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
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/08—Homopolymers or copolymers of acrylic acid 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
  • 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
• • 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
  • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
  • C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/16—Antifouling paints; Underwater paints
  • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
  • C09D5/1662—Synthetic film-forming substance
  • C09D5/1668—Vinyl-type polymers
• • 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
  • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
• • 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
  • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
  • D06M2101/02—Natural fibres, other than mineral fibres
  • D06M2101/04—Vegetal fibres
  • D06M2101/06—Vegetal fibres cellulosic
• • 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
  • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
  • D06M2101/16—Synthetic fibres, other than mineral fibres
  • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M2101/32—Polyesters
• • 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

Definitions

• the present invention is a water / oil repellent composition that can impart excellent water / oil repellency (particularly water repellency) and durability to articles such as fibers even when the amount of fluorine-containing monomer is reduced (in particular, The object is to provide a water repellent composition).
• a polymer or copolymer of a polymerizable monomer containing a fluoroalkyl, or a compound containing a fluoroalkyl is treated as an organic solvent solution or an aqueous dispersion into a fiber product, etc., and the surface thereof is water- and oil-repellent.
• a technique for imparting is known.
• Patent Documents 1 and 2 Attempts have been made to copolymerize a monomer having an adhesive group together with a fluoroalkyl-containing polymerizable monomer for the purpose of improving the durability of water and oil repellency against washing and dry cleaning. Also, attempts have been made to create economically superior water / oil repellent compositions by blending a polymer not containing fluoroalkyl and a polymer containing fluoroalkyl (Patent Documents 1 and 2). In addition, it has been proposed to use a polymerizable monomer having a specific structure as a polymer or copolymer that can be added without deteriorating antifouling performance or durability (Patent Document 3).
• Patent Document 5 discloses a liquid repellent for carpets characterized in that a fluoroalkyl-containing polymer and a polymer not containing fluoroalkyl are mixed, and both have a glass transition point or a melting point of 45 ° C. or higher ( Patent Document 6).
• JP-B-38-22487 Japanese Patent Publication No. 41-8579 JP-B 49-42878 JP 06-228241 JP 61-264081 US4043964
• the present inventors provide a water and oil repellent composition that exhibits high water and oil repellency even when the amount of fluorine monomer used is reduced and is excellent in durability.
• a polymer having a polymer unit having a specific chemical structure and a polymer having a polymer unit derived from a monomer containing a fluoroalkyl group also have outstanding water and oil repellency and durability by mixing an aqueous dispersion. It has been found that the above object can be achieved, and the present invention has been completed.
• the present invention provides a water-dispersed water / oil repellent composition
• a water-dispersed water / oil repellent composition comprising an aqueous medium, the following polymer (A) and the following polymer (B).
• Type water / oil repellent composition has remarkable water / oil repellency and durability. For this reason, this invention can reduce cost by reducing the usage-amount of a fluorine monomer, and can provide the water / oil repellent which exhibits high water / oil repellency and is excellent also in durability.
• the present invention includes the following polymer (A) and the following polymer (B), wherein the polymer (A) and the polymer (B) are not present in the same particle.
• An oil composition is provided.
• particles composed of the polymer (A) and particles composed of the polymer (B) exist separately in the aqueous dispersion.
• the present invention also provides an article treated with the water / oil repellent composition.
• acrylic acid and methacrylic acid are collectively referred to as (meth) acrylic acid.
• a polyfluoroalkyl group is referred to as an Rf group.
• the polymer (A) has a polymerization unit of the polymerizable monomer (a) of 50% by weight or more, and at least one polymerization unit of the polymerizable monomer (b) or the polymerizable monomer (c) is 50% by weight.
• polymerizable monomers (x) other than polymerizable monomers (a) and (b) for example, forming an unsaturated double bond) (Y) containing a polymerizable unit (y) having a halogen atom bonded to a carbon atom or a polymerizable monomer having a reactive group (z)), and a polymerizable unit and a polymerizable monomer of the polymerizable monomer (a)
• An addition polymer in which the total of the polymerized units of the body (b) and the polymerizable monomer (c) is 50% by weight or more is preferable.
