Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
• • 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
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • 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
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/564—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
  • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
  • D06M15/647—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences

Definitions

• the present invention relates to a dispersion and a textile product treated with the dispersion.
• Patent Document 1 describes a water repellent auxiliaries for non-fluorine-based water repellents, which contains organo-modified silicone of a specific structure.
• Patent Document 2 describes a surface treatment agent comprising (A) a water-repellent and oil-repellent polymer having repeating units derived from at least one water-repellent and oil-repellent monomer selected from a fluorine-containing monomer (A1) and a non-fluorine monomer (A2) having a hydrocarbon group with 7 to 40 carbon atoms, in an amount of 30 to 100% by weight relative to the water-repellent and oil-repellent polymer, (B) a silicone polymer of a specific structure, and (C) a liquid medium.
• A a water-repellent and oil-repellent polymer having repeating units derived from at least one water-repellent and oil-repellent monomer selected from a fluorine-containing monomer (A1) and a non-fluorine monomer (A2) having a hydrocarbon group with 7 to 40 carbon atoms, in an amount of 30 to 100% by weight relative to the water-repellent and oil-repellent polymer,
• Patent Document 1 aims to obtain a water-repellent auxiliary that can improve the durable water repellency of non-fluorinated water repellents
• Patent Document 2 aims to obtain a surface treatment agent that is excellent in water and oil repellency and slip resistance.
• these technologies did not provide sufficient processing stability for the organo-modified silicone in the treatment agent, or sufficient water wicking resistance (anti-wicking properties) and color of the textile product treated with the treatment agent.
• the present invention aims to solve the above problems and provide a dispersion liquid that can achieve excellent processing stability of organo-modified silicone and good water wicking resistance (anti-wicking properties) and color of textile products, a textile product treated with the dispersion liquid, and a method for manufacturing the textile product.
• R 20 , R 21 and R 22 each independently represent a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms
• R 23 represents a hydrocarbon group having 6 to 50 carbon atoms and an aromatic ring, or an alkyl group having 6 to 100 carbon atoms
• R 30 , R 31 , R 32 , R 33 , R 34 and R 35 each independently represent a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 6 to 50 carbon atoms and an aromatic ring, or an alkyl group having 6 to 100 carbon atoms
• a represents an integer of 0 or more
• b represents an integer of 1 or more
• (a+b) is 10 to 200, when a is 2 or more, a plurality of R 20 and R 21 may be the same or
• R 20 and R 21 each independently represent a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms, and a 1 is an integer of 30 or less.
• the amount of cyclic siloxane ( ⁇ ) represented by the following formula is 1000 mass ppm or less.
• the dispersion according to item 1, wherein R 23 in the general formula (1) is a saturated hydrocarbon group having 6 to 50 carbon atoms.
• the dispersion further comprises a hydrophobic polymer ( ⁇ ), 3.
• the acrylic polymer is represented by the following general formula (A-1): [In formula (A-1), R 1 represents a hydrogen atom or a methyl group, and R2 represents a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent. 4.
• the dispersion according to item 3 having a structural unit derived from a monomer (A1) represented by the following formula: [Item 5] 5.
• the acrylic polymer is represented by the following general formula (A-2): [In formula (A-2), R 11 represents a hydrogen atom or a methyl group; R 12 represents a divalent hydrocarbon group having 1 to 6 carbon atoms; Z represents an ester group or an amide group; W is a group represented by -CO-R 13 (wherein R 13 represents a monovalent hydrocarbon group having 1 to 4 carbon atoms), a -NH-CO-NH 2 group, or a group represented by the following formula (A-3): It represents a group represented by the following formula:
• the acrylic polymer is (B1) HLB is 7
• a polymerization step of polymerizing a monomer component which is a raw material of the hydrophobic polymer ( ⁇ )
• ⁇ organo-modified silicone
• a dispersion liquid, a textile product treated with the dispersion liquid, and a method for producing the textile product can be provided that can realize excellent processing stability of organo-modified silicone, and good water wicking resistance (anti-wicking properties) and color of textile products.
• R 20 , R 21 and R 22 each independently represent a hydrogen atom, a methyl group, an ethyl group, or an alkoxy group having 1 to 4 carbon atoms
• R 23 represents a hydrocarbon group having 6 to 50 carbon atoms and an aromatic ring, or an alkyl group having 6 to 100 carbon atoms
• R 30 , R 31 , R 32 , R 33 , R 34 and R 35 each independently represent a hydrogen atom, a methyl group, an ethyl group, an alkoxy group having 1 to 4 carbon atoms, a hydrocarbon group having 6 to 50 carbon atoms and an aromatic ring, or an alkyl group having 6 to 100 carbon atoms
• a represents an integer of 0 or more
• b represents an integer of 1 or more
• (a+b) is 10 to 200, when a is 2 or more, a plurality of R 20 and R 21
• a smaller amount of cyclic siloxane ( ⁇ ) in the dispersion is advantageous.
• the processing stability of the dispersion, the water wicking resistance of the textile product (anti-wicking property), and the color of the textile product are improved while maintaining the availability of the organo-modified silicone ( ⁇ ).
• a1 is an integer of 30 or less. In one embodiment, a1 is 3 or more. On the other hand, when a1 is a predetermined value or less, the product stability of the dispersion tends to be less adversely affected. In this respect, a1 is preferably 30 or less, or 20 or less, or 10 or less.
• the concentration of the cyclic siloxane ( ⁇ ) in the dispersion is, in one aspect, 1000 ppm by mass or less, preferably 500 ppm by mass or less, or 100 ppm by mass or less, or 10 ppm by mass or less, or 0 ppm by mass, from the viewpoints of anti-wicking properties, the hue of the textile product, and processing stability (gum-up properties).
• the amount of cyclic siloxane ( ⁇ ) can be confirmed using GC/MS (gas chromatograph mass spectrometer).
• the number of carbon atoms in the hydrocarbon group having 6 to 50 carbon atoms and having an aromatic ring, or the alkyl group having 6 to 100 carbon atoms is preferably 6 to 50, or 16 to 44, or 18 to 42, or 20 to 40, from the viewpoints of initial water repellency and durable water repellency.
• the molecular weight is preferably 6 to 50, or 8 to 40, or 8 to 36, or 8 to 24.
• examples of the hydrocarbon group having 6 to 50 carbon atoms and an aromatic ring include an aralkyl group having 6 to 50 carbon atoms, and a group represented by the following general formula (2):
• R 40 represents an alkylene group having 2 to 6 carbon atoms
• R 41 represents a single bond or an alkylene group having 1 to 4 carbon atoms
• c represents an integer of 0 to 3
• a plurality of R 41 may be the same or different.
• R 42 represents an alkylene group having 2 to 6 carbon atoms
• R 43 represents a single bond or an alkylene group having 1 to 4 carbon atoms
• d represents an integer of 0 to 3
• a plurality of R 43's may be the same or different.
• Examples of the group include a group represented by the following formula:
• the alkylene group in the general formulae (2) and (3) may be linear or branched.
• Examples of the aralkyl group having 6 to 50 carbon atoms include a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, a phenylhexyl group, and a naphthylethyl group.
• the phenylethyl group and the phenylpropyl group are preferred because they are easy to produce industrially and are readily available.
