JPH09131741A - Manufacture of foamed body - Google Patents
Manufacture of foamed bodyInfo
- Publication number
- JPH09131741A JPH09131741A JP7292687A JP29268795A JPH09131741A JP H09131741 A JPH09131741 A JP H09131741A JP 7292687 A JP7292687 A JP 7292687A JP 29268795 A JP29268795 A JP 29268795A JP H09131741 A JPH09131741 A JP H09131741A
- Authority
- JP
- Japan
- Prior art keywords
- foam
- liquid
- decompression chamber
- resin
- main body
- 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.)
- Pending
Links
Landscapes
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Molding Of Porous Articles (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、発泡体の製造方法
に関する。TECHNICAL FIELD The present invention relates to a method for producing a foam.
【０００２】[0002]
【従来の技術】特開昭６２−１３４４１号公報に開示さ
れている再膨張性プラスチックチップのように、独立気
泡樹脂発泡体からなり、一旦収縮状態になっていて、樹
脂の弾性回復力と、気泡膜（セル膜）を通しての外部か
ら独立気泡（セル）内への空気の透過とによって徐々に
形状が回復するようになっている遅延された形状回復性
を有する発泡体が、既に提案されている。2. Description of the Related Art Like a re-expandable plastic chip disclosed in Japanese Patent Laid-Open No. 62-13441, it is made of a closed-cell resin foam, is in a contracted state once, and has an elastic recovery force of the resin. A foam having a delayed shape recovery property has been already proposed in which the shape is gradually recovered by the permeation of air from the outside into the closed cell (cell) through the cell film (cell film). There is.
【０００３】すなわち、この発泡体は、上述のように、
当初収縮状態になっていて、徐々に形状が三次元方向に
膨らみ、略収縮前の元の独立気泡樹脂発泡体の厚みまで
回復するようになっているため、収縮状態時であれば、
嵩張らず搬送や施工性に優れている。しかも、形状回復
によってシール性や断熱性も備えたものとなり、断熱材
やシール材等として有望視されている。That is, this foam is, as described above,
Initially in a contracted state, the shape gradually swells in the three-dimensional direction, and is designed to recover to the original thickness of the closed-cell resin foam before the contraction.
It is not bulky and has excellent transportability and workability. In addition, the shape is restored to have a sealing property and a heat insulating property, and is considered to be promising as a heat insulating material or a sealing material.
【０００４】[0004]
【発明が解決しようとする課題】しかし、従来の上記発
泡体の製造方法は、液化ガスを含浸させたチップ状の樹
脂材料を水蒸気によって加熱発泡させて原料発泡体を得
たのち、この原料発泡体を直ちに大気圧下で冷却し、気
泡を収縮させることによって発泡体を得るようになって
いる。However, according to the conventional method for producing a foam, the chip-shaped resin material impregnated with a liquefied gas is heated and foamed by steam to obtain a raw foam, and then the raw foam is used. The body is immediately cooled under atmospheric pressure, and the foam is obtained by shrinking the bubbles.
【０００５】したがって、連続的に製造することができ
ず、生産性に問題がある。しかも、上述のように三次元
方向にのみ形状回復する発泡体しか得ることができなか
った。Therefore, it cannot be manufactured continuously, and there is a problem in productivity. Moreover, as described above, only a foam body which can recover the shape only in the three-dimensional direction can be obtained.
【０００６】本発明は、このような事情に鑑みて、任意
の方向に形状回復性を有する発泡体を連続的に製造する
ことができる発泡体の製造方法を提供することを目的と
している。In view of such circumstances, an object of the present invention is to provide a method for producing a foam capable of continuously producing a foam having a shape recovering property in an arbitrary direction.
【０００７】[0007]
【課題を解決するための手段】このような目的を達成す
るために、本発明にかかる発泡体の製造方法は、入口側
に設けられた減圧室本体から出口に到る経路が所望の液
体によって封止された減圧室の、前記減圧室本体に発泡
性樹脂材料を連続的に送り込み、減圧室本体内でこの発
泡性樹脂材料を減圧発泡させて原料発泡体を得たのち、
この原料発泡体を、前記液体内に通して液体中で液圧お
よび／または所望の圧縮手段を介して任意の方向から圧
縮し、出口側から所望速度で連続的に引き取るようにし
た。In order to achieve such an object, in the method for producing a foam according to the present invention, the path from the decompression chamber main body provided on the inlet side to the outlet is formed by a desired liquid. In the sealed decompression chamber, a foaming resin material is continuously fed to the decompression chamber body, and after foaming the foaming resin material in the decompression chamber body to obtain a raw material foam,
This raw material foam was passed through the liquid, compressed in the liquid from any direction via hydraulic pressure and / or desired compression means, and continuously drawn from the outlet side at a desired speed.
【０００８】上記構成において、発泡体を構成する樹脂
としては、特に限定されないが、圧縮永久歪み（ＪＩＳ
Ｋ ６７６７に準拠）が２０％以下のもの、特に１０
％以下のものが形状回復性に優れ好ましい。このような
樹脂としては、以下のような熱可塑性樹脂あるいは熱硬
化性樹脂等が挙げれる。In the above structure, the resin constituting the foam is not particularly limited, but the compression set (JIS
20% or less, especially 10
% Or less is preferable because of excellent shape recoverability. Examples of such a resin include the following thermoplastic resins and thermosetting resins.
