WO2013061954A1 - Dispersion aqueuse de polyisocyanate bloqué, composition d'agent de traitement de fibres et tissu - Google Patents

Dispersion aqueuse de polyisocyanate bloqué, composition d'agent de traitement de fibres et tissu Download PDF

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Publication number
WO2013061954A1
WO2013061954A1 PCT/JP2012/077333 JP2012077333W WO2013061954A1 WO 2013061954 A1 WO2013061954 A1 WO 2013061954A1 JP 2012077333 W JP2012077333 W JP 2012077333W WO 2013061954 A1 WO2013061954 A1 WO 2013061954A1
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Prior art keywords
polyisocyanate
mass
block polyisocyanate
water
aqueous dispersion
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PCT/JP2012/077333
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English (en)
Japanese (ja)
Inventor
祐一 三輪
朝比奈　芳幸
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旭化成ケミカルズ株式会社
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Application filed by 旭化成ケミカルズ株式会社 filed Critical 旭化成ケミカルズ株式会社
Priority to CN201280050501.XA priority Critical patent/CN103890034B/zh
Priority to JP2013540781A priority patent/JP5809705B2/ja
Priority to KR1020147004546A priority patent/KR101593855B1/ko
Publication of WO2013061954A1 publication Critical patent/WO2013061954A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
    • C08G18/022—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing isocyanurate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1875—Catalysts containing secondary or tertiary amines or salts thereof containing ammonium salts or mixtures of secondary of tertiary amines and acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/285—Nitrogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
    • C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
    • C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
    • C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
    • C08G18/8025—Masked aliphatic or cycloaliphatic polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • 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
    • 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
    • D06M15/568—Reaction products of isocyanates with polyethers
    • 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
    • D06M15/572—Reaction products of isocyanates with polyesters or polyesteramides
    • 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
    • D06M15/576—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them containing fluorine
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Definitions

  • the present invention relates to an aqueous dispersion of block polyisocyanate, a fiber treatment agent composition containing the same, and a fabric treated with the fiber treatment agent composition.
  • Fiber treatment agents are used to impart various functions to the fibers. Its functions include water and oil repellency to prevent the adhesion of water and oil, texture to make the comfort comfortable, and prevention of deformation of the sewn product.
  • a composition having a fluororesin having a perfluoroalkyl group having 8 or more carbon atoms has been used as a fiber treatment agent imparting water repellency.
  • a fluororesin having a perfluoroalkyl group having 8 or more carbon atoms may be decomposed to generate perfluorooctanoic acid, which is of concern for accumulation and toxicity when discharged into the environment. It has been pointed out that there is. For this reason, studies are being actively conducted to replace the fluorocarbon resin with a perfluoroalkyl group having 8 to 6 carbon atoms and generating no perfluorooctanoic acid.
  • a fluororesin having a perfluoroalkyl group having 6 or less carbon atoms may have lower performance such as water repellency after repeated washing than a resin having 8 or more carbon atoms. ing.
  • a block polyisocyanate to a fiber treatment agent
  • An object of the present invention is to provide an aqueous dispersion of a block polyisocyanate having good water dispersion stability and high coating strength, and a fiber treatment agent having excellent mechanical stability as a fluorine fiber treatment agent. It is to provide a composition and a fabric having high washing durability.
  • the present inventors have found that an aqueous dispersion of a block polyisocyanate having a component unit of a polyisocyanate and a specific compound achieves the above-mentioned problems, and has completed the present invention. That is, the present invention is as follows.
  • Block agent unit [2] The average dispersion particle diameter of the block polyisocyanate: The aqueous dispersion of the block polyisocyanate according to [1], wherein ⁇ satisfies the following formula 1.
  • the contact angle of water / isopropyl alcohol (mass ratio 1/1) after washing 10 times is 90 degrees or more, A fabric coated with a fluororesin having substantially no perfluoroalkyl group having 8 or more carbon atoms.
  • the retention rate of the contact angle of water / isopropyl alcohol (mass ratio 1/1) after 10 washings with respect to the contact angle of water / isopropyl alcohol (mass ratio 1/1) when washing is not performed is 94% or more.
  • the aqueous dispersion of the block polyisocyanate of the present invention has good water dispersion stability of the block polyisocyanate and can provide a coating film having high coating strength. Furthermore, the fiber treatment composition containing the water dispersion is excellent in mechanical stability, and the fabric treated with the fiber treatment composition has high washing durability.
  • the aqueous dispersion of the block polyisocyanate of the present invention is The block polyisocyanate having at least the following 1) to 3) component units and water are included, and the average dispersed particle diameter ⁇ of the block polyisocyanate is 1 to 250 nm.
  • the average dispersed particle size is preferably 1 to 180 nm, more preferably 1 to 80 nm. By being in the above-mentioned range, it tends to be more excellent in water dispersion stability and mechanical stability.
  • the average dispersed particle diameter referred to here is a volume average dispersed particle diameter, and can be measured in detail by the method described in Examples.