• the polymer (A) may not contain the polymerizable monomer (b) or (c) polymerization unit.
• the polymerizable monomer (a) is an (meth) acrylate having an Rf group or an acrylate having a halogen substituted at the ⁇ -position [hereinafter referred to as a monomer (a) or an Rf group-containing monomer. ].
• the (meth) acrylate having an Rf group or an acrylate having a halogen substituted at the ⁇ -position means a compound in which the Rf group is present in the alcohol residue part of (meth) acrylic acid or ⁇ -substituted acrylate ester.
• the Rf group is a group in which two or more hydrogen atoms of an alkyl group are substituted with fluorine atoms.
• the number of carbon atoms in the Rf20 group is preferably 2 to 20, particularly 4 to 16, particularly 4 to 6. When the number of carbon atoms is less than 2, the water repellency tends to decrease, and when it exceeds 20, the monomer (a) becomes solid at room temperature, and the sublimation property tends to be large and handling tends to be difficult.
• the Rf group may contain a halogen atom other than the fluorine atom.
• Other halogen atoms are preferably chlorine atoms.
• an etheric oxygen atom or a thioetheric sulfur atom may be inserted between carbon-carbon bonds in the Rf group.
• Examples of the structure of the terminal portion of the Rf group include CF 3 CF 2 —, (CF 3 ) 2 CF—, CHF 2 —, CH 2 F—, CClF 2 — and the like, with CF 3 CF 2 — being preferred.
• the Rf group is a group in which two or more hydrogen atoms of a saturated alkyl group are substituted with fluorine atoms.
• the ratio of fluorine atoms in the Rf group is preferably such that (number of fluorine atoms in the Rf group) / (number of fluorine atoms in the Rf group + number of hydrogen atoms in the Rf group) is 40% or more. In particular, the case of 60% or more is preferable.
• part or all of the hydrogen atoms may be substituted with chlorine atoms.
• the Rf group preferably has a linear or branched structure, and particularly preferably has a linear structure.
• the branched portion is preferably present near the end of the Rf group.
• the branched portion is preferably a short chain having about 1 to 4 carbon atoms.
• the preferred carbon number of the Rf group is 1-12.
• Particularly preferred as the Rf group is an Rf group containing a perfluoroalkyl group or a perfluoroalkyl group moiety when the proportion of the fluorine atom is substantially 100%.
• the perfluoroalkyl group also preferably has a linear structure.
• the linear perfluoroalkyl group C m F 2m + 1 — [where m is an integer of 2 to 20. ] Is preferable.
• Rf group is given below.
• structural isomer groups which are groups having different structures having the same molecular formula, are included.
• the Rf group and the polymerizable unsaturated group are bonded directly or indirectly through a bonding group, and are preferably bonded indirectly.
• the linking group is a divalent or higher linking group, and is preferably an alkylene group, an ester group, an amide group, an amino group, a urethane group, an ether group, a phenyleneoxy group, a sulfonyl group, or a linking group containing these structures.
• These Rf group-containing monomers are known or known compounds and can be easily synthesized from Rf group-containing alcohols, Rf group-containing carboxylic acids, Rf group-containing sulfonic acids, or the like.
• the Rf group-containing monomer in the present invention is preferably a compound having a structure in which one Rf group is linked to a polymerizable unsaturated group via a divalent linking group.
• Rf group-containing acrylate, Rf group-containing methacrylate, Rf group-containing styrene, Rf group-containing vinyl ester, and Rf group-containing fumarate are preferable.
• the Rf group-containing monomer in the present invention is particularly preferably a (meth) acrylate containing an Rf group or an acrylate chlorinated at the ⁇ -position from the viewpoint of versatility.
