JP2014224336A - Method for producing flame retardant fiber, flame retardant-processing agent, and flame-retardant processing aid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing flame retardant fiber which, when heat treating a textile material in a bath containing a flame retardant, can decrease stains (speck stains) on the textile material and tank stains (can body stain), and can impart good flame retardancy to the textile material; and to a flame retardant-processing agent and a flame-retardant processing aid which can be usd suitably for the production method.SOLUTION: The method for producing a flame retardant fiber includes a step of heat treating a textile material in a bath containing at least one flame retardant (A) selected from bromine-based flame retardants and phosphorous-based flame retardants, and a compound (B) such as a compound (B1) represented by the following general formula (1). In the formula, Ris a hydrocarbon group having 1 to 30 carbon atoms; Ris a hydrocarbon group having 1 to 30 carbon atoms or a functional group represented by the general formula (2); AO is an oxyalkylene group having 2 to 4 carbon atoms; and l is an integer between 0 and 50.

Description

  The present invention relates to a method for producing flame retardant fibers, a flame retardant processing agent for fibers, and a flame retardant processing aid for fibers. 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 agent for fibers which can be used suitably for this manufacturing method, and the flame-retardant processing aid for fibers.

  Conventionally, a flame retardant in which hexabromocyclododecane (HBCD) is dispersed or emulsified in water has been generally used in order to impart flame retardancy to fiber materials. However, hexabromocyclododecane is hardly decomposable and highly accumulative, and tends to be avoided as much as possible from the environment and human face.

  As an alternative to hexabromocyclododecane, bromine-based compounds disclosed in Patent Documents 1 to 4 are used. However, these brominated compounds are inferior in flame retardancy and poor in emulsification and dispersibility compared to hexabromocyclododecane. ) Is a problem. In order to improve the flame retardancy, in Patent Documents 5 to 7, the flame retardancy is improved by using tris (2,3-dibromopropyl) isocyanurate and a specific phosphate ester in combination. It is inferior in dyeing fastness such as light fastness and friction fastness (bleeding property). In Patent Document 8, emulsifiability and dispersibility are improved by using tris (2,3-dibromopropyl) isocyanurate and a specific surfactant in combination, but flame retardancy, emulsifiability and dispersibility are improved. Both are not compatible.

JP 2009-203595 A JP 2009-174109 A JP 2011-37966 A JP 2010-285714 A JP 2011-32588 A JP 2011-241519 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, the flame-retardant processing agent for fibers which can be used suitably for this manufacturing method, and the flame-retardant processing aid for fibers.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that when the fiber material is heat-treated in a bath, at least one flame retardant (A) selected from a bromine-based flame retardant and a phosphorus-based flame retardant. And the specific compound (B) was found to solve the problems of the present invention, and the present invention was achieved.

  That is, the method for producing a flame retardant fiber according to the present invention includes at least one flame retardant (A) selected from a brominated flame retardant and a phosphorus flame retardant, and a compound (B1) represented by the following general formula (1). ) And at least one compound (B) selected from polyester (B2) having a structural unit represented by the following general formula (3a) and a structural unit represented by the following general formula (3b): Among them, a step of heat-treating the fiber material is included.

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

(In the formula, R ³ 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. M is an integer of 1 to 4)

(In the formula, A ³ is a hydrocarbon group having 1 to 24 carbon atoms. A ⁴ is a hydrocarbon group having 1 to 24 carbon atoms. A ⁵ and A ⁶ are each independently 2 carbon atoms. And W is a carboxyl group, a functional group represented by the following general formula (4), a functional group represented by the following general formula (5), or a salt thereof. -100 and b are integers of 1 to 100. [A ⁵ O] _a or [A ⁶ O] A ⁵ O or A ⁶ O constituting _b may be the same or different.

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

  It is preferable that the method for producing a flame-retardant fiber of the present invention further contains a compound (C) represented by the following general formula (6) in the bath.

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

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

The melting point of the flame retardant (A) is preferably 40 to 150 ° C.
The brominated flame retardant is preferably tris (2,3-dibromopropyl) isocyanurate.

  The flame retardant processing agent for fibers of the present invention is used for imparting flame retardancy to a fiber material, and includes at least one flame retardant (A) selected from a brominated flame retardant and a phosphorus flame retardant, the above At least selected from the compound (B1) represented by the general formula (1) and the polyester (B2) having the structural unit represented by the general formula (3a) and the structural unit represented by the general formula (3b). It contains one kind of compound (B) and water.

  It is preferable that the flame retardant processing agent for fibers of the present invention further contains the compound (C) represented by the general formula (6).

  The flame-retardant processing aid for fibers of the present invention is for fibers used when flame-treating a fiber material using at least one flame retardant (A) selected from brominated flame retardants and phosphorus-based flame retardants. A flame retardant processing aid, comprising a compound (B1) represented by the general formula (1) and a structural unit represented by the general formula (3a) and a structural unit represented by the general formula (3b) It contains at least one compound (B) selected from polyester (B2) having Therefore, the flame retardant processing aid for fibers of the present invention does not contain a flame retardant.

  It is preferable that the flame retardant processing aid for fibers of the present invention further contains the compound (C) represented by the general formula (6).

