Gas forming agent composition

Abstract

A gas generating agent composition for a gas generating agent is provided, the gas generating agent composition containing guanidine nitrate, basic copper nitrate, and potassium perchlorate. In the gas generating agent composition, the content of potassium perchlorate is 12 parts by weight or more per 100 parts by weight of the total content of guanidine nitrate, basic copper nitrate, and potassium perchlorate. The gas generating agent composition further contains an amorphous oxide.

Description

Technical area

[0001] The present disclosure relates to a gas generating agent composition. background

[0002] In vehicle safety devices, such as airbags installed in vehicles, inflators employing a gas generating agent composition are used, and attempts have been made to ensure the product reliability of such inflators. While gas generating agent compositions are widely developed, attention is focused on guanidine nitrate and basic copper nitrate-type gas generating agent compositions, which use guanidine nitrate as the fuel component and basic copper nitrate as the oxidizer, from the viewpoint of minimizing the formation of toxic gases and achieving an excellent combustion rate.

[0003] For example, Patent Document 1 discloses a method for providing a guanidine nitrate and basic copper nitrate type gas generating agent composition having an excellent combustion rate by mixing a specific reducing agent and an oxidizing agent and subjecting the mixture to a specific roller compaction treatment in the production stage.

[0004] Furthermore, Patent Document 2 discloses a method for providing a guanidine nitrate and basic copper nitrate type gas generating agent composition containing potassium perchlorate, in which the content of guanidine nitrate, the content of basic copper nitrate, and the content of potassium perchlorate are each within a certain range, thereby improving combustion properties and heat resistance. Citation listPatent document Patent Document 1: JP 2009-511411 T Patent Document 2: JP 2018-154539 A Summary of the inventionTechnical problem

[0005] Typically, guanidine nitrate and basic copper nitrate type gas generating agent compositions were investigated, with the primary focus being on the burn rate, and potassium perchlorate was added in anticipation of further improvements in the burn rate.

[0006] The present inventors conducted further studies in a system in which potassium perchlorate is added to a guanidine nitrate and basic copper nitrate-type gas generating agent composition, and discovered that the ignition time is shortened as the mixing proportion of potassium perchlorate is increased. On the other hand, the present inventors also discovered that in a low-pressure environment, combustion becomes unstable and may be interrupted when the mixing proportion of potassium perchlorate reaches a certain value or more. In a case where a gas generating agent composition whose combustion is interrupted in a low-pressure environment is used in an inflator or the like, there is a risk that the combustion of the gas generating composition will be extinguished when the internal pressure of the inflator is low, such as during the initial or final stages of inflator operation.In such a case, the amount of gas to inflate the airbag may be insufficient and thus the necessary requirement to restrain the passenger may not be met.

[0007] Therefore, an object of the present disclosure is to provide a gas generating agent composition which has a short ignition time and in which combustion interruption does not easily occur in a low pressure environment. Solution to the task

[0008] As a result of intensive studies, the present inventors discovered that the above-mentioned problems can be solved by mixing a certain amount or more of potassium perchlorate into a guanidine nitrate and basic copper nitrate type gas generating agent composition and further adding an amorphous oxide, whereby the present inventors arrived at the present disclosure. [1] Gas generating agent composition comprising: Guanidine nitrate; basic copper nitrate; and potassium perchlorate, where in the gas-forming agent composition, a content of potassium perchlorate is 12 parts by weight or more, based on 100 parts by weight of the total content of guanidine nitrate, basic copper nitrate and potassium perchlorate, and the gas generating agent composition further contains an amorphous oxide. [2] The gas generating agent composition according to [1], wherein the amorphous oxide is one or more selected from the group consisting of silica gel, silicate glass, borosilicate glass, borate glass, aluminosilicate glass, aluminophosphate glass and aluminoborosilicate glass. [3] Gas generating agent composition according to [2], wherein the silica gel has an average specific surface area of 300 m 2 / g or more. [4] The gas generating agent composition according to any one of [1] to [3], wherein the total content of the amorphous oxide in the gas generating agent composition is 0.1 wt% to 10 wt%. [5] The gas generating agent composition according to any one of [1] to [4], wherein the amorphous oxide has an average aspect ratio of 8 or less. [6] The gas generating agent composition according to any one of [1] to [5], wherein the amorphous oxide has an average particle size of 1 µm to 100 µm. [7] Gas generating agent composition according to any one of [1] to [6], which does not comprise a binder. [8] Gas-forming agent composition according to [7], wherein the content of guanidine nitrate is 30 to 70 mass%. [9] A gas generating agent composition according to any one of [1] to [8], wherein the oxygen balance is -0.05 g / g to 0.05 g / g, wherein the oxygen balance is calculated on the basis of: (A) Guanidine nitrate, nitroguanidine, melamine, melamine cyanurate, 5-aminotetrazole, 5,5'-bitetrazol diammonium salt, guanylurea dinitramide, dicyanodicarbonamide, cyanuric acid, tartaric acid, sodium tartrate, succinic acid, 3-nitro-1,2,4-triazol-5-one, 2-nitroimino-5-nitrohexahydro-1,3,5-triazine and carbon-containing substances; (B) basic copper nitrate, strontium nitrate, basic copper carbonate, 5-AT-BCN complex, copper oxide, potassium perchlorate, potassium chlorate, potassium nitrate, sodium nitrate, ammonium nitrate, ammonium perchlorate, sodium perchlorate, copper(II) oxide, copper(I) oxide, phase-stabilized ammonium nitrate (AN / KN = 90 / 10) and phase-stabilized ammonium nitrate (AN / KN = 85 / 15); (C) Sodium carboxymethylcellulose, guar gum, polyacrylamide, hydroxyethylcellulose, hydroxypropylmethylcellulose, polyvinyl alcohol, ethylcellulose, polyvinylpyrrolidone, starch and silicone; and (D) Calcium stearate and magnesium stearate.

[10] The gas generating agent composition according to any one of [1] to [9], further comprising aluminum hydroxide.

[11] A gas generating agent molded article formed by molding the gas generating agent composition described in any one of [1] to

[10] into a pellet shape, a cylindrical shape having one hole, or a cylindrical shape having multiple holes.

