KR20140092455A - Polyamide Reinforced Resin Composition - Google Patents
Polyamide Reinforced Resin Composition Download PDFInfo
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- KR20140092455A KR20140092455A KR1020120156520A KR20120156520A KR20140092455A KR 20140092455 A KR20140092455 A KR 20140092455A KR 1020120156520 A KR1020120156520 A KR 1020120156520A KR 20120156520 A KR20120156520 A KR 20120156520A KR 20140092455 A KR20140092455 A KR 20140092455A
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- polyamide resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- 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
-
- 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
Abstract
The present invention relates to a polyamide resin composition, and more particularly, to a polyamide resin composition comprising a polyamide resin; Based on 100 parts by weight of the polyamide resin, 10 to 250 parts by weight of a polyphenylene ether resin; 10 to 80 parts by weight of glass fiber; 10 to 80 parts by weight of an inorganic reinforcement; And
And 2 to 20 parts by weight of a styrene-based impactproofing agent.
Description
The present invention relates to a polyamide resin composition used in the field of electric and electronic fields.
Polyamide resin, widely known as nylon resin, has excellent properties as an engineering plastic in stiffness, flexibility, abrasion resistance, solvent resistance and paintability, and is used in a large amount in various fields such as automobile, electric and electronic parts. The water absorption rate and the molding shrinkage ratio are large, and the use thereof is restricted for a product having a large size and a large size, and problems in handling have been caused. Therefore, in order to improve the dimensional stability and the water absorption rate, a technique of appropriately melting and mixing with polyphenyleneether or polyethylene oxide resin has been developed. In order to realize better mechanical properties, various fillers are used for mechanical Has increased the physical properties. However, it is insufficient to simultaneously satisfy excellent mechanical properties, dimensional stability, and excellent surface characteristics. When excessive glass fiber is added for excellent mechanical properties, the glass fiber is exposed on the surface of the product and the quality of the product is deteriorated. In order to solve this problem, the addition of other inorganic fillers reduces the quality of the surface There is a problem that the impact strength is decreased during the mechanical properties.
The present invention relates to a polyamide resin composition, and more particularly, to a polyamide resin composition which is excellent in overall rigidity, impact resistance and dimensional stability of a product, and particularly excellent in surface characteristics, such as an electric vehicle, a battery case of a hybrid vehicle, ≪ / RTI >
Electric vehicles, hybrid battery cases, battery covers, battery stacks, and battery mounts are essential parts of electric vehicles and hybrid vehicles. They must be used for a long time without any deformation due to vibration, shock, vibration, Should be excellent.
Particularly, attachments such as laser marking and sticker are applied to the surface of the injection molding, and the surface properties are demanded because of the many demands on the sensitivity quality.
The present invention aims to provide a polyamide resin composition which can exhibit excellent surface properties while exhibiting excellent rigidity, impact resistance and dimensional stability.
Accordingly, the present invention provides, as a first preferred embodiment, a polyamide resin; Based on 100 parts by weight of the polyamide resin, 10 to 250 parts by weight of a polyphenylene ether resin; 10 to 80 parts by weight of glass fiber; 10 to 80 parts by weight of an inorganic reinforcement; And 2 to 20 parts by weight of a styrene-based impactproofing agent.
The polyphenyl ether resin according to this embodiment may be used alone as a polyphenyl ether resin, or a mixture of a polyphenyl ether resin and a vinyl aromatic polymer may be used.
The glass fiber according to this embodiment may have a diameter of 8 to 15 탆 and a length of 2 to 5 mm.
The inorganic reinforcing material according to the embodiment may be at least one selected from talc, kaolin, calcium carbonate, olustonite and mica.
The styrene-type impactor according to the embodiment may be a polystyrene-polybutadiene-polystyrene triblock copolymer.
