KR20040042354A - Flame Retardant Thermoplastic Resin Composition - Google Patents
Flame Retardant Thermoplastic Resin Composition Download PDFInfo
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- KR20040042354A KR20040042354A KR1020020070626A KR20020070626A KR20040042354A KR 20040042354 A KR20040042354 A KR 20040042354A KR 1020020070626 A KR1020020070626 A KR 1020020070626A KR 20020070626 A KR20020070626 A KR 20020070626A KR 20040042354 A KR20040042354 A KR 20040042354A
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- flame retardant
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- 239000011342 resin composition Substances 0.000 title claims abstract description 22
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims description 57
- 239000003063 flame retardant Substances 0.000 title claims description 55
- 229920005992 thermoplastic resin Polymers 0.000 title claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229920001971 elastomer Polymers 0.000 claims abstract description 16
- 229920005990 polystyrene resin Polymers 0.000 claims abstract description 16
- 239000005060 rubber Substances 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 239000004593 Epoxy Substances 0.000 claims abstract description 12
- BDFBPPCACYFGFA-UHFFFAOYSA-N 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine Chemical compound BrC1=CC(Br)=CC(Br)=C1OC1=NC(OC=2C(=CC(Br)=CC=2Br)Br)=NC(OC=2C(=CC(Br)=CC=2Br)Br)=N1 BDFBPPCACYFGFA-UHFFFAOYSA-N 0.000 claims abstract description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 claims abstract description 3
- 229920001577 copolymer Polymers 0.000 claims abstract description 3
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 229920003049 isoprene rubber Polymers 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 230000003078 antioxidant effect Effects 0.000 claims 1
- 229920001169 thermoplastic Polymers 0.000 claims 1
- 239000004416 thermosoftening plastic Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 abstract 2
- 229920005989 resin Polymers 0.000 description 25
- 239000011347 resin Substances 0.000 description 25
- 239000000047 product Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- -1 2,4,6-tribromophenoxy Chemical group 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000012662 bulk polymerization Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000004335 antimony containing inorganic group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000002794 monomerizing effect Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
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- 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
- C08L25/08—Copolymers of styrene
- C08L25/10—Copolymers of styrene with conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
발명의 분야Field of invention
본 발명은 난연성을 갖는 스티렌계 수지 조성물에 관한 것이다. 보다 구체적으로 본 발명은 고무강화 폴리스티렌 수지 공중합체에 브로미네이티드 에폭시 올리고머(Brominated epoxy oligomer), 2,4,6-트리(2,4,6-트리브로모페녹시)-1,3,5-트리아진 및 난연 보조제를 혼합하여 이루어진 난연성이 우수한 스티렌계 수지 조성물에 관한 것이다.The present invention relates to a styrene resin composition having flame retardancy. More specifically, the present invention is a brominated epoxy oligomer, 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5 in a rubber-reinforced polystyrene resin copolymer The present invention relates to a styrene resin composition having excellent flame retardancy formed by mixing a triazine and a flame retardant aid.
발명의 배경Background of the Invention
일반적으로 스티렌계 수지는 가공성과 기계적 강도가 양호하여 주로 전기·전자제품의 외장재로 사용되고 있다. 그러나 수지는 그 자체로 불에 대한 저항성(flame resistance)이 없고 외부의 점화인자(ignition source)에 의해 불꽃이 점화되면 수지 자체가 연소를 도와주는 에너지로 작용하여 지속적으로 불을 확산시키게 된다. 근래에 들어 전자 제품 중 텔레비전의 경우 대형화, 박막화의 추세로 시장이 형성되고 있으며, 색상 또한 진한 색에서부터 엷은 색까지 넓어지고 있는 상황이다. 그러므로 이러한 분야에 적용되는 스티렌계 수지는 난연성 뿐만 아니라, 필히 성형성과 열 안정성을 동시에 충족시켜야하는 문제를 안고 있다.In general, styrene-based resins have good processability and mechanical strength, and are mainly used as exterior materials for electrical and electronic products. However, the resin itself does not have flame resistance, and when the spark is ignited by an external ignition source, the resin itself acts as an energy to assist combustion and continuously spreads the fire. In recent years, the market of TVs among electronic products is becoming larger and thinner, and the color is also expanding from dark to light colors. Therefore, the styrene-based resins applied to these fields have a problem of not only flame retardancy, but also must satisfy moldability and thermal stability at the same time.