  • Polyisocyanate unit having one or more diisocyanate monomer units selected from the group consisting of aliphatic diisocyanate monomers and alicyclic diisocyanate monomers 2) Polyethylene oxide units which are hydroxyl groups at one end 3) Block agent units
  • the block polyisocyanate of the present invention contains polyethylene oxide, which is a hydroxyl group at one end, which is a hydrophilic group, as a unit, and can reduce the average dispersed particle size with a smaller amount of hydrophilic groups than conventionally.
  • the average dispersed particle size of the blocked polyisocyanate preferably satisfies the following formula 1. By being in the above range, higher water dispersion stability and higher coating strength tend to be compatible. [Formula 1] 1 ⁇ ⁇ ⁇ 310-8 ⁇ A (A is the mass% of the polyethylene oxide unit which is a one-terminal hydroxyl group in the block polyisocyanate)
  • the block polyisocyanate of the present invention has a polyisocyanate unit.
  • the aliphatic diisocyanate monomer and the alicyclic diisocyanate monomer that can be used as a raw material for polyisocyanate do not contain a benzene ring in the structure.
  • the aliphatic diisocyanate monomer is not particularly limited, but is preferably one having 4 to 30 carbon atoms, such as tetramethylene-1,4-diisocyanate, pentamethylene-1,5-diisocyanate, hexamethylene diisocyanate (HDI), 2 2,4-trimethyl-hexamethylene-1,6-diisocyanate, lysine diisocyanate and the like.
  • the alicyclic diisocyanate is not particularly limited, but those having 8 to 30 carbon atoms are preferable.
  • IPDI isophorone diisocyanate
  • 1,3-bis (isocyanatemethyl) -cyclohexane 1,4′-dicyclohexylmethane diisocyanate.
  • Etc. is preferred because of weather resistance and industrial availability. Two or more of these can be used in combination.
  • a monovalent to hexavalent alcohol can be used as a raw material for the polyisocyanate used in the present invention.
  • Examples of 1 to 6-valent alcohols (polyols) that can be used as a raw material for the polyisocyanate of the present invention include non-polymerized polyols and polymerized polyols.
  • the non-polymerized polyol is a polyol that does not undergo polymerization history, and the polymerized polyol is a polyol obtained by polymerizing monomers.
  • Non-polymerized polyols include monoalcohols, diols, triols, tetraols and the like.
  • monoalcohols include, but are not limited to, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, s-butanol, n-pentanol, n-hexanol, n-octanol, Examples thereof include n-nonanol, 2-ethylbutanol, 2,2-dimethylhexanol, 2-ethylhexanol, cyclohexanol, methylcyclohexanol, ethylcyclohexanol and the like.
  • the diol is not particularly limited, and examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2- Butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,2-propanediol, 1,5-pentanediol, 2-methyl-2,3- Butanediol, 1,6-hexanediol, 1,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,3-dimethyl-2,3-butanediol, 2- Ethyl-hexanediol, 1,2-octanediol, 1,2-decanedio Le
  • the polymerization polyol is not particularly limited, and examples thereof include polyester polyol, polyether polyol, acrylic polyol, and polyolefin polyol.
  • Polyester polyol is not particularly limited, for example, succinic acid, adipic acid, sebacic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid or the like, or ethylene glycol, Obtained by ring-opening polymerization of ⁇ -caprolactone using a polyester polyol obtained by a condensation reaction with a single or mixture of polyhydric alcohols such as propylene glycol, diethylene glycol, neopentyl glycol, trimethylolpropane and glycerin, or a mixture thereof. Such as polycaprolactones.
  • the polyether polyol is not particularly limited.
  • hydroxides such as lithium, sodium and potassium, strong basic catalysts such as alcoholates and alkylamines, complex metal cyanide complexes such as metal porphyrins and hexacyanocobaltate zinc complexes
  • Polyether obtained by random or block addition of a single or mixture of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, and styrene oxide to a single or mixture of polyvalent hydroxy compounds
  • Examples include polyether polyols obtained by reacting an alkylene oxide with a polyol or a polyamine compound such as ethylenediamine.
  • examples include so-called polymer polyols obtained by polymerizing acrylamide or the like using these polyethers as a medium.
  • the polyisocyanate used in the present invention preferably contains an isocyanurate group.
  • a coating film cured using a polyisocyanate having an isocyanurate group has good weather resistance.
  • the polyisocyanate used in the present invention can also contain functional groups other than isocyanurate groups, for example, biuret groups, urea groups, uretdione groups, urethane groups, allophanate groups, oxadiazine trione groups and the like.
  • the polyisocyanate having an isocyanurate group can be obtained by, for example, carrying out an isocyanuration reaction with a catalyst or the like, stopping the reaction when a predetermined conversion rate is reached, and removing the diisocyanate monomer.
  • the isocyanuration reaction catalyst used in this case those having basicity are generally preferred. Specifically, (a) tetraalkylammonium hydroxides such as tetramethylammonium and tetraethylammonium, and weak organic acids such as acetic acid.
  • hydroxy weak ammonium salt such as hydroxyalkylammonium hydroxide and acetic acid such as trimethylhydroxypropylammonium, trimethylhydroxyethylammonium, triethylhydroxypropylammonium and triethylhydroxyethylammonium
  • Alkali metal salts of alkyl carboxylic acids such as myristic acid such as tin, zinc and lead, metal alcoholates such as (d) sodium and potassium, and (e) amino acids such as hexamethyldisilazane Le group-containing compound,
  • a Mannich bases in combination with tertiary amines and epoxy compounds include phosphorus compounds such as (h) tributylphosphine.
