TW202216940A - surface protection film - Google Patents

surface protection film Download PDF

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TW202216940A
TW202216940A TW111101602A TW111101602A TW202216940A TW 202216940 A TW202216940 A TW 202216940A TW 111101602 A TW111101602 A TW 111101602A TW 111101602 A TW111101602 A TW 111101602A TW 202216940 A TW202216940 A TW 202216940A
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weight
cation
bis
fluorine
imide
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舟木千尋
佐佐木翔悟
立川悠
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日商日東電工股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/04—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00—Presence of polyurethane

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)

Abstract

Provided is a surface protection film which comprises an adhesive layer, which is typically adhered to exposed surfaces of an optical member and an electronic member in order to prevent damage to the surfaces of the optical member and the electronic member during processing, assembly, inspection, transport, and the like in a process for manufacturing the optical member and the electronic member, and which sufficiently suppresses peeling electrostatic voltage. The optical member and the electronic member are not damaged during peeling. The surface protection film according to an embodiment of the present invention comprises an adhesive layer, an adhesive constituting the adhesive layer is formed from an adhesive composition containing a base polymer, an ionic compound, and a fluorine-based compound, and the surface free energy of the surface of the adhesive layer with respect to diiodomethane is 6-30 mJ/m2.

Description

表面保護膜surface protection film

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

於光學構件或電子構件之製造步驟中，為了防止該光學構件或該電子構件之表面於加工、組裝、檢查、運輸等時受損，通常在該光學構件或該電子構件之露出面貼附表面保護膜。於不再需要進行表面保護之時點，將此種表面保護膜從光學構件或電子構件剝離(專利文獻1)。In the manufacturing steps of optical components or electronic components, in order to prevent the surface of the optical component or the electronic component from being damaged during processing, assembly, inspection, transportation, etc., the surface is usually attached to the exposed surface of the optical component or the electronic component. protective film. When surface protection is no longer necessary, such a surface protection film is peeled off from an optical member or an electronic member (Patent Document 1).

通常，表面保護膜、及光學構件或電子構件之電氣絕緣性較高，會因摩擦或剝離而產生靜電。因此，於將表面保護膜從光學構件或電子構件剝離時亦容易產生靜電。於此種情形時，例如存在如下顧慮：若於靜電殘留之狀態下對液晶施加電壓，則發生液晶分子之配向損失，或產生面板缺陷。又，靜電之存在亦能夠成為吸引塵埃或使作業性下降之要因。Generally, surface protection films and optical members or electronic members have high electrical insulating properties, and static electricity is generated due to friction or peeling. Therefore, static electricity is easily generated even when the surface protective film is peeled off from an optical member or an electronic member. In such a case, for example, if a voltage is applied to the liquid crystal in a state where static electricity remains, the alignment loss of the liquid crystal molecules will occur, or a panel defect will occur. In addition, the presence of static electricity can also be a factor that attracts dust or reduces workability.

為了防止靜電，進行對表面保護膜施加抗靜電處理之操作。例如，報告有作為表面保護膜之表面層(面塗層及背面層)，藉由形成抗靜電層或施加抗靜電塗佈，而賦予抗靜電功能(專利文獻2及3)。In order to prevent static electricity, the operation of applying antistatic treatment to the surface protection film is performed. For example, it is reported that an antistatic function is imparted to the surface layer (topcoat layer and backside layer) as a surface protective film by forming an antistatic layer or applying an antistatic coating (Patent Documents 2 and 3).

又，為了對構成表面保護膜之黏著劑層本身賦予抗靜電性，採用了如下方法：使黏著劑層中含有作為抗靜電劑發揮功能之鹼金屬鹽或離子性液體等離子性化合物，並轉印至被黏著體(專利文獻4)。 [先前技術文獻] [專利文獻] In addition, in order to impart antistatic properties to the adhesive layer itself constituting the surface protective film, a method has been adopted in which the adhesive layer contains an alkali metal salt or an ionic compound such as an ionic liquid that functions as an antistatic agent, and transfers to the adherend (Patent Document 4). [Prior Art 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2004-223923號公報 [專利文獻3]日本專利特開2008-255332號公報 [專利文獻4]日本專利特開平9-165460號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2016-17109 [Patent Document 2] Japanese Patent Laid-Open No. 2004-223923 [Patent Document 3] Japanese Patent Laid-Open No. 2008-255332 [Patent Document 4] Japanese Patent Laid-Open No. 9-165460

[發明所欲解決之問題][Problems to be Solved by Invention]

本發明之課題在於提供一種充分地抑制剝離靜電壓而於剝離時不會使該光學構件或該電子構件破損之表面保護膜，該表面保護膜代表性而言為包含黏著劑層之表面保護膜，其於光學構件或電子構件之製造步驟中，為了防止該光學構件或該電子構件之表面於加工、組裝、檢查、運輸等時受損而貼合於該光學構件或該電子構件之露出面。 [解決問題之技術手段] An object of the present invention is to provide a surface protection film that sufficiently suppresses peeling electrostatic voltage and does not damage the optical member or the electronic member during peeling, typically a surface protection film containing an adhesive layer , which is attached to the exposed surface of the optical component or the electronic component in order to prevent the surface of the optical component or the electronic component from being damaged during processing, assembly, inspection, transportation, etc. during the manufacturing steps of the optical component or electronic component . [Technical means to solve problems]

本發明之實施方式之表面保護膜係包含黏著劑層者，且 構成該黏著劑層之黏著劑由黏著劑組合物形成， 該黏著劑組合物包含基礎聚合物、離子性化合物及氟系化合物， 該黏著劑層表面之對於二碘甲烷之表面自由能為6 mJ/m 2～30 mJ/m 2。 The surface protection film of the embodiment of the present invention includes an adhesive layer, and the adhesive constituting the adhesive layer is formed of an adhesive composition, and the adhesive composition includes a base polymer, an ionic compound and a fluorine-based compound, The surface free energy of the surface of the adhesive layer to diiodomethane is 6 mJ/m 2 to 30 mJ/m 2 .

於一實施方式中，上述離子性化合物相對於上述基礎聚合物100重量份之含有比率為0.2重量份以上。In one Embodiment, the content rate of the said ionic compound with respect to 100 weight part of said base polymers is 0.2 weight part or more.

於一實施方式中，上述氟系化合物相對於上述基礎聚合物100重量份之含有比率為0.05重量份以上。In one embodiment, the content ratio of the fluorine-based compound to 100 parts by weight of the base polymer is 0.05 parts by weight or more.

於一實施方式中，上述基礎聚合物為選自多元醇、胺基甲酸酯預聚物、丙烯酸系樹脂、橡膠系樹脂、矽酮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 polyols, urethane prepolymers, acrylic resins, rubber-based resins, and silicone-based resins.

於一實施方式中，將上述表面保護膜所包含之上述黏著劑層貼合於玻璃板，於溫度23℃下放置30分鐘，然後於溫度23℃下將該表面保護膜以剝離角度180度且剝離速度300 mm/分鐘從該玻璃板剝離，此時剝離力為0.005 N/25 mm～0.1 N/25 mm。In one embodiment, the above-mentioned adhesive layer included in the above-mentioned surface protection film is attached to a glass plate, and placed at a temperature of 23° C. for 30 minutes, and then the surface protection film is held at a temperature of 23° C. at a peeling angle of 180 degrees and The peeling speed was 300 mm/min from the glass plate, and the peeling force at this time was 0.005 N/25 mm to 0.1 N/25 mm.

本發明之實施方式之光學構件係貼合有上述表面保護膜者。The optical member which concerns on embodiment of this invention sticks the said surface protection film.

本發明之實施方式之電子構件係貼合有上述表面保護膜者。 [發明之效果] The electronic component which concerns on embodiment of this invention is what was bonded with the said surface protection film. [Effect of invention]

根據本發明，可提供一種充分地抑制剝離靜電壓而於剝離時不會使該光學構件或該電子構件破損之表面保護膜，該表面保護膜代表性而言為包含黏著劑層之表面保護膜，其於光學構件或電子構件之製造步驟中，為了防止該光學構件或該電子構件之表面於加工、組裝、檢查、運輸等時受損而貼合於該光學構件或該電子構件之露出面。According to the present invention, it is possible to provide a surface protection film that can sufficiently suppress the peeling electrostatic voltage so as not to damage the optical member or the electronic member during peeling, and the surface protection film is typically a surface protection film containing an adhesive layer , which is attached to the exposed surface of the optical component or the electronic component in order to prevent the surface of the optical component or the electronic component from being damaged during processing, assembly, inspection, transportation, etc. during the manufacturing steps of the optical component or electronic component .

≪≪A.表面保護膜≫≫ 本發明之實施方式之表面保護膜包含黏著劑層。 ≪≪A.Surface protection film≫≫ The surface protective film of the embodiment of the present invention includes an adhesive layer.

表面保護膜只要包含黏著劑層即可，亦可於不損害本發明之效果之範圍內，包含任意適當之其他構件。代表性而言，本發明之表面保護膜包含基材層及黏著劑層。The surface protective film only needs to include an adhesive layer, and may include any appropriate other members within a range that does not impair the effects of the present invention. Typically, the surface protective film of the present invention includes a substrate layer and an adhesive layer.

圖1係本發明之一實施方式之表面保護膜之概略剖視圖。於圖1中，表面保護膜10具備基材層1及黏著劑層2。於圖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 protection film according to an embodiment of the present invention. In FIG. 1 , the surface protective 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，於黏著劑層2之與基材層1相反一側之表面，可具備任意適當之剝離襯墊(有時亦稱為剝離片材或隔離件)(未圖示)以於使用之前予以保護等。作為剝離襯墊，可列舉例如：對紙或塑膠膜等基材(襯墊基材)之表面進行矽酮處理所得之剝離襯墊、對紙或塑膠膜等基材(襯墊基材)之表面利用聚烯烴系樹脂進行層壓所得之剝離襯墊等。In FIG. 1, any suitable release liner (sometimes also called release sheet or separator) (not shown) can be provided on the surface of the adhesive layer 2 opposite to the base material layer 1 for use protected before. As the release liner, for example, a release liner obtained by subjecting the surface of a substrate such as paper or a plastic film (liner substrate) to a silicone treatment, a release liner for a substrate such as paper or a plastic film (liner substrate), etc. A release liner etc. obtained by laminating the surface with a polyolefin-based resin.

作為用作襯墊基材之塑膠膜，可列舉例如：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。Examples of the plastic film used as the backing base material include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, and vinyl chloride copolymer. Film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate copolymer film, etc.

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, further preferably 5 μm to 400 μm, particularly 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, further preferably 15 μm to 400 μm, and particularly preferably 20 μm to 300 μm.

表面保護膜所包含之黏著劑層對於該二碘甲烷之表面自由能為6 mJ/m 2～30 mJ/m 2，更佳為8 mJ/m 2～30 mJ/m 2，進而較佳為10 mJ/m 2～30 mJ/m 2，尤佳為12 mJ/m 2～30 mJ/m 2。若表面保護膜所包含之黏著劑層之對於二碘甲烷之表面自由能處於上述範圍內，則可提供一種充分地抑制剝離靜電壓而於剝離時不會使被黏著體(代表性而言，光學構件或電子構件)破損之表面保護膜。若表面保護膜所包含之黏著劑層之對於二碘甲烷之表面自由能偏離上述範圍而過低，則有無法充分地抑制剝離靜電壓之虞。若表面保護膜所包含之黏著劑層之對於二碘甲烷之表面自由能偏離上述範圍而過高，則有污染被黏著體之虞。 The surface free energy of the adhesive layer included in the surface protection film to the diiodomethane is 6 mJ/m 2 ～ 30 mJ/m 2 , more preferably 8 mJ/m 2 ～ 30 mJ/m 2 , and more preferably 10 mJ/m 2 to 30 mJ/m 2 , more preferably 12 mJ/m 2 to 30 mJ/m 2 . If the surface free energy of the adhesive layer contained in the surface protection film to diiodomethane is within the above-mentioned range, it is possible to provide a product that can sufficiently suppress the peeling electrostatic voltage without causing the adherend (representatively, Optical components or electronic components) damaged surface protective film. If the surface free energy with respect to diiodomethane of the adhesive layer contained in the surface protection film deviates from the above-mentioned range and is too low, there is a possibility that the peeling electrostatic voltage cannot be sufficiently suppressed. If the surface free energy to diiodomethane of the adhesive layer included in the surface protection film deviates from the above range and is too high, there is a risk of contamination of the adherend.

再者，表面保護膜所包含之黏著劑層之對於二碘甲烷之表面自由能可如下文所述般容易地測定，藉由以該表面自由能處於上述規定範圍內之方式設計黏著劑層，可提供充分地抑制剝離靜電壓而於剝離時不會使被黏著體(代表性而言，光學構件或電子構件)破損之表面保護膜。此處，以上述黏著劑層作為設計點，於本發明中代表性而言有併用離子性化合物與氟系化合物、及氟化合物之選擇。而且，關於氟化合物之選擇，可列舉例如從特定範疇之氟化合物中選擇上述表面自由能處於上述規定範圍內之氟化合物，關於此種選擇行為，即便業者不反覆進行過度之試誤亦可實施。Furthermore, the surface free energy of the adhesive layer included in the surface protection film with respect to diiodomethane can be easily measured as described below, by designing the adhesive layer in such a way that the surface free energy is within the above-specified range, It is possible to provide a surface protection film that sufficiently suppresses peeling electrostatic voltage and does not damage an adherend (typically, an optical member or an electronic member) during peeling. Here, with the above-mentioned adhesive layer as a design point, typically in the present invention, there is an option to use an ionic compound, a fluorine-based compound, and a fluorine compound in combination. In addition, the selection of the fluorine compound includes, for example, selecting a fluorine compound whose surface free energy is within the predetermined range from among the fluorine compounds in a specific category. Such a selection can be carried out without excessive trial and error by the industry. .

關於表面保護膜所包含之黏著劑層，將其貼合於玻璃板後於溫度23℃下放置30分鐘，然後於溫度23℃下以剝離角度180度且剝離速度300 mm/分鐘將該表面保護膜從該玻璃板剝離，此時剝離力較佳為0.005 N/25 mm～0.1 N/25 mm，更佳為0.007 N/25 mm～0.08 N/25 mm，進而較佳為0.01 N/25 mm～0.05 N/25 mm，尤佳為0.01 N/25 mm～0.03 N/25 mm，最佳為0.01 N/25 mm～0.02 N/25 mm。若上述剝離力處於上述範圍內，則可提供一種不易發生容易地從被黏著體剝離之情況，代表性而言，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後不易發生剝離，且當需要進行剝離時可容易地剝離之表面保護膜。As for the adhesive layer included in the surface protection film, it was attached to a glass plate and then placed at a temperature of 23°C for 30 minutes, and then the surface was protected at a temperature of 23°C with a peeling angle of 180 degrees and a peeling speed of 300 mm/min. The film is peeled off from the glass plate, and the peeling force is preferably 0.005 N/25 mm to 0.1 N/25 mm, more preferably 0.007 N/25 mm to 0.08 N/25 mm, and more preferably 0.01 N/25 mm ~0.05 N/25 mm, preferably 0.01 N/25 mm ~ 0.03 N/25 mm, and most preferably 0.01 N/25 mm ~ 0.02 N/25 mm. If the peeling force is within the above-mentioned range, it is possible to provide a situation in which easy peeling from the adherend is unlikely to occur. The surface protection film is not easy to peel off after the exposed surface of the component, and can be easily peeled off when peeling is required.

