Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
  • D06M15/3568—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing silicon
• • 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
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
  • D06M13/144—Alcohols; Metal alcoholates
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
  • D06M13/503—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms without bond between a carbon atom and a metal or a boron, silicon, selenium or tellurium atom
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
  • D06M13/503—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms without bond between a carbon atom and a metal or a boron, silicon, selenium or tellurium atom
  • D06M13/507—Organic silicon compounds without carbon-silicon bond
• • 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
  • D06M15/21—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
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
• • 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
• • 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
  • D06M2200/11—Oleophobic properties
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
  • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
  • Y10T428/31935—Ester, halide or nitrile of addition polymer

Definitions

• the present invention relates to a surface treatment agent that imparts excellent antifouling properties to an object to be treated such as a textile product even after cleaning, and has high persistence.
• Japanese Patent Publication No. 48-86606 discloses a method for preventing stains by treating fibers with a homopolymer obtained by polymerizing an unsaturated carboxylic acid ester having a perfluoroalkyl group at both terminals. Is disclosed. However, this homopolymer has insufficient antifouling properties.
• Japanese Patent Publication No. 51-37767 discloses that (i) maleic acid or fumaric acid having a perfluoroalkyl group at one end and an aliphatic or aromatic group containing no fluorine atom at the other end. It is disclosed that by treating fibers with a polymer obtained by copolymerizing an acid ester and (ii) another polymerizable unsaturated compound, water repellency and oil repellency are imparted to the polymer.
• One end group of maleic acid or fumaric acid ester does not contain a fluorine atom, so its polymerizability is good. However, this polymer has poor water and oil repellency and poor antifouling properties.
• USP 3, 594, 353 have homopolymerized itaconic acid esters with perfluoroalkyl groups at both ends or one end, or have copolymerized with other polymerizable unsaturated compounds. It is disclosed that by treating the fiber with the polymer obtained as described above, the fiber is given water repellency and is provided with stain resistance to oil. However, this copolymer has insufficient water and oil repellency and stain resistance.
• the anti-fouling agents that have been conventionally proposed do not have sufficient water and oil repellency and anti-fouling properties, and do not have cleaning durability.
• the water / oil / oil repellency / antifouling treated carpet treated by the above-mentioned conventional method has the initial water / oil repellency and antifouling property immediately after the treatment. Although it was better than the above, it was not sufficient performance, and cleaning durability was also insufficient.
• An object of the present invention is to provide a surface treatment agent (for example, a treatment agent for Rippon pet) that provides sufficient water / oil repellency and antifouling durability before and after cleaning.
• a surface treatment agent for example, a treatment agent for Rippon pet
• the present invention provides a method for treating a fiber
• the value of the antifouling rate shown by the following formula after cleaning is 30% or more
• Antifouling rate (%) 100 ⁇ ( ⁇ ⁇ - ⁇ ⁇ ) / ⁇ ⁇
• ⁇ Number of clean Jung ( ⁇ is an integer from 1 to 20)
• the residual ratio of the surface treatment agent represented by the following formula is 10% or more.
• Knoop hardness (KH) of the surface treatment agent is 5 or more
• the present invention is a.
• a surface treatment agent comprising:
• a surface treatment agent comprising:
• the polymer (B) is a polymer (B)
• the polymer (D) is a homopolymer or a copolymer composed of (D-i) a non-fluorinated (meth) acrylic acid derivative monomer.
• the (B-iv) fluorine-containing monomer having a carbon-carbon double bond in the polymer (B) and the (C-ii) fluorine-containing monomer having a carbon-carbon double bond in the polymer (C) are as follows. It is similar.
• the weight average molecular weight of the polymers (B), (C) and (D) may be between 5,000 and 500,000, for example between 10,000 and 200,000 (measured by GPC).
• the metal alkoxide (A) is a hydrolyzable polymerizable organometallic compound and has at least one alkoxy group.
• the metal alkoxide (A) is, for example, a compound represented by the following general formula: R a (R 12 0) b M ⁇ 0-MR ” g (OR 12 ) h ⁇ f -R” d (OR 12 ) e
• each R 11 represents a methacryloxy group, an acryloxy group, an organic group containing a vinyl group, an alkyl group, a butyl group, an aryl group, or an organic group containing an epoxy group
• each R 12 represents an alkyl group, an alkoxyalkyl group.
