WO2015037385A1 - Composition de matériau de revêtement intérieur retardateur de flamme, matériau de revêtement intérieur retardateur de flamme, et procédé de production d'une composition de matériau de revêtement intérieur retardateur de flamme - Google Patents

Composition de matériau de revêtement intérieur retardateur de flamme, matériau de revêtement intérieur retardateur de flamme, et procédé de production d'une composition de matériau de revêtement intérieur retardateur de flamme Download PDF

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Publication number
WO2015037385A1
WO2015037385A1 PCT/JP2014/071331 JP2014071331W WO2015037385A1 WO 2015037385 A1 WO2015037385 A1 WO 2015037385A1 JP 2014071331 W JP2014071331 W JP 2014071331W WO 2015037385 A1 WO2015037385 A1 WO 2015037385A1
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Prior art keywords
flame retardant
mass
backing material
material composition
parts
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PCT/JP2014/071331
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English (en)
Japanese (ja)
Inventor
巧 進士
幸一郎 樋笠
学 倉田
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株式会社イーテック
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Priority to JP2015536498A priority Critical patent/JPWO2015037385A1/ja
Publication of WO2015037385A1 publication Critical patent/WO2015037385A1/fr

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    • 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
    • C08L33/18—Homopolymers or copolymers of nitriles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C09D5/027—Dispersing agents
    • 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
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C09D5/185—Intumescent paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/45—Anti-settling agents
    • 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
    • D06M13/08—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with halogenated hydrocarbons
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • 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
    • D06M13/165—Ethers
    • 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
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
    • 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
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D06M15/252—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing bromine
    • 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
    • D06M15/31—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated nitriles
    • 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
    • D06M15/53—Polyethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/693—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives 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
    • 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
    • D06M2200/30—Flame or heat resistance, fire retardancy properties

Definitions

  • the present invention relates to a flame retardant backing material composition, a flame retardant backing material, and a method for producing a flame retardant backing material composition. More specifically, the present invention relates to a composition for forming a flame retardant backing material for fabric, a flame retardant backing material formed from the flame retardant backing material composition, and a method for producing the flame retardant backing material composition.
  • halogen-based flame retardants have been used as backing materials for synthetic fiber products used for interiors such as vehicle seats and carpets.
  • brominated flame retardants such as decabromodiphenyl ether are widely used.
  • halogen-based flame retardants are known to have degradability, bioaccumulation properties, toxicity such as generation of harmful combustion gases, and environmental load is a concern.
  • Patent Documents 1 and 2 As a flame retardant other than halogen, use of a phosphorus flame retardant has been proposed (for example, Patent Documents 1 and 2). However, even if it is a phosphorus-type flame retardant, in the case of red phosphorus, although it is excellent in a flame retardance, there exists a problem which toxic gases, such as a phosphine, generate
  • halogen-based flame retardants Due to advances in high-temperature combustion technology that reduces the generation of dioxins and the like when burned as waste, the use of halogen-based flame retardants with excellent flame resistance and water resistance is being reviewed.
  • a halogen compound particularly a bromine compound
  • a surfactant or the like is used for stabilization in an aqueous dispersion.
  • this surfactant due to the influence of this surfactant, there has been a problem of a decrease in water resistance of the aqueous dispersion itself. For example, when water is applied to a polyester fiber fabric or the like, there is a problem that a part of the surfactant or flame retardant elutes on the surface and so-called creaking occurs.
  • the present invention has been made in view of such problems of the prior art, and the object of the present invention is bromine which exhibits sufficient flame resistance and fluff resistance, and which also copes with environmental problems.
  • An object of the present invention is to provide a flame retardant backing material composition containing a flame retardant.
  • the present inventors can achieve the above-mentioned problems by including a specific brominated flame retardant in a favorable dispersed state with a specific surfactant. As a result, the present invention has been completed.
  • the following flame retardant backing material composition flame retardant backing material, flame retardant backing material, and method for producing the flame retardant backing material composition are provided.
  • a flame retardant backing material composition is provided.
  • the polymer (A1) contained in the copolymer emulsion (A) has a reactive emulsifier (A2) of 1.0 to 5.0 with respect to 100 parts by mass (in terms of solid content) of monomers.
  • the polymer (A1) is composed of (1) a styrene / butadiene copolymer, (2) an ⁇ , ⁇ -unsaturated nitrile / conjugated diene copolymer, and (3) an acrylic polymer.