表面保護膜可藉由任意適當之方法來製造。作為此種製造方法，可按照例如以下方法等任意適當之製造方法來進行，即： (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)將在隔離件上塗佈黏著劑層之形成材料之溶液或熱熔融液所形成之黏著劑層轉移黏著至基材層上的方法； (3)將黏著劑層之形成材料擠出至基材層上並進行形成塗佈之方法； (4)將基材層與黏著劑層以兩層或多層擠出之方法； (5)於基材層上單層層壓黏著劑層之方法，或者將黏著劑層與層壓層一併進行二層層壓之方法；及 (6)將黏著劑層與膜或層壓層等基材層形成材料進行二層或多層層壓之方法。 The surface protective film can be produced by any appropriate method. As such a manufacturing method, it can be carried out according to any suitable manufacturing method such as the following method, namely: (1) A method of applying a solution or a hot melt solution of a material for forming the adhesive layer on the base material layer; (2) The method of transferring and adhering the adhesive layer formed by coating the solution of the forming material of the adhesive layer on the separator or the hot-melt solution to the base material layer; (3) A method of extruding the forming material of the adhesive layer onto the base material layer and forming a coating; (4) The method of extruding the base material layer and the adhesive layer in two or more layers; (5) A method of single-layer lamination of an adhesive layer on a base material layer, or a method of two-layer lamination of the adhesive layer and the lamination layer together; and (6) A method of laminating two or more layers of an adhesive layer and a substrate layer-forming material such as a film or a laminate layer.

作為塗佈之方法，可使用例如：輥式塗佈機法、缺角輪塗佈機法、模嘴塗佈機法、反向塗佈機法、絲網印刷法、凹版塗佈機法等。As the coating method, for example, a roll coater method, a notch coater method, a die nozzle coater method, a reverse coater method, a screen printing method, a gravure coater method, etc. can be used. .

本發明之實施方式之表面保護膜係充分地抑制剝離靜電壓而於剝離時不會使該光學構件或該電子構件破損之表面保護膜，該表面保護膜代表性而言為包含黏著劑層之表面保護膜，其於光學構件或電子構件之製造步驟中，為了防止該光學構件或該電子構件之表面於加工、組裝、檢查、運輸等時受損而貼合於該光學構件或該電子構件之露出面。The surface protection film of the embodiment of the present invention is a surface protection film which sufficiently suppresses the peeling electrostatic voltage and does not damage the optical member or the electronic member during peeling, and the surface protection film is typically a film containing an adhesive layer. Surface protective film, which is attached to 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, transportation, etc. during the manufacturing steps of the optical member or electronic member the exposed face.

本發明之實施方式之表面保護膜的對玻璃之剝離靜電壓較佳為3.0 kV以下，更佳為2.5 kV以下，進而較佳為2.0 kV以下，尤佳為1.7 kV以下，最佳為1.5 kV以下。關於對玻璃之剝離靜電壓之測定方法，將於下文進行敍述。The peeling electrostatic voltage to glass of the surface protective film according to the embodiment of the present invention is preferably 3.0 kV or less, more preferably 2.5 kV or less, still more preferably 2.0 kV or less, particularly preferably 1.7 kV or less, and most preferably 1.5 kV the following. The measurement method of the peeling electrostatic voltage with respect to glass will be described below.

本發明之實施方式之表面保護膜的對丙烯酸系樹脂板之剝離靜電壓較佳為4.0 kV以下，更佳為3.5 kV以下，進而較佳為3.0 kV以下，進而較佳為2.5 kV以下，尤佳為2.0 kV以下，最佳為1.5 kV以下。關於對丙烯酸系樹脂板之剝離靜電壓之測定方法，將於下文進行敍述。The peeling electrostatic voltage of the surface protective film of the embodiment of the present invention to the acrylic resin plate is preferably 4.0 kV or less, more preferably 3.5 kV or less, still more preferably 3.0 kV or less, still more preferably 2.5 kV or less, especially Preferably it is below 2.0 kV, and most preferably below 1.5 kV. The measurement method of the peeling electrostatic voltage with respect to an acrylic resin board will be described later.

本發明之實施方式之表面保護膜之霧度較佳為5%以下，更佳為4%以下，進而較佳為3%以下，尤佳為2.8%以下，最佳為2.5%以下。若本發明之實施方式之表面保護膜之霧度處於上述範圍內，則適宜用作貼合於光學構件或電子構件之露出面之表面保護膜。尤其是若可使本發明之實施方式之表面保護膜之霧度降低至3%以下，則本發明之實施方式之表面保護膜之檢查性進一步提高，故而更佳。關於霧度之測定方法，將於下文進行敍述。The haze of the surface protective film of the embodiment of the present invention is preferably 5% or less, more preferably 4% or less, still more preferably 3% or less, particularly preferably 2.8% or less, and most preferably 2.5% or less. If the haze of the surface protective film of the embodiment of the present invention is in the above-mentioned range, it is suitable for use as a surface protective film attached to the exposed surface of an optical member or an electronic member. In particular, if the haze of the surface protective film of the embodiment of the present invention can be reduced to 3% or less, the inspection property of the surface protective film of the embodiment of the present invention will be further improved, which is more preferable. The measurement method of the haze will be described below.

本發明之實施方式之表面保護膜的對玻璃之殘留接著力較佳為70%以上，更佳為80%以上，進而較佳為85%以上，尤佳為88%以上，最佳為90%以上。該對玻璃之殘留接著力係表面保護膜之黏著劑層之成分何種程度地轉印至被黏著體表面並是否造成污染之指標。該對玻璃之殘留接著率之值越高，則表面保護膜對被黏著體造成污染之可能性越低，該對玻璃之殘留接著率之值越低，則表面保護膜對被黏著體造成污染之可能性越高。關於該對玻璃之殘留接著率之測定方法，將於下文進行敍述。The residual adhesion to glass of the surface protective film of the embodiment of the present invention is preferably 70% or more, more preferably 80% or more, more preferably 85% or more, particularly preferably 88% or more, and most preferably 90% above. The residual adhesive force to the glass is an indicator of how much the components of the adhesive layer of the surface protection film are transferred to the surface of the adherend and whether it causes pollution. The higher the value of the residual adhesion rate to the glass, the lower the possibility that the surface protective film will contaminate the adherend, and the lower the value of the residual adhesion rate to the glass, the surface protective film will contaminate the adherend the higher the probability. The measurement method of the residual adhesion rate to glass will be described below.

≪A-1.黏著劑層≫ 黏著劑層係由黏著劑構成。黏著劑係由黏著劑組合物形成。即，藉由使由黏著劑組合物形成之黏著劑構成層形狀而成為黏著劑層。 ≪A-1. Adhesive layer≫ The adhesive layer is composed of an adhesive. The adhesive is formed from the adhesive composition. That is, it becomes an adhesive agent layer by making the adhesive agent formed from an adhesive agent composition into a layer shape.

黏著劑可規定為由黏著劑組合物形成者。其原因在於：對於黏著劑而言，由於黏著劑組合物會因加熱或紫外線照射等發生交聯反應等而成為黏著劑，故無法根據黏著劑之結構來直接特定黏著劑，且存在完全不切實際之情況(「不可能/不切實際之情況」)，因此藉由「由黏著劑組合物形成者」之規定而將黏著劑穩妥地特定為「物」。Adhesives can be defined as those formed from the adhesive composition. The reason for this is that, for the adhesive, since the adhesive composition will undergo a cross-linking reaction due to heating or ultraviolet irradiation, etc., and become an adhesive, it is impossible to directly specify the adhesive according to the structure of the adhesive, and there are completely incompatible adhesives. The actual situation ("impossible/impractical situation"), therefore, the adhesive is safely specified as "thing" by the "former from the adhesive composition" rule.

黏著劑層可藉由任意適當之方法形成。作為此種方法，可列舉例如將黏著劑組合物塗佈於任意適當之基材上，視需要進行加熱、乾燥，並視需要使其硬化，而於該基材上形成黏著劑層之方法。作為此種塗佈之方法，可列舉例如：凹版輥式塗佈機、逆輥塗佈機、接觸輥式塗佈機、浸漬輥塗佈機、棒式塗佈機、刮刀塗佈機、氣刀塗佈機、噴霧塗佈機、缺角輪塗佈機、直接塗佈機、輥刷塗佈機等方法。The adhesive layer can be formed by any suitable method. Such a method includes, for example, a method of applying an adhesive composition on any appropriate substrate, heating and drying as necessary, and curing as necessary, and forming an adhesive layer on the substrate. As such a coating method, for example, a gravure roll coater, a reverse roll coater, a touch roll coater, a dip roll coater, a bar coater, a knife coater, a gas Knife coater, spray coater, notch wheel coater, direct coater, roller brush coater and other methods.

關於黏著劑層之厚度，就能進一步表現本發明之效果之方面而言，較佳為0.5 μm～150 μm，更佳為1 μm～100 μm，進而較佳為2 μm～80 μm，尤佳為3 μm～50 μm，最佳為5 μm～30 μm。The thickness of the adhesive layer is preferably 0.5 μm to 150 μm, more preferably 1 μm to 100 μm, further preferably 2 μm to 80 μm, further preferably 2 μm to 80 μm. 3 μm to 50 μm, preferably 5 μm to 30 μm.

黏著劑組合物包含基礎聚合物、離子性化合物及氟系化合物。藉由使黏著劑組合物包含基礎聚合物、離子性化合物及氟系化合物，可提供一種充分地抑制剝離靜電壓而於剝離時不會使該光學構件或該電子構件破損之表面保護膜，該表面保護膜代表性而言為包含黏著劑層之表面保護膜，其於光學構件或電子構件之製造步驟中，為了防止該光學構件或該電子構件之表面於加工、組裝、檢查、運輸等時受損而貼合於該光學構件或該電子構件之露出面。The adhesive composition includes a base polymer, an ionic compound, and a fluorine-based compound. By including the base polymer, the ionic compound and the fluorine-based compound in the adhesive composition, it is possible to provide a surface protection film which sufficiently suppresses the peeling electrostatic voltage and does not damage the optical member or the electronic member during peeling. The surface protection film is typically a surface protection film containing an adhesive layer, which is used in the manufacturing steps of optical members or electronic members to prevent the surface of the optical member or the electronic member from being processed, assembled, inspected, transported, etc. damaged and attached to the exposed surface of the optical component or the electronic component.

於本發明中，藉由使黏著劑組合物除了包含基礎聚合物之外，還包含離子性化合物與氟系化合物兩者，可表現出本發明之效果。尤其是，藉由包含(併用)離子性化合物、與下文所述之較佳實施方式之氟系化合物(有時稱為「特定氟系化合物」)兩者，可顯著地表現出本發明之效果。推測其原因在於，藉由在黏著劑組合物中，使可表現出抗靜電效果之離子性化合物與氟系化合物(較佳為特定氟系化合物)併存，從而利用與氟系化合物(較佳為特定氟系化合物)之協同效應，使離子性化合物偏集存在於黏著劑層之表面側(與被黏著體貼合之側)。In this invention, the effect of this invention can be exhibited by making an adhesive composition contain both an ionic compound and a fluorine-type compound in addition to a base polymer. In particular, the effect of the present invention can be remarkably exhibited by including (combining) both an ionic compound and a fluorine-based compound (sometimes referred to as a "specific fluorine-based compound") of a preferred embodiment described below. . The reason for this is presumed to be that by coexisting an ionic compound that can exhibit an antistatic effect with a fluorine-based compound (preferably a specific fluorine-based compound) in the adhesive composition, the The synergistic effect of the specific fluorine-based compound) makes the ionic compound segregated on the surface side of the adhesive layer (the side attached to the adherend).

關於黏著劑組合物中之基礎聚合物之含有比率，以固形物成分換算計，較佳為60重量%～99.9重量%，更佳為65重量%～99.9重量%，進而較佳為70重量%～99.9重量%，尤佳為75重量%～99.9重量%，最佳為80重量%～99.9重量%。若黏著劑組合物中之基礎聚合物之含有比率以固形物成分換算計處於上述範圍內，則可提供一種充分地抑制剝離靜電壓而於剝離時不會使被黏著體(代表性而言，光學構件或電子構件)破損之表面保護膜。The content ratio of the base polymer in the adhesive composition is preferably 60% by weight to 99.9% by weight, more preferably 65% by weight to 99.9% by weight, and still more preferably 70% by weight in terms of solid content. ~ 99.9 wt %, particularly preferably 75 wt % to 99.9 wt %, and most preferably 80 wt % to 99.9 wt %. If the content ratio of the base polymer in the adhesive composition is within the above-mentioned range in terms of solid content, it is possible to provide a device that can sufficiently suppress the peeling electrostatic voltage without causing the adherend (typically, Optical components or electronic components) damaged surface protective film.

離子性化合物相對於基礎聚合物100重量份之含有比率較佳為0.2重量份以上，更佳為0.3重量份～5.0重量份，進而較佳為0.5重量份～3.0重量份，尤佳為0.7重量份～2.0重量份，最佳為0.8重量份～1.5重量份。若離子性化合物相對於基礎聚合物100重量份之含有比率處於上述範圍內，則可提供一種充分地抑制剝離靜電壓而於剝離時不會使被黏著體(代表性而言，光學構件或電子構件)破損之表面保護膜。若離子性化合物相對於基礎聚合物100重量份之含有比率偏離上述範圍而過低，則有無法充分地抑制剝離靜電壓之虞。若離子性化合物相對於基礎聚合物100重量份之含有比率偏離上述範圍而過高，則有污染被黏著體之虞。The content ratio of the ionic compound to 100 parts by weight of the base polymer is preferably 0.2 parts by weight or more, more preferably 0.3 parts by weight to 5.0 parts by weight, still more preferably 0.5 parts by weight to 3.0 parts by weight, and particularly preferably 0.7 parts by weight parts to 2.0 parts by weight, preferably 0.8 parts to 1.5 parts by weight. When the content ratio of the ionic compound with respect to 100 parts by weight of the base polymer is within the above-mentioned range, it is possible to provide a method that sufficiently suppresses the peeling electrostatic voltage without causing the adherend (typically, an optical member or electronic components) damaged surface protective film. If the content ratio of the ionic compound to 100 parts by weight of the base polymer deviates from the above-mentioned range and is too low, there is a possibility that the peeling electrostatic voltage cannot be sufficiently suppressed. If the content ratio of the ionic compound with respect to 100 parts by weight of the base polymer deviates from the above range and is too high, there is a possibility of contamination of the adherend.

氟系化合物相對於基礎聚合物100重量份之含有比率較佳為0.05重量份以上，更佳為0.1重量份～5.0重量份，進而較佳為0.15重量份～3.0重量份，尤佳為0.2重量份～2.0重量份，最佳為0.23重量份～1.5重量份。若氟系化合物相對於基礎聚合物100重量份之含有比率處於上述範圍內，則可提供一種充分地抑制剝離靜電壓而於剝離時不會使被黏著體(代表性而言，光學構件或電子構件)破損之表面保護膜。若氟系化合物相對於基礎聚合物100重量份之含有比率偏離上述範圍而過低，則有無法充分地抑制剝離靜電壓之虞。若氟系化合物相對於基礎聚合物100重量份之含有比率偏離上述範圍而過高，則有污染被黏著體之虞。The content ratio of the fluorine-based compound to 100 parts by weight of the base polymer is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight to 5.0 parts by weight, still more preferably 0.15 parts by weight to 3.0 parts by weight, and particularly preferably 0.2 parts by weight parts to 2.0 parts by weight, preferably 0.23 parts to 1.5 parts by weight. If the content ratio of the fluorine-based compound to 100 parts by weight of the base polymer is within the above-mentioned range, it is possible to provide a method that sufficiently suppresses the peeling electrostatic voltage without causing the adherend (typically, an optical member or an electronic member) to be peeled off. components) damaged surface protective film. If the content ratio of the fluorine-based compound to 100 parts by weight of the base polymer deviates from the above range and is too low, there is a possibility that the peeling electrostatic voltage cannot be sufficiently suppressed. If the content ratio of the fluorine-based compound to 100 parts by weight of the base polymer deviates from the above range and is too high, there is a possibility of contamination of the adherend.

