US20070135551A1 - Coating composition and vehicle interior material - Google Patents

Coating composition and vehicle interior material Download PDF

Info

Publication number
US20070135551A1
US20070135551A1 US11/636,471 US63647106A US2007135551A1 US 20070135551 A1 US20070135551 A1 US 20070135551A1 US 63647106 A US63647106 A US 63647106A US 2007135551 A1 US2007135551 A1 US 2007135551A1
Authority
US
United States
Prior art keywords
coating composition
flame retardant
halogen flame
ammonium polyphosphate
fine particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US11/636,471
Inventor
Harukazu Okuda
Ichiro Tanii
Norio Nakamura
Kazuyuki Matsumura
Akira Yamamoto
Toshiaki Ihara
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nissin Chemical Industry Co Ltd
Original Assignee
Nissin Chemical Industry Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nissin Chemical Industry Co Ltd filed Critical Nissin Chemical Industry Co Ltd
Assigned to NISSIN CHEMICAL INDUSTRY CO., LTD. reassignment NISSIN CHEMICAL INDUSTRY CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: IHARA, TOSHIAKI, MATSUMURA, KAZUKI, NAKAMURA, NORIO, OKUDA, HARUKAZU, TANII, ICHIRO, YAMAMOTO, AKIRA
Publication of US20070135551A1 publication Critical patent/US20070135551A1/en
Priority to US12/832,807 priority Critical patent/US7923074B2/en
Abandoned legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/32Phosphorus-containing compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D143/00Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/02Homopolymers or copolymers of monomers containing phosphorus
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/01Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016Flame-proofing or flame-retarding additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/29Compounds containing one or more carbon-to-nitrogen double bonds
    • C08K5/31Guanidine; Derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477Six-membered rings
    • C08K5/3492Triazines
    • C08K5/34928Salts
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/02Ingredients treated with inorganic substances
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02Emulsion paints including aerosols
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18Fireproof paints including high temperature resistant paints

