WO2018082876A1 - Silicone rubber composition for airbag coating - Google Patents

Silicone rubber composition for airbag coating Download PDF

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Publication number
WO2018082876A1
WO2018082876A1 PCT/EP2017/075806 EP2017075806W WO2018082876A1 WO 2018082876 A1 WO2018082876 A1 WO 2018082876A1 EP 2017075806 W EP2017075806 W EP 2017075806W WO 2018082876 A1 WO2018082876 A1 WO 2018082876A1
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Prior art keywords
group
airbag
silicon atom
compound
molecule
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PCT/EP2017/075806
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English (en)
French (fr)
Inventor
Yukihiko Asakawa
Kei HOSHINO
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Wacker Chemie Ag
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Publication of WO2018082876A1 publication Critical patent/WO2018082876A1/en

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    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

Definitions

  • the present invention relates to a silicone composition for a coating on a base cloth used for an airbag of an automobile and the like.
  • the present invention relates to a silicone rubber composition for a coating, which is excellent in elongation and is capable of forming a silicone cured film which is excellent in adhesiveness to base cloths, and thus can provide an airbag which is useful as an airbag such as a curtain airbag.
  • This airbag apparatus which deploys and is inflated during a collision for protecting a passenger is increasingly mounted.
  • This airbag apparatus includes a sensor that senses a strong shock caused by a collision, an inflator that generates gas, and an airbag that is inflated with the gas generated from the inflator.
  • a base cloth for the airbag a woven cloth made of synthetic fibers such as polyamide and polyester is used.
  • an untreated woven cloth does not satisfy strict requirements in terms of airtightness, heat resistance, and flame retardance against the high-pressure and high- temperature gas generated from the inflator. Therefore, there is generally used a product obtained by coating the base cloth with a silicone composition and curing the coating of the silicone
  • airbags which are actuated on the front of a passenger at a driver seat or a front passenger seat
  • various airbags are mounted.
  • the side curtain airbag is housed along a portion from the front pillar to the roof side for the purposes of protecting the head of a passenger and preventing a passenger from being thrown from a car when a vehicle is overturned during a collision.
  • the side curtain airbag is required to retain the state of deploying and being inflated for a certain time after actuated during a collision, unlike the airbag mounted at a driver seat or a front passenger seat.
  • Patent Literature 1 discloses a method of employing, for a silicone composition, an
  • organohydrogenpolysiloxane that has a silicon atom-bonded hydrogen atom only at both terminals of the molecular chain.
  • the ratio of the number of silicon atom-bonded hydrogen atoms only at both terminals of the molecular chain is increased to 30 to 60% of the number of all hydrogen atoms, thereby increasing the length of the molecular chain of the organopolysiloxane having an alkenyl group, which is a base compound, through a curing reaction.
  • a gas leak after the deployment and inflation of an airbag is suppressed.
  • the above-described silicone rubber composition had a problem as follows.
  • the ratio of the silicon atom-bonded hydrogen atoms only at both terminals of the molecular chain becomes higher, the length of the molecular chain increases thereby to enhance the elongation during the cutting of the cured product.
  • the ratio of hydrogen atoms other than those at both terminals of the molecular chain, which are involved in the adhesion to a base cloth drastically decreases. As a result, the adhesiveness to a base cloth significantly deteriorates.
  • Patent Literature 1 Japanese Patent Application Laid-Open No.
  • the present invention has been made in view of the above- described circumstances, and relates to a silicone composition for a coating on a base cloth used for an airbag of an automobile and the like.
  • An object of the present invention is to provide an airbag which is highly safe as an airbag such as a curtain airbag, a
  • silicone composition for an airbag coating, and an airbag base cloth in which the cured product of the silicon composition is excellent in elongation thereby to retain an intended internal pressure after the actuation of the airbag, and the cured film having excellent adhesiveness to a polyamide base cloth and a polyester base cloth can be formed even under high temperature and high humidity.
