CN111356722B - Bulk molding compound and method for packaging motor by using same - Google Patents
Bulk molding compound and method for packaging motor by using same Download PDFInfo
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- CN111356722B CN111356722B CN201880074066.1A CN201880074066A CN111356722B CN 111356722 B CN111356722 B CN 111356722B CN 201880074066 A CN201880074066 A CN 201880074066A CN 111356722 B CN111356722 B CN 111356722B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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Abstract
A bulk molding compound comprising (A) an unsaturated polyester, (B) a polymerizable monomer and (C) a reinforcing fiber, wherein the unsaturated polyester (A) is contained in an amount of 25 to 75 parts by mass based on 100 parts by mass of the total of the unsaturated polyester (A) and the polymerizable monomer (B), the polymerizable monomer (B) comprises (B1) vinyltoluene, and the bulk molding compound does not contain styrene or diallyl phthalate.
Description
Technical Field
The invention relates to bulk molding compound and a method for packaging a motor by using the same.
Background
Conventional bulk molding compounds (hereinafter, sometimes referred to as "BMC") often use styrene as a polymerizable monomer. However, it is known that styrene emits odor from the resin composition and the cured product thereof. In recent years, adverse effects of styrene on the environment and human body have been a problem, and regulations by autonomous bodies have been started as a target for limiting specific malodorous substances in the malodour prevention act. Further, explosion-proof facilities are required for various facilities used in the manufacturing process or molding process of BMCs using styrene, buildings, storage warehouses thereof, and the like.
To cope with this limitation, the following methods may be cited: forcibly volatilizing styrene by previously performing post-curing of the molded article at a temperature higher than the temperature at which the molded article is used, thereby releasing styrene remaining in the cured article; use of a specific curing agent for radical-polymerizable thermosetting resins suppresses the residual of unreacted unsaturated monomers such as styrene in cured products (see patent document 1); and the like.
Further, patent document 2 discloses: by using diallyl phthalate as the polymerizable monomer, not only is emission of styrene from the unsaturated polyester resin molding material and the molded article thereof eliminated, and therefore it is effective as a measure against the malodor prevention method, but also the flash point of the unsaturated polyester resin molding material is greatly increased, and thus explosion-proof equipment becomes unnecessary.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2007-146125
Patent document 2: japanese laid-open patent publication No. 2010-202812
Disclosure of Invention
Problems to be solved by the invention
However, in the method disclosed in patent document 1, the styrene emission itself cannot be eliminated. Further, when the motor is packaged using the BMC disclosed in patent document 2, there are problems as follows: due to the influence of diallyl phthalate, a coating film of a metal coil (wire coil) of a packaged motor gradually deteriorates, and electrical insulation performance remarkably decreases.
Accordingly, an object of the present invention is to provide a bulk molding compound having a flash point higher than that of a conventional bulk molding compound containing styrene, which does not generate a specific malodorous substance such as styrene from a cured product, and which does not deteriorate a coating film of a metal coil of a motor even when the motor is packaged.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found the following facts, thereby completing the present invention: the above problem can be solved by blending vinyltoluene in a specific mass ratio to the unsaturated polyester and not blending styrene and diallyl phthalate.
That is, the present invention is shown by the following [1] to [13 ].
[1] A bulk molding compound comprising (A) an unsaturated polyester, (B) a polymerizable monomer and (C) a reinforcing fiber, wherein the unsaturated polyester (A) is contained in an amount of 25 to 75 parts by mass based on 100 parts by mass of the total of the unsaturated polyester (A) and the polymerizable monomer (B), and the polymerizable monomer (B) contains vinyl toluene (B1), and wherein styrene and diallyl phthalate are not contained in the bulk molding compound.
[2] The bulk molding compound according to [1], wherein the bulk molding compound is used for motor packaging.
[3] The bulk molding compound according to [1] or [2], wherein the polymerizable monomer (B) further comprises (B2) (meth) acrylate.
[4] The bulk molding compound according to [3], wherein the (b 2) (meth) acrylate has two or more (meth) acryloyloxy groups.
[5] The bulk molding compound according to any one of [1] to [4], wherein the (C) reinforcing fiber is a glass fiber.
[6] The bulk molding compound according to any one of [1] to [5], wherein the curing agent (D) is contained in an amount of 1 to 7 parts by mass based on 100 parts by mass of the total of the unsaturated polyester (A) and the polymerizable monomer (B).
[7] A bulk molding compound as defined in any one of [1] to [6], wherein the low shrinkage agent (E) is contained in an amount of 10 to 40 parts by mass based on 100 parts by mass of the total of the unsaturated polyester (A) and the polymerizable monomer (B).
[8] The bulk molding compound according to any one of [1] to [7], wherein the inorganic filler (F) is contained in an amount of 200 to 500 parts by mass based on 100 parts by mass of the total of the unsaturated polyester (A) and the polymerizable monomer (B).