Definitions

  • This invention relates to coating compositions for vehicle interior materials such as car seats, car mats, and ceiling members, and vehicle interior materials coated therewith.
  • halogenated flame retardants such as decabromodiphenyl ether for imparting flame retardance.
  • non-halogen flame retardants have drawbacks of poor flame retardance and poor water resistance, as compared with the halogenated flame retardants.
  • JP-A 9-13037 discloses such a coating agent comprising a polyamide resin, acrylic resin or styrene resin although the resulting flame retardant is still less resistant to water.
  • JP-A 10-110083 and JP-A 2003-171878 disclose that ammonium polyphosphate particles can be admixed with acrylic emulsions in a stable manner when they are surface coated with melamine resins or the like.
  • the emulsion compatibility is improved.
  • the coating agent has a low degree of curing, coatings applied and dried to substrates, typically fabrics are not improved in water resistance. For example, a problem has been pointed out that the coating surface becomes slimy when contacted with water.
  • the coating agent has a higher degree of curing, the above problem is overcome, but formaldehyde is detectable, raising an environmental problem.
  • the known non-halogen flame retardants include metal hydroxides such as aluminum hydroxide and magnesium hydroxide and phosphate esters, which are considered less flame retardant than the halogenated flame retardants.
  • An object of the present invention is to provide a coating composition for use with vehicle interior materials such as car seats, car mats, and ceiling members, comprising a non-halogen flame retardant, which composition has physical properties comparable to coating compositions comprising conventional halogenated flame retardants. Another object is to provide a vehicle interior material coated with the coating composition.
  • the inventors have found that when a certain amount of a non-halogen flame retardant in which non-halogen flame retardant particles are surface coated with hydrophobic inorganic oxide fine particles is added to a synthetic resin emulsion, there is obtained a novel coating composition comprising a non-halogen flame retardant, which composition has physical properties comparable to coating compositions comprising conventional halogenated flame retardants.
  • This coating composition is suitable to apply to vehicle interior materials such as car seats, car mats, and ceiling members.
  • the present invention provides a coating composition
  • a coating composition comprising a synthetic resin emulsion and one or more non-halogen flame retardant in which phosphorus and nitrogen-containing non-halogen flame retardant particles are surface coated with hydrophobic inorganic oxide fine particles, the coated non-halogen flame retardant being added in an amount of 1 to 300 parts by weight per 100 parts by weight as solids of the synthetic resin emulsion.
  • a vehicle interior material coated with the composition is also contemplated.
  • the coating composition comprising a non-halogen flame retardant according to the invention has physical and flame retardant properties comparable to coating compositions comprising conventional halogenated flame retardants and is thus suitable to apply to vehicle interior members such as car seats, car mats and ceiling members.
  • the coating composition of the invention is defined as comprising a synthetic resin emulsion and a non-halogen flame retardant in which phosphorus and nitrogen-containing non-halogen flame retardant particles are surface coated with hydrophobic inorganic oxide fine particles, which retardant is simply referred to as “coated non-halogen flame retardant,” hereinafter.
  • the coated non-halogen flame retardant is added in an amount of 1 to 300 parts by weight per 100 parts by weight of solids of the synthetic resin emulsion.
  • the synthetic resin emulsions used herein include vinyl chloride resin base emulsions, (meth)acrylate resin base emulsions, styrene/acrylate copolymer base emulsions, urethane resin base emulsions, silicone resin base emulsions, fluororesin base emulsions, epoxy resin base emulsions, ethylene/vinyl acetate copolymer base emulsions, and rubber base emulsions such as styrene-butadiene rubber (SBR) and acrylonitrile-butadiene rubber (NBR) base emulsions. These emulsions may be used alone or in admixture of two or more.
  • SBR styrene-butadiene rubber
  • NBR acrylonitrile-butadiene rubber
  • (meth)acrylate resin base emulsions Preference is given to (meth)acrylate resin base emulsions, styrene/acrylate copolymer base emulsions, urethane resin base emulsions, ethylene/vinyl acetate copolymer base emulsions, and rubber base emulsions such as SBR and NBR.
  • (meth)acrylate resin refers to acrylate or methacrylate resins.
  • the above-listed synthetic resin emulsions may be synthesized by emulsion polymerization. Instead, any of commercially available synthetic resin emulsions may be used. Examples of commercially available synthetic resin emulsions include, but are not limited to, (meth)acrylate resin base emulsions such as Vinyblan 2598 by Nisshin Chemical Co., Ltd. and Aron A-104 by Toa Synthesis Co., Ltd.; styrene/acrylate copolymer base emulsions such as Vinyblan 2590 by Nisshin Chemical Co., Ltd.
  • urethane resin base emulsions such as Hydran HW-311 and HW-301 by Dainippon Ink & Chemicals, Inc. and Permarine UA-150 by Sanyo Chemical Industry Co., Ltd.
  • ethylene/vinyl acetate copolymer base emulsions such as Sumikaflex 400 and 752 by Sumitomo Chemical Co., Ltd. and Panflex OM-4000 by Kurare Co., Ltd.
  • rubber base emulsions such as Nalstar SR-100 and SR-112 by Nippon A&L Inc. and Nipol 1561 by Nippon Zeon Co., Ltd.
  • radical polymerization is generally employed for synthesis.
  • the starting monomers used are monomers containing unsaturated groups having a radical polymerization ability.
  • Suitable unsaturated group-containing monomers include ethylene and propylene; chlorine-containing monomers such as vinyl chloride and vinylidene chloride; vinyl carboxylate monomers such as vinyl acetate and vinyl propionate; aromatic vinyl monomers such as styrene and ⁇ -methylstyrene; conjugated diene monomers such as 1,3-butadiene and 2-methyl-1,3-butadiene; ethylenically unsaturated monocarboxylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate; ethylenically unsaturated dicarboxylic acid esters such as dimethyl itaconate, diethyl maleate, monobutyl maleate, monoethyl fumarate, and dibutyl fumarate; ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and
  • any well-known emulsion polymerization techniques may be employed.
  • the foregoing monomers and polymerization aids e.g., emulsifiers such as alkyl sulfate salts, polymerization initiators such as ammonium persulfate, chain transfer agents such as mercaptans, pH regulators such as sodium carbonate, antifoaming agents
  • emulsifiers such as alkyl sulfate salts
  • polymerization initiators such as ammonium persulfate
  • chain transfer agents such as mercaptans
  • pH regulators such as sodium carbonate
  • Suitable emulsifiers used in the emulsion polymerization include surfactants of the following classes (1) to (4), which may be used alone or in admixture of two or more.
  • surfactants are generally used in amounts of 0.3 to 20% by weight, preferably 0.5 to 10% by weight based on the weight of the monomers.
  • polymerization initiator used for the emulsion polymerization examples include persulfates such as ammonium persulfate, potassium persulfate; azo compounds such as 2,2′-diamidino-2,2′-azopropane dihydrogen chloride salt and azobisisobutyronitrile; and peroxides such as cumene hydroperoxide, benzoyl peroxide and hydrogen peroxide.
  • peroxides such as cumene hydroperoxide, benzoyl peroxide and hydrogen peroxide.
  • redox initiators such as potassium persulfate and sodium hydrogen sulfite are also useful.
  • the amount of the polymerization initiator used is generally 0.1 to 5% by weight, preferably 0.2 to 2% by weight based on the weight of the monomers.
  • the emulsion polymerization is generally conducted at a temperature of 10 to 90° C., desirably 50 to 80° C. and for a time of about 3 to about 20 hours.
  • This polymerization is desirably conducted in an atmosphere of an inert gas such as nitrogen gas.
  • the flame retardant used in the coating composition of the invention is a non-halogen flame retardant in which phosphorus and nitrogen-containing non-halogen flame retardant particles are surface coated with hydrophobic inorganic oxide fine particles.
  • Flame retardants containing only phosphorus include, for example, phosphoric acid esters, but are less flame retardant than the halogenated flame retardants.
  • the inventors select as the flame retardant component a flame retardant containing both phosphorus and nitrogen for achieving an improved flame retardant effect.
  • Examples of the phosphorus and nitrogen-containing non-halogen flame retardant include guanidine phosphate, ammonium phosphate, melamine phosphate, ammonium polyphosphate, ammonium polyphosphate surface treated with melamine, and ammonium polyphosphate surface treated with silicon compounds, which may be used alone or in admixture of two or more. Inter alia, ammonium polyphosphates are preferred. Useful ammonium polyphosphates are commercially available. These flame retardants are in the form of particles, preferably having an average particle size of 3 to 25 ⁇ m, especially 5 to 18 ⁇ m.
  • the average particle size is determined as a weight average value or median diameter, for example, using a particle size distribution analyzer relying on the laser light diffraction technique.
  • the silicon compound-surface-treated ammonium polyphosphate is preferably obtained by treating or coating surfaces of ammonium polyphosphate particles with an alkoxysilane containing a functional group such as carboxyl or amino group or a partial hydrolyzate thereof, using an in-liquid drying process.
  • hydrophobic inorganic oxide fine particles used herein are not particularly limited as long as they are hydrophobic inorganic oxides (i.e., having hydrophobic groups). Examples include, but are not limited to, hydrophobic silicon oxide, titanium oxide, zinc oxide, aluminum oxide, and cerium oxide. Inter alia, hydrophobic silicon oxide or silica is best suited from the cost and performance aspects.
