TWI555808B - Polyolefin based film - Google Patents
Polyolefin based film Download PDFInfo
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- TWI555808B TWI555808B TW101139899A TW101139899A TWI555808B TW I555808 B TWI555808 B TW I555808B TW 101139899 A TW101139899 A TW 101139899A TW 101139899 A TW101139899 A TW 101139899A TW I555808 B TWI555808 B TW I555808B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
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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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
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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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
- C09J125/02—Homopolymers or copolymers of hydrocarbons
- C09J125/04—Homopolymers or copolymers of styrene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
- C09J7/405—Adhesives in the form of films or foils characterised by release liners characterised by the substrate of the release liner
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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
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
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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
- B32B2405/00—Adhesive articles, e.g. adhesive tapes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2423/00—Presence of polyolefin
- C09J2423/006—Presence of polyolefin in the substrate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2423/00—Presence of polyolefin
- C09J2423/10—Presence of homo or copolymers of propene
- C09J2423/106—Presence of homo or copolymers of propene in the substrate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
Description
本發明係關於一種聚烯烴系薄膜，本發明的聚烯烴系薄膜係可使用於用於光學用途的稜鏡片等的零件、合成樹脂板(例如：建築材料用)、不鏽鋼板(例如：建築材料用)、鋁板、裝飾合板、鋼板、玻璃板、家電製品、精密機械等。又，前述聚烯烴系薄膜可適用於為了保護製造時的車體的表面，為了避免堆疊、保管、運送、於製造步驟中搬送物品時的損傷，以及為了避免二次加工(例如：彎曲加工或壓製加工)物品時的損傷。 The present invention relates to a polyolefin-based film which can be used for parts such as rugs for optical applications, synthetic resin sheets (for example, for building materials), and stainless steel sheets (for example, building materials). ), aluminum plate, decorative plywood, steel plate, glass plate, home appliances, precision machinery, etc. Further, the polyolefin-based film can be applied to protect the surface of the vehicle body during production, to avoid damage during stacking, storage, transportation, and conveyance of articles in the manufacturing process, and to avoid secondary processing (for example, bending processing or Damage during processing).
在以往，以被覆體的表面保護為目的之黏著薄膜係可用於建築材料或電氣、電子製品、汽車等的加工、保管、運送時，這樣的黏著薄膜在具有良好的黏著性的同時，使用後必須不會被黏著劑汙染到各表面，並且可輕易地剝離。 In the past, an adhesive film for the purpose of surface protection of a covering body can be used for processing, storage, and transportation of building materials, electrical, electronic products, automobiles, etc., and such an adhesive film has good adhesion and is used after use. It must not be contaminated by the adhesive to each surface and can be easily peeled off.
近年來，隨著上述之被覆體的多樣化，不僅可以看到被覆面為平滑者，而且亦可看到許多具有表面凹凸者。以具有表面凹凸之被覆體而言，可列舉例如：光學零件所使用之稜鏡片的稜鏡型的鏡片部等。相對於如稜鏡片之具有表面凹凸的被覆體，為了顯現使用上充分的黏著力，可考慮提高黏著層的黏著力等，使得即便接觸面積小也可獲得黏著力。 In recent years, with the diversification of the above-mentioned coverings, not only can the coating surface be smooth, but also many surface irregularities can be seen. The covering body having the surface unevenness may, for example, be a 镜片-type lens portion of a cymbal used for an optical component. In order to exhibit sufficient adhesion for use in a coated body having surface irregularities, for example, it is conceivable to increase the adhesion of the adhesive layer and the like so that an adhesive force can be obtained even if the contact area is small.
為了提高黏著層的黏著力，雖可藉由使用表現高黏著力的苯乙烯系彈性體等作為樹脂來作為主成分，但是 當提高黏著層的黏著力時，以輥狀態保管黏著薄膜，之後在轉出薄膜時，會產生黏結且會產生薄膜部分地伸長、變形等的問題。 In order to improve the adhesion of the adhesive layer, a styrene-based elastomer or the like which exhibits high adhesion can be used as a main component, but When the adhesive force of the adhesive layer is increased, the adhesive film is stored in a roll state, and then when the film is transferred out, adhesion occurs and the film is partially elongated and deformed.
作為上述的對策，可藉由將碳數4以上的α-烯烴(共)聚合物使用於離型層，試著改善轉出薄膜時的黏結(參照例如專利文獻1等)。然而，欲在於由聚丙烯系樹脂所構成的基材層的一面使用T字形模頭等擠壓聚丙烯系樹脂的一般溫度下，藉由共擠壓製膜來積層含有50重量%以上的碳數4以上的α-烯烴(共)聚合物之離型層時，會有所謂離型層的製膜性變差的缺陷。 As a countermeasure against the above, it is possible to improve the adhesion at the time of transferring the film by using an α-olefin (co)polymer having 4 or more carbon atoms in the release layer (see, for example, Patent Document 1). However, in order to laminate a polypropylene resin with a T-shaped die or the like on one surface of a base material layer made of a polypropylene resin, a film containing 50% by weight or more of carbon is deposited by co-extrusion film formation. When the release layer of the α-olefin (co)polymer is a number of 4 or more, there is a defect that the film forming property of the release layer is deteriorated.
[專利文獻1]日本特開2011-42757號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-42757
本發明所欲解決之課題在於提供一種薄膜的加工適應性優異的自黏性表面保護薄膜，其係對於被覆體表現出強大的黏著力且可使用在各式各樣的被覆體，同時以輥狀態保管黏著薄膜，之後在轉出薄膜時，也難以引起薄膜部分地伸長、變形等的問題。即，本發明之目的在於提供一種聚烯烴系薄膜，其不會產生表面粗糙的轉印，且不會抑制黏著性，並具有良好的剝離性及製膜性。 The object of the present invention is to provide a self-adhesive surface protective film which is excellent in processing suitability of a film, which exhibits strong adhesion to a covering body and can be used in various types of coverings while being rolled. In the state where the adhesive film is stored, it is difficult to cause partial elongation or deformation of the film when the film is transferred out. That is, an object of the present invention is to provide a polyolefin-based film which does not cause surface roughening transfer and which does not inhibit adhesiveness and which has excellent peelability and film formability.
本發明人等專心研究探討，結果發現可藉由將黏著層所使用的樹脂的摻合比設在規定的範圍，並且將離型 層所使用的樹脂的摻合比或表面粗度設在規定的範圍來解決上述的課題，而達成本發明。 The inventors of the present invention have intensively studied and found that the blending ratio of the resin used for the adhesive layer can be set within a prescribed range, and the release type is obtained. The present invention has been achieved by setting the blending ratio or surface roughness of the resin used in the layer to a predetermined range to solve the above problems.
即，本發明係關於一種聚烯烴系薄膜，其特徵在於構成黏著層的樹脂至少含有苯乙烯系彈性體(其中，以苯乙烯系聚合物嵌段與烯烴系聚合物嵌段的嵌段共聚物、苯乙烯系聚合物嵌段和苯乙烯與烯烴的無規共聚物嵌段之嵌段共聚物、及/或此等的氫化物為主成分而成)與聚烯烴系樹脂，聚烯烴系樹脂的摻合量為構成黏著層的樹脂成分中5重量%以上25重量%以下，構成離型層的樹脂至少含有聚丙烯系樹脂與碳數4以上的α-烯烴(共)聚合物，碳數4以上的α-烯烴(共)聚合物的摻合量為構成離型層的樹脂成分中5重量%以上小於25重量%，並藉由共擠壓在由聚丙烯系樹脂所構成的基材層的一面積層黏著層、在另一面積層離型層而成。 That is, the present invention relates to a polyolefin-based film characterized in that the resin constituting the adhesive layer contains at least a styrene-based elastomer (wherein a block copolymer of a styrene-based polymer block and an olefin-based polymer block) a styrene polymer block, a block copolymer of a random copolymer block of styrene and an olefin, and/or a hydride as a main component), a polyolefin resin, and a polyolefin resin. The blending amount is 5% by weight or more and 25% by weight or less based on the resin component constituting the adhesive layer, and the resin constituting the release layer contains at least a polypropylene resin and an α-olefin (co)polymer having a carbon number of 4 or more. The blending amount of the above-mentioned α-olefin (co)polymer is 5% by weight or more and less than 25% by weight in the resin component constituting the release layer, and is coextruded on the substrate composed of the polypropylene resin. One layer of the layer is adhered to the layer, and the other layer is separated from the layer.
在此情況下，前述碳數4以上的α-烯烴共聚物較佳為4-甲基-1-戊烯系(共)聚合物。 In this case, the α-olefin copolymer having 4 or more carbon atoms is preferably a 4-methyl-1-pentene-based (co)polymer.
又，在此情況下，離型層的表面粗度(SRa)較佳為0.20μm以上0.50μm以下。 Moreover, in this case, the surface roughness (SRa) of the release layer is preferably 0.20 μm or more and 0.50 μm or less.
又，在此情況下，前述基材層及離型層所使用的聚丙烯系樹脂的MFR(230℃、2.16Kgf)較佳為1.0~15g/10分鐘。 Moreover, in this case, the MFR (230 ° C, 2.16 Kgf) of the polypropylene resin used for the base material layer and the release layer is preferably 1.0 to 15 g/10 min.
此外，在此情況下，前述黏著層所使用的苯乙烯系彈性體的MFR(230℃、2.16Kgf)較佳為0.5~20g/10分鐘。 Further, in this case, the MFR (230 ° C, 2.16 Kgf) of the styrene-based elastomer used in the adhesive layer is preferably 0.5 to 20 g/10 min.
