JPH04292645A - Flame-retardant resin composition - Google Patents
Flame-retardant resin compositionInfo
- Publication number
- JPH04292645A JPH04292645A JP8090891A JP8090891A JPH04292645A JP H04292645 A JPH04292645 A JP H04292645A JP 8090891 A JP8090891 A JP 8090891A JP 8090891 A JP8090891 A JP 8090891A JP H04292645 A JPH04292645 A JP H04292645A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- weight
- polyethylene
- flame
- parts
- 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.)
- Granted
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 16
- 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 12
- 239000011342 resin composition Substances 0.000 title claims abstract description 5
- -1 polypropylene Polymers 0.000 claims abstract description 25
- 239000004743 Polypropylene Substances 0.000 claims abstract description 18
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920001155 polypropylene Polymers 0.000 claims abstract description 16
- 229920013716 polyethylene resin Polymers 0.000 claims abstract description 12
- 239000004709 Chlorinated polyethylene Substances 0.000 claims abstract description 10
- 239000000805 composite resin Substances 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 10
- 239000003381 stabilizer Substances 0.000 claims abstract description 7
- NZUPFZNVGSWLQC-UHFFFAOYSA-N 1,3,5-tris(2,3-dibromopropyl)-1,3,5-triazinane-2,4,6-trione Chemical compound BrCC(Br)CN1C(=O)N(CC(Br)CBr)C(=O)N(CC(Br)CBr)C1=O NZUPFZNVGSWLQC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000155 melt Substances 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 abstract description 13
- 239000000203 mixture Substances 0.000 abstract description 11
- 238000012360 testing method Methods 0.000 abstract description 5
- 229920000573 polyethylene Polymers 0.000 description 11
- 230000000694 effects Effects 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、シート成形可能で耐衝
撃性、耐振動疲労特性に優れたポリエチレン・ポリプロ
ピレン複合難燃性樹脂組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyethylene/polypropylene composite flame-retardant resin composition that can be formed into a sheet and has excellent impact resistance and vibration fatigue resistance.
【０００２】0002
【従来の技術】ポリエチレンやポリプロピレンの難燃化
方法は、数々提案されている。例えば燃焼時のドリップ
性が要求される場合には、塩素系の難燃剤が用いられた
り、ポリエチレン単体には、相容性が良いので塩素化ポ
リエチレンで高い難燃性を与える事が可能である。ポリ
プロピレン単体の難燃化も臭素系難燃剤と三酸化アンチ
モンの併用が有効な手段として取られている。またポリ
エチレンやポリプロピレンの難燃化剤としてトリス（２
，３−ジブロモプロピル）イソシアヌレートを添加する
方法も知られている。BACKGROUND OF THE INVENTION A number of methods have been proposed for making polyethylene and polypropylene flame retardant. For example, when drip properties are required during combustion, chlorine-based flame retardants are used, and chlorinated polyethylene can provide high flame retardancy because it is compatible with pure polyethylene. . The combined use of brominated flame retardants and antimony trioxide is an effective means of making polypropylene flame retardant. Tris (2) is also used as a flame retardant for polyethylene and polypropylene.
, 3-dibromopropyl) isocyanurate is also known.
【０００３】0003
【発明が解決しようとする課題】ポリエチレンとポリプ
ロピレンの複合樹脂の難燃化の場合は上記の単一な難燃
剤で有効なものが少なく、あっても配合量が多くなるた
め組成物の機械的特性を損なう場合が多い。更にメルト
フローレートの低いポリエチレン・ポリプロピレン複合
樹脂の場合は燃焼時の火垂れ現象が少ないし、火垂れし
ても残試験片に着火状態が続き難燃化が難しい。本発明
は、ＵＬ９４Ｖ−２で規定する難燃性を与え、機械特性
を低下させず、耐衝撃性、特に耐寒衝撃性、耐振動疲労
特性に優れたメルトフローレートの低いポリエチレン・
ポリプロピレン複合・難燃性樹脂組成物を提供すること
を目的とする。[Problems to be Solved by the Invention] In the case of flame retardant composite resins of polyethylene and polypropylene, there are few effective single flame retardants mentioned above, and even if there are, they must be blended in a large amount, so it is difficult to improve the mechanical strength of the composition. This often results in loss of characteristics. Furthermore, in the case of polyethylene/polypropylene composite resins with a low melt flow rate, there is little fire-drop phenomenon during combustion, and even if fire-drops occur, the remaining test piece remains ignited, making it difficult to make it flame retardant. The present invention is a low melt flow rate polyethylene that provides flame retardancy specified by UL94V-2, does not reduce mechanical properties, and has excellent impact resistance, especially cold impact resistance, and vibration fatigue resistance.
