Fastness improver composition and method for producing polyester dyeing fiber product

Abstract

In the case of dyeing and soaping treatment of polyester fibers, the fastness of the dyed polyester fiber products is improved. In the soaping treatment after dyeing of the polyester fibers, a soaping solution containing a specified polyester copolymer is used. The polyester copolymer contains dicarboxylic acid units and diol units. The dicarboxylic acid units include units derived from dicarboxylic acids having one or both sulfonic acid groups and sulfonate groups, and units derived from at least one of tricarboxylic acid units, at a rate of 5 mol% to 30 mol%. The diol units are derived from diols with a molecular weight of 48 or more and less than 900. The intramolecular content ratio of the dicarboxylic acid units in the polyester copolymer is 50% by mass or more and 75% by mass or less.

Description

Technical Field

[0001] This application discloses a fastness-enhancing agent composition and a method for manufacturing polyester dyed fiber articles. Background Technology

[0002] Generally, the dyeing of polyester fibers is carried out by dyeing with a dyeing solution containing dye at approximately 120–135°C, draining the dyeing solution, and then soaping with a soaping solution containing a soaping agent at approximately 60–100°C in a separate bath. This is known as the 2-bath 2-stage method. For example, Patent Document 1 discloses a 2-bath 2-stage method in which polyester fibers are dyed, removed, and then soaped with a reducing washing bath containing a liquid reducing agent composed of reducing sugars such as glucose at 85°C.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: International Publication No. 2020 / 196902 Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] Polyester dyed fiber products manufactured using the method disclosed in Patent Document 1 have potential for improved fastness. New technologies are needed to improve the fastness of polyester dyed fiber products.

[0008] Methods for solving problems

[0009] This application discloses several solutions as means to solve the above-mentioned problems.

[0010] (Option 1)

[0011] A fastness-enhancing composition comprising a polyester copolymer.

[0012] The above-mentioned polyester copolymer contains dicarboxylic acid units and diol units.

[0013] The aforementioned dicarboxylic acid unit comprises a unit derived from a dicarboxylic acid having one or both of a sulfonic acid group and a sulfonate group, and a unit derived from a tricarboxylic acid, comprising 5 mol% to 30 mol% of at least one of these units.

[0014] The aforementioned diol units are derived from diols with a molecular weight of 48 or higher and less than 900, and,

[0015] The intramolecular content of the dicarboxylic acid unit in the above-mentioned polyester copolymer is 50% by mass or more and 75% by mass or less.

[0016] (Option 2)

[0017] A manufacturing method for polyester-based dyed fiber products includes the following steps:

[0018] Polyester fibers are dyed.

[0019] The polyester fibers, after the above dyeing treatment, are subjected to soaping treatment in the same bath or separate bath with the dyeing solution; and

[0020] The polyester fibers after the above-mentioned soaping treatment are subjected to one or both of the following washing treatments: hot water washing and water washing.

[0021] One or both of the soaping solution used in the above-mentioned soaping treatment and the washing solution used in the above-mentioned washing treatment contain polyester copolymers.

[0022] The above-mentioned polyester copolymer contains dicarboxylic acid units and diol units.

[0023] The aforementioned dicarboxylic acid unit comprises a unit derived from a dicarboxylic acid having one or both of a sulfonic acid group and a sulfonate group, and a unit derived from a tricarboxylic acid, comprising 5 mol% to 30 mol% of at least one of these units.

[0024] The aforementioned diol units are derived from diols with a molecular weight of 48 or higher and less than 900, and,

[0025] The intramolecular content of the dicarboxylic acid unit in the above-mentioned polyester copolymer is 50% by mass or more and 75% by mass or less.

[0026] (Option 3)

[0027] According to the manufacturing method of Scheme 2, it includes the step of performing the above-mentioned soaping treatment on the above-mentioned dyed polyester fibers in the same bath as the above-mentioned dyeing solution.

[0028] The dyeing solution used in the above dyeing process contains the above-mentioned polyester copolymer, and

[0029] At least a portion of the polyester copolymer contained in the dyeing solution is utilized as at least a portion of the polyester copolymer contained in the soaping solution.

[0030] (Option 4)

[0031] According to the manufacturing method of Scheme 2 or 3, it includes the step of performing the above-mentioned soaping treatment on the above-mentioned dyed polyester fibers in the same bath as the above-mentioned dyeing solution, and

[0032] The soaping solution used in the above-mentioned soaping treatment is prepared by adding at least the above-mentioned polyester copolymer to the dyeing solution after the above-mentioned dyeing treatment.

[0033] (Option 5)

[0034] According to the manufacturing method of any one of Schemes 2 to 4, the amount of the polyester copolymer contained in the soaping liquid is 0.005 g / L or more and 5.0 g / L or less.

[0035] (Option 6)

[0036] According to the manufacturing method of any one of Schemes 2 to 5, the amount of the polyester copolymer contained in the washing liquid is 0.005 g / L or more and 5.0 g / L or less.

[0037] The effects of the invention

[0038] According to the compositions and manufacturing methods disclosed herein, for example, by using a soaping solution containing a specified polyester copolymer in the soaping process, it is possible to improve the fastness of polyester-dyed fiber articles to an effect equivalent to or greater than that of conventional dyeing and soaping processes.

[0039] In recent years, in addition to reducing processing costs through process optimization, environmental measures such as water conservation and CO2 reduction have led to an increase in the practice of performing dyeing and soaping treatments in the same bath (1 bath) (1-stage method). However, in the 1-bath 2-stage method, a significant decrease in fastness has been observed with respect to conventionally used soaping agents compared to the 2-bath 2-stage method. According to the composition and manufacturing method disclosed herein, good fastness can be obtained even when soaping treatment is performed in a 1-bath 2-stage manner.

[0040] Furthermore, according to the compositions and manufacturing methods disclosed herein, for example, by using a washing liquid containing a specified polyester copolymer in a washing process (hot water washing and / or water washing) after soaping treatment, it is possible to improve the fastness of polyester-based dyed fiber articles. Detailed Implementation

[0041] 1. Manufacturing method of polyester dyed fiber products

[0042] The following describes a method for manufacturing a polyester-based dyed fiber product according to one embodiment. The method includes: dyeing polyester fibers; soaping the dyed polyester fibers in a bath (1 bath) or a separate bath (2 bath) with a dyeing solution; and subjecting the soaped polyester fibers to one or both of a hot water wash and a water wash. Here, one or both of the soaping solution used in the soaping treatment and the washing solution used in the washing treatment comprise a polyester copolymer (polymer A). The polyester copolymer comprises dicarboxylic acid units and diol units. The dicarboxylic acid units comprise at least 5 mol% and 30 mol% of at least one of dicarboxylic acid units having one or both sulfonic acid groups and sulfonate groups, and units derived from tricarboxylic acids. The diol units are derived from diols with a molecular weight of 48 or more and less than 900. The intramolecular content of the dicarboxylic acid units in the polyester copolymer is 50% by mass or more and 75% by mass or less.

[0043] 1.1 Staining treatment

[0044] The manufacturing method disclosed herein includes dyeing polyester fibers. A dyeing solution is used in the dyeing process.

[0045] 1.1.1 Polyester fibers

[0046] Polyester fibers intended for dyeing can be any type of polyester fiber. These polyester fibers can be, for example, polyester fibers formed from homopolymers or copolymers of at least one selected from polyethylene terephthalate, 1,2-propylene terephthalate, 1,3-propylene terephthalate, and butylene terephthalate; or composite fibers selected from at least one type of blend, interweaving, and cross-knitting of polyester fibers with other synthetic fibers or natural fibers; or both. The form of the polyester fibers can be, for example, selected from at least one form selected from silk, knitted fabrics, woven fabrics, and nonwoven fabrics. Polyester fibers are preferably spun.

[0047] 1.1.2 Composition of the staining solution

[0048] The components of the dyeing solution may include water, organic solvents, and surfactants. Furthermore, the dyeing solution may contain acids, chelating agents, etc., for pH adjustment. Further, as described later, the dyeing solution may contain a specified polyester copolymer (polymer A). Alternatively, as described later, a specified polyester copolymer (polymer A) may be added to the dyeing solution after dyeing treatment.

[0049] The organic solvent can be, for example, an alcohol having 1 to 10 carbon atoms. Specifically, it can be at least one selected from methanol, ethanol, isopropanol, ethylene glycol monobutyl ether, and diethylene glycol monobutyl ether.

[0050] The surfactant is not particularly limited and can be any known surfactant. For example, it can be at least one selected from anionic surfactants, nonionic surfactants, and cationic surfactants.