  • silica which can be used herein is generally divided into two types: dry silicas which are typically obtained by decomposition of silicon halides or by heat reduction of silica sand followed by oxidation in air; and wet silicas which are typically obtained by direct decomposition of sodium silicate with mineral acids such as sulfuric acid.
  • Silica produced by a sol-gel method involving hydrolysis of alkoxysilanes is also acceptable.
  • silica is useful as long as it has been provided with hydrophobic groups such as alkyl groups, typically methyl, by treating with hydrophobic surface-treating agents including organosilazanes such as hexamethyldisilazane, organoalkoxysilanes such as methyltrimethoxysilane, and organopolysiloxanes such as organohydrogenpolysiloxanes.
  • hydrophobic surface-treating agents including organosilazanes such as hexamethyldisilazane, organoalkoxysilanes such as methyltrimethoxysilane, and organopolysiloxanes such as organohydrogenpolysiloxanes.
  • a measure of hydrophobicity is preferably represented by a degree of hydrophobicity, which is at least 45, preferably 50 to 70.
  • the degree of hydrophobicity is determined by a methanol titration test of adding silica fine particles to a methanol/water mixture for wetting the fine particles, and determining the percentage of methanol in the methanol/water mixture, as shown below.
  • A is titer of methanol (ml)
  • B is amount of deionized water (ml)
  • Lager values indicate higher hydrophobicity whereas smaller values indicate higher hydrophillicity.
  • the hydrophobic inorganic oxide fine particles typically hydrophobic silica fine particles have an average particle size sufficient to deposit on the phosphorus and nitrogen-containing non-halogen flame retardant particles, preferably from 0.001 to 5 ⁇ m. An average particle size of 0.001 to 2 ⁇ m is more preferred.
  • the shape of fine particles is not particularly limited and may be spherical or irregular.
  • Non-halogen flame retardant particles can be coated with the hydrophobic inorganic oxide fine particles by feeding 100 parts by weight of non-halogen flame retardant particles and 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight of hydrophobic inorganic oxide fine particles to a suitable mixer such as a ball mill, V-type mixer, ribbon mixer, or screw mixer, equipped with a high-speed agitation means having a revolution capability of about 100 to 5,000 rpm where they are agitated and mixed. Then the hydrophobic inorganic oxide fine particles deposit on and adhere to surfaces of the non-halogen flame retardant particles, yielding a coated non-halogen flame retardant.
  • a suitable mixer such as a ball mill, V-type mixer, ribbon mixer, or screw mixer
  • the coated non-halogen flame retardant preferably has an average particle size of 3 to 35 ⁇ m, especially 5 to 20 ⁇ m. In the practice of the invention, one or more coated non-halogen flame retardants may be used.
  • the synthetic resin emulsion and the coated non-halogen flame retardant are mixed in such a proportion that 1 to 300 parts by weight, preferably 5 to 200 parts by weight of the coated non-halogen flame retardant is present per 100 parts by weight as solids of the synthetic resin emulsion. Less than 1 part of the flame retardant provides an insufficient flame retardant effect whereas more than 300 parts of the flame retardant fails to provide a coating with a practical strength and increases the cost.
  • the coating composition of the invention may contain additives, for example, cellulosic water-soluble polymers such as hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose and methyl cellulose; synthetic water-soluble polymers such as fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, polyacrylic acid and salts thereof, polymethacrylic acid and salts thereof, polyacrylamide, and alkali viscosity buildup type acrylic emulsions; bases such as ammonia, triethylamine, and sodium hydroxide; polyethylene wax, anti-foaming agents, leveling agents, tackifiers, preservatives, anti-bacterial agents, and anti-rusting agents as long as they do not compromise the objects of the invention.
  • cellulosic water-soluble polymers such as hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose and methyl cellulose
  • synthetic water-soluble polymers such as fully saponified polyvinyl alcohol, partially sap
  • the coating composition of the invention is prepared by intimately mixing predetermined amounts of the foregoing components in a conventional manner.
  • the coating composition thus obtained should preferably have a solids content of 30 to 70% by weight, more preferably 40 to 60% by weight.
  • the coating composition thus obtained is advantageously applicable to various substrates which must be rendered flame retardant, for example, vehicle interior materials such as car seats, car mats and ceiling members.
  • any of well-known applicators such as gravure roll coaters, knife coaters, and reverse roll coaters may be used.
  • the substrates include woven fabrics and knitted goods of polyester, nylon or the like and non-woven fabrics of polyester, polypropylene or the like.
  • the composition may be used as such or after thickening with commercially available thickeners such as alkali viscosity buildup type acrylic emulsions.
  • the coating composition should preferably be adjusted to a viscosity of 10,000 to 50,000 mPa ⁇ s at 25° C., more preferably 20,000 to 40,000 mPa ⁇ s at 25° C., as measured by a Brookfield viscometer.
  • the coating weight of the coating composition is generally 30 to 600 g/m 2 , desirably 50 to 500 g/m 2 , in a dry state. After application, the coating is desirably dried at a temperature of about 100 to 180° C. for about 1 to 10 minutes.
  • Typical vehicle interior materials are car seats, car mats and ceiling members, for which not only flame retardance, but also texture are key features.
  • the texture is measured by the 45 degree cantilever method of JIS L1079 and expressed by stiffness.
  • the texture requirement differs depending on the identity of vehicle interior material.
  • a soft texture is required as expressed by a stiffness less than or equal to 100.
  • a hard texture is required as expressed by a stiffness of greater than 100.
  • the coating weight of the coating composition is desirably 30 to 200 g/m 2 in a dry state in the case of car seats, and the coating weight is desirably 300 to 600 g/m 2 in a dry state in the case of car mats and ceiling members.
  • a 3-L glass container equipped with a stirrer, reflux condenser and thermometer was thoroughly purged of air with nitrogen.
  • To the glass container were added 1,000 parts of deionized water, 20 parts of Emal 0 (Kao Co., Ltd., sodium laurylsulfate), and 30 parts of DKSNL-600 (Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene lauryl ether). Stirring was started.
  • the internal temperature of the container was raised to 80° C., whereupon a mixture of 580 parts butyl acrylate, 300 parts ethyl acrylate, 100 parts acrylonitrile and 20 parts acrylic acid was continuously fed over 4 hours and then a mixture of 4 parts ammonium persulfate and 50 parts water continuously fed over 4 hours. Thereafter, reaction was effected at 80° C. for one hour. The reaction solution was cooled to 30° C., yielding an acrylate resin base emulsion having a solids content of 49.5%.
  • This operation yielded silica-coated, organosilicon resin surface treated ammonium polyphosphate.
  • the coated ammonium polyphosphate was observed under a SEM, finding that silica fines adhered to surfaces of organosilicon resin surface treated ammonium polyphosphate particles to provide a dense and tight coverage.
  • ammonium polyphosphate FR CROS S 10 by Budenheim, average particle size 8 ⁇ m
  • a linear silicone fluid KF-96H by Shin-Etsu Chemical Co., Ltd.
  • the mixture was agitated for 30 minutes, and the toluene was removed under reduced pressure.
  • the residue was ground on a grinder, yielding silicone-treated ammonium polyphosphate having an average particle size of 10 ⁇ m.
  • a thickener Boncoat V by Dainippon Ink & Chemicals, Inc., alkali viscosity buildup type acrylic emulsion
  • 25% aqueous ammonia were added to the dispersion for thickening, yielding a coating composition having an increased viscosity of 30,000 ⁇ 3,000 mPa ⁇ s as measured at 25° C. by a Brookfield viscometer.
  • the formulation of these coating compositions is shown in Tables 2 and 3.
  • a predetermined amount of each coating composition was applied to a commercial polyester woven fabric with a weight of 400 g/m 2 and a commercial polypropylene non-woven fabric with a weight of 700 g/m 2 , and dried at 130° C. for 5 minutes, completing samples.
  • the samples of Examples and Comparative Examples were examined for sew line fatigue, flame retardance, water resistance, stiffness, formaldehyde emission, and heat resistance.
  • the samples of polyester woven fabric with a weight of 400 g/m 2 were used as car seats and examined for sew line fatigue, flame retardance, water resistance, stiffness, formaldehyde emission, and heat resistance, with the results shown in Table 4.
  • the samples of polypropylene non-woven fabric with a weight of 700 g/m 2 were used as car mats and examined for flame retardance, water resistance, stiffness, formaldehyde emission, and heat resistance, with the results shown in Table 5.
  • test methods and evaluation criteria are described below.
  • the specimen was mounted on a sew line fatigue testing machine (Yamaguchi Chemical Industry Co., Ltd.) which was operated under a load of 3 kg over 2,500 cycles. With the load of 3 kg kept applied, the sew line fatigue of the specimen was observed through a scale magnifier.
  • swipe line fatigue refers to the distance between the sewing thread moved in the loading direction by repeated fatigue and the thread within fabric located nearest thereto, measured in unit 0.1 mm. An average of measurements at two locations is the sew line fatigue of the test specimen.
  • a water droplet having a diameter of 5 mm was dropped on the coated surface of fabric. It was examined whether or not the coated surface became slimy.
  • a 2-L Tedlar® Bag (Dupont) was charged with 50 cm 2 of a sample, purged with nitrogen and sealed. The bag was held at 65° C. for 2 hours. Using a gas detector 91L (Gas Tech Co., Ltd.), formaldehyde was detected.
  • polyester woven fabric and polypropylene non-woven fabric coated with different coating compositions were heat treated at 150° C. for one hour, after which a change of color on the coating surface was visually examined.

