JP2006282788A - Polyolefin-based resin composition and its molding - Google Patents

Polyolefin-based resin composition and its molding Download PDF

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JP2006282788A
JP2006282788A JP2005102825A JP2005102825A JP2006282788A JP 2006282788 A JP2006282788 A JP 2006282788A JP 2005102825 A JP2005102825 A JP 2005102825A JP 2005102825 A JP2005102825 A JP 2005102825A JP 2006282788 A JP2006282788 A JP 2006282788A
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resin composition
polyolefin
based resin
nitrogen atom
hydrogen cyanide
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Inventor
Takehiko Nakamura
毅彦 中村
Shingo Takada
新吾 高田
Koji Tanaka
幸治 田中
Hideki Uchiumi
秀樹 内海
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polyolefin-based resin composition that controls generation of hydrogen cyanide in combustion even in combustion by conventional incineration facilities and contains organic pigment containing a nitrogen atom and its molding. <P>SOLUTION: The polyolefin-based resin and its molding comprise (A) a polyolefin-based resin, (B) organic pigment containing a nitrogen atom and (C) calcined dolomite or its hydrate. The polyolefin-based resin composition controls generation of hydrogen cyanide in its combustion in spite of containing organic pigment containing a nitrogen atom. Consequently, since the resin composition controls generation of poisonous gas in fire, it is suitable for a building material such as wallpaper, etc. Since the resin composition is incinerated with controlling generation of poisonous gas, the resin composition is suitably useful for various kinds of containers, waste bags, etc. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、燃焼時にシアン化水素の発生が抑制される窒素原子を有する有機顔料含有のポリオレフィン系樹脂組成物及びその成形品に関する。   The present invention relates to an organic pigment-containing polyolefin resin composition having a nitrogen atom that suppresses the generation of hydrogen cyanide during combustion, and a molded article thereof.

多くの有機顔料はその構造中に窒素原子を有するため、燃焼条件によってシアン化水素等の有毒ガスを発生する問題があった。特に火災時の燃焼では、燃焼温度が高くないため、シアン化水素の発生は避けられないものであった。   Many organic pigments have nitrogen atoms in their structures, and thus have a problem of generating toxic gases such as hydrogen cyanide depending on combustion conditions. Especially in the case of combustion in a fire, the generation temperature of hydrogen cyanide was inevitable because the combustion temperature was not high.

この問題を解決する方法としては、燃焼又は熱分解した際に有毒ガスが発生するおそれのある廃有機物を、超臨界水下で脱水素及び/又は酸化触媒と接触させ処理することにより、有毒ガスの発生を抑制する方法が提案されている(例えば、特許文献1参照。)。   As a method for solving this problem, a waste organic substance that may generate a toxic gas upon combustion or thermal decomposition is treated by contacting it with a dehydrogenation and / or oxidation catalyst under supercritical water. There has been proposed a method for suppressing the occurrence of (see, for example, Patent Document 1).

また、加熱分解処理中に発生した分解ガス(有毒ガス)を高温で燃焼することで有害物質を熱分解する方法が提案されている(例えば、特許文献2参照。)。しかしながら、これらの方法では、大規模な処理設備が必要となり、従来の焼却設備では処理できない問題があった。また、火災時の燃焼で、シアン化水素の発生を抑制する有効な手段もなかった。   In addition, a method has been proposed in which a harmful substance is thermally decomposed by burning a decomposition gas (toxic gas) generated during the heat decomposition treatment at a high temperature (see, for example, Patent Document 2). However, these methods require a large-scale treatment facility, and have a problem that the conventional incineration facility cannot treat. In addition, there was no effective means for suppressing the generation of hydrogen cyanide during combustion in a fire.

一方、仮焼ドロマイト又はその水和物を含有する塩化ビニル系樹脂組成物が提案されている(例えば、特許文献3参照。)。この樹脂組成物のベース樹脂は、本発明のポリオレフィン系樹脂ではなく塩化ビニル系樹脂であり、その目的もダイオキシン類の発生抑制であり、本発明の目的であるシアン化水素の発生抑制とは異なる。
特開平11−263871号公報 特開2002−172378号公報 特開2003−253070号公報
On the other hand, a vinyl chloride resin composition containing calcined dolomite or a hydrate thereof has been proposed (see, for example, Patent Document 3). The base resin of this resin composition is not a polyolefin resin of the present invention but a vinyl chloride resin, and its purpose is to suppress the generation of dioxins, which is different from the suppression of the generation of hydrogen cyanide, which is the object of the present invention.
JP-A-11-263871 JP 2002-172378 A JP 2003-253070 A