According to the production method of the present invention, when heat treating a fiber material in a bath containing a flame retardant, spec stains and can body contamination can be reduced, and flame retardant fibers having good flame retardancy can be obtained. it can.
The flame-retardant processing agent for fibers and the flame-retardant processing aid for fibers of the present invention can be suitably used in the production method of the present invention, and by using these, the fiber material is heat treated in a bath containing the flame retardant. In doing so, dirt (spec dirt) and pot dirt (can body contamination) on the fiber material can be reduced, and good flame retardancy 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 includes at least one flame retardant (A) selected from a brominated flame retardant and a phosphorus flame retardant, a compound (B1) represented by the general formula (1), and In a bath containing at least one compound (B) selected from the polyester (B2) having the structural unit represented by the general formula (3a) and the structural unit represented by the general formula (3b). And a step of heat-treating the fiber material. According to the production method of the present invention, when a fiber material is heat-treated in a bath containing a flame retardant, the flame retardant is deteriorated in emulsifiability and dispersibility, and stains on the fiber material due to foaming (hereinafter referred to as spec stain). ) And pot dirt (hereinafter referred to as 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 changes from solid to liquid or from liquid to solid when heat-treated in a bath and cooled, and the compound (B) and further the compound (C) are used. The effect of suppressing the decrease in emulsification and dispersibility of the flame retardant due to 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, 5,5-dimethyl-2- (
Phosphate esters such as 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), bisphenol A bis (dixylenyl phosphate) ) Condensed phosphoric acid esters such as dimethyl methylphosphonate, diethyl ethylphosphonate, dipropyl methylphosphonate, dibutyl methylphosphonate, dibutyl butylphosphonate Chill, diphenyl phenylphosphonate, dicresyl phenylphosphonate, dixylyl phenylphosphonate, phenyl cresyl phenylphosphonate, bis [(5-ethyl-2-methyl-1,3,2-dioxaphosphorinan-5-yl) Methyl] methylphosphonate-P, P′-dioxide, (5-ethyl-2-methyl-1,3,2-dioxaphosphorinan-5-yl) methyldimethylphosphonate-P-oxide phosphite; Hypophosphite esters such as methyl dimethylphosphinate, ethyl diethylphosphinate, propyl dimethylphosphinate, butyl diphenylphosphinate, phenyl diphenylphosphinate, cresyl diphenylphosphinate, xylyldiphenylphosphinate, metal salts of diethylphosphinate; Phi Oxide, triethylphosphine oxide, tri-n-propylphosphine oxide, tri-n-butylphosphine oxide, tri-n-hexylphosphine oxide, tri-n-octylphosphine oxide, tricyclohexylphosphine oxide, tolylphosphine oxide, tris -3-hydroxypropylphosphine oxide, tris (2-methylphenyl) phosphine oxide, tris (4-methylphenyl) phosphine oxide, tris (2,6-dimethylphenyl) phosphine oxide, tris (2,6-dimethoxyphenyl) phosphine Phosphines such as oxide, tribenzylphosphine oxide, 2- (diphenylphosphinyl) hydroquinone, triphenylphosphine oxide 10-benzyl-9,10-dihydro-9-oxo-10λ (5) -phosphaphenanthrene = 10-oxide, 10-phenoxy-9,10-dihydro-9-oxo-10λ (5) -phospha Phosphophenanthrene derivatives such as phenanthrene = 10-oxide; phosphoric ester amides such as diphenyl = (phenylamido) phosphate and phenyl = bis (phenylamido) phosphate; tris (1,3-dichloro-2-propyl) phosphate, tris (Chloropropyl) phosphate, tris (dichloropropyl) phosphate and other chlorine-containing phosphate esters; chlorine-containing condensed phosphate esters; phosphorus-containing polyester resins; hexaphenoxycyclotriphosphazenes, hexamethoxycyclotriphosphazenes, hexapropoxy Phosphazene such as cyclotriphosphazene, and the like.

  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 changes from solid to liquid or from liquid to solid when heat-treated in a bath and cooled, and the compound (B) and further the compound (C) are used. The effect of suppressing the decrease in emulsification and dispersibility of the flame retardant due to 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 at least one selected from the compound (B1) and the polyester (B2). By using the flame retardant (A) and the compound (B), the emulsifiability of the flame retardant (A) melted by the heat treatment is improved and the foaming property is suppressed to reduce spec stains and can body contamination. can do. Compound (B) may be used alone or in combination of two or more.

(Compound (B1))
The compound (B1) is a compound represented by the general formula (1). In formula (1), R ¹ is a hydrocarbon group having 1 to 30 carbon atoms. The hydrocarbon group may be linear or have a branched structure. Also, R ¹ may be one or two or more. 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 regarding 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.

In formula (1), A ¹ O is an oxyalkylene group having 2 to 4 carbon atoms, and may be one or more. 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.

  In formula (1), l is an integer of 0-50. Among these, l is preferably 1 to 30, more preferably 4 to 20, and more preferably 4 to 20 because it is excellent in emulsifying property of the flame retardant, suppresses foaming properties, and can reduce spec stains and can body contamination. 15 is particularly preferred.

In formula (1), Z is a single bond or a carbonyl group. When Z is a single bond, “—Z—R ² ” simply indicates “—R ² ”. Z is preferably a carbonyl group from the viewpoint that spec stain and can contamination can be further reduced.

In the formula (1), R ² is a hydrocarbon group having 1 to 30 carbon atoms or a functional group represented by the above general formula (2). The details of the hydrocarbon group having 1 to 30 carbon atoms and the preferred range thereof are the same as those for R ¹ . R ² is preferably an alkenyl group, an alkadienyl group, or a functional group represented by the general formula (2) from the viewpoint that spec stains and can contamination can be further reduced.

In formula (2), ^{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 described in R ¹ and having 1 to 24 carbon atoms.
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.

In formula (2), Y 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.

  In formula (2), m is an integer of 1-4. Among these, m is preferably 1 to 3 and m is particularly preferably 3 from the viewpoint that the flame retardant has excellent emulsifiability, can suppress foaming properties, and can reduce spec stains and can body contamination.

  The compound (B1) is preferably highly hydrophobic from the viewpoint of excellent emulsifiability and foam suppression properties of the flame retardant. For example, the compound (B1) does not dissolve in water at 20 ° C. It is preferable that the 1% aqueous solution of B1) is not uniform (separated and clouded).

(Polyester (B2))
The polyester (B2) is a polyester having a structural unit represented by the general formula (3a) and a structural unit represented by the general formula (3b). By using the flame retardant (A) and polyester (B2), the emulsifiability of the flame retardant (A) melted by heat treatment is improved and the foaming properties are suppressed to reduce spec stains and can body contamination. can do. Furthermore, by improving the dispersibility of dyes, polyester oligomers, etc., spec stains and can body contamination based on dyes and oligomers can be reduced.

In formula (3a), A ³ is a hydrocarbon group having 1 to 24 carbon atoms, and is a residue obtained by removing W from the A ³ W group. The number of carbon atoms in A ³ is 2 to 12 are preferred, 6 to 10 is more preferable. In formula (3b), A ⁴ is a hydrocarbon group having 1 to 24 carbon atoms. The number of carbon atoms of A ⁴ is 2 to 12 are preferred, 6 to 10 is more preferable.
The hydrocarbon group constituting A ³ or A ⁴ may have a straight chain or a branched structure, and may be one type or two or more types. Examples of the hydrocarbon group include an alkylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, and an arylene group. Examples of the alkylene group include methylene group, ethylene group, n-propylene group, iso-propylene group, n-butylene group, 1,2-dimethylethylene group, n-pentylene group, n-hexylene group, neopentylene group, octylene group, A 2-ethylhexylene group, a sebacylene group, etc. are mentioned. Examples of the alkenylene group include an ethylenylene group, an n-propynylene group, an iso-propynylene group, an n-butylenylene group, and a 1,2-dimethylethylenylene group. Examples of the alkynylene group include an alkynylene group derived from an acetylene structure. Examples of the arylene group include a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a methylphenylene group, a tolylene group, a xylylene group, a durylene group, a biphenylene group, and a naphthylene group. An alkylene group and an arylene group are preferable, and a 1,4-phenylene group and a 1,3-phenylene group are more preferable.

