CN110746762B - Polyphenylene ether resin composition, molded article, and method for improving fluctuation in burning time - Google Patents
Polyphenylene ether resin composition, molded article, and method for improving fluctuation in burning time Download PDFInfo
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- CN110746762B CN110746762B CN201910618404.XA CN201910618404A CN110746762B CN 110746762 B CN110746762 B CN 110746762B CN 201910618404 A CN201910618404 A CN 201910618404A CN 110746762 B CN110746762 B CN 110746762B
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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
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
- C08L71/123—Polyphenylene oxides not modified by chemical after-treatment
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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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The purpose of the present invention is to provide a polyphenylene ether resin composition containing glass fibers, which can be effectively used even in a use environment where long-term durability is required, and which has excellent heat resistance, mechanical properties, and handling properties, a molded article, and a method for improving the variation in burning time. A polyphenylene ether resin composition characterized by containing a polyphenylene ether (A), a styrene resin (B), a flame retardant (C) and a glass fiber (D); the content of each component relative to 100 mass% of the total amount of the components (A), (B), (C) and (D) is: (A) 20 to 84% by mass of the component (A), 0to 5% by mass of the component (B), 5 to 25% by mass of the component (C), and 11 to 50% by mass of the component (D); the component (C) comprises 0-97 mass% of bisphenol A bis (diphenyl phosphate) (C-1) and 100-3 mass% of a condensed phosphate ester flame retardant (C-2) represented by the following chemical formula (1) relative to 100 mass% of the component (C). (wherein R is1～R4Is 2, 6-xylyl, and n is 1-3. ) [ formula 1]
Description
Technical Field
The present invention relates to a polyphenylene ether resin composition, a molded article, and a method for improving variation in burning time.
Background
The polyphenylene ether resin is generally a resin obtained by blending a polyphenylene ether and a styrene resin at an arbitrary ratio depending on the level of heat resistance and molding flowability required, and further compounding an elastomer component, a flame retardant, an inorganic filler, a heat stabilizer, and other additive components as required to obtain a resin composition. Polyphenylene ether resins are widely used in the fields of home appliances OA, office equipment, information equipment, automobiles, and the like because they are excellent in heat resistance, mechanical properties, moldability, acid and alkali resistance, dimensional stability, electrical characteristics, and the like. Among these applications, there have been studies on polyphenylene ether resin compositions containing a large amount of fibrous inorganic fillers, particularly glass fibers, as polyphenylene ether resin compositions for use in cooling fans (propellers) of electric and electronic devices represented by information devices such as home appliances OA, office equipment, and PCs, and the like, which have recently been required to have extremely high heat resistance, mechanical properties such as flexural strength, tensile strength, and the like as thin-walled molded articles, and further, durability for withstanding long-term stress under high-temperature conditions.
On the other hand, in such applications, an extremely high flame-retardant level, which has not been achieved in the past, has been often required in recent years, and it is known that flame retardancy can be achieved to some extent by blending a flame retardant into a polyphenylene ether resin composition (which is obtained by blending a large amount of an inorganic filler into a polyphenylene ether resin) (for example, see patent documents 1 and 2).
Further, a technique for improving flame retardancy of a thin-walled molded article of a resin composition containing a polyphenylene ether resin and a large amount of glass fibers has been disclosed (for example, see patent document 3).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 8-183902
Patent document 2: japanese laid-open patent publication No. 10-168260
Patent document 3: japanese patent laid-open publication No. 2015-209518
Disclosure of Invention
Problems to be solved by the invention
However, in the past, in a resin composition containing a fibrous inorganic filler, since it has a burning persistence due to a wick effect, it has been very difficult to increase the flame retardancy to a high level even when a flame retardant is contained. Particularly, when a burning test is carried out by using thin-walled test pieces with the thickness of 2.0-0.5 mm according to UL94, the fluctuation of burning time among the test pieces is increased, and the required flame retardant grade can not be met; even when the techniques disclosed in patent documents 1 and 2 are used, sufficient flame retardancy is not necessarily obtained.
In addition, patent document 3 indeed shows that the flame retardancy of thin-walled molded articles is significantly improved, but the fluctuation of the burning time between test pieces is not sufficiently improved. Further, since the flame retardant is limited to a solid flame retardant having a low melting point such as triphenyl phosphate, there is a possibility that it is difficult from the viewpoint of handling properties; the frequency of cleaning the mold is increased and the work may be complicated due to the generation of mold MD (mold deposit) during molding; the molding working environment may be deteriorated due to the generation of a large amount of gas; etc., which is still not necessarily sufficient.
Accordingly, an object of the present invention is to provide a polyphenylene ether resin composition containing glass fibers, a molded article thereof, and a method for improving the variation in the burning time thereof, which can be effectively used even in a use environment where long-term durability is required, and which has excellent heat resistance, mechanical properties, and handling properties.
Means for solving the problems
The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that a polyphenylene ether resin composition containing 11 to 50 mass% of glass fibers can be made flame-retardant by blending a specific type of condensed phosphate-based flame retardant, thereby obtaining a resin composition having excellent heat resistance, mechanical properties, and handling properties, and have provided the present invention.
Namely, the present invention is as follows.
[1]
A polyphenylene ether resin composition characterized in that,
the composition comprises polyphenylene oxide (A), styrene resin (B), flame retardant (C) and glass fiber (D),
the content of each component relative to 100 mass% of the total amount of the above components (A), (B), (C) and (D) is: (A) 20 to 84% by mass of component (B), 0to 5% by mass of component (B), 5 to 25% by mass of component (C), and 11 to 50% by mass of component (D),
the component (C) contains 0to 97 mass% of bisphenol A bis (diphenyl phosphate) (C-1) and 100 to 3 mass% of a condensed phosphate flame retardant (C-2) represented by the following chemical formula (1) with respect to 100 mass% of the component (C).
[ solution 1]
(in the formula, R1～R4Is 2, 6-xylyl, and n is 1-3. )
[2]
The polyphenylene ether resin composition according to [1], wherein the total content of the components (A), (B), (C) and (D) is 90% by mass or more of the total polyphenylene ether resin composition.
[3]
The polyphenylene ether resin composition according to [1] or [2], wherein a part or all of the component (A) is a functionalized polyphenylene ether functionalized with a carboxylic acid or an acid anhydride.
[4]
The polyphenylene ether resin composition according to any one of [1] to [3], wherein the component (C) is a mixture of the component (C-1) and the component (C-2), and the component (C) contains 50 to 95% by mass of the component (C-1) and 50 to 5% by mass of the component (C-2), assuming that the component (C) is 100% by mass.
[5]
The polyphenylene ether resin composition according to any one of [1] to [4], wherein the composition has a flame retardancy rating of V-0 when a burning test is performed using a test piece having a thickness of 0.7mm in accordance with UL 94.
[6]
The polyphenylene ether resin composition according to [5], wherein the difference between the maximum number of seconds of combustion and the minimum number of seconds of combustion is 5.0 seconds or less when the vertical burning test is performed.
[7]
A molded article comprising the polyphenylene ether resin composition according to any one of [1] to [6 ].
[8]
The molded article as described in [7], wherein the molded article has a thickness of 0.5 to 2.0mm and a flame retardancy grade of V-0 when a vertical flame test is performed according to UL 94.
[9]
The molded article as recited in [7] or [8], wherein the molded article is a cooling fan of an electric/electronic device.
[10]
A method for improving the variation in burning time (difference between the minimum burning seconds and the maximum burning seconds) when a vertical burning test is carried out using a test piece having a thickness of 0.7mm according to UL94 in a polyphenylene ether resin composition containing a polyphenylene ether (A), a styrene resin (B), a flame retardant (C) and a glass fiber (D), the contents of the respective components being, relative to 100 mass% of the total amount of the components (A), (B), (C) and (D): (A) 20 to 84% by mass of component (B), 0to 5% by mass of component (B), 5 to 25% by mass of component (C), and 11 to 50% by mass of component (D),
the flame retardant (C) is a mixture containing 0-97 mass% of bisphenol A bis (diphenyl phosphate) (C-1) and 100-3 mass% of a condensed phosphate flame retardant (C-2) represented by the following chemical formula (1) relative to 100 mass% of the component (C).