The polyamide resin composition according to this embodiment has a molding shrinkage ratio of 0.3 to 1.0% as measured by the ASTM evaluation method D 955, a tensile strength of 800 kg / cm 2 to 1500 kg / cm 2 as measured by the ASTM evaluation method D 638, and an ASTM evaluation method D 790 and that by bending strength 1300kg / cm 2 to about 2400kg / cm 2, and a flexural modulus according to ASTM evaluation method D 790 40000kg / c cm 2 to 80000kg / cm 2, the impact strength according to ASTM evaluation method D 256 5kg · cm / cm To 20 kg · cm / cm.
The polyamide resin composition according to the present invention can exhibit excellent surface characteristics while ensuring rigidity, impact resistance and dimensional stability, and can be applied to parts such as an electric vehicle, a battery case for a hybrid vehicle, a battery housing, a battery stack, .
Hereinafter, the present invention will be described in more detail.
The present invention relates to a polyamide resin composition, Based on 100 parts by weight of the polyamide resin, 10 to 250 parts by weight of a polyphenylene ether resin; 10 to 80 parts by weight of glass fiber; 10 to 80 parts by weight of an inorganic reinforcement; And 2 to 20 parts by weight of an impact resistance.
[Polyamide resin]
The polyamide resin used in the present invention may be selected from polyamide 6, polyamide 66, or a mixture thereof.
The polyamide 6 and the polyamide 66 may be those having a relative viscosity of 2.5 to 3.3 (based on a value measured with 1 g of a polymer solution in 100 ml of 96% sulfuric acid at 20 캜). When the relative viscosity is less than 2.5, An excellent effect can not be obtained from the viewpoint of improving the stability, and if it is more than 3.3, surface defects and unformed phenomena may occur due to a decrease in flowability.
The number average molecular weight of the polyamide resin may be from 20,000 to 50,000. If the number average molecular weight is less than 20,000, the rigidity is deteriorated. If the number average molecular weight is more than 50,000, the flowability is poor due to high viscosity, .
On the other hand, the polyamide resin of the present invention may be used in the form of a chip for the production of the resin composition according to the present invention and sufficiently dried in a dehumidifying dryer.
[Polyphenylene ether resin]
In the present invention, a polyphenylene ether resin may be used alone, or a mixture of a polyphenylene ether resin and a vinyl aromatic polymer may be used.
Examples of the polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl- Ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl- (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diphenyl- Copolymers of poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3,6-trimethyl- 6-triethyl-1, 4-phenylene) ether. Among these, copolymers of poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3,6-trimethyl-1,4-phenylene) ether and poly (2,6- , 4-phenylene) ether are preferable, and poly (2,6-dimethyl-1,4-pinylene) ether is more preferable.
The degree of polymerization of the polyphenylene ether is not particularly limited, but in consideration of thermal stability and workability of the resin composition, it is preferable that the intrinsic viscosity is 0.2 to 0.8 dl / g when measured in chloroform solvent at 25 캜. The polyphenylene ether may be used alone, or two or more compounds may be mixed in an appropriate ratio.
The polyphenylene ether resin has good compatibility with the vinyl aromatic polymer. Therefore, in the present invention, a mixture of a polyphenylene ether resin and a vinyl aromatic polymer can also be used. Vinyl aromatic polymers include polystyrene, high impact polystyrene, polychlorostyrene, poly alpha-methyl styrene, and poly t-butyl styrene, which may be used alone or in a mixture of two or more. Of these, polystyrene or high-order polystyrene is preferred. The molecular weight of the vinyl aromatic polymer is not particularly limited. However, considering the thermal stability and workability of the resin composition, the weight average molecular weight is preferably 20,000 to 500,000.
The content of the polyphenylene ether resin or the mixture of the polyphenylene ether resin and the vinyl aromatic polymer may be 10 to 250 parts by weight based on 100 parts by weight of the polyamide resin. When the content is less than 10 parts by weight, the dimensional stability and the water absorption rate There is a problem that it is insufficient to improve the disadvantages. When the amount is more than 250 parts by weight, the flowability is lowered, and the injection moldability is lowered and unformed is formed.
