WO2005012417A1 - Flameproof thermoplastic resin composition - Google Patents

Flameproof thermoplastic resin composition Download PDF

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Publication number
WO2005012417A1
WO2005012417A1 PCT/KR2004/000969 KR2004000969W WO2005012417A1 WO 2005012417 A1 WO2005012417 A1 WO 2005012417A1 KR 2004000969 W KR2004000969 W KR 2004000969W WO 2005012417 A1 WO2005012417 A1 WO 2005012417A1
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WO
WIPO (PCT)
Prior art keywords
weight
parts
monomer
aromatic vinyl
phosphate
Prior art date
Application number
PCT/KR2004/000969
Other languages
French (fr)
Inventor
Soon Young Jin
Sang Hyun Hong
Sung Hee Ahn
Young Sik Ryu
Original Assignee
Cheil Industries Inc.
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Filing date
Publication date
Application filed by Cheil Industries Inc. filed Critical Cheil Industries Inc.
Priority to EP04748326A priority Critical patent/EP1651717A4/en
Priority to JP2006522500A priority patent/JP2007501307A/en
Publication of WO2005012417A1 publication Critical patent/WO2005012417A1/en
Priority to US11/348,536 priority patent/US20060183827A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
    • C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/527—Cyclic esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • C08K5/5357—Esters of phosphonic acids cyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen

Definitions

  • the present invention relates to a flame retardant thermoplastic resin composition. More particularly, the present invention relates to a flame retardant rubber-modified styrenic resin composition employing an oxaphosphorane compound as a flame retardant to a base resin consisting of rubber modified polystyrene resin.
  • a rubber modified styrenic resin is excellent in mold processability and mechanical properties, therefore, the resin has been widely applied to electric or electronic goods and office supplies.
  • the disadvantage could be observed , when the rubber modified styrenic resin is employed to heat-emitting products, because the styrenic resin is extremely easily flammable. Therefore, the methods for improving the flame-retardant property of the rubber-modified styrenic resin have been developed.
  • a widely known method for flame retardancy is that a halogen-containing compound is added to a rubber modified styrene-containing resin to give a good flame-retardant property.
  • halogen-containing compounds used in the method above are, for example, polybromodiphenyl ether, tetrabromobisphenol-A, epoxy compounds substituted by bromine.
  • an antimony-containing compound is commonly used along with the halogen-containing compound in order to increase flame retardancy.
  • the disadvantages could be observed that the halogen-containing compound results in the corrosion of the mold itself by the hydrogen halide gases released during the molding process and is fatally harmful due to the toxic gases liberated in case of fire
  • a polybromodiphenyl ether mamly used for a halogen-containmg flame retardant, can produce toxic gases such as dioxm or difuran during combustion.
  • U.S. patent No. 3,639,506 discloses resm composition using mono aromatic phosphoric acid ester such as triphenylphosphate to a blend of styrenic resin and polyphenylene ether resm.
  • mono aromatic phosphoric acid ester such as triphenylphosphate
  • deterioration of heat resistance and juicing crack phenomenon are observed du ⁇ ng molding process due to t ⁇ phenyl phosphate since the t ⁇ phenyl phosphate is highly volatile.
  • thermoplastic resin composition which has anti-dnppmg flame retardancy by employing oxaphosphorane compound to rubber modified styrenic resin.
  • the thermoplastic resm composition of the present invention does not show deterioration of heat resistance or volatility problem.
  • a further object of the present invention is to provide an environmentally friendly and non-toxic flame retardant thermoplastic resin composition which does not contain a halogen-containing compound.