＜A-1-1.基礎聚合物＞ 基礎聚合物較佳為選自多元醇、胺基甲酸酯預聚物、丙烯酸系樹脂、橡膠系樹脂、矽酮系樹脂中之至少一種。若基礎聚合物為選自多元醇、胺基甲酸酯預聚物、丙烯酸系樹脂、橡膠系樹脂、矽酮系樹脂中之至少一種，則可提供一種更充分地抑制剝離靜電壓而於剝離時使被黏著體(代表性而言，光學構件或電子構件)更不易破損之表面保護膜。 <A-1-1. Base polymer> The base polymer is preferably at least one selected from polyols, urethane prepolymers, acrylic resins, rubber-based resins, and silicone-based resins. If the base polymer is at least one selected from the group consisting of polyols, urethane prepolymers, acrylic resins, rubber-based resins, and silicone-based resins, it is possible to provide a method that more fully suppresses the peeling electrostatic voltage and reduces the peeling off. A surface protective film that makes the adherend (representatively, an optical member or an electronic member) less likely to be damaged.

[A-1-1-1.多元醇] 多元醇較佳為與多官能異氰酸酯化合物反應而成為胺基甲酸酯系樹脂。更具體而言，較佳為由含有多元醇及多官能異氰酸酯化合物之組合物形成胺基甲酸酯系樹脂，詳細而言，使含有多元醇及多官能異氰酸酯化合物之組合物硬化而形成胺基甲酸酯系樹脂。作為使含有多元醇及多官能異氰酸酯化合物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任意適當之方法，諸如使用塊狀聚合或溶液聚合等之胺基甲酸酯化反應方法等。 [A-1-1-1. Polyol] The polyol is preferably reacted with a polyfunctional isocyanate compound to form a urethane resin. More specifically, it is preferable to form a urethane resin from a composition containing a polyhydric alcohol and a polyfunctional isocyanate compound. Specifically, the composition containing a polyhydric alcohol and a polyfunctional isocyanate compound is hardened to form an amine group. Formate resin. As a method of hardening a composition containing a polyol and a polyfunctional isocyanate compound to form a urethane-based resin, any appropriate method such as block polymerization or solution can be adopted within the range not impairing the effects of the present invention The urethane reaction method of polymerization etc., etc.

多元醇可僅為1種，亦可為2種以上。Only one type of polyol may be used, or two or more types may be used.

作為多元醇，可較佳地列舉選自聚酯多元醇、聚醚多元醇、聚己內酯多元醇、聚碳酸酯多元醇、蓖麻油系多元醇中之至少一種。就更能表現本發明之效果之方面而言，作為多元醇，更佳為聚醚多元醇。As the polyol, at least one selected from the group consisting of polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol, and castor oil-based polyol can be preferably used. As the polyol, a polyether polyol is more preferable in that the effect of the present invention can be more exhibited.

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 esterification of a polyol component and an acid component.

作為多元醇成分，可列舉例如：乙二醇、二乙二醇、1,3-丁二醇、1,4-丁二醇、新戊二醇、3-甲基-1,5-戊二醇、2-丁基-2-乙基-1,3-丙二醇、2,4-二乙基-1,5-戊二醇、1,2-己二醇、1,6-己二醇、1,8-辛二醇、1,9-壬二醇、2-甲基-1,8-辛二醇、1,8-癸二醇、十八烷二醇、甘油、三羥甲基丙烷、季戊四醇、己三醇、聚丙二醇等。Examples of polyol components 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, octadecanediol, glycerin, trimethylolpropane , pentaerythritol, hexanetriol, polypropylene glycol, etc.

作為酸成分，可列舉例如：丁二酸、甲基丁二酸、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-萘二羧酸、4,4'-聯苯二羧酸、其等之酸酐等。Examples of the acid component include succinic acid, methylsuccinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid Alkanedioic acid, dimer acid, 2-methyl-1,4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, Phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalene dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, acid anhydrides thereof, and the like.

作為聚醚多元醇，可列舉例如如下聚醚多元醇，其係藉由以水、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)等作為起始劑，使環氧乙烷、環氧丙烷、環氧丁烷等環氧烷進行加成聚合所獲得。具體可列舉例如：聚乙二醇、聚丙二醇、聚1,4-丁二醇等。Examples of polyether polyols include polyether polyols prepared by using water, low molecular weight polyols (propylene glycol, ethylene glycol, glycerol, trimethylolpropane, pentaerythritol, etc.), bisphenols (bisphenols, etc.) Phenol A, etc.), dihydroxybenzene (catechol, resorcinol, hydroquinone, etc.), etc., are used as starting agents, and alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, etc. obtained by addition polymerization. Specifically, polyethylene glycol, polypropylene glycol, poly-1,4-butanediol, etc. are mentioned, for example.

作為聚己內酯多元醇，可列舉例如藉由ε-己內酯、σ-戊內酯等環狀酯單體之開環聚合所獲得之己內酯系聚酯二醇等。Examples of the polycaprolactone polyol include caprolactone-based polyester diols obtained by ring-opening polymerization of cyclic ester monomers such as ε-caprolactone and σ-valerolactone.

作為聚碳酸酯多元醇，可列舉例如如下聚碳酸酯多元醇等：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、碳酸乙丁酯、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2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化合物進行酯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含羥基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共聚而獲得之共聚聚醚系聚碳酸酯多元醇。The polycarbonate polyols include, for example, polycarbonate polyols obtained by polycondensing the above-mentioned polyol components with phosgene; Diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, dibenzyl carbonate and other carbonate diesters Polycarbonate polyols obtained by transesterification condensation; Copolycarbonate polyols obtained by using two or more of the above-mentioned polyol components; Obtained by esterification of the above-mentioned various polycarbonate polyols with carboxyl-containing compounds Polycarbonate polyols; polycarbonate polyols obtained by subjecting the above-mentioned various polycarbonate polyols to an etherification reaction with a hydroxyl-containing compound; Carbonate polyols; polycarbonate polyols obtained by transesterification of the above-mentioned various polycarbonate polyols with hydroxyl-containing compounds; polycondensation obtained by polycondensation reaction of the above-mentioned various polycarbonate polyols with dicarboxylic acid compounds Ester-based polycarbonate polyols; copolyether-based polycarbonate polyols obtained by copolymerizing the above-mentioned various polycarbonate polyols with alkylene oxide.

作為蓖麻油系多元醇，可列舉例如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。具體可列舉例如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。As a castor oil type polyol, the castor oil type polyol obtained by making a castor oil fatty acid react with the said polyol component is mentioned, for example. Specifically, for example, castor oil-based polyols obtained by reacting castor oil fatty acid and polypropylene glycol can be mentioned.

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處於上述範圍內，則可提供一種更不易發生容易地從被黏著體剝離之情況，代表性而言，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後更不易發生剝離，且當需要進行剝離時可更容易地剝離之表面保護膜。The number average molecular weight Mn of the polyol is preferably 300-100,000, more preferably 400-75,000, still more preferably 450-50,000, particularly preferably 500-30,000. If the number-average molecular weight Mn of the polyol is within the above-mentioned range, it is less likely to peel off the adherend easily. The exposed surface of the optical member or the electronic member is less likely to be peeled off later, and a surface protective film that can be peeled off more easily when peeling is required.

多元醇較佳為含有具有3個OH基且數量平均分子量Mn為300～100000之多元醇(A1)。多元醇(A1)可僅為1種，亦可為2種以上。The polyol is preferably a polyol (A1) having three OH groups and a number average molecular weight Mn of 300 to 100,000. Only one type of polyol (A1) may be used, or two or more types may be used.

多元醇中之多元醇(A1)之含有比率較佳為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%，尤佳為70重量%～100重量%，最佳為90重量%～100重量%。若多元醇中之多元醇(A1)之含有比率處於上述範圍內，則可提供一種更不易發生容易地從被黏著體剝離之情況，代表性而言，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後更不易發生剝離，且當需要進行剝離時可更容易地剝離之表面保護膜。The content ratio of the polyol (A1) in the polyol is preferably 5% by weight or more, more preferably 25% by weight to 100% by weight, more preferably 50% by weight to 100% by weight, and particularly preferably 70% by weight to 70% by weight. 100% by weight, preferably 90% by weight to 100% by weight. If the content ratio of the polyol (A1) in the polyol is within the above-mentioned range, it is possible to provide a situation where it is less likely to easily peel off from the adherend, and typically, in the manufacturing steps of optical members or electronic members , a surface protective film that is less likely to peel off after being attached to the exposed surface of the optical component or the electronic component, and can be peeled off more easily when peeling is required.

作為多元醇(A1)，較佳為含有具有3個OH基且數量平均分子量Mn為8000～20000之多元醇(A1a)。多元醇(A1a)可僅為1種，亦可為2種以上。The polyol (A1) preferably contains a polyol (A1a) having three OH groups and a number average molecular weight Mn of 8,000 to 20,000. Only one type of polyol (A1a) may be used, or two or more types may be used.

多元醇(A1)中之多元醇(A1a)之含有比率較佳為50重量%以上，更佳為60重量%～100重量%，進而較佳為70重量%～95重量%，尤佳為75重量%～93重量%，最佳為80重量%～90重量%。若多元醇(A1)中之多元醇(A1a)之含有比率處於上述範圍內，則可提供一種更不易發生容易地從被黏著體剝離之情況，代表性而言，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後更不易發生剝離，且當需要進行剝離時可更容易地剝離之表面保護膜。The content ratio of the polyol (A1a) in the polyol (A1) is preferably 50% by weight or more, more preferably 60% by weight to 100% by weight, further preferably 70% by weight to 95% by weight, and particularly preferably 75% by weight % by weight to 93% by weight, preferably 80% by weight to 90% by weight. If the content ratio of the polyol (A1a) in the polyol (A1) is within the above-mentioned range, it is possible to provide a situation where the peeling from the adherend is less likely to occur, and typically, in the case of an optical member or an electronic member In the manufacturing step, the surface protective film that is less likely to be peeled off after being attached to the exposed surface of the optical component or the electronic component, and can be peeled off more easily when peeling is required.

多元醇(A1a)之數量平均分子量Mn為8000～20000，較佳為8000～18000，更佳為8500～17000，進而較佳為9000～16000，尤佳為9500～15500，最佳為10000～15000。若多元醇(A1a)之數量平均分子量Mn處於上述範圍內，則可提供一種更不易發生容易地從被黏著體剝離之情況，代表性而言，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後更不易發生剝離，且當需要進行剝離時可更容易地剝離之表面保護膜。The number average molecular weight Mn of the polyol (A1a) is 8,000-20,000, preferably 8,000-18,000, more preferably 8,500-17,000, more preferably 9,000-16,000, particularly preferably 9,500-15,500, and most preferably 10,000-15,000 . If the number-average molecular weight Mn of the polyol (A1a) is within the above-mentioned range, a situation that is less likely to be easily peeled off from the adherend can be provided. A surface protective film that is less likely to peel off after being attached to the exposed surface of the optical member or the electronic member, and can be peeled off more easily when peeling is required.

多元醇(A1)亦可含有具有3個以上之OH基且數量平均分子量Mn為5000以下之多元醇(A1b)。多元醇(A1b)可僅為1種，亦可為2種以上。The polyol (A1) may contain a polyol (A1b) having three or more OH groups and having a number average molecular weight Mn of 5,000 or less. Only one type of polyol (A1b) may be used, or two or more types may be used.

多元醇(A1b)較佳為選自具有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)中之至少一種。The polyol (A1b) is preferably selected from the group consisting of polyols having 3 OH groups (triols), polyols having 4 OH groups (tetraols), polyols having 5 OH groups (pentanols), At least one of polyols (hexaols) with 6 OH groups.

多元醇(A1)中之多元醇(A1b)之含有比率較佳為50重量%以下，更佳為0重量%～40重量%，進而較佳為5重量%～30重量%，尤佳為7重量%～25重量%，最佳為10重量%～20重量%。若多元醇(A1)中之多元醇(A1b)之含有比率處於上述範圍內，則可提供一種更不易發生容易地從被黏著體剝離之情況，代表性而言，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後更不易發生剝離，且當需要進行剝離時可更容易地剝離之表面保護膜。The content ratio of the polyol (A1b) in the polyol (A1) is preferably 50% by weight or less, more preferably 0% by weight to 40% by weight, further preferably 5% by weight to 30% by weight, particularly preferably 7% by weight % by weight to 25% by weight, preferably 10% by weight to 20% by weight. If the content ratio of the polyol (A1b) in the polyol (A1) is within the above-mentioned range, it is possible to provide a situation in which peeling from the adherend is less likely to occur, and typically, in optical members or electronic members In the manufacturing step, the surface protective film that is less likely to be peeled off after being attached to the exposed surface of the optical component or the electronic component, and can be peeled off more easily when peeling is required.

多元醇(A1b)之數量平均分子量Mn較佳為500～5000，更佳為600～4500，進而較佳為700～4000，尤佳為800～3500，最佳為900～3300。若多元醇(A1b)之數量平均分子量Mn處於上述範圍內，則可提供一種更不易發生容易地從被黏著體剝離之情況，代表性而言，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後更不易發生剝離，且當需要進行剝離時可更容易地剝離之表面保護膜。若多元醇(A1b)之數量平均分子量Mn偏離上述範圍，則尤其存在黏著力之經時上升性變高之擔憂，而有無法表現出優異之二次加工性之虞。The number average molecular weight Mn of the polyol (A1b) is preferably 500-5000, more preferably 600-4500, further preferably 700-4000, particularly preferably 800-3500, and most preferably 900-3300. If the number-average molecular weight Mn of the polyol (A1b) is within the above-mentioned range, a situation that is less likely to be easily peeled off from the adherend can be provided. A surface protective film that is less likely to peel off after being attached to the exposed surface of the optical member or the electronic member, and can be peeled off more easily when peeling is required. If the number-average molecular weight Mn of the polyol (A1b) deviates from the above-mentioned range, there is a fear that the time-dependent increase in adhesive force in particular becomes high, and there is a possibility that the excellent secondary processability cannot be expressed.

於多元醇(A1b)為選自具有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)中之至少一種之情形時，其等之合計量係以於多元醇(A1)中之含有比率計，較佳為40重量%以下，更佳為0重量%～30重量%，進而較佳為3重量%～20重量%，尤佳為5重量%～15重量%，最佳為7重量%～10重量%。若多元醇(A1)中，多元醇(A1b)為選自具有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)中之至少一種之情形時其等之合計量處於上述範圍內，則可提供一種更不易發生容易地從被黏著體剝離之情況，代表性而言，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後更不易發生剝離，且當需要進行剝離時可更容易地剝離之表面保護膜。又，可成為透明性優異之表面保護膜。The polyol (A1b) is at least one selected from the group consisting of polyols having 4 OH groups (tetraols), polyols having 5 OH groups (pentanols), and polyols having 6 OH groups (hexaols) In one case, the total amount thereof is based on the content ratio in the polyol (A1), preferably 40% by weight or less, more preferably 0 to 30% by weight, and more preferably 3% by weight ~ 20% by weight, particularly preferably 5% by weight to 15% by weight, and most preferably 7% by weight to 10% by weight. If in the polyol (A1), the polyol (A1b) is selected from the group consisting of a polyol (tetraol) having 4 OH groups, a polyol (pentaol) having 5 OH groups, and a polyol having 6 OH groups In the case of at least one of (hexaol), when the total amount thereof is within the above-mentioned range, it is possible to provide a situation in which it is less likely to easily peel off from the adherend, and typically, in optical or electronic components In the manufacturing step, the surface protective film that is less likely to be peeled off after being attached to the exposed surface of the optical component or the electronic component, and can be peeled off more easily when peeling is required. Moreover, it can become a surface protective film excellent in transparency.

