JP6782741B2 - A crystalline radically polymerizable composition for encapsulating an in-vehicle ignition coil, an in-vehicle ignition coil encapsulant using the composition, and a method for producing the encapsulant. - Google Patents

Description

The present invention relates to a crystalline radically polymerizable composition for encapsulating an in-vehicle ignition coil, a granular material composed of the composition, an in-vehicle ignition coil encapsulant sealed by the composition, and an in-vehicle ignition coil seal. Regarding the manufacturing method of radicals.

An in-vehicle ignition coil mounted on an automobile is basically composed of a core made of a magnetic material, a primary bobbin, a primary coil, a secondary bobbin, a secondary coil and the like. A resin composition is filled between these parts for the purpose of maintaining insulation. A current flows directly through the primary coil connected to the battery, and a temporary voltage is obtained by self-induction action accompanied by a change in magnetic flux. This primary voltage is applied by the mutual induction action of the primary coil and the secondary coil to generate a spark discharge in the spark plug connected to the terminal. For this reason, thermosetting resin compositions having high electrical insulation and heat resistance are often used to seal the ignition coil for vehicles.

Recently, as an insulating treatment material for an in-vehicle ignition coil, a liquid epoxy resin and an epoxy resin composition having excellent electrical insulation, mechanical strength, fluidity, and dimensional stability, and an in-vehicle ignition sealed with the resin and the resin composition. A method for manufacturing a coil and the device is known (for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 2018-24734

An in-vehicle ignition coil molded product using a liquid epoxy resin and an epoxy resin composition is manufactured by a method such as casting, which is relatively poor in productivity. Further, the in-vehicle ignition coil molded body needs to be post-cured after molding in order to obtain the required molded product characteristics. Therefore, a highly productive manufacturing method is expected.

Therefore, the present invention is to provide a crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil, which is excellent in fluidity and insulation and has good handleability.

As a result of various studies on a composition containing at least a crystalline radical polymerizable compound from various viewpoints, the present inventor has found the crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil of the present invention. I arrived.

That is, the crystalline radically polymerizable composition for encapsulating an in-vehicle ignition coil of the present invention comprises a crystalline radically polymerizable compound having a glass transition point and a melting point , an inorganic filler, a silane coupling agent, and radical polymerization. It is characterized by containing at least an initiator.

Further, in a preferred embodiment of the crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil of the present invention, the crystalline radical polymerizable compound is a crystalline unsaturated polyester, a crystalline epoxy (meth) acrylate, or a crystalline crystal. It is characterized by containing one or more selected from urethane (meth) acrylate, crystalline polyester (meth) acrylate, crystalline polyether (meth) acrylate, crystalline radical polymerizable monomer, and crystalline radical polymerizable multimer. And.

Further, in a preferred embodiment of the crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil of the present invention, the crystalline radical polymerizable compound exhibits a melting point in the range of 30 to 150 ° C.

Further, in a preferred embodiment of the crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil of the present invention, the crystalline radical polymerizable composition is characterized in that it is solid at 23 ° C.

Further, in a preferred embodiment of the crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil of the present invention, the melt viscosity of the crystalline radical polymerizable composition by an enhanced flow tester is measured at a measurement temperature of 90 ° C. and a die. The diameter is 0.5 mm, the length is 1.0 mm, and the pressure is 7 to 1000 Pa · s at a pressure of 30 kgf / cm ² , or 1 to 7 Pa · s at a pressure of 1 kgf / cm ² .

Further, in a preferred embodiment of the crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil of the present invention, the inorganic filler is 50 to 95% by weight based on the total amount of the crystalline radical polymerizable composition. It is characterized by that.

Furthermore, in a preferred embodiment of the automotive ignition coil sealing crystalline radically polymerizable composition of the present invention, the proportion of the crystalline radical polymerizable compound to the radical polymerizable compound the total amount is 30 parts by weight or more It is a feature.

Further, in a preferred embodiment of the crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil of the present invention, the weight average molecular weight of the crystalline radical polymerizable compound is 100 to 100,000.

Further, the vehicle-mounted ignition coil encapsulant of the present invention is characterized in that it is sealed with the crystalline radical polymerizable composition for encapsulating the vehicle-mounted ignition coil of the present invention.

Further, the granular material of the present invention is characterized by comprising the crystalline radically polymerizable composition for encapsulating an in-vehicle ignition coil of the present invention.

Further, in the method for producing an in-vehicle ignition coil encapsulant of the present invention, the granules composed of the crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil of the present invention are insert-molded by an injection molding method or a transfer molding method. It is characterized by having a step of sealing an in-vehicle ignition coil by the method.

According to the crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil of the present invention, an effect excellent in handleability is exhibited. Further, according to the method for producing an in-vehicle ignition coil encapsulant of the present invention, a crystalline radical polymerizable composition having extremely low viscosity is obtained during heat melting during injection molding and transfer molding, so that the in-vehicle ignition coil is sealed. It has the advantageous effect of ensuring the fluidity required for stopping.

Further, according to the present invention, it is possible to provide an in-vehicle ignition coil encapsulant sealed with a crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil.

Further, according to the present invention, an in-vehicle ignition coil encapsulant having a step of encapsulating an in-vehicle ignition coil by an insert molding method for granules, powder, and a tablet made of a crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil. Manufacturing method can be provided.

The crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil of the present invention is characterized by containing at least a crystalline radical polymerizable compound, an inorganic filler, a silane coupling agent, and a radical polymerization initiator. To do. This is because, by using the crystalline radical polymerizable composition, it is possible to realize a polymerizable composition having excellent fluidity and excellent handling, as shown in Examples described later. In the present specification, the crystalline radical polymerizable composition for encapsulating the ignition coil for automobiles may be referred to as a crystalline radical polymerizable composition. Further, examples of the type of ignition coil include an ignition coil for magneto ignition, an ignition coil for battery ignition, an ignition coil for CDI ignition, and the like, and the composition of the present invention can be applied to any of the ignition coils. The ignition coil is used in a broad sense, and may include an ignition coil, a spark coil, and the like.

