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WO2025154271A1 - Agent de traitement déperlant pour fibres, produit fibreux déperlant et procédé de production de produit fibreux déperlant - Google Patents

Agent de traitement déperlant pour fibres, produit fibreux déperlant et procédé de production de produit fibreux déperlant

Info

Publication number
WO2025154271A1
WO2025154271A1 PCT/JP2024/001480 JP2024001480W WO2025154271A1 WO 2025154271 A1 WO2025154271 A1 WO 2025154271A1 JP 2024001480 W JP2024001480 W JP 2024001480W WO 2025154271 A1 WO2025154271 A1 WO 2025154271A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
repellent
carbon dioxide
supercritical carbon
units
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2024/001480
Other languages
English (en)
Japanese (ja)
Inventor
隆志 北本
勇雄 石丸
浩明 宮腰
照夫 堀
和正 廣垣
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sustaina Tech Co Ltd
Nicca Chemical Co Ltd
University of Fukui NUC
Original Assignee
Sustaina Tech Co Ltd
Nicca Chemical Co Ltd
University of Fukui NUC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sustaina Tech Co Ltd, Nicca Chemical Co Ltd, University of Fukui NUC filed Critical Sustaina Tech Co Ltd
Priority to PCT/JP2024/001480 priority Critical patent/WO2025154271A1/fr
Publication of WO2025154271A1 publication Critical patent/WO2025154271A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process

