reduced. On the other hand, when the ratio is more than 200 parts by weight, the exhaustibility of the flame retardant (A) may be reduced, the fastness may be reduced, or the slow dyeing effect may be increased when used together during dyeing.

  The method for producing a flame-retardant fiber of the present invention can be performed using, for example, a liquid dyeing machine, a beam dyeing machine, a cheese dyeing machine, or the like.

  In the method for producing the flame-retardant fiber of the present invention, in the bath, the compound (C) represented by the following general formula (2), the compound (D) represented by the following general formula (3) and the following general formula ( At least one selected from polyester (E) having a structural unit represented by 4a) and a structural unit represented by the following general formula (4b) and a compound (F) represented by the following general formula (5): Furthermore, it is preferable to contain. By using these compounds, the emulsifying dispersibility of the flame retardant (A) can be further improved, and spec stains and can body contamination can be reduced.

（ただし、式中、Ｒ^４は炭素数１〜３０の炭化水素基である。Ｒ^５は炭素数１〜３０の炭化水素基又は下記一般式（２ａ）で表される官能基である。Ａ^３Ｏは炭素数２〜４のオキシアルキレン基である。Ｚは単結合又はカルボニル基である。ｐは０〜５０の整数である。）

(However, in the formula, R ⁴ is a hydrocarbon group having 1 to 30 carbon atoms. R ⁵ is a hydrocarbon group having 1 to 30 carbon atoms or a functional group represented by the following general formula (2a). ³ O is an oxyalkylene group having 2 to 4 carbon atoms, Z is a single bond or a carbonyl group, and p is an integer of 0 to 50.)

（ただし、式中、Ｒ^６は水素原子又は炭素数１〜２４の炭化水素基である。Ｙ^１は炭素数７〜１６のアラルキル基である。ｑは１〜４の整数である。）

(In the formula, R ⁶ is a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms. Y ¹ is an aralkyl group having 7 to 16 carbon atoms. Q is an integer of 1 to 4.)

（ただし、式中、Ｒ^７は水素原子又は炭素数１〜２４の炭化水素基である。Ａ^４Ｏは炭素数２〜４のオキシアルキレン基である。Ｙ^２は炭素数７〜１６のアラルキル基である。Ｍ^２は水素原子又はアニオン性基である。ｓは０〜５０の整数である。ｒは１〜４の整数である。）

(In the formula, R ⁷ is a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms. A ⁴ O is an oxyalkylene group having 2 to 4 carbon atoms. Y ² is an aralkyl having 7 to 16 carbon atoms. M ² is a hydrogen atom or an anionic group, s is an integer of 0 to 50, r is an integer of 1 to 4)

（ただし、式中、Ａ^５は炭素数１〜２４の炭化水素基である。Ａ^７は炭素数１〜２４の炭化水素基である。Ａ^６及びＡ^８は、それぞれ独立して炭素数２〜８の炭化水素基である。Ｗは、カルボキシル基、下記一般式（４ｃ）で表される官能基、下記一般式（４ｄ）で表される官能基又はそれらの塩である。ａは１〜１００、ｂは１〜１００の整数である。[Ａ^６Ｏ]_ａ又は[Ａ^８Ｏ]_ｂを構成するＡ^６Ｏ又はＡ^８Ｏは、同一でもよく、異なっていてもよい。）

(However, in the formula, A ⁵ is a hydrocarbon group having 1 to 24 carbon atoms. A ⁷ is a hydrocarbon group having 1 to 24 carbon atoms. A ⁶ and A ⁸ are each independently 2 carbon atoms. It is a hydrocarbon group of ~ 8. W is a carboxyl group, a functional group represented by the following general formula (4c), a functional group represented by the following general formula (4d), or a salt thereof. -100 and b are integers of 1 to 100. [A ⁶ O] _a or [A ⁸ O] A ⁶ O or A ⁸ O constituting _b may be the same or different.

  In addition, about the detail and preferable range of these compounds (C), a compound (D), and a compound (E), with compound (B1), a compound (C), polyester (B2) of Unexamined-Japanese-Patent No. 2014-224336, and It is the same.

The compound (F) is a compound represented by the following general formula (5).

In the formula, R ⁸ , R ⁹ and R ¹⁰ are each independently a group represented by “—X—Y” or “—Y”. Therefore, R ⁸ , R ⁹ and R ¹⁰ may be the same or different.
X is a linear or branched alkylene group or a linear or branched alkenylene group. The number of carbon atoms of the alkylene group or alkenylene group is preferably from 1 to 10, more preferably from 1 to 8, still more preferably from 1 to 6, and particularly preferably from 1 to 4, from the viewpoint of emulsion dispersibility.

  Y is an organic group containing no hydrogen atom or halogen atom. Examples of the organic group having no halogen atom include an alkyl group, an alkenyl group, an aromatic hydrocarbon group, an alkyl ester group, an alkenyl ester group, an alkylamino group, a polyoxyalkylene group, a polyoxyalkylene alkyl ether group, and a glycidyl group. Can be mentioned. Of these, aromatic hydrocarbon groups, alkyl ester groups, alkenyl ester groups, alkylamino groups, polyoxyalkylene groups, and polyoxyalkylene alkyl ether groups are preferred from the viewpoint of emulsifying dispersibility, alkyl ester groups, alkenyl ester groups. More preferred are a polyoxyalkylene group and a polyoxyalkylene alkyl ether group.

To illustrate an organic group having no halogen atom in more _{detail, -R, -OH, -OCOR, -COOH} , -COOR, -NH 2, -CONHR, -OCONHR, -CHOCH 2, - (OCH 2 CH 2) _{n OH, - (OCH 2 CH} 2) n OCOR, -OCOCH 2 (OCH 2 CH 2) n OR, -OC 6 H 5-m [CH (CH 3) C 6 H 5] m, - (OCH 2 CH _{2) n OC 6 H 5-} m [CH (CH 3) C 6 H 5] m , and the like. R is an aromatic hydrocarbon group, an alkyl group or an alkenyl group. m is an integer of 1 to 3, and n is an integer of 1 to 50. Among these, from the viewpoint of emulsification and dispersibility, —OH, —OCOR, —COOH, —CONHR, — (OCH ₂ CH ₂ ) _n OH, — (OCH ₂ CH ₂ ) _n OCOR, —OCOCH ₂ (OCH ₂ CH _{2) n OR, -OC 6 H} 5-m [CH (CH 3) C 6 H 5] m, - (OCH 2 CH 2) n OC 6 H 5-m [CH (CH 3) C 6 H 5] _m is _{preferably, -OH, -OCOR, -COOH, -} (OCH 2 CH 2) n OH, - (OCH 2 CH 2) n OCOR, -OCOCH 2 (OCH 2 CH 2) n OR, -OC 6 H 5 _{-m [CH (CH 3) C} 6 H 5] m, - (OCH 2 CH 2) n OC 6 H 5-m [CH (CH 3) C 6 H 5] m is more preferable.