따라서 상기의 점을 감안하여 미국, 유럽 등의 국가에서는 전자제품의 화재에 대한 안정성을 보장하기 위하여 난연성을 갖는 수지만을 전자제품 외장재의 성형품 제조에 사용하도록 법제화하고 있다.Therefore, in view of the above, in the United States, Europe, etc., in order to ensure the stability of fire of electronic products, only the flame-retardant resin is required to be used to manufacture molded products of electronic exterior materials.
일반적으로 수지에 난연성을 부여하는 방법으로는 난연제와 난연 보조제를 첨가하는 첨가형 난연화법과 중합시 난연성 원자를 함유한 특수한 단량체(monomer)를 이용하여 수지를 제조하는 중합형 난연화법으로 나눌 수 있다. 이들 중 중합형 난연화법은 실험(pilot scale) 단계에서 많은 연구가 진행되었으나, 높은 비용과 난연성 달성의 어려움으로 인해 상업화된 제품은 출시되지 못하고 있는 실정이다. 따라서, 대부분의 상품화된 난연 수지는 컴파운딩(compounding)시 비활성원소인 할로겐 또는 인등을 함유한 난연제를 첨가하는 첨가형 난연화법에 의해 제조되고 있다.In general, a method of imparting flame retardancy to a resin may be classified into an additional flame retardant method of adding a flame retardant and a flame retardant aid, and a polymerized flame retardant method of preparing a resin using a special monomer containing a flame retardant atom during polymerization. Among them, polymerized flame retardation has been studied in a pilot scale stage, but commercialized products have not been released due to high cost and difficulty in achieving flame retardancy. Therefore, most commercialized flame retardant resins have been prepared by the addition flame retardant method of adding a flame retardant containing halogen or phosphorus, which is an inert element during compounding.
스티렌계 수지에 난연성을 부여하기 위해 난연제를 첨가하는 첨가형 난연화법은 주로 할로겐 함유 유기화합물과 안티몬함유 무기화합물 중에서 선택되는 한가지 혹은 한가지 이상의 성분을 수지에 첨가시켜 제조하게 된다. 그런데, 할로겐 함유 유기화합물은 주로 브롬 또는 염소화합물로서 스티렌계 수지에 첨가시 난연성은매우 우수한 반면 전반적인 물성에 심각한 저하를 일으키게 된다. 또한 열 안정성이 저하되는 문제가 있다. 따라서, 난연 수지를 제조하는데 있어서는 우수한 난연성을 유지하면서 물성 및 부수적인 영향을 최소화시키는 기술이 매우 중요하다.An additional flame retardant method in which a flame retardant is added to impart flame retardancy to a styrene resin is prepared by adding one or more components selected from halogen-containing organic compounds and antimony-containing inorganic compounds to the resin. By the way, the halogen-containing organic compound is mainly bromine or chlorine compound, when added to the styrene resin is very excellent in flame retardancy, but causes serious degradation in the overall physical properties. In addition, there is a problem that the thermal stability is lowered. Therefore, in manufacturing a flame retardant resin, a technique of minimizing physical properties and side effects while maintaining excellent flame retardancy is very important.
통상의 UL94 V-2 제품은 난연제의 분해에 의한 수지의 분해 촉진으로 연소시 빠른 시간 안에 수지의 드립(Drip)을 유발하도록 설계되어진다. 이러한 특징으로 인하여 난연제는 열에 의한 분해가 빨리 일어나도록 설계되어지나, 반면에 이러한 특징으로 수지의 통상적인 가공온도에서 난연제의 분해가 발생하여 수지 자체의 열 안정성이 저하되어 실버 스트릭크(silver streak) 불량, 혹은 밝은 색에서 검붉은 색으로의 열 변색이 일어나는 단점이 있다.Conventional UL94 V-2 products are designed to cause drips of resins in a short time during combustion by promoting decomposition of resins by decomposition of flame retardants. Due to this feature, the flame retardant is designed to cause thermal decomposition quickly, while this characteristic causes the decomposition of the flame retardant at the normal processing temperature of the resin, which lowers the thermal stability of the resin itself, thereby causing silver streak. There is a disadvantage, or heat discoloration from light to dark red color occurs.
