JPH10298380A - Flame retardant vinyl chloride resin composition - Google Patents
Flame retardant vinyl chloride resin compositionInfo
- Publication number
- JPH10298380A JPH10298380A JP10608997A JP10608997A JPH10298380A JP H10298380 A JPH10298380 A JP H10298380A JP 10608997 A JP10608997 A JP 10608997A JP 10608997 A JP10608997 A JP 10608997A JP H10298380 A JPH10298380 A JP H10298380A
- Authority
- JP
- Japan
- Prior art keywords
- pts
- acid compound
- red phosphorus
- weight
- vinyl chloride
- 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.)
- Abandoned
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は難燃性塩化ビニル樹
脂組成物に関するものである。The present invention relates to a flame-retardant vinyl chloride resin composition.
【０００２】[0002]
【従来の技術】例えば、塩化ビニル樹脂に難燃性を付与
する為にアンチモン系難燃剤（三酸化アンチモン等）、
金属水酸化物（水酸化アルミニウム、水酸化マグネシウ
ム等）等を添加することが行われているが、高い難燃性
を得る為にアンチモン系難燃剤を多量配合するとハロゲ
ン化水素ガスの発生量が多くなるという問題が生じた。
そこでこの発煙量を抑えて難燃化する為に、金属水酸化
物を多量配合すると機械的強度が低下すると共に可撓
性、加工性、耐寒性が低下してしまうという問題も生じ
た。即ち、上記組成の難燃性塩化ビニル樹脂組成物で
は、高い難燃性を得ようとすると塩化水素ガスの発煙量
が増大したり、機械的特性が劣化するという問題があっ
た。2. Description of the Related Art For example, an antimony-based flame retardant (antimony trioxide, etc.) for imparting flame retardancy to vinyl chloride resin,
Metal hydroxides (aluminum hydroxide, magnesium hydroxide, etc.) are added, but if high amounts of antimony-based flame retardants are added to obtain high flame retardancy, the amount of hydrogen halide gas generated will increase. A problem of increasing the number has arisen.
Therefore, when a large amount of a metal hydroxide is blended in order to suppress the amount of generated smoke and make it flame-retardant, there has been a problem that the mechanical strength is reduced and the flexibility, workability and cold resistance are reduced. That is, in the flame-retardant vinyl chloride resin composition having the above-mentioned composition, there is a problem that an attempt to obtain high flame retardancy results in an increase in the amount of generated hydrogen chloride gas smoke and a deterioration in mechanical properties.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、機械的特
性、発煙抑制性及び難燃性が改善された難燃性塩化ビニ
ル樹脂組成物を提供することを課題とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a flame-retardant vinyl chloride resin composition having improved mechanical properties, smoke suppressing properties and flame retardancy.
【０００４】[0004]
【課題を解決するための手段】本発明は、ポリ塩化ビニ
ル１００重量部に対して、金属水酸化物２０〜８０重量
部、モリブデン酸化合物及びリン酸化合物から選択され
る少なくとも１種２〜２５重量部及び赤リン１〜５重量
部を配合してなることを特徴とする難燃性塩化ビニル樹
脂組成物に関するものである。According to the present invention, at least one selected from the group consisting of 20 to 80 parts by weight of a metal hydroxide, a molybdate compound and a phosphoric acid compound is used for 100 parts by weight of polyvinyl chloride. The present invention relates to a flame-retardant vinyl chloride resin composition characterized by comprising 1 part by weight and 1 to 5 parts by weight of red phosphorus.
【０００５】本発明の難燃性塩化ビニル樹脂組成物（以
下、「本発明の組成物」ともいう）は、ポリ塩化ビニル
（ＰＶＣ）に金属水酸化物、モリブデン酸化合物及びリ
ン酸化合物から選択される少なくとも１種及び赤リンを
特定量配合してなる。金属水酸化物、モリブデン酸化合
物及びリン酸化合物から選択される少なくとも１種及び
赤リンの併用は、それら成分の触媒作用によりモリブデ
ン酸化合物単独使用時に比べて本発明の組成物の炭化形
成を促進し、かつハロゲン化水素ガスの発煙量を抑制
し、かつ本発明の組成物の難燃性を向上させる。[0005] The flame-retardant vinyl chloride resin composition of the present invention (hereinafter, also referred to as the "composition of the present invention") is prepared by adding polyvinyl chloride (PVC) to a metal hydroxide, a molybdate compound and a phosphate compound. And at least one red phosphorus and a specific amount of red phosphorus. The combined use of at least one selected from a metal hydroxide, a molybdate compound and a phosphoric acid compound and red phosphorus promotes the carbonization of the composition of the present invention by the catalytic action of these components as compared with the case where the molybdate compound is used alone. And suppresses the amount of smoke generated from the hydrogen halide gas, and improves the flame retardancy of the composition of the present invention.
