JP2020085349A - Resin composition for embolus, embolus using the same, igniter, and gas generator - Google Patents

Abstract

To provide a resin composition for embolus, an embolus using the same, an igniter, and a gas generator, which improves productivity, down-sizing the igniter by thinning the thickness of the embolus by improving strength of the embolus at high temperature, surely prevents an electrode pin from being projected, and also maintains a sealing property between the embolus and the electrode pin, and further maintains the sealing property without degrading in a heat cycle test.SOLUTION: A resin composition for embolus used for an igniter, having a resistance heating element, an ignition powder that ignites by heat generated by the resistance heating element, and an electrode pin connected to the resistance heating element, contains (A) epoxy resin, (B) hardener, and (C) organic filler.SELECTED DRAWING: Figure 1

Description

The present invention relates to an igniter used for a gas generator and a gas generator for operating an occupant safety protection device such as a seat belt pretensioner of an automobile, and more particularly to a resin composition suitable for plugging the igniter.

BACKGROUND ART Seat belt pretensioners and airbags are known as those that protect an occupant from an impact generated when a vehicle crashes. These pretensioners and the like operate by a large amount of gas introduced from the gas generator to protect the occupant. Further, the gas generator includes an igniter, a gas generating agent, etc. By igniting the igniter at the time of collision, the gas generating agent is ignited and burned to rapidly generate a large amount of gas.

An example of an igniter used in a gas generator is shown in FIG. In the igniter 1, an embolus 7 that is fitted in the cup 6 and that seals the igniting agent 2 is molded with a thermoplastic resin or the like. The embolus 7 is provided with two electrode pins 8 penetrating the embolus 7. Each of these electrode pins 8 projects into the cup 6 and electrically connects the bridge wire 3 to the tip. The ignition powder 2 is ignited and ignited by the heat generated by the bridge wire 3.

The igniter 1 is attached to a gas generator and is energized by a collision signal from a collision sensor to heat the bridge wire 3. The bridge wire 3 that has generated heat ignites and ignites the ignition powder 2. Then, the gas generating agent is ignited and burned by the generated pressure and heat generated by the combustion of the ignition powder 2, and the generated gas is ejected to the seat belt pretensioner, the airbag, or the like.

Among these igniters, a shape in which the embolus 7 and the insulating resin 5 are integrally molded with a thermoplastic resin has been proposed. As the thermoplastic resin, specifically, a resin obtained by mixing glass fiber or the like with a synthetic resin such as polybutylene terephthalate (PBT), nylon 6, or nylon 66 is used (for example, refer to Patent Document 1). ..

It has also been proposed to mold the emboli with a thermosetting resin such as unsaturated polyester (see, for example, Patent Document 2).

Further, Patent Document 3 proposes molding with a thermosetting resin such as an epoxy resin.

Further, Patent Document 4 discloses a gas generator including an igniter having an embolus composed of an insulating support portion made of an epoxy resin, a cylindrical metal sleeve, and a coating molding portion made of a thermoplastic resin.

Further, Patent Document 5 discloses an igniter having a solid body and an embolic plug made of a glass sheath and sealed with an epoxy resin.

Further, Patent Document 6 discloses a gas generator including an igniter having a header (emboli) made of a thermoplastic resin or a thermosetting resin which is an unsaturated polyester.

Further, Patent Document 7 discloses a gas generator including an igniter having a header (emboli) made of glass fiber reinforced resin.

Further, in Patent Document 8, a gas generator having a holder in which two insertion holes through which two electrode pins are individually inserted is formed and an igniter in which a hermetic material corresponding to an embolus is molded by an insulating resin Vessels are disclosed.

JP-A-2003-25950 (page 4 and FIG. 4) JP-A-2002-90097 (page 5) International Publication No. WO05/052496 Japanese Patent Laid-Open No. 2000-108838 (page 5) JP 2000-241099 A (4th and 5th pages) International Publication No. WO01/031281 International Publication No. WO01/031282 JP 2000-292100 A (FIG. 1)

As described above, in the conventional igniter, when the resin is used for the plug for sealing the ignition agent in the cup, it is common to use the thermoplastic resin. For this reason, when the igniter is used by being incorporated in a gas generator and a vehicle fire occurs during an automobile collision, or when the gas generant burns during a gas generator combustion test at a higher temperature than expected. There is a risk that the embolus made of a thermoplastic resin will be softened and two electrode pins penetrating the embolus will pop out due to the high gas pressure in the gas generator. In addition, if the thickness of the embolus is increased to prevent such a situation, the size of the igniter will increase accordingly, so the gas generator will also become larger, or the size of the gas generator will increase. If this is not possible, the fillable amount of gas generant will be reduced. Furthermore, the electrode pin and the part into which the electrode pin is inserted are made of metal, and in the case of an embolus manufactured by using those sealed with glass, the cost of parts is high and a process for melting the glass is required for manufacturing. Therefore, the manufacturing cost is high, resulting in an expensive emboli.

