JPH043728B2 - - Google Patents
Info
- Publication number
- JPH043728B2 JPH043728B2 JP23350883A JP23350883A JPH043728B2 JP H043728 B2 JPH043728 B2 JP H043728B2 JP 23350883 A JP23350883 A JP 23350883A JP 23350883 A JP23350883 A JP 23350883A JP H043728 B2 JPH043728 B2 JP H043728B2
- Authority
- JP
- Japan
- Prior art keywords
- blow
- weight
- polypropylene resin
- propylene
- ethylene
- 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.)
- Expired - Lifetime
Links
- -1 polypropylene Polymers 0.000 claims description 36
- 229920005989 resin Polymers 0.000 claims description 29
- 239000011347 resin Substances 0.000 claims description 29
- 239000004743 Polypropylene Substances 0.000 claims description 24
- 229920001155 polypropylene Polymers 0.000 claims description 24
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 15
- 239000005977 Ethylene Substances 0.000 claims description 15
- 229920005604 random copolymer Polymers 0.000 claims description 13
- 238000010103 injection stretch blow moulding Methods 0.000 claims description 10
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 150000001451 organic peroxides Chemical class 0.000 description 9
- 239000002667 nucleating agent Substances 0.000 description 8
- 239000008188 pellet Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 5
- 238000007664 blowing Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000000071 blow moulding Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Classifications
-
- 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
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
-
- 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
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/08—Biaxial stretching during blow-moulding
- B29C49/16—Biaxial stretching during blow-moulding using pressure difference for pre-stretching, e.g. pre-blowing
-
- 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
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/18—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor using several blowing steps
-
- 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
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/42—Component parts, details or accessories; Auxiliary operations
- B29C49/64—Heating or cooling preforms, parisons or blown articles
- B29C49/6472—Heating or cooling preforms, parisons or blown articles in several stages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
-
- 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
