JP7698464B2 - Fiber processing aids and polyester fiber processing agents - Google Patents

Description

The present invention relates to a fiber treatment auxiliary and a treatment agent for polyester fibers. More specifically, the present invention provides a treatment agent for polyester fibers that stabilizes the dispersion state of the dye when dyeing polyester fibers at high temperatures, and further provides a uniform dyed product without agglomerating the dye and flame retardant when used in combination with a flame retardant.

Polyester fibers are usually dyed using disperse dyes in a weakly acidic pH range in an aqueous solution system at high temperature and pressure of 110 to 140°C. In this case, the disperse dye itself generally contains a naphthalenesulfonic acid-based dispersant. However, high temperature and pressure can reduce the dispersibility of the dye, resulting in poor dyeing and dye aggregation, which can cause contamination of the dyed item and the dyeing machine. For this reason, a method is used to obtain a uniform dyed item by using a surfactant composition known as a dispersing and leveling agent.

Furthermore, in the dyeing process, it is common to use functional agents such as flame retardants and light fasteners in combination to impart functionality to the dyed item. In this case, the hydrophobic structures in the functional agents cause agglomeration with the dye, which can cause contamination of the dyed item and the dyeing machine, creating a problem.

Dyeing defects and contamination of dyeing machines require re-dyeing of the items to be dyed and frequent cleaning of the dyeing machines, which leads to increased running costs due to reduced energy efficiency and increased wastewater. Therefore, measures to eliminate dyeing defects and contamination of dyeing machines are required.

To solve these problems, developments are underway to develop dispersion leveling agents such as those described in Patent Documents 1 and 2, and flame retardants with a uniformly dispersed state such as those described in Patent Documents 3, 4, and 5.

Special Publication No. 2015-522721 JP 2014-047438 A JP 2019-6992 A Patent No. 6039326 JP 2014-189914 A

The objective of the present invention is to provide a fiber processing aid that can prevent dye aggregation and aggregation between dyes and functional agents when dyeing polyester and other fibers under high temperature and pressure, and when using dyes in combination with functional agents such as flame retardants, thereby providing uniformly dyed products.

The inventors have conducted extensive research to solve the above problems, and have found that by using a fiber treatment aid containing a combination of a specific anionic surfactant and a polyoxyalkylene polyhydric alcohol fatty acid ester when dyeing fibers such as polyester under high temperature and pressure, and when using a dye in combination with a functional agent such as a flame retardant, it is possible to suppress dye aggregation and prevent aggregation between the dye and the functional agent, thereby providing a uniformly dyed product. More specifically, the present invention has found that a polyester fiber treatment agent containing (A) an anionic surfactant represented by the following general formula (1), (B) an anionic surfactant represented by the following general formula (2), and (C) a polyoxyalkylene polyhydric alcohol fatty acid ester can solve the above problems, and has completed the present invention.

（式中、ｍは１～３の数であり、ｎ^３は５～６０の数であり、Ａ^３は炭素原子数２～４のアルキレン基であり、Ｍ’は水素原子、アンモニウムイオン、有機アンモニウムイオン、又は一価の金属イオンである）、
及び、
（Ｃ）ポリオキシアルキレン多価アルコール脂肪酸エステル ５～３５質量部
（ただし、（Ａ）成分、（Ｂ）成分、（Ｃ）成分の合計は１００質量部である）
を含有する、繊維処理助剤を提供する。
更に本発明はポリエステル繊維用である前記繊維処理助剤を提供する。さらには、前記繊維処理助剤を染色浴に添加する工程と、該染色浴中で繊維を染色して染色物を得る工程とを含むことを特徴とする、繊維染色物の製造方法を提供する。 That is, the present invention provides: (A) a compound represented by the following general formula (1): 40 to 90 parts by mass X ¹ -O-(A ¹ O) _n1 (A ² O) _n2 -X ² (1)
(wherein A ¹ is an ethylene group, A ² is an alkylene group having 3 or 4 carbon atoms, n ¹ is a number from 3 to 30, n ² is a number from 5 to 60, the mutual arrangement of A ¹ O and A ² O is not limited and may form a block unit or a random bond, X ¹ is a hydrogen atom, an alkyl or alkenyl group having 8 to 22 carbon atoms, -SO ₃ M, or -PO ₃ M, X ² is -SO ₃ M, or -PO ₃ M, and M is a hydrogen atom, an ammonium ion, an organic ammonium ion, or a monovalent metal ion).
(B) 5 to 25 parts by mass of a compound represented by the following general formula (2):

(In the formula, m is a number from 1 to 3, ⁿ³ is a number from 5 to 60, ^A3 is an alkylene group having 2 to 4 carbon atoms, and M' is a hydrogen atom, an ammonium ion, an organic ammonium ion, or a monovalent metal ion).
And,
(C) Polyoxyalkylene polyhydric alcohol fatty acid ester: 5 to 35 parts by mass (wherein the total of components (A), (B), and (C) is 100 parts by mass)
The present invention provides a fiber processing aid comprising:
The present invention further provides the fiber treatment auxiliary for polyester fibers, and a method for producing a dyed fiber product, comprising the steps of adding the fiber treatment auxiliary to a dyebath and dyeing a fiber in the dyebath to obtain a dyed product.

The fiber processing aid of the present invention suppresses the generation of aggregates of dyes and flame retardants during high-temperature dyeing processes of fibers such as polyester, and can provide a good, uniformly dyed product.

