WO2024058204A1 - Procédé de fabrication de fibres dotées de propriétés de répulsion des liquides - Google Patents

Procédé de fabrication de fibres dotées de propriétés de répulsion des liquides Download PDF

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WO2024058204A1
WO2024058204A1 PCT/JP2023/033331 JP2023033331W WO2024058204A1 WO 2024058204 A1 WO2024058204 A1 WO 2024058204A1 JP 2023033331 W JP2023033331 W JP 2023033331W WO 2024058204 A1 WO2024058204 A1 WO 2024058204A1
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compound
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liquid
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PCT/JP2023/033331
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達記 坂巻
昌弘 東
照夫 堀
和正 廣垣
功 田畑
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ダイキン工業株式会社
国立大学法人福井大学
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Publication of WO2024058204A1 publication Critical patent/WO2024058204A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/425—Carbamic or thiocarbamic acids or derivatives thereof, e.g. urethanes
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • 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

  • the present disclosure relates to a method for producing liquid-repellent fibers, and particularly to a method for producing liquid-repellent fibers using supercritical carbon dioxide as a processing medium.
  • Patent Document 1 a fiber or textile product is treated using a fiber treatment agent containing supercritical carbon dioxide or liquefied carbon dioxide, water, and a surfactant to form reverse micelles.
  • a processing method is disclosed.
  • Cited Document 1 does not specifically describe imparting liquid repellency to fibers. Moreover, the combination of water and a surfactant is essential, which can be industrially disadvantageous from the viewpoint of productivity. Furthermore, with the recent worsening of environmental problems, water is a precious resource, and reducing industrial usage and wastewater volume has become a major issue.
  • the present disclosure provides a novel method that can impart liquid repellency to fibers with reduced amounts of water and/or surfactants, and preferably without the use of water and/or surfactants. Take it as a challenge.
  • [Section 1] A method for producing liquid-repellent fibers, comprising a fiber treatment step of treating a fiber base material with a repellent containing a liquid-repellent compound using supercritical carbon dioxide as a treatment medium.
  • [Section 2] Item 2. The method for producing liquid-repellent fibers according to Item 1, wherein the liquid-repellent compound has a water contact angle of 35° or more.
  • the liquid repellent compound has the following formula: -X-R n [In the formula, X is a direct bond or a 1+n valent group, R is independently at each occurrence an aliphatic hydrocarbon group having 6 to 40 carbon atoms or a polysiloxane group, which may have a substituent; n is 1 or more and 3 or less. ] Item 3. The method for producing a liquid-repellent fiber according to item 1 or 2, which has a group represented by the following. [Section 4] Item 4.
  • Item 7 The method for producing a liquid-repellent fiber according to any one of Items 1 to 6, which has a repeating unit derived from a compound represented by the following.
  • Item 8 Item 8.
  • the liquid repellent compound is one or more base compounds selected from the group consisting of monosaccharides, polysaccharides, alcohols, polyols, carboxylic acids, polycarboxylic acids, and derivatives thereof, and the following formula: -X-R n [In the formula, X is a direct bond or a 1+n valent group, R is independently at each occurrence an aliphatic hydrocarbon group having 6 to 40 carbon atoms that may have a substituent; n is 1-3. ] Item 7.
  • the method for producing a liquid-repellent fiber according to any one of Items 1 to 6, which is a compound modified with a group represented by the following.
  • the base material compound is starch, cellulose, curdlan, pullulan, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa carrageenan, iota carrageenan, isomaltodextrin, xanthan gum, jella gum, tamarind seed gum, cycloamylose, glucose, Sucrose, mannitol, sorbitol, sorbitan, maltitol, stepioxide, dextrin, cyclodextrin, glycerin, polyglycerin, menthol, xylitol, sucralose, fructose, maltose, trehalose, lactosucrose, erythritol, vanillin, cholesterol, glucosamine
  • [Section 11] Item 11.
  • the liquid repellent compound has the following formula: A(-X-R n ) m
  • A is an m-valent group obtained by removing m hydrogen atoms from an aromatic ring or a nitrogen-containing heterocycle that may have a substituent
  • X is independently at each occurrence a direct bond or a 1+n valent group
  • R is independently at each occurrence an aliphatic hydrocarbon group having 6 to 40 carbon atoms that may have a substituent
  • n is independently in each occurrence from 1 to 3, m is 1 or more and 6 or less.
  • the method for producing a liquid-repellent fiber according to any one of Items 1 to 6, which is a compound represented by: [Section 15]
  • the liquid repellent compound has the following formula: A(-X-R n ) m [In the formula, A is an m-valent group obtained by removing m hydrogen atoms from an aromatic ring or a nitrogen-containing heterocycle that may have a substituent, X is independently at each occurrence a direct bond or a 1+n valent group; R is independently at each occurrence an aliphatic hydrocarbon group having 6 to 40 carbon atoms that may have a substituent; n is independently in each occurrence from 1 to 3, m is 1 or more and 6 or less. ] Item 7.
  • Item 16 The method for producing a liquid-repellent fiber according to item 14 or 15, which is a group represented by: [Section 17] Item 7. The method for producing a liquid-repellent fiber according to any one of Items 1 to 6, wherein the liquid-repellent compound is a reaction product of an isocyanate group-containing compound and an isocyanate-reactive compound. [Section 18] Item 7. The method for producing a liquid repellent fiber according to any one of Items 1 to 6, wherein the liquid repellent compound has a polysiloxane group. [Section 19] Item 19. The method for producing a liquid repellent fiber according to Item 18, wherein the liquid repellent compound has the polysiloxane group in a side chain.
  • the liquid repellent compound is Amine skeleton and the following formula: -X N -R n
  • X N is a direct bond or a 1+n valent group, R is independently at each occurrence an aliphatic hydrocarbon group having 6 to 40 carbon atoms that may have a substituent; n is an integer of 1 or more and 3 or less.
  • Item 7 has one or more aliphatic hydrocarbon-containing groups represented by Item 7.
  • the method for producing a liquid-repellent fiber according to any one of Items 1 to 6, wherein at least one of the aliphatic hydrocarbon-containing groups is an amine modified product bonded to a nitrogen atom of the amine skeleton. .
  • the amine skeleton is composed of a mono- to trivalent amino group and a chain saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group, which may be separated by an oxygen atom and/or a sulfur atom. , the repellent according to item 20.
  • Item 22 The method for producing a liquid-repellent fiber according to any one of Items 1 to 21, wherein the fiber is a polyester or polyester blend fiber.
  • Item 23 The method for producing liquid-repellent fibers according to any one of Items 1 to 22, wherein the water concentration in the treatment agent for treating the fiber base material is 0.001 mol/L or less.
  • [Section 24] A composition comprising a liquid repellent compound defined in any one of Items 1 to 21 and supercritical carbon dioxide.
  • [Section 25] A repellent agent comprising a liquid repellent compound defined in any one of Items 1 to 21 and supercritical carbon dioxide.
  • [Section 26] Item 22. A composition comprising a liquid repellent compound defined in any one of Items 1 to 21 or fibers treated with a water repellent.
  • various liquid-repellent compounds can be produced even if the amount of water and/or surfactant is reduced, preferably without using water and/or surfactant. can be used to impart liquid repellency to the fibers.
  • n-valent group means a group having n bonds, that is, a group forming n bonds.
  • n-valent organic group means an n-valent group containing carbon.
  • Such an organic group is not particularly limited, but may be a hydrocarbon group or a derivative thereof.
  • a hydrocarbon group derivative is a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the end of the hydrocarbon group or in the molecular chain. means.
  • hydrocarbon group refers to a group containing carbon and hydrogen, which is obtained by removing a hydrogen atom from a hydrocarbon.
  • hydrocarbon groups include, but are not particularly limited to, C 1-20 hydrocarbon groups, such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups.
  • aliphatic hydrocarbon group may be linear, branched, or cyclic, and may be saturated or unsaturated.
  • the hydrocarbon group may also contain one or more ring structures. Hydrocarbon groups may be substituted with one or more substituents.
  • the repellent in the present disclosure can impart liquid repellency to the fiber base material, and can function as at least one selected from the group consisting of a water repellent, an oil repellent, an oil resistance agent, and a water resistance agent. According to the present disclosure, even if the amount of water and/or surfactant in the repellent agent is reduced, liquid repellency can be favorably imparted to the fiber base material, so from an industrial viewpoint and/or an environmental protection viewpoint. It is advantageous from
  • the repellent agent in the present disclosure includes a liquid repellent compound.
  • the repellent agent in the present disclosure may be a liquid repellent compound alone.
  • the repellent agent in the present disclosure may contain supercritical carbon dioxide as a processing medium and/or other components in addition to the liquid repellent compound.
  • the repellent in the present disclosure is a compound having a fluoroalkyl group having 8 or more carbon atoms, a compound having a perfluoroalkyl group having 8 or more carbon atoms, a compound having a fluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group having 4 or more carbon atoms. It is not necessary to have any one selected from the group consisting of a compound having an alkyl group, a compound having a perfluoroalkyl group, a compound having a fluoroalkyl group, and a compound having a fluorine atom.
  • the repellent agent in the present disclosure can impart liquid repellency to a substrate even if it does not contain these fluorine compounds.
  • liquid repellent compound in the present disclosure is capable of attaching to a fiber base material and imparting liquid repellency to the fiber base material.
  • the water contact angle of the liquid repellent compound is 35° or more, 40° or more, 45° or more, 50° or more, 55° or more, 65° or more, 75° or more, 85° or more, 90° or more, or 100° or more. It's good to be there.
  • the water contact angle of the liquid repellent compound may be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less.
  • the water contact angle is the static contact angle of a liquid-repellent compound to a spin-coated film, as shown in Examples, and the contact angle after 1 second of dropping 2 ⁇ L of water on the spin-coating film. It refers to what is obtained by measuring.
  • the solubility parameter (SP value) of the liquid repellent compound is 6 or more, 7 or more, 7.5 or more, 8 or more, 8.5 or more, 9 or more, 9.5 or more, 10 or more, 10.5 or more, 11 or more, It may be 11.5 or more, or 12 or more, preferably 8 or more, more preferably 9 or more.
  • the solubility parameter (SP value) of the liquid repellent compound is 18 or less, 16 or less, 15.5 or less, 15 or less, 14.5 or less, 14 or less, 13.5 or less, 13 or less, 12.5 or less, 12 or less, It may be 11.5 or less, or 11 or less, preferably 14 or less, more preferably 12 or less.
  • the solubility parameter is defined as the square root of the cohesive energy density, which is the cohesive energy divided by the molar molecular volume.
  • the amount of liquid repellent compound dissolved in supercritical carbon dioxide (25 MPa, 120°C) is 0.001 mg/mL or more, 0.005 mg/mL or more, 0.01 mg/mL or more, 0.05 mg/mL or more, 0. It may be 1 mg/mL or more, 0.5 mg/mL or more, or 1 mg/mL or more, preferably 0.005 mg/mL or more, more preferably 0.01 mg/mL or more.
  • the amount of the liquid repellent compound dissolved in supercritical carbon dioxide (25 MPa, 120° C.) is 50 mg/mL or less, 10 mg/mL or less, 5 mg/mL or less, 1 mg/mL or less, 0.5 mg/mL or less, or 0. It may be 1 mg/mL or less, preferably 5 mg/mL or less, more preferably 1 mg/mL or less.
  • the dust absorption rate of the liquid repellent compound may be 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, preferably 50% or more, more preferably 80% or more. , particularly preferably 90% or more.
  • the dust absorption rate is a 100% ratio obtained by dividing the weight of the liquid-repellent compound attached to the fiber by the weight of the liquid-repellent compound dissolved in supercritical carbon dioxide during treatment and multiplying the result by 100.
  • the melting point of the liquid repellent compound may be 60°C or higher, 80°C or higher, 100°C or higher, 110°C or higher, 120°C or higher, 130°C or higher, 140°C or higher, or 150°C or higher; is preferably higher than the processing temperature.
  • liquid-repellent compounds include, but are not limited to, acrylic polymer-type liquid-repellent compounds, matrix-modified liquid-repellent compounds, ring-modified liquid-repellent compounds, and isocyanate-based liquid repellent compounds, as detailed below.
  • liquid-repellent compounds include liquid-repellent compounds and polysiloxane group-containing liquid-repellent compounds.
  • the liquid repellent compound may be a combination of multiple types (for example, two or three types) of liquid repellent compounds.
  • the liquid-repellent compound preferably has a monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms, which may have a substituent.
  • the hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group, preferably an aliphatic hydrocarbon group, especially a saturated aliphatic hydrocarbon group (alkyl group). It is preferable that The hydrocarbon group may be cyclic, linear or branched, preferably linear.
  • the number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, preferably 10 or more, more preferably 12 or more.
  • the number of carbon atoms in the hydrocarbon group may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, more preferably 25 or less.
  • the monovalent hydrocarbon group having 6 or more and 40 or less carbon atoms which may have a substituent may correspond to R described below.
  • the hydrocarbon group having 6 or more and 40 or less carbon atoms which may have a substituent in the present disclosure may be a hydrocarbon group having a substituent, or may be an unsubstituted hydrocarbon group.
  • substituents include -OR', -N(R') 2 , -COOR', and halogen atoms (wherein R' is independently a hydrogen atom or a carbon number 1 to 4 hydrocarbon groups).
  • the substituent may or may not have active hydrogen.
  • the number of substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0.
  • the amount of carbon atoms relative to the total amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably It is 75 mol% or more.
  • the amount of carbon atoms relative to the total amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.
  • a group having 6 to 40 carbon atoms may have 1 to 3 (eg, 1) -OR' (particularly -OH) as a substituent (eg, other than at the terminal).
  • the liquid repellent compound has 2 or more, 5 or more, 10 or more, 25 or more, 50 or more, 75 or more, 100 or more, 300 or more, or 500 or more hydrocarbon groups per molecule. It preferably has 10 or more hydrocarbon groups.
  • the liquid repellent compound may have up to 1000, up to 500, up to 300, up to 100, up to 75, or up to 50 hydrocarbon groups per molecule.
  • the amount of hydrocarbon groups having 6 to 40 carbon atoms (especially aliphatic hydrocarbon groups) that may have substituents is 1% by weight or more, 3% by weight or more, 5% by weight or more in the liquid repellent compound. , 10% by weight or more, 20% by weight or more, or 30% by weight or more, preferably 5% by weight or more.
  • the amount of hydrocarbon groups having 6 to 40 carbon atoms (especially aliphatic hydrocarbon groups) which may have substituents is 80% by weight or less, 70% by weight or less, 60% by weight or less in the liquid repellent compound. , 50% by weight or less, 40% by weight or less, 30% by weight or less, or 25% by weight or less, preferably 70% by weight or less.
  • the liquid repellent compound in the present disclosure includes a fluoroalkyl group having 8 or more carbon atoms, a perfluoroalkyl group having 8 or more carbon atoms, a fluoroalkyl group having 4 or more carbon atoms, a perfluoroalkyl group having 4 or more carbon atoms, and a perfluoroalkyl group. , a fluoroalkyl group, and a fluorine atom. Even if the liquid repellent compound does not contain these fluorine-containing groups, it can impart liquid repellency to the substrate.
