JP2011231276A - Flame-retardant resin composition, resin sheet, and resin molded article - Google Patents
Flame-retardant resin composition, resin sheet, and resin molded article Download PDFInfo
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- JP2011231276A JP2011231276A JP2010105057A JP2010105057A JP2011231276A JP 2011231276 A JP2011231276 A JP 2011231276A JP 2010105057 A JP2010105057 A JP 2010105057A JP 2010105057 A JP2010105057 A JP 2010105057A JP 2011231276 A JP2011231276 A JP 2011231276A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 63
- 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 59
- 239000011342 resin composition Substances 0.000 title claims abstract description 47
- 229920005989 resin Polymers 0.000 title claims abstract description 42
- 239000011347 resin Substances 0.000 title claims abstract description 42
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 20
- 239000010452 phosphate Substances 0.000 claims abstract description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 19
- -1 polypropylene Polymers 0.000 claims abstract description 18
- 239000004743 Polypropylene Substances 0.000 claims abstract description 8
- 150000002148 esters Chemical class 0.000 claims abstract description 8
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 150000002367 halogens Chemical class 0.000 claims abstract description 7
- 229920001155 polypropylene Polymers 0.000 claims abstract description 7
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 3
- 239000000956 alloy Substances 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 claims abstract description 3
- 229920005672 polyolefin resin Polymers 0.000 claims description 19
- 239000000155 melt Substances 0.000 claims description 12
- 150000001336 alkenes Chemical class 0.000 claims description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920001169 thermoplastic Polymers 0.000 claims description 2
- 239000004416 thermosoftening plastic Substances 0.000 claims description 2
- 229920006230 thermoplastic polyester resin Polymers 0.000 abstract description 11
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 238000002485 combustion reaction Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 238000004898 kneading Methods 0.000 description 6
- 238000007666 vacuum forming Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 230000007774 longterm Effects 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001384 propylene homopolymer Polymers 0.000 description 3
- 239000004114 Ammonium polyphosphate Substances 0.000 description 2
- 229920003355 Novatec® Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229940057995 liquid paraffin Drugs 0.000 description 2
- RLAWWYSOJDYHDC-BZSNNMDCSA-N lisinopril Chemical compound C([C@H](N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(O)=O)C(O)=O)CC1=CC=CC=C1 RLAWWYSOJDYHDC-BZSNNMDCSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- MEZLKOACVSPNER-GFCCVEGCSA-N selegiline Chemical compound C#CCN(C)[C@H](C)CC1=CC=CC=C1 MEZLKOACVSPNER-GFCCVEGCSA-N 0.000 description 2
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- MWVJKIZKNCNWHE-UHFFFAOYSA-N bis(1,6-dimethylcyclohexa-2,4-dien-1-yl) hydrogen phosphate Chemical compound C1(C(C=CC=C1)C)(C)OP(OC1(C(C=CC=C1)C)C)(O)=O MWVJKIZKNCNWHE-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical class [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、燃焼時における有害ガスの発生を抑えた非ハロゲン系の難燃性樹脂組成物に関する。また、この難燃性樹脂組成物で構成された樹脂シート、樹脂成形品に関する。 The present invention relates to a non-halogen flame retardant resin composition that suppresses the generation of harmful gases during combustion. Moreover, it is related with the resin sheet comprised by this flame-retardant resin composition, and a resin molded product.
従来、オレフィン系樹脂の難燃化手段としては、リン酸塩系難燃剤を始めとして、ハロゲン系難燃剤、赤リンやポリリン酸アンモニウムに代表される無機リン系難燃剤、トリアリールリン酸エステル化合物に代表される有機リン系難燃剤、金属水酸化物や難燃助剤である酸化アンチモン、メラミン化合物を単独又は組み合わせて用いることが広く知られている。 Conventionally, as flame retardant means for olefin resins, phosphate flame retardants, halogen flame retardants, inorganic phosphorus flame retardants typified by red phosphorus and ammonium polyphosphate, triaryl phosphate compounds It is widely known to use an organic phosphorus flame retardant represented by the above, metal hydroxides, antimony oxides which are flame retardant aids, and melamine compounds alone or in combination.
その中でも、環境保護の観点から、非ハロゲン系難燃性樹脂が求められており、リン酸塩系の難燃剤と組み合わせた難燃性樹脂組成物が提案されている。
例えば、特許文献１には、オレフィン系樹脂に対してリン酸塩系の難燃剤と二酸化ケイ素および高級カルボン酸を配合してなる、難燃性オレフィン系樹脂組成物が開示されている。
Among these, from the viewpoint of environmental protection, non-halogen flame retardant resins are required, and flame retardant resin compositions in combination with phosphate flame retardants have been proposed.
For example, Patent Document 1 discloses a flame retardant olefin resin composition obtained by blending a phosphate flame retardant, silicon dioxide, and a higher carboxylic acid with an olefin resin.
一方、特許文献２には、ポリプロピレン系樹脂とポリエステル系樹脂の相溶性を改善するために、ポリプロピレン系樹脂、ポリエステル系樹脂およびグラフト変性ポリオレフィン系樹脂からなる樹脂組成物が開示されている。 On the other hand, Patent Document 2 discloses a resin composition comprising a polypropylene resin, a polyester resin and a graft-modified polyolefin resin in order to improve the compatibility between the polypropylene resin and the polyester resin.
