TW201945491A

TW201945491A - Surface protection film

Info

Publication number: TW201945491A
Application number: TW108113373A
Authority: TW
Inventors: 佐佐木翔悟; 髙橋智一; 越智元気
Original assignee: 日商日東電工股份有限公司
Priority date: 2018-04-25
Filing date: 2019-04-17
Publication date: 2019-12-01
Also published as: JP7137961B2; WO2019208148A1; JP2019189763A; TWI791819B; KR102475546B1; CN112041405A; KR20210004984A

Abstract

Provided is a surface protection film which does not readily peel off the adherend and can be inhibited from coming to have an extremely high peel force with the lapse of time even when having a high initial peel force just after application to the adherend, and the application of which to adherends less soils the adherend surfaces. The surface protection film of the present invention includes a pressure-sensitive adhesive layer. This surface protection film, when applied to a glass plate by bonding the pressure-sensitive adhesive layer to the glass plate, allowed to stand at 23 DEG C for 30 minutes, and then peeled at 23 DEG C from the glass plate at a peel angle of 180 DEG and a peel rate of 300 mm/min, has a peel force A of 0.024-0.50 N/25 mm. This surface protection film, when applied to a glass plate by bonding the pressure-sensitive adhesive layer thereof to the glass plate, allowed to stand at 100 DEG C for 2 days, and then peeled at 23 DEG C from the glass plate at a peel angle of 180 DEG and a peel rate of 300 mm/min, has a peel force, which is expressed by B. Then the surface protection film has a degree of peel force increase with time, which is calculated by (B/A)*100, of 1,000% or less.

Description

表面保護膜Surface protection film

本發明係關於一種表面保護膜。The invention relates to a surface protection film.

於光學構件或電子構件之製造步驟中，加工、組裝、檢查、輸送等時，為防止該光學構件或該電子構件之表面損傷，通常於該光學構件或該電子構件之露出面貼附表面保護膜。此種表面保護膜於不需要表面保護之時點，自光學構件或電子構件剝離(專利文獻1)。In the manufacturing steps of an optical component or an electronic component, in order to prevent surface damage of the optical component or the electronic component during processing, assembly, inspection, transportation, etc., a surface protection is usually attached to the exposed surface of the optical component or the electronic component. membrane. Such a surface protection film is peeled from an optical member or an electronic member when surface protection is not required (Patent Document 1).

於貼附有此種表面保護膜之光學構件或電子構件中，如上所述於欲剝離表面保護膜時，重要的是僅於該表面保護膜與該光學構件或該電子構件之界面順滑地剝離。In an optical member or an electronic member to which such a surface protective film is attached, as described above, when the surface protective film is to be peeled off, it is important that only the interface between the surface protective film and the optical member or the electronic member is smooth. Peel off.

然而，於光學構件或電子構件具備薄玻璃或障壁膜等易於破損之構件之情形時，若欲剝離貼附之表面保護膜，則即使於使用先前之具備輕剝離性之表面保護膜之情形時，有時亦會因剝離力而導致該易於破損之構件破損。However, in the case where the optical member or the electronic member is provided with a thin glass or a barrier film, which is easily damaged, if the attached surface protective film is to be peeled off, even when the previous surface protective film having light peelability is used, Sometimes, the easy-to-break component is damaged due to the peeling force.

又，於光學構件或電子構件之製造步驟中，為防止於加工、組裝、檢查、輸送等時之該光學構件或該電子構件之表面損傷而於該光學構件或該電子構件之露出面貼附之表面保護膜常常於保持貼附之狀態下保管。於該情形時，若於保持貼附先前之表面保護膜之狀態下保管，則存在黏著力經時上升，導致重剝離化之問題。In addition, in the manufacturing steps of the optical member or the electronic member, in order to prevent the surface of the optical member or the electronic member from being damaged during processing, assembly, inspection, and transportation, the optical member or the electronic member is attached to the exposed surface of the optical member or the electronic member. The surface protective film is often kept in a state of being attached. In this case, if it is stored in a state where the previous surface protection film is attached, there is a problem that the adhesive force rises over time, resulting in re-peeling.

故而，報告有一種表面保護膜，其具備較之先前之具備輕剝離性之表面保護膜更輕之剝離性，即超輕剝離性(專利文獻2)。Therefore, there has been reported a surface protection film having lighter peelability, that is, ultra-light peelability, than a conventional surface protective film having light peelability (Patent Document 2).

藉由對表面保護膜賦予超輕剝離性，可減低貼附後之初期之剝離力，並且可抑制經時之重剝離化。然而，若對表面保護膜賦予超輕剝離性，則例如根據光學構件或電子構件之製造步驟之條件等，於該製造步驟中，有時貼附於該光學構件或該電子構件之露出面之該表面保護膜會發生剝離。By providing ultra-light peelability to the surface protective film, it is possible to reduce the peeling force at the initial stage after attaching, and to suppress heavy peeling over time. However, if the surface protective film is provided with ultra-light peelability, for example, depending on the conditions of the manufacturing steps of the optical member or the electronic member, the manufacturing step may be attached to the exposed surface of the optical member or the electronic member. The surface protection film is peeled.

另一方面，若為抑制如上述之剝離而加大貼附表面保護膜後之初期之剝離力，則存在剝離力經時上升導致重剝離化之問題。On the other hand, in order to suppress the peeling as described above, if the initial peeling force is increased after the surface protective film is attached, there is a problem that the peeling force rises with time and re-peeling occurs.

作為減輕剝離力之方法，考慮使表面保護膜所具有之黏著劑層中含有大量先前之剝離劑。然而，此種方法中存在如下問題：若於光學構件或電子構件等被黏著體貼附表面保護膜後進行剝離，則因剝離劑所導致之該被黏著體表面之污染之程度變大，即使欲於污染之該被黏著體表面重新貼附表面保護膜，亦因該被黏著體表面之污染而導致難以貼附。As a method for reducing the peeling force, it is considered that a large amount of the previous peeling agent is contained in the adhesive layer of the surface protective film. However, this method has the following problems: If the surface protection film is peeled off after the adherend is attached to an adherend such as an optical member or an electronic component, the degree of contamination of the adherend surface due to the release agent becomes large, even if it is desired Reattaching a surface protection film to the surface of the adherend that is contaminated is also difficult to attach due to the contamination of the surface of the adherend.

如上所述，有如下要求：代表性的為於光學構件或電子構件之製造步驟中，貼附於被黏著體之表面保護膜難以發生剝離；即使於被黏著體貼附表面保護膜後之初期之剝離力較大，亦可抑制經時之重剝離化；可降低因貼附表面保護膜而導致之被黏著體表面之污染性。
[先前技術文獻]
[專利文獻]As described above, there are the following requirements: Representatively, it is difficult to peel off the surface protective film attached to the adherend during the manufacturing steps of the optical member or electronic component; even after the surface protective film is attached to the adherend, The peeling force is large, which can inhibit the heavy peeling over time; it can reduce the contamination of the surface of the adherend caused by the surface protection film.
[Prior technical literature]
[Patent Literature]

[專利文獻1]日本專利特開2016-17109號公報
[專利文獻2]日本專利特開2017-160422號公報[Patent Document 1] Japanese Patent Laid-Open No. 2016-17109
[Patent Document 2] Japanese Patent Laid-Open No. 2017-160422

[發明所欲解決之問題][Problems to be solved by the invention]

本發明之課題在於提供一種表面保護膜，其不會自被黏著體容易地剝離，即使貼附於被黏著體後之初期之剝離力較大，亦可抑制經時之重剝離化，因貼附於被黏著體而導致之該被黏著體表面之污染性較低。
[解決問題之技術手段]The object of the present invention is to provide a surface protection film that does not easily peel off from an adherend, and even if the initial peeling force after being attached to the adherend is large, it can suppress re-peeling over time. The pollution of the surface of the adherend caused by the adherence to the adherend is low.
[Technical means to solve the problem]

本發明之表面保護膜係具有黏著劑層之表面保護膜，並且
將該表面保護膜之該黏著劑層貼合於玻璃板於溫度23℃下放置30分鐘後，於溫度23℃下將該表面保護膜自該玻璃板以剝離角度180度、剝離速度300 mm/分鐘進行剝離時之剝離力A為0.024 N/25 mm～0.50 N/25 mm，
將該表面保護膜之該黏著劑層貼合於玻璃板於溫度100℃下放置2日後，於溫度23℃下將該表面保護膜自該玻璃板以剝離角度180度、剝離速度300 mm/分鐘進行剝離，將此時之剝離力設為B時，以(B/A)×100算出之剝離力經時上升率為1000%以下。The surface protective film of the present invention is a surface protective film having an adhesive layer, and the adhesive layer of the surface protective film is bonded to a glass plate and left at a temperature of 23 ° C for 30 minutes, and then the surface is maintained at a temperature of 23 ° C. The peeling force A when the protective film was peeled from the glass plate at a peeling angle of 180 degrees and a peeling speed of 300 mm / min was 0.024 N / 25 mm to 0.50 N / 25 mm.
After the adhesive layer of the surface protection film was bonded to a glass plate and left at a temperature of 100 ° C for 2 days, the surface protection film was peeled from the glass plate at a temperature of 23 ° C at a peeling angle of 180 degrees and a peeling speed of 300 mm / min. When peeling was performed and the peeling force at this time was set to B, the increase rate of the peeling force over time calculated by (B / A) × 100 was 1000% or less.

於一實施形態中，將上述表面保護膜之上述黏著劑層貼合於玻璃板於23℃下放置7日後，於溫度23℃下將該表面保護膜自該玻璃板以剝離角度180度、剝離速度300 mm/分鐘進行剝離，將此時之剝離力設為C時，以(C/A)×100算出之剝離力經時上升率為160%以下。In one embodiment, after the above-mentioned adhesive layer of the surface protection film is bonded to a glass plate and left at 23 ° C for 7 days, the surface protection film is peeled from the glass plate at a temperature of 23 ° C at a peeling angle of 180 degrees and peeled off. Peeling was performed at a speed of 300 mm / minute, and when the peeling force at this time was set to C, the rate of increase in peeling force over time calculated by (C / A) × 100 was 160% or less.

於一實施形態中，本發明之表面保護膜之23℃下之對玻璃板之殘留接著率為50%以上。In one embodiment, the surface adhesion film of the present invention has a residual adhesion rate to a glass plate at 23 ° C. of 50% or more.

於一實施形態中，構成上述黏著劑層之黏著劑係自黏著劑組合物形成，該黏著劑組合物含有基礎聚合物與聚矽氧系添加劑及/或氟系添加劑。In one embodiment, the adhesive constituting the adhesive layer is formed from a self-adhesive composition, and the adhesive composition contains a base polymer and a silicone-based additive and / or a fluorine-based additive.

於一實施形態中，上述黏著劑組合物含有脂肪酸酯。In one embodiment, the adhesive composition contains a fatty acid ester.

於一實施形態中，上述聚矽氧系添加劑為選自含矽氧烷鍵之化合物、含羥基之聚矽氧系化合物、含交聯性官能基之聚矽氧系化合物中之至少一種。In one embodiment, the polysiloxane additive is at least one selected from a compound containing a siloxane bond, a polysiloxane compound containing a hydroxyl group, and a polysiloxane compound containing a crosslinkable functional group.

於一實施形態中，上述氟系添加劑為選自含氟之化合物、含羥基之氟系化合物、含交聯性官能基之氟系化合物中之至少一種。In one embodiment, the fluorine-based additive is at least one selected from a fluorine-containing compound, a hydroxyl-containing fluorine-based compound, and a crosslinkable functional group-containing fluorine-based compound.

於一實施形態中，上述基礎聚合物為選自胺基甲酸酯預聚物、多元醇、丙烯酸系樹脂、橡膠系樹脂、聚矽氧系樹脂中之至少一種。In one embodiment, the base polymer is at least one selected from the group consisting of a urethane prepolymer, a polyol, an acrylic resin, a rubber resin, and a silicone resin.

本發明之光學構件係貼著有本發明之表面保護膜者。The optical member of the present invention is the one to which the surface protective film of the present invention is attached.

本發明之電子構件係貼著有本發明之表面保護膜者。
[發明之效果]The electronic component of the present invention is a person having the surface protective film of the present invention attached thereto.
[Effect of the invention]

根據本發明，可提供一種表面保護膜，其不會自被黏著體容易地剝離，即使貼附於被黏著體後之初期之剝離力較大，亦可抑制經時之重剝離化，因貼附於被黏著體而導致之該被黏著體表面之污染性較低。According to the present invention, it is possible to provide a surface protection film that does not easily peel off from an adherend, and even if the initial peeling force after being attached to the adherend is large, it can suppress re-peeling over time. The pollution of the surface of the adherend caused by the adherence to the adherend is low.

≪≪A.表面保護膜≫≫
本發明之表面保護膜具有黏著劑層。本發明之表面保護膜只要具有黏著劑層，則可於不損害本發明之效果之範圍內，具備任意合適之其他構件。代表性的為本發明之表面保護膜具有基材層與黏著劑層。≪≪A. Surface protective film≫≫
The surface protection film of the present invention has an adhesive layer. As long as the surface protective film of the present invention has an adhesive layer, it can be provided with any other suitable member as long as the effect of the present invention is not impaired. The surface protection film of the present invention typically has a base material layer and an adhesive layer.

圖1係根據本發明之一實施形態之表面保護膜之概略截面圖。圖1中，表面保護膜10具備基材層1與黏著劑層2。圖1中，基材層1與黏著劑層2直接積層。FIG. 1 is a schematic cross-sectional view of a surface protective film according to an embodiment of the present invention. In FIG. 1, the surface protection film 10 includes a base material layer 1 and an adhesive layer 2. In FIG. 1, the substrate layer 1 and the adhesive layer 2 are directly laminated.

圖1中，可於黏著劑層2之基材層1之相反側之表面，以至使用前為止之保護等為目的，而具備任意合適之剝離襯墊(有時亦稱為剝離片材、隔離件)(未圖示)。作為剝離襯墊，例如可列舉：紙或塑膠膜等基材(襯墊基材)之表面經聚矽氧處理之剝離襯墊、紙或塑膠膜等基材(襯墊基材)之表面藉由聚烯烴系樹脂而層壓之剝離襯墊等。至於作為襯墊基材之塑膠膜，例如可列舉：聚乙烯膜、聚丙烯膜、聚丁烯膜、聚丁二烯膜、聚甲基戊烯膜、聚氯乙烯膜、氯乙烯共聚物膜、聚對苯二甲酸乙二酯膜、聚對苯二甲酸丁二酯膜、聚胺基甲酸酯膜、乙烯-乙酸乙烯酯共聚物膜等。至於作為襯墊基材之塑膠膜，較佳為聚乙烯膜。In FIG. 1, any suitable release liner (sometimes referred to as a release sheet, isolation) may be provided on the surface on the opposite side of the base material layer 1 of the adhesive layer 2 for the purpose of protection until use. (Not shown). Examples of the release liner include: a surface of a substrate (liner substrate) such as paper or a plastic film that has been treated with silicone, and a surface of a substrate (liner substrate) such as paper or a plastic film. A release liner or the like laminated with a polyolefin resin. As for the plastic film used as the backing substrate, for example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, and vinyl chloride copolymer film can be cited. , Polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate copolymer film, and the like. As for the plastic film used as the substrate of the cushion, a polyethylene film is preferred.

剝離襯墊之厚度較佳為1 μm～500 μm，更佳為3 μm～450 μm，進而較佳為5 μm～400 μm，尤佳為10 μm～300 μm。The thickness of the release liner is preferably 1 μm to 500 μm, more preferably 3 μm to 450 μm, still more preferably 5 μm to 400 μm, and even more preferably 10 μm to 300 μm.

表面保護膜之厚度較佳為5 μm～500 μm，更佳為10 μm～450 μm，進而較佳為15 μm～400 μm，尤佳為20 μm～300 μm。The thickness of the surface protective film is preferably 5 μm to 500 μm, more preferably 10 μm to 450 μm, still more preferably 15 μm to 400 μm, and even more preferably 20 μm to 300 μm.

作為本發明之表面保護膜，將表面保護膜之黏著劑層貼合於玻璃板於溫度23℃下放置30分鐘後，於溫度23℃下將該表面保護膜自該玻璃板以剝離角度180度、剝離速度300 mm/分鐘進行剝離時之剝離力A較佳為0.024 N/25 mm～0.50 N/25 mm，更佳為0.024 N/25 mm～0.40 N/25 mm，進而較佳為0.024 N/25 mm～0.30 N/25 mm，尤佳為0.024 N/25 mm～0.20 N/25 mm，最佳為0.024 N/25 mm～0.10 N/25 mm。若上述剝離力A為上述範圍內，則本發明之表面保護膜可變得難以自被黏著體容易地剝離。若上述剝離力A為上述範圍內，則代表性的為於光學構件或電子構件之製造步驟中，貼附於該光學構件或該電子構件之露出面之本發明之表面保護膜可變得難以發生剝離。再者，關於上述剝離力A之測定之詳細內容於下文敍述。As the surface protection film of the present invention, the adhesive layer of the surface protection film is bonded to a glass plate and left at a temperature of 23 ° C for 30 minutes, and then the surface protection film is peeled from the glass plate at a temperature of 180 ° at a temperature of 23 ° C. 3. Peeling force A when peeling speed is 300 mm / min. The peeling force A is preferably 0.024 N / 25 mm to 0.50 N / 25 mm, more preferably 0.024 N / 25 mm to 0.40 N / 25 mm, and still more preferably 0.024 N. / 25 mm to 0.30 N / 25 mm, particularly preferably 0.024 N / 25 mm to 0.20 N / 25 mm, and most preferably 0.024 N / 25 mm to 0.10 N / 25 mm. When the said peeling force A exists in the said range, it becomes difficult for the surface protection film of this invention to peel easily from an adherend. If the peeling force A is within the above range, the surface protection film of the present invention, which is typically attached to the exposed surface of the optical member or the electronic member in the manufacturing steps of the optical member or the electronic member, may become difficult. Peeling occurred. The details of the measurement of the peeling force A are described below.

作為本發明之表面保護膜，將表面保護膜之黏著劑層貼合於玻璃板於溫度100℃下放置2日後，於溫度23℃下將該表面保護膜自該玻璃板以剝離角度180度、剝離速度300 mm/分鐘進行剝離時之剝離力B較佳為0.20 N/25 mm～1.0 N/25 mm，更佳為0.25 N/25 mm～0.95 N/25 mm，進而較佳為0.30 N/25 mm～0.90 N/25 mm，尤佳為0.35 N/25 mm～0.85 N/25 mm，最佳為0.40 N/25 mm～0.80 N/25 mm。若上述剝離力B為上述範圍內，則本發明之表面保護膜可抑制經時之重剝離化。再者，關於上述剝離力B之測定之詳細內容於下文敍述。As the surface protection film of the present invention, after the adhesive layer of the surface protection film was bonded to a glass plate and left at a temperature of 100 ° C for 2 days, the surface protection film was peeled from the glass plate at a temperature of 23 ° C at a peeling angle of 180 degrees, The peeling speed B when the peeling speed is 300 mm / minute is preferably 0.20 N / 25 mm to 1.0 N / 25 mm, more preferably 0.25 N / 25 mm to 0.95 N / 25 mm, and further preferably 0.30 N / 25 mm to 0.90 N / 25 mm, particularly preferably 0.35 N / 25 mm to 0.85 N / 25 mm, and most preferably 0.40 N / 25 mm to 0.80 N / 25 mm. When the peeling force B is within the above range, the surface protective film of the present invention can suppress heavy peeling over time. The details of the measurement of the peeling force B are described below.

作為本發明之表面保護膜，關於上述剝離力A與上述剝離力B，以(B/A)×100算出之剝離力經時上升率較佳為1000%以下，更佳為950%以下，進而較佳為900%以下，尤佳為850%以下，最佳為800%以下。關於上述剝離力經時上升率之下限，較佳為450%以上。若上述剝離力經時上升率為上述範圍內，則本發明之表面保護膜即使於貼附於被黏著體後之初期之剝離力較大，亦可抑制經時之重剝離化。As the surface protective film of the present invention, with respect to the peeling force A and the peeling force B, the peeling force rise rate calculated with (B / A) × 100 over time is preferably 1,000% or less, more preferably 950% or less, and further It is preferably 900% or less, particularly preferably 850% or less, and most preferably 800% or less. The lower limit of the rate of increase in the peeling force with time is preferably 450% or more. If the time-dependent increase rate of the peeling force is within the above range, the surface protective film of the present invention can suppress re-peeling with time even if the initial peeling force after being attached to the adherend is large.

作為本發明之表面保護膜，將表面保護膜之黏著劑層貼合於玻璃板於23℃下放置7日後，於溫度23℃下將該表面保護膜自該玻璃板以剝離角度180度、剝離速度300 mm/分鐘進行剝離時之剝離力C較佳為0.024 N/25 mm～0.50 N/25 mm，更佳為0.024 N/25 mm～0.40 N/25 mm，進而較佳為0.024 N/25 mm～0.30 N/25 mm，尤佳為0.024 N/25 mm～0.20 N/25 mm，最佳為0.024 N/25 mm～0.10 N/25 mm。若上述剝離力C為上述範圍內，則本發明之表面保護膜可抑制經時之重剝離化。再者，關於上述剝離力C之測定之詳細內容於下文敍述。As the surface protective film of the present invention, after the adhesive layer of the surface protective film was bonded to a glass plate and left at 23 ° C for 7 days, the surface protective film was peeled from the glass plate at a temperature of 23 ° C at a peeling angle of 180 degrees and peeled off. The peeling force C when peeling at a speed of 300 mm / min is preferably 0.024 N / 25 mm to 0.50 N / 25 mm, more preferably 0.024 N / 25 mm to 0.40 N / 25 mm, and still more preferably 0.024 N / 25 mm to 0.30 N / 25 mm, particularly preferably 0.024 N / 25 mm to 0.20 N / 25 mm, and most preferably 0.024 N / 25 mm to 0.10 N / 25 mm. When the peeling force C is within the above range, the surface protective film of the present invention can suppress heavy peeling over time. The details of the measurement of the peeling force C are described below.

作為本發明之表面保護膜，關於上述剝離力A與上述剝離力C，以(C/A)×100算出之剝離力經時上升率較佳為160%以下，更佳為155%以下，進而較佳為150%以下，尤佳為145%以下，最佳為140%以下。關於上述剝離力經時上升率之下限，較佳為80%以上。若上述剝離力經時上升率為上述範圍內，則本發明之表面保護膜即使於貼附於被黏著體後之初期之剝離力較大，亦可抑制經時之重剝離化。As the surface protective film of the present invention, with respect to the peeling force A and the peeling force C, the rate of increase in peeling force calculated with (C / A) × 100 over time is preferably 160% or less, more preferably 155% or less, and It is preferably 150% or less, particularly preferably 145% or less, and most preferably 140% or less. The lower limit of the rate of increase in the peeling force with time is preferably 80% or more. If the time-dependent increase rate of the peeling force is within the above range, the surface protective film of the present invention can suppress re-peeling with time even if the initial peeling force after being attached to the adherend is large.

本發明之表面保護膜之殘留接著率較佳為50%以上，更佳為60%～100%，進而較佳為70%～100%，尤佳為80%～100%，最佳為85%～100%。若上述殘留接著率為上述範圍內，則本發明之表面保護膜可表現因貼附於被黏著體而導致之該被黏著體表面之污染性較低之效果。再者，關於殘留接著率之測定之詳細內容於下文敍述。The residual adhesion rate of the surface protective film of the present invention is preferably 50% or more, more preferably 60% to 100%, even more preferably 70% to 100%, particularly preferably 80% to 100%, and most preferably 85%. ~ 100%. If the above-mentioned residual adhesion rate is within the above range, the surface protective film of the present invention can exhibit the effect of low contamination on the surface of the adherend caused by sticking to the adherend. The details of the measurement of the residual adhesion rate are described below.

本發明之表面保護膜可藉由任意合適之方法而製造。作為此種製造方法，例如可依據
(1)將黏著劑層之形成材料之溶液或熱熔融液塗佈於基材層上之方法；
(2)將黏著劑層之形成材料之溶液或熱熔融液塗佈於隔離件上，將所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並形成塗佈於基材層上之方法；
(4)以雙層或多層擠出基材層與黏著劑層之方法；
(5)於基材層上單層層壓黏著劑層之方法或將黏著劑層與層壓層一起雙層層壓之方法；
(6)將黏著劑層與膜或層壓層等基材層形成材料進行雙層或多層層壓之方法；
等任意合適之製造方法而進行。The surface protective film of the present invention can be produced by any appropriate method. As such a manufacturing method, for example,
(1) A method of applying a solution or a hot-melt solution of the material forming the adhesive layer on the substrate layer;
(2) A method of applying a solution or a hot-melt solution of a material for forming an adhesive layer on a separator, and transferring the formed adhesive layer to a substrate layer;
(3) a method of extruding the forming material of the adhesive layer and forming a coating on the substrate layer;
(4) A method of extruding the base material layer and the adhesive layer in two or more layers;
(5) a method of laminating an adhesive layer on a single layer on a substrate layer or a method of double-layer laminating an adhesive layer and a laminate layer together;
(6) A method of double-layer or multi-layer lamination of an adhesive layer and a substrate layer forming material such as a film or a laminate layer;
And other suitable manufacturing methods.

作為塗佈之方法，例如可使用：輥式塗佈法、缺角輪塗佈(comma coat)法、模嘴塗佈法、反向塗佈法、絲網印刷法、凹版塗佈法等。As a coating method, for example, a roll coating method, a comma coat method, a die coating method, a reverse coating method, a screen printing method, or a gravure coating method can be used.

≪A-1.基材層≫
基材層可僅為1層，亦可為2層以上。基材層可為經延伸者。≪A-1. Substrate layer≫
The base layer may be only one layer, or may be two or more layers. The substrate layer may be an stretcher.

基材層之厚度較佳為4 μm～450 μm，更佳為8 μm～400 μm，進而較佳為12 μm～350 μm，尤佳為16 μm～250 μm。The thickness of the substrate layer is preferably 4 μm to 450 μm, more preferably 8 μm to 400 μm, still more preferably 12 μm to 350 μm, and even more preferably 16 μm to 250 μm.

