WO2014069489A1 - Polybutylene terephthalate resin composition - Google Patents
Polybutylene terephthalate resin composition Download PDFInfo
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- WO2014069489A1 WO2014069489A1 PCT/JP2013/079325 JP2013079325W WO2014069489A1 WO 2014069489 A1 WO2014069489 A1 WO 2014069489A1 JP 2013079325 W JP2013079325 W JP 2013079325W WO 2014069489 A1 WO2014069489 A1 WO 2014069489A1
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- resin composition
- polybutylene terephthalate
- flame retardant
- terephthalate resin
- antimony
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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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- 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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/016—Flame-proofing or flame-retarding additives
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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
- C08K3/34—Silicon-containing compounds
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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
Definitions
- the present invention relates to a polybutylene terephthalate resin composition.
- Polybutylene terephthalate resin is widely used as a material for various molded products such as automobile parts and electric / electronic parts because it has excellent mechanical and electrical properties.
- the above molded body is generally required to have high flame retardancy. Therefore, in order to obtain a molded product having high flame retardancy, studies have been made to improve the flame retardancy of a composition containing a polybutylene terephthalate resin.
- the polybutylene terephthalate resin composition with improved flame retardancy include, for example, compositions described in Patent Documents 1 to 6.
- the present invention has been made to solve the above-described problems, and an object of the present invention is to provide a polybutylene terephthalate resin composition for obtaining a molded product having high flame retardancy and excellent mechanical properties.
- the present inventors have found that a polybutylene terephthalate resin composition containing polybutylene terephthalate, a predetermined amount of talc, a brominated flame retardant, and an antimony flame retardant aid can solve the above problems, and The invention has been completed. More specifically, the present invention provides the following.
- a polybutylene terephthalate resin composition includes polybutylene terephthalate, talc as a flame retardant, a brominated flame retardant, and an antimony flame retardant aid,
- the polybutylene terephthalate resin composition in which the content of talc as the flame retardant in the polybutylene terephthalate resin composition is more than 1% by mass to less than 5% by mass with respect to the total amount of the polybutylene terephthalate resin composition. object.
- the content of talc as the flame retardant in the polybutylene terephthalate resin composition is 5 with respect to the total amount of talc as the flame retardant, the brominated flame retardant and the antimony flame retardant auxiliary.
- the polybutylene terephthalate resin composition according to (1) which is ⁇ 30% by mass.
- the total amount of bromine atoms in the bromine-based flame retardant and antimony atoms in the antimony-based flame retardant aid in the polybutylene terephthalate resin composition is the organic content in the polybutylene terephthalate resin composition.
- the ratio (bromine atom / antimony atom) of the mass of bromine atoms in the brominated flame retardant and the mass of antimony atoms in the antimony flame retardant aid in the polybutylene terephthalate resin composition is The polybutylene terephthalate resin composition according to any one of (1) to (3), which is 1/2 to 4/1.
- a polybutylene terephthalate resin composition for obtaining a molded product having high flame retardancy and excellent mechanical properties.
- the polybutylene terephthalate resin composition of the present invention (hereinafter also referred to as the “resin composition of the present invention”) comprises polybutylene terephthalate, a predetermined amount of talc, a brominated flame retardant, and an antimony flame retardant. Including auxiliaries.
- each component in the polybutylene terephthalate resin composition of the present invention will be described.
- Polybutylene terephthalate is a dicarboxylic acid component containing at least terephthalic acid or an ester-forming derivative thereof (C 1 -C 6 alkyl ester, acid halide, etc.) and an alkylene glycol (1,4-carbon atom) having at least 4 carbon atoms. Butanediol) or a glycol component containing an ester-forming derivative thereof.
- the polybutylene terephthalate in the present invention may be a homopolybutylene terephthalate or a copolymer containing 60 mol% or more (particularly 75 mol% or more and 95 mol% or less) of a butylene terephthalate unit.
- dicarboxylic acid components (comonomer components) other than terephthalic acid and its ester-forming derivatives include, for example, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-dicarboxydiphenyl ether, etc.
- C 8 -C 14 aromatic dicarboxylic acids C 4 -C 16 alkyl dicarboxylic acids such as succinic acid, adipic acid, azelaic acid and sebacic acid; C 5 -C 10 cycloalkyl dicarboxylic acids such as cyclohexane dicarboxylic acid And ester-forming derivatives of these dicarboxylic acid components (C 1 -C 6 alkyl ester derivatives, acid halides, etc.).
- These dicarboxylic acid components can be used alone or in combination of two or more.
- glycol components (comonomer components) other than 1,4-butanediol include, for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene glycol, hexamethylene glycol, neopentyl glycol, 1 , alkylene glycol C 2 ⁇ C 10 and 3-octanediol; diethylene glycol, triethylene glycol, polyoxyalkylene glycol and dipropylene glycol; cyclohexanedimethanol, alicyclic diols such as hydrogenated bisphenol a; bisphenol a, Aromatic diols such as 4,4'-dihydroxybiphenyl; ethylene oxide 2 mol adduct of bisphenol A, propylene oxide 3 mol adduct of bisphenol A The alkylene oxide adduct of C 2 ⁇ C 4 of bisphenol A; or ester-forming derivatives of these glycols (acetylated
- polybutylene terephthalate copolymers obtained by copolymerizing the comonomer components described above can be suitably used as polybutylene terephthalate.
- polybutylene terephthalate a homopolybutylene terephthalate polymer and a polybutylene terephthalate copolymer may be used in combination.
- the amount of terminal carboxyl groups of polybutylene terephthalate is not particularly limited as long as the object of the present invention is not impaired, but is preferably 30 meq / kg or less, more preferably 25 meq or less.
- Use of polybutylene terephthalate having a terminal carboxyl group content in such a range is preferable in that the mechanical properties of the molded product obtained from the polybutylene terephthalate resin composition are particularly excellent.
- the melt flow rate of polybutylene terephthalate is not particularly limited as long as the object of the present invention is not impaired, but is preferably 5 g / 10 min or more and 100 g / 10 min or less. More preferably, they are 10 g / 10min or more and 80 g / 10min or less. Use of polybutylene terephthalate having a melt flow rate in such a range is preferable in that the moldability of the resulting polybutylene terephthalate resin composition is particularly excellent.
- the melt flow rate of polybutylene terephthalate is measured in accordance with ISO 1133, for example, under conditions of a temperature of 235 ° C. and a load of 2160 g.
- the content of polybutylene terephthalate in the resin composition of the present invention is not particularly limited, and can be appropriately determined by adjusting the content of talc and the like described later, for example, with respect to the total amount of the polybutylene terephthalate resin composition, It may be 30 to 80% by mass, preferably 45 to 65% by mass.
- the resin composition of the present invention contains talc as a flame retardant.
- Talc is a kind of silicate mineral and includes magnesium hydroxide and silicate.
- talc has been added to a polybutylene terephthalate resin composition as a reinforcing agent, a nucleating agent, an electrical property improver, a high thermal conductive agent, and the like.
- talc acts as an excellent flame retardant in the polybutylene terephthalate resin composition containing talc together with the brominated flame retardant and antimony flame retardant auxiliary described later.
- the flame retardant is imparted to a molded product obtained from the resin composition, but mechanical properties may not be sufficient.
- the resin composition of the present invention containing talc a molded article having high flame retardancy can be obtained without sacrificing mechanical properties.
- the reason why the molded product obtained from the resin composition of the present invention has high flame retardance is assumed to be due to the following reason. That is, when talc is contained in the resin composition constituting the molded body, a foamed carbonized layer is formed on the surface of the molded body when the molded body burns, and this carbonized layer functions as a heat insulating layer. It is presumed that it will be a non-flammable form. It is known that the intomescent flame retardant form is excellent in flame retardancy, and the molded product obtained from the resin composition of the present invention is likely to have this form at the time of combustion.
- the polybutylene terephthalate resin composition of the present invention contains talc in an amount of more than 1% by mass to less than 5% by mass with respect to the total amount of the polybutylene terephthalate resin composition.
- talc content is 1% by mass or less based on the total amount of the resin composition, not only the maximum heat generation rate of the resin composition is increased, but also in the UL-94 standard vertical combustion test of Underwriters Laboratories. Since the absorbent cotton is easily ignited by dripping, the flame retardancy of the molded product obtained from the resin composition is not sufficient.
- the content of talc is 5% by mass or more with respect to the total amount of the resin composition, the mechanical properties of the molded product obtained from the resin composition may be deteriorated.
- the maximum heat generation rate of the resin composition is particularly small, it is preferable in that the flame retardancy of the resulting molded product is particularly high.
- polybutylene terephthalate resin composition of the present invention 5 to 30% by mass, preferably based on the total amount of talc, bromine-based flame retardant (described later) and antimony-based flame retardant auxiliary (described later) Preferably contains 10 to 20% by mass of talc.
- the resin composition of the present invention contains a brominated flame retardant as a flame retardant.
- the brominated flame retardant used in the present invention is not particularly limited as long as it is a bromine-containing organic compound and can flame retardant polymer materials such as polybutylene terephthalate, and is commercially available for polymer materials. Various flame retardants can be used.
- the bromine content in the brominated flame retardant is preferably 20% by mass or more. If the bromine content is low, it is necessary to use a large amount of flame retardant in order to obtain the desired flame retardancy, and the mechanical properties of the molded product obtained from the resin composition of the present invention may be impaired. Therefore, it is not preferable.
- the type of flame retardant is not particularly limited.
- halogen-containing flame retardant, phosphorus-containing flame retardant, nitrogen-containing flame retardant, sulfur-containing flame retardant, silicon-containing flame retardant, alcohol flame retardant, inorganic flame retardant, aromatic resin examples include flame retardants.
- a halogen-containing flame retardant is preferable, and a bromine-containing flame retardant is more preferable.
- Brominated flame retardants include brominated acrylic resins, brominated styrene resins, brominated polycarbonate resins, brominated epoxy resins, brominated polyaryl ether compounds, brominated aromatic imide compounds, brominated bisaryl compounds, Examples thereof include brominated tri (aryloxy) triazine compounds.
- a bromine-containing epoxy resin is preferable because the rigidity, impact resistance, fluidity, heat resistance, and weather resistance can be improved in a balanced manner.
- the bromine-containing epoxy resin a resin whose end is sealed may be used. It is preferable to use a bromine-containing epoxy resin whose ends are sealed because the fluidity of the resin composition at the time of molding becomes high.
- bisphenol A type epoxy resins are particularly preferred.