[ solution 2]
(in the formula, R1～R4Is 2, 6-xylyl, and n is 1-3. )
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided a polyphenylene ether resin composition containing glass fibers, a molded article thereof, and a method for improving variation in combustion time thereof, which can be effectively used even in a use environment where long-term durability is required, and which has excellent heat resistance, mechanical properties, and handling properties.
Detailed Description
The following describes in detail a specific embodiment of the present invention (hereinafter referred to as "the present embodiment"). The present invention is not limited to the following description, and can be implemented by being variously modified within the scope of the gist thereof.
[ resin composition ]
The polyphenylene ether resin composition of the present embodiment is characterized by containing a polyphenylene ether (a), a styrene resin (B), a flame retardant (C), and a glass fiber (D); the content of each component relative to 100 mass% of the total amount of the above components (A), (B), (C) and (D) is: (A) 20 to 84% by mass of component (A), 0to 5% by mass of component (B), 5 to 25% by mass of component (C), and 11 to 50% by mass of component (D); the component (C) contains 0to 97 mass% of bisphenol A bis (diphenyl phosphate) (C-1) and 100 to 3 mass% of a condensed phosphate flame retardant (C-2) represented by the following chemical formula (1) with respect to 100 mass% of the component (C).
[ solution 3]
(in the formula, R1～R4Is 2, 6-xylyl, and n is 1-3. )
(polyphenylene ether (A))
The polyphenylene ether (a) (hereinafter, the polyphenylene ether is also referred to simply as "PPE") of the present embodiment will be described.
Polyphenylene ether (a) in the present embodiment is preferably a homopolymer (homopolymer) or a copolymer (copolymer) having a repeating unit (structural unit) represented by chemical formula (2) and/or chemical formula (3).
[ solution 4]
[ solution 5]
Wherein, in the above chemical formulas (2) and (3), R3、R4、R5、R6、R7And R8Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 9 carbon atoms, or a halogen atom. Wherein R is7And R8Not simultaneously hydrogen atoms.
The alkyl group preferably has 1 to 3 carbon atoms, the aryl group preferably has 6 to 8 carbon atoms, and the monovalent residue preferably has a hydrogen atom.
The number of repeating units represented by the above chemical formulae (2) and (3) is not particularly limited, since it varies depending on the molecular weight distribution of polyphenylene ether (a).
Representative examples of homopolymers of polyphenylene ether include poly (2, 6-dimethyl-1, 4-phenylene) ether, poly (2-methyl-6-ethyl-1, 4-phenylene) ether, poly (2, 6-diethyl-1, 4-phenylene) ether, poly (2-ethyl-6-n-propyl-1, 4-phenylene) ether, poly (2, 6-di-n-propyl-1, 4-phenylene) ether, poly (2-methyl-6-n-butyl-1, 4-phenylene) ether, poly (2-ethyl-6-isopropyl-1, 4-phenylene) ether, poly (2-methyl-6-chloroethyl-1, 4-phenylene) ether, poly (2-ethyl-6-n-butyl-1, 4-phenylene) ether, poly (2-ethyl-6-isopropyl-1, 4-phenylene) ether, poly (2-6-ethyl-6-chloroethyl-1, 4-phenylene) ether, poly (2-1, 4-phenylene) ether, poly (2-one, poly (p) ether, e, poly (p) ether, poly (p) ether, p), poly (p, p), and poly (p) ether, p, Poly (2-methyl-6-hydroxyethyl-1, 4-phenylene) ether and poly (2-methyl-6-chloroethyl-1, 4-phenylene) ether, and the like.
Examples of the polyphenylene ether copolymer include, but are not limited to, copolymers having a polyphenylene ether structure represented by chemical formula (2) and/or chemical formula (3) as a main repeating unit, such as a copolymer of 2, 6-dimethylphenol and 2,3, 6-trimethylphenol, a copolymer of 2, 6-dimethylphenol and o-cresol, and a copolymer of 2,3, 6-trimethylphenol and o-cresol.
Among polyphenylene ethers, poly (2, 6-dimethyl-1, 4-phenylene) ether is preferred.
In the polyphenylene ether (A), the concentration of terminal OH groups is preferably 0.4 to 2.0, more preferably 0.6 to 1.3 per 100 monomer units constituting the polyphenylene ether, from the viewpoint of sufficient adhesion to the glass fiber as the component (D).
The terminal OH group concentration of PPE was calculated by NMR measurement.
One of the above polyphenylene ethers (A) may be used alone, or two or more of them may be used in combination.
In the present embodiment, it is preferable that the polyphenylene ether chain at least partially contains R in the chemical formula (2)3、R4Structures that are each methyl (as well as structures derived from such structures described below).
Polyphenylene ether (A) may contain, as a partial structure, any of various phenylene ether units other than the phenylene ether units represented by the above chemical formulae (2) and (3), as long as the heat resistance of the resin composition is not excessively lowered.
Examples of the phenylene ether units other than the phenylene ether units represented by the above chemical formulae (2) and (3) include, but are not limited to, 2- (dialkylaminomethyl) -6-methylphenylene ether units, 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether units, and the like described in, for example, Japanese patent application laid-open Nos. H01-297428 and 63-301222.
In the polyphenylene ether (A), a repeating unit such as active self-crosslinking quinone may be bonded in a small amount to the main chain of the polyphenylene ether.
Further, polyphenylene ether (a) preferably has a structure in which a part or all of the structural units constituting polyphenylene ether is replaced with a functionalized polyphenylene ether by reacting (modifying) the polyphenylene ether with a functionalizing agent containing 1 or more functional groups selected from the group consisting of a carboxyl group, an acid anhydride group, an amide group, an imide group, an amine group, an orthoester group, a hydroxyl group, and a group derived from an ammonium carboxylate salt.
In particular, from the viewpoint of improving adhesion to the glass fiber as the component (D) of the present application, improving heat resistance, mechanical properties and the like, it is preferable that a part or the whole of the polyphenylene ether (a) is a functionalized polyphenylene ether functionalized by reacting a polyphenylene ether with an acid anhydride such as maleic anhydride, and a carboxylic acid such as malic acid, citric acid, fumaric acid, and the like, and it is more preferable to be a maleic anhydride-modified polyphenylene ether obtained by reacting a polyphenylene ether with maleic anhydride. The maleic anhydride-modified polyphenylene ether can be obtained, for example, as follows: the maleic anhydride-modified polyphenylene ether is obtained by mixing 2 to 5 parts by mass of maleic anhydride with respect to 100 parts by mass of polyphenylene ether in a tumbler mixer, feeding the mixture into a twin-screw extruder, and melt-kneading the mixture at a temperature of 270 to 335 ℃.
In the polyphenylene ether (a), the concentration of the functionalized modified terminal is preferably 0.1 to 10, more preferably 0.1 to 3.0, and further preferably 0.1 to 1.0 per 100 monomer units constituting the polyphenylene ether, from the viewpoint of further improving the adhesion to the glass fiber of the component (D).
The modified end concentration of PPE can be calculated by NMR measurement.
The ratio (Mw/Mn value) of the weight average molecular weight Mw to the number average molecular weight Mn of the polyphenylene ether (A) is preferably 2.0 to 5.5, more preferably 2.5 to 4.5, and still more preferably 3.0 to 4.5.
The Mw/Mn value is preferably 2.0 or more in view of molding processability of the resin composition, and preferably 5.5 or less in view of mechanical properties of the resin composition.
In addition, the number average molecular weight Mn of the polyphenylene ether (A) is preferably 8000 to 28000, more preferably 12000 to 24000, and further preferably 14000 to 22000, from the viewpoint of moldability and mechanical properties.
Here, the weight average molecular weight Mw and the number average molecular weight Mn are obtained from polystyrene-equivalent molecular weights measured by GPC (gel permeation chromatography).
The reduced viscosity of the polyphenylene ether (A) is preferably in the range of 0.25 to 0.65 dL/g. More preferably 0.30 to 0.55dL/g, and still more preferably 0.33 to 0.42 dL/g.
