JP2800282B2 - Method for producing thermoplastic resin composition - Google Patents

Method for producing thermoplastic resin composition

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Publication number
JP2800282B2
JP2800282B2 JP17748389A JP17748389A JP2800282B2 JP 2800282 B2 JP2800282 B2 JP 2800282B2 JP 17748389 A JP17748389 A JP 17748389A JP 17748389 A JP17748389 A JP 17748389A JP 2800282 B2 JP2800282 B2 JP 2800282B2
Authority
JP
Japan
Prior art keywords
thermoplastic resin
kneading
expandable graphite
resin composition
heat
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 - Lifetime
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JP17748389A
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Japanese (ja)
Other versions
JPH0341161A (en
Inventor
武嗣 鈴木
春雄 坂上
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Kasei Chemical Co Ltd
Original Assignee
Nippon Kasei Chemical Co Ltd
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Priority to JP17748389A priority Critical patent/JP2800282B2/en
Publication of JPH0341161A publication Critical patent/JPH0341161A/en
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Description

【発明の詳細な説明】 [産業上の利用分野] 本発明は難燃性の改善された熱可塑性樹脂組成物に関
する。本発明の組成物はプラスチック成形の分野で利用
される。
The present invention relates to a thermoplastic resin composition having improved flame retardancy. The composition of the present invention is used in the field of plastic molding.

[従来の技術] 熱可塑性樹脂、とりわけポリエチレン、ポリプロピレ
ン、ポリスチレン、ポリ塩化ビニール等の汎用樹脂製品
は、日用品、玩具、電化製品、建築資材等の分野できわ
めて多量に生産、使用されているが、何れも高温下で融
解し、また、火焔に接すると容易に燃焼するため、各種
の方法で難燃化処理が施されている。難燃化方法として
広く用いられている方法には、ハロゲン化合物、ハロゲ
ン化リン酸エステル化合物、金属水酸化物、金属酸化
物、三酸化アンチモン等を樹脂に含有させる方法があ
る。
[Prior art] Thermoplastic resins, especially general-purpose resin products such as polyethylene, polypropylene, polystyrene, and polyvinyl chloride, are produced and used in extremely large quantities in the fields of daily necessities, toys, electric appliances, building materials, and the like. Since all of them melt at high temperatures and burn easily when they come into contact with a flame, they have been subjected to flame retarding treatment by various methods. As a method widely used as a flame retarding method, there is a method in which a resin contains a halogen compound, a halogenated phosphate compound, a metal hydroxide, a metal oxide, antimony trioxide, or the like.

また、かかる目的を達成する別の手段として、米国特
許第3,574,644号にはポリエチレンに熱膨張性黒鉛を添
加することにより難燃性を高める方法が提案されてい
る。
Further, as another means for achieving such an object, US Pat. No. 3,574,644 proposes a method of increasing flame retardancy by adding thermally expandable graphite to polyethylene.

しかしながら、従来公知の方法で得られる熱膨張性黒
鉛を含有する熱可塑性樹脂組成物は難燃性が必ずしも良
好でないばかりでなく、熱膨張性黒鉛を混練する際、該
熱膨張性黒鉛に含有される硫酸を主成分とすると思われ
る酸性ガスが発生し、装置を腐食する恐れがある等の問
題が認められた。
However, the thermoplastic resin composition containing the heat-expandable graphite obtained by a conventionally known method is not only not necessarily excellent in flame retardancy, but also contained in the heat-expandable graphite when kneading the heat-expandable graphite. However, problems such as the generation of an acidic gas presumably containing sulfuric acid as a main component and the possibility of corroding the apparatus were observed.

[発明が解決しようとする課題] 本発明は、熱膨張性黒鉛を熱可塑性樹脂に添加、混練
する際、有害な酸性ガスの発生がなく、かつ、難燃性の
優れた熱可塑性樹脂組成物を製造する方法を提供しよう
とするものである。
[Problems to be Solved by the Invention] The present invention relates to a thermoplastic resin composition which does not generate harmful acidic gas when adding and kneading thermally expandable graphite to a thermoplastic resin and has excellent flame retardancy. It is intended to provide a method for producing the.