- bromophenol is preferably used for end-capping the bromine-containing epoxy resin, but tribromophenol is particularly preferably used among bromophenols.
- the polybutylene terephthalate resin composition may contain a plurality of types of flame retardants.
- the content of the brominated flame retardant in the resin composition of the present invention is preferably 5 to 50% by mass and more preferably 5 to 20% by mass with respect to the total amount of the polybutylene terephthalate resin composition.
- the resin composition of the present invention contains an antimony flame retardant aid as a flame retardant aid.
- the antimony flame retardant aid used in the present invention is not particularly limited as long as it contains antimony and provides a good flame retardant effect, so long as the object of the present invention is not impaired.
- Specific examples of the antimony flame retardant aid preferably used in the present invention include antimony trioxide, antimony tetraoxide, antimony pentoxide, sodium antimonate, antimony halide and the like. These antimony flame retardant aids can be used in combination of two or more.
- An antimony flame retardant aid may be used in combination with a flame retardant aid such as aluminum hydroxide, magnesium hydroxide, or zinc sulfide.
- the form of the antimony-based flame retardant aid is not particularly limited, but is preferably in the form of particles, and more preferably in the form of particles having an average particle size of 0.1 to 10 ⁇ m.
- the content of the antimony flame retardant aid in the resin composition of the present invention can be appropriately determined in relation to the content of the bromine flame retardant.
- the total amount of bromine atoms in the bromine-based flame retardant and antimony atoms in the antimony-based flame retardant aid is the total amount of organic components in the polybutylene terephthalate resin composition. It may be 1 to 5 mol / kg.
- the ratio (bromine atom / antimony atom) between the mass of bromine atoms in the brominated flame retardant and the mass of antimony atoms in the antimony flame retardant auxiliary is 1/2. It may be up to 4/1.
- compositions other than the above components may be blended in the polybutylene terephthalate resin composition of the present invention.
- Specific examples include fillers (glass fibers and the like), anti-dripping agents (polytetrafluoroethylene and the like), antioxidants, antistatic agents, mold release agents, colorants and the like.
- the other content in the resin composition of the present invention may be 0 to 50% by mass, preferably 10 to 40% by mass, based on the total amount of the polybutylene terephthalate resin composition. .
- the specific embodiment of the method for preparing the polybutylene terephthalate resin composition of the present invention is not particularly limited.
- the polybutylene terephthalate resin composition is prepared by a well-known facility and method as a method for preparing the resin composition or a molded product thereof. Can be prepared.
- necessary components can be mixed and kneaded using a single or twin screw extruder or other melt kneader to prepare pellets for molding.
- a plurality of extruders or other melt kneaders may be used.
- the kneading temperature (cylinder temperature) of the resin composition is preferably 250 ° C.
- the kneading temperature is higher than 280 ° C., the decomposition of the resin tends to proceed during the kneading, and when it is lower than 250 ° C., the dispersion state of each component in the obtained polybutylene terephthalate resin composition may not be excellent.
- the melt viscosity of the polybutylene terephthalate resin composition of the present invention is moderately high.
- the melt viscosity is a value indicating the fluidity of the resin composition.
- the melt viscosity of the resin composition is low, the resin is easily decomposed and there is a possibility that the mechanical properties obtained from the resin composition are lowered.
- the resin composition of the present invention since the decrease in melt viscosity is suppressed, good mechanical properties are imparted to the molded product obtained from the resin composition.
- the melt viscosity of the resin composition is measured according to ISO11443.
- a conventionally known molding method for example, a method such as injection molding, extrusion molding, compression molding, blow molding, vacuum molding, foam molding, rotational molding, gas injection molding, etc.
- Various molded bodies can be molded.
- the molded body obtained by the above method is excellent in flame retardancy. Specifically, the molded body satisfies the V-0 standard in the UL-94 standard vertical combustion test of Underwriters Laboratories. Moreover, the molded object obtained by the above methods is excellent in mechanical characteristics.
- the mechanical properties of the molded product can be determined by evaluating tensile properties (tensile strength and tensile elongation) in accordance with ISO527-1,2.
- the molded product obtained by molding the resin composition of the present invention has the above properties, it can be preferably used as an electric / electronic component, OA device component, home appliance component, automobile component, mechanical mechanism component, or the like.
- PATOX-M Glass fiber: Nitto Boseki Co., Ltd., “average fiber diameter ⁇ 13 ⁇ m chopped strand”
- Anti-drip agent “Fullon CD-076” manufactured by Asahi Glass Co., Ltd.
- “Br + Sb” represents the mass of bromine atoms in the brominated flame retardant and antimony atoms in the antimony based flame retardant aid relative to the total amount of organic components in the polybutylene terephthalate resin composition.
- the ratio (unit: mol / kg) is shown.
- “Br / Sb” indicates the ratio (bromine atom / antimony atom) of bromine atoms in the brominated flame retardant and antimony atoms in the antimony flame retardant auxiliary in the polybutylene terephthalate resin composition.
- “B / (B + C + D)” indicates a ratio (unit:%) between the total amount of the components indicated in the B column in Tables 1 and 2 and the total amount of the components indicated in the B to D columns.
- test piece (0.75 mm thickness) produced by injection molding each resin composition at a molding temperature of 250 ° C. and a mold temperature of 80 ° C. conforms to the UL-94 standard vertical combustion test of Underwriters Laboratories. The flammability was evaluated. The evaluation was performed on five test pieces manufactured from each resin composition. The number of test pieces that dripped during combustion and the test piece in which the absorbent cotton under the test piece was ignited by dripping. Each was counted. The results are shown in the “Dripping” section of Table 2. In the “dripping” section of Table 2, the numbers outside the parentheses are the number of test pieces that dripped during combustion, and the numbers in parentheses ignite the absorbent cotton under the test pieces by dripping. This is the number of test specimens.
- the resin composition of the present invention has a high melt viscosity value, it can be seen that the resin in the resin composition is suppressed from being decomposed and a molded article having excellent physical properties can be obtained. Moreover, it turns out that the molded object obtained from the resin composition of this invention is not only high in a flame retardance but excellent in a tensile characteristic. That is, according to the resin composition of this invention, it turns out that the molded object which has high flame retardance is obtained, without impairing mechanical characteristics.
- a resin composition having a talc content within the range of the present invention has a small maximum heat generation rate and a molded product having high flame retardancy.
- the reason is assumed to be due to the following mechanism. That is, as shown in FIG. 2, when the appearance of the test piece after the combustion test was examined, the test piece obtained from the resin composition of Example 3 (including talc) was the same as the resin composition of Comparative Example 7 (talc In comparison with the test piece obtained from the above (not included), foaming was observed on the surface, and it had a swollen appearance.
- the resin composition constituting the test piece contains talc, a foamed carbonized layer is formed on the surface of the test piece when the test piece burns, and this carbonized layer functions as a heat insulating layer. It is presumed to show a messengertic flame retardant form. Therefore, according to the resin composition in which the content of talc is within the range of the present invention, it becomes easy to obtain an intumescent flame retardant form at the time of combustion, and it is considered that a molded body having high flame retardancy can be obtained.
Abstract
To provide a polybutylene terephthalate resin composition for obtaining a molded body that has high flame retardancy and excellent mechanical characteristics.
The present invention provides a polybutylene terephthalate resin composition which contains a polybutylene terephthalate, talc that serves as a flame retardant, a bromine-based flame retardant and an antimony-based flame retardant assistant. In this polybutylene terephthalate resin composition, the content of the talc that serves as a flame retardant is more than 1% by mass but less than 5% by mass relative to the total mass of the polybutylene terephthalate resin composition.
Description
本発明は、ポリブチレンテレフタレート樹脂組成物に関する。
The present invention relates to a polybutylene terephthalate resin composition.
ポリブチレンテレフタレート樹脂は、優れた機械的特性、電気的特性等を有するため、自動車部品、電気・電子部品等の種々の成形体の材料として広く利用されている。
Polybutylene terephthalate resin is widely used as a material for various molded products such as automobile parts and electric / electronic parts because it has excellent mechanical and electrical properties.
そして、上記の成形体は、一般的に高い難燃性を有することが求められる。そのため、難燃性が高い成形体を得るために、ポリブチレンテレフタレート樹脂を含む組成物の難燃性を改善するための検討がなされてきた。難燃性が改善されたポリブチレンテレフタレート樹脂組成物の例として、例えば、特許文献１乃至６に記載の組成物が挙げられる。
And, the above molded body is generally required to have high flame retardancy. Therefore, in order to obtain a molded product having high flame retardancy, studies have been made to improve the flame retardancy of a composition containing a polybutylene terephthalate resin. Examples of the polybutylene terephthalate resin composition with improved flame retardancy include, for example, compositions described in Patent Documents 1 to 6.
しかし、従来のポリブチレンテレフタレート樹脂組成物から得られる成形体は、高い難燃性が付与されてはいるものの、機械的特性等のその他の特性が十分でない可能性があった。
However, although a molded product obtained from a conventional polybutylene terephthalate resin composition is imparted with high flame retardancy, other properties such as mechanical properties may not be sufficient.
本発明は上記課題を解決するためになされたものであり、高い難燃性及び優れた機械的特性を有する成形体を得るためのポリブチレンテレフタレート樹脂組成物を提供することを目的とする。
The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a polybutylene terephthalate resin composition for obtaining a molded product having high flame retardancy and excellent mechanical properties.
本発明者らは、ポリブチレンテレフタレートと、所定量のタルクと、臭素系難燃剤と、アンチモン系難燃助剤とを含むポリブチレンテレフタレート樹脂組成物によれば上記課題を解決できることを見出し、本発明を完成するに至った。より具体的には、本発明は以下のものを提供する。
The present inventors have found that a polybutylene terephthalate resin composition containing polybutylene terephthalate, a predetermined amount of talc, a brominated flame retardant, and an antimony flame retardant aid can solve the above problems, and The invention has been completed. More specifically, the present invention provides the following.
（１） ポリブチレンテレフタレート樹脂組成物であって、
上記ポリブチレンテレフタレート樹脂組成物はポリブチレンテレフタレートと、難燃剤としてのタルクと、臭素系難燃剤と、アンチモン系難燃助剤とを含み、
上記ポリブチレンテレフタレート樹脂組成物中における、上記難燃剤としてのタルクの含有量が、上記ポリブチレンテレフタレート樹脂組成物の合計量に対して１質量％超～５質量％未満であるポリブチレンテレフタレート樹脂組成物。 (1) A polybutylene terephthalate resin composition,
The polybutylene terephthalate resin composition includes polybutylene terephthalate, talc as a flame retardant, a brominated flame retardant, and an antimony flame retardant aid,
The polybutylene terephthalate resin composition in which the content of talc as the flame retardant in the polybutylene terephthalate resin composition is more than 1% by mass to less than 5% by mass with respect to the total amount of the polybutylene terephthalate resin composition. object.