  • the liquid repellent compound in the present disclosure is The following formula: -X-R n [In the formula, X is a direct bond or a 1+n valent group, R is independently at each occurrence an aliphatic hydrocarbon group having 6 to 40 carbon atoms that may have a substituent; n is 1 or more and 3 or less. ] It is preferable to have a group represented by When the liquid repellent compound has the group, it is possible to impart good liquid repellency to the fiber base material.
  • X is a direct bond or a 1+n valent group.
  • n may be 1-3, 2-3, 1-2, 1, 2, or 3.
  • the molecular weight of X may be 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.
  • the molecular weight of X may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more.
  • X 1 is a non-hydrocarbon linker.
  • X 1 is a direct bond or a divalent or higher valence group.
  • the valence of X 1 may be 2-4, 2-3, or 2. It is preferable that X 1 is not only a direct bond.
  • the molecular weight of X 1 may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.
  • the molecular weight of X 1 may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more.
  • X 2 is a hydrocarbon linker, and is a hydrocarbon group having 1 to 40 carbon atoms.
  • X 2 is a divalent or higher group.
  • the valence of X 2 may be, for example, 2-4, 2-3, or 2.
  • the carbon number of X 2 may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more.
  • the carbon number of X 2 may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.
  • X 2 may be a cyclic, branched, or straight chain hydrocarbon group.
  • X 2 may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, such as an aliphatic hydrocarbon group (eg, a saturated aliphatic hydrocarbon group).
  • -(CH 2 ) p - (p is 1 to 40, for example 1 to 10)
  • a linear hydrocarbon group having 1 to 40 carbon atoms, for example 1 to 10 unsaturated bonds
  • each occurrence of R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
  • X examples include -X 1 - or -X 1 -X 2 -X 1 -.
  • X may have an amide group, urea group or urethane group.
  • R is a monovalent aliphatic hydrocarbon group having 6 or more and 40 or less carbon atoms which may have a substituent.
  • R may be cyclic, branched, or linear, preferably branched or linear, and more preferably linear.
  • R is preferably a saturated aliphatic hydrocarbon group (alkyl group) that may have a substituent.
  • the carbon number of R may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, preferably 10 or more, more preferably 12 or more.
  • the carbon number of R may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, more preferably 25 or less.
  • the liquid repellent compound may be an acrylic polymer (acrylic polymer type liquid repellent compound).
  • the acrylic polymer type liquid repellent compound contains repeating units derived from the hydrocarbon monomers shown below. Furthermore, it may contain repeating units derived from crosslinkable monomers, halogenated olefin monomers, and/or other monomers.
  • Q is a hydrogen atom, a monovalent organic group or a halogen atom
  • X 2 is a hydrocarbon group having 1 to 40 carbon atoms
  • a 1+n-valent group consisting of one or more selected from the group consisting of, R is an aliphatic hydrocarbon group having 6 to 40 carbon atoms that may have a substituent, n is 1-3.
  • It may be a polymer having a repeating unit derived from a
  • X is represented by the following formula: -X 1 - or -X 1 -X 2 -X 1 -
  • X 2 is a hydrocarbon group having 1 to 40 carbon atoms.
  • It may be a group represented by
  • Q is a hydrogen atom, a monovalent organic group, or a halogen atom.
  • monovalent organic groups include cyano groups, aliphatic hydrocarbon groups having 1 to 6 carbon atoms (eg, alkyl groups, alkenyl groups, etc.), and aromatic groups having 5 to 12 carbon atoms.
  • halogen atoms include fluorine, chlorine, bromine, iodine, and the like.
  • Q may be a hydrogen atom, a halogen atom, a methyl group, a cyano group, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, such as a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, It is a cyano group, preferably a hydrogen atom, a methyl group, a chlorine atom, especially a hydrogen atom or a methyl group.
  • the hydrocarbon monomer may include a hydrocarbon monomer containing an amide group, urea group, or urethane group in X.
  • the hydrocarbon monomer may be a combination of a hydrocarbon monomer having an amide group, urea group, or urethane group and a hydrocarbon monomer having no amide group, urea group, or urethane group. .
  • the hydrocarbon monomer may be only a non-cyclic hydrocarbon group-containing monomer, but may also include a cyclic hydrocarbon group-containing monomer.
  • the cyclic hydrocarbon group-containing monomer is a monomer having a cyclic hydrocarbon group, and may be a monomer having one ethylenically unsaturated double bond and a cyclic hydrocarbon group.
  • the cyclic hydrocarbon group-containing monomer preferably has a (meth)acrylic group as an ethylenically unsaturated double bond, for example, a (meth)acrylate group or a (meth)acrylamide group as an ethylenically unsaturated double bond. It may have.
  • the cyclic hydrocarbon group may be alicyclic or aromatic, and is preferably alicyclic.
  • the cyclic hydrocarbon group may be saturated or unsaturated, preferably saturated.
  • the cyclic hydrocarbon group may be a monocyclic group, a polycyclic group, or a bridged ring group, and a bridged ring group is preferred.
  • the cyclic hydrocarbon group may have a chain group (for example, a linear or branched hydrocarbon group).
  • the number of carbon atoms in the cyclic hydrocarbon group may be 4 or more, 6 or more, or 8 or more, and may be 30 or less, 26 or less, 22 or less, 18 or less, or 14 or less.
  • cyclic hydrocarbon group examples include cyclohexyl group, t-butylcyclohexyl group, adamantyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, bornyl group, isobornyl group, norbornyl group, Cyclopentanyl group, dicyclopentenyl group, benzyl group, phenyl group, naphthyl group, 2-t-butylphenyl group, residues obtained by removing one or more hydrogen atoms from these groups (e.g., cyclohexylene group, adamane group) tyrene group, phenylene group, naphthylene group, etc.) and groups which are substituted products thereof.
  • groups e.g., cyclohexylene group, adamane group
  • cyclic hydrocarbon group-containing monomers include cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, Dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl- Examples include 2-adamantyl (meth)acrylate and compounds in which these acrylates are substituted with acrylamide. These may be used alone or in combination of two or more.
  • hydrocarbon monomer examples include as follows.
  • the compound of the chemical formula below is an acrylic compound in which the ⁇ -position is a hydrogen atom, but the ⁇ -position may be any other Q.
  • a methacrylic compound in which the ⁇ -position is a methyl group and an ⁇ -compound in which the ⁇ -position is a chlorine atom It may be a chloroacrylic compound or the like.
  • the acrylic polymeric liquid repellent compound may have repeating units derived from halogenated olefin monomers. It is preferable that the halogenated olefin monomer does not have a fluorine atom.
  • the halogenated olefin monomer is preferably an olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine, bromine, or iodine atoms.
  • the halogenated olefin monomer is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms and having 1 to 5 chlorine atoms.
  • halogenated olefin monomers are vinyl halides such as vinyl chloride, vinyl bromide, vinyl iodide, vinylidene halides such as vinylidene chloride, vinylidene bromide, vinylidene iodide.
  • Vinyl chloride is preferred because it has high water repellency (especially durability of water repellency).
  • the presence of repeating units derived from halogenated olefin monomers increases the washing durability provided by the acrylic polymer type liquid repellent compound.
  • the acrylic polymer type liquid repellent compound may have a repeating unit derived from a crosslinkable monomer.
  • the crosslinking monomer is a monomer capable of imparting crosslinking properties to a polymer, and has at least two selected from the group consisting of a reactive group and an olefinic carbon-carbon double bond. good.
  • the crosslinking monomer may be a compound having at least two ethylenically unsaturated double bonds, or a compound having at least one ethylenically unsaturated double bond and at least one reactive group.
  • the crosslinkable monomer preferably has a (meth)acrylic group as an ethylenically unsaturated double bond, for example, a (meth)acrylate group or a (meth)acrylamide group as an ethylenically unsaturated double bond. You can.
  • reactive groups include hydroxyl group, epoxy group, chloromethyl group, blocked isocyanate group, amino group, carboxyl group, carbonyl group, isocyanate group, and the like.
  • crosslinkable monomers include diacetone (meth)acrylamide, N-methylol (meth)acrylamide, hydroxyethyl (meth)acrylamide, glycidyl (meth)acrylate, hydroxymethyl (meth)acrylate, and hydroxyethyl (meth)acrylamide.
  • the acrylic polymer type liquid repellent compound may contain repeating units derived from monomers other than the above-mentioned monomers.
  • monomers include, for example, acrylonitrile, alkoxypolyalkylene glycol (meth)acrylate, dimethylaminoethyl (meth)acrylate, organosiloxane-containing (meth)acrylate, vinyl acetate, vinyl alkyl ether, etc. .
  • Other monomers are not limited to these examples. These may be used alone or in combination of two or more.
  • the amount of the repeating unit derived from the hydrocarbon monomer is 5% by weight or more, 15% by weight or more, 20% by weight or more, 25% by weight or more, 35% by weight with respect to the acrylic polymer liquid repellent compound.
  • the content may be 45% by weight or more, 55% by weight or more, or 65% by weight or more.
  • the amount of the repeating unit derived from the hydrocarbon monomer is 98% by weight or less, 95% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight with respect to the acrylic polymer liquid repellent compound. or 60% by weight or less.
  • hydrocarbon monomers having an amide group, urea group, or urethane group are 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, and 20% by weight. The content may be 30% by weight or more, 50% by weight or more, or 75% by weight or more.
  • the hydrocarbon monomer having an amide group, urea group, or urethane group accounts for 80% by weight or less, 60% by weight or less, 40% by weight or less, or 20% by weight or less. It's fine.
  • cyclic hydrocarbon group-containing monomers are 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, 30% by weight or more, 50% by weight or more It may be at least 75% by weight, or at least 75% by weight.
  • the cyclic hydrocarbon group-containing monomer may be 80% by weight or less, 60% by weight or less, 40% by weight or less, or 20% by weight or less.
  • the amount of the repeating unit derived from the halogenated olefin monomer is 3% by weight or more, 5% by weight or more, 10% by weight or more, 15% by weight or more, or 20% by weight with respect to the acrylic polymer liquid repellent compound. % or more, 25% by weight or more, or 35% by weight or more.
  • the amount of the repeating unit derived from the halogenated olefin monomer is 80% by weight or less, 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight with respect to the acrylic polymer liquid repellent compound. The amount may be 30% by weight or less, 20% by weight or less, or 10% by weight or less, preferably 60% by weight or less.
  • the amount of the repeating unit derived from the cyclic hydrocarbon group-containing monomer is 0.5% by weight or more, 1% by weight or more, 3% by weight or more, or 4% by weight with respect to the acrylic polymer liquid repellent compound. It may be more than that.
  • the amount of the repeating unit derived from the halogenated olefin monomer is 30% by weight or less, 20% by weight or less, 15% by weight or less, 10% by weight or less, 7.5 It may be less than or equal to 5% by weight. It may be.
  • the amount of the repeating unit derived from the crosslinkable monomer is 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight based on the acrylic polymer liquid repellent compound. % or more, or 20% or more by weight.
  • the amount of the repeating unit derived from the crosslinkable monomer is 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less based on the acrylic polymer liquid repellent compound. , or 20% by weight or less.
  • the amount of repeating units derived from other monomers is 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight based on the acrylic polymer liquid repellent compound. or more, or 20% by weight or more.
  • the amount of repeating units derived from other monomers is 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, based on the acrylic polymer liquid repellent compound. Or it may be 20% by weight or less.
  • the weight average molecular weight of the acrylic polymer liquid repellent compound may be 500 or more, 1000 or more, 2500 or more, 5000 or more, 10000 or more, 25000 or more, or 50000 or more, and 5000 or more is preferable.
  • the weight average molecular weight of the acrylic polymer type liquid repellent compound may be 1,000,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 25,000 or less, or 10,000 or less, and 100,000 or less is preferable.
  • the acrylic polymer type liquid-repellent compound can be produced by a known polymerization method, and the conditions for the polymerization reaction can be arbitrarily selected.
  • Examples of such polymerization methods include solution polymerization, suspension polymerization, emulsion polymerization, and condensation polymerization.
  • solution polymerization a method is adopted in which monomers are dissolved in an organic solvent in the presence of a polymerization initiator, and after nitrogen substitution, the solution is heated and stirred at a temperature in the range of 30 to 120°C for 1 to 10 hours.
  • the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, and the like. Can be mentioned.
  • the polymerization initiator is used in an amount of 0.01 to 20 parts by weight, for example 0.01 to 10 parts by weight, based on 100 parts by weight of the monomer.
  • Organic solvents are inert to the monomers and dissolve them, such as esters (for example, esters having 2 to 40 carbon atoms, specifically ethyl acetate, butyl acetate), ketones (for example, carbon It may be a ketone having 2 to 40 carbon atoms, specifically methyl ethyl ketone, diisobutyl ketone, methyl isobutyl ketone), or an alcohol (for example, an alcohol having 1 to 40 carbon atoms, specifically ethanol, butanol, isopropyl alcohol). .
  • esters for example, esters having 2 to 40 carbon atoms, specifically ethyl acetate, butyl acetate
  • ketones for example, carbon It may be a ketone having 2 to 40 carbon atoms, specifically methyl ethyl ketone, diisobutyl ketone, methyl isobutyl ketone
  • an alcohol for example, an alcohol having 1 to 40 carbon atoms, specifically
  • organic solvents include acetone, chloroform, HCHC225, isopropyl alcohol, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate.
  • the organic solvent is used in an amount of 10 to 3,000 parts by weight, for example, 50 to 2,000 parts by weight, based on a total of 100 parts by weight of the monomers.
  • emulsion polymerization a method is adopted in which monomers are emulsified in water in the presence of a polymerization initiator and an emulsifier, and after nitrogen substitution, polymerization is carried out by stirring at a temperature in the range of 50 to 80°C for 1 to 20 hours.
  • Polymerization initiators include benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexylhydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutyramidine dihydrochloride, Water-soluble products such as sodium oxide, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypoxide, etc. Oil-soluble materials such as barreto and diisopropyl peroxydicarbonate are used.
  • the polymerization initiator is used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the monomer.
  • monomers are micronized in water and polymerized using an emulsifying device that can apply strong crushing energy, such as a high-pressure homogenizer or an ultrasonic homogenizer.
  • an emulsifying device that can apply strong crushing energy, such as a high-pressure homogenizer or an ultrasonic homogenizer.
  • strong crushing energy such as a high-pressure homogenizer or an ultrasonic homogenizer.
  • various anionic, cationic, or nonionic emulsifiers can be used as the emulsifier, and are used in an amount of 0.5 to 20 parts by weight based on 100 parts by weight of the monomer. Preference is given to using anionic and/or nonionic and/or cationic emulsifiers.
  • a compatibilizing agent such as a water-soluble organic solvent or a low molecular weight monomer to make these monomers sufficiently compatible.
  • a compatibilizer it is possible to improve emulsifying properties and copolymerizability.
  • the above-mentioned organic solvents may be used.
  • examples include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, ethanol, etc., and 1 to 50 parts by weight, for example 10 to 40 parts by weight, per 100 parts by weight of water. A range of parts by weight may be used.
  • examples of low molecular weight monomers include methyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, etc., and 1 to 50 parts by weight, based on 100 parts by weight of the total amount of monomers, For example, it may be used in a range of 10 to 40 parts by weight.
  • a chain transfer agent may be used in the polymerization.
