CN112236478A - Flame-retardant polybutylene terephthalate resin composition - Google Patents
Flame-retardant polybutylene terephthalate resin composition Download PDFInfo
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- CN112236478A CN112236478A CN201980037649.1A CN201980037649A CN112236478A CN 112236478 A CN112236478 A CN 112236478A CN 201980037649 A CN201980037649 A CN 201980037649A CN 112236478 A CN112236478 A CN 112236478A
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- polybutylene terephthalate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Abstract
The object is to provide a polybutylene terephthalate resin composition which contains a halogenated epoxy flame retardant and has excellent flame retardancy. The above object is achieved by setting the content of the organic solvent in the halogenated epoxy flame retardant to a predetermined amount or less and setting the total content of epoxy groups in the polybutylene terephthalate resin composition as a whole to a predetermined amount or less.
Description
Technical Field
The present invention relates to a flame-retardant polybutylene terephthalate resin composition, a method for producing a flame-retardant polybutylene terephthalate resin composition, and a molded article obtained from the flame-retardant polybutylene terephthalate resin composition.
Background
Polybutylene terephthalate resins (PBT resins) are widely used as engineering plastics for various applications such as electric and electronic components because of their excellent electrical properties. In these applications, flame retardancy is required for the materials used in order to prevent ignition due to electrical leakage (tracking) or the like. Polybutylene terephthalate resins are insufficient in flame retardancy themselves, and therefore, are used in the form of a flame-retardant resin composition to which a flame retardant is added.
Patent document 1 describes a method for producing a brominated epoxy compound-based flame retardant. This production method is characterized in that an aromatic epoxy compound such as a diglycidyl ether of an alcohol containing an aromatic nucleus, a diglycidyl ether or polyglycidyl ether of a polyhydric phenol, a diglycidyl ester of an aromatic dibasic acid, a monoglycidyl ether of an alkylphenol, a monoglycidyl ether of a hydroxybenzoic acid, a polyglycidyl amine based on a (β -methyl) epichlorohydrin adduct of p-aminophenol, an aromatic diamine or polyamine, or the like, or a chlorohydrin compound serving as a precursor thereof is brominated by adding bromine, and the obtained brominated bromohydrin compound or brominated chlorohydrin compound is ring-closed epoxidized by dehydrobromination or dehydrochlorination using an alkali metal hydroxide.
Patent document 2 describes a brominated epoxy compound-based flame retardant for engineering thermoplastics. The molecular weight of the flame retardant is preferably 7000-50000 daltons, and the epoxy equivalent is preferably more than 10000 g/eq.
Further, it has been known that molecular weight, epoxy equivalent, and the like have an influence on thickening of an epoxy compound. In order to suppress the mixing of the carbide generated by the thickening into the Black foreign matter (BS: Black Speck) in the molded article, the ranges of the molecular weight and the epoxy equivalent have been adjusted conventionally. For example, patent document 3 describes that the use of an epoxy compound having an epoxy equivalent of 600 to 1500g/eq can suppress the generation of black foreign matter in a molded article of a polybutylene terephthalate resin composition.
Documents of the prior art
Patent document
Patent document 1: japanese examined patent publication No. 60-016952
Patent document 2: japanese patent No. 5143419
Patent document 3: japanese patent No. 6100983
Disclosure of Invention
Problems to be solved by the invention
The present invention addresses the problem of providing a polybutylene terephthalate resin composition that contains a halogenated epoxy flame retardant and has excellent flame retardancy.
Means for solving the problems
The present inventors have conducted intensive studies in order to solve the above problems, and as a result, have found that: the above object can be achieved by setting the content of the organic solvent in the halogenated epoxy flame retardant to a predetermined amount or less and the total content of epoxy groups in the polybutylene terephthalate resin composition as a whole to a predetermined amount or less, and the present invention has been completed.
That is, the present invention relates to the following (1) to (9).
(1) A flame-retardant polybutylene terephthalate resin composition characterized by containing: polybutylene terephthalate resin; and a halogenated epoxy flame retardant, wherein the content of an organic solvent selected from the group consisting of toluene, methyl isobutyl ketone, methyl ethyl ketone and acetone in the halogenated epoxy flame retardant is 50ppm or less, and the total content of epoxy groups in the entire composition is 0.0155mol/kg or less.
