JP3307670B2 - Method for producing thermoplastic polyester elastomer foam - Google Patents
Method for producing thermoplastic polyester elastomer foamInfo
- Publication number
- JP3307670B2 JP3307670B2 JP10052292A JP10052292A JP3307670B2 JP 3307670 B2 JP3307670 B2 JP 3307670B2 JP 10052292 A JP10052292 A JP 10052292A JP 10052292 A JP10052292 A JP 10052292A JP 3307670 B2 JP3307670 B2 JP 3307670B2
- Authority
- JP
- Japan
- Prior art keywords
- polyester elastomer
- thermoplastic polyester
- foam
- present
- foamed
- 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
Description
【０００１】[0001]
【産業上の利用分野】本発明は熱可塑性ポリエステルエ
ラストマーの低倍率の発泡体の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a low-magnification foam of a thermoplastic polyester elastomer.
【０００２】[0002]
【従来の技術】従来知られている発泡体として一般的な
材料はポリスチレン、ポリエチレン等で熱可塑性ポリエ
ステルエラストマーの発泡体は現在実用化されていな
い。2. Description of the Related Art Polystyrene, polyethylene and the like are generally known as conventional foams, and thermoplastic polyester elastomer foams have not been put into practical use at present.
【０００３】[0003]
【発明が解決しようとする課題】熱可塑性ポリエステル
エラストマーのように高結晶性の材料の場合には、金型
表面に接触することにより急速に温度低下する部分は未
発泡状態となり、また中央部は樹脂温度によって固化速
度が異なり、発泡状態の均一なものを得ることができ
ず、しかも非発泡表面層が薄いものを得ることができな
かった。発泡が不均一であると、荷重が加えられるよう
な用途では、発泡体全体に均一に荷重が加わらない欠点
を生じ、また非発泡表面層が厚すぎると、弾性率が高
く、振動吸収材のような用途では、その効果が発揮され
にくい。In the case of a highly crystalline material such as a thermoplastic polyester elastomer, a portion where the temperature is rapidly lowered by contact with the surface of the mold is in an unfoamed state, and the central portion is in an unfoamed state. The solidification rate differs depending on the resin temperature, so that a uniform foamed state could not be obtained, and a thin non-foamed surface layer could not be obtained. If the foam is non-uniform, in applications where a load is applied, there is a disadvantage that the load is not applied uniformly to the entire foam, and if the non-foam surface layer is too thick, the elastic modulus is high and the In such applications, the effect is hardly exhibited.
【０００４】[0004]
【課題を解決するための手段】そこでかかる課題を解決
するために表面の未発泡層の厚み制御と均一な発泡につ
いて鋭意検討した結果、本発明に到達した。即ち、５０
℃≦融点−結晶化温度≦１００℃、１≦還元粘度≦３及
び２≦メルトフローインデックス（ｇ／１０ｍｉｎ）≦
４０の特性を有する熱可塑性ポリエステルエラストマー
１００重量部に対して、熱分解型発泡剤を１〜２０重量
部配合し、該配合物を射出成形機によって射出成形する
ことを特徴とする熱可塑性ポリエステルエラストマー発
泡体の製造方法である。In order to solve the above-mentioned problems, the present inventors have made intensive studies on the control of the thickness of the unfoamed layer on the surface and the uniform foaming. As a result, the present invention has been reached. That is, 50
℃ ≦ melting point−crystallization temperature ≦ 100 ° C., 1 ≦ reduced viscosity ≦ 3 and 2 ≦ melt flow index (g / 10 min) ≦
A thermoplastic polyester elastomer, wherein 1 to 20 parts by weight of a pyrolytic foaming agent is blended with 100 parts by weight of a thermoplastic polyester elastomer having the characteristics of 40, and the blend is injection-molded by an injection molding machine. This is a method for producing a foam.
【０００５】本発明における熱可塑性ポリエステルエラ
ストマーとは、高融点ポリエステルセグメントと分子量
４００〜６０００の低融点重合体セグメントとからなる
ブロック共重合体であり、高融点ポリエステルセグメン
ト構成部分だけで高重合体を形成した場合の融点が１５
０℃以上であり、低融点重合体セグメント構成部分のみ
で測定した場合の融点ないし軟化点が８０℃以下である
ような構成部分からなる熱可塑性ポリエステルエラスト
マーであり、その熱可塑性ポリエステルエラストマーの
融点は８０℃以上である。[0005] The thermoplastic polyester elastomer in the present invention is a block copolymer comprising a high melting polyester segment and a low melting polymer segment having a molecular weight of 400 to 6000. Melting point of 15 when formed
0 ° C. or higher, a thermoplastic polyester elastomer comprising a component having a melting point or softening point of 80 ° C. or less when measured only at the low melting polymer segment component, and the melting point of the thermoplastic polyester elastomer is 80 ° C. or higher.