[0051] Anionic surfactants can be, for example, selected from at least one of the following substances:

[0052] Sulfate, phosphate, or salts of olefinic adducts of aliphatic alcohols (aliphatic alcohols have 1 to 22 carbon atoms);

[0053] Sulfate, phosphate, or salts thereof of polyalkylene glycols obtained from olefin oxides having 2 to 4 carbon atoms;

[0054] Sulfate, phosphate, or salts thereof of mono- or polystyrene-oxidized olefinic phenols;

[0055] Sulfates, phosphates, or salts thereof of mono- or polystyrene-based alkyl (alkyl group with 1 to 22 carbon atoms) phenol oxide olefin adducts;

[0056] Alkyl (8-22 carbon atoms) benzenesulfonic acid or its salt;

[0057] Alkyl (8-22 carbon atoms) sulfonic acid or its salt;

[0058] α-olefin sulfonic acids or their salts having 8 to 22 carbon atoms; and

[0059] Alkyl esters of α-sulfonyl fatty acids (α-sulfonyl fatty acids with 8 to 22 carbon atoms and alkyl groups with 1 to 12 carbon atoms) or their salts.

[0060] The salt may be, for example, selected from at least one of alkali metal salts, alkaline earth metal salts, ammonium salts, and alkanolamine salts.

[0061] Nonionic surfactants can be, for example, selected from at least one of the following substances:

[0062] olefinic adducts of aliphatic alcohols (1-22 carbon atoms) or their fatty acid esters (8-24 carbon atoms);

[0063] Polyalkylene glycols or their fatty acid esters (fatty acids with 8 to 24 carbon atoms) obtained from olefin oxides with 2 to 4 carbon atoms;

[0064] Oxidized olefinic adducts of mono- or polystyrene-based phenols or their fatty acid esters (fatty acids with 8 to 24 carbon atoms); and

[0065] Fatty acid (fatty acid with 8 to 24 carbon atoms) esters of mono- or polystyrene-based alkyl (alkyl group with 1 to 22 carbon atoms) phenol oxide olefin adducts.

[0066] Cationic surfactants can be, for example, selected from benzalkonium chloride; reactants of trialkylamines having one or two long-chain alkyl groups with quaternizing agents; reactants of mono- or dialkylamine oxidized olefin adducts with quaternizing agents; alkylpyridines. The salt; at least one quaternary ammonium surfactant. The long-chain alkyl group of the above-mentioned trialkylamine may have, for example, 6 to 24 carbon atoms, and the remaining alkyl group of the above-mentioned trialkylamine may have, for example, 1 to 5 carbon atoms. The alkyl group of the above-mentioned mono- or dialkylamine may have, for example, 6 to 24 carbon atoms. The above-mentioned alkylene oxide may be, for example, an alkylene oxide having 2 to 4 carbon atoms, and their addition molar number may be, for example, 2 to 50. The above-mentioned quaternizing agent may be, for example, at least one selected from alkyl halides having 1 to 5 carbon atoms and dialkyl sulfuric acid having 1 to 5 carbon atoms. The above-mentioned alkylpyridine The number of carbon atoms in the alkyl group of the salt can be, for example, 3 to 24.

[0067] From the viewpoint of superior leveling and staining properties, the dyeing solution preferably contains at least one surfactant selected from anionic and nonionic surfactants.

[0068] There is no particular limitation on the amount of surfactants, etc., contained in the dyeing solution. From the viewpoint of superior leveling and staining properties, the amount of surfactant contained in the dyeing solution is preferably 0 g / L or more and 25 g / L or less, more preferably 0.015 g / L or more and 6.0 g / L or less.

[0069] 1.1.3 Other conditions in staining treatment

[0070] There are no particular limitations on other conditions in the dyeing process; conditions that enable the above-mentioned polyester fibers to be dyed using the dyeing solution shall be adopted. Examples of such conditions include the following.

[0071] 1.1.3.1 Bath ratio in staining treatment

[0072] The ratio of polyester fiber to dyeing solution varies depending on the desired performance, and can be, for example, 1:3 to 1:30, preferably 1:5 to 1:25, and more preferably 1:5 to 1:20.

[0073] 1.1.3.2 Dyes

[0074] Any dye capable of coloring polyester fibers is acceptable. Disperse dyes, for example, are suitable. The amount of dye used can be appropriately selected. For example, it can be above 0.001% owf and below 20% owf.

[0075] 1.1.3.3 Dyeing Machinery

[0076] There are no particular limitations on the dyeing machinery used in the dyeing process; conventional materials can be used. Examples include liquid flow dyeing machines, rope dyeing machines, roll dyeing machines, spool dyeing machines, bobbin dyeing machines, austenitic dyeing machines, and high-pressure jet dyeing machines.

[0077] 1.1.3.4 Staining temperature and staining time

[0078] The polyester fibers are brought into contact with the dyeing solution using the dyeing machinery described above, thereby performing the dyeing process. The dyeing temperature and time can be handled under the same conditions as before. For example, the dyeing solution can be heated to approximately 40–60°C, typically with a slow increase in temperature over approximately 50–80 minutes, or, if faster dyeing is desired, with a slow increase over approximately 30–50 minutes, followed by a high-temperature treatment at 120–140°C (preferably 125–135°C) for approximately 0–90 minutes, preferably 30–60 minutes.

[0079] 1.2 Soap washing treatment

[0080] The manufacturing method disclosed herein includes performing a soaping treatment on the dyed polyester fibers in the same bath or separate bath with the dyeing solution. Here, the soaping solution used for the soaping treatment may contain the polyester copolymer (polymer A) described later.

[0081] 1.2.1 Soap Wash

[0082] The soaping solution may contain polymer A. Furthermore, the soaping solution may contain other components besides polymer A. If the washing solution in the washing process described later contains polymer A, the soaping solution may or may not contain polymer A. If the washing solution described later does not contain polymer A, the soaping solution contains polymer A.

[0083] 1.2.1.1 Polymer A

[0084] Polymer A comprises dicarboxylic acid units and diol units. Polymer A is obtained, for example, by transesterification, direct polymerization, etc.

[0085] (Dicarboxylic acid unit)

[0086] The dicarboxylic acid units constituting polymer A comprise at least 5 mol% and 30 mol% of at least one of a dicarboxylic acid unit (unit X) having one or both of a sulfonic acid group and a sulfonate group, and a unit (unit Y) constituting a tricarboxylic acid unit. In other words, the dicarboxylic acid units constituting polymer A comprise at least 5 mol% and 30 mol% of one or both of units X and units Y, and the remainder is composed of dicarboxylic acid units other than units X and units Y. The dicarboxylic acid units constituting polymer A preferably comprise at least 5 mol% and 15 mol% of unit X derived from a dicarboxylic acid having one or both of a sulfonic acid group and a sulfonate group, more preferably at least 5 mol% and 12 mol% or less. Alternatively, the dicarboxylic acid units constituting polymer A preferably comprise at least 8 mol% and 20 mol% of unit Y derived from a tricarboxylic acid, more preferably at least 10 mol% and 20 mol% or less. When the dicarboxylic acid units constituting polymer A have units X derived from dicarboxylic acids having one or both of sulfonic acid and sulfonate groups, if there are too few units X, the solubility in water may decrease, and the dye may become poorly dispersed during dyeing and soaping processes. On the other hand, if there are too many, it will be difficult to obtain sufficient fastness. The same applies when the dicarboxylic acid units constituting polymer A have units Y derived from tricarboxylic acids.

[0087] Furthermore, "a unit derived from a tricarboxylic acid" can be expressed as "a unit derived from a dicarboxylic acid having an additional carboxyl group or carboxylate group." That is, in this application, "a unit derived from a tricarboxylic acid" is exceptionally considered as one type of "dicarboxylic acid unit." On the other hand, in this application, "a unit derived from a polycarboxylic acid with four or more members" is not considered as a "dicarboxylic acid unit."

[0088] The dicarboxylic acid unit constituting polymer A can be derived from aliphatic dicarboxylic acids or aromatic dicarboxylic acids, but is preferably derived from aromatic dicarboxylic acids. Aromatic dicarboxylic acids can be, for example, selected from at least one of terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, β-hydroxyethoxybenzoic acid, and p-hydroxybenzoic acid. Wherein, when the dicarboxylic acid unit constituting polymer A includes one or both of terephthalic acid and isophthalic acid, superior properties are readily obtained. Aliphatic dicarboxylic acids can be, for example, selected from at least one of adipic acid, sebacic acid, dodecanoic acid, maleic acid, and succinic acid. These dicarboxylic acids can be acid anhydrides or ester derivatives of lower alcohols or diols.

