WO2024058205A1 - Repellent - Google Patents

Repellent Download PDF

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Publication number
WO2024058205A1
WO2024058205A1 PCT/JP2023/033336 JP2023033336W WO2024058205A1 WO 2024058205 A1 WO2024058205 A1 WO 2024058205A1 JP 2023033336 W JP2023033336 W JP 2023033336W WO 2024058205 A1 WO2024058205 A1 WO 2024058205A1
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Prior art keywords
weight
group
parts
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compound
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PCT/JP2023/033336
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French (fr)
Japanese (ja)
Inventor
達記 坂巻
秀幸 池内
諒 芥
昌弘 東
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ダイキン工業株式会社
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Publication of WO2024058205A1 publication Critical patent/WO2024058205A1/en

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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
    • D06M13/02—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons
    • D06M13/03—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons with unsaturated hydrocarbons, e.g. alkenes, or alkynes
    • 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
    • D06M13/02—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons
    • D06M13/03—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons with unsaturated hydrocarbons, e.g. alkenes, or alkynes
    • D06M13/07—Aromatic hydrocarbons
    • 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
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them

Definitions

  • the present disclosure relates to repellents and products (particularly textile or paper products) treated with the repellents.
  • Patent Document 1 describes an aliphatic group having 14 to 100 carbon atoms, an aromatic group having 14 to 100 carbon atoms, or an aromatic group having 14 to 100 carbon atoms via a divalent linking group to the heterocycle that is the parent skeleton. It is known that a compound having 100 heterocyclic groups bonded thereto is used as a component of a metal surface treatment agent.
  • Patent Document 1 The compound in the metal surface treatment agent described in Patent Document 1 has a heterocycle as an essential component, and there is no description or suggestion of the use of a hydrocarbon aromatic ring. Moreover, Patent Document 1 is a metal surface treatment agent, and is not intended to treat textile products or paper products.
  • An object of the present disclosure is to provide a novel repellent that contains a compound having a hydrocarbon aromatic ring as a parent skeleton and can impart liquid repellency to textile products and/or paper products.
  • A is an m-valent group obtained by removing m hydrogen atoms from a hydrocarbon aromatic ring 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 from 6 to 40 carbon atoms which may have a substituent; n is an integer of 1 or more and 3 or less, independently in each occurrence, m is an integer of 1 or more and 6 or less.
  • X 2 is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent.
  • Item 5 The repellent according to any one of items 1 to 4, which is a group represented by the following.
  • R' is a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent.
  • the repellent agent in the present disclosure can impart liquid repellency to textile products and/or paper products.
  • 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 derivative of a hydrocarbon group 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 agent in the present disclosure is one that imparts liquid repellency to a base material (e.g., a fiber base material, a paper base material), and is selected from the group consisting of a water repellent, an oil repellent, an oil resistant agent, and a water resistant agent. can function as at least one.
  • a base material e.g., a fiber base material, a paper base material
  • the repellent in the present disclosure includes compound ⁇ .
  • the repellent in the present disclosure may be compound ⁇ alone.
  • the repellent in the present disclosure may contain other components such as a liquid medium in addition to the 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.
  • the compound ⁇ in the present disclosure is capable of attaching to a substrate and imparting liquid repellency to the substrate.
  • the water contact angle of 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.
  • the angle is preferably at least 40°, for example at least 60°.
  • the water contact angle of 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 compound ⁇ with respect to the spin-coated film, as shown in Examples. 2 ⁇ L of water is dropped onto the spin-coated film, and the contact angle is measured 1 second after the droplet has landed. It means what you can get by doing.
  • the HD (hexadecane) contact angle of compound ⁇ may be 10° or more, 15° or more, 25° or more, 35° or more, 55° or more, 60° or more, or 65° or more.
  • the HD contact angle of compound ⁇ may be 100° or less, 90° or less, or 75° or less.
  • good liquid repellency particularly oil repellency
  • the HD contact angle is the static contact angle of the compound ⁇ with respect to the spin-coated film, as shown in the examples. 2 ⁇ L of HD is dropped onto the spin-coated film, and the contact angle is measured 1 second after the droplet has landed. It means what you can get by doing.
  • the compound ⁇ is 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, a perfluoroalkyl group, a fluorocarbon It is not necessary to have any one selected from the group consisting of an alkyl group and a fluorine atom. Even if the compound ⁇ does not contain these fluorine-containing groups, it can impart liquid repellency to the substrate.
  • Compound ⁇ in the present disclosure does not need to have an active hydrogen-containing group.
  • active hydrogen group-containing groups include amino groups, hydroxy groups, and carboxyl groups.
  • the compound ⁇ in the present disclosure does not need to have a hydroxy group from the viewpoint of improving liquid repellency.
  • Compound ⁇ in the present disclosure has the following formula: A(-X-R n ) m
  • A is an m-valent group obtained by removing m hydrogen atoms from a hydrocarbon aromatic ring 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 from 6 to 40 carbon atoms which may have a substituent
  • n is an integer of 1 or more and 3 or less, independently in each occurrence, m is an integer of 1 or more and 6 or less.
  • A is an m-valent group obtained by removing m hydrogen atoms from a hydrocarbon aromatic ring which may have a substituent.
  • m may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more, preferably 2 or more (eg, 3 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.
  • aromatic hydrocarbon rings examples include benzene, naphthalene, anthracene, phenanthrene, tetracene, pentacene, pyrene, coronene, and the like.
  • the aromatic hydrocarbon ring may have a substituent.
  • substituents on the aromatic hydrocarbon ring include, but are not limited to, -OR', -N(R') 2 , -COOR' (wherein R' is a hydrogen atom or a group having 1 to 4 carbon atoms).
  • halogen atom C 1-6 alkyl group, C 2-6 alkenyl group, C 2-6 alkynyl group, C 3- which may be substituted with one or more halogen atoms selected from 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 5-10 membered heteroaryl group
  • 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 5-10 membered heteroaryl group
  • halogen atom selected from 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 5-10 membered heteroary
  • the number of carbon atoms in the aromatic hydrocarbon ring may be 6 or more, 8 or more, or 10 or more.
  • the number of carbon atoms in the aromatic hydrocarbon ring may be 30 or less, 20 or less, 16 or less, 12 or more, or 8 or less.
  • the aromatic hydrocarbon ring may be a fused polycyclic ring containing a plurality of aromatic carbon atoms and/or non-aromatic hydrocarbons (for example, 2 to 5, preferably 2 to 3).
  • 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 2 is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent; It may be a 1+n-valent group consisting of one or more selected from the group consisting of:
  • X 2 is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent; It may be a 1+n-valent group consisting of one or more selected from the group consisting of:
  • the right side of the group described as X is bonded to R.
  • 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.
  • 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.
  • the hydrocarbon group having 1 to 40 carbon atoms which may have a substituent in R' 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).
  • X2 is a hydrocarbon linker, which is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent.
  • the hydrocarbon group having 1 to 40 carbon atoms which may have a substituent and which is X 2 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).
  • 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 have a substituent and may be a cyclic, branched chain, 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
  • R' is independently at each occurrence a carbon number of 1 to 40 (for example, 1 to 20, 1 to 12, 1 to 8, or 1 to 4) which may have a hydrogen atom or a substituent. ) is a hydrocarbon group.
  • X examples include -X 1 - or -X 1 -X 2 -X 1 -.
  • X may have an amide group, a urea group or a urethane group.
  • the NR' group in the amide group, urea group, or urethane group does not need to be adjacent to an aromatic ring.
  • 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, 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.
  • R a monovalent aliphatic hydrocarbon group having 6 to 40 carbon atoms and which may have a substituent
  • R may be a hydrocarbon group having a substituent, but may be an unsubstituted hydrocarbon group. It may be a base.
  • 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).
  • Method for producing compound ⁇ The method for modifying the hydrocarbon group having 6 or more and 40 or less carbon atoms which may have a substituent on the aromatic hydrocarbon ring 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 a hydrocarbon aromatic ring may be carried out by reacting with a hydrocarbon group-containing reactant.
  • the hydrocarbon group-containing reactant is a compound having a hydrocarbon group and a group capable of reacting with a functional group possessed by an aromatic hydrocarbon ring.
  • the aromatic hydrocarbon ring 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 hydrocarbon aromatic ring 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 hydrocarbon aromatic ring and the hydrocarbon group are bonded via a urethane bond.
  • Compound ⁇ is obtained.
  • a urea bond can be formed, for example, by reacting an amino group-containing hydrocarbon aromatic ring with a hydrocarbon group-containing isocyanate group (or by reacting an isocyanate group-containing hydrocarbon aromatic ring with a hydrocarbon group-containing amine). may be done.
  • a catalyst may be used as appropriate during the reaction. For example, by reacting an amino group-containing aromatic hydrocarbon ring with 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 hydrocarbon aromatic ring and the hydrocarbon group form a urea bond.
  • a compound ⁇ is obtained which is bound via .
  • the aromatic hydrocarbon ring and the hydrocarbon group may be bonded via an ester bond.
  • the ester bond is formed, for example, by reacting a hydroxyl group-containing hydrocarbon aromatic ring with a hydrocarbon group-containing carboxylic acid (or by reacting a carboxylic acid-containing hydrocarbon aromatic ring with a hydrocarbon group-containing alcohol). You can.
  • An acylation catalyst, condensing agent, etc. may be used during the reaction. For example, by reacting a hydroxyl group-containing aromatic hydrocarbon ring and 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 hydrocarbon aromatic ring and the hydrocarbon group form an ester bond.
  • a bound compound ⁇ is obtained.
  • the aromatic hydrocarbon ring and the hydrocarbon group may be bonded via an amide bond.
  • An amide bond can be formed, for example, by reacting an amino group-containing hydrocarbon aromatic ring with a hydrocarbon group-containing carboxylic acid (or by reacting a carboxylic acid-containing hydrocarbon aromatic ring with a hydrocarbon group-containing amine). may be done.
  • An acylation catalyst, condensing agent, etc. may be used during the reaction.
  • the amino group reacts with the carboxylic acid, and the hydrocarbon aromatic ring and the hydrocarbon group form an amide bond.
  • a compound ⁇ is obtained which is bound via .
  • the aromatic hydrocarbon ring and the hydrocarbon group may be bonded via an ether bond.
  • the ether bond is formed, for example, by reacting a halogen-containing hydrocarbon aromatic ring with a hydrocarbon group-containing alcohol (or by reacting a hydroxyl group-containing hydrocarbon aromatic ring with a hydrocarbon group-containing halide). Good too. An acid catalyst, a base catalyst, etc. may be used during the reaction.
  • the hydrocarbon group-containing alcohol acts as a nucleophile, and the hydrocarbon aromatic ring and the carbonized A compound ⁇ in which a hydrogen group is bonded via an ether bond is obtained.
  • the amount of compound ⁇ in the repellent 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, 30% by weight or more. It may be more than % by weight.
  • the amount of 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 or less in the repellent. It may be.
  • 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.
  • the repellent may be a dispersion or a solution.
  • 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 (e.g., alcohol, polyhydric alcohol such as glycol solvent, ether form (e.g. monoether form) of polyhydric alcohol, etc.). . These may be used alone or in combination of two or more.
  • a compound having at least one hydroxy group e.g., alcohol, polyhydric alcohol such as glycol solvent, ether form (e.g. monoether form) of polyhydric alcohol, etc.
  • ether form e.g. monoether form of polyhydric alcohol, etc.
  • the amount of the liquid medium 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 or more, per 1 part by weight (or 10 parts by weight, or 100 parts by weight) of the compound ⁇ . It may be 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 or less, per 1 part by weight of the compound ⁇ (or 10 parts by weight, or 100 parts by weight). It may be 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less.
  • the amount of water 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 or more, 30 parts by weight or more, based on 1 part by weight (or 10 parts by weight, or 100 parts by weight) of the compound ⁇ . It may be at least 40 parts by weight, or at least 50 parts by weight.
  • 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 or less, per 1 part by weight of the compound ⁇ (or 10 parts by weight, or 100 parts by weight). It may be 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight 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 or more, per 1 part by weight (or 10 parts by weight, or 100 parts by weight) of the compound ⁇ . It may be 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 or less, per 1 part by weight of the compound ⁇ (or 10 parts by weight, or 100 parts by weight). It may be 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight 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.
  • 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 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 having an HLB (hydrophilic-hydrophobic balance) of less than 15 (particularly 5 or less) and a compound having an HLB of 15 or more.
  • An example of a compound having an HLB of less than 15 is a sorbitan fatty acid ester.
  • An example of a compound having an HLB of 15 or more is a polyoxyethylene alkyl ether.
  • the weight ratio of the compound having an HLB of less than 15 to the compound having an HLB of 15 or more may be 90:10 to 20:80, for example 85:15 to 55:45.
  • the nonionic surfactant may be used alone or in combination of two or more kinds.
  • 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 the 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 or more, 15 parts by weight or more, based on 100 parts by weight of the compound ⁇ .
  • the amount may be at least 20 parts by weight, 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 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 or less, based on 100 parts by weight of the compound ⁇ . It may be 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 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 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 or more, based on 100 parts by weight of the compound ⁇ .
  • the amount may be 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, 30 parts by weight, based on 100 parts by weight of the compound ⁇ . 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 or more, based on 100 parts by weight of the compound ⁇ .
  • the amount may be 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, 30 parts by weight, based on 100 parts by weight of compound ⁇ . 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 compound ⁇ . , 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 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 or less, 30 parts by weight or less, based on 100 parts by weight of the compound ⁇ .
  • 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 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 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 compound ⁇ . , 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 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 or less, 30 parts by weight or less, based on 100 parts by weight of the compound ⁇ .
  • the amount may be up to 20 parts by weight, up to 10 parts by weight, or up to 5 parts by weight.
  • the repellent may contain components other than the above components.
  • examples of other ingredients include polysaccharides, paper strength agents, flocculants, retention improvers, coagulants, binder resins, anti-slip agents, sizing agents, paper strength agents, fillers, antistatic agents, and preservatives. , ultraviolet absorbers, antibacterial agents, deodorants, fragrances, etc. These may be used alone or in combination of two or more.
  • water and/or oil repellent agents dispersants, texture control agents, softeners, flame retardants, paint fixing agents, anti-wrinkle agents, drying rate regulators, crosslinking agents, and Film aids, compatibilizers, antifreeze agents, viscosity modifiers, ultraviolet absorbers, antioxidants, pH adjusters, insect repellents, antifoaming agents, anti-shrinkage agents, anti-wrinkle agents, shape retention agents, drapes properties retention agent, ironability improver, whitening agent, whitening agent, fabric softening clay, dye transfer prevention agent such as polyvinylpyrrolidone, polymer dispersant, stain remover, scum dispersant, 4,4-bis(2 - Fluorescent brighteners such as sulfostyryl)biphenyldisodium (Tinopal CBS-X manufactured by Ciba Specialty Chemicals), dye fixatives, anti-fading agents such as 1,4-bis(3-aminopropyl)piperaz
  • anti-fouling agents for example, nonionic polymer compounds consisting of alkylene terephthalate and/or alkylene isophthalate units and polyoxyalkylene units (for example, FR627 manufactured by Gooh Kagaku Kogyo), SRC-1 manufactured by Clariant Japan, etc.) are blended. can do. These may be used alone or in combination of two or more.
  • polysaccharide examples include starch, xanthan gum, karaya gum, welan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, pullulan, and the like.
  • the polysaccharide may be a substituted modified polysaccharide, particularly a modified polysaccharide having a hydroxyl group or a cationic group introduced therein.
  • Paper strength enhancer, flocculant, retention improver or coagulant examples include styrene polymers (styrene/maleic acid polymers, styrene/acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, Melamine-formaldehyde polymer, polyamide amine-epichlorohydrin polymer, polyacrylamide polymer, polyamine polymer, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensate, condensate of alkylene dichloride and polyalkylene polyamine, dicyandiamide formalin Examples include condensates, dimethyldiallylammonium chloride polymers, and olefin/maleic anhydride polymers.
  • sizing agent examples include cellulose-reactive sizing agents such as rosin-based sizing agents such as rosin-based soaps, rosin-based emulsions/dispersions, cellulose-reactive sizing agents such as alkyl and alkenyl succinic anhydrides (ASA) emulsions/dispersions of acid anhydrides such as alkenyl and alkyl ketene dimers (AKD) and multimers, and anionic, cationic and amphoteric polymers of ethylenically unsaturated monomers, such as styrene and acrylates. Examples include copolymers.
  • ASA alkyl and alkenyl succinic anhydrides
  • ALD alkenyl and alkyl ketene dimers
  • anionic, cationic and amphoteric polymers of ethylenically unsaturated monomers such as styrene and acrylates. Examples include copolymers.
  • 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.
  • An ultraviolet absorber is a drug that has the effect of protecting against ultraviolet rays, and is a component that absorbs ultraviolet rays, 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 or more, based on 100 parts by weight of the compound ⁇ .
  • the amount may be 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, 40 parts by weight, based on 100 parts by weight of 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.
  • a method for manufacturing a product treated with a repellent in the present disclosure includes a treatment step of treating a substrate with the repellent described above.
  • Treatment means applying a repellent to a substrate by dipping, spraying, coating, etc. Through the treatment, the 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 substrate treated with the repellent in the present disclosure is not limited, but is preferably a textile product or a paper product.
  • base materials for textile products include natural fibers of animal and plant origin such as cotton, linen, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, and semi-synthetic fibers such as rayon and acetate.
  • synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene
  • semi-synthetic fibers such as rayon and acetate.
  • Examples include synthetic fibers, glass fibers, carbon fibers, inorganic fibers such as asbestos fibers, and mixed fibers thereof.
  • Textile products include woven, knitted and non-woven fabrics, cloth in the form of clothing and carpets; Processing may be performed.
  • base materials for 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, old newspapers, and old magazines.
  • Examples include paper made of waste paper pulp such as used cardboard or deinked waste paper, containers made of paper, and molded objects made of paper.
  • Specific examples of paper products include food 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, and kraft paper. , neutral printing writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, molded paper (mold container), etc.
  • Substrates treated with the repellent of the present disclosure are not limited to textiles or paper products, but may also include stones, filters (e.g., electrostatic filters), dust masks, fuel cell parts (e.g., gas diffusion Examples include electrodes and gas diffusion supports), glass, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster.
  • filters e.g., electrostatic filters
  • dust masks e.g., electrostatic filters
  • fuel cell parts e.g., gas diffusion Examples include electrodes and gas diffusion supports
  • glass wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster.
  • the repellent of the present disclosure can be applied to a substrate as a treatment agent (particularly a surface treatment agent) by a conventionally known method.
  • a treatment method the repellent according to the present disclosure is dispersed and diluted in an organic solvent or water if necessary, and then attached to the surface of the base material by a known method such as dip coating, spray coating, foam coating, etc. It may be a method of drying. After drying, a textile product is obtained to which the solid components of the repellent are attached. Further, if necessary, curing may be performed by applying together with a suitable crosslinking agent.
  • 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 repellent can be applied to the substrate by any of the methods known for treating substrates with liquids.
  • the substrate may be soaked in the repellent, or the solution may be applied or sprayed onto the substrate.
  • the treated base material is preferably dried and cured by heating in order to develop liquid repellency.
  • the heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C or 100°C to 120°C. In the present disclosure, good performance can be obtained even with low temperature heating (eg, 100° C. to 140° C.).
  • the heating time may be from 5 seconds to 60 minutes, for example from 30 seconds to 3 minutes.
  • the solution may be applied to the paper, or the solution may be attached or sprayed onto the paper, or the solution may be mixed with pulp slurry before paper making.
  • the treatment may be an external addition treatment or an internal addition treatment.
  • the repellent may be applied to the textile by a cleaning process, such as in a laundering or dry cleaning process.
  • Examples of the paper base material include paper, a container made of paper, and a molded article made of paper (for example, a pulp mold).
  • Examples of methods for treating paper base materials include external addition treatment or internal addition treatment.
  • Paper can be manufactured by conventionally known papermaking methods.
  • An internal addition treatment method in which a repellent is added to the pulp slurry before papermaking, or an external addition treatment method in which a repellent is applied to paper after papermaking can be used.
  • the internal addition treatment method may refer to a treatment method in which a repellent is added to the pulp slurry before papermaking.
  • the internal addition treatment method includes a step of adding a repellent to the pulp slurry and stirring and mixing, and a pulp composition prepared in this step is sucked and dehydrated through a mesh having a predetermined shape, and the pulp composition is deposited and molded into a pulp mold.
  • the method may include one or more of the steps of forming an intermediate and molding and drying the pulp mold intermediate using a heated mold to obtain paper, a container made of paper, and a molded article made of paper. Good, but not limited to this.
  • the treated paper may optionally be subjected to a heat treatment, depending on the nature of the paper, after brief drying at room or elevated temperature.
  • the temperature of the heat treatment may be 150°C or higher, 180°C or higher, or 210°C or higher, and may be 300°C or lower, 250°C or lower, or 200°C or lower, particularly from 80°C to 180°C. By performing heat treatment in such a temperature range, excellent oil resistance, water resistance, etc. can be exhibited.
  • the size press which is an external addition treatment method, can be divided into the following types depending on the coating method.
  • One coating method involves supplying coating liquid (size liquid) to a nip formed by passing paper between two rubber rolls, creating a pool of coating liquid called a pond, and passing paper through this pool to coat both sides of the paper.
  • This is a so-called pound-type two-roll size press that applies a size liquid to the surface.
  • Other coating methods include a gate roll type in which the size liquid is applied by a surface transfer type, and a rod metering size press. In pound-type two-roll size presses, the size liquid easily penetrates into the inside of the paper, and in surface transfer type, size liquid components tend to stay on the surface of the paper.
  • the coating layer stays on the surface of the paper more easily than in the pound-type two-roll size press, and more coating layers are formed on the surface than in the pound-type two-roll size press.
  • performance can be imparted to paper even when the former pound-type two-roll size press is used.
  • the paper treated in this way can optionally, after brief drying at room temperature or at elevated temperatures, have a temperature range of up to 300°C, for example up to 200°C, in particular from 80°C to 180°C, depending on the nature of the paper. By being accompanied by heat treatment, it can exhibit excellent oil resistance, water resistance, etc.
  • the present disclosure can be used in gypsum board base paper, coated base paper, medium-quality paper, general liner and core, neutral pure white roll paper, neutral liner, rust-proof liner, metal interleaving paper, kraft paper, etc. It can also be used in neutral printing writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure sensitive base paper, neutral inkjet paper and neutral information paper.
  • Pulp raw materials include bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulp such as ground wood pulp, mechanical pulp or thermomechanical pulp, used newspaper, used magazine, used corrugated paper, or treated pulp. Any waste paper pulp, such as ink waste paper, can be used. Furthermore, a mixture of the above pulp raw materials and synthetic fibers such as asbestos, polyamide, polyimide, polyester, polyolefin, and polyvinyl alcohol can also be used.
  • Sizing agents can be added to improve the water resistance of paper.
  • sizing agents are cationic sizing agents, anionic sizing agents, and rosin-based sizing agents (eg, acidic rosin-based sizing agents, neutral rosin-based sizing agents).
  • the amount of sizing agent may be from 0.01 to 5% by weight relative to the pulp.
  • paper-making agents such as starch, modified starch, carboxymethyl cellulose, polyamide polyamine-epichlorohydrin resin, flocculants, fixing agents, retention improvers, and dyes are added to the paper as necessary.
  • Additives used in paper manufacturing such as fluorescent dyes, slime control agents, antifoaming agents, etc. can be used.
  • starch and modified starch are used.
  • a repellent agent can be applied to the paper using a size press, a gate roll coater, a bill blade coater, a calender, etc. using starch, polyvinyl alcohol, dye, coating color, anti-slip agent, etc.
  • the amount of the liquid repellent compound contained in the coating layer is preferably 0.01 to 2.0 g/m 2 , particularly 0.1 to 1.0 g/m 2 .
  • the coating layer is preferably formed of a repellent and starch and/or modified starch.
  • the solid content of the paper repellent in the coating layer is preferably 2 g/m 2 or less.
  • the amount of repellent is 0.01 to 50 parts by weight or 0.01 to 30 parts by weight, for example 0.01 to 10 parts by weight, especially 0. It is preferable to mix the repellent with the pulp in an amount of 2 to 5.0 parts by weight.
  • the paper has oil resistance even when using the so-called pound type two-roll size press process, in which the processing liquid is stored between rolls and the base paper is passed through the processing liquid between the rolls at a desired roll speed and nip pressure. can be granted.
  • the paper base material may contain additives such as a sizing agent, a paper strength agent, a flocculant, a retention agent, or a coagulant.
  • Additives may be nonionic, cationic, anionic or amphoteric.
  • the ionic charge density of the additive may be -10000 to 10000 ⁇ eq/g, preferably -4000 to 8000 ⁇ eq/g, and more preferably -1000 to 7000 ⁇ eq/g.
  • Additives (solid content or active ingredients) such as sizing agents, paper strength agents, flocculants, retention agents, or coagulants are generally contained in an amount of 0.1 to 10% by weight (for example, 0.2 to 10% by weight) based on the pulp. 5.0% by weight).
  • the repellent is preferably anionic.
  • Additives eg, sizing agents, paper strength agents, flocculants, retention agents, or coagulants
  • liquid-repellent compounds can be added to the pulp slurry.
  • additives e.g.
  • sizing agents include alkyl ketene dimers, alkenyl succinic anhydrides, styrenic polymers (styrene/maleic acid polymers, styrene /acrylic acid polymer), urea-formaldehyde polymer, polyethyleneimine, melamine-formaldehyde polymer, polyamidoamine-epichlorohydrin polymer, polyacrylamide polymer, polyamine polymer, polydiallyldimethylammonium chloride, alkylamine
  • 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 at least one functional group (hereinafter sometimes referred to as a "specific functional group") selected from the group consisting of monovalent groups represented by (indicating an alkyl group).
  • Examples of M 1 include H, K, Na, or an 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 at least one compound 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.
  • a method for producing a polycarboxylic acid polymer includes, for example, adding a radical polymerization initiator to an aqueous solution of the above-mentioned monomer and/or its salt, and reacting the mixture at 30 to 150°C for 2 to 5 hours.
  • a radical polymerization initiator such as methanol, ethanol, isopropyl alcohol, or an aqueous solvent such as acetone may be added to the aqueous solution of the above-mentioned monomer and/or its salt.
  • radical polymerization initiator examples include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, redox-based polymerization initiators such as combinations of persulfates and sodium bisulfite, hydrogen peroxide, and water-soluble azo-based 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 (e.g., octyl thioglycolate) may be added to adjust the degree of polymerization.
  • a chain transfer agent e.g., 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.
  • phosphoric acid ester compound for example, a commercially available product such as "Phosphanol ML-200" (manufactured by Toho Chemical Industry Co., Ltd., trade name) 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.
  • a treatment solution was prepared by dissolving the compound in chloroform at a rate of 22.5 mg/mL.
  • a polyethylene terephthalate cloth (fabric weight: 88 g/m 2 , 70 denier, gray) was immersed in this treatment solution, air-dried, and then dried at 150° C. for 3 minutes.
  • a wet paper strength agent and a sizing agent are added to this pulp slurry, and paper with a paper density of 0.58 g/cm3 and a basis weight of 45 g/m2 is externally added using a Fourdrinier paper machine (size press processing). It was used as a base paper.
  • the oil resistance (KIT value) of this base paper was 0, and the water resistance (Cobb value) was 52 g/m 2 .
  • a treatment solution prepared by dissolving the compound in chloroform at a rate of 14.9 mg/mL was applied to this base paper using a Baker applicator with a gap of 0 mil, and drying was repeated three times.
  • a treated paper was prepared by drying at °C for 1 minute.
  • Example 1 Compound 1 was used to evaluate contact angle, fabric water repellency, KIT test, and paper water repellency.
  • Example 2 Evaluation was performed in the same manner as in Example 1, except that Compound 2 was used instead of Compound 1.
  • Example 3 Evaluation was performed in the same manner as in Example 1, except that Compound 3 was used instead of Compound 1.
  • Example 5 Evaluation was performed in the same manner as in Example 4, except that Compound 5 was used in place of Compound 4.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
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Abstract

Provided is a novel repellent which contains a compound including an aromatic hydrocarbon ring as a base skeleton and can impart liquid-repellent properties to textile products and/or paper products. The repellent contains a compound α represented by formula A(-X-Rn)m [wherein A is an m-valent group formed by removing m hydrogen atoms from an optionally substituted, aromatic hydrocarbon ring, X, independently on each appearance, is a direct bond or a (1+n)-valent group, R, independently on each appearance, is an optionally substituted, C6-C40 aliphatic hydrocarbon group, n, independently on each appearance, is an integer of 1-3, and m is an integer of 1-6].