[12] A side airbag inflator comprising: Gas generating agent composition described in one of [1] to

[10] .

[13] A side airbag inflator comprising: Gas generating agent shaped article described in

[11] . Advantageous effects of the invention

[0009] According to the present disclosure, a gas generating agent composition having a short ignition time and in which combustion interruption does not easily occur in a low-pressure environment can be provided. Description of the embodiments

[0010] In the following, embodiments of the present disclosure will be described in detail, but each configuration, a combination of configurations, and the like in each embodiment are examples, and addition, omission, substitution, and other changes can be made as appropriate without departing from the spirit of the present disclosure. The present disclosure is not limited by the embodiments and is limited only by the claims.

[0011] In the present disclosure, a numerical range expressed by "to" means a range including the numerical values described before and after "to" as the lower limit and upper limit. Specifically, "A to B" means a value that is A or more and B or less.

[0012] Furthermore, the term “A or B” in the present disclosure may be read as “at least one of the group consisting of A and B”.

[0013] Furthermore, in the present disclosure, “a plurality of” means “two or more.” Gas forming agent composition

[0014] A gas generating agent composition according to an embodiment of the present disclosure (also referred to simply as "gas generating agent composition") is a gas generating agent composition containing guanidine nitrate, basic copper nitrate and potassium perchlorate, wherein in the gas-generating agent composition, the content of potassium perchlorate is 12 parts by weight or more, based on 100 parts by weight of the total content of guanidine nitrate, basic copper nitrate and potassium perchlorate, and the gas generating agent composition further contains an amorphous oxide.

[0015] The present inventors discovered that in a system where potassium perchlorate is added to a known gas-generating agent composition of guanidine nitrate and basic copper nitrate, the time required for ignition is shortened by increasing the mixing ratio of potassium perchlorate. On the other hand, combustion becomes unstable in a low-pressure environment and is unfortunately interrupted when the mixing ratio of potassium perchlorate is at a certain level or higher.

[0016] Therefore, the inventors conducted intensive studies and discovered that a gas generating agent composition in which combustion interruption hardly occurs in a low-pressure environment even when the mixing ratio of potassium perchlorate is high can be prepared by mixing an amorphous oxide. Typically, in a low-pressure environment, a residue of the burned portion is easily dispersed, and heat transfer to the unburned portion is delayed, resulting in combustion interruption. However, the present inventors suspected that the reason why combustion interruption does not easily occur in a low-pressure environment with the gas generating agent composition of the present disclosure is that the residue is not easily dispersed and heat transfer is facilitated because the composition contains amorphous oxide.

[0017] Note that in the present disclosure, the low pressure environment means an environment with a pressure of 1 MPa or less. Guanidine nitrate

[0018] The gas-forming agent composition contains guanidine nitrate as a combustion component. The guanidine nitrate can be a product manufactured by a known process or a commercially available product.

[0019] The content of guanidine nitrate in the gas generating agent composition is not particularly limited, but is preferably 30 to 70 wt%, and more preferably 40 to 60 wt%, and in particular, when the composition is prepared by a wet process (when the composition contains a binder), the content is even more preferably 40 to 50 wt%, and when the composition is prepared by a dry process (when the composition does not contain a binder), the content of guanidine nitrate is even more preferably 50 wt% to 60 wt%.

[0020] When the guanidine nitrate content is equal to or less than the upper limit of the above range, the formation of a large amount of harmful carbon monoxide due to a lack of the oxidizing component can be prevented and the carrying capacity can be improved. When the content is equal to or greater than the lower limit of the above range, the amount of gas generated is reduced and an increase in nitrogen oxides due to excess oxygen can be prevented.

[0021] In particular, in a case where the composition is prepared by a dry method (when the composition does not contain a binder), if the content of guanidine nitrate in the composition is less than 30 mass%, it becomes difficult to mold the composition, and if the content thereof exceeds 70 mass%, the composition can be molded but has insufficient strength. Basic copper nitrate

[0022] The gas-generating agent composition contains basic copper nitrate as the first oxidizing agent. The basic copper nitrate can be a product produced by a known process or a commercially available product.

[0023] The content of basic copper nitrate in the gas generating agent composition is not particularly limited, but is usually from 10 to 60 wt%, preferably from 10 to 50 wt%, particularly preferably from 10 to 40 wt%, and even more preferably from 15 to 40 wt%.

[0024] When the basic copper nitrate content is equal to or less than the upper limit of the above range, the amount of gas generated decreases, making it easier to prevent an increase in nitrogen oxides due to excess oxygen. When the basic copper nitrate content is equal to or greater than the lower limit of the above range, the combustion temperature can be lowered while maintaining oxygen balance. Potassium perchlorate

[0025] The gas-generating agent composition contains potassium perchlorate as a second oxidizing agent. The potassium perchlorate can be a product manufactured by a known process or a commercially available product.

[0026] The content of potassium perchlorate is not particularly limited as long as its content is 12 parts by weight or more per 100 parts by weight of the total content of the guanidine nitrate, the basic copper nitrate and the potassium perchlorate in the gas generating agent composition, but the content of potassium perchlorate is preferably 12 parts by weight to 35 parts by weight, more preferably 12.5 parts by weight to 30 parts by weight, and even more preferably 12 parts by weight to 25 parts by weight.

[0027] When the above content is equal to or less than the upper limit of the above-described range, phenomena such as airbag damage due to excessive combustion temperature can be easily prevented. When the content is equal to or greater than the lower limit of the above-described range, the ignition time of the gas generating agent composition can be improved.

[0028] The total content of the guanidine nitrate, the basic copper nitrate and the potassium perchlorate in the gas generating agent composition is not particularly limited, but is usually 85 wt%, or more preferably from 90 wt% to 99.5 wt%, and even more preferably from 93 wt% to 99.5 wt%.

[0029] When the content thereof is equal to or less than the upper limit of the above-described range, the effect of the amorphous oxide can be exhibited. When the content is equal to or greater than the lower limit of the above-described range, the ignition time of the gas generating agent composition can be improved.

[0030] In the gas generating agent composition, the ratio of the content (weight) of potassium perchlorate times 100 to the content (weight) of guanidine nitrate (potassium perchlorate content (weight) × 100 / guanidine nitrate content (weight)) is not particularly limited, but is usually from 10 to 70, preferably from 10 to 60, particularly preferably from 10 to 55, even more preferably from 15 to 55, and particularly from 18 to 50.

