JP2835264B2 - Thermoplastic resin composition for foam molding - Google Patents
Thermoplastic resin composition for foam moldingInfo
- Publication number
- JP2835264B2 JP2835264B2 JP15804393A JP15804393A JP2835264B2 JP 2835264 B2 JP2835264 B2 JP 2835264B2 JP 15804393 A JP15804393 A JP 15804393A JP 15804393 A JP15804393 A JP 15804393A JP 2835264 B2 JP2835264 B2 JP 2835264B2
- Authority
- JP
- Japan
- Prior art keywords
- thermoplastic resin
- foam molding
- weight
- azodicarbonamide
- parts
- 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
Links
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は発泡成形用熱可塑性樹脂
組成物に関し、更に詳しくは射出成形時の昇華性残渣に
よる金型汚染がなく且つ発泡成形用マスターバッチにし
た場合、その保管時にアンモニア臭気のない発泡成形用
熱可塑性樹脂組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition for foam molding, and more particularly to a thermoplastic resin composition which is free from mold contamination due to a sublimable residue during injection molding and is made into a masterbatch for foam molding. The present invention relates to an odorless thermoplastic resin composition for foam molding.
【０００２】[0002]
【従来の技術】従来、アゾジカルボンアミドは自己消火
性の為安全性が高く、又、発生ガス量が多い為、熱可塑
性樹脂の発泡剤として広く使用されている。アゾジカル
ボンアミドを用いて熱可塑性樹脂を発泡させる場合、発
泡させる熱可塑性樹脂の種類及び加工温度等の発泡条件
によって、アゾジカルボンアミドの分解挙動が異なる場
合があり、特に樹脂の発泡に適正な溶融温度に発泡剤の
分解温度を合致させる必要から、アゾジカルボンアミド
の分解を制御する尿素、炭酸鉛、エタノールアミン、重
炭酸ナトリウム、酸化亜鉛等、各種の発泡助剤を添加す
ることが知られている。2. Description of the Related Art Conventionally, azodicarbonamide has been widely used as a foaming agent for thermoplastic resins because of its high self-extinguishing property and high safety, and because of the large amount of generated gas. When foaming a thermoplastic resin using azodicarbonamide, the decomposition behavior of the azodicarbonamide may differ depending on the foaming conditions such as the type of thermoplastic resin to be foamed and the processing temperature, and particularly, appropriate melting for foaming the resin. It is known to add various foaming aids such as urea, lead carbonate, ethanolamine, sodium bicarbonate, and zinc oxide that control the decomposition of azodicarbonamide because it is necessary to match the decomposition temperature of the blowing agent to the temperature. I have.
【０００３】又、熱可塑性樹脂にこれら発泡剤を加えて
成形加工するにあたっては、発泡剤粉末の周囲への飛
散、発泡剤の不均一な分散による発泡むら、成形機投入
時の材料の食いこみ不良等を防ぐ為、熱可塑性樹脂に発
泡剤を高濃度で混練した発泡成形用マスターバッチが使
用されている。[0003] In addition, when a foaming agent is added to a thermoplastic resin for molding, the foaming agent powder is scattered around, the foaming agent is unevenly dispersed due to uneven dispersion of the foaming agent, and the material is entrapped at the time of injection into a molding machine. In order to prevent defects and the like, a masterbatch for foam molding in which a foaming agent is kneaded at a high concentration with a thermoplastic resin is used.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、アゾジ
カルボンアミドにこれら発泡助剤を添加しても、射出成
形時に熱分解によるガスと共に発生したシアメリット、
シアヌル酸等の昇華性残渣が金型表面やガス抜き孔等に
積層して金型汚染物として付着し、成形不良を起こすと
いう問題がある。又、汚染物除去の為。成形能率の低下
をきたすという問題がある。However, even if these foaming aids are added to azodicarbonamide, shear merit generated together with gas by thermal decomposition during injection molding,
There is a problem that a sublimable residue such as cyanuric acid is deposited on a mold surface or a gas vent hole and adheres as mold contaminants to cause molding failure. Also, to remove contaminants. There is a problem that the molding efficiency is reduced.
【０００５】又、熱可塑性樹脂にアゾジカルボンアミド
と上記発泡助剤を高濃度で添加した発泡成形用マスター
バッチは、貯蔵タンクに入れ保管しておくとアンモニア
臭気が発生し、作業環境が悪化するという問題があっ
た。Further, a masterbatch for foam molding in which azodicarbonamide and the above-mentioned foaming assistant are added at a high concentration to a thermoplastic resin generates ammonia odor when stored in a storage tank and deteriorates the working environment. There was a problem.