  • the molecular weight of the polymer can be changed depending on the amount of chain transfer agent used.
  • chain transfer agents include mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, and thioglycerol (particularly alkyl mercaptans (for example, having 1 to 40 carbon atoms)), inorganic salts such as sodium hypophosphite, sodium bisulfite, etc. etc.
  • the amount of the chain transfer agent used may range from 0.01 to 10 parts by weight, for example from 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of monomers.
  • the liquid repellent compound may be a liquid repellent compound obtained by modifying a base material compound with a hydrocarbon group having 6 or more and 40 or less carbon atoms that may have a substituent (base material modified type liquid repellent compound).
  • the base material-modified liquid repellent compound is one or more base materials selected from the group consisting of one or more compounds selected from monosaccharides, polysaccharides, alcohols, polyols, carboxylic acids, and polyvalent carboxylic acids, and derivatives thereof.
  • a compound the following formula: -X-R n [In the formula, X is a direct bond or a 1+n valent group, R is independently at each occurrence an aliphatic hydrocarbon group having 6 to 40 carbon atoms that may have a substituent; n is 1 or more and 3 or less. ] It may be a compound in which the group represented by is modified.
  • matrix compounds include starch, cellulose, curdlan, pullulan, carrageenan, guar gum, chitin, chitosan, locust bean gum, kappa carrageenan, iota carrageenan, isomaltodextrin, xanthan gum, jella gum, tamarind seed gum, cycloamylose, Glucose, sucrose, mannitol, sorbitol, sorbitan, maltitol, stepioxide, dextrin, cyclodextrin, glycerin, polyglycerin, menthol, xylitol, sucralose, fructose, maltose, trehalose, lactosucrose, erythritol, vanillin, cholesterol, glucosamine, catechin, Anthocyanin, quercetin, citric acid, malic acid, gluconic acid, alginic acid, butyric acid
  • the base material compound may be a polymer (for example, a condensate or a crosslinked product) of the compounds exemplified above.
  • suitable polymers include glycerin polymers or citric acid polymers.
  • the condensation reaction or crosslinking reaction to obtain the polymer is not limited, and any known method for proceeding polymerization in the functional group of the base material compound can be used, and the reaction can be carried out using a known catalyst, dehydration condensation agent, crosslinking agent, etc. Good too.
  • catalysts, dehydration condensation agents, and crosslinking agents include acids such as p-toluenesulfonic acid, acetic acid, trifluoroacetic acid, hydrochloric acid, sulfuric acid, and fluoroboric acid; acetic acid chloride, propionic acid chloride, benzoic acid chloride, etc.
  • the matrix compound may have a hydroxy group.
  • the matrix compound may have a carboxy group.
  • the weight average molecular weight of the base material compound may be 500 or more, 1000 or more, 2500 or more, 5000 or more, 10000 or more, 25000 or more, 50000 or more, 100000 or more, or 250000 or more.
  • the weight average molecular weight of the acrylic polymer type liquid repellent compound may be 1,000,000 or less, 750,000 or less, 500,000 or less, 250,000 or less, 100,000 or less, 50,000 or less, 25,000 or less, or 10,000 or less.
  • the method for modifying the hydrocarbon group having 6 or more and 40 or less carbon atoms which may have a substituent on the base material compound is not particularly limited.
  • methods such as urethane bond formation reaction, urea bond formation reaction, ester bond formation reaction, amide bond formation reaction, and ether bond formation reaction can be used.
  • an acylating agent, a condensing agent, a catalyst, etc. are used as appropriate.
  • a method for modifying a hydrocarbon group having 6 or more and 40 or less carbon atoms which may have a substituent on the base material compound may be carried out by reacting it with a hydrocarbon group-containing reactant.
  • the hydrocarbon group-containing reactant is a compound having an aliphatic hydrocarbon group and a group capable of reacting with a functional group of a base material compound.
  • the base material compound and the hydrocarbon group may be bonded via a urethane bond.
  • the urethane bond may be formed, for example, by reacting a hydroxyl group-containing base compound with an aliphatic hydrocarbon-containing isocyanate.
  • a tin catalyst or an amine can be used as a catalyst during the reaction.
  • the hydroxyl group reacts with the isocyanate group, and the base compound and the hydrocarbon group are bonded via urethane bonds.
  • a matrix-modified liquid-repellent compound is obtained.
  • the base material compound and the hydrocarbon group may be bonded via a urea bond.
  • the urea bond can be formed, for example, by reacting an amino group-containing base compound with an aliphatic hydrocarbon group-containing isocyanate group (or by reacting an isocyanate group-containing base compound with an aliphatic hydrocarbon group-containing amine). , may be formed.
  • a catalyst may be used as appropriate during the reaction. For example, by reacting an amino group-containing base material compound and an aliphatic hydrocarbon-containing isocyanate in an organic solvent for a certain period of time, the amino group reacts with the isocyanate group, and the base material compound and the hydrocarbon group are bonded via urea bonds.
  • a matrix-modified liquid repellent compound is obtained.
  • the base material compound and the hydrocarbon group may be bonded via an ester bond.
  • the ester bond is formed, for example, by reacting a hydroxyl group-containing base compound with an aliphatic hydrocarbon group-containing carboxylic acid (or by reacting a carboxylic acid-containing base compound with an aliphatic hydrocarbon group-containing alcohol), may be formed.
  • An acylation catalyst, condensing agent, etc. may be used during the reaction.
  • the hydroxyl group reacts with the carboxylic acid, and the base material compound and the hydrocarbon group form an ester bond.
  • a matrix-modified liquid repellent compound is obtained.
  • the base material compound and the hydrocarbon group may be bonded via an amide bond.
  • the amide bond can be formed, for example, by reacting an amino group-containing base compound with an aliphatic hydrocarbon group-containing carboxylic acid (or by reacting a carboxylic acid-containing base compound with an aliphatic hydrocarbon group-containing amine). , may be formed.
  • An acylation catalyst, condensing agent, etc. may be used during the reaction.
  • the amino group reacts with the carboxylic acid, and the base compound and the hydrocarbon group form an amide bond.
  • a matrix-modified liquid repellent compound is obtained which is bonded via the .
  • Ether bonds can be formed, for example, by reacting a halogen-containing base compound with an aliphatic hydrocarbon group-containing alcohol (or by reacting a hydroxyl group-containing base compound with an aliphatic hydrocarbon group-containing halide). may be done. An acid catalyst, a base catalyst, etc. may be used during the reaction.
  • the aliphatic hydrocarbon group-containing alcohol acts as a nucleophile, and the base material compound
  • a base material-modified liquid repellent compound is obtained in which the base material-modified liquid repellent compound and the hydrocarbon group are bonded via an ether bond.
  • the liquid-repellent compound is a liquid-repellent compound (ring-modified liquid-repellent compound) modified with an aliphatic hydrocarbon group having 6 to 40 carbon atoms that may have a substituent on an aromatic ring or a nitrogen-containing heterocycle. There may be.
  • the ring-modified liquid repellent compound is The following formula: A(-X-R n ) m
  • A is an m-valent group obtained by removing m hydrogen atoms from an aromatic ring or a nitrogen-containing heterocycle that may have a substituent
  • X is independently at each occurrence a direct bond or a 1+n valent group
  • R is independently at each occurrence an aliphatic hydrocarbon group having 6 to 40 carbon atoms that may have a substituent
  • n is independently in each occurrence from 1 to 3, m is 1 or more and 6 or less.
  • It may be a compound represented by
  • A is an m-valent group.
  • m may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more, preferably 2 or more.
  • m may be 6 or less, 5 or less, 4 or less, 3 or less, or 2 or less, preferably 4 or less.
  • A is an m-valent group obtained by removing m hydrogen atoms from an aromatic ring or nitrogen-containing heterocycle which may have a substituent.
  • aromatic rings include hydrocarbon aromatic rings such as benzene ring, naphthalene ring, anthracene ring, and phenanthrene ring; heteroaromatic rings such as pyridine ring, pyrimidine ring, quinoline ring, furan ring, pyrrole ring, and pyrazole ring; Can be mentioned.
  • nitrogen-containing heterocycles include non-aromatic nitrogen-containing heterocycles such as pyrrolidine, pyrazolidine, triazolidine, oxazolidine, isoxazolidine, thiazolidine, isothiazolidine, piperidine, piperazine, and morpholine; pyrrole ring, imidazole ring, pyrazole ring, and oxazole.
  • aromatic nitrogen-containing heterocycles such as ring, isoxazole ring, thiazole ring, isothiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, oxazine ring, and thiazine ring.
  • the aromatic ring or nitrogen-containing heterocycle may have a substituent.
  • the aromatic ring or nitrogen-containing heterocycle that may have a substituent are not particularly limited, but for example, -OR', -N(R') 2 , -COOR' (wherein R' is hydrogen atom or hydrocarbon group having 1 to 4 carbon atoms), halogen atom, C 1-6 alkyl group, C 2-6 alkenyl group, which may be substituted with one or more halogen atoms, C 2-6 alkynyl group, C 3-10 cycloalkyl group, C 3-10 unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, 5-10 membered unsaturated heterocyclyl group, C 6-10 aryl group, and to 10-membered heteroaryl groups.
  • the aromatic ring or nitrogen-containing heterocycle may be a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring, or an 8-membered ring.
  • the aromatic ring or nitrogen-containing heterocycle may be a fused polycyclic ring containing 2 to 5 (preferably 2 to 3) 4- to 8-membered rings.
  • the ring-modified liquid repellent compound may be a polymer (for example, a condensate or a crosslinked product) of the above ring-modified liquid repellent compound. Polymerization may proceed through the substituent that A has in the polymer.
  • the condensation reaction or crosslinking reaction to obtain the polymer is not limited, and any known method for advancing polymerization in the functional group of A may be used, and known catalysts, dehydration condensation agents, crosslinking agents, etc. may be used. good.
  • catalysts, dehydration condensation agents, and crosslinking agents include acids such as p-toluenesulfonic acid, acetic acid, trifluoroacetic acid, hydrochloric acid, sulfuric acid, and fluoroboric acid; acetic acid chloride, propionic acid chloride, benzoic acid chloride, etc.
  • the method for modifying a hydrocarbon group having 6 or more and 40 or less carbon atoms which may have a substituent on an aromatic ring or a nitrogen-containing heterocycle is not particularly limited.
  • methods such as urethane bond formation reaction, urea bond formation reaction, ester bond formation reaction, amide bond formation reaction, and ether bond formation reaction can be used.
  • an acylating agent, a condensing agent, a catalyst, etc. are used as appropriate.
  • a method for modifying a hydrocarbon group having 6 to 40 carbon atoms that may have a substituent on an aromatic ring or a nitrogen-containing heterocycle may be carried out by reacting with a hydrocarbon group-containing reactant.
  • the hydrocarbon group-containing reactant is a compound having an aliphatic hydrocarbon group and a group capable of reacting with a functional group included in an aromatic ring or a nitrogen-containing heterocycle.
  • the aromatic ring or nitrogen-containing heterocycle and the hydrocarbon group may be bonded via a urethane bond.
  • the urethane bond may be formed, for example, by reacting a hydroxyl group-containing aromatic ring or a nitrogen-containing heterocycle with an aliphatic hydrocarbon-containing isocyanate.
  • a tin catalyst or an amine can be used as a catalyst during the reaction.
  • the hydroxyl group reacts with the isocyanate group, and the aromatic ring or nitrogen-containing heterocycle and the hydrocarbon group react.
  • a ring-modified liquid repellent compound bonded via a urethane bond is obtained.
  • the aromatic ring or nitrogen-containing heterocycle and the hydrocarbon group may be bonded via a urea bond.
  • the urea bond can be formed, for example, by reacting an amino group-containing aromatic ring or nitrogen-containing heterocycle with a hydrocarbon group-containing isocyanate group (or by reacting an isocyanate group-containing aromatic ring or nitrogen-containing heterocycle with a hydrocarbon group-containing amine). may be formed by A catalyst may be used as appropriate during the reaction.
  • a ring-modified liquid repellent compound in which a hydrogen group is bonded to a urea bond is obtained.
  • ester bond The aromatic ring or nitrogen-containing heterocycle and the hydrocarbon group may be bonded via an ester bond.
  • the ester bond can be formed, for example, by reacting a hydroxyl group-containing aromatic ring or nitrogen-containing heterocycle with a hydrocarbon group-containing carboxylic acid (or by reacting a carboxylic acid-containing aromatic ring or nitrogen-containing heterocycle with a hydrocarbon group-containing alcohol). ) may be formed.
  • An acylation catalyst, condensing agent, etc. may be used during the reaction.
  • a hydroxyl group-containing aromatic ring or nitrogen-containing heterocycle with a hydrocarbon group-containing carboxylic acid in an organic solvent for a certain period of time, the hydroxyl group reacts with the carboxylic acid, and the aromatic ring or nitrogen-containing heterocycle and the hydrocarbon group react.
  • a ring-modified liquid repellent compound in which the and is bonded via an ester bond is obtained.
  • the aromatic ring or nitrogen-containing heterocycle and the hydrocarbon group may be bonded via an amide bond.
  • the amide bond can be formed, for example, by reacting an amino group-containing aromatic ring or a nitrogen-containing heterocycle with a hydrocarbon group-containing carboxylic acid (or by reacting a carboxylic acid-containing aromatic ring or nitrogen-containing heterocycle with a hydrocarbon group-containing amine). may be formed by An acylation catalyst, condensing agent, etc. may be used during the reaction.
  • a ring-modified liquid repellent compound in which a hydrogen group is bonded via an amide bond is obtained.
  • the aromatic ring or nitrogen-containing heterocycle and the hydrocarbon group may be bonded via an ether bond.
  • the ether bond can be formed, for example, by reacting a halogen-containing aromatic ring or nitrogen-containing heterocycle with a hydrocarbon group-containing alcohol (or by reacting a hydroxyl group-containing aromatic ring or nitrogen-containing heterocycle with a hydrocarbon group-containing halide). ) may be formed.
  • An acid catalyst, a base catalyst, etc. may be used during the reaction.
  • the hydrocarbon group-containing alcohol acts as a nucleophile, and the aromatic ring or A ring-modified liquid repellent compound in which a nitrogen-containing heterocycle and a hydrocarbon group are bonded via an ether bond is obtained.
  • the liquid repellent compound may be a liquid repellent compound (isocyanate-based liquid repellent compound) that is a reaction product of an isocyanate group-containing compound and an isocyanate-reactive compound, and preferably has a carbon number that may have a substituent. It may be an isocyanate-based liquid repellent compound having 6 or more and 40 or less hydrocarbon groups.
  • diisocyanates examples include 4,4'-methylene diphenylene diisocyanate (MDI), 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, o-, m-, and p-xylylene diisocyanate, 4,4' -diisocyanatodiphenyl ether, 3,3'-dichloro-4,4'-diisocyanatodiphenylmethane, 4,4'-diphenyldiisocyanate, 4,4'-diisocyanatodibenzyl, 3,3'-dimethoxy-4 , 4'-diisocyanatodiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenyl, 2,2'-dichloro-5,5'-dimethoxy-4,4'-diisocyanatodiphenyl, 1,3-diisocyanatobenzene, 1,
  • triisocyanates examples include aliphatic triisocyanates such as 1,3,6-hexamethylene triisocyanate, and aromatic triisocyanates such as tri-(4-isocyanatophenyl)-methane.
