JPS6042432A - Foamed particle - Google Patents
Foamed particleInfo
- Publication number
- JPS6042432A JPS6042432A JP14968183A JP14968183A JPS6042432A JP S6042432 A JPS6042432 A JP S6042432A JP 14968183 A JP14968183 A JP 14968183A JP 14968183 A JP14968183 A JP 14968183A JP S6042432 A JPS6042432 A JP S6042432A
- Authority
- JP
- Japan
- Prior art keywords
- foamed
- resin
- block copolymer
- particles
- crosslinking
- 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.)
- Granted
Links
Abstract
Description
【発明の詳細な説明】
本発明は、高度のゴム弾性を示す発泡成形体を製造する
ｔこめの成形材料としてすぐれた性質を有する、熱可塑
性エラストマー樹脂の発泡粒子に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to foamed particles of thermoplastic elastomer resin that have excellent properties as a molding material for producing foamed molded articles exhibiting a high degree of rubber elasticity.
高度のゴム弾性を示す発泡成形体としては従来ポリウレ
タンフォームが代表的なものであるが、これは気泡が連
続気胞であるため、圧縮特性において劣り、また高価で
あるという欠点があった。Conventionally, polyurethane foam has been typical as a foamed molded product exhibiting a high degree of rubber elasticity, but since the cells are open cells, this has disadvantages in that it has poor compression properties and is expensive.
近年、熱可塑性エラストマー樹脂の品質改良が進んだ結
果、多くの点でポリウレタン樹脂よりもすぐれているも
のが安価に利用できるようになっているから、これをポ
リスチレン、ポリオレフィン等の熱可塑性樹脂について
広〈実施されている発泡成形法、すなわちこれらの樹脂
の粒子を予備的に発泡させて発泡粒子としたのち成形用
型内で加熱することにより発泡粒子を再発泡させるとと
もに粒子同士を融着させて成形する方法によって発泡成
形することができれば、高物性の弾性発泡成形体が高能
率で得られる筈である。しかしながら、期待に反して、
熱可塑性エラストマー樹脂はポリスチレンやポリオレフ
ィンと同様に溶融状態で発泡させて成形しようとすると
、一応発泡はするものの、その後の収縮が大きく、この
ため変形（収縮を含む）が甚しくしかも気泡が粗大１こ
なるなど、とうてい満足な成形体は得られない。In recent years, as a result of improvements in the quality of thermoplastic elastomer resins, products that are superior to polyurethane resins in many respects are now available at lower prices. (The currently practiced foam molding method involves preliminary foaming of these resin particles to form foamed particles, and then heating them in a mold to re-foam the foamed particles and fuse the particles together.) If foam molding can be performed using a molding method, an elastic foam molded product with high physical properties can be obtained with high efficiency. However, contrary to expectations,
When thermoplastic elastomer resin is foamed in a molten state and molded in the same way as polystyrene and polyolefin, although it will foam for a while, it will subsequently shrink significantly, resulting in severe deformation (including shrinkage) and large bubbles. A completely satisfactory molded product cannot be obtained.
本発明者らは、上述のように困難な熱可塑性エラストマ
ー樹脂の発泡成形を原料樹脂の面から改良を加えること
により可能にすることに想到し、種々検討を重ねた結果
、ポリアミド系エラストマー樹脂を架橋処理してイυら
れるエラストマーが、従来の熱可塑性エラストマー樹脂
にはみられないすぐれた発泡成形性を有することを知っ
た。The present inventors came up with the idea of making the difficult foam molding of thermoplastic elastomer resin possible by improving the raw material resin as described above, and as a result of various studies, we developed polyamide-based elastomer resin. It has been found that the elastomer produced by crosslinking has excellent foam moldability not found in conventional thermoplastic elastomer resins.