Abstract

A coating composition comprising 100 pbw as solids of a synthetic resin emulsion and 1-300 pbw of a non-halogen flame retardant in which P and N-containing non-halogen flame retardant particles are surface coated with hydrophobic inorganic oxide fine particles is applicable to vehicle interior materials.

Description

    CROSS-REFERENCE TO RELATED APPLICATION
  • This non-provisional application claims priority under 35 U.S.C. §119(a) on Patent Application No. 2005-357289 filed in Japan on Dec. 12, 2005, the entire contents of which are hereby incorporated by reference.
  • TECHNICAL FIELD
  • This invention relates to coating compositions for vehicle interior materials such as car seats, car mats, and ceiling members, and vehicle interior materials coated therewith.
  • BACKGROUND ART
  • Most coating agents applied to vehicle interior materials such as car seats, car mats, and ceiling members in the prior art are halogenated flame retardants such as decabromodiphenyl ether for imparting flame retardance. The recent concern about the environment demands to replace conventional halogenated flame retardants by non-halogen flame retardants. The non-halogen flame retardants, however, have drawbacks of poor flame retardance and poor water resistance, as compared with the halogenated flame retardants.
  • To overcome these problems, an attempt was made to encapsulate a water-soluble non-halogen flame retardant such as ammonium polyphosphate with a coating agent. JP-A 9-13037 discloses such a coating agent comprising a polyamide resin, acrylic resin or styrene resin although the resulting flame retardant is still less resistant to water.
  • JP-A 10-110083 and JP-A 2003-171878 disclose that ammonium polyphosphate particles can be admixed with acrylic emulsions in a stable manner when they are surface coated with melamine resins or the like. The emulsion compatibility is improved. However, if the coating agent has a low degree of curing, coatings applied and dried to substrates, typically fabrics are not improved in water resistance. For example, a problem has been pointed out that the coating surface becomes slimy when contacted with water. On the other hand, if the coating agent has a higher degree of curing, the above problem is overcome, but formaldehyde is detectable, raising an environmental problem.
  • In addition to the ammonium polyphosphate, the known non-halogen flame retardants include metal hydroxides such as aluminum hydroxide and magnesium hydroxide and phosphate esters, which are considered less flame retardant than the halogenated flame retardants.
  • There exists a need for coating compositions comprising non-halogen flame retardants having physical properties comparable to coating compositions comprising conventional halogenated flame retardants.
  • SUMMARY OF THE INVENTION
  • An object of the present invention is to provide a coating composition for use with vehicle interior materials such as car seats, car mats, and ceiling members, comprising a non-halogen flame retardant, which composition has physical properties comparable to coating compositions comprising conventional halogenated flame retardants. Another object is to provide a vehicle interior material coated with the coating composition.
  • The inventors have found that when a certain amount of a non-halogen flame retardant in which non-halogen flame retardant particles are surface coated with hydrophobic inorganic oxide fine particles is added to a synthetic resin emulsion, there is obtained a novel coating composition comprising a non-halogen flame retardant, which composition has physical properties comparable to coating compositions comprising conventional halogenated flame retardants. This coating composition is suitable to apply to vehicle interior materials such as car seats, car mats, and ceiling members.
  • Therefore, the present invention provides a coating composition comprising a synthetic resin emulsion and one or more non-halogen flame retardant in which phosphorus and nitrogen-containing non-halogen flame retardant particles are surface coated with hydrophobic inorganic oxide fine particles, the coated non-halogen flame retardant being added in an amount of 1 to 300 parts by weight per 100 parts by weight as solids of the synthetic resin emulsion. A vehicle interior material coated with the composition is also contemplated.
  • BENEFITS OF THE INVENTION
  • The coating composition comprising a non-halogen flame retardant according to the invention has physical and flame retardant properties comparable to coating compositions comprising conventional halogenated flame retardants and is thus suitable to apply to vehicle interior members such as car seats, car mats and ceiling members.
  • DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • The coating composition of the invention is defined as comprising a synthetic resin emulsion and a non-halogen flame retardant in which phosphorus and nitrogen-containing non-halogen flame retardant particles are surface coated with hydrophobic inorganic oxide fine particles, which retardant is simply referred to as “coated non-halogen flame retardant,” hereinafter. The coated non-halogen flame retardant is added in an amount of 1 to 300 parts by weight per 100 parts by weight of solids of the synthetic resin emulsion.
  • Emulsion
  • The synthetic resin emulsions used herein include vinyl chloride resin base emulsions, (meth)acrylate resin base emulsions, styrene/acrylate copolymer base emulsions, urethane resin base emulsions, silicone resin base emulsions, fluororesin base emulsions, epoxy resin base emulsions, ethylene/vinyl acetate copolymer base emulsions, and rubber base emulsions such as styrene-butadiene rubber (SBR) and acrylonitrile-butadiene rubber (NBR) base emulsions. These emulsions may be used alone or in admixture of two or more. Preference is given to (meth)acrylate resin base emulsions, styrene/acrylate copolymer base emulsions, urethane resin base emulsions, ethylene/vinyl acetate copolymer base emulsions, and rubber base emulsions such as SBR and NBR. It is noted that the term “(meth)acrylate resin” refers to acrylate or methacrylate resins.
  • The above-listed synthetic resin emulsions may be synthesized by emulsion polymerization. Instead, any of commercially available synthetic resin emulsions may be used. Examples of commercially available synthetic resin emulsions include, but are not limited to, (meth)acrylate resin base emulsions such as Vinyblan 2598 by Nisshin Chemical Co., Ltd. and Aron A-104 by Toa Synthesis Co., Ltd.; styrene/acrylate copolymer base emulsions such as Vinyblan 2590 by Nisshin Chemical Co., Ltd. and Movinyl 975A by Clariant Polymer Co., Ltd.; urethane resin base emulsions such as Hydran HW-311 and HW-301 by Dainippon Ink & Chemicals, Inc. and Permarine UA-150 by Sanyo Chemical Industry Co., Ltd.; ethylene/vinyl acetate copolymer base emulsions such as Sumikaflex 400 and 752 by Sumitomo Chemical Co., Ltd. and Panflex OM-4000 by Kurare Co., Ltd.; and rubber base emulsions such as Nalstar SR-100 and SR-112 by Nippon A&L Inc. and Nipol 1561 by Nippon Zeon Co., Ltd.
  • When the foregoing synthetic resin emulsions are prepared by emulsion polymerization, radical polymerization is generally employed for synthesis. The starting monomers used are monomers containing unsaturated groups having a radical polymerization ability.
  • Examples of suitable unsaturated group-containing monomers include ethylene and propylene; chlorine-containing monomers such as vinyl chloride and vinylidene chloride; vinyl carboxylate monomers such as vinyl acetate and vinyl propionate; aromatic vinyl monomers such as styrene and α-methylstyrene; conjugated diene monomers such as 1,3-butadiene and 2-methyl-1,3-butadiene; ethylenically unsaturated monocarboxylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate; ethylenically unsaturated dicarboxylic acid esters such as dimethyl itaconate, diethyl maleate, monobutyl maleate, monoethyl fumarate, and dibutyl fumarate; ethylenically unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids such as itaconic acid, maleic acid, and fumaric acid; epoxy group-containing monomers such as glycidyl methacrylate; alcoholic hydroxyl group-containing monomers such as 2-hydroxyethyl methacrylate; alkoxyl group-containing monomers such as methoxyethyl acrylate; nitrile group-containing monomers such as acrylonitrile; amide group-containing monomers such as acrylic amide; amino group-containing monomers such as dimethylaminoethyl methacrylate; and monomers having at least two ethylenically unsaturated groups in a molecule such as divinyl benzene and allyl methacrylate.
  • For the emulsion polymerization, any well-known emulsion polymerization techniques may be employed. The foregoing monomers and polymerization aids (e.g., emulsifiers such as alkyl sulfate salts, polymerization initiators such as ammonium persulfate, chain transfer agents such as mercaptans, pH regulators such as sodium carbonate, antifoaming agents) may be added together at the initial, or continuously over the course. Alternatively, some of them may be added continuously or in divided portions during the polymerization.
  • Suitable emulsifiers used in the emulsion polymerization include surfactants of the following classes (1) to (4), which may be used alone or in admixture of two or more.
    • (1) Anionic surfactants, such as alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate ester salts, alkylbenzene sulfonate salts, alkyldiphenylether disulfonate salts, alkyl naphthalene sulfonate salts, fatty acid salts, dialkylsulfosuccinate salts, alkylphosphate salts, polyoxyethylene alkylphenyl phosphate ester salts.
    • (2) Nonionic surfactants, such as polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyalkylene alkyl ethers, polyoxyethylene derivatives, glycerin fatty acid esters, polyoxyethylene hardened castor oil, polyoxyethylene alkyl amines, alkyl alkanol amides, or acetylene alcohol, acetylene glycol and ethylene oxide addition products thereof.