[9] The bulk molding compound according to any one of [1] to [8], wherein the release agent (G) is contained in an amount of 1 to 20 parts by mass based on 100 parts by mass of the total of the unsaturated polyester (A) and the polymerizable monomer (B).
[10] The bulk molding compound according to any one of [1] to [9], wherein the reinforcing fiber (C) is contained in an amount of 15 to 50 parts by mass based on 100 parts by mass of the total of the unsaturated polyester (A) and the polymerizable monomer (B).
[11] A method of packaging a motor using the bulk molding compound according to any one of [1] to [10 ].
[12] A molded article comprising a cured product of the bulk molding compound according to any one of [1] to [10 ].
[13] A method for producing a molded article, comprising the step of curing the bulk molding compound according to any one of [1] to [10] by heating and pressing.
Effects of the invention
According to the present invention, there can be provided a bulk molding compound having a flash point higher than that of a conventional bulk molding compound containing styrene, causing no generation of a specific malodorous substance such as styrene from a cured product, and preventing deterioration of a coating film of a metal coil of a motor even when the motor is packaged.
Detailed Description
The bulk molding compound (hereinafter, sometimes abbreviated as "vinyltoluene-based BMC") of the present invention contains, as essential components, (A) an unsaturated polyester, (B1) vinyltoluene as (B) a polymerizable monomer, and (C) a reinforcing fiber, and does not contain styrene or diallyl phthalate.
In the present specification and claims, "not containing styrene and diallyl phthalate" means that the content of styrene and diallyl phthalate in the vinyltoluene BMC is 0.1 mass% or less, respectively, and is not excluded even if impurities and the like are mixed together with other components.
[ (A) unsaturated polyester ]
The unsaturated polyester (a) used in the present invention is not particularly limited in its kind as long as it is obtained by polycondensing a polyol, an unsaturated polybasic acid and, if necessary, a saturated polybasic acid. The unsaturated polyester (a) used in the present invention can be synthesized by a known synthesis method.
Examples of the polyhydric alcohol used as a raw material of the unsaturated polyester (a) include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, pentanediol, hexanediol, neopentyl glycol, hydrogenated bisphenol a, glycerin, and the like. Among them, ethylene glycol, propylene glycol, neopentyl glycol, hydrogenated bisphenol a, and bisphenol a are preferable. These polyols may be used alone, or two or more thereof may be used.
Examples of the unsaturated polybasic acid used as a raw material of the unsaturated polyester (a) include maleic acid, maleic anhydride, fumaric acid, citraconic acid, and itaconic acid. Examples of the saturated polybasic acid include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, chloromono acid, succinic acid, adipic acid, sebacic acid, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, endomethylenetetrahydrophthalic anhydride, and the like. Among them, maleic anhydride, fumaric acid, isophthalic acid, and terephthalic acid are preferable. These unsaturated polybasic acids and saturated polybasic acids may be used alone or in combination of two or more.
(A) The unsaturated polyester preferably has a weight average molecular weight of 4000 to 35000, more preferably 6000 to 20000, and most preferably 8000 to 15000. When the weight average molecular weight of the unsaturated polyester (a) is 4000 to 35000, moldability becomes more favorable. In the present specification, the term "weight average molecular weight" refers to a value obtained by measuring at room temperature under the following conditions using gel permeation chromatography (Shodex GPC-101 manufactured by Showa Denko K.K.) using a standard polystyrene calibration curve.
A chromatographic column: SHOWA-HAZ ELECTRICITY MADE LF-804
Temperature of the column: 40 deg.C
Sample preparation: (A) 0.2% by mass tetrahydrofuran solution of unsaturated polyester
Flow rate: 1 mL/min
Eluent: tetrahydrofuran (THF)
A detector: RI-71S
(A) The unsaturated degree of the unsaturated polyester is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, most preferably 70 to 100 mol%. When the unsaturated degree of the unsaturated polyester is 50 to 100 mol%, the moldability becomes further favorable. (A) The unsaturation degree of the unsaturated polyester can be calculated by the following formula using the moles of the unsaturated polybasic acid and the saturated polybasic acid used as the raw materials.
Unsaturation (mole%) = { (moles of unsaturated polybasic acid)/(moles of unsaturated polybasic acid + moles of saturated polybasic acid) } × 100
The unreacted unsaturated polybasic acid after the synthesis of the unsaturated polyester (a) is contained in the polymerizable monomer (B).
[ (B) polymerizable monomer ]
The polymerizable monomer (B) used in the present invention is a compound having a polymerizable unsaturated group copolymerizable with the unsaturated polyester (a), and contains vinyl toluene (B1) as an essential component.