  As the flame retardant (A) to be added to the bath, the flame retardant processing agent of the present invention to be described later may be used. A brominated flame retardant and / or a phosphorus flame retardant is emulsified, dissolved, and dispersed in water or the like in advance. Each flame retardant processing chemical may be used. In order to emulsify, dissolve and disperse the flame retardant (A) in water or the like, the above-mentioned compound (C), compound (D), polyester (E), compound (F) or other surfactants are used. be able to.

  Examples of the surfactant include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants, and nonionic surfactants are preferred in terms of excellent emulsifiability of the flame retardant (A). An anionic surfactant is preferable in that the dispersibility of (A) is excellent.

  The anionic surfactant is not particularly limited, and examples thereof include alkyl sulfate salts, alkyl aryl sulfate salts, polycyclic aryl sulfate salts, polyoxyalkylene alkyl ether sulfate salts, polyoxyalkylene alkyl aryl ether sulfate salts (polyoxyalkylenes). Nonylphenyl ether sulfate salts), polyoxyalkylene polycyclic aryl sulfate salts (polyoxyalkylene tristyryl phenyl ether sulfate salts, polyoxyalkylene distyryl phenyl ether sulfate salts, polyoxyalkylene styryl phenyl ether sulfate salts, polyoxyalkylene styryl salts Methyl phenyl ether sulfate salt, polyoxyalkylene distyryl methyl phenyl ether Fate salt, polyoxyalkylene tristyryl methyl phenyl ether sulfate salt, polyoxyalkylene benzyl phenyl ether sulfate salt, polyoxyalkylene dibenzyl phenyl ether sulfate salt, polyoxyalkylene cumyl phenyl ether sulfate salt, polyoxyalkylene dicumyl phenyl ether Sulfate salts, polyoxyalkylene naphthyl ether sulfate salts, etc.), polyoxyalkylene alkyl polyhydric alcohol ether sulfate salts, alkyl sulfonate salts, α-olefin sulfonate salts, alkyl aryl sulfonate salts, alkyl aryl disulfonate salts (alkyl diphenyl disulfonate salts) Etc.), bis (polyoxyalkylene styryl phenyl ether) succinate Stealsulfonate salt, alkylsulfosuccinate, alkyl phosphate salt, alkylaryl phosphate salt, polyoxyalkylene alkyl ether phosphate salt, polyoxyalkylene alkyl aryl ether phosphate salt, polycyclic aryl ether phosphate salt, polyoxyalkylene polycyclic aryl ether phosphate Salt, polyoxyalkylene alkyl polyhydric alcohol ether phosphate salt, aromatic sulfonate (alkyl naphthalene sulfonate, naphthalene sulfonate, etc.), aromatic sulfonic acid formalin condensate salt (alkyl naphthalene sulfonic acid formalin condensate salt, Naphthalenesulfonic acid formalin condensate salt, creosote oil sulfonate based formalin condensate, etc.), melamine sulfonate condensate, bisphenol Rusuruhon acid salt condensate, alkyl carboxylate salts, polyoxyalkylene alkyl ether carboxylate salt, polycarboxylate, Turkey red oil, lignin sulfonate salts and the like.

  As the alkyl group constituting these anionic surfactants, methyl group, ethyl group, propyl group, butyl group, hexyl group, 2-ethylhexyl group, decyl group, lauryl group, isodecyl group, tridecyl group, cetyl group, stearyl group , An oleyl group, a behenyl group, and the like, which may have an unsaturated bond, may be primary, secondary, or tertiary, and may have a straight chain or a branched structure.

  Similarly, examples of the alkylaryl group include tolyl group, xylyl group, cumyl group, octylphenyl group, 2-ethylhexylphenyl group, nonylphenyl group, decylphenyl group, methylnaphthyl group and the like. There is no limitation.

  Similarly, as the polycyclic aryl group, styrylphenyl group, styrylmethylphenyl group, styrylnonylphenyl group, alkylstyrylphenyl group, tristyrylphenyl group, distyrylphenyl group, distyrylmethylphenyl group, tristyrylphenyl group, benzyl A phenyl group, a dibenzylphenyl group, an alkyldiphenyl group, a diphenyl group, a cumylphenyl group, a naphthyl group and the like can be mentioned, and the position and number of substituents are not limited.

  Similarly, examples of the polyhydric alcohol include sorbitol, sorbitol, sorbide, sorbitan, pentaerythritol, trimethylolpropane, glycerin, neopentyl glycol, xylitol, erythritol, alkanolamine, and saccharides.

  Similarly, examples of the polyoxyalkylene group include a polyoxyethylene group, a polyoxypropylene group, and a polyoxybutylene group, and a polyoxyethylene group and a polyoxypropylene group are preferable. In the case of two or more types, any of a block adduct, an alternating adduct, or a random adduct may be configured. Moreover, it is preferable that a polyoxyalkylene group contains a polyoxyethylene group essential. The proportion of the polyoxyethylene group in the polyoxyalkylene group is preferably 40 mol% or more, more preferably 50 mol%, still more preferably 60 mol% or more, and particularly preferably 80 mol% or more. 1-50 are preferable, as for the addition mole number of an oxyalkylene group, 3-30 are more preferable, and 5-20 are more preferable.

  When the 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. Examples of the alkali metal include sodium, potassium, lithium and the like. Examples of the alkaline earth metal include magnesium, calcium, and barium. Organic amines include alkylamines (trimethylamine, triethylamine, monomethylamine, dimethylamine, etc.), alkanolamines (monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, dimethylethanolamine, diethyl) Ethanolamine etc.). Examples of quaternary ammonium include tetramethylammonium, tetraethylammonium, tetramethanolammonium, and tetraethanolammonium. These anionic surfactants may be used alone or in combination of two or more.

  Among these anionic surfactants, the compound (D) is preferable in that it has excellent dispersibility of the flame retardant and is excellent in reducing dirt on the fiber material and contamination of the can.

