Polyamide resin composition and molded article manufactured therefrom

Abstract

The present disclosure relates to a polyamide resin composition and a molded article manufactured therefrom. The polyamide resin composition comprises: a polyamide resin and a polyketone resin as resin components; a heat-activated glass filler including low-melting point glass; glass fibers; and a flame retardant.

Description

Polyamide resin composition and molded article made therefrom

[0001] The invention relates to a polyamide resin composition and a molded article manufactured therefrom.

[0002] Recently, advancements in electronic product technology have led to the miniaturization, high integration, and high performance of electronic products. Particularly in the case of electric vehicles, battery safety has become a critical issue, requiring characteristics that prevent thermal conduction in the event of thermal runaway caused by vehicle accidents or battery problems.

[0003] To protect lives and property from battery explosions and fires, thermal runaway and heat transfer must be prevented. Conventionally, this has been achieved by using multi-layered insulating materials such as mica and aerogel. However, these methods have the disadvantages of complex manufacturing processes and being economically unfeasible.

[0004] To address this, plastic materials capable of preventing thermal runaway and heat transfer in a single process through injection molding are being proposed.

[0005] However, materials capable of preventing such thermal runaway and heat transfer may impair extrusion and injection moldability, making processing difficult, and in severe cases, may even render processing impossible.

[0006] The present disclosure provides a polyamide resin composition and a molded article manufactured therefrom, which has excellent flame retardancy, fire resistance, and flame resistance by forming a hard char when irradiated with a flame, thereby providing excellent prevention of thermal runaway and heat transfer, and simultaneously has excellent extrusion and injection moldability, making it easy to process.

[0007] One embodiment provides a polyamide resin composition comprising polyamide resin and polyketone resin as resin components; a thermally active glass filler comprising low-melting point glass; glass fibers; and a flame retardant.

[0008] Another embodiment provides a molded article made from the above polyamide resin composition.

[0009] A polyamide resin composition according to one embodiment has excellent flame retardancy, fire resistance, and flame resistance by forming a hard char when irradiated with a flame, and has excellent effects in preventing thermal runaway and heat transfer, and at the same time has excellent extrusion and injection moldability, making it easy to process.

[0010] A molded article according to another embodiment has the advantage of being applicable to fields requiring flame retardancy, fire resistance, and flame resistance.

[0011] Hereinafter, embodiments of the present disclosure are described in detail so that those skilled in the art to which the present disclosure pertains can easily implement them. However, the present disclosure may be embodied in various different forms and is not limited to the embodiments described herein.

[0012] Throughout this specification, when a part is described as "comprising" a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but may include additional components. Furthermore, the singular form includes the plural form unless specifically stated otherwise in the text.

[0013] Polyamide resin composition

[0014] A polyamide resin composition according to one embodiment comprises polyamide resin and polyketone resin as resin components; a thermally active glass filler including low-melting point glass; glass fibers; and a flame retardant. A polyamide resin composition according to one embodiment includes polyamide resin to ensure extrusion and injection moldability, thereby facilitating processing; and includes polyketone resin as a resin component together with polyamide resin to maintain the strength of the char even after exposure to flame. Additionally, by including low-melting point glass and a flame retardant, excellent flame retardancy, fire resistance, and flame resistance can be secured by maintaining and strengthening the shape of the char at the beginning of the flame.

[0015] Polyamide resin

[0016] Polyamide resin is a polymer containing amide groups in its polymer main chain, polymerized using amino acids, lactams, or diamines and dicarboxylic acids as the main components. Polyamide resin serves as the base resin for resin compositions and has excellent mechanical strength, heat resistance, and moldability.

[0017] For example, the amino acid may be 6-aminocaproic acid, 11-aminoundecanic acid, 12-aminododecanoic acid, or para-aminomethylbenzoic acid. The lactam may be ε-caprolactam, or ω-laurolactam. The diamine may be an aliphatic, alicyclic, or aromatic diamine such as tetramethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylenediamine, paraxylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminopropyl)piperazine, aminoethylpiperazine, etc. The dicarboxylic acid may be an aliphatic, alicyclic, or aromatic dicarboxylic acid such as adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanoic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid. Polyamide homopolymers or copolymers derived from these raw materials may be used individually or in the form of a mixture.

[0018] For example, the polyamide resin may include polycaprolactam (polyamide 6), poly(11-aminoundecanic acid) (polyamide 11), polylauryllactam (polyamide 12), poly4,6-tetramethylenediamine adipic acid (polyamide 4,6), polyhexamethyleneadipamide (polyamide 6,6), polyhexaethylene azelamide (polyamide 6,9), polyhexaethylene sebacarmid (polyamide 6,10), polyhexaethylene dodecanodiamide (polyamide 6,12), polyamide 6 / 6,10 copolymer, polyamide 6 / 6,6 copolymer, polyamide 6 / 12 copolymer, or a mixture thereof.

