JP4564876B2 - Polyethylene resin for container lid - Google Patents
Polyethylene resin for container lid Download PDFInfo
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- JP4564876B2 JP4564876B2 JP2005110205A JP2005110205A JP4564876B2 JP 4564876 B2 JP4564876 B2 JP 4564876B2 JP 2005110205 A JP2005110205 A JP 2005110205A JP 2005110205 A JP2005110205 A JP 2005110205A JP 4564876 B2 JP4564876 B2 JP 4564876B2
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- 229920013716 polyethylene resin Polymers 0.000 title claims description 54
- -1 polyethylene Polymers 0.000 claims description 19
- 239000004698 Polyethylene Substances 0.000 claims description 14
- 229920000573 polyethylene Polymers 0.000 claims description 14
- 229920005678 polyethylene based resin Polymers 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 12
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 11
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- 239000011342 resin composition Substances 0.000 claims description 8
- 238000005452 bending Methods 0.000 claims description 7
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 239000002685 polymerization catalyst Substances 0.000 claims description 6
- 230000003068 static effect Effects 0.000 claims description 4
- 239000003039 volatile agent Substances 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 description 18
- 238000000465 moulding Methods 0.000 description 12
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 239000005977 Ethylene Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 230000000379 polymerizing effect Effects 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 235000013361 beverage Nutrition 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- 238000000748 compression moulding Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000012968 metallocene catalyst Substances 0.000 description 3
- 239000011990 phillips catalyst Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 206010027146 Melanoderma Diseases 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 235000014214 soft drink Nutrition 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 235000009569 green tea Nutrition 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 229940028444 muse Drugs 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- GMVPRGQOIOIIMI-DWKJAMRDSA-N prostaglandin E1 Chemical compound CCCCC[C@H](O)\C=C\[C@H]1[C@H](O)CC(=O)[C@@H]1CCCCCCC(O)=O GMVPRGQOIOIIMI-DWKJAMRDSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
- 235000021260 warm beverage Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Closures For Containers (AREA)
- Wrappers (AREA)
Description
本発明は、清涼飲料等の液体を収容する容器の蓋用ポリエチレン系樹脂に関し、詳しくは成形性、高流動性、剛性と耐衝撃性とのバランス、耐ストレスクラック性、滑り性、低臭気性、食品安全性に優れ、かつ高温時においても比較的容易にカット出来るポリエチレン系樹脂に関する。特に、本発明のポリエチレン系樹脂は、ポリエチレンテレフタレート（以下、ＰＥＴともいう）製ボトル等の飲料容器に用いられる容器蓋に好適な材料であり、剛性が高く、易開封性に優れた容器蓋を提供できる。なおかつ、高速成形に優れ、内容物に異味を与えるような添加剤も含まず、内容物に異臭を与えるような炭化水素揮発分が少ない、容器蓋に好適な材料を提供するものである。 The present invention relates to a polyethylene-based resin for lids of containers that contain liquids such as soft drinks, and more specifically, moldability, high fluidity, balance between rigidity and impact resistance, stress crack resistance, slipperiness, and low odor. The present invention relates to a polyethylene resin that is excellent in food safety and can be cut relatively easily even at high temperatures. In particular, the polyethylene resin of the present invention is a material suitable for container lids used for beverage containers such as polyethylene terephthalate (hereinafter also referred to as PET) bottles, and has a highly rigid and easy-open container lid. Can be provided. In addition, the present invention provides a material suitable for a container lid that is excellent in high-speed molding, does not contain additives that give taste to the contents, and has a small amount of hydrocarbon volatile matter that gives a strange odor to the contents.
従来、清涼飲料水等の容器として、ポリエチレンテレフタレート製の容器（ボトル）が用いられ、その蓋としてアルミニウム金属製の蓋が用いられていたが、近年、リサイクル性等の環境保全の観点からポリオレフィン製の蓋（キャップ）が用いられるようになってきた。 Conventionally, a container (bottle) made of polyethylene terephthalate has been used as a container for soft drinks, and a lid made of aluminum metal has been used as its cover. Recently, it is made of polyolefin from the viewpoint of environmental conservation such as recyclability. Lids (caps) have come to be used.
さらに、ポリオレフィン製のキャップ成形サイクルを短縮し、生産効率を上げるため、高流動性のポリオレフィンにて射出成形および圧縮成形を行う試みがなされており、この中でポリエチレンはポリプロピレンに比べ融点が低いため、成形サイクルを短縮できる点で注目され、さらに、ポリエチレンはキャップ開閉時の滑り性も良好であるため、好ましい。 Furthermore, in order to shorten the polyolefin cap molding cycle and increase production efficiency, attempts have been made to perform injection molding and compression molding with high-fluidity polyolefins, among which polyethylene has a lower melting point than polypropylene. In view of the fact that the molding cycle can be shortened, polyethylene is preferable because it has a good sliding property when the cap is opened and closed.
また、経済上の理由からキャップの肉厚を薄くすることも要求されているため、薄い肉厚による剛性低下で内圧によって変形しシール部から内容物が漏れないようにするため高い剛性が求められている。 Moreover, since it is required to reduce the thickness of the cap for economic reasons, high rigidity is required in order to prevent the contents from leaking from the seal part due to deformation caused by internal pressure due to the reduction in rigidity due to the thin thickness. ing.
最近では緑茶などの飲料入り容器を加温器にて加温し販売する態様が現れてきた。
この加温販売においては、加温時でも形状を保持できるよう更なる高剛性化および高温時のキャップ締め付けによる割れが発生しないことが要求される。
Recently, a mode has appeared in which containers containing beverages such as green tea are heated and sold with a heater.
In this warming sale, it is required that the rigidity is further increased so that the shape can be maintained even during warming and that cracks due to cap tightening at high temperatures do not occur.
例えば２種類のポリエチレンを順次重合もしくはブレンドすることにより得られるポリエチレン組成物は耐ストレスクラック性、耐衝撃性等に優れており、コンテナー、ボトル、フィルム等に使用されているが、高速成形に対応しうる高流動性、高温時の切れ性の満足するものが得られず、加温販売用キャップには使用されていない。一方、近年の成形サイクル向上のための流動性を重視したポリエチレンでは一般に耐ストレスクラック性が不足する。また、単に剛性を重視した高密度のポリエチレンでも耐ストレスクラック性は同様に劣る。例えば、特許文献１に記載されたポリエチレン組成物では、耐ストレスクラック性は良いものの、高サイクル成形性および高剛性化の点では不十分である。 For example, polyethylene composition obtained by sequentially polymerizing or blending two types of polyethylene is excellent in stress crack resistance, impact resistance, etc., and is used for containers, bottles, films, etc. High fluidity and high cutting performance at high temperatures are not obtained, and it is not used for heated sales caps. On the other hand, polyethylene with emphasis on fluidity for improving molding cycles in recent years generally lacks stress crack resistance. Moreover, the stress crack resistance is similarly inferior even with high-density polyethylene that emphasizes rigidity. For example, the polyethylene composition described in Patent Document 1 has good stress crack resistance, but is insufficient in terms of high cycle moldability and high rigidity.
