JP7473166B2 - Foam Resin Sheet - Google Patents
Foam Resin Sheet Download PDFInfo
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- JP7473166B2 JP7473166B2 JP2020057815A JP2020057815A JP7473166B2 JP 7473166 B2 JP7473166 B2 JP 7473166B2 JP 2020057815 A JP2020057815 A JP 2020057815A JP 2020057815 A JP2020057815 A JP 2020057815A JP 7473166 B2 JP7473166 B2 JP 7473166B2
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- antistatic agent
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- foamed resin
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- 229920005989 resin Polymers 0.000 title claims description 47
- 239000011347 resin Substances 0.000 title claims description 47
- 239000006260 foam Substances 0.000 title description 3
- 239000002216 antistatic agent Substances 0.000 claims description 68
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 229920000728 polyester Polymers 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- 229920000098 polyolefin Polymers 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 229920013716 polyethylene resin Polymers 0.000 claims description 9
- 229920005678 polyethylene based resin Polymers 0.000 claims description 8
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 229920001684 low density polyethylene Polymers 0.000 description 25
- 239000004702 low-density polyethylene Substances 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 23
- 238000004140 cleaning Methods 0.000 description 22
- 239000004721 Polyphenylene oxide Substances 0.000 description 15
- 229920000570 polyether Polymers 0.000 description 15
- 239000011521 glass Substances 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 239000004604 Blowing Agent Substances 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 6
- 239000004088 foaming agent Substances 0.000 description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- -1 and for example Polymers 0.000 description 5
- 230000000740 bleeding effect Effects 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000001282 iso-butane Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Landscapes
- Buffer Packaging (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
本発明は、表面保護用または包装用の発泡樹脂シートの改良、詳しくは、高温環境下における帯電防止剤のブリードアウトを抑制できる発泡樹脂シートに関するものである。 The present invention relates to an improvement to a foamed resin sheet for surface protection or packaging, specifically to a foamed resin sheet that can suppress the bleeding out of antistatic agents in high-temperature environments.
周知のとおり、クリーンルームで製造される液晶ディスプレイ用のガラス基板や半導体素子等の電子部品は、空気中の汚染物質によって表面が汚染されることにより品質の低下(リーク電流の増大等)を招き易いため、これらを運搬・保管する際には、ガラス基板や電子部品を表面保護シートや包装シートで覆って汚染物質から保護する必要がある。 As is well known, electronic components such as glass substrates for liquid crystal displays and semiconductor elements manufactured in clean rooms are susceptible to deterioration in quality (such as increased leakage current) due to surface contamination by airborne contaminants, so when transporting or storing these items, the glass substrates and electronic components must be covered with surface protective sheets or packaging sheets to protect them from contaminants.
また、上記表面保護用または包装用シートとしては、緩衝性に優れた発泡樹脂シートが好適に使用されるが、発泡樹脂シートは帯電して周囲の塵埃を引き寄せ易いため、帯電状態で保護シートを剥がしたり包装材を開封したりすると、引き寄せられた塵埃がガラス基板や電子部品に付着してガラス基板等の表面を汚染する問題が生じる。 In addition, foamed resin sheets with excellent cushioning properties are preferably used as the above-mentioned surface protection or packaging sheets. However, foamed resin sheets become electrically charged and tend to attract surrounding dust. Therefore, if the protective sheet is peeled off or the packaging material is opened while the sheet is in an electrically charged state, the attracted dust will adhere to the glass substrate or electronic components, causing the surface of the glass substrate, etc. to become contaminated.
そこで、従来においては、ポリオレフィン系の発泡樹脂シートに高分子型帯電防止剤を添加して上記表面汚染の問題を解消する技術も開発されているが(例えば、特許文献１参照)、この種の発泡樹脂シートでは、夏場の高温環境下において樹脂材料中に添加した帯電防止剤がシート表面にブリードアウトしてしまうという問題があった。 Therefore, a technology has been developed to solve the above-mentioned problem of surface contamination by adding a polymeric antistatic agent to a polyolefin-based foamed resin sheet (see, for example, Patent Document 1). However, this type of foamed resin sheet has the problem that the antistatic agent added to the resin material bleeds out onto the sheet surface in high temperature environments in summer.
また上記高分子型帯電防止剤を添加した発泡樹脂シートの場合、ブリードアウトしたシート表面の白粉(帯電防止剤)を蒸留水等で洗い流すことが難しかったため、白粉が残留した状態で発泡樹脂シートを使用せざるを得なかった。そのため、ガラス基板や半導体素子等の電子部品に白粉が付着して製品の品質低下を招く要因となった。 In addition, in the case of foamed resin sheets to which the above-mentioned polymer-type antistatic agent has been added, it was difficult to wash off the bleed-out white powder (antistatic agent) on the surface of the sheet with distilled water, etc., so the foamed resin sheet had to be used with the white powder remaining. As a result, the white powder adhered to electronic components such as glass substrates and semiconductor elements, causing a decrease in product quality.
本発明は、上記従来技術の問題を解決することを目的としており、要約すると優れた帯電防止機能を有し、更に高温環境下における帯電防止剤のブリードアウトを抑制することもでき、しかも、洗浄性にも優れた発泡樹脂シートを提供することにある。 The present invention aims to solve the problems of the conventional technology described above, and in summary, to provide a foamed resin sheet that has excellent antistatic properties, can suppress the bleed-out of antistatic agents in high-temperature environments, and is also easy to clean.
本発明者は、上記課題の解決手段として、ポリエチレン系樹脂を主成分とする発泡樹脂シートにおいて、帯電防止剤として、数平均分子量5000以上、かつ、シリコーン非含有のポリエステル系高分子型帯電防止剤をポリエチレン系樹脂100重量部に対して2.0重量部～8.0重量部添加すると共に、ＨＬＢ値が18以上の親水化剤をポリエチレン系樹脂100重量部に対して0.1～0.45重量部添加して、シートの表面固有抵抗値が1×108～1×1014Ωとなるようにした点に特徴がある。 As a means for solving the above problems, the inventors have added, to a foamed resin sheet mainly composed of polyethylene resin, 2.0 to 8.0 parts by weight of a non-silicone polyester-based polymer-type antistatic agent having a number average molecular weight of 5000 or more per 100 parts by weight of polyethylene resin as an antistatic agent, and 0.1 to 0.45 parts by weight of a hydrophilizing agent having an HLB value of 18 or more per 100 parts by weight of polyethylene resin, so that the surface resistivity of the sheet is 1 x 10 8 to 1 x 10 14 Ω.
また上記ポリエステル系高分子型帯電防止剤については、帯電防止効果を向上させるためにブリードし易い数平均分子量10000以上のものを使用するのが好ましい。 In addition, for the polyester-based polymer-type antistatic agent, it is preferable to use one with a number average molecular weight of 10,000 or more, which is easy to bleed, in order to improve the antistatic effect.
また上記ポリエステル系高分子型帯電防止剤については、帯電防止効果を向上させるためにブリードし易い融点80℃以上100℃未満のものを使用するのが好ましい。 In addition, for the polyester-based polymer-type antistatic agent, it is preferable to use one with a melting point of 80°C or higher but less than 100°C, which is prone to bleeding, in order to improve the antistatic effect.
また本発明では、上記ポリエステル系高分子型帯電防止剤に加えて、数平均分子量5000未満のポリオレフィン系高分子型帯電防止剤をポリエチレン系樹脂100重量部に対して0.05～1.0重量部添加し、かつ、前記ポリオレフィン系高分子型帯電防止剤の添加量をポリエステル系高分子型帯電防止剤の添加量よりも少なくすることによってコストダウンを図ることもできる。 In the present invention, in addition to the above-mentioned polyester-based polymer type antistatic agent, 0.05 to 1.0 part by weight of a polyolefin-based polymer type antistatic agent having a number average molecular weight of less than 5,000 is added per 100 parts by weight of the polyethylene-based resin, and the amount of the polyolefin-based polymer type antistatic agent added is made smaller than the amount of the polyester-based polymer type antistatic agent added, thereby achieving cost reduction.
また上記ポリオレフィン系高分子型帯電防止剤については、帯電防止効果の持続性を高めるためにブリードし難い融点100℃以上のものを使用するのが好ましい。 In addition, for the polyolefin-based polymer-type antistatic agent, it is preferable to use one with a melting point of 100°C or higher that is less likely to bleed in order to increase the durability of the antistatic effect.
また上記親水化剤については、洗浄性を向上させるためにＨＬＢ値の高いポリエチレングリコールを使用するのが好ましい。 As for the hydrophilizing agent, it is preferable to use polyethylene glycol with a high HLB value to improve cleaning properties.
本発明では、ポリエチレン系樹脂を主成分とする発泡樹脂シートにおいて、シリコーンを含有しないポリエステル系高分子型帯電防止剤を所定量添加することによって、優れた帯電防止機能が得られるだけでなく、夏場の高温環境下においても帯電防止剤のブリードアウト(白粉発生)を抑制することが可能となる。 In the present invention, by adding a specified amount of a polyester-based polymer-type antistatic agent that does not contain silicone to a foamed resin sheet whose main component is a polyethylene-based resin, not only is it possible to obtain excellent antistatic properties, but it is also possible to suppress the bleeding out (white powder generation) of the antistatic agent even in high-temperature environments in the summer.
また本発明では、発泡樹脂シートにＨＬＢ値が18以上の親水化剤も所定量添加しているため、発泡樹脂シートの表面に付着した汚れも蒸留水で洗い流すことが容易となる。また本発明では、ブリードアウトし難い帯電防止剤を使用しているため、洗浄性を向上させる親水化剤の添加量を抑制することもできる。 In addition, in the present invention, a specified amount of a hydrophilizing agent with an HLB value of 18 or more is added to the foamed resin sheet, so dirt adhering to the surface of the foamed resin sheet can be easily washed away with distilled water. In addition, in the present invention, an antistatic agent that does not easily bleed out is used, so the amount of hydrophilizing agent added to improve cleaning properties can be reduced.
次に、本発明を実施するための具体的態様及び好ましい条件について説明する Next, we will explain the specific aspects and preferred conditions for implementing the present invention.
[発泡樹脂シートの製造方法]
本発明の発泡樹脂シートは、ポリエチレン系樹脂を主成分とする主原料に、発泡剤、ポリエステル系高分子型帯電防止剤、及び親水化剤を添加し、これらの材料を押出成形機内に投入して加熱混練し、シート状(好ましくは厚さ0.2～2.0mmのシート状)に押出発泡成形して製造する。また帯電防止剤として、ポリエステル系高分子型帯電防止剤だけでなくポリオレフィン系高分子型帯電防止剤を併用することもできる。
[Method of manufacturing foam resin sheet]
The foamed resin sheet of the present invention is produced by adding a foaming agent, a polyester-based polymer-type antistatic agent, and a hydrophilizing agent to a main raw material mainly composed of a polyethylene-based resin, feeding these materials into an extrusion molding machine, kneading them under heat, and extruding and foaming them into a sheet (preferably a sheet having a thickness of 0.2 to 2.0 mm). As the antistatic agent, a polyolefin-based polymer-type antistatic agent can be used in combination with the polyester-based polymer-type antistatic agent.
[発泡樹脂シートの主材料]
本発明の発泡樹脂シートの主原料に関しては、ポリエチレン系樹脂を主成分とする樹脂であれば問題なく、例えば、低密度ポリエチレン(LDPE)や高密度ポリエチレン(HDPE)、これらの樹脂とポリエチレン系以外の樹脂を混ぜたもの等を採用することができる。その中でも特に密度0.90～0.93g/cm3の低密度ポリエチレンの使用が好ましい。
[Main material of foam resin sheet]
Regarding the main raw material of the foamed resin sheet of the present invention, there is no problem as long as the resin is mainly composed of a polyethylene-based resin, and for example, low-density polyethylene (LDPE), high-density polyethylene (HDPE), a mixture of these resins with a resin other than polyethylene-based resins, etc. Among them, the use of low-density polyethylene with a density of 0.90 to 0.93 g/cm3 is particularly preferable.
[発泡剤]
また上記発泡剤に関しては、プロパン、ノルマルブタン、イソブタン、ノルマルペンタン、イソペンタン、ノルマルヘキサン、イソヘキサン等の脂肪族炭化水素、シクロペンタン、シクロヘキサン等の脂環式炭化水素、塩化メチル、塩化エチル等の塩化炭化水素、1，1，1，2－テトラフロロエタン、1，1－ジフロロエタン等のフッ化炭化水素、ジメチル
エーテル、ジエチルエーテル、エチルエーテル等のエーテル類、ジメチルカーボネート、メタノール、エタノール等の有機系物理発泡剤、酸素、窒素、二酸化炭素、空気、水等の無機系発泡剤を好適に使用できる。またこれらの発泡剤は、単独または２種以上を混合して使用することもできる。
[Foaming agent]
As for the blowing agent, aliphatic hydrocarbons such as propane, normal butane, isobutane, normal pentane, isopentane, normal hexane, isohexane, etc., alicyclic hydrocarbons such as cyclopentane, cyclohexane, etc., chlorinated hydrocarbons such as methyl chloride, ethyl chloride, etc., fluorinated hydrocarbons such as 1,1,1,2-tetrafluoroethane, 1,1-difluoroethane, etc., ethers such as dimethyl ether, diethyl ether, ethyl ether, etc., organic physical blowing agents such as dimethyl carbonate, methanol, ethanol, etc., inorganic blowing agents such as oxygen, nitrogen, carbon dioxide, air, water, etc. can be suitably used. These blowing agents can be used alone or in combination of two or more.
また特に上記発泡剤の中でも、ポリエチレン系樹脂との相溶性、発泡性に優れた有機系物理発泡剤の使用が好ましく、具体的にはノルマルブタン、イソブタン、またはこれらの混合物を主成分とするものを使用することが好ましい。なお、物理発泡剤ではないがアゾジカルボンアミド等の分解型発泡剤も使用することができる。 Among the above blowing agents, it is particularly preferable to use organic physical blowing agents that have excellent compatibility with polyethylene resins and foaming properties, and specifically, it is preferable to use those whose main components are normal butane, isobutane, or a mixture of these. Although not a physical blowing agent, decomposition type blowing agents such as azodicarbonamide can also be used.
また、上記発泡剤の添加量は、発泡剤の種類、目的とする保護シートの密度に応じて調整する。具体的には、発泡剤としてイソブタンなどの物理発泡剤を採用する場合には、その配合比率を、ポリエチレン系樹脂100重量部当たり4～35重量部、好ましくは5～30重量部、より好ましくは6～25重量部とする。 The amount of the foaming agent added is adjusted according to the type of foaming agent and the desired density of the protective sheet. Specifically, when a physical foaming agent such as isobutane is used as the foaming agent, the blending ratio is 4 to 35 parts by weight, preferably 5 to 30 parts by weight, and more preferably 6 to 25 parts by weight per 100 parts by weight of the polyethylene resin.
[ポリエステル系高分子型帯電防止剤]
また上記ポリエステル系高分子型帯電防止剤に関しては、数平均分子量5000以上で、かつ、シリコーン非含有のものを使用する。またその中でも特にブリードし易い数平均分子量10000以上、融点80℃以上100℃未満のポリエーテルエステル系高分子型帯電防止剤を使用するのが好ましい。またポリエステル系高分子型帯電防止剤の添加量については、ポリエチレン系樹脂100重量部に対して2.0重量部～8.0重量部(好ましくは、3.0重量部～6.0重量部)の範囲内で添加する。
[Polyester-based polymeric antistatic agent]
The polyester-based polymer-type antistatic agent used has a number-average molecular weight of 5000 or more and is silicone-free. Among these, it is preferable to use a polyetherester-based polymer-type antistatic agent with a number-average molecular weight of 10000 or more and a melting point of 80° C. or more and less than 100° C., which is particularly prone to bleeding. The polyester-based polymer-type antistatic agent is added in an amount within the range of 2.0 to 8.0 parts by weight (preferably 3.0 to 6.0 parts by weight) per 100 parts by weight of the polyethylene resin.
[ポリオレフィン系高分子型帯電防止剤]
また上記ポリオレフィン系高分子型帯電防止剤に関しては、数平均分子量5000未満のポリオレフィン系高分子型帯電防止剤を使用する。またその中でも特にブリードし難い融点100℃以上のポリエーテルオレフィン系高分子型帯電防止剤を使用するのが好ましい。またポリオレフィン系高分子型帯電防止剤の添加量については、ポリエチレン系樹脂100重量部に対して0.05～1.0重量部(好ましくは、0.1重量部～0.3重量部)の範囲内で添加して、ポリエステル系高分子型帯電防止剤の添加量よりも少なくする。
[Polyolefin-based polymer-type antistatic agent]
As for the polyolefin-based polymer-type antistatic agent, a polyolefin-based polymer-type antistatic agent with a number average molecular weight of less than 5000 is used. Among them, it is preferable to use a polyetherolefin-based polymer-type antistatic agent with a melting point of 100° C. or more, which is particularly difficult to bleed. The amount of the polyolefin-based polymer-type antistatic agent added is within the range of 0.05 to 1.0 part by weight (preferably 0.1 to 0.3 part by weight) per 100 parts by weight of the polyethylene resin, which is less than the amount of the polyester-based polymer-type antistatic agent added.
[親水化剤]
また上記親水化剤については、ＨＬＢ値18以上(好ましくはＨＬＢ値19以上)の界面活性剤を使用する。その中でも特にＨＬＢ値の高いポリエチレングリコールを使用することが好ましい。また親水化剤の添加量については、ポリエチレン系樹脂100重量部に対して0.1～0.45重量部の範囲内で添加する。
[Hydrophilic agent]
As for the hydrophilizing agent, a surfactant with an HLB value of 18 or more (preferably an HLB value of 19 or more) is used. Among them, it is preferable to use polyethylene glycol, which has a particularly high HLB value. The amount of the hydrophilizing agent added is within the range of 0.1 to 0.45 parts by weight per 100 parts by weight of the polyethylene resin.
[シートの表面固有抵抗値]
本発明の発泡樹脂シートは、シートの表面固有抵抗値が1×108～1×1014Ω、好ましくは1×109～1×1012Ω、より好ましくは1×1010～1×1011Ωとなるようにする。なお本発明における「表面固有抵抗値」は、JIS C 1303:1972（高絶縁抵抗計）に準拠する表面抵抗測定装置を用いて測定された値である。
[Surface resistivity of sheet]
The foamed resin sheet of the present invention has a surface resistivity of 1×10 8 to 1×10 14 Ω, preferably 1×10 9 to 1×10 12 Ω, and more preferably 1×10 10 to 1×10 11 Ω. The "surface resistivity" in the present invention is a value measured using a surface resistance measuring device conforming to JIS C 1303:1972 (high insulation resistance meter).
［その他の添加剤］
また本発明の発泡樹脂シートを製造する際に、気泡力を高めたり抑えたりする気泡調整剤を添加することもでき、この気泡調整剤には有機系(ポリテトラフルオロエチレンなど)のものや無機系のものを適宜選択できる。また必要に応じて、着色剤、紫外線防止剤、酸化防止剤などの種々の添加剤を使用することもできる。
[Other additives]
In addition, when producing the foamed resin sheet of the present invention, a bubble control agent that increases or decreases the bubble power can be added, and the bubble control agent can be appropriately selected from organic (such as polytetrafluoroethylene) and inorganic types. In addition, various additives such as colorants, ultraviolet inhibitors, and antioxidants can be used as necessary.
[効果の実証試験]
次に本発明の効果の実証試験について説明する。本試験では、帯電防止剤の種類及び添加量、親水化剤の添加量が異なる発泡樹脂シートのサンプルを複数作製し、これら各サンプル(下記の実施例１～４及び比較例１～２)の表面固有抵抗値および洗浄前後の接触角の測定を行い、洗浄後における呼気試験の評価を行った。
[Demonstration test of effectiveness]
Next, a demonstration test of the effect of the present invention will be described. In this test, a number of foamed resin sheet samples were prepared with different types and amounts of antistatic agents and different amounts of hydrophilizing agents, and the surface resistivity and contact angle before and after cleaning of each of these samples (Examples 1 to 4 and Comparative Examples 1 and 2 described below) were measured, and a breath test after cleaning was performed to evaluate the results.
「実施例１」
本実施例では、発泡樹脂シートの主原料に低密度ポリエチレン(96.1wt％)を使用する一方、帯電防止剤としてポリエーテルエステル系高分子型帯電防止剤を低密度ポリエチレン100重量部に対し3.6重量部(3.5wt％)添加すると共に、親水化剤としてポリエチレングリコールを低密度ポリエチレン100重量部に対し0.4重量部(0.4wt％)添加した。またポリエーテルエステル系高分子型帯電防止剤には、融点93℃、数平均分子量19100のものを使用した。
"Example 1"
In this example, low-density polyethylene (96.1 wt%) was used as the main raw material of the foamed resin sheet, while 3.6 parts by weight (3.5 wt%) of a polyether ester-based high-molecular-weight antistatic agent was added to 100 parts by weight of low-density polyethylene as an antistatic agent, and 0.4 parts by weight (0.4 wt%) of polyethylene glycol was added to 100 parts by weight of low-density polyethylene as a hydrophilizing agent. The polyether ester-based high-molecular-weight antistatic agent used had a melting point of 93°C and a number-average molecular weight of 19,100.
「実施例３」
本実施例では、発泡樹脂シートの主原料に低密度ポリエチレン(95.6wt％)を使用する一方、帯電防止剤としてポリエーテルエステル系高分子型帯電防止剤を低密度ポリエチレン100重量部に対し5.3重量部(5.0wt％)添加すると共に、親水化剤としてポリエチレングリコールを低密度ポリエチレン100重量部に対し0.4重量部(0.4wt％)添加した。またポリエーテルエステル系高分子型帯電防止剤には、融点93℃、数平均分子量19100のものを使用した。
" Example 3 "
In this example, low-density polyethylene (95.6 wt%) was used as the main raw material of the foamed resin sheet, while 5.3 parts by weight (5.0 wt%) of a polyether ester-based high-molecular-weight antistatic agent was added to 100 parts by weight of low-density polyethylene as an antistatic agent, and 0.4 parts by weight (0.4 wt%) of polyethylene glycol was added to 100 parts by weight of low-density polyethylene as a hydrophilizing agent. The polyether ester-based high-molecular-weight antistatic agent used had a melting point of 93°C and a number-average molecular weight of 19,100.
「実施例２」
本実施例では、発泡樹脂シートの主原料に低密度ポリエチレン(94.6wt％)を使用する一方、帯電防止剤としてポリエーテルエステル系高分子型帯電防止剤を低密度ポリエチレン100重量部に対し4.2重量部(4.0wt％)添加すると共に、親水化剤としてポリエチレングリコールを低密度ポリエチレン100重量部に対し0.4重量部(0.4wt％)添加した。またポリエーテルエステル系高分子型帯電防止剤には、融点93℃、数平均分子量19100のものを使用した。
" Example 2 "
In this example, low-density polyethylene (94.6 wt%) was used as the main raw material of the foamed resin sheet, while 4.2 parts by weight (4.0 wt%) of a polyether ester-based high-molecular-weight antistatic agent was added to 100 parts by weight of low-density polyethylene as an antistatic agent, and 0.4 parts by weight (0.4 wt%) of polyethylene glycol was added to 100 parts by weight of low-density polyethylene as a hydrophilizing agent. The polyether ester-based high-molecular-weight antistatic agent used had a melting point of 93°C and a number-average molecular weight of 19,100.
「実施例４」
本実施例では、発泡樹脂シートの主原料に低密度ポリエチレン(94.3wt％)を使用する一方、帯電防止剤としてポリエーテルエステル系高分子型帯電防止剤を低密度ポリエチレン100重量部に対し5.3重量部(5.0wt％)、ポリエーテルオレフィン系高分子型帯電防止剤を低密度ポリエチレン100重量部に対し0.1重量部(0.1wt％)添加し、親水化剤としてポリエチレングリコールを低密度ポリエチレン100重量部に対し0.4重量部(0.4wt％)添加した。またポリエーテルエステル系高分子型帯電防止剤には、融点93℃、数平均分子量19100のものを使用し、ポリエーテルオレフィン系高分子型帯電防止剤には、融点136℃、数平均分子量14000のものを使用した。
"Example 4"
In this embodiment, low-density polyethylene (94.3 wt%) was used as the main raw material of the foamed resin sheet, while 5.3 parts by weight (5.0 wt%) of a polyether ester-based polymer-type antistatic agent was added to 100 parts by weight of low-density polyethylene as an antistatic agent, 0.1 parts by weight (0.1 wt%) of a polyether olefin-based polymer-type antistatic agent was added to 100 parts by weight of low-density polyethylene as an antistatic agent, and 0.4 parts by weight (0.4 wt%) of polyethylene glycol was added to 100 parts by weight of low-density polyethylene as a hydrophilizing agent. The polyether ester-based polymer-type antistatic agent had a melting point of 93°C and a number average molecular weight of 19100, and the polyether olefin-based polymer-type antistatic agent had a melting point of 136°C and a number average molecular weight of 14000.
「比較例１」
本比較例では、発泡樹脂シートの主原料に低密度ポリエチレン(91.6wt％)を使用する一方、帯電防止剤としてポリエーテルオレフィン系高分子型帯電防止剤を低密度ポリエチレン100重量部に対し8.7重量部(8.0wt％)添加すると共に、親水化剤としてポリエチレングリコールを低密度ポリエチレン100重量部に対し0.4重量部(0.4wt％)添加した。またポリエーテルオレフィン系高分子型帯電防止剤には、融点136℃、数平均分子量14000のものを使用した。
"Comparative Example 1"
In this comparative example, low-density polyethylene (91.6 wt%) was used as the main raw material of the foamed resin sheet, while 8.7 parts by weight (8.0 wt%) of a polyetherolefin-based polymer-type antistatic agent was added to 100 parts by weight of the low-density polyethylene as an antistatic agent, and 0.4 parts by weight (0.4 wt%) of polyethylene glycol was added to 100 parts by weight of the low-density polyethylene as a hydrophilizing agent. The polyetherolefin-based polymer-type antistatic agent used had a melting point of 136°C and a number-average molecular weight of 14,000.
「比較例２」
本比較例では、発泡樹脂シートの主原料に低密度ポリエチレン(92.0wt％)を使用する一方、帯電防止剤としてポリエーテルオレフィン系高分子型帯電防止剤を低密度ポリエチレン100重量部に対し8.7重量部(8.0wt％)添加した。また本比較例では、親水化剤を添加せず、ポリエーテルオレフィン系高分子型帯電防止剤に融点136℃、数平均分子量14000のものを使用した。
"Comparative Example 2"
In this comparative example, low-density polyethylene (92.0 wt%) was used as the main raw material of the foamed resin sheet, while 8.7 parts by weight (8.0 wt%) of a polyether olefin-based polymer-type antistatic agent was added to 100 parts by weight of the low-density polyethylene as an antistatic agent. In this comparative example, no hydrophilizing agent was added, and a polyether olefin-based polymer-type antistatic agent with a melting point of 136°C and a number-average molecular weight of 14,000 was used.
「比較例３」
本比較例では、発泡樹脂シートの主原料に低密度ポリエチレン(92.6wt％)を使用する一方、帯電防止剤としてポリエーテルエステル系高分子型帯電防止剤を低密度ポリエチレン100重量部に対し5.4重量部(5.0wt％)、ポリエーテルオレフィン系高分子型帯電防止剤を低密度ポリエチレン100重量部に対し2.2重量部(2.0wt％)添加し、親水化剤としてポリエチレングリコールを低密度ポリエチレン100重量部に対し0.4重量部(0.4wt％)添加した。また本比較例では、ポリエーテルオレフィン系高分子型帯電防止剤に融点136℃、数平均分子量14000のものを使用した。
In this comparative example, low-density polyethylene (92.6 wt%) was used as the main raw material of the foamed resin sheet, while 5.4 parts by weight (5.0 wt%) of a polyether ester-based polymer-type antistatic agent was added to 100 parts by weight of low-density polyethylene as an antistatic agent, 2.2 parts by weight (2.0 wt%) of a polyether olefin-based polymer-type antistatic agent was added to 100 parts by weight of low-density polyethylene as an antistatic agent, and 0.4 parts by weight (0.4 wt%) of polyethylene glycol was added to 100 parts by weight of low-density polyethylene as a hydrophilizing agent. In this comparative example, the polyether olefin-based polymer-type antistatic agent used had a melting point of 136°C and a number-average molecular weight of 14,000.
＜表面固有抵抗値の測定＞
本試験では、上記実施例１～４及び比較例１～２の発泡樹脂シートを、温度20℃、相対湿度65％の条件下で24時間調湿した後、表面抵抗値測定装置（超絶縁計SM-8220 HIOKI社製）を用いて各発泡シートの表面固有抵抗値を測定した。なお表面抵抗値測定装置は、JIS C 1303:1972（高絶縁抵抗計）に準拠している。
<Measurement of Surface Resistivity>
In this test, the foamed resin sheets of Examples 1 to 4 and Comparative Examples 1 and 2 were conditioned for 24 hours under conditions of a temperature of 20°C and a relative humidity of 65%, and then the surface resistivity of each foamed sheet was measured using a surface resistance measuring device (Super Insulation Meter SM-8220, manufactured by HIOKI Corporation). The surface resistance measuring device complies with JIS C 1303:1972 (High Insulation Resistance Meter).
[測定結果]
その結果、各発泡樹脂シートの表面固有抵抗値は、実施例１：8．7×1010Ω、実施例２：7．8×1010Ω、実施例３：2．4×1010Ω、実施例４：9.6×1010Ω、比較例１；3．3×1011Ω、比較例２：3．3×1011Ω、比較例３：1．4×1015Ωとなり、実施例１～４の方が比較例１～３よりも表明固有抵抗値が小さいことが確認できた。
[Measurement result]
As a result, the surface resistivity values of each foamed resin sheet were as follows: Example 1: 8.7×10 10 Ω, Example 2: 7.8×10 10 Ω, Example 3: 2.4×10 10 Ω, Example 4: 9.6×10 10 Ω, Comparative Example 1: 3.3×10 11 Ω, Comparative Example 2: 3.3×10 11 Ω, Comparative Example 3: 1.4×10 15 Ω. It was confirmed that Examples 1 to 4 had smaller surface resistivity values than Comparative Examples 1 to 3.
＜洗浄前後の接触角の測定＞
本試験では、上記実施例１～４及び比較例１～２の発泡樹脂シート(寸法：15cm×15cm)を、同サイズのガラス板の上に乗せ、更にその上に5kgの重りを乗せて、恒温恒湿槽(CSH-111 エスペック社製)内で加速試験を行なった。またシートの加熱は、(１)20℃・60％ＲＨから60℃・90％ＲＨまで1時間で昇温、(２)60℃・90％ＲＨで1時間保持、(３)60℃・90％ＲＨから20℃・60％ＲＨまで1時間で降温、(４)20℃・60％ＲＨで1時間保持、を1サイクルとして90サイクル行なった。
<Measurement of contact angle before and after cleaning>
In this test, the foamed resin sheets (dimensions: 15 cm x 15 cm) of Examples 1 to 4 and Comparative Examples 1 and 2 were placed on a glass plate of the same size, and a weight of 5 kg was placed on top of that, and an accelerated test was performed in a thermo-hygrostat (CSH-111, manufactured by Espec Corp.) The sheets were heated in 90 cycles, with one cycle consisting of (1) increasing the temperature from 20°C and 60% RH to 60°C and 90% RH in one hour, (2) maintaining the temperature at 60°C and 90% RH for one hour, (3) decreasing the temperature from 60°C and 90% RH to 20°C and 60% RH in one hour, and (4) maintaining the temperature at 20°C and 60% RH for one hour.
また上記加速試験を行った後、ガラス板を蒸留水で洗浄し、温度30℃、相対湿度0％にて24時間乾燥した。そして、洗浄前と洗浄後のガラス板表面における蒸留水の接触角を接触角計（品番：DMs-601、協和界面科学（株）製）を用いて測定した。 After the accelerated test, the glass plate was washed with distilled water and dried for 24 hours at a temperature of 30°C and a relative humidity of 0%. The contact angle of distilled water on the glass plate surface before and after washing was measured using a contact angle meter (model number: DMs-601, manufactured by Kyowa Interface Science Co., Ltd.).
[測定結果]
その結果、各発泡樹脂シートの接触角は、実施例１：24.3度(洗浄前)4.1度(洗浄後)、実施例２：24.8度(洗浄前)4.4度(洗浄後)、実施例３：25.6度(洗浄前)4.3度(洗浄後)、実施例４：25.9度(洗浄前)4.4度(洗浄後)、比較例１：29.6度(洗浄前)5.0度(洗浄後)、比較例２：38.9度(洗浄前)13.6度(洗浄後)となった。これにより実施例１～４の方が比較例１～２よりも洗浄前の接触角が小さく、高温環境化におけるブリードアウトが抑えられていることが確認できた。また洗浄後の接触角に関しても、実施例１～実施例４の方が比較例１～２よりも小さく、ブリードアウトした帯電防止剤の洗浄性に優れていることが確認できた。
[Measurement result]
As a result, the contact angles of each foamed resin sheet were as follows: Example 1: 24.3 degrees (before cleaning) 4.1 degrees (after cleaning), Example 2: 24.8 degrees (before cleaning) 4.4 degrees (after cleaning), Example 3: 25.6 degrees (before cleaning) 4.3 degrees (after cleaning), Example 4: 25.9 degrees (before cleaning) 4.4 degrees (after cleaning), Comparative Example 1: 29.6 degrees (before cleaning) 5.0 degrees (after cleaning), Comparative Example 2: 38.9 degrees (before cleaning) 13.6 degrees (after cleaning). This confirmed that Examples 1 to 4 had smaller contact angles before cleaning than Comparative Examples 1 and 2, and that bleeding out in a high temperature environment was suppressed. In addition, with regard to the contact angles after cleaning, Examples 1 to 4 were smaller than Comparative Examples 1 and 2, and it was confirmed that the cleaning properties of the bleed-out antistatic agent were excellent.
＜洗浄後における呼気試験＞
本試験では、上記洗浄後の実施例１～４及び比較例１～２の発泡樹脂シートについて、温度23℃、相対湿度50％の室内で発泡樹脂シートを載せたガラス表面に息を吹きかけ、曇りの状態を目視によって観察し、次の基準にて判定した。○：曇らない、△：やや曇りが見られる、×：全面が曇る
<Breath test after washing>
In this test, for the foamed resin sheets of Examples 1 to 4 and Comparative Examples 1 and 2 after the above cleaning, breath was blown onto the glass surface on which the foamed resin sheet was placed in a room at a temperature of 23°C and a relative humidity of 50%, and the state of fogging was visually observed and rated according to the following criteria: ◯: no fogging, △: some fogging observed, ×: fogging over the entire surface.
[評価結果]
その結果、実施例１～４の発泡樹脂シートを載せたガラス表面は何れも曇らなかったのに対し、比較例１の発泡樹脂シートを載せたガラス表面は少し曇りが見られ、また比較例２の発泡樹脂シートを載せたガラス表面は全面に曇りが見られた。これにより実施例１～実施例４の方が比較例１～２よりもブリードアウトした帯電防止剤の洗浄性に優れていることが確認できた。上記試験の結果をまとめた表を以下に示す。
As a result, none of the glass surfaces on which the foamed resin sheets of Examples 1 to 4 were placed became cloudy, whereas the glass surface on which the foamed resin sheet of Comparative Example 1 was placed became slightly cloudy, and the glass surface on which the foamed resin sheet of Comparative Example 2 was placed became cloudy over the entire surface. This confirmed that Examples 1 to 4 were better at cleaning the bled-out antistatic agent than Comparative Examples 1 and 2. The results of the above tests are summarized in a table below.
Claims (5)
帯電防止剤として、数平均分子量5000以上、かつ、シリコーン非含有のポリエステル系高分子型帯電防止剤がポリエチレン系樹脂100重量部に対して2.0重量部～8.0重量部添加されると共に、このポリエステル系高分子型帯電防止剤に加えて、ポリオレフィン系高分子型帯電防止剤がポリエチレン系樹脂100重量部に対して0.05～0.3重量部添加されると共に、ＨＬＢ値が18以上の親水化剤がポリエチレン系樹脂100重量部に対して0.1～0.45重量部添加されており、シートの表面固有抵抗値が1×10 8 ～1×10 12 Ωであることを特徴とする発泡樹脂シート。 In a foamed resin sheet mainly composed of a polyethylene resin,
A foamed resin sheet comprising an antistatic agent, which is a polyester-based polymer-type antistatic agent having a number average molecular weight of 5000 or more and not containing silicone , added in an amount of 2.0 to 8.0 parts by weight per 100 parts by weight of polyethylene-based resin, and in addition to this polyester-based polymer-type antistatic agent, which is a polyolefin-based polymer-type antistatic agent, added in an amount of 0.05 to 0.3 part by weight per 100 parts by weight of polyethylene-based resin , and which is a hydrophilizing agent having an HLB value of 18 or more, added in an amount of 0.1 to 0.45 part by weight per 100 parts by weight of polyethylene-based resin, and which has a surface resistivity of 1×10 8 to 1×10 12 Ω .
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003512487A (en) | 1999-10-18 | 2003-04-02 | アトフィナ | Polyetheresteramide and antistatic polymer composition containing the same |
| JP2008303298A (en) | 2007-06-07 | 2008-12-18 | Jsp Corp | Polyolefin resin extrusion foamed sheet, and glass substrate interleaving paper and glass susbtrate packaging material including the foamed sheet |
| JP2014136755A (en) | 2013-01-17 | 2014-07-28 | Sekisui Plastics Co Ltd | Polyethylene-based resin foamed sheet |
| JP2016169330A (en) | 2015-03-13 | 2016-09-23 | 積水化成品工業株式会社 | Polyethylene resin foam sheet |
| JP2017095593A (en) | 2015-11-24 | 2017-06-01 | 酒井化学工業株式会社 | Polyethylene foam resin sheet |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003512487A (en) | 1999-10-18 | 2003-04-02 | アトフィナ | Polyetheresteramide and antistatic polymer composition containing the same |
| JP2008303298A (en) | 2007-06-07 | 2008-12-18 | Jsp Corp | Polyolefin resin extrusion foamed sheet, and glass substrate interleaving paper and glass susbtrate packaging material including the foamed sheet |
| JP2014136755A (en) | 2013-01-17 | 2014-07-28 | Sekisui Plastics Co Ltd | Polyethylene-based resin foamed sheet |
| JP2016169330A (en) | 2015-03-13 | 2016-09-23 | 積水化成品工業株式会社 | Polyethylene resin foam sheet |
| JP2017095593A (en) | 2015-11-24 | 2017-06-01 | 酒井化学工業株式会社 | Polyethylene foam resin sheet |
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| JP2021155574A (en) | 2021-10-07 |
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