< (b 1) vinyltoluene
Among vinyltoluenes, there are three isomers of o-vinyltoluene, m-vinyltoluene, and p-vinyltoluene, which are monomers that are liquid at ordinary temperature. As the (b 1) vinyltoluene, o-vinyltoluene, m-vinyltoluene and p-vinyltoluene may be used, and they may be used alone or in combination of two or more. The flash point of the vinyltoluene-based BMC using (B1) vinyltoluene as the polymerizable monomer (B) is higher than that of the conventional BMC using styrene. The flash point of the conventional BMC resulting from a flash point of 31 ℃ of styrene is about 36 ℃, whereas the flash point of the vinyltoluene-based BMC of the present invention resulting from a flash point of 54 ℃ of vinyltoluene is completely above 40 ℃ which is the threshold value of flammable solids in the second class of flammable solids prescribed by the fire protection act. Further, by using (B2) (meth) acrylate as the polymerizable monomer (B), the flash point of the resin composition can be further improved. As a result, various devices used in the BMC manufacturing process or molding process, and explosion-proof equipment such as buildings and storage warehouses thereof are not required, and an economical effect that the storage amount of BMC is not limited can be obtained.
< (b 2) (meth) acrylate
In the present specification, "(meth) acrylate" means an ester compound having at least one (meth) acryloyloxy group. "(meth) acrylate" means at least one selected from the group consisting of methacrylate and acrylate. In addition to the above-mentioned (B1) vinyltoluene, (B2) (meth) acrylate is preferably used in combination as the (B) polymerizable monomer. The (b 2) (meth) acrylate is not particularly limited, but is preferably a (meth) acrylate having two or more (meth) acryloyloxy groups, from the viewpoints of improving the flash point of BMC to further improve safety, increasing the crosslink density of a cured product, and increasing the glass transition temperature to cope with use in a wide temperature range. Examples of the (meth) acrylate having two or more (meth) acryloyloxy groups include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, glycerol di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and the like. Among them, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and trimethylolpropane tri (meth) acrylate are preferable. These (meth) acrylates may be used alone, or two or more thereof may be used.
In the vinyltoluene-based BMC of the present invention, the amount of the unsaturated polyester (a) to be blended is required to be 25 to 75 parts by mass, preferably 30 to 70 parts by mass, based on 100 parts by mass of the total of the unsaturated polyester (a) (solid state) and the polymerizable monomer (B). When the amount of the unsaturated polyester (a) is less than 25 parts by mass, moldability when heat and pressure are applied to BMC is remarkably lowered. On the other hand, when the blending amount of the unsaturated polyester (a) exceeds 75 parts by mass, the kneading property of the resin composition is remarkably lowered, and it is difficult to prepare BMC.
[ (C) reinforcing fiber ]
The vinyltoluene-based BMC of the present invention must contain (C) a reinforcing fiber. Examples of the reinforcing fibers include glass fibers, organic fibers, and carbon fibers. In packaging the motor, glass fiber is preferred. The glass fiber is preferably chopped strand glass (chopped strand glass) having a fiber length of 3.0 to 12.5mm, more preferably 3.0 to 9.0mm, and most preferably 3 to 6mm. (C) Two or more types of reinforcing fibers having different fiber lengths may be used. The amount of the reinforcing fiber (C) is preferably 15 to 50 parts by mass, and more preferably 20 to 45 parts by mass, based on 100 parts by mass of the total of the unsaturated polyester (a) and the polymerizable monomer (B). If the amount of the reinforcing fiber (C) is 15 parts by mass or more, the strength of the molded article becomes good. On the other hand, if the blending amount of the (C) reinforcing fiber is 50 parts by mass or less, the fluidity of BMC becomes good at the time of molding, and the coil is not damaged at the time of packaging the motor, for example.
[ (D) curing agent ]
The vinyltoluene-based BMC of the present invention may further contain (D) a curing agent. The curing agent (D) is preferably an organic peroxide, and may be appropriately selected in consideration of curing conditions, storage stability, and the like. Examples of the curing agent (D) include t-butyl peroctoate (t-butyl peroxoctoate), benzoyl peroxide, 1,1-di-t-butyl peroxide-3,3,5-trimethylcyclohexane, t-butyl peroxyisopropylcarbonate, t-butyl peroxybenzoate, dicumyl peroxide, and di-t-butyl peroxide. These (D) curing agents may be used alone, or two or more thereof may be used. The amount of the curing agent (D) is preferably 1 to 7 parts by mass, more preferably 2 to 5 parts by mass, based on 100 parts by mass of the total of the unsaturated polyester (a) and the polymerizable monomer (B). When the amount of the curing agent (D) is 1 part by mass or more, the curing reaction during molding occurs uniformly, and the physical properties and the appearance of the molded article become good. On the other hand, if the amount of the curing agent is 7 parts by mass or less, the storage stability of the vinyltoluene-based BMC becomes good and the workability is improved.