Description

撥剤repellent
　本開示は、撥剤、及び当該撥剤によって処理された製品（特に、繊維製品又は紙製品）に関する。 The present disclosure relates to repellents and products (particularly textile or paper products) treated with the repellents.
　近年、各種基材に撥液性（撥水性及び／又は撥油性）を付与することができる非フッ素系撥剤の開発が進められている。 In recent years, progress has been made in the development of non-fluorine-based repellents that can impart liquid repellency (water repellency and/or oil repellency) to various substrates.
　特許文献１には母骨格である複素環に二価の連結基を介して炭素原子数が１４乃至１００の脂肪族基、炭素原子数が１４乃至１００の芳香族基または炭素原子数が１４乃至１００の複素環基を結合させた化合物を金属表面処理剤の成分として用いることが知られている。 Patent Document 1 describes an aliphatic group having 14 to 100 carbon atoms, an aromatic group having 14 to 100 carbon atoms, or an aromatic group having 14 to 100 carbon atoms via a divalent linking group to the heterocycle that is the parent skeleton. It is known that a compound having 100 heterocyclic groups bonded thereto is used as a component of a metal surface treatment agent.
特開２００１－２４７９８１号公報Japanese Patent Application Publication No. 2001-247981
　特許文献１に記載の金属表面処理剤における化合物は複素環を必須成分としており、炭化水素芳香環を用いた場合について記載も示唆もされていない。また、特許文献１は金属表面処理剤であって、繊維製品や紙製品を処理対象とするものではない。 The compound in the metal surface treatment agent described in Patent Document 1 has a heterocycle as an essential component, and there is no description or suggestion of the use of a hydrocarbon aromatic ring. Moreover, Patent Document 1 is a metal surface treatment agent, and is not intended to treat textile products or paper products.
　本開示は、炭化水素芳香環を母骨格とする化合物を含有し、繊維製品及び／又は紙製品に撥液性を付与できる新規な撥剤を提供することを目的とする。 An object of the present disclosure is to provide a novel repellent that contains a compound having a hydrocarbon aromatic ring as a parent skeleton and can impart liquid repellency to textile products and/or paper products.
　本開示は以下の態様を含む：
［項１］
下記式：
Ａ（－Ｘ－Ｒｎ）ｍ
［式中、
Ａは置換基を有してよい炭化水素芳香環からｍ個の水素原子を取り除いたｍ価の基であり、
Ｘは、各出現において独立して、直接結合又は１＋ｎ価の基であり、
Ｒは、各出現において独立して、置換基を有してよい炭素数６以上４０以下の脂肪族炭化水素基であり、
ｎは、各出現において独立して、１以上３以下の整数であり、
ｍは１以上６以下の整数である。］
で表される化合物αを含む、撥剤。
［項２］
Ｒの炭素数が１２以上である、項１に記載の撥剤。
［項３］
前記化合物αが２個以上のＲを有する、項１又は２に記載の撥剤。
［項４］
Ｘが、
直接結合、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ（＝Ｏ）２－、－ＮＲ’－、－Ｃ（ＯＲ’）Ｒ’－、及び－Ｃ（ＯＲ’）（－）２、（式中、Ｒ’は、各出現において独立して、水素原子又は置換基を有してよい炭素数１～４０の炭化水素基である。）からなる群から選択される一以上から構成されるＸ１と、
置換基を有してよい炭素数１～４０の炭化水素基であるＸ２と、
からなる群から選択される一以上から構成される１＋ｎ価の基である、項１～３のいずれか一項に記載の撥剤。
［項５］
Ｘが、
－Ｘ１－、又は、
－Ｘ１－Ｘ２－Ｘ１－
［式中、
Ｘ１が、各出現において独立して、
直接結合、
－Ｏ－、
－Ｏ－Ｃ(＝Ｏ)－、
－Ｏ－Ｃ(＝Ｏ)－Ｏ－、
－Ｏ－Ｃ(＝Ｏ)－ＮＲ’－、
－ＮＲ’－、
－ＮＲ’－Ｃ(＝Ｏ)－、
－ＮＲ’－Ｃ(＝Ｏ)－Ｏ－、
－ＮＲ’－Ｃ(＝Ｏ)－ＮＲ’－、
－Ｃ(＝Ｏ)－、
－Ｃ(＝Ｏ)－Ｏ－、
－Ｃ(＝Ｏ)－ＮＲ’－、
－ＳＯ２－、
－ＳＯ２ＮＲ’－、
－Ｃ（ＯＲ’）Ｒ’－、又は
－Ｃ（ＯＲ’）（－）２
（式中、
Ｒ’は、各出現において独立して、水素原子又は置換基を有してよい炭素数１～４０の炭化水素基である。）
で表される基であり、
Ｘ２が置換基を有してよい炭素数１～４０の炭化水素基である。］
で表される基である、項１～４のいずれか一項に記載の撥剤。
［項６］
Ｘが
－Ｏ－Ｃ（＝Ｏ）－ＮＲ’－、
－Ｃ（＝Ｏ）－ＮＲ’－、
－ＳＯ２ＮＨ－、
－Ｃ（ＯＲ’）Ｒ’－、又は
－Ｃ（ＯＲ’）（－）２
［式中、
Ｒ’は、水素原子又は置換基を有してよい炭素数１～４０の炭化水素基である。］
である、項１～５のいずれか一項に記載の撥剤。
［項７］
前記化合物αがヒドロキシ基を有してもよいアルキル基である、項１～６のいずれか一項に記載の撥剤。
［項８］
水、有機溶媒、又は水と有機溶媒との混合物とを含み、分散液又は溶液である、項１～７のいずれか一項に記載の撥剤。
［項９］
多糖類、紙力増強剤、凝集剤、定着剤、歩留まり向上剤、凝結剤、シリコーンワックス、及びブロックドイソシアネートからなる群から選択される一以上を含む、項１～８のいずれか一項に記載の撥剤。
［項１０］
繊維製品用である、項１～９のいずれか一項に記載の撥剤。
［項１１］
紙製品用である、項１～９のいずれか一項に記載の撥剤。
［項１２］
フッ素原子を有しない、項１～１１のいずれか一項に記載の撥剤。
［項１３］
項１～１２のいずれか一項に記載の撥剤によって処理された繊維製品。
［項１４］
項１～１２のいずれか一項に記載の撥剤によって処理された紙製品。 The present disclosure includes the following aspects:
[Section 1]
The following formula:
A(-X-R n ) m
[In the formula,
A is an m-valent group obtained by removing m hydrogen atoms from a hydrocarbon aromatic ring 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 from 6 to 40 carbon atoms which may have a substituent;
n is an integer of 1 or more and 3 or less, independently in each occurrence,
m is an integer of 1 or more and 6 or less. ]
A repellent containing the compound α represented by.
[Section 2]
Item 2. The repellent according to Item 1, wherein R has 12 or more carbon atoms.
[Section 3]
Item 3. The repellent according to Item 1 or 2, wherein the compound α has two or more R's.
[Section 4]
X is
Direct bond, -O-, -C(=O)-, -S(=O) 2 -, -NR'-, -C(OR')R'-, and -C(OR')(-) 2 , (wherein each occurrence of R' is independently a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent.) X 1 to be done,
X 2 is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent;
Item 4. The repellent according to any one of Items 1 to 3, which is a 1+n-valent group consisting of one or more members selected from the group consisting of:
[Section 5]
X is
-X 1 -, or
-X 1 -X 2 -X 1 -
[In the formula,
X 1 independently in each occurrence,
direct binding,
-O-,
-OC(=O)-,
-O-C(=O)-O-,
-OC(=O)-NR'-,
-NR'-,
-NR'-C(=O)-,
-NR'-C(=O)-O-,
-NR'-C(=O)-NR'-,
-C(=O)-,
-C(=O)-O-,
-C(=O)-NR'-,
-SO 2 -,
-SO 2 NR'-,
-C(OR')R'- or -C(OR')(-) 2
(In the formula,
R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent. )
is a group represented by
X 2 is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent. ]
Item 5. The repellent according to any one of items 1 to 4, which is a group represented by the following.
[Section 6]
X is -OC(=O)-NR'-,
-C(=O)-NR'-,
-SO2NH- ,
-C(OR')R'- or -C(OR')(-) 2
[In the formula,
R' is a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent. ]
The repellent according to any one of Items 1 to 5, which is.
[Section 7]
Item 7. The repellent according to any one of Items 1 to 6, wherein the compound α is an alkyl group that may have a hydroxy group.
[Section 8]
Item 8. The repellent according to any one of Items 1 to 7, which contains water, an organic solvent, or a mixture of water and an organic solvent, and is a dispersion or solution.
[Section 9]
Any one of Items 1 to 8, containing one or more selected from the group consisting of polysaccharides, paper strength agents, flocculants, fixing agents, retention improvers, coagulants, silicone waxes, and blocked isocyanates. Repellent listed.
[Section 10]
Item 10. The repellent according to any one of Items 1 to 9, which is for use in textile products.
[Section 11]
Item 10. The repellent according to any one of Items 1 to 9, which is for paper products.
[Section 12]
Item 12. The repellent according to any one of Items 1 to 11, which does not have a fluorine atom.
[Section 13]
Item 13. A textile product treated with the repellent according to any one of Items 1 to 12.
[Section 14]
A paper product treated with the repellent agent according to any one of items 1 to 12.
　本開示における撥剤は繊維製品及び／又は紙製品に撥液性を付与できる。 The repellent agent in the present disclosure can impart liquid repellency to textile products and/or paper products.
＜用語の定義＞
　本明細書において用いられる場合、「ｎ価の基」とは、ｎ個の結合手を有する基、すなわちｎ個の結合を形成する基を意味する。また、「ｎ価の有機基」とは、炭素を含有するｎ価の基を意味する。かかる有機基としては、特に限定されないが、炭化水素基又はその誘導体であり得る。炭化水素基の誘導体とは、炭化水素基の末端又は分子鎖中に、１つ又はそれ以上のＮ、Ｏ、Ｓ、Ｓｉ、アミド、スルホニル、シロキサン、カルボニル、カルボニルオキシ等を有している基を意味する。 <Definition of terms>
As used herein, the term "n-valent group" means a group having n bonds, that is, a group forming n bonds. Moreover, "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 derivative of a hydrocarbon group 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.
　本明細書において用いられる場合、「炭化水素基」とは、炭素及び水素を含む基であって、炭化水素から水素原子を脱離させた基を意味する。かかる炭化水素基としては、特に限定されるものではないが、Ｃ１－２０炭化水素基、例えば、脂肪族炭化水素基、芳香族炭化水素基等が挙げられる。上記「脂肪族炭化水素基」は、直鎖状、分枝鎖状又は環状のいずれであってもよく、飽和又は不飽和のいずれであってもよい。また、炭化水素基は、１つ又はそれ以上の環構造を含んでいてもよい。炭化水素基は、１つ又はそれ以上の置換基により置換されていてもよい。 As used herein, the term "hydrocarbon group" refers to a group containing carbon and hydrogen, which is obtained by removing a hydrogen atom from a hydrocarbon. Such hydrocarbon groups include, but are not particularly limited to, C 1-20 hydrocarbon groups, such as aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The above-mentioned "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.
　本明細書において、「各出現において独立して」、「互いにそれぞれ独立して」、「それぞれ独立して」又はこれと同様の表現が明示的に記載されているか否かに関わらず、例外である旨の記載がある場合を除き、化学構造中に複数出現し得る用語（記号）が定義される場合、出現毎に独立して当該定義が適用される。 In this specification, whether or not "independently on each occurrence", "independently of each other", "independently of each other", or similar expressions are expressly stated, there are no exceptions. Unless otherwise stated, when a term (symbol) that can occur multiple times in a chemical structure is defined, the definition is applied independently for each occurrence.
＜撥剤＞
　本開示における撥剤は基材（例えば、繊維基材、紙基材）に撥液性を付与するものであり、撥水剤、撥油剤、耐油剤、及び耐水剤からなる群から選択される少なくとも一として機能し得る。 <Repellent>
The repellent agent in the present disclosure is one that imparts liquid repellency to a base material (e.g., a fiber base material, a paper base material), and is selected from the group consisting of a water repellent, an oil repellent, an oil resistant agent, and a water resistant agent. can function as at least one.
　本開示における撥剤は化合物αを含む。本開示における撥剤は化合物α単独であってもよい。本開示における撥剤は、化合物α以外に、液状媒体等のその他成分を含んでもよい。 The repellent in the present disclosure includes compound α. The repellent in the present disclosure may be compound α alone. The repellent in the present disclosure may contain other components such as a liquid medium in addition to the compound α.
　本開示における撥剤は炭素数８以上のフルオロアルキル基を有する化合物、炭素数８以上のパーフルオロアルキル基を有する化合物、炭素数４以上のフルオロアルキル基を有する化合物、炭素数４以上のパーフルオロアルキル基を有する化合物、パーフルオロアルキル基を有する化合物、フルオロアルキル基を有する化合物、及びフッ素原子を有する化合物からなる群から選択されるいずれかを有しなくてもよい。本開示における撥剤は、これらのフッ素化合物を含まなくても、基材に撥液性を付与し得る。 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.
〔化合物α〕
　本開示における化合物αは、基材に付着して、基材に撥液性を付与し得るものである。 [Compound α]
The compound α in the present disclosure is capable of attaching to a substrate and imparting liquid repellency to the substrate.
　化合物αの水接触角は３５°以上、４０°以上、４５°以上、５０°以上、５５°以上、６５°以上、７５°以上、８５°以上、９０°以上、又は１００°以上であってよく、好ましくは４０°以上、例えば６０°以上である。化合物αの水接触角は１６０°以下、１４０°以下、１３０°以下、１２０°以下、１１０°以下、１００°以下、又は９０°以下であってよい。化合物αが上記の下限以上の水接触角を有することにより、基材に良好に撥液性（特に撥水性）を付与し得る。水接触角とは、実施例に示すように化合物αのスピンコート膜に対する静的接触角であって、スピンコート膜上に、２μＬの水を滴下し、着滴１秒後の接触角を測定して得られるものをいう。 The water contact angle of compound α 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. The angle is preferably at least 40°, for example at least 60°. The water contact angle of compound α may be 160° or less, 140° or less, 130° or less, 120° or less, 110° or less, 100° or less, or 90° or less. When the compound α has a water contact angle equal to or greater than the above lower limit, good liquid repellency (particularly water repellency) can be imparted to the base material. The water contact angle is the static contact angle of compound α with respect to the spin-coated film, as shown in Examples. 2 μL of water is dropped onto the spin-coated film, and the contact angle is measured 1 second after the droplet has landed. It means what you can get by doing.
　化合物αのＨＤ（ヘキサデカン）接触角は１０°以上、１５°以上、２５°以上、３５°以上、５５°以上、６０°以上、又は６５°以上であってよい。化合物αのＨＤ接触角は１００°以下、９０°以下、又は７５°以下であってよい。化合物αが上記の下限以上のＨＤ接触角を有することにより、基材に良好に撥液性（特に撥油性）を付与し得る。ＨＤ接触角とは、実施例に示すように化合物αのスピンコート膜に対する静的接触角であって、スピンコート膜上に、２μＬのＨＤを滴下し、着滴１秒後の接触角を測定して得られるものをいう。 The HD (hexadecane) contact angle of compound α may be 10° or more, 15° or more, 25° or more, 35° or more, 55° or more, 60° or more, or 65° or more. The HD contact angle of compound α may be 100° or less, 90° or less, or 75° or less. When the compound α has an HD contact angle equal to or greater than the above lower limit, good liquid repellency (particularly oil repellency) can be imparted to the base material. The HD contact angle is the static contact angle of the compound α with respect to the spin-coated film, as shown in the examples. 2 μL of HD is dropped onto the spin-coated film, and the contact angle is measured 1 second after the droplet has landed. It means what you can get by doing.
　本開示における化合物αは炭素数８以上のフルオロアルキル基、炭素数８以上のパーフルオロアルキル基、炭素数４以上のフルオロアルキル基、炭素数４以上のパーフルオロアルキル基、パーフルオロアルキル基、フルオロアルキル基、及びフッ素原子からなる群から選択されるいずれかを有しなくてもよい。化合物αがこれらのフッ素含有基を含まなくても、基材に撥液性を付与し得る。 In the present disclosure, the compound α is 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, a perfluoroalkyl group, a fluorocarbon It is not necessary to have any one selected from the group consisting of an alkyl group and a fluorine atom. Even if the compound α does not contain these fluorine-containing groups, it can impart liquid repellency to the substrate.
　本開示における化合物αは活性水素含有基を有しなくてもよい。活性水素基含有基の例としてはアミノ基、ヒドロキシ基、又はカルボキシル基が挙げられる。特に本開示における化合物αは撥液性向上の観点からヒドロキシ基を有しなくてもよい。 Compound α in the present disclosure does not need to have an active hydrogen-containing group. Examples of active hydrogen group-containing groups include amino groups, hydroxy groups, and carboxyl groups. In particular, the compound α in the present disclosure does not need to have a hydroxy group from the viewpoint of improving liquid repellency.
　本開示における化合物αは下記式：
Ａ（－Ｘ－Ｒｎ）ｍ
［式中、
Ａは置換基を有してよい炭化水素芳香環からｍ個の水素原子を取り除いたｍ価の基であり、
Ｘは、各出現において独立して、直接結合又は１＋ｎ価の基であり、
Ｒは、各出現において独立して、置換基を有してよい炭素数６以上４０以下の脂肪族炭化水素基であり、
ｎは、各出現において独立して、１以上３以下の整数であり、
ｍは１以上６以下の整数である。］
で表される。 Compound α in the present disclosure 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 a hydrocarbon aromatic ring 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 from 6 to 40 carbon atoms which may have a substituent;
n is an integer of 1 or more and 3 or less, independently in each occurrence,
m is an integer of 1 or more and 6 or less. ]
It is expressed as
［Ａ］
　Ａは置換基を有してよい炭化水素芳香環からｍ個の水素原子を取り除いたｍ価の基である。ｍは１以上、２以上、３以上、４以上、又は５以上であってよく、好ましくは２以上（例えば３以上）である。ｍは６以下、５以下、４以下、３以下、又は２以下であってよく、好ましくは４以下である。 [A]
A is an m-valent group obtained by removing m hydrogen atoms from a hydrocarbon aromatic ring which may have a substituent. m may be 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more, preferably 2 or more (eg, 3 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.
　炭化水素芳香環の例としては、ベンゼン、ナフタレン、アントラセン、フェナントレン、テトラセン、ペンタセン、ピレン、コロネン等が挙げられる。 Examples of aromatic hydrocarbon rings include benzene, naphthalene, anthracene, phenanthrene, tetracene, pentacene, pyrene, coronene, and the like.
　炭化水素芳香環は置換基を有してよい。炭化水素芳香環の置換基の例は、特に限定されないが、例えば、－ＯＲ’、－Ｎ（Ｒ’）２、－ＣＯＯＲ’（式中、Ｒ’は、水素原子又は炭素数１～４の炭化水素基である）、ハロゲン原子、１個またはそれ以上のハロゲン原子により置換されていてもよい、Ｃ１－６アルキル基、Ｃ２－６アルケニル基、Ｃ２－６アルキニル基、Ｃ３－１０シクロアルキル基、Ｃ３－１０不飽和シクロアルキル基、５～１０員のヘテロシクリル基、５～１０員の不飽和ヘテロシクリル基、Ｃ６－１０アリール基および５～１０員のヘテロアリール基から選択される１個またはそれ以上の基が挙げられる。 The aromatic hydrocarbon ring may have a substituent. Examples of substituents on the aromatic hydrocarbon ring include, but are not limited to, -OR', -N(R') 2 , -COOR' (wherein R' is a hydrogen atom or a group having 1 to 4 carbon atoms). hydrocarbon group), halogen atom, C 1-6 alkyl group, C 2-6 alkenyl group, C 2-6 alkynyl group, C 3- which may be substituted with one or more halogen atoms selected from 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 5-10 membered heteroaryl group One or more groups are included.
　炭化水素芳香環の炭素数は６以上、８以上、又は１０以上であってよい。炭化水素芳香環の炭素数は３０以下、２０以下、１６以下、１２以上、又は８以下であってよい。 The number of carbon atoms in the aromatic hydrocarbon ring may be 6 or more, 8 or more, or 10 or more. The number of carbon atoms in the aromatic hydrocarbon ring may be 30 or less, 20 or less, 16 or less, 12 or more, or 8 or less.
　炭化水素芳香環は、芳香環炭素及び／又は非芳香族炭化水素を複数（例えば２～５個、好ましくは２～３個）含む縮合多環であってもよい。 The aromatic hydrocarbon ring may be a fused polycyclic ring containing a plurality of aromatic carbon atoms and/or non-aromatic hydrocarbons (for example, 2 to 5, preferably 2 to 3).
［Ｘ］