本発明は上記知見に基くものであって、容易に高品質の
弾性発泡成形体を与える発泡粒子、すなわも発泡粒子を
構成する樹脂か結晶性ポリアミドセグメントおよびポリ
エーテルセグメントを有するブロック共重合体からなる
熱可塑性エラストマー樹脂の架橋処理物であってメルＦ
インデクスが４０ｇ／”１０分をこえず熱キシレン不溶
解残渣が６０％をこえないもの上りなることを特徴とす
る発泡粒子を提供するものである（但しメルトインデク
スおよび熱キシレン不溶解残渣の値は後記測定法による
）。The present invention is based on the above findings, and is based on foamed particles that can easily produce high-quality elastic foam molded articles, that is, a block copolymer having resin or crystalline polyamide segments and polyether segments constituting the foamed particles. A crosslinked thermoplastic elastomer resin consisting of Mel F
The present invention provides foamed particles characterized in that the index does not exceed 40 g/''10 minutes and the thermal xylene insoluble residue does not exceed 60% (however, the values of the melt index and the thermal xylene insoluble residue do not exceed 60%). (according to the measurement method described below).
一般に、架橋可能な熱可塑性合成樹脂を架橋処理すると
、処理炭に応してその溶融時の流動性が低下し、ついに
は熱可塑性を失う、に至る。このような物性の変化は、
特定の用途においては好ましいものとなることがあるが
、一般的には、溶融押出成形や成形物の後加工（たとえ
ば延伸処理）を困難にするから、架橋処理が実際に熱可
塑性０１脂を改質する手段として利用されている例は少
なく、ポリオレフィンの架橋など、ごく限られた例があ
るにすぎない。そして熱可塑性エラストマー樹脂の分野
においては、この樹脂の最大の特長すなわちエラストマ
ーとしては異例の熱可塑性を減殺して成形性を悪化させ
るとともにその生命とするゴム弾性をも低下させること
が予想されるためか、架橋処理をあえて施すことが検討
された例はほとんど見当らない。特に熱可塑性ポリアミ
ドエラストマー樹脂については、それが架橋可能か否か
もわかっていなかったから、本発明で特定された範囲で
架橋処理されたこの１ｊｊ脂およびその予備発泡粒子が
すくれた発泡成形性を獲得し、しかも物理的性質や化学
的性質の点でもほとんど劣化せず、むしろ改良されるこ
とは、全く予想外のことであった。Generally, when a crosslinkable thermoplastic synthetic resin is crosslinked, its fluidity during melting decreases depending on the treated charcoal, and eventually the resin loses its thermoplasticity. These changes in physical properties are
While this may be preferable in certain applications, crosslinking does not actually modify the thermoplastic 01 resin, as it generally makes melt extrusion and post-processing of the molded product (e.g., stretching) difficult. There are only a few examples where it has been used as a means of quality control, and there are only a few examples, such as crosslinking of polyolefins. In the field of thermoplastic elastomer resins, it is expected that this resin's greatest feature, that is, its thermoplasticity, which is unusual for an elastomer, will be diminished, worsening its moldability, and also reducing its vital rubber elasticity. However, there are almost no examples in which the use of crosslinking treatment has been considered. In particular, it was not known whether thermoplastic polyamide elastomer resin could be crosslinked or not, so this 1JJ resin and its pre-expanded particles, which were crosslinked within the range specified in the present invention, achieved excellent foam moldability. However, it was completely unexpected that there was almost no deterioration in terms of physical and chemical properties, but rather improvements.
本発明による発泡粒子は、上述のようにポリアミド系エ
ラストマー１１ＪＩ脂を架橋処理したものからなるが、
架橋による樹脂の分子構造の変化は、熱キシレン不溶解
残渣の増加により、間接的に知ることができる。すなわ
ち、未架橋のポリアミド系エラストマーは熱キシレンに
完全に溶解するが、架橋度を大にするにつれて熱キシレ
ン不溶解残渣は増加し、最大６０〜８５％程度に達する
。本発明による発泡粒子は、熱キシレン不溶解残渣が６
０％をこえない程度に架橋処理されそれにより樹脂が好
ましくは０ 、５ ｇ／１０分以上、特に好ましくは１
〜２５ｇ／１０分のメルトインデクスを示す溶融時流動
性を保持しているものである。共重合体分子鎖中で架橋
結合が形成されている部位は、まだ完全に解明されては
いないが、主としてポリエーテルからなるソフトセグメ
ントと考えられる。The foamed particles according to the present invention are made of polyamide elastomer 11JI resin subjected to crosslinking treatment as described above.