    • (3) Cationic surfactants, such as alkyl trimethylammonium chlorides, dialkyl dimethylammonium chlorides, alkylbenzylammonium chlorides, and alkylamine salts.
    • (4) Polymerizable surfactants having a double bond with a radical polymerization ability in a molecule, such as alkylallylsulfosuccinic acid salts, methacryloyl polyoxyalkylene sulfate ester salts, polyoxyethylene nonylpropenylphenyl ether sulfate ester salts.
  • These surfactants are generally used in amounts of 0.3 to 20% by weight, preferably 0.5 to 10% by weight based on the weight of the monomers.
  • Examples of the polymerization initiator used for the emulsion polymerization include persulfates such as ammonium persulfate, potassium persulfate; azo compounds such as 2,2′-diamidino-2,2′-azopropane dihydrogen chloride salt and azobisisobutyronitrile; and peroxides such as cumene hydroperoxide, benzoyl peroxide and hydrogen peroxide. Well-known redox initiators such as potassium persulfate and sodium hydrogen sulfite are also useful. The amount of the polymerization initiator used is generally 0.1 to 5% by weight, preferably 0.2 to 2% by weight based on the weight of the monomers.
  • The emulsion polymerization is generally conducted at a temperature of 10 to 90° C., desirably 50 to 80° C. and for a time of about 3 to about 20 hours. This polymerization is desirably conducted in an atmosphere of an inert gas such as nitrogen gas.
  • Flame Retardant
  • The flame retardant used in the coating composition of the invention is a non-halogen flame retardant in which phosphorus and nitrogen-containing non-halogen flame retardant particles are surface coated with hydrophobic inorganic oxide fine particles.
  • Flame retardants containing only phosphorus include, for example, phosphoric acid esters, but are less flame retardant than the halogenated flame retardants. The inventors select as the flame retardant component a flame retardant containing both phosphorus and nitrogen for achieving an improved flame retardant effect.
  • Examples of the phosphorus and nitrogen-containing non-halogen flame retardant include guanidine phosphate, ammonium phosphate, melamine phosphate, ammonium polyphosphate, ammonium polyphosphate surface treated with melamine, and ammonium polyphosphate surface treated with silicon compounds, which may be used alone or in admixture of two or more. Inter alia, ammonium polyphosphates are preferred. Useful ammonium polyphosphates are commercially available. These flame retardants are in the form of particles, preferably having an average particle size of 3 to 25 μm, especially 5 to 18 μm. It is noted that the average particle size is determined as a weight average value or median diameter, for example, using a particle size distribution analyzer relying on the laser light diffraction technique. The silicon compound-surface-treated ammonium polyphosphate is preferably obtained by treating or coating surfaces of ammonium polyphosphate particles with an alkoxysilane containing a functional group such as carboxyl or amino group or a partial hydrolyzate thereof, using an in-liquid drying process.
  • It has been found that excellent water repellency is exerted by coating surfaces of phosphorus and nitrogen-containing non-halogen flame retardant particles with hydrophobic inorganic oxide fine particles.
  • The hydrophobic inorganic oxide fine particles used herein are not particularly limited as long as they are hydrophobic inorganic oxides (i.e., having hydrophobic groups). Examples include, but are not limited to, hydrophobic silicon oxide, titanium oxide, zinc oxide, aluminum oxide, and cerium oxide. Inter alia, hydrophobic silicon oxide or silica is best suited from the cost and performance aspects.
  • The silica which can be used herein is generally divided into two types: dry silicas which are typically obtained by decomposition of silicon halides or by heat reduction of silica sand followed by oxidation in air; and wet silicas which are typically obtained by direct decomposition of sodium silicate with mineral acids such as sulfuric acid. Silica produced by a sol-gel method involving hydrolysis of alkoxysilanes is also acceptable. Any type of silica is useful as long as it has been provided with hydrophobic groups such as alkyl groups, typically methyl, by treating with hydrophobic surface-treating agents including organosilazanes such as hexamethyldisilazane, organoalkoxysilanes such as methyltrimethoxysilane, and organopolysiloxanes such as organohydrogenpolysiloxanes.
  • A measure of hydrophobicity is preferably represented by a degree of hydrophobicity, which is at least 45, preferably 50 to 70. The degree of hydrophobicity is determined by a methanol titration test of adding silica fine particles to a methanol/water mixture for wetting the fine particles, and determining the percentage of methanol in the methanol/water mixture, as shown below.
  • [Measurement of Hydrophobicity]
    • (1) Charge 0.2 g of sample to a 500 ml-flask.
    • (2) Add 50 ml of deionized water thereto and agitate the mixture with a stirrer.
    • (3) Drop methanol to the mixture from a buret while agitating, and read the dropping amount of methanol when sample is wholly dispersed to deionized water.
    • (4) Calculate hydrophobicity from the following equation.
      Hydrophobicity=100/(A+B)
      wherein
  • A is titer of methanol (ml)
  • B is amount of deionized water (ml)
  • Lager values indicate higher hydrophobicity whereas smaller values indicate higher hydrophillicity.
  • The hydrophobic inorganic oxide fine particles, typically hydrophobic silica fine particles have an average particle size sufficient to deposit on the phosphorus and nitrogen-containing non-halogen flame retardant particles, preferably from 0.001 to 5 μm. An average particle size of 0.001 to 2 μm is more preferred. The shape of fine particles is not particularly limited and may be spherical or irregular.
  • Surfaces of the non-halogen flame retardant particles can be coated with the hydrophobic inorganic oxide fine particles by feeding 100 parts by weight of non-halogen flame retardant particles and 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight of hydrophobic inorganic oxide fine particles to a suitable mixer such as a ball mill, V-type mixer, ribbon mixer, or screw mixer, equipped with a high-speed agitation means having a revolution capability of about 100 to 5,000 rpm where they are agitated and mixed. Then the hydrophobic inorganic oxide fine particles deposit on and adhere to surfaces of the non-halogen flame retardant particles, yielding a coated non-halogen flame retardant.
  • The coated non-halogen flame retardant preferably has an average particle size of 3 to 35 μm, especially 5 to 20 μm. In the practice of the invention, one or more coated non-halogen flame retardants may be used.
  • The synthetic resin emulsion and the coated non-halogen flame retardant (i.e., phosphorus and nitrogen-containing non-halogen flame retardant particles surface coated with hydrophobic inorganic oxide fine particles) are mixed in such a proportion that 1 to 300 parts by weight, preferably 5 to 200 parts by weight of the coated non-halogen flame retardant is present per 100 parts by weight as solids of the synthetic resin emulsion. Less than 1 part of the flame retardant provides an insufficient flame retardant effect whereas more than 300 parts of the flame retardant fails to provide a coating with a practical strength and increases the cost.
  • In addition to the above-mentioned components, the coating composition of the invention may contain additives, for example, cellulosic water-soluble polymers such as hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose and methyl cellulose; synthetic water-soluble polymers such as fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, polyacrylic acid and salts thereof, polymethacrylic acid and salts thereof, polyacrylamide, and alkali viscosity buildup type acrylic emulsions; bases such as ammonia, triethylamine, and sodium hydroxide; polyethylene wax, anti-foaming agents, leveling agents, tackifiers, preservatives, anti-bacterial agents, and anti-rusting agents as long as they do not compromise the objects of the invention.
  • The coating composition of the invention is prepared by intimately mixing predetermined amounts of the foregoing components in a conventional manner. The coating composition thus obtained should preferably have a solids content of 30 to 70% by weight, more preferably 40 to 60% by weight.
  • The coating composition thus obtained is advantageously applicable to various substrates which must be rendered flame retardant, for example, vehicle interior materials such as car seats, car mats and ceiling members.
  • In applying the coating composition to substrates, any of well-known applicators, such as gravure roll coaters, knife coaters, and reverse roll coaters may be used. The substrates include woven fabrics and knitted goods of polyester, nylon or the like and non-woven fabrics of polyester, polypropylene or the like.
  • In applying the coating composition to substrates, the composition may be used as such or after thickening with commercially available thickeners such as alkali viscosity buildup type acrylic emulsions. On use, the coating composition should preferably be adjusted to a viscosity of 10,000 to 50,000 mPa·s at 25° C., more preferably 20,000 to 40,000 mPa·s at 25° C., as measured by a Brookfield viscometer.
  • The coating weight of the coating composition is generally 30 to 600 g/m2, desirably 50 to 500 g/m2, in a dry state. After application, the coating is desirably dried at a temperature of about 100 to 180° C. for about 1 to 10 minutes.