　Ｘは、直接結合又は１＋ｎ価の基である。ｎは１～３、２～３、１～２、１、２、又は３であってよい。 [X]
X is a direct bond or a 1+n valent group. n may be 1-3, 2-3, 1-2, 1, 2, or 3.
　Ｘの分子量は３０００以下、２５００以下、２０００以下、１５００以下、１０００以下、７５０以下、又は５００以下であってよい。Ｘの分子量は１０以上、５０以上、１００以上、２００以上、３００以上、５００以上、又は７５０以上であってよい。 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は、
直接結合、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ（＝Ｏ）２－、－ＮＲ’－、－Ｃ（ＯＲ’）Ｒ’－、及び－Ｃ（ＯＲ’）（－）２、（式中、Ｒ’は、各出現において独立して、水素原子又は置換基を有してよい炭素数１～４０（例えば、１～２０、１～１２、１～８、又は１～４）の炭化水素基である。）からなる群から選択される一以上から構成されるＸ１と、
置換基を有してよい炭素数１～４０の炭化水素基であるＸ２と、
からなる群から選択される一以上から構成される１＋ｎ価の基であってよい。なお、本明細書において、Ｘとして記載している基は右がＲに結合する。 X is
Direct bond, -O-, -C(=O)-, -S(=O) 2 -, -NR'-, -C(OR')R'-, and -C(OR')(-) 2 , (wherein R' is independently at each occurrence a carbon number of 1 to 40 (for example, 1 to 20, 1 to 12, 1 to 8, or 1 to 4) which may have a hydrogen atom or a substituent. ) is a hydrocarbon group consisting of one or more selected from the group consisting of
X 2 is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent;
It may be a 1+n-valent group consisting of one or more selected from the group consisting of: In addition, in this specification, the right side of the group described as X is bonded to R.
［Ｘ１］
　Ｘ１は非炭化水素のリンカーである。 [X 1 ]
X 1 is a non-hydrocarbon linker.
　Ｘ１は、直接結合若しくは二価以上の基である。Ｘ１の価数は２～４、２～３、又は２であってよい。Ｘ１は直接結合のみでないことが好ましい。 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. Preferably, X 1 is not only a direct bond.
　Ｘ１の分子量は２０００以下、１５００以下、１０００以下、７５０以下、又は５００以下であってよい。Ｘ１の分子量は１０以上、５０以上、１００以上、２００以上、３００以上、又は５００以上であってよい。 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.
　Ｘ１は、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ（＝Ｏ）２－、－ＮＲ’－、－Ｃ（ＯＲ’）Ｒ’－、及び－Ｃ（ＯＲ’）（－）２（式中、Ｒ’は、各出現において独立して、水素原子又は置換基を有してよい炭素数１～４０（例えば、１～２０、１～１２、１～８、又は１～４）の炭化水素基である。）からなる群から選択される一以上から構成される。 X 1 is -O-, -C(=O)-, -S(=O) 2 -, -NR'-, -C(OR')R'-, and -C(OR')(-) 2 (wherein R' is independently at each occurrence a carbon number of 1 to 40 (for example, 1 to 20, 1 to 12, 1 to 8, or 1 to 4) which may have a hydrogen atom or a substituent. ) is a hydrocarbon group consisting of one or more selected from the group consisting of ).
　Ｒ’における置換基を有してよい炭素数１～４０の炭化水素基は、置換基を有する炭化水素基であってもよいが、無置換の炭化水素基であってもよい。ここで、置換基の例としては、－ＯＲ’、－Ｎ（Ｒ’）２、－ＣＯＯＲ’、及びハロゲン原子等（式中、Ｒ’は、各出現において独立して、水素原子又は炭素数１～４の炭化水素基である）が挙げられ。置換基は活性水素を有してよいし、有していなくてもよい。置換基の数は、６個以下、５個以下、４個以下、３個以下、２個以下、１個以下、又は０であってよい。置換基を有する炭化水素基において、炭素原子及びヘテロ原子の合計量に対する炭素原子の量が７０ｍｏｌ％以上、８０ｍｏｌ％以上、９０ｍｏｌ％以上、９５ｍｏｌ％以上、又は９９ｍｏｌ％以上であってよく、好ましくは７５ｍｏｌ％以上である。置換基を有する炭化水素基において、炭素原子及びヘテロ原子の合計量に対する炭素原子の量が９５ｍｏｌ％以下、９０ｍｏｌ％以下、８５ｍｏｌ％以下、又は８０ｍｏｌ％以下であってよい。例えば、炭素数６以上４０以下の基は、置換基として１～３個（例えば１個）の－ＯＲ’（特に－ＯＨ）を（例えば末端以外において）有してよい。 The hydrocarbon group having 1 to 40 carbon atoms which may have a substituent in R' may be a hydrocarbon group having a substituent, or may be an unsubstituted hydrocarbon group. Here, examples of 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. In the hydrocarbon group having a substituent, 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. In the hydrocarbon group having a substituent, 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. For example, 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).
　Ｘ１の例としては、
直接結合、
－Ｏ－、
－Ｏ－Ｃ(＝Ｏ)－、
－Ｏ－Ｃ(＝Ｏ)－Ｏ－、
－Ｏ－Ｃ(＝Ｏ)－ＮＲ’－、
－ＮＲ’－、
－ＮＲ’－Ｃ(＝Ｏ)－、
－ＮＲ’－Ｃ(＝Ｏ)－Ｏ－、
－ＮＲ’－Ｃ(＝Ｏ)－ＮＲ’－、
－Ｃ(＝Ｏ)－、
－Ｃ(＝Ｏ)－Ｏ－、
－Ｃ(＝Ｏ)－ＮＲ’－、
－ＳＯ２－、
－ＳＯ２ＮＲ’－、
－Ｃ（ＯＲ’）Ｒ’－、
－Ｃ（ＯＲ’）（－）２等
（式中、Ｒ’は、各出現において独立して、水素原子又は置換基を有してよい炭素数１～４０（例えば、１～２０、１～１２、１～８、又は１～４）の炭化水素基である。）
が挙げられる。 As an example of X1 ,
direct binding,
-O-,
-OC(=O)-,
-O-C(=O)-O-,
-OC(=O)-NR'-,
-NR'-,
-NR'-C(=O)-,
-NR'-C(=O)-O-,
-NR'-C(=O)-NR'-,
-C(=O)-,
-C(=O)-O-,
-C(=O)-NR'-,
-SO 2 -,
-SO 2 NR'-,
-C(OR')R'-,
-C(OR')(-) 2 etc. (wherein R' is independently at each occurrence a carbon number of 1 to 40 (for example, 1 to 20, 1 to 40) which may have a hydrogen atom or a substituent; 12, 1 to 8, or 1 to 4).)
can be mentioned.
［Ｘ２］
　Ｘ２は炭化水素のリンカーであり、置換基を有してよい炭素数１～４０の炭化水素基である。 [ X2 ]
X2 is a hydrocarbon linker, which is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent.
　Ｘ２である、置換基を有してよい炭素数１～４０の炭化水素基は、置換基を有する炭化水素基であってもよいが、無置換の炭化水素基であってもよい。ここで、置換基の例としては、－ＯＲ’、－Ｎ（Ｒ’）２、－ＣＯＯＲ’、及びハロゲン原子等（式中、Ｒ’は、各出現において独立して、水素原子又は炭素数１～４の炭化水素基である）が挙げられ。置換基は活性水素を有してよいし、有していなくてもよい。置換基の数は、６個以下、５個以下、４個以下、３個以下、２個以下、１個以下、又は０であってよい。置換基を有する炭化水素基において、炭素原子及びヘテロ原子の合計量に対する炭素原子の量が７０ｍｏｌ％以上、８０ｍｏｌ％以上、９０ｍｏｌ％以上、９５ｍｏｌ％以上、又は９９ｍｏｌ％以上であってよく、好ましくは７５ｍｏｌ％以上である。置換基を有する炭化水素基において、炭素原子及びヘテロ原子の合計量に対する炭素原子の量が９５ｍｏｌ％以下、９０ｍｏｌ％以下、８５ｍｏｌ％以下、又は８０ｍｏｌ％以下であってよい。例えば、炭素数６以上４０以下の基は、置換基として１～３個（例えば１個）の－ＯＲ’（特に－ＯＨ）を（例えば末端以外において）有してよい。 The hydrocarbon group having 1 to 40 carbon atoms which may have a substituent and which is X 2 may be a hydrocarbon group having a substituent, or may be an unsubstituted hydrocarbon group. Here, examples of 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. In the hydrocarbon group having a substituent, 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. In the hydrocarbon group having a substituent, 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. For example, 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).
　Ｘ２は、二価以上の基である。Ｘ２の価数は例えば、２～４、２～３、又は２であってよい。 X 2 is a divalent or higher group. The valence of X 2 may be, for example, 2-4, 2-3, or 2.
　Ｘ２の炭素数は、１以上、２以上、３以上、４以上、６以上、８以上、１０以上、１２以上、１４以上、１６以上、又は１８以上であってよい。Ｘ２の炭素数は４０以下、３５以下、３０以下、２５以下、２０以下、１５以下、１０以下、又は５以下であってよい。 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.
　Ｘ２は、置換基を有していてもよく、環状、分岐鎖、又は直鎖の炭化水素基であってよい。Ｘ２は、芳香族炭化水素基、又は脂肪族炭化水素基であってよく、例えば脂肪族炭化水素基（例えば飽和の脂肪族炭化水素基）であってよい。 X 2 may have a substituent and may be a cyclic, branched chain, 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).
　Ｘ２の例としては、
－(ＣＨ２）ｐ－（ｐは１～４０、例えば１～１０である）、
炭素数１～４０、例えば１～１０の不飽和結合を有する直鎖状の炭化水素基、
炭素数１～４０、例えば１～１０の枝分かれ構造を有する炭化水素基、
－(ＣＨ２）ｑ－Ｃ６Ｈ４－(ＣＨ２）ｒ－（ｑ及びｒはそれぞれ独立して０～４０、例えば１～１０であり、－Ｃ６Ｈ４－はフェニレン基である）
等が挙げられる。 As an example of X2 ,
-(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,
A hydrocarbon group having a branched structure having 1 to 40 carbon atoms, for example 1 to 10 carbon atoms,
-(CH 2 ) q -C 6 H 4 -(CH 2 ) r - (q and r are each independently 0 to 40, for example 1 to 10, and -C 6 H 4 - is a phenylene group)
etc.
［Ｘの例］
　Ｘの例を説明する。なお、下記において、Ｒ’は、各出現において独立して、水素原子又は置換基を有してよい炭素数１～４０（例えば、１～２０、１～１２、１～８、又は１～４）の炭化水素基である。 [Example of X]
An example of X will be explained. In addition, in the following, R' is independently at each occurrence a carbon number of 1 to 40 (for example, 1 to 20, 1 to 12, 1 to 8, or 1 to 4) which may have a hydrogen atom or a substituent. ) is a hydrocarbon group.
　Ｘの好ましい例としては－Ｘ１－又は－Ｘ１－Ｘ２－Ｘ１－が挙げられる。
　Ｘは、
－Ｘ１－、又は、－Ｘ１－Ｘ２－Ｘ１－
［式中、
Ｘ１が、各出現において独立して、
直接結合、
－Ｏ－、
－Ｏ－Ｃ(＝Ｏ)－、
－Ｏ－Ｃ(＝Ｏ)－Ｏ－、
－Ｏ－Ｃ(＝Ｏ)－ＮＲ’－、
－ＮＲ’－、
－ＮＲ’－Ｃ(＝Ｏ)－、
－ＮＲ’－Ｃ(＝Ｏ)－Ｏ－、
－ＮＲ’－Ｃ(＝Ｏ)－ＮＲ’－、
－Ｃ(＝Ｏ)－、
－Ｃ(＝Ｏ)－Ｏ－、
－Ｃ(＝Ｏ)－ＮＲ’－、
－ＳＯ２－、
－ＳＯ２ＮＲ’－、
－Ｃ（ＯＲ’）Ｒ’－、又は
－Ｃ（ＯＲ’）（－）２
（式中、Ｒ’は、各出現において独立して、水素原子又は置換基を有してよい炭素数１～４０（例えば、１～２０、１～１２、１～８、又は１～４）の炭化水素基である。）
であり、
Ｘ２が置換基を有してよい炭素数１～４０の炭化水素基である。］
で表される基であることが好ましい。これにより、基材に良好に撥液性を付与し得る。 Preferred examples of X include -X 1 - or -X 1 -X 2 -X 1 -.
X is
-X 1 - or -X 1 -X 2 -X 1 -
[In the formula,
X 1 independently in each occurrence,
direct binding,
-O-,
-OC(=O)-,
-O-C(=O)-O-,
-OC(=O)-NR'-,
-NR'-,
-NR'-C(=O)-,
-NR'-C(=O)-O-,
-NR'-C(=O)-NR'-,
-C(=O)-,
-C(=O)-O-,
-C(=O)-NR'-,
-SO 2 -,
-SO 2 NR'-,
-C(OR')R'- or -C(OR')(-) 2
(In the formula, R' independently at each occurrence has a hydrogen atom or a carbon number of 1 to 40 (for example, 1 to 20, 1 to 12, 1 to 8, or 1 to 4) which may have a substituent. is a hydrocarbon group.)
and
X 2 is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent. ]
A group represented by is preferable. Thereby, good liquid repellency can be imparted to the base material.
　Ｘは、アミド基、ウレア基又はウレタン基を有してよい。そのようなＸの例としては、
－Ｏ－Ｃ(＝Ｏ)－ＮＲ’－、
－ＮＲ’－Ｃ(＝Ｏ)－、
－ＮＲ’－Ｃ(＝Ｏ)－Ｏ－、
－ＮＲ’－Ｃ(＝Ｏ)－ＮＲ’－
－Ｃ(＝Ｏ)－ＮＲ’－
等を含む基が挙げられる。アミド基、ウレア基又はウレタン基におけるＮＲ’基が芳香環に隣接していなくてもよい。 X may have an amide group, a urea group or a urethane group. An example of such an X is
-OC(=O)-NR'-,
-NR'-C(=O)-,
-NR'-C(=O)-O-,
-NR'-C(=O)-NR'-
-C(=O)-NR'-
and the like. The NR' group in the amide group, urea group, or urethane group does not need to be adjacent to an aromatic ring.
　Ｘの例としては、Ｘが二価の場合、－Ｘ１－、－Ｘ１－Ｃ(＝Ｏ)－、－Ｃ(＝Ｏ)－Ｘ１－、－Ｘ１－Ｃ(＝Ｏ)－Ｘ１－、－Ｘ１－Ｘ２－、－Ｘ１－Ｘ２－Ｘ１－、－Ｘ１－Ｘ２－Ｘ１－Ｃ（＝Ｏ）－、－Ｘ１－Ｘ２－Ｃ（＝Ｏ）－Ｘ１－、－Ｘ１－Ｘ２－Ｘ１－Ｃ（＝Ｏ）－Ｘ１－、－Ｘ１－Ｘ２－Ｘ１－Ｘ２－等が挙げられる。 Examples of X include, when X is divalent, -X 1 -, -X 1 -C(=O)-, -C(=O)-X 1 -, -X 1 -C(=O)- X 1 -, -X 1 -X 2 -, -X 1 -X 2 -X 1 -, -X 1 -X 2 -X 1 -C(=O)-, -X 1 -X 2 -C(= O)-X 1 -, -X 1 -X 2 -X 1 -C(=O)-X 1 -, -X 1 -X 2 -X 1 -X 2 -, and the like.
　Ｘの例としては、Ｘが三価の場合、－Ｘ１（－）２、－Ｘ１－Ｘ１（－）２、－Ｘ１－Ｘ２（－Ｘ１－）２、－Ｘ２（－Ｘ１－）２、－Ｘ２（－Ｘ１－Ｃ(＝Ｏ)－）２、－Ｘ２（－Ｃ(＝Ｏ)－Ｘ１－）２、－Ｘ２（－Ｘ１－Ｃ(＝Ｏ)－Ｘ１－）２、－Ｘ２（－Ｘ１－Ｘ２－）２、－Ｘ２（－Ｘ１－Ｘ２－Ｘ１－）２、－Ｘ２（－Ｘ１－Ｘ２－Ｘ１－Ｃ（＝Ｏ）－）２、－Ｘ２（－Ｘ１－Ｘ２－Ｃ（＝Ｏ）－Ｘ１－）２、－Ｘ２（－Ｘ１－Ｘ２－Ｘ１－Ｃ（＝Ｏ）－Ｘ１－）２、－Ｘ２（－Ｘ１－Ｘ２－Ｘ１－Ｘ２－）２等が挙げられる。
等が挙げられる。 Examples of X include, when X is trivalent, -X 1 (-) 2 , -X 1 -X 1 (-) 2 , -X 1 -X 2 (-X 1 -) 2 , -X 2 ( -X 1 -) 2 , -X 2 (-X 1 -C(=O)-) 2 , -X 2 (-C(=O)-X 1 -) 2 , -X 2 (-X 1 -C (=O)-X 1 -) 2 , -X 2 (-X 1 -X 2 -) 2 , -X 2 (-X 1 -X 2 -X 1 -) 2 , -X 2 (-X 1 - X 2 -X 1 -C(=O)-) 2 , -X 2 (-X 1 -X 2 -C(=O)-X 1 -) 2 , -X 2 (-X 1 -X 2 -X 1 -C(=O)-X 1 -) 2 , -X 2 (-X 1 -X 2 -X 1 -X 2 -) 2 and the like.
etc.
　Ｘの例としては、Ｘが四価の場合、－Ｘ１－Ｘ２（－Ｘ１－）３、－Ｘ２（－Ｘ１－）３、－Ｘ２（－Ｘ１－Ｃ(＝Ｏ)－）３、－Ｘ２（－Ｃ(＝Ｏ)－Ｘ１－）３、－Ｘ２（－Ｘ１－Ｃ(＝Ｏ)－Ｘ１－）３、－Ｘ２（－Ｘ１－Ｘ２－）３、－Ｘ２（－Ｘ１－Ｘ２－Ｘ１－）３、－Ｘ２（－Ｘ１－Ｘ２－Ｘ１－Ｃ（＝Ｏ）－）３、－Ｘ２（－Ｘ１－Ｘ２－Ｃ（＝Ｏ）－Ｘ１－）３、－Ｘ２（－Ｘ１－Ｘ２－Ｘ１－Ｃ（＝Ｏ）－Ｘ１－）３、－Ｘ２（－Ｘ１－Ｘ２－Ｘ１－Ｘ２－）３等が挙げられる。 Examples of X include -X 1 -X 2 (-X 1 -) 3 , -X 2 (-X 1 -) 3 , -X 2 (-X 1 -C(=O )-) 3 , -X 2 (-C(=O)-X 1 -) 3 , -X 2 (-X 1 -C(=O)-X 1 -) 3 , -X 2 (-X 1 - X 2 -) 3 , -X 2 (-X 1 -X 2 -X 1 -) 3 , -X 2 (-X 1 -X 2 -X 1 -C(=O)-) 3 , -X 2 ( -X 1 -X 2 -C(=O)-X 1 -) 3 , -X 2 (-X 1 -X 2 -X 1 -C(=O)-X 1 -) 3 , -X 2 (- X 1 -X 2 -X 1 -X 2 -) 3 and the like.
　Ｘの具体例としては、Ｘが二価の場合、－Ｏ－、－Ｏ－Ｃ(＝Ｏ)－、－Ｏ－Ｃ(＝Ｏ)－Ｏ－、－Ｏ－Ｃ(＝Ｏ)－ＮＲ’－、－Ｏ－Ｘ２－Ｓ(＝Ｏ)２－ＮＲ’－、－Ｏ－Ｘ２－ＮＲ’－、－Ｏ－Ｘ２－ＮＲ’－Ｓ(＝Ｏ)２－、－Ｏ－Ｘ２－ＮＲ’－Ｃ（＝Ｏ）－、－Ｏ－Ｘ２－ＮＲ’－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｘ２－ＮＲ’－Ｃ（＝Ｏ）－ＮＲ’－、－Ｏ－Ｘ２－ＮＲ’－Ｘ２－、－Ｏ－Ｘ２－Ｏ－、－Ｏ－Ｘ２－Ｏ－Ｃ（＝Ｏ）－、－Ｏ－Ｘ２－Ｏ－Ｃ（＝Ｏ）－ＮＲ’－、－Ｏ－Ｘ２－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｘ２－Ｃ（＝Ｏ）－ＮＲ’－、－Ｏ－Ｘ２－Ｏ－Ｘ２－、－Ｏ－Ｘ２－、－ＮＲ’－、－ＮＲ’－Ｃ(＝Ｏ)－、－ＮＲ’－Ｃ(＝Ｏ)－Ｏ－、－ＮＲ’－Ｃ(＝Ｏ)－ＮＲ’－、－ＮＲ’－Ｘ２－Ｓ(＝Ｏ)２－ＮＲ’－、－ＮＲ’－Ｘ２－ＮＲ’－、－ＮＲ’－Ｘ２－ＮＲ’－Ｓ(＝Ｏ)２－、－ＮＲ’－Ｘ２－ＮＲ’－Ｃ（＝Ｏ）－、－ＮＲ’－Ｘ２－ＮＲ’－Ｃ（＝Ｏ）－Ｏ－、－ＮＲ’－Ｘ２－ＮＲ’－Ｃ（＝Ｏ）－ＮＲ’－、－ＮＲ’－Ｘ２－ＮＲ’－Ｘ２－、－ＮＲ’－Ｘ２－Ｏ－、－ＮＲ’－Ｘ２－Ｏ－Ｃ（＝Ｏ）－、－ＮＲ’－Ｘ２－Ｏ－Ｃ（＝Ｏ）－ＮＲ’－、－ＮＲ’－Ｘ２－Ｏ－Ｘ２－、－ＮＲ’－Ｘ２－Ｃ（＝Ｏ）－Ｏ－、－ＮＲ’－Ｘ２－Ｃ（＝Ｏ）－ＮＲ’－、－ＮＲ’－Ｘ２－、－Ｃ(＝Ｏ)－、－Ｃ(＝Ｏ)－Ｏ－、－Ｃ(＝Ｏ)－ＮＲ’－、－Ｃ(＝Ｏ)－Ｓ－、－ＳＯ２－、－ＳＯ２ＮＲ’－、－Ｃ（ＯＲ’）（Ｒ’）（－）、等が挙げられる。 Specific examples of X include -O-, -O-C(=O)-, -O-C(=O)-O-, -O-C(=O)-NR when X is divalent. '-, -O-X 2 -S(=O) 2 -NR'-, -O-X 2 -NR'-, -O-X 2 -NR'-S(=O) 2 -, -O- X 2 -NR'-C(=O)-, -O-X 2 -NR'-C(=O)-O-, -O-X 2 -NR'-C(=O)-NR'-, -O-X 2 -NR'-X 2 -, -O-X 2 -O-, -O-X 2 -O-C(=O)-, -O-X 2 -O-C(=O) -NR'-, -O-X 2 -C(=O)-O-, -O-X 2 -C(=O)-NR'-, -O-X 2 -O-X 2 -, -O -X 2 -, -NR'-, -NR'-C(=O)-, -NR'-C(=O)-O-, -NR'-C(=O)-NR'-, -NR '-X 2 -S(=O) 2 -NR'-, -NR'-X 2 -NR'-, -NR'-X 2 -NR'-S(=O) 2 -, -NR'-X 2 -NR'-C(=O)-, -NR'-X 2 -NR'-C(=O)-O-, -NR'-X 2 -NR'-C(=O)-NR'- , -NR'-X 2 -NR'-X 2 -, -NR'-X 2 -O-, -NR'-X 2 -O-C(=O)-, -NR'-X 2 -O- C(=O)-NR'-, -NR'-X 2 -O-X 2 -, -NR'-X 2 -C(=O)-O-, -NR'-X 2 -C(=O ) -NR'-, -NR'-X 2 -, -C(=O)-, -C(=O)-O-, -C(=O)-NR'-, -C(=O)- Examples include S-, -SO 2 -, -SO 2 NR'-, -C(OR')(R')(-) , and the like.
　Ｘの具体例としては、Ｘが三価の場合、－Ｘ２（－Ｏ－）２－、－Ｘ２（－Ｏ－Ｃ(＝Ｏ)－）２－、－Ｘ２（－Ｏ－Ｃ(＝Ｏ)－Ｏ－）２－、－Ｘ２（－Ｏ－Ｃ(＝Ｏ)－ＮＲ’－）２－、－Ｘ２（－Ｏ－Ｘ２－Ｓ(＝Ｏ)２－ＮＲ’－）２－、－Ｘ２（－Ｏ－Ｘ２－ＮＲ’－）２－、－Ｘ２（－Ｏ－Ｘ２－ＮＲ’－Ｓ(＝Ｏ)２－）２－、－Ｘ２（－Ｏ－Ｘ２－ＮＲ’－Ｃ（＝Ｏ）－）２－、－Ｘ２（－Ｏ－Ｘ２－ＮＲ’－Ｃ（＝Ｏ）－Ｏ－）２－、－Ｘ２（－Ｏ－Ｘ２－ＮＲ’－Ｃ（＝Ｏ）－ＮＲ’－）２－、－Ｘ２（－Ｏ－Ｘ２－ＮＲ’－Ｘ２－）２－、－Ｘ２（－Ｏ－Ｘ２－Ｏ－）２－、－Ｘ２（－Ｏ－Ｘ２－Ｏ－Ｃ（＝Ｏ）－）２－、－Ｘ２（－Ｏ－Ｘ２－Ｏ－Ｃ（＝Ｏ）－ＮＲ’－）２－、－Ｘ２（－Ｏ－Ｘ２－Ｃ（＝Ｏ）－Ｏ－）２－、－Ｘ２（－Ｏ－Ｘ２－Ｃ（＝Ｏ）－ＮＲ’－）２－、－Ｘ２（－Ｏ－Ｘ２－Ｏ－Ｘ２－）２－、－Ｘ２（－Ｏ－Ｘ２－）２－、－Ｘ２（－ＮＲ’－）２－、－Ｘ２（－ＮＲ’－Ｃ(＝Ｏ)－）２－、－Ｘ２（－ＮＲ’－Ｃ(＝Ｏ)－Ｏ－）２－、－Ｘ２（－ＮＲ’－Ｃ(＝Ｏ)－ＮＲ’－）２－、－Ｘ２（－ＮＲ’－Ｘ２－Ｓ(＝Ｏ)２－ＮＲ’－）２－、－Ｘ２（－ＮＲ’－Ｘ２－ＮＲ’－）２－、－Ｘ２（－ＮＲ’－Ｘ２－ＮＲ’－Ｓ(＝Ｏ)２－）２－、－Ｘ２（－ＮＲ’－Ｘ２－ＮＲ’－Ｃ（＝Ｏ）－）２－、－Ｘ２（－ＮＲ’－Ｘ２－ＮＲ’－Ｃ（＝Ｏ）－Ｏ－）２－、－Ｘ２（－ＮＲ’－Ｘ２－ＮＲ’－Ｃ（＝Ｏ）－ＮＲ’－）２－、－Ｘ２（－ＮＲ’－Ｘ２－ＮＲ’－Ｘ２－）２－、－Ｘ２（－ＮＲ’－Ｘ２－Ｏ－）２－、－Ｘ２（－ＮＲ’－Ｘ２－Ｏ－Ｃ（＝Ｏ）－）２－、－Ｘ２（－ＮＲ’－Ｘ２－Ｏ－Ｃ（＝Ｏ）－ＮＲ’－）２－、－Ｘ２（－ＮＲ’－Ｘ２－Ｏ－Ｘ２－）２－、－Ｘ２（－ＮＲ’－Ｘ２－Ｃ（＝Ｏ）－Ｏ－）２－、－Ｘ２（－ＮＲ’－Ｘ２－Ｃ（＝Ｏ）－ＮＲ’－）２－、－Ｘ２（－ＮＲ’－Ｘ２－）２－、－Ｘ２（－Ｃ(＝Ｏ)－）２－、－Ｘ２（－Ｃ(＝Ｏ)－Ｏ－）２－、－Ｘ２（－Ｃ(＝Ｏ)－ＮＲ’－）２－、－Ｘ２（－Ｃ(＝Ｏ)－Ｓ－）２－、－Ｘ２（－ＳＯ２－）２－、－Ｘ２（－ＳＯ２ＮＲ’－）２－、－Ｘ２（－Ｃ（ＯＲ’）（Ｒ’）（－））２－、－Ｃ（ＯＲ’）（－）２、等が挙げられる。 Specific examples of X include, when X is trivalent, -X 2 (-O-) 2 -, -X 2 (-O-C(=O)-) 2 -, -X 2 (-O-C (=O)-O-) 2 -, -X 2 (-O-C(=O)-NR'-) 2 -, -X 2 (-O-X 2 -S(=O) 2 -NR' -) 2 -, -X 2 (-O-X 2 -NR'-) 2 -, -X 2 (-O-X 2 -NR'-S(=O) 2 -) 2 -, -X 2 ( -O-X 2 -NR'-C(=O)-) 2 -, -X 2 (-O-X 2 -NR'-C(=O)-O-) 2 -, -X 2 (-O -X 2 -NR'-C(=O)-NR'-) 2 -, -X 2 (-O-X 2 -NR'-X 2 -) 2 -, -X 2 (-O-X 2 - O-) 2 -, -X 2 (-O-X 2 -OC(=O)-) 2 -, -X 2 (-O-X 2 -O-C(=O)-NR'-) 2 -, -X 2 (-O-X 2 -C(=O)-O-) 2 -, -X 2 (-O-X 2 -C(=O)-NR'-) 2 -, -X 2 (-O-X 2 -O-X 2 -) 2 -, -X 2 (-O-X 2 -) 2 -, -X 2 (-NR'-) 2 -, -X 2 (-NR' -C(=O)-) 2 -, -X 2 (-NR'-C(=O)-O-) 2 -, -X 2 (-NR'-C(=O)-NR'-) 2 -, -X 2 (-NR'-X 2 -S(=O) 2 -NR'-) 2 -, -X 2 (-NR'-X 2 -NR'-) 2 -, -X 2 (- NR'-X 2 -NR'-S(=O) 2 -) 2 -, -X 2 (-NR'-X 2 -NR'-C(=O)-) 2 -, -X 2 (-NR '-X 2 -NR'-C(=O)-O-) 2 -, -X 2 (-NR'-X 2 -NR'-C(=O)-NR'-) 2 -, -X 2 (-NR'-X 2 -NR'-X 2 -) 2 -, -X 2 (-NR'-X 2 -O-) 2 -, -X 2 (-NR'-X 2 -O-C( =O)-) 2 -, -X 2 (-NR'-X 2 -OC(=O)-NR'-) 2 -, -X 2 (-NR'-X 2 -O-X 2 - ) 2 -, -X 2 (-NR'-X 2 -C(=O)-O-) 2 -, -X 2 (-NR'-X 2 -C(=O)-NR'-) 2 - , -X 2 (-NR'-X 2 -) 2 -, -X 2 (-C(=O)-) 2 -, -X 2 (-C(=O)-O-) 2 -, -X 2 (-C(=O)-NR'-) 2 -, -X 2 (-C(=O)-S-) 2 -, -X 2 (-SO 2 -) 2 -, -X 2 (- SO 2 NR'-) 2 -, -X 2 (-C(OR')(R')(-)) 2 -, -C(OR')(-) 2, and the like.
　Ｘの具体例としては、Ｘが四価の場合、－Ｘ２（－Ｏ－）３－、－Ｘ２（－Ｏ－Ｃ(＝Ｏ)－）３－、－Ｘ２（－Ｏ－Ｃ(＝Ｏ)－Ｏ－）３－、－Ｘ２（－Ｏ－Ｃ(＝Ｏ)－ＮＲ’－）３－、－Ｘ２（－Ｏ－Ｘ２－Ｓ(＝Ｏ)２－ＮＲ’－）３－、－Ｘ２（－Ｏ－Ｘ２－ＮＲ’－）３－、－Ｘ２（－Ｏ－Ｘ２－ＮＲ’－Ｓ(＝Ｏ)２－）３－、－Ｘ２（－Ｏ－Ｘ２－ＮＲ’－Ｃ（＝Ｏ）－）３－、－Ｘ２（－Ｏ－Ｘ２－ＮＲ’－Ｃ（＝Ｏ）－Ｏ－）３－、－Ｘ２（－Ｏ－Ｘ２－ＮＲ’－Ｃ（＝Ｏ）－ＮＲ’－）３－、－Ｘ２（－Ｏ－Ｘ２－ＮＲ’－Ｘ２－）３－、－Ｘ２（－Ｏ－Ｘ２－Ｏ－）３－、－Ｘ２（－Ｏ－Ｘ２－Ｏ－Ｃ（＝Ｏ）－）３－、－Ｘ２（－Ｏ－Ｘ２－Ｏ－Ｃ（＝Ｏ）－ＮＲ’－）３－、－Ｘ２（－Ｏ－Ｘ２－Ｃ（＝Ｏ）－Ｏ－）３－、－Ｘ２（－Ｏ－Ｘ２－Ｃ（＝Ｏ）－ＮＲ’－）３－、－Ｘ２（－Ｏ－Ｘ２－Ｏ－Ｘ２－）３－、－Ｘ２（－Ｏ－Ｘ２－）３－、－Ｘ２（－ＮＲ’－）３－、－Ｘ２（－ＮＲ’－Ｃ(＝Ｏ)－）３－、－Ｘ２（－ＮＲ’－Ｃ(＝Ｏ)－Ｏ－）３－、－Ｘ２（－ＮＲ’－Ｃ(＝Ｏ)－ＮＲ’－）３－、－Ｘ２（－ＮＲ’－Ｘ２－Ｓ(＝Ｏ)２－ＮＲ’－）３－、－Ｘ２（－ＮＲ’－Ｘ２－ＮＲ’－）３－、－Ｘ２（－ＮＲ’－Ｘ２－ＮＲ’－Ｓ(＝Ｏ)２－）３－、－Ｘ２（－ＮＲ’－Ｘ２－ＮＲ’－Ｃ（＝Ｏ）－）３－、－Ｘ２（－ＮＲ’－Ｘ２－ＮＲ’－Ｃ（＝Ｏ）－Ｏ－）３－、－Ｘ２（－ＮＲ’－Ｘ２－ＮＲ’－Ｃ（＝Ｏ）－ＮＲ’－）３－、－Ｘ２（－ＮＲ’－Ｘ２－ＮＲ’－Ｘ２－）３－、－Ｘ２（－ＮＲ’－Ｘ２－Ｏ－）３－、－Ｘ２（－ＮＲ’－Ｘ２－Ｏ－Ｃ（＝Ｏ）－）３－、－Ｘ２（－ＮＲ’－Ｘ２－Ｏ－Ｃ（＝Ｏ）－ＮＲ’－）３－、－Ｘ２（－ＮＲ’－Ｘ２－Ｏ－Ｘ２－）３－、－Ｘ２（－ＮＲ’－Ｘ２－Ｃ（＝Ｏ）－Ｏ－）３－、－Ｘ２（－ＮＲ’－Ｘ２－Ｃ（＝Ｏ）－ＮＲ’－）３－、－Ｘ２（－ＮＲ’－Ｘ２－）３－、－Ｘ２（－Ｃ(＝Ｏ)－）３－、－Ｘ２（－Ｃ(＝Ｏ)－Ｏ－）３－、－Ｘ２（－Ｃ(＝Ｏ)－ＮＲ’－）３－、－Ｘ２（－Ｃ(＝Ｏ)－Ｓ－）３－、－Ｘ２（－ＳＯ２－）３－、－Ｘ２（－ＳＯ２ＮＲ’－）３－、－Ｘ２（－Ｃ（ＯＲ’）（Ｒ’）（－））３－、等が挙げられる。 Specific examples of X include, when X is tetravalent, -X 2 (-O-) 3 -, -X 2 (-O-C(=O)-) 3 -, -X 2 (-O-C (=O)-O-) 3 -, -X 2 (-O-C(=O)-NR'-) 3 -, -X 2 (-O-X 2 -S(=O) 2 -NR' -) 3 -, -X 2 (-O-X 2 -NR'-) 3 -, -X 2 (-O-X 2 -NR'-S(=O) 2 -) 3 -, -X 2 ( -O-X 2 -NR'-C(=O)-) 3 -, -X 2 (-O-X 2 -NR'-C(=O)-O-) 3 -, -X 2 (-O -X 2 -NR'-C(=O)-NR'-) 3 -, -X 2 (-O-X 2 -NR'-X 2 -) 3 -, -X 2 (-O-X 2 - O-) 3 -, -X 2 (-O-X 2 -OC(=O)-) 3 -, -X 2 (-O-X 2 -O-C(=O)-NR'-) 3 -, -X 2 (-O-X 2 -C(=O)-O-) 3 -, -X 2 (-O-X 2 -C(=O)-NR'-) 3 -, -X 2 (-O-X 2 -O-X 2 -) 3 -, -X 2 (-O-X 2 -) 3 -, -X 2 (-NR'-) 3 -, -X 2 (-NR' -C(=O)-) 3 -, -X 2 (-NR'-C(=O)-O-) 3 -, -X 2 (-NR'-C(=O)-NR'-) 3 -, -X 2 (-NR'-X 2 -S(=O) 2 -NR'-) 3 -, -X 2 (-NR'-X 2 -NR'-) 3 -, -X 2 (- NR'-X 2 -NR'-S(=O) 2 -) 3 -, -X 2 (-NR'-X 2 -NR'-C(=O)-) 3 -, -X 2 (-NR '-X 2 -NR'-C(=O)-O-) 3 -, -X 2 (-NR'-X 2 -NR'-C(=O)-NR'-) 3 -, -X 2 (-NR'-X 2 -NR'-X 2 -) 3 -, -X 2 (-NR'-X 2 -O-) 3 -, -X 2 (-NR'-X 2 -O-C( =O)-) 3 -, -X 2 (-NR'-X 2 -OC(=O)-NR'-) 3 -, -X 2 (-NR'-X 2 -O-X 2 - ) 3 -, -X 2 (-NR'-X 2 -C(=O)-O-) 3 -, -X 2 (-NR'-X 2 -C(=O)-NR'-) 3 - , -X 2 (-NR'-X 2 -) 3 -, -X 2 (-C(=O)-) 3 -, -X 2 (-C(=O)-O-) 3 -, -X 2 (-C(=O)-NR'-) 3 -, -X 2 (-C(=O)-S-) 3 -, -X 2 (-SO 2 -) 3 -, -X 2 (- Examples thereof include SO 2 NR'-) 3 -, -X 2 (-C(OR')(R')(-)) 3 -, and the like.