(2) The flame-retardant polybutylene terephthalate resin composition according to the item (1), wherein the halogenated epoxy flame retardant has an epoxy equivalent of 30000g/eq or more.
(3) The flame-retardant polybutylene terephthalate resin composition according to the item (1) or (2), wherein the halogenated epoxy flame retardant is a brominated epoxy flame retardant.
(4) The flame-retardant polybutylene terephthalate resin composition according to any one of (1) to (3), which further contains a flame-retardant auxiliary selected from the group consisting of antimony pentoxide, antimony trioxide and sodium antimonate.
(5) The flame-retardant polybutylene terephthalate resin composition according to any one of (1) to (4), wherein a molded article obtained from the flame-retardant polybutylene terephthalate resin composition has a flammability of V-0 at 0.8mmt in accordance with flammability UL94 standard.
(6) The flame-retardant polybutylene terephthalate resin composition according to any one of (1) to (5), which further contains an amorphous resin.
(7) The flame-retardant polybutylene terephthalate resin composition according to the item (6), wherein the non-crystalline resin is an acrylonitrile-styrene copolymer resin.
(8) The process for producing a flame-retardant polybutylene terephthalate resin composition according to any one of (1) to (7).
(9) A molded article obtained from the flame-retardant polybutylene terephthalate resin composition of any one of (1) to (7).
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a polybutylene terephthalate resin composition containing a halogenated epoxy flame retardant and having excellent flame retardancy can be provided.
Detailed Description
Hereinafter, one embodiment of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be carried out by appropriately changing the embodiments within a range not to impair the effects of the present invention.
[ flame-retardant polybutylene terephthalate resin composition ]
Hereinafter, the details of each component of the flame-retardant polybutylene terephthalate resin composition according to the present embodiment will be described by way of example.
(polybutylene terephthalate resin)
The polybutylene terephthalate resin (PBT resin) is a resin comprising at least terephthalic acid or an ester-forming derivative thereof (C)1-6Alkyl ester, acid halide, etc.) and a diol component containing at least an alkylene diol having 4 carbon atoms (1, 4-butanediol) or an ester-forming derivative thereof (e.g., an acetylated compound), and a polycondensation product thereof. In the present embodiment, the polybutylene terephthalate resin is not limited to a homopolymeric polybutylene terephthalate resin, and may be a copolymer containing 60 mol% or more of a butylene terephthalate unit.
The amount of terminal carboxyl groups of the polybutylene terephthalate resin is not particularly limited as long as the object of the present invention is not impaired, and is preferably 30meq/kg or less, and more preferably 25meq/kg or less.
The intrinsic viscosity of the polybutylene terephthalate resin is not particularly limited as long as it does not impair the object of the present invention, and is preferably 0.60dL/g to 1.2dL/g, more preferably 0.65dL/g to 0.9 dL/g. When a polybutylene terephthalate resin having an intrinsic viscosity within such a range is used, the moldability of the resulting polybutylene terephthalate resin composition becomes particularly excellent. Further, it is also possible to blend polybutylene terephthalate resins having different intrinsic viscosities to adjust the intrinsic viscosities. For example, a polybutylene terephthalate resin having an intrinsic viscosity of 0.9dL/g can be prepared by blending a polybutylene terephthalate resin having an intrinsic viscosity of 1.0dL/g with a polybutylene terephthalate resin having an intrinsic viscosity of 0.7 dL/g. The intrinsic viscosity of the polybutylene terephthalate resin can be measured, for example, in o-chlorophenol at a temperature of 35 ℃.
In the preparation of polybutylene terephthalate resin, when an aromatic dicarboxylic acid other than terephthalic acid or an ester-forming derivative thereof is used as a comonomer component, for example, C-containing compounds such as isophthalic acid, phthalic acid, 2, 6-naphthalenedicarboxylic acid, and 4, 4' -dicarboxydiphenyl ether can be used6-14The aromatic dicarboxylic acid of (a); amber (Succinum)C acid, adipic acid, azelaic acid, sebacic acid, etc2-16Alkane dicarboxylic acids of (a); cyclohexanedicarboxylic acid and the like C5-10Cycloalkanedicarboxylic acids of (a); ester-forming derivatives (C) of these dicarboxylic acid components1-6Alkyl ester derivatives, acid halides, etc.). These dicarboxylic acid components may be used alone or in combination of two or more.