【０００６】従って本発明は、射出成形時の昇華性残渣
による金型汚染がなく且つ発泡成形用マスターバッチに
した場合、その保管時にアンモニア臭気のない発泡成形
用熱可塑性樹脂組成物を提供することを目的としてい
る。Accordingly, an object of the present invention is to provide a thermoplastic resin composition for foam molding which is free from mold contamination by a sublimable residue during injection molding and has no ammonia odor during storage when the master batch for foam molding is stored. It is an object.
【０００７】[0007]
【課題を解決する為の手段】上記目的は以下の本発明に
よって達成される。即ち、本発明は、熱可塑性樹脂１０
０重量部に、アゾジカルボンアミド１〜８０重量部、炭
酸亜鉛０．２〜７５重量部及び焼明ばん０．０２〜２０
重量部を加えてなることを特徴とする発泡成形用熱可塑
性樹脂組成物である。The above objects are achieved by the present invention described below. That is, the present invention relates to the thermoplastic resin 10
0 parts by weight, 1 to 80 parts by weight of azodicarbonamide, 0.2 to 75 parts by weight of zinc carbonate and 0.02 to 20 parts of alum
A thermoplastic resin composition for foam molding characterized by adding parts by weight.
【０００８】[0008]
【作用】アゾジカルボンアミドに、炭酸亜鉛及び焼明ば
んを併用して発泡成形用熱可塑性樹脂組成物とすること
によって、射出成形時の昇華性残渣による金型汚染がな
く且つ発泡成形用マスターバッチにした場合、その保管
時にアンモニア臭気のない発泡成形用熱可塑性樹脂組成
物を提供することが出来る。かかる作用は、該樹脂組成
物中においては、炭酸亜鉛は射出成形時の昇華性残渣低
減の効果の他に、アゾジカルボンアミドの分解温度を低
下させる効果を示し、又、焼明ばんはアンモニア脱臭の
効果の他に、アゾジカルボンアミドの分解温度を低下さ
せる効果を示す為と考えられる。[Function] By using azodicarbonamide in combination with zinc carbonate and calcined alum to form a thermoplastic resin composition for foam molding, there is no mold contamination due to sublimable residues during injection molding, and a masterbatch for foam molding. In this case, it is possible to provide a thermoplastic resin composition for foam molding which does not have an ammonia odor during storage. In the resin composition, zinc carbonate exhibits the effect of reducing the decomposition temperature of azodicarbonamide in addition to the effect of reducing sublimable residues during injection molding. In addition to the effect described above, it is considered that the effect of lowering the decomposition temperature of azodicarbonamide is exhibited.
【０００９】[0009]
【好ましい実施態様】次に好ましい実施態様を挙げて本
発明を更に詳細に説明する。本発明の発泡成形用熱可塑
性樹脂組成物を構成するアゾジカルボンアミドに併用さ
れる炭酸亜鉛は、炭酸亜鉛(ZnCO3)又は塩基性炭酸亜鉛
(xZnCO3・3Zn(OH)2・H2O：式中ｘ＝１〜２である）であ
る。又、本発明で使用される焼明ばんは、化学式K2SO4・
Al(SO4)3で示される化合物であり、いずれも公知の材料
である。BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to preferred embodiments. Zinc carbonate used in combination with the azodicarbonamide constituting the thermoplastic resin composition for foam molding of the present invention is zinc carbonate (ZnCO 3 ) or basic zinc carbonate.
(xZnCO 3 .3Zn (OH) 2 .H 2 O: where x = 1 to 2). The alum used in the present invention has a chemical formula of K 2 SO 4.
A compound represented by Al (SO 4 ) 3 , all of which are known materials.
【００１０】本発明で使用さ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、ポリブテ
ン−１、エチレン−プロピレンコーポリマー、エチレン
−酢酸ビニルコーポリマー、エチレン−アクリル酸メチ
ルコーポリマー、ポリスチレン、ＡＢＳ樹脂、ＡＳ樹
脂、メチルメタクリレート樹脂及びポリアミド等が挙げ
られる。The thermoplastic resins used in the present invention include, for example, polyethylene, polypropylene, polybutene-1, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, polystyrene, ABS resin , AS resin, methyl methacrylate resin and polyamide.