Further, when a mixture of a polyphenylene ether resin and a vinyl aromatic polymer is used, the mixture may contain 70 to 99% by weight of a polyphenylene ether resin and 1 to 30% by weight of a vinyl aromatic polymer. When the content of the vinyl aromatic polymer is more than 30% by weight, the flowability is excessively increased. However, when the amount of the vinyl aromatic polymer is more than 30% by weight, The injection moldability is deteriorated and the strength is lowered.
[Fiberglass]
The glass fiber according to the present invention may have a chop shape having a diameter of 8 to 15 mu m and a length of 2 to 5.0 mm and a surface treated with a coupling agent.
If the diameter is less than 8 占 퐉, the glass fiber is easily broken and it is not enough to improve the rigidity. When the diameter exceeds 15 占 퐉, the rigidity is improved, but the appearance quality is not obtained due to the problem of projecting on the surface.
If the length is less than 2 mm, the rigidity is not improved due to the short glass fiber length. If the length exceeds 5 mm, the rigidity is improved, but the excellent appearance quality can not be obtained due to the protrusion due to the long length.
The coupling agent is preferably a silane-based material having an organic functional group such as a vinyl group, an epoxy group, a mercaptan group or an amine group.
In the present invention, the glass fiber content may be 10 to 80 parts by weight based on 100 parts by weight of the polyamide resin. When the content of the glass fiber is less than 10 parts by weight, the effect of imparting rigidity is insignificant. When the amount of the glass fiber exceeds 80 parts by weight, the glass fiber protrudes to the surface to deteriorate appearance quality and the stiffening effect is excellent. Can occur.
The glass fiber used in the composition of the present invention is glass fiber called G or K glass and contains calcium oxide (CaO), silicon dioxide (SiO 2 ) and aluminum oxide (Al 2 O 3 ) as main components, 10 to 20% by weight of silicon dioxide, 50 to 70% by weight of silicon dioxide, and 2 to 15% by weight of aluminum oxide.
A polyamide resin composition for an electric vehicle, a battery case for a hybrid vehicle, a battery housing, a battery stack, and a battery support requires a tensile strength of 800 to 1500 kg / cm 2 and a flexural strength of 1100 to 2000 kg / cm 2. The glass fibers may be contained in the amounts as described above.
The kind of the glass fiber is not particularly limited, but it is preferable to use a glass fiber for effective expression of rigidity.
[Inorganic reinforcement]
In the present invention, the inorganic reinforcement may be selected from among talc, kaolin, calcium carbonate, olustonite and mica, and the average size (average length of the longest axis) may be 5 to 13 탆. Those having a size exceeding 13 占 퐉 have poor surface characteristics and poor fluidity, and an inorganic reinforcing material having a size of less than 5 占 퐉 is poor in workability. It is possible to increase the glass fiber content of the multi-faced fiber only for strength reinforcement. However, since the fluidity and the surface property are not good, inorganic reinforcement can be used to reinforce the strength and secure the fluidity.
When the inorganic reinforcement material is surface-treated with an organic functional group such as a vinyl group, an epoxy group, a mercaptan group or an amine group, the inorganic reinforcing material is more compatible with polyamide and more effective.
In the present invention, the content of the inorganic reinforcing material may be 10 to 80 parts by weight based on 100 parts by weight of the polyamide resin. If the content of the inorganic reinforcing material is less than 10 parts by weight, the surface improving effect by the inorganic reinforcing material becomes insignificant. If the amount is more than 100 parts by weight, the impact strength is lowered.
[Styrene-based impact resistant agent]
The impact resistant agent used in the present invention is a styrene-based impact resistant agent derived from a vinyl aromatic monomer, and may be a diblock or radial triblock copolymer of AB or ABA type.