  • the amount of these catalysts used is selected from the range of 10 ppm to 1% with respect to the total mass of the diisocyanate and polyol as raw materials.
  • these isocyanuration reaction catalysts are inactivated by addition of acidic substances such as phosphoric acid and acidic phosphoric acid esters that neutralize the catalyst, thermal decomposition, and chemical decomposition.
  • the yield of polyisocyanate is 10 to 70% by mass. Polyisocyanates obtained in high yields tend to have high viscosities.
  • the reaction temperature of the isocyanurate reaction is preferably 20 ° C. or higher from the viewpoint of increasing the reactivity, and preferably 200 ° C. or lower from the viewpoint of suppressing product coloring and side reaction generation. More preferably, it is 50 to 150 ° C.
  • the diisocyanate monomer is removed by a thin film evaporator, extraction or the like, and the polyisocyanate is substantially free of the diisocyanate monomer.
  • the residual unreacted diisocyanate concentration in the obtained polyisocyanate is preferably 3% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less from the viewpoint of increasing curability.
  • the viscosity of the polyisocyanate that can be used in the present invention is 100 to 30000 mPa ⁇ s at 25 ° C., preferably 500 to 10000 mPa ⁇ s, more preferably 550 to 4000 mPa ⁇ s.
  • the number average molecular weight of the polyisocyanate used in the present invention is preferably 500 to 2000, more preferably 550 to 1000.
  • the statistical average number of isocyanate groups (number of isocyanate average functional groups) possessed by one molecule of the polyisocyanate is preferably 4 or more from the viewpoint of enhancing the crosslinkability, and the viewpoint of improving the solubility in a solvent and the dispersion stability in water. To 20 or less. More preferably, it is 4-15, and still more preferably 4-9.
  • the isocyanate group concentration in the polyisocyanate is preferably 5 to 25% by mass, more preferably 10 to 24% by mass, and still more preferably 15 to 24% by mass.
  • the block polyisocyanate of the present invention has a polyethylene oxide unit that is a hydroxyl group at one end.
  • Polyethylene oxide which is a hydroxyl group at one end is a compound having a hydroxyl group at one end of polyethylene oxide, and is a compound obtained by adding ethylene oxide to a starting monoalcohol.
  • the starting monoalcohol preferably has 1 to 10 carbon atoms.
  • the starting monoalcohol is not particularly limited, and examples thereof include methanol, ethanol, 2-propanol, n-butanol, sec-butanol, 2-ethyl-1-hexanol and the like. Of these, the preferred starting monoalcohol is methanol.
  • the molecular weight of polyethylene oxide which is a hydroxyl group at one end, is preferably 300 to 2000, more preferably 300 to 1500, and still more preferably 500 to 1000.
  • the block polyisocyanate of this invention has a block agent unit (unit derived from a block agent).
  • the blocking agent is a compound having one active hydrogen in the molecule, for example, alcohol compounds, alkylphenol compounds, phenol compounds, active methylene compounds, mercaptan compounds, acid amide compounds, acid imide compounds. Imidazole compounds, urea compounds, oxime compounds, amine compounds, imide compounds, pyrazole compounds, and the like. Examples of more specific blocking agents are shown below.
  • Alcohol compounds methanol, ethanol, 2-propanol, n-butanol, sec-butanol, 2-ethyl-1-hexanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, etc.
  • Alkylphenol compounds mono- and dialkylphenols having an alkyl group having 4 or more carbon atoms as a substituent, such as n-propylphenol, i-propylphenol, n-butylphenol, sec-butylphenol, t-butylphenol, n Monoalkylphenols such as hexylphenol, 2-ethylhexylphenol, n-octylphenol, n-nonylphenol, di-n-propylphenol, diisopropylphenol, isopropylcresol, di-n-butylphenol, di-t-butylphenol, di- dialkylphenols such as sec-butylphenol, di-n-octylphenol, di-2-ethylhexylphenol, and di-n-nonylphenol; (3) phenolic compounds; phenol, cresol, ethylphenol, styrenated phenol, hydroxybenzoic acid ester, etc
  • Urea compounds (9) Urea compounds; urea, thiourea, ethylene urea, etc. (10) Oxime compounds; formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, cyclohexanone oxime, etc. (11) Amine compounds; diphenylamine, aniline, carbazole, di-n-propylamine, diisopropylamine, isopropylethylamine, etc. (12) imine compounds; ethyleneimine, polyethyleneimine, and the like; and (13) pyrazole compounds; pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole, and the like.
  • Preferred blocking agents are amine compounds (preferably aliphatic amine compounds) or pyrazole compounds, and more preferred blocking agents are pyrazole compounds, with 3,5-dimethylpyrazole being particularly preferred.
  • a pyrazole compound, particularly 3,5-dimethylpyrazole the curability tends to be more excellent at low temperature or short time drying.