Changes in the molecular structure of the resin due to crosslinking can be indirectly known by the increase in thermal xylene insoluble residue. That is, an uncrosslinked polyamide elastomer completely dissolves in hot xylene, but as the degree of crosslinking increases, the amount of residue insoluble in hot xylene increases, reaching a maximum of about 60 to 85%. The foamed particles according to the present invention have a heat xylene insoluble residue of 6
The resin is cross-linked to an extent not exceeding 0%, so that the resin is preferably 0.5 g/10 minutes or more, particularly preferably 1.
It maintains fluidity when melted showing a melt index of ~25 g/10 minutes. Although the site where crosslinks are formed in the copolymer molecular chain has not yet been completely elucidated, it is thought to be a soft segment mainly composed of polyether.
本発明による発泡粒子を構成する架橋エラストマーの原
料樹脂として好ましいのは、ポリアミド系エラストマー
樹脂の中でもポリラウリンラクタムーポリテＹラバイド
ロアランブロック共重合体である。但しこの重合体のソ
７）セグメント１よ、ポリテトラハイドロ７ランのはか
にアンピン酸、アセ′ライン酸、トデカンニ酸等の第三
成分に由来する基を含んでいてもよい。またこの共重合
体の中でも特に好ましいのは、ポリラウリンラクタムセ
グメンＦを３０〜８０重景％、ポリテトラハイドロ７ラ
ンセグメントを２０〜５０重景％、それぞれ含有するも
のである。この樹脂は、上記本発明による発泡粒子を構
成するエラストマー樹脂に要求されるメルトインデクス
を維持しながら発泡成形性その他の性質においてすぐれ
たエラストマー樹脂を与える点で、１匹のポリアミド系
エラストマー樹脂よりもすぐれている。Among polyamide-based elastomer resins, polylaurinlactam-polyte-Y-labide-loalane block copolymer is preferred as the raw material resin for the crosslinked elastomer constituting the expanded particles of the present invention. However, the segment 1 of this polymer may contain a group derived from a third component such as ampic acid, ace'laic acid, todecanoic acid, etc. of polytetrahydro-7. Particularly preferred among these copolymers are those containing 30 to 80 weight percent of polylaurin lactam segment F and 20 to 50 weight percent of polytetrahydro7 run segment, respectively. This resin is superior to a single polyamide-based elastomer resin in that it provides an elastomer resin with excellent foam moldability and other properties while maintaining the melt index required for the elastomer resin constituting the expanded particles of the present invention. It is excellent.
ポリアミド系エラストマー１７１脂から本発明による発
泡粒子用の架橋エラストマー樹脂を製造するための架橋
法は、ポリオレフィン樹脂等の架橋処理に採用される化
学架橋、電子線架橋、放射線架橋なと、いずれの方法ｌ
こよってもよいが、最も適当なのは、化学架橋である。The crosslinking method for producing the crosslinked elastomer resin for foamed particles according to the present invention from the polyamide elastomer 171 resin may be any of chemical crosslinking, electron beam crosslinking, and radiation crosslinking that are employed for crosslinking of polyolefin resins, etc. l
Although various methods are possible, the most suitable method is chemical crosslinking.
架橋剤としては、Ｌ−７チルクミルパーオキサイド、ジ
クミルパーオキサイド、２．５−ン゛メチルー２，５−
ノーし一ブチルパーオキシー３−ヘキシン、２，２−ビ
ス（ｔ−ブチルパーオキシ）プロパン、ビス（１−ブチ
ルパーオキシ）ノフェニルシランなどが適当である。処
理に際しては、水、エタノール、エチレングリコールな
どを分散媒として樹脂粒子を懸濁させ、また適当な架橋
助剤を併用するとよい。As a crosslinking agent, L-7 thicumyl peroxide, dicumyl peroxide, 2.5-methyl-2,5-
Suitable examples include 1-butylperoxy-3-hexyne, 2,2-bis(t-butylperoxy)propane, and bis(1-butylperoxy)nophenylsilane. During the treatment, the resin particles may be suspended using water, ethanol, ethylene glycol, or the like as a dispersion medium, and a suitable crosslinking aid may be used in combination.