In formula (3a) and formula (3b), A ⁵ and A ⁶ are each independently a hydrocarbon group having 2 to 8 carbon atoms. The number of carbon atoms of A ⁵ and ^{A 6} are, 2-6 preferably, 2 to 5 is more preferred. Examples of the hydrocarbon group having 2 to 8 carbon atoms include methylene group, ethylene group, n-propylene group, iso-propylene group, n-butylene group, 1,2-dimethylethylene group, n-pentylene group, and n-hexylene group. , Neopentylene group, octylene group, ethylenylene group, n-propynylene group, iso-propynylene group, n-butylenylene group, 1,2-dimethylethylenylene group, 1,4-phenylene group, 1,3-phenylene group, 1, 2-phenylene group, methylphenylene group, tolylene group, xylylene group and the like can be mentioned. a is an integer of 1 to 100, preferably 1 to 60, more preferably 1 to 50, and still more preferably 1 to 10. b is an integer of 1-100, 1-60 are preferable, 1-50 are more preferable, and 1-10 are more preferable.
A ^{5 O} constituting the _[A ^{5 O]} _a may be the same, can have also different. If they are different, any of a block adduct, an alternating adduct, or a random adduct may be configured. The ^{A 6} constituting the ^{[A 6} O] _b O may be the same or may be different. If they are different, any of a block adduct, an alternating adduct, or a random adduct may be configured.

  W is a carboxyl group, a functional group represented by the general formula (4), a functional group represented by the general formula (5), or a salt thereof. Among these, a salt with a carboxyl group and a functional group represented by the general formula (4) are preferable. The salt may be an alkali metal salt, alkaline earth metal salt, ammonium salt, organic amine salt, 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.).

The A ³ W group of the formula (3a) is represented by the following general formula (7) from the viewpoint that the effects of the present invention can be further exerted, and spec stains and can body contamination based on dyes and oligomers can be reduced. The indicated functional groups or salts thereof are preferred.

The A ³ W group of the formula (3a) is represented by the following general formula (8) from the viewpoint that the effects of the present invention can be further exerted and spec stains and can body contamination based on dyes and oligomers can be reduced. ) Is preferred.

  In the polyester (B2), the total weight ratio ((3a + 3b) / B2) of the structural unit represented by the general formula (3a) and the structural unit represented by the general formula (3b) is 0.5 to 1. Preferably, 0.8-1 is more preferable.

  The molar ratio (3a / 3b) between the structural unit represented by the general formula (3a) and the structural unit represented by the general formula (3b) is preferably 1/99 to 50/50, and 5/95 to 40 /. 60 is more preferable, and 5/95 to 30/70 is more preferable. The combination form of the structural unit represented by the general formula (3a) and the structural unit represented by the general formula (3b) may be random or block.

  The weight average molecular weight of the polyester (B2) is preferably 2000 to 300000, more preferably 2000 to 200000, and further preferably 3000 to 150,000.

  Examples of polyester (B2) include polyester (B2-1) represented by the following general formula (3), polyester (B2-2) derived from polyester (B2-1), and the like.

In Formula (3), A ⁷ is —OH, —O (A ⁵ O) _a A ⁸ or —O (A ⁶ O) _b A ⁸ .
Wherein (3), ^{A 8} is a hydrogen atom or ^{-A 3 W-COOH, -A 4} -COOH or salts thereof. The salt is the same as that described for W.

  In formula (3), c is an integer of 1 to 2000, preferably 1 to 1000, more preferably 1 to 200, and still more preferably 1 to 100. d is an integer of 1 to 2000, preferably 1 to 1000, more preferably 5 to 1000, and still more preferably 10 to 1000.

The combination form of the structural unit related to c and the structural unit related to d may be random or block. The ratio of c and d (c / d) is preferably 1/99 to 50/50, more preferably 5/95 to 40/60, and even more preferably 5/95 to 30/70. of polyester (B2-1) The weight average molecular weight is preferably 2000 to 300000, more preferably 2000 to 200000, and further preferably 3000 to 150,000.

The polyester ester (B2-1) can be produced by a known polyester production method, transesterification or esterification and then polycondensation. For example, presence of component (1) consisting of dicarboxylic acid (or anhydride or ester thereof), component (2) consisting of dicarboxylic acid having A ³ W group (or anhydride or ester thereof) and diol (3) Then, esterification or transesterification is performed at 100 to 230 ° C. to remove water or alcohol, and a polyester compound having a weight average molecular weight of about 500 to 2,000 is obtained. Next, the temperature and the degree of reduced pressure are gradually increased, and finally, the reaction is performed at 200 to 300 ° C. at a reduced pressure of 100 mmHg or less for 0.5 to 50 hours to increase the molecular weight. At this time, a catalyst may be used. As the catalyst, a known catalyst used for esterification, transesterification or polyesterification may be used.

  Examples of the component (1) include terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dimer acid and dihydric acid such as these anhydrides. Or esters thereof. In addition, a component (1) shall not contain a component (2).

  As the component (2), trimellitic acid, pyromellitic acid, dicarboxylic acid having a functional group represented by the general formula (8) (for example, at both ends of the functional group represented by the general formula (8)) And those having a carboxyl group) and their anhydrides or esters thereof.

  Examples of the diol (3) include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, nonanediol, neopentyl glycol, diethylene glycol, triethylene glycol, polytetramethylene glycol, polyethylene glycol, and hydroxyl groups at both ends. Examples thereof include a random copolymer or block copolymer of ethylene oxide and propylene oxide, cyclohexanedimethanol, and the like.

  Examples of dicarboxylic acid esters include dimethyl ester, diethyl ester, dipropyl ester, and dibutyl ester of dicarboxylic acid.

  The polyester (B2-2) is a polyester derived from the polyester (B2-1). Specifically, the polyester (B2-2) is a polyester derivative obtained by reacting with a hydroxyl group, a carboxyl group, a vinyl group, or the like of the polyester (B2-1). As the compound to be reacted, a compound having a hydroxyl group (nonionic surfactant such as alcohol, higher alcohol, polyhydric alcohol, polyoxyalkylene alkyl ether, etc.), a compound having a carboxyl group (fatty acid, acid, amino acid, sulfoisophthalate) Acid), acid anhydride (acetic anhydride, trimellitic anhydride, pyromellitic anhydride, phthalic anhydride, maleic anhydride, succinic anhydride, itaconic anhydride, etc.), hydroxycarboxylic acid or anhydride thereof (lactic acid, ε -Caprolactam, lactide, etc.), amine (aliphatic amine, aminosilicone, etc.), epoxy, carbonate, isocyanate, (meth) acrylic acid ester, (meth) acrylic acid, cationizing agent (eg epichlorohydrin), etc. It is done.