• R 40 is preferably an alkylene group having 2 to 4 carbon atoms, and c is preferably 0 or 1, and more preferably 0, in terms of ease of industrial production and availability.
• R is preferably an alkylene group having 2 to 4 carbon atoms
• d is preferably 0 or 1, and more preferably 0, in terms of ease of industrial production and availability.
• the above-mentioned hydrocarbon group having an aromatic ring and a carbon number of 6 to 50 the above-mentioned aralkyl group having a carbon number of 6 to 50 and the group represented by the above-mentioned general formula (2) are preferred in that they are easy to produce industrially and are readily available, and the above-mentioned aralkyl group having a carbon number of 6 to 50 is more preferred in that it can improve the water repellency of the resulting textile product.
• alkyl group having 6 to 100 carbon atoms may be linear or branched.
• alkyl groups having 6 to 100 carbon atoms include octyl, nonyl, decyl, undecyl, dodecyl, myristyl, cetyl, stearyl, 1-hexacosenyl (C26), 1-octacosenyl (C28), 1-triacontenyl (C30), and 1-dotriacontenyl (C32).
• R 20 , R 21 and R 22 are each preferably independently a hydrogen atom or a methyl group, and more preferably a methyl group.
• R 23 is preferably a saturated hydrocarbon having 6 to 50 carbon atoms, and the number of carbon atoms is more preferably 16 to 44, or 18 to 42, or 20 to 40. From the viewpoint of chalk mark resistance, in general formula (1), R 23 is preferably a saturated hydrocarbon having 6 to 50 carbon atoms, and the number of carbon atoms is more preferably 8 to 40, or 8 to 36, or 8 to 24.
• a is an integer of 0 or more. In terms of ease of industrial production, ease of availability, and superior peel strength of the resulting fiber product against resin coating, a is preferably 40 or less, and more preferably 30 or less.
• (a+b) is 10 to 200. From the viewpoint of ease of industrial production and availability, (a+b) is preferably 20 to 100, and more preferably 40 to 60. When (a+b) is within the above range, the silicone itself tends to be easier to produce and handle.
• silicones having SiH groups include methylhydrogensilicones with a degree of polymerization of 10 to 200, or copolymers of dimethylsiloxane and methylhydrogensiloxane. Among these, copolymers of dimethylsiloxane and methylhydrogensiloxane are preferred from the viewpoint of water repellency.
• the aromatic compound having a vinyl group is a compound derived from the hydrocarbon group having 6 to 50 carbon atoms and an aromatic ring in R 23 in the above general formula (1).
• aromatic compounds having a vinyl group include styrene, ⁇ -methylstyrene, vinylnaphthalene, allyl phenyl ether, allyl naphthyl ether, allyl-p-cumyl phenyl ether, allyl-o-phenyl phenyl ether, allyl-tri(phenylethyl)-phenyl ether, and allyl-tri(2-phenylpropyl)phenyl ether.
• the above ⁇ -olefin is a compound from which the alkyl group having 6 to 100 carbon atoms in R 23 in the above general formula (1) is derived.
• the ⁇ -olefin include ⁇ -olefins having 6 to 100 carbon atoms, such as 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-hexacosene (C26), 1-octacosene (C28), 1-triacontene (C30), and 1-dotriacontene (C32).
• the hydrosilylation reaction may be carried out by reacting the silicone having a SiH group with the aromatic compound having a vinyl group and the ⁇ -olefin in a stepwise or all-at-once reaction, if necessary, in the presence of a catalyst.
• the amounts of the silicone having a SiH group, the aromatic compound having a vinyl group, and the ⁇ -olefin used in the hydrosilylation reaction can be appropriately selected depending on the SiH group equivalent weight of the silicone having a SiH group, the number average molecular weight, etc.
• Catalysts used in hydrosilylation reactions include, for example, platinum and palladium compounds, with platinum compounds being preferred.
• platinum compounds include platinum(IV) chloride.
• the reaction conditions for the hydrosilylation reaction are not particularly limited and can be adjusted as appropriate.
• the reaction temperature is, for example, 10 to 200°C, and preferably 50 to 150°C.
• the reaction time can be, for example, 3 to 12 hours when the reaction temperature is 50 to 150°C.
• the hydrosilylation reaction is preferably carried out in an inert gas atmosphere.
• inert gas include nitrogen and argon.
• the reaction proceeds without a solvent, but a solvent may be used.
• solvents include dioxane, methyl isobutyl ketone, toluene, xylene, and butyl acetate.
• the dispersion may further contain a dispersion aid.
• a dispersion aid from the viewpoint of allowing the organo-modified silicone ( ⁇ ) to exist in a well-dispersed state (emulsified state in one embodiment) in the dispersion, one or more selected from a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an amphoteric surfactant may be used as the dispersion aid (emulsion aid in one embodiment).
• the content of the dispersion aid is preferably 0.5 to 50 parts by mass, more preferably 1 to 40 parts by mass, and even more preferably 1 to 30 parts by mass, relative to 100 parts by mass of the organo-modified silicone ( ⁇ ).
• a dispersion aid may be used when polymerizing or dispersing (emulsifying in one embodiment) the hydrophobic polymer ( ⁇ ) described below.
• the dispersion aid used may be the same as that used when dispersing (emulsifying in one embodiment) the organo-modified silicone ( ⁇ ).
• the content of the dispersion aid is preferably 0.5 to 50 parts by mass, more preferably 1 to 40 parts by mass, and even more preferably 1 to 30 parts by mass, relative to 100 parts by mass of the hydrophobic polymer ( ⁇ ).
• the content of the dispersion aid is 0.5 parts by mass or more, the dispersion stability of the hydrophobic polymer ( ⁇ ) in the dispersion tends to be further improved, and when it is 50 parts by mass or less, the water repellency of the textile product treated with the dispersion tends to be further improved.
• cationic surfactant examples include monoalkyltrimethylammonium salts having 8 to 24 carbon atoms, dialkyldimethylammonium salts having 8 to 24 carbon atoms, monoalkylamine acetates having 8 to 24 carbon atoms, dialkylamine acetates having 8 to 24 carbon atoms, and alkylimidazoline quaternary salts having 8 to 24 carbon atoms.
• monoalkyltrimethylammonium salts having 12 to 18 carbon atoms and dialkyldimethylammonium salts having 12 to 18 carbon atoms are preferred.
• Suitable examples of the cationic surfactant include stearyltrimethylammonium sulfate and stearyltrimethylammonium chloride.
• cationic surfactants may be used alone or in combination of two or more.
• Nonionic Surfactant examples include alcohols, polycyclic phenols, amines, amides, fatty acids, polyhydric alcohol fatty acid esters, oils and fats, polypropylene glycol, and alkylene oxide adducts thereof.
• the alcohols include linear or branched alcohols or alkenols having 8 to 24 carbon atoms, and compounds represented by the following general formula (AL-1): [In the formula, R 51 and R 52 each independently represent a linear or branched alkyl group having 1 to 8 carbon atoms or a linear or branched alkenyl group having 2 to 8 carbon atoms.] Or the following general formula (AL-2): [In the formula, R 53 represents a linear or branched alkyl group having 1 to 8 carbon atoms or a linear or branched alkenyl group having 2 to 8 carbon atoms.] Examples of the acetylene alcohol include acetylene alcohol represented by the following formula:
• polycyclic phenols include monohydric phenols such as phenol and naphthol that may have a hydrocarbon group having 1 to 12 carbon atoms, or their styrene (e.g., styrene, ⁇ -methylstyrene, or vinyltoluene) adducts, or their benzyl chloride reactants.