In addition, when the embolus is molded from the unsaturated polyester composition, it takes a relatively long time to be completely cured, resulting in poor productivity. When a peroxide is used as a curing reaction initiator, there is a problem in that the peroxide is unstable and easily decomposes, resulting in poor workability.

Furthermore, when the embolus is molded with an epoxy resin composition, because of its dimensional stability, it is necessary to highly fill the filler component, so that the molded body becomes extremely brittle, and stress and impact, etc. There is a problem that a defect occurs.
A heat cycle test (JIS60068-2-14) is often used as a method for evaluating this problem, but an embolus having sufficient resistance to the heat cycle test has not yet been developed.

In order to solve the above problems, there is also a method of sealing the electrode pins firmly so as to seal them with a glass sheath, but it is difficult to say that the productivity is necessarily excellent because the processing is performed at a high temperature for a long time. Similarly, when the embolus portion is composed of a number of members, there is a problem of sealing property between the members. Further, there is also a problem that the number of parts is increased and it takes time to manufacture.

An object of the present invention is to improve productivity and to improve the strength of the embolus at high temperature, thereby making it possible to reduce the thickness of the embolus and downsize the igniter, and to reliably prevent the electrode pin from popping out. The resin composition for embolization, which secures the sealing property between the embolus and the electrode pin, and further maintains the sealing property without deterioration even in a heat cycle test, and an igniter using the same, and gas generation Is to provide a container.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an embolic resin composition that sufficiently satisfies the above performance can be obtained.
That is, the present invention relates to the following 1) to 14).
1)
An embolic resin composition used for an igniter having a resistance heating element, an explosive which is ignited by heat generated by the resistance heating element, and an electrode pin connected to the resistance heating element,
An embolic resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) an organic filler.
2)
The embolic resin composition as described in 1) above, wherein the organic filler (C) is fine silicone particles.
3)
The embolic resin composition according to 1) or 2), wherein the organic filler (C) is fine particles having a median diameter of 100 μm or less.
4)
The embolic resin composition according to any one of 1) to 3) above, wherein the content of the organic filler (C) in the embolic resin composition is 1% by mass or more and 80% by mass or less.
5)
The embolic resin composition according to any one of 1) to 4) above, wherein the curing agent (B) is an amine curing agent.
6)
The embolic resin composition according to any one of 1) to 5) above, wherein the curing agent (B) is an aromatic amine curing agent.
7)
The embolic resin according to any one of 1) to 6) above, wherein the content of the (B) curing agent is 0.6 or more and 2.5 or less when expressed by the curing agent equivalent (f value). Composition.
8)
The embolic resin composition according to any one of 1) to 7) above, wherein the (A) epoxy resin is a liquid epoxy resin.
9)
The embolic resin composition according to any one of 1) to 8) above, wherein the (A) epoxy resin is a bisphenol F type epoxy resin.
10)
The embolic resin composition according to any one of 1) to 9) above, which further comprises (D) an inorganic filler.
11)
The embolic resin composition according to 10) above, wherein the inorganic filler (D) is silica.
12)
An embolus in which an electronic pin is held by the resin composition for embolization according to any one of 1) to 11) above, and the resin composition can be visually recognized from the bottom surface.
13)
An igniter in which an electrode pin is held by the embolic resin composition according to any one of 1) to 11) above.
14)
A gas generator comprising a cup filled with a gas generating agent for generating gas by combustion, the igniter according to the above 13) arranged inside the cup, and a holder for holding the cup.

Since the embolic resin composition of the present invention is formed of a thermosetting resin, the embolus has sufficient strength even at high temperatures, and prevents the electrode pin from coming off from the embolism because the embolism does not soften at high temperatures. it can. By doing so, compared to the case of using a thermoplastic resin, it is possible to secure the strength necessary to prevent the electrode pins from popping out even if the thickness of the embolus is reduced. Can be miniaturized.

Sectional drawing which shows an example of an igniter Front view of the emboli of the present invention Rear view of the emboli of the present invention Right side view of the embolus of the present invention Left side view of the embolus of the present invention Plan view of the emboli of the present invention Bottom view of the emboli of the present invention Sectional drawing in the AA line of the right view of the embolus of this invention.

