JP6436583B2 - Method for producing cyclic olefin-based resin expanded particles and method for producing expanded molded body - Google Patents
Method for producing cyclic olefin-based resin expanded particles and method for producing expanded molded body Download PDFInfo
- Publication number
- JP6436583B2 JP6436583B2 JP2016054035A JP2016054035A JP6436583B2 JP 6436583 B2 JP6436583 B2 JP 6436583B2 JP 2016054035 A JP2016054035 A JP 2016054035A JP 2016054035 A JP2016054035 A JP 2016054035A JP 6436583 B2 JP6436583 B2 JP 6436583B2
- Authority
- JP
- Japan
- Prior art keywords
- particles
- foamed
- foaming
- cyclic olefin
- resin
- 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.)
- Active
Links
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
本発明は、環状オレフィン系樹脂発泡粒子の製造方法及び発泡成形体の製造方法に関する。更に詳しくは、本発明は、良好な外観を有する発泡成形体を製造するための環状オレフィン系樹脂発泡粒子の製造方法、その方法により得られる環状オレフィン系樹脂発泡粒子を型内発泡成型して発泡成形体を得る発泡成形体の製造方法に関する。 The present invention relates to a process for producing a preparation and foamed molded cycloolefin resin foamed particles child. More particularly, the present invention provides foaming process for producing a molded article cycloolefin resin foamed particles for producing a cyclic olefin based resin foamed particles obtained by the method and mold expansion molding having a good appearance foaming The present invention relates to a method for producing a foamed molded product for obtaining a molded product .
環状オレフィン系樹脂は、従来の非環状オレフィン系樹脂に比べて熱的安定性、化学的安定性、弾性率等の物性が優れており、光学フィルム等の光学分野、包装材料分野、医療・検査機器分野、電子デバイス分野等に幅広く使用されている。発泡体の分野においても、環状オレフィンを基材樹脂とした種々の発泡体が提案されている。
ところで、環状オレフィン系樹脂を基材樹脂とする発泡体の製法としては、例えば特許文献１（特開２０１３−１８９４８４号公報）のような押出発泡法がよく知られている。しかしながら、この方法で得られる発泡体は、棒状もしくはボード状であるため、単純な形状の発泡体しか得ることができなかった。従って、押出発泡法では、複雑な形状をした発泡体を得ることは困難であった。
Cyclic olefin resins have better physical properties such as thermal stability, chemical stability, and elastic modulus than conventional non-cyclic olefin resins, and include optical fields such as optical films, packaging materials, and medical / inspection. Widely used in the field of equipment and electronic devices. Also in the field of foams, various foams using a cyclic olefin as a base resin have been proposed.
By the way, as a manufacturing method of the foam which uses cyclic olefin resin as base resin, the extrusion foaming method like patent document 1 (Unexamined-Japanese-Patent No. 2013-189484) is known well, for example. However, since the foam obtained by this method is rod-shaped or board-shaped, only a simple foam can be obtained. Therefore, it has been difficult to obtain a foam having a complicated shape by the extrusion foaming method.
複雑な形状の発泡体を得る方法としては、発泡粒子を金型内で発泡及び融着させる型内発泡成型法が知られている。この方法では、所望の形状に対応する空間を有する金型を用意し、その空間内に発泡粒子を充填し、加熱により発泡粒子を発泡及び融着させることで、複雑な形状を有する発泡成形体を得ることができる。この方法が、例えば、特許文献２（特開平８−３３３４７１号公報）及び特許文献３（特開２０１０−１８９５８２号公報）に提案されている。具体的には、特許文献２の実施例では、環状オレフィン系樹脂粒子に対し発泡剤としてイソブタンを含浸して発泡性粒子を作製し、発泡性粒子を加熱発泡させることで発泡粒子を作製し、その後発泡粒子を金型内で加熱発泡(二次発泡)させて成形して得られる発泡成形体が記載されている。また、特許文献３の実施例では、環状オレフィン系樹脂粒子に対し発泡剤としてブタン、ペンタンを含浸して発泡性粒子を作製し、発泡性粒子を加熱発泡させることで発泡粒子を作製し、その後発泡粒子を金型内で加熱発泡(二次発泡)させて成形して得られる発泡成形体が開示されている。 As a method for obtaining a foam having a complicated shape, an in-mold foam molding method in which foamed particles are foamed and fused in a mold is known. In this method, a mold having a space corresponding to a desired shape is prepared, the foamed particles are filled in the space, and the foamed particles are foamed and fused by heating, whereby a foamed molded product having a complicated shape. Can be obtained. This method is proposed, for example, in Patent Document 2 (Japanese Patent Laid-Open No. 8-333471) and Patent Document 3 (Japanese Patent Laid-Open No. 2010-189582). Specifically, in the example of Patent Document 2, the foamed particles are produced by impregnating cyclobutane resin particles with isobutane as a foaming agent to produce foamable particles, and the foamable particles are heated and foamed. A foam molded article obtained by molding foamed particles by heat foaming (secondary foaming) in a mold is described. Moreover, in the Example of patent document 3, a foaming particle is produced by impregnating a cyclic olefin resin particle with butane and pentane as a foaming agent to produce foaming particles, and then heating and foaming the foaming particles. A foamed molded article obtained by molding foamed particles by heat foaming (secondary foaming) in a mold is disclosed.
特許文献２及び３では、発泡成形体の作製に、ブタン、イソブタン、ペンタン等の有機系物理発泡剤が使用されている。しかし、有機系物理発泡剤は、樹脂への可塑効果が強く、かつ樹脂からの気散速度が遅いため、その樹脂本来の耐熱性を発揮するには十分にアニールする必要があった。そのため、生産性改善の観点から発泡剤を変更することが望まれている。加えて、近年、有機系物理発泡剤が環境に与える影響が懸念されており、この観点からも、発泡剤を変更することが望まれている。 In Patent Documents 2 and 3, organic physical foaming agents such as butane, isobutane, and pentane are used for producing foamed molded articles. However, since the organic physical foaming agent has a strong plasticizing effect on the resin and a low air diffusion rate from the resin, it has to be sufficiently annealed to exhibit the heat resistance inherent to the resin. Therefore, it is desired to change the foaming agent from the viewpoint of improving productivity. In addition, in recent years, there is a concern about the influence of organic physical foaming agents on the environment, and from this viewpoint, it is desired to change the foaming agent.
本発明の発明者等は、このような状況を鑑みて、無機系物理発泡剤を使用して発泡成形体を作製する検討を行った。その結果、環状オレフィン系樹脂粒子を無機系物理発泡剤で発泡させて発泡粒子を作製し、その発泡粒子を型内成形して発泡成形体を得るには特許文献２の段落０００７及び０００８でも指摘される以下の課題が発生することを見い出した。 In view of such a situation, the inventors of the present invention studied to produce a foamed molded article using an inorganic physical foaming agent. As a result, it is pointed out in paragraphs 0007 and 0008 of Patent Document 2 that foamed particles are produced by foaming cyclic olefin-based resin particles with an inorganic physical foaming agent, and the foamed particles are molded in-mold to obtain a foamed molded product. We found that the following problems occur.
即ち、一般に、発泡剤を用いて製造した直後の発泡粒子内には発泡剤が含有される。このような発泡剤が多量に含まれた発泡粒子を使用して型内成形を行なうと、最終的には発泡剤は空気と置換されることになる。しかし、成形中、発泡剤が気散する速度の方が、成形体中に空気が進入してくる速度よりも速いため、成形体が収縮する原因となる。これを防止するため、製造直後の発泡粒子に含まれる発泡剤を、型内成形に先立ち、一旦空気と置換させる方法が一般に採用されている。そして、必要に応じて加圧空気や加圧窒素等を使用して発泡粒子内の内圧を高めた後、型内成形が行なわれている。 That is, generally, the foaming agent is contained in the foamed particles immediately after the production using the foaming agent. When in-mold molding is performed using expanded particles containing a large amount of such a foaming agent, the foaming agent is eventually replaced with air. However, since the speed at which the foaming agent diffuses during molding is faster than the speed at which air enters the molded body, this causes the molded body to shrink. In order to prevent this, generally employed is a method in which the foaming agent contained in the foamed particles immediately after production is once replaced with air prior to in-mold molding. And after increasing the internal pressure in foamed particles using pressurized air, pressurized nitrogen, etc. as needed, in-mold fabrication is performed.
製造直後の発泡粒子内に存在する発泡剤を空気と置換するには、通常の鎖状オレフィン系樹脂（例えば、ポリエチレン）の発泡粒子の場合には、発泡粒子を網槽内にて大気圧下で適当な時間放置することで実施される。ところが、環状オレフィン系樹脂の発泡粒子の場合には、鎖状オレフィン系樹脂発泡粒子のように、発泡剤と空気とを完全に置換してしまうと、その後の型内成形に先立ち、加圧空気等を使用して発泡粒子内圧を高め、この発泡粒子を使用して型内成形しても、各発泡粒子の膨張が十分に行われず(いわゆる成形時の発泡不足が生じ)、良好な発泡成形体が得られないという課題がある。 In order to replace the foaming agent present in the foamed particles immediately after production with air, in the case of foamed particles of a normal chain olefin resin (for example, polyethylene), the foamed particles are placed under atmospheric pressure in a mesh tank. It is carried out by leaving it for a suitable time. However, in the case of foamed particles of cyclic olefin-based resin, if the blowing agent and air are completely replaced as in the case of chain-shaped olefin-based resin foamed particles, pressurized air is used prior to subsequent in-mold molding. Even if foamed particles are used to increase the internal pressure of the foamed particles, and the foamed particles are molded in the mold, the foamed particles are not sufficiently expanded (so-called foaming shortage occurs during molding), and good foamed molding There is a problem that the body cannot be obtained.
特許文献２では、発泡粒子に残存した発泡剤が気散する前に成形を行なうことで上記課題を解決している。しかし、一般に、無機系物理発泡剤は有機系物理発泡剤に比べて樹脂外への気散が速い。従って、無機系物理発泡剤を使用して環状オレフィン系樹脂の発泡粒子を作製し、型内成形し、発泡成形体を得る際に、特許文献２と同様の方法にて良好な発泡成形体を得ることは困難である。そのため、特許文献２に記載された方法以外で、発泡粒子の膨張を十分に行い（いわゆる成形時に十分発泡させ)、良好な発泡成形体を得る対策を考案する必要があった。 In patent document 2, the said subject is solved by performing shaping | molding before the foaming agent which remain | survived in the expanded particle disperses. However, in general, the inorganic physical foaming agent has a faster air diffusion out of the resin than the organic physical foaming agent. Therefore, when foamed particles of a cyclic olefin resin are prepared using an inorganic physical foaming agent and molded in-mold to obtain a foamed molded product, a good foamed molded product is obtained by the same method as in Patent Document 2. It is difficult to get. Therefore, in addition to the method described in Patent Document 2, it is necessary to devise a measure for sufficiently expanding the expanded particles (sufficiently foaming at the time of so-called molding) to obtain a good foamed molded product.
