WO2015037385A1 - Flame-retardant lining material composition, flame-retardant lining material, and method for producing flame-retardant lining material composition - Google Patents

Flame-retardant lining material composition, flame-retardant lining material, and method for producing flame-retardant lining material composition Download PDF

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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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flame retardant
mass
backing material
material composition
parts
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Japanese (ja)
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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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    • 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
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    • 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
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    • 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
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    • 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
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    • 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
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    • D06M2200/30—Flame or heat resistance, fire retardancy properties

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

Abstract

Provided is a flame-retardant lining material composition which has sufficient flame retardancy and sufficient resistance to water mark formation and contains a bromine-containing flame retardant agent that deals with environmental concerns. A flame-retardant lining material composition comprising: a copolymer emulsion (A); a flame retardant agent (B1) having a bromine content of 60% or more and a molecular weight of 1000 or more; and a surfactant (B2) which can disperse and stabilize the flame retardant agent (B1), is anionic and contains an ammonium salt. The flame retardant agent (B1) is contained in an amount of 50 to 200 parts by mass (in terms of solid content) relative to 100 parts by mass (in terms of solid content) of the copolymer emulsion (A), and the surfactant (B2) is contained in an amount of 0.5 to 5.0 parts by mass (in terms of solid content) relative to 100 parts by mass (in terms of solid content) of the flame retardant agent (B1).

Description

難燃裏打材組成物、難燃裏打材、及び難燃裏打材組成物の製造方法Flame retardant backing material composition, flame retardant backing material, and method for producing flame retardant backing material composition
　本発明は、難燃裏打材組成物、難燃裏打材、及び難燃裏打材組成物の製造方法に関する。更に詳しくは、布用の難燃裏打材を形成する組成物、難燃裏打材組成物により形成される難燃裏打材、及び難燃裏打材組成物の製造方法に関する。 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.
　従来、車両のシートやカーペット等の内装に用いられる合成繊維系製品の裏打材として、ハロゲン系難燃剤が用いられている。例えば、デカブロモジフェニルエーテル等の臭素系難燃剤が広く用いられている。しかしながら、ハロゲン系難燃剤は、分解性、生体内蓄積性、有害燃焼ガス発生等の毒性を有することが知られており、環境負荷が懸念されている。 Conventionally, halogen-based flame retardants have been used as backing materials for synthetic fiber products used for interiors such as vehicle seats and carpets. For example, brominated flame retardants such as decabromodiphenyl ether are widely used. However, 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.
　ハロゲン系以外の難燃剤として、リン系難燃剤の使用が提案されている（例えば、特許文献１、２等）。しかしながら、リン系難燃剤であっても、赤リンの場合には、難燃性に優れるが、燃焼時にホスフィン等の有毒ガスが発生する問題がある。ポリリン酸アンモニウムの場合には、水溶性であるため、水分に溶出し、キワツキが発生しやすいという問題がある。耐水性を向上させたメラミン／ホルムアルデヒド処理されたマイクロカプセル化ポリリン酸アンモニウムの場合には、耐水性や耐キワツキ性は改善されるものの、ＶＯＣ（揮発性有機化合物）であるホルムアルデヒドの発生が問題として指摘されている。 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 | occur | produce at the time of combustion. In the case of ammonium polyphosphate, since it is water-soluble, there is a problem in that it is easily eluted by moisture and is likely to generate wrinkles. In the case of melamine / formaldehyde-treated microencapsulated ammonium polyphosphate with improved water resistance, water resistance and fluff resistance are improved, but the generation of formaldehyde as a VOC (volatile organic compound) is a problem. It has been pointed out.
特開２００６－２３３１５２号公報JP 2006-233152 A 特開２０１２－２１２４７号公報JP 2012-21247 A
　廃棄物として燃焼した場合のダイオキシン等の発生を削減する高温燃焼技術等の進歩により、難燃性や耐水性に優れるハロゲン系難燃剤の使用が見直されつつある。ハロゲン系化合物、特に臭素系化合物を難燃剤として用いる場合、水分散液中での安定化のために界面活性剤等が用いられる。しかしながら、この界面活性剤の影響で水分散液自体の耐水性の低下が問題となっていた。例えば、ポリエステル系繊維布帛等に水がかかった場合、界面活性剤や難燃剤の一部が表面に溶出し、いわゆるキワツキが発生する問題があった。 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. When a halogen compound, particularly a bromine compound, is used as a flame retardant, a surfactant or the like is used for stabilization in an aqueous dispersion. However, 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.
　本発明は、このような従来技術が有する問題点に鑑みてなされたものであり、その課題とするところは、十分な難燃性及び耐キワツキ性を示し、且つ、環境問題にも対応した臭素系難燃剤を含む難燃裏打材組成物を提供することにある。 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.
　本発明者らは上記課題を達成すべく鋭意検討した結果、特定の臭素系難燃剤を、特定の界面活性剤により良好な分散状態で含有させることによって、上記課題を達成することが可能であることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above-mentioned problems, 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.
　即ち、本発明によれば、以下に示す難燃裏打材組成物、難燃裏打材、及び難燃裏打材組成物の製造方法が提供される。 That is, according to the present invention, the following flame retardant backing material composition, flame retardant backing material, and method for producing the flame retardant backing material composition are provided.
［１］　共重合エマルジョン（Ａ）と、臭素含有率が６０％以上であり、且つ、分子量が１０００以上である難燃剤（Ｂ１）と、前記難燃剤（Ｂ１）を分散安定化させると共に、アニオン性であり、且つ、アンモニウム塩を有する界面活性剤（Ｂ２）と、を含み、前記共重合エマルジョン（Ａ）１００質量部（固形分換算）に対して、前記難燃剤（Ｂ１）５０～２００質量部（固形分換算）を含有し、前記難燃剤（Ｂ１）１００質量部（固形分換算）に対して、前記界面活性剤（Ｂ２）０．５～５．０質量部（固形分換算）を含有する難燃裏打材組成物。 [1] Dispersing and stabilizing the copolymer emulsion (A), the flame retardant (B1) having a bromine content of 60% or more and a molecular weight of 1000 or more, and the anion anion And a surfactant (B2) having an ammonium salt, and 50 to 200 parts by mass of the flame retardant (B1) with respect to 100 parts by mass (in terms of solid content) of the copolymer emulsion (A). Parts (in terms of solid content) and 0.5 to 5.0 parts by mass (in terms of solid content) of the surfactant (B2) with respect to 100 parts by mass (in terms of solid content) of the flame retardant (B1). A flame retardant backing material composition.
［２］　金属酸化物を更に含む前記［１］に記載の難燃裏打材組成物。 [2] The flame retardant backing material composition according to [1], further including a metal oxide.
［３］　前記共重合エマルジョン（Ａ）に含有されるポリマー（Ａ１）が、単量体の総量１００質量部（固形分換算）に対して、反応性乳化剤（Ａ２）１．０～５．０質量部（固形分換算）を用いて重合されたポリマーである前記［１］又は［２］に記載の難燃裏打材組成物。 [3] 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 flame retardant backing material composition according to the above [1] or [2], which is a polymer polymerized using part by mass (in terms of solid content).
［４］　前記ポリマー（Ａ１）が、（１）スチレン・ブタジエン系共重合体、（２）α、β－不飽和ニトリル・共役ジエン系共重合体、及び（３）アクリル系重合体からなる群より選択される少なくとも一種の重合体を含有する前記［１］～［３］のいずれかに記載の難燃裏打材組成物。 [4] The polymer (A1) is composed of (1) a styrene / butadiene copolymer, (2) an α, β-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.
［５］　前記［１］～［４］のいずれかに記載の難燃裏打材組成物により形成された難燃裏打材。 [5] A flame retardant backing material formed from the flame retardant backing material composition according to any one of [1] to [4].
［６］　臭素含有率が６０％以上であり、且つ、分子量が１０００以上である難燃剤（Ｂ１）を、アニオン性であり、且つ、アンモニウム塩を有する界面活性剤（Ｂ２）を用いて分散安定化させた水分散体（Ｂ）を得る難燃剤水分散体（Ｂ）調製工程と、前記水分散体（Ｂ）と、共重合エマルジョン（Ａ）を混合する混合工程と、を含む難燃裏打材組成物の製造方法。 [6] Dispersion stability of the flame retardant (B1) having a bromine content of 60% or more and a molecular weight of 1000 or more using an anionic surfactant (B2) having an ammonium salt 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.
［７］　単量体の総量１００質量部（固形分換算）に対して、反応性乳化剤（Ａ２）１．０～５．０質量部（固形分換算）を用いて重合させて、ポリマー（Ａ１）を含有する共重合エマルジョン（Ａ）を得る共重合エマルジョン（Ａ）調製工程を更に有する前記［６］に記載の難燃裏打材組成物の製造方法。 [7] 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 The method for producing a flame retardant backing material composition according to the above [6], further comprising a step of preparing a copolymer emulsion (A) to obtain a copolymer emulsion (A).