【０００６】本発明でいう融点（Ｔｍ）、結晶化温度
（Ｔｃ）とはＡＳＴＭＤ−３４１８に準じて得られる値
である。Ｔｍ−Ｔｃが５０℃より小さい場合には、固化
速度が早すぎて未発泡表面層が厚く形成され、又１００
℃より大きい場合には、固化速度が遅すぎて成形サイク
ルが著しく長くなる問題が発生する。The melting point (Tm) and crystallization temperature (Tc) referred to in the present invention are values obtained according to ASTM D-3418. When Tm-Tc is less than 50 ° C., the solidification rate is too fast to form a thick unfoamed surface layer.
If the temperature is higher than 0 ° C., there is a problem that the solidification rate is too slow and the molding cycle becomes extremely long.
【０００７】本発明における熱可塑性ポリエステルエラ
ストマーの還元粘度（ηsp/c）とメルトフローインデッ
クス（ＭＩ）は、１≦ηsp/c≦３、および２≦メルトフ
ローインデックス≦４０であることが必要である。この
条件と前記の固化速度の条件を満足することにより、熱
可塑性ポリエステルエラストマーにおいて非発泡の表面
層が薄く、かつ中央部に均一な粒子径を持つ発泡層が形
成される。ここでいうηsp/cとはポリエステルエラスト
マーをフェノール／テトラクロロエタン（６０／４０重
量比）混合溶媒で３０℃で測定した値である。[0007] The reduced viscosity (ηsp / c) and melt flow index (MI) of the thermoplastic polyester elastomer in the present invention must satisfy 1 ≦ ηsp / c ≦ 3 and 2 ≦ melt flow index ≦ 40. . By satisfying this condition and the above-mentioned condition of the solidification rate, a non-foamed surface layer of the thermoplastic polyester elastomer is thin, and a foamed layer having a uniform particle diameter is formed at the center. Here, ηsp / c is a value obtained by measuring the polyester elastomer in a phenol / tetrachloroethane (60/40 weight ratio) mixed solvent at 30 ° C.
【０００８】本発明でいうメルトフローインデックスと
はＪＩＳＫ−７２１０に準じて２３０℃で得られる値で
ある。ηsp/cが１未満及びメルトフローインデックスが
４０を越えると発泡状態が不均一になる。またηsp/cが
３より大きく、メルトフローインデックスが２未満の場
合には発泡不足や非発泡表面層が厚くなる結果になる。The melt flow index referred to in the present invention is a value obtained at 230 ° C. according to JIS K-7210. When ηsp / c is less than 1 and the melt flow index exceeds 40, the foamed state becomes uneven. When ηsp / c is greater than 3 and the melt flow index is less than 2, foaming is insufficient and the non-foamed surface layer becomes thick.
【０００９】本発明で使用する熱分解型発泡剤とは、熱
により分解ガスを発生させるタイプの発泡剤であり、無
機系、有機系のいずれでもよいが、ガスの発生温度範囲
が狭く、かつガスの発生量も多いことから有機系の発泡
剤が好ましい。有機系のものとしてはアゾ化合物、ヒド
ラジン誘導体、セミカルバジド化合物、アジ化合物、ニ
トロソ化合物、トリアゾール化合物等であり、これらの
例として、アゾジカルボンアミド（ＡＤＣＡ）、バリウ
ムアゾシガルボキシレート、ジニトロソペンタメチレン
テトラミン（ＤＰＴ）、Ｐ，Ｐ′−オキシビス（ベンゼ
ンスルホニルヒドラジッド）などを挙げることができる
が、熱可塑性ポリエステルエラストマーの融点との関係
から、ＡＤＣＡやＤＰＴが好ましい。The thermal decomposition type foaming agent used in the present invention is a type of foaming agent that generates a decomposition gas by heat, and may be either inorganic or organic, but has a narrow gas generation temperature range and Organic foaming agents are preferred because they generate a large amount of gas. Organic compounds include azo compounds, hydrazine derivatives, semicarbazide compounds, azide compounds, nitroso compounds, triazole compounds, and the like. Examples thereof include azodicarbonamide (ADCA), barium azocigarboxylate, and dinitrosopentamethylene. Examples thereof include tetramine (DPT) and P, P'-oxybis (benzenesulfonyl hydrazide), and ADCA and DPT are preferable in view of the relationship with the melting point of the thermoplastic polyester elastomer.