이에 대하여, 본 발명자들은 상기 문제점을 극복하기 위하여 고무강화 폴리스티렌 수지 공중합체에 주 난연제인 할로겐 화합물들과 난연 보조제인 삼산화안티몬을 조합하여 첨가함으로써 UL94 V-2 제품의 난연성을 유지하면서 열 안정성을 보강시켜 밝은색 제품에 적용은 물론 대형제품의 사출성형에 적합한 난연성 열가소성 수지 조성물을 개발하기에 이른 것이다.On the other hand, the present inventors reinforce the thermal stability while maintaining the flame retardancy of UL94 V-2 products by adding a combination of halogen compounds as the main flame retardant and antimony trioxide as the flame retardant to the rubber-reinforced polystyrene resin copolymer to overcome the above problems. It is to develop a flame-retardant thermoplastic resin composition suitable for injection molding of large products as well as applied to light products.
본 발명의 목적은 난연성이 우수한 UL94 V-2 스티렌계 수지 조성물을 제공하기 위한 것이다.An object of the present invention is to provide a UL94 V-2 styrene resin composition excellent in flame retardancy.
본 발명의 다른 목적은 고온에서의 사용이 가능하고 열 변색이 방지되도록 열 안정성을 향상시킨 난연성 스티렌계 수지 조성물을 제공하기 위한 것이다.Another object of the present invention is to provide a flame retardant styrene resin composition which can be used at a high temperature and improves thermal stability to prevent thermal discoloration.
본 발명의 상기 및 기타 목적들은 하기 설명되는 본 발명에 의하여 모두 달성될 수 있다.The above and other objects of the present invention can be achieved by the present invention described below.
본 발명의 난연성 스티렌계 열가소성 수지 조성물은 (A) 고무강화 폴리스티렌 수지 100 중량부; (B) 브로미네이티드 에폭시 올리고머(Brominated epoxy oligomer) 1 내지 5 중량부; (C) 2,4,6-트리(2,4,6-트리브로모페녹시)-1,3,5-트리아진 5 내지 10 중량부; 및 (D) 난연 보조제 0.5 내지 5 중량부로 이루어지며, 이들 각각의 성분에 대한 상세한 설명은 다음과 같다.Flame retardant styrene-based thermoplastic resin composition of the present invention (A) 100 parts by weight of rubber-reinforced polystyrene resin; (B) 1 to 5 parts by weight of brominated epoxy oligomer; (C) 5 to 10 parts by weight of 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine; And (D) 0.5 to 5 parts by weight of flame retardant auxiliaries, the details of each of which are as follows.
(A) 고무강화 폴리스티렌 수지(A) Rubber reinforced polystyrene resin
본 발명에 의한 고무강화 폴리스티렌 수지는 고무와 방향족 모노알케닐 단량체 및/또는 알킬 에스테르 단량체를 혼합하고 여기에 중합 개시제를 사용하여 중합시켜 제조된다.The rubber-reinforced polystyrene resin according to the present invention is prepared by mixing a rubber with an aromatic monoalkenyl monomer and / or an alkyl ester monomer and polymerizing it using a polymerization initiator.
상기 고무로는 부타디엔형 고무류, 이소프렌형 고무류, 부타디엔과 스티렌의 공중합체류 또는 알킬아크릴레이트 고무류 등으로 이루어진 군으로부터 선택된 고무 5 내지 15 중량부로 사용하는 것이 바람직하다.The rubber is preferably used in an amount of 5 to 15 parts by weight of a rubber selected from the group consisting of butadiene rubbers, isoprene rubbers, copolymers of butadiene and styrene, alkyl acrylate rubbers and the like.
