JP7183792B2 - ポリオレフィン系樹脂発泡体とその製造方法及び、粘着テープ - Google Patents
ポリオレフィン系樹脂発泡体とその製造方法及び、粘着テープ Download PDFInfo
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- JP7183792B2 JP7183792B2 JP2018554788A JP2018554788A JP7183792B2 JP 7183792 B2 JP7183792 B2 JP 7183792B2 JP 2018554788 A JP2018554788 A JP 2018554788A JP 2018554788 A JP2018554788 A JP 2018554788A JP 7183792 B2 JP7183792 B2 JP 7183792B2
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- polyolefin resin
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- resin foam
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- 239000013464 silicone adhesive Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
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- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/56—After-treatment of articles, e.g. for altering the shape
- B29C44/5627—After-treatment of articles, e.g. for altering the shape by mechanical deformation, e.g. crushing, embossing, stretching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/56—After-treatment of articles, e.g. for altering the shape
- B29C44/5627—After-treatment of articles, e.g. for altering the shape by mechanical deformation, e.g. crushing, embossing, stretching
- B29C44/5636—After-treatment of articles, e.g. for altering the shape by mechanical deformation, e.g. crushing, embossing, stretching with the addition of heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
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- B29C44/5672—After-treatment of articles, e.g. for altering the shape by mechanical deformation, e.g. crushing, embossing, stretching by stretching the foam, e.g. to open the cells
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/20—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 for porous or cellular articles, e.g. of foam plastics, coarse-pored
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- C08J5/18—Manufacture of films or sheets
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- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
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- C09J201/00—Adhesives based on unspecified macromolecular compounds
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- B29C44/34—Auxiliary operations
- B29C44/36—Feeding the material to be shaped
- B29C44/46—Feeding the material to be shaped into an open space or onto moving surfaces, i.e. to make articles of indefinite length
- B29C44/50—Feeding the material to be shaped into an open space or onto moving surfaces, i.e. to make articles of indefinite length using pressure difference, e.g. by extrusion or by spraying
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
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- C08J2201/00—Foams characterised by the foaming process
- C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