【０００９】〔熱可塑性樹脂〕ポリエチレン，ポリプロ
ピレン，エチレン−プロピレン共重合体，エチレン−プ
ロピレン−ジエン共重合体，エチレン−酢酸ビニル共重
合体等のオレフィン系樹脂、ポリメチルアクリレート，
ポリメチルメタクレート，エチレン−エチルアクリレー
ト共重合体等のアクリル系樹脂、ブタジエン−スチレ
ン，アクリロニトリル−スチレン，スチレン，スチレン
−ブタジエン−スチレン，スチレン−イソプレン−スチ
レン，スチレン−アクリル酸等のスチレン系樹脂、アク
リロニトリル−ポリ塩化ビニル，ポリ塩化ビニル−エチ
レン等の塩化ビニル系樹脂、ポリフッ化ビニル，ポリフ
ッ化ビニリデン等のフッ化ビニル系樹脂、６−ナイロ
ン，６・６−ナイロン，１２−ナイロン等のアミド樹
脂、ポリエチレンテレフタレート，ポリブチレンテレフ
タレート等の飽和エステル系樹脂、ポリカーボネート、
ポリフェニレンオキサイド、ポリアセタール、ポリフェ
ニレンスルフィド、シリコーン樹脂、熱可塑性ウレタン
樹脂、ポリエーテルエーテルケトン、ポリエーテルイミ
ド、各種エラストマーやこれらの架橋体。[Thermoplastic Resin] Olefin resin such as polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-vinyl acetate copolymer, polymethyl acrylate,
Acrylic resins such as polymethylmethacrylate and ethylene-ethyl acrylate copolymers, styrene-based resins such as butadiene-styrene, acrylonitrile-styrene, styrene, styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-acrylic acid, etc. Vinyl chloride resins such as acrylonitrile-polyvinyl chloride, polyvinyl chloride-ethylene, vinyl fluoride resins such as polyvinyl fluoride and polyvinylidene fluoride, amide resins such as 6-nylon, 6,6-nylon, 12-nylon Saturated polyethylene resin such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate,
Polyphenylene oxide, polyacetal, polyphenylene sulfide, silicone resin, thermoplastic urethane resin, polyether ether ketone, polyether imide, various elastomers and cross-linked products thereof.
【００１０】〔熱硬化性樹脂〕エポキシ系樹脂、フェノ
ール系樹脂、メラミン系樹脂、ウレタン系樹脂、イミド
系樹脂、ユリア系樹脂、シリコーン系樹脂、不飽和ポリ
エステル系樹脂の硬化物等。 〔天然樹脂〕天然ゴム、セルロース、デンプン、蛋白
質、うるしなどの樹液等なお、これらの樹脂は単独で用
いても２種以上併用しても良い。[Thermosetting Resin] A cured product of epoxy resin, phenol resin, melamine resin, urethane resin, imide resin, urea resin, silicone resin, unsaturated polyester resin, and the like. [Natural resin] Sap of natural rubber, cellulose, starch, protein, urushi, etc. These resins may be used alone or in combination of two or more.
【００１１】また、上記樹脂の中でも、特に形状回復性
に優れるものとして、オレフィン樹脂、スチレン系樹
脂、アミド系樹脂、アクリル共重合体、軟質ポリウレタ
ン、軟質塩化ビニル樹脂、ポリアセタール、シリコーン
樹脂、各種エラストマーが特に挙げられる。原料発泡体
の独立気泡率は、本発明の発泡体として必要とする回復
量により決まり、６０％〜１００％が好ましい。Among the above-mentioned resins, olefin resins, styrene resins, amide resins, acrylic copolymers, soft polyurethanes, soft vinyl chloride resins, polyacetals, silicone resins and various elastomers are particularly excellent in shape recovery. Is especially mentioned. The closed cell ratio of the raw material foam is determined by the amount of recovery required for the foam of the present invention, and is preferably 60% to 100%.
【００１２】本発明で使用される発泡剤としては、特に
限定されないが、たとえば、分解型の発泡剤としてアゾ
ジカルボンアミド（ＡＤＣＡ）、アゾビスイソブチロニ
トリル（ＡＩＢＮ）、ジニトロソペンタメチレンテトラ
ミン（ＤＰＴ）、ｐ−トルエンスルホニルヒドラジド
（ＴＳＨ）、ベンゼンスルホニルヒドラジド（ＢＳＨ）
及び、重炭酸ナトリウムなどが挙げられ、揮発型の発泡
剤として炭酸ガス、プロパン、メチルエーテル、ペンタ
ン、１，１−ジクロロ−１−フルオロエタンなどの気体
およびエーテル、石油エーテル、アセトン、エタノール
などの揮発性液体が挙げられる。The foaming agent used in the present invention is not particularly limited. For example, decomposition type foaming agents such as azodicarbonamide (ADCA), azobisisobutyronitrile (AIBN) and dinitrosopentamethylenetetramine ( DPT), p-toluenesulfonyl hydrazide (TSH), benzenesulfonyl hydrazide (BSH)
And sodium bicarbonate and the like, and as a volatile type foaming agent, carbon dioxide gas, propane, methyl ether, pentane, gas such as 1,1-dichloro-1-fluoroethane and ether and petroleum ether, acetone, ethanol and the like. Volatile liquids may be mentioned.
【００１３】また、これらの発泡剤のうち、炭酸ガス
等、透過性の大きいガスを用いることが好ましい。ま
た、これら発泡剤と共に、発泡速度を調節する発泡助剤
を添加してもよい。因に、発泡速度を速める発泡助剤と
して、ステアリン酸亜鉛，ステアリン酸カルシウム等の
金属石けん、亜鉛華，硝酸亜鉛等の無機塩、アジピン
酸，シュウ酸等の酸類が挙げられ、発泡速度を遅延する
発泡助剤として、マレイン酸，フタル酸等の有機酸、無
水マレイン酸，無水フタル酸等の有機酸無水物、ジブチ
ル錫マレート，塩化錫等の錫化合物が挙げられる。Of these foaming agents, it is preferable to use a gas having high permeability such as carbon dioxide gas. Further, a foaming aid for controlling the foaming rate may be added together with these foaming agents. As foaming aids for increasing the foaming speed, metal soaps such as zinc stearate and calcium stearate, inorganic salts such as zinc white and zinc nitrate, and acids such as adipic acid and oxalic acid are used, and the foaming speed is retarded. Examples of the foaming assistant include organic acids such as maleic acid and phthalic acid, organic acid anhydrides such as maleic anhydride and phthalic anhydride, and tin compounds such as dibutyltin malate and tin chloride.
【００１４】発泡助剤は、使用する樹脂，発泡剤，助剤
の種類によって異なるが、通常熱可塑性樹脂１００重量
部に対して０．１〜２重量部程度の添加割合で添加され
ることが好ましい。すなわち、添加量が０．１重量部以
下では、効果が小さく、２重量部以上では飽和状態とな
り、それ以上の添加効果がなくなる恐れがある。The foaming aid varies depending on the type of resin, foaming agent and auxiliary used, but is usually added in an addition ratio of about 0.1 to 2 parts by weight with respect to 100 parts by weight of the thermoplastic resin. preferable. That is, when the amount is 0.1 part by weight or less, the effect is small, and when the amount is 2 parts by weight or more, the state is saturated, and there is a possibility that the effect of further addition may be lost.