[0019] The polyamide resin may include, for example, polyamide 6. Polyamide 6 may be prepared from ε-caprolactam or 6-aminocaproic acid, and may additionally be copolymerized with other monomers. More specifically, the polyamide resin may include polyamide 6 alone. That is, it may consist only of polyamide 6.

[0020] The relative viscosity of the polyamide resin may be 1.8 to 3.4. Here, the relative viscosity may be measured by adding 1 g of polyamide resin to 100 ml of 96% sulfuric acid at 20°C using a viscometer. When the relative viscosity of the polyamide resin satisfies the above range, it can exhibit excellent mechanical strength and maintain appropriate fluidity during injection molding.

[0021] The number average molecular weight of the polyamide resin may be 20,000 g / mol to 50,000 g / mol. If the number average molecular weight is less than 20,000 g / mol, there is a problem with reduced stiffness, and if it exceeds 50,000 g / mol, there may be problems during melt mixing due to poor flowability caused by high viscosity.

[0022] The melting temperature of the polyamide resin may be 200°C to 250°C, 205°C to 240°C, or 210°C to 235°C. If the melting temperature of the polyamide resin is less than 200°C, the polymer resin may not melt, making processing difficult, and if the melting temperature of the polyamide resin is greater than 250°C, the polyketone resin mixed as a resin component may harden, making processing difficult.

[0023] Polyketone resin

[0024] The polyamide resin composition further includes polyketone resin as a resin component in addition to the polyamide resin. Compared to engineering plastics widely used in various industrial fields, such as polyamide, polyester, and polycarbonate, polyketone resin is characterized by excellent physical and chemical properties, including heat resistance, chemical resistance, barrier properties (fuel permeability), and wear resistance.

[0025] Polyketone resins may include aliphatic and / or aromatic polyketone resins.

[0026] For example, a polyketone resin may include repeating units represented by the following chemical formula 1.

[0027] [Chemical Formula 1]

[0028]

[0029] In the above chemical formula 1, R may be a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, and n may be an integer from 10 to 1,000. More specifically, R may be a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms or a substituted or unsubstituted arylene group having 6 to 50 carbon atoms.

[0030] The polyketone resin may include an aliphatic polyketone resin, in which case, in the above formula 1, R may be a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, for example, an unsubstituted alkylene group having 1 to 30 carbon atoms, an unsubstituted alkylene group having 1 to 15 carbon atoms, an unsubstituted alkylene group having 1 to 10 carbon atoms, or an unsubstituted alkylene group having 2 to 5 carbon atoms. In the above formula 1, R may be an unsubstituted ethylene group or an unsubstituted propylene group.

[0031] Polyketone resins may contain repeating units represented by the chemical formula 2 below.

[0032] [Chemical Formula 2]

[0033]

[0034] In the above chemical formula 2, R1 and R2 may each be independently unsubstituted alkylene groups having 2 to 5 carbon atoms, n1+n2 may be an integer from 10 to 1,000, and R1 and R2 may be different from each other.

[0035] For example, in the above chemical formula 2, R1 may be an unsubstituted ethylene group and R2 may be an unsubstituted propylene group. In this case, n1 and n2 can be appropriately adjusted according to the purpose. For example, n1 may be an integer from 5 to 1,000 and n2 may be an integer from 5 to 1,000.

[0036] The number average molecular weight of the polyketone resin may be 20,000 g / mol to 90,000 g / mol. If the number average molecular weight is less than 20,000 g / mol, there is a problem with reduced stiffness, and if it exceeds 90,000 g / mol, problems may occur during melt mixing due to poor flowability caused by high viscosity.

[0037] The melting temperature of the polyketone resin may be 190°C to 240°C, 195°C to 230°C, or 200°C to 225°C. If the melting temperature of the polyketone resin is less than 190°C, the molecular resin may not melt, making processing difficult, and if the melting temperature of the polyketone resin is greater than 240°C, the polyketone may become excessively hardened and carbonized, making processing difficult.

[0038] In a polyamide resin composition, the content of the resin component (specifically, the combined content of the polyamide resin and the polyketone resin) may be included in an amount of 30% to 70% by weight with respect to 100% by weight of the polyamide resin composition, for example, 30% to 60% by weight, or 30% to 50% by weight. When the content of the resin component in the polyamide resin composition satisfies the above range, the extrusion molding and injection processability is excellent, making processing easy; however, if it falls outside the range, extrusion and / or injection may be difficult, making it difficult to manufacture the product.