[0089] Dicarboxylic acids having one or both of a sulfonic acid group and a sulfonate group can have a sulfonic acid group and / or a sulfonate group attached to the various dicarboxylic acids described above. The sulfonate group can be, for example, a metal salt group such as a Li salt, Na salt, K salt, or Mg salt, or an amine salt group such as ammonia or triethanolamine. A group of alkali metal salts, especially a Na salt group, is particularly preferred. Dicarboxylic acids having one or both of a sulfonic acid group and a sulfonate group can be, for example, at least one selected from sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, their salts, their dimethyl esters, diethyl esters, diphenyl esters, and other ester derivatives thereof.

[0090] Tricarboxylic acids (dicarboxylic acids additionally having one or both of a carboxylic acid group and a carboxylate group) may have a carboxylic acid group and / or a carboxylate group attached to the various dicarboxylic acids described above. The carboxylate group may be, for example, a metal salt group such as Li salt, Na salt, K salt, Mg salt, or an amine salt group such as ammonia or triethanolamine. A group of alkali metal salts, especially Na salts, is particularly preferred. As a tricarboxylic acid (a dicarboxylic acid containing a carboxylic acid group), it may be, for example, at least one selected from trimellitic acid, pyromellitic acid, 1,2,3-benzenetricarboxylic acid, their salts, their dimethyl esters, diethyl esters, diphenyl esters, and other ester derivatives.

[0091] The dicarboxylic acid unit constituting polymer A can include, for example, a unit derived from dicarboxylic acid a1 that does not have a sulfonic acid group or a sulfonate group and does not conform to a tricarboxylic acid, and a unit derived from dicarboxylic acid a2 that has one or both of a sulfonic acid group and a sulfonate group and does not conform to a tricarboxylic acid. Alternatively, the dicarboxylic acid unit constituting polymer A can include, for example, a unit derived from dicarboxylic acid a1 that does not have a sulfonic acid group or a sulfonate group and does not conform to a tricarboxylic acid, and a unit derived from tricarboxylic acid a3 (additionally having one dicarboxylic acid selected from one or both of a carboxylic acid group and a carboxylate group). The carbon skeleton of dicarboxylic acid a1, the carbon skeleton of dicarboxylic acid a2, and the carbon skeleton of tricarboxylic acid a3 can be of the same type or different types. The dicarboxylic acid unit constituting polymer A may include, for example, units derived from one or both of terephthalic acid and isophthalic acid, which are dicarboxylic acids a1 that do not have sulfonic acid groups and sulfonate groups and do not conform to tricarboxylic acids; and may also include units derived from sulfoisophthalic acid, which are dicarboxylic acids a2 that have one or both of sulfonic acid groups and sulfonate groups and do not conform to tricarboxylic acids. Specific examples of tricarboxylic acid a3 are as described above.

[0092] The dicarboxylic acid units constituting polymer A can be, for example, units derived from dicarboxylic acids with a molecular weight of 100 or more and 300 or less. The dicarboxylic acid units constituting polymer A and the polyacid units constituting the aforementioned polyester fibers can be of the same type or different types.

[0093] (Polycarboxylic acid units other than dicarboxylic acid units)

[0094] In addition to the dicarboxylic acid mentioned above, polymer A may also contain, for example, units derived from 4- to 6-membered polycarboxylic acids such as tetracarboxylic acid, pentacarboxylic acid, and hexacarboxylic acid as structural units. In polymer A, the proportion of dicarboxylic acid units in the total polycarboxylic acid units may be, for example, more than 50 mol%, more than 60 mol%, more than 70 mol%, more than 80 mol%, more than 90 mol%, more than 95 mol%, or more than 99 mol%. Furthermore, the proportion of polycarboxylic acid units other than dicarboxylic acid units in the total polycarboxylic acid units may be, for example, less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, less than 10 mol%, less than 5 mol%, or less than 1 mol%.

[0095] (Diol unit)

[0096] The diol units constituting polymer A are derived from diols with a molecular weight of 48 or more and less than 900. The molecular weight of this diol is preferably 60 or more and less than 600, more preferably 60 or more and less than 300, and even more preferably 60 or more and less than 200. If the molecular weight of the diol is too low, sufficient water solubility may not be achieved, resulting in poor stability in the bath. On the other hand, if the molecular weight is too high, excessive water solubility may occur, adversely affecting the fastness improvement performance.

[0097] The diol unit constituting polymer A can be derived from aliphatic or aromatic diols, but is preferably derived from aliphatic diols. Examples of such diols include alkylene glycols and polyalkylene glycols. The diol can be at least one selected from polyethylene glycol, ethylene glycol, alkylene glycols with 3 or more carbon atoms, neopentyl glycol, polypropylene glycol, poloxamer (registered trademark) type surfactants, and ethylene oxide adducts of bisphenol A. Among these, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol with a molecular weight of 200 to 600, 1,4-butanediol, and neopentyl glycol are preferred. The diol unit constituting polymer A and the polyol unit constituting the above-mentioned polyester fiber can be of the same type or different types.

[0098] (Multi-hydroxy compound units other than diol units)

[0099] In addition to the diols mentioned above, polymer A may also contain, for example, units derived from 3- to 6-membered polyhydroxy compounds such as triols, tetraols, pentaols, and hexaols as structural units. In polymer A, the proportion of diol units in the total polyhydroxy compound units may be, for example, more than 50 mol%, more than 60 mol%, more than 70 mol%, more than 80 mol%, more than 90 mol%, more than 95 mol%, or more than 99 mol%. Furthermore, the proportion of polyhydroxy compound units other than diol units in the total polyhydroxy compound units may be, for example, less than 50 mol%, less than 40 mol%, less than 30 mol%, less than 20 mol%, less than 10 mol%, less than 5 mol%, or less than 1 mol%.

[0100] (Weight-average molecular weight of polymer A)

[0101] The weight-average molecular weight of polymer A is not particularly limited. When the dicarboxylic acid units constituting polymer A include units derived from dicarboxylic acids having one or both sulfonic acid groups and sulfonate groups, the weight-average molecular weight of polymer A can be, for example, 2000 or more and 80000 or less, or 5000 or more and 70000 or less. When the dicarboxylic acid units constituting polymer A include units derived from tricarboxylic acids, the weight-average molecular weight of polymer A can be, for example, 2000 or more and 80000 or less, or 2000 or more and 20000 or less. When the weight-average molecular weight of polymer A is within such a range, the fastness of polyester-based dyed fiber products can be further improved. Furthermore, the term "weight-average molecular weight" in this application is determined by size exclusion chromatography using an HLC-8120 (manufactured by Tosoh Corporation), a TSK-GEL Super AWM-H column (manufactured by Tosoh Corporation), and a mobile phase of 10 mM LiBr-DMF, with polystyrene as the standard.

[0102] (The intramolecular ratio of dicarboxylic acid units in polymer A)

[0103] The intramolecular content of dicarboxylic acid units in polymer A is 50% by mass or more and 75% by mass or less, preferably 55% by mass or more and 75% by mass or less, and more preferably 60% by mass or more and 75% by mass or less. Both excessively low and excessively high ratios make it difficult to obtain sufficient fastness.

[0104] (Amount of polymer A contained in the soaping solution)

[0105] The amount of polymer A contained in the soaping solution is not particularly limited. The amount of polymer A contained in the soaping solution is preferably 0.005 g / L or more and 5.0 g / L or less, more preferably 0.010 g / L or more and 3.0 g / L or less, and even more preferably 0.1 g / L or more and 2.5 g / L or less.

[0106] 1.2.1.2 Components other than polymer A

[0107] The soaping solution may contain components other than polymer A. Examples of components other than polymer A include well-known ingredients used in soaping processes (alkalis, reducing agents, etc.). Furthermore, the soaping solution may contain water, organic solvents, surfactants, etc. These may be derived from the dyeing solution. Details regarding organic solvents, surfactants, etc., are as described above. Additionally, the soaping solution may contain acids, chelating agents, etc., for pH adjustment.

[0108] The reducing agent can be, for example, at least one selected from dithionite, sodium dithionite, thiourea dioxide, and reducing sugars (D-glucose, D-xylose, etc.). In this case, the pH adjuster can be, for example, an alkaline substance such as caustic soda or soda ash. From the viewpoint of soaping effect, caustic soda is preferred as the reducing agent when using at least one selected from dithionite, sodium dithionite, thiourea dioxide, and reducing sugars. Alternatively, from the same viewpoint, soda ash can be used as the pH adjuster when using at least one selected from dithionite, sodium dithionite, and thiourea dioxide.

[0109] The reducing agent can be, for example, at least one sulfinic acid or its salt selected from sodium hydroxymethyl sulfinate, etc., and the pH adjuster in this case can be, for example, an acidic substance such as acetic acid or formic acid.

