TWI575042B - A pressure-sensitive adhesive film or sheet, surface protection film or sheet, and use of the pressure-sensitive adhesive film or sheet for the surface protection of an article - Google Patents
A pressure-sensitive adhesive film or sheet, surface protection film or sheet, and use of the pressure-sensitive adhesive film or sheet for the surface protection of an article Download PDFInfo
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Description
本發明係關於一種感壓型黏著薄膜或片、表面保護薄膜或片、以及將感壓型黏著薄膜或片使用於保護物品表面之方法。 The present invention relates to a pressure sensitive adhesive film or sheet, a surface protective film or sheet, and a method of using a pressure sensitive adhesive film or sheet for protecting the surface of an article.
黏著薄膜或片係作為用以保護製品之表面不受灰塵之附著、污染、劃傷等之表面保護薄膜使用。 The adhesive film or sheet is used as a surface protective film for protecting the surface of the product from dust, adhesion, scratches, and the like.
近年來，亦用作精密電子零件之表面保護薄膜。 In recent years, it has also been used as a surface protection film for precision electronic parts.
對黏著薄膜或片要求黏著層與被黏附體之黏著力適度較強。該所謂適度之強度，係指並無自然地自身剝離或因較輕之振動或衝擊而脫落之情況的強度，且指於剝離時不於被黏附體表面殘留黏著層而可順利地剝離的強度。 It is required that the adhesion between the adhesive layer and the adherend is moderately strong for the adhesive film or sheet. The term "appropriate strength" refers to the strength which does not naturally peel off by itself or falls off due to light vibration or impact, and refers to the strength which can be smoothly peeled off without leaving an adhesive layer on the surface of the adherend at the time of peeling. .
滿足此種要求特性之黏著薄膜或片存在包含乙烯-乙酸乙烯酯共聚合體之薄膜或片。 An adhesive film or sheet that satisfies such a desired property is present in a film or sheet comprising an ethylene-vinyl acetate copolymer.
專利文獻1(日本專利特開平6-145616號)中記載有一種表面保護薄膜，其特徵在於包含黏著層，該黏著層係相對於具有乙酸乙烯酯含量3~7重量%及熔融流動速率2~20g/10分鐘之乙烯-乙酸乙烯酯共聚合體100重量份而含有黏著賦予劑0.5~2重量份者。該表面保護薄膜被認為發揮適度之初始黏著力，即便實施加熱處理、尤其是 紫外線(UV，Ultraviolet)照射，亦無黏著力明顯上升之情況，又，亦無對被保護物之污染性。 A surface protective film comprising an adhesive layer having a vinyl acetate content of 3 to 7% by weight and a melt flow rate of 2 to 4 is described in Patent Document 1 (Japanese Patent Laid-Open No. Hei 6-146516). 100 parts by weight of the ethylene-vinyl acetate copolymer of 20 g/10 minutes and 0.5 to 2 parts by weight of the adhesion-imparting agent. The surface protection film is considered to exert a moderate initial adhesion even after heat treatment, especially Ultraviolet (UV, Ultraviolet) irradiation, there is no obvious increase in adhesion, and there is no pollution to the protected material.
專利文獻2(日本專利特開2008-255233號)中記載有一種黏著薄膜或片，其包含：聚丙烯樹脂基材層(A)；及黏著層(B)，該黏著層(B)包含乙酸乙烯酯單位含量為7.5~50重量%之乙烯-乙酸乙烯酯共聚合體。 An adhesive film or sheet comprising: a polypropylene resin base material layer (A); and an adhesive layer (B) containing acetic acid is described in Patent Document 2 (Japanese Patent Laid-Open Publication No. 2008-255233). An ethylene-vinyl acetate copolymer having a vinyl ester unit content of from 7.5 to 50% by weight.
該黏著薄膜或片被認為基材層與黏著層之層間接著強度較高，黏著層對被黏著對象物品面具有適度之黏著力，且，該基材層之軟化溫度、熱變形溫度等熱特性、拉伸強度、耐衝擊性、剛性等機械特性、霧度、光澤、光穿透度等光學特性優異，而且幾乎無魚眼之產生，表面平滑且外觀亦極其良好。 The adhesive film or sheet is considered to have a higher bonding strength between the substrate layer and the adhesive layer, and the adhesive layer has a moderate adhesion to the surface of the object to be adhered, and the thermal properties such as softening temperature and heat distortion temperature of the substrate layer. It has excellent optical properties such as tensile strength, impact resistance, and rigidity, such as haze, gloss, and light transmittance, and has almost no fish eyes. The surface is smooth and the appearance is extremely good.
另一方面，專利文獻3(日本專利特開2010-171419號)中記載有一種太陽電池用密封材片，其包含(A)乙烯-乙酸乙烯酯共聚合體樹脂、及與(A)之相溶性較高之(B)C9系芳香族烴樹脂之氫化物，且上述(B)C9系芳香族烴樹脂之氫化物之氫化率為40%以上。 On the other hand, a sealing sheet for a solar cell comprising (A) an ethylene-vinyl acetate copolymer resin and compatibility with (A) is described in the patent document 3 (Japanese Patent Laid-Open Publication No. 2010-171419). The (B) hydride of the C9 aromatic hydrocarbon resin is higher, and the hydrogenation rate of the hydride of the (B) C9 aromatic hydrocarbon resin is 40% or more.