  • the flameproof thermoplastic resin composition according to the present invention comprises (A) 100 parts by weight of a rubber modified styrenic resin containing (a ⁇ 20 to 100 % by weight of graft copolymer prepared by graft-polymerizing 5 to 65 parts by weight of a rubber polymer, 35 to 95 parts by weight of an aromatic vinyl monomer, 1 to 20 parts by weight of a monomer copolymerizable with said aromatic vinyl monomer and 0 to 15 parts by weight of a monomer for providing processability and heat resistance; and (a 2 ) 0 to 80 % by weight of copolymer prepared by polymerizing 60 to 90 parts by weight of an aromatic vinyl monomer, 10 to 40 parts by weight of a monomer copolymerizable with said aromatic vinyl monomer and 0 to 30 parts by weight of a monomer for providing processability and heat resistance; (B) 0.1 to 15 parts by weight of an oxaphosphorane compound; and (C) 0 to 20 parts by weight of an aromatic phosphoric acid ester
  • the rubber modified styrenic resin according to the present invention is a polymer wherein rubber phase polymers are dispersed in the form of particles in a matrix obtained by polymerizing an aromatic vinyl monomer and a vinyl group-containing monomer, which can be polymerized therewith, in the presence of a rubber phase polymer.
  • Such rubber-modified styrenic resin is prepared by a known method such as emulsion polymerization, suspension polymerization or bulk polymerization, and is conventionally produced by an extrusion with a styrene-containing graft copolymer resin and a styrene-containing copolymer resin.
  • both a styrene-containing graft copolymer resin and a styrene-containing copolymer resin are prepared together in one process.
  • a styrene-containing graft copolymer resin and a styrene-containing copolymer resin may be prepared separately.
  • the contents of rubber in a final rubber-modified styrenic resin to the total weight of the base resin are preferably in 5 to 30 % by weight.
  • a graft copolymer resin can be used alone or in combination with a copolymer resin in consideration of compatibility thereof.
  • the graft copolymer of the present invention is prepared by graft -polymerizing rubber polymer, aromatic vinyl monomer, copolymerizable monomer with said aromatic vinyl monomer and monomer which provides processability and heat resistance;
  • the rubber polymer are diene rubbers such as polybutadiene, poly(styrene-butadiene), poly(acrylonitrile-butadiene), etc; saturated rubbers in which hydrogen is added to said diene-containing rubber; isoprene rubbers; acryl rubbers such as a polybutyl acrylic acid; and a terpolymer of ethylene-propylene-diene (EPDM).
  • a diene-containing rubber more preferably a butadiene-containing rubber.
  • the content of rubber polymer in the graft copolymer resin is preferably in the range of 5 to 65 parts by weight based on the total weight of a graft copolymer resin.
  • aromatic vinyl monomer are styrene, ⁇ -methyl styrene, p-methyl styrene, etc. In the above examples, styrene is the most preferable.
  • the content of aromatic vinyl monomer in the graft copolymer resin is preferably in the range of 35 to 95 parts by weight based on the total weight of a graft copolymer resin.
  • At least one copolymerizable monomer may be introduced and applied to the aromatic vinyl monomers.
  • the copolymerizable monomer is a cyanide vinyl-containing compound such as acrylonitrile or an unsaturated nitrile-containing compound such as methacrylonitrile.
  • the copolymerizable monomer is used in an amount of 1 to 20 parts by weight.
  • other monomers such as acrylic acid, methacryl acid, maleic anhydride and N-substituted maleimide can be added in the graft polymerization.
  • the amounts of the monomers are in the range of 0 to 15 parts by weight based on the graft copolymer resin.
  • the average size of rubber particles is preferably in the range of from 0.1 to 4 .
  • the copolymer resin of the present invention is prepared copolymerizing aromatic vinyl monomer, copolymerizable monomer with the aromatic vinyl monomer, and monomer which provides processability and heat resistance depending on the ratio and compatibility between monomers except rubber in the graft copolymer.
  • the examples of the aromatic vinyl monomer are styrene, -methylstyrene, p-methylstyrene, etc. Styrene is the most preferable.
  • the aromatic vinyl monomer in the total copolymer resin is contained in the amount of 60 to 90 parts by weight. At least one copolymerizable monomer may be introduced and applied to the aromatic vinyl monomers.
  • the examples of the copolymerizable monomer are cyanide vinyl group-containing compounds such as acrylonitrile and unsaturated nitrile-containing compounds such as methacrylonitrile. It is preferable that 10 to 40 parts by weight of the copolymerizable monomer to the total copolymer is employed. In addition, 0 to 30 parts by weight of other monomers such as acrylic acid, methacrylic acid, maleic anhydride and N-substituted maleimide may be added and copolymerized thereto.