Among these dicarboxylic acid components, C such as isophthalic acid is more preferable6-12The aromatic dicarboxylic acid of (a); and C such as adipic acid, azelaic acid and sebacic acid4-12An alkane dicarboxylic acid.
In the production of the polybutylene terephthalate resin, when a diol component other than 1, 4-butanediol is used as a comonomer component, for example, C such as ethylene glycol, propylene glycol, trimethylene glycol, 1, 3-butanediol, hexamethylene glycol, neopentyl glycol, 1, 3-octanediol, etc., can be used2-10An alkylene glycol of (a); polyoxyalkylene glycols such as diethylene glycol, triethylene glycol, and dipropylene glycol; alicyclic diols such as cyclohexanedimethanol and hydrogenated bisphenol a; aromatic diols such as bisphenol a and 4, 4' -dihydroxybiphenyl; bisphenol A C such as bisphenol A ethylene oxide two-mole adduct and bisphenol A propylene oxide three-mole adduct2-4Alkylene oxide adducts of (a); or an ester-forming derivative (such as an acetylated product) of such a diol. These diol components may be used alone or in combination of two or more.
Among these diol components, C such as ethylene glycol and trimethylene glycol is more preferable2-6An alkylene glycol of (a); polyoxyalkylene glycols such as diethylene glycol; or alicyclic diols such as cyclohexanedimethanol.
Examples of the comonomer component that can be used in addition to the dicarboxylic acid component and the diol component include aromatic hydroxycarboxylic acids such as 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and 4-carboxy-4' -hydroxybiphenyl; aliphatic hydroxycarboxylic acids such as glycolic acid and hydroxycaproic acid; c such as propiolactone, butyrolactone, valerolactone or caprolactone (. epsilon. -caprolactone)3-12A lactone; ester-forming derivatives (C) of these comonomer components1-6Alkyl ester derivatives, acid halides, acetylates, etc.).
The content of the polybutylene terephthalate resin is preferably 30 to 90 mass%, more preferably 40 to 80 mass%, and still more preferably 50 to 70 mass% of the total mass of the resin composition.
(halogenated epoxy flame retardant)
The epoxy compound used in the halogenated epoxy flame retardant of the present invention contains 1 or more epoxy groups in 1 molecule. As the epoxy compound, an aromatic epoxy compound is preferably used from the viewpoint of improving thermal stability and hydrolysis resistance. Examples of the aromatic epoxy compound include biphenyl type epoxy compounds, bisphenol a type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, and the like.
Further, as the epoxy compound, two or more compounds may be used in any combination.
The epoxy equivalent of the epoxy compound is preferably 30000 g/equivalent (g/eq) or more, more preferably 32000g/eq or more, still more preferably 34000g/eq or more, still more preferably 36000g/eq or more, and particularly preferably 36500g/eq or more. When the epoxy equivalent is in this range, the molded article obtained from the flame retardant polybutylene terephthalate resin composition of the present invention can have good appearance, and the occurrence of deposits on the screw of an extruder or a molding machine during molding can be suppressed. In addition, the flexural modulus of the molded article obtained from the flame-retardant polybutylene terephthalate resin composition of the present invention can be made to be a good value.
The halogenated epoxy flame retardant of the present invention is preferably a brominated epoxy flame retardant.
As described above, the halogenated epoxy flame retardant of the present invention has a content of the organic solvent selected from the group consisting of toluene, methyl isobutyl ketone, methyl ethyl ketone and acetone of 50ppm or less. The content of the organic solvent is preferably 40ppm or less, more preferably 30ppm or less, further preferably 20ppm or less, further preferably 10ppm or less, and particularly preferably 8ppm or less. When the content of the organic solvent in the halogenated epoxy flame retardant is in this range, the molded article obtained from the flame-retardant polybutylene terephthalate resin composition of the present invention can have good appearance, and the formation of deposits on the screw of an extruder or a molding machine during molding can be suppressed. In addition, the flexural modulus of the molded article obtained from the flame-retardant polybutylene terephthalate resin composition of the present invention can be made to be a good value.