關於多元醇(A1b)中選自具有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)中之至少一種之含有比率，相對於多元醇(A1)整體，較佳為未達10重量%，更佳為7重量%以下，進而較佳為5重量%以下，尤佳為3重量%以下，最佳為1重量%以下。若多元醇(A1b)中之選自具有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)中之至少一種之含有比率處於上述範圍內，則可提供一種更不易發生容易地從被黏著體剝離之情況，代表性而言，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後更不易發生剝離，且當需要進行剝離時可更容易地剝離之表面保護膜。又，若多元醇(A1b)中之選自具有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)中之至少一種之含有比率偏離上述範圍，則有表面保護膜之透明性下降之虞。Regarding the polyol (A1b), at least one selected from the group consisting of polyols having 4 OH groups (tetraols), polyols having 5 OH groups (pentanols), and polyols having 6 OH groups (hexaols) The content ratio of one is preferably less than 10 wt %, more preferably 7 wt % or less, more preferably 5 wt % or less, particularly preferably 3 wt % or less, with respect to the entire polyol (A1), most preferably It is 1 weight% or less. If the polyol (A1b) is selected from the polyol with 4 OH groups (tetraol), the polyol with 5 OH groups (pentaol), and the polyol with 6 OH groups (hexaol) If the content ratio of at least one of them is within the above-mentioned range, a situation that is less likely to be easily peeled off from the adherend can be provided. The exposed surface of the electronic component is less likely to be peeled off, and the surface protective film can be peeled off more easily when peeling is required. Also, if the polyol (A1b) is selected from the group consisting of a polyol having 4 OH groups (tetraol), a polyol having 5 OH groups (pentaol), and a polyol having 6 OH groups (hexaol) When the content ratio of at least one of them deviates from the above-mentioned range, the transparency of the surface protective film may be lowered.

多元醇(A1)亦可含有具有4個以上之OH基且數量平均分子量Mn為20000以下之多元醇(A1c)。多元醇(A1c)可僅為1種，亦可為2種以上。The polyol (A1) may contain a polyol (A1c) having four or more OH groups and having a number average molecular weight Mn of 20,000 or less. Only one type of polyol (A1c) may be used, or two or more types may be used.

多元醇(A1)中之具有4個以上之OH基且數量平均分子量Mn為20000以下之多元醇(A1c)之含有比率較佳為未達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。若多元醇(A1)中之具有4個以上之OH基之數量平均分子量Mn為20000以下之多元醇(A1c)之含有比率處於上述範圍內，則可提供一種更不易發生容易地從被黏著體剝離之情況，代表性而言，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後更不易發生剝離，且當需要進行剝離時可更容易地剝離之表面保護膜。又，可成為透明性優異之表面保護膜。In the polyol (A1), the content ratio of the polyol (A1c) having 4 or more OH groups and the number average molecular weight Mn of 20,000 or less is preferably less than 70% by weight, more preferably 60% by weight or less, and more It is preferably 50% by weight or less, more preferably 40% by weight or less, and most preferably 30% by weight or less. If the content ratio of the polyol (A1c) having 4 or more OH groups and the number-average molecular weight Mn of 20,000 or less in the polyol (A1) is within the above-mentioned range, it is possible to provide a product that is less likely to easily separate from the adherend. In the case of peeling, typically, in the manufacturing step of an optical member or an electronic member, it is less likely to peel off after being attached to the exposed surface of the optical member or the electronic member, and it can be peeled off more easily when peeling is required. surface protective film. Moreover, it can become a surface protective film excellent in transparency.

[A-1-1-2.胺基甲酸酯預聚物] 胺基甲酸酯預聚物較佳為與多官能異氰酸酯化合物反應而成為胺基甲酸酯系樹脂。更具體而言，較佳為由含有胺基甲酸酯預聚物與多官能異氰酸酯化合物之組合物形成胺基甲酸酯系樹脂，詳細而言，使含有胺基甲酸酯預聚物與多官能異氰酸酯化合物之組合物硬化而形成胺基甲酸酯系樹脂。作為使含有多元醇與多官能異氰酸酯化合物之組合物硬化而形成胺基甲酸酯系樹脂之方法，可採用任意適當之製造方法，只要使用所謂「胺基甲酸酯預聚物」作為原料來製造胺基甲酸酯系樹脂即可。 [A-1-1-2. Urethane Prepolymer] The urethane prepolymer is preferably reacted with a polyfunctional isocyanate compound to form a urethane resin. More specifically, it is preferable to form a urethane resin from a composition containing a urethane prepolymer and a polyfunctional isocyanate compound. The composition of the polyfunctional isocyanate compound hardens to form a urethane resin. As a method of hardening a composition containing a polyol and a polyfunctional isocyanate compound to form a urethane resin, any appropriate production method can be adopted, as long as a so-called "urethane prepolymer" is used as a raw material. What is necessary is just to manufacture a urethane resin.

再者，本發明之說明中，「胺基甲酸酯預聚物」係指於胺基甲酸酯樹脂之製造中業者通常所稱之「胺基甲酸酯預聚物」，與A-1-1-1項中所說明之「多元醇」不同。Furthermore, in the description of the present invention, "urethane prepolymer" refers to what is commonly called "urethane prepolymer" in the manufacture of urethane resin, and A- The "polyol" described in Item 1-1-1 is different.

胺基甲酸酯預聚物可僅為1種，亦可為2種以上。Only one type of urethane prepolymer may be used, or two or more types may be used.

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 3,000 to 1,000,000.

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)分別單獨地，或者以(a1)與(a2)之混合物之形式，在觸媒存在下或無觸媒條件下與多官能異氰酸酯化合物反應而成者。聚酯多元醇(a1)可僅為1種，亦可為2種以上。聚醚多元醇(a2)可僅為1種，亦可為2種以上。The urethane prepolymer is preferably a polyurethane polyol, more preferably the polyester polyol (a1) or the polyether polyol (a2) is used alone, or as (a1) and (a1) In the form of mixture of a2), it is formed by reacting with a polyfunctional isocyanate compound in the presence or absence of a catalyst. Only one type of polyester polyol (a1) may be used, or two or more types may be used. Only one type of polyether polyol (a2) may be used, or two or more types may be used.

作為聚酯多元醇(a1)，可使用任意適當之聚酯多元醇。作為此種聚酯多元醇(a1)，可列舉例如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，可列舉例如：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，可列舉例如：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)，除上述以外，還可列舉使聚己內酯、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. As such a polyester polyol (a1), the polyester polyol obtained by making an acid component and a diol component react, for example is mentioned. As an acid component, terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, trimellitic acid, etc. are mentioned, for example. As a glycol component, for example, ethylene glycol, propylene glycol, diethylene glycol, butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'- Dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol; as polyol components, glycerin, trihydroxy Methyl propane, pentaerythritol, etc. As the polyester polyol (a1), in addition to the above, those obtained by ring-opening polymerization of lactones such as polycaprolactone, poly(β-methyl-γ-valerolactone), and polyvalerolactone can be used. Polyester polyols, etc.

作為聚酯多元醇(a1)之分子量，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Mn較佳為100～100000。若數量平均分子量Mn未達100，則有反應性變高而容易凝膠化之虞。若數量平均分子量Mn超過100000，則有反應性變低，進而聚胺基甲酸酯多元醇本身之凝聚力變小之虞。關於聚酯多元醇(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%。As the molecular weight of the polyester polyol (a1), a low molecular weight to a high molecular weight can be used. As the molecular weight of the polyester polyol (a1), the number average molecular weight Mn is preferably 100 to 100,000. If the number average molecular weight Mn is less than 100, the reactivity may become high, and there is a possibility that gelation is likely to occur. When the number average molecular weight Mn exceeds 100,000, there is a possibility that the reactivity will become low and the cohesive force of the polyurethane polyol itself will become small. The usage-amount of the polyester polyol (a1) is preferably 0 mol % to 90 mol % in the polyol constituting the polyurethane polyol.

作為聚醚多元醇(a2)，可使用任意適當之聚醚多元醇。作為此種聚醚多元醇(a2)，可列舉例如藉由使用水、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、四氫呋喃等氧

Figure 111101602-1
(oxirane)化合物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，可列舉例如聚丙二醇、聚乙二醇、聚1,4-丁二醇等官能基數為2以上之聚醚多元醇。As the polyether polyol (a2), any appropriate polyether polyol can be used. As such polyether polyol (a2), for example, ethylene oxide, epoxy Oxygen such as propane, butylene oxide, tetrahydrofuran
Figure 111101602-1
(oxirane) polyether polyol obtained by polymerizing compounds. Specific examples of such polyether polyol (a2) include polyether polyols having 2 or more functional groups, such as polypropylene glycol, polyethylene glycol, and poly-1,4-butanediol.

作為聚醚多元醇(a2)之分子量，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Mn較佳為100～100000。若數量平均分子量Mn未達100，則有反應性變高而容易凝膠化之虞。若數量平均分子量Mn超過100000，則有反應性變低，進而聚胺基甲酸酯多元醇本身之凝聚力變小之虞。關於聚醚多元醇(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%。As the molecular weight of the polyether polyol (a2), a low molecular weight to a high molecular weight can be used. As the molecular weight of the polyether polyol (a2), the number average molecular weight Mn is preferably 100 to 100,000. If the number average molecular weight Mn is less than 100, the reactivity may become high, and there is a possibility that gelation is likely to occur. When the number average molecular weight Mn exceeds 100,000, there is a possibility that the reactivity will become low and the cohesive force of the polyurethane polyol itself will become small. The usage-amount of the polyether polyol (a2) is preferably 0 mol % to 90 mol % in the polyol constituting the polyurethane polyol.

關於聚醚多元醇(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、異佛爾酮二胺、苯二甲胺等多胺類等並進行併用。Regarding the polyether polyol (a2), a part of it may be replaced with ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, and pentaerythritol as necessary Diols such as ethylenediamine, N-aminoethylethanolamine, isophoronediamine, and polyamines such as xylylenediamine are used in combination.

作為聚醚多元醇(a2)，可僅使用2官能性聚醚多元醇，亦可一部分或全部使用數量平均分子量Mn為100～100000且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)，若一部分或全部使用數量平均分子量Mn為100～100000且1分子中具有至少3個以上之羥基之聚醚多元醇，則可使黏著力與再剝離性之平衡良好。於此種聚醚多元醇中，若數量平均分子量Mn未達100，則有反應性變高而容易凝膠化之虞。又，於此種聚醚多元醇中，若數量平均分子量Mn超過100000，則有反應性變低，進而聚胺基甲酸酯多元醇本身之凝聚力變小之虞。此種聚醚多元醇之數量平均分子量Mn更佳為100～10000。As the polyether polyol (a2), only a bifunctional polyether polyol may be used, or a part or all of a polyether polyol having a number average molecular weight Mn of 100 to 100,000 and having at least three or more hydroxyl groups in one molecule may be used. . As the polyether polyol (a2), if a part or all of a polyether polyol having a number average molecular weight Mn of 100 to 100,000 and having at least 3 or more hydroxyl groups in one molecule is used, the adhesive force and the releasability can be balanced. good. In such a polyether polyol, when the number average molecular weight Mn is less than 100, the reactivity becomes high and there is a possibility that gelation is likely to occur. Moreover, in such a polyether polyol, when the number average molecular weight Mn exceeds 100,000, there is a possibility that the reactivity will become low and the cohesion force of the polyurethane polyol itself will become small. The number average molecular weight Mn of such a polyether polyol is more preferably 100-10,000.

作為獲得聚胺基甲酸酯多元醇時可使用之觸媒，可使用任意適當之觸媒。作為此種觸媒，可列舉例如：三級胺系化合物、有機金屬系化合物等。Any appropriate catalyst can be used as a catalyst that can be used when obtaining a polyurethane polyol. As such a catalyst, a tertiary amine compound, an organometallic compound, etc. are mentioned, for example.

作為三級胺系化合物，可列舉例如：三乙胺、三伸乙二胺、1,8-二氮雜雙環(5,4,0)-十一碳烯-7(DBU)等。As a tertiary amine type compound, triethylamine, triethylenediamine, 1, 8- diazabicyclo (5,4,0)-undecene-7 (DBU) etc. are mentioned, for example.

作為有機金屬系化合物，可列舉例如：錫系化合物、非錫系化合物等。As an organometallic compound, a tin type compound, a non-tin type compound, etc. are mentioned, for example.

作為錫系化合物，可列舉例如：二氯化二丁基錫、氧化二丁基錫、二溴化二丁基錫、二馬來酸二丁基錫、二月桂酸二丁基錫(DBTDL)、二乙酸二丁基錫、硫化二丁基錫、硫化三丁基錫、氧化三丁基錫、乙酸三丁基錫、三乙基乙醇錫、三丁基乙醇錫、氧化二辛基錫、氯化三丁基錫、三氯乙酸三丁基錫、2-乙基己酸錫等。Examples of tin-based compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, Tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate, etc.

作為非錫系化合物，可列舉例如如下等：二氯化二丁基鈦、鈦酸四丁酯、三氯化丁氧基鈦等鈦系化合物；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。Examples of non-tin-based compounds include titanium-based compounds such as dibutyltitanium dichloride, tetrabutyl titanate, and butoxytitanium trichloride; lead oleate, lead 2-ethylhexanoate, Lead compounds such as lead benzoate and lead naphthenate; iron compounds such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; naphthenic acid Zinc-based compounds such as zinc and zinc 2-ethylhexanoate; zirconium-based compounds such as zirconium naphthenate.

於在獲得聚胺基甲酸酯多元醇時使用觸媒之情形時，若為存在聚酯多元醇與聚醚多元醇這兩種多元醇之系統，則其反應性會有所不同，因此於單獨觸媒之系統中容易產生凝膠化或反應溶液渾濁之問題。因此，藉由在獲得聚胺基甲酸酯多元醇時使用兩種觸媒，容易對反應速度、觸媒之選擇性等進行控制，而能解決該等問題。作為此種兩種觸媒之組合，可列舉例如：三級胺/有機金屬系、錫系/非錫系、錫系/錫系，較佳為錫系/錫系，更佳為二月桂酸二丁基錫與2-乙基己酸錫之組合。關於上述二月桂酸二丁基錫與2-乙基己酸錫之組合之調配比，以重量比計，2-乙基己酸錫/二月桂酸二丁基錫較佳為未達1，更佳為0.2～0.6。若調配比為1以上，則有因觸媒活性之平衡而變得容易凝膠化之虞。In the case of using a catalyst to obtain a polyurethane polyol, if it is a system of two polyols, a polyester polyol and a polyether polyol, the reactivity will be different. In the system of single catalyst, the problem of gelation or turbidity of the reaction solution is easy to occur. Therefore, by using two catalysts when obtaining a polyurethane polyol, it becomes easy to control a reaction rate, selectivity of a catalyst, etc., and these problems can be solved. As a combination of such two catalysts, for example, tertiary amine/organometallic, tin/non-tin, tin/tin, preferably tin/tin, more preferably dilauric acid A combination of dibutyltin and tin 2-ethylhexanoate. Regarding the above-mentioned compounding ratio of the combination of dibutyltin dilaurate and tin 2-ethylhexanoate, in terms of weight ratio, tin 2-ethylhexanoate/dibutyltin dilaurate is preferably less than 1, more preferably 0.2 ~0.6. When the compounding ratio is 1 or more, there is a possibility that gelation is likely to occur due to the balance of catalyst activity.

於在獲得聚胺基甲酸酯多元醇時使用觸媒之情形時，觸媒之使用量係相對於聚酯多元醇(a1)、聚醚多元醇(a2)及多官能異氰酸酯化合物之總量，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 polyfunctional isocyanate compound , preferably 0.01% by weight to 1.0% by weight.