• M represents a metal
• the metal alkoxide (A) has, for example, the general formula:
• R 11 represents a methacryloxy group, an acryloxy group, a vinyl group-containing organic group, an alkyl group, a butyl group, an aryl group, or an epoxy group-containing organic group
• R 12 represents an alkyl group, an alkoxyalkyl group, or Represents an aryl group
• M represents a metal
• m is 2-5, especially 3 or 4
• n is 0-2, especially 0 or 1
• m + n 3-5, especially 4.
• the number of alkyl groups of the metal alkoxide (A) may be 1 to 12, for example, 1 to 4.
• the alkyl group (! ⁇ ! Povy! ⁇ 12 ) has, for example, 1 to 6 carbon atoms.
• the aryl group has, for example, 6 to 18 carbon atoms.
• the number of carbon atoms of the organic group containing a bull group and the organic group containing an epoxy group are, for example, 2 to 6.
• Examples of the organic group containing a butyl group include a vinyl group.
• Examples of the epoxy group-containing organic group include a glycidyl group.
• the number of carbon atoms of the alkoxy group is, for example, 1 to 6, and the number of carbon atoms of the alkyl group may be 1 to 6.
• M metal
• Si silicon
• Ti titanium
• Al aluminum
• Zr zirconia
• tin Sn
• Fe iron
• metal alkoxides (A) are examples of metal alkoxides (A).
• Methyltri X toxic silane [CH 3 Si (OCH2 CH 3 ) 3 ] (trifunctional)
• the monomer (B-i) having a carbon-carbon double bond and a metal alkoxide group may have a metal alkoxide group having at least one (for example, three) alkoxy group.
• Metal alkoxide groups are, for example,
• M is a metal such as Si, Ti, Al, Zn, Sn, Fe, etc.
• R 3 is an alkyl group having 1 to 4 carbon atoms, and n is:! ⁇ 3.
• a monomer (B—i) having a carbon-carbon double bond and a metal alkoxide group has the formula:
• R 4 , R 5 , R 6 and R 7 may be the same or different and are hydrogen or an alkyl group having 1 to 4 carbon atoms, and A 1 is a direct bond or divalent M 1 is a metal such as Si, Ti, Al, Zn, Sn, Fe, and n is :! Use 3 to 3.
• Examples of the monomer (B-i) having a carbon-carbon double bond and a metal alkoxide group include an alkoxysilyl group-containing monomer and an alkoxytitanium group-containing monomer.
• alkoxysilyl group-containing monomer examples include the following.
• CH 2 CHS i (OCH 3 ) (Butyltrimethoxysilane)
• CH 2 C— COCH 2 CH 2 CH 2 Si (OCH 3 ) 3
• alkoxytitanium group-containing monomer examples include the following.
• CH 2 C— C-0-Ti (OiC 3 H 7 ) 3
• the amount of the monomer (B-i) having a carbon-carbon double bond and a metal alkoxide group is 0.1 to 200 parts by weight, for example, 50 to 100 parts by weight, per 100 parts by weight of the metal alkoxide (A). : It may be 100 parts by weight.
• Non-fluorinated (meth) acrylic acid derivative monomers (B-ii) and (C-i) and (D-i) have good adhesion to the object even after cleaning with force .
• the non-fluorinated (meth) acrylic acid derivative monomer does not include (meth) acrylic acid itself.
• Atharylate is alkyl (meth) acrylate, polyalkylene glycol It may be selected from the group consisting of coal (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, and glycerol mono (meth) acrylate.
• (Meth) acrylates can be used alone or in combination of two or more.
• the alkyl (meth) acrylate has, for example, the following structural formula.
• X is a hydrogen atom or a methyl group
• n is 1 to 22 (eg, 1 to 10).
• alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n —Octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, etc. Is mentioned.
• the polyalkylene glycol (meth) acrylate has, for example, the following structural formula.
• R 21 and R 23 are hydrogen or a methyl group
• R 22 is an alkylene group having 2 to 6 carbon atoms
• n is! Represents an integer of ⁇ 50.
• polyalkylene glycol (meth) acrylates include:
• n 2, 5 or 8.
• R 31 is a hydrogen atom or a methyl group.
• Glycerol mono (meth) acrylate has the formula:
• R 41 is a hydrogen atom or a methyl group.