The reduced viscosity of polyphenylene ether (A) is preferably 0.25dL/g or more in view of sufficient mechanical properties, and 0.65dL/g or less in view of moldability.
The reduced viscosity can be measured at 30 ℃ using a chloroform solution at 0.5g/dL using an Ubbelohde viscometer.
The polyphenylene ether (A) is usually obtained in the form of powder, and the preferred particle size thereof is 1 to 1000. mu.m, more preferably 10 to 700. mu.m, and particularly preferably 100 to 500. mu.m. From the viewpoint of handling property during processing, it is preferably 1 μm or more, and from the viewpoint of suppressing generation of an unmelted product during melt kneading, it is preferably 1000 μm or less.
In the resin composition of the present embodiment, the content of polyphenylene ether (a) is within a range of 20 to 84 mass% in 100 mass% of the total amount of polyphenylene ether (a), styrene resin (B), flame retardant (C) and glass fiber (D). The content of polyphenylene ether (A) is preferably in the range of 35 to 60 mass%, more preferably 40 to 55 mass%.
The content of polyphenylene ether (a) is preferably 20 mass% or more in terms of imparting sufficient heat resistance and flame retardancy, and is preferably 84 mass% or less in terms of moldability.
(styrene resin (B))
In the resin composition of the present embodiment, the styrene-based resin (B) is a polymer obtained by polymerizing a styrene-based compound or a styrene-based compound and a compound copolymerizable with the styrene-based compound in the presence or absence of a rubber polymer.
The styrene resin (B) may be used alone or in combination of two or more.
Examples of the styrene compound include, but are not limited to, styrene, α -methylstyrene, 2, 4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, and ethylstyrene. In particular, styrene is preferable from the viewpoint of the availability of the raw material.
Examples of the compound copolymerizable with the styrene compound include, but are not limited to, methacrylates such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; maleic anhydride and the like.
The amount of the compound copolymerizable with the styrene compound is preferably 30% by mass or less, more preferably 15% by mass or less, based on 100% by mass of the total amount of the styrene compound and the compound copolymerizable with the styrene compound.
Examples of the rubbery polymer include, but are not limited to, conjugated diene rubbers, copolymers of conjugated dienes and aromatic vinyl compounds, and ethylene-propylene copolymer rubbers, and more specifically, polybutadiene, styrene-butadiene random copolymers, styrene-butadiene block copolymers, and partially or substantially completely hydrogenated polymers thereof.
Among the above-mentioned styrenic resins, a polymer or copolymer obtained by polymerization or copolymerization in the presence of a rubber polymer is referred to as a rubber-reinforced styrenic resin, and a polymer or copolymer obtained by polymerization or copolymerization in the absence of a rubber polymer is referred to as a non-rubber-reinforced styrenic resin.
As the styrene resin (B), a styrene resin which is not reinforced with rubber, such as general-purpose polystyrene (GPPS), is preferable in view of mechanical properties of the molded article.
In the resin composition of the present embodiment, the content of the styrene resin (B) is within a range of 0to 5 mass% in the total amount of 100 mass% of the polyphenylene ether (a), the styrene resin (B), the flame retardant (C), and the glass fiber (D). Preferably in the range of 0to 3 mass%.
The styrene resin (B) is preferably added from the viewpoint of improving the molding flowability of the resin composition of the present embodiment, and is preferably blended in an amount of 5 mass% or less from the viewpoint of imparting sufficient mechanical properties and flame retardancy.
(flame retardant (C))
The flame retardant (C) used in the resin composition of the present embodiment is preferably a flame retardant comprising 0to 97 mass% of bisphenol A bis (diphenyl phosphate) (C-1) and 100 to 3 mass% of a condensed phosphate ester flame retardant (C-2) represented by the following formula (1) with respect to 100 mass% of the component (C) in terms of reduction of environmental load and flame retardancy.
[ solution 6]
R of the above chemical formula (1)1～R4Is 2, 6-xylyl, and n is selected from 1 to 3. n is preferably 1 or 2, and n is more preferably 1.
By using a mixture containing 0to 97 mass% of (C-1) and 100 to 3 mass% of (C-2) with respect to 100 mass% of the component (C) as the flame retardant (C), the fluctuation of the burning time between test pieces when the vertical burning test (according to UL94) is performed, which will be described later, can be improved.
In the resin composition of the present embodiment, it is preferable to combine the above (C-1) and (C-2) with the above flame retardant (C) in order to impart sufficient flame retardancy, improve the fluctuation of burning time between test pieces when a vertical burning test (according to UL94) described later is performed, improve the impact strength, and prevent the adhesion of MD to a mold. When the content of the component (C) is 100% by mass, the combination of (C-1)97 to 30% by mass and (C-2)3 to 70% by mass is preferable, the combination of (C-1)97 to 50% by mass and (C-2)3 to 50% by mass is more preferable, the combination of (C-1)95 to 50% by mass and (C-2)5 to 50% by mass is even more preferable, and the combination of (C-1)95 to 70% by mass and (C-2)5 to 30% by mass is particularly preferable.
In the resin composition of the present embodiment, the content of the flame retardant (C) is within a range of 5 to 25 mass% in 100 mass% of the total amount of the polyphenylene ether (a), the styrene resin (B), the flame retardant (C), and the glass fiber (D). The content of the flame retardant (C) is preferably 8 to 20 mass%, more preferably 10 to 15 mass%.
The flame retardant (C) is preferably contained in an amount of 5 mass% or more in order to improve the flame retardancy of the resin composition of the present embodiment, and is preferably contained in an amount of 25 mass% or less in order to maintain sufficient mechanical properties and heat resistance.
(glass fiber (D))
The glass fiber (D) is compounded in the resin composition of the present embodiment for the purpose of improving the mechanical strength.
As the glass of the glass fiber (D), known glass can be used, and examples thereof include E glass, C glass, S glass, and a glass. The glass fiber (D) is a fiber-shaped glass, and is distinguished from a bulk glass flake or a glass powder.
The average fiber diameter of the glass fibers (D) is preferably within a range of 5 to 15 μm, more preferably 7 to 13 μm. The thickness is preferably 5 μm or more from the viewpoint of reduction in rigidity, heat resistance, impact resistance, durability and the like of a molded article due to fiber breakage at the time of extrusion or molding and production stability, and is preferably 15 μm or less from the viewpoint of imparting sufficient mechanical properties and maintaining the surface appearance of the molded article.
The average length of the glass fibers (D) is preferably 0.5mm or more, more preferably 1mm or more from the viewpoint of imparting sufficient rigidity and handleability, and is preferably 10mm or less, more preferably 6mm or less from the viewpoint of handleability.
The glass fiber (D) used in the present embodiment may be surface-treated with a surface treating agent, for example, a silane compound. The silane compound used in the surface treatment agent is generally a silane compound used in the case of surface treatment of a glass filler, a mineral filler, or the like. Specific examples thereof include vinyl silane compounds such as vinyltrichlorosilane, vinyltriethoxysilane, and γ -methacryloxypropyltrimethoxysilane, epoxy silane compounds such as γ -glycidoxypropyltrimethoxysilane, sulfur silane compounds such as bis- (3-triethoxysilylpropyl) tetrasulfide, mercapto silane compounds such as γ -mercaptopropyltrimethoxysilane, and aminosilane compounds such as γ -aminopropyltriethoxysilane, and γ -ureidopropyltriethoxysilane. Particularly preferred silane compounds for the purpose of the present invention are aminosilane compounds. These silane compounds may be used alone or in combination of two or more. Further, the surface treatment may be performed by a mixture of these silane compounds and a sizing agent such as an epoxy-based sizing agent or a urethane-based sizing agent.
In the resin composition of the present embodiment, the content of the glass fiber (D) is within a range of 11 to 50 mass% in 100 mass% of the total amount of the polyphenylene ether (a), the styrene resin (B), the flame retardant (C), and the glass fiber (D). The content of the glass fiber (D) is preferably in the range of 15 to 40 mass%, more preferably in the range of 25 to 35 mass%.