また、特許文献２および特許文献３で提案されているポリエチレン系樹脂組成物により容器および蓋の耐ストレスクラック性を向上させることが可能となったが、加温用の容器としては更なる高剛性が望まれており、切れ性、剛性、耐ストレスクラック性とのバランスが不十分で、加温販売容器の蓋には使用されていないのが現状である。さらに、一般的に成形サイクルが上がらず、高速成形できないことが問題となっている。 Moreover, although it became possible to improve the stress crack resistance of a container and a lid | cover by the polyethylene-type resin composition proposed by patent document 2 and patent document 3, it is still higher rigidity as a container for heating. However, the balance between cutting ability, rigidity, and stress crack resistance is insufficient, and it is currently not used for lids of heated sales containers. Furthermore, the molding cycle generally does not increase, and it is a problem that high-speed molding cannot be performed.
本発明の目的は、成形性、高流動性、剛性と耐衝撃性とのバランス、耐ストレスクラック性、滑り性に優れ、比較的容易にカットでき、また、添加剤無添加および低揮発性による低味低臭性に優れ、かつ高速成形性に優れるポリエチレン系樹脂で、特にＰＥＴボトル等の飲料容器に用いられる容器蓋に好適な材料を提供することにある。本発明のポリエチレン系樹脂を用いることにより、剛性が高く、加温（６０℃程度）時の開栓でも易開口性があり、タンパーエビデント性付与のためのブリッジの切れが良く、割れず、また、高速成形性、成形ハイサイクル性に優れた容器蓋を提供することができる。 The object of the present invention is excellent in moldability, high fluidity, balance between rigidity and impact resistance, stress crack resistance, slipperiness, can be cut relatively easily, and has no additive and low volatility. An object of the present invention is to provide a material suitable for a container lid used for a beverage container such as a PET bottle, which is a polyethylene resin excellent in low taste and low odor and excellent in high-speed moldability. By using the polyethylene-based resin of the present invention, the rigidity is high, it is easy to open even when heated (about 60 ° C.), the bridge for imparting tamper evidence is good, the crack is not broken, Moreover, the container lid excellent in the high-speed moldability and the shaping | molding high cycle property can be provided.
そこで本発明者らは成形性、高流動性、剛性、耐ストレスクラック性等の性能を有する容器蓋用ポリエチレン系樹脂組成物を開発すべく鋭意研究を重ねた結果、これらの特性を満足する容器蓋用ポリエチレン系樹脂を発明するに至った。 Therefore, as a result of intensive research to develop a polyethylene-based resin composition for container lids having performances such as moldability, high fluidity, rigidity, and stress crack resistance, the present inventors have obtained a container that satisfies these characteristics. It came to invent the polyethylene-type resin for lids.
すなわち本発明の第１は、以下のａ）〜ｆ）の性状を有することを特徴とする容器蓋用ポリエチレン系樹脂である。
ａ）ＭＦＲ（温度１９０℃において荷重２．１６Ｋｇで測定。以下同じ）が０．５〜１０ｇ／１０ｍｉｎであってＨＬＭＦＲ（温度１９０℃において荷重２１．６Ｋｇで測定。以下同じ）が１００〜５００ｇ／１０ｍｉｎであり、かつＨＬＭＦＲ／ＭＦＲが５０〜２００である、
ｂ）密度が０．９５８ｇ／ｃｍ３以上、
ｃ）射出成形試料の曲げ弾性率が１０００ＭＰａ以上、
ｄ）射出成形試料の定ひずみＥＳＣＲが１０〜４０時間、
ｅ）引張破壊伸びが１００％以下、
ｆ）キャピラリーレオメーターによる２００℃のせん断速度２００ｓｅｃ−１の溶融粘度が４００Ｐａ・Ｓ以下。
That is, the first of the present invention is a polyethylene resin for container lids having the following properties a) to f).
a) MFR (measured at a load of 2.16 Kg at a temperature of 190 ° C., hereinafter the same) is 0.5 to 10 g / 10 min and HLMFR (measured at a load of 21.6 Kg at a temperature of 190 ° C., the same shall apply hereinafter) is from 100 to 500 g / 10 min and HLMFR / MFR is 50-200,
b) Density of 0.958 g / cm 3 or more,
c) The bending elastic modulus of the injection molded sample is 1000 MPa or more,
d) Constant strain ESCR of the injection molded sample is 10 to 40 hours,
e) Tensile elongation at break of 100% or less,
f) A melt viscosity at a shear rate of 200 sec −1 at 200 ° C. measured by a capillary rheometer is 400 Pa · S or less.
本発明の第２は、前記ポリエチレン系樹脂が、本発明の第１に加えて、さらに下記要件ｇ）〜ｈ）の性状をも有することを特徴とする容器蓋用ポリエチレン樹脂である。
ｇ）炭化水素揮発分が８０ｐｐｍ以下、
ｈ）静摩擦係数が０．３５以下。
According to a second aspect of the present invention, there is provided a polyethylene resin for container lids, wherein the polyethylene-based resin further has the following requirements g) to h) in addition to the first aspect of the present invention.
g) The hydrocarbon volatile content is 80 ppm or less,
h) Static friction coefficient is 0.35 or less.
本発明の第３は、前記ポリエチレン系樹脂が、
（Ａ）ＨＬＭＦＲが０．１ｇ／１０ｍｉｎを越え１０ｇ／１０ｍｉｎ以下、密度が０．９３５ｇ／ｃｍ３以上のポリエチレン系樹脂を１０質量部以上４５質量部未満、および
（Ｂ）ＭＦＲが３０ｇ／１０ｍｉｎ以上、密度が０．９６１ｇ／ｃｍ３以上のポリエチレン系樹脂５５質量部より多く９０質量部以下（Ａ＋Ｂ＝１００質量部）
からなることを特徴とする本発明の第１または第２の容器蓋用ポリエチレン系樹脂である。
According to a third aspect of the present invention, the polyethylene resin is
(A) HLMFR exceeds 0.1 g / 10 min to 10 g / 10 min or less, and a polyethylene resin having a density of 0.935 g / cm 3 or more is 10 to 45 parts by mass, and (B) MFR is 30 g / 10 min or more. More than 55 parts by mass of polyethylene resin having a density of 0.961 g / cm 3 or more and 90 parts by mass or less (A + B = 100 parts by mass)
It is the 1st or 2nd polyethylene resin for container lids of this invention characterized by consisting of.
