JP2011168737A - Foamed sheet and manufacturing method therefor - Google Patents
Foamed sheet and manufacturing method therefor Download PDFInfo
- Publication number
- JP2011168737A JP2011168737A JP2010035783A JP2010035783A JP2011168737A JP 2011168737 A JP2011168737 A JP 2011168737A JP 2010035783 A JP2010035783 A JP 2010035783A JP 2010035783 A JP2010035783 A JP 2010035783A JP 2011168737 A JP2011168737 A JP 2011168737A
- Authority
- JP
- Japan
- Prior art keywords
- density polyethylene
- foamed sheet
- high density
- melt
- extruder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 44
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 44
- 239000012968 metallocene catalyst Substances 0.000 claims abstract description 18
- 238000004898 kneading Methods 0.000 claims abstract description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000005977 Ethylene Substances 0.000 claims abstract 3
- 230000000379 polymerizing effect Effects 0.000 claims abstract 3
- 239000006260 foam Substances 0.000 claims description 24
- 229920001684 low density polyethylene Polymers 0.000 claims description 9
- 239000004702 low-density polyethylene Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims 1
- 238000003825 pressing Methods 0.000 claims 1
- 238000005187 foaming Methods 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 8
- 229920000573 polyethylene Polymers 0.000 abstract description 6
- 239000004698 Polyethylene Substances 0.000 abstract description 5
- -1 polyethylene Polymers 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 16
- 238000001816 cooling Methods 0.000 description 6
- 239000001273 butane Substances 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 239000004088 foaming agent Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920001748 polybutylene Polymers 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
本発明は、発泡シート及びその製造方法に関する。 The present invention relates to a foam sheet and a method for producing the same.
従来から、高密度ポリエチレンからなる様々な発泡シートやその製造方法が紹介されている。例えば、密度０．９４５ｇ／ｃｍ3以上の高密度ポリエチレン９５〜５０重量％と、ポリブテン−１を５〜５０重量％との混合組成物１００重量部に対して核形成物質０．０１〜５重量部を添加した混合物を押出機内で溶融可塑化し、揮発性発泡剤５〜５０重量部と均一に混合した後、冷却しつつ低圧帯へ押出すポリエチレン系発泡体の製造方法が紹介されている。（例えば、特許文献１参照） Conventionally, various foamed sheets made of high-density polyethylene and their production methods have been introduced. For example, a nucleation substance of 0.01 to 5% by weight with respect to 100 parts by weight of a mixed composition of 95 to 50% by weight of high density polyethylene having a density of 0.945 g / cm 3 or more and 5 to 50% by weight of polybutene-1. A method for producing a polyethylene foam that is melt-plasticized in an extruder and uniformly mixed with 5 to 50 parts by weight of a volatile foaming agent and then extruded into a low-pressure zone while cooling is introduced. (For example, see Patent Document 1)
また、密度０．９３５ｇ／ｃｍ3以上、融点１１７℃以上の高密度ポリエチレンから形成された径０．０５〜３ｍｍの微細気泡の集合体からなり、見かけ比重０．０１２〜０．１０、引張比強度１５０Ｋｇ／ｃｍ3以上、圧縮回復率８０％以上、加熱収縮率５０％以下である多泡質材料が紹介されている。（例えば、特許文献２参照） Further, it is composed of an aggregate of fine bubbles having a diameter of 0.05 to 3 mm formed from high density polyethylene having a density of 0.935 g / cm 3 or more and a melting point of 117 ° C. or more, and has an apparent specific gravity of 0.012 to 0.10 and a tensile ratio. A polyfoam material having a strength of 150 kg / cm 3 or more, a compression recovery rate of 80% or more, and a heat shrinkage rate of 50% or less has been introduced. (For example, see Patent Document 2)