또한 상기 단량체로는 방향족 모노알케닐 단량체, 아크릴산 또는 메타크릴산의 알킬에스테르 단량체 중에서 선택된 1종 또는 1종 이상의 단량체를 85 내지 95 중량부 투입하는 것이 바람직하다.In addition, the monomer is preferably 85 to 95 parts by weight of one or more monomers selected from aromatic monoalkenyl monomers, alkyl ester monomers of acrylic acid or methacrylic acid.
상기 중합개시제로는 벤조일 퍼옥사이드, t-부틸 하이드로 퍼옥사이드, 아세틸 퍼옥사이드, 큐멘하이드로 퍼옥사이드에서 선택된 1종 혹은 1종 이상의 개시제를 이용하여 괴상 중합시켜서 상기 수지를 제조할 수 있다.As the polymerization initiator, the resin may be prepared by bulk polymerization using one or more initiators selected from benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, and cumene hydroperoxide.
상기 고무강화 폴리스티렌 수지는 괴상 중합, 현탁 중합, 유화 중합 또는 이들의 혼합방법을 사용하여 제조될 수 있으며, 상기 중합방법들 중 괴상 중합방법이 바람직하게 사용될 수 있다.The rubber-reinforced polystyrene resin may be prepared using a bulk polymerization, suspension polymerization, emulsion polymerization or a mixture thereof, and among the polymerization methods, a bulk polymerization method may be preferably used.
(B) 브로미네이티드 에폭시 올리고머(Brominated epoxy oligomer)(B) Brominated epoxy oligomer
본 발명에서 UL94 V-2 난연을 유지하기 위하여 멜트(melt)형 할로겐 난연제, 특히 브롬계 난연제를 사용한다. 상기 브롬계 난연제로는 브로미네이티드 에폭시 올리고머(Brominated epoxy oligomer)가 바람직하다.In the present invention, a melt halogen flame retardant, particularly a bromine flame retardant, is used to maintain UL94 V-2 flame retardant. The brominated flame retardant is preferably a brominated epoxy oligomer.
상기 브로미네이티드 에폭시 올리고머(Brominated epoxy oligomer)는 하기 화학식(I)으로 표시된다:The brominated epoxy oligomer is represented by formula (I):
상기 식에서 n은 1 또는 2이다.Wherein n is 1 or 2.
상기 멜트형 할로겐화 난연제(B)는 고무강화 폴리스티렌 수지(A) 100 중량부에 대하여 1 내지 5 중량부를 사용하는 것이 바람직하다. 1 중량부 이하를 첨가하였을 경우에는 난연 시간초과가 발생하며, 5 중량부 이상을 사용하였을 경우에는 내후성에 문제가 발생하게 된다. 그러나, 본 발명에서는 2,4,6-트리(2,4,6-트리브로모페녹시)-1,3,5-트리아진(C)과 삼산화안티몬(D)을 함께 적용함으로써 이와 같은 문제점을 해결하였다.The melt halogenated flame retardant (B) is preferably used 1 to 5 parts by weight based on 100 parts by weight of rubber-reinforced polystyrene resin (A). When 1 part by weight or less is added, a flame retardant timeout occurs, and when 5 parts by weight or more is used, a problem occurs in weather resistance. However, in the present invention, such problems by applying 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine (C) and antimony trioxide (D) together Solved.
(C) 2,4,6-트리(2,4,6-트리브로모페녹시)-1,3,5-트리아진(C) 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine
본 발명에서는 알리파틱 할로겐화 난연제(B)가 열 안정성에 문제가 있으므로 열 안정성을 향상시키기 위하여 2,4,6-트리(2,4,6-트리브로모페녹시)-1,3,5-트리아진을 주 난연제로 사용한다. 상기 2,4,6-트리(2,4,6-트리브로모페녹시)-1,3,5-트리아진 난연제를 첨가함으로써 UL94 V-2 제품의 난연성을 유지하면서 열 안정성을 보강하고 수지의 내후성을 향상시킬 뿐만 아니라, 밝은 색 제품에 적용은 물론 성형성이 우수한 난연성 열가소성 수지 조성물을 제조할 수 있게 된 것이다.In the present invention, since the aliphatic halogenated flame retardant (B) has a problem in thermal stability, in order to improve thermal stability, 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5- Triazine is used as the main flame retardant. By adding the 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine flame retardant, the thermal stability of the UL94 V-2 product is reinforced and the resin is reinforced. In addition to improving the weather resistance of the present invention, it is possible to prepare a flame retardant thermoplastic resin composition having excellent moldability as well as being applied to a bright color product.