本発明の第４は、前記ポリエチレン系樹脂が、ポリエチレン重合触媒残渣失活剤以外の添加剤を含まないことを特徴とする本発明の第１乃至第３のいずれかの容器蓋用ポリエチレン系樹脂である。 According to a fourth aspect of the present invention, the polyethylene resin for a container lid according to any one of the first to third aspects of the present invention is characterized in that the polyethylene resin does not contain an additive other than the polyethylene polymerization catalyst residue deactivator. It is.
本発明の第５は、前記容器が飲料用容器の容器であることを特徴とする本発明の第１乃至第４のいずれかの容器蓋用ポリエチレン系樹脂である。 A fifth aspect of the present invention is the polyethylene lid resin for a container lid according to any one of the first to fourth aspects of the present invention, wherein the container is a container for a beverage container.
本発明の第６は、本発明の第１乃至第５において、前記容器がポリエチレンテレフタレート製ボトルであることを特徴とする容器蓋用ポリエチレン系樹脂である。 A sixth aspect of the present invention is a polyethylene resin for container lids according to the first to fifth aspects of the present invention, wherein the container is a polyethylene terephthalate bottle.
本発明の第７は、前記ポリエチレン系樹脂が、多段重合又は混合により、
（Ａ）ＨＬＭＦＲが０．１ｇ／１０ｍｉｎを越え１０ｇ／１０ｍｉｎ以下、密度が０．９３５ｇ／ｃｍ３以上のポリエチレン系樹脂を１０質量部以上４５質量部未満、および
（Ｂ）ＭＦＲが３０ｇ／１０ｍｉｎ以上、密度が０．９６１ｇ／ｃｍ３以上のポリエチレン系樹脂５５質量部より多く９０質量部以下（Ａ＋Ｂ＝１００質量部）
からなるポリエチレン系樹脂とすることを特徴とする本発明の第１乃至第６のいずれかの容器蓋用ポリエチレン系樹脂の製造方法である。
In the seventh aspect of the present invention, the polyethylene resin is obtained by multistage polymerization or mixing.
(A) HLMFR exceeds 0.1 g / 10 min to 10 g / 10 min or less, and a polyethylene resin having a density of 0.935 g / cm 3 or more is 10 to 45 parts by mass, and (B) MFR is 30 g / 10 min or more. More than 55 parts by mass of polyethylene resin having a density of 0.961 g / cm 3 or more and 90 parts by mass or less (A + B = 100 parts by mass)
A method for producing a polyethylene-based resin for a container lid according to any one of the first to sixth aspects of the present invention, characterized in that the polyethylene-based resin is made of.
本発明の容器蓋用ポリエチレン系樹脂は、成形性、高流動性、剛性と耐衝撃性とのバランス、耐ストレスクラック性、滑り性、低臭気性、食品安全性に優れ、かつ高温時においても比較的容易にカットできるポリエチレン系樹脂である。特にＰＥＴボトル等の飲料容器に用いられる容器蓋に好適な材料であり、剛性が高く、易開封性に優れた容器蓋を提供できる。なおかつ、高速成形性に優れ、内容物に異臭を与えるような炭化水素揮発分が少ない、容器蓋に好適な材料を提供できる。 The polyethylene resin for container lids of the present invention is excellent in moldability, high fluidity, balance between rigidity and impact resistance, stress crack resistance, slipperiness, low odor, food safety, and even at high temperatures. It is a polyethylene resin that can be cut relatively easily. In particular, it is a material suitable for a container lid used for beverage containers such as PET bottles, and can provide a container lid having high rigidity and excellent openability. In addition, it is possible to provide a material suitable for a container lid, which is excellent in high-speed moldability and has a small amount of hydrocarbon volatiles that give a strange odor to the contents.
本発明におけるポリエチレン系樹脂は、チーグラー触媒、フィリップス触媒、メタロセン触媒等の公知の各種触媒を用いてエチレンを主として重合することにより得られる。例えば、一般的には、チタン、ジルコニウム等の遷移金属化合物、マグネシウム化合物からなるチーグラー触媒、酸化クロム系触媒を代表とするフィリップス触媒およびジルコニウム、ハフニウム、チタン等の遷移金属化合物に少なくとも１つのシクロペンタジエニル基または置換シクロペンタジエニル基を有するメタロセン系触媒を重合触媒として重合することにより得られる。重合に際しては、エチレンを単独で重合するか、またはエチレンと炭素数３〜１８のα−オレフィンから選ばれる１種またはそれ以上のコモノマーを所定の密度になるよう共重合することにより得られる。共重合するα−オレフィンの代表例としては例えばプロピレン、１−ブテン、１−ヘキセン、１−オクテン、４−メチル−１ペンテン等が挙げられる。本発明のポリエチレンとしては、これらのエチレン単独重合体またはエチレン・α−オレフィン共重合体を単独で、または適宜に混合して使用することができる。 The polyethylene resin in the present invention can be obtained by mainly polymerizing ethylene using various known catalysts such as a Ziegler catalyst, a Phillips catalyst, and a metallocene catalyst. For example, in general, transition metal compounds such as titanium and zirconium, Ziegler catalysts composed of magnesium compounds, Phillips catalysts typified by chromium oxide-based catalysts, and transition metal compounds such as zirconium, hafnium, and titanium have at least one cyclopenta It can be obtained by polymerizing a metallocene catalyst having a dienyl group or a substituted cyclopentadienyl group as a polymerization catalyst. In the polymerization, it is obtained by polymerizing ethylene alone or by copolymerizing ethylene and one or more comonomers selected from C3-C18 α-olefins to a predetermined density. Representative examples of the α-olefin to be copolymerized include propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene and the like. As the polyethylene of the present invention, these ethylene homopolymers or ethylene / α-olefin copolymers can be used alone or in an appropriate mixture.
該ポリエチレン樹脂は、ａ）温度１９０℃、荷重２．１６ＫｇにおけるＭＦＲが０．５〜１０ｇ／１０ｍｉｎ、好ましくは０．８〜６ｇ／１０ｍｉｎ、さらに好ましくは０．７〜３．５ｇ／１０ｍｉｎの範囲である。さらに、温度１９０℃、荷重２１．６ＫｇにおけるＨＬＭＦＲが１００〜５００ｇ／１０ｍｉｎ、好ましくは１１０〜４５０ｇ／１０ｍｉｎ、さらに好ましくは１２０〜３２０ｇ／１０ｍｉｎ、かつＨＬＭＦＲ／ＭＦＲが５０〜２００、好ましくは５５〜１５０、さらに好ましくは６０〜１１０の範囲である。 The polyethylene resin has a) MFR at a temperature of 190 ° C. and a load of 2.16 kg of 0.5 to 10 g / 10 min, preferably 0.8 to 6 g / 10 min, more preferably 0.7 to 3.5 g / 10 min. It is. Furthermore, HLMFR at a temperature of 190 ° C. and a load of 21.6 kg is 100 to 500 g / 10 min, preferably 110 to 450 g / 10 min, more preferably 120 to 320 g / 10 min, and HLMFR / MFR is 50 to 200, preferably 55 to 150. More preferably, it is the range of 60-110.