The glass fiber (D) is preferably contained in an amount of 11 mass% or more in terms of improving the mechanical properties of the resin composition of the present embodiment, and preferably contained in an amount of 50 mass% or less in terms of maintaining sufficient moldability and imparting flame retardancy.
In the polyphenylene ether resin composition of the present embodiment, the total content of the components (a), (B), (C), and (D) is preferably 90 mass% or more of the total polyphenylene ether resin composition, from the viewpoint of further improving heat resistance, mechanical properties, flame retardancy, and surface appearance of a molded article. The content is more preferably 95% by mass or more, and may be 100% by mass.
(other materials)
The resin composition of the present embodiment may contain a styrene-based thermoplastic elastomer, a phenol terpene resin, or the like in a range that does not significantly reduce heat resistance, mechanical properties, flame retardancy, and surface appearance of a molded article. The content of these components may be in the range of 1 to 5% by mass relative to 100% by mass of the resin composition. The content is more preferably in the range of 1 to 4 mass%, and still more preferably 1 to 3 mass%. The content is preferably 1% by mass or more in view of exhibiting a sufficient effect of addition, and is preferably 5% by mass or less in view of maintaining physical properties.
The resin composition of the present embodiment may contain stabilizers such as an antioxidant, an ultraviolet absorber, and a heat stabilizer, a coloring agent, a releasing agent, and the like, in an amount that does not significantly reduce the heat resistance, mechanical properties, flame retardancy, and surface appearance of the molded article, and these may be contained in the resin composition of the present invention in a proportion of 0.001 to 3 mass%. The content is preferably in the range of 0.01 to 2 mass%, more preferably 0.2 to 1 mass%.
The content is preferably 0.001% by mass or more from the viewpoint of exhibiting a sufficient effect of addition, and is preferably 3% by mass or less from the viewpoint of maintaining physical properties.
The resin composition of the present embodiment may contain an inorganic filler other than glass fiber in a range not significantly deteriorating mechanical properties, impact resistance and flame retardancy, and the filler may be contained in an amount of 0.5 to 10% by mass in the resin composition of the present invention. Preferably 1 to 10 mass%, more preferably 2 to 8 mass%. Examples of the inorganic filler other than glass fiber include, but are not limited to, carbon fiber, mica, glass flake, talc, ground glass fiber, chlorite, and the like.
[ Properties of resin composition ]
The flame retardancy grade (UL-94) of the resin composition of the present embodiment is preferably V-0 when a vertical burning test is performed according to UL94 using a long test piece having a thickness of 0.7mm, from the viewpoint of preventing the spread of fire due to ignition, such as inside a device of a thin-walled molded article. In the case of performing the vertical burning test according to UL94 using 5 test pieces, the difference between the minimum number of seconds of burning and the maximum number of seconds of burning measured at the time of the first flame contact and the second flame contact (5 pieces × 2 times, total 10 times of flame contact) is preferably within 5 seconds, more preferably within 4 seconds.
When the resin composition of the present embodiment is used for a cooling fan of an electric/electronic device, the difference between the minimum number of seconds of combustion and the maximum number of seconds of combustion is preferably 4 seconds or less, more preferably 3 seconds or less, from the viewpoint of stability of flame retardancy.
The flame retardancy grade, the minimum number of seconds to burn and the maximum number of seconds to burn of the resin composition can be measured specifically by the methods described in the examples below.
When the resin composition of the present embodiment is used for a thin-walled molded article, the tensile strength (measured at 23 ℃ according to ISO 527) of the resin composition is preferably 120MPa or more in view of shape retention during use and prevention of cracking. More preferably 130MPa or more, and still more preferably 140MPa or more.
The tensile strength of the resin composition can be measured specifically by the method described in the examples below.
The resin composition of the present embodiment preferably has a bending strength (measured at 23 ℃ according to ISO 178) of 170MPa or more in view of shape retention when a thin molded article is used. More preferably 180MPa or more, and still more preferably 190MPa or more.
The flexural strength of the resin composition can be measured specifically by the method described in the examples below.
The Charpy impact strength (measured at 23 ℃ in accordance with ISO 179) of the resin composition of the present embodiment is preferably 7kJ/m in terms of preventing cracking at high-speed use2The above. More preferably 10kJ/m2The above.
Specifically, the charpy impact strength of the resin composition can be measured by the method described in the examples below.
The Melt Flow Rate (MFR) (measured at 250 ℃ under a load of 10kg in accordance with ISO 1133) of the resin composition of the present embodiment is preferably 3g/10min or more, from the viewpoint of moldability into a thin molded article. More preferably 5g/10min or more.
The MFR of the resin composition can be measured specifically by the method described in the examples below.
The resin composition of the present embodiment preferably has a Deformation Temperature Under Load (DTUL) (measured by the flat drawing method according to ISO75 under a load of 1.82 MPa) of 100 ℃ or higher, from the viewpoint of durability of the thin-walled molded article when used at high temperatures. More preferably 125 ℃ or higher, and still more preferably 135 ℃ or higher.
The DTUL of the resin composition can be measured specifically by the method described in the examples below.
[ method for producing resin composition ]
The resin composition of the present embodiment can be produced by melt-kneading the component (a), the component (B), the component (C), the component (D), and other materials as necessary.
The conditions for producing the resin composition of the present embodiment may be, for example, conditions for producing the resin composition of the present invention by melt-kneading the components (a), (B), (C), and (D) of the present invention at once, but the present invention is not limited thereto. From the viewpoint of improving mechanical properties and sufficiently achieving the effects of the present invention, it is preferable that polyphenylene ether (a) is previously melt-kneaded with a reactive compound such as a carboxylic acid or an acid anhydride to be reacted to produce a functionalized polyphenylene ether component, and then a part or all of polyphenylene ether (a) before substitution functionalization is used, and is melt-kneaded with components (B), (C), (D) and other components of the present invention in the next step to produce the resin composition of the present invention.
In addition, from the viewpoint of providing sufficient heat resistance and mechanical properties, it is preferable to melt-knead the components (a), (B), and other components in advance, and then mix and melt-knead the components (C) and (D).
In the method for producing a resin composition according to the present embodiment, a twin-screw extruder is preferably used in order to stably produce a large amount of the resin composition from the viewpoint of production efficiency, but the method is not limited thereto.
The diameter of the screw of the double-screw extruder is preferably in the range of 25-90 mm. More preferably 40 to 70 mm. For example, the following methods can be mentioned as suitable methods: a method of melt-kneading under conditions of a cylinder temperature of 270 to 330 ℃, a screw rotation speed of 150 to 450rpm, and an extrusion rate of 40 to 220kg/h, using a ZSK40MC twin-screw extruder (manufactured by Werner & Pfleiderer, Germany, number of cylinders 13, screw diameter of 40mm, and L/D of 50; screw mode having 2 kneading disks L, 6 kneading disks R, and 4 kneading disks N); a method of melt kneading under conditions of a cylinder temperature of 270 to 330 ℃, a screw rotation speed of 150 to 500rpm, and an extrusion rate of 200 to 600kg/h using a TEM58SS twin-screw extruder (manufactured by Toshiba mechanical Co., Ltd., number of barrels 13, a screw diameter of 58mm, and an L/D of 53; screw mode having 2 kneading disks L, 14 kneading disks R, and 2 kneading disks N).
In the above "L/D", the above "L" is the "length of the screw cylinder" of the extruder, and the above "D" is the "diameter of the screw cylinder".
In the production of the resin composition of the present embodiment using a twin-screw extruder, it is preferable that the component (a), the component (B), and the component (C-2) are supplied from a supply port (top feed port) at the most upstream portion of the extruder, the component (C-1) is supplied from a supply port (liquid-adding nozzle) provided midway in the extruder, and the component (D) is supplied by pressing the raw material provided midway in the extruder into a supply port (side feed port) from the viewpoint of heat resistance of the material and imparting mechanical properties.
[ molded article ]
A molded article made of the resin composition of the present embodiment can be obtained by molding the resin composition.