[0039] The weight ratio (A / B) of the polyamide resin (A) and the polyketone resin (B) in the polyamide resin composition may be 1 to 3.9, for example, 1 to 3.5, 1 to 3, or 1 to 2.5. When the weight ratio of the polyamide resin and the polyketone resin in the polyamide resin composition satisfies the above range, the extrusion molding and injection processability are excellent, making processing easy, and the flame retardancy, fire resistance, and flame resistance are excellent, so the effect of preventing thermal runaway and heat transfer may be excellent.

[0040] Thermally active glass filler

[0041] A thermally active glass filler refers to glass that is included as a filler in a polyamide resin composition and performs the role of reinforcing char through thermal activation at a specific temperature. The thermally active glass filler includes low-melting-point glass. Low-melting-point glass refers to glass with a lower softening point compared to ordinary quartz glass, for example, glass with a softening point of less than 600°C. More specifically, the low-melting-point glass may have a softening point of 300°C to 450°C, or 350°C to 450°C.

[0042] In a polyamide resin composition according to one embodiment, by including a low-melting-point glass that satisfies the range of the softening point, the glass component can be easily melted by the heat when the resin component of the molded article obtained by molding or curing the resin composition mixed therewith burns, thereby forming a glass film on the surface of the resin molded article. In addition, if char is formed on the surface of the resin molded article during combustion, the char can be reinforced by the molten glass. As a result, the flame retardancy, fire resistance, and flame resistance of the resin molded article can be improved. On the other hand, if the softening point of the low-melting-point glass is less than 300°C, the glass melts by the heat when the resin component burns, but the viscosity of the glass is lowered and it becomes easier to melt, making it difficult to form a glass film on the surface of the resin molded article, and consequently, the flame retardancy, fire resistance, and flame resistance may be reduced. In addition, if the softening point of low-melting point glass exceeds 600°C, it is difficult to form a glass film on the surface of the resin molded product when the resin component burns, and as a result, flame retardancy, fire resistance, and flame resistance may be reduced.

[0043] Low-melting point glass may include known chemical components such as P2O5, Al2O3, and B2O3 without limitation. For example, low-melting point glass may further include ZnO, SO3, Li2O, Na2O, and K2O in addition to P2O5, Al2O3, and B2O3. Here, the content of each component may be appropriately adjusted according to the purpose, and other components may be included in addition to the aforementioned components.

[0044] The low-melting point glass may further include other components within a range that does not impede the effects of the present invention. For example, to adjust the flow characteristics or stability of the glass, it may further include MgO, CaO, SrO, BaO, B, etc., and may further include oxides of metals such as Ti, Fe, Co, Ni, Sn, Zr, Mo, Pb, Na, etc. The components included in the low-melting point glass may be appropriately selected and used according to the softening point of the low-melting point glass, and may include known components in addition to the aforementioned components.

[0045] Low-melting point glass may be in powder form. When the low-melting point glass is in powder form, the average particle size (D of the low-melting point glass powder) 50 The average particle size of the low-melting point glass powder may be 0.5㎛ to 20㎛, 1㎛ to 18㎛, or 5㎛ to 15㎛. If the average particle size of the low-melting point glass powder is less than 0.5㎛, manufacturing costs may increase, which may reduce price competitiveness, and if the average particle size of the low-melting point glass powder exceeds 20㎛, the mechanical properties of the resin molded article may deteriorate. The average particle size of the low-melting point glass powder may be measured using a laser scattering particle size measuring device.

[0046] Low-melting point glass can be obtained by mixing and melting glass raw materials to ensure that specific components have an appropriate composition using known methods and apparatus, then solidifying them to produce a glass cullet of low-melting point glass, and subsequently grinding it to have an average particle size satisfying the above range. For example, grinding to obtain the powder can be performed using known methods, such as wet grinding methods like a medium stirring mill, a colloid mill, or a wet ball mill, or dry grinding methods like a jet mill, a dry ball mill, or a roll crusher, and a combination of multiple grinding methods can be used. Additionally, after grinding, classification treatment can be further performed to obtain only low-melting point glass powder with an average particle size satisfying the above range, and the classification treatment method can also be any known method without limitation, such as using a wind-type classifier or a sieve.

[0047] Low-melting point glass can achieve flame retardancy, fire resistance, and flame resistance of the polyamide resin composition, and at the same time, can be controlled to an appropriate content to ensure easy processing by securing extrusion and injection moldability.

[0048] The above-described thermally active glass filler may further include medium-to-high temperature glass along with the aforementioned low-melting point glass. The medium-to-high temperature glass refers to glass having a softening point higher than that of the aforementioned low-melting point glass, for example, glass having a softening point of 600°C or higher. The softening point of the medium-to-high temperature glass may be 600°C to 900°C, 650°C to 850°C, or 700°C to 800°C.