對基材層之未附設黏著劑層之面，以退繞容易之捲繞體之形成等為目的，例如可對基材層添加脂肪醯胺、聚伸乙基亞胺、長鏈烷基系添加劑等進行脫模處理，或設置包含聚矽氧系、長鏈烷基系、氟系等任意合適之剝離劑之塗層。To the surface of the base material layer without the adhesive layer, for the purpose of forming an unrolled roll easily, for example, fatty base, polyethylenimine, and long-chain alkyl systems can be added to the base material layer. Additives and the like are subjected to a release treatment, or a coating layer including any suitable release agent such as a polysiloxane-based, long-chain alkyl-based, or fluorine-based is provided.

作為基材層之材料，可根據用途而採用任意合適之材料。例如可列舉：塑膠、紙、金屬膜、不織布等。較佳為塑膠。即，基材層較佳為塑膠膜。基材層可包含一種材料，亦可包含兩種以上之材料。例如，可包含兩種以上之塑膠。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. Preferred is plastic. That is, the substrate layer is preferably a plastic film. The substrate layer may include one kind of material, and may also include two or more kinds of materials. For example, two or more plastics may be included.

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；以乙烯成分為共聚成分之嵌段系、無規系、接枝系等之丙烯系共聚物；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、超低密度等之乙烯系聚合物；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 having an ethylene component as a copolymerization component; and a thermoplastic polyolefin prepared directly by a reactor. (reactor TPO); low density, high density, linear low density, ultra low density, etc. ethylene-based polymers; ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-acrylic acid Ethylene copolymers, such as ethylene copolymers, ethylene-butyl acrylate copolymers, ethylene-methacrylic acid copolymers, and ethylene-methyl methacrylate copolymers.

基材層視需要可含有任意合適之添加劑。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。基材層中可含有之添加劑之種類、數目、量可根據目的而適宜設定。尤其，於基材層之材料為塑膠之情形時，以劣化防止等為目的，較佳為含有上述添加劑之幾種。就耐候性提高等之觀點而言，作為添加劑，尤佳為抗氧化劑、紫外線吸收劑、光穩定劑、填充劑。The substrate layer may contain any suitable additives as necessary. 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 base material layer can be appropriately set according to the purpose. In particular, when the material of the base material layer is plastic, for the purpose of preventing deterioration, it is preferable to include several of the above-mentioned additives. From the viewpoint of improving the weather resistance, etc., the additives are particularly preferably an antioxidant, an ultraviolet absorber, a light stabilizer, and a filler.

作為抗氧化劑，可採用任意合適之抗氧化劑。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、硫系耐熱穩定劑、酚-磷系抗氧化劑等。作為抗氧化劑之含有比例，相對於基材層之基礎樹脂(基材層為摻合物之情形時該摻合物為基礎樹脂)，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 suitable 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-resistant stabilizer, and a phenol-phosphorus-based antioxidant. The content ratio 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 (when the base material layer is a blend). , And more preferably 0.01% by weight to 0.2% by weight.

作為紫外線吸收劑，可採用任意合適之紫外線吸收劑。作為此種紫外線吸收劑，例如可列舉：苯并***系紫外線吸收劑、三系紫外線吸收劑、二苯甲酮系紫外線吸收劑等。作為紫外線吸收劑之含有比例，相對於形成基材層之基礎樹脂(基材層為摻合物之情形時該摻合物為基礎樹脂)，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 absorbent, any suitable ultraviolet absorbent can be used. As such an ultraviolet absorber, a benzotriazole-type ultraviolet absorber, a tri-type ultraviolet absorber, a benzophenone-type ultraviolet absorber, etc. are mentioned, for example. 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 material layer (when the base material layer is a blend). % Or less, and more preferably 0.01 to 0.5% by weight.

作為光穩定劑，可採用任意合適之光穩定劑。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。作為光穩定劑之含有比例，相對於形成基材層之基礎樹脂(基材層為摻合物之情形時該摻合物為基礎樹脂)，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 suitable 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 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). % Or less, and more preferably 0.01 to 0.5% by weight.

作為填充劑，可採用任意合適之填充劑。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。作為填充劑之含有比例，相對於形成基材層之基礎樹脂(基材層為摻合物之情形時該摻合物為基礎樹脂)，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 suitable 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 material layer (when the base material layer is a blend). 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，亦可較佳地列舉：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, a surfactant, an inorganic salt, a polyhydric alcohol, a metal compound, carbon, and other inorganic-based, low-molecular-weight, and high-molecular-weight antistatic agents can also be preferably cited. In particular, in terms of contamination and maintaining adhesiveness, a high molecular weight antistatic agent or carbon is preferred.

≪A-2.黏著劑層≫
黏著劑層可包含黏著劑。黏著劑可自黏著劑組合物形成。≪A-2. Adhesive layer≫
The adhesive layer may include an adhesive. The adhesive may be formed from an adhesive composition.

黏著劑層可藉由任意合適之方法而形成。作為此種方法，例如可列舉：將黏著劑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：藉由輥式塗佈、凹版塗佈、反向塗佈、輥式刷塗、噴塗、氣刀塗佈法、模嘴塗佈等之擠出塗佈等。The adhesive layer can be formed by any suitable method. As such a method, the method of apply | coating an adhesive composition on a base material layer, and forming an adhesive layer on a base material layer is mentioned, for example. Examples of such a coating method include extrusion coating by roll coating, gravure coating, reverse coating, roll brush coating, spray coating, air knife coating, and die coating. Cloth, etc.

黏著劑層之厚度較佳為1 μm～150 μm，更佳為2 μm～140 μm，進而較佳為3 μm～130 μm，進而較佳為4 μm～120 μm，進而較佳為5 μm～100 μm，進而較佳為10 μm～90 μm，尤佳為20 μm～85 μm，最佳為30 μm～80 μm。The thickness of the adhesive layer is preferably 1 μm to 150 μm, more preferably 2 μm to 140 μm, still more preferably 3 μm to 130 μm, still more preferably 4 μm to 120 μm, and still more preferably 5 μm to 100 μm, more preferably 10 μm to 90 μm, particularly preferably 20 μm to 85 μm, and most preferably 30 μm to 80 μm.

黏著劑組合物較佳為含有基礎聚合物與聚矽氧系添加劑及/或氟系添加劑。The adhesive composition preferably contains a base polymer and a polysiloxane-based additive and / or a fluorine-based additive.

黏著劑組合物中之基礎聚合物與聚矽氧系添加劑與氟系添加劑之總量之含有比例較佳為50重量%～100重量%，更佳為60重量%～100重量%，進而較佳為70重量%～100重量%，尤佳為75重量%～100重量%，最佳為80重量%～100重量%。若黏著劑組合物中之基礎聚合物與聚矽氧系添加劑與氟系添加劑之總量之含有比例為上述範圍內，則本發明之表面保護膜可變得更難以自被黏著體容易地剝離，可進一步抑制經時之重剝離化，可進一步表現因貼附於被黏著體而導致之該被黏著體表面之污染性較低之效果。The content ratio of the total amount of the base polymer, the polysiloxane-based additive and the fluorine-based additive in the adhesive composition is preferably 50% to 100% by weight, more preferably 60% to 100% by weight, and further preferably It is 70 to 100% by weight, more preferably 75 to 100% by weight, and most preferably 80 to 100% by weight. If the content ratio of the total amount of the base polymer, the polysiloxane-based additive, and the fluorine-based additive in the adhesive composition is within the above range, the surface protective film of the present invention may become more difficult to peel off from the adherend more easily. It can further suppress the re-peeling with time, and can further exhibit the effect of lower pollution of the surface of the adherend caused by being adhered to the adherend.

關於黏著劑組合物中之聚矽氧系添加劑及/或氟系添加劑之含量，作為相對於基礎聚合物100重量份之聚矽氧系添加劑與氟系添加劑之總量，較佳為0.001重量份～50重量份，更佳為0.005重量份～25重量份，進而較佳為0.01重量份～10重量份，進而較佳為0.01重量份～1重量份，進而較佳為0.01重量份～0.50重量份，尤佳為0.01重量份～0.30重量份，最佳為0.01重量份～0.28重量份。若黏著劑組合物中之聚矽氧系添加劑及/或氟系添加劑之含量為上述範圍內，則本發明之表面保護膜可變得更難以自被黏著體容易地剝離，可進一步抑制經時之重剝離化，可進一步表現因貼附於被黏著體而導致之該被黏著體表面之污染性較低之效果。The content of the polysiloxane-based additive and / or the fluorine-based additive in the adhesive composition is preferably 0.001 part by weight based on 100 parts by weight of the total amount of the polysiloxane-based additive and the fluorine-based additive. To 50 parts by weight, more preferably 0.005 to 25 parts by weight, still more preferably 0.01 to 10 parts by weight, still more preferably 0.01 to 1 part by weight, and still more preferably 0.01 to 0.50 part by weight Parts, particularly preferably 0.01 to 0.30 parts by weight, and most preferably 0.01 to 0.28 parts by weight. If the content of the polysiloxane-based additive and / or the fluorine-based additive in the adhesive composition is within the above range, the surface protective film of the present invention can be more difficult to be easily peeled off from the adherend, and the aging time can be further suppressed. The heavy peeling can further show the effect of lower contamination on the surface of the adherend caused by sticking to the adherend.

即，於黏著劑組合物中含有聚矽氧系添加劑但不含氟系添加劑之情形時，聚矽氧系添加劑相對於基礎聚合物100重量份之含有比例較佳為0.001重量份～50重量份，更佳為0.005重量份～25重量份，進而較佳為0.01重量份～10重量份，進而較佳為0.01重量份～1重量份，進而較佳為0.01重量份～0.50重量份，尤佳為0.01重量份～0.30重量份，最佳為0.01重量份～0.28重量份。若黏著劑組合物中之聚矽氧系添加劑之含量為上述範圍內，則本發明之表面保護膜可變得更難以自被黏著體容易地剝離，可進一步抑制經時之重剝離化，可進一步表現因貼附於被黏著體而導致之該被黏著體表面之污染性較低之效果。That is, when the polysiloxane additive is contained in the adhesive composition but the fluorine-based additive is not contained, the content ratio of the polysiloxane additive to 100 parts by weight of the base polymer is preferably 0.001 to 50 parts by weight. , More preferably 0.005 to 25 parts by weight, still more preferably 0.01 to 10 parts by weight, still more preferably 0.01 to 1 part by weight, still more preferably 0.01 to 0.50 parts by weight, and even more preferably It is 0.01 to 0.30 parts by weight, and most preferably 0.01 to 0.28 parts by weight. If the content of the polysiloxane-based additive in the adhesive composition is within the above range, the surface protective film of the present invention can be more difficult to be easily peeled off from the adherend, which can further suppress re-peeling over time. The effect of lower contamination on the surface of the adherend caused by sticking to the adherend is further exhibited.

又，於黏著劑組合物中不含聚矽氧系添加劑且含有氟系添加劑之情形時，氟系添加劑相對於基礎聚合物100重量份之含有比例較佳為0.001重量份～50重量份，更佳為0.005重量份～25重量份，進而較佳為0.01重量份～10重量份，進而較佳為0.01重量份～1重量份，進而較佳為0.01重量份～0.50重量份，尤佳為0.01重量份～0.30重量份，最佳為0.01重量份～0.28重量份。若黏著劑組合物中之氟系添加劑之含量為上述範圍內，則本發明之表面保護膜可變得更難以自被黏著體容易地剝離，可進一步抑制經時之重剝離化，可進一步表現因貼附於被黏著體而導致之該被黏著體表面之污染性較低之效果。When the adhesive composition does not contain a polysiloxane-based additive and contains a fluorine-based additive, the content ratio of the fluorine-based additive to 100 parts by weight of the base polymer is preferably 0.001 to 50 parts by weight, more preferably 0.005 to 25 parts by weight, more preferably 0.01 to 10 parts by weight, still more preferably 0.01 to 1 part by weight, still more preferably 0.01 to 0.50 parts by weight, and even more preferably 0.01 Part by weight to 0.30 part by weight, most preferably 0.01 part by weight to 0.28 part by weight. If the content of the fluorine-based additive in the adhesive composition is within the above range, the surface protective film of the present invention can be more difficult to peel off easily from the adherend, which can further suppress re-peeling over time, and can further express The effect of the pollution of the surface of the adherend caused by being adhered to the adherend is low.

又，於黏著劑組合物中含有聚矽氧系添加劑與氟系添加劑之兩者之情形時，聚矽氧系添加劑與氟系添加劑之合計相對於基礎聚合物100重量份之含有比例較佳為0.001重量份～50重量份，更佳為0.005重量份～25重量份，進而較佳為0.01重量份～10重量份，進而較佳為0.01重量份～1重量份，進而較佳為0.01重量份～0.50重量份，尤佳為0.01重量份～0.30重量份，最佳為0.01重量份～0.28重量份。若黏著劑組合物中之聚矽氧系添加劑與氟系添加劑之總含量為上述範圍內，則本發明之表面保護膜可變得更難以自被黏著體容易地剝離，可進一步抑制經時之重剝離化，可進一步表現因貼附於被黏著體而導致之該被黏著體表面之污染性較低之效果。In the case where both the polysiloxane additive and the fluorine additive are contained in the adhesive composition, the content ratio of the total of the polysiloxane additive and the fluorine additive to 100 parts by weight of the base polymer is preferably 0.001 to 50 parts by weight, more preferably 0.005 to 25 parts by weight, still more preferably 0.01 to 10 parts by weight, still more preferably 0.01 to 1 part by weight, and still more preferably 0.01 part by weight 0.5 to 0.50 parts by weight, particularly preferably 0.01 to 0.30 parts by weight, and most preferably 0.01 to 0.28 parts by weight. If the total content of the polysiloxane-based additive and the fluorine-based additive in the adhesive composition is within the above-mentioned range, the surface protective film of the present invention may become more difficult to be easily peeled off from the adherend, and the aging time may be further suppressed. The heavy peeling can further express the effect of lower contamination on the surface of the adherend caused by the adherence to the adherend.

＜A-2-1.基礎聚合物＞
基礎聚合物較佳為選自胺基甲酸酯預聚物、多元醇、丙烯酸系樹脂、橡膠系樹脂、聚矽氧系樹脂中之至少一種。若基礎聚合物為選自胺基甲酸酯預聚物、多元醇、丙烯酸系樹脂、橡膠系樹脂、聚矽氧系樹脂中之至少一種，則本發明之表面保護膜可變得更難以自被黏著體容易地剝離，可進一步抑制經時之重剝離化，可進一步表現因貼附於被黏著體而導致之該被黏著體表面之污染性較低之效果。＜ A-2-1. Base polymer ＞
The base polymer is preferably at least one selected from the group consisting of a urethane prepolymer, a polyol, an acrylic resin, a rubber resin, and a silicone resin. If the base polymer is at least one selected from the group consisting of a urethane prepolymer, a polyol, an acrylic resin, a rubber-based resin, and a silicone resin, the surface protective film of the present invention may become more difficult to self-protect The adherend can be easily peeled off, which can further suppress the re-peeling over time, and can further exhibit the effect of lower contamination on the surface of the adherend caused by sticking to the adherend.

[A-2-1-a.胺基甲酸酯預聚物]
胺基甲酸酯預聚物較佳為聚胺基甲酸酯多元醇，更佳為使聚酯多元醇(a1)或聚醚多元醇(a2)分別單獨，或以(a1)與(a2)之混合物，於觸媒存在下或無觸媒下，與有機聚異氰酸酯化合物(a3)反應而成者。[A-2-1-a. Urethane prepolymer]
The urethane prepolymer is preferably a polyurethane polyol, and more preferably, the polyester polyol (a1) or the polyether polyol (a2) is alone, or (a1) and (a2) ), In the presence or absence of a catalyst, reacted with an organic polyisocyanate compound (a3).

作為聚酯多元醇(a1)，可使用任意合適之聚酯多元醇。作為此種聚酯多元醇(a1)，例如可列舉：使酸成分與二醇成分反應而獲得之聚酯多元醇。作為酸成分，例如可列舉：對苯二甲酸、己二酸、壬二酸、癸二酸、鄰苯二甲酸酐、間苯二甲酸、偏苯三甲酸等。作為二醇成分，例如可列舉：乙二醇、丙二醇、二乙二醇、丁二醇、1,6-己二醇、3-甲基-1,5-戊二醇、3,3'-二羥甲基庚烷、聚氧乙二醇、聚氧丙二醇、1,4-丁二醇、新戊二醇、丁基乙基戊二醇，作為多元醇成分，可列舉：甘油、三羥甲基丙烷、季戊四醇等。作為聚酯多元醇(a1)，其他亦可列舉：將聚己內酯、聚(β-甲基-γ-戊內酯)、聚戊內酯等內酯類開環聚合而獲得之聚酯多元醇等。As the polyester polyol (a1), any appropriate polyester polyol can be used. Examples of such a polyester polyol (a1) include a polyester polyol obtained by reacting an acid component with a diol component. Examples of the acid component include terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, trimellitic acid, and the like. Examples of the diol component include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and 3,3'- Dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, and butylethylpentanediol. Examples of the polyol component include glycerol, trihydroxy Methylpropane, pentaerythritol, etc. Examples of the polyester polyol (a1) include polyesters obtained by ring-opening polymerization of lactones such as polycaprolactone, poly (β-methyl-γ-valerolactone), and polyvalerolactone. Polyols, etc.

作為聚酯多元醇(a1)之分子量，自低分子量至高分子量均可使用。作為聚酯多元醇(a1)之分子量，數量平均分子量較佳為100～100000。若數量平均分子量未達100，則存在反應性變高，易於凝膠化之虞。若數量平均分子量超過100000，則存在反應性變低，進而聚胺基甲酸酯多元醇自身之凝集力變小之虞。聚酯多元醇(a1)之使用量於構成聚胺基甲酸酯多元醇之多元醇中，較佳為0莫耳%～90莫耳%。The molecular weight of the polyester polyol (a1) can be used from a low molecular weight to a high molecular weight. As the molecular weight of the polyester polyol (a1), the number average molecular weight is preferably 100 to 100,000. If the number average molecular weight is less than 100, there is a possibility that the reactivity becomes high and the gelation is liable to occur. If the number average molecular weight exceeds 100,000, the reactivity may be lowered, and the cohesive force of the polyurethane polyol itself may be reduced. The amount of the polyester polyol (a1) used in the polyol constituting the polyurethane polyol is preferably 0 mol% to 90 mol%.

作為聚醚多元醇(a2)，可使用任意合適之聚醚多元醇。作為此種聚醚多元醇(a2)，例如可列舉：藉由使用水、丙二醇、乙二醇、甘油、三羥甲基丙烷等低分子量多元醇作為起始劑，使環氧乙烷、環氧丙烷、環氧丁烷、四氫呋喃等環氧乙烷(oxirane)化合物進行聚合而獲得之聚醚多元醇。作為此種聚醚多元醇(a2)，具體而言，例如可列舉：聚丙二醇、聚乙二醇、聚四亞甲基二醇等官能基數為2以上之聚醚多元醇。As the polyether polyol (a2), any appropriate polyether polyol can be used. As such a polyether polyol (a2), for example, ethylene oxide, a cyclic ring, etc. are used by using a low molecular weight polyol, such as water, propylene glycol, ethylene glycol, glycerol, and trimethylolpropane, as an initiator. A polyether polyol obtained by polymerizing an oxirane compound such as propylene oxide, butylene oxide, and tetrahydrofuran. Specific examples of such a polyether polyol (a2) include polyether polyols having two or more functional groups such as polypropylene glycol, polyethylene glycol, and polytetramethylene glycol.

作為聚醚多元醇(a2)之分子量，自低分子量至高分子量均可使用。作為聚醚多元醇(a2)之分子量，數量平均分子量較佳為100～100000。若數量平均分子量未達100，則存在反應性變高，易於凝膠化之虞。若數量平均分子量超過100000，則存在反應性變低，進而聚胺基甲酸酯多元醇自身之凝集力變小之虞。聚醚多元醇(a2)之使用量於構成聚胺基甲酸酯多元醇之多元醇中，較佳為0莫耳%～90莫耳%。The molecular weight of the polyether polyol (a2) can be used from a low molecular weight to a high molecular weight. As the molecular weight of the polyether polyol (a2), the number average molecular weight is preferably 100 to 100,000. If the number average molecular weight is less than 100, there is a possibility that the reactivity becomes high and the gelation is liable to occur. If the number average molecular weight exceeds 100,000, the reactivity may be lowered, and the cohesive force of the polyurethane polyol itself may be reduced. The amount of the polyether polyol (a2) used in the polyol constituting the polyurethane polyol is preferably 0 mol% to 90 mol%.

聚醚多元醇(a2)可視需要將其一部分替換為乙二醇、1,4-丁二醇、新戊二醇、丁基乙基戊二醇、甘油、三羥甲基丙烷、季戊四醇等二醇類或乙二胺、N-胺基乙基乙醇胺、異佛酮二胺、苯二甲胺等多元胺類等而併用。Polyether polyol (a2) can be partially replaced with ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerol, trimethylolpropane, pentaerythritol, etc. Alcohols, polyamines such as ethylenediamine, N-aminoethylethanolamine, isophoronediamine, xylylenediamine, and the like are used in combination.

作為聚醚多元醇(a2)，可僅使用雙官能性之聚醚多元醇，亦可部分使用或全部使用數量平均分子量為100～100000且於1分子中具有至少3個以上之羥基之聚醚多元醇。若部分使用或全部使用數量平均分子量為100～100000且於1分子中具有至少3個以上之羥基之聚醚多元醇作為聚醚多元醇(a2)，則黏著力與再剝離性之平衡可變得良好。於此種聚醚多元醇中，若數量平均分子量未達100，則存在反應性變高，易於凝膠化之虞。又，於此種聚醚多元醇中，若數量平均分子量超過100000，則存在反應性變低，進而聚胺基甲酸酯多元醇自身之凝集力變小之虞。此種聚醚多元醇之數量平均分子量更佳為100～10000。As the polyether polyol (a2), only a difunctional polyether polyol may be used, or a polyether having a number average molecular weight of 100 to 100,000 and having at least 3 hydroxyl groups in one molecule may be used partially or entirely. Polyol. If a polyether polyol having a number-average molecular weight of 100 to 100,000 and having at least 3 hydroxyl groups in one molecule is used as the polyether polyol (a2), the balance between adhesion and re-peelability is variable. Well. In such a polyether polyol, if the number average molecular weight is less than 100, there is a possibility that the reactivity becomes high and the gelation is liable to occur. Moreover, in such a polyether polyol, if the number average molecular weight exceeds 100,000, there is a possibility that the reactivity becomes low and the cohesive force of the polyurethane polyol itself becomes small. The number average molecular weight of such a polyether polyol is more preferably 100 to 10,000.

作為有機聚異氰酸酯化合物(a3)，可使用任意合適之有機聚異氰酸酯化合物。作為此種有機聚異氰酸酯化合物(a3)，例如可列舉：芳香族聚異氰酸酯、脂肪族聚異氰酸酯、芳香脂肪族聚異氰酸酯、脂環族聚異氰酸酯等。As the organic polyisocyanate compound (a3), any appropriate organic polyisocyanate compound can be used. Examples of such an organic polyisocyanate compound (a3) include an aromatic polyisocyanate, an aliphatic polyisocyanate, an aromatic aliphatic polyisocyanate, and an alicyclic polyisocyanate.

作為芳香族聚異氰酸酯，例如可列舉：1,3-伸苯基二異氰酸酯、4,4'-二苯基二異氰酸酯、1,4-伸苯基二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、4,4'-甲苯胺二異氰酸酯、2,4,6-三異氰酸酯甲苯、1,3,5-三異氰酸酯苯、聯大茴香胺二異氰酸酯、4,4'-二苯醚二異氰酸酯、4,4',4''-三苯基甲烷三異氰酸酯等。Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, and 4,4'-diphenylmethane. Diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, diisocyanate Anisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4' '-triphenylmethane triisocyanate, etc.

作為脂肪族聚異氰酸酯，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、2,3-伸丁基二異氰酸酯、1,3-伸丁基二異氰酸酯、十二亞甲基二異氰酸酯、2,4,4-三甲基六亞甲基二異氰酸酯等。Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, and 2,3 -Butylene diisocyanate, 1,3-butylene diisocyanate, dodecyl diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc.

作為芳香脂肪族聚異氰酸酯，例如可列舉：ω,ω'-二異氰酸酯基-1,3-二甲基苯、ω,ω'-二異氰酸酯基-1,4-二甲基苯、ω,ω'-二異氰酸酯基-1,4-二乙基苯、1,4-四甲基苯二甲基二異氰酸酯、1,3-四甲基苯二甲基二異氰酸酯等。Examples of the aromatic aliphatic polyisocyanate include ω, ω'-diisocyanate-1,3-dimethylbenzene, ω, ω'-diisocyanate-1,4-dimethylbenzene, ω, ω '-Diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

作為脂環族聚異氰酸酯，例如可列舉：3-異氰酸酯基甲基-3,5,5-三甲基環己基異氰酸酯、1,3-環戊烷二異氰酸酯、1,3-環己烷二異氰酸酯、1,4-環己烷二異氰酸酯、甲基-2,4-環己烷二異氰酸酯、甲基-2,6-環己烷二異氰酸酯、4,4'-亞甲基雙(環己基異氰酸酯)、1,4-雙(異氰酸酯基甲基)環己烷、1,4-雙(異氰酸酯基甲基)環己烷等。Examples of the alicyclic polyisocyanate include 3-isocyanatemethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, and 1,3-cyclohexane diisocyanate. , 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate) ), 1,4-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, and the like.

作為有機聚異氰酸酯化合物(a3)，可併用三羥甲基丙烷加成物、與水反應而成之縮二脲體、具有異氰尿酸酯環之三聚物等。As the organic polyisocyanate compound (a3), a trimethylolpropane adduct, a biuret body formed by reacting with water, a trimer having an isocyanurate ring, and the like can be used in combination.

作為獲得聚胺基甲酸酯多元醇時可使用之觸媒，可使用任意合適之觸媒。作為此種觸媒，例如可列舉：三級胺系化合物、有機金屬系化合物等。As a catalyst which can be used when obtaining a polyurethane polyol, any appropriate catalyst can be used. Examples of such a catalyst include tertiary amine compounds, organometallic compounds, and the like.