  • the present inventors have intensively conducted studies. As a result, they have found an formulation of a silicone rubber
  • composition for an airbag coating in which an organohydrogenpolysiloxane containing a silicone atom-bonded
  • the present invention is a silicone rubber
  • composition for an airbag coating including: (A) 100 parts by mass of a diorganopolysiloxane that contains two or more silicon atom- bonded alkenyl groups in one molecule and has a viscosity at 25°C of 100 to 500,000 mPa-s; (B-l) an organohydrogenpolysiloxane that contains one or more silicon atom-bonded hydrogen atoms in one molecule at a portion other than both terminals of the molecular chain thereof, and 0 or more hydrogen atoms at both terminals of the molecular chain thereof, and has a viscosity at 25°C of 1 to 2,000 mPa-s; (B-2) a linear organohydrogenpolysiloxane that contains a silicon atom-bonded hydrogen atom only at both terminals of the molecular chain thereof, and has a viscosity at 25°C of 1 to 2,000 mPa-s; (C) a micronized silica having a specific surface area by
  • the silicone rubber composition for an airbag coating may preferably include 0.05 to 10 parts by mass of (G) a component having a function of improving adhesiveness of the silicone
  • component (G) may be preferably one or more organometallic compounds selected from the group consisting of an organic titanium compound, an organic zirconia compound, and an organic aluminum compound.
  • the organohydrogenpolysiloxane (B-l) may preferably include a compound represented by general formula (1) below:
  • the organohydrogenpolysiloxane (B-l) may preferably have a
  • trimetylsiloxy group at both terminals of the molecular chain and contain at least one aromatic group bonded to a silicon atom in the molecule .
  • the airbag has an elongation of 800 ⁇ 6 or more when the cured product thereof is cut. Therefore, an intended internal pressure can be retained even after the deployment and inflation of the airbag. Furthermore, since adhesiveness to the base cloth is excellent even under the high-temperature and high-humidity environment, the airbag is normally actuated even when an inflator generates gas under an unexpected high pressure caused by
  • an airbag which is highly safe as an airbag such as a curtain airbag.
  • a component (A) is a diorganopolysiloxane having two or more silicon atom-bonded alkenyl groups in one molecule, and is a base compound of a silicone rubber composition having excellent rubber physical properties after cured.
  • the component (A) usually has an average composition formula represented by general formula (2) below:
  • R x s are the same as or different from each other, and each an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, and a is 1.7 to 2.1).
  • At least two of the monovalent hydrocarbon groups represented by Ri are selected from an alkenyl group such as a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a hexenyl group, and a
  • the other of the monovalent hydrocarbon groups represented by Ri is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 18 carbon atoms. Specific examples thereof may include: an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a 2-ethylhexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a dodecyl group; a
  • cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group
  • an aryl group such as a phenyl group, a tolyl group, a xylyl group, a biphenyl group, and a naphthyl group
  • an aralkyl group such as a benzyl group, a phenylethyl group, a phenylpropyl group, and a methylbenzyl group
  • hydrocarbon groups is substituted with a halogen atom, a cyano group, or the like, such as a chloromethyl group, a 2-bromoethyl group, a 3, 3, 3-trifluoropropyl group, a 3-chloropropyl group, and a
  • the required two or more alkenyl groups are preferably a vinyl group, and other groups are preferably a methyl group, a phenyl group, and a 3, 3, 3-trifluoropropyl group.
  • the required two or more alkenyl groups are preferably a vinyl group, and other groups are preferably a methyl group, a phenyl group, and a 3, 3, 3-trifluoropropyl group.
  • preferably 70 mol% or more, usually 80 mol% or more, of all RiS is a methyl group, in terms of physical properties of the cured product and economic efficiency.
  • the diorganopolysiloxane of the component (A) may be linear or branched.
  • Examples of the molecular structure may include: a
  • dimethylvinylsiloxy group a dimethylsiloxane-methylvinylsiloxane copolymer in which both terminals of the molecular chain are blocked with a dimethyl inylsiloxy group;
  • diorganopolysiloxane of The component (A) to be used is 100 to 500, 000 mPa-s, and preferably 1, 000 to 500, 000 mPa-s .
  • Two or more diorganopolysiloxanes having different viscosities are particularly preferably used so that the final viscosity of the silicone
  • composition is easily adjusted.
  • a component (B-l) is a component that causes the cured product of the silicone composition to crosslink and contributes to
  • the component (B-l) is an organohydrogenpolysiloxane that contains one or more silicon atom- bonded hydrogen atoms in one molecule, and is any
  • organohydrogenpolysiloxane other than an organohydrogenpolysiloxane that has a silicon atom-bonded hydrogen atom only at both terminals of the molecular chain.