The molded article of the present embodiment is particularly preferably a thin molded article having a thickness of 0.5 to 2.0mm and a flame retardancy grade of V-0 when a vertical burning test is carried out according to UL 94. In this case, the spread of fire due to ignition inside the device of the thin molded article can be prevented.
The method of molding the resin composition is not particularly limited, and examples thereof include injection molding, extrusion molding, vacuum molding, and air pressure molding, and injection molding is particularly preferable from the viewpoint of appearance characteristics and mass productivity of the molded article.
Suitable molded articles include cooling fans for electric and electronic devices because of their excellent heat resistance and mechanical strength and their remarkably excellent thin-wall flame retardancy.
[ method for improving fluctuation in Combustion time ]
The method for improving the fluctuation of the burning time of the polyphenylene ether resin composition of the present embodiment is a method for improving the fluctuation of the burning time (difference between the minimum burning seconds and the maximum burning seconds) when a vertical burning test is performed using a test piece having a thickness of 0.7mm according to UL94 in a polyphenylene ether resin composition containing polyphenylene ether (a), a styrene resin (B), a flame retardant (C), and glass fibers (D) in an amount of 100 mass% relative to the total amount of the components (a), (B), (C), and (D): (A) 20 to 84% by mass of component (B), 0to 5% by mass of component (B), 5 to 25% by mass of component (C), and 11 to 50% by mass of component (D),
the flame retardant (C) is a mixture containing 0-97 mass% of bisphenol A bis (diphenyl phosphate) (C-1) and 100-3 mass% of a condensed phosphate flame retardant (C-2) represented by the following chemical formula (1) relative to 100 mass% of the component (C).
[ solution 7]
(in the formula, R1～R4Is 2, 6-xylyl, and n is 1-3. )
In the polyphenylene ether resin composition, by using a mixture containing 0to 97% by mass of (C-1) and 100 to 3% by mass of (C-2) per 100% by mass of the component (C) as the flame retardant (C), it is possible to improve the fluctuation of the combustion time (difference between the minimum number of seconds of combustion and the maximum number of seconds of combustion) when the vertical combustion test is performed on a test piece having a thickness of 0.7mm according to UL 94.
The fluctuation in the burning time (difference between the minimum burning seconds and the maximum burning seconds) of the resin composition can be measured specifically by the methods described in the examples described below.
[ examples ]
The present invention will be described below by referring to specific examples and comparative examples. The present invention is not limited to these.
The methods and materials for measuring physical properties used in examples and comparative examples are as follows.
(1. temperature of deformation under load (DTUL))
Pellets of the resin compositions produced in examples and comparative examples were dried in a hot air dryer at 90 ℃ for 1 hour.
Using the dried resin composition, a dumbbell type a multipurpose test piece according to ISO3167 was molded by an injection molding machine (IS-80EPN, manufactured by toshiba machines corporation) having an ISO physical property test piece mold, setting a cylinder temperature of 300 ℃, a mold temperature of 90 ℃, an injection pressure of 50MPa (gauge pressure), an injection speed of 200mm/sec, and an extrusion time/cooling time of 20sec/20 sec. The resulting dumbbell-shaped test piece of multipurpose test piece type A was cut to prepare a test piece of 80 mm. times.10 mm. times.4 mm. Using the test piece, the Deformation Temperature Under Load (DTUL) (. degree.C.) was measured at 1.82MPa according to ISO75 by the flat pull method.
As an evaluation criterion, the higher the DTUL value, the more excellent the heat resistance.
(2. Charpy impact Strength)
The multipurpose A-type dumbbell test piece prepared in 1.5 above was cut to prepare a test piece of 80mm by 10mm by 4 mm. By using the test piece, it is possible to obtain,charpy impact strength (kJ/m) determined according to ISO179 at 23 ℃ (notched) (kJ/m)2)。
As an evaluation criterion, the higher the measured value, the more excellent the impact resistance.
(3. Molding Flow (MFR))
Pellets of the resin compositions produced in examples and comparative examples were dried in a hot air dryer at 90 ℃ for 1 hour. After drying, MFR (melt flow rate) (g/10min) was measured using a melt flow index meter (P-111, manufactured by Toyo Seiki Seisaku-sho Co., Ltd.) under conditions of a cylinder set temperature of 250 ℃ and a load of 10kg in accordance with ISO 1133.
As an evaluation criterion, the higher the measurement value, the better the molding fluidity.
(4. tensile Strength)
Tensile strength (MPa) was measured at 23 ℃ according to ISO527 using a multipurpose test piece type A dumbbell shaped molding piece of ISO3167 manufactured in 1.
As an evaluation criterion, the higher the measured value is, the more excellent the mechanical properties are judged to be, and particularly, when the measured value is 130MPa or more, it is judged to be preferable as the resin composition of the present embodiment.
(5. bending Strength)
The multipurpose A-type dumbbell test piece prepared in 1.5 above was cut to prepare a test piece of 80mm by 10mm by 4 mm. Using the test piece, the flexural strength (MPa) was measured at 23 ℃ in accordance with ISO 178.
As an evaluation criterion, the higher the measured value is, the more excellent the mechanical properties are judged to be, and particularly, when the measured value is 170MPa or more, it is judged to be preferable as the resin composition of the present embodiment.
(6. evaluation of mold MD)
Pellets of the resin compositions produced in examples and comparative examples were dried in a hot air dryer at 90 ℃ for 1 hour. The dried resin composition was continuously molded into a flat plate by using an injection molding machine (IS-80EPN, manufactured by toshiba machines corporation) equipped with a needle gate flat plate mold having a thickness of 150mm × 150mm × 2mm, and setting a cylinder temperature of 320 ℃, a mold temperature of 120 ℃, an injection pressure (gauge pressure) of 70MP), an injection speed (panel set value) of 85%, and an extrusion time/cooling time of 10sec/30 sec.
The case where MD adhesion was visually confirmed in the mold at the time of continuous molding of 100 shots or less was evaluated as x, the case where MD adhesion was visually confirmed in the mold after 200 shots was evaluated as Δ, the case where MD adhesion was not visually confirmed in the mold after 200 shots was evaluated as good, and the case where MD adhesion was not visually confirmed in the mold after 300 shots was evaluated as excellent.
As an evaluation criterion, excellent MD prevention is judged to be good when it is not less than good, and is particularly preferable as the resin composition of the present embodiment when it is not less than good.
(7. thin wall flame retardancy)
Using 5 long molded pieces having a thickness of 0.7mm, the flame retardancy was evaluated based on the UL-94 vertical flame test method. The number of seconds of combustion (5 sheets × 2 times, 10 times total flame contact) at the time of first flame contact and the time of second flame contact was measured for each of the elongated molded sheets, and the difference between the minimum number of seconds of combustion and the maximum number of seconds of combustion was calculated.
In particular, when the flame retardant rating is determined to be V-0 and the difference between the minimum number of seconds of combustion and the maximum number of seconds of combustion is within 5 seconds, it is determined that the flame retardant is preferable as the resin composition of the present embodiment.
[ raw materials ]
< polyphenylene Ether (A) >
(A-1)
Poly (2, 6-dimethyl-1, 4-phenylene) ether powder (A-1) having a reduced viscosity of 0.50dL/g (measured at 30 ℃ C. in a 0.5g/dL chloroform solution), a number average molecular weight of 18300, 0.71 terminal OH groups per 100 units, and 0.39N, N-dibutylaminomethyl groups per 100 units was prepared by solution polymerization (hereinafter, this may be abbreviated as "(A-1)").
(A-2)
The powder mixture was fed from a first raw material feed port (top feed port) of a twin-screw extruder (ZSK 25 extruder, manufactured by Coperion corporation) by mixing 97 parts by mass of the above (A-1) with 3 parts by mass of maleic anhydride (manufactured by Mitsubishi chemical corporation) by a tumble mixer, and melt-kneaded under conditions of a barrel temperature of 300 ℃, a screw rotation speed of 300rpm, an extrusion rate of 10kg/hr, and a degree of vacuum of 7.998kPa (60Torr) to obtain pellets (A-2) (hereinafter, this may be referred to as "(A-2)").