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/42—Component parts, details or accessories; Auxiliary operations
- B29C49/78—Measuring, controlling or regulating
- B29C2049/7879—Stretching, e.g. stretch rod
-
- 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
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/07—Preforms or parisons characterised by their configuration
- B29C2949/0715—Preforms or parisons characterised by their configuration the preform having one end closed
-
- 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
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
- B29C49/06—Injection blow-moulding
-
- 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
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/08—Biaxial stretching during blow-moulding
- B29C49/087—Means for providing controlled or limited stretch ratio
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】
本発明は、透明性が改良され、偏肉が少ないポ
リプロピレン樹脂製ブロー成形容器に関する。
ポリプロピレン樹脂は、耐熱性、耐薬品性、安
全衛生面に優れ、そのブロー成形品は剛性、衝撃
強度にも優れるため、食品容器、洗剤容器、医療
容器等に広く使用されている。しかしながら、ポ
リプロピレン樹脂のブロー成形品は透明性が不十
分であり、市場の要求を十分満足するものではな
い。
従来、ポリプロピレン樹脂の透明性を改良する
方法としては、造核剤を添加する方法、有機過酸
化物の存在または不存在下に熱減成する方法、プ
ロピレンにエチレンを共重合させる方法などが、
また成形加工法では、二軸延伸する方法などが知
られているが、通常のブロー成形法では、これら
の対策を行なつても製品が薄白く霞みがかかつた
様になり、十分な透明性をもつたブロー成形容器
を得ることができない。
また、従来から行なわれているブロー成形に用
いるポリプロピレン樹脂としては、成形性、耐衝
撃性、剛性などの面から、通常、JIS K−7210の
条件14で測定したメルトフローインデツクス
(MFI)が高々4g/10分程度のものであり、特
に1〜2g/10分程度のものが多く使用されてい
る。
一方、近年射出延伸ブロー成形法において、ポ
リプロピレン樹脂にも応用できる成形機が開発さ
れ、ブロー成形品も試作されているが、十分な透
明性と偏肉のないポリプロピレン樹脂製のブロー
成形容器は得られていないのが実状である。
本発明者らは、射出延伸ブロー成形法で透明性
に優れ、かつ偏肉のないポリプロピレン樹脂製の
ブロー成形容器を得るべく鋭意検討した結果、ポ
リプロピレン樹脂として、特定のMFIを有し、
極限粘度とMFIとが特定の関係にあり、かつ特
定のエチレン含有量であるプロピレンとエチレン
の共重合体を用いることにより、良好なブロー成
形容器を得ることができることを見出し、本発明
を完成するに到つた。
即ち、本発明は、プロピレンとエチレンのラン
ダム共重合体を射出延伸ブロー成形したポリプロ
ピレン樹脂製ブロー成形容器であつて、該プロピ
レン−エチレンランダム共重合体がエチレン含有
量が1〜6重量%で、メルトフローインデツクス
が4〜50g/10分で、かつ、135℃のテトラリン
溶液中で測定したその極限粘度〔η〕dl/g)と
メルトフローインデツクスMFI(g/10分)との
関係が、
1.70≦logMFI+5.20log〔η〕≦1.95
であるものであることを特徴とする透明性が改良
され、偏肉のないポリプロピレン樹脂製ブロー成
形容器である。
本発明に用いるポリプロピレン樹脂はプロピレ
ン−エチレンランダム共重合体であり、そのエチ
レン含有量は1〜6重量%であることがブロー成
形品の透明性の上から望ましく、かつ、MFIが
4〜50g/10分で、更に135℃のテトラリン溶液
中で測定した極限粘度〔η〕dl/g)とMFI
(g/10分)との関係が
1.70≦logMFI+5.20log〔η〕≦1.95
にあることが必要である。
エチレン含有量が1重量%未満であるものでは
偏肉性が著しく、成形性が不良となる。また、6
重量%を超えるものでは得られるブロー容器の剛
性が不足するため使用できないものとなる。
MFIが4g/10分未満では十分な透明性が得
られない。また、MFIが50g/10分を超えると
偏肉が著しくなるため、安定して、良好なブロー
成形容器を得ることができない。
また、logMFI+5.20log〔η〕の値が1.70未満で
は樹脂がベタ付き易すく、安定してブロー成形容
器が得られない。また、1.95を超えると十分な透