Further, in a preferred embodiment of the crystalline radically polymerizable composition for encapsulating an in-vehicle ignition coil of the present invention, the crystalline radically polymerizable compound is an unsaturated polyester, an epoxy (meth) acrylate, a urethane (meth) acrylate, or the like. It is characterized by containing one or more selected from polyester (meth) acrylate, polyether (meth) acrylate, radically polymerizable monomer, and radically polymerizable multimer.

Although crystallinity is omitted, specifically, the crystalline radically polymerizable compound is a crystalline unsaturated polyester, a crystalline epoxy (meth) acrylate, a crystalline urethane (meth) acrylate, or a crystalline polyester (meth). ) It can contain one or more selected from acrylate, crystalline polyether (meth) acrylate, crystalline radical polymerizable monomer, and crystalline radical polymerizable multimer. When these polymerizable compounds are used, the mechanical properties and handleability are improved (the crystallinity may be omitted even below).

In the present specification, the crystalline compound can be a compound having a glass transition point and a melting point. These temperatures can be confirmed by thermal analyzers such as DSC (Differential Scanning Calorimeter) and TGDTA (Differential Thermal Weight Simultaneous Measuring Device). The crystalline compound in the present invention can be a compound whose melting point can be confirmed by a thermal analyzer.

Further, in a preferred embodiment of the crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil of the present invention, the crystalline radical polymerizable compound is the crystalline radical polymerizable compound from the viewpoint of workability and moldability. Is characterized by having a melting point of 30 to 150 ° C., more preferably 30 to 120 ° C., and even more preferably 30 to 100 ° C. Crystalline radical polymerizable having a melting point in the range of 30 to 150 ° C. as compared with the case of using a crystalline radical polymerizable compound having a melting point of less than 30 ° C. or a crystalline radically polymerizable compound having a melting point higher than 150 ° C. This is because better handleability can be achieved by using a compound. When the melting point of the crystalline radical polymerizable compound is lower than the above range, it tends to become a liquid at room temperature, so that the crystalline radical polymerizable composition may not maintain a solid state. When the melting point of the crystalline radical polymerizable compound is higher than the above range, it is close to the molding temperature of the mold, so that the time from the start of flow to curing is shortened, and molding defects may occur.

Further, when only a crystalline radically polymerizable compound having a melting point of less than 30 ° C. is used, it tends to be difficult to obtain a solid crystalline radically polymerizable composition at 23 ° C. On the other hand, when only a crystalline radical polymerizable compound having a melting point higher than 150 ° C. is used, the cylinder temperature and the mold temperature are used when plasticizing the crystalline radical polymerizable composition in the cylinder in the injection molding method. Due to their proximity, they tend to be less stable in the cylinder.

Further, in a preferred embodiment of the crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil of the present invention, the crystalline radical polymerizable composition is prepared at 23 ° C. from the viewpoint of handleability of the crystalline radical polymerizable compound. It is characterized by being solid. The above range is set because the shape of the composition does not change under the manufacturing / molding / transporting environment of the crystalline radical polymerizable composition, so that continuous production is possible under general-purpose manufacturing equipment / conditions. The shape and volume of a solid can be easily changed by an external force.

Further, in a preferred embodiment of the crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil of the present invention, the melt viscosity of the crystalline radical polymerizable composition is measured by an enhanced flow tester from the viewpoint of fluidity. The temperature is 90 ° C., the diameter of the die is 0.5 mm, the length is 1.0 mm, the pressure is 7 to 1000 Pa · s at a pressure of 30 kgf / cm ² , or 1 to 7 Pa · s at a pressure of 1 kgf / cm ² , and more preferably 1 to 1. It can be in the range of 100 Pa · s. When the melt viscosity of the crystalline radical polymerizable composition is lower than the above range, many thin burrs are generated and the burrs are difficult to peel off from the mold, and further, the composition enters the gaps of the mold, which makes continuous molding difficult. If the melt viscosity is higher than the above range, the filling property is poor at the time of molding, and there is a risk that the product cannot be obtained.

Further, in a preferred embodiment of the crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil of the present invention, from the viewpoint of product quality, the inorganic filler is 50 with respect to the total amount of the crystalline radical polymerizable composition. It can be ~ 95% by weight, more preferably 55 to 93% by weight, and even more preferably 60 to 90% by weight. When the amount of the inorganic filler is less than the above range, the shrinkage rate is large and the molded product is deformed, and when the amount is more than the above range, the melt viscosity at the time of molding is high and the insert is loaded. This is because the insert may be damaged.

Furthermore, in a preferred embodiment of the automotive ignition coil sealing crystalline radically polymerizable composition of the present invention, from the viewpoint of maintaining the solid, of the crystalline radical polymerizable compound to the radical polymerizable compound the total amount, 30 wt The amount may be 40 parts by weight or more, more preferably 50 parts by weight or more, and more preferably 50 parts by weight or more. The reason for setting the above range is that if the proportion of the crystalline radically polymerizable compound is smaller than the above range, it may be difficult to become a solid.

Further, in a preferred embodiment of the crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil of the present invention, the weight average molecular weight of the crystalline radical polymerizable compound from the viewpoint of quality control of the crystalline radical polymerizable composition. However, it can be 100 to 100,000, more preferably 100 to 50,000, and even more preferably 150 to 30,000. The above range is defined as when the weight average molecular weight of the crystalline radical polymerizable compound is smaller than the above range, the crystalline radical polymerizable composition is unlikely to become a solid, and when it is larger than the above range, the crystalline radical polymerizable composition is crystalline radical polymerizable. This is because the molecular weight of the composition cannot be controlled with high accuracy, so that the compound properties and the composition properties may fluctuate.

Further, the vehicle-mounted ignition coil encapsulant of the present invention is characterized in that it is sealed with the crystalline radical polymerizable composition for encapsulating the vehicle-mounted ignition coil of the present invention.

Further, the granular material of the present invention is characterized by comprising the crystalline radically polymerizable composition for encapsulating an in-vehicle ignition coil of the present invention. Although it is a granular material, the present invention may be a powder, a tablet, or the like in addition to the granular material. That is, in the case of non-granular substances, the powder, tablet, etc. of the present invention can be composed of the crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil of the present invention.