上記ポリブチレンテレフタレート樹脂組成物はポリブチレンテレフタレートと、難燃剤としてのタルクと、臭素系難燃剤と、アンチモン系難燃助剤とを含み、
上記ポリブチレンテレフタレート樹脂組成物中における、上記難燃剤としてのタルクの含有量が、上記ポリブチレンテレフタレート樹脂組成物の合計量に対して１質量％超～５質量％未満であるポリブチレンテレフタレート樹脂組成物。 (1) A polybutylene terephthalate resin composition,
The polybutylene terephthalate resin composition includes polybutylene terephthalate, talc as a flame retardant, a brominated flame retardant, and an antimony flame retardant aid,
The polybutylene terephthalate resin composition in which the content of talc as the flame retardant in the polybutylene terephthalate resin composition is more than 1% by mass to less than 5% by mass with respect to the total amount of the polybutylene terephthalate resin composition. object.
（２） 上記ポリブチレンテレフタレート樹脂組成物中の上記難燃剤としてのタルクの含有量が、上記難燃剤としてのタルク、上記臭素系難燃剤及び上記アンチモン系難燃助剤の合計量に対して５～３０質量％である（１）に記載のポリブチレンテレフタレート樹脂組成物。
(2) The content of talc as the flame retardant in the polybutylene terephthalate resin composition is 5 with respect to the total amount of talc as the flame retardant, the brominated flame retardant and the antimony flame retardant auxiliary. The polybutylene terephthalate resin composition according to (1), which is ˜30% by mass.
（３） 上記ポリブチレンテレフタレート樹脂組成物中における、上記臭素系難燃剤中の臭素原子及び上記アンチモン系難燃助剤中のアンチモン原子の質量の合計量が、ポリブチレンテレフタレート樹脂組成物中の有機成分の合計量に対して１～５ｍｏｌ／ｋｇである（１）又は（２）に記載のポリブチレンテレフタレート樹脂組成物。
(3) The total amount of bromine atoms in the bromine-based flame retardant and antimony atoms in the antimony-based flame retardant aid in the polybutylene terephthalate resin composition is the organic content in the polybutylene terephthalate resin composition. The polybutylene terephthalate resin composition according to (1) or (2), which is 1 to 5 mol / kg based on the total amount of the components.
（４） 上記ポリブチレンテレフタレート樹脂組成物中における、上記臭素系難燃剤中の臭素原子の質量と、上記アンチモン系難燃助剤中のアンチモン原子の質量との比率（臭素原子／アンチモン原子）が、１／２～４／１である（１）から（３）のいずれかに記載のポリブチレンテレフタレート樹脂組成物。
(4) The ratio (bromine atom / antimony atom) of the mass of bromine atoms in the brominated flame retardant and the mass of antimony atoms in the antimony flame retardant aid in the polybutylene terephthalate resin composition is The polybutylene terephthalate resin composition according to any one of (1) to (3), which is 1/2 to 4/1.
本発明によれば、高い難燃性及び優れた機械的特性を有する成形体を得るためのポリブチレンテレフタレート樹脂組成物が提供される。
According to the present invention, there is provided a polybutylene terephthalate resin composition for obtaining a molded product having high flame retardancy and excellent mechanical properties.
以下、本発明の実施形態について説明する。なお、本発明は以下の実施形態に限定されない。
Hereinafter, embodiments of the present invention will be described. In addition, this invention is not limited to the following embodiment.
本発明のポリブチレンテレフタレート樹脂組成物（以下、「本発明の樹脂組成物」とも言う）は、ポリブチレンテレフタレートと、所定量の難燃剤としてのタルクと、臭素系難燃剤と、アンチモン系難燃助剤とを含む。以下、本発明のポリブチレンテレフタレート樹脂組成物中の各成分について説明する。
The polybutylene terephthalate resin composition of the present invention (hereinafter also referred to as the “resin composition of the present invention”) comprises polybutylene terephthalate, a predetermined amount of talc, a brominated flame retardant, and an antimony flame retardant. Including auxiliaries. Hereinafter, each component in the polybutylene terephthalate resin composition of the present invention will be described.
＜ポリブチレンテレフタレート＞
ポリブチレンテレフタレートとは、少なくともテレフタル酸又はそのエステル形成性誘導体（Ｃ１～Ｃ６のアルキルエステルや酸ハロゲン化物等）を含むジカルボン酸成分と、少なくとも炭素原子数４のアルキレングリコール（１，４－ブタンジオール）又はそのエステル形成性誘導体を含むグリコール成分とを重縮合して得られる化合物である。本発明におけるポリブチレンテレフタレートは、ホモポリブチレンテレフタレートであってもよく、ブチレンテレフタレート単位を６０モル％以上（特に７５モル％以上９５モル％以下）含有する共重合体であってもよい。 <Polybutylene terephthalate>
Polybutylene terephthalate is a dicarboxylic acid component containing at least terephthalic acid or an ester-forming derivative thereof (C 1 -C 6 alkyl ester, acid halide, etc.) and an alkylene glycol (1,4-carbon atom) having at least 4 carbon atoms. Butanediol) or a glycol component containing an ester-forming derivative thereof. The polybutylene terephthalate in the present invention may be a homopolybutylene terephthalate or a copolymer containing 60 mol% or more (particularly 75 mol% or more and 95 mol% or less) of a butylene terephthalate unit.
ポリブチレンテレフタレートとは、少なくともテレフタル酸又はそのエステル形成性誘導体（Ｃ１～Ｃ６のアルキルエステルや酸ハロゲン化物等）を含むジカルボン酸成分と、少なくとも炭素原子数４のアルキレングリコール（１，４－ブタンジオール）又はそのエステル形成性誘導体を含むグリコール成分とを重縮合して得られる化合物である。本発明におけるポリブチレンテレフタレートは、ホモポリブチレンテレフタレートであってもよく、ブチレンテレフタレート単位を６０モル％以上（特に７５モル％以上９５モル％以下）含有する共重合体であってもよい。 <Polybutylene terephthalate>
Polybutylene terephthalate is a dicarboxylic acid component containing at least terephthalic acid or an ester-forming derivative thereof (C 1 -C 6 alkyl ester, acid halide, etc.) and an alkylene glycol (1,4-carbon atom) having at least 4 carbon atoms. Butanediol) or a glycol component containing an ester-forming derivative thereof. The polybutylene terephthalate in the present invention may be a homopolybutylene terephthalate or a copolymer containing 60 mol% or more (particularly 75 mol% or more and 95 mol% or less) of a butylene terephthalate unit.
ポリブチレンテレフタレートにおいて、テレフタル酸及びそのエステル形成性誘導体以外のジカルボン酸成分（コモノマー成分）としては、例えば、イソフタル酸、フタル酸、２，６－ナフタレンジカルボン酸、４，４’－ジカルボキシジフェニルエーテル等のＣ８～Ｃ１４の芳香族ジカルボン酸；コハク酸、アジピン酸、アゼライン酸、セバシン酸等のＣ４～Ｃ１６のアルキルジカルボン酸；シクロヘキサンジカルボン酸等のＣ５～Ｃ１０のシクロアルキルジカルボン酸；これらのジカルボン酸成分のエステル形成性誘導体（Ｃ１～Ｃ６のアルキルエステル誘導体や酸ハロゲン化物等）が挙げられる。これらのジカルボン酸成分は、単独で又は２種以上を組み合わせて使用できる。
In polybutylene terephthalate, dicarboxylic acid components (comonomer components) other than terephthalic acid and its ester-forming derivatives include, for example, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-dicarboxydiphenyl ether, etc. C 8 -C 14 aromatic dicarboxylic acids; C 4 -C 16 alkyl dicarboxylic acids such as succinic acid, adipic acid, azelaic acid and sebacic acid; C 5 -C 10 cycloalkyl dicarboxylic acids such as cyclohexane dicarboxylic acid And ester-forming derivatives of these dicarboxylic acid components (C 1 -C 6 alkyl ester derivatives, acid halides, etc.). These dicarboxylic acid components can be used alone or in combination of two or more.
ポリブチレンテレフタレートにおいて、１，４－ブタンジオール以外のグリコール成分（コモノマー成分）としては、例えば、エチレングリコール、プロピレングリコール、トリメチレングリコール、１，３－ブチレングリコール、ヘキサメチレングリコール、ネオペンチルグリコール、１，３－オクタンジオール等のＣ２～Ｃ１０のアルキレングリコール；ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール等のポリオキシアルキレングリコール；シクロヘキサンジメタノール、水素化ビスフェノールＡ等の脂環式ジオール;ビスフェノールＡ、４，４’－ジヒドロキシビフェニル等の芳香族ジオール；ビスフェノールＡのエチレンオキサイド２モル付加体、ビスフェノールＡのプロピレンオキサイド３モル付加体等の、ビスフェノールＡのＣ２～Ｃ４のアルキレンオキサイド付加体；又はこれらのグリコールのエステル形成性誘導体（アセチル化物等）が挙げられる。これらのグリコール成分は、単独で又は２種以上を組み合わせて使用できる。
In polybutylene terephthalate, glycol components (comonomer components) other than 1,4-butanediol include, for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene glycol, hexamethylene glycol, neopentyl glycol, 1 , alkylene glycol C 2 ~ C 10 and 3-octanediol; diethylene glycol, triethylene glycol, polyoxyalkylene glycol and dipropylene glycol; cyclohexanedimethanol, alicyclic diols such as hydrogenated bisphenol a; bisphenol a, Aromatic diols such as 4,4'-dihydroxybiphenyl; ethylene oxide 2 mol adduct of bisphenol A, propylene oxide 3 mol adduct of bisphenol A The alkylene oxide adduct of C 2 ~ C 4 of bisphenol A; or ester-forming derivatives of these glycols (acetylated, etc.). These glycol components can be used alone or in combination of two or more.
以上説明したコモノマー成分を共重合したポリブチレンテレフタレート共重合体は、いずれもポリブチレンテレフタレートとして好適に使用できる。また、ポリブチレンテレフタレートとして、ホモポリブチレンテレフタレート重合体とポリブチレンテレフタレート共重合体とを組み合わせて使用してもよい。
Any of the polybutylene terephthalate copolymers obtained by copolymerizing the comonomer components described above can be suitably used as polybutylene terephthalate. Further, as polybutylene terephthalate, a homopolybutylene terephthalate polymer and a polybutylene terephthalate copolymer may be used in combination.
