Microplastic fiber reducing agent composition for textiles

Abstract

To provide a novel micro-plastic fiber reducing agent composition for fibers for reducing an amount of a micro-plastic fibers generated from the fibers generated when washing fibers.SOLUTION: A micro-plastic fiber reducing agent composition for fibers containing the following components (a) and the following components (b). (A) Components: (a1) cationized cellulose and derivatives thereof, (a2) component: at least one compound selected from the group consisting of a diallyl quaternary ammonium salt polymer, a diallyl quaternary ammonium salt / acrylamide copolymer, and a diallyl quaternary ammonium salt / acrylic acid copolymer, (a3) Components: one or more selected from the group consisting of cationized guar gum, cationic tara gum, cationized locust bean gum and derivatives thereof, and (a4) one or more cationic polymer selected from polyethyleneimine and its alkoxylates (b) components: predetermined anionic surfactant.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a microplastic fiber reducing agent composition for textiles and a method for reducing microplastic fibers in textiles. [Background technology]

[0002] In recent years, there has been growing concern about the impact of plastics on the marine environment. For example, there are fears that tiny plastic particles, such as microplastic beads, may flow into the ocean and enter the bodies of sea turtles, seabirds, and fish (and ultimately, humans). Microplastic pollution also includes microfibers (less than 5 mm in length) from synthetic fiber clothing. These synthetic microfibers are shed during fiber washing (laundry, scouring, etc.) and released into the sea, coastlines, rivers, lakes, and other bodies of water, and some are thought to end up in the soil.

[0003] Cellulose derivatives are known to be used as care compounds that can reduce pilling and fuzzing of clothing. For example, Patent Document 1 discloses a clothing care composition containing (a) a predetermined nonionic surfactant, (b) a polysaccharide polymer, and (c) a surfactant other than component (a). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2020-100723 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, simply reducing friction at the contact points between fibers was not enough to suppress the generation of microplastic fibers from the fibers during fiber washing. The present invention provides a novel microplastic fiber reducing agent composition for textiles and a method for reducing microplastic fibers, which reduce the amount of microplastic fibers generated from textiles during textile washing. In this invention, microplastic fibers refer to fibrous microplastics, and their fiber length is generally between 0.1 μm and less than 5 mm. Microplastic fibers are known to be present in the wastewater from washing textile products containing synthetic fibers, and are thought to be a portion of the synthetic fibers from those textile products that have fallen off. Microplastic fibers refer to textile waste or laundry waste. In this invention, the method for reducing microplastic fibers refers to a method for reducing the amount of microplastic fibers generated from fibers. In this invention, "textile cleaning" refers to the act of applying physical and / or chemical effects to a textile product through a processing liquid. The term "cleaning" here is not limited to the act of actually removing dirt and impurities from the textile product, but rather to any act of applying physical and / or chemical effects to the textile product in a manner that enables the removal of dirt and impurities. Specifically, the cleaning in this invention is preferably at least one of washing or textile scouring. For example, washing includes at least one of the following steps: a washing step, a rinsing step, a processing step using a laundry aid such as a fabric softener, or a dewatering step. Textile scouring is, for example, the act of removing impurities adhering to a textile product before dyeing, using a surfactant or the like. The cleaning in this invention may be performed using a machine such as a washing machine, or by hand. [Means for solving the problem]

[0006] The present invention relates to a microplastic fiber reducing agent composition for textiles, comprising the following components (a) and (b). (a) Components: One or more cationic polymers selected from the following components (a1) to (a4). (a1) Components: One or more selected from cationized cellulose and its derivatives. (a2) Components: One or more compounds selected from the group consisting of diallyl quaternary ammonium salt polymers, diallyl quaternary ammonium salt / acrylamide copolymers, and diallyl quaternary ammonium salt / acrylic acid copolymers. (a3) Components: One or more selected from cationized guar gum, cationized tara gum, cationized locust bean gum, and their derivatives. (a4) Components: One or more polymers selected from polyethyleneimine and its alkoxylated derivatives. (b) Components: One or more anionic surfactants selected from the following components (b1) and (b2). (b1) Ingredients: Alkylbenzenesulfonic acid or its salt (b2) Components: Polyoxyalkylene alkyl ether sulfate or salt thereof

[0007] Furthermore, the present invention relates to a method for reducing microplastic fibers in textiles, comprising contacting a chemical fiber with component (a) and component (b). [Effects of the Invention]

[0008] The present invention provides a novel microplastic fiber reducing agent composition for textiles and a microplastic fiber reducing method for reducing the amount of microplastic fibers generated from textiles during textile washing. [Modes for carrying out the invention]

[0009] <Microplastic Fiber Reducing Agent Composition for Textiles> The microplastic fiber reducing agent composition for textiles of the present invention contains the following component (a) and the following component (b). (a) Components: One or more cationic polymers selected from the following components (a1) to (a4). (a1) Components: One or more selected from cationized cellulose and its derivatives. (a2) Components: One or more compounds selected from the group consisting of diallyl quaternary ammonium salt polymers, diallyl quaternary ammonium salt / acrylamide copolymers, and diallyl quaternary ammonium salt / acrylic acid copolymers. (a3) Components: One or more selected from cationized guar gum, cationized tara gum, cationized locust bean gum, and their derivatives. (a4) Components: One or more polymers selected from polyethyleneimine and its alkoxylated derivatives. (b) Components: One or more anionic surfactants selected from the following components (b1) and (b2). (b1) Ingredients: Alkylbenzenesulfonic acid or its salt (b2) Components: Polyoxyalkylene alkyl ether sulfate or salt thereof

[0010] The microplastic fiber reducing agent composition for textiles of the present invention may be a microplastic fiber reducing agent composition for textile products. Furthermore, the microplastic fiber reducing agent composition for textiles of the present invention may be a microplastic fiber reducing agent composition for chemical fibers, and even more so, a microplastic fiber reducing agent composition for chemical fiber products. Furthermore, the microplastic fiber reducing agent composition for textiles of the present invention may be a microplastic fiber generation reducing agent composition for textiles that reduces the amount of microplastic fibers generated from textiles when textiles are washed. In this invention, microplastic fibers may be fibrous pieces 5 mm or smaller.

[0011] <(a) Components> Component (a) is one or more cationic polymers selected from the following components (a1) to (a4). In the present invention, a cationic polymer means a polymer having a cationic group in its molecule. The cationic group means one or more groups selected from quaternary ammonium groups and amino groups. The amino group is referred to as a cationic group in the present invention because it can become a cationic group in water depending on the pH. From the viewpoint of suppressing the discharge of microplastic fibers, one or more components selected from component (a1) are preferred for component (a). (a1) Components: One or more selected from cationized cellulose and its derivatives. (a2) Components: One or more compounds selected from the group consisting of diallyl quaternary ammonium salt polymers, diallyl quaternary ammonium salt / acrylamide copolymers, and diallyl quaternary ammonium salt / acrylic acid copolymers. (a3) Components: One or more selected from cationized guar gum, cationized tara gum, cationized locust bean gum, and their derivatives. (a4) Components: One or more polymers selected from polyethyleneimine and its alkoxylated derivatives.

[0012] (a) The weight-average molecular weight of the component is calculated by converting it to polyethylene glycol using GPC (gel permeation chromatography). The measurement conditions are as follows: • Column: TSKgel α-M Eluent: 50 mmol / L LiBr, 1% CH3COOH, Ethanol / Water = 3 / 7 ·Temperature: 40℃ ·Flow rate: 0.6mL / min

[0013] <(a1) component> (a1) Component is one or more selected from cationized cellulose and its derivatives. From the viewpoint of suppressing the discharge of microplastic fibers, one or more selected from cationized cellulose, cationized hydroxyalkyl cellulose, and alkylated cationized hydroxyalkyl cellulose are preferred for component (a1), and cationized hydroxyalkyl cellulose is more preferred.

[0014] As a precursor compound of component (a1), a cellulose polymer in which some or all of the hydrogen atoms of the hydroxyl groups of cellulose are substituted with a hydroxyalkyl group having 1 to 4 carbon atoms (hereinafter also referred to as a hydroxyalkyl substituted product) is an example from the viewpoint of suppressing the discharge of microplastic fibers. From the viewpoint of suppressing the discharge of microplastic fibers, a hydroxyalkyl group having 2 to 4 carbon atoms is preferred. As a hydroxyalkyl group having 2 to 4 carbon atoms, from the viewpoint of suppressing the discharge of microplastic fibers, for example, one or more groups selected from a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group are examples, and one or more groups selected from a hydroxyethyl group and a hydroxypropyl group are preferred. Component (a1) may be a compound in which a cationic group is introduced into a cellulose polymer selected from cellulose or its hydroxyalkyl substituted products.

[0015] (a1) The degree of substitution of the cationic groups in the cellulose polymer having cationic groups, which is component (a1), is preferably 0.001 or more, more preferably 0.005 or more, even more preferably 0.01 or more, and preferably 1 or less, more preferably 0.7 or less, and even more preferably 0.5 or less, from the viewpoint of suppressing the discharge of microplastic fibers.

[0016] From the viewpoint of suppressing the discharge of microplastic fibers, a cellulose polymer having a cationic group is a cellulose polymer in which a cationic group is bonded to a group obtained by removing a hydrogen atom from a hydroxyl group that is a precursor compound of component (a1), preferably the hydroxyalkyl substituted product, via a linking group, which is an alkylene group having 1 to 4 carbon atoms that may contain a hydroxyl group [hereinafter referred to as linking group (1)]. From the viewpoint of suppressing the emission of microplastic fibers, the cationic group is a group containing a nitrogen cation, and more preferably a quaternary ammonium group from the viewpoint of being able to solve the problems of the present invention.

[0017] The linking group (1) is an alkylene group having 1 to 4 carbon atoms, which may contain a hydroxyl group, from the viewpoint of suppressing the discharge of microplastic fibers. Examples of alkylene groups having 1 to 4 carbon atoms include one or more alkylene groups selected from linear alkylene groups having 1 to 4 carbon atoms, which may contain a hydroxyl group, and branched alkylene groups having 3 to 4 carbon atoms, which may contain a hydroxyl group, from the viewpoint of suppressing the discharge of microplastic fibers.

[0018] When the cationic group is a quaternary ammonium group, from the viewpoint of suppressing the emission of microplastic fibers, the three hydrocarbon groups other than the linking group (1) bonded to the quaternary ammonium group can each be independently a linear or branched hydrocarbon group having 1 to 4 carbon atoms. From the viewpoint of suppressing the emission of microplastic fibers, examples of linear hydrocarbon groups having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. From the viewpoint of suppressing the emission of microplastic fibers, examples of branched hydrocarbon groups having 3 to 4 carbon atoms include an isopropyl group, a sec-butyl group, a tert-butyl group, and an isobutyl group. From the viewpoint of suppressing the emission of microplastic fibers, a methyl group or an ethyl group is preferred as the linear hydrocarbon group having 1 to 4 carbon atoms. From the viewpoint of suppressing the discharge of microplastic fibers, the counterion of the quaternary ammonium group can be one or more counterions selected from alkyl sulfate ions having 1 to 3 carbon atoms, sulfate ions, phosphate ions, fatty acid ions having 1 to 3 carbon atoms, and halide ions. Among these, from the viewpoint of suppressing the discharge of microplastic fibers, it is preferably one or more selected from alkyl sulfate ions having 1 to 3 carbon atoms, sulfate ions, and halide ions, more preferably a halide ion. Examples of halide ions include fluoride ions, chloride ions, bromide ions, and iodide ions. From the viewpoint of suppressing the discharge of microplastic fibers, it is preferably one or more selected from chloride ions and bromide ions, more preferably a chloride ion. Note that the counterion may be a single type or two or more types.