• (Meth) acrylic group-containing nitrogen compounds include (meth) acrylamide, N, N-dimethylacrylamide, (meth) acrylonitrile, dimethylaminoethyl (meth) acrylate, and getylaminoethyl (meth) atali.
• the amount of the non-fluorinated (meth) acrylic acid derivative monomer (B-ii) and (C-i) and (D-i) is 0.1 to 200 parts by weight per 100 parts by weight of metal alkoxide (A), For example, it may be 0.25 to 10 parts by weight.
• Fluorine-containing compounds (B—iiii) and (E) having a functional group that reacts with a metal alkoxide are, for example,
• R represents a fluoroalkyl group
• X represents a reactive group selected from the group consisting of an alkoxysilane group, a carboxyl group, a hydroxyl group, an epoxy group, a phosphate group, a halogenated silyl group, a sulfonic acid group, an isocyanate and a blocked isocyanate group.
• the carbon number of the R f group may be from 3 to 21, especially from 7 to 17 carbon atoms.
• the R f group (fluoroalkyl group) may be CF 3 (CF 2 ) n CH 2 CH 2 — (n ⁇ 0).
• Fluorine-containing compound having a functional group that reacts with metal alkoxide (B- i ii) and (E) are particularly R f -OH or R f -S i (OR 31 ) 3 [where each R 31 is independently C i — 2 . It is an alkyl group. ].
• the fluorine-containing compounds (B-iiii) and (E) having a functional group that reacts with the metal alkoxide may be silane, alcohol, chlorosilane, epoxy, or phosphate.
• fluorine-containing compound having a functional group that reacts with the metal alkoxide examples include as follows.
• the amount of the fluorine-containing compounds (B-iii) and (E) having a functional group which reacts with the metal alkoxide is 0.150 parts by weight, for example, 1.05 parts by weight, per 100 parts by weight of the metal alkoxide (A). It may be 0 parts by weight.
• the fluorine-containing monomers (B-iv) and (C-ii) having a carbon-carbon double bond may be fluorine-containing (meth) acrylate, fluorine-containing maleate or fluorine-containing fumarate.
• fluorinated (meth) acrylate examples have the following structural formula.
• R f is a polyfluoroalkyl group having 6 16 carbon atoms or a polyether group having a perfluoro opening
• A is an alkylene group having 14 carbon atoms
• R ' is an alkyl group having 14 carbon atoms
• R 2 is an alkylene group having 14 carbon atoms
• HH ?, and X ⁇ 1 is a hydrogen atom or a methyl group.
• the polyfluoroalkyl group (R f group) may be a perfluoroalkyl group.
• Specific examples of the c- perfluoropolyether group are as follows.
• n is an integer of 30. ] CF 3 0 (CF (CF 3 ) CF 2 0) n (CF 2 0) m CF 2 ⁇ ,
• n is an integer of 2 to 30 and m is an integer of 3 to 70.
• n is an integer of 2 to 40 and m is an integer of 4 to 70.
• n is an integer of 3 to 30.
• the number average molecular weight (measured by 19 F-NMR) of the perfluoropolyether groups is preferably in the range of 500 to 5,000.
• fluorinated (meth) acrylate examples include as follows.
• the fluorine-containing maleate has the formula:
• R f is a perfluoroalkyl group having 3 to 21 carbon atoms
• a 11 is hydrogen or an alkyl group having 1 to 4 carbon atoms
• a 12 is an alkylene group having 1 to 4 carbon atoms.
• the fluorine-containing fumarate has the formula:
• R ⁇ is a perfluoro group having 3 to 21 carbon atoms
• ⁇ ⁇ 21 is hydrogen or an alkyl group having 1 to 4 carbon atoms
• ⁇ 22 is an alkylene group having 1 to 4 carbon atoms.
• the amount of the fluorine-containing monomer (B-iv) and (C-ii) having a carbon-carbon double bond is 0.1 to 50 parts by weight, for example, 1 to 100 parts by weight of the metal alkoxide (A). It may be from 0 to 5.0 parts by weight.
• the surface treatment agent of the present invention is a composition for an inorganic / organic hybrid material.
• Organic hybrid materials are formed from organic and inorganic components.
