Thermoplastic resin composition and article produced therefrom

Abstract

The present application provides a thermoplastic resin composition and an article produced therefrom. The thermoplastic resin composition includes 100 parts by weight of a polybutylene terephthalate resin, 3 to 33 parts by weight of a polycarbonate resin, 60 to 120 parts by weight of glass fibers, and 1 to 9 parts by weight of a glycidyl methacrylate-modified polyolefin, wherein the glass fibers and the glycidyl methacrylate-modified polyolefin are present in a weight ratio of 1:0.02 to 1:0.12. The thermoplastic resin composition has good properties in terms of glass adhesion, metal adhesion, impact resistance, and a balance therebetween.

Description

Technical Field

[0001] This invention relates to thermoplastic resin compositions and articles thereof. More specifically, this invention relates to thermoplastic resin compositions and articles thereof that exhibit good properties in terms of glass adhesion, metal adhesion, impact resistance, and a balance thereof. Background Technology

[0002] As engineered plastics, polyester resins, as well as blends of polyester and polycarbonate resins, exhibit useful properties and are used in a variety of fields, including internal and external materials for electrical / electronic products. However, polyester resins suffer from problems such as low crystallization rate, low mechanical strength, and low impact strength.

[0003] Therefore, various attempts have been made to improve the mechanical properties of polyester resins, including impact resistance and rigidity, by adding additives (such as inorganic fillers). For example, polybutylene terephthalate (PBT) resin reinforced with inorganic fillers (such as glass fiber) is often used as a material for automotive components. However, due to the limited improvement in impact resistance and rigidity, problems such as deterioration in glass adhesion and metal adhesion exist.

[0004] Therefore, there is a need to develop thermoplastic resin compositions that have good properties in terms of glass adhesion, metal adhesion, impact resistance, and a balance between them.

[0005] The background technology of this invention is disclosed in Korean Patent Registration No. 10-0709878, etc. Summary of the Invention

[0006] An aspect of the present invention is to provide thermoplastic resin compositions and articles thereof that have good properties in terms of glass adhesion, metal adhesion, impact resistance and a balance therebetween.

[0007] 1. One aspect of the present invention relates to a thermoplastic resin composition. The thermoplastic resin composition comprises: 100 parts by weight of polybutylene terephthalate resin; 3 to 33 parts by weight of polycarbonate resin; 60 to 120 parts by weight of glass fiber; and 1 to 9 parts by weight of glycidyl methacrylate-modified polyolefin, wherein the glass fiber and the glycidyl methacrylate-modified polyolefin are present in a weight ratio of 1:0.02 to 1:0.12.

[0008] 2. In Embodiment 1, the polybutylene terephthalate resin may have an intrinsic viscosity [η] of 0.5 dl / g to 1.5 dl / g, as measured according to ASTM D2857.

[0009] 3. In embodiment 1 or 2, the polycarbonate resin may have a weight-average molecular weight of 10,000 g / mol to 50,000 g / mol as measured by gel permeation chromatography (GPC).

[0010] 4. In embodiments 1 to 3, the glycidyl methacrylate-modified polyolefin may include 4 wt% to 15 wt% glycidyl methacrylate.

[0011] 5. In embodiments 1 to 4, the thermoplastic resin composition may have an average potential energy of 700 MJ to 870 MJ, which is calculated by the following process: according to the DuPont drop test method, by dropping a dart weighing 50 g to 900 g from a height of 5 cm to 100 cm onto the sample, measuring and averaging the potential energy values ​​when five samples, each with dimensions of 50 mm × 50 mm × 4 mm, are separated from a glass substrate with dimensions of 25 mm × 25 mm × 3 mm, wherein a urethane adhesive (HBFuller Ltd., EH9777BS) is applied to each sample at 110 °C to dimensions of 15 mm × 15 mm × 1 mm, and the glass substrate is bonded to the urethane adhesive, and then cured at 25 °C and 50% RH for 72 hours.

[0012] 6. In embodiments 1 to 5, the thermoplastic resin composition can have a metal bonding strength of 35 MPa to 50 MPa as measured on aluminum metal samples according to ISO 19095.

[0013] 7. In embodiments 1 to 6, the thermoplastic resin composition can have a notched cantilever beam impact strength of 9 kgf·cm / cm to 20 kgf·cm / cm, as measured on a 1 / 8" thick sample according to ASTM D256.

[0014] 8. Another aspect of the present invention relates to an article formed from a thermoplastic resin composition according to any one of embodiments 1 to 7.