  The cationic surfactant is not particularly limited. For example, quaternary ammonium salts (lauryl dimethyl benzyl ammonium chloride, cetyl trimethyl ammonium chloride, lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, cetyl pyridinium chloride, cetyl pyridinium bromide, Stearamide methylpyridinium chloride, etc.). 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 glycol, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl aryl ether (polyoxyalkylene nonyl phenyl ether, etc.), polyoxyalkylene polycyclic aryl ether (poly Oxyalkylene tristyryl phenyl ether, polyoxyalkylene distyryl phenyl ether, polyoxyalkylene styryl phenyl ether, polyoxyalkylene tristyryl methyl phenyl ether, polyoxyalkylene distyryl methyl phenyl ether, polyoxyalkylene benzyl phenyl ether, polyoxyalkylene Cumyl phenyl ether, polyoxyalkylene dicumyl phenyl ether, polyoxyalkylene na Tilethers, etc.), polyoxyalkylene alkylamines, polyoxyalkylene alkylamides, polyoxyalkylene fatty acid esters, polyoxyalkylene fatty acid diesters, polyoxyalkylene alkyl ether fatty acid esters, polyoxyalkylene alkyl aryl ether fatty acid esters, polyoxyalkylene polycycles Aryl ether fatty acid ester, polyoxyalkylene castor oil ether, polyoxyalkylene hydrogenated castor oil ether, polyoxyalkylene polyhydric alcohol ether and the like can be mentioned.

  The alkyl group, alkylaryl group, polycyclic aryl group, polyhydric alcohol and polyoxyalkylene group constituting these nonionic surfactants are the same as those exemplified for the anionic surfactant. As fatty acids constituting these nonionic surfactants, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, montanic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, ricinoleic acid, Examples include erucic acid, coconut oil fatty acid, palm oil fatty acid, palm kernel oil fatty acid, beef tallow fatty acid, castor oil fatty acid, rapeseed oil fatty acid and the like.

  Among these nonionic surfactants, the above-mentioned compound (C) and / or compound (D) is excellent in the emulsifying dispersibility of the flame retardant (A), and in reducing dirt on the fiber material and contamination of the can. preferable.

  The amphoteric surfactant is not particularly limited, and examples thereof include an amino acid type (such as laurylaminopropionate), a betaine type (such as lauryldimethylammonium betaine, stearyldimethylammonium betaine, and lauryldihydroxyethylbetaine). These amphoteric surfactants may be used alone or in combination of two or more.

  As a method of emulsifying, dissolving, and dispersing the flame retardant (A) in water or the like, a known method can be used. For example, a method of preparing a brominated flame retardant and / or a phosphorus flame retardant finely divided in advance and mixing a surfactant and water (Method 1); a brominated flame retardant and / or a phosphorus flame retardant, surface activity A method of dispersing and atomizing using an atomizer with mixing agent and water (Method 2); Mixing brominated flame retardant and / or phosphorus flame retardant with surfactant and water, and atomizing apparatus On the other hand, a bromine-based flame retardant and / or phosphorus-based flame retardant, a surfactant and water are mixed, dispersed and atomized using a micronizer, and blended (Method 3): A method of mixing bromine-based flame retardant and / or phosphorus-based flame retardant and surfactant, etc., optionally stirring, heating and dissolving to homogenize, adding water or the like while stirring to emulsify or disperse (Method 4).

  Examples of the micronizer include a bead mill, a sand grinder, and an attritor. If necessary, solvents, non-drying agents, antifoaming agents (silicone antifoaming agents, mineral oil antifoaming agents, polyether antifoaming agents, fatty acid (salt) antifoaming agents, phosphate antifoaming agents, etc.), Additives such as thickeners and inorganic salts may be added. The brominated flame retardant and / or the phosphorus based flame retardant may be fine particles of a coarse powder, or may be powdered while melting and solidifying a solid.

  As the compound (B) added to the bath, the flame retardant processing agent of the present invention described later and / or the flame retardant processing aid of the present invention described later may be used. Moreover, you may use the flame retardant processing chemical | medical agent containing the above-mentioned brominated flame retardant and / or phosphorus flame retardant, and a compound (B).

  Water is essential in the bath. The water may be pure water, distilled water, purified water, soft water, ion exchange water, industrial water, well water, tap water, or the like.

  In the method for producing a flame-retardant fiber of the present invention, it is preferable to include a pH adjuster in the bath. 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, trisodium phosphate, citric acid and the like. The pH in the bath is not limited, but the pH of the bath is preferably 2 to 9, more preferably 3 to 6 because the adhesion efficiency to the fiber material is high and can body contamination and drainage load can be reduced.

  The method for producing a flame-retardant fiber of the present invention preferably contains another surfactant in the bath, and more preferably contains a drug containing the surfactant. Examples of the surfactant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant. An anionic surfactant and a nonionic surfactant are preferred from the viewpoint of excellent emulsification or dispersibility.

  In the method for producing a flame-retardant fiber of the present invention, the content of the surfactant in the treatment bath is not particularly limited, but is preferably 0.01 to 10% by weight relative to the entire treatment bath. More preferably, the content is 01 to 5% by weight. When the content of the surfactant is less than 0.01% by weight, it may be impossible to reduce spec stains and can contamination due to the flame retardant. On the other hand, when the content of the surfactant is more than 10% by weight, the exhaustibility of the flame retardant (A) is reduced, the fastness is lowered, or the slow dyeing effect is large when used in combination with dyeing. May be.