本発明の目的は、従来の焼却設備で燃焼させても、燃焼時のシアン化水素の発生を抑制することのできる窒素原子を有する有機顔料含有のポリオレフィン系樹脂組成物及びその成形品を提供することである。   An object of the present invention is to provide an organic pigment-containing polyolefin-based resin composition having a nitrogen atom that can suppress generation of hydrogen cyanide during combustion even when burned in a conventional incineration facility, and a molded product thereof. is there.

本発明者は、上記課題を解決すべく鋭意検討した結果、窒素原子を有する有機顔料含有のポリオレフィン系樹脂組成物に仮焼ドロマイト又はその水和物を含有させることにより、燃焼時のシアン化水素の発生を抑制することができることを見出した。   As a result of intensive studies to solve the above problems, the present inventor has generated hydrogen cyanide during combustion by adding calcined dolomite or a hydrate thereof to a polyolefin resin composition containing an organic pigment having a nitrogen atom. It was found that it can be suppressed.

すなわち、本発明は、(A)ポリオレフィン系樹脂、
(B)窒素原子を有する有機顔料及び
(C)仮焼ドロマイト又はその水和物
を含有することを特徴とするポリオレフィン系樹脂組成物及びその成形物を提供するものである。
That is, the present invention provides (A) a polyolefin resin,
(B) An organic pigment having a nitrogen atom and (C) a calcined dolomite or a hydrate thereof are provided to provide a polyolefin resin composition and a molded product thereof.

本発明のポリオレフィン系樹脂組成物は、窒素原子を有する有機顔料を含有していても、その燃焼時のシアン化水素の発生を抑制することができる。このため、火災時の有毒ガスの発生を抑制できることから、壁紙等の建材に好適である。また、有毒ガスの発生を抑制した焼却処分が可能なので、各種容器、ゴミ袋等にも好適に用いることができる。   Even if the polyolefin resin composition of the present invention contains an organic pigment having a nitrogen atom, generation of hydrogen cyanide during combustion can be suppressed. For this reason, since generation | occurrence | production of the toxic gas at the time of a fire can be suppressed, it is suitable for building materials, such as a wallpaper. Moreover, since incineration disposal which suppressed generation | occurrence | production of toxic gas is possible, it can use suitably also for various containers, a garbage bag, etc.

本発明の用いられるポリオレフィン系樹脂(A)としては、例えば、ポリエチレン及びその共重合体、低分子量ポリエチレンワックス、ポリプロピレン及びプロピレンとプロピレン以外の重合性エチレン基を有するアルキレンとの共重合体等が挙げられる。また、これらの樹脂を単独で用いても、2種以上を併用しても良い。なお、これらのポリオレフィン系樹脂(A)の配合比率は、樹脂組成物中19.95〜99.9質量%である。   Examples of the polyolefin resin (A) used in the present invention include polyethylene and copolymers thereof, low molecular weight polyethylene wax, polypropylene and copolymers of propylene and alkylene having a polymerizable ethylene group other than propylene. It is done. These resins may be used alone or in combination of two or more. In addition, the compounding ratio of these polyolefin resin (A) is 19.95-99.9 mass% in a resin composition.

本発明の用いられる窒素原子を有する有機顔料(B)としては、窒素原子を有していれば特に制限なし用いることができるが、例えば、アゾ系顔料、アントラキノン系顔料、縮合多環系顔料、塩基性染料系顔料、酸性染料系顔料、有機蛍光顔料等が挙げられる。特に、フタロシアニン系顔料、ジスアゾ系顔料は窒素原子を多く有するため、シアン化水素の発生量が多いので、本発明によるシアン化水素の発生を抑制する効果が大きくなる。また、これらの有機顔料を単独で用いても、2種以上を併用しても良い。なお、これらの有機顔料(B)の配合比率は、樹脂組成物中0.05〜80質量%である。   The organic pigment (B) having a nitrogen atom used in the present invention can be used without particular limitation as long as it has a nitrogen atom. For example, an azo pigment, an anthraquinone pigment, a condensed polycyclic pigment, Examples include basic dye pigments, acid dye pigments, and organic fluorescent pigments. In particular, since phthalocyanine pigments and disazo pigments have a large amount of nitrogen atoms, a large amount of hydrogen cyanide is generated, so that the effect of suppressing the generation of hydrogen cyanide according to the present invention is increased. These organic pigments may be used alone or in combination of two or more. In addition, the compounding ratio of these organic pigments (B) is 0.05 to 80% by mass in the resin composition.

本発明に用いられる仮焼ドロマイト(C)は、塊状ドロマイト(カルシウムとマグネシウムの複合炭酸塩鉱物、化学組成:CaCO・MgCO)を仮焼温度900℃〜1200℃で加熱し、結晶内の炭酸部分をガスとして放出させ、その表面に多数の凹凸のあるスポンジ状にした酸化カルシウムと酸化マグネシウムの混合物である。また、仮焼ドロマイトの水和物は、仮焼ドロマイトを消化して水和物としたものであり、水酸化カルシウム(炭酸ガスが未分解の炭酸カルシウムを含む)と水酸化マグネシウム及び水と未反応の酸化マグネシウムの混合物である。なお、仮焼ドロマイト及びその水和物は、特開2003−253070に開示されているものを用いることができ、その平均粒径は0.1〜5μmのものが好ましい。仮焼ドロマイト又はその水和物(C)の配合比率は、樹脂組成物中の0.05〜80%質量%である。 The calcined dolomite (C) used in the present invention is obtained by heating massive dolomite (composite carbonate mineral of calcium and magnesium, chemical composition: CaCO 3 .MgCO 3 ) at a calcining temperature of 900 ° C. to 1200 ° C. This is a mixture of calcium oxide and magnesium oxide in which the carbonic acid portion is released as a gas and is made into a sponge shape with a large number of irregularities on the surface. In addition, the hydrate of calcined dolomite is obtained by digesting calcined dolomite to obtain a hydrate, which includes calcium hydroxide (including carbon dioxide in which carbon dioxide is undecomposed), magnesium hydroxide, water, It is a mixture of magnesium oxide in the reaction. In addition, the calcined dolomite and its hydrate can use what is disclosed by Unexamined-Japanese-Patent No. 2003-253070, and the average particle diameter has a preferable thing of 0.1-5 micrometers. The compounding ratio of calcined dolomite or its hydrate (C) is 0.05 to 80% by mass in the resin composition.

本発明のポリオレフィン系樹脂組成物には、必要に応じて、ポリオレフィン系以外の樹脂、金属石鹸、酸化防止剤、光安定剤等の添加剤を添加することができる。   If necessary, additives such as resins other than polyolefin resins, metal soaps, antioxidants, and light stabilizers can be added to the polyolefin resin composition of the present invention.

本発明のポリオレフィン系樹脂組成物は、該樹脂組成物中の成分(B)及び成分(C)を高濃度に含有するマスターバッチとしても用いることができる。この際の成分(A)〜(C)の各配合比率は、下記の範囲が好ましい。なお、このマスターバッチは、使用の際に所望とする濃度になるように、ポリオレフィン系樹脂(A)で希釈して用いる。
ポリオレフィン系樹脂(A):19.9〜99.8質量%
窒素原子を有する有機顔料(B):0.1〜80質量%
仮焼ドロマイト又はその水和物(C):0.1〜80質量%
The polyolefin resin composition of the present invention can also be used as a master batch containing the component (B) and the component (C) in the resin composition at a high concentration. The following ranges are preferable for each compounding ratio of components (A) to (C) at this time. In addition, this masterbatch is used by diluting with the polyolefin resin (A) so as to have a desired concentration in use.
Polyolefin resin (A): 19.9 to 99.8% by mass
Organic pigment having nitrogen atom (B): 0.1 to 80% by mass
Calcined dolomite or its hydrate (C): 0.1 to 80% by mass

本発明の成形物は、前記ポリオレフィン系樹脂組成物を用いて、押出成形、射出成形、カレンダー成形、Tダイ成形、インフレーション成形、真空成形等の成形方法により作製することができる。   The molded product of the present invention can be produced using the polyolefin resin composition by a molding method such as extrusion molding, injection molding, calendar molding, T-die molding, inflation molding, or vacuum molding.

本発明の成形物の具体例として、フィルム、シート、プレート、各種容器、繊維等が挙げられる。これらの中でも、使用後に焼却処分される各種容器やフィルムからなるゴミ袋が好適である。また、火災時に燃焼する可能性のあるシートからなる壁紙等の建材にも好適に用いることができる。   Specific examples of the molded product of the present invention include films, sheets, plates, various containers, fibers and the like. Among these, garbage bags made of various containers and films that are incinerated after use are suitable. Moreover, it can use suitably also for building materials, such as a wallpaper which consists of a sheet | seat which may burn at the time of a fire.

また、本発明の成形物は、燃焼時のシアン化水素の発生量を大幅に抑制できるが、そのシアン化水素の発生量は、750℃、10分間の燃焼で0.2mg/g以下であることが好ましい。   The molded product of the present invention can greatly suppress the amount of hydrogen cyanide generated during combustion, but the amount of hydrogen cyanide generated is preferably 0.2 mg / g or less after burning at 750 ° C. for 10 minutes.

以下、本発明を実施例により説明する。また、特に断わりのない限り「部」、「%」は質量基準である。   Hereinafter, the present invention will be described by way of examples. Unless otherwise specified, “parts” and “%” are based on mass.

(実施例1)
低密度ポリエチレン(日本ポリエチレン株式会社製「ノバテックLDPE LF−521H」)95.5部、ベンツイミダゾロン系有機顔料(クラリアント社製「PV FAST YELLOW HG」)1.5部及び仮焼ドロマイト水和物(用瀬電機株式会社製「デキシノン」)3部を押出機(田辺プラスチック機械株式会社製「VS−30系押出機」)にて溶融混合し、これをダイスからストランド状に押し出した後、カッティングして樹脂組成物のペレットを得た。
Example 1
95.5 parts of low density polyethylene (Nippon Polyethylene "Novatech LDPE LF-521H"), 1.5 parts of benzimidazolone organic pigment (Clariant "PV FAST YELLOW HG") and calcined dolomite hydrate 3 parts (“Dexinone” manufactured by Yose Electric Co., Ltd.) were melt mixed with an extruder (“VS-30 extruder” manufactured by Tanabe Plastic Machinery Co., Ltd.), extruded into a strand from a die, and then cut. Thus, pellets of the resin composition were obtained.

(実施例2)
実施例1で用いた低密度ポリエチレンを93.7部、仮焼ドロマイト水和物を4.8部に変更した以外は実施例1と同様に行い、樹脂組成物のペレットを得た。
(Example 2)
Except that the low density polyethylene used in Example 1 was changed to 93.7 parts and calcined dolomite hydrate was changed to 4.8 parts, it was carried out in the same manner as in Example 1 to obtain pellets of the resin composition.

(実施例3)
実施例1で用いた低密度ポリエチレンを92.5部、仮焼ドロマイト水和物を6部に変更した以外は実施例1と同様に行い、樹脂組成物のペレットを得た。
(Example 3)
Except that the low density polyethylene used in Example 1 was changed to 92.5 parts and calcined dolomite hydrate was changed to 6 parts, a resin composition pellet was obtained in the same manner as in Example 1.

(比較例1)
低密度ポリエチレン(日本ポリエチレン株式会社製「ノバテックLDPE LF−521H」)98.5部及びベンツイミダゾロン系有機顔料(クラリアント社製「PV FAST YELLOW HG」)1.5部を押出機(田辺プラスチック機械株式会社製「VS−30系押出機」)にて溶融混合し、これをダイスからストランド状に押し出した後、カッティングして樹脂組成物のペレットを得た。
(Comparative Example 1)
Extruder (Tanabe Plastic Machinery Co., Ltd.) 98.5 parts of low density polyethylene (“Novatech LDPE LF-521H” manufactured by Nippon Polyethylene Co., Ltd.) and 1.5 parts of Benzimidazolone organic pigment (“PV FAST YELLOW HG” manufactured by Clariant) It was melt-mixed with a “VS-30 extruder” manufactured by Co., Ltd., extruded into a strand from a die, and then cut to obtain a pellet of a resin composition.

(比較例2)
実施例1で用いた仮焼ドロマイト水和物3部を沈降性硫酸バリウム(バライト工業株式会社製「沈降性硫酸バリウムST」)3部に変更した以外は実施例1と同様に行い、樹脂組成物のペレットを得た。
(Comparative Example 2)
Resin composition was carried out in the same manner as in Example 1 except that 3 parts of the calcined dolomite hydrate used in Example 1 was changed to 3 parts of precipitated barium sulfate (“Precipitated Barium Sulfate ST” manufactured by Barite Industries Co., Ltd.). A product pellet was obtained.