ＨＬＭＦＲが１００ｇ／１０ｍｉｎ未満であると、ＭＦＲが０．５〜１０ｇ／１０ｍｉｎの範囲であっても高速成形性が劣る。また、ＭＦＲが１０ｇ／１０ｍｉｎを超えると、ＨＬＭＦＲが１００〜５００ｇ／１０ｍｉｎであっても、耐ストレスクラック性が劣り好ましくない一方、ＭＦＲが０．５ｇ／１０ｍｉｎ未満では、ＨＬＭＦＲが１００〜５００ｇ／１０ｍｉｎを達成することは困難であり、その結果当然ながら高速成形性が劣る。ＨＬＭＦＲ／ＭＦＲが５０より小さいと耐ストレスクラック性とブリッジ切れ性のバランスが取れず好ましくない。ＨＬＭＦＲ／ＭＦＲが２００より大きいと、同様に耐ストレスクラック性とブリッジ切れ性のバランスが取れず好ましくない。 When the HLMFR is less than 100 g / 10 min, the high-speed moldability is inferior even if the MFR is in the range of 0.5 to 10 g / 10 min. Further, when the MFR exceeds 10 g / 10 min, the stress crack resistance is inferior even if the HLMFR is 100 to 500 g / 10 min. Is difficult to achieve, and as a result, the high-speed moldability is naturally inferior. If HLMFR / MFR is less than 50, the balance between stress crack resistance and bridge breakability cannot be achieved. When HLMFR / MFR is larger than 200, the stress crack resistance and the bridge breakability are similarly unbalanced.
さらに本発明のポリエチレン系樹脂は、ｂ）密度が０．９５８ｇ／ｃｍ３以上、好ましくは０．９６０ｃｍ３以上である。密度を０．９５８ｇ／１０ｍｉｎ以上とすることにより高レベルの剛性を有し、高温時でもキャップが変形しにくい。密度が０．９５８ｇ／ｃｍ３に達しないものは剛性が劣り、キャップが変形しやすく好ましくない。密度の上限値は特に限定されないが、通常０．９８０ｇ／ｃｍ３程度である。 Furthermore polyethylene resin of the present invention, b) density of 0.958 g / cm 3 or more, preferably 0.960Cm 3 or more. By setting the density to 0.958 g / 10 min or more, the cap has a high level of rigidity and the cap is not easily deformed even at high temperatures. Those in which the density does not reach 0.958 g / cm 3 are not preferable because the rigidity is poor and the cap is easily deformed. The upper limit of the density is not particularly limited, but is usually about 0.980 g / cm 3 .
前記ポリエチレン系樹脂は、ｃ）射出成形試料の曲げ弾性率が１０００ＭＰａ以上である。より好ましい曲げ弾性率は１１００ＭＰａ以上、さらに好ましくは１３００ＭＰａ以上である。曲げ弾性率が１０００ＭＰａに達しないものは剛性が劣り、特に高温時にキャップが変形しやすい。曲げ弾性率の上限値は特に限定されないが、通常は２０００ＭＰａ程度である。 The polyethylene-based resin is c) the bending elastic modulus of the injection molded sample is 1000 MPa or more. A more preferable flexural modulus is 1100 MPa or more, and further preferably 1300 MPa or more. Those whose bending elastic modulus does not reach 1000 MPa have poor rigidity, and the cap is liable to be deformed particularly at high temperatures. The upper limit of the flexural modulus is not particularly limited, but is usually about 2000 MPa.
本発明において曲げ弾性率測定用試験片は射出成形にて２１０℃で４×１０×８０ｍｍの試験片を作製し、ＪＩＳ−Ｋ６９２２−２：１９９７準拠にて行った。 In the present invention, the test piece for measuring the flexural modulus was a 4 × 10 × 80 mm test piece manufactured at 210 ° C. by injection molding, and was performed in accordance with JIS-K6922-2: 1997.
前記ポリエチレン系樹脂は、ｄ）射出成形試料の定ひずみＥＳＣＲが１０〜４０時間であり、物性バランス、キャップ要求性能から通常１０〜２０時間である。これは一定ひずみ下での耐ストレスクラック性であり、具体的にはＪＩＳ−Ｋ６９２２−２：１９９７に従うものである。試料は１９０℃にて射出成形された１２０×１２０×２ｍｍの寸法の板から切り出した試料を用いるものである。 The polyethylene resin has d) a constant strain ESCR of an injection molded sample of 10 to 40 hours, and is usually 10 to 20 hours from the balance of physical properties and cap required performance. This is stress crack resistance under a constant strain, and specifically conforms to JIS-K6922-2: 1997. As the sample, a sample cut out from a plate having a size of 120 × 120 × 2 mm which is injection-molded at 190 ° C. is used.
この定ひずみＥＳＣＲが１０時間未満では、応力によりキャップが破壊しやすく、内容物の液漏れ原因となる。また、４０時間を超えるものでは、耐ストレスクラック性は良いものの、剛性と流動性のバランスが取れない。 If this constant strain ESCR is less than 10 hours, the cap is easily broken by the stress, which causes liquid leakage of the contents. Moreover, when it exceeds 40 hours, although the stress crack resistance is good, rigidity and fluidity cannot be balanced.
本発明のポリエチレン系樹脂は、前記特性の他に、ｅ）キャピラリーレオメーターによる２００℃のせん断速度２００ｓｅｃ−１の溶融粘度が４００Ｐａ・Ｓ以下であることが必要である。より好ましくは３８０Ｐａ・Ｓ以下、さらに好ましくは３５０Ｐａ・Ｓ以下である。これにより、高流動化が出来、高速成形が可能となるため、成形ハイサイクル化が可能となる。溶融粘度は、ＪＩＳ−Ｋ−７１９９：１９９９に準拠して測定し、具体的には、インテスコ社製インテスコ全自動キャピラリーレオメーターを用い、２００℃、ｄ＝１ｍｍ、Ｌ／Ｄ＝３０のキャピラリーを用いて測定を行う。 In addition to the above properties, the polyethylene resin of the present invention is required to have e) a melt viscosity of 200 Pa −1 at 200 ° C. measured by a capillary rheometer of 400 Pa · S or less. More preferably, it is 380 Pa * S or less, More preferably, it is 350 Pa * S or less. As a result, high fluidization can be achieved and high-speed molding is possible, so that molding high cycle can be achieved. The melt viscosity is measured according to JIS-K-7199: 1999. Specifically, an Intesco fully automatic capillary rheometer manufactured by Intesco is used, and a capillary at 200 ° C., d = 1 mm, L / D = 30 is measured. To make measurements.
