CN111051431A - Flame-retardant polybutylene terephthalate resin composition - Google Patents
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- CN111051431A CN111051431A CN201880053899.XA CN201880053899A CN111051431A CN 111051431 A CN111051431 A CN 111051431A CN 201880053899 A CN201880053899 A CN 201880053899A CN 111051431 A CN111051431 A CN 111051431A
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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
- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
- C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
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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
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
- C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
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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
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Abstract
[ problem ] to provide: a flame-retardant polybutylene terephthalate resin composition which is less likely to cause contact defects due to corrosion of contact metal by an arc in a circuit breaker and which can be used for parts such as arc extinguishing members. [ MEANS FOR solving PROBLEMS ] in a polybutylene terephthalate resin composition using a halogenated benzyl acrylate flame retardant as a flame retardant, a certain amount or more of a halogenated aromatic compound such as chlorobenzene is used in the production process of the flame retardant, thereby solving the above-mentioned problems.
Description
Technical Field
The present invention relates to a flame-retardant polybutylene terephthalate resin composition and a method for producing the same.
Background
Polybutylene terephthalate resins (PBT resins) are widely used as engineering plastics for various applications such as electric/electronic components because of their excellent electrical characteristics. In these applications, flame retardancy is required for the materials used in order to prevent ignition due to leakage of electricity or the like. Polybutylene terephthalate resin is used in the form of a flame-retardant resin composition containing a flame retardant because it has insufficient flame retardancy.
As a halogenated benzyl acrylate-based flame retardant added to a polybutylene terephthalate resin, pentabromobenzyl polyacrylate (PBBPA) is introduced in patent document 1. As a method for producing the flame retardant, the following method is exemplified in paragraph [0004] of patent document 1: a method of polymerizing pentabromobenzyl acrylate as a monomer in ethylene glycol monomethyl ether, methyl ethyl ketone or ethylene glycol dimethyl ether, or a method of polymerizing pentabromobenzyl acrylate in chlorobenzene.
Flame-retardant polybutylene terephthalate resin compositions containing such flame retardants are sometimes used for parts of circuit breakers (relays). On the other hand, patent document 2 describes: in circuit breakers, decomposition gases of halogen-based flame retardants cause corrosion of metals and contact defects, and non-halogen-based nitrogen-based flame retardants are disclosed to be advantageous.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2015-532350
Patent document 2: international publication No. 2002/078032 pamphlet
Disclosure of Invention
Problems to be solved by the invention
The object of the present invention is to provide: a flame-retardant polybutylene terephthalate resin composition which is less likely to cause contact defects due to corrosion of contact metal by an arc in a circuit breaker and which can be used for parts such as arc extinguishing members.
Means for solving the problems
The present inventors have found, in the course of their research, that a flame-retardant polybutylene terephthalate resin composition which is less likely to cause contact defects due to corrosion of contact metal by an arc and which can be used for parts such as arc extinguishing members, is less likely to cause contact defects in circuit breakers: the present inventors have found that the above-mentioned problems can be solved by adding a halogenated aromatic compound such as chlorobenzene in an amount of not less than a certain amount to a polybutylene terephthalate resin composition using a halogenated benzyl acrylate flame retardant as a flame retardant, particularly by adjusting the amount of the halogenated aromatic compound derived from a production process of the flame retardant, and have completed the present invention.
That is, the present invention relates to the following (1) to (9).
(1) A flame-retardant polybutylene terephthalate resin composition which contains a polybutylene terephthalate resin and a halogenated benzyl acrylate flame retardant, and is characterized in that the content of a halogenated aromatic compound other than the flame retardant is 0.5ppm to 5ppm as measured by headspace gas chromatography (heating at 150 ℃ for 1 hour).
(2) The flame-retardant polybutylene terephthalate resin composition according to (1), wherein the halogenated benzyl acrylate flame retardant is a brominated acrylic polymer represented by the general formula (I).