発明者等は、上記課題を解決すべく誠意研究を行なった結果、無機系物理発泡剤を使用して作製した環状オレフィン系樹脂発泡粒子が、特定の条件を満足する場合に型内成形に十分な発泡性を発揮し、それを用いることで外観の良好な発泡成形体を得ることができることを見出し、本発明を完成するに至った。
かくして本発明によれば、基材樹脂としての環状オレフィン系樹脂と、無機系物理発泡剤とを含む発泡性粒子を発泡させて型内成形用の発泡粒子を製造する方法であり、前記発泡は、２回以上のｎ回行われ、１回目の発泡で得られた発泡粒子が０．５１〜０．０５１ｇ／ｃｍ 3 の嵩密度Ｔ１を示し、ｎ回目の発泡で得られた発泡粒子が０．０５１〜０．００６８ｇ／ｃｍ 3 の嵩密度Ｔ２を示し、前記嵩密度Ｔ２が、前記嵩密度Ｔ１の０．６倍以下である条件で行われることを特徴とする環状オレフィン系樹脂発泡粒子の製造方法が提供される。
The inventors have conducted sincere research to solve the above problems, and as a result, the foamed cyclic olefin resin particles produced using an inorganic physical foaming agent are sufficient for in-mold molding when specific conditions are satisfied. The present inventors have found that a foamed molded article exhibiting excellent foamability and having a good appearance can be obtained by using it, and the present invention has been completed.
Thus, according to the present invention, there is provided a method for producing foamed particles for in-mold molding by foaming foamable particles containing a cyclic olefin resin as a base resin and an inorganic physical foaming agent. The foamed particles obtained by the first foaming exhibited a bulk density T1 of 0.51 to 0.051 g / cm 3 , and the foamed particles obtained by the nth foaming were 0. A cyclic olefin-based resin expanded particle having a bulk density T2 of .051 to 0.0068 g / cm 3 , wherein the bulk density T2 is 0.6 times or less of the bulk density T1 . A manufacturing method is provided.
更に、上記環状オレフィン系樹脂発泡粒子を得、前記環状オレフィン系樹脂発泡粒子を型内発泡成型して発泡成形体を得る発泡成形体の製造方法が提供される。 Further, the give the cyclic olefin-based resin foamed particles, method for producing a foamed molded to obtain a foamed molded product the cyclic olefin-based resin foamed particles were mold foam molding is provided.
本発明の製造方法によれば、外観の良好な発泡成形体を与え得る環状オレフィン系樹脂発泡粒子の製造方法を提供できる。
以下のいずれかの場合、外観のより良好な発泡成形体を与え得る環状オレフィン系樹脂発泡粒子の製造方法を提供できる。
（１）発泡が、２回以上のｎ回行われ、１回目の発泡で得られた発泡粒子が０．５１〜０．０５１ｇ／ｃｍ３の嵩密度Ｔ１を示し、ｎ回目の発泡で得られた発泡粒子が０．３４〜０．００６８ｇ／ｃｍ３の嵩密度Ｔ２を示す条件で行われる。
（２）嵩密度Ｔ２が、嵩密度Ｔ１の０．６倍以下である。
（３）無機系物理発泡剤が、二酸化炭素、窒素、酸素、空気及びアルゴンから選択される。
（４）環状オレフィン系樹脂が、鎖状オレフィン成分と環状オレフィン成分とから構成される共重合体から選択される。
（５）鎖状オレフィン成分が炭素数２〜６のエチレン系炭化水素に由来する成分であり、環状オレフィン成分が炭素数３〜１０の単環又は多環の炭化水素に由来する成分である。
（６）環状オレフィン系樹脂発泡粒子が、４０％以下の連続気泡率を有する。
According to the production method of the present invention, it is possible to provide a method for producing a cyclic olefin resin expanded particle capable of giving a foamed molded article having a good appearance.
In any of the following cases, it is possible to provide a method for producing foamed cyclic olefin resin particles that can give a foamed molded article with better appearance.
(1) Foaming is carried out n times at least twice, and the foamed particles obtained by the first foaming exhibit a bulk density T1 of 0.51 to 0.051 g / cm 3 and are obtained by the nth foaming. The expansion | swelling particle | grains carried out on the conditions which show the bulk density T2 of 0.34-0.0068g / cm < 3 >.
(2) The bulk density T2 is 0.6 times or less of the bulk density T1.
(3) The inorganic physical foaming agent is selected from carbon dioxide, nitrogen, oxygen, air and argon.
(4) The cyclic olefin resin is selected from a copolymer composed of a chain olefin component and a cyclic olefin component.
(5) The chain olefin component is a component derived from an ethylene hydrocarbon having 2 to 6 carbon atoms, and the cyclic olefin component is a component derived from a monocyclic or polycyclic hydrocarbon having 3 to 10 carbon atoms.
(6) The cyclic olefin-based resin expanded particles have an open cell ratio of 40% or less.
以下、本発明を詳細に説明する。
（環状オレフィン系樹脂発泡粒子の製造方法）
環状オレフィン系樹脂発泡粒子（以下、発泡粒子ともいう）は、基材樹脂としての環状オレフィン系樹脂と、無機系物理発泡剤とを含む発泡性粒子を発泡させることにより製造される。ここで、発泡は、１回以上行われ、１回目の発泡が０．５１〜０．０５１ｇ／ｃｍ３の嵩密度の発泡粒子を得る条件で行われる。
Hereinafter, the present invention will be described in detail.
(Manufacturing method of cyclic olefin resin expanded particles)
Cyclic olefin resin expanded particles (hereinafter, also referred to as expanded particles) are produced by foaming expandable particles containing a cyclic olefin resin as a base resin and an inorganic physical foaming agent. Here, foaming is performed at least once, and the first foaming is performed under the condition of obtaining expanded particles having a bulk density of 0.51 to 0.051 g / cm 3 .
（１）基材樹脂
基材樹脂は環状オレフィン系樹脂を含む。
環状オレフィン系樹脂は、鎖状オレフィン成分と環状オレフィン成分とから構成される共重合体の使用が好ましい。
鎖状オレフィン成分としては、エチレン、プロピレン、１−ブテン、１−ペンテン、１−へキセン、３−メチル−１−ブテン、３−メチル−１−ペンテン、３−エチル−１−ペンテン、４−メチル−１−ペンテン、４−メチル−１−へキセン、４，４−ジメチル−１−ヘキセン、４，４−ジメチル−１−ペンテン、４−エチル−１−へキセン、３−エチル−１−ヘキセン、１−オクテン、１−デセン、１−ドデセン、１−テトラデセン、１−ヘキサデセン、１−オクタデセン、１−エイコセン等の炭素数２〜２０のエチレン系炭化水素に由来する成分が挙げられる。この内、エチレン、プロピレン、イソブチレン、１−ブテン、１−ペンテン、１−ヘキセン等の炭素数２〜６のエチレン系炭化水素に由来する成分が好ましく、鎖状オレフィン成分として最も一般的であるエチレンに由来する成分が更に好ましい。
(1) Base resin The base resin contains a cyclic olefin resin.
The cyclic olefin resin is preferably a copolymer composed of a chain olefin component and a cyclic olefin component.
Examples of the chain olefin component include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4- Methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1- Examples include components derived from ethylene hydrocarbons having 2 to 20 carbon atoms such as hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene. Among these, components derived from ethylene hydrocarbons having 2 to 6 carbon atoms such as ethylene, propylene, isobutylene, 1-butene, 1-pentene and 1-hexene are preferable, and ethylene is the most common as a chain olefin component. A component derived from is more preferred.
環状オレフィン成分としては、炭素数３〜２０の単環又は多環の炭化水素に由来する成分が挙げられる。単官能オレフィン成分の具体例としては、シクロブテン、シクロペンテン、シクロヘプテン、シクロオクテン、シクロペンタジエン、１，３−シクロヘキサジエン等の単環式オレフィン、
ビシクロ〔２，２，１〕ヘプト−２−エン、５−メチル−ビシクロ〔２，２，１〕ヘプタ−２−エン、５，５−ジメチル−ビシクロ〔２，２，１〕ヘプト−２−エン、５−エチル−ビシクロ〔２，２，１〕ヘプト−２−エン、５−ブチル−ビシクロ〔２，２，１〕ヘプト−２−エン、５−エチリデン−ビシクロ〔２，２，１〕ヘプト−２−エン、５−ヘキシル−ビシクロ〔２，２，１〕ヘプト−２−エン、５−オクチル−ビシクロ〔２，２，１〕ヘプト−２−エン、５−オクタデシル−ビシクロ〔２，２，１〕ヘプト−２−エン、５−メチリデン−ビシクロ〔２，２，１〕ヘプト−２−エン、５−ビニル−ビシクロ〔２，２，１〕ヘプト−２−エン、５−プロペニル−ビシクロ〔２，２，１〕ヘプト−２−エン、ノルボルネン等の二環式オレフィン、
トリシクロ〔４，３，０，１２．５〕デカ−３，７−ジエン、トリシクロ〔４，３，０，１２．５〕デカ−３−エン、トリシクロ〔４，３，０，１２．５〕ウンデカ−３，７−ジエン又はトリシクロ〔４，３，０，１２．５〕ウンデカ−３，８−ジエン又はこれらの部分水素添加物（又はシクロペンタジエンとシクロヘキセンの付加物） であるトリシクロ〔４，３，０，１２．５〕ウンデカ−３−エン；５−シクロペンチル−ビシクロ〔２，２，１〕ヘプト−２−エン、５−シクロヘキシル−ビシクロ〔２，２，１〕ヘプト−２−エン、５−シクロヘキセニルビシクロ〔２，２，１〕ヘプト−２−エン、５−フェニル−ビシクロ〔２，２，１〕ヘプタ−２−エン等の三環式オレフィン、
Examples of the cyclic olefin component include components derived from monocyclic or polycyclic hydrocarbons having 3 to 20 carbon atoms. Specific examples of the monofunctional olefin component include monocyclic olefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, cyclopentadiene, 1,3-cyclohexadiene,
Bicyclo [2,2,1] hept-2-ene, 5-methyl-bicyclo [2,2,1] hept-2-ene, 5,5-dimethyl-bicyclo [2,2,1] hept-2-ene Ene, 5-ethyl-bicyclo [2,2,1] hept-2-ene, 5-butyl-bicyclo [2,2,1] hept-2-ene, 5-ethylidene-bicyclo [2,2,1] Hept-2-ene, 5-hexyl-bicyclo [2,2,1] hept-2-ene, 5-octyl-bicyclo [2,2,1] hept-2-ene, 5-octadecyl-bicyclo [2, 2,1] hept-2-ene, 5-methylidene-bicyclo [2,2,1] hept-2-ene, 5-vinyl-bicyclo [2,2,1] hept-2-ene, 5-propenyl- Bicyclic [2,2,1] hept-2-ene, norbornene, etc. Fin,
Tricyclo [4,3,0,1 2.5] dec-3,7-diene, tricyclo [4,3,0,1 2.5] dec-3-ene, tricyclo [4,3,0,1 2 .5 ] undeca-3,7-diene or tricyclo [4,3,0,1 2.5 ] undeca-3,8-diene or a partial hydrogenated product thereof (or an adduct of cyclopentadiene and cyclohexene). Tricyclo [4,3,0,1 2.5 ] undec-3-ene; 5-cyclopentyl-bicyclo [2,2,1] hept-2-ene, 5-cyclohexyl-bicyclo [2,2,1] hept Tricyclic olefins such as 2-ene, 5-cyclohexenylbicyclo [2,2,1] hept-2-ene, and 5-phenyl-bicyclo [2,2,1] hept-2-ene;