［Ｒ］
　Ｒは、置換基を有してよい炭素数６以上４０以下の一価の脂肪族炭化水素基である。Ｒは、環状、分岐鎖状、直鎖状であってよく、好ましくは分岐鎖状又は直鎖状であり、より好ましくは直鎖状である。Ｒは、置換基を有してよい飽和の脂肪族炭化水素基（アルキル基）であることが好ましい。 [R]
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, more preferably linear. R is preferably a saturated aliphatic hydrocarbon group (alkyl group) that may have a substituent.
　Ｒの炭素数は、６以上、８以上、１０以上、１２以上、１４以上、１６以上、又は１８以上であってよく、好ましくは１０以上、より好ましくは１２以上である。Ｒの炭素数は４０以下、３５以下、３０以下、２５以下、２０以下、１５以下、又は１０以下であってよく、好ましくは３０以下、より好ましくは２５以下である。 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.
　ここで、Ｒである、置換基を有してよい炭素数６以上４０以下の一価の脂肪族炭化水素基は、置換基を有する炭化水素基であってもよいが、無置換の炭化水素基であってもよい。ここで、置換基の例としては、－ＯＲ’、－Ｎ（Ｒ’）２、－ＣＯＯＲ’、及びハロゲン原子等（式中、Ｒ’は、各出現において独立して、水素原子又は炭素数１～４の炭化水素基である）が挙げられ。置換基は活性水素を有してよいし、有していなくてもよい。置換基の数は、６個以下、５個以下、４個以下、３個以下、２個以下、１個以下、又は０であってよい。置換基を有する炭化水素基において、炭素原子及びヘテロ原子の合計量に対する炭素原子の量が７０ｍｏｌ％以上、８０ｍｏｌ％以上、９０ｍｏｌ％以上、９５ｍｏｌ％以上、又は９９ｍｏｌ％以上であってよく、好ましくは７５ｍｏｌ％以上である。置換基を有する炭化水素基において、炭素原子及びヘテロ原子の合計量に対する炭素原子の量が９５ｍｏｌ％以下、９０ｍｏｌ％以下、８５ｍｏｌ％以下、又は８０ｍｏｌ％以下であってよい。例えば、炭素数６以上４０以下の基は、置換基として１～３個（例えば１個）の－ＯＲ’（特に－ＯＨ）を（例えば末端以外において）有してよい。 Here, R, a monovalent aliphatic hydrocarbon group having 6 to 40 carbon atoms and which may have a substituent, may be a hydrocarbon group having a substituent, but may be an unsubstituted hydrocarbon group. It may be a base. Here, examples of 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. In the hydrocarbon group having a substituent, 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. In the hydrocarbon group having a substituent, 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. For example, 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).
［化合物αの製造方法］
　炭化水素芳香環に置換基を有してよい炭素数６以上４０以下の炭化水素基を修飾方法としては特に限定されない。例えば、ウレタン結合形成反応、ウレア結合形成反応、エステル結合形成反応、アミド結合形成反応、及びエーテル結合形成反応等の方法を用いることができる。結合形成反応においては、アシル化剤、縮合剤、触媒等が適宜使用される。 [Method for producing compound α]
The method for modifying the hydrocarbon group having 6 or more and 40 or less carbon atoms which may have a substituent on the aromatic hydrocarbon ring is not particularly limited. For example, 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. In the bond-forming reaction, an acylating agent, a condensing agent, a catalyst, etc. are used as appropriate.
　炭化水素芳香環に置換基を有してよい炭素数６以上４０以下の炭化水素基を修飾する方法としては、炭化水素基含有反応体とを反応させることで行われてもよい。炭化水素基含有反応体とは、炭化水素基と、炭化水素芳香環が有する官能基と反応し得る基とを有する化合物である。 A method for modifying a hydrocarbon group having 6 or more and 40 or less carbon atoms which may have a substituent on a hydrocarbon aromatic ring may be carried out by reacting with a hydrocarbon group-containing reactant. The hydrocarbon group-containing reactant is a compound having a hydrocarbon group and a group capable of reacting with a functional group possessed by an aromatic hydrocarbon ring.
　炭化水素基含有反応体の例は次のとおりである。
Ｈ２Ｎ－Ｒ
ＨＯ－Ｒ
ＨＯ（Ｏ＝）Ｃ－Ｒ
Ｇ（Ｏ＝）Ｃ－Ｒ
ＲＣ（＝Ｏ）ＯＣ（＝Ｏ）Ｒ
Ｏ＝Ｃ＝Ｎ－Ｒ
Ｓ＝Ｃ＝Ｎ－Ｒ
（ＣＨ２ＯＣＨ）ＣＨ２ＯＲ
Ｇ－Ｒ
[式中、Ｒは６以上４０以下の脂肪族炭化水素基であり、上記で定義したとおりである。Ｇはハロゲン原子（特にＦ、Ｃｌ、Ｂｒ、又はＩ）である。] Examples of hydrocarbon group-containing reactants are:
H2NR
HO-R
HO(O=)CR
G(O=)CR
RC(=O)OC(=O)R
O=C=NR
S=C=NR
( CH2OCH ) CH2OR
G-R
[In the formula, R is an aliphatic hydrocarbon group of 6 or more and 40 or less, as defined above. G is a halogen atom (especially F, Cl, Br or I). ]
（ウレタン結合形成）
　炭化水素芳香環と炭化水素基とが、ウレタン結合を介して結合していてよい。ウレタン結合は、例えば、水酸基含有炭化水素芳香環と、脂肪族炭化水素含有イソシアネートを反応させることで、形成されてもよい。反応時に錫触媒やアミンを触媒として使用することができる。例えば、有機溶媒中で水酸基含有炭化水素芳香環と炭化水素基含有イソシアネートとを一定時間反応させることにより水酸基がイソシアネート基と反応し、炭化水素芳香環と炭化水素基とがウレタン結合を介して結合している化合物αが得られる。 (Urethane bond formation)
The aromatic hydrocarbon ring 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 hydrocarbon aromatic ring with an aliphatic hydrocarbon-containing isocyanate. A tin catalyst or an amine can be used as a catalyst during the reaction. For example, by reacting a hydroxyl group-containing aromatic hydrocarbon ring and a hydrocarbon group-containing isocyanate in an organic solvent for a certain period of time, the hydroxyl group reacts with the isocyanate group, and the hydrocarbon aromatic ring and the hydrocarbon group are bonded via a urethane bond. Compound α is obtained.
（ウレア結合形成）
　炭化水素芳香環と炭化水素基とが、ウレア結合を介して結合していてよい。ウレア結合は、例えば、アミノ基含有炭化水素芳香環と、炭化水素基含有イソシアネート基を反応させること（又は、イソシアネート基含有炭化水素芳香環と、炭化水素基含有アミンを反応させること）で、形成されてもよい。反応時に適宜触媒を利用してもよい。例えば、有機溶媒中でアミノ基含有炭化水素芳香環と脂肪族炭化水素含有イソシアネートとを一定時間反応させることにより、アミノ基がイソシアネート基と反応し、炭化水素芳香環と炭化水素基とがウレア結合を介して結合している化合物αが得られる。 (urea bond formation)
The aromatic hydrocarbon ring and the hydrocarbon group may be bonded via a urea bond. A urea bond can be formed, for example, by reacting an amino group-containing hydrocarbon aromatic ring with a hydrocarbon group-containing isocyanate group (or by reacting an isocyanate group-containing hydrocarbon aromatic ring with a hydrocarbon group-containing amine). may be done. A catalyst may be used as appropriate during the reaction. For example, by reacting an amino group-containing aromatic hydrocarbon ring with 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 hydrocarbon aromatic ring and the hydrocarbon group form a urea bond. A compound α is obtained which is bound via .
（エステル結合形成）
　炭化水素芳香環と炭化水素基とが、エステル結合を介して結合していてよい。エステル結合は、例えば、水酸基含有炭化水素芳香環と、炭化水素基含有カルボン酸を反応させること（又は、カルボン酸含有炭化水素芳香環と、炭化水素基含有アルコールを反応させること）で、形成されてもよい。反応時にアシル化触媒や縮合剤等を利用してもよい。例えば、有機溶媒中で水酸基含有炭化水素芳香環と炭化水素基含有カルボン酸とを一定時間反応させることにより、水酸基がカルボン酸と反応し、炭化水素芳香環と炭化水素基とがエステル結合を介して結合している化合物αが得られる。 (Ester bond formation)
The aromatic hydrocarbon ring and the hydrocarbon group may be bonded via an ester bond. The ester bond is formed, for example, by reacting a hydroxyl group-containing hydrocarbon aromatic ring with a hydrocarbon group-containing carboxylic acid (or by reacting a carboxylic acid-containing hydrocarbon aromatic ring with a hydrocarbon group-containing alcohol). You can. An acylation catalyst, condensing agent, etc. may be used during the reaction. For example, by reacting a hydroxyl group-containing aromatic hydrocarbon ring and 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 hydrocarbon aromatic ring and the hydrocarbon group form an ester bond. A bound compound α is obtained.
（アミド結合形成）
　炭化水素芳香環と炭化水素基とが、アミド結合を介して結合していてよい。アミド結合は、例えば、アミノ基含有炭化水素芳香環と、炭化水素基含有カルボン酸を反応させること（又は、カルボン酸含有炭化水素芳香環と、炭化水素基含有アミンを反応させること）で、形成されてもよい。反応時にアシル化触媒や縮合剤等を利用してもよい。例えば、有機溶媒中でアミノ基含有炭化水素芳香環と炭化水素基含有カルボン酸とを一定時間反応させることにより、アミノ基がカルボン酸と反応し、炭化水素芳香環と炭化水素基とがアミド結合を介して結合している化合物αが得られる。 (amide bond formation)
The aromatic hydrocarbon ring and the hydrocarbon group may be bonded via an amide bond. An amide bond can be formed, for example, by reacting an amino group-containing hydrocarbon aromatic ring with a hydrocarbon group-containing carboxylic acid (or by reacting a carboxylic acid-containing hydrocarbon aromatic ring with a hydrocarbon group-containing amine). may be done. An acylation catalyst, condensing agent, etc. may be used during the reaction. For example, by reacting an amino group-containing aromatic hydrocarbon ring and a hydrocarbon group-containing carboxylic acid in an organic solvent for a certain period of time, the amino group reacts with the carboxylic acid, and the hydrocarbon aromatic ring and the hydrocarbon group form an amide bond. A compound α is obtained which is bound via .
（エーテル結合形成）
　炭化水素芳香環と炭化水素基とが、エーテル結合を介して結合していてよい。エーテル結合は、例えば、ハロゲン含有炭化水素芳香環と、炭化水素基含有アルコールを反応させること（又は、水酸基含有炭化水素芳香環と、炭化水素基含有ハロゲン化物を反応させること）で、形成されてもよい。反応時に酸触媒、塩基触媒等を利用してもよい。例えば、有機溶媒中でハロゲン含有炭化水素芳香環と炭化水素基含有アルコールを、触媒下、加熱して反応させることにより、炭化水素基含有アルコールが求核剤として働いて、炭化水素芳香環と炭化水素基とがエーテル結合を介して結合している化合物αが得られる。 (ether bond formation)
The aromatic hydrocarbon ring and the hydrocarbon group may be bonded via an ether bond. The ether bond is formed, for example, by reacting a halogen-containing hydrocarbon aromatic ring with a hydrocarbon group-containing alcohol (or by reacting a hydroxyl group-containing hydrocarbon aromatic ring with a hydrocarbon group-containing halide). Good too. An acid catalyst, a base catalyst, etc. may be used during the reaction. For example, by heating and reacting a halogen-containing hydrocarbon aromatic ring and a hydrocarbon group-containing alcohol under a catalyst in an organic solvent, the hydrocarbon group-containing alcohol acts as a nucleophile, and the hydrocarbon aromatic ring and the carbonized A compound α in which a hydrogen group is bonded via an ether bond is obtained.
［化合物αの量］
　化合物αの量は、撥剤中、０．０１重量％以上、０．５重量％以上、１重量％以上、３重量％以上、５重量％以上、１０重量％以上、２０重量％以上、３０重量％以上であってよい。化合物αの量は、撥剤中、６０重量％以下、５０重量％以下、４０重量％以下、３０重量％以下、２０重量％以下、１０重量％以下、５重量％以下、又は３重量％以下であってよい。 [Amount of compound α]
The amount of compound α in the repellent 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, 30% by weight or more. It may be more than % by weight. The amount of compound α 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 or less in the repellent. It may be.
〔液状媒体〕
　本開示における撥剤は、液状媒体を含んでもよい。液状媒体は水、有機溶媒、又は水と有機溶媒との混合物であってよい。撥剤は分散液又は溶液であってよい。 [Liquid medium]
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. The repellent may be a dispersion or a solution.
　有機溶媒の例は、エステル（例えば、炭素数２～４０のエステル、具体的には、酢酸エチル、酢酸ブチル）、ケトン（例えば、炭素数２～４０のケトン、具体的には、メチルエチルケトン、ジイソブチルケトン）、アルコール（例えば、炭素数１～４０のアルコール、具体的には、イソプロピルアルコール）、芳香族系溶剤（例えば、トルエン及びキシレン）、石油系溶剤（例えば、炭素数５～１０のアルカン、具体的には、ナフサ、灯油）である。有機溶媒は水溶性有機溶媒であることが好ましい。水溶性有機溶媒は少なくとも一のヒドロキシ基を有している化合物（例えば、アルコール、グリコール系溶媒等の多価アルコール、多価アルコールのエーテル体（例えばモノエーテル体）等）を含んでいてもよい。これらは単独で用いてもよいし、又は二以上を併用してもよい。 Examples of organic solvents 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). Preferably, the organic solvent is a water-soluble organic solvent. The water-soluble organic solvent may contain a compound having at least one hydroxy group (e.g., alcohol, polyhydric alcohol such as glycol solvent, ether form (e.g. monoether form) of polyhydric alcohol, etc.). . These may be used alone or in combination of two or more.
［液状媒体の量］
　液状媒体の量は、化合物α１重量部（或いは１０重量部、又は１００重量部）に対して、１重量部以上、３重量部以上、５重量部以上、１０重量部以上、２０重量部以上、３０重量部以上、４０重量部以上、又は５０重量部以上であってよい。液状媒体の量は、化合物α１重量部（或いは１０重量部、又は１００重量部）に対して、２００重量部以下、１７５重量部以下、１５０重量部以下、１２５重量部以下、１００重量部以下、８０重量部以下、６０重量部以下、４０重量部以下、２０重量部以下、又は１０重量部以下であってよい。 [Amount of liquid medium]
The amount of the liquid medium 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 or more, per 1 part by weight (or 10 parts by weight, or 100 parts by weight) of the compound α. It may be 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 or less, per 1 part by weight of the compound α (or 10 parts by weight, or 100 parts by weight). It may be 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less.
　水の量は、化合物α１重量部（或いは１０重量部、又は１００重量部）に対して、１重量部以上、３重量部以上、５重量部以上、１０重量部以上、２０重量部以上、３０重量部以上、４０重量部以上、又は５０重量部以上であってよい。有機溶媒の量は、化合物α１重量部（或いは１０重量部、又は１００重量部）に対して、２００重量部以下、１７５重量部以下、１５０重量部以下、１２５重量部以下、１００重量部以下、８０重量部以下、６０重量部以下、４０重量部以下、２０重量部以下、又は１０重量部以下であってよい。 The amount of water 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 or more, 30 parts by weight or more, based on 1 part by weight (or 10 parts by weight, or 100 parts by weight) of the compound α. It may be at least 40 parts by weight, or at least 50 parts by weight. 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 or less, per 1 part by weight of the compound α (or 10 parts by weight, or 100 parts by weight). It may be 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less.
　有機溶媒の量は、化合物α１重量部（或いは１０重量部、又は１００重量部）に対して、１重量部以上、３重量部以上、５重量部以上、１０重量部以上、２０重量部以上、３０重量部以上、４０重量部以上、又は５０重量部以上であってよい。有機溶媒の量は、化合物α１重量部（或いは１０重量部、又は１００重量部）に対して、２００重量部以下、１７５重量部以下、１５０重量部以下、１２５重量部以下、１００重量部以下、８０重量部以下、６０重量部以下、４０重量部以下、２０重量部以下、又は１０重量部以下であってよい。 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 or more, per 1 part by weight (or 10 parts by weight, or 100 parts by weight) of the compound α. It may be 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 or less, per 1 part by weight of the compound α (or 10 parts by weight, or 100 parts by weight). It may be 80 parts by weight or less, 60 parts by weight or less, 40 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less.
〔界面活性剤〕
　撥剤は、界面活性剤を含んでもよい。界面活性剤は、ノニオン性界面活性剤、カチオン性界面活性剤、アニオン性界面活性剤、及び両性界面活性剤から選択された一種以上の界面活性剤を含んでもよい。 [Surfactant]
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.
［ノニオン性界面活性剤］
　ノニオン性界面活性剤の例としては、エーテル、エステル、エステルエーテル、アルカノールアミド、多価アルコール及びアミンオキシドが挙げられる。 [Nonionic surfactant]
Examples of nonionic surfactants include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols, and amine oxides.
　エーテルの例は、オキシアルキレン基（好ましくは、ポリオキシエチレン基）を有する化合物である。 An example of an ether is a compound having an oxyalkylene group (preferably a polyoxyethylene group).
　エステルの例は、アルコールと脂肪酸のエステルである。アルコールの例は、１～６価（特に２～５価）の炭素数１～５０（特に炭素数１０～３０）のアルコール（例えば、脂肪族アルコール）である。脂肪酸の例は、炭素数２～５０、特に炭素数５～３０の飽和又は不飽和の脂肪酸である。 Examples of esters are esters of alcohols and fatty acids. Examples of 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). Examples of fatty acids are saturated or unsaturated fatty acids having 2 to 50 carbon atoms, especially 5 to 30 carbon atoms.
　エステルエーテルの例は、アルコールと脂肪酸のエステルに、アルキレンオキシド（特にエチレンオキシド）を付加した化合物である。アルコールの例は、１～６価（特に２～５価）の炭素数１～５０（特に炭素数３～３０）のアルコール（例えば、脂肪族アルコール）である。脂肪酸の例は、炭素数２～５０、特に炭素数５～３０の飽和又は不飽和の脂肪酸である。 An example of an ester ether is a compound obtained by adding alkylene oxide (especially ethylene oxide) to an ester of alcohol and fatty acid. 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.
　アルカノールアミドの例は、脂肪酸とアルカノールアミンから形成されている。アルカノールアミドは、モノアルカノールアミド又はジアルカノールアミノであってよい。脂肪酸の例は、炭素数２～５０、特に炭素数５～３０の飽和又は不飽和の脂肪酸である。アルカノールアミンは、１～３のアミノ基及び１～５ヒドロキシル基を有する炭素数２～５０、特に５～３０のアルカノールであってよい。 Examples of alkanolamides are formed from fatty acids and alkanolamines. The alkanolamide may be a monoalkanolamide or a dialkanolamide. Examples of 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.
　多価アルコールは、２～５価の炭素数１０～３０のアルコールであってよい。
　アミンオキシドは、アミン（二級アミン又は好ましくは三級アミン）の酸化物（例えば炭素数５～５０）であってよい。 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).
　ノニオン性界面活性剤は、オキシアルキレン基（好ましくはポリオキシエチレン基）を有するノニオン性界面活性剤であることが好ましい。オキシアルキレン基におけるアルキレン基の炭素数は、２～１０であることが好ましい。ノニオン性界面活性剤の分子におけるオキシアルキレン基の数は、一般に、２～１００であることが好ましい。
　ノニオン性界面活性剤は、エーテル、エステル、エステルエーテル、アルカノールアミド、多価アルコール及びアミンオキシドからなる群から選択されており、オキシアルキレン基を有するノニオン性界面活性剤であることが好ましい。 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 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.
　ノニオン性界面活性剤は、直鎖状及び／又は分岐状の脂肪族（飽和及び／又は不飽和）基のアルキレンオキシド付加物、直鎖状及び／又は分岐状脂肪酸（飽和及び／又は不飽和）のポリアルキレングリコールエステル、ポリオキシエチレン（POE）／ポリオキシプロピレン（POP）共重合体（ランダム共重合体又はブロック共重合体）、アセチレングリコールのアルキレンオキシド付加物等であってよい。これらの中で、アルキレンオキシド付加部分及びポリアルキレングリコール部分の構造がポリオキシエチレン（POE）又はポリオキシプロピレン（POP）又はPOE/POP共重合体（ランダム共重合体であってもブロック共重合体であってよい）であるものが好ましい。
