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(12) United States Patent (10) Patent No.: US 8,871,843 B2 Lee (45) Date of Patent: Oct

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(12) United States Patent (10) Patent No.: US 8,871,843 B2 Lee (45) Date of Patent: Oct USOO887 1843B2 (12) United States Patent (10) Patent No.: US 8,871,843 B2 Lee (45) Date of Patent: Oct. 28, 2014 (54) HALOGEN-FREE FLAME RETARDANT 5,456,984 A 10/1995 Bishop et al. MATERAL 5,484,830 A 1/1996 Staendeke 5,648.436 A 7/1997 Janowitz et al. 5,925,700 A 7/1999 Imahashi (75) Inventor: Jean L. Lee, San Jose, CA (US) 5,955, 184 A 9, 1999 Honda et al. 5,994,429 A 11/1999 Honda et al. (73) Assignee: Apple Inc., Cupertino, CA (US) 6,140,411 A 10/2000 Schwanborn et al. 6,355,767 B1 * 3/2002 Takagi .......................... 528,196 (*) Notice: Subject to any disclaimer, the term of this 6,440,567 B1 8, 2002 Choate et al. 6,495,244 B1 12/2002 Andresakis et al. patent is extended or adjusted under 35 6,518,336 B1 2/2003 Yabuhara et al. U.S.C. 154(b) by 190 days. 6,642,288 B1 1 1/2003 Hulskotte 6,755,995 B1 6/2004 Hasegawa et al. (21) Appl. No.: 12/638,489 6,767,941 B2 7/2004 Van Der Speket al. 6,809,130 B2 10/2004 Chiou et al. 6,894, 101 B2 5, 2005 Paul et al. (22) Filed: Dec. 15, 2009 6,916,539 B2 7/2005 Cooray et al. 6,998,536 B2 2/2006 Barusseau et al. (65) Prior Publication Data 7,053,145 B1 5/2006 Tasaka et al. US 2011/O144244A1 Jun. 16, 2011 7,115,678 B2 10/2006 Ihara et al. 7,279.520 B2 10/2007 Hausmann et al. 7,323,504 B2 1/2008 Steenbakkers-Menting et al. (51) Int. Cl. 7,368,495 B2 5/2008 Ihara et al. CSK 3/28 (2006.01) 7,456,235 B2 11/2008 Heschke et al. CSK 3/22 (2006.01) 7.495,174 B2 2/2009 Hase et al. 7,939,591 B2* 5/2011 Tomoda ...... ... 524,284 C08K 3/26 (2006.01) 2001/00 16615 A1 8/2001 Sobkin et al. ................... 524.91 C08K 3/34 (2006.01) 2002fO155348 A1 10, 2002 Gitto CSK 3/38 (2006.01) 2005/008O165 A1* 4/2005 Gabriel ......................... 523,220 CSK5/05 (2006.01) 2006/0245607 A1 1 1/2006 Kynnos CSK 5/535 (2006.01) 2009, O151984 A1 6/2009 Fujimura CSK 5/545 (2006.01) CSK 5/7 (2006.01) FOREIGN PATENT DOCUMENTS CSK 5/45 (2006.01) WO WO 2006 123833 A1 * 11, 2006 COSL23/06 (2006.01) CSK 3/00 (2006.01) * cited by examiner COSL23/02 (2006.01) COSL 53/OO (2006.01) Primary Examiner — Angela C Scott (52) U.S. Cl. (74) Attorney, Agent, or Firm — Brownstein Hyatt Farber CPC ............... C08K 3/0058 (2013.01); C08L 23/06 Schreck, LLP (2013.01); C08L 53/00 (2013.01); C08L 23/02 (2013.01); C08K 3/34 (2013.01) (57) ABSTRACT USPC ............................ 524/186; 524/429; 524/492 The disclosure describes halogen free flame retardant resin (58) Field of Classification Search compositions comprising at least one thermoplastic polymer; USPC .......................................... 524/186, 429, 492 an inorganic filler; and a flame retardant additive, wherein the See application file for complete search history. flame retardant additive is an alkali metal nitrite; an alkaline earth metal nitrite; an alkali metal nitride; an alkaline earth (56) References Cited metal nitride; an alkali metal borate; an alkaline earth metal borate; an alkali metal silicide; an alkaline earth metal sili U.S. PATENT DOCUMENTS cide; an alkali metal silicate; or an alkaline earth metal sili 4,869,848 A 9/1989 Hasegawa et al. cate. Also described are computing systems having compo 4,879,332 A 11, 1989 Saito et al. nents formed of Such a halogen free, flame retardant resin. 4,996,255 A 2f1991 Davis et al. 5,286,775 A 2/1994 Bandyopadhyay 11 Claims, 1 Drawing Sheet U.S. Patent Oct. 28, 2014 US 8,871,843 B2 US 8,871,843 B2 1. 2 HALOGEN-FREE FLAME RETARDANT The inorganic filler can be one or more of carbon black, MATERAL white carbon, silica, Zirconium silicate, alumina, hydrated alumina, aluminum trihydrate, hydrated magnesium, barium BACKGROUND Sulfate, barium titanate, titanium oxide, magnesium oxide, molybdenum oxide, tin oxide, Zinc oxide, talc, mica, glass It has been estimated that about 10% of fires are caused by beads, hollow glass balls, clay, silicone oil, quartz, barium electrical faults of wiring and electrical equipment, and that carbonate, calcium carbonate, or magnesium carbonate. In these fires account for 19% of fire-related injuries. Some Some embodiments, one or more of such inorganic fillers can plastics are inherently resistant to fire. Such as polyvinylchlo also be excluded from the composition. The inorganic filler 10 can be present, for example, in about 1 wt.