しかしながら、特許文献１に記載された樹脂組成物は、ＵＬ規格のような１０秒程度の短時間の着炎では、Ｖ−０レベルの難燃性を示しているが、鉄道車両内装材に要求されるような９０秒を超える長時間の着炎では、延焼が大きく、また、炎を取り去った後の残炎があり、鉄道車両用材料燃焼試験規格での難燃性樹脂のランクには到達できていないという問題がある。また、難燃剤をオレフィン系樹脂に均一に分散させるために添加される高級カルボン酸等が、成形後その表面にブリードアウトしてくるという問題もある。 However, the resin composition described in Patent Document 1 shows flame retardancy of V-0 level when flameed for a short time of about 10 seconds as in the UL standard, but is required for a railway vehicle interior material. In such a long-lasting flame exceeding 90 seconds, the spread of fire is large, and there is a residual flame after removing the flame, reaching the rank of flame retardant resin in the rail vehicle material combustion test standard. There is a problem that it is not done. There is also a problem that higher carboxylic acid and the like added to uniformly disperse the flame retardant in the olefin resin bleed out to the surface after molding.
また、特許文献２に記載された樹脂組成物は、ポリエステル系樹脂を主体として、それに、オレフィン系樹脂を混合することによって、樹脂組成物の剛性、強度、表面性の向上を目的としたものであり、価格的に高価になるという問題がある。また、長時間の着炎に対する難燃性については一切開示されていない。 The resin composition described in Patent Document 2 is intended to improve the rigidity, strength, and surface properties of a resin composition by mixing a olefin resin with a polyester resin as a main component. There is a problem that it becomes expensive in price. Further, there is no disclosure of flame retardancy against long-term flames.
上記の点に鑑み、本発明の目的は、オレフィン系樹脂を主体とし、少ない熱可塑性ポリエステル樹脂の混合で、９０秒を超える長時間の着炎でも難燃性に優れた難燃性樹脂組成物を提供することである。また、この難燃性樹脂組成物で構成された樹脂シート、樹脂成形品を提供することである。 In view of the above points, an object of the present invention is to provide a flame retardant resin composition that is mainly composed of an olefin resin and has excellent flame retardancy even when flame is prolonged for more than 90 seconds by mixing a small amount of thermoplastic polyester resin. Is to provide. Moreover, it is providing the resin sheet comprised by this flame-retardant resin composition, and a resin molded product.
本発明者らは、係る現状に鑑み鋭意検討を重ねた結果、下記の構成を採用することにより、９０秒を超える長時間の着炎でも難燃性に優れた難燃性樹脂組成物が得られることを見出し本発明に到達した。 As a result of intensive studies in view of the present situation, the present inventors have obtained a flame retardant resin composition that is excellent in flame retardancy even with long-term flames exceeding 90 seconds by adopting the following configuration. The present invention has been found.
すなわち、本発明に係る難燃性樹脂組成物は、実質的にハロゲンを含まず、以下の（Ａ）〜（Ｄ）成分を必須成分とすることを特徴とする（請求項１）。
（Ａ）成分：２３０℃における溶融張力が３５〜６０ｍＮであるオレフィン系樹脂組成物
（Ｂ）成分：２７０℃における剪断速度１００ｓ−１で測定した溶融粘度が５００〜１５００Ｐａ・ｓである熱可塑性ポリエステル樹脂
（Ｃ１）成分：リン酸塩系難燃剤
（Ｄ）成分：ポリプロピレン系ポリマーアロイ相溶化剤
上記の発明において、好ましくは、さらに、（Ｃ２）成分：縮合リン酸エステル系難燃剤を含み（請求項２）、（Ｄ）成分が、無水マレイン酸変性オレフィン系樹脂である（請求項３）。
また、好ましくは、（Ａ）成分８０〜９５質量％と（Ｂ）成分５〜２０質量％からなる混合物１００質量部に対して、（Ｃ１）成分２０〜４０質量部、（Ｃ２）成分０〜１０質量部、（Ｄ）成分が５〜３０質量部とする（請求項４）。
That is, the flame-retardant resin composition according to the present invention is substantially free of halogen and has the following components (A) to (D) as essential components (claim 1).
Component (A): Olefin-based resin composition having a melt tension of 35 to 60 mN at 230 ° C. Component (B): Thermoplastic polyester having a melt viscosity of 500 to 1500 Pa · s measured at a shear rate of 100 s −1 at 270 ° C. Resin (C1) Component: Phosphate Flame Retardant (D) Component: Polypropylene Polymer Alloy Compatibilizer In the above invention, preferably, (C2) Component: Condensed Phosphate Ester Flame Retardant Item 2), Component (D) is a maleic anhydride-modified olefin resin (Claim 3).
Further, preferably, (C1) component 20 to 40 parts by mass, (C2) component 0 to 100 parts by mass of (A) component 80 to 95% by mass and (B) component 5 to 20% by mass. 10 mass parts and (D) component shall be 5-30 mass parts (Claim 4).
本発明に係る樹脂シートは、上記の難燃性樹脂組成物で構成されることを特徴とする（請求項５）。また、本発明に係る樹脂成形品は、上記の難燃性樹脂組成物で構成されることを特徴とする（請求項６）。 The resin sheet which concerns on this invention is comprised by said flame-retardant resin composition (Claim 5), It is characterized by the above-mentioned. Moreover, the resin molded product according to the present invention is composed of the flame retardant resin composition (claim 6).