  The method for producing a flame retardant fiber of the present invention may contain other chemicals in the bath. Other agents include dyes, pigments, optical brighteners, flame retardants, UV absorbers, penetrants, wetting agents, emulsifiers, chelating agents (polycarboxylic acids, polyacrylic acids, nitrilotriacetic acid (NTA), ethylenediamine tetra Acetic acid (EDTA), hydroxyethanediphosphonic acid, nitrilotrismethylenephosphonic acid, phosphonic acid, glutamic acid diacetic acid and their salts), metal sequestering agents, scouring agents, cleaning agents, leveling agents, slow dyeing agents, dispersing agents , Oligomer remover, carrier, soaping agent, bath softener, antistatic agent, water absorbing agent, hydrophilic agent, antifouling agent, SR agent (water-soluble polyester resin, polyester-polyalkylene glycol polycondensate, fluorine resin, etc.) , Antibacterial agent, deodorant, deodorant, antifungal agent, antiviral agent, antiallergen agent, pH slide agent, potential regulator, antifoaming agent (mineral oil, silicone ), Softener, water / oil repellent (fluorine resin, silicone resin, paraffin wax, etc.), deep colorant, hard finish, synthetic resin (polyester resin, acrylic resin, polyurethane resin, and composite resins thereof), Sewing improver (liquid paraffin, mineral oil, paraffin wax, silicone), crosslinking agent (carbodiimide, epoxy, isocyanate, oxazoline, etc.), solvent (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-dimethylpro 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, diethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol mono Ethyl ether, propylene glycol dimethyl ether, dipropylene glycol, dipropylene glycol Cole monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol, tripropylene glycol monomethyl ether, polypropylene glycol, hexylene glycol, benzyl alcohol, solfit, polyalkylene glycol, acetone, methyl ethyl ketone, 2-pentanone , 3-pentanone, 2-hexanone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, methyl lactate, ethyl lactate, pentyl lactate, diisopropyl ether, dioxane, tetrahydrofuran, pyridine, N, N-dimethylformamide N, N-dimethylacetamide, N-methylpyrrolidone, etc.), water-soluble polymer (polyvinyl alcohol) , Polyacrylic acid, polyacrylic acid ester, methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, xanthan gum, gum arabic, gelatin, polyvinyl pyrrolidone, polyethylene oxide, polyacrylamide, polystyrene sulfone Acid salt, polystyrene-maleic acid copolymer, methoxyethylene maleic anhydride copolymer, starch, alginic acid, solubilized starch, cationized starch, carboxymethyl starch, etc.). These may be used alone or in combination of two or more.

The flame-retardant fiber production method of the present invention preferably contains a dye in the bath. Examples of the dye include disperse dyes, cationic dyes, acid dyes, acid mordant dyes, metal complex dyes, direct dyes, reactive dyes, vat dyes, and the like, preferably disperse dyes and cationic dyes. A disperse dye is more preferable. The disperse dye is not particularly limited, and known dyes can be used. For example, Sumikaron dye, Kayalon Polyester dye, Miketon Polyester dye, Palanil dye, Dianix dye, TD dye, Kiwalon Polyester dye, Terasil dye, Foron dye, Serilene dye and the like can be mentioned.
The content of the dye is preferably 0.01 to 50% by weight, more preferably 0.01 to 20% by weight, and still more preferably 0.1 to 10% by weight with respect to the fiber material.

  In order to improve the light resistance of the fiber material, the flame retardant fiber production method of the present invention preferably contains a UV absorber in the bath as long as the effects of the present invention are not impaired. Examples of ultraviolet absorbers include 2- (2'-hydroxy-3'-t-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 "-hydroxy) butoxyphenyl] -5-chlorobenzotriazole, 2- (2 ', 4'-dihydroxy-5'-benzoylphenyl) -5-chlorobenzotriazole, 2- (2', 4'-dihydroxy -3'-benzoylphenyl) -5-chlorobenzotriazole, 2- (3'-benzoyl-2'-hydroxy-5'-methylphenyl) benzotria Benzotriazole UV absorbers such as 2-hydroxy-4-methoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, etc. Benzophenone ultraviolet absorber; 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyloxy) -phenol, 2,4-bis (2,4-dimethylphenyl) Triazines such as -6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2'-hydroxy-4'-propoxyphenyl) -4,6-diphenyl-s-triazine UV absorbers; benzoxazinone UV absorbers such as 2,2 '-(p-phenylene) di-3,1-benzoxazin-4-one; Cyanoacrylate ultraviolet absorbers such as ru-2-cyano-3,3-diphenyl acrylate and (2-ethylhexyl) -2-cyano-3,3-diphenyl acrylate; salicylate ultraviolet rays such as pt-butylphenyl salicylate An absorbent etc. are mentioned.

  The manufacturing method of the flame-retardant fiber of this invention may have the process (scouring process) of refine | purifying a fiber material before a flame-retardant process process. By performing the scouring step, impurities such as fiber material-derived material, spinning oil agent, spinning oil agent, knitting oil agent, weaving oil agent, and paste agent can be removed, and flame retardancy is improved. There is no particular limitation on the scouring treatment method, but the fiber material is immersed in a water-diluted bath at room temperature or higher, preferably at 50 ° C. or higher for 1 to 120 minutes, and then washed, rinsed, Perform dehydration, drying, etc. For example, it can be performed using a liquid dyeing machine, a beam dyeing machine, a cheese dyeing machine, or the like.

In the method for producing a flame-retardant fiber of the present invention, it is preferable to simultaneously perform the flame-retardant treatment step and the scouring step.
In addition, the method for producing a flame-retardant fiber of the present invention may include a processing step of processing a dye, the other flame retardant described above, an ultraviolet absorber, or the like on a fiber material before the flame-retardant treatment step. Good.
The method for producing a flame-retardant fiber of the present invention can perform rinsing, dehydration, drying and the like after the flame-retardant treatment step.

  The flame-retardant fiber manufacturing method of the present invention can perform a soaping process, a reduction cleaning process, and the like after the flame-retardant treatment process, and can remove components adhering to the surface without being exhausted by the fiber material. preferable. Examples of the component to be removed include a flame retardant (A), a dye, and a compound (B) that are not exhausted and are attached to the surface. Agents used in the soaping process and reduction cleaning process include scouring agents, cleaning agents, penetrants, soaping agents, reducing cleaning agents, wetting agents, emulsifiers, chelating agents, metal sequestering agents, surfactants, dispersants, Examples include foaming agents, oligomer removing agents, oxidizing agents, reducing agents (such as thiourea dioxide and hydrosulfite), alkali agents (such as caustic soda and soda ash), and acids. Although there is no restriction | limiting in particular in the processing method in a soaping process or a reduction | restoration washing process, in the state which immersed the fiber material in the bath diluted with water, it processes at normal temperature or more, Preferably it is 50 degreeC or more for 1 to 120 minutes, Then, Perform washing, rinsing, dehydration, drying, etc.

  The manufacturing method of the flame-retardant fiber of this invention may have the process process of another chemical | medical agent after a flame-retardant process process. Although there is no restriction | limiting in particular as a processing method, For example, after immersing a fiber material in the bath which diluted the processing chemical | medical agent with water and attaching the component of a processing chemical | medical agent, heat-treating and drying a fiber material. The temperature at this time is preferably 80 to 220 ° C, more preferably 100 ° C to 200 ° C.

  The adhesion can be performed by a padding method, a spray method, a coating method, or the like. Further, the heat treatment may be either a dry heat treatment or a 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. Processing agents at this time include dyes, pigments, optical brighteners, flame retardants, UV absorbers, penetrants, wetting agents, emulsifiers, chelating agents, metal sequestering agents, scouring agents, cleaning agents, antifoaming agents, and charging agents. Antibacterial agent, water absorbing agent, hydrophilic agent, antifouling agent, SR agent, antibacterial agent, deodorant, antifungal agent, deodorant, antiviral agent, antiallergen agent, softener, water / oil repellent, deep colorant , Hard finishes, synthetic resins, sewability improvers, crosslinking agents, solvents and the like. These may be used alone or in combination of two or more.