【０００６】金属水酸化物としては、水酸化アルミニ
ム、水酸化マグネシウム等が挙げられる。金属水酸化物
は、本発明の組成物中、ＰＶＣ１００重量部に対して２
０〜８０重量部配合されるが、好ましくは３０〜７０重
量部の範囲である。モリブデン酸化合物としては、モリ
ブデン酸カルシウム亜鉛、モリブデン酸カリウム、モリ
ブデン酸ナトリウム、モリブデン酸炭酸カルシウム、モ
リブデン酸アンモン等が挙げられ、リン酸化合物として
は燐酸亜鉛等が挙げられる。モリブデン酸化合物及びリ
ン酸化合物から選択される少なくとも１種、好ましくは
モリブデン酸化合物単独またはそれとリン酸化合物との
併用は、本発明の組成物中、ＰＶＣ１００重量部に対し
て２〜２５重量部配合されるが、好ましくは１０〜２５
重量部の範囲である。[0006] Examples of the metal hydroxide include aluminum hydroxide and magnesium hydroxide. Metal hydroxide is used in the composition of the present invention in an amount of 2 parts by weight per 100 parts by weight of PVC.
0 to 80 parts by weight, preferably 30 to 70 parts by weight. Examples of the molybdate compound include calcium zinc molybdate, potassium molybdate, sodium molybdate, calcium molybdate carbonate, and ammonium molybdate, and examples of the phosphate compound include zinc phosphate. At least one selected from a molybdate compound and a phosphate compound, preferably a molybdate compound alone or in combination with a phosphate compound, is used in the composition of the present invention in an amount of 2 to 25 parts by weight per 100 parts by weight of PVC. But preferably 10 to 25
It is in the range of parts by weight.
【０００７】赤リンとしては、通常の赤リンの他、無機
質または有機質で安定化した赤リンを包含する。ただ
し、安定化赤リンの安定化成分は、本発明の配合の計算
からは除外するものとする。赤リンは本発明の組成物
中、ＰＶＣ１００重量部に対して１〜５重量部配合され
る。[0007] The red phosphorus includes not only ordinary red phosphorus but also inorganic or organic stabilized red phosphorus. However, the stabilizing component of stabilized red phosphorus is excluded from the calculation of the formulation of the present invention. Red phosphorus is blended in the composition of the present invention in an amount of 1 to 5 parts by weight based on 100 parts by weight of PVC.
【０００８】本発明の組成物は上記成分の他、通常、可
塑剤、安定剤、充填剤等を含み得る。例えば、ＰＶＣ１
００重量部に対し、可塑剤は、３０〜６０重量部、安定
剤は２〜１０重量部、充填剤は５〜２０重量部を含むこ
とが好ましい。本発明の組成物に使用されるＰＶＣ、可
塑剤、安定剤、充填材等としては、従来公知の以下に例
示するものが挙げられる。[0008] In addition to the above components, the composition of the present invention can usually contain a plasticizer, a stabilizer, a filler and the like. For example, PVC1
It is preferable that the plasticizer contains 30 to 60 parts by weight, the stabilizer contains 2 to 10 parts by weight, and the filler contains 5 to 20 parts by weight with respect to 00 parts by weight. Examples of the PVC, plasticizer, stabilizer, filler and the like used in the composition of the present invention include the following known ones.