  • the examples of the rubber- modified styrenic resin (A) used in the present invention are acrylonitrile-butadiene-styrene (ABS) copolymer resin, acrylonitrile-ethylenepropylene rubber-styrene (AES) copolymer resin, acrylonitrile-acryl rubber-styrene (AAS) copolymer resin, and so on.
  • ABS acrylonitrile-butadiene-styrene
  • AES acrylonitrile-ethylenepropylene rubber-styrene
  • AAS acrylonitrile-acryl rubber-styrene copolymer resin
  • the oxaphosphorane compound of the present invention is represented by the following chemical Formula ( I ):
  • R ⁇ is hydrogen, - 4 alkyl or C 6 . 10 aryl; R 2 and R 3 are independently of each other hydrogen or C1- 4 alkyl; and n is 1 ⁇ 3.
  • Examples of the oxaphosphorane compound having the structural formula ( I ) include 2-methyl-2,5-dioxo-l-oxa-2-phosphorane and
  • the oxaphosphorane compound (B) of present invention may be used alone or in combination as a mixture. And the oxaphosphorane compound (B) is used in the amount of from 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight per 100 parts by weight of base resin.
  • Aromatic phosphoric acid ester compound used in the present invention is a compound having the following structural formular ( II ):
  • R 3 , R and R 5 independently of one another are hydrogen or Cj- 4 alkyl;
  • X is a C 6 . 20 aryl group or alkyl-substituted C 6 . 20 aryl group that are derivatives from a dialcohol derivative such as resorcinol, hydroquinol and bisphenol-A; and
  • n is 0-4.
  • the compound represented in the structural formula ( II ) is triphenyl phosphate, tri(2,6-dimethyl) phosphate, and the like, and where n is 1, the compounds include resorcinolbis(diphenyl) phosphate, resorcinolbis(2,6-dimethyl phenyl) phosphate, resorcinolbis(2,4-ditertiary butyl phenyl) phosphate, hydroquinolbis (2,6-dimethyl phenyl) phosphate, hydroquinolbis(2,4-ditertiary butyl phenyl) phosphate, and the like.
  • the compounds can be used alone or in combination therewith.
  • the aromatic phosphoric acid ester can be used in the amount of 0 to 20 parts by weight, preferably 0.1 to 15 parts by weight, more preferably 0.1 to 6 parts by weight per 100 parts by weight of base resin.
  • additives may be contained in the resin composition of the present invention.
  • the additives include heat stabilizers, anti-oxidants, light stabilizers, inorganic or organic pigments or dyes and/or inorganic filler.
  • the additives are employed in an amount of 0 to 30 parts by weight as per 100 parts by weight of base resin(A).
  • (a 2 ) Copolymer resin 75 parts of styrene, 25 parts of acrylonitrile, and 120 parts of deionized water were mixed. To the mixture, 0.2 parts of azobisisobutylonitrile (AIBN) 0.4 parts of tricalciumphosphate and 0.2 parts of mercaptan-containing chain transfer agent were added. The resultant solution was heated to 80 ° C for 90 minutes and kept for 180 minutes. The resultant was washed, dehydrated and dried.
  • AIBN azobisisobutylonitrile
  • SAN Styrene-acrylonitrile copolymer
  • the components as shown in Table 1 were mixed and the mixture was extruded at 180-250 °C with a conventional twin screw extruder in pellets.
  • the resin pellets were dried at 80 °C for 3 hours, and molded into test specimens using a 6 oz injection molding machine at 180-280 °C and barrel temperature of 40-80 TJ .
  • the flame retardancy of the test specimens was measured in accordance with UL94NB with a thickness of 1/8" and 1/12" respectively.
  • the impact strength was measured according to Izod impact strength ASTM D-256 A (1/8" notch).
  • the heat resistance was measured according to ASTM D- 1525 under 5 kg.
  • Comparative Examples 1 was conducted in the same manner as in Example 1 except that the oxaphosphorane compound was not used.