[0015] 9. Another aspect of the present invention relates to composite materials. The composite material includes a plastic component as an article of embodiment 8; a metal component adjacent to the plastic component; and a glass component bonded to the plastic component. Detailed Implementation

[0016] The embodiments of the present invention will be described in detail below.

[0017] The thermoplastic resin composition according to the present invention comprises: (A) polybutylene terephthalate resin; (B) polycarbonate resin; (C) glass fiber; and (D) glycidyl methacrylate-modified polyolefin.

[0018] As used in this article to represent a specific numerical range, "a to b" means "≥a and ≤b".

[0019] (A) Polybutylene terephthalate resin

[0020] The polybutylene terephthalate (PBT) resin according to the present invention, together with polycarbonate resin and a specific proportion of glass fiber and glycidyl methacrylate-modified polyolefin, is used to improve the properties of thermoplastic resin compositions in terms of glass adhesion, metal adhesion, impact resistance, and the balance between them, and can be used as a polybutylene terephthalate resin in typical thermoplastic resin compositions. For example, the polybutylene terephthalate resin can be prepared by polycondensation of a dicarboxylic acid component (such as terephthalic acid (TPA) and the like) and a diol component (such as 1,3-butanediol and 1,4-butanediol).

[0021] In some embodiments, the polybutylene terephthalate resin may have an intrinsic viscosity [η] of 0.5 dl / g to 1.5 dl / g, for example, 0.7 dl / g to 1.3 dl / g, as measured according to ASTM D2857. In some embodiments, the polybutylene terephthalate resin may have an intrinsic viscosity [η] of about 0.5 dl / g, 0.6 dl / g, 0.7 dl / g, 0.8 dl / g, 0.9 dl / g, 1.0 dl / g, 1.1 dl / g, 1.2 dl / g, 1.3 dl / g, 1.4 dl / g, or 1.5 dl / g. Further, according to some embodiments, the intrinsic viscosity [η] of the polybutylene terephthalate resin may be about any of the aforementioned values ​​to about any other of the aforementioned values. Within this range, the thermoplastic resin composition may exhibit good properties in terms of mechanical properties, metal adhesion, and injection processing performance.

[0022] (B) Polycarbonate resin

[0023] The polycarbonate resin according to the present invention, together with polybutylene terephthalate resin and a specific proportion of glass fiber and glycidyl methacrylate-modified polyolefin, is used to improve the properties of thermoplastic resin compositions in terms of glass adhesion, metal adhesion, impact resistance, and the balance between them, and can be a polycarbonate resin used in typical thermoplastic resin compositions. For example, the polycarbonate resin can be an aromatic polycarbonate resin prepared by reacting biphenol (an aromatic diol compound) with a precursor (such as phosgene, haloformate, or diester carbonate).

[0024] In some embodiments, biphenol may include, for example, 4,4'-diol, 2,2-bis(4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, and 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, but is not limited thereto. For example, biphenol can be 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane or 1,1-bis(4-hydroxyphenyl)cyclohexane, specifically 2,2-bis(4-hydroxyphenyl)propane, which is also known as bisphenol A.

[0025] In some embodiments, the polycarbonate resin may be a branched polycarbonate resin. For example, the polycarbonate resin may be a polycarbonate resin prepared by adding a trifunctional or higher-functional polyfunctional compound (specifically, a trivalent or higher-valent phenolic compound) in an amount of 0.05 mol% to 2 mol% based on the total moles of biphenyl used in the polymerization.

[0026] In some embodiments, the polycarbonate resin may be a homopolymer polycarbonate resin, a copolymer polycarbonate resin, or a blend thereof. The polycarbonate resin may be partially or completely replaced by an aromatic polyester-carbonate resin prepared by polymerization in the presence of an ester precursor (e.g., a difunctional carboxylic acid).

[0027] In some embodiments, the polycarbonate resin may have a weight-average molecular weight (Mw) of 10,000 g / mol to 50,000 g / mol, for example, 20,000 g / mol to 40,000 g / mol, as measured by gel permeation chromatography (GPC). Within this range, the thermoplastic resin composition may have good impact resistance and flowability (processing properties), etc.

[0028] In some embodiments, the polycarbonate resin may be present in an amount of 3 to 33 parts by weight, for example, 5 to 30 parts by weight, relative to 100 parts by weight of the polybutylene terephthalate resin. In some embodiments, the thermoplastic resin composition may include polycarbonate resin in an amount of about 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, or 33 parts by weight, relative to about 100 parts by weight of the polybutylene terephthalate resin. Furthermore, according to some embodiments, the polycarbonate resin may be present in an amount from about any of the aforementioned amounts to about any of the other aforementioned amounts. If the content of polycarbonate resin is less than 3 parts by weight relative to 100 parts by weight of polybutylene terephthalate resin, the thermoplastic resin composition may experience deterioration in glass adhesion and impact resistance, etc., and if the content of polycarbonate resin exceeds 33 parts by weight, the thermoplastic resin composition may experience deterioration in metal adhesion and flowability, etc.