本発明に係る難燃性樹脂組成物は、オレフィン系樹脂組成物である（Ａ）成分と熱可塑性ポリエステル樹脂である（Ｂ）成分に、難燃剤である（Ｃ１）成分とオレフィン系ポリマーアロイ相溶化剤である（Ｄ）成分を必須成分とする。 The flame retardant resin composition according to the present invention includes a component (A) that is an olefin resin composition and a component (B) that is a thermoplastic polyester resin, a component (C1) that is a flame retardant, and an olefin polymer alloy phase. The component (D), which is a solubilizer, is an essential component.
２７０℃における剪断速度１００ｓ−１で測定した溶融粘度が５００〜１５００Ｐａ・ｓである熱可塑性ポリエステル樹脂を用いることにより、燃焼時の溶融樹脂の垂れ落ちを防止することができる。また、樹脂表面に炭化層を保持して酸素遮断の役目をすると同時に、リン酸塩系難燃剤から発生した気泡の保持力を高め、断熱膜を形成する。これにより、長時間炎が当たっても燃焼が進まず、９０秒を超える長時間の着炎でも、延焼が少なく、難燃性に優れた樹脂組成物を得ることができる。さらに、少ない熱可塑性ポリエステル樹脂の混合で、難燃性を確保できるため、価格的に安価なものとすることができる。 By using a thermoplastic polyester resin having a melt viscosity of 500 to 1500 Pa · s measured at a shear rate of 100 s −1 at 270 ° C., dripping of the molten resin during combustion can be prevented. In addition, the carbonized layer is held on the resin surface to serve as an oxygen barrier, and at the same time, the holding power of bubbles generated from the phosphate flame retardant is increased, and a heat insulating film is formed. Thereby, even if a flame hits for a long time, combustion does not progress, and even if it is a flame for a long time exceeding 90 seconds, there are few fire spreads and the resin composition excellent in the flame retardance can be obtained. Furthermore, since flame retardance can be ensured by mixing a small amount of thermoplastic polyester resin, the cost can be reduced.
２３０℃における溶融張力が３５〜６０ｍＮであるオレフィン系樹脂組成物を用いることにより、上記の難燃性を向上させる効果を増大させるとともに、樹脂シートの真空成形性に優れ、射出成形品にも適用できる樹脂組成物を得ることができる。 By using an olefin-based resin composition having a melt tension at 230 ° C. of 35 to 60 mN, the effect of improving the flame retardancy is increased, and the vacuum formability of the resin sheet is excellent. A resin composition that can be obtained can be obtained.
また、オレフィン系の相溶化剤を加えて混練することにより、オレフィン系樹脂組成物と熱可塑性ポリエステル樹脂からなる混合物の特性を向上させるとともに、この相溶化剤が、難燃剤の分散剤としての効果を持ち、分散剤を加えなくても、良好に難燃剤が分散した難燃性樹脂組成物が得られる。 In addition, by adding and kneading an olefin-based compatibilizer, the characteristics of the mixture comprising the olefin-based resin composition and the thermoplastic polyester resin are improved, and this compatibilizer is effective as a flame retardant dispersant. Even if a dispersant is not added, a flame retardant resin composition in which a flame retardant is favorably dispersed can be obtained.
本発明に係る難燃性樹脂組成物は、ベースとなるオレフィン系樹脂組成物である（Ａ）成分と熱可塑性ポリエステル樹脂である（Ｂ）成分に、難燃剤である（Ｃ１）成分と、（Ａ）成分と（Ｂ）成分からなる混合物を均一な組成とするための相溶化剤である（Ｄ）成分を、インラインスクリュウタイプの押出機にて溶融混練した後、押出して得ることができる。
本発明に係る樹脂シートは、前記押出してペレット状にした材料を押出成形して製造することができる。また、前記押出してペレット状にした材料を射出成形して本発明に係る樹脂成形品を製造することができる。
The flame retardant resin composition according to the present invention includes a component (A) that is a base olefin resin composition and a component (B) that is a thermoplastic polyester resin, a component (C1) that is a flame retardant, and ( The component (D), which is a compatibilizing agent for making a mixture of the component A) and the component (B) uniform, can be obtained by melt-kneading with an in-line screw type extruder and then extruding.
The resin sheet according to the present invention can be manufactured by extruding the extruded material into a pellet. Moreover, the resin molded product according to the present invention can be manufactured by injection molding the extruded material.
（Ａ）成分のオレフィン系樹脂組成物は、プロピレン単独重合体、エチレンプロピレン共重合体、高密度ポリエチレン、低密度ポリエチレン等を使用することができ、これらを単独あるいは２種以上を混合して使用することができる。そして、２３０℃における溶融張力が３５〜６０ｍＮであるものを使用する。なお、オレフィン系樹脂組成物を構成する樹脂は、それぞれ１９０℃におけるメルトフローレートが１．０ｇ／１０ｍｉｎ以下とすることが好ましい。また、プロピレン単独重合体、エチレンプロピレンブロック共重合体、高密度ポリエチレンおよび低密度ポリエチレンで構成することが好ましい。これにより、真空成形の加熱時のドローダウンが小さく、真空成形性に優れた樹脂シート、及び射出成形も可能な難燃性樹脂組成物を得ることができる。 As the olefin resin composition of component (A), propylene homopolymer, ethylene propylene copolymer, high density polyethylene, low density polyethylene and the like can be used, and these are used alone or in admixture of two or more. can do. And the thing whose melt tension in 230 degreeC is 35-60 mN is used. In addition, it is preferable that the resin which comprises an olefin resin composition shall be 1.0 g / 10min or less in the melt flow rate in 190 degreeC, respectively. Moreover, it is preferable to comprise with a propylene homopolymer, an ethylene propylene block copolymer, a high density polyethylene, and a low density polyethylene. Thereby, the drawdown at the time of the heating of vacuum forming is small, and the flame-retardant resin composition which can also be injection-molded and the resin sheet excellent in vacuum moldability can be obtained.