상기 2,4,6-트리(2,4,6-트리브로모페녹시)-1,3,5-트리아진 화합물(C)은 하기화학식(II)으로 표시된다:The 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine compound (C) is represented by the following formula (II):
상기 2,4,6-트리(2,4,6-트리브로모페녹시)-1,3,5-트리아진 화합물(C)은 고무 강화 폴리스티렌 수지(A) 100 중량부에 대하여 5 내지 10 중량부를 사용하는 것이 바람직하다. 5 중량부 이하를 첨가하였을 경우에는 난연 효과 부족하며 10 중량부 이상을 사용하였을 경우에는 물성의 균형을 해치게 되므로 바람직하지 못하다.The 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine compound (C) is 5 to 10 based on 100 parts by weight of rubber-reinforced polystyrene resin (A) Preference is given to using parts by weight. When 5 parts by weight or less is added, the flame retardant effect is insufficient, and when 10 parts by weight or more is used, it is not preferable because it impairs the balance of physical properties.
(D) 난연 보조제(D) flame retardant supplements
본 발명에서는 브롬계 난연제의 난연성을 더욱 향상시키기 위한 보조 난연제가 첨가된다. 난연 보조제로는 삼산화 안티몬, 염화 파라핀, 포타슘설폰설페이트 및 이들의 혼합물로 이루어진 군으로부터 선택된 것을 사용하며, 삼산화안티몬을 사용하는 것이 바람직하다.In the present invention, an auxiliary flame retardant for further improving the flame retardancy of the brominated flame retardant is added. The flame retardant aid is selected from the group consisting of antimony trioxide, paraffin chloride, potassium sulfone sulfate and mixtures thereof, and antimony trioxide is preferably used.
난연 보조제(D)는 본 발명의 기초수지(A) 100 중량부에 대하여 0.5 내지 5 중량부를 사용하는 것이 바람직하다. 상기 난연 보조제(D)를 0.5 중량부 미만으로사용하는 경우에는 충분한 난연 효과를 얻을 수 없으며, 5 중량부를 초과하여 과량 사용하였을 경우에는 수지 조성물의 물성상의 균형을 해치게 되어 바람직하지 않다.It is preferable to use 0.5-5 weight part of a flame retardant adjuvant (D) with respect to 100 weight part of base resins (A) of this invention. When the flame retardant auxiliary (D) is used in less than 0.5 parts by weight, a sufficient flame retardant effect is not obtained, and when used in excess of 5 parts by weight, the balance of the physical properties of the resin composition is not preferable.
본 발명의 난연성 열가소성 수지 조성물은 상기의 구성성분 외에도 각각의 용도에 따라 무기 첨가제, 산화방지제, 기타 광 안정제, 안료 및 염료를 필요한 양으로 첨가할 수 있다.In addition to the above components, the flame retardant thermoplastic resin composition of the present invention may add inorganic additives, antioxidants, other light stabilizers, pigments, and dyes in necessary amounts depending on their respective uses.
본 발명의 수지 조성물은 여러 가지 제품의 성형에 사용될 수 있으며, 특히 열 안정성 및 UL94 V-2 난연성을 갖기 때문에 고온에서 사출되면서 난연성과 열 안정성이 요구되는 전기, 전자 제품의 하우징의 제조에 적합하다.The resin composition of the present invention can be used for molding a variety of products, and in particular, because it has thermal stability and UL94 V-2 flame retardancy, it is suitable for the manufacture of housings of electrical and electronic products requiring flame retardancy and thermal stability while being injected at high temperatures. .
본 발명은 하기의 실시예에 의하여 보다 더 잘 이해될 수 있으며, 하기의 실시예는 본 발명의 예시 목적을 위한 것이며 첨부된 특허청구범위에 의하여 한정되는 보호범위를 제한하고자 하는 것은 아니다.The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.
