JPH03281652A - Flame-retardant resin composition - Google Patents
Flame-retardant resin compositionInfo
- Publication number
- JPH03281652A JPH03281652A JP8098490A JP8098490A JPH03281652A JP H03281652 A JPH03281652 A JP H03281652A JP 8098490 A JP8098490 A JP 8098490A JP 8098490 A JP8098490 A JP 8098490A JP H03281652 A JPH03281652 A JP H03281652A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- weight
- polyalkylene terephthalate
- flame
- melamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 24
- 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 abstract description 18
- 239000011342 resin composition Substances 0.000 title claims description 6
- 229920001283 Polyalkylene terephthalate Polymers 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 13
- 239000000945 filler Substances 0.000 claims abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 239000011574 phosphorus Substances 0.000 claims abstract description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 14
- 229920000877 Melamine resin Polymers 0.000 claims description 12
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 9
- -1 polyethylene terephthalate Polymers 0.000 abstract description 15
- 239000003365 glass fiber Substances 0.000 abstract description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract description 3
- 239000005020 polyethylene terephthalate Substances 0.000 abstract description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 abstract description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 abstract 2
- 238000013329 compounding Methods 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229920001281 polyalkylene Polymers 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical compound O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical class OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- GTTBQSNGUYHPNK-UHFFFAOYSA-N hydroxymethylphosphonic acid Chemical compound OCP(O)(O)=O GTTBQSNGUYHPNK-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- YAFOVCNAQTZDQB-UHFFFAOYSA-N octyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC)OC1=CC=CC=C1 YAFOVCNAQTZDQB-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、ハロゲン系難燃剤を使用することなく難燃性
を改良したポリアルキレンテレフタレート樹脂組成物に
関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a polyalkylene terephthalate resin composition with improved flame retardancy without using a halogen flame retardant.
（従来の技術）
ポリエチレンテレフタレートやポリブチレンテレフタレ
ートに代表されるポリアルキレンテレフタレートは、そ
の優れた特性から電気および電子機器部品、自動車部品
などに広く使用されている。特に電気及び電子機器部品
分野では、火災に対する安全性を確保するために難燃性
を付与して使用される例が多い。(Prior Art) Polyalkylene terephthalates, represented by polyethylene terephthalate and polybutylene terephthalate, are widely used in electrical and electronic equipment parts, automobile parts, etc. due to their excellent properties. Particularly in the field of electrical and electronic equipment parts, they are often used with flame retardancy added to ensure safety against fire.
ポリアルキレンテレフタレート系樹脂に難燃性を付与す
るには、一般的にハロゲン系難燃剤を使用するが、ハロ
ゲン系難燃剤を使用すると、混合時及び成形時にハロゲ
ン系難燃剤の一部が分解し、フリーのハロゲンイオンや
ガスが発生し、混合混練機や射出成形機のシリンダーや
スクリュー及び金型の表面を腐蝕させたり、電子部品分
野では、部品の金属を腐蝕させ、接点不良や導通不良を
ひきおこしたりする。またハロゲン系難燃剤の中には、
分解発生するガスに極（少量ながら、毒性のあるものも
含まれる例がある。Halogen-based flame retardants are generally used to impart flame retardancy to polyalkylene terephthalate resins, but when halogen-based flame retardants are used, some of the halogen-based flame retardants decompose during mixing and molding. , free halogen ions and gases are generated, which corrode the surfaces of cylinders, screws, and molds in mixing and kneading machines and injection molding machines, and in the field of electronic components, corrode the metal of parts and cause poor contacts and poor continuity. It stirs things up. In addition, some halogen flame retardants include
There are cases where the gases generated by decomposition include extremely toxic substances, albeit in small amounts.
また、特公昭６０−３３８５０号公報では、ポリアルキ
レンテレフタレート系ポリエステルに対しメラミン・シ
アヌル酸付加物を３〜３０重量％添加して難燃化をはか
ることが提案されているが、この手法においても難燃性
のＵＬ規格には到達しえなかった。In addition, Japanese Patent Publication No. 60-33850 proposes adding 3 to 30% by weight of a melamine/cyanuric acid adduct to polyalkylene terephthalate polyester to make it flame retardant. It could not meet the UL standard for flame retardancy.