そしてまた、密度０．９３５ｇ／ｃｍ3以上、融点１１７℃以上の高密度ポリエチレンから形成された径０．０５〜３ｍｍの微細気泡の集合体からなり、見かけ比重０．００６７以上、０．０１２未満、引張比強度１５０Ｋｇ／ｃｍ3以上、圧縮回復率８０％以上、加熱収縮率５０％以下である多泡質材料が紹介されている。（例えば、特許文献３参照） Further, it is an aggregate of fine bubbles having a diameter of 0.05 to 3 mm formed from high density polyethylene having a density of 0.935 g / cm 3 or more and a melting point of 117 ° C. or more, and has an apparent specific gravity of 0.0067 or more and less than 0.012. A multi-foam material having a tensile specific strength of 150 kg / cm 3 or more, a compression recovery rate of 80% or more, and a heat shrinkage rate of 50% or less is introduced. (For example, see Patent Document 3)
さらにまた、１−ブテン重合体８０〜９９重量％、エチレン重合体２０〜１重量％、及び発泡剤から構成される無架橋発泡体用組成物が紹介されている。（例えば、特許文献４参照） Furthermore, a composition for non-crosslinked foams composed of 80 to 99% by weight of 1-butene polymer, 20 to 1% by weight of ethylene polymer, and a foaming agent is introduced. (For example, see Patent Document 4)
また、高密度ポリエチレン２０〜９５重量％と、ポリブテン−１を５〜８０重量％と、前記高密度ポリエチレンとポリブテン−１との合計１００重量部に対して３〜３０重量部の発泡剤とを含有する組成物からなる高密度ポリエチレン架橋発泡体も紹介されている。（例えば、特許文献５参照） Further, 20 to 95% by weight of high density polyethylene, 5 to 80% by weight of polybutene-1, and 3 to 30 parts by weight of a foaming agent with respect to 100 parts by weight in total of the high density polyethylene and polybutene-1. A high density polyethylene cross-linked foam comprising the composition it contains is also introduced. (For example, see Patent Document 5)
特許文献１〜５に開示されている従来技術は、高密度ポリエチレンを製造する際に使用する触媒を選択することで、当該高密度ポリエチレン自身の特性を改良し、高密度ポリエチレン発泡体の発泡状態を容易にコントロールできるようにしたり、ブリードアウトやべたつきが少なく、低臭性、耐熱性、耐衝撃性を向上した発泡体を製造することについては何ら検討がなされていない。 The prior art disclosed in Patent Documents 1 to 5 improves the properties of the high-density polyethylene itself by selecting a catalyst to be used when producing the high-density polyethylene, and the foamed state of the high-density polyethylene foam No studies have been made on the production of foams that can be easily controlled, have low bleed out and stickiness, and have improved low odor, heat resistance, and impact resistance.
また、従来の高密度ポリエチレン発泡体は、通常、チーグラー触媒を使用して重合した高密度ポリエチレンを発泡させることで製造されているが、この従来の高密度ポリエチレンは、発泡に適した温度範囲が狭く、発泡状態のコントロールが困難である。また、チーグラー触媒を使用して重合した高密度ポリエチレンは、分子量分布が広く、低分子量が多いため、その成分がブリードアウトし易く、改良が望まれている。 In addition, conventional high-density polyethylene foam is usually produced by foaming high-density polyethylene polymerized using a Ziegler catalyst, but this conventional high-density polyethylene has a temperature range suitable for foaming. Narrow and difficult to control the foamed state. Further, high-density polyethylene polymerized using a Ziegler catalyst has a wide molecular weight distribution and a large amount of low molecular weight, so that its components are easy to bleed out, and improvement is desired.
本発明は、このような事情に鑑みなされたものであり、高密度ポリエチレンを製造する際に使用する触媒を選択することで、当該高密度ポリエチレン自身の特性を改良し、発泡に適する温度範囲が広く、発泡状態のコントロールが容易であると共に、ブリードアウトやべたつきが少なく且つ優れた低臭性を有し、耐熱性、耐衝撃性を向上することができる発泡シート及びその製造方法を提供することを目的とする。 The present invention has been made in view of such circumstances, and by selecting a catalyst to be used when producing high-density polyethylene, the characteristics of the high-density polyethylene itself are improved, and a temperature range suitable for foaming is To provide a foamed sheet that is easy to control the foamed state, has little bleeding out and stickiness, has excellent low odor, can improve heat resistance and impact resistance, and a method for producing the same. With the goal.