[0031] An excessive increase in the amount of particulate residue that cannot even be captured by the inflator components can be prevented by setting the above ratio to be equal to or less than the upper limit of the above range. Furthermore, the ignition time of the gas generating agent composition can be improved by setting the ratio to be equal to or greater than the lower limit of the above range.

[0032] The oxygen balance calculated based on the components (A) and (B) described below in the gas generating agent composition is not particularly limited, but is usually from -0.05 g / g to 0.05 g / g, preferably from -0.05 g / g to 0.04 g / g, more preferably from -0.04 g / g to 0.04 g / g, even more preferably from -0.04 g / g to 0.03 g / g, and especially from -0.03 g / g to 0.03 g / g. The oxygen balance is an excess or deficiency of oxygen required for complete oxidation of the gas generating agent composition.

[0033] The oxygen balance is a positive value when there is an excess of oxygen and a negative value when there is a deficiency of oxygen.

[0034] The conditions for this oxygen balance are preferably satisfied as a parameter calculated based on the components (A) to (D) described below, but can also be satisfied as a parameter of the oxygen balance of the gas generating agent composition (the entire gas generating agent composition).

[0035] An increase in nitrogen oxides due to excess oxygen can be easily prevented by adjusting the oxygen balance to be equal to or less than the upper limit of the above range. Furthermore, an increase in carbon monoxide due to oxygen deficiency can be easily prevented by adjusting the oxygen balance to be equal to or greater than the lower limit of the above range.

[0036] The condition of the oxygen balance range described above is preferably satisfied as an oxygen balance calculated based on the following components (A) to (D). The components listed below are not essential components to the composition, but rather are components subject to oxygen balance calculation when included. Component (A) is a component corresponding to a fuel, component (B) is a component corresponding to an oxidizer, component (C) is a component corresponding to a binder, and component (D) is a component corresponding to a lubricant. In addition to these components, the gas generating agent composition may contain other components that affect the oxygen balance. (A) Guanidine nitrate, nitroguanidine, melamine, melamine cyanurate, 5-aminotetrazole, 5,5'-bitetrazol diammonium salt, guanylurea dinitramide, dicyanodicarbonamide, cyanuric acid, tartaric acid, sodium tartrate, succinic acid, 3-nitro-1,2,4-triazol-5-one, 2-nitroimino-5-nitrohexahydro-1,3,5-triazine and carbon-containing materials (e.g., activated carbon) (B) Basic copper nitrate, strontium nitrate, basic copper carbonate, 5-AT-BCN complex, copper oxide, potassium perchlorate, potassium chlorate, potassium nitrate, sodium nitrate, ammonium nitrate, ammonium perchlorate, sodium perchlorate, copper(II) oxide, copper(I) oxide, phase-stabilized ammonium nitrate (AN / KN = 90 / 10) and phase-stabilized ammonium nitrate (AN / KN = 85 / 15) (C) Sodium carboxymethylcellulose, guar gum, polyacrylamide, hydroxyethylcellulose, hydroxypropylmethylcellulose, polyvinyl alcohol, ethylcellulose, polyvinylpyrrolidone, starch and silicone (D) Calcium stearate and magnesium stearate

[0037] In the present disclosure, a term such as “phase-stabilized ammonium nitrate (AN / KN = 90 / 10)” means “ammonium nitrate (AN) phase-stabilized with potassium nitrate (KN) (based on the weight ratio AN / KN = 90 / 10)”.

[0038] Specific examples of the carbonaceous material in component (A) include activated carbon, coal, refined coal, carbon black, carbon products, solid crude oil, coal tar pitch, carbon fiber, tar, carbon, coke, graphite and the like.

[0039] A method for calculating the oxygen balance is described below.

[0040] Guanidine nitrate, for example, is oxidized by the following reaction. CH6N4O3 + O2 → 2N2 + CO2 + 3H2O

[0041] According to the following equation (1), the oxygen balance with respect to guanidine nitrate is -0.262 g / g. If the oxygen balances of basic copper nitrate and potassium perchlorate are calculated similarly from the oxidation reaction, the oxygen balance with respect to basic copper nitrate is 0.300 g / g, and the oxygen balance with respect to potassium perchlorate is 0.462 g / g. [Math. 1] Oxygen balance = amount of oxygen excess or deficiency Molecular weight of the material

[0042] For example, when the gas generating agent composition contains only guanidine nitrate, basic copper nitrate and potassium perchlorate as components (A) to (C), the oxygen balance calculated from components (A) to (C) is represented by the following equation, where a represents the content (wt%) of guanidine nitrate, b represents the content (wt%) of basic copper nitrate and c represents the content (wt%) of potassium perchlorate. Oxygen balance (g / g) of the gas-forming agent composition = {a × (−0.262) + b × 0.300 + c × 0.462} / 100

[0043] The numerical range of the oxygen balance described above is preferably satisfied as a parameter calculated based on components (A) to (D), but can also be satisfied as a parameter of the oxygen balance of the gas generating agent composition (the gas generating agent composition as a whole). When considered as the oxygen balance of the gas generating agent composition (the gas generating agent composition as a whole), the oxygen balance can be calculated from the respective oxygen balances of all components contributing to the oxygen balance in the composition.