(wherein X is a hydrogen atom or a bromine atom, at least 1 or more of X are bromine, and m is a number of 10 to 2000.)
(3) The flame-retardant polybutylene terephthalate resin composition according to the item (1) or (2), wherein the halogenated benzyl acrylate flame retardant is poly (pentabromobenzyl acrylate).
(4) The flame retardant polybutylene terephthalate resin composition according to any one of (1) to (3), wherein the halogenated aromatic compound other than the flame retardant is halogenated benzene.
(5) The flame retardant polybutylene terephthalate resin composition according to any one of (1) to (4), wherein the halogenated aromatic compound other than the aforementioned flame retardant is chlorobenzene.
(6) A process for producing a flame-retardant polybutylene terephthalate resin composition according to any one of (1) to (5), characterized in that a halogenated aromatic compound is used as a solvent in the production of a halogenated benzyl acrylate-based flame retardant.
(7) The process for producing a flame-retardant polybutylene terephthalate resin composition according to item (6), wherein the halogenated aromatic compound is halogenated benzene.
(8) The process for producing a flame-retardant polybutylene terephthalate resin composition according to the item (6) or (7), wherein the halogenated aromatic compound is chlorobenzene.
(9) The process for producing a flame-retardant polybutylene terephthalate resin composition according to any one of (6) to (8), wherein vacuum drying is performed.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided a flame-retardant polybutylene terephthalate resin composition which is less likely to cause contact defects due to corrosion of contact metal by an arc in a circuit breaker and which can be used for parts such as arc extinguishing members.
Detailed Description
One embodiment of the present invention will be described in detail below. The present invention is not limited to the following embodiments, and can be carried out with appropriate modifications within a range not impairing the effects of the present invention.
[ flame-retardant polybutylene terephthalate resin composition ]
The following will describe details of each component of the flame-retardant polybutylene terephthalate resin composition of the present embodiment as an example.
(polybutylene terephthalate resin)
The polybutylene terephthalate resin (PBT resin) is obtained by reacting a polybutylene terephthalate resin (PBT resin) containing at least terephthalic acid or an ester-forming derivative thereof (C)1-6Alkyl ester, acid halide, etc.) with an alkylene glycol (1, 4) containing at least 4 carbon atomsButanediol) or an ester-forming derivative thereof (e.g., an acetylated product) by polycondensation of a diol component. In the present embodiment, the polybutylene terephthalate resin is not limited to a homopolybutylene terephthalate resin, and may be a copolymer containing 60 mol% or more of a butylene terephthalate unit, or may be a copolymer containing 75 mol% or more and 95 mol% or less of a butylene terephthalate unit.
The amount of terminal carboxyl groups in the polybutylene terephthalate resin is not particularly limited as long as the object of the present invention is not impaired, but 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 or more and 1.2dL/g or less, and more preferably 0.65dL/g or more and 0.9dL/g or less. When a polybutylene terephthalate resin having an intrinsic viscosity within such a range is used, the obtained polybutylene terephthalate resin composition is particularly excellent in moldability. In addition, 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 such as isophthalic acid, phthalic acid, 2, 6-naphthalenedicarboxylic acid, 4' -dicarboxydiphenyl ether and the like can be used8-14The aromatic dicarboxylic acid of (a); c such as succinic acid, adipic acid, azelaic acid and sebacic acid4-16Alkane dicarboxylic acids of (a); cyclohexanedicarboxylic acid and the like C5-10Cycloalkanedicarboxylic acids of (a); ester-forming derivatives (C) of these dicarboxylic acid components1-6Alkyl of (2)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 preferable8-12And C such as adipic acid, azelaic acid and sebacic acid6-12An alkane dicarboxylic acid.
