Thermoplastic resin composition and molded article produced therefrom

Abstract

A thermoplastic resin composition according to the present invention comprises: about 100 parts by weight of a base material containing about 55 to about 75 wt% of a polyphenylene ether resin, about 10 to about 30 wt% of a rubber-modified polystyrene resin, and about 7 to about 15 wt% of glass beads; about 10 to about 20 parts by weight of an aromatic phosphate compound; about 0.8 to about 5 parts by weight of a metal phosphinate compound; about 0.1 to about 1 part by weight of dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO); and about 2 to about 8 parts by weight of a styrene-ethylene / butylene-styrene copolymer, wherein the weight ratio between the aromatic phosphate compound and the metal phosphinate compound is about 1:0.09 to about 1:0.4, and the weight ratio between the aromatic phosphate compound and the DOPO is about 1:0.006 to about 1:0.05. The thermoplastic resin composition has excellent rigidity, impact resistance, dimensional stability (bending properties), flame retardancy, and discoloration stability, and an excellent balance of said physical properties.

Description

Thermoplastic resin composition and molded article formed therefrom

[0001] The present invention relates to a thermoplastic resin composition and a molded article formed therefrom. More specifically, the present invention relates to a thermoplastic resin composition having excellent rigidity, impact resistance, dimensional stability (flexural characteristics), flame retardancy, discoloration stability, and a balance of these physical properties, and a molded article formed therefrom.

[0002]

[0003] Polyphenylene ether resin is an amorphous resin with excellent dimensional stability, insulation, heat resistance, and rigidity, but it has the problem of low resin flowability for injection molding. To solve this problem, polyphenylene ether resin is commercialized by alloying it with polystyrene-based resin. In addition, to use polyphenylene ether resin for applications such as covers for electrical / electronic products, a technology has been proposed to apply a phosphate-based flame retardant to impart flame retardancy while improving compatibility and flowability with the polystyrene-based resin to be alloyed.

[0004] However, in order to achieve suitable flame retardancy, an excessive amount of phosphate-based flame retardant is required, which may lead to a decrease in the mechanical properties of the resin composition. In addition, polyphenylene ether resin can cause a decrease in the discoloration stability of the resin composition and the molded article, and there is a problem that if the content of polystyrene-based resin is increased, the heat resistance and flame retardancy may decrease.

[0005] Therefore, there is a need to develop thermoplastic resin compositions with excellent rigidity, impact resistance, dimensional stability (flexural properties), flame retardancy, discoloration stability, and a balance of these physical properties.

[0006] The background technology of the present invention is disclosed in Korean registered patent No. 10-1718183, etc.

[0007]

[0008] The objective of the present invention is to provide a thermoplastic resin composition having excellent rigidity, impact resistance, dimensional stability (flexural characteristics), flame retardancy, discoloration stability, and a balance of these physical properties.

[0009] Another objective of the present invention is to provide a molded article formed from the thermoplastic resin composition.

[0010] The above and other objectives of the present invention can all be achieved by the present invention described below.

[0011]

[0012] 1. One aspect of the present invention relates to a thermoplastic resin composition. The thermoplastic resin composition comprises about 100 parts by weight of a base material comprising about 55 to about 75 parts by weight of a polyphenylene ether resin, about 10 to about 30 parts by weight of a rubber-modified polystyrene resin, and about 7 to about 15 parts by weight of glass beads; about 10 to about 20 parts by weight of an aromatic phosphate compound; about 0.8 to about 5 parts by weight of a metal phosphinate compound; and about 0.1 to about 1 part by weight of dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO). It comprises about 2 to about 8 parts by weight of a styrene-ethylene / butylene-styrene copolymer; wherein the weight ratio of the aromatic phosphate compound to the metal phosphinate compound is about 1:0.09 to about 1:0.4, and the weight ratio of the aromatic phosphate compound to the DOPO is about 1:0.006 to about 1:0.05.

[0013] 2. In the above 1 embodiment, the polyphenylene ether resin may include a repeating unit represented by the following chemical formula 1:

[0014] [Chemical Formula 1]

[0015]

[0016] In the above chemical formula 1, R1, R2, R3, and R4 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

[0017] 3. In the above 1 or 2 embodiments, the rubber-modified polystyrene resin may be a polymer prepared by polymerizing about 70 to about 97 weight percent of styrene in the presence of about 3 to about 30 weight percent of a rubbery polymer.

[0018] 4. In the above 1 to 3 embodiments, the glass beads may have an average particle size (D50) of about 1 to about 100 μm.

[0019] 5. In the above 1 to 4 embodiments, the aromatic phosphate compound may include one or more of bisphenol-A bis(diphenylphosphate), resorcinol bis(diphenylphosphate), resorcinol bis[bis(2,6-dimethylphenyl)phosphate], resorcinol bis[bis(2,4-ditertiarybutylphenyl)phosphate], hydroquinone bis[bis(2,6-dimethylphenyl)phosphate] and hydroquinone bis[bis(2,4-ditertiarybutylphenyl)phosphate].

[0020] 6. In the above embodiments 1 to 5, the metal phosphinate compound may be represented by the following chemical formula 2:

[0021] [Chemical Formula 2]

[0022]

[0023] In the above chemical formula 2, R1 and R2 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, M is Al, Zn, Mg, Ca, Sb, Sn, Ge, Ti, Fe, Zr, Ce, Bi, Sr, Mn, Li, or Na, and n is an integer from 1 to 4.

[0024] 7. In the above 1 to 6 embodiments, the styrene-ethylene / butylene-styrene copolymer may have a melt-flow index (MI) of about 10 to about 50 g / 10 min, measured at 200°C and 5 kgf according to ASTM D1238.

[0025] 8. In the above 1 to 7 embodiments, the thermoplastic resin composition may further include about 1 to about 5 parts by weight of glass fibers with respect to about 100 parts by weight of the base material.

[0026] 9. In the above 1 to 8 embodiments, the weight ratio of the rubber-modified polystyrene resin and the metal phosphinate compound may be about 1:0.01 to about 1:0.5.

[0027] 10. In the above 1 to 9 embodiments, the weight ratio of the polyphenylene ether resin and the DOPO may be about 1:0.0013 to about 1:0.0150.

[0028] 11. In the above embodiments 1 to 10, the thermoplastic resin composition may have a tensile elongation of about 7 to about 20% for a 3.2 mm thick specimen measured at 5 mm / min according to ASTM D638, and a tensile strength of about 520 to about 800 kgf / cm² for a 3.2 mm thick specimen measured at 5 mm / min according to ASTM D638. 2 It could be.

[0029] 12. In the above 1 to 11 embodiments, the thermoplastic resin composition may have a notched Izod impact strength of about 8 to about 16 kgf·cm / cm of a 1 / 8" thick specimen measured according to ASTM D256.

[0030] 13. In the above 1 to 12 embodiments, the thermoplastic resin composition may have a flow direction (MD) molding shrinkage rate of about 0.4 to about 0.8% and a vertical direction (TD) molding shrinkage rate of about 0.4 to about 0.8%, measured on a circular specimen with a thickness of 3.2 mm and a diameter of 100 mm according to ASTM D955.

[0031] 14. In the above 1 to 13 embodiments, the thermoplastic resin composition may have a flame retardancy of V-0 on a 0.8 mm thick specimen measured by the UL-94 vertical test method.

[0032] 15. Another aspect of the present invention relates to a molded article. The molded article is characterized by being formed from a thermoplastic resin composition according to any one of 1 to 14.

[0033]

[0034] The present invention has the effect of providing a thermoplastic resin composition having excellent rigidity, impact resistance, dimensional stability (flexural characteristics), flame retardancy, discoloration stability, and a balance of these physical properties, and a molded article formed therefrom.

[0035]

[0036] The present invention will be described in detail below.

[0037] The thermoplastic resin composition according to the present invention comprises (A) polyphenylene ether resin; (B) rubber-modified polystyrene resin; (C) glass beads; (D) aromatic phosphate compound; (E) metal phosphinate compound; (F) dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO); and (G) styrene-ethylene / butylene-styrene copolymer.

[0038] In this specification, "a to b" indicating a numerical range is defined as "≥a and ≤b".

[0039]

[0040] (A) Polyphenylene ether resin

[0041] A polyphenylene ether resin according to one embodiment of the present invention can be applied together with rubber-modified polystyrene resin, glass beads, aromatic phosphate compounds, metal phosphinate compounds, DOPO, and styrene-ethylene / butylene-styrene copolymers, etc., to improve the stiffness, impact resistance, dimensional stability (flexural properties), flame retardancy, discoloration stability, and the balance of physical properties thereof of a thermoplastic resin composition, and a polyphenylene ether resin used in a conventional thermoplastic resin composition may be used. For example, a polyphenylene ether resin comprising repeating units represented by the following chemical formula 1 may be used.

[0042] [Chemical Formula 1]

[0043]

[0044] In the above chemical formula 1, R1, R2, R3, and R4 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

[0045] In a specific example, the polyphenylene ether resin is a poly(1,4-phenylene) ether, a poly(2,6-dimethyl-1,4-phenylene) ether, a poly(2,6-diethyl-1,4-phenylene) ether, a poly(2,6-dipropyl-1,4-phenylene) ether, a poly(2-methyl-6-ethyl-1,4-phenylene) ether, a poly(2-methyl-6-propyl-1,4-phenylene) ether, a poly(2,6-diphenyl-1,4-phenylene) ether, a copolymer of a poly(2,6-dimethyl-1,4-phenylene) ether and a poly(2,3,6-trimethyl-1,4-phenylene) ether, and a poly(2,6-dimethyl-1,4-phenylene) ether and a poly(2,3,5-triethyl-1,4-phenylene) ether. Copolymers, etc. can be examples.

[0046] In a specific example, the polyphenylene ether resin may have a weight-average molecular weight of about 10,000 to about 50,000 g / mol, for example, about 20,000 to about 40,000 g / mol, as measured by gel permeation chromatography (GPC). Within this range, the heat resistance, mechanical properties, processability, etc. of the thermoplastic resin composition may be excellent.

[0047] In a specific example, the polyphenylene ether resin may be included in an amount of about 55 to about 75 weight%, for example, about 61 to about 72 weight%, of the total 100 weight% of the base material including polyphenylene ether resin, rubber-modified polystyrene resin, and glass beads. If the content of the polyphenylene ether resin is less than about 55 weight% of the total 100 weight% of the base material, there is a risk that the flame retardancy, stiffness (tensile strength), etc. of the thermoplastic resin composition will decrease, and if it exceeds about 75 weight%, there is a risk that the stiffness (tensile elongation), etc. of the thermoplastic resin composition will decrease.

[0048]

[0049] (B) Rubber-modified polystyrene resin

[0050] A rubber-modified polystyrene resin according to one embodiment of the present invention can be applied together with polyphenylene ether resin, glass beads, aromatic phosphate compounds, metal phosphinate compounds, DOPO, and styrene-ethylene / butylene-styrene copolymers to improve the stiffness, impact resistance, dimensional stability (flexural properties), flame retardancy, discoloration stability, and balance of physical properties of a thermoplastic resin composition. For example, a polymer prepared by polymerizing styrene in the presence of a rubbery polymer, such as a conventional high-impact polystyrene (HIPS) resin, can be used.

[0051] In a specific example, the rubbery polymer may be exemplified as a diene-based rubber such as butadiene rubber and acrylonitrile-butadiene rubber, a saturated rubber obtained by hydrogenating the diene-based rubber, isoprene rubber, an alkyl (meth)acrylate rubber having 2 to 10 carbon atoms, a copolymer of an alkyl (meth)acrylate having 2 to 10 carbon atoms and styrene, an ethylene-propylene-diene monomer terpolymer (EPDM), etc. These may be applied individually or in a mixture of two or more types. For example, diene-based rubber, alkyl (meth)acrylate rubber, etc. may be used, and specifically, butadiene rubber, butyl acrylate rubber, etc. may be used.

[0052] In a specific example, the rubbery polymer (rubber particles) may have an average particle size of 0.05 to 6 μm, for example, about 0.15 to about 4 μm, specifically about 0.25 to about 3.5 μm. Within this range, the impact resistance and appearance characteristics of the thermoplastic resin composition may be excellent. Here, the average particle size (z-mean) of the rubbery polymer (rubber particles) can be measured using a light scattering particle size analyzer (Malvern Panalytical, Nano ZS) by using a light scattering method.

[0053] In a specific example, the content of the rubbery polymer may be about 3 to about 30 weight%, for example, about 5 to about 20 weight%, of the total 100 weight% of the rubber-modified polystyrene resin. Within this range, the impact resistance, appearance characteristics, etc. of the thermoplastic resin composition may be excellent.

[0054] The content of the repeating unit derived from the above styrene may be about 70 to about 97 weight%, for example, about 80 to about 95 weight%, of the total 100 weight% of the rubber-modified polystyrene resin. Within this range, the moldability, impact resistance, appearance characteristics, etc. of the thermoplastic resin composition may be excellent.

[0055] In a specific example, the rubber-modified polystyrene resin may be polymerized by adding monomers such as acrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleimide during the polymerization of the rubber-modified polystyrene resin to impart properties such as chemical resistance, processability, and heat resistance to the thermoplastic resin composition. In this case, the amount of monomer added may be about 40% by weight or less with respect to 100% by weight of the total rubber-modified polystyrene resin. Within this range, chemical resistance, processability, and heat resistance can be imparted to the thermoplastic resin composition without deterioration of other physical properties.

[0056] In a specific example, the rubber-modified polystyrene resin may be polymerized by thermal polymerization without the presence of an initiator or polymerized in the presence of an initiator. Examples of the initiator include one or more peroxide-based initiators such as benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, and cumene hydroperoxide, and azo-based initiators such as azobis isobutyronitrile. The rubber-modified polystyrene resin may be polymerized by known polymerization methods such as bulk polymerization, suspension polymerization, and emulsion polymerization.

[0057] In a specific example, the rubber-modified polystyrene resin may be included in an amount of about 10 to about 30 weight%, for example, about 16 to about 27 weight%, of 100 weight% of the base material. If the content of the rubber-modified polystyrene resin is less than about 10 weight% of 100 weight% of the base material, there is a risk that the stiffness (tensile elongation), etc., of the thermoplastic resin composition will decrease, and if it exceeds about 30 weight%, there is a risk that the flame retardancy, stiffness (tensile strength), etc., of the thermoplastic resin composition will decrease.

[0058]

[0059] (C) Glass beads

[0060] A glass bead according to one embodiment of the present invention can be applied together with polyphenylene ether resin, rubber-modified polystyrene resin, aromatic phosphate compound, metal phosphinate compound, DOPO, and styrene-ethylene / butylene-styrene copolymer, etc., to improve the stiffness, impact resistance, dimensional stability (flexural properties), flame retardancy, discoloration stability, and the balance of physical properties thereof of a thermoplastic resin composition, and can use a glass bead used in a conventional thermoplastic resin composition.

[0061] In a specific example, the shape of the glass bead may be a bead, a drop, a sphere, or a ball. Additionally, the glass bead may be solid or hollow.

[0062] In a specific example, the glass beads may have an average particle size measured by scanning electron microscopy (SEM) of about 1 to about 100 μm, for example, about 1 to about 80 μm, for example, about 1 to about 60 μm, for example, about 5 to about 60 μm, for example, about 10 to about 50 μm. Within the above range, the mechanical properties, dimensional stability, appearance characteristics, etc. of the thermoplastic resin composition may be excellent. Here, the average particle size refers to the number average diameter, and means measuring D50 (the particle size at the point where the distribution rate is 50%).

[0063] In a specific example, the glass beads may have an aspect ratio, that is, the ratio of the longest diameter to the shortest diameter among the glass bead particles, of about 0.9 to about 1.1. Within this range, the mechanical properties, dimensional stability, appearance characteristics, etc. of the thermoplastic resin composition may be excellent.

[0064] In a specific example, the glass beads may be included in an amount of about 7 to about 15 weight%, for example, about 11 to about 14 weight%, of 100 weight% of the base material. If the content of the glass beads is less than about 7 weight% of 100 weight% of the base material, there is a risk that the stiffness (tensile strength), etc. of the thermoplastic resin composition will decrease, and if it exceeds about 15 weight%, there is a risk that the stiffness (tensile elongation), etc. of the thermoplastic resin composition will decrease.

[0065]

[0066] (D) Aromatic phosphate compounds

[0067] An aromatic phosphate compound according to one embodiment of the present invention can be applied together with polyphenylene ether resin, rubber-modified polystyrene resin, glass beads, metal phosphinate compound, DOPO, and styrene-ethylene / butylene-styrene copolymer, etc., to improve the stiffness, impact resistance, dimensional stability (flexural properties), flame retardancy, discoloration stability, and balance of physical properties of a thermoplastic resin composition, and an aromatic phosphate compound (phosphorus-based flame retardant) used in a conventional thermoplastic resin composition can be used.

[0068] In a specific example, the aromatic phosphate compound may include bisphenol-A bis(diphenyl phosphate), resorcinol bis(diphenyl phosphate), resorcinol bis[bis(2,6-dimethylphenyl)phosphate], resorcinol bis[bis(2,4-ditertiarybutylphenyl)phosphate], hydroquinone bis[bis(2,6-dimethylphenyl)phosphate], hydroquinone bis[bis(2,4-ditertiarybutylphenyl)phosphate], combinations thereof, etc. For example, bisphenol-A bis(diphenyl phosphate), oligomeric bisphenol-A bis(diphenyl phosphate), etc. may be used as the aromatic phosphate compound.

[0069] In a specific example, the aromatic phosphate compound may be included in an amount of about 10 to about 20 parts by weight, for example, about 11 to about 17 parts by weight, with respect to about 100 parts by weight of the base material. If the content of the aromatic phosphate compound is less than about 10 parts by weight with respect to about 100 parts by weight of the base material, there is a risk that the stiffness (tensile strength, etc.) of the thermoplastic resin composition may decrease, and if it exceeds about 20 parts by weight, there is a risk that the discoloration stability of the thermoplastic resin composition may decrease.

[0070]

[0071] (E) Metal phosphinate compounds

[0072] A metal phosphinate compound according to one embodiment of the present invention can be applied together with polyphenylene ether resin, rubber-modified polystyrene resin, glass beads, aromatic phosphate compounds, DOPO and styrene-ethylene / butylene-styrene copolymer, etc., to improve the stiffness, impact resistance, dimensional stability (flexural properties), flame retardancy, discoloration stability, and balance of physical properties thereof of a thermoplastic resin composition, and a compound represented by the following chemical formula 2 may be used.

[0073] [Chemical Formula 2]

[0074]

[0075] In the above chemical formula 2, R1 and R2 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, M is Al, Zn, Mg, Ca, Sb, Sn, Ge, Ti, Fe, Zr, Ce, Bi, Sr, Mn, Li, or Na, and n is an integer from 1 to 4.

[0076] In a specific example, aluminum diethyl phosphinate, zinc diethyl phosphinate, etc. can be used as the metal phosphinate compound.

[0077] In a specific example, the metal phosphinate compound may be included in an amount of about 0.8 to about 5 parts by weight, for example, about 1.5 to about 3 parts by weight, with respect to about 100 parts by weight of the base material. If the content of the metal phosphinate compound is less than about 0.8 parts by weight with respect to about 100 parts by weight of the base material, there is a risk that the flame retardancy, etc. of the thermoplastic resin composition may be reduced, and if it exceeds about 5 parts by weight, there is a risk that the impact resistance, stiffness (tensile elongation), etc. of the thermoplastic resin composition may be reduced.

[0078] In a specific example, the weight ratio of the rubber-modified polystyrene resin and the metal phosphinate compound may be about 1:0.01 to about 1:0.5, for example, about 1:0.02 to about 1:0.4. Within this range, the impact resistance, dimensional stability (flexural properties), flame retardancy, etc. of the thermoplastic resin composition may be superior.

[0079] In a specific example, the weight ratio of the aromatic phosphate compound and the metal phosphinate compound (aromatic phosphate compound : metal phosphinate compound) may be about 1 : 0.09 to about 1 : 0.4, for example, about 1 : 0.1 to about 1 : 0.3. If the weight ratio of the aromatic phosphate compound and the metal phosphinate compound is less than about 1 : 0.09, there is a risk that the flame retardancy of the thermoplastic resin composition may be reduced, and if it exceeds about 1 : 0.4, there is a risk that the impact resistance, stiffness (tensile elongation), etc. of the thermoplastic resin composition may be reduced.

[0080]

[0081] (F) dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)

[0082] According to one embodiment of the present invention, 9,10-dihydro-9-oxa-10-phosphahenanthrene-10-oxide (DOPO) can be applied together with polyphenylene ether resin, rubber-modified polystyrene resin, glass beads, aromatic phosphate compounds, metal phosphinate compounds, and styrene-ethylene / butylene-styrene copolymers to improve the stiffness, impact resistance, dimensional stability (flexural properties), flame retardancy, discoloration stability, and balance of physical properties of a thermoplastic resin composition, and DOPO used in conventional thermoplastic resin compositions can be applied.

[0083] In a specific example, the DOPO may be included in an amount of about 0.1 to about 1 part by weight, for example, about 0.1 to about 0.5 parts by weight, with respect to about 100 parts by weight of the base material. If the content of the DOPO is less than about 0.1 parts by weight with respect to about 100 parts by weight of the base material, there is a risk that the discoloration stability of the thermoplastic resin composition may be reduced, and if it exceeds about 1 part by weight, there is a risk that the impact resistance, stiffness (tensile strength), etc. of the thermoplastic resin composition may be reduced.

[0084] In a specific example, the weight ratio of the polyphenylene ether resin and the DOPO may be about 1:0.0013 to about 1:0.0150, for example, about 1:0.0014 to about 1:0.0078. Within this range, the discoloration stability, mechanical properties, and balance of properties of the thermoplastic resin composition may be superior.

[0085] In a specific example, the weight ratio of the aromatic phosphate compound and the DOPO (aromatic phosphate compound : DOPO) may be about 1 : 0.006 to about 1 : 0.05, for example, about 1 : about 0.007 to about 1 : about 0.04. If the weight ratio of the aromatic phosphate compound and the DOPO is less than about 1 : 0.006, there is a risk that the stiffness (tensile elongation) of the thermoplastic resin composition may decrease, and if it exceeds about 1 : 0.05, there is a risk that the impact resistance of the thermoplastic resin composition may decrease.

[0086]

[0087] (G) Styrene-ethylene / butylene-styrene copolymer

[0088] A styrene-ethylene / butylene-styrene copolymer (SEBS) according to one embodiment of the present invention can be applied together with polyphenylene ether resin, rubber-modified polystyrene resin, glass beads, aromatic phosphate compounds, metal phosphinate compounds, DOPO, etc., to improve the stiffness, impact resistance, dimensional stability (flexural properties), flame retardancy, discoloration stability, and balance of physical properties of a thermoplastic resin composition, and a styrene-ethylene / butylene-styrene copolymer applied to a conventional thermoplastic resin composition can be used.

[0089] In a specific example, the styrene-ethylene / butylene-styrene copolymer may have a melt-flow index (MI) of about 10 to about 50 g / 10 min, for example, about 12 to about 48 g / 10 min, measured at 200°C and 5 kgf according to ASTM D1238. Within this range, the impact resistance, dimensional stability, stiffness, fluidity, and appearance characteristics of the thermoplastic resin composition may be excellent.

[0090] In a specific example, the styrene-ethylene / butylene-styrene copolymer may be included in an amount of about 2 to about 8 parts by weight, for example, about 3 to about 7 parts by weight, with respect to about 100 parts by weight of the base material. If the content of the styrene-ethylene / butylene-styrene copolymer is less than about 2 parts by weight with respect to about 100 parts by weight of the base material, there is a risk that the impact resistance, etc. of the thermoplastic resin composition may be reduced, and if it exceeds about 8 parts by weight, there is a risk that the flame retardancy, stiffness (tensile strength), etc. of the thermoplastic resin composition may be reduced.

[0091]

[0092] (H) Glass fiber

[0093] A thermoplastic resin composition according to one embodiment of the present invention may further include glass fibers to improve mechanical properties such as stiffness and impact resistance.

[0094] In a specific embodiment, the glass fiber may be in the form of a fiber and may have a cross-section of various shapes, such as circular, elliptical, or rectangular. For example, using a fiber-shaped glass fiber with a circular and / or rectangular cross-section may be preferable in terms of mechanical properties.

[0095] In a specific example, the glass fiber with a circular cross section may have a cross-sectional diameter of about 5 to about 20 μm and a length before processing of about 2 to about 20 mm, and the glass fiber with a rectangular cross section may have a cross-sectional aspect ratio (major axis of the cross section / minor axis of the cross section) of about 1.5 to about 10, a minor axis of about 2 to about 10 μm, and a length before processing of about 2 to about 20 mm. Within the above range, the rigidity, processability, etc. of the thermoplastic resin composition may be improved.

[0096] In a specific example, the glass fiber may be treated with a conventional surface treatment agent. The surface treatment agent may include, but is not limited to, silane compounds, urethane compounds, epoxy compounds, etc.

[0097] In a specific example, when using the glass fiber, the content may be about 1 to about 5 parts by weight, for example, about 1 to about 4 parts by weight, with respect to about 100 parts by weight of the base material. Within this range, the rigidity, impact resistance, etc., may be superior without reducing the dimensional stability, etc., of the thermoplastic resin composition.

[0098]

[0099] A thermoplastic resin composition according to one embodiment of the present invention may further include additives included in conventional thermoplastic resin compositions. Examples of said additives include, but are not limited to, antioxidants, coupling agents (such as aminosilane coupling agents), surfactants, lubricants, release agents, nucleating agents, UV stabilizers, pigments, dyes, and mixtures thereof.

[0100] In a specific example, when using the above additive, the content may be about 0.001 to about 40 parts by weight, for example, about 0.1 to about 10 parts by weight, with respect to about 100 parts by weight of the base material.

[0101]

[0102] A thermoplastic resin composition according to one embodiment of the present invention may be in the form of pellets produced by mixing the above components and melt-extruding them using a conventional twin-screw extruder at about 250 to about 320°C, for example, about 280 to about 300°C.

[0103] In a specific example, the thermoplastic resin composition may have a tensile elongation of about 7 to about 20%, for example, about 7 to about 15%, of a 3.2 mm thick specimen measured under 5 mm / min conditions according to ASTM D638.

[0104] In a specific example, the thermoplastic resin composition has a tensile strength of about 520 to about 800 kgf / cm² of a 3.2 mm thick specimen measured at 5 mm / min according to ASTM D638. 2, for example, about 520 to about 700 kgf / cm² 2 It could be.

[0105] In a specific example, the thermoplastic resin composition may have a notched Izod impact strength of a 1 / 8" thick specimen measured according to ASTM D256 of about 8 to about 16 kgf·cm / cm, for example, about 8 to about 14 kgf·cm / cm.

[0106] In a specific example, the thermoplastic resin composition may have a flow direction (MD) molding shrinkage rate of about 0.4 to about 0.8%, for example, about 0.5 to about 0.7%, measured on a circular specimen with a thickness of 3.2 mm and a diameter of 100 mm according to ASTM D955, and a vertical direction (TD) molding shrinkage rate of about 0.4 to about 0.8%, for example, about 0.5 to about 0.7%.

[0107] In a specific example, the thermoplastic resin composition may have a flame retardancy of V-0 on a 0.8 mm thick specimen measured by the UL-94 vertical test method.

[0108] In a specific example, the thermoplastic resin composition may have a Yellow Index (YI) of about 25 to about 45, for example, about 30 to about 45, calculated from a transmission spectrum measured at wavelengths between 400 nm and 700 nm for a 2.5 mm thick specimen (length and width each of 600 mm) in accordance with ASTM D1925. Here, the Yellow Index (YI) was measured in transmission mode using a Color-Eye 7000A device from GretagMacbeth and included UV.

[0109]

[0110] The molded article according to the present invention is formed from the thermoplastic resin composition. The thermoplastic resin composition may be manufactured in the form of pellets, and the manufactured pellets may be produced into various molded articles (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such molding methods are well known to those skilled in the art to which the present invention belongs. Since the molded article has excellent rigidity, impact resistance, dimensional stability (flexural characteristics), flame retardancy, discoloration stability, and a balance of these physical properties, it is useful as a battery module, such as an EV battery panel busbar.

[0111]

[0112] The present invention is to be explained more specifically through the following examples, but these examples are for illustrative purposes only and should not be interpreted as limiting the invention.

[0113]

[0114] Examples

[0115] The specifications of each component used in the examples and comparative examples below are as follows.

[0116] (A) Polyphenylene ether resin

[0117] Poly(2,6-dimethyl-1,4-phenylene) ether (Manufacturer: Bluestar, Product Name: LXR-040) was used.

[0118] (B) Rubber-modified polystyrene resin

[0119] Impact-resistant polystyrene (HIPS) resin (Manufacturer: Idemitsu PS, Product Name: CT60) was used.

[0120] (C) Glass beads

[0121] Glass beads (Manufacturer: Sovitec, Product name: 1000AQ) were used.

[0122] (D) Aromatic phosphate compounds

[0123] Oligomer bisphenol-A bis(diphenyl phosphate) (BDP, Manufacturer: Yoke Chemical, Product Name: YOKE BDP) was used.

[0124] (E) Metal phosphinate compounds

[0125] Aluminum diethyl phosphinate (Manufacturer: Chempia, Product name: X-GUARD FR-133L) was used.

[0126] (F) DOPO

[0127] Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO, Manufacturer: Shouguang Weidong Chemical, Product Name: DOPO) was used.

[0128] (G) Styrene-ethylene / butylene-styrene copolymer

[0129] Styrene-ethylene / butylene-styrene copolymer (SEBS, manufacturer: Kraton, product name: G1651) was used.

[0130] (H) Glass fiber

[0131] Glass fiber (Manufacturer: Nippon Electric Glass, Product Name: T249) was used.

[0132]

[0133] Examples 1 to 14 and Comparative Examples 1 to 15

[0134] Each of the above components was added in the amounts listed in Tables 1, 2, 3, 4, and 5 below, and pellets were prepared by extrusion at approximately 280°C. A twin-screw extruder with L / D=36 and a diameter of 45 mm was used for extrusion. The prepared pellets were dried at approximately 80°C for at least 2 hours, and then injection molded in a 6 oz injection molding machine (molding temperature: approximately 300°C, mold temperature: approximately 80°C) to produce specimens. The physical properties of the prepared specimens were evaluated by the following method, and the results are shown in Tables 1, 2, 3, 4, and 5 below.

[0135]

[0136] Methods for measuring physical properties

[0137] (1) Tensile elongation (unit: %): According to ASTM D638, the tensile elongation of a 3.2 mm thick specimen was measured at a speed of 5 mm / min.

[0138] (2) Tensile strength (unit: kgf / cm²) 2 In accordance with ASTM D638, the tensile strength of a 3.2 mm thick specimen was measured at a speed of 5 mm / min.

[0139] (3) Notched Izod impact strength (unit: kgf·cm / cm): The notched Izod impact strength of a 1 / 8" thick specimen was measured according to ASTM D256.

[0140] (4) Molding shrinkage rate (unit: %): According to ASTM D955, the molding shrinkage rate in the flow direction (MD) and the molding shrinkage rate in the vertical direction (TD) of a circular specimen with a thickness of 3.2 mm and a diameter of 100 mm were measured.

[0141] (5) Flame retardancy: The flame retardancy of a 0.8 mm thick injection molded specimen was measured using the UL-94 vertical test method.

[0142] (6) Discoloration stability: The Yellow Index (YI) value was calculated according to ASTM D1925 from the transmission spectrum measured at wavelengths between 400 nm and 700 nm for a 2.5 mm thick specimen (length and width each were 600 mm). The Yellow Index was measured in transmission mode using a GretagMacbeth Color-Eye 7000A device, including UV. Discoloration stability was determined to be excellent when the Yellow Index was less than 45.

[0143]

[0144] Example 1 234567(A) (Weight%) 61667266656666(B) (Weight%) 27221623212222(C) (Weight%) 12121211141212(D) (Parts by weight) 14141414141117(E) (Parts by weight) 2222222(F) (Parts by weight) 0.20.20.20.20.20.20.20.2(G) (Parts by weight) 5555555(H) (Parts by weight)-------Tensile elongation 1210.8101191010 Tensile strength 530555570560550560570 Notched Izod impact strength 9.59.39.09.68.89.38.9MD Molding shrinkage rate 0.630.630.630.630.630.630.63TD Molding shrinkage rate 0.630.630.630.630.630.630.63 Flame retardancy V-0V-0V-0V-0V-0V-0V-0 Yellow index 40404040404040

[0145] * Parts by weight: Parts by weight relative to 100 parts by weight of base material (A+B+C)

[0146]

[0147] Example 891011121314(A) (Weight%) 6666666666666666(B) (Weight%) 22222222222222222(C) (Weight%) 1212121212121212(D) (Parts by weight) 14141414141414(E) (Parts by weight) 1.5322222(F) (Parts by weight) 0.20.20.10.50.20.20.2(G) (Parts by weight) 5555375(H) (Parts by weight)------2 Tensile elongation 9.27.58.88.68.88.68.6 Tensile strength 540.525540.530.550.525571 Notched Izod impact strength 9.58.59.78.99.510.99.2MD Molding shrinkage rate 0.620.620.620.620.620.620.57TD Molding shrinkage rate 0.620.620.620.620.620.620.620.62 Flame retardancy V-0V-0V-0V-0V-0V-0V-0 Yellow index 40394337414040

[0148] * Parts by weight: Parts by weight relative to 100 parts by weight of base material (A+B+C)

[0149]

[0150] Comparative Example 12345(A) (Weight%) 4982706266(B) (Weight%) 396251822(C) (Weight%) 121252012(D) (Parts by weight) 141414145(E) (Parts by weight) 22222(F) (Parts by weight) 0.20.20.20.20.2(G) (Parts by weight) 55555(H) (Parts by weight)-----Tensile Elongation 10514410 Tensile Strength 480590510530510 Notched Izod Impact Strength 11.58.210.38.59.4MD Molding Shrinkage 0.620.620.620.620.62TD Molding shrinkage rate 0.620.620.620.620.62 Flame retardancy V-1V-0V-0V-0V-0 Yellow index 4040404040

[0151] * Parts by weight: Parts by weight relative to 100 parts by weight of base material (A+B+C)

[0152]

[0153] Comparative Example 67891011(A) (Weight%) 6666666666666(B) (Weight%) 2222222222222(C) (Weight%) 121212121212(D) (Parts by weight) 141414141414(E) (Parts by weight) 0.562222(F) (Parts by weight) 0.20.20.0520.20.2(G) (Parts by weight) 555519(H) (Parts by weight)------Tensile Elongation 10.55.210.49.110.910.4 Tensile Strength 560560550510570490 Notched Izod Impact Strength 10.47.210.06.27.612.3MD Molding shrinkage rate 0.620.620.620.620.620.62TD Molding shrinkage rate 0.620.620.620.620.620.62 Flame retardancy V-1 V-0 V-0 V-0 V-0 V-1 Yellow index 414047294040

[0154] * Parts by weight: Parts by weight relative to 100 parts by weight of base material (A+B+C)

[0155]

[0156] Comparative Example 12131415(A) (Weight%) 66666666(B) (Weight%) 22222222(C) (Weight%) 12121212(D) (Parts by weight) 20102010(E) (Parts by weight) 1522(F) (Parts by weight) 0.20.20.11(G) (Parts by weight) 5555(H) (Parts by weight) ----(D):(E) (Weight ratio) 1:0.05 1:0.51:0.11:0.2(D):(F) (Weight ratio) 1:0.01 1:0.02 1:0.00 51:0.1 Tensile elongation 10.45.85.79.9 Tensile strength 560570530540 Notched Izod impact strength 9.87.19.87.7MD Molding shrinkage rate 0.620.620.620.62TD Molding shrinkage rate 0.620.620.620.62 Flame retardancy V-1 V-0 V-0 V-0 Yellow index 40404333

[0157] * Parts by weight: Parts by weight relative to 100 parts by weight of base material (A+B+C)

[0158]

[0159] From the above results, it can be seen that the thermoplastic resin composition of the present invention exhibits excellent stiffness (tensile elongation, tensile strength), impact resistance (notched Izod impact strength), dimensional stability (flexural characteristics, MD and TD molding shrinkage rates), flame retardancy (flame retardancy), discoloration stability (yellow index), and the balance of these physical properties.

[0160] On the other hand, in Comparative Example 1, where the content of polyphenylene ether resin is less than the range of the present invention and the content of rubber-modified polystyrene resin is greater than the range of the present invention, it can be seen that flame retardancy, stiffness (tensile strength), etc. are reduced; in Comparative Example 2, where the content of polyphenylene ether resin is greater than the range of the present invention and the content of rubber-modified polystyrene resin is less than the range of the present invention, it can be seen that stiffness (tensile elongation), etc. are reduced; in Comparative Example 3, where the content of glass beads is less than the range of the present invention, it can be seen that stiffness (tensile strength), etc. are reduced; and in Comparative Example 4, where the content of glass beads is greater than the range of the present invention, it can be seen that stiffness (tensile elongation), etc. are reduced. In Comparative Example 5, where the content of aromatic phosphate compound is less than the range of the present invention, it can be seen that stiffness (tensile strength), etc. is reduced, and it was confirmed that when the content of aromatic phosphate compound exceeds the range of the present invention, discoloration stability, etc. is reduced. In Comparative Example 6, where the content of the metal phosphinate compound is less than the range of the present invention, it can be seen that flame retardancy and the like are reduced, and in Comparative Example 7, where the content of the metal phosphinate compound exceeds the range of the present invention, it can be seen that impact resistance and stiffness (tensile elongation) are reduced. In Comparative Example 8, where the content of DOPO is less than the range of the present invention, it can be seen that discoloration stability and the like are reduced, and in Comparative Example 9, where the content of DOPO exceeds the range of the present invention, it can be seen that impact resistance and stiffness (tensile strength) are reduced. In Comparative Example 10, where the content of the styrene-ethylene / butylene-styrene copolymer is less than the range of the present invention, it can be seen that impact resistance and the like are reduced, and in Comparative Example 11, where the content of the styrene-ethylene / butylene-styrene copolymer exceeds the range of the present invention, it can be seen that flame retardancy and stiffness (tensile strength) are reduced.