[課題を解決するための手段] 上記問題点を解決するために、本発明者らは鋭意検討
した結果、特定の熱膨張性黒鉛と熱可塑性樹脂を特定の
温度条件下で混練することによって上記の課題を解決し
うることを見出した。即ち、本発明は、熱可塑性樹脂と
1重量%水分散液のpHが4.5以上の熱膨張性黒鉛を、該
熱可塑性樹脂と熱膨張性黒鉛の混練混合物の温度を210
℃以下に保持して混練することを特徴とする熱可塑性樹
脂組成物の製造方法を要旨とするものである。以下に本
発明を詳細に説明する。
Means for Solving the Problems In order to solve the above problems, the present inventors have conducted intensive studies and as a result, kneaded a specific heat-expandable graphite and a thermoplastic resin under a specific temperature condition, thereby Has been found to be able to solve the above problems. That is, in the present invention, a thermoplastic resin and a 1% by weight aqueous dispersion of a heat-expandable graphite having a pH of 4.5 or more are mixed with a kneaded mixture of the thermoplastic resin and the heat-expandable graphite at a temperature of 210%.
A gist of the present invention is a method for producing a thermoplastic resin composition, which comprises kneading while maintaining the temperature at a temperature of not more than ° C. Hereinafter, the present invention will be described in detail.

本発明に使用される熱膨張性黒鉛の原料黒鉛、製造方
法には特に制限はないが、その特性としては、1000℃で
10秒間、急激に加熱するときの膨張度が50〜250ml/gで
あることが望ましく、このような熱膨張性黒鉛は、例え
ば、98%濃硫酸と60%過酸化水素水の混合物中におよそ
20〜100メッシュに粉砕された黒鉛を、45℃以下で10分
〜30分接触させ、水洗、乾燥を行うことにより製造する
ことが出来る。
The raw graphite of the heat-expandable graphite used in the present invention, the production method is not particularly limited, but as its characteristics, at 1000 ℃
Desirably, the degree of expansion when rapidly heated for 10 seconds is 50 to 250 ml / g. Such a heat-expandable graphite is, for example, approximately in a mixture of 98% concentrated sulfuric acid and 60% hydrogen peroxide solution.
It can be produced by bringing graphite crushed to 20 to 100 mesh into contact at 45 ° C. or lower for 10 to 30 minutes, washing with water, and drying.

熱膨張性黒鉛の膨張度は、一般に該熱膨張性黒鉛の粒
度に左右され、粒度がおよそ80メッシュより細かくなる
と、膨張性が小さくなる傾向があり、150メッシュより
細かい場合は、膨張度が極端に低下し、その結果、熱可
塑性樹脂組成物製品の難燃化効果は著しく低下する。
The degree of expansion of the heat-expandable graphite generally depends on the particle size of the heat-expandable graphite.When the particle size is smaller than about 80 mesh, the expandability tends to be small.When the particle size is smaller than 150 mesh, the expansion degree is extremely large. As a result, the flame retardant effect of the thermoplastic resin composition product is significantly reduced.

従って、本発明で使用される熱膨張性黒鉛の粒度は、
100メッシュより大きいものが望ましい。一方、20メッ
シュより大きいものは膨張度も大きく、難燃性付与の点
では効果があるが、熱可塑性樹脂と混練する際、樹脂中
への分散性が低下することがある。
Therefore, the particle size of the thermally expandable graphite used in the present invention,
Those larger than 100 mesh are desirable. On the other hand, those having a size larger than 20 mesh have a large expansion degree and are effective in imparting flame retardancy, but when kneaded with a thermoplastic resin, dispersibility in the resin may be reduced.

熱膨張性黒鉛の粒度は、通常、これを製造する際の原
料黒鉛の粒度に依存しているので、粒度の調整を原料黒
鉛で行ってもよく、また膨張後の黒鉛を粉砕して分級し
て行ってもよい。
Since the particle size of the heat-expandable graphite usually depends on the particle size of the raw graphite at the time of manufacturing the same, the particle size may be adjusted with the raw graphite, and the expanded graphite may be pulverized and classified. You may go.

