JPH04149238A - Flame retardant silane-crosslinked polyolefin composition - Google Patents
Flame retardant silane-crosslinked polyolefin compositionInfo
- Publication number
- JPH04149238A JPH04149238A JP27714190A JP27714190A JPH04149238A JP H04149238 A JPH04149238 A JP H04149238A JP 27714190 A JP27714190 A JP 27714190A JP 27714190 A JP27714190 A JP 27714190A JP H04149238 A JPH04149238 A JP H04149238A
- Authority
- JP
- Japan
- Prior art keywords
- pts
- weight
- parts
- silane
- crosslinking
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 24
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 19
- 239000003063 flame retardant Substances 0.000 title claims description 12
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims description 9
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910000077 silane Inorganic materials 0.000 claims abstract description 16
- 238000004132 cross linking Methods 0.000 claims abstract description 15
- -1 silane compound Chemical class 0.000 claims abstract description 12
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 125000000962 organic group Chemical group 0.000 claims abstract description 5
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims abstract description 4
- 150000002736 metal compounds Chemical class 0.000 claims description 10
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 abstract description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000765 intermetallic Inorganic materials 0.000 abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000002655 kraft paper Substances 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- 125000006325 2-propenyl amino group Chemical group [H]C([H])=C([H])C([H])([H])N([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000003544 oxime group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- 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、低発煙性で加工性の良い難燃性シラン架橋ポ
リオレフィン組成物の改良に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to the improvement of flame-retardant silane-crosslinked polyolefin compositions with low smoke emission and good processability.
（従来の技術）
従来より、ポリオレフィンに特定のシラン化合物をグラ
フト化させたグラフトポリマーを架橋させてなるシラン
架橋ポリオレフィン組成物は、耐熱性、耐薬品性等が優
れることから多用されている。このようなシラン架橋ポ
リオレフィン組成物を難燃化するためにはハロゲン系の
難燃剤と添加する方法かあるか、燃焼時に塩化水素ガス
等の有害カスを発生するという欠点があるので、非ハロ
ゲン系の難燃剤即ち、水酸化マクネシウム、水酸化アル
ミニウム等の水和金属化合物を配合したもの（例えば特
開昭５９−６４６５３号）か−最北しつつある。(Prior Art) Silane-crosslinked polyolefin compositions, which are obtained by crosslinking a graft polymer obtained by grafting a specific silane compound onto a polyolefin, have been widely used because of their excellent heat resistance, chemical resistance, and the like. In order to make such silane-crosslinked polyolefin compositions flame retardant, there is a method of adding halogen-based flame retardants, or non-halogen-based flame retardants have the disadvantage of generating harmful gas such as hydrogen chloride gas when burned. Flame retardants, ie, those containing hydrated metal compounds such as magnesium hydroxide and aluminum hydroxide (for example, JP-A-59-64653), are becoming the most popular.
しかしなから、水和金属化合物は比較的低温で脱水反応
が開始するため水を生じ易く、この水分か架橋を促進す
るので、本来の架橋工程ではない押出し機中での混線工
程においていわゆる早期架橋を進行させてしまう。この
早期架橋によって組成物か固くなり、混線作業性および
押出し作業性が悪くなるという問題を生していた。また
、このような水分たけでなく、ポリオレフィンポリマー
自体に微Ｉに残存する重合触媒の分解残渣等の不純物も
押出し加工性を低下させるという問題があつた。However, since the dehydration reaction of hydrated metal compounds starts at a relatively low temperature, it is easy to generate water, and this water promotes crosslinking. will proceed. This early crosslinking causes a problem in that the composition becomes hard, resulting in poor cross-crossing workability and poor extrusion workability. In addition to this water content, impurities such as decomposition residues of polymerization catalysts remaining in a small amount in the polyolefin polymer itself also have a problem of deteriorating extrusion processability.
〈発明が解決しようとする課題）
以上の点に鑑みて、本発明はＭ燃性に優？１、しかも押
出し機中での混和物の早期架橋を抑制して混練作業性お
よび押出し作業性３大幅に向上させることのて゛きる難
燃性シ・ラン架橋ポリオドフィン組成物を提供づ゛るこ
とを目的とする。(Problems to be Solved by the Invention) In view of the above points, does the present invention have superior M flammability? 1. The purpose of the present invention is to provide a flame-retardant silane-crosslinked polyodofin composition that can suppress early crosslinking of the mixture in an extruder and significantly improve kneading workability and extrusion workability. shall be.
