KR20150067480A - Halogen based flame retardant glass fiber reinforced polyamide resin composition, and electronic product - Google Patents
Halogen based flame retardant glass fiber reinforced polyamide resin composition, and electronic product Download PDFInfo
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- KR20150067480A KR20150067480A KR1020130152900A KR20130152900A KR20150067480A KR 20150067480 A KR20150067480 A KR 20150067480A KR 1020130152900 A KR1020130152900 A KR 1020130152900A KR 20130152900 A KR20130152900 A KR 20130152900A KR 20150067480 A KR20150067480 A KR 20150067480A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with 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
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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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
- C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- 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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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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
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
- C08L2666/84—Flame-proofing or flame-retarding additives
Abstract
The present invention relates to a halogen-based flame-retardant glass fiber-reinforced polyamide resin composition and an electric / electronic component, and more particularly, to a flame retardant glass fiber- A halogen-flame-retardant glass fiber-reinforced polyamide resin composition having an excellent appearance, and an electric / electronic part made of the composition.
Description
More particularly, the present invention relates to a halogen-based flame-retardant glass fiber-reinforced polyamide resin composition and electric and electronic parts, Flame retardant glass fiber reinforced polyamide resin composition having excellent appearance, and electrical and electronic parts made of the composition.
Polyamide resin, which is a kind of engineering plastics, has excellent mechanical strength, abrasion resistance, heat resistance, chemical resistance, electrical insulation and arc resistance and is used in a wide range of applications such as automobiles, electric / electronic parts and industrial materials.
Especially, when it is used for electric and electronic parts and the like, flame retardancy is required as an important property in preparation for fire.
The polyamide resin itself has no flame retardant property, and therefore, a method of adding or copolymerizing a halogen compound or a non-halogen compound or a method of adding an inorganic compound or metal hydroxide has been studied for imparting flame retardancy.
The glass fiber-reinforced polyamide material in which the halogen-based flame retardant is blended to improve the flame retardancy should have excellent appearance characteristics when applied to electrical and electronic parts. However, when a large amount of flame retardant is used to secure the flame retardancy, flame retardancy can be ensured, but gas marks are generated on the appearance, and mechanical properties such as tensile properties are deteriorated. Therefore, development of a halogen-based flame-retardant glass fiber-reinforced polyamide resin composition capable of solving the problems is urgently required.
The present invention relates to a halogen-based flame-retardant glass fiber-reinforced polyamide resin composition for electrical and electronic devices, which has a flame retardancy and a good appearance, and relates to a styrene-maleimide-based copolymer An object of the present invention is to provide an electric and electronic part which is obtained by securing mechanical properties such as flame retardance, appearance and tensile strength while avoiding excessive use of a halogen-based flame retardant conventionally added.
In order to achieve the above object, the present invention provides a polyamide mixed resin; Styrene-maleimide-based copolymer; Halogen-based flame retardants; And a glass fiber. The present invention also provides a halogen-based flame-retardant glass fiber-reinforced polyamide resin composition.
The present invention also relates to a polyamide mixed resin; Styrene-maleimide-based copolymer; Halogen-based flame retardants; And glass fibers are extrusion-extruded under a barrel temperature of 280 to 300 占 폚 to produce a halogen-free glass fiber-reinforced polyamide resin.
Further, the present invention provides an electric / electronic part characterized by being molded with the above composition.
As described above, according to the present invention, when a large amount of flame retardant is used as a halogen-flame retardant glass fiber-reinforced polyamide resin composition based on mixed resin of polyamide, which is one kind of engineering plastics, excellent flame retardancy characteristics can be secured, And a tensile strength and a tensile strength of the flame retardant and the external appearance of the electrical and electronic parts manufactured by using the conventional halogen-containing flame retardant, while avoiding excessive use of the halogen- And mechanical properties such as tensile strength can be secured.
Hereinafter, the present invention will be described in detail.
The halogen-based flame retardant glass fiber-reinforced polyamide resin composition of the present invention comprises a polyamide mixed resin; Styrene-maleimide-based copolymer; Halogen-based flame retardants; And glass fibers.
The term "polyamide mixed resin" used in the present invention refers to a mixture of two or more polyamide resins unless otherwise specified.
As the polyamide mixed resin, for example, a lactam having a cyclic structure or a polycondensation of two or more kinds of w-amino acids may be used, and diacids and diamines may be used. Further, homopolyamides, copolyamide types can also be used.