  In the flame-retardant fiber of the present invention, it is preferable to process a water-soluble flame retardant after the flame-retardant treatment step. As the water-soluble flame retardant, salts such as phosphoric acid, phosphorous acid, hypophosphorous acid, tripolyphosphoric acid, polyphosphoric acid, sulfamic acid, and sulfuric acid are preferable. For example, ammonium polyphosphate, guanidine phosphate, guanidine sulfamate, Ammonium sulfamate, cyclic phosphonate, ethanolamine phosphate, guanidine dimethylphosphate, guanidine dimethylphosphinate, guanylurea phosphate, guanylurea methylphosphate, guanylurea methylphosphonate, hydroxyethanediphosphonate, nitrilotrismethylene Examples thereof include phosphonates.

  In the method for producing flame retardant fibers of the present invention, a synthetic resin emulsion such as an acrylic resin or a urethane resin or a synthetic resin solution may be processed after the flame retardant treatment step. There is no restriction | limiting in particular in a processing method, A coating, a pad, spray processing etc. can be mentioned. As the coating treatment, an air knife coater, a roll coater, a blade coater, a bar coater, a brush coater, a gravure coater or the like can be used. The synthetic resin emulsion or the synthetic resin solution may contain other components such as other flame retardants.

[Flame retardant processing agent]
The flame retardant processing agent of the present invention is used for imparting flame retardancy to a fiber material, and can be suitably used in the method for producing a flame retardant fiber of the present invention. The flame retardant processing agent of the present invention is a compound (B) which is a reaction product of at least one flame retardant (A) selected from a brominated flame retardant and a phosphorus flame retardant, an acid anhydride and an organic compound having a hydroxyl group. And water. When the flame retardant processing chemical contains the flame retardant (A) and the compound (B), the emulsifiability of the flame retardant (A) melted by the heat treatment is improved, and spec stains and can body contamination can be reduced. . Moreover, good flame retardancy can be imparted to the fiber material. About the detail of a flame retardant (A), a compound (B), and water, it is the same as that of what was described with the manufacturing method of the flame-retardant fiber of this invention.

The ratio of the flame retardant (A) in the flame retardant processing chemical is preferably 1 to 60% by weight, more preferably 10 to 50% by weight, and further preferably 20 to 50% by weight.
The proportion of the compound (B) in the flame retardant processing chemical is preferably 1 to 200 parts by weight, more preferably 1 to 100 parts by weight, and still more preferably 2 to 50 parts by weight with respect to 100 parts by weight of the flame retardant (A). . When the ratio is less than 1 part by weight, the spec stain and can contamination may not be reduced. On the other hand, when the ratio is more than 200 parts by weight, the stability of the flame retardant processing agent is lowered, the exhaustibility of the flame retardant (A) is lowered, the fastness is lowered, or the dye is used in combination at the time of dyeing. In some cases, the slow dyeing effect may be increased.

  The flame retardant processing chemical further includes a compound (C) represented by the general formula (2), a compound (D) represented by the general formula (3), and a structural unit represented by the general formula (4a). It is preferable to further contain at least one selected from polyester (E) having a structural unit represented by formula (4b) and compound (F) represented by formula (5). By further containing these, the emulsifying dispersibility of the flame retardant (A) can be improved, and spec stains and can body contamination can be reduced.

The median particle size (D ₅₀ ) of the flame retardant (A) in the flame retardant processing chemical is not particularly limited, but is preferably 5 μm or less from the viewpoint of excellent stability over time and more exerting the effects of the present invention. 0.2-2.0 micrometers is more preferable and 0.2-1.0 micrometer is still more preferable. When the median particle size exceeds 5 μm, stability over time and exhaustion may be inferior.

The method for emulsifying, dissolving, and dispersing the flame retardant (A) in water is the same as that described in the method for producing a flame retardant fiber of the present invention.
In the flame retardant processing agent of the present invention, the method of emulsifying, dissolving and dispersing the flame retardant (A) in water or the like can be carried out by the above-mentioned known methods, but the flame retardant (A) is emulsified in water or the like. After dissolving and dispersing, compound (B) emulsified with compound (D) may be blended.

  Moreover, the flame-retardant processing chemical | medical agent of this invention may contain another surfactant and another component in the range which does not inhibit the effect of this invention. Other surfactants and other components are the same as the components contained in the bath described in the method for producing flame-retardant fibers of the invention.

[Flame retardant processing aid]
The flame-retardant processing aid of the present invention is used when flame-treating a fiber material using at least one flame retardant (A) selected from bromine-based flame retardant and phosphorus-based flame retardant. That is, the agent which does not contain a flame retardant (A) is meant. The processing aid can be suitably used in the method for producing a flame retardant fiber of the present invention. In the method for producing a flame retardant fiber of the invention, the ratio of the flame retardant (A) to the compound (B) can be facilitated by using a flame retardant processing aid separately from the flame retardant processing agent. Adjustments that maximize the effects of are easy.

  The flame retardant processing aid of the present invention contains a compound (B) that is a reaction product of an acid anhydride and an organic compound having a hydroxyl group. About the detail of a compound (B), it is the same as that of what was described with the manufacturing method of the flame-retardant fiber of this invention. The proportion of the compound (B) in the flame retardant processing aid is preferably 1 to 99% by weight, more preferably 5 to 70% by weight, and still more preferably 10 to 50% by weight.

  The flame retardant processing aid of the present invention preferably contains water and a solvent, and improves the stability of the flame retardant processing aid and can be easily emulsified and solubilized when introduced into a bath. Since it can do, it is preferable to contain a solvent.

The flame-retardant processing aid of the present invention preferably further contains a compound (C) represented by the above general formula (2) and / or a compound (F) represented by the above general formula (5). About the detail of a compound (C) and a compound (F), it is the same as that of what was described with the manufacturing method of the flame-retardant fiber of this invention. The ratio of the compound (C) and / or the compound (F) in the flame retardant processing aid is preferably 1 to 99% by weight, more preferably 2 to 70% by weight, and still more preferably 20 to 70% by weight.
The flame retardant processing aid of the present invention is preferably a homogeneous transparent liquid because of its good stability over time, and the compound (B) is preferably emulsified when diluted with water.