• Rf group-containing monomers have the general formula: Rf-Q 1 -X 1 [Wherein, Rf represents a fluoroalkyl group, Q 1 represents a divalent organic group, and X 1 represents a monovalent organic group containing a polymerizable unsaturated group. ] Can be expressed as
• Q 1 represents a divalent organic group, and — (CH 2 ) n + p —, — (CH 2 ) n C (O) ONH (CH 2 ) p —, — (CH 2 ) n CONH (CH 2 ) P -,-(CH 2 ) n SO 2 NH (CH 2 ) p -,-(CH 2 ) n NHC (O) NH (CH 2 ) p- and the like are preferable.
• n and p are 0 or an integer of 1 or more
• n + p is an integer of 2 to 22.
• Q 1 is-(CH 2 ) n + p -,-(CH 2 ) n C (O) ONH (CH 2 ) p -,-(CH 2 ) n SO 2 NH (CH 2 ) p - a is and, p is an integer of 2 or more, when n + p is 2 to 6 are preferred, in particular n + p is in the case where 2-6 - (CH 2) n + p -, i.e., dimethylene Group to hexamethylene group is preferred.
• X 1 represents a monovalent organic group containing a polymerizable unsaturated group, a residue of an olefin, a residue of a vinyl ether, a residue of a vinyl ester, a residue of a (meth) acrylate, a styrene These residues are preferred.
• -CR 1 CH 2 or -OCH 2
• - ⁇ -CR 1 CH 2 as residues of olefins
• (meth) residues acrylates -OC (O) CR 1 CH 2
• a vinyl ether -OCR 1 CH 2 as the residue of the group
• -C (O) OCR 1 CH 2 as the residue of the vinyl ester
• R 1 is a hydrogen atom, a linear or branched alkyl group having 1 to 21 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a CFX 1 X 2 group (where X 1 and X 2 are Hydrogen atom, fluorine atom, chlorine atom, bromine atom or iodine atom), cyano group, linear or branched fluoroalkyl having 1 to 21 carbon atoms, substituted or unsubstituted benzyl group, substituted or non-substituted It is a substituted phenyl group, and ⁇ is a phenylene group.
• X 1 is preferably a residue of (meth) acrylates, and in particular when —R 1 is a hydrogen atom, a methyl group or a chlorine atom, —OC (O) CR 1 ⁇ CH 2 , that is, an acryloxy group Alternatively, a methacryloxy group or an ⁇ -chloroacryloxy group is preferable.
• Rf group-containing monomer in particular, from the viewpoints of polymerizability with other monomers, flexibility of the film formed on the fiber, adhesion to the substrate, solubility in a solvent, ease of emulsion polymerization, etc. ) Acrylates are preferred.
• One or more Rf group-containing monomers can be used.
• Rf group-containing monomer examples include, for example, the following, but are not limited thereto.
• Polymerizable monomer (b) has an alkyl group and does not have an Rf group (meth) acrylate [hereinafter referred to as monomer (b). ].
• the (meth) acrylate having an alkyl group refers to a compound in which the alkyl group is present in the alcohol residue portion of the (meth) acrylic acid ester.
• the alkyl group an alkyl group having 2 or more carbon atoms, for example, 2 to 30 carbon atoms (cyclic and chain alkyl groups), particularly a linear alkyl group is preferable.
• the monomer (b) examples include ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl ( Preferable examples include (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate and the like.
• the monomer (b) may be two or more polymerizable monomers having an alkyl group and no Rf group.
• Polymerizable monomer (c) is an acrylate having an alkyl group and not substituted with an Rf group and halogenated at the ⁇ -position [hereinafter referred to as monomer (c). ].
• the acrylate having an alkyl group and halogen-substituted at the ⁇ -position refers to a compound in which an ⁇ -position of an acrylate ester is halogen-substituted and the alkyl group is present in the alcohol residue portion.