Specific examples of the polyamide mixed resin include polyhexamethylenediamine adipamide (nylon 6,6), polyhexamethylenediamine sebacamide (nylon 6,10), polyhexamethylene lauroamide (nylon 6,12) , Polytetramethylenediamine adipamide (nylon 4,6), and at least one polyamide selected from at least one of polycaprolactam (nylon 6) and polylauroractam (nylon 12) A mixture of the second resin is preferable in terms of complementing the physical properties of the appearance.
As a specific example, the polyamide mixed resin may be a crystalline, semicrystalline or amorphous resin of 10 to 60 wt% of the polyamide first resin and 90 to 40 wt% of the second polyamide resin.
As another example, the polyamide mixed resin may be a crystalline, semicrystalline or amorphous resin of 20 to 40 wt% of the polyamide first resin and 60 to 80 wt% of the second polyamide resin.
Examples of the polyamide mixed resin include 40-85% by weight, 45-60% by weight, or 45-50% by weight of the total 100% by weight of the polyamide mixed resin, the styrene-maleimide copolymer, the halogen- % ≪ / RTI >
The styrene-maleimide-based copolymer is included for securing excellent appearance characteristics, and can improve the compatibility between the polyamide mixed resin and the halogen-based flame retardant.
The styrene-maleimide-based copolymer may be, for example, a copolymer of 40 to 60% by weight of a styrene-based monomer and 60 to 40% by weight of a maleimide-based monomer.
As a specific example, the styrene-maleimide-based copolymer may be a copolymer of 40 to 50% by weight of a styrene-based monomer, 40 to 59% by weight of a maleimide-based monomer, and 1 to 10% by weight of a maleic anhydride.
As another example, the styrene-maleimide-based copolymer may have a pyrolysis temperature of 300 ° C or higher, or 300 ° C to 400 ° C, as measured by a TGA (Thermogravimetric Analyzer).
The maleimide-based monomer may be at least one member selected from methylmaleimide, ethylmaleimide, butylmaleimide, cyclohexylmaleimide, and N-phenylmaleimide.
The styrene-maleimide-based copolymer may be used in an amount of 0.1 to 10% by weight, 0.1 to 5% by weight, or 0.5% by weight, based on 100% by weight of the total of the polyamide mixed resin, the styrene-maleimide copolymer, the halogen- To 5% by weight.
The halogen-based flame retardant may be, for example, a halogen-containing polystyrene resin. The halogen may be bromine, chlorine or the like.
As a specific example, the halogen-based flame retardant may be selected from a mixture of modified polystyrene containing a butadiene rubber and polystyrene resin, for example.
As another example, the halogen-based flame retardant may be a polystyrene-based resin containing 60 to 65% by weight of bromine.
The halogen-containing polystyrene-based resin may be, for example, 20 to 40% by weight or 20 to 25% by weight based on 100% by weight of the polyamide mixed resin, styrene-maleimide copolymer, halogen-based flame retardant and glass fiber .
The glass fibers may have a diameter of, for example, 10 to 20 μm, 10 to 15 μm, or 10 to 13 μm, and may have a length of 1 to 5 mm, or 2 to 3 mm.
As a specific example, the glass fiber may be surface treated with aminosilane as elliptical glass fiber.
In another example, the glass fibers have an aspect ratio (L / D) of length (glass fiber length L) / cross section (glass fiber cross section D) of 50 to 300, 200 to 300, 210 to 260, or 215 to 245 In the above range, the polypropylene resin composition maintains a very strong bonding force between the polymers to increase the rigidity, thereby playing a role of replacing expensive resins and metals in the processing of plastic parts such as automobiles in which stiffness is given priority. can do.
The cross section D corresponds to the longest side of the cross section when the cross section cut perpendicular to the longitudinal direction of the glass fiber is a rectangle, and the longest cross section when the cross section is elliptic cross section.
As another example, the glass fiber may have a rectangular or elliptical cross section cut perpendicular to the longitudinal direction.
As another example, when the cross section of the glass fiber cut in the direction perpendicular to the longitudinal direction is rectangular, the shortest side is 5 to 15 탆, or 7 to 11 탆, or the shortest diameter is 5 to 15 탆 when it is elliptical, or 7 to 10 [micro] m.
The glass fiber may be, for example, 10 to 30% by weight or 20 to 25% by weight based on 100% by weight of the total of the polyamide mixed resin, the styrene-maleimide copolymer, the halogen-based flame retardant and the glass fiber.