AB or ABA type diblock or radial triblock copolymer is a copolymer composed of a vinyl aromatic monomer and a block of a hydrogenated, partially hydrogenated or unhydrogenated unsaturated diene, and is an example of an AB diblock type block copolymer Include polystyrene-polybutadiene, polystyrene-polyisoprene, polyalpha methylstyrene-polybutadiene copolymers and their hydrogenated forms. Such AB diblock copolymers are widely known commercially, and representative examples thereof include SOLPRENE by PHILLIPS and KRATON D and KRATON G by KRATON Polymers. Examples of block copolymers of the ABA triblock type include polystyrene-polybutadiene-polystyrene, polystyrene-polyisoprene-polystyrene, polyalpha methylstyrene-polybutadiene-polyalpha methylstyrene, polyalpha metal styrene-polyisoprene- , And hydrogenated forms thereof. Such ABA triblock copolymers are also widely known commercially, and KRATON G of KRATON Polymers and SEPTON of KURARAY are representative.
The content of the styrene-based impactor may be 2 to 20 parts by weight based on 100 parts by weight of the polyamide resin. If the content of the styrene-based impactor is less than 2 parts by weight, There is a problem that the rigidity is lowered.
The styrene-based impactor used in the present invention may be a hydrogenated polystyrene-polybutadiene-polystyrene triblock copolymer.
The polyamide-reinforced resin composition can be produced by extruding each component as described above using an extruder. As a mixer, a twin-screw extruder may be used for kneading at 255 ° C to 280 ° C. In order to maximize the kneading of the resin composition, an extruder having three inlet ports is used to feed a polyamide resin and polyphenylene ether Resin and a styrene-based impact resistant agent are injected into the second inlet, the mineral reinforcement is injected into the second inlet, and the glass fiber is injected into the third inlet. In order to prevent pyrolysis of the composition during melt-kneading, it is desirable to minimize the residence time. In view of dispersibility, it is necessary to adjust the rotation of the screw in the optimum range.
As described above, the polyamide resin composition according to the present invention comprises a polyamide resin, a polyphenylene ether resin, a glass fiber, an inorganic reinforcing material, and a styrene-based impact resistant agent. The polyamide resin composition has excellent tensile strength, , Excellent in dimensional stability and surface characteristics while maintaining flexural modulus and impact strength.
Further, based on the rigidity of the polyamide resin and the moisture absorption properties of the polyphenylene ether resin, and the dimensional stability of the heat resistance, etc., mechanical strength can be secured with glass fiber, and excellent surface characteristics can be obtained while improving fluidity with an inorganic reinforcing material , Impact resistance can be improved by using a styrene-based impact-resistant agent.
In particular, although there are many technologies satisfying the respective characteristics in the past, there have been limitations in application to a composition for an electric vehicle, a battery case of a hybrid vehicle, a battery cover, a battery stack, and a battery holder. The present invention has been accomplished with a novel composition.
Hereinafter, the present invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.
Example 1 to 7
Each component having the composition shown in the following Table 1 was melted and kneaded in a twin-screw extruder heated to 255 ° C to 280 ° C, and then a polyamide resin composition was prepared in a chip state. The polyamide resin composition was dried at 85 ° C for 6 hours in a dehumidifying- And each specimen was manufactured at the same temperature as that in melting and kneading using a heated screw extruder and evaluated. The results are shown in Table 2 below.
Reinforcement 5
2 Asahi Kasei Chemicals PPE Xylon S201A
3 . KRATON G from KRATON Polymers
4 . Talc: PNA400
5 . Kaolin: Translink 445
6 KCC GLASS FIBER CS311
The resin compositions prepared in Examples and Comparative Examples were evaluated for their physical properties based on the following evaluation methods.
(Evaluation Items)
1) Molding shrinkage: Mold shrinkage in the direction of flow of 1/8 inch disc test piece was measured by ASTM evaluation method D 955.