　また、ノニオン性界面活性剤は、環境上の問題（生分解性、環境ホルモン等）から芳香族基を含まない構造が好ましい。 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. Among these, 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.
Furthermore, the nonionic surfactant preferably has a structure that does not contain an aromatic group due to environmental issues (biodegradability, endocrine disruptors, etc.).
　ノニオン性界面活性剤は、式：
　　　Ｒ1Ｏ－(ＣＨ２ＣＨ２Ｏ)p－(Ｒ2Ｏ)q－Ｒ3
[式中、Ｒ1は炭素数１～２２のアルキル基又は炭素数２～２２のアルケニル基又はアシル基であり、
Ｒ2のそれぞれは、独立的に同一又は異なって、炭素数３以上（例えば、３～１０）のアルキレン基であり、
Ｒ3は水素原子、炭素数１～２２のアルキル基又は炭素数２～２２のアルケニル基であり、
ｐは２以上の数であり、
ｑは0又は１以上の数である。]
で示される化合物であってよい。 Nonionic surfactants have the formula:
R 1 O-(CH 2 CH 2 O) p -(R 2 O) q - R 3
[In the formula, 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
　Ｒ1は、炭素数８～２０、特に１０～１８であることが好ましい。Ｒ1の好ましい具体例としては、ラウリル基、トリデシル基、オレイル基が挙げられる。
　Ｒ2の例は、プロピレン基、ブチレン基である。
　ノニオン性界面活性剤において、ｐは３以上の数（例えば、５～２００）であってよい。ｑは、２以上の数（例えば５～２００）であってよい。すなわち、－(Ｒ2Ｏ)q－がポリオキシアルキレン鎖を形成してもよい。
　ノニオン性界面活性剤は、中央に親水性のポリオキシエチレン鎖と疎水性のオキシアルキレン鎖（特に、ポリオキシアルキレン鎖）を含有したポリオキシエチレンアルキレンアルキルエーテルであってよい。疎水性のオキシアルキレン鎖としては、オキシプロピレン鎖、オキシブチレン鎖、スチレン鎖等が挙げられるが、中でも、オキシプロピレン鎖が好ましい。 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.
Examples of R 2 are propylene and butylene.
In nonionic surfactants, 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. Examples of the hydrophobic oxyalkylene chain include an oxypropylene chain, an oxybutylene chain, a styrene chain, and among them, an oxypropylene chain is preferred.
　ノニオン性界面活性剤の具体例には、エチレンオキシドとヘキシルフェノール、イソオクタチルフェノール、ヘキサデカノール、オレイン酸、アルカン（Ｃ１２－Ｃ１６）チオール、ソルビタンモノ脂肪酸（Ｃ７－Ｃ１９）又はアルキル（Ｃ１２－Ｃ１８）アミン等との縮合生成物が包含される。 Specific examples of 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.
　ポリオキシエチレンブロックの割合がノニオン性界面活性剤（コポリマー）の分子量に対して５～８０重量％、例えば３０～７５重量％、特に４０～７０重量％であることができる。
　ノニオン性界面活性剤の平均分子量は、一般に３００～５,０００、例えば、５００～３,０００である。
　ノニオン界面活性剤は、ＨＬＢ（親水性疎水性バランス）が１５未満（特に５以下）である化合物とＨＬＢが１５以上である化合物の混合物であってよい。ＨＬＢが１５未満である化合物の例は、ソルビタン脂肪酸エステルである。ＨＬＢが１５以上である化合物の例はポリオキシエチレンアルキルエーテルである。ＨＬＢ１５未満の化合物とＨＬＢ１５以上の化合物の重量比は、９０：１０～２０：８０、例えば８５：１５～５５：４５であってよい。
　ノニオン性界面活性剤は、一種単独であってよく、あるいは二種以上の混合物であってもよい。 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 having an HLB (hydrophilic-hydrophobic balance) of less than 15 (particularly 5 or less) and a compound having an HLB of 15 or more. An example of a compound having an HLB of less than 15 is a sorbitan fatty acid ester. An example of a compound having an HLB of 15 or more is a polyoxyethylene alkyl ether. The weight ratio of the compound having an HLB of less than 15 to the compound having an HLB of 15 or more may be 90:10 to 20:80, for example 85:15 to 55:45.
The nonionic surfactant may be used alone or in combination of two or more kinds.
［カチオン性界面活性剤］
　カチオン性界面活性剤は、アミド基を有しない化合物であることが好ましい。 [Cationic surfactant]
The cationic surfactant is preferably a compound that does not have an amide group.
　カチオン性界面活性剤は、アミン塩、４級アンモニウム塩、オキシエチレン付加型アンモニウム塩であってよい。カチオン性界面活性剤の具体例としては、特に限定されないが、アルキルアミン塩、アミノアルコール脂肪酸誘導体、ポリアミン脂肪酸誘導体、イミダゾリン等のアミン塩型界面活性剤、アルキルトリメチルアンモニム塩、ジアルキルジメチルアンモニウム塩、アルキルジメチルベンジルアンモニウム塩、ピリジニウム塩、アルキルイソキノリニウム塩、塩化ベンザルコニウム、塩化ベンゼトニウム等の４級アンモニウム塩型界面活性剤等が挙げられる。 The cationic surfactant may be an amine salt, a quaternary ammonium salt, or an oxyethylene addition type ammonium salt. Specific examples of 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.
　カチオン性界面活性剤の好ましい例は、
　Ｒ２１－Ｎ＋（－Ｒ２２）（－Ｒ２３）（－Ｒ２４）Ｘ－
［式中、Ｒ２１、Ｒ２２、Ｒ２３及びＲ２４は炭素数１～４０の炭化水素基、
Ｘはアニオン性基である。］
の化合物である。
　Ｒ２１、Ｒ２２、Ｒ２３及び－Ｒ２４の具体例は、アルキル基（例えば、メチル基、ブチル基、ステアリル基、パルミチル基）である。Xの具体例は、ハロゲン（例えば、塩素）、酸（例えば、塩酸、酢酸）である。
　カチオン性界面活性剤は、モノアルキルトリメチルアンモニウム塩（アルキルの炭素数４～４０）であることが特に好ましい。 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).
　カチオン性界面活性剤は、アンモニウム塩であることが好ましい。カチオン性界面活性剤は、式：
　Ｒ１ ｐ－Ｎ＋Ｒ２ ｑＸ－
［式中、Ｒ１はＣ１２以上（例えばＣ１２～Ｃ５０）の直鎖状及び／又は分岐状の脂肪族（飽和及び／又は不飽和）基、
Ｒ２はＨ又はＣ１～４のアルキル基、ベンジル基、ポリオキシエチレン基（オキシエチレン基の数例えば１（特に２、特別には３）～５０）
（ＣＨ３、Ｃ２Ｈ５が特に好ましい）、
Ｘはハロゲン原子（例えば、）、Ｃ１～Ｃ４の脂肪酸塩基、
ｐは１又は２、ｑは２又は３で、ｐ＋ｑ＝４である。］
で示されるアンモニウム塩であってよい。Ｒ１の炭素数は、１２～５０、例えば１２～３０であってよい。 Preferably, the cationic surfactant is an ammonium salt. Cationic surfactants have the formula:
R 1 p −N + R 2 q X −
[wherein R 1 is a C12 or more (for example, C 12 to C 50 ) linear and/or branched aliphatic (saturated and/or unsaturated) group,
R 2 is H or a C1-4 alkyl group, benzyl group, polyoxyethylene group (number of oxyethylene groups, for example, 1 (especially 2, especially 3) to 50)
( CH3 , C2H5 are particularly preferred) ,
X is a halogen atom (for example), a C 1 to C 4 fatty acid base,
p is 1 or 2, q is 2 or 3, and p+q=4. ]
It may be an ammonium salt represented by The number of carbon atoms in R 1 may be from 12 to 50, for example from 12 to 30.
　カチオン性界面活性剤の具体例には、ドデシルトリメチルアンモニウムアセテート、トリメチルテトラデシルアンモニウムクロライド、ヘキサデシルトリメチルアンモニウムブロマイド、トリメチルオクタデシルアンモニウムクロライド、（ドデシルメチルベンジル）トリメチルアンモニウムクロライド、ベンジルドデシルジメチルアンモニウムクロライド、メチルドデシルジ（ヒドロポリオキシエチレン）アンモニウムクロライド、ベンジルドデシルジ（ヒドロポリオキシエチレン）アンモニウムクロライド、Ｎ－［２－（ジエチルアミノ）エチル］オレアミド塩酸塩が包含される。 Specific examples of 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.
［アニオン性界面活性剤］
　アニオン性界面活性剤の例としては、アルキルエーテル硫酸塩、アルキル硫酸塩、アルケニルエーテル硫酸塩、アルケニル硫酸塩、オレフィンスルホン酸塩、アルカンスルホン酸塩、飽和又は不飽和脂肪酸塩、アルキル又はアルケニルエーテルカルボン酸塩、α－スルホン脂肪酸塩、Ｎ－アシルアミノ酸型界面活性剤、リン酸モノ又はジエステル型界面活性剤、及びスルホコハク酸エステルが挙げられる。 [Anionic surfactant]
Examples of anionic surfactants 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. Examples include acid salts, α-sulfone fatty acid salts, N-acylamino acid surfactants, phosphate mono- or diester surfactants, and sulfosuccinate esters.
［両性界面活性剤］
　両性界面活性剤の例としては、アラニン類、イミダゾリニウムベタイン類、アミドベタイン類、酢酸ベタイン等が挙げられ、具体的には、ラウリルベタイン、ステアリルベタイン、ラウリルカルボキシメチルヒドロキシエチルイミダゾリニウムベタイン、ラウリルジメチルアミノ酢酸ベタイン、脂肪酸アミドプロピルジメチルアミノ酢酸ベタイン等が挙げられる。 [Ampholytic surfactant]
Examples of amphoteric surfactants 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.
　界面活性剤はノニオン性界面活性剤、カチオン性界面活性剤、及び両性界面活性剤のそれぞれが一種又は２以上の組み合わせであってよい。 The surfactant may be one type or a combination of two or more of nonionic surfactants, cationic surfactants, and amphoteric surfactants.
［界面活性剤の量］
　界面活性剤の量は、化合物α１００重量部に対して、０．０１重量部以上、０．１重量部以上、１重量部以上、３重量部以上、５重量部以上、１０重量部以上、１５重量部以上、２０重量部以上、５０重量部以上、１００重量部以上、２００重量部以上、又は３００重量部以上であってよい。界面活性剤の量は、化合物α１００重量部に対して、５００重量部以下、３００重量部以下、２００重量部以下、１００重量部以下、７５重量部以下、５０重量部以下、３０重量部以下、２０重量部以下、１０重量部以下、５重量部以下、３重量部以下、又は１重量部以下であってよい。
であってよい。 [Amount of surfactant]
The amount of the 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 or more, 15 parts by weight or more, based on 100 parts by weight of the compound α. The amount may be at least 20 parts by weight, 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 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 or less, based on 100 parts by weight of the compound α. It may be 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, or 1 part by weight or less.
It may be.
〔シリコーン〕
　本開示における撥剤は、シリコーン（ポリオルガノシロキサン）を含んでもよい。シリコーンを含むことで、良好な撥液性に加え、風合いや耐久性を良好に兼ね備え得る。 〔silicone〕
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.
　シリコーンとしては、公知のシリコーンを用いることができ、シリコーンの例としては、ポリジメチルシロキサン、変性シリコーン（アミノ変性、エポキシ変性シリコーン、カルボキシ変性シリコーン、メチルハイドロジェンシリコーン等）が挙げられる。シリコーンはワックス状の性質を有するシリコーンワックスであってもよい。これらは単独で用いてもよいし、又は二以上を併用してもよい。 As the 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.
　シリコーンの重量平均分子量は、１０００以上、１００００以上、又は５００００以上であってよい。シリコーンの重量平均分子量は、５０００００以下、２５０００００以下、１０００００以下、又は５００００以下であってよい。 The weight average molecular weight of the silicone may be 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.
［シリコーンの量］
　シリコーンの量は、化合物α１００重量部に対して、０．１重量部以上、１重量部以上、３重量部以上、５重量部以上、１０重量部以上、１５重量部以上、２０重量部以上、５０重量部以上、１００重量部以上、２００重量部以上、又は３００重量部以上であってよい。シリコーンの量は、化合物α１００重量部に対して、５００重量部以下、３００重量部以下、２００重量部以下、１００重量部以下、７５重量部以下、５０重量部以下、４０重量部以下、３０重量部以下、２０重量部以下、１０重量部以下、又は５重量部以下であってよい。 [Amount of silicone]
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 or more, based on 100 parts by weight of the compound α. The amount may be 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, 30 parts by weight, based on 100 parts by weight of the compound α. parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.
〔ワックス〕
　本開示における撥剤は、ワックスを含んでもよい。ワックスを含むことで、撥液性を良好に基材に付与し得る。 〔wax〕
The repellent in the present disclosure may include wax. Including wax can impart good liquid repellency to the base material.
　ワックスの例としては、パラフィンワックス、マイクロクリスタリンワックス、フィッシャートロプシュワックス、ポリオレフィンワックス（ポリエチレンワックス、ポリプロピレンワックス等）、酸化ポリオレフィンワックス、シリコーンワックス、動植物蝋、及び鉱物蝋等が挙げられる。パラフィンワックスが好ましい。ワックスを構成する化合物の具体例は、ノルマルアルカン（例えば、トリコサン、テトラコサン、ペンタコサン、ヘキサコサン、ヘプタコサン、オクタコサン、ノナコサン、トリアコンタン、ヘントリアコンタン、ドトリアコンタン、トリトリアコンタン、テトラトリアコンタン、ペンタトリアコンタン、ヘキサトリアコンタン）、ノルマルアルケン（例えば、１－エイコセン、１－ドコセン、１－トリコセン、１－テトラコセン、１－ペンタコセン、１－ヘキサコセン、１－ヘプタコセン、１－オクタコセン、ノナコサン、トリアコンタン、ヘントリアコンタン、ドトリアコンタン、トリトリアコンタン、テトラトリアコンタン、ペンタトリアコンタン、ヘキサトリアコンタン）である。ワックスを構成する化合物の炭素数は、２０～６０、例えば、２５～４５であることが好ましい。ワックスの分子量は、２００～２０００、例えば２５０～１５００、３００～１０００であってよい。これらは単独で用いてもよいし、又は二以上を併用してもよい。 Examples of wax 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. Specific examples of 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. 1-eicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 1-heptacosene, 1-octacosene, nonacosane, triacontane, hexane), tritriacontane, dotriacontane, tritriacontane, tetratriacontane, pentatriacontane, hexatriacontane). 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.
　ワックスの融点は、５０℃以上、５５℃以上、６０℃以上、６５℃以上、又は７０℃以上であってよく、好ましくは５５℃以上、より好ましくは６０℃以上である。ワックスの融点は、JIS K 2235-1991に準拠して測定される。 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.
［ワックスの量］
　ワックスの量は、化合物α１００重量部に対して、０．１重量部以上、１重量部以上、３重量部以上、５重量部以上、１０重量部以上、１５重量部以上、２０重量部以上、５０重量部以上、１００重量部以上、２００重量部以上、又は３００重量部以上であってよい。ワックスの量は、化合物α１００重量部に対して、５００重量部以下、３００重量部以下、２００重量部以下、１００重量部以下、７５重量部以下、５０重量部以下、４０重量部以下、３０重量部以下、２０重量部以下、１０重量部以下、５重量部以下であってよい。 [Amount of wax]
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 or more, based on 100 parts by weight of the compound α. The amount may be 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, 30 parts by weight, based on 100 parts by weight of compound α. parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less.
〔有機酸〕
　撥剤は有機酸を含んでもよい。有機酸としては、公知のものを用いることができる。有機酸としては、カルボン酸、スルホン酸、スルフィン酸等が好ましく挙げられ、特にカルボン酸が好ましい。該カルボン酸としては、ギ酸、酢酸、プロピオン酸、酪酸、シュウ酸、コハク酸、グルタル酸、アジピン酸、リンゴ酸、クエン酸等が挙げられ、特にギ酸又は酢酸が好ましい。本開示においては、有機酸は、一種を用いてもよく、二種以上を組み合わせて用いてもよい。たとえば、ギ酸と酢酸とを組み合わせて用いてもよい。 [Organic acid]
The repellent may include an organic acid. As the 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. Examples of the 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. In the present disclosure, one type of organic acid may be used, or two or more types may be used in combination. For example, formic acid and acetic acid may be used in combination.
［有機酸の量］
　有機酸の量は、化合物α１００重量部に対して、０．１重量部以上、１重量部以上、３重量部以上、５重量部以上、１０重量部以上、１５重量部以上、２０重量部以上、５０重量部以上、１００重量部以上、２００重量部以上、又は３００重量部以上であってよい。有機酸の量は、化合物α１００重量部に対して、５００重量部以下、３００重量部以下、２００重量部以下、１００重量部以下、７５重量部以下、５０重量部以下、４０重量部以下、３０重量部以下、２０重量部以下、１０重量部以下、又は５重量部以下であってよい。撥剤のｐＨが、３～１０、例えば５～９、特に６～８となるように有機酸の量は調整されてもよい。撥剤は酸性（ｐＨ７以下、例えば６以下）であってもよい。 [Amount of organic acid]
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 compound α. , 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 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 or less, 30 parts by weight or less, based on 100 parts by weight of the compound α. It may be less than 20 parts by weight, less than 10 parts by weight, or less than 5 parts by weight. 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).
〔硬化剤〕
　撥剤は、硬化剤（活性水素反応性化合物又は活性水素含有化合物）を含んでよい。 [Curing agent]
The repellent may include a curing agent (active hydrogen-reactive compound or active hydrogen-containing compound).
　撥剤における硬化剤（架橋剤）は化合物αを良好に硬化させ得る。硬化剤は、化合物αの有する活性水素又は活性水素反応性基と反応する活性水素反応性化合物又は活性水素含有化合物であってよい。活性水素反応性化合物の例は、イソシアネート化合物、エポキシ化合物、クロロメチル基含有化合物、カルボキシル基含有化合物及びヒドラジド化合物である。活性水素含有化合物の例は、ヒドロキシル基含有化合物、アミノ基含有化合物及びカルボキシル基含有化合物、ケトン基含有化合物、ヒドラジド化合物及びメラミン化合物である。 The curing agent (crosslinking agent) in the repellent can cure compound α 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 compound α. Examples of active hydrogen-reactive compounds are isocyanate compounds, epoxy compounds, chloromethyl group-containing compounds, carboxyl group-containing compounds and hydrazide compounds. Examples of 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.
　硬化剤はイソシアネート化合物を含んでよい。イソシアネート化合物は、ポリイソシアネート化合物であってよい。ポリイソシアネート化合物は、１分子中にイソシアネート基を２個以上有する化合物である。ポリイソシアネート化合物は、架橋剤として働く。ポリイソシアネート化合物の例は、脂肪族ポリイソシアネート、脂環族ポリイソシアネート、芳香脂肪族ポリイソシアネート、芳香族ポリイソシアネート及びこれらポリイソシアネートの誘導体等を挙げることができる。イソシアネート化合物は、ブロックドイソシアネート化合物（例えばブロックドポリイソシアネート化合物であってよい）。ブロックイソシアネート化合物は、イソシアネート化合物のイソシアネート基をブロック剤でマスクし反応を抑制した化合物である。 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.
　脂肪族ポリイソシアネートの例は、トリメチレンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、ペンタメチレンジイソシアネート、１，２－プロピレンジイソシアネート、１，２－ブチレンジイソシアネート、２，３－ブチレンジイソシアネート、１，３－ブチレンジイソシアネート、２，４，４－又は２，２，４－トリメチルヘキサメチレンジイソシアネート、２，６－ジイソシアナトメチルカプロエートの脂肪族ジイソシアネート、及びリジンエステルトリイソシアネート、１，４，８－トリイソシアナトオクタン、１，６，１１－トリイソシアナトウンデカン、１，８－ジイソシアナト－４－イソシアナトメチルオクタン、１，３，６－トリイソシアナトヘキサン、２，５，７－トリメチル－１，８－ジイソシアナト－５－イソシアナトメチルオクタン等の脂肪族トリイソシアネート等である。これらは単独で用いてもよいし、又は二以上を併用して用いてもよい。 Examples of 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-isocyanatomethyloctane and other aliphatic triisocyanates. These may be used alone or in combination of two or more.
　脂環族ポリイソシアネートの例は、脂環族ジイソシアネート及び脂環族トリイソシアネート等である。脂環族ポリイソシアネートの具体例は、１，３－シクロペンテンジイソシアネート、３－イソシアナトメチル－３，５，５－トリメチルシクロヘキシルイソシアネート（イソホロンジイソシアネート）、１，３，５－トリイソシアナトシクロヘキサンである。これらは単独で用いてもよいし、又は二以上を併用して用いてもよい。 Examples of alicyclic polyisocyanates 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.
　芳香脂肪族ポリイソシアネートの例は、芳香脂肪族ジイソシアネート及び芳香脂肪族トリイソシアネートである。芳香脂肪族ポリイソシアネートの具体例は、１，３－若しくは１，４－キシリレンジイソシアネート又はその混合物、１，３－又は１，４－ビス（１－イソシアナト－１－メチルエチル）ベンゼン（テトラメチルキシリレンジイソシアネート）若しくはその混合物、１，３，５－トリイソシアナトメチルベンゼンである。これらは単独で用いてもよいし、又は二以上を併用して用いてもよい。 Examples of araliphatic polyisocyanates are 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.
　芳香族ポリイソシアネートの例は、芳香族ジイソシアネート、芳香族トリイソシアネート、芳香族テトライソシアネートである。芳香族ポリイソシアネートの具体例は、ｍ－フェニレンジイソシアネート、ｐ－フェニレンジイソシアネート、４，４’－ジフェニルジイソシアネート、１，５－ナフタレンジイソシアネート、２，４’－又は４，４’－ジフェニルメタンジイソシアネート若しくはその混合物、２，４－又は２，６－トリレンジイソシアネート若しくはその混合物、トリフェニルメタン－４，４’，４’’－トリイソシアネート、及び４，４’－ジフェニルメタン－２，２’，５，５’－テトライソシアネート等である。これらは単独で用いてもよいし、又は二以上を併用して用いてもよい。 Examples of aromatic polyisocyanates are aromatic diisocyanates, aromatic triisocyanates, and aromatic tetraisocyanates. Specific examples of 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. , 2,4- or 2,6-tolylene diisocyanate or mixtures thereof, triphenylmethane-4,4',4''-triisocyanate, and 4,4'-diphenylmethane-2,2',5,5' - Tetraisocyanate, etc. These may be used alone or in combination of two or more.
　ポリイソシアネートの誘導体は、例えば、上記したポリイソシアネート化合物のダイマー、トリマー、ビウレット、アロファネート、カルボジイミド、ウレトジオン、ウレトイミン、イソシアヌレート、イミノオキサジアジンジオン等の各種誘導体を挙げることができる。これらは単独で用いてもよいし、又は二以上を併用して用いてもよい。 Examples of the polyisocyanate derivative 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.
　これらポリイソシアネートは、一種又は二種以上を組合せて使用することができる。
　ポリイソシアネート化合物として、ポリイソシアネート化合物のイソシアネート基をブロック剤でブロックした化合物であるブロック化ポリイソシアネート化合物(ブロックイソシアネート)を使用することが好ましい。溶液中でも比較的安定であり、撥剤と同じ溶液中でも使用可能である等の理由からブロック化ポリイソシアネート化合物を使用することが好ましい。 These polyisocyanates can be used alone or in combination of two or more.
As the polyisocyanate compound, it is preferable to use a blocked polyisocyanate compound (blocked isocyanate), which 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.