  • the flame retardant backing material composition according to any one of [1] to [3], which contains at least one polymer selected from the above.
  • a flame retardant backing comprising: a flame retardant aqueous dispersion (B) preparation step for obtaining a water dispersion (B), and a mixing step of mixing the water dispersion (B) and the copolymer emulsion (A). Manufacturing method of material composition.
  • a total of 100 parts by mass (converted to solid content) of monomers is polymerized using 1.0 to 5.0 parts by mass (converted to solid content) of a reactive emulsifier (A2) to obtain a polymer (A1
  • A2 reactive emulsifier
  • the flame retardant backing material composition of the present invention exhibits sufficient flame retardancy and fluff resistance while containing a brominated flame retardant, and also responds to environmental problems.
  • the flame retardant backing material of the present invention exhibits sufficient flame retardancy and fluff resistance while containing a brominated flame retardant, and also responds to environmental problems.
  • the method for producing a flame retardant backing material composition of the present invention provides a flame retardant backing material composition containing a brominated flame retardant exhibiting sufficient flame retardancy and resistance to wrinkles and also addressing environmental problems. It is.
  • the flame retardant backing material composition is a composition comprising a copolymer emulsion (A), a flame retardant (B1), and a surfactant (B2) as essential components.
  • the flame retardant backing material composition can contain various additives as long as the flame retardancy, the resistance to flaking, and the environmental compatibility are not impaired.
  • the flame retardant backing material composition is flame retardant when conforming to “FMVSS-302” defined by the US automobile safety standards, that is, “JIS-D1201” defined by Japanese Industrial Standards. It means that
  • the term “kiwakki resistance” means that when moisture adheres to a fiber product and then the moisture evaporates and dries, no stain due to elution of the components of the flame retardant backing material occurs in the moisture adhering portion. It shall mean a characteristic.
  • the flame retardant (B1) is a bromine compound having a bromine content of 60% or more and a molecular weight of 1000 or more.
  • a bromine compound having a molecular weight of 1000 or more is less likely to accumulate in the living body and has excellent environmental compatibility compared to a bromine compound having a molecular weight of less than 1000.
  • a flame retardant (B1) has high flame retardance since a bromine content rate is 60% or more, a flame retardant (B1) has high flame retardance.
  • the bromine content of the flame retardant (B1) is a value measured by ion chromatography on a sample pretreated in accordance with the oxygen flask combustion method described in JIS K7229.
  • the molecular weight is a number average molecular weight measured by a time-of-flight mass spectrometer (TOF-MS).
  • Surfactant (B2) stabilizes the flame retardant (B1) in an aqueous dispersion of the flame retardant backing material composition.
  • the surfactant (B2) is a compound that is anionic and has an ammonium salt. Since the flame retardant (B1) is dispersed and stabilized in the flame retardant backing material composition by such a surfactant (B2), the flame retardant backing material composition may exhibit excellent flame retardancy. it can.
  • the content ratio of the flame retardant (B1) in the flame retardant backing material composition is 50 to 200 parts by mass (in terms of solids) with respect to 100 parts by mass (in terms of solids) of the copolymer emulsion (A).
  • the flame retardant backing material composition can exhibit sufficient flame retardancy.
  • the content ratio of the flame retardant (B1) to 200 parts by mass or less generation of wrinkles can be suppressed.
  • “Kiwatsuki” refers to a molded article containing a compound dissolved in water, when water adheres to the surface of the molded article, the compound elutes into the moisture, and then the above compound is evaporated by moisture evaporation. Refers to the phenomenon of precipitation on the surface of a molded product.
  • the flame retardant backing material composition when used as a material for forming a flame retardant backing material for a fiber, it may appear as a stain on the surface of the fiber. That is, in the present specification, “kicking resistance” means that components such as the flame retardant (B1) are deposited on the surface of the flame retardant backing material formed from the flame retardant backing material composition, and the creaking occurs. It means the performance to suppress.
  • the content ratio of the surfactant (B2) is 0.5 to 5.0 parts by mass (solid content conversion) with respect to 100 parts by mass (solid content conversion) of the flame retardant (B1). It is.
  • the content ratio of the surfactant (B2) 0.5 parts by mass or more, the dispersion stability of the flame retardant (B1) in the flame retardant backing material composition can be improved.