明性は得られない。
尚、1.70≦logMFI+5.20log〔η〕≦1.95
を満足するプロピレン−エチレンランダム共重合
体は、この樹脂に、少量の有機過酸化物を添加
し、あるいは添加することなく溶融してペレツト
化することにより得ることができる。
この目的に使用する有機過酸化物としては、た
とえばジクミルパーオキサイド、ジ−tブチルパ
ーオキサイド、2,5−ジメチル−2,5−ビス
(t−ブチルパーオキシ)ヘキサンなどがあげら
れ、中でも10時間半減期が110〜130℃の温度範囲
にあるものが好ましい。
なお、プロピレン−エチレンブロツク共重合体
では、本発明の透明性の優れたブロー成形容器を
得ることはできない。
本発明においては、透明性が更に良好になるの
で造核剤を添加しておくことができる。その場合
にはプロピレン−エチレンランダム共重合体に対
し1重量%以下が適当である。
更に、酸化防止剤、紫外線吸収剤、帯電防止
剤、滑剤、着色剤などの添加剤や他の樹脂やエラ
ストマーが添加配合されたものであつてもよい。
本発明の成形法である射出延伸ブロー成形法と
は、有底パリソンを射出成形によつて成形し、次
いで予備ブロー、延伸温度調整後、延伸ブローす
ることによつて製品を得る成形法であり、延伸の
方法としてはロツドによる機械的なたて延伸とエ
アー吹込による方法の組合せが行なわれる。この
成形法に適した成形機としては、例えば、日精
ASB機械株式会社製射出延伸ブロー成形機ASB
−50、ASB−150、ASB250、ASB−650等があ
げられる。
本発明において、特に優れた透明性を得るに
は、例えば成形機として射出延伸ブロー成形機
ASB−50を用いた場合、下記の条件が望ましい。
射出成形温度:200〜260℃
予備ブロー延伸倍率:縦1.0〜1.8倍
横1.2〜2.0倍
予備ブローエア圧力:3〜7Kg/cm2
延伸温度調整金型温度:90〜140℃
延伸ブロー延伸倍率:縦1.2〜3.5倍
横1.2〜6.0倍
延伸ブローエア圧力:4〜20Kg/cm2
本発明のポリプロピレン樹脂製ブロー成形容器
は、ポリプロピレン樹脂に安定剤、帯電防止剤、
紫外線吸収剤、着色剤、造核剤等の添加剤を添加
したのち、通常、上記射出延伸ブローによりその
胴部肉厚が0.2〜1.0mmに製造される。また、きわ
めて透明性に優れ、かつ耐熱性、耐衝撃性等にも
優れるので、その性質を利用して食品容器、洗剤
容器、シヤンプー容器、トイレタリー容器、医療
容器等に好適に使用できる。
以下、実施例により本発明を詳細に説明する。
なお、胴部霞度は日本電色社製のヘイズメータ
ーを用い、JIS K−6714に記載された方法に従つ
て測定したものである。
実施例 1
エチレン含有量が4重量%のプロピレン−エチ
レンランダム共重合体のパウダーに酸化防止剤な
どの添加剤および0.30重量%の造核剤と一緒に、
0.01重量%の有機過酸化物ルパゾール101(商標、
ルシドール吉富(株)製)を添加し、ヘンシルミキサ
ーで充分撹拌したのち、φ65mm押出機により240
℃で押出してペレツト化し、ポリプロピレン樹脂
ペレツトを得た。
得られたペレツトのMFIは14g/10分であり、
また〔η〕は1.35でlogMFI+5.20log〔η〕は1.82
であつた。
この樹脂を射出延伸ブロー成形機ASB−50に
より、下記条件で成形して、胴部直径70mm、内容
量500mlの丸型ボトルを成形した。
射出成形温度:220℃
射出成形金型温度:15℃
予備ブロー延伸倍率:縦1倍、横1.4倍
予備ブローエア圧力:5Kg/cm2
延伸温度調整金型温度:100℃
延伸ブロー延伸倍率:縦1.8倍、横1.2倍
延伸ブローエア圧力:9Kg/cm2
得られたボトルはその重量が24gであり、透明
性に極めて優れたポリプロピレン樹脂製ブロー成
形容器であつた。また、胴部の肉厚は0.53mmで霞
度は2.8%であり、内容液を入れたときの透明性
も良好であつた。
実施例 2
実施例1において、有機過酸化物ルパゾール
101の添加量を0.02重量%に変える以外は、実施
例1と同様にして、ポリプロピレン樹脂ペレツト
を得た。そのMFIは25g/10分であり、〔η〕は
1.22dl/gで、logMFI+2.20log〔η〕は1.85であ
つた。
この樹脂を用い、実施例1と同様にして射出延
伸ブロー成形ボトルを得、その胴部の肉厚、およ
び霞度を測定した。
測定結果を表1に示す。
実施例 3
エチレン含有量が5.5重量%であるプロピレン
−エチレンランダム共重合体のパウダーに、酸化
防止剤などの添加剤および0.30重量%の造核剤と
一緒に有機過酸化物ルパゾール101を0.02重量%
添加して、実施例1と同様にしてペレツト化しポ
リプロピレン樹脂ペレツトを得た。そのMFIは
41g/10分であり、〔η〕は1.10で、logMFI+
5.20log〔η〕は1.83であつた。
この樹脂を用い、実施例1と同様にして射出延
伸ブロー成形ボトルを得、その胴部の肉厚および
霞度を測定した。
測定結果を表1に示す。
実施例 4
エチレン含有量が1.5重量%のプロピレン−エ
チレンランダム共重合体のパウダーに酸化防止剤
などの添加剤および0.20重量%の造核剤と一緒
に、有機過酸化物パーカトツクス14(商標、化薬
ヌーリー(株)製)を0.005重量%添加し、実施例1
と同様にして、ポリプロピレン樹脂ペレツトを得
た。そのMFIは6g/10分であり、〔η〕は1.58
で、logMFI+5.20log〔η〕は1.81であつた。
この樹脂を用い、実施例1と同様にして、射出
延伸ブロー成形ボトルを得、その胴部の肉厚およ
び霞度を測定した。
測定結果を表1に示す。
比較例 1
ポリプロピレン樹脂としてエチレン含有量4重