  • polymeric isocyanates include polymethylene polyphenylisocyanate (PAPI).
  • Isocyanate-reactive compounds are compounds containing isocyanate-reactive groups, such as monofunctional, difunctional, and polyfunctional alcohols, thiols, amines, and the like.
  • isocyanate-reactive compounds include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, n-amyl alcohol, t-amyl alcohol, 2-ethylhexanol, glycidol.
  • (iso)stearyl alcohol behenyl alcohol, linear or branched long-chain alkanols such as alkyl alcohols with C6 to C40 alkyl chains; methyl or ethyl ether of polyethylene glycol, ethylene oxide and/or propylene oxide and polysiloxanes. Mention may be made of alcohols containing poly(oxyalkylene) groups, such as hydroxy-terminated methyl or ethyl ethers in random or block copolymers with alcohols containing (eg polydimethylsiloxane) groups.
  • Further examples include 1,4-butanediol, 1,6-hexanediol, 1-10-decanediol, 4,4'-isopropylidenediphenol (bisphenol A), glycerol, pentaerythritol, dipentaerythritol, etc.
  • Isocyanate-reactive compounds include amino-containing compounds such as octadecylamine, di(octadecyl)amine, 1,6-hexamethylene diamine, amino-terminated polyethylene oxide or propylene oxide or copolymers thereof, polyethylene oxide or polypropylene oxide, or these. and amino-terminated polysiloxanes such as polydimethylsiloxanes.
  • the isocyanate-based compound is a hydrocarbon group having 6 to 40 carbon atoms that may have a substituent (particularly a hydrocarbon group having 6 or more carbon atoms that may have a substituent) It is preferable to have 40 or less aliphatic hydrocarbon groups (corresponding to R above).
  • the isocyanate-based compound may be a polymer obtained by continuously reacting an isocyanate and an isocyanate-reactive compound.
  • the isocyanate-based liquid repellent compound has the following formula: L(-X-R n ) m
  • L is (a) one or more isocyanate group-containing compounds selected from the group consisting of isocyanates, diisocyanates, and polyisocyanates; (b) An m-valent urethane/amide that is a reaction product with one or more isocyanate-reactive compounds selected from the group consisting of compounds represented by the following general formulas (2a), (2b), and (2c).
  • X is independently at each occurrence a direct bond or a 1+n-valent group
  • R is independently at each occurrence an aliphatic hydrocarbon group having 6 to 40 carbon atoms that may have a substituent
  • n is independently in each occurrence from 1 to 3
  • m is 1 or more and 6 or less.
  • Rr is independently at each occurrence -H, -*, -C(O)-*, -(CH 2 CH 2 O) p (CH(CH 3 )CH 2 O) q H, -(CH 2 CH 2 O) p (CH (CH 3 ) CH 2 O) q -*, or -(CH 2 CH 2 O) p (CH (CH 3 ) CH 2 O) q C (O) -*, p is independently at each occurrence from 0 to 20; q is independently at each occurrence from 0 to 20; p+q is greater than 0,
  • the symbol * is the bond of L,
  • at least one of Rr is -H or -(CH 2 CH 2 O) p (CH(CH 3 )CH 2 O) q H, and at least one other of Rr is -*,
  • p, q, p' and q' are integers from 0 to 20 in the case of only one isocyanate-based liquid repellent compound, but in the case of an aggregate of multiple isocyanate-based liquid repellent compounds, May be expressed as an average value.
  • L in the isocyanate-based liquid repellent compound is a urethane skeleton prepared by a process comprising reacting an isocyanate group-containing compound (a) with an isocyanate-reactive compound (b), and such urethane/amide
  • the backbone may typically be polyvalent, but is not limited to this.
  • the isocyanate-reactive compound (b) has at least one -OH group, and when represented by general formula (2b), it has -OH group or - It has at least one COOH group.
  • -X-R n is bonded to each of the m bonds (indicated by the symbol *) present in the moiety derived from the isocyanate-reactive compound (b) (X is connected to the bond of L).
  • the "-X-R n " moiety is bonded to a bond (indicated by the symbol *) existing in the isocyanate-reactive compound (b) before the reaction.
  • the isocyanate-reactive compound (b) can be one type selected from the group consisting of compounds represented by general formulas (2a), (2b) and (2c), or a mixture of two or more types, among which , those represented by general formula (2a) are preferred.
  • the isocyanate group-containing compound (a) may be one selected from the group consisting of isocyanates, diisocyanates, and polyisocyanates, or a mixture of two or more of them.
  • the isocyanate group-containing compound (a) is a diisocyanate and/or polyisocyanate and the isocyanate-reactive compound (b) has a total of two or more -OH groups and/or -COOH groups, the reaction product obtained from these is , may optionally be a polymer, but is not limited thereto.
  • the isocyanate, diisocyanate, and polyisocyanate are preferably one or more selected from the group consisting of compounds represented by the following formulas (3a) to (3h).
  • isocyanate-based liquid repellent compounds examples include isocyanate-based liquid repellent compounds described in JP 2022-33218 (WO 2016/049278), Patent No. 6987847 (WO 2018/031534), WO 2021/251302, etc.
  • the liquid repellent compound may be a liquid repellent compound having a polysiloxane group (a liquid repellent compound containing a polysiloxane group). Similar to the aliphatic hydrocarbon group (R) having 6 or more and 40 or less carbon atoms which may have a substituent in the other liquid-repellent compounds mentioned above, the polysiloxane group can impart liquid repellency to the base material.
  • the polysiloxane group has the following formula: -[-Si(Rs 1 ) 2 -O-] a - [In the formula, Rs 1 is independently at each occurrence a hydrocarbon group or a reactive group having 1 to 40 carbon atoms; a is 5 or more and 10,000 or less. ] It may be expressed as
  • Rs 1 is a hydrocarbon group having 1 to 40 carbon atoms or a reactive group.
  • hydrocarbon groups having 1 to 40 carbon atoms include hydrocarbon groups having 1 to 5 carbon atoms (especially aliphatic hydrocarbon groups, especially alkyl groups) such as methyl group, ethyl group, propyl group, butyl group, pentyl group, etc. ) and a hydrocarbon group having 6 or more and 40 or less carbon atoms which may have a substituent.
  • the hydrocarbon group having 6 to 40 carbon atoms and which may have a substituent may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic group.
  • a group hydrocarbon group (alkyl group) is preferable.
  • the hydrocarbon group may be cyclic, linear or branched, preferably linear.
  • the number of carbon atoms in the hydrocarbon group may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, preferably 10 or more, more preferably 12 or more.
  • the number of carbon atoms in the hydrocarbon group may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, more preferably 25 or less.
  • the hydrocarbon group having 6 to 40 carbon atoms which may have a substituent may correspond to R described above, and the hydrocarbon group having 6 to 40 carbon atoms which may have a substituent as described above. The following explanation of the hydrocarbon group is incorporated.
  • reactive groups include functional groups such as hydroxyl groups, amino groups, mercapto groups, epoxy groups, carboxyl groups, halogen-substituted alkyl groups, vinyl groups, (meth)acrylate groups, and (meth)acrylamide groups, and silicon atoms. It is a group having a directly bonded hydrogen atom, etc.). These functional groups may be directly bonded to the silicon atom or may be bonded to an organic group directly bonded to the silicon atom.
  • the organic group may be a hydrocarbon group, for example an alkylene group or a divalent aromatic group.
  • the hydrocarbon group may have 2 to 12 carbon atoms, and the alkylene group preferably has 2 to 10 carbon atoms.
  • the divalent aromatic group preferably has 6 or more and 12 or less carbon atoms.
  • a may be 5 or more, 10 or more, 30 or more, 50 or more, 100 or more, 500 or more, 1000 or more, 2000 or more, or 3000 or more. a may be 10,000 or less, 7,500 or less, 5,000 or less, 3,000 or less, 1,500 or less, 1,000 or less, 500 or less, 300 or less, 100 or less, or 50 or less.
  • the amount of hydrocarbon groups having 1 to 40 carbon atoms may be 20 mol% or more, 40 mol% or more, 60 mol% or more, or 80 mol% or more, based on the total Rs 1 .
  • the amount of hydrocarbon groups having 1 to 40 carbon atoms may be 100 mol% or less, 90 mol% or less, 80 mol% or less, or 70 mol% or less, based on the total Rs 1 .
  • the amount of reactive groups (for example, the amount of -OH, -COOH, or -NR'2 ) is 5 mol% or more, 10 mol% or more, 20 mol% or more, or 30 mol% based on the sum of Rs 1 . % or more.
  • the amount of reactive groups (e.g., the amount of -OH, -COOH, or -NR' 2 ) is 50 mol % or less, 40 mol % or less, 30 mol % or less, or 20 mol % based on the sum of Rs 1 It may be the following.
  • the polysiloxane group may be present in the main chain, core, or side chain.
  • the polysiloxane group-containing liquid repellent compound may be combined with other liquid repellent compounds (e.g., acrylic polymer type liquid repellent compound).
  • other liquid repellent compounds e.g., acrylic polymer type liquid repellent compound.
  • matrix-modified liquid repellent compound, isocyanate-based liquid repellent compound) some or all of the aliphatic hydrocarbon groups (R) having 6 to 40 carbon atoms that may have substituents are replaced with polysiloxane groups. It may also be a compound substituted with .
  • the polysiloxane group may be present in the main chain or core of the polysiloxane group-containing liquid repellent compound.
  • the polysiloxane group-containing liquid-repellent compound does not need to have any structure other than polysiloxane, and the polysiloxane group-containing liquid-repellent compound has the following formula: (Rs 2 ) 3 Si-O-[-Si(Rs 1 ) 2 -O-] a -Si(Rs 2 ) 3 [In the formula, Rs 1 and a are as described above, Each occurrence of Rs 2 is independently a hydrocarbon group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or a reactive group. ] It may be expressed as
  • the polysiloxane group may be present in a side chain of a polysiloxane group-containing liquid repellent compound (for example, a side chain of an acrylic polymer type liquid repellent compound).
  • the side chain is a partial structure other than the main chain or core of the compound, and may be a terminal structure, for example.
  • the polysiloxane group When the polysiloxane group is present in the side chain, the polysiloxane group has the following formula: -[-Si(Rs 1 ) 2 -O-] a -Si(Rs 2 ) 3 [In the formula, Rs 1 and a are as described above, Each occurrence of Rs 2 is independently a hydrocarbon group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, or a reactive group. ] It may be expressed as
  • Rs 2 may be a hydrocarbon group having 1 to 40 carbon atoms or an alkoxy group having 1 to 40 carbon atoms.
  • the hydrocarbon group having 1 to 40 carbon atoms in Rs 2 is preferably an aliphatic hydrocarbon group, preferably an alkyl group, and preferably having 1 to 5 carbon atoms.
  • the alkoxy group having 1 to 40 carbon atoms in Rs 2 preferably has 1 to 5 carbon atoms, 1 to 3 carbon atoms, or 1 to 2 carbon atoms.
  • examples of reactive groups may be the same as Rs 1 .
  • the polysiloxane group-containing liquid repellent compound can be synthesized by a conventionally known method.
  • a polysiloxane group-containing liquid-repellent compound having a hydrocarbon group having 6 to 40 carbon atoms which may have a substituent may be methyl hydrogen silicone or a copolymer of dimethyl siloxane and methyl hydrogen siloxane. It can be obtained by modifying the ⁇ -olefin in a hydrosilylation reaction, using a catalyst such as a compound such as platinum or palladium, if necessary, to SiH during coalescence. Further, the polysiloxane group-containing liquid-repellent compound may be obtained by polymerizing an acrylic monomer containing a polysiloxane group or by reacting a reactive group of polysiloxane with a core compound.
  • the liquid repellent compound may be an amine-modified compound.
  • the molecular weight of the amine modified product may be 200 or more, 300 or more, 350 or more, 400 or more, 500 or more, 550 or more, or 750 or more.
  • the molecular weight of the amine modified product may be 3000 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 900 or less, 800 or less, 750 or less, or 500 or less.
  • the amine modified product in the present disclosure does not need to have an active hydrogen-containing group.
  • active hydrogen group-containing groups include amino groups (amino groups not adjacent to carbonyl groups, such as primary or secondary amino groups), hydroxy groups, and carboxyl groups.
  • the amine modifications in this disclosure may have no primary or secondary amino groups that are not adjacent to the carbonyl group.
  • the amine modified product has an amine skeleton and the following formula: -X N -R n [In the formula, X N is a direct bond or a 1+n valent group, R is independently at each occurrence an aliphatic hydrocarbon group having 6 to 40 carbon atoms that may have a substituent; n is an integer of 1 or more and 3 or less. ] has one or more aliphatic hydrocarbon-containing groups represented by The compound may be a compound in which at least one of the aliphatic hydrocarbon-containing groups is bonded to a nitrogen atom of the amine skeleton.
  • the amine modified product in the present disclosure has an amine skeleton.
  • the amine skeleton has one or more amino groups having a predetermined number of bonds (valence) obtained by removing a predetermined number of atoms or atomic groups (for example, hydrogen) from an amine compound.
  • the amino group in the amine skeleton means a group selected from the group consisting of -NH2 , -NH-, and -N(-) 2 , and is included in an amide group, a urethane group, a urea group, an imide, etc.
  • the amino group adjacent to the carbonyl group is also included.
  • the amine skeleton may be any aliphatic group or aromatic group having one or more amino groups, and does not exclude the presence of heteroatoms other than nitrogen.
  • the molecular weight of the amine skeleton may be 30 or more, 50 or more, 100 or more, 200 or more, 300 or more, 400 or more, or 500 or more.
  • the molecular weight of the amine skeleton may be 2800 or less, 2500 or less, 2000 or less, 1500 or less, 1000 or less, 750 or less, 600 or less, 450 or less, 300 or less, or 250 or less.
  • the number of carbon atoms in the amine skeleton may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more.
  • the number of carbon atoms in the amine skeleton may be 100 or less, 80 or less, 60 or less, 40 or less, 30 or less, 20 or less, 10 or less, or 5 or less, preferably 50 or less, especially 30 or less.
  • the amine skeleton has one or more amino groups.
  • the amino group is a monovalent to trivalent amino group, and is one or more groups selected from the group consisting of -NH 2 , -NH-, and -N(-) 2 .
  • the number of amino groups that the amine skeleton has may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, and preferably 2 or more.
  • the number of amino groups that the amine skeleton has may be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.
  • the amine skeleton has a hydrocarbon group (aliphatic hydrocarbon group or aromatic hydrocarbon group).
  • Hydrocarbon groups may be cyclic, branched, or linear. Hydrocarbon groups may be saturated or unsaturated (eg, saturated).
  • the hydrocarbon group may be separated by oxygen atoms and/or sulfur atoms, or may consist only of carbon atoms, nitrogen atoms, and hydrogen atoms.
  • the hydrocarbon group is a hydrocarbon group that may be separated by an oxygen atom and/or a sulfur atom (for example, a chain saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 aromatic hydrocarbon rings).
  • it may be a general hydrocarbon group (for example, a chain saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group having one or two aromatic hydrocarbon rings).
  • hydrocarbon group When the hydrocarbon group is separated by oxygen atoms and/or sulfur atoms, it has an ether, thioether, polyether, or polythioether structure.