  • organohydrogenpolysiloxane other than an organohydrogenpolysiloxane that has a silicon atom-bonded hydrogen atom only at both terminals of the molecular chain.
  • organohydrogenpolysiloxane may include methylhydrogenpolysiloxane, a dimethylsiloxane-methylhydrogensiloxane copolymer, a methylphenylsiloxane-methylhydrogensiloxane copolymer, cyclic methylhydrogenpolysiloxane, and a copolymer including a dimethylhydrogensiloxy unit and an S1O 4 / 2 unit.
  • the component (B- 1) is preferably an organohydrogenpolysiloxane that has a silicon atom-bonded hydrogen atom at both terminals of the molecular chain and also contains at least one silicon atom-bonded hydrogen atom in the molecular chain in the molecule.
  • m is more preferably 1 to 20
  • n is more preferably 10 to 100
  • t is 0.02 ⁇ t ⁇ 1.0, and further preferably 0.02 ⁇ t ⁇ 0.2.
  • the component (B-l) to be used is preferably an organohydrogenpolysiloxane that has a trimethylsiloxy group at both terminals in the molecular chain and at least one aromatic group in the molecule.
  • the aromatic group is preferably a phenyl group for economic reasons.
  • the viscosity at 25°C of the organohydrogenpolysiloxane of the component (B-l) is 1 to 2, 000 mPa-s, and preferably 2 to 1, 000 mPa-s . Also, one of the organohydrogenpolysiloxanes of the component (B-l) may be used alone, or two or more thereof may be used in combination. [0024]
  • a component (B-2) is a component that causes the cured product of the silicone composition to crosslink and contributes to enhanced elongation at break.
  • the component (B-2) is any linear
  • organohydrogenpolysiloxane which has a silicon atom-bonded hydrogen atom only at both terminals of the molecular chain. This enables the length of the molecular chain of the organopolysiloxane having an alkenyl group, which is a base compound, to be relatively easily increased by a curing reaction.
  • the component (B-2) is preferably an
  • organohydrogenpolysiloxane containing at least one aromatic group in the molecule from the viewpoint of the improvement in heat
  • the aromatic group is more preferably a phenyl group for economic reasons.
  • the viscosity at 25°C of the organohydrogenpolysiloxane of the component (B-2) is 1 to 2, 000 mPa-s, and preferably 2 to 1, 000 mPa-s .
  • one of the organohydrogenpolysiloxanes of the component (B-2) may be used alone, or two or more thereof may be used in combination. It is preferable to use a plurality of organohydrogenpolysiloxanes of the component (B-2), because the cured product is likely to have unevenly distributed crosslinking points thereby to relatively easily enhance the elongation of the cured product.
  • the total number of hydrogen atoms in the component (B-l) and the component (B-2) is preferably 1/5 to 7/1 per one alkenyl group of the component (A) .
  • the ratio of the total number of silicon atom- bonded hydrogen atoms contained in the component (B-2) relative to the total number of silicon atom-bonded hydrogen atoms contained in the component (B-l) and the component (B-2) is 10 to 60 ⁇ 6, more preferably 15 to 45%, and further preferably 15 to 30%. When the ratio is less than 10%, desired elongation at break becomes
  • the ratio is more than 60%, the hardness of the cured product decreases to a large extent, and the cured film cannot withstand a load of the rubbing impact during an adhesion test thereby to peel.
  • silica of a component (C) may include fumed silica, silica fume, precipitated silica, pyrogenic silica, colloidal silica, and diatomaceous earth, which have hydrophilicity and hydrophobicity. In particular, these are preferably fine powder.
  • the particle size and the specific surface area thereof are preferably 100 um or less and 50 m 2 /g or more, respectively. Also, the surface of the silica to be used may be previously treated with organosilane,
  • the added amount of the component (C) relative to 100 parts by mass of the component (A) is usually 5 to 50 parts by mass, and preferably 10 to 30 parts by mass.
  • One of these silicas may be used alone, or two or more thereof may be used in combination.
  • hydrophobization treatment agent may include organosilazane such as hexamethyldisilazane, halogenated silane such as methyltrichlorosilane, dimethyldichlorosilane, and trimethylchlorosilane, organoalkoxysilane in which these halogen atoms are substituted with an alkoxy group such as a methoxy group and an ethoxy group, and dimethyl silicone oil.