作為三級胺系化合物，例如可列舉：三乙胺、三乙二胺、1,8-二氮雜雙環(5,4,0)-十一烯-7(DBU)等。Examples of the tertiary amine-based compound include triethylamine, triethylenediamine, 1,8-diazabicyclo (5,4,0) -undecene-7 (DBU), and the like.

作為有機金屬系化合物，例如可列舉：錫系化合物、非錫系化合物等。Examples of the organometallic compound include a tin-based compound and a non-tin-based compound.

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、二丁基二順丁烯二酸錫、二丁基二月桂酸錫(DBTDL)、二丁基二乙酸錫、二丁基硫化錫、三丁基硫化錫、三丁基氧化錫、三丁基乙酸錫、三乙基乙醇錫、三丁基乙醇錫、二辛基氧化錫、三丁基氯化錫、三丁基三氯乙酸錫、2-乙基己酸錫等。Examples of the tin-based compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin maleate, and dibutyltin dilaurate ( (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltinoxide, tributyltinethanol, dioctyl oxide Tin, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate, and the like.

作為非錫系化合物，例如可列舉：二丁基二氯化鈦、鈦酸四丁酯、丁氧基三氯化鈦等鈦系化合物；油酸鉛、2-乙基己酸鉛、苯甲酸鉛、環烷酸鉛等鉛系化合物；2-乙基己酸鐵、乙醯丙酮酸鐵等鐵系化合物；苯甲酸鈷、2-乙基己酸鈷等鈷系化合物；環烷酸鋅、2-乙基己酸鋅等鋅系化合物；環烷酸鋯等鋯系化合物等。Examples of non-tin compounds include titanium compounds such as dibutyl titanium dichloride, tetrabutyl titanate, and titanium butoxy trichloride; lead oleate, lead 2-ethylhexanoate, and benzoic acid Lead compounds such as lead and lead naphthenate; iron compounds such as iron 2-ethylhexanoate and iron pyruvate; cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc naphthenate, Zinc compounds such as zinc 2-ethylhexanoate; zirconium compounds such as zirconium naphthenate.

於獲得聚胺基甲酸酯多元醇時使用觸媒之情形時，於存在聚酯多元醇與聚醚多元醇之兩種多元醇之系統中，由於其反應性之不同，若為單獨之觸媒系統，則易於產生凝膠化或反應溶液變渾濁之問題。因此，藉由於獲得聚胺基甲酸酯多元醇時使用兩種觸媒，變得易於控制反應速度、觸媒之選擇性等，可解決該等問題。作為此種兩種觸媒之組合，例如可列舉：三級胺/有機金屬系、錫系/非錫系、錫系/錫系，較佳為錫系/錫系，更佳為二丁基二月桂酸錫與2-乙基己酸錫之組合。其調配比以重量比計，2-乙基己酸錫/二丁基二月桂酸錫較佳為未達1，更佳為0.2～0.6。若調配比為1以上，則存在因觸媒活性之平衡而變得易於凝膠化之虞。In the case of using a catalyst when obtaining a polyurethane polyol, in a system in which two polyols, polyester polyol and polyether polyol, exist, due to the difference in reactivity, if it is a separate contact Media system, it is easy to cause gelation or turbidity of the reaction solution. Therefore, by using two catalysts when obtaining a polyurethane polyol, it becomes easy to control the reaction speed, the selectivity of the catalyst, etc., and these problems can be solved. Examples of the combination of these two catalysts include tertiary amines / organometallics, tins / non-tins, tins / tins, preferably tins / tins, and more preferably dibutyl A combination of tin dilaurate and tin 2-ethylhexanoate. The blending ratio is based on a weight ratio. The 2-ethylhexanoate / dibutyltin dilaurate is preferably less than 1, and more preferably 0.2 to 0.6. When the blending ratio is 1 or more, there is a possibility that the gelation is liable to occur due to the balance of catalyst activity.

於獲得聚胺基甲酸酯多元醇時使用觸媒之情形時，觸媒之使用量相對於聚酯多元醇(a1)與聚醚多元醇(a2)與有機聚異氰酸酯化合物(a3)之總量，較佳為0.01重量%～1.0重量%。In the case of using a catalyst when obtaining a polyurethane polyol, the amount of the catalyst used is relative to the total amount of the polyester polyol (a1), the polyether polyol (a2), and the organic polyisocyanate compound (a3). The amount is preferably 0.01% by weight to 1.0% by weight.

於獲得聚胺基甲酸酯多元醇時使用觸媒之情形時，反應溫度較佳為未達100℃，更佳為85℃～95℃。若成為100℃以上，則存在難以控制反應速度、交聯結構之虞，存在難以獲得具有特定分子量之聚胺基甲酸酯多元醇之虞。In the case of using a catalyst when obtaining a polyurethane polyol, the reaction temperature is preferably less than 100 ° C, and more preferably 85 ° C to 95 ° C. If it is 100 ° C or higher, it may be difficult to control the reaction rate and the crosslinked structure, and it may be difficult to obtain a polyurethane polyol having a specific molecular weight.

於獲得聚胺基甲酸酯多元醇時，可不使用觸媒。於該情形時，反應溫度較佳為100℃以上，更佳為110℃以上。又，於無觸媒下獲得聚胺基甲酸酯多元醇時，較佳為反應3小時以上。In obtaining the polyurethane polyol, a catalyst may not be used. In this case, the reaction temperature is preferably 100 ° C or higher, and more preferably 110 ° C or higher. When a polyurethane polyol is obtained without a catalyst, the reaction is preferably performed for 3 hours or more.

作為獲得聚胺基甲酸酯多元醇之方法，例如可列舉：1)將聚酯多元醇、聚醚多元醇、觸媒、有機聚異氰酸酯之全部量添加至燒瓶之方法，2)將聚酯多元醇、聚醚多元醇、觸媒添加至燒瓶並滴加有機聚異氰酸酯之方法。作為獲得聚胺基甲酸酯多元醇之方法，就控制反應之方面而言，較佳為2)之方法。As a method for obtaining a polyurethane polyol, for example, 1) a method of adding the entire amount of polyester polyol, polyether polyol, catalyst, and organic polyisocyanate to a flask, and 2) polyester A method of adding a polyhydric alcohol, a polyether polyol, and a catalyst to a flask and dropping an organic polyisocyanate dropwise. As a method for obtaining a polyurethane polyol, the method of 2) is preferable in terms of controlling the reaction.

於獲得聚胺基甲酸酯多元醇時，可使用任意合適之溶劑。作為此種溶劑，例如可列舉：甲基乙基酮、乙酸乙酯、甲苯、二甲苯、丙酮等。該等溶劑中，較佳為甲苯。In obtaining the polyurethane polyol, any suitable solvent may be used. Examples of such a solvent include methyl ethyl ketone, ethyl acetate, toluene, xylene, and acetone. Among these solvents, toluene is preferred.

[A-2-1-b.多元醇]
作為多元醇，例如較佳為聚酯多元醇、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。作為多元醇，更佳為聚醚多元醇。[A-2-1-b. Polyol]
As the polyol, for example, polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol, and castor oil-based polyol are preferred. The polyhydric alcohol is more preferably a polyether 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。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、間苯二甲酸、對苯二甲酸、1,4-萘二甲酸、4,4'-聯苯二羧酸、該等之酸酐等。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. 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, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, anhydrides thereof, and the like.

作為聚醚多元醇，例如可列舉：藉由以水、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)、二羥基苯(鄰苯二酚、間苯二酚、對苯二酚等)等為起始劑，使環氧乙烷、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、聚四亞甲基二醇等。Examples of the polyether polyol include water, low-molecular-weight polyols (propylene glycol, ethylene glycol, glycerol, trimethylolpropane, pentaerythritol, etc.), bisphenols (bisphenol A, etc.), and dihydroxy groups. Benzene (catechol, resorcinol, hydroquinone, etc.) as a starter, a polymer obtained by addition polymerization of ethylene oxide, propylene oxide, butylene oxide and the like Ether polyol. Specific examples include polyethylene glycol, polypropylene glycol, and polytetramethylene 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己內酯系聚酯二醇等。Examples of the polycaprolactone polyol include a caprolactone-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：使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；使上述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、乙基丁基碳酸、碳酸乙二酯、碳酸丙二酯、碳酸二苯酯、碳酸二苄酯等碳酸二酯類進行酯交換縮合而獲得之聚碳酸酯多元醇；併用兩種以上之上述多元醇成分而獲得之共聚聚碳酸酯多元醇；使上述各種聚碳酸酯多元醇與含羧基之化合物進行酯化而獲得之聚碳酸酯多元醇；使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；使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；使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；使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；使上述各種聚碳酸酯多元醇與環氧烷進行共聚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 subjecting the above-mentioned polyol component to a polycondensation reaction with phosgene; and the above-mentioned polyol component and dimethyl carbonate, diethyl carbonate, and dipropylene carbonate. Ester, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, dibenzyl carbonate, etc. A polycarbonate polyol; a copolymerized polycarbonate polyol obtained by using two or more of the above-mentioned polyol components; a polycarbonate polyol obtained by esterifying the various polycarbonate polyols described above with a carboxyl-containing compound; A polycarbonate polyol obtained by subjecting the various polycarbonate polyols described above to an etherification reaction with a hydroxyl-containing compound; a polycarbonate polyol obtained by subjecting the various polycarbonate polyols described above to an ester interchange reaction; A polycarbonate polyol obtained by subjecting the above-mentioned various polycarbonate polyols to a transesterification reaction with a hydroxyl-containing compound; the above-mentioned various polycarbonate polyols and a dicarboxylic acid A compound obtained by a polycondensation reaction of polyester polycarbonate polyols; so that the various polycarbonate polyol with an alkylene oxide is obtained by 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.

多元醇之數量平均分子量Mn較佳為300～100000，更佳為400～75000，進而較佳為450～50000，尤佳為500～30000。若多元醇之數量平均分子量Mn為上述範圍內，則本發明之表面保護膜可變得更難以自被黏著體容易地剝離，可進一步抑制經時之重剝離化。The number average molecular weight Mn of the polyol is preferably 300 to 100,000, more preferably 400 to 75,000, still more preferably 450 to 50,000, and even more preferably 500 to 30,000. When the number average molecular weight Mn of the polyhydric alcohol is within the above range, the surface protective film of the present invention can be made more difficult to be easily peeled from the adherend, and the heavy peeling over time can be further suppressed.

作為多元醇，較佳為含有具有3個OH基之數量平均分子量Mn為300～100000之多元醇(A1)。多元醇(A1)可僅為一種，亦可為兩種以上。The polyhydric alcohol is preferably a polyhydric alcohol (A1) containing a number average molecular weight Mn of 300 to 100,000 having three OH groups. The polyol (A1) may be only one kind, or two or more kinds.

多元醇中之多元醇(A1)之含有比例較佳為5重量%以上，更佳為25重量%～100重量%，進而較佳為50重量%～100重量%。若多元醇中之多元醇(A1)之含有比例為上述範圍內，則本發明之表面保護膜可變得更難以自被黏著體容易地剝離，可進一步抑制經時之重剝離化。The content of the polyol (A1) in the polyol is preferably 5% by weight or more, more preferably 25% to 100% by weight, and still more preferably 50% to 100% by weight. When the content ratio of the polyhydric alcohol (A1) in the polyhydric alcohol is within the above range, the surface protective film of the present invention can be more difficult to be easily peeled off from the adherend, and the re-peeling over time can be further suppressed.

多元醇(A1)之數量平均分子量Mn較佳為1000～100000，更佳為1200～80000，進而較佳為1500～70000，進而較佳為1750～50000，尤佳為1500～40000，最佳為2000～30000。若多元醇(A1)之數量平均分子量Mn為上述範圍內，則本發明之表面保護膜可變得更難以自被黏著體容易地剝離，可進一步抑制經時之重剝離化。The number average molecular weight Mn of the polyol (A1) is preferably 1,000 to 100,000, more preferably 1200 to 80,000, still more preferably 1,500 to 70,000, still more preferably 1750 to 50,000, even more preferably 1,500 to 40,000, and most preferably 2000 to 30,000. When the number average molecular weight Mn of the polyhydric alcohol (A1) is within the above range, the surface protective film of the present invention can be more difficult to be easily peeled off from the adherend, and the heavy peeling over time can be further suppressed.

多元醇可含有具有3個以上OH基之數量平均分子量Mn為20000以下之多元醇(A2)。多元醇(A2)可僅為一種，亦可為兩種以上。多元醇(A2)之數量平均分子量Mn較佳為100～20000，更佳為150～10000，進而較佳為200～7500，尤佳為300～6000，最佳為300～5000。若多元醇(A2)之數量平均分子量Mn脫離出上述範圍內，則尤其存在本發明之表面保護膜之剝離力之經時上升性變高之虞。作為多元醇(A2)，可較佳列舉：具有3個OH基之多元醇(三醇)、具有4個OH基之多元醇(四醇)、具有5個OH基之多元醇(五醇)、具有6個OH基之多元醇(六醇)。The polyol may contain a polyol (A2) having a number average molecular weight Mn of 3 or more OH groups of 20,000 or less. The polyol (A2) may be only one kind, or two or more kinds. The number average molecular weight Mn of the polyol (A2) is preferably from 100 to 20,000, more preferably from 150 to 10,000, even more preferably from 200 to 7,500, even more preferably from 300 to 6,000, and most preferably from 300 to 5,000. When the number average molecular weight Mn of the polyol (A2) deviates from the above range, there is a possibility that the time-rising property of the peeling force of the surface protective film of the present invention becomes high. As the polyhydric alcohol (A2), a polyhydric alcohol (triol) having 3 OH groups, a polyhydric alcohol (tetraol) having 4 OH groups, and a polyhydric alcohol (pentaol) having 5 OH groups can be exemplified. Polyols (hexaols) with 6 OH groups.

關於作為多元醇(A2)之具有4個OH基之多元醇(四醇)、具有5個OH基之多元醇(五醇)、具有6個OH基之多元醇(六醇)之總量，作為多元醇中之含有比例，較佳為70重量%以下，更佳為60重量%以下，進而較佳為40重量%以下，尤佳為30重量%以下。多元醇中，若作為多元醇(A2)之具有4個OH基之多元醇(四醇)、具有5個OH基之多元醇(五醇)、具有6個OH基之多元醇(六醇)之總量於多元醇中之含有比例為上述範圍，則可提供透明性優異之黏著劑層，又，本發明之表面保護膜可變得更難以自被黏著體容易地剝離，可進一步抑制經時之重剝離化。Regarding the total amount of a polyol (tetraol) having 4 OH groups, a polyol (pentaol) having 5 OH groups, and a polyol (hexaol) having 6 OH groups as the polyol (A2), The content of the polyol is preferably 70% by weight or less, more preferably 60% by weight or less, still more preferably 40% by weight or less, and even more preferably 30% by weight or less. Among the polyols, if the polyol (A2) is a polyol (tetraol) having 4 OH groups, a polyol (pentaol) having 5 OH groups, and a polyol (hexaol) having 6 OH groups The total content of the polyhydric alcohol in the above-mentioned range can provide an adhesive layer with excellent transparency. In addition, the surface protective film of the present invention can be more difficult to be easily peeled off from the adherend, which can further suppress the process. Time to peel off.

多元醇中之多元醇(A2)之含有比例較佳為95重量%以下，更佳為0重量%～75重量%。若多元醇中之多元醇(A2)之含有比例為上述範圍內，則本發明之表面保護膜可變得更難以自被黏著體容易地剝離，可進一步抑制經時之重剝離化。The content of the polyol (A2) in the polyol is preferably 95% by weight or less, and more preferably 0% to 75% by weight. When the content ratio of the polyhydric alcohol (A2) in the polyhydric alcohol is within the above range, the surface protective film of the present invention can be more difficult to be easily peeled off from the adherend, and the heavy peeling over time can be further suppressed.

作為多元醇(A2)之具有4個以上OH基之數量平均分子量Mn為20000以下之多元醇之含有比例相對於多元醇整體，較佳為未達70重量%，更佳為60重量%以下，進而較佳為50重量%以下，尤佳為40重量%以下，最佳為30重量%以下。若作為多元醇(A2)之具有4個以上OH基之數量平均分子量Mn為20000以下之多元醇之含有比例相對於多元醇整體為上述範圍，則可提供透明性優異之黏著劑層，又，本發明之表面保護膜可變得更難以自被黏著體容易地剝離，可進一步抑制經時之重剝離化。As for the polyol (A2), the content of the polyol having a number average molecular weight Mn of 4 or more having OH groups of 20,000 or less is preferably less than 70% by weight, and more preferably 60% by weight or less with respect to the entire polyol. It is more preferably 50% by weight or less, particularly preferably 40% by weight or less, and most preferably 30% by weight or less. If the content ratio of the polyol having the number average molecular weight Mn of 4 or more OH groups of 4 or more as the polyol (A2) is within the above range with respect to the entire polyol, an adhesive layer having excellent transparency can be provided. The surface protection film of the present invention can be made more difficult to be easily peeled off from the adherend, and it can further suppress heavy peeling over time.

[A-2-1-c.丙烯酸系樹脂]
作為丙烯酸系樹脂，於不損害本發明之效果之範圍內，例如可採用日本專利特開2013-241606號公報等中記載之公知之丙烯酸系黏著劑等任意合適之丙烯酸系黏著劑。[A-2-1-c. Acrylic resin]
As the acrylic resin, any suitable acrylic adhesive such as a known acrylic adhesive described in Japanese Patent Laid-Open No. 2013-241606 can be used as long as the effect of the present invention is not impaired.

丙烯酸系樹脂可於不損害本發明之效果之範圍內含有任意合適之成分。作為此種成分，例如可列舉：丙烯酸系樹脂以外之樹脂成分、黏著賦予劑、無機填充劑、有機填充劑、金屬粉、顏料、箔狀物、軟化劑、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、觸媒等。The acrylic resin may contain any appropriate component so long as the effect of the present invention is not impaired. Examples of such components include resin components other than acrylic resins, adhesion-imparting agents, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, and ultraviolet absorption. Agents, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts, etc.

[A-2-1-d.橡膠系樹脂]
作為橡膠系樹脂，可於不損害本發明之效果之範圍內，例如採用日本專利特開2015-074771號公報等中記載之公知之橡膠系黏著劑等任意合適之橡膠系黏著劑。該等可僅為一種，亦可為兩種以上。[A-2-1-d. Rubber-based resin]
As the rubber-based resin, any suitable rubber-based adhesive such as a known rubber-based adhesive described in Japanese Patent Laid-Open No. 2015-074771 can be used as long as the effect of the present invention is not impaired. These may be only one type or two or more types.

橡膠系樹脂可於不損害本發明之效果之範圍內含有任意合適之成分。作為此種成分，例如可列舉：橡膠系樹脂以外之樹脂成分、黏著賦予劑、無機填充劑、有機填充劑、金屬粉、顏料、箔狀物、軟化劑、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、觸媒等。The rubber-based resin may contain any appropriate component as long as the effect of the present invention is not impaired. Examples of such components include resin components other than rubber-based resins, adhesion-imparting agents, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, and ultraviolet absorption. Agents, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts, etc.

[A-2-1-e.聚矽氧系樹脂]
作為聚矽氧系黏著劑，可於不損害本發明之效果之範圍內，例如採用日本專利特開2014-047280號公報等中記載之公知之聚矽氧系黏著劑等任意合適之聚矽氧系黏著劑。該等可僅為一種，亦可為兩種以上。[A-2-1-e. Polysiloxane resin]
As the silicone adhesive, any suitable silicone such as a known silicone adhesive described in Japanese Patent Application Laid-Open No. 2014-047280 can be used as long as the effect of the present invention is not impaired. Department of adhesive. These may be only one type or two or more types.

聚矽氧系樹脂可於不損害本發明之效果之範圍內含有任意合適之成分。作為此種成分，例如可列舉：聚矽氧系樹脂以外之樹脂成分、黏著賦予劑、無機填充劑、有機填充劑、金屬粉、顏料、箔狀物、軟化劑、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、觸媒等。The polysiloxane resin may contain any appropriate component so long as the effect of the present invention is not impaired. Examples of such components include resin components other than polysiloxane resins, adhesion-imparting agents, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, UV absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts, etc.

＜A-2-2.聚矽氧系添加劑＞
聚矽氧系添加劑可於不損害本發明之效果之範圍內採用任意合適之聚矽氧系添加劑。作為此種聚矽氧系添加劑，較佳可列舉：選自含矽氧烷鍵之化合物、含羥基之聚矽氧系化合物、含交聯性官能基之聚矽氧系化合物中之至少一種。＜ A-2-2. Polysiloxane additives ＞
As the polysiloxane additive, any suitable polysiloxane additive can be used as long as the effect of the present invention is not impaired. As such a polysiloxane-based additive, preferably, at least one selected from the group consisting of a compound containing a siloxane bond, a polysiloxane compound containing a hydroxyl group, and a polysiloxane compound containing a crosslinkable functional group.

聚矽氧系添加劑可僅為一種，亦可為兩種以上。The polysiloxane-based additive may be only one kind, or two or more kinds.

作為含矽氧烷鍵之化合物，例如可列舉：於聚有機矽氧烷骨架(聚二甲基矽氧烷等)之主鏈或側鏈導入聚醚基之聚醚改性聚有機矽氧烷、於聚有機矽氧烷骨架之主鏈或側鏈導入聚酯基之聚酯改性聚有機矽氧烷、於聚有機矽氧烷骨架之主鏈或側鏈導入有機化合物之有機化合物導入聚有機矽氧烷、於(甲基)丙烯酸系樹脂導入聚有機矽氧烷之聚矽氧改性(甲基)丙烯酸系樹脂、於有機化合物導入聚有機矽氧烷之聚矽氧改性有機化合物、使有機化合物與聚矽氧化合物共聚而成之含聚矽氧之有機化合物等。作為此種含矽氧烷鍵之聚合物，作為市售品，例如可列舉：商品名「LE-302」(共榮社化學股份有限公司製造)、BYK-Chemie・Japan(股)製造之BYK系列之調平劑(「BYK-300」、「BYK-301/302」、「BYK-306」、「BYK-307」、「BYK-310」、「BYK-315」、「BYK-313」、「BYK-320」、「BYK-322」、「BYK-323」、「BYK-325」、「BYK-330」、「BYK-331」、「BYK-333」、「BYK-337」、「BYK-341」、「BYK-344」、「BYK-345/346」、「BYK-347」、「BYK-348」、「BYK-349」、「BYK-370」、「BYK-375」、「BYK-377」、「BYK-378」、「BYK-UV3500」、「BYK-UV3510」、「BYK-UV3570」、「BYK-3550」、「BYK-SILCLEAN3700」、「BYK-SILCLEAN3720」等)、Algin Chemie公司製造之AC系列之調平劑(「AC FS180」、「AC FS360」、「AC S20」等)、共榮社化學(股)製造之Polyflow系列之調平劑(「Polyflow KL-400X」、「Polyflow KL-400HF」、「Polyflow KL-401」、「Polyflow KL-402」、「Polyflow KL-403」、「Polyflow KL-404」等)、信越化學工業(股)製造之KP系列之調平劑(「KP-323」、「KP-326」、「KP-341」、「KP-104」、「KP-110」、「KP-112」等)、信越化學公司製造之X22系列、KF系列等、Dow Corning Toray(股)製造之調平劑(「LP-7001」、「LP-7002」、「8032ADDITIVE」、「57ADDITIVE」、「L-7604」、「FZ-2110」、「FZ-2105」、「67ADDITIVE」、「8618ADDITIVE」、「3ADDITIVE」、「56ADDITIVE」等)等。Examples of the compound containing a siloxane bond include a polyether-modified polyorganosiloxane in which a polyether group is introduced into a main chain or a side chain of a polyorganosiloxane frame (such as polydimethylsiloxane). Polyester-modified polyorganosiloxane introduced into the main chain or side chain of the polyorganosiloxane skeleton, and polyester-modified polyorganosiloxane introduced into the main chain or side chain of the polyorganosiloxane skeleton. Organosiloxane, polysiloxane modified (meth) acrylic resin introduced with polyorganosiloxane in (meth) acrylic resin, polysiloxane modified organic compound with polyorganosiloxane introduced in organic compound 2. Polysiloxane-containing organic compounds obtained by copolymerizing an organic compound with a polysiloxane. Examples of such a siloxane-containing polymer include commercially available products: "LE-302" (manufactured by Kyoeisha Chemical Co., Ltd.), and BYK manufactured by BYK-Chemie Japan Co., Ltd. Series of leveling agents ("BYK-300", "BYK-301 / 302", "BYK-306", "BYK-307", "BYK-310", "BYK-315", "BYK-313", "BYK-320", "BYK-322", "BYK-323", "BYK-325", "BYK-330", "BYK-331", "BYK-333", "BYK-337", "BYK -341 "," BYK-344 "," BYK-345 / 346 "," BYK-347 "," BYK-348 "," BYK-349 "," BYK-370 "," BYK-375 "," BYK -377 "," BYK-378 "," BYK-UV3500 "," BYK-UV3510 "," BYK-UV3570 "," BYK-3550 "," BYK-SILCLEAN3700 "," BYK-SILCLEAN3720 ", etc.), Algin Chemie AC series leveling agents ("AC FS180", "AC FS360", "AC S20", etc.) manufactured by the company, Polyflow series leveling agents ("Polyflow KL-400X", "Polyflow KL-400HF", "Polyflow KL-401", "Polyflow KL-402", "Polyflow "KL-403", "Polyflow KL-404", etc., KP series leveling agents ("KP-323", "KP-326", "KP-341", "KP- 104 '', `` KP-110 '', `` KP-112 '', etc.), X22 series manufactured by Shin-Etsu Chemical Co., Ltd., KF series, etc., leveling agents (`` LP-7001 '', `` LP-001 '' manufactured by Dow Corning Toray Co., Ltd. 7002 "," 8032ADDITIVE "," 57ADDITIVE "," L-7604 "," FZ-2110 "," FZ-2105 "," 67ADDITIVE "," 8618ADDITIVE "," 3ADDITIVE "," 56ADDITIVE ", etc.).