The pellet was dissolved in chloroform, and reprecipitated with methanol to extract a polyphenylene ether component. Thereafter, vacuum drying was carried out at 60 ℃ for 4 hours to obtain a powder of polyphenylene ether (A-2).
The obtained polyphenylene ether (A-2) powder can be obtained by1H-NMR was determined by subjecting1The integral value of peaks appearing at 2.5 to 4.0ppm in H-NMR was divided by the integral value of peaks at 6.0 to 7.0ppm derived from the aromatic ring of polyphenylene ether, and it was confirmed that polyphenylene ether monomer had 0.3 structures of the following chemical formula (4) per 100 units.
[ solution 8]
1H-NMR measurement conditions
The device comprises the following steps: JEOL-ECA500
And (3) observing a nucleus:1H
observation frequency: 500.16MHz
The determination method comprises the following steps: single pulse method
Pulse width: 7 musec
Waiting time: 5 seconds
Integration times: 512 times (twice)
Solvent: CDCl3
Sample concentration: 5 w%
Chemical shift standard: TMS 0.00ppm
< polystyrene (B) >
(B-1) General Purpose Polystyrene (GPPS) (trade name: Polystyrene 680 (registered trademark), manufactured by Asahi chemical Co., Ltd.) (hereinafter sometimes referred to as "(B-1)") was used.
< condensed phosphoric acid ester-based flame retardant (C) >
(C-1) bisphenol A bis (diphenylphosphate) (FR) (aromatic phosphate-based flame retardant, trade name: CR741 (registered trade name), manufactured by Dai chemical Co., Ltd.) (hereinafter, sometimes referred to as "(C-1)") was used.
(C-2) A compound (FR) represented by the following chemical formula (5) (solid state at room temperature (23 ℃) is used, and the trade name is PX-200 (registered trademark), manufactured by Daihuai chemical Co., Ltd.) (hereinafter, it may be referred to as "(C-2)").
[ solution 9]
< glass fiber (D) >
(D-1) Glass Fiber (GF) (trade name: EC 103 MM 910[ registered trademark ], manufactured by NSG VETROTEX corporation) (hereinafter, sometimes referred to as "(D-1)") having an average fiber diameter of 10 μm, which was surface-treated with an aminosilane compound, was used.
Comparative example 1
57 parts by mass of (A-1) was fed from the uppermost stream portion (top feed port) of a ZSK40MC twin-screw extruder (screw mode having 2 kneading discs L, 6 kneading discs R, and 4 kneading discs N) having a barrel number of 13 and a screw diameter of 40mm manufactured by Werner & Pfleiderer, Germany, 13 parts by mass of (C-1) was added from the midway barrel 5 using a liquid-feeding nozzle, 30 parts by mass of (D-1) was further fed from the midway barrel 8 side, and melt-kneaded under conditions of a barrel temperature of 300 ℃, a screw rotation speed of 300rpm, and an extrusion rate of 100kg/h to obtain a resin composition. The results of the physical property test of the resin composition are shown in table 1.
[ example 1]
57 parts by mass of (A-1) and 0.5 part by mass of (C-2) were fed from the uppermost stream portion (top feed port) by the twin-screw extruder used in comparative example 1, 12.5 parts by mass of (C-1) was added from the middle cylinder 5 using a liquid-feeding nozzle, and 30 parts by mass of (D-1) was fed from the middle cylinder 8 side, and melt-kneaded under conditions of a cylinder temperature of 300 ℃, a screw rotation speed of 300rpm, and an extrusion rate of 100kg/h to obtain a resin composition. The results of the physical property test of the resin composition are shown in table 1.
[ example 2]
57 parts by mass of (A-1) and 1 part by mass of (C-2) were fed from the uppermost stream portion (top feed port) by the twin-screw extruder used in comparative example 1, 12 parts by mass of (C-1) were added from the middle cylinder 5 using a liquid-feeding nozzle, and 30 parts by mass of (D-1) were further fed from the middle cylinder 8 side, and melt-kneaded under the conditions of a cylinder temperature of 300 ℃, a screw rotation speed of 300rpm, and an extrusion rate of 100kg/h, to obtain a resin composition. The results of the physical property test of the resin composition are shown in table 1.
[ example 3]
52 parts by mass of (A-1), 5 parts by mass of (A-2) and 1 part by mass of (C-2) were fed from the uppermost stream portion (top feed port) by the twin-screw extruder used in comparative example 1, 12 parts by mass of (C-1) were added from the middle cylinder 5 using a liquid-adding nozzle, and 30 parts by mass of (D-1) were fed from the middle cylinder 8 side, and melt-kneaded under the conditions of a cylinder temperature of 300 ℃, a screw rotation speed of 300rpm and an extrusion rate of 100kg/h, to obtain a resin composition. The results of the physical property test of the resin composition are shown in table 1.
[ example 4]
57 parts by mass of (A-1) and 3 parts by mass of (C-2) were fed from the uppermost stream portion (top feed port) by the twin-screw extruder used in comparative example 1, 10 parts by mass of (C-1) were added from the middle cylinder 5 using a liquid-feeding nozzle, and 30 parts by mass of (D-1) were further fed from the middle cylinder 8 side, and melt-kneaded under conditions of a cylinder temperature of 300 ℃, a screw rotation speed of 300rpm, and an extrusion rate of 100kg/h, to obtain a resin composition. The results of the physical property test of the resin composition are shown in table 1.
[ example 5]
57 parts by mass of (A-1) and 6 parts by mass of (C-2) were fed from the uppermost stream portion (top feed port) by the twin-screw extruder used in comparative example 1, 7 parts by mass of (C-1) were added from the middle cylinder 5 using a liquid-feeding nozzle, and 30 parts by mass of (D-1) were further fed from the middle cylinder 8 side, and melt-kneaded under conditions of a cylinder temperature of 300 ℃, a screw rotation speed of 300rpm, and an extrusion rate of 100kg/h, to obtain a resin composition. The results of the physical property test of the resin composition are shown in table 1.
[ example 6]
57 parts by mass of (A-1) and 8 parts by mass of (C-2) were fed from the uppermost stream portion (top feed port) by the twin-screw extruder used in comparative example 1, 5 parts by mass of (C-1) were added from the middle cylinder 5 using a liquid-feeding nozzle, and 30 parts by mass of (D-1) were further fed from the middle cylinder 8 side, and melt-kneaded under the conditions of a cylinder temperature of 300 ℃, a screw rotation speed of 300rpm, and an extrusion rate of 100kg/h, to obtain a resin composition. The results of the physical property test of the resin composition are shown in table 1.
[ example 7]
57 parts by mass of (A-1), 2 parts by mass of (C-1) and 11 parts by mass of (C-2) were fed from the uppermost stream portion (top feed port) by the twin-screw extruder used in comparative example 1, and 30 parts by mass of (D-1) were fed from the middle of the barrel 8 side, and melt-kneaded under conditions of a barrel temperature of 300 ℃, a screw rotation speed of 300rpm and an extrusion rate of 100kg/h, to obtain a resin composition. The results of the physical property test of the resin composition are shown in table 1.
[ example 8]
57 parts by mass of (A-1) and 13 parts by mass of (C-2) were fed from the uppermost stream portion (top feed port) by the twin-screw extruder used in comparative example 1, and 30 parts by mass of (D-1) were fed from the middle of the barrel 8 side, and melt-kneaded under conditions of a cylinder temperature of 300 ℃, a screw rotation speed of 300rpm, and an extrusion rate of 100kg/h, to obtain a resin composition. The results of the physical property test of the resin composition are shown in table 1.
Comparative example 2
61 parts by mass of (A-1) and 9 parts by mass of triphenyl phosphate (trade name: TPP [ registered trademark ]. manufactured by Daihachi chemical Co., Ltd.) as a phosphate-based flame retardant were fed from the uppermost stream portion (top feed port) by the twin-screw extruder used in comparative example 1, and 30 parts by mass of (D-1) was fed from the middle of the barrel 8 side and melt-kneaded under conditions of a cylinder temperature of 300 ℃, a screw rotation speed of 300rpm, and an extrusion rate of 100kg/h, to obtain a resin composition. The results of the physical property test of the resin composition are shown in table 1.