ポリブチレンテレフタレートの末端カルボキシル基量は、本発明の目的を阻害しない限り特に制限されないが、３０ｍｅｑ／ｋｇ以下が好ましく、２５ｍｅｑ以下がより好ましい。かかる範囲の末端カルボキシル基量のポリブチレンテレフタレートを用いると、ポリブチレンテレフタレート樹脂組成物から得られる成形体の機械的特性が特に優れる点で好ましい。
The amount of terminal carboxyl groups of polybutylene terephthalate is not particularly limited as long as the object of the present invention is not impaired, but is preferably 30 meq / kg or less, more preferably 25 meq or less. Use of polybutylene terephthalate having a terminal carboxyl group content in such a range is preferable in that the mechanical properties of the molded product obtained from the polybutylene terephthalate resin composition are particularly excellent.
また、ポリブチレンテレフタレートのメルトフローレートは本発明の目的を阻害しない範囲で特に制限されないが、５ｇ／１０ｍｉｎ以上１００ｇ／１０ｍｉｎ以下であるのが好ましい。さらに好ましくは１０ｇ／１０ｍｉｎ以上８０ｇ／１０ｍｉｎ以下である。かかる範囲のメルトフローレートのポリブチレンテレフタレートを用いると、得られるポリブチレンテレフタレート樹脂組成物の成形性が特に優れている点で好ましい。なお、ポリブチレンテレフタレートのメルトフローレートは、ＩＳＯ１１３３に準拠し、例えば温度２３５℃、荷重２１６０ｇの条件で測定する。
The melt flow rate of polybutylene terephthalate is not particularly limited as long as the object of the present invention is not impaired, but is preferably 5 g / 10 min or more and 100 g / 10 min or less. More preferably, they are 10 g / 10min or more and 80 g / 10min or less. Use of polybutylene terephthalate having a melt flow rate in such a range is preferable in that the moldability of the resulting polybutylene terephthalate resin composition is particularly excellent. The melt flow rate of polybutylene terephthalate is measured in accordance with ISO 1133, for example, under conditions of a temperature of 235 ° C. and a load of 2160 g.
本発明の樹脂組成物中のポリブチレンテレフタレートの含有量は特に限定されず、後述するタルク等の含有量と調整して適宜決定でき、例えば、ポリブチレンテレフタレート樹脂組成物の合計量に対して、３０～８０質量％、好ましくは４５～６５質量％であってもよい。
The content of polybutylene terephthalate in the resin composition of the present invention is not particularly limited, and can be appropriately determined by adjusting the content of talc and the like described later, for example, with respect to the total amount of the polybutylene terephthalate resin composition, It may be 30 to 80% by mass, preferably 45 to 65% by mass.
＜タルク＞
本発明の樹脂組成物には、難燃剤としてタルクが含まれる。タルクとは、ケイ酸塩鉱物の一種であり、水酸化マグネシウム及びケイ酸塩等を含む。 <Talc>
The resin composition of the present invention contains talc as a flame retardant. Talc is a kind of silicate mineral and includes magnesium hydroxide and silicate.
本発明の樹脂組成物には、難燃剤としてタルクが含まれる。タルクとは、ケイ酸塩鉱物の一種であり、水酸化マグネシウム及びケイ酸塩等を含む。 <Talc>
The resin composition of the present invention contains talc as a flame retardant. Talc is a kind of silicate mineral and includes magnesium hydroxide and silicate.
従来、タルクは、ポリブチレンテレフタレート樹脂組成物中に、強化剤、核剤、電気特性向上剤、高熱伝導剤等として添加されてきた。しかし、本発明者らの検討の結果、後述する臭素系難燃剤及びアンチモン系難燃助剤とともにタルクを含むポリブチレンテレフタレート樹脂組成物においては、タルクは優れた難燃剤として作用することを見出した。通常、ポリブチレンテレフタレート樹脂組成物に難燃剤が配合されていると、該樹脂組成物から得られる成形体に難燃剤が付与されるものの、機械的特性が十分でない可能性があった。しかし、タルクを含む本発明の樹脂組成物によれば、機械的特性を犠牲にすることなく、難燃性の高い成形体が得られる。
Conventionally, talc has been added to a polybutylene terephthalate resin composition as a reinforcing agent, a nucleating agent, an electrical property improver, a high thermal conductive agent, and the like. However, as a result of the study by the present inventors, it was found that talc acts as an excellent flame retardant in the polybutylene terephthalate resin composition containing talc together with the brominated flame retardant and antimony flame retardant auxiliary described later. . Usually, when a flame retardant is blended in the polybutylene terephthalate resin composition, the flame retardant is imparted to a molded product obtained from the resin composition, but mechanical properties may not be sufficient. However, according to the resin composition of the present invention containing talc, a molded article having high flame retardancy can be obtained without sacrificing mechanical properties.
従来は、例えば、難燃ポリプロピレン樹脂組成物にタルクを添加すると、該樹脂組成物から得られる成形体の難燃性が低下してしまうことが知られていた（清野充ら、「ＰＰの燃焼特性におよぼす難燃剤及びタルクの分布状態の影響」、成形加工、Ｖｏｌ．２２ Ｎｏ．５ ２０１０等を参照されたい）。このような知見からすれば、ポリプロピレン同様に結晶性樹脂であるポリブチレンテレフタレートと、タルクとが配合された樹脂組成物から得られる成形体の難燃性が高いという本発明の効果は予想外であると言える。本発明の樹脂組成物から得られる成形体の難燃性が高い理由は、下記の理由によるものと推察される。すなわち、成形体を構成する樹脂組成物にタルクが含まれていると、成形体の燃焼時に、発泡した炭化層が成形体表面に形成され、この炭化層が断熱層として機能し、いわゆるイントメッセント系難燃形態となると推測される。イントメッセント系難燃形態は難燃性に優れることが知られ、本発明の樹脂組成物から得られる成形体は、燃焼時にこの形態となりやすいために難燃性に優れるものと考えられる。
Conventionally, it has been known that, for example, when talc is added to a flame retardant polypropylene resin composition, the flame retardancy of a molded product obtained from the resin composition is reduced (Mitsuaki Seino et al., “Combustion of PP”). Influence of flame retardant and talc distribution state on properties ", molding process, Vol. 22, No. 5, 2010, etc.). Based on such knowledge, the effect of the present invention that the molded article obtained from a resin composition in which polybutylene terephthalate, which is a crystalline resin, and talc are blended like polypropylene is highly flame retardant is unexpected. It can be said that there is. The reason why the molded product obtained from the resin composition of the present invention has high flame retardance is assumed to be due to the following reason. That is, when talc is contained in the resin composition constituting the molded body, a foamed carbonized layer is formed on the surface of the molded body when the molded body burns, and this carbonized layer functions as a heat insulating layer. It is presumed that it will be a non-flammable form. It is known that the intomescent flame retardant form is excellent in flame retardancy, and the molded product obtained from the resin composition of the present invention is likely to have this form at the time of combustion.
本発明のポリブチレンテレフタレート樹脂組成物中には、ポリブチレンテレフタレート樹脂組成物の合計量に対して１質量％超～５質量％未満のタルクが含まれる。タルクの含有量が樹脂組成物の合計量に対して１質量％以下であると、樹脂組成物の最大発熱速度が大きくなるだけではなく、アンダーライターズ・ラボラトリーズのＵＬ－９４規格垂直燃焼試験においてドリッピングによる脱脂綿の着火が発生しやすくなるため、該樹脂組成物から得られる成形体の難燃性は十分ではない。タルクの含有量が樹脂組成物の合計量に対して５質量％以上であると、該樹脂組成物から得られる成形体の機械的特性が低下する可能性がある。タルクの含有量が樹脂組成物の合計量に対して２．０質量％～４．０質量％、好ましくは２．５質量％～３．５質量％であると、樹脂組成物の最大発熱速度が特に小さいため、得られる成形体の難燃性が特に高くなる点で好ましい。
The polybutylene terephthalate resin composition of the present invention contains talc in an amount of more than 1% by mass to less than 5% by mass with respect to the total amount of the polybutylene terephthalate resin composition. When the talc content is 1% by mass or less based on the total amount of the resin composition, not only the maximum heat generation rate of the resin composition is increased, but also in the UL-94 standard vertical combustion test of Underwriters Laboratories. Since the absorbent cotton is easily ignited by dripping, the flame retardancy of the molded product obtained from the resin composition is not sufficient. When the content of talc is 5% by mass or more with respect to the total amount of the resin composition, the mechanical properties of the molded product obtained from the resin composition may be deteriorated. When the talc content is 2.0% by mass to 4.0% by mass, preferably 2.5% by mass to 3.5% by mass, based on the total amount of the resin composition, the maximum heat generation rate of the resin composition Is particularly small, it is preferable in that the flame retardancy of the resulting molded product is particularly high.
本発明のポリブチレンテレフタレート樹脂組成物中には、タルクと、臭素系難燃剤（後述する）と、アンチモン系難燃助剤（後述する）との合計量に対して５～３０質量％、好ましくは１０～２０質量％のタルクが含まれることが好ましい。このような割合で樹脂組成物にタルクが配合されることにより、該樹脂組成物から得られる成形体の物性を損なわずに、臭素系難燃剤及びアンチモン系難燃助剤によって奏される難燃性をさらに向上させることができる。
In the polybutylene terephthalate resin composition of the present invention, 5 to 30% by mass, preferably based on the total amount of talc, bromine-based flame retardant (described later) and antimony-based flame retardant auxiliary (described later) Preferably contains 10 to 20% by mass of talc. By adding talc to the resin composition at such a ratio, the flame retardant produced by the brominated flame retardant and the antimony flame retardant aid is obtained without impairing the physical properties of the molded product obtained from the resin composition. The property can be further improved.
＜臭素系難燃剤＞
本発明の樹脂組成物には、難燃剤として臭素系難燃剤が含まれる。本発明において用いる臭素系難燃剤は、臭素を含有する有機化合物であって、ポリブチレンテレフタレート等の高分子材料を難燃化できるものであれば特に限定されず、高分子材料用に市販されている種々の難燃剤を使用することができる。 <Brominated flame retardant>
The resin composition of the present invention contains a brominated flame retardant as a flame retardant. The brominated flame retardant used in the present invention is not particularly limited as long as it is a bromine-containing organic compound and can flame retardant polymer materials such as polybutylene terephthalate, and is commercially available for polymer materials. Various flame retardants can be used.