  • the said content ratio of surfactant (B2) 5.0 mass parts or less, it can suppress that surfactant (B2) causes a fluff.
  • the flame retardant (B1) is a bromine compound having a bromine content of 60% or more and a molecular weight of 1000 or more.
  • the bromine content of the flame retardant (B1) is 60% or more, preferably 65% or more, more preferably 70% or more, and particularly preferably 80% or more.
  • the upper limit of the bromine content of the flame retardant (B1) is not particularly limited, the bromine content of the flame retardant (B1) is usually 85% or less due to structural limitations.
  • a flame retardant (B1) having a bromine content within these ranges a flame retardant having higher flame retardancy is used, so that the flame retardancy of the flame retardant backing material composition can be improved. it can.
  • the molecular weight of the flame retardant (B1) is 1000 or more, preferably 1500 or more, and more preferably 1800 or more.
  • the flame retardant (B1) is less likely to be accumulated in the living body, and environmental compatibility can be improved.
  • the upper limit of the molecular weight of the flame retardant (B1) is not particularly limited, but from the viewpoint of dispersion stability in the flame retardant backing material composition, the molecular weight of the flame retardant (B1) is preferably 30000 or less, More preferably, it is 10,000 or less, and particularly preferably 2000 or less.
  • the average particle size of the flame retardant (B1) is preferably 1 to 100 ⁇ m, more preferably 5 to 70 ⁇ m, and particularly preferably 10 to 60 ⁇ m.
  • the flame retardant (B1) having an average particle diameter of 100 ⁇ m or less the number of particles of the flame retardant (B1) can be relatively increased, and the flame retardant performance can be improved.
  • the lower limit of the average particle diameter of the flame retardant (B1) is not particularly limited, but since the molecular weight is 1000 or more, the substantial lower limit is 5 ⁇ m.
  • the flame retardant (B1) is not particularly limited as long as it is within the above bromine content and molecular weight ranges.
  • Examples thereof include compounds having a bromophenyl group (brominated aryl ether-containing compounds) as represented by the following general formula (1).
  • n is preferably 1 to 10
  • the compound represented by the general formula (1) preferably has three or more bromophenyl groups.
  • Brm represents a bromine addition number of 1 to 5
  • Brn represents a bromine addition number of 1 to 4
  • Brp represents a bromine addition number of 0 to 4.
  • A represents —R or —Br, and each R independently represents hydrogen, hydroxy group, alkyl group, aldehyde group, carbonyl group, vinyl group, alkali metal or alkali Indicates earth metal. Note that hydrogen, a hydroxy group, an alkyl group, an aldehyde group, a carbonyl group, a vinyl group, and the like may be ether-bonded.
  • the compound having a bromophenyl group is a compound having a bromophenyl group in which one or more hydrogen atoms are substituted with bromine atoms, and the more the number of hydrogen atoms in the bromophenyl group substituted with bromine atoms, the more preferable .
  • a tetrabromophenyl group and a pentabromophenyl group are particularly preferable.
  • Such a compound having a bromophenyl group has a relatively high bromine content and high flame retardancy.
  • a brominated polymer compound such as brominated polystyrene or brominated polyphenyl ether
  • a brominated polymer compound such as brominated polystyrene or brominated polyphenyl ether
  • 1,4-dipentabromophenyl ether-2,3,5,6-tetrabromobenzene, 1,5-dipentabromophenyl ether-2,3,4,6-tetrabromobenzene C 6 Br 5 —O—C 4 Br 4 —O—C 6 Br 5
  • 1,4-ditetrabromophenyl ether-2,3,5,6-tetrabromobenzene C 6 Br 4 —O—C 4 Brominated compounds such as Br 4 —O—C 6 Br 4
  • 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine can be used.
  • the content ratio of the flame retardant (B1) in the flame retardant backing material composition is 50 to 200 parts by mass (in terms of solids) with respect to 100 parts by mass (in terms of solids) of the copolymer emulsion (A) described later. It is preferably 100 to 200 parts by mass (in terms of solid content), more preferably 120 to 170 parts by mass (in terms of solid content).
  • the surfactant (B2) is a compound that stabilizes the flame retardant (B1) in an aqueous dispersion of the flame retardant backing material composition, is anionic, and has an ammonium salt.