本發明之聚烯烴系薄膜係對於被覆體表現出強大的 黏著力且可使用在各式各樣的被覆體，同時以輥狀態保管黏著薄膜，之後在轉出薄膜時，也難以引起薄膜部分地伸長、變形等的問題，並且具有薄膜的加工適應性優異的優點。即，依據本發明，可提供一種聚烯烴系薄膜，其不會產生表面粗糙的轉印，且不會抑制黏著性，並具有良好的剝離性及製膜性。 The polyolefin-based film of the present invention exhibits a strong effect on the covering. Adhesive force can be used in a wide variety of coatings, and the adhesive film can be stored in a roll state. Then, when the film is transferred out, it is difficult to cause partial elongation and deformation of the film, and the film has excellent processing suitability. The advantages. That is, according to the present invention, it is possible to provide a polyolefin-based film which does not cause surface rough transfer and which does not inhibit adhesiveness and which has good peelability and film formability.
以下，說明本發明之聚烯烴系薄膜(黏著薄膜)的實施形態。 Hereinafter, an embodiment of the polyolefin-based film (adhesive film) of the present invention will be described.
本發明之聚烯烴系薄膜需要以聚丙烯系樹脂為主成分的基材層，以此處使用的聚丙烯系樹脂而言，可列舉結晶性聚丙烯、丙烯與少量α-烯烴的無規共聚合、嵌段共聚物等，更詳細地說，以結晶性聚丙烯樹脂而言，可列舉一般擠壓成形等所使用之n-庚烷不溶性的同排丙烯均聚物或含有60重量%以上的丙烯之丙烯與其他α-烯烴的共聚物，可單獨或混合使用此丙烯均聚物或是丙烯與其他α-烯烴的共聚物。基材層較佳為含有50重量%以上的丙烯單位，更佳為含有60重量%以上的丙烯單位。丙烯若小於50重量%，則薄膜變得沒有韌性，且變得難以處理。 The polyolefin-based film of the present invention requires a base material layer containing a polypropylene-based resin as a main component, and examples of the polypropylene-based resin used herein include random polypropylene, propylene, and a small amount of α-olefin. In particular, the crystalline polypropylene resin may, for example, be an n-heptane-insoluble homopolymer propylene homopolymer used in general extrusion molding or the like, or may contain 60% by weight or more. The copolymer of propylene propylene and other α-olefins may be used singly or in combination as a copolymer of propylene or other α-olefin. The base material layer preferably contains 50% by weight or more of propylene units, more preferably 60% by weight or more of propylene units. When the amount of propylene is less than 50% by weight, the film becomes tackless and becomes difficult to handle.
在此，所謂n-庚烷不溶性係指在標示聚丙烯的結晶性的同時表明安全性，在本發明中，使用符合根據西元1982年2月 日本厚生省(the Ministry of Welfare)公告第20 號之n-庚烷不溶性(經25℃、60分鐘萃取時的洗提成分為150ppm以下[使用溫度超過100℃者為30ppm以下])者為較佳態樣。 Here, the term "n-heptane insoluble" means safety while indicating the crystallinity of the polypropylene, and in the present invention, the use is in accordance with the February 20, 1982, the Ministry of Welfare. The n-heptane insoluble property (the elution component at 25 ° C for 60 minutes is 150 ppm or less [30 ppm or less when the temperature exceeds 100 ° C) is preferable.
以丙烯與其他α-烯烴的共聚物的α-烯烴共聚合成分而言，較佳為碳數為2~8的α-烯烴，例如：乙烯或是1-丁烯、1-戊烯、1-己烯、4-甲基-1-戊烯等的C4以上的α-烯烴。在此，共聚物較佳為將丙烯與1種或2種以上的上述所例示的α-烯烴聚合而得到的無規或嵌段共聚物。所使用的聚丙烯系樹脂的熔融流動速率(melt flow rate)(MFR：230℃、2.16Kgf)較佳為1.0~15g/10min的範圍，更佳為2.0~10.0g/10min的範圍。又，亦可混合2種以上的丙烯與其他α-烯烴的共聚物來使用。 The α-olefin copolymerization component of the copolymer of propylene and another α-olefin is preferably an α-olefin having a carbon number of 2 to 8, such as ethylene or 1-butene or 1-pentene. An α-olefin of C4 or higher such as hexene or 4-methyl-1-pentene. Here, the copolymer is preferably a random or block copolymer obtained by polymerizing propylene with one or more kinds of the above-exemplified α-olefins. The melt flow rate (MFR: 230 ° C, 2.16 Kgf) of the polypropylene resin to be used is preferably in the range of 1.0 to 15 g/10 min, more preferably in the range of 2.0 to 10.0 g/10 min. Further, a copolymer of two or more kinds of propylene and another α-olefin may be used in combination.
此外，亦可將本發明所得到的薄膜進行產品加工時產生的廢薄膜作為回收原料而進行再造粒並添加到基材層，可藉由使用回收原料來抑制生產成本。 Further, the waste film produced by processing the film obtained by the present invention as a raw material for recycling can be regranulated and added to the substrate layer, and the production cost can be suppressed by using the recovered raw material.
本發明中的黏著層需要苯乙烯系彈性體及聚烯烴系樹脂，為了顯現高黏著力，必須使用苯乙烯系彈性體。 The adhesive layer in the present invention requires a styrene-based elastomer and a polyolefin-based resin, and in order to exhibit high adhesion, it is necessary to use a styrene-based elastomer.
又，考慮到黏著力與從輥狀態之薄膜的轉出性，則含有5重量%以上25重量%以下的聚烯烴系樹脂。藉由添加聚烯烴系樹脂，從黏著面側亦可降低對於離型面的剝離力。又，為了控制黏著力，亦可視需要地混合黏著賦予樹脂、軟化劑。 Further, in consideration of the adhesive force and the transfer property of the film from the roll state, the polyolefin resin is contained in an amount of 5 wt% or more and 25% by weight or less. By adding a polyolefin-based resin, the peeling force against the release surface can also be reduced from the side of the adhesive surface. Further, in order to control the adhesion, the adhesion-imparting resin and the softener may be mixed as needed.
苯乙烯系彈性體係可列舉苯乙烯-丁二烯-苯乙烯、苯乙烯-異戊二烯-苯乙烯、苯乙烯-乙烯/丁烯共聚物-苯 乙烯、苯乙烯-乙烯/丙烯共聚物-苯乙烯等的A-B-A型嵌段聚合物、苯乙烯-丁二烯、苯乙烯-異戊二烯、苯乙烯-乙烯/丁烯共聚物、苯乙烯-乙烯/丙烯共聚物等的A-B型嵌段聚合物、苯乙烯-丁二烯橡膠等的苯乙烯系無規共聚物以及該等的氫化物。 Examples of the styrene-based elastomer system include styrene-butadiene-styrene, styrene-isoprene-styrene, and styrene-ethylene/butene copolymer-benzene. ABA type block polymer of ethylene, styrene-ethylene/propylene copolymer-styrene, styrene-butadiene, styrene-isoprene, styrene-ethylene/butene copolymer, styrene- An AB type block polymer such as an ethylene/propylene copolymer, a styrene-based random copolymer such as styrene-butadiene rubber, or the like.
使用的苯乙烯系彈性體的熔融流動速率(MFR：230℃、2.16Kgf)較佳為0.5~20g/10分鐘的範圍，更佳為2.0~10.0g/10分鐘的範圍，再更佳為3~10g/10分鐘的範圍，特佳為4~7g/10分鐘的範圍。 The melt flow rate (MFR: 230 ° C, 2.16 Kgf) of the styrene-based elastomer to be used is preferably in the range of 0.5 to 20 g/10 min, more preferably in the range of 2.0 to 10.0 g/10 min, still more preferably 3 A range of ~10 g/10 minutes, particularly preferably in the range of 4 to 7 g/10 minutes.
黏著層中苯乙烯系彈性體的量較佳為45重量%以上，更佳為50重量%以上，再佳為60重量%以上，特佳為70重量%以上；較佳為99重量%以下，更佳為98重量%以下，再佳為97重量%以下，特佳為96重量%以下，最佳為95重量%以下。 The amount of the styrene-based elastomer in the adhesive layer is preferably 45% by weight or more, more preferably 50% by weight or more, still more preferably 60% by weight or more, particularly preferably 70% by weight or more, and preferably 99% by weight or less. It is more preferably 98% by weight or less, still more preferably 97% by weight or less, particularly preferably 96% by weight or less, and most preferably 95% by weight or less.
苯乙烯系彈性體中的苯乙烯成分最好為5重量%以上30重量%以下。若小於5重量%，則樹脂製作時的造粒變得困難；若超過25重量%，則黏著力會降低，變得難以獲得所需要的黏著力。再者，苯乙烯系彈性體中的苯乙烯成分較佳為10重量%以上20重量%以下，更佳為10重量%以上15重量%以下。又，苯乙烯系彈性體中的苯乙烯成分以外的成分較佳為由乙烯、丁烯等的成分所構成，苯乙烯成分以外的成分量在苯乙烯系彈性體中較佳為70~95重量%，更佳為75~90重量%，再佳為80~90重量%，再更佳為85~90重量%。 The styrene component in the styrene elastomer is preferably 5% by weight or more and 30% by weight or less. When it is less than 5% by weight, granulation during production of the resin becomes difficult, and if it exceeds 25% by weight, the adhesive force is lowered, and it is difficult to obtain a desired adhesive force. Further, the styrene component in the styrene elastomer is preferably 10% by weight or more and 20% by weight or less, more preferably 10% by weight or more and 15% by weight or less. Further, the component other than the styrene component in the styrene elastomer is preferably composed of a component such as ethylene or butylene, and the component amount other than the styrene component is preferably 70 to 95 by weight in the styrene elastomer. %, more preferably 75 to 90% by weight, still more preferably 80 to 90% by weight, still more preferably 85 to 90% by weight.