（発明が解決しようとする課題）
このような問題点を解決するための検討は種々なされて
きたが、有効な解決策は見い出されていない。(Problems to be Solved by the Invention) Various studies have been made to solve these problems, but no effective solution has been found.
本発明の課題は、ポリアルキレンテレフタレート樹脂の
成形時におけるハロゲン系難燃剤の分解、ガス発生等の
欠点を解決した、改良難燃性樹脂組成物を提供すること
である。An object of the present invention is to provide an improved flame-retardant resin composition that overcomes drawbacks such as decomposition of halogen flame retardants and gas generation during molding of polyalkylene terephthalate resins.
（課題を解決するための手段）
本発明者らは、かかる観点にもとづき鋭意検討をした結
果、ポリアルキレンテレフタレート樹脂に、メラミン・
シアヌル酸付加物とリン系難燃剤を配合することにより
、ハロゲン系難燃剤を使用せずに、相乗効果によりすぐ
れた難燃性を付与することが可能となり、本発明に到達
した。(Means for Solving the Problem) As a result of intensive studies based on this viewpoint, the present inventors have added melamine to polyalkylene terephthalate resin.
By blending a cyanuric acid adduct and a phosphorus-based flame retardant, it is possible to impart excellent flame retardancy due to a synergistic effect without using a halogen-based flame retardant, and the present invention has been achieved.
すなわち１本発明は、
下記成分を配合してなるポリアルキレンテレフタレート
系難燃性樹脂組成物である。That is, one aspect of the present invention is a polyalkylene terephthalate flame-retardant resin composition containing the following components.
（Ａ）ポリアルキレンテレフタレート樹脂１００１ｉ量
部に対し、
（Ｂ）充填材３０〜２５０重量部、
（Ｃ）メラミン・シアヌル駿付加物５〜５０重量部、及
び
（Ｄ）リン系難燃剤５御５０
本発明の（Ａ）成分であるポリアルキレンテレフタレー
ト樹脂とは、ジカルボン酸成分の少なくとも４０モル％
がテレフタル酸であるジカルボン酸成分とジオール成分
とを主成分とする縮合重合により得られるポリアルキレ
ンテレフタレート樹脂である。(A) 1001 parts by weight of polyalkylene terephthalate resin, (B) 30 to 250 parts by weight of filler, (C) 5 to 50 parts by weight of melamine/cyanuric adduct, and (D) 5 to 50 parts by weight of phosphorus flame retardant. The polyalkylene terephthalate resin which is component (A) of the present invention is at least 40 mol% of the dicarboxylic acid component.
This is a polyalkylene terephthalate resin obtained by condensation polymerization mainly consisting of a dicarboxylic acid component, which is terephthalic acid, and a diol component.
上記テレフタル酸以外のジカルボン酸成分としては、ア
ゼライン酸、セバシン酸、アジピン酸、ドデカンジカル
ボン酸を含む炭素数２〜２ｏの脂肪族ジカルボン酸、イ
ソフタル酸、オルトフタル酸、ナフタレンジカルボン酸
、ジフェニル−４４′−ジカルボン酸、ジフェニルエタ
ン−４。Dicarboxylic acid components other than the above-mentioned terephthalic acid include azelaic acid, sebacic acid, adipic acid, aliphatic dicarboxylic acids having 2 to 2 carbon atoms including dodecanedicarboxylic acid, isophthalic acid, orthophthalic acid, naphthalene dicarboxylic acid, diphenyl-44' -Dicarboxylic acid, diphenylethane-4.
４′−ジカルボン酸を含む芳香族ジカルボン酸又はシク
ロヘキサンジカルボン酸で代表される脂環式ジカルボン
酸の単独ないし混合物があげられる。Examples include aromatic dicarboxylic acids including 4'-dicarboxylic acid or alicyclic dicarboxylic acids represented by cyclohexanedicarboxylic acid, either singly or in mixtures.
上記ジオール成分としては、炭素数２〜２０の脂肪族グ
リコール、例えばエチレングリコール、プロピレングリ
コール、１．４−ブタンジオール、ネオペンチルグリコ
ール、１．５−ベンタンジオール、１．６−ヘキサンジ
オール、デカメチレングリコール、シクロヘキサンジメ
タールなど、及び、分子量４００〜６．０００の長鎖グ
リコール、例えばポリエチレングリコール、ポリ−１、
３−プロピレングリコール、ポリテトラメチレングリコ
ールなど、又はこれらの混合物があげられる。The diol component includes aliphatic glycols having 2 to 20 carbon atoms, such as ethylene glycol, propylene glycol, 1.4-butanediol, neopentyl glycol, 1.5-bentanediol, 1.6-hexanediol, decamethylene Glycols, cyclohexanedimether, etc., and long chain glycols with a molecular weight of 400 to 6,000, such as polyethylene glycol, poly-1,
Examples include 3-propylene glycol, polytetramethylene glycol, and mixtures thereof.