[ (E) Low shrinkage agent ]
The vinyltoluene-based BMC of the present invention may further contain (E) a low shrinkage agent. As the low shrinkage agent (E), those generally used in BMC can be used, and examples thereof include polystyrene, polyethylene, polymethyl methacrylate, polyvinyl acetate, saturated polyester, polycaprolactone, styrene-vinyl acetate block copolymer, and styrene-diene block copolymer. These (E) low shrinkage agents may be used alone or two or more of them may be used. The amount of the low shrinkage agent (E) is preferably 10 to 40 parts by mass, more preferably 15 to 35 parts by mass, based on 100 parts by mass of the total of the unsaturated polyester (a) and the polymerizable monomer (B). When the amount of the low shrinkage agent (E) is 10 parts by mass or more, the resulting molded article has a low shrinkage rate and good toughness, and therefore, cracks are less likely to occur in the molded article. On the other hand, if the blending amount of the low shrinkage agent (E) is 40 parts by mass or less, separation of thermoplastic components and the like do not occur, and the surface state of the molded article becomes extremely good.
[ (F) inorganic Filler ]
The vinyltoluene-based BMC of the present invention may further contain (F) an inorganic filler. The inorganic filler (F) is not particularly limited in terms of material, shape, etc., as long as the properties such as strength performance and appearance are not impaired, and examples thereof include inorganic powders such as silica, alumina, mica, aluminum hydroxide, calcium carbonate, gypsum, barium sulfate, clay, and talc. These (F) inorganic fillers may be used alone, or two or more kinds thereof may be used. The amount of the inorganic filler (F) is preferably 200 to 500 parts by mass, more preferably 300 to 400 parts by mass, based on 100 parts by mass of the total of the unsaturated polyester (a) and the polymerizable monomer (B). When the amount of the inorganic filler (F) is 200 parts by mass or more, the BMC is less sticky, the workability during BMC production and molding is good, and the shrinkage ratio of the molded article is small, so that the dimensional accuracy of the product is good. On the other hand, if the blending amount of the inorganic filler (F) is 500 parts by mass or less, the fluidity can be sufficiently ensured at the time of molding, and therefore, molding can be performed without damaging the coil, for example, at the time of packaging the motor. Further, if the blending amount of the inorganic filler (F) is 500 parts by mass or less, a weld crack at the weld joint portion is less likely to occur. The average particle diameter of the inorganic filler (F) is preferably 1 to 100. Mu.m, more preferably 1 to 50 μm, most preferably 1 to 30 μm. When the average particle diameter of the inorganic filler (F) is in the range of 1 to 100. Mu.m, both the inhibition of the aggregation of the inorganic filler (F) and the high filling can be achieved. In the present specification, the average particle diameter of the (F) inorganic filler is a value obtained by measuring the particle diameters of 10 particles in an observation image obtained by an electron microscope or an optical microscope and taking the arithmetic average of the particle diameters.
[ (G) Release agent ]
The vinyltoluene-based BMC of the present invention may further contain (G) a release agent. Examples of the (G) release agent include stearic acid, oleic acid, zinc stearate, calcium stearate, aluminum stearate, magnesium stearate, stearamide, oleamide, silicone oil, and synthetic wax. These release agents may be used alone, or two or more thereof may be used in combination. The amount of the release agent (G) is preferably 1 to 20 parts by mass, more preferably 5 to 15 parts by mass, based on 100 parts by mass of the total of the unsaturated polyester (a) and the polymerizable monomer (B). When the amount of the release agent (G) is 1 part by mass or more, the releasability at the time of molding is good and the productivity of the product is good. On the other hand, if the blending amount of the (G) release agent is 20 parts by mass or less, the release agent can be prevented from remaining on the surface of the molded article, and therefore the appearance of the molded article and the adhesion between the metal coil of the encapsulated motor and the resin composition become good.
In the vinyltoluene-based BMC of the present invention, various additives may be used in addition to the above-mentioned components within a range not impairing the performance. As such additives, there are various pattern materials in a granular form, a flake form, or a fibrous form; inorganic pigments such as titanium oxide and carbon black, colorants such as various organic pigments and dyes; a low profile agent anti-separation or compatibilizing agent; viscosity reducing agent; a polymerization inhibitor; tackifiers, and the like. These additives may be used alone or in combination of two or more, as required.
The vinyltoluene BMC of the present invention composed of the above components can be obtained by a method generally performed in the production of bulk molding compounds, for example, kneading the components using a kneader or the like under the following conditions. The components other than the (C) reinforcing fiber were put into a double arm kneader having a jacket temperature set in the range of 20 to 50 ℃, and kneaded for 20 to 60 minutes with a lid closed until the components were sufficiently dispersed to be putty (putty). After the resin composition is oil-ashed, the cap is opened, the (C) reinforcing fibers are slowly charged for 1 to 2 minutes while kneading, after the completion of the predetermined amount of charging, the cap is closed, and kneading is performed for 5 to 60 minutes until the bundle of the (C) reinforcing fibers is sufficiently defibered and uniformly dispersed. After completion of kneading, the obtained BMC was packaged with a laminate film of a polyethylene film and a polyethylene terephthalate film, a vinylon film, or the like.