量%MFI2g/10分、〔η〕2.10dl/g、logMFI
+5.20log〔η〕=1.98で、かつ造核剤0.3重量%を
含むプロピレン−エチレンランダム共重合体を用
い、実施例1と同様にして、丸型ボトルを成形し
た。
得られたボトルの胴部の肉厚および霞度を表1
に示す。
比較例 2
エチレン含有量が2重量%のプロピレン−エチ
レンランダム共重合体のパウダーに、酸化防止剤
などの添加剤の他に、有機過酸化物パーカドツク
ス14 0.24重量%と造核剤0.30重量%を添加し、
実施例1と同様にしてポリプロピレン樹脂ペレツ
トを得た。そのMFIは55g/10分であり、〔η〕
は1.09dl/gで、logMFI+5.20log〔η〕は1.93で
あつた。
このポリプロピレンを用いて、実施例1と同様
にして、射出延伸ブロー成形を行なつたが、ブロ
ー成形時に偏肉が著しくなり、良好な容器は得ら
れなかつた。
比較例 3
エチレン含有量0.5重量%のプロピレン−エチ
レンランダム共重合体のパウダーに酸化防止剤な
どの添加剤の他に、有機過酸化物ルパゾール101
0.10重量%と造核剤0.30重量%を添加し、実施例
1と同様にして、ポリプロピレン樹脂ペレツトを
得た。そのMFIは15g/10分であり、〔η〕は
1.33dl/gで、logMFI+5.20log〔η〕は1.82であ
つた。
このポリプロピレンを用いて、実施例1と同様
にして、射出延伸ブロー成形を行なつたが、ブロ
ー成形時の偏肉が著しく、良好な容器は得られな
かつた。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polypropylene resin blow-molded container with improved transparency and less uneven thickness. Polypropylene resin has excellent heat resistance, chemical resistance, and safety and hygiene, and its blow-molded products also have excellent rigidity and impact strength, so it is widely used for food containers, detergent containers, medical containers, etc. However, blow-molded products made of polypropylene resin have insufficient transparency and do not fully satisfy market demands. Conventionally, methods for improving the transparency of polypropylene resin include adding a nucleating agent, thermal degradation in the presence or absence of an organic peroxide, and copolymerizing propylene with ethylene.
In addition, there are known molding methods such as biaxial stretching, but with normal blow molding, even if these measures are taken, the product will look pale and hazy, and it is difficult to achieve sufficient transparency. It is not possible to obtain a blow-molded container with good properties. In addition, polypropylene resins used in conventional blow molding usually have a melt flow index (MFI) measured under condition 14 of JIS K-7210 in terms of moldability, impact resistance, and rigidity. It is about 4 g/10 minutes at most, and especially about 1 to 2 g/10 minutes is often used. On the other hand, in recent years, molding machines that can be applied to polypropylene resin have been developed in the injection stretch blow molding method, and blow molded products have also been prototyped. The reality is that this is not the case. The present inventors have conducted intensive studies to obtain a polypropylene resin blow molded container with excellent transparency and no uneven thickness by injection stretch blow molding.