この目的を達成するため本発明は、メタロセン触媒を使用して重合した高密度ポリエチレンを含有してなる発泡シートを提供するものである。この構成を備えた発泡シートは、主鎖の均一性及び側鎖の分岐度を調整し易いため、発泡に適する温度範囲が広く、発泡状態を容易にコントロールすることができる。また、メタロセン触媒を使用して重合した高密度ポリエチレンは、例えば、従来のチーグラー触媒を使用して重合した高密度ポリエチレンに比べ、分子量分布が狭く、低分子量成分が少ないため、低分子量成分がブリードアウトすることを抑制することができる。また、べたつきが少なく、ブロッキングし難いと共に、ポリエチレン臭が少ない等、低臭性に優れた発泡シートを提供することができる。また、メタロセン触媒を使用して重合した高密度ポリエチレンは、ラメラが小さくタイ分子が大きいので、発泡シートの耐熱性、耐衝撃性を向上することができる。 In order to achieve this object, the present invention provides a foamed sheet comprising high-density polyethylene polymerized using a metallocene catalyst. Since the foam sheet having this configuration is easy to adjust the uniformity of the main chain and the branching degree of the side chain, the temperature range suitable for foaming is wide and the foamed state can be easily controlled. In addition, high-density polyethylene polymerized using a metallocene catalyst has a narrow molecular weight distribution and low low-molecular weight components compared to high-density polyethylene polymerized using conventional Ziegler catalysts. Out can be suppressed. In addition, it is possible to provide a foamed sheet that is less sticky, difficult to block, and has a low odor such as a low polyethylene odor. Moreover, since the high density polyethylene polymerized using the metallocene catalyst has a small lamella and a large tie molecule, the heat resistance and impact resistance of the foamed sheet can be improved.
また、本発明に係る発泡シートは、前記メタロセン触媒を使用して重合した高密度ポリエチレンのメルトテンションが、１〜１５ｇであることが好ましい。メルトテンションが、１ｇ未満であると、気泡サイズが大きくなると共に、良好な発泡を行うことが困難になる虞がある。一方、メルトテンションが、１５ｇを超えると、押出機に負荷がかかり易くなる等、製造が困難になる虞がある。 The foam sheet according to the present invention preferably has a melt tension of 1 to 15 g of high-density polyethylene polymerized using the metallocene catalyst. If the melt tension is less than 1 g, the bubble size may increase and it may be difficult to perform good foaming. On the other hand, when the melt tension exceeds 15 g, there is a possibility that the production becomes difficult, for example, a load is easily applied to the extruder.
また、本発明に係る発泡シートは、前記メタロセン触媒を使用して重合した高密度ポリエチレンのＭＦＲが、１．５〜１０ｇ／１０ｍｉｎであることが好ましい。ＭＦＲが、１．５ｇ／１０ｍｉｎ未満であると、発泡シートの製造時に圧力が高くなり、押出機に負荷がかかり易くなる等、製造が困難になる虞がある。一方、ＭＦＲが、１０ｇ／１０ｍｉｎを超えると、発泡シートの強度が低くなる等、物性が低下する虞がある。 Moreover, it is preferable that MFR of the high density polyethylene polymerized using the said metallocene catalyst is 1.5-10 g / 10min. If the MFR is less than 1.5 g / 10 min, the pressure becomes high during the production of the foamed sheet, and it may be difficult to produce such as being easy to apply a load to the extruder. On the other hand, if the MFR exceeds 10 g / 10 min, the physical properties may be lowered, for example, the strength of the foamed sheet is lowered.
さらにまた、本発明に係る発泡シートは、発泡倍率が、２〜５０倍であることが好ましい。発泡倍率が、２倍未満であると、発泡シートが硬くなり過ぎて、用途にもよるが、緩衝性が低下する虞がある。一方、発泡倍率が、５０倍を超えると、発泡シートが柔らかくなり過ぎて、用途にもよるが、破れ易くなる等、物性が低下する虞がある。 Furthermore, the foam sheet according to the present invention preferably has an expansion ratio of 2 to 50 times. If the expansion ratio is less than 2, the foam sheet becomes too hard, and there is a possibility that the buffering property may be lowered depending on the application. On the other hand, if the expansion ratio exceeds 50 times, the foam sheet becomes too soft, and depending on the application, the physical properties may be lowered, such as being easily broken.