（Ｂ）成分の熱可塑性ポリエステル樹脂は、ポリエチレンテレフタレート、ポリブチレンテレフタレート等を使用することができ、これらを単独あるいは２種以上を混合して使用することができる。そして、２７０℃における剪断速度１００ｓ−１で測定した溶融粘度が５００〜１５００Ｐａ・ｓのものを使用する。溶融粘度が５００Ｐａ・ｓ未満であると、燃焼時の樹脂の垂れ落ち防止効果が小さく、難燃性が低下する。また、１５００Ｐａ・ｓを超えると、オレフィン系樹脂組成物との混練が困難となる。 As the thermoplastic polyester resin of component (B), polyethylene terephthalate, polybutylene terephthalate, or the like can be used, and these can be used alone or in admixture of two or more. And the thing of the melt viscosity 500-1500 Pa * s measured with the shear rate 100s- 1 in 270 degreeC is used. If the melt viscosity is less than 500 Pa · s, the effect of preventing dripping of the resin during combustion is small, and the flame retardancy is lowered. If it exceeds 1500 Pa · s, kneading with the olefin-based resin composition becomes difficult.
（Ｂ）成分の溶融粘度を上記の範囲とすることで、燃焼時の溶融樹脂の垂れ落ちを防止し、樹脂表面に炭化層を保持して酸素遮断の役目をすると同時に、リン酸塩系難燃剤から発生した気泡の保持力を高め、断熱膜を形成するため、長時間に炎が当たっても燃焼が進まず、難燃性が向上する。 By making the melt viscosity of the component (B) within the above range, it prevents dripping of the molten resin during combustion, holds a carbonized layer on the resin surface and serves to block oxygen, and at the same time, phosphate-based difficulty Since the retention of bubbles generated from the flame retardant is increased and a heat insulating film is formed, combustion does not proceed even if the flame hits for a long time, and flame retardancy is improved.
なお、垂れ落ち防止として、ポリテトラフルオルエチレン（ＰＴＦＥ）を添加する方法も報告されているが、ＰＴＦＥは、オレフィン系樹脂との相溶性が悪く、また高価なため大量に添加することができない。また、本発明が目的とする長時間の着炎に対する難燃効果は小さい。 A method of adding polytetrafluoroethylene (PTFE) has also been reported to prevent dripping, but PTFE has poor compatibility with olefin-based resins and is expensive and cannot be added in large quantities. . Moreover, the flame-retardant effect with respect to long-term flame which the objective of this invention is small.
また、（Ｂ）成分は結晶性樹脂であるため、２２５℃以上の融点を保持しており、融点以下の温度での真空成形の加熱時（１５０℃〜２００℃付近）のシートの垂れ下がり、すなわちドローダウンを小さくする効果も付与している。 In addition, since the component (B) is a crystalline resin, it has a melting point of 225 ° C. or higher, and the sheet hangs down during heating in vacuum forming at a temperature lower than the melting point (around 150 ° C. to 200 ° C.). It also has the effect of reducing drawdown.
上記（Ａ）成分と（Ｂ）成分からなる混合物は、（Ａ）成分８０〜９５質量％、（Ｂ）成分２０〜５質量％とすることが好ましい。（Ｂ）成分が５質量％未満では、難燃性の向上効果は小さく、９０秒を超える着炎に耐えられない。（Ｂ）成分の混合割合が大きくなるにしたがい難燃性向上効果は大きくなるが、相溶化剤の添加量が増加し、コスト高となる。 The mixture comprising the component (A) and the component (B) is preferably 80 to 95% by mass of the component (A) and 20 to 5% by mass of the component (B). When the component (B) is less than 5% by mass, the effect of improving the flame retardancy is small, and it cannot withstand the flame over 90 seconds. As the mixing ratio of the component (B) increases, the flame retardancy improving effect increases, but the amount of compatibilizer added increases and the cost increases.
（Ｃ１）成分のリン酸塩系難燃剤は、ポリリン酸アンモニウム化合物、リン酸アミン塩、ポリリン酸アミン塩等を使用することができる。例えば、ＡＤＥＫＡ製アデカスタブ「ＦＰ２１００」や「ＦＰ２２００」、クラリアントジャパン製「ＡＰ７５０」等が挙げられる。 As the phosphate flame retardant as the component (C1), an ammonium polyphosphate compound, an amine phosphate, an amine polyphosphate, or the like can be used. For example, ADEKA ADK STAB “FP2100” and “FP2200”, Clariant Japan “AP750” and the like can be mentioned.