The embolic resin composition of the present invention is an embolic resin composition used in an igniter having a resistance heating element, an explosive that is ignited by heat generated by the resistance heating element, and an electrode pin connected to the resistance heating element. (A) epoxy resin, (B) curing agent, and (C) organic filler.
[(A) Epoxy resin]
The embolic resin composition of the present invention contains (A) an epoxy resin. The epoxy resin is not particularly limited as long as it is a compound having a three-membered ring ether structure (hereinafter referred to as an epoxy group) such as an oxirane structure in the molecule, even if it has a glycidyl ether group, It may be obtained by oxidatively epoxidizing cycloalkene.

Examples of the type of epoxy resin include polyfunctional epoxy resins which are glycidyl ether compounds of polyphenol compounds, polyfunctional epoxy resins which are glycidyl ether compounds of various novolac resins, alicyclic epoxy resins, aliphatic epoxy resins, heterocyclic resins. Examples thereof include formula epoxy resins, glycidyl ester-based epoxy resins, glycidyl amine-based epoxy resins, and epoxy resins obtained by glycidylating halogenated phenols.

Examples of the polyfunctional epoxy resin which is a glycidyl ether of a polyphenol compound include phenol, cresol, bisphenol A, bisphenol F, bisphenol S, 4,4′-biphenylphenol, tetramethylbisphenol A, dimethylbisphenol A, tetramethylbisphenol. F, dimethylbisphenol F, tetramethylbisphenol S, dimethylbisphenol S, tetramethyl-4,4'-biphenol, dimethyl-4,4'-biphenylphenol, 1-(4-hydroxydiphenyl)-2-[4-( 1,1-bis-(4-hydroxydiphenyl)ethyl)phenyl]propane, 2,2′-methylene-bis(4-methyl-6-tert-butylphenol), 4,4′-butylidene-bis(3-methyl) -6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, phenols having a diisobrobilidene skeleton, phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene, phenolization Examples thereof include an epoxy resin which is a glycidyl ether of a polyphenol compound such as polybutadiene.

Examples of the polyfunctional epoxy resin which is a glycidyl ether of various novolac resins include various phenols such as phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, and naphthols as raw materials. Novolak resin, a phenol novolak resin having a xylylene skeleton, a phenol novolak resin having a dicyclopentadiene skeleton, a phenol novolac resin having a biphenyl skeleton, a glycidyl ether compound of various novolac resins such as a phenol novolac resin having a fluorene skeleton, and the like. ..

Examples of the alicyclic epoxy resin include alicyclic epoxy resins having a cyclohexane skeleton such as 3,4-epoxycyclohexylmethyl-3',4'-cyclohexylcarboxylate.

Examples of the aliphatic epoxy resin include glycidyl ethers of polyhydric alcohols such as 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, pentaerythritol, and xylylene glycol derivatives.

Examples of the heterocyclic epoxy resin include a heterocyclic epoxy resin having a heterocycle such as an isocyanuric ring and a hydantoin ring.

Examples of the glycidyl ester-based epoxy resin include epoxy resins made of carboxylic acids such as hexahydrophthalic acid diglycidyl ester and tetrahydrophthalic acid diglycidyl ester.

Examples of the glycidyl amine-based epoxy resin include epoxy resins in which amines such as aniline, toluidine, p-phenylenediamine, m-phenylenediamine, diaminodiphenylmethane derivative and diaminomethylbenzene derivative are glycidylated. Examples of the epoxy resin obtained by glycidylating halogenated phenols include brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolac, chlorinated bisphenol S, chlorinated bisphenol A and bromo. Examples thereof include epoxy resins obtained by glycidylating halogenated phenols such as phenol.

There are no particular restrictions on the use of these epoxy resins, which are appropriately selected depending on the intended use, but liquid epoxy resins are preferred as the epoxy resin of the present invention because of their ease of handling.
Further, from the viewpoint of electrical insulation, adhesiveness, water resistance, mechanical strength, workability, etc., a bisphenol type epoxy resin is preferable and a bisphenol F type epoxy resin is particularly preferable. It is not always necessary to use only one type of these epoxy resins, and two or more types may be appropriately used as a mixture.
From the viewpoint of thermal shock resistance, the epoxy equivalent is preferably in the range of 160 or more and 210 or less, and more preferably 175 or more and 200 or less.