於在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℃。若變為100℃以上，則有難以控制反應速度及交聯結構之虞，而有難以獲得具有規定分子量之聚胺基甲酸酯多元醇之虞。When a catalyst is used for obtaining a polyurethane polyol, the reaction temperature is preferably less than 100°C, more preferably 85°C to 95°C. When it becomes 100 degreeC or more, there exists a possibility that it may become difficult to control a reaction rate and a crosslinked structure, and there exists a possibility that it may become difficult to obtain the polyurethane polyol which has a predetermined molecular weight.

於獲得聚胺基甲酸酯多元醇時，亦可不使用觸媒。於該情形時，反應溫度較佳為100℃以上，更佳為110℃以上。又，於在無觸媒條件下獲得聚胺基甲酸酯多元醇時，較佳為使其反應3小時以上。When obtaining a polyurethane polyol, a catalyst may not be used. In this case, the reaction temperature is preferably 100°C or higher, more preferably 110°C or higher. Moreover, when obtaining a polyurethane polyol without a catalyst, it is preferable to make it react for 3 hours or more.

作為獲得聚胺基甲酸酯多元醇之方法，可列舉例如：1)將聚酯多元醇、聚醚多元醇、觸媒、多官能異氰酸酯化合物加入全量燒瓶中之方法；2)將聚酯多元醇、聚醚多元醇、觸媒加入燒瓶後滴加地添加多官能異氰酸酯化合物之方法。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 of obtaining a polyurethane polyol, for example, 1) a method of adding a polyester polyol, a polyether polyol, a catalyst, and a polyfunctional isocyanate compound to a total amount of a flask; 2) a polyester polyol The method of adding the polyfunctional isocyanate compound dropwise after adding the alcohol, polyether polyol and catalyst to the flask. As a method of 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，可使用任意適當之溶劑。作為此種溶劑，可列舉例如：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 can be used. As such a solvent, methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, etc. are mentioned, for example. Among these solvents, toluene is preferred.

[A-1-1-3.丙烯酸系樹脂] 作為丙烯酸系樹脂，可於不損害本發明之效果之範圍內，採用任意適當之丙烯酸系樹脂。丙烯酸系樹脂可僅為1種，亦可為2種以上。 [A-1-1-3. Acrylic resin] As the acrylic resin, any appropriate acrylic resin can be used within a range that does not impair the effects of the present invention. Only one type of acrylic resin may be used, or two or more types may be used.

關於丙烯酸系樹脂之重量平均分子量，就更能表現本發明之效果之方面而言，較佳為30萬～250萬，更佳為35萬～200萬，進而較佳為40萬～180萬，尤佳為50萬～150萬。The weight average molecular weight of the acrylic resin is preferably 300,000 to 2,500,000, more preferably 350,000 to 2,000,000, and further preferably 400,000 to 1,800,000, from the viewpoint of more capable of exhibiting the effects of the present invention, In particular, it is 500,000 to 1,500,000.

作為丙烯酸系樹脂，就更能表現本發明之效果之方面而言，較佳為由包含(a成分)烷基酯部分之烷基之碳數為4～12之(甲基)丙烯酸烷基酯、及(b成分)選自由具有OH基之(甲基)丙烯酸酯及(甲基)丙烯酸所組成之群中之至少一種的、組合物(B)藉由聚合而形成之丙烯酸系樹脂。(a成分)、(b成分)分別獨立地可僅為1種，亦可為2種以上。The acrylic resin is preferably an alkyl (meth)acrylate having 4 to 12 carbon atoms in an alkyl group including an alkyl ester moiety (component a), in terms of exhibiting the effects of the present invention. , and (b component) at least one selected from the group consisting of (meth)acrylate and (meth)acrylic acid having an OH group, the composition (B) is an acrylic resin formed by polymerization. (a component) and (b component) each independently may be only 1 type, and may be 2 or more types.

作為烷基酯部分之烷基之碳數為4～12之(甲基)丙烯酸烷基酯(a成分)，可列舉例如：(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸十一烷基酯、(甲基)丙烯酸十二烷基酯等。其中，就更能表現本發明之效果之方面而言，較佳為(甲基)丙烯酸正丁酯、(甲基)丙烯酸2-乙基己酯，更佳為丙烯酸正丁酯、丙烯酸2-乙基己酯。The alkyl (meth)acrylate (component a) having 4 to 12 carbon atoms in the alkyl ester moiety includes, for example, n-butyl (meth)acrylate and isobutyl (meth)acrylate. , 2nd butyl (meth)acrylate, 3rd butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, (meth)acrylic acid Octyl ester, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, ( Isodecyl meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, and the like. Among them, n-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are preferred, and n-butyl acrylate and 2- Ethylhexyl ester.

作為選自由具有OH基之(甲基)丙烯酸酯及(甲基)丙烯酸所組成之群中之至少一種(b成分)，可列舉例如：(甲基)丙烯酸羥乙酯、(甲基)丙烯酸羥丙酯、(甲基)丙烯酸羥丁酯等具有OH基之(甲基)丙烯酸酯、(甲基)丙烯酸等。其中，就更能表現本發明之效果之方面而言，較佳為(甲基)丙烯酸羥乙酯、(甲基)丙烯酸，更佳為丙烯酸羥乙酯、丙烯酸。As at least one (b component) selected from the group consisting of (meth)acrylate and (meth)acrylic acid having an OH group, for example, hydroxyethyl (meth)acrylate, (meth)acrylic acid may be mentioned. (meth)acrylates having OH groups, such as hydroxypropyl ester and hydroxybutyl (meth)acrylate, (meth)acrylic acid, and the like. Among them, hydroxyethyl (meth)acrylate and (meth)acrylic acid are preferred, and hydroxyethyl acrylate and acrylic acid are more preferred in terms of the effect of the present invention.

組合物(B)亦可含有除(a)成分及(b)成分外之共聚性單體。共聚性單體可僅為1種，亦可為2種以上。作為此種共聚性單體，可列舉例如如下等：伊康酸、馬來酸、富馬酸、丁烯酸、異丁烯酸、其等之酸酐(例如，馬來酸酐、伊康酸酐等含酸酐基單體)等含羧基單體(其中，(甲基)丙烯酸除外)；(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-甲氧基甲基(甲基)丙烯醯胺、N-丁氧基甲基(甲基)丙烯醯胺、N-羥乙基(甲基)丙烯醯胺等含醯胺基單體；(甲基)丙烯酸胺基乙酯、(甲基)丙烯酸二甲基胺基乙酯、(甲基)丙烯酸第三丁基胺基乙酯等含胺基單體；(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸甲基縮水甘油酯等含環氧基單體；丙烯腈或甲基丙烯腈等含氰基單體；N-乙烯基-2-吡咯啶酮、(甲基)丙烯醯𠰌啉、N-乙烯基哌啶酮、N-乙烯基哌𠯤、N-乙烯基吡咯、N-乙烯基咪唑、乙烯基吡啶、乙烯基嘧啶、乙烯基㗁唑等含雜環之乙烯系單體；乙烯基磺酸鈉等含磺酸基單體；2-羥乙基丙烯醯基磷酸酯等含磷酸基單體；環己基馬來醯亞胺、異丙基馬來醯亞胺等含亞胺基單體；異氰酸2-甲基丙烯醯氧基乙酯等含異氰酸酯基單體；(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異𦯉基酯等具有脂環式烴基之(甲基)丙烯酸酯；(甲基)丙烯酸苯酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸苄酯等具有芳香族烴基之(甲基)丙烯酸酯；乙酸乙烯酯、丙酸乙烯酯等乙烯酯；苯乙烯、乙烯基甲苯等芳香族乙烯系化合物；乙烯、丁二烯、異戊二烯、異丁烯等烯烴類或二烯類；乙烯基烷基醚等乙烯醚類；氯乙烯。The composition (B) may contain comonomers other than (a) component and (b) component. Only one type of copolymerizable monomer may be used, or two or more types may be used. Examples of such copolymerizable monomers include itaconic acid, maleic acid, fumaric acid, crotonic acid, methacrylic acid, and acid anhydrides thereof (for example, acid anhydrides such as maleic anhydride and itaconic anhydride) carboxyl group-containing monomers) and other carboxyl group-containing monomers (excluding (meth)acrylic acid); (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-methylol (methyl) base) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, etc. Amino-based monomers; amino-group-containing monomers such as aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and tert-butylaminoethyl (meth)acrylate; ( Epoxy group-containing monomers such as glycidyl meth)acrylate and methyl glycidyl (meth)acrylate; cyano group-containing monomers such as acrylonitrile or methacrylonitrile; N-vinyl-2-pyrrolidone , (meth)acrylonitrile, N-vinylpiperidone, N-vinylpiperidone, N-vinylpyrrole, N-vinylimidazole, vinylpyridine, vinylpyrimidine, vinyloxazole, etc. Heterocycle-containing vinyl monomers; sulfonic acid group-containing monomers such as sodium vinylsulfonate; phosphoric acid group-containing monomers such as 2-hydroxyethylacryloyl phosphate; cyclohexylmaleimide, isopropyl Isocyanate group-containing monomers such as maleimide; isocyanate group-containing monomers such as 2-methacryloyloxyethyl isocyanate; (meth)acrylate cyclopentyl, (meth)acrylate , (meth)acrylates with alicyclic hydrocarbon groups such as iso(meth)acrylates; phenyl(meth)acrylates, phenoxyethyl(meth)acrylates, benzyl(meth)acrylates (meth)acrylates with aromatic hydrocarbon groups; vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene and vinyltoluene; ethylene, butadiene, isoprene, isobutylene and other olefins or dienes; vinyl ethers such as vinyl alkyl ethers; vinyl chloride.

作為共聚性單體，亦可採用多官能性單體。多官能性單體係指於1分子中具有2個以上之乙烯性不飽和基之單體。作為乙烯性不飽和基，可於不損害本發明之效果之範圍內，採用任意適當之乙烯性不飽和基。作為此種乙烯性不飽和基，可列舉例如：乙烯基、丙烯基、異丙烯基、乙烯基醚基(乙烯基氧基)、烯丙醚基(烯丙氧基)等自由基聚合性官能基。作為多官能性單體，可列舉例如：己二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、(聚)乙二醇二(甲基)丙烯酸酯、(聚)丙烯乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基甲烷三(甲基)丙烯酸酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸乙烯酯、二乙烯苯、環氧丙烯酸酯、聚酯丙烯酸酯、丙烯酸胺基甲酸酯等。此種多官能性單體可僅為1種，亦可為2種以上。As a copolymerizable monomer, a polyfunctional monomer can also be used. The polyfunctional monomer system refers to a monomer having two or more ethylenically unsaturated groups in one molecule. As the ethylenically unsaturated group, any appropriate ethylenically unsaturated group can be used within a range not impairing the effects of the present invention. Examples of such ethylenically unsaturated groups include radically polymerizable functional groups such as vinyl groups, propenyl groups, isopropenyl groups, vinyl ether groups (vinyloxy groups), and allyl ether groups (allyloxy groups). base. As the polyfunctional monomer, for example, hexanediol di(meth)acrylate, butanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly) Propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate Esters, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, allyl(meth)acrylate, vinyl(meth)acrylate, divinylbenzene, cyclic Oxyacrylate, polyester acrylate, urethane acrylate, etc. Only one type of such a polyfunctional monomer may be sufficient as it, and two or more types may be sufficient as it.

作為共聚性單體，亦可採用(甲基)丙烯酸烷氧基烷基酯。作為(甲基)丙烯酸烷氧基烷基酯，可列舉例如：(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸甲氧基三乙二醇酯、(甲基)丙烯酸3-甲氧基丙酯、(甲基)丙烯酸3-乙氧基丙酯、(甲基)丙烯酸4-甲氧基丁酯、(甲基)丙烯酸4-乙氧基丁酯等。(甲基)丙烯酸烷氧基烷基酯可僅為1種，亦可為2種以上。As a comonomer, (meth)acrylic-acid alkoxyalkyl ester can also be used. Examples of alkoxyalkyl (meth)acrylates include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and methoxy (meth)acrylate. triethylene glycol, 3-methoxypropyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, (methyl) 4-ethoxybutyl acrylate, etc. Only one type of alkoxyalkyl (meth)acrylate may be used, or two or more types may be used.

關於烷基酯部分之烷基之碳數為4～12之(甲基)丙烯酸烷基酯(a成分)之含量，就更能表現本發明之效果之方面而言，相對於構成丙烯酸系聚合物之單體成分全量(100重量%)，較佳為30重量%以上，更佳為35重量%～99重量%，進而較佳為40重量%～98重量%，尤佳為50重量%～95重量%。Regarding the content of the alkyl (meth)acrylate (component a) having 4 to 12 carbon atoms in the alkyl ester moiety, the effect of the present invention can be more exhibited than the content of the acrylic polymer constituting the acrylic polymer. The total amount of monomer components (100% by weight) is preferably 30% by weight or more, more preferably 35% by weight to 99% by weight, more preferably 40% by weight to 98% by weight, and particularly preferably 50% by weight to 50% by weight. 95% by weight.

關於選自由具有OH基之(甲基)丙烯酸酯及(甲基)丙烯酸所組成之群中之至少一種(b成分)之含量，就更能表現本發明之效果之方面而言，相對於構成丙烯酸系聚合物之單體成分全量(100重量%)，較佳為1重量%以上，更佳為1重量%～30重量%，進而較佳為2重量%～20重量%，尤佳為3重量%～10重量%。Regarding the content of at least one (component b) selected from the group consisting of (meth)acrylate and (meth)acrylic acid having an OH group, the effect of the present invention can be more exhibited than the The total amount of monomer components (100% by weight) of the acrylic polymer is preferably 1% by weight or more, more preferably 1% by weight to 30% by weight, further preferably 2% by weight to 20% by weight, and particularly preferably 3% by weight % by weight to 10% by weight.

組合物(B)可於不損害本發明之效果之範圍內，含有任意適當之其他成分。作為此種其他成分，可列舉例如：聚合起始劑、鏈轉移劑、溶劑等。關於該等其他成分之含量，可於不損害本發明之效果之範圍內，採用任意適當之含量。The composition (B) may contain any appropriate other components within a range that does not impair the effects of the present invention. As such other components, a polymerization initiator, a chain transfer agent, a solvent, etc. are mentioned, for example. Regarding the content of these other components, any appropriate content can be adopted within a range not impairing the effects of the present invention.

聚合起始劑可根據聚合反應之種類，採用熱聚合起始劑或光聚合起始劑(光起始劑)等。聚合起始劑可僅為1種，亦可為2種以上。As the polymerization initiator, a thermal polymerization initiator or a photopolymerization initiator (photoinitiator), etc. can be used according to the type of the polymerization reaction. Only one type of polymerization initiator may be used, or two or more types may be used.

關於熱聚合起始劑，較佳為於藉由溶液聚合獲得丙烯酸系樹脂時能夠採用。作為此種熱聚合起始劑，可列舉例如：偶氮系聚合起始劑、過氧化物系聚合起始劑(例如，過氧化二苯甲醯、過氧化順丁烯二酸第三丁酯等)、氧化還原系聚合起始劑等。該等熱聚合起始劑中，尤佳為日本專利特開2002-69411號公報中揭示之偶氮系起始劑。此種偶氮系聚合起始劑係於聚合起始劑之分解物不易作為成為加熱產生氣體(釋氣)之產生原因之部分殘留於丙烯酸系樹脂中之方面較佳。作為偶氮系聚合起始劑，可列舉：2,2'-偶氮二異丁腈(以下，有時稱為AIBN)、2,2'-偶氮雙-2-甲基丁腈(以下，有時稱為AMBN)、2,2'-偶氮雙(2-甲基丙酸)二甲酯、4,4'-偶氮雙-4-氰基戊酸等。The thermal polymerization initiator can preferably be used when obtaining an acrylic resin by solution polymerization. Examples of such thermal polymerization initiators include azo-based polymerization initiators, peroxide-based polymerization initiators (for example, dibenzyl peroxide, tert-butyl peroxide maleate) etc.), redox-based polymerization initiators, etc. Among these thermal polymerization initiators, the azo initiator disclosed in Japanese Patent Laid-Open No. 2002-69411 is particularly preferred. Such an azo-based polymerization initiator is preferable in that the decomposed product of the polymerization initiator is unlikely to remain in the acrylic resin as a part that causes the generation of gas (outgas) generated by heating. As the azo-based polymerization initiator, 2,2'-azobisisobutyronitrile (hereinafter, sometimes referred to as AIBN), 2,2'-azobis-2-methylbutyronitrile (hereinafter, may be mentioned) , sometimes referred to as AMBN), 2,2'-azobis(2-methylpropionic acid) dimethyl ester, 4,4'-azobis-4-cyanovaleric acid, etc.