上記のジカルボン酸成分及びジオール成分よりなる代表
的なポリアルキレンチレフクレート樹脂の例は、ポリエ
チレンテレフタレート、ポリへキサメチレンチレフクレ
ート、ポリシクロヘキサンジメチレンテレフタレートな
どである。Typical examples of polyalkylene ethylene terephthalate resins comprising the above dicarboxylic acid component and diol component include polyethylene terephthalate, polyhexamethylene ethylene terephthalate, polycyclohexane dimethylene terephthalate, and the like.
これらのポリアルキレンテレフタレート樹脂は，フェノ
ールとテトラクロルエタンの１＝１重量比混合溶媒中で
、３０℃で測定した固有粘度が０、３以上、１．５以下
、好ましくは０．４以上，１．２以下である．０，３未
満では樹脂として期待される物性が得られず、また１．
５をこえると流動性が著しく悪くなり、成形しがたくな
る。These polyalkylene terephthalate resins have an intrinsic viscosity of 0.3 or more and 1.5 or less, preferably 0.4 or more and 1.5 or less, as measured at 30°C in a 1=1 weight ratio mixed solvent of phenol and tetrachloroethane. .2 or less. If it is less than 0.3, the expected physical properties of the resin cannot be obtained, and 1.
If it exceeds 5, the fluidity becomes extremely poor and it becomes difficult to mold.
次に本発明の（Ｂ）成分である充填材は、繊維状又は粒
状の有機物もしくは無機物である．ｍ雌状の充填材とし
ては、ガラス繊維、シラスガラス繊維、アルミナ繊維、
炭化ケイ素繊維、セラミックス繊維、アスベスト繊維、
石こう繊維、ステンレス繊維、ボロン繊維、炭素繊維、
ケブラー繊維などがあげられる。Next, the filler which is component (B) of the present invention is a fibrous or granular organic or inorganic material. Examples of the female filler include glass fiber, glass fiber, alumina fiber,
silicon carbide fiber, ceramic fiber, asbestos fiber,
Gypsum fiber, stainless steel fiber, boron fiber, carbon fiber,
Examples include Kevlar fiber.
また粒状の充填材としては、ワラストナイト、セリサイ
ト、カオリン、マイカ、クレー、ベントナイト、アスベ
スト、タルク、アルミナシリケートなどのケイ酸塩：ア
ルミナ、酸化ケイ素、酸化マグネシウム、酸化ジルコニ
ウム、酸化チタンなどの金属酸化物；炭酸カルシウム、
炭酸マグネシウム、ドロマイトなどの炭酸塩；硫酸カル
シウム、硫酸バリウムなどの硫酸塩：その他ガラスピー
ズ、ガラスフレーク、窒化ホウ素、炭化ケイ素などがあ
げられる。Granular fillers include wollastonite, sericite, kaolin, mica, clay, bentonite, asbestos, talc, silicates such as alumina silicate, alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, etc. Metal oxide; calcium carbonate,
Carbonates such as magnesium carbonate and dolomite; sulfates such as calcium sulfate and barium sulfate; and glass peas, glass flakes, boron nitride, and silicon carbide.
これら充填材は、１種または２種以上が用いられる。These fillers may be used alone or in combination of two or more.
上記の強化・充填材は必要ならば、シラン系及びチタン
系のカップリング剤で予備処理しても良い。The reinforcing/filling materials described above may be pretreated with silane-based and titanium-based coupling agents, if necessary.
これら充填剤のポリアルキレンチレフクレート１００重
量部に対する配合量は、３０〜２５０重量部、好ましく
は、３５〜２００重量部である。３０重量部未満では、
充填材としての効果は発現せず、２５０重量部をこえる
と成形時の流動性が悪く、実用的でない。The amount of these fillers added to 100 parts by weight of polyalkylene thirefrectate is 30 to 250 parts by weight, preferably 35 to 200 parts by weight. Less than 30 parts by weight,
It does not exhibit any effect as a filler, and if it exceeds 250 parts by weight, the fluidity during molding is poor, making it impractical.