【００１０】また上記発泡剤に加えて使用できる熱分解
助剤としては、ルイス酸特性を有する金属酸化物や脂肪
酸金属塩が好ましく、これらの化合物として、ステアリ
ン酸のバリウム塩や亜鉛塩、酸化亜鉛、酸化マグネシウ
ム等が挙げられる。脂肪酸金属塩が特に成形サイクルの
短縮に効果があり、最も好ましい。As the thermal decomposition aid which can be used in addition to the above foaming agent, metal oxides and fatty acid metal salts having Lewis acid properties are preferable. As these compounds, barium salts and zinc salts of stearic acid, zinc oxide , Magnesium oxide and the like. Fatty acid metal salts are particularly effective because they are particularly effective in shortening the molding cycle.
【００１１】また発泡剤の配合量は、熱可塑性ポリエス
テルエラストマー１００重量部に対し、１〜２０重量部
であり、配合量が１重量部未満では充分な発泡は得られ
ず、又２０重量部を越えると、本発明の効果が得られな
い。本発明の発泡体の比重は、好ましくは０．４〜１．
０であり、比重が０．４以下１．０以上では本発明の目
的であるところの性能が得にくくなる。本発明により得
られる発泡体の発泡倍率は、１．３〜３．０倍の低倍率
が好ましい。本発明の発泡体の非発泡表面層の厚みは１
〜０．０５ｍｍが好ましい。The amount of the foaming agent is from 1 to 20 parts by weight based on 100 parts by weight of the thermoplastic polyester elastomer. If the amount is less than 1 part by weight, sufficient foaming cannot be obtained. If it exceeds, the effect of the present invention cannot be obtained. The specific gravity of the foam of the present invention is preferably from 0.4 to 1.
When the specific gravity is 0.4 or less and 1.0 or more, it is difficult to obtain the performance as the object of the present invention. The expansion ratio of the foam obtained by the present invention is preferably as low as 1.3 to 3.0 times. The thickness of the non-foamed surface layer of the foam of the present invention is 1
~ 0.05 mm is preferred.
【００１２】発泡に使用する射出成形機は特に限定はな
いが、シャットオフノズルの射出成形機を使用するのが
好ましい。また熱分解型発泡剤の添加方法としては、パ
ウダーで配合することもできるが、マスターバッチの方
が発泡剤の分散性がよく、好ましい。The injection molding machine used for foaming is not particularly limited, but it is preferable to use a shut-off nozzle injection molding machine. As a method of adding the thermal decomposition type foaming agent, powder may be used, but a master batch is preferred because the foaming agent has better dispersibility.
【００１３】[0013]
【実施例】以下に実施例によって本発明をさらに詳しく
説明する。本発明はこれらの実施例に限定されるもので
ないことはいうまでもない。The present invention will be described in more detail with reference to the following examples. It goes without saying that the present invention is not limited to these examples.
【００１４】・非発泡表面層及び不均一発泡粒子径の検
査方法：発泡体を縦に解体し、その断面の非発泡表面層
厚み、最大発泡粒子径を実測した。Inspection method of non-foamed surface layer and non-uniform foamed particle diameter: The foam was disassembled vertically, and the thickness of the non-foamed surface layer and the maximum foamed particle diameter of the cross section were measured.
【００１５】実施例１〜２及び比較例１〜４ 縦、横、厚みの寸法(mm)が１００、１００、１２の成形
品を射出成形法で成形したときの非発泡非発泡表面層厚
み、最大発泡粒子径、サイクルタイム及び発泡体の状態
を調べた結果を以下に示す。なお成形条件は下記の通り
である。Examples 1 and 2 and Comparative Examples 1 to 4 The thickness of a non-foamed non-foamed surface layer when moldings having dimensions of 100, 100 and 12 in length, width and thickness (mm) were molded by injection molding. The results of examining the maximum foamed particle diameter, cycle time and foam state are shown below. The molding conditions are as follows.
【００１６】・成形条件： 成形機；住友重機製ＳＧ１２５型 金型 ；１００×１００×１２(mm) 射出圧；５００〜２０００(kg/cm2) マスターバッチ；永和化成（株）製ホリスレンＥＢ１０
６（５）（アゾ系熱分解型発泡剤５０重量％含有） 添加量；１０(wt)％Molding conditions: Molding machine; SG125 mold manufactured by Sumitomo Heavy Industries; 100 × 100 × 12 (mm) Injection pressure; 500-2000 (kg / cm 2 ) masterbatch; Hollislen EB10 manufactured by Eiwa Chemical Co., Ltd.