2) Tensile strength: A 1/8 inch sample was prepared according to ASTM D 638 and then measured.
3) Flexural strength and flexural modulus: A 1/8 inch specimen was prepared according to ASTM Evaluation Method D 790, and then measured
4) Impact strength: A 1/4 inch specimen was manufactured according to ASTM D 256, and measured.
5) Surface Property: The resin composition of the present invention, which was prepared after melt-kneading, was dried in a dehumidifying type dryer at 85 ° C for 6 hours and then extruded by a 150-ton injection molding machine to a width of 350 mm, a length of 100 mm, cavity (cavity) in diameter 7mm length 80mm is direct (direct) injection using a mold of square shape gate 280 ℃ temperature, the mold (mold) were fixed at a temperature of 20 ℃ only primary injection pressure without holding pressure 1,100kg / cm 2 , An injection time of 4 seconds, and a cooling time of 18 seconds, the appearance of the glass fiber at the gate portion and the flow mark were observed with naked eyes.
(kg / cm 2 )
(kg / cm 2 )
(kg / cm 2 )
(kg.cm/cm)
(%)
compare Yes 1 to 5
The polyamide resin compositions were prepared in the same manner as in Examples 1 to 7 with the composition shown in Table 3 below, and the respective test specimens were prepared by the same method, and the physical properties were evaluated. The measurement results are shown in Table 4 As shown.
Reinforcement 5
2 Asahi Kasei Chemicals PPE Xylon S201A
3 . KRATON G from KRATON Polymers
4 . Talc: PNA400
5 . Kaolin: Translink 445
6 KCC GLASS FIBER CS311
(kg / cm 2 )
(kg / cm 2 )
(kg / cm 2 )
(kg.cm/cm)
(%)
Claims (6)
With respect to 100 parts by weight of the polyamide resin,
10 to 250 parts by weight of a polyphenylene ether resin;
10 to 80 parts by weight of glass fiber;
10 to 80 parts by weight of an inorganic reinforcement; And
And 2 to 20 parts by weight of a styrene-based impactproofing agent.
Wherein the polyphenyl ether resin comprises a polyphenyl ether resin alone or a mixed resin of a polyphenyl ether resin and a vinyl aromatic polymer.
Wherein the glass fiber has a diameter of 8 to 15 mu m and a length of 2 to 5 mm.
Wherein the inorganic reinforcing material is at least one selected from the group consisting of talc, kaolin, calcium carbonate, olustonite and mica.
Wherein the styrene-based impact resistant agent is a polystyrene-polybutadiene-polystyrene triblock copolymer.
The molding shrinkage ratio according to the ASTM evaluation method D 955 is 0.3 to 1.0%
A tensile strength according to the ASTM evaluation method D 638 is 800 kg / cm 2 to 1500 kg / cm 2 ,
The flexural strength according to the ASTM evaluation method D 790 is 1300 kg / cm 2 to 2400 kg / cm 2 ,
The flexural modulus according to the ASTM Evaluation Method D 790 is 40000 kg / cm 2 to 80000 kg / cm 2
And the impact strength by the ASTM evaluation method D 256 is 5 kg · cm / cm to 20 kg · cm / cm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020120156520A KR20140092455A (en) | 2012-12-28 | 2012-12-28 | Polyamide Reinforced Resin Composition |
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020120156520A KR20140092455A (en) | 2012-12-28 | 2012-12-28 | Polyamide Reinforced Resin Composition |
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| KR20140092455A true KR20140092455A (en) | 2014-07-24 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170025664A (en) * | 2015-08-31 | 2017-03-08 | 코오롱플라스틱 주식회사 | Recycled polyamide resin composition and and molded article thereof |
-
2012
- 2012-12-28 KR KR1020120156520A patent/KR20140092455A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170025664A (en) * | 2015-08-31 | 2017-03-08 | 코오롱플라스틱 주식회사 | Recycled polyamide resin composition and and molded article thereof |
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