- C08J2201/026—Crosslinking before of after foaming
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- C08J2323/10—Homopolymers or copolymers of propene
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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- C08J2423/04—Homopolymers or copolymers of ethene
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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Landscapes
- Chemical & Material Sciences (AREA)
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Description
表裏両面の表面粗さSaの差=B面表面粗さSa-A面表面粗さSa
MD方向の平均気泡径の比=B面側MD方向の平均気泡径/A面側MD方向の平均気泡径
融点とは、示差走査熱量分析で得られた縦軸に融解熱容量(J/g)、横軸に温度をとったときに得られるDSC曲線の吸熱ピークから得られる最大の温度である。示差走査熱量計(DSC:セイコー電子工業株式会社製RDC220-ロボットDSC)を用いてサンプルを2mg準備し、窒素環境下において測定した。測定条件は、サンプルを200℃の温度まで昇温し溶融させた後、10℃/分の速度で-100℃の温度まで冷却させた時に得られる発熱ピークが結晶化温度であり、更に冷却させて階段状の変位点の中点にあたるのがガラス転移温度である。それから10℃/分の速度で昇温して、単位質量あたりの吸熱ピークを測定した。この二回目の昇温時に得られる融解による吸熱ピークの頂点を融点とした。
MFRとは、JIS K7210(1999)「プラスチック-熱可塑性プラスチックのメルトマスフローレート (MFR) およびメルトボリュームフローレイト (MVR) の試験方法」の附属書B(参考)「熱可塑性プラスチック材料の規格と指定とその試験条件」に基づきポリエチレン系樹脂(a2)は、温度190℃、荷重2.16kgf、ポリプロピレン系樹脂(a1)、熱可塑性エラストマー系樹脂(a3)は温度230℃、荷重2.16kgfの条件でメルトマスフローレート計(株式会社東洋精機製作所製メルトインデックサ型式F-B01)を使用し、手動切り取り法を採用し、ダイから10分間にでてきた樹脂の重量を測定した。
ポリオレフィン系樹脂の密度は、JIS K7112(1999)「プラスチック-非発泡プラスチックの密度及び比重の測定方法」に準じて測定した。
本発明においてポリオレフィン系樹脂発泡体の吸熱ピークとは示差走査熱量分析で得られた縦軸に融解熱容量(J/g)、横軸に温度をとったときに得られるDSC曲線での吸熱サイドのピークをいう。具体的には発泡体の気泡を事前にミキシングロールなどにより潰した後、約2mgの試験片を秤量、示差走査熱量計(DSC:セイコー電子工業株式会社製RDC220-ロボットDSC)を用いて、窒素環境下において測定した。測定条件は、サンプルを200℃の温度まで昇温し溶融させた後、10℃/分の速度で-50℃の温度まで冷却させ、それから再度10℃/分の速度で昇温して、DSC曲線を得る。この二回目の昇温時に得られるDSC曲線から求められる吸熱側にピークを有するピークを吸熱ピークと呼ぶ。
表面粗さは、三次元表面性状パラメータ:ISO 25178に準拠するキーエンス社製:VHX-600によりランダムに採取した3箇所の表面撮影を行い、その平均値を算術平均高さSaとした。
撮影間隔(高さ方向):20μm
フィルター:ガウシアンを使用。
作製したポリオレフィン系樹脂発泡体シートの断面を、走査型電子顕微鏡(SEM)(株式会社日立ハイテクノロジーズ製、S-3000N)を用いて50倍の倍率で観察し、得られた画像および計測ソフトを使用して気泡径(直径)を測定した。なお、気泡径は撮影した画像の1.5mm×1.5mm範囲内において長手方向(MD)および幅方向(TD)のそれぞれについて測定し、それぞれの方向における平均気泡径を算出した。なお、10個の視野において測定し、算術平均として求めた。
発泡体を約0.5mm四方に切断し、約100mgを0.1mgの精度で秤量する。140℃の温度のテトラリン200mlに3時間浸漬した後、100メッシュのステンレス製金網で自然濾過し、金網上の不溶解分を1時間120℃下で熱風オーブンにて乾燥する。次いで、シリカゲルを入れたデシケータ内で30分間冷却し、この不溶解分の質量を精密に秤量し、次の式に従って発泡体のゲル分率を百分率で算出する。
ポリオレフィン系樹脂発泡体のみかけ密度は、JIS K6767(1999)「発泡プラスチック-ポリエチレン-試験方法」に準じて測定・計算した値である。10cm2に切った発泡体の厚さを測定し、且つこの試験片の質量を秤量する。以下の式によって得られた値をみかけ密度とし、単位はkg/m3とする。
ポリオレフィン系樹脂発泡体の厚さは、ISO1923(1981)「発泡プラスチック及びゴム一線寸法の測定方法」に従って測定を行った。具体的には10cm2の面積を持つ円形測定子をつけたダイヤルゲージを用いて、一定の大きさに切った発泡体を平坦な台に静置させた上から発泡体表面に10gの一定圧力で接触させて測定する。
実施例と比較例で用いた評価方法については、次のとおりである。
発泡体に両面テープ(アクリル系両面テープ、恵比寿化成社製)を貼り付け、U字形状(発泡体の幅10mm、全長300mm)に打ち抜いて試験片を作製した。次いで、試験片の開放端(U字形状における開放された上部)が上方に来るように試験片を置き、両面テープの粘着剤層がアクリル板に接触するよう試験片の厚み方向から厚さ10mmのアクリル板2枚で挟んだ。次いで、試験片が厚み50%圧縮するように、試験片の厚み方向に押圧した。 そして、試験片のU字形状の内側に水を注ぎ、試験片の内側下端部からの水位が100mmとなるようにした。その後、24時間後および、48時間後の水漏れの有無を確認し、次のとおりで評価した。
◎:48時間水漏れが確認できなかった。
○:24時間水漏れが確認できなかった。
×:24時間未満で水漏れが確認された。
発泡体を5mm厚みになる様に鉄板の上に積層させる。その後、指で発泡体の上部を押さえて評価した。
○:指が沈み込み、十分な反発を感じる。
△:指の沈み込みが不十分、もしくは反発を感じない。
×:硬さを感じる。
発泡体を幅5mm、MD方向150mm×TD方向150mmに打ち抜いた試験片を用い、発泡体の両面に日立化成ポリマー社製「商品名:ハイボンYA790」ポリエステル系粘着剤を塗布し、表裏面に厚さ3mm、縦200mm×横200mmのSUS平板に貼り付けた後、手で引き剥がして評価した。
◎:粘着強度が強く、A面とB面で強度差を強く感じる。
○:A面とB面で強度差を強く感じる。
△:A面とB面で強度差を感じる。
×:A面とB面で強度差を感じない。
発泡体の表面に前記ポリエステル系粘着剤を塗布したときの表面を観察した。
○:表面に十分に粘着剤層が保持できている。
△:表面に粘着剤層が形成されているが薄い。しかし、塗布量を上げると保持できている。
×:粘着剤層の形成が不十分。
15cm角の発泡体を四方でクランプして200℃の成形機中で30秒保持した後の表面性を評価した。
○:表面性に問題なく、美麗である。
△:表面に若干の凹凸が生じる。
×:荒れが生じ、凹凸が激しくなる。
総合評価としては、止水性、クッション性、粘着強度差、粘着加工性、耐熱性の結果を元に実施した。
◎:◎が一つ以上あり、×および△が一つも無いもの。
○:×が一つも無く、△が一つあるもの。
△:×が一つも無く、△が二つあるもの。
×:△が三つ以上、または、×が一つ以上あるもの。
a-1:三井化学社製“タフマー”(登録商標)PN-3560
密度866kg/m3、MFR(230℃)=6.0g/10分、融点=160℃、
結晶融解エネルギー=17J/g、結晶化温度=107℃
a-2:プライムポリマ製“プライムTPO”(登録商標)M142E
密度900kg/m3、MFR(230℃)=10.0g/10分、融点=153℃、
結晶融解エネルギー=28J/g、結晶化温度=121℃
a-3:JSR製“JSR RB”(登録商標)RB-840
密度914kg/m3、MFR(230℃)=9.0g/10分、融点=126℃、
結晶融解エネルギー=14J/g、結晶化温度=90℃
a-4:三井化学社製“タフマー”(登録商標)PN-2070
密度867kg/m3、MFR(230℃)=7.0g/10分、融点=140℃、
結晶融解エネルギー=14J/g、結晶化温度=62℃ 。
b-1:日本ポリプロ製“ノバテック”(登録商標)PP EG6D
密度:900kg/m3、MFR(230℃)=0.8g/10分、融点=141℃
b-2:プライムポリマ製“プライムポリプロ“(登録商標)J452HAP
密度:900kg/m3、MFR(230℃)=3.5g/10分、融点=163℃。
日本ポリエチレン製“ノバテック”(登録商標)LL UJ960
密度:935kg/m3、MFR(190℃)=5g/10分、融点=126℃
EVA:東ソー製“ウルトラセン”(登録商標)636<エチレン酢酸ビニル共重合体樹脂>
密度941kg/m3、MFR(190℃)=2.5g/10分、融点=82℃ 。
発泡剤:アゾジカルボンアミド永和化成工業製“ビニホールAC#R”(登録商標)
架橋助剤:和光純薬工業製55%ジビニルベンゼン
酸化防止剤:BASF社製“IRGANOX”(登録商標)1010 。
実施例、比較例で実施した加工方法は、次のとおりである。
(1)スライス工程
厚み方向に二つ以上に裁断する工程のことで、スライス機により裁断する。
(2)加熱工程
150℃~180℃の温度で発泡体の両面を加熱する工程のことで、赤外線ヒータを用いる。
(3)延伸工程
巻き出しと巻き取りで速度差をつけることで延伸する工程のことで、駆動しているニップロールの速度をコントロールすることで延伸する。
(4)圧縮工程
厚み方向に圧縮して発泡体を圧延する工程のことで、ニップロールの間隙を元の発泡体の厚みよりも締めることで圧縮する。
実施例1~15と比較例1~13で作製した発泡体は、次のとおりである。
Claims (7)
- ポリオレフィン系樹脂および熱可塑性エラストマーを含有し、示差走査熱量計(DSC)による吸熱ピークが少なくとも110℃以上143℃以下および、153℃以上に存在し、発泡体を構成する樹脂100質量%中に熱可塑性エラストマー系樹脂を30質量%以上60質量%以下含むポリオレフィン系樹脂発泡体からなるポリオレフィン系樹脂発泡体シートであって、その表裏両面の表面粗さSa(算術平均高さ)が5μm以上80μm以下、下式で求められる表裏両面の表面粗さSaの差が20μm以上であり、かつ、表裏両面のMD方向の平均気泡径が100μm以上であり、下式で求められるB面側MD方向の平均気泡径とA面側MD方向の平均気泡径の比が1.2以上であることを特徴とするポリオレフィン系樹脂発泡体シート。
表裏両面の表面粗さSaの差=B面表面粗さSa-A面表面粗さSa
MD方向の平均気泡径の比=B面側MD方向の平均気泡径/A面側MD方向の平均気泡径 - ゲル分率が20%以上60%以下であることを特徴とする請求項1に記載のポリオレフィン系樹脂発泡体シート。
- 見かけ密度が50kg/m3以上165kg/m3以下、厚さが0.6mm以上1.4mm以下であることを特徴とする請求項1または2に記載のポリオレフィン系樹脂発泡体シート。
- ポリオレフィン系樹脂と熱可塑性エラストマーとを少なくとも含有する樹脂組成物を発泡し、発泡体シートを作製する工程と、該発泡体シートをMD-TD面に平行にスライスした発泡体シートを作製する工程(スライス工程)を有する請求項1ないし3の何れかに記載のポリオレフィン系樹脂発泡体シートの製造方法。
- 前記スライス工程を経た発泡体シートを加熱(加熱工程)してMD方向に105%以上120%以下に延伸する工程(延伸工程)を更に有することを特徴とする請求項4に記載のポリオレフィン系樹脂発泡体シートの製造方法。
- 前記スライス工程を経た発泡体シートまたは前記加熱・延伸工程を経た発泡体シートを圧縮する工程(圧縮工程)を更に含むことを特徴とする請求項4または5に記載のポリオレフィン系樹脂発泡体シートの製造方法。
- 請求項1ないし3のいずれかに記載のポリオレフィン系発泡体シートの片面または両面に接着材層を有する粘着テープ。
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