The vinyltoluene-based BMC of the present invention thus obtained can be used in various molding methods. For example, various molded articles can be obtained by molding by compression molding, transfer molding, or injection molding. In particular, the vinyltoluene-based BMC of the present invention is useful as a BMC for motor packaging in household electric appliances, such as refrigerators, washing machines, air conditioners, vacuum cleaners, and the like, hybrid vehicles, electric vehicles, industrial products, and the like, and can provide a molded article which does not generate a specific malodorous substance, does not degrade a coating film of a metal coil of a motor, and has moldability, molded article appearance, and molded article characteristics comparable to those of conventional BMCs.
[ examples ]
The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.
[ raw materials ]
The following substances were used.
(A) Unsaturated polyester
Unsaturated polyester ("Rigolac (registered trademark) M-500D", manufactured by Showa Denko K.K., ester of maleic anhydride and propylene glycol, weight-average molecular weight: about 13000, degree of unsaturation: 100%)
(B) Polymerizable monomer
Vinyltoluene (Rex industry Co., ltd.)
Ethylene Glycol Dimethacrylate (EGDMA) (product of Kyowa Kagaku K.K. "LIGHT ESTER EG")
Trimethylolpropane trimethacrylate (TMPTMA) (product of Kyoho chemical Co., ltd. "LIGHT ESTER TMP")
(C) Reinforcing fiber
Chopped glass fibers (ECS 03B-173, manufactured by Nippon Denshoku Co., ltd.; fiber length: 3 mm)
(D) Curing agent
Tert-butyl peroxybenzoate (TBB) (Perbutyl Z available from Nichikoku Co., ltd.)
Tert-butyl peroctoate (TBO) (Perbutyl O, manufactured by Nichikoku Co., ltd.)
(E) Low shrinkage agent
Styrene-vinyl acetate block copolymer (SVA) (model S501, nichikoku Co., ltd.)
(F) Inorganic filler
Aluminum hydroxide (HIGILITE H-32, manufactured by SHOWA DENKO K.K.; average particle diameter: 8 μm)
(G) Release agent
Calcium stearate (south Milan chemical industry Co., ltd.)
(others)
Diallyl phthalate (Osaka Caoda Co., ltd.)
Styrene (manufactured by Asahi Kasei Chemicals Co., ltd.)
[ preparation of unsaturated polyester solution ]
< preparation of unsaturated polyester solution 1 >
75 parts by mass of an unsaturated polyester (solid) was placed in a flask, heated and melted at 140 ℃ and 25 parts by mass of vinyl toluene was added thereto, and the mixture was dissolved by rotating a stirring blade at 200rpm, thereby obtaining an unsaturated polyester solution 1. The viscosity of the obtained unsaturated polyester solution 1 was measured at 25 ℃ and 20rpm using a BH type viscometer (manufactured by Tokyo Meter K.K.) and was 130 dPa.s.
< preparation of unsaturated polyester solution 2 >
An unsaturated polyester solution 2 was obtained in the same manner as in the unsaturated polyester solution 1 except that 75 parts by mass of the unsaturated polyester (solid) was changed to 80 parts by mass and 25 parts by mass of vinyl toluene was changed to 20 parts by mass. The viscosity of the unsaturated polyester solution 2 was measured in the same manner as the unsaturated polyester solution 1, and the result was 1440 dPas.
< preparation of unsaturated polyester solution 3 >
An unsaturated polyester solution 3 was obtained in the same manner as the unsaturated polyester solution 1 except that 75 parts by mass of the unsaturated polyester (solid) was changed to 50 parts by mass, and 25 parts by mass of vinyl toluene was changed to 50 parts by mass of ethylene glycol dimethacrylate. The viscosity of the unsaturated polyester solution 3 was measured in the same manner as the unsaturated polyester solution 1, and the result was 19 dpas.
< preparation of unsaturated polyester solution 4 >
50 parts by mass of styrene was added to 50 parts by mass of the unsaturated polyester (solid state) to dissolve the unsaturated polyester, thereby obtaining an unsaturated polyester solution 4. The viscosity of the unsaturated polyester solution 4 was measured in the same manner as the unsaturated polyester solution 1, and the result was 5 dpas.
[ preparation of BMC ]
The components shown in tables 1 and 2 (except for glass fibers) were kneaded at respective blending amounts using a twin arm kneader having a jacket temperature set at 30 ℃, and then a predetermined blending amount of glass fibers was added thereto and kneaded, thereby producing BMCs of examples 1 to 5 and comparative examples 1 and 3 to 5. In comparative example 2, the viscosity of the unsaturated polyester solution 2 used was very high, and therefore, the workability was poor, and the resulting mixture was not clay-like even when kneaded with a kneader, and thus BMC could not be produced.