テトラシクロ〔４，４，０，１２．５，１７．１０〕ドデカ−３−エン、８−メチルテトラシクロ〔４，４，０，１２．５，１７．１０〕ドデカ−３−エン、８−エチルテトラシクロ〔４，４，０，１２．５，１７．１０〕ドデカ−３−エン、８−メチリデンテトラシクロ〔４，４，０，１２．５，１７．１０〕ドデカ−３−エン、８−エチリデンテトラシクロ〔４，４，０，１２．５，１７．１０〕ドデカ−３−エン、８−ビニルテトラシクロ〔４，４，０，１２．５，１７．１０〕ドデカ−３−エン、８−プロペニル−テトラシクロ〔４，４，０，１２．５，１７．１０〕ドデカ−３−エン等の四環式オレフィン、
８−シクロペンチル−テトラシクロ〔４，４，０，１２．５，１７．１０〕ドデカ−３−エン、８−シクロヘキシル−テトラシクロ〔４，４，０，１２．５，１７．１０〕ドデカ−３−エン、８−シクロヘキセニル−テトラシクロ〔４，４，０，１２．５，１７．１０〕ドデカ−３−エン、８−フェニル−シクロペンチル−テトラシクロ〔４，４，０，１２．５，１７．１０〕ドデカ−３−エン、テトラシクロ〔７，４，１３．６，０１．９，０２．７〕テトラデカ−４，９，１１，１３−テトラエン、テトラシクロ〔８，４，１４．７，０１．１０，０３．８〕ペンタデカ−５，１０，１２，１４−テトラエン、ペンタシクロ〔６，６，１３．６，０２．７，０９．１４〕−４−ヘキサデセン、ペンタシクロ〔６，５，１，１３．６，０２．７，０９．１３〕−４−ペンタデセン、ペンタシクロ〔７，４，０，０２．７，１３．６，１１０．１３〕−４−ペンタデセン、ヘプタシクロ〔８，７，０，１２．９，１４．７，１１１．１７，０３．８，０１２．１６〕−５−エイコセン、ヘプタシクロ〔８，７，０，１２．９，０３．８，１４．７，０１２．１７，１１３．１６〕−１４−エイコセン等の四量体等の多環式オレフィン等に由来する成分が挙げられる。これらの環状オレフィンは、それぞれ単独で、あるいは２種類以上組み合わせて用いることができる。環状オレフィン成分は、炭素数３〜１０の単環又は多環の炭化水素に由来する成分がより好ましく、環状オレフィン成分として最も一般的であるノルボルネンに由来する成分であることが更に好ましい。
Tetracyclo [4,4,0,1 2.5 , 1 7.10 ] dodec-3-ene, 8-methyltetracyclo [4,4,0,1 2.5 , 1 7.10 ] dodec-3- ene, 8-ethyl-tetracyclododecene [4,4,0,1 2.5, 1 7.10] dodeca-3-ene, 8-methylidene-tetracyclo [4,4,0,1 2.5, 1 7 .10] dodeca-3-ene, 8-ethylidene tetracyclododecene [4,4,0,1 2.5, 1 7.10] dodeca-3-ene, 8-vinyl-tetracyclo [4,4,0,1 2.5, 1 7.10] dodeca-3-ene, 8-propenyl - tetracyclo [4,4,0,1 2.5, 1 7.10] dodeca-3 tetracyclic olefins such as ene,
8-cyclopentyl-- tetracyclo [4,4,0,1 2.5, 1 7.10] dodeca-3-ene, 8-cyclohexyl - tetracyclo [4,4,0,1 2.5, 1 7.10] dodeca-3-ene, 8-cyclohexenyl - tetracyclo [4,4,0,1 2.5, 1 7.10] dodeca-3-ene, 8-phenyl - cyclopentyl - tetracyclo [4,4,0,1 2.5, 1 7.10] dodeca-3-ene, tetracyclo [7,4,1 3.6, 0 1.9, 0 2.7] tetradeca -4,9,11,13- tetraene, tetracyclo [ 8,4,1 4.7, 0 1.10 0 3.8] pentadeca -5,10,12,14- tetraene, pentacyclo [6,6,1 3.6, 0 2.7, 0 9. 14 ] -4-hexadecene, pentacyclo [6, 5,1,1 3.6, 0 2.7, 0 9.13] -4-pentadecene, pentacyclo [7,4,0,0 2.7, 1 3.6, 1 10.13] -4- pentadecene, heptacyclo [8,7,0,1 2.9, 1 4.7, 1 11.17, 0 3.8, 0 12.16] -5-eicosene, heptacyclo [8,7,0,1 2 .9 , 0 3.8 , 1 4.7 , 0 12.17 , 1 13.16 ], components derived from polycyclic olefins such as tetramers such as 14- eicosene . These cyclic olefins can be used alone or in combination of two or more. The cyclic olefin component is preferably a component derived from a monocyclic or polycyclic hydrocarbon having 3 to 10 carbon atoms, and more preferably a component derived from norbornene, which is the most common cyclic olefin component.
環状オレフィン系樹脂は、５０〜１００質量％の環状オレフィン成分と５０〜０質量％の鎖状オレフィン成分とを含むことが好ましく、６０〜９０質量％の環状オレフィン成分と４０〜１０質量％の鎖状オレフィン成分とを含むことがより好ましい。
環状オレフィン系樹脂は、例えば、環状オレフィンと鎖状オレフィンとの付加重合のような公知の方法で製造できる。
基材樹脂は、環状オレフィン系樹脂以外の他の樹脂を含んでいてもよい。他の樹脂としては、アクリル系樹脂、飽和ポリエステル系樹脂、ＡＢＳ系樹脂、ポリスチレン系樹脂、ポリカーボネート系樹脂、及びポリフェニレンオキサイド系樹脂等が挙げられる。基材樹脂には、環状オレフィン系樹脂を５０質量％以上含むことが好ましい。
The cyclic olefin-based resin preferably includes 50 to 100% by mass of the cyclic olefin component and 50 to 0% by mass of the chain olefin component, and is preferably 60 to 90% by mass of the cyclic olefin component and 40 to 10% by mass of the chain. It is more preferable that a olefin component is included.
The cyclic olefin resin can be produced by a known method such as addition polymerization of a cyclic olefin and a chain olefin.
The base resin may contain a resin other than the cyclic olefin resin. Examples of other resins include acrylic resins, saturated polyester resins, ABS resins, polystyrene resins, polycarbonate resins, and polyphenylene oxide resins. The base resin preferably contains 50% by mass or more of a cyclic olefin resin.
（２）無機系物理発泡剤
無機系物理発泡剤（以下、発泡剤ともいう）としては、例えば、二酸化炭素、窒素、酸素、空気及びアルゴンが挙げられる。これら発泡剤は２種以上併用してもよい。
発泡剤の含有量（含浸量）は、基材樹脂１００質量部に対して、０．１〜１５質量部であることが好ましい。発泡剤の含有量が０．１質量部未満であると、発泡力が低くなり、良好に発泡させ難いことがある。含有量が１５質量部を超えると、可塑化効果が大きくなり、発泡時に収縮が起こりやすく、生産性が悪くなると共に、安定して所望の発泡倍数を得難くなることがある。より好ましい発泡剤の含有量は、１．０〜１０質量部である。
(2) Inorganic physical foaming agent Examples of the inorganic physical foaming agent (hereinafter also referred to as foaming agent) include carbon dioxide, nitrogen, oxygen, air, and argon. Two or more of these foaming agents may be used in combination.
It is preferable that content (impregnation amount) of a foaming agent is 0.1-15 mass parts with respect to 100 mass parts of base resin. When the content of the foaming agent is less than 0.1 parts by mass, the foaming power is low, and it may be difficult to foam well. When the content exceeds 15 parts by mass, the plasticizing effect is increased, shrinkage occurs easily during foaming, the productivity is deteriorated, and it is difficult to stably obtain a desired expansion ratio. A more preferable foaming agent content is 1.0 to 10 parts by mass.
（３）発泡
発泡は、１回以上行われるが、１回目の発泡が０．５１〜０．０５１ｇ／ｃｍ３の嵩密度の発泡粒子を得る条件で行われる。この嵩密度は、通常の発泡での嵩密度が０．３４〜０．０１０２ｇ／ｃｍ３（特許文献２段落００３３記載の嵩発泡倍率より算出。なお、基材樹脂の密度は１．０２ｇ／ｃｍ３とした。）であることを考慮すると、高い値である。好ましい嵩密度は０．３４〜０．０５７ｇ／ｃｍ３であり、より好ましい嵩密度は０．２０４〜０．０６８ｇ／ｃｍ３である。
発泡を２回以上行う場合、発泡の全回数をｎ回とすると、１回目の発泡で得られた発泡粒子が０．５１〜０．０５１ｇ／ｃｍ３の嵩密度Ｔ１を示し、ｎ回目の発泡で得られた発泡粒子が０．３４〜０．００６８ｇ／ｃｍ３の嵩密度Ｔ２を示す条件で行われることが好ましい。この条件では、外観良好な発泡成形体をより高倍で得ることが可能な発泡粒子を提供できる。ｎ回目のより好ましい嵩密度は０．１０２〜０．００７８ｇ／ｃｍ３であり、ｎ回目の更に好ましい嵩密度は０．０５１〜０．００８５ｇ／ｃｍ３である。また、嵩密度Ｔ２が、嵩密度Ｔ１の０．６倍以下であることが好ましく、０．０５〜０．５５倍であることがより好ましい。
(3) Foaming Foaming is performed at least once, but the first foaming is performed under the condition of obtaining foamed particles having a bulk density of 0.51 to 0.051 g / cm 3 . This bulk density is 0.34 to 0.0102 g / cm 3 (calculated from the bulk foaming ratio described in paragraph 0033 of Patent Document 2. The density of the base resin is 1.02 g / cm. 3 )), it is a high value. A preferred bulk density is 0.34 to 0.057 g / cm 3 , and a more preferred bulk density is 0.204 to 0.068 g / cm 3 .
When foaming is performed twice or more, if the total number of times of foaming is n, the foamed particles obtained by the first foaming exhibit a bulk density T1 of 0.51 to 0.051 g / cm 3 , and the nth foaming It is preferable that the foamed particles obtained in the above are carried out under the condition of showing a bulk density T2 of 0.34 to 0.0068 g / cm 3 . Under these conditions, it is possible to provide expanded particles capable of obtaining an expanded molded article having a good appearance at a higher magnification. More preferred bulk density of the n-th is 0.102~0.0078g / cm 3, more preferred bulk density of the n-th is 0.051~0.0085g / cm 3. Further, the bulk density T2 is preferably 0.6 times or less of the bulk density T1, and more preferably 0.05 to 0.55 times.
発泡性粒子を発泡させて発泡粒子を得る方法としては、発泡性粒子をスチーム（水蒸気）等により加熱して発泡させる方法が好適に使用される。
発泡時の発泡機には密閉耐圧の発泡容器を使用することが好ましい。また、スチームの圧力はゲージ圧にて０．１〜０．８ＭＰａであることが好ましく、０．２〜０．６ＭＰａであることがより好ましい。発泡時間は上記条件を満たすのに必要な時間であればよい。好ましい発泡時間は、５〜６００秒である。
発泡を２回以上行う方法としては、発泡粒子内に発泡剤を含浸させることで発泡力（２次等のｎ次発泡力）を付与した発泡粒子（以下、発泡性発泡粒子と称する）をスチーム（水蒸気）等により加熱して発泡させる方法が好適に使用される。得られた発泡粒子をｎ次発泡粒子と称する。この際、発泡機には密閉耐圧の発泡容器を使用することが好ましい。また、スチームの圧力はゲージ圧にて０．１〜０．８ＭＰａであることが好ましく、０．２〜０．６ＭＰａであることがより好ましい。発泡時間は上記条件を満たすのに必要な時間であればよい。好ましい発泡時間は、５〜６００秒である。
As a method for obtaining foamed particles by foaming the foamable particles, a method of foaming the foamable particles by heating with steam (water vapor) or the like is preferably used.