실시예Example
하기의 실시예 및 비교실시예에서 (A) 고무강화 폴리스티렌 수지로 제일모직의 HR-1360을 사용하였고, (B) 난연제로 상기 화학식(I)으로 표시되는 브로미네이티드 에폭시 올리고머(Brominated epoxy oligomer)를 사용하였고, (C) 주 난연제로 상기 화학식(II)으로 표시되는 2,4,6-트리(2,4,6-트리브로모페녹시)-1,3,5-트리아진을 사용하였고, (D) 난연 보조제로는 삼산화 안티몬을 사용하였다.In the following Examples and Comparative Examples (A) HR-1360 of Cheil Industries as a rubber-reinforced polystyrene resin, (B) Brominated epoxy oligomer represented by the formula (I) as a flame retardant (C) 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5-triazine represented by Formula (II) was used as the main flame retardant. , (D) Antimony trioxide was used as a flame retardant aid.
실시예 1-5 및 비교실시예 1-3Example 1-5 and Comparative Example 1-3
상기 구성성분들을 표 1에 나타낸 함량으로 투입하여 이루어진 수지 조성물을 텀블러(Tumbler)믹서로 균일하게 혼합시킨 후, 이축 압출기로 압출하여 펠렛 형태로 제조하고, 제조된 펠렛으로부터 사출성형에 의해 1/8"두께의 난연시편 및 열 안정성 시험시편을 제작하여 평가하였다.The resin composition prepared by adding the above components in the amounts shown in Table 1 was uniformly mixed with a tumbler mixer, extruded by a twin screw extruder to produce pellets, and produced by injection molding from 1/8 by injection molding. Thickness and flame-retardant specimens and thermal stability test specimens were fabricated and evaluated.
상기의 방법으로 제조된 수지 조성물의 난연성에 대한 측정은 UL-94 판정시험 방법에 따라 진행하였다. 참고로 V-2 등급은 시편에 점화가 되었을 때, 정해진 시간 이내에 불꽃을 시편 상에서 떨어 뜨려 소화를 시키는 수지에 주어지는 등급이다. 열 안정성 평가는 수지를 사출기 실린더 안에 체류(10분, 240℃)시킨 후 사출 성형시 시편에 나타나는 흑줄의 개수를 측정하여 평가하였다.Measurement of the flame retardancy of the resin composition prepared by the above method was carried out according to the UL-94 determination test method. For reference, the V-2 grade is given to resins that extinguish the flame by dropping the flame on the specimen within a specified time when the specimen is ignited. Thermal stability evaluation was evaluated by measuring the number of black streaks appearing in the specimen during injection molding after the resin stayed in the injection molding machine cylinder (10 minutes, 240 ℃).
실시예 1-5 및 비교실시예 1-3에서 제조된 수지의 물성을 표 1에 나타내었다. 실시예 1-5는 본 발명에 의한 범위로 난연제 및 난연 보조제를 사용한 경우이고, 비교실시예 1-3은 상기 범위를 벗어나서 사용한 경우이다.Table 1 shows the physical properties of the resins prepared in Examples 1-5 and Comparative Examples 1-3. Example 1-5 is a case where a flame retardant and a flame retardant adjuvant are used in the range by this invention, and Comparative Example 1-3 is a case where it used out of the said range.
