Polyamide composition and molded article made of the same with improved mechanical strength and reduced weight
11685833 · 2023-06-27
Assignee
- Hyundai Motor Company (Seoul, KR)
- Kia Motors Corporation (Seoul, KR)
- KTP Industries, Inc. (Gyeongsangbuk-do, KR)
Inventors
- Seul Yi (Seoul, KR)
- Boo Youn An (Busan, KR)
- Dae Sik Kim (Gyeonggi-do, KR)
- In Soo Han (Gyeonggi-do, KR)
- Kyeong Hoon Jang (Seoul, KR)
- Jin Gi Ahn (Seoul, KR)
- Byung Seok Kong (Gyeonggi-do, KR)
- Seong Won Seo (Gyeongsangbuk-do, KR)
Cpc classification
C08J5/249
CHEMISTRY; METALLURGY
C08K2201/003
CHEMISTRY; METALLURGY
C08L77/06
CHEMISTRY; METALLURGY
C08J2477/06
CHEMISTRY; METALLURGY
C08K5/005
CHEMISTRY; METALLURGY
B29C45/0001
PERFORMING OPERATIONS; TRANSPORTING
C08J5/10
CHEMISTRY; METALLURGY
C08K5/005
CHEMISTRY; METALLURGY
C08L77/06
CHEMISTRY; METALLURGY
C08J2377/06
CHEMISTRY; METALLURGY
International classification
C08L77/06
CHEMISTRY; METALLURGY
B29C45/00
PERFORMING OPERATIONS; TRANSPORTING
C08J5/24
CHEMISTRY; METALLURGY
Abstract
Disclosed herein are a polyamide composition and a molded article made of the same with improved mechanical strength and reduced weight. The molded article may include the polyamide composition that includes high flowable polyamide and polyphthalamide and a small-diameter fiber, thereby resulting in an improvement in mechanical strength while achieving excellent surface properties and high weight reduction.
Claims
1. A polyamide composition comprising: a primary resin comprising polyamide; a secondary resin comprising polyphthalamide; a fiber; and a heat-resistant agent, wherein the polyamide comprises one or more selected from the group consisting of polyamide 6, polyamide 66, polyamide 12, polyamide 6/66, polyamide 6/12, and polyamide 6/6T, wherein the polyphthalamide comprises polyphthalamide 6I, wherein the fiber comprises one or more selected from the group consisting of a glass fiber, a metal fiber, a carbon fiber, and a natural fiber, wherein the polyamide composition comprises the primary resin in an amount of about 50 to 58.5 parts by weight and the secondary resin in an amount of about 5.8 to 14.2 parts by weight, based on 100 parts by weight of the fiber.
2. The polyamide composition of claim 1, wherein the polyphthalamide has a coefficient of thermal expansion (CTE) of about 55.0 μm/m° C. to 70.0 μm/m° C. at a temperature of about 23° C. to 55° C., a melting point of about 260° C. to 300° C., and a glass transition temperature of about 110° C. to 150° C.
3. The polyamide composition of claim 1, wherein the fiber has a diameter of about 10 μm to 17 μm.
4. The polyamide composition of claim 1, wherein the heat-resistant agent comprises one or more selected from the group consisting of a phosphorus compound, a sulfur compound, and a metal salt compound.
5. The polyamide composition of claim 1, wherein the polyamide composition comprises the heat-resistant agent in an amount of about 1.6 to 3.4 parts by weight based on 100 parts by weight of the fiber.
6. A molded article produced by mixing a polyamide composition of claim 1 and injection molding thereof.
7. The molded article of claim 6, wherein the molded article has a tensile strength of about 315 MPa or more measured according to ISO 527, a flexural strength of about 450 MPa or greater measured according to ISO 178, and a Charpy impact strength of about 35 KJ/m.sup.2 or greater measured according to ISO 179/1eA.