  • Comparative Examples 2 was conducted in the same manner as in Example 1 except that the aromatic phosphoric acid ester compound was used as a flame retardant instead of the oxaphosphorane compound. The test results are presented in Table 1. Table 1
  • the resin compositions employing a oxaphosphorane compound as a flame retardant show good flame retardancy without deterioration of impact strength and heat resistance compared to comparative examples 1-2.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

The flameproof resin composition according to the present invention comprises (A) 100 parts by weight of a rubber modified polystyrene resin containing (a1) 20 to 100 % by weight of graft copolymer prepared by graft-polymerizing 5 to 65 parts by weight of a rubber polymer, 35 to 95 parts by weight of an aromatic vinyl monomer, 1 to 20 parts by weight of a monomer copolymerizable with said aromatic vinyl monomer and 0 to 15 parts by weight of a monomer for providing processability and heat resistance; and (a2) 0 to 80 % by weight of copolymer prepared by polymerizing 60 to 90 parts by weight of an aromatic vinyl monomer, 10 to 40 parts by weight of a monomer copolymerizable with said aromatic vinyl monomer and 0 to 30 parts by weight of a monomer for providing processability and heat resistance; (B) 0.1 to 15 parts by weight of an oxaphosphorane compound; and (C) 0 to 20 parts by weight of an aromatic phosphoric acid ester compound.

Description

FLAMEPROOF THERMOPLASTIC RESIN COMPOSITION
Field of the Invention
The present invention relates to a flame retardant thermoplastic resin composition. More particularly, the present invention relates to a flame retardant rubber-modified styrenic resin composition employing an oxaphosphorane compound as a flame retardant to a base resin consisting of rubber modified polystyrene resin.
Background of the Invention
A rubber modified styrenic resin is excellent in mold processability and mechanical properties, therefore, the resin has been widely applied to electric or electronic goods and office supplies. However, the disadvantage could be observed, when the rubber modified styrenic resin is employed to heat-emitting products, because the styrenic resin is extremely easily flammable. Therefore, the methods for improving the flame-retardant property of the rubber-modified styrenic resin have been developed. A widely known method for flame retardancy is that a halogen-containing compound is added to a rubber modified styrene-containing resin to give a good flame-retardant property. The examples of the halogen-containing compounds used in the method above are, for example, polybromodiphenyl ether, tetrabromobisphenol-A, epoxy compounds substituted by bromine. In addition, an antimony-containing compound is commonly used along with the halogen-containing compound in order to increase flame retardancy. However, the disadvantages could be observed that the halogen-containing compound results in the corrosion of the mold itself by the hydrogen halide gases released during the molding process and is fatally harmful due to the toxic gases liberated in case of fire Especially, since a polybromodiphenyl ether, mamly used for a halogen-containmg flame retardant, can produce toxic gases such as dioxm or difuran during combustion. So, a major concern in this field is to develop a flame retardant which is prepared without a halogen-contammg compound. U.S. patent No. 3,639,506 discloses resm composition using mono aromatic phosphoric acid ester such as triphenylphosphate to a blend of styrenic resin and polyphenylene ether resm. However, deterioration of heat resistance and juicing crack phenomenon are observed duπng molding process due to tπphenyl phosphate since the tπphenyl phosphate is highly volatile. In order to solve the above volatility problem, Japanese Patent Laid-open No. 7-043769 discloses that the use of phosphoric acid ester compound having a substituent containing 12 to 25 carbon atoms derived from TPP to a rubber-reinforced styrenic resin (HIPS), which may obtain anti-dπpping flame-retardancy. Further, Japanese Patent Laid-open No. 5-1079 discloses an aromatic diphosphate which contains phenyl linkage in its structure. However, in these cases, a large amount of flame retardant is needed to obtain anti-dπpping flame-retardancy, which leads to deteπoration of heat resistance. Accordingly, the present inventors have developed a flame retardant thermoplastic resin composition which has anti-dnppmg flame retardancy by employing oxaphosphorane compound to rubber modified styrenic resin. The thermoplastic resm composition of the present invention does not show deterioration of heat resistance or volatility problem.