本発明で使用される熱膨張性黒鉛は、その1重量%水
分散液のpHが4.5以上、好ましくは4.5〜10の範囲にある
ことが必要である。pHが4.5未満では混練作業中、酸性
ガスが発生し、また得られる熱可塑性樹脂組成物の難燃
性の改善も十分とはいえない。1重量%水分散液のpHが
4.5以上の熱膨張性黒鉛は、上記酸処理後の黒鉛の水洗
をくり返し、過剰の酸を除去することによっても得られ
るが、ある程度水洗を行った後、アンモニア、脂肪族低
級アミン、アルカリ金属化合物或いはアルカリ土類金属
化合物で中和して得ることもできる。熱可塑性樹脂組成
物の難燃性改善の点及び熱膨張性黒鉛の製造工程におけ
る排水処理の点からも、中和処理を施した熱膨張性黒鉛
を用いることが好ましい。
The 1-% by weight aqueous dispersion of the heat-expandable graphite used in the present invention needs to have a pH of 4.5 or more, preferably in the range of 4.5 to 10. If the pH is less than 4.5, an acidic gas is generated during the kneading operation, and the flame retardancy of the obtained thermoplastic resin composition is not sufficiently improved. PH of 1% by weight aqueous dispersion
Thermal expandable graphite of 4.5 or more can be obtained by repeatedly washing the graphite after the above-mentioned acid treatment and removing excess acid, but after washing to some extent, ammonia, aliphatic lower amine, alkali metal compound Alternatively, it can be obtained by neutralization with an alkaline earth metal compound. From the viewpoint of improving the flame retardancy of the thermoplastic resin composition and the wastewater treatment in the production process of the heat-expandable graphite, it is preferable to use the heat-expandable graphite subjected to the neutralization treatment.

脂肪族低級アミンとしては、モノメチルアミン、ジメ
チルアミン、トリメチルアミン、エチルアミン、プロピ
ルアミン、ブチルアミンが挙げられる。
Examples of the aliphatic lower amine include monomethylamine, dimethylamine, trimethylamine, ethylamine, propylamine, and butylamine.

アルカリ金属化合物及びアルカリ土類金属化合物とし
ては、カリウム、ナトリウム、カルシウム、バリウム又
はマグネシウムの水酸化物、酸化物、炭酸塩、硫酸塩、
有機酸塩から選ばれる化合物が挙げられる。
As the alkali metal compound and the alkaline earth metal compound, potassium, sodium, calcium, barium or magnesium hydroxide, oxide, carbonate, sulfate,
And compounds selected from organic acid salts.

これらの中、好ましい具体例としては、アンモニア、
苛性カリ、苛性ソーダ、炭酸カリ、炭酸ソーダ、ギ酸ソ
ーダ、酢酸ソーダ、クエン酸ソーダ、水酸化カルシウ
ム、水酸化バリウム、水酸化マグネシウム、炭酸カルシ
ウム、炭酸バリウム、炭酸マグネシウム、酢酸カルシウ
ム、酢酸バリウム、酢酸マグネシウム等が挙げられ、こ
れらの化合物は単独でも2種以上組合せて使用すること
もできる。
Among these, preferred specific examples include ammonia,
Caustic potash, caustic soda, potassium carbonate, sodium carbonate, sodium formate, sodium acetate, sodium citrate, calcium hydroxide, barium hydroxide, magnesium hydroxide, calcium carbonate, barium carbonate, magnesium carbonate, calcium acetate, barium acetate, magnesium acetate, etc. These compounds can be used alone or in combination of two or more.

これらの化合物は、酸処理後の黒鉛に含有される遊離
硫酸を中和する当量で使用され、該遊離硫酸との間で塩
を形成していることが望ましいが、過剰分は化合物のま
ま含有されていてもよい。即ち、黒鉛を酸処理し、水洗
後或は水洗工程で、アンモニア、脂肪族低級アミン、ア
ルカリ金属化合物或はアルカリ土類金属化合物をそのま
ま又は水との混合物として添加し、必要に応じてこれら
の化合物の過剰分を除去し、乾燥することにより熱膨張
性黒鉛を製造する。
These compounds are used in an amount equivalent to neutralize the free sulfuric acid contained in the graphite after the acid treatment, and it is desirable to form a salt with the free sulfuric acid. It may be. That is, graphite is acid-treated, and after washing with water or in a washing step, ammonia, an aliphatic lower amine, an alkali metal compound or an alkaline earth metal compound is added as it is or as a mixture with water, and if necessary, these are added. The excess of the compound is removed and dried to produce a thermally expandable graphite.