• the alkyl group an alkyl group having 2 or more carbon atoms, for example, 2 to 30 carbon atoms (cyclic and chain alkyl groups), particularly a linear alkyl group is preferable.
• the monomer (c) examples include ethyl ⁇ -chloroacrylate, n-butyl ⁇ -chloroacrylate, isobutyl ⁇ -chloroacrylate, t-butyl ⁇ -chloroacrylate, 2-ethylhexyl ⁇ -chloroacrylate, and isodecyl ⁇ ⁇ ⁇ .
• Preferred examples include -chloroacrylate, cetyl ⁇ -chloroacrylate, stearyl ⁇ -chloroacrylate, behenyl ⁇ -chloroacrylate, lauryl ⁇ -chloroacrylate, and cyclohexyl ⁇ -chloroacrylate.
• the monomer (c) may be two or more polymerizable monomers having an alkyl group and no Rf group.
• the polymer (A) contains a monomer (b) or a monomer (c) polymer unit
• the weight ratio of the polymerized units (c) is preferably 1 or more.
• the polymer (A) is a polymerizable monomer (x) other than the polymerizable monomers (a), (b), (c) (for example, carbon atoms forming an unsaturated double bond).
• the polymerizable monomer (c) are preferably an addition polymer having a total of 70% by weight or more based on the polymer.
• the proportion of the polymer units of the monomer (a) in the polymer (A) is preferably 50% by weight or more, for example 50 to 90% by weight, particularly 60 to 80% by weight, based on the polymer.
• the proportion of the polymerized units of the monomer (b) in the polymer (A) is preferably 50% by weight or less, for example 1 to 40% by weight, particularly 3 to 30% by weight, based on the polymer.
• the proportion of the polymerized units of the monomer (c) in the polymer (A) is 50% by weight or less, for example 0 to 40% by weight, particularly 0 to 30% by weight, particularly 1 to 10%, based on the polymer. It is preferable that it is weight%.
• the total of the monomer (a) polymer unit, the monomer (b) polymer unit, the monomer (c) polymer unit, and the monomer (x) polymer unit is based on the polymer (A). It is preferably 90% by weight or more, for example, 95 to 100% by weight.
• the proportion of the polymerized units of the monomer (x) is preferably 70% by weight or less, for example 0 to 40% by weight or less, particularly 1 to 30% by weight, based on the polymer (A).
• the monomer (x), particularly the monomer (y), may be a compound that does not contain a fluorine atom.
• the monomer (x) may be a copolymerizable monomer having a benzene ring.
• (meth) acrylates having a benzene ring are preferred.
• the benzene ring may have a substituent (for example, an alkyl group or alkoxy group having 1 to 10 carbon atoms, or a halogen atom).
• (meth) acrylate having a benzene ring phenyl (meth) acrylate, benzyl (meth) acrylate, or a compound in which a methyl group, a methoxy group, a chlorine atom or the like is bonded to these benzene rings is preferable.
• ethylene, styrenes, etc. may be sufficient.
• the halogen atom is directly bonded to the carbon atom constituting the main chain.
• a repeating unit is derived from a monomer in which a halogen atom is directly bonded to a carbon atom forming a carbon-carbon double bond (referred to as “main chain monomer having a halogen atom” in this specification). it can.
• main chain monomer having a halogen atom examples are fluorine, chlorine, bromine and iodine.
• main chain monomers having a halogen atom examples include vinyl halides such as vinyl chloride and vinyl fluoride, vinylidene halides such as vinylidene chloride and vinylidene fluoride, and chlorotrifluoroethylene. And ⁇ -chloro (meth) acrylate having a hydrocarbon group. Since ⁇ -chloro (meth) acrylates having a hydrocarbon group are contained in the monomer (c), they do not correspond to the monomer (y). As the monomer (y), vinyl chloride and vinylidene chloride are preferable.
• the main chain monomer having a halogen atom may be one kind or a combination of two or more kinds.