  • the surfactant (B2) is not particularly limited as long as it has such characteristics.
  • the surfactant (B2) include monoalkyl anion ammonium salts such as ammonium lauryl sulfate, ammonium myristyl sulfate, ammonium stearyl sulfate, ammonium oleyl sulfate, polyoxyethylene lauryl ether ammonium sulfate, polyoxyalkylene alkenyl ether ammonium sulfate, and polyacrylic acid.
  • a polymer having an anionic ammonium salt such as ammonium in the side chain can be used.
  • the content ratio of the surfactant (B2) in the flame retardant backing material composition is 0.5 to 5.0 parts by mass (in terms of solids) with respect to 100 parts by mass (in terms of solids) of the flame retardant (B1). 0.5 to 3.0 parts by mass (in terms of solid content), more preferably 0.5 to 2.0 parts by mass (in terms of solid content), and 1.5 to 2 parts by mass. Particularly preferred is 0.0 part by mass (in terms of solid content).
  • copolymer emulsion (A) is an aqueous emulsion containing a polymer (A1) which is a resin component constituting the flame retardant backing material composition.
  • the polymer (A1) is not particularly limited as long as it can be dispersed in a dispersion medium.
  • Specific examples include natural rubber, butadiene rubber, isoprene rubber, chloroprene rubber, styrene-butadiene copolymer rubber, butadiene- Examples include isoprene copolymer rubber, butadiene / styrene / isoprene copolymer rubber, acrylonitrile / butadiene copolymer rubber, and acrylic rubber.
  • At least one polymer selected from the group consisting of a styrene / butadiene copolymer, an ⁇ , ⁇ -unsaturated nitrile / conjugated diene copolymer, and an acrylate polymer preferable.
  • the polymer (A1) may be modified with at least one functional group.
  • the functional group include a carboxylic acid group, an N-methylol group, a glycidyl group, a hydroxyl group, and a sulfonic acid group.
  • a carboxylic acid group is preferable.
  • the content of the functional group in 100% by mass of the polymer (A1) is preferably 0.1 to 10.0% by mass, and preferably 0.5 to 5. More preferably, it is 0 mass%.
  • the flame retardant backing material composition containing the polymer (A1) having the functional group content of 0.1% by mass or more the stability of the flame retardant backing material can be made sufficient.
  • the polymer (A1) whose said content rate of a functional group is 10.0 mass% or less, the increase in manufacturing cost can be suppressed.
  • the particle diameter of the polymer (A1) is not particularly limited, but is preferably 100 to 300 nm, more preferably 150 to 250 nm, and particularly preferably 180 to 220 nm.
  • the polymer (A1) having a particle diameter within these ranges has an appropriate viscosity and is excellent in coating stability.
  • the flame retardant backing material composition preferably contains other flame retardant (B3) in addition to the copolymer emulsion (A), the flame retardant (B1) and the surfactant (B2).
  • the other flame retardant (B3) has a function as a flame retardant that can further improve the flame retardancy.
  • the other flame retardant (B3) include metal oxides such as antimony trioxide, antimony pentoxide, aluminum oxide, and magnesium oxide, ammonium phosphate, ammonium polyphosphate, ammonium sulfate, guanidine phosphate, and phosphate ester.
  • metal oxides such as antimony trioxide, antimony pentoxide, aluminum oxide, and magnesium oxide
  • Conventionally known flame retardants such as oxides such as zinc borate, metal hydroxides such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide and zinc hydroxide can be used.
  • the content ratio of the other flame retardant (B3) in the flame retardant backing material composition is 5 to 70 parts by mass (solid content conversion) with respect to 100 parts by mass (solid content conversion) of the flame retardant (B1). It is preferably 10 to 50 parts by mass (in terms of solid content), more preferably 20 to 40 parts by mass (in terms of solid content).
  • the flame retardancy of the flame retardant backing material composition can be further improved, and the wrinkles can be suppressed.
  • Dispersion medium (B4) The flame retardant backing material composition can use water as the dispersion medium (B4).
  • the dispersion medium (B4) may contain alcohols or ketones such as acetone.
  • the content of the dispersion medium (B4) can be appropriately adjusted according to the solid content concentration, viscosity, and the like of the flame retardant backing material composition.
  • the flame retardant backing material composition may further contain other additives.
  • additives include thickeners, antifoaming agents, fillers, dispersants, wetting agents, and pigments.