[0029] (C) Glass fiber

[0030] According to the present invention, glass fiber, together with polybutylene terephthalate resin, polycarbonate resin and a specific amount of glycidyl methacrylate-modified polyolefin, is used to improve the properties of thermoplastic resin compositions in terms of glass adhesion, metal adhesion, impact resistance and the balance therebetween, and can be used in typical thermoplastic resin compositions.

[0031] In some embodiments, the glass fibers may have a fiber shape and may have various cross-sectional shapes, such as circular, elliptical, and rectangular shapes. For example, glass fibers with circular and / or rectangular cross-sectional shapes may be preferred in terms of mechanical properties.

[0032] In some embodiments, glass fibers with a circular cross-section can have a cross-sectional diameter of 5 μm to 20 μm and a pre-processed length of 2 mm to 20 mm, as measured using a scanning electron microscope (SEM). Similarly, glass fibers with a rectangular cross-section can have an aspect ratio (the ratio of the long side length to the short side length on the cross-section) of 1.5 to 10, a short side length of 2 μm to 10 μm, and a pre-processed length of 2 mm to 20 mm, as measured using a scanning electron microscope. Within these ranges, the thermoplastic resin composition can exhibit good rigidity and processability, among other properties.

[0033] In some embodiments, the glass fibers can be surface-treated with typical surface treatment agents. Surface treatment agents may include, but are not limited to, silane compounds, urethane compounds, and epoxy compounds.

[0034] In some embodiments, relative to 100 parts by weight of polybutylene terephthalate resin, glass fiber may be present in an amount of 60 parts by weight to 120 parts by weight, for example, 70 parts by weight to 110 parts by weight. In some embodiments, relative to about 100 parts by weight of polybutylene terephthalate resin, the thermoplastic resin composition may be present in an amount of about 60 parts by weight, 61 parts by weight, 62 parts by weight, 63 parts by weight, 64 parts by weight, 65 parts by weight, 66 parts by weight, 67 parts by weight, 68 parts by weight, 69 parts by weight, 70 parts by weight, 71 parts by weight, 72 parts by weight, 73 parts by weight, 74 parts by weight, 75 parts by weight, 76 parts by weight, 77 parts by weight, 78 parts by weight, 79 parts by weight, 80 parts by weight, 81 parts by weight, 82 parts by weight, 83 parts by weight, 84 parts by weight, 85 parts by weight, 86 parts by weight, 87 parts by weight, 88 parts by weight, 89 parts by weight, etc. The amounts of 9 parts by weight, 90 parts by weight, 91 parts by weight, 92 parts by weight, 93 parts by weight, 94 parts by weight, 95 parts by weight, 96 parts by weight, 97 parts by weight, 98 parts by weight, 99 parts by weight, 100 parts by weight, 101 parts by weight, 102 parts by weight, 103 parts by weight, 104 parts by weight, 105 parts by weight, 106 parts by weight, 107 parts by weight, 108 parts by weight, 109 parts by weight, 110 parts by weight, 111 parts by weight, 112 parts by weight, 113 parts by weight, 114 parts by weight, 115 parts by weight, 116 parts by weight, 117 parts by weight, 118 parts by weight, 119 parts by weight, or 120 parts by weight comprise glass fiber. Further, according to some embodiments, the glass fiber may be present in amounts from about any of the aforementioned amounts to about any of the other aforementioned amounts. If the glass fiber content is less than 60 parts by weight relative to 100 parts by weight of polybutylene terephthalate resin, the thermoplastic resin composition may experience deterioration in impact resistance and flowability, and if the glass fiber content exceeds 120 parts by weight, the thermoplastic resin composition may experience deterioration in glass adhesion and metal adhesion, etc.

[0035] (D) Glycidyl methacrylate-modified polyolefin

[0036] According to the present invention, glycidyl methacrylate-modified polyolefins, together with polybutylene terephthalate resin, polycarbonate resin and a specific amount of glass fiber, are used to improve the properties of thermoplastic resin compositions in terms of glass adhesion, metal adhesion, impact resistance and the balance between them, and can be prepared by polymerization of glycidyl methacrylate compounds containing reactive functional groups with polyolefins (olefin homopolymers, olefin copolymers and olefin-(meth)acrylate copolymers, etc.).