  • organosilazane such as hexamethyldisilazane
  • halogenated silane such as methyltrichlorosilane, dimethyldichlorosilane, and trimethylchlorosilane
  • organoalkoxysilane organoalkoxysilane in which these halogen atoms are substituted with an alkoxy group such as a methoxy group and an ethoxy group, and dimethyl silicone oil.
  • hexamethyldisilazane is preferable.
  • An addition reaction catalyst of a component (D) is a catalyst that promotes an addition curing reaction between an alkenyl group and a silicon atom-bonded hydrogen atom, and that is known to those skilled in the art.
  • the addition reaction catalyst of the component (D) may include: platinum group metal such as platinum, rhodium, palladium, osmium, iridium, and ruthenium; a product obtained by fixing the platinum group metal to a particulate carrier material (for example, activated carbon, aluminum oxide, and silicon oxide) ; and a platinum compound such as platinum halide, a platinum- olefin complex, a platinum-alcohol complex, a platinum-alcoholate complex, a platinum-vinylsiloxane complex, dicyclopentadiene- platinum dichloride, cyclooctadiene-platinum dichloride, and cyclopentadiene-platinum dichloride .
  • a metal compound catalyst other than noble metal may be used.
  • a hydrosilylation iron catalyst there are used an iron—carbonyl complex catalyst, an iron catalyst having a cyclopentadienyl group as a ligand, an iron catalyst having a terpyridine-based ligand or having a terpyridine- based ligand and a bistrimethylsilylmethyl group, an iron catalyst having a bisiminopyridine ligand, an iron catalyst having a
  • bisiminoquinoline ligand an iron catalyst having an aryl group as a ligand, an iron catalyst having a cyclic or non-cyclic olefin group having an unsaturated group, and an iron catalyst having a cyclic or non-cyclic olefinyl group having an unsaturated group.
  • Other examples may include a hydrosilylation cobalt catalyst, a
  • hydrosilylation vanadium catalyst a hydrosilylation ruthenium catalyst, a hydrosilylation iridium catalyst, a hydrosilylation samarium catalyst, a hydrosilylation nickel catalyst, and a
  • the formulation amount of the addition reaction catalyst of the component (D) is an effective amount depending on the curing temperature and curing time intended in this use.
  • the formulation amount relative to the total mass of the silicone rubber composition is, in terms of the concentration of a catalyst metal element, 0.5 to 1,000 ppm, preferably 1 to 500 ppm, and more preferably 1 to 100 ppm.
  • the formulation amount is less than 0.5 ppm, an addition reaction becomes significantly slow.
  • the formulation amount is more than 1,000 ppm, the cost is increased, and economic efficiency is unfavorable.
  • An organosilicon compound of a component (E) is any organosilicon compound of a component (E)
  • organosilicon compound which has an epoxy group and a silicon atom- bonded alkoxy group in one molecule. More preferably, the
  • organosilicon compound of the component (E) has at least one epoxy group and at least two silicon atom-bonded alkoxy groups.
  • an epoxy group is preferably bonded to a silicon atom in the form of a glycidoxyalkyl group such as a glycidoxypropyl group, and an epoxy- containing cyclohexylalkyl group such as a 2, 3-epoxycyclohexylethyl group and a 3, 4-epoxycyclohexylethyl group.
  • Two or three epoxy groups may be contained in one molecule.
  • the silicon atom- bonded alkoxy group is preferably a methoxy group, an ethoxy group, and a propoxy group, as well as an alkyldialkoxysilyl group such as a methyldimethoxysilyl group, an ethyldimethoxysilyl group, a methyldiethoxysilyl group, and an ethyldiethoxysilyl group.
  • a functional group other than the above-described groups may be a functional group selected from an alkenyl group such as a vinyl group, a (meth) acryloxy group, a hydrosilyl group (SiH group), and an isocyanate group.
  • a siloxane compound of a component (F) is a component that imparts the function to control the change in viscosity of the silicone composition in a time-dependent manner.
  • the siloxane compound is a silane containing at least one silanol group (that is, a silicon atom-bonded hydroxyl group) in one molecule or a siloxane compound.
  • One of these siloxane compounds may be used alone, or two or more thereof may be used in combination.