[0019] From the viewpoint of suppressing the discharge of microplastic fibers, it is preferable to select the content of cationic groups in component (a1). The content of cationic groups in the cellulose polymer having cationic groups, which is component (a1), is calculated by replacing the cationic groups with nitrogen atoms. That is, the content of cationic groups in component (a1) can be determined by the content ratio of nitrogen atoms in component (a1). From the viewpoint of suppressing the discharge of microplastic fibers, the nitrogen atom content in component (a1) is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 4% by mass or less, even more preferably 3% by mass or less, even more preferably 2% by mass or less, even more preferably 1% by mass or less, even more preferably 0.6% by mass or less, and from the viewpoint of suppressing the discharge of microplastic fibers, it is preferably 0.05% by mass or more, more preferably 0.1% by mass or more. The nitrogen atom content in component (a1) can be determined by the method described in detail below in <<Method for measuring the nitrogen content and degree of alkyl substitution of component (a1)>.

[0020] (a1) The cellulose polymer having a cationic group, from the viewpoint of suppressing the discharge of microplastic fibers, may optionally be a cellulose polymer having a cationic group to which hydrocarbon groups having 1 to 18 carbon atoms are further bonded directly or via a linking group (hereinafter referred to as linking group (2)).

[0021] As for the aforementioned linking group (2), from the viewpoint of suppressing the discharge of microplastic fibers, one or more groups selected from alkylene oxy groups having 1 to 3 carbon atoms, which may have a hydroxyl group, polyoxyalkylene groups in which the alkylene group has 1 to 3 carbon atoms, carbonyl groups, carbonyl oxy groups, and oxycarbonyl groups are mentioned. A single linking group (2) may be one of the aforementioned linking groups, or it may be a combination of multiple types. Furthermore, the polysaccharide polymer may contain one type of linking group, or it may contain multiple types. In the present invention, when the hydrocarbon group is linked to the oxygen atom of the linking group (2), the number of carbon atoms in the hydrocarbon group of component (a1) represents the number of carbon atoms in the hydrocarbon group bonded to the oxygen atom. When the hydrocarbon group is linked via a carbonyl group, it becomes a structure with an acyl group bonded, and in this case, the number of carbon atoms in the hydrocarbon group of component (b1) represents the number of carbon atoms in the acyl group. Similarly, when linked via a carbonyloxy group and an oxycarbonyl group, the number of carbon atoms in those groups is also included. When introducing a hydrocarbon group into a cellulose polymer, if 1,2-epoxyalkane is used, it represents the number of carbon atoms in the aliphatic hydrocarbon group bonded to the ether group generated from the epoxy group. The epoxy group portion becomes linking group (2). For example, when introducing a hydrocarbon group into a cellulose polymer using 1,2-epoxytetradecane, the number of carbon atoms in the hydrocarbon group is 12. That is, an oxyethylene group, which is linking group (1), is bonded to the hydroxyl group of the cellulose polymer, and a C12 alkyl group (dodecyl group) is bonded via this linking group. The same applies when using alkyl glycidyl ethers.

[0022] (a1) Among the components, a cellulose polymer having a cationic group and a hydrocarbon group having 1 to 18 carbon atoms is a cellulose polymer in which a hydrocarbon group having 1 to 18 carbon atoms is bonded directly or via a linking group (2), preferably via a linking group (2), to the oxygen atoms obtained by removing hydrogen atoms from some or all of the hydroxyl groups of the cellulose polymer having a cationic group, either directly or via a linking group (2).

[0023] From the viewpoint of suppressing the emission of microplastic fibers, hydrocarbon groups having 1 to 18 carbon atoms preferably have 2 or more carbon atoms, more preferably 4 or more, even more preferably 6 or more, even more preferably 8 or more, even more preferably 10 or more, even more preferably 12 or more, and preferably 16 or less, more preferably 14 or less. From the viewpoint of suppressing the emission of microplastic fibers, aliphatic hydrocarbon groups are preferred.

[0024] (a1) The degree of substitution of the hydrocarbon group having 1 to 18 carbon atoms in the cellulose polymer having a cationic group and a hydrocarbon group having 1 to 18 carbon atoms is preferably 0.0001 or more, more preferably 0.001 or more, even more preferably 0.005 or more, and also preferably 0.4 or less, more preferably 0.2 or less, even more preferably 0.1 or less, even more preferably 0.08 or less, and even more preferably 0.06 or less. The degree of substitution of hydrocarbon groups having 1 to 18 carbon atoms in component (a1) can be determined by the method described in detail below in <<Method for measuring nitrogen content and alkyl substitution of component (a1)>.

[0025] The weight-average molecular weight of cellulose or its derivative, which is a precursor compound of component (a1) of the present invention, is preferably 1,000 or more, more preferably 10,000 or more, even more preferably 30,000 or more, even more preferably 50,000 or more, even more preferably 70,000 or more, even more preferably 100,000 or more, even more preferably 500,000 or more, even more preferably 1,000,000 or more, and even more preferably 5,000,000 or less, even more preferably 3,000,000 or less, and even more preferably 2,000,000 or less, from the viewpoint of suppressing the discharge of microplastic fibers. The weight-average molecular weight of this precursor compound can be calculated by converting it to polyethylene glycol using GPC (gel permeation chromatography).

[0026] (a1) The weight-average molecular weight of component (a1) is preferably 1,000 or more, more preferably 10,000 or more, even more preferably 30,000 or more, even more preferably 50,000 or more, even more preferably 70,000 or more, even more preferably 100,000 or more, even more preferably 500,000 or more, and even more preferably 1,000,000 or more, and even more preferably 5,000,000 or more, and even more preferably 1,000,000 or more, from the viewpoint of suppressing microplastic fiber discharge and suitability for incorporation into the composition, and is preferably 5,000,000 or less, more preferably 3,000,000 or less, and even more preferably 2,000,000 or less. This weight-average molecular weight can be calculated by converting to polyethylene glycol using GPC (gel permeation chromatography).

[0027] The precursor compound of component (a1) and the weight-average molecular weight of component (a1) are calculated by converting to polyethylene glycol using GPC (gel permeation chromatography). The measurement conditions are as follows: • Column: TSKgel α-M Eluent: 50 mmol / L LiBr, 1% CH3COOH, Ethanol / Water = 3 / 7 ·Temperature: 40℃ ·Flow rate: 0.6mL / min

[0028] <(a1) Method for measuring the nitrogen content and degree of alkyl substitution of component> (a1) The nitrogen content and degree of alkyl substitution of the cellulose derivative, which is component (a1), are measured by the following method. • Pretreatment of cellulose derivatives After dissolving 1 g of cellulose derivative in 100 g of water, the aqueous solution is placed in a dialysis membrane (Spectrapore, molecular weight cutoff 1000) and dialysis is performed for 2 days. The resulting aqueous solution is then freeze-dried using a freeze-dryer (eyela, FDU1100) to obtain a pre-treated cellulose derivative.

[0029] • Calculation of cation substrate amount using the Kjeldahl method 200 mg of the cellulose derivative pretreated by the method described above is accurately weighed, 10 mL of concentrated sulfuric acid and 1 Kjeldahl tablet (Merck) are added, and thermal decomposition is carried out using a Kjeldahl decomposition apparatus (BUCHI, K-432). After decomposition is complete, 30 mL of deionized water is added to the sample, and the nitrogen content (mass%) of the sample is determined using an automated Kjeldahl distillation apparatus (BUCHI, K-370), thereby calculating the mass of the cation group.

[0030] • Calculation of hydrocarbon group (alkyl group) mass using the Zeisel method 200 mg of cellulose derivative and 220 mg of adipic acid, pretreated by the method described above, are accurately weighed into a 10 mL vial (Mighty Vial No. 3), and 3 mL of internal standard solution (tetradecane / o-xylene = 1 / 25 (v / v)) and 3 mL of hydroiodic acid are added, and the vial is sealed. Calibration samples are also prepared by adding 2.4 mg or 9 mg of 1-iodododecane instead of the cellulose derivative. Each sample is heated at 160°C for 2 hours using a block heater (PIERCE, Reacti-Therm III Heating / Stirring module) while stirring with a stirrer tip. After the sample has cooled, the upper layer (o-xylene layer) is collected and analyzed by gas chromatography (GC) (Shimadzu Corporation, QD2010plus) under the following conditions. ·GC analysis conditions Column: Agilent HP-1 (Length: 30m, Liquid phase film thickness: 0.25μL, Inner diameter: 32mm) Split ratio: 20 Column temperature: 100°C (2 min) → 10°C / min → 300°C (15 min) Injector temperature: 300℃ Detector: HID Detector temperature: 330℃ Injection volume: 2 μL The mass of alkyl groups in the sample is determined from the amount of 1-iodododecane detected by GC.

[0031] (a1) The component is represented by the following general formula (I), and includes those in which substituted anhydrous glucose units are repeated. Component (a1) is substituted with nonionic or cationic hydrophobic substituents containing alkyl or arylalkyl groups having 8 to 24 carbon atoms, and cationic substituents of the following formula (II). Component (a1) contains an average of 0.0003 moles to 0.08 moles of the above substituents per mole of anhydrous glucose unit.

[0032] [ka]

[0033] (I) In the formula, R 1 ~R 3 Each of these is independently H, CH3, an alkyl group having 8 to 24 carbon atoms, a nonionic substituent containing an alkyl group having 8 to 24 carbon atoms or an arylalkyl group having 8 to 24 carbon atoms, a cationic substituent containing an alkyl group having 8 to 24 carbon atoms or an arylalkyl group having 8 to 24 carbon atoms, or a group represented by formula (II) below. d is a number between 4,000 and 10,000 representing the number of repetitions. R 1 ~R 3 If the substituent is an alkyl group or a substituent containing an alkyl or arylalkyl group, the alkyl groups of these substituents may be linear or branched.

[0034] [ka]

[0035] In formula (II), p is 0 or more and 10 or less, R 4 is H, CH3, an alkyl group having 8 or more and 24 or less carbon atoms, a group represented by the following formula (III), or a substituent containing an alkyl group having 8 or more and 24 or less carbon atoms other than the foregoing. R 4 when R is an alkyl group or a substituent containing an alkyl group, the alkyl group of these substituents may be linear or branched.

[0036]

Chemical Formula

[0037] In formula (III), R 5 and R 6 are each independently CH3 or C2H5, R 7 is H, CH3, an alkyl group having 8 or more and 24 or less carbon atoms or an arylalkyl group having 8 or more and 24 or less carbon atoms, R 8 is CH2CHOHCH2 or CH2CH2. Z is a water-soluble anion. Examples of Z include chloride ions and bromide ions.

[0038] R 1 is preferably a group represented by formula (II). R 1 when R is a group represented by formula (II), p is preferably 0 or more and 3 or less. Further, as R 4 , a group represented by formula (III) is preferable. In this case, R 5 to R 7 is preferably CH3, R 8 is preferably CH2CHOHCH2, and Z is preferably a chloride ion or a bromide ion.

[0039] R 1The average degree of substitution is preferably 0.0003 moles or more, and more preferably 0.0005 moles or more, per mole of anhydrous hydroglucose units. The upper limit is preferably 0.08 moles or less, more preferably 0.07 moles or less, and even more preferably 0.05 moles or less, per mole of anhydrous hydroglucose units.

[0040] R 2 The base represented by formula (II) is preferred. R 2 If the group is represented by equation (II), then p is preferably between 0 and 3. Also, R 4 The base represented by formula (III) is preferred. In this case, R 5 and R 6 CH3 is preferred, R 7 C q H (2q+1) Therefore, q is preferably between 8 and 14, more preferably between 10 and 18, and particularly preferably 12. 8 CH2CHOHCH2 is preferred for Z. Chloride ions and bromide ions are preferred for Z.