Description
DETAILED DESCRIPTION
(1) Hereinafter reference will now be made in detail to various embodiments of the present invention, examples of which are illustrated in the accompanying drawings and described below. While the invention will be described in conjunction with exemplary embodiments, it will be understood that present description is not intended to limit the invention to those exemplary embodiments. On the contrary, the invention is intended to cover not only the exemplary embodiments, but also various alternatives, modifications, equivalents and other embodiments, which may be included within the spirit and scope of the invention as defined by the appended claims.
(2) Throughout the invention, like reference numerals refer to like parts throughout the various figures and embodiments of the present invention. The drawings are not necessarily to scale and in some instances, proportions may have been exaggerated in order to clearly illustrate features of the embodiments. Although the terms first, second, etc. may be used herein to describe various elements, these elements should not be limited by these terms. These terms may be only used to distinguish one element from another element. For example, without deviating from the scope and spirit of the present invention, a first element may be referred to as a second element, and, similarly, a second element may also be referred to as a first element. As used herein, the singular forms “a”, “an” and “the” are intended to include the plural forms as well, unless context clearly indicates otherwise.
(3) It will be further understood that the terms “comprises/includes” and/or “comprising/including” when used in this specification, specify the presence of stated features, integers, steps, operations, elements, components, and/or groups thereof, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. In addition, it will be understood that when an element, such as a layer, a membrane, a region, or a plate, is referred to as being “above” or “on” another element, it can be “immediately above” the other element or intervening elements may also be present. In contrast, it will be understood that when an element, such as a layer, a membrane, a region, or a plate, is referred to as being “beneath” or “under” another element, it can be “immediately beneath” the other element or intervening elements may also be present.
(4) Unless otherwise indicated, it should be understood that all numbers, values, and/or expressions quantitatively expressing ingredients, reaction conditions, polymer compositions, and combinations used herein are modified in all instances by the term “about” since these are approximations that reflect various uncertainties in measurement occurring essentially to obtain such values among others. In addition, when numerical ranges are disclosed herein, these ranges are contiguous and include all values from a minimum value to a maximum value, inclusive of the maximum value, unless otherwise indicated. Furthermore, when these ranges refer to integers, the ranges include all integers from a minimum value to a maximum value, inclusive of the maximum value, unless otherwise indicated.
(5) In the specification, when ranges are described for variables, it will be understood that the ranges include all variable values inclusive of endpoints subsumed therein. It will be understood that, for example, the range “5 to 10” includes any subranges, such as 6 to 10, 7 to 10, 6 to 9, or 7 to 9, as well as values of 5, 6, 7, 8, 9, and 10, and also includes any values between integers suitable for the range such as 5.5, 6.5, 7.5, 5.5 to 8.5, and 6.5 to 9. In addition, it will be understood that, for example, the range “10% to 30%” includes any subranges, such as 10% to 15%, 12% to 18%, or 20% to 30%, as well as all integers of 10%, 11%, 12%, and 13%, inclusive of up to 30%, and also includes any values between integers suitable for the range such as 10.5%, 15.5%, and 25.5%.
(6) Unless otherwise indicated, all numbers, values, and/or expressions referring to quantities of ingredients, reaction conditions, polymer compositions, and formulations used herein are to be understood as modified in all instances by the term “about” as such numbers are inherently approximations that are reflective of, among other things, the various uncertainties of measurement encountered in obtaining such values.
(7) Further, unless specifically stated or obvious from context, as used herein, the term “about” is understood as within a range of normal tolerance in the art, for example within 2 standard deviations of the mean. “About” can be understood as within 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.5%, 0.1%, 0.05%, or 0.01% of the stated value. Unless otherwise clear from the context, all numerical values provided herein are modified by the term “about.”
(8) It is understood that the term “vehicle” or “vehicular” or other similar term as used herein is inclusive of motor vehicles in general such as passenger automobiles including sports utility vehicles (SUV), buses, trucks, various commercial vehicles, watercraft including a variety of boats and ships, aircraft, and the like, and includes hybrid vehicles, electric vehicles, plug-in hybrid electric vehicles, hydrogen-powered vehicles and other alternative fuel vehicles (e.g. fuels derived from resources other than petroleum). As referred to herein, a hybrid vehicle is a vehicle that has two or more sources of power, for example both gasoline-powered and electric-powered vehicles.