It was discovered that a good blow-molded container could be obtained by using a copolymer of propylene and ethylene that has a specific relationship between intrinsic viscosity and MFI and has a specific ethylene content, and completed the present invention. I reached it. That is, the present invention is a polypropylene resin blow-molded container made by injection stretch blow-molding a random copolymer of propylene and ethylene, wherein the propylene-ethylene random copolymer has an ethylene content of 1 to 6% by weight, The melt flow index is 4 to 50 g/10 minutes, and the relationship between the intrinsic viscosity [η] dl/g) and the melt flow index MFI (g/10 minutes) measured in a tetralin solution at 135°C is , 1.70≦logMFI+5.20log[η]≦1.95.This is a polypropylene resin blow-molded container with improved transparency and no uneven thickness. The polypropylene resin used in the present invention is a propylene-ethylene random copolymer, and the ethylene content is preferably 1 to 6% by weight from the viewpoint of transparency of the blow molded product, and the MFI is 4 to 50 g/ After 10 minutes, the intrinsic viscosity [η]dl/g) and MFI measured in the tetralin solution at 135℃
(g/10 minutes) is required to be 1.70≦logMFI+5.20log[η]≦1.95. If the ethylene content is less than 1% by weight, uneven thickness will be significant and moldability will be poor. Also, 6
If it exceeds % by weight, the resulting blow container will not have sufficient rigidity and cannot be used. If the MFI is less than 4 g/10 minutes, sufficient transparency cannot be obtained. Furthermore, if the MFI exceeds 50 g/10 minutes, the uneven thickness will become significant, making it impossible to obtain a stable and good blow-molded container. Furthermore, if the value of logMFI+5.20log [η] is less than 1.70, the resin tends to become sticky and a blow-molded container cannot be stably obtained. Furthermore, if it exceeds 1.95, sufficient transparency cannot be obtained. In addition, the propylene-ethylene random copolymer satisfying 1.70≦logMFI+5.20log[η]≦1.95 can be made into pellets by melting the resin with or without adding a small amount of organic peroxide. It can be obtained by Examples of organic peroxides used for this purpose include dicumyl peroxide, di-t-butyl peroxide, and 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, among others. Those with a 10 hour half-life in the temperature range of 110 to 130°C are preferred. Note that the blow-molded container of the present invention with excellent transparency cannot be obtained using a propylene-ethylene block copolymer. In the present invention, a nucleating agent can be added because the transparency is further improved. In that case, the appropriate amount is 1% by weight or less based on the propylene-ethylene random copolymer. Furthermore, additives such as antioxidants, ultraviolet absorbers, antistatic agents, lubricants, and colorants, as well as other resins and elastomers, may be added and blended. The injection stretch blow molding method, which is the molding method of the present invention, is a molding method in which a bottomed parison is molded by injection molding, and then a product is obtained by pre-blowing, stretching temperature adjustment, and stretch blowing. The stretching method is a combination of mechanical vertical stretching using a rod and air blowing. Examples of molding machines suitable for this molding method include Nissei
Injection stretch blow molding machine ASB manufactured by ASB Machinery Co., Ltd.
-50, ASB-150, ASB250, ASB-650, etc. In the present invention, in order to obtain particularly excellent transparency, for example, an injection stretch blow molding machine is used as a molding machine.
When using ASB-50, the following conditions are desirable. Injection molding temperature: 200-260℃ Pre-blow stretch ratio: Vertical 1.0-1.8 times Width 1.2-2.0 times Pre-blow air pressure: 3-7 Kg/cm 2 Stretching temperature adjustment mold temperature: 90-140℃ Stretch blow stretch ratio: Vertical Stretched 1.2 to 3.5 times horizontally 1.2 to 6.0 times Blow air pressure: 4 to 20 Kg/cm 2 The polypropylene resin blow molded container of the present invention contains a polypropylene resin containing a stabilizer, an antistatic agent,
After adding additives such as an ultraviolet absorber, a coloring agent, and a nucleating agent, the body is usually manufactured to have a body thickness of 0.2 to 1.0 mm by the above-mentioned injection stretch blowing. In addition, it has excellent transparency, heat resistance, and impact resistance, so it can be suitably used for food containers, detergent containers, shampoo containers, toiletry containers, medical containers, etc. by taking advantage of these properties. Hereinafter, the present invention will be explained in detail with reference to Examples. Incidentally, the body haze was measured using a haze meter manufactured by Nippon Denshoku Co., Ltd. according to the method described in JIS K-6714. Example 1 A propylene-ethylene random copolymer powder with an ethylene content of 4% by weight was mixed with additives such as an antioxidant and 0.30% by weight of a nucleating agent.