本発明で用いられる熱可塑性樹脂としては、例えば、
ポリエチレン、ポリプロピレン、ポリブチレン及びこれ
らのモノマーと酢酸ビニル、アクリル酸エステルとの共
重合体等のポリオレフィン樹脂類、ポリ塩化ビニル樹脂
類、ポリスチレン、アクリロニトリル−スチレン共重合
体、アクリロニトリル−ブタジエン−スチレン共重合体
等のスチレン系樹脂類、ポリエチレンテレフタレート等
のポリエステル系樹脂類、ナイロン等のアミド樹脂類、
ポリオキシメチレン等のエーテル系樹脂類の他、塩素化
ポリエチレン、ポリブタジエン、ポリイソプレン等のエ
ラストマー糖の各種樹脂類を代表的なものとして挙げる
ことが出来る。これらの中では、結晶化しにくい化学構
造を有し、融点が低く、溶融粘度が小さく、メルト・フ
ロー・レート(MFR)等で表される流動性の高いものが
より好適である。特に好適な樹脂としてはポリオレフィ
ン類、例えば密度が0.915〜0.935g/mlで融点が115℃未
満、JIS K−6760で規定される190℃におけるメルト・フ
ロー・レートが1〜100g/10minの低密度ポリエチレン、
メルト・フロー・レートが1〜100g/10min程度のポリプ
ロピレン或は酢酸ビニル含量が10〜90重量%のエチレン
−酢酸ビニルコポリマーを挙げることが出来る。
As the thermoplastic resin used in the present invention, for example,
Polyolefin resins such as polyethylene, polypropylene, polybutylene and copolymers of these monomers with vinyl acetate and acrylic acid esters, polyvinyl chloride resins, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer Such as styrene resins, polyester resins such as polyethylene terephthalate, amide resins such as nylon,
Representative resins include elastomeric resins such as chlorinated polyethylene, polybutadiene, and polyisoprene, in addition to ether-based resins such as polyoxymethylene. Among them, those having a chemical structure that is hardly crystallized, having a low melting point, a low melt viscosity, and a high fluidity represented by a melt flow rate (MFR) are more preferable. Particularly preferred resins are polyolefins, for example, having a density of 0.915 to 0.935 g / ml, a melting point of less than 115 ° C, and a low density having a melt flow rate at 190 ° C defined by JIS K-6760 of 1 to 100 g / 10min. polyethylene,
Examples thereof include polypropylene having a melt flow rate of about 1 to 100 g / 10 min or ethylene-vinyl acetate copolymer having a vinyl acetate content of 10 to 90% by weight.

本発明における熱可塑性樹脂組成物に対する熱膨張性
黒鉛の含有比率は、通常、3〜60%であって、3%未満
では難燃化が不十分な場合があり、また60%をこえると
樹脂の種類にもよるが、熱可塑性樹脂と混練する過程で
樹脂混合物の流動性が低下し、均一な混合組成物を得に
くい。
The content ratio of the heat-expandable graphite to the thermoplastic resin composition in the present invention is usually from 3 to 60%, and if it is less than 3%, the flame retardancy may be insufficient. Although it depends on the type, the fluidity of the resin mixture decreases during the process of kneading with the thermoplastic resin, and it is difficult to obtain a uniform mixed composition.

なお、本発明の熱可塑性樹脂組成物においては、通常
のプラスチック製品に使用される一般的な添加剤、即
ち、酸化防止剤、帯電防止剤、滑剤、架橋剤、染顔料、
充填剤等を添加、配合することに関しては特別の制限は
なく、従来公知の難燃剤を添加、併用しても良い。
Incidentally, in the thermoplastic resin composition of the present invention, general additives used in ordinary plastic products, namely, antioxidants, antistatic agents, lubricants, crosslinking agents, dyes and pigments,
There is no particular limitation on the addition and blending of a filler and the like, and a conventionally known flame retardant may be added and used in combination.

本発明の熱可塑性樹脂組成物を製造する方法として
は、熱可塑性樹脂原料と所定量の熱膨張性黒鉛をヘンシ
ェルミキサー、リボンブレンダー等通常使用される混合
装置によって攪拌混合し、次いで単軸又は二軸スクリュ
ー押出機、ニーダー、バンバリーミキサー等通常使用さ
れる混練機で混練するか、あるいは、加熱二本ロール等
を使用し、切り返し操作を行って混練する方法等を挙げ
ることが出来る。
As a method for producing the thermoplastic resin composition of the present invention, a thermoplastic resin raw material and a predetermined amount of thermally expandable graphite are stirred and mixed by a commonly used mixing device such as a Henschel mixer, a ribbon blender, and then a single-shaft or double-shaft. Examples of the method include kneading with a commonly used kneading machine such as a screw extruder, a kneader, and a Banbury mixer, or a method of kneading by performing a turning-back operation using a heated two rolls or the like.