Objects of the Invention
An object of the present invention is to provide a flame retardant thermoplastic resin composition with good flame retardancy by using oxaphosphorane compound as a flame retardant to a rubber modified styrenic resin. Another object of the present invention is to provide a flame retardant thermoplastic resin composition with good properties, such as impact strength and heat resistance. A further object of the present invention is to provide an environmentally friendly and non-toxic flame retardant thermoplastic resin composition which does not contain a halogen-containing compound. Other objects and advantages of this invention will be apparent from the ensuing disclosure and appended claims.
Summary of the Invention
The flameproof thermoplastic resin composition according to the present invention comprises (A) 100 parts by weight of a rubber modified styrenic resin containing (a^ 20 to 100 % by weight of graft copolymer prepared by graft-polymerizing 5 to 65 parts by weight of a rubber polymer, 35 to 95 parts by weight of an aromatic vinyl monomer, 1 to 20 parts by weight of a monomer copolymerizable with said aromatic vinyl monomer and 0 to 15 parts by weight of a monomer for providing processability and heat resistance; and (a2) 0 to 80 % by weight of copolymer prepared by polymerizing 60 to 90 parts by weight of an aromatic vinyl monomer, 10 to 40 parts by weight of a monomer copolymerizable with said aromatic vinyl monomer and 0 to 30 parts by weight of a monomer for providing processability and heat resistance; (B) 0.1 to 15 parts by weight of an oxaphosphorane compound; and (C) 0 to 20 parts by weight of an aromatic phosphoric acid ester compound.
Detailed Description of the Invention
(A) Rubber-modified styrenic resin The rubber modified styrenic resin according to the present invention is a polymer wherein rubber phase polymers are dispersed in the form of particles in a matrix obtained by polymerizing an aromatic vinyl monomer and a vinyl group-containing monomer, which can be polymerized therewith, in the presence of a rubber phase polymer. Such rubber-modified styrenic resin is prepared by a known method such as emulsion polymerization, suspension polymerization or bulk polymerization, and is conventionally produced by an extrusion with a styrene-containing graft copolymer resin and a styrene-containing copolymer resin. In a bulk polymerization, both a styrene-containing graft copolymer resin and a styrene-containing copolymer resin are prepared together in one process. In other polymerizations, a styrene-containing graft copolymer resin and a styrene-containing copolymer resin may be prepared separately. In either case, the contents of rubber in a final rubber-modified styrenic resin to the total weight of the base resin are preferably in 5 to 30 % by weight. In the rubber modified styrenic resin, a graft copolymer resin can be used alone or in combination with a copolymer resin in consideration of compatibility thereof.
(a^ Graft copolymer resin
The graft copolymer of the present invention is prepared by graft -polymerizing rubber polymer, aromatic vinyl monomer, copolymerizable monomer with said aromatic vinyl monomer and monomer which provides processability and heat resistance; Examples of the rubber polymer are diene rubbers such as polybutadiene, poly(styrene-butadiene), poly(acrylonitrile-butadiene), etc; saturated rubbers in which hydrogen is added to said diene-containing rubber; isoprene rubbers; acryl rubbers such as a polybutyl acrylic acid; and a terpolymer of ethylene-propylene-diene (EPDM). It is preferable to use a diene-containing rubber, more preferably a butadiene-containing rubber. The content of rubber polymer in the graft copolymer resin is preferably in the range of 5 to 65 parts by weight based on the total weight of a graft copolymer resin. Examples of aromatic vinyl monomer are styrene, α -methyl styrene, p-methyl styrene, etc. In the above examples, styrene is the most preferable. The content of aromatic vinyl monomer in the graft copolymer resin is preferably in the range of 35 to 95 parts by weight based on the total weight of a graft copolymer resin. At least one copolymerizable monomer may be introduced and applied to the aromatic vinyl monomers. It is preferred that the copolymerizable monomer is a cyanide vinyl-containing compound such as acrylonitrile or an unsaturated nitrile-containing compound such as methacrylonitrile. The copolymerizable monomer is used in an amount of 1 to 20 parts by weight. In addition, in order to give good characteristics of processability and heat resistance, other monomers such as acrylic acid, methacryl acid, maleic anhydride and N-substituted maleimide can be added in the graft polymerization. The amounts of the monomers are in the range of 0 to 15 parts by weight based on the graft copolymer resin. To acquire good impact strength and surface appearance when said graft copolymer is prepared, the average size of rubber particles is preferably in the range of from 0.1 to 4 .