• the organic components are non-fluorinated (meth) acrylic acid derivative monomer (B-ii) and
• the inorganic component is a metal alkoxide (A) and a monomer (B-i) having a carbon-carbon double bond and a metal alkoxide group.
• metal oxides particularly M0 2 (M metallic atom) based 3-dimensional microstructures (hereinafter, abbreviated as fine structure) was in, to disperse the polymer structure
• An inorganic / organic hybrid material having: The metal alkoxide (ie, the metal alkoxide (A) and the monomer (B—i) having a carbon-carbon double bond and a metal alkoxide group) are hydrolyzed and condensed by a sol-gel method to form a metal oxide. (e.g., M0 2) form a system microstructures.
• a polymer ie, polymer (B) or (C) or
• inorganic-organic hybrid material in which) is dispersed is formed.
• a covalent bond is formed between the metal alkoxide (A) and the polymer (B).
• Hydrogen bonds are formed between the metal alkoxide (A) and the polymer (C).
• No covalent bond is formed between the metal alkoxide (A) and the polymer (D).
• Inorganic / organic hybrid materials are suitable as surface treatment agents, especially as treatment agents for textile products, and have excellent antifouling durability and transparency, and are hydrophobic.
• a coating film of an inorganic / organic hybrid material is formed on a substrate.
• the substrate may be a polymeric material.
• the form of the substrate may be, for example, a film, a fiber, a cloth, or the like.
• the coating film of the inorganic / organic hybrid material may be composed of a roughened layer having fine irregularities formed on the entire surface and roughened. Maximum surface roughness of the uneven layer of the coating (R ro a J may be 0 ⁇ 001: 1 ⁇ . The thickness of the coating film is 0.01 to: 100 Aim.
• the film formed from inorganic and organic hybrid materials has a nup hardness (KH) of 5 or more.
• the Knoop hardness may be, for example, 6 or more, especially 8 or more.
• Nup hardness is measured with a Terazawa micro hardness tester (SM-2 manufactured by Taiyo Tester).
• the inorganic / organic hybrid material may have a contact angle with water of 100 ° or more.
• a catalyst eg, an acid or a base
• the hydrolysis product is dissolved or dispersed in a medium (water or organic solvent), and an initiator (and a cross-linking agent if necessary) and an emulsifier are added if necessary to obtain a hybrid material Z medium mixture.
• a medium water or organic solvent
• an initiator and a cross-linking agent if necessary
• an emulsifier are added if necessary to obtain a hybrid material Z medium mixture.
• the mixture is obtained by applying heat or light (UV light).
• organic solvents examples include alcohols (eg, methanol, ethanol), ethers (eg, benzoin methyl ether), amides (eg, N, N-dimethylformamide).
• initiators are peroxides (eg, ammonium peroxodisulfate, ammonium persulfate), benzoin methyl ether, benzoin ethyl ether.
• An example of a cross-linking agent is bisacrylamide (eg, N, N-methylenebisacrylamide).
• Emulsifiers, pH adjusters, etc. can be used to disperse inorganic and organic hybrid materials in water.
• the emulsifier examples include anionic surfactants such as alkyl sulfates, alkylaryl sulfate esters, alkyl phosphates, and fatty acid salts; and cationic surfactants such as alkylamines and alkyl quaternary amines.
• anionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, and block polyethers; carboxylic acid type (for example, amino acid Type, betaine type, etc.) and sulfonic acid type etc. can be used.
• These emulsifiers can be used alone or in combination of two or more.
• the pH is adjusted by adding at least one basic compound.
• the copolymer has a basic group such as an amino group or a imide group
• the pH is subsequently adjusted by adding at least one acidic compound.
• the copolymer has the acidic group and the basic group
• the hydrophilicity of the obtained copolymer is adjusted by adding at least one basic compound or at least one acidic compound according to the proportion of these groups and adjusting the pH. And the dispersibility of the polymer can be improved.
• Examples of the basic compound include amines such as ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, getylamine, triethylamine, ethanolamine, diethanolamine, and dimethylaminoethanol;
• Examples of the acidic compound include inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid, and nitric acid; formic acid, acetic acid, propionic acid, lactic acid, oxalic acid, and quinic acid. Acids, adipic acid, and organic acids such as (meth) acrylic acid, maleic acid, fumaric acid, and itaconic acid.
• the pW value during the pH adjustment is usually 6 to 10, preferably 7 to 8.
