CN112771115A - Flame-retardant polybutylene terephthalate resin composition - Google Patents
Flame-retardant polybutylene terephthalate resin composition Download PDFInfo
- Publication number
- CN112771115A CN112771115A CN201980063532.0A CN201980063532A CN112771115A CN 112771115 A CN112771115 A CN 112771115A CN 201980063532 A CN201980063532 A CN 201980063532A CN 112771115 A CN112771115 A CN 112771115A
- Authority
- CN
- China
- Prior art keywords
- polybutylene terephthalate
- terephthalate resin
- flame
- resin composition
- retardant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
- C08K3/34—Silicon-containing compounds
-
- 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
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention aims to provide a polybutylene terephthalate resin composition which contains a basic metal inorganic compound and has excellent flame retardancy. The above object is achieved by using a flame-retardant polybutylene terephthalate resin composition characterized by comprising a polybutylene terephthalate resin having a terminal carboxyl group amount of 50meq/kg or less, a basic metal inorganic compound, a brominated epoxy flame retardant and antimony trioxide, wherein the total content of epoxy groups in the entire composition is 0.010mol/kg or more and 0.020mol/kg or less.
Description
Technical Field
The present invention relates to a flame-retardant polybutylene terephthalate resin composition, a black foreign matter inhibitor, a method for inhibiting black foreign matter, 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) of 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 invention aims to provide a polybutylene terephthalate resin composition which contains a basic metal inorganic compound and has excellent flame retardancy.
Means for solving the problems
The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that: the above object can be achieved by using a flame-retardant polybutylene terephthalate resin composition characterized by containing a polybutylene terephthalate resin having a terminal carboxyl group amount of 50meq/kg or less, a basic metal inorganic compound and antimony trioxide, and having a total epoxy group content of 0.010mol/kg or more and 0.020mol/kg or less in the entire composition, 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 comprising: a polybutylene terephthalate resin having a terminal carboxyl group content of 50meq/kg or less, a basic metal inorganic compound, a brominated epoxy flame retardant, and antimony trioxide, wherein the total content of epoxy groups in the entire composition is 0.010mol/kg or more and 0.020mol/kg or less.
(2) The flame-retardant polybutylene terephthalate resin composition according to the item (1), wherein the basic metal inorganic compound is hydrotalcite and/or talc.
(3) The flame-retardant polybutylene terephthalate resin composition according to the item (1) or (2), wherein the content of the basic metal inorganic compound is 0.01 to 25 parts by mass relative to 100 parts by mass of the polybutylene terephthalate resin.
(4) The flame-retardant polybutylene terephthalate resin composition according to item (3), wherein the basic metal inorganic compound is a hydrotalcite that is contained in an amount of 0.01 to less than 5.0 parts by mass per 100 parts by mass of the polybutylene terephthalate resin.
(5) The flame-retardant polybutylene terephthalate resin composition according to item (3), wherein the basic metal inorganic compound contains 5.0 to 25 parts by mass of talc per 100 parts by mass of the polybutylene terephthalate resin.
(6) A black foreign matter inhibitor comprising the flame-retardant polybutylene terephthalate resin composition according to any one of (1) to (5).
(7) A method for suppressing black foreign matter, which comprises using the flame-retardant polybutylene terephthalate resin composition according to any one of (1) to (5).
(8) The process for producing a flame-retardant polybutylene terephthalate resin composition according to any one of (1) to (5).
(9) A molded article obtained from the flame-retardant polybutylene terephthalate resin composition of any one of (1) to (5).
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a polybutylene terephthalate resin composition containing a basic metal inorganic compound 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 more than 50meq/kg, but is not particularly limited as long as the object of the present invention is not impaired, and is preferably not more than 30meq/kg, and more preferably not more than 25 meq/kg.
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 obtained polybutylene terephthalate resin composition is particularly excellent in moldability. 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 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 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 preferable8-12The aromatic dicarboxylic acid of (a); and C such as adipic acid, azelaic acid and sebacic acid6-12An 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 2mol adduct and bisphenol A propylene oxide 3 mol 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.
The epoxy compound used in the brominated 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.
(basic metal inorganic Compound)
The basic metal inorganic compound contained in the flame-retardant polybutylene terephthalate resin composition of the present invention is preferably a layered silicate. The layered silicate is preferably talc, hydrotalcite, or the like. Further, as the basic metal inorganic compound contained in the flame-retardant polybutylene terephthalate resin composition of the present invention, a metal oxide is also preferable. The metal oxide is preferably magnesium oxide or zinc oxide.