(a2) Copolymer resin
The copolymer resin of the present invention is prepared copolymerizing aromatic vinyl monomer, copolymerizable monomer with the aromatic vinyl monomer, and monomer which provides processability and heat resistance depending on the ratio and compatibility between monomers except rubber in the graft copolymer. The examples of the aromatic vinyl monomer are styrene, -methylstyrene, p-methylstyrene, etc. Styrene is the most preferable. The aromatic vinyl monomer in the total copolymer resin is contained in the amount of 60 to 90 parts by weight. At least one copolymerizable monomer may be introduced and applied to the aromatic vinyl monomers. The examples of the copolymerizable monomer are cyanide vinyl group-containing compounds such as acrylonitrile and unsaturated nitrile-containing compounds such as methacrylonitrile. It is preferable that 10 to 40 parts by weight of the copolymerizable monomer to the total copolymer is employed. In addition, 0 to 30 parts by weight of other monomers such as acrylic acid, methacrylic acid, maleic anhydride and N-substituted maleimide may be added and copolymerized thereto. The examples of the rubber- modified styrenic resin (A) used in the present invention are acrylonitrile-butadiene-styrene (ABS) copolymer resin, acrylonitrile-ethylenepropylene rubber-styrene (AES) copolymer resin, acrylonitrile-acryl rubber-styrene (AAS) copolymer resin, and so on. The rubber modified styrenic resin (A) of the present invention is prepared by mixing 20-100 % by weight of the graft copolymer resin (a^ with 0-80 % by weight of the copolymer resin (a2).
(B) Oxaphosphorane compound
The oxaphosphorane compound of the present invention is represented by the following chemical Formula ( I ):
Figure imgf000008_0001
wherein R{ is hydrogen, -4 alkyl or C6.10 aryl; R2 and R3 are independently of each other hydrogen or C1-4 alkyl; and n is 1~3.
Examples of the oxaphosphorane compound having the structural formula ( I ) include 2-methyl-2,5-dioxo-l-oxa-2-phosphorane and
2-phenyl-2,5-dioxo-l-oxa-2- phosphorane. The oxaphosphorane compound (B) of present invention may be used alone or in combination as a mixture. And the oxaphosphorane compound (B) is used in the amount of from 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight per 100 parts by weight of base resin.
(C) Aromatic phosphoric acid ester compound The aromatic phosphoric acid ester compound used in the present invention is a compound having the following structural formular ( II ):
Figure imgf000008_0002
wherein R3, R and R5 independently of one another are hydrogen or Cj-4 alkyl; X is a C6.20 aryl group or alkyl-substituted C6.20 aryl group that are derivatives from a dialcohol derivative such as resorcinol, hydroquinol and bisphenol-A; and n is 0-4.
Where n is 0, the compound represented in the structural formular ( II ) is triphenyl phosphate, tri(2,6-dimethyl) phosphate, and the like, and where n is 1, the compounds include resorcinolbis(diphenyl) phosphate, resorcinolbis(2,6-dimethyl phenyl) phosphate, resorcinolbis(2,4-ditertiary butyl phenyl) phosphate, hydroquinolbis (2,6-dimethyl phenyl) phosphate, hydroquinolbis(2,4-ditertiary butyl phenyl) phosphate, and the like. The compounds can be used alone or in combination therewith. In the present invention, the aromatic phosphoric acid ester can be used in the amount of 0 to 20 parts by weight, preferably 0.1 to 15 parts by weight, more preferably 0.1 to 6 parts by weight per 100 parts by weight of base resin.
Other additives may be contained in the resin composition of the present invention. The additives include heat stabilizers, anti-oxidants, light stabilizers, inorganic or organic pigments or dyes and/or inorganic filler. The additives are employed in an amount of 0 to 30 parts by weight as per 100 parts by weight of base resin(A).
The present invention may be better understood by reference to the following examples that are intended for the purpose of illustration and are not to be construed as in any way limiting the scope of the present invention, which is defined in the claims appended hereto.