When a diol component other than 1, 4-butanediol is used as a comonomer component in the production of the polybutylene terephthalate resin, for example: c such as ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 3-butanediol, hexamethylene glycol, neopentyl glycol, 1, 3-octanediol2-10An 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; ethylene oxide 2 mol adduct of bisphenol A, propylene oxide 3 mol adduct of bisphenol A, and the like, bisphenol A C2-4An alkylene oxide adduct of (a); or an ester-forming derivative (acetylated product or the like) of these diols. These diol components may be used alone or in combination of two or more.
Among these diol components, C such as ethylene glycol and 1, 3-propanediol is more preferable2-6And polyoxyalkylene glycol such as diethylene glycol, and alicyclic glycol 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 diglycolic 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.
(benzyl ester of halogenated acrylate flame retardants)
The halogenated benzyl acrylate flame retardant used in the present invention includes brominated acrylic polymers represented by the following general formula (I).
Wherein at least 1 or more of X's are bromine. The number of X in one structural unit is 1 to 5, and preferably 3 to 5 in view of flame retardant effect. The average degree of polymerization m is 10 to 2000, preferably 15 to 1000. When the average polymerization degree is low, thermal stability is deteriorated, and when it exceeds 2000, moldability of the polybutylene terephthalate resin after addition is deteriorated. Further, the above brominated acrylic polymer may be used in 1 kind or in combination of two or more kinds.
The halogenated benzyl acrylate-based flame retardant used in the present invention is obtained by polymerizing a halogenated aromatic compound in a state of preferably 100ppm or more and 1500ppm or less, more preferably 120ppm or more and 1000ppm or less, further preferably 150ppm or more and 800ppm or less, and particularly preferably 200ppm or more and 500ppm or less, in addition to the above-mentioned brominated acrylic polymer as the flame retardant itself. The content of the halogenated aromatic compound other than the flame retardant can be determined, for example, as follows: the amount of gas generated during the heat treatment in the headspace of a sample obtained by pulverizing a halogenated benzyl acrylate flame retardant was determined based on the amount of gas generated from a halogenated aromatic compound by measuring the gas generated by the gas chromatography.
The brominated acrylic polymer represented by the general formula (I) can be obtained by polymerizing benzyl acrylate containing bromine alone, or by copolymerizing benzyl methacrylate or the like having a similar structure. As the bromine-containing benzyl acrylate, pentabromobenzyl acrylate, tetrabromobenzyl acrylate, tribromobenzyl acrylate or mixtures thereof can be cited. Among them, pentabromobenzyl acrylate is preferred. As the copolymerizable component, benzyl methacrylate may be mentioned methacrylate corresponding to the above-mentioned acrylate. Further, the monomer may be copolymerized with a vinyl monomer, and examples thereof include acrylic esters such as acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate and benzyl acrylate, methacrylic esters such as methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate and benzyl methacrylate, unsaturated carboxylic acids such as styrene, acrylonitrile, fumaric acid and maleic acid, anhydrides thereof, vinyl acetate and vinyl chloride. In addition, crosslinkable vinyl monomers, dimethyl phenyl diacrylate, dimethyl phenyl dimethacrylate, dimethyl phenyl tetrabromodiacrylate, butadiene, isoprene, and divinylbenzene may also be used. These are used in an equimolar amount or less, preferably 0.5-fold molar amount or less, with respect to benzyl acrylate and benzyl methacrylate.
An example of the above-mentioned method for producing a brominated acrylic polymer is shown below: the reaction is carried out by solution polymerization or bulk polymerization of a monomer of brominated acrylic acid to a prescribed degree of polymerization. In the case of solution polymerization, halogenated aromatic compounds such as halogenated benzene and chlorobenzene are preferably used as the solvent.