The purpose of the present invention is to provide a polypropylene composite flame-retardant resin composition.
【０００４】0004
【課題を解決するための手段】本発明はポリエチレン・
ポリプロン複合樹脂、特にそのメルトフローレートの低
い複合樹脂の難燃化について研究した結果各種の添加剤
を特定量組合せることが有効であることの発見にもとず
くものである。即ち、本発明はポリエチレン系樹脂とポ
リプロピレン系樹脂との重量比が１０／９０〜６０／４
０でメルトフローレートが０．２〜３．０ｇ／１０分（
２３０℃）の複合樹脂１００重量部、トリス（２，３−
ジブロモプロピル）イソシアヌレート２０〜４０重量部
、塩素化ポリエチレン５〜２５重量部、三酸化アンチモ
ン１０〜３５重量部、及び望ましくはこれらとさらに安
定剤０．５〜５重量部からなる難燃性ポリエチレン・ポ
リプロピレン複合樹脂組成物である。[Means for solving the problems] The present invention provides polyethylene
This is based on research into flame retardancy of polyprone composite resins, especially composite resins with low melt flow rates, and the discovery that combining specific amounts of various additives is effective. That is, in the present invention, the weight ratio of polyethylene resin and polypropylene resin is 10/90 to 60/4.
0, the melt flow rate is 0.2 to 3.0 g/10 min (
100 parts by weight of composite resin at 230°C), Tris (2,3-
flame-retardant polyethylene consisting of 20 to 40 parts by weight of dibromopropyl isocyanurate, 5 to 25 parts by weight of chlorinated polyethylene, 10 to 35 parts by weight of antimony trioxide, and preferably 0.5 to 5 parts by weight of a stabilizer.・It is a polypropylene composite resin composition.
【０００５】本発明においてポリエチレン系樹脂とはポ
リエチレン樹脂又はエチレンと他のα−オレフィンとの
共重合体である。ポリエチレン樹脂は密度が０．９３０
ｇ／ｃｍ２ 以上の中密度、及び高密度ポリエチレンが
好ましい。共重合体の場合、他のα−オレフィンとして
はプロピレン、ブテン−１、ヘキセン−１などであり、
これらの共重合割合は１０モル％以下が好ましい。プロ
ピレン系樹脂はホモ重合ポリプレン樹脂、又はプロピレ
ンとエチレンとの共重合体であり、その共重合割合は２
０モル％以下が好ましい。[0005] In the present invention, the polyethylene resin is a polyethylene resin or a copolymer of ethylene and other α-olefins. Polyethylene resin has a density of 0.930
Medium-density and high-density polyethylene of g/cm2 or higher are preferred. In the case of copolymers, other α-olefins include propylene, butene-1, hexene-1, etc.
The copolymerization ratio of these is preferably 10 mol% or less. Propylene resin is a homopolymerized polyprene resin or a copolymer of propylene and ethylene, and the copolymerization ratio is 2.
It is preferably 0 mol% or less.
【０００６】ポリエチレン系樹脂とポリプロピレン系樹
脂の組成割合は重量比で１０／９０〜６０／４０（ポリ
エチレン系樹脂が１０〜６０重量％、ポリプロピレン系
樹脂９０〜４０重量％）である。ポリエチレン系樹脂が
１０重量％未満では本発明の組成物を用いた成形品の耐
衝撃値が悪くなる。一方６０重量％を超えると成形品の
耐振動疲労特性の低下を来たす。この両者の組成物はメ
ルトフローレート（ＭＦＲと略記）が０．２〜３．０ｇ
／１０分である。ＭＦＲが０．２未満では成形性が悪く
、成形の吐出量が下がるばかりでなく成形品の外観も悪
くなる。また３．０を超えるとシート成形の場合安定し
た肉厚のシートが成形しにくい。The composition ratio of polyethylene resin and polypropylene resin is 10/90 to 60/40 by weight (10 to 60% by weight of polyethylene resin, 90 to 40% by weight of polypropylene resin). If the polyethylene resin content is less than 10% by weight, the impact resistance of the molded article using the composition of the present invention will be poor. On the other hand, if it exceeds 60% by weight, the vibration fatigue resistance of the molded article will deteriorate. Both compositions have a melt flow rate (abbreviated as MFR) of 0.2 to 3.0 g.