（Ｃ）成分であるメラミン・シアヌル酸付加物としては
、２，４．６−トリアミノ−１，３，５−トリアジンで
あるメラミンと２．４．６−ドリヒドロキシー１．３．
５−）リアジンまたはその互変異性物が形成する付加物
である。The melamine/cyanuric acid adduct, which is component (C), includes melamine, which is 2,4,6-triamino-1,3,5-triazine, and 2,4,6-dolyhydroxy-1,3.
5-) It is an adduct formed by riazine or its tautomer.
メラミン・シアヌル酸付加物を合成するには、メラミン
とシアヌル酸の混合モル比は任意でよいが、高純度品を
得るには等モルに近い方がよく、特にモル比１：１にな
ることが好ましい、また溶剤は水が好ましいが、水と混
和する溶剤、例えば低級アルコール、アセトン、メチル
エチルケトン、テトラヒドロフラン、ジメチルホルムア
ミド等を利用することができる。To synthesize a melamine/cyanuric acid adduct, the mixing molar ratio of melamine and cyanuric acid can be arbitrary, but to obtain a high-purity product, it is better to have a molar ratio close to equimolar, especially a molar ratio of 1:1. is preferred, and water is preferred as the solvent; however, solvents that are miscible with water, such as lower alcohols, acetone, methyl ethyl ketone, tetrahydrofuran, dimethylformamide, etc., can be used.
反応温度は任意であるが、反応時間とのかわあいより２
０〜１５０℃、好ましくは４０〜１００℃である。The reaction temperature is arbitrary, but depending on the reaction time, 2
The temperature is 0 to 150°C, preferably 40 to 100°C.
これらメラミン・シアヌル酸付加物のポリアルキレンテ
レフタレート１００重量部に対する配合量は、５〜５０
重量部、好ましくは１０〜４０重量部である。５重量部
未満ではリン系難燃剤と併用しても難燃性が充分でない
場合もあり、５０重量部をこえると機械的強度が実用的
なレベルを保持しえない場合もある。The blending amount of these melamine/cyanuric acid adducts per 100 parts by weight of polyalkylene terephthalate is 5 to 50 parts by weight.
Parts by weight, preferably 10 to 40 parts by weight. If it is less than 5 parts by weight, flame retardancy may not be sufficient even when used in combination with a phosphorus-based flame retardant, and if it exceeds 50 parts by weight, mechanical strength may not be maintained at a practical level.
（Ｄ）成分としてのリン系難燃剤としては、炭素数１〜
１２．好ましくは１〜８の直鎖又は分岐した脂肪族基、
芳香族基、脂環式基を有するアルコール又はフェノール
のホスフェート化合物、ホスホネート化合物であり、好
ましくは、トリフェニルホスフェート、トリクレジルホ
スフェート、クレジルジフェニルホスフェート、オクチ
ルジフェニルホスフェート、ジアルキルヒドロキシメチ
ルホスホネートである。The phosphorus flame retardant as component (D) has 1 to 1 carbon atoms.
12. Preferably 1 to 8 linear or branched aliphatic groups,
A phosphate compound or phosphonate compound of alcohol or phenol having an aromatic group or alicyclic group, preferably triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyldiphenyl phosphate, and dialkyl hydroxymethyl phosphonate.
これらリン系難燃剤のポリアルキレンテレフタレート１
００重量部に対する配合量は、５〜５０重量部、好まし
くは７〜４０重量部である。７重量部未満ではメラミン
・シアヌル酸付加物と併用しても難燃性が充分でない場
合があり、５０重量部をこえると機械的強度が実用レベ
ルを保持しえない場合もある。Polyalkylene terephthalate 1 of these phosphorus-based flame retardants
The blending amount for 00 parts by weight is 5 to 50 parts by weight, preferably 7 to 40 parts by weight. If it is less than 7 parts by weight, flame retardancy may not be sufficient even when used in combination with a melamine/cyanuric acid adduct, and if it exceeds 50 parts by weight, mechanical strength may not be maintained at a practical level.