The halogen-flame retardant glass fiber reinforced polyamide resin composition of the present invention can be suitably used as a lubricant, an antioxidant, a light stabilizer, a chain extender, a catalyst, a release agent, a pigment, a dye, an antistatic agent, an antibacterial agent, , A glass fiber, an anti-friction agent, a wear-resistant agent, and a coupling agent. The additive may be used within a range that does not adversely affect the physical properties of the halogen-based flame retardant glass fiber-reinforced polyamide resin composition of the present invention.
The halogen-based flame-retardant glass fiber-reinforced polyamide resin composition of the present invention is optionally mixed with the above additives in a mixer or a super mixer and then mixed with a twin-screw extruder, a single-screw extruder, kneading at 200 to 300 ° C or at a temperature range of 280 to 300 ° C using one of various mixing processing machines such as roll mills, kneaders or banbury mixers, And the pellet is sufficiently dried by using a dehumidifying dryer or a hot air drier and then injection-processed to produce a halogen-flame retardant glass fiber-reinforced polyamide resin.
According to the present invention, there is provided a flame-retardant glass fiber reinforced polyamide resin composition which is molded from the halogen-based flame retardant glass fiber-reinforced polyamide resin composition and has high appearance and moldability required for use in electric and electronic parts, flame retardancy of V- And the like can be provided.
The electric / electronic component may be, for example, an ejected electric / electronic component, and may be, for example, a circuit breaker, a switch, a connector, or the like.
Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention, but the present invention is not limited thereto.
[Example]
Example 1 to 4
The components shown in the following Table 1 were put into a super mixer in the stated amounts and mixed well and then the mixture was extruded using a twin-screw extruder at a barrel temperature of 280 to 300 ° C After melt-kneading, pellets were obtained by extrusion processing (using a pelletizer). The pellets were dried at 80 ° C. for 4 hours or more, injection molded, and left to stand at room temperature for 1 day. The specimens were used as test specimens.
Comparative Example 1 to 6
A specimen was prepared in the same manner as in Example 1, except that the ingredients shown in Table 1 were used in the stated amounts.
* (A) Polyamide mixed resin:
(A-1) polyhexamethylenediamine adipamide (nylon 6,6)
(A-2) Polycaprolactam (nylon 6)
* (B) Halogen Flame retardant :
Polystyrene resin containing 60-65% of bromine
(C) Styrene- Maleimide system Copolymer:
MS-L2A (ternary copolymer containing 47.5% by weight of styrene, 6.2% by weight of maleic anhydride, 46.3% by weight of N-phenylmaleimide and Mw of 135,000 g / mol) of Adeka Co.,
* (D) Glass fiber:
Glass fibers having a diameter of 10 to 13 占 퐉 and a length of 3 mm of Owens corning yarn and surface-treated with aminosilane.
[Test Example]
The properties of the samples prepared from the halogen-based flame-retardant glass fiber reinforced polyamide resin compositions prepared in Examples 1 to 4 and Comparative Examples 1 to 6 were measured by the following methods, and the results are shown in Table 2 below.
[Property measurement test]
* Flame retardancy: measured by UL94 method.
Appearance: The gas mark on the surface was visually observed. In Table 5, the gas mark is clear on the surface of the specimen without any gas marks. The lower the numerical value, the worse the gas mark becomes, and the numerical value 1 means that the gas marks are visible throughout the specimen appearance.
It was measured based on ASTM D638: tensile strength *.
* Flexural strength: measured based on ASTM D790.
* Izod impact strength (sample thickness 3.2mm): measured based on ASTM D256.
* HDT (heat distortion temperature, 18.6 kgf / C): measured according to ASTM D648.
(kg / cm2)
(kg / cm2)
(kg.cm/cm)
(18.6 kgf / [deg.] C)
As shown in Table 2, when the specimen made of the halogen-based flame retardant glass fiber reinforced polyamide resin composition according to the present invention was used (Examples 1 to 4), when the styrene-maleimide copolymer was not used 1 to 6), it was confirmed that they provided mechanical properties such as high appearance and moldability, flame retardancy of V-0 grade, tensile properties, bending properties and impact strength.