Further, in the method for producing an in-vehicle ignition coil encapsulant of the present invention, the granules composed of the crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil of the present invention are insert-molded by an injection molding method or a transfer molding method. It is characterized by having a step of sealing an in-vehicle ignition coil by the method.

The vehicle-mounted ignition coil encapsulant is basically composed of a magnetic core, a primary coil, and a secondary coil. The magnetic core is housed in a resin molded body case such as PPS, and the gap between the core and the case is sealed with an insulating resin composition. When the ignition coil for a vehicle is ignited, a voltage is applied, so that electrical insulation is required. Further, since the gap between the core and the case is narrow, good fluidity is required for the resin composition that seals the primary coil and the secondary coil. If the fluidity of the resin composition is poor, the resin composition may not be sufficiently filled in the coil windings, resulting in voids during molding, which may cause a short circuit. The composition of the present invention can be applied to an in-vehicle ignition coil encapsulant that requires electrical insulation and high fluidity.

A composition having a low melt viscosity and a good fluidity may have a problem in handleability because the composition is soft even at room temperature. In addition, the soft composition becomes lumpy, the composition is fused in the hopper in the injection molding method, the tablet molded in advance is fused in the transfer molding method, and the shape is changed to cause the tablet in the transfer molding machine. There is a risk that it will not fit in the insertion hole. The present invention exerts an excellent effect of having high productivity by achieving both fluidity and handleability.

<Manufacturing method of unsaturated polyester>
In one example, the unsaturated polyester used in the present invention comprises, for example, unsaturated polybasic acid, saturated polybasic acid and glycols by a known dehydration condensation reaction, and usually has an acid value of 2 to 40 mg-KOH / g. Can have. In the production of unsaturated polyester, unsaturated polybasic acid, unsaturated polybasic acid, unsaturated polybasic acid, and unsaturated polybasic acid have crystalline properties by appropriately selecting and combining the acid components, the selection and combination of glycols, and the blending ratio thereof. It can be polyester.

Examples of unsaturated polybasic acids include maleic acid, maleic anhydride, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, glutaconic acid and the like.

Saturated polybasic acids include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebatic acid, azelaic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, headet. Acids, tetrabrom phthalic anhydride and the like can be mentioned.

The glycols are ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, propylene glycol, diethylene glycol, and triethylene glycol. , Dipropylene glycol, neopentyl glycol, 1,3-butanediol, hydride bisphenol A, bisphenol A propylene oxide compound, cyclohexanedimethanol, dibrom neopentyl glycol and the like.

In the present invention, among crystalline unsaturated polyesters, fumaric acid is used as the unsaturated polybasic acid, isophthalic acid and terephthalic acid are used as the saturated polybasic acid, and ethylene glycol and 1,3-propanediol are mainly used as glycols. , 1,4-Butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, and cyclohexanedimethanol are preferably used as unsaturated polyesters.

<Manufacturing method of epoxy (meth) acrylate>
The epoxy (meth) acrylate used in the present invention can be produced by a method known per se. Epoxy having crystallization by appropriately selecting an epoxy resin and an unsaturated monobasic acid in the presence or absence of a known prohibiting agent and a known esterification catalyst, in an inert gas stream or in an air atmosphere ( It can be a meta) epoxy acrylate. If necessary, another radically polymerizable monomer or an organic solvent can be added for the purpose of lowering the melt viscosity of the reaction system for the reaction.

As an example, the epoxy (meth) acrylate in the present invention is obtained by adding acrylic acid or methacrylic acid to an epoxy resin having two or more glycidyl ether groups in one molecule, and the acrylate or methacrylate is added to the molecular terminal. It can be an epoxy (meth) acrylate having a double bond. An epoxy (meth) acrylate resin in which an epoxy (meth) acrylate is dissolved in a radically polymerizable monomer and / or a radically polymerizable multimer may be used. The epoxy resin having two or more glycidyl ether groups in one molecule is, for example, bisphenol A, bisphenol F, bisphenol S, etc., or a bisphenol type epoxy resin from these derivatives, bixilenol and bixilenol from a derivative thereof. Examples thereof include type epoxy resins, biphenol type epoxy resins from biphenols and derivatives thereof, naphthalene type epoxy resins from naphthalene and its derivatives, and epoxy resins such as novolak type epoxy resins, which may be used alone or in combination of two or more. Can be mixed and used. The epoxy equivalent, which is a measure of the molecular weight of the epoxy resin, is preferably 174 to 2000 eq / g.

<Manufacturing method of urethane (meth) acrylate>
Further, the urethane (meth) acrylate in the present invention is, for example, as an example, for example, a polyalcohol having two or more hydroxyl groups in one molecule and / or a polyester polyol and / or a polyether polyol and a diisocyanate at the molecular terminal. Isocyanates and / or one or more isocyanates in one molecule are reacted with an alcoholic hydroxyl group and a compound having one or more acrylate groups or methacrylate groups, or first, an alcoholic hydroxyl group and one or more acrylate groups or methacrylates are reacted. The compound having a group and diisocyanate are reacted so that an isocyanate group remains, and the remaining isocyanate group is reacted with a polyalcohol and / or a polyester polyol and / or a polyether polyol having two or more hydroxyl groups in one molecule. It can be a urethane acrylate having a double bond of acrylate or methacrylate at the molecular terminal obtained. In the production of urethane (meth) acrylate, a combination of isocyanate, polyalcohol and / or polyester polyol and / or polyether polyol, and a compound having an alcoholic hydroxyl group and one or more acrylate groups or methacrylate groups should be appropriately selected. Therefore, it can be made into a urethane (meth) epoxy acrylate having crystallinity. A urethane (meth) acrylate resin in which urethane acrylate or urethane methacrylate is dissolved in a radically polymerizable monomer such as styrene or diethylene glycol dimethacrylate and / or a radically polymerizable multimer may be used. These can be used alone or in mixtures of two or more.

Examples of the compound having an alcoholic hydroxyl group and one or more acrylate groups or methacrylate groups include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and phenoxyhydroxypropyl (meth). ) Acrylate, trimethylolpropane di (meth) acrylate, dipropylene glycol mono (meth) acrylate and the like can be used.

