JP3459035B2 - Crosslinkable flame-retardant resin composition - Google Patents
Crosslinkable flame-retardant resin compositionInfo
- Publication number
- JP3459035B2 JP3459035B2 JP35823497A JP35823497A JP3459035B2 JP 3459035 B2 JP3459035 B2 JP 3459035B2 JP 35823497 A JP35823497 A JP 35823497A JP 35823497 A JP35823497 A JP 35823497A JP 3459035 B2 JP3459035 B2 JP 3459035B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- flame
- retardant
- less
- 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.)
- Expired - Fee Related
Links
- 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 37
- 239000003063 flame retardant Substances 0.000 title claims description 36
- 239000011342 resin composition Substances 0.000 title claims description 21
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- -1 Organosilane compound Chemical class 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 9
- 230000005494 condensation Effects 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 9
- 150000004692 metal hydroxides Chemical class 0.000 claims description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 9
- 150000003254 radicals Chemical class 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229920005672 polyolefin resin Polymers 0.000 claims description 8
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- 238000004132 cross linking Methods 0.000 claims description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical group [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000002883 imidazolyl group Chemical group 0.000 claims description 3
- 150000001451 organic peroxides Chemical class 0.000 claims description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 1
- 150000001342 alkaline earth metals Chemical group 0.000 claims 1
- 238000005470 impregnation Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 238000002156 mixing Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 5
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、難燃樹脂組成物に
関する。TECHNICAL FIELD The present invention relates to a flame retardant resin composition.
【０００２】[0002]
【従来の技術】オレフィン系樹脂は安価でありながら、
加工性や耐薬品性に優れているため、様々な用途に用い
られている。しかしながら易燃性であるため、従来多く
の改良が試みられてきた。代表的な方法としてはハロゲ
ン系の難燃剤を配合する方法があるものの、ハロゲン系
難燃剤は燃焼時に有害なハロゲン含有ガスを発生すると
云う問題がある。ここで非ハロゲン系難燃剤として金属
水酸化物を添加する解決方法が知られている。しかしな
がら、金属水酸化物の場合、単独添加系では充分な難燃
性が得られず、他の成分とともに配合すると多重配合と
なって樹脂としての加工性が低下し、同時に加熱変形率
が増大する。2. Description of the Related Art Although olefin resins are inexpensive,
It has excellent workability and chemical resistance, and is used for various purposes. However, since it is flammable, many improvements have been attempted in the past. As a typical method, there is a method of blending a halogen-based flame retardant, but the halogen-based flame retardant has a problem that a harmful halogen-containing gas is generated during combustion. Here, a solution is known in which a metal hydroxide is added as a non-halogen flame retardant. However, in the case of metal hydroxides, sufficient flame retardancy cannot be obtained with a single addition system, and when compounded with other components, it becomes a multi-compound and the workability as a resin decreases, and at the same time the heat distortion rate increases. .
【０００３】[0003]
【発明が解決しようとする課題】本発明は、上記欠点を
解決する、すなわち、加工性が良好で、加熱変形率が低
く、充分な引張強度と伸び性とを有しながらも、ハロゲ
ン系難燃剤を用いない架橋性難燃樹脂組成物を提供する
ことを目的とする。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned drawbacks, that is, it has good workability, has a low heat deformation rate, and has sufficient tensile strength and extensibility, but it is difficult to use halogen-based compounds. An object is to provide a crosslinkable flame-retardant resin composition that does not use a flame retardant.