（課題を解決するための手段）
本発明はすなわち、ポリオレフィン１００重量部に、一
般ＡＲＲ’ Ｓｉ Ｙ２ （式中、Ｒは１価のオしフ
ィン性不飽和炭化水素基、）′は加水分解し得る１価の
有機基、Ｒ゛はＲまたは）′）で示されるシラン化合物
０．１〜１０重量部をクラフト化させたクラフトポリマ
ーに、硫酸ノ＜リウ、％０． １〜５重量部と水和金属
化合物２０〜２００重量部を配合し架橋させることとｔ
８徴とオる難燃性シラン架橋ポリオドフィン組成物に関
する。(Means for Solving the Problems) The present invention specifically provides 100 parts by weight of polyolefin with general ARR' Si Y2 (wherein R is a monovalent olefinic unsaturated hydrocarbon group, )' is a hydrolyzable To a kraft polymer obtained by krafting 0.1 to 10 parts by weight of a silane compound represented by the monovalent organic group (R' is R or )'), sulfuric acid, % 0. Blending and crosslinking 1 to 5 parts by weight and 20 to 200 parts by weight of a hydrated metal compound;
This invention relates to a flame-retardant silane-crosslinked polyodofin composition with eight characteristics.
本発明におけるグラフトポリマーは、ホ゛リオしフィン
１００重量部に−ｉ弐ＲＲ’ Ｓ］ Ｙｘで示されるシ
ラン化合物０，１〜１０重量部を有機過酸化物の存在下
で常法によりグラフト反応させることにより得られる。The graft polymer in the present invention is produced by grafting 0.1 to 10 parts by weight of a silane compound represented by -i2RR'S]Yx to 100 parts by weight of polymeric fins in the presence of an organic peroxide by a conventional method. It is obtained by
使用されるポリオしフィンとしては、ポリエチトン、ポ
リ１０ビトン、エチトンー酢酸ビニル共重合体（ＥＶＡ
、）、エチレン−アクリル酸エチル共重合体＜ＥＥＡ＞
−エチレン−αオドフィン共重合体等があり、こｔｚら
は単独あるいは２種以上を混合して使用することかで゛
きる。特にＥＶＡにおける酢酸ビニル含量およびＥ Ｅ
Ａにおけるアクリル酸エチル含量は５〜３０重Ｊ９ｏ
か好まし、く、こｆ′Ｌより少ないと充填剤の添加か歎
しく、才たこれより多いと加工性および機械的強度の低
下を生しる二とかある。また、ホ゛すブ）コビレン分ク
ラフト化する場合は、粒径５００μｍ以下の粉末状とし
て使用するのかシランＬ・化効本の点から望ましい
また、−殻式ＲＲ’ＳｉＹ、で示されるシラン化合物中
のＲは、］価のオレフィン性不飽和炭化水素基てあり、
具体的にはビニル基、アリル基、ツブニル基、シクロへ
キセニル基、シクロペンタジェニル基等があり、特にビ
ニル基が好ましい。Polyolefins used include polyethytone, poly10vitone, ethithone-vinyl acetate copolymer (EVA
), ethylene-ethyl acrylate copolymer <EEA>
-ethylene-α-odophin copolymers, etc., and these can be used alone or in combination of two or more. Especially vinyl acetate content in EVA and E E
The ethyl acrylate content in A is 5 to 30 weight J9o
However, if the amount is less than f'L, it is difficult to add a filler, and if it is more than this, the processability and mechanical strength may deteriorate. In addition, in the case of krafting the cobylene component, it is preferable to use it in the form of a powder with a particle size of 500 μm or less from the viewpoint of silane L. R is a valent olefinically unsaturated hydrocarbon group,
Specific examples thereof include vinyl group, allyl group, tubunyl group, cyclohexenyl group, and cyclopentagenyl group, with vinyl group being particularly preferred.
式中）′は、メトキシ基、エトキシ基、メトキシ基等の
アルコキシ基やアシロキシ基、オキシム基、アルキルア
ミノ基、アリルアミノ基のような加水分解し得る有機基
である。式中Ｒ″は、ＲまたはＹである。本発明におい
ては特にＲ“＝Ｙのもの、即ち３個の加水分解し得る有
機基を持つシラン化合物か好適し、具体的にはビニルト
リメトキシシランやビニルトリエトキシシランかある。In the formula, )' is an alkoxy group such as a methoxy group, an ethoxy group, or a methoxy group, or a hydrolyzable organic group such as an acyloxy group, an oxime group, an alkylamino group, or an allylamino group. In the formula, R'' is R or Y. In the present invention, R''=Y, that is, a silane compound having three hydrolyzable organic groups, is particularly preferred, and specifically vinyltrimethoxysilane or vinyltriethoxysilane.
グラフトポリマーにおける配合割合は、ポリオレフィン
］、 Ｏ０重量部に対して上記シラン化合物が０．１〜
１０重量部であり、シラン化合物か０゜１重量部より少
ないと充分なグラフト化が行われず、ひいては架橋度か
小さくなり、また１０重量部より多いと加工性および外
観か悪くなる。より好ましくは０．５〜５重量部の範囲
である。The blending ratio in the graft polymer is 0.1 to 0.1 to 0.0 parts by weight of the above-mentioned silane compound to 0 parts by weight of polyolefin].
If the amount is less than 0.1 part by weight of the silane compound, sufficient grafting will not occur and the degree of crosslinking will be reduced, and if it is more than 10 parts by weight, processability and appearance will be poor. More preferably, it is in the range of 0.5 to 5 parts by weight.
本発明における水和金属化合物は高温において水を脱離
する無ｔａ難燃剤であり、水酸化アルミニラＪ、（水和
アルミナ）、水酸化マグネシウム等を単独または混合し
て使用することができる。配合割合は、クラフトポリマ
ーにお＋するポリオレフィン３． （月）重量部に対し
て２０〜２００重量部である。配合量かこれより少ない
と難燃性が不充分であり、二へより多いと組成物の加工
性およびＳ械的特性か悪くなる。なお、早期架橋の防止
および得られた組成物の保管時の吸湿防止の面から、シ
ラン力・シブリング剤等で表面処、埋された水和金属化
合物を使用することかより好ましい。The hydrated metal compound in the present invention is a non-ta flame retardant that desorbs water at high temperatures, and aluminum hydroxide J, (hydrated alumina), magnesium hydroxide, etc. can be used alone or in combination. The blending ratio is 3. The kraft polymer + the polyolefin. The amount is 20 to 200 parts by weight (monthly). If the amount is less than this, the flame retardance will be insufficient, and if it is more than 2, the processability and mechanical properties of the composition will be poor. In addition, from the viewpoint of preventing early crosslinking and moisture absorption during storage of the obtained composition, it is more preferable to use a hydrated metal compound whose surface is treated or embedded with a silane force, a sibling agent, etc.
また、硫酸バリウ１、は水和金属化合物から脱離し！、
２７Ｊ（や、ホ゛リオトフィン自体に含まれる重合触媒
の分解残渣等の不純物を捕捉して、組成物の早期架橋を
防止するので、これを添加することにより長詩間の安定
した加工性、作業性を実現する。In addition, barium sulfate 1 is desorbed from the hydrated metal compound! ,
It traps impurities such as 27J (and the decomposition residue of the polymerization catalyst contained in the polymerization catalyst itself) and prevents early crosslinking of the composition, so its addition improves stable processability and workability over long periods. Realize.
配合割合は５クラフトポリマーにおけるポリオレフィン
１００重量部に対して０，１〜・５重量部である。配合
Ｖかこれより少ないと水や不純物の捕捉効果か小さく、
ひた５重量部を越えて配合しても効果は飽和して向上ぜ
す、むしろ加工性か低下する傾向にあり望ましくない。The blending ratio is 0.1 to .5 parts by weight per 100 parts by weight of the polyolefin in the 5 kraft polymer. If the formulation is V or less, the effect of trapping water and impurities will be small.
Even if the amount exceeds 5 parts by weight, the effect will be saturated and improved, but processability will tend to deteriorate, which is not desirable.
より好ましくは０１１〜２重量部の範囲である。More preferably, it is in the range of 0.011 to 2 parts by weight.
本発明の難燃性シラン架橋ポリオレフィン組成物は例え
ば次のようにして製造される。即ち、ポリオレフィンに
所定量の上記シラン化合物と遊離ラジカル発生剤（シタ
ミルパーオキサイド等の有機過酸化物）とを添加して常
法によりグラフトポリマーを製造し、これに硫酸バリウ
ムと水和金属化合物を所定量配合して充分混練する。こ
のようにして得られたグラフトポリマー混和物に、ジブ
チル錫ジラウレート（ＤＢＴＤＬ）のようなシラノール
縮合触媒を直接あるいはマスターバッチにしで加え、充
分混′ａ後、押出し機により所定形状に押出し成型する
。押出さｈを組成物を常温または加熱しなから少量の水
と反応させることによりシラン架橋を行って本発明のＮ
燃性シラン架橋ポリオレノ４ン組成物か製造される。The flame-retardant silane-crosslinked polyolefin composition of the present invention is produced, for example, as follows. That is, a predetermined amount of the above-mentioned silane compound and a free radical generator (organic peroxide such as cytamyl peroxide) are added to polyolefin to produce a graft polymer by a conventional method, and then barium sulfate and a hydrated metal compound are added to the graft polymer. Blend a predetermined amount and knead thoroughly. A silanol condensation catalyst such as dibutyltin dilaurate (DBTDL) is added directly or in the form of a masterbatch to the graft polymer mixture thus obtained, and after thorough mixing, it is extruded into a predetermined shape using an extruder. After extrusion, the composition is reacted with a small amount of water at room temperature or without heating to perform silane crosslinking to obtain the N of the present invention.
A flammable silane crosslinked polyolenon composition is produced.
なお、本発明においては、酸化防止剤や着色剤などの添
加剤を適宜配合しても良い。In addition, in the present invention, additives such as antioxidants and colorants may be appropriately blended.
（実施例） 本発明の実施例について説明する。(Example) Examples of the present invention will be described.
実施例１〜４
表に示す配合でポリオレフィンと、ビニルトリメトキシ
シラン・と、ジクミルパーオキサイド（有機過酸化物）
とをトライブレンドした後、常法によりクラフト化反応
させた９これに水酸化アルミニウム（ｔたは水酸化マグ
ネシウム）と硫酸バリウムを添加してコニ−グーで充分
混練した後、ＤＢＴＤＬのマスターバッチを少量添加し
てシート状に押出した。得られたシートを１００’Ｃの
沸騰水中１．ご１時間浸漬してシラン架橋と行い、これ
を試験片とした。なお、水和金属化合物はアミノシラン
系シランカップリンク剤を３２δ程度添加したのちベー
キンク処理したもの３使用した。Examples 1 to 4 Polyolefin, vinyltrimethoxysilane, and dicumyl peroxide (organic peroxide) in the formulation shown in the table.
After tri-blending them, a krafting reaction was carried out using a conventional method.To this, aluminum hydroxide (t or magnesium hydroxide) and barium sulfate were added and thoroughly kneaded with a coni-goo, followed by a DBTDL masterbatch. A small amount was added and extruded into a sheet. The obtained sheet was placed in boiling water at 100'C for 1. The sample was immersed for 1 hour to effect silane crosslinking, and this was used as a test piece. The hydrated metal compound used was one in which approximately 32 δ of an aminosilane-based silane coupling agent was added and then subjected to baking treatment.
得られた試験片を用いて、引張り強さと伸ひはＪＩＳ
Ｋ ６７６０に（１１ＩＩＩ１１厚さシート）、ま
た架橋度はＪＩＳ Ｃ３００５に、難燃性（酸素指数
）はＪＩＳ Ｋ ７２０１に（３閣厚さシート）そ
れぞれ準拠して測定した。加工性は、ブラヘンダープラ
ストグラフにより密閉系において２００°Ｃ１１００ｒ
ｐＨの条件で、各配合物を混練し、トルクが急激な上昇
を示すまでの時間を測定し、３０分以上を○、２５〜２
９分を△、２０分以下を×と評価した。結果を表に示す
。Using the obtained test piece, the tensile strength and elongation were determined according to JIS
The degree of crosslinking was measured in accordance with JIS C3005, and the flame retardancy (oxygen index) was measured in accordance with JIS K 7201 (3 thickness sheet). Processability is determined by Brahender Plastograph at 200°C 1100r in a closed system.
Each compound was kneaded under pH conditions, and the time until the torque showed a rapid increase was measured.
9 minutes was evaluated as △, and 20 minutes or less was evaluated as ×. The results are shown in the table.
比較−例１〜４
比較として、硫酸バリウムの配合量が過少の場合（比較
例１）、逆に過剰の場合（比較例２）、シラン化合物の
配合量が過剰の場合（比較例３）、水和金属化合物の配
合量が過剰の場合（比較例４）について、表に示す配合
で実施例１と同様にして試験片を製造し、同様の試験を
行った。結果を表に示す。Comparison - Examples 1 to 4 As a comparison, when the amount of barium sulfate blended is too little (Comparative Example 1), when the amount of barium sulfate is too much (Comparative Example 2), when the amount of silane compound is too much (Comparative Example 3), Regarding the case where the amount of the hydrated metal compound was excessive (Comparative Example 4), test pieces were manufactured in the same manner as in Example 1 using the formulations shown in the table, and the same tests were conducted. The results are shown in the table.
（以下余白）
（発明の効果）
以上、本発明の難燃性シラン架橋ポリオレフィン組成物
は、難燃性に優れ、しかも押出し機中での組成物の早期
架橋を抑制して混練作業性および押出し作業性を大幅に
向上させることかできる。(The following is a blank space) (Effects of the invention) As described above, the flame-retardant silane-crosslinked polyolefin composition of the present invention has excellent flame retardancy, and also suppresses early crosslinking of the composition in an extruder, improving kneading workability and extrusion. It can greatly improve work efficiency.
Claims (1)
ｉＹ＿２（式中、Ｒは１価のオレフィン性不飽和炭化水
素基、Ｙは加水分解し得る１価の有機基、Ｒ’はＲまた
はＹ）で示されるシラン化合物０．１〜１０重量部をグ
ラフト化させたグラフトポリマーに、硫酸バリウム０．
１〜５重量部と水和金属化合物２０〜２００重量部を配
合し架橋させることを特徴とする難燃性シラン架橋ポリ
オレフィン組成物。(1) 100 parts by weight of polyolefin, general formula RR'S
0.1 to 10 parts by weight of a silane compound represented by iY_2 (wherein R is a monovalent olefinic unsaturated hydrocarbon group, Y is a hydrolyzable monovalent organic group, and R' is R or Y). 0.0 barium sulfate was added to the grafted polymer.
A flame-retardant silane-crosslinked polyolefin composition characterized by blending and crosslinking 1 to 5 parts by weight and 20 to 200 parts by weight of a hydrated metal compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27714190A JPH04149238A (en) | 1990-10-15 | 1990-10-15 | Flame retardant silane-crosslinked polyolefin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27714190A JPH04149238A (en) | 1990-10-15 | 1990-10-15 | Flame retardant silane-crosslinked polyolefin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04149238A true JPH04149238A (en) | 1992-05-22 |
Family
ID=17579370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27714190A Pending JPH04149238A (en) | 1990-10-15 | 1990-10-15 | Flame retardant silane-crosslinked polyolefin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04149238A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6107413A (en) * | 1995-12-27 | 2000-08-22 | Sumitomo Bakelite Company Limited | Process for producing flame-retardant, silane-crosslinked polyolefin |
| JP2012177028A (en) * | 2011-02-25 | 2012-09-13 | Mitsubishi Chemicals Corp | Flame-retardant polyolefin resin composition and method of manufacturing the same |
| JP2018172701A (en) * | 2013-08-27 | 2018-11-08 | 古河電気工業株式会社 | Heat resistant silane crosslinked resin compact and production method thereof, heat resistant silane crosslinkable resin composition and production method thereof, silane master batch, and heat resistant product using heat resistant silane crosslinked resin compact |
-
1990
- 1990-10-15 JP JP27714190A patent/JPH04149238A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6107413A (en) * | 1995-12-27 | 2000-08-22 | Sumitomo Bakelite Company Limited | Process for producing flame-retardant, silane-crosslinked polyolefin |
| JP2012177028A (en) * | 2011-02-25 | 2012-09-13 | Mitsubishi Chemicals Corp | Flame-retardant polyolefin resin composition and method of manufacturing the same |
| JP2018172701A (en) * | 2013-08-27 | 2018-11-08 | 古河電気工業株式会社 | Heat resistant silane crosslinked resin compact and production method thereof, heat resistant silane crosslinkable resin composition and production method thereof, silane master batch, and heat resistant product using heat resistant silane crosslinked resin compact |
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