（Ｃ２）成分の縮合リン酸エステル系難燃剤は、ビスフェノールＡビス（ジフェニルホスフェート）、１，３フェニレンビス（ジキシレニル）ホスフェート等を使用することができる。例えば、ＡＤＥＫＡ製アデカスタブ「ＦＰ６００」、味の素ファインテクノ製レオフォス「ＢＡＰＰ」等が挙げられる。 As the (C2) component condensed phosphate ester flame retardant, bisphenol A bis (diphenyl phosphate), 1,3-phenylene bis (dixylenyl) phosphate, or the like can be used. For example, ADEKA ADK STAB “FP600”, AJINOMOTO FINE TECHNO REOFOS “BAPP” and the like can be mentioned.
なお、（Ｃ１）成分と（Ｃ２）成分とを併用することが好ましい。一般的に、原料である樹脂ペレットを粉末状フィラとともに溶融混練するときは、樹脂ペレットの表面に粉末状フィラを付着させる目的で、流動パラフィンなどの液状のものを添加することが行われている。しかし、流動パラフィンは、溶融混練後の樹脂組成物の難燃性を阻害する。一方、縮合リン酸エステル系難燃剤は液状であるため、樹脂ペレットの表面に粉末状のリン酸塩系難燃剤を付着させることができ、しかも、溶融混練後の樹脂組成物の難燃性を阻害することもない。 In addition, it is preferable to use (C1) component and (C2) component together. In general, when melt-kneading resin pellets as raw materials together with a powdery filler, a liquid material such as liquid paraffin is added for the purpose of attaching the powdery filler to the surface of the resin pellets. . However, liquid paraffin inhibits the flame retardancy of the resin composition after melt-kneading. On the other hand, since the condensed phosphate ester flame retardant is in a liquid state, a powdered phosphate flame retardant can be adhered to the surface of the resin pellets, and the flame retardancy of the resin composition after melt-kneading can be reduced. There is no hindrance.
（Ｃ１）成分及び（Ｃ２）成分の配合量は、（Ａ）成分と（Ｂ）成分からなる混合物１００質量部に対して、（Ｃ１）成分２０〜４０質量部、（Ｃ２）成分０〜１０質量部であることが好ましい。（Ｃ１）成分を上記の範囲とすることにより、難燃性及び樹脂シートの物性、特に耐衝撃性や引張り伸びを十分に確保することができる。また、（Ｃ２）成分を上記の範囲とすることにより、縮合リン酸エステル系難燃剤とオレフィン系樹脂とを十分に相溶させることができる。 The blending amount of the component (C1) and the component (C2) is 20 to 40 parts by mass of the component (C1) and 0 to 10 components of the component (C2) with respect to 100 parts by mass of the mixture composed of the component (A) and the component (B). It is preferable that it is a mass part. By setting the component (C1) within the above range, the flame retardancy and the physical properties of the resin sheet, particularly impact resistance and tensile elongation can be sufficiently secured. In addition, by setting the component (C2) within the above range, the condensed phosphate ester flame retardant and the olefin resin can be sufficiently compatible.
相溶化剤である（Ｄ）成分は、（Ａ）〜（Ｃ）成分を溶融混練するときに、（Ａ）成分と（Ｂ）成分を相溶させ均一なものとするための助剤であり、また、（Ａ）成分と（Ｂ）成分の樹脂に難燃剤である（Ｃ１）成分と（Ｃ２）成分の均一分散性を向上させる作用をも発揮する。相溶化剤としては、オレフィン系樹脂と熱可塑性ポリエステル樹脂との相溶化を促進するものであればよいが、なかでも、無水マレイン酸変性オレフィン系樹脂が、樹脂の相溶化剤と難燃剤の分散性向上効果が高い。無水マレイン酸変性オレフィン系樹脂としては、例えば、三洋化成製「ユーメックス１００１」が挙げられる。 The component (D), which is a compatibilizer, is an auxiliary agent for making the components (A) and (B) compatible and uniform when the components (A) to (C) are melt-kneaded. Moreover, the effect | action which improves the uniform dispersibility of (C1) component and (C2) component which are flame retardants to resin of (A) component and (B) component is also exhibited. Any compatibilizer may be used as long as it promotes compatibilization of the olefin resin and the thermoplastic polyester resin. Among them, the maleic anhydride-modified olefin resin is a dispersion of the resin compatibilizer and the flame retardant. The effect of improving properties is high. Examples of maleic anhydride-modified olefin resins include “Yumex 1001” manufactured by Sanyo Chemical.
（Ｄ）成分の配合量は、（Ａ）成分と（Ｂ）成分からなる混合物１００質量部に対して、（Ｄ）成分５〜３０質量部が好ましい。（Ｄ）成分を上記の範囲とすることにより、（Ａ）成分と（Ｂ）成分とを十分に相溶させることができ、（Ｃ）成分を十分に分散させることができる。また、材料をコンパウンド押出しでペレタイズするときのコンパウンド作業性も良好である。 The blending amount of the component (D) is preferably 5 to 30 parts by mass of the component (D) with respect to 100 parts by mass of the mixture composed of the component (A) and the component (B). By making (D) component into said range, (A) component and (B) component can fully be made compatible, and (C) component can fully be disperse | distributed. In addition, the compound workability when the material is pelletized by compound extrusion is also good.