【０００４】[0004]
【課題を解決するための手段】本発明の架橋性難燃樹脂
組成物は、請求項１に記載のとおり、オレフィン系樹脂
１００重量部に対し、化学式 ＲＲ’ＳｉＹ 3 （式中、Ｒ：一価のオレフィン性不飽和炭化水素基また
はヒドロカルボキシル基、Ｒ’：脂肪族飽和炭化水素基
またはＹ、Ｙ：加水反応により開裂可能な二重結合を有
している有機基）で示される有機シラン化合物０．０１
重量部以上１５重量部未満、イミダゾール基を有してい
る有機過酸化物からなる遊離ラジカル発生剤０．０１重
量部以上１０重量部以下、架橋促進剤として働くシラノ
ール縮合触媒０．０１重量部以上１０重量部以下を、プ
リプレグ方式により含浸させたものを押出機あるいはミ
キサーに投入して１７０℃以上２３０℃以下の温度でグ
ラフト化させてなる
シラングラフト化オレフィン系ベー
ス樹脂１００重量部に対して、１分子中に２つ以上の水
酸基を有する金属水酸化物を３０重量部以上２００重量
部以下、膨張黒鉛を３重量部以上４０重量部以下、及
び、ハロゲン元素とアミノ基とを共に有さないシリコー
ンを０．１重量部以上２０重量部以下、配合してなる架
橋性難燃樹脂組成物である。The crosslinkable flame-retardant resin composition of the present invention is an olefin resin as set forth in claim 1.
With respect to 100 parts by weight, the chemical formula RR'SiY 3 (wherein R is a monovalent olefinically unsaturated hydrocarbon group or
Is a hydrocarboxyl group, R ': an aliphatic saturated hydrocarbon group
Or Y, Y: having a double bond cleavable by hydrolysis
Organosilane compound represented by 0.01)
At least 15 parts by weight and having an imidazole group
0.01 weight of free radical generator consisting of organic peroxide
Silano that acts as a crosslinking accelerator in an amount of 10 parts by weight or more and 10 parts by weight or less
Pool condensation catalyst 0.01 parts by weight or more and 10 parts by weight or less
What is impregnated by the repreg method is used in an extruder or a mixer.
Put it in a kiser and turn it at a temperature of 170 ° C to 230 ° C.
30 parts by weight or more and 200 parts by weight of a metal hydroxide having two or more hydroxyl groups in one molecule, relative to 100 parts by weight of the silane-grafted olefin base resin formed by rafting.
Parts or less , 3 parts by weight or more and 40 parts by weight or less of expanded graphite, and 0.1 parts by weight or more and 20 parts by weight or less of a silicone having neither a halogen element nor an amino group, and a crosslinkable flame-retardant resin. It is a composition.
【０００５】[0005]
【発明の実施の形態】本発明で用いるシラングラフトオ
レフィン系ベース樹脂はオレフィン系樹脂を遊離ラジカ
ル発生剤及びシラノール縮合触媒の存在下で反応させて
得ることができる。このようなシラングラフトオレフィ
ン系ベース樹脂を用いることにより強度、伸び性の良好
な難燃樹脂組成物とすることができる。このときオレフ
ィン系樹脂１００重量部に対し、化学式ＲＲ’ＳｉＹ3
（Ｒ：ビニル基、アリル基、ブテニル基等一価のオレフ
ィン性不飽和炭化水素基またはヒドロカルボキシル基、
Ｒ’：メチル基、エチル基、プロピル基等脂肪族飽和炭
化水素基またはＹ、Ｙ：メトキシ基、エトキシ基等のア
ルコキシ基、またはアシルオキシ基、オキシモ等加水反
応により開裂可能な二重結合を有している有機基）で示
される有機シラン化合物０．０１重量部以上１５重量部
未満、ジクミルパーオキサイド等のイミダゾール基を有
している有機過酸化物からなる遊離ラジカル発生剤０．
０１重量部以上１０重量部以下、架橋促進剤として働く
ジブチル錫ジラウレートなどのシラノール縮合触媒０．
０１重量部以上１０重量部以下を、さらに必要に応じて
酸化防止剤０．１重量部以上６重量部以下をいわゆるプ
リプレグ方式によりヘンシェルミキサーなどで含浸させ
たものを押出機あるいはミキサーに投入して１７０℃以
上２３０℃以下の温度でグラフト化させることが望まし
い。BEST MODE FOR CARRYING OUT THE INVENTION The silane-grafted olefin base resin used in the present invention can be obtained by reacting an olefin resin in the presence of a free radical generator and a silanol condensation catalyst. By using such a silane-grafted olefin-based resin, it is possible to obtain a flame-retardant resin composition having good strength and extensibility. At this time, the chemical formula RR'SiY 3 is added to 100 parts by weight of the olefin resin.
(R: monovalent olefinically unsaturated hydrocarbon group such as vinyl group, allyl group, butenyl group or hydrocarboxyl group,
R ': a methyl group, an ethyl group, a propyl group or other saturated aliphatic hydrocarbon group, or Y, Y: an alkoxy group such as a methoxy group or an ethoxy group, or an acyloxy group or an oximo group having a double bond cleavable by a hydrolysis reaction. A free radical generator comprising an organic silane compound represented by 0.01 to 15 parts by weight and less than 15 parts by weight, and an organic peroxide having an imidazole group such as dicumyl peroxide.
01 parts by weight or more and 10 parts by weight or less of a silanol condensation catalyst such as dibutyltin dilaurate which acts as a crosslinking accelerator.
What was impregnated with 01 parts by weight or more and 10 parts by weight or less and, if necessary, 0.1 parts by weight or more and 6 parts by weight or less of an antioxidant by a so-called prepreg system was put into an extruder or a mixer. It is desirable to graft at a temperature of 170 ° C or higher and 230 ° C or lower.
【０００６】ここで、有機シラン化合物、遊離ラジカル
発生剤、シラノール縮合触媒の添加量がそれぞれ上記下
限値未満であると、充分にグラフト反応が進行せず、そ
の結果強度、伸び性の共に良好な難燃樹脂組成物とする
ことができない。一方、それぞれの成分を上記上限値を
超えて添加してもその効果は飽和しているため不経済で
あると共に、配合のバランスが崩れるため、むしろ難燃
樹脂組成物としたときの諸性能が低下する。なお、遊離
ラジカル発生剤及び縮合触媒の配合量はそれぞれ有機シ
ラン化合物の配合量の１／１５以上１／５以下が良好な
結果が得られ、最適な配合比は１／１０である。If the addition amount of each of the organic silane compound, the free radical generator and the silanol condensation catalyst is less than the above lower limit value, the graft reaction does not proceed sufficiently and, as a result, both strength and elongation are good. It cannot be a flame-retardant resin composition. On the other hand, even if each component is added in excess of the above upper limit, its effect is saturated and it is uneconomical, and since the balance of the composition is lost, the various performances when made into a flame retardant resin composition are rather descend. It should be noted that good results can be obtained when the blending amount of the free radical generator and the condensation catalyst is 1/15 or more and 1/5 or less of the blending amount of the organic silane compound, respectively, and the optimum blending ratio is 1/10.
【０００７】また、上記のように有機シラン化合物、遊
離ラジカル発生剤、シラノール縮合触媒をプリプレグ方
式で樹脂に含浸させてシラン架橋を行わせることが重要
である。すなわち、このときに難燃性付与成分が添加さ
れていないため、上記シラン架橋が難燃性付与成分によ
って妨害されることがなく、延いては架橋性難燃樹脂組
成物の難燃性その他の物性が良好なものとなる。なお、
本発明において、オレフィン系樹脂とは、ポリエチレ
ン、ポリプロピレンあるいは、エチレン系共重合体、た
とえばエチレン−エチルアクリレート共重合体やエチレ
ン−酢酸ビニル共重合体等を指す。ここで用いるオレフ
ィン系樹脂が直鎖低密度ポリエチレン７０重量部とエチ
レン−酢酸ビニル共重合体３０重量部との混合物である
と、難燃剤を多量に配合したことによる物性低下を効果
的に防ぐことができる。Further, it is important to impregnate the resin with the organic silane compound, the free radical generator, and the silanol condensation catalyst as described above in the prepreg system to carry out the silane crosslinking. That is, since the flame-retardant imparting component is not added at this time, the silane cross-linking is not disturbed by the flame-retardant imparting component, and thus the flame-retardant and other properties of the cross-linkable flame-retardant resin composition. It has good physical properties. In addition,
In the present invention, the olefin resin refers to polyethylene, polypropylene, or an ethylene copolymer such as an ethylene-ethyl acrylate copolymer or an ethylene-vinyl acetate copolymer. When the olefin resin used here is a mixture of 70 parts by weight of a linear low-density polyethylene and 30 parts by weight of an ethylene-vinyl acetate copolymer, it is possible to effectively prevent the physical properties from being deteriorated by adding a large amount of the flame retardant. You can
【０００８】また、本発明の難燃樹脂組成物は１分子中
に２つ以上の水酸基を有する金属水酸化物を含む。たと
えば水酸化アルミニウムや水酸化マグネシウム、水酸化
カルシウムなどである。このうちアルカリ土類金属水酸
化物であると取扱性が良好であり、良好な難燃性が得ら
れるため好ましく、また特に水酸化マグネシウムである
ことが望ましい。Further, the flame-retardant resin composition of the present invention contains a metal hydroxide having two or more hydroxyl groups in one molecule. For example, aluminum hydroxide, magnesium hydroxide, calcium hydroxide and the like. Of these, alkaline earth metal hydroxides are preferable because they are easy to handle and have good flame retardancy, and magnesium hydroxide is particularly preferable.
【０００９】一方、本発明で用いる膨張黒鉛は燃焼時に
その体積が５０倍以上１５０倍以下となるものことが望
ましい。すなわち、燃焼時に膨張黒鉛が膨張することに
よって、燃焼箇所への空気中の酸素の供給が制限され
て、その結果良好な難燃性が得られるが、燃焼時の体積
が５０倍未満にしかならない膨張黒鉛を用いると上記効
果が充分でなく、また膨張倍率が１５０倍超のものを用
いると、ベース樹脂の粘度低下に対し、膨張率が大きす
ぎるため、逆に酸素供給箇所を設けることとなる。ま
た、本発明においてシリコーンとはシリコーン重合体で
あり、本発明の趣旨から云って、有毒ガスの発生の原因
となるおそれのある、ハロゲン元素やシアノ基を有しな
いものであることが必要である。なお、本発明の難燃性
樹脂組成物の難燃性はきわめて高いため、ハロゲン元素
を含まないシリコーンを用いても充分な難燃性が得られ
る。On the other hand, the expanded graphite used in the present invention preferably has a volume of 50 times or more and 150 times or less at the time of combustion. That is, the expansion of the expanded graphite during combustion restricts the supply of oxygen in the air to the combustion site, resulting in good flame retardancy, but the volume during combustion is less than 50 times. If expanded graphite is used, the above-mentioned effect is not sufficient, and if expansion coefficient is more than 150 times, expansion coefficient is too large with respect to decrease in viscosity of the base resin, so that oxygen supply place is provided on the contrary. . Further, in the present invention, the silicone is a silicone polymer, and for the purpose of the present invention, it is necessary that the silicone does not have a halogen element or a cyano group that may cause generation of toxic gas. . Since the flame-retardant resin composition of the present invention has extremely high flame retardancy, sufficient flame retardancy can be obtained even when silicone containing no halogen element is used.
【００１０】その他の成分としてはリン系難燃剤等の難
燃助剤を適宜添加する。なおリン系難燃剤は炭化皮膜を
形成させ、その結果酸素を遮断する働きを有する。これ
ら原料をニーダー、ロールミル等の通常の混練手段によ
って混練して本発明の難燃性樹脂組成物とする。なお配
合比率としては、シラングラフトオレフィン系ベース樹
脂原料のオレフィン系樹脂１００重量部に対して、金属
水酸化物３０重量部以上２００重量部以下、膨張黒鉛３
重量部以上４０重量部以下、シリコーン０．１重量部以
上２０重量部以下である。ここで、金属水酸化物、膨張
黒鉛及びシリコーンの配合量がそれぞれ上記下限値未満
であると充分な難燃性が得られず、一方、それぞれの成
分を上記上限値を超えて添加してもその効果は飽和して
いるため不経済であると共に、配合のバランスが崩れる
ため、むしろ難燃樹脂組成物としたときの機械的性能が
低下する。As other components, a flame retardant auxiliary such as a phosphorus flame retardant is appropriately added. The phosphorus-based flame retardant functions to form a carbonized film and, as a result, to block oxygen. These raw materials are kneaded by an ordinary kneading means such as a kneader or a roll mill to obtain the flame-retardant resin composition of the present invention. The mixing ratio is 30 parts by weight or more and 200 parts by weight or less of the metal hydroxide and 3 parts by weight of the expanded graphite based on 100 parts by weight of the olefin-based resin as the raw material of the silane-grafted olefin-based resin.
It is from 40 parts by weight to 40 parts by weight, and from 0.1 parts by weight to 20 parts by weight of silicone. Here, if the blending amounts of the metal hydroxide, expanded graphite and silicone are each less than the lower limit value described above, sufficient flame retardancy cannot be obtained. On the other hand, even if each component is added in excess of the above upper limit value. Since the effect is saturated, it is uneconomical and the balance of the composition is lost, so that the mechanical performance of the flame-retardant resin composition is rather deteriorated.
【００１１】[0011]
【実施例】以下、本発明の実施例について説明する。実
施例・比較例で用いた原料の詳細について表１に記載し
た。EXAMPLES Examples of the present invention will be described below. Details of the raw materials used in Examples and Comparative Examples are shown in Table 1.
【００１２】[0012]
【表１】
表１に示した原料を表２〜６に示した配合比で配合しそ
れぞれ難燃樹脂組成物を得たが、このとき、まずオレフ
ィン系樹脂、有機シラン化合物、遊離ラジカル発生剤、
シラノール縮合触媒及び酸化防止剤をプリプレグ方式に
よりヘンシェルミキサーで含浸させたものを押出機ある
いはミキサーに投入して２００℃でグラフト化させた
後、水酸化マグネシウム、リン系難燃剤、膨張黒鉛、シ
リコーンを添加し混合して作製した。[Table 1] The raw materials shown in Table 1 were blended at the blending ratios shown in Tables 2 to 6 to obtain flame-retardant resin compositions. At this time, first, an olefin resin, an organic silane compound, a free radical generator,
After impregnating a silanol condensation catalyst and an antioxidant with a Henschel mixer by a prepreg method, put it into an extruder or a mixer and graft it at 200 ° C, then add magnesium hydroxide, a phosphorus-based flame retardant, expanded graphite, and silicone. It was prepared by adding and mixing.
【００１３】[0013]
【表２】 [Table 2]
【００１４】[0014]
【表３】 [Table 3]
【００１５】[0015]
【表４】 [Table 4]
【００１６】[0016]
【表５】 [Table 5]
【００１７】[0017]
【表６】 [Table 6]
【００１８】これら難燃樹脂組成物の評価を行った。Ｊ
ＩＳ・Ｋ７２０１に準拠し酸素指数酸素指数値、ＪＩＳ
・Ｃ３００５に準拠し加熱変形率、ＪＩＳ・Ｋ６７６０
に準拠し引張強さ、ＪＩＳ・Ｋ６７６０に準拠し伸びを
それぞれ評価し、また、加工性をラボプラストミル押出
加工性として評価した。なお、酸素指数値では３０以
上、加熱変形率では３０％以下、引張強さおよび伸びで
はそれぞれ１０ＭＰａ以上、１５０％以上であるとき、
それぞれ良好な性能があるとして「○」と評価し、これ
ら基準を満たさない場合「×」として評価した。また、
加工性ではそれぞれ組成物を用いて被覆電線を押し出し
成形によって作製し、得られた被覆電線の被覆を視認検
査によって評価し、何ら欠陥がない被覆電線が得られた
場合良好な加工性を有するとして「○」とし、欠陥があ
った被覆電線が得られた場合に「×」として評価した。
これら結果を表２〜表６に記載した。これら結果より、
本発明に係る難燃樹脂組成物は酸素指数値、加熱変形
率、引張強さ、伸び、及び加工性すべてを満足する優れ
たものであることが判る。The flame-retardant resin compositions were evaluated. J
Oxygen index according to ISK7201, oxygen index value, JIS
・ Heat deformation rate according to C3005, JIS ・ K6760
The tensile strength was evaluated in accordance with JIS K6760 and the elongation was evaluated in accordance with JIS K6760, and the workability was evaluated as Labo Plastomill extrusion processability. When the oxygen index value is 30 or more, the heat deformation rate is 30% or less, and the tensile strength and the elongation are 10 MPa or more and 150% or more, respectively,
Each of them was evaluated as “◯” because it had good performance, and was evaluated as “x” when these criteria were not satisfied. Also,
In terms of workability, a coated electric wire was produced by extrusion molding using each composition, and the coating of the obtained covered electric wire was evaluated by visual inspection, and if a coated electric wire without any defect was obtained, it was considered to have good workability. It was evaluated as “◯” and evaluated as “x” when a defective covered electric wire was obtained.
The results are shown in Tables 2 to 6. From these results,
It can be seen that the flame-retardant resin composition according to the present invention is an excellent composition that satisfies all of the oxygen index value, the heat deformation rate, the tensile strength, the elongation, and the processability.
【００１９】[0019]
【発明の効果】本発明の難燃樹脂組成物は有害なガスを
発生するおそれのあるハロゲン系難燃剤を用いないにも
拘わらず、加工性が良好で、加熱変形率が低く、充分な
引張強度と伸び性とを有する架橋性難燃樹脂組成物であ
る。EFFECTS OF THE INVENTION The flame-retardant resin composition of the present invention has good workability, low thermal deformation rate and sufficient tensile strength, even though it does not use a halogen-based flame retardant which may generate harmful gas. A crosslinkable flame-retardant resin composition having strength and extensibility.
Claims (6)
化学式 ＲＲ’ＳｉＹ 3 （式中、Ｒ：一価のオレフィン性不飽和炭化水素基また
はヒドロカルボキシル基、Ｒ’：脂肪族飽和炭化水素基
またはＹ、Ｙ：加水反応により開裂可能な二重結合を有
している有機基）で示される有機シラン化合物０．０１
重量部以上１５重量部未満、イミダゾール基を有してい
る有機過酸化物からなる遊離ラジカル発生剤０．０１重
量部以上１０重量部以下、架橋促進剤として働くシラノ
ール縮合触媒０．０１重量部以上１０重量部以下を、プ
リプレグ方式により含浸させたものを押出機あるいはミ
キサーに投入して１７０℃以上２３０℃以下の温度でグ
ラフト化させてなる シラングラフト化オレフィン系ベー
ス樹脂１００重量部に対して、 １分子中に２つ以上の水酸基を有する金属水酸化物を３
０重量部以上２００重量部以下、膨張黒鉛を３重量部以
上４０重量部以下、及び、ハロゲン元素とアミノ基とを
共に有さないシリコーンを０．１重量部以上２０重量部
以下、配合してなることを特徴とする架橋性難燃樹脂組
成物。1. To 100 parts by weight of an olefin resin,
Chemical formula RR'SiY 3 (In the formula, R: monovalent olefinically unsaturated hydrocarbon group or
Is a hydrocarboxyl group, R ': an aliphatic saturated hydrocarbon group
Or Y, Y: having a double bond cleavable by hydrolysis
Organosilane compound represented by 0.01)
At least 15 parts by weight and having an imidazole group
0.01 weight of free radical generator consisting of organic peroxide
Silano that acts as a crosslinking accelerator in an amount of 10 parts by weight or more and 10 parts by weight or less
Pool condensation catalyst 0.01 parts by weight or more and 10 parts by weight or less
What is impregnated by the repreg method is used in an extruder or a mixer.