  • a monool obtained by polymerizing an alkylene oxide having 3 or more carbon atoms is derived from a starting monoalcohol and an alkylene oxide having 3 or more carbon atoms.
  • the starting monoalcohol has 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 4 to 8 carbon atoms.
  • Specific examples of these monoalcohols include, but are not limited to, alcohols such as methanol, ethanol, 2-propanol, n-butanol, sec-butanol, and 2-ethyl-1-hexanol.
  • the alkylene oxide having 3 or more carbon atoms is not particularly limited, and examples thereof include propylene oxide, butylene oxide, cyclohexene oxide, styrene oxide, and the like, and propylene oxide is preferable.
  • the alkylene oxide having 3 or more carbon atoms is not particularly limited.
  • hydroxides such as lithium, sodium and potassium, strong basic catalysts such as alcoholates and alkylamines, metalloporphyrins, complex metal cyanides such as hexacyanocobaltate zinc complexes, etc.
  • these alkylene oxides can be obtained by adding one or a mixture of these alkylene oxides to the above starting monoalcohol.
  • the monool number average molecular weight obtained by polymerizing an alkylene oxide having 3 or more carbon atoms is preferably 300 or more from the viewpoint of improving the compatibility between the block polyisocyanate and the polyol. Moreover, 2000 or less is preferable from a viewpoint of making the hardness of the coating film obtained high. More preferably, it is 300-1500, and more preferably 350-1000.
  • the mass concentration of the components in the block polyisocyanate of the present invention will be described.
  • the component concentration of the polyethylene oxide unit which is a hydroxyl group at one end is preferably 15% by mass or more from the viewpoint of improving solubility in water and dispersibility.
  • 30 mass% or less is preferable from a viewpoint of making the intensity
  • the component concentration of the polyisocyanate unit when the block polyisocyanate of the present invention is 100% by mass is preferably 45% by mass or more from the viewpoint of increasing the isocyanate group concentration in order to increase curability, and 65% by mass.
  • the following is preferred. More preferably, it is 50 to 60% by mass.
  • the component concentration of the blocking agent unit when the block polyisocyanate of the present invention is 100% by mass is preferably 15% by mass or more from the viewpoint of increasing curability.
  • Increasing the component concentration of the blocking agent results in a decrease in the component concentration of polyethylene oxide, which is a hydroxyl group at one end. Therefore, in order to obtain good water dispersion stability, 30% by mass or less is preferable from the viewpoint of increasing the proportion of structural units derived from polyethylene oxide which is a hydroxyl group at one end. More preferably, it is 20 to 30% by mass.
  • the component concentrations of the polyethylene oxide unit, polyisocyanate unit, and blocking agent unit which are one-end hydroxyl groups in the block polyisocyanate of the present invention can be specified by, for example, 1 H-NMR, 13 C-NMR, etc. It is also possible to specify from the quantity.
  • the block polyisocyanate of the present invention includes those comprising a polyisocyanate unit and a polyethylene oxide unit which is a hydroxyl group at one terminal, and those comprising a polyisocyanate unit and a blocking agent unit.
  • the component concentration of the diisocyanate trimer in the block polyisocyanate of the present invention is preferably 5% by mass or more from the viewpoint of high hardness and high weather resistance of the resulting coating film. Moreover, 40 mass% or less is preferable from a viewpoint of making the elongation of the coating film obtained high. More preferably, it is 10 to 40% by mass, and still more preferably 10 to 30% by mass.
  • the diisocyanate trimer component is a block polyisocyanate derived from three diisocyanate monomer molecules and a polyisocyanate having three isocyanate groups per molecule and three blocking agent molecules.
  • the number average molecular weight of the block polyisocyanate of the present invention is preferably 1000 or more from the viewpoint of increasing the isocyanate group concentration in order to increase curability. Moreover, 3000 or less is preferable from a viewpoint of favorable compatibility with a polyol. More preferably, it is 1000-2500.
  • the concentration of the isocyanate group blocked with the blocking agent of the block polyisocyanate of the present invention is preferably 5% by mass or more from the viewpoint of increasing curability. Moreover, 15 mass% or less is preferable from a viewpoint of making the coating film obtained tough.
  • an aqueous dispersion of the block polyisocyanate of the present invention can be obtained.
  • An example of the manufacturing method will be described in detail.
  • polyisocyanate is reacted with polyethylene oxide which is a hydroxyl group at one end.
  • organometallic salts such as tin, zinc and lead, tertiary amine compounds, alcoholates of alkali metals such as sodium, and the like may be used as catalysts.
  • the reaction temperature is preferably ⁇ 20 ° C. or higher from the viewpoint of increasing the reactivity.
  • 150 degrees C or less is preferable from a viewpoint of suppressing a side reaction. More preferably, it is 30 to 100 ° C.
  • polyethylene oxide which is a hydroxyl group at one end does not remain in an unreacted state.
  • the water dispersion stability and curability of the blocked polyisocyanate may be lowered.
  • the residual isocyanate group of the polyisocyanate that has reacted with the polyethylene oxide that is the hydroxyl group at one end thus obtained is reacted with a blocking agent.