[0044] The oxygen balance of each component (A) to (D) is shown in Table 1 below. In Table 1, Al(OH)3 and basic magnesium carbonate are listed as components (E), which are substances that can be added, but these substances do not contribute to the oxygen balance (i.e., their oxygen balance is 0 g / g). [Table 1] Table 1 Component A Oxygen balance (g / g) composition Oxygen balance (g / g) Guanidine nitrate -0,262 C Sodium carboxymethylcellulose -1,004 Nitroguanidine -0,307 Guar gum -1,143 melamine -1,142 Polyacrylamide -1,688 Melamine cyanurate -0,847 Hydroxyethylcellulose -1,368 5-Aminotetrazole -0,658 Hydroxypropylmethylcellulose -1,474 5,5'-Bitetrazol diammonium salt -0,744 Polyvinyl alcohol -1,818 Guanylurea dinitramide -0,191 Ethylcellulose -1,761 A Dicyanodicarbonamide -1,142 Polyvinylpyrrolidone -1,725 Cyanuric acid -0,558 Strength -1,185 Tartaric acid -0,533 silicone -1,726 sodium tartrate -0,348 D Calcium stearate -2,741 succinic acid -0,949 Magnesium stearate -2,814 3-Nitro-1,2,4-triazol-5-one -0,246 E Al(OH)3 0 2-Nitroimino-5-nitrohexahydro-1,3,5-triazine -0,635 Basic magnesium carbonate 0 Carbonaceous material -2,664 Basic copper nitrate 0,300 Strontium nitrate 0,378 Basic copper carbonate 0,145 5-AT-BCN complex 0,052 copper oxide 0,201 B Potassium perchlorate 0,462 potassium chlorate 0,392 potassium nitrate 0,396 Sodium nitrate 0,471 Ammonium nitrate 0,200 Ammonium perchlorate 0,340 Sodium perchlorate 0,523 Copper(II) oxide 0,201 copper(I) oxide 0,112 Phase-stabilized ammonium nitrate (AN / KN = 90 / 10) 0,220 Phase-stabilized ammonium nitrate (AN / KN = 85 / 15) 0,229 Amorphous oxide

[0045] In addition to the above-mentioned components, the gas generating agent composition contains an amorphous oxide. By mixing the amorphous oxide into the gas generating agent composition, a sufficient combustion amount of the gas generating agent composition can be ensured while simultaneously ensuring a short ignition time.

[0046] The type of the amorphous oxide is not particularly limited, and examples include one or more substances selected from the group consisting of silica gel, silicate glass, borosilicate glass, borate glass, aluminosilicate glass, aluminophosphate glass, and aluminoborosilicate glass. The amorphous oxide is preferably one or more substances selected from the group consisting of silica gel, aluminophosphate glass, and aluminoborosilicate glass, and more preferably one or more substances selected from the group consisting of silica gel and aluminoborosilicate glass. From the viewpoint of a short combustion time in a low-pressure environment, the amorphous oxide is even more preferably silica gel. Note that the oxygen balance of the amorphous oxides specifically listed here is 0 g / g.

[0047] As the above-mentioned amorphous oxide, an oxide prepared by a known method or a commercially available product can be used.

[0048] The total content of the amorphous oxide in the gas generating agent composition is not particularly limited, but is preferably from 0.1 to 10 wt%, more preferably from 0.5 to 10 wt%, even more preferably from 0.5 to 5 wt%, and especially from 0.5 to 3 wt%.

[0049] An increase in the ignition time of the gas generating agent composition can be prevented by setting the above content equal to or less than the upper limit of the above range. Furthermore, the combustion interruption phenomenon in a low-pressure environment can be improved by setting the content equal to or greater than the lower limit of the above range.

[0050] The shape of the amorphous oxide is not particularly limited and may be, for example, a particulate or non-fibrous form. From the viewpoint of the density of the gas generating agent composition, the shape of the amorphous oxide is preferably a particulate form. In the present disclosure, particulate form means that the average aspect ratio is 8 or less.

[0051] The average aspect ratio of the amorphous oxide is not particularly limited, but is usually 8 or less, preferably 7.5 or less, and more preferably 7 or less. The lower limit is not particularly limited, but may be 1 or more.

[0052] When the average aspect ratio is equal to or smaller than the upper limit of the above range, the density of the gas-generating composition can be improved, which contributes to weight reduction of the inflator.

[0053] The average aspect ratio of the amorphous oxide can be calculated as follows. (1) In a case where the amorphous oxide can be collected from the gas generating agent composition, a plurality of amorphous oxides (at least ten amorphous oxide particles) are collected, each amorphous oxide is observed using a scanning electron microscope (SEM), a ratio of the major axis to the minor axis (major axis / minor axis) of each amorphous oxide is determined, and the average aspect ratio is calculated as an average value of the determined ratios.Otherwise, (2) in a case where the amorphous oxide cannot be collected from the gas generating agent composition, a cross section of the gas generating agent composition is observed using a scanning electron microscope (SEM), the ratio of the major axis to the minor axis (major axis / minor axis) of each amorphous oxide observed on the cross section is determined, and the average aspect ratio is calculated as the average value of the determined ratios.

[0054] When the amorphous oxide is in the form of particles, the average particle size is not particularly limited, but is usually from 0.1 µm to 100 µm, preferably from 0.5 µm to 100 µm, particularly preferably from 1 µm to 100 µm, even more preferably from 2 µm to 90 µm, and especially from 2 µm to 80 µm.

[0055] When the average particle size is within the above range, the effect of improvement against combustion interruption in a low pressure environment can be demonstrated.

[0056] The average particle size of the amorphous oxide can be calculated as follows. (1) In a case where the amorphous oxide can be collected from the gas generating agent composition, a plurality of amorphous oxides (at least ten amorphous oxides) are collected, each amorphous oxide is observed using a scanning electron microscope (SEM), the particle size of each amorphous oxide is determined, and the average particle size is calculated as the average value of the determined particle sizes. Otherwise, (2) in a case where the amorphous oxide cannot be collected from the gas generating agent composition, a cross-section of the gas generating agent composition is observed using a scanning electron microscope (SEM), the particle size of each amorphous oxide observed on the cross-section is determined, and the average particle size is calculated as the average value of the determined particle sizes.

[0057] In a case where silica gel, which is a porous material, is used as the amorphous oxide, the average specific surface area is not particularly limited, but is preferably 250 m 2 / g or more, and particularly preferably 300 m 2 / g or more, and is preferably 900 m 2 / g or less, particularly preferably 700 m 2 / g or less, and more preferably 500 m 2 / g or less. With respect to amorphous oxides other than porous materials such as silica gel, it is preferable to specify the average particle size within a preferred range instead of the average specific surface area.

[0058] When the average specific surface area is equal to or less than the upper limit of the above range, an increase in hygroscopicity of the gas generating agent composition can be more easily prevented. Furthermore, when the average specific surface area is equal to or greater than the lower limit of the above range, a decrease in combustibility can be more easily prevented.