【０００９】ＰＶＣとしては、通常、平均重合度ｐ＝１
１００〜２５００のものが挙げられる。可塑剤として
は、フタル酸エステル系｛例えば、ジオクチルフタレー
ト（ＤＯＰ）、ジイソノニルフタレート（ＤＩＮＰ）、
ジイソデシルフタレート（ＤＩＤＰ）、ジウンデシルフ
タレート（ＤＵＰ）等｝、トリメリット酸エステル系
｛例えば、トリオクチルトリメリテート（ＴＯＴＭ）、
トリノルマルオクチルトリメリテート（ＴｎＯＴＭ）
等｝、ポリエステル系等の高分子量可塑剤、例えば、ア
ジピン酸系ポリエステル〔商品名：ＰＮ−３５０（旭電
化（株）製）、ＰＮ−２５０（旭電化（株）製）
等〕）、エポキシ系（例えば、エポキシ化大豆油、エポ
キシ化アマニ油〔商品名：Ｏ−１３０Ｐ（旭電化（株）
製）、Ｏ−１８０Ａ（旭電化（株）製）等〕）等が挙げ
られる。[0009] As PVC, an average degree of polymerization p = 1
100 to 2500. Examples of the plasticizer include phthalate esters such as dioctyl phthalate (DOP), diisononyl phthalate (DINP),
Diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), etc., trimellitate esters, for example, trioctyl trimellitate (TOTM),
Tri-normal octyl trimellitate (TnOTM)
And high molecular weight plasticizers such as polyesters, for example, adipic acid-based polyesters (trade names: PN-350 (manufactured by Asahi Denka Co., Ltd.), PN-250 (manufactured by Asahi Denka Co., Ltd.))
Etc.)), epoxy type (for example, epoxidized soybean oil, epoxidized linseed oil [trade name: O-130P (Asahi Denka Co., Ltd.)
And O-180A (manufactured by Asahi Denka Co., Ltd.)]).
【００１０】安定剤としては、Ｐｂ系（例えば、三塩基
性硫酸鉛、ステアリン酸鉛）、Ｂａ−Ｚｎ系（例えば、
商品名：ＭＡＲＫ ＲＡＰ−１４（旭電化（株）製）、
ＭＡＲＫ ＡＣ−１８６（旭電化（株）製）等〕）、Ｃ
ａ−Ｚｎ系（例えば、〔商品名：ＭＡＲＫ ５９３（旭
電化（株）製）、ＭＡＲＫ ＳＰ−７０（旭電化（株）
製）、シナカレッドＮＬＣ（品川化工（株）製）
等〕）、Ｃａ系（例えば、ステアリン酸カルシウム）、
Ｚｎ系（例えば、ステアリン酸亜鉛）、Ｓｎ系（例え
ば、ジノルマルオクチル錫メルカプト、メチル錫メルカ
プト〔商品名：ＭＡＲＫ４６５（旭電化（株）製）、Ｍ
ＡＲＫ １９２０（旭電化（株）製）等〕）等が挙げら
れる。As a stabilizer, Pb-based (for example, tribasic lead sulfate, lead stearate), Ba-Zn-based (for example,
Product name: MARK RAP-14 (manufactured by Asahi Denka Co., Ltd.),
MARK AC-186 (manufactured by Asahi Denka Co., Ltd.)]), C
a-Zn type (for example, [trade name: MARK 593 (manufactured by Asahi Denka Co., Ltd.)), MARK SP-70 (Asahi Denka Co., Ltd.)
Manufactured), Shinaka Red NLC (manufactured by Shinagawa Kako Co., Ltd.)
Etc.)), Ca-based (for example, calcium stearate),
Zn-based (for example, zinc stearate), Sn-based (for example, dinormal octyltin mercapto, methyltin mercapto [trade name: MARK465 (manufactured by Asahi Denka Co., Ltd.)), M
ARK 1920 (manufactured by Asahi Denka Co., Ltd.)]).
【００１１】充填剤としては、炭酸カルシウム、焼成ク
レー、タルク、シリカ等が挙げられる。本発明の組成物
の用途は、特に制限されるべきものではなく構造部材、
保護部材等に広く用いられる。例えば、構造部材として
は、車両、航空機、船舶等の輸送機器用部材、建造物の
内外装材、家具、事務用具、家電・電子部材等が、ま
た、保護部材としては可燃性製品の保護材、電線、ケー
ブル等の絶縁体・シース等の保護材等が挙げられる。本
発明の組成物を樹脂化したものは、上記各成分を均一に
分散、混合することにより得られ、そして得られた樹脂
の部材または材料への成形加工は、従来公知の方法が適
用される。例えば、押し出し加工する場合は、シリンダ
ー温度１７０〜１９０℃を挙げることができる。Examples of the filler include calcium carbonate, calcined clay, talc, silica and the like. Use of the composition of the present invention is not particularly limited structural members,
Widely used for protection members and the like. For example, as structural members, members for transportation equipment such as vehicles, aircraft, ships, etc., interior and exterior materials of buildings, furniture, office tools, home appliances and electronic members, etc., and as protective members, protective materials for flammable products And insulating materials such as electric wires and cables, and protective materials such as sheaths. A resin of the composition of the present invention is obtained by uniformly dispersing and mixing the above-mentioned components, and a conventionally known method is applied to molding of the obtained resin into members or materials. . For example, when extruding, the cylinder temperature may be 170 to 190 ° C.
【００１２】[0012]
【実施例】以下、本発明の具体的実施例を説明するが、
本発明はこれに限定されるものではない。 実施例１〜７、比較例１〜４ 表１に記載の〜の成分（数値は、重量部）を用いて
塩化ビニル樹脂組成物を調製し、それらの特性を評価し
た。また、評価における目標値も記載した。成分の詳細
及び評価法は以下の通りである。 成分 重合度２０００、商品名 ＴＫ−２００Ｅ、信越化
学（株）製 ジ−２−エチルヘキシルフタレート 三菱化学
（株）製 商品名 ＫＥＭＧＡＲＤ ９１１Ａ、シャーウィン
・ウィリアムズ（株）製 商品名 ハイジライト Ｈ４２Ｍ、昭和電工（株）
製 商品名 ノーバレット＃１２０、燐化工業（株）製 商品名 ＶＩＧＯＴ−１０、白石カルシウム（株）
製 Ｓｂ2 Ｏ3 、商品名 ポリセーフ１００ＮＤ−Ｔ、
味の素（株）製 評価法 酸素指数：ＪＩＳ Ｋ ７２０１に準拠した。 発煙量：ＡＳＴＭ Ｅ ６６２ ＮＢＳ法に準拠した。 引張強さ（ＭＰａ）：ＪＩＳ Ｋ ６７６０に準拠し
た。 伸び（％）：ＪＩＳ Ｋ ６７６０に準拠した。Hereinafter, specific examples of the present invention will be described.
The present invention is not limited to this. Examples 1 to 7 and Comparative Examples 1 to 4 Vinyl chloride resin compositions were prepared using the components (values in parts by weight) shown in Table 1 and their properties were evaluated. The target values in the evaluation are also described. The details of the components and the evaluation method are as follows. Ingredients Degree of polymerization 2000, trade name TK-200E, Shin-Etsu Chemical Co., Ltd. di-2-ethylhexyl phthalate Mitsubishi Chemical Co., Ltd. trade name KEMARD 911A, Sherwin Williams Co., Ltd. trade name Heidilight H42M, Showa Denko (stock)
Product name: Nobaret # 120, product name: VIGOT-10, manufactured by Rinka Kogyo Co., Ltd., Shiraishi Calcium Co., Ltd.
Sb 2 O 3 , trade name Polysafe 100ND-T,
Evaluation method manufactured by Ajinomoto Co., Inc. Oxygen index: Based on JIS K7201. Smoke generation: based on ASTM E662 NBS method. Tensile strength (MPa): Based on JIS K 6760. Elongation (%): Based on JIS K 6760.
【００１３】[0013]
【表１】 [Table 1]
【００１４】表１からモリブデン酸化合物を含まない比
較例１及びモリブデン酸化合物を含むが金属水酸化物及
び赤リンを含まない比較例３は、発煙量が改善されず、
モリブデン酸化合物及び金属水酸化物を過剰に含む比較
例２は引張り強さが劣る。また、モリブデン酸化合物、
金属水酸化物及び赤リンの配合量が少ない本発明範囲外
の組成物である比較例４は、発煙量及び難燃性が改善さ
れないことが分かる。一方、モリブデン酸化合物、金属
水酸化物及び赤リンの配合割合が本発明の範囲である実
施例は、全ての評価項目において優れていることが分か
る。From Table 1, Comparative Example 1 containing no molybdate compound and Comparative Example 3 containing a molybdate compound but no metal hydroxide and red phosphorus showed no improvement in the amount of smoke generated.