  • the reaction temperature of this reaction and the reaction conditions such as the catalyst can be carried out in the same manner as in the above reaction.
  • a blocking agent or the like it is preferable to add a blocking agent or the like to completely disappear the isocyanate group.
  • These reactions can be performed in the presence of a solvent.
  • the solvent preferably contains no active hydrogen.
  • the block polyisocyanate concentration is 50% by mass or more, it is preferably maintained at a liquid temperature of 50 to 80 ° C. or 10% by mass or less and less than 50% by mass at a temperature of 20 to less than 50 ° C.
  • the average dispersed particle size of the block polyisocyanate may increase and precipitate or separate.
  • the present inventors have found that the method of adding water and the liquid temperature at the time of addition have a great influence on the average dispersed particle size of the blocked polyisocyanate, and that this influence varies depending on the concentration of the blocked polyisocyanate.
  • the amount of hydrophilic groups added has been increased.
  • the average dispersed particle size of the blocked polyisocyanate in the aqueous dispersion of the present invention can be controlled to 1 to 250 nm, preferably 1 to 180 nm, more preferably 1 to It can be controlled to 80 nm.
  • the average dispersion particle diameter: (phi) of block polyisocyanate can satisfy
  • the water dispersion of the block polyisocyanate of the present invention can contain up to 20% by mass of a solvent other than water.
  • a solvent other than water examples of the solvent in this case are not particularly limited.
  • the solvent may be used alone or in combination of two or more.
  • the solvent preferably has a solubility in water of 5% by mass or more, and specifically, dipropylene glycol dimethyl ether and dipropylene glycol monomethyl ether are preferable.
  • the block polyisocyanate concentration of the aqueous dispersion thus obtained is preferably 10 to 40%.
  • the fiber treatment agent composition of this invention contains the fluororesin which does not have a C8 or more perfluoroalkyl group substantially, and the aqueous dispersion of the said block polyisocyanate.
  • the fluororesin used in the present invention is a fluororesin substantially not containing a perfluoroalkyl group having 8 or more carbon atoms, and may contain a perfluorohexyl group having 6 carbon atoms.
  • the fluororesin include those polymerized using a fluorine-containing acrylate or methacrylate as a monomer.
  • the acrylate and methacrylate containing fluorine are not particularly limited, and specific examples include those containing a perfluoroalkyl group and having 3 to 6 carbon atoms. It has been pointed out that the perfluorooctyl group having 8 carbon atoms produces perfluorooctanoic acid, which is likely to accumulate in the environment and the human body.
  • the performance may be lower than that of 8 or more.
  • the block polyisocyanate of the present invention improves the mechanical stability of the fluororesin substantially free of perfluoroalkyl groups having 8 or more carbon atoms.
  • fluorine monomer In addition to the fluorine monomer, other monomers can be used in combination.
  • the following monomers can be used in combination. The following are mentioned as another monomer copolymerizable with the acrylate and / or methacrylate which have a perfluoroalkyl group.
  • the acrylic acid or methacrylic acid ester is not particularly limited. Hydroxyalkyl acrylate, hydroxyalkyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, alkylene diol acrylate, and the like.
  • Acrylamide or methacrylamides are not particularly limited.
  • acrylamide such as alkylene diol dimethacrylate, methacrylamide, N- methylol acrylamide, N- methylol methacrylamide, diacetone acrylamide, diacetone methacrylamide, methylolated di- Acetone acrylamide etc. are mentioned.
  • the maleic acid alkyl esters are not particularly limited, and examples thereof include dibutyl maleate.
  • the olefin is not particularly limited, and examples thereof include ethylene, propylene, butadiene, isoprene, vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride, and chloroprene.
  • the vinyl carboxylates are not particularly limited, and examples thereof include vinyl acetate.
  • styrenes include, but are not limited to, styrene, ⁇ -methyl styrene, ⁇ -methyl styrene, and the like.
  • Vinyl ethers are not particularly limited, and examples thereof include ethyl vinyl ether, cyclohexyl vinyl ether, and halogenated alkyl vinyl ether.
  • the amount ratio between the acrylate and / or methacrylate having a perfluoroalkyl group and the other monomer copolymerizable with these is the ratio of the acrylate having a perfluoroalkyl group and the acrylate having a perfluoroalkyl group among all monomers used for copolymerization.
  • the total of methacrylates is preferably 40% by mass or more, and more preferably 50 to 80% by mass.
  • copolymers can be produced by known polymerization methods such as solution polymerization, emulsion polymerization, suspension polymerization, etc., but are preferably produced by emulsion polymerization.
  • the thus obtained fluororesin and the aqueous dispersion of block polyisocyanate are suitably used for the treatment of fabric as a fiber treating agent composition.
  • the resin mass ratio of the aqueous dispersion of the fluororesin and the blocked polyisocyanate is 50:50 to 95: 5, preferably 70:30 to 95: 5, and more preferably 80:20 to 90:10. is there. By setting it as the above range, the water repellency tends to be more excellent.
  • the fiber treatment composition of the present invention includes flame retardants, dye stabilizers, antibacterial agents, antibacterial agents, antifungal agents, insect repellents, antifouling agents, antistatic agents, aminoplast resins, acrylic polymers, and glyoxal.