作為含羥基之聚矽氧系化合物，例如可列舉：於聚有機矽氧烷骨架(聚二甲基矽氧烷等)之主鏈或側鏈導入聚醚基之聚醚改性聚有機矽氧烷、於聚有機矽氧烷骨架之主鏈或側鏈導入聚酯基之聚酯改性聚有機矽氧烷、於聚有機矽氧烷骨架之主鏈或側鏈導入有機化合物之有機化合物導入聚有機矽氧烷、於(甲基)丙烯酸系樹脂導入聚有機矽氧烷之聚矽氧改性(甲基)丙烯酸系樹脂、於有機化合物導入聚有機矽氧烷之聚矽氧改性有機化合物、使有機化合物與聚矽氧化合物共聚而成之含聚矽氧之有機化合物等。於該等中，羥基可為聚有機矽氧烷骨架所具有，亦可為聚醚基、聚酯基、(甲基)丙烯醯基、有機化合物所具有。作為此種含羥基之聚矽氧，作為市售品，例如可列舉：商品名「X-22-4015」、「X-22-4039」、「KF6000」、「KF6001」、「KF6002」、「KF6003」、「X-22-170BX」、「X-22-170DX」、「X-22-176DX」、「X-22-176F」(信越化學工業股份有限公司製造)、BYK-Chemie・Japan(股)製造之「BYK-370」、「BYK-SILCLEAN3700」、「BYK-SILCLEAN3720」等。Examples of the hydroxyl-containing polysiloxane compound include a polyether-modified polyorganosiloxane in which a polyether group is introduced into a main chain or a side chain of a polyorganosiloxane frame (such as polydimethylsiloxane). Alkane, polyester-modified polyorganosiloxane introduced into the main chain or side chain of the polyorganosiloxane frame, and organic compound introduced into the main chain or side chain of the polyorganosiloxane frame Polyorganosiloxane, polysiloxane modified (meth) acrylic resin with polyorganosiloxane introduced into (meth) acrylic resin, polysiloxane modified organic with polyorganosiloxane introduced into organic compound Compounds, polysiloxane-containing organic compounds obtained by copolymerizing an organic compound and a polysiloxane. Among these, the hydroxyl group may be possessed by a polyorganosiloxane frame, or may be possessed by a polyether group, a polyester group, a (meth) acryl group, or an organic compound. As such a hydroxyl-containing polysiloxane, as a commercially available product, for example, trade names: "X-22-4015", "X-22-4039", "KF6000", "KF6001", "KF6002", " KF6003 "," X-22-170BX "," X-22-170DX "," X-22-176DX "," X-22-176F "(made by Shin-Etsu Chemical Industry Co., Ltd.), BYK-Chemie ・ Japan ( "BYK-370", "BYK-SILCLEAN3700", "BYK-SILCLEAN3720", etc.

作為含交聯性官能基之聚矽氧系化合物，例如可列舉：於聚有機矽氧烷骨架(聚二甲基矽氧烷等)之主鏈或側鏈導入聚醚基之聚醚改性聚有機矽氧烷、於聚有機矽氧烷骨架之主鏈或側鏈導入聚酯基之聚酯改性聚有機矽氧烷、於聚有機矽氧烷骨架之主鏈或側鏈導入有機化合物之有機化合物導入聚有機矽氧烷、於(甲基)丙烯酸系樹脂導入聚有機矽氧烷之聚矽氧改性(甲基)丙烯酸系樹脂、於有機化合物導入聚有機矽氧烷之聚矽氧改性有機化合物、使有機化合物與聚矽氧化合物共聚而成之含聚矽氧之有機化合物等。於該等中，交聯性官能基可為聚有機矽氧烷骨架所具有，亦可為聚醚基、聚酯基、(甲基)丙烯醯基、有機化合物所具有。作為交聯性官能基，可列舉：胺基、環氧基、巰基、羧基、異氰酸酯基、甲基丙烯酸酯基等。作為此種含異氰酸酯基之聚矽氧，作為市售品，例如可列舉：Dow Corning Toray(股)製造之「BY16-855」、「SF8413」、「BY16-839」、「SF8421」、「BY16-750」、「BY16-880」、「BY16-152C」、信越化學工業股份有限公司製造之「KF-868」、「KF-865」、「KF-864」、「KF-859」、「KF-393」、「KF-860」、「KF-880」、「KF-8004」、「KF-8002」、「KF-8005」、「KF-867」、「KF-8021」、「KF-869」、「KF-861」、「X-22-343」、「KF-101」、「X-22-2000」、「X-22-4741」、「KF-1002」、「KF-2001」、「X-22-3701E」、「X-22-164」、「X-22-164A」、「X-22-164B」、「X-22-164AS」、「X-22-2445」等。Examples of the crosslinkable functional group-containing polysiloxane compound include polyether modification in which a polyether group is introduced into a main chain or a side chain of a polyorganosiloxane frame (such as polydimethylsiloxane). Polyorganosiloxane, polyester modified polyorganosiloxane introduced into the main chain or side chain of the polyorganosiloxane framework, and organic compounds introduced into the main chain or side chain of the polyorganosiloxane framework Polyorganosiloxane is introduced into organic compounds, polysiloxane modified (meth) acrylic resin is introduced into (meth) acrylic resins, and polyorganosiloxane is introduced into polysiloxanes. Oxygen-modified organic compounds, polysiloxane-containing organic compounds made by copolymerizing organic compounds with polysiloxanes, and the like. Among these, the crosslinkable functional group may be possessed by a polyorganosiloxane skeleton, or may be possessed by a polyether group, a polyester group, a (meth) acrylfluorene group, or an organic compound. Examples of the crosslinkable functional group include an amine group, an epoxy group, a mercapto group, a carboxyl group, an isocyanate group, and a methacrylate group. Examples of such isocyanate-containing polysiloxanes include commercially available products such as "BY16-855", "SF8413", "BY16-839", "SF8421", "BY16" manufactured by Dow Corning Toray Co., Ltd. -750 "," BY16-880 "," BY16-152C "," KF-868 "," KF-865 "," KF-864 "," KF-859 "," KF "manufactured by Shin-Etsu Chemical Industry Co., Ltd. -393 "," KF-860 "," KF-880 "," KF-8004 "," KF-8002 "," KF-8005 "," KF-867 "," KF-8021 "," KF-869 " "," KF-861 "," X-22-343 "," KF-101 "," X-22-2000 "," X-22-4741 "," KF-1002 "," KF-2001 ", "X-22-3701E", "X-22-164", "X-22-164A", "X-22-164B", "X-22-164AS", "X-22-2445", etc.

＜A-2-3.氟系添加劑＞
氟系添加劑可於不損害本發明之效果之範圍內採用任意合適之氟系添加劑。作為此種氟系添加劑，較佳可列舉：選自含氟之化合物、含羥基之氟系化合物、含交聯性官能基之氟系化合物中之至少一種。＜ A-2-3. Fluorine Additives ＞
As the fluorine-based additive, any appropriate fluorine-based additive can be used as long as the effect of the present invention is not impaired. As such a fluorine-based additive, preferably, at least one selected from a fluorine-containing compound, a hydroxyl-containing fluorine-based compound, and a crosslinkable functional group-containing fluorine-based compound is mentioned.

氟系添加劑可僅為一種，亦可為兩種以上。The fluorine-based additive may be only one kind, or two or more kinds.

作為含氟之化合物，例如可列舉：具有氟脂肪族烴骨架之化合物、使有機化合物與氟化合物共聚而成之含氟之有機化合物、含有有機化合物之含氟之化合物等。作為氟脂肪族烴骨架，例如可列舉：氟甲烷、氟乙烷、氟丙烷、氟異丙烷、氟丁烷、氟異丁烷、氟第三丁烷、氟戊烷、氟己烷等氟C1-C10烷烴等。作為此種含氟之化合物，作為市售品，例如可列舉：AGC Seimi Chemical(股)製造之Surflon系列之調平劑(「S-242」、「S-243」、「S-420」、「S-611」、「S-651」、「S-386」等)、BYK-Chemie・Japan(股)製造之BYK系列之調平劑(「BYK-340」等)、Algin Chemie公司製造之AC系列之調平劑(「AC 110a」、「AC 100a」等)、DIC(股)製造之MEGAFAC系列之調平劑(「MEGAFAC F-114」、「MEGAFAC F-410」、「MEGAFAC F-444」、「MEGAFAC EXP TP-2066」、「MEGAFAC F-430」、「MEGAFAC F-472SF」、「MEGAFAC F-477」、「MEGAFAC F-552」、「MEGAFAC F-553」、「MEGAFAC F-554」、「MEGAFAC F-555」、「MEGAFAC R-94」、「MEGAFAC RS-72-K」、「MEGAFAC RS-75」、「MEGAFAC F-556」、「MEGAFAC EXP TF-1367」、「MEGAFAC EXP TF-1437」、「MEGAFAC F-558」、「MEGAFAC EXP TF-1537」等)、Sumitomo 3M(股)製造之FC系列之調平劑(「FC-4430」、「FC-4432」等)、NEOS(股)製造之FTERGENT系列之調平劑(「FTERGENT 100」、「FTERGENT 100C」、「FTERGENT 110」、「FTERGENT 150」、「FTERGENT 150CH」、「FTERGENT A-K」、「FTERGENT 501」、「FTERGENT 250」、「FTERGENT 251」、「FTERGENT 222F」、「FTERGENT 208G」、「FTERGENT 300」、「FTERGENT 310」、「FTERGENT 400SW」等)、北村化學產業(股)製造之PF系列之調平劑(「PF-136A」、「PF-156A」、「PF-151N」、「PF-636」、「PF-6320」、「PF-656」、「PF-6520」、「PF-651」、「PF-652」、「PF-3320」等)等。Examples of the fluorine-containing compound include a compound having a fluoroaliphatic hydrocarbon skeleton, a fluorine-containing organic compound obtained by copolymerizing an organic compound and a fluorine compound, and a fluorine-containing compound containing an organic compound. Examples of the fluoroaliphatic hydrocarbon skeleton include fluorine C1 such as fluoromethane, fluoroethane, fluoropropane, fluoroisopropane, fluorobutane, fluoroisobutane, fluorotributane, fluoropentane, and fluorohexane. -C10 alkane and the like. As such a fluorine-containing compound, as a commercially available product, for example, a Surflon series leveling agent ("S-242", "S-243", "S-420", "S-611", "S-651", "S-386", etc.), BYK series leveling agents ("BYK-340", etc.) manufactured by BYK-Chemie Japan, etc., manufactured by Algin Chemie AC series leveling agents (`` AC 110a '', `` AC 100a '', etc.), MEGAFAC series leveling agents (`` MEGAFAC F-114 '', `` MEGAFAC F-410 '', `` MEGAFAC F- 444 "," MEGAFAC EXP TP-2066 "," MEGAFAC F-430 "," MEGAFAC F-472SF "," MEGAFAC F-477 "," MEGAFAC F-552 "," MEGAFAC F-553 "," MEGAFAC F- 554 "," MEGAFAC F-555 "," MEGAFAC R-94 "," MEGAFAC RS-72-K "," MEGAFAC RS-75 "," MEGAFAC F-556 "," MEGAFAC EXP TF-1367 "," MEGAFAC EXP TF-1437 '', `` MEGAFAC F-558 '', `` MEGAFAC EXP TF-1537 '', etc.), FC series leveling agents (`` FC-4430 '', `` FC-4432 '', etc.) manufactured by Sumitomo 3M Co., Ltd. 、 FTERGENT series of leveling agents (`` FTERG ENT 100 "," FTERGENT 100C "," FTERGENT 110 "," FTERGENT 150 "," FTERGENT 150CH "," FTERGENT AK "," FTERGENT 501 "," FTERGENT 250 "," FTERGENT 251 "," FTERGENT 222F "," FTERGENT 208G "," FTERGENT 300 "," FTERGENT 310 "," FTERGENT 400SW ", etc.), PF series leveling agents (" PF-136A "," PF-156A "," PF " -151N "," PF-636 "," PF-6320 "," PF-656 "," PF-6520 "," PF-651 "," PF-652 "," PF-3320 ", etc.).

作為含羥基之氟系化合物，例如可使用先前公知之樹脂，例如可列舉：國際公開第94/06870號說明書、日本專利特開平8-12921號公報、日本專利特開平10-72569號公報、日本專利特開平4-275379號公報、國際公開第97/11130號說明書、國際公開第96/26254號說明書等中記載之含羥基之氟樹脂。作為其他含羥基之氟樹脂，例如可列舉：日本專利特開平8-231919號公報、日本專利特開平10-265731號公報、日本專利特開平10-204374號公報、日本專利特開平8-12922號公報等中記載之氟烯烴共聚物等。其他可列舉：於含羥基之化合物中具有氟化烷基之化合物之共聚物、使含氟之化合物與含羥基之化合物共聚而成之含氟之有機化合物、含有含羥基之有機化合物之含氟之化合物等。作為此種含羥基之氟系化合物，作為市售品，例如可列舉：商品名「Lumiflon」(旭硝子(股)製造)、商品名「Cefralcoat」(Central Glass(股)製造)、商品名「Zaflon」(東亞合成(股)製造)、商品名「ZEFFLE」(大金工業(股)製造)、商品名「MEGAFAC F-571」、「FLUONATE」(DIC(股)製造)等。As the hydroxyl-containing fluorine-based compound, conventionally known resins can be used, for example, International Publication No. 94/06870, Japanese Patent Laid-Open No. 8-12921, Japanese Patent Laid-Open No. 10-72569, and Japan The hydroxyl-containing fluororesin described in Japanese Patent Application Laid-Open No. 4-275379, International Publication No. 97/11130, International Publication No. 96/26254, and the like. Examples of other hydroxyl-containing fluorine resins include Japanese Patent Laid-Open No. 8-231919, Japanese Patent Laid-Open No. 10-265731, Japanese Patent Laid-Open No. 10-204374, and Japanese Patent Laid-Open No. 8-12922. Fluoroolefin copolymers and the like described in the bulletin and the like. Other examples include a copolymer of a compound having a fluorinated alkyl group in a compound containing a hydroxyl group, a fluorine-containing organic compound obtained by copolymerizing a fluorine-containing compound and a hydroxyl-containing compound, and a fluorine-containing organic compound containing a hydroxyl-containing organic compound. Of compounds, etc. As such a hydroxyl-containing fluorine-based compound, as a commercially available product, for example, the product name is "Lumiflon" (manufactured by Asahi Glass Co., Ltd.), the product name is "Cefralcoat" (manufactured by Central Glass Co., Ltd.), and the product name is "Zaflon "(Manufactured by Toa Kosei Co., Ltd.), trade name" ZEFFLE "(manufactured by Daikin Industries Co., Ltd.), trade name" MEGAFAC F-571 "," FLUONATE "(manufactured by DIC Co., Ltd.), etc.

作為含交聯性官能基之氟系化合物，例如可列舉：如全氟辛酸等之具有氟化烷基之羧酸化合物、於含交聯性官能基之化合物中具有氟化烷基之化合物之共聚物、使含氟之化合物與含交聯性官能基之化合物共聚而成之含氟之有機化合物、含有含交聯性官能基之化合物之含氟之化合物等。作為此種含交聯性官能基之氟系化合物，作為市售品，例如可列舉：商品名「MEGAFAC F-570」、「MEGAFAC RS-55」、「MEGAFAC RS-56」、「MEGAFAC RS-72-K」、「MEGAFAC RS-75」、「MEGAFAC RS-76-E」、「MEGAFAC RS-76-NS」、「MEGAFAC RS-78」、「MEGAFAC RS-90」(DIC(股)製造)等。Examples of the crosslinkable functional group-containing fluorine-based compound include a carboxylic acid compound having a fluorinated alkyl group such as perfluorooctanoic acid, and a copolymer of a compound having a fluorinated alkyl group among compounds having a crosslinkable functional group. 2. A fluorine-containing organic compound obtained by copolymerizing a fluorine-containing compound and a cross-linkable functional group-containing compound, a fluorine-containing compound containing a cross-linkable functional group-containing compound, and the like. As such a fluorine-containing compound containing a crosslinkable functional group, as a commercially available product, for example, trade names are "MEGAFAC F-570", "MEGAFAC RS-55", "MEGAFAC RS-56", and "MEGAFAC RS- 72-K "," MEGAFAC RS-75 "," MEGAFAC RS-76-E "," MEGAFAC RS-76-NS "," MEGAFAC RS-78 "," MEGAFAC RS-90 "(manufactured by DIC) Wait.

＜A-2-4.胺基甲酸酯系樹脂＞
上述作為基礎聚合物之胺基甲酸酯預聚物及多元醇可分別與多官能異氰酸酯化合物(B)組合，成為用以形成胺基甲酸酯系樹脂之組合物之成分。藉由採用如上述者作為用以形成胺基甲酸酯系樹脂之組合物之成分，本發明之表面保護膜可變得更難以自被黏著體容易地剝離，可進一步抑制經時之重剝離化。<A-2-4. Urethane resin>
The above-mentioned urethane prepolymer and polyol as the base polymer may be combined with the polyfunctional isocyanate compound (B), respectively, to become components of a composition for forming a urethane-based resin. By using the above as a component of the composition for forming a urethane-based resin, the surface protective film of the present invention can be made more difficult to peel off easily from the adherend, and the heavy peeling over time can be further suppressed. Into.

用以形成胺基甲酸酯系樹脂之組合物可於不損害本發明之效果之範圍內含有任意合適之其他成分。作為此種成分，例如可列舉：胺基甲酸酯系樹脂以外之樹脂成分、黏著賦予劑、無機填充劑、有機填充劑、金屬粉、顏料、箔狀物、軟化劑、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、觸媒等。The composition for forming a urethane-based resin may contain any appropriate other components within a range that does not impair the effects of the present invention. Examples of such components include resin components other than urethane resins, adhesion-imparting agents, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, and electrical conductivity. Agents, UV absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts, etc.

用以形成胺基甲酸酯系樹脂之組合物較佳為含有抗氧化劑、紫外線吸收劑、光穩定劑等抗劣化劑。藉由使用以形成胺基甲酸酯系樹脂之組合物含有抗劣化劑，即使將形成之黏著劑層貼附於被黏著體後於加溫狀態下保存，被黏著體亦難以產生糊劑殘留等抗糊劑殘留性可變得優異。抗劣化劑可僅為一種，亦可為兩種以上。作為抗劣化劑，尤佳為抗氧化劑。The composition for forming a urethane-based resin preferably contains an anti-deteriorating agent such as an antioxidant, an ultraviolet absorber, and a light stabilizer. The composition used to form the urethane-based resin contains an anti-deterioration agent, and even if the formed adhesive layer is attached to the adherend and stored under a warmed state, it is difficult for the adherend to generate a paste residue. Anti-paste residue can be excellent. The anti-deterioration agent may be only one kind, or two or more kinds. As the anti-deterioration agent, an antioxidant is particularly preferable.

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、丁基化羥基苯甲醚、2,6-二第三丁基-4-乙基苯酚、β-(3,5-二第三丁基-4-羥基苯基)丙酸硬脂酯等。Examples of the monophenol-based antioxidant include 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-tert-butyl-4-ethylphenol, β -(3,5-di-tert-butyl-4-hydroxyphenyl) stearate 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、雙[3,3'-雙-(4'-羥基-3'-第三丁基苯基)丁酸]二醇酯、1,3,5-三(3',5'-二第三丁基-4'-羥基苄基)-均三-2,4,6-(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-tert-butyl-4-hydroxybenzyl) benzene, tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-4 '-Hydroxyphenyl) propionate] methane, bis [3,3'-bis- (4'-hydroxy-3'-third butylphenyl) butanoic acid] glycol ester, 1,3,5- Tris (3 ', 5'-di-third-butyl-4'-hydroxybenzyl) -mesatri-2,4,6- (1H, 3H, 5H) trione, tocopherol and the like.

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***系紫外線吸收劑、水楊酸系紫外線吸收劑、草醯苯胺系紫外線吸收劑、氰基丙烯酸酯系紫外線吸收劑、三系紫外線吸收劑等。Examples of the ultraviolet absorber include a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a salicylic acid-based ultraviolet absorber, a chloranilide-based ultraviolet absorber, and a cyanoacrylate-based ultraviolet absorber. Agents, three series of ultraviolet absorbers, etc.

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***系紫外線吸收劑，例如可列舉：2-(2'-羥基-5'-甲基苯基)苯并***、2-(2'-羥基-5'-第三丁基苯基)苯并***、2-(2'-羥基-3',5'-二第三丁基苯基)苯并***、2-(2'-羥基-3'-第三丁基-5'-甲基苯基)-5-氯苯并***、2-(2'-羥基-3',5'-二第三丁基苯基)5-氯苯并***、2-(2'-羥基-3',5'-二第三戊基苯基)苯并***、2-(2'-羥基-4'-辛氧基苯基)苯并***、2-[2'-羥基-3'-(3'',4'',5'',6'',-四氫鄰苯二甲醯亞胺甲基)-5'-甲基苯基]苯并***、2,2'亞甲基雙[4-(1,1,3,3-四甲基丁基)-6-(2H-苯并***-2-基)苯酚]、2-(2'-羥基-5'-甲基丙烯醯氧基苯基)-2H-苯并***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-third-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-third-butyl -5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-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' ',-tetrahydrophthalimidemethyl) -5'-methylphenyl] benzotris Azole, 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.

作為氰基丙烯酸酯系紫外線吸收劑，例如可列舉：2-氰基-3,3'-二苯基丙烯酸2-乙基己酯、2-氰基-3,3'-二苯基丙烯酸乙酯等。Examples of the cyanoacrylate-based ultraviolet absorber include 2-ethylhexyl 2-cyano-3,3'-diphenylacrylate, and ethyl 2-cyano-3,3'-diphenylacrylate. Esters, etc.

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：癸二酸雙(2,2,6,6-四甲基-4-哌啶基)酯、癸二酸雙(1,2,2,6,6-五甲基-4-哌啶基)酯、癸二酸甲基-1,2,2,6,6-五甲基-4-哌啶基酯等。Examples of the hindered amine-based light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, and bis (1,2,2,6, sebacate, 6-pentamethyl-4-piperidinyl) ester, methyl sebacate-1,2,2,6,6-pentamethyl-4-piperidinyl ester 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、3,5-二第三丁基-4-羥基苄基-磷酸單乙醇鎳錯合物、二丁基二硫代胺基甲酸鎳、苯甲酸酯類型之淬滅劑、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 3,5-dithionyl Tributyl-4-hydroxybenzyl-nickel monophosphate nickel complex, nickel dibutyl dithiocarbamate, benzoate type quencher, nickel dibutyl dithiocarbamate, etc. .

[A-2-4-a.自含有胺基甲酸酯預聚物與多官能異氰酸酯化合物(B)之組合物形成之胺基甲酸酯系樹脂]
自含有胺基甲酸酯預聚物與多官能異氰酸酯化合物(B)之組合物形成之胺基甲酸酯系樹脂例如可列舉：自含有作為胺基甲酸酯預聚物之聚胺基甲酸酯多元醇與多官能異氰酸酯化合物(B)之組合物形成之胺基甲酸酯系樹脂。[A-2-4-a. Urethane-based resin formed from a composition containing a urethane prepolymer and a polyfunctional isocyanate compound (B)]
Examples of the urethane-based resin formed from a composition containing a urethane prepolymer and a polyfunctional isocyanate compound (B) include, for example, a self-containing urethane prepolymer A urethane resin formed from a combination of an ester polyol and a polyfunctional isocyanate compound (B).

胺基甲酸酯預聚物可僅為一種，亦可為兩種以上。The urethane prepolymer may be only one kind, or two or more kinds.

多官能異氰酸酯化合物(B)可僅為一種，亦可為兩種以上。The polyfunctional isocyanate compound (B) may be only one kind, or 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酯化反應之任意合適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：多官能脂肪族系異氰酸酯化合物、多官能脂環族系異氰酸酯、多官能芳香族系異氰酸酯化合物等。As the polyfunctional isocyanate compound (B), any appropriate polyfunctional isocyanate compound that can be used in the urethanization reaction can be used. Examples of such a polyfunctional isocyanate compound (B) include a polyfunctional aliphatic isocyanate compound, a polyfunctional alicyclic isocyanate, and a polyfunctional aromatic isocyanate compound.

作為多官能脂肪族系異氰酸酯化合物，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、十二亞甲基二異氰酸酯、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 the like. 1,3-butylene diisocyanate, dodecylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc.

作為多官能脂環族系異氰酸酯化合物，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、異佛酮二異氰酸酯、氫化二苯基甲烷二異氰酸酯、氫化苯二甲基二異氰酸酯、氫化甲苯二異氰酸酯、氫化四甲基苯二甲基二異氰酸酯等。Examples of the polyfunctional alicyclic isocyanate compound include 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, and the like. Hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, and the like.

作為多官能芳香族系二異氰酸酯化合物，例如可列舉：伸苯基二異氰酸酯、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、苯二甲基二異氰酸酯等。Examples of the polyfunctional aromatic diisocyanate compound include phenylene 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, Xylylene diisocyanate and the like.

作為多官能異氰酸酯化合物(B)，亦可列舉：如上述之各種多官能異氰酸酯化合物之三羥甲基丙烷加成物、與水反應而成之縮二脲體、具有異氰尿酸酯環之三聚物等。又，亦可併用該等。Examples of the polyfunctional isocyanate compound (B) include the trimethylolpropane adducts of various polyfunctional isocyanate compounds described above, biuret bodies formed by reacting with water, and isocyanurate rings Trimer and so on. Moreover, you may use these together.

含有胺基甲酸酯預聚物與多官能異氰酸酯化合物(B)之組合物中可於不損害本發明之效果之範圍內，含有任意合適之其他成分。作為此種其他成分，例如可列舉：聚胺基甲酸酯系樹脂以外之樹脂成分、黏著賦予劑、無機填充劑、有機填充劑、金屬粉、顏料、箔狀物、軟化劑、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、觸媒等。The composition containing a urethane prepolymer and a polyfunctional isocyanate compound (B) may contain any appropriate other component within the range which does not impair the effect of this invention. Examples of such other components include resin components other than polyurethane resins, adhesion-imparting agents, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, and anti-aging agents. , Conductive agent, ultraviolet absorber, antioxidant, light stabilizer, surface lubricant, leveling agent, anticorrosive agent, heat stabilizer, polymerization inhibitor, lubricant, solvent, catalyst, etc.