【００１１】アゾジカルボンアミドの発泡助剤として、
塩基性遷移金属炭酸塩を使用する方法が開示されている
（特開昭５６−５８３５号公報参照）。又、アゾジカル
ボンアミドの発泡助剤として明ばんを使用する方法が開
示されている（特公昭５１−２５１４号公報参照）。し
かしながら、両方法は、いずれも塩基性遷移金属炭酸塩
又は明ばんをアゾジカルボンアミドの発泡助剤として単
独で使用しており、且つ本発明において発泡助剤として
炭酸亜鉛と焼明ばんとの組合わせによる射出成形時の金
型汚染防止及び発泡成形用マスターバッチでのアンモニ
ア臭気の発生防止の効果は示唆されていない。As a foaming aid for azodicarbonamide,
A method using a basic transition metal carbonate is disclosed (see JP-A-56-5835). A method using alum as a foaming aid for azodicarbonamide is disclosed (see Japanese Patent Publication No. 51-2514). However, both methods use a basic transition metal carbonate or alum alone as a foaming aid for azodicarbonamide, and in the present invention, a combination of zinc carbonate and calcined alum as a foaming aid. The effect of preventing mold contamination during injection molding and preventing the generation of ammonia odor in a masterbatch for foam molding by combination is not suggested.
【００１２】熱可塑性樹脂に対するアゾジカルボンアミ
ドの添加量については、熱可塑性樹脂１００重量部に対
し、アゾジカルボンアミド１重量部未満では発泡効果が
少なく、一方、８０重量部を越えると成形性が悪くな
る。熱可塑性樹脂に対する炭酸亜鉛の添加量について
は、熱可塑性樹脂１００重量部に対し、炭酸亜鉛が０．
２重量部未満及び７５重量部を越えると、射出成形時の
昇華性残渣低減の効果がない。熱可塑性樹脂に対する焼
明ばんの添加量については、熱可塑性樹脂１００重量部
に対し、焼明ばんが０．０２重量部未満ではアンモニア
脱臭効果がない。一方、焼明ばんが２０重量部を越える
と射出成形時の昇華性残渣低減の効果がない。With respect to the amount of azodicarbonamide added to the thermoplastic resin, the foaming effect is small when the amount of azodicarbonamide is less than 1 part by weight and the moldability is poor when the amount is more than 80 parts by weight with respect to 100 parts by weight of the thermoplastic resin. Become. Regarding the amount of zinc carbonate added to the thermoplastic resin, the amount of zinc carbonate was 0.1 to 100 parts by weight of the thermoplastic resin.
If it is less than 2 parts by weight or more than 75 parts by weight, there is no effect of reducing sublimable residues during injection molding. Regarding the amount of the alum to be added to the thermoplastic resin, if the amount of the alum is less than 0.02 parts by weight with respect to 100 parts by weight of the thermoplastic resin, there is no ammonia deodorizing effect. On the other hand, if the burned alum exceeds 20 parts by weight, there is no effect of reducing sublimable residues during injection molding.
【００１３】本発明の発泡成形用熱可塑性樹脂組成物
は、本発明の目的達成を妨げない範囲において、前記添
加剤の他に、顔料、分散剤、樹脂安定剤又は他の発泡助
剤を添加してもよい。本発明の発泡成形用熱可塑性樹脂
組成物は、以上の成分を単に混合又は混練したのみのも
のでもよいし、発泡剤及び添加剤の濃度が低い範囲で
は、そのままで或は溶融混練してペレット化し、発泡成
形に供することが出来る。又、発泡剤及び添加剤の濃度
が高い範囲では、そのままで或は溶融混練してペレット
化し、発泡成形用のマスターバッチとすることが出来
る。混合、混練、ペレット化及び成形は慣用の方法でよ
い。The thermoplastic resin composition for foam molding of the present invention contains a pigment, a dispersant, a resin stabilizer or other foaming aids in addition to the above additives, as long as the object of the present invention is not hindered. May be. The thermoplastic resin composition for foam molding of the present invention may be one obtained by simply mixing or kneading the above components, or, as long as the concentration of the foaming agent and the additive is low, pellets as they are or melt-kneaded. And can be subjected to foam molding. In the range where the concentrations of the foaming agent and the additive are high, pellets can be used as they are or melt-kneaded to form a masterbatch for foam molding. Mixing, kneading, pelletizing and molding may be performed by a conventional method.