Put it in a kiser and turn it at a temperature of 170 ° C to 230 ° C.
With respect to 100 parts by weight of the silane-grafted olefin-based resin formed by rafting , 3 metal hydroxides having 2 or more hydroxyl groups in one molecule are used.
0 to 200 parts by weight , expanded graphite 3 parts by weight or less
40 parts by weight or less , and 0.1 parts by weight or more and 20 parts by weight of silicone having neither halogen element nor amino group
Hereinafter, a crosslinkable flame-retardant resin composition characterized by being blended.
ス樹脂のプリプレグ方式による含浸時において、シラン
グラフト化オレフィン系ベース樹脂１００重量部に対し
て酸化防止剤が０．１重量部以上６重量部以下添加され
ていることを特徴とする請求項１に記載の架橋性難燃樹
脂組成物。 2. The silane-grafted olefin-based ba
Of silane during the impregnation of the resin with the prepreg method.
Based on 100 parts by weight of grafted olefin base resin
0.1 to 6 parts by weight of antioxidant is added.
The crosslinkable flame-retardant tree according to claim 1, characterized in that
Fat composition.
樹脂がオレフィン系樹脂を遊離ラジカル発生剤及びシラ
ノール縮合触媒の存在下で反応させて得たものであるこ
とを特徴とする請求項１に記載の架橋性難燃樹脂組成
物。 3. The silane-grafted olefin base
The resin is an olefinic resin, a free radical generator and sila.
It was obtained by reacting in the presence of a nor condensation catalyst.
The crosslinkable flame-retardant resin composition according to claim 1,
object.
倍以上１５０倍以下となるものであることを特徴とする
請求項１または請求項２に記載の架橋性難燃樹脂組成
物。 4. The expanded graphite has a volume of 50 when burned.
It is characterized by being more than double and less than 150 times
The crosslinkable flame-retardant resin composition according to claim 1 or 2.
object.
酸化物であることを特徴とする請求項１ないし請求項３
のいずれかに記載の架橋性難燃樹脂組成物。 5. The above-mentioned metal hydroxide is alkaline earth metal water.
It is an oxide, The claim | item 1 thru | or 3 characterized by the above-mentioned.
The crosslinkable flame-retardant resin composition according to any one of 1.
であることを特徴とIs characterized by する請求項４に記載の架橋性難燃樹The crosslinkable flame retardant tree according to claim 4.
脂組成物。Fat composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35823497A JP3459035B2 (en) | 1997-12-25 | 1997-12-25 | Crosslinkable flame-retardant resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35823497A JP3459035B2 (en) | 1997-12-25 | 1997-12-25 | Crosslinkable flame-retardant resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11181189A JPH11181189A (en) | 1999-07-06 |
| JP3459035B2 true JP3459035B2 (en) | 2003-10-20 |
Family
ID=18458241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35823497A Expired - Fee Related JP3459035B2 (en) | 1997-12-25 | 1997-12-25 | Crosslinkable flame-retardant resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3459035B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4860308B2 (en) * | 2006-03-16 | 2012-01-25 | アイカ工業株式会社 | Flame retardant prepreg and incombustible decorative board |
| JP5827139B2 (en) * | 2012-01-20 | 2015-12-02 | 三井化学株式会社 | Flame retardant resin composition, method for producing the same, molded product thereof, and electric wire |
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1997
- 1997-12-25 JP JP35823497A patent/JP3459035B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11181189A (en) | 1999-07-06 |
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