以下、実施例により本発明を詳細に示す。ただし、本発明は以下の実施例により何ら制限されるものではない。
実施例に使用する材料は以下の通りである。
（Ａ）成分として、
（ａ）プロピレン単独重合体：住友化学工業製「ノーブレンＦＨ１０１６」
（ｂ）エチレンプロピレン共重合体：日本ポリプロ製「ノバテックＰＰ ＥＣ９」
（ｃ）高密度ポリエチレン：日本ポリエチレン製「ノバテックＨＤ ＨＹ４３４」
（ｄ）低密度ポリエチレン：住友化学工業製「スミカセンＦ１０２−０」
（Ｂ）成分として、
（ｅ）ポリエチレンテレフタレート：２７０℃における剪断速度１００ｓ−１で測定した溶融粘度３００Ｐａ・ｓ
（ｆ）ポリエチレンテレフタレート：２７０℃における剪断速度１００ｓ−１で測定した溶融粘度１０００Ｐａ・ｓ
（ｇ）ポリブチレンテレフタレート：２７０℃における剪断速度１００ｓ−１で測定した溶融粘度１０００Ｐａ・ｓ
（Ｃ１）成分として、
（ｈ）リン酸塩系難燃剤：ＡＤＥＫＡ製「ＦＰ２２００」
（Ｃ２）成分として、
（ｉ）縮合リン酸エステル系難燃剤：ＡＤＥＫＡ製「ＦＰ６００」
（Ｄ）成分として、
（ｊ）無水マレイン酸変性ＰＰ：三洋化成製「ユーメックス１００１」
実施例１〜８
各例毎にそれぞれ表１〜２に示す樹脂組成物を２軸押出し機で押出しペレット化し、射出成形による２．５mm厚の射出成形板と押出成形による厚さ２mmの樹脂シートを作製した。
Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited by the following examples.
The materials used in the examples are as follows.
As component (A),
(A) Propylene homopolymer: “Nobrene FH1016” manufactured by Sumitomo Chemical Co., Ltd.
(B) Ethylene propylene copolymer: “NOVATEC PP EC9” manufactured by Nippon Polypro Co., Ltd.
(C) High-density polyethylene: “Novatec HD HY434” manufactured by Nippon Polyethylene
(D) Low density polyethylene: “Sumikasen F102-0” manufactured by Sumitomo Chemical Co., Ltd.
As component (B),
(E) Polyethylene terephthalate: melt viscosity of 300 Pa · s measured at a shear rate of 100 s −1 at 270 ° C.
(F) Polyethylene terephthalate: melt viscosity of 1000 Pa · s measured at a shear rate of 100 s −1 at 270 ° C.
(G) Polybutylene terephthalate: melt viscosity of 1000 Pa · s measured at a shear rate of 100 s −1 at 270 ° C.
As component (C1),
(H) Phosphate flame retardant: “FP2200” manufactured by ADEKA
As component (C2),
(I) Condensed phosphate ester flame retardant: “FP600” manufactured by ADEKA
As component (D),
(J) Maleic anhydride modified PP: “Yumex 1001” manufactured by Sanyo Chemical
Examples 1-8
For each example, the resin compositions shown in Tables 1 and 2 were extruded and pelletized with a biaxial extruder to produce a 2.5 mm thick injection molded plate by injection molding and a 2 mm thick resin sheet by extrusion molding.
比較例１〜４
各例毎にそれぞれ表３に示す樹脂組成物を２軸押出し機で押出しペレット化し、射出成形による２．５mm厚の射出成形板と押出成形による厚さ２mmの樹脂シートを作製した。
Comparative Examples 1-4
For each example, the resin composition shown in Table 3 was extruded and pelletized with a biaxial extruder to produce a 2.5 mm thick injection molded plate by injection molding and a 2 mm thick resin sheet by extrusion molding.
上記実施例および比較例について、難燃性および真空成形性を評価した。その結果を表１〜３に併せて示した。なお、表中において、上記材料（ａ）〜（ｇ）は、（Ａ）成分：オレフィン系樹脂組成物と（Ｂ）成分：熱可塑性ポリエステル樹脂からなる混合物を１００質量％とした配合量（質量％）で、また、上記材料（ｈ）〜（ｊ）は、（Ａ）成分と（Ｂ）成分からなる混合物１００質量部に対する配合量（質量部）で、それぞれ記載している。 About the said Example and comparative example, the flame retardance and the vacuum moldability were evaluated. The result was combined with Tables 1-3, and was shown. In addition, in the table | surface, said material (a)-(g) is the compounding quantity (mass) which made the mixture which consists of (A) component: olefin resin composition and (B) component: thermoplastic polyester resin 100 mass%. In addition, the materials (h) to (j) are respectively described in the amount (parts by mass) based on 100 parts by mass of the mixture composed of the component (A) and the component (B).
