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KR-102963161-B1 - Polymer composition and articles manufactured therefrom

KR102963161B1KR 102963161 B1KR102963161 B1KR 102963161B1KR-102963161-B1

Abstract

The present application relates to a polymer composition comprising 20 wt% to 30 wt% of polycarbonate; 40 wt% to 60 wt% of polybutylene terephthalate; 5 wt% to 30 wt% of reinforcing fibers; 1 wt% to 10 wt% of glass bubbles; and 0.3 wt% to 2 wt% of an ester exchange inhibitor, all contents based on the total weight of the composition. The polymer composition according to the present invention has improved adhesion to metal (particularly aluminum) even after annealing and anodizing processes are applied.

Inventors

  • 왕, 리스
  • 왕, 샤오시앙

Assignees

  • 코베스트로 인텔렉쳐 프로퍼티 게엠베하 운트 콤파니 카게

Dates

Publication Date
20260511
Application Date
20200827
Priority Date
20190905

Claims (15)

  1. A polymer composition comprising the following, wherein all contents are based on the total weight of the composition: A). 20 wt% to 30 wt% of polycarbonate; B). 40 wt% to 60 wt% of polybutylene terephthalate; C). 5 wt% to 30 wt% of reinforcing fibers; D). 1 wt% to 10 wt% of glass bubbles, and E). 0.3 wt% to 2 wt% of an ester exchange inhibitor.
  2. A composition according to claim 1, wherein the polycarbonate is an aromatic polycarbonate derived from the reaction of a diphenol of formula (I) with a carbonate halide, phosgene, an aromatic dicarboxylic acid dihalide, or a benzene dicarboxylic acid dihalide: Here A is a single bond, C1 - C5 -alkylene, C2 - C5 -alkylidene, C5 - C6 -cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO2-, C6 - C12 - arylene to which an additional aromatic ring optionally containing a heteroatom can be condensed, or a group of formula (II) or (III): B is C1 - C12 -alkyl, methyl, halogen, chlorine, or bromine in each case, and x is 0, 1, or 2 independently in each case, and p is 1 or 0, and R5 and R6 can be independently selected from each other as hydrogen, C1 - C6 -alkyl, methyl, or ethyl, individually for each X', and X 1 is carbon, and m is an integer from 4 to 7, 4, or 5, and However, on at least one X 1 atom, R 5 and R 6 are both alkyl.
  3. In paragraph 2, the diphenol is 4,4'-dihydroxydiphenyl, bisphenol A, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4-hydroxyphenyl)-cyclohexane, 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl-sulfone and their brominated and sabrominated or chlorinated derivatives, 2,2-bis(3-chloro-4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane, or 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane; Diphenol of chemical formula (IVa): Here R1 represents hydrogen or C1 - C4 -alkyl, and R2 represents a C1 - C4 -alkyl or methyl group, and n represents 0, 1, 2, or 3; and A composition selected from diphenols of chemical formulas (IVb), (IVc) and (IVd): Here, R3 represents a C1 - C4 -alkyl, aralkyl, aryl, methyl, or phenyl group.
  4. In claim 1, the polycarbonate is based on bisphenol A (2,2-bis-(4-hydroxyphenyl)-propane) or is based on bisphenol A and 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC) having the formula (IVa"): The molar ratio of diphenol to bisphenol A of the formula (IVa") is 1% : 99% to 99% : 1%, 10% : 90% to 90% : 10%, 20% : 80% to 80% : 20%, or 30% : 70% to 70% : 30% Composition.
  5. A composition according to any one of claims 1 to 4, wherein the reinforcing fiber is glass fiber or selected from the group consisting of E-glass, S-glass, AR-glass, T-glass, D-glass, and R-glass.
  6. A composition according to any one of claims 1 to 4, wherein the diameter of the glass bubbles is 1 to 50 μm, 5 to 40 μm, or 10 to 35 μm.
  7. A composition according to any one of claims 1 to 4, wherein the ester exchange inhibitor is a phosphorus-containing stabilizer selected from acidic phosphate salts, phosphite compounds, and phospho-oxo acids.
  8. In claim 7, the acidic phosphate salt is selected from the group consisting of monozinc phosphate, sodium dihydrogen phosphate, potassium hydrogen phosphate, calcium hydrogen phosphate, sodium acid pyrophosphate, and mixtures thereof, and Phosphite compounds are selected from those of chemical formula (V): P-(OR 1 ) 3 (V) Here, each R1 is identical or different and independently represents hydrogen, an alkyl group, an aryl group, or any mixture thereof, provided that at least one of the R' groups is hydrogen or alkyl. The oxo-acid is selected from the group consisting of phosphoric acid, phosphoric acid, polyphosphoric acid, hypophosphoric acid and mixtures thereof; or Ester exchange inhibitors are phosphorus phosphate Composition.
  9. Articles including the following: metal substrate; and A plastic member manufactured from a polymer composition according to any one of claims 1 to 4 on a metal substrate.
  10. Article 9, wherein the metal substrate is an aluminum sheet.
  11. In paragraph 9, an article that is an outer shell for a mobile phone.
  12. A method for manufacturing an article comprising a plastic member manufactured from a metal substrate and a polymer composition according to any one of claims 1 to 4 on the metal substrate, comprising the following steps: A step of forming a plastic member on a metal substrate using a polymer composition according to any one of claims 1 to 4.
  13. In paragraph 12, a method of manufacturing an article comprising the following steps: Step S1: A step of treating the surface of a metal substrate to form nano-pores having a diameter of 10 nm to 30 nm in at least a portion of the surface of the metal substrate; and Step S2: A step of forming a plastic member on a metal substrate by injection molding the polymer composition onto a treated surface of a metal substrate.
  14. In paragraph 13, a method of manufacturing an article further comprising the following steps: Step S3: A step of applying annealing to the article from S2 at a temperature of 50°C to 200°C for 1-2 hours.
  15. In paragraph 14, a method of manufacturing an article further comprising the following steps: Step S4: A step of applying anodizing to the product from S3.