It is preferable to use a sealed pressure-resistant foaming container for the foaming machine at the time of foaming. Further, the steam pressure is preferably 0.1 to 0.8 MPa, more preferably 0.2 to 0.6 MPa in terms of gauge pressure. The foaming time may be a time required to satisfy the above conditions. The preferred foaming time is 5 to 600 seconds.
As a method of performing foaming twice or more, foamed particles (hereinafter referred to as expandable foamed particles) imparted with foaming power (secondary or other n-th foaming power) by impregnating the foamed particles with a foaming agent are steamed. A method of heating and foaming with (steam) or the like is preferably used. The obtained expanded particles are referred to as n-order expanded particles. At this time, it is preferable to use a closed pressure-resistant foaming container for the foaming machine. Further, the steam pressure is preferably 0.1 to 0.8 MPa, more preferably 0.2 to 0.6 MPa in terms of gauge pressure. The foaming time may be a time required to satisfy the above conditions. The preferred foaming time is 5 to 600 seconds.
（４）発泡性粒子
発泡性粒子は、例えば、環状オレフィン系の樹脂粒子に発泡剤を含浸させることにより得ることができる。
含浸方法としては、粒子を水系に分散させ撹拌させながら発泡剤を圧入することで含浸させる湿式含浸法や、密閉可能な容器に樹脂粒子を投入し、発泡剤を圧入して含浸させる実質的に水を使用しない乾式含浸法（気相含浸法）等が挙げられる。特に水を使用せずに含浸できる乾式含浸法が好ましい。樹脂粒子に発泡剤を含浸させる際の含浸圧、含浸時間及び含浸温度は特に限定されない。
含浸を効率的に行い、より一層良好な外観の発泡粒子及び発泡成形体を得る観点からは、含浸圧はゲージ圧にて０．１〜１０ＭＰａであることが好ましい。
含浸時間は、０．５〜２００時間以下であることが好ましい。０．５時間未満の場合、発泡剤の樹脂粒子への含浸量が低下するため、十分な発泡力が得られ難いことがある。２００時間より長い場合、生産性が低下することがある。より好ましい含浸時間は、１〜１００時間である。
(4) Expandable particles Expandable particles can be obtained, for example, by impregnating cyclic olefin resin particles with a foaming agent.
Examples of the impregnation method include a wet impregnation method in which particles are dispersed in an aqueous system and a foaming agent is press-fitted while stirring, or a resin particle is introduced into a sealable container, and the foaming agent is injected and impregnated substantially. Examples thereof include a dry impregnation method (gas phase impregnation method) that does not use water. In particular, a dry impregnation method capable of impregnation without using water is preferable. The impregnation pressure, impregnation time and impregnation temperature when impregnating the resin particles with the foaming agent are not particularly limited.
From the viewpoint of efficiently performing impregnation and obtaining foamed particles and a foamed molded article having a better appearance, the impregnation pressure is preferably 0.1 to 10 MPa in terms of gauge pressure.
The impregnation time is preferably 0.5 to 200 hours or less. When the time is less than 0.5 hours, the amount of the foaming agent impregnated into the resin particles is reduced, so that sufficient foaming power may not be obtained. When it is longer than 200 hours, productivity may be reduced. A more preferable impregnation time is 1 to 100 hours.
含浸温度は、０〜６０℃であることが好ましい。０℃未満の場合、所望の時間内に十分な含浸量を確保できないため十分な発泡力が得られ難いことがある。６０℃より高い場合、生産性が悪くなることがある。より好ましい含浸温度は、５〜５０℃である。
樹脂粒子は、公知の方法により得ることができる。例えば、環状オレフィン系樹脂を、必要に応じて他の添加剤と共に、押出機中で溶融混練して押出すことでストランドを得、得られたストランドを、空気中でカット、水中でカット、加熱しつつカットすることで、造粒する方法が挙げられる。樹脂粒子は、市販の樹脂粒子を使用してもよい。樹脂粒子には、必要に応じて、樹脂以外に他の添加剤が含まれていてもよい。他の添加剤としては、可塑剤、難燃剤、難燃助剤、帯電防止剤、展着剤、気泡調整剤、充填剤、着色剤、耐候剤、老化防止剤、滑剤、防曇剤、香料等が挙げられる。
The impregnation temperature is preferably 0 to 60 ° C. When the temperature is lower than 0 ° C., a sufficient foaming power may not be obtained because a sufficient impregnation amount cannot be secured within a desired time. When it is higher than 60 ° C., productivity may be deteriorated. A more preferable impregnation temperature is 5 to 50 ° C.
The resin particles can be obtained by a known method. For example, a cyclic olefin-based resin is melt-kneaded in an extruder together with other additives as necessary to obtain a strand, and the resulting strand is cut in air, cut in water, and heated. However, the method of granulating by cutting is mentioned. Commercially available resin particles may be used as the resin particles. The resin particles may contain other additives in addition to the resin, if necessary. Other additives include plasticizers, flame retardants, flame retardant aids, antistatic agents, spreading agents, foam control agents, fillers, colorants, weathering agents, anti-aging agents, lubricants, antifogging agents, and fragrances. Etc.
（環状オレフィン系樹脂発泡粒子）
発泡粒子の形状は特に限定されない。例えば、球状、円柱状等が挙げられる。この内、できるだけ球状に近いことが好ましい。即ち、発泡粒子の短径と長径との比ができるだけ１に近いことが好ましい。
発泡粒子は、１〜２０ｍｍの平均粒子径を有していることが好ましい。
発泡粒子は、外観のより良好な発泡成形体を得る観点から、４０％以下の連続気泡率を有することが好ましい。連続気泡率は２０％以下であることがより好ましく、１０％以下であることが更に好ましい。
(Cyclic olefin resin foam particles)
The shape of the expanded particles is not particularly limited. For example, spherical shape, cylindrical shape, etc. are mentioned. Of these, it is preferable that the shape be as spherical as possible. That is, it is preferable that the ratio of the minor axis to the major axis of the expanded particles is as close to 1 as possible.
The expanded particles preferably have an average particle diameter of 1 to 20 mm.
The foamed particles preferably have an open cell ratio of 40% or less from the viewpoint of obtaining a foamed molded article having a better appearance. The open cell ratio is more preferably 20% or less, and still more preferably 10% or less.
(発泡性発泡粒子)
発泡性発泡粒子は、例えば、環状オレフィン系の発泡粒子に発泡剤を含浸させ、発泡粒子気泡内の圧力を大気圧よりも高めることにより得ることができる。
発泡剤を含浸し、発泡粒子の気泡内の圧力を大気圧よりも高める方法としては、密閉可能な容器に発泡粒子を投入し、発泡剤を圧入して含浸させる乾式含浸法（気相含浸法）の使用が好ましい。発泡粒子に発泡剤を含浸させる際の含浸圧、含浸時間及び含浸温度は特に限定されない。ここで使用する発泡剤には、発泡粒子製造時の発泡剤：二酸化炭素、窒素、酸素、空気及びアルゴンを使用できる。内圧を付与するための圧力は、発泡粒子がつぶれてしまわない程度の圧力でかつ発泡力を付与できる範囲であることが望ましい。そのような圧力は、ゲージ圧にて０．０１〜１０ＭＰａであることが好ましく、０．１〜５ＭＰａであることがより好ましい。含浸時間は、０．５〜２００時間以下であることが好ましい。０．５時間未満の場合、発泡剤の発泡粒子への含浸量が低下するため、十分な発泡力が得られ難いことがある。２００時間より長い場合、生産性が低下することがある。より好ましい含浸時間は、１〜１００時間である。含浸温度は、０〜６０℃であることが好ましい。０℃未満の場合、所望の時間内に十分な含浸量を確保できないため十分な発泡力が得られ難いことがある。６０℃より高い場合、生産性が悪くなることがある。より好ましい含浸温度は、５〜５０℃である。
(Foaming foam particles)
The expandable foamed particles can be obtained, for example, by impregnating a cyclic olefin-based foamed particle with a foaming agent and increasing the pressure in the foamed particle bubbles above atmospheric pressure.
As a method of impregnating a foaming agent and increasing the pressure inside the foamed bubbles above the atmospheric pressure, a dry impregnation method (gas phase impregnation method) in which foam particles are introduced into a sealable container and the foaming agent is injected and impregnated. ) Is preferred. The impregnation pressure, impregnation time, and impregnation temperature when impregnating the foaming agent with the foamed particles are not particularly limited. As the foaming agent used here, a foaming agent at the time of producing foamed particles: carbon dioxide, nitrogen, oxygen, air and argon can be used. The pressure for applying the internal pressure is desirably a pressure that does not cause the foamed particles to be crushed and within a range in which the foaming force can be applied. Such pressure is preferably 0.01 to 10 MPa, more preferably 0.1 to 5 MPa in terms of gauge pressure. The impregnation time is preferably 0.5 to 200 hours or less. When the time is less than 0.5 hour, the amount of the foaming agent impregnated into the foamed particles is reduced, so that sufficient foaming power may not be obtained. When it is longer than 200 hours, productivity may be reduced. A more preferable impregnation time is 1 to 100 hours. The impregnation temperature is preferably 0 to 60 ° C. When the temperature is lower than 0 ° C., a sufficient foaming power may not be obtained because a sufficient impregnation amount cannot be secured within a desired time. When it is higher than 60 ° C., productivity may be deteriorated. A more preferable impregnation temperature is 5 to 50 ° C.
（発泡成形体）
発泡成形体は、上記発泡粒子又はｎ次発泡粒子を型内発泡成型して得られる。具体的には、発泡成形体は、例えば、発泡粒子又はｎ次発泡粒子に内圧を付与し、次いで発泡粒子又はｎ次発泡粒子を成形工程に付すことで得ることができる。
ここでの発泡粒子及びｎ次発泡粒子には、上記発泡性発泡粒子の欄に記載した方法と同様に、発泡力を付与しておくことが好ましい。
(Foamed molded product)
The foam molded body is obtained by in-mold foam molding of the foamed particles or n-order foamed particles. Specifically, the foamed molded product can be obtained, for example, by applying an internal pressure to the foamed particles or n-th order foamed particles, and then subjecting the foamed particles or n-th order foamed particles to a molding step.
It is preferable to give foaming power to the foamed particles and n-order foamed particles in the same manner as the method described in the column of expandable foamed particles.
内圧付与した発泡粒子を、発泡成形機の成形金型内に形成された成形空間に供給した後、加熱媒体を導入することで、所望の発泡成形体に型内成形できる。発泡成形機としては、ポリスチレン系樹脂製の発泡粒子から発泡成形体を製造する際に用いられるＥＰＳ成形機やポリプロピレン系樹脂製の発泡粒子から発泡成形体を製造する際に用いられる高圧仕様の成形機等を用いることができる。加熱媒体は、加熱時間が長くなると発泡粒子に収縮や融着不良が生じることがあるため、短時間に高エネルギーを与えうる加熱媒体が望まれるから、そのような加熱媒体としては水蒸気が好適である。
水蒸気の圧力は、ゲージ圧にて０．１〜０．８ＭＰａであることが好ましい。また、加熱時間は、５〜６００秒であることが好ましい。
発泡成形体は、種々の密度をとり得る。例えば、０．５１〜０．００６８ｇ／ｃｍ３の密度をとり得る。
発泡成形体は、特に限定されず、用途に応じて種々の形状をとり得る。例えば、発泡成形体は、建材（土木関係、住宅関係等）、自動車構造部材、風車等の構造部材、梱包材、複合部材としてのＦＲＰの芯材等の用途に応じて種々の形状をとり得る。
After supplying the expanded particles to which the internal pressure is applied to the molding space formed in the molding die of the foam molding machine, a desired foamed molded product can be molded in-mold by introducing a heating medium. As the foam molding machine, an EPS molding machine used when producing a foam molded body from polystyrene resin foam particles or a high-pressure molding used when producing a foam molded body from polypropylene resin foam particles. A machine or the like can be used. Since the heating medium may cause shrinkage or poor fusion of the foamed particles as the heating time becomes long, a heating medium that can give high energy in a short time is desired. Therefore, water vapor is suitable as such a heating medium. is there.