Examples The components to prepare flameproof thermoplastic resin compositions in Examples 1-3 and Comparative Examples 1-2 are as follows:
(A) Rubber modified styrenic resin
(ai) Graft-copolymer resin 50 parts of butadiene rubber latex, 36 parts of styrene, 14 parts of acrylonitrile, and 150 parts of deionized water were mixed. To the mixture, 1.0 part of potassium oleate, 0.4 parts of cumenhydroperoxide, 0.2 parts of mercaptan-containing chain transfer agent, 0.4 parts of glucose, 0.01 parts of ferrous sulfate hydrate, and 0.3 parts of sodium pyrophosphate were added. The blend was kept at 75 °C for 5 hours to obtain g-ABS latex. To the g-ABS latex,
0.4 parts of sulfuric acid was added, coagulated and dried to obtain rubber modified polystyrene resin (g-ABS) in a powder form.
(a2) Copolymer resin 75 parts of styrene, 25 parts of acrylonitrile, and 120 parts of deionized water were mixed. To the mixture, 0.2 parts of azobisisobutylonitrile (AIBN) 0.4 parts of tricalciumphosphate and 0.2 parts of mercaptan-containing chain transfer agent were added. The resultant solution was heated to 80 °C for 90 minutes and kept for 180 minutes. The resultant was washed, dehydrated and dried.
Styrene-acrylonitrile copolymer (SAN) was obtained.
(B) Oxaphosphorane compound
2-methyl-2,5-dioxo-l-oxa-2-phosphorane with a melting point of 102-104 °C was used.
(C) Aromatic phosphoric acid ester compound Resorcinol bis (2,6-dimethylphenyl)phosphate by Daihachi Chemical of Japan (product name: PX200) was used.
Examples 1-3
The components as shown in Table 1 were mixed and the mixture was extruded at 180-250 °C with a conventional twin screw extruder in pellets. The resin pellets were dried at 80 °C for 3 hours, and molded into test specimens using a 6 oz injection molding machine at 180-280 °C and barrel temperature of 40-80 TJ . The flame retardancy of the test specimens was measured in accordance with UL94NB with a thickness of 1/8" and 1/12" respectively. The impact strength was measured according to Izod impact strength ASTM D-256 A (1/8" notch). The heat resistance was measured according to ASTM D- 1525 under 5 kg.
Comparative Examples 1-2
Comparative Examples 1 was conducted in the same manner as in Example 1 except that the oxaphosphorane compound was not used. Comparative Examples 2 was conducted in the same manner as in Example 1 except that the aromatic phosphoric acid ester compound was used as a flame retardant instead of the oxaphosphorane compound. The test results are presented in Table 1. Table 1
Comparative Examp ;s Examples 1 2 " " 3 4 l" "2 " (a.) ""32 32 32 " 25~ " ""32 " " 32
(A)Rubber modified styrenic resin (a2) 68 68 68 75 68 68
(B)Oxaphosphorane compound 1 3 2 2 - (C)Aromatic phosphoric acid ester co >mmppoouunr idd - - 2 - 6 UL 94 flame retardancy (1/12") ~ '" " V-2 V-2 V-2 "V-2 Fail "" V-2 UL 94 flame retardancy (1/8") V-2 V-2 V-2 V-2 Fail V-2 Izod impact strength (kgf ■ cm/cm) 25 23 21 18 34 20 Vicat Softening Temperature(VST, °C ) ) 94 92 92 93 94 88
As shown above, the resin compositions employing a oxaphosphorane compound as a flame retardant show good flame retardancy without deterioration of impact strength and heat resistance compared to comparative examples 1-2.
The present invention can be easily carried out by an ordinary skilled person in the art. Many modifications and changes may be deemed to be with the scope of the present invention as defined in the following claims.