% to about 30 wt. ride (PVC). However, PVC is not suitable for many electron % of the composition. ics applications. Only about 12% of plastics used today con In some embodiments, the flame retardant additive can tain flame retardants. An increased use of flame retardants include an alkali metal nitrite or an alkaline earth metal would improve the safety of electrical wiring and electronic nitrite. The alkali metal nitrite or alkaline earth metal nitrite devices, and therefore reduce the number of fires caused by 15 can be, for example, lithium nitrite, Sodium nitrite, potassium electronic devices. nitrite, magnesium nitrite, or calcium nitrite. Halogenated flame retardants have been found to be effec In some embodiments, the flame retardant additive can tive in many plastics. However, environmental and health include an alkali metal nitride or an alkaline earth metal concerns have caused halogenated flame retardants to be less nitride. The alkali metal nitride or alkaline earth metal nitride desirable for electronic devices, and they are being increas can be, for example, lithium nitride, magnesium nitride, ingly regulated. beryllium nitride, or calcium nitride. A wide variety of flame retardant resin compositions have In some embodiments, the flame retardant additive can been developed to ensuring safety against fire, including include an alkali metal borate or an alkaline earth metal halogen free flame retardant resin compositions. Generally, borate. The alkali metal borate or alkaline earth metal borate halogen free flame resisting resin compositions contain inor 25 can be, for example, sodium metaborate, Sodium tetraborate, ganic fillers, such as aluminum hydroxide or magnesium NaBas, Na-Bo, NaBs, calcium aluminum triborate (jo hydroxide. The amount of the inorganic filler required to hachidolite), magnesium diboride, Suanite; johachidolite; obtain sufficiently high flame resisting effect is generally 30 LiBO: LiBO: CaBO; sodium metaborate; sodium tet to 70% by weight based of the composition. However, a raborate; NaBO(OH)4.8H2O, or disodium octaborate synthetic resin composition containing Such high contents of 30 tetrahydrate. inorganic filler generally do not exhibit Suitable physical In some embodiments, the flame retardant additive can characteristics, such as well-balanced strength, resulting in include an alkali metal silicide or an alkaline earth metal brittle products with poor processability. Accordingly, there silicide. The alkali metal silicide or alkaline earth metal sili is a need for new halogen-free flame retardants, as well as new cide can be, for example, Sodium silicide, potassium silicide, halogen-free plastics and resin materials. 35 rubidium silicide, cesium silicide magnesium silicide, or cal cium silicide. SUMMARY In some embodiments, the flame retardant additive can include an alkali metal silicate or an alkaline earth metal The invention provides halogen-free flame retardants, res silicate. The alkali metal silicate or alkaline earth metal sili ins that include halogen free flame retardants, and plastic 40 cate can be, for example, thaumasite, olivine; or epidote. components made from Such materials. In some embodi Any given embodiment can also include an antioxidant, ments, the invention relates to a composite resin molded Such as an amino acid, vitaminA, vitamin E, ascorbic acid, or article having excellent flame retardancy, electric insulation lipoic acid. Antioxidants can be included in about 0.5 parts to properties, and crack resistance, and produces only negligible 15 parts by weight, or in about any 0.5 part increment within amounts of toxic Substances during incineration, if any at all. 45 Such a range. In some embodiments, the composition can Accordingly, the invention provides a halogen free resin have a melt index of for example, about 0.1 g/10 minutes to composition that includes at least one thermoplastic polymer; about 10.0 g/10 minutes. an inorganic filler; and a flame retardant additive, wherein the In some embodiments, a halogen free resin composition flame retardant additive comprises an alkali metal nitrite; an includes about 70 parts to 30 parts by weight of at least one alkaline earth metal nitrite; an alkali metal nitride; an alkaline 50 thermoplastic polymer; about 30 parts to 70 parts by weight of earth metal nitride; an alkali metal borate; an alkaline earth an inorganic filler; and about 0.5 parts to 15 parts by weight of metal borate; an alkali metal silicide; an alkaline earth metal a flame retardant additive, wherein the flame retardant addi silicide; an alkali metal silicate; an alkaline earth metal sili tive includes an alkali metal nitrite; an alkaline earth metal cate; or a combination thereof. nitrite; an alkali metal nitride; an alkaline earth metal nitride; The thermoplastic polymer can include one or more of 55 analkali metal borate; analkaline earth metal borate; analkali polyethylene (PE); ethylene-vinyl acetate copolymer (EVA): metal silicide; an alkaline earth metal silicide; an alkali metal ethylene-ethyl acrylate copolymer (EEA): ethylene-methyl silicate; an alkaline earth metal silicate; or a combination methacrylate copolymer (EMMA); polypropylene (PP); thereof. polystyrene (PS); polyacrylonitrile; acrylonitrile-butadiene The invention further provides a computing system, input styrene copolymer (ABS); nylon-6: nylon-6.6; polycarbonate 60 device, or computer component comprising any of the com (PC); polyurethane; biaxially-oriented polyethylene tereph positions described above or herein.
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