[0049] In a polyamide resin composition according to one embodiment, by further including medium-high temperature glass satisfying the range of softening points, when a molded article of the polyamide resin composition is burned, the low-melting point glass can melt to reinforce the char when the softening point of the low-melting point glass is reached, and the medium-high temperature glass can melt to further reinforce the char when a higher softening point is reached. As a result, the strength of the char is improved, and excellent flame retardancy, fire resistance, and flame resistance may be achieved, and consequently, the effect of preventing thermal runaway and thermal retardation may be further improved.

[0050] The above medium-to-high temperature glass may be in the form of beads, and the average particle size (D) of the medium-to-high temperature glass beads 50 ) may be 5㎛ to 30㎛, 10㎛ to 28㎛, or 15㎛ to 25㎛.

[0051] The above medium-to-high temperature glass may contain SiO2 components, and due to said components, the softening point may be higher than that of low-melting point glass. In addition, the above medium-to-high temperature glass may include known components other than said components that satisfy the aforementioned softening point, and may further include, for example, CaO, Na2O, Al2O3, MgO, K2O, etc.

[0052] For example, the thermally active glass filler may be included in an amount of 15 to 60 parts by weight per 100 parts by weight of the resin component, and for example, in an amount of 17 to 58 parts by weight, 19 to 55 parts by weight, 20 to 55 parts by weight, or 25 to 50 parts by weight. Here, the resin component refers to the aforementioned polyamide resin and polyketone resin, and 100 parts by weight of the resin component refers to the content of the thermally active glass filler when the content of the aforementioned polyamide resin and polyketone resin is based on 100 parts by weight. When the content of the thermally active glass filler per 100 parts by weight of the resin component satisfies the above range, flame retardancy and fire resistance properties can be achieved, and at the same time, excellent mechanical properties and improved flowability may be advantageous for extrusion and injection molding processing. If the thermally active glass filler is included in an amount of less than 15 parts by weight per 100 parts by weight of the resin component, the strength of the char is weakened and flame retardancy, fire resistance, and flame resistance are reduced, which may impede thermal runaway and heat transfer delay. If the thermally active glass filler is included in an amount of more than 55 parts by weight per 100 parts by weight of the resin component, extrusion processing and injection molding performance may be inferior, making processing difficult, and in severe cases, processing may not be possible.

[0053] When the above-mentioned thermal active glass filler comprises low-melting point glass alone, the low-melting point glass may be included within the aforementioned weight range per 100 weight parts of the resin component. Meanwhile, when the above-mentioned thermal active glass filler further comprises medium-to-high temperature glass along with low-melting point glass, that is, when the thermal active glass filler is a mixture of low-melting point glass and medium-to-high temperature glass, the mixing weight ratio thereof may be, for example, 9:1 to 1:9. The above-mentioned mixing weight ratio may be adjusted according to the purpose, and the mixing weight ratio according to one embodiment may be, for example, 9:1 to 5:5, or 9:1 to 6:4, or 9:1 to 7:3. When the mixing weight ratio of the first low-melting point glass and the second low-melting point glass satisfies the above range, the char generated by the flame can be effectively reinforced, thereby improving flame retardancy, fire resistance, and flame resistance, and thus providing excellent effects in preventing thermal runaway and heat transfer.

[0054] glass fiber

[0055] Glass fibers can be included in a polyamide resin composition to improve mechanical strength and moldability.

[0056] The glass fiber may have a chop shape, and its diameter may be 4 µm to 20 µm or 8 µm to 16 µm, and its length may be 1.5 mm to 9 mm or 1.5 mm to 6 mm. When the diameter and length of the glass fiber satisfy the above ranges, mechanical strength and formability may be improved.

[0057] The cross-section of the glass fiber may be circular, elliptical, rectangular, or dumbbell-shaped with two connected circles. The aspect ratio of the cross-section of the glass fiber may vary depending on the shape of the cross-section of the glass fiber, for example, the aspect ratio of the cross-section of the glass fiber may be less than 4.5, less than 3, or less than 1.5. For example, if the cross-section of the glass fiber is circular, elliptical, or dumbbell-shaped with two connected circles, the aspect ratio of the cross-section of the glass fiber may be less than 1.5, and if the cross-section of the glass fiber is rectangular, the aspect ratio of the cross-section of the glass fiber may be less than 4.5.

[0058] The glass fiber may be a surface-treated glass fiber that mixes well with the aforementioned resin components without causing a chemical reaction, and, for example, the glass fiber may be treated with a coupling agent. As the coupling agent, a silane-based material having organic functional groups such as vinyl groups, epoxy groups, mercaptan groups, and amine groups may be used. In addition, the glass fiber may be mixed with other types of fibers, such as carbon fiber.