Definitions

  • Patent Document 2 describes a method for imparting functionality to a fiber structure, characterized in that when a functional agent is applied to the fiber structure in a supercritical fluid, the functional agent is applied while circulating the supercritical fluid.
  • One aspect of the present invention provides a water repellent treatment agent for fibers, which comprises a silicone resin containing M units contained in supercritical carbon dioxide.
  • Another aspect of the present invention provides a water-repellent textile product treated with the water-repellent textile treatment agent.
  • the present invention can provide a water-repellent treatment agent for textiles that enables water-repellent processing to be performed in supercritical carbon dioxide, which reduces pot staining and achieves sufficient water-repellent performance and washing durability (hence durable water repellency), despite the use of a silicone-based compound; a water-repellent textile product treated with the water-repellent treatment agent for textiles; and a method for producing the water-repellent textile product.
  • the water repellent treatment agent for fibers of this embodiment contains a silicone resin that includes M units.
  • a silicone resin containing M units is a silicone that contains M units and is a resin.
  • silicone resin means a silicone that has a three-dimensional network structure and is a solid at 25°C (i.e., has a melting point above 25°C).
  • Silicone resins containing M units preferably contain MQ, MDQ, MT, MTQ, MDT or MDTQ as constituent units. That is, as silicone resins containing M units, MQ resin, MT resin or MDT resin is generally known. Silicone resins containing M units may have a portion indicated as MDQ, MTQ or MDTQ.
  • M, D, T and Q are (R'') 3 SiO 0.5 unit, (R'') 2 SiO unit, R''SiO 1.5 unit and SiO 2 unit, respectively (wherein R'' is a monovalent organic group).
  • R'' is a monovalent hydrocarbon group, preferably a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 15 carbon atoms.
  • Suitable examples of the (R'') group are methyl group, ethyl group, benzyl group, phenyl group and the like.
  • the (R'') groups present in the silicone resin containing M units may be of one type or of two or more types.
  • Silicone resin has a three-dimensional network structure, which is believed to give it low fluidity, which is believed to provide the advantage that the attached drug is less likely to fall off the substrate.
  • M units it is believed that the organic groups, which are hydrophobic groups, are oriented in large numbers on the outermost surface of the particles, and therefore it is believed that the silicone resin has the advantage of exhibiting better water repellency than a silicone resin that does not contain M units.
  • the monovalent groups bonded to silicon atoms in one embodiment contain a hydrocarbon group, and optionally further contain any of hydrogen, amino groups, halogens (e.g., chlorine and bromine), alkoxy groups, etc.
  • the ratio of hydrocarbon groups out of the total number of monovalent groups bonded to silicon atoms is preferably 50% or more, or 70% or more, or 90% or more, or may be 100%.
  • the ratio of M units to 100 mol% of all constituent units is, from the viewpoint of water repellency, preferably 10 mol% or more, or 20 mol% or more, or 30 mol% or more, and preferably 90 mol% or less, or 80 mol% or less, or 70 mol% or less.
  • the molecular structure of the silicone resin can be confirmed by methods such as nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS).
  • silicone resins containing M units examples include MQ-1600 solid resin (trimethylsilyl group-containing polysiloxane) and MQ-1640 flake resin (a mixture of trimethylsilyl group-containing polysiloxane and polypropylsilsesquioxane), both of which are commercially available from Toray Dow Corning Co., Ltd.
  • MQ-1600 solid resin trimethylsilyl group-containing polysiloxane
  • MQ-1640 flake resin a mixture of trimethylsilyl group-containing polysiloxane and polypropylsilsesquioxane
  • the hardness of the silicone resin containing M units measured with a type A durometer in accordance with JIS K 6249:200313. Hardness test, is preferably 20 or more, more preferably 60 or more, from the viewpoint of water repellency. In one embodiment, the above hardness may be 80 or less, or 70 or less, from the viewpoint of affinity with supercritical carbon dioxide.
  • the weight average molecular weight of the silicone resin containing M units is preferably 1,000 or more, or 2,000 or more, or 3,000 or more, or 4,000 or more from the viewpoint of water repellency, and is preferably 50,000 or less, or 45,000 or less, or 40,000 or less from the viewpoint of affinity with supercritical carbon dioxide.
  • the weight average molecular weight is a polystyrene-equivalent molecular weight calculated from a GPC curve (elution curve) obtained by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • any solvent may be used, such as tetrahydrofuran, as long as it is capable of dissolving the sample.
  • the amount of silicone resin containing M units relative to the total amount of 100% by mass of the water repellent treatment agent for fibers is preferably 0.0006% by mass or more, or 0.006% by mass or more, or 0.03% by mass or more, from the viewpoint of obtaining good water repellency performance, and is preferably 3.0% by mass or less, or 2.5% by mass or less, or 2.0% by mass or less, from the viewpoint of suppressing pot fouling by allowing a desired amount of supercritical carbon dioxide to be present.
  • the water repellent treatment agent for fibers of this embodiment contains a silicone resin containing M units in supercritical carbon dioxide.
  • Supercritical carbon dioxide is carbon dioxide that exists in a supercritical state, that is, as a supercritical fluid that has properties of both a gas and a liquid. Silicone resins containing M units may be difficult to dissolve and/or disperse in liquid media due to their three-dimensional network structure, but they can be easily dissolved and/or dispersed in supercritical carbon dioxide. That is, by using supercritical carbon dioxide as a medium when applying silicone resins containing M units to water-repellent textile products, it is possible to make the silicone resins containing M units exist in the medium in a desired amount, for example, a relatively large amount.
  • XPS X-ray photoelectron spectroscopy
  • NMR nuclear magnetic resonance
  • a silicone resin containing M units is absorbed into the substrate and/or adhered to the substrate surface.
  • the substrate and the water repellent treatment agent for fibers are allowed to coexist in a supercritical carbon dioxide treatment device.
  • the supercritical carbon dioxide treatment device is a pressure resistant kettle, which may be made of, for example, thick stainless steel.
  • the supercritical carbon dioxide processing device has an openable door or lid, which is opened to place the substrate in the supercritical carbon dioxide processing device under atmospheric pressure.
