TWI756389B - Heat shrinkable film - Google Patents
Heat shrinkable film Download PDFInfo
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- TWI756389B TWI756389B TW107109425A TW107109425A TWI756389B TW I756389 B TWI756389 B TW I756389B TW 107109425 A TW107109425 A TW 107109425A TW 107109425 A TW107109425 A TW 107109425A TW I756389 B TWI756389 B TW I756389B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C61/00—Shaping by liberation of internal stresses; Making preforms having internal stresses; Apparatus therefor
- B29C61/06—Making preforms having internal stresses, e.g. plastic memory
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- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
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Abstract
Description
發明領域 Field of Invention
本發明是有關於一種熱收縮性膜。 The present invention relates to a heat shrinkable film.
本申請案根據2017年3月29日在日本所申請特願2017-064407號主張優先權，且在此援用其內容。 This application claims priority based on Japanese Patent Application No. 2017-064407 filed in Japan on March 29, 2017, and the content is incorporated herein by reference.
背景技術 Background technique
目前廣泛地使用熱收縮性膜作為容器的收縮包裝或收縮標籤。一般而言，熱收縮性膜是沿著預先設置於膜上的穿孔來斷開，並與容器分別廢棄、再循環。 Currently, heat shrinkable films are widely used as shrink wrapping or shrink labels for containers. Generally, the heat-shrinkable film is cut along the perforation previously provided in the film, and is discarded and recycled separately from the container.
對於熱收縮性膜除了要求收縮性、印刷適性、屬於環境取向素材及膜剛性強等外，還要求收縮加工性優異(例如不易產生皺褶或收縮不均等)、穿孔開封性優異、安裝性優異(例如安裝時不易引起標籤之破裂等)、自然收縮率低、保管時之膜安定性優異(例如保管時之膜不易產生皺褶或尺寸變化等)。 For heat-shrinkable films, in addition to shrinkability, printability, environmental orientation materials, and strong film rigidity, they are also required to have excellent shrinkage processability (for example, no wrinkles or uneven shrinkage, etc.), excellent perforation and unsealing properties, and excellent installation properties. (For example, it is not easy to cause the label to break during installation, etc.), the natural shrinkage rate is low, and the film stability during storage is excellent (for example, the film is not prone to wrinkles or dimensional changes during storage).
容器的收縮包裝或收縮標籤中所用熱收縮性膜包括聚氯乙烯系熱收縮性膜、聚酯系熱收縮性膜、聚苯乙烯系熱收縮性膜等(專利文獻1、2)。 The heat-shrinkable films used for shrink wrapping or shrink labels of containers include polyvinyl chloride-based heat-shrinkable films, polyester-based heat-shrinkable films, polystyrene-based heat-shrinkable films, and the like (Patent Documents 1 and 2).
聚氯乙烯系熱收縮性膜雖然收縮加工性、穿孔開封性、安裝性優異且自然收縮率低，但卻有焚化時產生有毒性含氯氣體等問題。又，聚酯系熱收縮性膜雖然保管時之膜安定性或剛性強度等優異，但卻有收縮加工性、穿孔開封性、安裝性不佳等問題。 Although the polyvinyl chloride-based heat-shrinkable film is excellent in shrink processability, perforation openability, and installability, and has a low natural shrinkage rate, it has problems such as the generation of toxic chlorine-containing gas during incineration. In addition, polyester-based heat-shrinkable films are excellent in film stability, rigidity, and the like during storage, but have problems such as poor shrink processability, perforation-opening properties, and mounting properties.
另一方面，雖然相較於使用上述其他材質之膜，聚苯乙烯系熱收縮性膜的收縮加工性、穿孔開封性、安裝性較為優異，但是自然收縮率高，在保管時之膜安定性方面會有問題。 On the other hand, the polystyrene-based heat-shrinkable film is superior in shrink processability, perforation-opening property, and mounting property compared to films using the other materials mentioned above, but the natural shrinkage rate is high, and the film is stable during storage. There will be problems.
先前技術文獻 prior art literature
專利文獻 Patent Literature
專利文獻1：日本特開2006-044219號公報 Patent Document 1: Japanese Patent Laid-Open No. 2006-044219
專利文獻2：日本特開2012-031339號公報 Patent Document 2: Japanese Patent Laid-Open No. 2012-031339
發明概要 Summary of Invention
本發明是有鑑於上述情形而成，目的在提供一種聚苯乙烯系熱收縮性膜，其具備優異之收縮加工性、穿孔開封性與安裝性，且相較於習知聚苯乙烯系熱收縮性膜，保管時之膜安定性更為提升。 The present invention is made in view of the above circumstances, and an object of the present invention is to provide a polystyrene-based heat-shrinkable film, which has excellent shrinkage processability, perforation openability, and installation properties, and which is compared with the conventional polystyrene-based heat-shrinkable film. , the stability of the film during storage is further improved.