Each component will be described in more detail below.
Component (A) is a compound represented by the following general formula (1): Component (A) is important in that it exhibits an effect of preventing dye aggregation and aggregation between the dye and functional agents such as a flame retardant during dyeing of polyester fibers under high temperature and pressure.
X ¹ -O-(A ¹ O) _n1 (A ² O) _n2 -X ² (1)
In the formula, A ¹ is an ethylene group. A ² is an alkylene group having 3 or 4 carbon atoms, preferably a propylene group having 3 carbon atoms. ^{n 1} is a number from 3 to 30, n ² is a number from 5 to 60, and the mutual arrangement of A ¹ O and A ² O is not limited and may form a block unit or a random bond. X ¹ is a hydrogen atom, an alkyl or alkenyl group having 8 to 22 carbon atoms, -SO ₃ M, or -PO ₃ M, and X ² is -SO ₃ M, or -PO ₃ M. M is a monovalent cation selected from a hydrogen atom, an ammonium ion, an organic ammonium ion, and a monovalent metal ion.

More specifically, component (A) is a polyoxyalkylene glycol sulfonate ester or a polyoxyalkylene glycol phosphate ester, a polyoxyalkylene fatty alcohol sulfonate ester, and a polyoxyalkylene fatty alcohol phosphate ester.

A ¹ O is an oxyethylene group, and A ² O is an oxyalkylene group having 3 or 4 carbon atoms. n ¹ or n ² represents the average number of moles of oxyalkylene added represented by (A ¹ O) and (A ² O), and does not have to be an integer. n ¹ is 3 to 30, preferably 5 to 25. If n ¹ is less than 3, the hydrophobicity of component (A) becomes high, and the dye and functional drug are likely to aggregate, which may deteriorate the dispersibility. If ^{n 1} is more than 30, the hydrophilicity of component (A) becomes high, and sufficient dispersibility cannot be exhibited. n ² is 5 to 60, preferably 10 to 50. If n ² is less than 5, the proportion of hydrophobic groups in the structure of component (A) becomes small, and sufficient surface activity and dispersibility cannot be exhibited. Furthermore, if ⁿ² is greater than 60, the proportion of hydrophobic groups in the structure of component (A) becomes too high, which may lead to aggregation of the dye and functional drug, resulting in poor dispersibility. The mutual arrangement of (A ¹ O) and (A ² O) (the order of addition of oxyalkylene groups) is not limited. The addition method when adding alkylene oxide may be either block addition or random addition.

^X1 is a hydrogen atom, an alkyl or alkenyl group having 8 to 22 carbon atoms, preferably 7 to 21 carbon atoms, -SO ₃ M, or -PO ₃ M, and ^X2 is -SO ₃ M, or -PO ₃ M. M is a hydrogen atom, an ammonium ion, an organic ammonium ion, or a monovalent metal ion. The monovalent metal ion is preferably a sodium ion or a potassium ion. Examples of the alkyl or alkenyl group having 8 to 22 carbon atoms, preferably 7 to 21 carbon atoms, include heptyl, octyl, nonyl, decyl, decenyl, undecyl, dodecyl, tridecyl, tridecenyl, tetradecyl, tetradecenyl, pentadecyl, hexadecyl, heptadecyl, heptadecenyl, octadecyl, isooctadecyl, nonadecenyl, icosyl, and henicosyl groups. Among these, octyl, decyl, dodecyl, and tridecyl groups are preferred.

In -SO ₃ M, M is a hydrogen atom, an ammonium ion, an organic ammonium ion, or a monovalent metal ion. The monovalent metal ion is preferably a sodium ion or a potassium ion. Preferably, M is an ammonium ion, an organic ammonium ion, a sodium ion, or a potassium ion. The functional group can be introduced into the polyoxyalkylene glycol by a general sulfonation or sulfation method. For example, it can be introduced by a method of reacting chlorosulfonic acid, sulfuric anhydride, sulfamic acid, sulfuric acid, or the like with the polyoxyalkylene glycol. More specifically, in the case of chlorosulfonic acid or sulfuric anhydride, the reaction temperature is 0 to 70°C, and in the case of sulfamic acid or sulfuric acid, the reaction temperature is 50 to 150°C. The state of the reaction is determined by measuring the amount of bound sulfuric acid, and the degree of anionization is usually 80% or more, preferably 85% or more.

In -PO ₃ M, M is a hydrogen atom, an ammonium ion, an organic ammonium ion, or a monovalent metal ion. The organic ammonium ion is an ammonium ion (NH ₄ ⁺ ) in which one or more of the four hydrogen atoms are replaced with an organic group such as an alkyl group or a hydroxyalkyl group, and examples thereof include a monoethanolammonium ion, a diethanolammonium ion, and a triethanolammonium ion. The monovalent metal ion is preferably a sodium ion or a potassium ion. Preferably, M is an ammonium ion, an organic ammonium ion, a sodium ion, or a potassium ion. The functional group can be introduced into the polyoxyalkylene glycol by a general phosphorylation method. For example, the functional group can be introduced by a method in which a phosphorylating agent such as phosphoric acid, polyphosphoric acid, phosphoric anhydride, or phosphorus oxychloride is reacted with the polyoxyalkylene glycol. More specifically, the reaction with phosphoric anhydride can be carried out in a nitrogen atmosphere at a reaction temperature of 30 to 150°C. The reaction is determined by measuring the acid value, and the degree of anionization is usually 90 mol% or more, preferably 95 mol% or more.

Examples of the compound represented by the general formula (1) include
Polyoxyethylene polyoxypropylene glycol monosulfate ammonium salt and metal (Na, K) salt Polyoxyethylene polyoxypropylene glycol disulfate ammonium salt and metal (Na, K) salt Polyoxyethylene polyoxypropylene glycol monophosphate ammonium salt and metal (Na, K) salt Polyoxyethylene polyoxypropylene glycol diphosphate ammonium salt and metal (Na, K) salt Polyoxyethylene polyoxypropylene octyl alcohol sulfate ammonium salt and metal (Na, K) salt Polyoxyethylene polyoxypropylene octyl alcohol phosphate ammonium salt and metal (Na, K) salt Polyoxyethylene polyoxypropylene lauryl alcohol sulfate ammonium salt and metal (Na, K) salt Polyoxyethylene polyoxypropylene lauryl alcohol phosphate ammonium salt and metal (Na, K) salt Polyoxyethylene polyoxypropylene trydecanol sulfate ammonium salt and metal (Na, K) salt Polyoxyethylene polyoxypropylene trydecanol phosphate ammonium salt and metal (Na, K) salt; polyoxyethylene polyoxypropylene oleyl alcohol sulfate ammonium salt and metal (Na, K) salt; polyoxyethylene polyoxypropylene oleyl alcohol phosphate ammonium salt and metal (Na, K) salt, etc.