In the polybutylene terephthalate resin composition of the present invention, the content of the basic metal inorganic compound is preferably 0.01 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the polybutylene terephthalate resin. When hydrotalcite is used as the basic metal inorganic compound, the content thereof is preferably 0.01 parts by mass or more and less than 5.0 parts by mass per 100 parts by mass of the polybutylene terephthalate resin. Further, when talc is used as the basic metal inorganic compound, the content thereof is preferably 5.0 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the polybutylene terephthalate resin.
(epoxy compound)
The epoxy compound used in the polybutylene terephthalate resin composition 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. In addition, as the epoxy compound, 2 or more compounds may be used in combination as desired.
The flame-retardant polybutylene terephthalate resin composition of the present invention has a total content of epoxy groups in the entire composition of 0.010mol/kg or more and 0.020mol/kg or less, preferably 0.012mol/kg or more and 0.018mol/kg or less, and more preferably 0.014mol/kg or more and 0.016mol/kg or less.
When the total epoxy content 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 adhering to the screw of an extruder or a molding machine during molding can be suppressed. In addition, the molded article obtained from the flame-retardant polybutylene terephthalate resin composition of the present invention can be made to have good hydrolysis resistance.
(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, and is preferably selected from the group consisting of antimony trioxide, antimony pentoxide, and sodium antimonate.
(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)
In the flame retardant polybutylene terephthalate resin composition of the present invention, a filler may be used as needed. 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.
[ Black foreign matter inhibitor and method for inhibiting Black foreign matter ]
The flame retardant polybutylene terephthalate resin composition of the present invention can be suitably used as a black foreign matter inhibitor. Further, the flame retardant polybutylene terephthalate resin composition of the present invention can be suitably used for a black foreign matter suppression method.
[ 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). The vacuum drying may be performed using an evaporator, an oven, or the like, which are generally used.
[ 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 in-vehicle component cases such as an ECU housing and a connector housing and in-vehicle electric components.
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 was confirmed by bringing the flame of a gas burner into contact with the lower end of a vertically held sample for 10 seconds, and if combustion was stopped within 30 seconds, the flame was brought into contact for 10 seconds, and the following criteria were satisfied.
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 to 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) Retained MI
The melt flow rate (g/10min) of pellets of the polybutylene terephthalate resin composition obtained in the same manner as in the evaluation of flame retardancy was measured according to ISO1133-1 or ISO1133-2 under conditions of 260 ℃, a load of 2.16kg, a residence time of 7 minutes, 15 minutes, 30 minutes, and 45 minutes. 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, and then melt-kneaded in the following procedure, and the amount of black deposits was visually observed, and the pellets were marked as "x", the pellets were marked as "Δ" when the deposits were remarkably generated, the pellets were marked as "o" when the deposits were small, and the pellets were marked as "excellent" when the deposits were hardly observed. 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 20rpm, 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) 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 at a cylinder temperature of 260 ℃ and a mold temperature of 80 ℃ to obtain a test piece for tensile property evaluation of ISO3167, and a tensile strength test was performed in accordance with ISO527-1, 2. Subsequently, a tensile strength test was similarly carried out using a test piece obtained by subjecting the test piece to a wet heat treatment at 121 ℃ and 2atm (saturated water vapor pressure) for 150 hours, and the hydrolysis resistance was evaluated by obtaining a tensile strength retention of 50% or more as "excellent", a tensile strength retention of less than 50% and more than 45% as "good", a tensile strength retention of less than 45% and more than 40% as "Δ", and a tensile strength retention of less than 40% as "x", respectively, with respect to the tensile strength retention before the wet heat treatment. 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 terminal carboxyl group concentration of 18meq/kg and an intrinsic viscosity of 0.88dL/g, manufactured by WinTech Polymer Co
AS resin: ningbo LG Yongxing Chemical Co., Ltd., AS RESIN 80HF, manufactured by Ltd
Glass fiber: ECS03T-127 (diameter: 13 μm, length: 3mm), manufactured by Nippon electric Nitro Kogyo Co., Ltd
Brominated epoxy flame retardant 1: brominated epoxy compound having an epoxy equivalent of 36800g/eq and a weight average molecular weight of about 18000
Brominated epoxy flame retardant 2: brominated epoxy compound having an epoxy equivalent of 19900g/eq and a weight average molecular weight of about 23000
Antimony trioxide: PATOX-M, manufactured by Japan concentrate Co
PTFE (anti-drip agent): polytetrafluoroethylene
Bis-A type epoxy resin: JeR 1004K (epoxy equivalent: 925g/eq), product of Mitsubishi chemical corporation
Releasing agent: pentaerythritol Tetrastearate (manufactured by Nichiba, "UNISTAR H476")
Carbon black: mitsubishi chemical corporation, MA600B
Antioxidant: tetrakis [ methylene-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] methane (product of BASFJAPAN, "Irganox 1010")
Basic compound 1: hydrotalcite (made by synergetics chemical industry, "DHT-4A-2")
Basic compound 2: talc (Talcum POWDER PKNN, manufactured by Linification Ltd.)