• styrene e.g., styrene, ⁇ -methylstyrene, or vinyltoluene
• amines include linear or branched aliphatic amines having 8 to 44 carbon atoms.
• Amids include linear or branched fatty acid amides with 8 to 44 carbon atoms.
• Polyhydric alcohol fatty acid esters include condensation products of polyhydric alcohols and carboxylic acids with 2 to 30 carbon atoms (including the carbon of the carboxyl group).
• Examples of such polyhydric alcohol fatty acid esters include sorbitan esters composed of sorbitan (alcohol) and carboxylic acids with 2 to 30 carbon atoms (including the carbon of the carboxyl group).
• the number of carbon atoms in the carboxylic acid constituting the sorbitan ester is 2 to 30, and preferably 5 to 21.
• the sorbitan ester may be a monocarboxylic acid ester of sorbitan and one carboxylic acid, a dicarboxylic acid ester of sorbitol and two carboxylic acids, or a tricarboxylic acid ester of sorbitol and three carboxylic acids, and is preferably a monocarboxylic acid ester.
• Sorbitan esters are represented by the following general formula (4): [In formula (4), R 61 represents an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms; R 64 , R 65 and R 66 each independently represent a hydrogen atom, -CO-R 61 , or -(CH 2 CH 2 O) e -(R 62 O) f -R 63 (wherein R 62 represents an alkylene group having 3 or more carbon atoms, R 63 represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms, e represents an integer of 2 or more, and f represents an integer of 0 or more).
• R 61 represents an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms
• R 64 , R 65 and R 66 each independently represent a hydrogen atom, -CO-R 61 , or -(CH 2 CH 2 O) e -(R 62 O) f -R 63
• R 62 represents an alkylene group having 3 or more carbon atoms
• R 63 represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms
• e represents an integer of 2 or more
• f represents an integer of 0 or more
• the compound may be represented by the formula:
• Examples of compounds represented by the above general formula (4) or (5) include sorbitan monolaurate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monooleate, sorbitan sesquistearate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, and polyoxyethylene sorbitan tristearate.
• Fats and oils include vegetable fats and oils, animal fats and oils, vegetable waxes, animal waxes, mineral waxes, hardened oils, etc.
• a combination of a linear or branched alcohol or alkenol having 8 to 24 carbon atoms and a sorbitan ester is more preferable, and a combination of a polyoxyethylene alkyl ether and a sorbitan fatty acid ester is particularly preferable.
• alkylene oxides examples include ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 1,4-butylene oxide, styrene oxide, epichlorohydrin, etc. From the viewpoints of having little effect on water repellency and improving the dispersibility (emulsification in one embodiment) of the organo-modified silicone ( ⁇ ) or the hydrophobic polymer ( ⁇ ), preferred alkylene oxides are ethylene oxide and 1,2-propylene oxide, and more preferred is ethylene oxide.
• the number of moles of alkylene oxide added is preferably 1 to 200, more preferably 3 to 100, and even more preferably 5 to 50. If the number of moles of alkylene oxide added is within the above range, it becomes easier to obtain high levels of water repellency and product stability.
• the HLB of the nonionic surfactant is preferably 2 to 18, more preferably 2 to 16. In terms of storage stability of the dispersion, it is more preferable to use two or more nonionic surfactants having different HLBs within the above range in combination.
• a nonionic surfactant is used for dispersing (emulsifying in one embodiment) the organo-modified silicone ( ⁇ ), it is preferable for the HLB to be within the above range in terms of obtaining good dispersibility.
• the HLB is preferably 7 to 18 in terms of forming a good aqueous dispersion, and taking into consideration the dispersion stability of the liquid polymer (during emulsion polymerization) or solid polymer (during dispersion polymerization) in the composition during and after emulsion polymerization or dispersion polymerization, the HLB is more preferably 9 to 15.
• the dispersion preferably further contains a hydrophobic polymer.
• the hydrophobic polymer may be one or more selected from the group consisting of acrylic polymers and urethane polymers.
• the dispersion preferably has a pH of 7 or less, more preferably 6 or less, and even more preferably 5 or less.
• the acrylic polymer is represented by the following general formula (A-1): [In formula (A-1), R 1 represents a hydrogen atom or a methyl group, and R2 represents a monovalent hydrocarbon group having 12 or more carbon atoms which may have a substituent.
• the monomer (A-1) (hereinafter, also referred to as component (A1)) has a structural unit derived therefrom.
• the hydrophobic polymer ( ⁇ ) may be composed only of structural units derived from the above-mentioned component (A1), or may further have one or more other structural units. At least one structural unit of the hydrophobic polymer ( ⁇ ) or a monomer corresponding to the structural unit (i.e., forming the structural unit) may have a functional group capable of reacting with a crosslinking agent, for example, at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group. In this case, the durable water repellency of the obtained textile product can be further improved.
• the isocyanate group may be protected with a blocking agent to form a blocked isocyanate group. When the functional group is an amino group, the texture of the obtained textile product can be further improved.
• R 12 may be linear or branched, may be a saturated or unsaturated hydrocarbon group, and may further have an alicyclic ring.
• the above (A2) component may be used alone or in combination of two or more types.
• the acrylic polymer can be obtained by emulsion polymerization or dispersion polymerization.
• the monomer component which is the raw material of the acrylic polymer, further contains a reactive activator (B) (hereinafter, also referred to as "component (B)").
• component (B) a reactive activator
• the acrylic polymer further contains a constitutional unit derived from the reactive activator (B).
• X is a linear or branched alkylene group having 1 to 6 carbon atoms, and from the viewpoint of the dispersion (emulsion in one embodiment) stability of the acrylic polymer of this embodiment, a linear alkylene group having 2 to 3 carbon atoms is more preferable.
• a 1 O is an alkyleneoxy group having 2 to 4 carbon atoms.
• the type and combination of A 1 O and the number m can be appropriately selected so as to fall within the above HLB range.
• m is preferably an integer of 1 to 80, and more preferably an integer of 1 to 60.
• m A 1 O may be the same or different.
• there are two or more types of A 1 O they may have a block addition structure or a random addition structure.
• the component (B1) represented by the above general formula (I-2) can be obtained by a conventionally known method and is not particularly limited. It can also be easily obtained from commercial products, such as "Latemul PD-420", “Latemul PD-430", and “Latemul PD-450” manufactured by Kao Corporation.
• R 4 is a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and having a polymerizable unsaturated group, such as a tridecenyl group, a tridecadienyl group, a tetradecenyl group, a tetradienyl group, a pentadecenyl group, a pentadecadienyl group, a pentadecatrienyl group, a heptadecenyl group, a heptadecadienyl group, a heptadecatrienyl group, etc. From the viewpoint of the dispersion (emulsion in one embodiment) stability of the acrylic polymer of this embodiment, R 4 is more preferably a monovalent unsaturated hydrocarbon group having 14 to 16 carbon atoms.