[ Table 1]
| Compounding amount (parts by mass) | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Unsaturated polyester solution 1 | 100.0 | 67.0 | 34.0 | 67.0 | 67.0 |
| Unsaturated polyester solution 2 | |||||
| Unsaturated polyester solution 3 | |||||
| Unsaturated polyester solution 4 | |||||
| Vinyl toluene | 33.0 | 66.0 | |||
| EGDMA | 33.0 | ||||
| TMPTMA | 33.0 | ||||
| Diallyl phthalate | |||||
| TBB | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 |
| TBO | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| SVA | 25.0 | 25.0 | 25.0 | 25.0 | 25.0 |
| Aluminum hydroxide | 350 | 350 | 350 | 350 | 350 |
| Calcium stearate | 10.0 | 10.0 | 10.0 | 10.0 | 10.0 |
| Chopped glass fiber | 30.0 | 30.0 | 30.0 | 30.0 | 30.0 |
[ Table 2]
| Compounding amount (parts by mass) | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| Unsaturated polyester solution 1 | 26.0 | 67.0 | |||
| Unsaturated polyester solution 2 | 100.0 | ||||
| Unsaturated polyester solution 3 | 100.0 | ||||
| Unsaturated polyester solution 4 | 100.0 | ||||
| Vinyl toluene | 74.0 | 28.0 | |||
| EGDMA | |||||
| TMPTMA | |||||
| Diallyl phthalate | 5.0 | ||||
| TBB | 2.5 | 2.5 | 2.5 | 2.5 | 2.5 |
| TBO | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| SVA | 25.0 | 25.0 | 25.0 | 25.0 | 25.0 |
| Aluminum hydroxide | 350 | 350 | 350 | 350 | 350 |
| Calcium stearate | 10.0 | 10.0 | 10.0 | 10.0 | 10.0 |
| Chopped glass fiber | 30.0 | 30.0 | 30.0 | 30.0 | 30.0 |
The pugs obtained in examples 1 to 5 and comparative examples 1 to 5 were evaluated for kneading property, coil deterioration property and flash point, and the cured products thereof were evaluated for appearance, residual styrene content and physical properties (flexural strength, tensile strength, charpy impact strength and insulation resistance) of the molded articles. The methods of the evaluations are shown below. In comparative example 2, BMC could not be produced, and thus only kneading property was evaluated.
[ evaluation of kneading Properties ]
The components shown in tables 1 and 2 were kneaded using a double arm kneader at respective mixing ratios, and as a result, a substance capable of producing BMC was indicated by "o" and a substance incapable of producing BMC even when kneaded was indicated by "x".
[ evaluation of deterioration Property of Metal coil ]
In a glass bottle, 10g of uncured BMC and 0.05g of a metal coil (enameled wire covered with polyester-nylon, 6 cm) were placed, and after sealing with a metal cap, treatment was carried out for 48 hours at 190 ℃ with a heat aging tester (Geer Oven STD45-P, toyobo Co., ltd.), and change in the coating film of the metal coil was visually observed. In comparison with the material obtained by heat treatment of the metal coil alone, the material having the same color tone of the coating and no peeling was indicated by "o", and the material having a difference in color tone of the coating or peeling of the coating was indicated by "x".
[ measurement of flash Point ]
The flash point of uncured BMC was measured using a SETA closed cup flash point measuring apparatus ("Model 13740-2" manufactured by Mitsui Kagaku Co., ltd.). 2g of uncured BMC was placed in a sample cell heated to the measurement temperature, and the cell was covered with a lid and held for 5 minutes. After 5 minutes, the cover plate (shutter) was opened and ignited, and the presence or absence of ignition was confirmed. When ignition was observed, the measurement temperature was lowered, and when no ignition was observed, the measurement temperature was raised, and the presence or absence of ignition was confirmed. The same operation was repeated, and the lowest temperature at which ignition was observed was set as the flash point.
[ evaluation of appearance of molded article ]
A BMC was molded under the following conditions, wherein the molded article was rated "O" for the absence of sink marks or unfilled portions on the surface, and the molded article was rated "X" for the presence of sink marks or unfilled portions on the surface.
A forming machine: 25 ton compression molding machine (Techno Marushichi manufactured by Kabushiki Kaisha)
Forming a mold: disc mold for measuring mold shrinkage according to JIS K6911.5.7
Forming temperature: 120 deg.C
Molding pressure: 70kg/cm 2
Pressurizing time: 300 seconds
Sample amount: 75g of
[ measurement of residual styrene amount in molded article ]
The residual styrene content in the molded article was determined by gas chromatography (GC-2014, shimadzu corporation). In the measurement of the residual styrene amount of the molded article, a pulverized product obtained by pulverizing the molded article (disk-shaped molded article for confirming the appearance of the molded article) with a pair of pliers was put into a glass bottle, immersed in acetone and sealed, extracted at 48 hours/25 ℃.
Temperature of the gasification chamber: 130 deg.C
Temperature of the column: 80 deg.C
Detector temperature: 130 deg.C
Retention time: 15 minutes
Detection time of styrene: 10.67 minutes
[ production of test piece for measuring physical Properties of molded article ]
(1) Bending strength, tensile strength, charpy impact strength
The BMC was molded under the following conditions to prepare a test piece.