　本発明の難燃裏打材組成物は、臭素系難燃剤を含みながら、十分な難燃性及び耐キワツキ性を示し、且つ、環境問題にも対応するものである。 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.
　本発明の難燃裏打材は、臭素系難燃剤を含みながら、十分な難燃性及び耐キワツキ性を示し、且つ、環境問題にも対応するものである。 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.
　本発明の難燃裏打材組成物の製造方法は、十分な難燃性及び耐キワツキ性を示し、且つ、環境問題にも対応した臭素系難燃剤を含む難燃裏打材組成物を提供するものである。 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.
　以下、本発明の実施の形態について説明するが、本発明は以下の実施の形態に限定されるものではなく、本発明の趣旨を逸脱しない範囲で、当業者の通常の知識に基づいて、以下の実施の形態に対し適宜変更、改良等が加えられたものも本発明の範囲に入ることが理解されるべきである。 Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments, and based on ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. It should be understood that modifications, improvements, and the like appropriately added to the embodiments described above fall within the scope of the present invention.
　以下、本発明の難燃裏打材組成物の一実施形態、本発明の難燃裏打材組成物の製造方法の一実施形態、及び本発明の難燃裏打材の一実施形態について、その詳細を説明する。 Hereinafter, details of one embodiment of the flame retardant backing material composition of the present invention, one embodiment of the method for producing the flame retardant backing material composition of the present invention, and one embodiment of the flame retardant backing material of the present invention will be described in detail. explain.
１．難燃裏打材組成物
　難燃裏打材組成物は、共重合エマルジョン（Ａ）と、難燃剤（Ｂ１）と、界面活性剤（Ｂ２）と、を必須の構成成分とする組成物である。難燃裏打材組成物は、これら必須の構成成分以外にも、難燃性、耐キワツキ性、環境対応性を損なわない限りにおいて、各種添加剤を含有することができる。 1. Flame retardant backing material composition 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. In addition to these 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.
　本明細書中、難燃性については、米国自動車安全基準で定める「ＦＭＶＳＳ－３０２」、即ち日本工業規格で定める「ＪＩＳ－Ｄ１２０１」に適合する場合に、難燃裏打材組成物が難燃性であることを意味するものとする。 In the present specification, regarding flame retardancy, 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
　本明細書中、耐キワツキ性とは、繊維製品に水分が付着し、その後水分が蒸発し乾燥した場合に、水分が付着した部分に、難燃裏打材の構成成分の溶出によるシミが生じない特性を意味するものとする。 In the present specification, 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.
　難燃剤（Ｂ１）は、臭素含有率が６０％以上であり、且つ、分子量が１０００以上である臭素化合物である。分子量が１０００以上の臭素化合物は、分子量が１０００未満の臭素化合物と比較して、生体内への蓄積が抑制され、環境対応性に優れる。また、難燃剤（Ｂ１）は、臭素含有率が６０％以上であるため、難燃性が高い。 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. Moreover, since a bromine content rate is 60% or more, a flame retardant (B1) has high flame retardance.
　本明細書中、難燃剤（Ｂ１）の臭素含有率は、ＪＩＳ　Ｋ７２２９に記載の酸素フラスコ燃焼法に準拠して前処理した試料を、イオンクロマトグラフィにより測定した値である。 In the present specification, 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.
　本明細書中、分子量は、飛行時間型質量分析計（ＴＯＦ－ＭＳ）により測定した数平均分子量である。 In the present specification, the molecular weight is a number average molecular weight measured by a time-of-flight mass spectrometer (TOF-MS).
　界面活性剤（Ｂ２）は、難燃剤（Ｂ１）を、難燃裏打材組成物の水分散体中で分散安定化させるものである。界面活性剤（Ｂ２）は、アニオン性であり、且つ、アンモニウム塩を有する化合物である。難燃剤（Ｂ１）は、このような界面活性剤（Ｂ２）によって難燃裏打材組成物中で分散安定化されているため、難燃裏打材組成物は優れた難燃性を発揮することができる。 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.
　難燃裏打材組成物中、難燃剤（Ｂ１）の含有比は、共重合エマルジョン（Ａ）１００質量部（固形分換算）に対して、５０～２００質量部（固形分換算）である。難燃剤（Ｂ１）の上記含有比を５０質量部以上とすることにより、難燃裏打材組成物は充分な難燃性を発揮することができる。難燃剤（Ｂ１）の上記含有比を２００質量部以下とすることにより、キワツキの発生を抑制することができる。 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). By setting the content ratio of the flame retardant (B1) to 50 parts by mass or more, the flame retardant backing material composition can exhibit sufficient flame retardancy. By setting the content ratio of the flame retardant (B1) to 200 parts by mass or less, generation of wrinkles can be suppressed.
　本明細書中、「キワツキ」とは、水に溶解した化合物を含む成形品において、成形品の表面に水分が付着した場合に、上記化合物が水分に溶出し、その後、水分の蒸発によって上記化合物が成形品の表面に析出する現象をいう。このように、成形品の表面に化合物が析出すると、難燃裏打材組成物を繊維用の難燃裏打材の形成材料として用いた場合、繊維の表面にシミとして現れることがある。即ち、本明細書中、「耐キワツキ性」とは、難燃裏打材組成物から形成される難燃裏打材の表面に、難燃剤（Ｂ１）等の成分が析出し、キワツキが発生することを抑制する性能を意味する。 In this specification, “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. Thus, when a compound precipitates on the surface of a molded article, when the flame retardant backing material composition is 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.
　難燃裏打材組成物中、界面活性剤（Ｂ２）の含有比は、難燃剤（Ｂ１）１００質量部（固形分換算）に対して、０．５～５．０質量部（固形分換算）である。界面活性剤（Ｂ２）の上記含有比を０．５質量部以上とすることにより、難燃裏打材組成物中での難燃剤（Ｂ１）の分散安定性を向上させることができる。界面活性剤（Ｂ２）の上記含有比を５．０質量部以下とすることにより、界面活性剤（Ｂ２）がキワツキの原因となることを抑制することができる。 In the flame retardant backing material composition, 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. By making 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. By making the said content ratio of surfactant (B2) 5.0 mass parts or less, it can suppress that surfactant (B2) causes a fluff.
　以下、本実施形態の難燃裏打材組成物の各構成成分について、更に詳細に説明する。まず、難燃剤（Ｂ１）、界面活性剤（Ｂ２）、共重合エマルジョン（Ａ）について、次いで、これら以外の添加剤（その他添加剤）について説明する。 Hereinafter, each component of the flame retardant backing material composition of the present embodiment will be described in more detail. First, the flame retardant (B1), the surfactant (B2), and the copolymer emulsion (A) will be described, and then other additives (other additives).
１－１．難燃剤（Ｂ１）
　難燃剤（Ｂ１）は、臭素含有率が６０％以上であり、且つ、分子量が１０００以上である臭素化合物である。 1-1. Flame retardant (B1)
The flame retardant (B1) is a bromine compound having a bromine content of 60% or more and a molecular weight of 1000 or more.
　難燃剤（Ｂ１）の臭素含有率は、上述の通り６０％以上であり、６５％以上であることが好ましく、７０％以上であることが更に好ましく、８０％以上であることが特に好ましい。難燃剤（Ｂ１）の臭素含有率の上限については特に制限されないが、構造上の制約から、難燃剤（Ｂ１）の臭素含有率は、通常８５％以下である。臭素含有率がこれらの範囲内である難燃剤（Ｂ１）を用いることにより、難燃性がより高い難燃剤を用いることになるため、難燃裏打材組成物の難燃性を向上させることができる。 As described above, 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. Although 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. By using 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.
　難燃剤（Ｂ１）の分子量は、上述の通り１０００以上であり、１５００以上であることが好ましく、１８００以上であることが更に好ましい。分子量がこれらの範囲内である難燃剤（Ｂ１）を用いることにより、難燃剤（Ｂ１）が、生体内で、より蓄積され難くなり、環境対応性を向上させることができる。難燃剤（Ｂ１）の分子量の上限については特に制限されないが、難燃裏打材組成物中での分散安定性等の観点から、難燃剤（Ｂ１）の分子量は、３００００以下であることが好ましく、１００００以下であることが更に好ましく、２０００以下であることが特に好ましい。 As described above, the molecular weight of the flame retardant (B1) is 1000 or more, preferably 1500 or more, and more preferably 1800 or more. By using the flame retardant (B1) having a molecular weight within these ranges, 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.