  In addition, the flame retardant processing aid of the present invention may contain other surfactants and other components as long as the effects of the present invention are not impaired. Other surfactants and other components are the same as the components contained in the bath described in the method for producing flame-retardant fibers of the invention.

[Flame-retardant fiber]
The flame retardant fiber is obtained by the method for producing a flame retardant fiber of the present invention. In the flame-retardant fiber, the flame retardant (A) is attached to the fiber material, and the compound (B) is usually removed from the fiber material.

  In flame-retardant fibers, the amount of flame retardant (A) attached to the fiber material is particularly limited because it varies depending on the type and structure of the fiber material and the type and amount of other fiber processing agents attached to the fiber material. However, it is preferably 0.01 to 50% by weight, more preferably 0.1 to 30% by weight, particularly preferably 0.5 to 15% by weight based on the flame-retardant fiber (the entire fiber including the deposit). . When the adhesion amount is less than 0.01% by weight, sufficient flame retardancy may not be imparted to the fiber material. On the other hand, if the adhesion amount exceeds 50% by weight, the resulting flame-retardant fiber may have a poor texture, and the flame-retardant effect may become saturated, which may not be economical. In addition, the adhesion amount as used in the field of this invention is a weight ratio with the flame retardant (A) adhering to the processed fiber material with respect to the dry weight of the processed fiber material.

  The adhesion weight ratio of brominated flame retardant and phosphorous flame retardant in the flame retardant fiber (brominated flame retardant / phosphorous flame retardant) is not particularly limited, but is preferably 100/0 to 5/95, 95/5 to 5/95 is more preferable, 95/5 to 50/50 is more preferable, and 95/5 to 70/30 is particularly preferable.

  In the flame-retardant fiber, the amount of the compound (B) attached to the fiber material is not particularly limited because the amount varies depending on the type and structure of the fiber material, the type of other processing agent attached to the fiber material, the amount of adhesion, and the like. However, 0-10 weight% is preferable with respect to a flame-retardant fiber, and 0-5 weight% is further more preferable.

  The flame retardant fiber preferably contains a dye. Examples of the dye include disperse dyes, cationic dyes, acid dyes, acid mordant dyes, metal complex dyes, direct dyes, reactive dyes, vat dyes, and the like, preferably disperse dyes and cationic dyes. A disperse dye is more preferable. 0.01-50 weight% is preferable with respect to a flame-retardant fiber, 0.01-20 weight% is more preferable, and 0.1-10 weight% is further more preferable.

  The flame retardant fiber preferably contains an ultraviolet absorber. As an ultraviolet absorber, the component similar to what was illustrated by the flame-retardant processing chemical | medical agent can be mentioned. 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 with respect to the flame retardant fiber.

  The flame retardant fiber may contain other components other than the above within a range not impairing the effects of the present invention. Other components include, for example, pigments, optical brighteners, matting agents, flame retardants, UV absorbers, penetrants, wetting agents, emulsifiers, chelating agents, metal sequestering agents, scouring agents, cleaning agents, and antifoaming agents. , Antistatic agent, water absorbing agent, hydrophilic agent, antifouling agent, SR agent, antibacterial agent, deodorant, antifungal agent, deodorant, antiviral agent, antiallergen agent, heat shield, softener, water repellent An oil repellent, a deep color agent, a hard finish, a synthetic resin, a sewability improver, a crosslinking agent, a solvent and the like can be mentioned. These may be used alone or in combination of two or more.

  Flame retardant fiber is used for interior materials of automobiles, airplanes, railways, ships, etc .; bedding such as futons, mattresses, sheets, pillows, covers, blankets, towels; clothing such as disaster hoods and fire clothes; curtains, blinds, sofas It can be used for many applications such as chairs, paper bags, blackout curtains, wallpaper, plywood for display, fiberboards, notebooks, construction sheets, carpets, tablecloths, cushions, shoji, bran, tents, and interiors.

  Flame retardant fibers are UL-94 vertical combustion test, UL-94 thin material vertical combustion test, JIS-L-1091 method A (micro burner method, Meckel burner method, horizontal method, vertical method), method B (surface) Combustion test), C method (burning rate test), D method (flame contact test), E method (oxygen index method test), JIS-D-1201, FMVSS-302 method (combustion test of automotive interior materials), etc. It is preferably used for applications that are applied to combustion tests.

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

〔Evaluation method〕
[Flame retardancy evaluation method]
1) Coil method The flame contact number was measured according to D method of JIS-L-1091. The vertical and horizontal measurements were made 5 times, and the minimum value was calculated. The minimum value is preferably 3 or more, and more preferably 4 or more.
2) 45 degree micro burner method The after flame time was measured according to A-1 method of JIS-L-1091. The vertical and horizontal measurements were made 5 times, and the maximum value was calculated. The maximum value is preferably 3 seconds or less, and more preferably 1 second or less.

[Evaluation method for spec-prevention and can body contamination]
The prepared flame retardant processing agent and the flame retardant processing aid are introduced into the mini color dedicated pot (450 mL in volume) into which water has been added so as to have the concentrations shown in Table 6 or 7, and the pH is adjusted to 4. with an acetic acid / sodium acetate buffer. 5 to prepare a flame retardant processing bath. Thereafter, Brian C-1820 (2 g / L, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), which is a knitting oil, was charged into the bath. The assumed fiber material amount at that time was 20 g, and the assumed bath ratio was 1:10.
Next, only the flame retardant processing bath was treated with a mini color. As processing conditions, the temperature was increased to 135 ° C. at a rate of 2 ° C. per minute, and 135 ° C. was maintained for 60 minutes. Then, when it cooled and became 60 degreeC, the flame-retardant processing bath was filtered using black filter paper. The specification prevention evaluation was performed according to the following criteria in a state where the black filter paper was naturally dried. In addition, the can body contamination was determined by the following criteria for the degree of contamination of the mini-color dedicated pot.

・ Evaluation criteria for specification prevention ○: The flame retardant hardly adheres to the filter paper.
○-: Oil spots or aggregates due to the flame retardant are slightly seen on the filter paper.
(Triangle | delta): The oil spot or aggregate by a flame retardant is seen in a part of filter paper (the intermediate level of (circle) and x).
×: Oil spots or aggregates due to the flame retardant are observed on the entire filter paper.

-Can body contamination evaluation criteria ○: There is almost no flame retardant stain in the mini color pot.
○-: Slightly contaminated flame retardant in mini color pot.
(Triangle | delta): The stain | pollution | contamination of a flame retardant is seen in a part in pot only for mini color.
X: Dirt of flame retardant is seen in the entire mini color pot.