本発明の組成物に対しては、本発明の目的を損なわない
範囲で、酸化防止剤、熱安定剤、紫外線吸収剤、可塑剤
、結晶核剤、結晶化促進剤、顔料、着色剤、帯電防止剤
などを配合することができる。The composition of the present invention may contain antioxidants, heat stabilizers, ultraviolet absorbers, plasticizers, crystal nucleating agents, crystallization promoters, pigments, coloring agents, electrostatic charges, etc., to the extent that does not impair the purpose of the present invention. An inhibitor or the like can be added.
本発明の難燃性樹脂組成物は、通常の溶融混練法で容易
に製造することができる。The flame-retardant resin composition of the present invention can be easily produced by a normal melt-kneading method.
以下実施例をあげて本発明を説明する。The present invention will be explained below with reference to Examples.
実施例
ポリアルキレンテレフタレート、強化・充填物、メラミ
ン・シアヌル酸付加物及びリン系難燃剤を表で示す割合
で配合し、４０ｍｍφ単軸押出機で溶融混線し、ベレッ
ト化した。Example Polyalkylene terephthalate, reinforcement/filler, melamine/cyanuric acid adduct, and phosphorous flame retardant were blended in the proportions shown in the table, melted and mixed in a 40 mmφ single screw extruder, and pelletized.
得られたベレットを１３０’Ｃ１５時間乾燥した後、日
本製鋼所社製Ｊ−１００射出成形機を用いて、金型温度
を８０℃で試験片を成形した後、難燃性についてＵＬ−
９４に定める手法にもとづき、１／３２インチの厚みで
検討した。After drying the obtained pellet at 130'C for 15 hours, a test piece was molded using a J-100 injection molding machine manufactured by Japan Steel Works, Ltd. at a mold temperature of 80°C.
Based on the method specified in 94, a thickness of 1/32 inch was investigated.
（発明の効果）
上記試験結果から明らかなように、本発明の組成と配合
量からなる組成物は、メラミン・シアヌル酸付加物又は
リン系難燃剤をそれぞれ単独で用いた組成物と比べて優
れた難燃性を示す。(Effects of the Invention) As is clear from the above test results, the composition consisting of the composition and blending amount of the present invention is superior to the composition using either the melamine/cyanuric acid adduct or the phosphorus flame retardant alone. It exhibits flame retardant properties.
Claims (1)
レフタレート系難燃性樹脂組成物 （Ａ）ポリアルキレンテレフタレート樹脂１００重量部
に対し、 （Ｂ）充填材３０〜２５０重量部、 （Ｃ）メラミン・シアヌル酸付加物５〜５０重量部、及
び （Ｄ）リン系難燃剤５〜５０重量部[Scope of Claims] A polyalkylene terephthalate flame-retardant resin composition characterized by containing the following components: (A) 100 parts by weight of polyalkylene terephthalate resin, (B) 30 to 250 parts by weight of filler, (C) melamine/cyanuric acid adduct 5 to 50 parts by weight, and (D) phosphorus flame retardant 5 to 50 parts by weight
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8098490A JPH03281652A (en) | 1990-03-30 | 1990-03-30 | Flame-retardant resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8098490A JPH03281652A (en) | 1990-03-30 | 1990-03-30 | Flame-retardant resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03281652A true JPH03281652A (en) | 1991-12-12 |
Family
ID=13733766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8098490A Pending JPH03281652A (en) | 1990-03-30 | 1990-03-30 | Flame-retardant resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03281652A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996037548A1 (en) * | 1995-05-23 | 1996-11-28 | Aicello Chemical Co., Ltd. | Flame-retardant resin composition |
| US5684071A (en) * | 1993-12-28 | 1997-11-04 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Additive for thermpolastic resins and flame retardant resin composition |
| WO1998056857A1 (en) * | 1997-06-13 | 1998-12-17 | Polyplastics Co., Ltd. | Flame-retardant thermoplastic polyester resin composition |
| NL1006525C2 (en) * | 1997-07-10 | 1999-01-12 | Dsm Nv | Halogen-free flame-retardant thermoplastic polyester composition. |
| EP0955338A2 (en) * | 1998-05-07 | 1999-11-10 | Basf Aktiengesellschaft | Flame protected polyester moulding matters |
| EP0955333A2 (en) * | 1998-05-07 | 1999-11-10 | Basf Aktiengesellschaft | Flame protected polyester moulding matters |