混練する際の温度条件としては、使用する熱可塑性樹
脂原料の融点以上、混練混合物の温度として210℃を上
限とする範囲である。
The temperature conditions for the kneading are not less than the melting point of the thermoplastic resin raw material to be used, and the upper limit of the temperature of the kneading mixture is 210 ° C.

一般に熱膨張性黒鉛の添加により混合物の流動性が樹
脂単独の場合より低下する傾向があるので融点より30℃
以上高い温度に設定して混練することがより有利であ
り、又、上限温度の設定については混練操作中の自己発
熱による温度上昇があるので200℃以下に設定すること
が好適である。
Generally, the flowability of the mixture tends to be lower than that of the resin alone due to the addition of thermally expandable graphite.
It is more advantageous to knead the mixture at a higher temperature, and the upper limit temperature is preferably set to 200 ° C. or less because there is a temperature rise due to self-heating during the kneading operation.

混練時間は、混練装置の種類、温度条件、樹脂の流動
性により異なるが、通常2分〜20分である。混練混合物
の温度が上限の210℃に近づくにつれ、混練時間を短く
設定する必要がある。一方、温度が低くなるにつれ、混
練効率が低下する傾向があり、より長い混練時間を要す
る。
The kneading time varies depending on the type of the kneading apparatus, the temperature condition, and the fluidity of the resin, but is usually 2 minutes to 20 minutes. As the temperature of the kneading mixture approaches the upper limit of 210 ° C., the kneading time needs to be set shorter. On the other hand, as the temperature decreases, the kneading efficiency tends to decrease, and a longer kneading time is required.

好適な混練条件としては、例えばバッチ方式のニーダ
ー、バンバリーミキサー等では170〜190℃(混合物温
度)で3〜5分間程度、又、連続式の押出スクリュー等
では170〜200℃(混合物温度)で滞留時間として1〜4
分程度である。
Suitable kneading conditions include, for example, 170 to 190 ° C. (mixture temperature) for about 3 to 5 minutes in a batch type kneader or Banbury mixer, and 170 to 200 ° C. (mixture temperature) for a continuous extrusion screw or the like. 1-4 residence time
Minutes.

本発明の熱可塑性樹脂組成物は、通常押出シート、射
出成形品等とすることが出来る他、発泡剤を添加して発
泡成形品として使用することもできる。更にマスターバ
ッチ、コンパウンドとしてその他の熱可塑性樹脂類によ
る希釈、あるいは他の樹脂との混合により成形品に供す
ることもできる。いずれの場合においても、熱膨張性黒
鉛の含有比率は要求される難燃性の度合に応じて適宜調
整することができることはいうまでもない。
The thermoplastic resin composition of the present invention can be generally used as an extruded sheet, an injection molded product, or the like, and can also be used as a foam molded product by adding a foaming agent. Further, it can be provided as a master batch or a compound to a molded product by dilution with other thermoplastic resins or by mixing with another resin. In any case, it goes without saying that the content ratio of the heat-expandable graphite can be appropriately adjusted according to the required degree of flame retardancy.

また、本発明により製造される熱可塑性樹脂組成物あ
るいはこれを用いた成形品については、更に、表面の美
装化、耐水化、難燃化等を目的として異種材料との組合
せによる複合材料を製造することも可能である。
In addition, for the thermoplastic resin composition produced by the present invention or a molded article using the same, a composite material in combination with a dissimilar material for the purpose of surface aesthetics, water resistance, flame retardancy, etc. It is also possible to manufacture.

以下本発明を実施例及び比較例により更に詳細に説明
するが、本発明はその要旨を超えない限り、以下の実施
例に限定されるものではない。なお、実施例及び比較例
において、「部」は「重量部」を、「%」は「重量%」
を示す。
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples as long as the gist is not exceeded. In Examples and Comparative Examples, “parts” means “parts by weight”, and “%” means “% by weight”.
Is shown.