  • the siloxane compound is an oligomer with usually 2 to 4 silicon atoms in the molecule.
  • siloxane compound of the component (F) may include silane such as trimethylsilanol, triethylsilanol,
  • trimethylsilanol, triethylsilanol, triisopropylsilanol, and triphenylsilanol are preferable, in terms of availability and industrial handleability.
  • the added amount of the component (F) relative to 100 parts by mass of the component (A) is usually 0.02 to 20 parts by mass, and preferably 0.1 to 10 parts by mass. When the added amount is less than 0.1 parts, the effect to control the viscosity of the silicone composition in a time-dependent manner is low. When it is more than 20 parts by mass, the curing rate becomes slow.
  • a component having the function of improving the adhesiveness of the silicone composition of a component (G) is not limited to a specific compound, and can be any compound which does not impair the object of the present invention.
  • a so-called silane coupling agent may be used.
  • the organic functional group is
  • a vinyl group preferably at least one of a vinyl group, a methacryl group, an acryl group, and an isocyanate group.
  • examples may include
  • methacryloxysilane such as 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane
  • furandione such as 3- trimethoxysilylpropyl succinic acid anhydride and dihydro-3- (3- (triethoxysilyl) propyl) -2, 5-furandione
  • the organic functional group may be bonded to a silicon atom via another group such as an alkylene group. This is preferable, because the use in combination with the component (E) promotes the effect.
  • an organometallic compound such as an organic titanium compound, an organic zirconium compound, and an organic aluminum compound. These organometallic compounds are not particularly limited as long as they serve as a condensation co- catalyst for promoting adhesion, and are further effectively used in combination with the above-described silane coupling agent.
  • Such a combination may include a combination of methacryloxy group-containing organoalkoxysilane and a titanium chelate compound and/or a zirconium chelate compound, a combination of dihydro-3- (3- (triethoxysilyl) propyl) -2, 5-furandione and a titanium chelate compound and/or a zirconium chelate compound, and a combination of methacryloxy group-containing
  • organoalkoxysilane dihydro-3- (3- (triethoxysilyl) propyl) -2, 5- furandione, and a titanium chelate compound and/or a zirconium chelate compound.
  • organometallic compound may include an organic titanic acid ester such as tetraisopropyl titanate and tetrabutyl titanate; a titanium-based condensation co-catalyst such as an organic titanium chelate compound such as
  • zirconium-based condensation co-catalyst such as an oxozirconium compound such as zirconium bis (2-ethylhexanoate) oxide and zirconium acetylacetonate (2-ethylhexanoate) oxide
  • an aluminum alcholate such as aluminum triethylate, aluminum triisopropylate, and aluminum tri (sec-butyrate)
  • an aluminum chelate compound such as
  • an aluminum-based condensation catalyst such as an aluminum acyloxy compound such as hydroxyaluminum bis (2-ethylhexanoate) .
  • an organic compound containing an isocyanate group in the molecule may be used other than the above- described organometallic compound.
  • Such an organic compound is not particularly limited and can be any organic compound, as long as it contains at least one isocyanate group in one molecule.
  • Examples of the organic compound containing an isocyanate group in the molecule may include benzyl isocyanate, tolylene diisocyanate, triallyl isocyanurate, trimethylhexamethylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, butane diisocyanate, pentane diisocyanate, tetramethylene-1, 4-diisocyanate,
  • diisocyanate tris (3-trimethoxysilylpropyl) isocyanurate, tris (3- triethoxysilylpropyl) isocyanurate, tris (3- propoxysilylpropyl) isocyanurate, and derivatives and precursors thereof.
  • organic compounds may be used alone, or two or more thereof may be used.
  • the organic compound is preferably used in combination with the above-described silane coupling agent.
  • the silicone composition according to the present invention can contain any additives known as additives to silicone rubber, as an optional component other than the above-described components (A) to (G) , within the range that does not impair the object of the present invention.
  • additives may include a
  • reinforcing filler a non-reinforcing filler, an adhesion promoter, a pigment, a dye, a curing inhibitor, a heat resistance promoter, a flame retardant, an antistatic agent, a conductivity promoter, an airtightness improving agent, a radiation shielding agent, an electromagnetic wave shielding agent, a preservative, a stabilizer, an organic solvent, a plasticizer, a fungicide, an
  • organopolysiloxane which contains one silicon atom-bonded hydrogen atom or alkenyl group in one molecule and which does not contain any other functional group, and a non-functional organopolysiloxane which does not contain a silicon atom-bonded hydrogen atom and alkenyl group.
