TWI500512B - Foamed resin sheet - Google Patents
Foamed resin sheet Download PDFInfo
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- TWI500512B TWI500512B TW099139762A TW99139762A TWI500512B TW I500512 B TWI500512 B TW I500512B TW 099139762 A TW099139762 A TW 099139762A TW 99139762 A TW99139762 A TW 99139762A TW I500512 B TWI500512 B TW I500512B
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
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- 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
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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- 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
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
- C08J2201/03—Extrusion of the foamable blend
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- 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
- C08J2389/00—Characterised by the use of proteins; Derivatives thereof
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- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L89/00—Compositions of proteins; Compositions of derivatives thereof
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Description
本發明係關於一種使用擠出機將聚丙烯系樹脂組合物擠出發泡而形成之樹脂發泡片材。The present invention relates to a resin foamed sheet formed by extrusion-expanding a polypropylene resin composition using an extruder.
先前,使樹脂組合物發泡成片狀所得之樹脂發泡片材被廣泛地利用於要求輕質性及緩衝性之用途中。Conventionally, a resin foamed sheet obtained by foaming a resin composition into a sheet form is widely used in applications requiring light weight and cushioning properties.
其中,藉由以聚丙烯系樹脂作為主成分之聚丙烯系樹脂組合物所形成的樹脂發泡片材由於價格相對低廉而得到廣泛使用。Among them, a resin foamed sheet formed of a polypropylene resin composition containing a polypropylene resin as a main component is widely used because of its relatively low cost.
此種樹脂發泡片材通常係將聚丙烯系樹脂組合物擠出發泡而連續地製造,並且不僅製造僅發泡樹脂層單層者,亦製造表面包含稱為膜層等之非發泡樹脂層者。Such a resin foamed sheet is usually produced by continuously foaming a polypropylene resin composition, and not only a single layer of a foamed resin layer but also a non-foamed resin called a film layer. Layer.
該樹脂發泡片材除直接以片狀用作玻璃板之緩衝片材等以外,亦用作藉由片材成形法製作發泡盤等具有立體結構之發泡成形品時的原材料。The resin foamed sheet is used as a material for forming a foamed molded article having a three-dimensional structure such as a foamed disk by a sheet forming method, in addition to being used as a buffer sheet for a glass sheet in a sheet form.
且說,業界關於此種發泡成形品之製作方法進行了各種研究,例如下述專利文獻1中,記載有藉由在聚丙烯系樹脂組合物中含有50質量%以上之高熔融張力聚丙烯樹脂(以下,亦稱為「HMS-PP」),而獲得成形性優異之樹脂發泡片材。In addition, various methods have been studied in the production of such a foamed molded article. For example, Patent Document 1 discloses that a polypropylene resin composition contains 50% by mass or more of a high melt tension polypropylene resin. (hereinafter, also referred to as "HMS-PP"), a resin foamed sheet excellent in moldability is obtained.
再者,將樹脂發泡片材成形加工成發泡盤等時,廣泛採用在加熱樹脂發泡片材而使之軟化之狀態下,藉由負壓(抽成真空)而使該樹脂發泡片材吸附於形成為盤形狀之成形模中的真空成形,或者於正壓下將樹脂發泡片材按壓於成形模中的稱為氣壓成形之成形方法。In addition, when the resin foamed sheet is formed into a foamed disk or the like, the resin is foamed by a vacuum (vacuum) by heating the resin foamed sheet and softening it. A forming method called air pressure forming in which a sheet is adsorbed in a forming die formed into a disk shape or a resin foamed sheet is pressed against a forming die under a positive pressure.
於上述真空成形或氣壓成形中,由於係一面握持樹脂發泡片材之周圍一面於該樹脂發泡片材中形成凹凸,故而樹脂發泡片材並非整體均質之狀態,例如若樹脂發泡片材產生厚度不均勻等,則容易藉由應力而延伸之厚度較薄之部位優先延伸,有時存在成形品產生外觀不良,或者成形品中形成斷裂部位之虞。In the above-described vacuum forming or air pressure forming, since the unevenness is formed in the resin foamed sheet while holding the periphery of the resin foamed sheet, the resin foamed sheet is not in a state of being homogeneous as a whole, for example, if the resin is foamed. When the sheet is uneven in thickness or the like, it is easy to extend the portion where the thickness is thin by the stress, and the appearance of the molded article may be poor, or the fracture portion may be formed in the molded article.
再者,使樹脂發泡片材形成為均質之狀態,係不僅供給至成形加工之樹脂發泡片材,而且將樹脂發泡片材以片狀直接使用之情形亦要求之事項。In addition, the resin foamed sheet is formed into a homogeneous state, and is required to be supplied not only to the resin foamed sheet which is formed, but also to the resin foamed sheet in the form of a sheet.
但是,要使樹脂發泡片材之整個面形成為均質之狀態較為困難,藉由擠出發泡而形成樹脂發泡片材時,存在於擠出方向上連續地產生表面光澤等質感之差異,從而在樹脂發泡片材之表面出現條紋花紋之情形。However, it is difficult to form the entire surface of the resin foamed sheet in a homogeneous state, and when the resin foamed sheet is formed by extrusion foaming, there is a difference in texture such as surface gloss continuously in the extrusion direction. Thus, a streak pattern appears on the surface of the resin foamed sheet.
另外,於樹脂發泡片材之表面觀看到此種條紋之大多情形時,表面光澤存在差異之部分不僅外觀不同,而且片材之厚度或密度(發泡度)等亦有微細之差別。Further, when most of such streaks are observed on the surface of the resin foamed sheet, the difference in surface gloss differs not only in appearance but also in the thickness or density (foaming degree) of the sheet.
因此,通常若樹脂發泡片材上產生此種條紋,則與表面觀察不到條紋之樹脂發泡片材相比在真空成形或氣壓成形中產生缺陷之可能性提高,故而要求防止此種條紋之產生。Therefore, in general, if such streaks are formed on the resin foamed sheet, the possibility of occurrence of defects in vacuum forming or air pressure forming is higher than that of the resin foamed sheet in which no streaks are observed on the surface, and thus it is required to prevent such streaks. Produced.
但是,迄今為止尚未確立起防止該條紋之方法,仍主要採取對症療法式之對策。However, the method of preventing the streaks has not been established so far, and countermeasures against symptomatic therapy are still mainly adopted.
例如係採取下述對策,根據經驗選擇不易產生條紋之擠出條件開始聚丙烯系樹脂組合物之擠出發泡,假設於所擠出之樹脂發泡片材上觀看到條紋時,則進一步微調擠出條件,找出條紋消失之條件然後取得製品。For example, the following measures are taken, and the extrusion foaming of the polypropylene resin composition is started by selecting an extrusion condition in which streaking is less likely to occur, and it is assumed that the streaks are observed on the extruded resin foamed sheet, and further fine-tuning is performed. Out of the conditions, find out the conditions under which the stripes disappear and then obtain the product.
如上所述,先前除調整擠出條件以外,並未確立用於防止條紋之具體手段,因此有時陷入只能於較窄之條件範圍中製作樹脂發泡片材的狀況。As described above, in the past, in addition to the adjustment of the extrusion conditions, a specific means for preventing the streaks has not been established, and therefore, the resin foamed sheet can be produced only in a narrow condition range.
專利文獻1:日本專利特開2003-236961號公報Patent Document 1: Japanese Patent Laid-Open Publication No. 2003-236961
本發明係鑒於如上所述之問題研究而成者,其目的在於提供一種藉由調整擠出條件以外之方式抑制條紋,而且容易製造成觀看不到條紋之狀態的樹脂發泡片材。The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a resin foamed sheet which is capable of suppressing streaks by adjusting the extrusion conditions and which is easy to manufacture in a state in which streaks are not observed.
本發明者為解決上述課題而進行了銳意研究,結果發現,藉由使所使用之聚丙烯系樹脂組合物為特定之組成可抑制條紋,從而完成本發明。The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that the present invention can be achieved by suppressing streaks by using a specific composition of the polypropylene resin composition to be used.
亦即,關於樹脂發泡片材之本發明之特徵在於:其係使用擠出機將以聚丙烯系樹脂成分作為主成分之聚丙烯系樹脂組合物擠出發泡而形成之樹脂發泡片材,且上述聚丙烯系樹脂組合物中,以於所包含之聚合物成分中所佔之比例為20質量%以上且未達50質量%的方式而含有高熔融張力聚丙烯樹脂。In other words, the present invention is characterized in that the resin foamed sheet is formed by extrusion-foaming a polypropylene-based resin composition containing a polypropylene-based resin component as a main component using an extruder. In the polypropylene resin composition, the high melt tension polypropylene resin is contained so that the ratio of the polymer component contained in the polymer component is 20% by mass or more and less than 50% by mass.
本發明中,由於聚合物成分中之高熔融張力聚丙烯樹脂係規定為特定之比例,故而可使得藉由擠出機進行擠出發泡時,不易在所獲得之樹脂發泡片材上產生條紋。In the present invention, since the high melt tension polypropylene resin in the polymer component is specified to be a specific ratio, it is difficult to cause streaking on the obtained resin foamed sheet when extrusion foaming is performed by an extruder. .
因此,可使擠出條件存在裕度,可簡便地獲得優質之樹脂發泡片材。Therefore, there is a margin in the extrusion conditions, and a high-quality resin foamed sheet can be easily obtained.
藉此,可提供均質之樹脂發泡片材,因此可提供一種藉由真空成形或氣壓成形等通常之片材成形法而賦予立體結構時,所獲得之成形品中產生外觀不良等之可能性較低之樹脂發泡片材。According to this, it is possible to provide a homogeneous resin foamed sheet, and therefore it is possible to provide a molded article having a poor appearance and the like when a three-dimensional structure is imparted by a usual sheet forming method such as vacuum forming or air pressure forming. Lower resin foamed sheet.
以下,例示具有將作為非發泡樹脂層之表面層、與發泡樹脂層積層之積層結構的樹脂發泡片材作為樹脂發泡片材,並對本發明之實施形態進行說明。In the following, a resin foamed sheet having a laminated structure of a non-foamed resin layer and a laminated structure of a foamed resin layered layer is exemplified as a resin foamed sheet, and an embodiment of the present invention will be described.
如圖1所示,本實施形態之樹脂發泡片材1具有構成上表面側與下表面側之各表面之非發泡樹脂層(表面層11、12)、與形成於其間之發泡樹脂層20的三層之積層結構。As shown in Fig. 1, the resin foamed sheet 1 of the present embodiment has a non-foamed resin layer (surface layers 11, 12) constituting each surface on the upper surface side and the lower surface side, and a foamed resin formed therebetween. The three-layer laminate structure of layer 20.
亦即,本實施形態之樹脂發泡片材1隔著該發泡樹脂層20而於其兩側包含非發泡樹脂層(表面層11、12)。In other words, the resin foam sheet 1 of the present embodiment includes a non-foamed resin layer (surface layers 11 and 12) on both sides of the foamed resin layer 20 via the foamed resin layer 20.
該表面層11、12均係使用以聚丙烯系樹脂作為主成分之聚丙烯系樹脂組合物形成為非發泡狀態。Each of the surface layers 11 and 12 is formed into a non-foamed state using a polypropylene-based resin composition containing a polypropylene-based resin as a main component.
本實施形態之樹脂發泡片材1中,對於圖1正面視上側之表面層11(以下亦稱為「第一表面層11」)、與下側之表面層12(以下亦稱為「第二表面層12」),並非必需使其構成一致,亦可使各層之厚度不相同。In the resin foamed sheet 1 of the present embodiment, the surface layer 11 on the upper side in the front view of FIG. 1 (hereinafter also referred to as "first surface layer 11") and the surface layer 12 on the lower side (hereinafter also referred to as "the first The two surface layers 12") do not have to be identical in composition, and the thickness of each layer may be different.