[0041] R 3 H is preferred.

[0042] R 2 The average degree of substitution of the cationic substituent is generally preferably 0.02 moles or more and 0.9 moles or less per mole of anhydrous glucose unit, more preferably 0.05 moles or more and 0.8 moles or less, even more preferably 0.1 moles or more and 0.6 moles or less, and even more preferably 0.15 moles or more and 0.35 moles or less.

[0043] (a1) Examples of commercially available cationized cellulose and its derivatives that can be used as components from the viewpoint of suppressing the discharge of microplastic fibers include the following: (cationized hydroxyethylcellulose) Polyquaternium-10 (o-[2-hydroxy-3-(trimethylammonio)propyl]hydroxyethylcellulose chloride): UCARE POLYMER JR-30M, UCARE POLYMER JR-400 (both from Dow Chemical), Poise C-60H, Poise C-150L (both from Kao Corporation), etc.

[0044] Other (a1) components that can be used to suppress the discharge of microplastic fibers include commercially available products such as Leoguard LP, GP, MGP, KGP, MLP (all are trade names, manufactured by Lion Corporation); UCARE LR-30M, LK; and Kachinaru HC-100 (trade name, manufactured by Toho Chemical Industry Co., Ltd.).

[0045] <(a2) component> (a2) The component is one or more compounds selected from the group consisting of diallyl quaternary ammonium salt polymers, diallyl quaternary ammonium salt / acrylamide copolymers, and diallyl quaternary ammonium salt / acrylic acid copolymers, from the viewpoint of suppressing the discharge of microplastic fibers.

[0046] Diallyl quaternary ammonium salt polymers are homopolymers of diallyl quaternary ammonium salts from the viewpoint of suppressing the discharge of microplastic fibers. Diallyl quaternary ammonium salt / acrylamide copolymers are copolymers of diallyl quaternary ammonium salt and acrylamide. Diallyl quaternary ammonium salt and acrylamide may be polymerized in block polymerization, random polymerization, or graft polymerization. As component (a2), from the viewpoint of suppressing the discharge of microplastic fibers, diallyl quaternary ammonium salt / acrylamide copolymers represented by the following general formula (IV) or (V) are preferred.

[0047] [ka]

[0048] [ka]

[0049] In equations (IV) and (V), R 33 and R 34 Each of these independently consists of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group, an aryl group, a hydroxyalkyl group, an amidealkyl group, a cyanoalkyl group, an alkoxyalkyl group, or a carboalkoxyalkyl group, R 35 , R 36 , R 37 and R 38 Each of the following independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group; X4 is an anion (such as a chloride ion, bromide ion, iodide ion, sulfate ion, sulfonate ion, methyl sulfate ion, or nitrate ion); g is a repeating unit; and h is a repeating unit.

[0050] From the perspective of suppressing the discharge of microplastic fibers, in formulas (IV) and (V), R 33 and R 34 As such, an alkyl group having 1 to 3 carbon atoms is preferred. From the perspective of suppressing the discharge of microplastic fibers, in formulas (IV) and (V), R 35 , R 36 , R 37 and R 38 A hydrogen atom is preferred as the element. From the viewpoint of suppressing the discharge of microplastic fibers, in formulas (IV) and (V), halide ions are preferred as X4. From the viewpoint of suppressing the discharge of microplastic fibers, the weight-average molecular weight of the diallyl quaternary ammonium salt / acrylamide copolymer is preferably 30,000 to 2,000,000, and more preferably 1,000,000 to 2,000,000. In this specification, the weight-average molecular weight of component (a2) refers to the value obtained by gel permeation chromatography (GPC) using polyethylene glycol as the standard substance. Examples of commercially available diallyl quaternary ammonium salt / acrylamide copolymers represented by formula (IV) or (V) include the trade names "Marquardt 100", "Marquardt 550", "Noverite 300", and "Noverite 302" (all manufactured by Lubrizol).

[0051] Diallyl quaternary ammonium salt / acrylic acid copolymer is a copolymer of diallyl quaternary ammonium salt and acrylic acid. The diallyl quaternary ammonium salt and acrylic acid may be polymerized in block polymerization, random polymerization, or graft polymerization.

[0052] The weight-average molecular weight of the diallyl quaternary ammonium salt / acrylic acid copolymer is preferably between 600,000 and 3,000,000, and more preferably between 1,000,000 and 2,000,000, from the viewpoint of suppressing the discharge of microplastic fibers.

[0053] <(a3) component> (a3) Component is one or more selected from cationized guar gum, cationized tara gum, cationized locust bean gum, and their derivatives. From the viewpoint of suppressing the discharge of microplastic fibers, component (a3) ​​is preferably represented by the following general formula (IX).

[0054] [ka]

[0055] [In formula (VI), J: guar gum residue; R] 71 : Alkylene group or hydroxyalkylene group; R 72 , R 73 , R 74 Each element may independently form a heterocycle containing an alkyl group, aryl group, aralkyl group, or nitrogen atom in the formula, with 1 to 10 carbon atoms; X5: Anion (chlorine, bromine, iodine, sulfuric acid, sulfonic acid, methylsulfuric acid, phosphoric acid, nitric acid, etc.); l: Repeating unit]

[0056] (a3) The weight-average molecular weight of component is preferably 100,000 or more, more preferably 200,000 or more, and even more preferably 500,000 or more, from the viewpoint of suppressing the discharge of microplastic fibers, and preferably 3,000,000 or less, more preferably 2,000,000 or less, and even more preferably 1,500,000 or less, from the viewpoint of suppressing the discharge of microplastic fibers and suitability for incorporation into the composition.

[0057] (a3) Examples of commercially available cationic polymers that can be used as components include the following, from the viewpoint of suppressing the discharge of microplastic fibers. (Cationized guar gum) JAGUAR Excel, JAGUAR C-17, JAGUAR C-14-S (all manufactured by Solvay (Novecare)), etc. (Cationized tara gum) Examples include Kachinaru CTR-100 (Toho Chemical Industry Co., Ltd.). (Cationized locust bean gum) Kachinaru CLB-100 (Toho Chemical Industry Co., Ltd.), etc.

[0058] <(a4) component> (a4) The component is one or more polymers selected from polyethyleneimine and its alkoxylated compounds, from the viewpoint of suppressing the discharge of microplastic fibers. Examples of polyethyleneimines include polymers composed of the constituent unit ethyleneimine-CH2CH2NH-. This polyethyleneimine main chain may branch when a hydrogen atom on a nitrogen atom is substituted by another chain of the constituent unit ethyleneimine. That is, the polyethyleneimine does not have a completely linear structure, but rather a branched chain structure containing primary, secondary, and tertiary amino nitrogens. As for the polyethyleneimine, from the viewpoint of suppressing the discharge of microplastic fibers, it is preferable that it has 10 or more active hydrogen atoms per molecule, more preferably 12 or more, more preferably 200 or fewer, and more preferably 100 or fewer.

[0059] The weight-average molecular weight of polyethyleneimine is preferably 200 or more, more preferably 500 or more, even more preferably 1,200 or more, and preferably 10,000 or less, more preferably 6,000 or less, even more preferably 3,000 or less, and even more preferably 2,000 or less, from the viewpoint of suppressing the discharge of microplastic fibers.

[0060] From the perspective of suppressing the discharge of microplastic fibers, polyethyleneimine alkoxylated compounds are ethylene oxide adducts of polyethyleneimine (hereinafter also referred to as "PEI"), and the average number of moles of ethylene oxide added is between 8 moles and 15 moles. In this specification, the average number of moles of ethylene oxide added to a polyethyleneimine alkoxylated product means the average number of moles of ethylene oxide added per mole of active hydrogen contained in the PEI. Polyethyleneimine alkoxylated compounds may be used individually or in combination of two or more.

[0061] PEI is obtained by polymerizing ethyleneimine and has a branched chain structure containing primary, secondary, and tertiary amine nitrogen atoms. From the viewpoint of suppressing the discharge of microplastic fibers, the weight-average molecular weight of PEI is preferably 200 to 2,000, more preferably 300 to 1,500, even more preferably 400 to 1,000, and particularly preferably 500 to 800. From the viewpoint of suppressing the discharge of microplastic fibers, PEI preferably has 8 to 15 active hydrogen atoms per molecule, more preferably 9 to 15, and even more preferably 10 to 15.

[0062] Polyethyleneimine alkoxylated compounds are obtained by adding ethylene oxide to PEI. One such method involves adding ethylene oxide to the starting material, PEI, at a temperature between 100°C and 180°C in the presence of a basic catalyst such as sodium hydroxide, potassium hydroxide, or sodium methylate.

[0063] Examples of polyethyleneimine alkoxylated compounds include the compound shown in formula (VII), from the viewpoint of suppressing the discharge of microplastic fibers. Synthetic or commercially available polyethyleneimine alkoxylated compounds may be used.

[0064] [ka]

[0065] [In formula (VII), R 22 m is an ethylene group. 22 This represents the average number of repeats of O), and is a number between 8 and 15. m corresponds to the average number of moles of ethylene oxide added to the polyethyleneimine alkoxylated product.

[0066] From the viewpoint of suppressing the discharge of microplastic fibers, the weight-average molecular weight of the polyethyleneimine alkoxylated product is preferably 1,000 to 80,000, more preferably 2,000 to 50,000, even more preferably 3,000 to 30,000, and even more preferably 5,000 to 20,000. In this specification, the weight-average molecular weight of component (a4) refers to the value obtained by gel permeation chromatography using polyethylene glycol as the standard substance.

[0067] (a4) Cationic polymers that can be used as components include, from the viewpoint of suppressing the discharge of microplastic fibers, for example, the polyethyleneimine ethylene oxide adduct obtained in Production Example 1 below (weight-average molecular weight of polyethyleneimine: 800, number of active hydrogens in one molecule of polyethyleneimine: 10, average number of moles of ethylene oxide added per mole of active hydrogen: 10). <Manufacturing Example 1> An autoclave containing polyethyleneimine (BASF, trade name "Lupasol FG") and water was degassed under vacuum and then purged with nitrogen. While heating the autoclave, ethylene oxide equivalent to 10 moles per mole of nitrogen atoms was added to ethoxylate the mixture, yielding an ethylene oxide adduct of polyethyleneimine.

[0068] (a) More specific examples of components include diallyl dialkyl quaternary ammonium salt (DMDAAC) / acrylamide (AM) copolymers such as Marcoat 550 (weight-average molecular weight: 1.6 million) [NALCO Corporation, copolymer of acrylamide and diallyldimethylammonium salt], Poise C-60H, Caticelo M-80, Poise C-150L [Kao Corporation, cationized cellulose (O-[2-hydroxy-3-(trimethylammonio)propyl]hydroxyethylcellulose chloride)], Jaguar C17, Jaguar C14 [Rhodia Corporation, cationized guar gum (guar hydroxypropyltriammonium chloride)].

[0069] <(b) Component> (b) Component is one or more anionic surfactants selected from components (b1) and (b2). From the viewpoint of suppressing the discharge of microplastic fibers, component (b) is preferably one or more selected from components (b2).

[0070] <(b1) component> (b1) Component is alkylbenzenesulfonic acid or a salt thereof. Component (b1) may be a linear alkylbenzenesulfonic acid or a salt thereof (LAS) having an alkyl group with 9 to 21 carbon atoms. Examples of components (b1) are compounds represented by the following general formula (b1). R 1b -B-SO3M (b1) [In formula (b1), R 1b R represents an alkyl group having 9 to 21 carbon atoms, B represents a benzene ring, and R is bonded to the carbon atom of B. 1b The carbon atom is a secondary carbon atom, and M represents a hydrogen atom, alkali metal, alkaline earth metal (1 / 2 atom), ammonium, or organic ammonium. R is bonded to B. 1b In contrast, the sulfonic acid group is bonded to the ortho, meta, or para position.