該太陽電池用密封材片被認為於進行熔融、加工等處理時之加工性優異，進而具有較高之透明性並且耐光性及耐熱性優異，穩定性較高。 The solar cell sealing material sheet is considered to have excellent workability when subjected to processing such as melting and processing, and has high transparency, excellent light resistance and heat resistance, and high stability.
專利文獻1：日本專利特開平6-145616號公報 Patent Document 1: Japanese Patent Laid-Open No. Hei 6-146516
專利文獻2：日本專利特開2008-255233號公報 Patent Document 2: Japanese Patent Laid-Open Publication No. 2008-255233
專利文獻3：日本專利特開2010-171419號公報 Patent Document 3: Japanese Patent Laid-Open Publication No. 2010-171419
專利文獻1(日本專利特開平6-145616號公報)中記載由乙酸乙烯酯含量3~7重量%之乙烯-乙酸乙烯酯共聚合體所構成之薄膜對被黏附體之黏著力不充分。因此，為獲得所需之黏著力，必需含有大量黏著賦予劑。 In the patent document 1 (JP-A-6-145616), it is described that the film composed of the ethylene-vinyl acetate copolymer having a vinyl acetate content of 3 to 7% by weight has insufficient adhesion to the adherend. Therefore, in order to obtain the desired adhesive force, it is necessary to contain a large amount of adhesion-imparting agent.
然而，若黏著層中含有大量黏著賦予劑，則於剝離黏著薄膜時黏著層變得容易殘留於被黏附體表面。即，對被黏附體之耐污染性降低。 However, if the adhesive layer contains a large amount of the adhesion-imparting agent, the adhesive layer tends to remain on the surface of the adherend when the adhesive film is peeled off. That is, the stain resistance to the adherend is lowered.
又，黏著賦予劑相對高價，進而亦有伴隨世界性需求增加之供給不穩定的擔憂，故而亦有欲減少黏著賦予劑之使用量之要求。 Further, since the adhesion-imparting agent is relatively expensive, and there is a concern that the supply of the world is increasing due to unstable supply, there is a demand for reducing the amount of the adhesion-imparting agent.
又，專利文獻2(日本專利特開2008-255233號公報)中記載之乙酸乙烯酯單位含量為7.5~50重量%之乙烯-乙酸乙烯酯共聚合體對被黏附體之黏著力亦不充分。又，黏著力較初始黏著力經時性地變強之經時性亢進的傾向較強。 Further, the ethylene-vinyl acetate copolymer having a vinyl acetate content of 7.5 to 50% by weight as described in the patent document 2 (Japanese Patent Laid-Open Publication No. 2008-255233) is also insufficient in adhesion to the adherend. Further, the adhesive strength tends to be stronger with the initial adhesive strength over time.
本發明係鑒於如上所述之課題而成者，提供一種感壓型黏著薄膜或片，該感壓型黏著薄膜或片於不對黏著層積極地進行加熱而於室溫條件下壓合於被黏附體之情形時，具有所需之黏著力，並且使黏著賦予劑之使用量減少。 The present invention has been made in view of the above problems, and provides a pressure-sensitive adhesive film or sheet which is pressed and adhered at room temperature without actively heating the adhesive layer. In the case of a body, it has a desired adhesive force and reduces the amount of the adhesion-imparting agent.
根據本發明，提供一種感壓型黏著薄膜或片，其具備黏著層，該黏著層包含：乙酸乙烯酯含量為7.5質量%以上且20質量%以下之乙烯-乙酸乙烯酯共聚合體；及氫化率於50%以上且未滿90%之範圍內之黏著賦予劑。 According to the present invention, there is provided a pressure-sensitive adhesive film or sheet comprising an adhesive layer comprising: an ethylene-vinyl acetate copolymer having a vinyl acetate content of 7.5% by mass or more and 20% by mass or less; and a hydrogenation rate An adhesion-imparting agent in a range of 50% or more and less than 90%.
進而，根據本發明，提供一種表面保護薄膜或片，其包含上述感壓型黏著薄膜或片。 Further, according to the present invention, there is provided a surface protective film or sheet comprising the above-mentioned pressure-sensitive adhesive film or sheet.
根據該發明，可獲得一種感壓型黏著薄膜或片，其藉由包含乙酸乙烯酯含量為7.5質量%以上且20質量%以下之乙烯-乙酸乙烯酯共聚合體、及氫化率為50%以上且未滿90%之黏著賦予劑，即便黏著劑賦予樹脂之添加量較少，亦具有所需之黏著力。 According to the invention, it is possible to obtain a pressure-sensitive adhesive film or sheet comprising an ethylene-vinyl acetate copolymer having a vinyl acetate content of 7.5% by mass or more and 20% by mass or less, and a hydrogenation ratio of 50% or more Less than 90% of the adhesion-imparting agent has a desired adhesive force even if the adhesive imparts less to the resin.