　難燃剤（Ｂ１）の平均粒子径は、１～１００μｍであることが好ましく、５～７０μｍであることが更に好ましく、１０～６０μｍであることが特に好ましい。平均粒子径が１００μｍ以下である難燃剤（Ｂ１）を用いることにより、難燃剤（Ｂ１）の粒子数を相対的に多くし、難燃性能を向上させることができる。難燃剤（Ｂ１）の平均粒子径の下限については、特に制限されないが、分子量が１０００以上であるため、実質的な下限値は５μｍである。 The average particle size of the flame retardant (B1) is preferably 1 to 100 μm, more preferably 5 to 70 μm, and particularly preferably 10 to 60 μm. By using the flame retardant (B1) having an average particle diameter of 100 μm 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 μm.
　難燃剤（Ｂ１）としては、上述の臭素含有率及び分子量の範囲内である限り、特に制限されない。例えば、下記一般式（１）に代表されるような、ブロモフェニル基を有する化合物（臭素化アリールエーテル含有化合物）を挙げることができる。 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).
Figure JPOXMLDOC01-appb-C000001
 　一般式（１）中、ｎは１～１０が好ましく、一般式（１）で表される化合物は、ブロモフェニル基を３つ以上有することが好ましい。一般式（１）中、Ｂｒｍは１～５の臭素付加数を示し、Ｂｒｎは１～４の臭素付加数を示し、Ｂｒｐは０～４の臭素付加数を示す。一般式（１）中、Ａは、－Ｒ、又は、－Ｂｒを示し、Ｒは、それぞれ独立に、水素、ヒドロキシ基、アルキル基、アルデヒド基、カルボニル基、ビニル基等や、アルカリ金属又はアルカリ土類金属等を示す。なお、水素、ヒドロキシ基、アルキル基、アルデヒド基、カルボニル基、ビニル基等は、エーテル結合されていても良い。
Figure JPOXMLDOC01-appb-C000001
 In the general formula (1), n is preferably 1 to 10, and the compound represented by the general formula (1) preferably has three or more bromophenyl groups. In the general formula (1), Brm represents a bromine addition number of 1 to 5, Brn represents a bromine addition number of 1 to 4, and Brp represents a bromine addition number of 0 to 4. In the general formula (1), 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.
　ブロモフェニル基を有する化合物としては、一つ以上の水素原子が臭素原子で置換されたブロモフェニル基を有する化合物であり、ブロモフェニル基の水素原子が臭素原子で置換された数が多くなるほど、好ましい。ブロモフェニル基としては、テトラブロモフェニル基、ペンタブロモフェニル基が特に好ましい。このようなブロモフェニル基を有する化合物は、臭素含有率が相対的に高く、難燃性が高い。 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 . As the bromophenyl group, 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.
　難燃剤（Ｂ１）としては、臭素化ポリスチレンや臭素化ポリフェニルエーテルなどの臭素化高分子化合物を用いることができる。具体的には、１，４－ジペンタブロモフェニルエーテル－２，３，５，６－テトラブロモベンゼン、１，５－ジペンタブロモフェニルエーテル－２，３，４，６－テトラブロモベンゼン（Ｃ６Ｂｒ５－Ｏ－Ｃ４Ｂｒ４－Ｏ－Ｃ６Ｂｒ５）、１，４－ジテトラブロモフェニルエーテル－２，３，５，６－テトラブロモベンゼン（Ｃ６Ｂｒ４－Ｏ－Ｃ４Ｂｒ４－Ｏ－Ｃ６Ｂｒ４）、２，４，６－トリス（２，４，６－トリブロモフェノキシ）－１，３，５－トリアジン等の臭素化化合物を用いることができる。 As the flame retardant (B1), a brominated polymer compound such as brominated polystyrene or brominated polyphenyl ether can be used. Specifically, 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 ) and 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine can be used.
　難燃剤（Ｂ１）の、難燃裏打材組成物中の含有比は、後述する共重合エマルジョン（Ａ）１００質量部（固形分換算）に対して、５０～２００質量部（固形分換算）であり、１００～２００質量部（固形分換算）であることが好ましく、１２０～１７０質量部（固形分換算）であることが更に好ましい。難燃剤（Ｂ１）の上記含有比をこれらの範囲内とすることにより、キワツキの発生を抑制しつつ、難燃性を向上させることができる。 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). By making the said content ratio of a flame retardant (B1) in these ranges, flame retardance can be improved, suppressing generation | occurrence | production of a wrinkle.
１－２．界面活性剤（Ｂ２）
　界面活性剤（Ｂ２）は、難燃剤（Ｂ１）を難燃裏打材組成物の水分散体中で分散安定化させるものであると共に、アニオン性であり、且つ、アンモニウム塩を有する化合物である。界面活性剤（Ｂ２）としては、このような特徴を有している限り特に限定されない。 1-2. Surfactant (B2)
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.
　界面活性剤（Ｂ２）としては、具体的には、ラウリル硫酸アンモニウム、ミリスチル硫酸アンモニウム、ステアリル硫酸アンモニウム、オレイル硫酸アンモニウム等のモノアルキルアニオンアンモニウム塩、ポリオキシエチレンラウリルエーテル硫酸アンモニウム、ポリオキシアルキレンアルケニルエーテル硫酸アンモニウム、ポリアクリル酸アンモニウム等のアニオンアンモニウム塩を側鎖に有するポリマー等を用いることができる。 Specific examples of 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.
　界面活性剤（Ｂ２）の、難燃裏打材組成物中の含有比は、難燃剤（Ｂ１）１００質量部（固形分換算）に対して、０．５～５．０質量部（固形分換算）であり、０．５～３．０質量部（固形分換算）であることが好ましく、０．５～２．０質量部（固形分換算）であることが更に好ましく、１．５～２．０質量部（固形分換算）であることが特に好ましい。界面活性剤（Ｂ２）の上記含有比をこれらの範囲内とすることにより、難燃裏打材組成物中での難燃剤（Ｂ１）の耐キワツキ性と分散安定性をより向上させることができる。 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). By setting the content ratio of the surfactant (B2) within these ranges, the fire resistance and dispersion stability of the flame retardant (B1) in the flame retardant backing material composition can be further improved.
１－３．共重合エマルジョン（Ａ）
　共重合エマルジョン（Ａ）は、難燃裏打材組成物を構成する樹脂成分であるポリマー（Ａ１）を含む水性エマルジョンである。 1-3. Copolymer emulsion (A)
The copolymer emulsion (A) is an aqueous emulsion containing a polymer (A1) which is a resin component constituting the flame retardant backing material composition.
　ポリマー（Ａ１）としては、分散媒中に分散可能なものである限り、特に制限されないが、具体例としては、天然ゴム、ブタジエンゴム、イソプレンゴム、クロロプレンゴム、スチレン・ブタジエン共重合ゴム、ブタジエン・イソプレン共重合ゴム、ブタジエン・スチレン・イソプレン共重合ゴム、アクリロニトリル・ブタジエン共重合ゴム、アクリルゴム等を挙げることができる。これらの中でも、スチレン・ブタジエン系共重合体、α，β－不飽和ニトリル・共役ジエン系共重合体、及びアクリル酸エステル系重合体からなる群より選択される少なくとも一種の重合体であることが好ましい。 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. Among these, at least one polymer selected from the group consisting of a styrene / butadiene copolymer, an α, β-unsaturated nitrile / conjugated diene copolymer, and an acrylate polymer. preferable.
　ポリマー（Ａ１）は、少なくとも一種の官能基で変性されたものであってもよい。官能基としては、例えば、カルボン酸基、Ｎ－メチロール基、グリシジル基、水酸基、スルホン酸基等を挙げることができる。これらの中でも、カルボン酸基が好ましい。 The polymer (A1) may be modified with at least one functional group. Examples of the functional group include a carboxylic acid group, an N-methylol group, a glycidyl group, a hydroxyl group, and a sulfonic acid group. Among these, a carboxylic acid group is preferable.
　ポリマー（Ａ１）が変性されたものである場合、ポリマー（Ａ１）１００質量％中、官能基の含有割合は、０．１～１０．０質量％であることが好ましく、０．５～５．０質量％であることが更に好ましい。官能基の上記含有割合が０．１質量％以上であるポリマー（Ａ１）を含有する難燃裏打材組成物を用いることにより、難燃裏打材の安定性を充分なものとすることができる。官能基の上記含有割合が１０．０質量％以下であるポリマー（Ａ１）とすることにより、製造コストの増加を抑えることができる。 In the case where the polymer (A1) is modified, 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%. By using 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. By making it 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.
　ポリマー（Ａ１）の粒子径は、特に限定されないが、１００～３００ｎｍであることが好ましく、１５０～２５０ｎｍであることが更に好ましく、１８０～２２０ｎｍであることが特に好ましい。これらの範囲内の粒子径を有するポリマー（Ａ１）は、適度な粘度となり、塗工安定性に優れる。 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.