[0059] The average specific surface area described above can be measured using a gas adsorption method. Additional components

[0060] The gas generating agent composition may contain components other than the above-described guanidine nitrate, basic copper nitrate, potassium perchlorate, and amorphous oxide (hereinafter referred to as "additional components"), and examples of the additional components include fuel components other than guanidine nitrate, oxidizers other than basic copper nitrate and potassium perchlorate, binders, lubricants, neutralizing agents, and other known additives.

[0061] Examples of fuel components other than guanidine nitrate include one or more selected from tetrazole compounds including 5-aminotetrazole and bitetrazole ammonium salt; guanidine compounds (except nitroguanidine) including guanidine nitrate and dicyandiamide; and triazine compounds including melamine, trimethylolmelamine, alkylated methylolmelamine, ammeline, ammelide, nitrates of melamine, perchlorates of melamine, trihydrazinotriazine, and nitrated melamine compounds. Furthermore, among the above-mentioned components (A), one other than these fuel components may also be used as a fuel component.

[0062] Examples of oxidizing agents other than basic copper nitrate and potassium perchlorate include one or more selected from basic cobalt nitrate, basic zinc nitrate, basic manganese nitrate, metal nitrates, ammonium nitrate, metal perchlorates, ammonium perchlorate, metal chlorates, and metal nitrites. Furthermore, among the above-mentioned components (B), an oxidizing agent other than these can also be used as an oxidizing agent.

[0063] Examples of the binder include one or more selected from carboxymethylcellulose (CMC), carboxymethylcellulose sodium salt (CMCNa), carboxymethylcellulose potassium salt, carboxymethylcellulose ammonium salt, cellulose acetate, cellulose acetate butyrate (CAB), ethylcellulose (EC), hydroxyethylcellulose (HEC), microcrystalline cellulose, polyacrylhydrazide, acrylamide-acrylic acid metal salt copolymers, polyacrylamide-polyacrylate composite copolymers, acrylic rubber, and silicone. In addition, among the above-mentioned components (C), a component other than these binders may also be used as a binder. The gas generating agent composition may or may not contain a binder.

[0064] Examples of the lubricant include one or more selected from calcium stearate, magnesium stearate and the like.

[0065] Examples of neutralizing agents include compounds containing one or more cations selected from alkali metals and alkaline earth metals. Such compounds include carbonates, silicates, nitrates, oxalates, peroxides, or oxides of alkali metals and alkaline earth metals, such as sodium carbonate, sodium silicate, sodium nitrate, sodium oxalate, strontium peroxide, calcium peroxide, magnesium oxide, strontium oxide, or calcium oxide.

[0066] Examples of other known additives include one or more selected from metal oxides such as cupric oxide, iron oxide, zinc oxide, cobalt oxide, manganese oxide, molybdenum oxide, nickel oxide, bismuth oxide, silicon dioxide, and aluminum oxide; metal hydroxides such as aluminum hydroxide, magnesium hydroxide, cobalt hydroxide, and iron hydroxide; cobalt carbonate, calcium carbonate; composite compounds of metal oxides or hydroxides such as acid clay, kaolin, talc, bentonite, and diatomaceous earth; acidic metal salts such as sodium silicate, mica molybdate, cobalt molybdate, and ammonium molybdate; and molybdenum disulfide, calcium stearate, silicon nitride, silicon carbide, metaboric acid, boric acid, and boric anhydride, and glass.

[0067] The gas generating agent composition may contain Al(OH)3 (aluminum hydroxide) as an additional component in addition to the above-mentioned components, and from the viewpoint of reducing the combustion temperature of the gas generating agent composition, this addition is advantageous when aminophosphate glass is used as the amorphous oxide.

[0068] When Al(OH)3 is used, the content of Al(OH)3 in the gas generating agent composition is not particularly limited, but from the viewpoint of reducing the combustion temperature of the gas generating agent composition, the content is preferably 0.5 wt% to 10 wt%, more preferably 1 wt% to 10 wt%, and even more preferably 1 wt% to 8 wt%.

[0069] The content of each component in the gas-generating agent composition can be analyzed using both general qualitative and quantitative methods. For example, the content can be analyzed by combining measurement results such as ion chromatography, FT-IR, ICP-AES, and XRD. The content of each component can also be calculated from the amounts of raw materials used in the gas-generating agent composition.

[0070] The gas generating agent composition can be molded into a desired shape for use and can be formed into a molded article (gas generating agent molded article) having a shape such as a pellet shape, a disc shape, a spherical shape, a rod shape, a cylindrical shape, a cylindrical shape with one hole, or a cylindrical shape with multiple holes, with particular preference given to a pellet shape, a cylindrical shape with one hole, or a cylindrical shape with multiple holes. These molded articles can be produced by a method in which water or an organic solvent is added to the gas generating agent composition, mixed, and then the mixture is subjected to extrusion molding, or by a method in which the mixture is subjected to compression molding using a tabletting machine or the like.

[0071] Since the gas generating agent composition according to an embodiment of the present disclosure has a high combustion rate, the molded article does not need to be made small, and a complicated production process is not required.

[0072] The gas generating agent composition according to an embodiment of the present disclosure or a molded article thereof (hereinafter referred to as the gas generating agent composition or the like, in various vehicles) can be applied, for example, to an airbag inflator for a driver's seat, an airbag inflator for a passenger's seat, a side airbag inflator, an inflatable curtain inflator, a knee bolster inflator, an inflatable seatbelt inflator, a tubular system inflator, or a pretensioner inflator. Among these, the gas generating agent composition or the like can be preferably applied to a side airbag inflator that requires early deployment and, in particular, requires a short ignition time and a sufficient combustion amount.

[0073] An inflator containing the gas generating agent composition or an article formed therefrom may be a pyro-type in which the gas source is only the gas generating agent, or a hybrid type in which a gas is supplied from both compressed gas, such as argon, and the gas generating agent.

[0074] The gas-generating agent composition or an article formed therefrom can also be used as an ignition agent, referred to as an amplifier (or booster), which serves to transfer the energy of an igniter or primer to the gas-generating agent. A method for producing a gas-generating agent composition

[0075] The method for producing the gas generating agent composition described above is not particularly limited, and the gas generating agent composition can be produced by a known method or by a combination of known methods. For example, the composition can be produced by preparing and mixing the desired raw materials. Specifically, the gas generating agent composition can be produced by a dry method in which the raw materials are mixed in a powdery state, or by a wet method in which the raw materials are mixed in the presence of water, an organic solvent, or the like.