關於光聚合起始劑，較佳為於藉由活性能量線聚合而獲得丙烯酸系聚合物時能夠採用。作為光聚合起始劑，可列舉例如：安息香醚系光聚合起始劑、苯乙酮系光聚合起始劑、α-酮醇系光聚合起始劑、芳香族磺醯氯系光聚合起始劑、光活性肟系光聚合起始劑、安息香系光聚合起始劑、苯偶醯系光聚合起始劑、二苯甲酮系光聚合起始劑、縮酮系光聚合起始劑、9-氧硫𠮿

Figure 111101602-2
系光聚合起始劑等等。The photopolymerization initiator can be preferably used when an acrylic polymer is obtained by active energy ray polymerization. As a photopolymerization initiator, for example, a benzoin ether-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, an α-keto alcohol-based photopolymerization initiator, an aromatic sulfonyl chloride-based photopolymerization initiator can be mentioned. Starter, photoactive oxime-based photopolymerization initiator, benzoin-based photopolymerization initiator, benzoin-based photopolymerization initiator, benzophenone-based photopolymerization initiator, ketal-based photopolymerization initiator , 9-oxysulfur
Figure 111101602-2
Department of photopolymerization initiator and so on.

作為安息香醚系光聚合起始劑，可列舉例如：安息香甲醚、安息香***、安息香丙醚、安息香異丙醚、安息香異丁醚、2,2-二甲氧基-1,2-二苯乙烷-1-酮、苯甲醚甲醚等。作為苯乙酮系光聚合起始劑，可列舉例如：2,2-二乙氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、1-羥基環己基苯基酮、4-苯氧基二氯苯乙酮、4-(第三丁基)二氯苯乙酮等。作為α-酮醇系光聚合起始劑，可列舉例如：2-甲基-2-羥基苯丙酮、1-[4-(2-羥乙基)苯基]-2-甲基丙烷-1-酮等。作為芳香族磺醯氯系光聚合起始劑，可列舉例如2-萘磺醯氯等。作為光活性肟系光聚合起始劑，可列舉例如1-苯基-1,1-丙烷二酮-2-(鄰乙氧基羰基)-肟等。作為安息香系光聚合起始劑，可列舉例如安息香等。作為苯偶醯系光聚合起始劑，可列舉例如苯偶醯等。作為二苯甲酮系光聚合起始劑，可列舉例如：二苯甲酮、苯甲醯苯甲酸、3,3'-二甲基-4-甲氧基二苯甲酮、聚乙烯二苯甲酮、α-羥基環己基苯基酮等。作為縮酮系光聚合起始劑，可列舉例如苯偶醯二甲基縮酮等。作為9-氧硫𠮿

Figure 111101602-2
系光聚合起始劑，可列舉例如：9-氧硫𠮿
Figure 111101602-2
、2-氯9-氧硫𠮿
Figure 111101602-2
、2-甲基9-氧硫𠮿
Figure 111101602-2
、2,4-二甲基9-氧硫𠮿
Figure 111101602-2
、異丙基9-氧硫𠮿
Figure 111101602-2
、2,4-二異丙基9-氧硫𠮿
Figure 111101602-2
、十二烷基9-氧硫𠮿
Figure 111101602-2
等。Examples of benzoin ether-based photopolymerization initiators include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and 2,2-dimethoxy-1,2-diphenyl. Ethan-1-one, anisole, etc. Examples of the acetophenone-based photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 1-hydroxycyclohexylbenzene ketone, 4-phenoxydichloroacetophenone, 4-(tert-butyl)dichloroacetophenone, etc. Examples of the α-ketoalcohol-based photopolymerization initiator include 2-methyl-2-hydroxypropiophenone, 1-[4-(2-hydroxyethyl)phenyl]-2-methylpropane-1 - Ketones etc. As an aromatic sulfonyl chloride-based photopolymerization initiator, 2-naphthalenesulfonyl chloride, etc. are mentioned, for example. As a photoactive oxime-based photopolymerization initiator, 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime etc. are mentioned, for example. As a benzoin type photopolymerization initiator, benzoin etc. are mentioned, for example. As a benzil-based photopolymerization initiator, for example, benzil and the like can be mentioned. Examples of benzophenone-based photopolymerization initiators include benzophenone, benzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyethylene diphenyl Methyl ketone, α-hydroxycyclohexyl phenyl ketone, etc. As a ketal type photopolymerization initiator, benzalkonium dimethyl ketal etc. are mentioned, for example. as 9-oxysulfur 𠮿
Figure 111101602-2
It is a photopolymerization initiator, for example: 9-oxysulfur 𠮿
Figure 111101602-2
, 2-chloro-9-oxysulfur
Figure 111101602-2
, 2-methyl 9-oxothio
Figure 111101602-2
, 2,4-dimethyl 9-oxothio
Figure 111101602-2
, isopropyl 9-oxothioate
Figure 111101602-2
, 2,4-diisopropyl 9-oxothio
Figure 111101602-2
, dodecyl 9-oxysulfur
Figure 111101602-2
Wait.

再者，於基礎聚合物為丙烯酸系樹脂之情形時，黏著劑組合物可包含交聯劑。藉由使用交聯劑，可提高黏著劑之凝聚力，更能表現本發明之效果。交聯劑可僅為1種，亦可為2種以上。Furthermore, when the base polymer is an acrylic resin, the adhesive composition may contain a crosslinking agent. By using the cross-linking agent, the cohesive force of the adhesive can be improved, and the effect of the present invention can be better exhibited. Only one type of crosslinking agent may be used, or two or more types may be used.

作為交聯劑，可列舉：多官能異氰酸酯系交聯劑、環氧系交聯劑、三聚氰胺系交聯劑、過氧化物系交聯劑，此外還可列舉：脲系交聯劑、金屬烷氧化物系交聯劑、金屬螯合物系交聯劑、金屬鹽系交聯劑、碳二醯亞胺系交聯劑、㗁唑啉系交聯劑、氮丙啶系交聯劑、胺系交聯劑等。其中，就更能表現本發明之效果之方面而言，較佳為選自由多官能異氰酸酯系交聯劑及環氧系交聯劑所組成之群中之至少一種。As the crosslinking agent, a polyfunctional isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, a melamine-based crosslinking agent, a peroxide-based crosslinking agent may be mentioned, and further, a urea-based crosslinking agent, a metal alkane may be mentioned. Oxide-based cross-linking agent, metal chelate-based cross-linking agent, metal salt-based cross-linking agent, carbodiimide-based cross-linking agent, oxazoline-based cross-linking agent, aziridine-based cross-linking agent, amine Department of cross-linking agents, etc. Among them, at least one kind selected from the group consisting of a polyfunctional isocyanate-based crosslinking agent and an epoxy-based crosslinking agent is preferable from the viewpoint that the effect of the present invention can be more exhibited.

作為多官能異氰酸酯系交聯劑，可列舉例如：1,2-二異氰酸乙二酯、1,4-伸丁基二異氰酸酯、1,6-六亞甲基二異氰酸酯等低級脂肪族聚異氰酸酯類；伸環戊基二異氰酸酯、伸環己基二異氰酸酯、異佛爾酮二異氰酸酯、氫化甲苯二異氰酸酯、氫化二甲苯二異氰酸酯等脂環族聚異氰酸酯類；2,4-甲苯二異氰酸酯、2,6-甲苯二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、苯二甲基二異氰酸酯等芳香族聚異氰酸酯類等。作為多官能異氰酸酯系交聯劑，例如亦可列舉：三羥甲基丙烷/甲苯二異氰酸酯加成物(Nippon Polyurethane工業股份有限公司製造之名為「Coronate L」之商品)、三羥甲基丙烷/六亞甲基二異氰酸酯加成物(Nippon Polyurethane工業股份有限公司製造之名為「Coronate HL」之商品)、名為「Coronate HX」之商品(Nippon Polyurethane工業股份有限公司)、三羥甲基丙烷/苯二甲基二異氰酸酯加成物(三井化學股份有限公司製造之名為「Takenate 110N」之商品)等市售品。Examples of polyfunctional isocyanate-based crosslinking agents include lower aliphatic polymers such as ethylene 1,2-diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate. Isocyanates; cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate and other alicyclic polyisocyanates; 2,4-toluene diisocyanate, 2 , Aromatic polyisocyanates such as 6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, etc. Examples of polyfunctional isocyanate-based crosslinking agents include trimethylolpropane/toluene diisocyanate adducts (products named "Coronate L" manufactured by Nippon Polyurethane Industrial Co., Ltd.), trimethylolpropane / Hexamethylene diisocyanate adduct (product named "Coronate HL" manufactured by Nippon Polyurethane Industrial Co., Ltd.), product named "Coronate HX" (Nippon Polyurethane Industrial Co., Ltd.), trimethylol Commercial products such as propane/xylylene diisocyanate adduct (product called "Takenate 110N" manufactured by Mitsui Chemicals Co., Ltd.).

作為環氧系交聯劑(多官能環氧化合物)，可列舉例如：N,N,N',N'-四縮水甘油基間苯二甲胺、二縮水甘油基苯胺、1,3-雙(N,N-二縮水甘油胺甲基)環己烷、1,6-己二醇二縮水甘油醚、新戊二醇二縮水甘油醚、乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、聚乙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚、山梨醇聚縮水甘油醚、丙三醇聚縮水甘油醚、季戊四醇聚縮水甘油醚、聚丙三醇聚縮水甘油醚、山梨醇酐聚縮水甘油醚、三羥甲基丙烷聚縮水甘油醚、己二酸二縮水甘油酯、鄰苯二甲酸二縮水甘油酯、三縮水甘油基-三(2-羥乙基)異氰尿酸酯、間苯二酚二縮水甘油醚、雙酚-S-二縮水甘油醚，此外還可列舉分子內具有2個以上之環氧基之環氧系樹脂等。作為環氧系交聯劑，亦可列舉名為「Tetrad C」之商品(三菱瓦斯化學股份有限公司製造)等市售品。Examples of epoxy-based crosslinking agents (polyfunctional epoxy compounds) include N,N,N',N'-tetraglycidyl-m-xylylenediamine, diglycidylaniline, 1,3-bis (N,N-diglycidylamine methyl)cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether , polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polypropylene glycol polyglycidyl ether, sorbitan polyglycidyl ether Glycidyl ether, trimethylolpropane polyglycidyl ether, diglycidyl adipate, diglycidyl phthalate, triglycidyl-tris(2-hydroxyethyl)isocyanurate, Resorcinol diglycidyl ether, bisphenol-S-diglycidyl ether, and epoxy resins having two or more epoxy groups in the molecule can also be used. As the epoxy-based crosslinking agent, commercially available products such as a product named "Tetrad C" (manufactured by Mitsubishi Gas Chemical Co., Ltd.) can also be mentioned.

關於黏著劑組合物中之交聯劑之含量，可於不損害本發明之效果之範圍內，採用任意適當之含量。作為此種含量，例如，就更能表現本發明之效果之方面而言，相對於丙烯酸系樹脂之固形物成分(100重量份)，較佳為0.05重量份～20重量份，更佳為0.1重量份～18重量份，進而較佳為0.5重量份～15重量份，尤佳為0.5重量份～10重量份。Regarding the content of the crosslinking agent in the adhesive composition, any appropriate content can be adopted within a range that does not impair the effects of the present invention. As such a content, for example, from the viewpoint of exhibiting the effects of the present invention, it is preferably 0.05 to 20 parts by weight, more preferably 0.1, with respect to the solid content (100 parts by weight) of the acrylic resin. Part by weight to 18 parts by weight, more preferably 0.5 part by weight to 15 parts by weight, particularly preferably 0.5 part by weight to 10 parts by weight.

[A-1-1-4.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，採用例如日本專利特開2015-074771號公報等中記載之公知之橡膠系黏著劑等、任意適當之橡膠系黏著劑中使用之橡膠系樹脂。其等可僅為1種，亦可為2種以上。 [A-1-1-4. Rubber-based resin] As the rubber-based resin, any suitable rubber-based adhesive such as the known rubber-based adhesive described in Japanese Patent Laid-Open No. 2015-074771 and the like can be used within a range that does not impair the effects of the present invention. Rubber-based resin. Only 1 type may be sufficient as these, and 2 or more types may be sufficient as them.

[A-1-1-5.矽酮系樹脂] 作為矽酮系樹脂，可於不損害本發明之效果之範圍內，採用例如日本專利特開2014-047280號公報等中記載之公知之矽酮系黏著劑等、任意適當之矽酮系黏著劑中使用之矽酮系樹脂。其等可僅為1種，亦可為2種以上。 [A-1-1-5. Silicone resin] As the silicone-based resin, any appropriate silicone-based adhesive, such as a known silicone-based adhesive described in Japanese Patent Laid-Open No. 2014-047280 and the like, can be used within a range that does not impair the effects of the present invention. Silicone resin used in Only 1 type may be sufficient as these, and 2 or more types may be sufficient as them.

＜A-1-2.胺基甲酸酯系樹脂＞ 如上所述，作為基礎聚合物之多元醇較佳為與多官能異氰酸酯化合物反應而成為胺基甲酸酯系樹脂。更具體而言，較佳為由含有多元醇及多官能異氰酸酯化合物之組合物形成胺基甲酸酯系樹脂，詳細而言，使含有多元醇及多官能異氰酸酯化合物之組合物硬化而形成胺基甲酸酯系樹脂。作為使含有多元醇及多官能異氰酸酯化合物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任意適當之方法，諸如使用塊狀聚合或溶液聚合等之胺基甲酸酯化反應方法等。 <A-1-2. Urethane resin> As described above, the polyol as the base polymer is preferably reacted with a polyfunctional isocyanate compound to form a urethane resin. More specifically, it is preferable to form a urethane resin from a composition containing a polyhydric alcohol and a polyfunctional isocyanate compound. Specifically, the composition containing a polyhydric alcohol and a polyfunctional isocyanate compound is hardened to form an amine group. Formate resin. As a method of hardening a composition containing a polyol and a polyfunctional isocyanate compound to form a urethane-based resin, any appropriate method such as block polymerization or solution can be adopted within the range not impairing the effects of the present invention The urethane reaction method of polymerization etc., etc.