作為自含有胺基甲酸酯預聚物與多官能異氰酸酯化合物(B)之組合物形成聚胺基甲酸酯系樹脂之方法，只要為使用所謂的「胺基甲酸酯預聚物」作為原料而製造聚胺基甲酸酯系樹脂之方法，則可採用任意合適之製造方法。As a method for forming a polyurethane resin from a composition containing a urethane prepolymer and a polyfunctional isocyanate compound (B), as long as a so-called "urethane prepolymer" is used as As a method for producing a polyurethane resin as a raw material, any appropriate production method can be adopted.

胺基甲酸酯預聚物之數量平均分子量Mn較佳為3000～1000000。The number average molecular weight Mn of the urethane prepolymer is preferably 3000 to 1,000,000.

胺基甲酸酯預聚物與多官能異氰酸酯化合物(B)中之NCO基與OH基之當量比作為NCO基/OH基，較佳為5.0以下，更佳為0.01～4.75，進而較佳為0.02～4.5，尤佳為0.03～4.25，最佳為0.05～4.0。若NCO基/OH基之當量比為上述範圍內，則本發明之表面保護膜可變得更難以自被黏著體容易地剝離，可進一步抑制經時之重剝離化。The equivalent ratio of the NCO group to the OH group in the urethane prepolymer and the polyfunctional isocyanate compound (B), as the NCO group / OH group, is preferably 5.0 or less, more preferably 0.01 to 4.75, and even more preferably 0.02 to 4.5, particularly preferably 0.03 to 4.25, and most preferably 0.05 to 4.0. When the equivalent ratio of the NCO group / OH group is within the above range, the surface protective film of the present invention can be more difficult to be easily peeled off from the adherend, and the heavy peeling over time can be further suppressed.

作為多官能異氰酸酯化合物(B)之含有比例，多官能異氰酸酯化合物(B)相對於胺基甲酸酯預聚物，較佳為0.01重量%～30重量%，更佳為0.05重量%～25重量%，進而較佳為0.1重量%～20重量%，尤佳為0.5重量%～17.5重量%，最佳為1重量%～15重量%。若多官能異氰酸酯化合物(B)之含有比例為上述範圍內，則本發明之表面保護膜可變得更難以自被黏著體容易地剝離，可進一步抑制經時之重剝離化。As the content ratio of the polyfunctional isocyanate compound (B), the polyfunctional isocyanate compound (B) is preferably 0.01% to 30% by weight, and more preferably 0.05% to 25% by weight relative to the urethane prepolymer. %, More preferably 0.1% to 20% by weight, particularly preferably 0.5% to 17.5% by weight, and most preferably 1% to 15% by weight. When the content ratio of the polyfunctional isocyanate compound (B) is within the above range, the surface protective film of the present invention can be more difficult to be easily peeled off from the adherend, and the re-peeling over time can be further suppressed.

[A-2-4-b.自含有多元醇與多官能異氰酸酯化合物(B)之組合物形成之胺基甲酸酯系樹脂]
自含有多元醇與多官能異氰酸酯化合物(B)之組合物形成之胺基甲酸酯系樹脂具體而言，較佳為使含有多元醇與多官能異氰酸酯化合物(B)之組合物硬化而獲得之胺基甲酸酯系樹脂。[A-2-4-b. Urethane-based resin formed from a composition containing a polyol and a polyfunctional isocyanate compound (B)]
Specifically, the urethane-based resin formed from a composition containing a polyol and a polyfunctional isocyanate compound (B) is preferably obtained by curing a composition containing a polyol and a polyfunctional isocyanate compound (B). Urethane resin.

多元醇可僅為一種，亦可為兩種以上。The polyol may be only one kind, or two or more kinds.

作為多官能異氰酸酯化合物(B)，可採用上述者。As the polyfunctional isocyanate compound (B), the above can be used.

多元醇(A)與多官能異氰酸酯化合物(B)中之NCO基與OH基之當量比作為NCO基/OH基，較佳為5.0以下，更佳為0.1～3.0，進而較佳為0.2～2.5，尤佳為0.3～2.25，最佳為0.5～2.0。若NCO基/OH基之當量比為上述範圍內，則本發明之表面保護膜可變得更難以自被黏著體容易地剝離，可進一步抑制經時之重剝離化。The equivalent ratio of the NCO group and the OH group in the polyol (A) and the polyfunctional isocyanate compound (B), as the NCO group / OH group, is preferably 5.0 or less, more preferably 0.1 to 3.0, and still more preferably 0.2 to 2.5. , Particularly preferably 0.3 to 2.25, and most preferably 0.5 to 2.0. When the equivalent ratio of the NCO group / OH group is within the above range, the surface protective film of the present invention can be more difficult to be easily peeled off from the adherend, and the heavy peeling over time can be further suppressed.

作為多官能異氰酸酯化合物(B)之含有比例，多官能異氰酸酯化合物(B)相對於多元醇，較佳為1.0重量%～30重量%，更佳為1.5重量%～27重量%，進而較佳為2.0重量%～25重量%，尤佳為2.3重量%～23重量%，最佳為2.5重量%～20重量%。若多官能異氰酸酯化合物(B)之含有比例為上述範圍內，則本發明之表面保護膜可變得更難以自被黏著體容易地剝離，可進一步抑制經時之重剝離化。As the content ratio of the polyfunctional isocyanate compound (B), the polyfunctional isocyanate compound (B) is preferably 1.0% to 30% by weight, more preferably 1.5% to 27% by weight, and still more preferably to the polyol. 2.0% to 25% by weight, particularly preferably 2.3% to 23% by weight, and most preferably 2.5% to 20% by weight. When the content ratio of the polyfunctional isocyanate compound (B) is within the above range, the surface protective film of the present invention can be more difficult to be easily peeled off from the adherend, and the re-peeling over time can be further suppressed.

聚胺基甲酸酯系樹脂具體而言，較佳為使含有多元醇與多官能異氰酸酯化合物(B)之組合物硬化而形成。作為使含有多元醇與多官能異氰酸酯化合物(B)之組合物硬化而形成胺基甲酸酯系樹脂之方法，可於不損害本發明之效果之範圍內，採用使用有塊狀聚合或溶液聚合等之胺基甲酸酯化反應方法等任意合適之方法。Specifically, the polyurethane resin is preferably formed by curing a composition containing a polyol and a polyfunctional isocyanate compound (B). As a method for curing a composition containing a polyhydric alcohol and a polyfunctional isocyanate compound (B) to form a urethane resin, it is possible to adopt block polymerization or solution polymerization within a range that does not impair the effects of the present invention. Any suitable method, such as a carbamate reaction method, etc.

為使含有多元醇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 and a polyfunctional isocyanate compound (B), a catalyst is preferably used. Examples of such a catalyst include an organometallic compound and a tertiary amine compound.

作為有機金屬系化合物，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，就反應速度與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 organometallic 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 preferable 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：乙醯丙酮酸鐵、2-乙基己酸鐵等。Examples of the iron-based compound include iron acetopyruvate 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、二丁基順丁烯二酸錫、二丁基二月桂酸錫、二丁基二乙酸錫、二丁基硫化錫、三丁基甲醇錫、三丁基乙酸錫、三乙基乙醇錫、三丁基乙醇錫、二辛基氧化錫、二辛基二月桂酸錫、三丁基氯化錫、三丁基三氯乙酸錫、2-乙基己酸錫等。Examples of the tin-based compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin maleate, dibutyltin dilaurate, and dibutyl. Tin diacetate, dibutyltin sulfide, tributyltin methoxide, tributyltin acetate, triethyltin alcohol, tributyltin ethanol, dioctyltin oxide, dioctyltin dilaurate, tributyltin Tin 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、乙醯丙酮酸鋯等。Examples of the zirconium-based compound include zirconium naphthenate and zirconium acetoacetate.

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、三乙二胺、1,8-二氮雜雙環(5,4,0)-十一烯-7等。Examples of the tertiary amine compound include triethylamine, triethylenediamine, 1,8-diazabicyclo (5,4,0) -undecene-7, and the like.

觸媒可僅為一種，亦可為兩種以上。又，可併用觸媒與交聯延遲劑等。觸媒之量相對於多元醇，較佳為0.005重量%～1.00重量%，更佳為0.01重量%～0.75重量%，進而較佳為0.01重量%～0.50重量%，尤佳為0.01重量%～0.20重量%。若觸媒之量為上述範圍內，則本發明之表面保護膜可變得更難以自被黏著體容易地剝離，可進一步抑制經時之重剝離化。The catalyst may be only one type, or two or more types. A catalyst, a cross-linking retarder, and the like may be used in combination. The amount of the catalyst is preferably 0.005% to 1.00% by weight, more preferably 0.01% to 0.75% by weight, more preferably 0.01% to 0.50% by weight, and particularly preferably 0.01% to 5% by weight relative to the polyol. 0.20% by weight. When the amount of the catalyst is within the above range, the surface protective film of the present invention can be more difficult to be easily peeled off from the adherend, and the heavy peeling over time can be further suppressed.

於含有多元醇與多官能異氰酸酯化合物(B)之組合物中，可於不損害本發明之效果之範圍內含有任意合適之其他成分。作為此種其他成分，例如可列舉：聚胺基甲酸酯系樹脂以外之樹脂成分、黏著賦予劑、無機填充劑、有機填充劑、金屬粉、顏料、箔狀物、軟化劑、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、觸媒等。The composition containing a polyhydric alcohol and a polyfunctional isocyanate compound (B) may contain any appropriate other component within the range which does not impair the effect of this invention. Examples of such other components include resin components other than polyurethane resins, adhesion-imparting agents, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, and anti-aging agents. , Conductive agent, ultraviolet absorber, antioxidant, light stabilizer, surface lubricant, leveling agent, anticorrosive agent, heat stabilizer, polymerization inhibitor, lubricant, solvent, catalyst, etc.

＜A-2-5.脂肪酸酯＞
黏著劑組合物較佳為含有脂肪酸酯。脂肪酸酯可僅為一種，亦可為兩種以上。若黏著劑組合物含有脂肪酸酯，則本發明之表面保護膜可變得更難以自被黏著體容易地剝離，可進一步抑制經時之重剝離化，可進一步表現因貼附於被黏著體而導致之該被黏著體表面之污染性較低之效果。<A-2-5. Fatty acid esters>
The adhesive composition preferably contains a fatty acid ester. There may be only one fatty acid ester or two or more fatty acid esters. If the adhesive composition contains a fatty acid ester, the surface protective film of the present invention can be more difficult to be easily peeled off from the adherend, which can further suppress re-peeling over time, and can further express the phenomenon of sticking to the adherend. As a result, the surface of the adherend is less polluting.

脂肪酸酯之數量平均分子量Mn較佳為100～800，更佳為150～750，進而較佳為200～700，尤佳為200～650，最佳為200～600。若脂肪酸酯之數量平均分子量Mn為上述範圍內，則本發明之表面保護膜可變得更難以自被黏著體容易地剝離，可進一步抑制經時之重剝離化，可進一步表現因貼附於被黏著體而導致之該被黏著體表面之污染性較低之效果。The number average molecular weight Mn of the fatty acid ester is preferably 100 to 800, more preferably 150 to 750, still more preferably 200 to 700, particularly preferably 200 to 650, and most preferably 200 to 600. When the number average molecular weight Mn of the fatty acid ester is within the above range, the surface protective film of the present invention can be more difficult to peel off easily from the adherend, which can further suppress re-peeling over time, and can further express the effect of sticking. The effect of lower pollution on the surface of the adherend caused by the adherend.

作為脂肪酸酯，可於不損害本發明之效果之範圍內採用任意合適之脂肪酸酯。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-乙基己酯、硬脂酸2-乙基己酯、山萮酸單甘油酯、2-乙基己酸鯨蠟酯、肉豆蔻酸異丙酯、棕櫚酸異丙酯、異硬脂酸膽固醇酯、甲基丙烯酸月桂酯、椰子油脂肪酸甲酯、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、硬脂酸硬脂酯、硬脂酸異十三烷基酯、2-乙基己酸三甘油酯、月桂酸丁酯、油酸辛酯等。As the fatty acid ester, any suitable fatty acid ester can be used as long as the effect of the present invention is not impaired. Examples of such fatty acid esters include polyoxyethylene bisphenol A laurate, butyl stearate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, and behenic acid monoester. Glyceride, cetyl 2-ethylhexanoate, isopropyl myristate, isopropyl palmitate, cholesterol isostearate, lauryl methacrylate, coconut oil fatty acid methyl esters, methyl laurate, Methyl oleate, methyl stearate, myristyl myristate, octyldodecyl myristate, pentaerythritol monooleate, pentaerythritol monostearate, pentaerythritol tetrapalmitate, stearic acid Stearate, isotridecyl stearate, triglyceryl 2-ethylhexanoate, butyl laurate, octyl oleate, and the like.

於黏著劑組合物含有脂肪酸酯之情形時，脂肪酸酯之含有比例相對於基礎聚合物100重量份，較佳為0.01重量份～50重量份，更佳為0.05重量份～45重量份，進而較佳為0.1重量份～40重量份，進而較佳為0.3重量份～35重量份，進而較佳為0.5重量份～30重量份，尤佳為0.5重量份～25重量份，最佳為0.5重量份～20重量份。若脂肪酸酯之含有比例相對於基礎聚合物100重量份為上述範圍內，則本發明之表面保護膜可變得更難以自被黏著體容易地剝離，可進一步抑制經時之重剝離化，可進一步表現因貼附於被黏著體而導致之該被黏著體表面之污染性較低之效果。When the adhesive composition contains a fatty acid ester, the content ratio of the fatty acid ester relative to 100 parts by weight of the base polymer is preferably 0.01 to 50 parts by weight, and more preferably 0.05 to 45 parts by weight. Still more preferably 0.1 to 40 parts by weight, still more preferably 0.3 to 35 parts by weight, still more preferably 0.5 to 30 parts by weight, even more preferably 0.5 to 25 parts by weight, and most preferably 0.5 to 20 parts by weight. If the content ratio of the fatty acid ester is within the above-mentioned range with respect to 100 parts by weight of the base polymer, the surface protective film of the present invention can be more difficult to be easily peeled off from the adherend, and the heavy peeling over time can be further suppressed. It can further express the effect that the pollution of the surface of the adherend caused by the adherence to the adherend is low.

＜A-2-6.其他成分＞
黏著劑組合物可於不損害本發明之效果之範圍內含有任意合適之其他成分。作為此種其他成分，例如可列舉：其他樹脂成分、黏著賦予劑、無機填充劑、有機填充劑、金屬粉、顏料、箔狀物、軟化劑、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、觸媒等。＜ A-2-6. Other ingredients ＞
The adhesive composition may contain any appropriate other components within a range that does not impair the effect of the present invention. Examples of such other components include other resin components, adhesion-imparting agents, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, ultraviolet absorbers, and anti-aging agents. Oxidants, light stabilizers, surface lubricants, leveling agents, anti-corrosive agents, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts, etc.

黏著劑組合物可包含含有氟有機陰離子之離子性液體。藉由使黏著劑組合物包含含有氟有機陰離子之離子性液體，可提供抗靜電性非常優異之黏著劑組合物。此種離子性液體可僅為一種，亦可為兩種以上。The adhesive composition may include an ionic liquid containing a fluorine organic anion. When the adhesive composition contains an ionic liquid containing a fluorine organic anion, an adhesive composition having excellent antistatic properties can be provided. Such an ionic liquid may be only one kind, or two or more kinds.

於本發明中，所謂離子性液體係指於25℃下呈液狀之熔融鹽(離子性化合物)。In the present invention, the ionic liquid system means a molten salt (ionic compound) which is liquid at 25 ° C.

作為離子性液體，只要為含有氟有機陰離子之離子性液體，則可於不損害本發明之效果之範圍內採用任意合適之離子性液體。作為此種離子性液體，較佳為包含氟有機陰離子與鎓陽離子之離子性液體。藉由採用包含氟有機陰離子與鎓陽離子之離子性液體作為離子性液體，可提供抗靜電性極其優異之黏著劑組合物。As the ionic liquid, as long as it is an ionic liquid containing a fluorine organic anion, any suitable ionic liquid can be used as long as the effect of the present invention is not impaired. As such an ionic liquid, an ionic liquid containing a fluorine organic anion and an onium cation is preferable. By using an ionic liquid containing a fluorine organic anion and an onium cation as the ionic liquid, an adhesive composition having excellent antistatic properties can be provided.

作為可構成離子性液體之鎓陽離子，可於不損害本發明之效果之範圍內採用任意合適之鎓陽離子。作為此種鎓陽離子，較佳為選自含氮之鎓陽離子、含硫之鎓陽離子、含磷之鎓陽離子中之至少一種。藉由選擇該等鎓陽離子，可提供抗靜電性極其優異之黏著劑組合物。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 onium cation, a sulfur-containing onium cation, and a phosphorus-containing onium cation. By selecting these onium cations, an adhesive composition having extremely excellent antistatic properties can be provided.

作為可構成離子性液體之鎓陽離子，較佳為選自具有通式(1)～(5)所表示之結構之陽離子中之至少一種。
[化1]
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).
[Chemical 1]

通式(1)中，Ra表示碳數4至20之烴基，可含有雜原子，Rb及Rc相同或不同，表示氫或碳數1至16之烴基，可含有雜原子。其中，於氮原子含有雙鍵之情形時，無Rc。In the general formula (1), Ra represents a hydrocarbon group having 4 to 20 carbon atoms and may contain heteroatoms, and Rb and Rc are the same or different and represent hydrogen or a hydrocarbon group having 1 to 16 carbon atoms and may contain heteroatoms. However, when the nitrogen atom contains a double bond, there is no Rc.

通式(2)中，Rd表示碳數2至20之烴基，可含有雜原子，Re、Rf及Rg相同或不同，表示氫或碳數1至16之烴基，可含有雜原子。In the general formula (2), Rd represents a hydrocarbon group having 2 to 20 carbon atoms and may contain 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 contain heteroatoms.

通式(3)中，Rh表示碳數2至20之烴基，可含有雜原子，Ri、Rj及Rk相同或不同，表示氫或碳數1至16之烴基，可含有雜原子。In the general formula (3), Rh represents a hydrocarbon group having 2 to 20 carbon atoms and may contain heteroatoms, and Ri, Rj and Rk are the same or different and represent hydrogen or a hydrocarbon group having 1 to 16 carbon atoms and may contain heteroatoms.

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至20之烴基，可含有雜原子。其中，於Z含有硫原子之情形時，無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, and may contain a hetero atom. However, when Z contains a sulfur atom, there is no Ro.

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.

作為通式(1)所表示之陽離子，例如可列舉：吡啶鎓陽離子、吡咯啶鎓陽離子、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)所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、1,1-二甲基吡咯啶鎓陽離子等吡啶鎓陽離子；1-乙基-1-甲基吡咯啶鎓陽離子、1-甲基-1-丙基吡咯啶鎓陽離子、1-甲基-1-丁基吡咯啶鎓陽離子、1-甲基-1-戊基吡咯啶鎓陽離子、1-甲基-1-己基吡咯啶鎓陽離子、1-甲基-1-庚基吡咯啶鎓陽離子、1-乙基-1-丙基吡咯啶鎓陽離子、1-乙基-1-丁基吡咯啶鎓陽離子、1-乙基-1-戊基吡咯啶鎓陽離子、1-乙基-1-己基吡咯啶鎓陽離子、1-乙基-1-庚基吡咯啶鎓陽離子、1,1-二丙基吡咯啶鎓陽離子、1-丙基-1-丁基吡咯啶鎓陽離子、1,1-二丁基吡咯啶鎓陽離子等吡咯啶鎓陽離子；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-methyl Pyridinium cation, 1-butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4-methyl Pyridinium cations such as pyridylium 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 , 1-propyl-1-butylpyrrolidinium cation, 1,1-dibutylpyrrolidine Pyrrolidinium cations such as cations; 1-propylpiperidinium cation, 1-pentylpiperidinium cation, 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidine Onium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium 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-dimethylpiperidine Piperidinium cations such as onium cations, 1,1-dipropylpiperidinium cations, 1,1-dibutylpiperidinium cations; 2-methyl-1-pyrroline cations; 1-ethyl-2- Phenylindole cation; 1,2-dimethylindole cation; 1-ethylcarbazole cation, etc.

該等之中，就可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-甲基吡咯啶鎓陽離子、1-甲基-1-丙基吡咯啶鎓陽離子、1-甲基-1-丁基吡咯啶鎓陽離子、1-甲基-1-戊基吡咯啶鎓陽離子、1-甲基-1-己基吡咯啶鎓陽離子、1-甲基-1-庚基吡咯啶鎓陽離子、1-乙基-1-丙基吡咯啶鎓陽離子、1-乙基-1-丁基吡咯啶鎓陽離子、1-乙基-1-戊基吡咯啶鎓陽離子、1-乙基-1-己基吡咯啶鎓陽離子、1-乙基-1-庚基吡咯啶鎓陽離子等吡咯啶鎓陽離子；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-丙基吡咯啶鎓陽離子、1-甲基-1-丙基哌啶鎓陽離子。Among these, 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-octyl Pyridinium cations such as methyl-4-methylpyridinium cation; 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butan Pyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexylpyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl Propyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-ethyl-1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium Cations, pyrrolidinium cations such as 1-ethyl-1-heptylpyrrolidinium cation; 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1 -Methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidine Onium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium cation, 1-ethyl-1-propylpiperidinium cation, 1-ethyl-1 -Butyl piperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, 1 -Piperidinium cations such as propyl-1-butylpiperidinium cation, etc., more preferably 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl-3-methyl Pyridinium cation, 1-octyl-4-methylpyridinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-propylpiperidinium cation.

作為通式(2)所表示之陽離子，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)所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 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, and 1-ethyl-3-methylimidazole. Onium cation, 1-butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methyl Imidazolium cation, 1-dodecyl-3-methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, Imidazolium cations such as 1-ethyl-2,3-dimethylimidazolium cation, 1-butyl-2,3-dimethylimidazolium cation, 1-hexyl-2,3-dimethylimidazolium cation ; 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2 , 3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation, etc. Hydropyrimidinium cation; 1,3-dimethyl-1,4-dihydropyrimidinium cation, 1,3-dimethyl-1,6-dihydropyrimidinium cation, 1,2,3-trimethyl -1,4-dihydropyrimidinium cation, 1,2,3-trimethyl-1,6- Hydropyrimidinium cation, 1,2,3,4-tetramethyl-1,4-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,6-dihydropyrimidinium cation, etc. Hydropyrimidinium cations and the like.

該等之中，就可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- Methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3 -Imidazolium cations such as 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)所表示之陽離子，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 and a pyrazolinium cation.

作為通式(3)所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 1-methylpyrazolium cation, 3-methylpyrazolium cation, and 1-ethyl-2-methylpyrazolinium cation. , 1-ethyl-2,3,5-trimethylpyrazolium cation, 1-propyl-2,3,5-trimethylpyrazolium cation, 1-butyl-2,3,5- Pyrazolium cations such as trimethylpyrazolium cation; 1-ethyl-2,3,5-trimethylpyrazolium cation, 1-propyl-2,3,5-trimethylpyrazolium Pyrazolinium cations such as onium cations, 1-butyl-2,3,5-trimethylpyrazolinium cations, and the like.

作為通式(4)所表示之陽離子，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被取代為烯基或烷氧基、進而環氧基者等。Examples of the cation represented by the general formula (4) include a tetraalkylammonium cation, a trialkylphosphonium cation, a tetraalkylphosphonium cation, or a part of the alkyl group substituted with an alkenyl group or an alkoxy group, and further a ring Oxygen and so on.

作為通式(4)所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, for example, tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetrapentylammonium cation, tetrahexylammonium cation, and tetraheptyl Ammonium 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, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, tetramethylsulfonium cation, tetraethylsulfonium cation, tetrabutylsulfonium cation, tetrahexylsulfonium cation, tetraoctylsulfonium cation, triethyl Methylphosphonium cation, tributylethylphosphonium cation, trimethyldecylphosphonium cation, diallyldimethylammonium cation, and the like.

該等之中，就可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之四烷基銨陽離子、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 Asymmetric tetraalkanes such as methylphosphonium cation, dibutylethylphosphonium cation, dimethyldecylphosphonium cation, triethylmethylphosphonium cation, tributylethylphosphonium cation, trimethyldecylphosphonium cation, etc. Ammonium cation, trialkylphosphonium cation, tetraalkylphosphonium cation, or N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium cation, glycidyl trimethyl Ammonium cation, diallyldimethylammonium cation, N, N-dimethyl-N-ethyl-N-propylammonium cation, N, N-dimethyl-N-ethyl-N-butyl Ammonium 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-diamine -N-propyl-N-hexylammonium cation, N, N-dimethyl-N-propyl-N-heptylammonium cation, N, N-dimethyl-N-butyl-N-hexylammonium 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-pentylammonium cation, triethylpropane Ammonium 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-dihexylammonium 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，可於不損害本發明之效果之範圍內採用任意合適之氟有機陰離子。此種氟有機陰離子可完全氟化(全氟化)，亦可部分氟化。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 can be fully fluorinated (perfluorinated) or partially fluorinated.

作為此種氟有機陰離子，例如可列舉：氟化之芳基磺酸根、全氟烷磺酸根、雙(氟磺醯基)醯亞胺、雙(全氟烷磺醯基)醯亞胺、氰基全氟烷磺醯胺、雙(氰基)全氟烷磺醯基甲基化物、氰基-雙-(全氟烷磺醯基)甲基化物、三(全氟烷磺醯基)甲基化物、三氟乙酸根、全氟烷化物、三(全氟烷磺醯基)甲基化物、(全氟烷磺醯基)三氟乙醯胺等。Examples of such fluoroorganic anions include fluorinated arylsulfonate, perfluoroalkanesulfonate, bis (fluorosulfonyl) fluorenimide, bis (perfluoroalkylsulfonyl) fluorenimide, and cyanide Perfluoroalkanesulfonamide, bis (cyano) perfluoroalkanesulfonylmethylate, cyano-bis- (perfluoroalkanesulfonyl) methylate, tris (perfluoroalkanesulfonyl) methyl Base compounds, trifluoroacetate, perfluoroalkylate, tris (perfluoroalkanesulfonyl) methylate, (perfluoroalkanesulfonyl) trifluoroacetamide, and the like.