  • One of these additives may be formulated alone, or two or more thereof may be formulated in combination.
  • the pigment may include titanium oxide, alumina silicate, iron oxide, zinc oxide, calcium carbonate, carbon black, rare earth oxides, chromium oxide, cobalt pigments, ultramarine blue, cerium silanolate, aluminum oxide, aluminum hydroxide, titanium yellow, carbon black, barium sulfate, precipitated barium sulfate, and mixtures thereof.
  • the curing inhibitor has the ability to adjust the curing rate of an addition reaction.
  • examples thereof may include an acetylene- based compound, hydrazines, triazoles, phosphines, and mercaptans .
  • Any curing inhibitor which is known as a compound having the curing suppression effect in the art can be used.
  • examples of such a compound may include a phosphorous-containing compound such as triphenylphosphine, a nitrogen-containing compound such as
  • tributylamine tetramethylethylenediamine, and benzotriazole
  • sulfur-containing compound an acetylene-based compound, a compound containing two or more alkenyl groups, a hydroperoxy compound, and a maleic acid derivative.
  • amino group-containing silane and an amino group-containing silicone compound may be used.
  • Specific examples thereof may include various "ene-ine" systems such as 3-methyl-3-pentene-l-ine and 3, 5-dimethyl-3-hexene- 1-ine; acetylene-based alcohol such as 3, 5-dimethyl-l-hexyne-3-ol, 1-ethynyl-l-cyclohexanol, and 2-phenyl-3-butyne-2-ol; known dialkyl, dialkenyl, and maleate and fumarate such as dialkoxyalkyl fumarate and maleate; and a compound which contains cyclovinylsiloxane .
  • acetylene-based alcohol such as 3, 5-dimethyl-l-hexyne-3-ol, 1-ethynyl-l-cyclohexanol, and 2-phenyl-3-butyne-2-ol
  • known dialkyl, dialkenyl, and maleate and fumarate such as dialkoxyalkyl fumarate and maleate
  • heat resistance promoter examples include cerium hydroxide, cerium oxide, iron oxide, fume titanium dioxide, and mixtures thereof.
  • the airtightness improving agent may be any agent which has the effect of reducing air permeability of the cured product, and can be an organic matter or an inorganic matter. Specific examples thereof may include urethane, polyvinyl alcohol, polyisobutylene, an isobutylene-isoprene copolymer, plate-like talc, mica, glass flakes, boehmite, various metal foils, powdered metal oxides, and mixtures thereof.
  • the silicone composition for an airbag coating according to the present invention can be manufactured by a method known to those skilled in the art, and the method is not limited. Examples of such a known method may include a method including previously mixing the components (A) , (B) , and (C) or components (A) , (C) , and (D) using a stirrer, or uniformly kneading the components (A) , (B) , and (C) or components (A) , (C) , and (D) using a two-roll, a kneader mixer, a pressurized kneader mixer, a high shear-type mixer such as a Ross mixer, an extruder, a continuous extruder, or the like, to prepare a silicone rubber base, and thereafter adding the components (E) , (F) ,
  • Another known example may include previously producing the components (A) and (B) or components (A) and (D) with an emulsifier in an emulsifying apparatus.
  • the silicone composition according to the present invention is preferably preserved in the form of at least two different components, so that curing does not previously proceed.
  • one of the components contain the organopolysiloxane (A) having an unsaturated bond, and the other contain the organohydrogenpolysiloxane (B) having a silicon atom- bonded hydrogen atom.
  • corresponding co-agents and additives are preferably contained in one or both of the components.
  • these different components may be preserved in an organic solvent such as toluene, xylene, hexane, white spirit, and mixtures thereof.
  • these different components may be emulsified with an emulsifier so that they are preserved in an aqueous emulsion state.
  • an emulsifier in order to prevent the risk of fire, the
  • the present invention relates to a silicone composition for a coating on a base cloth used for an airbag of an automobile and the like.
  • An airbag is obtained by sewing an airbag base cloth into a bag shape.
  • the airbag is mainly mounted for automobiles.