[0037] In some embodiments, the glycidyl methacrylate-modified polyolefin may comprise 4 wt% to 15 wt%, for example, 5 wt% to 12 wt% of glycidyl methacrylate. In some embodiments, based on the total weight (100 wt%) of the glycidyl methacrylate-modified polyolefin, the glycidyl methacrylate-modified polyolefin may include glycidyl methacrylate in amounts of about 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, or 15 wt%. Further, according to some embodiments, glycidyl methacrylate may be present in amounts of about any of the aforementioned amounts to about any of the other aforementioned amounts. Within this range, the thermoplastic resin composition (articles formed from the thermoplastic resin composition) may exhibit good properties such as glass adhesion, metal adhesion, impact resistance, and flowability.

[0038] In some embodiments, glycidyl methacrylate-modified polyolefins may include glycidyl methacrylate-ethylene copolymers, glycidyl methacrylate-methyl acrylate-ethylene copolymers, and combinations thereof.

[0039] In some embodiments, the glycidyl methacrylate-modified polyolefin may have a melt flow index of 2 g / 10 min to 8 g / 10 min, for example, 3 g / 10 min to 7 g / 10 min, as measured according to ASTM D1238 at 190°C and 2.16 kg. In some embodiments, the glycidyl methacrylate-modified polyolefin may have a melt flow index of about 2 g / 10 min, 3 g / 10 min, 4 g / 10 min, 5 g / 10 min, 6 g / 10 min, 7 g / 10 min, or 8 g / 10 min. Further, according to some embodiments, the melt flow index of the glycidyl methacrylate-modified polyolefin may be about any of the aforementioned melt flow indices to about any other of the aforementioned melt flow indices. Within this range, the thermoplastic resin composition (articles formed from the thermoplastic resin composition) may exhibit good glass adhesion and impact resistance, etc.

[0040] In some embodiments, the glycidyl methacrylate-modified polyolefin may be present in an amount of 1 to 9 parts by weight, for example, 2 to 8.2 parts by weight, relative to 100 parts by weight of polybutylene terephthalate resin. In some embodiments, the thermoplastic resin composition may be present in an amount of about 1 part by weight, 1.1 parts by weight, 1.2 parts by weight, 1.3 parts by weight, 1.4 parts by weight, 1.5 parts by weight, 1.6 parts by weight, 1.7 parts by weight, 1.8 parts by weight, 1.9 parts by weight, 2 parts by weight, 2.1 parts by weight, 2.2 parts by weight, 2.3 parts by weight, 2.4 parts by weight, 2.5 parts by weight, relative to about 100 parts by weight of polybutylene terephthalate resin. 2.6 parts by weight, 2.7 parts by weight, 2.8 parts by weight, 2.9 parts by weight, 3 parts by weight, 3.1 parts by weight, 3.2 parts by weight, 3.3 parts by weight, 3.4 parts by weight, 3.5 parts by weight, 3.6 parts by weight, 3.7 parts by weight, 3.8 parts by weight, 3.9 parts by weight, 4 parts by weight, 4.1 parts by weight, 4.2 parts by weight, 4.3 parts by weight, 4.4 parts by weight, 4.5 parts by weight, 4.6 parts by weight, 4.7 parts by weight, 4.8 parts by weight Parts by weight, 4.9 parts by weight, 5 parts by weight, 5.1 parts by weight, 5.2 parts by weight, 5.3 parts by weight, 5.4 parts by weight, 5.5 parts by weight, 5.6 parts by weight, 5.7 parts by weight, 5.8 parts by weight, 5.9 parts by weight, 6 parts by weight, 6.1 parts by weight, 6.2 parts by weight, 6.3 parts by weight, 6.4 parts by weight, 6.5 parts by weight, 6.6 parts by weight, 6.7 parts by weight, 6.8 parts by weight, 6.9 parts by weight, 7 parts by weight, 7.1 parts by weight The amounts of 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, or 9 parts by weight comprise glycidyl methacrylate-modified polyolefins. Further, according to some embodiments, the glycidyl methacrylate-modified polyolefins may be present in amounts from about any of the aforementioned amounts to about any of the other aforementioned amounts. If the content of glycidyl methacrylate-modified polyolefin is less than 1 part by weight relative to 100 parts by weight of polybutylene terephthalate resin, the thermoplastic resin composition may experience deterioration in glass adhesion and impact resistance, etc., and if the content of glycidyl methacrylate-modified polyolefin exceeds 9 parts by weight, the thermoplastic resin composition may experience deterioration in metal adhesion, flowability and injection processing performance, etc.