[Evaluation method for spec prevention 2 and can body contamination 2]
Except for changing the following points, the spec prevention property 2 and the can body contamination property 2 were evaluated in the same manner as the above-described evaluation method for the spec prevention property and can body contamination property.
-Instead of Brian C-1820 which is a knitting oil agent, Kayalon Polyester Black RV-SF300 (6 g / L, Nippon Kayaku Co., Ltd.) which is a disperse dye is used.
・ Use white filter paper instead of black filter paper.
-“Flame Retardant” should be read as “Flame Retardant and Dye” in the Standards for Evaluation of Anti-Spectability and the Standard for Evaluation of Contamination of Cans.

[Production Example of Phosphorus Flame Retardant (A-1)]
716 g of p-cresol (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.70% by weight, phenol 0.10% by weight, o-cresol 0.20% by weight) and aluminum chloride 16g were added, and phosphorus oxytrichloride at 80 ° C. 335 g was slowly added dropwise over 2 hours, and the generated hydrogen chloride was removed. After completion of dropping, the mixture was aged at 120 ° C. for 3 hours. The reaction product was cooled to 90 ° C., 500 g of 5 wt% sodium hydroxide solution was added, and the mixture was stirred at 90 ° C. for 1 hour. The aqueous phase was removed and the reaction was poured into cold water, washed for 1 hour, dehydrated, and further washed with water for 1 hour. After dehydration and drying, 770 g of a phosphorus-based flame retardant (A-1) having a purity of 99.1% tri-p-cresyl phosphate and a white solid having a melting point of 78 ° C. was obtained.

[Production Example of Compound (B)]
[Production Example 1]
Trimellitic anhydride and POE (13) styrenated phenol were mixed at a molar ratio of 1: 1 and stirred at 110 ° C. for 3 hours in a nitrogen atmosphere to obtain trimellitic anhydride and POE (13) styrenated phenol. The ester reaction product (B-1) was obtained.

[Production Examples 2 to 20]
In Production Example 1, the same procedure as in Production Example 1 except that the acid anhydride (b1) and the organic compound (b2) having a hydroxyl group shown in Table 1 were changed to their molar ratio (b1: b2) and reaction temperature / time. Thus, ester reaction products (B-2) to (B-20) were obtained.

In addition, it shows below about the detail of the organic compound (b2) which has a hydroxyl group of Table 1.
-POE (13) styrenated phenol POE (13) means that the average number of repeating oxyethylene groups is 13. The styrenation degree of styrenated phenol is mono: di: tri = 15: 50: 35 in weight ratio.
POE (10) styrenated cresol Cresol is p-cresol: m-cresol = 50: 50, and the styrenation degree of styrenated cresol is mono: di = 50: 50 by weight ratio.
POE (3) styrenated phenol The styrenation degree of styrenated phenol is mono: di: tri = 15: 50: 35 by weight ratio.
-POE (30) styrenated phenol The styrenation degree of styrenated phenol is mono: di: tri = 15: 50: 35 by weight ratio.
POEO (3/7 random) styrenated phenol POEO (3/7 random) means a random adduct having an average number of repeating oxyethylene groups and oxypropylene groups of 3 and 7. The styrenation degree of styrenated phenol is di: tri: tetra = 10: 80: 10 by weight ratio.

[Production Example of Compound (C-1)]
In a 2000 mL four-necked flask, 570 g of rapeseed oil fatty acid and 600 g of polyethylene glycol (average molecular weight 600) were added and stirred at 240 ° C. for 6 hours. 1114 g of a compound (C-1) that does not dissolve in 20 ° C. water containing rapeseed oil fatty acid diester of polyethylene glycol was obtained, and the acid value was 5.

[Production Example of Compound (D-1)]
In a 2000 mL four-necked flask, POE (13) styrenated phenol (POE (13) means that the average number of repeating oxyethylene groups is 13. In addition, the styrenation degree of styrenated phenol is expressed by weight ratio. Mono: di: tri = 15: 50: 35) 1335 g and 71 g of phosphoric anhydride were added and stirred at 130 ° C. for 6 hours. While cooling, 150 g of triethanolamine was added to obtain 1550 g of compound (D-1) containing the triethanolamine salt of sesquiphosphate of POE (13) styrenated phenol.

[Production Example of Compound (E-1)]
A 2000 mL four-necked flask was charged with 400 g of ethylene glycol, 200 g of neopentyl glycol, 332 g of terephthalic acid, and 498 g of isophthalic acid, and reacted at 200 ° C. for 4 hours while distilling off the generated water in a nitrogen atmosphere. Subsequently, 150 mg of antimony trioxide was added as a catalyst and reacted at 260 ° C. for 3 hours. Next, 96 g of trimellitic anhydride was added and reacted at 250 ° C. and normal pressure for 1 hour to obtain a polyester compound (E-1) having a weight average molecular weight of 5000.

[Production Example of Compound (F-1)]
A 500 mL four-necked flask is charged with 500 g of 1,3,5-tris (2-carboxyethyl) isocyanurate and 387 g of oleyl alcohol, and stirred at 210 ° C. for 3 hours while distilling off the generated water in a nitrogen atmosphere. As a result, 860 g of an ester reaction product (F-1) of 1,3,5-tris (2-carboxyethyl) isocyanurate and oleyl alcohol was obtained.

[Production Example of Compound (G-1)]
A 2000 mL four-necked flask was charged with 88 g of dimethyl terephthalate, 15 g of dimethyl sodium 5-sulfoisophthalate, 310 g of polyethylene glycol having a weight average molecular weight of 3000, 68 g of ethylene glycol, 150 mg of antimony trioxide, and 150 mg of zinc acetate. The reaction was carried out at 200 ° C. for 4 hours while distilling off the water to be distilled. Subsequently, the system was gradually reduced in pressure, and reacted at 260 ° C. and a reduced pressure of 5 mmHg for 3 hours to obtain a polyester compound (G-1) having a weight average molecular weight of 15000.