  • the number of hydrocarbon groups that the amine skeleton has may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more.
  • the number of hydrocarbon groups that the amine skeleton has may be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.
  • the amine skeleton may be composed of a mono- to trivalent amino group and a chain saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group, which may be separated by an oxygen atom and/or a sulfur atom.
  • the molar ratio of carbon atoms to nitrogen atoms (C/N ratio) in the amine skeleton may be 1 or more, 2 or more, 2.5 or more, 3 or more, 3.5 or more, or 4 or more.
  • the molar ratio of carbon atoms to nitrogen atoms (C/N ratio) in the amine skeleton is 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, 3.5 or less, 3 or less, 2.5 or less, or 2 It may be less than or equal to 6, preferably less than or equal to 6 or less than or equal to 4.
  • raw material amine compounds that are precursors of amine skeletons include alkyl amines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine; ethylenediamine, propylene diamine, butylene diamine, pentanediamine, and hexamethylene diamine.
  • cyclohexanediamine methylenebiscyclohexylamine
  • diethylenetriamine triethylenetetramine, tris(2-aminoethyl)amine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tris(2-aminoethyl)amine
  • propyl) amine tetrapropylene pentamine, pentapropylene hexamine, iminobispropylamine, dibutylene triamine, bis(2-aminoethoxy)ethane, bis(2-aminoethyl) ether, bis[2-(2-aminoethoxy) ethyl] ether, bis[2-(3-aminoprotoxy)ethyl] ether, polyalkylene polyamines such as spermine and spermidine; 1-aminopropanediol, 2-amino-1,3-propanedio
  • X N is a direct bond or a 1+n valent group, R is independently at each occurrence an aliphatic hydrocarbon group having 6 to 40 carbon atoms that may have a substituent; n is an integer of 1 or more and 3 or less.
  • It has one or more aliphatic hydrocarbon-containing groups represented by:
  • the number of aliphatic hydrocarbon-containing groups that the amine modified product has may be 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, or 6 or more, and preferably 2 or more.
  • the number of aliphatic hydrocarbon-containing groups that the amine modified product has may be 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, 3 or less, 2 or less, or 1.
  • At least one aliphatic hydrocarbon-containing group in the amine modified product is bonded to the nitrogen atom of the amine skeleton.
  • the ratio of the number of aliphatic hydrocarbon-containing groups bonded to the nitrogen atom of the amine skeleton is 10% or more, 30% or more, 60% or more, 80% or more, or 100%.
  • the ratio of the number of aliphatic hydrocarbon-containing groups bonded to the nitrogen atom of the amine skeleton is 75% or less, 50% or less, or 25% or less. % or less.
  • the aliphatic hydrocarbon-containing group that is not bonded to the nitrogen atom of the amine skeleton is bonded to another group (for example, a hydrocarbon group) that the amine skeleton has.
  • ⁇ XN X N is a direct bond or a 1+n valent group, preferably a 1+n valent group.
  • XN functions as a linker that connects the amine skeleton and n R's.
  • n is the number of R's bonded to XN , and may be an integer of 1 or more and 3 or less. n may be 1 or more, 2 or more, or 3 or more. n may be 3 or less, 2 or less, or 1 or less, for example 2 or less.
  • X N may be an aliphatic group (unsaturated aliphatic group or saturated aliphatic group) or an aromatic group.
  • the molecular weight of X N may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, 500 or more, or 750 or more.
  • the molecular weight of X N may be 2000 or less, 1500 or less, 1000 or less, 750 or less, 500 or less, or 300 or less.
  • X N may have a carbonyl group.
  • X N may have one or more selected from the group consisting of an amide group, a urea group, a urethane group, and an imide, or X N may have an amide group, a urea group, together with an amino group in the amine skeleton. , a urethane group, and an imide.
  • X N2 consisting of one or more selected from the group consisting of X N2 composed of one or more members selected from the group consisting of a divalent to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent to tetravalent hydrocarbon aromatic ring, and a divalent to tetravalent heterocycle and, It may be a 1+n-valent group consisting of one or more selected from the group consisting of.
  • the group described as X N is bonded to the amine skeleton on the left side and to R on the right side.
  • X N1 X N1 is a non-hydrocarbon linker.
  • X N1 is a direct bond or a divalent or higher group.
  • the valence of X N1 may be 2-4, 2-3, or 2.
  • X N1 is not only a direct bond.
  • the molecular weight of X N1 may be 10 or more, 50 or more, 100 or more, 200 or more, 300 or more, or 500 or more.
  • the molecular weight of X N1 may be 2000 or less, 1500 or less, 1000 or less, 750 or less, or 500 or less.
  • XN2 X N2 is a hydrocarbon or aromatic linker.
  • X N2 may be a hydrocarbon group or a non-hydrocarbon group (including heteroatoms).
  • X N2 may be aliphatic or aromatic, preferably aliphatic.
  • X N2 may be linear, branched, or cyclic.
  • X N2 is preferably linear.
  • X N2 is a divalent or higher group.
  • the valence of X N2 may be, for example, 2-4, 2-3, or 2.
  • the carbon number of X N2 may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more.
  • the carbon number of X N2 may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.
  • X N2 is composed of one or more members selected from the group consisting of a divalent to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent to tetravalent hydrocarbon aromatic ring, and a divalent to tetravalent heterocycle be done.
  • the di- to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be a cyclic, branched, or straight-chain hydrocarbon group, preferably a chain hydrocarbon group (especially a straight-chain hydrocarbon group). hydrogen group).
  • the di- to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms may be a saturated or unsaturated (eg, saturated) aliphatic hydrocarbon group.
  • the number of carbon atoms in the aliphatic hydrocarbon group having 1 to 20 carbon atoms may be 1 or more, 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, or 10 or more.
  • the aliphatic hydrocarbon having 1 to 20 carbon atoms may have 15 or less carbon atoms, 10 or less carbon atoms, or 5 or less carbon atoms.
  • divalent to tetravalent hydrocarbon aromatic rings include groups obtained by removing 2 to 4 hydrogen atoms from a hydrocarbon aromatic ring such as benzene, naphthalene, anthracene, phenanthrene, tetracene (naphthacene), pentacene, pyrene, and coronene. can be mentioned.
  • the number of ring atoms of the aromatic hydrocarbon ring is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12.
  • the aromatic hydrocarbon ring may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, -N(R') 2 ( In the formula, R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), a hydroxyl group, a carboxyl group, or a halogen atom.
  • R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms
  • a hydroxyl group a carboxyl group
  • a halogen atom a compound having 1 to 4 carbon atoms
  • the valence of the aromatic hydrocarbon ring may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.
  • the di- to tetravalent heterocycle may be an aliphatic group or an aromatic group.
  • divalent heterocycles include pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, and imidazole.
  • benzimidazole triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc., with 2 to 4 hydrogen atoms removed.
  • the number of ring atoms of the heterocycle is 3 to 20, 4 to 16, or 5 to 12, preferably 5 to 12.
  • the heterocycle may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, -N(R') 2 (in the formula , R' is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms), a hydroxyl group, a carboxyl group, or a halogen atom.
  • the valence of the heterocycle may be 2 or more, 3 or more, or 4, or 4 or less, 3 or less, or 2.
  • -(CH 2 ) p - (p is 1 to 20, for example 1 to 10)
  • a linear hydrocarbon group having 1 to 40 carbon atoms, for example 1 to 10 unsaturated bonds
  • each occurrence of R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
  • Examples of X N include, when X N is divalent, -X N1 -, -X N1 -X N2 -, -X N1 -X N2 -X N1 -, -X N1 -X N2 -X N1 -X N2 -, -X N2 -, -X N2 -X N1 -, -X N2 -X N1 -, -X N2 -X N1 -X N2 -, -X N2 -X N1 -X N2 -X N1 -, and the like.
  • Examples of X N include, when X N is trivalent, -X N1 (-) 2 , -X N1 -X N2 (-) 2 , -X N1 -(X N2 -) 2 , -X N1 -X N2 -X N1 (-) 2 , -X N1 -X N2 (-X N1 -) 2 , -X N1 -(X N2 -X N1 -) 2 , -X N1 -(X N2 -X N1 -) 2 , -X N1 -X N2 -X N1 -X N2 ( -) 2 , -X N1 -X N2 -X N1 -(X N2 -) 2, -X N1 -X N2 -(X N1 -X N2 -) 2, -X N1 -(X N2 -X N1 -X N2 -) 2 ; -X N2
  • Examples of X N include, when X N is tetravalent, -X N1 (-) 3 , -X N1 -X N2 (-) 3 , -X N1 -(X N2 -) 3 , -X N1 -X N2 -X N1 (-) 3 , -X N1 -X N2 (-X N1 -) 3 , -X N1 -(X N2 -X N1 -) 3 , -X N1 -(X N2 -X N1 -) 3 , -X N1 -X N2 -X N1 -X N2 ( -) 3 , -X N1 -X N2 -X N1 -(X N2 -) 3, -X N1 -X N2 -(X N1 -X N2 -) 3, -X N1 -(X N2 -X N1 -X N2 -) 3 ; -
  • X N are -X N1 -, -X N1 -X N2 -, -X N1 -X N2 -X N1 -, -X N1 -X N2 (-) 2 , -X N2 -, -X N2 -X N1 -, -X N2 -X N1 -X N2 -, -X N2 -X N1 (-) 2 , etc.
  • R is an aliphatic hydrocarbon group having 6 or more and 40 or less carbon atoms which may have a substituent.
  • R is branched or linear, more preferably linear.
  • R may be saturated or unsaturated.
  • R is preferably a saturated aliphatic hydrocarbon group (alkyl group).
  • the carbon number of R may be 6 or more, 8 or more, 10 or more, 12 or more, 14 or more, 16 or more, or 18 or more, preferably 10 or more, more preferably 12 or more.
  • the carbon number of R may be 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less, preferably 30 or less, more preferably 25 or less.
  • the hydrocarbon group may have a substituent, but is preferably unsubstituted.
  • substituents include -OR', -N(R') 2 , -COOR', and halogen atoms (wherein R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms at each occurrence).
  • R' is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms at each occurrence.
  • the substituent may or may not have active hydrogen.
  • the number of the substituents may be 6 or less, 5 or less, 4 or less, 3 or less, 2 or less, 1 or less, or 0.
  • the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more, preferably 75 mol% or more.
  • the amount of carbon atoms relative to the amount of carbon atoms and heteroatoms may be 95 mol% or less, 90 mol% or less, 85 mol% or less, or 80 mol% or less.
  • the hydrocarbon group may have 1 to 3 (eg, 1) -OR' (particularly -OH) as a substituent (eg, other than at the terminal position).
  • X N is independently at each occurrence a direct bond or a 1+n valent group
  • R is independently at each occurrence an aliphatic hydrocarbon group having 6 to 40 carbon atoms that may have a substituent
  • L 1 is independently at each occurrence a divalent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be separated by an oxygen atom and/or a sulfur atom
  • n is an integer of 1 or more and 3 or less, independently in each occurrence
  • p is an integer of 0 or more and 2 or less, independently
  • L 1 is a divalent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be interrupted by an oxygen atom and/or a sulfur atom, and is a cyclic, It may be a branched or straight chain hydrocarbon group, preferably a chain hydrocarbon group or an aromatic hydrocarbon group.
  • the hydrocarbon group in the above explanation of [amine skeleton] may be used, and the hydrocarbon group may be separated by an oxygen atom and/or a sulfur atom, or a carbon atom, a nitrogen atom, and a hydrogen atom. It may consist only of atoms.
  • L 1 may be, for example, a saturated or unsaturated (eg saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 aromatic hydrocarbon rings. It is preferable that L 1 is a cyclic group having both a ring (for example, an aromatic ring) and a chain structure (for example, a linear structure, ether oxygen, thioether sulfur), and specific examples include 1,3-phenylenebisalkylene. group, 1,4-phenylenebisalkylene group, diphenyletherdiyl group, diphenylthioetherdiyl group, and the like.
  • the number of carbon atoms in L 1 may be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more.
  • the number of carbon atoms in L 1 may be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 3 or less.
  • p is an integer of 0 to 2, independently at each occurrence, q is an integer of 0 to 2, independently at each occurrence, and p+q is -X N -R n ) p (-H) 2 in q .
  • p may independently at each occurrence be greater than or equal to 1, such as 2.
  • r is independently at each occurrence 0 or 1
  • s is independently at each occurrence 0 or 1
  • r+s is each N(-X N -R n ) r (-H) is 1 in s .
  • p may independently at each occurrence be greater than or equal to 1, such as 2.
  • the sum of all p's and all r's is 1 or more, ie, amine modified example 1 has one or more -X N -R n .
  • the sum of all p's and all r's may be 1 or more, 3 or more, 5 or more, 7 or more, 9 or more, 12 or more (the sum of all q's and all s's may be 0) ).
  • the sum of all p's and all r's may be 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, or 4 or less.
  • t is an integer from 0 to 10.
  • t may be 0 or more, 1 or more, 2 or more, 4 or more, or 6 or more, preferably 0 or more or 2 or more.
  • t may be 8 or less, 6 or less, 4 or less, or 3 or less.
  • ⁇ Amine modified example 2 Examples of other amine modified products include the following formula: N(-X N -R n ) p (-H) q -L 2 (-X N -R n ) u [In the formula, X N is independently at each occurrence a direct bond or a 1+n-valent group; R is independently at each occurrence an aliphatic hydrocarbon group having 6 to 40 carbon atoms that may have a substituent; L 2 is a 1+u-valent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be separated by an oxygen atom and/or a sulfur atom, n is an integer of 1 or more and 3 or less, independently in each occurrence, p is an integer from 0 to 2, q is an integer from 0 to 2, p+q is 2, u is an integer from 1 to 3, The sum of p and u is 1 or more. ] Examples include the compound represented by (Amine modified example 2).
  • L 2 is a 1+u-valent aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms, which may be interrupted by an oxygen atom and/or a sulfur atom, and is a cyclic, It may be a branched or straight chain hydrocarbon group, preferably a chain hydrocarbon group or an aromatic hydrocarbon group.
  • the hydrocarbon group in the above explanation of [amine skeleton] may be used, and the hydrocarbon group may be separated by an oxygen atom and/or a sulfur atom, or a carbon atom, a nitrogen atom, and a hydrogen atom. It may consist only of atoms.
  • L 2 may be, for example, a saturated or unsaturated (eg saturated) aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 2 aromatic hydrocarbon rings. It is preferable that L 2 is a cyclic group having both a ring (for example, an aromatic ring) and a chain structure (for example, a linear structure, ether oxygen, thioether sulfur), and specific examples include 1,3-phenylenebisalkylene. group, 1,4-phenylenebisalkylene group, diphenyletherdiyl group, diphenylthioetherdiyl group, and the like.
  • the number of carbon atoms in L 2 may be 2 or more, 3 or more, 4 or more, 6 or more, 8 or more, 10 or more, or 12 or more.
  • the number of carbon atoms in L2 may be 20 or less, 18 or less, 16 or less, 14 or less, 12 or less, 10 or less, 8 or less, 6 or less, 4 or less, or 3 or less.
  • p is an integer of 0 to 2
  • q is an integer of 0 to 2
  • p+q is 2.
  • p may be greater than or equal to 1, for example 2.