[0110] The reducing agent is preferably selected from at least one of dithionite, sodium dithionite, thiourea dioxide, and sodium hydroxymethyl sulfinate, and more preferably from at least one of dithionite, sodium dithionite, and thiourea dioxide. When such a reducing agent is combined with the above-mentioned polymer A, the fastness is more easily and significantly improved.

[0111] 1.2.2 Other conditions in soaping treatment

[0112] There are no particular limitations on other conditions in the soaping process; conditions that enable the polyester fibers to be soaped by the aforementioned soaping solution are adopted. Examples of such conditions include the following.

[0113] 1.2.2.1 Bath ratio in soap washing treatment

[0114] The ratio of polyester fiber to soaping solution varies depending on the desired performance, and can be, for example, 1:3 to 1:30, preferably 1:5 to 1:25, more preferably 1:5 to 1:20, and even more preferably 1:5 to 1:15.

[0115] 1.2.2.2 Soap washing treatment temperature and soap washing treatment time

[0116] The temperature for soaping can be the typical temperature used in dyeing processes, i.e., in the range of 60–140°C. However, considering the reduction in the physical properties and hand feel of the fiber products, a temperature of 70–100°C is preferred, and more preferably, 70–90°C. The soaping time can be, for example, 5–60 minutes. From the viewpoint of ensuring thorough soaping and suppressing the reduction in the physical properties of the fiber products, a time of 10–30 minutes is preferred.

[0117] 1.3. Two-bath, two-stage treatment (2-bath, 2-stage method)

[0118] As an example of the method of performing the above-mentioned dyeing and soaping treatments in a two-bath process (two-bath two-stage method), the following first method can be cited.

[0119] Method 1: After dyeing, discard the dyeing solution and re-prepare a soaping solution (soap bath) for soaping treatment.

[0120] 1.4. Simultaneous Bath Treatment (1 Bath 2-Stage Method)

[0121] As a method of performing the dyeing and soaping treatments in the same bath (1 bath), that is, performing the dyeing and soaping treatments in a 1-bath 2-stage process, specifically, after the dyeing treatment, the entire volume of the dyeing solution is not drained, leaving a portion or all of the residual dyeing solution, and the necessary ingredients are added during the soaping treatment. In this way, by performing the dyeing and soaping treatments in the same bath (1 bath), water and energy can be saved and energy can be reduced.

[0122] As with the 1-bath 2-stage method, when soaping is performed with residual components (dyes, etc.) from the dyeing solution in the soaping solution, the fastness of polyester-dyed fiber products is more likely to decrease. In contrast, in the manufacturing method disclosed herein, as described above, by including a polyester copolymer (polymer A) in the soaping solution, even when soaping is performed using the 1-bath 2-stage method, fastness equal to or better than that achieved with the conventional 2-bath 2-stage method for dyeing and soaping can be ensured.

[0123] In the manufacturing method disclosed herein, for example, a soaping solution can be prepared using 20% ​​to 100% by volume, 50% to 100% by volume, 70% to 100% by volume, or 90% to 100% by volume of the dyeing solution. If the dyeing solution is not drained after the dyeing treatment, 100% by volume of the dyeing solution is used as the soaping solution.

[0124] As a specific method for performing dyeing and soaping treatments in the same bath (1 bath), examples include the second and third methods described below. Furthermore, in the manufacturing method disclosed herein, as in the second method described below, even if the dyeing solution used for dyeing treatment contains a polyester copolymer (polymer A), the dyeing treatment of the polyester fibers using the dyeing solution is appropriately performed.

[0125] Method 2: The dyeing solution used in the dyeing process contains a polyester copolymer (polymer A), and at least a portion of the polymer A contained in the dyeing solution is utilized as at least a portion of the polymer A contained in the soaping solution. More specifically, for example, after dyeing with a dyeing solution containing polymer A, a soaping solution (soaping bath) is prepared by adding a pH adjuster and a reducing agent to the dyeing solution (dyeing bath), and a soaping treatment is performed.

[0126] Method 3: A method of soaping by adding at least one polyester copolymer (polymer A) to the dyeing solution (dyeing bath) after dyeing treatment. More specifically, for example, a method of soaping by adding a pH adjuster and a reducing agent, etc., to the dyeing solution (dyeing bath) after dyeing treatment along with polymer A.

[0127] Regarding methods 2 and 3 above, there are no particular limitations on the timing of adding pH adjusters and reducing agents to the dyeing solution after dyeing treatment. Preferably, the pH adjuster and reducing agent are added to the dyeing solution during cooling after dyeing treatment or after cooling to the temperature for soaping treatment (preferably after cooling to the temperature for soaping treatment). The timing for adding the polyester copolymer (polymer A) in method 3 is the same. Furthermore, in method 2, the polyester copolymer (polymer A) can be added to the dyeing solution after dyeing treatment with a dyeing solution containing the polyester copolymer (polymer A), or it can be omitted. In method 2, when the polyester copolymer (polymer A) is further added to the dyeing solution after dyeing treatment, the timing can be the same as described above.

[0128] 1.5 Washing treatment

[0129] The manufacturing method disclosed herein includes performing one or both of the following washing processes on the soaped polyester fibers: hot water washing and water washing. Here, the washing liquid used in the washing process may contain the aforementioned polymer A. Furthermore, the washing liquid may contain components other than polymer A. If the soaping liquid in the soaping process contains polymer A, the washing liquid in the washing process may or may not contain polymer A. If the soaping liquid does not contain polymer A, the washing liquid contains polymer A.

[0130] (Amount of polymer A contained in the detergent)

[0131] The amount of polymer A contained in the detergent solution is not particularly limited. The amount of polymer A contained in the detergent solution is preferably 0.005 g / L or more and 5.0 g / L or less, more preferably 0.010 g / L or more and 3.0 g / L or less, and even more preferably 0.1 g / L or more and 2.5 g / L or less.

[0132] (Components other than polymer A)

[0133] The washing solution may contain components other than polymer A. Examples of components other than polymer A include well-known ingredients used in hot water washing and / or water washing processes (pH adjusters, etc.).

[0134] (Other conditions during the washing process)

[0135] There are no particular limitations on other conditions in the washing process; conditions that allow the polyester fibers to be washed with hot water and / or water using the aforementioned washing solution are adopted. Examples of such conditions include the following.

[0136] (Liquor ratio in washing process)

[0137] The ratio of polyester fiber to washing liquid varies depending on the desired performance, and can be, for example, 1:3 to 1:30, preferably 1:5 to 1:25, more preferably 1:5 to 1:20, and even more preferably 1:5 to 1:15.

[0138] (Washing temperature and washing time)

[0139] The washing temperature can be a general processing temperature, for example, in the range of 20 to 100°C, preferably in the range of 30 to 90°C. The washing time can be, for example, 2 to 60 minutes. From the viewpoint of ensuring thorough washing and improving the quality of various physical properties of the fiber products, 5 to 30 minutes is preferred.

[0140] (Method for adding polymer A)

[0141] In the manufacturing method disclosed herein, good performance can be obtained when at least one of the dyeing solution, soaping solution, and washing solution contains the aforementioned polyester copolymer (polymer A). In particular, it is preferable that at least two or three of the dyeing solution, soaping solution, and washing solution contain the aforementioned polyester copolymer (polymer A). From the viewpoint that there is less variation in the hue of polyester-based dyed fiber articles, it is more preferable to add it to the soaping solution and washing solution.

[0142] 1.6 Other processing

[0143] The manufacturing method disclosed herein only requires the use of a specified polyester copolymer (polymer A), and involves dyeing and soaping treatments in a single bath (1 bath) or a separate bath (2 bath), followed by a washing treatment. It may further include various other treatments. For example, in the manufacturing method of this disclosure, scouring is preferably performed before the aforementioned dyeing treatment. Scouring is performed, for example, by using a scouring agent, in an intermittent manner using a rope-type or liquid flow dyeing machine, or in a continuous manner using a continuous scouring device. The scouring agent may be, for example, at least one selected from nonionic surfactants such as polyoxyalkylene ethers and polyoxyalkylene allyl ethers; mixtures of nonionic surfactants with anionic surfactants such as alkylbenzene sulfonates and aliphatic alcohol sulfates;

[0144] 2. Fastness improving agent composition

[0145] In addition to being a method for manufacturing the aforementioned polyester-based dyed fiber articles, the technology disclosed herein also has the aspect of being a fastness-enhancing agent composition. Specifically, one embodiment of the fastness-enhancing agent composition includes a polyester copolymer (polymer A). Here, the polyester copolymer includes dicarboxylic acid units and diol units. The dicarboxylic acid units include units derived from dicarboxylic acids having one or both sulfonic acid groups and sulfonate groups, and at least one of units derived from tricarboxylic acids, at a rate of 5 mol% to 30 mol% or less. The diol units are derived from diols with a molecular weight of 48 or more and less than 900. The intramolecular content ratio of the dicarboxylic acid units in the polyester copolymer is 50% by mass or more and 75% by mass or less.