進而，根據本發明，提供一種將上述感壓型黏著薄膜或片使用於保護物品表面之方法。 Further, according to the present invention, there is provided a method of using the above-mentioned pressure-sensitive adhesive film or sheet for protecting the surface of an article.
根據本發明，可提供一種感壓型黏著薄膜或片，其具有所需之黏著力，並且黏著賦予劑之使用量減少。 According to the present invention, it is possible to provide a pressure-sensitive adhesive film or sheet which has a desired adhesive force and a reduced amount of the adhesive-imparting agent.
上述目的、以及其他目的、特徵及優點係藉由以下所述之較佳實施形態而進一步明確。 The above and other objects, features, and advantages of the invention will be apparent from the embodiments described herein.
以下，對本發明之實施形態進行說明。 Hereinafter, embodiments of the present invention will be described.
本實施形態之感壓型黏著薄膜或片具備黏著層，該黏著層包含：乙酸乙烯酯含量為7.5質量%以上且20質量%以下之乙烯-乙酸乙烯酯共聚合體；及氫化率為50%以上且未滿90%之黏著賦予劑。 The pressure-sensitive adhesive film or sheet of the present embodiment includes an adhesive layer containing an ethylene-vinyl acetate copolymer having a vinyl acetate content of 7.5% by mass or more and 20% by mass or less; and a hydrogenation ratio of 50% or more And less than 90% of the adhesion imparting agent.
再者，關於本發明中之黏著層與被黏附體之黏著力，並非如熱熔接著劑之接著劑於熔點以上之加熱條件下，將黏著層壓合於被黏附體而進行接著者，而表示於未滿熔點之溫度環境下將黏著層壓合於被黏 附體而進行接著時之層間剝離強度。 Furthermore, the adhesive force of the adhesive layer and the adherend in the present invention is not adhered to the adherend by heating under the heating condition of the adhesive of the hot melt adhesive, and the adhesive is bonded to the adherend. Indicates that the adhesive is laminated to the adhesive under a temperature environment that is not full of melting point The adhesion strength of the layer at the time of the adhesion was carried out.
首先，對構成本實施形態之感壓型黏著薄膜或片之黏著層的各成分進行說明。 First, each component constituting the pressure-sensitive adhesive film or sheet of the present embodiment will be described.
本發明之必需成分即乙烯-乙酸乙烯酯共聚合體(EVA)為乙烯與乙酸乙烯酯之共聚合體。 The ethylene-vinyl acetate copolymer (EVA), an essential component of the present invention, is a copolymer of ethylene and vinyl acetate.
本發明之乙烯-乙酸乙烯酯共聚合體中，乙酸乙烯酯成分之單位含量為7.5質量%以上且20質量%以下，較佳為8質量%以上且15質量%以下，尤佳為9質量%以上且12質量%以下。若乙酸乙烯酯含量為上述範圍內，則可獲得具有適度之初始黏著力之感壓型黏著薄膜或片。 In the ethylene-vinyl acetate copolymer of the present invention, the unit content of the vinyl acetate component is 7.5% by mass or more and 20% by mass or less, preferably 8% by mass or more and 15% by mass or less, and particularly preferably 9% by mass or more. And 12% by mass or less. If the vinyl acetate content is within the above range, a pressure-sensitive adhesive film or sheet having an appropriate initial adhesion can be obtained.
若乙酸乙烯酯含量為上述下限值以上，則可獲得初始黏著力更優異之感壓型黏著薄膜或片。另一方面，若乙酸乙烯酯含量為上述上限值以下，則可獲得黏著力之經時性亢進受到抑制之感壓型黏著薄膜或片。即，對被黏附體之耐污染性更優異。 When the vinyl acetate content is at least the above lower limit value, a pressure-sensitive adhesive film or sheet having more excellent initial adhesion can be obtained. On the other hand, when the vinyl acetate content is at most the above upper limit value, a pressure-sensitive adhesive film or sheet in which the temporal increase in adhesion is suppressed can be obtained. That is, the stain resistance to the adherend is more excellent.
又，本實施形態之乙烯-乙酸乙烯酯共聚合體並無特別限定，190℃、2160g載重下之熔融流動速率(MFR)(依據JIS K7210-1999)較佳為1g/10分鐘以上且50g/10分鐘以下，尤佳為2g/10分鐘以上且30g/10分鐘以下。 Further, the ethylene-vinyl acetate copolymer of the present embodiment is not particularly limited, and the melt flow rate (MFR) at 190 ° C and a load of 2160 g (according to JIS K7210-1999) is preferably 1 g/10 min or more and 50 g/10. In the minute or less, it is particularly preferably 2 g/10 minutes or more and 30 g/10 minutes or less.
若MFR為上述下限值以上，則薄膜之平滑性及初始黏著力更優異。另一方面，若MFR為上述上限值以下，則低分子成分變少，故而薄膜之黏連性或對保護基材之耐污染性更優異。 When the MFR is at least the above lower limit value, the smoothness and initial adhesion of the film are more excellent. On the other hand, when the MFR is at most the above upper limit value, the low molecular component is reduced, and the adhesion of the film or the stain resistance to the protective substrate is further improved.
本發明之必需成分即黏著賦予劑係為了提高黏著層之黏著力而進行調配。 The adhesive-imparting agent which is an essential component of the present invention is formulated to improve the adhesion of the adhesive layer.
作為黏著賦予劑，例如可列舉：脂肪族系烴樹脂、芳香族系烴樹脂、脂肪族-芳香族共聚合體系烴樹脂、脂環式系烴樹脂等石油系樹脂之氫化物；蒎烯樹脂、薰草咔-茚系樹脂、萜酚系樹脂等萜烯系樹脂之氫化物；聚合松脂系樹脂之氫化物；(烷基)酚系樹脂之氫化物；二甲苯系樹脂之氫化物；苯乙烯系樹脂之氫化物等。該等之中，較佳為石油系樹脂之氫化物，尤佳為脂環式系烴樹脂之氫化物(亦稱為脂環式飽和烴樹脂)。 Examples of the adhesion-imparting agent include a hydrogenated product of a petroleum-based resin such as an aliphatic hydrocarbon resin, an aromatic hydrocarbon resin, an aliphatic-aromatic copolymerization hydrocarbon resin, or an alicyclic hydrocarbon resin; a terpene resin; a hydride of a terpene resin such as a quinone-based resin or a phenol-based resin; a hydride of a polymerized rosin-based resin; a hydride of an (alkyl) phenol-based resin; a hydride of a xylene-based resin; A hydride or the like of a resin. Among these, a hydride of a petroleum resin is preferred, and a hydride of an alicyclic hydrocarbon resin (also referred to as an alicyclic saturated hydrocarbon resin) is preferred.
該等黏著賦予劑中，亦可包含烯烴樹脂。 An olefin resin may be contained in these adhesion-imparting agents.
作為石油系樹脂之氫化物，可列舉以乙烯基甲苯、茚、α-甲基苯乙烯等C8~C10之乙烯基芳香族烴為主成分之樹脂之氫化物等。 The hydride of the petroleum-based resin may, for example, be a hydrogenated product of a resin containing a C 8 -C 10 vinyl aromatic hydrocarbon such as vinyl toluene, hydrazine or α-methyl styrene as a main component.
作為萜烯系樹脂之氫化物，例如可列舉α-蒎烯聚合體、β-蒎烯聚合體、雙戊烯聚合體、萜烯-苯酚共聚合體等之氫化物。 Examples of the hydrogenated product of the terpene-based resin include a hydrogenated product of an α-pinene polymer, a β-pinene polymer, a dipentene polymer, and a terpene-phenol copolymer.
作為聚合松脂系樹脂之氫化物，例如可列舉氫化松香、氫化松香之甘油酯或其聚合體、以及氫化松香之新戊四醇酯或其聚合體等。 Examples of the hydrogenated product of the polymerized rosin-based resin include hydrogenated rosin, hydrogenated rosin glyceride or a polymer thereof, and hydrogenated rosin pentaerythritol ester or a polymer thereof.
作為苯乙烯系樹脂之氫化物，例如可列舉苯乙烯系單體之均聚物、苯乙烯-烯烴共聚合體、乙烯基甲苯-α-甲基苯乙烯共聚合體等之氫化物。 Examples of the hydride of the styrene resin include a hydrogenated product of a homopolymer of a styrene monomer, a styrene-olefin copolymer, and a vinyltoluene-α-methylstyrene copolymer.
本發明之黏著賦予劑之氫化率為50%以上且未滿90%之範圍內，較佳為55%以上且80%以下之範圍內，尤佳為60%以上且70%以下之範圍內。 The hydrogenation rate of the adhesion-imparting agent of the present invention is in the range of 50% or more and less than 90%, preferably in the range of 55% or more and 80% or less, and more preferably in the range of 60% or more and 70% or less.
若氫化率於上述範圍內，則可以更少量而獲得具有所需之黏著力之感壓型黏著薄膜或片，因此可減少黏著賦予劑之使用量。 When the hydrogenation ratio is within the above range, a pressure-sensitive adhesive film or sheet having a desired adhesive strength can be obtained in a smaller amount, so that the amount of the adhesion-imparting agent can be reduced.
再者，上述氫化率可利用上述專利文獻3(日本專利特開2010-171419號公報)中記載之NMR(Nuclear Magnetic Resonance，核磁共振)測定法進行測定。具體而言，根據黏著賦予劑出現於1H-NMR之7ppm附近之芳環之H-圖譜面積並基於以下之(1)式進行計算。 In addition, the hydrogenation rate can be measured by the NMR (Nuclear Magnetic Resonance) measurement method described in the above-mentioned Patent Document 3 (JP-A-2010-171419). Specifically, the H-map area of the aromatic ring which appears in the vicinity of 7 ppm of 1H-NMR according to the adhesion-imparting agent is calculated based on the following formula (1).
氫化率={1-(黏著賦予劑之氫化物之圖譜面積/未氫化黏著賦予劑之圖譜面積)}×100(%)…(1) Hydrogenation rate = {1 - (area of the hydride of the adhesion-imparting agent / area of the map of the unhydrogenated adhesion-imparting agent)} × 100 (%) (1)
黏著賦予劑並無特別限定，依據JIS K2207-1996環球法而測定之軟化溫度較佳為80℃以上，更佳為85℃以上。若軟化溫度為上述下限值以上，則所獲得之感壓型黏著薄膜或片之初始黏著力更優異，且處理性亦優異。 The adhesion-imparting agent is not particularly limited, and the softening temperature measured according to the GIS K2207-1996 ring method is preferably 80 ° C or higher, more preferably 85 ° C or higher. When the softening temperature is at least the above lower limit value, the pressure-sensitive adhesive film or sheet obtained is excellent in initial adhesion and excellent in handleability.
又，黏著賦予劑並無特別限定，依據JIS K2207-1996環球法而測定之軟化溫度較佳為150℃以下，更佳為140℃以下。若軟化溫度為上述上限值以下，則可進一步抑制所獲得之感壓型黏著薄膜或片之黏著亢進。 Further, the adhesion-imparting agent is not particularly limited, and the softening temperature measured according to the GIS K2207-1996 ring method is preferably 150 ° C or lower, more preferably 140 ° C or lower. When the softening temperature is at most the above upper limit value, the adhesion of the pressure-sensitive adhesive film or sheet obtained can be further suppressed.
本實施形態之黏著賦予劑之含量並無特別限定，於將上述乙烯-乙酸乙烯酯共聚合體、與上述黏著賦予劑之合計量設為100質量份時，較佳為0.1質量份以上，更佳為0.3質量份以上，尤佳為0.5質量份以上。若黏著賦予劑之含量為上述下限值以上，則可獲得初始黏著力更優異之感壓型黏著薄膜或片。 The content of the adhesion-imparting agent of the present embodiment is not particularly limited, and when the total amount of the ethylene-vinyl acetate copolymer and the adhesion-imparting agent is 100 parts by mass, it is preferably 0.1 part by mass or more, and more preferably It is 0.3 parts by mass or more, and particularly preferably 0.5 parts by mass or more. When the content of the adhesion-imparting agent is at least the above lower limit value, a pressure-sensitive adhesive film or sheet having more excellent initial adhesion can be obtained.
又，上述黏著賦予劑之含量較佳為5.0質量份以下，更佳為3.0質量份以下，進而較佳為2.2質量份以下，尤佳為1.5質量份以下。若黏著賦予劑之含量為上述上限值以下，則可獲得黏著力之經時性亢進之 抑制、與對被黏附體之耐污染性之平衡更優異之感壓型黏著薄膜或片。 Further, the content of the adhesion-imparting agent is preferably 5.0 parts by mass or less, more preferably 3.0 parts by mass or less, further preferably 2.2 parts by mass or less, and particularly preferably 1.5 parts by mass or less. If the content of the adhesion-imparting agent is less than or equal to the above upper limit value, the adhesiveness is improved over time. A pressure-sensitive adhesive film or sheet that is more excellent in suppressing the balance with the stain resistance of the adherend.
又，本實施形態之黏著層中，亦可以無損黏著層之特性之程度，進而調配抗氧化劑、紫外線吸收劑、光穩定劑、及抗黏連劑(anti blocking agent)等高分子領域中通常使用之添加劑。 Further, in the adhesive layer of the present embodiment, the characteristics of the adhesive layer can be prevented, and the polymer, such as an antioxidant, an ultraviolet absorber, a light stabilizer, and an anti blocking agent, can be used in a polymer field. Additives.
本實施形態之感壓型黏著薄膜或片係例如藉由使包含上述乙烯-乙酸乙烯酯共聚合體、及上述黏著賦予劑之樹脂組成物成形為單層薄膜或片狀而獲得。於該情形時，所獲得之單層薄膜或片相當於本實施形態之黏著層。又，亦可藉由使用上述樹脂組成物於基材之至少一面形成黏著層而獲得。 The pressure-sensitive adhesive film or sheet of the present embodiment is obtained, for example, by molding a resin composition containing the ethylene-vinyl acetate copolymer and the adhesion-imparting agent into a single-layer film or sheet. In this case, the obtained single-layer film or sheet corresponds to the adhesive layer of the present embodiment. Further, it can also be obtained by forming an adhesive layer on at least one side of the substrate using the above resin composition.
通常，使用後者之使用上述樹脂組成物於基材之至少一面形成黏著層的方法。 Usually, a method of forming an adhesive layer on at least one side of a substrate using the above resin composition is used.
於使由上述樹脂組成物所構成之黏著層形成於基材之至少一面之情形時，作為所使用之基材，並無特別限定，可列舉使用聚酯、聚醯胺、聚烯烴等熱塑性樹脂之1種或2種以上而成之延伸或未延伸之各種熱塑性樹脂薄膜或片。 In the case where the adhesive layer composed of the resin composition is formed on at least one side of the substrate, the substrate to be used is not particularly limited, and examples thereof include thermoplastic resins such as polyester, polyamide, and polyolefin. One or two or more kinds of thermoplastic resin films or sheets which are extended or not extended.
此處，作為聚烯烴，可列舉：以聚丙烯、乙烯成分為共聚合成分之嵌段系或無規系之丙烯系聚合物；低密度聚乙烯、高密度聚乙烯、線性低密度或超低密度之聚乙烯等乙烯系聚合物；乙烯-丙烯共聚合體 等。 Here, examples of the polyolefin include a block system in which a polypropylene component and a vinyl component are copolymerized components, or a random propylene-based polymer; a low-density polyethylene, a high-density polyethylene, a linear low density or an ultra low temperature; Ethylene polymer such as polyethylene of density; ethylene-propylene copolymer Wait.
又，作為基材，亦可使用紙；金屬箔；不織布等。 Further, as the substrate, paper, metal foil, non-woven fabric or the like can also be used.
於本實施形態中，該等之中尤佳為包含聚乙烯、聚丙烯等聚烯烴之基材。 In the present embodiment, among these, a substrate comprising a polyolefin such as polyethylene or polypropylene is particularly preferable.
於使用包含聚烯烴之基材之情形時，可獲得黏著層與基材之層間接著性良好、又透明性優異之薄膜或片。 When a substrate containing a polyolefin is used, a film or sheet excellent in interlayer adhesion between the adhesive layer and the substrate and excellent in transparency can be obtained.
於基材使用熱塑性樹脂薄膜之情形時，為防止劣化等，視需要亦可於成為基材之熱塑性樹脂中進而調配例如抗氧化劑；紫外線吸收劑；受阻胺光穩定劑等光穩定劑；抗靜電劑；碳黑、氧化鈣、氧化鎂、氧化矽、氧化鋅、氧化鈦等填充劑或顏料等添加劑。 In the case where a thermoplastic resin film is used as the substrate, in order to prevent deterioration or the like, an antioxidant such as an antioxidant, a UV absorber, a hindered amine light stabilizer, or the like may be further formulated in a thermoplastic resin to be a substrate as needed; Additives such as fillers or pigments such as carbon black, calcium oxide, magnesium oxide, cerium oxide, zinc oxide, and titanium oxide.
基材之厚度並無特別限定，通常為1μm以上且500μm以下，較佳為10μm以上且200μm以下。 The thickness of the substrate is not particularly limited, but is usually 1 μm or more and 500 μm or less, and preferably 10 μm or more and 200 μm or less.
本實施形態之黏著層之形成所使用之上述樹脂組成物，例如藉由同時或逐次地乾摻或熔融摻合上述乙烯-乙酸乙烯酯共聚合體、上述黏著賦予劑、及視需要之其他添加劑而獲得。 The resin composition used for forming the adhesive layer of the present embodiment is, for example, simultaneously or sequentially blended or melt-blended with the ethylene-vinyl acetate copolymer, the adhesion-imparting agent, and other additives as needed. obtain.
乾摻時，可使用亨舍爾混合機、滾筒混合機等各種混合機。 In the case of dry blending, various mixers such as a Henschel mixer and a drum mixer can be used.
又，進行熔融摻合之情形時，可使用單軸或雙軸擠出機、班布里混合機、滾筒、捏合機等混練裝置，例如於140℃以上且230℃以下左右之溫度下進行熔融混練。 Further, in the case of melt blending, a kneading device such as a uniaxial or biaxial extruder, a Banbury mixer, a drum, or a kneader may be used, for example, melting at a temperature of about 140 ° C or more and 230 ° C or less. Mixed.
使包含本實施形態之樹脂組成物之黏著層形成至基材之方法例如 可依據如下之公知之方法而進行：將樹脂組成物之溶液或者熱熔融液塗佈於基材上之溶液塗佈法；依據溶液塗佈法塗佈於隔板基材上後，對所形成之黏著層進行轉移轉印之方法；將樹脂組成物擠出於基材上並進行形成塗佈之熱熔塗佈法；將基材與樹脂組成物以二層或三層以上之多層進行共擠出而成形之方法；於基材上將樹脂組成物以單層進行擠出層壓之方法；將接著層與樹脂組成物以二層進行擠出層壓之方法；將黏著層與薄膜或層壓層等支持基材形成材進行熱層壓之方法等。 A method of forming an adhesive layer containing the resin composition of the present embodiment to a substrate, for example It can be carried out according to a known method: a solution coating method in which a solution or a hot melt of a resin composition is applied onto a substrate; and after being applied to a separator substrate according to a solution coating method, the pair is formed. a method of transfer transfer of an adhesive layer; a hot melt coating method in which a resin composition is extruded on a substrate and a coating is formed; and the substrate and the resin composition are collectively composed of two or more layers. a method of extrusion molding; a method of extrusion laminating a resin composition in a single layer on a substrate; a method of extrusion laminating a bonding layer and a resin composition in two layers; and an adhesive layer and a film or A method of thermally laminating a substrate forming material such as a laminate layer or the like.
該等之中，較佳為將樹脂組成物與由熱塑性樹脂所構成之基材一併以利用膨脹法或T字模法之二層或三層以上之多層進行共擠出成形的方法。 Among these, a resin composition and a base material composed of a thermoplastic resin are preferably co-extruded by a plurality of layers of two or more layers by an expansion method or a T-die method.
於本實施形態中，形成於基材上之黏著層之厚度係根據黏著力等而適當地決定，通常較佳為設為1μm以上且250μm以下，進而較佳為設為5μm以上且100μm以下。 In the present embodiment, the thickness of the adhesive layer formed on the substrate is appropriately determined depending on the adhesive force or the like, and is usually preferably 1 μm or more and 250 μm or less, and more preferably 5 μm or more and 100 μm or less.
又，於不具有基材之單層薄膜或片之情形時，較佳為設為5μm以上且300μm以下，進而較佳為設為10μm以上且200μm以下。 Further, in the case of a single-layer film or sheet having no substrate, it is preferably 5 μm or more and 300 μm or less, and more preferably 10 μm or more and 200 μm or less.
本實施形態之感壓型黏著薄膜或片係以黏著層與較硬(剛性)之被黏附體之表面呈對向之方式不積極地進行加熱而僅利用壓力進行貼附。於不需要時用手容易地剝離，且於被黏附體之表面不殘留污染物。作為被黏附體，例如可列舉：合成樹脂板、裝飾層板、金屬板、塗裝鋼板等製品表面保護用等。 The pressure-sensitive adhesive film or sheet of the present embodiment is not actively heated so that the adhesive layer is opposed to the surface of the hard (rigid) adherend, and is attached only by pressure. It is easily peeled off by hand when it is not needed, and no contaminants remain on the surface of the adherend. Examples of the adherend include, for example, a surface of a product such as a synthetic resin sheet, a decorative laminate, a metal sheet, or a coated steel sheet.
又，可列舉：窗玻璃表面保護用、汽車之燒附塗裝時或印刷基板之焊料浸入時之表面保護用等。 Moreover, the surface protection for the surface protection of a window glass, the baking-coating of a car, or the soldering of a printed circuit board, etc. are mentioned.
進而，可列舉：作為液晶顯示裝置、電漿顯示裝置、有機薄膜EL(Electroluminescence，電致發光)裝置等之構成構件之液晶面板；反 射板、相位差板、角柱片、導光板、偏光板、電漿顯示面板、有機螢光體薄膜、透明電極、軟性印刷基板、剛性印刷基板等精密電子零件。本實施形態之感壓型黏著薄膜或片尤佳地用作該等表面保護用之薄膜或片。 Further, a liquid crystal panel which is a constituent member of a liquid crystal display device, a plasma display device, an organic thin film EL (Electroluminescence) device, or the like; Precision electronic components such as shot plates, phase difference plates, corner posts, light guide plates, polarizers, plasma display panels, organic phosphor films, transparent electrodes, flexible printed substrates, and rigid printed substrates. The pressure-sensitive adhesive film or sheet of the present embodiment is particularly preferably used as a film or sheet for surface protection.
作為其他本實施形態，可提供一種將上述感壓型黏著薄膜或片使用於保護物品表面之方法。成為表面保護之對象之物品例如可列舉上述被黏附體。 As another embodiment, a method of applying the pressure-sensitive adhesive film or sheet to protect the surface of the article can be provided. Examples of the article to be subjected to surface protection include the above-mentioned adherends.
以上，已對本發明之實施形態進行敍述，但該等為本發明之例示，亦可採用上述以外之各種構成。 The embodiments of the present invention have been described above, but these are examples of the present invention, and various configurations other than the above may be employed.
以下，利用實施例以及比較例說明本實施形態，但本實施形態並不限定於該等。 Hereinafter, the present embodiment will be described using the examples and the comparative examples, but the embodiment is not limited thereto.
實施例以及比較例中使用以下原料。 The following materials were used in the examples and comparative examples.
EVA1：乙烯-乙酸乙烯酯共聚合體(MFR=9g/10min，乙烯含量=90質量%，乙酸乙烯酯含量=10質量%) EVA1: ethylene-vinyl acetate copolymer (MFR = 9 g/10 min, ethylene content = 90% by mass, vinyl acetate content = 10% by mass)
黏著賦予劑1：脂環式飽和烴樹脂(荒川化學工業公司製造，Arkon M-90，軟化溫度90℃，氫化率60%以上且70%以下) Adhesive-imparting agent 1: alicyclic saturated hydrocarbon resin (manufactured by Arakawa Chemical Industries, Inc., Arkon M-90, softening temperature: 90 ° C, hydrogenation rate: 60% or more and 70% or less)
黏著賦予劑2：脂環式飽和烴樹脂(荒川化學工業公司製造，Arkon M-100，軟化溫度100℃，氫化率60%以上且70%以下) Adhesive-imparting agent 2: alicyclic saturated hydrocarbon resin (manufactured by Arakawa Chemical Industry Co., Ltd., Arkon M-100, softening temperature: 100 ° C, hydrogenation rate: 60% or more and 70% or less)
黏著賦予劑3：脂環式飽和烴樹脂(荒川化學工業公司製造，Arkon M-115，軟化溫度115℃，氫化率60%以上且70%以下) Adhesive-imparting agent 3: alicyclic saturated hydrocarbon resin (manufactured by Arakawa Chemical Industries, Inc., Arkon M-115, softening temperature: 115 ° C, hydrogenation rate: 60% or more and 70% or less)
黏著賦予劑4：脂環式飽和烴樹脂(荒川化學工業公司製造，Arkon M-135，軟化溫度135℃，氫化率60%以上且70%以下) Adhesive-imparting agent 4: alicyclic saturated hydrocarbon resin (manufactured by Arakawa Chemical Industries, Inc., Arkon M-135, softening temperature 135 ° C, hydrogenation rate of 60% or more and 70% or less)
黏著賦予劑5：脂環式飽和烴樹脂(荒川化學工業公司製造，Arkon P-100，軟化溫度100℃，氫化率90%以上) Adhesive-imparting agent 5: alicyclic saturated hydrocarbon resin (manufactured by Arakawa Chemical Industries, Inc., Arkon P-100, softening temperature: 100 ° C, hydrogenation rate: 90% or more)
．MFR：JIS K7210-1999(190℃，2160g載重) . MFR: JIS K7210-1999 (190 ° C, 2160 g load)
．軟化溫度：JIS K2207-1996(環球法) . Softening temperature: JIS K2207-1996 (Global Law)
使用40mm T字模成形機(NAKATANI機械公司製造)，對表1中記載之調配比例(質量份)之樹脂組成物以厚度90μm進行擠出加工，製作評價用薄膜。擠出加工係於樹脂溫度約180℃、加工速度10m/min之條件下進行。 Use 40mm The T-shaped molding machine (manufactured by NAKATANI Machinery Co., Ltd.) was subjected to extrusion processing on a resin composition having a blending ratio (parts by mass) described in Table 1 at a thickness of 90 μm to prepare a film for evaluation. The extrusion processing was carried out under the conditions of a resin temperature of about 180 ° C and a processing speed of 10 m / min.
依據JIS Z0237，將評價用薄膜(25mm寬)與作為被黏附體之丙烯酸系板(寬度30mm、長度150mm、厚度2mm)重疊，利用手動式輥(45mm寬，重量2Kg)壓合2次往返，獲得評價用樣品。將其於23℃×50%RH環境下靜置30分鐘後，以抽取速度=300mm/min、180度之角度進行剝離，進行黏著力之評價。再者，於本評價中，為減少測定差異之影響，各實施5次測定，將對最大值與最小值除外之3次測定值求得之平均值用作黏著力。 According to JIS Z0237, the film for evaluation (25 mm width) and the acrylic plate (width: 30 mm, length: 150 mm, thickness: 2 mm) as the adherend were superposed, and the manual roll (45 mm width, weight: 2 kg) was pressed twice. A sample for evaluation was obtained. This was allowed to stand in an environment of 23 ° C × 50% RH for 30 minutes, and then peeled off at an extraction speed of 300 mm/min and 180 degrees to evaluate the adhesion. In addition, in this evaluation, in order to reduce the influence of the measurement difference, the measurement was performed five times each, and the average value obtained from the three measurement values except the maximum value and the minimum value was used as the adhesion.
將以上之評價結果匯總於表1。 The above evaluation results are summarized in Table 1.
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| CN1142437A (en) * | 1995-06-08 | 1997-02-12 | 积水化学工业株式会社 | Middle film for laminated glass and the laminated glass products for the side windows of vehicles |
| TW200942591A (en) * | 2008-02-05 | 2009-10-16 | Mitsui Du Pont Polychemical | Tacky resin composition and pressure-sensitive adhesive film or sheet |
| JP2010171419A (en) * | 2008-12-27 | 2010-08-05 | Arakawa Chem Ind Co Ltd | Sealing material sheet for solar cell |
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| CN1142437A (en) * | 1995-06-08 | 1997-02-12 | 积水化学工业株式会社 | Middle film for laminated glass and the laminated glass products for the side windows of vehicles |
| TW200942591A (en) * | 2008-02-05 | 2009-10-16 | Mitsui Du Pont Polychemical | Tacky resin composition and pressure-sensitive adhesive film or sheet |
| JP2010171419A (en) * | 2008-12-27 | 2010-08-05 | Arakawa Chem Ind Co Ltd | Sealing material sheet for solar cell |
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