本発明のポリエチレン系樹脂は、酸化防止剤等の添加剤を含んでも良いが、ポリエチレン重合触媒残渣失活剤以外の添加剤を含まないことが望ましい。ポリエチレン重合触媒残渣失活剤としては金属石鹸等が挙げられ、特にステアリン酸カルシウム以外の添加剤を含まないものが好ましい。本発明の要件を満足することにより、添加剤またはその分解物が内溶液に抽出されることによる異味を防ぐことができる。特に容器の内容物が牛乳の場合には好ましい。また、添加剤に起因すると考えられる異物が成形機内に滞留し、製品に黒点として発生することが見受けられるが、本発明の要件を満足することにより、該黒点の発生を防止することが出来る。 The polyethylene resin of the present invention may contain an additive such as an antioxidant, but it is desirable that no additive other than the polyethylene polymerization catalyst residue deactivator be included. Examples of the polyethylene polymerization catalyst residue quencher include metal soaps, and those containing no additives other than calcium stearate are particularly preferable. By satisfying the requirements of the present invention, it is possible to prevent off-flavors due to extraction of the additive or its decomposition product into the internal solution. This is particularly preferable when the contents of the container are milk. In addition, it can be seen that foreign matter that is considered to be caused by the additive stays in the molding machine and is generated as a black spot in the product. However, by satisfying the requirements of the present invention, the occurrence of the black spot can be prevented.
本発明のポリエチレン系樹脂は、ｆ）炭化水素揮発分が８０ｐｐｍ以下、好ましくは５０ｐｐｍ以下であることが望ましい。本発明にいう炭化水素とは、少なくとも炭素及び水素を含む化合物をいい、通常ガスクロマトグラフィーにて測定されるもので、本発明の要件を満足することにより、容器の内容物の異臭を防ぐことができる。具体的にはポリエチレン系樹脂１ｇを２５ｍｌのガラス密閉容器に入れ、１３０℃で６０分加熱した際のへッドスペース中の空気をガスクロマトグラフィーにて揮発分を測定される。炭化水素揮発分は８０ｐｐｍ以下であることが望ましく、好ましくは７０ｐｐｍ以下、さらに好ましくは５０ｐｐｍ以下である。８０ｐｐｍを越えると異臭感を防ぐことが難しくなる。本発明において、炭化水素揮発分を所定の値以下にするためには、重合したポリエチレン系樹脂を揮発分除去操作、例えばスチームストリッピング処理、真空処理、窒素パージ処理、温風脱臭等を実施することにより達成することができる。 It is desirable that the polyethylene resin of the present invention has a f) hydrocarbon volatile content of 80 ppm or less, preferably 50 ppm or less. The hydrocarbon referred to in the present invention refers to a compound containing at least carbon and hydrogen, and is usually measured by gas chromatography. By satisfying the requirements of the present invention, the odor of the contents of the container is prevented. Can do. Specifically, 1 g of polyethylene resin is put in a 25 ml glass sealed container, and the volatile matter is measured by gas chromatography on the air in the head space when heated at 130 ° C. for 60 minutes. The hydrocarbon volatile content is desirably 80 ppm or less, preferably 70 ppm or less, and more preferably 50 ppm or less. When it exceeds 80 ppm, it becomes difficult to prevent a bad odor. In the present invention, in order to reduce the hydrocarbon volatile content to a predetermined value or less, the polymerized polyethylene resin is subjected to a volatile content removal operation such as steam stripping treatment, vacuum treatment, nitrogen purge treatment, hot air deodorization, etc. Can be achieved.
本発明のポリエチレン系樹脂は、ｈ）静摩擦係数が０．３５以下、好ましくは０．３０以下、更に好ましくは０．２５以下であることが望ましい。本発明にいう静摩擦係数は、ＪＩＳ−Ｋ−７１２５：１９９９に準拠して測定される。ただし、別法として、東芝機械製ＩＳ−１５０射出成形機を用いて１９０℃にて成形を行った１２０×１２０×２mmの平板を用い、新東科学社製トライポギア ミューズ９４ｉにて両面測定することも可能である。この値が０．３５を超えるものは、滑り性が悪く、キャップ開閉に支障がある。 The polyethylene resin of the present invention has h) a coefficient of static friction of 0.35 or less, preferably 0.30 or less, more preferably 0.25 or less. The static friction coefficient said to this invention is measured based on JIS-K-7125: 1999. However, as an alternative method, use a 120 × 120 × 2 mm flat plate molded at 190 ° C. using a Toshiba Machine IS-150 injection molding machine, and measure both sides with the Shinpo Kagaku Trypogear Muse 94i. Is also possible. When this value exceeds 0.35, the slipperiness is poor and there is a problem in opening and closing the cap.
本発明の容器蓋用ポリエチレン系樹脂は、上記ａ）〜ｆ）、好ましくは上記ａ）〜ｈ）の要件を満たすものであれば、単一のポリエチレン系重合体からなるものでもよい。もちろん、複数たとえば二種類またはそれ以上の異なる物性のポリエチレン系重合体からなるものでもよい。好ましいものとしては、以下に述べる（Ａ）成分１０質量部以上４５質量部未満、好ましくは２０質量部以上３５質量部未満と、（Ｂ）成分５５質量部より多く９０質量部以下、好ましくは６５質量部より多く８０質量部以下からなるもので、各成分を別々に重合して後でブレンドしたものでもよく、さらに好ましくは各成分を順次重合して得られるものを使用することができる。 The container lid polyethylene resin of the present invention may be composed of a single polyethylene polymer as long as it satisfies the requirements a) to f), preferably a) to h). Of course, it may be composed of a plurality of polyethylene polymers having two or more different physical properties. Preferred are (A) 10 parts by mass to less than 45 parts by mass, preferably 20 parts by mass to less than 35 parts by mass, and (B) more than 55 parts by mass and 90 parts by mass or less, preferably 65 parts described below. It is composed of more than 80 parts by mass and less than 80 parts by mass, and each component may be separately polymerized and blended later. More preferably, those obtained by sequentially polymerizing each component can be used.
ここで、成分（Ａ）を１０質量部以上とすることにより耐ストレスクラック性が向上し、３０質量部未満とすることにより成形性が向上する。成分（Ａ）のポリエチレン樹脂１０質量部未満の場合は耐ストレスクラック性が悪化、４５質量部以上の場合は成形性が悪化し好ましくない。 Here, the stress crack resistance is improved by setting the component (A) to 10 parts by mass or more, and the moldability is improved by setting it to less than 30 parts by mass. When the component (A) is less than 10 parts by mass of the polyethylene resin, the stress crack resistance is deteriorated, and when it is 45 parts by mass or more, the moldability is deteriorated.