  • Resins, melamine resins, natural waxes, silicone resins, thickeners, polymer compounds, and the like can be blended.
  • the fiber treatment agent composition of the present invention blended in this way is diluted with water as necessary and used.
  • the resin concentration after dilution is usually 0.5 to 5% by mass, preferably 0.5 to 3% by mass.
  • the fabric of the present invention is treated with the fiber treatment composition.
  • the fluororesin is used as a fiber treatment agent that imparts water repellency to the fabric.
  • Examples of the water repellency evaluation method include a spray test of JIS-L-1092 and a contact angle measurement of water / isopropyl alcohol (mass ratio 1/1).
  • water repellency (washing durability) after washing the fabric is also a very important performance.
  • One of the washing methods is JIS-L-0217-103.
  • the decrease in water repellency can be evaluated, for example, by comparing before washing and after 10 washings.
  • a fluororesin substantially not containing a perfluoroalkyl group having 8 or more carbon atoms is generally inferior in washing durability as compared with a fluororesin containing a perfluoroalkyl group having 8 or more carbon atoms.
  • the fabric treated with the fiber treating agent composition of the present invention can exhibit very excellent washing durability.
  • the fabric of the present invention is coated with a fluororesin having a contact angle of water / isopropyl alcohol (mass ratio 1/1) of 90 degrees or more after 10 washings and having substantially no perfluoroalkyl group having 8 or more carbon atoms. It is preferred that The contact angle after 10 washings is more preferably 90 degrees or more, and further preferably 92 degrees or more. By being the said range, it exists in the tendency which is excellent in washing durability.
  • the contact angle / contact angle before washing:%) is preferably 94% or more, more preferably 96% or more, and further preferably 98% or more. It exists in the tendency which is excellent by washing durability by being the said range.
  • the fluororesin substantially not containing a perfluoroalkyl group having 8 or more carbon atoms, which is coated on the fabric, can be identified by combustion ion chromatography and TOF-SIMS. Further, the polyisocyanate coated on the fabric can be specified by TOF-SIMS.
  • substantially free of a perfluoroalkyl group having 8 or more carbon atoms means that m / z 377, m / z 427, and m / z 461 are not measured by TOF-SIMS using the following apparatus. This is the case of detection.
  • TRIFT III manufactured by Physical Electronics
  • Primary ion Ga + Acceleration voltage: 15 kV Current: 600 pA
  • Analysis area 200 ⁇ m ⁇ 200 ⁇ m
  • Detected ion Positive ion Electron gun: Available
  • the treatment of the fiber using the fiber treatment agent composition of the present invention can be performed by attaching a resin to the fiber and then heating it.
  • the resin adhesion method include a pad method, a dipping method, a spray method, a coating method, and a printing method.
  • heating is performed at a temperature of 100 ° C. or higher.
  • heating is performed at a temperature of about 140 to 180 ° C. for 10 seconds to 10 minutes, preferably about 30 seconds to 3 minutes.
  • fabrics to which the treatment liquid of the present invention can be applied include natural fibers such as cotton, kapok, flax, hemp, burlap, manila hemp, sisal hemp, wool, cashmere, mohair, alpaca, camel hair, silk, and feathers, Recycled fibers such as rayon, polynosic, cupra and tencel, cellulose acetate fibers, semi-synthetic fibers such as promix, polyamide fibers, polyester fibers, acrylic fibers, polyolefin fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, polyurethane fibers, polyoxy Synthetic fibers such as methylene fiber, polytetrafluoroethylene fiber, benzoate fiber, polyparaphenylene bisbisthiazole fiber, polyparaphenylenebenzbisoxazole fiber, polyimide fiber, asbestos, glass fiber, carbon fiber, alumina fiber, silicon carbide fiber , Boron fiber, Tyranno fiber, inorganic whisker,-lock fiber, inorganic
  • Viscosity measurement The viscosity was measured using the following apparatus. Equipment: RE-80R (manufactured by Toki Sangyo) Rotor: Cone plate 1 ° 34 ' ⁇ R24 Measurement temperature: 25 ° C
  • the number average molecular weight was a polystyrene-based number average molecular weight determined by gel permeation chromatography using the following apparatus.
  • Apparatus HLC-802A (manufactured by Tosoh) Column: G1000HXL x 1 (Tosoh product) G2000HXL x 1 (Tosoh product) G3000HXL x 1 (Tosoh) Carrier: Tetrahydrofuran Flow rate: 0.6 mL / min Sample concentration: 1.0% by mass Injection volume: 20 ⁇ L Temperature: 40 ° C Detection method: Differential refractometer
  • Isocyanate group content of polyisocyanate Weigh accurately 1-3 g of polyisocyanate in an Erlenmeyer flask (Wg), and then add 20 ml of toluene to dissolve the polyisocyanate. Thereafter, 10 ml of a 2N di-n-butylamine toluene solution is added, and after mixing, left at room temperature for 15 minutes. Add 70 ml of isopropyl alcohol and mix. This solution is titrated with 1N hydrochloric acid solution (factor F) to an indicator.