実施例1〜8、比較例1〜3 第1表に示す熱膨張性黒鉛及び熱可塑性樹脂を第1表
に示す配合量及び混練条件で、下記の混練方法により
混練し、熱可塑性樹脂組成物を製造した。混練操作終了
時に、水で湿らせたpH試験紙を混練装置内に挿入して気
相のpHを調べたところ、酸性を呈さなかった。得られた
熱可塑性樹脂組成物を用いて下記のシート化方法によ
りシートを製造し、これらについて難燃性試験としてJI
S−K−7201に準拠して酸素指数を測定した。結果を第
1表に示す。
Examples 1 to 8, Comparative Examples 1 to 3 The thermally expandable graphite and thermoplastic resin shown in Table 1 were kneaded by the following kneading method under the mixing amounts and kneading conditions shown in Table 1, and a thermoplastic resin composition was obtained. Was manufactured. At the end of the kneading operation, a pH test paper moistened with water was inserted into the kneading apparatus, and the pH of the gas phase was examined. As a result, no acidity was exhibited. Using the obtained thermoplastic resin composition, a sheet was produced by the following sheeting method, and these were subjected to JI as a flame retardancy test.
The oxygen index was measured according to SK-7201. The results are shown in Table 1.

混練方法 ブラベンダー社製「ブラベンダープラスチコーダー」
のミキシングチャンバーを第1表に示す温度に設定し、
回転数を30rpmに設定し、このチャンバーに、第1表に
示す配合量の熱可塑性樹脂を入れ、樹脂が流動状態で混
練され始めた状態になってから、引続き第1表に示す配
合量の熱膨張性黒鉛をおよそ15秒を要して添加し続け
た。同じ条件に保持して混練操作を所定時間続けた。
Kneading method "Brabender Plasticorder" manufactured by Brabender
Set the mixing chamber at the temperature shown in Table 1,
The number of revolutions was set to 30 rpm, and the thermoplastic resin having the compounding amount shown in Table 1 was put into this chamber. After the resin began to be kneaded in a fluidized state, the mixing amount shown in Table 1 was continued. The addition of the heat-expandable graphite continued over approximately 15 seconds. The kneading operation was continued for a predetermined time while maintaining the same conditions.

シート化方法 予め200℃に設定された熱プレス装置に、120mm×10mm
×5mmの金属製のスペーサーを設置し、前記混練操作の
終了した混合物およそ7部を100kg/cm2で1分間加熱圧
締し、ついで解圧してシートを得た。
Sheeting method 120mm x 10mm in a hot press set to 200 ° C in advance
A metal spacer of × 5 mm was installed, and about 7 parts of the mixture after the kneading operation was heated and pressed at 100 kg / cm 2 for 1 minute, and then depressurized to obtain a sheet.

なお、使用した熱膨張性黒鉛及び熱可塑性樹脂の種類
を以下に示す。
The types of the heat-expandable graphite and the thermoplastic resin used are shown below.

熱膨張性黒鉛 A:粒度36〜80メッシュ、1000℃、10秒間の膨張度200ml/
g、NH3で中和処理 B:粒度36〜80メッシュ、1000℃、10秒間の膨張度200ml/
g、NaOHで中和処理 C:粒度36〜80メッシュ、1000℃、10秒間の膨張度190ml/
g、Ca(OH)で中和処理 D:粒度36〜80メッシュ、1000℃、10秒間の膨張度200ml/
g、水洗処理のみ 熱可塑性樹脂 PE:ポリエチレン 三菱化成(株)製「三菱ポリエチ−H
D JS110」MFR:11、d=0.952 PP:ポリプロピレン 三菱油化(株)製「ノーブレンFY
−6」MFR:2.3、d=0.90 EVA:エチレン−酢ビ共重合体 三井ポリケミカル(株)
製「エバフレックス150」MI:30(g/10min)、VA33% 第1表の結果から、本発明の製造方法によって得られ
た熱可塑性樹脂組成物は、きわめて高い難燃性を示すこ
とが明らかである。また、本発明の製造方法によれば、
酸性ガスの発生はみられず、樹脂組成物が酸性を示すこ
とがない。
Thermal expandable graphite A: Particle size 36-80 mesh, expansion degree at 1000 ° C for 10 seconds 200 ml /
g, neutralized B with NH 3: particle size 36 to 80 mesh, 1000 ° C., for 10 seconds inflation of 200ml /
g, neutralization treatment with NaOH C: particle size 36-80 mesh, 1000 ° C, swelling degree for 10 seconds 190 ml /
g, neutralization treatment with Ca (OH) 2 D: Particle size 36-80 mesh, 1000 ° C, swelling degree for 10 seconds 200ml /
g, washing only thermoplastic resin PE: polyethylene "Mitsubishi Polyethylene-H" manufactured by Mitsubishi Kasei Corporation
D JS110 ”MFR: 11, d = 0.954 PP: Polypropylene“ Nobrene FY ”manufactured by Mitsubishi Yuka Corporation
-6 "MFR: 2.3, d = 0.90 EVA: Ethylene-vinyl acetate copolymer Mitsui Polychemicals Co., Ltd.
"Evaflex 150" MI: 30 (g / 10min), VA33% From the results in Table 1, it is clear that the thermoplastic resin composition obtained by the production method of the present invention exhibits extremely high flame retardancy. It is. According to the production method of the present invention,
No acid gas is generated, and the resin composition does not show acidity.