• Y2 is a divalent group containing an alkyleneoxy group having 2 to 4 carbon atoms.
• the type, combination and number of added alkyleneoxy groups in Y2 can be appropriately selected so as to fall within the above-mentioned HLB range.
• they can have a block addition structure or a random addition structure.
• the alkyleneoxy group is more preferably an ethyleneoxy group.
• R4 represents a monovalent unsaturated hydrocarbon group having 13 to 17 carbon atoms and a polymerizable unsaturated group
• a 2 O represents an alkyleneoxy group having 2 to 4 carbon atoms
• n can be appropriately selected so as to fall within the above HLB range, and specifically, an integer of 1 to 50 is preferable, and when n is 2 or more, the n A 2 O's may be the same or different.
• Preferred is a compound represented by the following formula:
• R 4 in the compound represented by the above general formula (II-2) include the same as R 4 in the above general formula (II-1).
• a 2 O is an alkyleneoxy group having 2 to 4 carbon atoms.
• the type and combination of A 2 O and the number of n can be appropriately selected so as to be within the above HLB range.
• a 2 O is more preferably an ethyleneoxy group, and n is preferably an integer of 1 to 50, more preferably an integer of 5 to 20, and even more preferably an integer of 8 to 14.
• n is 2 or more, the n A 2 O may be the same or different.
• they may have a block addition structure or a random addition structure.
• the component (B2) used in this embodiment and represented by the above general formula (II-2) can be synthesized by adding an alkylene oxide to a phenol having a corresponding unsaturated hydrocarbon group using a conventionally known method, and is not particularly limited.
• it can be synthesized by adding a predetermined amount of alkylene oxide under pressure at 120 to 170°C using an alkali catalyst such as caustic soda or caustic potassium.
• Phenols having the corresponding unsaturated hydrocarbon group include pure products or mixtures produced industrially, as well as pure products or mixtures extracted and purified from plants, etc. Examples include 3-[8(Z),11(Z),14-pentadecatrienyl]phenol, 3-[8(Z),11(Z)-pentadecadienyl]phenol, 3-[8(Z)-pentadecenyl]phenol, 3-[11(Z)-pentadecenyl]phenol, etc., which are extracted from cashew nut shells, etc. and are collectively known as cardanol.
• the (B3) component used in this embodiment is a compound in which an alkylene oxide having 2 to 4 carbon atoms is added to an oil having a hydroxyl group and a polymerizable unsaturated group, and the oil has an HLB of 7 to 18.
• the oil having a hydroxyl group and a polymerizable unsaturated group include mono- or diglycerides of fatty acids that may contain hydroxyunsaturated fatty acids (palmitoleic acid, oleic acid, linoleic acid, ⁇ -linolenic acid, arachidonic acid, eicosapentaenoic acid, docosapentaenoic acid, etc.), and triglycerides of fatty acids that contain at least one hydroxyunsaturated fatty acid (ricinoleic acid, ricinoelaidic acid, 2-hydroxytetracosenoic acid, etc.).
• an alkylene oxide adduct of a triglyceride of a fatty acid containing at least one hydroxy unsaturated fatty acid is preferred
• an alkylene oxide adduct of castor oil (triglyceride of a fatty acid containing ricinoleic acid) having 2 to 4 carbon atoms is more preferred
• an ethylene oxide adduct of castor oil is even more preferred.
• the number of moles of added alkylene oxide can be appropriately selected so as to be within the above-mentioned HLB range, and in terms of the dispersion (emulsion in one embodiment) stability of the acrylic polymer of this embodiment, 20 to 50 moles is more preferred, and 25 to 45 moles is even more preferred. Furthermore, when there are two or more types of alkylene oxide, they can have a block addition structure or a random addition structure.
• the acrylic polymer further contains a structural unit derived from at least one monomer (C) (hereinafter also referred to as component (C)) selected from the group consisting of the following (C1), (C2), (C3) and (C4).
• (C2) The following general formula (C-2): [In formula (C-2), R 7 represents a hydrogen atom or a methyl group, and R 8 represents a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms which may have a substituent.] (Meth)acrylic acid ester monomer represented by the formula (hereinafter also referred to as component (C2)).
• (C4) The following general formula (C-4): [In formula (C-4), R 10 represents hydrogen or a methyl group, p represents an integer of 2 or more, S represents a (p+1)-valent organic group, and T represents a monovalent organic group having a polymerizable unsaturated group.] (Meth)acrylic acid ester monomer represented by the formula (hereinafter also referred to as component (C4)).
• the above-mentioned (C1) component is a (meth)acrylic acid ester monomer having a monovalent chain-like hydrocarbon group having 1 to 11 carbon atoms, which has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, an isocyanate group, and a (meth)acryloyloxy group in the ester portion.
• the above-mentioned monovalent chain-like hydrocarbon group having 1 to 11 carbon atoms preferably has at least one functional group selected from the group consisting of a hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group.
• the isocyanate group may be a blocked isocyanate group protected with a blocking agent.
• the (C1) component examples include 2-hydroxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate. These monomers may be used alone or in combination of two or more. Among them, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate are preferred in terms of improving the durable water repellency of the resulting textile product. Furthermore, dimethylaminoethyl (meth)acrylate is preferred in terms of improving the feel of the resulting textile product.
• the mass of the (C1) component to be blended is preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more, per 100 parts by mass of the (A1) component to be blended, from the viewpoint of water repellency.
• the mass of the (C1) component to be blended is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less, per 100 parts by mass of the (A1) component to be blended, from the viewpoint of water repellency.
• the (C2) component is a (meth)acrylic acid ester monomer having a monovalent cyclic hydrocarbon group having 1 to 11 carbon atoms in the ester portion, and examples of the cyclic hydrocarbon group include isobornyl, cyclohexyl, and dicyclopentanyl groups. These cyclic hydrocarbon groups may have a substituent such as an alkyl group. However, when the substituent is a hydrocarbon group, a hydrocarbon group is selected in which the total number of carbon atoms in the substituent and the cyclic hydrocarbon group is 11 or less. In addition, from the viewpoint of improving durable water repellency, it is preferable that these cyclic hydrocarbon groups are directly bonded to an ester bond.
• the mass of the (C2) component to be blended is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, per 100 parts by mass of the (A1) component to be blended, from the viewpoint of water repellency.
• the mass of the (C2) component to be blended is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, per 100 parts by mass of the (A1) component to be blended, from the viewpoint of water repellency.
• the above (C3) component is a methacrylic acid ester monomer in which an unsubstituted monovalent chain hydrocarbon group having 1 to 4 carbon atoms is directly bonded to the ester bond of the ester portion.
• the chain hydrocarbon group having 1 to 4 carbon atoms a linear hydrocarbon group having 1 to 2 carbon atoms and a branched hydrocarbon group having 3 to 4 carbon atoms are preferable.
• the chain hydrocarbon group having 1 to 4 carbon atoms for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, etc. are mentioned.
• Specific compounds include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and t-butyl methacrylate. These monomers may be used alone or in combination of two or more kinds. Among these, methyl methacrylate, isopropyl methacrylate, and t-butyl methacrylate are preferred, with methyl methacrylate being more preferred, as they can improve the durable water repellency of the resulting textile product.