【００１５】また、上記発泡体には、充填剤、補強繊
維、着色剤、紫外線吸収剤、酸化防止剤、難燃剤等を必
要に応じて混合されていても構わない。充填剤として
は、たとえば、炭酸カルシウム、タルク、クレー、酸化
マグネシウム、酸化亜鉛、カーボンブラック、二酸化ケ
イ素、酸化チタン、ガラス粉、ガラスビーズ等が挙げら
れる。Further, the above foam may be mixed with a filler, a reinforcing fiber, a colorant, an ultraviolet absorber, an antioxidant, a flame retardant and the like, if necessary. Examples of the filler include calcium carbonate, talc, clay, magnesium oxide, zinc oxide, carbon black, silicon dioxide, titanium oxide, glass powder, glass beads and the like.
【００１６】補強繊維としては、たとえば、ガラス繊
維、炭素繊維等が挙げられる。着色剤としては、たとえ
ば、酸化チタン等の顔料が挙げられる。酸化防止剤とし
ては、一般に用いれるものであれば、特に限定されず、
たとえば、テトラキス〔メチレン（３，５−ジ−ｔ−ブ
チル−４−ヒドロキシハイドロシンナメート）〕メタ
ン、チオジプロピオン酸ジラウリル、１，１，３−トリ
ス（２−メチル−４−ヒドロキシ−５−ｔ−ブチルフェ
ニル）ブタン等が挙げられる。Examples of the reinforcing fibers include glass fibers and carbon fibers. Examples of the coloring agent include pigments such as titanium oxide. The antioxidant is not particularly limited as long as it is generally used,
For example, tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane, dilauryl thiodipropionate, 1,1,3-tris (2-methyl-4-hydroxy-5- t-butylphenyl) butane and the like.
【００１７】難燃剤としては、ヘキサブロモフェニルエ
ーテル，デカブロモジフェニルエーテル等の臭素系難燃
剤、ポリリン酸アンモニウム、トリメチルホスフェー
ト、トリエチルホスフェート等の含リン酸系難燃剤、メ
ラミン誘導体、無機系難燃剤等の１種又は２種以上の混
合物が挙げられる。減圧室本体内の圧力は、特に限定さ
れないが、絶対圧力で０．０５〜０．９atm 程度が好ま
しく、０．０５〜０．５atm 程度がより好ましい。Examples of the flame retardant include bromine flame retardants such as hexabromophenyl ether and decabromodiphenyl ether, phosphoric acid flame retardants such as ammonium polyphosphate, trimethyl phosphate and triethyl phosphate, melamine derivatives and inorganic flame retardants. Examples include one kind or a mixture of two or more kinds. The pressure inside the decompression chamber body is not particularly limited, but is preferably about 0.05 to 0.9 atm in absolute pressure, more preferably about 0.05 to 0.5 atm.
【００１８】すなわち、０．０５atm を下回ると、圧縮
時に樹脂自体の変形の大部分が塑性変形となり、形状回
復性が損なわれ、０．９atm を超えると大気圧に戻して
も充分な回復量が得られず、結果として形状回復性も損
なわれる。減圧室の減圧室本体と出口とを封止する液体
としては、原料発泡体を構成する樹脂を溶解しない液体
であれば、水等、特に限定されないが、比重の大きい液
体の方が好ましい。That is, if it is less than 0.05 atm, most of the deformation of the resin itself becomes plastic deformation at the time of compression and the shape recoverability is impaired, and if it exceeds 0.9 atm, a sufficient recovery amount is obtained even if the pressure is returned to atmospheric pressure. Not obtained, and as a result, the shape recoverability is also impaired. The liquid for sealing the decompression chamber main body and the outlet of the decompression chamber is not particularly limited, such as water, as long as it does not dissolve the resin forming the raw material foam, but a liquid having a large specific gravity is preferable.
【００１９】すなわち、比重が大きいと、減圧室本体側
と、出口側との液面差を小さくすることができ、装置自
体をコンパクトにすることができる。なお、発泡体製造
時の液体の温度は、原料発泡体を構成する樹脂の軟化点
（非晶性樹脂についてはガラス転移点、結晶性樹脂につ
いては融点を軟化点とする）以下である。すなわち、液
体を軟化点以上の温度にして圧縮を行った場合、抜重後
の発泡体の形状回復能がなくなる恐れがある。That is, when the specific gravity is large, the liquid level difference between the decompression chamber main body side and the outlet side can be made small, and the apparatus itself can be made compact. The temperature of the liquid during the production of the foam is equal to or lower than the softening point of the resin constituting the raw material foam (the glass transition point for the amorphous resin, the melting point for the crystalline resin is the softening point). That is, when the liquid is compressed at a temperature equal to or higher than the softening point, there is a possibility that the shape recovery ability of the foamed body after weight removal may be lost.
【００２０】液圧以外の圧縮手段としては、無端ベル
ト、ロール、絞りダイ等で直接圧縮するもの、などが挙
げられ、これらを組み合わて用いることもできる。な
お、絞りダイで圧縮する方法の場合、液体はシリコーン
オイル等の潤滑性を備えたものが好ましい。また、液体
中の原料発泡体に所望の張力を与えるために、減圧室本
体の出口付近に原料発泡体を挟むようにピンチローラを
設けておくことが好ましい。Examples of the compression means other than the hydraulic pressure include direct compression with an endless belt, a roll, a drawing die and the like, and these may be used in combination. In the case of the method of compressing with a drawing die, the liquid preferably has a lubricating property such as silicone oil. Further, in order to apply a desired tension to the raw material foam in the liquid, it is preferable to provide a pinch roller near the outlet of the decompression chamber body so as to sandwich the raw material foam.