另外,上述發泡樹脂層20係藉由後述之方法將以聚丙烯系樹脂作為主成分之聚丙烯系樹脂組合物擠出發泡而形成者。In addition, the foamed resin layer 20 is formed by extrusion-foaming a polypropylene-based resin composition containing a polypropylene-based resin as a main component by a method described later.
另外,上述表面層11、12係將用於形成各表面層之聚丙烯系樹脂組合物,與用於以後述之方法形成上述發泡樹脂層20之上述聚丙烯系樹脂成分一起共擠出而形成者。Further, the surface layers 11 and 12 are obtained by coextruding a polypropylene resin composition for forming each surface layer together with the polypropylene resin component for forming the foamed resin layer 20 described later. Former.
形成上述表面層11、12與上述發泡樹脂層20所使用的聚丙烯系樹脂組合物通常係設置成適合於各層之組成,故而係使用組成互不相同者。The polypropylene resin composition used to form the surface layers 11 and 12 and the foamed resin layer 20 is usually set to be suitable for the composition of each layer, and therefore the compositions used are different from each other.
於本實施形態中,形成上述發泡樹脂層20所使用之聚丙烯系樹脂組合物重要的是,高熔融張力聚丙烯樹脂(HMS-PP)於聚丙烯系樹脂組合物所包含的聚合物成分中所佔之比例為20質量%以上且未達50質量%。In the present embodiment, it is important that the polypropylene resin composition used for the foamed resin layer 20 is a polymer component contained in a polypropylene resin composition having a high melt tension polypropylene resin (HMS-PP). The proportion in the middle is 20% by mass or more and less than 50% by mass.
作為該HMS-PP,可使用:分子藉由電子束等活性能量線之照射而切斷或交聯,從而於分子內形成自由末端長鏈分枝者,或者藉由化學交聯而於分子內形成自由末端長鏈分枝,從而獲得高熔融張力者。As the HMS-PP, a molecule can be cut or crosslinked by irradiation with an active energy ray such as an electron beam to form a free-end long-chain branch in a molecule, or in a molecule by chemical crosslinking. A free-chain long chain branch is formed to obtain a high melt tension.
另外,亦可使用將聚乙烯嵌段等烯烴嵌段導入至分子內,藉由以烯烴嵌段與聚丙烯嵌段形成嵌段共聚物而獲得高熔融張力者作為HMS-PP。Further, as the HMS-PP, a olefin block such as a polyethylene block may be introduced into a molecule, and a block copolymer may be formed by forming an olefin block and a polypropylene block to obtain a high melt tension.
作為該HMS-PP以外之聚丙烯系樹脂,可列舉實質上僅由丙烯成分構成之均聚丙烯樹脂(PP)。Examples of the polypropylene-based resin other than the HMS-PP include a homopolypropylene resin (PP) consisting essentially of only a propylene component.
再者,關於聚丙烯系樹脂是否為HMS-PP,不僅可藉由如上所述之分子結構上之差異進行判定,通常亦可根據其熔融張力而判定。In addition, whether or not the polypropylene resin is HMS-PP can be determined not only by the difference in molecular structure as described above, but also by the melt tension.
於本說明書中,所謂高熔融張力聚丙烯樹脂(HMS-PP),係指於熔體質量流率(MFR,melt mass-flow rate)為0.5 g/10 min以上、10 g/10 min以下之條件下,熔融張力為5 cN以上、50 cN以下者。In the present specification, the term "high melt tension polypropylene resin (HMS-PP)" means that the melt mass flow rate (MFR, melt mass-flow rate) is 0.5 g/10 min or more and 10 g/10 min or less. Under the conditions, the melt tension is 5 cN or more and 50 cN or less.
另外,關於該MFR,可依據JIS K7210(1999)之A法,於試驗溫度230℃、負載21.18 N(2.16 kgf)下進行測定,關於「熔融張力」,具體而言可藉由以下之方式進行測定。In addition, the MFR can be measured at a test temperature of 230 ° C and a load of 21.18 N (2.16 kgf) according to the method of JIS K7210 (1999), and the "melt tension" can be specifically performed by the following method. Determination.
亦即,關於「熔融張力」,可將作為試樣之聚丙烯系樹脂收容於沿垂直方向配置的內徑15 mm之氣缸內,於230℃之溫度下加熱5分鐘使之熔融後,自氣缸之上部***活塞,藉由該活塞,以擠出速度達到0.0773 mm/s(固定)之方式將熔融樹脂自氣缸之下端所設置的毛細管(模直徑:2.095 mm,模長度:8 mm,流入角度:90度(錐形))擠出成帶狀而進行測定。In other words, the "melt tension" can be obtained by accommodating the polypropylene resin as a sample in a cylinder having an inner diameter of 15 mm disposed in the vertical direction, heating at a temperature of 230 ° C for 5 minutes, and melting the cylinder. The upper part is inserted into the piston, and the capillary is set from the lower end of the cylinder by the extrusion speed of 0.0773 mm/s (fixed) (die diameter: 2.095 mm, mold length: 8 mm, inflow angle) : 90 degrees (taper)) was extruded into a strip shape and measured.
具體而言,可藉由將該擠出之帶狀物捲繞於配置在上述毛細管之下方的張力檢測滑輪上之後,使用捲取輥進行捲取而測定,將開始捲取時之初速度設為4 mm/s,並將之後之加速度設為12 mm/s2 而逐漸加快捲取速度,將藉由張力檢測滑輪所觀察到之張力急遽下降時的捲取速度確定為「斷裂點速度」,測定至觀察到該「斷裂點速度」為止之最大張力作為「熔融張力」。Specifically, the extruded ribbon can be wound around a tension detecting pulley disposed below the capillary, and then wound up by a take-up roll, and the initial speed at the start of winding can be set. When the acceleration is 4 mm/s and the acceleration is set to 12 mm/s 2 , the winding speed is gradually increased, and the winding speed when the tension is suddenly decreased by the tension detecting pulley is determined as the "breaking point speed". The maximum tension until the "breaking point velocity" was observed was measured as "melting tension".
再者,於本說明書中,即便導入有烯烴嵌段以具有一定程度之熔融張力的嵌段共聚物,上述測定所得的熔融張力之值小於上述之值者在本實施形態中亦無法作為於聚丙烯系樹脂組合物中之含量有規定的HMS-PP對待。Further, in the present specification, even if a block copolymer having an olefin block having a certain degree of melt tension is introduced, the value of the melt tension obtained by the above measurement is less than the above value, and in the present embodiment, it cannot be used as a polymer. The content of the propylene resin composition is determined by the specified HMS-PP.
以下,只要無特別記載,則用語「嵌段共聚物」或「嵌段PP」係表示含有烯烴嵌段與聚丙烯嵌段的嵌段共聚物中之熔融張力之值小於上述之值(不符合「HMS-PP」)者而使用。Hereinafter, unless otherwise stated, the term "block copolymer" or "block PP" means that the value of the melt tension in the block copolymer containing the olefin block and the polypropylene block is less than the above value (non-conformity) "HMS-PP" is used.
作為顯示上述熔融張力之值的HMS-PP之具體例,例如可列舉:由Borealis公司以商品名「WB130HMS」、「WB135HMS」及「WB140HMS」市售者。Specific examples of the HMS-PP which exhibits the above-mentioned value of the melt tension include those commercially available under the trade names "WB130HMS", "WB135HMS" and "WB140HMS" by the company Borealis.
另外,作為HMS-PP之具體例,亦可列舉由Basell公司以商品名「Pro-fax F814」市售者。Moreover, as a specific example of HMS-PP, the brand name "Pro-fax F814" by the company of Basell is also mentioned.
另外,作為HMS-PP之具體例,可列舉由Japan Polypropylene公司以商品名「FB3312」、「FB5100」、「FB7200」及「FB9100」市售者。In addition, as a specific example of the HMS-PP, those sold by the Japan Polypropylene Corporation under the trade names "FB3312", "FB5100", "FB7200", and "FB9100" are mentioned.
其中,若採用藉由化學交聯而於分子內形成自由末端長鏈分枝的Borealis公司之商品名「WB135HMS」等,則於可容易地使藉由擠出發泡形成發泡樹脂層20時之發泡度提高等方面而言較佳。In the case where the trade name "WB135HMS" of Borealis Co., Ltd., which forms a free-end long-chain branch in a molecule by chemical crosslinking, is used, the foamed resin layer 20 can be easily formed by extrusion foaming. It is preferable in terms of improvement in foaming degree and the like.
以於聚丙烯系樹脂組合物所包含之聚合物成分中為20質量%以上且未達50質量%之比例而含有該HMS-PP之事項重要的原因在於,若HMS-PP在全部聚合物成分中所佔之比例達到50質量%以上,則將該聚丙烯系樹脂組合物擠出發泡而製作樹脂發泡片材時容易產生條紋。The reason why the HMS-PP is contained in a ratio of 20% by mass or more to less than 50% by mass in the polymer component contained in the polypropylene resin composition is that if HMS-PP is in all the polymer components When the ratio of the polypropylene resin composition is 50% by mass or more, the polypropylene resin composition is extruded and foamed to form a resin foamed sheet, and streaks are likely to occur.
另外,將HMS-PP之下限值設為20質量%之原因在於,若HMS-PP之含量小於20質量%,則有可能難以使聚丙烯系樹脂組合物於良好之狀態下發泡,相反使得用以獲得合格品之擠出條件之選擇範圍變窄。In addition, the reason why the lower limit of HMS-PP is 20% by mass is that when the content of HMS-PP is less than 20% by mass, it may be difficult to foam the polypropylene resin composition in a good state. The selection range for the extrusion conditions for obtaining a good product is narrowed.
就上述觀點而言,HMS-PP在全部聚合物成分中之含量較佳為25質量%以上且未達50質量%,更佳為30質量%以上、45質量%以下。From the above viewpoints, the content of HMS-PP in the total polymer component is preferably 25% by mass or more and less than 50% by mass, more preferably 30% by mass or more and 45% by mass or less.
再者,包含該HMS-PP之全部聚丙烯系樹脂之合計量在形成發泡樹脂層20所使用的聚丙烯系樹脂組合物之全部聚合物成分中所佔的比例通常係設為80質量%以上,較佳為90質量%以上。In addition, the total amount of all the polypropylene-based resins including the HMS-PP is usually 80% by mass in the total polymer component of the polypropylene-based resin composition used for forming the foamed resin layer 20. The above is preferably 90% by mass or more.
作為該聚丙烯系樹脂以外的用於構成聚合物成分的聚合物,較佳為與聚丙烯系樹脂相容性較高之聚合物,例如可列舉:聚乙烯樹脂、乙烯-丙烯酸乙酯共聚物樹脂、乙烯-乙酸乙烯酯共聚物樹脂、聚丁烯樹脂、聚(4-甲基-1-戊烯)樹脂等聚烯烴系樹脂、或聚烯烴系之熱塑性彈性體(TPO)。The polymer constituting the polymer component other than the polypropylene resin is preferably a polymer having high compatibility with the polypropylene resin, and examples thereof include a polyethylene resin and an ethylene-ethyl acrylate copolymer. A polyolefin resin such as a resin, an ethylene-vinyl acetate copolymer resin, a polybutene resin, or a poly(4-methyl-1-pentene) resin, or a polyolefin-based thermoplastic elastomer (TPO).
另外,形成上述發泡樹脂層20所使用之聚丙烯系樹脂組合物中,除如上所述之聚合物成分以外,通常亦含有用於發泡之成分。Further, the polypropylene resin composition used to form the foamed resin layer 20 usually contains a component for foaming in addition to the polymer component as described above.