More preferred are polyoxyethylene polyoxypropylene glycol monosulfate ammonium salt and metal (Na, K) salt, polyoxyethylene polyoxypropylene glycol disulfate ammonium salt and metal (Na, K) salt, polyoxyethylene polyoxypropylene trydecanol sulfate ammonium salt and metal (Na, K) salt, polyoxyethylene polyoxypropylene lauryl alcohol phosphate ammonium salt and metal (Na, K) salt, polyoxyethylene polyoxypropylene trydecanol phosphate ammonium salt and metal (Na, K) salt, and the like.

The preparation of component (A) may be performed according to a conventionally known method. For example, (A) polyoxyalkylene glycol sulfonate ammonium salt and metal (Na, K) salt, or polyoxyalkylene glycol phosphate ammonium salt and metal (Na, K) salt can be produced by adding alkylene oxide to ethylene glycol, followed by the above-mentioned sulfonation method or phosphorylation method.
Furthermore, the polyoxyalkylene aliphatic alcohol sulfonate ammonium salt and metal (Na, K) salt, or the polyoxyalkylene aliphatic alcohol phosphate ammonium salt and metal (Na, K) salt can be produced, for example, by adding an alkylene oxide to an aliphatic alcohol under normal conditions, then adding a functional group by the above-mentioned sulfonation method or phosphorylation method, and then neutralizing as necessary.

The amount of component (A) contained in the fiber treatment aid of the present invention is 40 to 90% by mass, preferably 50 to 90% by mass, and more preferably 60 to 85% by mass, based on the total mass of the fiber treatment aid.

式中、ｍは１～３の数であり、ｎ^３は５～６０の数であり、Ａ^３は炭素原子数２～４のアルキレン基であり、Ｍ’は一価のカチオンであり、水素原子、アンモニウムイオン、有機アンモニウムイオン、及び一価の金属イオンから選ばれる。有機アンモニウムイオンとは、アンモニウムイオン（ＮＨ_４ ^＋）の四つの水素のうち、一つ以上をアルキル基やヒドロキシアルキル基などの有機基で置換したものであり、例えばモノエタノールアンモニウムイオン、ジエタノールアンモニウムイオン、トリエタノールアンモニウムイオン等が挙げられる。一価の金属イオンとは、好ましくはナトリウムイオン又はカリウムイオンである。好ましくは、Ｍ’はアンモニウムイオン、有機アンモニウムイオン、ナトリウムイオン、又はカリウムイオンである。
上記一般式（２）で表される化合物は、詳細には、ポリオキシアルキレンスチレン化フェニルエーテルサルフェートであり、染料及び難燃剤等の機能性薬剤の水溶液中の分散性を高める効果発揮する点で重要となる。尚、本発明において、Ｃ_６Ｈ_５－ＣＨ（ＣＨ_３）－で表される基をスチリル基という。また、該スチリル基がフェニルエーテルに結合した構造をスチレン化フェニルエーテルといい、スチリル基を有するフェノールをスチレン化フェノールという。 The component (B) is a compound represented by the following general formula (2).

In the formula, m is a number from 1 to 3, ⁿ³ is a number from 5 to 60, ^A3 is an alkylene group having 2 to 4 carbon atoms, and M' is a monovalent cation selected from a hydrogen atom, an ammonium ion, an organic ammonium ion, and a monovalent metal ion. The organic ammonium ion is an ammonium ion ( _NH4 ⁺ ) in which one or more of the four hydrogen atoms are replaced with an organic group such as an alkyl group or a hydroxyalkyl group, and examples of the organic ammonium ion include a monoethanolammonium ion, a diethanolammonium ion, and a triethanolammonium ion. The monovalent metal ion is preferably a sodium ion or a potassium ion. Preferably, M' is an ammonium ion, an organic ammonium ion, a sodium ion, or a potassium ion.
The compound represented by the above general formula (2) is, in detail, a polyoxyalkylene styrenated phenyl ether sulfate, and is important in that it exerts an effect of increasing the dispersibility of functional agents such as dyes and flame retardants in aqueous solutions. In the present invention, the group represented by C ₆ H ₅ -CH(CH ₃ )- is called a styryl group. Furthermore, a structure in which the styryl group is bonded to a phenyl ether is called a styrenated phenyl ether, and a phenol having a styryl group is called a styrenated phenol.

In the above formula (2), m represents the average number of moles of styryl groups added and does not have to be an integer. m is 1 to 3, and more preferably 2 to 3.

^A3 is an alkylene group having 2 to 4 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably an ethylene group having 2 carbon atoms. ⁿ³ is the average number of moles of oxyalkylene groups added, and is a number of 5 to 60, more preferably 8 to 50, and even more preferably 10 to 40.

Preferably, the above-mentioned (B) component includes ammonium salts and metal (Na, K) salts of polyoxyethylene tristyrenated phenyl ether sulfate.

Component (B) may be prepared according to a conventional method. For example, polyoxyethylene styrenated phenyl ether sulfate ammonium salt and metal (Na, K) salt can be produced by reacting phenol with styrene monomer under normal conditions, adding ethylene oxide, sulfonating using the method described above, and neutralizing as necessary.