【００２１】[0021]
【発明の実施の形態】以下に、本発明の実施の形態を図
面を参照しつつ詳しく説明する。図１は、本発明の実施
の形態をあらわしている。本発明の製造方法は、図１に
示すような製造装置１を用いて行うことができる。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below with reference to the drawings. FIG. 1 shows an embodiment of the present invention. The manufacturing method of the present invention can be performed using the manufacturing apparatus 1 as shown in FIG.
【００２２】すなわち、この製造装置１ａは、押出機２
と、減圧室３ａと、引取りローラ４，４とを備えてい
る。押出機２は、発泡剤となるガスを樹脂中に供給する
ガス供給装置２１を有し、その出口が減圧室３ａの入口
３１に臨んでいて、押出機２から連続的に押出成形され
る発泡性樹脂材料５ａが直ちに減圧室３ａ内に入るよう
になっている。That is, the manufacturing apparatus 1a includes the extruder 2
And the decompression chamber 3a and the take-up rollers 4 and 4. The extruder 2 has a gas supply device 21 for supplying a gas serving as a foaming agent into the resin, and its outlet faces the inlet 31 of the decompression chamber 3a, and foaming is continuously extruded from the extruder 2. The resin material 5a immediately enters the decompression chamber 3a.
【００２３】減圧室３ａは、出口３２が入口３１より低
い位置に設けられているとともに、入口３１から出口３
２に到る経路としての中間部３３が入口３１および出口
３２より低くなっている。そして、中間部３３に入口３
１と出口３２との間を封止するように所定量の液体６が
入れられるようになっている。The decompression chamber 3a is provided with the outlet 32 at a position lower than the inlet 31, and also from the inlet 31 to the outlet 3.
The intermediate portion 33 as a route to reach 2 is lower than the inlet 31 and the outlet 32. And the entrance 3 to the intermediate portion 33
A predetermined amount of liquid 6 is introduced so as to seal between 1 and the outlet 32.
【００２４】すなわち、液体６で封止された入口側の部
分が減圧室本体３４となっている。減圧室本体３４に
は、真空装置３５が接続されていて、液封された減圧室
本体３４内を所望の圧力に減圧できるようになっている
とともに、原料発泡体８ａを挟むようにピンチローラ３
７，３７が設けられている。また、中間部３３には、最
下端部付近に、減圧室３ａの中間部３３内の液体６を増
減させることができる液量調整装置３６が設けられてい
るとともに、図示していないが、無端ベルト、ローラ、
テンター等の規制手段や、ピンチローラ、絞りダイ等の
圧縮手段を必要に応じて設けることができるようになっ
ている。That is, the inlet side portion sealed with the liquid 6 is the decompression chamber body 34. A vacuum device 35 is connected to the decompression chamber main body 34 so as to reduce the pressure inside the liquid-sealed decompression chamber main body 34 to a desired pressure, and also to pinch the raw material foam 8a.
7, 37 are provided. Further, the intermediate portion 33 is provided with a liquid amount adjusting device 36 capable of increasing / decreasing the amount of the liquid 6 in the intermediate portion 33 of the decompression chamber 3a in the vicinity of the lowermost end portion, and although not shown, there is no end Belts, rollers,
A restricting means such as a tenter and a compressing means such as a pinch roller and a drawing die can be provided as needed.
【００２５】引取りローラ４，４は、その引取り速度を
自由に調整できるようになっている。したがって、この
製造装置１ａを用いれば、つぎのようにして所望の発泡
体９を製造することができる。The take-up rollers 4, 4 can freely adjust their take-up speed. Therefore, by using this manufacturing apparatus 1a, the desired foam 9 can be manufactured as follows.
【００２６】 減圧室３ａの入口３１側と出口側３２
との間を封止するように中間部３３に所望量の液体６を
満たし、入口３１側に減圧室本体３４をつくる。 真空装置３５によって減圧室本体３４内を所望の減
圧状態にする。この減圧度に応じて、液体６は、入口側
３１の方が出口側３２より高くなる。An inlet 31 side and an outlet side 32 of the decompression chamber 3a
The intermediate portion 33 is filled with a desired amount of the liquid 6 so as to seal the space between and, and the decompression chamber main body 34 is formed on the inlet 31 side. The inside of the decompression chamber body 34 is brought into a desired decompression state by the vacuum device 35. The liquid 6 becomes higher on the inlet side 31 than on the outlet side 32 depending on the degree of pressure reduction.
【００２７】 発泡剤となるガスをガス供給装置２１
から樹脂中に注入して発泡性樹脂材料５ａを押出機２か
ら入口３１を介して減圧室本体３４内に押し出す。これ
により、発泡性樹脂材料５ａが減圧室本体３４内で発泡
して原料発泡体８ａとなる。すなわち、発泡性樹脂材料
５ａを大気圧以下に減圧された空間で発泡させることに
より、得られた原料発泡体８ａの気泡内圧はほぼ減圧さ
れた空間の圧力とほぼ等しくなっている。The gas serving as the foaming agent is supplied to the gas supply device 21.
And the foamable resin material 5a is extruded from the extruder 2 into the decompression chamber main body 34 through the inlet 31. As a result, the foamable resin material 5a foams in the decompression chamber body 34 to become the raw material foam 8a. That is, by foaming the expandable resin material 5a in the space depressurized to the atmospheric pressure or lower, the internal pressure of the bubbles of the obtained raw material foam 8a is substantially equal to the pressure of the depressurized space.
【００２８】 原料発泡体８ａを中間部３３の液体６
内を通して、原料発泡体８ａに液体６内で所望の圧縮手
段によって所望方向から圧縮して原料発泡体８ａを構成
する樹脂の弾性変形領域内で収縮させて発泡体９を得
る。 得られた発泡体９を引取りローラ４，４で連続的に
引き取る。The raw material foam 8 a is mixed with the liquid 6 in the intermediate portion 33.
Through the inside, the raw material foam 8a is compressed in the liquid 6 from a desired direction by a desired compression means and contracted in the elastic deformation region of the resin forming the raw material foam 8a to obtain the foam 9. The foam 9 thus obtained is continuously taken up by the take-up rollers 4 and 4.