　ブロック剤は、遊離のイソシアネート基を封鎖するものである。ブロック化ポリイソシアネート化合物は、例えば、１００℃以上、例えば１３０℃以上に加熱することにより、イソシアネート基が再生し、ヒドロキシル基と容易に反応することができる。ブロック剤の例は、フェノール系化合物、ラクタム系化合物、脂肪族アルコール系化合物、オキシム系化合物等である。ポリイソシアネート化合物は、単独で又は二種以上を組合せて使用することができる。 The blocking agent blocks free isocyanate groups. When 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. Examples of 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.
　エポキシ化合物は、エポキシ基を有する化合物である。エポキシ化合物の例は、ポリオキシアルキレン基を有するエポキシ化合物、例えば、ポリグリセロールポリグリシジルエーテル及びポリプロピレングリコ－ルジグリシジルエ－テル；並びにソルビトールポリグリシジルエーテル等である。
　クロロメチル基含有化合物はクロロメチル基を有する化合物である。クロロメチル基含有化合物の例は、クロロメチルポリスチレン等である。
　カルボキシル基含有化合物はカルボキシル基を有する化合物である。カルボキシル基含有化合物の例は、(ポリ)アクリル酸、(ポリ)メタクリル酸等である。 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.
　ケトン基含有化合物の具体例としては、（ポリ）ジアセトンアクリルアミド、ジアセトンアルコール等が挙げられる。
　ヒドラジド化合物の具体例としては、ヒドラジン、カルボヒドラジド、アジピン酸ヒドラジド等が挙げられる。
　メラミン化合物の具体例としては、メラミン樹脂、メチルエーテル化メラミン樹脂等が挙げられる。 Specific examples of the ketone group-containing compound include (poly)diacetone acrylamide, diacetone alcohol, and the like.
Specific examples of the hydrazide compound include hydrazine, carbohydrazide, adipic acid hydrazide, and the like.
Specific examples of the melamine compound include melamine resin, methyl etherified melamine resin, and the like.
［硬化剤の量］
　硬化剤の量は、化合物α１００重量部に対して、０．１重量部以上、１重量部以上、３重量部以上、５重量部以上、１０重量部以上、１５重量部以上、２０重量部以上、５０重量部以上、１００重量部以上、２００重量部以上、又は３００重量部以上であってよい。硬化剤の量は、化合物α１００重量部に対して、５００重量部以下、３００重量部以下、２００重量部以下、１００重量部以下、７５重量部以下、５０重量部以下、４０重量部以下、３０重量部以下、２０重量部以下、１０重量部以下、５重量部以下であってよい。 [Amount of hardening agent]
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 compound α. , 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 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 or less, 30 parts by weight or less, based on 100 parts by weight of the compound α. The amount may be up to 20 parts by weight, up to 10 parts by weight, or up to 5 parts by weight.
〔他の成分〕
　撥剤は、上記成分以外の他の成分を含んでよい。他の成分の例としては、多糖類、紙力増強剤、凝集剤、歩留まり向上剤、凝結剤、バインダー樹脂、スリップ防止剤、サイズ剤、紙力増強剤、充填剤、帯電防止剤、防腐剤、紫外線吸収剤、抗菌剤、消臭剤、香料等が挙げられる。これらは単独で用いてもよいし、又は二以上を併用して用いてもよい。
前記の成分以外に、その他成分として、その他の撥水及び／又は撥油剤、分散剤、風合い調整剤、柔軟剤、難燃剤、塗料定着剤、防シワ剤、乾燥速度調整剤、架橋剤、造膜助剤、相溶化剤、凍結防止剤、粘度調整剤、紫外線吸収剤、酸化防止剤、ｐＨ調整剤、防虫剤、消泡剤、縮み防止剤、洗濯じわ防止剤、形状保持剤、ドレープ性保持剤、アイロン性向上剤、増白剤、白化剤、布地柔軟化クレイ、ポリビニルピロリドン等の移染防止剤、高分子分散剤、汚れ剥離剤、スカム分散剤、４，４－ビス（２－スルホスチリル）ビフェニルジナトリウム（チバスペシャルティケミカルズ製チノパールＣＢＳ－Ｘ）等の蛍光増白剤、染料固定剤、１，４－ビス（３－アミノプロピル）ピペラジン等の退色防止剤、染み抜き剤、繊維表面改質剤としてセルラーゼ、アミラーゼ、プロテアーゼ、リパーゼ、ケラチナーゼ等の酵素、抑泡剤、水分吸放出性等絹の風合い・機能を付与できるものとしてシルクプロテインパウダー、それらの表面改質物又は乳化分散液（例えばＫ－５０、Ｋ－３０、Ｋ－１０、Ａ－７０５、Ｓ－７０２、Ｌ－７１０、ＦＰシリーズ（出光石油化学）、加水分解シルク液（上毛）、シルクゲンＧソルブルＳ（一丸ファルコス））、汚染防止剤（例えばアルキレンテレフタレート及び／又はアルキレンイソフタレート単位とポリオキシアルキレン単位からなる非イオン性高分子化合物（例えば互応化学工業製ＦＲ６２７）、クラリアントジャパン製ＳＲＣ－１等）等を配合することができる。これらは単独で使用してもよく、また二以上を併用して使用してもよい。 [Other ingredients]
The repellent may contain components other than the above components. Examples of other ingredients include polysaccharides, paper strength agents, flocculants, retention improvers, coagulants, binder resins, anti-slip agents, sizing agents, paper strength agents, fillers, antistatic agents, and preservatives. , ultraviolet absorbers, antibacterial agents, deodorants, fragrances, etc. These may be used alone or in combination of two or more.
In addition to the above ingredients, other water and/or oil repellent agents, dispersants, texture control agents, softeners, flame retardants, paint fixing agents, anti-wrinkle agents, drying rate regulators, crosslinking agents, and Film aids, compatibilizers, antifreeze agents, viscosity modifiers, ultraviolet absorbers, antioxidants, pH adjusters, insect repellents, antifoaming agents, anti-shrinkage agents, anti-wrinkle agents, shape retention agents, drapes properties retention agent, ironability improver, whitening agent, whitening agent, fabric softening clay, dye transfer prevention agent such as polyvinylpyrrolidone, polymer dispersant, stain remover, scum dispersant, 4,4-bis(2 - Fluorescent brighteners such as sulfostyryl)biphenyldisodium (Tinopal CBS-X manufactured by Ciba Specialty Chemicals), dye fixatives, anti-fading agents such as 1,4-bis(3-aminopropyl)piperazine, stain removers, fibers Enzymes such as cellulase, amylase, protease, lipase, and keratinase as surface modifiers, foam suppressants, and silk protein powders that can impart the texture and functions of silk such as moisture absorption and release properties, and their surface modification products or emulsified dispersions. (For example, K-50, K-30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk liquid (Jomo), Silkgen G Soluble S (Ichimaru Falcos) )), anti-fouling agents (for example, nonionic polymer compounds consisting of alkylene terephthalate and/or alkylene isophthalate units and polyoxyalkylene units (for example, FR627 manufactured by Gooh Kagaku Kogyo), SRC-1 manufactured by Clariant Japan, etc.) are blended. can do. These may be used alone or in combination of two or more.
［多糖類］
　多糖類の例としては、澱粉、キサンタンガム、カラヤガム、ウェランガム、グアーガム、ペクチン、タマリンドガム、カラギーナン、キトサン、アラビアガム、ローカストビーンガム、セルロース、アルギン酸、寒天、デキストラン、及びプルラン等が挙げられる。多糖類は、置換されている変性多糖類であってよく、特に、水酸基やカチオン性基を導入した変性多糖類であってよい。 [Polysaccharide]
Examples of polysaccharides include starch, xanthan gum, karaya gum, welan gum, guar gum, pectin, tamarind gum, carrageenan, chitosan, gum arabic, locust bean gum, cellulose, alginic acid, agar, dextran, pullulan, and the like. The polysaccharide may be a substituted modified polysaccharide, particularly a modified polysaccharide having a hydroxyl group or a cationic group introduced therein.
［紙力増強剤、凝集剤、歩留まり向上剤又は凝結剤］
　紙力増強剤、凝集剤、歩留まり向上剤又は凝結剤の例としては、スチレン系重合体（スチレン／マレイン酸系重合体、スチレン／アクリル酸系重合体）、尿素‐ホルムアルデヒド重合体、ポリエチレンイミン、メラミン‐ホルムアルデヒド重合体、ポリアミドアミン‐エピクロルヒドリン重合体、ポリアクリルアミド系重合体、ポリアミン系重合体、ポリジアリルジメチルアンモニウムクロライド、アルキルアミン・エピクロルヒドリン縮合物、アルキレンジクロライドとポリアルキレンポリアミンの縮合物、ジシアンジアミド・ホルマリン縮合物、ジメチルジアリルアンモニウムクロライド重合体、及びオレフィン／無水マレイン酸重合体等が挙げられる [Paper strength enhancer, flocculant, retention improver or coagulant]
Examples of paper strength enhancers, flocculants, retention improvers, or coagulants include styrene polymers (styrene/maleic acid polymers, styrene/acrylic acid polymers), urea-formaldehyde polymers, polyethyleneimine, Melamine-formaldehyde polymer, polyamide amine-epichlorohydrin polymer, polyacrylamide polymer, polyamine polymer, polydiallyldimethylammonium chloride, alkylamine-epichlorohydrin condensate, condensate of alkylene dichloride and polyalkylene polyamine, dicyandiamide formalin Examples include condensates, dimethyldiallylammonium chloride polymers, and olefin/maleic anhydride polymers.
［サイズ剤］
　サイズ剤の例としては、セルロース反応性サイズ剤、例えばロジン系石鹸などのロジン系サイズ剤、ロジン系乳濁液／分散液、セルロース反応性サイズ剤、例えばアルキルおよびアルケニルコハク酸無水物（ＡＳＡ）などの酸無水物の乳濁液／分散液、アルケニルおよびアルキルケテン二量体（ＡＫＤ）および多量体、ならびにエチレン性不飽和モノマーのアニオン性、カチオン性および両性のポリマー、例えばスチレンとアクリレートとの共重合体があげられる。 [Sizing agent]
Examples of sizing agents include cellulose-reactive sizing agents such as rosin-based sizing agents such as rosin-based soaps, rosin-based emulsions/dispersions, cellulose-reactive sizing agents such as alkyl and alkenyl succinic anhydrides (ASA) emulsions/dispersions of acid anhydrides such as alkenyl and alkyl ketene dimers (AKD) and multimers, and anionic, cationic and amphoteric polymers of ethylenically unsaturated monomers, such as styrene and acrylates. Examples include copolymers.
［帯電防止剤］
　帯電防止剤の例としては、第４級アンモニウム塩、ピリジニウム塩、第１、第２、第３アミノ基等のカチオン性官能基を有すカチオン型帯電防止剤；スルホン酸塩や硫酸エステル塩、ホスホン酸塩、リン酸エステル塩等のアニオン性官能基を有するアニオン型帯電防止剤；アルキルベタイン及びその誘導体、イミダゾリン及びその誘導体、アラニン及びその誘導体等の両性型帯電防止剤、アミノアルコール及びその誘導体、グリセリン及びその誘導体、ポリエチレングリコール及びその誘導体等のノニオン型帯電防止剤等が挙げられる。これらのカチオン型、アニオン型、両性イオン型のイオン導電性基を有する単量体を重合若しくは共重合して得られたイオン導電性重合体であってもよい。これらは単独で使用してもよく、また二以上を併用してもよい。 [Antistatic agent]
Examples of antistatic agents 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.
［防腐剤］
　防腐剤は、主に、防腐力、殺菌力を強化し、長期保存中の防腐性を保つために用いられ得る。防腐剤としては、例えば、イソチアゾロン系有機硫黄化合物、ベンズイソチアゾロン系有機硫黄化合物、安息香酸類、２－ブロモ－２－ニトロ－１，３－プロパンジオール等が挙げられる。 [Preservative]
Preservatives can be used mainly to enhance preservative power and sterilizing power, and to maintain preservative properties during long-term storage. Examples of the preservative include isothiazolone organic sulfur compounds, benzisothiazolone organic sulfur compounds, benzoic acids, 2-bromo-2-nitro-1,3-propanediol, and the like.
［紫外線吸収剤］
　紫外線吸収剤は、紫外線を防御する効果のある薬剤であり、紫外線を吸収し、赤外線や可視光線等に変換して放出する成分である。紫外線吸収剤としては、例えば、アミノ安息香酸誘導体、サリチル酸誘導体、ケイ皮酸誘導体、ベンゾフェノン誘導体、アゾール系化合物、４－ｔ－ブチル－４'－メトキシベンゾイルメタン等が挙げられる。 [Ultraviolet absorber]
An ultraviolet absorber is a drug that has the effect of protecting against ultraviolet rays, and is a component that absorbs ultraviolet rays, 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.
［抗菌剤］
　抗菌剤は、繊維上での菌の増殖を抑え、さらには微生物の分解物由来の嫌なにおいの発生を抑える効果を有する成分である。抗菌剤としては、例えば、四級アンモニウム塩等のカチオン性殺菌剤、ビス－（２－ピリジルチオ－１－オキシド）亜鉛、ポリヘキサメチレンビグアニジン塩酸塩、８－オキシキノリン、ポリリジン等が挙げられる。 [Antibacterial agent]
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. Examples of 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.
［消臭剤］
　消臭剤としては、クラスターデキストリン、メチル－β－シクロデキストリン、２－ヒドロキシプロピル－β－シクロデキストリン、モノアセチル－β－シクロデキストリン、アシルアミドプロピルジメチルアミンオキシド、アミノカルボン酸系金属錯体（国際公開第２０１２／０９０５８０号記載のメチルグリシンジ酢酸３ナトリウムの亜鉛錯体）等が挙げられる。 [Deodorants]
Deodorants include cluster dextrin, methyl-β-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, monoacetyl-β-cyclodextrin, acylamidopropyldimethylamine oxide, aminocarboxylic acid metal complexes (International Publication Zinc complex of trisodium methylglycine diacetate described in No. 2012/090580), and the like.
［他の成分の量］
　他の成分の各量又は総量は、化合物α１００重量部に対して、０．１重量部以上、１重量部以上、３重量部以上、５重量部以上、１０重量部以上、１５重量部以上、２０重量部以上、５０重量部以上、１００重量部以上、２００重量部以上、又は３００重量部以上であってよい。他の成分の各量又は総量は、化合物α１００重量部に対して、５００重量部以下、３００重量部以下、２００重量部以下、１００重量部以下、７５重量部以下、５０重量部以下、４０重量部以下、３０重量部以下、２０重量部以下、１０重量部以下、５重量部以下であってよい。 [Amount of other ingredients]
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 or more, based on 100 parts by weight of the compound α. The amount may be 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, 40 parts by weight, based on 100 parts by weight of compound α. 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.
＜処理された繊維製品又は紙製品の製造方法＞
　本開示における撥剤で処理された製品の製造方法は、上述した撥剤で基材を処理する処理工程を含む。 <Method for manufacturing treated textile products or paper products>
A method for manufacturing a product treated with a repellent in the present disclosure includes a treatment step of treating a substrate with the repellent described above.
　「処理」とは、撥剤を、浸漬、噴霧、塗布等により基材に適用することを意味する。処理により、撥剤の有効成分である化合物αが基材の内部に浸透する及び／又は基材の表面に付着する。 "Treatment" means applying a repellent to a substrate by dipping, spraying, coating, etc. Through the treatment, the compound α, which is an active ingredient of the repellent, penetrates into the interior of the substrate and/or adheres to the surface of the substrate.
［基材］
　本開示における撥剤で処理される基材は限定されないが、好適には繊維製品又は紙製品である。 [Base material]
The substrate treated with the repellent in the present disclosure is not limited, but is preferably a textile product or a paper product.
　繊維製品の基材の例としては、綿、麻、羊毛、絹等の動植物性天然繊維、ポリアミド、ポリエステル、ポリビニルアルコール、ポリアクリロニトリル、ポリ塩化ビニル、ポリプロピレン等の合成繊維、レーヨン、アセテート等の半合成繊維、ガラス繊維、炭素繊維、アスベスト繊維等の無機繊維、あるいはこれらの混合繊維が挙げられる。繊維製品には、織物、編物及び不織布、衣料品形態の布及びカーペットが含まれるが、布とする前の状態の繊維、糸、中間繊維製品（例えば、スライバー又は粗糸等）に対して、処理がなされてもよい。 Examples of base materials for textile products include natural fibers of animal and plant origin such as cotton, linen, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, and semi-synthetic fibers such as rayon and acetate. Examples include synthetic fibers, glass fibers, carbon fibers, inorganic fibers such as asbestos fibers, and mixed fibers thereof. Textile products include woven, knitted and non-woven fabrics, cloth in the form of clothing and carpets; Processing may be performed.
　紙製品の基材の例としては、クラフトパルプあるいはサルファイトパルプ等の晒あるいは未晒化学パルプ、砕木パルプ、機械パルプあるいはサーモメカニカルパルプ等の晒あるいは未晒高収率パルプ、新聞古紙、雑誌古紙、段ボール古紙あるいは脱墨古紙等の古紙パルプ等からなる紙、紙でできた容器、紙でできた成形体等が挙げられる。紙製品の具体例としては、食品用包装用紙、石膏ボード原紙、コート原紙、中質紙、一般ライナー及び中芯、中性純白ロール紙、中性ライナー、防錆ライナー及び金属合紙、クラフト紙、中性印刷筆記用紙、中性コート原紙、中性ＰＰＣ用紙、中性感熱用紙、中性感圧原紙、中性インクジェット用紙及び中性情報用紙、モールド紙（モールド容器）等である。 Examples of base materials for 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, old newspapers, and old magazines. Examples include paper made of waste paper pulp such as used cardboard or deinked waste paper, containers made of paper, and molded objects made of paper. Specific examples of paper products include food 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, and kraft paper. , neutral printing writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure-sensitive base paper, neutral inkjet paper and neutral information paper, molded paper (mold container), etc.
　本開示の撥剤で処理される基材としては、繊維製品又は紙製品に限られず、他にも、石材、フィルター（例えば、静電フィルター）、防塵マスク、燃料電池の部品（例えば、ガス拡散電極及びガス拡散支持体）、ガラス、木、皮革、毛皮、石綿、レンガ、セメント、金属及び酸化物、窯業製品、プラスチック、塗面、及びプラスター等を挙げることができる。 Substrates treated with the repellent of the present disclosure are not limited to textiles or paper products, but may also include stones, filters (e.g., electrostatic filters), dust masks, fuel cell parts (e.g., gas diffusion Examples include electrodes and gas diffusion supports), glass, wood, leather, fur, asbestos, brick, cement, metals and oxides, ceramic products, plastics, painted surfaces, and plaster.
［処理方法］
　本開示の撥剤は、処理剤（特に表面処理剤）として、従来既知の方法により基材に適用することができる。処理の方法としては、本開示における撥剤を、必要により有機溶媒又は水に分散して希釈して、浸漬塗布、スプレー塗布、泡塗布等のような既知の方法により、基材の表面に付着させ、乾燥する方法であってよい。乾燥後、撥剤における固形成分が付着した繊維製品が得られる。また、必要ならば、適当な架橋剤と共に適用し、キュアリングを行ってもよい。本開示の撥剤に、必要により、さらに、撥水及び／又は撥油剤、スリップ防止剤、帯電防止剤、風合い調整剤、柔軟剤、抗菌剤、難燃剤、塗料定着剤、防シワ剤、乾燥速度調整剤、架橋剤、造膜助剤、相溶化剤、凍結防止剤、粘度調整剤、紫外線吸収剤、酸化防止剤、ｐＨ調整剤、防虫剤、消泡剤等の各種添加剤とを併用することも可能である。各種添加剤の例としては、上述の撥水剤組成物における「他の成分」で説明したものと同様であってよい。基材と接触させる処理剤における撥剤の濃度は、用途によって適宜変更されてよいが、０.０１～１０重量％、例えば０.０５～５重量％であってよい。 [Processing method]
The repellent of the present disclosure can be applied to a substrate as a treatment agent (particularly a surface treatment agent) by a conventionally known method. As a treatment method, the repellent according to the present disclosure is dispersed and diluted in an organic solvent or water if necessary, and then attached to the surface of the base material by a known method such as dip coating, spray coating, foam coating, etc. It may be a method of drying. After drying, a textile product is obtained to which the solid components of the repellent are attached. Further, if necessary, curing may be performed by applying together with a suitable crosslinking agent. If necessary, 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. 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. Examples of 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.