The content of the (A) epoxy resin in the embolic resin composition is preferably 5% by mass or more and 70% by mass or less.
The lower limit of the content is more preferably 10% by mass, further preferably 15% by mass, and particularly preferably 20% by mass.
The upper limit of the more preferable content is 60% by mass, further preferably 50% by mass, and particularly preferably 40% by mass.

[(B) Curing agent]
The embolic resin composition of the present invention contains (B) a curing agent.
Examples of the curing agent include acid anhydrides, amines, phenols, imidazoles and the like.

Examples of the acid anhydrides include aromatic carboxylic acids such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol trimellitic anhydride, and biphenyl tetracarboxylic anhydride. Anhydrides, anhydrides of aliphatic carboxylic acids such as azelaic acid, sebacic acid and dodecanedioic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, nadic acid anhydride, het acid anhydride, hymic acid anhydride, etc. And alicyclic carboxylic acid anhydrides thereof. Examples of the phthalic anhydride include 4-methylhexahydrophthalic anhydride.

Examples of amines include diaminodiphenylmethane, diaminodiphenylsulfone, 4,4'-diamino-3,3'-dimethyldiphenylmethane, diaminodiphenyl ether, diethylmethylbenzenediamine, 2-methyl-4,6-bis(methylthio)-1. , Aromatic amines such as 3-benzenediamine, aliphatic amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, tetramethylethylenediamine and hexamethylenediamine, and modified amines. Especially preferred are diethylmethylbenzenediamine and 4,4'-diamino-3,3'-dimethyldiphenylmethane.

Examples of the phenols include bisphenol A, tetrabromobisphenol A, bisphenol F, bisphenol S, 4,4′-biphenylphenol, 2,2′-methylene-bis(4-methyl-6-tert-butylphenol), 2, 2'-methylene-bis(4-ethyl-6-tert-butylphenol), 4,4'-butylylene-bis(3-methyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-) 4-hydroxy-5-tert-butylphenol), trishydroxyphenylmethane, pyrogallol, phenols having a diisobrobilidene skeleton, phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene, phenolized polybutadiene Polyphenol compounds such as, phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, brominated bisphenol A, bisphenol F, bisphenol S, naphthols, etc. Examples thereof include various novolac resins such as a phenol novolac resin having, a phenol novolac resin having a dicyclopentadiene skeleton, and a phenol novolac resin having a fluorene skeleton.

Examples of the imidazoles include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-. 2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6(2'-methylimidazole (1') ) Ethyl-s-triazine, 2,4-diamino-6(2′-undecylimidazole(1′))ethyl-s-triazine, 2,4-diamino-6(2′-ethyl,4-methylimidazole( 1′)) Ethyl-s-triazine, 2,4-diamino-6(2′-methylimidazole(1′))ethyl-s-triazine/isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2:3 addition. , 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyano Various imidazoles of ethoxymethylimidazole, and salts of these imidazoles with polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid, and oxalic acid. Be done.

Which of these curing agents is used is appropriately selected depending on the properties required for the ignition squib structure or workability, but is preferably a phenol novolac resin, amines, and more preferably amines. Is.
From the viewpoint of storage stability, aromatic amines are particularly preferable, and liquid aromatic amines represented by Etacure 100 Plus (manufactured by Mitsui Chemicals Fine) are particularly preferable.

The content of these curing agents is preferably 0.6 or more and 2.5 or less in terms of curing agent equivalent (f value). In the present specification, the curing agent equivalent (f value) means the equivalent of the functional group that reacts with the epoxy group of the epoxy resin, and the case of reacting without excess or deficiency is defined as 1.0. That is, for example, in the case of an amino group, two active hydrogens are present. Therefore, if there is one epoxy group and one amino group, the amine equivalent (f value) is 2.0.
The lower limit of the curing agent equivalent (f value) is more preferably 0.7, even more preferably 0.8, and particularly preferably 0.9.
The upper limit is more preferably 2.4, further preferably 2.3, and particularly preferably 2.2.
The most preferable range of the f value is larger than 2.0 and smaller than 2.2.

[(C) Organic filler]
The embolic resin composition of the present invention contains (C) an organic filler.
Examples of the organic filler include urethane fine particles, acrylic fine particles, styrene fine particles, styrene olefin fine particles, and silicone fine particles. The silicone fine particles are preferably KMP-594, KMP-597, KMP-598 (manufactured by Shin-Etsu Chemical Co., Ltd.), Trefil ^RTM E-5500, 9701, EP-2001 (manufactured by Toray Dow Corning), and the urethane fine particles are JB-. 800T, HB-800BK (Negami Kogyo Co., Ltd.), as styrene fine particles, Lavalon ^RTM T320C, T331C, SJ4400, SJ5400, SJ6400, SJ4300C, SJ5300C, SJ6300C (manufactured by Mitsubishi Chemical) are preferable, and as styrene olefin fine particles, Septon ^RTM SEPS2004, SEPS 2063 is preferred.
These organic fillers may be used alone or in combination of two or more. A core-shell structure may be formed by using two or more kinds. Of these, silicone fine particles are preferable.
Examples of the silicone fine particles include crosslinked organopolysiloxane powder and linear dimethylpolysiloxane crosslinked powder. Examples of the composite silicone rubber include those obtained by coating the surface of the above silicone rubber with a silicone resin (for example, polyorganosilsesquioxane resin). Among these fine particles, particularly preferred are linear dimethylpolysiloxane crosslinked powder of silicone rubber or silicone resin-coated linear dimethylpolysiloxane crosslinked powder of composite silicone rubber fine particles. These may be used alone or in combination of two or more. The silicone fine particles are preferably KMP-594 and KMP-598 (manufactured by Shin-Etsu Chemical Co., Ltd.).
The median diameter of the organic filler (C) is preferably 1 μm or more and 100 μm or less. The more preferable lower limit of the median diameter is 2 μm, the further preferable lower limit is 3 μm, and the particularly preferable lower limit is 4 μm. A more preferable upper limit is 80 μm, a still more preferable upper limit is 50 μm, and a particularly preferable upper limit is 30 μm.
The median diameter can be determined from particle size distribution measurement using a laser diffraction/scattering particle size distribution measuring device (dry type) (manufactured by Seishin Enterprise Co., Ltd.; LMS-30). The median diameter corresponds to 50% of the cumulative volume distribution when the horizontal axis indicates the particle diameter and the vertical axis indicates the cumulative volume distribution (%) from the volume-based data of the filler measured by the particle size distribution measurement. Means the particle size at that time.
When the (C) organic filler is contained, the content in the embolization resin composition is preferably 1% by mass or more and 80% by mass or less.
Further, the more preferable lower limit of the content is 2% by mass, the further more preferable lower limit is 3% by mass, and the particularly preferable lower limit is 4% by mass.
The more preferable upper limit of the content is 70% by mass, the still more preferable upper limit is 60% by mass, the particularly preferable upper limit is 50% by mass, and the most preferable upper limit is 45% by mass.

The organic filler used in the present invention is preferably a soft organic filler having a 10% displacement force of 2.0 MPa or less. This 10% displacement force can be measured with a micro compression tester (MCT-510) manufactured by Shimadzu Corporation.

[(D) Inorganic filler]
The embolic resin composition of the present invention may contain (D) an inorganic filler.
Examples of the inorganic filler (D) include silica, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, mica, clay, aluminum oxide, magnesium oxide, zirconium oxide, aluminum hydroxide, and water. Magnesium oxide, calcium silicate, aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos and the like, preferably fused silica, crystalline silica, calcium carbonate, aluminum oxide, Aluminum hydroxide and calcium silicate, more preferably fused silica, crystalline silica, aluminum oxide, calcium carbonate and the like may be used. The amount of these fillers used is preferably 10 to 95% by mass, more preferably 20 to 80% by mass, and particularly preferably 30 to 70% by mass of the embolization resin composition of the present invention, in accordance with required performance and workability. is there. Further, these fillers may be used alone or in combination of two or more.
Among the above-mentioned inorganic fillers, silica is most suitable for the embolic resin composition of the present invention. Silica is a substance having a chemical composition of SiO ₂ , and either crystalline silica or fused silica can be used in the present invention. By containing silica, the embolization resin composition of the present invention greatly improves mechanical strength and heat cycle resistance.
The shape is preferably spherical in order to impart fluidity to the embolus resin composition and improve workability, and the median diameter thereof is preferably 0.1 μm or more and 50 μm or less. The more preferable lower limit of the median diameter is 1 μm, the further preferable lower limit is 5 μm, and the particularly preferable lower limit is 10 μm. A more preferable upper limit is 45 μm, a still more preferable upper limit is 40 μm, and a particularly preferable upper limit is 35 μm.
The median diameter can be determined from particle size distribution measurement using a laser diffraction/scattering particle size distribution measuring device (dry type) (manufactured by Seishin Enterprise Co., Ltd.; LMS-30). The median diameter corresponds to 50% of the cumulative volume distribution when the horizontal axis indicates the particle diameter and the vertical axis indicates the cumulative volume distribution (%) from the volume-based data of the filler measured by the particle size distribution measurement. Means the particle size at that time.

The content of the inorganic filler (D) in the embolic resin composition is preferably 10% by mass or more and 85% by mass or less.
Further, the more preferable lower limit of the content is 20% by mass, the further more preferable lower limit is 30% by mass, and the particularly preferable lower limit is 40% by mass.
A more preferable upper limit of the content is 80% by mass, a still more preferable upper limit is 75% by mass, and a particularly preferable upper limit is 70% by mass.
In addition, as the embolic resin composition of the present invention, it is a particularly preferable embodiment to use the organic filler (C) and the inorganic filler (D) together.

The inorganic filler (D) may be surface-treated with a surface treatment agent such as a silane coupling agent, a hexamethyldisilazane compound, or a polysiloxane compound.
Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrisilane. Methoxysilane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxy Silane, vinyltrimethoxysilane, N-(2-(vinylbenzylamino)ethyl)3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyl Silane coupling agents such as trimethoxysilane, isopropyl (N-ethylaminoethylamino) titanate, isopropyl triisostearoyl titanate, titanium di(dioctyl pyrophosphate)oxyacetate, tetraisopropyl di(dioctyl phosphite) titanate, neo Titanium coupling agents such as alkoxytri(p-N-(β-aminoethyl)aminophenyl) titanate, Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxyzirconate, neoalkoxytris neodecanoyl. Zirconate, neoalkoxytris(dodecanoyl)benzenesulfonyl zirconate, neoalkoxytris(ethylenediaminoethyl)zirconate, neoalkoxytris(m-aminophenyl)zirconate, ammonium zirconium carbonate, Al-acetylacetonate, Al-methacrylate, Al Examples of the coupling agent include zirconium such as propionate, or an aluminum coupling agent, and a silicon coupling agent is preferable. By using a coupling agent, a cured product having excellent moisture resistance reliability and less deterioration in adhesive strength after moisture absorption can be obtained.

To the embolic resin composition of the present invention, (E) a curing accelerator, (F) a colorant, (G) a coupling agent, (H) a leveling agent, (I) a lubricant, etc. may be added as appropriate to other components. Can be done.

(E) Examples of the curing accelerator include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6(2'-methylimidazole (1′))Ethyl-s-triazine, 2,4-diamino-6(2′-undecylimidazole(1′))ethyl-s-triazine, 2,4-diamino-6(2′-ethyl,4 -Methylimidazole (1'))ethyl-s-triazine, 2,4-diamino-6(2'-methylimidazole (1'))ethyl-s-triazine-isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2:3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3. ,5-dicyanoethoxymethylimidazole various imidazoles, and those imidazoles and polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid and oxalic acid Salts, amides such as dicyandiamide, diaza compounds such as 1,8-diaza-bicyclo(5.4.0)undecene-7 and their phenols, salts with the above polycarboxylic acids or phosphinic acids, tetra, Ammonium salts such as butylammonium bromide, cetyltrimethylammonium bromide and trioctylmethylammonium bromide, phosphines such as triphenylphosphine and tetraphenylphosphonium tetraphenylborate, phenols such as 2,4,6-trisaminomethylphenol and amines Examples thereof include adducts and microcapsule type curing accelerators containing these curing agents in microcapsules. Which of these curing accelerators is used is appropriately selected depending on the properties required for the obtained transparent resin composition such as transparency, curing speed, and working conditions. When a curing accelerator is used, the content in the embolic resin composition is preferably 0.1% by mass or more and 5% by mass or less.

(F) The colorant is not particularly limited, and examples thereof include phthalocyanine, azo, disazo, quinacridone, anthraquinone, flavanthrone, perinone, perylene, dioxazine, condensed azo, various azomethine organic dyes, titanium oxide, lead sulfate, and chromium yellow. , Zinc yellow, chrome vermillion, valve shell, cobalt purple, navy blue, ultramarine, carbon black, chrome green, chromium oxide, cobalt green, and the like.