  As polyester (B2-2), the polyester obtained by reacting polyester (B2-1) and an acid anhydride is preferable. Examples of the acid anhydride include trimellitic anhydride, pyromellitic anhydride, phthalic anhydride, maleic anhydride, succinic anhydride, itaconic anhydride, and the like.

  The weight average molecular weight of the polyester (B2-2) is preferably 2000 to 300000, more preferably 2000 to 200000, and further preferably 3000 to 150,000.

<Compound (C)>
The flame-retardant fiber production method of the present invention preferably further contains a compound (C) represented by the general formula (6) in the bath. By further using the compound (C), the emulsification and dispersibility of the flame retardant (A) are improved, and the foaming property is suppressed by emulsifying the compound (B) to reduce spec stains and can body contamination. can do. Compound (C) may be used alone or in combination of two or more.

In formula (6), R ⁴ 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 described in R ¹ and having 1 to 24 carbon atoms.

R ⁴ is preferably a hydrogen atom or an alkyl group having 1 to 9 carbon atoms, and preferably a hydrogen atom or a methyl group from the viewpoint that the flame retardant is excellent in emulsification and dispersibility and can further reduce spec stains and can body contamination. More preferred is a methyl group. The position of R ⁴ may be any position, but the meta position and para position are preferred.

In General Formula (6), A ² O is an oxyalkylene group having 2 to 4 carbon atoms, and may be one or more. 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 include an oxyethylene group and an oxypropylene group from the viewpoint that the flame retardant is excellent in emulsification and dispersibility and can reduce spec stains and can body contamination. preferable.

In General Formula (6), Y ² 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, an α-methylstyryl 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.

  In general formula (6), M is a hydrogen atom or an anionic group. The anionic group is not particularly limited as long as it contains an anionic functional group. Carboxylate, alkylene carboxylate, sulfate ester salt, sulfonate ester salt, phosphate ester salt, phosphate monoester salt , Phosphoric acid diester salts, sesquiphosphate salts and the like. Of these, sulfate ester salts are preferred.

  The salt may be an alkali metal salt, alkaline earth metal salt, ammonium salt, organic amine salt, 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.).

  In general formula (6), n is an integer of 0-50. Among these, n is preferably 0 to 20, more preferably 0 to 15, and particularly preferably 0 to 5 from the viewpoint that the flame retardant is excellent in emulsification and dispersibility and can reduce spec stains and can body contamination.

  In general formula (6), p is an integer of 1-4. Among these, p is preferably 1 to 3, and 1 is particularly preferable from the viewpoint that the flame retardant is excellent in emulsification and dispersibility, and spec stains and can contamination can be reduced.

<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). ). More preferably, in addition to the flame retardant (A) and the compound (B), a step of heat-treating the fiber material in a bath containing the compound (C) is included. By immersing the fiber material in such a bath, the flame retardant (A) can be applied, and heat treatment can be performed in the state in which the fiber material is immersed to impart 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 ratio of the compound (B) in the bath is preferably 1 to 100 parts by weight, more preferably 1 to 50 parts by weight, and still more preferably 2 to 30 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 proportion is more than 100 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 in combination during dyeing.

  When the bath contains the compound (C), the ratio of the compound (C) in the bath is preferably 1 to 200 parts by weight, more preferably 1 to 100 parts by weight with respect to 100 parts by weight of the flame retardant (A). 1 to 50 parts by weight is more preferable. When the proportion is less than 1 part by weight, spec stains and can body 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.

  In the bath, the compound (B) is preferably emulsified or solubilized, and since the flame retardant is excellent in emulsification, dispersibility and foam suppression, it is emulsified or solubilized by the compound (C). More preferably, it is particularly preferably emulsified.

  The weight ratio (B / C) of the compound (B) to the compound (C) is preferably 100/0 to 1/99, more preferably 99/1 to 1/99, further preferably 95/5 to 5/95. 40/60 to 20/80 are particularly preferable.

  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.

  As the flame retardant (A) to be added to the bath, the flame retardant processing agent for fibers of the present invention described later may be used, and a brominated flame retardant and / or a phosphorus flame retardant is emulsified and dissolved in water or the like in advance. Each of the dispersed flame retardant processing chemicals may be used. In order to emulsify, dissolve and disperse the flame retardant (A) in water or the like, it is preferable to use a surfactant or the like.

  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 above-mentioned compound (C) is preferable in that it is excellent in dispersibility and foam suppression of the flame retardant, and is excellent in reducing dirt on the fiber material and can body contamination.

  The cationic surfactant is not particularly limited. 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 (B) and / or compound (C) is excellent in emulsifying and / or dispersibility and foam suppression of the flame retardant (A), and stains on the fiber material. It is preferable in that it is excellent in reducing can body contamination.

  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) to be added to the bath, the below-mentioned flame retardant processing agent for fibers of the present invention and / or the below-described flame retardant processing aid for fibers of the present invention 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).

  As the compound (C) to be added to the bath, the below-mentioned flame retardant processing agent for fibers of the present invention and / or the below-described flame retardant processing aid for fibers of the present invention 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 (C).

  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. Examples of the anionic surfactant include those described above, but in terms of foam suppression properties, alkyl phosphate salts, alkylaryl phosphate salts, polyoxyalkylene alkyl ether phosphate salts, polyoxyalkylene alkyl aryl ether phosphate salts, Phosphate salts such as polycyclic aryl ether phosphate salts, polyoxyalkylene polycyclic aryl ether phosphate salts and polyoxyalkylene alkyl polyhydric alcohol ether phosphate salts are preferred, and alkyl phosphate salts are more preferred.

  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.

  In the method for producing a flame-retardant fiber of the present invention, it is preferable that a carrier agent is not substantially contained in the bath. If the carrier agent is contained in the bath, the carrier agent is exhausted, so that the exhaustibility of the flame retardant (A) is inhibited, and it remains in the fiber material and may inhibit the flame retardancy. . As the carrier agent, aromatic halogen compounds (chlorobenzene, dichlorobenzene, trichlorobenzene, etc.), N-alkylphthalimide (N-methylphthalimide, N-ethylphthalimide, N-propylphthalimide, N-butylphthalimide, N-isopropylphthalimide, Nt-butylphthalimide, Ns-butylphthalimide, N-phenylphthalimide, etc.), aromatic carboxylates (benzyl benzoate, methyl benzoate, ethyl benzoate, butyl benzoate, etc.), alkylnaphthalenes (1- Methylnaphthalene, 2-methylnaphthalene, 2,3-dimethylnaphthalene, 1,3-dimethylnaphthalene, 1,4-dimethylnaphthalene, 1,5-dimethylnaphthalene, etc.), diphenyl ester, naphthol ester, Nol ether (ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, propylene glycol monophenyl ether, dipropylene glycol monophenyl ether, etc.), hydroxydiphenyl (o-phenylphenol, p-phenylphenol, etc.), dibenzyl ether, etc. It is done. Among these, it is particularly preferable that benzoic acid ester and dibenzyl ether are not substantially contained. It should be noted that “substantially free” means that the content of the carrier agent is preferably less than 0.01% by weight and more preferably less than 0.001% by weight with respect to the entire treatment bath in the treatment bath. preferable.