  • u is an integer of 1 or more and 3 or less. u is 1, 2 or 3, for example 2 or 3.
  • the sum of p and u is 1 or more, that is, amine modified example 2 has one or more -X N -R n .
  • the sum of all p's and u's may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more (the sum of all q's may be 0).
  • the sum of p and u may be 5 or less, 4 or less, 3 or less, or 2 or less.
  • the amine modified product may be a synthetic wax derived from animal or vegetable oils.
  • Synthetic waxes may be obtained by condensing fatty acids derived from animal or vegetable oils and aliphatic amines or amines containing aromatics. Examples of synthetic waxes include hydroxy fatty acid amide compounds, palmitic acid amide compounds, octadecanoic acid amide compounds, stearic acid amide compounds, arachidic acid amide compounds, behenic acid amide compounds, lignoceric acid amide compounds, oleic acid amide compounds, and linoleic acid amide compounds.
  • fatty acid amide compounds such as ⁇ -linolenic acid amide compounds, ⁇ -linolenic acid amide compounds, arachidonic acid amide compounds, icosapentaenoic acid amide compounds, and docosahexaenoic acid amide compounds.
  • Methods for producing amine modified products include, but are not limited to, a method in which various amines are synthesized by reacting an R group-containing carboxylic acid in the presence of a condensing agent if necessary; Examples include methods of synthesis by reacting acid chlorides, acid anhydrides, isocyanates, and the like.
  • the condensing agent may be a known condensing agent, such as DCC, EDCI, CDI, BOP, COMU, DMT-MM, DPPA, Py-Bop, and the like.
  • the amount of the liquid repellent compound is 0.01% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more in the processing agent. , 30% by weight or more.
  • the amount of the liquid repellent compound is 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, or 3% by weight in the processing agent. % or less.
  • the repellent in the present disclosure may include supercritical carbon dioxide.
  • Supercritical carbon dioxide refers to carbon dioxide placed at a temperature and pressure exceeding the critical temperature (31.1° C.) and critical pressure (7.38 MPa).
  • the supercritical carbon dioxide in the repellent functions as a treatment medium, and the repellent containing supercritical carbon dioxide is used as a treatment agent for treating the fiber base material.
  • Supercritical carbon dioxide is in a fluid state that cannot be said to belong to either the gas or liquid phase, and has excellent solubility for various components and fluidity that allows it to easily penetrate into the fine details of textile products.
  • the repellent agent (treatment agent) in the disclosure can impart good liquid repellency to textile products.
  • the repellent in the present disclosure may include a liquid medium.
  • the liquid medium may be water, an organic solvent, or a mixture of water and an organic solvent. Since the repellent in the present disclosure uses supercritical carbon dioxide as a processing medium, the amount of liquid medium in the repellent may be small, and the repellent does not need to contain a liquid medium.
  • organic solvents examples include esters (for example, esters having 2 to 40 carbon atoms, specifically ethyl acetate, butyl acetate), ketones (for example, ketones having 2 to 40 carbon atoms, specifically methyl ethyl ketone, diisobutyl ketones), alcohols (for example, alcohols having 1 to 40 carbon atoms, specifically isopropyl alcohol), aromatic solvents (for example, toluene and xylene), petroleum solvents (for example, alkanes having 5 to 10 carbon atoms, Specifically, naphtha, kerosene).
  • the organic solvent is a water-soluble organic solvent.
  • the water-soluble organic solvent may contain a compound having at least one hydroxy group (for example, alcohol, polyhydric alcohol such as glycol solvent, ether form of polyhydric alcohol (e.g. monoether form), etc.). . These may be used alone or in combination of two or more.
  • a compound having at least one hydroxy group for example, alcohol, polyhydric alcohol such as glycol solvent, ether form of polyhydric alcohol (e.g. monoether form), etc..
  • the amount of the liquid medium is 0.1 parts by weight or more, 0.5 parts by weight or more, 1 part by weight or more, 3 parts by weight per 1 part by weight (or 10 parts by weight, or 100 parts by weight) of the liquid repellent compound.
  • the amount may be 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, or 50 parts by weight or more.
  • the amount of the liquid medium is 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight per 1 part by weight (or 10 parts by weight, or 100 parts by weight of the liquid repellent compound).
  • parts by weight or less 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, 1 part by weight or less, 0.5 parts by weight or less, It may be 0.1 parts by weight or less, or 0, preferably 40 parts by weight or less, more preferably 10 parts by weight or less.
  • the amount of the liquid medium may be 0.000001 mol/L or more, 0.000003 mol/L or more, 0.000005 mol/L or more, or 0.00001 mol/L or more in the treatment agent.
  • the amount of the liquid medium is 0.001 mol/L or less, 0.0005 mol/L or less, 0.0001 mol/L or less, 0.00005 mol/L or less, 0.00001 mol/L or less, or 0 in the processing agent. It is well, preferably 0.0001 mol/L or less.
  • the amount of water is 0.1 parts by weight or more, 0.5 parts by weight or more, 1 part by weight or more, 3 parts by weight or more with respect to 1 part by weight (or 10 parts by weight, or 100 parts by weight) of the liquid repellent compound. , 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, or 50 parts by weight or more.
  • the amount of the organic solvent is 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight per 1 part by weight (or 10 parts by weight, or 100 parts by weight) of the liquid repellent compound.
  • parts by weight or less 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, 1 part by weight or less, 0.5 parts by weight or less, It may be 0.1 parts by weight or less, or 0, preferably 40 parts by weight or less, more preferably 10 parts by weight or less.
  • the amount of water in the treatment agent may be 0.000001 mol/L or more, 0.000003 mol/L or more, 0.000005 mol/L or more, or 0.00001 mol/L or more.
  • the amount of water in the treatment agent may be 0.001 mol/L or less, 0.0005 mol/L or less, 0.0001 mol/L or less, 0.00005 mol/L or less, 0.00001 mol/L or less, or 0. , preferably 0.0001 mol/L or less.
  • the amount of the organic solvent is 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 20 parts by weight with respect to 1 part by weight (or 10 parts by weight, or 100 parts by weight) of the liquid repellent compound. parts by weight or more, 30 parts by weight or more, 40 parts by weight or more, or 50 parts by weight or more.
  • the amount of the organic solvent is 200 parts by weight or less, 175 parts by weight or less, 150 parts by weight or less, 125 parts by weight or less, 100 parts by weight per 1 part by weight (or 10 parts by weight, or 100 parts by weight) of the liquid repellent compound.
  • the amount is more preferably 10 parts by weight or less.
  • the amount of the organic solvent may be 0.000001 mol/L or more, 0.000003 mol/L or more, 0.000005 mol/L or more, or 0.00001 mol/L or more in the treatment agent.
  • the amount of organic solvent in the treatment agent is 0.001 mol/L or less, 0.0005 mol/L or less, 0.0001 mol/L or less, 0.00005 mol/L or less, 0.00001 mol/L or less, or 0. It is well, preferably 0.0001 mol/L or less.
  • the repellent may include a surfactant.
  • the surfactant may include one or more surfactants selected from nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. Since the repellent in the present disclosure uses supercritical carbon dioxide as a processing medium, the components can be well dispersed, so the amount of surfactant in the repellent may be small, and the repellent does not contain a surfactant. You can.
  • Nonionic surfactant examples include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides.
  • An example of an ether is a compound having an oxyalkylene group (preferably a polyoxyethylene group).
  • esters are esters of alcohols and fatty acids.
  • alcohols are monovalent to hexavalent (especially divalent to pentavalent) alcohols having 1 to 50 carbon atoms (especially 10 to 30 carbon atoms) (eg, aliphatic alcohols).
  • fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.
  • an ester ether is a compound obtained by adding alkylene oxide (especially ethylene oxide) to an ester of alcohol and fatty acid.
  • alkylene oxide especially ethylene oxide
  • examples of alcohols are monovalent to hexavalent (especially divalent to pentavalent) alcohols having 1 to 50 carbon atoms (especially 3 to 30 carbon atoms) (eg, aliphatic alcohols).
  • Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.
  • alkanolamides are formed from fatty acids and alkanolamines.
  • the alkanolamide may be a monoalkanolamide or a dialkanolamide.
  • fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.
  • the alkanolamines may be alkanols having 2 to 50, especially 5 to 30 carbon atoms and having 1 to 3 amino groups and 1 to 5 hydroxyl groups.
  • the polyhydric alcohol may be a divalent to pentavalent alcohol having 10 to 30 carbon atoms.
  • the amine oxide may be an oxide (eg, having 5 to 50 carbon atoms) of an amine (secondary amine or preferably tertiary amine).
  • the nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene group).
  • the alkylene group in the oxyalkylene group preferably has 2 to 10 carbon atoms.
  • the number of oxyalkylene groups in the nonionic surfactant molecule is generally preferably from 2 to 100.
  • the nonionic surfactant is selected from the group consisting of ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides, and is preferably a nonionic surfactant having an oxyalkylene group.
  • Nonionic surfactants include alkylene oxide adducts of linear and/or branched aliphatic (saturated and/or unsaturated) groups, linear and/or branched fatty acids (saturated and/or unsaturated) polyalkylene glycol esters, polyoxyethylene (POE)/polyoxypropylene (POP) copolymers (random copolymers or block copolymers), alkylene oxide adducts of acetylene glycol, and the like.
  • POE polyoxyethylene
  • POP polyoxypropylene
  • the structure of the alkylene oxide addition part and polyalkylene glycol part is polyoxyethylene (POE), polyoxypropylene (POP), or POE/POP copolymer (even if it is a random copolymer or a block copolymer). ) is preferred.
  • the nonionic surfactant preferably has a structure that does not contain an aromatic group due to environmental issues (biodegradability, endocrine disruptors, etc.).
  • Nonionic surfactants have the formula: R 1 O-(CH 2 CH 2 O) p -(R 2 O) q - R 3
  • R 1 is an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or an acyl group
  • Each of R 2 is independently the same or different and is an alkylene group having 3 or more carbon atoms (for example, 3 to 10)
  • R 3 is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an alkenyl group having 2 to 22 carbon atoms
  • p is a number of 2 or more
  • q is 0 or a number of 1 or more.
  • It may be a compound represented by
  • R 1 preferably has 8 to 20 carbon atoms, particularly 10 to 18 carbon atoms. Preferred specific examples of R 1 include lauryl group, tridecyl group, and oleyl group.
  • R 2 are propylene and butylene.
  • p may be a number greater than or equal to 3 (eg, 5 to 200).
  • q may be a number greater than or equal to 2 (eg, 5 to 200). That is, -(R 2 O) q - may form a polyoxyalkylene chain.
  • the nonionic surfactant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) in the center.
  • a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (particularly a polyoxyalkylene chain) in the center.
  • the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, a styrene chain, and among them, an oxypropylene chain is preferred.
  • nonionic surfactants include ethylene oxide and hexylphenol, isooctatylphenol, hexadecanol, oleic acid, alkane (C 12 -C 16 ) thiols, sorbitan monofatty acids (C 7 -C 19 ) or alkyls. (C 12 -C 18 )condensation products with amines and the like are included.
  • the proportion of polyoxyethylene blocks can be from 5 to 80% by weight, for example from 30 to 75% by weight, in particular from 40 to 70% by weight, based on the molecular weight of the nonionic surfactant (copolymer).
  • the average molecular weight of the nonionic surfactant is generally from 300 to 5,000, for example from 500 to 3,000.
  • the nonionic surfactant may be a mixture of a compound with an HLB (hydrophilic-hydrophobic balance) of less than 15 (especially 5 or less) and a compound with an HLB of 15 or more.
  • An example of a compound with an HLB of less than 15 is sorbitan fatty acid ester.
  • An example of a compound having an HLB of 15 or more is polyoxyethylene alkyl ether.
  • the weight ratio of the compound with an HLB of less than 15 to the compound with an HLB of 15 or more may be from 90:10 to 20:80, for example from 85:15 to 55:45.
  • the nonionic surfactant may be used alone or in a mixture of two or more.
  • the cationic surfactant is preferably a compound that does not have an amide group.
  • the cationic surfactant may be an amine salt, a quaternary ammonium salt, or an oxyethylene addition type ammonium salt.
  • cationic surfactants include, but are not limited to, alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt type surfactants such as imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, Examples include quaternary ammonium salt type surfactants such as alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzalkonium chloride, and benzethonium chloride.
  • Preferred examples of cationic surfactants are: R 21 -N + (-R 22 ) (-R 23 ) (-R 24 ) X - [wherein R 21 , R 22 , R 23 and R 24 are hydrocarbon groups having 1 to 40 carbon atoms, X is an anionic group. ] It is a compound of Specific examples of R 21 , R 22 , R 23 and -R 24 are alkyl groups (eg, methyl group, butyl group, stearyl group, palmityl group). Specific examples of X are halogen (eg, chlorine), acid (eg, hydrochloric acid, acetic acid).
  • the cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (alkyl having 4 to 40 carbon atoms).
  • the cationic surfactant is an ammonium salt.
  • cationic surfactants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, methyldodecyl Included are di(hydropolyoxyethylene) ammonium chloride, benzyldodecyl di(hydropolyoxyethylene) ammonium chloride, and N-[2-(diethylamino)ethyl]oleamide hydrochloride.
  • anionic surfactant examples include alkyl ether sulfates, alkyl sulfates, alkenyl ether sulfates, alkenyl sulfates, olefin sulfonates, alkanesulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carbonates.
  • anionic surfactants include acid salts, ⁇ -sulfone fatty acid salts, N-acylamino acid surfactants, phosphate mono- or diester surfactants, and sulfosuccinate esters.
  • ampholytic surfactant examples include alanines, imidazolinium betaines, amidobetaines, acetic acid betaine, etc. Specifically, lauryl betaine, stearyl betaine, laurylcarboxymethylhydroxyethylimidazolinium betaine, Examples include lauryldimethylaminoacetic acid betaine and fatty acid amidopropyldimethylaminoacetic acid betaine.
  • the surfactant may be one type or a combination of two or more of nonionic surfactants, cationic surfactants, and amphoteric surfactants.
  • the amount of surfactant is 0.01 parts by weight or more, 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight, based on 100 parts by weight of the liquid repellent compound.
  • the amount may be 15 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, or 300 parts by weight or more.
  • the amount of surfactant is 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 30 parts by weight, based on 100 parts by weight of the liquid repellent compound.
  • parts by weight or less 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, 1 part by weight or less, 0.5 parts by weight or less, 0.3 parts by weight or less, 0.1 parts by weight or less, or It may be 0, preferably 10 parts by weight or less, more preferably 1 part by weight or less. It may be.
  • the repellent in the present disclosure may include silicone (polyorganosiloxane). By containing silicone, it can have good texture and durability in addition to good liquid repellency.
  • silicone known silicones can be used, and examples of silicones include polydimethylsiloxane and modified silicones (amino-modified silicones, epoxy-modified silicones, carboxy-modified silicones, methylhydrogen silicones, etc.).
  • the silicone may be a silicone wax having wax-like properties. These may be used alone or in combination of two or more.
  • the weight average molecular weight of the silicone may be 300 or more, 1000 or more, 10000 or more, or 50000 or more.
  • the weight average molecular weight of the silicone may be 500,000 or less, 2,500,000 or less, 100,000 or less, or 50,000 or less.