6 (5) (containing 50% by weight of an azo-based pyrolytic foaming agent) Amount added: 10 (wt)%
【００１７】なお比較例１〜４及び実施例２の重合体は
テレフタル酸／ブタンジオール／ポリオキシテトラメチ
レングリコール系ポリエステルエラストマーであり、実
施例１として用いた重合体はテレフタル酸／イソフタル
酸／／ブタンシオールポリオキシテトラメチレングリコ
ール系ポリエステルエラストマーである。実施例１と比
較例１〜２の結果について表１に、実施例２と比較例３
〜４の結果について表２にまとめた。The polymers of Comparative Examples 1 to 4 and Example 2 were terephthalic acid / butanediol / polyoxytetramethylene glycol polyester elastomer, and the polymer used in Example 1 was terephthalic acid / isophthalic acid // It is a butane thiol polyoxytetramethylene glycol-based polyester elastomer. Table 1 shows the results of Example 1 and Comparative Examples 1 and 2, and Example 2 and Comparative Example 3
Table 2 summarizes the results of Nos. To 4.
【００１８】[0018]
【表１】 [Table 1]
【００１９】[0019]
【表２】 [Table 2]
【００２０】比較例１は（融点−結晶化温度）が３０℃
で５０℃未満であるので最大発泡粒子径が大きく、又比
較例２は１１０℃で１００℃を越えるのでサイクルタイ
ムが長い。In Comparative Example 1, (melting point−crystallization temperature) was 30 ° C.
Is less than 50 ° C., the maximum expanded particle size is large, and Comparative Example 2 has a long cycle time at 110 ° C., exceeding 100 ° C.
【００２１】比較例３はメルトフローインデックスが４
２で４０より大きいので最大粒子径が大きく、非発泡表
面層の厚みも厚く、コアの状態も悪い。又比較例４は還
元粘度が５、メルトフローインデックス０．５で２未満
であるので最大粒子径が大きく、コアの状態も悪い。Comparative Example 3 had a melt flow index of 4
2, the maximum particle diameter is large, the thickness of the non-foamed surface layer is large, and the state of the core is poor. Comparative Example 4 has a reduced viscosity of 5 and a melt flow index of 0.5, which is less than 2, and therefore has a large maximum particle size and a poor core state.
【００２２】[0022]
【発明の効果】本発明は特定の固化速度で、特定の溶液
粘度と特定の溶融粘度の熱可塑性ポリエステルエラスト
マーを使用し、熱分解型発泡剤と組み合わせることによ
り、射出成形により、均一発泡で非発泡表面層の薄い熱
可塑性ポリエステルエラストマー発泡体の成形を可能に
する。The present invention uses a thermoplastic polyester elastomer having a specific solution viscosity and a specific melt viscosity at a specific solidification rate, and is combined with a pyrolysis type foaming agent. Enables molding of a thin thermoplastic polyester elastomer foam with a foamed surface layer.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C08J 9/06 - 9/10 ──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. 7 , DB name) C08J 9/06-9/10
Claims (1)
１≦還元粘度≦３及び２≦メルトフローインデックス
（ｇ／１０ｍｉｎ）≦４０の特性を有する熱可塑性ポリ
エステルエラストマー１００重量部に対して、熱分解型
発泡剤を１〜２０重量部配合し、該配合物を射出成形機
によって射出成形することを特徴とする熱可塑性ポリエ
ステルエラストマー発泡体の製造方法。(1) 50 ° C. ≦ melting point−crystallization temperature ≦ 100 ° C.
1 to 20 parts by weight of a pyrolytic foaming agent is blended with 100 parts by weight of a thermoplastic polyester elastomer having characteristics of 1 ≦ reduced viscosity ≦ 3 and 2 ≦ melt flow index (g / 10 min) ≦ 40, and A method for producing a thermoplastic polyester elastomer foam, comprising subjecting a product to injection molding using an injection molding machine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10052292A JP3307670B2 (en) | 1992-03-25 | 1992-03-25 | Method for producing thermoplastic polyester elastomer foam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10052292A JP3307670B2 (en) | 1992-03-25 | 1992-03-25 | Method for producing thermoplastic polyester elastomer foam |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05271453A JPH05271453A (en) | 1993-10-19 |
| JP3307670B2 true JP3307670B2 (en) | 2002-07-24 |
Family
ID=14276294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10052292A Expired - Fee Related JP3307670B2 (en) | 1992-03-25 | 1992-03-25 | Method for producing thermoplastic polyester elastomer foam |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3307670B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6867265B2 (en) * | 2017-09-29 | 2021-04-28 | 積水化成品工業株式会社 | High-gloss foam particles, foam moldings and methods for manufacturing them |
| JP6882967B2 (en) * | 2017-09-29 | 2021-06-02 | 積水化成品工業株式会社 | Ester-based elastomer foam particles, foam moldings and methods for producing them |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5829329B2 (en) * | 1980-06-02 | 1983-06-22 | 東レ株式会社 | polyester elastomer foam |
-
1992
- 1992-03-25 JP JP10052292A patent/JP3307670B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05271453A (en) | 1993-10-19 |
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