【００２９】因に、液体６中で、図２に示すように、原
料発泡体８ａの幅方向の両端部８１，８１を、たとえ
ば、無端ベルト８２，８２と受板８３とによって上下か
ら挟持して幅方向に収縮しないように規制するととも
に、引取りロール４，４による引取り速度を調整してピ
ンチローラ３７，３７と引取りローラ４，４との間の原
料発泡体８ａおよび発泡体９に所定の張力を加え原料発
泡体８ａがその進行方向に収縮しないように規制する
と、液体６の圧力によって原料発泡体８ａが厚み方向の
みに収縮した発泡体９を得ることができる。As shown in FIG. 2, both ends 81, 81 of the raw material foam 8a in the width direction are clamped from above and below by the endless belts 82, 82 and the receiving plate 83, for example, in the liquid 6. Of the raw material foam 8a and the foam 9 between the pinch rollers 37, 37 and the take-up rollers 4, 4 by adjusting the take-up speed by the take-up rolls 4, 4 so as not to shrink in the width direction. When a predetermined tension is applied to the raw material foam 8a so that the raw material foam 8a is not contracted in the traveling direction, the raw material foam 8a can be contracted only in the thickness direction by the pressure of the liquid 6 to obtain the foam 9.
【００３０】また、引取りロール４，４による引取り速
度を調整してピンチローラ３７，３７と引取りローラ
４，４との間の原料発泡体８ａおよび発泡体９に所定の
張力を加え原料発泡体８ａがその進行方向に収縮しない
ように規制するだけにすると、液体６の圧力によって原
料発泡体８ａの進行方向を除く周囲から均等に収縮した
発泡体９を得ることができる。Further, by adjusting the take-up speed by the take-up rolls 4 and 4, a predetermined tension is applied to the raw material foam 8a and the foam 9 between the pinch rollers 37 and 37 and the take-up rollers 4 and 4, and the raw material is applied. If only the foam 8a is restricted so as not to shrink in the traveling direction, the foam 9 uniformly contracted by the pressure of the liquid 6 from the periphery excluding the traveling direction of the raw material foam 8a can be obtained.
【００３１】さらに、引取りローラ４，４による引取り
速度を遅くしてピンチローラ３７，３７と引取りローラ
４，４との間の原料発泡体８ａおよび発泡体９に所定の
張力を加えないようにすると、進行方向に収縮した、す
なわち、三次元的に収縮した発泡体９を得ることができ
る。Further, the take-up speed by the take-up rollers 4 and 4 is slowed so that a predetermined tension is not applied to the raw material foam 8a and the foam 9 between the pinch rollers 37 and 37 and the take-up rollers 4 and 4. By doing so, it is possible to obtain the foam 9 that contracts in the traveling direction, that is, contracts three-dimensionally.
【００３２】また、液体６として潤滑性を有するシリコ
ーンオイル等を用いるとともに、図３に示すように、液
体６中に所望の断面形状の絞りダイ７を設ければ、原料
発泡体８ａを絞りダイ７の断面形状に収縮した発泡体９
を得ることができる。この製造方法によれば、以上のよ
うに、所望の方向に収縮した遅延された形状回復性を有
する発泡体９を連続的に得ることができる。すなわち、
用途に応じた所望形状の発泡体９を生産性よく製造する
ことができる。Further, if a silicone oil having lubricity is used as the liquid 6 and a drawing die 7 having a desired sectional shape is provided in the liquid 6 as shown in FIG. 3, the raw material foam 8a is drawn. Foam 9 shrunk to 7 cross-sectional shape
Can be obtained. According to this manufacturing method, as described above, it is possible to continuously obtain the foam 9 that is contracted in the desired direction and has the delayed shape recovery property. That is,
It is possible to produce the foam 9 having a desired shape according to the use with high productivity.
【００３３】また、原料発泡体を減圧下で発泡させて得
るため、高倍率の発泡体を得ることができるとともに、
減圧度を変えることにより、発泡倍率も容易に変更でき
る。しかも、減圧発泡のあと、直ちに液圧をかけるた
め、大気圧下で収縮させる場合に比べ原料発泡体を早期
に収縮させることができ生産性がより向上する。また、
減圧室本体３４部分のシールを液体６によって行ってい
るため、シール部材の磨耗等の問題もなく、製造装置１
ａのメンテナンスも容易である。Further, since the raw material foam is obtained by foaming it under reduced pressure, it is possible to obtain a high-magnification foam and
The foaming ratio can be easily changed by changing the degree of vacuum. Moreover, since the liquid pressure is applied immediately after the foaming under reduced pressure, the raw material foam can be contracted earlier than in the case of contracting under the atmospheric pressure, and the productivity is further improved. Also,
Since the liquid 6 is used to seal the decompression chamber main body 34, there is no problem such as wear of the seal member, and the manufacturing apparatus 1
Maintenance of a is also easy.
【００３４】図４は本発明の製造方法の他の実施の形態
をあらわしている。図４に示すように、この製造方法で
は、予備発泡された予備発泡体または熱分解型発泡剤を
含有する発泡原反を発泡性樹脂材料５ｂと、減圧室３ｂ
の入口３８の手前にピンチローラ１１，１１を有し、入
口３８内周面に潤滑剤が塗布されるか、入口３８内周面
がフッ素樹脂等の摩擦係数の小さい樹脂で形成されるな
どしてシール性を保持するようにするとともに、減圧室
３ｂの入口３８側内壁面に沿ってヒータ３９が設けられ
た製造装置１ｂとを用いる以外は、上記の実施の形態と
同様にして発泡体９を得ることができる。FIG. 4 shows another embodiment of the manufacturing method of the present invention. As shown in FIG. 4, in this manufacturing method, a foamed raw material containing a pre-foamed pre-foamed body or a pyrolytic foaming agent is used as a foaming resin material 5b and a decompression chamber 3b.
Has a pinch roller 11, 11 in front of the inlet 38 of the, and a lubricant is applied to the inner peripheral surface of the inlet 38, or the inner peripheral surface of the inlet 38 is formed of a resin having a small friction coefficient such as a fluororesin. To maintain the sealing property and to use the manufacturing apparatus 1b in which the heater 39 is provided along the inner wall surface of the decompression chamber 3b on the inlet 38 side, in the same manner as in the above embodiment. Can be obtained.