(Total epoxy group content of the flame-retardant polybutylene terephthalate resin composition as a whole)
As described above, the total content of epoxy groups in the flame retardant polybutylene terephthalate resin composition of the present invention is 0.0155mol/kg or less. The total content of epoxy groups in the entire composition is preferably 0.0152mol/kg or less, more preferably 0.0150mol/kg or less, still more preferably 0.0149mol/kg or less, and particularly preferably 0.0148mol/kg or less. By setting the total content of epoxy groups in the flame retardant polybutylene terephthalate resin composition in this range, the molded article obtained from the flame retardant polybutylene terephthalate resin composition of the present invention can have good appearance, and the occurrence of deposits on the screw of an extruder or a molding machine during molding can be suppressed. In addition, the flexural modulus of the molded article obtained from the flame-retardant polybutylene terephthalate resin composition of the present invention can be made to be a good value.
(flame retardant auxiliary)
The flame-retardant polybutylene terephthalate resin composition of the present invention preferably further contains a flame-retardant auxiliary. The flame retardant aid is not particularly limited, but is preferably a flame retardant aid selected from the group consisting of antimony pentoxide, antimony trioxide, and sodium antimonate, and more preferably antimony pentoxide or antimony trioxide.
(amorphous resin)
The flame retardant polybutylene terephthalate resin composition of the present invention preferably further contains an amorphous resin. By further containing an amorphous resin, warpage of a molded article obtained from the flame-retardant polybutylene terephthalate resin composition can be suppressed. The amorphous resin is preferably an acrylonitrile-styrene copolymer resin.
(Filler)
The composition of the present invention may use a filler as required. The incorporation of such a filler is preferable for obtaining excellent properties such as mechanical strength, heat resistance, dimensional stability, and electrical properties, and is effective particularly for the purpose of improving rigidity. The filler is used in the form of fiber, powder, or plate depending on the purpose.
Examples of the fibrous filler include glass fibers, asbestos fibers, carbon fibers, silica/alumina fibers, zirconia fibers, boron nitride fibers, silicon nitride fibers, boron fibers, potassium titanate fibers, and fibrous materials of metals such as stainless steel, aluminum, titanium, copper, and brass. Organic fibrous materials having a high melting point such as polyamide, fluororesin and acrylic resin may be used.
Examples of the particulate filler include silicates such as carbon black, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, and wollastonite; metal oxides such as iron oxide, titanium oxide, and aluminum oxide; metal carbonates such as calcium carbonate and magnesium carbonate; metal sulfates such as calcium sulfate and barium sulfate; and silicon carbide, silicon nitride, boron nitride, various metal powders, and the like.
Further, examples of the plate-like inorganic filler include mica, glass flake, and various metal foils.
The type of the filler is not particularly limited, and 1 or more fillers may be added. In particular, potassium titanate fiber, mica, talc, and wollastonite are preferably used.
The amount of the filler added is not particularly limited, and is preferably 200 parts by mass or less with respect to 100 parts by mass of the polybutylene terephthalate resin. When the filler is excessively added, moldability is poor and toughness is reduced.
(additives)
Further, in the composition of the present invention, a known substance usually added to a thermoplastic resin or the like may be added and used in combination in order to impart desired characteristics other than flame retardancy depending on the purpose. For example, stabilizers such as antioxidants, ultraviolet absorbers and light stabilizers, antistatic agents, lubricants, mold release agents, colorants such as dyes and pigments, and plasticizers may be blended. In particular, it is effective to add an antioxidant for improving heat resistance.
[ method for producing flame-retardant polybutylene terephthalate resin composition ]
The flame-retardant polybutylene terephthalate resin composition of the present invention may be in the form of a powder-granule mixture or a molten mixture (melt-kneaded product) such as pellets. The method for producing the polybutylene terephthalate resin composition according to one embodiment of the present invention is not particularly limited, and the polybutylene terephthalate resin composition can be produced by using an apparatus and a method known in the art. For example, pellets for molding can be prepared by mixing necessary components and kneading the mixture using a single-screw or twin-screw extruder or other melt kneading device. Various extruders or other melt-kneading apparatuses can be used. Further, all the components may be charged from the hopper at the same time, or a part of the components may be charged from the side inlet.
The flame-retardant polybutylene terephthalate resin composition of the present invention is preferably produced by vacuum drying (vacuuming). Vacuum drying may be performed using a commonly used rotary evaporator, oven, or the like.