• the amount of the polymerized unit of the monomer (y) is preferably 40% by weight or less, for example 0 to 30% by weight, particularly 1 to 25% by weight, based on the polymer (A).
• Examples of the polymerizable monomer (z) having a reactive group include an epoxy group, halogen atom, hydroxyl group, amide group, amino group, imino group, alkoxysilyl group, N-methylol group, N-alkyloxyalkyl group, block A reactive group other than the polymerizable unsaturated bond such as an isocyanate group may be contained.
• Examples of the reactive group-containing polymerizable monomer (z) include 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylamide, and N-methylol (meth).
• hydroxyl group-containing (meth) acrylate examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (oxyethylene / oxy) Propylene) glycol mono (meth) acrylate, glycerin mono (meth) acrylate, trimethylolpropane mono (meth) acrylate and the like are preferable.
• a blocked product of a reaction product obtained by reacting a hydroxyl group-containing (meth) acrylate and a polyisocyanate in a ratio in which at least one isocyanate group remains A reaction product obtained by reacting a hydroxyl group-containing (meth) acrylate and a polyisocyanate derivative having at least one blocked isocyanate group and at least one free isocyanate group is preferred.
• polyisocyanates examples include aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate, or alicyclic polyisocyanates such as isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, and bis (isocyanate methyl) cyclohexane, and These nurate modified bodies, prepolymer modified bodies, burette modified bodies and the like can be mentioned, and aliphatic diisocyanates or alicyclic diisocyanates are preferable.
• aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate
• alicyclic polyisocyanates such as isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, and bis (is
• Examples of the blocking agent for obtaining a blocked isocyanate group include oximes, alkyl ketoximes, phenols, ⁇ -diketones, malonic esters, lactams, alkanols, and the like.
• Specific examples of the blocking agent include cyclohexane oxime, methyl ethyl ketoxime, phenol, cresol, acetylacetone, diethyl malonate, isopropanol, t-butanol, ⁇ -caprolactam, maleic imide, sodium bisulfite and the like. Cyclohexane oxime, methyl ethyl keto oxime and the like are preferable.
• the amount of the polymerized units of the monomer (z) in the polymer (A) is preferably 10% by weight or less, for example, 0.1 to 8% by weight with respect to the polymer (A).
• the amount of the polymerization units of the monomer (x) excluding the monomer (y) and the monomer (z) is 30% by weight or less, for example, 0 to 10% by weight with respect to the polymer (A). It is preferable.
• a polymerization method for obtaining the polymer (A) when the polymerization is carried out by an emulsion polymerization method or a dispersion polymerization method, there is a method of polymerizing the above polymerizable monomer by adding a polymerization initiator in the presence of an emulsifier and a polymerization medium.
• the emulsifier is not particularly limited, and one or more known or well-known emulsifiers of nonionic type, cationic type, anionic type and amphoteric type may be employed.
• the amount of the emulsifier is preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of the polymerizable monomer, and particularly preferably about 1 to 10 parts by weight from the viewpoint of water / oil repellency and dispersion stability.
• the polymerization medium is a medium containing water, and an organic solvent may be included if desired.
• organic solvent water-soluble organic solvents are preferable, and organic solvents such as esters, ketones, and ethers (alcohols) are preferable.
• ester-based organic solvent ethyl acetate, butyl acetate, diethyl succinate and the like are preferable.
• ketone-based organic solvent methyl ethyl ketone, methyl isobutyl ketone, acetone and the like are preferable, and as the ether-based (alcohol-based) organic solvent.
• the organic solvent is preferably an ether-based (alcohol-based) organic solvent from the viewpoint of low flammability.
• the ratio of water and organic solvent is not particularly limited, and any ratio may be used.
• the amount of the organic solvent may be 100 parts by weight or less, for example, 1 to 10 parts by weight with respect to 100 parts by weight of water.
• the amount of the polymerization medium may be 0.5 to 100 parts by weight, for example 1 to 20 parts by weight with respect to 1 part by weight of the polymerizable monomer.