【００３５】すなわち、予備発泡された予備発泡体また
は熱分解型発泡剤を含有する発泡原反からなる発泡性樹
脂材料５ｂは、ピンチロール１１，１１によって所定速
度で減圧室３ｂの入口３８から所望の減圧度に減圧され
た減圧室本体３４内へ送りこまれるのであるが、発泡性
樹脂材料５ｂが予備発泡体であれば、減圧室本体３４側
に送り込まれるとヒータ３９によって樹脂の軟化点付
近、発泡原反であれば、発泡剤の分解温度まで加熱され
たのち減圧下でそれぞれ発泡し原料発泡体８ｂとなり、
以下同様にして発泡体９を得ることができる。That is, the expandable resin material 5b made of a pre-foamed pre-foamed material or a foamed raw material containing a pyrolytic foaming agent is desired from the inlet 38 of the decompression chamber 3b at a predetermined speed by the pinch rolls 11, 11. Although it is fed into the decompression chamber main body 34 decompressed to the decompression degree, if the expandable resin material 5b is a pre-foamed body, when it is fed to the decompression chamber main body 34 side, the heater 39 causes the vicinity of the softening point of the resin, If it is a raw material foam, it is heated to the decomposition temperature of the foaming agent and then foamed under reduced pressure to form the raw material foam 8b.
The foam 9 can be obtained in the same manner.
【００３６】[0036]
【実施例】つぎに、本発明の実施例を詳しく説明する。 （実施例１）減圧室３ａの全長が２０ｍである図１に示
す装置１ａを用いて以下のとおりに発泡体９を製造し
た。EXAMPLES Next, examples of the present invention will be described in detail. (Example 1) Foam 9 was manufactured as follows using apparatus 1a shown in FIG. 1 in which decompression chamber 3a has a total length of 20 m.
【００３７】まず、減圧室３ａの中間部３３に、液体６
として水をはるとともに、減圧室本体３４部分を絶対圧
で０．２atm に減圧した。また、この時の入口３１側と
出口側３２の水位差は、約８ｍであった。First, the liquid 6 is placed in the intermediate portion 33 of the decompression chamber 3a.
As the water was poured, the pressure reducing chamber main body 34 was depressurized to 0.2 atm by absolute pressure. The water level difference between the inlet 31 side and the outlet side 32 at this time was about 8 m.
【００３８】つぎに、低密度ポリエチレン（三菱油化社
製 ＺＣ３０ 融点１１０℃）に樹脂１００ｇ当たり炭
酸ガスを１．２ｇ圧入し、押出機２の直径２．０mmの円
形口金から連続的に減圧室本体３４内に発泡性樹脂材料
５ａとして押出成形し、減圧室本体３４内で発泡させ、
直径１０mm、発泡倍率２９倍、独立気泡率８５％の原料
発泡体８ａを連続的に得るとともに、この原料発泡体８
ａを中間部３３の水中を通して出口３２側に導入し、２
５８ｍ／分（圧縮所要時間５秒）で引取りロール４，４
によって引き取って発泡体９を連続的に得た。Next, 1.2 g of carbon dioxide gas per 100 g of resin was injected into low-density polyethylene (ZC30, melting point 110 ° C., manufactured by Mitsubishi Petrochemical Co., Ltd.), and the decompression chamber was continuously discharged from the circular die of the extruder 2 having a diameter of 2.0 mm. Extrusion molding as a foamable resin material 5a in the main body 34, foaming in the decompression chamber main body 34,
A raw material foam 8a having a diameter of 10 mm, a foaming ratio of 29 times, and a closed cell rate of 85% is continuously obtained.
a through the water of the intermediate portion 33 to the outlet 32 side,
Take-up rolls 4, 4 at 58 m / min (compression time 5 seconds)
Then, the foamed body 9 was continuously obtained by taking out.
【００３９】得られた発泡体９は製造直後その直径が
４．５mmであったが、その後もガス透過によって１時間
程で直径４mmまで収縮した。そして、この発泡体９を常
温常圧下３０日間放置したところ、直径約９mmまで二次
元的に形状回復した。The obtained foam 9 had a diameter of 4.5 mm immediately after its production, but thereafter it contracted to a diameter of 4 mm in about 1 hour due to gas permeation. When the foam 9 was left standing for 30 days at room temperature and pressure, the shape was two-dimensionally recovered to a diameter of about 9 mm.
【００４０】（実施例２）減圧室３ｂの全長が２０ｍで
ある図４に示す装置１ｂを用いて以下のとおりに発泡体
９を製造した。まず、減圧室３ｂの中間部３３に、液体
６としてジメチルシリコーンオイル（東レ・ダウコーニ
ング・シリコーン社製、比重０．９７）をはるととも
に、減圧室本体３４部分を絶対圧で０．３atm に減圧し
た。そして、この時の入口３８側と出口側の液面差は、
約７ｍであった。また、ヒータ３９としては赤外線ヒー
タを用い、ヒータ３９の加熱温度としては、２４０℃に
設定した。Example 2 Foam 9 was manufactured as follows using the apparatus 1b shown in FIG. 4 in which the total length of the decompression chamber 3b was 20 m. First, dimethyl silicone oil (manufactured by Toray Dow Corning Silicone Co., Ltd., specific gravity 0.97) is applied as liquid 6 to the intermediate portion 33 of the decompression chamber 3b, and the decompression chamber main body 34 is adjusted to 0.3 atm in absolute pressure. The pressure was reduced. The liquid level difference between the inlet 38 side and the outlet side at this time is
It was about 7 m. An infrared heater was used as the heater 39, and the heating temperature of the heater 39 was set to 240 ° C.
【００４１】つぎに、 ・低密度ポリエチレン（住友化学社製 Ｇ２０１） １００重量部 ・アゾジカルボンアミド ５重量部 ・酸化亜鉛 ２重量部 を配合してなる樹脂組成物を押出機により、幅２００m
m、厚さ３mmに押し出した後、７５０kv×４Ｍrad の条
件で電子線架橋を行って発泡原反を得た。Next, 100 parts by weight of low-density polyethylene (G201 manufactured by Sumitomo Chemical Co., Ltd.), 5 parts by weight of azodicarbonamide, and 2 parts by weight of zinc oxide were used to prepare a resin composition having a width of 200 m by an extruder.
After extruding to a thickness of 3 mm and a thickness of 3 mm, electron beam crosslinking was carried out under the condition of 750 kv × 4 Mrad to obtain a foamed raw fabric.
【００４２】この発泡原反を１００℃に温め、発泡性樹
脂材料５ｂとしてピンチロール１１，１１によって３ｍ
／分の速度で減圧室３ｂの入口３８から減圧室本体３４
内に送り込んで減圧室本体３４内で減圧発泡させ、幅６
００mm、厚さ９mm、発泡倍率２９倍、独立気泡率８５％
の原料発泡体８ｂを得るとともに、減圧室本体３４の出
口側に設けたピンチロール３７，３７で９ｍ／分の線速
で液体６中に送り込むとともに、液体６中に設けた入口
の断面形状が９mm×６００mmで出口の断面形状が５mm×
４００mmの図３に示すような絞りダイ７を通してこの原
料発泡体８ｂを収縮させたのち、引取りロール４，４に
よって７ｍ／分の速度で連続的に引き取って断面形状が
５mm×４００mmの発泡体を得た。This foamed raw fabric is heated to 100 ° C., and as the foamable resin material 5b, 3 m is obtained by the pinch rolls 11 and 11.
From the inlet 38 of the decompression chamber 3b to the decompression chamber main body 34 at a speed of 1 / min.
It is sent into the inside of the decompression chamber main body 34 to be decompressed and foamed, and the width 6
00 mm, thickness 9 mm, expansion ratio 29 times, closed cell rate 85%
In addition to obtaining the raw material foam 8b, the pinch rolls 37, 37 provided on the outlet side of the decompression chamber body 34 are fed into the liquid 6 at a linear velocity of 9 m / min, and the sectional shape of the inlet provided in the liquid 6 9mm x 600mm, the cross-sectional shape of the exit is 5mm x
This raw material foam 8b was shrunk through a 400 mm drawing die 7 as shown in FIG. 3, and then continuously taken by the take-up rolls 4 and 4 at a speed of 7 m / min to obtain a foam having a cross-sectional shape of 5 mm × 400 mm. Got
【００４３】得られた発泡体を５mm×４００mm×６００
mmに裁断し、常温常圧下で３０日間放置したところ、
７．５mm×５５０mm×７３０mmまで三次元的に形状が回
復した。The obtained foam is 5 mm × 400 mm × 600
When cut into mm and left at room temperature and pressure for 30 days,
The shape recovered three-dimensionally up to 7.5 mm x 550 mm x 730 mm.
【００４４】（比較例１） ・スチレン−アクリロニトリル共重合体（旭化成工業社製、スライラックＡＳ７ ６９） １００重量部 ・タルク（日本タルク社製 ＭＳ） ０．２重量部 を配合してなる樹脂組成物を、スクリュー押出機（φ５
０mm、Ｌ／Ｄ＝３０）のホッパーに投入し、押出機内で
溶融混練した。なお、押出機のシリンダー温度は、ホッ
パーから押出機先端に向かって１９０℃、２０５℃、２
２０℃、２２０℃に設定しておいた。(Comparative Example 1) 100 parts by weight of styrene-acrylonitrile copolymer (Asahi Kasei Kogyo Co., Ltd., Slylac AS7 69) Talc (MS of Nippon Talc Co., Ltd.) 0.2 parts by weight resin composition Screw extruder (φ5
It was put into a hopper of 0 mm and L / D = 30) and melt-kneaded in the extruder. The cylinder temperature of the extruder is 190 ° C, 205 ° C, 2 ° C from the hopper toward the tip of the extruder.
It was set to 20 ° C and 220 ° C.
【００４５】つぎに、スクリュー先端部に設けられた発
泡材注入部から、発泡剤としてトリクロロモノフルオロ
メタンを上記樹脂組成物１００ｇ当たり３２ｇの割合で
投入し、引続き１００℃になるまで充分に冷却し、直径
φ０．８mmのノズル多数個を有した口金からストランド
状に５kg／ｈの押出量で押し出し、直ちに冷却シ、カッ
ターにて直径１mm、長さ３mmのペレット状未発泡粒子を
得た。Next, trichloromonofluoromethane was added as a foaming agent at a ratio of 32 g per 100 g of the resin composition from a foaming material injection portion provided at the tip of the screw, and then sufficiently cooled to 100 ° C. Then, it was extruded in a strand shape from a die having a large number of nozzles having a diameter of 0.8 mm at an extrusion rate of 5 kg / h, and immediately cooled, and a pellet-shaped unexpanded particle having a diameter of 1 mm and a length of 3 mm was obtained with a cutter.
【００４６】このペレット状未発泡粒子を室温にて熟成
放置後、ゲージ圧０．３kg／cm2 のスチーム雰囲気で４
５秒間加熱し発泡させたのち、得られた発泡体を１０℃
に冷却したところ、発泡体が１０分後３次元方向に自然
収縮して形状回復性の発泡体が得られた。The pelletized unexpanded particles were aged at room temperature and then left in a steam atmosphere with a gauge pressure of 0.3 kg / cm 2.
After heating for 5 seconds to foam, the resulting foam is heated to 10 ° C.
After cooling for 10 minutes, the foam spontaneously shrank in the three-dimensional direction to obtain a shape-recoverable foam.
【００４７】得られた発泡体は、発泡倍率が３５．５倍
で、３０日間常温、常圧で放置したところ、発泡倍率が
１６４倍まで３次元的に形状が回復した。また、独立気
泡率は９２％であった。なお、上記実施例１，２および
比較例１において、発泡倍率、独立気泡率は、以下のよ
うにして求めた。The foamed product thus obtained had an expansion ratio of 35.5 and was left for 30 days at room temperature and normal pressure, and the foaming ratio was restored three-dimensionally up to 164 times. Further, the closed cell rate was 92%. In Examples 1 and 2 and Comparative Example 1, the expansion ratio and the closed cell ratio were determined as follows.
【００４８】〔発泡倍率〕得られた発泡体から縦３５mm
×横３５mmの小片を切り出し、その小片を、水が入れら
れたメスシリンダー内に沈めて、その体積Ａを測定する
とともに、電子天秤を用いてその重量を測定する。そし
て、得られた発泡体の重量を、発泡体の小片の体積Ａで
除し、発泡体の密度を算出し、発泡倍率＝用いた樹脂の
密度／発泡密度の式により求める。[Expansion ratio] 35 mm in length from the obtained foam
× A small piece of 35 mm in width is cut out, the small piece is submerged in a measuring cylinder containing water, and its volume A is measured, and its weight is measured using an electronic balance. Then, the weight of the obtained foam is divided by the volume A of the small piece of the foam, the density of the foam is calculated, and the expansion ratio = the density of the resin used / the foam density is determined.
【００４９】〔独立気泡率〕空気比較式比重計１０００
型（東京サイエンス社製）を用い、１〜１／２〜１気圧
法で体積Ｂ（独立気泡体積＋樹脂体積）を測定する。そ
して、独立気泡率＝（体積Ｂ−重量／樹脂の密度）／
（体積Ａ−重量／樹脂の密度）の式により求める。[Independent bubble ratio] Air-comparison specific gravity meter 1000
Using a mold (manufactured by Tokyo Science Co., Ltd.), the volume B (closed cell volume + resin volume) is measured by the 1-1 / 2-1 atmosphere method. And closed cell rate = (volume B-weight / resin density) /
It is determined by the formula (volume A-weight / resin density).
【００５０】[0050]
【発明の効果】本発明にかかる発泡体の製造方法は、以
上のように構成されているので、所望方向に収縮した遅
延した形状回復性を有する発泡体を連続して製造するこ
とができる。また、原料発泡体を減圧下で発泡させて得
るため、高倍率の発泡体を得ることができるとともに、
液量を変えるなどして収縮度も容易に変更できる。EFFECTS OF THE INVENTION Since the method for producing a foam according to the present invention is constructed as described above, it is possible to continuously produce a foam having a delayed shape recovery property which shrinks in a desired direction. Further, since the raw material foam is obtained by foaming under reduced pressure, it is possible to obtain a high-magnification foam,
The degree of shrinkage can be easily changed by changing the liquid volume.
【００５１】しかも、減圧発泡のあと、直ちに液圧をか
けるため、大気圧下で収縮させる場合に比べ原料発泡体
を早期に収縮させる。すなわち、断熱材やシール材やい
ろいろな用途に使用できる発泡体を安価に生産性よく製
造することができる。また、減圧室本体部分のシールを
液体によって行っているため、シール部材の磨耗等の問
題もなく、製造装置のメンテナンスも容易である。Moreover, since the liquid pressure is applied immediately after the foaming under reduced pressure, the raw material foam is contracted earlier than when the foaming is contracted under the atmospheric pressure. That is, a heat insulating material, a sealing material, and a foam that can be used for various purposes can be manufactured at low cost with high productivity. Further, since the depressurizing chamber main body is sealed with a liquid, there is no problem such as wear of the seal member, and maintenance of the manufacturing apparatus is easy.
【図１】本発明にかかる発泡体の製造方法の１例をあら
わす説明図である。FIG. 1 is an explanatory view showing an example of a method for producing a foam according to the present invention.
【図２】図１の製造方法の圧縮方法の１例をあらわす説
明図である。FIG. 2 is an explanatory diagram showing an example of a compression method of the manufacturing method of FIG.
【図３】図１の製造方法の圧縮方法の他例をあらわす説
明図である。FIG. 3 is an explanatory diagram showing another example of the compression method of the manufacturing method of FIG.
【図４】本発明にかかる圧縮装置の他の例をあらわす説
明図である。FIG. 4 is an explanatory diagram showing another example of the compression device according to the present invention.
１ａ 製造装置 １ｂ 製造装置 ３ａ 減圧室 ３ｂ 減圧室 ３１ 入口 ３２ 出口 ３３ 中間部（経路） ３４ 減圧室本体 ３８ 入口 ５ａ 発泡性樹脂材料 ５ｂ 発泡性樹脂材料 ６ 液体 ７ 絞りダイ（圧縮手段） ８ａ 原料発泡体 ８ｂ 原料発泡体 ９ 発泡体 1a Manufacturing apparatus 1b Manufacturing apparatus 3a Decompression chamber 3b Decompression chamber 31 Inlet 32 Outlet 33 Intermediate part (path) 34 Decompression chamber main body 38 Inlet 5a Expandable resin material 5b Expandable resin material 6 Liquid 7 Drawing die (compressing means) 8a Raw material foaming Body 8b Raw material foam 9 Foam
Claims (1)
到る経路が所望の液体によって封止された減圧室の、前
記減圧室本体に発泡性樹脂材料を連続的に送り込み、減
圧室本体内でこの発泡性樹脂材料を減圧発泡させて原料
発泡体を得たのち、この原料発泡体を、前記液体内に通
して液体中で液圧および／または所望の圧縮手段を介し
て任意の方向から圧縮し、出口側から所望速度で連続的
に引き取ることを特徴とする発泡体の製造方法。1. A decompression chamber in which a path from a decompression chamber main body provided on an inlet side to an outlet is sealed by a desired liquid, and a foamable resin material is continuously fed into the decompression chamber main body to form a decompression chamber. After the foamable resin material is foamed in the main body under reduced pressure to obtain a raw material foam, the raw material foam is passed through the liquid, and in the liquid, liquid pressure and / or any desired compression means is applied to the raw material foam. A method for producing a foam, which comprises compressing from a direction and continuously withdrawing from an outlet side at a desired speed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7292687A JPH09131741A (en) | 1995-11-10 | 1995-11-10 | Manufacture of foamed body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7292687A JPH09131741A (en) | 1995-11-10 | 1995-11-10 | Manufacture of foamed body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09131741A true JPH09131741A (en) | 1997-05-20 |
Family
ID=17785006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7292687A Pending JPH09131741A (en) | 1995-11-10 | 1995-11-10 | Manufacture of foamed body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09131741A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003053850A (en) * | 2001-08-10 | 2003-02-26 | Inoac Corp | Melamine foam molded object, method for manufacturing the same and washing appliance |
-
1995
- 1995-11-10 JP JP7292687A patent/JPH09131741A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003053850A (en) * | 2001-08-10 | 2003-02-26 | Inoac Corp | Melamine foam molded object, method for manufacturing the same and washing appliance |
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