  • Typical vehicle interior materials are car seats, car mats and ceiling members, for which not only flame retardance, but also texture are key features. The texture is measured by the 45 degree cantilever method of JIS L1079 and expressed by stiffness. The texture requirement differs depending on the identity of vehicle interior material. In the case of car seats, a soft texture is required as expressed by a stiffness less than or equal to 100. In the case of car mats and ceiling members, on the other hand, a hard texture is required as expressed by a stiffness of greater than 100. In general, the coating weight of the coating composition is desirably 30 to 200 g/m2 in a dry state in the case of car seats, and the coating weight is desirably 300 to 600 g/m2 in a dry state in the case of car mats and ceiling members.
  • EXAMPLE
  • Preparation Examples (PE), Examples (EX), and Comparative Examples (CE) are given below for further illustrating the invention although the invention is not limited to these Examples. All parts and % are by weight.
  • Preparation Example 1
  • A 3-L glass container equipped with a stirrer, reflux condenser and thermometer was thoroughly purged of air with nitrogen. To the glass container were added 1,000 parts of deionized water, 20 parts of Emal 0 (Kao Co., Ltd., sodium laurylsulfate), and 30 parts of DKSNL-600 (Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene lauryl ether). Stirring was started.
  • The internal temperature of the container was raised to 80° C., whereupon a mixture of 580 parts butyl acrylate, 300 parts ethyl acrylate, 100 parts acrylonitrile and 20 parts acrylic acid was continuously fed over 4 hours and then a mixture of 4 parts ammonium persulfate and 50 parts water continuously fed over 4 hours. Thereafter, reaction was effected at 80° C. for one hour. The reaction solution was cooled to 30° C., yielding an acrylate resin base emulsion having a solids content of 49.5%.
  • Preparation Examples 2 to 4
  • Several emulsions were obtained by effecting emulsion polymerization as in Preparation Example 1. The composition of the emulsions of Preparation Examples 1 to 4 and a commercial synthetic resin emulsion is shown in Table 1.
  • Preparation Example 5
  • To a ribbon mixer were fed 100 parts of ammonium polyphosphate (Pecoflame TC204P by Clariant, average particle size 8 μm) and 10 parts of hydrophobic silica (degree of hydrophobicity 45, average particle size 1.6 μm) which had been hydrophobized by contacting dry silica having a specific surface area of 120 m2/g with dimethyldichlorosilane diluted with nitrogen and steam at 500° C. such that a carbon content per unit surface area fell in the range of 6.0 to 7.0×10−5 g/m3. The mixer was operated at a high speed of 1,000 rpm for one minute for agitation mixing. This operation yielded silica-coated ammonium polyphosphate. The coated ammonium polyphosphate was observed under a scanning electron microscope (SEM), finding that silica fines adhered to surfaces of ammonium polyphosphate particles to provide a dense and tight coverage.
  • Preparation Example 6
  • To a ribbon mixer were fed 100 parts of ammonium polyphosphate surface treated with amino-containing silicone oligomer (FRX-304 by Shin-Etsu Chemical Co., Ltd., average particle size 8 μm) and 10 parts of hydrophobic silica (degree of hydrophobicity 45, average particle size 1.6 μm) which had been hydrophobized by contacting dry silica having a specific surface area of 120 m2/g with dimethyldichlorosilane diluted with nitrogen and steam at 500° C. such that a carbon content per unit surface area fell in the range of 6.0 to 7.0×10−5 g/m3. The mixer was operated at a high speed (1,000 rpm) for one minute for agitation mixing. This operation yielded silica-coated, organosilicon resin surface treated ammonium polyphosphate. The coated ammonium polyphosphate was observed under a SEM, finding that silica fines adhered to surfaces of organosilicon resin surface treated ammonium polyphosphate particles to provide a dense and tight coverage.
  • Preparation Example 7
  • To 100 parts of ammonium polyphosphate (FR CROS S 10 by Budenheim, average particle size 8 μm) were added 5 parts of a linear silicone fluid (KF-96H by Shin-Etsu Chemical Co., Ltd.) and 100 parts of toluene. The mixture was agitated for 30 minutes, and the toluene was removed under reduced pressure. The residue was ground on a grinder, yielding silicone-treated ammonium polyphosphate having an average particle size of 10 μm.
  • Examples 1 to 7 and Comparative Examples 1 to 8
  • To a stainless steel container was added 100 parts of each of the emulsions of Preparation Examples 1 to 4 or a commercial emulsion. Agitation was started. With agitation continued, a predetermined amount of a dispersion liquid (solids 60%) of each of the treated ammonium polyphosphates of Preparation Examples 5 to 7 or commercial ammonium polyphosphate in water with the aid of a surfactant Latemul ASK (by Kao Corp.) was added, followed by one hour of agitation. Thereafter, deionized water was added for adjusting the solids content to 50±1%. Then a thickener Boncoat V (by Dainippon Ink & Chemicals, Inc., alkali viscosity buildup type acrylic emulsion) and 25% aqueous ammonia were added to the dispersion for thickening, yielding a coating composition having an increased viscosity of 30,000±3,000 mPa·s as measured at 25° C. by a Brookfield viscometer. The formulation of these coating compositions is shown in Tables 2 and 3.
  • A predetermined amount of each coating composition was applied to a commercial polyester woven fabric with a weight of 400 g/m2 and a commercial polypropylene non-woven fabric with a weight of 700 g/m2, and dried at 130° C. for 5 minutes, completing samples.
  • The samples of Examples and Comparative Examples were examined for sew line fatigue, flame retardance, water resistance, stiffness, formaldehyde emission, and heat resistance. The samples of polyester woven fabric with a weight of 400 g/m2 were used as car seats and examined for sew line fatigue, flame retardance, water resistance, stiffness, formaldehyde emission, and heat resistance, with the results shown in Table 4. The samples of polypropylene non-woven fabric with a weight of 700 g/m2 were used as car mats and examined for flame retardance, water resistance, stiffness, formaldehyde emission, and heat resistance, with the results shown in Table 5.
  • The test methods and evaluation criteria are described below.
  • 1. Sew Line Fatigue
  • Two pairs of pieces of 10 cm wide and 10 cm long were cut out from each of warp and weft directions. To the back surface of each piece, a urethane foam slab (density 0.02 g/cm3, thickness 5 mm) and a backing fabric (nylon spun-bonded fabric, 40 g/m2) of the same size were laid to form a laminate. Two laminates were laid with their front surfaces mated each other. Using a sewing machine, the assembly was sewed at 1 cm inside from the side edge. In this way, two sets of specimens were prepared for each of warp and weft directions. The specimen was mounted on a sew line fatigue testing machine (Yamaguchi Chemical Industry Co., Ltd.) which was operated under a load of 3 kg over 2,500 cycles. With the load of 3 kg kept applied, the sew line fatigue of the specimen was observed through a scale magnifier.
  • The term “sew line fatigue” refers to the distance between the sewing thread moved in the loading direction by repeated fatigue and the thread within fabric located nearest thereto, measured in unit 0.1 mm. An average of measurements at two locations is the sew line fatigue of the test specimen.
  • Rating Criterion
      • ◯: moving distance≦2.2 mm
      • ×: moving distance>2.2 mm
        2. Flame Retardance
  • Examined by the test method of US Federal Motor Vehicle Safety Standard FMVS S-302.
  • Rating Criterion for Car Seat
      • ◯: burnt distance≦38 mm
      • ×: burnt distance>38 mm
  • Rating Criterion for Car Mat
      • ◯: burnt distance≦38 mm+burning time≦60 sec or burning rate≦10 cm/min
      • ×: burnt distance>38 mm+burning time>60 sec+burning rate>10 cm/min
        3. Water Resistance
  • A water droplet having a diameter of 5 mm was dropped on the coated surface of fabric. It was examined whether or not the coated surface became slimy.
  • Rating Criterion
      • ⊚: not slimy, no penetration of water into coated surface
      • ◯: not slimy
      • Δ: somewhat slimy
      • ×: heavily slimy
        4. Stiffness
  • Examined by the 45° cantilever method of JIS L1079 (5.17 A method). The higher the stiffness, the harder felt was the sample.
  • Rating Criterion for Car Seat
      • ◯: stiffness≦100
      • ×: stiffness>100
  • Rating Criterion for Car Mat
      • ◯: stiffness>100
      • ×: stiffness≦100
        5. Formaldehyde Emission
  • A 2-L Tedlar® Bag (Dupont) was charged with 50 cm2 of a sample, purged with nitrogen and sealed. The bag was held at 65° C. for 2 hours. Using a gas detector 91L (Gas Tech Co., Ltd.), formaldehyde was detected.
  • Rating Criterion
      • ◯: no formaldehyde
      • ×: formaldehyde detected
        6. Heat Resistance
  • The samples of polyester woven fabric and polypropylene non-woven fabric coated with different coating compositions were heat treated at 150° C. for one hour, after which a change of color on the coating surface was visually examined.
      • Rating A: no color change
      • Rating B: yellowed
  • Rating C: materially yellowed
    TABLE 1
    Resin emulsion
    Composition solids (%)
    Solids
    St MMA BA EA AN AA GMA (%)
    Preparation 58 30 10 2 49.5
    Example 1
    Preparation 20 72 5 3 50.3
    Example 2
    Preparation 80 18 2 50.5
    Example 3
    Preparation 65 32 3 49.8
    Example 4
    Hydran HW-301 urethane resin base emulsion, 45
    Dainippon Ink & Chemicals, Inc.
    Sumikaflex 752 ethylene/vinyl acetate resin base emulsion, 50
    Sumitomo Chemical Co., Ltd.
    Nalstar SR-112 SBR base emulsion, Nippon A&L Inc. 50