[0076] When the gas generating agent composition is used as a molded article, the molded article can be produced by using a tabletting machine to compression-mold the mixture prepared by the above dry method, or the molded article can be produced by extruding the mixture prepared by the above wet method with an extruder, followed by cutting and drying. The production conditions in these methods for producing the molded article are not particularly limited and can be appropriately adjusted depending on the purpose. For example, when the extrusion molding method is adopted, molding a body with a thin sheet is easier than the compression molding method, and therefore a molded article can be produced even with a composition having a slow burning rate.Furthermore, the extrusion molding process is suitable for mass production because molding can be completed in a relatively short time. Furthermore, using the extrusion molding process, a molded article with a complex shape, such as a shape without a hole, a shape with a hole, or a shape with multiple holes, can be produced, thus achieving various combustion properties.

[0077] When preparing the gas-generating agent composition, when molding is performed using the above-mentioned tabletting machine, a lubricant is preferably used. The type of the lubricant is not particularly limited, and examples include calcium stearate, magnesium stearate, sucrose fatty acid esters, and talc. The content of the lubricant in the gas-generating agent composition can be from 0.1 mass% to 1 mass% or from 0.15 mass% to 0.6 mass%.

[0078] When measuring each feature in the present disclosure, unless otherwise specified, the measurement sample is kept in an environment identical to the measurement environment for 2 hours or more before measurement. Furthermore, unless otherwise specified, the measurement temperature, humidity, and pressure are set to normal temperature (26 ± 2°C), normal humidity (59 ± 5% RH), and normal pressure (atmospheric pressure). Examples

[0079] The present disclosure will be described in more detail below with reference to examples. However, the present disclosure should not be construed as being limited to the following examples. Test 1 Preparation of the gas-forming agent composition Comparative Example 1

[0080] The raw materials were prepared in the proportions shown in Table 2, and these raw materials were then mixed with water equal to 0.16 times the total weight of the raw materials. The mixture was then extruded with an extrusion molding machine at a shear rate of 200 / s to 1000 / s using a 3.4 mm die. The diameter of the resulting sample, when shrunk, was 3.2 mm after drying. The sample prepared by this extrusion was cut into lengths of 2.6 to 2.9 mm to form cylindrical pellets. To remove the water, the pellets were allowed to stand at normal temperature for 48 hours or more as a preliminary drying step and then dried in a dryer at 110 °C for 72 hours or more, thereby preparing a gas-generating agent composition (oxygen balance: -0.01 g / g).This oxygen balance is the oxygen balance calculated based on the components (A) to (D) described above, and the same applies to other examples and comparative examples. Comparison example 2

[0081] The raw materials were prepared in the proportions shown in Table 2, and these raw materials were then mixed with water 0.16 times the total weight of the raw materials, after which a gas generating agent composition (oxygen balance: -0.01 g / g) was prepared in the same manner as in Comparative Example 1. Comparison example 3

[0082] The raw materials were prepared in the proportions shown in Table 2, and these raw materials were blended, and then the mixture was granulated. Subsequently, 0.15 wt% of calcium stearate, based on the total weight of the raw materials, was added as a lubricant. The mixture was then compression-molded using a tabletting machine at 19 to 22 kN to produce a gas-generating agent composition (oxygen balance: -0.01 g / g) in the form of cylindrical pellets with a bottom diameter of 3.2 mm and a height of 2.6 to 2.9 mm. Comparison example 4

[0083] The raw materials were prepared in the proportions shown in Table 2, and these raw materials were then mixed with water 0.16 times the total weight of the raw materials, after which a gas generating agent composition (oxygen balance: -0.01 g / g) was prepared in the same manner as in Comparative Example 1. Comparison example 5

[0084] The raw materials were prepared in the proportions shown in Table 2, and these raw materials were then mixed with water 0.16 times the total weight of the raw materials, after which a gas generating agent composition (oxygen balance: -0.01 g / g) was prepared in the same manner as in Comparative Example 1. Comparison example 6

[0085] The raw materials were prepared in the proportions shown in Table 2, and these raw materials were then mixed with water 0.16 times the total weight of the raw materials, after which a gas generating agent composition (oxygen balance: -0.01 g / g) was prepared in the same manner as in Comparative Example 1. Example 1

[0086] The raw materials were prepared in the proportions shown in Table 2, and these raw materials were mixed, after which a gas generating agent composition (oxygen balance: -0.01 g / g) was prepared in the same manner as in Comparative Example 3. As the aluminoborosilicate glass, one with an average particle size of 11 µm and an average length of 75 µm (average aspect ratio: 6.82) was used. Example 2

[0087] The raw materials were prepared in the proportions shown in Table 2, and these raw materials were then mixed with water 0.16 times the total weight of the raw materials, after which a gas generating agent composition (oxygen balance: -0.01 g / g) was prepared in the same manner as in Comparative Example 1. The silica gel used was one with an average particle size of 3 to 5 µm, an average aspect ratio of 1 to 1.2, and an average specific surface area of 300 m 2 / g is used. Example 3

[0088] The raw materials were prepared in the proportions shown in Table 2, and these raw materials were then mixed with water 0.16 times the total weight of the raw materials, after which a gas generating agent composition (oxygen balance: -0.01 g / g) was prepared in the same manner as in Comparative Example 1. The aluminoborosilicate glass used was one with an average particle size of 11 µm, an average length of 75 µm, and an average aspect ratio of 6.82. Combustion test under atmospheric pressure

[0089] 100 g of the gas generating agent composition was placed on a SUS plate, and at a test site under atmospheric pressure, a nickel-chromium wire was brought into contact with a portion of it. A predetermined current was passed through the nickel-chromium wire, the gas generating agent composition was ignited by the fusion energy thereof, and the 100 g of the gas generating agent composition was burned. Then, it was confirmed whether a portion of the unburned gas generating agent composition remained (combustion was interrupted) or whether the entire gas generating agent composition was completely burned. The confirmation results are shown in Table 2. In Table 2, A means that complete combustion was achieved, and B means that combustion was interrupted.