| US6737455B2 (en) | 2000-12-15 | 2004-05-18 | General Electric Company | Flame retardant polyester compositions |
| US6780905B2 (en) | 2001-06-27 | 2004-08-24 | Bayer Aktiengesellschaft | Flame-proof polyester molding compositions comprising ZnS |
| US7135509B2 (en) | 2002-09-25 | 2006-11-14 | Toray Industries, Inc. | Flame-retardant polybutylene terephthalate resin composition and formed article |
| JP2010533777A (en) * | 2007-07-16 | 2010-10-28 | エフアールエックス ポリマーズ、インク． | Flame retardant engineering polymer composition |
| WO2011159897A1 (en) | 2010-06-16 | 2011-12-22 | Federal-Mogul Powertrain, Inc. | Flame-retardant compound, continuous materials and products constructed therefrom and methods of manufacture thereof |
| US10167377B2 (en) | 2013-01-22 | 2019-01-01 | Frx Polymers, Inc. | Phosphorus containing epoxy compounds and compositions therefrom |
| CN113643867A (en) * | 2021-10-13 | 2021-11-12 | 浙江荣泰电工器材股份有限公司 | Mica piece with high surface tear strength and forming method thereof |
-
1990
- 1990-03-30 JP JP8098490A patent/JPH03281652A/en active Pending
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5684071A (en) * | 1993-12-28 | 1997-11-04 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Additive for thermpolastic resins and flame retardant resin composition |
| WO1996037548A1 (en) * | 1995-05-23 | 1996-11-28 | Aicello Chemical Co., Ltd. | Flame-retardant resin composition |
| WO1998056857A1 (en) * | 1997-06-13 | 1998-12-17 | Polyplastics Co., Ltd. | Flame-retardant thermoplastic polyester resin composition |
| US6433045B1 (en) | 1997-06-13 | 2002-08-13 | Polyplastics Co., Ltd. | Flame-retardant thermoplastic polyester resin composition |
| NL1006525C2 (en) * | 1997-07-10 | 1999-01-12 | Dsm Nv | Halogen-free flame-retardant thermoplastic polyester composition. |
| WO1999002606A1 (en) * | 1997-07-10 | 1999-01-21 | Dsm N.V. | Halogen-free flame-retardant thermoplastic polyester or polyamide composition |
| EP0955338A3 (en) * | 1998-05-07 | 1999-12-22 | Basf Aktiengesellschaft | Flame protected polyester moulding matters |
| EP0955333A3 (en) * | 1998-05-07 | 1999-12-22 | Basf Aktiengesellschaft | Flame protected polyester moulding matters |
| EP0955333A2 (en) * | 1998-05-07 | 1999-11-10 | Basf Aktiengesellschaft | Flame protected polyester moulding matters |
| EP0955338A2 (en) * | 1998-05-07 | 1999-11-10 | Basf Aktiengesellschaft | Flame protected polyester moulding matters |
| US6737455B2 (en) | 2000-12-15 | 2004-05-18 | General Electric Company | Flame retardant polyester compositions |
| US6780905B2 (en) | 2001-06-27 | 2004-08-24 | Bayer Aktiengesellschaft | Flame-proof polyester molding compositions comprising ZnS |
| US7135509B2 (en) | 2002-09-25 | 2006-11-14 | Toray Industries, Inc. | Flame-retardant polybutylene terephthalate resin composition and formed article |
| JP2010533777A (en) * | 2007-07-16 | 2010-10-28 | エフアールエックス ポリマーズ、インク． | Flame retardant engineering polymer composition |
| JP2013177614A (en) * | 2007-07-16 | 2013-09-09 | Frx Polymers Inc | Flame-retardant engineering polymer composition |
| WO2011159897A1 (en) | 2010-06-16 | 2011-12-22 | Federal-Mogul Powertrain, Inc. | Flame-retardant compound, continuous materials and products constructed therefrom and methods of manufacture thereof |
| US10167377B2 (en) | 2013-01-22 | 2019-01-01 | Frx Polymers, Inc. | Phosphorus containing epoxy compounds and compositions therefrom |
| CN113643867A (en) * | 2021-10-13 | 2021-11-12 | 浙江荣泰电工器材股份有限公司 | Mica piece with high surface tear strength and forming method thereof |
| CN113643867B (en) * | 2021-10-13 | 2021-12-31 | 浙江荣泰电工器材股份有限公司 | Mica piece with high surface tear strength and forming method thereof |
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