本発明の樹脂組成物には、難燃剤として臭素系難燃剤が含まれる。本発明において用いる臭素系難燃剤は、臭素を含有する有機化合物であって、ポリブチレンテレフタレート等の高分子材料を難燃化できるものであれば特に限定されず、高分子材料用に市販されている種々の難燃剤を使用することができる。 <Brominated flame retardant>
The resin composition of the present invention contains a brominated flame retardant as a flame retardant. The brominated flame retardant used in the present invention is not particularly limited as long as it is a bromine-containing organic compound and can flame retardant polymer materials such as polybutylene terephthalate, and is commercially available for polymer materials. Various flame retardants can be used.
臭素系難燃剤に含まれる臭素の含有量は、２０質量％以上であることが好ましい。臭素の含有量が少ないと、所望の難燃性を得るために多量の難燃剤を使用する必要が生じ、本発明の樹脂組成物から得られる成形体の機械的特性が損なわれる可能性があるため好ましくない。
The bromine content in the brominated flame retardant is preferably 20% by mass or more. If the bromine content is low, it is necessary to use a large amount of flame retardant in order to obtain the desired flame retardancy, and the mechanical properties of the molded product obtained from the resin composition of the present invention may be impaired. Therefore, it is not preferable.
難燃剤の種類は特に限定されず、例えば、ハロゲン含有難燃剤、リン含有難燃剤、窒素含有難燃剤、イオウ含有難燃剤、ケイ素含有難燃剤、アルコール系難燃剤、無機系難燃剤、芳香族樹脂難燃剤等が挙げられる。本発明においては、ハロゲン含有難燃剤が好ましく、臭素含有難燃剤がより好ましい。臭素含有難燃剤としては、臭素含有アクリル系樹脂、臭素含有スチレン系樹脂、臭素含有ポリカーボネート系樹脂、臭素含有エポキシ系樹脂、臭素化ポリアリールエーテル化合物、臭素化芳香族イミド化合物、臭素化ビスアリール化合物、臭素化トリ（アリールオキシ）トリアジン化合物等が挙げられる。剛性、耐衝撃性、流動性、耐熱性、耐候性をバランスよく向上させられるという理由で臭素含有エポキシ系樹脂が好ましい。
The type of flame retardant is not particularly limited. For example, halogen-containing flame retardant, phosphorus-containing flame retardant, nitrogen-containing flame retardant, sulfur-containing flame retardant, silicon-containing flame retardant, alcohol flame retardant, inorganic flame retardant, aromatic resin Examples include flame retardants. In the present invention, a halogen-containing flame retardant is preferable, and a bromine-containing flame retardant is more preferable. Brominated flame retardants include brominated acrylic resins, brominated styrene resins, brominated polycarbonate resins, brominated epoxy resins, brominated polyaryl ether compounds, brominated aromatic imide compounds, brominated bisaryl compounds, Examples thereof include brominated tri (aryloxy) triazine compounds. A bromine-containing epoxy resin is preferable because the rigidity, impact resistance, fluidity, heat resistance, and weather resistance can be improved in a balanced manner.
臭素含有エポキシ系樹脂としては、末端が封止されたものを使用してもよい。末端を封止した臭素含有エポキシ系樹脂を使用すれば、成形時の樹脂組成物の流動性が高くなるため好ましい。末端封止された臭素含有エポキシ系樹脂のうちビスフェノールＡ型エポキシ系樹脂が特に好ましい。また、通常、臭素含有エポキシ系樹脂の末端封止にはブロモフェノールが好ましく使用されるが、ブロモフェノールのうちトリブロモフェノールが特に好ましく使用される。なお、ポリブチレンテレフタレート樹脂組成物には、複数の種類の難燃剤が含まれていてもよい。
As the bromine-containing epoxy resin, a resin whose end is sealed may be used. It is preferable to use a bromine-containing epoxy resin whose ends are sealed because the fluidity of the resin composition at the time of molding becomes high. Of the bromine-containing epoxy resins end-capped, bisphenol A type epoxy resins are particularly preferred. Usually, bromophenol is preferably used for end-capping the bromine-containing epoxy resin, but tribromophenol is particularly preferably used among bromophenols. The polybutylene terephthalate resin composition may contain a plurality of types of flame retardants.
本発明の樹脂組成物中の臭素系難燃剤の含有量は、ポリブチレンテレフタレート樹脂組成物の合計量に対して、５～５０質量％が好ましく、５～２０質量％がより好ましい。樹脂組成物中の臭素系難燃剤の含有量を上記の範囲とすることで、機械的特性を犠牲にすることなく、良好な難燃性を有する成形体が得られる樹脂組成物を調製できる。
The content of the brominated flame retardant in the resin composition of the present invention is preferably 5 to 50% by mass and more preferably 5 to 20% by mass with respect to the total amount of the polybutylene terephthalate resin composition. By setting the content of the brominated flame retardant in the resin composition within the above range, it is possible to prepare a resin composition from which a molded article having good flame retardancy can be obtained without sacrificing mechanical properties.
＜アンチモン系難燃助剤＞
本発明の樹脂組成物には、難燃助剤としてアンチモン系難燃助剤が含まれる。本発明において用いるアンチモン系難燃助剤は、アンチモンを含有し、良好な難燃効果が得られるものであれば、本発明の目的を阻害しない範囲で特に限定されない。本発明において好適に使用されるアンチモン系難燃助剤の具体例としては、三酸化アンチモン、四酸化アンチモン、五酸化アンチモン、アンチモン酸ナトリウム、ハロゲン化アンチモン等が挙げられる。これらのアンチモン系難燃助剤は２種以上を組み合わせて使用できる。アンチモン系難燃助剤を、水酸化アルミニウム、水酸化マグネシウム、硫化亜鉛等の難燃助剤と組み合わせて使用してもよい。 <Antimony flame retardant aid>
The resin composition of the present invention contains an antimony flame retardant aid as a flame retardant aid. The antimony flame retardant aid used in the present invention is not particularly limited as long as it contains antimony and provides a good flame retardant effect, so long as the object of the present invention is not impaired. Specific examples of the antimony flame retardant aid preferably used in the present invention include antimony trioxide, antimony tetraoxide, antimony pentoxide, sodium antimonate, antimony halide and the like. These antimony flame retardant aids can be used in combination of two or more. An antimony flame retardant aid may be used in combination with a flame retardant aid such as aluminum hydroxide, magnesium hydroxide, or zinc sulfide.
本発明の樹脂組成物には、難燃助剤としてアンチモン系難燃助剤が含まれる。本発明において用いるアンチモン系難燃助剤は、アンチモンを含有し、良好な難燃効果が得られるものであれば、本発明の目的を阻害しない範囲で特に限定されない。本発明において好適に使用されるアンチモン系難燃助剤の具体例としては、三酸化アンチモン、四酸化アンチモン、五酸化アンチモン、アンチモン酸ナトリウム、ハロゲン化アンチモン等が挙げられる。これらのアンチモン系難燃助剤は２種以上を組み合わせて使用できる。アンチモン系難燃助剤を、水酸化アルミニウム、水酸化マグネシウム、硫化亜鉛等の難燃助剤と組み合わせて使用してもよい。 <Antimony flame retardant aid>
The resin composition of the present invention contains an antimony flame retardant aid as a flame retardant aid. The antimony flame retardant aid used in the present invention is not particularly limited as long as it contains antimony and provides a good flame retardant effect, so long as the object of the present invention is not impaired. Specific examples of the antimony flame retardant aid preferably used in the present invention include antimony trioxide, antimony tetraoxide, antimony pentoxide, sodium antimonate, antimony halide and the like. These antimony flame retardant aids can be used in combination of two or more. An antimony flame retardant aid may be used in combination with a flame retardant aid such as aluminum hydroxide, magnesium hydroxide, or zinc sulfide.
アンチモン系難燃助剤の形態は特に限定されないが、粒子状であるのが好ましく、平均粒子径０．１～１０μｍの粒子状であるのがより好ましい。
The form of the antimony-based flame retardant aid is not particularly limited, but is preferably in the form of particles, and more preferably in the form of particles having an average particle size of 0.1 to 10 μm.
本発明の樹脂組成物中のアンチモン系難燃助剤の含有量は、臭素系難燃剤の含有量との関係で適宜決定できる。例えば、ポリブチレンテレフタレート樹脂組成物中における、臭素系難燃剤中の臭素原子及びアンチモン系難燃助剤中のアンチモン原子の質量の合計量が、ポリブチレンテレフタレート樹脂組成物中の有機成分の合計量に対して１～５ｍｏｌ／ｋｇであってもよい。また、ポリブチレンテレフタレート樹脂組成物中における、臭素系難燃剤中の臭素原子の質量と、アンチモン系難燃助剤中のアンチモン原子の質量との比率（臭素原子／アンチモン原子）が、１／２～４／１であってもよい。アンチモン系難燃助剤が上記を満たすように配合されることで、臭素系難燃剤による難燃性付与効果を効果的に高めることができる。
The content of the antimony flame retardant aid in the resin composition of the present invention can be appropriately determined in relation to the content of the bromine flame retardant. For example, in the polybutylene terephthalate resin composition, the total amount of bromine atoms in the bromine-based flame retardant and antimony atoms in the antimony-based flame retardant aid is the total amount of organic components in the polybutylene terephthalate resin composition. It may be 1 to 5 mol / kg. In the polybutylene terephthalate resin composition, the ratio (bromine atom / antimony atom) between the mass of bromine atoms in the brominated flame retardant and the mass of antimony atoms in the antimony flame retardant auxiliary is 1/2. It may be up to 4/1. By blending the antimony flame retardant auxiliary so as to satisfy the above, it is possible to effectively enhance the flame retardancy imparting effect by the bromine flame retardant.
＜その他の成分＞
本発明のポリブチレンテレフタレート樹脂組成物には、上記の成分以外の成分が配合されていてもよい。具体的には、充填剤（ガラス繊維等）、滴下防止剤（ポリテトラフルオロエチレン等）、酸化防止剤、帯電防止剤、離型剤、着色剤等を挙げることができる。 <Other ingredients>
Components other than the above components may be blended in the polybutylene terephthalate resin composition of the present invention. Specific examples include fillers (glass fibers and the like), anti-dripping agents (polytetrafluoroethylene and the like), antioxidants, antistatic agents, mold release agents, colorants and the like.