聚烯烴系樹脂並無特別限制，可列舉結晶性聚丙烯 、丙烯與少量的α-烯烴的共聚物、低密度聚乙烯、高密度聚乙烯、乙烯與少量的α-烯烴的共聚物、乙烯與不飽和羧酸或不飽和羧酸酯的共聚物、聚苯乙烯等。其中，聚丙烯系樹脂係因基材層為聚丙烯系樹脂所構成，從熔態黏度(melt viscosity)等的關係來看，亦可適宜地使用。使用的聚烯烴系樹脂的熔融流動速率(MFR：230℃、2.16Kgf)較佳為1.0~100.0g/10min的範圍，更佳為2.0~30.0g/10min的範圍，再佳為2~10g/10min的範圍，特佳為2~7g/10min的範圍。 The polyolefin resin is not particularly limited, and examples thereof include crystalline polypropylene. a copolymer of propylene and a small amount of an α-olefin, a low-density polyethylene, a high-density polyethylene, a copolymer of ethylene and a small amount of an α-olefin, a copolymer of ethylene and an unsaturated carboxylic acid or an unsaturated carboxylic acid ester, and a poly Styrene and the like. In particular, the polypropylene resin is composed of a polypropylene resin, and can be suitably used from the viewpoint of a melt viscosity or the like. The melt flow rate (MFR: 230 ° C, 2.16 Kgf) of the polyolefin-based resin to be used is preferably in the range of 1.0 to 100.0 g/10 min, more preferably in the range of 2.0 to 30.0 g/10 min, and further preferably 2 to 10 g/ The range of 10 min is particularly preferably in the range of 2 to 7 g/10 min.
黏著層(構成黏著層的樹脂成分)中的聚烯烴系樹脂的摻合量為5重量%以上25重量%以下的範圍。聚烯烴系樹脂的摻合量若超過25重量%，則根據使用的樹脂會使黏著力降低且無法獲得充分的黏著力。聚烯烴系樹脂的摻合量若小於5重量%，則無法對黏著層的黏著力變化有貢獻。又，亦無法對薄膜黏著層對於離型層的剝離力有貢獻。聚烯烴系樹脂的摻合量較佳為6重量%以上18重量%以下，更佳為6重量%以上15重量%以下。 The blending amount of the polyolefin-based resin in the adhesive layer (the resin component constituting the adhesive layer) is in the range of 5% by weight to 25% by weight. When the blending amount of the polyolefin resin exceeds 25% by weight, the adhesive force is lowered depending on the resin to be used, and sufficient adhesion cannot be obtained. When the blending amount of the polyolefin resin is less than 5% by weight, it is not possible to contribute to the change in the adhesive force of the adhesive layer. Moreover, it is also impossible to contribute to the peeling force of the film adhesive layer to the release layer. The blending amount of the polyolefin resin is preferably 6% by weight or more and 18% by weight or less, more preferably 6% by weight or more and 15% by weight or less.
黏著層中的苯乙烯系彈性體與聚烯烴系樹脂的重量比(苯乙烯系彈性體/聚烯烴系樹脂)較佳為75/25~95/5，更佳為82/18~94/6，再佳為85/15~94/6。 The weight ratio of the styrene elastomer to the polyolefin resin in the adhesive layer (styrene elastomer/polyolefin resin) is preferably 75/25 to 95/5, more preferably 82/18 to 94/6. , then good for 85/15~94/6.
黏著賦予樹脂係可列舉例如：脂肪族烴樹脂、芳香族烴樹脂、脂環族烴樹脂、萜樹脂、苯并呋喃-茚樹脂、苯乙烯系樹脂、松脂樹脂等，其中較佳為脂環族烴樹脂(例如：石油樹脂)。黏著賦予樹脂的分子量並無特別的限制，可適當地設定，惟分子量若變小，則可能會導致從 黏著層至黏附體的質量遷移(mass transport)或重剝離化等，另一方面，分子量若變大，則因為有黏著力的提升效果變差之傾向，故黏著賦予樹脂的數量平均分子量較佳為1000~10萬左右。黏著層中的黏著賦予樹脂的摻合量較佳為5重量%以上30重量%以下的範圍，黏著賦予樹脂的摻合量若超過30重量%，則由於黏著賦予樹脂的分子量低，造成熔態黏度變得極低，使得在進行使用T字形模頭等之共擠壓製膜時，與以聚丙烯系樹脂為主成分的基材層間的積層變得困難。又，黏著層中的黏著賦予樹脂的摻合量若小於5重量%，則有對黏著層的黏著力變化無法有貢獻的擔憂。黏著賦予樹脂的摻合量更佳為6重量%以上25重量%以下，再佳為6重量%以上20重量%以下，再更佳為6重量%以上15重量%以下，特佳為6重量%以上10重量%以下。 Examples of the adhesive-imparting resin include an aliphatic hydrocarbon resin, an aromatic hydrocarbon resin, an alicyclic hydrocarbon resin, an anthracene resin, a benzofuran-indene resin, a styrene resin, a rosin resin, and the like, and among them, an alicyclic group is preferred. Hydrocarbon resin (for example: petroleum resin). The molecular weight of the adhesion-imparting resin is not particularly limited and may be appropriately set, but if the molecular weight is small, it may cause On the other hand, if the molecular weight is increased, the effect of improving the adhesion is deteriorated, so that the number average molecular weight of the adhesion-imparting resin is preferable. It is about 1000~100,000. The blending amount of the adhesion-imparting resin in the adhesive layer is preferably in the range of 5% by weight to 30% by weight, and if the blending amount of the tackifying resin is more than 30% by weight, the molecular weight of the adhesive-imparting resin is low, resulting in a molten state. When the viscosity is extremely low, it is difficult to laminate the base layer with the polypropylene resin as a main component when performing co-extrusion film formation using a T-shaped die or the like. When the amount of the adhesion-imparting resin in the adhesive layer is less than 5% by weight, there is a concern that the adhesion of the adhesive layer does not contribute to the change. The blending amount of the tackifying resin is more preferably 6% by weight or more and 25% by weight or less, still more preferably 6% by weight or more and 20% by weight or less, still more preferably 6% by weight or more and 15% by weight or less, particularly preferably 6% by weight or less. Above 10% by weight or less.
以軟化劑而言，可列舉例如：低分子量的二烯系聚合物、聚異丁烯、氫化聚異戊二烯、氫化聚丁二烯或該等的衍生物、聚丁烯等。軟化劑的分子量並無特別的限制，可適當地設定，惟分子量若變小，則可能會導致從黏著層至黏附體的質量遷移或重剝離化等，另一方面，分子量若變大，則因為有黏著力的提升效果變差之傾向，故軟化劑的數量平均分子量較佳為1000~10萬左右。 Examples of the softening agent include a low molecular weight diene polymer, polyisobutylene, hydrogenated polyisoprene, hydrogenated polybutadiene or the like, polybutene, and the like. The molecular weight of the softener is not particularly limited and may be appropriately set. However, if the molecular weight is small, mass migration or heavy peeling from the adhesive layer to the adherend may occur, and if the molecular weight is increased, Since the adhesion improving effect tends to be poor, the number average molecular weight of the softener is preferably about 1,000 to 100,000.
又，黏著層所使用的黏著賦予樹脂或軟化劑係依據種類而為液體或粉體，亦有在擠壓時汙染擠壓機的物質。這樣的問題係可藉由將黏著賦予樹脂或軟化劑與聚烯烴系樹脂母料化而使用來改善，因此較佳為將黏著賦予 樹脂或軟化劑與聚烯烴系樹脂母料化而使用。 Further, the adhesive-imparting resin or softener used in the adhesive layer is a liquid or a powder depending on the type, and there is also a substance which contaminates the extruder at the time of extrusion. Such a problem can be improved by using a binder-imparting resin or a softener and a polyolefin-based resin as a masterbatch, and therefore it is preferable to impart adhesion. The resin or softener is used as a masterbatch with a polyolefin resin.
黏著層中的苯乙烯系彈性體、黏著賦予樹脂與聚烯烴系樹脂的重量比(苯乙烯系彈性體/黏著賦予樹脂/聚烯烴系樹脂)較佳為45/25/30~90/5/5，更佳為60/20/20~90/5/5，再佳為70/15/15~90/5/5。 The weight ratio of the styrene-based elastomer, the adhesion-imparting resin, and the polyolefin-based resin in the adhesive layer (styrene-based elastomer/adhesive-imparting resin/polyolefin-based resin) is preferably 45/25/30 to 90/5/ 5, better is 60/20/20~90/5/5, and then better is 70/15/15~90/5/5.
本發明之聚烯烴系薄膜的黏著力在23℃下對於丙烯酸板為200~900cN/25mm的範圍，但較佳為考慮到使用於各式各樣的被覆體。若黏著力小於200cN/25mm，則有些被覆體在保護時會產生捲曲等，無法肩負作為保護薄膜的機能。另一方面，若黏著力超過900cN/25mm，則有從被覆體剝離薄膜時無法順利剝離之虞。黏著力係可藉由變更黏著層的樹脂組成或厚度等而適當地設定。黏著力更佳為300cN/25mm以上900cN/25mm以下，再更佳為400cN/25mm以上800cN/25mm以下。 The adhesiveness of the polyolefin-based film of the present invention is in the range of 200 to 900 cN/25 mm for the acrylic plate at 23 ° C, but it is preferably used in various types of coatings. If the adhesion is less than 200 cN/25 mm, some of the coverings may be curled during protection and cannot be used as a protective film. On the other hand, when the adhesive force exceeds 900 cN/25 mm, there is a possibility that the film cannot be smoothly peeled off when the film is peeled off from the covering. The adhesive force can be appropriately set by changing the resin composition or thickness of the adhesive layer. The adhesive force is preferably 300 cN/25 mm or more and 900 cN/25 mm or less, and more preferably 400 cN/25 mm or more and 800 cN/25 mm or less.