• the aqueous medium in the aqueous dispersion is essentially composed of water, but may contain an organic solvent such as an alcohol up to several weight% in some cases.
• the metal chelate compound (F) has the following general formula:
• R 5 1 and R 5 2 may be the same or different, represents the number 1-6 alkyl group having a carbon 1? 5 3 Arukiru group or a carbon number of 1 to 5 carbon atoms It represents 1 to 16 alkoxyl groups.
• These metal chelate compounds (F) promote the condensation reaction during the polycondensation of the metal alkoxide (A) and the monomer (B-i) having a carbon-carbon double bond and a metal alkoxide group. it is conceivable that.
• the alkyl group of R 5 1 and R 5 2 of carbon number 1-6 for example, a methyl group, Echiru group, n- propyl group, isopropyl radical, n Straight-chain or branched-chain alkyl groups such as -butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group and n-hexyl group.
• the alkyl group having 1 to 5 carbon atoms for R 5 for example, a methyl group, Echiru group, n - propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group, t- butyl group And a linear or branched alkyl group such as an n-pentyl group.
• the alkoxyl group having 1 to 16 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, Examples thereof include an n-butoxy group, an isobutoxy group, a sec-butoxy group, a t-butoxy group, a lauryl group, and a stearyl group.
• metal chelate compound (F) examples include tri-n-butoxy'ethylacetoacetate zirconium, di-n-butoxybis (ethylacetate acetate) zirconium, and n-butoxy'tris (ethylamine).
• Bis (acetyl acetate) titanium chelate compounds such as titanium; disopropoxy / ethyl acetate acetate aluminum, disopropoxy / acetyl acetate aluminum, isopropoxy 'bis (ethyl acetate) Acetate) Aluminum, isopropoxy 'bis (acetyl acetate) aluminum, tris (acetyl acetate) aluminum, tris (ethyl acetate acetate) aluminum, monoacetyl acetate' bis (ethyl acetate acetate) And the like.
• the metal chelate compounds (F) can be used alone or in combination of two or more.
• the mixing ratio of the metal chelate compound (F) is usually 0.01 to 50 parts by weight, preferably 0.1 to 50 parts by weight, more preferably 0.5 to 50 parts by weight, per 100 parts by weight of the metal alkoxide (A). 10 parts by weight.
• the keto compound (G) has the following general formula:
• the] 3-keto compound (G) is coordinated with a metal atom in the metal chelate compound (F) at the time of preparing the aqueous dispersion, whereby the metal alkoxide (A), carbon-carbon dioxide It is considered that the action of accelerating the condensation reaction with the monomer (B-i) having a heavy bond and a metal alkoxide group is appropriately suppressed, and the action of further improving the storage stability of the obtained composition is achieved.
• Such a / 3-keto compound (G) include acetylacetone and acetylacetone.
• -keto compounds (G) acetylacetone and ethyl acetoacetate are particularly preferred.
• the -keto compound (G) can be used alone or in combination of two or more.
• 3-The keto compound (G) is mixed with a metal chelate compound
• the aqueous dispersion of the surface treatment agent of the present invention may contain the metal chelate compound (F) and the] 3-keto compound (G), but may contain various other additives as required. it can. That is, in order to enhance the antifouling property of the fiber, at least one kind of colloidal silica and / or colloidal alumina (hereinafter collectively referred to as “(H) colloidal addition lj”) is blended. can do.
• the colloidal silica is a dispersion in which high-purity silica anhydride is dispersed in water and / or a hydrophilic organic solvent, and has an average particle size of usually 5 to 100 nm, preferably 10 to 50 nm, and a solid content of The concentration is usually 10-40 weight. / 0 or so.
• colloidal silicas are, for example, Snowtex, methanol silica sol, and isopropanol silica sol (all manufactured by Nissan Chemical Industries, Ltd.).
• the colloidal alumina is an alumina sol using water as a dispersion medium and having a pH in the range of 2.5 to 6 or an alumina sol using a hydrophilic organic solvent as a dispersion medium, and the average particle size is usually 5 to 200 nm.
• the solids concentration is usually between 5 and 25 weight, preferably between 10 and 100 nm. / About 0 .
• alumina for example, synthetic alumina, boehmite, pseudo-boehmite and the like are used.