上記成分（Ａ）のポリエチレン系樹脂は、ＨＬＭＦＲが０．１ｇ／１０ｍｉｎを越え１０ｇ／１０ｍｉｎ以下、好ましくは１ｇ／１０ｍｉｎを越え１０ｇ／１０ｍｉｎ以下、密度が０．９３５ｇ／ｃｍ３以上、成分（Ｂ）のポリエチレン系樹脂は、ＭＦＲが３０ｇ／１０ｍｉｎ以上、密度が０．９６１ｇ／ｃｍ３以上である。 The polyethylene resin of component (A) has an HLMFR of more than 0.1 g / 10 min to 10 g / 10 min or less, preferably more than 1 g / 10 min to 10 g / 10 min or less, a density of 0.935 g / cm 3 or more, component (B ) Has an MFR of 30 g / 10 min or more and a density of 0.961 g / cm 3 or more.
ここで成分（Ａ）のポリエチレン系樹脂のＨＬＭＦＲが０．１ｇ／１０ｍｉｎ以下の場合は流動性が悪化し成形性が不良となり、１０ｇ／１０ｍｉｎを超える場合は耐ストレスクラック性が悪化する。 Here, when the HLMFR of the polyethylene resin of the component (A) is 0.1 g / 10 min or less, the fluidity deteriorates and the moldability becomes poor, and when it exceeds 10 g / 10 min, the stress crack resistance deteriorates.
また成分（Ａ）のポリエチレン系樹脂の密度が０．９３５ｇ／ｃｍ３に達しない場合は剛性が不十分となる。成分（Ａ）のポリエチレン系樹脂の密度の上限としては特に限定されないが、通常は０．９５５ｇ／ｃｍ３程度である。 Further, when the density of the polyethylene-based resin as the component (A) does not reach 0.935 g / cm 3 , the rigidity becomes insufficient. The upper limit of the density of the polyethylene-based resin as the component (A) is not particularly limited, but is usually about 0.955 g / cm 3 .
上記成分（Ｂ）のポリエチレン系樹脂は、ＭＦＲが３０ｇ／１０ｍｉｎ未満の場合は流動性が悪化し、密度が０．９６１ｇ／ｃｍ３未満の場合は剛性が低下するおそれがある。成分（Ｂ）のポリエチレン系樹脂のＭＦＲの上限は特に制限されないが、通常５００ｇ／１０ｍｉｎ以下である。成分（Ａ）と成分（Ｂ）を混合した組成物のＭＦＲが０．５〜１０ｇ／１０ｍｉｎ、ＨＬＭＦＲが１００〜５００ｇ／１０ｍｉｎ、ＨＬＭＦＲ／ＭＦＲが５０〜２００なる関係を満たす限度において、ポリエチレン系樹脂のＭＦＲの上限は特に制限されない。また、このポリエチレン系樹脂の密度の上限値も特に制限されないが、通常は０．９８０ｇ／ｃｍ３程度である。 When the MFR is less than 30 g / 10 min, the polyethylene resin as the component (B) has poor fluidity, and when the density is less than 0.961 g / cm 3 , the rigidity may be lowered. The upper limit of the MFR of the polyethylene resin as the component (B) is not particularly limited, but is usually 500 g / 10 min or less. In the composition satisfying the relationship of MFR of 0.5 to 10 g / 10 min, HLMFR of 100 to 500 g / 10 min, and HLMFR / MFR of 50 to 200 in the composition obtained by mixing component (A) and component (B) The upper limit of the MFR is not particularly limited. The upper limit of the density of the polyethylene resin is not particularly limited, but is usually about 0.980 g / cm 3 .
本発明のポリエチレン系樹脂は、成分（Ａ）および成分（Ｂ）のポリエチレン系樹脂を連続的にまたは別個にそれぞれ重合し、それらをブレンドすることによっても本発明の容器蓋用ポリエチレン系樹脂とすることができる。重合操作の容易さや組成の均質性確保の容易さ等の理由から、好ましくは直列に接続した複数の重合反応器、たとえば２基の重合反応器で順次連続的に重合して得られるものが好適である。いずれにせよ重合用の触媒としては、前記したチーグラー触媒、フィリップス触媒、メタロセン触媒等のシングルサイト触媒等の各種触媒を用いることができる。重合は有機溶媒中、液状単量体中あるいは気相中で行うことができる。直列に接続した複数の重合反応器で順次連続的に重合する、いわゆる多段重合においては、たとえば一段目においてエチレンあるいはさらにα−オレフィンを加えて共重合させて第一段目では高分子量成分となるポリエチレン系樹脂（成分（Ａ）に相当）を製造し、引き続き同じ重合系中にエチレンおよび水素を導入して、第二段で低分子量成分となるポリエチレン系樹脂（成分（Ｂ）に相当）を製造し、その結果高分子量成分と低分子量成分とを含むポリエチレン系樹脂を調製することができる。 The polyethylene resin of the present invention is obtained by polymerizing the polyethylene resins of component (A) and component (B) either continuously or separately, and blending them to obtain the polyethylene resin for container lids of the present invention. be able to. For reasons such as ease of polymerization operation and ease of ensuring homogeneity of composition, preferably those obtained by successively polymerizing in a plurality of polymerization reactors connected in series, for example, two polymerization reactors in sequence It is. In any case, as the polymerization catalyst, various catalysts such as the above-mentioned Ziegler catalyst, Phillips catalyst, single site catalyst such as metallocene catalyst can be used. The polymerization can be carried out in an organic solvent, in a liquid monomer or in the gas phase. In so-called multistage polymerization in which polymerization is performed sequentially in a plurality of polymerization reactors connected in series, for example, ethylene or further α-olefin is added and copolymerized in the first stage to become a high molecular weight component in the first stage. A polyethylene resin (corresponding to component (A)) is manufactured, and then ethylene and hydrogen are introduced into the same polymerization system, and a polyethylene resin (corresponding to component (B)) that becomes a low molecular weight component in the second stage. As a result, a polyethylene resin containing a high molecular weight component and a low molecular weight component can be prepared.
なお、多段重合の場合、二段目以降の重合域で生成するポリエチレン系樹脂の量とその性状については、各段における樹脂生成量（未反応ガス分析等により把握できる）を求め、樹脂の物性は各段の後でそれぞれ抜出した樹脂の物性を測定し、物性の加成性から換算して求めることができる。 In the case of multi-stage polymerization, the amount of polyethylene resin produced in the second and subsequent polymerization zones and their properties are determined by determining the amount of resin produced in each stage (which can be determined by analysis of unreacted gas, etc.). Can be obtained by measuring the physical properties of the resin extracted after each stage and converting from the additivity of the physical properties.