そしてまた、本発明に係る発泡シートは、低密度ポリエチレンと、前記メタロセン触媒を使用して重合した高密度ポリエチレンとを溶融混練した混合物を含有してもよい。このように前記両ポリエチレンを溶融混練した混合物を含有することで、発泡シートの成形性が改善される。なお、低密度ポリエチレンを混合する場合は、発泡シートの物性を良好に維持するため、低密度ポリエチレンの混合率を４０％以下にすることが好ましい。 The foamed sheet according to the present invention may contain a mixture obtained by melt-kneading low density polyethylene and high density polyethylene polymerized using the metallocene catalyst. Thus, the moldability of a foam sheet is improved by containing the mixture which melt-kneaded both the said polyethylene. In addition, when mixing low density polyethylene, in order to maintain the physical property of a foam sheet favorably, it is preferable to make the mixing rate of low density polyethylene into 40% or less.
そしてまた、本発明に係る発泡シートは、密度が、０．９３５〜０．９６ｇ／ｃｍ3である。密度が、０．９３５ｇ／ｃｍ3未満であると、発泡シートの可撓性が高くなり過ぎて、当該発泡シートの腰が弱くなり、用途にもよるが、扱い難くなる虞がある。一方、密度が、０．９６ｇ／ｃｍ3を超えると、発泡シートの可撓性が低くなり過ぎて、当該発泡シートの腰が強くなり、用途にもよるが、扱い難くなる虞がある。 Moreover, the foamed sheet according to the present invention has a density of 0.935 to 0.96 g / cm 3 . When the density is less than 0.935 g / cm 3 , the flexibility of the foamed sheet becomes too high, and the foamed sheet becomes weak and may be difficult to handle depending on the application. On the other hand, when the density exceeds 0.96 g / cm 3 , the flexibility of the foamed sheet becomes too low, the foamed sheet becomes stiff, and depending on the application, it may be difficult to handle.
また、本発明は、メタロセン触媒を使用した高密度ポリエチレンを押出機に供給し、当該高密度ポリエチレンに揮発性ガスを圧入し、溶融混練する工程と、前記溶融混練された混練物を前記押出機から放出する工程と、前記放出された混練物を延伸する工程と、を備えた発泡シートの製造方法を提供するものである。 The present invention also includes a step of supplying high-density polyethylene using a metallocene catalyst to an extruder, press-fitting a volatile gas into the high-density polyethylene, melt-kneading, and the melt-kneaded kneaded product into the extruder. And a step of stretching the discharged kneaded product. A method for producing a foamed sheet is provided.
メタロセン触媒を使用して重合した高密度ポリエチレンは、例えば、従来のチーグラー触媒を使用して重合した高密度ポリエチレンに比べ、分子量分布が狭く、低分子量成分が少ないため、低分子量成分がブリードアウトすることを抑制することができる。また、べたつきが少なく、ブロッキングし難いと共に、ポリエチレン臭が少ない等、低臭性に優れている。 High-density polyethylene polymerized using a metallocene catalyst, for example, has a narrower molecular weight distribution and fewer low-molecular weight components than conventional high-density polyethylene polymerized using a Ziegler catalyst, so the low-molecular weight components bleed out. This can be suppressed. In addition, it is less sticky, difficult to block, and has low odor properties such as low polyethylene odor.
本発明に係る発泡シートは、メタロセン触媒を使用して重合した高密度ポリエチレンを含有しているため、発泡に適する温度範囲が広く、発泡状態のコントロールが容易であると共に、ブリードアウトやべたつきが少なく且つ優れた低臭性を有し、耐熱性、耐衝撃性を向上することができる。 Since the foamed sheet according to the present invention contains high-density polyethylene polymerized using a metallocene catalyst, the temperature range suitable for foaming is wide, the foamed state is easily controlled, and bleed-out and stickiness are low. In addition, it has excellent low odor and can improve heat resistance and impact resistance.
本発明に係る発泡シートの製造方法によれば、発泡状態を容易にコントロール可能であり、ブリードアウトやべたつきが少なく、低臭性に優れ、耐熱性、耐衝撃性を向上した発泡シートを提供することができる。 According to the method for producing a foamed sheet according to the present invention, a foamed sheet that can easily control the foamed state, has little bleed out and stickiness, is excellent in low odor, and has improved heat resistance and impact resistance is provided. be able to.