In particular, the styrene-maleimide-based copolymer according to Examples 1 to 4, which showed changes in the content of the styrene-maleimide-based copolymer, proved that the styrene-maleimide-based copolymer exhibited excellent effects even in a very small amount as in Example 1. [
As a result, according to the present invention, a halogen-based flame retardant glass fiber-reinforced polyamide resin composition for electrical and electronic devices having flame retardancy and appearance can be obtained by introducing a styrene-maleimide copolymer having high- It has been found that the produced electrical and electronic parts can be provided with improved appearance characteristics while securing mechanical properties such as flame retardance and tensile strength while avoiding excessive use of halogen-based flame retardants conventionally added.
Claims (17)
Halogen flame retardant glass fiber reinforced polyamide resin composition.
The polyamide mixed resin may include polyhexamethylene diamine adipamide (nylon 6,6), polyhexamethylene sebasamide (nylon 6,10), polyhexamethylenediamine lauroamide (nylon 6,12), and polytetra (Nylon 6) and polylaurolactam (nylon 12), and at least one polyamide resin selected from at least one polyamide resin selected from the group consisting of polycaprolactam (nylon 6) and polylauroractam Characterized in that it is a mixture
Halogen flame retardant glass fiber reinforced polyamide resin composition.
Wherein the polyamide mixed resin is a resin comprising 10 to 60 wt% of a polyamide first resin and 90 to 60 wt% of a polyamide second resin
Halogen flame retardant glass fiber reinforced polyamide resin composition.
Wherein the polyamide mixed resin is 40-85 wt% of 100 wt% of the total of the polyamide mixed resin, the styrene-maleimide copolymer, the halogen-based flame retardant, and the glass fiber
Halogen flame retardant glass fiber reinforced polyamide resin composition.
Wherein the styrene-maleimide-based copolymer is a copolymer of 40 to 60% by weight of a styrene-based monomer and 40 to 60% by weight of a maleimide-based monomer
Halogen flame retardant glass fiber reinforced polyamide resin composition.
Wherein the styrene-maleimide-based copolymer is a copolymer of 40 to 50 wt% of styrene-based monomer, 40 to 59 wt% of maleimide-based monomer, and 1 to 10 wt% of maleic anhydride
Halogen flame retardant glass fiber reinforced polyamide resin composition.
The styrene-maleimide-based copolymer is a copolymer having a thermal decomposition temperature of 300 ° C or higher as measured by a TGA (Thermogravimetric Analyzer)
Halogen flame retardant glass fiber reinforced polyamide resin composition.
Wherein the styrene-maleimide-based copolymer is 0.1 to 10% by weight based on 100% by weight of the total of the polyamide mixed resin, the styrene-maleimide copolymer, the halogen-based flame retardant and the glass fiber
Halogen flame retardant glass fiber reinforced polyamide resin composition.
Wherein the halogen-based flame retardant is a halogen-containing polystyrene-based resin
Halogen flame retardant glass fiber reinforced polyamide resin composition.
Wherein the halogen-based flame retardant is a polystyrene-based resin containing 60 to 65% by weight of bromine
Halogen flame retardant glass fiber reinforced polyamide resin composition.
Wherein the halogen-containing polystyrene-based resin is 20 to 40% by weight of a total of 100% by weight of the polyamide mixed resin, the styrene-maleimide copolymer, the halogen-based flame retardant and the glass fiber
Halogen flame retardant glass fiber reinforced polyamide resin composition.
Characterized in that the glass fiber is surface-treated with aminosilane and has a diameter of 10 to 20 mu m and a length of 1 to 5 mm
Halogen flame retardant glass fiber reinforced polyamide resin composition.
Wherein the glass fiber is 10 to 30 wt% of 100 wt% of the total of the polyamide mixed resin, the styrene-maleimide copolymer, the halogen-based flame retardant, and the glass fiber
Halogen flame retardant glass fiber reinforced polyamide resin composition.
The composition can be used as a lubricant, an antioxidant, a light stabilizer, a chain extender, a catalyst, a release agent, a pigment, a dye, an antistatic agent, an antimicrobial agent, a processing aid, a metal deactivator, a fuming inhibitor, an inorganic filler, And at least one additive selected from coupling agents
Halogen flame retardant glass fiber reinforced polyamide resin composition.
Wherein the electric / electronic part is a circuit breaker, a switch, or a connector
Electric and electronic parts.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20240026695A (en) | 2022-08-22 | 2024-02-29 | 천인숙 | Manufacturing method of engineering plastic composition for electric vehicle with flame retardant properties and multi-color realizatio |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20240026695A (en) | 2022-08-22 | 2024-02-29 | 천인숙 | Manufacturing method of engineering plastic composition for electric vehicle with flame retardant properties and multi-color realizatio |
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