(9) The present invention relates to a polyamide composition and a molded article made of the same.
(10) The polyamide composition includes a primary resin containing polyamide, a secondary resin containing polyphthalamide, a fiber (e.g., long fiber), and a heat-resistant agent.
(11) Hereinafter, the primary resin, secondary resin, fiber, and heat-resistant agent included in the polyamide composition of the present invention will be described separately.
(12) Primary Resin
(13) The primary resin includes polyamide. Preferably, the primary resin may include one or more selected from the group consisting of polyamide 6, polyamide 66, polyamide 12, polyamide 6/66, polyamide 6/12, polyamide 6/6T, and polyamide 6/61. The primary resin may suitably include polyamide 66.
(14) The polyamide 66 may be prepared by condensation polymerization of a hexamethylenediamine monomer and an adipic acid monomer.
(15) As a result of measurement using a formic acid, the polyamide 66 may have a relative viscosity of about 34.0 to 37.0 and a weight average molecular weight ranging from about 10,000 to 21,000 g/mol.
(16) The primary resin may be included in an amount of about 50 to 58.5 parts by weight based on 100 parts by weight of the fiber. When the amount of the primary resin is greater than about 58.5 parts by weight, the effect of the secondary resin may not be sufficient, with the consequence that it is difficult to decrease the crystallization temperature of the polyamide composition to result in deterioration of the appearance surface quality of the molded article. On the other hand, when the amount of the primary resin is less than about 50 parts by weight, the effect of the secondary resin may be relatively excessive, with the consequence that the phase separation between the resins occurs to result in deterioration of the mechanical rigidity of the molded article.
(17) Secondary Resin
(18) The secondary resin includes aromatic polyamide. For example, the secondary resin contains polyphthalamide.
(19) The polyphthalamide may have a density of about 1.00 g/cc or more, preferably about 1.10 to 2.00 g/cc. The polyphthalamide may have a mold shrinkage of about 0.001 cm/cm to 0.005 cm/cm measured according to ISO 294-4 and ISO 2577, a coefficient of thermal expansion (CTE) of about 55.0 μm/m° C. to 70.0 μm/m° C. measured at a temperature of about 23 to 55° C. according to ISO 11359-1, a melting point of about 260° C. to 300° C. measured according to ISO 11357-1, and a glass transition temperature of about 110° C. to 150° C.
(20) Preferably, the polyphthalamide may include amorphous polyphthalamide 61. For example, the polyphthalamide may include only polyamide 61 as a base material.
(21) The amorphous polyphthalamide may be mixed with the polyamide 66 as the primary resin to decrease the crystallization temperature of the polyamide composition, resulting in an improvement in the appearance surface of the molded article and an enhancement in the physical strength or the like of the molded article. When the polyphthalamide contains crystalline polyamide such as polyamide 6T or polyamide 6/6 commonly used, the flowability of the polyamide composition may not be improved, which may lead to breakage of the fiber and restriction on the contact area with the fiber.
(22) The secondary resin may be included in an amount of about 5.8 to 14.2 parts by weight based on 100 parts by weight of the fiber. Preferably, the secondary resin may be included in an amount of 9 to 12 parts by weight. When the amount of the secondary resin is less than about 5.8 parts by weight, the flowability of the polyamide composition may not be improved. On the other hand, when the amount of the secondary resin is greater than about 14.2 parts by weight, the phase separation between the resins may occur to cause a reduction in the mechanical strength of the molded article.
(23) Long Fiber
(24) The fiber may suitably have a diameter of about 10 to 17 μm. Preferably, the fiber may have a diameter of about 13 to 14 μm. When the diameter of the fiber is less than about 10 μm, there may be an increasing probability that the fiber is broken without enduring the shear stress applied during the impregnation of the resin, resulting in a productivity reduction. On the other hand, when the diameter of the fiber is greater than about 17 μm, the contact area with the resin may be reduced to result in deterioration of the mechanical strength of the molded article.