The above-mentioned brominated acrylic polymer is preferably washed with water and/or an aqueous solution containing alkali (earth) metal ions in order to remove reaction by-products such as residual sodium polyacrylate. The aqueous solution containing an alkali (earth) metal ion can be easily obtained by charging an alkali (earth) metal salt into water, but is most suitable as a hydroxide of an alkali (earth) metal (for example, calcium hydroxide) containing no chloride ion, phosphate ion or the like. When calcium hydroxide is used as the alkali (earth) metal salt, the calcium hydroxide is usually soluble in about 0.126g of water at 20 ℃ and the concentration of the aqueous solution is not particularly limited as long as the concentration is a concentration up to the solubility. The method of washing with water and/or an aqueous solution containing an alkali (earth) metal ion is not particularly limited, and a method of immersing the brominated acrylic polymer in water and/or an aqueous solution containing an alkali (earth) metal ion for an appropriate time or the like may be used. The above-mentioned brominated acrylic polymer having been subjected to the cleaning treatment with water and/or an aqueous solution containing an alkali (earth) metal ion has a dry solid content of usually 100ppm or less in the hot water-extracted component, and when such a brominated acrylic polymer is used, foreign matters are hardly generated on the surface of the molded article.
In the flame-retardant polybutylene terephthalate resin composition of the present invention, the content of the halogenated aromatic compound other than the flame retardant is 0.5ppm or more and 5ppm or less, preferably 0.8ppm or more and 4ppm or less, and more preferably 1.0ppm or more and 3ppm or less. When the flame retardant polybutylene terephthalate resin composition of the present invention is used for a circuit breaker or the like, the halogenated aromatic compound other than the flame retardant is contained in the above range, whereby generation of an arc-extinguishing gas can be promoted, and contact defects due to an arc can be suppressed. As the gas that functions as an arc extinguishing gas, various gases such as the above-described gas derived from a halogenated aromatic compound and an inert gas are known, and a decomposition gas derived from a polybutylene terephthalate resin may be included therein. The content of the halogenated aromatic compound other than the flame retardant can be determined, for example, as follows: the amount of gas generated during the heat treatment in the headspace of a sample obtained by pulverizing the polybutylene terephthalate resin composition was measured by gas chromatography and determined based on the amount of gas generated from the halogenated aromatic compound.
In the flame retardancy of the resin, an antimony-based flame retardant aid is preferably used in combination. Typical examples of the flame retardant aid include antimony trioxide, antimony tetraoxide, antimony pentaoxide, sodium pyroantimonate, and the like. Further, in order to prevent delayed burning due to dripping of burning resin, it is also preferable to use an anti-dripping agent such as polytetrafluoroethylene in combination.
The addition ranges of the brominated acrylic polymer and the antimony-based flame retardant aid to the resin are preferably 3 to 30 parts by mass of the polymer and 1 to 20 parts by mass of the antimony-based flame retardant aid to 100 parts by mass of the polybutylene terephthalate resin. When the amount of the brominated acrylic polymer and the antimony-based flame retardant aid added is too small, sufficient flame retardancy cannot be imparted, and when it is too large, the physical properties of the molded article may be deteriorated.
(Filler)
Fillers may be used as required in the composition of the present invention. The compounding 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 may be in the form of fibers, powder, or plate, as required.
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 metal fibrous materials 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 carbon black, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, silicates such as wollastonite, oxides of metals such as iron, titanium and aluminum, carbonates of metals such as calcium carbonate and magnesium carbonate, sulfates of metals such as calcium sulfate and barium sulfate, silicon carbide, silicon nitride, boron nitride, and various metal powders.
Examples of the plate-like inorganic filler include mica, glass flakes, and various metal foils.
The type of the filler is not particularly limited, and 1 or more fillers may be added. Particularly, 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 based on 100 parts by mass of the polybutylene terephthalate resin. If the filler is added excessively, moldability is poor and toughness is lowered.
(additives)
In order to impart desired characteristics other than flame retardancy, a known substance usually added to a thermoplastic resin or the like may be further added to the composition of the present invention in combination according to the purpose. For example, any of 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 added. 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 the essential components and kneading them using a single-screw or twin-screw extruder or other melt kneading apparatus. A plurality of extruders or other melt-kneading apparatuses may be used. Further, all the components may be fed from the hopper at the same time, or a part of the components may be fed from the side feed port.
The flame-retardant polybutylene terephthalate resin composition of the present invention is preferably produced by vacuum drying (vacuuming). The vacuum drying may be performed by using an evaporator, an oven, or the like, which are generally used.
(examples)
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. The characteristic evaluation was performed by the following method.
(1) Halogenated aromatic content, arc suppressing gas generation
The materials dry-blended with the components and compositions (parts by mass) shown in table 1 were supplied to a twin-screw extruder (manufactured by japan steel-making corporation) having a screw of 30mm phi, melt-kneaded at 260 ℃, and pellets of the obtained polybutylene terephthalate resin composition were pulverized to obtain a sample, 5g of the sample was taken, left at 150 ℃ for 1 hour in a 20ml headspace, and then held at 50 ℃ for 1 minute using an apparatus, HP58 5890A manufactured by Yokogawa-Hewlett-Packard Company, column HR-1701(0.32mm diameter × 30m), and then heated at 5 ℃/minute, the amount of gas generation derived from the halogenated aromatic compound was measured by gas chromatography, the content of the halogenated aromatic compound was expressed in ppm, and the state of gas generation was evaluated, the case where generation of arc-extinguishing gas was confirmed was ○, and the case where generation of arc-extinguishing gas was not confirmed was evaluated was x, the results are shown in table 1.
(2) Corrosiveness of metal
Materials dry-blended with the components and compositions (parts by mass) shown in Table 1 were supplied to a mixer having
The pellets of the polybutylene terephthalate resin composition (50 g) obtained were placed in a 300ml glass stopper bottle together with a 1cm × 1cm silver plate and stoppered, and left to stand in a 120 ℃ gear box for 200 hours, and then the surface of the silver plate was visually observed to evaluate that no corrosion occurred as ◎, that almost no corrosion occurred as ○, that little corrosion occurred as △, and that remarkable corrosion occurred as x, and the results were shown in table 1.
(3) Flame retardancy
Materials dry-blended with the components and compositions (parts by mass) shown in table 1 were fed to a twin-screw extruder (manufactured by japan steel-making corporation) having a screw of 30mm phi, melt-kneaded at 260 ℃, and pellets of the obtained polybutylene terephthalate resin composition were dried at 140 ℃ for 3 hours, then injection-molded at a cylinder temperature of 250 ℃ and a mold temperature of 70 ℃, and test pieces of 1/32 inches in thickness were produced according to UL94 and evaluated for combustibility. The results are shown in Table 1.
[ Table 1]
The N.D. in the table is represented as a detection limit (0.1ppm) or less.
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 WinTech Polymer Ltd
Flame retardant 1: pentabromobenzyl polyacrylate (halogenated aromatic compound content except for flame retardant 150ppm) polymerized using chlorobenzene as solvent
Flame retardant 2: polypentacromobenzyl acrylate polymerized using chlorobenzene as a solvent (halogenated aromatic compound content except for flame retardant 250ppm)
Flame retardant 3: polypentacromobenzyl acrylate polymerized using ethylene glycol monomethyl ether as a solvent (halogenated aromatic compound content except for flame retardant: 8ppm)
Flame retardant 4: polypentacromobenzyl acrylate polymerized using chlorobenzene as solvent (halogenated aromatic compound content 1800ppm except flame retardant)
Flame retardant auxiliary agent: antimony trioxide
Anti-dripping agent: polytetrafluoroethylene
Antioxidant: tetrakis [ methylene-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] methane (product of BASF Japan Ltd. "Irganox 1010")
Releasing agent: low molecular weight polyethylene (SANWAX 161-P, product of Sanyo chemical industries Co., Ltd.)
Claims (9)
1. A flame-retardant polybutylene terephthalate resin composition characterized by containing:
polybutylene terephthalate resin, and
the halogenated benzyl acrylate is a flame retardant,
the content of the halogenated aromatic compound other than the flame retardant is 0.5ppm to 5ppm, as measured by headspace gas chromatography at 150 ℃ for 1 hour under heating.
2. The flame-retardant polybutylene terephthalate resin composition according to claim 1, wherein the halogenated benzyl acrylate-based flame retardant is a brominated acrylic polymer represented by the general formula (I),
wherein X is a hydrogen atom or a bromine atom, at least 1 or more of X are bromine, and m is a number of 10 to 2000.
3. The flame retardant polybutylene terephthalate resin composition according to claim 1 or 2, wherein the halogenated benzyl acrylate-based flame retardant is pentabromobenzyl polyacrylate.
4. The flame retardant polybutylene terephthalate resin composition according to any one of claims 1 to 3, wherein the halogenated aromatic compound other than the flame retardant is halogenated benzene.
5. The flame retardant polybutylene terephthalate resin composition according to any one of claims 1 to 4, wherein the halogenated aromatic compound other than the flame retardant is chlorobenzene.
6. A process for producing a flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 5, wherein a halogenated aromatic compound is used as a solvent in the production of the halogenated benzyl acrylate-based flame retardant.
7. The method for producing a flame-retardant polybutylene terephthalate resin composition according to claim 6, wherein the halogenated aromatic compound is halogenated benzene.
8. The method for producing a flame-retardant polybutylene terephthalate resin composition according to claim 6 or 7, wherein the halogenated aromatic compound is chlorobenzene.
9. The method for producing a flame-retardant polybutylene terephthalate resin composition according to any one of claims 6 to 8, wherein vacuum drying is performed.
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| JP2017-159370 | 2017-08-22 | ||
| JP2017159370A JP7079578B2 (en) | 2017-08-22 | 2017-08-22 | Flame-retardant polybutylene terephthalate resin composition |
| PCT/JP2018/030796 WO2019039464A1 (en) | 2017-08-22 | 2018-08-21 | Flame-retardant polybutylene terephthalate resin composition |
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| JP2013057009A (en) * | 2011-09-08 | 2013-03-28 | Mitsubishi Engineering Plastics Corp | Polyester resin composition, and molded body |
| CN103608367A (en) * | 2011-04-14 | 2014-02-26 | 溴化合物有限公司 | Process for the preparation of the monomer pentabromobenzyl acrylate and polymerization thereof |
| WO2017043334A1 (en) * | 2015-09-11 | 2017-03-16 | 三菱エンジニアリングプラスチックス株式会社 | Polyester-based resin composition and production method for same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB2096830B (en) * | 1981-04-13 | 1984-09-26 | Electricity Council The Isc Ch | Electrical circuit interrupter |
| KR100528152B1 (en) * | 2001-11-20 | 2005-11-15 | 미쓰비시덴키 가부시키가이샤 | Circuit breaker |
| EP2578633A4 (en) * | 2010-05-27 | 2014-06-04 | Wintech Polymer Ltd | Polybutylene terephthalate resin composition |
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| EP2942367B1 (en) * | 2014-05-05 | 2018-07-11 | LANXESS Deutschland GmbH | Polyester compounds |
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| CN103608367A (en) * | 2011-04-14 | 2014-02-26 | 溴化合物有限公司 | Process for the preparation of the monomer pentabromobenzyl acrylate and polymerization thereof |
| JP2013057009A (en) * | 2011-09-08 | 2013-03-28 | Mitsubishi Engineering Plastics Corp | Polyester resin composition, and molded body |
| WO2017043334A1 (en) * | 2015-09-11 | 2017-03-16 | 三菱エンジニアリングプラスチックス株式会社 | Polyester-based resin composition and production method for same |
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| TWI780210B (en) | 2022-10-11 |
| JP7079578B2 (en) | 2022-06-02 |
| TW201920410A (en) | 2019-06-01 |
| JP2019038865A (en) | 2019-03-14 |
| CN111051431B (en) | 2023-03-31 |
| WO2019039464A1 (en) | 2019-02-28 |
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