/10 minutes. If the MFR is less than 0.2, moldability is poor, not only does the molding output rate decrease, but the appearance of the molded product also deteriorates. Moreover, when it exceeds 3.0, it is difficult to form a sheet with a stable thickness in the case of sheet molding.
【０００７】本発明は上記組成物１００重量部にトリス
（２，３−ジブロモプロピル）イソシアヌレート２０〜
４０重量部、好適には２５〜３５重量部、塩素化ポリエ
チレン５〜２５重量部、三酸化アンチモン１０〜３５重
量部を混合使用する。トリス（２，３−ジブロモプロピ
ル）イソシアヌレートが５重量部未満の場合は、難燃性
を与える効果が少なく４０重量部を超えると衝撃強度の
低下が大きくなるので好ましくない。[0007] The present invention provides 100 parts by weight of the above composition with 20 to
A mixture of 40 parts by weight, preferably 25 to 35 parts by weight, 5 to 25 parts by weight of chlorinated polyethylene, and 10 to 35 parts by weight of antimony trioxide is used. If the amount of tris(2,3-dibromopropyl) isocyanurate is less than 5 parts by weight, the effect of imparting flame retardance will be small, and if it exceeds 40 parts by weight, the impact strength will decrease significantly, which is not preferable.
【０００８】塩素化ポリエチレンを入れることで本発明
に供するメルトフローレートの低いポリエチレン・ポリ
プロピレン複合樹脂には、燃焼時溶融滴下をして自己消
火させる効果が出現する。塩素化ポリエチレンの配合量
は５〜２５重量部であり好適には１０〜２０重量部であ
る。５重量部未満では、難燃性を付与する効果が少なく
２５重量部を超える場合には、押出成形加工性が悪くな
ると共に剛性の低下も大きくなる。By adding chlorinated polyethylene, the polyethylene/polypropylene composite resin with a low melt flow rate used in the present invention has the effect of self-extinguishing by melting and dripping during combustion. The amount of chlorinated polyethylene blended is 5 to 25 parts by weight, preferably 10 to 20 parts by weight. If it is less than 5 parts by weight, the effect of imparting flame retardance will be small, and if it exceeds 25 parts by weight, extrusion processability will be poor and the rigidity will be greatly reduced.
【０００９】三酸化アンチモンは少ないと難燃効果が不
十分であり、多過ぎると組成物の成形品の耐衝撃性が低
下することから１０〜３５重量部を配合するが、トリス
（２，３−ジブロモプロピル）イソシアヌレートと塩素
化ポリエチレンの合計配合量の１／３〜１／２の量が好
ましい。樹脂加工時の熱安定性及び成形加工品の機械特
性低下防止のため安定剤を０．５〜５重量部配合するこ
とが好ましい。安定剤としては、有機錫系化合物、鉛系
安定剤、無機塩類金属石ケン類等を使用できる。本発明
の組成物には必要に応じて酸化防止剤、滑剤、顔料等を
適当量添加することができる。If the amount of antimony trioxide is too small, the flame retardant effect will be insufficient, and if it is too large, the impact resistance of the molded product of the composition will decrease. - dibromopropyl) isocyanurate and chlorinated polyethylene in an amount of 1/3 to 1/2 of the total amount. It is preferable to mix 0.5 to 5 parts by weight of a stabilizer in order to provide thermal stability during resin processing and to prevent deterioration of the mechanical properties of the molded product. As the stabilizer, organic tin compounds, lead stabilizers, inorganic salt metal soaps, etc. can be used. Appropriate amounts of antioxidants, lubricants, pigments, etc. can be added to the composition of the present invention, if necessary.
【００１０】以下に本発明の実施例と比較例を示す。実
施例と比較例にある測定項目に供した試料は各配合量を
ドライブレンドした後、５０ｍｍ径の単軸押出機で押出
し造粒したものである。ＵＬ９４Ｖ−２試験は該造粒物
を２３０℃で熱プレスした１．６ｍｍ厚シート品から試
験片を得た。アイゾット衝撃試験は上記と同じ方法で３
．０ｍｍ厚シート品から試験片を得た。Examples and comparative examples of the present invention are shown below. The samples used for the measurement items in Examples and Comparative Examples were obtained by dry-blending the respective blending amounts and then extruding and granulating them using a single-screw extruder with a diameter of 50 mm. For the UL94V-2 test, a test piece was obtained from a 1.6 mm thick sheet product obtained by hot pressing the granules at 230°C. The Izod impact test was performed using the same method as above.