[0059] Glass fibers may be included in an amount of 10 to 150 parts by weight per 100 parts by weight of the resin component, or in an amount of 15 to 145 parts by weight, 20 to 140 parts by weight, 25 to 135 parts by weight, or 30 to 135 parts by weight. Here, the resin component refers to the aforementioned polyamide resin and polyketone resin, and 100 parts by weight of the resin component refers to the content of glass fibers when the content of the aforementioned polyamide resin and polyketone resin is based on 100 parts by weight. When the content of glass fibers per 100 parts by weight of the resin component satisfies the above range, flame retardancy and fire resistance properties can be achieved, and at the same time, excellent mechanical properties and improved flowability may be advantageous for extrusion and injection molding processing. When glass fibers are included in an amount of less than 10 parts by weight per 100 parts by weight of resin components, the strength of the char is weakened and the refractory and flame resistance are reduced, which may hinder thermal runaway and the delay of heat transfer. When glass fibers are included in an amount of more than 150 parts by weight per 100 parts by weight of resin components, the mechanical strength may be improved, but processing may be difficult due to the difficulty of injection molding and extrusion.

[0060] flame retardant

[0061] Flame retardants can improve the flame retardancy rating and electrical properties of polyamide resin compositions. Examples of flame retardants include halogen flame retardants and non-halogen flame retardants. Halogen flame retardants may use halogen elements selected from bromine, chlorine, and fluorine, either alone or in a mixture; specifically, examples include halogenated polystyrene. Due to recent regulations stemming from environmental issues, non-halogen flame retardants may be used. Examples of non-halogen flame retardants include phosphorus-based flame retardants, inorganic flame retardants, and melamine-based flame retardants.

[0062] The flame retardant may include a non-halogen flame retardant, for example, a phosphorus-based flame retardant alone, or a mixture of a phosphorus-based flame retardant and a melamine-based flame retardant. When the flame retardant is a mixture of a phosphorus-based flame retardant and a melamine-based flame retardant, the weight ratio of the mixture of the phosphorus-based flame retardant and the melamine-based flame retardant may be 1:1 to 4:1, for example, 2:1 to 4:1, or 3:1. If a flame retardant other than those listed as types of flame retardants is used as the flame retardant, the strength of the char material (Char) is weakened, fire resistance and flame resistance are reduced, and expansion occurs, which may impede the suppression of thermal runaway and heat transfer.

[0063] The above-mentioned phosphorus-based flame retardant may include ammonium phosphate, ammonium polyphosphate, aluminum diethyl phosphinate, aluminum hypophosphite, or a combination thereof, and the above-mentioned melamine-based flame retardant may include melamine phosphate, melamine polyphosphate, melamine cyanurate, melamine pyrophosphate, or a combination thereof.

[0064] The flame retardant may be included in an amount of 15 to 70 parts by weight, 20 to 70 parts by weight, or 25 to 68 parts by weight per 100 parts by weight of the resin component. Here, the resin component refers to the aforementioned polyamide resin and polyketone resin, and 100 parts by weight of the resin component refers to the content of the flame retardant when the content of the aforementioned polyamide resin and polyketone resin is based on 100 parts by weight. When the content of the flame retardant per 100 parts by weight of the resin component satisfies the above range, flame retardancy and fire resistance properties can be achieved, and at the same time, excellent mechanical properties and improved flowability may be advantageous for extrusion and injection molding processing. If the flame retardant is included in an amount of less than 15 parts by weight per 100 parts by weight of the resin component, it may be difficult to achieve the required flame retardant grade V-0 and electrical properties in the product, and if the flame retardant is included in an amount of more than 70 parts by weight per 100 parts by weight of the resin component, mechanical properties may be degraded, and processing may be difficult due to injection and extrusion.

[0065] Other additives

[0066] The polyamide resin composition may further include other additives as needed. For example, it may include plasticizers, photodegradation inhibitors, heat inhibitors, impact inhibitors, antioxidants, release agents, dyes, pigments, UV absorbers, nucleating agents, lubricants, or combinations thereof, provided that they are commonly used in the industry, they may be used without limitation.

[0067] The content of other additives can be appropriately added within a range that does not impair the desired physical properties of the polyamide resin composition.

[0068] molded product

[0069] A molded article according to another embodiment is manufactured from the aforementioned polyamide resin composition. The aforementioned molded article has the advantage of being applicable to fields requiring flame retardancy and fire resistance. Specifically, the molded article can be used as a peripheral component of an electric vehicle battery, for example, as a housing, busbar, side cover, rear cover, etc.