本發明之實施態樣具有以下方面。 Embodiments of the present invention have the following aspects.
[1]一種熱收縮性膜，其含有聚苯乙烯系樹脂，並且，浸漬於70℃之水中10秒鐘時主收縮方向之熱收縮率為 15%以下，浸漬於98℃之水中10秒鐘時主收縮方向之熱收縮率為60%以上，與主收縮方向呈正交方向之艾門朵夫撕裂強度在3~10N/mm之範圍內，主收縮方向之艾門朵夫撕裂強度在10~20N/mm之範圍內，於85℃下放置5分鐘時主收縮方向之收縮應力為4.0N/mm2以下，於40℃下放置7日時主收縮方向之收縮率為1.5%以下。 [1] A heat-shrinkable film comprising a polystyrene resin and having a thermal shrinkage rate of 15% or less in the main shrinkage direction when immersed in water at 70°C for 10 seconds, and immersed in water at 98°C for 10 seconds When the thermal shrinkage in the main shrinkage direction is more than 60%, the Emmendorf tear strength in the direction perpendicular to the main shrinkage direction is in the range of 3~10N/mm, and the Emmendorf tear strength in the main shrinkage direction is in the range of 3~10N/mm. In the range of 10~20N/mm, the shrinkage stress in the main shrinkage direction is 4.0N/ mm2 or less when placed at 85℃ for 5 minutes, and the shrinkage rate in the main shrinkage direction when placed at 40℃ for 7 days is less than 1.5%.
[2]一種熱收縮性膜之製造方法，係製造前述熱收縮性膜之方法，其中前述熱收縮性膜係藉由於擠出成形後針對主收縮方向進行延伸而形成，且前述延伸係以餘熱溫度成為100℃以上、延伸溫度及熱固定溫度成為90℃以上、延伸倍率成為4.9以上之方式進行延伸。 [2] A method of manufacturing a heat-shrinkable film, which is a method of manufacturing the aforementioned heat-shrinkable film, wherein the aforementioned heat-shrinkable film is formed by extending in a main shrinking direction after extrusion molding, and the aforementioned extending is performed with waste heat Stretching is performed so that the temperature is 100° C. or higher, the stretching temperature and the heat setting temperature are 90° C. or higher, and the stretching ratio is 4.9 or higher.
本發明之熱收縮性膜具備優異之收縮加工性、穿孔開封性與安裝性，且相較於習知聚苯乙烯系熱收縮性膜，保管時之膜安定性更為提升。 The heat-shrinkable film of the present invention has excellent shrinkage processability, perforation and unsealing properties, and installation properties, and compared with the conventional polystyrene-based heat-shrinkable film, the film stability during storage is further improved.
用以實施發明之形態 Form for carrying out the invention
本發明之熱收縮性膜(以下亦記作「本膜」)含有聚苯乙烯系樹脂。 The heat-shrinkable film of the present invention (hereinafter also referred to as "this film") contains a polystyrene resin.
(聚苯乙烯系樹脂) (polystyrene resin)
聚苯乙烯系樹脂只要是熱收縮性膜之製造用途中所用公知者即可，可列舉如：苯乙烯-丁二烯共聚物、苯乙烯-丁二烯-苯乙烯共聚物、苯乙烯-乙烯-丁二烯-苯乙烯共聚物、苯乙烯-乙烯基．聚異戊二烯-苯乙烯共聚物等聚苯乙 烯系熱可塑性彈性體；苯乙烯-甲基丙烯酸共聚物、苯乙烯-甲基丙烯酸甲酯共聚物、苯乙烯-甲基丙烯酸乙酯共聚物、苯乙烯-甲基丙烯酸丁酯共聚物、苯乙烯-甲基丙烯酸苯酯共聚物等耐衝擊性苯乙烯系樹脂。於該等之中，可單獨使用1種，亦可使用2種以上。 The polystyrene-based resin may be any known one used for the production of heat-shrinkable films, and examples thereof include styrene-butadiene copolymers, styrene-butadiene-styrene copolymers, and styrene-ethylene copolymers. -Butadiene-styrene copolymer, styrene-vinyl. Polystyrene such as polyisoprene-styrene copolymer Ethylene thermoplastic elastomer; styrene-methacrylic acid copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, benzene Impact-resistant styrene-based resins such as ethylene-phenyl methacrylate copolymers. Among these, one type may be used alone, or two or more types may be used.