    St: styrene

    MMA: methyl methacrylate

    BA: butyl acrylate

    EA: ethyl acrylate

    AN: acrylonitrile

    AA: acrylic acid

    GMA: glycidyl methacrylate
  • TABLE 2
    Coating composition for car seat
    Amount of composition, as solids (pbw)
    Example Comparative Example
    1 2 3 1 2 3 4 5
    Preparation 100 100 100 100
    Example 1
    Preparation 100 100 100
    Example 2
    Hydran 100
    HW-301
    Preparation 150 150 0.5
    Example 5
    Preparation 150 400
    Example 6
    Preparation 150
    Example 7
    Terrages 100
    C-30
    Terrages 100
    C-60

    Terrages C-30: Chisso Corp., melamine-coated ammonium polyphosphate

    Terrages C-60: Chisso Corp., melamine/formaldehyde-coated ammonium polyphosphate
  • TABLE 3
    Coating composition for car mat
    Amount of composition, as solids (pbw)
    Example Comparative Example
    4 5 6 7 6 7 8
    Preparation 100 50 100 100
    Example 3
    Preparation 100 100
    Example 4
    Sumikaflex 752 50
    Nalstar SR-112 100
    Preparation 50 50
    Example 5
    Preparation 50 70 0.5
    Example 6
    Terrages C-30 10
    Terrages C-60 15
  • TABLE 4
    Test results of car seats
    Example Comparative Example
    1 2 3 1 2 3 4 5
    Dry coating 140 120 100 100 110 160 140 110
    weight (g/m2)
    Sew line X
    fatigue
    Flame X
    retardance
    Water Δ/X Δ/X
    resistance
    Stiffness
    Formaldehyde X
    Heat A A A A C C B A
    resistance
  • TABLE 5
    Test results of car mats
    Example Comparative Example
    4 5 6 7 6 7 8
    Dry coating 360 380 380 430 420 420 460
    weight (g/m2)
    Flame X
    retardance
    Water Δ/X
    resistance
    Stiffness
    Formaldehyde X
    Heat A A A A B B B
    resistance
  • Japanese Patent Application No. 2005-357289 is incorporated herein by reference.
  • Although some preferred embodiments have been described, many modifications and variations may be made thereto in light of the above teachings. It is therefore to be understood that the invention may be practiced otherwise than as specifically described without departing from the scope of the appended claims.

Claims (9)

1. A coating composition comprising
100 parts by weight as solids of a synthetic resin emulsion and
1 to 300 parts by weight of at least one non-halogen flame retardant in which phosphorus and nitrogen-containing non-halogen flame retardant particles are surface coated with hydrophobic inorganic oxide fine particles.
2. The coating composition of claim 1, wherein said synthetic resin emulsion is selected from the group consisting of (meth)acrylate resin base emulsions, styrene/acrylate copolymer base emulsions, urethane resin base emulsions, ethylene/vinyl acetate copolymer base emulsions, rubber base emulsions, and mixtures thereof.
3. The coating composition of claim 1, wherein the particulate phosphorus and nitrogen-containing non-halogen flame retardant is selected from the group consisting of guanidine phosphate, ammonium phosphate, melamine phosphate, ammonium polyphosphate, melamine-surface-treated ammonium polyphosphate, silicon compound-surface-treated ammonium polyphosphate, and mixtures thereof.
4. The coating composition of claim 3, wherein the particulate phosphorus and nitrogen-containing non-halogen flame retardant is ammonium polyphosphate.
5. The coating composition of claim 3, wherein the particulate phosphorus and nitrogen-containing non-halogen flame retardant is silicon compound-surface-treated ammonium polyphosphate.
6. The coating composition of claim 1, wherein the hydrophobic inorganic oxide fine particles are hydrophobic silica fine particles.
7. The coating composition of claim 1, wherein the coated non-halogen flame retardant has an average particle size of 3 to 35 μm.
8. The coating composition of claim 1, wherein the hydrophobic inorganic oxide fine particles have an average particle size of 0.001 to 5 μm.
9. A vehicle interior material coated with the composition of claim 1.
US11/636,471 2005-12-12 2006-12-11 Coating composition and vehicle interior material Abandoned US20070135551A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US12/832,807 US7923074B2 (en) 2005-12-12 2010-07-08 Method for preparing a vehicle interior material

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005-357289 2005-12-12
JP2005357289 2005-12-12

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US12/832,807 Division US7923074B2 (en) 2005-12-12 2010-07-08 Method for preparing a vehicle interior material

Publications (1)

Publication Number Publication Date
US20070135551A1 true US20070135551A1 (en) 2007-06-14

Family

ID=38140296

Family Applications (2)

Application Number Title Priority Date Filing Date
US11/636,471 Abandoned US20070135551A1 (en) 2005-12-12 2006-12-11 Coating composition and vehicle interior material
US12/832,807 Expired - Fee Related US7923074B2 (en) 2005-12-12 2010-07-08 Method for preparing a vehicle interior material

Family Applications After (1)

Application Number Title Priority Date Filing Date
US12/832,807 Expired - Fee Related US7923074B2 (en) 2005-12-12 2010-07-08 Method for preparing a vehicle interior material

Country Status (3)

Country Link
US (2) US20070135551A1 (en)
KR (1) KR20070062441A (en)
CN (2) CN104278526A (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100152335A1 (en) * 2007-04-26 2010-06-17 Yong Jong Lee Fire retardancy and shape retention reinforced polyester
US20110170945A1 (en) * 2008-10-11 2011-07-14 D-Box Technologies Inc. Link member for motion-enabled movie theatre chair
WO2011154332A1 (en) * 2010-06-07 2011-12-15 Basf Se Encapsulated flameproofing agents for polymers
WO2014139639A1 (en) * 2013-03-09 2014-09-18 Clariant International Ltd Pulverulent coated flame retardant
US8859643B2 (en) 2010-06-07 2014-10-14 Basf Se Encapsulated flame retardants for polymers
CN104403427A (en) * 2014-11-19 2015-03-11 常熟市万象涂料有限公司 Fireproof and anti-corrosion composite coating
CN107384105A (en) * 2017-09-06 2017-11-24 苏州纽东精密制造科技有限公司 A kind of automobile using fireproof coating and preparation method thereof
CN109971033A (en) * 2017-12-27 2019-07-05 广东生益科技股份有限公司 Containing phosphorus silicon fire retardant, preparation method, fire-proof resin composition, prepreg and metal-clad laminate
WO2019246419A1 (en) * 2018-06-22 2019-12-26 David Ratchford Systems and methods for smoker-friendly vehicles
CN114008145A (en) * 2019-04-29 2022-02-01 阿克佐诺贝尔国际涂料股份有限公司 Halogen-free non-intumescent flame retardant coating composition

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010062438A2 (en) * 2008-11-26 2010-06-03 Avery Dennison Corporation Printable flame retardant polymeric film
WO2013152224A1 (en) * 2012-04-06 2013-10-10 Polyone Corporation Polyolefin intumescent phosphorous flame retardant system
CN103740216B (en) * 2013-12-20 2016-09-07 南通昂申金属材料有限公司 A kind of anti-rust coating composition and preparation method thereof
CN104194504A (en) * 2014-08-27 2014-12-10 苏州诚晟信息技术有限公司 Nano fire-resistant paint, and preparation method and application thereof
CN104910700A (en) * 2015-06-18 2015-09-16 郭小曼 Nano antibacterial fireproof coating
JP7012007B2 (en) * 2016-04-18 2022-01-27 昭和電工株式会社 Fiber treatment agents, manufacturing methods for processed fiber products, and processed fiber products
CN106833336A (en) * 2017-02-23 2017-06-13 沈阳华进交通科技有限公司 It is a kind of into charcoal halogen-free environment-friendly type flame-proof coating
WO2021192767A1 (en) * 2020-03-27 2021-09-30 株式会社ユポ・コーポレーション Aqueous flame-retardant coating composition and flame-retardant thermoplastic resin film