[0070] Physical properties

[0071] The molded article is manufactured from the aforementioned polyamide resin composition, and when evaluating extrusion characteristics, the strand is well formed and easily caught in the cutter, making cutting easy, so the extrusion characteristics are excellent, and when evaluating fire resistance and flame resistance (Torch & Air), the maximum number of cycles is 10 or more, and the flame retardancy grade is V-0, so the flame retardancy is excellent.

[0072] Hereinafter, embodiments are described in detail so that those skilled in the art can easily implement the present invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein.

[0073] Example 1

[0074] Polyamide 6 (Manufacturer: Meida, Product Name: M2000) as a polyamide resin with a melting point of 220°C, Hyosung's POKETONE M130F product as a polyketone resin with a melting point of 210°C, a thermally active glass filler with a softening point of 405°C, in powder form, and an average particle size of the powder (D 50 The low-melting point glass of NIHON HORO YURAKU’s RCY-LF40 product, which has a thickness of 10㎛, a softening point of 730℃, a bead shape, and an average particle size of the beads (D 50A polyamide resin composition was prepared by mixing medium-to-high temperature glass of SOVITEC’s Microperl 215 product with a diameter of 20㎛ in a weight ratio of 8:2, glass fiber of NEG’s 262H product with a diameter of 10.5㎛, a length of 3mm, and an aspect ratio of about 1, and a mixture of aluminum hypophosphite as a phosphorus-based flame retardant and melamine cyanurate as a melamine-based flame retardant in a weight ratio of 3:1 to form the composition shown in Table 1 below, and melt-kneading the mixture in a twin-screw extruder heated to 240℃.

[0075]

[0076] Examples 2 to 3 and Comparative Examples 1 to 8

[0077] A polyamide resin composition was prepared in the same manner as in Example 1, except that the content of the polyamide resin, polyketone resin, heat-activated glass filler, glass fiber, and flame retardant in Example 1 was varied as shown in Table 1 below.

[0078] Here, the content of the resin component is described with respect to 100% by weight of the polyamide resin composition, and the weight ratio of the polyamide resin to the polyketone resin (polyamide resin / polyketone resin) within the resin component is described. The content of the thermally active glass filler, glass fiber, and flame retardant is described based on 100 parts by weight of the resin component. In the column describing the content ratio of the polyamide resin and the polyketone resin, if either one is absent, the present component is described, and in that case, the content of the resin component in the polyamide resin composition is the same as the content of the present component.

[0079] Resin component, thermally active glass filler, glass fiber, flame retardant Content of resin component in polyamide resin composition (weight%) Polyamide resin / Polyketone resin Example 1: 30 23.31 33.36 6.7 Example 2: 30 150 13.350 Example 3: 50 2.33 30 40 Comparative Example 1: 26 2.35 7.7 15 3.8 7 3.1 Comparative Example 2: 35 Polyketone resin 42.98 5.75 7.1 Comparative Example 3: 35 Polyamide resin 42.98 5.75 7.1 Comparative Example 4: 50 43.31 30 40 Comparative Example 5: 30 93.31 50 50 Comparative Example 6: 35 2.51 4.31 14.35 7.1 Comparative Example 7: 35 2.55 7.1 11 4.31 4.3 Comparative Example 8352.557.157.171.4

[0080]

[0081] Evaluation example

[0082] 1. Extrusion Characteristics

[0083] The polyamide resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 8 were evaluated as high, medium, and low based on the following criteria in an extrusion process using a 25 mm diameter twin-screw extruder. In the evaluation method below, cases evaluated as medium may have slightly inferior extrusion characteristics compared to cases evaluated as high, but since processing is possible, the desired processability can be achieved in cases evaluated as medium and high.

[0084] Evaluation Method

[0085] - Top: When the polyamide resin composition passes through the extruder die without degradation, the strand catches well on the cutter, and cutting is possible without problems

[0086] - Middle: Cases where the polyamide resin composition passes through the extruder die without degradation, the strands grip the cutter well, and cutting is possible, but the strands frequently break and need to be re-grabbed.

[0087] - H: Cases where the polyamide resin composition decomposes as it passes through the extruder, causing swelling or flow out when exiting the extruder die, preventing strand formation and making cutting itself impossible.

[0088]

[0089] 2. Evaluation of fire resistance and flame resistance

[0090] A specimen with a width of 150 mm, a length of 150 mm, and a thickness of 2 mm was prepared by injection molding a molded article according to the polyamide resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 8. After being mounted on the stand of a flame evaluation device, a high-temperature flame of 1200°C was irradiated for 15 seconds from a distance of 80 mm, and thereafter, high-pressure air of 4 bar was irradiated for 5 seconds from the same distance (80 mm) using a 3 mm diameter air gun (1 st Cycle). The above process 1 st Considered as cycles, the process was repeated for n cycles until the specimen was destroyed or damaged, such as by being punctured, burning, or flames leaking from the back of the specimen. The number of cycles was recorded at the point when the specimen was destroyed or damaged to evaluate the maximum number of cycles the material could withstand, which is shown in Table 2. Here, a higher number of cycles indicates superior fire resistance and flame resistance.