  • the inside of the supercritical carbon dioxide processing device is preferably provided with a mechanism for holding the substrate, such as a cylindrical tube.
  • the supercritical carbon dioxide processing device is preferably equipped with a mechanism for stirring the fluid within the device. This can reduce unevenness in the absorption and/or adhesion of the silicone resin containing M units to the substrate.
  • a pipe for injecting the water repellent treatment agent for fibers into the supercritical carbon dioxide treatment device and a pipe for discharging the water repellent treatment agent for fibers from the supercritical carbon dioxide treatment device may be installed between the supercritical carbon dioxide treatment device and the preparation tank, and a pump may be installed between the pipes and driven.
  • a pump may be installed between the pipes and driven.
  • the other components may be introduced into the device in a form mixed with the silicone resin containing M units or separately from the silicone resin containing M units.
  • the organic solvent may be introduced from a location in the supercritical carbon dioxide treatment device that does not come into contact with the substrate and the silicone resin containing M units at any timing before the supercritical carbon dioxide becomes a supercritical fluid, or any other component other than the silicone resin containing M units and the organic solvent may be dissolved in the organic solvent and introduced into the supercritical carbon dioxide treatment device at a location that does not come into contact with the substrate.
  • the amount of silicone resin containing M units contained in the supercritical carbon dioxide is preferably 0.01% o.w.f. or more. If the amount of silicone resin containing M units is too small, sufficient water repellency may not be obtained. On the other hand, if the amount of silicone resin containing M units is too large, the silicone resin containing M units dissolved and/or dispersed in the supercritical carbon dioxide may become saturated, and the silicone resin may remain in the device, causing problems such as pot staining. From these points of view, the above amount is preferably 0.01% o.w.f. or more, or 0.1% o.w.f. or more, or 0.5% o.w.f. or more, or 0.7% o.w.f.
  • the pressure inside the supercritical carbon dioxide treatment device may be within a range in which the carbon dioxide inside the supercritical carbon dioxide treatment device is in a supercritical state, but may be adjusted appropriately depending on the type and amount of the silicone resin containing M units, substrate, etc. If the pressure is high, the energy required to generate supercritical carbon dioxide increases. On the other hand, the higher the pressure, the easier it is for the silicone resin containing M units to dissolve and/or disperse in supercritical carbon dioxide. From these viewpoints, the preferred pressure is 13 to 50 MPa, the more preferred pressure is 15 to 40 MPa, and the even more preferred pressure is 17 to 30 MPa.
  • the temperature inside the supercritical carbon dioxide treatment device may be within a range in which the carbon dioxide inside the supercritical carbon dioxide treatment device is in a supercritical state, but may be adjusted appropriately depending on the type and amount of the silicone resin containing M units, substrate, etc. If the temperature is high, the energy required to generate supercritical carbon dioxide increases, and the silicone resin containing M units becomes difficult to dissolve and/or disperse in supercritical carbon dioxide. On the other hand, if the temperature is too low, the diffusion movement of the water repellent treatment agent for fibers in supercritical carbon dioxide decreases, and the silicone resin containing M units becomes difficult to adhere to the substrate surface or to be absorbed into the substrate. From these viewpoints, the preferred temperature is 40°C to 130°C, more preferably 40°C to 110°C, and even more preferably 40°C to 100°C.
  • the time for treating the substrate in supercritical carbon dioxide is 10 minutes or more. If the time is long, the energy required to generate supercritical carbon dioxide increases. On the other hand, if the time is short, the silicone resin containing M units may not adhere sufficiently to the substrate surface or may not be sufficiently absorbed into the substrate, resulting in uneven exhaustion and/or adhesion of the silicone resin containing M units. From these viewpoints, the preferred time is 20 to 240 minutes, the more preferred time is 20 to 210 minutes, and the even more preferred time is 20 to 180 minutes.
  • the discharge valve is opened and the fluid is discharged from inside the supercritical carbon dioxide treatment device.
  • the discharge speed is as slow as possible.
  • the substrate contains polyethylene terephthalate (PET)
  • PET polyethylene terephthalate
  • an excessively high discharge speed can easily cause a sudden drop in pressure, which can lead to the generation of PET oligomers, so it is desirable to slow down the discharge speed.
  • the substrate to which the silicone resin containing M units has been exhausted and/or adhered is taken out as the desired water repellent textile product.
  • the carbon dioxide gas may be separated and recovered from the remaining components of the water repellent treatment agent for fibers (i.e., silicone resin containing M units, etc.) by reducing pressure or other methods.
  • the recovered carbon dioxide may be introduced into the carbon dioxide supply line described above as a gas or liquefied.
  • the materials and substrates for manufacturing water-repellent textile products were prepared as follows:
  • MQ resin trimethylsilyl group-containing polysiloxane, manufactured by Dow Corning Toray Co., Ltd., product name: MQ-1600, hardness: 60, weight average molecular weight: 10,000, solid at 25°C
  • Dimethyl silicone manufactured by Dow Corning Toray Co., Ltd., product name: SH-200, 100 cst (value at 25°C), weight average molecular weight: 12,000, liquid at 25°C
  • Metal hydrogen silicone (a non-resin silicone compound) Methylhydrogen silicone (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KF-99, functional group equivalent: 60 g/mol, weight average molecular weight: 1,000, liquid at 25° C.)
  • Hardness The hardness was measured according to JIS K 6249:200313. Hardness test using a type A durometer (manufactured by Major Co., Ltd., model number: GSD-719J).
  • Example 5 Water-repellent textile product 5 was produced in the same manner as in Example 3, except that the pressure inside the treatment device was changed to 15 MPa.
  • Water-repellent textile product 9 was produced in the same manner as in Example 3, except that the silicone resin containing M units was changed to dimethyl silicone.
  • Si content is less than 100 ppm 4: Si content is 100 ppm or more and less than 300 ppm 3: Si content is 300 ppm or more and less than 1,000 ppm 2: Si content is 1,000 ppm or more and less than 5,000 ppm 1: Si content is 5,000 ppm or more