[0146] Details regarding the polyester copolymer (polymer A) contained in the fastness-enhancing composition are as described above. The fastness-enhancing composition disclosed herein may, for example, contain other components besides polymer A. Details regarding other components besides polymer A are also as described above. The fastness-enhancing composition disclosed herein can be used, for example, during the dyeing of polyester fibers, during the soaping treatment of dyed polyester fibers, or after the soaping treatment.

[0147] 3. Supplement

[0148] Furthermore, the above description explains that the "dicarboxylic acid unit" constituting the polyester copolymer (polymer A) exceptionally includes "a unit derived from a tricarboxylic acid (a unit derived from a dicarboxylic acid having one or both of a carboxylic acid group and a carboxylate group)". On the other hand, assuming that "dicarboxylic acid unit" and "unit derived from a tricarboxylic acid" are distinguished, the polyester copolymer (polymer A) of this disclosure can also be expressed as one or both of the following polyester copolymers A1 and A2. That is, the technology of this disclosure also has the aspect of being a fastness-enhancing agent composition comprising one or both of the following polyester copolymers A1 and A2, and the aspect of being a method for manufacturing polyester-based dyed fiber articles using one or both of the following polyester copolymers A1 and A2.

[0149] (Polyester copolymer A1)

[0150] Polyester copolymer A1 comprises dicarboxylic acid units A1-1 and diol units A1-2.

[0151] The aforementioned dicarboxylic acid unit A1-1 comprises 5 mol% and less than 30 mol% of units derived from dicarboxylic acids having one or both of a sulfonic acid group and a sulfonate group.

[0152] The aforementioned diol unit A1-2 is derived from diols with a molecular weight of 48 or higher and less than 900, and,

[0153] The intramolecular content of the dicarboxylic acid unit A1-1 in the above-mentioned polyester copolymer A1 is 50% by mass or more and 75% by mass or less.

[0154] (Polyester copolymer A2)

[0155] Polyester copolymer A2 comprises dicarboxylic acid units A2-1, diol units A2-2, and tricarboxylic acid units A2-3.

[0156] The proportion of the above-mentioned tricarboxylic acid unit A2-3 in the total of the above-mentioned dicarboxylic acid unit A2-1 and the above-mentioned tricarboxylic acid unit A2-3 is more than 5 mol% and less than 30 mol%.

[0157] The aforementioned diol unit A2-2 is derived from diols with a molecular weight of 48 or higher and less than 900.

[0158] The total intramolecular content of the dicarboxylic acid unit A2-1 and the tricarboxylic acid unit A2-3 in the above-mentioned polyester copolymer A2 is 50% by mass or more and 75% by mass or less.

[0159] In polyester copolymer A2, dicarboxylic acid unit A2-1 may or may not include unit X derived from dicarboxylic acids having one or both sulfonic acid groups and sulfonate groups. The total proportion of unit X and unit Y derived from tricarboxylic acids in dicarboxylic acid unit A2-1 may be more than 5 mol% and less than 30 mol%.

[0160] Example

[0161] The manufacturing method of this disclosure will be further described below while showing embodiments, but the manufacturing method of this disclosure is not limited to the following embodiments. In the manufacturing method of this disclosure, various conditions can be adopted as long as the purpose is achieved without departing from its spirit.

[0162] 1. Preparation of polyester copolymer (polymer A)

[0163] 1.1 Synthesis Example 1

[0164] 155.4 g (0.8 mol) of dimethyl terephthalate, 59.2 g (0.2 mol) of sodium dimethyl 5-sulfoisophthalate, 62 g of ethylene glycol, 12 g of polyethylene glycol with a molecular weight of 600, and 0.1 g of zinc acetate were added to a reaction vessel. The mixture was stirred under a nitrogen atmosphere, and the temperature was increased from 150 °C to 230 °C over approximately 3 hours to induce a transesterification reaction, allowing the volatiles to distill off the system. Next, 0.1 g of tetrabutyl titanate was added, and the pressure was slowly reduced to approximately 10 kPa. The reaction was carried out at 250 °C for 2 hours, yielding approximately 224 g of a polyester copolymer. The obtained polyester copolymer contained approximately 72% by mass of dicarboxylic acid units, with a weight-average molecular weight of 19,000.

[0165] 1.2 Synthesis Example 2

[0166] 165.1 g (0.85 mol) of dimethyl terephthalate, 44.4 g (0.15 mol) of sodium dimethyl 5-sulfoisophthalate, 62 g of ethylene glycol, 12 g of polyethylene glycol with a molecular weight of 600, and 0.1 g of zinc acetate were added to a reaction vessel. The reaction was carried out in the same manner as in Synthesis Example 1, yielding approximately 219 g of a polyester copolymer. The resulting polyester copolymer contained approximately 71% by mass of dicarboxylic acid units and had a weight-average molecular weight of 6,500.

[0167] 1.3 Synthesis Example 3

[0168] 174.8 g (0.9 mol) of dimethyl terephthalate, 29.6 g (0.1 mol) of sodium dimethyl 5-sulfoisophthalate, 31 g of ethylene glycol, 52 g of neopentyl glycol, 12 g of polyethylene glycol with a molecular weight of 600, and 0.1 g of zinc acetate were added to a reaction vessel. The reaction was carried out in the same manner as in Synthesis Example 1, yielding approximately 235 g of a polyester copolymer. The resulting polyester copolymer contained approximately 65% ​​by mass of dicarboxylic acid units and had a weight-average molecular weight of 65,000.

[0169] 1.4 Synthesis Example 4

[0170] 174.8 g (0.9 mol) of dimethyl terephthalate, 29.6 g (0.1 mol) of sodium dimethyl 5-sulfoisophthalate, 106 g of diethylene glycol, and 0.1 g of zinc acetate were added to a reaction vessel, and the reaction was carried out in the same manner as in Synthesis Example 1, yielding approximately 244 g of a polyester copolymer. The obtained polyester copolymer contained approximately 62% by mass of dicarboxylic acid units and had a weight-average molecular weight of 9,000.

[0171] 1.5 Synthesis Example 5

[0172] 116.5 g (0.6 mol) of dimethyl terephthalate, 49.8 g (0.3 mol) of isophthalic acid, 29.6 g (0.1 mol) of sodium dimethyl 5-sulfoisophthalate, 62 g of ethylene glycol, 12 g of polyethylene glycol with a molecular weight of 600, and 0.1 g of zinc acetate were added to a reaction vessel. The reaction was carried out in the same manner as in Synthesis Example 1, yielding approximately 214 g of a polyester copolymer. The resulting polyester copolymer contained approximately 70% by mass of dicarboxylic acid units and had a weight-average molecular weight of 16,000.

[0173] 1.6 Synthesis Example 6

[0174] 155.4 g (0.8 mol) of dimethyl terephthalate, 14.6 g (0.1 mol) of adipic acid, 29.6 g (0.1 mol) of sodium dimethyl 5-sulfoisophthalate, 49.6 g of ethylene glycol, 20.8 g of neopentyl glycol, and 0.1 g of zinc acetate were added to a reaction vessel. The reaction was carried out in the same manner as in Synthesis Example 1, yielding approximately 206 g of a polyester copolymer. The resulting polyester copolymer contained approximately 71% by mass of dicarboxylic acid units and had a weight-average molecular weight of 22,000.

[0175] 1.7 Synthesis Example 7

[0176] 145.7 g (0.75 mol) of dimethyl terephthalate, 31.5 g (0.15 mol) of trimellitic acid, 23.0 g (0.1 mol) of dodecanoic acid, 23 g of ethylene glycol, 23 g of 1,4-butanediol, 39 g of neopentyl glycol, and 0.1 g of zinc acetate were added to a reaction vessel. The reaction was carried out in the same manner as in Synthesis Example 1, yielding approximately 228 g of a polyester copolymer. The resulting polyester copolymer contained approximately 68% by mass of dicarboxylic acid units and had a weight-average molecular weight of 2,800.