Description

Polymer composition and articles manufactured therefrom The present invention relates to a polymer composition, in particular to a polymer composition for use in combination with a metal substrate for an electronic device, and an article made therefrom. Metal housings are widely used in electronic devices such as mobile phones or personal information terminals (PDAs). Antennas are also important components of electronic devices. Metal housings can provide electromagnetic shielding to antennas located within them, and thus, antenna signals are often shielded by the metal housing. Currently, to ensure the communication quality of electronic devices, slots are opened on metal housings to allow antenna signals to reach the outside of the housing. Plastic resin is filled into the slots to connect the parts separated by the slots. The plastic resin can be applied using nanomolding technology (NMT). The NMT process mechanically bonds the plastic resin to the metal by etching the metal surface and injection molding the plastic resin onto the etched surface of the metal. Therefore, high bonding strength between the plastic resin and the metal is important in these applications. U.S. patent application US2017/0029615 discloses a glass fiber reinforced, blended thermoplastic composition, wherein a molded article made from the composition of the invention may have a bonding strength of more than 25 MPa, which is insufficient for certain applications. WO2017/187384 discloses a thermoplastic composition comprising a polymeric base resin, a glass fiber component, and a laser direct structuring additive. The polymeric base resin comprises polybutylene terephthalate, polyamide, polycarbonate, poly(p-phenylene oxide), or a combination thereof. When bonded to an aluminum alloy, the thermoplastic composition has a nanomolding technology (NMT) bonding strength of at least about 20 MPa. Additionally, many plastic resins used to connect separated parts of metal-based housings generally have high dielectric constants, which will adversely affect the antenna's ability to receive and/or emit signals. Research has been conducted to adjust the dielectric constant by modifying the components of plastic resins. However, it was found that when the dielectric constant of the plastic resin meets the requirements for use in metal-based housings, mechanical properties, specifically the bonding strength to the metal, deteriorate. In addition, it is desirable that the plastic resin be able to maintain the lightweight characteristics of the thin-walled metal-based housing. Despite significant investigation and development research, there is still a demand for plastic materials to be used in combination with metal housings for electrical devices that strike a good balance between lightness and bonding strength, particularly with respect to aluminum, which is often used for metal housings for mobile phones. The present invention aims to provide a plastic material to be used in combination with a metal housing for an electrical device, which strikes a good balance between lightness and bonding strength and dielectric constant, as well as metal, particularly metal housings often used for mobile phones. Accordingly, according to one aspect, the present invention provides a polymer composition comprising the following, wherein all contents are based on the total weight of the composition: A). 20 wt% to 30 wt% of polycarbonate; B). 40 wt% to 60 wt% of polybutylene terephthalate; C). 5 wt% to 30 wt% of reinforcing fibers; D). 1 wt% to 10 wt% of glass bubbles, and E). 0.3 wt% to 2 wt% of an ester exchange inhibitor. The polymer composition according to the present invention has improved adhesion to metal (particularly aluminum) even after chemical etching and anodizing processes are applied. The polymer composition according to the present invention has a bonding strength of more than 30 megapascals (MPa) when bonded to aluminum or its alloy. Additionally, due to the presence of glass bubbles, a lightweight plastic member can be manufactured from the polymer composition according to the present invention. The polymer composition according to the present invention can be used to manufacture an article comprising a metal substrate and a plastic member made from the polymer composition according to the present invention on the same. According to another aspect, the present invention provides an article comprising the following: metal substrate; and A plastic member manufactured from a polymer composition according to the present invention on a metal substrate. According to another additional aspect, the present invention provides a method for manufacturing an article comprising the following steps: A step of forming a plastic member on a metal substrate using a polymer composition according to the present invention. Other objects, features, aspects, and advantages of the present invention will become much more clearly apparent when reading the following de