  • thickener examples include xanthan gum, polyacrylic acid, ammonium polyacrylate, sodium polyacrylate, carboxymethylcellulose (CMC), sodium carboxymethylcellulose (CMCNa), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), methyl
  • examples thereof include vinyl ether maleic anhydride copolymer, sodium alginate, propylene glycol ester alginate, pectin, xanthan gum, locust bean gum, guar gum, arabian galactan, sodium hyaluronate and the like.
  • the content ratio of the thickener is 0.01 to 5 parts by mass (solid content) with respect to 100 parts by mass (in terms of solid content) of the copolymer emulsion (A). Conversion), and more preferably 0.1 to 5 parts by mass (in terms of solid content).
  • antifoaming agent examples include silicon-based, mineral oil-based, acetylene-based compounds, alcohols and the like.
  • the content of the antifoaming agent is 0.01 to 5 parts by mass (solid content) with respect to 100 parts by mass (in terms of solid content) of the copolymer emulsion (A). Conversion), and more preferably 0.1 to 5 parts by mass (in terms of solid content).
  • filler examples include aluminum hydroxide, magnesium hydroxide, calcium carbonate, and clay.
  • filler content in the case of adding a filler as an additive can be appropriately adjusted according to the type of filler.
  • the content ratio of the filler is 10 to 150 parts by mass (in terms of solids) with respect to 100 parts by mass (in terms of solids) of the copolymer emulsion (A).
  • it is 50 to 100 parts by mass (in terms of solid content).
  • dispersant examples include polycarboxylate compounds, polyphosphate compounds, sulfate compounds, nonionic compounds, acetylene compounds, and the like.
  • the content ratio of the dispersant is 0.01 to 5 parts by mass (in terms of solids) with respect to 100 parts by mass (in terms of solids) of the copolymer emulsion (A). It is preferably 0.1 to 1 part by mass (in terms of solid content).
  • a method for producing a flame retardant backing material composition comprises a step of preparing a flame retardant aqueous dispersion (B), an aqueous dispersion (B), and a copolymer emulsion (A). And a mixing step.
  • the manufacturing method of a flame-retardant backing material composition may further include a copolymer emulsion (A) preparation step.
  • the flame retardant aqueous dispersion (B) preparation step, copolymer emulsion (A) preparation step, and mixing step will be described in order.
  • the flame retardant aqueous dispersion (B) preparation process comprises an aqueous dispersion (B) obtained by dispersing and stabilizing a flame retardant (B1) using a surfactant (B2). It is a process to obtain.
  • the flame retardant (B1) is the above-mentioned flame retardant (B1), the bromine content is 60% or more, and the molecular weight is 1000 or more.
  • Surfactant (B2) is the above-mentioned surfactant (B2), is anionic, and has an ammonium salt.
  • Other flame retardants (B3) may be added here.
  • the flame retardant (B1) is dispersed and stabilized by the surfactant (B2), so that the flame retardant (B1) does not agglomerate with each other, or the flame retardant does not settle, and the like. Among them, it is possible to sufficiently exhibit the function as a flame retardant.
  • an aqueous dispersion (B) in which the flame retardant (B1) is dispersed and stabilized using the surfactant (B2) for example, a mixture containing the flame retardant (B1) and the surfactant (B2) is used.
  • a method of stirring the liquid at a high speed a method using a bead mill, a ball mill, etc., a method using a three roll, etc.
  • other additives may be added and mixed in the flame retardant aqueous dispersion (B) preparation step.
  • Step of preparing copolymer emulsion (A) is a step of obtaining copolymer emulsion (A) containing polymer (A1) by polymerization using reactive emulsifier (A2).
  • the method for synthesizing the polymer (A1) contained in the copolymer emulsion (A) is not particularly limited, and various conventionally known polymerization methods such as radical polymerization, anionic polymerization, and cationic polymerization can be employed. Among these, as a polymerization method of the polymer (A1), radical polymerization is preferable, and synthesis by emulsion polymerization using the reactive emulsifier (A2) is particularly preferable.
  • a monomer capable of forming each constituent unit of the various polymers (A1) described above can be used as a raw material monomer for synthesizing the polymer (A1).