[0041] In some embodiments, glass fiber and glycidyl methacrylate-modified polyolefin may be present in a weight ratio (C:D) of 1:0.02 to 1:0.12, for example, 1:0.02 to 1:0.10. In some embodiments, glass fiber and glycidyl methacrylate-modified polyolefin may be present in a weight ratio (C:D) of about 1:0.02, 1:0.03, 1:0.04, 1:0.05, 1:0.06, 1:0.07, 1:0.08, 1:0.09, 1:0.10, 1:0.11, or 1:0.12. If the weight ratio of glass fiber to glycidyl methacrylate-modified polyolefin is less than 1:0.02, the thermoplastic resin composition may experience deterioration in glass adhesion, metal adhesion, and impact resistance, etc., and if the weight ratio of glass fiber to glycidyl methacrylate-modified polyolefin exceeds 1:0.12, the thermoplastic resin composition may experience deterioration in impact resistance, flowability, and injection processing performance, etc.

[0042] The thermoplastic resin composition according to one embodiment of the invention may further include additives used in typical thermoplastic resin compositions. Examples of additives may include, but are not limited to, flame retardants, antioxidants, anti-dripping agents, lubricants, mold release agents, nucleating agents, antistatic agents, stabilizers, pigments, dyes, and mixtures thereof. In the thermoplastic resin composition, the additive may be present in an amount of 0.001 to 40 parts by weight, for example, 0.1 to 10 parts by weight, relative to 100 parts by weight of polybutylene terephthalate resin. In some embodiments, the thermoplastic resin composition may be present in amounts of approximately 0.001 parts by weight, 0.002 parts by weight, 0.003 parts by weight, 0.004 parts by weight, 0.005 parts by weight, 0.006 parts by weight, 0.007 parts by weight, 0.008 parts by weight, 0.009 parts by weight, 0.01 parts by weight, 0.02 parts by weight, 0.03 parts by weight, 0.04 parts by weight, 0.05 parts by weight, 0.06 parts by weight, 0.07 parts by weight, 0.08 parts by weight, 0.09 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, and 0.4 parts by weight relative to approximately 100 parts by weight of polybutylene terephthalate resin. The additive is included in amounts of 8 parts by weight, 0.9 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 27 parts by weight, 28 parts by weight, 29 parts by weight, 30 parts by weight, 31 parts by weight, 32 parts by weight, 33 parts by weight, 34 parts by weight, 35 parts by weight, 36 parts by weight, 37 parts by weight, 38 parts by weight, 39 parts by weight, or 40 parts by weight. Further, according to some embodiments, the additive may be present in amounts from about any of the aforementioned amounts to about any of the other aforementioned amounts.

[0043] According to one embodiment of the invention, a thermoplastic resin composition can be prepared into spheres by mixing the aforementioned components and then melt extruding them in a typical twin-bar extruder at 240°C to 300°C, for example, 260°C to 290°C.