次に、本発明の実施形態に係る発泡シート及びその製造方法について説明する。 Next, the foam sheet and the manufacturing method thereof according to the embodiment of the present invention will be described.
メタロセン触媒を使用して重合した高密度ポリエチレンを押出機に供給し、シリンダーの途中より揮発性ガス（ブタン）を圧入し、約２３０℃で溶融混練し、当該押出機の口部先端に装着されたサーキュラダイスにより常圧下に放出し、環状冷却装置で所定の円周（実施例１では、幅が１１００ｍｍ）になるまで延伸した。その後、これを押出し方向に沿って切り開き、厚さ約１ｍｍ、発泡倍率３０倍の発泡シート（発明品１）を製作した。なお、発明品１の特性を表１に示す。 High density polyethylene polymerized using a metallocene catalyst is supplied to the extruder, volatile gas (butane) is injected from the middle of the cylinder, melted and kneaded at about 230 ° C, and attached to the tip of the mouth of the extruder. The product was discharged under normal pressure with a circular die and stretched to a predetermined circumference (in Example 1, the width was 1100 mm) with an annular cooling device. Then, this was cut open along the extrusion direction to produce a foam sheet (Invention 1) having a thickness of about 1 mm and a foaming ratio of 30 times. The characteristics of Invention 1 are shown in Table 1.
メタロセン触媒を使用して重合した高密度ポリエチレンと、密度０．９２５ｇ／ｃｍ3、メルトインデックス５．０の低密度ポリエチレン（ＬＤＰＥ）を、それぞれ７０：３０の割合で押出機に供給し、シリンダーの途中より揮発性ガス（ブタン）を圧入し、約２３０℃で溶融混練して口部先端に装着されたサーキュラダイスにより、常圧下に放出し、環状冷却装置で所定の円周（実施例２では、幅が１１００ｍｍ）になるまで延伸した。その後、これを押出方向に沿って切り開き、厚さ約２ｍｍ、発泡倍率１５倍の発泡シート（発明品２）を作製した。なお、発明品２の特性を表１に示す。 High density polyethylene polymerized using a metallocene catalyst and low density polyethylene (LDPE) having a density of 0.925 g / cm 3 and a melt index of 5.0 are fed to the extruder at a ratio of 70:30 respectively. A volatile gas (butane) is injected from the middle, melted and kneaded at about 230 ° C., and released under normal pressure by a circular die attached to the tip of the mouth, and a predetermined circumference (in Example 2) by an annular cooling device. And the width was 1100 mm). Then, this was cut open along the extrusion direction to produce a foam sheet (Invention product 2) having a thickness of about 2 mm and a foaming ratio of 15 times. Table 1 shows the characteristics of Invention Product 2.
メタロセン触媒を使用して重合した高密度ポリエチレンと、帯電防止剤（三洋化成工業：ペレスタット３００）を９０：１０の割合で押出機に供給し、シリンダーの途中より揮発性ガス（ブタン）を圧入し、約２３０℃で溶融混練して口部先端に装着されたサーキュラダイスにより、常圧下に放出し、環状冷却装置で所定の円周（実施例３では、幅が１１００ｍｍ）になるまで延伸した。その後、これを押出方向に沿って切り開き、厚さ約０．５ｍｍ、２５倍の発泡シート（発明品３）を作製した。なお、発明品３の特性を表１に示す。 A high-density polyethylene polymerized using a metallocene catalyst and an antistatic agent (Sanyo Kasei Kogyo: Pelestat 300) are supplied to the extruder at a ratio of 90:10, and volatile gas (butane) is injected from the middle of the cylinder. Then, it was discharged under normal pressure by a circular die that was melt-kneaded at about 230 ° C. and attached to the tip of the mouth, and stretched to a predetermined circumference (in Example 3, the width was 1100 mm) with an annular cooling device. Then, this was cut open along the extrusion direction, and a foamed sheet (Invention product 3) having a thickness of about 0.5 mm and 25 times was produced. The characteristics of Invention 3 are shown in Table 1.