(其他樹脂) (other resins)
本膜在無損本發明效果之範圍內，亦可含有聚苯乙烯系樹脂以外的樹脂作為其他樹脂。其他樹脂可為熱收縮性膜之製造用途中所用公知者。其他樹脂可列舉如：烯烴系樹脂(丙烯系樹脂等)、聚酯系樹脂、丙烯酸系樹脂等。該等其他樹脂成分可單獨使用1種，亦可使用2種以上。 The present film may contain resins other than polystyrene-based resins as other resins within a range that does not impair the effects of the present invention. Other resins may be well-known ones used in the manufacture of heat-shrinkable films. Other resins include, for example, olefin-based resins (acrylic-based resins, etc.), polyester-based resins, acrylic-based resins, and the like. These other resin components may be used individually by 1 type, and may use 2 or more types.
(樹脂成分之含量) (content of resin component)
在將構成本膜的全體樹脂質量之合計設為100%時，聚苯乙烯系樹脂之含量宜為50~100質量%，且以80~100質量%更佳。 The content of the polystyrene resin is preferably 50 to 100 mass %, and more preferably 80 to 100 mass %, when the total mass of the resin constituting the present film is 100%.
(熱收縮性膜) (heat shrinkable film)
將本膜浸漬於70℃之水中10秒鐘時，主收縮方向之熱收縮率(以下亦記作「熱收縮率1」)為15%以下，且以5~15%為佳，以7~12%更佳。若熱收縮率1為15%以下，則可使膜在一般蒸氣通道下之收縮穩定，並防止皺褶或收縮不均等，收縮加工性會變得良好。 When the film is immersed in water at 70°C for 10 seconds, the thermal shrinkage rate in the main shrinkage direction (hereinafter also referred to as "thermal shrinkage rate 1") is 15% or less, preferably 5~15%, and 7~ 12% is better. If the thermal shrinkage ratio 1 is 15% or less, the shrinkage of the film under a general steam passage can be stabilized, and wrinkles and uneven shrinkage can be prevented, and the shrinkage processability can be improved.
將本膜浸漬於98℃之水中10秒鐘時，主收縮方向之熱收縮率(以下亦記作「熱收縮率2」)為60%以上，且以60~80%為佳，以65~75%更佳。若熱收縮率2為60% 以上，則收縮性優異，且可對各種容器進行安裝，並可防止收縮不足所致安裝障礙。 When the film is immersed in water at 98°C for 10 seconds, the thermal shrinkage rate in the main shrinkage direction (hereinafter also referred to as "thermal shrinkage rate 2") is 60% or more, preferably 60~80%, and 65~ 75% is better. If the thermal shrinkage rate 2 is 60% As described above, the shrinkability is excellent, and various containers can be attached, and installation failure due to insufficient shrinkage can be prevented.
將本膜浸漬於100℃之水中10秒鐘時，主收縮方向之熱收縮率(以下亦記作「熱收縮率3」)為60%以上，且以60~80%為佳，以65~75%更佳。若熱收縮率3為60%以上，則收縮性優異，且可對各種容器進行安裝，並可防止收縮不足所致安裝障礙。 When the film is immersed in water at 100°C for 10 seconds, the thermal shrinkage rate in the main shrinkage direction (hereinafter also referred to as "thermal shrinkage rate 3") is 60% or more, preferably 60~80%, and 65~ 75% is better. When the thermal shrinkage rate 3 is 60% or more, the shrinkability is excellent, and various containers can be mounted, and troubles in mounting due to insufficient shrinkage can be prevented.
又，熱收縮率2與熱收縮率3的差(△23)宜為±1%以內。若△23為±1%以內，則可對各種容器進行安裝，並可進一步地防止收縮不足所致安裝障礙。 In addition, the difference (Δ 23 ) between the thermal shrinkage rate 2 and the thermal shrinkage rate 3 is preferably within ±1%. If Δ23 is within ±1%, it is possible to mount various containers and further prevent mounting obstacles due to insufficient shrinkage.
於本發明中，「熱收縮率」是根據JIS Z1709，於70±0.5℃、98±0.5℃及100±0.5℃中分別測定之值。 In the present invention, the "thermal shrinkage rate" is a value measured at 70±0.5°C, 98±0.5°C, and 100±0.5°C, respectively, according to JIS Z1709.