• the mass of the (C3) component to be blended is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more, per 100 parts by mass of the (A1) component to be blended, from the viewpoint of water repellency.
• the mass of the (C3) component to be blended is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, per 100 parts by mass of the (A1) component to be blended, from the viewpoint of water repellency.
• compounds include ethoxylated isocyanuric acid triacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate.
• These monomers may be used alone or in combination of two or more.
• tetramethylolmethane tetraacrylate and ethoxylated isocyanuric acid triacrylate are more preferred because they can improve the durable water repellency of the resulting textile product.
• the mass of the (C4) component to be blended is preferably 0.1 parts by mass or more, and more preferably 0.5 parts by mass or more, per 100 parts by mass of the (A1) component to be blended, from the viewpoint of water repellency.
• the mass of the (C4) component to be blended is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less, per 100 parts by mass of the (A1) component to be blended, from the viewpoint of water repellency.
• the mass of the (C) component to be blended is preferably 0.1 parts by mass or more, and more preferably 0.5 parts by mass or more, per 100 parts by mass of the (A1) component to be blended, from the viewpoint of water repellency.
• the mass of the (C) component to be blended is preferably 30 parts by mass or less, and more preferably 25 parts by mass or less, per 100 parts by mass of the (A1) component to be blended, from the viewpoint of water repellency.
• the acrylic polymer further contains a constituent unit derived from one or more monomers (VC) selected from the group consisting of vinyl chloride and vinylidene chloride (in the present disclosure, also referred to as “(VC) component”).
• VC monomers selected from the group consisting of vinyl chloride and vinylidene chloride
• the (VC) component is preferably vinyl chloride from the viewpoint of maintaining the texture of the textile product.
• the amount of the (VC) component to be blended is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more, per 100 parts by mass of the (A1) component to be blended, from the viewpoints of water repellency, durable water repellency, and peel strength.
• the amount of the (VC) component to be blended is preferably 100 parts by mass or less, and more preferably 75 parts by mass or less, per 100 parts by mass of the (A1) component to be blended, from the viewpoints of water repellency, durable water repellency, and texture.
• the acrylic polymer may further contain a structural unit derived from a monofunctional monomer (D) (hereinafter also referred to as component (D)) copolymerizable with the component (A1) within a range that does not impair the effects of the present invention.
• component (D) monofunctional monomer
• Examples of the (D) component include (meth)acryloylmorpholine, (meth)acrylic acid esters having a hydrocarbon group, (meth)acrylic acid, fumaric acid esters, maleic acid esters, fumaric acid, maleic acid, (meth)acrylamide, N-methylol acrylamide, vinyl ethers, vinyl esters, ethylene, styrene, and other vinyl monomers that do not contain fluorine other than the (VC) component.
• the (meth)acrylic acid esters having a hydrocarbon group may have a substituent such as a vinyl group, a hydroxyl group, an amino group, an epoxy group, an isocyanate group, or a blocked isocyanate group in the hydrocarbon group, or may have a substituent other than a group that can react with a crosslinking agent, such as a quaternary ammonium group, and may have an ether bond, an ester bond, an amide bond, or a urethane bond.
• Examples of the (meth)acrylic acid esters include methyl acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, and ethylene glycol di(meth)acrylate.
• (meth)acryloylmorpholine is more preferred because it can improve the peel strength of the resulting textile product against the coating.
• the weight-average molecular weight of the acrylic polymer in this embodiment is preferably 30,000 or more.
• the weight-average molecular weight is 30,000 or more, the water repellency of the resulting textile product tends to be further improved.
• the weight-average molecular weight of the acrylic polymer is more preferably 100,000 or more. In this case, the resulting textile product can exhibit more sufficient water repellency.
• the upper limit of the weight-average molecular weight of the acrylic polymer is preferably about 5 million.
• the weight average molecular weight of an acrylic polymer refers to the value measured using a GPC (gel permeation chromatography) device (for example, Tosoh Corporation's GPC "HLC-8020") at a column temperature of 40°C and a flow rate of 1.0 ml/min, using tetrahydrofuran as the eluent, and converted into standard polystyrene.
• GPC gel permeation chromatography
• the melt viscosity of the acrylic polymer at 105°C is preferably 1000 Pa ⁇ s or less.
• the melt viscosity at 105°C is 1000 Pa ⁇ s or less, the texture of the resulting textile product tends to be easily maintained.
• the melt viscosity of the acrylic polymer is 1000 Pa ⁇ s or less, when the acrylic polymer is dispersed (emulsified in one embodiment) to form a dispersion, the acrylic polymer can be prevented from precipitating or settling, so that the storage stability of the dispersion tends to be easily maintained.
• the melt viscosity at 105°C is more preferably 500 Pa ⁇ s or less. In this case, the resulting textile product etc. will have a better texture while exhibiting sufficient water repellency. From the viewpoint of water repellency, the melt viscosity of the acrylic polymer at 105°C may be, for example, 10 Pa ⁇ s or more, 50 Pa ⁇ s or more, or 100 Pa ⁇ s or more.
• the "melt viscosity at 105°C” refers to the viscosity measured using an elevated flow tester (e.g., CFT-500 manufactured by Shimadzu Corporation) by placing 1 g of an acrylic polymer in a cylinder equipped with a die (length 10 mm, diameter 1 mm), holding the temperature at 105°C for 6 minutes, and applying a load of 100 kg f/ cm2 with a plunger.
• an elevated flow tester e.g., CFT-500 manufactured by Shimadzu Corporation
• urethane polymer examples include hydrophobic compounds having a structural unit derived from a polyfunctional compound represented by the following general formula (UI-1) and a structural unit derived from an isocyanate compound represented by the following general formula (UII).
• d represents an integer of 1 or more
• e represents an integer of 2 or more
• (d+e) is 3 to 6
• R U31 represents a (d+e)-valent organic group
• W 1 represents a divalent group which is an ester group, an amide group, a urethane group or a urea group
• R U32 represents a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms
• V 1 represents a hydroxy group, an amino group or a carboxy group, with the proviso that two or more of the e V 1s are hydroxy groups and/or amino groups.
• W1 represents a divalent group which is an ester group, an amide group, a urethane group or a urea group.
• W1 is preferably an ester group or a urethane group from the viewpoints of water repellency, durable water repellency (particularly washability) and water soak prevention.
• R U32 examples include a nonyl group, a decyl group, an undecyl group, a dodecyl group (a lauryl group), a myristyl group, a pentadecyl group, a cetyl group, a heptadecyl group, a stearyl group, a nonadecyl group, an eicosyl group, a heneicosyl group, and a behenyl group.
• R U32 may be a residue obtained by removing a reactive group from a reactive hydrocarbon compound having a reactive group capable of reacting with a functional group possessed by the polyfunctional compound A.
• the reactive hydrocarbon compound include higher fatty acids having 8 to 24 carbon atoms (note that the carbon number includes the carbon of the carbonyl group), higher aliphatic alcohols, higher aliphatic monoisocyanates, and higher aliphatic amines.
• higher aliphatic alcohols examples include lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetanol, stearyl alcohol, oleyl alcohol, eicosanol, heneicosanol, and behenyl alcohol.