A forming machine: 150 ton compression molding machine (Techno Marushichi manufactured by Kabushiki Kaisha)
Forming a mold: molding die for various test pieces described below
Bending strength: JIS K6911 5.17.1
Tensile strength: JIS K6911.18.1
Charpy impact strength: JIS K6911.20
Forming temperature: 120 deg.C
Molding pressure: 70kg/cm 2
Pressurizing time: 300 seconds
Sample amount: the volume of each test piece described in JIS K6911 was defined as X the specific gravity of the BMC molded article X1.05.
(2) Insulation resistance
Test pieces were prepared under the following conditions.
A forming machine: 75 ton compression molding machine (Techno Marushichi manufactured by Kabushiki Kaisha)
Forming a mold: mold for molding insulation resistance test piece described in JIS K6911.12.1
Forming temperature: 120 deg.C
Molding pressure: 70kg/cm 2
Pressurizing time: 600 seconds
Sample amount: the volume of the insulation resistance test piece described in JIS K6911.12.1 was defined as X the specific gravity of the BMC molded product was defined as X1.05.
[ Properties of molded article ]
The test was carried out according to the test methods described in JIS K6911 using the following apparatus.
Bending strength, tensile strength: autograph AG-Xplus (product of Shimadzu corporation)
Charpy impact strength: impact tester IM-103 (manufactured by Shanghai Kabushiki Kaisha)
Insulation resistance: super insulation meter SM-8210 (Toya electric Co., ltd.)
The evaluation results are shown in tables 3 and 4.
[ Table 3]
[ Table 4]
From the results shown in Table 3, it was found that the BMC of examples 1 to 5 was excellent in kneading property and deterioration property of metal coil, sufficiently high in flash point, free from appearance abnormality of cured product, and excellent in physical properties of various molded articles even when the residual styrene content was not more than the detection limit of the apparatus. In particular, in examples 4 and 5 in which vinyltoluene and (meth) acrylate were used in combination as the (B) polymerizable monomer, the flash point of BMC was higher.
On the other hand, in comparative example 1 in which the amount of the unsaturated polyester (a) blended was small, many sink marks having a diameter of about 2mm were generated on the surface of the molded article, and the value of the insulation resistance was greatly reduced from that in the normal state after boiling.
In comparative example 3 using only (meth) acrylate as the polymerizable monomer (B), sink marks having a diameter of about 2mm were generated on the surface of the molded article, and pores were generated in the outer peripheral portion of the molded article. In addition, the BMC of comparative example 3 had very low various strength properties.
In comparative example 4 in which vinyltoluene and diallyl phthalate were used in combination as the polymerizable monomer (B), the deterioration of the metal coil coating after the evaluation of the deterioration property of the metal coil was large, the color tone of the coating was changed to black, and peeling was observed in a part of the coating.
In comparative example 5 using only styrene as the polymerizable monomer (B), the residual styrene content of the molded article was as much as 0.23 mass%, and styrene odor was also generated from the cured molded article. In comparative example 5, BMC had a flash point of 36 ℃ and satisfied the flammability of the second class of flammable solids (flash point less than 40 ℃) in the fire control Law, and therefore, it was necessary to take measures in accordance with the fire control Law in each step.
Claims (13)
1. A bulk molding compound comprising an unsaturated polyester (A), a polymerizable monomer (B) and reinforcing fibers (C),
the unsaturated polyester (A) is contained in an amount of 25 to 75 parts by mass based on 100 parts by mass of the total of the unsaturated polyester (A) and the polymerizable monomer (B),
(B) The polymerizable monomer contains (b 1) vinyl toluene as an essential component,
the bulk molding compound does not contain styrene and diallyl phthalate.
2. The bulk molding compound of claim 1,
the bulk molding compound is used for motor packaging.
3. Bulk moulding compound according to claim 1 or 2,
the polymerizable monomer (B) further contains a (B2) (meth) acrylate.
4. The bulk molding compound of claim 3,
the (b 2) (meth) acrylate has two or more (meth) acryloyloxy groups.
5. Bulk moulding compound according to claim 1 or 2,
the (C) reinforcing fiber is a glass fiber.
6. Bulk moulding compound according to claim 1 or 2,
the curing agent (D) is contained in an amount of 1 to 7 parts by mass based on 100 parts by mass of the total of the unsaturated polyester (A) and the polymerizable monomer (B).
7. Bulk moulding compound according to claim 1 or 2,
the low shrinkage agent (E) is contained in an amount of 10 to 40 parts by mass based on 100 parts by mass of the total of the unsaturated polyester (A) and the polymerizable monomer (B).
8. Bulk moulding compound according to claim 1 or 2,
the unsaturated polyester (A) and the polymerizable monomer (B) are contained in an amount of 200 to 500 parts by mass based on 100 parts by mass of the total of the unsaturated polyester (A) and the polymerizable monomer (B).