該等氟有機陰離子之中，更佳為全氟烷磺酸根、雙(氟磺醯基)醯亞胺、雙(全氟烷磺醯基)醯亞胺，更具體而言，例如為三氟甲磺酸根、五氟乙磺酸根、七氟丙磺酸根、九氟丁磺酸根、雙(氟磺醯基)醯亞胺、雙(三氟甲磺醯基)醯亞胺。Among the fluoroorganic anions, more preferred are perfluoroalkanesulfonate, bis (fluorosulfofluorenyl) fluorenimide, and bis (perfluoroalkanesulfonyl) fluorenimide, and more specifically, for example, trifluoro Methanesulfonate, pentafluoroethanesulfonate, heptafluoropropanesulfonate, nonafluorobutanesulfonate, bis (fluorosulfonyl) fluorenimide, bis (trifluoromethanesulfonyl) sulfonium imine.

作為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中適宜選擇而使用。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-甲基吡啶鎓三氟甲磺酸鹽、1-乙基-3-甲基吡啶鎓五氟乙磺酸鹽、1-乙基-3-甲基吡啶鎓七氟丙磺酸鹽、1-乙基-3-甲基吡啶鎓九氟丁磺酸鹽、1-丁基-3-甲基吡啶鎓三氟甲磺酸鹽、1-丁基-3-甲基吡啶鎓雙(三氟甲磺醯基)醯亞胺、1-丁基-3-甲基吡啶鎓雙(五氟乙磺醯基)醯亞胺、1-辛基-4-甲基吡啶鎓雙(氟磺醯基)醯亞胺、1,1-二甲基吡咯啶鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-乙基吡咯啶鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-丙基吡咯啶鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-丙基吡咯啶鎓雙(氟磺醯基)醯亞胺、1-甲基-1-丁基吡咯啶鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-戊基吡咯啶鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-己基吡咯啶鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-庚基吡咯啶鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-1-丙基吡咯啶鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-1-丁基吡咯啶鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-1-戊基吡咯啶鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-1-己基吡咯啶鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-1-庚基吡咯啶鎓雙(三氟甲磺醯基)醯亞胺、1,1-二丙基吡咯啶鎓雙(三氟甲磺醯基)醯亞胺、1-丙基-1-丁基吡咯啶鎓雙(三氟甲磺醯基)醯亞胺、1,1-二丁基吡咯啶鎓雙(三氟甲磺醯基)醯亞胺、1-丙基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-戊基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1,1-二甲基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-乙基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-丙基哌啶鎓雙(三氟甲磺醯基)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(三氟甲磺醯基)醯亞胺、1-甲基-1-戊基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-己基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-庚基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-1-丙基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-1-丁基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-1-戊基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-1-己基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-1-庚基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1,1-二丙基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-丙基-1-丁基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1,1-二丁基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1,1-二甲基吡咯啶鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-乙基吡咯啶鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-丙基吡咯啶鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-丁基吡咯啶鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-戊基吡咯啶鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-己基吡咯啶鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-庚基吡咯啶鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-1-丙基吡咯啶鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-1-丁基吡咯啶鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-1-戊基吡咯啶鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-1-己基吡咯啶鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-1-庚基吡咯啶鎓雙(五氟乙磺醯基)醯亞胺、1,1-二丙基吡咯啶鎓雙(五氟乙磺醯基)醯亞胺、1-丙基-1-丁基吡咯啶鎓雙(五氟乙磺醯基)醯亞胺、1,1-二丁基吡咯啶鎓雙(五氟乙磺醯基)醯亞胺、1-丙基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-戊基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1,1-二甲基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-乙基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-丙基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-丁基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-戊基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-己基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-甲基-1-庚基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-1-丙基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-1-丁基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-1-戊基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-1-己基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-1-庚基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1,1-二丙基哌啶鎓雙(五氟乙磺醯基)醯亞胺,1-丙基-1-丁基哌啶鎓雙(五氟乙磺醯基)醯亞胺、1,1-二丁基哌啶鎓雙(五氟乙磺醯基)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-甲基咪唑鎓三氟甲磺酸鹽、1-乙基-3-甲基咪唑鎓七氟丙磺酸鹽、1-乙基-3-甲基咪唑鎓九氟丁磺酸鹽、1-乙基-3-甲基咪唑鎓雙(三氟甲磺醯基)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(五氟乙磺醯基)醯亞胺、1-乙基-3-甲基咪唑鎓三(三氟甲磺醯基)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-甲基咪唑鎓三氟甲磺酸鹽、1-丁基-3-甲基咪唑鎓全氟丁磺酸鹽、1-丁基-3-甲基咪唑鎓雙(三氟甲磺醯基)醯亞胺、1-己基-3-甲基咪唑鎓三氟甲磺酸鹽、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(三氟甲磺醯基)醯亞胺、1-乙基-2,3,5-三甲基吡唑鎓雙(三氟甲磺醯基)醯亞胺、1-丙基-2,3,5-三甲基吡唑鎓雙(三氟甲磺醯基)醯亞胺、1-丁基-2,3,5-三甲基吡唑鎓雙(三氟甲磺醯基)醯亞胺、1-乙基-2,3,5-三甲基吡唑鎓雙(五氟乙磺醯基)醯亞胺、1-丙基-2,3,5-三甲基吡唑鎓雙(五氟乙磺醯基)醯亞胺、1-丁基-2,3,5-三甲基吡唑鎓雙(五氟乙磺醯基)醯亞胺、1-乙基-2,3,5-三甲基吡唑鎓(三氟甲磺醯基)三氟乙醯胺、1-丙基-2,3,5-三甲基吡唑鎓(三氟甲磺醯基)三氟乙醯胺、1-丁基-2,3,5-三甲基吡唑鎓(三氟甲磺醯基)三氟乙醯胺、三甲基丙基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-乙基-N-丙基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-乙基-N-丁基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-乙基-N-戊基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-乙基-N-己基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-乙基-N-庚基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-乙基-N-壬基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N,N-二丙基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-丙基-N-丁基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-丙基-N-戊基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-丙基-N-己基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-丙基-N-庚基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-丁基-N-己基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-丁基-N-庚基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N-戊基-N-己基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-N,N-二己基銨雙(三氟甲磺醯基)醯亞胺、三甲基庚基銨雙(三氟甲磺醯基)醯亞胺、N,N-二乙基-N-甲基-N-丙基銨雙(三氟甲磺醯基)醯亞胺、N,N-二乙基-N-甲基-N-戊基銨雙(三氟甲磺醯基)醯亞胺、N,N-二乙基-N-甲基-N,N-庚基銨雙(三氟甲磺醯基)醯亞胺、N,N-二乙基-N-丙基-N-戊基銨雙(三氟甲磺醯基)醯亞胺、三乙基丙基銨雙(三氟甲磺醯基)醯亞胺、三乙基戊基銨雙(三氟甲磺醯基)醯亞胺、三乙基庚基銨雙(三氟甲磺醯基)醯亞胺、N,N-二丙基-N-甲基-N-乙基銨雙(三氟甲磺醯基)醯亞胺、N,N-二丙基-N-甲基-N-戊基銨雙(三氟甲磺醯基)醯亞胺、N,N-二丙基-N-丁基-N-己基銨雙(三氟甲磺醯基)醯亞胺、N,N-二丙基-N,N-二己基銨雙(三氟甲磺醯基)醯亞胺、N,N-二丁基-N-甲基-N-戊基銨雙(三氟甲磺醯基)醯亞胺、N,N-二丁基-N-甲基-N-己基銨雙(三氟甲磺醯基)醯亞胺、三辛基甲基銨雙(三氟甲磺醯基)醯亞胺、N-甲基-N-乙基-N-丙基-N-戊基銨雙(三氟甲磺醯基)醯亞胺、1-丁基吡啶鎓(三氟甲磺醯基)三氟乙醯胺、1-丁基-3-甲基吡啶鎓(三氟甲磺醯基)三氟乙醯胺,1-乙基-3-甲基咪唑鎓(三氟甲磺醯基)三氟乙醯胺、四己基銨雙(三氟甲磺醯基)醯亞胺、二烯丙基二甲基銨三氟甲磺酸鹽、二烯丙基二甲基銨雙(三氟甲磺醯基)醯亞胺、二烯丙基二甲基銨雙(五氟乙磺醯基)醯亞胺、N,N-二乙基-N-甲基-N-(2-甲氧基乙基)銨三氟甲磺酸鹽、N,N-二乙基-N-甲基-N-(2-甲氧基乙基)銨雙(三氟甲磺醯基)醯亞胺、N,N-二乙基-N-甲基-N-(2-甲氧基乙基)銨雙(五氟乙磺醯基)醯亞胺、縮水甘油基三甲基銨三氟甲磺酸鹽、縮水甘油基三甲基銨雙(三氟甲磺醯基)醯亞胺、縮水甘油基三甲基銨雙(五氟乙磺醯基)醯亞胺、二烯丙基二甲基銨雙(三氟甲磺醯基)醯亞胺、二烯丙基二甲基雙(五氟乙磺醯基)醯亞胺、鋰雙(三氟甲磺醯基)醯亞胺、鋰雙(氟磺醯基)醯亞胺等。As a specific example of an ionic liquid, it can select suitably from the combination of the said cationic component and the said anionic component, and can use it. Specific examples of such an ionic liquid include 1-hexylpyridinium bis (fluorosulfonyl) fluorenimine, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1- Ethyl-3-methylpyridinium pentafluoroethanesulfonate, 1-ethyl-3-methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutanesulfonic acid Salt, 1-butyl-3-methylpyridinium triflate, 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) fluorenimine, 1-butyl-3 -Methylpyridinium bis (pentafluoroethanesulfonyl) fluorenimide, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) fluorenimide, 1,1-dimethylpyrrolidinium Bis (trifluoromethanesulfonyl) fluorenimide, 1-methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) fluorenimine, 1-methyl-1-propylpyrrolidinium Bis (trifluoromethanesulfonyl) fluorenimide, 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) fluorenimide, 1-methyl-1-butylpyrrolidinium bis ( Trifluoromethanesulfonyl) fluorenimine, 1-methyl-1-pentylpyrrolidinium bis (trifluoromethanesulfonyl) fluorenimine, 1-methyl-1-hexylpyrrolidinium bis (tri Flumethanesulfonyl) fluorenimine, 1-methyl-1-heptylpyrrolidinium bis (trifluoromethyl) Fluorenyl) fluorenimine, 1-ethyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) fluorenimine, 1-ethyl-1-butylpyrrolidinium bis (trifluoromethanesulfonate) Fluorenyl) fluorenimine, 1-ethyl-1-pentylpyrrolidinium bis (trifluoromethanesulfonyl) fluorenimide, 1-ethyl-1-hexylpyrrolidinium bis (trifluoromethanesulfonyl) Sulfonyl) imine, 1-ethyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl) fluorenimide, 1,1-dipropylpyrrolidinium bis (trifluoromethanesulfonyl) Fluorenimine, 1-propyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) fluorenimide, 1,1-dibutylpyrrolidinium bis (trifluoromethanesulfonyl) fluorene Amine, 1-propylpiperidinium bis (trifluoromethanesulfonyl) fluorenimide, 1-pentylpiperidinium bis (trifluoromethanesulfonyl) fluorenimide, 1,1-dimethylpiperidine Pyridinium bis (trifluoromethanesulfonyl) fluorenimide, 1-methyl-1-ethylpiperidinium bis (trifluoromethanesulfonyl) fluorenimide, 1-methyl-1-propylpiperidine Pyridinium bis (trifluoromethanesulfonyl) fluorenimide, 1-methyl-1-propylpiperidinium bis (fluorosulfonyl) fluorenimide, 1-methyl-1-butylpiperidinium Bis (trifluoromethanesulfonyl) fluorenimide, 1-methyl-1-pentylpiperidinium bis (trifluoromethanesulfonyl) fluorenimide, 1-methyl-1-hexyl Piperidinium bis (trifluoromethanesulfonyl) fluorenimide, 1-methyl-1-heptyl piperidinium bis (trifluoromethanesulfonyl) fluorenimide, 1-ethyl-1-propyl Piperidinium bis (trifluoromethanesulfonyl) fluorenimide, 1-ethyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) fluorenimide, 1-ethyl-1-pentyl Piperidinium bis (trifluoromethanesulfonyl) fluorenimide, 1-ethyl-1-hexyl piperidinium bis (trifluoromethanesulfonyl) fluorenimide, 1-ethyl-1-heptylpiperium Pyridinium bis (trifluoromethanesulfonyl) fluorenimide, 1,1-dipropylpiperidinium bis (trifluoromethanesulfonyl) fluorenimide, 1-propyl-1-butylpiperidinium Bis (trifluoromethanesulfonyl) fluorenimide, 1,1-dibutylpiperidinium bis (trifluoromethanesulfonyl) fluorenimide, 1,1-dimethylpyrrolidinium bis (pentafluoro Ethylsulfonyl) fluorenimine, 1-methyl-1-ethylpyrrolidinium bis (pentafluoroethanesulfonyl) fluorenimine, 1-methyl-1-propylpyrrolidinium bis (pentafluoro Ethylsulfonyl) fluorenimine, 1-methyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) fluorenimine, 1-methyl-1-pentylpyrrolidinium bis (pentafluoro Ethylsulfonyl) fluorenimine, 1-methyl-1-hexylpyrrolidinium bis (pentafluoroethanesulfonyl) fluorenimine, 1-methyl-1-heptylpyrrolidinium bis ( Fluoroethanesulfonyl) fluorenimine, 1-ethyl-1-propylpyrrolidinium bis (pentafluoroethanesulfonyl) fluorenimine, 1-ethyl-1-butylpyrrolidinium bis (penta Fluoroethanesulfonyl) fluorenimide, 1-ethyl-1-pentylpyrrolidinium bis (pentafluoroethanesulfonyl) fluorenimide, 1-ethyl-1-hexylpyrrolidinium bis (pentafluoro Ethylsulfonyl) fluorenimine, 1-ethyl-1-heptylpyrrolidinium bis (pentafluoroethanesulfonyl) fluorenimide, 1,1-dipropylpyrrolidinium bis (pentafluoroethanesulfonate) Fluorenyl) fluorenimine, 1-propyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonylfluorenyl) fluorenimide, 1,1-dibutylpyrrolidinium bis (pentafluoroethanesulfonylfluorenyl) ) Fluorenimine, 1-propylpiperidinium bis (pentafluoroethanesulfonyl) fluorenimide, 1-pentylpiperidinium bis (pentafluoroethanesulfonyl) fluorenimide, 1,1-bis Methyl piperidinium bis (pentafluoroethanesulfonyl) fluorenimide, 1-methyl-1-ethylpiperidinium bis (pentafluoroethanesulfonyl) fluorenimide, 1-methyl-1- Propylpiperidinium bis (pentafluoroethanesulfonyl) fluorenimide, 1-methyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) fluorenimide, 1-methyl-1- Amyl piperidinium bis (pentafluoroethanesulfonyl) fluorenimide, 1-methyl-1-hexyl piperidinium bis (pentafluoroethanesulfonyl) fluorenimine, 1-methyl-1-heptylpiperidinium bis (pentafluoroethanesulfonyl) fluorenimide, 1-ethyl-1-propylpiperidinium bis (pentafluoroethanesulfonyl) fluorenimine, 1-ethyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) fluorenimide, 1-ethyl-1-pentylpiperidinium bis (pentafluoroethanesulfonyl) fluorenimine, 1-ethyl-1-hexylpiperidinium bis (pentafluoroethanesulfonyl) fluorenimide, 1-ethyl-1-heptylpiperidinium bis (pentafluoroethanesulfonyl) fluorenimine, 1 1,1-dipropylpiperidinium bis (pentafluoroethanesulfonyl) fluorenimide, 1-propyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) fluorenimine, 1,1 -Dibutylpiperidinium bis (pentafluoroethanesulfonyl) fluorenimine, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazolium heptafluorobutane Acid salt, 1-ethyl-3-methylimidazolium triflate, 1-ethyl-3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl-3-methylimidazolium Nonafluorobutanesulfonate, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) fluorene imine, 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) fluorene Imine, 1-ethyl-3-methylimidazolium bis (pentafluoroethanesulfonyl) fluorenimide, 1-ethyl-3-methylimidazolium tris (trifluoromethanesulfonyl) methyl Compounds, 1-butyl-3-methylimidazolium trifluoroacetate, 1-butyl-3-methylimidazolium heptafluorobutyrate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate Acid salt, 1-butyl-3-methylimidazolium perfluorobutanesulfonate, 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) fluorenimine, 1-hexyl-3 -Methylimidazolium triflate, 1-hexyl-3-methylimidazolium bis (fluorosulfonyl) fluorenimine, 1,2-dimethyl-3-propylimidazolium bis (tri Flumethanesulfonyl) fluorenimide, 1-ethyl-2,3,5-trimethylpyrazolium bis (trifluoromethanesulfonyl) fluorenimide, 1-propyl-2,3,5 -Trimethylpyrazolium bis (trifluoromethanesulfonyl) fluorenimine, 1-butyl-2,3,5-trimethylpyrazolium bis (trifluoromethanesulfonyl) fluorenimine, 1-ethyl-2,3,5-trimethylpyrazolium bis (pentafluoroethanesulfonyl) fluorenimine, 1-propyl-2,3,5-trimethylpyrazolium bis (penta Fluoroethanesulfonyl) fluorenimine, 1-butyl-2,3,5-trimethylpyrazolium bis (pentafluoroethanesulfonyl) fluorenimine, 1-ethyl-2,3,5 -Trimethylpyrazolium (trifluoromethanesulfonyl) trifluoroacetamidine, 1-propyl-2,3,5-trimethylpyrazolium (trifluoromethanesulfonyl) trifluoroacetamidine Amine, 1-butyl-2,3,5-trimethylpyrazole Onium (trifluoromethanesulfonyl) trifluoroacetamide, trimethylpropylammonium bis (trifluoromethanesulfonyl) fluorenimine, N, N-dimethyl-N-ethyl-N-propyl Bis (trifluoromethanesulfonyl) fluorenimide, N, N-dimethyl-N-ethyl-N-butylammonium bis (trifluoromethanesulfonyl) fluorenimide, N, N- Dimethyl-N-ethyl-N-pentylammonium bis (trifluoromethanesulfonyl) fluorenimine, N, N-dimethyl-N-ethyl-N-hexylammonium bis (trifluoromethanesulfonate) Fluorenyl) fluorenimine, N, N-dimethyl-N-ethyl-N-heptylammonium bis (trifluoromethanesulfonyl) fluorenimine, N, N-dimethyl-N-ethyl -N-nonylammonium bis (trifluoromethanesulfonyl) fluorenimide, N, N-dimethyl-N, N-dipropylammonium bis (trifluoromethanesulfonyl) fluorenimide, N, N-dimethyl-N-propyl-N-butylammonium bis (trifluoromethanesulfonyl) fluorenimine, N, N-dimethyl-N-propyl-N-pentylammonium bis (tri Flumethanesulfonyl) fluorenimine, N, N-dimethyl-N-propyl-N-hexylammonium bis (trifluoromethanesulfonyl) fluorenimine, N, N-dimethyl-N- Propyl-N-heptylammonium bis (trifluoromethanesulfonyl) fluorenimide, N, N-dimethyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) fluorenimide , N, N-dimethyl-N-butyl-N-heptylammonium bis (trifluoromethanesulfonyl) fluorenimine, N, N-dimethyl -N-pentyl-N-hexylammonium bis (trifluoromethanesulfonyl) fluorenimide, N, N-dimethyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) fluorenimide , Trimethylheptylammonium bis (trifluoromethanesulfonyl) fluorenimide, N, N-diethyl-N-methyl-N-propylammonium bis (trifluoromethanesulfonyl) fluorenimide , N, N-diethyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) fluorenimine, N, N-diethyl-N-methyl-N, N-heptane Bis (trifluoromethanesulfonyl) fluorenimide, N, N-diethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) fluorenimide, triethylpropane Bis (trifluoromethanesulfonyl) fluorenimide, triethylpentylammonium bis (trifluoromethanesulfonyl) fluorenimide, triethylheptylammonium bis (trifluoromethanesulfonyl) sulfonium Imine, N, N-dipropyl-N-methyl-N-ethylammonium bis (trifluoromethanesulfonyl) fluorenimide, N, N-dipropyl-N-methyl-N-pentyl Bis (trifluoromethanesulfonyl) fluorenimide, N, N-dipropyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) fluorenimide, N, N-di Propyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) fluorenimine, N, N-dibutyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) Hydrazone, N, N-dibutyl-N-methyl-N-hexylammonium bis (trifluoromethyl) Fluorenyl) fluorenimine, trioctylmethylammonium bis (trifluoromethanesulfonylfluorenyl) fluorenimine, N-methyl-N-ethyl-N-propyl-N-pentylammonium bis (trifluoro Methanesulfonyl) fluorenimine, 1-butylpyridinium (trifluoromethanesulfonyl) trifluoroacetamidine, 1-butyl-3-methylpyridinium (trifluoromethanesulfonyl) trifluoro Ethylamine, 1-ethyl-3-methylimidazolium (trifluoromethanesulfonyl) trifluoroacetamidine, tetrahexylammonium bis (trifluoromethanesulfonyl) fluorenimine, diallyldiamine Methylammonium trifluoromethanesulfonate, diallyldimethylammonium bis (trifluoromethanesulfonyl) sulfonium imine, diallyldimethylammonium bis (pentafluoroethanesulfonyl) sulfonium Amine, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium triflate, N, N-diethyl-N-methyl-N- ( 2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) phosphonium imine, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (penta Fluoroethanesulfonyl) fluorenimide, glycidyltrimethylammonium triflate, glycidyltrimethylammonium bis (trifluoromethanesulfonyl) fluorenimine, glycidyltrimethyl Ammonium bis (pentafluoroethanesulfonyl) fluorenimide, diallyldimethylammonium bis (trifluoromethanesulfonyl) sulfonium imine Diallyldimethylammonium bis (pentafluoroethanesulfonyl sulfo acyl) (PEI), lithium bis (trifluoromethanesulfonyl acyl) (PEI), lithium bis (fluorosulfonyl acyl) (PEI) 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-甲基吡啶鎓三氟甲磺酸鹽、1-乙基-3-甲基吡啶鎓五氟乙磺酸鹽、1-乙基-3-甲基吡啶鎓七氟丙磺酸鹽、1-乙基-3-甲基吡啶鎓九氟丁磺酸鹽、1-丁基-3-甲基吡啶鎓三氟甲磺酸鹽、1-丁基-3-甲基吡啶鎓雙(三氟甲磺醯基)醯亞胺、1-辛基-4-甲基吡啶鎓雙(氟磺醯基)醯亞胺、1-甲基-1-丙基吡咯啶鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-丙基吡咯啶鎓雙(氟磺醯基)醯亞胺、1-甲基-1-丙基哌啶鎓雙(三氟甲磺醯基)醯亞胺、1-甲基-1-丙基哌啶鎓雙(氟磺醯基)醯亞胺、1-乙基-3-甲基咪唑鎓三氟甲磺酸鹽、1-乙基-3-甲基咪唑鎓七氟丙磺酸鹽、1-乙基-3-甲基咪唑鎓雙(三氟甲磺醯基)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(三氟甲磺醯基)醯亞胺、鋰雙(三氟甲磺醯基)醯亞胺、鋰雙(氟磺醯基)醯亞胺。Among the ionic liquids, 1-hexylpyridinium bis (fluorosulfonyl) fluorenimine, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, and 1-ethyl-3 are more preferable. -Methylpyridinium pentafluoroethanesulfonate, 1-ethyl-3-methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutanesulfonate, 1- Butyl-3-methylpyridinium triflate, 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) fluorenimine, 1-octyl-4-methylpyridine Onium bis (fluorosulfonyl) fluorenimine, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) fluorenimine, 1-methyl-1-propylpyrrolidinium bis (Fluorosulfenyl) fluorenimine, 1-methyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) fluorenimide, 1-methyl-1-propylpiperidinium bis (fluoro Sulfonyl) fluorenimine, 1-ethyl-3-methylimidazolium triflate, 1-ethyl-3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl-3 -Methylimidazolium bis (trifluoromethanesulfonyl) fluorenimide, 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) fluorenimide, 1-hexyl-3-methylimidazolium Bis (fluorosulfonyl) fluorenimide, trimethylpropylammonium bis (trifluoromethanesulfonyl) fluorenimide, lithium bis ( Acyl-fluoro-methanesulfonamide) (PEI), lithium bis (fluorosulfonyl acyl) (PEI).

離子性液體可使用市售者，亦可以如下述之方式而合成。作為離子性液體之合成方法，只要可獲得目標離子性液體，則並無特別限定，通常可使用如文獻「離子性液體-開發之最前沿與未來-」(CMC Publishing(股)發行)中所記載之鹵化物法、氫氧化物法、酸酯法、錯合法及中和法等。A commercially available ionic liquid can be used, and it can also be synthesized as follows. The synthesis method of the ionic liquid is not particularly limited as long as the target ionic liquid can be obtained. Generally, it can be used as described in the document "Ionic Liquids-Forefront of Development and Future-" (CMC Publishing) Documented halide method, hydroxide method, ester method, error method and neutralization method.

下文中關於鹵化物法、氫氧化物法、酸酯法、錯合法及中和法，以含氮之鎓鹽為例，揭示其合成方法，而關於其他含硫之鎓鹽、含磷之鎓鹽等其他離子性液體，亦可藉由相同之方法而獲得。In the following, the halide method, hydroxide method, acid ester method, error method and neutralization method are taken as examples to explain the synthesis method of nitrogen-containing onium salts, while other sulfur-containing onium salts and phosphorus-containing oniums are disclosed. Other ionic liquids such as salts can also be obtained by the same method.

鹵化物法係藉由如反應式(1)～(3)所示之反應而進行之方法。首先，使三級胺與鹵代烷反應而獲得鹵化物(反應式(1)，作為鹵素，使用氯、溴、碘)。The halide method is a method carried out by a reaction shown in reaction formulae (1) to (3). First, a tertiary amine is reacted with a haloalkane to obtain a halide (Reaction formula (1): As the halogen, chlorine, bromine, and iodine are used).