[0071] From the perspective of reducing the discharge of microplastic fibers, in general formula (b1), R 1b This is an alkyl group having 9 or more carbon atoms, preferably 10 or more, more preferably 11 or more, and preferably 18 or fewer, more preferably 16 or fewer, and even more preferably 14 or fewer. In general formula (b1), M is preferably a hydrogen atom, an alkali metal such as sodium or potassium, an alkaline earth metal (half an atom) such as magnesium or calcium, or an organic ammonium, from the viewpoint of suppressing the discharge of microplastic fibers. The organic ammonium salt may be a salt of an amine used as a pH adjuster. From the viewpoint of suppressing the discharge of microplastic fibers, M is more preferably an alkali metal such as sodium or potassium, an alkanol ammonium such as monoethanolammonium or diethanolammonium, and even more preferably sodium.

[0072] <(b2) component> (b2) Component is a polyoxyalkylene alkyl ether sulfate ester or a salt thereof (AES, APES, etc.). Examples of (b2) components include compounds represented by the following general formula (b2). R 2b -O-[(PO)m (EO) n ]-SO3M (b2) [In formula (b2), R 2b ∫ represents an alkyl group having 8 to 22 carbon atoms, with the carbon atom bonded to the oxygen atom being the first carbon atom; PO represents a propylene oxy group; EO represents an ethylene oxy group; EO and PO are either block-type or random-type bonds, regardless of the bonding order of PO and EO; m and n are the average number of added moles, where m is between 0 and 5, and n is between 0.1 and 16; and M represents a hydrogen atom, alkali metal, alkaline earth metal (1 / 2 atom), ammonium, or organic ammonium.

[0073] From the perspective of reducing the discharge of microplastic fibers, in general formula (b2), R 2b The alkyl group is preferably one with 9 or more carbon atoms, more preferably 10 or more, even more preferably 12 or more, and preferably 18 or fewer carbon atoms, more preferably 16 or fewer, and even more preferably 14 or fewer carbon atoms. 2b A linear alkyl group is preferred. From the viewpoint of suppressing the discharge of microplastic fibers, in general formula (b2), m is preferably 4 or less, more preferably 3 or less, even more preferably 2 or less, and 0 or more. m may also be 0. From the viewpoint of suppressing the discharge of microplastic fibers, in general formula (b2), n is preferably 0.5 or more, more preferably 1 or more, even more preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 4 or less. In general formula (b2), M is preferably a hydrogen atom, an alkali metal such as sodium or potassium, an alkaline earth metal (half an atom) such as magnesium or calcium, or an organic ammonium, from the viewpoint of suppressing the discharge of microplastic fibers. The organic ammonium salt may be a salt of an amine used as a pH adjuster. From the viewpoint of suppressing the discharge of microplastic fibers, M is more preferably an alkali metal such as sodium or potassium, an alkanol ammonium such as monoethanolammonium or diethanolammonium, and even more preferably sodium.

[0074] From the viewpoint of suppressing the discharge of microplastic fibers, the (b2) component is preferably a polyoxyalkylene alkyl ether sulfate sodium salt in which the alkyl group has 12 or more carbon atoms and 14 or fewer carbon atoms, the average number of added propylene oxy groups is 0 or more and 4 or fewer, and the average number of added ethylene oxy groups is 1 or more and 4 or fewer. That is, from the viewpoint of suppressing the discharge of microplastic fibers, the (b2) component is R in the general formula (b2). 2b A compound in which is an alkyl group having 12 to 14 carbon atoms, m is 0 to 4, n is 1 to 4, and M is sodium is preferred.

[0075] <Composition of Microplastic Fiber Reducing Agent Composition for Textiles> The microplastic fiber reducing agent composition for textiles of the present invention contains component (a) in an amount of preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more, from the viewpoint of suppressing the discharge of microplastic fibers, and preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less, from the viewpoint of suppressing the discharge of microplastic fibers and suitability for incorporation into the composition.

[0076] The microplastic fiber reducing agent composition for textiles of the present invention contains component (b) in an amount of preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, from the viewpoint of suppressing the discharge of microplastic fibers, and preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less, from the viewpoint of suppressing the discharge of microplastic fibers and suitability for incorporation into the composition.

[0077] In the microplastic fiber reducing agent composition for textiles of the present invention, the mass ratio (a) / (b) of the content of component (a) to the content of component (b) is preferably 0.01 or more, more preferably 0.05 or more, even more preferably 0.1 or more, even more preferably 0.15 or more, and even more preferably 0.2 or more, from the viewpoint of suppressing microplastic fiber discharge and suitability for incorporation into the composition, and from the viewpoint of suppressing microplastic fiber discharge, suitability for incorporation into the composition and defoaming properties, is preferably 1 or less, more preferably 0.8 or less, and even more preferably 0.5 or less.

[0078] The microplastic fiber reducing agent composition for textiles of the present invention is used such that the concentration of component (a) at the time of use is preferably 1 ppm or more, more preferably 5 ppm or more, and even more preferably 10 ppm or more, from the viewpoint of suppressing the discharge of microplastic fibers, and preferably 2,500 ppm or less, more preferably 2,000 ppm or less, even more preferably 1,000 ppm or less, even more preferably 500 ppm or less, even more preferably 100 ppm or less, and even more preferably 50 ppm or less, from the viewpoint of suppressing the discharge of microplastic fibers and the fluidity of the liquid.

[0079] The microplastic fiber reducing agent composition for textiles of the present invention is used such that the concentration of component (b) at the time of use is preferably 10 ppm or more, more preferably 50 ppm or more, even more preferably 100 ppm or more, and preferably 500 ppm or less, more preferably 250 ppm or less, and even more preferably 150 ppm or less, from the viewpoint of suppressing the discharge of microplastic fibers.

[0080] <(c) component> The microplastic fiber reducing agent composition for textiles of the present invention may optionally contain (c) an antimicrobial compound having a diphenyl ether skeleton [hereinafter referred to as component (c)] from the viewpoint of suppressing the discharge of microplastic fibers.

[0081] (c) Regarding the components, an antibacterial compound is defined as a compound that shows a growth inhibition zone when an antibacterial test is performed using a cloth to which 1% by mass of the relevant compound has been uniformly attached to cotton cloth #2003, according to the method of JIS L 1902 "Test method for antibacterial properties of textile products".

[0082] (c) Component is one or more antimicrobial compounds selected from antimicrobial compounds having a diphenyl ether skeleton, from the viewpoint of suppressing the discharge of microplastic fibers. (c) Component is preferably an antimicrobial compound having a diphenyl ether skeleton and containing a halogen atom, for example, from the viewpoint of suppressing the discharge of microplastic fibers. Specifically, (c) component is 5-chloro-2-(2,4-dichlorophenoxy)phenol (common name: triclosan) and 4,4'-dichloro-2-hydroxydiphenyl ether (common name: diclosan), from the viewpoint of suppressing the discharge of microplastic fibers, and diclosan and triclosan are preferred, with diclosan being more preferred.

[0083] The microplastic fiber reducing agent composition for textiles of the present invention contains component (c) in an amount of preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and even more preferably 0.05% by mass or more, from the viewpoint of suppressing the discharge of microplastic fibers, and preferably 0.5% by mass or less, more preferably 0.25% by mass or less, and even more preferably 0.15% by mass or less, from the viewpoint of suppressing the discharge of microplastic fibers and suitability for incorporation into the composition.

[0084] The microplastic fiber reducing agent composition for textiles of the present invention is used such that the concentration of component (c) at the time of use is preferably 0.1 ppm or more, more preferably 0.3 ppm or more, and even more preferably 0.5 ppm or more, from the viewpoint of suppressing the discharge of microplastic fibers, and preferably 5 ppm or less, more preferably 2.5 ppm or less, and even more preferably 1.5 ppm or less, from the viewpoint of suppressing the discharge of microplastic fibers and suitability for incorporation into compositions.

[0085] In the microplastic fiber reducing agent composition for textiles of the present invention, the mass ratio (c) / (a) of the content of component (c) to the content of component (a) is preferably 0.001 or more, more preferably 0.005 or more, and even more preferably 0.01 or more, from the viewpoint of suppressing microplastic fiber discharge, and from the viewpoint of suppressing microplastic fiber discharge and suitability for incorporation into the composition, it is preferably 5 or less, more preferably 1 or less, and even more preferably 0.1 or less.

[0086] <(d) component> The microplastic fiber reducing agent composition for textiles of the present invention may optionally contain (d) a surfactant [excluding components (b) and (c)] [hereinafter referred to as component (d)].

[0087] (d) Component is one or more selected from (d1) anionic surfactants (excluding component (b)) (hereinafter referred to as component (d1)), (d2) nonionic surfactants (hereinafter referred to as component (d2)), (d3) cationic surfactants (excluding component (c)) (hereinafter referred to as component (d3)), and (d4) amphoteric surfactants (hereinafter referred to as component (d4)).

[0088] Examples of anionic surfactants for component (d1) include internal olefin sulfonate or its salt, alkyl carboxylic acid or its salt, alkyl sulfonate or its salt, α-olefin sulfonate or its salt, alkyl sulfate ester or its salt (AS), alkyl phosphate ester or its salt, α-sulfo fatty acid methyl ester or its salt (MES), fatty acid or its salt, alkyl sulfosuccinic acid or its salt.

[0089] (d1) Examples of salts of component (d1) include alkali metal salts such as sodium salts and potassium salts; and alkanolamine salts such as monoethanolamine salts and diethanolamine salts, with alkali metal salts such as sodium salts and potassium salts being preferred.

[0090] (d2) The nonionic surfactant of component (d2) may be one or more nonionic surfactants selected from aliphatic alcohol alkoxylates and aliphatic ester alkoxylates.

[0091] Examples of aliphatic alcohol alkoxylates include alkylene oxide adducts of aliphatic alcohols and their terminal methyl ether adducts. The aforementioned aliphatic alcohols include aliphatic alcohols having aliphatic hydrocarbon groups with preferably 9 or more carbon atoms, more preferably 10 or more, even more preferably 12 or more, and preferably 18 or fewer carbon atoms, more preferably 16 or fewer, and even more preferably 14 or fewer carbon atoms. Primary alcohols are preferred among the aliphatic alcohols. The aforementioned aliphatic hydrocarbon group may be an alkyl group or an alkenyl group, with alkyl groups being preferred. The aliphatic hydrocarbon group is either linear or branched, with linear being preferred. The alkylene oxide is preferably one or more selected from ethylene oxide and propylene oxide. When the alkylene oxide includes ethylene oxide and propylene oxide, it may be in a block-bonded or random-bonded form. The average number of moles of alkylene oxide added is preferably 1 or more, more preferably 5 or more, even more preferably 10 or more, and preferably 70 or less, more preferably 50 or less, and even more preferably 30 or less.

[0092] Examples of aliphatic ester alkoxylates include alkylene oxide adducts of fatty acids and their terminally methylated products. The aforementioned fatty acids include fatty acids having aliphatic hydrocarbon groups with a carbon number of preferably 9 or more, more preferably 10 or more, even more preferably 12 or more, even more preferably 14 or more, even more preferably 16 or more, and preferably 20 or less, more preferably 18 or less. The aforementioned aliphatic hydrocarbon group may be an alkyl group or an alkenyl group, with alkyl groups being preferred. The aliphatic hydrocarbon group is either linear or branched, with linear being preferred. The alkylene oxide is preferably one or more selected from ethylene oxide and propylene oxide, with ethylene oxide being more preferred. When the alkylene oxide includes ethylene oxide and propylene oxide, it may be in a block-bonded or random-bonded form. The average number of added moles of alkylene oxide is preferably 1 or more, more preferably 5 or more, even more preferably 10 or more, and preferably 50 or less, more preferably 35 or less, and even more preferably 20 or less. As the aliphatic ester alkoxylate, fatty acid methyl ester ethoxylates are preferred.