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, a compound (B), and a compound (C) 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 for textiles]
The flame-retardant processing agent for fibers of the present invention is used for imparting flame retardancy to fiber materials, and can be suitably used in the method for producing flame-retardant fibers of the present invention. The flame retardant processing agent for fibers of the present invention includes at least one flame retardant (A) selected from a brominated flame retardant and a phosphorus flame retardant, the compound (B1) represented by the above general formula (1), and the above general It contains at least one compound (B) selected from polyester (B2) having a structural unit represented by the formula (3a) and a structural unit represented by the general formula (3b), and water. By containing the flame retardant (A) and the compound (B), the flame retardant processing chemical improves the emulsifiability of the flame retardant (A) melted by the heat treatment, and suppresses foaming properties, thereby reducing specs. And can 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.

1-60 weight% is preferable, the ratio of the flame retardant (A) to the flame-retardant processing chemical | medical agent for textiles is more preferable, 10-50 weight% is more preferable, and 20-50 weight% is further more preferable.
The ratio of the compound (B) in the flame retardant processing chemical is preferably 1 to 100, more preferably 1 to 50 parts by weight, and even more preferably 2 to 30 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 proportion is more than 100 parts by weight, the stability of the flame retardant processing agent for fibers decreases, the exhaustibility of the flame retardant (A) decreases, the fastness decreases, When used in combination, the slow dyeing effect may increase.

  It is preferable that the flame retardant processing agent for fibers further contains the compound (C) represented by the general formula (6). By further containing the compound (C), the emulsifiability and dispersibility of the flame retardant (A) are improved, and the foaming property is suppressed by emulsifying the compound (B), thereby preventing speck dirt and can body contamination. Can be reduced.

  The ratio of the compound (C) 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 1 to 50 parts by weight with respect to 100 parts by weight of the flame retardant (A). If the proportion is less than 1 part by weight, spec stains and can contamination may not be reduced. On the other hand, when the proportion is more than 200 parts by weight, the stability of the flame retardant processing agent for fibers decreases, the exhaustibility of the flame retardant (A) decreases, the fastness decreases, When used in combination, the effect of slow dyeing may increase.

  The weight ratio (B / C) of the compound (B) to the compound (C) is preferably 100/0 to 1/99, more preferably 99/1 to 1/99, further preferably 95/5 to 5/95. 50/50 to 5/95 are particularly preferred.

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.

  In order to emulsify, dissolve and disperse the flame retardant (A) in water, a surfactant other than the compound (B) and the compound (C) may be used as long as the effects of the present invention are not impaired. The surfactant is the same as that described in the method for producing a flame-retardant fiber of the present invention.

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, the compound (B) emulsified with the compound (C) may be blended.

  In addition, the flame retardant processing agent of the present invention may contain other surfactants and other components other than the flame retardant (A), the compound (A) and the compound (B) as long as the effects of the present invention are not impaired. Good. 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 for textiles]
The flame-retardant processing aid for fibers of the present invention is used when flame-treating a fiber material using at least one flame retardant (A) selected from a brominated flame retardant and a phosphorus-based flame retardant. is there. That is, it means an agent that does not contain the flame retardant (A). 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, by using a flame retardant processing aid for fibers separately from the flame retardant processing agent for fibers, the ratio of the flame retardant (A) and the compound (B), and further the compound (C ) Can be easily adjusted, and adjustment to maximize the effects of the present invention is facilitated.

  The flame-retardant processing aid for fibers of the present invention is represented by the compound (B1) represented by the general formula (1) and the structural unit represented by the general formula (3a) and the general formula (3b). It contains at least one compound (B) selected from polyester (B2) having a structural unit. 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 fiber flame retardant processing aid is preferably 1 to 99% by weight, more preferably 5 to 70% by weight, and even more preferably 10 to 50% by weight.

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

It is preferable that the flame retardant processing aid for fibers of the present invention further contains the compound (C) represented by the general formula (6). About the detail of a compound (C), 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 (C) in the fiber flame retardant processing aid is preferably 1 to 99% by weight, more preferably 2 to 70% by weight, and even more preferably 20 to 70% by weight.
The flame retardant processing aid for fibers 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. .

  The total weight ratio of the compound (B) and the compound (C) in the flame retardant processing aid for fibers is good in stability over time, can be made into a uniform transparent liquid, and is diluted with water (B ) Is preferably 20 to 100% by weight, more preferably 40 to 95% by weight, and still more preferably 50 to 95% by weight.

  The weight ratio (B / C) of the compound (B) to the compound (C) is preferably 100/0 to 1/99, more preferably 99/1 to 1/99, further preferably 95/5 to 5/95. 40/60 to 20/80 are particularly preferable.

  In addition, the flame retardant processing aid of the present invention may contain other surfactants and other components other than the compound (A) and the compound (B) 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) and the compound (C) are 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) and / or the compound (C) attached to the fiber material is the condition such as the type and structure of the fiber material, the type and the amount of other processing agent attached to the fiber material, etc. However, it is preferably 0 to 10% by weight, more preferably 0 to 5% by weight based on the flame-retardant fiber.

  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 methods for spec-prevention, can body contamination and foaming]
Into a mini color dedicated pot (volume 450 mL) charged with water, the prepared flame retardant processing chemical is added to a concentration of 1 g / L and flame retardant processing aid to a concentration of 1 g / L, and acetic acid / sodium acetate buffer solution. To adjust the pH to 4.5 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 10 g, and the assumed bath ratio was 1:20.
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 foam property evaluation inside a pot was performed on the following references | standards. Moreover, 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 a mini color.
X: Dirt of flame retardant is seen in the entire mini color pot.

-Foam property evaluation method ○: Almost no bubbles are seen in the mini color pot.
(Triangle | delta): A bubble is seen in the pot only for a mini color, and a foam volume is below half of the space volume of a pot.
X: Foam is seen in the mini color dedicated pot, and the foam volume is more than half the space volume of the 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 Compound (B)]
[Production Example 1]
In a 2000 mL four-necked flask, 280 g of oleic acid, POE (13) styrenated phenol (POE (13) means that the average number of repeating oxyethylene groups is 13. Also, styrenation of styrenated phenol The degree is mono: di: tri = 15: 50: 35 in weight ratio.) 890 g was added and stirred at 240 ° C. for 6 hours. 1152 g of a compound (B-1) containing POE (13) styrenated phenol oleate and not dissolved in water at 20 ° C. was obtained, and the acid value was 5.