0.01% by weight of the organic peroxide Lupasol 101 (trademark,
(manufactured by Lucidor Yoshitomi Co., Ltd.) was added, thoroughly stirred with a Henshil mixer, and then
The mixture was extruded and pelletized at ℃ to obtain polypropylene resin pellets. The MFI of the pellets obtained was 14 g/10 min.
Also, [η] is 1.35 and logMFI + 5.20log [η] is 1.82
It was hot. This resin was molded using an injection stretch blow molding machine ASB-50 under the following conditions to form a round bottle with a body diameter of 70 mm and a content capacity of 500 ml. Injection molding temperature: 220℃ Injection mold temperature: 15℃ Pre-blow stretching ratio: 1x vertically, 1.4x horizontally Pre-blowing air pressure: 5Kg/cm 2 Stretching temperature adjustment mold temperature: 100°C Stretching blow stretching ratio: 1.8 vertically Stretching by 1.2 times in width and 1.2 times in width Blow air pressure: 9 Kg/cm 2 The weight of the obtained bottle was 24 g, and it was a blow-molded container made of polypropylene resin with extremely excellent transparency. In addition, the wall thickness of the body was 0.53 mm, the haze level was 2.8%, and the transparency when the liquid was added was also good. Example 2 In Example 1, the organic peroxide Lupazole
Polypropylene resin pellets were obtained in the same manner as in Example 1, except that the amount of 101 added was changed to 0.02% by weight. Its MFI is 25g/10min, and [η] is
At 1.22dl/g, logMFI+2.20log[η] was 1.85. Using this resin, an injection stretch blow molded bottle was obtained in the same manner as in Example 1, and the wall thickness and haze of the body were measured. The measurement results are shown in Table 1. Example 3 To a powder of propylene-ethylene random copolymer having an ethylene content of 5.5% by weight, 0.02% by weight of the organic peroxide Lupazol 101 was added together with additives such as antioxidants and 0.30% by weight of a nucleating agent. %
and pelletized in the same manner as in Example 1 to obtain polypropylene resin pellets. The MFI is
41g/10min, [η] is 1.10, logMFI+
5.20log [η] was 1.83. Using this resin, an injection stretch blow molded bottle was obtained in the same manner as in Example 1, and the wall thickness and haze of the body were measured. The measurement results are shown in Table 1. Example 4 A powder of propylene-ethylene random copolymer having an ethylene content of 1.5% by weight was mixed with the organic peroxide Perkatox 14 (Trademark, Chemical Example 1
Polypropylene resin pellets were obtained in the same manner as above. Its MFI is 6g/10min and [η] is 1.58
So, logMFI+5.20log [η] was 1.81. Using this resin, an injection stretch blow molded bottle was obtained in the same manner as in Example 1, and the wall thickness and haze of the body were measured. The measurement results are shown in Table 1. Comparative Example 1 Polypropylene resin with ethylene content of 4% by weight MFI2g/10min, [η]2.10dl/g, logMFI
A round bottle was molded in the same manner as in Example 1 using a propylene-ethylene random copolymer having +5.20 log [η] = 1.98 and containing 0.3% by weight of a nucleating agent. Table 1 shows the wall thickness and haze of the body of the obtained bottle.