【００１４】[0014]
【実施例】次に実施例及び比較例を挙げて本発明を更に
具体的に説明する。尚、マスターバッチのアンモニア発
生量、分解開始温度及びガス発生量は次の様にして測定
した。 （１）アンモニア発生量 マスターバッチ３５０ｇを５００ｍｌの内蓋付きの密閉
式ポリビンに入れる。これを密栓し、６０℃で５時間加
熱する。３０分間放冷後、開封しアンモニアガス検知管
（北川式検知管）の先端を５ｃｍマスターバッチ中に差
し込んだ状態で測定する。Next, the present invention will be described more specifically with reference to examples and comparative examples. The ammonia generation amount, decomposition start temperature, and gas generation amount of the master batch were measured as follows. (1) Amount of generated ammonia 350 g of a master batch is put into a 500 ml hermetically sealed polybin with an inner lid. This is sealed and heated at 60 ° C. for 5 hours. After leaving to cool for 30 minutes, measurement is performed with the end opened and the end of an ammonia gas detection tube (Kitakawa type detection tube) inserted into a 5 cm master batch.
【００１５】（２）分解開始温度 マスターバッチを熱分析機器（ＴＧ−ＤＳＣ）で測定す
る（昇温速度１０℃／ｍｉｎ．）。 （３）発生ガス量 試料を精秤して試験管に入れ、適量の流動パラフィンを
加える。この試験管を２００℃のシリコン浴中に浸漬
し、発生するガス量を測定する。最初の１分間は装置内
の空気膨張とみなし、その後２０分間のガス発生量を測
定する。(2) Decomposition start temperature The master batch is measured by a thermal analyzer (TG-DSC) (heating rate: 10 ° C./min.). (3) Amount of generated gas A sample is precisely weighed and put into a test tube, and an appropriate amount of liquid paraffin is added. This test tube is immersed in a silicon bath at 200 ° C., and the amount of generated gas is measured. The first minute is regarded as air expansion in the apparatus, and the amount of gas generated for the next 20 minutes is measured.
【００１６】実施例１ アゾジカルボンアミド（ユニホームＡＺＨ：大塚化学薬
品（株）製）２０重量部、炭酸亜鉛（正同化学（株）
製）１４重量部、焼明ばん（タイエースＫ−２０：大明
化学工業（株）製）１重量部、酸化チタン（タイペーク
ＣＲ−５０：石原産業（株）製）７重量部及び低密度ポ
リエチレン（サンテックＬＤＭ６５２５：旭化成工業
（株）製））５８重量部をヘンシェルミキサーで１〜３
分間混合する。次いでこの混合物を押出成形機（３０ｍ
ｍ単軸ベント式押出成形機）に供し約１１０℃にて押出
し、ペレタイザーでペレット化して本発明の発泡成形用
マスターバッチを得た。Example 1 20 parts by weight of azodicarbonamide (Uniform AZH: manufactured by Otsuka Chemical Co., Ltd.) and zinc carbonate (Seido Chemical Co., Ltd.)
14 parts by weight, 1 part by weight of Yakimyoban (Thai Ace K-20: manufactured by Daimei Chemical Industry Co., Ltd.), 7 parts by weight of titanium oxide (Taipec CR-50: manufactured by Ishihara Sangyo Co., Ltd.) and low density polyethylene ( Suntech LDM6525: manufactured by Asahi Kasei Kogyo Co., Ltd.)
Mix for a minute. This mixture was then extruded into an extruder (30 m
m single-screw vent-type extrusion molding machine), extruded at about 110 ° C, and pelletized with a pelletizer to obtain a foaming masterbatch of the present invention.
【００１７】この発泡成形用マスターバッチは、（１）
の方法で測定したアンモニア発生量が３ｐｐｍと少な
く、保管時のアンモニア臭気による作業環境悪化の問題
が改善された。ここで得られた発泡成形用マスターバッ
チ１００重量部に対し、ポリプロピレン９００重量部の
割合でスクリュー式射出成形機に供給し、成形温度２３
０℃にて金型にて成形した。成形後の金型は昇華性残渣
の付着がなく、良好な状態であった。結果を下記表１に
示す。The masterbatch for foam molding comprises (1)
The amount of generated ammonia measured by the method described in (1) was as small as 3 ppm, and the problem of deterioration of the working environment due to ammonia odor during storage was improved. 100 parts by weight of the obtained masterbatch for foam molding was supplied to a screw-type injection molding machine at a ratio of 900 parts by weight of polypropylene, and a molding temperature of 23 parts.
It was molded in a mold at 0 ° C. The mold after molding was in a good state without adhesion of sublimable residues. The results are shown in Table 1 below.