[0090] The meaning of the abbreviations in Table 2 is given below. The same applies to the other tables. - GN: guanidine nitrate; - BCN: Basic copper nitrate - KClO4: potassium perchlorate - Al(OH)3: aluminum hydroxide - CMCNa: carboxymethylcellulose sodium salt

[0091] It should be noted that the mixing ratios in Table 2 can be considered as the content proportions of the components in the gas generating agent composition. 5 cm 3 -Bomb 10% ignition time

[0092] A predetermined amount of 0.7 g of the above-mentioned gas-forming agent composition was placed in a 5-cm 3 -Bomb test apparatus and ignited in a low temperature environment (-40 °C) by a ZPP-containing ignition powder, and the time until 10% of the maximum pressure was reached was defined as the ignition time. [Table 2] Table 2 Production process Mixing ratio Mixing ratio with GN + BCN + KClO4 to 100 parts by weight Combustion quantity 5 cm 3 -Bomb 10% ignition time (when set to -40 °C) GN BCN KClO4 Al(OH)3 CMCNa Aluminoborosilicate glass Aluminophosphate glass Silicon dioxide GN BCN KClO4 % by weight % by weight % by weight % by weight % by weight % by weight % by weight % by weight parts by weight parts by weight parts by weight - milliseconds Comparison example 1 Wet process 43,00 52,00 0,00 0,00 5,00 0,00 0,00 0,00 45,26 54,74 0,00 A 7,6 Comparison example 2 Wet process 50,60 37,45 8,95 0,00 3,00 0,00 0,00 0,00 52,16 38,61 9,23 A 4,5 Comparison example 3 Dry process 58,44 29,56 12,00 0,00 0,00 0,00 0,00 0,00 58,44 29,56 12,00 B 3,6 Comparison example 4 Wet process 46,84 36,16 12,00 0,00 5,00 0,00 0,00 0,00 49,31 38,06 12,63 B 3,9 Comparison example 5 Wet process 46,31 35,69 12,00 1,00 5,00 0,00 0,00 0,00 49,27 37,97 12,77 B 3,9 Comparison example 6 Wet process 45,24 34,76 12,00 3,00 5,00 0,00 0,00 0,00 49,17 37,78 13,04 B 4,2 Example 1 Dry process 57,38 28,62 12,00 0,00 0,00 2,00 0,00 0,00 58,55 29,20 12,24 A 3,5 Example 2 Wet process 46,31 35,69 12,00 0,00 5,00 0,00 0,00 1,00 49,27 37,97 12,77 A 4,0 Example 3 Wet process 46,18 33,42 13,40 0,00 5,00 2,00 0,00 0,00 49,66 35,94 14,41 A 4,0

[0093] Table 2 shows that the ignition time becomes shorter with increasing the blending ratio of potassium perchlorate in the gas generating agent composition. On the other hand, in the embodiments where no amorphous oxide was added, combustion was interrupted when the blending ratio of potassium perchlorate was 11 wt% or more, while in the embodiments where an amorphous oxide was added, complete combustion was achieved while maintaining a short ignition time, even when the blending ratio of potassium perchlorate was 11 wt% or more. Comparison example 7

[0094] The raw materials were prepared in the proportions shown in Table 3, and these raw materials were then mixed with water 0.16 times the total weight of the raw materials, after which a gas generation composition (oxygen balance: -0.01 g / g) was prepared in the same manner as in Comparative Example 1. Comparative example 8

[0095] The raw materials were prepared in the proportions shown in Table 3, and these raw materials were then mixed with water 0.16 times the total weight of the raw materials, after which a gas generation composition (oxygen balance: -0.01 g / g) was prepared in the same manner as in Comparative Example 1. Comparison example 9

[0096] The raw materials were prepared and mixed in the proportions shown in Table 3, and then a gas-forming composition (oxygen balance: -0.01 g / g) was prepared in the same manner as in Comparative Example 3. Example 4

[0097] The raw materials were prepared and mixed in the proportions shown in Table 3, and a gas-forming composition (oxygen balance: -0.01 g / g) was prepared in the same manner as in Comparative Example 3. As the aluminophosphate glass, one with an average particle size of 30 to 65 µm and an average aspect ratio of 1 to 2 was used.

[0098] The properties of each of the above-mentioned gas-generating compositions were evaluated by the same tests as the above-mentioned atmospheric pressure combustion test and the 5-cm 3 bomb with 10% ignition time using 100 g of the gas-evolving composition. The evaluation results are shown in Table 3. [Table 3] Table 3 Production process Mixing ratio Mixing ratio with GN + BCN + KClO4 to 100 parts by weight Combustion quantity 5 cm 3 -Bomb 10% ignition time (when set to -40 °C) GN BCN KClO4 Al(OH)3 CMCNa Aluminoborosilicate glass Aluminophosphate glass Silicon dioxide GN BCN KClO4 % by weight % by weight % by weight % by weight % by weight % by weight % by weight % by weight parts by weight parts by weight parts by weight - milliseconds Comparison example 7 Wet process 45,34 42,86 6,80 0,00 5,00 0,00 0,00 0,00 47,73 45,12 7,16 A 6,7 Comparative example 8 Wet process 40,71 49,29 0,00 5,00 5,00 0,00 0,00 0,00 45,23 54,77 0,00 A 10,4 Comparison example 9 Dry process 56,35 24,65 14,00 5,00 0,00 0,00 0,00 0,00 59,32 25,95 14,74 B 3,8 Example 4 Dry process 56,35 24,65 14,00 4,00 0,00 0,00 1,00 0,00 59,32 25,95 14,74 A 4,2

[0099] Table 3 shows that the ignition time becomes shorter with increasing the blending ratio of potassium perchlorate in the gas generating agent composition. On the other hand, in the embodiments where no amorphous oxide was added, combustion was interrupted when the blending ratio of potassium perchlorate was 11 wt% or more, while in the embodiment where an amorphous oxide was added, complete combustion was achieved while maintaining a short ignition time even when the blending ratio of potassium perchlorate was 11 wt% or more. Test 2 Preparation of the gas-forming agent composition Reference Example 1