使所得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係銨、鋰、鈉、鉀等與目標陰離子形成鹽之陽離子)進行反應而獲得目標離子性液體(R₄ NA)。The resulting halide with an anion having an ionic liquid of the target structure (A ^-) of an acid (HA) or a salt (MA, M Department of ammonium, lithium, sodium and potassium salts of the cationic and anionic target is formed) obtained by reacting certain Ionic liquid (R ₄ NA).

[化2]
(1)R₃ N＋RX→R₄ NX(X：Cl、Br、I)
(2)R₄ NX＋HA→R₄ NA+HX
(3)R₄ NX＋MA→R₄ NA+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.)

氫氧化物法係藉由如反應式(4)～(8)所示之反應而進行之方法。首先，使鹵化物(R₄ NX)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(Ag₂ O)之反應(反應式(6))而獲得氫氧化物(R₄ NOH)(作為鹵素，使用氯、溴、碘)。The hydroxide method is a method carried out by a reaction shown in reaction formulae (4) to (8). First, a 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 hydroxide (R ₄ NOH) (as halogen, chlorine, bromine, and iodine are used).

關於所得氫氧化物，以與上述鹵化法相同之方式使用反應式(7)～(8)之反應，藉此獲得目標離子性液體(R₄ NA)。Regarding the obtained hydroxide, the reaction of the reaction formulae (7) to (8) was used in the same manner as the above-mentioned halogenation method, thereby obtaining a target ionic liquid (R ₄ NA).

[化3]
(4)R₄ NX＋H₂ O→R₄ NOH+1/2H₂ +1/2X₂ (X：Cl、Br、I)
(5)R₄ NX＋P-OH→R₄ NOH＋P-X(P-OH：OH型離子交換樹脂)
(6)R₄ NX＋1/2Ag₂ O＋1/2H₂ O→R₄ NOH＋AgX
(7)R₄ NOH＋HA→R₄ NA＋H₂ O
(8)R₄ NOH＋MA→R₄ NA＋MOH(M：NH₄ 、Li、Na、K、Ag等)[Chemical 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 ＋ P-X (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.)

酸酯法係藉由如反應式(9)～(11)所示之反應而進行之方法。首先，使三級胺(R₃ N)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磺酸、甲基膦酸、甲酸等有機酸之酯等)。The acid ester method is a method carried out by a reaction shown in the reaction formulae (9) to (11). 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 sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, or carbonic acid is used. Esters of organic acids such as sulfonic acid, methylphosphonic acid, formic acid, etc.).

關於所得酸酯物，以與上述鹵化法相同之方式使用反應式(10)～(11)之反應，藉此獲得目標離子性液體(R₄ NA)。又，亦可藉由使用三氟甲磺酸甲酯、三氟乙酸甲酯等作為酸酯，而直接獲得離子性液體。Regarding the obtained acid ester, the reaction of the reaction formulae (10) to (11) was used in the same manner as the above-mentioned halogenation method, thereby obtaining a target ionic liquid (R ₄ NA). Moreover, an ionic liquid can also be obtained directly by using methyl trifluoromethanesulfonate, methyl trifluoroacetate, etc. as an acid ester.

[化4]
[Chemical 4]

中和法係藉由如反應式(12)所示之反應而進行之方法。可藉由使三級胺與CF₃ COOH、CF₃ SO₃ H、(CF₃ SO₂ )₂ NH、(CF₃ SO₂ )₃ CH、(C₂ F₅ SO₂ )₂ NH等有機酸反應而獲得。The neutralization method is a method performed by a reaction shown in 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)R₃ N＋HZ→R₃ HN⁺ Z^-
[HZ：CF₃ COOH、CF₃ SO₃ H、(CF₃ SO₂ )₂ NH、(CF₃ SO₂ )₃ CH、(C₂ F₅ SO₂ )₂ NH等有機酸][Chemical 5]
_{(12) R 3 N + HZ} → R 3 HN + Z -
[HZ: 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)

上述反應式(1)～(12)中記載之R表示氫或碳數1至20之烴基，可含有雜原子。R in the above reaction formulae (1) to (12) represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, and may contain 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溶性而有所變化，故而無法一概而論，但通常相對於基礎聚合物100重量份，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，尤佳為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調整為上述範圍內，可提供抗靜電性非常優異之黏著劑組合物。若離子性液體之上述調配量未達0.01重量份，則存在無法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，則存在對被黏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, so it cannot be generalized, but it is usually 0.001 to 50 parts by weight relative to 100 parts by weight of the base polymer. Parts, 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. By adjusting the blending amount of the ionic liquid within the above range, an adhesive composition having excellent antistatic properties can be provided. If the amount of the ionic liquid is less than 0.01 part by weight, there is a possibility that sufficient antistatic properties cannot be obtained. If the above-mentioned blending amount of the ionic liquid exceeds 50 parts by weight, there is a tendency that contamination of an adherend increases.

黏著劑組合物可於不損害本發明之效果之範圍內含有改性聚矽氧油。藉由使黏著劑組合物含有改性聚矽氧油，可表現抗靜電特性之效果。尤其，藉由併用離子性液體，可更進一步有效地表現抗靜電特性之效果。The adhesive composition may contain a modified silicone oil to the extent that the effects of the present invention are not impaired. When the adhesive composition contains a modified silicone oil, the effect of antistatic properties can be exhibited. In particular, by using an ionic liquid in combination, the effect of antistatic properties can be more effectively exhibited.

於黏著劑組合物含有改性聚矽氧油之情形時，其含有比例相對於基礎聚合物100重量份，較佳為0.001重量份～50重量份，更佳為0.005重量份～40重量份，進而較佳為0.007重量份～30重量份，尤佳為0.008重量份～20重量份，最佳為0.01重量份～10重量份。藉由將改性聚矽氧油之含有比例調整為上述範圍內，可更進一步有效地表現抗靜電特性之效果。When the adhesive composition contains modified silicone oil, its content ratio is preferably 0.001 to 50 parts by weight, more preferably 0.005 to 40 parts by weight relative to 100 parts by weight of the base polymer. It is more preferably 0.007 to 30 parts by weight, particularly preferably 0.008 to 20 parts by weight, and most preferably 0.01 to 10 parts by weight. By adjusting the content ratio of the modified polysiloxane to be within the above range, the effect of antistatic properties can be more effectively exhibited.

作為改性聚矽氧油，可於不損害本發明之效果之範圍內採用任意合適之改性聚矽氧油。作為此種改性聚矽氧油，例如可列舉：可自信越化學工業(股)獲取之改性聚矽氧油。As the modified silicone oil, any suitable modified silicone oil can be used within a range that does not impair the effects of the present invention. Examples of such modified silicone oils include modified silicone oils that can be obtained with confidence from the Chemical Industry Co., Ltd.

作為改性聚矽氧油，較佳為聚醚改性聚矽氧油。藉由採用聚醚改性聚矽氧油，可更進一步有效地表現抗靜電特性之效果。As the modified silicone oil, a polyether-modified silicone oil is preferred. By using polyether modified silicone oil, the effect of antistatic properties can be further effectively expressed.

作為聚醚改性聚矽氧油，可列舉：側鏈型之聚醚改性聚矽氧油、兩末端型之聚醚改性聚矽氧油等。該等之中，就可充分更有效地表現抗靜電特性之效果之方面而言，較佳為兩末端型之聚醚改性聚矽氧油。Examples of the polyether-modified silicone oil include a polyether-modified silicone oil of a side chain type, and a polyether-modified silicone oil of both ends. Among these, a two-terminal type polyether-modified silicone oil is preferred in terms of sufficiently and more effectively expressing the effect of the antistatic property.

≪≪B.用途≫≫
本發明之表面保護膜可變得難以自被黏著體容易地剝離，可抑制經時之重剝離化，可表現因貼附於被黏著體而導致之該被黏著體表面之污染性較低之效果。故而，可較佳地用於光學構件或電子構件之表面保護。本發明之光學構件係貼著有本發明之表面保護膜者。本發明之電子構件係貼著有本發明之表面保護膜者。
[實施例]≪≪B. Uses≫≫
The surface protective film of the present invention can be difficult to be easily peeled from the adherend, can inhibit heavy peeling over time, and can show that the surface of the adherend is less polluting due to adhesion to the adherend. effect. Therefore, it can be preferably used for surface protection of optical components or electronic components. The optical member of the present invention is the one to which the surface protective film of the present invention is attached. The electronic component of the present invention is a person having the surface protective film of the present invention attached thereto.
[Example]

以下，藉由實施例具體說明本發明，但本發明不受該等實施例任何限定。再者，實施例等中之試驗及評價方法如下所述。再者，記載為「份」之情形時，只要無特別說明則表示「重量份」，記載為「%」之情形時，只要無特別說明則表示「重量%」。Hereinafter, the present invention will be specifically described by 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, when it is described as "part", it means "weight part" unless otherwise specified, and when it is described as "%", it means "weight%" unless otherwise specified.

＜自玻璃板之剝離力A(溫度23℃下放置30分鐘後)＞
將剝離隔離件之表面保護膜(寬25 mm×長140 mm)之黏著劑層側以2 kg手壓輥1次往復地貼合於玻璃板(鈉鈣玻璃，松浪硝子工業股份有限公司製造)，於23℃之環境溫度下放置30分鐘。
藉由拉伸試驗機測定以上述方式獲得之評價用試樣。作為拉伸試驗機，使用島津製作所公司製造之商品名「Autograph AG-Xplus HS 6000 mm/min高速型(AG-50NX plus)」。將評價用試樣設置於拉伸試驗機，開始拉伸試驗。具體而言，測定將表面保護膜自上述玻璃板剝離時之負荷，將此時之平均負荷作為表面保護膜之自玻璃板之剝離力A。拉伸試驗之條件為：試驗環境溫度：23℃，剝離角度：180度，剝離速度(拉伸速度)：300 mm/分鐘。＜ Peeling force A from glass plate (after standing for 30 minutes at 23 ° C) ＞
The adhesive layer side of the surface protective film (width 25 mm × length 140 mm) of the release separator was laminated to a glass plate (soda-lime glass, manufactured by Songlang Glass Industry Co., Ltd.) with a 2 kg hand roller once and back. , Place at ambient temperature of 23 ° C for 30 minutes.
The evaluation sample obtained in the above manner was measured by a tensile tester. As a tensile testing machine, a brand name "Autograph AG-Xplus HS 6000 mm / min high-speed type (AG-50NX plus)" manufactured by Shimadzu Corporation was used. The sample for evaluation was set in the tensile tester, and the tensile test was started. Specifically, the load when the surface protective film was peeled from the glass plate was measured, and the average load at this time was taken as the peeling force A of the surface protective film from the glass plate. The conditions of the tensile test are: test ambient temperature: 23 ° C, peeling angle: 180 degrees, peeling speed (tensile speed): 300 mm / min.

＜自玻璃板之剝離力B(溫度100℃下放置2日後)＞
將剝離隔離件之表面保護膜(寬25 mm×長140 mm)之黏著劑層側以2 kg手壓輥1次往復地貼合於玻璃板(鈉鈣玻璃，松浪硝子工業股份有限公司製造)，於100℃之溫度環境下放置2日。
藉由拉伸試驗機測定以上述方式獲得之評價用試樣。作為拉伸試驗機，使用島津製作所公司製造之商品名「Autograph AG-Xplus HS 6000 mm/min高速型(AG-50NX plus)」。將評價用試樣設置於拉伸試驗機，開始拉伸試驗。具體而言，測定將表面保護膜自上述玻璃板剝離時之負荷，將此時之平均負荷作為表面保護膜之自玻璃板之剝離力B。拉伸試驗之條件為：試驗環境溫度：23℃，剝離角度：180度，剝離速度(拉伸速度)：300 mm/分鐘。＜ Peeling force B from glass plate (after standing at 100 ° C for 2 days) ＞
The adhesive layer side of the surface protective film (width 25 mm × length 140 mm) of the release separator was laminated to a glass plate (soda-lime glass, manufactured by Songlang Glass Industry Co., Ltd.) with a 2 kg hand roller once and back. , Place at 100 ℃ for 2 days.
The evaluation sample obtained in the above manner was measured by a tensile tester. As a tensile testing machine, a brand name "Autograph AG-Xplus HS 6000 mm / min high-speed type (AG-50NX plus)" manufactured by Shimadzu Corporation was used. The sample for evaluation was set in the tensile tester, and the tensile test was started. Specifically, the load at the time of peeling the surface protective film from the glass plate was measured, and the average load at this time was taken as the peeling force B of the surface protective film from the glass plate. The conditions of the tensile test are: test ambient temperature: 23 ° C, peeling angle: 180 degrees, peeling speed (tensile speed): 300 mm / min.

＜自玻璃板之剝離力C(溫度23℃下放置7日後)＞
將剝離隔離件之表面保護膜(寬25 mm×長140 mm)之黏著劑層側以2 kg手壓輥1次往復地貼合於玻璃板(鈉鈣玻璃，松浪硝子工業股份有限公司製造)，於23℃之溫度環境下放置7日。
藉由拉伸試驗機測定以上述方式獲得之評價用試樣。作為拉伸試驗機，使用島津製作所公司製造之商品名「Autograph AG-Xplus HS 6000 mm/min高速型(AG-50NX plus)」。將評價用試樣設置於拉伸試驗機，開始拉伸試驗。具體而言，測定將表面保護膜自上述玻璃板剝離時之負荷，將此時之平均負荷作為表面保護膜之自玻璃板之剝離力C。拉伸試驗之條件為：試驗環境溫度：23℃，剝離角度：180度，剝離速度(拉伸速度)：300 mm/分鐘。＜ Peeling force C from glass plate (after standing for 7 days at 23 ° C) ＞
The adhesive layer side of the surface protective film (width 25 mm × length 140 mm) of the release separator was laminated to a glass plate (soda-lime glass, manufactured by Songlang Glass Industry Co., Ltd.) with a 2 kg hand roller once and back. , Place at 23 ℃ for 7 days.
The evaluation sample obtained in the above manner was measured by a tensile tester. As a tensile testing machine, a brand name "Autograph AG-Xplus HS 6000 mm / min high-speed type (AG-50NX plus)" manufactured by Shimadzu Corporation was used. The sample for evaluation was set in the tensile tester, and the tensile test was started. Specifically, the load when the surface protective film was peeled from the glass plate was measured, and the average load at this time was taken as the peeling force C of the surface protective film from the glass plate. The conditions of the tensile test are: test ambient temperature: 23 ° C, peeling angle: 180 degrees, peeling speed (tensile speed): 300 mm / min.

＜23℃下之對玻璃板之殘留接著率＞
將剝離隔離件之表面保護膜之黏著劑層側以2 kg手壓輥1次往復地貼合於整面玻璃板(松浪硝子製造，1.35 mm×10 cm×10 cm)，於溫度23℃、濕度55%RH之環境下保管24小時後，以0.3 m/min之速度剝離表面保護膜，準備完成處理之玻璃板。
繼而，於溫度23℃、濕度55%RH之環境下，將切斷為長150 mm之19 mm寬之No.31B膠帶(日東電工(股)製造，基材厚：25 μm)以2 kg手壓輥1次往復地貼附於上述完成處理之玻璃板之剝離表面保護膜之面。於溫度23℃、濕度55%RH之環境下，固化30分鐘後，使用拉伸試驗機(島津製作所公司製造之商品名「Autograph AG-Xplus HS 6000 mm/min高速型(AG-50NX plus)」)，以剝離角度：180度、剝離速度：300 mm/min進行剝離，測定黏著力a。
另外，對未進行如上述之表面保護膜之貼合與剝離之處理之玻璃板(松浪硝子製造，1.35 mm×10 cm×10 cm)，亦以與上述相同之方式，測定19 mm寬之No.31B膠帶之黏著力b。
藉由下述式算出殘留接著率。
殘留接著率(%)＝(黏著力a/黏著力b)×100
該殘留接著率係成為表面保護膜之黏著劑層之成分對於被黏著體以何種程度轉印至被黏著體之表面並造成污染之指標。殘留接著率之值越高，越成為難以因黏著劑層之成分而污染被黏著體之表面之表面保護膜，殘留接著率之值越低，越成為容易因黏著劑層之成分而污染被黏著體之表面之表面保護膜。<Residual Adhesion to Glass Plate at 23 ° C>
Adhere the adhesive layer side of the surface protective film of the release separator to the entire glass plate (made by Songlang Glass, 1.35 mm × 10 cm × 10 cm) back and forth with a 2 kg hand roller at a temperature of 23 ° C, After storage for 24 hours in an environment with a humidity of 55% RH, the surface protective film was peeled off at a speed of 0.3 m / min to prepare a glass plate for processing.
Then, under the environment of a temperature of 23 ° C and a humidity of 55% RH, it was cut into a No. 31B tape (made by Nitto Denko Co., Ltd., substrate thickness: 25 μm) with a length of 150 mm and a width of 19 mm, with a weight of 2 kg. The pressing roller is attached to the surface of the peeled surface protective film of the glass plate that has been processed above and back once and for all. After curing for 30 minutes in an environment with a temperature of 23 ° C and a humidity of 55% RH, a tensile tester (trade name "Autograph AG-Xplus HS 6000 mm / min high-speed type (AG-50NX plus)" manufactured by Shimadzu Corporation is used. ), Peeling was performed at a peeling angle: 180 degrees and a peeling speed: 300 mm / min, and the adhesive force a was measured.
In addition, for a glass plate (made by Songlang Glass, 1.35 mm × 10 cm × 10 cm) that has not been subjected to the above-mentioned bonding and peeling of the surface protective film, a 19 mm wide No Adhesion of .31B tape b.
The residual adhesion rate was calculated by the following formula.
Residual adhesion rate (%) = (adhesion a / adhesion b) × 100
The residual adhesion rate is an index of how much the components of the adhesive layer of the surface protection film are transferred to the surface of the adherend and cause pollution. The higher the value of the residual adhesion rate, the more it becomes a surface protective film that is difficult to contaminate the surface of the adherend due to the components of the adhesive layer. Surface protection film on the surface of the body.

[製造例1]
於裝備有1 L圓底可分離式燒瓶、可分離式蓋、分液漏斗、溫度計、氮氣導入管、李比希冷卻器、真空密封圈、攪拌棒、攪拌翼之聚合用實驗裝置中，投入聚丙二醇(製品名「Sunnix PP-2000」，三洋化成公司製造)：150 g、聚酯多元醇(製品名「Kuraray Polyol P-2010」，Kuraray公司製造)：150 g、作為溶劑之甲苯(Tosoh公司製造)：110 g、作為觸媒之二月桂酸二丁基錫(IV)(和光純藥工業公司製造)：0.041 g，一面攪拌，一面於常溫下實施氮氣置換1小時。其後，於氮氣流入下，一面攪拌，一面投入六亞甲基二異氰酸酯(製品名「HDI」，Tosoh公司製造)：33.5 g，藉由水浴以實驗裝置內溶液溫度成為90±2℃之方式進行控制並且保持4小時後，投入聚丙二醇(製品名「GP1000」，三洋化成公司製造)：74.9 g，藉由水浴以實驗裝置內溶液溫度成為90±2℃之方式進行控制並且保持2小時後，投入六亞甲基二異氰酸酯(製品名「HDI」，Tosoh公司製造)：25.4 g，藉由水浴以實驗裝置內溶液溫度成為90±2℃之方式進行控制並且保持2小時，獲得胺基甲酸酯預聚物溶液A。再者，聚合中途，為防止因聚合中之溫度控制及黏度上升而導致之攪拌性下降，適宜滴加甲苯。滴加之甲苯之總量為320 g。胺基甲酸酯預聚物溶液A之固形物成分濃度為50重量%。[Manufacturing example 1]
Polypropylene glycol was charged into a polymerization experimental apparatus equipped with a 1 L round bottom separable flask, a separable lid, a separating funnel, a thermometer, a nitrogen introduction tube, a Liebich cooler, a vacuum seal, a stirring rod, and a stirring wing. (Product name "Sunnix PP-2000", manufactured by Sanyo Chemical Co., Ltd.): 150 g, polyester polyol (product name "Kuraray Polyol P-2010", manufactured by Kuraray Corporation): 150 g, toluene as a solvent (manufactured by Tosoh Corporation) ): 110 g, dibutyltin (IV) dilaurate (manufactured by Wako Pure Chemical Industries, Ltd.) as a catalyst: 0.041 g, and nitrogen substitution at room temperature for 1 hour while stirring. After that, under nitrogen inflow, while stirring, hexamethylene diisocyanate (product name "HDI", manufactured by Tosoh Corporation) was added: 33.5 g, and the solution temperature in the experimental device was set to 90 ± 2 ° C by a water bath. After controlling and maintaining for 4 hours, put polypropylene glycol (product name "GP1000", manufactured by Sanyo Chemical Co., Ltd.): 74.9 g, and control with a water bath so that the solution temperature in the experimental device becomes 90 ± 2 ° C and hold for 2 hours , Put hexamethylene diisocyanate (product name "HDI", manufactured by Tosoh Corporation): 25.4 g, control with a water bath so that the solution temperature in the experimental device becomes 90 ± 2 ° C, and keep it for 2 hours to obtain aminomethyl Ester prepolymer solution A. Moreover, in the middle of the polymerization, in order to prevent the stirring property from being lowered due to the temperature control and viscosity increase during the polymerization, toluene was suitably added dropwise. The total amount of toluene added dropwise was 320 g. The solid content concentration of the urethane prepolymer solution A was 50% by weight.

[實施例1]
如表1所示，調配以聚合物固形物成分換算計為100重量份之製造例1中獲得之胺基甲酸酯預聚物溶液A、以固形物成分換算計為5.2重量份之異氰酸酯系交聯劑(商品名「Coronate HL」，Nippon Polyurethane股份有限公司製造)、以固形物成分換算計為0.5重量份之耐熱穩定劑(商品名「Irganox 1010」，BASF製造)、以固形物成分換算計為0.01重量份之含氟之聚合物(商品名「F-571」，DIC股份有限公司製造)、以固形物成分換算計為1重量份之脂肪酸酯(商品名「SALACOS 816」，Nisshin OilliO股份有限公司製造)，以整體之固形物成分成為45重量%之方式以乙酸乙酯進行稀釋，獲得黏著劑組合物(1)。
將所得黏著劑組合物(1)以乾燥後之厚度成為75 μm之方式塗佈於包含聚酯樹脂之基材(商品名「T100-75S」，厚度75 μm，三菱樹脂股份有限公司製造)，於乾燥溫度130℃、乾燥時間3分鐘之條件下進行硬化乾燥。如此，於基材上製作自黏著劑組合物(1)形成之黏著劑層(1)。
繼而，對於所得黏著劑層(1)之表面，於一個面貼合實施有聚矽氧處理之厚度25 μm之包含聚酯樹脂之隔離件(商品名「MRF25」，厚度25 μm，Mitsubishi Chemical公司製造)之聚矽氧處理面，獲得表面保護膜(1)。
所得表面保護膜(1)於常溫下進行7日老化，進行評價。剝離片材於即將評價之前剝離。結果示於表2。[Example 1]
As shown in Table 1, the urethane prepolymer solution A obtained in Production Example 1 based on 100 parts by weight of polymer solid content was blended, and 5.2 parts by weight of isocyanate based on solid content was prepared. Crosslinking agent (trade name "Coronate HL", manufactured by Nippon Polyurethane Co., Ltd.), a heat-resistant stabilizer (trade name "Irganox 1010", manufactured by BASF) based on solid content conversion, and solid content conversion 0.01 parts by weight of a fluorine-containing polymer (trade name "F-571", manufactured by DIC Corporation), and 1 part by weight of a fatty acid ester (trade name "SALACOS 816", Nisshin, based on solid content conversion) (Manufactured by OilliO Co., Ltd.), and diluted with ethyl acetate so that the solid content of the whole became 45% by weight, to obtain an adhesive composition (1).
Applying the obtained adhesive composition (1) to a substrate containing a polyester resin so that the thickness after drying becomes 75 μm (trade name “T100-75S”, thickness 75 μm, manufactured by Mitsubishi Resin Co., Ltd.), Hardening and drying were performed at a drying temperature of 130 ° C and a drying time of 3 minutes. In this way, an adhesive layer (1) formed from the adhesive composition (1) was prepared on the substrate.
Then, on the surface of the obtained adhesive layer (1), a 25 μm-thick polyester resin-containing separator (trade name “MRF25”, 25 μm thick, Mitsubishi Chemical Co., Ltd.) was subjected to polysiloxane treatment on one surface. (Manufactured), a surface treated with polysiloxane to obtain a surface protection film (1).
The obtained surface protective film (1) was aged at room temperature for 7 days and evaluated. The release sheet was peeled off immediately before evaluation. The results are shown in Table 2.

[實施例2]
如表1所示，除將脂肪酸酯(商品名「SALACOS 816」，Nisshin OilliO股份有限公司製造)之調配量變更為以固形物成分換算計為5重量份以外，以與實施例1相同之方式進行，製作自黏著劑組合物(2)形成之黏著劑層(2)，獲得表面保護膜(2)。結果示於表2。[Example 2]
As shown in Table 1, except that the blending amount of fatty acid ester (trade name "SALACOS 816", manufactured by Nisshin OilliO Co., Ltd.) was changed to 5 parts by weight in terms of solid content conversion, it was the same as in Example 1. The method is carried out to produce an adhesive layer (2) formed from the adhesive composition (2) to obtain a surface protective film (2). The results are shown in Table 2.

[實施例3]
如表1所示，除將脂肪酸酯(商品名「SALACOS 816」，Nisshin OilliO股份有限公司製造)之調配量變更為以固形物成分換算計為15重量份以外，以與實施例1相同之方式進行，製作自黏著劑組合物(3)形成之黏著劑層(3)，獲得表面保護膜(3)。結果示於表2。[Example 3]
As shown in Table 1, except that the blending amount of fatty acid ester (trade name "SALACOS 816", manufactured by Nisshin OilliO Co., Ltd.) was changed to 15 parts by weight in terms of solid content conversion, it was the same as in Example 1. The method is performed to produce an adhesive layer (3) formed from the adhesive composition (3), and a surface protective film (3) is obtained. The results are shown in Table 2.