本発明のポリエチレン系樹脂には、各種公知の添加剤、充填材等を適宜の量で添加でき、添加剤としては例えば酸化防止剤（フェノール系、リン系、イオウ系）、滑剤、帯電防止剤、光安定剤、紫外線吸収剤、着色剤、顔料、染料等を１種または２種以上適宜併用することができ、充填材としては例えばタルク、マイカ等を使用できるが、本発明の第２に基づく発明においては、本発明の要件を満たす限りにおいて上記各種添加剤は使用しない方が好ましい。 Various known additives, fillers, and the like can be added to the polyethylene resin of the present invention in appropriate amounts. Examples of the additives include antioxidants (phenolic, phosphorus, and sulfur), lubricants, and antistatic agents. , Light stabilizers, ultraviolet absorbers, colorants, pigments, dyes and the like can be used in combination of one or more as appropriate, and as the filler, for example, talc, mica, etc. can be used. In the invention based thereon, it is preferable not to use the various additives as long as the requirements of the present invention are satisfied.
本発明に係るポリエチレン系樹脂はＰＥＴボトル等の容器の蓋として好適なものである。本発明の樹脂を用いる蓋の成形法は、特に限定されないが、射出成形、圧縮成形等の成形方法が好ましく用いられる。 The polyethylene resin according to the present invention is suitable as a lid for containers such as PET bottles. The lid molding method using the resin of the present invention is not particularly limited, but a molding method such as injection molding or compression molding is preferably used.
得られる蓋は、ＰＥＴボトル等の容器、特に加温して販売される温飲料の容器蓋として好適なものである。 The obtained lid is suitable for containers such as PET bottles, especially for warm drinks sold by heating.
以下に実施例を挙げて本発明を更に具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples.
下記実施例および比較例におけるポリエチレン系樹脂の物性測定法は以下の通りである。
ＭＦＲ： ＪＩＳ−Ｋ６９２２−２：１９９７
密度 ： ＪＩＳ−Ｋ６９２２−１，２：１９９７
曲げ弾性率： ＪＩＳ−Ｋ６９２２−２：１９９７
引張破壊伸び：ＪＩＳ−Ｋ７１１３：１９９５（２号型試験片）
定ひずみＥＳＣＲ：ＪＩＳ−Ｋ６９２２−２：１９９７
摩擦係数：ＪＩＳ−Ｋ−７１２５：１９９９
The physical property measuring methods of polyethylene resins in the following examples and comparative examples are as follows.
MFR: JIS-K6922-2: 1997
Density: JIS-K6922-1, 2: 1997
Flexural modulus: JIS-K6922-2: 1997
Tensile elongation at break: JIS-K7113: 1995 (No. 2 type test piece)
Constant strain ESCR: JIS-K6922-2: 1997
Friction coefficient: JIS-K-7125: 1999
炭化水素揮発分：ポリエチレン系樹脂１ｇを２５ｍｌのガラス密閉容器に入れ、１３０℃で６０分加熱した際のへッドスペース中の空気をガスクロマトグラフィーにて揮発分を測定する。 Hydrocarbon volatiles: 1 g of polyethylene resin is put in a 25 ml glass sealed container, and the air in the head space when heated at 130 ° C. for 60 minutes is measured by gas chromatography.
溶融粘度：ＪＩＳ−Ｋ−７１９９：１９９９に準拠し、具体的には、インテスコ社製インテスコ全自動キャピラリーレオメーターを用い、２００℃、ｄ＝１ｍｍ、Ｌ／Ｄ＝３０のキャピラリーを用いて測定を行う。 Melt viscosity: Based on JIS-K-7199: 1999, specifically, using an Intesco fully automatic capillary rheometer manufactured by Intesco, using a capillary at 200 ° C., d = 1 mm, L / D = 30 Do.
成形性：高速にて圧縮成形し、キャップ（５００ｍｌのＰＥＴボトル）を正常に成形できるかを評価した。キャップは市販キャップと同一形状（外形約３ｃｍ、長さ約２ｃｍ）のタンパーエビデント性付与のためのブリッジを有するものを一体成形した。良好に問題なく成形できるものは○、流動性が悪くそのため押出機のモーター負荷が大きくなり押出しが困難であったり、所定の形状（キャップ）に成形できないものを×とした。 Moldability: It was evaluated whether the cap (500 ml PET bottle) can be molded normally by compression molding at high speed. A cap having a bridge for imparting tamper evidence having the same shape as the commercially available cap (outer dimension: about 3 cm, length: about 2 cm) was integrally formed. A sample that could be molded well without problems was rated as “◯”, and a product that was poor in fluidity and therefore had a large motor load on the extruder and was difficult to extrude or could not be molded into a predetermined shape (cap).
キャップブリッジ切れ性：５００ｍｌのＰＥＴボトルに水を入れ、得られたキャップ（ブリッジ構造を有するもの）により閉栓し、６５℃に加温した状態にて人力で螺合している栓を開栓した。そして、開栓時のブリッジの切断状況を観察した。 Cap bridge breakability: Water was put into a 500 ml PET bottle, and the obtained cap (having a bridge structure) was closed, and the cap screwed by human power was opened in a state heated to 65 ° C. . And the cutting condition of the bridge at the time of opening was observed.
チーグラー触媒を用いてコモノマーとしてブテン−１を用いスラリー重合法により連続二段重合装置を用いて表１に示した成分（Ａ）を重合後、成分（Ｂ）を重合してポリエチレン系樹脂を得た。それらの配合比、樹脂のＭＦＲ、ＨＬＭＦＲを各測定値とともに併せて示した。即ち、第一段目の重合ではモノマーとしてエチレンおよびブテン−１を供給し、第二段目の重合ではエチレンを供給して製造し、スチームストリッピング処理を施した。第二段目で製造される成分（Ｂ）の量（配合比）、その物性などは、各段の後の未反応ガス分析から各段の生産量をそれぞれ求め、さらに第一段目の後と第二段目の後で得られた樹脂成分の物性をそれぞれ測定し、加成性から換算して求めた。［実施例１］のポリエチレン系樹脂は、曲げ弾性率、耐ストレスクラック性（定ひずみＥＳＣＲ）、成形性（溶融粘度）、揮発分、キャップブリッジ切れ性のいずれも良好であった。 After polymerization of component (A) shown in Table 1 using a continuous two-stage polymerization apparatus by a slurry polymerization method using butene-1 as a comonomer with a Ziegler catalyst, component (B) is polymerized to obtain a polyethylene resin. It was. The blending ratio, MFR and HLMFR of the resin are shown together with each measured value. That is, ethylene and butene-1 were supplied as monomers in the first-stage polymerization, and ethylene was supplied in the second-stage polymerization to produce a steam stripping treatment. The amount (compounding ratio) of the component (B) produced in the second stage, its physical properties, etc. are obtained from the unreacted gas analysis after each stage, and the production amount of each stage is obtained. And the physical properties of the resin component obtained after the second stage were measured and calculated from the additivity. The polyethylene resin of [Example 1] had good bending elastic modulus, stress crack resistance (constant strain ESCR), moldability (melt viscosity), volatile matter, and cap bridge breakability.