(25) There is commonly used a fiber having a relatively large diameter to minimize the breakage of the fiber. Preferably, the fiber may have a relatively small diameter, because the breakage of the fiber can be minimized due to using the high flowable primary resin and the amorphous secondary resin, thereby maximizing the contact area between the resin and the fiber to enhance the mechanical strength of the molded article.
(26) The fiber may suitably have a length of about 5 to 25 mm, preferably about 9 to 12 mm.
(27) The fiber may include one or more selected from the group consisting of a glass fiber, a metal fiber, a carbon fiber, a polymer fiber, and a natural fiber. The polymer fiber may suitably include, for example, at least one of an aramid fiber, a polyethylene terephthalate fiber, a polyetherether ketone fiber, an ultrahigh molecular weight polyethylene fiber, a liquid crystal polymer fiber, a polyacrylonitrile fiber, an arylate fiber, a rayon fiber, and a polyamide fiber.
(28) Heat-Resistant Agent
(29) The heat-resistant agent may reduce polymer pyrolysis. Since the polyamide composition is produced in a high-temperature environment, it is very important to prevent the polymer pyrolysis. Accordingly, in order to suppress the polymer pyrolysis in such a high-temperature environment, the heat-resistant agent may suitably be used.
(30) The heat-resistant agent may include one or more selected from the group consisting of a phosphorus compound, a sulfur compound, and a metal salt compound.
(31) The heat-resistant agent may be included in an amount of about 1.6 to 3.4 parts by weight based on 100 parts by weight of the fiber. When the amount of the heat-resistant agent is less than about 1.6 parts by weight, the effect of the heat-resistant agent may be insignificant. On the other hand, when the amount of the heat-resistant agent is greater than about 3.4 parts by weight, the heat-resistant agent itself may act as impurities, since the heat-resistant agent is excessively used more than necessary, resulting in deterioration of the mechanical strength of the molded article.
(32) Molded Article
(33) The molded article may be produced by mixing the polyamide composition as described herein and injection molding thereof.
(34) The polyamide composition may be applied to a vehicle component, preferably a vehicle cowl cross beam (CCB) made of metal. For example, the molded article made of the polyamide composition may be advantageous in that the molded article is high in mechanical strength enough to be used for the vehicle CCB of the vehicle and is light in weight much higher than that made of existing metal materials.
(35) The molded article may be superior to that made of existing polyamide compositions in tensile strength, flexural strength, and Charpy impact strength. Particularly, the molded article may have a tensile strength of about 315 MPa or greater measured at a test rate of 50 mm/min according to ISO 527, a flexural strength of about 450 MPa or greater measured at a test rate of 10 mm/min according to ISO 178, and a Charpy impact strength of about 35 KJ/m.sup.2 or greater measured at a temperature of 23° C. according to ISO 179/1eA.
EXAMPLE
(36) Hereinafter, the present invention will be described in more detail with reference to examples. However, these examples are only for illustrating the present invention and the scope of the invention is not limited thereto.
(37) The compositions used in Example according to an exemplary embodiment of the present invention and Comparative Examples are as follows:
(38) Polyamide 66: 21ZLV (available from Acend);
(39) Polyphthalamide 61: M5000 (available from Evonik);
(40) Long Fiber: 423H (available from NEG); and
(41) Heat-Resistant Agent: KN333HSMB (available from KOLON plastics).
Example 1: Production of Molded Article Using Polyamide Composition
(42) A glass fiber was prepared having an average length of 10 mm and a diameter of 13 μm. Based on 100 parts by weight of the glass fiber, 54.2 parts by weight of polyamide 66 as a primary resin, 10 parts by weight of polyphthalamide 61 as a secondary resin, and 2.5 parts by weight of a heat-resistant agent were prepared separately and mixed with each other in a double-axial mixer (TEX-30), so that a mixture thereof is impregnated with the prepared glass fiber. Then, a pellet was prepared having a length of about 10 mm.