[實施例4]
如表1所示，除將含氟之聚合物(商品名「F-571」，DIC股份有限公司製造)之調配量變更為以固形物成分換算計為0.05重量份以外，以與實施例1相同之方式進行，製作自黏著劑組合物(4)形成之黏著劑層(4)，獲得表面保護膜(4)。結果示於表2。[Example 4]
As shown in Table 1, except that the blending amount of the fluorine-containing polymer (trade name "F-571", manufactured by DIC Corporation) was changed to 0.05 parts by weight in terms of solid content conversion, it was the same as in Example 1. In the same manner, an adhesive layer (4) formed from the adhesive composition (4) was produced, and a surface protective film (4) was obtained. The results are shown in Table 2.

[實施例5]
如表1所示，除將含氟之聚合物(商品名「F-571」，DIC股份有限公司製造)之調配量變更為以固形物成分換算計為0.05重量份，將肪酸酸酯(商品名「SALACOS 816」，Nisshin OilliO股份有限公司製造)之調配量變更為以固形物成分換算計為5重量份以外，以與實施例1相同之方式進行，製作自黏著劑組合物(5)形成之黏著劑層(5)，獲得表面保護膜(5)。結果示於表2。[Example 5]
As shown in Table 1, in addition to changing the blending amount of the fluorine-containing polymer (trade name "F-571", manufactured by DIC Corporation) to 0.05 parts by weight in terms of solid content, the fatty acid ester ( Trade name "SALACOS 816" (manufactured by Nisshin OilliO Co., Ltd.) was changed to 5 parts by weight in terms of solid content, and the same procedure as in Example 1 was performed to prepare a self-adhesive composition (5) The formed adhesive layer (5) obtains a surface protective film (5). The results are shown in Table 2.

[實施例6]
如表1所示，除將含氟之聚合物(商品名「F-571」，DIC股份有限公司製造)之調配量變更為以固形物成分換算計為0.05重量份，將肪酸酸酯(商品名「SALACOS 816」，Nisshin OilliO股份有限公司製造)之調配量變更為以固形物成分換算計為15重量份以外，以與實施例1相同之方式進行，製作自黏著劑組合物(6)形成之黏著劑層(6)，獲得表面保護膜(6)。結果示於表2。[Example 6]
As shown in Table 1, in addition to changing the blending amount of the fluorine-containing polymer (trade name "F-571", manufactured by DIC Corporation) to 0.05 parts by weight in terms of solid content, the fatty acid ester ( Trade name "SALACOS 816" (manufactured by Nisshin OilliO Co., Ltd.) was changed to 15 parts by weight in terms of solid content, and the same procedure as in Example 1 was performed to produce a self-adhesive composition (6) The formed adhesive layer (6) obtains a surface protective film (6). The results are shown in Table 2.

[實施例7]
如表1所示，除將異氰酸酯系交聯劑(商品名「Coronate HL」，Nippon Polyurethane股份有限公司製造)之調配量變更為以固形物成分換算計為3.9重量份，將肪酸酸酯(商品名「SALACOS 816」，Nisshin OilliO股份有限公司製造)之調配量變更為以固形物成分換算計為5重量份以外，以與實施例1相同之方式進行，製作自黏著劑組合物(7)形成之黏著劑層(7)，獲得表面保護膜(7)。結果示於表2。[Example 7]
As shown in Table 1, except that the blending amount of the isocyanate-based crosslinking agent (trade name "Coronate HL", manufactured by Nippon Polyurethane Co., Ltd.) was changed to 3.9 parts by weight in terms of solid content, the fatty acid ester ( Trade name "SALACOS 816" (manufactured by Nisshin OilliO Co., Ltd.). The compounding amount was changed to 5 parts by weight in terms of solid content. The same procedure as in Example 1 was performed to prepare a self-adhesive composition (7). The formed adhesive layer (7) obtains a surface protective film (7). The results are shown in Table 2.

[實施例8]
如表1所示，除將異氰酸酯系交聯劑(商品名「Coronate HL」，Nippon Polyurethane股份有限公司製造)之調配量變更為以固形物成分換算計為3.9重量份，將含氟之聚合物(商品名「F-571」，DIC股份有限公司製造)之調配量變更為以固形物成分換算計為0.05重量份，將肪酸酸酯(商品名「SALACOS 816」，Nisshin OilliO股份有限公司製造)之調配量變更為以固形物成分換算計為5重量份以外，以與實施例1相同之方式進行，製作自黏著劑組合物(8)形成之黏著劑層(8)，獲得表面保護膜(8)。結果示於表2。[Example 8]
As shown in Table 1, the amount of the isocyanate-based crosslinking agent (trade name "Coronate HL", manufactured by Nippon Polyurethane Co., Ltd.) was changed to 3.9 parts by weight in terms of solid content, and the fluorine-containing polymer was changed. (Brand name "F-571", manufactured by DIC Corporation) The blending amount was changed to 0.05 parts by weight in terms of solid content conversion, and fatty acid ester (brand name "SALACOS 816", manufactured by Nisshin OilliO Corporation) ) Was changed to 5 parts by weight in terms of solid content, and was performed in the same manner as in Example 1. An adhesive layer (8) formed from the adhesive composition (8) was produced to obtain a surface protective film. (8). The results are shown in Table 2.

[實施例9]
如表1所示，除將異氰酸酯系交聯劑(商品名「Coronate HL」，Nippon Polyurethane股份有限公司製造)之調配量變更為以固形物成分換算計為2.6重量份，將含氟之聚合物(商品名「F-571」，DIC股份有限公司製造)之調配量變更為以固形物成分換算計為0.10重量份，將肪酸酸酯(商品名「SALACOS 816」，Nisshin OilliO股份有限公司製造)之調配量變更為以固形物成分換算計為5重量份以外，以與實施例1相同之方式進行，製作自黏著劑組合物(9)形成之黏著劑層(9)，獲得表面保護膜(9)。結果示於表2。[Example 9]
As shown in Table 1, the amount of the isocyanate-based crosslinking agent (trade name "Coronate HL", manufactured by Nippon Polyurethane Co., Ltd.) was changed to 2.6 parts by weight in terms of solid content, and the fluorine-containing polymer was changed. (Brand name "F-571", manufactured by DIC Corporation) The blending amount was changed to 0.10 parts by weight in terms of solid content conversion, and fatty acid ester (brand name "SALACOS 816", manufactured by Nisshin OilliO Corporation) The amount of) was changed to 5 parts by weight in terms of solid content, and the same procedure as in Example 1 was performed to prepare an adhesive layer (9) formed from the adhesive composition (9) to obtain a surface protective film. (9). The results are shown in Table 2.

[實施例10]
如表1所示，除將異氰酸酯系交聯劑(商品名「Coronate HL」，Nippon Polyurethane股份有限公司製造)之調配量變更為以固形物成分換算計為2.6重量份，將含氟之聚合物(商品名「F-571」，DIC股份有限公司製造)之調配量變更為以固形物成分換算計為0.20重量份，將肪酸酸酯(商品名「SALACOS 816」，Nisshin OilliO股份有限公司製造)之調配量變更為以固形物成分換算計為5重量份以外，以與實施例1相同之方式進行，製作自黏著劑組合物(10)形成之黏著劑層(10)，獲得表面保護膜(10)。結果示於表2。[Example 10]
As shown in Table 1, the amount of the isocyanate-based crosslinking agent (trade name "Coronate HL", manufactured by Nippon Polyurethane Co., Ltd.) was changed to 2.6 parts by weight in terms of solid content, and the fluorine-containing polymer was changed. (Brand name "F-571", manufactured by DIC Corporation). The blending amount was changed to 0.20 parts by weight in terms of solid content. The fatty acid ester (brand name "SALACOS 816", manufactured by Nisshin OilliO Corporation) ) Was changed to 5 parts by weight in terms of solid content conversion, and was performed in the same manner as in Example 1. An adhesive layer (10) formed from the adhesive composition (10) was prepared to obtain a surface protective film. (10). The results are shown in Table 2.

[實施例11]
如表1所示，除將異氰酸酯系交聯劑(商品名「Coronate HL」，Nippon Polyurethane股份有限公司製造)之調配量變更為以固形物成分換算計為9.5重量份以外，以與實施例1相同之方式進行，製作自黏著劑組合物(11)形成之黏著劑層(11)，獲得表面保護膜(11)。結果示於表2。[Example 11]
As shown in Table 1, except that the blending amount of the isocyanate-based cross-linking agent (trade name "Coronate HL", manufactured by Nippon Polyurethane Co., Ltd.) was changed to 9.5 parts by weight in terms of solid content, the same composition as in Example 1 was used. In the same manner, an adhesive layer (11) formed from the adhesive composition (11) was prepared to obtain a surface protective film (11). The results are shown in Table 2.

[實施例12]
如表1所示，除將異氰酸酯系交聯劑(商品名「Coronate HL」，Nippon Polyurethane股份有限公司製造)之調配量變更為以固形物成分換算計為12.7重量份以外，以與實施例1相同之方式進行，製作自黏著劑組合物(12)形成之黏著劑層(12)，獲得表面保護膜(12)。結果示於表2。[Example 12]
As shown in Table 1, except that the compounding amount of the isocyanate-based cross-linking agent (trade name "Coronate HL", manufactured by Nippon Polyurethane Co., Ltd.) was changed to 12.7 parts by weight in terms of solid content conversion, the same composition as in Example 1 was used. In the same manner, an adhesive layer (12) formed from the adhesive composition (12) was produced to obtain a surface protective film (12). The results are shown in Table 2.

[實施例13]
如表1所示，除使用以固形物成分換算計為0.05重量份之含羥基之聚矽氧(商品名「X-22-4015」，信越化學工業股份有限公司製造)，代替含氟之聚合物(商品名「F-571」，DIC股份有限公司製造)，將肪酸酸酯(商品名「SALACOS 816」，Nisshin OilliO股份有限公司製造)之調配量變更為以固形物成分換算計為5重量份以外，以與實施例1相同之方式進行，製作自黏著劑組合物(13)形成之黏著劑層(13)，獲得表面保護膜(13)。結果示於表2。[Example 13]
As shown in Table 1, a hydroxyl-containing polysiloxane (trade name "X-22-4015", manufactured by Shin-Etsu Chemical Industry Co., Ltd.) was used in addition to 0.05 parts by weight in terms of solid content, instead of fluorine-containing polymerization. (Trade name "F-571", manufactured by DIC Corporation), and the amount of fatty acid ester (trade name "SALACOS 816", manufactured by Nishin OilliO Corporation) was changed to 5 in terms of solid content conversion Except for the part by weight, it carried out similarly to Example 1, and produced the adhesive layer (13) formed from the adhesive composition (13), and obtained the surface protective film (13). The results are shown in Table 2.

[實施例14]
如表1所示，除使用以固形物成分換算計為3.2重量份之異氰酸酯系交聯劑(商品名「Coronate HX」，Nippon Polyurethane股份有限公司製造)，代替異氰酸酯系交聯劑(商品名「Coronate HL」，Nippon Polyurethane股份有限公司製造)，將含氟之聚合物(商品名「F-571」，DIC股份有限公司製造)之調配量變更為以固形物成分換算計為0.05重量份，將肪酸酸酯(商品名「SALACOS 816」，Nisshin OilliO股份有限公司製造)之調配量變更為以固形物成分換算計為5重量份以外，以與實施例1相同之方式進行，製作自黏著劑組合物(14)形成之黏著劑層(14)，獲得表面保護膜(14)。結果示於表2。[Example 14]
As shown in Table 1, the isocyanate-based crosslinking agent (trade name "Coronate HX", manufactured by Nippon Polyurethane Co., Ltd.) was used in place of 3.2 parts by weight in terms of solid content, instead of the isocyanate-based crosslinking agent (trade name ""CoronateHL", manufactured by Nippon Polyurethane Co., Ltd.). The compounding amount of the fluorine-containing polymer (trade name "F-571", manufactured by DIC Co., Ltd.) was changed to 0.05 parts by weight in terms of solid content. Fatty acid ester (trade name "SALACOS 816", manufactured by Nisshin OilliO Co., Ltd.) was changed to 5 parts by weight in terms of solid content, and the same procedure as in Example 1 was performed to produce a self-adhesive An adhesive layer (14) formed from the composition (14) to obtain a surface protective film (14). The results are shown in Table 2.

[實施例15]
如表1所示，除使用以固形物成分換算計為5.6重量份之異氰酸酯系交聯劑(商品名「Coronate HX」，Nippon Polyurethane股份有限公司製造)，代替異氰酸酯系交聯劑(商品名「Coronate HL」，Nippon Polyurethane股份有限公司製造)，將肪酸酸酯(商品名「SALACOS 816」，Nisshin OilliO股份有限公司製造)之調配量變更為以固形物成分換算計為5重量份以外，以與實施例1相同之方式進行，製作自黏著劑組合物(15)形成之黏著劑層(15)，獲得表面保護膜(15)。結果示於表2。[Example 15]
As shown in Table 1, an isocyanate-based cross-linking agent (trade name "Coronate HX", manufactured by Nippon Polyurethane Co., Ltd.) was used instead of an isocyanate-based cross-linking agent (trade name ""CoronateHL", manufactured by Nippon Polyurethane Co., Ltd., and the amount of fatty acid esters (trade name "SALACOS 816", manufactured by Nisshin OilliO Co., Ltd.) was changed to 5 parts by weight in terms of solid content conversion. The same procedure as in Example 1 was performed to prepare an adhesive layer (15) formed from the adhesive composition (15) to obtain a surface protective film (15). The results are shown in Table 2.

[比較例1]
如表1所示，除將異氰酸酯系交聯劑(商品名「Coronate HL」，Nippon Polyurethane股份有限公司製造)之調配量變更為以固形物成分換算計為3.9重量份，不使用含氟之聚合物(商品名「F-571」，DIC股份有限公司製造)與肪酸酸酯(商品名「SALACOS 816」，Nisshin OilliO股份有限公司製造)以外，以與實施例1相同之方式進行，製作自黏著劑組合物(C1)形成之黏著劑層(C1)，獲得表面保護膜(C1)。結果示於表2。[Comparative Example 1]
As shown in Table 1, except that the blending amount of the isocyanate-based crosslinking agent (trade name "Coronate HL", manufactured by Nippon Polyurethane Co., Ltd.) was changed to 3.9 parts by weight in terms of solid content conversion, no fluorine-containing polymerization was used. Except that the product (trade name "F-571", manufactured by DIC Corporation) and fatty acid ester (trade name "SALACOS 816", manufactured by Nishin OilliO Corporation) were performed in the same manner as in Example 1, and produced from An adhesive layer (C1) formed from the adhesive composition (C1) to obtain a surface protective film (C1). The results are shown in Table 2.

[比較例2]
如表1所示，除不使用含氟之聚合物(商品名「F-571」，DIC股份有限公司製造)與肪酸酸酯(商品名「SALACOS 816」，Nisshin OilliO股份有限公司製造)以外，以與實施例1相同之方式進行，製作自黏著劑組合物(C2)形成之黏著劑層，獲得表面保護膜(C2)。結果示於表2。[Comparative Example 2]
As shown in Table 1, except that a fluorine-containing polymer (trade name "F-571", manufactured by DIC Corporation) and fatty acid ester (trade name "SALACOS 816", manufactured by Nisshin OilliO Corporation) are not used. In the same manner as in Example 1, an adhesive layer formed from the adhesive composition (C2) was produced to obtain a surface protective film (C2). The results are shown in Table 2.

[比較例3]
如表1所示，除將含氟之聚合物(商品名「F-571」，DIC股份有限公司製造)之調配量變更為以固形物成分換算計為0.05重量份，不使用肪酸酸酯(商品名「SALACOS 816」，Nisshin OilliO股份有限公司製造)以外，以與實施例1相同之方式進行，製作自黏著劑組合物(C3)形成之黏著劑層(C3)，獲得表面保護膜(C3)。結果示於表2。[Comparative Example 3]
As shown in Table 1, except that the blending amount of the fluorine-containing polymer (trade name "F-571", manufactured by DIC Corporation) was changed to 0.05 parts by weight in terms of solid content, no fatty acid ester was used. (Product name: "SALACOS 816", manufactured by Nisshin OilliO Co., Ltd.), the same procedure as in Example 1 was performed to prepare an adhesive layer (C3) formed from the adhesive composition (C3) to obtain a surface protective film ( C3). The results are shown in Table 2.

[比較例4]
如表1所示，除將肪酸酸酯(商品名「SALACOS 816」，Nisshin OilliO股份有限公司製造)變更為以固形物成分換算計為5重量份，不使用含氟之聚合物(商品名「F-571」，DIC股份有限公司製造)以外，以與實施例1相同之方式進行，製作包含黏著劑組合物(C4)之黏著劑層，獲得表面保護膜(C4)。結果示於表2。[Comparative Example 4]
As shown in Table 1, except that the fatty acid ester (trade name "SALACOS 816", manufactured by Nisshin OilliO Co., Ltd.) was changed to 5 parts by weight in terms of solid content conversion, a fluorine-containing polymer (trade name Except for "F-571" (manufactured by DIC Corporation), an adhesive layer containing an adhesive composition (C4) was produced in the same manner as in Example 1 to obtain a surface protective film (C4). The results are shown in Table 2.

[比較例5]
如表1所示，除使用以固形物成分換算計為1.0重量份之聚矽氧剝離劑(商品名「KS-776A」，信越化學工業股份有限公司製造)，代替含氟之聚合物(商品名「F-571」，DIC股份有限公司製造)，不使用肪酸酸酯(商品名「SALACOS 816」，Nisshin OilliO股份有限公司製造)以外，以與實施例1相同之方式進行，製作自黏著劑組合物(C5)形成之黏著劑層(C5)，獲得表面保護膜(C5)。結果示於表2。[Comparative Example 5]
As shown in Table 1, in addition to using 1.0 parts by weight of a polysiloxane stripper (trade name "KS-776A", manufactured by Shin-Etsu Chemical Industry Co., Ltd.) in terms of solid content conversion, a fluorine-containing polymer (commodity The name "F-571", manufactured by DIC Corporation) was used in the same manner as in Example 1 except that no fatty acid ester (trade name "SALACOS 816", manufactured by Nishin OilliO Corporation) was used, and a self-adhesive was produced. An adhesive layer (C5) formed by the adhesive composition (C5) to obtain a surface protective film (C5). The results are shown in Table 2.

[比較例6]
如表1所示，除使用以固形物成分換算計為100重量份之市售之胺基甲酸酯預聚物溶液(商品名「CYABINE SH-109」，TOYOCHEM股份有限公司製造)，代替製造例1中獲得之胺基甲酸酯預聚物溶液A，使用以固形物成分換算計為3.6重量份之異氰酸酯系交聯劑(商品名「Coronate HX」，Nippon Polyurethane股份有限公司製造)，代替異氰酸酯系交聯劑(商品名「Coronate HL」，Nippon Polyurethane股份有限公司製造)，將含氟之聚合物(商品名「F-571」，DIC股份有限公司製造)之調配量變更為以固形物成分換算計為1重量份，不使用肪酸酸酯(商品名「SALACOS 816」，Nisshin OilliO股份有限公司製造)以外，以與實施例1相同之方式進行，獲得自黏著劑組合物(C6)形成之黏著劑層(C6)，獲得表面保護膜(C6)。結果示於表2。[Comparative Example 6]
As shown in Table 1, a commercially available urethane prepolymer solution (trade name "CYABINE SH-109", manufactured by TOYOCHEM Co., Ltd.) was used instead of 100 parts by weight in terms of solid content. The urethane prepolymer solution A obtained in Example 1 was replaced with an isocyanate-based crosslinking agent (trade name "Coronate HX", manufactured by Nippon Polyurethane Co., Ltd.) which was 3.6 parts by weight in terms of solid content. Isocyanate-based cross-linking agent (trade name "Coronate HL", manufactured by Nippon Polyurethane Co., Ltd.). The amount of fluorine-containing polymer (trade name "F-571", manufactured by DIC Co., Ltd.) was changed to solid. The component conversion was 1 part by weight, and a self-adhesive composition (C6) was obtained in the same manner as in Example 1 except that no fatty acid ester (trade name "SALACOS 816", manufactured by Nisshin OilliO Co., Ltd.) was used. The formed adhesive layer (C6) obtained a surface protective film (C6). The results are shown in Table 2.

[表1]
[Table 1]

[表2]
[Table 2]

[實施例16～30]
分別對實施例1～15中獲得之表面保護膜(1)～(15)，剝離隔離件，將黏著劑層側貼著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」)，獲得貼著有表面保護膜之光學構件。[Examples 16 to 30]
For the surface protective films (1) to (15) obtained in Examples 1 to 15, the separator was peeled off, and the adhesive layer side was stuck to a polarizing plate (made by Nitto Denko Corporation, trade name " TEG1465DUHC ") to obtain an optical member with a surface protective film.

[實施例31～45]
分別對實施例1～15中獲得之表面保護膜(1)～(15)，剝離隔離件，將黏著劑層側貼著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」)，獲得貼著有表面保護膜之電子構件。
[產業上之可利用性][Examples 31 to 45]
For the surface protective films (1) to (15) obtained in Examples 1 to 15, the separator was peeled off, and the adhesive layer side was stuck to a conductive film (made by Nitto Denko Corporation, trade name) "ELECRYSTA V270L-TFMP") to obtain electronic components with a surface protective film.
[Industrial availability]

本發明之表面保護膜可用於任意合適之用途。較佳為本發明之表面保護膜較佳地用於光學構件或電子構件之領域。The surface protective film of the present invention can be used for any suitable application. The surface protection film of the present invention is preferably used in the field of optical members or electronic members.

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係根據本發明之一實施形態之表面保護膜之概略截面圖。FIG. 1 is a schematic cross-sectional view of a surface protective film according to an embodiment of the present invention.

Claims

一種表面保護膜，其係具有黏著劑層者，並且將該表面保護膜之該黏著劑層貼合於玻璃板於溫度23℃下放置30分鐘後，於溫度23℃下將該表面保護膜自該玻璃板以剝離角度180度、剝離速度300 mm/分鐘進行剝離時之剝離力A為0.024 N/25 mm～0.50 N/25 mm，將該表面保護膜之該黏著劑層貼合於玻璃板於溫度100℃下放置2日後，於溫度23℃下將該表面保護膜自該玻璃板以剝離角度180度、剝離速度300 mm/分鐘進行剝離，將此時之剝離力設為B時，以(B/A)×100算出之剝離力經時上升率為1000%以下。A surface protective film having an adhesive layer, and After the adhesive layer of the surface protection film was bonded to a glass plate and left at a temperature of 23 ° C for 30 minutes, the surface protection film was peeled from the glass plate at a temperature of 23 ° C at a peeling angle of 180 degrees and a peeling speed of 300 mm / The peeling force A when peeling in minutes is 0.024 N / 25 mm to 0.50 N / 25 mm, After the adhesive layer of the surface protection film was bonded to a glass plate and left at a temperature of 100 ° C for 2 days, the surface protection film was peeled from the glass plate at a temperature of 23 ° C at a peeling angle of 180 degrees and a peeling speed of 300 mm / min. When peeling was performed and the peeling force at this time was set to B, the increase rate of the peeling force over time calculated by (B / A) × 100 was 1000% or less.

如請求項1之表面保護膜，其中將上述表面保護膜之上述黏著劑層貼合於玻璃板於23℃下放置7日後，於溫度23℃下將該表面保護膜自該玻璃板以剝離角度180度、剝離速度300 mm/分鐘進行剝離，將此時之剝離力設為C時，以(C/A)×100算出之剝離力經時上升率為160%以下。For example, the surface protection film of claim 1, wherein the above-mentioned adhesive layer of the surface protection film is bonded to a glass plate and left at 23 ° C for 7 days, and then the surface protection film is peeled from the glass plate at a temperature of 23 ° C. The peeling was performed at 180 degrees and a peeling speed of 300 mm / minute. When the peeling force at this time was set to C, the time-dependent increase rate of the peeling force calculated by (C / A) × 100 was 160% or less.

如請求項1或2之表面保護膜，其中23℃下之對玻璃板之殘留接著率為50%以上。For example, if the surface protection film of item 1 or 2 is required, the residual adhesion rate to the glass plate at 23 ° C is more than 50%.

如請求項1至3中任一項之表面保護膜，其中構成上述黏著劑層之黏著劑係自黏著劑組合物形成，該黏著劑組合物含有基礎聚合物與聚矽氧系添加劑及/或氟系添加劑。The surface protective film according to any one of claims 1 to 3, wherein the adhesive constituting the above-mentioned adhesive layer is formed from a self-adhesive composition, the adhesive composition comprising a base polymer and a polysiloxane additive and / or Fluorine-based additives.

如請求項4之表面保護膜，其中上述黏著劑組合物含有脂肪酸酯。The surface protective film according to claim 4, wherein the adhesive composition contains a fatty acid ester.

如請求項4或5之表面保護膜，其中上述聚矽氧系添加劑為選自含矽氧烷鍵之化合物、含羥基之聚矽氧系化合物、含交聯性官能基之聚矽氧系化合物中之至少一種。The surface protective film according to claim 4 or 5, wherein the polysiloxane additive is selected from the group consisting of a compound containing a siloxane bond, a polysiloxane compound containing a hydroxyl group, and a polysiloxane compound containing a crosslinkable functional group. At least one of them.

如請求項4至6中任一項之表面保護膜，其中上述氟系添加劑為選自含氟之化合物、含羥基之氟系化合物、含交聯性官能基之氟系化合物中之至少一種。The surface protective film according to any one of claims 4 to 6, wherein the fluorine-based additive is at least one selected from a fluorine-containing compound, a hydroxyl-containing fluorine-based compound, and a crosslinkable functional group-containing fluorine-based compound.

如請求項4至7中任一項之表面保護膜，其中上述基礎聚合物為選自胺基甲酸酯預聚物、多元醇、丙烯酸系樹脂、橡膠系樹脂、聚矽氧系樹脂中之至少一種。The surface protective film according to any one of claims 4 to 7, wherein the base polymer is selected from the group consisting of a urethane prepolymer, a polyol, an acrylic resin, a rubber resin, and a silicone resin. At least one.

一種光學構件，其係貼著有如請求項1至8中任一項之表面保護膜者。An optical member to which a surface protective film according to any one of claims 1 to 8 is attached.

一種電子構件，其係貼著有如請求項1至8中任一項之表面保護膜者。An electronic component to which a surface protective film according to any one of claims 1 to 8 is attached.