  • the reactive emulsifier (A2) used for the synthesis of the polymer (A1) includes a reactive emulsifier containing a sulfonic acid group and / or a sulfate group; a reactive emulsifier containing a carboxyl group and / or a carboxylate group; phosphoric acid Reactive emulsifiers containing groups and / or salts thereof; reactive emulsifiers containing phosphate groups; allyl group-containing sulfonic acids such as allylsulfonic acid and 2-methylallylsulfonic acid or salts thereof; isoprenesulfonic acids or their Salt; (meth) acryloyl group-containing sulfonic acids such as 2-sulfoethyl (meth) acrylate and 2-sulfopropyl (meth) acrylate or salts thereof; (meth) acrylamide such as (meth) acrylamide-t-butylsulfonic acid Examples thereof
  • the reactive emulsifier (A2) commercially available products having, for example, the following trade names having sulfonic acid groups and salts thereof include “Latemul S-180” (manufactured by Kao Corporation), “Latemul S-180A” ( (Manufactured by the company), “Eleminol JS-2” (manufactured by Sanyo Chemical Industries, Ltd.), “Eleminol JS-20” (manufactured by the company), “Eleminor RS-30” (manufactured by the company), etc .; those having sulfate groups and salts thereof “AQUALON HS-10” (Daiichi Kogyo Seiyaku Co., Ltd.), “AQUALON HS-1025” (manufactured by the company), “AQUARON KH-05” (manufactured by the company), “AQUALON KH-10” (manufactured by the company) "Adekaria soap SE-10" (manufact
  • the reactive emulsifier (A2) may be used alone or in combination of two or more.
  • the reactive emulsifiers and sulfate groups having a sulfonic acid group and / or a sulfate group because they are excellent in flame retardancy as a backing material, mechanical stability, and film water resistance.
  • / or a reactive emulsifier having a salt thereof, and a reactive emulsifier having a sulfonic acid group and / or a sulfate group is more preferable.
  • the amount of the reactive emulsifier (A2) used is 1.0 to 5.0 with respect to 100 parts by mass (in terms of solid content) of the total amount of raw material monomers of the polymer (A1). It is preferable to use a part by mass (in terms of solid content), more preferably 1.0 to 3.0 parts by mass (in terms of solid content), and 1.0 to 2.0 parts by mass (in terms of solid content). It is particularly preferred.
  • the viscosity of the resulting polymer (A1) is suppressed from excessively increasing, and is more excellent in workability and coatability. It becomes possible to obtain a flame retardant backing material composition.
  • a non-reactive emulsifier may be used in addition to the reactive emulsifier (A2).
  • a known emulsifier can be used.
  • a nonionic emulsifier, an anionic emulsifier, or the like can be used.
  • These non-reactive emulsifiers may be used in combination with the reactive emulsifier (A2).
  • the polymerization initiator used for the synthesis of the polymer (A1) is not particularly limited as long as it does not inhibit the emulsion polymerization using the reactive emulsifier (A2) described above.
  • the mixing step is a step of mixing the copolymer emulsion (A) obtained by the above-described preparation steps and the flame retardant aqueous dispersion (B).
  • the method of mixing the copolymer emulsion (A) and the flame retardant aqueous dispersion (B) is not particularly limited, and a conventionally known method can be adopted. If necessary, other additives may be added and mixed in this mixing step.
  • the flame retardant backing material composition can form a flame retardant backing material applied to the back surface of textile products such as carpets, sheets, mats and interiors.
  • textile products to which the flame retardant backing material is applied include synthetic fibers such as nylon, polyester, rayon, vinylon, and acrylic, as well as textile products formed of vegetable fibers such as cotton, hemp, and jute. it can.
  • the method for applying the flame retardant backing material is not particularly limited, and examples thereof include a roll coater method, a direct coating method, a knife coating method, and a spray coating method.
  • the roll coater method is a method in which after a backing agent is applied to a fiber product, the fiber is sufficiently impregnated with the backing agent using a roll coater and then dried.
  • the solid content concentration of the flame retardant backing material or the flame retardant backing material composition is preferably 20% or more, more preferably 30% or more, and particularly preferably 40% or more.
  • the viscosity of the flame retardant backing material or the flame retardant backing material composition is preferably about 1,000 to 100,000 mPa ⁇ s, more preferably about 5,000 to 80,000 mPa ⁇ s, and preferably about 10,000 to 70,000 mPa ⁇ s. Particularly preferred.