本発明のポリブチレンテレフタレート樹脂組成物には、上記の成分以外の成分が配合されていてもよい。具体的には、充填剤（ガラス繊維等）、滴下防止剤（ポリテトラフルオロエチレン等）、酸化防止剤、帯電防止剤、離型剤、着色剤等を挙げることができる。 <Other ingredients>
Components other than the above components may be blended in the polybutylene terephthalate resin composition of the present invention. Specific examples include fillers (glass fibers and the like), anti-dripping agents (polytetrafluoroethylene and the like), antioxidants, antistatic agents, mold release agents, colorants and the like.
本発明の樹脂組成物中のその他の含有量は、その合計量が、ポリブチレンテレフタレート樹脂組成物の合計量に対して、０～５０質量％、好ましくは１０～４０質量％であってもよい。
The other content in the resin composition of the present invention may be 0 to 50% by mass, preferably 10 to 40% by mass, based on the total amount of the polybutylene terephthalate resin composition. .
＜ポリブチレンテレフタレート樹脂組成物の調製方法＞
本発明のポリブチレンテレフタレート樹脂組成物の調製方法の具体的態様は特に限定されるものではなく、一般に樹脂組成物又はその成形体の調製法として公知の設備と方法により、ポリブチレンテレフタレート樹脂組成物を調製することができる。例えば、必要な成分を混合し、１軸又は２軸の押出機又はその他の溶融混練装置を使用して混練し、成形用ペレットとして調製することができる。また、押出機又はその他の溶融混練装置は複数使用してもよい。また、樹脂組成物の混練温度（シリンダー温度）は２５０℃以上２８０℃以下が好ましく、より好ましくは２５０℃以上２７０℃以下である。混練温度が２８０℃より高いと混練中に樹脂の分解が進行しやすく、２５０℃より低いと得られるポリブチレンテレフタレート樹脂組成物中の各成分の分散状態が優れない場合があり好ましくない。 <Preparation method of polybutylene terephthalate resin composition>
The specific embodiment of the method for preparing the polybutylene terephthalate resin composition of the present invention is not particularly limited. Generally, the polybutylene terephthalate resin composition is prepared by a well-known facility and method as a method for preparing the resin composition or a molded product thereof. Can be prepared. For example, necessary components can be mixed and kneaded using a single or twin screw extruder or other melt kneader to prepare pellets for molding. A plurality of extruders or other melt kneaders may be used. The kneading temperature (cylinder temperature) of the resin composition is preferably 250 ° C. or higher and 280 ° C. or lower, more preferably 250 ° C. or higher and 270 ° C. or lower. When the kneading temperature is higher than 280 ° C., the decomposition of the resin tends to proceed during the kneading, and when it is lower than 250 ° C., the dispersion state of each component in the obtained polybutylene terephthalate resin composition may not be excellent.
本発明のポリブチレンテレフタレート樹脂組成物の調製方法の具体的態様は特に限定されるものではなく、一般に樹脂組成物又はその成形体の調製法として公知の設備と方法により、ポリブチレンテレフタレート樹脂組成物を調製することができる。例えば、必要な成分を混合し、１軸又は２軸の押出機又はその他の溶融混練装置を使用して混練し、成形用ペレットとして調製することができる。また、押出機又はその他の溶融混練装置は複数使用してもよい。また、樹脂組成物の混練温度（シリンダー温度）は２５０℃以上２８０℃以下が好ましく、より好ましくは２５０℃以上２７０℃以下である。混練温度が２８０℃より高いと混練中に樹脂の分解が進行しやすく、２５０℃より低いと得られるポリブチレンテレフタレート樹脂組成物中の各成分の分散状態が優れない場合があり好ましくない。 <Preparation method of polybutylene terephthalate resin composition>
The specific embodiment of the method for preparing the polybutylene terephthalate resin composition of the present invention is not particularly limited. Generally, the polybutylene terephthalate resin composition is prepared by a well-known facility and method as a method for preparing the resin composition or a molded product thereof. Can be prepared. For example, necessary components can be mixed and kneaded using a single or twin screw extruder or other melt kneader to prepare pellets for molding. A plurality of extruders or other melt kneaders may be used. The kneading temperature (cylinder temperature) of the resin composition is preferably 250 ° C. or higher and 280 ° C. or lower, more preferably 250 ° C. or higher and 270 ° C. or lower. When the kneading temperature is higher than 280 ° C., the decomposition of the resin tends to proceed during the kneading, and when it is lower than 250 ° C., the dispersion state of each component in the obtained polybutylene terephthalate resin composition may not be excellent.
本発明のポリブチレンテレフタレート樹脂組成物の溶融粘度は適度に高い。溶融粘度は、樹脂組成物の流動性を示す値である。樹脂組成物の溶融粘度が低い場合は樹脂が分解しやすく、該樹脂組成物から得られる機械的特性の低下を招く可能性がある。本発明の樹脂組成物は、溶融粘度の低下が抑制されているため、該樹脂組成物から得られる成形体には良好な機械的特性が付与されている。樹脂組成物の溶融粘度は、ＩＳＯ１１４４３に準拠して測定する。
The melt viscosity of the polybutylene terephthalate resin composition of the present invention is moderately high. The melt viscosity is a value indicating the fluidity of the resin composition. When the melt viscosity of the resin composition is low, the resin is easily decomposed and there is a possibility that the mechanical properties obtained from the resin composition are lowered. In the resin composition of the present invention, since the decrease in melt viscosity is suppressed, good mechanical properties are imparted to the molded product obtained from the resin composition. The melt viscosity of the resin composition is measured according to ISO11443.
＜成形体の製造方法＞
本発明のポリブチレンテレフタレート樹脂組成物を用いて、従来公知の成形方法（例えば、射出成形、押出成形、圧縮成形、ブロー成形、真空成形、発泡成形、回転成形、ガスインジェクション成形等の方法）で、種々の成形体を成形することができる。 <Method for producing molded body>
Using the polybutylene terephthalate resin composition of the present invention, a conventionally known molding method (for example, a method such as injection molding, extrusion molding, compression molding, blow molding, vacuum molding, foam molding, rotational molding, gas injection molding, etc.) Various molded bodies can be molded.
本発明のポリブチレンテレフタレート樹脂組成物を用いて、従来公知の成形方法（例えば、射出成形、押出成形、圧縮成形、ブロー成形、真空成形、発泡成形、回転成形、ガスインジェクション成形等の方法）で、種々の成形体を成形することができる。 <Method for producing molded body>
Using the polybutylene terephthalate resin composition of the present invention, a conventionally known molding method (for example, a method such as injection molding, extrusion molding, compression molding, blow molding, vacuum molding, foam molding, rotational molding, gas injection molding, etc.) Various molded bodies can be molded.
上記のような方法で得られた成形体は、難燃性に優れる。具体的には、該成形体は、アンダーライターズ・ラボラトリーズのＵＬ－９４規格垂直燃焼試験におけるＶ－０の規格を満たす。また、上記のような方法で得られた成形体は、機械的特性に優れる。成形体の機械的特性は、ＩＳＯ５２７－１，２に準拠して、引張り特性（引張り強度及び引張り伸び）を評価することで判断できる。
The molded body obtained by the above method is excellent in flame retardancy. Specifically, the molded body satisfies the V-0 standard in the UL-94 standard vertical combustion test of Underwriters Laboratories. Moreover, the molded object obtained by the above methods is excellent in mechanical characteristics. The mechanical properties of the molded product can be determined by evaluating tensile properties (tensile strength and tensile elongation) in accordance with ISO527-1,2.
本発明の樹脂組成物を成形して得られる成形体は、上記の性質を有するため、電気・電子部品、ＯＡ機器部品、家電機器部品、自動車部品、機械機構部品等として好ましく使用できる。
Since the molded product obtained by molding the resin composition of the present invention has the above properties, it can be preferably used as an electric / electronic component, OA device component, home appliance component, automobile component, mechanical mechanism component, or the like.
以下、実施例により本発明をさらに詳しく説明するが、本発明はこれらに限定されるものではない。
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
＜材料＞
ポリブチレンテレフタレート樹脂（表中、「ＰＢＴ」）；ウィンテックポリマー社製、メルトフローレートは４１ｇ／１０ｍｉｎである。
タルク；日本タルク（株）社製、「タルク３Ａ」
マイカ；西日本貿易（株）社製、「スゾライトマイカ１５０－Ｓ」
炭酸カルシウム（表中、「炭酸Ｃａ」）；東洋ファインケミカル（株）社製、「ホワイトンＰ－３０」
酸化亜鉛；三井金属鉱業（株）社製、「酸化亜鉛一種」
酸化マグネシウム（表中、「酸化Ｍｇ」）；協和化学工業（株）社製、「キョーワマグＭＦ－１５０」
ベーマイト；Ｎａｂａｌｔｅｃ社製、「ＡＣＴＩＬＯＸ Ｂ６０」
臭素系難燃剤１（表中、「難燃剤１」）；臭素含有エポキシ樹脂（ＩＣＬ－ＩＰ社製、「Ｆ３１００」、末端封止有り）
臭素系難燃剤２（表中、「難燃剤２」）；臭素含有エポキシ樹脂（ＩＣＬ－ＩＰ社製、「Ｆ２１００」、末端封止無し）
アンチモン系難燃助剤（表中、「難燃助剤」）；三酸化アンチモン（日本精鉱（株）社製、「ＰＡＴＯＸ－Ｍ」）
ガラス繊維；日東紡績（株）社製、「平均繊維径φ１３μｍチョップドストランド」
滴下防止剤；旭硝子（株）社製、「フルオンＣＤ－０７６」 <Material>
Polybutylene terephthalate resin (in the table, “PBT”); manufactured by Wintech Polymer Co., Ltd., melt flow rate is 41 g / 10 min.
Talc: “Talc 3A” manufactured by Nippon Talc Co., Ltd.
Mica: “Szolite Mica 150-S” manufactured by West Japan Trading Co., Ltd.
Calcium carbonate (“Ca carbonate” in the table); manufactured by Toyo Fine Chemical Co., Ltd., “Whiteon P-30”
Zinc oxide; made by Mitsui Mining & Smelting Co., Ltd. “Zinc oxide”
Magnesium oxide (“Mg oxide” in the table); “Kyowa Mag MF-150” manufactured by Kyowa Chemical Industry Co., Ltd.
Boehmite; Navaltec, “ACTILOX B60”
Brominated flame retardant 1 (“Flame retardant 1” in the table); Bromine-containing epoxy resin (ICL-IP, “F3100”, with end-capping)
Brominated flame retardant 2 (in the table, "Flame retardant 2"); Bromine-containing epoxy resin (ICL-IP, "F2100", no end-capping)
Antimony flame retardant aid (in the table, “Flame retardant aid”); Antimony trioxide (Nippon Seiko Co., Ltd. “PATOX-M”)
Glass fiber: Nitto Boseki Co., Ltd., “average fiber diameter φ13 μm chopped strand”
Anti-drip agent: “Fullon CD-076” manufactured by Asahi Glass Co., Ltd.