本膜之與主收縮方向呈正交方向(以下亦記作「MD方向」)的艾門朵夫撕裂強度在3~10N/mm之範圍內，且宜在3~8N/mm之範圍內，更宜在3~6N/mm之範圍內。若MD方向之艾門朵夫撕裂強度在3~10N/mm之範圍內，則穿孔開封性優異。在此，「穿孔開封性優異」是指例如將使用本膜的標籤等藉由沿著與標籤之主收縮方向呈正交方向設置的穿孔斷開時，標籤不會在主收縮方向裂開而可輕易地自容器剝下標籤。 The Emmendorf tear strength of the film in the direction orthogonal to the main shrinkage direction (hereinafter also referred to as "MD direction") is in the range of 3~10N/mm, and preferably in the range of 3~8N/mm , preferably in the range of 3~6N/mm. If the Emmendorf tear strength in the MD direction is in the range of 3 to 10 N/mm, the perforation and opening properties are excellent. Here, "excellent perforation openability" means that, for example, when a label or the like using the present film is cut by a perforation provided in a direction perpendicular to the main shrinkage direction of the label, the label will not be split in the main shrinkage direction. The label can be easily peeled off the container.
本膜之主收縮方向(以下亦記作「TD方向」)的艾門朵夫撕裂強度在10~20N/mm之範圍內，且宜在10~17N/mm之範圍內，更宜在10~14N/mm之範圍內。 若TD方向之艾門朵夫撕裂強度在10~20N/mm之範圍內，則穿孔開封性優異。 The Emmendorf tear strength of the film in the main shrinking direction (hereinafter also referred to as "TD direction") is in the range of 10~20N/mm, and it should be in the range of 10~17N/mm, more preferably in the range of 10 within the range of ~14N/mm. If the Emmendorf tear strength in the TD direction is in the range of 10 to 20 N/mm, the perforation and unsealing properties are excellent.
於本發明中，「艾門朵夫撕裂強度」是根據JIS K7128-2，針對MD方向及TD方向，將所測定之值除以膜厚度所得之值。 In the present invention, "Emmendorph tear strength" is a value obtained by dividing the measured value by the film thickness in the MD direction and the TD direction in accordance with JIS K7128-2.
將本膜於85℃下放置5分鐘時，主收縮方向之收縮應力為4.0N/mm2以下，且以3.5N/mm2以下為佳，以3.0N/mm2以下更佳。若主收縮方向之收縮應力為4.0N/mm2以下，則在將使用本膜的標籤安裝於容器等時，可防止該標籤自穿孔破裂，因此安裝性優異。 When the film is left at 85°C for 5 minutes, the shrinkage stress in the main shrinkage direction is 4.0 N/mm 2 or less, preferably 3.5 N/mm 2 or less, and more preferably 3.0 N/mm 2 or less. When the shrinkage stress in the main shrinkage direction is 4.0 N/mm 2 or less, when the label using the film is attached to a container or the like, the label can be prevented from being ruptured from the perforation, and thus the attachability is excellent.
於本發明中，「收縮應力」是針對主收縮方向之長度為80mm、寬度為25mm的試料片，於具備荷重元之夾頭中以夾頭間50mm保持的狀態下投入85℃之烘箱內，並放置5分鐘時所測定平均單位截面積之最大應力。 In the present invention, the "shrinkage stress" refers to a test piece with a length of 80 mm and a width of 25 mm in the main shrinkage direction, which is placed in an oven at 85° C. in a state of holding 50 mm between the chucks in a chuck with a load cell, And the maximum stress per unit cross-sectional area measured when placed for 5 minutes.
將本膜於40℃下放置7日時，主收縮方向之收縮率(以下亦記作「自然收縮率」)為1.5%以下，且以1.2%以下為佳，以1.0%以下更佳。若自然收縮率為1.5%以下，則可減低保管中的收縮，且保管中的膜不易引起皺褶或尺寸變化，保管時之膜安定性優異。 When the film is left at 40°C for 7 days, the shrinkage rate in the main shrinkage direction (hereinafter also referred to as "natural shrinkage rate") is 1.5% or less, preferably 1.2% or less, and more preferably 1.0% or less. When the natural shrinkage rate is 1.5% or less, the shrinkage during storage can be reduced, and the film during storage is less likely to cause wrinkles or dimensional changes, and the film stability during storage is excellent.
自然收縮率是將主收縮方向長度為500mm之試樣於40℃下放置7日時的主收縮方向之收縮率，且為藉由下式(I)所算出之值。 The natural shrinkage rate is the shrinkage rate in the main shrinkage direction when a sample whose main shrinkage direction length is 500 mm is left at 40° C. for 7 days, and is a value calculated by the following formula (I).
自然收縮率[%]={[(500)-(放置後的長度[mm])]/(500)}×100．．．(I) Natural shrinkage rate [%]={[(500)-(length after placement [mm])]/(500)}×100. . . (I)
本膜可為由聚苯乙烯系樹脂所構成的單層膜，亦可為多層膜，該多層膜具有由聚苯乙烯系樹脂所構成的最表層；以及由聚苯乙烯系樹脂與其他樹脂所構成的其他層。又，本膜可為透明膜，若由印刷適性之觀點來看，則亦可為不透明膜或白色等的有色膜。 The film can be a single-layer film composed of polystyrene resin, or a multi-layer film, the multi-layer film has an outermost layer composed of polystyrene resin; and a polystyrene resin and other resins. other layers of composition. In addition, this film may be a transparent film, and may be an opaque film or a colored film such as white from the viewpoint of printability.
於熱收縮性膜中亦可含有填充材、安定劑、抗氧化劑、紫外線吸收劑、抗靜電劑、滑劑等添加物。 The heat-shrinkable film may contain additives such as fillers, stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, and lubricants.
於單層膜之情形時，本膜之厚度宜為20~80μm，且以40~60μm更佳。 In the case of a single-layer film, the thickness of the film is preferably 20-80 μm, and more preferably 40-60 μm.
於多層膜之情形時，本膜之最表層厚度宜為2~8μm，且以4~6μm更佳，其他層之厚度合計宜為18~78μm，且以16~54μm更佳。 In the case of a multi-layer film, the thickness of the outermost layer of the film is preferably 2-8 μm, preferably 4-6 μm, and the total thickness of other layers is preferably 18-78 μm, and preferably 16-54 μm.
(使用例) (Example of use)
熱收縮性膜並無特殊限制，主要使用作為瓶罐容器之標籤。當使用作為標籤時，為了提升設計性，亦可對熱收縮性膜施以印刷。 There are no special restrictions on heat shrinkable films, and they are mainly used as labels for bottles and cans. When using it as a label, in order to improve designability, you may apply printing to a heat-shrinkable film.
將由熱收縮性膜所構成的標籤安裝於瓶罐容器之方法例如可舉：將熱收縮性膜切割成預定長度，並將該經切割之膜之端部彼此接合而作成筒狀體，且將瓶罐容器***該筒狀體後，加熱而使其收縮。 A method of attaching a label made of a heat-shrinkable film to a bottle container includes, for example, cutting the heat-shrinkable film into a predetermined length, joining ends of the cut film to form a cylindrical body, and After the bottle-can container is inserted into the cylindrical body, it is heated and shrunk.
(熱收縮性膜之製造方法) (Manufacturing method of heat shrinkable film)
本膜可藉由公知方法(T字模法、充氣法等，於多層膜之情形時為該等之共擠出法)製得。舉例言之，雖不限於此，但宜將材料自業已加熱成160~240℃的壓鑄模擠出成 形為扁平狀或管狀，並將所製得未延伸物朝主收縮方向(TD方向)及與其呈正交之方向(MD方向)進行雙軸延伸。此時，可為MD方向與TD方向之逐次雙軸延伸，亦可為同時雙軸延伸。 The film can be produced by known methods (T-die method, inflation method, etc., in the case of multilayer films, these co-extrusion methods). For example, although not limited to this, it is advisable to extrude the material from a die-casting die that has been heated to 160~240°C. The shape is flat or tubular, and the obtained unstretched object is biaxially stretched toward the main shrinkage direction (TD direction) and the direction perpendicular to it (MD direction). At this time, successive biaxial stretching in the MD direction and the TD direction may be employed, or simultaneous biaxial stretching may be employed.
另，TD方向之延伸宜藉由預熱步驟、延伸步驟及熱固定步驟三步驟來進行。 In addition, the stretching in the TD direction is preferably carried out in three steps: a preheating step, an extending step, and a thermal fixing step.
本實施形態之膜宜於前述製造方法之進行TD方向延伸步驟的步驟中，以餘熱溫度為100℃以上、延伸溫度及熱固定溫度為90℃以上進行延伸，並以延伸倍率成為4.9以上之方式進行。藉由於該條件下進行延伸步驟，可將膜之自然收縮率作成適切值。 The film of this embodiment is preferably stretched at a residual heat temperature of 100° C. or higher, a stretching temperature and a heat-fixing temperature of 90° C. or higher, and a stretching ratio of 4.9 or higher in the step of performing the TD-direction stretching step of the aforementioned manufacturing method. conduct. By performing the stretching step under this condition, the natural shrinkage rate of the film can be adjusted to an appropriate value.
(作用效果) (Effect)
如以上所說明，本發明之熱收縮性膜滿足上述各物性值，因此，具備優異之收縮加工性、穿孔開封性與安裝性，且相較於習知聚苯乙烯系熱收縮性膜，保管時之膜安定性更為提升。 As described above, the heat-shrinkable film of the present invention satisfies the above-mentioned physical property values, and therefore has excellent shrink processability, perforation and unsealing properties, and mounting properties, and compared with the conventional polystyrene-based heat-shrinkable film, the Membrane stability is further improved.
實施例 Example
以下，藉由實施例具體說明本發明，惟本發明並不受限於以下記載。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the following description.
實施例中的熱收縮性膜之各物性值之測定與各評價項目之評價依據以下記載及基準來進行。 The measurement of each physical property value of the heat-shrinkable film in an Example and the evaluation of each evaluation item were performed based on the following description and a reference|standard.
(熱收縮率) (thermal shrinkage rate)
根據JIS Z1709，測定於70±0.5℃(「熱收縮率1」之測定溫度)、98±0.5℃(「熱收縮率2」之測定溫度)及100± 0.5℃(「熱收縮率3」之測定溫度)中的熱收縮性膜之熱收縮率。 According to JIS Z1709, measured at 70±0.5°C (measurement temperature of “thermal shrinkage rate 1”), 98±0.5°C (measurement temperature of “thermal shrinkage rate 2”), and 100± The thermal shrinkage rate of the heat-shrinkable film in 0.5°C (the measurement temperature of "thermal shrinkage rate 3").
(艾門朵夫撕裂強度) (Emendorff tear strength)
根據JIS K7128-2，針對熱收縮性膜之MD方向及TD方向測定撕裂力，並分別除以熱收縮性膜之厚度而算出。 According to JIS K7128-2, tearing force was measured about the MD direction and TD direction of a heat-shrinkable film, and it divided by the thickness of a heat-shrinkable film, respectively, and calculated.
(收縮應力) (shrinkage stress)
針對主收縮方向之長度為80mm、寬度為25mm的試料片，將於85℃下放置5分鐘時所測定應力之最大值設為收縮應力。 The maximum value of the stress measured when the length in the main shrinkage direction is 80 mm and the width is 25 mm is defined as the shrinkage stress.
(自然收縮率) (natural shrinkage)
在將熱收縮性膜之主收縮方向之長度為500mm的試樣於40℃下放置7日後，測定試樣之長度，並藉由下式(I)來算出。 After leaving the sample whose length in the main shrinkage direction of the heat-shrinkable film is 500 mm at 40° C. for 7 days, the length of the sample was measured and calculated by the following formula (I).
自然收縮率[%]={[(500)-(放置後的長度[mm])]/(500)}×100．．．(I) Natural shrinkage rate [%]={[(500)-(length after placement [mm])]/(500)}×100. . . (I)
將熱收縮性膜切割成預定寬度與長度，並將該切割過的熱收縮性膜之端部彼此接合，作成熱收縮性膜之主收縮方向構成圓周方向的筒狀體標籤。然後，將瓶罐容器***該筒狀體後，藉由使其熱收縮而安裝標籤。以目視觀察熱收縮後的標籤外觀，並評價收縮加工性、安裝性。 The heat-shrinkable film is cut into predetermined widths and lengths, and the ends of the cut heat-shrinkable films are joined to each other to form a cylindrical label in which the main shrinkage direction of the heat-shrinkable film constitutes the circumferential direction. Then, after inserting the bottle-can container into the cylindrical body, a label is attached by thermally shrinking it. The external appearance of the label after heat shrinkage was visually observed, and the shrink processability and mountability were evaluated.
(收縮加工性) (shrinkage workability)
藉由目視，判定熱收縮後的標籤上有無皺褶及收縮不均，並藉由下述基準來評價。 The presence or absence of wrinkles and shrinkage unevenness on the label after heat shrinkage was determined by visual observation, and evaluated by the following criteria.
○：無論是皺褶或收縮不均皆未產生。 ○: Neither wrinkles nor uneven shrinkage occurred.
×：產生皺褶或收縮不均。 ×: Wrinkles or uneven shrinkage occurred.
(安裝性) (installability)
藉由目視，判定熱收縮後的標籤上有無破裂，並藉由下述基準來評價。 The presence or absence of cracks on the label after heat shrinking was judged by visual observation, and it was evaluated by the following criteria.
○：未產生破裂。 ○: No cracking occurred.
×：產生破裂。 ×: Cracks occurred.
(穿孔開封性) (perforation openability)
將業已預先在與主收縮方向呈正交方向加入穿孔的上述筒狀體之標籤安裝於瓶罐容器。不過，穿孔是藉由以4mm間隔加入長度1mm的孔洞來形成，並於穿孔之方向(MD方向)在寬度20mm、長度200mm的範圍設置二條。然後，用指尖撕裂標籤之穿孔，並判定是否沿著設置於MD方向的穿孔裂開。 The label of the above-mentioned cylindrical body, which has been perforated in the direction orthogonal to the main shrinking direction in advance, is attached to the bottle and can container. However, the perforations were formed by adding holes of 1 mm in length at intervals of 4 mm, and two perforations were provided in the range of 20 mm in width and 200 mm in length in the direction of the perforations (MD direction). Then, the perforation of the label is torn with a fingertip, and it is determined whether or not the perforation provided in the MD direction is split.
○：標籤沿著穿孔裂開。 ○: The label is split along the perforation.
×：標籤未沿著穿孔裂開，或是標籤在並非TD方向的方向裂開。 ×: The label is not split along the perforation, or the label is split in a direction other than the TD direction.
(保管時之膜安定性) (Film stability during storage)
將熱收縮性膜於40℃下保管7日後，藉由目視判定熱收縮性膜上有無皺褶或尺寸變化，並藉由下述基準，評價保管時之膜安定性。 After the heat-shrinkable film was stored at 40° C. for 7 days, the presence or absence of wrinkles or dimensional changes on the heat-shrinkable film was visually judged, and the film stability during storage was evaluated by the following criteria.
○：相較於習知品，未產生皺褶或尺寸變化。 ○: Compared with the conventional product, no wrinkle or dimensional change occurred.
×：與習知品同等地產生皺褶或尺寸變化。 ×: Wrinkles or dimensional changes occurred in the same manner as conventional products.
<實施例1> <Example 1>
(聚苯乙烯系熱收縮性膜之原料) (raw material for polystyrene heat-shrinkable film)
以下所述實施例之聚苯乙烯系熱收縮性膜採用由以下成分所構成的三層構造。 The polystyrene-based heat-shrinkable films of Examples described below have a three-layer structure composed of the following components.
聚苯乙烯系熱收縮性膜之中間層使用屬於苯乙烯-丁二烯共聚物的SBC(A)與SBC(B)之混合物作為原料。 A mixture of SBC (A) and SBC (B), which are styrene-butadiene copolymers, is used as a raw material for the intermediate layer of the polystyrene-based heat-shrinkable film.
聚苯乙烯系熱收縮性膜之兩外層使用苯乙烯-丁二烯共聚物(SBC(A))及耐衝擊性聚苯乙烯系樹脂(表1中記作「HiPS」)之混合物作為原料。 The two outer layers of the polystyrene-based heat-shrinkable film used a mixture of a styrene-butadiene copolymer (SBC(A)) and an impact-resistant polystyrene-based resin (referred to as "HiPS" in Table 1) as raw materials.
表1中顯示各構成成分之菲卡軟化點與熔體質量流動速率(表1中記作「MFR」)，以及各層的構成成分之成分比。 Table 1 shows the Fika softening point and the melt mass flow rate (referred to as "MFR" in Table 1) of each constituent component, and the component ratio of the constituent components of each layer.
(聚苯乙烯系熱收縮性膜之製造) (Manufacture of polystyrene heat-shrinkable film)
以表1所示摻合量混合聚苯乙烯系熱收縮性膜之原料，並自維持在200℃的三層壓鑄模共擠出而製得三層構造之聚苯乙烯系膜胚料。該膜胚料兩外層之厚度為34μm，中間層之厚度為270μm。其次，將該膜胚料於85℃下朝MD方向延伸處理成1.35倍，並製得厚度250μm之由聚苯乙烯系樹脂所構成的延伸膜。再者，將已朝該MD方向施行延伸處理的膜以105℃預熱10秒鐘後，於98℃下朝TD方 向延伸成5.00倍，然後，保持97℃下延伸約15秒鐘的狀態後進行冷卻，並製得聚苯乙烯系熱收縮性膜。 The raw materials of the polystyrene-based heat-shrinkable film were mixed in the blending amounts shown in Table 1, and co-extruded from a three-layer casting mold maintained at 200° C. to obtain a three-layer structure polystyrene-based film blank. The thickness of the two outer layers of the film blank is 34 μm, and the thickness of the middle layer is 270 μm. Next, the film blank was stretched 1.35 times in the MD direction at 85° C. to obtain a stretched film made of polystyrene resin with a thickness of 250 μm. In addition, after preheating the film stretched in the MD direction at 105° C. for 10 seconds, the film was heated in the TD direction at 98° C. It extended to 5.00 times, and after maintaining the state extended for about 15 seconds at 97 degreeC, it cooled, and the polystyrene-type heat-shrinkable film was produced.
<比較例1> <Comparative Example 1>
除了如表2所示般變更延伸條件外，作成與實施例1相同而製得聚苯乙烯系熱收縮性膜。 Except having changed the drawing conditions as shown in Table 2, it carried out similarly to Example 1, and produced the polystyrene-type heat-shrinkable film.
<比較例2> <Comparative Example 2>
(聚酯系熱收縮性膜之原料) (raw material of polyester heat-shrinkable film)
以下所述比較例2之聚酯系熱收縮性膜為單層構造，並使用SK化學公司製P-SF之聚酯系樹脂(表1中記作「聚酯(A)」)與住化色料(SUMIKA COLOR)公司製EPM7E-325之矽膠母料(表1中記作「矽膠MB」)之混合物作為原料。 The polyester-based heat-shrinkable film of Comparative Example 2 described below has a single-layer structure, and uses P-SF polyester-based resin (referred to as "polyester (A)" in Table 1) manufactured by SK Chemical Co., Ltd. and Sumika A mixture of silicone masterbatch EPM7E-325 (referred to as "silicone MB" in Table 1) manufactured by SUMIKA COLOR Co., Ltd. was used as the raw material.
表1中顯示所使用聚酯A的玻璃轉移點(表1中記作「Tg」)與極限黏度(表1中記作「IV」)、以及構成膜的成分之成分比。 Table 1 shows the glass transition point (represented as "Tg" in Table 1) and the limiting viscosity (referred to as "IV" in Table 1) of the polyester A used, and the component ratios of the components constituting the film.
(聚酯系熱收縮性膜之製造) (Manufacture of polyester heat-shrinkable film)
以表1所示摻合量混合聚酯系熱收縮性膜之原料，並自維持在260℃的壓鑄模擠出而製得厚度200μm之單層構 造之聚酯系膜胚料。除了使用該單層構造之膜胚料以及如表2所示般變更延伸條件外，作成與實施例1相同而製得聚酯系熱收縮性膜。 The raw materials of the polyester-based heat-shrinkable film were mixed in the blending amounts shown in Table 1, and extruded from a die-casting die maintained at 260° C. to obtain a single-layer structure with a thickness of 200 μm. Made of polyester film blanks. A polyester-based heat-shrinkable film was produced in the same manner as in Example 1, except that the film blank of the single-layer structure was used and the stretching conditions were changed as shown in Table 2.
表3中顯示藉由上述方法針對各例中所製得熱收縮性膜測定各物性值的結果。 Table 3 shows the results of measuring the physical property values of the heat-shrinkable films produced in the respective examples by the above-mentioned methods.
又，表4中顯示藉由上述基準針對各評價項目進行評價的結果。 In addition, Table 4 shows the result of evaluating each evaluation item by the above-mentioned criteria.
如表3、表4所示，相較於自然收縮率大於1.5%的比較例1之聚苯乙烯系熱收縮性膜，實施例1之聚苯乙烯系熱收縮性膜於保管時之膜安定性更為提升。 As shown in Tables 3 and 4, compared to the polystyrene heat-shrinkable film of Comparative Example 1 with a natural shrinkage rate greater than 1.5%, the polystyrene-based heat-shrinkable film of Example 1 was stable during storage. Sex is more enhanced.
相較於實施例1之熱收縮性膜，使用聚酯系樹脂的比較例2之聚酯系熱收縮性膜的收縮加工性、安裝性及穿孔開封性差。 Compared with the heat-shrinkable film of Example 1, the polyester-based heat-shrinkable film of Comparative Example 2 using a polyester-based resin was inferior in shrink processability, mountability, and perforation-opening property.
(無)(without)
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| AR (1) | AR111191A1 (en) |
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| JP2002285020A (en) * | 2001-03-23 | 2002-10-03 | Gunze Ltd | White film for heat-shrinkable label, heat-shrinkable label made of the film and container whit label fitted by shrinking |
| JP5286763B2 (en) * | 2006-12-20 | 2013-09-11 | 東洋紡株式会社 | Heat-shrinkable polystyrene film and method for producing the same |
| JP3189169U (en) * | 2013-12-13 | 2014-02-27 | 日本ポリエチレン株式会社 | Easy opening bag, easy tear film and easy tear tape |
| JP5948719B2 (en) * | 2014-09-29 | 2016-07-06 | 積水フィルム株式会社 | Multilayer heat shrinkable film and method for producing the same |
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