Comparative Examples 1 to 8
(43) Polyamide compositions were prepared as indicated in the following Table 1 and pallets were prepared in the same manner as in the above Example 1.
(44) TABLE-US-00001 TABLE 1 Heat- Long Primary Secondary Resistant Fiber Resin Resin Agent (part by (part by (part by (part by weight) weight) weight) weight) Ex. 1 100 54.2 10 2.5 Comp. Ex. 1 50.0 5 2.5 Comp. Ex. 2 58.0 15 2.5 Comp. Ex. 3 54.2 10 2.5 Comp. Ex. 4 54.2 10 1.5 Comp. Ex. 5 54.2 10 3.5 Comp. Ex. 6 54.2 15 1.7 Comp. Ex. 7 54.2 5 1.7 Comp. Ex. 8 54.2 10 2.5 The primary resins, secondary resins, long fibers, and heat-resistant agents in Comparative Examples 1, 2, and 4 to 7 are the same as those in Example 1. The long fiber in Comparative Example 3 has a diameter of 18 μm. The secondary resin in Comparative Example 8 contains polyamide 6T and polyamide 6I in a weight ratio of 1:2.
Experimental Example
(45) Molded articles were produced by injection molding of the pellets in Example 1 and Comparative Examples 1 to 8, and their tensile strength, flexural strength, and impact strength were then measured as indicated in the following Table 2.
(46) TABLE-US-00002 TABLE 2 Tensile Flexural Impact Strength (MPa) Strength (MPa) Strength (MPa) Ex. 1 320 460 37.8 Comp. Ex. 1 305 430 30.6 Comp. Ex. 2 315 435 31.5 Comp. Ex. 3 280 380 28.7 Comp. Ex. 4 302 415 31.8 Comp. Ex. 5 310 412 32.4 Comp. Ex. 6 312 428 30.4 Comp. Ex. 7 301 426 30.0 Comp. Ex. 8 315 415 32.8 The tensile strength was measured at a test rate of 50 mm/min according to ISO 527. The flexural strength was measured at a test rate of 10 mm/min according to ISO 178. The impact strength was measured at a temperature of 23° C. according to ISO 179/1eA.
(47) As shown in the measurement result in the above Table 2, the mechanical strength in Comparative Example 1 was less than that in Example 1 since in Comparative Example 1, the secondary resin was included in a very small amount so that the flowability of the resin is not sufficiently improved.
(48) In Comparative Example 2, the secondary resin was contained excessively above a certain amount so that the phase separation between resins occurred to result in deterioration of mechanical strength.
(49) In Comparative Example 3, the diameter of the long fiber was increased above a certain range so that the contact area with the resin was reduced to result in deterioration of mechanical strength.
(50) In Comparative Example 4, the effect of the heat-resistant agent was significantly reduced to result in a reduction in material stability.
(51) In Comparative Example 5, the heat-resistant agent itself acted as impurities to result in deterioration of mechanical strength.
(52) The results in Comparative Examples 6 and 7 were similar to those in Comparative Examples 1 and 2.
(53) In Comparative Example 8, the flowability of the resin may be reduced to result in deterioration of mechanical strength.
(54) According to various exemplary embodiments of the present invention, the novel polyamide composition can be used to produce the molded article with excellent mechanical strength.
(55) In addition, the long-fiber-reinforced thermoplastic (LFT) can achieve weight reduction while exhibiting mechanical strength similar to that of metal used for the vehicle cowl cross beam (CCB).
(56) Furthermore, the polyamide composition can be used to produce the molded article with improved surface quality.
(57) The present invention is not limited to the above effects. It should be understood that the present invention includes all effects which can be inferred from the above description of the present invention.
(58) The invention has been described in detail with reference to various exemplary embodiments thereof. However, it will be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.