　撥剤は、基材を液体で処理するために知られている方法のいずれかによって基材に適用することができる。基材を撥剤に浸してよく、あるいは、基材に溶液を付着又は噴霧してよい。処理された基材は、撥液性を発現させるために、好ましくは、加熱により乾燥及びキュアリングが行われる。加熱温度は例えば１００℃～２００℃、１００℃～１７０℃又は１００℃～１２０℃であってよい。本開示において低温加熱（例えば、１００℃～１４０℃）であっても良好な性能が得られる。本開示において加熱時間は５秒～６０分であってよく、例えば３０秒～３分であってよい。繊維製品が紙であるときには、紙に塗工してよく、あるいは、紙に溶液を付着又は噴霧してよく、あるいは、抄造前のパルプスラリーと混合して処理してもよい。処理は外添処理であっても、内添処理であってもよい。あるいは、撥剤はクリーニング法によって繊維製品に適用してよく、例えば、洗濯適用又はドライクリーニング法等において繊維製品に適用してよい。 The repellent can be applied to the substrate by any of the methods known for treating substrates with liquids. The substrate may be soaked in the repellent, or the solution may be applied or sprayed onto the substrate. The treated base material is preferably dried and cured by heating in order to develop liquid repellency. The heating temperature may be, for example, 100°C to 200°C, 100°C to 170°C or 100°C to 120°C. In the present disclosure, good performance can be obtained even with low temperature heating (eg, 100° C. to 140° C.). In the present disclosure, the heating time may be from 5 seconds to 60 minutes, for example from 30 seconds to 3 minutes. When the textile product is paper, the solution may be applied to the paper, or the solution may be attached or sprayed onto the paper, or the solution may be mixed with pulp slurry before paper making. The treatment may be an external addition treatment or an internal addition treatment. Alternatively, the repellent may be applied to the textile by a cleaning process, such as in a laundering or dry cleaning process.
［紙の処理］
　紙基材としては、紙、紙でできた容器、紙でできた成形体（例えばパルプモールド）などが挙げられる。
紙基材を処理する方法としては、外添処理または内添処理する工程が挙げられる。 [Paper processing]
Examples of the paper base material include paper, a container made of paper, and a molded article made of paper (for example, a pulp mold).
Examples of methods for treating paper base materials include external addition treatment or internal addition treatment.
　紙は、従来既知の抄造方法によって製造できる。抄造前のパルプスラリーに撥剤を添加する内添処理方法、又は抄造後の紙に撥剤を適用する外添処理方法を用いることができる。 Paper can be manufactured by conventionally known papermaking methods. An internal addition treatment method in which a repellent is added to the pulp slurry before papermaking, or an external addition treatment method in which a repellent is applied to paper after papermaking can be used.
　内添処理方法は抄造前のパルプスラリーに撥剤を添加する処理方法を意味してよい。内添処理方法として、パルプスラリーに撥剤を添加して攪拌混合する工程と、当該工程で調製したパルプ組成物を所定形状の網状体を介して吸引脱水してパルプ組成物を堆積さてパルプモールド中間体を形成する工程と、当該パルプモールド中間体を加温された成形型によって成型乾燥することで、紙、紙でできた容器、紙でできた成形体を得る工程の一以上を含んでもよいが、この限りではない。処理された紙は、室温又は高温での簡単な乾燥後に、任意に、紙の性質に依存して熱処理を施してもよい。熱処理の温度は１５０℃以上、１８０℃以上、又は２１０℃以上であってよく、３００℃以下、２５０℃以下、又は２００℃以下であってよく、特に８０℃～１８０℃であってよい。斯かる温度範囲で熱処理を行うことにより、優れた耐油性及び耐水性等を示し得る。 The internal addition treatment method may refer to a treatment method in which a repellent is added to the pulp slurry before papermaking. The internal addition treatment method includes a step of adding a repellent to the pulp slurry and stirring and mixing, and a pulp composition prepared in this step is sucked and dehydrated through a mesh having a predetermined shape, and the pulp composition is deposited and molded into a pulp mold. The method may include one or more of the steps of forming an intermediate and molding and drying the pulp mold intermediate using a heated mold to obtain paper, a container made of paper, and a molded article made of paper. Good, but not limited to this. The treated paper may optionally be subjected to a heat treatment, depending on the nature of the paper, after brief drying at room or elevated temperature. The temperature of the heat treatment may be 150°C or higher, 180°C or higher, or 210°C or higher, and may be 300°C or lower, 250°C or lower, or 200°C or lower, particularly from 80°C to 180°C. By performing heat treatment in such a temperature range, excellent oil resistance, water resistance, etc. can be exhibited.
　外添処理方法のサイズプレスは、塗布方式によって以下のように分けることも可能である。
　１つの塗布方式は、２本のゴムロールの間に紙を通して形成されるニップ部に塗布液（サイズ液）を供給し、ポンドと呼ばれる塗液溜りを作り、この塗液溜りに紙を通して紙の両面にサイズ液を塗布する、いわゆるポンド式ツーロールサイズプレスである。他の塗布方式は、サイズ液を表面転写型により塗布するゲートロール型、及び、ロッドメタリングサイズプレスである。ポンド式ツーロールサイズプレスにおいてサイズ液は紙の内部まで浸透しやすく、表面転写型においてサイズ液成分は紙の表面に留まりやすい。表面転写型は、ポンド式ツーロールサイズプレスと比べて、塗布層が紙の表面に留まりやすく、表面に形成される塗布層がポンド式ツーロールサイズプレスより多い。本開示では、前者のポンド式２ロールサイズプレスを用いた場合でも紙に性能を付与できる。このように処理された紙は、室温又は高温での簡単な乾燥後に、任意に、紙の性質に依存して３００℃まで、例えば２００℃まで、特に８０℃～１８０℃の温度範囲をとり得る熱処理を伴うことで、優れた耐油性及び耐水性等を示し得る。 The size press, which is an external addition treatment method, can be divided into the following types depending on the coating method.
One coating method involves supplying coating liquid (size liquid) to a nip formed by passing paper between two rubber rolls, creating a pool of coating liquid called a pond, and passing paper through this pool to coat both sides of the paper. This is a so-called pound-type two-roll size press that applies a size liquid to the surface. Other coating methods include a gate roll type in which the size liquid is applied by a surface transfer type, and a rod metering size press. In pound-type two-roll size presses, the size liquid easily penetrates into the inside of the paper, and in surface transfer type, size liquid components tend to stay on the surface of the paper. In the surface transfer type, the coating layer stays on the surface of the paper more easily than in the pound-type two-roll size press, and more coating layers are formed on the surface than in the pound-type two-roll size press. In the present disclosure, performance can be imparted to paper even when the former pound-type two-roll size press is used. The paper treated in this way can optionally, after brief drying at room temperature or at elevated temperatures, have a temperature range of up to 300°C, for example up to 200°C, in particular from 80°C to 180°C, depending on the nature of the paper. By being accompanied by heat treatment, it can exhibit excellent oil resistance, water resistance, etc.
　本開示は、石膏ボード原紙、コート原紙、中質紙、一般ライナー及び中芯、中性純白ロール紙、中性ライナー、防錆ライナー及び金属合紙、クラフト紙などにおいて使用することができる。また、中性印刷筆記用紙、中性コート原紙、中性ＰＰＣ用紙、中性感熱用紙、中性感圧原紙、中性インクジェット用紙及び中性情報用紙においても用いることができる。 The present disclosure can be used in gypsum board base paper, coated base paper, medium-quality paper, general liner and core, neutral pure white roll paper, neutral liner, rust-proof liner, metal interleaving paper, kraft paper, etc. It can also be used in neutral printing writing paper, neutral coated base paper, neutral PPC paper, neutral thermal paper, neutral pressure sensitive base paper, neutral inkjet paper and neutral information paper.
　パルプ原料としては、クラフトパルプあるいはサルファイトパルプ等の晒あるいは未晒化学パルプ、砕木パルプ、機械パルプあるいはサーモメカニカルパルプ等の
晒あるいは未晒高収率パルプ、新聞古紙、雑誌古紙、段ボール古紙あるいは脱墨古紙等の古紙パルプのいずれも使用することができる。また、上記パルプ原料と石綿、ポリアミド、ポリイミド、ポリエステル、ポリオレフィン、ポリビニルアルコール等の合成繊維との混合物も使用することができる。 Pulp raw materials include bleached or unbleached chemical pulp such as kraft pulp or sulfite pulp, bleached or unbleached high-yield pulp such as ground wood pulp, mechanical pulp or thermomechanical pulp, used newspaper, used magazine, used corrugated paper, or treated pulp. Any waste paper pulp, such as ink waste paper, can be used. Furthermore, a mixture of the above pulp raw materials and synthetic fibers such as asbestos, polyamide, polyimide, polyester, polyolefin, and polyvinyl alcohol can also be used.
　サイズ剤を加えて、紙の耐水性を向上させることができる。サイズ剤の例は、カチオン性サイズ剤、アニオン性サイズ剤、ロジン系サイズ剤（例えば、酸性ロジン系サイズ剤、中性ロジン系サイズ剤）である。サイズ剤の量は、パルプに対して０．０１～５重量％であってよい。 Sizing agents can be added to improve the water resistance of paper. Examples of sizing agents are cationic sizing agents, anionic sizing agents, and rosin-based sizing agents (eg, acidic rosin-based sizing agents, neutral rosin-based sizing agents). The amount of sizing agent may be from 0.01 to 5% by weight relative to the pulp.
　紙には必要に応じて、通常使用される程度の製紙用薬剤として、澱粉、変性澱粉、カルボキシメチルセルロース、ポリアミドポリアミン－エピクロルヒドリン樹脂等の紙力増強剤、凝集剤、定着剤、歩留り向上剤、染料、蛍光染料、スライムコントロール剤、消泡剤等の紙の製造で使用される添加剤を使用することができる。澱粉及び変性澱粉を用いることが好ましい。必要により、澱粉、ポリビニルアルコール、染料、コーティングカラー、防滑剤等を用いて、サイズプレス、ゲートロールコーター、ビルブレードコーター、キャレンダー等によって、撥剤を紙に塗布することができる。 As necessary, paper-making agents such as starch, modified starch, carboxymethyl cellulose, polyamide polyamine-epichlorohydrin resin, flocculants, fixing agents, retention improvers, and dyes are added to the paper as necessary. Additives used in paper manufacturing such as fluorescent dyes, slime control agents, antifoaming agents, etc. can be used. Preferably, starch and modified starch are used. If necessary, a repellent agent can be applied to the paper using a size press, a gate roll coater, a bill blade coater, a calender, etc. using starch, polyvinyl alcohol, dye, coating color, anti-slip agent, etc.
　外添においては、塗布層に含まれる撥液性化合物の量が０．０１～２．０ｇ／ｍ２、特に０．１～１．０ｇ／ｍ２であることが好ましい。塗布層は、撥剤と澱粉及び／又は変性澱粉によって形成されることが好ましい。塗布層における紙用撥剤の固形分量は２ｇ／ｍ２以下であることが好ましい。
　内添においては、紙を形成するパルプ１００重量部に対して、撥剤の量が０．０１～５０重量部又は０．０１～３０重量部、例えば０．０１～１０重量部、特に０．２～５．０重量部となるように、撥剤をパルプと混合することが好ましい。 In external addition, the amount of the liquid repellent compound contained in the coating layer is preferably 0.01 to 2.0 g/m 2 , particularly 0.1 to 1.0 g/m 2 . The coating layer is preferably formed of a repellent and starch and/or modified starch. The solid content of the paper repellent in the coating layer is preferably 2 g/m 2 or less.
In internal addition, the amount of repellent is 0.01 to 50 parts by weight or 0.01 to 30 parts by weight, for example 0.01 to 10 parts by weight, especially 0. It is preferable to mix the repellent with the pulp in an amount of 2 to 5.0 parts by weight.
　外添において、ロールとロールの間に処理液をため、任意のロールスピードとニップ圧で、ロール間の処理液に原紙を通す、いわゆるポンド式２ロールサイズプレス処理を用いても紙に耐油性を付与することができる。 In external addition, the paper has oil resistance even when using the so-called pound type two-roll size press process, in which the processing liquid is stored between rolls and the base paper is passed through the processing liquid between the rolls at a desired roll speed and nip pressure. can be granted.
　外添処理において、紙基材はサイズ剤、紙力増強剤、凝集剤、歩留まり剤又は凝結剤などの添加剤を含んでよい。添加剤はノニオン性、カチオン性、アニオン性又は両性であってよい。添加剤のイオン電荷密度は－１００００～１００００　μｅｑ／ｇ、好ましくは－４０００～８０００　μｅｑ／ｇであり、より好ましくは－１０００～７０００　μｅｑ／ｇであってよい。サイズ剤、紙力増強剤、凝集剤、歩留まり剤又は凝結剤などの添加剤（固形分又は活性成分）は、パルプに対して、一般に、０．１～１０重量％（例えば、０．２～５．０重量％）の量で使用できる。カチオン性の添加剤（例えば、サイズ剤、紙力増強剤、凝集剤、歩留まり剤又は凝結剤）を含む紙基材の場合は、撥剤はアニオン性であることが好ましい。 In the external addition treatment, the paper base material may contain additives such as a sizing agent, a paper strength agent, a flocculant, a retention agent, or a coagulant. Additives may be nonionic, cationic, anionic or amphoteric. The ionic charge density of the additive may be -10000 to 10000 μeq/g, preferably -4000 to 8000 μeq/g, and more preferably -1000 to 7000 μeq/g. Additives (solid content or active ingredients) such as sizing agents, paper strength agents, flocculants, retention agents, or coagulants are generally contained in an amount of 0.1 to 10% by weight (for example, 0.2 to 10% by weight) based on the pulp. 5.0% by weight). In the case of paper substrates containing cationic additives (eg sizing agents, paper strength agents, flocculants, retention agents or coagulants), the repellent is preferably anionic.
　内添処理において、パルプ濃度が０．５～５．０重量％（例えば、２．５～４．０重量％）であるパルプスラリーを抄紙することが好ましい。パルプスラリーに添加剤（例えば、サイズ剤、紙力増強剤、凝集剤、歩留まり剤又は凝結剤など）及び撥液性化合物を添加することができる。添加剤（例えば、サイズ剤、紙力増強剤、凝集剤、歩留まり剤又は凝結剤など）の例は、アルキルケテンダイマー、アルケニル無水コハク酸、スチレン系重合体（スチレン／マレイン酸系重合体、スチレン／アクリル酸系重合体）、尿素－ホルムアルデヒド重合体、ポリエチレンイミン、メラミン－ホルムアルデヒド重合体、ポリアミドアミン－エピクロルヒドリン重合体、ポリアクリルアミド系重合体、ポリアミン系重合体、ポリジアリルジメチルアンモニウムクロライド、アルキルアミン・エピクロルヒドリン縮合物、アルキレンジクロライドとポリアルキレンポリアミンの縮合物、ジシアンジアミド・ホルマリン縮合物、ジメチルジアリルアンモニウムクロライド重合体、オレフィン／無水マレイン酸重合体である。 In the internal addition treatment, it is preferable to make paper from a pulp slurry having a pulp concentration of 0.5 to 5.0% by weight (for example, 2.5 to 4.0% by weight). Additives (eg, sizing agents, paper strength agents, flocculants, retention agents, or coagulants) and liquid-repellent compounds can be added to the pulp slurry. Examples of additives (e.g. sizing agents, paper strength agents, flocculants, retention agents or coagulants) include alkyl ketene dimers, alkenyl succinic anhydrides, styrenic polymers (styrene/maleic acid polymers, styrene /acrylic acid polymer), urea-formaldehyde polymer, polyethyleneimine, melamine-formaldehyde polymer, polyamidoamine-epichlorohydrin polymer, polyacrylamide polymer, polyamine polymer, polydiallyldimethylammonium chloride, alkylamine These are epichlorohydrin condensates, alkylene dichloride and polyalkylene polyamine condensates, dicyandiamide/formalin condensates, dimethyldiallylammonium chloride polymers, and olefin/maleic anhydride polymers.
［繊維製品の前処理］
　繊維製品は、本開示の撥剤で処理する前に前処理されていてもよい。繊維製品の前処理を行うことで、撥剤で処理後の繊維製品に優れた堅牢性を付与し得る。 [Pre-treatment of textile products]
The textile may be pretreated prior to treatment with the repellent of the present disclosure. By pre-treating the textile product, it is possible to impart excellent fastness to the textile product after being treated with a repellent.
　繊維製品の前処理の例は、反応性第四級アンモニウム塩との反応等によるカチオン化処理、スルホン化、カルボキシル化、リン酸化等のアニオン化処理、アニオン化処理後のアセチル化処理、ベンゾイル化処理、カルボキシメチル化処理、グラフト化処理、タンニン酸処理、高分子コーティング処理等が挙げられる。 Examples of pretreatment for textile products 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.
　繊維製品を前処理する方法としては、限定されないが、従来既知の方法により繊維製品を前処理することができる。前処理液を必要により有機溶媒又は水に分散して希釈して、浸漬塗布、スプレー塗布、泡塗布等のような既知の方法により、繊維製品の表面に付着させ、乾燥する方法であってよい。求める処理の程度に応じて前処理液のｐＨ及び温度等が調整されてよい。繊維製品を前処理する方法の一例として、繊維製品を炭化水素系撥水剤で前処理する方法について詳述する。 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. As an example of a method for pre-treating textile products, a method for pre-treating textile products with a hydrocarbon water repellent will be described in detail.
　繊維製品の前処理方法は、繊維に－ＳＯ３Ｍ１（式中、Ｍ１は一価のカチオンを示す）で示される１価の基、－ＣＯＯＭ２（式中、Ｍ２は一価のカチオンを示す）で示される１価の基、及び－Ｏ－Ｐ（Ｏ）（ＯＸ１）（ＯＸ２）（式中、Ｘ１及びＸ２はそれぞれ独立に水素原子又は炭素数１～２２のアルキル基を示す）で示される１価の基からなる群より選ばれる少なくとも一種の官能基（以下、「特定官能基」という場合もある）を付与する工程を備えてもよい。 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 at least one functional group (hereinafter sometimes referred to as a "specific functional group") selected from the group consisting of monovalent groups represented by (indicating an alkyl group).
　Ｍ１としては、Ｈ、Ｋ、Ｎａ又は置換基を有してよいアンモニウムイオンが挙げられる。Ｍ２としては、Ｈ、Ｋ、Ｎａ又は置換基を有してよいアンモニウムイオンが挙げられる。Ｘ１又はＸ２がアルキル基である場合、炭素数１～２２のアルキル基であることが好ましく、炭素数４～１２のアルキル基であることがより好ましい。 Examples of M 1 include H, K, Na, or an ammonium ion which may have a substituent. Examples of M 2 include H, K, Na, or ammonium ion which may have a substituent. When 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.
　上記特定官能基を含む繊維（以下、「官能基含有繊維」という場合もある）は、例えば、以下の方法により用意することができる。
（ｉ）繊維材料に、上記特定官能基を有する化合物を付着させる。なお、化合物の付着は、上記特定官能基が十分な量で残される範囲で化合物の一部と繊維の一部とが化学的に結合している状態であってもよい。
（ｉｉ）繊維を構成する材料に上記特定官能基が直接導入されている繊維を用意する。 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.
(i) 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.
　（ｉ）の場合、例えば、繊維材料を、上記特定官能基を有する化合物の一種以上が含まれる前処理液で処理する官能基導入工程により、官能基含有繊維を得ることができる。 In the case of (i), for example, 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.
　繊維材料の素材としては、特に制限はなく、綿、麻、絹、羊毛等の天然繊維、レーヨン、アセテート等の半合成繊維、ポリアミド（ナイロン等）、ポリエステル、ポリウレタン、ポリプロピレン等の合成繊維及びこれらの複合繊維、混紡繊維等が挙げられる。繊維材料の形態は繊維（トウ、スライバー等）、糸、編物（交編を含む）、織物（交織を含む）、不織布等のいずれの形態であってもよい。 There are no particular restrictions on 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.
　本実施形態においては、得られる繊維製品の撥水性が良好になる観点から、ポリアミド及びポリエステルを素材として含む繊維材料を用いることが好ましく、特に、ナイロン６、ナイロン６，６等のナイロン、ポリエチレンテレフタレート（ＰＥＴ）、ポリトリメチルテレフタレート、ポリ乳酸等のポリエステル、及びこれらが含まれる混合繊維を用いることが好ましい。 In this embodiment, from the viewpoint of improving the water repellency of the obtained textile product, it is preferable to use 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.
　上記－ＳＯ３Ｍ１を有する化合物としては、フェノール系高分子を用いることができる。このようなフェノール系高分子としては、例えば、下記一般式で表される化合物を少なくとも一種含むものが挙げられる。 As the compound having -SO 3 M 1 , a phenolic polymer can be used. Examples of such phenolic polymers include those containing at least one compound represented by the following general formula.
Figure JPOXMLDOC01-appb-I000001