[Production Example 2]
In a 2000 mL four-necked flask, 280 g of stearic acid, POE (10) styrenated cresol (cresol is p-cresol: m-cresol = 50: 50, and the styrenation degree of styrenated cresol is mono: di = 50 by weight ratio. : 50.) 680 g was added and stirred at 240 ° C. for 6 hours. 940 g of a compound (B-2) containing a stearic acid ester of POE (10) styrenated cresol and not dissolved in water at 20 ° C. was obtained, and the acid value was 4.

[Production Example 3]
In a 2000 mL four-necked flask, 560 g of stearic acid and 600 g of polyethylene glycol (average molecular weight 600) were added and stirred at 240 ° C. for 6 hours. 1120 g of a compound (B-3) containing a stearic acid diester of polyethylene glycol and not soluble in water at 20 ° C. was obtained, and the acid value was 4.

[Production Example 4]
In a 2000 mL four-necked flask, 402 g of coconut oil fatty acid and 310 g of polyethylene glycol (average molecular weight 300) were added and stirred at 240 ° C. for 6 hours. 700 g of a compound (B-4) containing polyethylene glycol palm oil fatty acid diester and not soluble in water at 20 ° C. was obtained, and the acid value was 4.

[Production Example 5]
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 (B-5) containing rapeseed oil fatty acid diester of polyethylene glycol and not soluble in water at 20 ° C. was obtained, and the acid value was 5.

[Production Example 6]
In a 2000 mL four-necked flask, 570 g of rapeseed oil fatty acid and 1000 g of a polyethylene glycol polypropylene glycol block copolymer (weight ratio of oxyethylene and oxypropylene is 60:40, average molecular weight 1000) were added and stirred at 240 ° C. for 6 hours. 1513 g of a compound (B-6) containing rapeseed oil fatty acid diester of polyethylene glycol and not soluble in water at 20 ° C. was obtained, and the acid value was 5.

[Production Example 7]
Into a 2000 mL four-necked flask, 670 g of castor oil fatty acid and 600 g of polyethylene glycol (average molecular weight 600) were added and stirred at 240 ° C. for 6 hours. 1113 g of a compound (B-7) containing castor oil fatty acid diester of polyethylene glycol and not soluble in water at 20 ° C. was obtained, and the acid value was 5.

[Production Example 8]
In a 2000 mL four-necked flask, 400 g of coconut oil fatty acid and 1500 g of a polypropylene glycol block copolymer (the weight ratio of oxyethylene and oxypropylene is 30:70. Average molecular weight 2000) were added and stirred at 250 ° C. for 8 hours. 1857 g of a compound (B-8) containing a coconut oil fatty acid diester of a polypropylene glycol block copolymer and not soluble in water at 20 ° C. was obtained, and the acid value was 4.

[Production Example 9]
In a 2000 mL four-necked flask, 370 g of behenic acid and 1500 g of a polypropylene glycol block copolymer (the weight ratio of oxyethylene and oxypropylene is 40:60. Average molecular weight 1500) were added and stirred at 250 ° C. for 8 hours. 1837 g of a compound (B-9) containing a behenic acid diester of a polypropylene glycol block copolymer and not soluble in water at 20 ° C. was obtained, and the acid value was 4.

[Production Example 10]
In a 2000 mL four-necked flask, 200 g of lauric acid and 860 g of POEO (4/8 block) dibenzylphenol were added and stirred at 240 ° C. for 6 hours. 1040 g of a compound (B-10) containing POEO (4/8 block) lauric acid ester of dibenzylphenol and not soluble in water at 20 ° C. was obtained, and the acid value was 5.

[Production Example 11]
A 2000 mL four-necked flask is charged with 300 g of ethylene glycol, 200 g of diethylene glycol, 90 g of 1,4-butanediol, 332 g of terephthalic acid, 332 g of isophthalic acid, and 146 g of adipic acid, and at 200 ° C. while distilling off the generated water under nitrogen. The reaction was performed for 4 hours. Subsequently, 150 mg of antimony trioxide was added as a catalyst, the system was gradually reduced in pressure, and reacted at 240 ° C. and a reduced pressure of 20 mmHg for 3 hours. Next, 192 g of trimellitic anhydride was added and reacted at 250 ° C. and normal pressure for 1 hour to obtain a polyester compound (B-11) having a weight average molecular weight of 8500. This was poured into 2000 g of water containing 40 g of caustic soda and dissolved, and then adjusted with water to obtain a 30% by weight aqueous solution of the polyester compound (B-11).

[Production Example 12]
A 2000 mL four-necked flask is charged with 300 g of ethylene glycol, 200 g of polyethylene glycol having a weight average molecular weight of 2000, 332 g of terephthalic acid, 332 g of isophthalic acid, and 202 g of sebacic acid, and is distilled at 200 ° C. while distilling off the generated water under nitrogen. Time reaction was performed. Subsequently, 150 mg of antimony trioxide was added as a catalyst, the system was gradually reduced in pressure, and reacted at 260 ° C. and a reduced pressure of 5 mmHg for 3 hours. Next, 192 g of trimellitic anhydride was added and reacted at 250 ° C. and normal pressure for 1 hour to obtain a polyester compound (B-12) having a weight average molecular weight of 15000. This was poured into 2000 g of water containing 40 g of caustic soda, dissolved, and then adjusted with water to obtain a 30% by weight aqueous solution of the polyester compound (B-12).

[Production Example 13]
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 under nitrogen. 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 (B-13) having a weight average molecular weight of 5000. This was poured into 2000 g of water containing 17 g of ammonia, dissolved, and then adjusted with water to obtain a 30% by weight aqueous solution of the polyester compound (B-13).

[Production Example 14]
A 2000 mL four-necked flask is charged with 400 g of ethylene glycol, 200 g of diethylene glycol, 166 g of terephthalic acid, 166 g of isophthalic acid, 9 g of maleic acid, and 19 g of trimellitic anhydride, and the resulting water is distilled off under nitrogen for 4 hours at 200 ° C. Reaction was performed. Subsequently, 150 mg of antimony trioxide was added as a catalyst and reacted at 260 ° C. for 3 hours. Next, 113 g of polyoxyethylene (20) distyrylphenyl ether was added and reacted at 250 ° C. and a reduced pressure of 5 mmHg for 3 hours to obtain a polyester compound (B-14) having a weight average molecular weight of 10,000. This was poured into 2000 g of water containing 2 g of ammonia, dissolved, and then adjusted with water to obtain a 30% by weight aqueous solution of the polyester compound (B-14).