．． A test piece was obtained from a 0 mm thick sheet product.
【００１１】尚、表１中に示した各成分は下記に示すと
うりである。
ポリエチレン樹脂 （商品名 ショウレックス
Ｓ６００２，昭和電工（株）製）
ポリプロピレン樹脂（商品名 ショウアロマー Ｓ
Ｋ７１１，昭和電工（株）製）
トリス（２，３−ジブロモプロピル）イソシアヌレート
（商品名 ＡＦＲ１００２，旭ガラス（株）製）塩素
化ポリエチレン（商品記号 ４０４Ｂ，昭和電工（株
）製）
三酸化アンチモン （三国精練（株）製）安定剤（商
品名 Ｓｔａｎｎ ＢＭ，三協有機合成（株）製）
カーボンブラック （三菱化成（株）製）[0011] Each component shown in Table 1 is as shown below. Polyethylene resin (product name: Shorex)
S6002, manufactured by Showa Denko Co., Ltd.) Polypropylene resin (product name: Showaromer S
K711, manufactured by Showa Denko K.K.) Tris (2,3-dibromopropyl) isocyanurate (product name AFR1002, manufactured by Asahi Glass Co., Ltd.) Chlorinated polyethylene (product code 404B, manufactured by Showa Denko K.K.) Antimony trioxide (manufactured by Mikuni Seiren Co., Ltd.) Stabilizer (product name: Stann BM, manufactured by Sankyo Organic Gosei Co., Ltd.) Carbon black (manufactured by Mitsubishi Kasei Co., Ltd.)
【００１２
】0012
]
【表１】[Table 1]
【００１３】[0013]
【発明の効果】本組成物は、トリス（２，３−ジブロモ
プロピル）イソシアヌレートと塩素化ポリエチレンと三
酸化アンチモンを特定量併用することにより、ポリエチ
レンとポリプロピレン複合樹脂でメルトフローレートの
低いものについて成形性と成形加工品の耐衝撃値及び振
動疲労特性を損なうことなく、ＵＬ９４Ｖ−２の難燃性
を達成できる。Effects of the Invention: This composition can be used for polyethylene and polypropylene composite resins with low melt flow rates by using a specific amount of tris(2,3-dibromopropyl) isocyanurate, chlorinated polyethylene, and antimony trioxide. Flame retardancy of UL94V-2 can be achieved without impairing the moldability, impact resistance value, and vibration fatigue properties of the molded product.
Claims (2)
系樹脂との重量比が１０／９０〜６０／４０でメルトフ
ローレートが０．２〜３．０ｇ／１０分である複合樹脂
１００重量部、トリス（２，３−ジブロモプロピル）イ
ソシアヌレート２０〜４０重量部、塩素化ポリエチレン
５〜２５重量部、三酸化アンチモン１０〜３５重量部か
らなる難燃性樹脂組成物。1. 100 parts by weight of a composite resin having a weight ratio of polyethylene resin and polypropylene resin of 10/90 to 60/40 and a melt flow rate of 0.2 to 3.0 g/10 min, Tris (2 , 3-dibromopropyl) isocyanurate, 5 to 25 parts by weight of chlorinated polyethylene, and 10 to 35 parts by weight of antimony trioxide.
１記載の難燃性樹脂組成物。2. The flame-retardant resin composition according to claim 1, containing 0.5 to 5 parts by weight of a stabilizer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8090891A JP2938209B2 (en) | 1991-03-19 | 1991-03-19 | Flame retardant resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8090891A JP2938209B2 (en) | 1991-03-19 | 1991-03-19 | Flame retardant resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04292645A true JPH04292645A (en) | 1992-10-16 |
| JP2938209B2 JP2938209B2 (en) | 1999-08-23 |
Family
ID=13731482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8090891A Expired - Lifetime JP2938209B2 (en) | 1991-03-19 | 1991-03-19 | Flame retardant resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2938209B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012500880A (en) * | 2008-08-29 | 2012-01-12 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Flame retardant polyolefin composition |
-
1991
- 1991-03-19 JP JP8090891A patent/JP2938209B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012500880A (en) * | 2008-08-29 | 2012-01-12 | アクゾ ノーベル ナムローゼ フェンノートシャップ | Flame retardant polyolefin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2938209B2 (en) | 1999-08-23 |
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