The water vapor pressure is preferably 0.1 to 0.8 MPa in terms of gauge pressure. The heating time is preferably 5 to 600 seconds.
The foamed molded product can have various densities. For example, a density of 0.51 to 0.0068 g / cm 3 can be taken.
The foamed molded product is not particularly limited, and can take various shapes depending on applications. For example, the foamed molded body can take various shapes depending on applications such as building materials (civil engineering-related, housing-related, etc.), structural members such as automobile structural members, windmills, packaging materials, and FRP core materials as composite members. .
次に実施例を挙げて本発明を更に詳しく説明するが、本発明はこれらに限定されるものではない。
＜発泡粒子の嵩密度＞
発泡粒子約１０００ｃｍ３を、メスシリンダー内に１０００ｃｍ３の目盛りまで充填する。なお、メスシリンダーを水平方向から目視し、発泡粒子が１つでも１０００ｃｍ３の目盛りに達していれば、その時点で発泡粒子のメスシリンダー内への充填を終了する。次に、メスシリンダー内に充填した発泡粒子の質量を小数点以下２位の有効数字で秤量し、その質量をＷｇとする。そして、下記式により発泡粒子の嵩密度は求められる。
嵩密度（ｇ／ｃｍ３）＝Ｗ／１０００
また、嵩倍数は下記式により求められる。
嵩倍数＝基材樹脂の密度（ｇ／ｃｍ３）／嵩密度（ｇ／ｃｍ３）
ここで、基材樹脂の密度（ｇ／ｃｍ３）はＩＳＯ１１８３に準じた方法で測定する。
EXAMPLES Next, although an Example is given and this invention is demonstrated in more detail, this invention is not limited to these.
<Bulk density of expanded particles>
Fill the graduated cylinder with approximately 1000 cm 3 of expanded particles to a scale of 1000 cm 3 . When the graduated cylinder is visually observed from the horizontal direction and at least one expanded particle reaches the scale of 1000 cm 3 , the filling of the expanded particle into the graduated cylinder is terminated at that point. Next, the mass of the expanded particles filled in the graduated cylinder is weighed with two significant figures after the decimal point, and the mass is defined as Wg. And the bulk density of foamed particle is calculated | required by a following formula.
Bulk density (g / cm 3 ) = W / 1000
The bulk multiple is obtained by the following formula.
Bulk multiple = density of base resin (g / cm 3 ) / bulk density (g / cm 3 )
Here, the density (g / cm 3 ) of the base resin is measured by a method according to ISO 1183.
＜平均粒子径＞
粒子約２５ｇをロータップ型篩振とう機（飯田製作所社製）を用いて、篩目開き２６．５ｍｍ、２２．４ｍｍ、１９．０ｍｍ、１６．０ｍｍ、１３．２ｍｍ、１１．２０ｍｍ、９．５０ｍｍ、８．８０ｍｍ、６．７０ｍｍ、５．６６ｍｍ、４．７６ｍｍ、４．００ｍｍ、３．３５ｍｍ、２．８０ｍｍ、２．３６ｍｍ、２．００ｍｍ、１．７０ｍｍ、１．４０ｍｍ、１．１８ｍｍ、１．００ｍｍ、０．８５ｍｍ、０．７１ｍｍ、０．６０ｍｍ、０．５０ｍｍ、０．４２５ｍｍ、０．３５５ｍｍ、０．３００ｍｍ、０．２５０ｍｍ、０．２１２ｍｍ、０．１８０ｍｍのＪＩＳ標準篩（ＪＩＳ Ｚ８８０１）で１０分間分級する。篩網上の試料質量を測定し、その結果から得られた累積質量分布曲線を元にして累積質量が５０％となる粒子径（メディアン径）を平均粒子径とする。
<Average particle size>
About 25 g of the particles were sieved using a low-tap type sieve shaker (manufactured by Iida Seisakusho Co., Ltd.) 26.5 mm, 22.4 mm, 19.0 mm, 16.0 mm, 13.2 mm, 11.20 mm, 9.50 mm. 8.80 mm, 6.70 mm, 5.66 mm, 4.76 mm, 4.00 mm, 3.35 mm, 2.80 mm, 2.36 mm, 2.00 mm, 1.70 mm, 1.40 mm, 1.18 mm, 1 .00mm, 0.85mm, 0.71mm, 0.60mm, 0.50mm, 0.425mm, 0.355mm, 0.300mm, 0.250mm, 0.212mm, 0.180mm JIS standard sieve (JIS Z8801) Classify for 10 minutes. The sample mass on the sieve mesh is measured, and based on the cumulative mass distribution curve obtained from the result, the particle diameter (median diameter) at which the cumulative mass is 50% is defined as the average particle diameter.
＜連続気泡率＞
体積測定空気比較式比重計の試料カップを準備し、この試料カップの８０％程度を満たす量の発泡粒子の全質量Ａ（ｇ）を測定する。発泡粒子全体の体積Ｂ（ｃｍ３）を、空気比較式比重計を用いて１−１／２−１気圧法により測定する。空気比較式比重計は、標準球(大２８．９ｃｃ 小８．５ｃｃ）にて補正を行う。なお、体積測定空気比較式比重計は、例えば、東京サイエンス社から商品名「空気比較式比重計１０００型」にて市販されている。続いて、金網製の容器を準備する。この金網製の容器を水中に浸漬し、水中に浸漬した状態における金網製の容器の質量Ｃ（ｇ）を測定する。次に、この金網製の容器内に前記発泡粒子を全量入れた上で、この金網製の容器を水中に浸漬し、容器を数回振って、容器と発泡粒子に付着した気泡を除去後、水中に浸漬した状態における金網製の容器とこの金網製容器に入れた発泡粒子の全量とを併せた質量Ｄ（ｇ）を測定する。なお、水中の質量測定に用いる電子天びんは、例えば、大和製衡社から商品名「電子天びんＨＢ３０００」にて市販されている。そして、下記式により発泡粒子の見掛け体積Ｅ（ｃｍ３）を算出する。この見掛け体積Ｅと前記発泡粒子全体の体積Ｂ（ｃｍ３）に基づいて下記式により発泡粒子の連続気泡率を算出する。なお、水１ｇの体積を１ｃｍ３とする。また、測定に用いる発泡粒子はすべてカッターにて二等分としたものとし、試験数は３とする。試料は、ＪＩＳ Ｋ７１００−１９９９ 記号２３／５０、２級の環境下で１６時間態調節した後、ＪＩＳ Ｋ７１００−１９９９ 記号２３／５０、２級の環境下で測定を行う。
Ｅ＝Ａ＋（Ｃ−Ｄ）
連続気泡率（％）＝１００×（Ｅ−Ｂ）／Ｅ
<Open cell ratio>
A sample cup of a volumetric air comparison hydrometer is prepared, and the total mass A (g) of the expanded particles in an amount satisfying about 80% of the sample cup is measured. The volume B (cm 3 ) of the entire expanded particles is measured by the 1-1 / 2-1 atmospheric pressure method using an air comparison type hydrometer. The air-comparing hydrometer is corrected with a standard sphere (large 28.9 cc, small 8.5 cc). In addition, the volumetric air comparison type hydrometer is commercially available, for example, from Tokyo Science Co., Ltd. under the trade name “Air Comparison Type Hydrometer 1000”. Subsequently, a wire mesh container is prepared. This metal mesh container is immersed in water, and the mass C (g) of the metal mesh container in the state immersed in water is measured. Next, after all the foamed particles are put in the wire mesh container, the wire mesh container is immersed in water, and the container is shaken several times to remove bubbles adhering to the container and the foam particles. The mass D (g) of the wire mesh container in the state immersed in water and the total amount of the expanded particles put in the wire mesh container is measured. An electronic balance used for mass measurement in water is commercially available, for example, under the trade name “Electronic Balance HB3000” from Daiwa Seisakusha. Then, the apparent volume E (cm 3 ) of the expanded particles is calculated by the following formula. Based on the apparent volume E and the volume B (cm 3 ) of the whole expanded particle, the open cell ratio of the expanded particle is calculated by the following formula. The volume of 1 g of water is 1 cm 3 . In addition, all the foamed particles used for the measurement are bisected by a cutter, and the number of tests is three. The sample is conditioned in a JIS K7100-1999 symbol 23/50, second grade environment for 16 hours, and then measured in a JIS K7100-1999 symbol 23/50, second grade environment.
E = A + (CD)
Open cell ratio (%) = 100 × (EB) / E
＜発泡成形体の密度＞
発泡成形体（成形後、４０℃で２０時間以上乾燥させたもの）から切り出した試験片（例７５×３００×３０ｍｍ）の質量（ａ）と体積（ｂ）をそれぞれ有効数字３桁以上になるように測定し、式（ａ）／（ｂ）により発泡成形体の密度（ｇ／ｃｍ３）を求める。
また、倍数は下記式により求められる。
倍数＝基材樹脂の密度（ｇ／ｃｍ３）／発泡成形体の密度（ｇ／ｃｍ３）
ここで、基材樹脂の密度（ｇ／ｃｍ３）はＩＳＯ１１８３に準じた方法で測定する。
<Density of foam molding>
The mass (a) and volume (b) of a test piece (example 75 × 300 × 30 mm) cut out from a foamed molded product (after being molded and dried at 40 ° C. for 20 hours or more) each have three or more significant figures. And the density (g / cm 3 ) of the foamed molded product is obtained from the formula (a) / (b).
The multiple is obtained by the following formula.
Multiple = density of base resin (g / cm 3 ) / density of foamed molded product (g / cm 3 )
Here, the density (g / cm 3 ) of the base resin is measured by a method according to ISO 1183.
＜発泡粒子の製造例１＞
ポリプラスチックス社製の環状ポリオレフィンの樹脂粒子（ＴＯＰＡＳ ６０１３Ｆ−０４：エチレン−ノルボルネン共重合体、平均粒子径３．０ｍｍ、密度１．０２ｇ／ｃｍ３）をオートクレーブ内にいれ、炭酸ガスボンベからオートクレーブ内に炭酸ガスを導入し、ゲージ圧４．０ＭＰａにて室温（約２５℃）下で７２時間保持した。オートクレーブの圧力を開放し、得られた発泡性粒子を取り出した後、高圧発泡槽に導入し、ゲージ圧０．５５ＭＰａの蒸気（水蒸気）にて２０秒加熱することで発泡を行った。得られた一次発泡粒子（１回目の発泡で得られた発泡粒子）の嵩倍数は１２倍（嵩密度０．０８５ｇ／ｃｍ３）であった。
<Production Example 1 of Expanded Particle>
Cyclic polyolefin resin particles (TOPAS 6013F-04: ethylene-norbornene copolymer, average particle size 3.0 mm, density 1.02 g / cm 3 ) manufactured by Polyplastics Co., Ltd. are placed in an autoclave, and the carbon dioxide gas cylinder is placed in the autoclave. Carbon dioxide gas was introduced into the flask and held at a gauge pressure of 4.0 MPa at room temperature (about 25 ° C.) for 72 hours. The pressure of the autoclave was released, and the resulting expandable particles were taken out, introduced into a high-pressure foaming tank, and foamed by heating for 20 seconds with steam (water vapor) having a gauge pressure of 0.55 MPa. The resulting primary foamed particles (foamed particles obtained by the first foaming) were 12 times in bulk (bulk density 0.085 g / cm 3 ).