表１に示した各成分、コモノマーを用いて［実施例１］と同様に行なった。表１に示したように、得られたポリエチレン系樹脂は、曲げ弾性率、耐ストレスクラック性（定ひずみＥＳＣＲ）、成形性（溶融粘度）、揮発分、キャップブリッジ切れ性のいずれも良好であった。 It carried out similarly to [Example 1] using each component and comonomer shown in Table 1. As shown in Table 1, the obtained polyethylene resin had good bending elastic modulus, stress crack resistance (constant strain ESCR), moldability (melt viscosity), volatile matter, and cap bridge breakability. It was.
表１に示した各成分、コモノマーを用いて［実施例１］と同様に行なった。表１に示したように、得られたポリエチレン系樹脂は、曲げ弾性率、耐ストレスクラック性（定ひずみＥＳＣＲ）、成形性（溶融粘度）、揮発分、キャップブリッジ切れ性のいずれも良好であった。 It carried out similarly to [Example 1] using each component and comonomer shown in Table 1. As shown in Table 1, the obtained polyethylene resin had good bending elastic modulus, stress crack resistance (constant strain ESCR), moldability (melt viscosity), volatile matter, and cap bridge breakability. It was.
［比較例１］
成分（Ｂ）のみから成るＨＬＭＦＲ／ＭＦＲが小さく、引張り伸びが大きいポリエチレン系樹脂を用いて［実施例１］と同様に試験した。その結果、表２に示すように耐ストレスクラック性および流動性が不良であった。
[Comparative Example 1]
The test was performed in the same manner as in [Example 1] using a polyethylene resin having a small HLMFR / MFR composed of only the component (B) and a large tensile elongation. As a result, as shown in Table 2, the stress crack resistance and fluidity were poor.
［比較例２］
表２に示す成分（Ａ）、成分（Ｂ）の樹脂の配合比でヘンシェルミキサーで均一に混合後、押出機を用いて溶融混練してペレットを製造した。［実施例１］と同様に試験を行なった結果、ＨＬＭＦＲ、ＨＬＭＦＲ／ＭＦＲが小さく、耐ストレスクラック性、流動性が不良であった。
[Comparative Example 2]
After uniformly mixing with a Henschel mixer at the resin (A) and component (B) blending ratios shown in Table 2, pellets were produced by melting and kneading using an extruder. As a result of performing the test in the same manner as in [Example 1], HLMFR and HLMFR / MFR were small, and the stress crack resistance and fluidity were poor.
［比較例３］
［実施例１］の連続二段重合装置を用いて表２に示す成分（Ａ）、成分（Ｂ）を重合して樹脂を得た。得られた樹脂は表２に示すように密度が低く剛性が低かった。剛性が低いため、キャップの変形が起きた。
[Comparative Example 3]
Using the continuous two-stage polymerization apparatus of [Example 1], components (A) and (B) shown in Table 2 were polymerized to obtain a resin. As shown in Table 2, the obtained resin had low density and low rigidity. Due to the low rigidity, cap deformation occurred.
Claims (5)
（Ｂ）ＭＦＲが３０ｇ／１０ｍｉｎ以上、密度が０．９６１〜０．９８０ｇ／ｃｍ ３ のポリエチレン系樹脂５５質量部より多く９０質量部以下（Ａ＋Ｂ＝１００質量部）
からなる容器蓋用ポリエチレン系樹脂組成物であって、
以下のａ）〜ｆ）の性状を有することを特徴とする容器蓋用ポリエチレン系樹脂組成物。
ａ）ＭＦＲ（温度１９０℃において荷重２．１６Ｋｇで測定。以下同じ）が０．５〜１０ｇ／１０ｍｉｎであってＨＬＭＦＲ（温度１９０℃において荷重２１．６Ｋｇで測定。以下同じ）が１００〜５００ｇ／１０ｍｉｎであり、かつＨＬＭＦＲ／ＭＦＲが５０〜２００である、
ｂ）密度が０．９６０〜０．９８０ｇ／ｃｍ ３ 、
ｃ）射出成形試料の曲げ弾性率が１０００〜２０００ＭＰａ以上、
ｄ）射出成形試料の定ひずみＥＳＣＲが１０〜４０時間、
ｅ）引張破壊伸びが１００％以下、
ｆ）キャピラリーレオメーターによる２００℃のせん断速度２００ｓｅｃ−１の溶融粘度が４００Ｐａ・Ｓ以下。 (A) 10 to 10 parts by weight of a polyethylene resin having an HLMFR of more than 0.1 g / 10 min and not more than 10 g / 10 min and a density of 0.935 to 0.955 g / cm 3 , and (B) MFR of 30 g / 10 min or more and more than 55 parts by mass of polyethylene resin having a density of 0.961 to 0.980 g / cm 3 and 90 parts by mass or less (A + B = 100 parts by mass)
A polyethylene-based resin composition for container lids, comprising:
A polyethylene-based resin composition for container lids having the following properties a) to f).
a) MFR (measured at a load of 2.16 Kg at a temperature of 190 ° C., the same applies hereinafter) is 0.5 to 10 g / 10 min and HLMFR (measured at a load of 21.6 Kg at a temperature of 190 ° C., the same applies hereinafter) of 100 to 500 g / 10 min and HLMFR / MFR is 50-200,
b) a density of 0.960-0.980 g / cm 3 ,
c) The bending elastic modulus of the injection molded sample is 1000 to 2000 MPa or more,
d) Constant strain ESCR of the injection molded sample is 10 to 40 hours,
e) Tensile elongation at break of 100% or less,
f) Melt viscosity at 200 ° C. shear rate of 200 ° C.- 1 by a capillary rheometer is 400 Pa · S or less.
ｇ）炭化水素揮発分が８０ｐｐｍ以下、
ｈ）静摩擦係数が０．３５以下。 The polyethylene resin composition for container lids according to claim 1, further having the properties of the following requirements g) to h).
g) hydrocarbon volatiles of 80 ppm or less,
h) Static friction coefficient is 0.35 or less.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108602998A (en) * | 2014-11-07 | 2018-09-28 | 韩华道达尔有限公司 | Plastic bottle closure polyethylene resin composition and molded product prepared therefrom |
| CN108602998B (en) * | 2014-11-07 | 2021-01-05 | 韩华道达尔有限公司 | Polyethylene resin composition for plastic bottle caps and molded article produced therefrom |
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| JP2005320526A (en) | 2005-11-17 |
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