[ example 9]
54 parts by mass of (A-1), 3 parts by mass of (B-1) and 3 parts by mass of (C-2) were fed from the uppermost stream portion (top feed port) by the twin-screw extruder used in comparative example 1, 10 parts by mass of (C-1) were added from the middle cylinder 5 using a liquid-adding nozzle, and 30 parts by mass of (D-1) were fed from the middle cylinder 8 side, and melt-kneaded under the conditions of a cylinder temperature of 300 ℃, a screw rotation speed of 300rpm and an extrusion rate of 100kg/h, to obtain a resin composition. The results of the physical property test of the resin composition are shown in table 1.
[ example 10]
52 parts by mass of (A-1), 5 parts by mass of (B-1) and 3 parts by mass of (C-2) were fed from the uppermost stream portion (top feed port) by the twin-screw extruder used in comparative example 1, 10 parts by mass of (C-1) were added from the middle cylinder 5 using a liquid-adding nozzle, and 30 parts by mass of (D-1) were fed from the middle cylinder 8 side, and melt-kneaded under the conditions of a cylinder temperature of 300 ℃, a screw rotation speed of 300rpm and an extrusion rate of 100kg/h, to obtain a resin composition. The results of the physical property test of the resin composition are shown in table 1.
Comparative example 3
51 parts by mass of (A-1), 6 parts by mass of (B-1) and 3 parts by mass of (C-2) were fed from the uppermost stream portion (top feed port) by the twin-screw extruder used in comparative example 1, 10 parts by mass of (C-1) were added from the middle cylinder 5 using a liquid-adding nozzle, and 30 parts by mass of (D-1) were fed from the middle cylinder 8 side, and melt-kneaded under the conditions of a cylinder temperature of 300 ℃, a screw rotation speed of 300rpm and an extrusion rate of 100kg/h, to obtain a resin composition. The results of the physical property test of the resin composition are shown in table 1.
[ example 11]
45 parts by mass of (A-1) and 4 parts by mass of (C-2) were fed from the uppermost stream portion (top feed port) of the twin-screw extruder used in comparative example 1, 11 parts by mass of (C-1) were added from the middle cylinder 5 using a liquid-feeding nozzle, and 40 parts by mass of (D-1) were fed from the middle cylinder 8 side, and melt-kneaded under conditions of a cylinder temperature of 300 ℃, a screw rotation speed of 300rpm, and an extrusion rate of 100kg/h, to obtain a resin composition. The results of the physical property test of the resin composition are shown in table 1.
Comparative example 4
45 parts by mass of (A-1) and 15 parts by mass of phenyl phosphazenate (trade name: Rabile FP-110[ registered trade name ]. manufactured by Volvariella pharmaceutical Co., Ltd.) as a phosphazene flame retardant were fed from the most upstream part (top feed port) by the twin-screw extruder used in the above comparative example 1, and 40 parts by mass of (D-1) was fed from the cylinder 8 side in the middle, and melt-kneaded under conditions of a cylinder temperature of 300 ℃, a screw rotation speed of 300rpm, and an extrusion rate of 100 kg/hr to obtain a resin composition. The results of the physical property test of the resin composition are shown in table 1.
[ example 12]
68 parts by mass of (A-1) and 4 parts by mass of (C-2) were fed from the uppermost stream portion (top feed port) of the twin-screw extruder used in comparative example 1, 13 parts by mass of (C-1) were added from the middle cylinder 5 using a liquid-feeding nozzle, and 15 parts by mass of (D-1) were further fed from the middle cylinder 8 side, and melt-kneaded under conditions of a cylinder temperature of 300 ℃, a screw rotation speed of 300rpm, and an extrusion rate of 100kg/h, to obtain a resin composition. The results of the physical property test of the resin composition are shown in table 1.
[ example 13]
80 parts by mass of (A-1), 3 parts by mass of (A-2), and 1 part by mass of (C-2) were fed from the uppermost stream portion (top feed port) by the twin-screw extruder used in comparative example 1, 5 parts by mass of (C-1) were added from the middle cylinder 5 using a liquid-feeding nozzle, and 11 parts by mass of (D-1) were fed from the middle cylinder 8 side, and melt-kneaded under the conditions of a cylinder temperature of 300 ℃, a screw rotation speed of 300rpm, and an extrusion rate of 100kg/h, to obtain a resin composition. The results of the physical property test of the resin composition are shown in table 1.
[ example 14]
23 parts by mass of (A-1), 2 parts by mass of (B-1) and 8 parts by mass of (C-2) were fed from the uppermost stream portion (top feed port) of the twin-screw extruder used in comparative example 1, 17 parts by mass of (C-1) were added from the middle cylinder 5 using a liquid-adding nozzle, and 50 parts by mass of (D-1) were further fed from the middle cylinder 8 side, and melt-kneaded under conditions of a cylinder temperature of 300 ℃, a screw rotation speed of 300rpm and an extrusion rate of 100kg/h, to obtain a resin composition. The results of the physical property test of the resin composition are shown in table 1.
[ example 15]
54 parts by mass of (A-1), 3 parts by mass of (C-2), and 3 parts by mass of a phenolterpene resin (trade name: YS Polymer T160[ registered trademark ]. Yasuhara Chemical Co.) were fed from the uppermost stream portion (top feed port) by a twin-screw extruder used in the above comparative example 1, 10 parts by mass of (C-1) were added from the midway cylinder 5 using a liquid-adding nozzle, and 30 parts by mass of (D-1) were further fed from the midway cylinder 8 side, and melt-kneaded under conditions of a cylinder temperature of 300 ℃, a screw rotation speed of 300rpm, and an extrusion rate of 100kg/h, to obtain a resin composition. The results of the physical property test of the resin composition are shown in table 1.
As shown in Table 1, in the resin composition of comparative example 1, since the component (C) contained only (C-1) and not (C-2), the fluctuation in the number of seconds of combustion among test pieces in the combustion test was large, and the flame retardancy was insufficient.
In the resin compositions of examples 1 to 8 and 11 to 15, the blending amounts of the components (A), (C) and (D) were within the ranges specified in the present application, so that the fluctuation in the number of seconds of burning between test pieces in the burning test was extremely small and the balance of other physical properties was good. In particular, in examples 2 to 5 and 11 to 15, no MD (mold deposit) adhesion was observed on the mold after the continuous molding of 300 shots. On the other hand, in examples 1 and 6 to 8, no MD adhesion was confirmed on the mold up to 200 injections, but MD was slightly confirmed after 300 injections. That is, in examples 2 to 5 and 11 to 15, it was confirmed that the MD adhesion on the mold tends to be further improved by containing these two components in a ratio of (C1) of 50 to 95% by mass and (C2) of 50 to 5% by mass. The reason for this is not clear, but it is presumed that by having (C-1) and (C-2) present in the composition in the above ratio, the MD component is more likely to adhere to the surface layer portion side of the molded article than the mold surface, and the MD is less likely to accumulate on the mold.
In example 3, the DTUL, charpy impact strength, tensile strength, and flexural strength tend to be improved as compared with example 2. It is believed that this is because the combination of the component (A-1) and the component (A-2) which is a modified polyphenylene ether functionalized with maleic anhydride improves the adhesion between the resin component and the glass fiber which is the component (D-1).
In comparative example 2, the use of components other than the component (C) of the present invention as a flame retardant component generates a large amount of gas during molding, and is not necessarily sufficient in the working environment. In addition, significant MD was confirmed on the mold in the vicinity of more than 20 shots of continuous molding. Although the physical properties and the flame retardancy were good in grade, the combustion test showed large variation in the number of seconds of combustion between test pieces.
In examples 9 and 10, since the blending amounts of the components (A), (B), (C) and (D) were within the range of the present application, the fluctuation in the number of seconds of combustion among test pieces in the combustion test was small, and the balance of other physical properties was also good. In comparative example 3, the blending amount of the component (B) is out of the range specified in the present invention, and the flame retardancy is remarkably lowered. And also, the fluctuation in the number of seconds of combustion among the test pieces in the combustion test was large.