The polyalcohol having two or more hydroxyl groups in one molecule includes, for example, neopentyl glycol, ethylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1, , 4-Butandiol, 1,5-Pentanediol, 1,6-Hexanediol, 1,7-Heptanediol, 1,8-Octanediol, 1,9-Nonandiol, 1,10-Decandiol, Propylene Glycol, diethylene glycol, dipropylene glycol, trimethylene glycol, hydrogenated bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, etc. are used for polyester polyols having two or more hydroxyl groups in one molecule. Polyalcohols such as neopentyl glycol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, trimethylene glycol, hydrogenated bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, adipic acid, (anhydrous) A saturated polyester polyol having a molecular weight of 1000 to 2000 obtained from a dehydration condensation reaction with a polybasic acid such as phthalic acid, isophthalic acid, terephthalic acid, or trimellitic acid, and a polyether polyol having two or more hydroxyl groups in the above molecule. Uses polyethylene glycol, polypropylene glycols having a molecular weight of 300 to 2000 obtained by the ring-opening reaction of ethylene oxide or propylene oxide, polycaprolactone obtained by the ring-opening reaction of caprolactone, etc., alone or in combination of two or more. can do.

As the compound having two or more isocyanate groups in one molecule, aromatic and / or aliphatic polyisocyanate compounds are used, for example, tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,6-hexa. Methylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, trifunctional isocyanate having an isocyanurate ring in which a bifunctional isocyanate compound is triquantized, isocyanate prepolymer modified with a commercially available polyol, and the like can be mentioned. Can be done. These can be used alone or in combination of two or more.

<Manufacturing method of polyester (meth) acrylate>
Further, the polyester (meth) acrylate in the present invention is, for example, at the molecular terminal obtained by esterification of a polyester polyol with acrylic acid or methacrylic acid, or a reaction between an acid-terminated polyester and an acrylate or methacrylate having a glycidyl group. It can be a polyester acrylate having a double bond of an acrylate or a methacrylate, or a polyester methacrylate. In the production of polyester (meth) acrylate, crystalline polyester (meth) acrylate can be obtained by appropriately selecting polyester polyol and acrylic acid or methacrylic acid, or acid-terminated polyester and acrylate or methacrylate having a glycidyl group. .. A polyester acrylate resin or a polyester methacrylate resin in which polyester acrylate or polyester methacrylate is dissolved in a radically polymerizable monomer such as styrene or diethylene glycol dimethacrylate and / or a radically polymerizable multimer may be used. These can be used alone or in mixtures of two or more.

<Manufacturing method of polyether (meth) acrylate>
Further, the polyether (meth) acrylate in the present invention is obtained, for example, by esterification of a polyether polyol with acrylic acid or methacrylic acid, or a reaction of an acid-terminated polyether with an acrylate or methacrylate having a glycidyl group. It can be a polyether acrylate or a polyether methacrylate having a double bond of acrylate or methacrylate at the end of the molecule. In the production of a polyether (meth) acrylate, a crystalline polyester (meth) acrylate is obtained by appropriately selecting a polyether polyol and acrylic acid or methacrylic acid, or an acid-terminated polyester and an acrylate or methacrylate having a glycidyl group. Can be done. It may be a polyether acrylate resin in which a polyether acrylate or a polyether methacrylate is dissolved in a radically polymerizable monomer such as styrene or diethylene glycol dimethacrylate and / or a radically polymerizable multimer, or a polyether methacrylate resin. These can be used alone or in mixtures of two or more.

In a preferred embodiment, the crystalline radically polymerizable monomer solid at 30 to 150 ° C. in the present invention is an ethoxylated isocyanuric acid triacrylate (melting point about 50 ° C.), polyethylene glycol di (meth) acrylate (melting point 35 to 35 ° C. 53 ° C), methoxypolyethylene glyco (meth) acrylate (melting point 33-40 ° C), behenyl acrylate (melting point 46 ° C), tetramethylpiperinidyl methacrylate (melting point 56-60 ° C), trimetalyl isocyanurate (melting point 83-87) ℃), Diacetoneacrylamide (melting point about 56 ℃), Itaconic acid dimethyl ester (melting point 36 ℃), Vinyl stearate (melting point 36 ℃), N-vinylcarbazole (melting point 67 ℃), N-methylolacrylamide (melting point 71- 75 ° C.), acrylamide (melting point 84 ° C.), tolylene diallyl carbamate (melting point 85-110 ° C.), maleimide (melting point 93 ° C.), acenaftylene (melting point 95 ° C.), and the like. When these crystalline radically polymerizable compounds are used, the handleability is improved.

As the radically polymerizable monomer in the present invention, a radically polymerizable monomer that is liquid at room temperature can be used as long as the object is not impaired. For example, vinyl aromatic compounds such as styrene monomer having a vinyl group, α-methylstyrene, vinyltoluene, α-chlorostyrene; vinyl acetate, vinyl propionate, vinyl lactate, vinyl butyrate, Beova monomer (manufactured by Shell Chemical Co., Ltd.), etc. Vinyl esters: (meth) acrylic acid esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and the like can be mentioned.

Bifunctionals such as triallyl cyanurate, diethylene glycol dimethacrylate, diallyl tetrabromphthalate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 1,6-hexanediol diacrylate, diallyl phthalate having an allyl group, and triallyl isocyanurate. The above radical polymerizable monomer can be used. These radically polymerizable monomers may be used alone or in combination of two or more.

As the radically polymerizable multimer in the present invention, diallyl phthalate prepolymer, tike prepolymer, epoxy prepolymer, urethane prepolymer, and acrylate prepolymer can be used. These radically polymerizable multimers may be used alone or in combination of two or more.

An inorganic filler can be blended in the crystalline radically polymerizable composition for encapsulating an in-vehicle ignition coil of the present invention. Examples of the inorganic filler include calcium carbonate, magnesium carbonate, barium carbonate, calcium hydroxide, aluminum hydroxide, magnesium hydroxide, magnesium oxide, alumina, silica, zinc oxide, mica, aluminum nitride, and boron nitride. Of these, silica is preferable from the viewpoint of fluidity. These may be used alone or in combination of two or more.