作為該用於發泡之成分,例如可列舉:於擠出溫度下變成氣體狀態之氣體成分,成為藉由該氣體成分形成氣泡時之核的成核劑,或於擠出溫度下發生熱分解而產生氣體之熱分解型發泡劑等。Examples of the component for foaming include a gas component which becomes a gas state at an extrusion temperature, a nucleating agent which forms a core when bubbles are formed by the gas component, or thermal decomposition at an extrusion temperature. A thermal decomposition type foaming agent which generates a gas or the like.
作為上述氣體成分,可列舉:丙烷、丁烷、戊烷等脂肪族烴,氮氣、二氧化碳、水等。Examples of the gas component include aliphatic hydrocarbons such as propane, butane, and pentane, nitrogen gas, carbon dioxide, and water.
再者,該等氣體成分可單獨使用亦可併用複數種。Further, the gas components may be used singly or in combination of plural kinds.
作為上述成核劑,例如可列舉:滑石、雲母、二氧化矽、矽藻土、氧化鋁、氧化鈦、氧化鋅、氧化鎂、氫氧化鎂、氫氧化鋁、氫氧化鈣、碳酸鉀、碳酸鈣、碳酸鎂、硫酸鉀、硫酸鋇、玻璃珠等無機化合物粒子,聚四氟乙烯等有機化合物粒子等。Examples of the nucleating agent include talc, mica, cerium oxide, diatomaceous earth, alumina, titanium oxide, zinc oxide, magnesium oxide, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, potassium carbonate, and carbonic acid. Inorganic compound particles such as calcium, magnesium carbonate, potassium sulfate, barium sulfate, and glass beads, and organic compound particles such as polytetrafluoroethylene.
該成核劑例如可以母料方式而含於發泡樹脂層之形成材料中,藉由將上述成核劑用作以5質量%以上、50質量%以下之範圍內的任意比例而分散於基質樹脂中之母料,可使成核劑所發揮之效果大於其使用量。The nucleating agent may be contained in the forming material of the foamed resin layer in the form of a masterbatch, for example, and the nucleating agent may be dispersed in the matrix at any ratio within a range of 5 mass% or more and 50 mass% or less. The masterbatch in the resin can make the effect of the nucleating agent greater than the amount used.
另外,作為加熱分解型之發泡劑,例如可列舉:偶氮雙甲醯胺、碳酸氫鈉、碳酸氫鈉與檸檬酸之混合物等。Further, examples of the heat-decomposable foaming agent include azobisformamide, sodium hydrogencarbonate, a mixture of sodium hydrogencarbonate and citric acid, and the like.
關於該加熱分解型之發泡劑,藉由將其以10質量%以上、50質量%以下之範圍內之任意比例分散於基質樹脂中作為母料,亦可提高其效果。The heat-decomposable foaming agent can be used as a masterbatch by dispersing it in a matrix resin at any ratio within a range of 10% by mass or more and 50% by mass or less, thereby improving the effect.
另外,形成發泡樹脂層20所使用的聚丙烯系樹脂組合物中,亦可與形成普通的樹脂製品所利用之樹脂組合物同樣地含有各種添加劑,例如可適宜含有:抗氧化劑、抗老化劑、加工助劑等。In addition, the polypropylene resin composition used for forming the foamed resin layer 20 may contain various additives similarly to the resin composition used for forming a general resin product, and may contain, for example, an antioxidant or an anti-aging agent. , processing aids, etc.
再者,本實施形態之樹脂發泡片材1於直接以片材形狀用作玻璃板之緩衝材料之情形,或將其成形加工成作為精選肉、鮮魚等之展示用容器等而通用之發泡盤之情形等較多之情形時,要求抑制其因靜電而帶電。In addition, the resin foamed sheet 1 of the present embodiment is used as a cushioning material for a glass sheet in the form of a sheet, or is formed into a container for display such as selected meat or fresh fish. In the case of a large number of cases of the bubble disk, it is required to suppress the charging due to static electricity.
因此,較佳為在用於形成表面層11、12之聚丙烯系樹脂組合物中,含有非離子性抗靜電劑。Therefore, it is preferred to contain a nonionic antistatic agent in the polypropylene resin composition for forming the surface layers 11 and 12.
作為該非離子性抗靜電劑,例如可列舉:醇系抗靜電劑、醚系抗靜電劑、酯系抗靜電劑、酯‧醚系抗靜電劑等。Examples of the nonionic antistatic agent include an alcohol-based antistatic agent, an ether-based antistatic agent, an ester-based antistatic agent, and an ester/ether-based antistatic agent.
另外,作為上述非離子性抗靜電劑,例如亦可列舉:胺系抗靜電劑、或醯胺系抗靜電劑等含氮型之抗靜電劑。In addition, examples of the nonionic antistatic agent include nitrogen-based antistatic agents such as an amine antistatic agent and a guanamine antistatic agent.
相對於聚丙烯系樹脂組合物中所包含之聚合物成分100質量份,該非離子性抗靜電劑通常以0.5質量份以上、5.0質量份以下之比例而含於聚丙烯系樹脂組合物中。The nonionic antistatic agent is usually contained in the polypropylene resin composition in an amount of 0.5 parts by mass or more and 5.0 parts by mass or less based on 100 parts by mass of the polymer component contained in the polypropylene resin composition.
作為上述醇系抗靜電劑,例如可列舉:聚乙二醇(或聚氧化乙烯)、聚(氧化乙烯)-聚(氧化丙烯)嵌段共聚物等聚氧化烯等。Examples of the alcohol-based antistatic agent include polyoxyalkylenes such as polyethylene glycol (or polyethylene oxide) and poly(ethylene oxide)-poly(oxypropylene) block copolymer.
再者,上述醇型抗靜電劑中,氧化烯之聚合度通常為1以上、300以下(例如5以上、200以下),較佳為10以上、150以下(例如10以上、100以下)。In the alcohol type antistatic agent, the degree of polymerization of the alkylene oxide is usually 1 or more and 300 or less (for example, 5 or more and 200 or less), preferably 10 or more and 150 or less (for example, 10 or more and 100 or less).
更佳為15以上,50以下左右。More preferably 15 or more, and 50 or less.
作為上述醚系抗靜電劑,例如可列舉:聚氧乙烯辛醚、聚氧乙烯月桂基醚、聚氧乙烯鯨蠟基醚等聚氧乙烯烷基醚;聚氧乙烯辛基苯醚、聚氧乙烯壬基苯醚等聚氧乙烯烷基苯醚等。Examples of the ether-based antistatic agent include polyoxyethylene alkyl ethers such as polyoxyethylene octyl ether, polyoxyethylene lauryl ether, and polyoxyethylene cetyl ether; polyoxyethylene octylphenyl ether and polyoxygen A polyoxyethylene alkyl phenyl ether such as vinyl nonylphenyl ether.
作為上述酯系抗靜電劑,例如可列舉乙二醇、丙二醇、三羥甲基丙烷、甘油、(聚)甘油、季戊四醇、去水山梨醇、山梨糖醇、蔗糖等多元醇與脂肪酸之酯等多元醇脂肪酸酯,例如可列舉:單硬脂酸甘油酯等甘油脂肪酸酯、去水山梨醇單油酸酯等去水山梨醇脂肪酸酯、蔗糖單硬脂酸酯等蔗糖脂肪酸酯等。Examples of the ester-based antistatic agent include esters of a polyhydric alcohol such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, (poly)glycerin, pentaerythritol, sorbitan, sorbitol, and sucrose, and a fatty acid. Examples of the polyhydric alcohol fatty acid esters include glycerin fatty acid esters such as glyceryl monostearate, sorbitan fatty acid esters such as sorbitan monooleate, and sucrose fatty acid esters such as sucrose monostearate. Wait.
作為上述酯‧醚系抗靜電劑,例如可列舉:聚氧乙烯甘油硬脂酸酯、聚氧乙烯甘油油酸酯等聚氧乙烯甘油脂肪酸酯;聚氧乙烯去水山梨醇硬脂酸酯等聚氧乙烯去水山梨醇脂肪酸酯;聚氧乙烯蔗糖脂肪酸酯等聚氧乙烯多元醇脂肪酸酯。Examples of the ester ‧ ether antistatic agent include polyoxyethylene glycerin fatty acid esters such as polyoxyethylene glyceryl stearate and polyoxyethylene glycerol oleate; and polyoxyethylene sorbitan stearate; Polyoxyethylene sorbitan fatty acid ester such as polyoxyethylene sorbitan fatty acid ester; polyoxyethylene polyol fatty acid ester such as polyoxyethylene sucrose fatty acid ester.
另外,例如亦可列舉聚氧乙烯蓖麻油及聚氧乙烯氫化蓖麻油等。Further, examples thereof include polyoxyethylene castor oil and polyoxyethylene hydrogenated castor oil.
作為上述含氮型之抗靜電劑,例如可列舉:聚氧乙烯月桂胺等分子中具有碳數6以上、24以下左右之烷基結構的聚氧乙烯烷基胺;聚氧乙烯硬脂醯胺等分子中具有碳數6以上、24以下左右之脂肪酸結構的聚氧乙烯脂肪酸醯胺;N-乙醇烷基胺等N-烷醇烷基胺、或N,N-二乙醇烷基胺等N,N-烷醇烷基胺等烷醇烷基胺;N-乙醇硬脂醯胺等N-烷醇脂肪酸醯胺、或N,N-二乙醇硬脂醯胺等N,N-烷醇脂肪酸醯胺等烷醇脂肪酸醯胺。Examples of the nitrogen-containing antistatic agent include polyoxyethylene alkylamines having an alkyl group having a carbon number of 6 or more and 24 or less in a molecule such as polyoxyethylene laurylamine; polyoxyethylene stearylamine; a polyoxyethylene fatty acid decylamine having a fatty acid structure having a carbon number of 6 or more and 24 or less, or an N-alkanol alkylamine such as N-ethanol alkylamine or N, N-diethanol alkylamine or the like An alkanol alkylamine such as an N-alkanol alkylamine; an N-alkanol fatty acid decylamine such as N-ethanol stearylamine or an N,N-alkanol fatty acid such as N,N-diethanol stearylamine An alkanol fatty acid guanamine such as guanamine.
再者,作為構成上述非離子性抗靜電劑之烷基或脂肪酸,通常可列舉碳數6以上、24以下左右者。In addition, examples of the alkyl group or the fatty acid constituting the nonionic antistatic agent include those having a carbon number of 6 or more and 24 or less.
脂肪酸可列舉:飽和脂肪酸(例如,癸酸、月桂酸、肉豆蔻酸、棕櫚酸、硬脂酸等碳數6以上、24以下之飽和脂肪酸;油酸等不飽和脂肪酸。Examples of the fatty acid include saturated fatty acids (for example, saturated fatty acids having 6 or more and 24 or less carbon atoms such as capric acid, lauric acid, myristic acid, palmitic acid, and stearic acid; and unsaturated fatty acids such as oleic acid.
另外,除該非離子性抗靜電劑以外,亦可併用陰離子系抗靜電劑、陽離子系抗靜電劑、兩性系抗靜電劑、高分子型抗靜電劑,作為上述陰離子系低分子型抗靜電劑,可列舉烷基磺酸鹽等,作為陽離子系低分子型抗靜電劑,可列舉四烷基銨鹽等,作為兩性系低分子型抗靜電劑,可列舉烷基甜菜鹼等。Further, in addition to the nonionic antistatic agent, an anionic antistatic agent, a cationic antistatic agent, an amphoteric antistatic agent, or a polymeric antistatic agent may be used in combination as the anionic low molecular antistatic agent. The alkyl sulfonate or the like is exemplified, and the cation-based low-molecular-weight antistatic agent may, for example, be a tetraalkylammonium salt. Examples of the amphoteric low-molecular-weight antistatic agent include alkylbetaine and the like.