[0177] 1.8 Synthesis Example 8

[0178] 172.8 g (0.89 mol) of dimethyl terephthalate, 23.1 g (0.11 mol) of trimellitic acid, 39 g of ethylene glycol, 39 g of neopentyl glycol, and 0.1 g of zinc acetate were added to a reaction vessel, and the reaction was carried out in the same manner as in Synthesis Example 1, yielding approximately 213 g of a polyester copolymer. The obtained polyester copolymer contained approximately 69% by mass of dicarboxylic acid units and had a weight-average molecular weight of 4,100.

[0179] 1.9 Comparative Synthesis Example 1

[0180] 116.5 g (0.6 mol) of dimethyl terephthalate, 118.4 g (0.4 mol) of sodium dimethyl 5-sulfoisophthalate, 62 g of ethylene glycol, 24 g of polyethylene glycol with a molecular weight of 600, and 0.1 g of zinc acetate were added to a reaction vessel. The reaction was carried out in the same manner as in Synthesis Example 1, yielding approximately 256 g of a polyester copolymer. The resulting polyester copolymer contained approximately 71% by mass of dicarboxylic acid units and had a weight-average molecular weight of 29,000.

[0181] 1.10 Comparative Synthesis Example 2

[0182] 126.2 g (0.65 mol) of dimethyl terephthalate, 103.6 g (0.35 mol) of sodium dimethyl 5-sulfoisophthalate, 62 g of ethylene glycol, 120 g of polyethylene glycol with a molecular weight of 600, and 0.1 g of zinc acetate were added to a reaction vessel. The reaction was carried out in the same manner as in Synthesis Example 1, yielding approximately 347 g of a polyester copolymer. The resulting polyester copolymer contained approximately 53% by mass of dicarboxylic acid units and had a weight-average molecular weight of 41,000.

[0183] 1.11 Comparative Synthesis Example 3

[0184] 174.8 g (0.9 mol) of dimethyl terephthalate, 29.6 g (0.1 mol) of sodium dimethyl 5-sulfoisophthalate, 62 g of ethylene glycol, 310 g of polyethylene glycol with a molecular weight of 3100, and 0.1 g of zinc acetate were added to a reaction vessel. The reaction was carried out in the same manner as in Synthesis Example 1, yielding approximately 512 g of a polyester copolymer. The resulting polyester copolymer contained approximately 32% by mass of dicarboxylic acid units and had a weight-average molecular weight of 85,000.

[0185] 1.12 Comparative Synthesis Example 4

[0186] 116.5 g (0.6 mol) of dimethyl terephthalate, 118.4 g (0.4 mol) of sodium dimethyl 5-sulfoisophthalate, 57 g of ethylene glycol, 86 g of polyethylene glycol with a molecular weight of 1000, and 0.1 g of zinc acetate were added to a reaction vessel. The reaction was carried out in the same manner as in Synthesis Example 1, yielding approximately 314 g of a polyester copolymer. The resulting polyester copolymer contained approximately 59% by mass of dicarboxylic acid units and had a weight-average molecular weight of 31,000.

[0187] 1.13 Comparative Synthesis Example 5

[0188] 186.2 g (0.96 mol) of dimethyl terephthalate, 11.8 g (0.04 mol) of sodium dimethyl 5-sulfoisophthalate, 31 g of ethylene glycol, 12 g of polyethylene glycol with a molecular weight of 600, 52 g of neopentyl glycol, and 0.1 g of zinc acetate were added to a reaction vessel. The reaction was carried out in the same manner as in Synthesis Example 1, yielding approximately 229 g of a polyester copolymer. The resulting polyester copolymer contained approximately 64% by mass of dicarboxylic acid units and had a weight-average molecular weight of 19,000.

[0189] 1.14 Comparative Synthesis Example 6

[0190] 135.8 g (0.7 mol) of dimethyl terephthalate, 88.8 g (0.3 mol) of sodium dimethyl 5-sulfoisophthalate, 62 g of ethylene glycol, and 0.1 g of zinc acetate were added to a reaction vessel, and the reaction was carried out in the same manner as in Synthesis Example 1, yielding approximately 223 g of a polyester copolymer. The resulting polyester copolymer contained approximately 76% by mass of dicarboxylic acid units and had a weight-average molecular weight of 30,000.

[0191] Regarding the various polyester copolymers involved in the above synthetic examples and comparative synthetic examples, Table 1 below shows the amount (mol%) of units derived from a specific dicarboxylic acid (a dicarboxylic acid having one or both of sulfonic acid groups and sulfonate groups) in all dicarboxylic acid units, the intramolecular content ratio of the aforementioned dicarboxylic acid units in the polyester copolymer, and the weight-average molecular weight of the polyester copolymer.

[0192] Table 1

[0193]

[0194] 2. Preparation of soap and detergent

[0195] 2.1 Soap Detergent A-1

[0196] 25.0 parts by weight of the polyester copolymer obtained in Synthesis Example 1 and 75.0 parts by weight of water were added to a mixing tank and mixed uniformly at 80-90°C to obtain soaping agent A-1.

[0197] 2.2 Soap detergents A-2~A-8, B-1~B-6

[0198] Using the ingredients shown in Table 2 below, and otherwise operated in the same manner as soaping agent A-1, soaping agents A-2 to A-8 and B-1 to B-6 were obtained.

[0199]

[0200] 2.3 Soap detergents C-1 to C-6 (Prior art)

[0201] The ingredients shown in Table 3 below were added to a mixing vessel and mixed uniformly at 50-60°C to obtain soaping agents C-1 to C-6.

[0202] Table 3

[0203]

[0204] 3. Dyeing and soaping treatment

[0205] 3.1 Method 1 (2-bath 2-stage method): Examples 1-1, 1-2, Comparative Examples 1-1, 2-1, 3-1, 1-2, 2-2 and 3-2

[0206] Polyester fibers were dyed and soaped using a 2-bath, 2-stage process.

[0207] 3.1.1 Staining treatment

[0208] Using 100% polyester fabric as the test fabric, and a MINI-COLOR dyeing machine (Rapid) as the test equipment, the test fabric was added to a dyeing solution with the following composition at a liquor ratio of 1:15, and the dyeing treatment was carried out at 130°C for 60 minutes (heating from 60°C at 2°C / min).

[0209] <Composition of the staining solution>

[0210] 80% acetic acid 0.4 g / L

[0211] Staining auxiliary agent NICCA SUNSOLT RM-3406 0.5g / L

[0212] Disperse dyes

[0213] Foron Rubine (made by ARCHROMA) 4.5%owf

[0214] or

[0215] Disperse Black (Xinghejiang Shouzhi) 7.5% owf

[0216] 3.1.2 Soap washing treatment

[0217] After the above dyeing treatment, the dyeing solution was cooled to about 80°C and then drained. A soaping solution with the following composition was prepared again and soaped at 80°C for 20 minutes at a liquor ratio of 1:15.

[0218] <Composition of soap wash>

[0219] Soap detergent 0 or 1 g / L

[0220] 48% caustic soda, 0.8 or 1.0 g / L

[0221] Sodium dithionite 0.8 or 1.0 g / L

[0222] 3.1.3 Washing and other treatments, etc.

[0223] The polyester fibers treated with the above soaping were then washed, dehydrated, and dried to obtain polyester dyed fiber products. The washing solution used for washing did not contain soaping agent.

[0224] 3.2 Method 2 (1-bath 2-stage method): Examples 2-3, Comparative Examples 4-7

[0225] Polyester fibers are dyed by combining dyeing auxiliaries and soaping agents in a dyeing solution. Then, a soaping solution is prepared by adding chemicals to the dyeing bath and soaping is performed.

[0226] 3.2.1 Staining treatment

[0227] Using 100% polyester fabric as the test fabric, and a MINI-COLOR dyeing machine (Rapid) as the test equipment, the test fabric was added to a dyeing bath with the following composition at a liquor ratio of 1:15, and dyeing was performed at 130°C for 60 minutes (increasing the temperature from 60°C by 2°C / min).

[0228] <Composition of the staining bath>

[0229] 80% acetic acid 0.4 g / L

[0230] Staining auxiliary NICCA SUNSOLT RM-3406 0.5g / L

[0231] Soap detergent 0 or 1 g / L

[0232] Disperse dyes

[0233] Foron Rubine (made by ARCHROMA) 4.5%owf

[0234] or

[0235] Disperse Black (Xinghejiang Shouzhi) 7.5% owf

[0236] 3.2.2 Soap washing treatment

[0237] After the above dyeing treatment, the dyeing solution was cooled to about 80°C, and the following agents were added to prepare a soaping solution. The soaping treatment was then carried out at 80°C for 20 minutes. Here, the following agents were added at a ratio of 1 g / L, with the ratio of polyester fiber to soaping solution being 1:15.