[発明の効果] 本発明により、熱可塑性樹脂に熱膨張性黒鉛を添加、
混練する際、混練混合物が酸性を示すことがなく、かつ
得られる熱可塑性樹脂組成物の難燃性をきわめて高くす
ることが可能となった。
[Effects of the Invention] According to the present invention, a heat-expandable graphite is added to a thermoplastic resin,
When kneading, the kneading mixture did not show acidity, and the flame retardancy of the obtained thermoplastic resin composition could be made extremely high.

フロントページの続き (58)調査した分野(Int.Cl.6,DB名) C08K 3/00 - 13/08 C08J 3/00 - 3/28Continuation of the front page (58) Field surveyed (Int. Cl. 6 , DB name) C08K 3/00-13/08 C08J 3/00-3/28

Claims (1)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】熱可塑性樹脂と、1重量%水分散液のpHが
4.5以上の熱膨張性黒鉛を、該熱可塑性樹脂と熱膨張性
黒鉛の混練混合物の温度を210℃以下に保持して混練す
ることを特徴とする熱可塑性樹脂組成物の製造方法。
1. The pH of a thermoplastic resin and a 1% by weight aqueous dispersion are
A method for producing a thermoplastic resin composition, comprising kneading 4.5 or more thermally expandable graphite while maintaining the temperature of a kneaded mixture of the thermoplastic resin and the thermally expandable graphite at 210 ° C. or lower.
JP17748389A 1989-07-10 1989-07-10 Method for producing thermoplastic resin composition Expired - Lifetime JP2800282B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP17748389A JP2800282B2 (en) 1989-07-10 1989-07-10 Method for producing thermoplastic resin composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP17748389A JP2800282B2 (en) 1989-07-10 1989-07-10 Method for producing thermoplastic resin composition

Publications (2)

Publication Number Publication Date
JPH0341161A JPH0341161A (en) 1991-02-21
JP2800282B2 true JP2800282B2 (en) 1998-09-21

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Country Link
JP (1) JP2800282B2 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3069509B2 (en) * 1995-04-10 2000-07-24 株式会社日立製作所 Non-aqueous secondary battery and method for producing graphite powder
DE19603424A1 (en) * 1996-01-31 1997-08-07 Friedhelm Schneider Molded parts from intumescent mixtures and process for producing the same
JP2002069201A (en) * 2000-08-29 2002-03-08 Nitto Kako Kk Flame-retardant rubber article and manufacturing method therefor
KR100418048B1 (en) * 2001-09-13 2004-02-11 극동씰테크 주식회사 Resin-bonded carbon materials composition and preparation thereof
JP4723875B2 (en) * 2005-02-21 2011-07-13 株式会社エス・ジー・シー Fireproof eaves ceiling panel with self-sealing function and manufacturing method thereof
JP5082020B2 (en) * 2011-02-04 2012-11-28 積水化学工業株式会社 Method for producing exfoliated graphite-polymer composite material
JP2019094409A (en) * 2017-11-21 2019-06-20 積水化学工業株式会社 Fire-resistant resin composition and molded body

Also Published As

Publication number Publication date
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