The amount of component (B) contained in the fiber processing aid of the present invention is 5 to 25% by mass, preferably 5 to 20% by mass, and more preferably 8 to 18% by mass, based on the total mass of the fiber processing aid.

The component (C) is a polyoxyalkylene polyhydric alcohol fatty acid ester, and is preferably a compound represented by the following general formula (3). This compound is a necessary component for eliminating uneven dyeing during dyeing and obtaining a uniformly dyed product.
[H-(OA ⁴ ) _n4 -O-] _r R ¹ [-O-(A ⁵ O) _n5 -C(=O)-R ² ] _s (3)
In the above formula (3), R ¹ is a residue obtained by removing two or more hydroxy groups from a polyhydric alcohol having 2 to 30 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 2 to 6 carbon atoms, and having a valence of 2 to 8, preferably a valence of 2 to 6, and more preferably a valence of 2 to 4.
^A4 is a divalent alkylene group having 2 to 4 carbon atoms, and is preferably ethylene having 2 carbon atoms. ⁿ⁴ is the average number of moles of oxyalkylene added divided by (r+s), and is a number from 1 to 80, preferably 1 to 40, more preferably 2 to 30, and even more preferably 3 to 25.
^R2 is an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 2 to 30 carbon atoms, and is preferably an octyl group, a dodecyl group, a hexadecyl group, an octadecyl group, an octadecenyl group, or an isooctadecyl group.
^A5 is a divalent alkylene group having 2 to 4 carbon atoms, and is preferably ethylene having 2 carbon atoms. ⁿ⁵ is the average number of moles of alkylene oxide added divided by (r+s), and is a number from 1 to 80, preferably 1 to 40, more preferably 2 to 30, and even more preferably 3 to 25.
r and s are integers satisfying 0≦r≦7, 1≦s≦8, and 2≦r+s≦8. Preferably, r is an integer of 0 to 1, and s is an integer of 2 to 6.

The component (C) is an ester of a dihydric to octahydric, preferably dihydric to hexahydric, polyhydric alcohol and a fatty acid. Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, trimethylolpropane, glycerin, pentaerythritol, sorbitol, etc. Examples of the fatty acid include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, stearic acid, and behenic acid.
The above component (C) is preferably a fatty acid ester of a polyoxyethylene polyhydric alcohol, and more preferably polyoxyethylene glycol dioleyl ester, polyoxyethylene glycerol trioleyl ester, or the like.

In the above component (C), the average number of moles of ethylene oxide added is 3 to 40, preferably 6 to 30, and more preferably 8 to 25 moles. If the number of moles of ethylene oxide added is less than 3, the hydrophobicity becomes high and the dye may aggregate, causing staining of the dyed material. If it is 40 moles or more, the hydrophilicity becomes high and the dyeing uniformity of the dyed material may be insufficient.

(C) Polyoxyethylene polyhydric alcohol fatty acid esters may be prepared according to conventional methods. For example, they can be produced by adding ethylene oxide to a polyhydric alcohol and then reacting with a fatty acid, or by reacting a polyhydric alcohol with a fatty acid to synthesize an ester and then adding ethylene oxide to it.

The amount of component (C) contained in the fiber treatment aid of the present invention is 5 to 35% by mass, preferably 8 to 30% by mass, and more preferably 10 to 25% by mass, based on the total mass of the fiber treatment aid.

The mass ratio of the (A) component, the (B) component, and the (C) component [(A)/(B)/(C)] is 40 to 90/5 to 25/5 to 35. Preferably, the mass ratio [(A)/(B)/(C)] is 50 to 80/5 to 20/10 to 30. However, the total of the (A), (B), and (C) components is 100. This allows the fiber treatment aid of the present invention to prevent the aggregation of the dye and the aggregation of the dye and the functional agent during dyeing under high temperature and high pressure, and to maintain a uniformly dispersed state. If the mass ratio of the (A) component to the (B) and (C) components is less than the lower limit, sufficient dispersion performance cannot be obtained under dyeing conditions under high temperature and high pressure. Also, if the mass ratio of the (A) component is greater than the upper limit, the uniformity of dyeing required for dyeing is insufficient, and the dyeing performance is reduced.

The method for producing the fiber treatment aid of the present invention is not particularly limited, and may be any method known in the art. For example, components (A), (B), and (C) are mixed by placing each component in a container and then uniformly mixing at a temperature of 40 to 60°C. The fiber treatment aid may contain water and/or a solvent to improve the appearance stability of the agent and its solubility when added to the dye solution.

The fiber treatment aid of the present invention is used in the dyeing and functional agent treatment process of fibers such as polyester. Examples of polyester fibers include polyester fibers, cationic dyeable polyester fibers, regenerated polyester fibers, and polyester fibers consisting of two or more of these. Other fibers include textile products consisting of blends of the above polyester fibers with natural fibers (cotton, linen, silk, wool, etc.), semi-synthetic fibers (rayon, acetates, etc.), and other synthetic fibers (nylon, acrylic, polyamide, polyurethane, polyethylene, polypropylene, etc.). The fiber treatment aid of the present invention is preferably a fiber treatment aid for polyester fibers.

The form of the fiber product is not particularly limited, and may be short fiber, long fiber, yarn, woven fabric, knitted fabric, nonwoven fabric, etc.

In dyeing using the fiber treatment aid of the present invention, additives such as flame retardants such as bromine-based flame retardants or phosphorus-based flame retardants, deodorants, antibacterial agents, softeners, water absorbents, water and oil repellents, smoothing agents, penetrants, antistatic agents, chelating agents, antioxidants, defoamers, carrier agents, fixing agents, light stabilizers, ultraviolet absorbers, thickeners, and yellowing inhibitors can be used as necessary within the range that does not inhibit the effects of the present invention. These additives can be used simultaneously with the dyeing process of polyester fibers using the fiber treatment aid of the present invention and/or in the pre-treatment process and/or post-treatment process. The present invention can also provide a fiber treatment agent, preferably a treatment agent for polyester fibers, containing the fiber treatment aid consisting of the above components (A) to (C) and optionally the other additives described above. The blending amount may be appropriately adjusted according to the conventionally known fiber treatment agents.