架橋による原料樹脂の改質は架橋度にほぼ比例する形で
進むか呟ポリアミド系エラストマー樹脂改質法として考
えるならば架橋処理の程度に下限はないが、発泡成形が
可能なエラストマーを得るためには、架橋は熱キシレン
不溶解残渣が少なくとも０．５％に達するまで進めるこ
とが望ましい。Modification of the raw material resin by crosslinking proceeds in a manner roughly proportional to the degree of crosslinking.When considered as a polyamide-based elastomer resin modification method, there is no lower limit to the degree of crosslinking, but in order to obtain an elastomer that can be foam-molded, It is desirable that the crosslinking proceed until at least 0.5% of hot xylene insoluble residue is reached.
」二連のようにして得られる架橋ポリアミドエラストマ
ー樹脂から本発明の発泡粒子を製造するのは容易であっ
て、この樹脂の粒子を、ポリスチレンやポリオレフィン
の発泡粒子を製造する場合と同様に、例えば特公昭５６
−１３４４号公報記載の方法により発泡させればよい。It is easy to produce the foamed particles of the present invention from the crosslinked polyamide elastomer resin obtained in two series, and the particles of this resin can be prepared by, for example, producing foamed particles of polystyrene or polyolefin. Special Public Service 1986
It may be foamed by the method described in Japanese Patent No.-1344.
すなわち、上記架橋ｔｊｔ脂の粒子に揮発性溶剤型発泡
剤を吸収させ、更に分散媒と共に密閉容器中で加圧下に
加熱したのち分散媒と共に容器内よりも低圧の雰囲気に
放出して発泡させる。用いる発泡剤としては、ｔｊｌ脂
粒子に浸透することので終る低沸点の有機化合物（通常
−５０〜１１０°Ｃ程度の沸点を有するもの）が適当で
ある。その具体例としては、プロパン、ブタン、ペンタ
ン、ヘキサン、ヘプタン等の脂肪族炭化水素類；シクロ
７タン、シクロペンタン等の環式脂肪族炭化水素類；ト
リクロロフルオロメタン、ジクロロフルオロメタン、ジ
クロロジフルオロメタン、ジクロロテトラフルオロエタ
ン、メチルクロライド、エチルクロライド、／チレンク
ロライド等のハロゲン化炭化水素類などがある。発泡剤
を樹脂粒子に吸収させるには、常温で、または加熱下に
、両者を接触させればよいが、この工程は、独立に行う
ほか、樹脂粒子を分散媒と共に密閉容器中で加熱する工
程と同時に行なってもよい。その場合は、未処理の樹脂
粒子、発泡剤および分散媒を密閉容器に仕込み、撹拌し
ながら昇温する。あるいは密閉容器内で未処理樹脂粒子
および分散媒を加熱し、所定の温度に達するまでの任意
の段階で、発泡剤を密閉容器内に注入し混合する。分散
媒としては水を用いることがで終る。分散媒に樹脂粒子
を分散させて密閉容器中で加熱するに当り、分散媒には
ほかに分散剤たとえば酸化アルミニウム、酸化チタン、
塩基性炭酸マグネシウム、塩基性炭酸亜鉛、炭酸カルシ
ウム等の微粉末を添加して樹脂粒子の融着を防止しても
よい。分散剤の添加量は、樹脂粒子１００重量部当り通
常０．０１〜１０重量部程度にする二とが望ましい。加
熱工程における加熱温度は、樹脂の軟化温度基」二、樹
脂粒子間の融着が起こらない程度の温度であればよい。That is, particles of the crosslinked TJT resin are allowed to absorb a volatile solvent-based foaming agent, and then heated together with a dispersion medium under pressure in a closed container, and then released together with the dispersion medium into an atmosphere at a lower pressure than the inside of the container to cause foaming. As the blowing agent to be used, it is appropriate to use a low-boiling organic compound (usually having a boiling point of about -50 to 110°C) that penetrates into the TJL fat particles. Specific examples include aliphatic hydrocarbons such as propane, butane, pentane, hexane, and heptane; cyclic aliphatic hydrocarbons such as cyclo7tane and cyclopentane; trichlorofluoromethane, dichlorofluoromethane, and dichlorodifluoromethane. , dichlorotetrafluoroethane, methyl chloride, ethyl chloride, and halogenated hydrocarbons such as ethylene chloride. In order to absorb the blowing agent into the resin particles, the two may be brought into contact at room temperature or under heating, but this step can be carried out independently or by heating the resin particles together with a dispersion medium in a closed container. It may be done at