[0044] In some embodiments, the thermoplastic resin composition may have an average potential energy of 700 MJ to 870 MJ, for example, 730 MJ to 860 MJ, calculated by the following process: according to the DuPont drop test method, by dropping a dart weighing 50 g to 900 g from a height of 5 cm to 100 cm onto the sample, measuring and averaging the potential energy values ​​when five samples, each with dimensions of 50 mm × 50 mm × 4 mm, are separated from a glass substrate with dimensions of 25 mm × 25 mm × 3 mm, wherein a urethane adhesive (HBFuller Ltd., EH9777BS) is applied to each sample at 110 °C to dimensions of 15 mm × 15 mm × 1 mm, and the glass substrate is bonded to the urethane adhesive, followed by curing at 25 °C and 50% RH for 72 hours. In some embodiments, the thermoplastic resin composition may have a concentration of about 700 MJ, 701 MJ, 702 MJ, 703 MJ, 704 MJ, 705 MJ, 706 MJ, 707 MJ, 708 MJ, 709 MJ, 710 MJ, 711 MJ, 712 MJ, 713 MJ, 714 MJ, 715 MJ, 716 MJ, 717 MJ, 718 MJ, 719 MJ, 720 MJ, 721 MJ, 722 MJ, 723 MJ, 724 MJ, or 725 MJ. 726MJ, 727MJ, 728MJ, 729MJ, 730MJ, 731MJ, 732MJ, 733MJ, 734MJ, 735MJ, 736MJ, 737MJ, 738MJ, 739MJ, 740MJ , 741MJ, 742MJ, 743MJ, 744MJ, 745MJ, 746MJ, 747MJ, 748MJ, 749MJ, 750MJ, 751MJ, 752MJ, 753MJ, 754MJ, 755M J, 756MJ, 757MJ, 758MJ, 759MJ, 760MJ, 761MJ, 762MJ, 763MJ, 764MJ, 765MJ, 766MJ, 767MJ, 768MJ, 769MJ, 770 MJ, 771MJ, 772MJ, 773MJ, 774MJ, 775MJ, 776MJ, 777MJ, 778MJ, 779MJ, 780MJ, 781MJ, 782MJ, 783MJ, 784MJ, 78 5MJ, 786MJ, 787MJ, 788MJ, 789MJ, 790MJ, 791MJ, 792MJ, 793MJ, 794MJ, 795MJ, 796MJ, 797MJ, 798MJ, 799MJ, 8 00MJ, 801MJ, 802MJ, 803MJ, 804MJ, 805MJ, 806MJ, 807MJ, 808MJ, 809MJ, 810MJ, 811MJ, 812MJ, 813MJ, 814MJ,815MJ, 816MJ, 817MJ, 818MJ, 819MJ, 820MJ, 821MJ, 822MJ, 823MJ, 824MJ, 825MJ, 826MJ, 827MJ, 828MJ, 8 29MJ, 830MJ, 831MJ, 832MJ, 833MJ, 834MJ, 835MJ, 836MJ, 837MJ, 838MJ, 839MJ, 840MJ, 841MJ, 842MJ, 84 The average potential energy is 3 MJ, 844 MJ, 845 MJ, 846 MJ, 847 MJ, 848 MJ, 849 MJ, 850 MJ, 851 MJ, 852 MJ, 853 MJ, 854 MJ, 855 MJ, 856 MJ, 857 MJ, 858 MJ, 859 MJ, 860 MJ, 861 MJ, 862 MJ, 863 MJ, 864 MJ, 865 MJ, 866 MJ, 867 MJ, 868 MJ, 869 MJ, or 870 MJ. Further, according to some embodiments, the average potential energy of the thermoplastic resin composition can be about any of the aforementioned average potential energies to about any other of the aforementioned average potential energies.

[0045] In some embodiments, the thermoplastic resin composition, measured on aluminum-based metal samples according to ISO 19095, may have a metal-bond strength of 35 MPa to 50 MPa, for example, 35 MPa to 45 MPa. In some embodiments, the thermoplastic resin composition may have a metal-bond strength of 35 MPa, 36 MPa, 37 MPa, 38 MPa, 39 MPa, 40 MPa, 41 MPa, 42 MPa, 43 MPa, 44 MPa, 45 MPa, 46 MPa, 47 MPa, 48 MPa, 49 MPa, or 50 MPa. Further, according to some embodiments, the metal-bond strength of the thermoplastic resin composition may be about any of the aforementioned metal-bond strengths to about any other of the aforementioned metal-bond strengths.

[0046] In some embodiments, the thermoplastic resin composition may have a notched cantilever beam impact strength of 9 kgf·cm / cm to 20 kgf·cm / cm, for example, 9 kgf·cm / cm to 15 kgf·cm / cm, as measured according to ASTM D256 on a 1 / 8" thick sample. In some embodiments, the thermoplastic resin composition may have a notched cantilever beam impact strength of about 9 kgf·cm / cm, 10 kgf·cm / cm, 11 kgf·cm / cm, 12 kgf·cm / cm, 13 kgf·cm / cm, 14 kgf·cm / cm, 15 kgf·cm / cm, 16 kgf·cm / cm, 17 kgf·cm / cm, 18 kgf·cm / cm, 19 kgf·cm / cm, or 20 kgf·cm / cm. Further, according to some embodiments, the notched cantilever beam impact strength of the thermoplastic resin composition may be about any of the aforementioned notched cantilever beam impact strengths to about any other of the aforementioned notched cantilever beam impact strengths.

[0047] The article according to the invention is formed from the above-described thermoplastic resin composition. The thermoplastic resin composition can be prepared into the form of microspheres. The prepared microspheres can be produced into various articles (products) by various molding methods (such as injection molding, extrusion, vacuum molding, and casting). These molding methods are well known to those skilled in the art. The article has good properties in terms of glass adhesion, metal adhesion, flowability, impact resistance, and a balance between them, and can be used as an internal / external material for electrical / electronic products, internal / external materials for automobiles, and internal / external materials for portable electronic communication devices, etc.

[0048] The composite material according to the invention may include a plastic component as the article; a metal component adjacent to the plastic component; and a glass component bonded to the plastic component.