• a water-soluble or oil-soluble polymerization initiator is preferable, and general-purpose initiators such as persulfate-based, azo-based, peroxide-based, and redox-based initiators can be used depending on the polymerization temperature.
• the polymerization temperature is not particularly limited, but is preferably 20 ° C to 150 ° C.
• a chain transfer agent may be included for the purpose of controlling the molecular weight. Mercaptans can be preferably used as the chain transfer agent.
• a mixture comprising a polymerizable monomer, water, and an emulsifier may be treated with a homomixer or a high-pressure emulsifier, and predispersed in advance.
• the polymer (A) (first polymer) synthesized by the above method is preferably present as fine particles in the medium.
• the particle diameter of the fine particles of the polymer (A) is preferably 0.001 to 1 ⁇ m, for example 0.01 to 0.5 ⁇ m. Within this range, the amount of the emulsifier may be small in order to obtain a stable dispersion, the water / oil repellency is high, and the polymer fine particles are stably present in the medium.
• the particle diameter can be measured with a dynamic light scattering device, an electron microscope, or the like.
• the average particle size is usually included in the above preferred range.
• the polymer (B) does not contain a polymerized unit of the polymerizable monomer (a), and the total of at least one polymerized unit of the polymerizable monomer (c) and the polymerizable monomer (y) is 10% by weight. % Or more of the polymerizable monomer (b) or polymerizable monomer (x) excluding the polymer (y) or polymerizable monomer (z) having a reactive group It is preferable that it is an addition polymer containing the following polymerization unit.
• the polymer (B) may be a weight body that does not contain a fluorine atom.
• Monomers (a), (b), (c), (x), (y), (z) in the polymer (B) are monomers (a), (b) in the polymer (A). , (C), (x), (y), (z) have the same meaning.
• the monomer (a) does not exist in the polymer (B).
• Monomers (b), (c), (x), (y), (z) in the polymer (B) are monomers (b), (c), (x) in the polymer (A).
• (Y), (z) may be the same or different.
• Each of the monomers (b), (c), (x), (y), and (z) may be used in two or more types.
• the amount of the monomer (b) (relative to the polymer) is not more than 90% by weight, for example 5 to 80% by weight, in particular 10 to 70% by weight, especially 30 to
• the amount of the monomer (c) is, for example, 0 to 8% by weight, particularly 0.5 to 5% by weight, and the amount of the monomer (y) is 20% by weight or more, for example, 25 to It is preferably 85% by weight, particularly preferably 30 to 80% by weight.
• the total amount of the monomer (c) and the monomer (y) is 10% by weight or more, for example, 20 to 90% by weight, and particularly preferably 30 to 80% by weight.
• the amount of the monomer (x) excluding the monomer (y) and the monomer (z) is 40% by weight or less, for example, 0 to 30% by weight, particularly 0 to 20% by weight.
• the amount of z) is preferably 10% by weight or less, for example 0.1 to 8% by weight.
• the polymerization method for obtaining the polymer (B) emulsion polymerization, suspension polymerization and the like are preferable as in the polymerization method for obtaining the polymer (A), and emulsion polymerization is particularly preferable. It can be obtained in a state where the polymer (B) is dispersed as particles in an aqueous solvent (also referred to as a dispersion) by emulsion polymerization or the like.
• an aqueous solvent also referred to as a dispersion
• Emulsion polymerization is preferably performed using a polymerization initiator.
• a peroxide or an azo compound is preferable, and an azo compound is particularly preferable.
• the azo compound include the oil-soluble polymerization initiator described in the polymer (A), 2,2′-azobis (2-methylpropionamidine) hydrochloride, 2,2′-azobis [2- (2 Preferred examples include water-soluble polymerization initiators such as -imidazolin-2-yl) propane] hydrochloride and 2,2'-azobis [2- (2-imidazolin-2-yl) propane] sulfate hydrate.