メタロセン触媒を使用して重合した高密度ポリエチレンと、密度０．９２５ｇ／ｃｍ3、ＭＦＲ５．０の低密度ポリエチレン（ＬＤＰＥ）と、帯電防止剤（三洋化成工業：ペレスタット３００）を、それぞれ６０：３０：１０の割合で押出機に供給し、シリンダーの途中より揮発性ガス（ブタン）を圧入し、約２３０℃で溶融混練して口部先端に装着されたサーキュラダイスにより、常圧下に放出し、環状冷却装置で所定の円周（実施例４では、幅が１１００ｍｍ）になるまで延伸した。その後、これを押出方向に沿って切り開き、厚さ約１ｍｍ、発泡倍率１０倍の発泡シート（発明品４）を作製した。なお、発明品４の特性を表１に示す。 A high-density polyethylene polymerized using a metallocene catalyst, a low-density polyethylene (LDPE) with a density of 0.925 g / cm 3 and MFR 5.0, and an antistatic agent (Sanyo Chemical Industries: Pelestat 300), respectively, 60:30 : Supplied to the extruder at a ratio of 10, volatile gas (butane) is injected from the middle of the cylinder, melted and kneaded at about 230 ° C., and released under normal pressure by a circular die attached to the tip of the mouth, It extended | stretched until it became the predetermined | prescribed circumference (In Example 4, width is 1100 mm) with the annular cooling device. Thereafter, this was cut open along the extrusion direction to produce a foam sheet (Invention 4) having a thickness of about 1 mm and a foaming ratio of 10 times. The characteristics of Invention 4 are shown in Table 1.
［比較例１］
チーグラー触媒を使用して重合した高密度ポリエチレンを使用し、実施例１と同様の条件で発泡シートを製造することを試みたが、正常な特性を有する発泡シート（比較品１）を得ることができなかった。なお、比較品１の特性を表１に示す。
[Comparative Example 1]
An attempt was made to produce a foamed sheet under the same conditions as in Example 1 using high-density polyethylene polymerized using a Ziegler catalyst, but obtaining a foamed sheet (Comparative Product 1) having normal characteristics. could not. The characteristics of the comparative product 1 are shown in Table 1.
［比較例２〜４］
メタロセン触媒を使用して重合した高密度ポリエチレンを使用し、実施例１と同様の条件で発泡シートを製造することを試みたが、正常な特性を有する発泡シート（比較品２〜４）を得ることができなかった。なお、比較品２〜４の特性を表１に示す。
[Comparative Examples 2 to 4]
An attempt was made to produce a foamed sheet under the same conditions as in Example 1 using high-density polyethylene polymerized using a metallocene catalyst, but a foamed sheet (comparative products 2 to 4) having normal characteristics was obtained. I couldn't. Table 1 shows the characteristics of the comparative products 2 to 4.
表１から、発明品１〜４は、成形性に優れ、良好な発泡倍率を得ることができ、比較品１〜４は、発泡させることができず、発泡シートとしての機能を付与することができないことが判る。 From Table 1, the inventive products 1 to 4 are excellent in moldability and can obtain a good foaming ratio, and the comparative products 1 to 4 cannot be foamed and can give a function as a foam sheet. I understand that I can't.
次に、発明品１の加熱収縮率をＪＩＳ Ｋ ６７６７に準拠して測定した。なお、この測定の際に、発明品１は表２に示す温度で加熱した。また、加熱収縮率は、マシン方向（ＭＤ）及び幅方向（ＴＤ）について測定した。この結果を表２に示す。 Next, the heat shrinkage rate of Invention Product 1 was measured according to JIS K 6767. In this measurement, Invention 1 was heated at the temperature shown in Table 2. The heat shrinkage rate was measured in the machine direction (MD) and the width direction (TD). The results are shown in Table 2.
また、発明品１について、ヘッドスペース・ガスクロマトグラフ（ＨＳＧＣ）により、無極性成分のデータ及び極性成分のデータを測定した。なお、測定は、サンプル量を１ｇ重量換算とし、サンプルを８０℃で１時間加熱した後に発生した揮発物質を、島津キャピラリガスクロマトシステム（ＧＣ−２０１４）により測定し、ピークエリアを算出することで行った。この結果を図１及び図２に各々示す。 Moreover, about the invention product 1, the data of the nonpolar component and the data of the polar component were measured by the head space gas chromatograph (HSGC). Note that the measurement is performed by measuring the volatile matter generated after heating the sample at 80 ° C. for 1 hour using the Shimadzu capillary gas chromatographic system (GC-2014) by calculating the peak area by converting the sample amount to 1 g weight. went. The results are shown in FIGS. 1 and 2, respectively.