【００１８】実施例２ アゾジカルボンアミド、酸化亜鉛（亜鉛華１号特製：堺
化学工業（株）製）、炭酸亜鉛、焼明ばん、酸化チタン
及び低密度ポリエチレンを実施例１と同様に処理し、試
験を行った。結果を下記表１に示す。 実施例３ 実施例２と同じ材料で配合だけ変更し、実施例２と同様
に処理し、試験を行った。結果を下記表１に示す。Example 2 Azodicarbonamide, zinc oxide (Zinc Hua No. 1 manufactured by Sakai Chemical Industry Co., Ltd.), zinc carbonate, alum, titanium oxide and low-density polyethylene were treated in the same manner as in Example 1. The test was performed. The results are shown in Table 1 below. Example 3 The same materials as in Example 2 were used except that the composition was changed, and the same treatment as in Example 2 was performed and a test was performed. The results are shown in Table 1 below.
【００１９】比較例１ アゾジカルボンアミド、酸化亜鉛、焼明ばん、酸化チタ
ン及び低密度ポリエチレンを実施例１と同様に処理し、
試験を行った。結果を下記表１に示す。 比較例２ アゾジカルボンアミド、重炭酸ナトリウム（粉砕食重：
旭硝子（株）製）、酸化亜鉛、焼明ばん、酸化チタン及
び低密度ポリエチレンを実施例１と同様に処理し、試験
を行った。結果を下記表１に示す。Comparative Example 1 Azodicarbonamide, zinc oxide, calcined alum, titanium oxide and low density polyethylene were treated in the same manner as in Example 1,
The test was performed. The results are shown in Table 1 below. Comparative Example 2 Azodicarbonamide, sodium bicarbonate (ground weight:
Asahi Glass Co., Ltd.), zinc oxide, calcined alum, titanium oxide and low-density polyethylene were treated in the same manner as in Example 1 and tested. The results are shown in Table 1 below.
【００２０】比較例３ アゾジカルボンアミド、炭酸亜鉛、酸化チタン及び低密
度ポリエチレンを実施例１と同様に処理し、試験を行っ
た。結果を下記表１に示す。Comparative Example 3 Azodicarbonamide, zinc carbonate, titanium oxide and low density polyethylene were treated in the same manner as in Example 1 and tested. The results are shown in Table 1 below.
【００２１】[0021]
【表１】 [Table 1]
【００２２】[0022]
【発明の効果】以上の如き発明によれば、射出成形時に
昇華性残渣による金型汚染のない、又マスターバッチで
の保管時におけるアンモニア臭気による作業環境悪化の
問題のない発泡成形用熱可塑性樹脂を提供することが出
来る。According to the invention as described above, the thermoplastic resin for foam molding has no problem of mold contamination due to sublimable residue at the time of injection molding, and has no problem of deteriorating the working environment due to ammonia odor during storage in a master batch. Can be provided.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭56−5835（ＪＰ，Ａ) 特開 平４−178484（ＪＰ，Ａ) 特公 昭51−2514（ＪＰ，Ｂ１) (58)調査した分野(Int.Cl.6，ＤＢ名) C08J 9/04 - 9/10 C08K 3/26,3/30,5/23──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-56-5835 (JP, A) JP-A-4-178484 (JP, A) JP-B-51-2514 (JP, B1) (58) Field (Int.Cl. 6 , DB name) C08J 9/04-9/10 C08K 3 / 26,3 / 30,5 / 23
Claims (1)
ルボンアミド１〜８０重量部、炭酸亜鉛０．２〜７５重
量部及び焼明ばん０．０２〜２０重量部を加えてなるこ
とを特徴とする発泡成形用熱可塑性樹脂組成物。1. A method comprising adding 1 to 80 parts by weight of azodicarbonamide, 0.2 to 75 parts by weight of zinc carbonate and 0.02 to 20 parts by weight of alum to 100 parts by weight of a thermoplastic resin. Thermoplastic resin composition for foam molding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15804393A JP2835264B2 (en) | 1993-06-04 | 1993-06-04 | Thermoplastic resin composition for foam molding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15804393A JP2835264B2 (en) | 1993-06-04 | 1993-06-04 | Thermoplastic resin composition for foam molding |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06345888A JPH06345888A (en) | 1994-12-20 |
| JP2835264B2 true JP2835264B2 (en) | 1998-12-14 |
Family
ID=15663046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15804393A Expired - Lifetime JP2835264B2 (en) | 1993-06-04 | 1993-06-04 | Thermoplastic resin composition for foam molding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2835264B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4694225B2 (en) * | 2005-03-10 | 2011-06-08 | 株式会社フジクラ | Method for reducing water absorption of coaxial cable and method for reducing tan δ of coaxial cable |
-
1993
- 1993-06-04 JP JP15804393A patent/JP2835264B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06345888A (en) | 1994-12-20 |
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