In comparative example 4, components other than the component (C) of the present application were used as the flame retardant component, and the molding flowability was low and the molding processability was not necessarily sufficient. In addition, MD generation was confirmed around more than 50 injections in continuous molding. The combustion test was conducted with a large fluctuation in the number of seconds of combustion between the test pieces.
In particular, in examples 1 to 4, molded articles having a thickness of 2.0mm and a thickness of 0.5mm were produced and subjected to a vertical burning test, and the result was V-0.
Industrial applicability
The polyphenylene ether resin composition of the present invention has heat resistance, mechanical properties such as tensile strength and flexural strength, and the like, which can be effectively used even in a use environment where long-term durability is required, and further has excellent flame retardancy in a combustion test using a thin molded sheet, and is extremely small in mold MD and gas generation during continuous molding, and can be effectively used as a resin molded article used for a long period of time under high temperature conditions, particularly a cooling fan for electric/electronic equipment.
Claims (14)
1. A polyphenylene ether resin composition characterized in that,
the composition comprises polyphenylene oxide (A), styrene resin (B), flame retardant (C) and glass fiber (D),
the content of each component relative to 100 mass% of the total amount of the components (A), (B), (C) and (D) is: (A) 20 to 84% by mass of component (B), 0to 5% by mass of component (B), 5 to 25% by mass of component (C), and 11 to 50% by mass of component (D),
the component (C) comprises 0to 97 mass% of bisphenol A bis (diphenyl phosphate) (C-1) and 100 to 3 mass% of a condensed phosphate flame retardant (C-2) represented by the following chemical formula (1) with respect to 100 mass% of the component (C),
[ solution 1]
In the formula (1), R1～R4Is 2, 6-xylyl, and n is 1-3.
2. The polyphenylene ether resin composition according to claim 1, wherein the total content of the components (A), (B), (C) and (D) is 90% by mass or more of the total polyphenylene ether resin composition.
3. The polyphenylene ether resin composition according to claim 1 or 2, wherein a part or all of the component (A) is a functionalized polyphenylene ether functionalized with a carboxylic acid or an acid anhydride.
4. The polyphenylene ether resin composition according to claim 1 or 2, wherein the component (C) is a mixture of the component (C-1) and the component (C-2), and the component (C) contains 50 to 95% by mass of the component (C-1) and 50 to 5% by mass of the component (C-2) with respect to 100% by mass of the component (C).
5. The polyphenylene ether resin composition according to claim 3, wherein the component (C) is a mixture of the component (C-1) and the component (C-2), and the component (C) contains 50 to 95% by mass of the component (C-1) and 50 to 5% by mass of the component (C-2) in an amount of 100% by mass.
6. The polyphenylene ether resin composition according to any one of claims 1, 2 and 5, wherein the composition has a flame retardancy rating of V-0 when subjected to a vertical burning test according to UL94 using a test piece having a thickness of 0.7 mm.
7. The polyphenylene ether resin composition according to claim 3, wherein the composition has a flame retardancy rating of V-0 when subjected to a vertical burning test according to UL94 using a test piece having a thickness of 0.7 mm.
8. The polyphenylene ether resin composition according to claim 4, wherein the composition has a flame retardancy rating of V-0 when subjected to a vertical burning test according to UL94 using a test piece having a thickness of 0.7 mm.
9. The polyphenylene ether resin composition according to claim 6, wherein the difference between the maximum number of seconds of combustion and the minimum number of seconds of combustion is 5.0 seconds or less when the vertical burning test is performed.
10. The polyphenylene ether resin composition according to claim 7 or 8, wherein the difference between the maximum number of seconds of combustion and the minimum number of seconds of combustion is 5.0 seconds or less when the vertical combustion test is performed.
11. A molded article comprising the polyphenylene ether resin composition according to any one of claims 1 to 10.
12. The molding according to claim 11, wherein the molding has a thickness of 0.5 to 2.0mm and a flame retardancy rating of V-0 when subjected to a vertical flame test according to UL 94.
13. The molded body according to claim 11 or 12, wherein the molded body is a cooling fan for electric/electronic equipment.
14. A method for improving the fluctuation of burning time in a vertical burning test conducted using a test piece having a thickness of 0.7mm according to UL94 in a polyphenylene ether resin composition containing a polyphenylene ether (A), a styrene resin (B), a flame retardant (C) and a glass fiber (D), the contents of the respective components being such that the difference between the minimum burning seconds and the maximum burning seconds is 100 mass% relative to the total amount of the components (A), (B), (C) and (D): (A) 20 to 84% by mass of component (B), 0to 5% by mass of component (B), 5 to 25% by mass of component (C), and 11 to 50% by mass of component (D),
a mixture containing 0to 97% by mass of bisphenol A bis (diphenyl phosphate) (C-1) and 100 to 3% by mass of a condensed phosphate flame retardant (C-2) represented by the following chemical formula (1) based on 100% by mass of the component (C) is used as the flame retardant (C),
[ solution 2]
In the formula (1), R1～R4Is 2, 6-xylyl, and n is 1-3.
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| JP2018137972A JP7062546B2 (en) | 2018-07-23 | 2018-07-23 | Polyphenylene ether-based resin composition, molded product, and method for improving variation in burning time |
| JP2018-137972 | 2018-07-23 |
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| CN102675852A (en) * | 2012-04-10 | 2012-09-19 | 江苏启蓝新材料有限公司 | Halogen-free flame-retardant polyphenyl ether composition |
| CN105340024A (en) * | 2013-07-05 | 2016-02-17 | 旭化成化学株式会社 | Electrical component equipped with insulating resin molded article and method for stabilizing flame retardancy |
| JP2017179343A (en) * | 2016-03-28 | 2017-10-05 | 旭化成株式会社 | Polyphenylene ether resin composition |
| CN107892807A (en) * | 2016-10-04 | 2018-04-10 | 旭化成株式会社 | Fire retardant resin composition |
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| JP2000119515A (en) * | 1998-10-14 | 2000-04-25 | Mitsubishi Engineering Plastics Corp | Polyamide resin composition |
| JPH1180535A (en) * | 1997-09-04 | 1999-03-26 | Sumitomo Chem Co Ltd | Thermoplastic resin composition |
| JP4381637B2 (en) | 2001-05-21 | 2009-12-09 | 帝人化成株式会社 | Thermoplastic resin composition and chassis molded product |
| ATE548426T1 (en) * | 2001-11-30 | 2012-03-15 | Polyplastics Co | FLAME-RESISTANT RESIN COMPOSITION |
| JP6231429B2 (en) | 2014-04-28 | 2017-11-15 | 旭化成株式会社 | Polyphenylene ether-based resin composition and molded body, and method for producing polyphenylene ether-based resin composition |
| JP6472331B2 (en) | 2015-06-01 | 2019-02-20 | 旭化成株式会社 | Fan molded product |
| JP2017119739A (en) | 2015-12-28 | 2017-07-06 | 三菱エンジニアリングプラスチックス株式会社 | Resin composition and molding |
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2018
- 2018-07-23 JP JP2018137972A patent/JP7062546B2/en active Active
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102675852A (en) * | 2012-04-10 | 2012-09-19 | 江苏启蓝新材料有限公司 | Halogen-free flame-retardant polyphenyl ether composition |
| CN105340024A (en) * | 2013-07-05 | 2016-02-17 | 旭化成化学株式会社 | Electrical component equipped with insulating resin molded article and method for stabilizing flame retardancy |
| JP2017179343A (en) * | 2016-03-28 | 2017-10-05 | 旭化成株式会社 | Polyphenylene ether resin composition |
| CN107892807A (en) * | 2016-10-04 | 2018-04-10 | 旭化成株式会社 | Fire retardant resin composition |
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| JP7062546B2 (en) | 2022-05-06 |
| TWI735891B (en) | 2021-08-11 |
| CN110746762A (en) | 2020-02-04 |
| TW202007728A (en) | 2020-02-16 |
| JP2020015788A (en) | 2020-01-30 |
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