[ molded article obtained from flame-retardant polybutylene terephthalate resin composition ]
The flame retardant polybutylene terephthalate resin composition of the present invention can be preferably used as electric/electronic parts such as relays, switches, connectors, drivers, sensors, transformer frames, junction boxes, covers, switches, sockets, coils, plugs, and the like, particularly parts around power supplies. Further, the resin composition can be suitably used as a molding material for automotive parts such as vehicle-mounted part housings such as an ECU housing and a connector housing and vehicle-mounted electric parts.
The method for obtaining a molded article using the flame-retardant polybutylene terephthalate resin composition is not particularly limited, and a known method can be used. For example, the flame-retardant polybutylene terephthalate resin composition can be produced by charging the flame-retardant polybutylene terephthalate resin composition into an extruder, melt-kneading the composition to prepare pellets, charging the pellets into an injection molding machine equipped with a predetermined mold, and injection-molding the pellets.
The molded article preferably has a flammability of 0.8mmt based on the flammability UL94 standard of V-0. The combustibility V-0 can be confirmed by bringing the flame of a gas burner into contact with the lower end of a vertically held sample for 10 seconds, stopping combustion for 30 seconds or less, and then bringing the flame into contact for 10 seconds, and satisfying the following criteria.
None of the samples continued to burn for 10 seconds or more after any flame contact.
10 flame contacts were made on 5 specimens, the total burning time not exceeding 50 seconds.
The sample that did not burn until the fixing jig position.
Samples without burning particles dropping off the cotton wool placed under the sample, which could cause ignition.
No red-hot samples lasted more than 30 seconds after the second flame contact.
(examples)
The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples as long as the invention does not exceed the gist thereof.
(1) Flame retardancy
The materials obtained by dry blending the components and compositions (parts by mass) shown in Table 1 were charged into a twin-screw extruder (made by Nippon Steel Co., Ltd.) having a screw diameter of 30mm, melt-kneaded at 260 ℃ and dried at 140 ℃ for 3 hours, and then injection-molded under conditions of a cylinder temperature of 250 ℃ and a mold temperature of 70 ℃ to prepare test pieces having a thickness of 1.6mm and 0.8mm according to UL94, and the test pieces were evaluated for flammability, and when V-0 is satisfied, they were marked as "O" and when V-0 is not satisfied, they were marked as "X". The results are shown in Table 1.
(2) Resistance to hydrolysis
Pellets of a polybutylene terephthalate resin composition obtained in the same manner as in the evaluation of flame retardancy were dried at 140 ℃ for 3 hours, and then injection-molded into a test piece for tensile property evaluation of ISO3167 under conditions of a cylinder temperature of 250 ℃ and a mold temperature of 70 ℃, and a tensile strength test was performed in accordance with ISO527-1, 2. Subsequently, the test piece was subjected to a wet heat treatment at 122 ℃ and 2atm (saturated water vapor pressure) for 100 hours, and the tensile strength test was similarly carried out using the product obtained therefrom, whereby the tensile strength retention was determined to be "good" when the tensile strength retention was 50% or more and "x" when the tensile strength retention was less than 50% with respect to the tensile strength retention before the wet heat treatment, and the hydrolysis resistance was evaluated. The results are shown in Table 1.
(3) Attachment for screw
Pellets of a polybutylene terephthalate resin composition obtained in the same manner as in the evaluation of flame retardancy were dried at 140 ℃ for 3 hours, then melt-kneaded in the following procedure, and the amount of black deposits was visually observed, and the pellets were marked as "x" when the deposits were remarkably generated, as "o" when the deposits were less, and as "excellent" when the deposits were less. The results are shown in Table 1.
Step 1: using LABO PLASTMIL manufactured by Toyo Seiki K.K., the polybutylene terephthalate resin composition was extruded for 10 minutes under conditions of a cylinder temperature of 275 ℃ and a screw rotation speed of 20 rpm.
Step 2: the screw was stopped at a cylinder temperature of 275 ℃ to allow the polybutylene terephthalate resin composition in the cylinder to stay for 120 minutes.
And step 3: the cylinder temperature was set to 275 ℃ and the screw speed was set to 21rpm, and purging (purge) was performed for 10 minutes with the polybutylene terephthalate resin composition.
And 4, step 4: the cylinder temperature was set to 275 ℃ and the screw speed was set to 60rpm, and purging was performed with the polyethylene resin for 5 minutes.
And 5: the cylinder temperature was set to 200 ℃ and the screw rotation speed was set to 60rpm, and the mixture was purged with a purge material "LIOCLEAN-Z" manufactured by TOYO COLOR K.K. for 5 minutes.
Step 6: the screw was pulled out, lightly wiped with cotton cloth, and after removing the purging material, the amount of black deposit on the screw was observed.
(4) Flexural modulus
Pellets of a polybutylene terephthalate resin composition obtained in the same manner as in the evaluation of flame retardancy were dried at 140 ℃ for 3 hours, and then injection-molded into a bending test piece of 80mm × 10mm × 4mm under conditions of a cylinder temperature of 250 ℃ and a mold temperature of 70 ℃, and the pellets were subjected to a bending test at a pressing speed of 2.0 mm/minute and an inter-fulcrum distance of 64mm in accordance with ISO178, and evaluated as "O" when the bending modulus was 10000MPa or more and "X" when the bending modulus was less than 10000 MPa. The results are shown in Table 1.
[ Table 1]
The details of each component described in table 1 are as follows.
PBT resin: polybutylene terephthalate resin having a carboxyl end group concentration of 18meq/kg and an intrinsic viscosity of 0.88dL/g, manufactured by Geiger plastics Co., Ltd
Glass fiber: ECS03T-127 (diameter: 13 μm, length: 3mm), manufactured by Nippon Denshoku K.K
AS resin: ningbo LG Yongxing Chemical Co., Ltd., AS RESIN 80HF, manufactured by Ltd
Brominated epoxy flame retardant 1: brominated epoxy compound having an epoxy equivalent of 36800g/eq, an organic solvent content of 5ppm and a weight average molecular weight of about 18000
Brominated epoxy flame retardant 2: brominated epoxy compound having an epoxy equivalent of 43200g/eq, an organic solvent amount of 0ppm and a weight average molecular weight of about 20000
Brominated epoxy flame retardant 3: brominated epoxy compound having an epoxy equivalent of 28600g/eq, an organic solvent content of 60ppm and a weight average molecular weight of about 9000
Brominated epoxy flame retardant 4: brominated epoxy compound having an epoxy equivalent of 19900g/eq, an organic solvent content of 4ppm and a weight average molecular weight of about 23000
Brominated polyacrylate flame retardant: polyacrylic acid pentabromobenzyl ester FR-1025 (epoxy equivalent: 0g/eq), manufactured by ICL JAPAN Co., Ltd
Antimony trioxide: PATOX-M, manufactured by Japan concentrate Co., Ltd
Antimony pentoxide: sunepoch NA-1030 made by Nissan chemical industries, Ltd
Epoxy resin (stabilizer): mitsubishi chemical corporation, jER 1004K (epoxy equivalent: 925g/eq)
PTFE (anti-drip agent): polytetrafluoroethylene
Antioxidant: tetrakis [ methylene-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] methane (manufactured by BASF JAPAN corporation, "IRGANOX 1010")
Releasing agent: low molecular weight polyethylene (manufactured by Sanyo chemical industries Co., Ltd., "SUNWAX 161-P")
Carbon black: mitsubishi chemical corporation, MA600B
As shown in Table 1, the molded articles obtained from the flame retardant polybutylene terephthalate resin compositions of examples 1 to 9 satisfying the constitution of claim 1 of the present application are all excellent in appearance, and no deposit adhering to the screw is generated at the time of molding. In addition, any of the examples showed excellent flexural modulus.
On the other hand, the polybutylene terephthalate resin compositions of comparative examples 1 and 4, in which the content of the organic solvent in the halogenated epoxy flame retardant is not within the range of claim 1, exhibited poor appearance of the molded articles, and adhered to the screw during molding occurred.
In addition, the polybutylene terephthalate resin compositions of comparative examples 2, 4 and 5, in which the total content of epoxy groups in the entire composition was not within the range of claim 1, were poor in appearance of molded articles, and adhered to a screw during molding was generated.
Further, the molded article obtained from the polybutylene terephthalate resin composition of comparative example 3, in which the total content of epoxy groups in the entire composition is out of the range of claim 1, had a poor bending modulus.
Claims (9)
1. A flame-retardant polybutylene terephthalate resin composition characterized by containing:
polybutylene terephthalate resin; and
a halogenated epoxy flame retardant having a content of an organic solvent selected from the group consisting of toluene, methyl isobutyl ketone, methyl ethyl ketone and acetone of 50ppm or less,
the total content of epoxy groups in the entire composition is 0.0155mol/kg or less.
2. The flame-retardant polybutylene terephthalate resin composition according to claim 1, wherein the halogenated epoxy flame retardant has an epoxy equivalent of 30000g/eq or more.
3. The flame retardant polybutylene terephthalate resin composition according to claim 1 or 2, wherein the halogenated epoxy flame retardant is a brominated epoxy flame retardant.
4. The flame retardant polybutylene terephthalate resin composition according to any one of claims 1 to 3, which further contains a flame retardant auxiliary selected from the group consisting of antimony pentoxide, antimony trioxide and sodium antimonate.
5. The flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 4, wherein a molded article obtained from the flame-retardant polybutylene terephthalate resin composition has a flammability of V-0 at 0.8mmt in accordance with the flammability UL94 standard.
6. The flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 5, which further contains an amorphous resin.
7. The flame retardant polybutylene terephthalate resin composition according to claim 6, wherein the non-crystalline resin is an acrylonitrile-styrene copolymer resin.
8. The method for producing a flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 7.
9. A molded article obtained from the flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 7.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018107688 | 2018-06-05 | ||
| JP2018-107688 | 2018-06-05 | ||
| PCT/JP2019/022257 WO2019235505A1 (en) | 2018-06-05 | 2019-06-05 | Flame-retardant polybutylene terephthalate resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112236478A true CN112236478A (en) | 2021-01-15 |
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| JP (1) | JP7454495B2 (en) |
| CN (1) | CN112236478B (en) |
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| WO (1) | WO2019235505A1 (en) |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06157873A (en) * | 1992-11-17 | 1994-06-07 | Dainippon Ink & Chem Inc | Flame-retardant thermoplastic resin composition, flame retardant and production of flame retardant |
| JPH0741651A (en) * | 1992-11-18 | 1995-02-10 | Omron Corp | Polyethylene terephthalate resin composition and relay, switch, connector and sensor |
| CN1735654A (en) * | 2003-01-13 | 2006-02-15 | 溴化物有限公司 | Flame-retardant for engineering thermoplastic applications |
| CN101613520A (en) * | 2008-06-26 | 2009-12-30 | 胜技高分子株式会社 | Flame retardance poly mutual-phenenyl two acid bromide two alcohol ester resin combination and molding |
| CN105377983A (en) * | 2013-06-13 | 2016-03-02 | 胜技高分子株式会社 | Polybutylene terephthalate resin composition and injection-molded article |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6317223B2 (en) | 2014-09-22 | 2018-04-25 | 三菱エンジニアリングプラスチックス株式会社 | Resin pellet manufacturing method and resin pellet manufacturing apparatus |
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- 2019-06-05 WO PCT/JP2019/022257 patent/WO2019235505A1/en active Application Filing
- 2019-06-05 JP JP2020523135A patent/JP7454495B2/en active Active
- 2019-06-05 CN CN201980037649.1A patent/CN112236478B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06157873A (en) * | 1992-11-17 | 1994-06-07 | Dainippon Ink & Chem Inc | Flame-retardant thermoplastic resin composition, flame retardant and production of flame retardant |
| JPH0741651A (en) * | 1992-11-18 | 1995-02-10 | Omron Corp | Polyethylene terephthalate resin composition and relay, switch, connector and sensor |
| CN1735654A (en) * | 2003-01-13 | 2006-02-15 | 溴化物有限公司 | Flame-retardant for engineering thermoplastic applications |
| CN101613520A (en) * | 2008-06-26 | 2009-12-30 | 胜技高分子株式会社 | Flame retardance poly mutual-phenenyl two acid bromide two alcohol ester resin combination and molding |
| CN105377983A (en) * | 2013-06-13 | 2016-03-02 | 胜技高分子株式会社 | Polybutylene terephthalate resin composition and injection-molded article |
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| Publication number | Publication date |
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| JP7454495B2 (en) | 2024-03-22 |
| CN112236478B (en) | 2023-03-14 |
| WO2019235505A1 (en) | 2019-12-12 |
| TW202003684A (en) | 2020-01-16 |
| JPWO2019235505A1 (en) | 2021-06-10 |
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