本發明之聚烯烴系薄膜可視需要地使其含有周知的添加劑，例如亦可使其含有潤滑劑、抗結塊劑、熱安定劑、抗氧化劑、抗靜電劑、耐光劑、耐衝擊改質劑等，其中較佳為使黏著層表面的低分子量物質小於1mg/m2。 The polyolefin-based film of the present invention may optionally contain a known additive, and may, for example, contain a lubricant, an anti-caking agent, a heat stabilizer, an antioxidant, an antistatic agent, a light stabilizer, and an impact modifier. And preferably, wherein the low molecular weight substance on the surface of the adhesive layer is less than 1 mg/m 2 .
在此，黏著層表面的低分子量物質的測定係依據下列次序來實施。使用乙醇等的不侵蝕構成黏著層的樹脂之有機溶劑洗淨黏著層表面後，以蒸發器等將有機溶劑從該洗淨液去除之後，將秤重其殘渣所求得的數值除以洗淨後的黏著層表面的表面積而求得。在此，若存在有1mg/m2以上的殘渣，則黏著層表面與黏附體表面之間將存在有異物，導致接觸面積減少、凡得瓦力降低，因此 黏著力降低而不佳。在添加添加劑的情形下，需要選擇高分子型等的添加劑、或是探討添加量及添加方法等，使其沒有對黏著層的遷移、轉印。 Here, the measurement of the low molecular weight substance on the surface of the adhesive layer is carried out in the following order. After washing the surface of the adhesive layer with an organic solvent such as ethanol which does not attack the resin constituting the adhesive layer, the organic solvent is removed from the cleaning solution by an evaporator or the like, and the value obtained by weighing the residue is divided by washing. The surface area of the surface of the adhesive layer is obtained. Here, if there is a residue of 1 mg/m 2 or more, foreign matter is present between the surface of the adhesive layer and the surface of the adherend, and the contact area is reduced, and the vanaural force is lowered, so that the adhesive force is not lowered. In the case of adding an additive, it is necessary to select an additive such as a polymer type, or to investigate the addition amount and the addition method, etc., so that migration and transfer of the adhesive layer are not performed.
本發明之聚烯烴系薄膜係於與積層於基材層的一面的黏著層相反之面形成離型層，藉此即便將黏著薄膜彼此重疊，黏著薄膜彼此的黏結亦少，尤其是以輥狀態保管黏著薄膜，之後在轉出薄膜時，也難以引起薄膜部分地伸長、變形等的問題，薄膜的加工適應性優異。為了即使將黏著薄膜彼此重疊也不會使黏著薄膜彼此的黏結產生，有效的作法是於離型層形成表面凹凸，並減少與黏著層的接觸面積。 The polyolefin-based film of the present invention is formed by forming a release layer on the surface opposite to the adhesive layer laminated on one surface of the base material layer, whereby even if the adhesive films are overlapped with each other, the adhesive films are less bonded to each other, particularly in a roll state. When the adhesive film is stored, it is difficult to cause partial elongation or deformation of the film when the film is transferred out, and the film has excellent processing suitability. In order to prevent the adhesion of the adhesive films to each other even if the adhesive films are overlapped with each other, it is effective to form surface irregularities on the release layer and to reduce the contact area with the adhesive layer.
為了形成如上述之表面凹凸，有效的作法是混合非相溶的樹脂至聚丙烯系樹脂。藉由這樣做，可以墊狀地形成一個表面粗糙的層。再者，藉由使用丙烯-乙烯嵌段共聚物作為聚丙烯系樹脂，不用使用非相溶的樹脂，亦可期待同樣的效果。再者，當然亦可將非相溶的樹脂添加到丙烯-乙烯嵌段共聚物。 In order to form the surface unevenness as described above, it is effective to mix the incompatible resin to the polypropylene resin. By doing so, a rough surface layer can be formed in a mat shape. Further, by using a propylene-ethylene block copolymer as the polypropylene-based resin, the same effect can be expected without using an incompatible resin. Further, it is of course also possible to add an incompatible resin to the propylene-ethylene block copolymer.
以不相溶於聚丙烯系樹脂的樹脂而言，可適宜地使用4-甲基-1-戊烯系(共)聚合物等的碳數4以上的α-烯烴(共)聚合物，其他亦可列舉低密度聚乙烯、高密度聚乙烯、乙烯與少量的α-烯烴的共聚物、乙烯與乙酸乙烯酯的共聚物、聚苯乙烯、聚酯系樹脂、聚醯胺系樹脂等。尤其是4-甲基-1-戊烯系(共)聚合物不僅以墊狀使表面粗糙，亦可預期藉由降低薄膜表面的表面自由能而使剝離性 進一步的提升。在本發明中，以離型層而言，可列舉碳數4以上的α-烯烴(共)聚合物與聚丙烯系樹脂(例如：丙烯-乙烯嵌段共聚物或同元聚丙烯)、碳數4以上的α-烯烴(共)聚合物、聚丙烯系樹脂(例如：丙烯-乙烯嵌段共聚物或同元聚丙烯)、與低密度聚乙烯等的組合。 In the resin which is insoluble in the polypropylene resin, an α-olefin (co)polymer having 4 or more carbon atoms such as a 4-methyl-1-pentene-based (co)polymer can be suitably used. Examples thereof include low density polyethylene, high density polyethylene, a copolymer of ethylene and a small amount of an α-olefin, a copolymer of ethylene and vinyl acetate, a polystyrene, a polyester resin, and a polyamide resin. In particular, the 4-methyl-1-pentene (co)polymer not only roughens the surface in the form of a mat, but is also expected to be releasable by reducing the surface free energy of the surface of the film. Further improvement. In the present invention, examples of the release layer include an α-olefin (co)polymer having a carbon number of 4 or more and a polypropylene resin (for example, a propylene-ethylene block copolymer or a homopolypropylene), and carbon. A combination of an alpha-olefin (co)polymer having a number of 4 or more, a polypropylene resin (for example, a propylene-ethylene block copolymer or a homopolypropylene), and a low density polyethylene.
離型層(構成離型層的樹脂成分)中的碳數4以上的α-烯烴(共)聚合物的摻合量為5重量%以上25重量%以下的範圍。碳數4以上的α-烯烴(共)聚合物的摻合量超過25重量%時，若欲在使用T字形模頭等擠壓聚丙烯系樹脂的一般溫度下藉由共擠壓製膜在由聚丙烯系樹脂所構成的基材層的一面上積層離型層，則離型層的製膜性會變差。碳數4以上的α-烯烴(共)聚合物的摻合量若小於5重量%，則對離型層的剝離力改善沒有貢獻。碳數4以上的α-烯烴(共)聚合物的摻合量較佳為7重量%以上24重量%以下。又，碳數4以上的α-烯烴(共)聚合物的分子量若變小，則可能會導致從離型層對黏著層的質量遷移等，因此黏著賦予樹脂的數量平均分子量較佳為1萬~100萬左右。 The blending amount of the α-olefin (co)polymer having 4 or more carbon atoms in the release layer (resin component constituting the release layer) is in the range of 5% by weight to 25% by weight. When the blending amount of the α-olefin (co)polymer having 4 or more carbon atoms exceeds 25% by weight, it is desired to form a film by co-extrusion at a general temperature at which a polypropylene resin is extruded using a T-shaped die or the like. When a release layer is formed on one surface of a base material layer made of a polypropylene resin, the film formability of the release layer is deteriorated. When the blending amount of the α-olefin (co)polymer having 4 or more carbon atoms is less than 5% by weight, the release force of the release layer does not contribute to improvement. The blending amount of the α-olefin (co)polymer having 4 or more carbon atoms is preferably 7% by weight or more and 24% by weight or less. Further, when the molecular weight of the α-olefin (co)polymer having 4 or more carbon atoms is small, migration from the release layer to the mass of the adhesive layer may occur, and therefore the number average molecular weight of the adhesion-imparting resin is preferably 10,000. ~1 million or so.
離型層中的聚丙烯系樹脂與碳數4以上的α-烯烴(共)聚合物的重量比(聚丙烯系樹脂/碳數4以上的α-烯烴(共)聚合物)較佳為95/5~75/25，更佳為93/7~76/24。 The weight ratio of the polypropylene resin in the release layer to the α-olefin (co)polymer having 4 or more carbon atoms (polypropylene resin/α-olefin (co)polymer having 4 or more carbon atoms) is preferably 95. /5~75/25, more preferably 93/7~76/24.
將低密度聚乙烯使用在離型層時，低密度聚乙烯的摻合量在構成離型層的樹脂成分100重量%中較佳為10~40重量%，更佳為15~35重量%。 When the low-density polyethylene is used in the release layer, the blending amount of the low-density polyethylene is preferably 10 to 40% by weight, more preferably 15 to 35% by weight, based on 100% by weight of the resin component constituting the release layer.
鑒於本發明中的黏著層的樹脂組成，較佳為將離型層表面的平均表面粗度SRa設為0.20μm以上0.50μm以下 。藉由這樣做，可提升耐黏結性與黏附體的保護性能。使離型層的表面粗度降低到比0.20μm低時，將薄膜作成輥形態時的薄膜的轉出性會變差。將離型層的表面粗度提高到比0.50μm高時，會有離型層的表面凹凸轉印到黏著層的表面、黏著力顯著降低的情形。 In view of the resin composition of the adhesive layer in the present invention, it is preferred to set the average surface roughness SRa of the surface of the release layer to 0.20 μm or more and 0.50 μm or less. . By doing so, the adhesion resistance and the protective properties of the adherend can be improved. When the surface roughness of the release layer is lowered to be lower than 0.20 μm, the film transfer property when the film is formed into a roll form is deteriorated. When the surface roughness of the release layer is raised to be higher than 0.50 μm, the surface unevenness of the release layer is transferred to the surface of the adhesive layer, and the adhesion is remarkably lowered.
此時，離型層的表面凹凸係更佳為使其成為如以表面的平均表面粗度SRa計為0.25μm以上0.45μm以下之表面。 In this case, the surface unevenness of the release layer is more preferably a surface having a surface roughness of SRa of 0.25 μm or more and 0.45 μm or less.
從將黏著薄膜作成輥形態時的薄膜轉出性的觀點來看，對於本發明之聚烯烴系薄膜的黏著面的離型面之剝離力在23℃下較佳為200cN/25mm以下的範圍。剝離力若超過200cN/25mm，則於將黏著薄膜作成輥形態時的薄膜轉出會產生薄膜部分地伸長、變形等的問題。剝離力可藉由變更離型層中的碳數4以上的α-烯烴共聚物的添加量或表面粗度而適當地設定。 The peeling force of the release surface of the adhesive surface of the polyolefin-based film of the present invention is preferably in the range of 200 cN/25 mm or less at 23 ° C from the viewpoint of the film-transfer property when the adhesive film is formed into a roll form. When the peeling force exceeds 200 cN/25 mm, the film is ejected when the adhesive film is formed into a roll form, which causes a problem that the film is partially elongated and deformed. The peeling force can be appropriately set by changing the addition amount or surface roughness of the α-olefin copolymer having 4 or more carbon atoms in the release layer.
再者，對於黏著薄膜的黏著面的離型面之剝離力的下限作為實際的值係1cN/25mm左右，進一步為5cN/25mm左右。 Further, the lower limit of the peeling force of the release surface of the adhesive surface of the adhesive film is about 1 cN/25 mm, and further about 5 cN/25 mm.
本發明中的聚烯烴系薄膜的黏著層的厚度較佳為1μm以上小於30μm。黏著層的厚度若小於1μm，則使用共擠壓的穩定製膜變得困難；若為30μm以上，則會成為在成本方面不利的薄膜。 The thickness of the adhesive layer of the polyolefin-based film of the present invention is preferably 1 μm or more and less than 30 μm. When the thickness of the adhesive layer is less than 1 μm, it is difficult to form a film by co-extrusion, and if it is 30 μm or more, it is a film which is disadvantageous in terms of cost.
此時，增大黏著力時，考慮到其黏性，較佳為增加厚度。藉由增加黏著層的厚度，容易增加與黏附體的接觸面積。黏著層的厚度較佳為2μm以上20μm以下，更佳 為3μm以上15μm以下，特佳為4μm以上8μm以下。 At this time, when the adhesive force is increased, it is preferable to increase the thickness in consideration of the viscosity. By increasing the thickness of the adhesive layer, it is easy to increase the contact area with the adherend. The thickness of the adhesive layer is preferably 2 μm or more and 20 μm or less, more preferably It is 3 μm or more and 15 μm or less, and particularly preferably 4 μm or more and 8 μm or less.
本發明之聚烯烴系薄膜的基材層的厚度較佳為5μm以上小於100μm，更佳為10μm以上小於75μm，再佳為15μm以上小於40μm。基材層的厚度若小於5μm，則有韌性變差、在作為保護薄膜黏貼在被覆體上時容易產生皺摺、無法充分地獲得黏著力之問題，若為100μm以上，則會成為在成本方面不利的薄膜。 The thickness of the base material layer of the polyolefin-based film of the present invention is preferably 5 μm or more and less than 100 μm, more preferably 10 μm or more and less than 75 μm, still more preferably 15 μm or more and less than 40 μm. When the thickness of the base material layer is less than 5 μm, the toughness is deteriorated, and wrinkles are likely to occur when the protective film is adhered to the covering, and the adhesive strength cannot be sufficiently obtained. When the thickness is 100 μm or more, the cost is increased. Unfavorable film.
本發明之聚烯烴系薄膜的離型層的厚度較佳為1μm以上小於30μm。離型層的厚度若小於1μm，則使用共擠壓的穩定製膜變得困難；若為30μm以上，則會成為在成本方面不利的薄膜。離型層的厚度較佳為2μm以上20μm以下，更佳為3μm以上15μm以下，特佳為4μm以上8μm以下。 The thickness of the release layer of the polyolefin-based film of the present invention is preferably 1 μm or more and less than 30 μm. When the thickness of the release layer is less than 1 μm, it is difficult to form a film by co-extrusion, and if it is 30 μm or more, it is a film which is disadvantageous in terms of cost. The thickness of the release layer is preferably 2 μm or more and 20 μm or less, more preferably 3 μm or more and 15 μm or less, and particularly preferably 4 μm or more and 8 μm or less.
本發明之聚烯烴系薄膜係由含有上述樹脂成分的基材層、黏著層、離型層的各層所構成，各層只要發揮本發明的效果，亦可為1層或2層以上。構成各層的樹脂亦可使用例如單軸、雙軸的擠壓機等，維持在熔融狀態將其送出至進料套組(feed block)型的T字形模頭並積層擠壓，而作成至少3層的聚烯烴系薄膜。各層的擠壓機的溫度亦可為了使各層為熔融狀態，而考慮適宜各層所使用的成分的成形溫度來適當地調節，亦可在例如200℃~260℃的範圍下調節。T字形模頭的溫度可與上述溫度相同。從T字形模頭到鑄造輥(casting roll)的捲取速度只要為使各層成為合適厚度的速度即可，例如為10m/min~50m/min，較佳為10m/min~30m/min。 The polyolefin-based film of the present invention is composed of each of a base layer, an adhesive layer, and a release layer containing the above-described resin component, and each layer may have one or two or more layers as long as the effects of the present invention are exhibited. The resin constituting each layer may be, for example, a uniaxial or biaxial extruder or the like, and maintained in a molten state and sent out to a feed block type T-shaped die and laminated to form at least 3 A layer of a polyolefin-based film. The temperature of the extruder of each layer may be appropriately adjusted in consideration of the molding temperature of the components used for each layer in order to make each layer in a molten state, and may be adjusted, for example, in the range of 200 ° C to 260 ° C. The temperature of the T-shaped die can be the same as the above temperature. The winding speed from the T-shaped die to the casting roll may be a speed at which each layer has a suitable thickness, and is, for example, 10 m/min to 50 m/min, preferably 10 m/min to 30 m/min.
本發明之聚烯烴系薄膜作為輥的形態係在處理上為佳，薄膜輥的寬度及捲繞長度的上限並無特殊的限制，但從處理的容易性來看，一般為寬度1.5m以下，捲繞長度在薄膜厚度30μm時較佳為6000m以下。又，作為捲取的核心，一般可使用3吋、6吋、8吋等的塑膠核心或金屬製的核心。又，從加工的適合性來看，較佳為以長度200m以上、寬度450mm以上的尺寸來捲取的薄膜輥。 The polyolefin-based film of the present invention is preferably used as a roll, and the upper limit of the width and the winding length of the film roll is not particularly limited. However, from the viewpoint of ease of handling, the width is generally 1.5 m or less. The winding length is preferably 6000 m or less at a film thickness of 30 μm. Further, as the core of the winding, a plastic core such as 3 吋, 6 吋, or 8 或 or a metal core can be generally used. Moreover, from the viewpoint of the suitability for processing, a film roll wound up to a size of 200 m or more and a width of 450 mm or more is preferable.
本發明之黏著薄膜係可使用於用於光學用途的稜鏡片等的零件、合成樹脂板(例如：建築材料用)、不鏽鋼板(例如：建築材料用)、鋁板、裝飾合板、鋼板、玻璃板、家電製品、精密機械等。又，本發明之聚烯烴系薄膜可適用於為了保護製造時的車體的表面，為了避免堆疊、保管、運送、於製造步驟中搬送物品時的損傷，以及為了避免二次加工(例如：彎曲加工或壓製加工)物品時的損傷。 The adhesive film of the present invention can be used for parts such as crepe sheets for optical applications, synthetic resin sheets (for example, for building materials), stainless steel sheets (for example, for building materials), aluminum sheets, decorative plywood, steel sheets, and glass sheets. , home appliances, precision machinery, etc. Moreover, the polyolefin-based film of the present invention can be suitably used for the purpose of protecting the surface of the vehicle body during production, in order to avoid damage during stacking, storage, transportation, and transportation of articles in the manufacturing process, and to avoid secondary processing (for example, bending) Damage when processing or pressing) the article.
本案係根據於2011年10月31日申請的日本專利申請案第2011-238935號來主張優先權的利益，於2011年10月31日申請的日本專利申請案第2011-238935號的說明書的全部內容被本案引用作為參考。 The present application claims the priority of the Japanese Patent Application No. 2011-238935, filed on Oct. 31, 2011. The content is cited as a reference in this case.
接著，列舉實施例以進一步說明本發明，惟本發明只要不脫離其要旨，則不受到下述的實施例所限定。還有，以下的實施例、比較例中的物性評價方法係如以下所述。 The present invention will be further illustrated by the following examples, but the invention is not limited by the examples described below. The physical property evaluation methods in the following examples and comparative examples are as follows.
依據JIS-Z-0237(2000)黏著帶與黏著片試驗方法，以下述的方法進行測定。 The measurement was carried out in the following manner in accordance with JIS-Z-0237 (2000) Adhesive tape and adhesive sheet test method.
準備50mm×150mm的丙烯酸板(三菱RAYON(股)製：ACRYLITE(註冊商標)3mm厚)作為黏附體，於薄膜製造時的捲繞方向切取150mm、於與其垂直的方向切取25mm的試驗片作為試驗片，使用質量2000g的橡膠滾筒(滾筒表面的彈簧硬度80Hs、厚度6mm的橡膠層所被覆之寬度45mm、直徑(包含橡膠層)95mm者)，以5mm/秒的速度對黏附體與試驗片進行1來回的壓黏。壓黏後，以使用島津製作所(股)製「Autograph(註冊商標)」(AGS-J)以300mm/分鐘的速度將在溫度23℃、相對濕度65%的環境下放置30分鐘者進行180度剝離時的阻力值作為黏著力[cN/25mm]。180度剝離係指將測定剝離時的阻力值時的丙烯酸板與薄膜的剝離角度保持在180度。 A 50 mm × 150 mm acrylic plate (manufactured by Mitsubishi Rayon Co., Ltd.: ACRYLITE (registered trademark) 3 mm thick) was prepared as a bonded body, and a test piece of 150 mm was cut in the winding direction at the time of film production, and a test piece of 25 mm was cut in a direction perpendicular thereto. For the sheet, a rubber roller having a mass of 2000 g (the spring hardness of the roller surface was 80 Hs, the rubber layer having a thickness of 6 mm was covered with a width of 45 mm, and the diameter (including the rubber layer) was 95 mm), and the adherend and the test piece were applied at a speed of 5 mm/sec. 1 back and forth pressure bonding. After being pressure-bonded, the product was placed at a temperature of 23 ° C and a relative humidity of 65% for 30 minutes at an altitude of 300 mm/min using "Autograph (registered trademark)" (AGS-J) manufactured by Shimadzu Corporation. The resistance value at the time of peeling was used as the adhesive force [cN/25 mm]. The 180-degree peeling means that the peeling angle of the acrylic sheet and the film when the resistance value at the time of peeling is measured is maintained at 180 degrees.
測定時準備厚度190μm、尺寸25mm×170mm的聚酯片作為測定試料的銲條裸端(exposed core)，於經壓黏黏著薄膜與丙烯酸板的測定試料的黏著薄膜側的一端，在黏貼處15mm的寬度下使用思高膠帶(Scotch Tape)黏貼，作成測定時的銲條裸端。將測定試料的示意圖表示於圖1。測定係對一個樣品實施3次，以其平均值作為其樣品的黏著力。 At the time of measurement, a polyester sheet having a thickness of 190 μm and a size of 25 mm×170 mm was prepared as an exposed core of the electrode for measuring the sample, and the end of the pressure-sensitive adhesive film and the acrylic film on the side of the adhesive film was 15 mm at the adhesive portion. Apply the Scotch Tape under the width to make the bare end of the electrode during the measurement. A schematic diagram of the measurement sample is shown in Fig. 1. The measurement system was performed three times on one sample, and the average value was used as the adhesion of the sample.
於丙烯酸板(三菱RAYON(股)製：ACRYLITE(註冊商標)3mm厚)50mm×150mm整面黏貼雙面膠帶(日東電工(股)製：No.535A)，以成為試驗片的黏著面的方式，於雙 面膠帶的另一面黏貼150mm(薄膜製造時的捲繞方向)×50mm(與薄膜製造時的捲繞方向垂直的方向)的試驗片。 For the acrylic sheet (Mitsubishi RAYON Co., Ltd.: ACRYLITE (registered trademark) 3mm thick) 50mm × 150mm double-sided tape (Nitto Electric Co., Ltd.: No. 535A), in order to become the adhesive surface of the test piece Yu Yushuang The other side of the surface tape was adhered to a test piece of 150 mm (winding direction at the time of film production) × 50 mm (direction perpendicular to the winding direction at the time of film production).
於薄膜製造時的捲繞方向切取150mm、於與其垂直的方向切取25mm的試驗片作為新的試驗片，將其黏著面與丙烯酸板透過雙面膠帶黏貼的試驗片的離型面重疊在一起後，使用質量2000g的橡膠滾筒(滾筒表面的彈簧硬度80Hs、厚度6mm的橡膠層所被覆之寬度45mm、直徑(包含橡膠層)95mm者)，以5mm/秒的速度對離型面與試驗片進行1來回的壓黏。壓黏後，以使用島津製作所(股)製「Autograph(註冊商標)」(AGS-J)以300mm/分鐘的速度將在溫度23℃、相對濕度65%的環境下放置30分鐘者進行180度剝離時的阻力值作為剝離力[cN/25mm]。 A test piece of 25 mm was cut in the winding direction at the time of film production, and a test piece of 25 mm was cut in a direction perpendicular thereto as a new test piece, and the adhesive surface was overlapped with the release surface of the test piece to which the acrylic plate was adhered through the double-sided tape. Using a rubber roller of 2000 g (the spring hardness of the roller surface is 80 Hs, the rubber layer having a thickness of 6 mm is covered with a width of 45 mm, and the diameter (including the rubber layer) is 95 mm), and the release surface and the test piece are performed at a speed of 5 mm/sec. 1 back and forth pressure bonding. After being pressure-bonded, the product was placed at a temperature of 23 ° C and a relative humidity of 65% for 30 minutes at an altitude of 300 mm/min using "Autograph (registered trademark)" (AGS-J) manufactured by Shimadzu Corporation. The resistance value at the time of peeling was taken as the peeling force [cN/25 mm].
測定時準備厚度190μm、尺寸25mm×170mm的聚酯片作為測定試料的銲條裸端，於150mm×25mm的試驗片的一端，在黏貼處15mm的寬度下使用思高膠帶黏貼，作成測定時的銲條裸端。測定係對一個樣品實施3次，以其平均值作為其樣品的剝離力。 At the time of measurement, a polyester sheet having a thickness of 190 μm and a size of 25 mm × 170 mm was prepared as the bare end of the electrode for measuring the sample, and was adhered to the end of the test piece of 150 mm × 25 mm at a width of 15 mm at the adhesion point, and the electrode was measured at the time of measurement. Bare end. The measurement system was performed three times on one sample, and the average value was taken as the peeling force of the sample.
使用小坂研究所(股)製的接觸式三維中心面表面粗度計(型式ET-30HK)，在以下條件下利用探針法來測定離型層的表面的中心面平均粗度(SRa)。條件係如下所述，取3次測定的平均值作為數值。 The center-surface average roughness (SRa) of the surface of the release layer was measured by a probe method under the following conditions using a contact three-dimensional center surface roughness meter (type ET-30HK) manufactured by Otaru Research Institute Co., Ltd. The conditions are as follows, and the average value of the three measurements is taken as a numerical value.
探針尖端半徑：0.5μm Probe tip radius: 0.5μm
探針壓：20mgf Probe pressure: 20mgf
截止值：80μm Cutoff: 80μm
測定長：1000μm Measurement length: 1000μm
測定速度：100μm/秒 Measurement speed: 100 μm / sec
測定間隔：2μm Measurement interval: 2μm
使用KEYENCE製的數位顯微鏡(VHX-200F)，以倍率100倍拍攝薄膜黏著面的數位影像。不那麼容易發生來自離型層的轉印者為○，轉印很嚴重者為×。 A digital microscope (VHX-200F) manufactured by KEYENCE was used to take a digital image of the adhesive surface of the film at a magnification of 100 times. It is not so easy for the transferor from the release layer to be ○, and the transfer to be severe is ×.
製造薄膜時能以均勻的厚度製膜者為○，無法以均勻的厚度製膜者為×。 When a film is produced, it is possible to form a film with a uniform thickness of ○, and it is not possible to form a film with a uniform thickness.
在240℃下使用120mm 單軸擠壓機將100wt%的同元聚丙烯樹脂(住友化學製：FLX80E4、MFR：7.5g/10min)熔態擠壓而作成基材層。 Use 120mm at 240 ° C A uniaxial extruder melt-extruded 100 wt% of the homopolypropylene resin (manufactured by Sumitomo Chemical Co., Ltd.: FLX80E4, MFR: 7.5 g/10 min) to form a substrate layer.
在220℃下使用90mm 單軸擠壓機將85wt%的苯乙烯系彈性體(ASAHI KASEI CHEMICALS製：Tuftec(註冊商標)H1221、苯乙烯共聚合比12wt%、MFR：4.5g/10min)、7.5wt%的同元聚丙烯樹脂(住友化學製：FS2011DG3、MFR：2.5g/10min)、與7.5wt%的石油樹脂(荒川化學工業製：ARKON(註冊商標)P125)熔態擠壓而作成黏著層。 Use 90mm at 220 °C A uniaxial extruder consists of 85 wt% of a styrene-based elastomer (manufactured by ASAHI KASEI CHEMICALS: Tuftec (registered trademark) H1221, styrene copolymerization ratio of 12 wt%, MFR: 4.5 g/10 min), and 7.5 wt% of homopolymers. Acrylic resin (manufactured by Sumitomo Chemical Co., Ltd.: FS2011DG3, MFR: 2.5 g/10 min), and 7.5 wt% of petroleum resin (ARKON (registered trademark) P125 manufactured by Arakawa Chemical Industry Co., Ltd.) were melt-extruded to form an adhesive layer.
在250℃下使用90mm 單軸擠壓機將62wt%的同元聚丙烯樹脂(住友化學製：FLX80E4、MFR：7.5g/10min) 、30wt%的低密度聚乙烯樹脂(宇部興產製：R300)、與8wt%的聚甲基戊烯(三井化學製：RT31)熔態擠壓而作成離型層。 Use 90mm at 250 °C The uniaxial extruder has 62 wt% of the same polypropylene resin (manufactured by Sumitomo Chemical Co., Ltd.: FLX80E4, MFR: 7.5 g/10 min), 30 wt% of low-density polyethylene resin (manufactured by Ube Industries: R300), and 8 wt% Polymethylpentene (manufactured by Mitsui Chemicals: RT31) was melt-extruded to form a release layer.
基材層、黏著層、離型層各自使用各擠壓機維持在經熔融的狀態下，在245℃的3層T字形模頭(進料套組型、唇閥(lip)寬度850mm、唇閥間隙1mm)內進行積層擠壓。將經擠壓的薄膜以20m/min速度對溫度30℃的鑄造輥捲取，並冷卻固化而得到基材層厚度為28μm、黏著層厚度為6μm、離型層厚度為6μm的3種3層的未延伸薄膜。 The base material layer, the adhesive layer, and the release layer were each maintained in a molten state at a temperature of 245 ° C in a three-layer T-shaped die (feed set type, lip width (850 mm) width, lip) Lamination is carried out in a valve gap of 1 mm). The extruded film was taken up at a speed of 20 m/min against a casting roll at a temperature of 30 ° C, and solidified by cooling to obtain three kinds of three layers having a substrate layer thickness of 28 μm, an adhesive layer thickness of 6 μm, and a release layer thickness of 6 μm. Unstretched film.
黏著層、基材層係按照實施例1，將離型層變更成下述內容，使用與實施例1同樣的製法獲得3種3層的未延伸薄膜。 Adhesive layer and base material layer According to Example 1, the release layer was changed to the following, and three kinds of three-layer unstretched films were obtained by the same method as in Example 1.
在250℃下使用90mm 單軸擠壓機將56wt%的丙烯-乙烯嵌段共聚物(日本聚丙烯製：BC3HF)、20wt%的低密度聚乙烯樹脂(宇部興產製：R300)、與24wt%的聚甲基戊烯(三井化學製：RT31)熔態擠壓而作成離型層。 Use 90mm at 250 °C The uniaxial extruder has 56 wt% of a propylene-ethylene block copolymer (made of Japanese polypropylene: BC3HF), 20 wt% of a low-density polyethylene resin (manufactured by Ube Industries: R300), and 24 wt% of polymethyl pentane. The olefin (manufactured by Mitsui Chemicals: RT31) is melt-extruded to form a release layer.
基材層係按照實施例1，將黏著層、離型層變更成下述內容，使用與實施例1同樣的製法獲得3種3層的未延伸薄膜。 In the substrate layer, the adhesive layer and the release layer were changed to the following contents in the same manner as in Example 1, and three kinds of three-layer unstretched films were obtained by the same method as in Example 1.
在220℃下使用90mm 單軸擠壓機將以80/7.5/12.5 wt%的比例混合苯乙烯系彈性體(ASAHI KASEI CHEMICALS製：Tuftec(註冊商標)H1221、苯乙烯共聚合比12wt%、MFR：4.5g/10min)、石油樹脂(荒川化學工業製：ARKON(註冊商標)P125)、與同元聚丙烯樹脂(住友化學製：FS2011DG3、MFR：2.5g/10min)者熔態擠壓而作成黏著層。 Use 90mm at 220 °C The uniaxial extruder will mix a styrene-based elastomer at a ratio of 80/7.5/12.5 wt% (manufactured by ASAHI KASEI CHEMICALS: Tuftec (registered trademark) H1221, styrene copolymerization ratio 12 wt%, MFR: 4.5 g/10 min) A petroleum resin (made by Arakawa Chemical Co., Ltd.: ARKON (registered trademark) P125), and a homopolypropylene resin (manufactured by Sumitomo Chemical Co., Ltd.: FS2011DG3, MFR: 2.5 g/10 min) were melt-extruded to form an adhesive layer.
在250℃下使用90mm 單軸擠壓機將72wt%的丙烯-乙烯嵌段共聚物(日本聚丙烯製：BC3HF)、20wt%的低密度聚乙烯樹脂(宇部興產製：R300)、與8wt%的聚甲基戊烯(三井化學製：RT31)熔態擠壓而作成離型層。 Use 90mm at 250 °C The uniaxial extruder has 72 wt% of a propylene-ethylene block copolymer (made of Japanese polypropylene: BC3HF), 20 wt% of a low-density polyethylene resin (manufactured by Ube Industries: R300), and 8 wt% of polymethyl pentane The olefin (manufactured by Mitsui Chemicals: RT31) is melt-extruded to form a release layer.
基材層係按照實施例1，將黏著層、離型層變更成下述內容，使用與實施例1同樣的製法獲得3種3層的未延伸薄膜。 In the substrate layer, the adhesive layer and the release layer were changed to the following contents in the same manner as in Example 1, and three kinds of three-layer unstretched films were obtained by the same method as in Example 1.
在240℃下使用90mm 單軸擠壓機將以90/10wt%的比例混合苯乙烯系彈性體(ASAHI KASEI CHEMICALS製：Tuftec(註冊商標)H1221、苯乙烯共聚合比12wt%、MFR：4.5g/10min)與同元聚丙烯樹脂(住友化學製：FS2011 DG3、MFR：2.5g/10min)者熔態擠壓而作成黏著層。 Use 90mm at 240 ° C The uniaxial extruder will mix a styrene-based elastomer in a ratio of 90/10 wt% (manufactured by ASAHI KASEI CHEMICALS: Tuftec (registered trademark) H1221, styrene copolymerization ratio: 12 wt%, MFR: 4.5 g/10 min) and the same element. Polypropylene resin (manufactured by Sumitomo Chemical Co., Ltd.: FS2011 DG3, MFR: 2.5 g/10 min) was melt-extruded to form an adhesive layer.
在250℃下使用90mm 單軸擠壓機將72wt%的丙烯-乙烯嵌段共聚物(日本聚丙烯製：BC3HF)、20wt%的低密度聚乙烯樹脂(宇部興產製：R300)、與8wt%的聚甲基戊 烯(三井化學製：RT31)熔態擠壓而作成離型層。 Use 90mm at 250 °C The uniaxial extruder has 72 wt% of a propylene-ethylene block copolymer (made of Japanese polypropylene: BC3HF), 20 wt% of a low-density polyethylene resin (manufactured by Ube Industries: R300), and 8 wt% of polymethyl pentane The olefin (manufactured by Mitsui Chemicals: RT31) is melt-extruded to form a release layer.
基材層係按照實施例1，將黏著層、離型層變更成下述內容，使用與實施例1同樣的製法獲得3種3層的未延伸薄膜。 In the substrate layer, the adhesive layer and the release layer were changed to the following contents in the same manner as in Example 1, and three kinds of three-layer unstretched films were obtained by the same method as in Example 1.
在240℃下使用90mm 單軸擠壓機將以90/10wt%的比例混合苯乙烯系彈性體(ASAHI KASEI CHEMICALS製：Tuftec(註冊商標)H1221、苯乙烯共聚合比12wt%、MFR：4.5g/10min)與同元聚丙烯樹脂(住友化學製：FS2011 DG3、MFR：2.5g/10min)者熔態擠壓而作成黏著層。 Use 90mm at 240 ° C The uniaxial extruder will mix a styrene-based elastomer in a ratio of 90/10 wt% (manufactured by ASAHI KASEI CHEMICALS: Tuftec (registered trademark) H1221, styrene copolymerization ratio: 12 wt%, MFR: 4.5 g/10 min) and the same element. Polypropylene resin (manufactured by Sumitomo Chemical Co., Ltd.: FS2011 DG3, MFR: 2.5 g/10 min) was melt-extruded to form an adhesive layer.
在250℃下使用90mm 單軸擠壓機將92wt%的丙烯-乙烯嵌段共聚物(日本聚丙烯製：BC3HF)、8wt%的聚甲基戊烯(三井化學製：RT31)、與20wt%的低密度聚乙烯樹脂(宇部興產製：R300)熔態擠壓而作成離型層。 Use 90mm at 250 °C The uniaxial extruder has 92 wt% of a propylene-ethylene block copolymer (made of Japanese polypropylene: BC3HF), 8 wt% of polymethylpentene (manufactured by Mitsui Chemicals, Inc.: RT31), and 20 wt% of a low-density polyethylene resin. (Ube Industries: R300) is melt extruded to form a release layer.
基材層係按照實施例1，將黏著層、離型層變更成下述內容，使用與實施例1同樣的製法獲得3種3層的未延伸薄膜。 In the substrate layer, the adhesive layer and the release layer were changed to the following contents in the same manner as in Example 1, and three kinds of three-layer unstretched films were obtained by the same method as in Example 1.
在240℃下使用90mm 單軸擠壓機將以90/10wt%的比例混合苯乙烯系彈性體(ASAHI KASEI CHEMICALS製：Tuftec(註冊商標)H1221、苯乙烯共聚合比12wt%、MFR：4.5g/10min)與同元聚丙烯樹脂(住友化學製：FS2011 DG3、MFR：2.5g/10min)者熔態擠壓而作成黏著層。 Use 90mm at 240 ° C The uniaxial extruder will mix a styrene-based elastomer in a ratio of 90/10 wt% (manufactured by ASAHI KASEI CHEMICALS: Tuftec (registered trademark) H1221, styrene copolymerization ratio: 12 wt%, MFR: 4.5 g/10 min) and the same element. Polypropylene resin (manufactured by Sumitomo Chemical Co., Ltd.: FS2011 DG3, MFR: 2.5 g/10 min) was melt-extruded to form an adhesive layer.
在250℃下使用90mm 單軸擠壓機將88wt%的同元聚丙烯樹脂(住友化學製：FLX80E4、MFR：7.5g/10min)與12wt%的聚甲基戊烯(三井化學製：RT31)熔態擠壓而作成離型層。 Use 90mm at 250 °C A uniaxial extruder made 88 wt% of the isotactic polypropylene resin (manufactured by Sumitomo Chemical Co., Ltd.: FLX80E4, MFR: 7.5 g/10 min) and 12 wt% of polymethylpentene (manufactured by Mitsui Chemicals Co., Ltd.: RT31). Release layer.
基材層、黏著層係按照實施例1，將離型層變更成下述內容，使用與實施例1同樣的製法獲得3種3層的未延伸薄膜。 The base material layer and the adhesive layer were changed to the following contents in the same manner as in Example 1, and three types of three-layer unstretched films were obtained by the same method as in Example 1.
在250℃下使用90mm 單軸擠壓機將100wt%的丙烯-乙烯嵌段共聚物(日本聚丙烯製：BC4FC)熔態擠壓而作成離型層。 Use 90mm at 250 °C A uniaxial extruder melt-extruded 100 wt% of a propylene-ethylene block copolymer (manufactured by Nippon Polypropylene: BC4FC) to form a release layer.
基材層、黏著層係按照實施例1，將離型層變更成下述內容，使用與實施例1同樣的製法獲得3種3層的未延伸薄膜。 The base material layer and the adhesive layer were changed to the following contents in the same manner as in Example 1, and three types of three-layer unstretched films were obtained by the same method as in Example 1.
在250℃下使用90mm 單軸擠壓機將66wt%的同元聚丙烯樹脂(住友化學製：FLX80E4、MFR：7.5g/10min)、30wt%的低密度聚乙烯樹脂(宇部興產製：R300)、與4wt%的聚甲基戊烯(三井化學製：RT31)熔態擠壓而作成離型層。 Use 90mm at 250 °C The uniaxial extruder has 66 wt% of the isotactic polypropylene resin (manufactured by Sumitomo Chemical Co., Ltd.: FLX80E4, MFR: 7.5 g/10 min), 30 wt% of low-density polyethylene resin (manufactured by Ube Industries: R300), and 4 wt% Polymethylpentene (manufactured by Mitsui Chemicals: RT31) was melt-extruded to form a release layer.
基材層、黏著層係按照實施例1，將離型層變更成下述內容，雖然使用與實施例1相同的製法獲得3種3層的未延伸薄膜，但是其厚度精度差且無法獲得能承受評價的薄膜。 The base layer and the adhesive layer were changed to the following contents in the same manner as in Example 1. Although three kinds of three-layer unstretched films were obtained by the same method as in Example 1, the thickness precision was poor and the energy was not obtained. A film that is evaluated.
在250℃下使用90mm 單軸擠壓機將50wt%的同元聚丙烯樹脂(住友化學製：FLX80E4、MFR：7.5g/10min)與50wt%的聚甲基戊烯(三井化學製：RT31)熔態擠壓而作成離型層。 Use 90mm at 250 °C A uniaxial extruder made 50 wt% of the same polypropylene resin (manufactured by Sumitomo Chemical Co., Ltd.: FLX80E4, MFR: 7.5 g/10 min) and 50 wt% of polymethylpentene (manufactured by Mitsui Chemicals: RT31). Release layer.
基材層係按照實施例1，將黏著層、離型層變更成下述內容，使用與實施例1同樣的製法獲得3種3層的未延伸薄膜。 In the substrate layer, the adhesive layer and the release layer were changed to the following contents in the same manner as in Example 1, and three kinds of three-layer unstretched films were obtained by the same method as in Example 1.
使用90mm 單軸擠壓機將100wt%的苯乙烯系彈性體(ASAHI KASEI CHEMICALS製：Tuftec(註冊商標)H1221、苯乙烯共聚合比12wt%、MFR：4.5g/10min)熔態擠壓而作成黏著層。 Use 90mm A uniaxial extruder melt-extruded 100 wt% of a styrene-based elastomer (manufactured by ASAHI KASEI CHEMICALS: Tuftec (registered trademark) H1221, styrene copolymerization ratio: 12 wt%, MFR: 4.5 g/10 min) to form an adhesive layer. .
在250℃下使用90mm 單軸擠壓機將84wt%的丙烯-乙烯嵌段共聚物(日本聚丙烯製：BC3HF)與16wt%的聚甲基戊烯(三井化學製：RT31)熔態擠壓而作成離型層。 Use 90mm at 250 °C A uniaxial extruder melt-extruded 84 wt% of a propylene-ethylene block copolymer (made by Japan Polypropylene: BC3HF) and 16 wt% of polymethylpentene (manufactured by Mitsui Chemicals: RT31) to form a release layer.
將上述結果表示於表1、2、3。 The above results are shown in Tables 1, 2 and 3.
從表1~3明顯得知，實施例1~6所獲得的薄膜在作為保護薄膜使用時，具有在實用上足夠的黏著力，亦無表面粗糙的轉印，將薄膜作為輥轉出時的剝離性亦良好，製膜性亦良好。 It is apparent from Tables 1 to 3 that the films obtained in Examples 1 to 6 have practically sufficient adhesive force and no surface roughness transfer when used as a protective film, and when the film is used as a roll. The peelability is also good, and the film forming property is also good.
另一方面，比較例1及2及4所獲得的薄膜，其將薄膜作為輥轉出時的剝離性並不能說是良好。在比較例3的製法中，其製膜性差且無法獲得能承受評價的薄膜。像這樣的比較例所獲得的薄膜皆為品質差、實用性低。 On the other hand, in the films obtained in Comparative Examples 1 and 2 and 4, the peeling property when the film was transferred as a roll was not considered to be good. In the production method of Comparative Example 3, the film forming property was poor and a film capable of withstanding evaluation could not be obtained. The films obtained in the comparative examples like this were all of poor quality and low in practicality.
本發明之聚烯烴系薄膜係可使用於合成樹脂板(例如：建築材料用)、不鏽鋼板(例如：建築材料用)、鋁板、裝飾合板、鋼板、玻璃板、家電製品、精密機械等。又，本發明之聚烯烴系薄膜可適用於為了保護製造時的車體的表面，為了避免堆疊、保管、運送、於製造步驟中搬送物品時的損傷，以及為了避免二次加工(例如：彎曲加工或壓製加工)物品時的損傷，對產業界的貢獻很大。 The polyolefin-based film of the present invention can be used for synthetic resin sheets (for example, for building materials), stainless steel sheets (for example, for building materials), aluminum sheets, decorative plywood, steel sheets, glass sheets, home electric appliances, precision machines, and the like. Moreover, the polyolefin-based film of the present invention can be suitably used for the purpose of protecting the surface of the vehicle body during production, in order to avoid damage during stacking, storage, transportation, and transportation of articles in the manufacturing process, and to avoid secondary processing (for example, bending) Damage to the industry when processing or pressing) has a great contribution to the industry.
1‧‧‧上部夾頭 1‧‧‧ upper chuck
2‧‧‧聚酯片 2‧‧‧ polyester sheet
3‧‧‧丙烯酸板 3‧‧‧Acrylic board
4‧‧‧思高膠帶 4‧‧‧Sco tape
5‧‧‧黏著薄膜 5‧‧‧Adhesive film
6‧‧‧下部夾頭 6‧‧‧Lower chuck
7‧‧‧拉伸方向 7‧‧‧Stretching direction
第1圖係測定試料的示意圖。 Figure 1 is a schematic diagram of the measurement sample.
Claims (5)
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| JP (1) | JP6015352B2 (en) |
| KR (1) | KR101978535B1 (en) |
| CN (1) | CN103906818B (en) |
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| KR101791803B1 (en) * | 2013-07-26 | 2017-10-30 | 미쯔이가가꾸가부시끼가이샤 | Surface protective film |
| CN107142032B (en) * | 2017-05-03 | 2020-12-08 | 张家港康得新光电材料有限公司 | Self-adhesion protective film |
| JP7287863B2 (en) * | 2018-08-09 | 2023-06-06 | 東レフィルム加工株式会社 | laminated film |
| CN110872474A (en) * | 2018-08-31 | 2020-03-10 | 翊圣企业股份有限公司 | Base film for cutting piece adhesive film and manufacturing method thereof |
| KR20210148093A (en) | 2019-03-29 | 2021-12-07 | 도레이 필름 카코우 가부시키가이샤 | laminated film |
| WO2020212905A1 (en) * | 2019-04-17 | 2020-10-22 | Nitto Denko Corporation | Multilayer co-extruded films and article containing same |
| JP7306228B2 (en) | 2019-11-08 | 2023-07-11 | 三菱ケミカル株式会社 | Laminated film, Laminated film for flexible printed circuit board process |
| CN112126364A (en) * | 2020-09-21 | 2020-12-25 | 广东东立新材料科技股份有限公司 | Adhesive layer composition, self-adhesive film and application thereof |
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| CN101189317A (en) * | 2005-06-06 | 2008-05-28 | 积水化学工业株式会社 | Surface protective film |
| CN102015942A (en) * | 2008-04-30 | 2011-04-13 | 东洋纺织株式会社 | Pressure-sensitive adhesive film |
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| JP2713519B2 (en) * | 1991-01-31 | 1998-02-16 | 積水化学工業株式会社 | Surface protection film |
| JP4367082B2 (en) * | 2002-10-25 | 2009-11-18 | 三菱化学ポリエステルフィルム株式会社 | Release agent and release sheet |
| JP4693599B2 (en) * | 2005-11-04 | 2011-06-01 | 積水化学工業株式会社 | Method for producing surface protective film |
| JP4573854B2 (en) * | 2006-05-31 | 2010-11-04 | 日本ポリプロ株式会社 | Biaxially stretched self-adhesive protective film |
| JP5047575B2 (en) * | 2006-09-29 | 2012-10-10 | 三井化学株式会社 | Surface protection film |
| JP5288733B2 (en) * | 2007-05-31 | 2013-09-11 | 出光ユニテック株式会社 | Surface protection film |
| JP5503129B2 (en) * | 2008-09-29 | 2014-05-28 | 積水化学工業株式会社 | Masking tape and manufacturing method thereof |
| JP5280902B2 (en) * | 2009-03-18 | 2013-09-04 | 積水化学工業株式会社 | Surface protection sheet for prism sheet |
| JP5600905B2 (en) * | 2009-08-24 | 2014-10-08 | 東洋紡株式会社 | Adhesive film |
| JP2011042757A (en) | 2009-08-24 | 2011-03-03 | Mitsui Chemicals Inc | Surface protection film |
| JP5489729B2 (en) * | 2010-01-08 | 2014-05-14 | 三井化学株式会社 | Resin composition and film containing the same |
| JPWO2011096351A1 (en) * | 2010-02-02 | 2013-06-10 | 三井化学東セロ株式会社 | Surface protection film |
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| CN101189317A (en) * | 2005-06-06 | 2008-05-28 | 积水化学工业株式会社 | Surface protective film |
| CN102015942A (en) * | 2008-04-30 | 2011-04-13 | 东洋纺织株式会社 | Pressure-sensitive adhesive film |
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| JP6015352B2 (en) | 2016-10-26 |
| JP2013117019A (en) | 2013-06-13 |
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| WO2013065578A1 (en) | 2013-05-10 |
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