[0238] <Pharmaceuticals>

[0239] 48% caustic soda 1g / L

[0240] Sodium dithionite or thiourea dioxide 1g / L

[0241] 3.2.3 Washing and other treatments, etc.

[0242] The polyester fibers treated with the above soaping were then washed, dehydrated, and dried to obtain polyester dyed fiber products. The washing solution used for the washing process was made to be free of soaping agents.

[0243] 3.3 Method 3 (1-bath 2-stage method): Examples 4-15, Comparative Examples 8-20

[0244] Polyester fibers are dyed using dyeing auxiliaries in a dyeing bath. Then, soaping solution is prepared by adding soaping agent and chemicals to the dyeing bath, followed by soaping treatment.

[0245] 3.3.1 Staining treatment

[0246] Using 100% polyester fabric as the test fabric, and a MINI-COLOR dyeing machine (Rapid) as the test equipment, the test fabric was added to a dyeing solution with the following composition at a liquor ratio of 1:15, and the dyeing treatment was carried out at 130°C for 60 minutes (heating from 60°C at 2°C / min).

[0247] <Composition of the staining solution>

[0248] 80% acetic acid 0.4 g / L

[0249] Staining auxiliary NICCA SUNSOLT RM-3406 0.5g / L

[0250] Disperse dyes

[0251] Foron Rubine (made by ARCHROMA) 4.5%owf

[0252] or

[0253] Disperse Black (Xinghejiang Shouzhi) 7.5% owf

[0254] 3.3.2 Soap washing treatment

[0255] After the above dyeing treatment, the dyeing solution was cooled to about 80°C, and a soaping solution was prepared by adding the following agents. The solution was then soaped at 80°C for 20 minutes. Here, the following agents were added in the following amounts, with a polyester fiber to soaping solution ratio of 1:15.

[0256] <Pharmaceuticals>

[0257] 1g / L of soap detergent

[0258] 48% caustic soda or 1 or 5 g / L soda ash

[0259] Sodium dithionite or thiourea dioxide 1g / L

[0260] 3.3.3 Washing treatment

[0261] The polyester fibers treated with the above soaping were then washed, dehydrated, and dried to obtain polyester dyed fiber products. The washing solution used for the washing process was made to be free of soaping agents.

[0262] 3.4 Others (1-stage 2-bath method): Examples 16-26, Comparative Examples 21-22

[0263] The above describes the case where only one specified soaping agent is added to the dyeing solution or soaping solution. The following describes the case where multiple soaping agents are added in combination to the soaping solution, and the case where soaping agents are added to the washing solution used in the washing process (hot water washing and / or water washing) after soaping treatment.

[0264] 3.4.1 Examples 16-18

[0265] 3.4.1.1 Dyeing and soaping treatment

[0266] After dyeing in the same manner as in method 3 above, the dyeing solution was cooled to approximately 80°C. A soaping solution was prepared by adding the following agents as desired, and then soaping was performed at 80°C for 20 minutes. Here, the following agents were added in the following amounts, with a polyester fiber to soaping solution bath ratio of 1:15.

[0267] Soap detergent 0 or 0.5 g / L

[0268] 48% caustic soda 1g / L

[0269] Sodium dithionite or thiourea dioxide 1g / L

[0270] 3.4.1.2 Washing treatment

[0271] After the above-described soaping treatment, a washing solution was prepared by adding the following agents, and then subjected to a hot water wash at 80°C or a water wash at 30°C for 20 minutes. Here, the amount of the following agents was adjusted as described below, with a polyester fiber to washing solution ratio of 1:15. Then, dehydration and drying were performed to obtain polyester dyed fiber products.

[0272] <Pharmaceuticals>

[0273] Soap detergent A-3 0.5g / L or 1g / L

[0274] 3.4.2 Examples 19-22, Comparative Example 21

[0275] The dyeing solution after dyeing was soaped by adding 80% acetic acid and soaping agent C-5 (liquid reducing agent, equivalent to the substance disclosed in Patent Document 1). Otherwise, the dyeing and soaping processes were performed in the same manner as in Method 3. Details are as follows.

[0276] 3.4.2.1 Staining treatment

[0277] Using 100% polyester fabric as the test fabric, and a MINI-COLOR dyeing machine (Rapid) as the test equipment, the test fabric was added to a dyeing bath with the following composition at a liquor ratio of 1:15, and the dyeing treatment was carried out at 130°C for 60 minutes (heating from 60°C at 2°C / min).

[0278] <Composition of the staining solution>

[0279] 80% acetic acid 0.4 g / L

[0280] Staining auxiliary NICCA SUNSOLT RM-3406 0.5g / L

[0281] Disperse dyes

[0282] Foron Rubine (made by ARCHROMA) 4.5%owf

[0283] or

[0284] Disperse Black (Xinghejiang Shouzhi) 7.5% owf

[0285] 3.4.2.2 Soap washing treatment

[0286] After the above dyeing treatment, the dyeing solution was cooled to approximately 80°C. A soaping solution was prepared by adding the following agents, and then soaping was performed at 80°C for 20 minutes. Here, the amount of the following agents was adjusted as described below, with a polyester fiber to soaping solution ratio of 1:15.

[0287] <Pharmaceuticals>

[0288] 80% acetic acid 0.5 g / L

[0289] Soap detergent C-5 (liquid reducing agent) 1g / L

[0290] Soap detergent A-3 0 or 0.5 g / L or 1 g / L

[0291] 3.4.2.3 Washing Treatment A: Example 19, Comparative Example 21

[0292] The polyester fibers treated with the above soaping were then washed, dehydrated, and dried to obtain polyester dyed fiber products. The washing solution used for the washing process was made to be free of soaping agents.

[0293] 3.4.2.4 Washing Treatment B: Examples 20-22

[0294] After the above-described soaping treatment, a washing solution was prepared by adding the following agents, and then subjected to a hot water wash at 80°C or a water wash at 30°C for 20 minutes. Here, the amount of the following agents was adjusted as described below, with a polyester fiber to washing solution ratio of 1:15. Then, dehydration and drying were performed to obtain polyester dyed fiber products.

[0295] <Pharmaceuticals>

[0296] Soap detergent A-3 0.5g / L or 1g / L

[0297] 3.4.3 Examples 23-26, Comparative Example 22

[0298] Polyester fibers are dyed using dyeing auxiliaries in a dyeing bath. Then, a soaping solution is prepared by adding soaping agents and chemicals to the dyeing bath, followed by soaping treatment and hot water washing or water washing. Details are as follows.

[0299] 3.4.3.1 Staining treatment

[0300] Using 100% polyester fabric as the test fabric, and a MINI-COLOR dyeing machine (Rapid) as the test equipment, the test fabric was added to a dyeing bath with the following composition at a liquor ratio of 1:15, and the dyeing treatment was carried out at 130°C for 60 minutes (heating from 60°C at 2°C / min).

[0301] <Composition of the staining solution>

[0302] 80% acetic acid 0.4 g / L

[0303] Staining auxiliary NICCA SUNSOLT RM-3406 0.5g / L

[0304] Disperse dyes

[0305] Foron Rubine (made by ARCHROMA) 4.5%owf

[0306] or

[0307] Disperse Black (Xinghejiang Shouzhi) 7.5% owf

[0308] 3.4.3.2 Soap washing treatment

[0309] After the above dyeing treatment, the dyeing solution was cooled to approximately 80°C. A soaping solution was prepared by adding the following agents, and then soaping was performed at 80°C for 20 minutes. Here, the amount of the following agents was adjusted as described below, with a polyester fiber to soaping solution ratio of 1:15.

[0310] <Pharmaceuticals>

[0311] 48% caustic soda 1g / L

[0312] Soap detergent C-6 (liquid reducing agent) 1g / L

[0313] Soap detergent A-3 0 or 0.5 g / L or 1 g / L

[0314] 3.4.3.3 Washing Treatment A: Example 23, Comparative Example 22

[0315] The polyester fibers treated with the above soaping were then washed, dehydrated, and dried to obtain polyester dyed fiber products. The washing solution used for the washing process was made to be free of soaping agents.

[0316] 3.4.3.4 Washing Treatment B: Examples 24-26

[0317] After the above-described soaping treatment, a washing solution is prepared by adding the following agents, followed by hot water washing at 80°C or water washing at 30°C for 20 minutes. Here, the amount of the following agents was adjusted as described below, with a bath ratio of polyester fiber to washing solution of 1:15. Then, dehydration and drying are performed to obtain polyester dyed fiber products.