the same time. In that case, untreated resin particles, a blowing agent, and a dispersion medium are placed in a closed container, and the temperature is raised while stirring. Alternatively, untreated resin particles and a dispersion medium are heated in a closed container, and at any stage until a predetermined temperature is reached, a blowing agent is injected into the closed container and mixed. Water is used as the dispersion medium. When dispersing resin particles in a dispersion medium and heating it in a closed container, the dispersion medium also contains dispersants such as aluminum oxide, titanium oxide,
Fine powder of basic magnesium carbonate, basic zinc carbonate, calcium carbonate, etc. may be added to prevent resin particles from fusing. The amount of the dispersant added is preferably about 0.01 to 10 parts by weight per 100 parts by weight of the resin particles. The heating temperature in the heating step may be a temperature based on the softening temperature of the resin, which does not cause fusion between resin particles.
好ましい温度はもちろん原料樹脂の種類により異なるが
、通常１１０〜１５０℃である。この温度が高すぎると
粒子同士の融着により次の発泡工程に移すことが困難に
なるはかりでなく、気泡の破壊が起こって独立気泡率の
低い発泡粒子となってしまう。また加熱時間は特に限定
されないが、この加熱中に発泡剤を吸収させる場合は、
発泡剤が粒子中に均一に吸収されるまで処理する必要が
あること、いうまでもない。このあと、密閉容器の内容
物を容器内圧よりも低い圧力の雰囲気に放出して発泡剤
を気化させることにより樹脂粒子を発泡させる。分散媒
として水を用いた場合、上記のようにして発泡させる雰
囲気はふつう常圧の大気でよい。The preferred temperature naturally varies depending on the type of raw material resin, but is usually 110 to 150°C. If this temperature is too high, particles will fuse together, making it difficult to proceed to the next foaming step, and the cells will be destroyed, resulting in foamed particles with a low closed cell ratio. The heating time is not particularly limited, but if the foaming agent is absorbed during this heating,
It goes without saying that it is necessary to process until the blowing agent is uniformly absorbed into the particles. Thereafter, the resin particles are foamed by releasing the contents of the sealed container into an atmosphere having a pressure lower than the internal pressure of the container to vaporize the foaming agent. When water is used as a dispersion medium, the atmosphere in which foaming is carried out as described above may generally be atmospheric pressure.
本発明による発泡粒子の発泡倍率は、上記の製造条件を
調整することに上り、約５〜３０倍とし、主た粒径は１
〜１０帥とすることが望ましい。The expansion ratio of the expanded particles according to the present invention is approximately 5 to 30 times by adjusting the above manufacturing conditions, and the main particle size is 1
It is desirable to set it to ~10 degrees.
本発明による発泡粒子は、型内発泡成形法によって、ポ
リウレタンフォームなみの高弾性発泡成形体とすること
かで外る。すなわち、常温常圧下に養生したのち、望ま
しくは無機ガス、有機力又まｔこはこれらの混合物中、
加圧下に養生し、次いで成形用型内に充填し、水蒸気吹
込みにより加熱して成形する。The foamed particles according to the present invention can be molded into a highly elastic foamed product similar to polyurethane foam by an in-mold foaming method. That is, after curing at room temperature and pressure, preferably an inorganic gas and an organic gas are added to the mixture.