［式中、Ｘ２は－ＳＯ３Ｍ３（式中、Ｍ３は１価のカチオンを示す）又は下記一般式で表される基を表し、ｎは２０～３０００の整数である。］
Figure JPOXMLDOC01-appb-I000001

[wherein, 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. ]
Figure JPOXMLDOC01-appb-I000002

［式中、Ｍ４は１価のカチオンを表す。］
Figure JPOXMLDOC01-appb-I000002

[In the formula, M 4 represents a monovalent cation. ]
　上記Ｍ３としては、Ｈ、Ｋ、Ｎａ又は置換基を有してよいアンモニウムイオンが挙げられる。 Examples of M 3 include H, K, Na, or ammonium ion which may have a substituent.
　上記Ｍ４としては、Ｈ、Ｋ、Ｎａ又は置換基を有してよいアンモニウムイオンが挙げられる。 Examples of M 4 include H, K, Na, or ammonium ion which may have a substituent.
　上記一般式で表される化合物は、例えば、フェノールスルホン酸のホルマリン縮合物、スルホン化ビスフェノールＳのホルマリン縮合物であってもよい。 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.
　上記－ＣＯＯＭ２を有する化合物としては、ポリカルボン酸系ポリマーが挙げられる。 Examples of the compound having -COOM 2 include polycarboxylic acid polymers.
　ポリカルボン酸系ポリマーとしては、例えば、アクリル酸、メタクリル酸、マレイン酸等をモノマーとして用いて従来公知のラジカル重合法で合成したポリマー、又は、市販されているものを使用することができる。 As the 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.
　ポリカルボン酸系ポリマーの製造方法としては、例えば、上記モノマー及び／又はその塩の水溶液にラジカル重合開始剤を添加して、３０～１５０℃で２～５時間加熱反応させる方法が挙げられる。このとき、上記モノマー及び／又はその塩の水溶液に、メタノール、エタノール、イソプロピルアルコール等のアルコール類やアセトン等の水性溶剤を添加してもよい。ラジカル重合開始剤としては、例えば、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等の過硫酸塩、過硫酸塩と重亜硫酸ナトリウム等の組み合わせによるレドックス系重合開始剤、過酸化水素、水溶性アゾ系重合開始剤等が挙げられる。これらのラジカル重合開始剤は単独で使用してもよく、又は二以上を併用してもよい。さらに、ラジカル重合の際には、重合度を調整する目的で連鎖移動剤（例えば、チオグリコール酸オクチル）を添加してもよい。 A method for producing a polycarboxylic acid polymer includes, for example, adding a radical polymerization initiator to an aqueous solution of the above-mentioned monomer and/or its salt, and reacting the mixture 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 above-mentioned monomer and/or its salt. Examples of the radical polymerization initiator include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, redox-based polymerization initiators such as combinations of persulfates and sodium bisulfite, hydrogen peroxide, and water-soluble azo-based 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 (e.g., octyl thioglycolate) may be added to adjust the degree of polymerization.
　ラジカル重合には、上記モノマーのほかに共重合可能なモノマーを使用することができる。共重合可能なモノマーとしては、エチレン、塩化ビニル、酢酸ビニル等のビニル系モノマー、アクリルアミド、アクリレート類、メタクリレート類等が挙げられる。アクリレート類及びメタクリレート類は、ヒドロキシル基等の置換基を有してよい炭素数１～３の炭化水素基を有するものが好ましい。このようなアクリレート類又はメタクリレート類としては、メチルアクリレート、メチルメタクリレート、エチルアクリレート、エチルメタクリレート、２－ヒドロキシエチルアクリレート、２－ヒドロキシエチルメタクリレート、プロピルアクリレート、プロピルメタクリレート等が挙げられる。これらの共重合可能なモノマーは、単独で使用してもよく、又は二以上を併用してもよい。 In addition to the above monomers, copolymerizable monomers can be used for radical polymerization. Examples of 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. Examples of such acrylates or methacrylates 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.
　ポリカルボン酸系ポリマー中のカルボキシル基はフリーであっても、アルカリ金属やアミン系化合物等によって中和されていてもよい。アルカリ金属としては、ナトリウム、カリウム、リチウム等が挙げられ、アミン系化合物としてはアンモニア、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等が挙げられる。 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. Examples of alkali metals include sodium, potassium, and lithium, and examples of amine compounds include ammonia, monoethanolamine, diethanolamine, triethanolamine, and the like.
　ポリカルボン酸系ポリマーの重量平均分子量は、得られる繊維製品の撥水性が良好となる観点から、１０００～２００００が好ましく、３０００～１５０００がより好ましい。 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.
　ポリカルボン酸系ポリマーは、「ネオクリスタル７７０」（日華化学株式会社製、商品名）、「セロポールＰＣ－３００」（三洋化成工業株式会社製、商品名）等の市販品を用いることができる。 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. .
　上記－Ｏ－Ｐ（Ｏ）（ＯＸ１）（ＯＸ２）を有する化合物としては、例えば、下記一般式で表されるリン酸エステル化合物が挙げられる。
Figure JPOXMLDOC01-appb-I000003
［式中、Ｘ１又はＸ２は上記と同義であり、Ｘ３は炭素数１～２２のアルキル基を示す。］ Examples of the compound having -OP(O)(OX 1 )(OX 2 ) include phosphoric ester compounds represented by the following general formula.
Figure JPOXMLDOC01-appb-I000003
[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. ]
　上記リン酸エステル化合物としては、アルキルエステル部分が、炭素数１～２２のアルキル基であるリン酸モノエステル、ジエステル及びトリエステル、並びにこれらの混合物を用いることができる。 As the above-mentioned 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.
　得られる繊維製品の撥水性が良好となる観点から、ラウリルリン酸エステル、デシルリン酸エステルを用いることが好ましい。 From the viewpoint of improving the water repellency of the resulting textile product, it is preferable to use lauryl phosphate and decyl phosphate.
　リン酸エステル化合物は、例えば、「フォスファノールＭＬ－２００」（東邦化学工業株式会社製、商品名）等の市販品を用いることができる。 As the phosphoric acid ester compound, for example, a commercially available product such as "Phosphanol ML-200" (manufactured by Toho Chemical Industry Co., Ltd., trade name) can be used.
　上記特定官能基を有する化合物の一種以上が含まれる前処理液は、例えば、上述した化合物の水溶液とすることができる。また、前処理液には、酸、アルカリ、界面活性剤、キレート剤等を含有させてもよい。 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.
　繊維材料を上記前処理液で処理する方法としては、例えば、パディング処理、浸漬処理、スプレー処理、コーティング処理が挙げられる。パディング処理としては、例えば、繊維染色加工辞典（昭和３８年、日刊工業新聞社発行）の３９６～３９７頁や色染化学ＩＩＩ（１９７５年、実教出版株式会社発行）の２５６～２６０頁に記載のパディング装置を用いた方法が挙げられる。コーティング処理としては、例えば、染色仕上機器総覧（昭和５６年、繊維社発行）の４７３～４７７頁に記載のコーティング機を用いる方法が挙げられる。浸漬処理としては、例えば、染色仕上機器総覧（昭和５６年、繊維社発行）の１９６～２４７頁に記載のバッチ式染色機を用いる方法が挙げられ、液流染色機、気流染色機、ドラム染色機、ウインス染色機、ワッシャー染色機、チーズ染色機等を用いることができる。スプレー処理としては、例えば、圧搾空気で処理液を霧状にして吹き付けるエアースプレーや、液圧霧化方式のエアースプレーを用いた方法が挙げられる。このときの処理液の濃度や付与後の熱処理等の処理条件は、その目的や性能等の諸条件を考慮して、適宜調整することができる。また、前処理液が水を含有する場合は、繊維材料に付着させた後に水を除去するために乾燥させることが好ましい。乾燥方法としては、特に制限はなく、乾熱法、湿熱法のいずれであってもよい。乾燥温度も特に制限されないが、例えば、室温～２００℃で１０秒～数日間乾燥させればよい。必要に応じて、乾燥後に１００～１８０℃の温度で１０秒～５分間程度加熱処理してもよい。 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. As 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. Moreover, when 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.
　なお、繊維材料が染色されるものである場合、前処理液による処理は、染色前でも、染色と同浴で行ってもよいが、還元ソーピングを行う場合は、その過程で吸着した上記特定官能基を有する化合物（例えば、フェノール系高分子化合物等）が、脱落してしまうおそれがあるので、染色後の還元ソーピング後に行うことが好ましい。 In addition, if the fiber material is to be dyed, 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.
　浸漬処理における処理温度は、６０～１３０℃とすることができる。処理時間は、５～６０分とすることができる。 The treatment temperature in the dipping treatment can be 60 to 130°C. Treatment time can be 5 to 60 minutes.
　前処理液による官能基導入工程は、上記特定官能基を有する化合物の付着量が、繊維材料１００重量部に対し、１．０～７．０重量部になる量で処理することが好ましい。この範囲内であると、耐久撥水性及び風合いを高水準で両立させることができる。 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.
　前処理液は、ｐＨを３～５に調整することが好ましい。ｐＨ調整は、酢酸、リンゴ酸等のｐＨ調整剤を用いることができる。 The pH of the pretreatment liquid is preferably adjusted to 3 to 5. For pH adjustment, a pH adjuster such as acetic acid or malic acid can be used.
　前処理液には、上記特定官能基を有する化合物を塩析効果により有効に繊維材料に吸着させるために塩を併用することもできる。使用できる塩としては、例えば、塩化ナトリウ
ム、炭酸ナトリウム、硫酸アンモニウム、硫酸ナトリウムが挙げられる。 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. Examples of salts that can be used include sodium chloride, sodium carbonate, ammonium sulfate, and sodium sulfate.
　前処理液による官能基導入工程では、過剰に処理された上記特定官能基を有する化合物を除去することが好ましい。除去方法としては、水洗による方法が挙げられる。十分な除去を行うことにより、後段の撥水加工において撥水性の発現が阻害されることを抑制することができ、加えて、得られる繊維製品の風合が良好となる。また、得られる官能基含有繊維は、炭化水素系撥水剤に接触させる前に、十分乾燥させておくことが好ましい。 In the functional group introduction step using the pretreatment liquid, it is preferable to remove the excessively treated compound having the specific functional group. Examples of 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.
　（ｉｉ）繊維を構成する材料に上記特定官能基が直接導入されている繊維としては、例えば、カチオン可染ポリエステル（ＣＤ－ＰＥＴ）が挙げられる。 (ii) 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).
　官能基含有繊維は、得られる繊維製品の撥水性が良好となる観点から、表面のゼータ電位が－１００～－０．１ｍＶであることが好ましく、－５０～－１ｍＶであることがより好ましい。繊維の表面のゼータ電位は、例えば、ゼータ電位・粒径測定システムＥＬＳＺ－１０００ＺＳ（大塚電子株式会社製）にて測定することができる。 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.).
　以上、実施形態を説明したが、特許請求の範囲の趣旨及び範囲から逸脱することなく、形態や詳細の多様な変更が可能なことが理解されるであろう。 Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims.
　以下、実施例を挙げて本開示を詳しく説明するが、本開示はこれらの実施例に限定されるものではない。 Hereinafter, the present disclosure will be described in detail with reference to Examples, but the present disclosure is not limited to these Examples.
＜試験方法＞
　試験の手順は次のとおりである。 <Test method>
The test procedure is as follows.
［水接触角］
　撥液性化合物の固形分濃度１．０％の溶液を、シリコンウェハー上にスピンコートし、平滑なスピンコート膜を得た。スピンコート膜上に、２μＬの水を滴下し、着滴１秒後の接触角を撥液性化合物の水接触角とした。 [Water contact angle]
A solution of a liquid repellent compound having a solid content concentration of 1.0% was spin-coated onto a silicon wafer to obtain a smooth spin-coated film. 2 μL of water was dropped onto the spin-coated film, and the contact angle 1 second after the droplet landed was taken as the water contact angle of the liquid-repellent compound.
［ＨＤ接触角］
　撥液性化合物の固形分濃度１．０％の溶液を、シリコンウェハー上にスピンコートし、平滑なスピンコート膜を得た。スピンコート膜上に、２μＬのＨＤを滴下し、着滴１秒後の接触角を撥液性化合物のＨＤ接触角とした。 [HD contact angle]
A solution of a liquid repellent compound having a solid content concentration of 1.0% was spin-coated onto a silicon wafer to obtain a smooth spin-coated film. 2 μL of HD was dropped onto the spin-coated film, and the contact angle 1 second after the droplet was deposited was defined as the HD contact angle of the liquid-repellent compound.
［処理布の作製］
　化合物をクロロホルムに２２．５ｍｇ/ｍＬの割合で溶解させ、処理液を調製した。この処理液に、ポリエチレンテレフタレート布（目付８８ｇ/ｍ２、７０デニール、グレー）を浸漬させ、風乾の後１５０℃で３分間乾燥させた。 [Preparation of treated cloth]
A treatment solution was prepared by dissolving the compound in chloroform at a rate of 22.5 mg/mL. A polyethylene terephthalate cloth (fabric weight: 88 g/m 2 , 70 denier, gray) was immersed in this treatment solution, air-dried, and then dried at 150° C. for 3 minutes.
［布撥水性能］
　処理布に対し、水を１滴付着させ、１５秒後に水はじきの様子、拭った後の染み具合を目視で判断した。
水滴をはじいており、拭った後に染みた跡がない：〇
水滴をはじいているが、拭った後に染みた跡がある：△
水滴が濡れ広がって、染みる：× [Fabric water repellency]
One drop of water was applied to the treated cloth, and after 15 seconds, the appearance of water repellency and the degree of staining after wiping were visually judged.
It is repelling water droplets and there are no stains after wiping: 〇 Water droplets are being repelled, but there are stains after wiping: △
Water droplets get wet, spread, and stain: ×
［処理紙の作製］
　木材パルプとして、ＬＢＫＰ（広葉樹さらしクラフトパルプ）とＮＢＫＰ（針葉樹さらしクラフトパルプ）の重量比率が、６０重量％と４０重量％で、かつ、パルプのろ水度が４００ｍｌ（Ｃａｎａｄｉａｎ Ｓｔａｎｄａｒｄ Ｆｒｅｅｎｅｓｓ）のパルプスラリーを調製し、このパルプスラリーに湿潤紙力剤、サイズ剤を添加して長網抄紙機により、紙密度が０．５８ｇ／ｃｍ３の坪量４５ｇ／ｍ２の紙を外添処理（サイズプレス処理）の原紙として使用した。この原紙の耐油性（ＫＩＴ値）は０、耐水性（Ｃｏｂｂ値）は５２ｇ／ｍ２であった。 [Preparation of treated paper]
A pulp slurry in which the weight ratio of LBKP (hardwood bleached kraft pulp) and NBKP (softwood bleached kraft pulp) is 60% by weight and 40% by weight as wood pulp, and the freeness of the pulp is 400ml (Canadian Standard Freeness). A wet paper strength agent and a sizing agent are added to this pulp slurry, and paper with a paper density of 0.58 g/cm3 and a basis weight of 45 g/m2 is externally added using a Fourdrinier paper machine (size press processing). It was used as a base paper. The oil resistance (KIT value) of this base paper was 0, and the water resistance (Cobb value) was 52 g/m 2 .
　この原紙に対して、化合物をクロロホルムに１４．９ｍｇ/ｍＬの割合で溶解させた処理液を、ギャップを０milの設定したベーカー式アプリケータ―で塗工し乾燥を繰り返す操作を三回行い、１４０℃で１分乾燥することで処理紙を作製した。 A treatment solution prepared by dissolving the compound in chloroform at a rate of 14.9 mg/mL was applied to this base paper using a Baker applicator with a gap of 0 mil, and drying was repeated three times. A treated paper was prepared by drying at ℃ for 1 minute.
［ＫＩＴ試験］
　３Ｍキットテスト（ＴＡＰＰＩ Ｔ－５５９ｃｍ－０２）により測定した。３Ｍキットテスト法は、ヒマシ油、トルエン、ヘプタンが配合された試験油を処理紙の表面におき、１５秒後に試験油を拭った際、処理紙への油染みの有無により評価した。キット番号１～６の試験油にて試験を実施し、染みが見られなかった最大のキット番号を耐油性の評価結果とした。 [KIT test]
Measured by 3M kit test (TAPPI T-559cm-02). In the 3M kit test method, a test oil containing castor oil, toluene, and heptane was placed on the surface of treated paper, and when the test oil was wiped 15 seconds later, the treated paper was evaluated by the presence or absence of oil stains. Tests were conducted using test oils with kit numbers 1 to 6, and the highest kit number with no stains was taken as the oil resistance evaluation result.
［紙撥水性能］
　処理紙に対し水を１滴付着させ、１５秒後に拭ったのちの染みの有無を目視で判断した。
拭った後に染みた跡がない：〇
拭った後に染みた跡がある：× [Paper water repellency]
One drop of water was applied to the treated paper, and after 15 seconds it was wiped and the presence or absence of stains was visually determined.
There are no stain marks after wiping: 〇 There are stain marks after wiping: ×
＜化合物１の合成＞
　ステアリルアミン４．４４ｇを脱水テトラヒドロフラン　１５．０ｍＬに溶解後、１，３，５－ベンゼントリカルボン酸トリエチル　１．３ｇを添加し、オイルバス温度５２℃で一晩撹拌した。翌日、室温まで冷却後、ろ過して乾燥させることで下記に示す化合物１を３．１８ｇ得た。
Figure JPOXMLDOC01-appb-I000004
 <Synthesis of compound 1>
After dissolving 4.44 g of stearylamine in 15.0 mL of dehydrated tetrahydrofuran, 1.3 g of triethyl 1,3,5-benzenetricarboxylate was added, and the mixture was stirred overnight at an oil bath temperature of 52°C. The next day, after cooling to room temperature, the mixture was filtered and dried to obtain 3.18 g of Compound 1 shown below.
Figure JPOXMLDOC01-appb-I000004
＜化合物２の合成＞
　マグネシウム　０．５８gとヨウ素　１粒を脱水テトラヒドロフラン　４０　ｍLに溶解後、１－ブロモオクタデカン　４ｇ添加し、室温で攪拌した。２０分後、１－ブロモオクタデカン　４ｇ添加し、さらに２時間室温で攪拌した。２時間後、反応溶液を氷浴で冷却後、ジメチルイソフタレート１ｇを３回に分けて添加し、一晩撹拌した。翌日、３Ｎ塩酸で中和後、ろ過し、得られた固体をアセトン、ジエチルエーテルで洗浄することで下記に示す化合物２を３．１９ｇ得た。
Figure JPOXMLDOC01-appb-I000005
 <Synthesis of compound 2>
After dissolving 0.58 g of magnesium and 1 grain of iodine in 40 mL of dehydrated tetrahydrofuran, 4 g of 1-bromooctadecane was added, and the mixture was stirred at room temperature. After 20 minutes, 4 g of 1-bromooctadecane was added, and the mixture was further stirred at room temperature for 2 hours. After 2 hours, the reaction solution was cooled in an ice bath, and 1 g of dimethyl isophthalate was added in three portions, followed by stirring overnight. The next day, the mixture was neutralized with 3N hydrochloric acid, filtered, and the resulting solid was washed with acetone and diethyl ether to obtain 3.19 g of Compound 2 shown below.
Figure JPOXMLDOC01-appb-I000005
＜化合物３の合成＞
　フロログルシノール０．５ｇを脱水テトラヒドロフラン　２０．０ｍＬに溶解後、イソシアン酸オクタデシル　３．７５ｇ、トリエチルアミン　１．７１ｍL、ジブチルチンジラウレート　3滴の順に添加し、オイルバス温度６０℃で一晩加熱攪拌した。翌朝、冷却後、ろ過した。得られた固体をアセトン、メタノール、ジクロロメタンで洗浄することで下記に示す化合物３を３．２７ｇ得た。
Figure JPOXMLDOC01-appb-I000006
 <Synthesis of compound 3>
After dissolving 0.5 g of phloroglucinol in 20.0 mL of dehydrated tetrahydrofuran, 3.75 g of octadecyl isocyanate, 1.71 mL of triethylamine, and 3 drops of dibutyltin dilaurate were added in this order, and the mixture was heated and stirred overnight at an oil bath temperature of 60°C. The next morning, after cooling, it was filtered. The obtained solid was washed with acetone, methanol, and dichloromethane to obtain 3.27 g of Compound 3 shown below.
Figure JPOXMLDOC01-appb-I000006
＜化合物４の合成＞
　既知化合物であり、Tetrahedron Letters (1999), 40(29), 5323-5326を参照して下記に示す化合物４を得た。
Figure JPOXMLDOC01-appb-I000007
 <Synthesis of compound 4>
Compound 4, which is a known compound and is shown below, was obtained with reference to Tetrahedron Letters (1999), 40(29), 5323-5326.
Figure JPOXMLDOC01-appb-I000007
＜化合物５の合成＞
　既知化合物であり、United States, US20220089508 A1 2022-03-24を参照して下記に示す化合物５を得た。
Figure JPOXMLDOC01-appb-I000008
 <Synthesis of compound 5>
Compound 5, which is a known compound and is shown below, was obtained with reference to United States, US20220089508 A1 2022-03-24.
Figure JPOXMLDOC01-appb-I000008
＜実施例１＞
　化合物１を用いて、接触角、布撥水性能、ＫＩＴ試験、紙撥水性能の評価を実施した。 <Example 1>
Compound 1 was used to evaluate contact angle, fabric water repellency, KIT test, and paper water repellency.
＜実施例２＞
　化合物１に代えて化合物２を用いた以外は、実施例１と同様に評価を実施した。 <Example 2>
Evaluation was performed in the same manner as in Example 1, except that Compound 2 was used instead of Compound 1.
＜実施例３＞
　化合物１に代えて化合物３を用いた以外は、実施例１と同様に評価を実施した。 <Example 3>
Evaluation was performed in the same manner as in Example 1, except that Compound 3 was used instead of Compound 1.
＜比較例１＞
　化合物で処理せずにシリコンシリコンウェハー、ポリエチレンテレフタレート布、原紙に対し、実施例１と同様の性能評価を実施した。 <Comparative example 1>
Performance evaluations similar to those in Example 1 were performed on silicon wafers, polyethylene terephthalate cloth, and base paper without treatment with compounds.
＜実施例４＞
　化合物４を用いて、接触角、布撥水性能の評価を実施した。 <Example 4>
Compound 4 was used to evaluate contact angle and fabric water repellency.
＜実施例５＞
　化合物４に代えて化合物５を用いた以外は、実施例４と同様に評価を実施した。 <Example 5>
Evaluation was performed in the same manner as in Example 4, except that Compound 5 was used in place of Compound 4.
　試験結果を下記表にまとめる。 The test results are summarized in the table below.
［表１：接触角試験］
Figure JPOXMLDOC01-appb-I000009

 [Table 1: Contact angle test]
Figure JPOXMLDOC01-appb-I000009
［表２：布試験］
Figure JPOXMLDOC01-appb-I000010

 [Table 2: Fabric test]
Figure JPOXMLDOC01-appb-I000010
［表３：紙試験］
Figure JPOXMLDOC01-appb-I000011
 [Table 3: Paper test]
Figure JPOXMLDOC01-appb-I000011

Claims (14)

  1. 下記式：
    Ａ（－Ｘ－Ｒｎ）ｍ
    ［式中、
    Ａは置換基を有してよい炭化水素芳香環からｍ個の水素原子を取り除いたｍ価の基であり、
    Ｘは、各出現において独立して、直接結合又は１＋ｎ価の基であり、
    Ｒは、各出現において独立して、置換基を有してよい炭素数６以上４０以下の脂肪族炭化水素基であり、
    ｎは、各出現において独立して、１以上３以下の整数であり、
    ｍは１以上６以下の整数である。］
    で表される化合物αを含む、撥剤。     The following formula:
    A(-X-R n ) m
    [In the formula,
    A is an m-valent group obtained by removing m hydrogen atoms from a hydrocarbon aromatic ring 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 from 6 to 40 carbon atoms which may have a substituent;
    n is an integer of 1 or more and 3 or less, independently in each occurrence,
    m is an integer of 1 or more and 6 or less. ]
    A repellent containing the compound α represented by.
  2. Ｒの炭素数が１２以上である、請求項１に記載の撥剤。 The repellent according to claim 1, wherein R has 12 or more carbon atoms.
  3. 前記化合物αが２個以上のＲを有する、請求項１又は２に記載の撥剤。 The repellent according to claim 1 or 2, wherein the compound α has two or more R.
  4. Ｘが、
    直接結合、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ（＝Ｏ）２－、－ＮＲ’－、－Ｃ（ＯＲ’）Ｒ’－、及び－Ｃ（ＯＲ’）（－）２、（式中、Ｒ’は、各出現において独立して、水素原子又は置換基を有してよい炭素数１～４０の炭化水素基である。）からなる群から選択される一以上から構成されるＸ１と、
    置換基を有してよい炭素数１～４０の炭化水素基であるＸ２と、
    からなる群から選択される一以上から構成される１＋ｎ価の基である、請求項１～３のいずれか一項に記載の撥剤。     X is
    Direct bond, -O-, -C(=O)-, -S(=O) 2 -, -NR'-, -C(OR')R'-, and -C(OR')(-) 2 , (wherein each occurrence of R' is independently a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent.) X 1 to be done,
    X 2 is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent;
    The repellent according to any one of claims 1 to 3, which is a 1+n-valent group consisting of one or more selected from the group consisting of:
  5. Ｘが、
    －Ｘ１－、又は、
    －Ｘ１－Ｘ２－Ｘ１－
    ［式中、
    Ｘ１が、各出現において独立して、
    直接結合、
    －Ｏ－、
    －Ｏ－Ｃ(＝Ｏ)－、
    －Ｏ－Ｃ(＝Ｏ)－Ｏ－、
    －Ｏ－Ｃ(＝Ｏ)－ＮＲ’－、
    －ＮＲ’－、
    －ＮＲ’－Ｃ(＝Ｏ)－、
    －ＮＲ’－Ｃ(＝Ｏ)－Ｏ－、
    －ＮＲ’－Ｃ(＝Ｏ)－ＮＲ’－、
    －Ｃ(＝Ｏ)－、
    －Ｃ(＝Ｏ)－Ｏ－、
    －Ｃ(＝Ｏ)－ＮＲ’－、
    －ＳＯ２－、
    －ＳＯ２ＮＲ’－、
    －Ｃ（ＯＲ’）Ｒ’－、又は
    －Ｃ（ＯＲ’）（－）２
    （式中、
    Ｒ’は、各出現において独立して、水素原子又は置換基を有してよい炭素数１～４０の炭化水素基である。）
    で表される基であり、
    Ｘ２が置換基を有してよい炭素数１～４０の炭化水素基である。］
    で表される基である、請求項１～４のいずれか一項に記載の撥剤。     X is
    -X 1 -, or
    -X 1 -X 2 -X 1 -
    [In the formula,
    X 1 independently in each occurrence,
    direct binding,
    -O-,
    -OC(=O)-,
    -O-C(=O)-O-,
    -OC(=O)-NR'-,
    -NR'-,
    -NR'-C(=O)-,
    -NR'-C(=O)-O-,
    -NR'-C(=O)-NR'-,
    -C(=O)-,
    -C(=O)-O-,
    -C(=O)-NR'-,
    -SO 2 -,
    -SO 2 NR'-,
    -C(OR')R'- or -C(OR')(-) 2
    (In the formula,
    R' is independently at each occurrence a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent. )
    is a group represented by
    X 2 is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent. ]
    The repellent according to any one of claims 1 to 4, which is a group represented by:
  6. Ｘが
    －Ｏ－Ｃ（＝Ｏ）－ＮＲ’－、
    －Ｃ（＝Ｏ）－ＮＲ’－、
    －ＳＯ２ＮＨ－、
    －Ｃ（ＯＲ’）Ｒ’－、又は
    －Ｃ（ＯＲ’）（－）２
    ［式中、
    Ｒ’は、水素原子又は置換基を有してよい炭素数１～４０の炭化水素基である。］
    である、請求項１～５のいずれか一項に記載の撥剤。     X is -O-C(=O)-NR'-,
    —C(═O)—NR′—,
    -SO 2 NH-,
    -C(OR')R'- or -C(OR')(-) 2
    [Wherein,
    R' is a hydrogen atom or a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent.]
    The repellent according to any one of claims 1 to 5,
  7. 前記化合物αがヒドロキシ基を有してもよいアルキル基である、請求項１～６のいずれか一項に記載の撥剤。 The repellent according to any one of claims 1 to 6, wherein the compound α is an alkyl group that may have a hydroxy group.
  8. 水、有機溶媒、又は水と有機溶媒との混合物とを含み、分散液又は溶液である、請求項１～７のいずれか一項に記載の撥剤。 The repellent according to any one of claims 1 to 7, which contains water, an organic solvent, or a mixture of water and an organic solvent, and is in the form of a dispersion or a solution.
  9. 多糖類、紙力増強剤、凝集剤、定着剤、歩留まり向上剤、凝結剤、シリコーンワックス、及びブロックドイソシアネートからなる群から選択された一以上を含む、請求項１～８のいずれか一項に記載の撥剤。 Any one of claims 1 to 8, comprising one or more selected from the group consisting of polysaccharides, paper strength agents, flocculants, fixing agents, retention improvers, coagulants, silicone waxes, and blocked isocyanates. The repellent described in .
  10. 繊維製品用である、請求項１～９のいずれか一項に記載の撥剤。 The repellent according to any one of claims 1 to 9, which is used for textile products.
  11. 紙製品用である、請求項１～９のいずれか一項に記載の撥剤。 The repellent according to any one of claims 1 to 9, which is used for paper products.
  12. フッ素原子を有しない、請求項１～１１のいずれか一項に記載の撥剤。 The repellent according to any one of claims 1 to 11, which does not have a fluorine atom.
  13. 請求項１～１２のいずれか一項に記載の撥剤によって処理された繊維製品。 A textile product treated with a repellent according to any one of claims 1 to 12.
  14. 請求項１～１２のいずれか一項に記載の撥剤によって処理された紙製品。 A paper product treated with a repellent according to any one of claims 1 to 12.
PCT/JP2023/033336 2022-09-14 2023-09-13 Repellent WO2024058205A1 (en)

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JPS6314764A (en) * 1986-07-03 1988-01-21 ヘキスト　アクチェンゲゼルシャフト Urethane comprising fatty fluoroalcohol, isocyanate and aromatic compound, manufacture and use
JPH02760A (en) * 1987-12-29 1990-01-05 Hoechst Ag Urethane made from fluorinated aliphatic alcohol, isocyanate, and substituted aromatic compound, and manufacture and use of said urethane
JP2004532196A (en) * 2001-03-09 2004-10-21 チバ　スペシャルティ　ケミカルズ　ホールディング　インコーポレーテッド Permanent surface modifier
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JPS58134072A (en) * 1982-02-01 1983-08-10 チバ−ガイギ−・アクチエンゲゼルシヤフト Perfluoroalkylphenols and naphthols, manufacture and use
JPS6314764A (en) * 1986-07-03 1988-01-21 ヘキスト　アクチェンゲゼルシャフト Urethane comprising fatty fluoroalcohol, isocyanate and aromatic compound, manufacture and use
JPH02760A (en) * 1987-12-29 1990-01-05 Hoechst Ag Urethane made from fluorinated aliphatic alcohol, isocyanate, and substituted aromatic compound, and manufacture and use of said urethane
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