＜発泡粒子の製造例２＞
ポリプラスチックス社製の環状ポリオレフィンの樹脂粒子（ＴＯＰＡＳ ５０１３Ｆ−０４：エチレン−ノルボルネン共重合体、平均粒子径３．０ｍｍ、密度１．０２ｇ/ｃｍ３）をオートクレーブ内にいれ、炭酸ガスボンベからオートクレーブ内に炭酸ガスを導入し、ゲージ圧４．０ＭＰａにて２０℃下で７２時間保持した。オートクレーブの圧力を開放し、得られた発泡性粒子を取り出した後、高圧発泡槽に導入し、ゲージ圧０．１５ＭＰａの蒸気（水蒸気）にて６０秒加熱することで発泡を行った。得られた一次発泡粒子（１回目の発泡で得られた発泡粒子）の嵩倍数は４倍（嵩密度０．２５５ｇ／ｃｍ３）であった。
<Production Example 2 of Expanded Particle>
Cyclic polyolefin resin particles (TOPAS 5013F-04: ethylene-norbornene copolymer, average particle size 3.0 mm, density 1.02 g / cm 3 ) manufactured by Polyplastics Co., Ltd. are placed in an autoclave, and the carbon dioxide gas cylinder is placed in the autoclave. Carbon dioxide gas was introduced into the flask and held at 20 ° C. under a gauge pressure of 4.0 MPa for 72 hours. The pressure of the autoclave was released, and the resulting expandable particles were taken out, introduced into a high-pressure foaming tank, and foamed by heating for 60 seconds with steam (water vapor) having a gauge pressure of 0.15 MPa. The resulting primary foamed particles (foamed particles obtained by the first foaming) had a bulk multiple of 4 times (bulk density of 0.255 g / cm 3 ).
＜発泡粒子の製造例３＞
ポリプラスチックス社製の環状ポリオレフィンの樹脂粒子（ＴＯＰＡＳ ５０１３Ｆ−０４：エチレン−ノルボルネン共重合体、平均粒子径３．０ｍｍ、密度１．０２ｇ/ｃｍ３）をオートクレーブ内にいれ、炭酸ガスボンベからオートクレーブ内に炭酸ガスを導入し、ゲージ圧４．０ＭＰａにて２０℃下で７２時間保持した。オートクレーブの圧力を開放し、得られた発泡性粒子を取り出した後、高圧発泡槽に導入し、ゲージ圧０．３５ＭＰａの蒸気（水蒸気）にて６０秒加熱することで発泡を行った。得られた一次発泡粒子（１回目の発泡で得られた発泡粒子）の嵩倍数は１８倍（嵩密度０．０５６７ｇ／ｃｍ３）であった。
<Production Example 3 of Expanded Particle>
Cyclic polyolefin resin particles (TOPAS 5013F-04: ethylene-norbornene copolymer, average particle size 3.0 mm, density 1.02 g / cm 3 ) manufactured by Polyplastics Co., Ltd. are placed in an autoclave, and the carbon dioxide gas cylinder is placed in the autoclave. Carbon dioxide gas was introduced into the flask and held at 20 ° C. under a gauge pressure of 4.0 MPa for 72 hours. The pressure of the autoclave was released, and the resulting expandable particles were taken out, introduced into a high-pressure foaming tank, and foamed by heating for 60 seconds with steam (water vapor) having a gauge pressure of 0.35 MPa. The resulting primary foamed particles (foamed particles obtained by the first foaming) were 18 times in bulk (bulk density 0.0567 g / cm 3 ).
＜発泡粒子の製造例４／実施例１〜３及び１０に使用＞
発泡粒子の製造例１にて得られた発泡粒子を再度オートクレーブ内にいれ、窒素ボンベからオートクレーブ内に窒素を導入し、ゲージ圧１．０ＭＰａにて室温下で７２時間保持した。オートクレーブの圧力を開放し発泡性発泡粒子を取り出した後、高圧発泡槽に導入し、ゲージ圧０．３５ＭＰａの蒸気にて６０秒加熱することで再発泡を行った。得られた二次発泡粒子の嵩倍数は２５倍（嵩密度０．０４０８ｇ／ｃｍ３）であった。また、発泡粒子の連続気泡率は装置測定下限以下（≦３％）であった。
<Production Example 4 of foamed particles / used in Examples 1 to 3 and 10>
The foamed particles obtained in Production Example 1 of foamed particles were again placed in the autoclave, nitrogen was introduced into the autoclave from the nitrogen cylinder, and held at room temperature for 72 hours at a gauge pressure of 1.0 MPa. After releasing the pressure of the autoclave and taking out the foamable foamed particles, the foamed foamed particles were introduced into a high-pressure foaming tank and re-foamed by heating with steam having a gauge pressure of 0.35 MPa for 60 seconds. The resulting secondary expanded particles had a bulk magnification of 25 times (bulk density 0.0408 g / cm 3 ). Further, the open cell ratio of the expanded particles was below the apparatus measurement lower limit (≦ 3%).
＜発泡粒子の製造例５／実施例４〜６に使用＞
発泡粒子の製造例２にて得られた発泡粒子を再度オートクレーブ内にいれ、窒素ボンベからオートクレーブ内に窒素を導入し、ゲージ圧１．０ＭＰａにて室温下で２４時間保持した。オートクレーブの圧力を開放し発泡性発泡粒子を取り出した後、高圧発泡槽に導入し、ゲージ圧０．４０ＭＰａの蒸気にて３０秒加熱することで再発泡を行った。得られた二次発泡粒子の嵩倍数は９倍（嵩密度０．１１３３ｇ／ｃｍ３）であった。また、発泡粒子の連続気泡率は装置測定下限以下（≦３％）であった。
<Used in Production Example 5 / Examples 4 to 6 of Expanded Particles>
The expanded particles obtained in Production Example 2 of expanded particles were again placed in the autoclave, nitrogen was introduced into the autoclave from the nitrogen cylinder, and the mixture was held at room temperature at a gauge pressure of 1.0 MPa for 24 hours. After releasing the pressure of the autoclave and taking out the foamable foamed particles, the foamed foamed particles were introduced into a high-pressure foaming tank and re-foamed by heating with steam having a gauge pressure of 0.40 MPa for 30 seconds. The secondary expanded particles thus obtained had a bulk multiple of 9 times (bulk density 0.1133 g / cm 3 ). Further, the open cell ratio of the expanded particles was below the apparatus measurement lower limit (≦ 3%).
＜発泡粒子の製造例６／実施例７〜９に使用＞
発泡粒子の製造例３にて得られた発泡粒子を再度オートクレーブ内にいれ、窒素ボンベからオートクレーブ内に窒素を導入し、ゲージ圧１．０ＭＰａにて室温下で２４時間保持した。オートクレーブの圧力を開放し発泡性発泡粒子を取り出した後、高圧発泡槽に導入し、ゲージ圧０．３５ＭＰａの蒸気にて３０秒加熱することで再発泡を行った。得られた二次発泡粒子の嵩倍数は３９倍（嵩密度０．０２６２ｇ／ｃｍ３）であった。また、発泡粒子の連続気泡率は４％であった。
<Used for Production Example 6 / Examples 7 to 9 of Expanded Particle>
The expanded particles obtained in Production Example 3 of expanded particles were again placed in an autoclave, nitrogen was introduced into the autoclave from a nitrogen cylinder, and the resultant was kept at a gauge pressure of 1.0 MPa at room temperature for 24 hours. After releasing the pressure of the autoclave and taking out the foamable foamed particles, the foamed foamed particles were introduced into a high-pressure foaming tank and re-foamed by heating with steam having a gauge pressure of 0.35 MPa for 30 seconds. The resulting secondary expanded particles had a bulk multiple of 39 times (bulk density 0.0262 g / cm 3 ). The open cell ratio of the expanded particles was 4%.
＜発泡粒子の製造例７／比較例１〜４に使用＞
ポリプラスチックス社製の環状ポリオレフィンの樹脂粒子（ＴＯＰＡＳ ６０１３Ｆ−０４）をオートクレーブ内にいれ、炭酸ガスボンベからオートクレーブ内に炭酸ガスを導入し、ゲージ圧４．０ＭＰａにて室温下で７２時間保持した。オートクレーブの圧力を開放し、得られた発泡性粒子を取り出した後、高圧発泡槽に導入し、ゲージ圧０．５５ＭＰａの蒸気にて６０秒加熱することで発泡を行った。得られた一次発泡粒子の嵩倍数は２５倍（嵩密度０．０４０８ｇ／ｃｍ３）であった。また、発泡粒子の連続気泡率は４３％であった。
<Used for Production Example 7 / Comparative Examples 1-4 for Expanded Particles>
Cyclic polyolefin resin particles (TOPAS 6013F-04) manufactured by Polyplastics Co., Ltd. were placed in an autoclave, carbon dioxide was introduced into the autoclave from a carbon dioxide gas cylinder, and held at room temperature at a gauge pressure of 4.0 MPa for 72 hours. The pressure of the autoclave was released, and the resulting expandable particles were taken out, introduced into a high-pressure foaming tank, and foamed by heating for 60 seconds with steam having a gauge pressure of 0.55 MPa. The resulting primary expanded particles had a bulk multiple of 25 times (bulk density 0.0408 g / cm 3 ). Further, the open cell ratio of the expanded particles was 43%.
＜実施例１；発泡粒子の多段発泡性評価＞
製造例４にて得られた発泡粒子を再度オートクレーブ内にいれ、窒素ボンベからオートクレーブ内に窒素を導入し、ゲージ圧１．０ＭＰａにて室温下で７２時間保持した。オートクレーブの圧力を開放し、得られた発泡性発泡粒子を取り出した後、高圧発泡槽に導入し、ゲージ圧０．３５ＭＰａの蒸気にて６０秒加熱することで再発泡を行った。得られた三次発泡粒子の嵩倍数は５０倍（嵩密度０．０２０４ｇ／ｃｍ３）であった。
＜実施例２；発泡粒子の多段発泡性評価＞
製造例４にて得られた発泡粒子を再度オートクレーブ内にいれ、窒素ボンベからオートクレーブ内に窒素を導入し、ゲージ圧１．０ＭＰａにて室温下で７２時間保持した。オートクレーブの圧力を開放し、得られた発泡性発泡粒子を取り出した後、高圧発泡槽に導入し、ゲージ圧０．３５ＭＰａの蒸気にて１８０秒加熱することで再発泡を行った。得られた三次発泡粒子の嵩倍数は６３倍（嵩密度０．０１６２ｇ／ｃｍ３）であった。
<Example 1; Evaluation of multistage foamability of expanded particles>
The expanded particles obtained in Production Example 4 were again placed in the autoclave, nitrogen was introduced into the autoclave from the nitrogen bomb, and held at room temperature for 72 hours at a gauge pressure of 1.0 MPa. After releasing the pressure of the autoclave and taking out the expandable foam particles obtained, the foamed foam particles were introduced into a high-pressure foaming tank and re-foamed by heating with steam having a gauge pressure of 0.35 MPa for 60 seconds. The volume expansion factor of the obtained tertiary expanded particles was 50 times (bulk density 0.0204 g / cm 3 ).
<Example 2; Evaluation of multistage foamability of expanded particles>
The expanded particles obtained in Production Example 4 were again placed in the autoclave, nitrogen was introduced into the autoclave from the nitrogen bomb, and held at room temperature for 72 hours at a gauge pressure of 1.0 MPa. The pressure of the autoclave was released, and the obtained expandable foam particles were taken out, introduced into a high-pressure foam tank, and re-foamed by heating with steam having a gauge pressure of 0.35 MPa for 180 seconds. The bulk expansion factor of the obtained tertiary expanded particles was 63 times (bulk density 0.0162 g / cm 3 ).