[0093] (d2) Examples of components include nonionic surfactants represented by the following general formula (d2-1). R 1d -(CO) p O-(AO) q -R 2d (d2-1) [In the formula, R 1d R is an aliphatic hydrocarbon group having 9 to 18 carbon atoms, 2d is a hydrogen atom or a methyl group, CO is a carbonyl group, p is a number of 0 or 1, and AO is one or more alkylene oxy groups selected from C2 alkylene oxy groups and C3 alkylene oxy groups. If AO contains C2 alkylene oxy groups and C3 alkylene oxy groups, the C2 alkylene oxy groups and C3 alkylene oxy groups may be bonded in a block type or a random type. q is the average number of moles added, and is a number between 1 and 70.

[0094] In formula (d2-1), R 1d The number of carbon atoms is 9 or more, preferably 10 or more, more preferably 12 or more, and 18 or less, preferably 16 or less, more preferably 14 or less. R 1dExamples include alkyl groups or alkenyl groups, with alkyl groups being preferred. The aliphatic hydrocarbon group may be linear or branched, with linear being preferred. R 2d This is either a hydrogen atom or a methyl group, with a hydrogen atom being preferred.

[0095] In equation (d2-1), p is a number that is either 0 or 1. In formula (d2-1), q is 1 or greater, preferably 5 or greater, more preferably 10 or greater, and 70 or less, preferably 50 or less, more preferably 25 or less.

[0096] In formula (d2-1), AO is one or more alkylene oxy groups selected from C2 alkylene oxy groups and C3 alkylene oxy groups. If AO includes C2 alkylene oxy groups and C3 alkylene oxy groups, the C2 alkylene oxy groups and C3 alkylene oxy groups may be in block bonds or random bonds.

[0097] The (d2) component has an average degree of polymerization (or average number of added moles) of a C2 alkylene oxy group, i.e., an ethylene oxy group (hereinafter sometimes referred to as an EO group), which is preferably 3 or more, more preferably 5 or more, even more preferably 10 or more, and preferably 70 or less, more preferably 50 or less, and even more preferably 25 or less.

[0098] The (d2) component has an average degree of polymerization (or average number of added moles) of a C3 alkylene oxy group, i.e., a propylene oxy group (hereinafter sometimes referred to as a PO group), which is preferably 0 or more, more preferably 1 or more, even more preferably 2 or more, and preferably 5 or less, more preferably 4 or less.

[0099] (d2) If the component contains an EO group and a PO group, the EO group and the PO group may be randomly bonded or block-bonded, preferably block-bonded, and more preferably block-bonded in the order EOPOEO or POEO relative to the alkyl ether.

[0100] Examples of cationic surfactants for component (d3) include compounds represented by the following general formula (d3-1).

[0101] [ka]

[0102] [In equation (d3-1), R 3d R is a chain-like hydrocarbon group having 8 to 24 carbon atoms. 4d R is a chain hydrocarbon group having 8 to 24 carbon atoms, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms. 5d and R 6d Each is independently an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms, and X - This is an alkyl sulfate ion or halide ion having 1 to 3 carbon atoms.

[0103] In general formula (d3-1), R 3d The number of carbon atoms in the chain-like hydrocarbon group is preferably 9 or more, more preferably 10 or more, preferably 18 or less, more preferably 14 or less, and even more preferably 12 or less.

[0104] In general formula (d3-1), R 4d R is a chain hydrocarbon group having 8 to 24 carbon atoms, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms. 4d The number of carbon atoms in the chain-like hydrocarbon group is preferably 9 or more, more preferably 10 or more, preferably 18 or less, more preferably 14 or less, and even more preferably 12 or less. R 4d The chain-like hydrocarbon group is preferably an alkyl group or an alkenyl group, with alkyl groups being more preferred.

[0105] In general formula (d3-1), R 5d , R 6dThese are, independently, an alkyl group having 1 to 3 carbon atoms, such as a methyl group or an ethyl group, or a hydroxyalkyl group having 1 to 3 carbon atoms.

[0106] In general formula (d3-1), R 3d , R 4d Specific examples of the chain-like hydrocarbon group include the octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, and hexadecyl group, with the nonyl group and decyl group being preferred, and the decyl group being particularly preferred.

[0107] Specific examples of hydroxyalkyl groups having 1 to 3 carbon atoms in general formula (d3-1) include hydroxymethyl, hydroxyethyl, and hydroxypropyl groups. - is CH3SO4 - CH3CH2SO4 - , or halide ions.

[0108] More specific compounds represented by the general formula (d3-1) include one or more compounds selected from N-ethyl-N,N-dimethyltetradecylammonium salt, trimethylhexadecylammonium salt, N,N-dioctyl-N,N-dimethylammonium salt, N,N-dinonyl-N,N-dimethylammonium salt, N,N-didecyl-N,N-dimethylammonium salt, N,N-dioctyl-N-ethyl-N-methylammonium salt, N,N-dinonyl-N-ethyl-N-methylammonium salt, and N,N-didecyl-N-ethyl-N-methylammonium salt, and mono-long-chain ammonium salts and di-long-chain ammonium salts can also be used in combination. The counterions for these salts are CH3SO4 - CH3CH2SO4 - or halide ions such as chloride ions.

[0109] Bispyridinium compounds are another example of cationic surfactants. Examples of bispyridinium compounds include those described in British Patent No. 1533952, Japanese Unexamined Patent Publication No. 52-105228, and International Publication No. 2014 / 100807. Specifically, preferred bispyridinium compounds are those represented by the following general formula (d3-2) and the following general formula (d3-3).

[0110] [ka]

[0111] [In the formula, Y is an alkylene or alkenylene group having 4 to 18 carbon atoms, and R 7d Each of the following represents an alkyl group having 6 to 18 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, or a phenyl group with or without halogen substitution. A is an anion. q is 1 or 2, r is 1 or 2, and q × r = 2.

[0112] A is a monovalent or divalent anion, such as chlorides, bromides, phosphates, orthosilicates, organic acids, for example, formula R 8d -COO - It can be anion from compounds such as organic acids or alkyl (1 to 40 carbon atoms) sulfonic acids. Here, R 8d A is hydrogen, hydroxyl, or an alkyl group having 1 to 40 carbon atoms. A may be an anion from an acidic agent, which is a pH adjusting agent as described later.

[0113] Examples of organic acids corresponding to the anion of A include acetic acid, propionic acid, phosphoric acid, glycolic acid, pyruvic acid, oxalic acid, maleic acid, malonic acid, succinic acid, fumaric acid, tartaric acid, citric acid, benzoic acid, cinnamic acid, mandelic acid, methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, glycyrrhizic acid, salicylic acid, stearic acid, phosphonic acid, trifluoroacetic acid, cyanoacetic acid, 4-cyanobenzoic acid, 2-chlorobenzoic acid, 2-nitrobenzoic acid, phenoxyacetic acid, and benzenesulfonic acid.

[0114] Preferred bispyridinium compounds are compounds of general formula (d3-3), and further octenidine dihydrochloride (in general formula (d3-3), R 7d is a compound wherein each is an n-octyl group, Y is an n-decenyl group, A is Cl, q is 1, r is 2, CAS No. 70775-75-6). In the microplastic fiber reducing agent composition for fibers of the present invention, the cationic surfactant may be used alone, or two or more thereof may be used in combination.

[0115] Examples of the amphoteric surfactant as component (d4) include betaine-type amphoteric surfactants and amine oxide-type amphoteric surfactants. Specifically, one or more amphoteric surfactants selected from sulfobetaine, carbobetaine and amine oxide can be mentioned.

[0116] Examples of sulfobetaines include N-alkyl-N,N-dimethyl-N-sulfopropylammonium sulfobetaine wherein the alkyl group preferably has 10 to 18 carbon atoms, N-alkyl-N,N-dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine wherein the alkyl group has 10 to 18 carbon atoms, N-alkanoylaminopropyl-N,N-dimethyl-N-sulfopropylammonium sulfobetaine wherein the alkanoyl group has 10 to 18 carbon atoms, and N-alkanoylaminopropyl-N,N-dimethyl-N-(2-hydroxysulfopropyl)ammonium sulfobetaine wherein the alkanoyl group has 10 to 18 carbon atoms.

[0117] Examples of carbobetaines include N-alkyl-N,N-dimethyl-N-carboxymethylammonium betaine wherein the alkyl group has 10 to 18 carbon atoms, and compounds represented by the following general formula (d4-1).

[0118]

Chemical Formula

[0119] [In formula (d4-1), R 9d represents an alkyl group or an alkenyl group having 7 to 21 carbon atoms, and R 10d represents a propylene group, and R 11d and R 12d each independently represent an alkyl group having 1 to 3 carbon atoms.]]

[0120] As the amine oxide, a compound represented by the following general formula (d4-2) is preferable.

[0121] Chemical Formula

[0122] [In formula (d4-2), R 13d represents a hydrocarbon group having 7 to 22 carbon atoms, preferably an alkyl group or an alkenyl group, more preferably an alkyl group, and R 14d and R 15d , which are the same or different, each represent an alkyl group having 1 to 3 carbon atoms. D represents a -NHC(=O)- group or a -C(=O)NH- group, and E represents an alkylene group having 1 to 5 carbon atoms. p and q satisfy p=0 and q=0, or p=1 and q=1.]]

[0123] The composition for reducing microplastic fibers for fibers of the present invention contains component (d) in an amount of preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 5% by mass or more, and from the viewpoint of formulation suitability of the composition, the content is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less.

[0124] The microplastic fiber reducing agent composition for textiles of the present invention is used such that the concentration of component (d) at the time of use is preferably 5 ppm or more, more preferably 10 ppm or more, and even more preferably 20 ppm or more, from the viewpoint of suitability for incorporation into the composition, and preferably 200 ppm or less, more preferably 150 ppm or less, and even more preferably 100 ppm or less, from the viewpoint of suppression of microplastic fiber discharge, suitability for incorporation into the composition, and defoaming properties.

[0125] The microplastic fiber reducing agent composition for textiles of the present invention has a ratio of the content of component (b) to the total content of surfactants contained in the composition ((b) / total content of surfactants) which is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, and even more preferably 80% by mass or more, from the viewpoint of suppressing the discharge of microplastic fibers, and preferably 100% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less, from the viewpoint of suitability for incorporation into the composition. The ratio ((b) / total content of surfactants) may be 100% by mass. Furthermore, the total content of surfactants contained in the microplastic fiber reducing agent composition for textiles of the present invention may be the sum of the content of component (b) and component (d).

[0126] The microplastic fiber reducing agent composition for textiles of the present invention may contain water. The water is used as the remainder other than components (a), (b), (c), (d) and the optional components described later. Water that is free of impurities and moderately purified is preferably used. Well water and industrial water can also be used. From the viewpoint of suppressing the discharge of microplastic fibers, for example, tap water, purified water, and ion-exchanged water are preferred. The microplastic fiber reducing agent composition for textiles of the present invention may contain water in an amount of preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, and preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less, from the viewpoint of compositional stability.

[0127] <Other ingredients> The microplastic fiber reducing agent composition for textiles of the present invention may contain, as further optional components, components known to be used in detergents and fabric softeners, such as the following components (1) to (12), to the extent that they do not affect the effects of the present invention.

[0128] (1) pH adjuster The pH adjuster may contain an acidic or alkaline agent. The acidifying agent may be one or more selected from organic acids and inorganic acids. As for organic acids, from the viewpoint of fiber persistence, one or more can be selected from citric acid, malic acid, acetic acid, succinic acid, tartaric acid, fumaric acid, lactic acid, propionic acid, oxalic acid, glutaric acid, adipic acid, gallic acid, melitic acid, cinnamic acid, salicylic acid, phthalic acid, benzoic acid, pyruvic acid, oxaloacetic acid, and aconitic acid. Examples of inorganic acids include one or more selected from hydrochloric acid, phosphoric acid, sulfuric acid, boric acid, and carbonic acid. Examples of alkaline agents include inorganic alkaline agents such as alkali metal hydroxides and alkali metal carbonates, and alkanolamines in which one to three groups bonded to the nitrogen atom are alkanol groups having 2 to 4 carbon atoms, and the remaining groups are alkyl groups having 1 to 4 carbon atoms or hydrogen atoms. Of these, hydroxyalkyl groups and hydroxyethyl groups are preferred for the alkanol groups. Other than the alkanol groups, hydrogen atoms or methyl groups are preferred, and hydrogen atoms are particularly preferred. Examples of alkanolamines include alkanolamines such as 2-aminoethanol, N-methylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, diethanolamine, N-methyldiethanolamine, and triethanolamine.

[0129] (2) Chelating agents Specific examples of chelating agents include, for example, aminopolyacetic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and hydroxyethyliminodiacetic acid, or their salts; organic acids such as citric acid, lactic acid, tartaric acid, and malic acid, or their salts; 1-hydroxyethylidene-1,1-diphosphonic acid, diethylenetriaminepenta(methylenephosphonic acid), and alkali metal or lower amine salts thereof.

[0130] (3) Anti-redeposition agents and / or polymer-based dispersants From the viewpoint of fiber persistence, examples of anti-redeposition agents and / or polymer-based dispersants include polyacrylic acid, polymaleic acid, and carboxymethylcellulose.

[0131] (4) Bleach From the standpoint of fiber persistence, examples of bleaching agents include hydrogen peroxide, sodium percarbonate, and sodium perborate.

[0132] (5) Bleach activator Examples of bleach activators include tetraacetylethylenediamine and bleach activators represented by general formulas (I-2) to (I-7) of Japanese Patent Publication No. 6-316700.

[0133] (6) Enzymes From the viewpoint of fiber persistence, the enzymes include one or more enzymes selected from amylase, sucrase, maltase, lactase, pullulanase, fructofuranosidase, cellulase, protease, and lipase.

[0134] (7) Fluorescent dyes Examples of fluorescent dyes include those commercially available as Chinopearl CBS (trade name, manufactured by Ciba Specialty Chemicals) and Whitex SA (trade name, manufactured by Sumitomo Chemical).

[0135] (8) Antioxidants Examples of antioxidants include known antioxidant compounds such as 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, methyl ester (commercially available from Raschig USA (Arlington, Texas, United States) under the trademark name RALOX® 35), butylhydroxytoluene (common name: BHT), butylhydroxyanisole (common name: BHA), distyrenated cresol, ascorbic acid (common name: vitamin C), tocopherol (common name: vitamin E), coffee bean extract (chlorogenic acid), green tea extract (catechin), or known inorganic salts such as sodium sulfite and sodium bisulfite.

[0136] (9) Dyes, antimicrobial preservatives, UV protectants, silicones and other antifoaming agents

[0137] (10) Organic solvents having hydroxyl groups As the organic solvent having a hydroxyl group, one or more compounds selected from the following components (10-1) to (10-6) are used.

[0138] (10-1) Components: Monohydric alcohol having an aliphatic hydrocarbon group with 2 to 6 carbon atoms. (10-1) Examples of components include monohydric alcohols selected from ethanol, 1-propanol, 2-propanol, and 1-butanol.

[0139] (10-2) Components: Divalent to hexavalent alcohols with 2 to 6 carbon atoms. (10-2) Examples of components include dihydric or trihydric alcohols selected from ethylene glycol, propylene glycol, butylene glycol, 2-methyl-2,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, and glycerin. 2-methyl-2,4-pentanediol is also known as hexylene glycol.

[0140] (10-3) Components: Polyalkylene glycol containing alkylene glycol units with 2 to 4 carbon atoms. (10-3) Examples of components include polyalkylene glycols selected from diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol with a weight-average molecular weight of 400 to 4,000, and polypropylene glycol with a weight-average molecular weight of 400 to 4,000.

[0141] (10-4) Components: Monoalkyl ether of (mono or poly)alkylene glycol having alkylene glycol units with 2 to 4 carbon atoms and alkyl groups with 1 to 4 carbon atoms. (10-4) Examples of components include compounds selected from diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol.

[0142] (10-5) Components: Alkyl glyceryl ether having an alkyl group with 1 to 8 carbon atoms (10-5) Examples of components include alkyl glyceryl ethers selected from 1-methylglyceryl ether, 2-methylglyceryl ether, 1,3-dimethylglyceryl ether, 1-ethylglyceryl ether, 1,3-diethylglyceryl ether, triethylglyceryl ether, 1-pentylglyceryl ether, 2-pentylglyceryl ether, 1-octylglyceryl ether, and 2-ethylhexylglyceryl ether.

[0143] (10-6) Components: Aromatic alkyl ether of (mono or poly)alkylene glycol having alkylene glycol units with 2 or 3 carbon atoms. (10-6) Examples of components include compounds selected from 2-phenoxyethanol, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, polyethylene glycol monophenyl ether with an average molecular weight of approximately 480, 2-benzyloxyethanol, and diethylene glycol monobenzyl ether.

[0144] In the above-mentioned components (10-4) and (10-6), the term "(mono or poly)alkylene glycol" means monoalkylene glycol or polyalkylene glycol. Furthermore, "polyalkylene glycol" means containing two to nine alkylene glycol units.

[0145] (11) Hydrotrope Hydrotropes are organic compounds having an anionic group, and further include alkylbenzene carboxylic acids or alkylbenzene sulfonic acids or salts thereof, which contain one or two alkyl groups selected from methyl, ethyl, or propyl groups and have one sulfonic acid group or carboxylic acid group, as well as benzoic acid or salts thereof. More specifically, these include p-toluenesulfonic acid, cumenesulfonic acid, metaxylenesulfonic acid, and benzoic acid, and alkali metal salts are preferred.

[0146] (12)Fragrance Fragrances have a masking effect and, in some cases, can even be a base material with deodorizing properties of their own. As fragrances, for example, those described in "Basic Knowledge of Fragrances and Perfumery," edited by Motoki Nakajima, published by Sangyo Tosho Co., Ltd., 4th printing April 20, 2005, and those described in Japanese Patent Publication No. 10-507793 can be used. In addition, the fragrance technology described in Japanese Patent Publication No. 2014-213072 can be used, and silicate ester fragrances and microencapsulated fragrances can also be used.

[0147] The microplastic fiber reducing agent composition of the present invention has a pH at 25°C, measured by the method described below, which is preferably 4 or higher, more preferably 5 or higher, and preferably 12 or lower, and more preferably 11 or lower, from the viewpoint of suppressing the discharge of microplastic fibers. [Method for measuring pH] Connect the pH measuring composite electrode (HORIBA glass ground-joint sleeve type) to the pH meter (HORIBA pH / ion meter F-23) and turn on the power. Use saturated potassium chloride aqueous solution (3.33 mol / L) as the internal solution for the pH electrode. Next, fill 100 mL beakers with pH 4.01 standard solution (phthalate standard solution), pH 6.86 (neutral phosphate standard solution), and pH 9.18 standard solution (borate standard solution), and immerse them in a 25°C constant temperature bath for 30 minutes. Immerse the pH measuring electrode in the standard solutions adjusted to constant temperature for 3 minutes and perform calibration in the order of pH 6.86 → pH 9.18 → pH 4.01. Adjust the sample to be measured (the microplastic fiber reducing agent composition for textiles of the present invention) to 25°C, immerse the electrode of the pH meter in the sample, and measure the pH after 1 minute.

[0148] <Textiles> The chemical fibers treated with the microplastic fiber reducing agent composition for fibers of the present invention are fibers including synthetic fibers (which may also include fibers other than synthetic fibers), and the fibers in the present invention also include fibers such as yarn. The fibers may be provided as test pieces having a predetermined size. Furthermore, the fibers are not limited to one fiber, but may include multiple fibers.

[0149] Synthetic fibers include, for example, polyamide fibers (nylon, etc.), polyester fibers (polyester, etc.), polyacrylonitrile fibers (acrylic, etc.), polyvinyl alcohol fibers (vinylon, etc.), polyvinyl chloride fibers (polyvinyl chloride, etc.), polyvinylidene chloride fibers (vinylidene, etc.), polyolefin fibers (polyethylene, polypropylene, etc.), polyurethane fibers (polyurethane, etc.), polyvinyl chloride / polyvinyl alcohol copolymer fibers (polycloral, etc.), polyalkylene parahydroxybenzoate fibers (benzoate, etc.), and polyfluoroethylene fibers (polytetrafluoroethylene, etc.). In addition, semi-synthetic fibers obtained by chemically extracting, dissolving, and spinning naturally derived components include protein fibers (milk protein casein fiber, Promix, etc.) and cellulose fibers (rayon, polynosic, cupro, acetate, etc.).

[0150] <Textile products> The microplastic fiber reducing agent composition for textiles of the present invention can also be used to treat textile products. In the present invention, "textile products" refers to woven fabrics, knitted fabrics, nonwoven fabrics, and other fabrics made from synthetic fibers or other chemical fibers such as cotton, as well as products such as undershirts, T-shirts, dress shirts, blouses, slacks, hats, handkerchiefs, towels, knitwear, socks, underwear, tights, and masks obtained using the same. From the viewpoint of suppressing the emission of microplastic fibers, textile products are textile products containing chemical fibers. From the viewpoint of suppressing the emission of microplastic fibers, the content of chemical fibers in the textile product is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, even more preferably 50% by mass or more, and 100% by mass or less. The content of chemical fibers in the textile product may be 100% by mass.

[0151] The microplastic fiber reducing agent composition for textiles of the present invention can be used as a microplastic fiber reducing agent in detergent compositions, softener compositions, treatment compositions, or spray treatment compositions. The microplastic fiber reducing agent composition for textiles of the present invention may be a microplastic fiber reducing agent for textiles that contains the above-mentioned optional components such as component (a), component (b), optionally component (c), and optionally component (d) as an active ingredient for reducing the amount of microplastic fibers.

[0152] The viscosity of the microplastic fiber reducing agent composition for textiles of the present invention at 25°C is preferably 15 mPa·s or less, more preferably 10 mPa·s or less, even more preferably 5 mPa·s or less, and preferably 1.0 mPa·s or more, more preferably 1.5 mPa·s or more, and even more preferably 2.0 mPa·s or more, from the viewpoint of suitability for spraying in a container equipped with a sprayer. The viscosity of the microplastic fiber reducing agent composition for textiles of the present invention was measured using a Type B viscometer (model BM) manufactured by Tokyo Keiki Co., Ltd., with rotor No. 1 attached. The composition was filled into a 200 mL tall glass beaker, adjusted to 25 ± 0.3 °C in a water bath, and the rotor speed was set to 60 r / min. The viscosity was measured 60 seconds after the start of the measurement.