The material is cured under pressure, then filled into a mold, heated by steam injection, and molded.
本発明による発泡粒子は、上記型内成形におり・てポリ
スチレンやポリオレフィンの発泡粒子とほぼ同程度のす
くれた成形性を示し、成形時の収縮はほとんどない。ま
た、判られる成形体は、表面が平滑で、微細かつ均一な
気泡を含有し、更に、架橋ポリアミドエラストマーのす
ぐれた特性に基づき、良好なコム弾性、引張強度、低温
特性、耐摩耗性、耐薬品性、耐水性、耐熱性、接着性、
染料親和性、および適度の親水性を備えている６−呟ポ
リウレタン７す一ムよりも高性能の発泡成形体として、
断熱材、衣料、敷物、寝具、建材、インテリア、自動車
用品、包装材料など、多くの分野で利用することができ
る。The foamed particles according to the present invention exhibit almost the same level of moldability as the foamed particles of polystyrene or polyolefin when molded in a mold as described above, and exhibit almost no shrinkage during molding. In addition, the molded product has a smooth surface, contains fine and uniform air bubbles, and, based on the excellent properties of the crosslinked polyamide elastomer, has good comb elasticity, tensile strength, low temperature properties, abrasion resistance, and resistance. Chemical resistance, water resistance, heat resistance, adhesiveness,
As a foamed molded product with higher performance than the 6-mole polyurethane 7 unit, which has dye affinity and moderate hydrophilicity,
It can be used in many fields such as insulation, clothing, rugs, bedding, building materials, interiors, automotive supplies, and packaging materials.
以下実施例を示して本発明を説明する。なおこの明細書
に示したメルトインデクスおよび熱キシレン不溶解残渣
の測定法は次のとおりである。The present invention will be explained below with reference to Examples. The methods for measuring the melt index and hot xylene insoluble residue shown in this specification are as follows.
メルトインデクス： ＡＳＴＭ Ｄ１２３８のＢ法によ
る。Melt index: According to method B of ASTM D1238.
惧し、測定温度は２５０°Ｃとし、荷重はｓｏｏｏｇ、
−ｉ゛リフイス径２．１龍、オリフィス高さは８ｖｎと
した。Therefore, the measurement temperature was 250°C, the load was sooog,
-i゛The orifice diameter was 2.1mm, and the orifice height was 8vn.
熱えシレン不）容ガツ残渣：精秤した試料約１ｇを１０
１）ｃｃの沸騰キシレンで処理したのち熱時濾過し、残
渣を真空乾燥後精秤し、試料重量１こ月する百分率をめ
る。Residue: Approximately 1 g of accurately weighed sample is
1) After treatment with cc of boiling xylene, filter while hot, and accurately weigh the residue after vacuum drying, and calculate the percentage of the sample weight in 1 month.
実施例および比較例
ポリラウリンラクタムをハードセグメントとしポリエー
テルエステル（テトラハイドロアランとドデ′カンニ酸
との共重合物；重合度的１０００）をソ７）セグメント
とするポリアミド系エラストマー・グイアミド−ＰＡＥ
（グイセル化学工業社製品； Ｔ＋ｎ＝ １５２°Ｃ）
の粒子（平均直径２晴；平均長さ３ｍｍ）１００重量部
を０．５重量部の微粒子状酸化アルミニウムと共に２０
０重量部の水の中に分散させる。分散液に更に架橋剤・
ジクミルパーオキサイドを加え、オートクレーブ中で撹
拌しながら１５０℃まで３°Ｃ／分の昇温速度で昇温さ
せ、その後１５０℃で１８０分間、加熱して架橋処理を
行う。Examples and Comparative Examples Polyamide elastomer guamide-PAE with polylaurin lactam as a hard segment and polyether ester (copolymer of tetrahydroalane and dode'cannic acid; degree of polymerization: 1000) as a 7) segment
(Product from Gwisel Chemical Industry Co., Ltd.; T+n=152°C)
100 parts by weight of particles (average diameter 2 mm; average length 3 mm) were mixed with 0.5 parts by weight of finely divided aluminum oxide.