상기 표 1의 결과로부터, 멜트형 할로겐계 난연제인 브로미네이티드 에폭시 올리고머(Brominated epoxy oligomer)와 2,4,6-트리(2,4,6-트리브로모페녹시)-1,3,5-트리아진이 동시에 사용된 실시예 1-5에서 난연도 및 열 안정성이 동시에 우수하였다. 멜트형 할로겐계 난연제인 브로미네이티드 에폭시 올리고머(Brominated epoxy oligomer)를 사용한 비교실시예 2는 난연도는 우수하였으나 열 안정성이 매우 낮은 것으로 나타났으며, 난연제로 2,4,6-트리 (2,4,6-트리브로모페녹시)-1,3,5-트리아진을 사용한 비교실시예 1과3의 경우는 난연성이 저하되었다. 비교실시예 1의 경우 난연제의 분해에 의한 수지의 분해 촉진으로 연소시 빠른 시간 안에 수지의 드립(Drip)을 유발하도록 하여야 하는데 수지의 분해 촉진이 잘 안되었다.From the results in Table 1, brominated epoxy oligomers, 2,4,6-tri (2,4,6-tribromophenoxy) -1,3,5, which are melt halogen flame retardants -The flame retardancy and thermal stability were excellent simultaneously in Example 1-5 in which triazine was used simultaneously. Comparative Example 2 using a brominated epoxy oligomer, which is a melt halogen flame retardant, showed excellent flame retardancy but very low thermal stability. As a flame retardant, 2,4,6-tree (2, In the case of Comparative Examples 1 and 3 using 4,6-tribromophenoxy) -1,3,5-triazine, the flame retardance decreased. In Comparative Example 1, it is necessary to induce a drip of the resin in a short time during combustion due to the decomposition of the resin by the decomposition of the flame retardant.
본 발명은 고무강화 폴리스티렌 수지 공중합체에 알리파틱 할로겐계 난연제인 브로미네이티드 에폭시 올리고머(Brominated epoxy oligomer)와2,4,6-트리(2,4,6-트리브로모페녹시)-1,3,5-트리아진을 동시에 사용함으로써 난연성과 열 안정성이 동시에 우수한 열가소성 수지 조성물을 제공하는 발명의 효과를 갖는다.The present invention relates to a rubber reinforced polystyrene resin copolymer, a brominated epoxy oligomer, which is an aliphatic halogen flame retardant, and 2,4,6-tri (2,4,6-tribromophenoxy) -1, By using 3,5-triazine simultaneously, the invention has the effect of providing a thermoplastic resin composition having excellent flame retardancy and thermal stability.
본 발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.
Claims (6)
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| KR20040042354A true KR20040042354A (en) | 2004-05-20 |
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| Application Number | Title | Priority Date | Filing Date |
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| KR1020020070626A Ceased KR20040042354A (en) | 2002-11-14 | 2002-11-14 | Flame Retardant Thermoplastic Resin Composition |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100653689B1 (en) * | 2004-06-09 | 2006-12-04 | 삼성전자주식회사 | Salicide process using a double metal layer and a method of manufacturing a semiconductor device using the same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5284604A (en) * | 1991-05-09 | 1994-02-08 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Flame retarded thermoplastic composition |
| JPH09208793A (en) * | 1996-02-06 | 1997-08-12 | Japan Synthetic Rubber Co Ltd | Flame retardant resin composition |
| JPH10176095A (en) * | 1996-12-19 | 1998-06-30 | Daicel Chem Ind Ltd | Flame resistant styrenic resin composition |
| JP2001164076A (en) * | 1999-12-10 | 2001-06-19 | Mitsubishi Chemicals Corp | Flame retardant styrenic resin composition |
| KR20020021522A (en) * | 2000-09-15 | 2002-03-21 | 성재갑 | Transparent thermoplastic resin composition having superior fireproof properties |
-
2002
- 2002-11-14 KR KR1020020070626A patent/KR20040042354A/en not_active Ceased
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5284604A (en) * | 1991-05-09 | 1994-02-08 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Flame retarded thermoplastic composition |
| JPH09208793A (en) * | 1996-02-06 | 1997-08-12 | Japan Synthetic Rubber Co Ltd | Flame retardant resin composition |
| JPH10176095A (en) * | 1996-12-19 | 1998-06-30 | Daicel Chem Ind Ltd | Flame resistant styrenic resin composition |
| JP2001164076A (en) * | 1999-12-10 | 2001-06-19 | Mitsubishi Chemicals Corp | Flame retardant styrenic resin composition |
| KR20020021522A (en) * | 2000-09-15 | 2002-03-21 | 성재갑 | Transparent thermoplastic resin composition having superior fireproof properties |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100653689B1 (en) * | 2004-06-09 | 2006-12-04 | 삼성전자주식회사 | Salicide process using a double metal layer and a method of manufacturing a semiconductor device using the same |
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