ポリブチレンテレフタレート樹脂（表中、「ＰＢＴ」）；ウィンテックポリマー社製、メルトフローレートは４１ｇ／１０ｍｉｎである。
タルク；日本タルク（株）社製、「タルク３Ａ」
マイカ；西日本貿易（株）社製、「スゾライトマイカ１５０－Ｓ」
炭酸カルシウム（表中、「炭酸Ｃａ」）；東洋ファインケミカル（株）社製、「ホワイトンＰ－３０」
酸化亜鉛；三井金属鉱業（株）社製、「酸化亜鉛一種」
酸化マグネシウム（表中、「酸化Ｍｇ」）；協和化学工業（株）社製、「キョーワマグＭＦ－１５０」
ベーマイト；Ｎａｂａｌｔｅｃ社製、「ＡＣＴＩＬＯＸ Ｂ６０」
臭素系難燃剤１（表中、「難燃剤１」）；臭素含有エポキシ樹脂（ＩＣＬ－ＩＰ社製、「Ｆ３１００」、末端封止有り）
臭素系難燃剤２（表中、「難燃剤２」）；臭素含有エポキシ樹脂（ＩＣＬ－ＩＰ社製、「Ｆ２１００」、末端封止無し）
アンチモン系難燃助剤（表中、「難燃助剤」）；三酸化アンチモン（日本精鉱（株）社製、「ＰＡＴＯＸ－Ｍ」）
ガラス繊維；日東紡績（株）社製、「平均繊維径φ１３μｍチョップドストランド」
滴下防止剤；旭硝子（株）社製、「フルオンＣＤ－０７６」 <Material>
Polybutylene terephthalate resin (in the table, “PBT”); manufactured by Wintech Polymer Co., Ltd., melt flow rate is 41 g / 10 min.
Talc: “Talc 3A” manufactured by Nippon Talc Co., Ltd.
Mica: “Szolite Mica 150-S” manufactured by West Japan Trading Co., Ltd.
Calcium carbonate (“Ca carbonate” in the table); manufactured by Toyo Fine Chemical Co., Ltd., “Whiteon P-30”
Zinc oxide; made by Mitsui Mining & Smelting Co., Ltd. “Zinc oxide”
Magnesium oxide (“Mg oxide” in the table); “Kyowa Mag MF-150” manufactured by Kyowa Chemical Industry Co., Ltd.
Boehmite; Navaltec, “ACTILOX B60”
Brominated flame retardant 1 (“Flame retardant 1” in the table); Bromine-containing epoxy resin (ICL-IP, “F3100”, with end-capping)
Brominated flame retardant 2 (in the table, "Flame retardant 2"); Bromine-containing epoxy resin (ICL-IP, "F2100", no end-capping)
Antimony flame retardant aid (in the table, “Flame retardant aid”); Antimony trioxide (Nippon Seiko Co., Ltd. “PATOX-M”)
Glass fiber: Nitto Boseki Co., Ltd., “average fiber diameter φ13 μm chopped strand”
Anti-drip agent: “Fullon CD-076” manufactured by Asahi Glass Co., Ltd.
＜ポリブチレンテレフタレート樹脂組成物の製造＞
上記の材料を以下の表１及び２に示す割合（単位は質量％）でドライブレンドし、３０ｍｍφのスクリューを有する２軸押出機（（株）日本製鋼所製）にホッパーから供給して２５０℃で溶融混練し、ペレット状のポリブチレンテレフタレート樹脂組成物を得た。 <Production of polybutylene terephthalate resin composition>
The above materials are dry blended in the proportions shown in Tables 1 and 2 below (unit: mass%) and supplied from a hopper to a twin screw extruder (manufactured by Nippon Steel Works) having a 30 mmφ screw at 250 ° C. And kneaded to obtain a pellet-shaped polybutylene terephthalate resin composition.
上記の材料を以下の表１及び２に示す割合（単位は質量％）でドライブレンドし、３０ｍｍφのスクリューを有する２軸押出機（（株）日本製鋼所製）にホッパーから供給して２５０℃で溶融混練し、ペレット状のポリブチレンテレフタレート樹脂組成物を得た。 <Production of polybutylene terephthalate resin composition>
The above materials are dry blended in the proportions shown in Tables 1 and 2 below (unit: mass%) and supplied from a hopper to a twin screw extruder (manufactured by Nippon Steel Works) having a 30 mmφ screw at 250 ° C. And kneaded to obtain a pellet-shaped polybutylene terephthalate resin composition.
なお、表１及び２中、「Ｂｒ＋Ｓｂ」は、ポリブチレンテレフタレート樹脂組成物中の有機成分の合計量に対する、臭素系難燃剤中の臭素原子及びアンチモン系難燃助剤中のアンチモン原子の質量の割合（単位；ｍｏｌ／ｋｇ）を示す。また、「Ｂｒ／Ｓｂ」は、ポリブチレンテレフタレート樹脂組成物中における、臭素系難燃剤中の臭素原子と、アンチモン系難燃助剤中のアンチモン原子との比率（臭素原子／アンチモン原子）を示す。「Ｂ／（Ｂ＋Ｃ＋Ｄ）」は、表１及び２中のＢ欄にされた成分の合計量と、Ｂ乃至Ｄ欄にされた成分の合計量との比率（単位：％）を示す。
In Tables 1 and 2, “Br + Sb” represents the mass of bromine atoms in the brominated flame retardant and antimony atoms in the antimony based flame retardant aid relative to the total amount of organic components in the polybutylene terephthalate resin composition. The ratio (unit: mol / kg) is shown. “Br / Sb” indicates the ratio (bromine atom / antimony atom) of bromine atoms in the brominated flame retardant and antimony atoms in the antimony flame retardant auxiliary in the polybutylene terephthalate resin composition. . “B / (B + C + D)” indicates a ratio (unit:%) between the total amount of the components indicated in the B column in Tables 1 and 2 and the total amount of the components indicated in the B to D columns.
＜評価＞
実施例及び比較例の樹脂組成物について、各種評価を以下の方法で行った。評価結果を表１及び２ならびに図１に示した。 <Evaluation>
Various evaluation was performed with the following method about the resin composition of an Example and a comparative example. The evaluation results are shown in Tables 1 and 2 and FIG.
実施例及び比較例の樹脂組成物について、各種評価を以下の方法で行った。評価結果を表１及び２ならびに図１に示した。 <Evaluation>
Various evaluation was performed with the following method about the resin composition of an Example and a comparative example. The evaluation results are shown in Tables 1 and 2 and FIG.
［溶融粘度（ＭＶ）の測定］
ＩＳＯ１１４４３に準拠し、温度２６０℃、せん断速度１０００ｓ－１で測定した。 [Measurement of melt viscosity (MV)]
In accordance with ISO 11443, measurement was performed at a temperature of 260 ° C. and a shear rate of 1000 s −1 .
ＩＳＯ１１４４３に準拠し、温度２６０℃、せん断速度１０００ｓ－１で測定した。 [Measurement of melt viscosity (MV)]
In accordance with ISO 11443, measurement was performed at a temperature of 260 ° C. and a shear rate of 1000 s −1 .
［滞留溶融粘度保持率（滞留ＭＶ保持率）の測定］
ＩＳＯ１１４４３に準拠し、温度２６０℃、シリンダー滞留時間３０分、せん断速度１０００ｓ－１で測定し、［溶融粘度（ＭＶ）の測定］において測定した溶融粘度（ＭＶ）で除した。 [Measurement of retention melt viscosity retention (retention MV retention)]
In accordance with ISO 11443, measurement was performed at a temperature of 260 ° C., a cylinder residence time of 30 minutes, a shear rate of 1000 s −1 , and divided by the melt viscosity (MV) measured in [Measurement of Melt Viscosity (MV)].
ＩＳＯ１１４４３に準拠し、温度２６０℃、シリンダー滞留時間３０分、せん断速度１０００ｓ－１で測定し、［溶融粘度（ＭＶ）の測定］において測定した溶融粘度（ＭＶ）で除した。 [Measurement of retention melt viscosity retention (retention MV retention)]
In accordance with ISO 11443, measurement was performed at a temperature of 260 ° C., a cylinder residence time of 30 minutes, a shear rate of 1000 s −1 , and divided by the melt viscosity (MV) measured in [Measurement of Melt Viscosity (MV)].
［引張り強度（ＴＳ）及び引張り伸び（ＴＥ）の測定］
各樹脂組成物を、成形温度２５０℃、金型温度８０℃で、射出成形して試験片を作製した。得られた試験片について、ＩＳＯ５２７－１，２に準拠し、引張り強さ及び引張り伸びの測定を行った。 [Measurement of tensile strength (TS) and tensile elongation (TE)]
Each resin composition was injection molded at a molding temperature of 250 ° C. and a mold temperature of 80 ° C. to prepare test pieces. The obtained test piece was measured for tensile strength and tensile elongation according to ISO527-1,2.
各樹脂組成物を、成形温度２５０℃、金型温度８０℃で、射出成形して試験片を作製した。得られた試験片について、ＩＳＯ５２７－１，２に準拠し、引張り強さ及び引張り伸びの測定を行った。 [Measurement of tensile strength (TS) and tensile elongation (TE)]
Each resin composition was injection molded at a molding temperature of 250 ° C. and a mold temperature of 80 ° C. to prepare test pieces. The obtained test piece was measured for tensile strength and tensile elongation according to ISO527-1,2.
［難燃性の評価］
各樹脂組成物を、成形温度２５０℃、金型温度８０℃で、射出成形して製造した試験片（０．７５ｍｍ厚み）について、アンダーライターズ・ラボラトリーズのＵＬ－９４規格垂直燃焼試験に準拠して燃焼性を評価した。評価は、各樹脂組成物から製造した試験片５本に対して行い、燃焼中にドリッピングが発生した試験片の本数、及び、ドリッピングにより試験片下部の脱脂綿に火が着いた試験片の本数をそれぞれ数えた。その結果は、表２の「ドリッピング」の項に示した。表２の「ドリッピング」の項において、括弧外の数字は、燃焼中にドリッピングが発生した試験片の本数であり、括弧内の数字は、ドリッピングにより試験片下部の脱脂綿に火が着いた試験片の本数である。 [Evaluation of flame retardancy]
The test piece (0.75 mm thickness) produced by injection molding each resin composition at a molding temperature of 250 ° C. and a mold temperature of 80 ° C. conforms to the UL-94 standard vertical combustion test of Underwriters Laboratories. The flammability was evaluated. The evaluation was performed on five test pieces manufactured from each resin composition. The number of test pieces that dripped during combustion and the test piece in which the absorbent cotton under the test piece was ignited by dripping. Each was counted. The results are shown in the “Dripping” section of Table 2. In the “dripping” section of Table 2, the numbers outside the parentheses are the number of test pieces that dripped during combustion, and the numbers in parentheses ignite the absorbent cotton under the test pieces by dripping. This is the number of test specimens.