[0049] In some implementations, the plastic component can be directly adjacent to the metal component without an adhesive between them. For example, the plastic and metal components can be integrally formed together via insert-injection molding.

[0050] In some embodiments, the metal component may include at least one metal selected from aluminum, titanium, iron, and zinc.

[0051] In some implementations, the plastic and glass components can be bonded to each other using an adhesive. For example, after the product (plastic and metal components) manufactured by insert-injection molding (using CNC processes, etc.) has been machined into the desired shape, the glass component can be bonded to it.

[0052] The invention will now be described in more detail with reference to embodiments. However, it should be noted that these embodiments are for illustrative purposes only and should not be construed as limiting the invention in any way.

[0053] Example

[0054] Details of the components used in the examples and comparative examples are as follows.

[0055] (A) Polybutylene terephthalate resin

[0056] Polybutylene terephthalate resin (PBT, manufacturer: Shinkong Synthetic Fibers, product name: Shinite K006, intrinsic viscosity [η]: approx. 1.3 dl / g) was used.

[0057] (B) Polycarbonate resin

[0058] Bisphenol polycarbonate resin (PC, manufacturer: Rakuten Chemical Co., Ltd., weight average molecular weight: approximately 25,000 g / mol) was used.

[0059] (C) Glass fiber

[0060] Flat glass fiber (manufacturer: Nittobo, product name: CSG 3PA-820, short side length: approx. 7μm, aspect ratio on cross section: approx. 4, pre-processed length: approx. 3mm).

[0061] (D) Glycidyl methacrylate-modified polyolefin

[0062] (D1) Using glycidyl methacrylate-modified polyolefin (manufacturer: Arkema, product name: AX-8900, glycidyl methacrylate content: 8wt%).

[0063] (D2) Use glycidyl methacrylate-modified polyolefin (manufacturer: Arkema, product name: AX-8670T, glycidyl methacrylate content: 9wt%).

[0064] (D3) Use of glycidyl methacrylate-modified polyolefin (manufacturer: Sumitomo, product name: BF-7B, glycidyl methacrylate content: 12wt%).

[0065] (D4) Use glycidyl methacrylate-modified polyolefin (manufacturer: Arkema, product name: AX-8750, glycidyl methacrylate content: 5wt%).

[0066] (E) Use ethylene / methyl acrylate copolymer (manufacturer: DuPont, product name: Elvaloy AC1330).

[0067] Examples 1 to 12 and Comparative Examples 1 to 9

[0068] The aforementioned components were mixed in the amounts listed in Tables 1 to 4, and then extruded at 260°C to prepare the thermoplastic resin composition into microspheres. Here, extrusion was performed using a twin-bar extruder (L / D: 44, Φ: 45 mm). The prepared microspheres were dried at 80°C for 4 hours or longer, and then injection molded using a 6 oz injection molding machine (molding temperature: approximately 270°C, mold temperature: approximately 120°C) to prepare samples. The following properties of the prepared samples were evaluated. The results are shown in Tables 1, 2, 3, and 4.

[0069] Feature evaluation

[0070] (1) Average potential energy (unit: MJ): The average potential energy was calculated as follows: according to the DuPont drop test method, the potential energy values ​​measured when five samples, each with a size of 50mm×50mm×4mm, were separated from a glass substrate with a size of 25mm×25mm×3mm by dropping darts weighing 50g to 900g from a height of 5cm to 100cm onto the sample were averaged. In this test, urethane adhesive (HBFuller Ltd., EH9777BS) was applied to each sample with a size of 15mm×15mm×1mm at 110°C, and the glass substrate was bonded to the urethane adhesive. The samples were then cured at 25°C and 50%RH for 72 hours.

[0071] (2) Metal-to-metal bond strength (unit: MPa): The metal-to-metal bond strength was measured according to ISO 19095 after an aluminum metal sample was bonded to a thermoplastic resin composition sample by embedding-injection molding. Here, the metal sample was an aluminum metal sample from Geo Nation Ltd. that had undergone TRI surface treatment to promote adhesion between the metal sample and the resin sample. Each of the metal sample and the resin sample had dimensions of 1.2 cm × 4 cm × 0.3 cm, and the metal-to-metal bond strength between them was measured after the samples were bonded together to have an adhesive area of ​​1.2 cm × 0.3 cm.

[0072] (3) Notched cantilever beam impact resistance (unit: kgf·cm / cm): The notched cantilever beam impact strength was measured on a 1 / 8" thick sample according to ASTM D256.