As the inorganic filler, one having an average particle diameter of 100 μm or less, preferably 0.01 to 50 μm, can be used. By using the inorganic filler having the above average particle size, it is possible to obtain a crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil having excellent fluidity and strength during molding.

In the crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil of the present invention, various additives that adhere to an inorganic filler and a reinforcing material, for example, a (meth) acrylate compound having a polar group and a coupling agent are blended. Can be done.

The (meth) acrylate compound having a polar group is not particularly limited, and examples thereof include a (meth) acrylate compound in which a substituent containing an atom other than carbon and hydrogen is ester-bonded, and examples of the substituent include a hydroxyl group and an epoxy. Examples thereof include a group, a glycidyl ether group, a tetrahydrofurfuryl group, an isocyanate group, a carboxyl group, an alkoxysilyl group, a phosphate ester group, a lactone group, an oxetane group, a tetrahydropyranyl group and an amino group. The coupling agent is not particularly limited, but for example, a silane-based coupling agent, a titanate-based coupling agent, or the like can be used, and the silane coupling agent is, for example, an epoxysilane-based, aminosilane-based, or cationicsilane. Systems, vinylsilane-based, acrylicsilane-based, mercaptosilane-based, and composite systems thereof and the like can be used.

Of these, an acrylic silane coupling agent is preferable from the viewpoint of improving strength. In addition, any additive can be used as long as the object of the present invention is not impaired.

In the crystalline radical polymerizable composition for encapsulating an vehicle-mounted ignition coil of the present invention, a heat-decomposable organic peroxide usually used in unsaturated polyester resin compositions and radically polymerizable compositions as a radical polymerization initiator. Or a polymerization inhibitor can be used.

Examples of organic peroxides include t-butyl peroxy-2-ethylhexyl monocarbonate, 1,1-di (t-hexyl peroxy) cyclohexane, and 1,1-di (t-butyl peroxy) -3,3. Examples thereof include 5-trimethylcyclohexane, t-butyl peroxyoctate, benzoyl peroxide, methyl ethyl ketone peroxide, acetylacetone peroxide, t-butyl peroxybenzoate, and dicumyl peroxide. These may be used alone or in combination of two or more.

Among these, from the viewpoint of molding conditions and storage stability, it is preferable to use an organic peroxide having a 10-hour half-life temperature of 100 ° C. or higher, and specifically, dicumyl peroxide can be preferably used.

Examples of the polymerization inhibitor include hydroquinone, monomethyl ether hydroquinone, toluhydroquinone, di-t-4-methylphenol, monomethyl ether hydroquinone, phenothiazine, t-butylcatechol, parabenzoquinone, quinones such as pyrogallol, and 2,6-di t-. Phenols such as butyl-p-cresol, 2,2-methylene-bisu (4-methyl-6-t-butylphenol), 1,1,3-tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane Phenols, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-methoxy-2,2, Piperidine such as 6,6-tetramethylpiperidine-1-oxyl, 4-carboxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 2,2,6,6-tetramethylpiperidine-1-oxyl -1-Oxyls can be mentioned. By using these, thickening during filling during molding can be suppressed, and a radically polymerizable composition having a low melt viscosity can be obtained. These may be used alone or in combination of two or more.

In the crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil of the present invention, a reinforcing material can be blended. By using the reinforcing material, it is possible to obtain a crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil having excellent strength characteristics and dimensional stability.

As the reinforcing material used in the present invention, glass fibers used in fiber reinforced plastics such as BMC (bulk molding compound) and SMC (sheet molding compound) are usually used, but are limited to glass fibers. However, other than that can be used.

Glass fibers include silicate glass, E glass (non-alkali glass for electricity), C glass (alkali-containing glass for chemicals), A glass (acid resistant glass), and S glass (high-strength glass) made from silicate glass. Glass fibers such as, etc. can be mentioned, and those made into long fibers (roving), short fibers (chopped strands), and milled fibers can be used. Further, as these glass fibers, those which have been subjected to surface treatment can also be used.

Further, in the crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil of the present invention, other inorganic fillers may be appropriately used as long as the fluidity of the composition and the characteristics of the encapsulant are not impaired. Can be blended.

Examples of these include oxides and hydrates thereof, inorganic foamed particles, hollow particles such as silica balloons, and the like.

A mold release agent can be used in the crystalline radically polymerizable composition for encapsulating an in-vehicle ignition coil of the present invention. As the release agent, waxes such as fatty acid-based, fatty acid metal salt-based, and mineral-based waxes generally used for thermosetting resins can be used, and in particular, fatty acid-based, fatty acid metal salt-based, which are excellent in heat-resistant discoloration. And waxes can be preferably used.

Specific examples of these release agents include stearic acid, zinc stearate, aluminum stearate, calcium stearate, paraffin wax and the like. These release agents may be used alone or in combination of two or more.

As the mold release agent, an external mold release agent such as a mold release agent of a type to be sprayed or applied to a mold or a molding material containing a mold release agent can also be used, if necessary.

In the present invention, in addition to these compounding components, a curing catalyst, a polymerization inhibitor, a colorant, a thickener, a wet dispersant, a surface conditioner, and a reduction agent for adjusting the curing conditions of the crystalline radical polymerizable composition. A thickener, a flow modifier, other organic additives, an inorganic additive and the like can be appropriately blended as needed.

<Method for producing crystalline radically polymerizable composition>
The crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil of the present invention is a kneader or an extruder capable of heating and pressurizing after mixing each component and mixing them sufficiently uniformly using a mixer, a blender or the like. It can be prepared by, etc., granulated and manufactured.

Further, the granules, powders and tablets of the present invention are characterized by comprising the crystalline radical polymerizable composition for encapsulating an vehicle-mounted ECU substrate of the present invention. The granular material composed of the crystalline radically polymerizable composition for encapsulating the vehicle-mounted ignition coil of the present invention may be in the form of pellets.

Further, the vehicle-mounted ignition coil encapsulant of the present invention is characterized in that granules, powders and tablets made of the crystalline radically polymerizable composition for encapsulating the vehicle-mounted ignition coil of the present invention are molded and sealed. To do. The in-vehicle ignition coil encapsulant can be molded by a conventional method by a molding method of various thermosetting compositions.