Disperse in 0 parts by weight of water. A crosslinking agent/
Dicumyl peroxide is added, and the temperature is raised to 150° C. at a rate of 3° C./min while stirring in an autoclave, and then heated at 150° C. for 180 minutes to perform a crosslinking treatment.
架橋剤の添加量を０〜２．０重量部の範囲で種々変更し
て上記処理を行ない、５種類の架橋エラストマーｔｉｔ
脂を得た。The above treatment was carried out by varying the amount of crosslinking agent added in the range of 0 to 2.0 parts by weight, and five types of crosslinked elastomers were obtained.
I got fat.
各例樹脂の特性を表１に示す。Table 1 shows the properties of each example resin.
次に樹脂粒子１００重量部に対し水３００重量部および
発泡剤（ジクロロノフルオロメタン）１８重量部を混合
したものをオートクレーブに入れ、１２８℃に列温後、
窒素ガスで背圧をかけながらオートクレーブ底部の排出
口を開いて内容物を大気中に放出する方法により、上記
処理後の樹脂粒子ならびに市販のポリエステル系エラス
トマー樹脂（比較例３）および熱可塑性ポリウレタン系
エラストマー樹脂（比較例４）から発泡粒子を製造した
。Next, a mixture of 100 parts by weight of resin particles, 300 parts by weight of water and 18 parts by weight of a blowing agent (dichloronofluoromethane) was placed in an autoclave, and heated to 128°C.
By applying back pressure with nitrogen gas and opening the outlet at the bottom of the autoclave to release the contents into the atmosphere, the treated resin particles as well as commercially available polyester elastomer resin (Comparative Example 3) and thermoplastic polyurethane resin were prepared. Expanded particles were produced from an elastomer resin (Comparative Example 4).
次に各発泡粒子は、大気中に４８時間放置後、３５℃・
２゜５ Ｋｇ／ｃｍ２Ｇの空気で４８時間加圧養生して
がら、２０ｍｍＸ３００ ＋ｎｍＸ ３００ ｍｍの成
形用金型に充填し、３．５ Ｋｇ／ｃｍ２Ｇの水蒸気を
吹込んで再発泡と粒子間融着を起こさせることにより、
板状に成形した。Next, each foamed particle was left in the atmosphere for 48 hours and then heated to 35°C.
While pressurizing and curing with air at 2.5 Kg/cm2G for 48 hours, it was filled into a 20 mm x 300 + nm x 300 mm mold, and water vapor at 3.5 Kg/cm2G was blown to cause re-foaming and interparticle fusion. By causing
It was formed into a plate shape.
上記のようにして得られた発泡粒子および発泡成形体の
性状を表２に示す。Table 2 shows the properties of the expanded particles and expanded molded product obtained as described above.
表 １
架橋剤使用量 熱キシレン不 メルトインデ（重量ｆｉ
ｌｓ） 溶解残渣（％） クス（８／１０分）比較例１
０ ０ Ｇ２
実施例１ １）、５ ２．５ ２９
実施例２ ０，６ １９．１ １７
実施例３ ０．８ ３８．０ ５
比較例２ ２．０ Ｇｏ、２ ０Table 1 Amount of crosslinking agent used Hot xylene-free melt inde (weight fi
ls) Dissolution residue (%) Sox (8/10 minutes) Comparative example 1
0 0 G2 Example 1 1), 5 2.5 29 Example 2 0,6 19.1 17 Example 3 0.8 38.0 5 Comparative example 2 2.0 Go, 2 0
Claims (5)
おいて、該発泡粒子を構成する樹脂が結晶性ポリアミド
セグメントおよびポリエーテルセグメントを有するブロ
ック共重合体からなる熱可塑性エラストマー樹脂の架橋
処理物であってノルトインデクスが４０ｇ／１０分をこ
えず熱キシレン不溶解残渣が６０％をこえないものより
なることを特徴とする発泡粒子。(1) In foamed particles for producing thermoplastic synthetic resin foam molded articles, the resin constituting the foamed particles is a crosslinked thermoplastic elastomer resin made of a block copolymer having a crystalline polyamide segment and a polyether segment. 1. A foamed particle characterized in that the Nord index does not exceed 40 g/10 minutes and the thermal xylene insoluble residue does not exceed 60%.