• Examples of higher aliphatic monoisocyanates include decyl isocyanate, undecyl isocyanate, dodecyl isocyanate, myristyl isocyanate, pentadecyl isocyanate, cetyl isocyanate, stearyl isocyanate, eicosyl isocyanate, and behenyl isocyanate.
• higher aliphatic amines examples include decylamine, laurylamine, myristylamine, stearylamine, and behenylamine.
• V 1 represents a hydroxy group, an amino group, or a carboxy group. From the viewpoint of durable water repellency, V 1 is preferably a hydroxy group or an amino group.
• the hydrophobic group represented by [-W 1 -R U32 ] can be introduced, for example, by reacting 1 mole or more of the reactive hydrocarbon compound with 1 mole of the polyfunctional compound A so that the number e of unreacted functional groups in the polyfunctional compound A is 2 or more, using a conventionally known synthesis method, i.e., esterification reaction, amidation reaction or urethane reaction.
• the polyfunctional compound represented by the above general formula (UI-1) is not particularly limited, but is preferably at least one selected from the group consisting of polyfunctional compounds represented by the following general formula (UI-2), polyfunctional compounds represented by the following general formula (UI-3), and polyfunctional compounds represented by the following general formula (UI-4).
• W 4 represents a divalent group which is an ester group, an amide group, a urethane group, or a urea group
• R 76 represents a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms.
• R 77 represents an alkylene group having 2 to 3 carbon atoms.
• R 78 represents an alkylene group having 2 to 3 carbon atoms
• R 79 represents a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms
• W 5 represents a divalent group which is an ester group, an amide group, a urethane group, or a urea group.
• W 6 represents a carbonyl group or an amide group
• R 80 represents a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms.
• the multiple W 2s may be the same or different.
• the multiple R 43s may be the same or different.
• the multiple R 44s may be the same or different.
• R 44 corresponds to R U32 in the above general formula (UI-1).
• the multiple R 42s may be the same or different.
• the multiple V 2s may be the same or different.
• V2 is a hydroxy group, an amino group, or a carboxy group. From the viewpoint of durable water repellency, V2 is preferably a hydroxy group or an amino group.
• W3 is a divalent group which is an ester group, an amide group, a urethane group, or a urea group. From the viewpoints of water repellency, durable water repellency (particularly washability), and water soak prevention, W3 is preferably an ester group or a urethane group.
• W4 is a divalent group which is an ester group, an amide group, a urethane group, or a urea group. From the viewpoints of water repellency, durable water repellency (particularly washability), and water soak prevention, W4 is preferably an ester group, an amide group, or a urethane group.
• R 79 is a linear or branched monovalent hydrocarbon group having 8 to 24 carbon atoms.
• R 79 corresponds to R U32 in general formula (UI-1) above.
• W5 is a divalent group which is an ester group, an amide group, a urethane group, or a urea group. From the viewpoints of water repellency, durable water repellency (particularly washability), and water soak prevention, W5 is preferably an ester group, an amide group, or a urethane group.
• n1 represents an integer of 2 or more, and R 91 and R 92 each independently represent a linear or branched monovalent hydrocarbon group having 10 to 24 carbon atoms.
• n1 represents an integer of 2 or more, and is preferably an integer from 2 to 100, more preferably from 2 to 50, from the viewpoints of water repellency, durable water repellency (particularly washability), resistance to water penetration, dispersion stability of the hydrophobic compound, and ease of handling of the polymer.
• n2 represents an integer of 2 or more
• n3 represents an integer of 1 or more
• R 93 each independently represents a linear or branched monovalent hydrocarbon group having 10 to 24 carbon atoms.
• n2 represents an integer of 2 or more, and is preferably an integer from 2 to 200, more preferably from 2 to 100, from the viewpoints of water repellency, durable water repellency (particularly washability), resistance to water penetration, dispersion stability of the hydrophobic compound, and ease of handling of the polymer.
• n3 represents an integer of 1 or more, and is preferably an integer from 1 to 3, more preferably 1, from the viewpoints of water repellency, durable water repellency (particularly washability), water soak resistance, and dispersion stability of hydrophobic compounds.
• n4 represents an integer of 2 or more, and R 94 each independently represents a linear or branched monovalent hydrocarbon group having 10 to 24 carbon atoms.
• n4 represents an integer of 2 or more, and is preferably an integer from 2 to 200, more preferably from 2 to 100, from the viewpoints of water repellency, durable water repellency (particularly washability), resistance to water penetration, dispersion stability of the hydrophobic compound, and ease of handling of the polymer.
• n5 represents an integer of 2 or more
• R X represents the following formula (R-1):
• n5 represents an integer of 2 or more, and is preferably an integer from 2 to 100, more preferably from 2 to 50, from the viewpoints of water repellency, durable water repellency (particularly washability), resistance to water penetration, dispersion stability of the hydrophobic compound, and ease of handling of the polymer.
• hydrophobic compound having a partial structure represented by the above general formula (UIII-2) is a compound represented by the following formula (UIII-5).
• n6 represents an integer of 2 or more
• n7 represents an integer of 1 or more
• R X represents a monovalent organic group represented by formula (R-1) above.
• n6 represents an integer of 2 or more, and is preferably an integer from 2 to 200, more preferably from 2 to 100, from the viewpoints of water repellency, durable water repellency (particularly washability), resistance to water penetration, dispersion stability of the hydrophobic compound, and ease of handling of the polymer.
• n7 represents an integer of 1 or more, and is preferably an integer from 1 to 3, more preferably 1, from the viewpoints of water repellency, durable water repellency (particularly washability), water penetration resistance, and dispersion stability of hydrophobic compounds.
• hydrophobic compound having a partial structure represented by the above general formula (UIII-3) is a compound represented by the following formula (UIII-6).
• n8 represents an integer of 2 or more
• R x represents a monovalent organic group represented by formula (R-1) above.
• n8 represents an integer of 2 or more, and is preferably an integer from 2 to 200, more preferably from 2 to 100, from the viewpoints of water repellency, durable water repellency (particularly washability), resistance to water penetration, dispersion stability of the hydrophobic compound, and ease of handling of the polymer.
• the hydrophobic compound according to this embodiment preferably has a blocked isocyanate group protected with a blocking agent.
• the ratio of blocked isocyanate groups to the total number of isocyanate groups and blocked isocyanate groups contained in the hydrophobic compound is preferably 80% or more, more preferably 90% or more, and even more preferably 100%.
• Examples of the blocked isocyanate group protected with a blocking agent include a group represented by the following general formula: (-NH-CO-B) [In the formula, B is a group derived from a blocking agent.] Examples of the group include a group represented by the following formula:
• Blocking agents include, for example, pyrazoles such as 3,5-dimethylpyrazole, 3-methylpyrazole, 3,5-dimethyl-4-nitropyrazole, 3,5-dimethyl-4-bromopyrazole, and pyrazole; alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and tert-butyl alcohol; phenols such as phenol, methylphenol, chlorophenol, p-isobutylphenol, p-tert-butylphenol, p-isoamylphenol, p-octylphenol, and p-nonylphenol;
• the blocking agent include active methylene compounds such as dimethyl malonate, diethyl malonate, acetylacetone, methyl acetoacetate, and ethyl acetoacetate; oximes such as formaldoxime, acetaldoxime, acetone oxime
• One type of blocking agent may be used alone, or two or more types may be used in combination.