[0091]

[0092] 3. Flame retardancy

[0093] Molded articles prepared according to the polyamide resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 8 were tested for flame retardancy according to the UL94 standard by measuring test specimens of 125 mm × 13 mm × 1.5 mm using a flammability meter via the vertical combustion test method, and the results are shown in Table 2 below. The degree of flame retardancy is indicated by grades V-0 to V-2, where V-0 indicates the best flame retardancy and V-2 indicates poor flame retardancy.

[0094] Extrusion Characteristics, Fire Resistant and Flame Resistance, Flame Retardancy Example 1 Medium 15V-0 Example 2 Medium 15V-0 Example 3 Phase 14V-0 Comparative Example 1 Low-- Comparative Example 2 Low-- Comparative Example 3 Phase 2V-0 Comparative Example 4 Medium 7V-0 Comparative Example 5 Phase 7V-0 Comparative Example 6 Medium 5V-0 Comparative Example 7 Medium 4V-2 Comparative Example 8 Medium 3V-0

[0095]

[0096] result

[0097] Referring to Tables 1 and 2, even though the heat-activated glass filler, glass fiber, and flame retardant contained in the polyamide resin composition were all included within the appropriate range, the polyamide resin composition of Comparative Example 1, in which the total content of polyamide resin and polyketone resin as resin components was 26 wt%, which is below the appropriate range, was evaluated as low during the extrusion characteristics evaluation. Furthermore, the results of the fire resistance and flame resistance (Torch & Air) evaluation and the flame retardancy evaluation could not be measured. This is because the polyamide resin composition of Comparative Example 1 was not easy to extrude, strand formation did not occur due to the decomposition of the flame retardant and resin components, and cutting also failed, so the product could not be manufactured.

[0098] Meanwhile, although the heat-activated glass filler, glass fiber, and flame retardant contained in the polyamide resin composition are all included within an appropriate range and the total content of the resin component is 35 weight%, unlike Comparative Example 1, Comparative Example 2, which does not contain polyamide resin, has very inferior extrusion characteristics and, as with Comparative Example 1, the results of the fire resistance and flame resistance evaluation and the flame retardancy evaluation could not be measured. This is because, in the case of the polyamide resin composition of Comparative Example 2, strand formation did not occur due to the decomposition of the polyketone resin, and cutting also failed, so the product could not be made.

[0099] In addition, in the case of Comparative Example 3, which does not include polyketone resin as a resin component as in Comparative Example 2 but includes polyamide resin, unlike Comparative Example 2, it was found that the extrusion characteristics were excellent and the flame retardancy rating was also excellent at V-0, but the maximum cycle was 2 when evaluating fire resistance and flame resistance, which was very inferior.

[0100] When comparing Example 3 and Comparative Example 4, the content of the resin component in the polyamide resin composition is the same at 50 wt%, and the content of the remaining heat-activated glass filler, glass fiber, and flame retardant is also the same; however, the ratio of polyamide resin to polyketone resin in the resin component differs. Specifically, Comparative Example 4 has a ratio of polyamide resin to polyketone resin of 4, containing a small amount of polyketone compared to Example 3. When evaluating fire resistance and flame resistance, the maximum cycle was evaluated as 7, confirming that the effect of preventing thermal runaway and heat transfer is relatively inferior.

[0101] Meanwhile, when comparing Examples 1 to 3 with Comparative Example 5, in the case of Examples 1 to 3, where the polyketone resin content in the resin component is included in an appropriate ratio of polyamide resin and polyketone resin, the extrusion characteristics were evaluated as medium or high, making product processing easy, while at the same time, the flame retardancy was excellent, and when evaluating fire resistance and flame resistance, the maximum cycle was evaluated to be 10 or more, confirming that the effect of preventing thermal runaway and heat transfer is very excellent. On the other hand, when the weight ratio of polyamide resin to polyketone resin is 9, meaning the polyketone resin is included in an excessively small amount, the maximum cycle when evaluating fire resistance and flame resistance was limited to 7.

[0102] Through this, it can be confirmed that when the content of the resin component in the polyamide resin composition is included within an appropriate range, and both polyamide resin and polyketone resin are included as resin components, and the weight ratio of polyamide resin and polyketone resin is included within an appropriate range, the extrusion characteristics are excellent, making extrusion processing and injection molding easy, while at the same time having excellent flame retardancy, and the maximum number of cycles for fire resistance and flame resistance is evaluated to be 10 or more, resulting in a very excellent effect in preventing thermal runaway and heat transfer.