The present invention provides a method for producing a dyed fiber , which comprises the steps of adding the fiber treatment aid to a dyebath and dyeing a fiber in the dyebath to obtain a dyed product. The dyeing method for fibers such as polyester may follow a conventionally known method. For example, a fabric to be dyed, a dye, other additives for imparting functionality, and the fiber treatment aid of the present invention may be added to a dyebath liquid adjusted to pH 4.5 to 6.0, and dyeing may be performed at any dyeing temperature using a dyeing machine. The dyeing temperature may be 80° C. to 150° C., preferably 100° C. to 140° C., and the pressure may be 0.00 MPa to 0.80 MPa, preferably 0.05 MPa to 0.60 MPa.
Alternatively, the above-mentioned components (A), (B), and (C) may be added separately to the dye bath in the above-mentioned mass ratio. That is, the present invention also provides a method for producing a dyed fiber product, comprising the steps of adding the components (A), (B), and (C) to a dye bath, and dyeing a fiber in the dye bath to obtain a dyed product. As described above, the blending mass ratio [(A)/(B)/(C)] of the components (A), (B), and (C) is 40 to 90/5 to 25/5 to 35, and preferably the mass ratio [(A)/(B)/(C)] is 50 to 80/5 to 20/10 to 30. However, the total of the components (A), (B), and (C) is 100.

The composition of the dye bath may follow that of a conventionally known dyeing method. The amount of fiber processing aid added to the dye bath may be adjusted as appropriate, but is preferably 0.01 to 2 g, and more preferably 0.05 to 1.5 g, per 1 L of dye bath. When the above components (A), (B), and (C) are added separately, the total amount of the above components (A), (B), and (C) is preferably 0.01 to 2 g, and more preferably 0.05 to 1.5 g, per 1 L of dye bath.

The present invention will be described in more detail below with examples and comparative examples, but the present invention is not limited to the following examples.

Preparation of Component (A) [Synthesis Example 1]
Component (A1):
A 5 L autoclave was charged with 150 g of diethylene glycol and 3.5 g of potassium hydroxide, and the inside of the autoclave was thoroughly replaced with nitrogen, after which the temperature was raised to 140° C. and 622 g of ethylene oxide was gradually added. After the reaction of ethylene oxide was completed, the temperature was cooled to 120° C., and subsequently 1640 g of propylene oxide was gradually added and thoroughly reacted, followed by cooling to obtain polyoxyethylene (10 mol) polyoxypropylene (20 mol) glycol.
Next, 480 g of the obtained polyoxyethylene (10 mol) polyoxypropylene (20 mol) glycol, 29.1 g of sulfamic acid, and 18.0 g of urea were charged into a 1 L glass flask, and the temperature was gradually raised to 120° C. to react the mixture, thereby obtaining polyoxyethylene (10 mol) polyoxypropylene (20 mol) glycol monosulfate ammonium salt. The anion purity of the product synthesized by combined sulfuric acid was 87.6%.

[Synthesis Example 2]
Ingredient (A2):
A 5 L autoclave was charged with 150 g of diethylene glycol and 4.6 g of potassium hydroxide, and the inside of the autoclave was thoroughly replaced with nitrogen, after which the temperature was raised to 140° C. and 622 g of ethylene oxide was gradually added. After the reaction of ethylene oxide was completed, the temperature was cooled to 120° C., and subsequently 2460 g of propylene oxide was gradually added and thoroughly reacted, followed by cooling to obtain polyoxyethylene (10 mol) polyoxypropylene (30 mol) glycol.
Next, 687 g of the above polyoxyethylene (10 mol) polyoxypropylene (30 mol) glycol, 29.1 g of sulfamic acid, and 18.0 g of urea were charged into a 1 L glass flask, and the temperature was gradually raised to 120° C. to react the mixture, thereby obtaining polyoxyethylene (10 mol) polyoxypropylene (30 mol) glycol monosulfate ammonium salt. The anion purity of the product synthesized by combined sulfuric acid was 88.1%.

[Synthesis Example 3]
Ingredient (A3):
687 g of polyoxyethylene (10 mol) polyoxypropylene (30 mol) glycol obtained in Synthesis Example 2 above, 43.6 g of sulfamic acid, and 18.0 g of urea were charged and gradually heated to 120° C. to react, yielding a mixture of polyoxyethylene (10 mol) polyoxypropylene (30 mol) glycol monosulfate ammonium salt and polyoxyethylene (10 mol) polyoxypropylene (30 mol) glycol disulfate ammonium salt. The anion purity of the product synthesized by combined sulfuric acid was 131.2%.

[Synthesis Example 4]
Ingredients (A4):
687 g of polyoxyethylene (10 mol) polyoxypropylene (30 mol) glycol obtained in Synthesis Example 2 above, 58.1 g of sulfamic acid, and 24.0 g of urea were charged and gradually heated to 120° C. to react, yielding a mixture of polyoxyethylene (10 mol) polyoxypropylene (30 mol) glycol monosulfate ammonium salt and polyoxyethylene (10 mol) polyoxypropylene (30 mol) glycol disulfate ammonium salt. The anion purity of the product synthesized by combined sulfuric acid was 175.8%.