＜実施例３；発泡粒子の多段発泡性評価＞
製造例４にて得られた発泡粒子を再度オートクレーブ内にいれ、窒素ボンベからオートクレーブ内に窒素を導入し、ゲージ圧１．０ＭＰａにて室温下で７２時間保持した。オートクレーブの圧力を開放し、得られた発泡性発泡粒子を取り出した後、高圧発泡槽に導入し、ゲージ圧０．３５ＭＰａの蒸気にて６００秒加熱することで再発泡を行った。得られた三次発泡粒子の嵩倍数は７２倍（嵩密度０．０１４２ｇ／ｃｍ３）であった。
<Example 3; Evaluation of multi-stage foamability of expanded particles>
The expanded particles obtained in Production Example 4 were again placed in the autoclave, nitrogen was introduced into the autoclave from the nitrogen bomb, and held at room temperature for 72 hours at a gauge pressure of 1.0 MPa. After releasing the pressure of the autoclave and taking out the foamable foam particles obtained, the foamed foam particles were introduced into a high-pressure foaming tank and re-foamed by heating with steam having a gauge pressure of 0.35 MPa for 600 seconds. The bulk expansion factor of the obtained tertiary expanded particles was 72 times (bulk density 0.0142 g / cm 3 ).
＜実施例４；発泡粒子の多段発泡性評価＞
製造例５にて得られた発泡粒子を再度オートクレーブ内にいれ、窒素ボンベからオートクレーブ内に窒素を導入し、ゲージ圧１．０ＭＰａにて室温下で２４時間保持した。オートクレーブの圧力を開放し、得られた発泡性発泡粒子を取り出した後、高圧発泡槽に導入し、ゲージ圧０．３５ＭＰａの蒸気にて６０秒加熱することで再発泡を行った。得られた三次発泡粒子の嵩倍数は２５倍（嵩密度０．０４０８ｇ／ｃｍ３）であった。
<Example 4; Evaluation of multistage foamability of expanded particles>
The expanded particles obtained in Production Example 5 were again placed in the autoclave, nitrogen was introduced into the autoclave from the nitrogen bomb, and held at a gauge pressure of 1.0 MPa at room temperature for 24 hours. After releasing the pressure of the autoclave and taking out the expandable foam particles obtained, the foamed foam particles were introduced into a high-pressure foaming tank and re-foamed by heating with steam having a gauge pressure of 0.35 MPa for 60 seconds. The volume expansion factor of the obtained tertiary expanded particles was 25 times (bulk density 0.0408 g / cm 3 ).
＜実施例５；発泡粒子の多段発泡性評価＞
製造例５にて得られた発泡粒子を再度オートクレーブ内にいれ、窒素ボンベからオートクレーブ内に窒素を導入し、ゲージ圧１．０ＭＰａにて室温下で２４時間保持した。オートクレーブの圧力を開放し、得られた発泡性発泡粒子を取り出した後、高圧発泡槽に導入し、ゲージ圧０．３５ＭＰａの蒸気にて１２０秒加熱することで再発泡を行った。得られた三次発泡粒子の嵩倍数は３４倍（嵩密度０．０３ｇ／ｃｍ３）であった。
＜実施例６；発泡粒子の多段発泡性評価＞
製造例５にて得られた発泡粒子を再度オートクレーブ内にいれ、窒素ボンベからオートクレーブ内に窒素を導入し、ゲージ圧１．０ＭＰａにて室温下で２４時間保持した。オートクレーブの圧力を開放し、得られた発泡性発泡粒子を取り出した後、高圧発泡槽に導入し、ゲージ圧０．３５ＭＰａの蒸気にて１８０秒加熱することで再発泡を行った。得られた三次発泡粒子の嵩倍数は７０倍（嵩密度０．０１４６ｇ／ｃｍ３）であった。
<Example 5: Evaluation of multistage foamability of expanded particles>
The expanded particles obtained in Production Example 5 were again placed in the autoclave, nitrogen was introduced into the autoclave from the nitrogen bomb, and held at a gauge pressure of 1.0 MPa at room temperature for 24 hours. After releasing the pressure of the autoclave and taking out the foamable foam particles obtained, the foamed foam particles were introduced into a high-pressure foaming tank and re-foamed by heating with steam having a gauge pressure of 0.35 MPa for 120 seconds. The volume expansion factor of the obtained tertiary expanded particles was 34 times (bulk density 0.03 g / cm 3 ).
<Example 6: Evaluation of multi-stage foamability of expanded particles>
The expanded particles obtained in Production Example 5 were again placed in the autoclave, nitrogen was introduced into the autoclave from the nitrogen bomb, and held at a gauge pressure of 1.0 MPa at room temperature for 24 hours. The pressure of the autoclave was released, and the obtained expandable foam particles were taken out, introduced into a high-pressure foam tank, and re-foamed by heating with steam having a gauge pressure of 0.35 MPa for 180 seconds. The bulk expansion factor of the obtained tertiary expanded particles was 70 times (bulk density 0.0146 g / cm 3 ).
＜実施例７；発泡粒子の多段発泡性評価＞
製造例６にて得られた発泡粒子を再度オートクレーブ内にいれ、窒素ボンベからオートクレーブ内に窒素を導入し、ゲージ圧１．０ＭＰａにて室温下で２４時間保持した。オートクレーブの圧力を開放し、得られた発泡性発泡粒子を取り出した後、高圧発泡槽に導入し、ゲージ圧０．３５ＭＰａの蒸気にて３０秒加熱することで再発泡を行った。得られた三次発泡粒子の嵩倍数は９４倍（嵩密度０．０１０９ｇ／ｃｍ３）であった。
＜実施例８；発泡粒子の多段発泡性評価＞
製造例６にて得られた発泡粒子を再度オートクレーブ内にいれ、窒素ボンベからオートクレーブ内に窒素を導入し、ゲージ圧１．０ＭＰａにて室温下で２４時間保持した。オートクレーブの圧力を開放し、得られた発泡性発泡粒子を取り出した後、高圧発泡槽に導入し、ゲージ圧０．３５ＭＰａの蒸気にて６０秒加熱することで再発泡を行った。得られた三次発泡粒子の嵩倍数は１１４倍（嵩密度０．００８９ｇ／ｃｍ３）であった。
<Example 7: Evaluation of multistage foamability of expanded particles>
The expanded particles obtained in Production Example 6 were again placed in the autoclave, nitrogen was introduced into the autoclave from the nitrogen bomb, and held at a gauge pressure of 1.0 MPa at room temperature for 24 hours. After releasing the pressure of the autoclave and taking out the foamable foam particles obtained, the foamed foam particles were introduced into a high-pressure foaming tank and re-foamed by heating with steam having a gauge pressure of 0.35 MPa for 30 seconds. The volume expansion factor of the obtained tertiary expanded particles was 94 times (bulk density 0.0109 g / cm 3 ).
<Example 8: Evaluation of multistage foamability of foamed particles>
The expanded particles obtained in Production Example 6 were again placed in the autoclave, nitrogen was introduced into the autoclave from the nitrogen bomb, and held at a gauge pressure of 1.0 MPa at room temperature for 24 hours. After releasing the pressure of the autoclave and taking out the expandable foam particles obtained, the foamed foam particles were introduced into a high-pressure foaming tank and re-foamed by heating with steam having a gauge pressure of 0.35 MPa for 60 seconds. The bulk expansion factor of the obtained tertiary expanded particles was 114 times (bulk density 0.0089 g / cm 3 ).
＜実施例９；発泡粒子の多段発泡性評価＞
製造例６にて得られた発泡粒子を再度オートクレーブ内にいれ、窒素ボンベからオートクレーブ内に窒素を導入し、ゲージ圧１．０ＭＰａにて室温下で２４時間保持した。オートクレーブの圧力を開放し、得られた発泡性発泡粒子を取り出した後、高圧発泡槽に導入し、ゲージ圧０．３５ＭＰａの蒸気にて１８０秒加熱することで再発泡を行った。得られた三次発泡粒子の嵩倍数は９３倍（嵩密度０．０１１０ｇ／ｃｍ３）であった。
＜実施例１０；発泡粒子の成形性評価＞
製造例４にて得られた発泡粒子を再度オートクレーブ内にいれ、窒素ボンベからオートクレーブ内に窒素を導入し、ゲージ圧１．０ＭＰａにて室温下で７２時間保持した。オートクレーブの圧力を開放し、得られた発泡性発泡粒子を取り出した後、高圧成形機を用いて発泡成形を実施した。具体的には、縦４００ｍｍ×横３００ｍｍ×厚さ３０ｍｍの内寸の成形用金型内に発泡粒子を充填し、ゲージ圧０．３５ＭＰａの蒸気を２４０秒導入して加熱し、冷却することで発泡成形体を得た。得られた成形体を室温下で乾燥させたところ、倍数２５倍相当の成形体（密度０．０４０８ｇ／ｃｍ３）が得られた。得られた成形体の外観は良好であった。
<Example 9: Evaluation of multistage foamability of expanded particles>
The expanded particles obtained in Production Example 6 were again placed in the autoclave, nitrogen was introduced into the autoclave from the nitrogen bomb, and held at a gauge pressure of 1.0 MPa at room temperature for 24 hours. The pressure of the autoclave was released, and the obtained expandable foam particles were taken out, introduced into a high-pressure foam tank, and re-foamed by heating with steam having a gauge pressure of 0.35 MPa for 180 seconds. The volume expansion factor of the obtained tertiary expanded particles was 93 times (bulk density 0.0110 g / cm 3 ).
<Example 10: Evaluation of moldability of expanded particles>
The expanded particles obtained in Production Example 4 were again placed in the autoclave, nitrogen was introduced into the autoclave from the nitrogen bomb, and held at room temperature for 72 hours at a gauge pressure of 1.0 MPa. After releasing the pressure of the autoclave and taking out the expandable foamed particles, foam molding was performed using a high-pressure molding machine. Specifically, foaming particles are filled into a molding die having an internal dimension of 400 mm in length, 300 mm in width, and 30 mm in thickness, steam with a gauge pressure of 0.35 MPa is introduced for 240 seconds, heated, and cooled. A foamed molded product was obtained. When the obtained molded body was dried at room temperature, a molded body (density 0.0408 g / cm 3 ) corresponding to a multiple of 25 times was obtained. The appearance of the obtained molded body was good.
＜比較例１；発泡粒子の多段発泡性評価＞
製造例７にて得られた発泡粒子を再度オートクレーブ内にいれ、窒素ボンベからオートクレーブ内に窒素を導入し、ゲージ圧１．０ＭＰａにて室温下で７２時間保持した。オートクレーブの圧力を開放し、得られた発泡性発泡粒子を取り出した後、高圧発泡槽に導入し、ゲージ圧０．３５ＭＰａの蒸気にて１５秒加熱することで再発泡を行った。得られた二次発泡粒子の嵩倍数は３３倍（嵩密度０．０３０９ｇ／ｃｍ３）であった。
＜比較例２；発泡粒子の多段発泡性評価＞
製造例７にて得られた発泡粒子を再度オートクレーブ内にいれ、窒素ボンベからオートクレーブ内に窒素を導入し、ゲージ圧１．０ＭＰａにて室温下で７２時間保持した。オートクレーブの圧力を開放し、得られた発泡性発泡粒子を取り出した後、高圧発泡槽に導入し、ゲージ圧０．３５ＭＰａの蒸気にて６０秒加熱することで再発泡を行った。得られた二次発泡粒子の嵩倍数は４０倍（嵩密度０．０２５５ｇ／ｃｍ３）であった。
<Comparative Example 1; Evaluation of multi-stage foamability of foamed particles>
The expanded particles obtained in Production Example 7 were again placed in the autoclave, nitrogen was introduced into the autoclave from the nitrogen bomb, and held at room temperature for 72 hours at a gauge pressure of 1.0 MPa. After releasing the pressure of the autoclave and taking out the foamable foam particles obtained, the foamed foam particles were introduced into a high-pressure foaming tank and re-foamed by heating with steam having a gauge pressure of 0.35 MPa for 15 seconds. The resulting secondary expanded particles had a bulk magnification of 33 times (bulk density: 0.0309 g / cm 3 ).