  • bromine content of the flame retardant was measured by ion chromatography on a sample pretreated in accordance with the oxygen flask combustion method described in JIS K7229.
  • the pretreated sample was diluted 20 times and measured by ion chromatography, and the bromine concentration was calculated by the following formula.
  • the environmental compatibility of the flame retardant was evaluated by measuring the number average molecular weight of the flame retardant.
  • the number average molecular weight of the flame retardant was measured using a time-of-flight mass spectrometer (TOF-MS).
  • TOF-MS time-of-flight mass spectrometer
  • JMS-T100GCV AccuTOF GCv 4G manufactured by JEOL (JEOL Ltd.) was used as a measuring device, and the measurement was performed at room temperature.
  • the environmental assessment was conducted according to the following criteria. Good: Number average molecular weight 1000 or more (in vivo accumulation is suppressed) Impossible: Number average molecular weight less than 1000
  • Example 1 to 30 Comparative Examples 1 to 26
  • the flame retardant backing materials of Examples 1 to 30 and Comparative Examples 1 to 26 and fiber products using these flame retardant backing materials were produced as follows.
  • the following monomers were used as raw material monomers for the polymer for preparing the copolymer emulsion at the following blending ratio.
  • the total of the following monomer components (a) and (b) was 100 parts by mass.
  • Monomer component (a) ethylenically unsaturated carboxylic acid monomer: Acrylic acid (manufactured by Toagosei Co., Ltd.) 1.0 part by mass monomer component (b) (acrylic ester monomer): 2-ethylhexyl acrylate (Toagosei Co., Ltd.) 92.0 parts by mass Butyl acrylate (Toagosei Co., Ltd.) 3.0 parts by mass Acrylonitrile (Mitsubishi Rayon Co., Ltd.) 4.0 parts by mass
  • the polymers of Examples and Comparative Examples were synthesized as follows. First, 0.04 parts by mass of an emulsifier and 41 parts by mass of water that had been dispersed in water in advance were charged into a reaction vessel and stirred under a nitrogen stream to prepare an emulsifier dispersion. The temperature of the emulsifier dispersion was raised to 70 ° C. Next, a mixed solution of the monomer components (a) and (b) (a total of 100 parts by mass of the monomer components (a) and (b)), 27 parts by mass of water, and 2 parts by mass of an emulsifier are added. It pre-emulsified by stirring.
  • This pre-emulsified monomer solution and a catalyst aqueous solution (0.05% ammonium persulfate aqueous solution) prepared in advance were dropped into the reaction vessel in parallel at 80 ° C. over about 3 hours. . After completion of the dropwise addition, the mixture was kept at 80 ° C. for about 1 hour. After cooling, 0.5 part by mass of 25% aqueous ammonia was added. In this way, an acrylic emulsion, that is, a copolymer emulsion, having a solid content concentration of 54.5%, a viscosity of 900 mPa ⁇ s, and a polymer particle diameter of around 200 nm was obtained.
  • the flame retardant aqueous dispersion was prepared by stirring a flame retardant, a surfactant and water at high speed (peripheral speed 2000 m / min) using a TK automixer manufactured by Special Machinery Co., Ltd.
  • the prepared copolymer emulsion, the flame retardant aqueous dispersion, and other additives are mixed using a paddle type stirrer, and used as a flame retardant backing material, that is, a flame retardant backing material.
  • a composition was prepared.
  • a fiber product was produced as follows.
  • a flame-retardant backing material was applied to a polyester fiber cloth having a length of 300 mm and a width of 200 mm by a coating method using a blade coater.
  • the flame retardant (B1) having a bromine content of 60% or more and a molecular weight of 1000 or more Containing 50 to 200 parts by mass (in terms of solid content) of 100 parts by mass (in terms of solid content) of the copolymer emulsion (A) and a specific amount of the specific surfactant (B2) It can be seen that the composition exhibits sufficient flame retardancy and resistance to flaking and is also compatible with environmental problems.
  • the surfactant (B2) that is anionic and has an ammonium salt is used as a flame retardant (B1).
  • a flame retardant backing material composition containing 0.5 to 5.0 parts by mass (in terms of solid content) with respect to 100 parts by mass (in terms of solid content) and containing a specific amount of a specific flame retardant (B1) is sufficient. It can be seen that it exhibits excellent flame retardancy and resistance to flares and is also compatible with environmental problems.
  • the flame retardant backing material composition containing polymers synthesized using various emulsifiers exhibits sufficient flame retardancy and fluff resistance, and also responds to environmental problems. It can be seen that Among them, when a polymer is synthesized by using a reactive emulsifier at a compounding ratio of 1.0 to 5.0 parts by mass (solid content conversion) with respect to 100 parts by mass (solid content conversion) of the total amount of monomers, It can be seen that the wrinkle resistance is remarkably improved.
  • the flame retardant backing material composition of the present invention can be used as a flame retardant backing material for polyester fiber products and the like.
  • the flame-retardant backing material of the present invention can be used as a backing material for textile products such as sheets, mats, interiors, etc. for automobiles and aircraft.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

L'invention porte sur une composition de matériau de revêtement intérieur retardateur de flamme, qui présente une ininflammabilité suffisante et une résistance suffisante à la formation de filigranes et contient un agent retardateur de flamme contenant du chrome, qui résout des problèmes environnementaux. La composition de matériau de revêtement intérieur retardateur de flamme, comprend une émulsion d'un copolymère (A) ; un agent retardateur de flamme (B1) ayant une teneur en brome de 60 % ou plus et une masse moléculaire de 1000 ou plus ; et un tensioactif (B2) qui peut disperser et stabiliser l'agent retardateur de flamme (B1), est anionique et contient un sel d'ammonium. L'agent retardateur de flamme (B1) est contenu en une quantité de 50 à 200 parties en masse (exprimées en extrait sec) pour 100 parties en masse (exprimées en extrait sec) de l'émulsion de copolymère (A), et le tensioactif (B2) est contenu en une quantité de 0,5 à 5,0 parties en masse (exprimées en extrait sec) pour 100 parties en masse (exprimées en extrait sec) de l'agent retardateur de flamme (B1).
PCT/JP2014/071331 2013-09-12 2014-08-12 Composition de matériau de revêtement intérieur retardateur de flamme, matériau de revêtement intérieur retardateur de flamme, et procédé de production d'une composition de matériau de revêtement intérieur retardateur de flamme WO2015037385A1 (fr)

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Cited By (2)

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WO2019203812A1 (fr) * 2018-04-18 2019-10-24 Arconic Inc. Composition ignifuge et panneau composite
CN115490907A (zh) * 2022-11-02 2022-12-20 南宁斤美新材料科技有限公司 一种耐高温防油污复合塑料的制备方法

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JP2007522281A (ja) * 2004-01-27 2007-08-09 ビー．ジー．・ポリマーズ・エー．・シー．・エー．・リミテッド 臭素化ポリマーおよびそれらを含む難燃製品
JP2007534824A (ja) * 2004-04-26 2007-11-29 ブローミン コンパウンズ リミテッド 繊維製品用難燃剤水性分散液及びその製造方法
JP2013006932A (ja) * 2011-06-23 2013-01-10 Henkel Japan Ltd シーラー用樹脂組成物
JP2014152415A (ja) * 2013-02-08 2014-08-25 Matsumoto Yushi Seiyaku Co Ltd 繊維用難燃加工薬剤、難燃性繊維の製造方法及び難燃性繊維

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JP2007522281A (ja) * 2004-01-27 2007-08-09 ビー．ジー．・ポリマーズ・エー．・シー．・エー．・リミテッド 臭素化ポリマーおよびそれらを含む難燃製品
JP2007534824A (ja) * 2004-04-26 2007-11-29 ブローミン コンパウンズ リミテッド 繊維製品用難燃剤水性分散液及びその製造方法
JP2013006932A (ja) * 2011-06-23 2013-01-10 Henkel Japan Ltd シーラー用樹脂組成物
JP2014152415A (ja) * 2013-02-08 2014-08-25 Matsumoto Yushi Seiyaku Co Ltd 繊維用難燃加工薬剤、難燃性繊維の製造方法及び難燃性繊維

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WO2019203812A1 (fr) * 2018-04-18 2019-10-24 Arconic Inc. Composition ignifuge et panneau composite
CN115490907A (zh) * 2022-11-02 2022-12-20 南宁斤美新材料科技有限公司 一种耐高温防油污复合塑料的制备方法
CN115490907B (zh) * 2022-11-02 2023-07-28 揭阳市冠业塑料制品有限公司 一种耐高温防油污复合塑料的制备方法

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