[Production Example 15]
A 2000 mL four-necked flask is charged with 400 g of ethylene glycol, 236 g of 1,6-hexanediol, 332 g of terephthalic acid, 332 g of isophthalic acid, and 520 g of M-ester (manufactured by Sanko Co., Ltd.), and the generated water is distilled off under nitrogen. The reaction was carried out at 200 ° C. for 4 hours. Subsequently, 150 mg of antimony trioxide was added as a catalyst, the system was gradually reduced in pressure, and reacted at 260 ° C. and a reduced pressure of 5 mmHg for 3 hours. Next, 46 g of trimellitic anhydride was added and reacted at 250 ° C. and normal pressure for 1 hour to obtain a polyester compound (B-15) having a weight average molecular weight of 20000. This was poured into 2000 g of water containing 40 g of caustic soda, dissolved, and then adjusted with water to obtain a 30% by weight aqueous solution of the polyester compound (B-15).

[Production Example 16]
In a 2000 mL four-necked flask, 500 g of ethylene glycol, 332 g of terephthalic acid, and 520 g of M-ester (manufactured by Sanko Co., Ltd.) were charged, and the reaction was carried out at 200 ° C. for 4 hours while distilling off the generated water. Subsequently, 150 mg of antimony trioxide was added as a catalyst, 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 (B-16) having a weight average molecular weight of 13,000. This was poured into 2000 g of water containing 6 g of ammonia, dissolved, and then adjusted with water to obtain a 30% by weight aqueous solution of the polyester compound (B-16).

[Production Example 17]
A 2000 mL four-necked flask was charged with 425 g of a polyester compound (B-11) and 9 g of maleic anhydride, and reacted at 150 ° C. for 1 hour under nitrogen. This was poured into 1000 g of water containing 60 g of caustic soda and dissolved, and then 72 g of acrylic acid and 1 g of ammonium persulfate were added, reacted at 80 ° C. for 3 hours, adjusted with water, and a polyester compound having a weight average molecular weight of 9000 (B- 17) 30% by weight aqueous solution was obtained.

[Production Example 18]
A 2000 mL four-necked flask was charged with 500 g of a polyester compound (B-13), 22 g of pyromellitic anhydride, and 29 g of 5-sulfoisophthalic acid dimethyl sodium salt, and reacted at 250 ° C. for 1 hour under nitrogen. This was put into 1000 g of water containing 14 g of caustic soda and adjusted with water to obtain a 30 wt% aqueous solution of a polyester compound (B-18) having a weight average molecular weight of 6000.

[Production Example 19]
A 2000 mL four-necked flask was charged with 500 g of a polyester compound (B-13), 8 g of maleic anhydride and 7 g of succinic anhydride, and reacted at 150 ° C. for 1 hour under nitrogen. This was put into 1000 g of water containing 20 g of dimethylethanolamine, and adjusted with water to obtain a 30 wt% aqueous solution of a polyester compound (B-19) having a weight average molecular weight of 6000.

[Production Example 20]
A 2000 mL four-necked flask is charged with 88 g of dimethyl terephthalate, 15 g of sodium dimethyl 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 depressurized and reacted at 260 ° C. and a reduced pressure of 5 mmHg for 3 hours to obtain a polyester compound (D-1) having a weight average molecular weight of 15000 and not a compound (B). This was dissolved in 300 g of N, N-dimethylformamide and then adjusted with water to obtain a 30% by weight aqueous solution of the polyester compound (D-1).

[Production Example of Compound (C)]
[Production Example 21]
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, and 1550 g of a compound (C-1) containing a triethanolamine salt of sesquiphosphate of POE (13) styrenated phenol was obtained.

[Production Example 22]
In a 2000 mL four-necked flask, 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. .) 1000 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, and 1217 g of compound (C-2) containing the triethanolamine salt of sesquiphosphate of POE (10) styrenated cresol was obtained.

[Production Example 23]
In a 2000 mL four-neck flask, POE (3) styrenated nonylphenol (nonylphenol is p-nonylphenol: m-nonylphenol = 90: 10, and the styrenation degree of styrenated nonylphenol is mono: di = 50: 50 by weight ratio). ) 842 g, phosphoric anhydride 47 g, and 75% phosphoric acid 44 g were added and stirred at 130 ° C. for 6 hours. While cooling, 150 g of triethanolamine was added, and 1070 g of compound (C-3) containing the triethanolamine salt of POE (10) styrenated nonylphenol phosphate was obtained.

[Production Example 24]
In a 2000 mL four-necked flask, POE (4) styrenated cresol (cresol is p-cresol: m-cresol = 30: 70, and the styrenation degree of styrenated cresol is mono: di = 50: 50 by weight ratio. ) 958 g and sulfamic acid 200 g were added and stirred at 130 ° C. for 4 hours. 1149 g of compound (C-4) containing an ammonium salt of POE (4) styrenated cresol sulfate was obtained.

[Production Example 25]
In a 2000 mL four-necked flask, POEO (3/7 random) styrenated phenol (POEO (3/7 random) is a random adduct having an average number of repetitions of oxyethylene groups and oxypropylene groups of 3 and 7. The degree of styrenation of the styrenated phenol is di: tri: tetra = 10: 80: 10 by weight ratio.) 1780 g and 200 g of sulfamic acid were added and stirred at 130 ° C. for 4 hours. 1966 g of a compound (C-5) containing an ammonium salt of POEO (3/7 random) styrenated phenol sulfate was obtained.

[Production Example 26]
In a 2000 mL four-necked flask, 1080 g of POE (3) styrenated phenol (degree of styrenation of styrenated phenol is di: tri: tetra = 10: 80: 10 by weight ratio) and 200 g of sulfamic acid are placed at 130 ° C. For 4 hours. 1266 g of a compound (C-6) containing an ammonium salt of POE (3) styrenated phenol sulfate was obtained.

[Production Example 27]
In a 2000 mL four-necked flask, POE (30) α-methylstyrenated cresol (cresol is p-cresol: m-cresol = 30: 70, and α-methylstyrenated cresol has α-methylstyrenated degree by weight ratio. Mono: di = 50: 50) 1593 g and 100 g of sulfamic acid were added and stirred at 130 ° C. for 4 hours. 1589 g of a compound (C-7) containing an ammonium salt of POE (30) α-methylstyrenated cresol was obtained.