• the weight average molecular weight (Mw) of the hydrophobic compound of this embodiment may be preferably 2,000 to 100,000, more preferably 2,000 to 50,000, and even more preferably 2,000 to 20,000, from the viewpoints of water repellency, durable water repellency (particularly washability), water soak prevention, and dispersion stability of the hydrophobic compound.
• the weight average molecular weight of the hydrophobic compound is measured by GPC (gel permeation chromatography) and is a value converted into standard polystyrene.
• the amount of the compound represented by the above general formula (UII) is preferably (0.8 to 1.20) x 2/e moles, more preferably (0.80 to 0.99) x 2/e moles, and even more preferably (0.85 to 0.95) x 2/e moles, relative to 1 mole of the polyfunctional compound represented by the above general formula (UI-1).
• it is more preferably (1.01 to 1.20) x 2/e moles, and even more preferably (1.05 to 1.15) x 2/e moles.
• the amount of hydrophobic polymer ( ⁇ ) relative to 100 parts by mass of the total of organo-modified silicone ( ⁇ ) and hydrophobic polymer ( ⁇ ) is preferably 1 part by mass or more, or 5 parts by mass or more, or 10 parts by mass or more from the viewpoint of initial water repellency and durable water repellency, and is preferably 99 parts by mass or less, or 95 parts by mass or less, or 90 parts by mass or less from the viewpoint of initial water repellency and durable water repellency.
• the dispersion includes a liquid medium.
• the liquid medium includes water and optionally further includes an organic solvent.
• the ratio of water to the total liquid medium (100 mass%) is 50 mass% or more. The amount of the liquid medium in the dispersion may be adjusted so that the content of the organo-modified silicone ( ⁇ ) and any other components in the dispersion is within a desired range.
• the dispersion contains an organic solvent (also referred to as a poorly water-soluble organic solvent in the present disclosure) in which the amount of water required to dissolve 1 g of the organic solvent at 20 ° C. is more than 10 mL as a liquid medium. In one embodiment, the amount of water required to dissolve 1 g of the organic solvent is more than 30 mL, preferably more than 100 mL, and more preferably more than 1000 mL.
• Such a poorly water-soluble organic solvent contributes to stable dispersion of the organo-modified silicone ( ⁇ ) (for example, formation of an emulsion in which the organo-modified silicone ( ⁇ ) is stably dispersed), and therefore contributes to the formation of a dispersion having excellent storage stability.
• the amount of water required to dissolve 1 g of the organic solvent is a value measured by the following method in accordance with JIS K8001:2017.
• More than 100 mL and not more than 1,000 mL The product did not dissolve in 100 mL of water within 30 minutes, but dissolved in 1,000 mL of water within 30 minutes. More than 1000 mL: Did not dissolve in 1000 mL of water within 30 minutes.
• An example of the amount of water required to dissolve 1 g of an organic solvent is as follows.
• ⁇ Isoparaffin isoparaffin with 10 to 16 carbon atoms
• ⁇ Mineral oil kinematic viscosity at 30°C: 20 mm 2 /s
• 1000 mL ⁇ Mineral spirits (boiling point: 180 to 200°C): more than 1000 mL ⁇ Ester (2,2,4-trimethyl-1,3-pentanediol diisobutyrate): more than 1000 mL
• TPG Tripropylene glycol
• DPG Dipropylene glycol
• ⁇ Butyl diglycol 1 mL or less
• the poorly water-soluble organic solvent promotes the dispersion of the organo-modified silicone ( ⁇ ) (in one embodiment, O/W emulsion), thereby contributing to improving the dispersion stability (in one embodiment, emulsion stability) of the organo-modified silicone ( ⁇ ) in the water-containing medium.
• the poorly water-soluble organic solvent preferably has a structure composed of carbon and hydrogen (i.e., a hydrocarbon structure) in the molecule, in that the effect of improving the dispersion stability of the organo-modified silicone ( ⁇ ) is good.
• preferred poorly water-soluble organic solvents include, for example, esters (specific examples are 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, ethyl acetate, butyl acetate, butyl glycol acetate, etc.), ketones (specific examples are methyl isobutyl ketone, etc.), ethers (specific examples are dibutyl diglycol, diethylene glycol mono-2-ethylhexyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethyl glycol mono-2-ethylhexy
• the isoparaffin preferably has 4 or more carbon atoms, and more preferably has 9 to 20 carbon atoms.
• examples of such isoparaffins include IP Solvent IP-2028 (isoparaffin having 10 to 16 carbon atoms, manufactured by Idemitsu Kosan Co., Ltd.).
• Examples of the mineral oil include mineral oils having a kinetic viscosity of 50 mm 2 /s or less at 30° C., and more specifically, normal undecane, normal dodecane, normal tridecane, normal tetradecane, paraffin, and the like.
• the kinetic viscosity is a value measured by a method conforming to JIS K 2283:2000.
• the carbon number of the paraffin may be, for example, 10 to 16.
• the mineral oil may be used alone or in combination of two or more kinds. In the case of a combination of two or more kinds, it is preferable that they are mutually compatible.
• the mineral oil may be a commercially available product, and examples thereof include Cactus Normal Paraffin N-12D, Cactus Normal Paraffin YHNP, and Cactus Normal Paraffin N-14 (all available from ENEOS Corporation).
• the amount of poorly water-soluble organic solvent in the dispersion is preferably 0.5 to 500 parts by mass, more preferably 1 to 400 parts by mass, even more preferably 1 to 300 parts by mass, and particularly preferably 1 to 200 parts by mass, per 100 parts by mass of organo-modified silicone ( ⁇ ), from the viewpoint of dispersion stability of the organo-modified silicone ( ⁇ ).
• the amount of poorly water-soluble organic solvent is preferably in the above range, since the storage stability and water repellency of the dispersion are good.
• the total concentration of the organo-modified silicone ( ⁇ ) and hydrophobic polymer ( ⁇ ) in the dispersion may be changed as appropriate depending on the application, but may be, for example, 0.01 to 70 mass %, or 0.05 to 50 mass %.
• the concentration of the above ⁇ additional components> in the dispersion may be changed as appropriate depending on the application, but may be, for example, 20 mass % or less, or 5 mass % or less.
• the method of pretreatment is not limited, and a conventionally known method may be used.
• the pretreatment liquid may be dispersed and diluted in an organic solvent and/or water as necessary, and applied to the substrate by a known method such as immersion, spraying, or foam application, and then dried.
• the pH, temperature, etc. of the pretreatment liquid may be adjusted depending on the desired degree of pretreatment.
• a base material containing at least one type of functional group (hereinafter, sometimes referred to as a "specific functional group”) can be obtained by the following method.
• a compound having a specific functional group is attached to a substrate.
• the substrate may be functionalized with a treatment agent containing a compound having a specific functional group (hereinafter, functionalizing treatment agent).
• functionalizing treatment agent a treatment agent containing a compound having a specific functional group
• a portion of the compound may chemically bond to the substrate.