  • Wg Erlenmeyer flask
  • the titration value was set to 2 ml, the same operation was performed without polyisocyanate, the titration value was set to V1 ml, and the isocyanate group content of the polyisocyanate was calculated from the following formula.
  • Isocyanate group content (mass%) (V1-V2) ⁇ F ⁇ 42 / (W ⁇ 1000) ⁇ 100
  • isocyanate average functional group number polyisocyanate number average molecular weight (Mn) ⁇ isocyanate group content (mass%) ⁇ 0.01) / 42
  • Average dispersed particle size (volume average dispersed particle size): The volume average particle diameter was measured using the following apparatus. Equipment: Nanotrac UPA-EX150 (manufactured by Nikkiso) Solvent: Water Temperature: 23 ° C
  • Coating strength Using TENSILON RTE-1210 (manufactured by A & D), the coating strength was measured under the following conditions. The coating film was cured at 150 ° C. for 30 minutes. The breaking strength of the coating film at this time was recorded. The larger the value, the higher the strength.
  • Water repellency test A spray test of JIS-L-1092 was conducted, and the wet state of the surface was observed and evaluated. The evaluation was as follows. The higher the value, the better the water repellency. 5: There was no wetness or adhesion of water droplets on the surface. 4: Although it did not get wet on the surface, it showed adhesion of small water droplets. 3: Shows small individual water droplets on the surface. 2: Shows wetness on half of the surface, with small individual wetness penetrating the fabric. 1: The entire surface showed wetness.
  • TRIFT III manufactured by Physical Electronics
  • Primary ion Ga + Acceleration voltage: 15 kV Current: 600 pA
  • Analysis area 200 ⁇ m ⁇ 200 ⁇ m
  • Detected ion Positive ion Electron gun: Available
  • the viscosity of the obtained polyisocyanate at 25 ° C. was 25,000 mPa ⁇ s, the isocyanate group content was 19.9% by mass, the number average molecular weight was 1080, and the isocyanate average functional group number was 5.1.
  • the viscosity of the obtained polyisocyanate at 25 ° C. was 2700 mPa ⁇ s, the isocyanate content was 21.7%, the number average molecular weight was 660, and the number of isocyanate average functional groups was 3.4.
  • Example 1 100 parts by mass of the polyisocyanate obtained in Production Example 1 in the same reactor as in Production Example 1, 1.5 parts by mass of monool (trade name “Exenol 908” manufactured by Asahi Glass Co., Ltd.), polyethylene oxide which is a hydroxyl group at one end (Nippon Emulsifier Co., Ltd., trade name “MPG-081”) 42.5 parts by mass, Urethane catalyst (Nitto Kasei Kogyo Co., Ltd., trade name “Neostan U-810”) 0.01 parts by mass was charged with nitrogen. The atmosphere was maintained at 80 ° C. for 2 hours.
  • the concentration of the block polyisocyanate in the aqueous dispersion of the obtained block polyisocyanate was 30.0% by mass, the concentration of water was 70.0% by mass, the average dispersed particle size was 25 nm, and the water dispersion stability was good. there were.
  • Example 1 (Examples 2 to 5, 7 to 9) Except as described in Table 1, the same procedure as in Example 1 was performed. The results are shown in Table 1.
  • Example 6 100 parts by mass of the polyisocyanate obtained in Production Example 1 in the same reactor as in Production Example 1, 1.5 parts by mass of monool (trade name “Exenol 908” manufactured by Asahi Glass Co., Ltd.), polyethylene oxide which is a hydroxyl group at one end (Nippon Emulsifier Co., Ltd., trade name “MPG-081”) 42.5 parts by mass, Urethane catalyst (Nitto Kasei Kogyo Co., Ltd., trade name “Neostan U-810”) 0.01 parts by mass was charged with nitrogen. The atmosphere was maintained at 80 ° C. for 2 hours.
  • the concentration of the block polyisocyanate in the aqueous dispersion of the obtained block polyisocyanate was 30.0% by mass, the concentration of water was 70.0% by mass, the average dispersed particle size was 100 nm, and the water dispersion stability was good. there were.
  • the concentration of the block polyisocyanate in the aqueous dispersion of the obtained block polyisocyanate is 30.0% by mass, the concentration of water is 70.0% by mass, the average dispersed particle size is 262 nm, and the water dispersion stability is poor. Met.
  • dialkyl (cured beef tallow) dimethylammonium chloride and 30 parts of polyoxyethylene polyoxypropylene block polymer are added and stirring is started. Thereto, 221 parts by mass of water are gradually added, and after the addition is completed, the mixture is further dispersed by a homomixer. Thereafter, methyl isobutyl ketone was distilled off under reduced pressure to obtain an emulsion having a solid content of 45% and an average dispersed particle size of 170 nm.