Shown below. Comparative Example 2 In addition to additives such as antioxidants, 0.24% by weight of the organic peroxide Percadox 14 and 0.30% by weight of a nucleating agent were added to a propylene-ethylene random copolymer powder with an ethylene content of 2% by weight. Add,
Polypropylene resin pellets were obtained in the same manner as in Example 1. Its MFI is 55g/10min, [η]
was 1.09dl/g, and logMFI+5.20log[η] was 1.93. Using this polypropylene, injection stretch blow molding was carried out in the same manner as in Example 1, but thickness unevenness became significant during blow molding, and a good container could not be obtained. Comparative Example 3 In addition to additives such as antioxidants, organic peroxide Lupasol 101 was added to powder of propylene-ethylene random copolymer with an ethylene content of 0.5% by weight.
Polypropylene resin pellets were obtained in the same manner as in Example 1 by adding 0.10% by weight and 0.30% by weight of a nucleating agent. Its MFI is 15g/10min, and [η] is
At 1.33dl/g, logMFI+5.20log[η] was 1.82. Using this polypropylene, injection stretch blow molding was performed in the same manner as in Example 1, but the thickness deviation during blow molding was significant and a good container could not be obtained. 【table】
Claims (1)
射出延伸ブロー成形したポリプロピレン樹脂製ブ
ロー成形容器であつて、該プロピレン−エチレン
ランダム共重合体がエチレン含有量が1〜6重量
%で、メルトフローインデツクスが4〜50g/10
分で、かつ135℃のテトラリン溶液中で測定した
極限粘度〔η〕(dl/g)とメルトフローインデ
ツクスMFI(g/10分)との関係が 1.70≦logMFI+5.20log〔η〕≦1.95 であるものであることを特徴とする透明性が改良
され、偏肉のないポリプロピレン樹脂製ブロー成
形容器。[Scope of Claims] 1. A polypropylene resin blow-molded container obtained by injection stretch blow-molding a random copolymer of propylene and ethylene, wherein the propylene-ethylene random copolymer has an ethylene content of 1 to 6% by weight. , melt flow index is 4-50g/10
The relationship between the intrinsic viscosity [η] (dl/g) and the melt flow index MFI (g/10 min) measured in a tetralin solution at 135°C is 1.70≦logMFI+5.20log[η]≦1.95. A blow molded polypropylene resin container with improved transparency and no uneven thickness.
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58233508A JPS60125630A (en) | 1983-12-13 | 1983-12-13 | Blow molded container with improved transparency |
EP84115106A EP0151741A3 (en) | 1983-12-13 | 1984-12-10 | Injection stretch-blow molded container and resin composition therefor |
EP87110734A EP0251340B1 (en) | 1983-12-13 | 1984-12-10 | Injection stretch-blow molding process |
DE3486446T DE3486446T2 (en) | 1983-12-13 | 1984-12-10 | Injection blow molding |
CA000469959A CA1240446A (en) | 1983-12-13 | 1984-12-12 | Injection stretch-blow molded container and resin composition therefor |
AU36543/84A AU554076B2 (en) | 1983-12-13 | 1984-12-12 | Ethylene-propylene copolymer compositions and containers |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58233508A JPS60125630A (en) | 1983-12-13 | 1983-12-13 | Blow molded container with improved transparency |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60125630A JPS60125630A (en) | 1985-07-04 |
JPH043728B2 true JPH043728B2 (en) | 1992-01-24 |
Family
ID=16956125
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP58233508A Granted JPS60125630A (en) | 1983-12-13 | 1983-12-13 | Blow molded container with improved transparency |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60125630A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101157397A (en) * | 2006-01-16 | 2008-04-09 | 东莞佳鸿机械制造有限公司 | Transfusion container for blow molding shaping as well as its preparing method and material |
-
1983
- 1983-12-13 JP JP58233508A patent/JPS60125630A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS60125630A (en) | 1985-07-04 |
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