[Synthesis Example 5]
Ingredients (A5):
A 5 L autoclave was charged with 150 g of diethylene glycol and 5.4 g of potassium hydroxide, and the inside of the autoclave was thoroughly replaced with nitrogen, after which the temperature was raised to 140° C. and 1,245 g of ethylene oxide was gradually added. After the reaction of ethylene oxide was completed, the temperature was cooled to 120° C., and subsequently 2,460 g of propylene oxide was gradually added and thoroughly reacted, followed by cooling to obtain polyoxyethylene (20 mol) polyoxypropylene (30 mol) glycol.
Next, 819 g of the obtained polyoxyethylene (20 mol) polyoxypropylene (30 mol) glycol, 29.1 g of sulfamic acid, and 18.0 g of urea were charged into a 1 L glass flask, and the temperature was gradually raised to 120° C. to react the mixture, thereby obtaining polyoxyethylene (20 mol) polyoxypropylene (30 mol) glycol monosulfate ammonium salt. The anion purity of the product synthesized by combined sulfuric acid was 87.9%.

[Synthesis Example 6]
Ingredient (A6):
819g of polyoxyethylene (20 mol) polyoxypropylene (30 mol) glycol obtained in Synthesis Example 5 above, 43.6g of sulfamic acid, and 18.0g of urea were charged and gradually heated to 120°C to react, yielding a mixture of polyoxyethylene (20 mol) polyoxypropylene (30 mol) glycol monosulfate ammonium salt and polyoxyethylene (20 mol) polyoxypropylene (30 mol) glycol disulfate ammonium salt. The anion purity of the product synthesized by combined sulfuric acid was 129.8%.

[Synthesis Example 7]
Ingredient (A7):
819 g of polyoxyethylene (20 mol) polyoxypropylene (30 mol) glycol obtained in Synthesis Example 5 above, 58.1 g of sulfamic acid, and 24.0 g of urea were charged and gradually heated to 120° C. to react, yielding a mixture of polyoxyethylene (20 mol) polyoxypropylene (30 mol) glycol monosulfate ammonium salt and polyoxyethylene (20 mol) polyoxypropylene (30 mol) glycol disulfate ammonium salt. The anion purity of the product synthesized by combined sulfuric acid was 173.3%.

[Synthesis Example 8]
Ingredients (A8):
A 5 L autoclave was charged with 600 g of tridecanol and 5.6 g of potassium hydroxide, and the inside of the autoclave was thoroughly replaced with nitrogen, after which the temperature was raised to 150° C. and 1,320 g of ethylene oxide was gradually added. After the reaction of ethylene oxide was completed, the temperature was cooled to 120° C., and then 870 g of propylene oxide was gradually added and allowed to react sufficiently, followed by cooling to obtain polyoxyethylene (10 mol) polyoxypropylene (5 mol) tridecanol ether.
Next, 558 g of the obtained polyoxyethylene (10 mol) polyoxypropylene (5 mol) tridecanol ether, 58.2 g of sulfamic acid, and 36.0 g of urea were charged into a 1 L glass flask, and the temperature was gradually raised to 120° C. to react the mixture, thereby obtaining polyoxyethylene (10 mol) polyoxypropylene (5 mol) tridecanol ether monosulfate ammonium salt. The anion purity of the product synthesized by combined sulfuric acid was 92.3%.

Synthesis of component (B) [Synthesis Example 9]
Ingredient (B1):
A 5L autoclave was charged with 400g of styrenated phenol (main component: tristyrenated phenol) and 2.5g of potassium hydroxide, and the inside of the kettle was fully replaced with nitrogen, and then the temperature was raised to 150°C and 880g of ethylene oxide was gradually added to obtain polyoxyethylene (20 moles) styrenated phenyl ether. Next, 500g of the obtained polyoxyethylene (20 moles) styrenated phenyl ether, 37.9g of sulfamic acid, and 23.4g of urea were charged into a 1L glass flask, and the temperature was gradually raised and reacted at 120°C to obtain polyoxyethylene (20 moles) styrenated phenyl ether sulfate ammonium salt. The anion purity of the synthesis by combined sulfuric acid was 85% or more. The average number of moles of styryl groups added was 2.8 moles.

[Synthesis Example 10]
Component (B2):
A 5L autoclave was charged with 400g of styrenated phenol (main component: tristyrenated phenol) and 3.0g of potassium hydroxide, and the inside of the kettle was fully replaced with nitrogen, and then the temperature was raised to 150°C and 1100g of ethylene oxide was gradually added to obtain polyoxyethylene (25 moles) styrenated phenyl ether. Next, 500g of the obtained polyoxyethylene (25 moles) styrenated phenyl ether, 32.3g of sulfamic acid, and 20.0g of urea were charged into a 1L glass flask, and the temperature was gradually raised and reacted at 120°C to obtain polyoxyethylene (25 moles) styrenated phenyl ether sulfate ammonium salt. The anion purity of the synthesis by combined sulfuric acid was 85% or more. The average number of moles of styryl groups added was 2.8 moles.

[Synthesis Example 11]
Component (B3):
A 5L autoclave was charged with 400g of styrenated phenol (main component: tristyrenated phenol) and 3.4g of potassium hydroxide, and the inside of the autoclave was fully replaced with nitrogen. The temperature was raised to 150°C, and 1320g of ethylene oxide was gradually added to obtain polyoxyethylene (30 moles) styrenated phenyl ether. Next, 500g of the obtained polyoxyethylene (30 moles) styrenated phenyl ether, 28.2g of sulfamic acid, and 17.4g of urea were charged into a 1L glass flask, and the temperature was gradually raised to 120°C to react, thereby obtaining polyoxyethylene (30 moles) styrenated phenyl ether sulfate ammonium salt. The anion purity of the synthesis by combined sulfuric acid was 85% or more. The average number of moles of styryl groups added was 2.8 moles.

Synthesis of Component (C) [Synthesis Example 12]
Component (C1):
300g of glycerin and 6.3g of potassium hydroxide were charged into a 5L autoclave, and the inside of the autoclave was thoroughly replaced with nitrogen. Then, the temperature was raised to 150°C, and 2870g of ethylene oxide was gradually added to obtain polyoxyethylene (20 moles) glycerol ether. Next, 500g of the obtained polyoxyethylene (20 moles) glycerol ether, 1.8g of potassium hydroxide, and 428g of oleic acid were charged into a 1L glass flask, and the temperature was gradually raised to 180°C to react, thereby obtaining polyoxyethylene (20 moles) glycerol trioleyl ester. The end point was confirmed by the acid value, and the amount of unreacted oleic acid was less than 0.3%.

[Synthesis Example 13]
Component (C2):
In a 1L glass flask, 400g of polyethylene glycol with a molecular weight of 600, 1.5g of potassium hydroxide, and 361g of oleic acid were charged, and the temperature was gradually raised to 180°C to react, obtaining polyoxyethylene glycol (600) dioleyl ester. The end point was confirmed by the acid value, and the amount of unreacted oleic acid was less than 0.3%. The average number of moles of ethylene oxide added was 13 moles.

Fiber treatment auxiliaries were prepared by mixing (A1) to (A8), (B1) to (B3), and (C1) to (C2) obtained in the above Synthesis Examples in the mass ratios shown in Table 1. The treatment agents were subjected to evaluation tests by the following methods.
In each evaluation test, in order to maintain the dilution property into the test liquid and the stability of the mixed liquid, the fiber treatment auxiliary having the composition shown in Table 1 was diluted with water before use.

The comparative components are as follows:
(Component D1)
In a 1 L glass flask, 400 g of polyethylene glycol having a molecular weight of 400, 97.1 g of sulfamic acid, and 60.0 g of urea were charged, and the temperature was gradually raised to 120° C. to cause a reaction, thereby obtaining polyethylene glycol (400) monosulfate ammonium salt.
(Component D2)
In a 5 L autoclave, 400 g of oleyl alcohol and 3.5 g of potassium hydroxide were charged, and the inside of the autoclave was thoroughly replaced with nitrogen, and then the temperature was raised to 150° C. and 1,313 g of ethylene oxide was gradually added. After the reaction, polyoxyethylene (20) oleyl ether was obtained.

Other common active ingredient components used in the comparative examples include polyoxyethylene (10) polyoxypropylene (30) glycol, polyoxyethylene (20) polyoxypropylene (30) glycol, and dodecylbenzenesulfonic acid.

[Performance evaluation test method]
(1) High-temperature and high-pressure dyeing test using flame retardant (preparation of test solution)
A test liquid was prepared by adding 10 g/L of a brominated flame retardant, 1 g/L of a disperse dye (red, C.I. 60), 0.3 g/L of acetic acid, and 0.4 g of a fiber treatment auxiliary shown in Table 1 to 1 L of water as a solvent and mixing them.
(Dyeing test)
A test cloth of unprocessed polyester fabric and the above test liquid of 10 times the weight of the test cloth were placed in the pot of the dyeing tester, and dyeing treatment was performed for 30 minutes at 0.30 MPa and 130°C. After dyeing, the test cloth was removed from the pot, washed with water, and dried to check whether there was uneven dyeing or dirt due to aggregates on the test cloth. In addition, the inside of the pot after dyeing was checked to check whether there was any adhesion of aggregates. The less uneven dyeing or aggregates, the better the dispersion ability. The dispersion performance was evaluated according to the following criteria.
(evaluation)
. . . No uneven dyeing or stains, and no pot agglomerates.
◯: No uneven dyeing or stains, but slight pot agglomerations were observed.
.DELTA.: Slight unevenness in dyeing, dye stains, and pot agglomerates were observed.
×: Many uneven dyeing spots, dye stains, and many pot agglomerates were observed.

(2) Confirmation of agglomerates upon heating at high temperature The test liquid prepared in (1) above was heated while being mixed in a glass container, and heated for 10 minutes under boiling temperature conditions of 95°C to 105°C. After heating, filtration was performed using a funnel and a test cloth, and the amount of agglomerates remaining on the filter cloth that were generated upon boiling and evaporation of the test liquid was confirmed. Fewer agglomerates indicate superior dispersion ability. The presence and amount of agglomerates were visually confirmed, and evaluation was performed according to the following criteria.
(evaluation)
. . . No dirt was observed on the filter cloth.
○: One or two small aggregates are observed on the filter cloth.
.DELTA.: Many small aggregates were observed on the filter cloth.
×: Many large aggregates are observed on the filter cloth.

(3) High temperature dispersibility test of dyes (preparation of test solution)
0.7 g/L of disperse dye (red or blue), 0.3 g/L of acetic acid, and 0.4 g/L of the fiber treatment aid shown in Table 1 were added to 1 L of water as a solvent and mixed to prepare test solutions for red and blue. As the disperse dye, C.I.60 was used for red, and C.I.73 was used for blue. The dispersibility of each of the red and blue was confirmed by the following method.
(Dyeing test)
A polyester jersey test cloth was set in a color pet type dyeing tester, and a test liquid 15 times the weight of the test cloth was poured in. After the temperature of the tester was raised to 125°C, the test cloth was quickly cooled, washed with water and dried, and the amount and density of spots generated on the test cloth were confirmed and evaluated according to the following criteria.
(evaluation)
. . . Both red and blue were dyed uniformly with no spots.
◯: A faint spot is observed in at least one of the red and blue colors.
.DELTA.: Dark spots are observed in at least one of the red and blue colors.
×: Dark spots are observed over the entire test cloth in both red and blue.