• Such colloids like alumina for example, alumina sol - 100, sol - 2 00, alumina sol - O (above, manufactured by Nissan Chemical Industries, Ltd.) are commercially available under the trade names such.
• the (H) colloidal additive can be used alone or in combination of two or more.
• the blending ratio of the colloidal additive is calculated on a solid basis in terms of the copolymer (ie, the polymers (B), (C) and (D)).
• the amount is usually 30 parts by weight or less, preferably 20 parts by weight or less, for example, 0.1 to 20 parts by weight with respect to 100 parts by weight.
• Curing can be performed by heat (for example, heating at 100 to 150 ° C.).
• the inorganic / organic hybrid material (surface treating agent) of the present invention can be applied to a substrate (object to be treated) by a conventionally known method.
• the surface treating agent is diluted with an organic solvent or water and applied to the object to be treated (for example, Rippet) by a known method such as dip coating, spray coating, foam coating, or the like. Attached to the surface of the processed material.
• the concentration of inorganic / organic hybrid material in the dip solution is 0.05 to 30 weight. /. It may be.
• concentration of the inorganic / organic hybrid material in the treatment liquid may be 0.1 to 5% by weight.
• the article treated with the surface treatment agent of the present invention may be a fiber product.
• it is preferably a carpet.
• fiber products For example, natural animal and plant fibers such as cotton, hemp, wool, and silk; synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene; semi-synthetic fibers such as rayon and acetate; and glass fibers. And inorganic fibers such as carbon fiber and asbestos fiber, or a mixed fiber thereof. Since the processing agent of the present invention has excellent resistance to detergent solutions and brushing (mechanical), it can be suitably used for nylon and polypropylene carpets.
• the textile product may be in any form of fiber, yarn, cloth and the like.
• the forceet may be formed after treating the fiber or yarn with the surface treatment agent, or the formed cartridge may be formed. May be treated with a surface treatment agent.
• Objects to be treated with the surface treatment agent of the present invention include fiber products, glass, paper, wood, leather, fur, asbestos, brick, cement, metal, stone, concrete and concrete.
• Examples include oxides, ceramic products, plastics, painted surfaces, plasters, building materials, rubber, optical waveguides, and contact lenses.
• a member for an image forming apparatus can be mentioned.
• the image forming apparatus include a copying machine, a printer, a facsimile, and a multifunction peripheral thereof.
• the shape of the member include various shapes such as a roll shape, a blade shape, and a belt shape. Specifically, photoreceptors, charging rolls, charging brushes, charging blades, developing rolls, intermediate transfer rolls, intermediate transfer belts, paper transfer rolls, transfer fixing belts, fixing rolls, fixing belts, pressure rolls, pressure belts , A paper feed roll, a paper feed belt, a separation claw, a cleaning blade, a cleaning roll, and the like, but are not limited to these names.
• the present invention is not limited to members for electrophotographic image forming apparatuses using powder toner, and is not limited to toner jet systems, liquid toner systems, ink jet systems, sublimation systems, and thermal transfer systems. It is needless to say that the present invention can be applied to a member for use. Furthermore, it is also useful as an antireflection agent for liquid crystal display devices and display surfaces, as a surface treatment agent for waveguides, interlayer insulating films, and heat exchangers for air conditioners.
• the value of the antifouling rate after cleaning was determined to be 30% or more by the following formula.
• Antifouling rate (%) 100 X ( ⁇ ⁇ - ⁇ ⁇ ) / ⁇ ⁇
• ⁇ Number of cleanings ( ⁇ is an integer from 20 to 20)
• the antifouling test is performed in accordance with AATCC-II-123-1995, and the cleaning is performed in accordance with AATCC-TM-138-1992.
• L, *, 3, b, * are the object colors calculated by the L * a * b * system of the carpet after the antifouling test, and /, a, and b are the carpets before the antifouling test. Of L * a * b * The object colors are shown respectively. ]
• the antifouling ratio can maintain a value of 30% or more, for example, 50% or more when the number of times of cleaning is 3, preferably 5, more preferably 10, more preferably 15, especially 20 times.
• Carpets can maintain an antifouling rate of preferably at least 20%, more preferably at least 30%, after one cycle of contamination, cleaning and recontamination.
• the value of the residual ratio of the surface treating agent after cleaning represented by the following formula, Is 10% or more
• Residual ratio (%) 1 00 ⁇ A 2 / A)
• I R intensity ratio (Si-O-Si group absorption peak area) / (Nylon amide group absorption peak area)
• the absorption peak area of the S i -OS i group is the peak area calculated in the integration interval of 100 to 981 cm- 1 .
• the absorption peak area of the amide group of nylon is a peak area calculated in an integration interval of 1673 to 1583 cm- 1 .
• the value of the residual ratio of the coating film after cleaning may be 10% or more, for example, 10% or more, particularly 30% or more.
• the refractive index of the coating film is 1.35 or less, for example, 1.32 or less, 1.30. May be.
• the refractive index of the coating is measured using a white light refractometer (Abbe refractometer).
• the refractive index for the light source is measured by using white light that has been replaced with sodium D-line using a compensator.
• Parts represent parts by weight unless otherwise specified.
• the test was performed as follows.
• a film of inorganic / organic hybrid material (thickness 1 / m) is formed on a glass plate.
• the Knoop hardness of the film is measured with a Terasawa microhardness tester (SM-2 manufactured by Taiyo Tester Co., Ltd.).
• oil repellency was measured using AATCC-TM-118-19666, by placing several drops (approximately 4 mm in diameter) of the test solution shown in Table II in two places on the sample cloth and immersing it after 30 seconds. And the highest point of the oil repellency provided by the test solution that does not show immersion is defined as oil repellency. Table II
• the antifouling property of the pets treated with the surface treating agent was evaluated by the following method according to AATCC-TM-123-995.
• the e-Lumi / Le used here is cylindrical, with a diameter of 12.0 cm at the inner bottom and a height of 9.5 cm. After that, the excess dry soil that had adhered was thoroughly suctioned with a household vacuum cleaner, and the color difference ( ⁇ ) on the carpet surface was measured using a colorimeter (Minolta CR-310). Ask for.
• composition of Lysoil is as follows. Table I I 1
• the force-treated dough treated with the surface treating agent is "cleaned" according to the method of AATCC TM-138-1992. Details of the cleaning are as follows.
• the rotation speed of the test table is 20 rpm
• the rotation speed of the flyer is 240 rpm
• the cleaning / testing machine, cum, and water injection nozzle are not used.
• the residual ratio of the nip film treated with the surface treating agent is determined by the following method.
• the nylon film before and after cleaning was cut to 5.5 x 1.5 cm, and the surface of the coating film was analyzed by the IR ATR method (Perkin Elmer FT-IR 1760X). Find the survival rate.
• TEOS tetraethoxysilane
• CH 2 C (CH 3 ) C00 (CR, CH 2 0) 9 CH 3 10 parts
• CH 2 C (CH 3 ) COO (CH 2 CH (CH 3 ) 0)) 2 H 4 parts
• CR, C (CH,) C00CH, CH (OH) CH ? OH 1 part, tetraethoxysilane 30 parts, ethanol 120 parts were added, 9 parts of 0.5N hydrochloric acid were added while stirring, and the mixture was stirred at room temperature for 24 hours to cause hydrolysis and polycondensation reaction.
• Product 5 was prepared in exactly the same manner as in Synthesis Example 1 except that 5 parts of methacrylic acid (MA A) was used instead of 5 parts of methyl methacrylate in Synthesis Example 1.
• MA A methacrylic acid
• Synthesis Example 1 1.5 parts of n-decyltriethoxysilane (long-chain alkyl compound) was used instead of 1.5 parts of heptadecafluoro-1,1,2,2-tetrahydrodecyltriethoxysilane (fluorine-containing compound) A product 6 was prepared in exactly the same manner as in Synthesis Example 1 except that this was performed.
• Product 7 was prepared in exactly the same manner as in Synthesis Example 1 except that 30 parts of methyl methacrylate was used in Synthesis Example 1 instead of 15 parts of 3-methacryloxypropyltrimethoxysilane and 15 parts of tetraethoxysilane.
• Product 8 was prepared in exactly the same manner as in Synthesis Example 4, except that 30 parts of polyalkylene glycol methacrylate was used instead of 30 parts of tetraethoxysilane.
• the product 1, N, N-dimethylformamide (DMF) obtained in Synthesis Example 1 was mixed in the amounts shown in Table A to prepare a mixture.