[Production Example of Flame Retardant Chemicals a1 to a22]
The compounding components (parts by weight) shown in Tables 2 and 3 were added to a Despa-type stirrer and sufficiently stirred and dispersed at 25 ° C. Thereafter, the obtained slurry was microparticulated for 6 hours at 25 ° C. using Starmill ZRS (manufactured by Ashizawa Finetech Co., Ltd.) to prepare flame retardant processing chemicals. In addition, the compound (D-2) shown in Tables 2 and 3 is POE (10) styrenated phenol. POE (10) styrenated phenol is polyoxyethylene styrenated phenol and means that the average number of repeating oxyethylene groups is 10. Moreover, the styrenation degree of styrenated phenol is mono: di: tri = 10: 80: 10 by weight ratio. The tris (2,3-dibromopropyl) isocyanurate in Tables 1 and 2 uses FCP-660CN (melting point 115 ° C.) (manufactured by Suzuyu Chemical Co., Ltd.), and ethylenebistetrabromophthalimide is SAYTEX BT-93 (melting point 456). ° C) (Albemarle Japan Co., Ltd.) was used, and FCP-65 (melting point 115 ° C) (Suzuyu Chemical Co., Ltd.) was used as the bis (3,5-dibromo-4-dibromopropyloxyphenyl) sulfone. Triphenylphosphine oxide uses TPPO (melting point 150 ° C.) (manufactured by Keisei Kasei Co., Ltd.), and triphenyl phosphate uses TPP (melting point 49 ° C.) (manufactured by Daihachi Chemical Industry Co., Ltd.), naphthyl diphenyl phosphate. Used NDPP (melting point: 52 ° C.) (manufactured by Daihachi Chemical Industry Co., Ltd.).

[Production Examples of Flame Retardant Processing Aids b1 to b34]
The compounding components (parts by weight) shown in Tables 4 to 6 were respectively added to a blender and sufficiently stirred at 20 ° C. to prepare flame retardant processing aids.

(Examples 1-68, Comparative Examples 1-18)
Using the flame retardant processing chemicals and flame retardant processing aids shown in Tables 7 and 8, respectively, the anti-spec specification and the can body contamination were evaluated.
Next, using the prepared flame retardant processing agent and flame retardant processing aid, flame retardant processing was performed under the following flame retardant processing conditions to obtain a flame retardant polyester fiber. The obtained flame-retardant polyester fiber (shown as “processed up” in the table) was evaluated for flame retardancy. Moreover, about the obtained flame-retardant polyester fiber, after washing and washing 5 times by the method of JIS-L-1091 (shown as “after 5 times of washing” in the table), and by the method of JIS-L-1018 After performing dry cleaning 5 times (shown as “after 5 DC” in the table), the flame retardancy was evaluated. These results are shown in Tables 7 and 8.

[Flame retardant processing]
In a mini color dyeing pot (volume 450 mL) of a mini color dyeing machine (manufactured by Teksam Giken Co., Ltd.), 2 g / L of Marpon ISD-1 (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), which is a scouring agent for water and dyeing. Marpomarvelin B-70 (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) as a dye, 1 g / L of a flame retardant processing agent and a flame retardant processing aid were added in amounts shown in Tables 3 and 4, followed by Kayalon Polyester Black RV- SF300 (2 wt% owf, manufactured by Nippon Kayaku Co., Ltd.) was added while being dissolved in water at 30 to 35 ° C., and then adjusted to pH 4.5 with an acetic acid / sodium acetate buffer to prepare a dyeing bath.
Next, 10 g of polyester tropical raw machine was put into the prepared dyeing bath and treated with a mini color. The bath ratio at that time was 1:20. As processing conditions, the temperature was raised to 135 ° C. at a rate of 2 ° C. per minute and maintained at 135 ° C. for 30 minutes. Then, when it cooled and became 70 degreeC, the dyeing bath was discarded and it washed with water for 5 minutes.
Next, a bath containing 1 g / L of Marpomarvelin S-1520 (manufactured by Matsumoto Yushi Seiyaku Co., Ltd.), hydrosulfite 2 g / L, and caustic soda 2 g / L as a soaping agent, with a bath ratio of 1:20 and a temperature of 80 ° C. Then, a soaping treatment was performed for 15 minutes, washed with water, and dried at 160 ° C. for 1 minute to obtain a flame-retardant polyester fiber.

  Examples 1 to 68 are all excellent in flame retardancy, anti-spec specifications, and can contamination. On the other hand, Comparative Examples 1-18 are inferior in any one in a flame retardance, specification prevention property, and can body contamination.

Claims (10)

  In a bath containing at least one flame retardant (A) selected from a brominated flame retardant and a phosphorus flame retardant and a compound (B) which is a reaction product of an acid anhydride and an organic compound having a hydroxyl group, a fiber material The manufacturing method of a flame-retardant fiber including the process of heat-processing. The method for producing flame retardant fibers according to claim 1, wherein the compound (B) is a compound represented by the following general formula (1).

(In the formula (1), R and R ² are each independently an organic group. A ¹ O is an oxyalkylene group having 2 to 4 carbon atoms. L is a number from 0 to 50.) m is a number from 1 to 5. M ¹ is a hydrogen atom or an alkaline group.)   The manufacturing method of the flame-retardant fiber of Claim 1 or 2 whose ratio of the said compound (B) is 1-200 weight part with respect to 100 weight part of said flame retardants (A).   The method for producing a flame-retardant fiber according to any one of claims 1 to 3, wherein the brominated flame retardant is tris (2,3-dibromopropyl) isocyanurate.   Flame retardant processing containing at least one flame retardant (A) selected from a brominated flame retardant and a phosphorus flame retardant, a compound (B) which is a reaction product of an acid anhydride and an organic compound having a hydroxyl group, and water Drugs. The flame retardant processing agent according to claim 5, wherein the compound (B) is a compound represented by the following general formula (1).

(In the formula (1), R and R ² are each independently an organic group. A ¹ O is an oxyalkylene group having 2 to 4 carbon atoms. L is a number from 0 to 50.) m is a number from 1 to 5. M ¹ is a hydrogen atom or an alkaline group.)   The flame retardant processing agent according to claim 5 or 6, wherein a ratio of the compound (B) is 1 to 200 parts by weight with respect to 100 parts by weight of the flame retardant (A).   The flame retardant processing agent according to any one of claims 5 to 7, wherein the brominated flame retardant is tris (2,3-dibromopropyl) isocyanurate. A flame retardant processing aid used in combination with at least one flame retardant (A) selected from a brominated flame retardant and a phosphorus flame retardant,
A flame retardant processing aid containing a compound (B) which is a reaction product of an acid anhydride and an organic compound having a hydroxyl group. The flame retardant processing aid according to claim 9, wherein the compound (B) is a compound represented by the following general formula (1).

(In the formula (1), R and R ² are each independently an organic group. A ¹ O is an oxyalkylene group having 2 to 4 carbon atoms. L is a number from 0 to 50.) m is a number from 1 to 5. M ¹ is a hydrogen atom or an alkaline group.)