又，如上所述，作為基礎聚合物之胺基甲酸酯預聚物較佳為與多官能異氰酸酯化合物反應而成為胺基甲酸酯系樹脂。更具體而言，較佳為由含有胺基甲酸酯預聚物及多官能異氰酸酯化合物之組合物形成胺基甲酸酯系樹脂，詳細而言，使含有胺基甲酸酯預聚物及多官能異氰酸酯化合物之組合物硬化而形成胺基甲酸酯系樹脂。作為使含有多元醇及多官能異氰酸酯化合物之組合物硬化而形成胺基甲酸酯系樹脂之方法，可採用任意適當之製造方法，只要為使用所謂之「胺基甲酸酯預聚物」作為原料而製造胺基甲酸酯系樹脂即可。Moreover, as mentioned above, it is preferable that the urethane prepolymer which is a base polymer reacts with a polyfunctional isocyanate compound, and becomes a urethane resin. More specifically, it is preferable to form a urethane resin from a composition containing a urethane prepolymer and a polyfunctional isocyanate compound. The composition of the polyfunctional isocyanate compound hardens to form a urethane resin. As a method of hardening a composition containing a polyol and a polyfunctional isocyanate compound to form a urethane-based resin, any appropriate production method can be adopted as long as a so-called "urethane prepolymer" is used as the What is necessary is just to manufacture a urethane-type resin using a raw material.

即，胺基甲酸酯系樹脂之較佳之一實施方式係由含有多元醇及多官能異氰酸酯化合物之組合物形成之胺基甲酸酯系樹脂。胺基甲酸酯系樹脂之較佳之另一實施方式係由含有胺基甲酸酯預聚物及多官能異氰酸酯化合物之組合物形成之胺基甲酸酯系樹脂。That is, a preferable embodiment of the urethane-based resin is a urethane-based resin formed from a composition containing a polyhydric alcohol and a polyfunctional isocyanate compound. Another preferred embodiment of the urethane resin is a urethane resin formed from a composition containing a urethane prepolymer and a polyfunctional isocyanate compound.

[A-1-2-1.由含有多元醇及多官能異氰酸酯化合物之組合物形成之胺基甲酸酯系樹脂][A-1-2-1. Urethane resin formed from a composition containing a polyol and a polyfunctional isocyanate compound]

多官能異氰酸酯化合物可僅為1種，亦可為2種以上。Only one type of polyfunctional isocyanate compound may be used, or two or more types may be used.

作為多官能異氰酸酯化合物，可採用胺基甲酸酯化反應中可使用之任意適當之多官能異氰酸酯化合物。作為此種多官能異氰酸酯化合物，可列舉例如：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、多官能芳香脂肪族系異氰酸酯化合物等。As the polyfunctional isocyanate compound, any appropriate polyfunctional isocyanate compound that can be used in the urethane reaction can be used. As such a polyfunctional isocyanate compound, a polyfunctional aliphatic isocyanate compound, a polyfunctional alicyclic isocyanate, a polyfunctional aromatic isocyanate compound, a polyfunctional aromatic aliphatic isocyanate compound etc. are mentioned, for example.

作為多官能脂肪族系異氰酸酯化合物，可列舉例如：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-丙二異氰酸酯、1,3-伸丁基二異氰酸酯、2,3-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-propane diisocyanate, 1,2-propylene diisocyanate, 3-butylene diisocyanate, 2,3-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，可列舉例如：異氰酸3-異氰酸基甲基-3,5,5-三甲基環己基酯、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、異佛爾酮二異氰酸酯、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(異氰酸基甲基)環己烷、1,4-雙(異氰酸基甲基)環己烷、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。As the polyfunctional alicyclic isocyanate compound, for example, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1 ,3-cyclohexanediisocyanate, 1,4-cyclohexanediisocyanate, isophorone diisocyanate, methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate Isocyanates, 4,4'-methylenebis(cyclohexylisocyanate), 1,4-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane , hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethyl xylylene diisocyanate, etc.

作為多官能芳香族系二異氰酸酯化合物，可列舉例如：1,3-伸苯基二異氰酸酯、1,4-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、2,4,6-三異氰酸酯甲苯、1,3,5-三異氰酸酯苯、4,4'-二苯醚二異氰酸酯、4,4'-聯苯二異氰酸酯、1,5-萘二異氰酸酯、4,4',4''-三苯基甲烷三異氰酸酯、聯大茴香胺二異氰酸酯、苯二甲基二異氰酸酯等。As the polyfunctional aromatic diisocyanate compound, for example, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5- Triisocyanate benzene, 4,4'-diphenyl ether diisocyanate, 4,4'-biphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4',4''-triphenylmethane triisocyanate, biphenyl Anisidine diisocyanate, xylylene diisocyanate, etc.

作為多官能芳香脂肪族系異氰酸酯化合物，可列舉例如：ω,ω'-二異氰酸酯-1,3-二甲基苯、ω,ω'-二異氰酸酯-1,4-二甲基苯、ω,ω'-二異氰酸酯-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。As the polyfunctional aromatic aliphatic isocyanate compound, for example, 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, etc.

作為多官能異氰酸酯化合物，亦可列舉：如上所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、及具有異氰尿酸酯環之三聚物等。又，亦可併用其等。Examples of the polyfunctional isocyanate compound include trimethylolpropane adducts of various polyfunctional isocyanate compounds as described above, biurets obtained by reacting with water, and trimers having an isocyanurate ring. things etc. Moreover, you may use these etc. together.

關於多元醇及多官能異氰酸酯化合物中之NCO基與OH基之當量比，以NCO基/OH基計，較佳為5.0以下，更佳為0.1～3.0，進而較佳為0.2～2.5，進而較佳為0.3～2.5，進而較佳為0.3～2.0，尤佳為0.5～2.0，最佳為0.5～1.8。若NCO基/OH基之當量比處於上述範圍內，則可提供一種不易發生容易地從被黏著體剝離之情況，代表性而言，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後不易發生剝離，且當需要進行剝離時可容易地剝離之表面保護膜。又，若NCO基/OH基之當量比處於上述範圍內，則能夠降低霧度。尤其是，若可使霧度降低至3%以下，則本發明之實施方式之表面保護膜之檢查性進一步提高。The equivalent ratio of NCO groups to OH groups in the polyol and the polyfunctional isocyanate compound is, in terms of NCO groups/OH groups, preferably 5.0 or less, more preferably 0.1 to 3.0, still more preferably 0.2 to 2.5, and still more Preferably it is 0.3-2.5, More preferably, it is 0.3-2.0, More preferably, it is 0.5-2.0, Most preferably, it is 0.5-1.8. When the equivalent ratio of NCO groups/OH groups is within the above range, it is possible to provide a situation where it is difficult to easily peel off the adherend. A surface protective film that does not easily peel off after the exposed surface of the optical member or the electronic member, and can be easily peeled off when peeling is required. Moreover, when the equivalent ratio of NCO group / OH group exists in the said range, haze can be reduced. In particular, if the haze can be reduced to 3% or less, the inspectability of the surface protection film according to the embodiment of the present invention will be further improved.

關於多官能異氰酸酯化合物之含有比率，相對於多元醇，多官能異氰酸酯化合物較佳為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%，進而較佳為2.3重量%～23重量%，進而較佳為2.3重量%～18重量%，尤佳為2.5重量%～18重量%，最佳為2.5重量%～16重量%。若多官能異氰酸酯化合物之含有比率處於上述範圍內，則可提供一種不易發生容易地從被黏著體剝離之情況，代表性而言，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後不易發生剝離，且當需要進行剝離時可容易地剝離之表面保護膜。又，若多官能異氰酸酯化合物之含有比率處於上述範圍內，則能夠降低霧度。尤其是，若可使霧度降低至3%以下，則本發明之實施方式之表面保護膜之檢查性進一步提高。The content ratio of the polyfunctional isocyanate compound is preferably 1.0% by weight to 30% by weight, more preferably 1.5% by weight to 27% by weight, and still more preferably 2.0% by weight to 25% by weight relative to the polyol. %, more preferably 2.3% by weight to 23% by weight, still more preferably 2.3% by weight to 18% by weight, particularly preferably 2.5% by weight to 18% by weight, and most preferably 2.5% by weight to 16% by weight. If the content ratio of the polyfunctional isocyanate compound is within the above-mentioned range, it is possible to provide a situation where it is difficult to easily peel off the adherend, and typically, in the manufacturing process of an optical member or an electronic member, the optical member is attached to the optical member. A surface protection film that does not easily peel off after the exposed surface of the component or the electronic component, and can be easily peeled off when peeling is required. Moreover, when the content ratio of a polyfunctional isocyanate compound exists in the said range, haze can be reduced. In particular, if the haze can be reduced to 3% or less, the inspectability of the surface protection film according to the embodiment of the present invention will be further improved.

為了使含有多元醇及多官能異氰酸酯化合物之組合物硬化，較佳為使用觸媒。作為此種觸媒，可列舉例如：有機金屬系化合物、三級胺化合物等。觸媒可僅為1種，亦可為2種以上。In order to harden the composition containing a polyol and a polyfunctional isocyanate compound, it is preferable to use a catalyst. As such a catalyst, an organometallic compound, a tertiary amine compound, etc. are mentioned, for example. Only one type of catalyst may be used, or two or more types may be used.

作為有機金屬系化合物，可列舉例如：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。其中，就反應速度及黏著劑層之適用期之方面而言，較佳為鐵系化合物、錫系化合物。Examples of the organometallic compound include iron-based compounds, tin-based compounds, titanium-based compounds, zirconium-based compounds, lead-based compounds, cobalt-based compounds, zinc-based compounds, and the like. Among them, an iron-based compound and a tin-based compound are preferred in terms of the reaction rate and the pot life of the adhesive layer.

作為鐵系化合物，可列舉例如：乙醯丙酮酸鐵、2-乙基己酸鐵等。Examples of the iron-based compound include iron acetylacetonate, iron 2-ethylhexanoate, and the like.

作為錫系化合物，可列舉例如：二氯化二丁基錫、氧化二丁基錫、二溴化二丁基錫、馬來酸二丁基錫、二月桂酸二丁基錫、二乙酸二丁基錫、硫化二丁基錫、三丁基甲醇錫、乙酸三丁基錫、三乙基乙醇錫、三丁基乙醇錫、氧化二辛基錫、二月桂酸二辛基錫、氯化三丁基錫、三氯乙酸三丁基錫、2-乙基己酸錫等。Examples of tin-based compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin maleate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, and tributylmethanol. Tin, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, dioctyltin dilaurate, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate Wait.

作為鈦系化合物，可列舉例如：二氯化二丁基鈦、鈦酸四丁酯、三氯化丁氧基鈦等。As a titanium type compound, dibutyl titanium dichloride, tetrabutyl titanate, butoxy titanium trichloride, etc. are mentioned, for example.

作為鋯系化合物，可列舉例如：環烷酸鋯、乙醯丙酮酸鋯等。As a zirconium-type compound, zirconium naphthenate, zirconium acetopyruvate, etc. are mentioned, for example.

作為鉛系化合物，可列舉例如：油酸鉛、2-乙基己酸鉛、苯甲酸鉛、環烷酸鉛等。As a lead-type compound, lead oleate, lead 2-ethylhexanoate, lead benzoate, lead naphthenate etc. are mentioned, for example.

作為鈷系化合物，可列舉例如：2-乙基己酸鈷、苯甲酸鈷等。As a cobalt-type compound, cobalt 2-ethylhexanoate, cobalt benzoate, etc. are mentioned, for example.

作為鋅系化合物，可列舉例如：環烷酸鋅、2-乙基己酸鋅等。As a zinc-based compound, zinc naphthenate, zinc 2-ethylhexanoate, etc. are mentioned, for example.

作為三級胺化合物，可列舉例如：三乙胺、三伸乙二胺、1,8-二氮雜雙環-(5,4,0)-十一碳烯-7等。As a tertiary amine compound, triethylamine, triethylenediamine, 1,8-diazabicyclo-(5,4,0)-undecene-7 etc. are mentioned, for example.

關於觸媒之量，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%。若觸媒之量處於上述範圍內，則可提供一種不易發生容易地從被黏著體剝離之情況，代表性而言，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後不易發生剝離，且當需要進行剝離時可容易地剝離之表面保護膜。The amount of the catalyst is preferably 0.005% by weight to 1.00% by weight, more preferably 0.01% by weight to 0.75% by weight, still more preferably 0.01% by weight to 0.50% by weight, and particularly preferably 0.01% by weight with respect to the polyol. % to 0.20% by weight. If the amount of the catalyst is within the above-mentioned range, it is possible to provide a situation where it is difficult to easily peel off the adherend. A surface protection film that is not easy to peel off after the exposed surface of the electronic component, and can be peeled off easily when peeling is required.

含有多元醇及多官能異氰酸酯化合物之組合物中，可於不損害本發明之效果之範圍內，包含任意適當之其他成分。作為此種其他成分，可列舉例如：抗氧化劑、紫外線吸收劑、光穩定劑、樹脂成分、黏著賦予劑、交聯延遲劑、無機填充劑、有機填充劑、金屬粉、顏料、箔狀物、軟化劑、防老化劑、導電劑、表面潤滑劑、調平劑、防腐劑、耐熱穩定劑、聚合抑制劑、潤滑劑、溶劑等。In the composition containing a polyol and a polyfunctional isocyanate compound, any appropriate other components may be contained in the range which does not impair the effect of this invention. Examples of such other components include antioxidants, ultraviolet absorbers, light stabilizers, resin components, adhesion imparting agents, crosslinking retarders, inorganic fillers, organic fillers, metal powders, pigments, foils, Softeners, anti-aging agents, conductive agents, surface lubricants, leveling agents, preservatives, heat-resistant stabilizers, polymerization inhibitors, lubricants, solvents, etc.

該等其他成分中，包含抗氧化劑、紫外線吸收劑、光穩定劑等防劣化劑為較佳之實施方式。藉由使黏著劑組合物包含防劣化劑，可使防糊劑殘留性優異，諸如即便將形成之黏著劑層貼附於被黏著體之後於加溫狀態下保存，亦不易於被黏著體殘留糊劑等。防劣化劑可僅為1種，亦可為2種以上。作為防劣化劑，尤佳為抗氧化劑。Among these other components, it is a preferred embodiment to contain anti-deterioration agents such as antioxidants, ultraviolet absorbers, and light stabilizers. By including the anti-deterioration agent in the adhesive composition, it is possible to have excellent paste residue resistance, such as being less likely to remain on the adherend even if the formed adhesive layer is attached to the adherend and then stored in a heated state Paste etc. Only one type of anti-deterioration agent may be used, or two or more types may be used. As an anti-deterioration agent, an antioxidant is especially preferable.

作為抗氧化劑，可列舉例如：自由基鏈禁止劑、過氧化物分解劑等。As an antioxidant, a radical chain inhibitor, a peroxide decomposer, etc. are mentioned, for example.

作為自由基鏈禁止劑，可列舉例如：酚系抗氧化劑、胺系抗氧化劑等。As a radical chain inhibitor, a phenolic antioxidant, an amine antioxidant, etc. are mentioned, for example.

作為過氧化物分解劑，可列舉例如：硫系抗氧化劑、磷系抗氧化劑等。As a peroxide decomposer, a sulfur-based antioxidant, a phosphorus-based antioxidant, etc. are mentioned, for example.

作為酚系抗氧化劑，可列舉例如：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。As a phenolic antioxidant, a monophenolic antioxidant, a bisphenolic antioxidant, a polymer type phenolic antioxidant, etc. are mentioned, for example.

作為單酚系抗氧化劑，可列舉例如：2,6-二-第三丁基-對甲酚、丁基化羥基大茴香醚、2,6-二-第三丁基-4-乙基苯酚、硬脂-β-(3,5-二-第三丁基-4-羥基苯基)丙酸酯等。Examples of monophenol-based antioxidants include 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, and 2,6-di-tert-butyl-4-ethylphenol , stearyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, etc.

作為雙酚系抗氧化劑，可列舉例如：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 bisphenol-based antioxidants include 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl- 6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylene bis(3-methyl-6-tertiary butylphenol), 3,9-bis[1,1-dimethyl-2-[beta-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl ] 2,4,8,10-tetraoxaspiro[5,5]undecane, etc.