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

Le but de la présente invention est de mettre à disposition : un agent de traitement déperlant pour fibres pouvant assurer, dans du dioxyde de carbone supercritique, une finition déperlante qui permet d'obtenir moins de taches et des performances déperlantes et une durabilité au lavage suffisantes (par conséquent, une déperlance durable), même si un composé à base de silicone est utilisé en son sein ; un produit fibreux déperlant traité avec ledit agent de traitement déperlant pour fibres ; et un procédé de production dudit produit fibreux déperlant. Un mode de réalisation de la présente invention concerne un agent de traitement déperlant pour fibres, dans lequel une résine de silicone comprenant M motifs est contenue dans du dioxyde de carbone supercritique.
PCT/JP2024/001480 2024-01-19 2024-01-19 Agent de traitement déperlant pour fibres, produit fibreux déperlant et procédé de production de produit fibreux déperlant Pending WO2025154271A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2024/001480 WO2025154271A1 (fr) 2024-01-19 2024-01-19 Agent de traitement déperlant pour fibres, produit fibreux déperlant et procédé de production de produit fibreux déperlant

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2024/001480 WO2025154271A1 (fr) 2024-01-19 2024-01-19 Agent de traitement déperlant pour fibres, produit fibreux déperlant et procédé de production de produit fibreux déperlant

Publications (1)

Publication Number Publication Date
WO2025154271A1 true WO2025154271A1 (fr) 2025-07-24

Family

ID=96470920

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2024/001480 Pending WO2025154271A1 (fr) 2024-01-19 2024-01-19 Agent de traitement déperlant pour fibres, produit fibreux déperlant et procédé de production de produit fibreux déperlant

Country Status (1)

Country Link
WO (1) WO2025154271A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000220074A (ja) * 1998-11-26 2000-08-08 Toray Ind Inc 繊維用処理剤および繊維構造物の製造方法
WO2008069041A1 (fr) * 2006-12-01 2008-06-12 Teijin Fibers Limited Procédé destiné à attribuer une fonction à un polymère moulé et appareil destiné à ceci
JP2016513191A (ja) * 2013-02-28 2016-05-12 シーオーツーネクサス 高密度化流体を使用する耐久撥水剤の適用およびアクティブ化
WO2017010551A1 (fr) * 2015-07-15 2017-01-19 日立化成株式会社 Matériau composite d'aérogel
WO2019131456A1 (fr) * 2017-12-25 2019-07-04 日華化学株式会社 Composition d'agent hydrofuge, et procédé de production de produit fibreux hydrofuge

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000220074A (ja) * 1998-11-26 2000-08-08 Toray Ind Inc 繊維用処理剤および繊維構造物の製造方法
WO2008069041A1 (fr) * 2006-12-01 2008-06-12 Teijin Fibers Limited Procédé destiné à attribuer une fonction à un polymère moulé et appareil destiné à ceci
JP2016513191A (ja) * 2013-02-28 2016-05-12 シーオーツーネクサス 高密度化流体を使用する耐久撥水剤の適用およびアクティブ化
WO2017010551A1 (fr) * 2015-07-15 2017-01-19 日立化成株式会社 Matériau composite d'aérogel
WO2019131456A1 (fr) * 2017-12-25 2019-07-04 日華化学株式会社 Composition d'agent hydrofuge, et procédé de production de produit fibreux hydrofuge

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