<Comparative Example 2; Evaluation of multi-stage foamability of expanded particles>
The expanded particles obtained in Production Example 7 were again placed in the autoclave, nitrogen was introduced into the autoclave from the nitrogen bomb, and held at room temperature for 72 hours at a gauge pressure of 1.0 MPa. After releasing the pressure of the autoclave and taking out the expandable foam particles obtained, the foamed foam particles were introduced into a high-pressure foaming tank and re-foamed by heating with steam having a gauge pressure of 0.35 MPa for 60 seconds. The resulting secondary expanded particles had a bulk magnification of 40 times (bulk density: 0.0255 g / cm 3 ).
＜比較例３；発泡粒子の多段発泡性評価＞
製造例７にて得られた発泡粒子を再度オートクレーブ内にいれ、窒素ボンベからオートクレーブ内に窒素を導入し、ゲージ圧１．０ＭＰａにて室温下で７２時間保持した。オートクレーブの圧力を開放し、得られた発泡性発泡粒子を取り出した後、高圧発泡槽に導入し、ゲージ圧０．３５ＭＰａの蒸気にて１８０秒加熱することで再発泡を行った。得られた二次発泡粒子の嵩倍数は３７倍（嵩密度０．０２７６ｇ／ｃｍ３）であった。
＜比較例４；発泡粒子の成形性評価＞
製造例７にて得られた発泡粒子を再度オートクレーブ内にいれ、窒素ボンベからオートクレーブ内に窒素を導入し、ゲージ圧１．０ＭＰａにて室温下で７２時間保持した。オートクレーブの圧力を開放し、得られた発泡性発泡粒子を取り出した後、高圧成形機を用いて発泡成形を実施した。具体的には、縦４００ｍｍ×横３００ｍｍ×厚さ３０ｍｍの内寸の成形用金型内に発泡粒子を充填し、ゲージ圧０．３５ＭＰａの蒸気を１８０秒導入して加熱し、冷却することで発泡成形体を得た。得られた成形体は二次発泡力不足によるボイドが見られた。なお、得られた成形体は、倍数２５倍相当（密度０．０４０８ｇ／ｃｍ３）であった。
実施例１〜９及び比較例１〜３の結果を表１に、実施例１０及び比較例４の結果を表２に示す。
<Comparative Example 3; Evaluation of multi-stage foamability of expanded particles>
The expanded particles obtained in Production Example 7 were again placed in the autoclave, nitrogen was introduced into the autoclave from the nitrogen bomb, and held at room temperature for 72 hours at a gauge pressure of 1.0 MPa. The pressure of the autoclave was released, and the obtained expandable foam particles were taken out, introduced into a high-pressure foam tank, and re-foamed by heating with steam having a gauge pressure of 0.35 MPa for 180 seconds. The resulting secondary expanded particles had a bulk magnification of 37 times (bulk density 0.0276 g / cm 3 ).
<Comparative Example 4: Moldability evaluation of expanded particles>
The expanded particles obtained in Production Example 7 were again placed in the autoclave, nitrogen was introduced into the autoclave from the nitrogen bomb, and held at room temperature for 72 hours at a gauge pressure of 1.0 MPa. After releasing the pressure of the autoclave and taking out the expandable foamed particles, foam molding was performed using a high-pressure molding machine. Specifically, foaming particles are filled into a molding die having an internal dimension of 400 mm long × 300 mm wide × 30 mm thick, steam with a gauge pressure of 0.35 MPa is introduced for 180 seconds, heated, and cooled. A foamed molded product was obtained. In the obtained molded product, voids due to insufficient secondary foaming power were observed. In addition, the obtained molded object was equivalent to 25 times (density 0.0408 g / cm < 3 >).
The results of Examples 1 to 9 and Comparative Examples 1 to 3 are shown in Table 1, and the results of Example 10 and Comparative Example 4 are shown in Table 2.
発泡性は、発泡率（実施例：３回目の嵩倍数÷２回目の嵩倍数、比較例：２回目の嵩倍数÷１回目の嵩倍数）が
・１．７以上である場合を○
・１．７未満である場合を×
とする。
The foaming property is obtained when the foaming ratio (Example: 3rd bulk multiple / second bulk multiple, comparative example: second bulk multiple / first bulk multiple) is 1.7 or more.
・ If less than 1.7 ×
And
外観は、
・良好な場合を○
・ボイドがある場合を×
とする。
Appearance is
・ ○
・ If there is a void ×
And
製造例４では、嵩倍数１２倍（嵩密度；０．０８５ｇ／ｃｍ３）の発泡粒子に、窒素で内圧付与し、再度発泡を行うことで嵩倍数２５倍（嵩密度；０．０４０８ｇ／ｃｍ３）発泡粒子を作製している。一方、製造例７では、樹脂粒子から直接嵩倍数２５倍（嵩密度；０．０４０８ｇ／ｃｍ３）の発泡粒子を作製している。表１から、１回目の発泡を抑制した実施例１〜９は、２．０倍以上の再発泡性を示したのに対し、抑制しなかった比較例１〜３は、最大再発泡性が１．６倍であった。表２から、１回目の発泡を抑制した方が、より良好な成形体を作製できることがわかる。 In Production Example 4, by applying an internal pressure to the foamed particles having a bulk multiple of 12 times (bulk density; 0.085 g / cm 3 ) with nitrogen and foaming again, the bulk multiple is 25 times (bulk density; 0.0408 g / cm). 3 ) Foamed particles are produced. On the other hand, in Production Example 7, foamed particles having a bulk multiple of 25 times (bulk density: 0.0408 g / cm 3 ) are produced directly from the resin particles. From Table 1, Examples 1-9 which suppressed the foaming of the 1st time showed re-foaming property of 2.0 times or more, whereas Comparative Examples 1-3 which did not suppress have the maximum re-foaming property. It was 1.6 times. From Table 2, it can be seen that a better molded body can be produced by suppressing the first foaming.
Claims (6)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015059992 | 2015-03-23 | ||
| JP2015059992 | 2015-03-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2016180098A JP2016180098A (en) | 2016-10-13 |
| JP6436583B2 true JP6436583B2 (en) | 2018-12-12 |
Family
ID=57131246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2016054035A Active JP6436583B2 (en) | 2015-03-23 | 2016-03-17 | Method for producing cyclic olefin-based resin expanded particles and method for producing expanded molded body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6436583B2 (en) |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2904842B2 (en) * | 1989-02-20 | 1999-06-14 | 三井化学株式会社 | Foamable polymer composition and foam |
| JP3207219B2 (en) * | 1991-06-20 | 2001-09-10 | 旭化成株式会社 | Low-expanded particles of polyolefin resin and method for producing the same |
| JP3165503B2 (en) * | 1992-03-30 | 2001-05-14 | 出光興産株式会社 | Foamable resin composition and foam |
| JP3403436B2 (en) * | 1992-11-12 | 2003-05-06 | 三井化学株式会社 | Expandable polymer particles and foams |
| JP3526660B2 (en) * | 1995-06-07 | 2004-05-17 | 株式会社ジェイエスピー | In-mold foaming particles and in-mold foam molding |
| JPH0938967A (en) * | 1995-07-31 | 1997-02-10 | Mitsui Petrochem Ind Ltd | Cyclic olefin based resin foamable pellet, preparation of said foamable pellet, and preparation of cyclic olefin basedresin foamable body |
| DE19619813A1 (en) * | 1995-10-30 | 1997-11-20 | Hoechst Ag | Polymer foams |
| JPH10176077A (en) * | 1996-12-19 | 1998-06-30 | Kanegafuchi Chem Ind Co Ltd | Polyolefin-based resin preexpanded particle and its production |
| JP4014262B2 (en) * | 1997-09-29 | 2007-11-28 | 三井化学株式会社 | Foam and its use |
| JP5308184B2 (en) * | 2009-02-19 | 2013-10-09 | Ｄｍノバフォーム株式会社 | Expandable resin particles |
-
2016
- 2016-03-17 JP JP2016054035A patent/JP6436583B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2016180098A (en) | 2016-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7326023B2 (en) | Thermoplastic elastomer foamed particles and molded products thereof | |
| EP3124521B1 (en) | High-density polyethylene mixed resin particles, composite resin particles, foamed particles and foamed molded body | |
| EP3339358B1 (en) | Polypropylene resin foamed particles, method for producing polypropylene resin foamed particles and polypropylene resin in-mold foam-molded article | |
| JP2016188321A (en) | Foamed particle and foamed molding | |
| JP3207219B2 (en) | Low-expanded particles of polyolefin resin and method for producing the same | |
| JPWO2009041361A1 (en) | Polypropylene resin composition for foaming and method for producing injection foam molding using the same | |
| BR112020010372A2 (en) | particle foams for aircraft interior applications | |
| Guo et al. | Fabrication of high temperature polyphenylsulfone nanofoams using high pressure liquid carbon dioxide | |
| JP6436583B2 (en) | Method for producing cyclic olefin-based resin expanded particles and method for producing expanded molded body | |
| EP3235860A1 (en) | Polypropylene resin foamed particles | |
| JP6529458B2 (en) | Cyclic olefin-based resin foam particles, method for producing the same, and foam molded article | |
| JPWO2016147919A1 (en) | Polypropylene-based resin expanded particles and method for producing the same | |
| EP3381976B1 (en) | Method for producing polypropylene-based resin foamed particles, polypropylene-based resin foamed particles, and in-mold foam molded article | |
| JP2014077123A (en) | Styrene-modified thermoplastic polyester resin particles and method for manufacturing the same; expandable styrene-modified thermoplastic polyester resin particles; styrene-modified thermoplastic polyester resin prefoamed particles; and styrene-modified thermoplastic polyester resin foam molding | |
| EP3012287B1 (en) | Polypropylene resin foamed particles having excellent flame resistance and conductivity and polypropylene resin-type in-mold foam molded body | |
| JP3560238B2 (en) | Method for producing expanded polypropylene resin particles, expanded polypropylene resin particles, and expanded molded article in polypropylene resin mold | |
| JP4831647B2 (en) | Polypropylene resin foam particles | |
| JP6392657B2 (en) | Foamed particles and foamed molded body | |
| JP2001018943A (en) | Container and its manufacture | |
| JP4128850B2 (en) | Method for producing in-mold foam molded product of polypropylene resin expanded particles | |
| JP2005015592A (en) | Manufacturing process of in-mold foamed molded article | |
| JP7311672B1 (en) | Method for producing expanded beads and expanded beads | |
| JP7191495B2 (en) | Expandable polyolefin composition and method | |
| WO2020261694A1 (en) | Modified expandable particles and molded object obtained from expandable particles | |
| JP2023118261A (en) | Polypropylene-based resin composition and injection foam molded body thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20170911 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20180417 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20180418 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180605 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20181107 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20181112 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6436583 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |