JP5253123B2 - 圧縮充填法によるポリプロピレン系樹脂型内発泡成形体の製造方法 - Google Patents
圧縮充填法によるポリプロピレン系樹脂型内発泡成形体の製造方法 Download PDFInfo
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- JP5253123B2 JP5253123B2 JP2008313332A JP2008313332A JP5253123B2 JP 5253123 B2 JP5253123 B2 JP 5253123B2 JP 2008313332 A JP2008313332 A JP 2008313332A JP 2008313332 A JP2008313332 A JP 2008313332A JP 5253123 B2 JP5253123 B2 JP 5253123B2
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- polypropylene resin
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- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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Classifications
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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
- B29C44/36—Feeding the material to be shaped
- B29C44/38—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length
- B29C44/44—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length in solid form
- B29C44/445—Feeding the material to be shaped into a closed space, i.e. to make articles of definite length in solid form in the form of expandable granules, particles or beads
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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
- B29C44/3442—Mixing, kneading or conveying the foamable material
- B29C44/3446—Feeding the blowing agent
- B29C44/3453—Feeding the blowing agent to solid plastic material
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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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- 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
- B29C44/3415—Heating or cooling
- B29C44/3426—Heating by introducing steam in the mould
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B29K2023/10—Polymers of propylene
- B29K2023/12—PP, i.e. polypropylene
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Description
(1) 次の工程を経て得られるポリプロピレン系樹脂多段発泡粒子を用いる、圧縮充填法によるポリプロピレン系樹脂型内発泡成形体の製造方法。
重量平均分子量(Mw)と数平均分子量(Mn)の比(Mw/Mn)が3.6以上であるポリプロピレン系樹脂を基材樹脂とするポリプロピレン系樹脂粒子を耐圧容器内で分散媒に分散させ、発泡剤として二酸化炭素を含む発泡剤を添加した後、ポリプロピレン系樹脂粒子の軟化温度以上の温度に加熱し、ポリプロピレン系樹脂粒子内に二酸化炭素を含む発泡剤を含浸させたのち、耐圧容器の一端を開放してポリプロピレン系樹脂粒子を耐圧容器内よりも低圧の雰囲気中に放出することによりポリプロピレン系樹脂発泡粒子を製造する工程、
得られたポリプロピレン系樹脂発泡粒子をさらに発泡させ、ポリプロピレン系樹脂多段発泡粒子を製造する工程。
(2)ポリプロピレン系樹脂粒子の基材となるポリプロピレン系樹脂が、エチレンを共重合単量体成分として含むランダム共重合体であることを特徴とする(1)に記載のポリプロピレン系樹脂型内発泡成形体の製造方法。
測定機器 :Waters社製Alliance GPC 2000型 ゲルパーミエーションクロマトグラフィー(GPC)
カラム :TSKgel GMH6−HT 2本、
TSKgel GMH6−HTL 2本(それぞれ、内径7.5mm×長さ300mm、東ソー社製)
移動相 :o−ジクロロベンゼン(0.025%BHT含有)
カラム温度:140℃
流速 :1.0mL/min
試料濃度 :0.15%(W/V)−o−ジクロロベンゼン
注入量 :500μL
分子量較正:ポリスチレン換算(標準ポリスチレンによる較正)
1)予備加熱工程:移動型、固定型の蒸気弁11、ドレン弁12及び排気弁14を開いた状態で下記両面加熱時よりも低圧の蒸気を金型内に流す。加熱時間は1〜20秒程度である。
2)一方加熱工程:移動型蒸気弁を閉、固定型蒸気弁を開、移動型ドレン弁を開、固定型ドレン弁を閉及び排気弁14を開の状態で両面加熱時よりも低圧の蒸気を金型内に流す。加熱時間は1〜20秒程度である。
3)逆一方加熱工程:移動型蒸気弁を開、固定型蒸気弁を閉、移動型ドレン弁を閉、固定型ドレン弁を開及び排気弁を開の状態で両面加熱時よりも低圧の蒸気を金型内に流す。加熱時間は1〜20秒程度である。
4)両面加熱工程(本加熱工程):移動型、固定型の蒸気弁を開、移動型、固定型のドレン弁を閉の状態で蒸気を金型内に流す。加熱時間は7〜30秒程度である。両面加熱工程で型窩内は最も高い温度となる。このときの加熱温度が上記116〜152℃である。
DSC比は、示差走査熱量計を用いて、圧縮成形に供する前(多段発泡後)のポリプロピレン系樹脂多段発泡粒子5〜6mgを10℃/minの昇温速度で40℃から220℃まで昇温する際に得られる、2つのピークを有する融解曲線にから求める。該融解ピークのうち低温側の融解ピーク熱量Qlと、高温側の融解ピーク熱量Qhから算出した、高温側の融解ピークの比率Qh/(Ql+Qh)×100で表されるパラメータである。
円筒状容器に発泡粒子を充填し、容器の開口部を越えた発泡粒子を取り除いて容器内の発泡粒子の重量を測定し、発泡粒子の重量を容器体積で除して嵩密度を求める。
型内発泡成形体の重量w(g)および水没体積v(cm3)を求め、樹脂の密度d(g/cm3)から次式により求める。
発泡倍率=d×v/w
得られた型内発泡成形体を25℃で2時間静置し、次いで75℃に温調した恒温室内に15時間静置した後、取り出し、25℃で放冷した。該型内発泡成形体における発泡粒子充填口にある発泡粒子を軽く爪で引き掻き、発泡粒子が一粒でも剥がれた場合を融着状態が不良、剥がれない場合を融着状態が良好、であるとした。後記するように成形機は2カ所の発泡粒子充填口を有する。充填口付近融着状態の評価は4ショットの型内発泡成形を行い、4個の型内発泡成形体にある合計8カ所の充填口付近の融着状態を評価した。表1における充填口付近融着状態の評価の数字は8カ所の充填口付近の不良であった個数を示す。例えば、数字が0の場合は8カ所すべての発泡粒子充填口付近の融着状態が良好である場合である。数字が1の場合は8カ所中、1カ所の発泡粒子充填口付近の融着状態が不良であるが他の7カ所は良好である場合である。
得られた成形体密度(g/L)を実重量と水没法による体積から算出し、これを、使用したポリプロピレン系樹脂多段発泡粒子の嵩密度(g/L)で除した値を圧縮比とした。
得られた型内発泡成形体を25℃で2時間静置し、次いで75℃に温調した恒温室内に15時間静置した後、取り出し、25℃で放冷した。該型内発泡成形体を割った際に発泡粒子内で破断している粒子の割合を検査し、その割合を融着率とした。
基材樹脂として、表1に示した特性を有するポリプロピレン系樹脂を使用した。樹脂1〜3はエチレンを共重合単量体成分として含有するポリプロピレン樹脂であり、樹脂2および3は減成処理によって得られたポリプロピレン樹脂である。この樹脂100重量部に対し、親水性物質としてグリセリンを0.2重量部、発泡核剤としてタルクを0.02重量部添加してドライブレンドし、押出機内で溶融混練した後、円形ダイよりストランド状に押出し、水冷後、カッターで切断し、一粒の重量が1.3mg/粒、ほぼ円柱形状の樹脂粒子を得た。得られた樹脂粒子100重量部、水200重量部、塩基性第三リン酸カルシウム0.5重量部、アルキルスルフォン酸ソーダ0.01重量部を耐圧オートクレーブ中に仕込んだ。
発泡剤としてブタンを使用し、発泡条件として表1に記載の条件を使用し、二段発泡せず除圧発泡(一段発泡)によって一挙に嵩密度18.8g/Lの発泡粒子を得たほかは実施例1と同様にして発泡粒子を製造した。得られた発泡粒子を用い表1に示した型内発泡成形条件を用いたほかは実施例1と同様に型内発泡成形体を製造した。型内発泡成形体の評価結果を表1に示す。表1から明らかなように実施例1と同じ樹脂を使用し、発泡粒子の発泡倍率はほぼ同じであるにもかかわらず型内発泡成形体の発泡粒子充填口付近の粒子融着状態はよくなかった。
2 発泡粒子供給口
3 加圧ガス入口
4 金型
5 固定型
6 移動型
7 型窩
8 通気口
9 スチームチャンバー
10 蒸気ライン
11 蒸気弁
12 ドレン弁
13 金型ガス圧力調整バルブ
14 排気弁
15 排気口
16 充填機
17 発泡粒子充填用加圧ガス入口
18 発泡粒子充填口
19 ピストンプラグ
20 均圧ライン
Claims (2)
- 次の工程を経て得られるポリプロピレン系樹脂多段発泡粒子を用いる、圧縮充填法によるポリプロピレン系樹脂型内発泡成形体の製造方法。
重量平均分子量(Mw)と数平均分子量(Mn)の比(Mw/Mn)が3.6以上であるポリプロピレン系樹脂を基材樹脂とするポリプロピレン系樹脂粒子を耐圧容器内で分散媒に分散させ、発泡剤として二酸化炭素を含む発泡剤を添加した後、ポリプロピレン系樹脂粒子の軟化温度以上の温度に加熱し、ポリプロピレン系樹脂粒子内に二酸化炭素を含む発泡剤を含浸させたのち、耐圧容器の一端を開放してポリプロピレン系樹脂粒子を耐圧容器内よりも低圧の雰囲気中に放出することによりポリプロピレン系樹脂発泡粒子を製造する工程、
得られたポリプロピレン系樹脂発泡粒子をさらに発泡させ、ポリプロピレン系樹脂多段発泡粒子を製造する工程。 - ポリプロピレン系樹脂粒子の基材となるポリプロピレン系樹脂が、エチレンを共重合単量体成分として含有するランダム共重合体であることを特徴とする請求項1に記載のポリプロピレン系樹脂型内発泡成形体の製造方法。
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