Comparative Example 2, which contains a molybdate compound and a metal hydroxide in excess, has poor tensile strength. A molybdate compound;
It can be seen that Comparative Example 4, which is a composition containing less amounts of metal hydroxide and red phosphorus, which is out of the range of the present invention, does not improve the amount of smoke and the flame retardancy. On the other hand, it can be seen that the examples in which the mixing ratios of the molybdate compound, metal hydroxide and red phosphorus are within the scope of the present invention are excellent in all evaluation items.
【００１５】[0015]
【発明の効果】本発明の難燃性塩化ビニル樹脂組成物
は、ＰＶＣに金属水酸化物、モリブデン酸化合物及びリ
ン酸化合物から選択される少なくとも１種及び赤リンを
特定量配合することにより、酸化状況下において炭化形
成を促進し、かつハロゲン化水素ガスの発煙量を抑制
し、かつ難燃性を向上させる。The flame-retardant vinyl chloride resin composition of the present invention is obtained by blending at least one selected from a metal hydroxide, a molybdic acid compound and a phosphoric acid compound and red phosphorus into PVC in a specific amount. It promotes carbonization under oxidizing conditions, suppresses the amount of smoke generated from hydrogen halide gas, and improves flame retardancy.
Claims (2)
金属水酸化物２０〜８０重量部、モリブデン酸化合物及
びリン酸化合物から選択される少なくとも１種２〜２５
重量部及び赤リン１〜５重量部を配合してなることを特
徴とする難燃性塩化ビニル樹脂組成物。[Claim 1] 100 parts by weight of polyvinyl chloride,
20 to 80 parts by weight of metal hydroxide, at least one selected from molybdate compounds and phosphoric acid compounds
A flame-retardant vinyl chloride resin composition characterized by comprising 1 part by weight of red phosphorus and 1 to 5 parts by weight of red phosphorus.
あり、モリブデン酸化合物が、モリブデン酸カルシウム
亜鉛であることを特徴とする請求項１記載の難燃性塩化
ビニル樹脂組成物。2. The flame-retardant vinyl chloride resin composition according to claim 1, wherein the metal hydroxide is aluminum hydroxide and the molybdate compound is calcium zinc molybdate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10608997A JPH10298380A (en) | 1997-04-23 | 1997-04-23 | Flame retardant vinyl chloride resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10608997A JPH10298380A (en) | 1997-04-23 | 1997-04-23 | Flame retardant vinyl chloride resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10298380A true JPH10298380A (en) | 1998-11-10 |
Family
ID=14424832
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10608997A Abandoned JPH10298380A (en) | 1997-04-23 | 1997-04-23 | Flame retardant vinyl chloride resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10298380A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030040954A (en) * | 2001-11-17 | 2003-05-23 | 엘지전선 주식회사 | High inflammable and low emitting smoke material composition |
| KR100435032B1 (en) * | 2001-11-17 | 2004-06-09 | 엘지전선 주식회사 | Low emitting smoke and high inflammable material composition |
| KR100863282B1 (en) * | 2006-09-14 | 2008-10-15 | 동국대학교 산학협력단 | Synthetic method for metal hydroxide phosphate |
| KR100863285B1 (en) * | 2006-09-14 | 2008-10-15 | 동국대학교 산학협력단 | Flame retardant agent including metal hydroxide phosphate for PVC flame retardant |
-
1997
- 1997-04-23 JP JP10608997A patent/JPH10298380A/en not_active Abandoned
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030040954A (en) * | 2001-11-17 | 2003-05-23 | 엘지전선 주식회사 | High inflammable and low emitting smoke material composition |
| KR100435032B1 (en) * | 2001-11-17 | 2004-06-09 | 엘지전선 주식회사 | Low emitting smoke and high inflammable material composition |
| KR100863282B1 (en) * | 2006-09-14 | 2008-10-15 | 동국대학교 산학협력단 | Synthetic method for metal hydroxide phosphate |
| KR100863285B1 (en) * | 2006-09-14 | 2008-10-15 | 동국대학교 산학협력단 | Flame retardant agent including metal hydroxide phosphate for PVC flame retardant |
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