(評価用フィルムの作成)
実施例1〜3及び比較例1、2で得られた樹脂組成物のペレットをインフレーションフィルム成形機(トミー機械工業株式会社製「TMS−30−24」)を用いて成形しフィルムを作製した。
(Creation of evaluation film)
Pellets of the resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were molded using an inflation film molding machine (“TMS-30-24” manufactured by Tommy Machinery Co., Ltd.) to produce a film.

(燃焼試験)
日本工業規格JIS K7217−1983「プラスチック燃焼ガスの分析方法」に準拠して、上記で得られたフィルムを0.1g採取し、750℃で10分間燃焼して、シアン化水素の発生量を測定した。
(Combustion test)
In accordance with Japanese Industrial Standard JIS K7217-1983 “Analyzing Method of Plastic Combustion Gas”, 0.1 g of the film obtained above was sampled, burned at 750 ° C. for 10 minutes, and the amount of hydrogen cyanide generated was measured.

実施例1〜3及び比較例1、2の評価結果を表1に示す。   The evaluation results of Examples 1 to 3 and Comparative Examples 1 and 2 are shown in Table 1.

Figure 2006282788
Figure 2006282788

表1に示した結果から、実施例1〜3で得た本発明のポリオレフィン系樹脂組成物の燃焼時のシアン化水素の発生量は0.09〜0.12mg/gであり、仮焼ドロマイト水和物を配合しなかった比較例1のシアン化水素の発生量0.51mg/gと比較し、燃焼時のシアン化水素の発生量を約1/5にまで大幅に抑制できることが確認できた。   From the results shown in Table 1, the amount of hydrogen cyanide generated during combustion of the polyolefin resin compositions of the present invention obtained in Examples 1 to 3 was 0.09 to 0.12 mg / g, and calcined dolomite hydration As compared with the amount of hydrogen cyanide generated in Comparative Example 1 in which no product was added, 0.51 mg / g, it was confirmed that the amount of hydrogen cyanide generated during combustion could be significantly suppressed to about 1/5.

比較例2は、仮焼ドロマイト又はその水和物でない無機フィラーを配合した例であるが、シアン化水素の発生量が0.35mg/gとなり、燃焼時のシアン化水素の発生が抑制できないことが確認できた。


Comparative Example 2 is an example in which an inorganic filler that is not calcined dolomite or its hydrate is blended, and the amount of hydrogen cyanide generated was 0.35 mg / g, and it was confirmed that the generation of hydrogen cyanide during combustion could not be suppressed. .


Claims (4)

(A)ポリオレフィン系樹脂、
(B)窒素原子を有する有機顔料及び
(C)仮焼ドロマイト又はその水和物
を含有することを特徴とするポリオレフィン系樹脂組成物。
(A) polyolefin resin,
(B) A polyolefin resin composition comprising an organic pigment having a nitrogen atom and (C) calcined dolomite or a hydrate thereof.
前記ポリオレフィン系樹脂(A)の含有量が19.95〜99.9質量%、窒素原子を有する有機顔料(B)の含有量が0.05〜80質量%、仮焼ドロマイト及び/又はその水和物(C)の含有量が0.05〜80質量%である請求項1記載のポリオレフィン系樹脂組成物。 The content of the polyolefin resin (A) is 19.95 to 99.9% by mass, the content of the organic pigment (B) having a nitrogen atom is 0.05 to 80% by mass, calcined dolomite and / or water thereof The polyolefin resin composition according to claim 1, wherein the content of the sum (C) is 0.05 to 80% by mass. 前記仮焼ドロマイト又はその水和物(C)の平均粒径が0.1〜5μmである請求項1又は2記載のポリオレフィン系樹脂組成物。 The polyolefin resin composition according to claim 1 or 2, wherein an average particle diameter of the calcined dolomite or a hydrate (C) thereof is 0.1 to 5 µm. 請求項1〜3のいずれか1項記載のポリオレフィン系樹脂組成物からなることを特徴とする成形物。


A molded article comprising the polyolefin resin composition according to any one of claims 1 to 3.


JP2005102825A 2005-03-31 2005-03-31 Polyolefin-based resin composition and its molding Pending JP2006282788A (en)

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