[0153] <Method for reducing microplastic fibers in textiles> The present invention provides a method for reducing microplastic fibers in textiles, which involves contacting a chemical fiber with the following component (a) and component (b). (a) Components: One or more cationic polymers selected from the following components (a1) to (a4). (a1) Components: One or more selected from cationized cellulose and its derivatives. (a2) Components: One or more compounds selected from the group consisting of diallyl quaternary ammonium salt polymers, diallyl quaternary ammonium salt / acrylamide copolymers, and diallyl quaternary ammonium salt / acrylic acid copolymers. (a3) Components: One or more selected from cationized guar gum, cationized tara gum, cationized locust bean gum, and their derivatives. (a4) Components: One or more polymers selected from polyethyleneimine and its alkoxylated derivatives. (b) Components: One or more anionic surfactants selected from the following components (b1) and (b2). (b1) Ingredients: Alkylbenzenesulfonic acid or its salt (b2) Components: Polyoxyalkylene alkyl ether sulfate or salt thereof

[0154] In the method for reducing microplastic fibers for textiles of the present invention, component (a), component (b), optional component (c), optional component (d), and other optional components can be adapted to the preferred embodiments described in the microplastic fiber reducing agent composition for textiles of the present invention. The ratio of the content of each component is the same as that described in the preferred embodiments described in the microplastic fiber reducing agent composition for textiles of the present invention. Furthermore, chemical fibers include the chemical fibers described in the composition of microplastic fiber reducing agents for textiles and chemical fibers contained in textile products.

[0155] In the method for reducing microplastic fibers in textiles of the present invention, the microplastic fiber reducing agent composition for textiles of the present invention may be brought into direct contact with the chemical fibers, or the microplastic fiber reducing agent composition for textiles of the present invention may be diluted with water and brought into contact with the chemical fibers. The present invention may be a method for reducing microplastic fibers in textiles, in which a treatment solution containing the microplastic fiber reducing agent composition of the present invention and water is brought into contact with a synthetic fiber. In the method for reducing microplastic fibers for textiles according to the present invention, the method for bringing the microplastic fiber reducing agent composition for textiles of the present invention or a treatment liquid containing the composition into contact with chemical fibers includes spraying, coating, immersion, and the like.

[0156] The present invention may be a method for reducing the amount of microplastic fibers generated from textiles, which reduces the amount of microplastic fibers generated from chemical fibers when chemical fibers are washed.

[0157] A preferred method for spraying the treatment solution onto the fibers is to fill a container with a sprayer with the treatment solution of the present invention and spray it onto the fibers to bring them into contact. Alternatively, when applying the treatment solution to the fibers, it may be applied directly to the fibers, or it may be applied to the fibers by carrying it on an applicator such as a cloth or brush, thereby bringing it into contact with the fibers.

[0158] The aforementioned treatment solution is preferably prepared by diluting the microplastic fiber reducing agent composition for textiles of the present invention with water. Specifically, the dilution ratio of the microplastic fiber reducing agent composition for textiles of the present invention is preferably 500 times or more, more preferably 800 times or more, and preferably 5,000 times or less, and more preferably 3,000 times or less, from the viewpoint of suppressing microplastic fiber discharge and ensuring the composition's formulation stability.

[0159] The pH of the processing solution at 25°C is preferably 4 or higher, more preferably 5 or higher, and preferably 12 or lower, and more preferably 11 or lower, from the viewpoint of suppressing the discharge of microplastic fibers. The pH of the treatment solution at 25°C can be measured by the same method as the method for measuring the pH of the microplastic fiber reducing agent composition for textiles of the present invention described above. In this case, the microplastic fiber reducing agent composition for textiles is replaced with the treatment solution containing the microplastic fiber reducing agent composition for textiles, and the pH of the treatment solution is measured.

[0160] The treatment liquid is preferably water having hardness. From the viewpoint of suppressing the discharge of microplastic fibers, the hardness of the water is preferably 1°dH or higher, more preferably 2°dH or higher, even more preferably 3.5°dH or higher, even more preferably 5°dH or higher, even more preferably 7°dH or higher, and preferably 20°dH or lower, more preferably 18°dH or lower, and even more preferably 15°dH or lower.

[0161] Herein, German hardness (°dH) as used herein refers to the concentration of calcium and magnesium in water, expressed as a CaCO3 equivalent concentration of 1 mg / L (ppm) = approximately 0.056°dH (1°dH = 17.8 ppm). The calcium and magnesium concentrations for this German hardness are determined by chelation titration using ethylenediaminetetraacetate disodium salt. The specific method for measuring the German hardness of water as used herein is shown below.

[0162] <Method for measuring water hardness in Germany> 〔reagent〕 • 0.01 mol / L EDTA-2Na solution: A 0.01 mol / L aqueous solution of disodium ethylenediaminetetraacetate (titration solution, 0.01 M EDTA-Na2, manufactured by Sigma-Aldrich). ·Universal BT indicator (product name: Universal BT Co., Ltd., manufactured by Dojindo Laboratories) • Ammonia buffer solution for hardness measurement (67.5g of ammonium chloride dissolved in 570mL of 28w / v% ammonia water, with the total volume diluted to 1000mL using deionized water) [Measuring hardness] (1) Take 20 mL of water to be used as the sample into a conical beaker using a volumetric pipette. (2) Add 2 mL of ammonia buffer solution for hardness measurement. (3) Add 0.5 mL of Universal BT indicator. Confirm that the solution is reddish-purple after adding the indicator. (4) While shaking the conical beaker well, add the 0.01 mol / L EDTA·2Na solution dropwise from the burette, and the titration endpoint is reached when the sample water turns blue. (5) The total hardness is calculated using the following formula. Hardness (°dH)=T×0.01×F×56.0774×100 / A T:0.01mol / L Titration amount of EDTA・2Na solution (mL) A: Sample volume (20 mL, volume of water used as the sample) F: Factor of 0.01 mol / L EDTA-2Na solution

[0163] The concentration of component (a) in the microplastic fiber reducing agent composition for textiles that is brought into contact with the chemical fibers, or in the treatment liquid containing the composition, is preferably 0.1 ppm or more, more preferably 0.5 ppm or more, even more preferably 1 ppm or more, even more preferably 5 ppm or more, and even more preferably 25 ppm or more, from the viewpoint of suppressing the discharge of microplastic fibers, and preferably 1,000 ppm or less, more preferably 500 ppm or less, and even more preferably 100 ppm or less, from the viewpoint of the fluidity of the composition.

[0164] The concentration of component (b) in the microplastic fiber reducing agent composition for textiles that is brought into contact with the chemical fibers, or in the treatment liquid containing the composition, is preferably 1 ppm or more, more preferably 10 ppm or more, and even more preferably 20 ppm or more, from the viewpoint of suppressing the discharge of microplastic fibers, and preferably 1,500 ppm or less, more preferably 1,000 ppm or less, and even more preferably 500 ppm or less, from the viewpoint of suppressing the discharge of microplastic fibers and suitability for incorporation into the composition.

[0165] The concentration of component (c) in the microplastic fiber reducing agent composition for fibers that comes into contact with the chemical fibers, or in the treatment solution containing the composition, is preferably 0.01 ppm or more, more preferably 0.05 ppm or more, and even more preferably 0.1 ppm or more, from the viewpoint of suppressing the discharge of microplastic fibers, and preferably 10 ppm or less, more preferably 5 ppm or less, and even more preferably 1 ppm or less, from the viewpoint of suppressing the discharge of microplastic fibers and suitability for incorporation into the composition.

[0166] The concentration of component (d) in the microplastic fiber reducing agent composition for fibers that comes into contact with the chemical fibers, or in the treatment solution containing the composition, is preferably 0.1 ppm or more, more preferably 1 ppm or more, and even more preferably 10 ppm or more, from the viewpoint of suppressing the discharge of microplastic fibers, and preferably 1,000 ppm or less, more preferably 800 ppm or less, and even more preferably 600 ppm or less, from the viewpoint of suppressing the discharge of microplastic fibers and suitability for incorporation into the composition.

[0167] Furthermore, the temperature of the microplastic fiber reducing agent composition for fibers that comes into contact with the chemical fibers, or the treatment liquid containing the composition, is preferably 0°C or higher, more preferably 5°C or higher, even more preferably 10°C or higher, even more preferably 20°C or higher, and preferably 60°C or lower, more preferably 50°C or lower, and even more preferably 40°C or lower, from the viewpoint of suppressing the discharge of microplastic fibers.

[0168] In the method for reducing microplastic fibers for textiles of the present invention, the value of the bath ratio, which is expressed as the ratio of the mass (kg) of the fiber (textile product) to the amount (L) of the cleaning solution, i.e., the value of the amount (L) of the cleaning solution / the mass (kg) of the fiber (hereinafter, this ratio may also be referred to as the bath ratio), is preferably 3 or more, more preferably 10 or more, even more preferably 12 or more, and from the viewpoint of suppressing the discharge of microplastic fibers, preferably 30 or less, more preferably 20 or less, and even more preferably 18 or less.

[0169] In the method for reducing microplastic fibers for textiles of the present invention, the processing time for the fibers and textile products is preferably 1 minute or more, more preferably 2 minutes or more, even more preferably 3 minutes or more, from the viewpoint of suppressing the discharge of microplastic fibers, and preferably 5 hours or less, more preferably 3 hours or less, even more preferably 1 hour or less, and even more preferably 30 minutes or less.

[0170] The present invention's method for reducing microplastic fibers in textiles is also suitable for rotary processing methods. A rotary processing method refers to a processing method in which fibers or textile products that are not fixed to a rotating machine are rotated around a rotating shaft together with a cleaning solution. The rotary processing method can be carried out using a rotary washing machine. Specific examples of rotary washing machines include top-loading washing machines, twin-tub washing machines, drum washing machines, pulsator-type or agitator-type washing machines, small washing machines, and washing machines with automatic dispensing functions. These rotary washing machines can be those commercially available for household or industrial use.

[0171] In the present invention's method for reducing microplastic fibers in textiles, it is preferable to bring a microplastic fiber reducing agent composition for textiles containing component (a) and component (b), or a treatment solution containing the composition, into contact with a chemical fiber. Furthermore, the present invention may be a method for reducing microplastic fibers in textiles, comprising (a) bringing component (a) into contact with a chemical fiber, and (b) bringing component (b) into contact with a chemical fiber. Furthermore, from the viewpoint of suppressing the discharge of microplastic fibers, the present invention provides a method for reducing microplastic fibers in textiles in which component (a) is brought into contact with a chemical fiber, and then component (b) is brought into contact with the chemical fiber that has been brought into contact with component (a). [Examples]

[0172] <Examples 1 and 2> A microplastic fiber reducing agent composition for textiles (MPF reducing agent composition) was prepared using the formulations described in Tables 1 and 2, containing the following components (a), (b), an optional (c), and an optional (d). This microplastic fiber reducing agent composition for textiles was diluted 500 times with water to prepare a treatment solution containing the microplastic fiber reducing agent composition for textiles, and the effect of the microplastic fiber reducing agent composition on reducing the amount of microplastic fibers discharged was evaluated. In the description of the examples and in Tables 1 and 2, microplastic fibers may be abbreviated as MPF.