[0161] In addition, even if the content of the aromatic phosphate compound and the metal phosphinate compound falls within the range of the present invention, it can be seen that in Comparative Example 12, where the weight ratio of the aromatic phosphate compound and the metal phosphinate compound is less than the range of the present invention, flame retardancy, etc. is reduced, and in Comparative Example 13, where the weight ratio of the aromatic phosphate compound and the metal phosphinate compound exceeds the range of the present invention, impact resistance, stiffness (tensile elongation), etc. are reduced, and even if the content of the aromatic phosphate compound and DOPO falls within the range of the present invention, it can be seen that in Comparative Example 14, where the weight ratio of the aromatic phosphate compound and DOPO is less than the range of the present invention, stiffness (tensile elongation), etc. is reduced, and in Comparative Example 15, where the weight ratio of the aromatic phosphate compound and DOPO exceeds the range of the present invention, impact resistance, etc. is reduced.

[0162]

[0163] The present invention has been described above with reference to embodiments. Those skilled in the art will understand that the present invention may be embodied in modified forms without departing from the essential characteristics of the invention. Therefore, the disclosed embodiments should be considered in an illustrative rather than a restrictive sense. The scope of the invention is defined by the claims, not by the foregoing description, and all variations within the scope of equivalents should be interpreted as being included in the invention.

Claims

1. About 100 parts by weight of a base material comprising about 55 to about 75 weight% of polyphenylene ether resin, about 10 to about 30 weight% of rubber-modified polystyrene resin, and about 7 to about 15 weight% of glass beads; About 10 to about 20 parts by weight of an aromatic phosphate compound; About 0.8 to about 5 parts by weight of a metal phosphinate compound; About 0.1 to about 1 part by weight of dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO); and It comprises about 2 to about 8 parts by weight of a styrene-ethylene / butylene-styrene copolymer; and The weight ratio of the aromatic phosphate compound and the metal phosphinate compound is about 1:0.09 to about 1:0.4, and A thermoplastic resin composition characterized by the weight ratio of the aromatic phosphate compound and the DOPO being about 1:0.006 to about 1:0.

05.

2. A thermoplastic resin composition according to claim 1, characterized in that the polyphenylene ether resin comprises a repeating unit represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, R1, R2, R3, and R4 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

3. A thermoplastic resin composition according to claim 1 or 2, wherein the rubber-modified polystyrene resin is a polymer prepared by polymerizing about 70 to about 97 weight percent of styrene in the presence of about 3 to about 30 weight percent of a rubbery polymer.

4. A thermoplastic resin composition according to any one of claims 1 to 3, wherein the glass beads have an average particle size of about 1 to about 100 μm.

5. A thermoplastic resin composition according to any one of claims 1 to 4, wherein the aromatic phosphate compound comprises one or more of bisphenol-A bis(diphenylphosphate), resorcinol bis(diphenylphosphate), resorcinol bis[bis(2,6-dimethylphenyl)phosphate], resorcinol bis[bis(2,4-ditertiarybutylphenyl)phosphate], hydroquinone bis[bis(2,6-dimethylphenyl)phosphate], and hydroquinone bis[bis(2,4-ditertiarybutylphenyl)phosphate].

6. A thermoplastic resin composition according to any one of claims 1 to 5, wherein the metal phosphinate compound is represented by the following chemical formula 2: [Chemical Formula 2] In the above chemical formula 2, R1 and R2 are each independently an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, M is Al, Zn, Mg, Ca, Sb, Sn, Ge, Ti, Fe, Zr, Ce, Bi, Sr, Mn, Li, or Na, and n is an integer from 1 to 4.

7. A thermoplastic resin composition according to any one of claims 1 to 6, wherein the styrene-ethylene / butylene-styrene copolymer has a melt flow index of about 10 to about 50 g / 10 min measured at 200°C and 5 kgf in accordance with ASTM D1238.

8. A thermoplastic resin composition according to any one of claims 1 to 7, wherein the thermoplastic resin composition further comprises about 1 to about 5 parts by weight of glass fibers with respect to about 100 parts by weight of the base material.

9. A thermoplastic resin composition characterized in that, in any one of claims 1 to 8, the weight ratio of the rubber-modified polystyrene resin and the metal phosphinate compound is about 1:0.01 to about 1:0.

5.

10. A thermoplastic resin composition characterized in that, in any one of claims 1 to 9, the weight ratio of the polyphenylene ether resin to the DOPO is about 1:0.0013 to about 1:0.0150.

11. In any one of claims 1 to 10, the thermoplastic resin composition has a tensile elongation of about 7 to about 20% for a 3.2 mm thick specimen measured at 5 mm / min in accordance with ASTM D638, and a tensile strength of about 520 to about 800 kgf / cm² for a 3.2 mm thick specimen measured at 5 mm / min in accordance with ASTM D638. 2 A thermoplastic resin composition characterized by being 12. A thermoplastic resin composition according to any one of claims 1 to 11, wherein the thermoplastic resin composition has a notched Izod impact strength of about 8 to about 16 kgf·cm / cm of a 1 / 8" thickness specimen measured according to ASTM D256.

13. A thermoplastic resin composition according to any one of claims 1 to 12, wherein the thermoplastic resin composition has a flow direction (MD) molding shrinkage rate of about 0.4 to about 0.8% and a vertical direction (TD) molding shrinkage rate of about 0.4 to about 0.8%, measured on a circular specimen with a thickness of 3.2 mm and a diameter of 100 mm in accordance with ASTM D955.

14. A thermoplastic resin composition according to any one of claims 1 to 13, wherein the thermoplastic resin composition is characterized by having a flame retardancy of V-0 on a 0.8 mm thick specimen measured by the UL-94 vertical test method.

15. A molded article characterized by being formed from a thermoplastic resin composition according to any one of claims 1 to 14.

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