9. Bulk moulding compound according to claim 1 or 2,
the release agent (G) is contained in an amount of 1 to 20 parts by mass based on 100 parts by mass of the total of the unsaturated polyester (A) and the polymerizable monomer (B).
10. Bulk moulding compound according to claim 1 or 2,
the reinforcing fiber (C) is contained in an amount of 15 to 50 parts by mass based on 100 parts by mass of the total of the unsaturated polyester (A) and the polymerizable monomer (B).
11. A method of encapsulating a motor using the bulk molding compound of any one of claims 1-10.
12. A molded article comprising a cured product of the bulk molding compound according to any one of claims 1 to 10.
13. A method for producing a molded article, comprising the step of curing the bulk molding compound according to any one of claims 1 to 10 by heating and pressing.
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| JP2017221596 | 2017-11-17 | ||
| JP2017-221596 | 2017-11-17 | ||
| PCT/JP2018/033609 WO2019097824A1 (en) | 2017-11-17 | 2018-09-11 | Bulk molding compound and method for encapsulating motor using same |
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| CN111356722A CN111356722A (en) | 2020-06-30 |
| CN111356722B true CN111356722B (en) | 2022-12-30 |
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| Country | Link |
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| JP (1) | JP7108629B2 (en) |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09227665A (en) * | 1996-02-26 | 1997-09-02 | Kobe Steel Ltd | Heat-resistant unsaturated polyester resin composition, heat-resistant fiber reinforced composite material, and heat-resistant molding comprising the same |
| JP2005054068A (en) * | 2003-08-05 | 2005-03-03 | Showa Highpolymer Co Ltd | Unsaturated polyester resin, unsaturated polyester resin composite, and cured product of the resin composite |
| JP2008174629A (en) * | 2007-01-18 | 2008-07-31 | Matsushita Electric Ind Co Ltd | Molding material and molded part |
| JP2010202812A (en) * | 2009-03-05 | 2010-09-16 | Daiso Co Ltd | Diallyl phthalate crosslinked low shrinkage unsaturated polyester resin composition for molding and molded article of the same |
| CN102504123A (en) * | 2011-11-08 | 2012-06-20 | 桂林电器科学研究院 | Self-lubricating wear-resisting unsaturated polyester molding compound and preparation method thereof |
| JP2013209510A (en) * | 2012-03-30 | 2013-10-10 | Dainippon Toryo Co Ltd | Fiber-reinforced resin molding coating composition, fiber-reinforced resin molding obtained by applying the coating composition, and method for producing the fiber-reinforced resin molding |
| CN103987747A (en) * | 2011-12-14 | 2014-08-13 | 昭和电工株式会社 | Unsaturated polyester resin composition and encapsulated motor |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11150894A (en) * | 1997-11-19 | 1999-06-02 | Mitsuba Corp | Molding material for coil of motor |
| JP2001226573A (en) * | 2000-02-10 | 2001-08-21 | Showa Highpolymer Co Ltd | Unsaturated polyester resin composition |
-
2018
- 2018-09-11 WO PCT/JP2018/033609 patent/WO2019097824A1/en active Application Filing
- 2018-09-11 JP JP2019553708A patent/JP7108629B2/en active Active
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09227665A (en) * | 1996-02-26 | 1997-09-02 | Kobe Steel Ltd | Heat-resistant unsaturated polyester resin composition, heat-resistant fiber reinforced composite material, and heat-resistant molding comprising the same |
| JP2005054068A (en) * | 2003-08-05 | 2005-03-03 | Showa Highpolymer Co Ltd | Unsaturated polyester resin, unsaturated polyester resin composite, and cured product of the resin composite |
| JP2008174629A (en) * | 2007-01-18 | 2008-07-31 | Matsushita Electric Ind Co Ltd | Molding material and molded part |
| JP2010202812A (en) * | 2009-03-05 | 2010-09-16 | Daiso Co Ltd | Diallyl phthalate crosslinked low shrinkage unsaturated polyester resin composition for molding and molded article of the same |
| CN102504123A (en) * | 2011-11-08 | 2012-06-20 | 桂林电器科学研究院 | Self-lubricating wear-resisting unsaturated polyester molding compound and preparation method thereof |
| CN103987747A (en) * | 2011-12-14 | 2014-08-13 | 昭和电工株式会社 | Unsaturated polyester resin composition and encapsulated motor |
| JP2013209510A (en) * | 2012-03-30 | 2013-10-10 | Dainippon Toryo Co Ltd | Fiber-reinforced resin molding coating composition, fiber-reinforced resin molding obtained by applying the coating composition, and method for producing the fiber-reinforced resin molding |
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| Publication number | Publication date |
|---|---|
| JP7108629B2 (en) | 2022-07-28 |
| JPWO2019097824A1 (en) | 2020-10-01 |
| CN111356722A (en) | 2020-06-30 |
| WO2019097824A1 (en) | 2019-05-23 |
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