  • the bag is to be inflated when an accident occurs, thereby to secure the safety of a driver and a passenger.
  • the airbag base cloth is usually woven with a synthetic fiber such as polyamide and polyethylene
  • the coating composition according to the present invention is applied onto the synthetic fiber woven fabric for airbags .
  • polyamide fiber woven fabrics such as nylon 6, nylon 66, and nylon 46, aramid fiber woven fabrics, polyester fiber woven fabrics represented by polyalkylene
  • the coating composition according to the present invention is applied onto flat woven fabrics, bag-shaped woven fabrics, and hose-shaped woven fabrics depending on the type of an airbag, which include 10 to 5000 decitex threads. From the viewpoint of
  • woven fabrics including 50 to 1000 decitex threads are preferable.
  • drying may be performed after the scouring treatment of the base cloth, and thereafter coating with the coating composition according to the present invention may be performed.
  • coating with the coating composition according to the present invention may be performed before the drying after the scouring treatment, and thereafter drying may be performed such that the drying of the scouring liquid and the curing of the coating
  • composition are simultaneously achieved. Also, the coating
  • composition according to the present invention may be directly applied to the base cloth which is not subjected to a scouring treatment completely.
  • the coating with the coating composition according to the present invention can be performed by a generally used method.
  • Examples of such a method may include immersion and padding, brushing, flow coating, spraying, roller coating, gravure coating, comma coater, textile printing, knife coating, Meyer bar, air brush, slop padding, and roll coating.
  • immersion and padding brushing, flow coating, spraying, roller coating, gravure coating, comma coater, textile printing, knife coating, Meyer bar, air brush, slop padding, and roll coating.
  • One or a combination of these methods is performed depending on circumstances. Also, when one coating method is performed, the coating is not necessarily
  • the number of cured films after coating is not necessarily one, and may be two or more.
  • an additional component may be formulated, or additional processing may be performed on the surface of the cured film after coating. Also, another cured film having such functions may be further formed.
  • the drying and curing after coating is usually performed in a heating device which can generate heat with hot air, infrared rays, gas burners, heat exchangers, or other energy sources. It is noted that this drying and curing can be performed with not only commonly used heating devices but also any device having a drying ability to achieve intended drying and curing. Examples thereof may include a heating roll calendar, a heatable bonding press, a heatable daylight press, a high-temperature kiss roll, a hot air dryer, and a
  • a heating device have a plurality of temperature zones set during curing, in order to prevent the formation of bubbles in the cured film.
  • preliminary drying can be performed in a first temperature zone of 60 to 150°C, preferably 80 to 130°C, and further preferably 90 to 120°C, and curing can be performed in a subsequent second temperature zone of up to 300°C.
  • the temperature range of 120 to 250°C is preferable.
  • preliminary drying be performed such that the temperature of a material to be cured reaches 170°C or higher at least once.
  • the retention time necessary for curing is preferably about 0.5 to 30 minutes, depending on the weight of coating, the heat
  • a dimethylpolysiloxane solution as the component (D) , which contained as a platinum content a platinum- divinyltetramethyldisiloxane complex in an amount of 1%, and 0.1 parts of ethynylcyclohexanol were added.
  • the mixture was thoroughly mixed in a stirring and mixing device to prepare a rubber base.
  • a silicone composition for an airbag coating was manufactured by adding necessary additives to this rubber base.
  • a base cloth there were used a polyamide base cloth which is a flat woven fabric including a 470 decitex thread, and a polyester base cloth including a 555 decitex thread, both having been scoured.
  • the base cloth was coated with the silicone composition for an airbag coating using a knife coater, and the coating was cured in a drying furnace at a temperature of 180°C for a curing time of 60 seconds .
  • the obtained silicone composition was press-cured at a temperature of 170°C for a curing time of 5 minutes to prepare a cured sheet having a thickness of 2 mm. This was measured for hardness (type A durometer) and elongation at break in accordance with JIS K 6249.
  • the adhesion state of the cured film was observed in a rubbing test.
  • the coated fabric was cut out to obtain a sample having a length of 10 cm and a width of 5 cm.
  • a rubbing test was performed while a 10 N load was applied on the cured film.
  • the measurement was performed using an INC-1507-A scrub tester (manufactured by Imoto Machinery Co., Ltd.) in accordance with ISO 5981.