Further, since the crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil of the present invention is a dry type and has good thermal stability at the time of melting, injection molding method, injection compression molding method, and transfer can be used as molding methods. A melt heating molding method such as a molding method or a compression molding method can be preferably used.

Among these, an injection molding method using an injection molding machine and a transfer molding method using a transfer molding machine are particularly suitable, the molding time is shortened by the injection molding method, and many molded bodies are molded at one time by the transfer molding method. It is possible to manufacture an in-vehicle ignition coil encapsulant having a complicated shape.

<Method for automotive ignition coil encapsulant and automotive ignition coil encapsulant>
The in-vehicle ignition coil encapsulant of the present invention can be produced by encapsulating electrical and electronic components by an insert molding method using the in-vehicle ignition coil encapsulating crystalline radical polymerizable composition of the present invention. .. Here, the crystalline radical-polymerizable composition for encapsulating an in-vehicle ignition coil of the present invention contains all the components constituting the crystalline radical-polymerizable composition even if they are separately preliminarily heat-kneaded. A part or all of the mixture may be mixed and heat-kneaded immediately before the mold injection.

The temperature and pressure of the crystalline radical polymerizable composition at the time of mold injection are not particularly limited, but when an injection molding machine is used, the crystalline radical polymerizable composition temperature is 60 to 130 ° C. and the mold temperature is 130 to 190. When the temperature of the crystalline radical polymerizable composition is 0.1 to 10 MPa, the mold temperature of the transfer molding machine is 130 to 190 ° C., and the pressure of the crystalline radical polymerizable composition is 0.1 to 10 MPa, the temperature of the crystalline radical polymerizable composition is 0.1 to 10 MPa. It is preferable because the damage is reduced.

The method for molding the vehicle-mounted ignition coil of the present invention is not particularly limited. For example, the vehicle-mounted ignition coil mounted on an automobile is basically a core made of a magnetic material, a primary bobbin, a primary coil, and a secondary coil. Since it is composed of a secondary bobbin, a secondary coil, etc., a process of inserting an ignition coil including these primary coils, a secondary coil, a core (for example, a magnetic core), etc. into a case, and an in-vehicle vehicle of the present invention in the case. The step of encapsulating and curing the crystalline radical polymerizable composition for encapsulating the ignition coil for sealing the ignition coil can be included.

Hereinafter, one embodiment of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

<Production example of a radically polymerizable composition for encapsulating an in-vehicle ignition coil>
Examples 1-11, Reference Example 1, and Comparative Examples 1-2
The crystalline or amorphous radical polymerizable compositions of Examples 1 to 11 shown in Table 2, Reference Example 1 and Comparative Examples 1 to 2 shown in Table 3 are blended in the amounts shown in Tables 2 and 3 below. The mixture was mixed and uniformly prepared using a kneader capable of heating and cooling under pressure, and then the preparation was put into an extruder and hot-cut to obtain granules. Some granular and massive radically polymerizable compositions were powdered using a pulverizer.

The obtained radically polymerizable composition and the like were prepared by using a hydraulic molding machine (manufactured by Toho Press Mfg. Co., Ltd.) until the mold temperature was 165 ° C., the curing time was 180 seconds, or the test piece could be obtained. The physical properties of the molded test piece were evaluated by the methods described below, and are shown in Tables 2 and 3, respectively.

The following ingredients were used as compounding ingredients.
(1) Polymerizable compound 1. Crystalline radically polymerizable compound 1: Phthalic acid-based unsaturated polyester (condensate of terephthalic acid, fumaric acid and 1,6-hexanediol)
2. Crystalline radically polymerizable compound 2: Urethane methacrylate (2-hydroxyethyl methacrylate adduct of 1,6-hexamethylene diisocyanate)
3. 3. Crystalline radically polymerizable compound 3: Urethane acrylate (2-hydroxyethyl acrylate adduct of 1,6-hexamethylene diisocyanate)
4. Crystalline Radical Polymerizable Monomer 1: Ethoxylated Isocyanuric Acid Triacrylate (A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.)
5. Amorphous radically polymerizable compound 1: Phthalate-based unsaturated polyester (Yupika 8552H manufactured by Japan U-Pica Co., Ltd.)
6. Amorphous radical polymerizable compound 2: Bisphenol A type epoxy methacrylate (methacrylic acid adduct of bisphenol A type epoxy resin)
7. Radical Polymerizable Monomer 1: Dialyl Phthalate Monomer (Daiso Dup Monomer manufactured by Osaka Soda Co., Ltd.)
8. Radical Polymerizable Monomer 2: Diethylene Glycol Dimethacrylate (2G manufactured by Shin-Nakamura Chemical Co., Ltd.)

(2) Inorganic filler 1. Inorganic filler 1: Fused silica (Made by Denka Co., Ltd., average particle size 24 μm)
2. Inorganic filler 2: Calcium carbonate (Made by Nitto Powder Co., Ltd., average particle size 2 μm)

(3) Additives 1. Silane coupling agent: Methacrylic silane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.)
2. Radical Polymerization Initiator: Dicumyl Peroxide (Park Mill D, manufactured by NOF CORPORATION)
3. 3. Release agent: Zinc stearate (GF-200 manufactured by NOF CORPORATION)
4. Polymerization inhibitor: Perabenzoquinone (PBQ manufactured by Seiko Kagaku Co., Ltd.)
5. Colorant: Carbon black (CB40 manufactured by Mitsubishi Chemical Corporation)

<Characteristics of polymerizable compounds>
The melting points and weight average molecular weights of the crystalline or amorphous radical polymerizable compounds and the radically polymerizable monomers were measured and shown in Table 1.

<Compound properties, composition properties, physical property evaluation method>

(1) Melting point The radically polymerizable compound shown in Table 1 is placed in an aluminum pan with 10 mg of the measurement sample using a differential scanning calorimeter "DSC6220" (manufactured by Seiko Instruments Co., Ltd.), and the lid is pressed to seal it. It was measured from 60 ° C. to 200 ° C. at a heating rate of 10 ° C./min. The endothermic peak of the obtained curve was taken as the melting point. The results are shown in Table 1. The measurement of the liquid compound at 23 ° C. was stopped.

(2) Weight average molecular weight The weight average molecular weight of the radically polymerizable compound shown in Table 1 is obtained by dissolving the polymerizable compound in tetrahydrofuran (THF) at 1.0% by weight and using GPC (gel permeation chromatography) to polystyrene. Measured by conversion. The measurement conditions are shown below. The results are shown in Table 1. However, even if the strict standards are not met, depending on the desired application, required quality, etc., even if the weight average molecular weight is less than 100 or larger than 100,000, it may be suitable, so consider it as a guideline. It's good.
Equipment Equipment: Showa Denko Corporation Shodex GPC-101
Column: Showa Denko KKF-802, 803, 804, 805
Solvent, carrier solution: THF
Flow rate: 1.0 ml / min Sample concentration: 1.0%
Temperature: 40 ° C
Sample injection volume: 200 μl
Detector: Differential refractometer detector

(3) JIS K 7215 was used as a reference for the hardness measurement method. The hardness of the crystalline or amorphous radically polymerizable compositions of Examples 1 to 11 shown in Table 2, Reference Examples 1 and 2 shown in Table 3 is measured by a durometer (West Tokyo Precision Co., Ltd. WR- It was measured by 105D). The radically polymerizable composition whose temperature was adjusted to 90 ° C. was formed into a flat plate of about 100 mm × 100 mm × 10 mm and cooled and solidified in a thermostatic chamber at 23 ° C. The radically polymerizable composition before curing, which was temperature-controlled at 23 ° C., was placed on a horizontal hard table. The pressure reference surface of the durometer is pressed against the surface of the radically polymerizable composition as quickly as possible without impact while keeping parallel to the surface of the radically polymerizable composition, and the pressure reference surface and the radically polymerizable composition are pressed together. It adhered well. Within 1 second, the maximum indicated value of the pointer of the indicator was read promptly. The results are shown in Tables 2 and 3. The target hardness was 10, 20 or more was excellent, 10 or more was good, and less than 10 was acceptable.

(4) Melt Viscosity The crystalline or amorphous radical polymerizable composition of Examples 1 to 11 shown in Table 2, Reference Example 1 and Comparative Examples 1 to 2 shown in Table 3 was added to an enhanced flow tester (Co., Ltd.). ) The melt viscosity was measured with CFT-100EX) manufactured by Shimadzu Corporation. With a length of 1mm die diameter 0.5 mm, put a radical polymerizable composition in the cylinder sample insertion hole heated to 90 ℃, 30kgf / cm ² or after preheating at 240 seconds, the piston at a pressure of 1 kgf / cm ² The radical polymerizable composition was allowed to flow out from the nozzle of the die, and the melt viscosity was determined from a portion having good linearity. The results are shown in Tables 2 and 3. The target melt viscosity was 1 to 1000 Pa · s, the composition having 1 to 100 Pa · s was excellent, and 100 to 1000 Pa · s was good.

(5) EIMS T-901 was used as a reference for the flow length measurement method. Auxiliary ram type equipped with a spiral flow mold using the crystalline or amorphous radical polymerizable compositions of Examples 1 to 11 shown in Table 2, Reference Example 1 and Comparative Examples 1 to 2 shown in Table 3. The flow length was measured with a transfer molding machine. The spiral flow mold was heated to 165 ° C. The spiral flow mold used had a material injection port at the center, and a semicircular spiral groove having a radius of 1.6 mm was provided starting from the injection port. A predetermined amount of the radically polymerizable composition was weighed so that the thickness of the cal was in the range of 1 to 10 mm. The plunger was raised, the radically polymerizable composition was put into a pot, and a pressure of 3.2 MPa was immediately applied to start transfer molding. The movement of the plunger stopped, and 180 seconds after the start of measurement, the mold was opened and the molded product was taken out. The number obtained by adding 1/2 of the length of the tip of the molded product to the glossy portion or the length of the glossy portion and the length of the low-density portion at the tip was read. The results are shown in Tables 2 and 3. The target flow length was 50 cm, 100 cm or more was excellent, 50 cm or more was good, and less than 50 cm was acceptable. However, even if the strict standard is not cleared, the conditions may be met even if it is less than 50 cm depending on the desired application, required quality, etc., so it may be considered as a guideline.

(6) The molding shrinkage measurement method conformed to JIS K6911. Using the crystalline or amorphous radical polymerizable compositions of Examples 1 to 11 shown in Table 2, Reference Example 1 and Comparative Examples 1 and 2 shown in Table 3, compression using a shrinkage rate measuring mold. A test piece was prepared by molding. The radically polymerizable composition was placed in a mold whose temperature was adjusted to 165 ° C. and heated under pressure for 3 minutes. The test piece was immediately removed from the mold and stored at a constant temperature and humidity of 23 ° C. and a humidity of 55% RH for 24 hours. A total of four dimensions were measured, two on the front surface and two on the back surface, along the measurement lines perpendicular to the outer shape of the annular band protruding from the front and back of the test piece. The outer shape of the groove of the mold corresponding to the test piece was measured up to 0.01 mm under the same conditions, and the molding shrinkage rate was calculated. The results are shown in Tables 2 and 3. The target molding shrinkage was 0.5%, 0.2% or less was excellent, 0.2 to 0.5% or less was good, and 0.5% or more was acceptable. However, even if the above strict standards are not met, the conditions may be met even if it exceeds 0.5% depending on the desired application, required quality, etc., so it should be considered as a guideline. Is.

(7) The glass transition point measurement was based on JIS K7224-4. The crystalline or amorphous radical polymerizable compositions of Examples 1 to 11 shown in Table 2, Reference Examples 1 and 2 shown in Table 3 were placed in a plate mold whose temperature was adjusted to 165 ° C. It was. The mold was quickly closed and pressure heat molding was performed. After curing, the mold was opened to obtain a flat molded piece. A test piece for measuring the glass transition point was obtained by cutting a flat plate-shaped molded piece into a strip shape. Dynamic viscoelasticity (RSA-G2 manufactured by TA Instruments Co., Ltd.) was measured at a heating rate of 2 ° C./min in a range of 30 to 250 ° C. and a frequency of 10 Hz. The Tanδ peak temperature was taken as the glass transition point. The results are shown in Tables 2 and 3. The target glass transition point was 125 ° C, 125 ° C or higher was good, and less than 125 ° C was acceptable. However, even if the strict standards are not cleared, the conditions may be met even if the temperature is lower than 125 ° C. depending on the desired application, required quality, etc., so it may be considered as a guideline.

(8) The dielectric breakdown strength measurement method conformed to JIS K6911. The crystalline or amorphous radical polymerizable compositions of Examples 1 to 11 shown in Table 2, Reference Examples 1 and 2 shown in Table 3 were placed in a plate mold whose temperature was adjusted to 165 ° C. The mold was quickly closed and pressure heat molding was performed. After curing, the mold was opened to obtain a flat molded piece. A test piece for measuring dielectric breakdown strength was obtained by cutting from a flat plate-shaped molded piece. Dielectric breakdown strength (YST-243-100RHO, a dielectric breakdown tester manufactured by Yamayo Testing Machine Co., Ltd.) uses a Φ20 sphere / Φ25 cylinder as an electrode in silicone oil at a temperature of 23 ° C, and applies a voltage in a 20-second step method. And measured. The results are shown in Tables 2 and 3. The target dielectric breakdown strength was 10 kV / mm, 12 kV / mm or more was good, and less than 10 kV / mm was acceptable. However, even if the strict standard is not cleared, the conditions may be met even if it is less than 10 kV / mm depending on the required quality and the like, so it may be considered as a guideline.

<Evaluation result>
As shown in Tables 2 and 3, it was found that the crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil in the present invention is excellent in handleability. Further, in particular, Examples 1 to 8 and 11 of the crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil in the present invention are excellent in handleability because they are solid at 23 ° C., and have low melt viscosity and are good. It was. It has been found that the crystalline radically polymerizable composition for encapsulating an in-vehicle ignition coil in the present invention shows excellent results as a whole.

Example 9 is a crystalline radically polymerizable composition having a different amount of the inorganic filler compounded in Example 1. The hardness of the composition was 3, which was soft. Further, the melt viscosity was 0.5 Pa · s, which was a low viscosity composition, the molding shrinkage rate was large, and the dielectric breakdown strength was low, but other characteristics were good.

Example 10 is a crystalline radical-polymerizable composition obtained by changing the crystalline radical-polymerizable compound of Example 5 to a radical-polymerizable compound which is a room temperature liquid and changing the blending ratio of the radical-polymerizable compound. Since the amount of the crystalline radical polymerizable compound was small, the hardness of the composition was 0, which was soft, and the result was that the glass transition point was low, but other properties were good.

Reference Example 1 is a crystalline radically polymerizable composition in which the blending amount of the inorganic filler of Example 8 is changed. The melting start temperature was not observed because the flow stopped during the measurement. In addition, the melt viscosity was high and the flow length was short, but other characteristics were good.

Therefore, even in Examples 9 and 10 and Reference Example 1, the conditions may be met depending on the desired application, required quality, etc., so it may be considered as a guideline, and good characteristics can be obtained. It turned out to be applicable to the required applications.

Further, both Comparative Examples 1 and 2 had a higher melt viscosity than the crystallinity (Comparative Example 1 can be compared with Example 4), resulting in inferior handleability and the like.

As described above, it has been found that the crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil containing at least a crystalline radical polymerizable compound has excellent handleability and good fluidity.

Since the crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil of the present invention and the molded product using the same are excellent in electrical insulation and heat resistance, the durability of the in-vehicle ignition coil encapsulant is improved. It is possible.

Claims (11)

A crystalline radical for encapsulating an in-vehicle ignition coil, which comprises at least a crystalline radical polymerizable compound having a glass transition point and a melting point , an inorganic filler, a silane coupling agent, and a radical polymerization initiator. Polymerizable composition. The crystalline radically polymerizable compound includes crystalline unsaturated polyester, crystalline epoxy (meth) acrylate, crystalline urethane (meth) acrylate, crystalline polyester (meth) acrylate, crystalline polyether (meth) acrylate, and crystalline. The crystalline radical polymerizable composition for encapsulating an automotive ignition coil according to claim 1, further comprising one or more selected from a radically polymerizable monomer and a crystalline radically polymerizable multimer. The crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil according to claim 1 or 2, wherein the crystalline radical polymerizable compound exhibits a melting point in the range of 30 to 150 ° C. The crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil according to any one of claims 1 to 3, wherein the crystalline radical polymerizable composition is solid at 23 ° C. The melt viscosity of the crystalline radical polymerizable composition by the enhanced flow tester is 7 to 1000 Pa · s at a measurement temperature of 90 ° C., a die diameter of 0.5 mm, a length of 1.0 mm, and a pressure of 30 kgf / cm ² . The crystalline radical polymerizable composition for encapsulating an vehicle-mounted ignition coil according to any one of claims 1 to 4, wherein the pressure is 1 to 7 Pa · s at a pressure of 1 kgf / cm ² . The vehicle-mounted ignition coil encapsulation according to any one of claims 1 to 5, wherein the inorganic filler is 50 to 95% by weight based on the total amount of the crystalline radical polymerizable composition. Crystalline radically polymerizable composition. The crystallinity for encapsulating an in-vehicle ignition coil according to any one of claims 1 to 6, wherein the ratio of the crystalline radically polymerizable compound to the total amount of the radically polymerizable compound is 30 parts by weight or more. Radical polymerizable composition. The crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil according to any one of claims 1 to 7, wherein the crystalline radical polymerizable compound has a weight average molecular weight of 100 to 100,000. .. An in-vehicle ignition coil encapsulant sealed with the crystalline radical polymerizable composition for encapsulating an in-vehicle ignition coil according to any one of claims 1 to 8. A granular material comprising the crystalline radically polymerizable composition for encapsulating an in-vehicle ignition coil according to any one of claims 1 to 8. The vehicle-mounted ignition according to claim 10, further comprising a step of sealing the electrical and electronic parts by an injection molding method and an insert molding method by a transfer molding method for the granular material composed of the crystalline radically polymerizable composition for sealing the vehicle-mounted ignition coil. A method for manufacturing a coil sealant.