Basic compound 3: potassium acetate (60, K.acetate, manufactured by Dadong chemical Co., Ltd.)
Basic compound 4: magnesium oxide (manufactured by Kyowa chemical industries, Ltd., "KYOWAMAG MF 150")
Basic compound 5: zinc oxide (manufactured by Sanjing Metal mining Co., Ltd.)
Basic compound 6: carbodiimide Compound (manufactured by RASCHIG, "Stabilizer 9000")
The carbodiimide compound is not a basic metal inorganic compound, and is referred to as a basic compound 6 for convenience.
As shown in Table 1, the molded articles obtained from the flame retardant polybutylene terephthalate resin compositions of examples 1 to 13 satisfying the constitution of claim 1 of the present application were all excellent in appearance, and no significant occurrence of deposits adhering to the screw was observed at the time of molding. Furthermore, no correlation between changes in retained MI and screw deposit was observed.
On the other hand, the molded articles obtained from the polybutylene terephthalate resin compositions of comparative examples 1 to 5, which are outside the scope of claim 1 of the present application, are poor in appearance and have deposits adhering to the screw during molding. Further, the molded article obtained from the polybutylene terephthalate resin composition of comparative example 5 was poor in hydrolysis resistance.
Further, according to examples 1 to 3 and 7, when hydrotalcite is added as the alkali compound, the amount added is 1.0 part by mass or more per 100 parts by mass of the polybutylene terephthalate resin, which is advantageous in suppressing the deposit adhering to the screw, and is 2.5 parts by mass or less, which is advantageous in hydrolysis resistance.
Further, according to examples 4 to 6, when talc is added as the alkali compound in an amount of 10.0 parts by mass or more and 15.0 parts by mass or less based on 100 parts by mass of the polybutylene terephthalate resin, the adhesion to the screw is suppressed and the hydrolysis resistance is improved with a good balance.
Claims (9)
1. A flame-retardant polybutylene terephthalate resin composition, characterized by comprising:
a polybutylene terephthalate resin having a terminal carboxyl group amount of 50meq/kg or less;
basic metal inorganic compounds;
brominated epoxy flame retardants; and
antimony trioxide, namely antimony trioxide, which is a mixture of antimony trioxide,
the total content of epoxy groups in the entire composition is 0.010mol/kg or more and 0.020mol/kg or less.
2. The flame retardant polybutylene terephthalate resin composition according to claim 1, wherein the basic metal inorganic compound is hydrotalcite and/or talc.
3. The flame-retardant polybutylene terephthalate resin composition according to claim 1 or 2, wherein the content of the basic metal inorganic compound is 0.01 to 25 parts by mass relative to 100 parts by mass of the polybutylene terephthalate resin.
4. The flame-retardant polybutylene terephthalate resin composition according to claim 3, wherein the basic metal inorganic compound is one containing hydrotalcite in an amount of 0.01 to less than 5.0 parts by mass per 100 parts by mass of the polybutylene terephthalate resin.
5. The flame-retardant polybutylene terephthalate resin composition according to claim 3, wherein the basic metal inorganic compound contains 5.0 parts by mass or more and 25 parts by mass or less of talc per 100 parts by mass of the polybutylene terephthalate resin.
6. A black foreign matter inhibitor comprising the flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 5.
7. A method for suppressing black foreign matter, which comprises using the flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 5.