１－４．その他難燃剤（Ｂ３）
　難燃裏打材組成物は、上述の共重合エマルジョン（Ａ）、上述の難燃剤（Ｂ１）、界面活性剤（Ｂ２）に加えて、その他難燃剤（Ｂ３）を含有していることが好ましい。その他難燃剤（Ｂ３）は、難燃剤（Ｂ１）に加えて、難燃性を更に向上させることが可能な難燃剤としての機能を有する。 1-4. Other flame retardants (B3)
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). In addition to the flame retardant (B1), the other flame retardant (B3) has a function as a flame retardant that can further improve the flame retardancy.
　その他難燃剤（Ｂ３）としては、具体的には、三酸化アンチモン、五酸化アンチモン、酸化アルミニウム、酸化マグネシウム等の金属酸化物、リン酸アンモニウム、ポリリン酸アンモニウム、硫酸アンモニウム、リン酸グアニジン、リン酸エステル、ホウ酸亜鉛等の酸化物、水酸化アルミニウム、水酸化マグネシウム、水酸化ジルコニウム、水酸化亜鉛等の金属水酸化物など、従来公知の難燃剤を用いることができる。 Specific examples of 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. 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.
　その他難燃剤（Ｂ３）の、難燃裏打材組成物中の含有比は、難燃剤（Ｂ１）１００質量部（固形分換算）に対して、５～７０質量部（固形分換算）であることが好ましく、１０～５０質量部（固形分換算）であることが更に好ましく、２０～４０質量部（固形分換算）であることが特に好ましい。その他難燃剤（Ｂ３）の上記含有比をこれらの範囲内とすることにより、難燃裏打材組成物の難燃性を更に向上させ、また、キワツキを抑制することができる。 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). In addition, by setting the above content ratio of the flame retardant (B3) within these ranges, the flame retardancy of the flame retardant backing material composition can be further improved, and the wrinkles can be suppressed.
１－５．分散媒（Ｂ４）
　難燃裏打材組成物は、分散媒（Ｂ４）として、水を用いることができる。分散媒（Ｂ４）は、アルコール、或いはアセトン等のケトン類等を含有していても良い。難燃裏打材組成物中、分散媒（Ｂ４）の含有量は、難燃裏打材組成物の固形分濃度や粘度等に応じて、適宜調節することができる。 1-5. 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. In the flame retardant backing material composition, 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.
１－６．その他添加剤
　難燃裏打材組成物は、更にその他添加剤を含有していても良い。その他添加剤としては、例えば、増粘剤、消泡剤、充填剤、分散剤、濡れ剤、顔料等を挙げることができる。 1-6. Other Additives The flame retardant backing material composition may further contain other additives. Examples of other additives include thickeners, antifoaming agents, fillers, dispersants, wetting agents, and pigments.
　増粘剤としては、例えば、キサンタンガム、ポリアクリル酸、ポリアクリル酸アンモニウム、ポリアクリル酸ナトリウム、カルボキシメチルセルロース（ＣＭＣ）、カルボキシメチルセルロースナトリウム（ＣＭＣＮａ）、ポリビニルアルコール（ＰＶＡ）、ポリビニルピロリドン（ＰＶＰ）、メチルビニルエーテル無水マレイン酸共重合体、アルギン酸ナトリウム、アルギン酸プロピレングリコールエステル、ペクチン、ザンタンガム、ローカストビーンガム、グアーガム、アラビアノガラクタン、ヒアルロン酸ナトリウム等を挙げることができる。 Examples of the thickener 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.
　その他添加剤として増粘剤を添加する場合には、増粘剤の含有比は、共重合エマルジョン（Ａ）１００質量部（固形分換算）に対して、０．０１～５質量部（固形分換算）であることが好ましく、０．１～５質量部（固形分換算）であることが更に好ましい。 When a thickener is added as another additive, 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).
　消泡剤としては、例えば、シリコン系、鉱物油系、アセチレン系化合物、アルコール類等を挙げることができる。 Examples of the antifoaming agent include silicon-based, mineral oil-based, acetylene-based compounds, alcohols and the like.
　その他添加剤として消泡剤を添加する場合には、消泡剤の含有比は、共重合エマルジョン（Ａ）１００質量部（固形分換算）に対して、０．０１～５質量部（固形分換算）であることが好ましく、０．１～５質量部（固形分換算）であることが更に好ましい。 When an antifoaming agent is added as an additive, 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).
　充填剤としては、例えば、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、クレー等を挙げることができる。 Examples of the filler include aluminum hydroxide, magnesium hydroxide, calcium carbonate, and clay.
　その他添加剤として充填剤を添加する場合の充填剤の含有量は、充填剤の種類に応じて適宜調整することができる。例えば、充填剤が水酸化アルミニウムの場合、充填剤の含有比は、共重合エマルジョン（Ａ）１００質量部（固形分換算）に対して、１０～１５０質量部（固形分換算）であることが好ましく、５０～１００質量部（固形分換算）であることが更に好ましい。 Other filler content in the case of adding a filler as an additive can be appropriately adjusted according to the type of filler. For example, when the filler is aluminum hydroxide, 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). Preferably, it is 50 to 100 parts by mass (in terms of solid content).
　分散剤としては、例えば、ポリカルボン酸塩系化合物、ポリリン酸塩系化合物、硫酸塩系化合物、非イオン系化合物、アセチレン系化合物等を挙げることができる。 Examples of the dispersant include polycarboxylate compounds, polyphosphate compounds, sulfate compounds, nonionic compounds, acetylene compounds, and the like.
　その他添加剤として分散剤を添加する場合には、分散剤の含有比は、共重合エマルジョン（Ａ）１００質量部（固形分換算）に対して、０．０１～５質量部（固形分換算）であることが好ましく、０．１～１質量部（固形分換算）であることが更に好ましい。 When a dispersant is added as another additive, 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).
２．難燃裏打材組成物の製造方法
　難燃裏打材組成物の製造方法は、難燃剤水分散体（Ｂ）調製工程と、水分散体（Ｂ）と、共重合エマルジョン（Ａ）とを混合する混合工程と、を含むものである。また、難燃裏打材組成物の製造方法は、共重合エマルジョン（Ａ）調製工程を更に含んでいても良い。以下、難燃剤水分散体（Ｂ）調製工程、共重合エマルジョン（Ａ）調製工程、混合工程について、順に説明する。 2. Method for producing flame retardant backing material composition 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. Moreover, the manufacturing method of a flame-retardant backing material composition may further include a copolymer emulsion (A) preparation step. Hereinafter, the flame retardant aqueous dispersion (B) preparation step, copolymer emulsion (A) preparation step, and mixing step will be described in order.
２－１．難燃剤水分散体（Ｂ）調製工程
　難燃剤水分散体（Ｂ）調製工程は、難燃剤（Ｂ１）を、界面活性剤（Ｂ２）を用いて分散安定化させた水分散体（Ｂ）を得る工程である。難燃剤（Ｂ１）は、上述の難燃剤（Ｂ１）であり、臭素含有率が６０％以上であり、且つ、分子量が１０００以上である。界面活性剤（Ｂ２）は、上述の界面活性剤（Ｂ２）であり、アニオン性であり、且つ、アンモニウム塩を有するものである。ここに、その他難燃剤（Ｂ３）を添加しても良い。 2-1. Flame retardant aqueous dispersion (B) preparation process 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.
　難燃剤（Ｂ１）は、界面活性剤（Ｂ２）により分散安定化されることにより、難燃剤（Ｂ１）同士が凝集したり、難燃剤が沈降等したりすることなく、難燃裏打材組成物中で難燃剤としての機能を充分に発揮することが可能である。 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.
　難燃剤（Ｂ１）を、界面活性剤（Ｂ２）を用いて分散安定化させた水分散体（Ｂ）を得る方法としては、例えば、難燃剤（Ｂ１）及び界面活性剤（Ｂ２）を含む混合液を高速撹拌する方法、ビーズミル、ボールミル等による方法、３本ロール等による方法等を挙げることができる。必要な場合、この難燃剤水分散体（Ｂ）調製工程において、その他添加剤を添加し、混合しても良い。 As a method for obtaining 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. Examples thereof include 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. If necessary, other additives may be added and mixed in the flame retardant aqueous dispersion (B) preparation step.
２－２．共重合エマルジョン（Ａ）調製行程
　共重合エマルジョン（Ａ）調製工程は、反応性乳化剤（Ａ２）を用いて重合させて、ポリマー（Ａ１）を含有する共重合エマルジョン（Ａ）を得る工程である。 2-2. Step of preparing copolymer emulsion (A) The step of preparing copolymer emulsion (A) is a step of obtaining copolymer emulsion (A) containing polymer (A1) by polymerization using reactive emulsifier (A2).
　共重合エマルジョン（Ａ）に含有されるポリマー（Ａ１）の合成方法としては、特に限定されず、ラジカル重合、アニオン重合、カチオン重合等、従来公知の各種重合方法を採用することができる。それらの中でも、ポリマー（Ａ１）の重合方法としては、ラジカル重合が好ましく、特に、反応性乳化剤（Ａ２）を用いた乳化重合による合成が特に好ましい。 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.
　ポリマー（Ａ１）を合成するための原料単量体としては、上述の各種ポリマー（Ａ１）の各構成単位を形成し得るモノマーを用いることができる。 As a raw material monomer for synthesizing the polymer (A1), a monomer capable of forming each constituent unit of the various polymers (A1) described above can be used.
　ポリマー（Ａ１）の合成に用いられる反応性乳化剤（Ａ２）としては、スルホン酸基及び／又はサルフェート基を含有する反応性乳化剤；カルボキシル基及び／又はカルボキシレート基を含有する反応性乳化剤；リン酸基及び／又はその塩を含有する反応性乳化剤；リン酸エステル基を含有する反応性乳化剤；アリルスルホン酸、２－メチルアリルスルホン酸等のアリル基含有スルホン酸類又はその塩；イソプレンスルホン酸類又はその塩；（メタ）アクリル酸２－スルホエチル、（メタ）アクリル酸２－スルホプロピル等の（メタ）アクリロイル基含有スルホン酸類又はその塩；（メタ）アクリルアミド－ｔ－ブチルスルホン酸等の（メタ）アクリルアミド基含有スルホン酸類又はその塩などが挙げられる。 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 include group-containing sulfonic acids or salts thereof.
　反応性乳化剤（Ａ２）として、市販品では、例えば、以下商品名で、スルホン酸基及びその塩を有するものとして、「ラテムルＳ－１８０」（花王株式会社製）、「ラテムルＳ－１８０Ａ」（同社製）、「エレミノールＪＳ－２」（三洋化成工業株式会社製）、「エレミノールＪＳ－２０」（同社製）、「エレミノールＲＳ－３０」（同社製）等；サルフェート基及びその塩を有するものとして、「アクアロンＨＳ－１０」（第一工業製薬株式会社製）、「アクアロンＨＳ－１０２５」（同社製）、「アクアロンＫＨ－０５」（同社製）、「アクアロンＫＨ－１０」（同社製）、「アデカリアソープＳＥ－１０」（株式会社ＡＤＥＫＡ製）、「アデカリアソープＳＥ－２０」（同社製）、「アデカリアソープＳＲ－１０２５」（同社製）、「ラテムルＰＤ－１０４」（花王株式会社製）等；リン酸基及びその塩を有するものとして、「ニューフロンティアＡ－２２９Ｅ」（第一工業製薬株式会社製）、「アデカリアソープＰＰ－７０」（株式会社ＡＤＥＫＡ製）、「アデカリアソープＰＰＥ－７１０」（同社製）等；非イオン性親水基を有するものとして、「アクアロンＲＮ－１０」（第一工業製薬株式会社製）、「アクアロンＲＮ－２０」（同社製）、「アクアロンＲＮ－３０」（同社製）、「アクアロンＲＮ－５０」（同社製）等が挙げられる。 As 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" (manufactured by ADEKA Corporation), "Adekaria soap SE-20" (manufactured by the company), "Adekaria soap SR-1025" (manufactured by the company), “Latemul PD-104” (manufactured by Kao Corporation) and the like; those having a phosphate group and a salt thereof, “New Frontier A-229E” (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), “Adekaria Soap PP-70” ( Adeka Soap PPE-710 (manufactured by Adeka Co., Ltd.), etc .; “AQUALON RN-10” (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), “AQUALON RN-” 20 ”(manufactured by the company),“ Aqualon RN-30 ”(manufactured by the company),“ Aqualon RN-50 ”(manufactured by the company), and the like.
　反応性乳化剤（Ａ２）は、１種単独使用でもよく２種以上を併用してもよい。上述の反応性乳化剤（Ａ２）の中でも、裏打材としての難燃性、機械的安定性、及び皮膜耐水性等に優れることから、スルホン酸基及び／又はサルフェート基を有する反応性乳化剤、硫酸基及び／又はその塩を有する反応性乳化剤が好ましく、スルホン酸基及び／又はサルフェート基を有する反応性乳化剤がより好ましい。 The reactive emulsifier (A2) may be used alone or in combination of two or more. Among the above-mentioned reactive emulsifiers (A2), 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. And / 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.
　ポリマー（Ａ１）を合成するに際して、反応性乳化剤（Ａ２）の使用量を、ポリマー（Ａ１）の原料単量体の総量１００質量部（固形分換算）に対して、１．０～５．０質量部（固形分換算）とすることが好ましく、１．０～３．０質量部（固形分換算）とすることが更に好ましく、１．０～２．０質量部（固形分換算）とすることが特に好ましい。反応性乳化剤（Ａ２）の上記使用量を１．０質量部以上とすることにより、反応性乳化剤（Ａ２）の効果を充分に発揮させ、乳化重合を良好に進行させることができる。反応性乳化剤（Ａ２）の上記使用量を５．０質量部以下とすることにより、得られるポリマー（Ａ１）の粘度が過度に上昇することを抑制し、より加工性や塗工性に優れた難燃裏打材組成物を得ることが可能となる。 In synthesizing the polymer (A1), 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. By making the said usage-amount of a reactive emulsifier (A2) into 1.0 mass part or more, the effect of a reactive emulsifier (A2) can fully be exhibited, and emulsion polymerization can be advanced favorable. By making the use amount of the reactive emulsifier (A2) 5.0 parts by mass or less, 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.
　ポリマー（Ａ１）の合成に用いる乳化剤として、上記反応性乳化剤（Ａ２）以外にも、非反応性乳化剤を用いても良い。非反応性乳化剤としては、公知の乳化剤を用いることができ、例えば、ノニオン系乳化剤、アニオン系乳化剤等を用いることができる。これら非反応性乳化剤は、反応性乳化剤（Ａ２）と併用しても良い。 As an emulsifier used for the synthesis of the polymer (A1), a non-reactive emulsifier may be used in addition to the reactive emulsifier (A2). As the non-reactive emulsifier, a known emulsifier can be used. For example, 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).
　ポリマー（Ａ１）の合成に用いる重合開始剤は、上述の反応性乳化剤（Ａ２）を用いた乳化重合を阻害するものでない限り、特に制限されない。 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.
２－３．混合工程
　混合工程は、上述の各調製工程により得られた共重合エマルジョン（Ａ）と、難燃剤水分散体（Ｂ）と、を混合する工程である。 2-3. Mixing step 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).
　共重合エマルジョン（Ａ）と、難燃剤水分散体（Ｂ）とを混合する方法は、特に制限なく、従来公知の方法を採用することができる。必要な場合、この混合工程において、その他添加剤を添加し、混合しても良い。 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.
３．難燃裏打材
　難燃裏打材組成物は、例えば、カーペット、シート、マット、内装等の繊維製品において、裏面に塗布される難燃性の裏打材を形成することができる。 3. Flame Retardant Backing Material 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.
　難燃裏打材を塗布する対象の繊維製品としては、ナイロン、ポリエステル、レーヨン、ビニロン、アクリル等の合成繊維の他、綿、麻、ジュート等の植物繊維等で形成される繊維製品を挙げることができる。 Examples of 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.
　難燃裏打材を塗布する方法としては、特に限定されないが、例えば、ロールコーター法、ダイレクトコート法、ナイフコート法、スプレーコート法などを挙げることができる。ロールコーター法は、バッキング剤を繊維製品に塗布した後に、ロールコーターにてバッキング剤を繊維に十分に含浸させ、次いで乾燥することで仕上げる方法である。 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.
　難燃裏打材又は難燃裏打材組成物の固形分濃度は、２０％以上であることが好ましく、３０％以上であることが更に好ましく、４０％以上であることが特に好ましい。難燃裏打材又は難燃裏打材組成物の固形分濃度を、上述の範囲内とすることにより、難燃裏打材としての加工性や塗工性を良好なものとすることができる。 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. By setting the solid content concentration of the flame retardant backing material or the flame retardant backing material composition within the above-mentioned range, the workability and coating properties as the flame retardant backing material can be improved.
　難燃裏打材又は難燃裏打材組成物の粘度は、１０００～１０００００ｍＰａ・ｓ程度であることが好ましく、５０００～８００００ｍＰａ・ｓ程度であることが更に好ましく、１００００～７００００ｍＰａ・ｓ程度であることが特に好ましい。難燃裏打材又は難燃裏打材組成物の粘度を、上述の範囲内とすることにより、難燃裏打材としての加工性や塗工性を良好なものとすることができる。 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. By setting the viscosity of the flame retardant backing material or the flame retardant backing material composition within the above-mentioned range, the workability and coating properties as the flame retardant backing material can be improved.
　以下、本発明を実施例に基づいて具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.
　まず、各実施例、比較例の難燃裏打材組成物の性能の評価方法ついて説明し、次いで、各実施例、比較例の難燃裏打材組成物の調製方法及び評価結果について説明する。 First, a method for evaluating the performance of the flame retardant backing material composition of each example and comparative example will be described, and then a method for preparing the flame retardant backing material composition of each example and comparative example and evaluation results will be described.