Claims

What is claimed is:
1. A flame retardant thermoplastic resin composition comprising: (A) 100 parts by weight of a rubber modified polystyrene resin containing (a^ 20 to 100 % by weight of graft copolymer prepared by graft-polymerizing 5 to 65 parts by weight of a rubber polymer, 35 to 95 parts by weight of an aromatic vinyl monomer, 1 to 20 parts by weight of a monomer copolymerizable with said aromatic vinyl monomer and 0 to 15 parts by weight of a monomer for providing processability and heat resistance; and (a2) 0 to 80 % by weight of copolymer prepared by polymerizing 60 to 90 parts by weight of an aromatic vinyl monomer, 10 to 40 parts by weight of a monomer copolymerizable with said aromatic vinyl monomer and 0 to 30 parts by weight of a monomer for providing processability and heat resistance; (B) 0.1 to 15 parts by weight of an oxaphosphorane compound represented by the following formula ( I ):
Figure imgf000013_0001
wherein R! is hydrogen, C^ alkyl or C6.10 aryl; R2 and R3 are independently of each other hydrogen or Cμ alkyl; and n is 1-3; and (C) 0 to 20 parts by weight of an aromatic phosphoric acid ester compound represented by the following formula ( II ):
Figure imgf000014_0001
wherein R3, 4 and R5 independently of one another are hydrogen or Cμ alkyl; X is a C6.20 aryl group or alky .-substituted C6.20 aryl group that are derivatives from a dialcohol derivative such as resorcinol, hydroquinol and bisphenol-A; and n is 0-4.
2. The flame retardant thermoplastic resin composition as defined in claim 1 , wherein said rubber polymer is selected from the group consisting of diene rubbers, saturated rubbers in which hydrogen is added to said diene-containing rubber, isoprene rubbers; acryl rubbers; and a terpolymer of ethylene-propylene-diene (EPDM); said aromatic vinyl monomer is selected from the group consisting of styrene, α -methyl styrene, p-methyl styrene; said monomer copolymerizable with said aromatic vinyl monomer is selected from cyanide vinyl-containing compounds and unsaturated nitrile-containing compounds; said monomer for providing processability and heat resistance is selected from the group consisting of acrylic acid, methacryl acid, maleic anhydride and N-substituted maleimide.
3. The flame retardant thermoplastic resin composition as defined in claim 1, wherein said oxaphosphorane compound (B) is selected from the group consisting of 2-methyl-2,5-dioxo- 1 -oxa-2-phosphorane and 2-phenyl-2,5-dioxo-l-oxa-2-phosphorane.
4. The flame retardant thermoplastic resin composition as defined in claim 1 , wherein said aromatic phosphoric acid ester compound (C) is selected from the group consisting of triphenyl phosphate, tri(2,6-dimethyl) phosphate, resorcinolbis (diphenyl) phosphate, resorcinolbis (2,6-dimethyl phenyl) phosphate, resorcinolbis (2,4-ditertiary butyl phenyl) phosphate, hydroquinolbis (2,6-dimethyl phenyl) phosphate, hydroquinolbis (2,4-ditertiary butyl phenyl) phosphate.
5. The flame retardant thermoplastic resin composition as defined in claim 1 , wherein said aromatic phosphoric acid ester compound (C) is 0.1 to 15 parts by weight.
PCT/KR2004/000969 2003-08-04 2004-04-27 Flameproof thermoplastic resin composition WO2005012417A1 (en)

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WO2013085097A1 (en) * 2011-12-06 2013-06-13 제일모직주식회사 Phosphorus-based compound having novel structure, preparation method thereof, and flame retardant thermoplastic resin composition containing same
KR101411008B1 (en) * 2010-12-22 2014-06-23 제일모직주식회사 Novel phosphorus compound, method for preparing thereof and flame retardant thermoplastic resin composition containing the same
US10774266B2 (en) * 2018-09-25 2020-09-15 Elite Electronic Material (Zhongshan) Co., Ltd. Flame retardant compound, method of making the same, resin composition and article made therefrom

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KR100962174B1 (en) * 2007-12-10 2010-06-10 제일모직주식회사 Sterically Hindered Phenolic Phosphonates and Flame Retardant Polycarbonate Resin Composition Containing Them
JP2014177596A (en) * 2013-03-15 2014-09-25 Ricoh Co Ltd Recycled resin composition, molding, image forming apparatus, and method for producing recycled resin composition
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KR20230037218A (en) * 2021-09-09 2023-03-16 롯데케미칼 주식회사 Thermoplastic resin composition and article produced therefrom

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