[0318] <Pharmaceuticals>

[0319] Soap detergent A-3 0.5g / L or 1g / L

[0320] 4. Evaluation of polyester-based dyed fiber products

[0321] 4.1 Evaluation of wash fastness

[0322] Wash fastness was determined using method A-2 of JIS L0844:2011, with fastness judged by grayscale level of staining (JIS L 0805:2005). A higher rating indicates better fastness. Furthermore, each rating is divided into four sub-groups to represent subtle differences in colorfastness. For example, between ratings 4 and 5, the sub-groups are 4.3, 4.5, and 4.8. The same applies to other ratings.

[0323] 4.2 Evaluation of dry and wet rubbing fastness

[0324] Dry and wet rubbing fastness were tested using the friction tester type II (mechanical vibration) method according to JIS L0849:2013, and were evaluated in the same manner as washing fastness.

[0325] 5. Evaluation Results

[0326] The evaluation results are shown in Tables 4 to 8 below.

[0327]

[0328] Table 5

[0329]

[0330]

[0331]

[0332]

[0333] The results shown in Tables 4-8 reveal the following information.

[0334] (1) Comparative Examples 1-1, 2-1, 3-1, 1-2, 2-2, and 3-2, along with Examples 1-1 and 1-2, illustrate the effect of reducing the reducing dose on fastness in the 2-bath 2-stage treatment involved in the first method. It can be seen that Examples 1-1 and 1-2 show less reduction in fastness compared to the comparative examples, and an improvement in fastness in the 2-bath 2-stage treatment can be expected.

[0335] (2) In the case of the 1 bath 2 stage treatment involved in the second method, according to the results of Examples 2 and 3 and Comparative Examples 4 to 7, even if the specified polyester copolymer is used during dyeing, the fastness of polyester dyed fiber products can be improved.

[0336] (3) In the case of the 1-bath 2-stage treatment involved in Method 3, Examples 4-15 showed excellent fastness compared to Comparative Examples 8-15, which used a soaping agent made from a relatively synthetic resin, Comparative Examples 16-20, which used an active agent-based soaping agent to date, Comparative Example 21, which used an acidic reducing agent, and Comparative Example 22, which used a reducing sugar. The fastness was at least equal to that of the 2-bath 2-stage treatment in Comparative Example 1. Furthermore, both caustic soda and soda ash were effective when used in the soaping process.

[0337] (4) In the case of the 1-bath 2-stage treatment involved in the third method, as can be seen from the results of Examples 7, 16-18, 20-22, and 24-26, detergent A-3 only needs to be added to either the soaping treatment or the washing treatment (hot water washing treatment and / or water washing treatment), or it can be added separately. Furthermore, excellent fastness was also obtained by adding detergent A-3 to the hot water washing solution or the water washing solution. At this time, it can be seen that detergent A-3 can be added to both the soaping solution and the washing solution (hot water washing solution and / or water washing solution). Furthermore, as in Examples 19 and 23, by further adding detergent A-3 to Comparative Example 21, which used an acidic reducing agent, and Comparative Example 22, which used a reducing sugar, excellent fastness was obtained compared to the respective comparative examples. However, as can be seen from the comparison of Examples 4 to 26, the reducing agent combined with the soaping agent is preferably a sulfur-containing compound (in particular, selected from at least one of dithionite, sodium dithionite, thiourea dioxide and sodium hydroxymethyl sulfinate).

[0338] Based on the above results, if a polyester copolymer satisfying (1) to (5) below is used, an improvement in fastness during the 2-bath 2-stage treatment can be expected. Furthermore, even with a 1-bath 2-stage method, a decrease in fastness can be suppressed, and products of the same or higher quality as those obtained by the 2-bath 2-stage method can be obtained. This achieves CO2 reduction due to process optimization and water conservation due to reduced drainage. The polyester copolymer satisfying (1) to (5) below can be used, for example, as a fastness improver. In addition, this polyester copolymer can be used, for example, as shown in the above examples, as a component added to the soaping solution (soaping agent), or as a detergent added to the washing liquid during hot water washing and / or water washing after soaping.

[0339] (1) The above polyester copolymer contains dicarboxylic acid units and diol units.

[0340] (2) The above-mentioned dicarboxylic acid unit includes a unit derived from a dicarboxylic acid having one or both of a sulfonic acid group and a sulfonate group, and a unit derived from a tricarboxylic acid having a content of 5 mol% or more and 30 mol% or less.

[0341] (3) The above diol units are derived from diols with a molecular weight of 48 or more and less than 900.

[0342] (4) The intramolecular content of the dicarboxylic acid unit in the above polyester copolymer is 50% by mass or more and 75% by mass or less.

Claims

1. A fastness-enhancing composition comprising a polyester copolymer, The polyester copolymer comprises dicarboxylic acid units and diol units. The dicarboxylic acid unit comprises a unit derived from a dicarboxylic acid having one or both of a sulfonic acid group and a sulfonate group, and at least one unit derived from a tricarboxylic acid, comprising 5 mol% to 30 mol% of each. The diol units constituting the polyester copolymer are composed only of units derived from diols with a molecular weight of 48 or more and less than 900, and, The intramolecular content of the dicarboxylic acid units in the polyester copolymer is 50% by mass or more and 75% by mass or less. The fastness-enhancing agent composition comprises at least one of the following as a reducing agent: dithionite, sodium dithionite, thiourea dioxide, and sodium hydroxymethyl sulfinate.

2. A manufacturing method for polyester-based dyed fiber products, comprising the following steps: Polyester fibers are dyed. The dyed polyester fibers are subjected to a soaping treatment in a separate bath with the dyeing solution; and The polyester fibers after the soaping treatment are subjected to one or both of the following washing treatments: hot water washing and water washing. One or both of the soaping solution used in the soaping treatment and the washing solution used in the washing treatment contain a polyester copolymer. The polyester copolymer comprises dicarboxylic acid units and diol units. The dicarboxylic acid unit comprises a unit derived from a dicarboxylic acid having one or both of a sulfonic acid group and a sulfonate group, and at least one unit derived from a tricarboxylic acid, comprising 5 mol% to 20 mol% of each. The diol unit is derived from a diol with a molecular weight of 48 or greater and less than 900, and, The intramolecular content of the dicarboxylic acid units in the polyester copolymer is 50% by mass or more and 75% by mass or less. The soaping solution contains at least one of the following as a reducing agent: dithionite, sodium dithionite, thiourea dioxide, and sodium hydroxymethyl sulfinate.

3. A manufacturing method for polyester-based dyed fiber products, comprising the following steps: Polyester fibers are dyed. The dyed polyester fibers are subjected to a soaping treatment in the same bath as the dyeing solution; and The polyester fibers after the soaping treatment are subjected to one or both of the following washing treatments: hot water washing and water washing. The soaping solution used in the soaping treatment is prepared by adding at least a polyester copolymer and a reducing agent to the dyeing solution after the dyeing treatment. The polyester copolymer comprises dicarboxylic acid units and diol units. The dicarboxylic acid unit comprises a unit derived from a dicarboxylic acid having one or both of a sulfonic acid group and a sulfonate group, and at least one unit derived from a tricarboxylic acid, comprising 5 mol% to 20 mol% of each. The diol unit is derived from a diol with a molecular weight of 48 or greater and less than 900, and, The intramolecular content of the dicarboxylic acid units in the polyester copolymer is 50% by mass or more and 75% by mass or less. The reducing agent is selected from at least one of dithionite, sodium dithionite, thiourea dioxide, and sodium hydroxymethyl sulfinate.

4. In the manufacturing method according to claim 2 or 3, the amount of the polyester copolymer contained in the soaping liquid is 0.005 g / L or more and 5.0 g / L or less.

5. A manufacturing method for polyester-based dyed fiber products, comprising the following steps: Polyester fibers are dyed. The dyed polyester fibers are subjected to soaping treatment in the same bath or separate bath with the dyeing solution; and The polyester fibers after the soaping treatment are subjected to one or both of the following washing treatments: hot water washing and water washing. The washing solution used in the washing process contains a polyester copolymer. The polyester copolymer comprises dicarboxylic acid units and diol units. The dicarboxylic acid unit comprises a unit derived from a dicarboxylic acid having one or both of a sulfonic acid group and a sulfonate group, and at least one unit derived from a tricarboxylic acid, comprising 5 mol% to 30 mol% of each. The diol unit is derived from a diol with a molecular weight of 48 or greater and less than 900, and, The intramolecular content of the dicarboxylic acid units in the polyester copolymer is 50% by mass or more and 75% by mass or less. The soaping solution used in the soaping treatment contains at least one of the following as a reducing agent: dithionite, sodium dithionite, thiourea dioxide, and sodium hydroxymethyl sulfinate. The amount of the polyester copolymer contained in the washing liquid is more than 0.005 g / L and less than 5.0 g / L.

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