[0073] Table 1

[0074]

[0075] Table 2

[0076]

[0077] Table 3

[0078]

[0079] Table 4

[0080]

[0081] The results show that the thermoplastic resin composition according to the present invention exhibits good properties in terms of glass adhesion (average potential energy), metal adhesion (metal bond strength), impact resistance (notched cantilever beam impact strength), and the balance between them.

[0082] Conversely, it can be seen that the thermoplastic resin composition of Comparative Example 1, prepared using insufficient polycarbonate resin, exhibits deterioration in glass adhesion and impact resistance; the thermoplastic resin composition of Comparative Example 2, prepared using excessive polycarbonate resin, exhibits deterioration in metal adhesion; the thermoplastic resin composition of Comparative Example 3, prepared using insufficient glass fiber, exhibits deterioration in impact resistance; and the thermoplastic resin composition of Comparative Example 4, prepared using excessive glass fiber, exhibits deterioration in glass adhesion and metal adhesion. Furthermore, it can be seen that the thermoplastic resin composition of Comparative Example 5, prepared using insufficient glycidyl methacrylate-modified polyolefin, exhibits deterioration in glass adhesion and impact resistance; and the thermoplastic resin composition of Comparative Example 6, prepared using excessive glycidyl methacrylate-modified polyolefin, exhibits deterioration in metal adhesion. It can be seen that the thermoplastic resin composition of Comparative Example 7, prepared by using ethylene / methyl acrylate copolymer (E) instead of glycidyl methacrylate-modified polyolefin, exhibits deterioration in glass adhesion and metal adhesion. Furthermore, it can be seen that, compared with glass fiber and glycidyl methacrylate-modified polyolefin within the content range of the present invention, thermoplastic resin compositions with a weight ratio (C:D1)(1:0.137) less than 1:0.12 (Comparative Example 8) exhibit deterioration in impact resistance, etc., and thermoplastic resin compositions with a weight ratio (C:D1)(1:0.018) greater than 1:0.02 (Comparative Example 9) exhibit deterioration in glass adhesion, metal adhesion and impact resistance, etc.

[0083] Although some exemplary embodiments have been described herein, those skilled in the art will understand that these embodiments are given by way of illustration only, and modifications, variations, and alterations may be made without departing from the spirit and scope of the invention. Therefore, the embodiments should not be construed as limiting the technical spirit of the invention, but rather as illustrative of it. The scope of the invention should be interpreted according to the appended claims to cover all modifications or variations derived from the appended claims and their equivalents.

Claims

1. A thermoplastic resin composition comprising the following: 100 parts by weight of polybutylene terephthalate resin; 3 to 33 parts by weight of bisphenol A polycarbonate resin; 60 to 120 parts by weight of glass fiber; and 1 to 9 parts by weight of glycidyl methacrylate-modified polyolefin, The glass fiber and the glycidyl methacrylate-modified polyolefin are present in a weight ratio of 1:0.02 to 1:0.

12. The thermoplastic resin composition described herein has an average potential energy of 700 MJ to 870 MJ, which is calculated by the following procedure: according to the DuPont drop test method, the potential energy values ​​of five samples, each with dimensions of 50 mm × 50 mm × 4 mm, are measured and averaged when they are separated from a glass substrate with dimensions of 25 mm × 25 mm × 3 mm by dropping a dart weighing 50 g to 900 g from a height of 5 cm to 100 cm onto the sample. A 15 mm × 15 mm × 1 mm dimension of urethane adhesive is applied to each sample at 110 °C, and the glass substrate is bonded to the urethane adhesive, followed by curing at 25 °C and 50% RH for 72 hours. The glycidyl methacrylate-modified polyolefin comprises 4 wt% to 15 wt% glycidyl methacrylate.

2. The thermoplastic resin composition according to claim 1, wherein the polybutylene terephthalate resin has an intrinsic viscosity of 0.5 dl / g to 1.5 dl / g as measured according to ASTM D2857.

3. The thermoplastic resin composition according to claim 1, wherein the polycarbonate resin has a weight-average molecular weight of 10,000 g / mol to 50,000 g / mol as measured by gel permeation chromatography.

4. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a metal bonding strength of 35 MPa to 50 MPa as measured on an aluminum metal sample according to ISO 19095.

5. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a notched cantilever beam impact strength of 9 kgf·cm / cm to 20 kgf·cm / cm as measured on a 1 / 8" thick sample according to ASTM D256.

6. An article formed from a thermoplastic resin composition according to any one of claims 1 to 5.

7. A composite material, comprising: Plastic components as the article according to claim 6; Metal components adjacent to the plastic component; and A glass component bonded to the plastic component.

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