（１）臭素含有率
　難燃剤の臭素含有率は、ＪＩＳ　Ｋ７２２９に記載の酸素フラスコ燃焼法に準拠して前処理した試料を、イオンクロマトグラフィにより測定した。 (1) Bromine content The 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.
　試料の前処理として、具体的には、酸素フラスコ燃焼法において、難燃剤試料２ｍｇを燃焼し、発生した気体を、抱水ヒドラジンを一滴含有する超純水に吸収させ、２５ｍＬに定容した。次に、前処理された試料を、２０倍に希釈してイオンクロマトグラフィにより測定し、下記計算式により臭素濃度を算出した。
Figure JPOXMLDOC01-appb-M000002
 Specifically, as a sample pretreatment, in the oxygen flask combustion method, 2 mg of a flame retardant sample was burned, and the generated gas was absorbed in ultrapure water containing one drop of hydrazine hydrate, and the volume was adjusted to 25 mL. Next, the pretreated sample was diluted 20 times and measured by ion chromatography, and the bromine concentration was calculated by the following formula.
Figure JPOXMLDOC01-appb-M000002
　イオンクロマトグラフィの測定条件は、以下の通りであった。
　　機器名：ダイオネクス製ＩＣＳ－２０００
　　カラム：ＩｏｎＰＡＣ　ＡＧ１８、ＡＳ１８（直径４ｍｍ×長さ２５０ｍｍ）
　　溶離液：ＫＯＨグラジエント（溶離液ジェネレータ使用）
　　試料注入量：５０μＬ
　　検出器：電気伝導度検出器 The measurement conditions for ion chromatography were as follows.
Device name: DIC-2000 manufactured by Dionex
Column: IonPAC AG18, AS18 (diameter 4 mm x length 250 mm)
Eluent: KOH gradient (using eluent generator)
Sample injection volume: 50 μL
Detector: Electric conductivity detector
（２）環境対応性評価
　難燃剤の環境対応性を、難燃剤の数平均分子量を測定することにより評価した。難燃剤の数平均分子量は、飛行時間型質量分析計（ＴＯＦ－ＭＳ）を用いて測定した。測定装置として、ＪＥＯＬ社（日本電子株式会社）製「ＪＭＳ－Ｔ１００ＧＣＶ　ＡｃｃｕＴＯＦ　ＧＣｖ　４Ｇ」を使用し、測定温度条件としては、常温で測定した。環境対応性評価は、以下の判定基準に従った。
　　良：数平均分子量１０００以上（生体内蓄積性が抑制される）
　　不可：数平均分子量１０００未満 (2) Evaluation of environmental compatibility 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). “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
（３）難燃性評価
　難燃裏打材を用いて作製した繊維製品の難燃性を、米国自動車安全基準「ＦＭＶＳＳ　３０２」、即ち日本工業規格「ＪＩＳ－Ｄ１２０１」に準じて評価した。繊維製品としては、難燃裏打材の塗布量が、乾燥状態で、それぞれ４０ｇ／ｍ３、及び８０ｇ／ｍ３となるように塗布した、２種類の繊維製品を用いた。難燃性評価は、以下の判定基準に従った。
　　優：燃焼速度０～１００ｍｍ／ｍｉｎ未満
　　不可：燃焼速度１００ｍｍ／ｍｉｎ以上 (3) Flame Retardancy Evaluation The flame retardancy of a textile product produced using a flame retardant backing material was evaluated according to US automobile safety standard “FMVSS 302”, that is, Japanese Industrial Standard “JIS-D1201”. The textile coating amount of the flame燃裏punching material, in the dry state, was coated to a 40 g / m 3, and 80 g / m 3 respectively, using two kinds of textiles. The flame retardant evaluation was in accordance with the following criteria.
Excellent: Burning speed 0 to less than 100 mm / min Impossible: Burning speed 100 mm / min or more
（４）分散安定性評価
　難燃裏打材組成物の分散安定性は、分散直後の粘度（分散直後粘度）と、分散させてから５０℃で７日間放置後の粘度（放置後粘度）とを測定し、下記計算式により算出される粘度経時変化率を評価した。
　　粘度経時変化率＝［（放置後粘度－分散直後粘度）／分散直後粘度］×１００
　分散安定性評価は、以下の判定基準に従った。
　　良：粘度経時変化率が１００％以下
　　不可：粘度経時変化率が１００％超、又は、分散直後に固化する場合 (4) Evaluation of dispersion stability The dispersion stability of the flame retardant backing material composition is determined by the viscosity immediately after dispersion (viscosity immediately after dispersion) and the viscosity after standing for 7 days at 50 ° C. after dispersion (viscosity after standing). The viscosity was measured with the following formula to evaluate the rate of change with time of viscosity.
Viscosity change rate with time = [(viscosity after standing-viscosity immediately after dispersion) / viscosity immediately after dispersion] × 100
The dispersion stability was evaluated according to the following criteria.
Good: Viscosity change rate with time is 100% or less Impossible: Viscosity change rate with time exceeds 100%, or solidifies immediately after dispersion
（５）耐キワツキ性評価
　難燃裏打材を用いて作製した繊維製品についての耐キワツキ性を評価した。具体的には、以下の方法により評価した。まず、上記繊維製品からなる、長さ３０ｍｍ、幅３０ｍｍに裁断した試験片を水平な台の上に載置した。試験片の中心部に熱湯（８５～９０℃の蒸留水）を１～３ｍＬ滴下し、常温で２４時間放置して、乾燥させた。乾燥後の試験片を観察し、以下の判定基準に従い着色の有無を評価した。
　　優：着色しなかった
　　良：ほとんど着色しなかった
　　可：僅かに着色した
　　不可：著しく着色した (5) Evaluation of resistance to wrinkles Evaluation of resistance to wrinkles was performed on fiber products produced using a flame-retardant backing material. Specifically, the evaluation was performed by the following method. First, a test piece made of the above-described textile product and cut into a length of 30 mm and a width of 30 mm was placed on a horizontal table. 1 to 3 mL of hot water (85 to 90 ° C. distilled water) was added dropwise to the center of the test piece and left to stand at room temperature for 24 hours to dry. The test piece after drying was observed and the presence or absence of coloring was evaluated according to the following criteria.
Excellent: Not colored Good: Little colored Good: Slightly colored Not acceptable: Remarkably colored
（実施例１～３０、比較例１～２６）
　実施例１～３０、及び比較例１～２６の難燃裏打材、及びこれら難燃裏打材を用いた繊維製品を以下のように作製した。 (Examples 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.
　共重合エマルジョンを調製するためのポリマーの原料単量体として、以下の単量体を以下の配合比で用いた。なお、下記単量体成分（ａ）及び（ｂ）の合計を１００質量部とした。
単量体成分（ａ）（エチレン系不飽和カルボン酸単量体）：
　アクリル酸（東亞合成社製）　１．０質量部
単量体成分（ｂ）（アクリル酸エステル単量体）：
　２－エチルヘキシルアクリレート（東亞合成社製）　９２．０質量部
　ブチルアクリレート（東亞合成社製）　３．０質量部
　アクリロニトリル（三菱レーヨン社製）　４．０質量部 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
　上記単量体成分を用いて、各実施例及び比較例のポリマーを以下のように合成した。まず、予め水に分散させておいた乳化剤０．０４質量部と水４１質量部とを、反応容器に仕込み、窒素気流下において撹拌して、乳化剤分散液を調製した。乳化剤分散液の温度を７０℃まで昇温した。次いで、単量体成分（ａ）及び（ｂ）の混合溶液（単量体成分（ａ）及び（ｂ）の合計１００質量部）と、水２７質量部と、乳化剤２質量部とを加え、撹拌することによりプレ乳化した。このプレ乳化した単量体溶液と、予め調製しておいた触媒水溶液（０．０５％過硫酸アンモニウム水溶液）とを、並列にて、８０℃で、約３時間かけて、反応容器中に滴下した。滴下終了後、引き続き８０℃で約１時間保温した。冷却後、２５％アンモニア水０．５質量部を加えた。このようにして、固形分濃度５４．５％、粘度９００ｍＰａ・ｓ、ポリマー粒子径２００ｎｍ前後のアクリルエマルジョン、即ち、共重合エマルジョンを得た。 Using the above monomer components, 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.
　難燃剤水分散体は、難燃剤と界面活性剤と水を、特殊機械社製のＴＫオートミキサーを使用して高速撹拌（周速度２０００ｍ／ｍｉｎ）して調製した。 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.
　次に、調製した共重合エマルジョンと、難燃剤水分散体と、その他添加剤とを、パドル式撹拌機を使用して混合し、難燃裏打材として使用する水性エマルジョン、即ち、難燃裏打材組成物を調製した。 Next, 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.
　調製した難燃裏打材組成物を難燃裏打材として、以下のようにして、繊維製品を作製した。長さ３００ｍｍ、幅２００ｍｍのポリエステル製の繊維布に、ブレードコーターによる塗工方法により難燃裏打材を塗布した。 Using the prepared flame retardant backing material composition as a flame retardant backing material, 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.
　得られた難燃裏打材及び繊維製品を用いて、各種評価を実施した。評価結果を表１～表５に示す。 Various evaluations were performed using the obtained flame-retardant backing material and fiber products. The evaluation results are shown in Tables 1 to 5.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　表１～表５中、乳化剤としては、以下のものを用いた。
［反応性乳化剤１］：α－スルホ－ω－（１－（アルコキシ）メチル－２－（２－プロペニルオキシ）エトキシ）－ポリ（オキシ－１，２－エタンジイル）アンモニウム塩（ＡＤＥＫＡ社製「アデカリアソープＳＲ－１０２５（商品名）」）
［反応性乳化剤２］：アルキルアリルスルホコハク酸塩（三洋化成工業社製「エレミノールＪＳ－２０（商品名）」）
［反応性乳化剤３］：ポリオキシエチレンノニルプロペニルフェニルエーテル硫酸エステルアンモニウム（第一工業製薬社製「アクアロンＨＳ－１０（商品名）」）
［反応性乳化剤４］：ポリオキシアルキレンアルケニルエーテル硫酸アンモニウム（花王社製「ラテムルＰＤ－１０４（商品名）」）
［非反応性乳化剤１（ノニオン系乳化剤）］：ポリオキシエチレンアルキルエーテル（花王社製「エマルゲン１１０８（商品名）」）
［非反応性乳化剤２（アニオン系乳化剤）］：ドデシルベンゼンスルホン酸ナトリウム（花王社製「ネオペレックスＧ（商品名）」）
［非反応性乳化剤３（アニオン系乳化剤）］：ラウリル硫酸アンモニウム（花王社製「ラテムルＡＤ２５（商品名）」） In Tables 1 to 5, the following were used as emulsifiers.
[Reactive emulsifier 1]: α-sulfo-ω- (1- (alkoxy) methyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl) ammonium salt (“ADEKA” manufactured by ADEKA) Rear soap SR-1025 (trade name) ")
[Reactive emulsifier 2]: Alkylallylsulfosuccinate (“Eleminol JS-20 (trade name)” manufactured by Sanyo Chemical Industries)
[Reactive emulsifier 3]: Ammonium polyoxyethylene nonylpropenyl phenyl ether sulfate (“AQUALON HS-10 (trade name)” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
[Reactive emulsifier 4]: Ammonium polyoxyalkylene alkenyl ether sulfate (“Latemul PD-104 (trade name)” manufactured by Kao Corporation)
[Non-reactive emulsifier 1 (nonionic emulsifier)]: polyoxyethylene alkyl ether (“Emulgen 1108 (trade name)” manufactured by Kao Corporation)
[Non-reactive emulsifier 2 (anionic emulsifier)]: Sodium dodecylbenzenesulfonate (Neoperex G (trade name) manufactured by Kao)
[Non-reactive emulsifier 3 (anionic emulsifier)]: ammonium lauryl sulfate (“Latemul AD25 (trade name)” manufactured by Kao Corporation)
　表１～表５中、難燃剤としては、以下のものを用いた。
［難燃剤１］：Ｃｈｅｍｔｕｒａ　Ｃｏｒｐｏｒａｔｉｏｎ社製「Ｅｍｅｒａｌｄ　Ｉｎｎｏｖａｔｉｏｎ　１０００（商品名）」〔数平均分子量１８７０、臭素含有率８０％〕
［難燃剤２］：２，４，６－トリス（２，４，６－トリブロモフェノキシ）－１，３，５－トリアジン（第一工業製薬社製「ピロガードＳＲ－２４５（商品名）」）〔数平均分子量１０７０、臭素含有率６７％〕
［難燃剤３］：臭素化ポリスチレン（鈴裕化学社製「ファイアカットＦ－８０００（商品名）」）〔数平均分子量３００００、臭素含有率６６％〕
［難燃剤４］：デカブロムシフェニルエーテル（東ソー社製「フレームカット１１０Ｒ（商品名）」）〔数平均分子量９６０、臭素含有率８２％〕
［難燃剤５］：デカブロムジフェニルエタン（Ｃｈｅｍｔｕｒａ　Ｃｏｒｐｏｒａｔｉｏｎ社製「Ｆｉｒｅ　Ｍａｓｔｅｒ　２１００Ｒ（商品名）」）〔数平均分子量９７０、臭素含有率８１％〕
［難燃剤６］：ＴＢＡ－ビス（２，３－ジブロモプロピルエーテル）（鈴裕化学社製「ファイアカットＰ－６８０（商品名）」）〔数平均分子量８６０、臭素含有率７３％〕
［難燃剤７］：ビス［３，５－ジブロモ－４－（２，３－ジブロモプロポキシ）フェニル］スルホン（鈴裕化学社製「ファイアカットＰ－６５ＣＮ（商品名）」）〔数平均分子量９６０、臭素含有率６５％〕
［難燃剤８］：トリアリルイソシアヌレート６臭化物（鈴裕化学社製「ファイアカットＦＣＰ－６５Ｎ（商品名）」）〔数平均分子量７２０、臭素含有率６６％〕
［難燃剤９］：テトラブロモビスフェノールＡ（東ソー社製「フレームカット１２０Ｇ（商品名）」）〔数平均分子量５４０、臭素含有率５９％〕
［その他難燃剤１］：三酸化アンチモン（日本精鉱社製「ＰＡＴＯＸ－Ｍ（商品名）」） In Tables 1 to 5, the following were used as flame retardants.
[Flame retardant 1]: “Emerald Innovation 1000 (trade name)” manufactured by Chemtura Corporation [number average molecular weight 1870, bromine content 80%]
[Flame Retardant 2]: 2,4,6-Tris (2,4,6-tribromophenoxy) -1,3,5-triazine (“Pyroguard SR-245 (trade name)” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) [Number average molecular weight 1070, bromine content 67%]
[Flame Retardant 3]: Brominated polystyrene (“Fire Cut F-8000 (trade name)” manufactured by Suzuhiro Chemical Co., Ltd.) [number average molecular weight 30000, bromine content 66%]
[Flame Retardant 4]: Decaboromsiphenyl ether (“Frame Cut 110R (trade name)” manufactured by Tosoh Corporation) [Number average molecular weight 960, bromine content 82%]
[Flame Retardant 5]: Decabromodiphenylethane (“Fire Master 2100R (trade name)” manufactured by Chemtura Corporation) [number average molecular weight 970, bromine content 81%]
[Flame Retardant 6]: TBA-bis (2,3-dibromopropyl ether) (“Fire Cut P-680 (trade name)” manufactured by Suzuhiro Chemical Co., Ltd.) [number average molecular weight 860, bromine content 73%]
[Flame Retardant 7]: Bis [3,5-dibromo-4- (2,3-dibromopropoxy) phenyl] sulfone (“Fire Cut P-65CN (trade name)” manufactured by Suzuhiro Chemical Co., Ltd.) [number average molecular weight 960 , Bromine content 65%]
[Flame Retardant 8]: triallyl isocyanurate hexabromide (“Fire Cut FCP-65N (trade name)” manufactured by Suzuhiro Chemical Co., Ltd.) [number average molecular weight 720, bromine content 66%]
[Flame Retardant 9]: Tetrabromobisphenol A (“Frame Cut 120G (trade name)” manufactured by Tosoh Corporation) [number average molecular weight 540, bromine content 59%]
[Other flame retardant 1]: Antimony trioxide (“PATOX-M (trade name)” manufactured by Nippon Seiko Co., Ltd.)
　表１～表５中、界面活性剤としては、以下のものを用いた。
［界面活性剤１］：ラウリル硫酸アンモニウム（花王社製「ラテムルＡＤ２５（商品名）」）
［界面活性剤２］：ポリオキシエチレンラウリルエーテル硫酸アンモニウム（第一工業製薬社製「ハイテールＬＡ－１０（商品名）」）
［界面活性剤３］：ポリオキシアルキレンアルケニルエーテル硫酸アンモニウム（花王社製「ラテムルＰＤ－１０４（商品名）」）
［界面活性剤４］：ポリアクリル酸アンモニウム（第一工業製薬社製「シャロールＤＣ－４０２Ｐ（商品名）」）
［界面活性剤５］：アセチレングリコール系界面活性剤（日信化学工業社製「サーフィノールＣＴ－１３６（商品名）」）
［界面活性剤６］：ポリオキシエチレンアルキルエーテル（花王社製「エマルゲン１１０８（商品名）」）
［界面活性剤７］：ドデシルベンゼンスルホン酸ナトリウム（花王社製「ネオペレックスＧ（商品名）」）
［界面活性剤８］：ポリカルボン酸ナトリウム（サンノプコ社製「ＳＮディスパーサント５０３４（商品名）」） In Tables 1 to 5, the following were used as surfactants.
[Surfactant 1]: Ammonium lauryl sulfate (“Latemul AD25 (trade name)” manufactured by Kao Corporation)
[Surfactant 2]: Polyoxyethylene lauryl ether ammonium sulfate (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., “High Tail LA-10 (trade name)”)
[Surfactant 3]: Ammonium polyoxyalkylene alkenyl ether sulfate (“Latemul PD-104 (trade name)” manufactured by Kao Corporation)
[Surfactant 4]: Ammonium polyacrylate (“Charol DC-402P (trade name)” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
[Surfactant 5]: Acetylene glycol surfactant (“Surfinol CT-136 (trade name)” manufactured by Nissin Chemical Industry Co., Ltd.)
[Surfactant 6]: Polyoxyethylene alkyl ether (“Emulgen 1108 (trade name)” manufactured by Kao Corporation)
[Surfactant 7]: Sodium dodecylbenzenesulfonate (“Neoperex G (trade name)” manufactured by Kao Corporation)
[Surfactant 8]: Sodium polycarboxylate (“SN Dispersant 5034 (trade name)” manufactured by San Nopco)
　表１～表５中、その他添加剤としては、以下のものを用いた。
［消泡剤］：シリコン（東レ・ダウコーニング社製「ＦＳアンチフォーム０１３Ａ（商品名）」）
［増粘剤］：ポリアクリル酸（サンノプコ社製「ＳＮシックナー６１８（商品名）」） In Tables 1 to 5, the following were used as other additives.
[Antifoamer]: Silicone (“FS Antifoam 013A (trade name)” manufactured by Toray Dow Corning)
[Thickener]: Polyacrylic acid (“SN thickener 618 (trade name)” manufactured by San Nopco)
　表１に記載の実施例１～１０と、表２に記載の比較例１～１２との比較により、臭素含有率が６０％以上であり、且つ、分子量が１０００以上である難燃剤（Ｂ１）を、共重合エマルジョン（Ａ）１００質量部（固形分換算）に対して５０～２００質量部（固形分換算）含有すると共に、特定の界面活性剤（Ｂ２）を特定量含有する難燃裏打材組成物は、十分な難燃性及び耐キワツキ性を示し、且つ、環境問題にも対応したものであることが判る。 According to a comparison between Examples 1 to 10 shown in Table 1 and Comparative Examples 1 to 12 shown in Table 2, 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.
　表３に記載の実施例１１～２１と、表４に記載の比較例１３～２４との比較により、アニオン性であり、且つ、アンモニウム塩を有する界面活性剤（Ｂ２）を難燃剤（Ｂ１）１００質量部（固形分換算）に対して０．５～５．０質量部（固形分換算）含有すると共に、特定の難燃剤（Ｂ１）を特定量含有する難燃裏打材組成物は、十分な難燃性及び耐キワツキ性を示し、且つ、環境問題にも対応したものであることが判る。 By comparing Examples 11 to 21 shown in Table 3 with Comparative Examples 13 to 24 shown in Table 4, 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.
　表５に記載の実施例２２～３０より、各種乳化剤を用いて合成されたポリマーを含む難燃裏打材組成物は、十分な難燃性及び耐キワツキ性を示し、且つ、環境問題にも対応したものであることが判る。中でも、反応性乳化剤を、単量体の総量１００質量部（固形分換算）に対して１．０～５．０質量部（固形分換算）の配合比で用いてポリマーを合成した場合に、耐キワツキ性が顕著に向上していることが判る。 From Examples 22 to 30 shown in Table 5, 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.
　本発明の難燃裏打材組成物は、ポリエステル系繊維製品等の難燃裏打材として用いることが可能である。本発明の難燃裏打材は、自動車や航空機等のシート、マット、内装等の繊維製品の裏打材として用いることが可能である。 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.

Claims (7)

  1. 　共重合エマルジョン（Ａ）と、
    　臭素含有率が６０％以上であり、且つ、分子量が１０００以上である難燃剤（Ｂ１）と、
    　前記難燃剤（Ｂ１）を分散安定化させると共に、アニオン性であり、且つ、アンモニウム塩を有する界面活性剤（Ｂ２）と、
    を含み、
    　前記共重合エマルジョン（Ａ）１００質量部（固形分換算）に対して、前記難燃剤（Ｂ１）５０～２００質量部（固形分換算）を含有し、前記難燃剤（Ｂ１）１００質量部（固形分換算）に対して、前記界面活性剤（Ｂ２）０．５～５．０質量部（固形分換算）を含有する難燃裏打材組成物。     Copolymer emulsion (A),
    A flame retardant (B1) having a bromine content of 60% or more and a molecular weight of 1000 or more;
    The flame retardant (B1) is dispersed and stabilized, an anionic surfactant (B2) having an ammonium salt,
    Including
    It contains 50 to 200 parts by mass (in terms of solid content) of the flame retardant (B1) with respect to 100 parts by mass (in terms of solid content) of the copolymer emulsion (A), and 100 parts by mass (in terms of solids) of the flame retardant (B1). The flame retardant backing material composition containing 0.5 to 5.0 parts by mass (in terms of solid content) of the surfactant (B2) with respect to (in terms of the component).
  2. 　金属酸化物を更に含む請求項１に記載の難燃裏打材組成物。 The flame retardant backing material composition according to claim 1, further comprising a metal oxide.
  3. 　前記共重合エマルジョン（Ａ）に含有されるポリマー（Ａ１）が、単量体の総量１００質量部（固形分換算）に対して、反応性乳化剤（Ａ２）１．０～５．０質量部（固形分換算）を用いて重合されたポリマーである請求項１又は２に記載の難燃裏打材組成物。 The polymer (A1) contained in the copolymer emulsion (A) is 1.0 to 5.0 parts by mass of the reactive emulsifier (A2) with respect to 100 parts by mass (in terms of solid content) of monomers. The flame retardant backing material composition according to claim 1, which is a polymer polymerized using a solid content conversion.
  4. 　前記ポリマー（Ａ１）が、（１）スチレン・ブタジエン系共重合体、（２）α、β－不飽和ニトリル・共役ジエン系共重合体、及び（３）アクリル系重合体からなる群より選択される少なくとも一種の重合体を含有する請求項１～３のいずれか一項に記載の難燃裏打材組成物。 The polymer (A1) is selected from the group consisting of (1) a styrene / butadiene copolymer, (2) an α, β-unsaturated nitrile / conjugated diene copolymer, and (3) an acrylic polymer. The flame retardant backing material composition according to any one of claims 1 to 3, comprising at least one polymer.
  5. 　請求項１～４のいずれか一項に記載の難燃裏打材組成物により形成された難燃裏打材。 A flame retardant backing material formed from the flame retardant backing material composition according to any one of claims 1 to 4.
  6. 　臭素含有率が６０％以上であり、且つ、分子量が１０００以上である難燃剤（Ｂ１）を、アニオン性であり、且つ、アンモニウム塩を有する界面活性剤（Ｂ２）を用いて分散安定化させた水分散体（Ｂ）を得る難燃剤水分散体（Ｂ）調製工程と、
    　前記水分散体（Ｂ）と、共重合エマルジョン（Ａ）を混合する混合工程と、
    を含む難燃裏打材組成物の製造方法。     A flame retardant (B1) having a bromine content of 60% or more and a molecular weight of 1000 or more was dispersed and stabilized by using an anionic surfactant (B2) having an ammonium salt. Flame retardant water dispersion (B) preparation step for obtaining water dispersion (B);
    A mixing step of mixing the aqueous dispersion (B) and the copolymer emulsion (A);
    A method for producing a flame retardant backing material composition comprising:
  7. 　単量体の総量１００質量部（固形分換算）に対して、反応性乳化剤（Ａ２）１．０～５．０質量部（固形分換算）を用いて重合させて、ポリマー（Ａ１）を含有する共重合エマルジョン（Ａ）を得る共重合エマルジョン（Ａ）調製工程を更に有する請求項６に記載の難燃裏打材組成物の製造方法。 Polymerization is carried out using 1.0 to 5.0 parts by mass of the reactive emulsifier (A2) (in terms of solid content) with respect to 100 parts by mass (in terms of solid content) of the monomer, and the polymer (A1) is contained. The method for producing a flame retardant backing material composition according to claim 6, further comprising a step of preparing a copolymer emulsion (A) to obtain a copolymer emulsion (A).
PCT/JP2014/071331 2013-09-12 2014-08-12 Flame-retardant lining material composition, flame-retardant lining material, and method for producing flame-retardant lining material composition WO2015037385A1 (en)

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CN115490907A (en) * 2022-11-02 2022-12-20 南宁斤美新材料科技有限公司 Preparation method of high-temperature-resistant oil-stain-resistant composite plastic

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