另外,作為上述高分子型抗靜電劑,可列舉:聚氧化乙烯、聚氧化丙烯、聚乙二醇、聚酯醯胺、聚醚酯醯胺等離子聚合物或其四級銨鹽,以及聚醚-聚烯烴嵌段共聚物(聚醚系嵌段與聚烯烴系嵌段之嵌段共聚物)等烯烴系嵌段與親水性嵌段之共聚物等。Further, examples of the polymer type antistatic agent include ionic polymers such as polyethylene oxide, polypropylene oxide, polyethylene glycol, polyester decylamine, and polyether decylamine, or a quaternary ammonium salt thereof, and a polyether. - a copolymer of an olefin block and a hydrophilic block such as a polyolefin block copolymer (a block copolymer of a polyether block and a polyolefin block).
該非離子性抗靜電劑或陰離子系抗靜電劑、陽離子系抗靜電劑、兩性系抗靜電劑等低分子型之抗靜電劑係滲出至樹脂發泡片材1之表面,產生稱為所謂「滲出(bleedout)」之現象而發揮抗靜電功能。The low-molecular type antistatic agent such as a nonionic antistatic agent, an anionic antistatic agent, a cationic antistatic agent, or an amphoteric antistatic agent oozes to the surface of the resin foamed sheet 1, and is called so-called "exudation". (bleedout) phenomenon to play an antistatic function.
因此,用於形成表面層11、12之聚丙烯系樹脂組合物中,較佳為與上述非離子性抗靜電劑一起含有促進該非離子性抗靜電劑滲出之成分。Therefore, in the polypropylene resin composition for forming the surface layers 11 and 12, it is preferred to contain a component which promotes bleeding of the nonionic antistatic agent together with the nonionic antistatic agent.
作為促進該非離子性抗靜電劑滲出之成分,為乙烯-α-烯烴共聚物或低密度聚乙烯樹脂之任一種且結晶度為20%以上、55%以下之樹脂特別有效果。The component which promotes the bleed out of the nonionic antistatic agent is any one of an ethylene-α-olefin copolymer or a low-density polyethylene resin and has a crystallinity of 20% or more and 55% or less.
該乙烯-α-烯烴共聚物或低密度聚乙烯樹脂可在用於形成表面層11、12之聚丙烯系樹脂組合物中單獨含有1種,亦可含有複數種。The ethylene-α-olefin copolymer or the low-density polyethylene resin may be contained alone or in a plurality of types in the polypropylene resin composition for forming the surface layers 11 and 12.
另外,亦可將乙烯-α-烯烴共聚物之1種以上與低密度聚乙烯樹脂之1種以上混合而作為促進非離子性抗靜電劑滲出之成分。In addition, one or more of the ethylene-α-olefin copolymers may be mixed with one or more of the low-density polyethylene resins to form a component that promotes bleed out of the nonionic antistatic agent.
再者,為促進非離子性抗靜電劑滲出,該等之合計量較佳為在聚丙烯系樹脂組合物之聚合物成分中為20質量%以上,更佳為25質量%以上。In addition, in order to promote the bleed out of the nonionic antistatic agent, the total amount of these is preferably 20% by mass or more, and more preferably 25% by mass or more based on the polymer component of the polypropylene resin composition.
另外,上限通常為40質量%左右,該等之合計量較佳為35質量%以下。Further, the upper limit is usually about 40% by mass, and the total amount of these is preferably 35% by mass or less.
該乙烯-α-烯烴共聚物或低密度聚乙烯樹脂之結晶度可藉由JIS K7121:1987「塑膠之轉移溫度測定方法」進行測定。The crystallinity of the ethylene-α-olefin copolymer or the low-density polyethylene resin can be measured by JIS K7121:1987 "Method for measuring the transfer temperature of plastics".
具體而言,可使用SII Nano Technology公司製造之示差掃描熱析儀(DSC)裝置「DSC6220型」,在測定容器中裝入約7 mg試樣,於氮氣流量30 ml/min下以10℃/min之升溫(冷卻)速度升溫(冷卻),並將DSC曲線偏離基線之點作為熔解(結晶化)之起始點,將DSC曲線再次返回至基線之點作為其等之結束點,測定熔解熱量及結晶化熱量,藉由下式求出結晶度。Specifically, a differential scanning calorimeter (DSC) device "DSC6220 type" manufactured by SII Nano Technology Co., Ltd. can be used, and a sample of about 7 mg is placed in the measuring container at 10 ° C under a nitrogen flow rate of 30 ml/min. The temperature rise (cooling) of min is increased (cooling), and the point at which the DSC curve deviates from the baseline is taken as the starting point of melting (crystallization), and the DSC curve is returned to the point of the baseline again as the end point of the measurement, and the heat of fusion is measured. And the heat of crystallization, the crystallinity was determined by the following formula.
結晶度(%)=(結晶化熱量(mJ)/完全結晶之熔解熱量(mJ))×100Crystallinity (%) = (heat of crystallization (mJ) / heat of fusion of complete crystallization (mJ)) × 100
(其中,完全結晶熔解熱量(理論值)為285.7 mJ/mg)。(Where the total crystal melting heat (theoretical value) is 285.7 mJ/mg).
聚丙烯系樹脂組合物之聚合物成分可僅由上述HMS-PP、及用以促進該非離子性抗靜電劑滲出之成分構成,亦可於該等中進而適宜添加以上作為上述發泡樹脂層20之形成材料而記載的HMS-PP以外之聚丙烯系樹脂,或者與該聚丙烯系樹脂之親和性較高之烯烴系樹脂或TPO。The polymer component of the polypropylene resin composition may be composed only of the above-mentioned HMS-PP and a component for promoting the bleeding of the nonionic antistatic agent, and may be further added as the above-mentioned foamed resin layer 20 in these. A polypropylene-based resin other than HMS-PP described as a material to be formed, or an olefin-based resin or TPO having high affinity with the polypropylene-based resin.
再者,該聚丙烯系樹脂組合物由於係構成樹脂發泡片材1之表面者,因此可視需要含有使該表面發揮出欲使之具備之功能的各種添加劑。In addition, since the polypropylene resin composition constitutes the surface of the resin foamed sheet 1, it is necessary to contain various additives which allow the surface to function as desired.
例如,可含有耐候劑、抗老化劑而防止樹脂發泡片材1或發泡盤劣化,或者含有助滑劑而提高光滑性等。For example, a weathering agent or an anti-aging agent may be contained to prevent deterioration of the resin foamed sheet 1 or the foamed disk, or a slip aid may be added to improve smoothness and the like.
或者,亦可含有顏料進行著色而提高美觀度等。Alternatively, the pigment may be colored to improve the appearance and the like.
再者,本實施形態之樹脂發泡片材1中,與並非必需使第一表面層11與第二表面層12各自之厚度相同同樣,用於形成第一表面層11與第二表面層12的聚丙烯系樹脂組合物之調配內容亦可不同。Further, in the resin foamed sheet 1 of the present embodiment, the first surface layer 11 and the second surface layer 12 are formed in the same manner as the thicknesses of the first surface layer 11 and the second surface layer 12 are not necessarily the same. The content of the polypropylene resin composition may vary.
例如,亦可僅使相當於發泡盤之外側之側含有顏料而實施著色,使相當於發泡盤之內側之側為自然色(或者白色)。For example, the side corresponding to the outer side of the foaming disk may be colored, and the side corresponding to the inner side of the foaming disk may be a natural color (or white).
另外,對於上述非離子系抗靜電劑等,亦可使其等僅含於相當於發泡盤之外側之側,而使相當於內側之側不含有該等。In addition, the non-ionic antistatic agent or the like may be contained only on the side corresponding to the outer side of the foaming disk, and the side corresponding to the inner side may not be contained.
上述樹脂發泡片材1中的第一表面層11、第二表面層12、以及發泡樹脂層20之各層之厚度並無特別限定,第一表面層11或第二表面層12通常設為50 μm以上、150 μm以下之範圍內的任意厚度。The thickness of each of the first surface layer 11, the second surface layer 12, and the foamed resin layer 20 in the resin foamed sheet 1 is not particularly limited, and the first surface layer 11 or the second surface layer 12 is usually set to Any thickness in the range of 50 μm or more and 150 μm or less.
另外,發泡樹脂層20通常係形成為0.5 mm以上、5.0 mm以下之範圍內之任意厚度,密度(表觀密度)係設為0.15 g/cm3 以上、0.6 g/cm3 以下。Further, the foamed resin layer 20 is usually formed to have any thickness in the range of 0.5 mm or more and 5.0 mm or less, and the density (apparent density) is set to be 0.15 g/cm 3 or more and 0.6 g/cm 3 or less.
此種樹脂發泡片材1可使用製造樹脂發泡片材通常使用之擠出機,對上述聚丙烯系樹脂組合物實施擠出發泡而製造。Such a resin foamed sheet 1 can be produced by extrusion foaming the above-mentioned polypropylene resin composition using an extruder generally used for producing a resin foamed sheet.
以下,參照圖2、圖3,對樹脂發泡片材1之製造方法進行詳細說明。Hereinafter, a method of manufacturing the resin foamed sheet 1 will be described in detail with reference to FIGS. 2 and 3.
再者,圖2係樹脂發泡片材之製造裝置之概略構成圖,圖3係表示圖2中所示之匯流模具(符號XH)之內部狀態的剖面圖。2 is a schematic configuration diagram of a manufacturing apparatus of a resin foamed sheet, and FIG. 3 is a cross-sectional view showing an internal state of the manifold (symbol XH) shown in FIG.
另外,圖4係表示將聚丙烯系樹脂組合物擠出發泡時之狀態,且係表示圖2之虛線A所示之部分的狀態。In addition, FIG. 4 shows a state in which the polypropylene resin composition is extruded and foamed, and shows a state shown by a broken line A in FIG. 2 .
該圖2中所示之樹脂發泡片材之製造裝置包括:作為串列式擠出機(tandem extruder)之第1擠出機70、及作為單擠出機(single extruder)之第2擠出機80的兩系列之擠出機。The apparatus for producing a resin foamed sheet shown in Fig. 2 includes a first extruder 70 as a tandem extruder and a second extrusion as a single extruder. Two series of extruders for the machine 80.
另外包括:匯流模具XH,於該等擠出機中熔融混練後之樹脂組合物在其中匯流;及圓形模具CD,其具備用以將於該匯流模具XH中匯流之樹脂組合物呈筒狀噴出的圓環狀之噴出孔。Further, the method includes: a manifold mold XH in which the resin composition melt-kneaded in the extruders is merged; and a circular mold CD having a resin composition for converging in the manifold mold XH in a cylindrical shape A circular orifice that is ejected.
另外,該製造裝置包括:冷卻裝置CL,其將自圓形模具CD呈筒狀噴出之樹脂發泡片材空氣冷卻;心軸MD,用以將該筒狀之樹脂發泡片材擴徑而使之成為特定大小之筒狀;切割裝置,對通過該心軸MD後之樹脂發泡片材沿擠出方向進行切割,從而分割成2片之片材(未圖示;圖2中僅示出上下分割之狀態);及捲取輥92,用以在使經切割之樹脂發泡片材1通過複數個輥91後進行捲取。Further, the manufacturing apparatus includes: a cooling device CL that air-cools the resin foamed sheet which is ejected from the circular mold CD in a cylindrical shape; and a mandrel MD for expanding the cylindrical resin foamed sheet by The cylindrical foaming sheet is cut into two sheets (not shown; only And a take-up roll 92 for winding up the cut resin foamed sheet 1 after passing through a plurality of rolls 91.