  • the amount of silicone is 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight based on 100 parts by weight of the liquid repellent compound. parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, or 300 parts by weight or more.
  • the amount of silicone is 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, based on 100 parts by weight of the liquid repellent compound. , 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.
  • the repellent in the present disclosure may include wax. Including wax can impart good liquid repellency to the base material.
  • wax examples include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyolefin wax (polyethylene wax, polypropylene wax, etc.), oxidized polyolefin wax, silicone wax, animal and vegetable wax, and mineral wax. Paraffin wax is preferred.
  • compounds constituting the wax include normal alkanes (e.g., tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane) Contane, hexatriacontane), normal alkenes (e.g., tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, tritriacontane, tetratriacont
  • the number of carbon atoms in the compound constituting the wax is preferably 20 to 60, for example 25 to 45.
  • the molecular weight of the wax may be from 200 to 2000, for example from 250 to 1500, from 300 to 1000. These may be used alone or in combination of two or more.
  • the melting point of the wax may be 50°C or higher, 55°C or higher, 60°C or higher, 65°C or higher, or 70°C or higher, preferably 55°C or higher, more preferably 60°C or higher.
  • the melting point of wax is measured in accordance with JIS K 2235-1991.
  • the amount of wax is 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight based on 100 parts by weight of the liquid repellent compound. parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, or 300 parts by weight or more.
  • the amount of wax is 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, based on 100 parts by weight of the liquid repellent compound. , 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.
  • the repellent may include an organic acid.
  • organic acid known organic acids can be used.
  • Preferred examples of the organic acid include carboxylic acid, sulfonic acid, and sulfinic acid, with carboxylic acid being particularly preferred.
  • carboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, glutaric acid, adipic acid, malic acid, citric acid, etc., with formic acid or acetic acid being particularly preferred.
  • one type of organic acid may be used, or two or more types may be used in combination.
  • formic acid and acetic acid may be used in combination.
  • the amount of organic acid is 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, based on 100 parts by weight of the liquid repellent compound.
  • the amount may be at least 50 parts by weight, at least 100 parts by weight, at least 200 parts by weight, or at least 300 parts by weight.
  • the amount of organic acid is 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 40 parts by weight, based on 100 parts by weight of the liquid repellent compound.
  • the amount may be 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.
  • the amount of organic acid may be adjusted so that the pH of the repellent is 3 to 10, for example 5 to 9, particularly 6 to 8.
  • the repellent may be acidic (pH 7 or less, for example 6 or less).
  • the repellent may include a curing agent (active hydrogen-reactive compound or active hydrogen-containing compound).
  • the curing agent (crosslinking agent) in the repellent can cure the liquid repellent compound well.
  • the curing agent may be an active hydrogen-reactive compound or an active hydrogen-containing compound that reacts with the active hydrogen or active hydrogen-reactive group of the liquid-repellent compound.
  • active hydrogen-reactive compounds are isocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds and hydrazide compounds.
  • active hydrogen-containing compounds are hydroxyl group-containing compounds, amino group-containing compounds and carboxyl group-containing compounds, ketone group-containing compounds, hydrazide compounds and melamine compounds.
  • the curing agent may include an isocyanate compound.
  • the isocyanate compound may be a polyisocyanate compound.
  • a polyisocyanate compound is a compound having two or more isocyanate groups in one molecule.
  • Polyisocyanate compounds act as crosslinking agents. Examples of polyisocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, aromatic polyisocyanates, and derivatives of these polyisocyanates.
  • the isocyanate compound may be a blocked isocyanate compound (eg, a blocked polyisocyanate compound).
  • a blocked isocyanate compound is a compound in which the isocyanate group of an isocyanate compound is masked with a blocking agent to suppress the reaction.
  • aliphatic polyisocyanates are trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene Diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, aliphatic diisocyanate of 2,6-diisocyanatomethylcaproate, and lysine ester triisocyanate, 1,4,8-triisocyanate Octane, 1,6,11-triisocyanatooundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, 2,5,7-trimethyl-1,8-diisocyanato -5-isocyanatomethyloct
  • alicyclic polyisocyanates examples include alicyclic diisocyanates and alicyclic triisocyanates. Specific examples of the alicyclic polyisocyanate are 1,3-cyclopentene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), and 1,3,5-triisocyanatocyclohexane. These may be used alone or in combination of two or more.
  • araliphatic polyisocyanates examples include araliphatic diisocyanates and araliphatic triisocyanates.
  • Specific examples of araliphatic polyisocyanates include 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene (tetramethyl xylylene diisocyanate) or a mixture thereof, 1,3,5-triisocyanatomethylbenzene. These may be used alone or in combination of two or more.
  • aromatic polyisocyanates are aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates.
  • aromatic polyisocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate, or mixtures thereof.
  • triphenylmethane-4,4',4''-triisocyanate triphenylmethane-4,4',4''-triisocyanate
  • 4,4'-diphenylmethane-2,2',5,5' - Tetraisocyanate etc.
  • polyisocyanate derivative examples include various derivatives of the polyisocyanate compounds described above, such as dimer, trimer, biuret, allophanate, carbodiimide, uretdione, uretoimine, isocyanurate, and iminooxadiazinedione. These may be used alone or in combination of two or more.
  • polyisocyanates can be used alone or in combination of two or more.
  • a blocked polyisocyanate compound blocked isocyanate
  • blocked isocyanate is a compound in which the isocyanate groups of a polyisocyanate compound are blocked with a blocking agent. It is preferable to use a blocked polyisocyanate compound because it is relatively stable even in a solution and can be used in the same solution as the repellent.
  • the blocking agent blocks free isocyanate groups.
  • the blocked polyisocyanate compound is heated to, for example, 100° C. or higher, for example, 130° C. or higher, the isocyanate groups are regenerated and can easily react with hydroxyl groups.
  • blocking agents include phenolic compounds, lactam compounds, aliphatic alcohol compounds, oxime compounds, and the like.
  • Polyisocyanate compounds can be used alone or in combination of two or more.
  • An epoxy compound is a compound having an epoxy group.
  • examples of epoxy compounds are epoxy compounds having polyoxyalkylene groups, such as polyglycerol polyglycidyl ether and polypropylene glycol diglycidyl ether; and sorbitol polyglycidyl ether.
  • a chloromethyl group-containing compound is a compound having a chloromethyl group.
  • An example of a chloromethyl group-containing compound is chloromethyl polystyrene.
  • a carboxyl group-containing compound is a compound having a carboxyl group. Examples of carboxyl group-containing compounds are (poly)acrylic acid, (poly)methacrylic acid, and the like.
  • ketone group-containing compound examples include (poly)diacetone acrylamide, diacetone alcohol, and the like.
  • hydrazide compound include hydrazine, carbohydrazide, adipic acid hydrazide, and the like.
  • melamine compound examples include melamine resin, methyl etherified melamine resin, and the like.
  • the amount of the curing agent is 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, based on 100 parts by weight of the liquid repellent compound.
  • the amount may be at least 50 parts by weight, at least 100 parts by weight, at least 200 parts by weight, or at least 300 parts by weight.
  • the amount of the curing agent is 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, 40 parts by weight, based on 100 parts by weight of the liquid repellent compound.
  • the amount may be 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.
  • the repellent may contain components other than the above components.
  • other components include water and/or oil repellents, antislip agents, antistatic agents, preservatives, ultraviolet absorbers, antibacterial agents, deodorants, perfumes, and the like. These may be used alone or in combination of two or more.
  • other ingredients include texture adjusters, softeners, antibacterial agents, flame retardants, paint fixing agents, anti-wrinkle agents, drying rate regulators, crosslinking agents, film forming aids, compatibilizers, and anti-freezing agents.
  • viscosity modifiers such as polyvinylpyrrolidone, polymer dispersant, stain remover, scum dispersant, 4,4-bis(2-sulfostyryl)biphenyl disodium (Ciba Specialty) Fluorescent brighteners such as Chinopal CBS-X (manufactured by Chemicals), dye fixatives, antifading agents such as 1,4-bis(3-aminopropyl)piperazine, stain removers, and cellulase, amylase, and protease as fiber surface modifiers.
  • dye transfer prevention agent such as polyvinylpyrrolidone, polymer dispersant, stain remover, scum dispersant, 4,4-bis(2-sulfostyryl)biphenyl disodium (Ciba Specialty) Fluorescent brighteners such as Chinopal CBS-X (manufactured by Chemicals), dye fixatives, antifading agents such as 1,4-bis(3
  • enzymes such as lipase and keratinase, foam inhibitors, and silk protein powders that can impart the texture and functions of silk such as moisture absorption and release properties, their surface modified products, and emulsified dispersions.
  • antistatic agents examples include quaternary ammonium salts, pyridinium salts, cationic antistatic agents having cationic functional groups such as primary, secondary, and tertiary amino groups; sulfonate salts and sulfate ester salts; Anionic antistatic agents having anionic functional groups such as phosphonates and phosphate ester salts; amphoteric antistatic agents such as alkyl betaines and derivatives thereof, imidazolines and derivatives thereof, alanine and derivatives thereof, amino alcohols and derivatives thereof , nonionic antistatic agents such as glycerin and its derivatives, polyethylene glycol and its derivatives, and the like.
  • An ion conductive polymer obtained by polymerizing or copolymerizing monomers having ion conductive groups of cation type, anion type, or amphoteric type may be used. These may be used alone or in combination of two or more.
  • Preservatives can be used mainly to enhance preservative power and sterilizing power, and to maintain preservative properties during long-term storage.
  • the preservative include isothiazolone organic sulfur compounds, benzisothiazolone organic sulfur compounds, benzoic acids, 2-bromo-2-nitro-1,3-propanediol, and the like.
  • a UV absorber is a drug that has the effect of protecting against UV rays, and is a component that absorbs UV rays and converts them into infrared rays, visible rays, etc. and releases them.
  • Examples of the ultraviolet absorber include aminobenzoic acid derivatives, salicylic acid derivatives, cinnamic acid derivatives, benzophenone derivatives, azole compounds, and 4-t-butyl-4'-methoxybenzoylmethane.
  • Antibacterial agents are components that have the effect of suppressing the growth of bacteria on fibers and further suppressing the generation of unpleasant odors derived from decomposition products of microorganisms.
  • antibacterial agents include cationic bactericides such as quaternary ammonium salts, bis-(2-pyridylthio-1-oxide) zinc, polyhexamethylene biguanidine hydrochloride, 8-oxyquinoline, polylysine, and the like.
  • Deodorants include cluster dextrin, methyl- ⁇ -cyclodextrin, 2-hydroxypropyl- ⁇ -cyclodextrin, monoacetyl- ⁇ -cyclodextrin, acylamidopropyldimethylamine oxide, aminocarboxylic acid metal complexes (International Publication Zinc complex of trisodium methylglycine diacetate described in No. 2012/090580), and the like.
  • Each amount or total amount of other components is 0.1 parts by weight or more, 1 part by weight or more, 3 parts by weight or more, 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight based on 100 parts by weight of the liquid repellent compound. parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, 100 parts by weight or more, 200 parts by weight or more, or 300 parts by weight or more. Each amount or total amount of other components is 500 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 100 parts by weight or less, 75 parts by weight or less, 50 parts by weight or less, based on 100 parts by weight of the liquid repellent compound. , 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, and 5 parts by weight or less.
  • the method for producing liquid-repellent fibers in the present disclosure includes a fiber treatment step of treating a fiber base material with a repellent containing a liquid-repellent compound using supercritical carbon dioxide as a treatment medium.
  • the repellent agent (processing agent) for treating the fiber base material contains a liquid repellent compound and supercritical carbon dioxide. Through the treatment, the liquid repellent compound, which is an active ingredient of the repellent, penetrates into the interior of the substrate and/or adheres to the surface of the substrate.
  • the repellent of the present disclosure may further include a water and/or oil repellent, an anti-slip agent, an antistatic agent, a texture control agent, a softener, an antibacterial agent, a flame retardant, a paint fixing agent, an anti-wrinkle agent, and a drying agent.
  • a water and/or oil repellent used in combination with various additives such as speed regulators, crosslinking agents, film forming aids, compatibilizers, antifreeze agents, viscosity regulators, ultraviolet absorbers, antioxidants, pH regulators, insect repellents, antifoaming agents, etc. It is also possible to do so.
  • various additives may be the same as those explained in the section of "other components" in the water repellent composition described above.
  • the concentration of the repellent in the treatment agent brought into contact with the substrate may be changed as appropriate depending on the use, but may be 0.01 to 10% by weight, for example 0.05 to 5% by weight.
  • the processing temperature in the processing container is set to 31.1°C or higher (preferably 40°C or higher), which is the critical temperature of carbon dioxide, and the processing pressure is set to the critical temperature of carbon dioxide. 7.38 MPa or more (preferably 10 MPa or more), supercritical carbon dioxide is used as a treatment medium, and the fiber base material placed in the treatment tank is treated with a repellent containing a liquid-repellent compound.
  • the processing temperature may be 31.1°C or higher, 40°C or higher, 50°C or higher, 60°C or higher, 70°C or higher, 80°C or higher, or 100°C or higher.
  • the processing temperature may be 200°C or less, 150°C or less, 120°C or less, 100°C or less, 80°C or less, or 60°C or less.
  • the treatment temperature may vary depending on the type of repellent used, treatment conditions, desired physical properties, etc.
  • the processing pressure may be 7.38 MPa or more, 8 MPa or more, 10 MPa or more, 15 MPa or more, 20 MPa or more, or 25 MPa or more.
  • the processing pressure may be 100 MPa or less, 75 MPa or less, 50 MPa or less, 30 MPa or less, 25 MPa or less, or 20 MPa or less.
  • the processing pressure may vary depending on the type of repellent used, processing conditions, desired physical properties, etc.
  • the processing time may be 10 seconds or more, 1 minute or more, 3 minutes or more, 5 minutes or more, 10 minutes or more, 20 minutes or more, or 30 minutes or more.
  • the treatment time may be 300 minutes or less, 240 minutes or less, 180 minutes or less, 120 minutes or less, 60 minutes or less, 30 minutes or less, 15 minutes or less, or 5 minutes or less.
  • the treatment temperature may vary depending on the type of repellent used, treatment conditions, desired physical properties, etc.
  • fiber base material examples include animal and plant natural fibers such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, and rayon and acetate.
  • synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, and rayon and acetate.
  • Semi-synthetic fibers, glass fibers, carbon fibers, inorganic fibers such as asbestos fibers, or mixed fibers thereof can be used.
  • Textile products include woven, knitted and non-woven fabrics, cloth in the form of clothing and carpets; Processing may be performed.
  • suitable fibrous substrates in this disclosure include polyester or polyester blend fibers.
  • a paper product may be used as the fiber base material.
  • paper products include bleached or unbleached chemical pulps such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulps such as ground wood pulp, mechanical pulp or thermomechanical pulp, used newspapers, used magazines, and used cardboard.
  • examples include paper made of waste paper pulp such as deinked waste paper, containers made of paper, and molded objects made of paper.
  • paper products include packaging paper, gypsum board base paper, coated base paper, medium-quality paper, general liner and core, neutral pure white roll paper, neutral liner, rust-proof liner and metal interleaving paper, kraft paper, medium-quality paper, These include neutral printing writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper, neutral information paper, molded paper (mold container), etc.