［比較例５］
次に、比較として、密度０．９２５ｇ／ｃｍ3、ＭＦＲ５．０の低密度ポリエチレンを押出機に供給し、シリンダーの途中より揮発性ガス（ブタン）を圧入し、約１６０℃で溶融混練し、当該押出機の口部先端に装着されたサーキュラダイスにより常圧下に放出し、環状冷却装置で所定の円周（比較例５では、幅が１１００ｍｍ）になるまで延伸した。その後、これを押出し方向に沿って切り開き、厚さ約１ｍｍ、発泡倍率３０倍の発泡シート（比較品５）を製作した。
[Comparative Example 5]
Next, as a comparison, low density polyethylene having a density of 0.925 g / cm 3 and MFR 5.0 is supplied to the extruder, volatile gas (butane) is injected from the middle of the cylinder, and melt-kneaded at about 160 ° C., The product was discharged under normal pressure by a circular die attached to the tip of the mouth of the extruder, and stretched to a predetermined circumference (in Comparative Example 5, the width was 1100 mm) with an annular cooling device. Then, this was cut open along the extrusion direction to produce a foam sheet (Comparative Product 5) having a thickness of about 1 mm and a foaming ratio of 30 times.
次に、比較品５について、発明品１と同様の方法で加熱収縮率を測定した。この結果を表２に示す。表２から、発明品１は、比較品５に比べ、加熱収縮率が小さく、寸法安定性に優れていることが判る。 Next, the heat shrinkage ratio of the comparative product 5 was measured by the same method as that of the inventive product 1. The results are shown in Table 2. From Table 2, it can be seen that Invention Product 1 has a smaller heat shrinkage and superior dimensional stability than Comparative Product 5.
また、比較品５について、発明品１と同様に、ヘッドスペース・ガスクロマトグラフ（ＨＳＧＣ）により、無極性成分のデータ及び極性成分のデータを測定した。この結果をこの結果を図１及び図２に各々示す。 Moreover, about the comparative product 5, similarly to the invention product 1, the data of the nonpolar component and the data of the polar component were measured by the head space gas chromatograph (HSGC). This result is shown in FIGS. 1 and 2, respectively.
図１及び図２から、発明品１は、比較品５に比べ、アウトガスが少ないことが判る。 From FIG. 1 and FIG. 2, it can be seen that the inventive product 1 has less outgas than the comparative product 5.
Claims (5)
前記溶融混練された混練物を前記押出機から放出する工程と、
前記放出された混練物を延伸する工程と、
を備えた発泡シートの製造方法。 Supplying a high density polyethylene obtained by polymerizing ethylene using a metallocene catalyst to an extruder, pressing a volatile gas into the high density polyethylene, and melt-kneading;
Discharging the melt-kneaded kneaded material from the extruder;
Stretching the discharged kneaded product;
The manufacturing method of the foam sheet provided with.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010035783A JP2011168737A (en) | 2010-02-22 | 2010-02-22 | Foamed sheet and manufacturing method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010035783A JP2011168737A (en) | 2010-02-22 | 2010-02-22 | Foamed sheet and manufacturing method therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2011168737A true JP2011168737A (en) | 2011-09-01 |
Family
ID=44683184
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2010035783A Pending JP2011168737A (en) | 2010-02-22 | 2010-02-22 | Foamed sheet and manufacturing method therefor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2011168737A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001505605A (en) * | 1996-12-05 | 2001-04-24 | モービル・オイル・コーポレーション | Foamed high density polyethylene |
| JP2004155454A (en) * | 2002-11-06 | 2004-06-03 | Japan Polyolefins Co Ltd | Insulating polyethylene container and method for producing the same |
| WO2009044690A1 (en) * | 2007-10-02 | 2009-04-09 | Sekisui Chemical Co., Ltd. | Stretched thermoplastic resin foam sheet and process for production of the same |
| JP2010242081A (en) * | 2009-03-19 | 2010-10-28 | Asahi Kasei Chemicals Corp | Polyethylene resin foam molded article, foam sheet, food packaging container, and method for producing the same |
| JP2011006626A (en) * | 2009-06-29 | 2011-01-13 | Tosoh Corp | Polyethylene open-cell foam and process for producing the same |
-
2010
- 2010-02-22 JP JP2010035783A patent/JP2011168737A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001505605A (en) * | 1996-12-05 | 2001-04-24 | モービル・オイル・コーポレーション | Foamed high density polyethylene |
| JP2004155454A (en) * | 2002-11-06 | 2004-06-03 | Japan Polyolefins Co Ltd | Insulating polyethylene container and method for producing the same |
| WO2009044690A1 (en) * | 2007-10-02 | 2009-04-09 | Sekisui Chemical Co., Ltd. | Stretched thermoplastic resin foam sheet and process for production of the same |
| JP2010242081A (en) * | 2009-03-19 | 2010-10-28 | Asahi Kasei Chemicals Corp | Polyethylene resin foam molded article, foam sheet, food packaging container, and method for producing the same |
| JP2010242056A (en) * | 2009-03-19 | 2010-10-28 | Asahi Kasei Chemicals Corp | Non-crosslinked extruded foam sheet made of polyethylene resin |
| JP2010242057A (en) * | 2009-03-19 | 2010-10-28 | Asahi Kasei Chemicals Corp | Glass substrate slip |
| JP2011006626A (en) * | 2009-06-29 | 2011-01-13 | Tosoh Corp | Polyethylene open-cell foam and process for producing the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5498162B2 (en) | Polypropylene resin foamed particles and molded articles thereof | |
| JP5873098B2 (en) | Method for producing foamable thermoplastic beads with improved foamability | |
| CN101469085B (en) | Polyolefin resin expanded particles | |
| JP6547628B2 (en) | Polyethylene-based resin foam particles, polyethylene-based resin in-mold foam molded article and method for producing the same | |
| JP7227526B1 (en) | Expanded polyethylene resin particles and method for producing the same | |
| JP5314411B2 (en) | Method for producing polypropylene resin expanded particle molded body, and molded body | |
| JP2019515112A (en) | Z-HFO-1336mzz blowing agent for foaming thermoplastic polymers containing polystyrene | |
| CN106604956A (en) | Expanded article, and expanded particles used to produce same | |
| JP5863531B2 (en) | Polyethylene resin composition for foaming and polyethylene resin foam sheet | |
| JP4157206B2 (en) | Polypropylene resin foamed particles and molded polypropylene resin foam particles | |
| TWI704175B (en) | Composite resin particle and expandable particle thereof, expanded particle and expanded molded article | |
| JP2010209224A (en) | Polyvinylidene fluoride resin expanded particle and polyvinylidene fluoride resin expanded particle molding | |
| JP6318655B2 (en) | Foam and production method thereof | |
| JP6961411B2 (en) | Polyethylene-based non-crosslinked extruded foam | |
| CN103881274A (en) | Polyvinylidene fluoride resin expanded beads, method for producing polyvinylidene fluoride resin expanded beads, and molded articles of polyvinylidene fluoride resin expanded beads | |
| JP2011168737A (en) | Foamed sheet and manufacturing method therefor | |
| JP7265528B2 (en) | Method for making foam beads using modified ethylene-based polymer | |
| WO2016147775A1 (en) | Polyethylene resin foam particles having antistatic performance, and polyethylene resin in-mold foam-molded article and method for manufacturing same | |
| JP7191117B2 (en) | foam particles | |
| JP6404164B2 (en) | Seed polymerization seed particles, composite resin particles, expandable particles, expanded particles, and composite resin foam moldings | |
| JP2016006142A (en) | Resin composition and foam comprising the same | |
| JP2018070735A (en) | Foamed particle and method for producing foamed particle molding | |
| JP3580357B2 (en) | Polypropylene resin foam sheet | |
| JPH03103449A (en) | Foamed low-density polyethylene resin and production thereof | |
| WO2015137353A1 (en) | Composite resin particles, foamable particles, pre-foamed particles, and foam molded body |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20130204 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20140109 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140114 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140313 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20140328 |