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5171259A (en) * 1990-04-02 1992-12-15 Kanji Inoue Device for nonoperatively occluding a defect
US5304131A (en) * 1991-07-15 1994-04-19 Paskar Larry D Catheter
US5350399A (en) * 1991-09-23 1994-09-27 Jay Erlebacher Percutaneous arterial puncture seal device and insertion tool therefore
US5477856A (en) * 1991-02-15 1995-12-26 Lundquist; Ingemar H. Torquable catheter and torquable tubular member for use therewith
US5876399A (en) * 1997-05-28 1999-03-02 Irvine Biomedical, Inc. Catheter system and methods thereof
US20020077687A1 (en) * 2000-12-14 2002-06-20 Ahn Samuel S. Catheter assembly for treating ischemic tissue
US20030005797A1 (en) * 1999-05-03 2003-01-09 Hopper Ryan K. Clamp device
US6586059B1 (en) * 1998-05-07 2003-07-01 Dany Felix Marie Michiels Flame retardant/heat resistant material
US20050277711A1 (en) * 2004-06-14 2005-12-15 Nissin Chemical Industry Co., Ltd. Vehicle interior material coating composition and vehicle interior material
US20060192186A1 (en) * 2004-02-16 2006-08-31 Shin-Etsu Chemical Co., Ltd. Flame retardant additives, emulsion type coating compositions, and flame retardant compositions
US7226467B2 (en) * 1999-04-09 2007-06-05 Evalve, Inc. Fixation device delivery catheter, systems and methods of use

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1020590A (en) * 1973-05-21 1977-11-08 Gulf Research And Development Company Hydrogen fluoride alkylation of iso-paraffins in the presence of trifluoromethanesulfonic acid
US5286759A (en) * 1991-03-08 1994-02-15 The Dow Chemical Company Foaming system for rigid urethane and isocyanurate foams
JPH08134455A (en) 1994-11-08 1996-05-28 Mitsui Toatsu Chem Inc Modified ammonium polyphosphate
JPH0913037A (en) 1995-07-03 1997-01-14 Nippon Carbide Ind Co Inc Capsuled flame retardant composition
JPH10110083A (en) 1996-10-07 1998-04-28 Chisso Corp Flame-retardant acrylic resin composition
JP2003171878A (en) 2001-12-03 2003-06-20 Aisin Chem Co Ltd Flame-retardant backing material
CN100427544C (en) 2003-11-26 2008-10-22 株式会社E-Tec Non-halogen flame resistant base material and carpet for vehicle or airplane use
JP2005179642A (en) 2003-11-26 2005-07-07 Emulsion Technology Co Ltd Non-halogenic flame-retardant backing material and carpet for vehicle or airplane
US7722939B2 (en) * 2004-09-01 2010-05-25 Appleton Papers, Inc. Adhesively securable stock materials

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5171259A (en) * 1990-04-02 1992-12-15 Kanji Inoue Device for nonoperatively occluding a defect
US5477856A (en) * 1991-02-15 1995-12-26 Lundquist; Ingemar H. Torquable catheter and torquable tubular member for use therewith
US5304131A (en) * 1991-07-15 1994-04-19 Paskar Larry D Catheter
US5350399A (en) * 1991-09-23 1994-09-27 Jay Erlebacher Percutaneous arterial puncture seal device and insertion tool therefore
US5876399A (en) * 1997-05-28 1999-03-02 Irvine Biomedical, Inc. Catheter system and methods thereof
US6586059B1 (en) * 1998-05-07 2003-07-01 Dany Felix Marie Michiels Flame retardant/heat resistant material
US7226467B2 (en) * 1999-04-09 2007-06-05 Evalve, Inc. Fixation device delivery catheter, systems and methods of use
US20030005797A1 (en) * 1999-05-03 2003-01-09 Hopper Ryan K. Clamp device
US20020077687A1 (en) * 2000-12-14 2002-06-20 Ahn Samuel S. Catheter assembly for treating ischemic tissue
US20060192186A1 (en) * 2004-02-16 2006-08-31 Shin-Etsu Chemical Co., Ltd. Flame retardant additives, emulsion type coating compositions, and flame retardant compositions
US20050277711A1 (en) * 2004-06-14 2005-12-15 Nissin Chemical Industry Co., Ltd. Vehicle interior material coating composition and vehicle interior material

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100152335A1 (en) * 2007-04-26 2010-06-17 Yong Jong Lee Fire retardancy and shape retention reinforced polyester
US8142689B2 (en) * 2007-04-26 2012-03-27 Encepkorea Co., Ltd. Fire retardancy and shape retention reinforced polyester
US20110170945A1 (en) * 2008-10-11 2011-07-14 D-Box Technologies Inc. Link member for motion-enabled movie theatre chair
WO2011154332A1 (en) * 2010-06-07 2011-12-15 Basf Se Encapsulated flameproofing agents for polymers
US8859643B2 (en) 2010-06-07 2014-10-14 Basf Se Encapsulated flame retardants for polymers
WO2014139639A1 (en) * 2013-03-09 2014-09-18 Clariant International Ltd Pulverulent coated flame retardant
CN104403427A (en) * 2014-11-19 2015-03-11 常熟市万象涂料有限公司 Fireproof and anti-corrosion composite coating
CN107384105A (en) * 2017-09-06 2017-11-24 苏州纽东精密制造科技有限公司 A kind of automobile using fireproof coating and preparation method thereof
CN109971033A (en) * 2017-12-27 2019-07-05 广东生益科技股份有限公司 Containing phosphorus silicon fire retardant, preparation method, fire-proof resin composition, prepreg and metal-clad laminate
WO2019246419A1 (en) * 2018-06-22 2019-12-26 David Ratchford Systems and methods for smoker-friendly vehicles
CN114008145A (en) * 2019-04-29 2022-02-01 阿克佐诺贝尔国际涂料股份有限公司 Halogen-free non-intumescent flame retardant coating composition

Also Published As

Publication number Publication date
KR20070062441A (en) 2007-06-15
US7923074B2 (en) 2011-04-12
CN101033359A (en) 2007-09-12
CN104278526A (en) 2015-01-14
US20100272911A1 (en) 2010-10-28

Similar Documents

Publication Publication Date Title
US7923074B2 (en) Method for preparing a vehicle interior material
US7820079B2 (en) Vehicle interior material coating composition and vehicle interior material
US20090215932A1 (en) Coating composition for car interior material and car interior material
JP2006028488A (en) Coating composition for vehicular interior finishing material and the vehicular interior finishing material
US20060241229A1 (en) Aqueous flame retardant resin composition
US5663224A (en) Process for preparing an aqueous dispersion
JP5019029B2 (en) Coating composition and vehicle interior material
JP5847177B2 (en) Sound reduction material with emulsion polymer stabilized with protective colloid
WO2007023820A1 (en) Emulsion for vibration damper
US20140024740A1 (en) Carpet backing compositions prepared from recycled paint
KR101398310B1 (en) Aqueous resin composition
US7932338B2 (en) Brominated polymers, and fire retardant articles comprising them
JP4378918B2 (en) Antifouling agent
JP5274784B2 (en) Flame retardant resin aqueous emulsion and process for producing the same
JP5201781B2 (en) Coating composition for vehicle interior material and vehicle interior material
JP7377594B2 (en) Anti-adhesive agent for unvulcanized rubber and anti-adhesive aqueous dispersion for unvulcanized rubber
JP5738672B2 (en) Flame retardant resin composition
EP2547706B1 (en) Polymer latex useful for the production of textile floor coverings
JP4469706B2 (en) Back retardant resin aqueous composition for backing
JP2013049858A (en) Coating composition for vehicular interior material, and vehicular interior material
JP2004224816A (en) Aqueous non-slip coating material composition
JP2020164716A (en) Flame-retardant resin composition and method for producing flame-retardant resin composition
JPH0379652A (en) Aqueous coating composition
JP2019065095A (en) Flame-retardant resin composition
JPH03143972A (en) Underfloor member of automobile

Legal Events

Date Code Title Description
AS Assignment

Owner name: NISSIN CHEMICAL INDUSTRY CO., LTD., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:OKUDA, HARUKAZU;TANII, ICHIRO;NAKAMURA, NORIO;AND OTHERS;REEL/FRAME:018699/0600

Effective date: 20061205

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION