TW202003219A - Polyolefin resin laminated foam sheet and spacer paper for glass plates composed of the same capable of providing excellent washability for packaged objects such as glass plates even under high temperature and humidity - Google Patents

Polyolefin resin laminated foam sheet and spacer paper for glass plates composed of the same capable of providing excellent washability for packaged objects such as glass plates even under high temperature and humidity Download PDF

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TW202003219A
TW202003219A TW108107854A TW108107854A TW202003219A TW 202003219 A TW202003219 A TW 202003219A TW 108107854 A TW108107854 A TW 108107854A TW 108107854 A TW108107854 A TW 108107854A TW 202003219 A TW202003219 A TW 202003219A
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polyethylene glycol
surface layer
mass
foam sheet
parts
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TW108107854A
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Chinese (zh)
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TWI779172B (en
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岩崎聰
西本敬
竹内亮平
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日商Ｊｓｐ 股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/025—Polyolefin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00—Polyalkenes
    • B32B2323/04—Polyethylene
    • B32B2323/046—LDPE, i.e. low density polyethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Laminated Bodies (AREA)
  • Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
  • Buffer Packaging (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Packaging Frangible Articles (AREA)

Abstract

The invention provides a laminated foam sheet and a spacer sheet for glass plates using the same. The laminated foam sheet of the invention may be used as a laminated foam sheet that can be used as spacer paper for glass plates, and may provide excellent washability for packaged objects such as glass plates even under high temperature and humidity. The solution of the invention is a laminated foam sheet, which has a polyolefin resin foam layer and a polyolefin resin surface layer next laminated on at least one side of the foam layer, wherein the surface layer is blended with polyethylene glycol (PEG). The aforementioned polyethylene glycol (PEG) is composed of first polyethylene glycol (PEG1) being liquid at 25 DEG C and second polyethylene glycol (PEG2) being solid at 25 DEG C. With respect to the polyolefin resin composing the surface layer as 100 mass portions, the blending amount of first polyethylene glycol (PEG1) in the surface layer is above 0.5 mass portions and below 10 mass portions. With respect to the blending amount of first polyethylene glycol (PEG1) in the surface layer as 100 mass portions, the blending amount of second polyethylene glycol (PEG2) in the surface layer is above 3 mass portions.

Description

聚烯烴系樹脂積層發泡片材及由該積層發泡片材構成之玻璃板用間隔紙Polyolefin-based resin laminated foamed sheet and spacer paper for glass plate composed of the laminated foamed sheet

發明領域 本發明涉及一種聚烯烴系樹脂積層發泡片材及由該積層發泡片材構成之玻璃板用間隔紙。Field of invention The present invention relates to a polyolefin-based resin laminated foam sheet and a spacer for a glass plate composed of the laminated foam sheet.

發明背景 聚烯烴系樹脂積層發泡片材具優異的柔軟性及緩衝性，可防止被包裝物損傷、刮傷等。所以，該積層發泡片材長久以來廣泛作為家電製品、玻璃器具、陶器等之包裝材使用。而且，近幾年隨著薄型電視之開發及需求擴大，聚烯烴系樹脂積層發泡片材也開始廣泛作為液晶顯示器、電漿顯示器、用於電致發光顯示器等顯示面板之製造或運輸的玻璃板用間隔紙使用。Background of the invention The polyolefin-based resin laminated foam sheet has excellent flexibility and cushioning properties, and can prevent damage and scratching of the packaged object. Therefore, the laminated foam sheet has long been widely used as packaging materials for household appliances, glassware, pottery, and the like. In addition, in recent years, with the development and demand expansion of thin TVs, polyolefin-based resin laminated foam sheets have also been widely used as glass for the manufacture or transportation of display panels such as liquid crystal displays, plasma displays, and electroluminescent displays. The board uses spacer paper.

玻璃板用間隔紙是夾裝在玻璃板間使用的片材。一般而言，玻璃板用間隔紙是在保管或運輸玻璃板等將多片玻璃板一起處理時，為了防止玻璃板產生損傷或破損之疑慮所用。The spacer paper for glass plates is a sheet used for sandwiching between glass plates. In general, the spacer paper for glass plates is used to prevent the glass plate from being damaged or damaged when storing or transporting the glass plates and processing a plurality of glass plates together.

於顯示器等使用玻璃板時，一般會以水等來洗滌玻璃板之表面。伴隨近幾年顯示器之高精細化，針對顯示器用玻璃板要求更高的品質。所以，現多要求能透過洗滌使玻璃板之表面狀態維持在非常乾淨的狀態。也因此，針對玻璃用間隔紙，漸漸要求必須是不會阻礙玻璃板等被包裝物之可洗性者、或是可賦予玻璃板等被包裝物優異可洗性者。When a glass plate is used for a display, etc., the surface of the glass plate is generally washed with water or the like. With the high definition of displays in recent years, higher quality is required for glass plates for displays. Therefore, it is now required to maintain the surface state of the glass plate in a very clean state through washing. Therefore, with respect to the spacer paper for glass, it is gradually required that those that do not hinder the washability of the packaged object such as a glass plate or that can impart excellent washability to the packaged object such as a glass plate.

針對所述要求，譬如專利文獻1中提出一種使表面層含有聚乙二醇等親水性化合物之聚烯烴系樹脂積層發泡片材。該聚烯烴系樹脂積層發泡片材作為包裝用片材使用時，可提升被包裝用片材包裝之被包裝物的可洗性上升。所以，即使有異物等從包裝用片材轉移至被包裝物上，仍可藉由實施以水等洗滌被包裝物的方式而輕易去除被包裝物表面的汙垢。 先前技術文獻 專利文獻In response to the above requirements, for example, Patent Document 1 proposes a polyolefin-based resin laminated foam sheet in which the surface layer contains a hydrophilic compound such as polyethylene glycol. When this polyolefin-based resin laminated foam sheet is used as a packaging sheet, the washability of the packaged object packaged by the packaging sheet can be improved. Therefore, even if foreign substances or the like are transferred from the packaging sheet to the packaged object, it is still possible to easily remove dirt on the surface of the packaged object by performing washing of the packaged object with water or the like. Prior technical literature Patent Literature

專利文獻1：日本特開第2010-42556號公報Patent Document 1: Japanese Patent Laid-Open No. 2010-42556

發明概要 發明欲解決之課題 近幾年，在保管或運輸等時，玻璃板等被包裝物被放置在高溫多濕之氣體環境下的情況有所增加。在高溫多濕之氣體環境下使用舊有的聚烯烴系樹脂積層發泡片材時，有玻璃板等被包裝物之可洗性賦予略顯不足之情況。Summary of the invention Problems to be solved by invention In recent years, in storage or transportation, the situation that the packaged objects such as glass plates are placed in a high-temperature and humid gas environment has increased. When using old polyolefin-based resin laminated foam sheets in a high-temperature and humid gas environment, the washability of the packaged objects such as glass plates may be slightly insufficient.

本發明目的在於提供一種積層發泡片材及利用所述積層發泡片材之玻璃板用間隔紙，該積層發泡片材即使在高溫多濕下也能賦予玻璃板等被包裝物優異的可洗性。 用以解決課題之手段An object of the present invention is to provide a laminated foam sheet and a spacer paper for a glass plate using the laminated foam sheet, the laminated foam sheet can provide an excellent packaged object such as a glass sheet even under high temperature and humidity Washability. Means to solve the problem

本發明主旨如下： (1)一種聚烯烴系樹脂積層發泡片材，係具有聚烯烴系樹脂發泡層與聚烯烴系樹脂表面層的積層發泡片材，其中該聚烯烴系樹脂表面層積層接著在該發泡層之至少單面側；其特徵在於： 前述表面層摻混有聚乙二醇(PEG)， 前述聚乙二醇(PEG)係由在25℃下為液體之前述第1聚乙二醇(PEG1)與在25℃下為固體之第2聚乙二醇(PEG2)構成； 相對於構成前述表面層之聚烯烴系樹脂100質量份，前述表面層中之前述第1聚乙二醇(PEG1)的摻混量為0.5質量份以上且10質量份以下； 相對於前述表面層中之第1聚乙二醇(PEG1)的摻混量100質量份，前述表面層中之前述第2聚乙二醇(PEG2)的摻混量為3質量份以上； (2)如上述(1)記載之聚烯烴系樹脂積層發泡片材，其中前述第1聚乙二醇(PEG1)之數量平均分子量為100以上且800以下； (3)如上述(1)或(2)記載之聚烯烴系樹脂積層發泡片材，其中前述第2聚乙二醇(PEG2)之數量平均分子量為2000以上； (4)如上述(1)至(3)中任一項記載之聚烯烴系樹脂積層發泡片材，其中前述第2聚乙二醇(PEG2)之凝固點為超過50℃之溫度； (5)如上述(1)至(4)中任一項記載之聚烯烴系樹脂積層發泡片材，其中相對於前述表面層中之前述第1聚乙二醇(PEG1)的摻混量100質量份，前述表面層中之前述第2聚乙二醇(PEG2)的摻混量為3質量份以上且100質量份以下； (6)如上述(1)至(5)中任一項記載之聚烯烴系樹脂積層發泡片材，其中相對於構成前述表面層之聚烯烴系樹脂100質量份，前述聚乙二醇(PEG)之總摻混量為15質量份以下； (7)如上述(1)至(6)中任一項記載之聚烯烴系樹脂積層發泡片材，其中於前述表面層摻混有高分子型抗靜電劑，且相對於構成前述表面層之聚烯烴系樹脂100質量份，該高分子型抗靜電劑之摻混量為2質量份以上且30質量份以下； (8)如上述(1)至(7)中任一項記載之聚烯烴系樹脂積層發泡片材，其中構成前述發泡層之聚烯烴系樹脂為低密度聚乙烯，且構成前述表面層之聚烯烴系樹脂為低密度聚乙烯； (9)一種玻璃板用間隔紙，係由如上述(1)至(8)中任一項記載之聚烯烴系樹脂積層發泡片材構成。The gist of the present invention is as follows: (1) A polyolefin-based resin laminated foamed sheet, which is a laminated foamed sheet having a polyolefin-based resin foamed layer and a polyolefin-based resin surface layer, wherein the polyolefin-based resin surface layered layer is then laminated on the At least one side of the foam layer; characterized by: The aforementioned surface layer is blended with polyethylene glycol (PEG), The polyethylene glycol (PEG) is composed of the first polyethylene glycol (PEG1) that is liquid at 25°C and the second polyethylene glycol (PEG2) that is solid at 25°C; The blending amount of the first polyethylene glycol (PEG1) in the surface layer is 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polyolefin resin constituting the surface layer; The blending amount of the second polyethylene glycol (PEG2) in the surface layer is 3 mass parts or more with respect to 100 mass parts of the blending amount of the first polyethylene glycol (PEG1) in the surface layer; (2) The polyolefin resin laminated foamed sheet as described in (1) above, wherein the number average molecular weight of the first polyethylene glycol (PEG1) is 100 or more and 800 or less; (3) The polyolefin resin laminated foamed sheet as described in (1) or (2) above, wherein the number average molecular weight of the second polyethylene glycol (PEG2) is 2000 or more; (4) The polyolefin-based resin laminated foam sheet according to any one of (1) to (3) above, wherein the freezing point of the second polyethylene glycol (PEG2) is a temperature exceeding 50°C; (5) The polyolefin resin laminated foamed sheet according to any one of (1) to (4) above, wherein the blending amount with respect to the first polyethylene glycol (PEG1) in the surface layer 100 parts by mass, the blending amount of the second polyethylene glycol (PEG2) in the surface layer is 3 parts by mass or more and 100 parts by mass or less; (6) The polyolefin-based resin laminated foamed sheet according to any one of (1) to (5) above, wherein the polyethylene glycol (based on 100 parts by mass of the polyolefin-based resin constituting the surface layer is PEG) The total blending amount is less than 15 parts by mass; (7) The polyolefin-based resin laminated foam sheet as described in any one of (1) to (6) above, wherein a polymer antistatic agent is blended in the surface layer, and is formed relative to the surface layer 100 parts by mass of polyolefin resin, and the blending amount of the polymer antistatic agent is 2 parts by mass or more and 30 parts by mass or less; (8) The polyolefin-based resin laminated foam sheet according to any one of (1) to (7) above, wherein the polyolefin-based resin constituting the foam layer is low-density polyethylene and constitutes the surface layer The polyolefin resin is low density polyethylene; (9) A spacer paper for a glass plate, which is composed of a polyolefin-based resin laminated foam sheet as described in any one of (1) to (8) above.

發明效果 本發明之積層發泡片材係聚烯烴系樹脂積層發泡片材，即使其在高溫多濕下，仍可賦予玻璃板等被包裝物優異的可洗性。而且使用積層發泡片材之本發明之玻璃板用間隔紙，即使在高溫多濕下仍可賦予玻璃板優異的可洗性。Invention effect The laminated foamed sheet of the present invention is a polyolefin-based resin laminated foamed sheet, and even if it is under high temperature and high humidity, it can still impart excellent washability to a packaged object such as a glass plate. Moreover, the spacer paper for glass plates of the present invention using a laminated foam sheet can give glass plates excellent washability even under high temperature and humidity.

用以實施發明之形態 本發明之積層發泡片材具有聚烯烴系樹脂發泡層(以下有時會僅稱作發泡層)與聚烯烴系樹脂表面層(以下有時會僅稱作表面層)。Forms for carrying out the invention The laminated foamed sheet of the present invention has a polyolefin-based resin foamed layer (hereinafter sometimes referred to simply as a foamed layer) and a polyolefin-based resin surface layer (hereinafter sometimes referred to simply as a surface layer).

(積層發泡片材之平均厚度) 本發明之積層發泡片材的平均厚度並無特別限制，積層發泡片材之平均厚度大概為0.05mm以上且10mm以下。積層發泡片材之平均厚度若在上述範圍內，即使作為玻璃板用間隔紙使用，也不會增大體積且可確保充分的緩衝性。由上述觀點來看，積層發泡片材之平均厚度的下限宜為0.07mm，較佳為0.1mm，更佳為0.12mm。而且積層發泡片材之平均厚度的上限宜為1.0mm，較佳為0.5mm，更佳為0.3mm。(Average thickness of laminated foam sheet) The average thickness of the laminated foam sheet of the present invention is not particularly limited, and the average thickness of the laminated foam sheet is approximately 0.05 mm or more and 10 mm or less. If the average thickness of the laminated foam sheet is within the above range, even if it is used as a spacer for glass plates, the volume will not increase and sufficient cushioning properties can be ensured. From the above viewpoint, the lower limit of the average thickness of the laminated foam sheet is preferably 0.07 mm, preferably 0.1 mm, and more preferably 0.12 mm. The upper limit of the average thickness of the laminated foam sheet is preferably 1.0 mm, preferably 0.5 mm, and more preferably 0.3 mm.

(特定積層發泡片材之平均厚度) 本發明中之積層發泡片材的平均厚度係以在積層發泡片材的整個範圍於寬度方向以1cm間隔進行測定之積層發泡片材所有厚度(mm)之算術平均值來特定。譬如在使用擠製機之製造方法來製造積層發泡片材時，寬度方向意指順沿積層發泡片材面之方向且相對於積層發泡片材之擠製方向呈正交的方向。(Average thickness of specific laminated foam sheet) The average thickness of the laminated foam sheet in the present invention is specified by the arithmetic average of all thicknesses (mm) of the laminated foam sheet measured at intervals of 1 cm in the width direction over the entire range of the laminated foam sheet. For example, when manufacturing the laminated foam sheet using the manufacturing method of an extruder, the width direction means a direction along the surface of the laminated foam sheet and orthogonal to the extrusion direction of the laminated foam sheet.

(發泡層) 本發明之積層發泡片材的發泡層係用以聚烯烴系樹脂作為基材樹脂之發泡體所形成之層。成為基材樹脂之聚烯烴系樹脂係令源自烯烴系單體之成分單元比率為50莫耳%以上的樹脂。聚烯烴系樹脂可舉聚乙烯系樹脂、聚丙烯系樹脂、聚丁烯系樹脂等。聚烯烴系樹脂中，在柔軟性更為優異的觀點下，以聚乙烯系樹脂尤佳。(Foam layer) The foamed layer of the laminated foamed sheet of the present invention is a layer formed using a polyolefin-based resin as a base resin foam. The polyolefin-based resin used as the base resin is a resin having a ratio of component units derived from olefin-based monomers of 50 mol% or more. Examples of polyolefin resins include polyethylene resins, polypropylene resins, and polybutene resins. Among the polyolefin resins, polyethylene resins are particularly preferred from the viewpoint of more excellent flexibility.

聚乙烯系樹脂可舉如高密度聚乙烯、低密度聚乙烯、直鏈狀低密度聚乙烯、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯共聚物、乙烯-丙烯-1-丁烯共聚物、乙烯-丁烯-1共聚物、乙烯-1-己烯共聚物、乙烯-4-甲基-1-戊烯共聚物、或乙烯-1-辛烯共聚物、又或更甚者其等之2種以上混合物等。Examples of the polyethylene-based resin include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, ethylene-propylene-1-butene copolymer, Ethylene-butene-1 copolymer, ethylene-1-hexene copolymer, ethylene-4-methyl-1-pentene copolymer, or ethylene-1-octene copolymer, or even more, etc. 2 or more mixtures.

該等聚乙烯系樹脂中又以低密度聚乙烯為佳。另，在本說明書中，低密度聚乙烯係密度為890kg/m3 以上且935kg/m3 以下之聚乙烯系樹脂，且宜密度為900kg/m3 以上且930kg/m3 以下的聚乙烯系樹脂。Among these polyethylene resins, low density polyethylene is preferred. Also, in the present specification, low-density polyethylene of a density 890kg / m 3 or more and 935kg / m 3 or less of polyethylene resin, and a suitable density of 900kg / m 3 or more and 930kg / m 3 or less of polyethylene Resin.

聚丙烯系樹脂可舉丙烯均聚物、或丙烯與其他烯烴等之共聚物。可與丙烯共聚之其他烯烴可舉如乙烯或1-丁烯、異丁烯、1-戊烯、3-甲基-1-丁烯、1-己烯、3,4-二甲基-1-丁烯、1-庚烯、或是3-甲基-1-己烯等碳數4至10之α-烯烴。Examples of polypropylene-based resins include propylene homopolymers or copolymers of propylene and other olefins. Other olefins copolymerizable with propylene include ethylene or 1-butene, isobutene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3,4-dimethyl-1-butene Α-olefins having 4 to 10 carbon atoms, such as ene, 1-heptene, or 3-methyl-1-hexene.

亦可在不損害本發明效果之範圍內於聚烯烴系樹脂添加苯乙烯系樹脂等其他樹脂、或是乙烯丙烯橡膠或苯乙烯-丁二烯-苯乙烯嵌段共聚物等之彈性體等。在此情況下，令構成發泡層之聚烯烴系樹脂的添加量為100質量份時，其他樹脂或彈性體等之添加量宜為25質量份以下，且10質量份以下較佳，5質量份以下尤佳。Other resins such as styrene resins, or elastomers such as ethylene propylene rubber, styrene-butadiene-styrene block copolymers, etc. may be added to the polyolefin-based resin within a range that does not impair the effects of the present invention. In this case, when the addition amount of the polyolefin resin constituting the foamed layer is 100 parts by mass, the addition amount of other resins or elastomers is preferably 25 parts by mass or less, and preferably 10 parts by mass or less, 5 parts by mass The following is especially good.

又，亦可在不損及本發明效果之範圍內於聚烯烴系樹脂添加1種或2種以上之添加劑。添加劑可舉如氣泡調整劑、成核劑、抗氧化劑、熱穩定劑、耐候劑、紫外線吸收劑、阻燃劑、抗菌劑、抗收縮劑等機能性添加劑、無機充填劑等。In addition, one kind or two or more kinds of additives may be added to the polyolefin-based resin as long as the effects of the present invention are not impaired. Additives include functional additives such as bubble regulators, nucleating agents, antioxidants, heat stabilizers, weathering agents, ultraviolet absorbers, flame retardants, antibacterial agents, anti-shrinking agents, inorganic fillers, and the like.

(積層發泡片材之視密度) 本發明之積層發泡片材的視密度宜為20kg/m3 以上且450kg/m3 以下。積層發泡片材之視密度若在上述範圍內，積層發泡片材不僅柔軟性優異，保形性及壓縮強度等機械強度亦佳。從積層發泡片材的柔軟性觀點來看，該視密度之上限宜為300kg/m3 ，較宜為200kg/m3 。而且從積層發泡片材之機械強度或彈性強度的觀點來看，該視密度之下限宜為30kg/m3 ，較宜為40kg/m3 ，更宜為50kg/m3 。(Visual density of laminated foam sheet) The apparent density of the laminated foam sheet of the present invention is preferably 20 kg/m 3 or more and 450 kg/m 3 or less. If the apparent density of the laminated foam sheet is within the above range, the laminated foam sheet not only has excellent flexibility, but also has good mechanical strength such as shape retention and compressive strength. From the viewpoint of the flexibility of the laminated foamed sheet, the upper limit of the apparent density is preferably 300 kg/m 3 , and more preferably 200 kg/m 3 . Moreover, from the viewpoint of the mechanical strength or elastic strength of the laminated foam sheet, the lower limit of the apparent density is preferably 30 kg/m 3 , more preferably 40 kg/m 3 , and even more preferably 50 kg/m 3 .

積層發泡片材之視密度係從積層發泡片材裁切出試驗片，將其試驗片之質量(kg)除以從其試驗片之外形尺寸求得的體積(m3 )後所得之值來特定。The apparent density of the laminated foamed sheet is obtained by cutting out the test piece from the laminated foamed sheet and dividing the mass (kg) of the test piece by the volume (m 3 ) obtained from the shape dimension of the test piece Value to be specific.

(表面層) 本發明之積層發泡片材的表面層係積層接著於發泡層之表面、背面中之至少單面側，且位在積層發泡片材之最表面側。並且，亦可在發泡層與表面層之間形成有中間層。中間層可舉如由對發泡層與表面層這兩層具有接著性之樹脂所構成之層。 表面層之厚度並無特別限定，可在不損及發泡層之緩衝性的範圍內適宜決定。譬如，其中一側之表面層的平均厚度宜小於發泡層之平均厚度。此外，於兩面具備表面層之積層發泡片材中，兩面之表面層的平均厚度總宜小於發泡層之平均厚度。又，此處所提表面層之平均厚度可以下列方法製得。首先，將積層發泡片材於寬度方向裁切形成切割面後，在該切割面於片材整個範圍沿著寬度方向以1cm間隔拍攝放大照片。然後測定所拍攝之各點的表面層厚度(mm)，算出該等之算術平均後所得的平均厚度。在積層發泡片材上隨機選出3處進行上述測定後，以所算出之前述3處的平均厚度之值的算術平均值為表面層之平均厚度。(Surface layer) The surface layer of the laminated foamed sheet of the present invention is laminated on at least one side of the front and back surfaces of the foamed layer, and is located on the outermost surface side of the laminated foamed sheet. Furthermore, an intermediate layer may be formed between the foam layer and the surface layer. The intermediate layer may be, for example, a layer composed of a resin having adhesion to both the foam layer and the surface layer. The thickness of the surface layer is not particularly limited, and can be appropriately determined within a range that does not impair the cushioning property of the foam layer. For example, the average thickness of the surface layer on one side is preferably smaller than the average thickness of the foam layer. In addition, in a laminated foam sheet having surface layers on both sides, the average thickness of the surface layers on both sides should always be smaller than the average thickness of the foam layer. In addition, the average thickness of the surface layer mentioned here can be obtained by the following method. First, after cutting the laminated foam sheet in the width direction to form a cut surface, an enlarged photograph of the cut surface is taken at 1 cm intervals along the width direction over the entire range of the sheet. Then, the thickness (mm) of the surface layer of each point photographed is measured, and the average thickness obtained after the arithmetic average of these is calculated. After randomly selecting 3 places on the laminated foam sheet and performing the above measurement, the arithmetic average of the calculated values of the average thickness of the above 3 places is taken as the average thickness of the surface layer.

表面層係以聚烯烴系樹脂作為基材樹脂之樹脂組成物所形成之層。成為基材樹脂之聚烯烴系樹脂及摻混於其中之其他樹脂或添加劑等可使用與針對發泡層所述者相同之物。 舉例來說，表面層宜為非發泡層。在此所提非發泡層，係在不用為使樹脂發泡所用之發泡劑等條件下所形成的樹脂層。上述非發泡層包含在製造過程中偶然發生或混入之氣泡所內生的樹脂層。The surface layer is a layer formed of a resin composition using a polyolefin resin as a base resin. The polyolefin resin used as the base resin and other resins or additives blended therein may be the same as those described for the foamed layer. For example, the surface layer is preferably a non-foamed layer. The non-foamed layer mentioned here is a resin layer formed without using a foaming agent or the like for foaming the resin. The above-mentioned non-foamed layer includes a resin layer that is generated by bubbles that accidentally occur or are mixed in during the manufacturing process.

在本發明之積層發泡片材中，構成發泡層及表面層之聚烯烴系樹脂可使用相同樹脂，亦可在發泡層與表面層使用互異的樹脂。積層發泡片材以發泡層與表面層彼此相同種類的樹脂形成時，發泡層與表面層之接著性會變高。若從發泡層與表面層之接著性觀點來看，不僅發泡層，對於表面層亦宜使用低密度聚乙烯。In the laminated foamed sheet of the present invention, the polyolefin resin constituting the foamed layer and the surface layer may use the same resin, or may use mutually different resins for the foamed layer and the surface layer. When the laminated foam sheet is formed of the same type of resin as the foam layer and the surface layer, the adhesion between the foam layer and the surface layer becomes higher. From the viewpoint of adhesion between the foam layer and the surface layer, not only the foam layer but also the surface layer is preferably low-density polyethylene.

表面層之基重就單面而言宜為0.5g/m2 以上，且0.7g/m2 以上較佳，1.0g/m2 以上更佳。表面層之基重若滿足上述範圍，所期望之被包裝物的可洗性便可充分提高。若從被包裝物之可洗性觀點來看，該表面層之基重上限並無特別限制。若從緩衝性及輕量性的觀點來看，其上限宜為100g/m2 ，且60g/m2 較佳，50g/m2 更佳。The basis weight of the surface layer is preferably 0.5 g/m 2 or more for one side, and preferably 0.7 g/m 2 or more, and more preferably 1.0 g/m 2 or more. If the basis weight of the surface layer satisfies the above range, the desired washability of the packaged object can be sufficiently improved. From the viewpoint of the washability of the packaged object, the upper limit of the basis weight of the surface layer is not particularly limited. From the viewpoint of cushioning properties and lightness, the upper limit is preferably 100 g/m 2 , and 60 g/m 2 is more preferable, and 50 g/m 2 is more preferable.

本發明中之表面層的基重[g/m2 ]在藉由使用擠製機之製造方法來製造積層發泡片材時，可從積層發泡片材製造時之表面層的吐出量X[kg/h]、所得積層發泡片材之寬度W[m]及每單位時間可製造之積層發泡片材的長度L[m/h]，由以下式(1)求得。另，於發泡層之兩面側積層表面層時，係從各表面層之吐出量求出各表面層之基重。The basis weight [g/m 2 ] of the surface layer in the present invention can be discharged from the surface layer at the time of manufacturing the laminated foam sheet when the laminated foam sheet is manufactured by the manufacturing method using an extruder [kg/h], the width W [m] of the obtained laminated foam sheet and the length L [m/h] of the laminated foam sheet that can be manufactured per unit time are obtained by the following formula (1). In addition, when the surface layers are laminated on both sides of the foam layer, the basis weight of each surface layer is obtained from the discharge amount of each surface layer.

[數學式1]

Figure 02_image001
[Mathematical formula 1]
Figure 02_image001

(聚乙二醇(PEG)) 於本發明之積層發泡片材的表面層摻混有聚乙二醇(PEG)。摻混在表面層中之聚乙二醇(PEG)係由第1聚乙二醇(PEG1)與第2聚乙二醇(PEG2)構成。(Polyethylene glycol (PEG)) The surface layer of the laminated foam sheet of the present invention is blended with polyethylene glycol (PEG). The polyethylene glycol (PEG) blended in the surface layer is composed of the first polyethylene glycol (PEG1) and the second polyethylene glycol (PEG2).

本發明之積層發泡片材即使是設置在高溫多濕之氣體環境下，仍可賦予玻璃板等被包裝物優異的可洗性。本發明之積層發泡片材即使在高溫多濕下仍可賦予被包裝物優異可洗性的理由尚不明確，但吾人以為有下列所示2項理由。Even if the laminated foamed sheet of the present invention is placed in a high-temperature and humid gas environment, it can still give excellent washability to a packaged object such as a glass plate. The reason why the laminated foam sheet of the present invention can impart excellent washability to the packaged object even under high temperature and humidity is not clear, but I think there are two reasons as shown below.

第一，本發明之積層發泡片材摻混有在25℃下為液體之第1聚乙二醇以及在25℃下為固體之第2聚乙二醇(PEG2)，因此可壓低積層發泡片材之吸水率。因此，吾人認為，即使被放置在高溫多濕之氣體環境下，塵、埃等也不易附著於積層發泡片材之表面。此外，藉由壓低積層發泡片材之吸水率，可抑制為汙垢主因之大氣中的有機物、或水分中所含氫離子或鈣離子等不純物與空氣中之水分一同附著於積層發泡片材上的疑慮。 所以，使用本發明之積層發泡片材作為包裝材時，透過該積層發泡片材可有效抑制塵、埃、上述有機物或上述不純物等等異物附著於被包裝物上、汙染被包裝物的情況。First, the laminated foam sheet of the present invention is blended with the first polyethylene glycol that is liquid at 25°C and the second polyethylene glycol (PEG2) that is solid at 25°C, so the laminated hair can be suppressed Water absorption of foam sheet. Therefore, I think that even if it is placed in a high-temperature and humid gas environment, dust, dust, etc. will not easily adhere to the surface of the laminated foam sheet. In addition, by lowering the water absorption of the laminated foam sheet, it is possible to suppress impurities such as organic matter in the atmosphere, hydrogen ions or calcium ions contained in the moisture, and moisture in the air to adhere to the laminated foam sheet Doubts. Therefore, when the laminated foamed sheet of the present invention is used as a packaging material, the foreign matter such as dust, angstrom, the above-mentioned organic matter or the above-mentioned impurities can be effectively inhibited from adhering to the packaged object and contaminating the packaged object through the laminated foamed sheet Happening.

第二，吾人認為本發明之積層發泡片材即使被放置在高溫多濕之氣體環境下，第1聚乙二醇(PEG1)也能更均勻地從表面層溢出至被包裝物上。 即，表面層中所含第1聚乙二醇(PEG1)會從表面層溢出而附著於被包裝物之表面，所以在洗滌該被包裝物時能輕易洗去表面的汙垢。惟，在25℃下為液體之第1聚乙二醇(PEG1)有在表面層變成液滴而存在不均之傾向。所以，溢出時，第1聚乙二醇(PEG1)很難均勻移動到被包裝物上。相對地，本發明之積層發泡片材藉由第2聚乙二醇(PEG2)之存在而可使第1聚乙二醇(PEG1)均勻地分散在表面層上。因此，吾人認為本發明之積層發泡片材可使親水性化合物之第1聚乙二醇(PEG1)更輕易地從表面層均勻移動至被包裝物上。其結果，在洗滌被包裝物時，可抑制被包裝物洗淨不均的情況，給予良好的可洗性。Secondly, I think that even if the laminated foamed sheet of the present invention is placed in a high-temperature and humid gas environment, the first polyethylene glycol (PEG1) can overflow from the surface layer onto the package more uniformly. That is, the first polyethylene glycol (PEG1) contained in the surface layer overflows from the surface layer and adheres to the surface of the packaged object, so the surface dirt can be easily washed away when the packaged object is washed. However, the first polyethylene glycol (PEG1), which is liquid at 25°C, tends to become droplets on the surface layer and there is a tendency to be uneven. Therefore, when overflowing, it is difficult for the first polyethylene glycol (PEG1) to move evenly onto the packaged object. In contrast, the laminated foam sheet of the present invention can uniformly disperse the first polyethylene glycol (PEG1) on the surface layer by the presence of the second polyethylene glycol (PEG2). Therefore, I think that the laminated foam sheet of the present invention can make the first polyethylene glycol (PEG1) of the hydrophilic compound more easily move uniformly from the surface layer to the packaged object. As a result, when washing the packaged object, uneven cleaning of the packaged object can be suppressed, and good washability can be provided.

基於上述理由，吾人認為，本發明之積層發泡片材即使在高溫多濕下仍可賦予被包裝物優異的可洗性。Based on the above reasons, I believe that the laminated foam sheet of the present invention can impart excellent washability to the packaged object even under high temperature and high humidity.

(聚乙二醇之摻混量) 相對於構成表面層之聚烯烴系樹脂100質量份，表面層中之聚乙二醇(PEG)的總摻混量宜為15質量份以下。表面層中之聚乙二醇(PEG)的總摻混量若在上述範圍內，即可做出即使在高溫多濕之氣體環境下仍可賦予玻璃板等被包裝物更優異之可洗性的積層發泡片材。基於上述觀點，聚乙二醇(PEG)之摻混量上限以12質量份較佳，10質量份更佳。並且，聚乙二醇(PEG)之摻混量下限宜超過0.5質量份為1.0質量份。(Mixed amount of polyethylene glycol) The total blending amount of polyethylene glycol (PEG) in the surface layer is preferably 15 parts by mass or less with respect to 100 parts by mass of the polyolefin resin constituting the surface layer. If the total blending amount of polyethylene glycol (PEG) in the surface layer is within the above range, it can be made to give the glass plate and other packaged objects more excellent washability even in a high-temperature and humid gas environment Laminated foam sheet. From the above viewpoint, the upper limit of the blending amount of polyethylene glycol (PEG) is preferably 12 parts by mass, more preferably 10 parts by mass. In addition, the lower limit of the blending amount of polyethylene glycol (PEG) should preferably exceed 1.0 part by mass to 1.0 part by mass.

(第1聚乙二醇(PEG1)) 表面層中之第1聚乙二醇(PEG1)係在25℃下為液體之聚乙二醇。藉由前述第1聚乙二醇(PEG1)在25℃下為液體，第1聚乙二醇(PEG1)就更容易從表面層溢出，從而可賦予被包裝物優異的可洗性。基於上述觀點，第1聚乙二醇(PEG1)在23℃下為液體較佳，在10℃下為液體更佳，在0℃為液體尤佳。(1st polyethylene glycol (PEG1)) The first polyethylene glycol (PEG1) in the surface layer is polyethylene glycol which is liquid at 25°C. When the first polyethylene glycol (PEG1) is liquid at 25° C., the first polyethylene glycol (PEG1) is more likely to overflow from the surface layer, thereby giving the packaged article excellent washability. From the above viewpoint, the first polyethylene glycol (PEG1) is preferably liquid at 23°C, more preferably liquid at 10°C, and particularly preferably liquid at 0°C.

(第1聚乙二醇(PEG1)之數量平均分子量) 第1聚乙二醇(PEG1)之數量平均分子量宜為100以上且800以下。第1聚乙二醇(PEG1)之數量平均分子量若為上述範圍內，第1聚乙二醇(PEG1)便容易從表面層溢出，而可賦予被包裝物優異的可洗性。基於上述觀點，第1聚乙二醇(PEG1)之數量平均分子量的下限以150較佳，200更佳。而且，第1聚乙二醇(PEG1)之數量平均分子量的上限以700較佳，600更佳。(Number average molecular weight of the first polyethylene glycol (PEG1)) The number average molecular weight of the first polyethylene glycol (PEG1) is preferably 100 or more and 800 or less. If the number average molecular weight of the first polyethylene glycol (PEG1) is within the above range, the first polyethylene glycol (PEG1) easily overflows from the surface layer, and can impart excellent washability to the packaged object. From the above viewpoint, the lower limit of the number average molecular weight of the first polyethylene glycol (PEG1) is preferably 150, more preferably 200. Furthermore, the upper limit of the number average molecular weight of the first polyethylene glycol (PEG1) is preferably 700, more preferably 600.

(數量平均分子量的特定方法) 第1聚乙二醇(PEG1)之數量平均分子量可藉由從羥值算出之周知方法求得。(Specific method of number average molecular weight) The number average molecular weight of the first polyethylene glycol (PEG1) can be obtained by a well-known method for calculating the hydroxyl value.

(第1聚乙二醇(PEG1)之摻混量) 相對於構成前述表面層之聚烯烴系樹脂100質量份，表面層中之前述第1聚乙二醇(PEG1)的摻混量為0.5質量份以上且10質量份以下。第1聚乙二醇(PEG1)之摻混量的比率若為上述範圍內，積層發泡片材即可賦予被包裝物更為優異的可洗性。基於上述觀點，第1聚乙二醇(PEG1)之摻混量的下限以1.0質量份較佳，2質量份更佳。並且，第1聚乙二醇(PEG1)之摻混量的上限以8質量份較佳，6質量份更佳。(The blending amount of the first polyethylene glycol (PEG1)) The blending amount of the first polyethylene glycol (PEG1) in the surface layer is 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polyolefin resin constituting the surface layer. If the ratio of the blending amount of the first polyethylene glycol (PEG1) is within the above range, the laminated foam sheet can give the packaged object more excellent washability. From the above viewpoint, the lower limit of the blending amount of the first polyethylene glycol (PEG1) is preferably 1.0 part by mass, more preferably 2 parts by mass. In addition, the upper limit of the blending amount of the first polyethylene glycol (PEG1) is preferably 8 parts by mass, more preferably 6 parts by mass.

第1聚乙二醇(PEG1)可從市場入手。在本發明中，可作為第1聚乙二醇(PEG1)使用之市售物可舉如FUJIFILM Wako Pure Chemical Co.製造之「Polyethylene Glycol 300」等。The first polyethylene glycol (PEG1) can be obtained from the market. In the present invention, commercially available products that can be used as the first polyethylene glycol (PEG1) include, for example, "Polyethylene Glycol 300" manufactured by FUJIFILM Wako Pure Chemical Co.

(第2聚乙二醇(PEG2)) 表面層中之第2聚乙二醇(PEG2)係在25℃下為固體之聚乙二醇。在25℃下為固體之第2聚乙二醇(PEG2)藉由與在25℃下為液體之第1聚乙二醇(PEG1)一起摻混在積層發泡片材之表面層中，積層發泡片材即使被放置在高溫多濕之氣體環境下，仍可賦予玻璃板等被包裝物更優異的可洗性。(Second polyethylene glycol (PEG2)) The second polyethylene glycol (PEG2) in the surface layer is polyethylene glycol which is solid at 25°C. The second polyethylene glycol (PEG2), which is solid at 25°C, is blended with the first polyethylene glycol (PEG1), which is liquid at 25°C, in the surface layer of the laminated foam sheet. Even if the foam sheet is placed in a high-temperature and humid gas environment, it can still give the glass plate and other packaged objects more excellent washability.

(第2聚乙二醇(PEG2)之數量平均分子量) 若從可在高溫多濕下更加提升玻璃板等被包裝物之可洗性的觀點來看，前述第2聚乙二醇(PEG2)之數量平均分子量宜為2000以上，且2500以上較佳，3000以上更佳。第2聚乙二醇(PEG2)之數量平均分子量的上限大致為20000。(The number average molecular weight of the second polyethylene glycol (PEG2)) From the standpoint of improving the washability of packaged objects such as glass plates under high temperature and humidity, the number average molecular weight of the second polyethylene glycol (PEG2) is preferably 2000 or more, and preferably 2500 or more. More than 3000 is better. The upper limit of the number average molecular weight of the second polyethylene glycol (PEG2) is approximately 20,000.

(數量平均分子量的特定方法) 第2聚乙二醇(PEG2)之數量平均分子量可藉由與前述之第1聚乙二醇(PEG1)之數量平均分子量相同的方法求得。(Specific method of number average molecular weight) The number average molecular weight of the second polyethylene glycol (PEG2) can be obtained by the same method as the aforementioned number average molecular weight of the first polyethylene glycol (PEG1).

(第2聚乙二醇(PEG2)之凝固點) 此外，若從可在高溫多濕下更加提升玻璃板等被包裝物之可洗性的觀點來看，第2聚乙二醇(PEG2)之凝固點宜為超過50℃之溫度，且52℃以上較佳，55℃以上更佳。第2聚乙二醇(PEG2)之凝固點的上限大致為65℃。(The freezing point of the second polyethylene glycol (PEG2)) In addition, from the viewpoint of further improving the washability of packaged objects such as glass plates under high temperature and humidity, the freezing point of the second polyethylene glycol (PEG2) is preferably a temperature exceeding 50°C and 52°C or higher Preferably, it is more preferably above 55°C. The upper limit of the freezing point of the second polyethylene glycol (PEG2) is approximately 65°C.

(凝固點的特定方法) 第2聚乙二醇(PEG2)之凝固點可藉由JIS K 0065(1992年)中記載之方法等求得。(Specific method of freezing point) The freezing point of the second polyethylene glycol (PEG2) can be obtained by the method described in JIS K 0065 (1992).

(第2聚乙二醇(PEG2)之摻混量) 相對於前述表面層中之第1聚乙二醇(PEG1)的摻混量100質量份，表面層中之第2聚乙二醇(PEG2)的摻混量為3質量份以上。第2聚乙二醇(PEG2)之摻混量若太少，當其被放置在高溫多濕之氣體環境下時，恐無法給予玻璃板等被包裝物充分的可洗性。基於上述觀點，相對於前述表面層中之第1聚乙二醇(PEG1)的摻混量100質量份，表面層中之第2聚乙二醇(PEG2)的摻混量較宜為5質量份以上。(The blending amount of the second polyethylene glycol (PEG2)) The blending amount of the second polyethylene glycol (PEG2) in the surface layer is 3 mass parts or more with respect to 100 mass parts of the blending amount of the first polyethylene glycol (PEG1) in the surface layer. If the blending amount of the second polyethylene glycol (PEG2) is too small, when it is placed in a high-temperature and humid gas environment, it may not give sufficient washability to the packaged objects such as glass plates. Based on the above viewpoint, the blending amount of the second polyethylene glycol (PEG2) in the surface layer is preferably 5 masses relative to the blending amount of the first polyethylene glycol (PEG1) in the surface layer of 100 parts by mass More than.

表面層中之第2聚乙二醇(PEG2)的摻混量上限並無特別限定，惟若從積層發泡片材之製造穩定性的觀點來看，相對於前述表面層中之第1聚乙二醇(PEG1)的摻混量100質量份，宜為100質量份以下。 尤其，若從上述可洗性之給予及製造穩定性的觀點來看，相對於構成表面層之聚烯烴系樹脂100質量份，表面層中之聚乙二醇(PEG)的總摻混量為15質量份以下；且相對於表面層中之第1聚乙二醇(PEG1)的摻混量100質量份，表面層中之第2聚乙二醇(PEG2)的摻混量為3質量份以上且100質量份以下為佳。The upper limit of the blending amount of the second polyethylene glycol (PEG2) in the surface layer is not particularly limited, but from the viewpoint of the manufacturing stability of the laminated foam sheet, it is The blending amount of ethylene glycol (PEG1) is 100 parts by mass, preferably 100 parts by mass or less. In particular, from the viewpoint of giving the above washability and manufacturing stability, the total blending amount of polyethylene glycol (PEG) in the surface layer is 100 parts by mass of the polyolefin resin constituting the surface layer as 15 parts by mass or less; and with respect to 100 parts by mass of the first polyethylene glycol (PEG1) in the surface layer, the amount of the second polyethylene glycol (PEG2) in the surface layer is 3 parts by mass It is preferably at least 100 parts by mass.

第2聚乙二醇(PEG2)可從市場入手。在本發明中，可作為第2聚乙二醇(PEG2)使用之市售物可舉如FUJIFILM Wako Pure Chemical Co.製造之「Polyethylene Glycol 6000」等。The second polyethylene glycol (PEG2) can be obtained from the market. In the present invention, commercially available products that can be used as the second polyethylene glycol (PEG2) include "Polyethylene Glycol 6000" manufactured by FUJIFILM Wako Pure Chemical Co. and the like.

此外，本發明之積層發泡片材於表面層含有第1聚乙二醇(PEG1)以及第2聚乙二醇(PEG2)。所以，即使在高溫多濕之氣體環境下，積層發泡片材相對於被包裝物之剝離強度仍小。因此，譬如在將被包裝物提起取出時，可抑制由積層發泡片材構成之包裝材追隨被包裝物與被包裝物一同被提起的情況。其結果，在使用被包裝物時可有良好的作業性。In addition, the laminated foam sheet of the present invention contains the first polyethylene glycol (PEG1) and the second polyethylene glycol (PEG2) in the surface layer. Therefore, even in a high-temperature and humid gas environment, the peel strength of the laminated foam sheet relative to the packaged object is still small. Therefore, for example, when the packaged object is lifted out, it can be suppressed that the packaging material composed of the laminated foam sheet follows the packaged object and the packaged object to be lifted together. As a result, good workability can be achieved when using the object to be packaged.

(抗靜電劑) 本發明之積層發泡片材可在不損及本發明目的效果之範圍內於表面層摻混抗靜電劑。抗靜電劑宜使用高分子型抗靜電劑。高分子型抗靜電劑可舉聚醚-聚烯烴共聚物、離子聚合物樹脂等。聚醚-聚烯烴共聚物可舉以下列商品名販售之物：三洋化成工業股份有限公司製「Pelestat(商標)VL300」、「Pelestat(商標)300」、「Pelestat HC250」、「Pelectron(商標)HS」、「Pelectron PVH」、「Pelectron LMP」等。離子聚合物樹脂可舉如以下列商品名販售之物：Du Pont-Mitsui Polychemicals Co., Ltd.製「Entira(商標)SD100」、「Entira MK400」等。(Antistatic agent) The laminated foamed sheet of the present invention can be blended with an antistatic agent on the surface layer within a range that does not impair the effect of the present invention. Antistatic agent should use polymer antistatic agent. The polymer type antistatic agent includes polyether-polyolefin copolymer, ionomer resin and the like. Examples of polyether-polyolefin copolymers sold under the following trade names: "Pelestat (trademark) VL300", "Pelestat (trademark) 300", "Pelestat HC250", "Pelectron (trademark)" manufactured by Sanyo Chemical Industry Co., Ltd. )HS", "Pelectron PVH", "Pelectron LMP", etc. Examples of ionic polymer resins are those sold under the following trade names: "Entira (trademark) SD100", "Entira MK400" manufactured by Du Pont-Mitsui Polychemicals Co., Ltd., etc.

(表面電阻率) 本發明之積層發泡片材的表面電阻率宜為1×108 Ω以上且1×1014 Ω以下。積層發泡片材之表面電阻率若為上述範圍內，積層發泡片材即可展現充分的抗靜電性。基於上述觀點，積層發泡片材之表面電阻率宜為5×1013 Ω以下，且1×1013 Ω以下更佳。(Surface resistivity) The surface resistivity of the laminated foam sheet of the present invention is preferably 1×10 8 Ω or more and 1×10 14 Ω or less. If the surface resistivity of the laminated foam sheet is within the above range, the laminated foam sheet can exhibit sufficient antistatic properties. From the above viewpoint, the surface resistivity of the laminated foam sheet is preferably 5×10 13 Ω or less, and more preferably 1×10 13 Ω or less.

積層發泡片材之表面電阻率可依據JIS K 6271(2008年)進行測定。即，將包含積層發泡片材之表面層而裁切成預定尺寸之試驗片放置在溫度20℃、相對濕度30%之氣體環境下36小時，進行試驗片之狀態調節。然後用經狀態調節之試驗片，依據JIS K 6271(2008年)，在施加電壓500V之條件下開始施加電壓經過1分鐘後，求出試驗片中積層發泡片材之表面層之表面部分的表面電阻率，並以此作為積層發泡片材之表面電阻率。The surface resistivity of the laminated foam sheet can be measured according to JIS K 6271 (2008). That is, the test piece including the surface layer of the laminated foam sheet and cut to a predetermined size was placed in a gas environment at a temperature of 20°C and a relative humidity of 30% for 36 hours to adjust the state of the test piece. Then, using a state-adjusted test piece, according to JIS K 6271 (2008), after applying the voltage for 1 minute under the condition of an applied voltage of 500 V, the surface part of the surface layer of the laminated foamed sheet in the test piece was obtained Surface resistivity, and use this as the surface resistivity of the laminated foam sheet.

相對於構成表面層之聚烯烴系樹脂100質量份，前述高分子型抗靜電劑之摻混量宜為2質量份以上且30質量份以下。抗靜電劑之摻混量若在上述範圍內，積層發泡片材即有優異的抗靜電性能。基於上述觀點，相對於前述構成表面層之聚烯烴系樹脂100質量份，抗靜電劑之摻混量為3質量份以上且25質量份以下較佳，5質量份以上且20質量份以下更佳。The blending amount of the polymer antistatic agent is preferably 2 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the polyolefin resin constituting the surface layer. If the blending amount of the antistatic agent is within the above range, the laminated foam sheet has excellent antistatic performance. From the above viewpoint, the blending amount of the antistatic agent is preferably 3 parts by mass or more and 25 parts by mass or less, and more preferably 5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polyolefin resin constituting the surface layer. .

(積層發泡片材之製造方法) 本發明之積層發泡片材譬如可藉由使用環狀模具之共擠製法來製造。首先，將發泡層形成用聚烯烴系樹脂與視需求添加之氣泡調整劑等添加劑供給至發泡層形成用擠製機。接著將包含聚烯烴系樹脂及添加劑之混合物進行加熱捏合並進一步壓入物理發泡劑後，再將混合物與物理發泡劑捏合而獲得發泡層形成用樹脂熔融物。另一方面，將表面層形成用聚烯烴系樹脂、聚乙二醇與視需求添加之抗靜電劑等添加劑供給至表面層形成用擠製機後，進行加熱捏合而獲得表面層形成用樹脂熔融物。然後將發泡層形成用樹脂熔融物與表面層形成用樹脂熔融物導入共擠製用環狀模具中，進行共擠製發泡。藉此形成一於發泡層積層有表面層之筒狀積層發泡體，並且該筒狀積層發泡體擴大徑長的同時進行牽引並予以切割，即可獲得積層發泡片材。(Manufacturing method of laminated foam sheet) The laminated foam sheet of the present invention can be produced by, for example, a co-extrusion method using a ring die. First, an additive such as a polyolefin resin for forming a foamed layer and a bubble regulator added as needed is supplied to an extruder for forming a foamed layer. Next, after the mixture containing the polyolefin-based resin and the additives is heated and kneaded and further pressed into the physical foaming agent, the mixture and the physical foaming agent are kneaded again to obtain a resin melt for forming a foamed layer. On the other hand, after supplying additives such as polyolefin resin for surface layer formation, polyethylene glycol, and antistatic agent added as needed to the extruder for surface layer formation, it is heated and kneaded to obtain resin melt for surface layer formation Thing. Then, the resin melt for foam layer formation and the resin melt for surface layer formation are introduced into a ring die for co-extrusion, and co-extrusion foaming is performed. Thereby, a cylindrical laminated foam having a surface layer laminated on the foamed layer is formed, and the cylindrical laminated foam is pulled and cut while expanding the diameter to obtain a laminated foam sheet.

在積層發泡片材之製造方法中，要獲得表面層形成用樹脂熔融物，可添加第1聚乙二醇(PEG1)與第2聚乙二醇(PEG2)作為聚乙二醇。此時，第1聚乙二醇(PEG1)與第2聚乙二醇(PEG2)之添加方法並無特別限定。譬如，可將第1聚乙二醇(PEG1)與第2聚乙二醇(PEG2)同時供給至表面層形成用擠製機，或可分別供給至表面層形成用擠製機。而且，第2聚乙二醇(PEG2)可與聚烯烴系樹脂一起供給至表面層形成用擠製機，或可預先加熱使其成為液狀後，使用液中泵等供給至表面層形成用擠製機。第1聚乙二醇(PEG1)亦可使用液中泵供給至表面層形成用擠製機。此外，亦可將第1聚乙二醇(PEG1)與第2聚乙二醇(PEG2)預先與表面層形成用聚烯烴系樹脂捏合使其母料化後再供給至表面層形成用擠製機。In the manufacturing method of the laminated foam sheet, to obtain the resin melt for forming the surface layer, the first polyethylene glycol (PEG1) and the second polyethylene glycol (PEG2) may be added as polyethylene glycol. At this time, the method of adding the first polyethylene glycol (PEG1) and the second polyethylene glycol (PEG2) is not particularly limited. For example, the first polyethylene glycol (PEG1) and the second polyethylene glycol (PEG2) may be simultaneously supplied to the extruder for surface layer formation, or may be separately supplied to the extruder for surface layer formation. Furthermore, the second polyethylene glycol (PEG2) may be supplied to the extruder for surface layer formation together with the polyolefin-based resin, or may be heated in advance to be liquid, and then supplied to the surface layer formation using an in-liquid pump or the like Extruder. The first polyethylene glycol (PEG1) can also be supplied to the extruder for surface layer formation using an in-liquid pump. In addition, the first polyethylene glycol (PEG1) and the second polyethylene glycol (PEG2) may be kneaded with the polyolefin resin for surface layer formation in advance to form a master batch, and then supplied to the extrusion for surface layer formation machine.

形成發泡層時使用之氣泡調整劑可使用有機系氣泡調整劑或無機系氣泡調整劑中之任一種。無機系氣泡調整劑可舉硼酸鋅、硼酸鎂、硼砂等硼酸金屬鹽、氯化鈉、氫氧化鋁、滑石、沸石、二氧化矽、碳酸鈣、重碳酸鈣等。另，有機系氣泡調整劑可舉磷酸-2,2-亞甲基雙(4,6-三級丁基苯基)鈉、苯甲酸鈉、苯甲酸鈣、苯甲酸鋁、硬脂酸鈉等。另外，檸檬酸與重碳酸鈉、或檸檬酸之鹼金屬鹽(alkali salt)與重碳酸鈉等的組合物等亦可作為氣泡調整劑使用。再者，該等所例示之各氣泡調整劑亦可2種以上混合使用。As the bubble adjuster used when forming the foamed layer, any one of an organic bubble adjuster or an inorganic bubble adjuster can be used. Examples of the inorganic bubble regulator include metal borate salts such as zinc borate, magnesium borate, and borax, sodium chloride, aluminum hydroxide, talc, zeolite, silica, calcium carbonate, and bicarbonate. In addition, the organic bubble regulator may include sodium 2,2-methylene bis(4,6-tertiary butylphenyl) phosphate, sodium benzoate, calcium benzoate, aluminum benzoate, sodium stearate, and the like. In addition, a combination of citric acid and sodium bicarbonate, or an alkali metal salt of citric acid, sodium bicarbonate, and the like can also be used as a bubble regulator. In addition, each of these illustrated bubble adjusters can also be used in mixture of 2 or more types.

而且，上述中基於發泡層之氣泡徑長容易調整的觀點來看，氣泡調整劑宜使用滑石。另，相對於構成發泡層之聚烯烴系樹脂100質量份，氣泡調整劑宜在大概0.1質量份以上且3質量份以下之範圍內作添加，且較宜為0.2質量份以上且2質量份以下。In addition, from the viewpoint of easy adjustment of the bubble diameter of the foamed layer, talc is preferably used as the bubble adjuster. In addition, with respect to 100 parts by mass of the polyolefin resin constituting the foamed layer, the bubble regulator is preferably added in a range of approximately 0.1 parts by mass or more and 3 parts by mass or less, and more preferably 0.2 parts by mass or more and 2 parts by mass. the following.

物理發泡劑只要是可應用於製造積層發泡片材之發泡層者，即可無特別限制地使用。物理發泡劑可使用無機系物理發泡劑或有機系物理發泡劑。無機系物理發泡劑可舉如氧、氮、二氧化碳、空氣等。有機系物理發泡劑可舉如丙烷、正丁烷、異丁烷、正戊烷、異戊烷、正己烷、異己烷或環己烷等脂肪族烴；氯甲基或氯乙基等氯化烴；1,1,1,2-四氟乙烷、1,1-二氟乙烷、1,3,3,3-四氟丙烯或1-氯-3,3,3-三氟丙烯等氟化烴；二甲基醚或甲基乙基醚等醚類；或是甲醇或乙醇等醇類等。再者，上述物理發泡劑亦可將2種以上混合使用。The physical foaming agent can be used without particular limitation as long as it can be applied to the foaming layer for manufacturing a laminated foam sheet. As the physical foaming agent, an inorganic physical foaming agent or an organic physical foaming agent can be used. Examples of the inorganic physical blowing agent include oxygen, nitrogen, carbon dioxide, and air. Organic physical blowing agents include aliphatic hydrocarbons such as propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, isohexane or cyclohexane; chlorine such as chloromethyl or chloroethyl Hydrocarbon; 1,1,1,2-tetrafluoroethane, 1,1-difluoroethane, 1,3,3,3-tetrafluoropropene or 1-chloro-3,3,3-trifluoropropene Fluorinated hydrocarbons; ethers such as dimethyl ether or methyl ethyl ether; or alcohols such as methanol or ethanol. In addition, the said physical foaming agent can also be used in mixture of 2 or more types.

該等物理發泡劑中，若從可穩定實施共擠製法而穩定獲得良好的發泡層的觀點來看，物理發泡劑宜使用正丁烷、異丁烷或該等之混合物。Among these physical blowing agents, n-butane, isobutane or a mixture of these is preferably used as the physical blowing agent from the viewpoint that a co-extrusion method can be stably carried out and a good foamed layer can be stably obtained.

(玻璃板用間隔紙) 本發明之積層發泡片材可作為玻璃板用間隔紙使用。玻璃板用間隔紙係可用夾裝在玻璃板之間者，可防止玻璃板彼此因接觸而破損。使用所述玻璃板用間隔紙之玻璃板，可舉液晶顯示器等顯示器用玻璃板。顯示器用玻璃板在拆除夾裝在玻璃板之間的玻璃板用間隔紙後，通常會個別用水等洗滌後使用。此時，玻璃板之表面若有塵、埃、有機物等接觸，會很難以水等沖洗塵、埃、有機物等。關於這點，玻璃板用間隔紙若是由本發明之積層發泡片材構成，則聚乙二醇便會順利地從積層發泡片材移動至玻璃板表面上，而且用水等洗滌個別的玻璃板時，能輕易地洗去附著在玻璃板表面上的塵、埃、有機物等。(Spacer for glass plate) The laminated foam sheet of the present invention can be used as a spacer for glass plates. The spacer paper for glass plates can be clamped between glass plates to prevent the glass plates from being damaged due to contact. Examples of the glass plate using the spacer paper for glass plates include glass plates for displays such as liquid crystal displays. After removing the spacer for the glass plate sandwiched between the glass plates, the glass plate for display is usually washed separately with water or the like. At this time, if the surface of the glass plate is exposed to dust, dust, organic matter, etc., it will be difficult to wash the dust, dust, organic matter, etc. with water. In this regard, if the spacer for glass plates is composed of the laminated foamed sheet of the present invention, polyethylene glycol will smoothly move from the laminated foamed sheet to the surface of the glass sheet, and the individual glass sheets are washed with water, etc. At the same time, it can easily wash off the dust, angstroms, organic matter, etc. attached to the surface of the glass plate.

此外，玻璃板用間隔紙有時也會以夾裝在玻璃板之間的狀態放在高溫多濕氣體環境下。關於這點，玻璃板用間隔紙若是由本發明之積層發泡片材構成，即可壓低積積層發泡片材的吸水率，所以即使被放在高溫多濕之氣體環境下，積層發泡片材表面也不易附著塵、埃、有機物等。因此，可有效抑制塵、埃、有機物等經由積層發泡片材附著於玻璃板而汙染玻璃板的情況。In addition, the spacer paper for glass plates is sometimes placed in a high-temperature and humid gas environment in a state of being sandwiched between glass plates. In this regard, if the spacer for glass plates is composed of the laminated foam sheet of the present invention, the water absorption of the laminated foam sheet can be reduced, so even if it is placed in a high-temperature and humid gas environment, the laminated foam sheet The surface of the wood is also not easy to adhere to dust, dust, organic matter, etc. Therefore, it is possible to effectively prevent dust, angstroms, organic matter, etc. from adhering to the glass plate via the laminated foam sheet and contaminating the glass plate.

再者，本發明之積層發泡片材如上述，即使在高溫多濕氣體環境下其與被包裝物之剝離強度仍小。因此，譬如在將板狀的被包裝物提起取出時，積層發泡片材不會追隨被包裝物與被包裝物一同被提起，作業性良好。此點同樣支持本發明之積層發泡片材可適合作為玻璃板用間隔紙使用。Furthermore, as described above, the laminated foam sheet of the present invention has a low peel strength from the packaged object even in a high-temperature and humid gas environment. Therefore, for example, when the plate-shaped object to be packaged is lifted out, the laminated foamed sheet will not be lifted along with the object to be packaged, and the workability is good. This point also supports that the laminated foam sheet of the present invention can be suitably used as a spacer for glass plates.

另，本發明之積層發泡片材不只是僅發泡層單面積層有表面層者，亦可為兩面積層有表面層者。使用積層發泡片材作為玻璃板用間隔紙時，宜發泡層之兩面積層有表面層。於發泡層兩面具備表面層之玻璃板用間隔紙在夾裝在玻璃板之間時，可使與玻璃板用間隔紙接觸之2片玻璃板兩者一起降低汙染性且提升可洗性。In addition, the laminated foamed sheet of the present invention is not only a foamed layer having a surface layer in a single-area layer, but also a two-area layer having a surface layer. When using a laminated foam sheet as a spacer for glass plates, it is preferable that the two layers of the foam layer have surface layers. When the spacer paper for a glass plate provided with a surface layer on both sides of the foam layer is sandwiched between glass plates, the two glass plates in contact with the spacer paper for a glass plate can both reduce contamination and improve washability.

以下根據實施例來詳細說明本發明。惟，本發明不受實施例限定。 實施例The present invention will be described in detail below based on examples. However, the present invention is not limited by the examples. Examples

聚烯烴系樹脂係使用低密度聚乙烯(密度922kg/m3 )(表2中以LDPE1之簡稱表示)(股份有限公司NUC製，品名NUC8321)。For the polyolefin-based resin system, low-density polyethylene (density 922 kg/m 3 ) (indicated by the abbreviation of LDPE1 in Table 2) (manufactured by NUC Corporation, product name NUC8321) is used.

聚乙二醇(表1、表2中以PEG之簡稱表示)如表1所示使用了PEG300、PEG600、PEG4000、PEG6000之4種。PEG300、PEG600對應第1聚乙二醇(表2中以PEG1之簡稱表示)，PEG4000、PEG6000則對應第2聚乙二醇(表2中以PEG2之簡稱表示)。Polyethylene glycol (denoted by the abbreviation of PEG in Tables 1 and 2) uses four types of PEG300, PEG600, PEG4000, and PEG6000 as shown in Table 1. PEG300 and PEG600 correspond to the first polyethylene glycol (denoted by the abbreviation of PEG1 in Table 2), and PEG4000 and PEG6000 correspond to the second polyethylene glycol (denoted by the abbreviation of PEG2 in Table 2).

[表1]

Figure 02_image003
[Table 1]
Figure 02_image003

抗靜電劑係使用高分子型抗靜電劑之聚醚-聚烯烴共聚物(表2中以ASP1之簡稱表示)(三洋化成工業股份有限公司製，商品名Pelestat(商標)300，體積電阻率1×108 (Ω・cm))。The antistatic agent is a polyether-polyolefin copolymer using a polymer type antistatic agent (referred to as ASP1 in Table 2) (manufactured by Sanyo Chemical Industry Co., Ltd., trade name Pelestat (trademark) 300, volume resistivity 1 ×10 8 (Ω・cm)).

物理發泡劑係使用由正丁烷70質量%與異丁烷30質量%所構成之混合丁烷。The physical blowing agent is a mixed butane composed of 70% by mass of n-butane and 30% by mass of isobutane.

氣泡調整劑係使用氣泡調整劑母料，該氣泡調整劑母料係對低密度聚乙烯80質量%摻混20質量%之滑石(松村產業股份有限公司製，商品名HI-FILLER #12)而成。The bubble adjuster system uses a bubble adjuster masterbatch, which mixes low-density polyethylene with 80% by mass of 20% by mass of talc (Matsumura Industries Co., Ltd., trade name HI-FILLER #12). to make.

發泡層形成用擠製機係使用由內徑90mm之第一擠製機與內徑120mm之第二擠製機構成的串接擠製機，表面層形成用擠製機則使用內徑50mm且L/D=50之第三擠製機。並且將第二擠製機與第三擠製機的各個出口連結至共擠製用環狀模具，使後述之各個樹脂熔融物可在共擠製用環狀模具內積層。此外將各實施例及各比較例中之積層發泡片材設計成發泡層之平均厚度為0.1464mm，且兩面之表面層的平均厚度分別為0.0018mm。The extruder for forming the foamed layer is a tandem extruder composed of a first extruder with an inner diameter of 90 mm and a second extruder with an inner diameter of 120 mm, and an extruder for forming a surface layer with an inner diameter of 50 mm And the third extruder with L/D=50. In addition, each outlet of the second extruder and the third extruder is connected to a ring die for co-extrusion, so that each resin melt described later can be stacked in the ring die for co-extrusion. In addition, the laminated foam sheets in the examples and comparative examples were designed so that the average thickness of the foam layer was 0.1464 mm, and the average thickness of the surface layers on both sides was 0.0018 mm.

實施例1至7 (調製發泡層形成用樹脂熔融物) 將低密度聚乙烯系樹脂與相對於該樹脂100質量份為1.5質量份之氣泡調整劑母料供給至第一擠製機並進行熔融、捏合而做出調整成約200℃之樹脂熔融物。其次，壓入相對於該樹脂100質量份為10質量份之混合丁烷，接著傳送至連接在第一擠製機之下游側的第二擠製機，將擠製樹脂溫度調整至115℃而做成發泡層形成用樹脂熔融物後，導入前述共擠製用環狀模具中。Examples 1 to 7 (Preparation of resin melt for foam layer formation) A low-density polyethylene-based resin and a bubble adjuster masterbatch of 1.5 parts by mass with respect to 100 parts by mass of the resin were supplied to the first extruder and melted and kneaded to prepare a resin melt adjusted to about 200°C. Next, press into the mixed butane of 10 parts by mass relative to 100 parts by mass of the resin, and then transfer to the second extruder connected to the downstream side of the first extruder to adjust the temperature of the extruded resin to 115°C. After forming the resin melt for forming the foamed layer, it is introduced into the aforementioned ring die for co-extrusion.

(調製表面層形成用樹脂熔融物) 另一方面，將表2所示之量的低密度聚乙烯系樹脂與高分子型抗靜電劑以及表2所示之量、種類的第1聚乙二醇(PEG1)及第2聚乙二醇(PEG2)供給至第三擠製機並進行熔融、捏合，將擠製樹脂溫度調整至115℃而做出表面層形成用樹脂熔融物後，導入前述共擠製用環狀模具中。另外，前述PEG1係透過與第三擠製機連結之液中泵供給，PEG2則是與低密度聚乙烯系樹脂一起添加至第三擠製機。(Preparation of resin melt for forming surface layer) On the other hand, the amount of low-density polyethylene resin and polymer antistatic agent shown in Table 2 and the amounts and types of first polyethylene glycol (PEG1) and second polyethylene glycol shown in Table 2 After the alcohol (PEG2) is supplied to the third extruder, it is melted and kneaded, and the temperature of the extruded resin is adjusted to 115°C to prepare a resin melt for forming a surface layer, and then introduced into the aforementioned ring die for co-extrusion. In addition, the aforementioned PEG1 is supplied through the liquid pump connected to the third extruder, and PEG2 is added to the third extruder together with the low-density polyethylene resin.

使已導入共擠製用環狀模具中之表面層形成用樹脂熔融物在已導入共擠製用環狀模具中之發泡層形成用樹脂熔融物的外側與內側匯流並積層後，從上述環狀模具以吐出量130kg/hr擠製至大氣中，做成筒狀積層發泡體。此時，將筒狀積層發泡體擴大徑長使吹開比(blow-up ratio)成為2.8，並同時以捲收速度67m/min捲收且沿著擠製方向進行切割。藉此製造出表面層/發泡層/表面層之3層構成的積層發泡片材(寬度約1400mm)。另，以上述條件所製造之積層發泡片材的表面層(單側面)基重為1.7g/m2 。After the resin melt for forming the surface layer introduced into the ring mold for co-extrusion is merged and laminated on the outside and inside of the resin melt for forming the foam layer introduced into the ring mold for co-extrusion, from the above The ring-shaped die was extruded into the atmosphere at a discharge rate of 130 kg/hr to make a cylindrical laminated foam. At this time, the diameter of the cylindrical laminate foam was expanded to a blow-up ratio of 2.8, and at the same time, it was wound at a winding speed of 67 m/min and cut along the extrusion direction. By this, a laminated foam sheet (width about 1400 mm) composed of three layers of surface layer/foam layer/surface layer was produced. In addition, the basis weight of the surface layer (one side) of the laminated foam sheet produced under the above conditions was 1.7 g/m 2 .

針對所得積層發泡片材如以下方式測定平均厚度、視密度、表面電阻率、吸水率及玻璃板剝離強度。並且如下評估玻璃板可洗性。結果列於表2。For the obtained laminated foamed sheet, the average thickness, apparent density, surface resistivity, water absorption rate, and glass plate peel strength were measured as follows. And the washability of the glass plate was evaluated as follows. The results are shown in Table 2.

(積層發泡片材之平均厚度) 在積層發泡片材之整個範圍沿著寬度方向以1cm間隔測定片材之厚度(mm)，並以其等之算術平均算出平均厚度。在積層發泡片材上隨機選出3處進行前述測定後，以所算出之前述3處的平均厚度之值的算術平均值為積層發泡片材之平均厚度(mm)。(Average thickness of laminated foam sheet) The thickness (mm) of the sheet was measured at intervals of 1 cm along the width direction over the entire range of the laminated foam sheet, and the average thickness was calculated by the arithmetic average of the same. After randomly selecting 3 places on the laminated foam sheet and performing the aforementioned measurement, the arithmetic average of the calculated values of the average thickness of the above 3 places is the average thickness (mm) of the laminated foam sheet.

(積層發泡片材之視密度) 在積層發泡片材之擠製方向隨機選出5處，並針對各個場所在片材整個範圍上裁切出片材寬×寬100mm而準備了5個試驗片。然後測定各試驗片之質量(kg)並從外形尺寸求出體積(m3 )後，將上述質量(kg)除以上述體積(m3 )而求出各試驗片之視密度(kg/m3 )，並以所得之值的算術平均值為視密度(kg/m3 )。(Visual density of laminated foam sheet) Five places were randomly selected in the extrusion direction of the laminated foam sheet, and 5 trials were prepared for each place to cut out the sheet width × width 100mm over the entire range of the sheet sheet. Then, the mass (kg) of each test piece is measured and the volume (m 3 ) is obtained from the external dimensions, and the apparent density (kg/m) of each test piece is obtained by dividing the mass (kg) by the volume (m 3 ). 3 ), and take the arithmetic mean of the obtained values as the apparent density (kg/m 3 ).

(積層發泡片材之表面電阻率) 積層發泡片材之表面電阻率係根據JIS K 6271(2008年)進行測定。具體上，係從積層發泡片材隨機裁切出長100mm×寬100mm之試驗片後，在溫度20℃、相對濕度30%之氣體環境下放置36小時來施行試驗片之狀態調節。接著，在施加電壓500V之條件下針對各個試驗片的兩面施加電壓。開始施加電壓經過1分鐘後，測定試驗片之表面電阻率，並以其等之算術平均值(試驗片5片×兩面[n=10])為積層發泡片材的表面電阻率(Ω)。(Surface resistivity of laminated foam sheet) The surface resistivity of the laminated foam sheet is measured according to JIS K 6271 (2008). Specifically, after randomly cutting out a test piece having a length of 100 mm and a width of 100 mm from the laminated foam sheet, the state of the test piece is adjusted by placing it in a gas environment at a temperature of 20° C. and a relative humidity of 30% for 36 hours. Next, a voltage was applied to both surfaces of each test piece under an applied voltage of 500V. After 1 minute from the start of voltage application, the surface resistivity of the test piece was measured, and the arithmetic mean value (5 test pieces × two sides [n=10]) of the test piece was used as the surface resistivity (Ω) of the laminated foam sheet .

(積層發泡片材之吸水率) 以下述方式測定積層發泡片材之吸水率(質量ppm)。首先從積層發泡片材裁切出5片寬500mm×長400mm之大小的試驗片，在溫度25℃且濕度50%RH及溫度50℃且濕度80%RH之2種條件下保管24小時。然後，在遮斷空氣之密閉空間中以180℃使試驗片乾燥，去除水分以外之氣化物後，選擇性地使水分吸附於分子篩性吸附劑(Nacalai Tesque Inc.製，分子篩3A°)，並從其質量變化按以下式(2)求出吸水率(質量ppm)。並且以其算術平均值作為積層發泡片材之吸水率(ppm)。另，RH表示相對濕度。(Water absorption rate of laminated foam sheet) The water absorption rate (mass ppm) of the laminated foamed sheet was measured in the following manner. First, five test pieces with a width of 500 mm and a length of 400 mm were cut out from the laminated foam sheet, and stored for 24 hours under two conditions of a temperature of 25° C. and a humidity of 50% RH and a temperature of 50° C. and a humidity of 80% RH. Then, the test piece was dried at 180°C in a closed space where the air was blocked, and after removing gaseous substances other than moisture, the moisture was selectively adsorbed on a molecular sieve adsorbent (manufactured by Nacalai Tesque Inc., molecular sieve 3A°), and From the change in mass, the water absorption rate (mass ppm) was determined according to the following formula (2). The arithmetic mean value is used as the water absorption rate (ppm) of the laminated foam sheet. In addition, RH represents relative humidity.

[數學式2]

Figure 02_image005
[Mathematical formula 2]
Figure 02_image005

惟，上述式(2)中，M1 表示試驗片乾燥前之質量(g)，M2 表示吸水後之吸附劑質量(g)，M3 表示吸水前之吸附劑質量(g)。However, in the above formula (2), M 1 represents the mass (g) of the test piece before drying, M 2 represents the mass (g) of the adsorbent after water absorption, and M 3 represents the mass (g) of the adsorbent before water absorption.

(玻璃板剝離強度) 以下述方式測定積層發泡片材與玻璃板之剝離強度(玻璃板剝離強度)(N)。首先，從積層發泡片材裁切出5片寬60mm×長90mm之尺寸的試驗片後，將切出之5片試驗片與5片玻璃板交錯重疊並以荷重25g/cm2 壓接7天。然後測定將壓接於玻璃板之試驗片在100mm/min之速度下進行剝離時的荷重，並以此為剝離強度(N)。求出各試驗片剝離時的剝離強度(N)之值的算術平均值並列於表2。剝離強度之測定係在溫度25℃且濕度50%RH及溫度50℃且濕度80%RH之2種條件下進行。(Glass plate peel strength) The peel strength (glass plate peel strength) (N) of the laminated foam sheet and the glass plate was measured in the following manner. First, after cutting out 5 test pieces with a width of 60 mm × a length of 90 mm from the laminated foam sheet, the cut 5 test pieces and 5 glass plates are alternately overlapped and crimped with a load of 25 g/cm 2 7 day. Then, the load when peeling the test piece crimped to the glass plate at a speed of 100 mm/min was measured, and this was used as the peel strength (N). The arithmetic mean value of the peeling strength (N) at the time of peeling of each test piece was calculated and shown in Table 2. The measurement of the peel strength is performed under two conditions of a temperature of 25°C and a humidity of 50% RH and a temperature of 50°C and a humidity of 80% RH.

(玻璃板可洗性) 玻璃板可洗性係藉由玻璃板之可洗性的評估試驗作評估。玻璃板之可洗性的評估試驗係在常溫保管條件與高溫多濕保管條件之2種條件下以下述方式實施。即，在使積層發泡片材與玻璃板接觸之狀態下(荷重條件：3.8g/cm2 )，於溫度25℃且濕度50%RH下保管24小時(常溫保管條件)後，將積層發泡片材剝離後洗滌玻璃板，並測定玻璃板之面中與積層發泡片材之接觸面中的水接觸角。以及，在使積層發泡片材與玻璃板接觸之狀態下，於溫度50℃且濕度80%RH下保管24小時(高溫多濕保管條件)後，將積層發泡片材剝離後洗滌玻璃板，並測定玻璃板之面中與積層發泡片材之接觸面中的水接觸角(測定環境條件：溫度25℃、濕度50%RH)。另，水接觸角之測定係使用接觸角計DM500R(協和界面科學股份有限公司製)進行，並於附液量1.5μL、附液後5秒後進行測定。(Glass plate washability) The glass plate washability is evaluated by the evaluation test of the glass plate washability. The evaluation test of the washability of the glass plate was carried out in the following manner under two kinds of storage conditions at normal temperature and storage conditions at high temperature and high humidity. That is, in a state where the laminated foamed sheet is in contact with the glass plate (load condition: 3.8 g/cm 2 ), after storing at a temperature of 25° C. and a humidity of 50% RH for 24 hours (normal temperature storage conditions), the laminate is released After the foam sheet is peeled off, the glass plate is washed, and the water contact angle between the surface of the glass plate and the contact surface of the laminated foam sheet is measured. And, in a state where the laminated foam sheet is in contact with the glass plate, after storing at a temperature of 50° C. and a humidity of 80% RH for 24 hours (high-temperature and humid storage conditions), the laminated foam sheet is peeled off and the glass plate is washed , And measure the water contact angle between the surface of the glass plate and the contact surface of the laminated foam sheet (measurement environmental conditions: temperature 25 ℃, humidity 50% RH). In addition, the measurement of the water contact angle was performed using a contact angle meter DM500R (manufactured by Kyowa Interface Science Co., Ltd.), and the measurement was performed 5 seconds after the amount of the attached liquid and 1.5 seconds after the attached liquid.

根據洗滌後之玻璃板上之水接觸角的測定結果，按以下評估基準來評估玻璃板可洗性。 ○(玻璃板可洗性良好)：洗滌後之水接觸角小於10° ×(玻璃板可洗性不良)：洗滌後之水接觸角為10°以上According to the measurement results of the water contact angle on the glass plate after washing, the washability of the glass plate was evaluated according to the following evaluation criteria. ○(Good washability of glass plate): The water contact angle after washing is less than 10° ×(Poor washability of glass plate): The water contact angle after washing is above 10°

比較例1 除了未使用第2聚乙二醇(PEG2)而僅用第1聚乙二醇(PEG1)以外，以與實施例1同樣方式製得積層發泡片材。使用所得積層發泡片材，以與實施例1同樣方式測定平均厚度(mm)、發泡層之視密度(kg/m3 )、表面電阻率(Ω)、吸水率(質量ppm)、玻璃板剝離強度(N)。並且實施玻璃板可洗性之評估試驗。結果列於表2。所得積層發泡片材在高溫多濕條件下吸水率高、玻璃可洗性差。Comparative Example 1 A laminated foam sheet was produced in the same manner as in Example 1, except that the second polyethylene glycol (PEG2) was not used and only the first polyethylene glycol (PEG1) was used. Using the obtained laminated foamed sheet, the average thickness (mm), apparent density of the foamed layer (kg/m 3 ), surface resistivity (Ω), water absorption rate (mass ppm), glass were measured in the same manner as in Example 1. Board peel strength (N). And carry out the evaluation test of the washability of the glass plate. The results are shown in Table 2. The resulting laminated foam sheet has a high water absorption rate under high temperature and humidity conditions, and poor glass washability.

比較例2 除了使用表2所示之物作為第1聚乙二醇(PEG1)以外，以與比較例1同樣方式製得積層發泡片材。使用所得積層發泡片材，以與實施例1同樣方式測定平均厚度、發泡層之視密度、表面電阻率、吸水率、玻璃板剝離強度。並且實施玻璃板可洗性之評估試驗。結果列於表2。與比較例1同樣地，所得積層發泡片材在高溫多濕條件下吸水率高、玻璃可洗性差。Comparative example 2 A laminated foam sheet was produced in the same manner as in Comparative Example 1 except that the materials shown in Table 2 were used as the first polyethylene glycol (PEG1). Using the obtained laminated foam sheet, the average thickness, the apparent density of the foam layer, the surface resistivity, the water absorption rate, and the glass sheet peel strength were measured in the same manner as in Example 1. And carry out the evaluation test of the washability of the glass plate. The results are shown in Table 2. As in Comparative Example 1, the resulting laminated foam sheet had high water absorption under high-temperature and high-humidity conditions, and poor glass washability.

比較例3 除了未使用第1聚乙二醇(PEG1)而僅用第2聚乙二醇(PEG2)以外，以與實施例1同樣方式製得積層發泡片材。使用所得積層發泡片材，以與實施例1同樣方式測定平均厚度、發泡層之視密度、表面電阻率、吸水率、玻璃板剝離強度。並且實施玻璃板可洗性之評估試驗。結果列於表2。所得積層發泡片材雖有壓低吸水率，但玻璃可洗性非常差。Comparative Example 3 A laminated foam sheet was produced in the same manner as in Example 1, except that the first polyethylene glycol (PEG1) was not used and only the second polyethylene glycol (PEG2) was used. Using the obtained laminated foam sheet, the average thickness, the apparent density of the foam layer, the surface resistivity, the water absorption rate, and the glass sheet peel strength were measured in the same manner as in Example 1. And carry out the evaluation test of the washability of the glass plate. The results are shown in Table 2. Although the obtained laminated foamed sheet has a reduced water absorption rate, glass washability is very poor.

[表2]

Figure 02_image007
[Table 2]
Figure 02_image007

(無)(no)

Claims (9)

一種聚烯烴系樹脂積層發泡片材，係具有聚烯烴系樹脂發泡層與聚烯烴系樹脂表面層的積層發泡片材，其中該聚烯烴系樹脂表面層積層接著在該發泡層之至少單面側；其特徵在於： 前述表面層摻混有聚乙二醇(PEG)， 前述聚乙二醇(PEG)係由在25℃下為液體之第1聚乙二醇(PEG1)與在25℃下為固體之第2聚乙二醇(PEG2)構成； 相對於構成前述表面層之聚烯烴系樹脂100質量份，前述表面層中之前述第1聚乙二醇(PEG1)的摻混量為0.5質量份以上且10質量份以下； 相對於前述表面層中之前述第1聚乙二醇(PEG1)的摻混量100質量份，前述表面層中之前述第2聚乙二醇(PEG2)的摻混量為3質量份以上。A polyolefin-based resin laminated foamed sheet, which is a laminated foamed sheet having a polyolefin-based resin foamed layer and a polyolefin-based resin surface layer, wherein the polyolefin-based resin surface laminated layer is followed by the foamed layer At least one side; characterized by: The aforementioned surface layer is blended with polyethylene glycol (PEG), The aforementioned polyethylene glycol (PEG) is composed of a first polyethylene glycol (PEG1) that is liquid at 25°C and a second polyethylene glycol (PEG2) that is solid at 25°C; The blending amount of the first polyethylene glycol (PEG1) in the surface layer is 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polyolefin resin constituting the surface layer; The blending amount of the second polyethylene glycol (PEG2) in the surface layer is 3 parts by mass or more with respect to 100 mass parts of the blending amount of the first polyethylene glycol (PEG1) in the surface layer. 如請求項1之聚烯烴系樹脂積層發泡片材，其中前述第1聚乙二醇(PEG1)之數量平均分子量為100以上且800以下。The polyolefin resin laminated foamed sheet according to claim 1, wherein the number average molecular weight of the first polyethylene glycol (PEG1) is 100 or more and 800 or less. 如請求項1或2之聚烯烴系樹脂積層發泡片材，其中前述第2聚乙二醇(PEG2)之數量平均分子量為2000以上。The polyolefin resin laminated foamed sheet according to claim 1 or 2, wherein the number average molecular weight of the aforementioned second polyethylene glycol (PEG2) is 2000 or more. 如請求項1至3中任一項之聚烯烴系樹脂積層發泡片材，其中前述第2聚乙二醇(PEG2)之凝固點為超過50℃之溫度。The polyolefin resin laminated foamed sheet according to any one of claims 1 to 3, wherein the freezing point of the aforementioned second polyethylene glycol (PEG2) is a temperature exceeding 50°C. 如請求項1至4中任一項之聚烯烴系樹脂積層發泡片材，其中相對於前述表面層中之前述第1聚乙二醇(PEG1)的摻混量100質量份，前述表面層中之前述第2聚乙二醇(PEG2)的摻混量為3質量份以上且100質量份以下。The polyolefin-based resin laminated foamed sheet according to any one of claims 1 to 4, wherein the surface layer is added to 100 parts by mass of the blending amount of the first polyethylene glycol (PEG1) in the surface layer Among them, the blending amount of the aforementioned second polyethylene glycol (PEG2) is 3 parts by mass or more and 100 parts by mass or less. 如請求項1至5中任一項之聚烯烴系樹脂積層發泡片材，其中相對於構成前述表面層之聚烯烴系樹脂100質量份，前述聚乙二醇(PEG)之總摻混量為15質量份以下。The polyolefin resin laminated foamed sheet according to any one of claims 1 to 5, wherein the total blending amount of the polyethylene glycol (PEG) is 100 parts by mass of the polyolefin resin constituting the surface layer. 15 parts by mass or less. 如請求項1至6中任一項之聚烯烴系樹脂積層發泡片材，其中於前述表面層摻混有高分子型抗靜電劑，且相對於構成前述表面層之聚烯烴系樹脂100質量份，該高分子型抗靜電劑之摻混量為2質量份以上且30質量份以下。The polyolefin resin laminated foamed sheet according to any one of claims 1 to 6, wherein the surface layer is blended with a polymer-type antistatic agent, and is relative to 100 mass of the polyolefin resin constituting the surface layer Parts, the blending amount of the polymer antistatic agent is 2 parts by mass or more and 30 parts by mass or less. 如請求項1至7中任一項之聚烯烴系樹脂積層發泡片材，其中構成前述發泡層之聚烯烴系樹脂為低密度聚乙烯， 且構成前述表面層之聚烯烴系樹脂為低密度聚乙烯。The polyolefin resin laminated foam sheet according to any one of claims 1 to 7, wherein the polyolefin resin constituting the foam layer is low density polyethylene, And the polyolefin resin constituting the surface layer is low density polyethylene. 一種玻璃板用間隔紙，係由如請求項1至8中任一項之聚烯烴系樹脂積層發泡片材構成。A spacer paper for a glass plate is composed of a polyolefin resin laminated foamed sheet according to any one of claims 1 to 8.
TW108107854A 2018-06-01 2019-03-08 Polyolefin resin laminated foam sheet and spacer paper for glass plate composed of the laminated foam sheet TWI779172B (en)

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