Examples of the coupling agent (G) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2-(3,4-epoxycyclohexyl). Ethyltrimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyl Trimethoxysilane, vinyltrimethoxysilane, N-(2-(vinylbenzylamino)ethyl)3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3- Silane coupling agents such as chloropropyltrimethoxysilane, isopropyl (N-ethylaminoethylamino) titanate, isopropyltriisostearoyl titanate, titanium di(dioctyl pyrophosphate)oxyacetate, tetraisopropyl di(dioctyl phosphite) titanate , Titanium-based coupling agents such as neoalkoxytri(p-N-(β-aminoethyl)aminophenyl) titanate, Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxyzirconate, neoalkoxytris neo. Decanoyl zirconate, neoalkoxy tris(dodecanoyl)benzenesulfonyl zirconate, neoalkoxy tris(ethylenediaminoethyl) zirconate, neoalkoxy tris(m-aminophenyl)zirconate, ammonium zirconium carbonate, Al-acetylacetonate, Al-methacrylate Examples thereof include zirconium such as Al-propionate and aluminum-based coupling agents, and silicon-based coupling agents are preferable. By using a coupling agent, a cured product having excellent moisture resistance reliability and less deterioration in adhesive strength after moisture absorption can be obtained.

(H) As the leveling agent, for example, oligomers having a weight average molecular weight of 4000 to 12000, which are made of acrylates such as ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, epoxidized soybean fatty acid, epoxidized abiethyl alcohol, hydrogenated castor oil, Examples include titanium-based coupling agents.

(I) Examples of the lubricant include hydrocarbon lubricants such as paraffin wax, microwax and polyethylene wax, higher fatty acid lubricants such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and behenic acid, stearylamide, Higher fatty acid amide lubricants such as palmitylamide, oleylamide, methylenebisstearamide, ethylenebisstearamide, hydrogenated castor oil, butyl stearate, ethylene glycol monostearate, pentaerythritol (mono-, di-, tri- Or tetra-) higher fatty acid ester lubricants such as stearate, cetyl alcohol, stearyl alcohol, polyethylene glycol, alcohol lubricants such as polyglycerol, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, Examples thereof include metal soaps such as ricinoleic acid and naphthenic acid, which are metal salts of magnesium, calcium, cadmium, barium, zinc, lead and the like, and natural waxes such as cartew wax, candelilla wax, beeswax, and montan wax.

To prepare this embolic fat composition, (A) epoxy resin, (B) curing agent, (C) organic filler, if necessary (D) inorganic filler, etc., and if the compounding ingredients are solid, a Henschel mixer , Using a compounding machine such as a Nauta mixer, kneading with a kneader, extruder, heating roll, etc. at 80 to 120° C., cooling and pulverizing to obtain a resin composition for embolization as a powder. On the other hand, when the blended components are liquid, the blended components are uniformly dispersed using a planetary mixer or the like to obtain an embolization resin composition. When the viscosity of the liquid composition is high and the workability is poor, a solvent can be added to adjust the viscosity suitable for the work. Further, the solid composition may be used in a liquid state. In this case, the solid embolic resin composition obtained by the above method may be dissolved in a solvent to form a liquid. Alternatively, each compounding component may be dissolved in a solvent to form a liquid composition. The solvent used in this case is not particularly limited as long as it is a solvent usually used. When the embolic resin composition thus obtained is solid, it is generally made into pellets, molded with a molding machine such as a low-pressure transfer molding machine, and then heated to 100 to 200° C. to be cured. In the case of a liquid, it is cast in a mold or dispensed, and then heated at 100 to 200° C. to be cured to obtain an embolus. In the igniter of the present invention, for example, an electrode pin is installed on the obtained embolus of the present invention, a resistance heating element is created in the electrode portion, and a gunpowder which is ignited by the heat generated by the resistance heating element is assembled by a known or well-known process. Can be obtained at.

Further, the igniter, a case for accommodating the ignition powder, an igniter case obtained by caulking, and a cup filled with a gas generating agent for generating gas by combustion, according to a predetermined configuration, The gas generator of the present invention can be obtained by caulking by a known method.

[Preparation of Embolic Resin Composition]
After the components shown in Table 1 were mixed and kneaded with a three-roll mill, embolic resin compositions and embolic resin compositions for comparative examples were obtained.
Example 1 and Comparative Example 2 are set as embolic resin compositions, and branch numbers 1 to 6 (Example) and 1 to 2 (Comparative Example) are set depending on the difference in composition.

Epoxy resin described in the table 1: Bisphenol F type epoxy resin jER807: manufactured by Mitsubishi Chemical, epoxy equivalent 170
Curing agent 1: Liquid aromatic amine ETACURE 100 PLUS: manufactured by Mitsui Chemicals Fine (active hydrogen equivalent 44.5)
Curing agent 2: Dicyandiamide DICY7: Mitsubishi Chemical's organic filler 1: Silicone rubber powder KMP-598: Shin-Etsu Chemical Co., Ltd., median diameter 13 μm, 10% displacement force 0.6 MPa
Organic filler 2: Silicone rubber powder KMP-597: manufactured by Shin-Etsu Chemical, median diameter 5 μm, 10% displacement force 0.6 MPa
Accelerator: U-CAT3512T: San-Apro acrylic resin: dipentaerythritol hexaacrylate KAYARAD DPHA: Nippon Kayaku polymerization initiator: 2,2'-azobis(2-methylpropionitrile): Tokyo Kasei inorganic filler: spherical Silica filler FB-74X: made by Denka, median diameter 30 μm

[Preparation and characterization of emboli]
In Examples 1-3, 5 and 6, and Comparative Example 1-1, first, the hole on the bottom surface of the cup (inner diameter 7 mm, height 4 mm) was closed with a heat-resistant tape, and then a hole was formed in the center of the cup with a needle. An embolus was obtained by heating at 200° C. for 1 hour after dispensing with the electrode pin pierced and fixed in the hole. Example 1-4 was heated by the same operation at 160° C. for 3 hours, and Comparative Example 1-2 was heated by the same operation at 150° C. for 1 hour to obtain an embolus. After curing, the tape was peeled off, and the electrode pin protruding from the eyelet was scraped off by polishing.
Example 2 and Comparative Example 2 are set as emboli, and branch numbers 1 to 6 (Example) and 1 to 2 (Comparative Example) are set in the embolic resin composition used.

[Adhesion]
For adhesion, a base (1.5 cm square, thickness 0.5 cm) having a hole with a diameter of about 3 mm was fixed, an electrode pin was passed through from under the hole, and fixed with a helical tooth. Then, the maximum test force was measured at 10 mm/min. In addition, the measurement was performed with Autograph AG-Xplus (manufactured by Shimadzu Corporation).
○: 200 N or more △: 150 N or more and less than 200 N ×: less than 150 N

[Heat shock resistance]
Regarding thermal shock resistance, 3 samples were each carried out under conditions of low temperature −40° C. and high temperature 120° C. for 50 cycles (30 minutes at each temperature), the surface was observed after the test, and the number of samples with cracks was counted.
○: All without cracks △: 1-2 cracks with ×: All cracks

From the above results, it was shown that the embolic resin composition of the present invention has good properties. Further, the resin composition for embolization other than the epoxy resin containing no organic filler had insufficient adhesion and thermal shock resistance.

The igniter using the embolic resin composition of the present invention can firmly bond the electrode pin and the embolus body, and thus can easily produce the igniter.

1 Ignition device 2 Ignition charge 3 Bridge wire 4 Insulator 5 Insulating resin 6 Cup 7 Embolt 8 Electrode pin

Claims (14)

An embolic resin composition used for an igniter having a resistance heating element, an explosive which is ignited by heat generated by the resistance heating element, and an electrode pin connected to the resistance heating element,
An embolic resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) an organic filler. The embolic resin composition according to claim 1, wherein the (C) organic filler is silicone fine particles. The embolic resin composition according to claim 1 or 2, wherein the (C) organic filler is fine particles having a median diameter of 100 µm or less. The embolic resin composition according to any one of claims 1 to 3, wherein the content of the organic filler (C) in the embolic resin composition is 1% by mass or more and 80% by mass or less. The embolic resin composition according to any one of claims 1 to 4, wherein the curing agent (B) is an amine curing agent. The embolic resin composition according to any one of claims 1 to 5, wherein the curing agent (B) is an aromatic amine curing agent. The embolic resin composition according to any one of claims 1 to 6, wherein the content of the (B) curing agent is 0.6 or more and 2.5 or less when expressed as a curing agent equivalent (f value). object. The embolic resin composition according to any one of claims 1 to 7, wherein the (A) epoxy resin is a liquid epoxy resin. The embolic resin composition according to any one of claims 1 to 8, wherein the (A) epoxy resin is a bisphenol F type epoxy resin. The embolic resin composition according to any one of claims 1 to 9, which further comprises (D) an inorganic filler. The embolic resin composition according to claim 10, wherein the inorganic filler (D) is silica. An embolus in which an electronic pin is held by the embolization resin composition according to any one of claims 1 to 11, and the resin composition can be visually recognized from a bottom surface. An igniter in which an electrode pin is held by the embolic resin composition according to any one of claims 1 to 11. A gas generator comprising: a cup filled with a gas generating agent for generating gas by combustion; an igniter according to claim 13 disposed inside the cup; and a holder for holding the cup.

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