上述第1擠出機70係用於形成發泡樹脂層20之擠出機,於其上游側之擠出機(以下,亦稱為「上游側擠出機70a」)中設置有:料斗71,用於投入用以形成發泡樹脂層20之聚丙烯系樹脂組合物,及氣體導入部72,用於向氣缸內供給烴等氣體成分。The first extruder 70 is an extruder for forming the foamed resin layer 20, and an extruder (hereinafter also referred to as "upstream side extruder 70a") on the upstream side thereof is provided with a hopper 71. The polypropylene resin composition for forming the foamed resin layer 20 and the gas introduction portion 72 for supplying a gas component such as hydrocarbon into the cylinder.
另外,於該上游側擠出機70a之下游側,具備用於將含有上述氣體成分之聚丙烯系樹脂組合物(以下亦稱為「發泡性樹脂組合物」)熔融混練並噴出至匯流模具XH中之擠出機(以下,亦稱為「下游側擠出機70b」)。In addition, on the downstream side of the upstream side extruder 70a, a polypropylene resin composition (hereinafter also referred to as "foaming resin composition") containing the gas component is melted and kneaded and discharged to a manifold. An extruder in XH (hereinafter also referred to as "downstream side extruder 70b").
另外,上述第2擠出機80係用以形成第一表面層11及第二表面層12之擠出機,其係構成為:自料斗81投入非發泡狀態之用於形成表面層之聚丙烯系樹脂組合物(以下亦稱為「非發泡性樹脂組合物」),於氣缸內部熔融混練該非發泡性樹脂組合物並噴出至匯流模具XH中。Further, the second extruder 80 is an extruder for forming the first surface layer 11 and the second surface layer 12, and is configured to form a surface layer from the hopper 81 in a non-foamed state. The propylene resin composition (hereinafter also referred to as "non-foaming resin composition") melts and kneads the non-foamable resin composition in the interior of the cylinder and ejects it into the manifold mold XH.
上述匯流模具XH如圖3所示之其概略剖面圖般,形成有:自圖3正面視右側朝向左側貫通中心部之第一樹脂流路W1;用以使樹脂於該第一樹脂流路W1之中途流入至該第一樹脂流路W1內之第二樹脂流路W2;及用以使樹脂於較該第二樹脂流路W2之更上游側(圖3正面視右側)流入至該第一樹脂流路W1內之第三樹脂流路W3。As shown in the schematic cross-sectional view of the manifold mold XH, a first resin flow path W1 penetrating from the right side toward the left side of the center portion of FIG. 3 is formed, and the resin is applied to the first resin flow path W1. a second resin flow path W2 flowing into the first resin flow path W1 in the middle; and flowing the resin to the first upstream side (the right side in the front view of FIG. 3) of the second resin flow path W2 The third resin flow path W3 in the resin flow path W1.
上述第二樹脂流路W2係形成為可使樹脂組合物自於形成樹脂流路W1之壁面開口的圓環狀之縫隙S1流入至樹脂流路W1中,上述第三樹脂流路W3係形成為與在上述第一樹脂流路W1之中心部配置有開口端之管體P連接,可使樹脂組合物流入至第一樹脂流路W1之中心部。The second resin flow path W2 is formed such that the resin composition can flow into the resin flow path W1 from the annular slit S1 opening the wall surface of the resin flow path W1, and the third resin flow path W3 is formed as The tube body P having the opening end disposed at the center of the first resin flow path W1 is connected to the center portion of the first resin flow path W1.
上述第一樹脂流路W1於其上游側與第1擠出機70連接,下游側與圓形模具CD連接,上述第2樹脂流路W2及上述第三樹脂流路W3經由分配管D與第2擠出機80連接,以可使非發泡性樹脂組合物自第2擠出機80流入。The first resin flow path W1 is connected to the first extruder 70 on the upstream side thereof, the downstream side is connected to the circular die CD, and the second resin flow path W2 and the third resin flow path W3 are connected via the distribution pipe D and the 2 The extruder 80 is connected so that the non-expandable resin composition can flow from the second extruder 80.
亦即,具備本實施形態之匯流模具XH可使得於第一樹脂流路W1之下游側,形成非發泡性樹脂組合物/發泡性樹脂組合物/非發泡性樹脂組合物之三重結構的圓柱狀之樹脂流,並將該等樹脂朝圓形模具CD中供給。In other words, the bus bar mold XH of the present embodiment can form a triple structure of the non-foaming resin composition/expandable resin composition/non-foaming resin composition on the downstream side of the first resin flow path W1. The cylindrical resin flow is supplied to the circular mold CD.
另外,圓形模具CD係形成為可使自匯流模具XH流入的三重(自中心朝向外側為「非發泡性樹脂組合物」/「發泡性樹脂組合物」/「非發泡性樹脂組合物」)之圓柱狀之樹脂組合物流變為圓筒狀流並自圓環狀之噴出孔共擠出。In addition, the circular mold CD is formed into a triple weight (flowable resin composition) / "foaming resin composition" / "non-foaming resin combination" from the center toward the outside. The cylindrical resin composition stream of the material "" becomes a cylindrical flow and is coextruded from the annular discharge hole.
藉由上述裝置製作樹脂發泡片材可列舉下述方法:首先自第1擠出機70之料斗71投入用於形成發泡樹脂層20的聚丙烯系樹脂組合物,且向第2擠出機80中投入用以形成表面層11、12之聚丙烯系樹脂組合物,在各擠出機內,於樹脂之熔融溫度以上之溫度下實施熔融混練後自圓形模具CD中共擠出。The resin foamed sheet is produced by the above-described apparatus. First, a polypropylene resin composition for forming the foamed resin layer 20 is introduced from the hopper 71 of the first extruder 70, and the second extrusion is performed. The polypropylene resin composition for forming the surface layers 11 and 12 is introduced into the machine 80, and is melt-kneaded at a temperature equal to or higher than the melting temperature of the resin in each extruder, and then coextruded from the circular die CD.
再者,各樹脂組合物可將各成分預先形成為均質之混合狀態然後投入至料斗中,亦可分別將各成分投入至料斗後在擠出機內混合。Further, each of the resin compositions may be formed into a homogeneous mixed state in advance and then introduced into a hopper, or each component may be separately charged into a hopper and then mixed in an extruder.
該等擠出機中之第1擠出機70中,由於需要將用於發泡之成分熔融混練,故而係自設置於上游側擠出機70a上之氣體導入部72壓入氣體成分並與熔融樹脂混合。In the first extruder 70 of the extruder, since it is necessary to melt and knead the components for foaming, the gas introduction unit 72 provided in the upstream side extruder 70a presses the gas component and The molten resin is mixed.
自上述圓形模具CD之共擠出可藉由如下方式而實施:將於第1擠出機70之上游側擠出機70a中熔融混練之發泡性樹脂組合物,在下游側擠出機70b中調整為適合於擠出發泡之溫度並輸送至匯流模具XH中,另一方面,於第2擠出機80中,將非發泡性樹脂組合物調整為適合形成第一、第二表面層11、12之溫度並輸送至匯流模具XH中,預先於匯流模具XH內形成熔融樹脂之積層結構。The co-extrusion from the circular mold CD can be carried out by expanding and kneading the foamable resin composition in the extruder 70a on the upstream side of the first extruder 70, and on the downstream side extruder. 70b is adjusted to be suitable for the temperature of extrusion foaming and transported to the manifold mold XH, and on the other hand, in the second extruder 80, the non-foamable resin composition is adjusted to form the first and second surfaces. The temperatures of the layers 11, 12 are transferred to the manifold mold XH, and a laminated structure of molten resin is formed in advance in the manifold mold XH.
繼而,使於匯流模具XH內匯流之各樹脂組合物自圓形模具CD之圓環狀之噴出孔中共擠出,從而藉由各聚丙烯系樹脂組合物形成具有包含發泡樹脂層20或表面層11、12之積層結構的圓筒狀之發泡體。Then, each of the resin compositions that are converged in the manifold mold XH is co-extruded from the annular discharge holes of the circular mold CD, thereby forming the foamed resin layer 20 or the surface by the respective polypropylene resin compositions. A cylindrical foam having a laminated structure of layers 11 and 12.
然後,使上述發泡體緊附於直徑大於圓形模具CD之噴出孔的心軸MD之外周面上使之於周方向上延伸並加以冷卻,利用切斷工具(未圖示)將經冷卻之發泡體上下一分為二,獲得帶狀之樹脂發泡片材1,並分別捲取於輥92上。Then, the foam is adhered to the outer peripheral surface of the mandrel MD having a diameter larger than the discharge hole of the circular die CD so as to extend in the circumferential direction and cooled, and cooled by a cutting tool (not shown). The foam was divided into two, and a strip-shaped resin foamed sheet 1 was obtained and wound up on a roll 92, respectively.
此時,藉由在用於形成發泡樹脂層20之聚丙烯系樹脂組合物中含有HMS-PP,可於良好之發泡狀態下將其擠出。At this time, by containing HMS-PP in the polypropylene resin composition for forming the foamed resin layer 20, it can be extruded in a good foaming state.
再者,上述圓筒狀之發泡體在噴出後立即伴隨著發泡度之增大而厚度增大,從而使表觀體積膨脹。Further, immediately after the discharge, the cylindrical foam has a thickness which increases in accordance with an increase in the degree of foaming, thereby expanding the apparent volume.
此外,該發泡體不僅於厚度方向上體積膨脹,於周方向上亦產生體積膨脹。Further, the foam not only expands in volume in the thickness direction but also expands in volume in the circumferential direction.
另外,上述圓筒狀之發泡體藉由輥92之牽引力而向心軸MD之方向移動,且伴隨該移動而逐漸擴徑接近心軸MD之外徑。Further, the cylindrical foam is moved in the direction of the mandrel MD by the pulling force of the roller 92, and gradually increases in diameter to approach the outer diameter of the mandrel MD in accordance with the movement.
因此,如圖4所示,若擠出後之周方向之膨脹速度在該發泡體FB之擴徑速度以下,則特別出現問題之可能性較低,但是通常於圓形模具CD之附近膨脹速度較高,因此會於發泡體FB中形成鬆弛部FE。Therefore, as shown in Fig. 4, if the expansion speed in the circumferential direction after extrusion is below the expansion speed of the foam FB, the possibility of occurrence of a problem is low, but it is usually expanded near the circular mold CD. Since the speed is high, the slack portion FE is formed in the foam FB.
亦即,若假想以圓形模具CD之噴出孔所描繪之圓作為上底,以面向該圓形模具CD的心軸MD之端面MDa所描繪之圓作為下底的橫向之圓錐台形狀,則圓形模具CD與心軸MD之間之發泡體FB中受到輥92之牽引力之作用的部位FT(以下亦稱為「張力部FT」),以沿著上述圓錐台形狀之側面之傾斜的形態在圓形模具CD與心軸MD之間移動,上述鬆弛部FE通過較上述側面之更內側在圓形模具CD與心軸MD之間移動。That is, if a circle drawn by the ejection hole of the circular die CD is assumed to be the upper base, and a circle drawn toward the end face MDa of the mandrel MD of the circular die CD is used as the lateral truncated cone shape of the lower bottom, A portion FT (hereinafter also referred to as "tension portion FT") which is subjected to the traction force of the roller 92 in the foam FB between the circular die CD and the mandrel MD, so as to be inclined along the side of the truncated cone shape The form moves between the circular die CD and the mandrel MD, and the slack portion FE moves between the circular die CD and the mandrel MD through the inner side of the side face.
並且,於如此之情形時,通常該發泡體FB中會形成複數個鬆弛部FE,圓形模具CD附近形成為鬆弛部FE與張力部FT於周方向上交替形成之狀態。Further, in such a case, a plurality of slack portions FE are usually formed in the foam FB, and the vicinity of the circular die CD is formed in a state in which the slack portion FE and the tension portion FT are alternately formed in the circumferential direction.
再者,發泡體FB之體積膨脹通常於稍離開圓形模具CD之部位結束,伴隨擴徑之進行,鬆弛部FE受到周方向之張力,因此於靠近心軸MD之部位通常觀察不到鬆弛。Further, the volume expansion of the foam FB is usually completed at a portion slightly away from the circular mold CD, and the relaxation portion FE is subjected to tension in the circumferential direction as the diameter expansion progresses. Therefore, no relaxation is generally observed in a portion close to the mandrel MD. .
但是其間至鬆弛部FE消除為止期間,鬆弛部FE與張力部FT上所施加之延伸、或冷卻風之接觸方式(冷卻條件)產生差異,片材厚度或密度等產生差異,導致通過心軸MD後之樹脂發泡片材上形成因上述鬆弛部FE與上述張力部FT之存在而引起之條紋花紋。However, during the period until the relaxation portion FE is eliminated, the relaxation portion FE is different from the extension applied by the tension portion FT or the cooling air contact method (cooling condition), and the thickness or density of the sheet is different, resulting in a pass through the mandrel MD. A stripe pattern due to the presence of the slack portion FE and the tension portion FT is formed on the subsequent resin foam sheet.
本實施形態之聚丙烯系樹脂組合物由於HMS-PP之含量規定有上限,故而發泡行為溫和,自圓形模具CD中擠出後之體積膨脹較為緩慢。Since the polypropylene resin composition of the present embodiment has an upper limit due to the content of HMS-PP, the foaming behavior is mild, and the volume expansion after extrusion from the circular die CD is relatively slow.
因此,發泡體FB中不易產生較大之鬆弛,發泡體FB上所施加之延伸對整體大致均勻地發揮作用,冷卻條件亦變得大致均勻,因此可抑制條紋。Therefore, the foam FB is less likely to cause a large slack, and the extension applied to the foam FB acts substantially uniformly on the whole, and the cooling conditions are also substantially uniform, so that the streaks can be suppressed.
再者,如上所述,若HMS-PP之含量未達下限值,則難以獲得良好之發泡狀態。Further, as described above, if the content of HMS-PP is less than the lower limit, it is difficult to obtain a good foaming state.
再者,藉由加快牽引速度(每單位時間內樹脂發泡片材由輥92捲取之長度),可提高發泡體FB之擴徑速度,因此藉此亦可一定程度地抑制條紋,但是由於上述體積膨脹係瞬時產生,故而與調整聚丙烯系樹脂組合物中之HMS-PP之含量相比,抑制條紋之效果較小。Further, by increasing the pulling speed (the length of the resin foamed sheet wound by the roll 92 per unit time), the expansion speed of the foam FB can be increased, so that the streaks can be suppressed to some extent. Since the volume expansion is instantaneously generated, the effect of suppressing the streaks is small as compared with the content of the HMS-PP in the adjustment of the polypropylene resin composition.
而且,若過度提高牽引速度,則亦會導致發泡體FB中產生較大之張力,故而亦可認為藉由調整聚丙烯系樹脂組合物中之HMS-PP之含量而抑制條紋之方法係更為簡便之方法。Further, if the pulling speed is excessively increased, a large tension is generated in the foam FB. Therefore, it is considered that the method of suppressing the streaking by adjusting the content of the HMS-PP in the polypropylene resin composition is more For the convenience of the method.
再者,該牽引速度亦取決於所製作之樹脂發泡片材之種類或厚度等,但通常設為2 m/min以上、10 m/min以下。Further, the pulling speed is also dependent on the type or thickness of the resin foamed sheet to be produced, but is usually 2 m/min or more and 10 m/min or less.
另外,同樣地,藉由將圓形模具CD之口徑(d1:噴出口之內側圓與外側圓之間的中間圓之直徑)與心軸MD之輪廓(d2)之比率(d2/d1)設為較大比率,增大周方向上之延伸,亦可一定程度地抑制條紋,但此時之效果亦小於調整HMS-PP之含量時獲得之效果。Further, similarly, the ratio (d2/d1) of the circular mold CD diameter (d1: the diameter of the intermediate circle between the inner circle and the outer circle of the discharge port) and the contour (d2) of the mandrel MD is set. For a larger ratio, the extension in the circumferential direction is increased, and the streaks are also suppressed to some extent, but the effect at this time is also smaller than that obtained when the content of HMS-PP is adjusted.
再者,通常該比率(d2/d1)係設為1.9以上、3.2以下,圓形模具CD之縫隙間隙通常係自0.3 mm以上、1.5 mm以下之範圍內選擇。In addition, the ratio (d2/d1) is usually 1.9 or more and 3.2 or less, and the gap gap of the circular mold CD is usually selected from the range of 0.3 mm or more and 1.5 mm or less.
進而,藉由調整發泡劑,可一定程度地控制體積膨脹之行為,但若過度減少發泡劑之含量,則當然有樹脂發泡片材無法顯示良好之發泡狀態之虞。Further, by adjusting the foaming agent, the behavior of volume expansion can be controlled to some extent. However, if the content of the foaming agent is excessively reduced, it is of course possible that the resin foamed sheet does not exhibit a good foaming state.
就該觀點而言,亦可認為藉由HMS-PP之含量而抑制條紋之方法係簡便之方法。From this point of view, it is also considered that the method of suppressing streaking by the content of HMS-PP is a simple method.
再者,例如若發泡劑使用丁烷(正丁烷、異丁烷、或者該等之混合液)等時,通常相對於聚合物成分100質量份之比例為1質量份以上、6質量份以下。In the case of using a butane (n-butane, isobutane, or a mixture thereof), for example, the ratio of the polymer component to 100 parts by mass is usually 1 part by mass or more and 6 parts by mass. the following.
如此製作之樹脂發泡片材厚度或發泡狀態均為均質。The thickness or foaming state of the resin foamed sheet thus produced was homogeneous.
另外,於表面層11、12中,由於結晶度為20%以上、55%以下之乙烯-α-烯烴共聚物或結晶度為20%以上、55以下之低密度聚乙烯樹脂與非離子性抗靜電劑一起含於該等層中,故而該非離子性抗靜電劑可較快地滲出至表面。Further, in the surface layers 11 and 12, an ethylene-α-olefin copolymer having a crystallinity of 20% or more and 55% or less or a low-density polyethylene resin having a crystallinity of 20% or more and 55 or less and nonionic resistance The electrostatic agent is contained together in the layers, so that the nonionic antistatic agent can bleed out to the surface relatively quickly.
藉此,於常溫下例如表面電阻率降低至1×1013 Ω/□以下,可發揮抗靜電性能。Thereby, for example, the surface resistivity is lowered to 1 × 10 13 Ω/□ or less at normal temperature, and the antistatic property can be exhibited.
因此,無需設置至發揮出所期望之抗靜電性能為止之熟化時間等,或者即便設置,該熟化時間亦可於短期間內結束,故而製造樹脂發泡片材後短時間後即可使用,可縮短該樹脂發泡片材之庫存時間。Therefore, it is not necessary to set the aging time or the like until the desired antistatic performance is exhibited, or the aging time can be completed in a short period of time even if it is provided, so that the resin foamed sheet can be used after a short period of time, and can be shortened. The stock time of the resin foamed sheet.
另外,上述樹脂發泡片材由於其物性均質化,故而藉由片材成形法等進行成形加工時,因產生局部之延伸而導致成形品發生「外觀不良」或「裂紋」之可能性較低。In addition, since the resin foamed sheet is homogenized in physical properties, it is less likely to cause "defective appearance" or "crack" in the molded article due to local stretching during the forming process by a sheet forming method or the like. .
亦即,對於提高成形品之良率有用。That is, it is useful for improving the yield of a molded article.
再者,若樹脂發泡片材之表面形成條紋,該樹脂發泡片材之厚度變得不均勻,則厚度較厚之部分首先接觸成形模,其結果,滲出至該部分之抗靜電劑容易向並未與成形模緊密接觸之部分移動。Further, if the surface of the resin foamed sheet is striped, and the thickness of the resin foamed sheet becomes uneven, the thicker portion first contacts the forming mold, and as a result, the antistatic agent which is exuded to the portion is easily formed. Moves to a portion that is not in close contact with the forming die.
並且,於片材成形法中,由於樹脂發泡片材為加熱狀態,故而抗靜電劑之移動性亦提高,若樹脂發泡片材之厚度變得不均勻,則有可能於成形品之表面形成抗靜電劑變濃之部位、與失去抗靜電性之部位。Further, in the sheet forming method, since the resin foamed sheet is in a heated state, the mobility of the antistatic agent is also improved, and if the thickness of the resin foamed sheet becomes uneven, it may be on the surface of the molded article. A portion where the antistatic agent is concentrated and a portion where the antistatic property is lost are formed.
亦即,可認為,使表面層11、12與成形模接觸而藉由片材成形法製作成形品之情形時,可特別適宜地使用本實施形態之樹脂發泡片材。In other words, when the surface layers 11 and 12 are brought into contact with the molding die and the molded article is produced by the sheet forming method, the resin foamed sheet of the present embodiment can be particularly suitably used.
再者,於本實施形態中,係一面例示具有覆蓋發泡樹脂層之兩面之表面層的三層結構之樹脂發泡片材一面說明本發明之實施形態,但於具有四層以上之積層結構之情形時,使用擠出機將如上所述之聚丙烯系樹脂組合物擠出發泡而形成發泡樹脂層時發揮抑制條紋之效果的方面亦與上述例示相同。In the present embodiment, a resin foamed sheet having a three-layer structure covering the surface layers of both surfaces of the foamed resin layer is described as an embodiment of the present invention, but has a laminated structure of four or more layers. In the case where the polypropylene resin composition as described above is extrusion-foamed by an extruder to form a foamed resin layer, the effect of suppressing streaking is also the same as the above-described example.
另外,表面層僅形成於發泡樹脂層之單面側之情形、或發泡樹脂層單層之情形亦同樣。Further, the case where the surface layer is formed only on one side of the foamed resin layer or the single layer of the foamed resin layer is also the same.
進而,於將複數層發泡樹脂層共擠出等情形時,藉由利用本實施形態之聚丙烯系樹脂組合物亦可發揮出抑制條紋之效果。Further, when the plurality of layers of the foamed resin layer are coextruded, the effect of suppressing streaking can be exhibited by using the polypropylene resin composition of the present embodiment.
再者,於此省略進行更詳細之說明,關於樹脂組合物或其擠出發泡技術、或者樹脂發泡片材或其製造方法等之技術事項的公知事項,可於不顯著損害本發明之效果之範圍內採用於本發明中。Further, the detailed description of the resin composition, its extrusion foaming technique, or the resin foamed sheet or the method for producing the same can be omitted without significantly impairing the effects of the present invention. Within the scope of the invention.
以下,列舉實施例更詳細地說明本發明,但本發明並不限定於該等實施例。Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples.
使用與如圖2所示之裝置構成同類之設備製作樹脂發泡片材。A resin foamed sheet was produced using the same apparatus as that shown in Fig. 2.
亦即,以於自第1擠出機70流入發泡性樹脂組合物之樹脂流路W1的上游側及下游側之兩部位,自第2擠出機80經由分枝管D而流入非發泡性樹脂組合物之方式,將第1、第2擠出機連接於匯流模具XH,於該匯流模具XH之下游側連接圓形模具CD,實施共擠出。In other words, the two portions of the upstream side and the downstream side of the resin flow path W1 that has flowed into the foamable resin composition from the first extruder 70 flow from the second extruder 80 through the branch pipe D. In the embodiment of the foamed resin composition, the first and second extruders are connected to the manifold mold XH, and the circular mold CD is connected to the downstream side of the manifold mold XH to perform co-extrusion.
首先,作為用於熔融混合發泡樹脂層之形成材料之第1擠出機,準備包含口徑為90 mm之單軸擠出機(上游側擠出機),以及連接於該單軸擠出機之口徑為115 mm之單軸擠出機(下游側擠出機)的串列型擠出機。First, as a first extruder for melt-blending a material for forming a foamed resin layer, a single-axis extruder (upstream side extruder) having a diameter of 90 mm is prepared, and is connected to the single-axis extruder. A tandem extruder of a single-axis extruder (downstream side extruder) having a diameter of 115 mm.
繼而,將含有包含39質量%之比例的由Borealis公司以商品名「WB135」而市售之HMS-PP、55質量%之比例的由Japan Polypropylene公司以商品名「BC6C」而市售之嵌段PP、6質量%之比例的由SunAllomer公司以商品名「Q-100F」而市售之TPO的聚合物成分,及將該等聚合物成分之合計量設為100質量份時為0.5質量份的碳酸氫鈉-檸檬酸系發泡劑(大日精化公司製造之母料,商品名「Finecell Master PO410K」)的發泡樹脂層形成用之聚丙烯系樹脂組合物,供給至上游側之口徑為90 mm的單軸擠出機之料斗中,於該擠出機中以200℃~210℃之溫度進行加熱熔融後,以相對於該熔融樹脂100質量份之比例為4質量份之方式壓入作為氣體成分之丁烷(異丁烷/正丁烷=35/65質量%)並混練。Then, a block commercially available from Japan Polypropylene Co., Ltd. under the trade name "BC6C" containing a ratio of 39% by mass of HMS-PP marketed by Borealis Corporation under the trade name "WB135" and a ratio of 55 mass% is contained. The polymer component of the TPO commercially available under the trade name "Q-100F" by the company Sun Anyomer, and the total amount of the polymer components is 0.5 parts by mass, based on 100 parts by mass of PP and 6 mass%. The polypropylene resin composition for forming a foamed resin layer of a sodium hydrogencarbonate-citric acid-based foaming agent (a masterbatch manufactured by Dairi Seiki Co., Ltd., trade name "Finecell Master PO410K") is supplied to the upstream side. In a hopper of a 90 mm single-axis extruder, it is heated and melted at a temperature of 200 ° C to 210 ° C in the extruder, and then pressed in a ratio of 4 parts by mass based on 100 parts by mass of the molten resin. Butane (isobutane/n-butane = 35/65 mass%) as a gas component was kneaded.
將該發泡性樹脂組合物供給至下游側之擠出機中,降低發泡性樹脂組合物之溫度,以120 kg/h之噴出量供給至連接於擠出機前端之匯流模具XH中。The foamable resin composition was supplied to an extruder on the downstream side to lower the temperature of the foamable resin composition, and was supplied to a header mold XH connected to the tip end of the extruder at a discharge amount of 120 kg/h.
另一方面,作為用於熔融混合表面層之形成材料之第2擠出機,準備口徑為65 mm之單軸擠出機。On the other hand, as a second extruder for forming a material for melt-mixing the surface layer, a single-axis extruder having a diameter of 65 mm was prepared.
繼而,將含有包含70質量%之比例的由BoreaIis公司以商品名「WB135」而市售之HMS-PP、30質量%之比例的由日本聚乙烯公司以商品名「KS240T」(結晶度:26%)而市售之乙烯-α-烯烴共聚物的聚合物成分,及將該等聚合物成分之合計量設為100質量份時為2.0質量份的非離子性抗靜電劑(花王公司製造,商品名「TS-2B」)的表面層形成用之聚丙烯系樹脂組合物供給至第2擠出機之料斗中,以200℃之溫度進行加熱熔融。Then, the product of the Japanese polyethylene company under the trade name "KS240T" (crystallinity: 26) containing a ratio of 70% by mass of HMS-PP marketed under the trade name "WB135" by BoreaIis Co., Ltd., containing 30% by mass. %) a polymer component of a commercially available ethylene-α-olefin copolymer, and a nonionic antistatic agent (manufactured by Kao Corporation, 2.0 parts by mass) when the total amount of the polymer components is 100 parts by mass. The polypropylene resin composition for forming a surface layer of the product name "TS-2B" was supplied to a hopper of a second extruder, and was heated and melted at a temperature of 200 °C.
繼而,將該熔融狀態之(非發泡性之)聚丙烯系樹脂組合物於具有分枝流路之分配管中一分為二後,使其自於匯流模具之樹脂流路之中央部開口之管體、及於樹脂流路之外周部開口之縫隙兩者,以各者之合計量為15 kg/h之量而噴出,使發泡性樹脂組合物之內層側與外層側積層匯流,然後自連接於匯流模具前端之圓形模具(口徑為140 mm,縫隙間隙為1.0 mm)以135 kg/h之樹脂噴出量呈圓筒狀地共擠出,藉此形成隔著發泡樹脂層而於其內外兩側積層有非發泡之表面層的圓筒狀之發泡體。Then, the molten (non-foaming) polypropylene resin composition is divided into two in a distribution pipe having a branching flow path, and then opened from the central portion of the resin flow path of the manifold. Both the tube body and the slit opening in the peripheral portion of the resin flow path are ejected in an amount of 15 kg/h in total, and the inner layer side and the outer layer side layer of the expandable resin composition are converged. Then, a circular mold (with a diameter of 140 mm and a gap of 1.0 mm) connected to the front end of the manifold is cylindrically coextruded at a resin discharge amount of 135 kg/h, thereby forming a foamed resin. The layer has a cylindrical foam having a non-foamed surface layer laminated on both inner and outer sides thereof.
使該藉由擠出發泡所製作的圓筒狀之發泡體緊附於直徑:414 mm×長度:500 mm之冷卻用心軸上進行擴徑,並且自空氣冷卻環對其外表面吹附空氣而使之冷卻,用切割器於在該心軸之周方向上呈對稱(展開180度)之2點處切開,藉此製作2片帶狀之樹脂發泡片材。The cylindrical foam produced by extrusion foaming is attached to a cooling mandrel having a diameter of 414 mm × length: 500 mm, and the air is blown from the outer surface of the air cooling ring. Further, it was cooled, and cut by a cutter at two points which were symmetrical (expanded by 180 degrees) in the circumferential direction of the mandrel, thereby producing two strip-shaped resin foamed sheets.
依據JIS K 6911-1995,對所獲得的實施例1之樹脂發泡片材測定表面電阻率。再者,係將預處理時間設為24小時而進行測定。The surface resistivity of the obtained resin foamed sheet of Example 1 was measured in accordance with JIS K 6911-1995. Further, the measurement was carried out by setting the pretreatment time to 24 hours.
具體而言,將一邊為10 cm的平面正方形之試片於溫度22℃、濕度60%之環境下放置24小時後,於溫度22℃、濕度60%之環境下,使用試驗裝置(Advantest公司製造,數位超高電阻/微量電流計R8340及電阻率測試盒(resistivity chamber)R12702A),以約30 N之負載於試片上壓接電極,施加500 V之電壓,測定經過1分鐘後之電阻值,藉由下式計算出表面電阻率。Specifically, a test piece of a flat square having a side of 10 cm was allowed to stand in an environment of a temperature of 22 ° C and a humidity of 60% for 24 hours, and then a test apparatus (manufactured by Advantest) was used in an environment of a temperature of 22 ° C and a humidity of 60%. , the digital ultra-high resistance/micro current meter R8340 and the resistivity test chamber R12702A), the electrode is crimped on the test piece with a load of about 30 N, and a voltage of 500 V is applied to measure the resistance value after 1 minute. The surface resistivity was calculated by the following formula.
ρs=π(D+d)/(D-d)×RsΡs=π(D+d)/(D-d)×Rs
其中,among them,
ρs:表面電阻率(Ω/□)Ρs: surface resistivity (Ω/□)
D:表面之環狀電極之內徑(cm)(電阻率測試盒R12702A中為7 cm)D: inner diameter (cm) of the ring electrode on the surface (7 cm in the resistivity test box R12702A)
d:表面電極之內圓之外徑(cm)(電阻率測試盒R12702A中為5 cm)d: outer diameter (cm) of the inner circle of the surface electrode (5 cm in the resistivity test box R12702A)
Rs:表面電阻(Ω)Rs: surface resistance (Ω)
結果觀測到3.5×1012 Ω/□之表面電阻率之值。As a result, a value of surface resistivity of 3.5 × 10 12 Ω/□ was observed.
另外,該樹脂發泡片材中未觀測到顯眼之條紋。Further, no conspicuous streaks were observed in the resin foamed sheet.
繼而,藉由片材成形法製作發泡盤,結果獲得外觀美麗且機械強度亦優異之發泡盤。Then, a foamed disk was produced by a sheet forming method, and as a result, a foamed disk having a beautiful appearance and excellent mechanical strength was obtained.
於用以形成表面層之聚丙烯系樹脂組合物中,代替日本聚乙烯公司製造之乙烯-α-烯烴共聚物(KS240T),而使用由日本聚乙烯公司以商品名「LD400」市售的結晶度為50%之低密度聚乙烯(PE)樹脂,除此以外,以與實施例1相同之方式製造樹脂發泡片材,製作發泡盤。In the polypropylene resin composition for forming the surface layer, instead of the ethylene-α-olefin copolymer (KS240T) manufactured by Nippon Polyethylene Co., Ltd., a crystal commercially available from Nippon Polyethylene Co., Ltd. under the trade name "LD400" is used. A resin foamed sheet was produced in the same manner as in Example 1 except that a low-density polyethylene (PE) resin having a degree of 50% was used, and a foamed disk was produced.
對該實施例2之樹脂發泡片材,以與實施例1相同之方式測定表面電阻率,結果得知其具有5.0×1012 Ω/□之表面電阻率。The surface resistivity of the resin foamed sheet of Example 2 was measured in the same manner as in Example 1. As a result, it was found to have a surface resistivity of 5.0 × 10 12 Ω/□.
而且,未觀測到顯眼之條紋,藉由該樹脂發泡片材所形成之發泡盤外觀美麗且機械強度優異。Further, no conspicuous streaks were observed, and the foamed disc formed by the resin foamed sheet was beautiful in appearance and excellent in mechanical strength.
於用以形成表面層之聚丙烯系樹脂組合物中,代替日本聚乙烯公司製造之乙烯-α-烯烴共聚物(KS240T),而使用由日本聚乙烯公司以商品名「LF441B」市售的結晶度為53%之低密度聚乙烯(PE)樹脂,除此以外,以與實施例1相同之方式製造樹脂發泡片材,製作發泡盤。In the polypropylene resin composition for forming the surface layer, in place of the ethylene-α-olefin copolymer (KS240T) manufactured by Nippon Polyethylene Co., Ltd., a crystal commercially available from Nippon Polyethylene Co., Ltd. under the trade name "LF441B" is used. A resin foamed sheet was produced in the same manner as in Example 1 except that a low-density polyethylene (PE) resin having a degree of 53% was used, and a foamed disk was produced.
對該實施例3之樹脂發泡片材,以與實施例1相同之方式測定表面電阻率,結果得知其具有6.5×1012 Ω/□之表面電阻率。The surface resistivity of the resin foamed sheet of Example 3 was measured in the same manner as in Example 1. As a result, it was found to have a surface resistivity of 6.5 × 10 12 Ω/□.
而且,未觀測到顯眼之條紋,藉由該樹脂發泡片材所形成之發泡盤外觀美麗且機械強度優異。Further, no conspicuous streaks were observed, and the foamed disc formed by the resin foamed sheet was beautiful in appearance and excellent in mechanical strength.
於用以形成表面層之聚丙烯系樹脂組合物中,代替日本聚乙烯公司製造之乙烯-α-烯烴共聚物(KS240T),而使用由住友化學工業公司以商品名「Erichsen VL-100」市售的結晶度為36%之超低密度聚乙烯(PE)樹脂,除此以外,以與實施例1相同之方式製造樹脂發泡片材,製作發泡盤。In the polypropylene resin composition for forming the surface layer, in place of the ethylene-α-olefin copolymer (KS240T) manufactured by Nippon Polyethylene Co., Ltd., the product name "Erichsen VL-100" by Sumitomo Chemical Industries Co., Ltd. is used. A resin foamed sheet was produced in the same manner as in Example 1 except that an ultra-low-density polyethylene (PE) resin having a crystallinity of 36% was sold, and a foamed disk was produced.
對該實施例4之樹脂發泡片材,以與實施例1相同之方式測定表面電阻率,結果得知其具有4.0×1012 Ω/□之表面電阻率。The surface resistivity of the resin foamed sheet of Example 4 was measured in the same manner as in Example 1. As a result, it was found to have a surface resistivity of 4.0 × 10 12 Ω / □.
而且,未觀測到顯眼之條紋,藉由該樹脂發泡片材所形成之發泡盤外觀美麗且機械強度優異。Further, no conspicuous streaks were observed, and the foamed disc formed by the resin foamed sheet was beautiful in appearance and excellent in mechanical strength.
將用以形成發泡樹脂層之聚丙烯系樹脂組合物中的HMS-PP(WB135)之比例代替39質量%而設為25質量%,或者將嵌段PP(BC6C)之比例代替55質量%而設為69質量%,除此以外,以與實施例1相同之方式製造樹脂發泡片材,製作發泡盤。The ratio of HMS-PP (WB135) in the polypropylene resin composition for forming the foamed resin layer was set to 25% by mass instead of 39% by mass, or the ratio of the block PP (BC6C) was replaced by 55% by mass. A resin foamed sheet was produced in the same manner as in Example 1 except that the amount was 69% by mass, and a foamed disk was produced.
對該實施例5之樹脂發泡片材,以與實施例1相同之方式測定表面電阻率,結果得知其具有3.5×1012 Ω/□之表面電阻率。The surface resistivity of the resin foamed sheet of Example 5 was measured in the same manner as in Example 1. As a result, it was found to have a surface resistivity of 3.5 × 10 12 Ω/□.
而且,未觀測到顯眼之條紋,藉由該樹脂發泡片材所形成之發泡盤外觀美麗且機械強度優異。Further, no conspicuous streaks were observed, and the foamed disc formed by the resin foamed sheet was beautiful in appearance and excellent in mechanical strength.
於用以形成表面層之聚丙烯系樹脂組合物中,將聚合物成分設為HMS-PP(WB135)100質量%,除此以外,以與實施例1相同之方式製造樹脂發泡片材,製作發泡盤。A resin foamed sheet was produced in the same manner as in Example 1 except that the polymer component was 100% by mass of HMS-PP (WB135) in the polypropylene resin composition for forming the surface layer. Make a foaming tray.
對該實施例6之樹脂發泡片材,以與實施例1相同之方式測定表面電阻率,結果顯示4.5×1013 Ω/□之表面電阻率。The surface resistivity of the resin foamed sheet of Example 6 was measured in the same manner as in Example 1. As a result, the surface resistivity of 4.5 × 10 13 Ω / □ was shown.
而且,於樹脂發泡片材本身並未觀測到顯眼之條紋,藉由該樹脂發泡片材所形成之發泡盤外觀美麗且機械強度優異。Further, no conspicuous streaks were observed in the resin foamed sheet itself, and the foamed disc formed by the resin foamed sheet was beautiful in appearance and excellent in mechanical strength.
除不於用以形成表面層之聚丙烯系樹脂組合物中含有非離子性抗靜電劑以外,以與實施例1相同之方式製造樹脂發泡片材,製作發泡盤。A resin foamed sheet was produced in the same manner as in Example 1 except that a nonionic antistatic agent was contained in the polypropylene resin composition for forming the surface layer, and a foamed disk was produced.
對該實施例7之樹脂發泡片材,以與實施例1相同之方式測定表面電阻率,結果顯示6.5×1015 Ω/□之表面電阻率。The surface resistivity of the resin foamed sheet of Example 7 was measured in the same manner as in Example 1, and as a result, the surface resistivity of 6.5 × 10 15 Ω / □ was shown.
而且,於樹脂發泡片材本身並未觀測到顯眼之條紋,藉由該樹脂發泡片材所形成之發泡盤外觀美麗且機械強度優異。Further, no conspicuous streaks were observed in the resin foamed sheet itself, and the foamed disc formed by the resin foamed sheet was beautiful in appearance and excellent in mechanical strength.
除不於用以形成表面層之聚丙烯系樹脂組合物中含有非離子性抗靜電劑以外,以與實施例5相同之方式製造樹脂發泡片材,製作發泡盤。A resin foamed sheet was produced in the same manner as in Example 5 except that a nonionic antistatic agent was contained in the polypropylene resin composition for forming the surface layer, and a foamed disk was produced.
對該實施例8之樹脂發泡片材,以與實施例1相同之方式測定表面電阻率,結果顯示6.5×1015 Ω/□之表面電阻率。The surface resistivity of the resin foamed sheet of Example 8 was measured in the same manner as in Example 1, and as a result, the surface resistivity of 6.5 × 10 15 Ω / □ was shown.
而且,於樹脂發泡片材本身並未觀測到顯眼之條紋,藉由該樹脂發泡片材所形成之發泡盤外觀美麗且機械強度優異。Further, no conspicuous streaks were observed in the resin foamed sheet itself, and the foamed disc formed by the resin foamed sheet was beautiful in appearance and excellent in mechanical strength.
將用以形成發泡樹脂層之聚丙烯系樹脂組合物中的HMS-PP(WB135)之比例代替39質量%而設為18質量%,或者將嵌段PP(BC6C)之比例代替55質量%而設為76質量%,除此以外,以與實施例1相同之方式製造樹脂發泡片材,製作發泡盤。The proportion of HMS-PP (WB135) in the polypropylene resin composition for forming the foamed resin layer was set to 18% by mass instead of 39% by mass, or the ratio of the block PP (BC6C) was replaced by 55% by mass. A resin foamed sheet was produced in the same manner as in Example 1 except that the amount was 76% by mass, and a foamed disk was produced.
對該比較例1之樹脂發泡片材,以與實施例1相同之方式測定表面電阻率,結果得知其具有3.5×1012 Ω/□之表面電阻率。The surface resistivity of the resin foamed sheet of Comparative Example 1 was measured in the same manner as in Example 1. As a result, it was found to have a surface resistivity of 3.5 × 10 12 Ω/□.
但是,樹脂發泡片材並未發泡至具有充分之厚度,儘管未觀測到顯眼之條紋,但藉由該樹脂發泡片材所形成之發泡盤之機械強度較各實施例之情形差。However, the resin foamed sheet was not foamed to have a sufficient thickness, and although no conspicuous streaks were observed, the mechanical strength of the foamed disk formed by the resin foamed sheet was inferior to that of the respective examples. .
將用以形成發泡樹脂層之聚丙烯系樹脂組合物中的HMS-PP(WB135)之比例代替39質量%而設為50質量%,或者將嵌段PP(BC6C)之比例代替55質量%而設為44質量%,除此以外,以與實施例1相同之方式製造樹脂發泡片材,製作發泡盤。The ratio of HMS-PP (WB135) in the polypropylene resin composition for forming the foamed resin layer was changed to 39% by mass instead of 39% by mass, or the ratio of the block PP (BC6C) was replaced by 55% by mass. A resin foamed sheet was produced in the same manner as in Example 1 except that the amount was 44% by mass, and a foamed disk was produced.
對該比較例2之樹脂發泡片材,以與實施例1相同之方式測定表面電阻率,結果得知其具有3.5×1012 Ω/□之表面電阻率。The surface resistivity of the resin foamed sheet of Comparative Example 2 was measured in the same manner as in Example 1. As a result, it was found to have a surface resistivity of 3.5 × 10 12 Ω/□.
但是,樹脂發泡片材之條紋顯眼,藉由該樹脂發泡片材所形成之發泡盤可見孔洞不良,難以獲得良好外觀之發泡盤。However, the streaks of the resin foamed sheet are conspicuous, and the foamed disc formed of the resin foamed sheet can be found to have poor pores, and it is difficult to obtain a foamed disc having a good appearance.
以上之實施例、比較例之研究結果示於下述比較表(表1)中。The results of the above examples and comparative examples are shown in the following comparison table (Table 1).
由上述亦可知,根據本發明,可提供一種條紋得到抑制,適合作為具有立體結構之發泡成形品之形成材料的樹脂發泡片材。As described above, according to the present invention, it is possible to provide a resin foamed sheet which is suitable as a material for forming a foamed molded article having a three-dimensional structure.
1...樹脂發泡片材1. . . Resin foam sheet
11...第一表面層(非發泡樹脂層)11. . . First surface layer (non-foamed resin layer)
12...第二表面層(非發泡樹脂層)12. . . Second surface layer (non-foamed resin layer)
20...發泡樹脂層20. . . Foamed resin layer
70...第1擠出機70. . . First extruder
70a...上游側擠出機70a. . . Upstream side extruder
70b...下游側擠出機70b. . . Downstream side extruder
71、81...料斗71, 81. . . hopper
72...氣體導入部72. . . Gas introduction
80...第2擠出機80. . . 2nd extruder
91...輥91. . . Roll
92...捲取輥92. . . Take-up roll
A...虛線A. . . dotted line
CD...圓形模具CD. . . Round mold
CL...冷卻裝置CL. . . Cooling device
D...分配管(分枝管)D. . . Distribution tube (branch tube)
FE...鬆弛部FE. . . Slack
FT...張力部FT. . . Tension section
MD...心軸MD. . . Mandrel
MDa...端面MDa. . . End face
P...管體P. . . Tube body
S1...縫隙S1. . . Gap
W1...第一樹脂流路W1. . . First resin flow path
W2...第二樹脂流路W2. . . Second resin flow path
W3...第三樹脂流路W3. . . Third resin flow path
XH...匯流模具XH. . . Confluence mould
圖1係表示本實施形態之樹脂發泡片材之結構的剖面圖。Fig. 1 is a cross-sectional view showing the structure of a resin foamed sheet of the present embodiment.
圖2係表示本實施形態之樹脂發泡片材之製造裝置之構成的概略圖。Fig. 2 is a schematic view showing the configuration of a manufacturing apparatus of a resin foamed sheet of the embodiment.
圖3係表示匯流模具之結構的剖面圖。Fig. 3 is a cross-sectional view showing the structure of a manifold.
圖4係表示「條紋」之形成過程的概略圖。Fig. 4 is a schematic view showing a process of forming "streaks".
1...樹脂發泡片材1. . . Resin foam sheet
11...第一表面層(非發泡樹脂層)11. . . First surface layer (non-foamed resin layer)
12...第二表面層(非發泡樹脂層)12. . . Second surface layer (non-foamed resin layer)
20...發泡樹脂層20. . . Foamed resin layer
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JP2020163614A (en) * | 2019-03-28 | 2020-10-08 | 積水化成品工業株式会社 | Method for manufacturing biodegradable resin foam sheet |
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