• the specific functional group may be at least one selected from the group consisting of a monovalent group represented by, for example, -SO 3 M 1 (wherein M 1 is a monovalent cation), a monovalent group represented by -COOM 2 (wherein M 2 is a monovalent cation), and a monovalent group represented by -O-P(O)(OX 1 )(OX 2 ) (wherein X 1 and X 2 are each independently a hydrogen atom or an alkyl group having 1 to 22 carbon atoms).
• M 1 and M 2 may be, for example, H, K, Na, or an ammonium ion which may have a substituent.
• the number of carbon atoms is preferably 1 to 22, or 4 to 12.
• the compound having the above-mentioned -SO 3 M 1 is a phenol-based polymer.
• the phenol-based polymer is a compound represented by the following general formula: [wherein X 2 represents a hydrogen atom, —SO 3 M 3 (wherein M 3 represents a hydrogen atom or a monovalent cation), a hydroxyphenylsulfonyl group, or a group represented by the following general formula: (In the formula, M4 represents a hydrogen atom or a monovalent cation.) and n is an integer of 3 to 500.
• the weight percent of SO3 in the compound is preferably 0.5% or more, or 3% or more, or 5% or more, and is preferably 40% or less, or 30% or less, or 20% or less.
• Each of M3 and M4 may be H, K, Na, or an 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, or a formalin condensate of phenolsulfonic acid and bisphenol S, or a formalin condensate of sulfonated bisphenol S and bisphenol S, or a formalin condensate of phenolsulfonic acid and phenol.
• Examples of the compound having -COOM 2 include polycarboxylic acid polymers.
• the polycarboxylic acid polymer may be a polymer obtained by a conventionally known radical polymerization method using acrylic acid, methacrylic acid, maleic acid, or the like as a monomer.
• a monomer copolymerizable with the monomer may be used.
• Examples of the copolymerizable monomers include ethylene, vinyl monomers (vinyl chloride, vinyl acetate, etc.), acrylamide, acrylates, methacrylates, and the like.
• a method for producing a polycarboxylic acid polymer includes adding a radical polymerization initiator to an aqueous solution of the above-mentioned monomer and/or its salt (and optionally a monomer copolymerizable with the monomer) and heating the solution at 30°C to 150°C for 2 to 5 hours.
• An aqueous solvent for example, an alcohol such as methanol, ethanol, isopropyl alcohol, or 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 polymerization initiators that are combinations of persulfates and sodium bisulfite, hydrogen peroxide, and water-soluble azo polymerization initiators. These radical polymerization initiators may be used alone or in combination of two or more.
• a chain transfer agent e.g., octyl thioglycolate
• the carboxyl group in the polycarboxylic acid polymer may be free or neutralized with a neutralizing agent such as an alkali metal or an amine compound.
• alkali metals include sodium, potassium, and lithium
• examples of amine compounds include ammonia, monoethanolamine, diethanolamine, and triethanolamine.
• the polycarboxylic acid polymer may be a commercially available product such as "Neo Crystal 770" (product name, manufactured by Nicca Chemical Co., Ltd.) or "Ceropol PC-300” (product name, manufactured by Sanyo Chemical Industries, Ltd.).
• the compound having the above-mentioned --O--P(O)(OX 1 )(OX 2 ) is, for example, a compound represented by the following general formula: [In the formula, X1 and X2 are defined as above, and X3 represents an alkyl group having 1 to 22 carbon atoms.]
• Examples of the phosphate ester compounds include those represented by the following formula: Examples of the phosphate ester compound include a phosphate monoester whose alkyl ester moiety is an alkyl group having 1 to 22 carbon atoms, a phosphate diester whose alkyl ester moiety is an alkyl group having 1 to 22 carbon atoms, a phosphate triester whose alkyl ester moiety is an alkyl group having 1 to 22 carbon atoms, and mixtures thereof. From the viewpoint of the water repellency of the resulting textile product, lauryl phosphate and decyl phosphate are particularly preferred.
• the phosphate ester compound may be a commercially available product such as "Phosphanol ML-200" (product name, manufactured by Toho Chemical Industry Co., Ltd.).
• the functionalizing agent may be used, for example, as an aqueous solution.
• a functionalizing solution may contain an acid, an alkali, a surfactant, a chelating agent, etc., as necessary.
• the functionalizing solution may further contain a salt, for example, in order to effectively adsorb a compound having a specific functional group to a substrate by a salting-out effect.
• salts include sodium chloride, sodium carbonate, ammonium sulfate, and sodium sulfate.
• the functionalizing solution may be used to subject a substrate to, for example, padding, immersion, spraying, or coating.
• the functionalization treatment liquid contains a solvent such as water
• the drying method is not particularly limited and may be either a dry heat method or a wet heat method.
• the drying temperature and drying time are also not particularly limited and may be, for example, from room temperature to 200°C and from 10 seconds to several days. If necessary, after drying, a heat treatment may be performed at 100°C to 180°C for 10 seconds to 5 minutes.
• the functionalization treatment may be carried out before dyeing or in the same bath as the dyeing.
• the functionalization treatment it is preferable to carry out the functionalization treatment after dyeing and reduction soaping in order to prevent compounds having specific functional groups (e.g., phenolic polymer compounds, etc.) attached to the substrate from falling off during soaping.
• hot melt it is preferable to use a moisture-curing resin that reacts with moisture in the air, and in practice, it is more preferable to use one that melts in a temperature range of about 80 to 150°C.
• the hot melt resin is melted while taking into consideration the melting point of the resin and its viscosity when melted.
• the molten resin is then applied onto the woven or knitted fabric or the moisture-permeable waterproof layer, and is matured while being cooled at room temperature to form an adhesive layer.
• the woven or knitted fabric and the moisture-permeable waterproof layer can then be bonded together via the adhesive layer and pressed together.
• the mixed solution was irradiated with ultrasonic waves to emulsify and disperse all the monomers.
• 0.2 g of azobis(isobutylamidine) dihydrochloride and 0.08 g of dodecyl mercaptan were added to the mixed liquid, and radical polymerization was carried out at 60° C. for 6 hours under a nitrogen atmosphere while continuously injecting 6.0 g of vinyl chloride so as to maintain the internal pressure of the autoclave at 0.3 MPa, thereby obtaining an acrylic polymer emulsion (acrylic polymer 2) containing 30.0% by mass of an acrylic polymer.
• the mixed solution was irradiated with ultrasonic waves to emulsify and disperse all the monomers.
• the mixed solution was irradiated with ultrasonic waves to emulsify and disperse all the monomers.
• Each of the treated fabrics was immersed in 100 g of the dispersion liquid for each Example and Comparative Example at normal pressure and 20 ⁇ 5°C for 30 seconds, and then heat-treated at 150°C for 2 minutes to obtain a textile product.
• the obtained textile product was subjected to the following evaluations.
• the color difference ⁇ E*ab was calculated from the L*a*b* values measured by SCI measurement using a Minolta spectrophotometer CM-3700A, Spectra Magic NX CM-S100W, light source D65, field of view 10 degrees, UV 100%, and the hue value was calculated. The smaller the color difference, the better.

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• 2024
  • 2024-12-17 JP JP2025519823A patent/JPWO2025142621A1/ja active Pending
  • 2024-12-17 WO PCT/JP2024/044540 patent/WO2025142621A1/ja active Pending

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