8. The method for producing a flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 5.
9. A molded article obtained from the flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 5.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018-183368 | 2018-09-28 | ||
| JP2018183368 | 2018-09-28 | ||
| PCT/JP2019/038468 WO2020067564A1 (en) | 2018-09-28 | 2019-09-30 | Flame retardant polybutylene terephthalate resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112771115A true CN112771115A (en) | 2021-05-07 |
| CN112771115B CN112771115B (en) | 2023-03-24 |
Family
ID=69951324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201980063532.0A Active CN112771115B (en) | 2018-09-28 | 2019-09-30 | Flame-retardant polybutylene terephthalate resin composition |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6726378B1 (en) |
| CN (1) | CN112771115B (en) |
| TW (1) | TWI814911B (en) |
| WO (1) | WO2020067564A1 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (9)
| 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 |
| JP2002128998A (en) * | 2000-10-30 | 2002-05-09 | Teijin Ltd | Flame-retardant polyester resin composition |
| JP2002285002A (en) * | 2001-03-23 | 2002-10-03 | Sankyo Organic Chem Co Ltd | Flame-retarded thermoplastic resin composition |
| JP2007100237A (en) * | 2005-10-03 | 2007-04-19 | Kaneka Corp | Flame-retardant polyester-based artificial hair |
| JP2008115209A (en) * | 2006-10-31 | 2008-05-22 | Toray Ind Inc | Thermoplastic resin composition |
| CN101275010B (en) * | 2007-03-26 | 2012-08-08 | 上海金发科技发展有限公司 | Flame-proof reinforced Valox compound and preparation thereof |
| JP6177252B2 (en) * | 2012-10-29 | 2017-08-09 | ウィンテックポリマー株式会社 | Polybutylene terephthalate resin composition |
| WO2017010337A1 (en) * | 2015-07-16 | 2017-01-19 | ウィンテックポリマー株式会社 | Polybutylene terephthalate resin composition |
-
2019
- 2019-09-30 CN CN201980063532.0A patent/CN112771115B/en active Active
- 2019-09-30 WO PCT/JP2019/038468 patent/WO2020067564A1/en active Application Filing
- 2019-09-30 JP JP2020502489A patent/JP6726378B1/en active Active
- 2019-10-01 TW TW108135469A patent/TWI814911B/en active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2020067564A1 (en) | 2021-02-15 |
| CN112771115B (en) | 2023-03-24 |
| WO2020067564A1 (en) | 2020-04-02 |
| TWI814911B (en) | 2023-09-11 |
| TW202014469A (en) | 2020-04-16 |
| JP6726378B1 (en) | 2020-07-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1697451B1 (en) | Flame-retardant polyester composition | |
| WO2007037450A9 (en) | Flame-retardant polybutylene terephthalate resin composition | |
| US7375167B2 (en) | Hydrolysis-resistance composition | |
| CN109689782B (en) | Polybutylene terephthalate resin composition and molded article | |
| EP3647367B1 (en) | Thermoplastic polyester resin composition and molded article thereof | |
| JP4334221B2 (en) | Flame retardant reinforced polyamide resin composition | |
| CN110997805A (en) | Flame-retardant polybutylene terephthalate resin composition | |
| CN110418819B (en) | Thermoplastic polyester resin composition and molded article | |
| CN112236478B (en) | Flame-retardant polybutylene terephthalate resin composition | |
| KR101632571B1 (en) | Halogen-free flame retardant polyester resin composition with good mechanical properties and molded article thereof | |
| CN112771115B (en) | Flame-retardant polybutylene terephthalate resin composition | |
| JP7454342B2 (en) | Flame-retardant polybutylene terephthalate resin composition for electrical insulation parts | |
| WO2012174575A2 (en) | Process for preparing amine-modified polyester resins with improved melt flow | |
| WO2011132655A1 (en) | Polybutylene terephthalate resin composition and method for producing polybutylene terephthalate resin composition | |
| US20160280885A1 (en) | Resin composition and resin molded article | |
| JP2020007390A (en) | Flame-retardant polybutylene terephthalate resin composition for electric insulation components | |
| CN112041397B (en) | Resin composition for antistatic member | |
| JP7182396B2 (en) | Flame-retardant polybutylene terephthalate resin composition | |
| JP3761598B2 (en) | Polybutylene terephthalate resin molded product | |
| JP7368977B2 (en) | Flame retardant polybutylene terephthalate resin composition | |
| CN114174426B (en) | Flame retardant polybutylene terephthalate resin composition | |
| JP2019156891A (en) | Thermoplastic polyester resin composition and molding thereof | |
| CN111051431B (en) | Flame-retardant polybutylene terephthalate resin composition | |
| CN114793439A (en) | Polybutylene terephthalate resin composition, molded article, viscosity increase inhibitor for polybutylene terephthalate resin composition, and hydrolysis inhibitor for molded article formed from polybutylene terephthalate resin composition | |
| JP2020203963A (en) | Method for producing flame-retardant thermoplastic polyester resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |