TWI661020B - Urethane-based pressure-sensitive adhesive and surface protective film using the pressure-sensitive adhesive - Google Patents
Urethane-based pressure-sensitive adhesive and surface protective film using the pressure-sensitive adhesive Download PDFInfo
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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- G—PHYSICS
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/16—Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings
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- G—PHYSICS
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
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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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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Abstract
本發明提供一種抗靜電性非常優異,抗糊劑殘留性或二次加工性亦優異之胺甲酸乙酯系黏著劑。又,本發明提供一種表面保護膜,其係將此種胺甲酸乙酯系黏著劑用於黏著劑層者,且抗靜電性非常優異,抗糊劑殘留性或二次加工性亦優異。又,本發明提供一種貼附有此種表面保護膜之光學構件或電子構件。本發明之胺甲酸乙酯系黏著劑係包含胺甲酸乙酯系樹脂之胺甲酸乙酯系黏著劑,且該胺甲酸乙酯系樹脂係將含有多元醇(A)及多官能異氰酸酯化合物(B)之組合物硬化而獲得之胺甲酸乙酯系樹脂;該多元醇(A)與該多官能異氰酸酯化合物(B)中之NCO基與OH基之當量比以NCO基/OH基計,超過1.0且為5.0以下;該胺甲酸乙酯系黏著劑包含含有氟有機陰離子之離子性液體。 The present invention provides a urethane-based adhesive that is very excellent in antistatic properties and excellent in paste residue resistance or secondary processability. In addition, the present invention provides a surface protective film, which uses such a urethane-based adhesive for an adhesive layer, and has very good antistatic properties, and excellent paste residue resistance or secondary processability. The present invention also provides an optical member or an electronic member to which such a surface protective film is attached. The urethane-based adhesive of the present invention is an urethane-based adhesive containing a urethane-based resin, and the urethane-based resin will contain a polyol (A) and a polyfunctional isocyanate compound (B Urethane resin obtained by curing the composition; the equivalent ratio of NCO group to OH group in the polyol (A) and the polyfunctional isocyanate compound (B) is more than 1.0 in terms of NCO group / OH group It is 5.0 or less; the urethane-based adhesive contains an ionic liquid containing a fluorine organic anion.
Description
本發明係關於一種胺甲酸乙酯系黏著劑。本發明之胺甲酸乙酯系黏著劑儘管為先前通常作為容易糊劑殘留者而已知之胺甲酸乙酯系黏著劑,但抗糊劑殘留性非常優異。本發明又關於一種使用此種胺甲酸乙酯系黏著劑之表面保護膜。本發明之表面保護膜具有基材層及黏著劑層,並較佳用於例如貼附於光學構件或電子構件之表面以保護該表面之用途。 The present invention relates to a urethane-based adhesive. Although the urethane-based adhesive of the present invention is an urethane-based adhesive generally known as a paste-sustaining agent, it is excellent in paste-resistance. The present invention also relates to a surface protection film using such a urethane-based adhesive. The surface protection film of the present invention has a base material layer and an adhesive layer, and is preferably used, for example, for attaching a surface of an optical member or an electronic member to protect the surface.
LCD(liquid crystal display,液晶顯示器)、有機EL(Electro-Luminescence,電激發光)顯示器、使用該等之觸控面板、照相機之透鏡部、電子設備等光學構件或電子構件,為防止於加工、組裝、檢查、運輸等時之表面之損傷,通常於露出面側貼附有表面保護膜。於無需表面保護之時間點,將此種表面保護膜自光學構件或電子構件剝離。 LCD (liquid crystal display, liquid crystal display), organic EL (Electro-Luminescence) display, the use of such touch panels, camera lens parts, electronic components such as electronic devices or electronic components, in order to prevent processing, For surface damage during assembly, inspection, and transportation, a surface protective film is usually attached to the exposed surface. At the point when no surface protection is required, such a surface protection film is peeled from the optical member or the electronic member.
此種表面保護膜,自光學構件或電子構件之製造步驟,經過組裝步驟、檢查步驟、運輸步驟等,直至最終出貨,持續使用相同之表面保護膜之情況日益增多。於該情形時,此種表面保護膜於各步驟中藉由手工作業而貼附、剝離、再貼附之情形較多。 Such surface protection films are increasingly used from the manufacturing steps of optical components or electronic components, through assembly steps, inspection steps, transportation steps, etc., until the final shipment, and the same surface protection film is continuously used. In this case, such a surface protection film is often attached, peeled off, and reattached by manual operation in each step.
於藉由手工作業而貼附表面保護膜之情形時,有於被接著體與表面保護膜之間捲入氣泡之情形。因此,報告有一些用以提高表面保護膜之潤濕性,以於貼附時不捲入氣泡之技術。例如,已知黏著劑層使用具有潤濕速率較快之矽酮樹脂之表面保護膜。然而,於將矽酮樹脂用於黏著劑層之情形時,其黏著劑成分易於污染被接著體,從而於用作用以保護光學構件或電子構件等特別要求低污染之構件之表面的表面保護膜時有問題。 When the surface protection film is attached by hand, there may be a case where air bubbles are caught between the adherend and the surface protection film. Therefore, there are some techniques reported to improve the wettability of the surface protection film so that air bubbles are not involved during the attachment. For example, it is known that the adhesive layer uses a surface protective film having a silicone resin with a faster wetting rate. However, when a silicone resin is used for the adhesive layer, the adhesive component tends to contaminate the adherend, and thus it is used as a surface protective film for protecting the surface of a member requiring particularly low pollution such as an optical member or an electronic member. There are problems.
作為源自黏著劑成分之污染較少之表面保護膜,已知黏著劑層使用丙烯酸系樹脂之表面保護膜。然而,黏著劑層使用丙烯酸系樹脂之表面保護膜的潤濕性較差,因此,於藉由手工作業而貼附表面保護膜之情形時,有於被接著體與表面保護膜之間捲入氣泡之情形。另外,於將丙烯酸系樹脂用於黏著劑層之情形時,有於剝離時易於產生糊劑殘留之問題,從而用作用以保護光學構件或電子構件等特別避忌雜質混入之構件之表面的表面保護膜時有問題。 As a surface protection film with less contamination due to an adhesive component, it is known to use an acrylic resin surface protection film for the adhesive layer. However, the surface protective film using an acrylic resin for the adhesive layer has poor wettability. Therefore, when the surface protective film is attached by hand, bubbles may be caught between the adherend and the surface protective film. Situation. In addition, when an acrylic resin is used for an adhesive layer, there is a problem that a paste residue is liable to occur during peeling, and thus it is used as a surface protection for protecting the surface of a member such as an optical member or an electronic member that is particularly resistant to the inclusion of impurities. There is a problem with the membrane.
作為可兼具優異之潤濕性、低污染性、以及糊劑殘留減少之表面保護膜,最近報告有黏著劑層使用胺甲酸乙酯系黏著劑之表面保護膜(例如參照專利文獻1)。 As a surface protective film that can have both excellent wettability, low staining properties, and reduced paste residue, a surface protective film using a urethane-based adhesive as an adhesive layer has recently been reported (for example, refer to Patent Document 1).
然而,先前之胺甲酸乙酯系黏著劑作為易於糊劑殘留者為已知。例如,若於貼附於被接著體之後於加溫狀態下保存,則有易於在被接著體上產生糊劑殘留之問題。 However, conventional urethane-based adhesives are known as those which are liable to paste residue. For example, if it is stored in a heated state after being attached to an adherend, there is a problem that a paste residue is liable to be generated on the adherend.
另外,於將表面保護膜以手工作業而貼附於被接著體之情形時,要求優異之潤濕性,並且輕剝離性。其原因在於,於將貼附於被接著體之表面保護膜剝離之後,重新貼附於被接著體並再次用作表面保護膜。即便潤濕性良好,若剝離較重,則於剝離表面保護膜時該表面保護膜發生變形,從而無法再次用作表面保護膜。為了避免此種問題,用於光學構件或電子構件之表面保護膜強烈要求所謂之再加工 性:可多次貼附而不捲入氣泡並且可較輕剝離而不變形。然而,迄今報告之黏著劑層使用胺甲酸乙酯系黏著劑之表面保護膜有如下問題:使黏著劑層之黏著力經時上升性較高,貼附於被接著體之狀態長期持續,則重剝離化且再加工性較差。 In addition, when a surface protection film is attached to a to-be-adhered body by a manual operation, excellent wettability and light peelability are required. The reason for this is that after the surface protective film attached to the adherend is peeled off, it is reattached to the adherend and used again as the surface protective film. Even if the wettability is good, if the peeling is heavy, the surface protective film is deformed when the surface protective film is peeled, so that it cannot be used as a surface protective film again. In order to avoid such a problem, a surface protective film for an optical member or an electronic member is strongly requested for so-called reprocessing. Properties: Can be attached multiple times without being trapped in air bubbles and can be peeled off lightly without deformation. However, the surface protective film using a urethane-based adhesive for the adhesive layer reported so far has the following problems: the adhesive force of the adhesive layer is increased over time, and the state of being adhered to the adherend is sustained for a long period of time. Peeling and poor reworkability.
另外,如上文所述,於無需表面保護之時間點將表面保護膜自光學構件或電子構件等被接著體剝離。此時,表面保護膜之基材層、或光學構件、或電子構件等包含塑膠材料作為構成材料因此電絕緣性較高,於摩擦或剝離時產生靜電。因此,於將表面保護膜自偏光板等光學構件剝離時亦產生靜電,若於殘留此種靜電之狀態下對液晶施加電壓,則液晶分子之配向損失或者產生面板之缺損。 In addition, as described above, the surface protection film is peeled from the adherend such as an optical member or an electronic member at a point in time when no surface protection is required. At this time, the base material layer of the surface protection film, the optical member, or the electronic member contains a plastic material as a constituent material, and therefore has high electrical insulation properties, and generates static electricity during friction or peeling. Therefore, static electricity is also generated when the surface protective film is peeled off from an optical member such as a polarizing plate. If a voltage is applied to the liquid crystal in a state where such static electricity remains, the alignment of the liquid crystal molecules is lost or the panel is damaged.
[專利文獻1]日本專利特開2006-182795 [Patent Document 1] Japanese Patent Laid-Open No. 2006-182795
本發明之課題在於提供一種胺甲酸乙酯系黏著劑,其抗靜電性非常優異並且抗糊劑殘留性或再加工性亦優異。本發明之課題在於提供一種表面保護膜,其係黏著劑層使用此種胺甲酸乙酯系黏著劑者,且抗靜電性非常優異並且抗糊劑殘留性或再加工性亦優異。本發明之課題在於提供一種貼附有此種表面保護膜之光學構件或電子構件。 The object of the present invention is to provide a urethane-based adhesive, which is very excellent in antistatic properties and excellent in paste residue resistance and reworkability. The object of the present invention is to provide a surface protection film whose adhesive layer uses such a urethane-based adhesive, and which has excellent antistatic properties and excellent paste residue or reworkability. An object of the present invention is to provide an optical member or an electronic member to which such a surface protective film is attached.
本發明之胺甲酸乙酯系黏著劑係包含胺甲酸乙酯系樹脂者,且該胺甲酸乙酯系樹脂係將包含多元醇(A)及多官能異氰酸酯化合物(B)之組合物硬化而獲得之胺甲酸乙酯系樹脂;該多元醇(A)與該多官能異氰酸酯化合物(B)中之NCO基與OH基之當量比以NCO基/OH基計超過1.0且為5.0以下;且 該胺甲酸乙酯系黏著劑包含含有氟有機陰離子之離子性液體。 The urethane-based adhesive of the present invention includes a urethane-based resin, and the urethane-based resin is obtained by curing a composition containing a polyol (A) and a polyfunctional isocyanate compound (B). An urethane-based resin; the equivalent ratio of the NCO group to the OH group in the polyol (A) and the polyfunctional isocyanate compound (B) exceeds 1.0 and is 5.0 or less based on the NCO group / OH group; and This urethane-based adhesive contains an ionic liquid containing a fluorine organic anion.
於較佳之實施形態中,上述離子性液體由上述氟有機陰離子與鎓陽離子構成。 In a preferred embodiment, the ionic liquid is composed of the fluorine organic anion and the onium cation.
於較佳之實施形態中,上述鎓陽離子係選自含氮鎓陽離子、含硫鎓陽離子及含磷鎓陽離子中之至少一種。 In a preferred embodiment, the onium cation is at least one selected from the group consisting of a nitrogen-containing cation, a sulfur-containing cation, and a phosphorus-containing cation.
於較佳之實施形態中,上述多元醇(A)包含數量平均分子量Mn為400~20000之多元醇。 In a preferred embodiment, the polyol (A) includes a polyol having a number average molecular weight Mn of 400 to 20,000.
於較佳之實施形態中,上述多官能異氰酸酯化合物(B)相對於上述多元醇(A)之含有比率為5重量%~60重量%。 In a preferred embodiment, the content ratio of the polyfunctional isocyanate compound (B) to the polyol (A) is 5 to 60% by weight.
本發明之表面保護膜具有:基材層及黏著劑層,該黏著劑層包含本發明之胺甲酸乙酯系黏著劑。 The surface protection film of the present invention includes a substrate layer and an adhesive layer, and the adhesive layer includes the urethane-based adhesive of the present invention.
本發明之光學構件係貼附有本發明之表面保護膜者。 The optical member of the present invention is one to which the surface protective film of the present invention is attached.
本發明之電子構件係貼附有本發明之表面保護膜者。 The electronic component of the present invention is one to which the surface protective film of the present invention is attached.
根據本發明,可提供一種抗靜電性非常優異並且抗糊劑殘留性或再加工性亦優異之胺甲酸乙酯系黏著劑。又,根據本發明,可提供一種表面保護膜,其係黏著劑層使用此種胺甲酸乙酯系黏著劑者,且抗靜電性非常優異並且抗糊劑殘留性或再加工性亦優異。又,根據本發明,可提供一種貼附有此種表面保護膜之光學構件或電子構件。 According to the present invention, it is possible to provide an urethane-based adhesive which is very excellent in antistatic properties and excellent in paste residue resistance or reworkability. In addition, according to the present invention, a surface protective film can be provided in which the urethane-based adhesive is used as the adhesive layer, and the antistatic property is very excellent, and the paste residual property or reworkability is also excellent. Furthermore, according to the present invention, it is possible to provide an optical member or an electronic member to which such a surface protection film is attached.
1‧‧‧基材層 1‧‧‧ substrate layer
2‧‧‧黏著劑層 2‧‧‧ Adhesive layer
10‧‧‧表面保護膜 10‧‧‧ surface protective film
圖1係本發明之較佳之實施形態之表面保護膜的概略剖面圖。 FIG. 1 is a schematic cross-sectional view of a surface protective film according to a preferred embodiment of the present invention.
本發明之胺甲酸乙酯系黏著劑包含胺甲酸乙酯系樹脂。 The urethane-based adhesive of the present invention contains a urethane-based resin.
本發明之胺甲酸乙酯系樹脂於胺甲酸乙酯系黏著劑中之含有比率之下限值較佳為40重量%以上,更佳為50重量%以上,進而較佳為55重量%以上,進而較佳為60重量%,特別較佳為65重量%,最佳為70重量%,上限值較佳為99.999重量%以下,更佳為99.99重量%以下,進而較佳為99.9重量%以下,進而較佳為99重量%以下,特別較佳為95重量%以下,最佳為90重量%以下。將本發明之胺甲酸乙酯系樹脂於胺甲酸乙酯系黏著劑中之含有比率於上述範圍內調整,可提供一種例如抗靜電性非常優異並且抗糊劑殘留性或再加工性亦優異之胺甲酸乙酯系黏著劑。 The lower limit value of the content ratio of the urethane-based resin in the urethane-based adhesive of the present invention is preferably 40% by weight or more, more preferably 50% by weight or more, and still more preferably 55% by weight or more. It is more preferably 60% by weight, particularly preferably 65% by weight, most preferably 70% by weight, and the upper limit value is preferably 99.999% by weight or less, more preferably 99.99% by weight or less, and still more preferably 99.9% by weight or less. It is further preferably 99% by weight or less, particularly preferably 95% by weight or less, and most preferably 90% by weight or less. Adjusting the content ratio of the urethane-based resin in the urethane-based adhesive of the present invention within the above-mentioned range can provide, for example, a very excellent antistatic property and excellent anti-paste residue or reworkability. Urethane-based adhesive.
胺甲酸乙酯系樹脂係將含有多元醇(A)及多官能異氰酸酯化合物(B)之組合物硬化而獲得之胺甲酸乙酯系樹脂。 The urethane-based resin is an urethane-based resin obtained by curing a composition containing a polyol (A) and a polyfunctional isocyanate compound (B).
作為多元醇(A),可僅為一種,或者可為兩種以上。 As the polyol (A), there may be only one kind, or two or more kinds.
作為多元醇(A),只要為具有兩個以上之OH基之多元醇即可,可採用任何適當之多元醇。作為此種多元醇(A),例如可列舉具有兩個OH基之多元醇(二醇)、具有三個OH基之多元醇(三醇)、具有四個OH基之多元醇(四醇)、具有五個OH基之多元醇(五醇),及具有六個OH基之多元醇(六醇)等。 As the polyol (A), any polyol may be used as long as it is a polyol having two or more OH groups. Examples of such a polyol (A) include a polyol (diol) having two OH groups, a polyol (triol) having three OH groups, and a polyol (tetraol) having four OH groups. , A polyol (pentaol) having five OH groups, and a polyol (hexaol) having six OH groups.
於本發明中,作為多元醇(A),較佳為採用具有三個OH基之多元醇(三醇)作為必需成分。若如此作為多元醇(A),採用具有三個OH基之多元醇(三醇)作為必需成分,則可提供一種例如抗靜電性非常優異並且抗糊劑殘留性或再加工性亦優異之胺甲酸乙酯系黏著劑。具有三個OH基之多元醇(三醇)於多元醇(A)中之含有比率較佳為50重量%~100重量%,更佳為70重量%~100重量%,進而較佳為80重量%~100重量%,進而較佳為90重量%~100重量%,特別較佳為95重量%~100重量%,最佳為實質上100重量%。 In the present invention, as the polyol (A), a polyol (triol) having three OH groups is preferably used as an essential component. By using a polyhydric alcohol (triol) having three OH groups as an essential component as the polyhydric alcohol (A) in this way, it is possible to provide, for example, an amine having excellent antistatic properties and excellent paste residue or reworkability. Ethyl formate-based adhesive. The content ratio of the polyol (triol) having three OH groups in the polyol (A) is preferably 50% to 100% by weight, more preferably 70% to 100% by weight, and even more preferably 80% by weight. % To 100% by weight, more preferably 90% to 100% by weight, particularly preferably 95% to 100% by weight, and most preferably substantially 100% by weight.
作為多元醇(A),較佳為包含數量平均分子量Mn為400~20000之 多元醇。數量平均分子量Mn為400~20000之多元醇於多元醇(A)中之含有比率較佳為50重量%~100重量%,更佳為70重量%~100重量%,進而較佳為90重量%~100重量%,特別較佳為95重量%~100重量%,最佳為實質上100重量%。將數量平均分子量Mn為400~20000之多元醇於多元醇(A)中之含有比率於上述範圍內調整,可提供一種抗靜電性非常優異並且抗糊劑殘留性或再加工性亦優異之胺甲酸乙酯系黏著劑。 As the polyol (A), it is preferred to include a number average molecular weight Mn of 400 to 20,000. Polyol. The content ratio of the polyol having a number average molecular weight Mn of 400 to 20,000 in the polyol (A) is preferably 50% to 100% by weight, more preferably 70% to 100% by weight, and even more preferably 90% by weight. ~ 100% by weight, particularly preferably from 95% to 100% by weight, and most preferably substantially 100% by weight. Adjusting the content ratio of the polyol with a number average molecular weight Mn of 400 to 20,000 in the polyol (A) within the above range can provide an amine having excellent antistatic properties and excellent paste residue or reworkability. Ethyl formate-based adhesive.
於本發明中,作為多元醇(A),於採用具有三個OH基之多元醇(三醇)作為必需成分之情形時,較佳為併用數量平均分子量Mn為7000~20000之三醇、數量平均分子量Mn為2000~6000之三醇及數量平均分子量Mn為400~1900之三醇,更佳為併用數量平均分子量Mn為8000~15000之三醇、數量平均分子量Mn為2000~5000之三醇及數量平均分子量Mn為500~1800之三醇,且進而較佳為併用數量平均分子量Mn為8000~12000之三醇、數量平均分子量Mn為2000~4000之三醇及數量平均分子量Mn為500~1500之三醇。若併用上述三種三醇,則可提供一種例如抗靜電性非常優異並且抗糊劑殘留性或再加工性亦優異之胺甲酸乙酯系黏著劑。 In the present invention, when a polyol (triol) having three OH groups is used as an essential component as the polyol (A), it is preferred to use a triol having a number average molecular weight Mn of 7,000 to 20,000 in combination. Triol having an average molecular weight Mn of 2,000 to 6000 and triol having a number average molecular weight Mn of 400 to 1900, more preferably a triol having a number average molecular weight Mn of 8000 to 15000 and a triol having a number average molecular weight Mn of 2,000 to 5,000 And triol having a number average molecular weight Mn of 500 to 1800, and further preferably a triol having a number average molecular weight Mn of 8000 to 12000, a triol having a number average molecular weight Mn of 2000 to 4000, and a number average molecular weight Mn of 500 to 1500 triol. When the three triols are used in combination, for example, a urethane-based adhesive having excellent antistatic properties and excellent paste residue or reworkability can be provided.
作為多元醇(A),例如可列舉:聚酯多元醇、聚醚多元醇、聚己內酯多元醇、聚碳酸酯多元醇、蓖麻油系多元醇等。 Examples of the polyol (A) include polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol, and castor oil-based polyol.
作為聚酯多元醇,例如可藉由多元醇成分與酸成分之酯化反應而獲得。 The polyester polyol can be obtained, for example, by an esterification reaction between a polyol component and an acid component.
作為多元醇成分,例如可列舉:乙二醇、二乙二醇、1,3-丁二醇、1,4-丁二醇、新戊二醇、3-甲基-1,5-戊二醇、2-丁基-2-乙基-1,3-丙二醇、2,4-二乙基-1,5-戊二醇、1,2-己二醇、1,6-己二醇、1,8-辛二醇、1,9-壬二醇、2-甲基-1,8-辛二醇、1,8-癸二醇、十八烷二醇、甘油、三羥甲基丙烷、季戊四醇、己三醇、聚丙二醇等。 Examples of the polyol component include ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, and 3-methyl-1,5-pentanediol. Alcohol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,8-decanediol, stearyl glycol, glycerol, trimethylolpropane , Pentaerythritol, hexanetriol, polypropylene glycol, etc.
作為酸成分,例如可列舉:琥珀酸、甲基琥珀酸、己二酸、庚二酸、壬二酸、癸二酸、1,12-十二烷二酸、1,14-十四烷二酸、二聚酸、2-甲基-1,4-環己烷二羧酸、2-乙基-1,4-環己烷二羧酸、對苯二甲酸、間苯二甲酸、鄰苯二甲酸、1,4-萘二羧酸、4,4'-聯苯二羧酸、該等之酸酐等。 Examples of the acid component include succinic acid, methylsuccinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, and 1,14-tetradecanedioic acid. Acid, dimer acid, 2-methyl-1,4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, o-benzene Dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, anhydrides thereof, and the like.
作為聚醚多元醇,例如可列舉:以水、低分子多元醇(丙二醇、乙二醇、甘油、三羥甲基丙烷、季戊四醇等)、雙酚類(雙酚A等)或二羥基苯(鄰苯二酚、間苯二酚、氫醌等)等為起始劑,對環氧乙烷、環氧丙烷、環氧丁烷等環氧烷進行加成聚合而獲得之聚醚多元醇。具體而言,例如可列舉:聚乙二醇、聚丙二醇、聚丁二醇等。 Examples of the polyether polyol include water, low molecular polyols (propylene glycol, ethylene glycol, glycerol, trimethylolpropane, pentaerythritol, etc.), bisphenols (bisphenol A, etc.), and dihydroxybenzene ( Catechol, resorcinol, hydroquinone, etc.) are polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide. Specific examples include polyethylene glycol, polypropylene glycol, and polybutylene glycol.
作為聚己內酯多元醇,例如可列舉:藉由ε-己內酯、σ-戊內酯等環狀酯單體之開環聚合而獲得之內酯系聚酯二醇等。 Examples of the polycaprolactone polyol include a lactone-based polyester diol obtained by ring-opening polymerization of a cyclic ester monomer such as ε-caprolactone and σ-valerolactone.
作為聚碳酸酯多元醇,例如可列舉:對上述多元醇成分與光氣進行縮聚反應而獲得之聚碳酸酯多元醇;藉由對多元醇成分與碳酸二甲酯、碳酸二乙酯、碳酸二丙酯、碳酸二異丙酯、碳酸二丁酯、碳酸乙基丁酯、碳酸伸乙酯、碳酸伸丙酯、碳酸二苯酯、碳酸二苄酯等碳酸二酯進行酯交換縮合而獲得之聚碳酸酯多元醇;將兩種以上之上述多元醇成分併用獲得之共聚聚碳酸酯多元醇;對上述各種聚碳酸酯多元醇與含羧基之化合物進行酯化反應而獲得之聚碳酸酯多元醇;藉由對上述各種聚碳酸酯多元醇與含羥基之化合物進行醚化反應而獲得之聚碳酸酯多元醇;對上述各種聚碳酸酯多元醇與酯化合物進行酯交換反應而獲得之聚碳酸酯多元醇;對上述各種聚碳酸酯多元醇與含羥基之化合物進行酯交換反應而獲得之聚碳酸酯多元醇;對上述各種聚碳酸酯多元醇與二羧酸化合物進行縮聚反應而獲得之聚酯系聚碳酸酯多元醇;對上述各種聚碳酸酯多元醇與環氧烷進行共聚反應而獲得之共聚聚醚系聚碳酸酯多元醇等。 Examples of the polycarbonate polyol include: a polycarbonate polyol obtained by performing a polycondensation reaction of the above-mentioned polyol component and phosgene; and a polyol component and dimethyl carbonate, diethyl carbonate, and dicarbonate It is obtained by transesterification of carbonic acid diesters such as propyl ester, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, and dibenzyl carbonate. Polycarbonate polyols; copolymerized polycarbonate polyols obtained by combining two or more of the above-mentioned polyol components; polycarbonate polyols obtained by esterifying the various polycarbonate polyols described above with carboxyl-containing compounds ; A polycarbonate polyol obtained by performing an etherification reaction on the above-mentioned various polycarbonate polyols and a hydroxyl-containing compound; a polycarbonate obtained by performing an ester interchange reaction on the above-mentioned various polycarbonate polyols and an ester compound Polyols; Polycarbonate polyols obtained by transesterifying the above-mentioned various polycarbonate polyols with hydroxyl-containing compounds; Polyester-based carboxylic acid compound obtained by a polycondensation reaction of a polycarbonate polyol; of the above polycarbonate polyol with an alkylene oxide obtained by the copolymerization of copolyether polycarbonate-based polyol.
作為蓖麻油系多元醇,例如可列舉:使蓖麻油脂肪酸與上述多元醇成分反應而獲得之蓖麻油系多元醇。具體而言例如可列舉:使蓖麻油脂肪酸與聚丙二醇反應而獲得之蓖麻油系多元醇。 Examples of the castor oil-based polyol include a castor oil-based polyol obtained by reacting a castor oil fatty acid with the above-mentioned polyol component. Specific examples include castor oil-based polyols obtained by reacting castor oil fatty acids with polypropylene glycol.
多官能異氰酸酯化合物(B)可僅為一種,或者可為兩種以上。 The polyfunctional isocyanate compound (B) may be only one kind, or may be two or more kinds.
作為多官能異氰酸酯化合物(B),可採用可用於胺基甲酸乙酯化反應之任意適當之多官能異氰酸酯化合物。作為此種多官能異氰酸酯化合物(B),例如可列舉:多官能脂肪族異氰酸酯化合物、多官能脂環族異氰酸酯化合物、多官能芳香族異氰酸酯化合物等。 As the polyfunctional isocyanate compound (B), any appropriate polyfunctional isocyanate compound that can be used in the urethane reaction can be used. Examples of such a polyfunctional isocyanate compound (B) include a polyfunctional aliphatic isocyanate compound, a polyfunctional alicyclic isocyanate compound, and a polyfunctional aromatic isocyanate compound.
作為多官能脂肪族異氰酸酯化合物,例如可列舉:三亞甲基二異氰酸酯、四亞甲基二異氰酸酯、六亞甲基二異氰酸酯、五亞甲基二異氰酸酯、1,2-伸丙基二異氰酸酯、1,3-伸丁基二異氰酸酯、伸十二烷基二異氰酸酯、2,4,4-三甲基六亞甲基二異氰酸酯等。 Examples of the polyfunctional aliphatic isocyanate compound include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, and 1 , 3-butylene diisocyanate, dodecyl diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc.
作為多官能脂環族異氰酸酯化合物,例如可列舉:1,3-環戊烯二異氰酸酯、1,3-環己烷二異氰酸酯、1,4-環己烷二異氰酸酯、異佛爾酮二異氰酸酯、氫化二苯基甲烷二異氰酸酯、氫化苯二亞甲基二異氰酸酯、氫化甲苯二異氰酸酯、氫化四甲基苯二亞甲基二異氰酸酯等。 Examples of the polyfunctional alicyclic isocyanate compound include 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, Hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, and the like.
作為多官能芳香族二異氰酸酯化合物,例如可列舉:苯二異氰酸酯、2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、2,2'-二苯基甲烷二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、4,4'-甲苯胺二異氰酸酯、4,4'-二苯基醚二異氰酸酯、4,4'-二苯基二異氰酸酯、1,5-萘二異氰酸酯、苯二亞甲基二異氰酸酯。 Examples of the polyfunctional aromatic diisocyanate compound include benzene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, and 4,4'- Diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, benzenediphenyl Methylene diisocyanate.
作為多官能異氰酸酯化合物(B),亦可列舉:如上所述之多官能異氰酸酯化合物之三羥甲基丙烷加合物、與水反應之縮二脲、具有異氰脲酸酯環之三聚物等。另外,亦可併用該等。 Examples of the polyfunctional isocyanate compound (B) include the trimethylolpropane adduct of the polyfunctional isocyanate compound described above, biuret that reacts with water, and a terpolymer having an isocyanurate ring. Wait. In addition, these may be used in combination.
多官能異氰酸酯化合物(B)之含有比率相對於多元醇(A),多官能異氰酸酯化合物(B)較佳為5重量%~60重量%,更佳為8重量%~60重 量%,進而較佳為10重量%~60重量%。將多官能異氰酸酯化合物(B)之含有比率於上述範圍內調整,可提供一種例如抗靜電性非常優異並且抗糊劑殘留性或再加工性亦優異之胺甲酸乙酯系黏著劑。 The content ratio of the polyfunctional isocyanate compound (B) is preferably 5 to 60% by weight, and more preferably 8 to 60% by weight relative to the polyol (A). The amount is preferably 10% by weight to 60% by weight. By adjusting the content ratio of the polyfunctional isocyanate compound (B) within the above range, for example, it is possible to provide an urethane-based adhesive that is very excellent in antistatic properties and excellent in paste residue resistance or reworkability.
多元醇(A)與多官能異氰酸酯化合物(B)中之NCO基與OH基之當量比以NCO基/OH基計超過1.0且為5.0以下,較佳為1.1~5.0,更佳為1.2~4.0,進而較佳為1.5~3.5,特別較佳為1.8~3.0。將NCO基/OH基之當量比於上述範圍內調整,可提供一種例如抗靜電性非常優異並且抗糊劑殘留性或再加工性亦優異之胺甲酸乙酯系黏著劑。 The equivalent ratio of the NCO group to the OH group in the polyol (A) and the polyfunctional isocyanate compound (B) exceeds 1.0 and is 5.0 or less in terms of the NCO group / OH group, preferably 1.1 to 5.0, and more preferably 1.2 to 4.0. , More preferably 1.5 to 3.5, and particularly preferably 1.8 to 3.0. Adjusting the equivalent ratio of the NCO group / OH group within the above range can provide, for example, an urethane-based adhesive that is very excellent in antistatic properties and excellent in paste residue resistance or reworkability.
胺甲酸乙酯系樹脂係將包含多元醇(A)及多官能異氰酸酯化合物(B)之組合物硬化而獲得。此種組合物中,於無損本發明之效果之範圍內,除了多元醇(A)及多官能異氰酸酯化合物(B)以外,亦可包含任意適當之其他成分。作為此種其他成分,例如可列舉:觸媒、胺甲酸乙酯系樹脂以外之其他樹脂成分、增黏劑、無機填充劑、有機填充劑、金屬粉末、顏料、箔狀物、軟化劑、塑化劑、抗老化劑、導電劑、抗氧化劑、紫外線吸收劑、光穩定劑、表面潤滑劑、調平劑、抗腐蝕劑、耐熱穩定劑、聚合抑制劑、潤滑劑、溶劑等。 The urethane-based resin is obtained by curing a composition containing a polyol (A) and a polyfunctional isocyanate compound (B). Such a composition may contain any appropriate other components in addition to the polyol (A) and the polyfunctional isocyanate compound (B), as long as the effect of the present invention is not impaired. Examples of such other components include catalysts, resin components other than urethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, and plastics. Chemical agents, anti-aging agents, conductive agents, antioxidants, ultraviolet absorbers, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat-resistant stabilizers, polymerization inhibitors, lubricants, solvents, etc.
胺甲酸乙酯系樹脂較佳為包含如抗氧化劑、紫外線吸收劑、光穩定劑之防劣化劑。藉由胺甲酸乙酯系樹脂包含防劣化劑,即便於貼附於被接著體之後於加溫狀態下保存,於被接著體亦不易產生糊劑殘留等抗糊劑殘留性優異。防劣化劑可僅為一種,或者可為兩種以上。作為防劣化劑,特別較佳為抗氧化劑。 The urethane-based resin preferably contains an anti-deterioration agent such as an antioxidant, an ultraviolet absorber, and a light stabilizer. Since the urethane-based resin contains an anti-deterioration agent, even if it is stored in a warmed state after being adhered to the adherend, it is difficult to cause paste residues such as paste residues to be excellent in the adherend. The anti-deterioration agent may be only one kind, or may be two or more kinds. As the deterioration preventing agent, an antioxidant is particularly preferable.
防劣化劑之含有比率相對於多元醇(A),較佳為0.01重量%~20重量%,更佳為0.02重量%~15重量%,進而較佳為0.03重量%~10重量%,進而較佳為0.05重量%~7重量%,進而較佳為0.1重量%~5重量%,特別較佳為0.1重量%~3重量%,最佳為0.1重量%~1重量%。將防劣化劑之含有比率於上述範圍內調整,即便於貼附於被接著體之後 於加溫狀態下保存,於被接著體上亦不易產生糊劑殘留等可使抗糊劑殘留性進一步優異。若防劣化劑之含有比率過少,則有變得無法充分表現抗糊劑殘留性之虞。若防劣化劑之含有比率過多,則有如下之虞:產生對成本方面不利之問題,產生無法維持黏著特性之問題,或者產生被接著體被污染之問題。 The content ratio of the anti-deterioration agent is preferably 0.01% to 20% by weight, more preferably 0.02% to 15% by weight, and still more preferably 0.03% to 10% by weight relative to the polyol (A). It is preferably 0.05% to 7% by weight, more preferably 0.1% to 5% by weight, particularly preferably 0.1% to 3% by weight, and most preferably 0.1% to 1% by weight. Adjust the content ratio of the anti-deterioration agent within the above range, even after attaching to the adherend It can be stored in a warmed state, and paste residues are not easily generated on the adherend, which can further improve paste residue resistance. If the content ratio of the anti-deterioration agent is too small, there is a possibility that the anti-paste residue property may not be sufficiently expressed. If the content ratio of the anti-deterioration agent is too large, there is a possibility that a problem that is disadvantageous in terms of cost, a problem that the adhesion characteristics cannot be maintained, or a problem that the adherend is contaminated.
作為抗氧化劑,例如可列舉:自由基鏈抑制劑、過氧化物分解劑等。 Examples of the antioxidant include a radical chain inhibitor, a peroxide decomposer, and the like.
作為自由基鏈抑制劑,例如可列舉:酚系抗氧化劑、胺系抗氧化劑等。 Examples of the free radical chain inhibitor include phenol-based antioxidants and amine-based antioxidants.
作為過氧化物分解劑,例如可列舉:硫系抗氧化劑、磷系抗氧化劑等。 Examples of the peroxide decomposition agent include sulfur-based antioxidants and phosphorus-based antioxidants.
作為酚系抗氧化劑,例如可列舉:單酚系抗氧化劑、雙酚系抗氧化劑、高分子型酚系抗氧化劑等。 Examples of the phenol-based antioxidant include a monophenol-based antioxidant, a bisphenol-based antioxidant, and a polymer-type phenol-based antioxidant.
作為單酚系抗氧化劑,例如可列舉:2,6-二-第三丁基-對甲酚、丁基化羥基茴香醚、2,6-二-第三丁基-4-乙基苯酚、硬脂基-β-(3,5-二-第三丁基-4-羥基苯基)丙酸酯等。 Examples of the monophenol-based antioxidant include 2,6-di-third-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-third-butyl-4-ethylphenol, Stearyl-β- (3,5-di-third-butyl-4-hydroxyphenyl) propionate and the like.
作為雙酚系抗氧化劑,例如可列舉:2,2'-亞甲基雙(4-甲基-6-第三丁基苯酚)、2,2'-亞甲基雙(4-乙基-6-第三丁基苯酚)、4,4'-硫代雙(3-甲基-6-第三丁基苯酚)、4,4'-亞丁基雙(3-甲基-6-第三丁基苯酚)、3,9-雙[1,1-二甲基-2-[β-(3-第三丁基-4-羥基-5-甲基苯基)丙醯氧基]乙基]2,4,8,10-四氧雜螺[5,5]十一烷等。 Examples of the bisphenol-based antioxidant include 2,2'-methylenebis (4-methyl-6-third-butylphenol) and 2,2'-methylenebis (4-ethyl- 6-third butylphenol), 4,4'-thiobis (3-methyl-6-third butylphenol), 4,4'-butylenebis (3-methyl-6-third Butylphenol), 3,9-bis [1,1-dimethyl-2- [β- (3-third-butyl-4-hydroxy-5-methylphenyl) propanyloxy] ethyl ] 2,4,8,10-tetraoxaspiro [5,5] undecane and the like.
作為高分子型酚系抗氧化劑,例如可列舉:1,1,3-三(2-甲基-4-羥基-5-第三丁基苯基)丁烷、1,3,5-三甲基-2,4,6-三(3,5-二-第三丁基-4-羥基苄基)苯、四-[亞甲基-3-(3',5'-二-第三丁基-4'-羥基苯基)丙酸酯]甲烷、二[3,3'-二-(4'-羥基-3'-第三丁基苯基)丁酸]乙二醇酯、1,3,5-三(3',5'-二-第三丁基-4'-羥基苄基)-均三嗪-2,4,6-(1H,3H,5H)三酮、生育 酚等。 Examples of the polymer-type phenolic antioxidant include 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane and 1,3,5-trimethyl -2,4,6-tris (3,5-di-third-butyl-4-hydroxybenzyl) benzene, tetra- [methylene-3- (3 ', 5'-di-third-butyl -4'-hydroxyphenyl) propionate] methane, di [3,3'-bis- (4'-hydroxy-3'-third butylphenyl) butanoic acid] ethylene glycol ester, 1, 3,5-tris (3 ', 5'-di-tertiary-butyl-4'-hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) trione, fertility Phenol and so on.
作為硫系抗氧化劑,例如可列舉:3,3'-硫代二丙酸二月桂酯、3,3'-硫代二丙酸二肉豆蔻酯、3,3'-硫代二丙酸二硬脂酯等。 Examples of the sulfur-based antioxidant include: 3,3'-thiodipropionate dilauryl, 3,3'-thiodipropionate dimyristyl, and 3,3'-thiodipropionate Stearyl ester, etc.
作為磷系抗氧化劑,例如可列舉:亞磷酸三苯酯、亞磷酸二苯基異癸酯、亞磷酸苯基二異癸酯等。 Examples of the phosphorus-based antioxidant include triphenyl phosphite, diphenyl isodecyl phosphite, and phenyl diisodecyl phosphite.
作為紫外線吸收劑,例如可列舉:二苯甲酮系紫外線吸收劑、苯并三唑系紫外線吸收劑、水楊酸系紫外線吸收劑、草醯替苯胺系紫外線吸收劑、氰基丙烯酸酯系紫外線吸收劑、三嗪系紫外線吸收劑等。 Examples of the ultraviolet absorber include a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a salicylic acid-based ultraviolet absorber, a chlorhexidine-based ultraviolet absorber, and a cyanoacrylate-based ultraviolet light Absorbers, triazine-based ultraviolet absorbers, and the like.
作為二苯甲酮系紫外線吸收劑,例如可列舉:2,4-二羥基二苯甲酮、2-羥基-4-甲氧基二苯甲酮、2-羥基-4-辛氧基二苯甲酮、2-羥基-4-十二烷氧基二苯甲酮、2,2'-二羥基-4-二甲氧基二苯甲酮、2,2'-二羥基-4,4'-二甲氧基二苯甲酮、2-羥基-4-甲氧基-5-磺基二苯甲酮、雙(2-甲氧基-4-羥基-5-苯甲醯基苯基)甲烷等。 Examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy-4-octyloxybenzophenone. Methanone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-dimethoxybenzophenone, 2,2'-dihydroxy-4,4 ' -Dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5-benzylidenephenyl) Methane, etc.
作為苯并三唑系紫外線吸收劑,例如可列舉:2-(2'-羥基-5'-甲基苯基)苯并三唑、2-(2'-羥基-5'-第三丁基苯基)苯并三唑、2-(2'-羥基-3',5'-二-第三丁基苯基)苯并三唑、2-(2'-羥基-3'-第三丁基-5'-甲基苯基)-5-氯苯并三唑、2-(2'-羥基-3',5'-二-第三丁基苯基)5-氯苯并三唑、2-(2'-羥基-3',5'-二-第三戊基苯基)苯并三唑、2-(2'-羥基-4'-辛氧基苯基)苯并三唑、2-[2'-羥基-3'-(3",4",5",6"-四氫苯二甲醯亞胺甲基)-5'-甲基苯基]苯并三唑、2,2'-亞甲基雙[4-(1,1,3,3-四甲基丁基)-6-(2H-苯并三唑-2-基)苯酚]、2-(2'-羥基-5'-甲基丙烯醯氧基苯基)-2H-苯并三唑等。 Examples of the benzotriazole-based ultraviolet absorber include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-5'-third butyl) Phenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tertiary butyl -5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-third-butylphenyl) 5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-third-pentylphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- [2'-Hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydroxylylenediimidemethyl) -5'-methylphenyl] benzotriazole, 2 , 2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2'- Hydroxy-5'-methacryloxyphenyl) -2H-benzotriazole and the like.
作為水楊酸系紫外線吸收劑,例如可列舉:水楊酸苯酯、水楊酸對第三丁基苯酯、水楊酸對辛基苯酯等。 Examples of the salicylic acid-based ultraviolet absorber include phenyl salicylate, p-tert-butylphenyl salicylate, and p-octylphenyl salicylate.
作為氰基丙烯酸系紫外線吸收劑,例如可列舉:2-乙基己基-2- 氰基-3,3'-二苯基丙烯酸酯、乙基-2-氰基-3,3'-二苯基丙烯酸酯等。 Examples of the cyanoacrylic ultraviolet absorber include 2-ethylhexyl-2- Cyano-3,3'-diphenylacrylate, ethyl-2-cyano-3,3'-diphenylacrylate, and the like.
作為光穩定劑,例如可列舉:受阻胺系光穩定劑、紫外線穩定劑等。 Examples of the light stabilizer include a hindered amine light stabilizer, an ultraviolet stabilizer, and the like.
作為受阻胺系光穩定劑,例如可列舉:[雙(2,2,6,6-四甲基-4-哌啶基)癸二酸酯]、雙(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、1,2,2,6,6-五甲基-4-哌啶基癸二酸甲酯等。 Examples of the hindered amine light stabilizer include [bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate] and bis (1,2,2,6,6 -Pentamethyl-4-piperidinyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidinylsebacate and the like.
作為紫外線穩定劑,例如可列舉:雙(辛基苯基)硫化鎳、[2,2'-硫代雙(4-第三辛基苯酚)]-正丁基胺鎳、鎳錯合物-3,5-二-第三丁基-4-羥基苄基-磷酸單乙酯、二丁基二硫代胺基甲酸鎳、苯甲酸酯型之猝滅劑、二丁基二硫代胺基甲酸鎳等。 Examples of the ultraviolet stabilizer include bis (octylphenyl) nickel sulfide, [2,2'-thiobis (4-third octylphenol)]-n-butylamine nickel, and nickel complex- 3,5-Di-tert-butyl-4-hydroxybenzyl-monoethyl phosphate, nickel dibutyldithiocarbamate, benzoate type quencher, dibutyl dithioamine Nickel formate and so on.
作為防劣化劑,較佳為具有受阻酚結構之防劣化劑。於包含具有受阻酚結構之防劣化劑作為防劣化劑之情形時,其含有比率相對於多元醇(A)較佳為0.01重量%~10重量%,更佳為0.05重量%~10重量%,進而較佳為0.1重量%~10重量%。將具有受阻酚結構之防劣化劑之含有比率於上述範圍內調整,即便於貼附於被接著體之後於加溫狀態下保存,於被接著體上亦不易產生糊劑殘留等,可使抗糊劑殘留性進一步優異。若具有受阻酚結構之防劣化劑之含有比率過小,則有無法充分表現抗糊劑殘留性之虞。若具有受阻酚結構之防劣化劑之含有比率過多,則有如下之虞:產生對成本方面不利之問題,或產生無法維持黏著特性之問題,或者產生被接著體被污染之問題。 As the deterioration preventing agent, a deterioration preventing agent having a hindered phenol structure is preferred. In the case where an anti-degradation agent having a hindered phenol structure is included as an anti-degradation agent, the content ratio thereof is preferably 0.01% to 10% by weight, and more preferably 0.05% to 10% by weight relative to the polyol (A). It is more preferably 0.1% by weight to 10% by weight. The content ratio of the anti-deterioration agent with a hindered phenol structure is adjusted within the above range, and even if it is stored in a heated state after being adhered to the adherend, it is difficult to produce paste residues on the adherend, etc. The paste residue is further excellent. If the content of the anti-deterioration agent having a hindered phenol structure is too small, there is a possibility that the anti-paste residue property may not be sufficiently expressed. If the content ratio of the anti-deterioration agent having a hindered phenol structure is too large, there is a possibility that a problem that is disadvantageous in terms of cost, a problem that the adhesion characteristics cannot be maintained, or a problem that the adherend is contaminated.
作為具有受阻酚結構之防劣化劑,只要為例如具有於結合有苯酚之OH基之芳香族環上碳原子之鄰接碳原子之至少一者結合第三丁基等位阻較大之基之受阻酚結構之防劣化劑即可,可採用任意適當之防劣化劑。考慮到與先前相比,使用具有此種受阻酚結構之防劣化劑之特定防劣化劑,可使抑制多元醇之分子量降低之效果非常大,因此,可表現抗糊劑殘留性與先前相比特別優異之效果。 As the anti-deterioration agent having a hindered phenol structure, for example, as long as it has at least one adjacent carbon atom of a carbon atom on an aromatic ring bonded to an OH group bonded to phenol, a third butyl group such as a sterically hindered group is blocked. A phenol-based deterioration preventing agent is sufficient, and any appropriate deterioration preventing agent can be used. Considering that the use of a specific anti-deterioration agent having such a hindered phenol structure as an anti-deterioration agent can greatly reduce the molecular weight reduction of the polyol compared to the previous one, the anti-paste residue performance can be compared with the previous one. Particularly excellent effect.
作為此種具有受阻酚結構之防劣化劑,具體而言例如可列舉:二丁基羥基甲苯(BHT);商品名「IRGANOX 1010」(巴斯夫製造)、商品名「IRGANOX 1010FF」(巴斯夫製造)、商品名「IRGANOX 1035」(巴斯夫製造)、商品名「IRGANOX 1035FF」(巴斯夫製造)、商品名「IRGANOX 1076」(巴斯夫製造)、商品名「IRGANOX 1076FD」(巴斯夫製造)、商品名「IRGANOX 1076DWJ」(巴斯夫製造)、商品名「IRGANOX 1098」(巴斯夫製造)、商品名「IRGANOX 1135」(巴斯夫製造)、商品名「IRGANOX 1330」(巴斯夫製造)、商品名「IRGANOX 1726」(巴斯夫製造)、商品名「IRGANOX 1425WL」(巴斯夫製造)、商品名「IRGANOX 1520L」(巴斯夫製造)、商品名「IRGANOX 245」(巴斯夫製造)、商品名「IRGANOX 245FF」(巴斯夫製造)、商品名「IRGANOX 259」(巴斯夫製造)、商品名「IRGANOX 3114」(巴斯夫製造)、商品名「IRGANOX 565」(巴斯夫製造)、商品名「IRGANOX 295」(巴斯夫製造)等受阻酚系抗氧化劑;商品名「TINUVIN P」(巴斯夫製造)、商品名「TINUVIN P FL」(巴斯夫製造)、商品名「TINUVIN 234」(巴斯夫製造)、商品名「TINUVIN 326」(巴斯夫製造)、商品名「TINUVIN 326FL」(巴斯夫製造)、商品名「TINUVIN 328」(巴斯夫製造)、商品名「TINUVIN 329」(巴斯夫製造)、商品名「TINUVIN 329FL」(巴斯夫製造)等苯并三唑系紫外線吸收劑;商品名「TINUVIN 213」(巴斯夫製造)、商品名「TINUVIN 571」(巴斯夫製造)等液狀紫外線吸收劑;商品名「TINUVIN 1577ED」(巴斯夫製造)等三嗪系紫外線吸收劑;商品名「TINUVIN 120」(巴斯夫製造)等苯甲酸酯系紫外線吸收劑;商品名「TINUVIN 144」(巴斯夫製造)等受阻胺系光穩定劑等。 Specific examples of such a deterioration preventing agent having a hindered phenol structure include dibutyl hydroxytoluene (BHT); trade names "IRGANOX 1010" (manufactured by BASF), trade names "IRGANOX 1010FF" (manufactured by BASF), Trade name "IRGANOX 1035" (manufactured by BASF), trade name "IRGANOX 1035FF" (manufactured by BASF), trade name "IRGANOX 1076" (manufactured by BASF), trade name "IRGANOX 1076FD" (manufactured by BASF), trade name "IRGANOX 1076DWJ" (Made by BASF), trade name `` IRGANOX 1098 '' (made by BASF), trade name `` IRGANOX 1135 '' (made by BASF), trade name `` IRGANOX 1330 '' (made by BASF), trade name `` IRGANOX 1726 '' (made by BASF), product Name "IRGANOX 1425WL" (made by BASF), trade name "IRGANOX 1520L" (made by BASF), trade name "IRGANOX 245" (made by BASF), trade name "IRGANOX 245FF" (made by BASF), trade name "IRGANOX 259" ( (Made by BASF), trade name "IRGANOX 3114" (made by BASF), trade name "IRGANOX 565" (made by BASF), trade name "IRGANOX 295" (bath Hindered phenol-based antioxidants, etc .; trade name "TINUVIN P" (manufactured by BASF), trade name "TINUVIN P FL" (manufactured by BASF), trade name "TINUVIN 234" (manufactured by BASF), trade name "TINUVIN 326" ( BASF), trade name `` TINUVIN 326FL '' (manufactured by BASF), trade name `` TINUVIN 328 '' (manufactured by BASF), trade name `` TINUVIN 329 '' (manufactured by BASF), trade name `` TINUVIN 329FL '' (manufactured by BASF), etc. Triazole-based UV absorbers; liquid UV absorbers such as "TINUVIN 213" (manufactured by BASF) and "TINUVIN 571" (manufactured by BASF); triazine-based UV rays such as "TINUVIN 1577ED" (manufactured by BASF) Absorbents; benzoate-based UV absorbers such as the brand name "TINUVIN 120" (manufactured by BASF); hindered amine-based light stabilizers such as the brand name "TINUVIN 144" (manufactured by BASF).
胺甲酸乙酯系樹脂較佳為包含脂肪酸酯。藉由胺甲酸乙酯系樹脂包含脂肪酸酯,可提高潤濕速率。脂肪酸酯可僅為一種,或者可為 兩種以上。 The urethane-based resin preferably contains a fatty acid ester. When the urethane-based resin contains a fatty acid ester, the wetting rate can be increased. The fatty acid ester may be only one or may be More than two.
脂肪酸酯之含有比率相對於多元醇(A),較佳為5重量%~50重量%,更佳為7重量%~40重量%,進而較佳為8重量%~35重量%,特別較佳為9重量%~30重量%,最佳為10重量%~20重量%。於將脂肪酸酯之含有比率於上述範圍內調整,可進一步提高潤濕速率。若脂肪酸酯之含有比率過小,則有無法充分提高潤濕速率之虞。若脂肪酸酯之含有比率過多,則有如下之虞:產生成本方面不利之問題,或產生無法維持黏著特性之問題,或者產生被接著體被污染之問題。 The content ratio of the fatty acid ester relative to the polyol (A) is preferably 5% to 50% by weight, more preferably 7% to 40% by weight, and still more preferably 8% to 35% by weight, and is particularly preferable. It is preferably 9% to 30% by weight, and most preferably 10% to 20% by weight. Adjusting the content ratio of the fatty acid ester within the above range can further increase the wetting rate. If the content ratio of the fatty acid ester is too small, there is a possibility that the wetting rate cannot be sufficiently increased. If the content ratio of the fatty acid ester is too large, there may be a problem that it is disadvantageous in terms of cost, a problem that the adhesion characteristics cannot be maintained, or a problem that the adherend is contaminated.
脂肪酸酯之數量平均分子量Mn較佳為200~400,更佳為210~395,進而較佳為230~380,特別較佳為240~360,最佳為270~340。藉由將脂肪酸酯之數量平均分子量Mn於上述範圍內調整,可進一步提高潤濕速率。若脂肪酸酯之數量平均分子量Mn過小,則有即便添加份數較多,潤濕速率亦不提高之虞。若脂肪酸酯之數量平均分子量Mn過大,則有乾燥時之黏著劑之硬化性惡化,從而不僅對潤濕特性造成不良影響,而且對其他黏著特性亦造成不良影響之虞。 The number average molecular weight Mn of the fatty acid ester is preferably 200 to 400, more preferably 210 to 395, still more preferably 230 to 380, particularly preferably 240 to 360, and most preferably 270 to 340. By adjusting the number average molecular weight Mn of the fatty acid ester within the above range, the wetting rate can be further increased. If the number average molecular weight Mn of the fatty acid ester is too small, there is a possibility that the wetting rate will not increase even if the number of added components is large. If the number average molecular weight Mn of the fatty acid ester is too large, the hardenability of the adhesive during drying may be deteriorated, which may adversely affect not only the wetting characteristics but also other adhesive characteristics.
於無損本發明之效果之範圍內,作為脂肪酸酯,可採用任意適當之脂肪酸酯。作為此種脂肪酸酯,例如可列舉:聚氧乙烯雙酚A月桂酸酯、硬脂酸丁酯、棕櫚酸2-乙基己基酯、硬脂酸2-乙基己基酯、二十二烷酸單甘油酯、2-乙基己酸十六烷基酯、肉豆蔻酸異丙酯、棕櫚酸異丙酯、異硬脂酸膽甾醇酯、甲基丙烯酸月桂酯、椰油酸甲酯、月桂酸甲酯、油酸甲酯、硬脂酸甲酯、肉豆蔻酸肉豆蔻酯、肉豆蔻酸辛基十二烷基酯、季戊四醇單油酸酯、季戊四醇單硬脂酸酯、季戊四醇四棕櫚酸酯、硬脂酸硬脂基酯、硬脂酸異十三烷基酯、2-乙基己酸甘油三酯、月桂酸丁酯、油酸辛酯等。 As long as the effect of the present invention is not impaired, any appropriate fatty acid ester can be used as the fatty acid ester. Examples of such fatty acid esters include polyoxyethylene bisphenol A laurate, butyl stearate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, and behenane Acid monoglyceride, cetyl 2-ethylhexanoate, isopropyl myristate, isopropyl palmitate, cholesteryl isostearate, lauryl methacrylate, methyl cocoate, Methyl laurate, methyl oleate, methyl stearate, myristyl myristate, octyl dodecyl myristate, pentaerythritol monooleate, pentaerythritol monostearate, pentaerythritol tetrapalmitate Esters, stearyl stearate, isotridecyl stearate, 2-ethylhexanoate triglyceride, butyl laurate, octyl oleate, and the like.
胺甲酸乙酯系樹脂較佳為包含調平劑。藉由胺甲酸乙酯系樹脂包含調平劑,可防止由橘皮造成之外觀不均。調平劑可僅為一種,或 者可為兩種以上。 The urethane-based resin preferably contains a leveling agent. By including a leveling agent in the urethane-based resin, uneven appearance due to orange peel can be prevented. Leveling agent can be only one, or It can be two or more.
調平劑之含有比率相對於多元醇(A),較佳為0.001重量%~1重量%,更佳為0.002重量%~0.5重量%,進而較佳為0.003重量%~0.1重量%,特別較佳為0.004重量%~0.05重量%,最佳為0.005重量%~0.01重量%。藉由將調平劑之含有比率於上述範圍內調整,可進一步防止由橘皮造成之外觀不均。若調平劑之含有比率過小,則有無法防止由橘皮造成之外觀不均之虞。若調平劑之含有比率過多,則有如下之虞:產生成本方面不利之問題,或無法維持黏著特性之問題,或者產生被接著體被污染之問題。 The content ratio of the leveling agent is preferably 0.001% by weight to 1% by weight, more preferably 0.002% by weight to 0.5% by weight, and further preferably 0.003% by weight to 0.1% by weight relative to the polyol (A). It is preferably 0.004% to 0.05% by weight, and most preferably 0.005% to 0.01% by weight. By adjusting the content ratio of the leveling agent within the above range, it is possible to further prevent the appearance unevenness caused by the orange peel. If the content ratio of the leveling agent is too small, the appearance unevenness caused by the orange peel may not be prevented. If the content ratio of the leveling agent is too large, there may be a problem that it is disadvantageous in terms of cost, a problem that the adhesive properties cannot be maintained, or a problem that the adherend is contaminated.
作為調平劑,於無損本發明之效果之範圍,可採用任意適當之調平劑。作為此種調平劑,例如可列舉:丙烯酸系調平劑,氟系調平劑、矽系調平劑等。作為丙烯酸系調平劑,可列舉:POLYFLOW No.36、POLYFLOW No.56、POLYFLOW No.85HF、POLYFLOW No.99C(均為共榮社化學公司製造)等。作為氟系調平劑,可列舉:MEGAFACE F470N、MEGAFACE F556(均為DIC公司製造)等。作為矽系調平劑,可列舉GRANDIC PC4100(DIC公司製造)等。 As the leveling agent, any appropriate leveling agent can be used as long as the effect of the present invention is not impaired. Examples of such a leveling agent include an acrylic leveling agent, a fluorine leveling agent, and a silicon leveling agent. Examples of the acrylic leveling agent include POLYFLOW No. 36, POLYFLOW No. 56, POLYFLOW No. 85HF, and POLYFLOW No. 99C (all manufactured by Kyoeisha Chemical Co., Ltd.). Examples of the fluorine-based leveling agent include MEGAFACE F470N, MEGAFACE F556 (both manufactured by DIC Corporation), and the like. Examples of the silicon-based leveling agent include GRANDIC PC4100 (manufactured by DIC Corporation).
於無損本發明之效果之範圍內,作為使含有多元醇(A)及多官能異氰酸酯化合物(B)之組合物硬化而獲得胺甲酸乙酯系樹脂之方法,可採用使用塊狀聚合、或溶液聚合等之胺基甲酸乙酯化反應方法等任意適當之方法。然而,有於經由所謂胺甲酸乙酯預聚物獲得之胺甲酸乙酯系樹脂中未表現本發明之效果之虞,因此作為將含有多元醇(A)及多官能異氰酸酯化合物(B)之組合物硬化而獲得胺甲酸乙酯系樹脂之方法,較佳為經由胺甲酸乙酯預聚物獲得胺甲酸乙酯系樹脂之方法以外的方法。 As a method for obtaining a urethane-based resin by curing a composition containing a polyol (A) and a polyfunctional isocyanate compound (B) as long as the effect of the present invention is not impaired, block polymerization or a solution can be used. Any appropriate method such as a urethane reaction method such as polymerization. However, there is a possibility that the effect of the present invention may not be exhibited in an urethane-based resin obtained through a so-called urethane prepolymer. Therefore, it is a combination of a polyol (A) and a polyfunctional isocyanate compound (B) The method for obtaining a urethane-based resin by curing the material is preferably a method other than a method for obtaining a urethane-based resin through a urethane prepolymer.
為了將含有多元醇(A)與多官能異氰酸酯化合物(B)之組合物硬化,較佳為使用觸媒。作為此種觸媒,例如可列舉:有機金屬系化合 物、三級胺化合物等。 In order to harden a composition containing a polyol (A) and a polyfunctional isocyanate compound (B), it is preferable to use a catalyst. Examples of such catalysts include organometallic compounds Compounds, tertiary amine compounds, etc.
作為有機金屬化合物,例如可列舉:鐵系化合物、錫系化合物、鈦系化合物、鋯系化合物、鉛系化合物、鈷系化合物、鋅系化合物等。該等之中,就反應速率及黏著劑層之適用期之方面而言,較佳為鐵系化合物、錫系化合物。 Examples of the organic metal compound include iron-based compounds, tin-based compounds, titanium-based compounds, zirconium-based compounds, lead-based compounds, cobalt-based compounds, and zinc-based compounds. Among these, an iron-based compound and a tin-based compound are preferred in terms of the reaction rate and the pot life of the adhesive layer.
作為鐵系化合物,例如可列舉:乙醯丙酮鐵、2-乙基己酸鐵等。 Examples of the iron-based compound include iron acetoacetate and iron 2-ethylhexanoate.
作為錫系化合物,例如可列舉:二丁基二氯化錫、二丁基氧化錫、二丁基二溴化錫、馬來酸二丁基錫、二月桂酸二丁基錫、二乙酸二丁基錫、二丁基硫化錫、三丁基甲氧基錫、乙酸三丁基錫、三乙基乙氧基錫、三丁基乙氧基錫、氧化二辛基錫、二月桂酸二辛基錫、三丁基氯化錫、三氯乙酸三丁基錫、2-乙基己酸錫等。 Examples of the tin-based compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin maleate, dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin. Tin sulfide, tributyltin methoxide, tributyltin acetate, triethylethoxytin, tributylethoxytin, dioctyltin oxide, dioctyltin dilaurate, tributyltin chloride , Tributyltin trichloroacetate, tin 2-ethylhexanoate and the like.
作為鈦系化合物,例如可列舉:二丁基二氯化鈦、鈦酸四丁酯、丁氧基三氯化鈦等。 Examples of the titanium-based compound include dibutyl titanium dichloride, tetrabutyl titanate, and butoxy titanium trichloride.
作為鋯系化合物,例如可列舉:環烷酸鋯、乙醯丙酮鋯等。 Examples of the zirconium-based compound include zirconium naphthenate and zirconium acetoacetone.
作為鉛系化合物,例如可列舉:油酸鉛、2-乙基己酸鉛、苯甲酸鉛、環烷酸鉛等。 Examples of the lead-based compound include lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate.
作為鈷系化合物,例如可列舉:2-乙基己酸鈷、苯甲酸鈷等。 Examples of the cobalt-based compound include cobalt 2-ethylhexanoate and cobalt benzoate.
作為鋅系化合物,例如可列舉:環烷酸鋅、2-乙基己酸鋅等。 Examples of the zinc-based compound include zinc naphthenate and zinc 2-ethylhexanoate.
作為三級胺化合物,例如可列舉:三乙胺、三伸乙基二胺、1,8-二氮雜雙環(5,4,0)十一碳-7-烯等。, Examples of the tertiary amine compound include triethylamine, triethylenediamine, 1,8-diazabicyclo (5,4,0) undec-7-ene, and the like. ,
觸媒可僅為一種,或者可為兩種以上。另外,可併用觸媒與交聯延遲劑等。觸媒之量相對於多元醇(A),較佳為0.02重量%~0.10重量%,更佳為0.02重量%~0.08重量%,進而較佳為0.02重量%~0.06重量%,特別較佳為0.02重量%~0.05重量%。於將觸媒之量於上述範圍內調整,可提供一種例如抗靜電性非常優異並且抗糊劑殘留性或再加工性亦更優異之胺甲酸乙酯系黏著劑。 The catalyst may be only one type, or may be two or more types. In addition, a catalyst, a cross-linking retarder, and the like may be used in combination. The amount of the catalyst is preferably 0.02% by weight to 0.10% by weight, more preferably 0.02% by weight to 0.08% by weight, and more preferably 0.02% by weight to 0.06% by weight relative to the polyol (A), and particularly preferably 0.02% to 0.05% by weight. When the amount of the catalyst is adjusted within the above range, for example, a urethane-based adhesive having excellent antistatic properties and excellent paste residue or reworkability can be provided.
本發明之胺甲酸乙酯系黏著劑包含含有氟有機陰離子之離子性液體。藉由本發明之胺甲酸乙酯系黏著劑包含含有氟有機陰離子之離子性液體,可提供一種抗靜電性非常優異之胺甲酸乙酯系黏著劑。本發明之胺甲酸乙酯系黏著劑所含之離子性液體可僅為一種,或者可為兩種以上。 The urethane-based adhesive of the present invention contains an ionic liquid containing a fluorine organic anion. Since the urethane-based adhesive of the present invention contains an ionic liquid containing a fluorine organic anion, an urethane-based adhesive having excellent antistatic properties can be provided. The urethane-based adhesive of the present invention may contain only one ionic liquid or two or more ionic liquids.
於本發明中,所謂離子性液體意指於25℃下呈液狀之熔融鹽(離子性化合物)。 In the present invention, the ionic liquid means a molten salt (ionic compound) that is liquid at 25 ° C.
於無損本發明之效果之範圍內,只要離子性液體為包含氟有機陰離子之液體,則可採用任意適當之離子性液體。作為此種離子性液體,較佳為例如由氟有機陰離子與鎓陽離子構成之離子性液體。作為離子性液體,藉由採用由氟有機陰離子與鎓陽離子構成之離子性液體,可提供一種抗靜電性能極其非常優異之胺甲酸乙酯系黏著劑。 As long as the effect of the present invention is not impaired, any appropriate ionic liquid may be used as long as the ionic liquid is a liquid containing a fluorine organic anion. As such an ionic liquid, for example, an ionic liquid composed of a fluorine organic anion and an onium cation is preferable. As an ionic liquid, by using an ionic liquid composed of a fluorine organic anion and an onium cation, an urethane-based adhesive having extremely excellent antistatic properties can be provided.
作為可構成離子性液體之鎓陽離子,於無損本發明之效果之範圍內,可採用任意適當之鎓陽離子。作為此種鎓陽離子,較佳為選自含氮鎓陽離子、含硫鎓陽離子、含磷鎓陽離子中之至少一種。藉由選擇該等鎓陽離子,可提供一種抗靜電性能極其非常優異之胺甲酸乙酯系黏著劑。 As the onium cation that can constitute an ionic liquid, any appropriate onium cation can be used as long as the effect of the present invention is not impaired. Such an onium cation is preferably at least one selected from the group consisting of a nitrogen-containing cation, a sulfur-containing cation, and a phosphorus-containing cation. By selecting these onium cations, it is possible to provide an urethane-based adhesive with extremely excellent antistatic properties.
作為可構成離子性液體之鎓陽離子,較佳為選自具有由通式(1)~(5)表示之結構之陽離子中之至少一種。 The onium cation capable of constituting an ionic liquid is preferably at least one selected from cations having a structure represented by the general formulae (1) to (5).
於通式(1)中,Ra表示碳數4~20之烴基,可包含雜原子,Rb及Rc相同或不同,表示氫或碳數1~16之烴基,可包含雜原子。然而,於氮原子包含雙鍵之情形時,不存在Rc。 In the general formula (1), Ra represents a hydrocarbon group having 4 to 20 carbon atoms and may include a hetero atom, and Rb and Rc are the same or different and represent hydrogen or a hydrocarbon group having 1 to 16 carbon atoms and may include a hetero atom. However, when the nitrogen atom contains a double bond, Rc does not exist.
於通式(2)中,Rd表示碳數2~20之烴基,可包含雜原子,並且Re、Rf及Rg相同或不同,表示氫或碳數1~16之烴基,可包含雜原子。 In the general formula (2), Rd represents a hydrocarbon group having 2 to 20 carbon atoms and may include heteroatoms, and Re, Rf and Rg are the same or different and represent hydrogen or a hydrocarbon group having 1 to 16 carbon atoms and may include heteroatoms.
於通式(3)中,Rh表示碳數2~20之烴基,可包含雜原子,Ri、Rj及Rk相同或不同,表示氫或碳數1~16之烴基,可包含雜原子。 In the general formula (3), Rh represents a hydrocarbon group having 2 to 20 carbon atoms, and may include heteroatoms. Ri, Rj, and Rk are the same or different and represent hydrogen or a hydrocarbon group having 1 to 16 carbon atoms, which may include heteroatoms.
於通式(4)中,Z表示氮原子、硫原子或磷原子,Rl、Rm、Rn及Ro相同或不同,表示碳數1~20之烴基,可包含雜原子。其中於Z為硫原子之情形時,不存在Ro。 In the general formula (4), Z represents a nitrogen atom, a sulfur atom, or a phosphorus atom, R1, Rm, Rn, and Ro are the same or different, and represent a hydrocarbon group having 1 to 20 carbon atoms, which may include a hetero atom. However, when Z is a sulfur atom, Ro does not exist.
於通式(5)中,X表示Li原子、Na原子或K原子。 In the general formula (5), X represents a Li atom, a Na atom, or a K atom.
作為由通式(1)表示之陽離子,例如可列舉:吡啶鎓陽離子、吡咯烷鎓陽離子、哌啶鎓陽離子、具有吡咯啉骨架之陽離子、具有吡咯骨架之陽離子等。 Examples of the cation represented by the general formula (1) include a pyridinium cation, a pyrrolidinium cation, a piperidinium cation, a cation having a pyrroline skeleton, and a cation having a pyrrole skeleton.
作為通式(1)表示之陽離子之具體例,例如可列舉:1-乙基吡啶鎓陽離子、1-丁基吡啶鎓陽離子、1-己基吡啶鎓陽離子、1-乙基-3-甲基吡啶鎓陽離子、1-丁基-3-甲基吡啶鎓陽離子、1-己基-3-甲基吡啶鎓陽離子、1-丁基-4-甲基吡啶鎓陽離子、1-辛基-4-甲基吡啶鎓陽離子、1-丁基-3,4-二甲基吡啶鎓陽離子、1,1-二甲基吡咯烷鎓陽離子等吡咯烷鎓陽離子;1-乙基-1-甲基吡咯烷鎓陽離子、1-甲基-1-丙基吡咯烷鎓陽離子、1-甲基-1-丁基吡咯烷鎓陽離子、1-甲基-1-戊基吡咯烷鎓陽離子、1-甲基-1-己基吡咯烷鎓陽離子、1-甲基-1-庚基吡咯烷鎓陽離子、1-乙基-1-丙基吡咯烷鎓陽離子、1-乙基-1-丁基吡咯烷鎓陽離子、1-乙基-1-戊基吡咯烷鎓陽離子、1-乙基-1-己基吡咯烷鎓陽離子、1-乙基-1-庚基吡咯烷鎓陽離子、1,1-二丙基吡咯烷鎓陽離子、 1-丙基-1-丁基吡咯烷鎓陽離子、1,1-二丁基吡咯烷鎓陽離子等吡啶烷鎓陽離子;1-丙基哌啶鎓陽離子、1-戊基哌啶鎓陽離子、1-甲基-1-乙基哌啶鎓陽離子、1-甲基-1-丙基哌啶鎓陽離子、1-甲基-1-丁基哌啶鎓陽離子、1-甲基-1-戊基哌啶鎓陽離子、1-甲基-1-己基哌啶鎓陽離子、1-甲基-1-庚基哌啶鎓陽離子、1-乙基-1-丙基哌啶鎓陽離子、1-乙基-1-丁基哌啶鎓陽離子、1-乙基-1-戊基哌啶鎓陽離子、1-乙基-1-己基哌啶鎓陽離子、1-乙基-1-庚基哌啶鎓陽離子、1-丙基-1-丁基哌啶鎓陽離子、1,1-二甲基哌啶鎓陽離子、1,1-二丙基哌啶鎓陽離子、1,1-二丁基哌啶鎓陽離子等哌啶鎓陽離子;2-甲基-1-吡咯啉陽離子;1-乙基-2-苯基吲哚陽離子;1,2-二甲基吲哚陽離子;1-乙基咔唑陽離子等。 Specific examples of the cation represented by the general formula (1) include 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, and 1-ethyl-3-methylpyridine. Onium cation, 1-butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4-methyl Pyrrolidinium cations such as pyridinium cation, 1-butyl-3,4-dimethylpyridinium cation, 1,1-dimethylpyrrolidinium cation; 1-ethyl-1-methylpyrrolidinium cation , 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1- Hexylpyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1- Ethyl-1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation, 1-ethyl-1-heptylpyrrolidinium cation, 1,1-dipropylpyrrolidinium cation , Pyridinium cations such as 1-propyl-1-butylpyrrolidinium cation, 1,1-dibutylpyrrolidinium cation; 1-propylpiperidinium cation, 1-pentylpiperidinium cation, 1 -Methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentyl Piperidinium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium cation, 1-ethyl-1-propylpiperidinium cation, 1-ethyl 1-Butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation , 1-propyl-1-butylpiperidinium cation, 1,1-dimethylpiperidinium cation, 1,1-dipropylpiperidinium cation, 1,1-dibutylpiperidinium cation And other piperidinium cations; 2-methyl-1-pyrroline cations; 1-ethyl-2-phenylindole cations; 1,2-dimethylindole cations; 1-ethylcarbazole cations and the like.
該等之中,就可更進一步表現本發明之效果之方面而言,較佳可列舉:1-乙基吡啶鎓陽離子、1-丁基吡啶鎓陽離子、1-己基吡啶鎓陽離子、1-乙基-3-甲基吡啶鎓陽離子、1-丁基-3-甲基吡啶鎓陽離子、1-己基-3-甲基吡啶鎓陽離子、1-丁基-4-甲基吡啶鎓陽離子、1-辛基-4-甲基吡啶鎓陽離子等吡啶鎓陽離子;1-乙基-1-甲基吡咯烷鎓陽離子、1-甲基-1-丙基吡咯烷鎓陽離子、1-甲基-1-丁基吡咯烷鎓陽離子、1-甲基-1-戊基吡咯烷鎓陽離子、1-甲基-1-己基吡咯烷鎓陽離子、1-甲基-1-庚基吡咯烷鎓陽離子、1-乙基-1-丙基吡咯烷鎓陽離子、1-乙基-1-丁基吡咯烷鎓陽離子、1-乙基-1-戊基吡咯烷鎓陽離子、1-乙基-1-己基吡咯烷鎓陽離子、1-乙基-1-庚基吡咯烷鎓陽離子等吡咯烷鎓陽離子;1-甲基-1-乙基哌啶鎓陽離子、1-甲基-1-丙基哌啶鎓陽離子、1-甲基-1-丁基哌啶鎓陽離子、1-甲基-1-戊基哌啶鎓陽離子、1-甲基-1-己基哌啶鎓陽離子、1-甲基-1-庚基哌啶鎓陽離子、1-乙基-1-丙基哌啶鎓陽離子、1-乙基-1-丁基哌啶鎓陽離子、1-乙基-1-戊基哌啶鎓陽離子、1-乙基-1-己基哌啶鎓陽離子、1-乙基-1-庚基哌 啶鎓陽離子、1-丙基-1-丁基哌啶鎓陽離子等哌啶鎓陽離子等;更佳為1-己基吡啶鎓陽離子、1-乙基-3-甲基吡啶鎓陽離子、1-丁基-3-甲基吡啶鎓陽離子、1-辛基-4-甲基吡啶鎓陽離子、1-甲基-1-丙基吡咯烷鎓陽離子、1-甲基-1-丙基哌啶鎓陽離子。 Among them, in terms of further exhibiting the effects of the present invention, preferred examples include 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, and 1-ethyl 3-methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1- Pyridinium cations such as octyl-4-methylpyridinium cation; 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1- Butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexylpyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1- Ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-ethyl-1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidine Pyrrolidinium cations such as onium cations, 1-ethyl-1-heptylpyrrolidinium cations; 1-methyl-1-ethylpiperidinium cations, 1-methyl-1-propylpiperidinium cations, 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiper Pyridinium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium cation, 1-ethyl-1-propylpiperidinium cation, 1-ethyl- 1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperium Piperidinium cations such as a pyridinium cation, 1-propyl-1-butylpiperidinium cation, etc .; more preferably 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butane 3-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-propylpiperidinium cation .
作為通式(2)表示之陽離子,例如可列舉:咪唑鎓陽離子、四氫嘧啶鎓陽離子、二氫嘧啶鎓陽離子等。 Examples of the cation represented by the general formula (2) include an imidazolium cation, a tetrahydropyrimidinium cation, and a dihydropyrimidinium cation.
作為通式(2)表示之陽離子之具體例,例如可列舉:1,3-二甲基咪唑鎓陽離子、1,3-二乙基咪唑鎓陽離子、1-乙基-3-甲基咪唑鎓陽離子、1-丁基-3-甲基咪唑鎓陽離子、1-己基-3-甲基咪唑鎓陽離子、1-辛基-3-甲基咪唑鎓陽離子、1-癸基-3-甲基咪唑鎓陽離子、1-十二烷基-3-甲基咪唑鎓陽離子、1-十四烷基-3-甲基咪唑鎓陽離子、1,2-二甲基-3-丙基咪唑鎓陽離子、1-乙基-2,3-二甲基咪唑鎓陽離子、1-丁基-2,3-二甲基咪唑鎓陽離子、1-己基-2,3-二甲基咪唑鎓陽離子等咪唑鎓陽離子;1,3-二甲基-1,4,5,6-四氫嘧啶鎓陽離子、1,2,3-三甲基-1,4,5,6-四氫嘧啶鎓陽離子、1,2,3,4-四甲基-1,4,5,6-四氫嘧啶鎓陽離子、1,2,3,5-四甲基-1,4,5,6-四氫嘧啶鎓陽離子等四氫嘧啶鎓陽離子;1,3-二甲基-1,4-二氫嘧啶鎓陽離子、1,3-二甲基-1,6-二氫嘧啶鎓陽離子、1,2,3-三甲基-1,4-二氫嘧啶鎓陽離子、1,2,3-三甲基-1,6-二氫嘧啶鎓陽離子、1,2,3,4-四甲基-1,4-二氫嘧啶鎓陽離子、1,2,3,4-四甲基-1,6-二氫嘧啶鎓陽離子等二氫嘧啶鎓陽離子等。 Specific examples of the cation represented by the general formula (2) include, for example, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, and 1-ethyl-3-methylimidazolium. Cation, 1-butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium Onium cation, 1-dodecyl-3-methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, 1 -Ethyl-2,3-dimethylimidazolium cation, 1-butyl-2,3-dimethylimidazolium cation, 1-hexyl-2,3-dimethylimidazolium cation, and other imidazolium cations; 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2, Tetrahydrogen such as 3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation Pyrimidinium cations; 1,3-dimethyl-1,4-dihydropyrimidinium cations, 1,3-dimethyl-1,6-dihydropyrimidinium cations, 1,2,3-trimethyl- 1,4-dihydropyrimidinium cation, 1,2,3-trimethyl-1,6-di Dihydrogen such as pyrimidinium cation, 1,2,3,4-tetramethyl-1,4-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,6-dihydropyrimidinium cation Pyrimidinium cations and the like.
該等之中,就可更進一步表現本發明之效果之方面而言,較佳為1,3-二甲基咪唑鎓陽離子、1,3-二乙基咪唑鎓陽離子、1-乙基-3-甲基咪唑鎓陽離子、1-丁基-3-甲基咪唑鎓陽離子、1-己基-3-甲基咪唑鎓陽離子、1-辛基-3-甲基咪唑鎓陽離子、1-癸基-3-甲基咪唑鎓陽離子、1-十二烷基-3-甲基咪唑鎓陽離子、1-十四烷基-3-甲基咪唑鎓陽離子等咪唑鎓陽離子,更佳為1-乙基-3-甲基咪唑鎓陽離子、1-己基- 3-甲基咪唑鎓陽離子。 Among these, from the viewpoint of further exhibiting the effects of the present invention, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, and 1-ethyl-3 are preferred. -Methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl- Imidazolium cations such as 3-methylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, more preferably 1-ethyl- 3-methylimidazolium cation, 1-hexyl- 3-methylimidazolium cation.
作為通式(3)表示之陽離子,例如可列舉:吡唑鎓陽離子、吡唑啉鎓陽離子等。 Examples of the cation represented by the general formula (3) include a pyrazolium cation, a pyrazolinium cation, and the like.
作為通式(3)表示之陽離子之具體例,例如可列舉:1-甲基吡唑鎓陽離子、3-甲基吡唑鎓陽離子、1-乙基-2-甲基吡唑啉鎓陽離子、1-乙基-2,3,5-三甲基吡唑鎓陽離子、1-丙基-2,3,5-三甲基吡唑鎓陽離子、1-丁基-2,3,5-三甲基吡唑鎓陽離子等吡唑鎓陽離子;1-乙基-2,3,5-三甲基吡唑啉鎓陽離子、1-丙基-2,3,5-三甲基吡唑啉鎓陽離子、1-丁基-2,3,5-三甲基吡唑啉鎓陽離子等吡唑啉鎓陽離子等。 Specific examples of the cation represented by the general formula (3) include, for example, 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2-methylpyrazolinium cation, 1-ethyl-2,3,5-trimethylpyrazolium cation, 1-propyl-2,3,5-trimethylpyrazolium cation, 1-butyl-2,3,5-tris Pyrazolium cations such as methylpyrazolium cations; 1-ethyl-2,3,5-trimethylpyrazolium cations, 1-propyl-2,3,5-trimethylpyrazolium cations Cations, pyrazolinium cations such as 1-butyl-2,3,5-trimethylpyrazolinium cation, and the like.
作為通式(4)表示之陽離子,例如可列舉:四烷基銨陽離子、三烷基鋶陽離子、四烷基鏻陽離子、或上述烷基之一部分經烯基或烷氧基進而環氧基取代而成者等。 Examples of the cation represented by the general formula (4) include a tetraalkylammonium cation, a trialkylphosphonium cation, a tetraalkylphosphonium cation, or an alkyl group substituted with an alkenyl group or an alkoxy group and then an epoxy group. Finished and so on.
作為通式(4)表示之陽離子之具體例,例如可列舉:四甲基銨陽離子、四乙基銨陽離子、四丁基銨陽離子、四戊基銨陽離子、四己基銨陽離子、四庚基銨陽離子、三乙基甲基銨陽離子、三丁基乙基銨陽離子、三甲基丙基銨陽離子、三甲基癸基銨陽離子、N,N-二乙基-N-甲基-N-(2-甲氧基乙基)銨陽離子、縮水甘油基三甲基銨陽離子、三甲基鋶陽離子、三乙基鋶陽離子、三丁基鋶陽離子、三己基鋶陽離子、二乙基甲基鋶陽離子、二丁基乙基鋶陽離子、二甲基癸基鋶陽離子、四甲基鏻陽離子、四乙基鏻陽離子、四丁基鏻陽離子、四己基鏻陽離子、四辛基鏻陽離子、三乙基甲基鏻陽離子、三丁基乙基鏻陽離子、三甲基癸基鏻陽離子、二烯丙基二甲基銨陽離子等。 Specific examples of the cation represented by the general formula (4) include a tetramethylammonium cation, a tetraethylammonium cation, a tetrabutylammonium cation, a tetrapentylammonium cation, a tetrahexylammonium cation, and a tetraheptylammonium cation. Cation, triethylmethylammonium cation, tributylethylammonium cation, trimethylpropylammonium cation, trimethyldecylammonium cation, N, N-diethyl-N-methyl-N- ( 2-methoxyethyl) ammonium cation, glycidyl trimethylammonium cation, trimethylphosphonium cation, triethylphosphonium cation, tributylphosphonium cation, trihexylphosphonium cation, diethylmethylphosphonium cation , Dibutylethylphosphonium cation, dimethyldecylphosphonium cation, tetramethylphosphonium cation, tetraethylphosphonium cation, tetrabutylphosphonium cation, tetrahexylphosphonium cation, tetraoctylphosphonium cation, triethylformyl Methyl sulfonium cation, tributylethylsulfonium cation, trimethyldecylsulfonium cation, diallyldimethylammonium cation, and the like.
該等之中,就可更進一步表現本發明之效果之方面而言,較佳可列舉:三乙基甲基銨陽離子、三丁基乙基銨陽離子、三甲基癸基銨陽離子、二乙基甲基鋶陽離子、二丁基乙基鋶陽離子、二甲基癸基鋶陽離子、三乙基甲基鏻陽離子、三丁基乙基鏻陽離子、三甲基癸基鏻 陽離子等非對稱四烷基銨陽離子、三烷基鋶陽離子、四烷基鏻陽離子;或N,N-二乙基-N-甲基-N-(2-甲氧基乙基)銨陽離子、縮水甘油基三甲基銨陽離子、二烯丙基二甲基銨陽離子、N,N-二甲基-N-乙基-N-丙基銨陽離子、N,N-二甲基-N-乙基-N-丁基銨陽離子、N,N-二甲基-N-乙基-N-戊基銨陽離子、N,N-二甲基-N-乙基-N-己基銨陽離子、N,N-二甲基-N-乙基-N-庚基銨陽離子、N,N-二甲基-N-乙基-N-壬基銨陽離子、N,N-二甲基-N,N-二丙基銨陽離子、N,N-二乙基-N-丙基-N-丁基銨陽離子、N,N-二甲基-N-丙基-N-戊基銨陽離子、N,N-二甲基-N-丙基-N-己基銨陽離子、N,N-二甲基-N-丙基-N-庚基銨陽離子、N,N-二甲基-N-丁基-N-己基銨陽離子、N,N-二乙基-N-丁基-N-庚基銨陽離子、N,N-二甲基-N-戊基-N-己基銨陽離子、N,N-二甲基-N,N-二己基銨陽離子、三甲基庚基銨陽離子、N,N-二乙基-N-甲基-N-丙基銨陽離子、N,N-二乙基-N-甲基-N-戊基銨陽離子、N,N-二乙基-N-甲基-N-庚基銨陽離子、N,N-二乙基-N-丙基-N-戊基銨陽離子、三乙基丙基銨陽離子、三乙基戊基銨陽離子、三乙基庚基銨陽離子、N,N-二丙基-N-甲基-N-乙基銨陽離子、N,N-二丙基-N-甲基-N-戊基銨陽離子、N,N-二丙基-N-丁基-N-己基銨陽離子、N,N-二丙基-N,N-二己基銨陽離子、N,N-二丁基-N-甲基-N-戊基銨陽離子、N,N-二丁基-N-甲基-N-己基銨陽離子、三辛基甲基銨陽離子、N-甲基-N-乙基-N-丙基-N-戊基銨陽離子等,更佳為三甲基丙基銨陽離子。 Among these, in terms of further exhibiting the effects of the present invention, preferred examples include triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, and diethyl Methylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, triethylmethylsulfonium cation, tributylethylsulfonium cation, trimethyldecylsulfonium Asymmetric tetraalkylammonium cation, trialkylphosphonium cation, tetraalkylphosphonium cation; or N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium cation, Glycidyltrimethylammonium cation, diallyldimethylammonium cation, N, N-dimethyl-N-ethyl-N-propylammonium cation, N, N-dimethyl-N-ethyl -N-butylammonium cation, N, N-dimethyl-N-ethyl-N-pentylammonium cation, N, N-dimethyl-N-ethyl-N-hexylammonium cation, N, N-dimethyl-N-ethyl-N-heptylammonium cation, N, N-dimethyl-N-ethyl-N-nonylammonium cation, N, N-dimethyl-N, N- Dipropylammonium cation, N, N-diethyl-N-propyl-N-butylammonium cation, N, N-dimethyl-N-propyl-N-pentylammonium cation, N, N- Dimethyl-N-propyl-N-hexylammonium cation, N, N-dimethyl-N-propyl-N-heptylammonium cation, N, N-dimethyl-N-butyl-N- Hexyl ammonium cation, N, N-diethyl-N-butyl-N-heptylammonium cation, N, N-dimethyl-N-pentyl-N-hexylammonium cation, N, N-dimethyl -N, N-dihexylammonium cation, trimethylheptylammonium cation, N, N-diethyl-N-methyl-N-propylammonium cation, N, N-diethyl -N-methyl-N-pentylammonium cation, N, N-diethyl-N-methyl-N-heptylammonium cation, N, N-diethyl-N-propyl-N-pentyl Ammonium cation, triethylpropylammonium cation, triethylpentylammonium cation, triethylheptylammonium cation, N, N-dipropyl-N-methyl-N-ethylammonium cation, N, N -Dipropyl-N-methyl-N-pentylammonium cation, N, N-dipropyl-N-butyl-N-hexylammonium cation, N, N-dipropyl-N, N-dihexyl Ammonium cation, N, N-dibutyl-N-methyl-N-pentylammonium cation, N, N-dibutyl-N-methyl-N-hexylammonium cation, trioctylmethylammonium cation, N-methyl-N-ethyl-N-propyl-N-pentylammonium cation and the like, more preferably trimethylpropylammonium cation.
作為可構成離子性液體之氟有機陰離子,於無損本發明之效果之範圍內,可採用任意適當之氟有機陰離子。此種氟有機陰離子可完全經氟化(全氟化),或者可部分經氟化。 As a fluorine organic anion which can constitute an ionic liquid, any appropriate fluorine organic anion can be used as long as the effect of the present invention is not impaired. Such fluoroorganic anions may be fully fluorinated (perfluorinated) or may be partially fluorinated.
作為此種氟有機陰離子,例如可列舉:經氟化之芳基磺酸酯、全氟烷烴磺酸酯、雙(氟磺醯基)醯亞胺、雙(全氟烷烴磺醯基)醯亞胺、氰基全氟烷烴磺醯胺、雙(氰基)全氟烷烴磺醯基甲基化物、氰基- 雙(全氟烷烴磺醯基)甲基化物、三(全氟烷烴磺醯基)甲基化物、三氟乙酸酯、全氟烷基化物、三(全氟烷烴磺醯基)甲基化物、(全氟烷烴磺醯基)三氟乙醯胺等。 Examples of such fluoroorganic anions include fluorinated arylsulfonates, perfluoroalkanesulfonates, bis (fluorosulfonyl) fluorenimines, and bis (perfluoroalkanesulfonyl) fluorenes. Amines, cyanoperfluoroalkanesulfonamides, bis (cyano) perfluoroalkanesulfonamidomethylates, cyano- Bis (perfluoroalkanesulfonyl) methylate, tris (perfluoroalkanesulfonyl) methylate, trifluoroacetate, perfluoroalkylate, tris (perfluoroalkanesulfonyl) methylate , (Perfluoroalkanesulfonyl) trifluoroacetamide and the like.
該等氟有機陰離子之中,更佳為全氟烷基磺酸酯、雙(氟磺醯基)醯亞胺、雙(全氟烷烴磺醯基)醯亞胺,更具體而言例如為三氟甲基磺酸酯、五氟乙基磺酸酯、七氟丙基磺酸酯、九氟丁基磺酸酯、雙(氟磺醯基)醯亞胺、雙(三氟甲基磺醯基)醯亞胺。 Among the fluoroorganic anions, more preferred are perfluoroalkylsulfonate, bis (fluorosulfofluorenyl) fluorenimide, and bis (perfluoroalkanesulfonyl) fluorenimide, and more specifically, for example, tris Fluoromethanesulfonate, pentafluoroethylsulfonate, heptafluoropropylsulfonate, nonafluorobutylsulfonate, bis (fluorosulfonyl) fluorenimide, bis (trifluoromethylsulfonium) Amidyl) imine.
作為本發明之胺甲酸乙酯系黏著劑中所含之離子性液體之具體例,可自上述陽離子成分與上述陰離子成分之組合適當選擇使用。作為此種離子性液體之具體例,例如可列舉:1-己基吡啶鎓雙(氟磺醯基)醯亞胺、1-乙基-3-甲基吡啶鎓三氟甲基磺酸鹽、1-乙基-3-甲基吡啶鎓五氟乙基磺酸鹽、1-乙基-3-甲基吡啶鎓七氟丙基磺酸鹽、1-乙基-3-甲基吡啶鎓九氟丁基磺酸鹽、1-丁基-3-甲基吡啶鎓三氟甲基磺酸鹽、1-丁基-3-甲基吡啶鎓雙(三氟甲基磺醯基)醯亞胺、1-丁基-3-甲基吡啶鎓雙(五氟乙基磺醯基)醯亞胺、1-辛基-4-甲基吡啶鎓雙(氟磺醯基)醯亞胺、1,1-二甲基吡咯烷鎓雙(三氟甲基磺醯基)醯亞胺、1-甲基-1-乙基吡咯烷鎓雙(三氟甲基磺醯基)醯亞胺、1-甲基-1-丙基吡咯烷鎓雙(三氟甲基磺醯基)醯亞胺、1-甲基-1-丙基吡咯烷鎓雙(氟磺醯基)醯亞胺、1-甲基-1-丁基吡咯烷鎓雙(三氟甲基磺醯基)醯亞胺、1-甲基-1-戊基吡咯烷鎓雙(三氟甲基磺醯基)醯亞胺、1-甲基-1-己基吡咯烷鎓雙(三氟甲基磺醯基)醯亞胺、1-甲基-1-庚基吡咯烷鎓雙(三氟甲基磺醯基)醯亞胺、1-乙基-1-丙基吡咯烷鎓雙(三氟甲基磺醯基)醯亞胺、1-乙基-1-丁基吡咯烷鎓雙(三氟甲基磺醯基)醯亞胺、1-乙基-1-戊基吡咯烷鎓雙(三氟甲基磺醯基)醯亞胺、1-乙基-1-己基吡咯烷鎓雙(三氟甲基磺醯基)醯亞胺、1-乙基-1-庚基吡咯烷鎓雙(三氟甲基磺醯基)醯亞胺、1,1-二丙基吡咯烷鎓雙(三氟甲基磺醯基)醯亞胺、1-丙基-1-丁基 吡咯烷鎓雙(三氟甲基磺醯基)醯亞胺、1,1-二丁基吡咯烷鎓雙(三氟甲基磺醯基)醯亞胺、1-丙基哌啶鎓雙(三氟甲基磺醯基)醯亞胺、1-戊基哌啶鎓雙(三氟甲基磺醯基)醯亞胺、1,1-二甲基哌啶鎓雙(三氟甲基磺醯基)醯亞胺、1-甲基-1-乙基哌啶鎓雙(三氟甲基磺醯基)醯亞胺、1-甲基-1-丙基哌啶鎓雙(三氟甲基磺醯基)醯亞胺、1-甲基-1-丙基哌啶鎓雙(氟磺醯基)醯亞胺、1-甲基-1-丁基哌啶鎓雙(三氟甲基磺醯基)醯亞胺、1-甲基-1-戊基哌啶鎓雙(三氟甲基磺醯基)醯亞胺、1-甲基-1-己基哌啶鎓雙(三氟甲基磺醯基)醯亞胺、1-甲基-1-庚基哌啶鎓雙(三氟甲基磺醯基)醯亞胺、1-乙基-1-丙基哌啶鎓雙(三氟甲基磺醯基)醯亞胺、1-乙基-1-丁基哌啶鎓雙(三氟甲基磺醯基)醯亞胺、1-乙基-1-戊基哌啶鎓雙(三氟甲基磺醯基)醯亞胺、1-乙基-1-己基哌啶鎓雙(三氟甲基磺醯基)醯亞胺、1-乙基-1-庚基哌啶鎓雙(三氟甲基磺醯基)醯亞胺、1,1-二丙基哌啶鎓雙(三氟甲基磺醯基)醯亞胺、1-丙基-1-丁基哌啶鎓雙(三氟甲基磺醯基)醯亞胺、1,1-二丁基哌啶鎓雙(三氟甲基磺醯基)醯亞胺、1,1-二甲基吡咯烷鎓雙(五氟乙基磺醯基)醯亞胺、1-甲基-1-乙基吡咯烷鎓雙(五氟乙基磺醯基)醯亞胺、1-甲基-1-丙基吡咯烷鎓雙(五氟乙基磺醯基)醯亞胺、1-甲基-1-丁基吡咯烷鎓雙(五氟乙基磺醯基)醯亞胺、1-甲基-1-戊基吡咯烷鎓雙(五氟乙基磺醯基)醯亞胺、1-甲基-1-己基吡咯烷鎓雙(五氟乙基磺醯基)醯亞胺、1-甲基-1-庚基吡咯烷鎓雙(五氟乙基磺醯基)醯亞胺、1-乙基-1-丙基吡咯烷鎓雙(五氟乙基磺醯基)醯亞胺、1-乙基-1-丁基吡咯烷鎓雙(五氟乙基磺醯基)醯亞胺、1-乙基-1-戊基吡咯烷鎓雙(五氟乙基磺醯基)醯亞胺、1-乙基-1-己基吡咯烷鎓雙(五氟乙基磺醯基)醯亞胺、1-乙基-1-庚基吡咯烷鎓雙(五氟乙基磺醯基)醯亞胺、1,1-二丙基吡咯烷鎓雙(五氟乙基磺醯基)醯亞胺、1-丙基-1-丁基吡咯烷鎓雙(五氟乙基磺醯基)醯亞胺、1,1-二丁基吡咯烷鎓雙(五氟乙基磺醯基)醯亞胺、1-丙基哌啶鎓雙(五氟乙基磺 醯基)醯亞胺、1-戊基哌啶鎓雙(五氟乙基磺醯基)醯亞胺、1,1-二甲基哌啶鎓雙(五氟乙基磺醯基)醯亞胺、1-甲基-1-乙基哌啶鎓雙(五氟乙基磺醯基)醯亞胺、1-甲基-1-丙基哌啶鎓雙(五氟乙基磺醯基)醯亞胺、1-甲基-1-丁基哌啶鎓雙(五氟乙基磺醯基)醯亞胺、1-甲基-1-戊基哌啶鎓雙(五氟乙基磺醯基)醯亞胺、1-甲基-1-己基哌啶鎓雙(五氟乙基磺醯基)醯亞胺、1-甲基-1-庚基哌啶鎓雙(五氟乙基磺醯基)醯亞胺、1-乙基-1-丙基哌啶鎓雙(五氟乙基磺醯基)醯亞胺、1-乙基-1-丁基哌啶鎓雙(五氟乙基磺醯基)醯亞胺、1-乙基-1-戊基哌啶鎓雙(五氟乙基磺醯基)醯亞胺、1-乙基-1-己基哌啶鎓雙(五氟乙基磺醯基)醯亞胺、1-乙基-1-庚基哌啶鎓雙(五氟乙基磺醯基)醯亞胺、1,1-二丙基哌啶鎓雙(五氟乙基磺醯基)醯亞胺、1-丙基-1-丁基哌啶鎓雙(五氟乙基磺醯基)醯亞胺、1,1-二丁基哌啶鎓雙(五氟乙基磺醯基)醯亞胺、1-乙基-3-甲基咪唑鎓三氟乙酸鹽、1-乙基-3-甲基咪唑鎓七氟丁酸鹽、1-乙基-3-甲基咪唑鎓三氟甲基磺酸鹽、1-乙基-3-甲基咪唑鎓七氟丙基磺酸鹽、1-乙基-3-甲基咪唑鎓九氟丁基磺酸鹽、1-乙基-3-甲基咪唑鎓雙(三氟甲基磺醯基)醯亞胺、1-乙基-3-甲基咪唑鎓雙(氟磺醯基)醯亞胺、1-乙基-3-甲基咪唑鎓雙(五氟乙基磺醯基)醯亞胺、1-乙基-3-甲基咪唑鎓三(三氟甲基磺醯基)甲基化物、1-丁基-3-甲基咪唑鎓三氟乙酸鹽、1-丁基-3-甲基咪唑鎓七氟丁酸鹽、1-丁基-3-甲基咪唑鎓三氟甲基磺酸鹽、1-丁基-3-甲基咪唑鎓全氟丁基磺酸鹽、1-丁基-3-甲基咪唑鎓雙(三氟甲基磺醯基)醯亞胺、1-己基-3-甲基咪唑鎓三氟甲基磺酸鹽、1-己基-3-甲基咪唑鎓雙(氟磺醯基)醯亞胺、1,2-二甲基-3-丙基咪唑鎓雙(三氟甲基磺醯基)醯亞胺、1-乙基-2,3,5-三甲基吡唑鎓雙(三氟甲基磺醯基)醯亞胺、1-丙基-2,3,5-三甲基吡唑鎓雙(三氟甲基磺醯基)醯亞胺、1-丁基-2,3,5-三甲基吡唑鎓雙(三氟甲基磺醯基)醯亞胺、1-乙基-2,3,5-三甲基吡唑鎓雙(五氟乙基磺醯基)醯亞胺、1-丙基-2,3,5- 三甲基吡唑鎓雙(五氟乙基磺醯基)醯亞胺、1-丁基-2,3,5-三甲基吡唑鎓雙(五氟乙基磺醯基)醯亞胺、1-乙基-2,3,5-三甲基吡唑鎓(三氟甲基磺醯基)三氟乙醯胺、1-丙基-2,3,5-三甲基吡唑鎓(三氟甲基磺醯基)三氟乙醯胺、1-丁基-2,3,5-三甲基吡唑鎓(三氟甲基磺醯基)三氟乙醯胺、三甲基丙基銨雙(三氟甲基磺醯基)醯亞胺、N,N-二甲基-N-乙基-N-丙基銨雙(三氟甲基磺醯基)醯亞胺、N,N-二甲基-N-乙基-N-丁基銨雙(三氟甲基磺醯基)醯亞胺、N,N-二甲基-N-乙基-N-戊基銨雙(三氟甲基磺醯基)醯亞胺、N,N-二甲基-N-乙基-N-己基銨雙(三氟甲基磺醯基)醯亞胺、N,N-二甲基-N-乙基-N-庚基銨雙(三氟甲基磺醯基)醯亞胺、N,N-二甲基-N-乙基-N-壬基銨雙(三氟甲基磺醯基)醯亞胺、N,N-二甲基-N,N-二丙基銨雙(三氟甲基磺醯基)醯亞胺、N,N-二甲基-N-丙基-N-丁基銨雙(三氟甲基磺醯基)醯亞胺、N,N-二甲基-N-丙基-N-戊基銨雙(三氟甲基磺醯基)醯亞胺、N,N-二甲基-N-丙基-N-己基銨雙(三氟甲基磺醯基)醯亞胺、N,N-二甲基-N-丙基-N-庚基銨雙(三氟甲基磺醯基)醯亞胺、N,N-二甲基-N-丁基-N-己基銨雙(三氟甲基磺醯基)醯亞胺、N,N-二甲基-N-丁基-N-庚基銨雙(三氟甲基磺醯基)醯亞胺、N,N-二甲基-N-戊基-N-己基銨雙(三氟甲基磺醯基)醯亞胺、N,N-二甲基-N,N-二己基銨雙(三氟甲基磺醯基)醯亞胺、三甲基庚基銨雙(三氟甲基磺醯基)醯亞胺、N,N-二乙基-N-甲基-N-丙基銨雙(三氟甲基磺醯基)醯亞胺、N,N-二乙基-N-甲基-N-戊基銨雙(三氟甲基磺醯基)醯亞胺、N,N-二乙基-N-甲基-N,N-庚基銨雙(三氟甲基磺醯基)醯亞胺、N,N-二乙基-N-丙基-N-戊基銨雙(三氟甲基磺醯基)醯亞胺、三乙基丙基銨雙(三氟甲基磺醯基)醯亞胺、三乙基戊基銨雙(三氟甲基磺醯基)醯亞胺、三乙基庚基銨雙(三氟甲基磺醯基)醯亞胺、N,N-二丙基-N-甲基-N-乙基銨雙(三氟甲基磺醯基)醯亞胺、N,N-二丙基-N-甲基-N-戊基銨雙(三氟甲基磺醯基)醯亞胺、N,N-二丙基-N-丁基-N-己基銨雙(三氟甲基磺醯基) 醯亞胺、N,N-二丙基-N,N-二己基銨雙(三氟甲基磺醯基)醯亞胺、N,N-二丁基-N-甲基-N-戊基銨雙(三氟甲基磺醯基)醯亞胺、N,N-二丁基-N-甲基-N-己基銨雙(三氟甲基磺醯基)醯亞胺、三辛基甲基銨雙(三氟甲基磺醯基)醯亞胺、N-甲基-N-乙基-N-丙基-N-戊基銨雙(三氟甲基磺醯基)醯亞胺、1-丁基吡啶鎓(三氟甲基磺醯基)三氟乙醯胺、1-丁基-3-甲基吡啶鎓(三氟甲基磺醯基)三氟乙醯胺、1-乙基-3-甲基咪唑鎓(三氟甲基磺醯基)三氟乙醯胺、四己基銨雙(三氟甲基磺醯基)醯亞胺、二烯丙基二甲基銨三氟甲基磺酸鹽、二烯丙基二甲基銨雙(三氟甲基磺醯基)醯亞胺、二烯丙基二甲基銨雙(五氟乙基磺醯基)醯亞胺、N,N-二乙基-N-甲基-N-(2-甲氧基乙基)銨三氟甲基磺酸鹽、N,N-二乙基-N-甲基-N-(2-甲氧基乙基)銨雙(三氟甲基磺醯基)醯亞胺、N,N-二乙基-N-甲基-N-(2-甲氧基乙基)銨雙(五氟乙基磺醯基)醯亞胺、縮水甘油基三甲基銨三氟甲基磺酸鹽、縮水甘油基三甲基銨雙(三氟甲基磺醯基)醯亞胺、縮水甘油基三甲基銨雙(五氟乙基磺醯基)醯亞胺、二烯丙基二甲基銨雙(三氟甲基磺醯基)醯亞胺、二烯丙基二甲基雙(五氟乙基磺醯基)醯亞胺、雙(三氟甲基磺醯基)醯亞胺鋰、雙(氟磺醯基)醯亞胺鋰等。 Specific examples of the ionic liquid contained in the urethane-based adhesive of the present invention can be appropriately selected and used from the combination of the above-mentioned cationic component and the above-mentioned anionic component. Specific examples of such an ionic liquid include 1-hexylpyridinium bis (fluorosulfonyl) fluorenimine, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1 -Ethyl-3-methylpyridinium pentafluoroethylsulfonate, 1-ethyl-3-methylpyridinium heptafluoropropylsulfonate, 1-ethyl-3-methylpyridinium nonafluoro Butylsulfonate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis (trifluoromethylsulfonyl) fluorenimine, 1-butyl-3-methylpyridinium bis (pentafluoroethylsulfonyl) fluorenimide, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) fluorenimide, 1,1 -Dimethylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimine, 1-methyl-1-ethylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimine, 1-methyl Propyl-1-propylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimide, 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) fluorenimine, 1-methyl 1-Butylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimine, 1-methyl-1-pentylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimine, 1- Methyl-1-hexylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimine, 1-methyl 1-heptylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimine, 1-ethyl-1-propylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimine, 1 -Ethyl-1-butylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimine, 1-ethyl-1-pentylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimine , 1-ethyl-1-hexylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimine, 1-ethyl-1-heptylpyrrolidinium bis (trifluoromethylsulfonyl) fluorene Amine, 1,1-dipropylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimine, 1-propyl-1-butyl Pyrrolidinium bis (trifluoromethylsulfonyl) fluorenimide, 1,1-dibutylpyrrolidinium bis (trifluoromethylsulfonyl) phosphonium imine, 1-propylpiperidinium bis ( Trifluoromethylsulfonyl) fluorenimide, 1-pentylpiperidinium bis (trifluoromethylsulfonyl) fluorenimide, 1,1-dimethylpiperidinium bis (trifluoromethylsulfonium) (Fluorenyl) fluorenimine, 1-methyl-1-ethylpiperidinium bis (trifluoromethylsulfonyl) fluorenimide, 1-methyl-1-propylpiperidinium bis (trifluoromethyl) Sulfofluorenyl) fluorenimine, 1-methyl-1-propylpiperidinium bis (fluorosulfonyl) fluorenimine, 1-methyl-1-butylpiperidinium bis (trifluoromethyl) Sulfonyl) fluorenimine, 1-methyl-1-pentylpiperidinium bis (trifluoromethylsulfonyl) fluorenimide, 1-methyl-1-hexylpiperidinium bis (trifluoromethyl) Sulfofluorenyl) fluorenimine, 1-methyl-1-heptylpiperidinium bis (trifluoromethylsulfonyl) fluorenimide, 1-ethyl-1-propylpiperidinium bis (tri Fluoromethylsulfonyl) fluorenimine, 1-ethyl-1-butylpiperidinium bis (trifluoromethylsulfonyl) fluorenimide, 1-ethyl-1-pentylpiperidinium bis (Trifluoromethylsulfonyl) fluorenimine, 1-ethyl-1-hexylpiperidinium bis (trifluoromethylsulfonyl) fluorenimide, 1-ethyl-1-heptylpiperyl Onium bis (trifluoromethylsulfonyl) fluorenimide, 1,1-dipropylpiperidinium bis (trifluoromethylsulfonyl) fluorenimide, 1-propyl-1-butylpiperidine Onium bis (trifluoromethylsulfonyl) fluorenimide, 1,1-dibutylpiperidinium bis (trifluoromethylsulfonyl) fluorenimide, 1,1-dimethylpyrrolidinium bis (Pentafluoroethylsulfonyl) fluorenimine, 1-methyl-1-ethylpyrrolidinium bis (pentafluoroethylsulfonyl) fluorenimine, 1-methyl-1-propylpyrrolidine Onium bis (pentafluoroethylsulfonyl) fluorenimide, 1-methyl-1-butylpyrrolidinium bis (pentafluoroethylsulfonyl) fluorenimine, 1-methyl-1-pentyl Pyrrolidinium bis (pentafluoroethylsulfonyl) fluorenimide, 1-methyl-1-hexylpyrrolidinium bis (pentafluoroethylsulfonyl) fluorenimide, 1-methyl-1-heptanium Pyrrolidinium bis (pentafluoroethylsulfonyl) fluorenimide, 1-ethyl-1-propylpyrrolidinium bis (pentafluoroethylsulfonyl) fluorenimide, 1-ethyl-1 -Butylpyrrolidinium bis (pentafluoroethylsulfonyl) fluorenimide, 1-ethyl-1-pentylpyrrolidinium bis (pentafluoroethylsulfonyl) fluorenimide, 1-ethyl 1-hexylpyrrolidinium bis (pentafluoroethylsulfonyl) fluorenimine, 1-ethyl-1-heptylpyrrolidinium bis (pentafluoro Sulfofluorenyl) fluorenimine, 1,1-dipropylpyrrolidinium bis (pentafluoroethylsulfonyl) fluorenimine, 1-propyl-1-butylpyrrolidinium bis (pentafluoroethyl) Sulfofluorenyl) fluorenimine, 1,1-dibutylpyrrolidinium bis (pentafluoroethylsulfonyl) fluorenimide, 1-propylpiperidinium bis (pentafluoroethylsulfonate) (Fluorenyl) fluorenimine, 1-pentylpiperidinium bis (pentafluoroethylsulfonyl) fluorenimide, 1,1-dimethylpiperidinium bis (pentafluoroethylsulfonyl) fluorenimide Amine, 1-methyl-1-ethylpiperidinium bis (pentafluoroethylsulfonyl) fluorenimide, 1-methyl-1-propylpiperidinium bis (pentafluoroethylsulfonyl) Fluorenimine, 1-methyl-1-butylpiperidinium bis (pentafluoroethylsulfonyl) fluorenimide, 1-methyl-1-pentylpiperidinium bis (pentafluoroethylsulfonium) Sulfonyl) imine, 1-methyl-1-hexylpiperidinium bis (pentafluoroethylsulfonyl) fluorenimide, 1-methyl-1-heptylpiperidinium bis (pentafluoroethylsulfonate) Fluorenyl) fluorenimine, 1-ethyl-1-propylpiperidinium bis (pentafluoroethylsulfonyl) fluorenimide, 1-ethyl-1-butylpiperidinium bis (pentafluoroethyl) Sulfofluorenyl) fluorenimine, 1-ethyl-1-pentylpiperidinium bis (pentafluoroethylsulfonyl) fluorenimide, 1-ethyl-1-hexylpiperidinium bis (pentafluoro Ethylsulfonyl) fluorenimine, 1-ethyl-1-heptylpiperidinium bis (pentafluoroethylsulfonyl) fluorenimide, 1,1-dipropylpiperidinium bis (pentafluoro) Ethylsulfonyl) fluorenimine, 1-propyl-1-butylpiperidinium bis (pentafluoroethylsulfonyl) fluorenimide, 1,1-dibutylpiperidinium bis (pentafluoro) Ethyl Sulfonyl) fluorenimine, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazolium heptafluorobutyrate, 1-ethyl-3-methyl Imidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium heptafluoropropylsulfonate, 1-ethyl-3-methylimidazolium nonafluorobutylsulfonate, 1- Ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide, 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) fluorenimide, 1-ethyl- 3-methylimidazolium bis (pentafluoroethylsulfonyl) fluorenimide, 1-ethyl-3-methylimidazolium tris (trifluoromethylsulfonyl) methylate, 1-butyl- 3-methylimidazolium trifluoroacetate, 1-butyl-3-methylimidazolium heptafluorobutyrate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butane 3-methylimidazolium perfluorobutylsulfonate, 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimine, 1-hexyl-3-methylimidazole Onium trifluoromethanesulfonate, 1-hexyl-3-methylimidazolium bis (fluorosulfonyl) fluorenimine, 1,2-dimethyl-3-propylimidazolium bis (trifluoromethyl) Sulfonyl) fluorenimine, 1-ethyl-2,3,5-trimethylpyrazolium bis (trifluoromethylsulfonyl) fluorene Amine, 1-propyl-2,3,5-trimethylpyrazolium bis (trifluoromethylsulfonyl) fluorenimine, 1-butyl-2,3,5-trimethylpyrazolium Bis (trifluoromethylsulfonyl) fluorenimide, 1-ethyl-2,3,5-trimethylpyrazolium bis (pentafluoroethylsulfonyl) fluorenimide, 1-propyl- 2,3,5- Trimethylpyrazolium bis (pentafluoroethylsulfonyl) fluorenimide, 1-butyl-2,3,5-trimethylpyrazolium bis (pentafluoroethylsulfonyl) fluorenimide 1-ethyl-2,3,5-trimethylpyrazolium (trifluoromethylsulfonyl) trifluoroacetamide, 1-propyl-2,3,5-trimethylpyrazolium (Trifluoromethylsulfonyl) trifluoroacetamidamine, 1-butyl-2,3,5-trimethylpyrazolium (trifluoromethylsulfonyl) trifluoroacetamidamine, trimethyl Propylammonium bis (trifluoromethylsulfonyl) fluorenimide, N, N-dimethyl-N-ethyl-N-propylammonium bis (trifluoromethylsulfonyl) fluorenimide, N , N-dimethyl-N-ethyl-N-butylammonium bis (trifluoromethylsulfonyl) fluorenimine, N, N-dimethyl-N-ethyl-N-pentylammonium bis (Trifluoromethylsulfonamido) fluorenimine, N, N-dimethyl-N-ethyl-N-hexylammonium bis (trifluoromethylsulfonamido) fluorenimine, N, N-dimethyl -N-ethyl-N-heptylammonium bis (trifluoromethylsulfonyl) fluorenimine, N, N-dimethyl-N-ethyl-N-nonylammonium bis (trifluoromethyl) Sulfonyl) fluorenimine, N, N-dimethyl-N, N-dipropylammonium bis (trifluoromethylsulfonyl) fluorenimine, N, N-dimethyl-N-propyl -N-butylammonium bis (trifluoromethylsulfonyl) fluorenimine, N, N-dimethyl-N-propyl- N-pentylammonium bis (trifluoromethylsulfonyl) fluorenimine, N, N-dimethyl-N-propyl-N-hexylammonium bis (trifluoromethylsulfonyl) fluorenimine, N, N-dimethyl-N-propyl-N-heptylammonium bis (trifluoromethylsulfonyl) fluorenimine, N, N-dimethyl-N-butyl-N-hexylammonium bis (Trifluoromethylsulfonyl) fluorenimine, N, N-dimethyl-N-butyl-N-heptylammonium bis (trifluoromethylsulfonyl) fluorenimine, N, N-di Methyl-N-pentyl-N-hexylammonium bis (trifluoromethylsulfonyl) fluorenimine, N, N-dimethyl-N, N-dihexylammonium bis (trifluoromethylsulfonylsulfonyl) ) Iminoimide, trimethylheptylammonium bis (trifluoromethylsulfonyl) imino, N, N-diethyl-N-methyl-N-propylammonium bis (trifluoromethylsulfonate) (Fluorenyl) fluorenimine, N, N-diethyl-N-methyl-N-pentylammonium bis (trifluoromethylsulfonyl) fluorenimine, N, N-diethyl-N-formyl -N, N-heptylammonium bis (trifluoromethylsulfonyl) fluorenimine, N, N-diethyl-N-propyl-N-pentylammonium bis (trifluoromethylsulfonyl) ) Fluorenimine, triethylpropylammonium bis (trifluoromethylsulfonyl) fluorenimide, triethylpentylammonium bis (trifluoromethylsulfonyl) fluorenimine, triethylheptyl Ammonium bis (trifluoromethylsulfonyl) phosphonium imine, N, N-di -N-methyl-N-ethylammonium bis (trifluoromethylsulfonyl) fluorenimine, N, N-dipropyl-N-methyl-N-pentylammonium bis (trifluoromethyl Sulfonyl) fluorenimine, N, N-dipropyl-N-butyl-N-hexylammonium bis (trifluoromethylsulfonyl) Fluorenimine, N, N-dipropyl-N, N-dihexylammonium bis (trifluoromethylsulfonyl) fluorenimine, N, N-dibutyl-N-methyl-N-pentyl Ammonium bis (trifluoromethylsulfonyl) fluorenimide, N, N-dibutyl-N-methyl-N-hexylammonium bis (trifluoromethylsulfonyl) fluorenimide, trioctylmethyl Ammonium bis (trifluoromethylsulfonyl) fluorenimide, N-methyl-N-ethyl-N-propyl-N-pentylammonium bis (trifluoromethylsulfonyl) fluorenimide, 1-butylpyridinium (trifluoromethylsulfonyl) trifluoroacetamide, 1-butyl-3-methylpyridinium (trifluoromethylsulfonyl) trifluoroacetamide, 1-ethyl 3-methylimidazolium (trifluoromethylsulfonyl) trifluoroacetamidine, tetrahexylammonium bis (trifluoromethylsulfonyl) fluorenimide, diallyldimethylammonium trifluoro Methanesulfonate, diallyldimethylammonium bis (trifluoromethylsulfonyl) fluorenimide, diallyldimethylammonium bis (pentafluoroethylsulfonyl) sulfonium imine, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium trifluoromethanesulfonate, N, N-diethyl-N-methyl-N- (2 -Methoxyethyl) ammonium bis (trifluoromethylsulfonyl) phosphonium imine, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (penta (Fluoroethylsulfonyl) Imine, glycidyl trimethylammonium trifluoromethanesulfonate, glycidyl trimethylammonium bis (trifluoromethylsulfonyl) sulfonium imine, glycidyl trimethylammonium bis (pentafluoro Ethylsulfonyl) fluorenimide, diallyldimethylammonium bis (trifluoromethylsulfonyl) fluorenimide, diallyldimethylbis (pentafluoroethylsulfonyl) fluorene Imines, lithium bis (trifluoromethylsulfonyl) fluorenimide, lithium bis (fluorosulfonyl) fluorenimide, and the like.
該等離子性液體之中,更佳為1-己基吡啶鎓雙(氟磺醯基)醯亞胺、1-乙基-3-甲基吡啶鎓三氟甲基磺酸鹽、1-乙基-3-甲基吡啶鎓五氟乙基磺酸鹽、1-乙基-3-甲基吡啶鎓七氟丙基磺酸鹽、1-乙基-3-甲基吡啶鎓九氟丁基磺酸鹽、1-丁基-3-甲基吡啶鎓三氟甲基磺酸鹽、1-丁基-3-甲基吡啶鎓雙(三氟甲基磺醯基)醯亞胺、1-辛基-4-甲基吡啶鎓雙(氟磺醯基)醯亞胺、1-甲基-1-丙基吡咯烷鎓雙(三氟甲基磺醯基)醯亞胺、1-甲基-1-丙基吡咯烷鎓雙(氟磺醯基)醯亞胺、1-甲基-1-丙基哌啶鎓雙(三氟甲基磺醯基)醯亞胺、1-甲基-1-丙基哌啶鎓雙(氟磺醯基)醯亞胺、1-乙基-3-甲基咪唑鎓三氟甲基磺酸鹽、1-乙基-3-甲基咪唑 鎓七氟丙基磺酸鹽、1-乙基-3-甲基咪唑鎓雙(三氟甲基磺醯基)醯亞胺、1-乙基-3-甲基咪唑鎓雙(氟磺醯基)醯亞胺、1-己基-3-甲基咪唑鎓雙(氟磺醯基)醯亞胺、三甲基丙基銨雙(三氟甲基磺醯基)醯亞胺、雙(三氟甲基磺醯基)醯亞胺鋰、雙(氟磺醯基)醯亞胺鋰。 Among the ionic liquids, 1-hexylpyridinium bis (fluorosulfonyl) fluorenimine, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, and 1-ethyl- 3-methylpyridinium pentafluoroethylsulfonate, 1-ethyl-3-methylpyridinium heptafluoropropylsulfonate, 1-ethyl-3-methylpyridinium nonafluorobutylsulfonic acid Salt, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis (trifluoromethylsulfonyl) fluorenimine, 1-octyl 4-methylpyridinium bis (fluorosulfonyl) fluorenimide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimine, 1-methyl-1 -Propylpyrrolidinium bis (fluorosulfonyl) fluorenimine, 1-methyl-1-propylpiperidinium bis (trifluoromethylsulfonyl) fluorenimine, 1-methyl-1- Propylpiperidinium bis (fluorosulfonyl) fluorenimine, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazole Onium heptafluoropropylsulfonate, 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide, 1-ethyl-3-methylimidazolium bis (fluorosulfonium) Stilbene) imine, 1-hexyl-3-methylimidazolium bis (fluorosulfonyl) fluorenimide, trimethylpropylammonium bis (trifluoromethylsulfonyl) fluorenimide, bis (tris Lithium fluoromethylsulfonyl) fluorenimide, lithium bis (fluorosulfonyl) fluorenimide.
離子性液體可使用市售者,但亦可按照如下方式合成。作為離子性液體之合成方法,只要獲得目標離子性液體即可,並無特別限定,但通常使用文獻「離子性液體-開發之最前線與未來-」(CMC股份有限公司出版發行)記載之鹵化物法、氫氧化物法、酸酯法、錯合法、及中和法等。 Commercially available ionic liquids can be used, but they can also be synthesized as follows. The method of synthesizing the ionic liquid is not particularly limited as long as the target ionic liquid is obtained, but the halogenation described in the document "Ionic Liquids-Frontline and Future of Development" (published and issued by CMC Corporation) is usually used. Physical method, hydroxide method, ester method, error method, and neutralization method.
關於下述鹵化物法、氫氧化物法、酸酯法、錯合法、及中和法,以含氮鎓鹽作為例表示其合成方法,但其他之含硫鎓鹽、含磷鎓鹽等,亦可藉由與其他離子性液體同樣之方法而獲得。 Regarding the following halide method, hydroxide method, ester method, error method, and neutralization method, the nitrogen-containing onium salt is taken as an example to describe the synthesis method, but other sulfonium-containing salts, phosphonium-containing salts, etc. It can also be obtained by the same method as other ionic liquids.
鹵化物法係藉由反應式(1)~(3)表示之反應進行的方法。首先,使三級胺與鹵化烷基進行反應而獲得鹵化物(反應式(1),使用氯、溴、碘作為鹵素)。 The halide method is a method performed by a reaction represented by the reaction formulae (1) to (3). First, a tertiary amine is reacted with a halogenated alkyl group to obtain a halide (Reaction formula (1) using chlorine, bromine, and iodine as a halogen).
藉由使所獲得之鹵化物與具有目標離子性液體之陰離子結構(A-)之酸(HA)或鹽(MA、M表示銨、鋰、鈉、鉀等與目標陰離子形成鹽之陽離子)反應而獲得目標離子性液體(R4NA)。 Halide obtained by making the structure of the target anion having an ionic liquids (A -) acid (HA), or of a salt (MA, M represents an ammonium, lithium, sodium and potassium salts of the target anion cation) Reaction The target ionic liquid (R 4 NA) was obtained.
[化2](1) R3N+RX→R4NX (X:Cl,Br,I)(2) R4NX+HA→R4NA+HX(3) R4NX+MA→R4NA+MX (M:NH4,Li,Na,K,Ag等) (Chemical 2) (1) R 3 N + RX → R 4 NX (X: Cl, Br, I) (2) R 4 NX + HA → R 4 NA + HX (3) R 4 NX + MA → R 4 NA + MX (M: NH 4 , Li, Na, K, Ag, etc.)
氫氧化物法係藉由反應式(4)~(8)表示之反應進行的方法。首先,將鹵化物(R4NX)藉由離子交換膜法電解(反應式(4))、OH型離子交換樹脂法(反應式(5))或與氧化銀(Ag2O)之反應(反應式(6)),獲得氫 氧化物(R4NOH)(使用氯、溴或碘作為鹵素)。 The hydroxide method is a method in which a reaction represented by the reaction formulae (4) to (8) is performed. First, the halide (R 4 NX) is electrolyzed by an ion exchange membrane method (Reaction formula (4)), an OH-type ion exchange resin method (Reaction formula (5)), or a reaction with silver oxide (Ag 2 O) ( Reaction formula (6)) to obtain a hydroxide (R 4 NOH) (using chlorine, bromine, or iodine as a halogen).
對所獲得之氫氧化物,藉由與上述鹵化法同樣之方式,使用反應式(7)~(8)之反應,藉此獲得目標之離子性液體(R4NA)。 The obtained hydroxide was obtained in the same manner as in the above-mentioned halogenation method, using the reactions of reaction formulae (7) to (8), thereby obtaining the target ionic liquid (R 4 NA).
[化3](4) R4NX+H2O→R4NOH+1/2H2+1/2X2 (X:Cl,Br,I)(5) R4NX+P-OH→R4NOH+P-X (P-OH:OH型離子交換樹脂)(6) R4NX+1/2Ag2O+1/2H2O→R4NOH+AgX(7) R4NOH+HA→R4NA+H2O(8) R4NOH+MA→R4NA+MOH (M:NH4,Li,Na,K,Ag等) (Chem. 3) (4) R 4 NX + H 2 O → R 4 NOH + 1 / 2H 2 + 1 / 2X 2 (X: Cl, Br, I) (5) R 4 NX + P-OH → R 4 NOH + PX (P-OH: OH-type ion exchange resin) (6) R 4 NX + 1 / 2Ag 2 O + 1 / 2H 2 O → R 4 NOH + AgX (7) R 4 NOH + HA → R 4 NA + H 2 O (8) R 4 NOH + MA → R 4 NA + MOH (M: NH 4 , Li, Na, K, Ag, etc.)
酸酯法係藉由反應式(9)~(11)所示之反應進行的方法。首先,使三級胺(R3N)與酸酯反應而獲得酸酯物(反應式(9),作為酸酯,使用硫酸、亞硫酸、磷酸、亞磷酸、碳酸等無機酸之酯,或甲基磺酸、甲基膦酸、甲酸等有機酸之酯等)。 The acid ester method is a method in which a reaction shown in reaction formulae (9) to (11) is performed. First, a tertiary amine (R 3 N) is reacted with an acid ester to obtain an acid ester (Reaction formula (9), as the acid ester, an ester of an inorganic acid such as sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, or carbonic acid, or Esters of organic acids such as methanesulfonic acid, methylphosphonic acid, formic acid, etc.).
對所獲得之酸酯物,藉由與上述鹵化物同樣之方式使用反應式(10)~(11)之反應,獲得目標離子性液體(R4NA)。另外,亦可藉由使用三氟甲基磺酸甲酯、三氟乙酸甲酯等作為酸酯,直接獲得離子性液體。 With respect to the obtained acid ester, the reaction of the reaction formulae (10) to (11) was used in the same manner as the above-mentioned halide to obtain a target ionic liquid (R 4 NA). In addition, an ionic liquid can also be directly obtained by using methyl trifluoromethanesulfonate, methyl trifluoroacetate, or the like as an acid ester.
中和法係藉由反應式(12)表示之反應進行的方法。可藉由使三級胺與CF3COOH、CF3SO3H、(CF3SO2)2NH、(CF3SO2)3CH、(C2F5SO2)2NH等有機酸反應而獲得。 The neutralization method is a method performed by a reaction represented by the reaction formula (12). The tertiary amine can be reacted with organic acids such as CF 3 COOH, CF 3 SO 3 H, (CF 3 SO 2 ) 2 NH, (CF 3 SO 2 ) 3 CH, (C 2 F 5 SO 2 ) 2 NH, etc. And get.
[化5](12) R3N+HZ→R3HN+Z-[HZ:CF3COOH,CF3SO3H,(CF3SO2)2NH,(CF3SO2)3CH,(C2F5SO2)2NH等有機酸] [Formula 5] (12) R 3 N + HZ → R 3 HN + Z - [HZ: CF 3 COOH, CF 3 SO 3 H, (CF 3 SO 2) 2 NH, (CF 3 SO 2) 3 CH, (C 2 F 5 SO 2 ) 2 NH and other organic acids]
反應式(1)~(12)中記載之R表示氫或碳數1~20之烴基,可包含雜原子。 R in the reaction formulae (1) to (12) represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, and may include a hetero atom.
作為離子性液體之調配量,根據所使用之聚合物與離子性液體之相容性而發生變化,無法一概定義,但通常,相對於100重量份之胺甲酸乙酯系樹脂,較佳為0.001重量份~50重量份,更佳為0.01重量份~40重量份,進而較佳為0.01重量份~30重量份,特別較佳為0.01重量份~20重量份,最佳為0.01重量份~10重量份。藉由將離子性液體之調配量於上述範圍內調整,可提供一種抗靜電性非常優異之胺甲酸乙酯系黏著劑。若離子性液體之調配量未達0.01重量份,則有未獲得充分之抗靜電特性之虞。若離子性液體之上述調配量超過50重量份,則有對被接著體之污染增加之傾向。 The formulation amount of the ionic liquid varies depending on the compatibility between the polymer used and the ionic liquid, and cannot be defined in general. However, it is generally preferably 0.001 to 100 parts by weight of the urethane resin. Part by weight to 50 parts by weight, more preferably 0.01 to 40 parts by weight, still more preferably 0.01 to 30 parts by weight, particularly preferably 0.01 to 20 parts by weight, and most preferably 0.01 to 10 parts by weight Parts by weight. By adjusting the blending amount of the ionic liquid within the above range, a urethane-based adhesive having excellent antistatic properties can be provided. If the blending amount of the ionic liquid is less than 0.01 part by weight, there is a possibility that sufficient antistatic properties may not be obtained. If the amount of the ionic liquid to be formulated exceeds 50 parts by weight, contamination of the adherend tends to increase.
於無損本發明之效果之範圍內,本發明之胺甲酸乙酯系黏著劑除了如上所述之胺甲酸乙酯系樹脂、離子性液體以外,亦可包含任意適當之其他成分。作為此種其他成分,例如可列舉:胺甲酸乙酯系樹脂以外之其他樹脂成分、增黏劑、無機填充劑、有機填充劑、金屬粉、顏料、箔狀物、軟化劑、塑化劑、抗老化劑、導電劑、紫外線吸收劑、抗氧化劑、光穩定劑、表面潤滑劑、調平劑、抗腐蝕劑、耐熱 穩定劑、聚合抑制劑、潤滑劑、溶劑等。 As long as the effect of the present invention is not impaired, the urethane-based adhesive of the present invention may contain any appropriate other components in addition to the urethane-based resin and the ionic liquid as described above. Examples of such other components include resin components other than urethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, plasticizers, Anti-aging agent, conductive agent, ultraviolet absorber, antioxidant, light stabilizer, surface lubricant, leveling agent, anti-corrosive agent, heat resistance Stabilizers, polymerization inhibitors, lubricants, solvents, etc.
本發明之胺甲酸乙酯系黏著劑可包含改性矽酮油。藉由本發明之胺甲酸乙酯系黏著劑包含改性矽酮油,可更進一步有效表現本發明之效果。 The urethane-based adhesive of the present invention may include a modified silicone oil. When the urethane-based adhesive of the present invention contains a modified silicone oil, the effect of the present invention can be further effectively expressed.
於本發明之胺甲酸乙酯系黏著劑包含改性矽酮油之情形時,其含有比率相對於100重量份胺甲酸乙酯系樹脂,較佳為0.001重量份~50重量份,更佳為0.01重量份~40重量份,進而較佳為0.01重量份~30重量份,特別較佳為0.01重量份~20重量份,最佳為0.01重量份~10重量份。藉由將改性矽酮油之含有比率調整於上述範圍內,可更進一步有效地表現本發明之效果。 When the urethane-based adhesive of the present invention contains a modified silicone oil, its content ratio is preferably 0.001 to 50 parts by weight, and more preferably 100 parts by weight relative to the urethane-based resin. 0.01 to 40 parts by weight, more preferably 0.01 to 30 parts by weight, particularly preferably 0.01 to 20 parts by weight, and most preferably 0.01 to 10 parts by weight. By adjusting the content ratio of the modified silicone oil within the above range, the effect of the present invention can be more effectively expressed.
於無損本發明之效果之範圍內,作為改性矽酮油,可採用任意適當之改性矽酮油。作為此種改性矽酮油,例如可列舉可自信越化學工業股份有限公司獲取之改性矽酮油。 As long as the effect of the present invention is not impaired, as the modified silicone oil, any appropriate modified silicone oil can be used. As such a modified silicone oil, for example, a modified silicone oil that can be obtained from Shinsei Yue Chemical Industry Co., Ltd. is mentioned.
作為改性矽酮油,較佳為聚醚改性矽酮油。藉由採用聚醚改性矽酮油,可更進一步有效地表現本發明之效果。 The modified silicone oil is preferably a polyether-modified silicone oil. By using polyether-modified silicone oil, the effect of the present invention can be further effectively expressed.
作為聚醚改性矽酮油,可列舉:側鏈型聚醚改性矽酮油、兩末端型聚醚改性矽酮油等。該等之中,就可進一步充分有效表現本發明之效果之方面而言,較佳為兩末端型聚醚改性矽酮油。 Examples of the polyether-modified silicone oil include a side chain-type polyether-modified silicone oil, and both-end-type polyether-modified silicone oil. Among these, a two-terminal polyether-modified silicone oil is preferable in that the effect of the present invention can be sufficiently and effectively exhibited.
本發明之胺甲酸乙酯系黏著劑之抗靜電性非常優異,且相對於玻璃板之剝離帶電電壓之絕對值較佳為未達4.0kV,更佳為3.5kV以下,進而較佳為3.0kV以下,進而較佳為2.5kV以下,進而較佳為2.0kV以下,進而較佳為1.5kV以下,進而較佳為1.0kV以下,特別較佳為0.5kV以下,最佳為0.3kV以下。藉由上述剝離帶電電壓在上述範圍內,本發明之胺甲酸乙酯系黏著劑之抗靜電性非常優異。 The urethane-based adhesive of the present invention has excellent antistatic properties, and the absolute value of the peeling charging voltage with respect to the glass plate is preferably less than 4.0 kV, more preferably 3.5 kV or less, and further preferably 3.0 kV. Hereinafter, it is more preferably 2.5 kV or less, still more preferably 2.0 kV or less, still more preferably 1.5 kV or less, still more preferably 1.0 kV or less, particularly preferably 0.5 kV or less, and most preferably 0.3 kV or less. When the peeling charging voltage is within the above range, the urethane-based adhesive of the present invention is very excellent in antistatic properties.
本發明之胺甲酸乙酯系黏著劑對玻璃板之黏著力,以剛貼附於 玻璃板之後之初始黏著力計,較佳為0.5N/25mm以下,更佳為0.005N/25mm~0.5N/25mm,進而較佳為0.005N/25mm~0.4N/25mm,特別較佳為0.005N/25mm~0.3N/25mm,最佳為0.01N/25mm~0.2N/25mm。藉由上述初始黏著力在上述範圍內,本發明之胺甲酸乙酯系黏著劑具有適度之初始黏著性,可表現進一步優異之再加工性。 The adhesive force of the urethane-based adhesive of the present invention to a glass plate is just adhered to The initial adhesion meter after the glass plate is preferably 0.5N / 25mm or less, more preferably 0.005N / 25mm ~ 0.5N / 25mm, even more preferably 0.005N / 25mm ~ 0.4N / 25mm, and particularly preferably 0.005 N / 25mm ~ 0.3N / 25mm, preferably 0.01N / 25mm ~ 0.2N / 25mm. With the above-mentioned initial adhesive force being within the above range, the urethane-based adhesive of the present invention has a moderate initial adhesiveness and can exhibit further excellent reworkability.
再者,上述初始黏著力之測定可藉由如下方式進行:將具有包含本發明之胺甲酸乙酯系黏著劑之黏著劑層之表面保護膜切斷成寬度25mm且長度150mm,作為評價用試樣,於溫度23℃、濕度50%RH之氣氛下,藉由將2.0kg輥往復一次,將評價用試樣之黏著劑層面貼附於玻璃板(松浪硝子工業股份有限公司製造,商品名:Micro Slide Glass S),於溫度23℃、濕度50%RH之氣氛下固化30分鐘,其後,使用通用拉伸試驗機(美蓓亞股份有限公司製造,產品名:TCM-1kNB),以剝離角度180°、拉伸速度300mm/min進行剝離,測定黏著力。 In addition, the measurement of the above-mentioned initial adhesive force can be performed by cutting a surface protective film having an adhesive layer containing the urethane-based adhesive of the present invention into a width of 25 mm and a length of 150 mm as an evaluation test. In a sample at a temperature of 23 ° C and a humidity of 50% RH, the 2.0 kg roll was reciprocated once, and the adhesive layer of the sample for evaluation was attached to a glass plate (Matsulang Glass Industrial Co., Ltd., trade name: Micro Slide Glass S), cured in an atmosphere at a temperature of 23 ° C. and a humidity of 50% RH for 30 minutes. Thereafter, a general-purpose tensile tester (manufactured by Minebea Corporation, product name: TCM-1kNB) was used to peel off The peeling was performed at an angle of 180 ° and a tensile speed of 300 mm / min, and the adhesive force was measured.
本發明之胺甲酸乙酯系黏著劑對玻璃板之黏著力,於貼附於玻璃板並於50℃×50%RH×7天後,較佳為0.5N/25mm以下,更佳為0.005N/25mm~0.5N/25mm,進而較佳為0.005N/25mm~0.4N/25mm,特別較佳為0.005N/25mm~0.3N/25mm,最佳為0.01N/25mm~0.2N/25mm。藉由上述黏著力在上述範圍內,本發明之胺甲酸乙酯系黏著劑可表現進一步優異之再加工性。 The adhesion of the urethane-based adhesive of the present invention to a glass plate is preferably 0.5N / 25mm or less, more preferably 0.005N after being attached to the glass plate and at 50 ° C × 50% RH × 7 days. /25mm~0.5N/25mm, more preferably 0.005N / 25mm ~ 0.4N / 25mm, particularly preferably 0.005N / 25mm ~ 0.3N / 25mm, and most preferably 0.01N / 25mm ~ 0.2N / 25mm. When the above-mentioned adhesive force is within the above range, the urethane-based adhesive of the present invention can exhibit further excellent reworkability.
再者,上述黏著力之測定可藉由如下方式進行:藉由與對玻璃板之初始黏著力相同之方法製作評價用試樣,藉由與初始黏著力相同之方法,測定於溫度50℃、濕度50%RH下保存7天之後的黏著力。 In addition, the measurement of the above-mentioned adhesion can be performed by preparing a sample for evaluation by the same method as the initial adhesion to the glass plate, and measuring the temperature at 50 ° C. by the same method as the initial adhesion. Adhesion after storage for 7 days at 50% RH.
本發明之胺甲酸乙酯系黏著劑對玻璃板之黏著力,於貼附於玻璃板並於60℃×90%RH×7天後,較佳為0.5N/25mm以下,更佳為0.005N/25mm~0.5N/25mm,進而較佳為0.005N/25mm~0.4N/25 mm,特別較佳為0.005N/25mm~0.3N/25mm,最佳為0.01N/25mm~0.2N/25mm。藉由上述黏著力在上述範圍內,本發明之胺甲酸乙酯系黏著劑可表現進一步優異之再加工性。 The adhesion force of the urethane-based adhesive of the present invention to a glass plate is preferably 0.5N / 25mm or less, more preferably 0.005N after being attached to the glass plate and 60 ° C × 90% RH × 7 days. /25mm~0.5N/25mm, more preferably 0.005N / 25mm ~ 0.4N / 25 mm, particularly preferably 0.005N / 25mm ~ 0.3N / 25mm, and most preferably 0.01N / 25mm ~ 0.2N / 25mm. When the above-mentioned adhesive force is within the above range, the urethane-based adhesive of the present invention can exhibit further excellent reworkability.
再者,上述黏著力之測定可藉由如下方法進行:藉由與對玻璃板之初始黏著力相同之方法製作評價用試樣;並藉由與初始黏著力相同之方法測定於溫度60℃、濕度90%RH下保存7天後之黏著力。 In addition, the measurement of the above-mentioned adhesive force can be performed by the following methods: preparing the sample for evaluation by the same method as the initial adhesion to the glass plate; and measuring the temperature at 60 ° C. by the same method as the initial adhesion. Adhesion after storage for 7 days at 90% RH.
本發明之胺甲酸乙酯系黏著劑對玻璃板之黏著力於貼附於玻璃板並於85℃×50%RH×7天後,較佳為0.5N/25mm以下,更佳為0.005N/25mm~0.5N/25mm,進而較佳為0.005N/25mm~0.4N/25mm,特別較佳為0.005N/25mm~0.3N/25mm,最佳為0.01N/25mm~0.2N/25mm。藉由上述黏著力在上述範圍內,本發明之胺甲酸乙酯系黏著劑可表現進一步優異之再加工性。 The adhesion force of the urethane-based adhesive of the present invention to a glass plate is preferably 0.5N / 25mm or less, more preferably 0.005N / after being attached to the glass plate and 85 ° C × 50% RH × 7 days. 25mm ~ 0.5N / 25mm, more preferably 0.005N / 25mm ~ 0.4N / 25mm, particularly preferably 0.005N / 25mm ~ 0.3N / 25mm, and most preferably 0.01N / 25mm ~ 0.2N / 25mm. When the above-mentioned adhesive force is within the above range, the urethane-based adhesive of the present invention can exhibit further excellent reworkability.
再者,上述黏著力之測定可藉由如下方式進行:藉由與對玻璃板之初始黏著力相同之方法製作評價用試樣;並藉由與初始黏著力相同之方法測定於溫度85℃、濕度50%RH下保存7天之後的黏著力。 In addition, the measurement of the above-mentioned adhesive force can be performed as follows: a sample for evaluation is prepared by the same method as the initial adhesion to the glass plate; and the temperature is measured at 85 ° C. by the same method as the initial adhesion. Adhesion after storage for 7 days at 50% RH.
本發明之胺甲酸乙酯系黏著劑對玻璃板之黏著力,於剛貼附於玻璃板之後,貼附於玻璃板並於50℃×50%RH×7天後,於60℃×90%RH×7天後,以及於85℃×50%RH×7天後,均較佳為0.5N/25mm以下,更佳為0.005N/25mm~0.5N/25mm,進而較佳為0.005N/25mm~0.4N/25mm,特別較佳為0.005N/25mm~0.3N/25mm,最佳為0.01N/25mm~0.2N/25mm。藉由上述黏著力在上述範圍內,本發明之胺甲酸乙酯系黏著劑可表現進一步優異之再加工性。 The adhesive force of the urethane-based adhesive of the present invention to the glass plate is immediately after being attached to the glass plate, and then attached to the glass plate at 50 ° C × 50% RH × 7 days, at 60 ° C × 90% After RH × 7 days, and after 85 ° C × 50% RH × 7 days, it is preferably 0.5N / 25mm or less, more preferably 0.005N / 25mm to 0.5N / 25mm, and still more preferably 0.005N / 25mm ~ 0.4N / 25mm, particularly preferably 0.005N / 25mm ~ 0.3N / 25mm, and most preferably 0.01N / 25mm ~ 0.2N / 25mm. When the above-mentioned adhesive force is within the above range, the urethane-based adhesive of the present invention can exhibit further excellent reworkability.
本發明之胺甲酸乙酯系黏著劑較佳為透明性較高。藉由本發明之胺甲酸乙酯系黏著劑之透明性較高,於貼附於光學構件或電子構件之表面之狀態下可準確進行檢查等。本發明之胺甲酸乙酯系黏著劑之霧度較佳為5%以下,更佳為4%以下,進而較佳為3%以下,特別較佳 為2%以下,最佳為1%以下。 The urethane-based adhesive of the present invention preferably has high transparency. Since the urethane-based adhesive of the present invention has high transparency, it can be accurately inspected in a state of being attached to the surface of an optical member or an electronic member. The haze of the urethane-based adhesive of the present invention is preferably 5% or less, more preferably 4% or less, still more preferably 3% or less, and particularly preferably It is 2% or less, preferably 1% or less.
再者,上述霧度之測定係使用霧度計HM-150(村上色彩技術研究所股份有限公司製造),根據JIS-K-7136,藉由霧度(%)=(Td/Tt)×100(Td:漫透射率,Tt:總透光率)進行計算。 In addition, the above haze is measured by using a haze meter HM-150 (manufactured by Murakami Color Technology Research Institute Co., Ltd.), and according to JIS-K-7136, the haze (%) = (Td / Tt) × 100 (Td: diffuse transmittance, Tt: total light transmittance) were calculated.
本發明之表面保護膜為較佳用於光學構件或電子構件之表面保護之表面保護膜。本發明之表面保護膜具有基材層及黏著劑層且該黏著劑層包含本發明之胺甲酸乙酯系黏著劑。 The surface protection film of the present invention is a surface protection film which is preferably used for surface protection of an optical member or an electronic member. The surface protection film of the present invention has a substrate layer and an adhesive layer, and the adhesive layer includes the urethane-based adhesive of the present invention.
圖1係本發明之較佳實施形態之表面保護膜的概略剖面圖。表面保護膜10具備基材層1及黏著劑層2。本發明之表面保護膜亦可根據需要具有任意適當之其他層(未圖示)。 FIG. 1 is a schematic cross-sectional view of a surface protective film according to a preferred embodiment of the present invention. The surface protection film 10 includes a base material layer 1 and an adhesive layer 2. The surface protective film of the present invention may have any appropriate other layer (not shown) as required.
為了對基材層1之未附設黏著劑層2之面形成可容易回捲之捲繞體,例如,可對基材層添加脂肪醯胺、聚乙烯亞胺、長鏈烷基系添加劑等進行剝離處理,或者可設置包含聚矽氧系、長鏈烷基系、氟系等任意適當之剝離劑的塗層。 In order to form a rolled body that can be easily rolled back on the surface of the base material layer 1 without the adhesive layer 2 attached thereto, for example, fatty base, polyethyleneimine, and long-chain alkyl-based additives can be added to the base material layer. The peeling process may be provided with a coating layer containing any appropriate release agent such as a polysiloxane-based, long-chain alkyl-based, or fluorine-based one.
本發明之表面保護膜可貼合具有剝離性之剝離襯墊。 The surface protective film of the present invention can be bonded to a release liner having releasability.
本發明之表面保護膜之厚度可根據用途,設定為任意適當之厚度。就充分表現本發明之效果之觀點而言,較佳為10μm~300μm,更佳為15μm~250μm,進而較佳為20μm~200μm,特別較佳為25μm~150μm。 The thickness of the surface protective film of the present invention can be set to any appropriate thickness depending on the application. From the viewpoint of fully expressing the effects of the present invention, it is preferably 10 μm to 300 μm, more preferably 15 μm to 250 μm, still more preferably 20 μm to 200 μm, and particularly preferably 25 μm to 150 μm.
本發明之表面保護膜之抗靜電性非常優異且相對於玻璃板之剝離帶電電壓之絕對值較佳為未達4.0kV,更佳為3.5kV以下,進而較佳為3.0kV以下,進而較佳為2.5kV以下,進而較佳為2.0kV以下,進而較佳為1.5kV以下,進而較佳為1.0kV以下,特別較佳為0.5kV以下,最佳為0.3kV以下。藉由上述剝離帶電電壓在上述範圍內,本發明之表面保護膜之抗靜電性非常優異。 The surface protection film of the present invention has excellent antistatic properties and the absolute value of the peeling charging voltage relative to the glass plate is preferably less than 4.0 kV, more preferably 3.5 kV or less, still more preferably 3.0 kV or less, and more preferably It is 2.5 kV or less, further preferably 2.0 kV or less, still more preferably 1.5 kV or less, still more preferably 1.0 kV or less, particularly preferably 0.5 kV or less, and most preferably 0.3 kV or less. When the peeling charging voltage is within the above range, the antistatic property of the surface protective film of the present invention is very excellent.
本發明之表面保護膜對玻璃板之黏著力,以剛貼附於玻璃板之後之初始黏著力計,較佳為0.5N/25mm以下,更佳為0.005N/25mm~0.5N/25mm,進而較佳為0.005N/25mm~0.4N/25mm,特別較佳為0.005N/25mm~0.3N/25mm,最佳為0.01N/25mm~0.2N/25mm。藉由上述初始黏著力在上述範圍內,本發明之表面保護膜具有適度之初始黏著性且可表現進一步優異之再加工性。 The adhesion of the surface protective film of the present invention to the glass plate is preferably 0.5N / 25mm or less, more preferably 0.005N / 25mm to 0.5N / 25mm, based on the initial adhesion force immediately after being attached to the glass plate, and further It is preferably 0.005N / 25mm to 0.4N / 25mm, particularly preferably 0.005N / 25mm to 0.3N / 25mm, and most preferably 0.01N / 25mm to 0.2N / 25mm. With the above-mentioned initial adhesive force being within the above range, the surface protective film of the present invention has moderate initial adhesion and can exhibit further excellent reworkability.
再者,上述初始黏著力之測量可藉由如下方式進行:將表面保護膜切斷成寬度25mm且長度150mm,製成評價用試樣,於溫度23℃、濕度50%RH之氣氛下,藉由將2.0kg輥往復一次,將評價用試樣之黏著劑層表面貼附於玻璃板(松浪硝子工業股份有限公司製造,商品名:Micro Slide Glass S),於溫度23℃、濕度50%RH之氣氛下固化30分鐘,其後,利用通用拉伸試驗機(美蓓亞股份有限公司製造,產品名:TCM-1kNB),於剝離角度180°、拉伸速度300mm/min下,進行剝離而測定黏著力。 In addition, the measurement of the initial adhesive force can be performed by cutting the surface protective film into a width of 25 mm and a length of 150 mm to prepare a sample for evaluation, and in an atmosphere at a temperature of 23 ° C and a humidity of 50% RH, A 2.0 kg roller was reciprocated once, and the surface of the adhesive layer of the sample for evaluation was attached to a glass plate (manufactured by Songlang Glass Industry Co., Ltd., trade name: Micro Slide Glass S) at a temperature of 23 ° C and a humidity of 50% RH. It was cured in an atmosphere for 30 minutes, and then peeled using a universal tensile tester (manufactured by Minebea Corporation, product name: TCM-1kNB) at a peeling angle of 180 ° and a tensile speed of 300 mm / min Determination of adhesion.
本發明之表面保護膜對玻璃板之黏著力,於貼附於玻璃板並於50℃×50%RH×7天後,較佳為0.5N/25mm以下,更佳為0.005N/25mm~0.5N/25mm,進而較佳為0.005N/25mm~0.4N/25mm,特別較佳為0.005N/25mm~0.3N/25mm,最佳為0.01N/25mm~0.2N/25mm。藉由上述黏著力在上述範圍內,本發明之表面保護膜可表現進一步優異之再加工性。 The adhesion of the surface protective film of the present invention to a glass plate is preferably 0.5N / 25mm or less, more preferably 0.005N / 25mm ~ 0.5 after being adhered to the glass plate and 50 ° C × 50% RH × 7 days. N / 25mm, more preferably 0.005N / 25mm ~ 0.4N / 25mm, particularly preferably 0.005N / 25mm ~ 0.3N / 25mm, and most preferably 0.01N / 25mm ~ 0.2N / 25mm. With the above-mentioned adhesive force being within the above range, the surface protective film of the present invention can exhibit further excellent reworkability.
再者,上述黏著力之測定可藉由如下方式進行:藉由與對玻璃板之初始黏著力相同之方法製作評價用試樣;並藉由與初始黏著力相同之方法測定於溫度50℃、濕度50%RH下保存7天後之黏著力。 In addition, the measurement of the above-mentioned adhesive force can be performed as follows: a sample for evaluation is prepared by the same method as the initial adhesion to the glass plate; and the temperature is measured at 50 ° C. by the same method as the initial adhesion. Adhesion after 7 days storage at 50% RH.
本發明之表面保護膜對玻璃板之黏著力,於貼附於玻璃板並於60℃×90%RH×7天後,較佳為0.5N/25mm以下,更佳為0.005N/25mm~0.5N/25mm,進而較佳為0.005N/25mm~0.4N/25mm,特別 較佳為0.005N/25mm~0.3N/25mm,最佳為0.01N/25mm~0.2N/25mm。藉由上述黏著力在上述範圍內,本發明之表面保護膜可表現進一步優異之再加工性。 The adhesion of the surface protective film of the present invention to a glass plate is preferably 0.5N / 25mm or less, more preferably 0.005N / 25mm ~ 0.5 after being adhered to the glass plate and 60 ° C × 90% RH × 7 days. N / 25mm, more preferably 0.005N / 25mm ~ 0.4N / 25mm, especially It is preferably 0.005N / 25mm to 0.3N / 25mm, and most preferably 0.01N / 25mm to 0.2N / 25mm. With the above-mentioned adhesive force being within the above range, the surface protective film of the present invention can exhibit further excellent reworkability.
再者,上述黏著力之測定可藉由如下方式進行:藉由與對玻璃板之初始黏著力相同之方法製作評價用試樣;並藉由與初始黏著力相同之方法測定於溫度60℃、濕度90%RH下保存7天之後的黏著力。 In addition, the measurement of the above-mentioned adhesive force can be performed as follows: a sample for evaluation is prepared by the same method as the initial adhesion to the glass plate; and the temperature is measured at 60 ° C. by the same method as the initial adhesion. Adhesion after storage for 7 days at 90% RH.
本發明之表面保護膜對玻璃板之黏著力,於貼附於玻璃板並於85℃×50%RH×7天後,較佳為0.5N/25mm以下,更佳為0.005N/25mm~0.5N/25mm,進而較佳為0.005N/25mm~0.4N/25mm,特別較佳為0.005N/25mm~0.3N/25mm,最佳為0.01N/25mm~0.2N/25mm。藉由上述黏著力在上述範圍內,本發明之表面保護膜可表現進一步優異之再加工性。 The adhesion of the surface protective film of the present invention to a glass plate is preferably 0.5N / 25mm or less, more preferably 0.005N / 25mm ~ 0.5 after being attached to the glass plate and at 85 ° C × 50% RH × 7 days. N / 25mm, more preferably 0.005N / 25mm ~ 0.4N / 25mm, particularly preferably 0.005N / 25mm ~ 0.3N / 25mm, and most preferably 0.01N / 25mm ~ 0.2N / 25mm. With the above-mentioned adhesive force being within the above range, the surface protective film of the present invention can exhibit further excellent reworkability.
再者,上述黏著力之測定可藉由如下方式進行:藉由與對玻璃板之初始黏著力相同之方法製作評價用試樣;並藉由與初始黏著力相同之方法測定於溫度85℃、濕度50%RH下保存7天後的黏著力。 In addition, the measurement of the above-mentioned adhesive force can be performed as follows: a sample for evaluation is prepared by the same method as the initial adhesion to the glass plate; and the temperature is measured at 85 ° C. by the same method as the initial adhesion. Adhesion after storage for 7 days at 50% RH.
本發明之表面保護膜對玻璃板之黏著力,於剛貼附於玻璃板之後,貼附於玻璃板並於50℃×50%RH下×7天後,於60℃×90%RH×7天後,以及於85℃×50%RH×7天後,均較佳為0.5N/25mm以下,更佳為0.005N/25mm~0.5N/25mm,進而較佳為0.005N/25mm~0.4N/25mm,特別較佳為0.005N/25mm~0.3N/25mm,最佳為0.01N/25mm~0.2N/25mm。藉由上述黏著力在上述範圍內,本發明之表面保護膜可表現進一步優異之再加工性。 The adhesive force of the surface protective film of the present invention on the glass plate is immediately after being attached to the glass plate, and then attached to the glass plate at 50 ° C × 50% RH × 7 days, and then at 60 ° C × 90% RH × 7 After 5 days, and after 85 ° C × 50% RH × 7 days, it is preferably 0.5N / 25mm or less, more preferably 0.005N / 25mm ~ 0.5N / 25mm, and still more preferably 0.005N / 25mm ~ 0.4N / 25mm, particularly preferably 0.005N / 25mm to 0.3N / 25mm, and most preferably 0.01N / 25mm to 0.2N / 25mm. With the above-mentioned adhesive force being within the above range, the surface protective film of the present invention can exhibit further excellent reworkability.
本發明之表面保護膜較佳為透明性較高。藉由本發明之表面保護膜之透明性較高,於貼附於光學構件或電子構件之表面之狀態下可準確進行檢查等。本發明之表面保護膜之霧度較佳為5%以下,更佳為4%以下,進而較佳為3%以下,特別較佳為2%以下,最佳為1%以 下。再者,對霧度之測定與上述相同。 The surface protection film of the present invention is preferably highly transparent. Since the surface protection film of the present invention has high transparency, it can be accurately inspected and the like in a state of being attached to the surface of an optical member or an electronic member. The haze of the surface protective film of the present invention is preferably 5% or less, more preferably 4% or less, further preferably 3% or less, particularly preferably 2% or less, and most preferably 1% or less. under. The measurement of the haze is the same as described above.
黏著劑層包含本發明之胺甲酸乙酯系黏著劑。本發明之胺甲酸乙酯系黏著劑於黏著劑層中之含有比率較佳為50重量%~100重量%,更佳為70重量%~100重量%,進而較佳為90重量%~100重量%,特別較佳為95重量%~100重量%,最佳為98重量%~100重量%。將本發明之胺甲酸乙酯系黏著劑於黏著劑層中之含有比率於上述範圍內調整,可提供一種抗糊劑殘留性非常優異之表面保護膜。 The adhesive layer contains the urethane-based adhesive of the present invention. The content ratio of the urethane-based adhesive in the adhesive layer of the present invention is preferably 50% to 100% by weight, more preferably 70% to 100% by weight, and still more preferably 90% to 100% by weight. %, Particularly preferably 95% to 100% by weight, and most preferably 98% to 100% by weight. By adjusting the content ratio of the urethane-based adhesive of the present invention in the adhesive layer within the above-mentioned range, a surface protective film having excellent paste resistance can be provided.
作為黏著劑層之厚度,可根據用途,採用任意適當之厚度。黏著劑層之厚度較佳為1μm~100μm,更佳為3μm~50μm,進而較佳為5μm~30μm。 As the thickness of the adhesive layer, any appropriate thickness can be adopted depending on the application. The thickness of the adhesive layer is preferably 1 μm to 100 μm, more preferably 3 μm to 50 μm, and even more preferably 5 μm to 30 μm.
黏著劑層可藉由任意適當之製造方法而製造。作為此種製造方法,例如可列舉將作為黏著劑層之形成材料之組合物塗佈於基材層上,於基材層上形成黏著劑層之方法。作為此種塗佈之方法,例如可列舉:輥塗、凹版塗佈、逆向塗佈、輥刷、噴塗、氣刀塗佈法、利用模頭塗佈機等之擠出塗佈等。 The adhesive layer can be manufactured by any appropriate manufacturing method. As such a manufacturing method, the method of apply | coating the composition which is a forming material of an adhesive layer on a base material layer, and forming an adhesive layer on a base material layer are mentioned, for example. Examples of such a coating method include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, extrusion coating using a die coater, and the like.
作為基材層之厚度,可根據用途,採用任意適當之厚度。基材層之厚度較佳為5μm~300μm,更佳為10μm~250μm,進而較佳為15μm~200μm,特別較佳為20μm~150μm。 As the thickness of the base material layer, any appropriate thickness can be adopted depending on the application. The thickness of the substrate layer is preferably 5 μm to 300 μm, more preferably 10 μm to 250 μm, still more preferably 15 μm to 200 μm, and particularly preferably 20 μm to 150 μm.
基材層可為單層,或者可為兩層以上之積層體。基材層可為經延伸者。 The substrate layer may be a single layer, or may be a laminate of two or more layers. The substrate layer may be an stretcher.
作為基材層之材料,可根據用途,採用任意適當之材料。例如可列舉:塑膠、紙、金屬膜、不織布等。更佳為塑膠。基材層可由一種材料構成,或者可由兩種以上材料構成。例如,上述層可由兩種以上之塑膠構成。 As a material of the base material layer, any appropriate material can be adopted depending on the application. Examples include plastic, paper, metal film, and non-woven fabric. More preferably, it is plastic. The base material layer may be composed of one material, or may be composed of two or more materials. For example, the above layer may be composed of two or more plastics.
作為上述塑膠,例如可列舉:聚酯系樹脂、聚醯胺系樹脂、聚烯烴系樹脂等。作為聚酯系樹脂,例如可列舉:聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯等。作為聚烯烴系樹脂,例如可列舉:烯烴單體之均聚物、烯烴單體之共聚物等。作為聚烯烴系樹脂,具體而言例如可列舉:均聚丙烯;使用乙烯成分作為共聚成分之嵌段系、無規系、接枝系等丙烯系共聚物;反應器直接製備熱塑性聚烯烴(reactor TPO);低密度、高密度、線性低密度、超低密度等乙烯系聚合物;乙烯-丙烯共聚物、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-丙烯酸丁酯共聚物、乙烯-甲基丙烯酸共聚物、乙烯-甲基丙烯酸甲酯共聚物等乙烯系共聚物等。 Examples of the plastic include polyester resins, polyamide resins, and polyolefin resins. Examples of the polyester-based resin include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Examples of the polyolefin-based resin include a homopolymer of an olefin monomer and a copolymer of an olefin monomer. Specific examples of the polyolefin-based resin include: homopolypropylene; block-based, random-based, and graft-based propylene-based copolymers using an ethylene component as a copolymerization component; and a reactor directly preparing a thermoplastic polyolefin (reactor) TPO); low density, high density, linear low density, ultra-low density and other ethylene-based polymers; ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer Products, ethylene-butyl acrylate copolymers, ethylene-methacrylic acid copolymers, ethylene-methyl methacrylate copolymers, and other ethylene-based copolymers.
基材層可根據需要包含任意適當之添加劑。作為基材層中可含有之添加劑,例如可列舉:抗氧化劑、紫外線吸收劑、光穩定劑、抗靜電劑、填充劑、顏料等。基材層可含有之添加劑之種類、數、量可根據目的適當設定。尤其,於基材層之材料為塑膠之情形時,為了防止劣化等,較佳為含有幾種上述添加劑。就提高耐氣候性之觀點而言,作為添加劑,特別較佳可列舉:抗氧化劑、紫外線吸收劑、光穩定劑、填充劑。 The base material layer may contain any appropriate additive as needed. Examples of the additives that can be contained in the substrate layer include antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, fillers, pigments, and the like. The type, number, and amount of additives that can be contained in the substrate layer can be appropriately set according to the purpose. In particular, when the material of the base material layer is plastic, it is preferable to contain several of the aforementioned additives in order to prevent deterioration and the like. From the viewpoint of improving weather resistance, particularly preferred additives include antioxidants, ultraviolet absorbers, light stabilizers, and fillers.
作為抗氧化劑,可採用任意適當之抗氧化劑。作為此種抗氧化劑,例如可列舉:酚系抗氧化劑、磷系加工熱穩定劑、內酯系加工熱穩定劑、硫系熱穩定劑、酚-磷系抗氧化劑等。抗氧化劑之含有比率相對於基材層之基礎樹脂(於基材層為摻合物之情形時,其摻合物為基礎樹脂),較佳為1重量%以下,更佳為0.5重量%以下,進而較佳為0.01重量%~0.2重量%。 As the antioxidant, any appropriate antioxidant can be used. Examples of such an antioxidant include a phenol-based antioxidant, a phosphorus-based processing heat stabilizer, a lactone-based processing heat stabilizer, a sulfur-based heat stabilizer, and a phenol-phosphorus-based antioxidant. The content of the antioxidant is preferably 1% by weight or less, and more preferably 0.5% by weight or less, relative to the base resin of the base material layer (in the case where the base material layer is a blend, the blend is a base resin). , And more preferably 0.01% by weight to 0.2% by weight.
作為紫外線吸收劑,可採用任意適當之紫外線吸收劑。作為此種紫外線吸收劑,例如可列舉:苯并三唑系紫外線吸收劑、三嗪系紫 外線吸收劑、二苯甲酮系紫外線吸收劑等。紫外線吸收劑之含有比率相對於形成基材層之基礎樹脂(於基材層為摻合物之情形時,其摻合物為基礎樹脂),較佳為2重量%以下,更佳為1重量%以下,進而較佳為0.01重量%~0.5重量%。 As the ultraviolet absorber, any appropriate ultraviolet absorber can be used. Examples of such ultraviolet absorbers include benzotriazole-based ultraviolet absorbers and triazine-based violet. External absorbers, benzophenone-based ultraviolet absorbers, and the like. The content ratio of the ultraviolet absorber is preferably 2% by weight or less, and more preferably 1% by weight relative to the base resin forming the base layer (when the base layer is a blend, the blend is a base resin). % Or less, and more preferably 0.01% by weight to 0.5% by weight.
作為光穩定劑,可採用任意適當之光穩定劑。作為此種光穩定劑,例如可列舉:受阻胺系光穩定劑、苯甲酸酯系光穩定劑等。光穩定劑之含有比率相對於形成基材層之基礎樹脂(於基材層為摻合物之情形時,其摻合物為基礎樹脂),較佳為2重量%以下,更佳為1重量%以下,進而較佳為0.01重量%~0.5重量%。 As the light stabilizer, any appropriate light stabilizer can be used. Examples of such a light stabilizer include a hindered amine light stabilizer, a benzoate light stabilizer, and the like. The content ratio of the light stabilizer relative to the base resin forming the base layer (when the base layer is a blend, the blend is a base resin) is preferably 2% by weight or less, and more preferably 1% by weight % Or less, and more preferably 0.01% by weight to 0.5% by weight.
作為填充劑,可採用任意適當之填充劑。作為此種填充劑,例如可列舉無機系填充劑等。作為無機系填充劑,具體而言例如可列舉:碳黑、氧化鈦、氧化鋅等。填充劑之含有比率相對於形成基材層之基礎樹脂(於基材層為摻合物之情形時,其摻合物為基礎樹脂),較佳為20重量%以下,更佳為10重量%以下,進而較佳為0.01重量%~10重量%。 As the filler, any appropriate filler can be used. Examples of such a filler include an inorganic filler. Specific examples of the inorganic filler include carbon black, titanium oxide, and zinc oxide. The content of the filler is preferably 20% by weight or less, and more preferably 10% by weight, relative to the base resin forming the base layer (when the base layer is a blend, the blend is a base resin). Hereinafter, it is more preferably 0.01% by weight to 10% by weight.
進而,作為添加劑,以賦予抗靜電性為目的,亦較佳可列舉:界面活性劑、無機鹽、多元醇、金屬化合物、碳等無機系、低分子量系及高分子量系抗靜電劑。尤其,就污染、維持黏著性之觀點而言,較佳為高分子量系抗靜電劑或碳。 Further, as an additive, for the purpose of imparting antistatic properties, preferably, surfactants, inorganic salts, polyhydric alcohols, metal compounds, carbon, and other inorganic-based, low-molecular-weight, and high-molecular-weight antistatic agents are also mentioned. In particular, a high molecular weight antistatic agent or carbon is preferred from the viewpoint of contamination and maintaining adhesiveness.
本發明之表面保護膜可藉由任意適當之方法而製造。作為此種製造方法,例如可依據如下之任意適當之製造方法進行:(1)將黏著劑層之形成材料(例如,含有作為本發明之胺甲酸乙酯系黏著劑之原料之多元醇(A)與多官能異氰酸酯化合物(B)之組合物)的溶液或熱熔融液塗佈於基材層上之方法;(2)根據其,將於隔膜上塗佈、形成之黏著劑層轉移至基材層上 之方法;(3)將黏著劑層之形成材料擠出於基材層上形成塗佈之方法;(4)將基材層與黏著劑層擠出為兩層或多層之方法;(5)於基材層上將黏著劑層單層層壓之方法,或者將層壓層與黏著劑層一併兩層層壓之方法;或者(6)將黏著劑層與膜或層壓層等基材層形成材料兩層層壓或多層層壓之方法等。 The surface protective film of the present invention can be produced by any appropriate method. Such a manufacturing method can be performed, for example, according to any appropriate manufacturing method as follows: (1) A material for forming an adhesive layer (for example, a polyol (A containing a raw material of the urethane-based adhesive of the present invention (A ) And a method of applying a solution of a composition of the polyfunctional isocyanate compound (B)) or a hot melt to the substrate layer; (2) according to the method, the adhesive layer coated and formed on the separator is transferred to the substrate Wood layer Method; (3) a method of extruding the material for forming the adhesive layer on the substrate layer to form a coating; (4) a method of extruding the substrate layer and the adhesive layer into two or more layers; (5) A method of laminating a single layer of an adhesive layer on a substrate layer, or a method of laminating two layers of a laminate layer and an adhesive layer together; or (6) a method of laminating an adhesive layer with a film or a laminate layer The material layer forming method is a method of laminating two layers or a plurality of layers.
本發明之胺甲酸乙酯系黏著劑可用於任意適當之用途。較佳為本發明之胺甲酸乙酯系黏著劑由於抗糊劑殘留性非常優異,故而藉由用作表面保護膜之黏著劑層,該表面保護膜可較佳用於光學構件或電子構件之表面保護。貼附有本發明之表面保護膜之光學構件或電子構件可以手工作業而多次貼附、剝離。 The urethane-based adhesive of the present invention can be used for any appropriate application. Since the urethane-based adhesive of the present invention is excellent in paste resistance, the surface protective film can be preferably used for an optical member or an electronic member by using the adhesive layer as a surface protective film. Surface protection. The optical member or electronic member to which the surface protection film of the present invention is attached can be manually attached and peeled off multiple times.
以下,藉由實施例對本發明進行具體說明,但本發明並不受該等實施例之任何限定。再者,實施例等中之試驗及評價方法如以下所述。再者,只要無特記事項,記載為「份」之情形意指「重量份」,且只要無特記事項,記載為「%」之情形意指「重量%」。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In addition, the test and evaluation method in an Example etc. are as follows. In addition, as long as there is no special note, the case described as "part" means "weight part", and as long as there is no special note, the case described as "%" means "weight%".
將表面保護膜切割為寬度70mm且長度130mm,並且具有隔膜之情形時,將隔膜剝離,其後,將2kg輥於預先除電之未處理玻璃(松浪硝子股份有限公司製造,尺寸1.35mm×10cm×10cm)往復一次。此時,表面保護膜成為自玻璃突出30cm之狀態。於23℃×50%RH之環境下放置一天之後,將自玻璃突出30cm之一個端部固定於自動捲繞機並以成為剝離角度150°、剝離速度10m/min之方式剝離。然後,利用固定於距表面保護膜10cm之位置之電位測定機(春日 電機公司製造,KSD-0103),測定剝離帶電電壓。該測定係於23℃×50%RH之環境下進行。 When the surface protective film was cut to a width of 70 mm and a length of 130 mm and a separator was used, the separator was peeled off, and then a 2 kg roll was rolled on untreated glass (made by Songlang Glass Co., Ltd., dimensions 1.35 mm × 10 cm × 10cm). At this time, the surface protection film was in a state of protruding 30 cm from the glass. After being left in an environment of 23 ° C. × 50% RH for one day, one end protruding from the glass by 30 cm was fixed to an automatic winder and peeled at a peeling angle of 150 ° and a peeling speed of 10 m / min. Then, a potentiometer (Kasuga (Manufactured by Denki Co., Ltd., KSD-0103), and measured the peeling electrification voltage. This measurement was performed in an environment of 23 ° C × 50% RH.
將表面保護膜切斷為寬度25mm且長度150mm,製成評價用試樣。於溫度23℃、濕度50%RH氣氛下,藉由將2.0kg輥往復一次,將評價用試樣之黏著劑層面貼附於玻璃板(松浪硝子工業股份有限公司製造,商品名:Micro Slide Glass S),於溫度23℃、濕度50%RH之氣氛下固化30分鐘,其後,利用通用拉伸試驗機(美蓓亞股份有限公司製造,產品名:TCM-1kNB),於剝離角度180°、拉伸速度300mm/min下進行剝離,測定黏著力。 The surface protective film was cut into a width of 25 mm and a length of 150 mm to prepare a sample for evaluation. At a temperature of 23 ° C. and a humidity of 50% RH, the 2.0 kg roll was reciprocated once, and the adhesive layer of the sample for evaluation was attached to a glass plate (manufactured by Songlang Glass Industry Co., Ltd., trade name: Micro Slide Glass S), curing in an atmosphere at a temperature of 23 ° C. and a humidity of 50% RH for 30 minutes, and then using a universal tensile tester (manufactured by Minebea Corporation, product name: TCM-1kNB) at a peel angle of 180 ° 2. Peel at a tensile speed of 300 mm / min, and measure the adhesion.
將表面保護膜切斷為寬度25mm且長度150mm,製成評價用試樣。於溫度23℃、濕度50%RH之氣氛下,藉由將2.0kg輥往復一次,將評價用試樣之黏著劑層面貼附於玻璃板(松浪硝子工業股份有限公司製造,商品名:Micro Slide Glass S),於濕度23℃、濕度50%RH之氣氛下固化30分鐘,其後,於溫度50℃、濕度50%RH保存7天,其後,利用通用拉伸試驗機(美蓓亞股份有限公司製造,產品名:TCM-1kNB),於剝離角度180°、拉伸速度300mm/min下進行剝離,測定黏著力。 The surface protective film was cut into a width of 25 mm and a length of 150 mm to prepare a sample for evaluation. In an atmosphere at a temperature of 23 ° C and a humidity of 50% RH, the 2.0 kg roll was reciprocated once, and the adhesive layer of the evaluation sample was attached to a glass plate (manufactured by Songlang Glass Industry Co., Ltd., trade name: Micro Slide Glass S), cured in an atmosphere with a humidity of 23 ° C and a humidity of 50% RH for 30 minutes, and then stored at a temperature of 50 ° C and a humidity of 50% RH for 7 days. Thereafter, a universal tensile tester (Minebea Corp. Co., Ltd., product name: TCM-1kNB), peeled at a peeling angle of 180 ° and a tensile speed of 300 mm / min, and measured the adhesive force.
將表面保護膜切斷為寬度25mm且長度150mm,製成評價用試樣。於溫度23℃、濕度50%RH之氣氛下,藉由將2.0kg輥往復一次,將評價用試樣之黏著劑層面貼附於玻璃板(松浪硝子工業股份有限公司製造,商品名:Micro Slide Glass S),於溫度23℃、濕度50%RH之氣氛下固化30分鐘,其後,於溫度60℃、濕度90%RH下保存7天,其 後,利用通用拉伸試驗機(美蓓亞股份有限公司製造,產品名:TCM-1kNB),於剝離角度180°、拉伸速度300mm/min下,進行剝離,測定黏著力。 The surface protective film was cut into a width of 25 mm and a length of 150 mm to prepare a sample for evaluation. In an atmosphere at a temperature of 23 ° C and a humidity of 50% RH, the 2.0 kg roll was reciprocated once, and the adhesive layer of the evaluation sample was attached to a glass plate (manufactured by Songlang Glass Industry Co., Ltd., trade name: Micro Slide Glass S), cured in an atmosphere at a temperature of 23 ° C and a humidity of 50% RH for 30 minutes, and then stored at a temperature of 60 ° C and a humidity of 90% RH for 7 days. Then, a universal tensile tester (manufactured by Minebea Co., Ltd., product name: TCM-1kNB) was used to perform peeling at a peeling angle of 180 ° and a tensile speed of 300 mm / min to measure the adhesive force.
將表面保護膜切斷為寬度25mm且長度150mm,製作評價用試樣。於溫度23℃、濕度50%RH之氣氛下,藉由將2.0kg輥往復一次,將評價用試樣之黏著劑層面貼附於玻璃板(松浪硝子工業股份有限公司製造,商品名:Micro Slide Glass S),於溫度23℃、濕度50%RH之氣氛下固化30分鐘,其後,於溫度85℃、濕度50%RH下保存7天,其後,利用通用拉伸試驗機(美蓓亞股份有限公司製造,產品名:TCM-1kNB),以剝離角度180°、拉伸速度300mm/min進行剝離,測定黏著力。 The surface protective film was cut into a width of 25 mm and a length of 150 mm to prepare a sample for evaluation. In an atmosphere at a temperature of 23 ° C and a humidity of 50% RH, the 2.0 kg roll was reciprocated once, and the adhesive layer of the evaluation sample was attached to a glass plate (manufactured by Songlang Glass Industry Co., Ltd., trade name: Micro Slide Glass S), cured in an atmosphere at a temperature of 23 ° C and a humidity of 50% RH for 30 minutes, and then stored at a temperature of 85 ° C and a humidity of 50% RH for 7 days. Thereafter, a universal tensile tester (Minebea (Product name: TCM-1kNB), peeled at a peeling angle of 180 ° and a tensile speed of 300 mm / min, and the adhesive force was measured.
將作為多元醇(A)之85重量份之具有三個OH基之多元醇的PREMINOL S3011(旭硝子股份有限公司製造,Mn=10000)、13重量份之具有三個OH基之多元醇之SANNIX GP-3000(三洋化成工業股份有限公司製造,Mn=3000)、2重量份之具有三個OH基之多元醇之SANNIX GP-1000(三洋化成工業股份有限公司製造,Mn=1000),作為多官能異氰酸酯化合物(B)之18重量份之多官能脂環族異氰酸酯化合物的CORONATE HX(日本聚胺酯工業股份有限公司製造),0.04重量份之觸媒(日本化學產業股份有限公司製造,商品名:Nacem Ferric Iron),作為防劣化劑之0.50重量份之Irganox 1010(巴斯夫製造),30重量份之脂肪酸酯(棕櫚酸異丙酯,花王股份有限公司製造,商品名:EXCEPARL IPP,Mn=299),0.01重量份之1-乙基-3-甲基咪唑鎓雙(三氟甲基磺醯基)醯亞胺(第一工業製藥股份有限公司製造,IL210)、及作為稀釋溶劑之241重量份之乙酸乙酯加以混合,然後利用分散機進 行攪拌,獲得胺甲酸乙酯系黏著劑組合物。 As the polyol (A), 85 parts by weight of a polyol having three OH groups of PREMINOL S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000) and 13 parts by weight of SANNIX GP of a polyol having three OH groups -3000 (manufactured by Sanyo Chemical Industry Co., Ltd., Mn = 3000), 2 parts by weight of SANNIX GP-1000 (manufactured by Sanyo Chemical Industry Co., Ltd., Mn = 1000), as multifunctional 18 parts by weight of polyfunctional alicyclic isocyanate compound CORONATE HX (manufactured by Japan Polyurethane Industry Co., Ltd.) of isocyanate compound (B), 0.04 parts by weight of catalyst (manufactured by Japan Chemical Industry Co., Ltd., trade name: Nacem Ferric Iron), 0.50 parts by weight of Irganox 1010 (manufactured by BASF), 30 parts by weight of fatty acid esters (isopropyl palmitate, manufactured by Kao Corporation, trade name: EXCEPARL IPP, Mn = 299), 0.01 part by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., IL210), and 241 parts by weight of a diluting solvent Ethyl acetate Mixed, and then into a disperser Stirring was performed to obtain a urethane-based adhesive composition.
利用浸漬輥將所獲得之胺甲酸乙酯系黏著劑組合物塗佈於包含聚酯樹脂之基材「Lumirror S10」(厚度:38μm,東麗工業股份有限公司製造)上,使乾燥後之厚度成為12μm,然後於乾燥溫度130℃、乾燥時間2分鐘之條件下使其固化並乾燥。以如此方式,製作於基材上包含胺甲酸乙酯系黏著劑(1)之黏著劑層。 The obtained urethane-based adhesive composition was coated on a substrate “Lumirror S10” (thickness: 38 μm, manufactured by Toray Industries, Ltd.) containing a polyester resin with a dipping roller, and the thickness after drying was obtained. It became 12 micrometers, and it solidified and dried under the conditions of the drying temperature of 130 degreeC, and the drying time of 2 minutes. In this manner, an adhesive layer containing a urethane-based adhesive (1) on the substrate was prepared.
繼而,將於一個面進行聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(1)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protective film (1).
評價結果示於表1。 The evaluation results are shown in Table 1.
除將1-乙基-3-甲基咪唑鎓雙(三氟甲基磺醯基)醯亞胺之量變更為0.1重量份以外,以與實施例1相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(2)之黏著劑層。 Except that the amount of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide was changed to 0.1 part by weight, it was produced on the substrate in the same manner as in Example 1 and included Adhesive layer of urethane-based adhesive (2).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(2)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm that was subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (2).
評價結果示於表1。 The evaluation results are shown in Table 1.
除將1-乙基-3-甲基咪唑鎓雙(三氟甲基磺醯基)醯亞胺之量變更為1重量份以外,以與實施例1相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(3)之黏著劑層。 Except that the amount of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide was changed to 1 part by weight, it was produced on the substrate in the same manner as in Example 1 and included Adhesive layer of urethane-based adhesive (3).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(3)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which was subjected to a silicone treatment on one side, was adhered to the surface of the adhesive layer to obtain a surface protective film (3).
評價結果示於表1。 The evaluation results are shown in Table 1.
除將1-乙基-3-甲基咪唑鎓雙(三氟甲基磺醯基)醯亞胺之量變更為10重量份以外,以與實施例1相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(4)之黏著劑層。 Except that the amount of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide was changed to 10 parts by weight, it was produced on the substrate in the same manner as in Example 1 and contained on the substrate. Adhesive layer of urethane-based adhesive (4).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(4)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (4).
評價結果示於表1。 The evaluation results are shown in Table 1.
除將0.01重量份之1-乙基-3-甲基咪唑鎓雙(三氟甲基磺醯基)醯亞胺變更為0.01重量份之1-乙基-3-甲基咪唑鎓雙(氟磺醯基)醯亞胺(第一工業製藥股份有限公司製造,AS210)以外,以與實施例1相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(4)之黏著劑層。 Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (fluoro A pressure-sensitive adhesive layer containing a urethane-based pressure-sensitive adhesive (4) was prepared on the substrate in the same manner as in Example 1 except for the sulfo) imide (manufactured by Daiichi Kogyo Co., Ltd., AS210). .
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(4)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (4).
評價結果示於表1。 The evaluation results are shown in Table 1.
除將1-乙基-3-甲基咪唑鎓雙(氟磺醯基)醯亞胺之量變更為0.1重量份以外,以與實施例5相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(6)之黏著劑層。 Except that the amount of 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) fluorenimide was changed to 0.1 part by weight, the same method as in Example 5 was used to prepare a substrate containing ethyl carbamate. Adhesive layer of the ester-based adhesive (6).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(6)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm that was subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (6).
評價結果示於表1。 The evaluation results are shown in Table 1.
除將1-乙基-3-甲基咪唑鎓雙(氟磺醯基)醯亞胺之量變更為1重量份以外,以與實施例5相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(7)之黏著劑層。 Except that the amount of 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) fluorenimide was changed to 1 part by weight, in the same manner as in Example 5, an ethyl carbamate was produced on the substrate. Adhesive layer of the ester-based adhesive (7).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(7)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protective film (7).
評價結果示於表1。 The evaluation results are shown in Table 1.
除將1-乙基-3-甲基咪唑鎓雙(氟磺醯基)醯亞胺之量變更為10重量份以外,以與實施例5相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(8)之黏著劑層。 Except that the amount of 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) fluorenimine was changed to 10 parts by weight, in the same manner as in Example 5, ethyl carbamate was produced on the substrate. Adhesive layer of the ester-based adhesive (8).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(8)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm that is subjected to a silicone treatment on one side is bonded to the surface of the adhesive layer to obtain a surface protection film (8).
評價結果示於表1。 The evaluation results are shown in Table 1.
除將0.01重量份之1-乙基-3-甲基咪唑鎓雙(三氟甲基磺醯基)醯亞胺變更為0.01重量份之1-乙基-3-甲基咪唑鎓七氟丙基磺酸鹽(三菱材料電子化成股份有限公司製造,EMI-EF31)以外,以與實施例1相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(9)之黏著劑層。 Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of 1-ethyl-3-methylimidazolium heptafluoropropene An adhesive layer containing a urethane-based adhesive (9) on a substrate was prepared in the same manner as in Example 1 except for a sulfonic acid salt (manufactured by Mitsubishi Materials Electrochemical Corporation, EMI-EF31).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(9)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (9).
評價結果示於表2。 The evaluation results are shown in Table 2.
除將1-乙基-3-甲基咪唑鎓七氟丙基磺酸鹽之量變更為0.1重量份 以外,以與實施例9相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(10)之黏著劑層。 In addition to changing the amount of 1-ethyl-3-methylimidazolium heptafluoropropylsulfonate to 0.1 parts by weight Other than that, in the same manner as in Example 9, an adhesive layer containing a urethane-based adhesive (10) on a substrate was prepared.
繼而,將於一表面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(10)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm that is subjected to a silicone treatment on one surface is adhered to the surface of the adhesive layer to obtain a surface protection film (10).
評價結果示於表2。 The evaluation results are shown in Table 2.
除將1-乙基-3-甲基咪唑鎓七氟丙基磺酸鹽之量變更為1重量份以外,以與實施例9相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(11)之黏著劑層。 Except that the amount of 1-ethyl-3-methylimidazolium heptafluoropropylsulfonate was changed to 1 part by weight, a urethane-based adhesive was produced on the substrate in the same manner as in Example 9. The adhesive layer of the agent (11).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(11)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm that was subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (11).
評價結果示於表2。 The evaluation results are shown in Table 2.
除將1-乙基-3-甲基咪唑鎓七氟丙基磺酸鹽之量變更為10重量份以外,以與實施例9相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(12)之黏著劑層。 Except that the amount of 1-ethyl-3-methylimidazolium heptafluoropropylsulfonate was changed to 10 parts by weight, a urethane-based adhesive was produced on the substrate in the same manner as in Example 9. The adhesive layer of the agent (12).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(12)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (12).
評價結果示於表2。 The evaluation results are shown in Table 2.
除將0.01重量份之1-乙基-3-甲基咪唑鎓雙(三氟甲基磺醯基)醯亞胺變更為0.01重量份之1-乙基-3-甲基咪唑鎓三氟甲基磺酸鹽(三菱材料電子化成公司製造,EMI-EF11)以外,以與實施例1相同之方式,製 作於基材上包含胺甲酸乙酯系黏著劑(13)之黏著劑層。 Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of 1-ethyl-3-methylimidazolium trifluoromethane Except for sulfonic acid salt (manufactured by Mitsubishi Materials Electrochemical Corporation, EMI-EF11), in the same manner as in Example 1, An adhesive layer containing a urethane-based adhesive (13) on a substrate.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(13)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (13).
評價結果示於表2。 The evaluation results are shown in Table 2.
除將1-乙基-3-甲基咪唑鎓三氟甲基磺酸鹽之量變更為0.1重量份以外,以與實施例13相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(14)之黏著劑層。 Except that the amount of 1-ethyl-3-methylimidazolium trifluoromethanesulfonate was changed to 0.1 part by weight, a urethane-based adhesive was produced on the substrate in the same manner as in Example 13 The adhesive layer of the agent (14).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(14)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (14).
評價結果示於表2。 The evaluation results are shown in Table 2.
除將1-乙基-3-甲基咪唑鎓三氟甲基磺酸鹽之量變更為1重量份以外,以與實施例13相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(15)之黏著劑層。 Except that the amount of 1-ethyl-3-methylimidazolium trifluoromethanesulfonate was changed to 1 part by weight, a urethane-based adhesive was produced on the substrate in the same manner as in Example 13 The adhesive layer of the agent (15).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(15)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (15).
評價結果示於表2。 The evaluation results are shown in Table 2.
除將1-乙基-3-甲基咪唑鎓三氟甲基磺酸鹽之量變更為10重量份以外,以與實施例13相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(16)之黏著劑層。 Except that the amount of 1-ethyl-3-methylimidazolium trifluoromethanesulfonate was changed to 10 parts by weight, a urethane-based adhesive was produced on the substrate in the same manner as in Example 13 The adhesive layer of the agent (16).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂 之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(16)。 Next, a 25 μm-thick polyester resin containing polysiloxane will be treated on one side. The silicone-treated surface of the substrate is adhered to the surface of the adhesive layer to obtain a surface protection film (16).
評價結果示於表2。 The evaluation results are shown in Table 2.
除將0.01重量份之1-乙基-3-甲基咪唑鎓雙(三氟甲基磺醯基)醯亞胺變更為0.01重量份之1-己基-3-甲基咪唑鎓雙(氟磺醯基)醯亞胺(三菱材料電子化成股份有限公司製造,HMI-FSI)以外,以與實施例1相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(17)之黏著劑層。 Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of 1-hexyl-3-methylimidazolium bis (fluorosulfonic acid) An adhesive containing urethane-based adhesive (17) on the substrate was produced in the same manner as in Example 1 except for fluorenyl) imine (manufactured by Mitsubishi Materials Electrochemical Corporation, HMI-FSI). Floor.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(17)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (17).
評價結果示於表3。 The evaluation results are shown in Table 3.
除將1-己基-3-甲基咪唑鎓雙(氟磺醯基)醯亞胺之量變更為0.1重量份以外,以與實施例17相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(18)之黏著劑層。 Except that the amount of 1-hexyl-3-methylimidazolium bis (fluorosulfonyl) fluorenimide was changed to 0.1 part by weight, a urethane was prepared on the substrate in the same manner as in Example 17 The adhesive layer of the adhesive (18).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(18)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm that was subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (18).
評價結果示於表3。 The evaluation results are shown in Table 3.
除將1-己基-3-甲基咪唑鎓雙(氟磺醯基)醯亞胺之量變更為1重量份以外,以與實施例17相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(19)之黏著劑層。 Except that the amount of 1-hexyl-3-methylimidazolium bis (fluorosulfonyl) fluorenimide was changed to 1 part by weight, a urethane was prepared on the substrate in the same manner as in Example 17 The adhesive layer of the adhesive (19).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜 (19)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm which is subjected to a silicone treatment on one side is bonded to the surface of the adhesive layer to obtain a surface protective film. (19).
評價結果示於表3。 The evaluation results are shown in Table 3.
除將1-己基-3-甲基咪唑鎓雙(氟磺醯基)醯亞胺之量變更為10重量份以外,以與實施例17相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(20)之黏著劑層。 Except that the amount of 1-hexyl-3-methylimidazolium bis (fluorosulfonyl) fluorenimide was changed to 10 parts by weight, a urethane was included on the substrate in the same manner as in Example 17. The adhesive layer of the adhesive (20).
然後,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(20)。 Then, a silicone-treated surface of a substrate containing a polyester resin and having a thickness of 25 μm subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (20).
評價結果示於表3。 The evaluation results are shown in Table 3.
除將0.01重量份之1-乙基-3-甲基咪唑鎓雙(三氟甲基磺醯基)醯亞胺變更為0.01重量份之1-乙基-3-甲基吡啶鎓九氟丁基磺酸鹽(三菱材料電子化成股份有限公司製造,EtMePy-EF41)以外,以與實施例1相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(21)之黏著劑層。 Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimine to 0.01 parts by weight of 1-ethyl-3-methylpyridinium nonafluorobutane An adhesive layer containing a urethane-based adhesive (21) on a substrate was prepared in the same manner as in Example 1 except for a sulfonic acid salt (manufactured by Mitsubishi Materials Electrochemical Corporation, EtMePy-EF41).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(21)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (21).
評價結果示於表3。 The evaluation results are shown in Table 3.
除將1-乙基-3-甲基吡啶鎓九氟丁基磺酸鹽之量變更為0.1重量份以外,以與實施例21相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(22)之黏著劑層。 Except that the amount of 1-ethyl-3-methylpyridinium nonafluorobutyl sulfonate was changed to 0.1 parts by weight, a urethane-based adhesive was produced on the substrate in the same manner as in Example 21 The adhesive layer of the agent (22).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(22)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (22).
評價結果示於表3。 The evaluation results are shown in Table 3.
除將1-乙基-3-甲基吡啶鎓九氟丁基磺酸鹽之量變更為1重量份以外,以與實施例21相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(23)之黏著劑層。 Except that the amount of 1-ethyl-3-methylpyridinium nonafluorobutyl sulfonate was changed to 1 part by weight, a urethane-based adhesive was produced on the substrate in the same manner as in Example 21 The adhesive layer of the agent (23).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(23)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (23).
評價結果示於表3。 The evaluation results are shown in Table 3.
除將1-乙基-3-甲基吡啶鎓九氟丁基磺酸鹽之量變更為10重量份以外,以與實施例21相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(24)之黏著劑層。 Except that the amount of 1-ethyl-3-methylpyridinium nonafluorobutylsulfonate was changed to 10 parts by weight, a urethane-based adhesive was produced on the substrate in the same manner as in Example 21 The adhesive layer of the agent (24).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(24)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (24).
評價結果示於表3。 The evaluation results are shown in Table 3.
除將0.01重量份之1-乙基-3-甲基咪唑鎓雙(三氟甲基磺醯基)醯亞胺變更為0.01重量份之1-乙基-3-甲基吡啶鎓七氟丙基磺酸鹽(三菱材料電子化成股份有限公司製造,EtMePy-EF31)以外,以與實施例1相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(25)之黏著劑層。 Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimine to 0.01 parts by weight of 1-ethyl-3-methylpyridinium heptafluoropropene An adhesive layer containing a urethane-based adhesive (25) on a substrate was prepared in the same manner as in Example 1 except for a sulfonic acid salt (manufactured by Mitsubishi Materials Electrochemical Corporation, EtMePy-EF31).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(25)。 Then, a silicone-treated surface of a substrate containing a polyester resin and having a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (25).
評價結果示於表4。 The evaluation results are shown in Table 4.
除將1-乙基-3-甲基吡啶鎓七氟丙基磺酸鹽之量變更為0.1重量份以外,以與實施例25相同之方式,於基材上製作包含胺甲酸乙酯系黏著劑(26)之黏著劑層。 A urethane-based adhesive was produced on the substrate in the same manner as in Example 25 except that the amount of 1-ethyl-3-methylpyridinium heptafluoropropylsulfonate was changed to 0.1 part by weight. The adhesive layer of the agent (26).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(26)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (26).
評價結果示於表4。 The evaluation results are shown in Table 4.
除將1-乙基-3-甲基吡啶鎓七氟丙基磺酸鹽之量變更為1重量份以外,以與實施例25相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(27)之黏著劑層。 Except that the amount of 1-ethyl-3-methylpyridinium heptafluoropropylsulfonate was changed to 1 part by weight, a urethane-based adhesive was produced on the substrate in the same manner as in Example 25. The adhesive layer of the agent (27).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(27)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (27).
評價結果示於表4。 The evaluation results are shown in Table 4.
除將1-乙基-3-甲基吡啶鎓七氟丙基磺酸鹽之量變更為10重量份以外,以與實施例25相同之方式,於基材上製作包含胺甲酸乙酯系黏著劑(28)之黏著劑層。 A urethane-based adhesive was prepared on the substrate in the same manner as in Example 25 except that the amount of 1-ethyl-3-methylpyridinium heptafluoropropylsulfonate was changed to 10 parts by weight. The adhesive layer of the agent (28).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(28)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm that was subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (28).
評價結果示於表4。 The evaluation results are shown in Table 4.
除將0.01重量份之1-乙基-3-甲基咪唑鎓雙(三氟甲基磺醯基)醯亞 胺變更為0.01重量份之1-乙基-3-甲基吡啶鎓五氟乙基磺酸鹽(三菱材料電子化成股份有限公司製造,EtMePy-EF21)以外,以與實施例1相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(29)之黏著劑層。 In addition to 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorene Except that the amine was changed to 0.01 parts by weight of 1-ethyl-3-methylpyridinium pentafluoroethylsulfonate (manufactured by Mitsubishi Materials Electrochemical Corporation, EtMePy-EF21), in the same manner as in Example 1, An adhesive layer containing a urethane-based adhesive (29) on a substrate is prepared.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(29)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm that was subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (29).
評價結果示於表4。 The evaluation results are shown in Table 4.
除將1-乙基-3-甲基吡啶鎓五氟乙基磺酸鹽之量變更為0.1重量份以外,以與實施例29相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(30)之黏著劑層。 Except that the amount of 1-ethyl-3-methylpyridinium pentafluoroethylsulfonate was changed to 0.1 part by weight, a urethane-based adhesive was produced on the substrate in the same manner as in Example 29. The adhesive layer of the agent (30).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(30)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (30).
評價結果示於表4。 The evaluation results are shown in Table 4.
除將1-乙基-3-甲基吡啶鎓五氟乙基磺酸鹽之量變更為1重量份以外,以與實施例29相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(31)之黏著劑層。 Except that the amount of 1-ethyl-3-methylpyridinium pentafluoroethylsulfonate was changed to 1 part by weight, a urethane-based adhesive was produced on the substrate in the same manner as in Example 29. The adhesive layer of the agent (31).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(31)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (31).
評價結果示於表4。 The evaluation results are shown in Table 4.
除將1-乙基-3-甲基吡啶鎓五氟乙基磺酸鹽之量變更為10重量份以外,以與實施例29相同之方式,於基材上製作包含胺甲酸乙酯系黏 著劑(32)之黏著劑層。 Except that the amount of 1-ethyl-3-methylpyridinium pentafluoroethylsulfonate was changed to 10 parts by weight, a urethane-based adhesive was prepared on the substrate in the same manner as in Example 29. Adhesive layer of the adhesive (32).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(32)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one side is adhered to the surface of the adhesive layer to obtain a surface protection film (32).
評價結果示於表4。 The evaluation results are shown in Table 4.
除將0.01重量份之1-乙基-3-甲基咪唑鎓雙(三氟甲基磺醯基)醯亞胺變更為0.01重量份之1-乙基-3-甲基吡啶鎓三氟甲基磺酸鹽(三菱材料電子化成股份有限公司製造,EtMePy-EF11)以外,以與實施例1相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(33)之黏著劑層。 Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of 1-ethyl-3-methylpyridinium trifluoromethane An adhesive layer containing a urethane-based adhesive (33) on a substrate was prepared in the same manner as in Example 1 except for a sulfonic acid salt (manufactured by Mitsubishi Materials Electrochemical Corporation, EtMePy-EF11).
然後,將於一個面進行聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(33)。 Then, a silicone-treated surface of a substrate containing a polyester resin and having a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (33).
評價結果示於表5。 The evaluation results are shown in Table 5.
除將1-乙基-3-甲基吡啶鎓三氟甲基磺酸鹽之量變更為0.1重量份以外,以與實施例33相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(34)之黏著劑層。 Except that the amount of 1-ethyl-3-methylpyridinium trifluoromethanesulfonate was changed to 0.1 part by weight, a urethane-based adhesive was produced on the substrate in the same manner as in Example 33. The adhesive layer of the agent (34).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(34)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (34).
評價結果示於表5。 The evaluation results are shown in Table 5.
除將1-乙基-3-甲基吡啶鎓三氟甲基磺酸鹽之量變更為1重量份以外,以與實施例33相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(35)之黏著劑層。 A urethane-based adhesive was produced on the substrate in the same manner as in Example 33 except that the amount of 1-ethyl-3-methylpyridinium trifluoromethanesulfonate was changed to 1 part by weight. The adhesive layer of the agent (35).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(35)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (35).
評價結果示於表5。 The evaluation results are shown in Table 5.
除將1-乙基-3-甲基吡啶鎓三氟甲基磺酸鹽之量變更為10重量份以外,以與實施例33相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(36)之黏著劑層。 Except that the amount of 1-ethyl-3-methylpyridinium trifluoromethanesulfonate was changed to 10 parts by weight, a urethane-based adhesive was produced on the substrate in the same manner as in Example 33. The adhesive layer of the agent (36).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層之表面,獲得表面保護膜(36)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (36).
評價結果示於表5。 The evaluation results are shown in Table 5.
除將0.01重量份之1-乙基-3-甲基咪唑鎓雙(三氟甲基磺醯基)醯亞胺變更為0.01重量份之1-丁基-3-甲基吡啶鎓雙(三氟甲基磺醯基)醯亞胺(日本Carlit製造,CIL312)以外,以與實施例1相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(37)之黏著劑層。 Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of 1-butyl-3-methylpyridinium bis (tri A pressure-sensitive adhesive layer containing a urethane-based pressure-sensitive adhesive (37) on the substrate was prepared in the same manner as in Example 1 except for fluoromethylsulfonyl) fluorene imine (CIL312, manufactured by Japan Carlit).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(37)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (37).
評價結果示於表5。 The evaluation results are shown in Table 5.
除將1-丁基-3-甲基吡啶鎓雙(三氟甲基磺醯基)醯亞胺之量變更為0.1重量份以外,以與實施例37相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(38)之黏著劑層。 A substrate was prepared in the same manner as in Example 37 except that the amount of 1-butyl-3-methylpyridinium bis (trifluoromethylsulfonyl) fluorenimide was changed to 0.1 part by weight. Adhesive layer of urethane-based adhesive (38).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂 之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(38)。 Next, a 25 μm-thick polyester resin containing polysiloxane will be treated on one side. The silicone-treated surface of the substrate is adhered to the surface of the adhesive layer to obtain a surface protection film (38).
評價結果示於表5。 The evaluation results are shown in Table 5.
除將1-丁基-3-甲基吡啶鎓雙(三氟甲基磺醯基)醯亞胺之量變更為1重量份以外,以與實施例37相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(39)之黏著劑層。 A substrate was prepared in the same manner as in Example 37 except that the amount of 1-butyl-3-methylpyridinium bis (trifluoromethylsulfonyl) fluorenimide was changed to 1 part by weight. Adhesive layer of urethane-based adhesive (39).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(39)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (39).
評價結果示於表5。 The evaluation results are shown in Table 5.
除將1-丁基-3-甲基吡啶鎓雙(三氟甲基磺醯基)醯亞胺之量變更為10重量份以外,以與實施例37相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(40)之黏著劑層。 Except that the amount of 1-butyl-3-methylpyridinium bis (trifluoromethylsulfonyl) fluorenimide was changed to 10 parts by weight, the same method as in Example 37 was used to prepare a substrate. Adhesive layer of urethane-based adhesive (40).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(40)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface is adhered to the surface of the adhesive layer to obtain a surface protection film (40).
評價結果示於表5。 The evaluation results are shown in Table 5.
除將0.01重量份之1-乙基-3-甲基咪唑鎓雙(三氟甲基磺醯基)醯亞胺變更為0.01重量份之1-丁基-3-甲基吡啶鎓三氟甲基磺酸鹽(日本Carlit公司製造,CIL313)以外,以與實施例1相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(41)之黏著劑層。 Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of 1-butyl-3-methylpyridinium trifluoromethane An adhesive layer containing a urethane-based adhesive (41) on a substrate was prepared in the same manner as in Example 1 except for a sulfonic acid salt (CIL313, manufactured by Japan Carlit Corporation).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜 (41)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is bonded to the surface of the adhesive layer to obtain a surface protective film. (41).
評價結果示於表6。 The evaluation results are shown in Table 6.
除將1-丁基-3-甲基吡啶鎓三氟甲基磺酸鹽之量變更為0.1重量份以外,以與實施例41相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(42)之黏著劑層。 Except that the amount of 1-butyl-3-methylpyridinium trifluoromethanesulfonate was changed to 0.1 part by weight, a urethane-based adhesive was produced on the substrate in the same manner as in Example 41. The adhesive layer of the agent (42).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(42)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface is adhered to the surface of the adhesive layer to obtain a surface protection film (42).
評價結果示於表6。 The evaluation results are shown in Table 6.
除將1-丁基-3-甲基吡啶鎓三氟甲基磺酸鹽之量變更為1重量份以外,以與實施例41相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(43)之黏著劑層。 A urethane-based adhesive was produced on the substrate in the same manner as in Example 41 except that the amount of 1-butyl-3-methylpyridinium trifluoromethanesulfonate was changed to 1 part by weight. The adhesive layer of the agent (43).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(43)。 Then, a silicone-treated surface of a substrate containing a polyester resin and having a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (43).
評價結果示於表6。 The evaluation results are shown in Table 6.
除將1-丁基-3-甲基吡啶鎓三氟甲基磺酸鹽之量變更為10重量份以外,以與實施例41相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(44)之黏著劑層。 A urethane-based adhesive was produced on the substrate in the same manner as in Example 41 except that the amount of 1-butyl-3-methylpyridinium trifluoromethanesulfonate was changed to 10 parts by weight. The adhesive layer of the agent (44).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(44)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (44).
評價結果示於表6。 The evaluation results are shown in Table 6.
除將0.01重量份之1-乙基-3-甲基咪唑鎓雙(三氟甲基磺醯基)醯亞胺變更為0.01重量份之1-己基吡啶鎓雙(氟磺醯基)醯亞胺(三菱材料電子化成股份有限公司製造,HxPy-FSI)以外,以與實施例1相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(45)之黏著劑層。 Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of 1-hexylpyridinium bis (fluorosulfonyl) fluorene Except for amines (manufactured by Mitsubishi Materials Electrochemical Corporation, HxPy-FSI), an adhesive layer containing a urethane-based adhesive (45) on a substrate was prepared in the same manner as in Example 1.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(45)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (45).
評價結果示於表6。 The evaluation results are shown in Table 6.
除將1-己基吡啶鎓雙(氟磺醯基)醯亞胺之量變更為0.1重量份以外,以與實施例45相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(46)之黏著劑層。 Except that the amount of 1-hexylpyridinium bis (fluorosulfonyl) fluorenimide was changed to 0.1 part by weight, a urethane-based adhesive (46 ) 'S adhesive layer.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(46)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (46).
評價結果示於表6。 The evaluation results are shown in Table 6.
除將1-己基吡啶鎓雙(氟磺醯基)醯亞胺之量變更為1重量份以外,以與實施例45相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(47)之黏著劑層。 A urethane-based adhesive (47) was prepared on the substrate in the same manner as in Example 45 except that the amount of 1-hexylpyridinium bis (fluorosulfonyl) fluorenimide was changed to 1 part by weight. ) 'S adhesive layer.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(47)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (47).
評價結果示於表6。 The evaluation results are shown in Table 6.
除將1-己基吡啶鎓雙(氟磺醯基)醯亞胺之量變更為10重量份以外,以與實施例45相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(48)之黏著劑層。 Except that the amount of 1-hexylpyridinium bis (fluorosulfofluorenyl) fluorenimine was changed to 10 parts by weight, a urethane-based adhesive (48 ) 'S adhesive layer.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(48)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (48).
評價結果示於表6。 The evaluation results are shown in Table 6.
除將0.01重量份之1-乙基-3-甲基咪唑鎓雙(三氟甲基磺醯基)醯亞胺變更為0.01重量份之1-辛基-4-甲基吡啶鎓雙(氟磺醯基)醯亞胺(第一工業製藥股份有限公司製造,MP403),以與實施例1相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(49)之黏著劑層。 Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of 1-octyl-4-methylpyridinium bis (fluoro Sulfonyl) fluorene imine (manufactured by Daiichi Kogyo Co., Ltd., MP403) was prepared in the same manner as in Example 1, and an adhesive layer containing a urethane-based adhesive (49) on a substrate was prepared.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(49)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm that was subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (49).
評價結果示於表7。 The evaluation results are shown in Table 7.
除將1-辛基-4-甲基吡啶鎓雙(氟磺醯基)醯亞胺之量變更為0.1重量份以外,以與實施例49相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(50)之黏著劑層。 Except that the amount of 1-octyl-4-methylpyridinium bis (fluorosulfonyl) fluorenimine was changed to 0.1 part by weight, the same procedure as in Example 49 was performed to include ethyl carbamate on the substrate. Adhesive layer of the ester-based adhesive (50).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(50)。 Then, a silicone-treated surface of a substrate containing a polyester resin and having a thickness of 25 μm subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (50).
評價結果示於表7。 The evaluation results are shown in Table 7.
除將1-辛基-4-甲基吡啶鎓雙(氟磺醯基)醯亞胺之量變更為1重量 份以外,以與實施例49相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(51)之黏著劑層。 In addition to changing the amount of 1-octyl-4-methylpyridinium bis (fluorosulfonyl) fluorenimine to 1 weight Except for the components, an adhesive layer containing a urethane-based adhesive (51) on a substrate was prepared in the same manner as in Example 49.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(51)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (51).
評價結果示於表7。 The evaluation results are shown in Table 7.
除將1-辛基-4-甲基吡啶鎓雙(氟磺醯基)醯亞胺之量變更為10重量份以外,以與實施例49相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(52)之黏著劑層。 Except that the amount of 1-octyl-4-methylpyridinium bis (fluorosulfonyl) fluorenimide was changed to 10 parts by weight, in the same manner as in Example 49, ethyl carbamate was produced on the substrate. Adhesive layer of the ester-based adhesive (52).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(52)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (52).
評價結果示於表7。 The evaluation results are shown in Table 7.
除將0.01重量份之1-乙基-3-甲基咪唑鎓雙(三氟甲基磺醯基)醯亞胺變更為0.01重量份之三甲基丙基銨雙(三氟甲基磺醯基)醯亞胺(東洋合成工業股份有限公司製造,TMPA-TFSI),以與實施例1相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(53)之黏著劑層。 Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of trimethylpropylammonium bis (trifluoromethylsulfonium) Base) fluorene imine (manufactured by Toyo Kogyo Co., Ltd., TMPA-TFSI), in the same manner as in Example 1, an adhesive layer containing a urethane-based adhesive (53) on a substrate was prepared.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(53)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (53).
評價結果示於表7。 The evaluation results are shown in Table 7.
除將三甲基丙基銨雙(三氟甲基磺醯基)醯亞胺之量變更為0.1重量份以外,以與實施例53相同之方式,製作於基材上包含胺甲酸乙酯系 黏著劑(54)之黏著劑層。 Except that the amount of trimethylpropylammonium bis (trifluoromethylsulfonyl) fluorenimide was changed to 0.1 part by weight, a urethane system was produced on the substrate in the same manner as in Example 53. Adhesive layer of adhesive (54).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(54)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (54).
評價結果示於表7。 The evaluation results are shown in Table 7.
除將三甲基丙基銨雙(雙三氟甲基磺醯基)醯亞胺之量變更為1重量份以外,以與實施例53相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(55)之黏著劑層。 Except that the amount of trimethylpropylammonium bis (bistrifluoromethylsulfonyl) sulfonium imine was changed to 1 part by weight, a urethane was included on the substrate in the same manner as in Example 53. The adhesive layer of the adhesive (55).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(55)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (55).
評價結果示於表7。 The evaluation results are shown in Table 7.
除將三甲基丙基銨雙(雙三氟甲基磺醯基)醯亞胺之量變更為10重量份以外,以與實施例53相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(56)之黏著劑層。 Except that the amount of trimethylpropylammonium bis (bistrifluoromethylsulfonyl) fluorenimide was changed to 10 parts by weight, a urethane was prepared on the substrate in the same manner as in Example 53. The adhesive layer of the adhesive (56).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(56)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface is adhered to the surface of the adhesive layer to obtain a surface protection film (56).
評價結果示於表7。 The evaluation results are shown in Table 7.
除將0.01重量份之1-乙基-3-甲基咪唑鎓雙(三氟甲基磺醯基)醯亞胺變更為0.01重量份之1-甲基-1-丙基吡咯烷鎓雙(三氟甲基磺醯基)醯亞胺(第一工業製藥股份有限公司製造,IL220)以外,以與實施例1相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(57)之黏著劑層。 Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of 1-methyl-1-propylpyrrolidinium bis ( A urethane-based adhesive (57) was produced on the substrate in the same manner as in Example 1 except for trifluoromethylsulfonyl) fluorenimine (IL220 manufactured by Daiichi Kogyo Co., Ltd.). Adhesive layer.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(57)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (57).
評價結果示於表8。 The evaluation results are shown in Table 8.
除將1-甲基-1-丙基吡咯烷鎓雙(三氟甲基磺醯基)醯亞胺之量變更為0.1重量份以外,以與實施例57相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(58)之黏著劑層。 A substrate was prepared on the substrate in the same manner as in Example 57 except that the amount of 1-methyl-1-propylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimide was changed to 0.1 part by weight. An adhesive layer containing a urethane-based adhesive (58).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(58)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (58).
評價結果示於表8。 The evaluation results are shown in Table 8.
除將1-甲基-1-丙基吡咯烷鎓雙(三氟甲基磺醯基)醯亞胺之量變更為1重量份以外,以與實施例57相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(59)之黏著劑層。 A substrate was prepared on the substrate in the same manner as in Example 57 except that the amount of 1-methyl-1-propylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimide was changed to 1 part by weight. An adhesive layer containing a urethane-based adhesive (59).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(59)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm that is subjected to a silicone treatment on one side is bonded to the surface of the adhesive layer to obtain a surface protection film (59).
評價結果示於表8。 The evaluation results are shown in Table 8.
除將1-甲基-1-丙基吡咯烷鎓雙(三氟甲基磺醯基)醯亞胺之量變更為10重量份以外,以與實施例57相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(60)之黏著劑層。 A substrate was prepared on the substrate in the same manner as in Example 57 except that the amount of 1-methyl-1-propylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimide was changed to 10 parts by weight. An adhesive layer containing a urethane-based adhesive (60).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜 (60)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is bonded to the surface of the adhesive layer to obtain a surface protective film. (60).
評價結果示於表8。 The evaluation results are shown in Table 8.
除將0.01重量份之1-乙基-3-甲基咪唑鎓雙(三氟甲基磺醯基)醯亞胺變更為0.01重量份之1-甲基-1-丙基吡咯烷鎓雙(氟磺醯基)醯亞胺(第一工業製藥股份有限公司製造,AS120)以外,以與實施例1相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(61)之黏著劑層。 Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of 1-methyl-1-propylpyrrolidinium bis ( An adhesive containing a urethane-based adhesive (61) on the substrate was prepared in the same manner as in Example 1 except for fluorosulfonyl) fluorenimine (manufactured by Daiichi Kogyo Co., Ltd., AS120). Floor.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(61)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (61).
評價結果示於表8。 The evaluation results are shown in Table 8.
除將1-甲基-1-丙基吡咯烷鎓雙(氟磺醯基)醯亞胺之量變更為0.1重量份以外,以與實施例61相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(62)之黏著劑層。 Except that the amount of 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) fluorenimine was changed to 0.1 part by weight, a carbamic acid was produced on the substrate in the same manner as in Example 61. Adhesive layer of ethyl-based adhesive (62).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(62)。 Next, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (62).
評價結果示於表8。 The evaluation results are shown in Table 8.
除將1-甲基-1-丙基吡咯烷鎓雙(氟磺醯基)醯亞胺之量變更為1重量份以外,以與實施例61相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(63)之黏著劑層。 Except that the amount of 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) fluorenimine was changed to 1 part by weight, carbamic acid was produced on the substrate in the same manner as in Example 61. Adhesive layer of ethyl-based adhesive (63).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(63)。 Then, a silicone-treated surface of a substrate containing a polyester resin and having a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (63).
評價結果示於表8。 The evaluation results are shown in Table 8.
除將1-甲基-1-丙基吡咯烷鎓雙(氟磺醯基)醯亞胺之量變更為10重量份以外,以與實施例61相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(64)之黏著劑層。 Except that the amount of 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) fluorenimide was changed to 10 parts by weight, a carbamic acid was produced on the substrate in the same manner as in Example 61. Adhesive layer of ethyl-based adhesive (64).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(64)。 Next, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (64).
評價結果示於表8。 The evaluation results are shown in Table 8.
除將0.01重量份之1-乙基-3-甲基咪唑鎓雙(三氟甲基磺醯基)醯亞胺變更為0.01重量份之1-甲基-1-丙基哌啶鎓雙(三氟甲基磺醯基)醯亞胺(第一工業製藥股份有限公司製造,IL230)以外,以與實施例1相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(65)之黏著劑層。 Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of 1-methyl-1-propylpiperidinium bis ( Except for trifluoromethylsulfonyl) fluorene imine (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., IL230), a urethane-based adhesive (65) was produced on the substrate in the same manner as in Example 1. Adhesive layer.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(65)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (65).
評價結果示於表9。 The evaluation results are shown in Table 9.
除將1-甲基-1-丙基哌啶鎓雙(三氟甲基磺醯基)醯亞胺之量變更為0.1重量份以外,以與實施例65相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(66)之黏著劑層。 A substrate was prepared on the substrate in the same manner as in Example 65 except that the amount of 1-methyl-1-propylpiperidinium bis (trifluoromethylsulfonyl) fluorenimide was changed to 0.1 part by weight. An adhesive layer containing a urethane-based adhesive (66).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(66)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (66).
評價結果示於表9。 The evaluation results are shown in Table 9.
除將1-甲基-1-丙基哌啶鎓雙(三氟甲基磺醯基)醯亞胺之量變更為1重量份以外,以與實施例65相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(67)之黏著劑層。 A substrate was prepared on the substrate in the same manner as in Example 65 except that the amount of 1-methyl-1-propylpiperidinium bis (trifluoromethylsulfonyl) fluorenimide was changed to 1 part by weight. An adhesive layer containing a urethane-based adhesive (67).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(67)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (67).
評價結果示於表9。 The evaluation results are shown in Table 9.
除將1-甲基-1-丙基哌啶鎓雙(三氟甲基磺醯基)醯亞胺之量變更為10重量份以外,以與實施例65相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(68)之黏著劑層。 Except that the amount of 1-methyl-1-propylpiperidinium bis (trifluoromethylsulfonyl) fluorenimide was changed to 10 parts by weight, it was produced on the substrate in the same manner as in Example 65. An adhesive layer containing a urethane-based adhesive (68).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(68)。 Then, a silicone-treated surface of a substrate containing a polyester resin and having a thickness of 25 μm subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (68).
評價結果示於表9。 The evaluation results are shown in Table 9.
除將0.01重量份之1-乙基-3-甲基咪唑鎓雙(三氟甲基磺醯基)醯亞胺變更為0.01重量份之1-甲基-1-丙基哌啶鎓雙(氟磺醯基)醯亞胺(第一工業製藥股份有限公司製造,AS130)以外,以與實施例1相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(69)之黏著劑層。 Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of 1-methyl-1-propylpiperidinium bis ( An adhesive containing a urethane-based adhesive (69) on the substrate was prepared in the same manner as in Example 1 except for fluorosulfonyl) fluorenimine (manufactured by Daiichi Kogyo Co., Ltd., AS130). Floor.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(69)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (69).
評價結果示於表9。 The evaluation results are shown in Table 9.
除將1-甲基-1-丙基哌啶鎓雙(氟磺醯基)醯亞胺之量變更為0.1重量份以外,以與實施例69相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(70)之黏著劑層。 Except that the amount of 1-methyl-1-propylpiperidinium bis (fluorosulfofluorenyl) fluorenimide was changed to 0.1 part by weight, carbamic acid was produced on the substrate in the same manner as in Example 69. Adhesive layer of ethyl-based adhesive (70).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(70)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface is adhered to the surface of the adhesive layer to obtain a surface protection film (70).
評價結果示於表9。 The evaluation results are shown in Table 9.
除將1-甲基-1-丙基哌啶鎓雙(氟磺醯基)醯亞胺之量變更為1重量份以外,以與實施例69相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(71)之黏著劑層。 Except that the amount of 1-methyl-1-propylpiperidinium bis (fluorosulfofluorenyl) fluorenimide was changed to 1 part by weight, carbamic acid was produced on the substrate in the same manner as in Example 69. Adhesive layer of ethyl-based adhesive (71).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(71)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (71).
評價結果示於表9。 The evaluation results are shown in Table 9.
除將1-甲基-1-丙基哌啶鎓雙(氟磺醯基)醯亞胺之量變更為10重量份以外,以與實施例69相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(72)之黏著劑層。 Except that the amount of 1-methyl-1-propylpiperidinium bis (fluorosulfofluorenyl) fluorenimine was changed to 10 parts by weight, uramic acid was produced on the substrate in the same manner as in Example 69. Adhesive layer of ethyl-based adhesive (72).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(72)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (72).
評價結果示於表9。 The evaluation results are shown in Table 9.
除將0.01重量份之1-乙基-3-甲基咪唑鎓雙(三氟甲基磺醯基)醯亞胺變更為0.01重量份之雙(三氟甲基磺醯基)醯亞胺鋰(森田化學工業股 份有限公司製造,Li-TFSI)以外,以與實施例1相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(73)之黏著劑層。 Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of lithium bis (trifluoromethylsulfonyl) sulfonium imine (Morita Chemical Industry Co., Ltd. Except for Li-TFSI, manufactured by Co., Ltd., in the same manner as in Example 1, an adhesive layer containing a urethane-based adhesive (73) on a substrate was prepared.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(73)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (73).
評價結果示於表10。 The evaluation results are shown in Table 10.
除將雙(三氟甲基磺醯基)醯亞胺鋰之量變更為0.1重量份以外,以與實施例73相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(74)之黏著劑層。 A urethane-based adhesive (74) was produced on the substrate in the same manner as in Example 73 except that the amount of lithium bis (trifluoromethylsulfonyl) fluorenimide was changed to 0.1 part by weight. Adhesive layer.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(74)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface is bonded to the surface of the adhesive layer to obtain a surface protection film (74).
評價結果示於表10。 The evaluation results are shown in Table 10.
除將雙(三氟甲基磺醯基)醯亞胺鋰之量變更為1重量份以外,以與實施例73相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(75)之黏著劑層。 A urethane-based adhesive (75) was produced on the substrate in the same manner as in Example 73 except that the amount of lithium bis (trifluoromethylsulfonyl) fluorenimide was changed to 1 part by weight. Adhesive layer.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(75)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (75).
評價結果示於表10。 The evaluation results are shown in Table 10.
除將雙(三氟甲基磺醯基)醯亞胺鋰之量變更為10重量份以外,以與實施例73相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(76)之黏著劑層。 A urethane-based adhesive (76) was produced on the substrate in the same manner as in Example 73 except that the amount of lithium bis (trifluoromethylsulfonyl) fluorenimide was changed to 10 parts by weight. Adhesive layer.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(76)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one side is adhered to the surface of the adhesive layer to obtain a surface protection film (76).
評價結果示於表10。 The evaluation results are shown in Table 10.
除將0.01重量份之1-乙基-3-甲基咪唑鎓雙(三氟甲基磺醯基)醯亞胺變更為0.01重量份之雙(氟磺醯基)醯亞胺鋰(森田化學工業股份有限公司製造,Li-TFSI)以外,以與實施例1相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(77)之黏著劑層。 In addition to changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of lithium bis (fluorosulfonyl) fluorenimide (Morita Chemicals) Except for Li-TFSI (manufactured by Industrial Co., Ltd.), an adhesive layer containing a urethane-based adhesive (77) on a substrate was prepared in the same manner as in Example 1.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(77)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protective film (77).
評價結果示於表10。 The evaluation results are shown in Table 10.
除將雙(氟磺醯基)醯亞胺鋰之量變更為0.1重量份以外,以與實施例77相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(78)之黏著劑層。 An adhesive containing a urethane-based adhesive (78) on the substrate was produced in the same manner as in Example 77 except that the amount of lithium bis (fluorosulfonyl) fluorenimide was changed to 0.1 part by weight. Floor.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(78)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface is adhered to the surface of the adhesive layer to obtain a surface protective film (78).
評價結果示於表10。 The evaluation results are shown in Table 10.
除將雙(氟磺醯基)醯亞胺鋰之量變更為1重量份以外,以與實施例77相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(79)之黏著劑層。 An adhesive containing a urethane-based adhesive (79) on the substrate was produced in the same manner as in Example 77 except that the amount of lithium bis (fluorosulfonyl) fluorenimide was changed to 1 part by weight. Floor.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂 之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(79)。 Next, a 25 μm-thick polyester resin containing polysiloxane will be treated on one side. The silicone-treated surface of the base material is adhered to the surface of the adhesive layer to obtain a surface protection film (79).
評價結果示於表10。 The evaluation results are shown in Table 10.
除將雙(氟磺醯基)醯亞胺鋰之量變更為10重量份以外,以與實施例77相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(80)之黏著劑層。 An adhesive containing a urethane-based adhesive (80) on the substrate was produced in the same manner as in Example 77 except that the amount of lithium bis (fluorosulfonyl) fluorenimide was changed to 10 parts by weight. Floor.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(80)。 Then, a silicone-treated surface of a substrate containing a polyester resin and having a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protective film (80).
評價結果示於表10。 The evaluation results are shown in Table 10.
除進而添加0.001重量份之兩末端型聚醚改性矽酮油(信越化學工業股份有限公司製造,KF-6004)作為製造胺甲酸乙酯系黏著劑組合物時之調配物以外,以與實施例5相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(81)之黏著劑層。 Except for adding 0.001 parts by weight of a two-terminal polyether-modified silicone oil (Shin-Etsu Chemical Industry Co., Ltd., KF-6004) as a formulation when manufacturing a urethane-based adhesive composition, In the same manner as in Example 5, an adhesive layer containing a urethane-based adhesive (81) on a substrate was prepared.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(81)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protective film (81).
評價結果示於表11。 The evaluation results are shown in Table 11.
除進而添加0.001重量份之兩末端型聚醚改性矽酮油(信越化學工業股份有限公司製造,KF-6004)作為製造胺甲酸乙酯系黏著劑組合物之調配物以外,以與實施例6相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(82)之黏著劑層。 Except for adding 0.001 parts by weight of a two-terminal polyether-modified silicone oil (Shin-Etsu Chemical Industry Co., Ltd., KF-6004) as a formulation for producing a urethane-based adhesive composition, the same procedure as in the examples was performed. 6 In the same manner, an adhesive layer containing a urethane-based adhesive (82) on the substrate was prepared.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂 之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(82)。 Next, a 25 μm-thick polyester resin containing polysiloxane will be treated on one side. The silicone-treated surface of the substrate is adhered to the surface of the adhesive layer to obtain a surface protection film (82).
評價結果示於表11。 The evaluation results are shown in Table 11.
除進而添加0.001重量份之兩末端型聚醚改性矽酮油(信越化學工業股份有限公司製造,KF-6004)作為製造胺甲酸乙酯系黏著劑組合物時之調配物以外,以與實施例7相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(83)之黏著劑層。 Except for adding 0.001 parts by weight of a two-terminal polyether-modified silicone oil (Shin-Etsu Chemical Industry Co., Ltd., KF-6004) as a formulation when manufacturing a urethane-based adhesive composition, In the same manner as in Example 7, an adhesive layer containing a urethane-based adhesive (83) on a substrate was prepared.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(83)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (83).
評價結果示於表11。 The evaluation results are shown in Table 11.
除進而調配0.001重量份之兩末端型聚醚改性矽酮油(信越化學工業股份有限公司製造,KF-6004)作為製造胺甲酸乙酯系黏著劑組合物之調配物以外,以與實施例8相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(84)之黏著劑層。 Except that 0.001 part by weight of a two-terminal polyether-modified silicone oil (Shin-Etsu Chemical Industry Co., Ltd., KF-6004) was further formulated as a formulation for producing a urethane-based adhesive composition, the same procedures as in the examples 8 In the same manner, an adhesive layer containing a urethane-based adhesive (84) on a substrate was prepared.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(84)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (84).
評價結果示於表11。 The evaluation results are shown in Table 11.
除進而添加0.1重量份之兩末端型聚醚改性矽酮油(信越化學工業股份有限公司製造,KF-6004)作為製造胺甲酸乙酯系黏著劑組合物時之調配物以外,以與實施例5相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(85)之黏著劑層。 Except for adding 0.1 parts by weight of a two-terminal polyether-modified silicone oil (Shin-Etsu Chemical Industry Co., Ltd., KF-6004) as a formulation when producing a urethane-based adhesive composition, In the same manner as in Example 5, an adhesive layer containing a urethane-based adhesive (85) on a substrate was prepared.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(85)。 Next, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (85).
評價結果示於表11。 The evaluation results are shown in Table 11.
除進而添加0.1重量份之兩末端型聚醚改性矽酮油(信越化學工業股份有限公司製造,KF-6004)作為製造胺甲酸乙酯系黏著劑組合物時之調配物以外,以與實施例6相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(86)之黏著劑層。 Except for adding 0.1 parts by weight of a two-terminal polyether-modified silicone oil (Shin-Etsu Chemical Industry Co., Ltd., KF-6004) as a formulation when producing a urethane-based adhesive composition, In the same manner as in Example 6, an adhesive layer containing a urethane-based adhesive (86) on a substrate was prepared.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(86)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (86).
評價結果示於表11。 The evaluation results are shown in Table 11.
除進而添加0.1重量份之兩末端型聚醚改性矽酮油(信越化學工業股份有限公司製造,KF-6004)作為製造胺甲酸乙酯系黏著劑組合物時之調配物以外,以與實施例7相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(87)之黏著劑層。 Except for adding 0.1 parts by weight of a two-terminal polyether-modified silicone oil (Shin-Etsu Chemical Industry Co., Ltd., KF-6004) as a formulation when producing a urethane-based adhesive composition, In the same manner as in Example 7, an adhesive layer containing a urethane-based adhesive (87) on a substrate was prepared.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(87)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (87).
評價結果示於表11。 The evaluation results are shown in Table 11.
除進而添加0.1重量份之兩末端型聚醚改性矽酮油(信越化學工業股份有限公司製造,KF-6004)作為製造胺甲酸乙酯系黏著劑組合物時之調配物以外,以與實施例8相同之方式,製作於基材上包含胺甲酸 乙酯系黏著劑(88)之黏著劑層。 Except for adding 0.1 parts by weight of a two-terminal polyether-modified silicone oil (Shin-Etsu Chemical Industry Co., Ltd., KF-6004) as a formulation when producing a urethane-based adhesive composition, In the same manner as in Example 8 Adhesive layer of ethyl-based adhesive (88).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(88)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (88).
評價結果示於表11。 The evaluation results are shown in Table 11.
除進而添加1重量份之兩末端型聚醚改性矽酮油(信越化學工業股份有限公司製造,KF-6004)作為製造胺甲酸乙酯系黏著劑組合物時之調配物,以與實施例5相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(89)之黏著劑層。 In addition, 1 part by weight of a two-terminal polyether-modified silicone oil (Shin-Etsu Chemical Industry Co., Ltd., KF-6004) was added as a formulation when the urethane-based adhesive composition was manufactured, in accordance with the examples. 5 In the same manner, an adhesive layer containing a urethane-based adhesive (89) on a substrate was prepared.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(89)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (89).
評價結果示於表12。 The evaluation results are shown in Table 12.
除進而添加1重量份之兩末端型聚醚改性矽酮油(信越化學工業股份有限公司製造,KF-6004)作為製造胺甲酸乙酯系黏著劑組合物時之調配物以外,以與實施例6相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(90)之黏著劑層。 Except for the addition of 1 part by weight of a two-terminal polyether-modified silicone oil (Shin-Etsu Chemical Industry Co., Ltd., KF-6004) as a formulation when producing a urethane-based adhesive composition, In the same manner as in Example 6, an adhesive layer containing a urethane-based adhesive (90) on a substrate was prepared.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(90)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (90).
評價結果示於表12。 The evaluation results are shown in Table 12.
除進而調配1重量份之兩末端型聚醚改性矽酮油(信越化學工業股份有限公司製造,KF-6004)作為製造胺甲酸乙酯系黏著劑組合物時之 調配物以外,以與實施例7相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(91)之黏著劑層。 In addition, 1 part by weight of a two-terminal polyether-modified silicone oil (KF-6004, manufactured by Shin-Etsu Chemical Co., Ltd.) is used as a urethane-based adhesive composition. Except for the preparation, an adhesive layer containing a urethane-based adhesive (91) on the substrate was prepared in the same manner as in Example 7.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(91)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface is bonded to the surface of the adhesive layer to obtain a surface protection film (91).
評價結果示於表12。 The evaluation results are shown in Table 12.
除進而添加1重量份之兩末端型聚醚改性矽酮油(信越化學工業股份有限公司製造,KF-6004),作為製造胺甲酸乙酯系黏著劑組合物時之調配物以外,以與實施例8相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(92)之黏著劑層。 In addition to adding 1 part by weight of a two-terminal polyether-modified silicone oil (manufactured by Shin-Etsu Chemical Industry Co., Ltd., KF-6004), as a formulation when producing a urethane-based adhesive composition, In the same manner as in Example 8, an adhesive layer containing a urethane-based adhesive (92) on the substrate was prepared.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(92)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (92).
評價結果示於表12。 The evaluation results are shown in Table 12.
除進而添加0.001重量份之側鏈型聚醚改性矽酮油(信越化學工業股份有限公司製造,KF-353)作為製造胺甲酸乙酯系黏著劑組合物時之調配物以外,以與實施例5相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(93)之黏著劑層。 Except for adding 0.001 parts by weight of a side chain polyether-modified silicone oil (Shin-Etsu Chemical Industry Co., Ltd., KF-353) as a formulation when manufacturing a urethane-based adhesive composition, In the same manner as in Example 5, an adhesive layer containing a urethane-based adhesive (93) on a substrate was prepared.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(93)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (93).
評價結果示於表12。 The evaluation results are shown in Table 12.
除進而添加0.001重量份之側鏈型聚醚改性矽酮油(信越化學工業 股份有限公司製造,KF-353)作為製造胺甲酸乙酯系黏著劑組合物時之調配物以外,以與實施例6相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(94)之黏著劑層。 In addition, 0.001 parts by weight of a side chain polyether-modified silicone oil was added (Shin-Etsu Chemical Industry Co., Ltd. Co., Ltd., KF-353) was prepared in the same manner as in Example 6 except that it was used as a formulation when producing a urethane-based adhesive composition, and a urethane-based adhesive (94 ) 'S adhesive layer.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(94)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (94).
評價結果示於表12。 The evaluation results are shown in Table 12.
除進而添加0.001重量份之側鏈型聚醚改性矽酮油(信越化學工業股份有限公司製造,KF-353)作為製造胺甲酸乙酯系黏著劑組合物時之調配物以外,以與實施例7相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(95)之黏著劑層,。 Except for adding 0.001 parts by weight of a side chain polyether-modified silicone oil (Shin-Etsu Chemical Industry Co., Ltd., KF-353) as a formulation when manufacturing a urethane-based adhesive composition, In the same manner as in Example 7, an adhesive layer containing a urethane-based adhesive (95) on a substrate was prepared.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(95)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (95).
評價結果示於表12。 The evaluation results are shown in Table 12.
除進而添加0.001重量份之側鏈型聚醚改性矽酮油(信越化學工業股份有限公司製造,KF-353)作為製造胺甲酸乙酯系黏著劑組合物時之調配物以外,以與實施例8相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(96)之黏著劑層。 Except for adding 0.001 parts by weight of a side chain polyether-modified silicone oil (Shin-Etsu Chemical Industry Co., Ltd., KF-353) as a formulation when manufacturing a urethane-based adhesive composition, In the same manner as in Example 8, an adhesive layer containing a urethane-based adhesive (96) on a substrate was prepared.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(96)。 Then, a silicone-treated surface of a substrate containing a polyester resin and having a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (96).
評價結果示於表12。 The evaluation results are shown in Table 12.
除進而添加0.1重量份之側鏈型聚醚改性矽酮油(信越化學工業股份有限公司製造,KF-353)作為製造胺甲酸乙酯系黏著劑組合物時之調配物以外,以與實施例5相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(97)之黏著劑層。 In addition to adding 0.1 parts by weight of a side chain polyether-modified silicone oil (KF-353, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) as a formulation when producing a urethane-based adhesive composition, In the same manner as in Example 5, an adhesive layer containing a urethane-based adhesive (97) on a substrate was prepared.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(97)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (97).
評價結果示於表13。 The evaluation results are shown in Table 13.
除進而添加0.1重量份之側鏈型聚醚改性矽酮油(信越化學工業股份有限公司製造,KF-353)作為製造胺甲酸乙酯系黏著劑組合物時之調配物以外,以與實施例6相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(98)之黏著劑層。 In addition to adding 0.1 parts by weight of a side chain polyether-modified silicone oil (KF-353, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) as a formulation when producing a urethane-based adhesive composition, In the same manner as in Example 6, an adhesive layer containing a urethane-based adhesive (98) on a substrate was prepared.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(98)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (98).
評價結果示於表13。 The evaluation results are shown in Table 13.
除進而添加0.1重量份之側鏈型聚醚改性矽酮油(信越化學工業股份有限公司製造,KF-353)作為製造胺甲酸乙酯系黏著劑組合物時之調配物以外,以與實施例7相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(99)之黏著劑層。 In addition to adding 0.1 parts by weight of a side chain polyether-modified silicone oil (KF-353, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) as a formulation when producing a urethane-based adhesive composition, In the same manner as in Example 7, an adhesive layer containing a urethane-based adhesive (99) on a substrate was prepared.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(99)。 Next, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which was subjected to a silicone treatment on one side, was adhered to the surface of the adhesive layer to obtain a surface protection film (99).
評價結果示於表13。 The evaluation results are shown in Table 13.
除進而添加0.1重量份之側鏈型聚醚改性矽酮油(信越化學工業股份有限公司製造,KF-353)作為製造胺甲酸乙酯系黏著劑組合物時之調配物以外,以與實施例8相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(100)之黏著劑層。 In addition to adding 0.1 parts by weight of a side chain polyether-modified silicone oil (KF-353, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) as a formulation when producing a urethane-based adhesive composition, In the same manner as in Example 8, an adhesive layer containing a urethane-based adhesive (100) on a substrate was prepared.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(100)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (100).
評價結果示於表13。 The evaluation results are shown in Table 13.
除進而添加1重量份之側鏈型聚醚改性矽酮油(信越化學工業股份有限公司製造,KF-353)作為製造胺甲酸乙酯系黏著劑組合物時之調配物以外,以與實施例5相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(101)之黏著劑層。 Except for adding 1 part by weight of a side chain type polyether-modified silicone oil (KF-353, manufactured by Shin-Etsu Chemical Co., Ltd.) as a formulation when manufacturing a urethane-based adhesive composition, In the same manner as in Example 5, an adhesive layer containing a urethane-based adhesive (101) on a substrate was prepared.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(101)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (101).
評價結果示於表13。 The evaluation results are shown in Table 13.
除進而添加1重量份之側鏈型聚醚改性矽酮油(信越化學工業股份有限公司製造,KF-353)作為製造胺甲酸乙酯系黏著劑組合物時之調配物以外,以與實施例6相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(102)之黏著劑層。 Except for adding 1 part by weight of a side chain type polyether-modified silicone oil (KF-353, manufactured by Shin-Etsu Chemical Co., Ltd.) as a formulation when manufacturing a urethane-based adhesive composition, In the same manner as in Example 6, an adhesive layer containing a urethane-based adhesive (102) on a substrate was prepared.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(102)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface is adhered to the surface of the adhesive layer to obtain a surface protection film (102).
評價結果示於表13。 The evaluation results are shown in Table 13.
除進而添加1重量份之側鏈型聚醚改性矽酮油(信越化學工業股份有限公司製造,KF-353)作為製造胺甲酸乙酯系黏著劑組合物時之調配物以外,以與實施例7相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(103)之黏著劑層。 Except for adding 1 part by weight of a side chain type polyether-modified silicone oil (KF-353, manufactured by Shin-Etsu Chemical Co., Ltd.) as a formulation when manufacturing a urethane-based adhesive composition, In the same manner as in Example 7, an adhesive layer containing a urethane-based adhesive (103) on a substrate was prepared.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(103)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (103).
評價結果示於表13。 The evaluation results are shown in Table 13.
除進而添加1重量份之側鏈型聚醚改性矽酮油(信越化學工業股份有限公司製造,KF-353)作為製造胺甲酸乙酯系黏著劑組合物時之調配物以外,以與實施例8相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(104)之黏著劑層。 Except for adding 1 part by weight of a side chain type polyether-modified silicone oil (KF-353, manufactured by Shin-Etsu Chemical Co., Ltd.) as a formulation when manufacturing a urethane-based adhesive composition, In the same manner as in Example 8, an adhesive layer containing a urethane-based adhesive (104) on a substrate was prepared.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(104)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (104).
評價結果示於表13。 The evaluation results are shown in Table 13.
除不使用脂肪酸酯及1-乙基-3-甲基咪唑鎓雙(三氟甲基磺醯基)醯亞胺以外,以與實施例1相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(C1)之黏著劑層。 Except that fatty acid ester and 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide were not used, the same method as in Example 1 was used to prepare a base material containing carbamic acid. Adhesive layer of ethyl-based adhesive (C1).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(C1)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (C1).
評價結果示於表14。 The evaluation results are shown in Table 14.
除不使用1-乙基-3-甲基咪唑鎓雙(三氟甲基磺醯基)醯亞胺以外,以與實施例1相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(C2)之黏著劑層。 Except that 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimine was not used, a urethane-based adhesive was produced on the substrate in the same manner as in Example 1 Adhesive layer of the agent (C2).
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(C2)。 Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protective film (C2).
評價結果示於表14。 The evaluation results are shown in Table 14.
除不使用脂肪酸酯及1-乙基-3-甲基咪唑鎓雙(三氟甲基磺醯基)醯亞胺;進而使用0.08重量份之EMBILIZER OL-1(東京精細化工股份有限公司製造)代替0.04重量份之Nacem Ferric Iron作為觸媒以外,以與實施例1相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(C3)之黏著劑層。 In addition to not using fatty acid esters and 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide; 0.08 parts by weight of EMBILIZER OL-1 (manufactured by Tokyo Fine Chemicals Co., Ltd.) ) In the same manner as in Example 1 except that 0.04 parts by weight of Nacem Ferric Iron was used as a catalyst, an adhesive layer containing a urethane-based adhesive (C3) on a substrate was prepared.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(C3)。 Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protective film (C3).
評價結果示於表14。 The evaluation results are shown in Table 14.
除不使用1-乙基-3-甲基咪唑鎓雙(三氟甲基磺醯基)醯亞胺;進而使用0.08重量份之EMBILIZER OL-1(東京精細化工股份有限公司製造)代替0.04重量份之Nacem Ferric Iron作為觸媒以外,以與實施例1相同之方式,製作於基材上包含胺甲酸乙酯系黏著劑(C4)之黏著劑層。 Except that 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimine is not used; furthermore, 0.08 parts by weight of EMBILIZER OL-1 (manufactured by Tokyo Fine Chemicals Co., Ltd.) is used instead of 0.04 weight An adhesive layer containing a urethane-based adhesive (C4) on a substrate was prepared in the same manner as in Example 1 except that Nacem Ferric Iron was used as a catalyst.
繼而,將於一個面實施聚矽氧處理之厚度25μm之包含聚酯樹脂 之基材之聚矽氧處理面貼合於黏著劑層的表面,獲得表面保護膜(C4)。 Next, a 25 μm-thick polyester resin containing polysiloxane will be treated on one side. The silicone-treated surface of the base material was bonded to the surface of the adhesive layer to obtain a surface protection film (C4).
評價結果示於表14。 The evaluation results are shown in Table 14.
將實施例4中獲得之表面保護膜(4)貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有表面保護膜之光學構件。 The surface protective film (4) obtained in Example 4 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member to obtain an optical member with a surface protective film attached thereto.
將實施例8中獲得之表面保護膜(8)貼附於作為光學構件之偏光板 (日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有表面保護膜之光學構件。 The surface protective film (8) obtained in Example 8 was attached to a polarizing plate as an optical member (Manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC"), an optical member with a surface protective film attached was obtained.
將實施例12中獲得之表面保護膜(12)貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有表面保護膜之光學構件。 The surface protective film (12) obtained in Example 12 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, and an optical member to which a surface protective film was attached was obtained.
將實施例16中獲得之表面保護膜(16)貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有表面保護膜之光學構件。 The surface protective film (16) obtained in Example 16 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, and an optical member to which a surface protective film was attached was obtained.
將實施例20中獲得之表面保護膜(20)貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有表面保護膜之光學構件。 The surface protective film (20) obtained in Example 20 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member to obtain an optical member with a surface protective film attached thereto.
將實施例24中獲得之表面保護膜(24)貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有表面保護膜之光學構件。 The surface protective film (24) obtained in Example 24 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, and an optical member with a surface protective film attached was obtained.
將實施例28中獲得之表面保護膜(28)貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有表面保護膜之光學構件。 The surface protective film (28) obtained in Example 28 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, to obtain an optical member with a surface protective film attached thereto.
將實施例32中獲得之表面保護膜(32)貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有表面保護膜之光學構件。 The surface protective film (32) obtained in Example 32 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, and an optical member with a surface protective film attached was obtained.
將實施例36中獲得之表面保護膜(36)貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有表面保護膜之光學構件。 The surface protective film (36) obtained in Example 36 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member to obtain an optical member with a surface protective film attached thereto.
將實施例40中獲得之表面保護膜(40)貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有表面保護膜之光學構件。 The surface protective film (40) obtained in Example 40 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member to obtain an optical member with a surface protective film attached thereto.
將實施例44中獲得之表面保護膜(44)貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有表面保護膜之光學構件。 The surface protective film (44) obtained in Example 44 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, and an optical member with a surface protective film attached was obtained.
將實施例48中獲得之表面保護膜(48)貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有表面保護膜之光學構件。 The surface protective film (48) obtained in Example 48 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, and an optical member to which a surface protective film was attached was obtained.
將實施例52中獲得之表面保護膜(52)貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有表面保護膜之光學構件。 The surface protective film (52) obtained in Example 52 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, and an optical member to which a surface protective film was attached was obtained.
將實施例56中獲得之表面保護膜(56)貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有表面保護膜之光學構件。 The surface protective film (56) obtained in Example 56 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member to obtain an optical member with a surface protective film attached thereto.
將實施例60中獲得之表面保護膜(60)貼附於作為光學構件之偏光 板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有表面保護膜之光學構件。 The surface protective film (60) obtained in Example 60 was attached to polarized light as an optical member Plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") to obtain an optical member with a surface protective film attached thereto.
將實施例60中獲得之表面保護膜(60)貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有表面保護膜之光學構件。 The surface protective film (60) obtained in Example 60 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, and an optical member with a surface protective film attached was obtained.
將實施例64中獲得之表面保護膜(64)貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有表面保護膜之光學構件。 The surface protective film (64) obtained in Example 64 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, and an optical member to which a surface protective film was attached was obtained.
將實施例68中獲得之表面保護膜(68)貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有表面保護膜之光學構件。 The surface protective film (68) obtained in Example 68 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member to obtain an optical member to which a surface protective film was attached.
將實施例72中獲得之表面保護膜(72)貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有表面保護膜之光學構件。 The surface protective film (72) obtained in Example 72 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, and an optical member to which a surface protective film was attached was obtained.
將實施例76中獲得之表面保護膜(76)貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有表面保護膜之光學構件。 The surface protective film (76) obtained in Example 76 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member to obtain an optical member with a surface protective film attached thereto.
將實施例80中獲得之表面保護膜(80)貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有表面保護膜之光學構件。 The surface protective film (80) obtained in Example 80 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member to obtain an optical member with a surface protective film attached thereto.
將實施例84中獲得之表面保護膜(84)貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有表面保護膜之光學構件。 The surface protective film (84) obtained in Example 84 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, and an optical member to which a surface protective film was attached was obtained.
將實施例88中獲得之表面保護膜(88)貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有表面保護膜之光學構件。 The surface protective film (88) obtained in Example 88 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member to obtain an optical member with a surface protective film attached thereto.
將實施例92中獲得之表面保護膜(92)貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有表面保護膜之光學構件。 The surface protective film (92) obtained in Example 92 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member to obtain an optical member with a surface protective film attached thereto.
將實施例96中獲得之表面保護膜(96)貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有表面保護膜之光學構件。 The surface protective film (96) obtained in Example 96 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member to obtain an optical member with a surface protective film attached thereto.
將實施例100中獲得之表面保護膜(100)貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有表面保護膜之光學構件。 The surface protective film (100) obtained in Example 100 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, and an optical member to which a surface protective film was attached was obtained.
將實施例104中獲得之表面保護膜(104)貼附於作為光學構件之偏光板(日東電工股份有限公司製造,商品名「TEG1465DUHC」),獲得貼附有表面保護膜之光學構件。 The surface protective film (104) obtained in Example 104 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, and an optical member with a surface protective film attached was obtained.
將實施例4中獲得之表面保護膜(4)貼附於作為電子構件之導電性 膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有表面保護膜之電子構件。 The surface protection film (4) obtained in Example 4 was attached to the electrical conductivity as an electronic component Film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP"), and an electronic component with a surface protective film attached.
將實施例8中獲得之表面保護膜(8)貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有表面保護膜之電子構件。 The surface protection film (8) obtained in Example 8 was attached to a conductive film as an electronic component (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") to obtain an electron with a surface protection film attached thereto. member.
將實施例12中獲得之表面保護膜(12)貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有表面保護膜之電子構件。 The surface protection film (12) obtained in Example 12 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with a surface protection film attached was obtained. member.
將實施例16中獲得之表面保護膜(16)貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有表面保護膜之電子構件。 The surface protection film (16) obtained in Example 16 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with a surface protection film attached was obtained. member.
將實施例20中獲得之表面保護膜(20)貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有表面保護膜之電子構件。 The surface protection film (20) obtained in Example 20 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with a surface protection film attached was obtained member.
將實施例24中獲得之表面保護膜(24)貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有表面保護膜之電子構件。 The surface protection film (24) obtained in Example 24 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with the surface protection film attached was obtained. member.
將實施例28中獲得之表面保護膜(28)貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有表面保護膜之電子構件。 The surface protection film (28) obtained in Example 28 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with the surface protection film attached was obtained member.
將實施例32中獲得之表面保護膜(32)貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有表面保護膜之電子構件。 The surface protection film (32) obtained in Example 32 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with a surface protection film attached was obtained. member.
將實施例36中獲得之表面保護膜(36)貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有表面保護膜之電子構件。 The surface protection film (36) obtained in Example 36 was attached to a conductive film as an electronic component (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") to obtain an electron with a surface protection film attached thereto. member.
將實施例40中獲得之表面保護膜(40)貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有表面保護膜之電子構件。 The surface protective film (40) obtained in Example 40 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with the surface protective film attached was obtained. member.
將實施例44中獲得之表面保護膜(44)貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有表面保護膜之電子構件。 The surface protection film (44) obtained in Example 44 was attached to a conductive film as an electronic component (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") to obtain an electron with a surface protection film attached thereto. member.
將實施例48中獲得之表面保護膜(48)貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有表面保護膜之電子構件。 The surface protection film (48) obtained in Example 48 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with the surface protection film attached was obtained. member.
將實施例52中獲得之表面保護膜(52)貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有表面保護膜之電子構件。 The surface protective film (52) obtained in Example 52 was attached to a conductive film as an electronic component (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") to obtain an electron with the surface protective film attached thereto. member.
將實施例56中獲得之表面保護膜(56)貼附於作為電子構件之導電 性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有表面保護膜之電子構件。 The surface protection film (56) obtained in Example 56 was attached to a conductive material as an electronic component A protective film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") was obtained as an electronic component with a surface protective film attached.
將實施例56中獲得之表面保護膜(56)貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有表面保護膜之電子構件。 The surface protection film (56) obtained in Example 56 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with a surface protection film attached was obtained. member.
將實施例60中獲得之表面保護膜(60)貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有表面保護膜之電子構件。 The surface protection film (60) obtained in Example 60 was attached to a conductive film as an electronic component (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") to obtain an electron with a surface protection film attached thereto. member.
將實施例64中獲得之表面保護膜(64)貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有表面保護膜之電子構件。 The surface protection film (64) obtained in Example 64 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with the surface protection film attached was obtained member.
將實施例68中獲得之表面保護膜(68)貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有表面保護膜之電子構件。 The surface protection film (68) obtained in Example 68 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with a surface protection film attached was obtained member.
將實施例72中獲得之表面保護膜(72)貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有表面保護膜之電子構件。 The surface protection film (72) obtained in Example 72 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with the surface protection film attached was obtained. member.
將實施例76中獲得之表面保護膜(76)貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有表面保護膜之電子構件。 The surface protection film (76) obtained in Example 76 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with a surface protection film attached was obtained. member.
將實施例80中獲得之表面保護膜(80)貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有表面保護膜之電子構件。 The surface protective film (80) obtained in Example 80 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with the surface protective film attached was obtained. member.
將實施例84中獲得之表面保護膜(84)貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有表面保護膜之電子構件。 The surface protection film (84) obtained in Example 84 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with the surface protection film attached was obtained. member.
將實施例88中獲得之表面保護膜(88)貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有表面保護膜之電子構件。 The surface protection film (88) obtained in Example 88 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with the surface protection film attached was obtained member.
將實施例92中獲得之表面保護膜(92)貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有表面保護膜之電子構件。 The surface protection film (92) obtained in Example 92 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with a surface protection film attached was obtained. member.
將實施例96中獲得之表面保護膜(96)貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有表面保護膜之電子構件。 The surface protection film (96) obtained in Example 96 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with a surface protection film attached was obtained. member.
將實施例100中獲得之表面保護膜(100)貼附於作為電子構件之導電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有表面保護膜之電子構件。 The surface protection film (100) obtained in Example 100 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with a surface protection film attached was obtained. member.
將實施例104中獲得之表面保護膜(104)貼附於作為電子構件之導 電性膜(日東電工股份有限公司製造,商品名「ELECRYSTA V270L-TFMP」),獲得貼附有表面保護膜之電子構件。 The surface protective film (104) obtained in Example 104 was attached as a guide for electronic components. Electrical film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP"), an electronic component with a surface protective film attached.
本發明之胺甲酸乙酯系黏著劑可用於任意適當之用途。較佳為本發明之胺甲酸乙酯系黏著劑之抗靜電性非常優異且抗糊劑殘留性或再加工性亦優異,因此,藉由用作表面保護膜之黏著劑層,該表面保護膜可較佳用於光學構件或電子構件之表面保護。 The urethane-based adhesive of the present invention can be used for any appropriate application. The urethane-based adhesive of the present invention is preferably excellent in antistatic properties and excellent in paste residue resistance or reworkability. Therefore, the surface protective film is used as an adhesive layer for a surface protective film. It can be preferably used for surface protection of optical components or electronic components.
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