[Production Example 28]
Into a 2000 mL four-necked flask, 765 g of POE (3) styrenated phenol (the styrenated phenol has a styrenation degree of mono: di: tri = 15: 50: 35) and 100 g of monochloroacetic acid were added at 130 ° C. For 6 hours. While cooling, 105 g of diethanolamine was added, and 961 g of a compound (C-8) containing POE (3) diethanolamine salt of methyl carboxylic acid of styrenated phenol was obtained.

[Production example of phosphorus flame retardant]
[Production Example 29]
(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)) 716g and aluminum chloride 16g were put, and oxytrichloride at 80 ° C Phosphorus (335 g) was slowly added dropwise over 2 hours to remove generated hydrogen chloride, and after completion of the addition, the mixture was aged for 3 hours at 120 ° C. The reaction product was cooled to 90 ° C., and 500 g of 5% caustic soda solution was added. Stirred for 1 hour at 90 ° C. The aqueous phase was removed and the reaction was poured into cold water, washed for 1 hour, dehydrated, further washed with water for 1 hour, dehydrated, dried and tri-p-cresyl phosphate. 770 g of a phosphorus-based flame retardant (A-1) having a melting point of 78 ° C. and a white solid having a purity of 99.1% was obtained.

[Production Example of Flame Retardant Chemicals a1 to a22]
The compounding components (parts by weight) shown in Tables 1 and 2 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. The POE (10) styrenated cresol shown in Table 1 is polyoxyethylene styrenated cresol, which means that the average number of oxyethylene group repeats is 10. The styrenation degree of styrenated cresol is mono: di: tri = 10: 80: 10 by weight ratio. As the cresol, m-cresol: p-cresol = 50-60: 40-50 (weight ratio) was used. 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 example of flame retardant processing aids b1 to b40]
The compounding components (parts by weight) shown in Tables 3 to 6 were respectively added to a blender and sufficiently stirred at 20 ° C. to prepare flame retardant processing aids.

(Examples 1-77, Comparative Examples 1-20)
Using the prepared flame retardant processing chemicals and flame retardant processing aids shown in Tables 7 to 10, the anti-spec specifications, can body contamination, and foamability 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 4-6.

[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 77 are excellent in all of flame retardancy, specification prevention, can body contamination, and foamability. On the other hand, Comparative Examples 1-20 are inferior in any one in a flame retardance, specification prevention property, a can body contamination property, and foamability.

Claims (10)

At least one flame retardant (A) selected from a brominated flame retardant and a phosphorus flame retardant, a compound (B1) represented by the following general formula (1), and a structural unit represented by the following general formula (3a) And a step of heat-treating the fiber material in a bath containing at least one compound (B) selected from polyester (B2) having a structural unit represented by the following general formula (3b): For producing a conductive fiber.

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

(In the formula, R ³ 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. M is an integer of 1 to 4)

(In the formula, A ³ is a hydrocarbon group having 1 to 24 carbon atoms. A ⁴ is a hydrocarbon group having 1 to 24 carbon atoms. A ⁵ and A ⁶ are each independently 2 carbon atoms. And W is a carboxyl group, a functional group represented by the following general formula (4), a functional group represented by the following general formula (5), or a salt thereof. -100 and b are integers of 1 to 100. [A ⁵ O] _a or [A ⁶ O] A ⁵ O or A ⁶ O constituting _b may be the same or different.

  The method for producing flame-retardant fibers according to claim 1, wherein the ratio of the compound (B) is 1 to 100 parts by weight with respect to 100 parts by weight of the flame retardant (A). The method for producing flame-retardant fibers according to claim 1 or 2, further comprising a compound (C) represented by the following general formula (6) in the bath.

(In the formula, R ⁴ is a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms. A ² O is an oxyalkylene group having 2 to 4 carbon atoms. Y ² is an aralkyl having 7 to 16 carbon atoms. M is a hydrogen atom or an anionic group, n is an integer of 0 to 50, and p is an integer of 1 to 4.)   The manufacturing method of the flame-retardant fiber of Claim 3 whose ratio of the said compound (C) is 1-200 weight part with respect to 100 weight part of said flame retardants (A).   The manufacturing method of the flame-retardant fiber in any one of Claims 1-4 whose melting | fusing point of the said flame retardant (A) is 40-150 degreeC.   The method for producing a flame-retardant fiber according to any one of claims 1 to 5, wherein the brominated flame retardant is tris (2,3-dibromopropyl) isocyanurate. At least one flame retardant (A) selected from a brominated flame retardant and a phosphorus flame retardant, a compound (B1) represented by the following general formula (1), and a structural unit represented by the following general formula (3a); A flame retardant processing agent for fibers, containing at least one compound (B) selected from polyester (B2) having a structural unit represented by the following general formula (3b) and water.

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

(In the formula, R ³ 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. M is an integer of 1 to 4)

(In the formula, A ³ is a hydrocarbon group having 1 to 24 carbon atoms. A ⁴ is a hydrocarbon group having 1 to 24 carbon atoms. A ⁵ and A ⁶ are each independently 2 carbon atoms. And W is a carboxyl group, a functional group represented by the following general formula (4), a functional group represented by the following general formula (5), or a salt thereof. -100 and b are integers of 1 to 100. [A ⁵ O] _a or [A ⁶ O] A ⁵ O or A ⁶ O constituting _b may be the same or different.

Furthermore, the flame-retardant processing agent for fibers of Claim 7 containing the compound (C) represented by following General formula (6).

(In the formula, R ⁴ is a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms. A ² O is an oxyalkylene group having 2 to 4 carbon atoms. Y ² is an aralkyl having 7 to 16 carbon atoms. M is a hydrogen atom or an anionic group, n is an integer of 0 to 50, and p is an integer of 1 to 4.) A flame-retardant processing aid for fibers used when flame-treating a fiber material using at least one flame retardant (A) selected from a brominated flame retardant and a phosphorus-based flame retardant,
The compound (B1) represented by the following general formula (1) and a polyester (B2) having a structural unit represented by the following general formula (3a) and a structural unit represented by the following general formula (3b) are selected. A flame retardant processing aid for fibers containing at least one compound (B).

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

(In the formula, R ³ 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. M is an integer of 1 to 4)

(In the formula, A ³ is a hydrocarbon group having 1 to 24 carbon atoms. A ⁴ is a hydrocarbon group having 1 to 24 carbon atoms. A ⁵ and A ⁶ are each independently 2 carbon atoms. And W is a carboxyl group, a functional group represented by the following general formula (4), a functional group represented by the following general formula (5), or a salt thereof. -100 and b are integers of 1 to 100. [A ⁵ O] _a or [A ⁶ O] A ⁵ O or A ⁶ O constituting _b may be the same or different.

Furthermore, the flame-retardant processing aid for fibers of Claim 9 containing the compound (C) represented by following General formula (6).

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