[0103] Meanwhile, assuming that the weight ratio of polyamide resin and polyketone resin is within the appropriate range and the content of the resin component is within the appropriate range, Comparative Examples 6 and 8, which contain an excessively small amount of thermally active glass filler or an excessive amount of flame retardant compared to Examples 1 to 3, show that the extrusion characteristics are inferior compared to the examples, resulting in reduced extrusion processing and injection molding performance, making product processing difficult. Additionally, the maximum number of cycles for fire resistance and flame resistance is evaluated as 5 and 3, respectively, confirming that the effect of preventing thermal runaway and heat transfer is very inferior. Furthermore, Comparative Example 7, which contains a small amount of flame retardant, shows that the extrusion characteristics are inferior compared to the examples, resulting in reduced extrusion processing and injection molding performance, making product processing difficult. In addition to having inferior fire resistance and flame resistance, it can be confirmed that the flame retardant grade is V-2, indicating very inferior flame retardancy.

[0104] Through this, it was confirmed that even when the resin component is included within an appropriate range and the weight ratio of polyamide resin to polyketone resin within the resin component is within an appropriate range, and the content of thermally active glass filler and flame retardant is within an appropriate range, the extrusion characteristics are excellent, making product processing easier without reducing extrusion processing and injection molding performance, while simultaneously exhibiting excellent flame retardancy, fire resistance, and flame resistance, thereby providing excellent effects in preventing thermal runaway and heat transfer.

[0105]

[0106] Although preferred embodiments have been described in detail above, the scope of the rights is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concepts defined in the following claims are also included within the scope of the rights.

Claims

1. Polyamide resin and polyketone resin as resin components; a thermally active glass filler including low-melting point glass; glass fiber; and a flame retardant, Polyamide resin composition.

2. In Paragraph 1, The above polyamide resin is composed of polyamide 6, Polyamide resin composition.

3. In Paragraph 1, The above polyketone resin comprises repeating units represented by the following chemical formula 2, Polyamide resin composition: [Chemical Formula 2] In the above chemical formula 2, R1 and R2 are each independently unsubstituted alkylene groups having 2 to 5 carbon atoms, n1+n2 is an integer from 10 to 1,000, and R1 and R2 are different from each other.

4. In Paragraph 1, The melting temperature of the above polyamide resin is 200°C to 250°C, and The melting temperature of the above polyketone resin is 190℃ to 240℃, Polyamide resin composition.

5. In Paragraph 1, In the above polyamide resin composition, the content of the resin component is included in an amount of 30% to 70% by weight based on 100% by weight of the polyamide resin composition, Polyamide resin composition.

6. In Paragraph 1, In the above polyamide resin composition, the weight ratio (A / B) of the polyamide resin (A) and the polyketone resin (B) is 1 to 3.9, Polyamide resin composition.

7. In Paragraph 1, The above low-melting point glass has a softening point of 300°C to 450°C, and The above low-melting point glass is in powder form, and The average particle size of the above powder is 0.5㎛ to 20㎛, Polyamide resin composition.

8. In Paragraph 1, The above-mentioned thermally active glass filler further includes medium-to-high temperature glass, and The above medium-to-high temperature glass has a softening point of 600℃ or higher, and The above medium-to-high temperature glass is in the form of beads, and The average particle size of the beads is 5㎛ to 30㎛, Polyamide resin composition.

9. In Paragraph 1, The above thermally active glass filler is included in an amount of 15 to 60 parts by weight per 100 parts by weight of the resin component, Polyamide resin composition.

10. In Paragraph 1, The above glass fiber has a chopped shape, The diameter is 4㎛ to 20㎛, and The length is 1.5 mm to 9 mm, Polyamide resin composition.

11. In Paragraph 1, The above glass fiber is included in an amount of 10 to 150 parts by weight per 100 parts by weight of the resin component, Polyamide resin composition.

12. In Paragraph 1, The above flame retardant includes a non-halogen flame retardant, and The above-mentioned non-halogen flame retardant comprises a phosphorus-based flame retardant alone or a mixture of a phosphorus-based flame retardant and a melamine-based flame retardant. Polyamide resin composition.

13. In Paragraph 12, In the case where the above flame retardant is a mixture of a phosphorus-based flame retardant and a melamine-based flame retardant, The mixing weight ratio of the above phosphorus-based flame retardant and melamine-based flame retardant is 1:1 to 4:1, Polyamide resin composition.

14. In Paragraph 1, The flame retardant is included in an amount of 15 to 70 parts by weight per 100 parts by weight of the resin component, Polyamide resin composition.

15. Manufactured from a polyamide resin composition according to claim 1, Molded product.

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