また、表中に示した各特性は、次のようにして評価した。
（１）溶融張力：キャピラリーレオメーター（東洋精機製「キャピログラフ１Ｂ」）を使用し、２３０℃で加熱溶融した樹脂を、長さ１０mm、内径１mmのキャピラリーを通して押出す。このときの押出速度は１０mm／分である。押出された溶融樹脂フィラメントを、テンションプーリを介して引取りロールで巻き取る。このときの引張速度は３mm／分である。そして、テンションプーリにかかる力を溶融張力として測定する。
（２）溶融粘度：キャピログラフ（ノズル径：１．０mm、ノズル長：１０mm）を使用した。なお、燃焼時は高温度で、樹脂の流動は自重のみで発生するため、温度２７０℃、剪断速度１００ｓ−１の条件で測定した。
（３）難燃性：厚み２．５mm、幅５０mm、長さ６０mmの射出成形試験片を用い、試験片を水平に４５°傾斜させて固定して、その中央に３０mm〜４０mmのローソク火炎を当て、燃焼により、試験片に１０mm程度の貫通孔が発生するまでの時間（穴あき時間）と、火炎を除去した後に残炎が消えるまでの時間（残炎時間）を測定した。なお、この方法で、穴あき時間が１８０秒以上であれば、鉄道車両用内装材の０．５ｃｃアルコール燃焼（約９０秒燃焼）の難燃性ランクに相当する。
（４）ドローダウン性：真空成形機（布施真空製「ＣＵＰＦ−１０１３−ＰＷＢ」）を使用し、真空成形機のクランプ（大きさ：１０００mm×８００mm）に、厚み２mmの樹脂シートをセットし、加熱後のクランプ中央部の樹脂シートの垂下がり量を測定した。このとき、加熱条件は、ヒータ温度上下３６０℃、加熱時間９０秒とした。
（５）真空成形後型形状再現性：真空成形機（布施真空製「ＣＵＰＦ−１０１３−ＰＷＢ」）を使用し、凸型成形品（形状：縦幅８００mm×横幅６００mm×高さ１５０mm）を成形したときの型形状再現性、コーナ再現性、皺発生の有無、変形、ゆがみの大きさについて、目視により成形性の良否を判断した。このとき、成形前の樹脂シートは１０００mm×１０００mm×厚み２mmである。なお、評価は下記により行なった。
◎：外観の異常、ゆがみ変形なく良好，○：型形状再現性は良好も天面にゆがみ発生，△：皺、変形発生，×：成形不可
Each characteristic shown in the table was evaluated as follows.
(1) Melt tension: Using a capillary rheometer (“Capillograph 1B” manufactured by Toyo Seiki Co., Ltd.), a resin heated and melted at 230 ° C. is extruded through a capillary having a length of 10 mm and an inner diameter of 1 mm. The extrusion speed at this time is 10 mm / min. The extruded molten resin filament is wound up by a take-up roll through a tension pulley. The tensile speed at this time is 3 mm / min. Then, the force applied to the tension pulley is measured as the melt tension.
(2) Melt viscosity: Capillograph (nozzle diameter: 1.0 mm, nozzle length: 10 mm) was used. The temperature was 270 ° C. and the shear rate was 100 s −1 because the resin flow was generated only by its own weight during combustion.
(3) Flame retardancy: Using an injection-molded test piece with a thickness of 2.5 mm, a width of 50 mm, and a length of 60 mm, the test piece is horizontally tilted 45 ° and fixed, and a candle flame of 30 mm to 40 mm is placed in the center. The time until a through hole of about 10 mm was generated in the test piece by contact and combustion (perforation time) and the time until the after flame disappeared after the flame was removed (after flame time) were measured. In this method, if the perforated time is 180 seconds or more, it corresponds to the flame retardance rank of 0.5 cc alcohol combustion (combustion of about 90 seconds) of the interior material for railway vehicles.
(4) Drawdown property: Using a vacuum forming machine (“CUPF-1013-PWB” manufactured by Cloth Vacuum), a resin sheet having a thickness of 2 mm is set on a clamp (size: 1000 mm × 800 mm) of the vacuum forming machine, The amount of sag of the resin sheet at the center of the clamp after heating was measured. At this time, the heating conditions were a heater temperature up and down 360 ° C. and a heating time of 90 seconds.
(5) Mold shape reproducibility after vacuum forming: Using a vacuum forming machine (“CUPF-1013-PWB” manufactured by Fuse Vacuum), a convex mold product (shape: vertical width 800 mm × horizontal width 600 mm × height 150 mm) is formed. The mold form reproducibility, the corner reproducibility, the presence or absence of wrinkles, the deformation, and the size of distortion were judged visually to determine whether the moldability was good. At this time, the resin sheet before molding is 1000 mm × 1000 mm × thickness 2 mm. The evaluation was performed as follows.
◎: Appearance abnormality, good without distortion deformation, ○: Good mold shape reproducibility but distortion on top surface, △: Flaw, deformation occurrence, ×: Impossible molding
比較例３〜４に示すように、（Ｂ）成分を含有していない系では、難燃剤（Ｃ１）及び（Ｃ２）成分を、（Ａ）成分と（Ｂ）成分からなる混合物１００質量部に対して２６．７質量部（比較例３）〜３１．９質量部（比較例４）添加しても、穴あきまでの時間が６０〜９０秒と短く、また火炎を取り去ったあとの残炎が２０秒〜延焼まで発生している。このレベルでは、長時間の着炎に対する難燃性が不充分である。 As shown in Comparative Examples 3 and 4, in the system not containing the component (B), the flame retardants (C1) and (C2) components are added to 100 parts by mass of the mixture composed of the components (A) and (B). On the other hand, even when 26.7 parts by mass (Comparative Example 3) to 31.9 parts by mass (Comparative Example 4) are added, the time until drilling is as short as 60 to 90 seconds, and the after flame after removing the flame From 20 seconds to the spread of fire. At this level, the flame retardancy against long-term flame is insufficient.