  • the surface state was visually observed to see whether or not a pinhole or peeling exists .
  • the coated fabric was retained under the environment of a temperature of 80°C and a relative humidity of 95% for 500 hours.
  • methylhydrogenpolysiloxane (hydrogen content: 0.01%) in which both terminals were blocked with a dimethylhydrogensiloxy group, and the viscosity at 25°C was 1000 mPa-s .
  • the mixture was thoroughly mixed in a stirring and mixing device. It is noted that the ratio of the total number of silicon atom-bonded hydrogen atoms contained in the component (B-2) in this formulation was 27% relative to the total number of hydrogen atoms .
  • this prepared product was applied onto each of the polyamide base cloth and the polyester cloth with
  • the coating was cured in a drying furnace to manufacture a coated cloth. Two coated cloths were manufactured for each of the polyamide base cloth and the polyester cloth.
  • One of the manufactured coated cloths was left to stand at room temperature for 24 hours. Thereafter, the adhesion state was observed in a rubbing test. As a result, a pinhole and/or peeling were not observed even after rubbing 1200 times in each of the polyamide base cloth and the polyester cloth, and favorable
  • a product was manufactured according to the same formulation as Example 1, except that 0.5 parts of an organohydrogenpolysiloxane represented by formula (1) below (hydrogen content: 0.05%) in which the viscosity at 25°C was 165 mPa-s was further added as the
  • the ratio of the total number of silicon atom-bonded hydrogen atoms contained in the component (B-2) in this formulation was 24% relative to the total number of hydrogen atoms.
  • Example 2 Similarly to Example 1, in each base cloth, a pinhole and/or peeling were not observed after rubbing 1200 times or more in the rubbing test after the coated film was left to stand at room
  • a product was manufactured according to the formulation of Example 2, except that 0.25 parts of a
  • a product was manufactured in the formulation of Example 3, except that 5 parts of a methylhydrogenpolysiloxane (hydrogen content: 0.18%) in which both terminals were blocked with a
  • methylhydrogenpolysiloxane (hydrogen content: 0.01%) in which both terminals were blocked with a dimethylhydrogensiloxy group, and the viscosity at 25°C was 1000 mPa-s .
  • a product was manufactured according to the formulation of Example 3, except that the 3-glycidoxypropyltrimethoxysilane as the component (E) was not contained.
  • a product was manufactured according to the formulation of Example 3, except that the titanium ethylacetoacetate as the component (G) was not contained.
  • a pinhole and/or peeling were observed when rubbing 600 times in the rubbing test after the coated film was left to stand at room temperature for 24 hours, and when rubbing 200 times after wet heat.
  • a pinhole and/or peeling were observed when rubbing 300 times in an initial stage, and when rubbing 100 times after wet heat.
  • the hardness of the cured sheet was 24, and the elongation at break was 830%.
  • the present invention relates to a silicone composition for a coating on a base cloth used for an airbag of an
  • the cured product of the silicone composition according to the present invention is excellent in elongation, an intended internal pressure can be retained after the actuation of an airbag, and the cured film having excellent adhesiveness to a polyamide base cloth and a polyester base cloth can be formed even under high temperature and high humidity.
  • the silicone composition according to the present invention can be suitably used for an airbag which is highly safe as an airbag such as a curtain airbag.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Air Bags (AREA)
  • Paints Or Removers (AREA)
PCT/EP2017/075806 2016-11-07 2017-10-10 Silicone rubber composition for airbag coating WO2018082876A1 (en)

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JP2016217158A JP6757648B2 (ja) 2016-11-07 2016-11-07 エアバッグコーティング用シリコーンゴム組成物
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JP6831237B2 (ja) * 2016-12-27 2021-02-17 旭化成ワッカーシリコーン株式会社 コーティング用シリコーンゴム組成物
JP2020147686A (ja) * 2019-03-14 2020-09-17 信越化学工業株式会社 エアーバッグコーティング用シリコーンゴム組成物
JP7434522B2 (ja) * 2019-07-30 2024-02-20 ダウ シリコーンズ コーポレーション エアバッグ用のシリコーンコーティング
WO2024247071A1 (ja) * 2023-05-29 2024-12-05 信越化学工業株式会社 シリコーン粘着剤組成物および粘着性物品、密着向上剤

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