各樹脂組成物を、成形温度２５０℃、金型温度８０℃で、射出成形して製造した試験片（０．７５ｍｍ厚み）について、アンダーライターズ・ラボラトリーズのＵＬ－９４規格垂直燃焼試験に準拠して燃焼性を評価した。評価は、各樹脂組成物から製造した試験片５本に対して行い、燃焼中にドリッピングが発生した試験片の本数、及び、ドリッピングにより試験片下部の脱脂綿に火が着いた試験片の本数をそれぞれ数えた。その結果は、表２の「ドリッピング」の項に示した。表２の「ドリッピング」の項において、括弧外の数字は、燃焼中にドリッピングが発生した試験片の本数であり、括弧内の数字は、ドリッピングにより試験片下部の脱脂綿に火が着いた試験片の本数である。 [Evaluation of flame retardancy]
The test piece (0.75 mm thickness) produced by injection molding each resin composition at a molding temperature of 250 ° C. and a mold temperature of 80 ° C. conforms to the UL-94 standard vertical combustion test of Underwriters Laboratories. The flammability was evaluated. The evaluation was performed on five test pieces manufactured from each resin composition. The number of test pieces that dripped during combustion and the test piece in which the absorbent cotton under the test piece was ignited by dripping. Each was counted. The results are shown in the “Dripping” section of Table 2. In the “dripping” section of Table 2, the numbers outside the parentheses are the number of test pieces that dripped during combustion, and the numbers in parentheses ignite the absorbent cotton under the test pieces by dripping. This is the number of test specimens.
［最大発熱速度の測定］
４０ｍｍ×１３ｍｍ×０．７５ｍｍの試験片に、マルチカロリメータ（東洋精機製作所社製、ＭＣＭ－２）によって５０ｋＷ／ｍ２の輻射熱を照射し、燃焼時の発熱速度を測定し、発熱速度の最大値を最大発熱速度（ＰＨＲＲとも呼ばれる）とした。 [Measurement of maximum heat generation rate]
The test piece of 40 mm x 13 mm x 0.75 mm was irradiated with 50 kW / m 2 of radiant heat using a multi calorimeter (manufactured by Toyo Seiki Seisakusho Co., Ltd., MCM-2), and the heat generation rate during combustion was measured. Was the maximum heat generation rate (also called PHRR).
４０ｍｍ×１３ｍｍ×０．７５ｍｍの試験片に、マルチカロリメータ（東洋精機製作所社製、ＭＣＭ－２）によって５０ｋＷ／ｍ２の輻射熱を照射し、燃焼時の発熱速度を測定し、発熱速度の最大値を最大発熱速度（ＰＨＲＲとも呼ばれる）とした。 [Measurement of maximum heat generation rate]
The test piece of 40 mm x 13 mm x 0.75 mm was irradiated with 50 kW / m 2 of radiant heat using a multi calorimeter (manufactured by Toyo Seiki Seisakusho Co., Ltd., MCM-2), and the heat generation rate during combustion was measured. Was the maximum heat generation rate (also called PHRR).
表１及び２に示される通り、本発明の樹脂組成物は、溶融粘度の値が高いため、樹脂組成物中の樹脂の分解が抑制され、物性に優れた成形体が得られることが分かる。また、本発明の樹脂組成物から得られる成形体は、難燃性が高いだけではなく、引張り特性に優れることが分かる。つまり、本発明の樹脂組成物によれば、機械的特性を損なわずに高い難燃性を有する成形体が得られることが分かる。
As shown in Tables 1 and 2, since the resin composition of the present invention has a high melt viscosity value, it can be seen that the resin in the resin composition is suppressed from being decomposed and a molded article having excellent physical properties can be obtained. Moreover, it turns out that the molded object obtained from the resin composition of this invention is not only high in a flame retardance but excellent in a tensile characteristic. That is, according to the resin composition of this invention, it turns out that the molded object which has high flame retardance is obtained, without impairing mechanical characteristics.
また、図１に示される通り、タルクの含有量が本発明の範囲内である樹脂組成物は、最大発熱速度の値が小さく、難燃性が高い成形体が得られることが分かる。その理由は、下記の機構によるものと推察される。すなわち、図２に示される通り、燃焼試験後の試験片の外観を検討すると、実施例３の樹脂組成物（タルクを含む）から得た試験片は、比較例７の樹脂組成物（タルクを含まない）から得た試験片と比較すると、表面に発泡が認められ、膨らんだ外観を有していた。これは、試験片を構成する樹脂組成物にタルクが含まれていると、試験片の燃焼時に、発泡した炭化層が試験片表面に形成され、この炭化層が断熱層として機能し、いわゆるイントメッセント系難燃形態となることを示すと推測される。したがって、タルクの含有量が本発明の範囲内である樹脂組成物によれば、燃焼時にイントメッセント系難燃形態となりやすくなるので、難燃性が高い成形体が得られるものと考えられる。
Further, as shown in FIG. 1, it can be seen that a resin composition having a talc content within the range of the present invention has a small maximum heat generation rate and a molded product having high flame retardancy. The reason is assumed to be due to the following mechanism. That is, as shown in FIG. 2, when the appearance of the test piece after the combustion test was examined, the test piece obtained from the resin composition of Example 3 (including talc) was the same as the resin composition of Comparative Example 7 (talc In comparison with the test piece obtained from the above (not included), foaming was observed on the surface, and it had a swollen appearance. This is because if the resin composition constituting the test piece contains talc, a foamed carbonized layer is formed on the surface of the test piece when the test piece burns, and this carbonized layer functions as a heat insulating layer. It is presumed to show a messentic flame retardant form. Therefore, according to the resin composition in which the content of talc is within the range of the present invention, it becomes easy to obtain an intumescent flame retardant form at the time of combustion, and it is considered that a molded body having high flame retardancy can be obtained.
Claims (4)
- ポリブチレンテレフタレート樹脂組成物であって、
前記ポリブチレンテレフタレート樹脂組成物はポリブチレンテレフタレートと、難燃剤としてのタルクと、臭素系難燃剤と、アンチモン系難燃助剤とを含み、
前記ポリブチレンテレフタレート樹脂組成物中における、前記難燃剤としてのタルクの含有量が、前記ポリブチレンテレフタレート樹脂組成物の合計量に対して１質量％超～５質量％未満であるポリブチレンテレフタレート樹脂組成物。 A polybutylene terephthalate resin composition comprising:
The polybutylene terephthalate resin composition includes polybutylene terephthalate, talc as a flame retardant, a brominated flame retardant, and an antimony flame retardant aid.
A polybutylene terephthalate resin composition in which the content of talc as the flame retardant in the polybutylene terephthalate resin composition is more than 1% by mass to less than 5% by mass with respect to the total amount of the polybutylene terephthalate resin composition. object. - 前記ポリブチレンテレフタレート樹脂組成物中の前記難燃剤としてのタルクの含有量が、前記難燃剤としてのタルク、前記臭素系難燃剤及び前記アンチモン系難燃助剤の合計量に対して５～３０質量％である請求項１に記載のポリブチレンテレフタレート樹脂組成物。 The content of talc as the flame retardant in the polybutylene terephthalate resin composition is 5 to 30 mass with respect to the total amount of talc as the flame retardant, the brominated flame retardant and the antimony flame retardant auxiliary. The polybutylene terephthalate resin composition according to claim 1, which is%.
- 前記ポリブチレンテレフタレート樹脂組成物中における、前記臭素系難燃剤中の臭素原子及び前記アンチモン系難燃助剤中のアンチモン原子の質量の合計量が、ポリブチレンテレフタレート樹脂組成物中の有機成分の合計量に対して１～５ｍｏｌ／ｋｇである請求項１又は２に記載のポリブチレンテレフタレート樹脂組成物。 In the polybutylene terephthalate resin composition, the total amount of bromine atoms in the bromine-based flame retardant and antimony atoms in the antimony-based flame retardant aid is the sum of the organic components in the polybutylene terephthalate resin composition. The polybutylene terephthalate resin composition according to claim 1 or 2, which is 1 to 5 mol / kg based on the amount.
- 前記ポリブチレンテレフタレート樹脂組成物中における、前記臭素系難燃剤中の臭素原子の質量と、前記アンチモン系難燃助剤中のアンチモン原子の質量との比率（臭素原子／アンチモン原子）が、１／２～４／１である請求項１から３のいずれか１項に記載のポリブチレンテレフタレート樹脂組成物。 In the polybutylene terephthalate resin composition, the ratio (bromine atom / antimony atom) between the mass of bromine atoms in the brominated flame retardant and the mass of antimony atoms in the antimony flame retardant auxiliary is 1 / The polybutylene terephthalate resin composition according to any one of claims 1 to 3, which is 2 to 4/1.
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| WO2020067564A1 (en) * | 2018-09-28 | 2020-04-02 | ポリプラスチックス株式会社 | Flame retardant polybutylene terephthalate resin composition |
| JP6726378B1 (en) * | 2018-09-28 | 2020-07-22 | ポリプラスチックス株式会社 | Flame-retardant polybutylene terephthalate resin composition |
| WO2021020095A1 (en) * | 2019-07-31 | 2021-02-04 | ポリプラスチックス株式会社 | Flame-retardant poly(butylene terephthalate) resin composition |
| JP2021024880A (en) * | 2019-07-31 | 2021-02-22 | ポリプラスチックス株式会社 | Flame-retardant polybutylene terephthalate resin composition |
| JP7454343B2 (en) | 2019-07-31 | 2024-03-22 | ポリプラスチックス株式会社 | Flame retardant polybutylene terephthalate resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104781342A (en) | 2015-07-15 |
| CN109777049A (en) | 2019-05-21 |
| JP6177252B2 (en) | 2017-08-09 |
| JPWO2014069489A1 (en) | 2016-09-08 |
| TW201430048A (en) | 2014-08-01 |
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