• a chain transfer agent may be added during the polymerization reaction.
• the chain transfer agent the chain transfer agents mentioned in the description of the polymer (A) can be preferably used.
• An emulsifier may be present in the dispersion of the polymer (B).
• the emulsifier the nonionic emulsifier, the cationic emulsifier, the anionic emulsifier or the amphoteric emulsifier described in the polymer (A) is preferable.
• Emulsifiers can be used alone or in combination of two or more. When an emulsifier having different ionicity is used in combination, a combination of a nonionic emulsifier and a cationic emulsifier, or a combination of a nonionic emulsifier and an amphoteric emulsifier is preferable.
• the amount of the emulsifier is preferably 1 to 20 parts by weight with respect to 100 parts by weight of the polymer (B).
• the average particle size of the polymer (B) is preferably 0.001 to 1 ⁇ m, particularly preferably 0.03 to 0.5 ⁇ m.
• the average particle size is less than 0.03 ⁇ m, a large amount of an emulsifier or a self-emulsifiable polymerizable monomer is required to obtain a stable dispersion, which may reduce water repellency.
• it exceeds 0.5 ⁇ m there is a possibility that the particles settle.
• the polymer (A) and the polymer (B) do not exist in the same particle, but form separate particles.
• the water / oil repellent composition of the present invention is separately polymerized for each, forming separate particles to obtain a dispersion, It is preferable to prepare by mixing the respective dispersions.
• the ratio of the polymer (A) or the polymer (B) is within the above range, the water / oil repellency is excellent, and the water / oil repellency durability is also excellent.
• the polymer concentration (solid content concentration) in the water / oil repellent composition is preferably 0.1 to 50% by weight.
• Two or more types of polymers may be used for each of the polymer (A) and the polymer (B).
• various properties other than the polymer (A) or the polymer (B), and the polymer repellency may be used as necessary to express various physical properties in articles such as textiles.
• a water agent, an oil repellent, a catalyst for promoting crosslinking, a texture modifier, an antistatic agent, a penetrating agent, an insect repellent, a flame retardant, an anti-wrinkle preventing agent, a dye stabilizer, a pH adjuster, and the like may be blended.
• the water / oil repellent composition of the present invention is applied to an article after being diluted to an arbitrary concentration according to the purpose or application.
• a water repellent processing method for an article any method is adopted depending on the type of the article, the preparation form of the composition, and the like.
• a method of adhering to the surface of the article by a coating method such as dipping or coating and drying is employed.
• it may be applied together with an appropriate crosslinking agent and subjected to heat treatment.
• a method of immersing the article in a water / oil repellent composition containing the polymer (A) and the polymer (B) is preferable.
• a water repellent processing method of immersing an article in a composition containing the polymer (B) and not containing the polymer (A) and then dipping in a composition containing the polymer (A) and not containing the polymer (B) is also preferable because an equivalent effect can be obtained.
• the article (base material or article to be treated) treated with the water / oil repellent composition (treating agent) of the present invention is not particularly limited, and in addition to textiles, stones, filters (for example, electrostatic filters) ), Dust masks, glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painted surfaces, plasters and the like. Fiber, fiber fabric, fiber knitted fabric and the like are preferable.
• fibers include animal and vegetable natural 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, glass fibers, Examples thereof include inorganic fibers such as carbon fibers, or mixed fibers thereof.
• An article treated with the water / oil repellent composition of the present invention has excellent water repellency and excellent durability.
• the article to be treated is treated with a treating agent.
• Treatment means that a treatment agent is applied to an object to be treated by dipping, spraying, coating, or the like.
• the fluoropolymer which is an active ingredient of the treatment agent penetrates into the treatment object and / or adheres to the surface of the treatment object.
• % and parts mean “% by weight” and “parts by weight” unless otherwise specified.
• the characteristics were measured as follows. When treating a water / oil repellent T / C fabric, the polymer dispersion is diluted with water so that the solid content is 30% by weight, and water is used so that the concentration of the 30% by weight dispersion is 3.2%.
• a treatment solution by diluting with After immersing T / C cloth (twill, 200 g / m 2 , undyed cloth) in the treatment liquid, squeezing with mangle at 4 kg / cm 2 , 4 m / min and heat-treating at 170 ° C. for 1 minute, Evaluate water and oil repellency. Similarly, the treatment liquid is prepared by diluting with water so that the concentration of the 30 wt% dispersion becomes 4.8%.
• Average particle size The average particle size of the dispersed particles is measured using a laser light scattering method (Fiber-Optics Particle Analyzer FPAR-1000 manufactured by Otsuka Electronics Co., Ltd.).
• n-butyl acrylate is n-BA
• N-methylolacrylamide is N-MAM
• 3-chloro-2-hydroxypropyl methacrylate is TM
• lauryl mercaptan is L-SH
• n-butyl methacrylate is n-BMA
• t-Butyl methacrylate is t-BMA
• stearyl acrylate is StA
• lauryl acrylate LA
• vinyl chloride is VCl
• 3,3,4,4,5,5,6,6,7,7,8,8,8- Tridecafluorooctyl methacrylate is 13FMA
• 2,2,3,3,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluoro-nonyl acrylate is 17FA It was written.
• di-cured tallow alkyldimethylammonium chloride is described as C2ABT, sorbitan monopalmitate as PP-40R, polyethylene glycol lauryl ether as K220, and polyoxyethylene oleyl ether as BO50.
• Tripropylene glycol was described as TPG, and 2,2′-azobis (2-amidinopropane) dihydrochloride was described as NC-32W.
• Synthesis example 1 In a 500 mL container, n-BA (63.11 g), N-MAM (1.26 g), TM (0.63 g), L-SH (0.9 g), emulsifier C2ABT (0.91 g), PP-40R (1.22 g), K220 (5.25 g), BO50 (1.3 g), water (103.4 g), TPG (18.62 g) were added, and the mixture was mixed with a homomixer. After the dispersion, the mixture was treated with an ultrasonic emulsifier while cooling for 5 minutes to obtain an emulsion of the monomer mixture.
• This emulsion was put into a 500 mL separable flask equipped with a cooling tube, a nitrogen introduction tube, and a thermometer. After purging with nitrogen, NC-32W (0.38 g) as an initiator was dissolved in water (4 g) and added. Thereafter, the temperature was raised to 60 ° C., followed by polymerization for 3 hours to obtain a dispersion of non-fluorinated polymer particles having a solid content of 35.3% and an average particle size of 0.109 ⁇ m (207.1 g).
• Synthesis Examples 2 to 16 In the same manner as in Synthesis Example 1, the monomer mixture shown in Table 3 was emulsified. When VCl was used as a monomer, a 500 mL stainless steel autoclave was used. The mixture was placed in a separable flask and polymerized to obtain various non-fluorine polymer particles.
• Examples 1-6, Comparative Examples 1-6 Dispersion mixtures obtained by blending the dispersions of polymer particles obtained in Synthesis Examples 1 to 16 with water so that the solid content concentration is 30% by weight are blended at the mixing ratios shown in Tables 7 to 10. It was.
• Test Examples 1-6 The polymer particle dispersions obtained in Examples 1 to 6 were evaluated for water / oil repellency. The evaluation results are shown in Table 11.
• Comparative Test Examples 1-6 The polymer particle dispersions obtained in Comparative Examples 1 to 6 were evaluated for water / oil repellency. The evaluation results are shown in Table 12.
• Test Examples 7-8 and Comparative Test Examples 11-12 With respect to various fabrics obtained by treating the aqueous resin dispersions shown in Tables 14 and 15 by the method shown in Test Example 1, the water and oil repellency washing durability was evaluated. The evaluation results are shown in Tables 14-15.

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