  • the textile may be pretreated prior to treatment with the repellent of the present disclosure.
  • pre-treating the textile product it is possible to impart excellent fastness to the textile product after being treated with a repellent.
  • pretreatment for textile products examples include cationization treatment such as reaction with reactive quaternary ammonium salts, anionization treatment such as sulfonation, carboxylation, and phosphorylation, acetylation treatment after anionization treatment, and benzoylation treatment. treatment, carboxymethylation treatment, grafting treatment, tannic acid treatment, polymer coating treatment, etc.
  • the method for pre-treating textile products is not limited, but textile products can be pre-treated by conventionally known methods.
  • the pretreatment liquid may be dispersed and diluted in an organic solvent or water if necessary, and then applied to the surface of the textile product by a known method such as dip coating, spray coating, foam coating, etc., and then dried. .
  • the pH, temperature, etc. of the pretreatment liquid may be adjusted depending on the degree of treatment desired.
  • a method for pre-treating textile products a method for pre-treating textile products with a hydrocarbon water repellent will be described in detail.
  • the pretreatment method for textile products involves treating the fibers with a monovalent group represented by -SO 3 M 1 (wherein M 1 represents a monovalent cation), -COOM 2 (wherein M 2 represents a monovalent cation), and -COOM 2 (wherein M 2 represents a monovalent cation). (representing a cation), and -O-P(O)(OX 1 )(OX 2 ) (wherein, X 1 and X 2 are each independently a hydrogen atom or a carbon number of 1 to 22
  • the method may include a step of imparting one or more functional groups (hereinafter sometimes referred to as "specific functional groups") selected from the group consisting of monovalent groups represented by alkyl groups.
  • Examples of M 1 include H, K, Na, or ammonium ion which may have a substituent.
  • M 2 include H, K, Na, or ammonium ion which may have a substituent.
  • X 1 or X 2 is an alkyl group, it is preferably an alkyl group having 1 to 22 carbon atoms, more preferably an alkyl group having 4 to 12 carbon atoms.
  • the fiber containing the above specific functional group (hereinafter sometimes referred to as "functional group-containing fiber") can be prepared, for example, by the following method.
  • a compound having the above specific functional group is attached to the fiber material. Note that the attachment of the compound may be such that part of the compound and part of the fiber are chemically bonded to each other as long as a sufficient amount of the specific functional group remains.
  • (ii) Prepare a fiber in which the above specific functional group is directly introduced into the material constituting the fiber.
  • a functional group-containing fiber can be obtained by a functional group introduction step of treating the fiber material with a pretreatment liquid containing one or more of the above-mentioned specific functional group-containing compounds.
  • the materials used for the fiber materials including natural fibers such as cotton, hemp, silk, and wool, semi-synthetic fibers such as rayon and acetate, synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, and polypropylene, and synthetic fibers such as these. Examples include composite fibers, blended fibers, etc.
  • the form of the fibrous material may be any form such as fiber (tow, sliver, etc.), yarn, knitted fabric (including interwoven fabric), woven fabric (including interwoven fabric), nonwoven fabric, etc.
  • a textile material containing polyamide and polyester as raw materials, and in particular, nylon such as nylon 6, nylon 6,6, polyethylene terephthalate, etc. It is preferable to use polyesters such as (PET), polytrimethyl terephthalate, and polylactic acid, and mixed fibers containing these.
  • a phenolic polymer can be used as the compound having -SO 3 M 1 .
  • examples of such phenolic polymers include those containing one or more compounds represented by the following general formula.
  • X 2 represents -SO 3 M 3 (in the formula, M 3 represents a monovalent cation) or a group represented by the following general formula, and n is an integer of 20 to 3000.
  • M 4 represents a monovalent cation.
  • M 3 examples include H, K, Na, or ammonium ion which may have a substituent.
  • Examples of M 4 include H, K, Na, or ammonium ion which may have a substituent.
  • the compound represented by the above general formula may be, for example, a formalin condensate of phenolsulfonic acid or a formalin condensate of sulfonated bisphenol S.
  • Examples of the compound having -COOM 2 include polycarboxylic acid polymers.
  • polycarboxylic acid polymer for example, a polymer synthesized by a conventionally known radical polymerization method using acrylic acid, methacrylic acid, maleic acid, etc. as a monomer, or a commercially available polymer can be used.
  • Examples of the method for producing polycarboxylic acid-based polymers include a method in which a radical polymerization initiator is added to an aqueous solution of the monomer and/or its salt, and the mixture is heated and reacted at 30 to 150° C. for 2 to 5 hours. At this time, an alcohol such as methanol, ethanol, isopropyl alcohol, or an aqueous solvent such as acetone may be added to the aqueous solution of the monomer and/or its salt.
  • a radical polymerization initiator is added to an aqueous solution of the monomer and/or its salt, and the mixture is heated and reacted at 30 to 150° C. for 2 to 5 hours.
  • an alcohol such as methanol, ethanol, isopropyl alcohol, or an aqueous solvent such as acetone may be added to the aqueous solution of the monomer and/or its salt.
  • radical polymerization initiators examples include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, redox polymerization initiators made from combinations of persulfates and sodium bisulfite, hydrogen peroxide, and water-soluble azo-based initiators. Examples include polymerization initiators. These radical polymerization initiators may be used alone or in combination of two or more. Furthermore, during radical polymerization, a chain transfer agent (for example, octyl thioglycolate) may be added for the purpose of adjusting the degree of polymerization.
  • a chain transfer agent for example, octyl thioglycolate
  • copolymerizable monomers can be used for radical polymerization.
  • copolymerizable monomers include vinyl monomers such as ethylene, vinyl chloride, and vinyl acetate, acrylamide, acrylates, and methacrylates.
  • the acrylates and methacrylates preferably have a hydrocarbon group having 1 to 3 carbon atoms which may have a substituent such as a hydroxyl group.
  • acrylates or methacrylates examples include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, propyl acrylate, propyl methacrylate, and the like. These copolymerizable monomers may be used alone or in combination of two or more.
  • the carboxyl group in the polycarboxylic acid polymer may be free or may be neutralized with an alkali metal, an amine compound, or the like.
  • alkali metals include sodium, potassium, and lithium
  • amine compounds include ammonia, monoethanolamine, diethanolamine, triethanolamine, and the like.
  • the weight average molecular weight of the polycarboxylic acid polymer is preferably from 1,000 to 20,000, more preferably from 3,000 to 15,000, from the viewpoint of improving the water repellency of the resulting textile product.
  • polycarboxylic acid polymer As the polycarboxylic acid polymer, commercially available products such as "Neocrystal 770" (manufactured by NICCA Chemical Co., Ltd., trade name) and "Ceropol PC-300” (manufactured by Sanyo Chemical Industries, Ltd., trade name) can be used. .
  • Examples of the compound having -OP(O)(OX 1 )(OX 2 ) include phosphoric ester compounds represented by the following general formula. [In the formula, X 1 or X 2 has the same meaning as above, and X 3 represents an alkyl group having 1 to 22 carbon atoms. ]
  • phosphoric acid ester compound phosphoric acid monoesters, diesters, and triesters in which the alkyl ester moiety is an alkyl group having 1 to 22 carbon atoms, and mixtures thereof can be used.
  • lauryl phosphate and decyl phosphate From the viewpoint of improving the water repellency of the resulting textile product, it is preferable to use lauryl phosphate and decyl phosphate.
  • phosphate ester compound for example, commercially available products such as "Phosphanol ML-200" (product name, manufactured by Toho Chemical Industry Co., Ltd.) can be used.
  • the pretreatment liquid containing one or more of the compounds having the above-mentioned specific functional groups can be, for example, an aqueous solution of the above-mentioned compounds. Further, the pretreatment liquid may contain an acid, an alkali, a surfactant, a chelating agent, and the like.
  • Examples of methods for treating the fiber material with the above pretreatment liquid include padding treatment, dipping treatment, spray treatment, and coating treatment.
  • the padding process is described, for example, on pages 396-397 of Fiber Dyeing Processing Dictionary (1960, published by Nikkan Kogyo Shimbun) and pages 256-260 of Color Dyeing Chemistry III (1975, published by Jikkyo Publishing Co., Ltd.)
  • One example is a method using a padding device.
  • the coating treatment for example, a method using a coating machine described on pages 473 to 477 of Dyeing and Finishing Equipment General Directory (1981, published by Senshi-sha) can be mentioned.
  • Examples of the dipping treatment include a method using a batch dyeing machine as described in the Dyeing and Finishing Equipment Directory (1981, Sensensha Publishing), pages 196 to 247; A dyeing machine, a wince dyeing machine, a washer dyeing machine, a cheese dyeing machine, etc. can be used.
  • Examples of the spray treatment include a method using an air spray method in which the treatment liquid is atomized using compressed air, and a method using a hydraulic atomization type air spray method.
  • the processing conditions such as the concentration of the processing liquid and the heat treatment after application can be appropriately adjusted in consideration of various conditions such as the purpose and performance.
  • the pretreatment liquid contains water, it is preferable to dry it to remove water after adhering it to the fiber material.
  • the drying method is not particularly limited and may be either a dry heat method or a wet heat method.
  • the drying temperature is not particularly limited either, but it may be dried at room temperature to 200° C. for 10 seconds to several days. If necessary, after drying, heat treatment may be performed at a temperature of 100 to 180° C. for about 10 seconds to 5 minutes.
  • the treatment with the pretreatment liquid may be carried out before dyeing or in the same bath as dyeing, but when performing reduction soaping, the above-mentioned specific functionalities adsorbed in the process may be Since there is a risk that the group-containing compound (for example, a phenolic polymer compound, etc.) may fall off, it is preferable to perform this after reduction soaping after dyeing.
  • the group-containing compound for example, a phenolic polymer compound, etc.
  • the treatment temperature in the dipping treatment can be 60 to 130°C.
  • Treatment time can be 5 to 60 minutes.
  • the step of introducing a functional group using a pretreatment liquid is preferably carried out in such an amount that the amount of the compound having the specific functional group deposited is 1.0 to 7.0 parts by weight based on 100 parts by weight of the fiber material. Within this range, both durable water repellency and texture can be achieved at a high level.
  • the pH of the pretreatment liquid is preferably adjusted to 3 to 5.
  • a pH adjuster such as acetic acid or malic acid can be used.
  • a salt can also be used in the pretreatment liquid in order to effectively adsorb the compound having the above-mentioned specific functional group onto the fiber material through a salting-out effect.
  • salts that can be used include sodium chloride, sodium carbonate, ammonium sulfate, and sodium sulfate.
  • the functional group introduction step using the pretreatment liquid it is preferable to remove the excessively treated compound having the specific functional group.
  • the removal method include washing with water. By sufficiently removing it, it is possible to prevent the development of water repellency from being inhibited in the subsequent water repellent treatment, and in addition, the texture of the obtained textile product is improved. Further, it is preferable that the obtained functional group-containing fiber is sufficiently dried before being brought into contact with the hydrocarbon water repellent.
  • Examples of fibers in which the above-mentioned specific functional groups are directly introduced into the material constituting the fibers include cationic dyeable polyester (CD-PET).
  • the surface zeta potential of the functional group-containing fiber is preferably -100 to -0.1 mV, more preferably -50 to -1 mV, from the viewpoint of improving the water repellency of the obtained textile product.
  • the zeta potential on the surface of the fiber can be measured, for example, with a zeta potential/particle size measuring system ELSZ-1000ZS (manufactured by Otsuka Electronics Co., Ltd.).
  • Test procedure is as follows.
  • Example 1 A polyethylene terephthalate cloth (basis weight 88 g/m2, 70 denier, gray) was cut and weighed (about 1 g). 40 mg of compound 1 was supported on the glass filter. The polyethylene terephthalate cloth and the glass filter supporting compound 1 were placed in a 10 mL processing container and set in a supercritical carbon dioxide processing device. Then, supercritical carbon dioxide at a pressure of 25 MPa was injected and processed at a temperature of 120°C for 30 minutes. After a predetermined time, the supercritical carbon dioxide was discharged to obtain a liquid-repellent fiber. The repellent adhesion rate to the cloth at this time was calculated to be 0.65% by weight.
  • Example 2 A liquid-repellent fiber was obtained in the same manner as in Example 1, except that Compound 2 was used in place of Compound 1. The rate of adhesion of the repellent to the cloth was calculated to be 0.87% by weight.
  • Example 3 A liquid-repellent fiber was obtained in the same manner as in Example 1, except that Compound 3 was used instead of Compound 1. The rate of adhesion of the repellent to the cloth was calculated to be 0.73% by weight.
  • Example 4 A liquid-repellent fiber was obtained in the same manner as in Example 1, except that Compound 4 was used in place of Compound 1. The rate of adhesion of the repellent to the cloth was calculated to be 0.62% by weight.
  • Example 5 A liquid-repellent fiber was obtained in the same manner as in Example 1, except that Compound 5 was used in place of Compound 1. The rate of adhesion of the repellent to the cloth was calculated to be 0.28% by weight.
  • Example 6 A liquid-repellent fiber was obtained in the same manner as in Example 1, except that Compound 6 was used instead of Compound 1.
  • the rate of adhesion of the repellent to the cloth was calculated to be 0.27% by weight.
  • the fiber base materials in Examples 1 to 5 and Comparative Example 1 were evaluated for water repellency.

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Abstract

L'invention a pour objet de fournir un procédé qui permet de procurer des propriétés de répulsion des liquides à des fibres, y compris dans le cas où la quantité d'eau et/ou de tensio-actif est réduite, et de préférence même dans le cas où aucune eau ni aucun tensio-actif n'est mis en œuvre. Plus précisément, l'invention concerne un procédé de fabrication de fibres dotées de propriétés de répulsion des liquides qui inclut une étape de traitement de fibres au cours de laquelle un substrat de fibres est traité à l'aide d'un répulsif contenant un composé doté de propriétés de répulsion des liquides en mettant en œuvre un dioxyde de carbone supercritique en tant que milieu de traitement. Ainsi, l'invention fournit un procédé qui permet de procurer des propriétés de répulsion des liquides à des fibres, y compris dans le cas où la quantité d'eau et/ou de tensio-actif est réduite, et de préférence même dans le cas où aucune eau ni aucun tensio-actif n'est mis en œuvre.
PCT/JP2023/033331 2022-09-14 2023-09-13 Procédé de fabrication de fibres dotées de propriétés de répulsion des liquides WO2024058204A1 (fr)

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JPS525400A (en) * 1975-06-30 1977-01-17 Allied Chem Modification of fiber by fluorocarbon
JP2002511907A (ja) * 1997-05-30 2002-04-16 マイセル・テクノロジーズ 表面処理
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
WO2001044209A1 (fr) * 1999-12-14 2001-06-21 3M Innovative Properties Company Composes de triazine et leur utilisation en tant qu'agent hydrofuge
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WO2019026593A1 (fr) * 2017-07-31 2019-02-07 ダイキン工業株式会社 Composition hydrofuge
JP2021075609A (ja) * 2019-11-07 2021-05-20 荒川化学工業株式会社 撥水剤組成物、撥水性繊維製品及び撥水性繊維製品の製造方法
JP2021155492A (ja) * 2020-03-25 2021-10-07 太陽化学株式会社 撥水剤

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