また、比較例１〜２に示すように、（Ｂ）成分を含有していても、その溶融粘度が低い系においては、同じように難燃剤（Ｃ１）及び（Ｃ２）成分を２６．７質量部（比較例１）〜３１．９質量部（比較例２）添加することにより、穴あき時間、残炎時間が改良されているものの、樹脂シートにおけるドローダウンが大きく真空成形性が不充分である。 Further, as shown in Comparative Examples 1 and 2, in the system having a low melt viscosity even when the component (B) is contained, the flame retardant (C1) and the component (C2) are similarly 26.7 masses. Part (Comparative Example 1) to 31.9 parts by mass (Comparative Example 2), the perforation time and afterflame time are improved, but the drawdown in the resin sheet is large and the vacuum moldability is insufficient. is there.
実施例１〜３に示すように、２７０℃における剪断速度１００ｓ−１で測定した溶融粘度が１０００Ｐａ・ｓであるポリエチレンテレフタレートを配合した系においては、難燃剤（Ｃ１）及び（Ｃ２）成分を２６．７質量部（実施例１、２）〜３１．９質量部（実施例３）添加することにより、穴あき時間が大幅に改良されており、また、樹脂シートにおけるドローダウンが小さく真空成形性も良好である。
なお、実施例３〜４では、穴あき時間が２４０秒以上の結果が得られており、鉄道車両用材料の燃焼規格の難燃性ランクに適合するレベルにある。
As shown in Examples 1 to 3, in a system in which polyethylene terephthalate having a melt viscosity of 1000 Pa · s measured at a shear rate of 100 s −1 at 270 ° C. was blended, 26 flame retardant (C1) and (C2) components were added. The addition of 7 parts by mass (Examples 1 and 2) to 31.9 parts by mass (Example 3) significantly improves the perforation time, and the resin sheet has a small drawdown and a vacuum formability. Is also good.
In Examples 3 to 4, a result of a perforation time of 240 seconds or more was obtained, which is at a level compatible with the flame retardance rank of the combustion standard for railcar materials.
実施例５〜６に示すように、（Ａ）成分が、ポリプロピレンもしくはポリエチレン単独でも、（Ｂ）成分との混合物であれば、長時間の着炎に対する難燃性が充分確保できる。
また、実施例７〜８に示すように、（Ｂ）成分が、ポリブチレンテレフタレートでも、同様の効果を得ることができる。
実施例１〜８に示すように、本発明の樹脂組成物は、いずれも良好な真空成形性を得ることができる。
As shown in Examples 5 to 6, even when the component (A) is polypropylene or polyethylene alone, if it is a mixture with the component (B), sufficient flame retardancy against long-term flame can be secured.
Further, as shown in Examples 7 to 8, even when the component (B) is polybutylene terephthalate, the same effect can be obtained.
As shown in Examples 1 to 8, the resin compositions of the present invention can obtain good vacuum moldability.
以上のことから判るように、（Ａ）成分と（Ｂ）成分からなる混合物に、リン酸塩系難燃剤（好ましくは、さらに縮合リン酸エステル系難燃剤）と、適度な相溶化剤を組み合わせ、溶融混合した樹脂組成物とすることにより、従来困難であった非ハロゲン系難燃性オレフィン系樹脂を提供することが可能となる。これにより、車両内装品、医療機器部品などの工業部品に適用でき、本発明の工業的価値はきわめて大なるものである。 As can be seen from the above, a phosphate flame retardant (preferably a condensed phosphate ester flame retardant) and an appropriate compatibilizer are combined with a mixture comprising the components (A) and (B). By using a melt-mixed resin composition, it is possible to provide a non-halogen flame-retardant olefin resin that has been difficult in the past. Accordingly, the present invention can be applied to industrial parts such as vehicle interior parts and medical equipment parts, and the industrial value of the present invention is extremely large.
Claims (6)
（Ａ）成分：２３０℃における溶融張力が３５〜６０ｍＮであるオレフィン系樹脂組成物
（Ｂ）成分：２７０℃における剪断速度１００ｓ−１で測定した溶融粘度が５００〜１５００Ｐａ・ｓである熱可塑性ポリエステル樹脂
（Ｃ１）成分：リン酸塩系難燃剤
（Ｄ）成分：ポリプロピレン系ポリマーアロイ相溶化剤 A flame-retardant resin composition which contains substantially no halogen and contains the following components (A) to (D) as essential components.
Component (A): Olefin-based resin composition having a melt tension of 35 to 60 mN at 230 ° C. Component (B): Thermoplastic polyester having a melt viscosity of 500 to 1500 Pa · s measured at a shear rate of 100 s −1 at 270 ° C. Resin (C1) component: Phosphate flame retardant (D) component: Polypropylene polymer alloy compatibilizer
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH08157700A (en) * | 1994-12-06 | 1996-06-18 | Kanegafuchi Chem Ind Co Ltd | Resin composition |
| JP2001342357A (en) * | 2000-06-02 | 2001-12-14 | Polyplastics Co | Flame-retardant resin composition |
| WO2003046083A1 (en) * | 2001-11-30 | 2003-06-05 | Polyplastics Co., Ltd. | Flame-retardant resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH08157700A (en) * | 1994-12-06 | 1996-06-18 | Kanegafuchi Chem Ind Co Ltd | Resin composition |
| JP2001342357A (en) * | 2000-06-02 | 2001-12-14 | Polyplastics Co | Flame-retardant resin composition |
| WO2003046083A1 (en) * | 2001-11-30 | 2003-06-05 | Polyplastics Co., Ltd. | Flame-retardant resin composition |
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