  • A-1 Polyisocyanate of Production Example 1
  • A-2 Polyisocyanate of Production Example 2
  • A-3 Isocyanurate type polyisocyanate of IPDI monomer (trade name “VESTANAT T1890 / 100” of Evonik Degussa)
  • B Monool (Asahi Glass Co., Ltd., “Exenol 908”)
  • C Polyethylene oxide (trade name of Nippon Emulsifier Co., Ltd., “MPG-081”)
  • D-1 3,5-dimethylpyrazole
  • D-2 Methyl ethyl ketoxime
  • E Urethane catalyst (trade name of Nitto Kasei Co., Ltd., “Neostan U-810”)
  • F Dipropylene glycol dimethyl ether
  • Example 10 Dimethylaminoethanol of aqueous polyester polyol “SETAL6306 SS-60 (trade name)” (manufactured by NUPLEX, hydroxyl group concentration 2.7% by mass (resin standard), acid value 43 mgKOH / g (resin standard), resin solid content 60%) 100 parts by mass of the neutralized product, 133 parts by mass of the aqueous dispersion of the block polyisocyanate obtained in Example 1 and 52 parts by mass of dipropylene glycol monomethyl ether were mixed to prepare a coating material having a solid content of 35% by mass. This paint was applied to an applicator on a polypropylene plate to a dry film thickness of 30 ⁇ m. After setting at room temperature for 15 minutes, the coating film was cured at 150 ° C. for 30 minutes. The coating film strength was 22 MPa.
  • Example 11 to 18, Comparative Examples 5 to 8 The same procedure as in Example 10 was carried out except that the aqueous dispersion of blocked polyisocyanate described in Table 2 was used. Table 2 shows the results of coating strength.
  • Example 19 Fluorine fiber treating agent “Asahi Guard AG-E061 (trade name)” (manufactured by Asahi Glass Co., Ltd., 20% solid content) 90 parts by mass and 6.7 parts by mass of an aqueous dispersion of the block polyisocyanate obtained in Example 1 Then, 3.3 parts by mass of water was mixed to prepare a mixed solution having a solid content of 20% by mass. As a result of measuring the mechanical stability of this mixed solution, the aggregate generation rate was 0.03% by mass.
  • test fabric was washed according to JIS-L-0217-103.
  • the detergent used was the product name Attack of Kao Corporation. Evaluation was performed at 10 washings. The contact angle after washing was 93 degrees, and the water repellency test was 5.
  • Example 20 to 27, Comparative Examples 9 to 12 The same operation as in Example 19 was carried out except that the aqueous dispersion of blocked polyisocyanate described in Table 2 was used.
  • Table 3 shows the results of the aggregate generation rate, contact angle, and water repellency test.
  • aqueous dispersion of the block polyisocyanate of the present invention and the fiber treatment composition containing the same can be suitably used in the field of water repellents for fibers and the like.

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Abstract

La présente invention a pour but de proposer : une dispersion aqueuse de polyisocyanate bloqué ayant une stabilité favorable de dispersion aqueuse, apte à atteindre une résistance élevée de revêtement, présentant une excellente stabilité mécanique en tant qu'agent de traitement de fibres dopé par fluor et apte à produire un tissu ayant une lessivabilité élevée ; et une composition d'agent de traitement de fibres contenant cette dispersion. La dispersion aqueuse de polyisocyanate bloqué contient de l'eau et un polyisocyanate bloqué ayant au moins des unités composantes (1-3) et a un diamètre moyen de particule dispersée du polyisocyanate bloqué de φ=1-250 nm. 1) Une unité polyisocyanate ayant au moins un type d'unité monomère diisocyanate choisie dans un groupe consistant en les monomères diisocyanates aliphatiques et les monomères diisocyanates alicycliques. 2) Une unité poly(oxyde d'éthylène) ayant un groupe hydroxyle sur une extrémité. 3) Une unité agent de blocage.
PCT/JP2012/077333 2011-10-25 2012-10-23 Dispersion aqueuse de polyisocyanate bloqué, composition d'agent de traitement de fibres et tissu WO2013061954A1 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
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JP2014065833A (ja) * 2012-09-26 2014-04-17 Asahi Kasei Chemicals Corp 水性ブロックポリイソシアネート、繊維処理剤組成物、及び繊維
JP2014210882A (ja) * 2013-04-19 2014-11-13 旭化成ケミカルズ株式会社 ブロックポリイソシアネート組成物、水分散体、繊維処理剤組成物及び布帛
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JP2014210882A (ja) * 2013-04-19 2014-11-13 旭化成ケミカルズ株式会社 ブロックポリイソシアネート組成物、水分散体、繊維処理剤組成物及び布帛
WO2018102387A1 (fr) * 2016-11-29 2018-06-07 Lanxess Solutions Us Inc. Prépolymères à terminaison isocyanate à blocs ayant des propriétés améliorées de traitement
JP2020019877A (ja) * 2018-07-31 2020-02-06 旭化成株式会社 水分散ブロックポリイソシアネート組成物、水分散体、水系コーティング組成物及びコーティング基材
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JP2020125422A (ja) * 2019-02-06 2020-08-20 東ソー株式会社 低温解離型水系ブロックポリイソシアネート及びこれを含有する塗料
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JP2020143231A (ja) * 2019-03-07 2020-09-10 旭化成株式会社 ブロックポリイソシアネート組成物、水系塗料組成物及び塗膜
JP7287795B2 (ja) 2019-03-07 2023-06-06 旭化成株式会社 ブロックポリイソシアネート組成物、水系塗料組成物及び塗膜

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