(4) Even dyeing test A polyester woven test cloth was prepared by dyeing in advance with 1% by weight of disperse dye (red, blue, and yellow, respectively) based on the weight of the test cloth (original dyed cloth). A white cloth (untreated test cloth) of the same weight as the dyed test cloth was placed in the pot of the dyeing tester, and a test liquid (a mixture of 0.3 g/L of acetic acid and 0.4 g/L of the fiber processing assistant shown in Table 1 added to 1 L of water) was added in an amount 20 times the weight of the test cloth, and the dyeing treatment was performed at 130°C for 30 minutes. After the treatment, the test cloth was taken out, washed with water, dried, and the dyeing state of the test cloth was confirmed. The more the dye was transferred from the previously dyed cloth to the white cloth, the higher the transfer ability of the dye during the dyeing treatment and the better the ability of even dyeing. The dye transfer ability of each of red, blue, and yellow was confirmed, and the ability of even dyeing was evaluated comprehensively.
(evaluation)
◎: Both the original-dyed fabric and the test fabric are dyed evenly without any unevenness. ◯: The color of the original-dyed fabric is slightly darker, but dyed evenly.
△: The color of the original dyed fabric is slightly dark and uneven dyeing can be seen.
×: There is a large difference in color between the original dyed fabric and the test fabric, and uneven dyeing has occurred.

As shown in Tables 1 and 2 above, the fiber processing aid of the present invention can suppress the generation of aggregates between the dye and the flame retardant during a dyeing process at high temperatures, including a flame retardant addition process, and can simultaneously exhibit good dyeability.
The fiber processing aid of the present invention can suppress the generation of aggregates of dyes and flame retardants, particularly in dyeing processes of polyester fibers at high temperatures, and can give good dyed products with uniform dyeing.

Claims (8)

(A) A compound represented by the following general formula (1): 40 to 90 parts by mass X ¹ -O-(A ¹ O) _n1 (A ² O) _n2 -X ² (1)
(wherein A ¹ is an ethylene group, A ² is an alkylene group having 3 or 4 carbon atoms, n ¹ is a number from 3 to 30, n ² is a number from 5 to 60, the mutual arrangement of A ¹ O and A ² O is not limited and may form a block unit or a random bond, X ¹ is a hydrogen atom, an alkyl or alkenyl group having 8 to 22 carbon atoms, -SO ₃ M, or -PO ₃ M, X ² is -SO ₃ M, or -PO ₃ M, and M is a hydrogen atom, an ammonium ion, an organic ammonium ion, or a monovalent metal ion).
(B) 5 to 25 parts by mass of a compound represented by the following general formula (2):
(In the formula, m is a number from 1 to 3, ⁿ³ is a number from 5 to 60, ^A3 is an alkylene group having 2 to 4 carbon atoms, and M' is a hydrogen atom, an ammonium ion, an organic ammonium ion, or a monovalent metal ion).
And,
(C) Polyoxyalkylene polyhydric alcohol fatty acid ester: 5 to 35 parts by mass (wherein the total of components (A), (B), and (C) is 100 parts by mass)
A processing aid for polyester fibers comprising: The component (C) is represented by the following general formula (3):
[H-(OA ⁴ ) _n4 -O-] _r R ¹ [-O-(A ⁵ O) _n5 -C(=O)-R ² ] _s
(3)
(In the formula, R ¹ is a residue obtained by removing two or more hydroxy groups from a dihydric to octahydric polyhydric alcohol having 2 to 30 carbon atoms, A ⁴ is an alkylene group having 2 to 4 carbon atoms, n ⁴ is a number from 1 to 80, R ² is an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 2 to 30 carbon atoms, A ⁵ is an alkylene group having 2 to 4 carbon atoms, n ⁵ is a number from 1 to 80, and r and s are integers satisfying the relationships 0≦r≦7, 1≦s≦8, and 2≦r+s≦8.)
2. The polyester fiber processing aid according to claim 1, wherein the formula is 3. The polyester fiber processing aid according to claim 1, wherein component (C) is a polyoxyethylene polyhydric alcohol fatty acid ester. 4. The polyester fiber processing aid according to claim 1, wherein in the formulas (1) and (2), M and M' are each independently an ammonium ion, an organic ammonium ion, a sodium ion, or a potassium ion. A method for producing a dyed fiber product, comprising the steps of: adding the polyester fiber processing aid according to any one of claims 1 to 4 to a dyebath; and dyeing polyester fiber in the dyebath to obtain a dyed product. The method according to claim 5 , wherein the amount of the polyester fiber processing aid added is 0.01 to 2 g per 1 L of the dye bath. A step of adding the following components (A), (B), and (C) to a dyebath:
(A) A compound represented by the following general formula (1): 40 to 90 parts by mass X ¹ -O-(A ¹ O) _n1 (A 2 O) _n2 -X ² (1) per 100 parts by mass of the total of the components (A), ( ^B ), and (C).
(wherein A ¹ is an ethylene group, A ² is an alkylene group having 3 or 4 carbon atoms, n ¹ is a number from 3 to 30, n ² is a number from 5 to 60, the mutual arrangement of A ¹ O and A ² O is not limited and may form a block unit or a random bond, X ¹ is a hydrogen atom, an alkyl or alkenyl group having 8 to 22 carbon atoms, -SO ₃ M, or -PO ₃ M, X ² is -SO ₃ M, or -PO ₃ M, and M is a hydrogen atom, an ammonium ion, an organic ammonium ion, or a monovalent metal ion).
(B) A compound represented by the following general formula (2): 5 to 25 parts by mass per 100 parts by mass of the total of the components (A), (B), and (C)
(In the formula, m is a number from 1 to 3, ⁿ³ is a number from 5 to 60, ^A3 is an alkylene group having 2 to 4 carbon atoms, and M' is a hydrogen atom, an ammonium ion, an organic ammonium ion, or a monovalent metal ion).
A method for producing a dyed fiber product, comprising: (C) 5 to 35 parts by mass of a polyoxyalkylene polyhydric alcohol fatty acid ester per 100 parts by mass of the total of the components (A), (B), and (C); and dyeing a polyester fiber in the dyebath to obtain a dyed product. The method according to claim 7 , wherein the total amount of the components (A), (B), and (C) is 0.01 to 2 g per 1 L of the dye bath.