ントおよびポリテトラハイドロフランセグメントを有す
るブロック共重合体である特許請求の範囲第１項記載の
発泡粒子。(2) The expanded particles according to claim 1, wherein the block copolymer is a block copolymer having a polylaurinlactam segment and a polytetrahydrofuran segment.
ント３０〜８０重景％およびポリテトラハイドロ７ラン
セグメント２０〜５０重量％を含有するものである特許
請求の範囲第２項記載の発泡粒子。(3) The expanded particles according to claim 2, wherein the block copolymer contains 30 to 80% by weight of polylaurinlactam segments and 20 to 50% by weight of polytetrahydro-7 segments.
１０分である特許請求の範囲第１項記載の発泡粒子。(4) The melt index of the crosslinked product is 1 to 251+/
The foamed particles according to claim 1, wherein the foaming time is 10 minutes.
４５％である特許請求の範囲第１項記載の発泡粒子。(5) The thermal xylene insoluble residue of the cross-linked product is 0.5~
45%. The expanded particles according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14968183A JPS6042432A (en) | 1983-08-18 | 1983-08-18 | Foamed particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14968183A JPS6042432A (en) | 1983-08-18 | 1983-08-18 | Foamed particle |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6042432A true JPS6042432A (en) | 1985-03-06 |
| JPH0417977B2 JPH0417977B2 (en) | 1992-03-26 |
Family
ID=15480491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14968183A Granted JPS6042432A (en) | 1983-08-18 | 1983-08-18 | Foamed particle |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6042432A (en) |
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| JP2016188342A (en) * | 2015-03-30 | 2016-11-04 | 積水化成品工業株式会社 | Amide foamed resin particle and foamed molding |
| JP2017066279A (en) * | 2015-09-30 | 2017-04-06 | 積水化成品工業株式会社 | Surface modified expandable particle, manufacturing method of foam particle and manufacturing method of foam molded body |
| JP2017066197A (en) * | 2015-09-28 | 2017-04-06 | 積水化成品工業株式会社 | Surface modified expandable particle, manufacturing method of foam particle and manufacturing method of foam molded body |
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| JP2017179122A (en) * | 2016-03-30 | 2017-10-05 | 積水化成品工業株式会社 | Polyamide resin foam sheet, laminated sheet, foam molding, and method for producing polyamide resin foam sheet |
| WO2017220671A1 (en) | 2016-06-23 | 2017-12-28 | Basf Se | Method for producing foam particles made of thermoplastic elastomers with polyamide segments |
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-
1983
- 1983-08-18 JP JP14968183A patent/JPS6042432A/en active Granted
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| CN106687511B (en) * | 2014-09-30 | 2020-02-21 | 积水化成品工业株式会社 | Amide elastomer foamed particles, method for producing same, foamed molded article, and method for producing foamed molded article |
| JP2016188342A (en) * | 2015-03-30 | 2016-11-04 | 積水化成品工業株式会社 | Amide foamed resin particle and foamed molding |
| JP2017066197A (en) * | 2015-09-28 | 2017-04-06 | 積水化成品工業株式会社 | Surface modified expandable particle, manufacturing method of foam particle and manufacturing method of foam molded body |
| JP2017066279A (en) * | 2015-09-30 | 2017-04-06 | 積水化成品工業株式会社 | Surface modified expandable particle, manufacturing method of foam particle and manufacturing method of foam molded body |
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| US10959357B2 (en) | 2017-09-07 | 2021-03-23 | Murata Manufacturing Co., Ltd. | Circuit block assembly |
| CN110294860A (en) * | 2018-03-21 | 2019-10-01 | 加久企业股份有限公司 | Elastic composite material processing procedure and its finished product |
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Also Published As
| Publication number | Publication date |
|---|---|
| JPH0417977B2 (en) | 1992-03-26 |
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