• the product 3, obtained in Synthesis Example 3, and N, N-dimethylformamide (DMF) were mixed in the amounts shown in Table A to prepare a mixed solution (solution C).
• the glass transition point of the compound (product 3) was 110 ° C.
• Emulsion polymerization of product 1 (emulsion A)
• Product 1 obtained in Synthesis Example 1 pure water, n-laurylmercaptan (LSH), polyoxyethylene alkynolepheninole ether ether ammonium sulfate (Hytenol N-17, anionic emulsifier), polyoxyethylene Table A shows alkylphenyl ether (Nonion HS-220, nonionic emulsifier), polyoxyethylene sorbitan monolaurate (Nonion LT-221, nonionic emulsifier), and dipropylene glycol monomethyl ether (DPM). The mixture was mixed in the amounts shown in Table 1 to prepare a mixture.
• LSH n-laurylmercaptan
• Hytenol N-17 anionic emulsifier
• Table A shows alkylphenyl ether (Nonion HS-220, nonionic emulsifier), polyoxyethylene sorbitan monolaurate (Nonion LT-221, nonionic emulsifier), and diprop
• the mixture is emulsified by an ultrasonic emulsifier, and the obtained emulsion is placed in a 1 L four-necked flask equipped with a reflux condenser, a nitrogen inlet, a thermometer, and a stirrer. Dissolved oxygen was removed by nitrogen replacement. Next, an initiator, ammonium persulfate (APS), was charged in the amount shown in Table A. The copolymerization reaction was carried out at 60 ° C. for 8 hours under stirring to obtain a copolymer (emulsion A). The glass transition point of the copolymer was 109 ° C.
• Emulsion polymerization of product 2 (emulsion B)
• a copolymer (emulsion B) was obtained in exactly the same manner as in Production Example 4, except that Product 2 was used instead of Product 1 used in Production Example 4.
• the glass transition point of the copolymer was 108 ° C.
• Production Example 6 A copolymer (solution D) was obtained in exactly the same manner as in Production Example 1, except that Product 4, isopropyl alcohol (IPA) was used instead of Product 1 and DMF used in Production Example 1. .
• the glass transition temperature of the copolymer was 105 ° C.
• a copolymer (solution E) was obtained in exactly the same manner as in Production Example 1 except that Product 5 was used instead of Product 1 used in Production Example 1.
• a copolymer (solution F) was obtained in exactly the same manner as in Production Example 1 except that Product 6 was used instead of Product 1 used in Production Example 1.
• Emulsion polymerization of product 5 (emulsion C)
• a copolymer (emulsion C) was obtained in exactly the same manner as in Production Example 4 except that Product 5 was used instead of Product 1 used in Production Example 1.
• Emulsion polymerization of product 6 Emulsion D
• a copolymer (emulsion D) was obtained in exactly the same manner as in Production Example 4, except that Product 6 was used instead of Product 1 used in Production Example 5.
• a copolymer (solution G) was obtained in exactly the same manner as in Production Example 1, except that Product 7 was used instead of Product 1 used in Production Example 1.
• a copolymer (solution H) was obtained in exactly the same manner as in Production Example 1, except that Product 8 was used instead of Product 1 used in Production Example 1. Table A
• Solution A obtained in Production Example 1 was diluted with N, N-dimethylformamide (DMF) to prepare a solution having a solid content of 3% by weight.
• DMF N, N-dimethylformamide
• Solution B obtained in Production Example 2 was diluted with N, N-dimethylformamide (DMF) to obtain a solid content of 3 wt. A / 0 solution was prepared. This was evaluated in the same manner as in Example 1.
• Solution C obtained in Production Example 3 was diluted with N, N-dimethylformamide (DMF) to prepare a liquid having a solid content of 3% by weight. This was evaluated in the same manner as in Example 1.
• DMF N, N-dimethylformamide
• Emulsion A obtained in Production Example 4 was diluted with pure water to have a solid content of 3 weight. / 0 solution was prepared.
• Example 6 Solution D obtained in Production Example 6 was diluted with ethanol to have a solid content of 3 wt. A / 0 solution was prepared. This was evaluated in the same manner as in Example 1.
• the surface treatment agent which consists of an inorganic-organic hybrid material which maintains sufficient water-repellency and oil-repellency before and after cleaning, the persistence of a coating film, and antifouling property, and provides durability is obtained.

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