[0100] The raw materials were prepared in the proportions shown in Table 4 and these raw materials were mixed, after which a gas generating agent composition was prepared in the same manner as in Comparative Example 3. Reference example 2

[0101] The raw materials were prepared in the proportions shown in Table 4 and these raw materials were mixed, after which a gas generating agent composition was prepared in the same manner as in Comparative Example 3. Reference example 3

[0102] The raw materials were prepared in the proportions shown in Table 4 and these raw materials were mixed, after which a gas generating agent composition was prepared in the same manner as in Comparative Example 3. Reference example 4

[0103] The raw materials were prepared in the proportions shown in Table 4 and these raw materials were mixed, after which a gas generating agent composition was prepared in the same manner as in Comparative Example 3. Load capacity test

[0104] A pellet of the gas-generating agent composition was clamped between flat metal fixtures and diametrically compressed. A load was applied using a compression tester. The point at which the pellet cracked and broke was measured as the load-bearing capacity. The evaluation results are shown in Table 4. [Table 4] Table 4 Production process Mixing ratio Mixing ratio with GN + BCN + KClO4 to 100 parts by weight Load capacity GN BCN KClO4 Al(OH)3 CMCNa Aluminoborosilicate glass Aluminophosphate glass Silicon dioxide GN BCN % by weight % by weight % by weight % by weight % by weight % by weight % by weight % by weight parts by weight parts by weight Kgf Reference example 1 Dry process 30 70 0 0 0 0 0 0 30 70 14,14 Reference example 2 Dry process 50 50 0 0 0 0 0 0 50 50 16,71 Reference example 3 Dry process 70 30 0 0 0 0 0 0 70 30 10,69 Reference example 4 Dry process 100 0 0 0 0 0 0 0 100 0 3,06

[0105] Table 4 shows that a gas generating agent composition with excellent carrying capacity can be prepared by adjusting the amount of GN in the gas generating agent composition within a certain range. In the system of the present embodiment containing GN and BCN as the main components, the content ratio of GN is important in terms of carrying capacity, but the carrying capacity is not easily affected by other substances such as BCN, KClO4, and amorphous oxide. Therefore, it is expected that the same tendency will be observed even when substances such as KClO4 and amorphous oxide are included. Industrial applicability

[0106] The gas generating agent composition according to the present disclosure has a short ignition time, and combustion interruption is less likely to occur in a low-pressure environment. Therefore, the gas generating agent composition can be completely combusted with a short ignition time even when the pressure inside the inflator becomes low, such as in the initial or final stages of inflator operation. When the gas generating agent composition is used in an airbag, a sufficient amount of gas can be ensured to inflate the airbag, and the requirements necessary to restrain a passenger can be more easily met. QUOTES CONTAINED IN THE DESCRIPTION

[0000] This list of documents submitted by the applicant was generated automatically and is included solely for the convenience of the reader. This list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions. Cited patent literature

[0000] JP 2009-511411 T

[0004] JP 2018-154539 A

[0004]

Claims

[1] Gas generating agent composition comprising: Guanidine nitrate; basic copper nitrate; and potassium perchlorate, where in the gas-forming agent composition, a content of potassium perchlorate is 12 parts by weight or more, based on 100 parts by weight of the total content of guanidine nitrate, basic copper nitrate and potassium perchlorate, and the gas generating agent composition further contains an amorphous oxide. [2] The gas generating agent composition according to claim 1, wherein the amorphous oxide is one or more selected from the group consisting of silica gel, silicate glass, borosilicate glass, borate glass, aluminosilicate glass, aluminophosphate glass and aluminoborosilicate glass. [3] The gas generating agent composition according to claim 2, wherein the silica gel has an average specific surface area of 300 m 2 / g or more. [4] The gas generating agent composition according to any one of claims 1 to 3, wherein the total content of the amorphous oxide in the gas generating agent composition is 0.1 wt% to 10 wt%. [5] The gas generating agent composition according to any one of claims 1 to 4, wherein the amorphous oxide has an average aspect ratio of 8 or less. [6] The gas generating agent composition according to any one of claims 1 to 5, wherein the amorphous oxide has an average particle size of 1 µm to 100 µm. [7] A gas generating agent composition according to any one of claims 1 to 6, which does not comprise a binder. [8] The gas generating agent composition according to claim 7, wherein the content of guanidine nitrate is 30 to 70 mass%. [9] A gas generating agent composition according to any one of claims 1 to 8, wherein the oxygen balance is -0.05 g / g to 0.05 g / g, wherein the oxygen balance is calculated on the basis of: (A) Guanidine nitrate, nitroguanidine, melamine, melamine cyanurate, 5-aminotetrazole, 5,5'-bitetrazol diammonium salt, guanylurea dinitramide, dicyanodicarbonamide, cyanuric acid, tartaric acid, sodium tartrate, succinic acid, 3-nitro-1,2,4-triazol-5-one, 2-nitroimino-5-nitrohexahydro-1,3,5-triazine and carbon-containing substances; (B) basic copper nitrate, strontium nitrate, basic copper carbonate, 5-AT-BCN complex, copper oxide, potassium perchlorate, potassium chlorate, potassium nitrate, sodium nitrate, ammonium nitrate, ammonium perchlorate, sodium perchlorate, copper(II) oxide, copper(I) oxide, phase-stabilized ammonium nitrate (AN / KN = 90 / 10) and phase-stabilized ammonium nitrate (AN / KN = 85 / 15); (C) Sodium carboxymethylcellulose, guar gum, polyacrylamide, hydroxyethylcellulose, hydroxypropylmethylcellulose, polyvinyl alcohol, ethylcellulose, polyvinylpyrrolidone, starch and silicone; and (D) Calcium stearate and magnesium stearate. [10] A gas generating agent composition according to any one of claims 1 to 9, further comprising aluminum hydroxide. [11] A gas generating agent molded article formed by molding the gas generating agent composition described in any one of claims 1 to 10 into a pellet shape, a cylindrical shape having one hole, or a cylindrical shape having multiple holes. [12] A side airbag inflator comprising: Gas generating agent composition as described in any one of claims 1 to 10. [13] A side airbag inflator comprising: Gas generating agent shaped article described in claim 11.