[0173] 1.Ingredients <(a) Components> (a1) component (a1-1)C-HEC(1.5 million): Cationized hydroxyethylcellulose (hydroxyethylcellulose hydroxypropyltrimethylammonium chloride ether), weight-average molecular weight 1.5 million, product name Poise C-150L, ​​manufactured by Kao Corporation. (a1-2) C-HEC (600,000): Cationized hydroxyethylcellulose (hydroxyethylcellulose hydroxypropyltrimethylammonium chloride ether), weight-average molecular weight 600,000, product name Poise C-60H, manufactured by Kao Corporation. (a1-3) AC-HEC (1 million): Alkylated cationized hydroxyethylcellulose, weight-average molecular weight 1 million

[0174] <(a1-3) Manufacturing example> AC-HEC (a1-3) was manufactured by the following method. 90 g of hydroxyethylcellulose (HEC) (Natrosol 250HR (weight-average molecular weight: 1,000,000, viscosity in 1% aqueous solution: 2,000 mPa·s, degree of substitution of hydroxyethyl group: 2.5), manufactured by ASHLAND) was placed in a 1 L separable flask equipped with a thermometer and a stirrer fitted with a borosilicate glass rod with a polytetrafluoroethylene stirring blade (blade diameter: 8 cm), and nitrogen flow was performed. 389.7 g of isopropyl alcohol (hereinafter referred to as IPA) and 70.4 g of deionized water were added, and the mixture was stirred at 200 rpm for 5 minutes. Then, 10.2 g of 48% sodium hydroxide aqueous solution was added, and the mixture was stirred for a further 15 minutes. Next, 3.6 g of lauryl glycidyl ether (hereinafter also referred to as "LA-EP", Epogosei LA(D), manufactured by Yokkaichi Gosei Co., Ltd.) was added, and the alkylation reaction was carried out at 80°C for 13 hours. Next, 17.2g of glycidyltrimethylammonium chloride (hereinafter also referred to as "GMAC," SY-GTA80, manufactured by Sakamoto Pharmaceutical Co., Ltd.) was added, and a cationization reaction was carried out at 50°C for 1.5 hours. After that, 10.2g of 90% aqueous acetic acid solution was added, and a neutralization reaction was carried out by stirring for 30 minutes. The obtained suspension was evenly transferred to two 500 mL centrifuge tubes and centrifuged using a high-speed refrigerated centrifuge (CR21G III, Hitachi Koki Co., Ltd.). The supernatant was removed by decantation, and the same volume as the removed supernatant was added to an 85% IPA aqueous solution, and the mixture was redispersed. The centrifugation and redispersion operations were repeated, and after the third centrifugation, the precipitate was removed. The obtained precipitate was dried under reduced pressure at 80°C for 12 hours using a vacuum dryer (VR-420, manufactured by Toyo Seisakusho Co., Ltd.), and then crushed using an extreme mill (MX-1200XTM, manufactured by WARING Inc.) to obtain powdered alkylated cationized hydroxyethyl cellulose (a1-3).

[0175] ·(a2) component (a2) MQ550 (1.6 million): Dimethyldiallylammonium chloride / acrylamide copolymer solution, product name Merquat550, manufactured by Ondeo-Nalco, weight-average molecular weight 1.6 million ·(a3) component (a3) Jaguar Excel: Cationized guar gum, JAGUAR EXCEL, manufactured by Sanshin Co., Ltd. · Component (a4) (a4) PEI: Polyethyleneimine, product name Sokalan HP20, manufactured by BASF <Component (a')> (a') HEC: Hydroxyethyl cellulose, viscosity of 2 mass% aqueous solution: 4,500 to 6,500 mPa·s, product name Natrosol 250MR, manufactured by ASHLAND

[0176] <Component (b)> · Component (b1) (b1) LAS: Sodium dodecylbenzenesulfonate, trade name "Neopelex G-25", manufactured by Kao Corporation · Component (b2) (b2) ES: Sodium polyoxyethylene lauryl ether sulfate (average added moles of oxyethylene: 2), trade name "Emal 227", manufactured by Kao Corporation <Component (c)> (c) Dichlosan: 4,4'-dichloro-2-hydroxydiphenyl ether, trade name "Tinosan HP100", manufactured by BASF <Component (d)> (d) E110L: Polyoxyethylene lauryl ether, average added moles of oxyethylene: 10, trade name "Emulgen 110", manufactured by Kao Corporation <Water> · Tap water: Water from Wakayama City

[0177] 2. Evaluation of MPF discharge suppression performance (2-1) Examples 1-1 to 1-11, 2-1 to 2-7, Comparative Examples 1-1 to 1-4 Six pieces of 6 cm × 6 cm polyester cloth (prepared by cutting BODYDRY V-neck black T-shirt (model number: CL2815H) manufactured by Gunze Co., Ltd.) were placed into a standard bottle (PS-NO.11 manufactured by As One Corporation) containing 0.1 mL of the MPF reducing agent composition shown in Tables 1 and 2 and 49.9 mL of tap water (at ambient temperature). In Examples 2-5 to 2-7 with different bath ratios, 8 pieces, 10 pieces, and 15 pieces of the polyester cloth were placed into the standard bottles, respectively. Thereafter, the standard bottle was capped and shaken for 10 minutes at 25°C and 150 rpm in a small constant-temperature shaking incubator (manufactured by TAITEC Corporation, model number: BR-23FP), and this step was defined as the washing step. Subsequently, only the cloth was taken out, transferred into a standard bottle containing 50 mL of Wakayama City water, and the same shaking operation was performed for 3 minutes to serve as the rinsing step. After each step, only the cloth was removed from the standard bottle, the remaining washing solution was collected, and the MPF emission amount was quantified by the following MPF counting method.

[0178] (2-2) Examples 1 to 12 Into a 200 mL beaker (manufactured by IWAKI), component (a) and 100 mL of ion-exchanged water were added so as to achieve the concentrations shown in Table 1, thereby preparing an aqueous dispersion containing component (a). The aforementioned six polyester cloth pieces were added to this aqueous dispersion so that they were completely immersed, and the mixture was left to stand for 1 hour. Thereafter, the polyester cloth pieces were taken out from the aqueous dispersion, spread on a wire mesh, and air-dried overnight. Six polyester cloth pieces that had undergone these treatment steps were placed in a standard bottle (PS-NO.11 manufactured by As One Corporation) containing 50 mL of tap water (temperature as is), and component (b) was further added to the standard bottle so as to achieve the concentration shown in Table 1. Under the same conditions as in (2-1), the standard bottle was capped, shaken in a small shaking incubator, and after the washing step was performed, the rinsing step was subsequently performed. After each step, only the cloth was removed from the standard bottle, the remaining washing solution was collected, and the MPF emission amount was quantified by the following MPF counting method.

[0179] 3. Quantification of MPF emission amount by MPF counting method (for details, see Japanese Patent Application No. 2022-153246) (3-1) Preparation of measurement samples The washing water obtained in the aforementioned washing and rinsing processes was poured entirely into a petri dish (AS ONE Corporation Azunol Petri Dish, 90 mm in diameter, 15 mm in height) with the lid removed. After rinsing the walls of the standard bottle with a small amount of tap water, this rinse water was also added to the petri dish. At this time, any coarse fibers and impurities that were clearly not MPF and were visible to the naked eye were manually removed using tweezers. Then, the entire mixture was gently stirred with a dropper or similar tool to ensure that the MPF particles did not overlap, and the mixture was left to stand for about 1 minute until the MPF settled at the bottom of the petri dish, and this was used as the measurement sample. (3-2) Scan The aforementioned measurement samples were scanned using a home-use scanner (Seiko Epson Corporation GT-X820). Scan conditions: "Professional mode", Image type: 48-bit color, Resolution: 600dpi, Unsharp mask effect: "Medium" (3-3) Counting by image processing The image file created in (3-2) was loaded into ImageJ, and the number of MPFs was counted after the following image processing steps. The percentage of MPF emissions for each MPF reducing agent composition was calculated, with the MPF emissions calculated in Comparative Example 1-1 set to 100%, and this percentage was expressed as MPF emissions (%). A smaller MPF emission value indicates a microplastic fiber reducing agent composition with a higher MPF emission reduction effect. The following image processing steps were performed automatically by a computer based on pre-stored settings. 1. Image > Type > 8Bit 2. Process > Subtract Background... > Rolling ball radius: 50 pixels (Check Light background) 3. Select the area inside the petri dish you want to analyze in a circular shape, and then set the threshold automatically using Image > Adjust > Threshold. 4. In Analyze > Analyze Particles, set the size to "3-Infinity" and output the summary. 5. Obtain the count value from the output Summary.

[0180] [Table 1]

[0181] [Table 2]

Claims

1. A method for reducing microplastic fibers in textiles, comprising contacting a textile product containing chemical fibers with a treatment solution containing the following components: (a) in an amount of 1 ppm to 100 ppm, (b) in an amount of 10 ppm to 500 ppm, and water. (a) Component: One or more cationic polymers selected from the following components (a2) to (a4). (a2) Components: One or more compounds selected from the group consisting of diallyl quaternary ammonium salt polymers, diallyl quaternary ammonium salt / acrylamide copolymers, and diallyl quaternary ammonium salt / acrylic acid copolymers. (a3) Components: One or more selected from cationized guar gum, cationized tara gum, cationized locust bean gum, and their derivatives. (a4) Components: One or more polymers selected from polyethyleneimine and its alkoxylated compounds. (b) Component: One or more anionic surfactants selected from the following components (b1) and (b2). (b1) Ingredients: Alkylbenzenesulfonic acid or its salt (b2) Components: Polyoxyalkylene alkyl ether sulfate or salt thereof

2. The method for reducing microplastic fibers for textiles according to Claim 1, wherein component (a4) is one or more selected from polyethyleneimine ethylene oxidized products having an average number of added moles of ethylene oxide of 8 or more and 15 or less.

3. The method for reducing microplastic fibers for textiles according to Claim 1, wherein component (b) comprises component (b2).

4. The method for reducing microplastic fibers for textiles according to Claim 1, wherein the processing liquid further contains 0.1 ppm to 10 ppm of the following component (c). (c) Component: Antimicrobial compound having a diphenyl ether skeleton

5. The method for reducing microplastic fibers for textiles according to Claim 1, wherein the ratio of the content of component (b) to the total content of surfactants contained in the treatment liquid ((b) / total content of surfactants) is 40% by mass or more.

6. The method for reducing microplastic fibers for textiles according to Claim 1, wherein component (b1) is a linear alkylbenzene sulfonic acid having an alkyl group having 9 to 21 carbon atoms or a salt thereof, and component (b2) is a compound represented by the following general formula (b2). R 2b -O-[(PO) m (EO) n ]-SO 3 M (b2) [In formula (b2), R 2b represents an alkyl group having 8 to 22 carbon atoms, the carbon atom bonded to the oxygen atom is the first carbon atom, PO represents a propyleneoxy group, EO represents an ethyleneoxy group, EO and PO are either block-type or random-type bonds, the bonding order of PO and EO is irrelevant, m and n are the average number of added moles, m is between 0 and 5, and n is between 0.1 and 16, and M represents a hydrogen atom, alkali metal, alkaline earth metal (half atom), ammonium, or organic ammonium.]

7. The method for reducing microplastic fibers for textiles according to Claim 1, wherein the bath ratio value, which is the ratio of the mass (kg) of the textile product containing the chemical fibers to the amount (L) of the treatment liquid, is 3 or more and 25 or less, i.e., [amount of treatment liquid (L)] / [mass (kg) of the textile product containing the chemical fibers].

8. The method for reducing microplastic fibers for textiles according to Claim 1, wherein the time for contacting the textile product containing the chemical fibers with the treatment liquid is 1 minute or more and 30 minutes or less.

9. The method for reducing microplastic fibers for textiles according to claim 8, wherein the processing time is 1 minute or more and 10 minutes or less.

10. The method for reducing microplastic fibers for textiles according to Claim 1, wherein the processing liquid is a cleaning liquid, and the bath ratio value, which is the ratio of the mass (kg) of the textile product containing the chemical fibers to the amount (L) of the cleaning liquid, is 3 or more and 25 or less, and after cleaning, one rinse is performed.

Images