作為高分子型酚系抗氧化劑，可列舉例如：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)酪酸]乙二醇酯、1,3,5-三(3',5'-二-第三丁基-4'-羥基苄基)-S-三嗪-2,4,6-(1H,3H,5H)三酮、生育酚等。Examples of high molecular weight phenolic antioxidants include 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl base-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tetra-[methylene-3-(3',5'-di-tert-butyl) yl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-tert-butylphenyl)butyric acid]glycol ester, 1,3 ,5-Tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, tocopherol, etc. .

作為硫系抗氧化劑，可列舉例如：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 sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and di-3,3'-thiodipropionate. Stearyl ester, etc.

作為磷系抗氧化劑，可列舉例如：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。As a phosphorus antioxidant, triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, etc. are mentioned, for example.

作為紫外線吸收劑，可列舉例如：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、三嗪系紫外線吸收劑等。Examples of the ultraviolet absorber include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, oxaniline-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers agents, triazine-based UV absorbers, etc.

作為二苯甲酮系紫外線吸收劑，可列舉例如：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-octyloxydiphenyl 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-benzylphenyl) Methane etc.

作為苯并***系紫外線吸收劑，可列舉例如：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, 2-(2'-hydroxy-5'-tert-butyl) Phenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl) base-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-pentylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-[2'-Hydroxy-3'-(3'',4'',5'',6'',-tetrahydrophthalimidomethyl)-5'-methylphenyl] Benzotriazole, 2,2'methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2 -(2'-hydroxy-5'-methacryloyloxyphenyl)-2H-benzotriazole and the like.

作為水楊酸系紫外線吸收劑，可列舉例如：水楊酸苯酯、水楊酸對第三丁基苯酯、水楊酸對辛基苯酯等。As a salicylic acid type ultraviolet absorber, phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, etc. are mentioned, for example.

作為氰基丙烯酸酯系紫外線吸收劑，可列舉例如：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 cyanoacrylate-based ultraviolet absorbers include 2-cyano-3,3'-diphenylacrylic acid-2-ethylhexyl, 2-cyano-3,3'-diphenylacrylic acid ethyl ester, etc.

作為光穩定劑，可列舉例如：受阻胺系光穩定劑、紫外線穩定劑等。As a light stabilizer, a hindered amine light stabilizer, an ultraviolet-ray stabilizer, etc. are mentioned, for example.

作為受阻胺系光穩定劑，可列舉例如：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-哌啶酯等。Examples of hindered amine-based light stabilizers include bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6, sebacic acid) 6-Pentamethyl-4-piperidinyl) ester, methyl-1,2,2,6,6-pentamethyl-4-piperidinyl sebacate, etc.

作為紫外線穩定劑，可列舉例如：雙(辛基苯基)硫化鎳、[2,2'-硫代雙(4-第三辛基苯酚)]-正丁胺鎳鹽、鎳錯合物-3,5-二-第三丁基-4-羥基苄基-磷酸單乙醇鹽、二丁基二硫代胺基甲酸鎳、苯甲酸酯型猝滅劑、二丁基二硫代胺基甲酸鎳等。Examples of UV stabilizers include bis(octylphenyl)nickel sulfide, [2,2'-thiobis(4-tert-octylphenol)]-n-butylamine nickel salt, nickel complex- 3,5-Di-tert-butyl-4-hydroxybenzyl-phosphate monoethanolate, nickel dibutyldithiocarbamate, benzoate type quencher, dibutyldithiocarbamate Nickel formate etc.

[A-1-2-2.由含有胺基甲酸酯預聚物及多官能異氰酸酯化合物之組合物形成之胺基甲酸酯系樹脂] 多官能異氰酸酯化合物可僅為1種，亦可為2種以上。 [A-1-2-2. Urethane-based resin formed from a composition containing a urethane prepolymer and a polyfunctional isocyanate compound] Only one type of polyfunctional isocyanate compound may be used, or two or more types may be used.

作為多官能異氰酸酯化合物，可採用能用於胺基甲酸酯化反應之任意適當之多官能異氰酸酯化合物。作為此種多官能異氰酸酯化合物，可列舉例如A-1-2項中所說明「多官能異氰酸酯化合物」。As the polyfunctional isocyanate compound, any appropriate polyfunctional isocyanate compound that can be used in the urethane reaction can be used. As such a polyfunctional isocyanate compound, the "polyfunctional isocyanate compound" demonstrated in the item A-1-2 is mentioned, for example.

含有胺基甲酸酯預聚物及多官能異氰酸酯化合物之組合物中，可於不損害本發明之效果之範圍內，包含任意適當之其他成分。作為此種其他成分，可列舉例如：抗氧化劑、紫外線吸收劑、光穩定劑、樹脂成分、黏著賦予劑、交聯延遲劑、無機填充劑、有機填充劑、金屬粉、顏料、箔狀物、軟化劑、防老化劑、導電劑、表面潤滑劑、調平劑、防腐劑、耐熱穩定劑、聚合抑制劑、潤滑劑、溶劑等。In the composition containing the urethane prepolymer and the polyfunctional isocyanate compound, any appropriate other components may be contained within the range not impairing the effects of the present invention. Examples of such other components include antioxidants, ultraviolet absorbers, light stabilizers, resin components, adhesion imparting agents, crosslinking retarders, inorganic fillers, organic fillers, metal powders, pigments, foils, Softeners, anti-aging agents, conductive agents, surface lubricants, leveling agents, preservatives, heat-resistant stabilizers, polymerization inhibitors, lubricants, solvents, etc.

該等其他成分之中，包含抗氧化劑、紫外線吸收劑、光穩定劑等防劣化劑為較佳之實施方式。藉由使黏著劑組合物包含防劣化劑，可使防糊劑殘留性優異，諸如即便將形成之黏著劑層貼附於被黏著體之後於加溫狀態下保存亦不易於被黏著體殘留糊劑等。防劣化劑可僅為1種，亦可為2種以上。作為防劣化劑，尤佳為抗氧化劑。關於抗氧化劑、紫外線吸收劑、光穩定劑之詳細情況，可引用A-1-2-1項中之說明。Among these other components, it is a preferred embodiment to include anti-deterioration agents such as antioxidants, ultraviolet absorbers, and light stabilizers. By including the anti-deterioration agent in the adhesive composition, it is possible to have excellent anti-paste residue properties, for example, even if the formed adhesive layer is attached to the adherend and then stored in a heated state, the adherend is not likely to remain in the adherend. agent, etc. Only one type of anti-deterioration agent may be used, or two or more types may be used. As an anti-deterioration agent, an antioxidant is especially preferable. For details of antioxidants, ultraviolet absorbers, and light stabilizers, the descriptions in item A-1-2-1 can be cited.

關於胺基甲酸酯預聚物及多官能異氰酸酯化合物中之NCO基與OH基之當量比，以NCO基/OH基計，較佳為5.0以下，更佳為0.01～3.0，進而較佳為0.02～2.0，進而較佳為0.03～2.0，進而較佳為0.03～1.9，尤佳為0.05～1.9，最佳為0.05～1.8。若NCO基/OH基之當量比處於上述範圍內，則可提供一種不易發生容易地從被黏著體剝離，代表性而言，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後不易發生剝離，且當需要進行剝離時可容易地剝離之表面保護膜。又，若NCO基/OH基之當量比處於上述範圍內，則能夠降低霧度。尤其是，若可使霧度降低至3%以下，則本發明之實施方式之表面保護膜之檢查性進一步提高。The equivalent ratio of NCO groups to OH groups in the urethane prepolymer and the polyfunctional isocyanate compound is preferably 5.0 or less, more preferably 0.01 to 3.0, and still more preferably NCO groups/OH groups. 0.02 to 2.0, more preferably 0.03 to 2.0, still more preferably 0.03 to 1.9, particularly preferably 0.05 to 1.9, and most preferably 0.05 to 1.8. If the equivalent ratio of NCO group/OH group is within the above range, it is possible to provide a product that does not easily peel off from the adherend, typically, in the manufacturing process of an optical member or an electronic member, the optical member is attached to the optical member. Or a surface protective film that does not easily peel off after the exposed surface of the electronic component, and can be easily peeled off when peeling is required. Moreover, when the equivalent ratio of NCO group / OH group exists in the said range, haze can be reduced. In particular, if the haze can be reduced to 3% or less, the inspectability of the surface protection film according to the embodiment of the present invention will be further improved.

關於多官能異氰酸酯化合物之含有比率，相對於胺基甲酸酯預聚物，多官能異氰酸酯化合物較佳為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%～25重量%，進而較佳為0.5重量%～25重量%，進而較佳為0.5重量%～23重量%，尤佳為1重量%～23重量%，最佳為1重量%～21重量%。若多官能異氰酸酯化合物之含有比率處於上述範圍內，則可提供一種不易發生容易地從被黏著體剝離之情況，代表性而言，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後不易發生剝離，且當需要進行剝離時可容易地剝離之表面保護膜。又，若多官能異氰酸酯化合物之含有比率處於上述範圍內，則能夠降低霧度。尤其是，若可使霧度降低至3%以下，則本發明之實施方式之表面保護膜之檢查性進一步提高。The content ratio of the polyfunctional isocyanate compound is preferably 0.01% by weight to 30% by weight, more preferably 0.05% by weight to 25% by weight, and still more preferably 0.01% by weight to 25% by weight relative to the urethane prepolymer. 0.1% by weight to 25% by weight, more preferably 0.5% by weight to 25% by weight, more preferably 0.5% by weight to 23% by weight, more preferably 1% by weight to 23% by weight, and most preferably 1% by weight to 21% by weight. If the content ratio of the polyfunctional isocyanate compound is within the above-mentioned range, it is possible to provide a situation where it is difficult to easily peel off the adherend, and typically, in the manufacturing process of an optical member or an electronic member, the optical member is attached to the optical member. A surface protection film that does not easily peel off after the exposed surface of the component or the electronic component, and can be easily peeled off when peeling is required. Moreover, when the content ratio of a polyfunctional isocyanate compound exists in the said range, haze can be reduced. In particular, if the haze can be reduced to 3% or less, the inspectability of the surface protection film according to the embodiment of the present invention will be further improved.

＜A-1-3.離子性化合物＞ 作為離子性化合物，可於不損害本發明之效果之範圍內，採用任意適當之離子性化合物。作為此種離子性化合物，較佳為離子性液體，更佳為包含氟有機陰離子之離子性液體。藉由使黏著劑組合物除了包含基礎聚合物之外，還包含離子性化合物與下文所述之氟系化合物兩者，可提供一種充分地抑制剝離靜電壓而於剝離時不使該光學構件或該電子構件破損之表面保護膜，該表面保護膜代表性而言為包含黏著劑層之表面保護膜，其於光學構件或電子構件之製造步驟中，為了防止該光學構件或該電子構件之表面於加工、組裝、檢查、運輸等時受損而貼合於該光學構件或該電子構件之露出面。 <A-1-3. Ionic compound> As the ionic compound, any appropriate ionic compound can be used within a range that does not impair the effects of the present invention. As such an ionic compound, an ionic liquid is preferable, and an ionic liquid containing a fluorine organic anion is more preferable. By making the adhesive composition contain both the ionic compound and the fluorine-based compound described below in addition to the base polymer, it is possible to provide a method of sufficiently suppressing the peeling electrostatic voltage without causing the optical member or the optical member to be peeled off. The surface protective film of the electronic component is damaged, and the surface protective film is typically a surface protective film containing an adhesive layer. In the manufacturing process of the optical component or the electronic component, in order to prevent the surface of the optical component or the electronic component Damaged during processing, assembly, inspection, transportation, etc., and attached to the exposed surface of the optical component or the electronic component.

離子性化合物可僅為1種，亦可為2種以上。Only one type of ionic compound may be used, or two or more types may be used.

離子性液體意指於25℃下呈液狀之熔鹽(離子性化合物)。The ionic liquid means a molten salt (ionic compound) that is liquid at 25°C.

作為離子性液體，可於不損害本發明之效果之範圍內，採用任意適當之離子性液體。作為此種離子性液體，較佳為包含氟有機陰離子之離子性液體，更佳為由氟有機陰離子與鎓陽離子構成之離子性液體。藉由採用由氟有機陰離子與鎓陽離子構成之離子性液體，並且藉由與下文所述之氟系化合物併用，可提供一種更充分地抑制剝離靜電壓而於剝離時使該光學構件或該電子構件更不易破損之表面保護膜，該表面保護膜代表性而言為包含黏著劑層之表面保護膜，其於光學構件或電子構件之製造步驟中，為了防止該光學構件或該電子構件之表面於加工、組裝、檢查、運輸等時受損而貼合於該光學構件或該電子構件之露出面。As the ionic liquid, any appropriate ionic liquid can be used within the range that does not impair the effects of the present invention. As such an ionic liquid, an ionic liquid containing a fluoroorganic anion is preferable, and an ionic liquid consisting of a fluoroorganic anion and an onium cation is more preferable. By using an ionic liquid composed of a fluorine organic anion and an onium cation, and by using it in combination with the fluorine-based compound described below, it is possible to provide a more sufficient suppression of the peeling electrostatic voltage to make the optical member or the electron during peeling off. The surface protective film of which the component is less likely to be damaged, the surface protective film is typically a surface protective film containing an adhesive layer, which is used in the manufacturing steps of the optical component or electronic component, in order to prevent the surface of the optical component or the electronic component from being damaged. Damaged during processing, assembly, inspection, transportation, etc., and attached to the exposed surface of the optical component or the electronic component.

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，採用任意適當之鎓陽離子。作為此種鎓陽離子，較佳為選自含氮鎓陽離子、含硫鎓陽離子、含磷鎓陽離子中之至少一種。藉由選擇該等鎓陽離子，並且藉由與下文所述之氟系化合物併用，可提供一種更充分地抑制剝離靜電壓而於剝離時使該光學構件或該電子構件更不易破損之表面保護膜，該表面保護膜代表性而言為包含黏著劑層之表面保護膜，其於光學構件或電子構件之製造步驟中，為了防止該光學構件或該電子構件之表面於加工、組裝、檢查、運輸等時受損而貼合於該光學構件或該電子構件之露出面。As the onium cation that can constitute the ionic liquid, any appropriate onium cation can be used within a range that does not impair the effects of the present invention. Such an onium cation is preferably at least one selected from the group consisting of nitrogen-containing onium cations, sulfur-containing onium cations, and phosphorus-containing onium cations. By selecting these onium cations and using them in combination with the fluorine-based compounds described below, a surface protection film that more fully suppresses the peeling electrostatic voltage and makes the optical member or the electronic member less likely to be damaged during peeling can be provided. , the surface protective film is typically a surface protective film comprising an adhesive layer, in the manufacturing steps of the optical member or electronic member, in order to prevent the surface of the optical member or the electronic member from being processed, assembled, inspected, transported Isochronically damaged and attached to the exposed surface of the optical member or the electronic member.

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]

Figure 02_image001
The onium cation that can constitute the ionic liquid is preferably at least one selected from the group consisting of cations having structures represented by general formulae (1) to (5). [hua 1]
Figure 02_image001

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

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

通式(3)中，Rh表示碳數2～20之烴基，可含有雜原子，Ri、Rj及Rk相同或不同，表示氫或碳數1～16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 a heteroatom, 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 a heteroatom.

通式(4)中，Z表示氮原子、硫原子或磷原子，Rl、Rm、Rn及Ro相同或不同，表示碳數1～20之烴基，可含有雜原子。其中，於Z為硫原子之情形時，無Ro。In the general formula (4), Z represents a nitrogen atom, a sulfur atom or a phosphorus atom, and R1, Rm, Rn and Ro are the same or different, represent a hydrocarbon group having 1 to 20 carbon atoms, and may contain a hetero atom. However, when Z is 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，可列舉例如：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 pyridinium cations, pyrrolidinium cations, piperidinium cations, cations having a pyrroline skeleton, and cations having a pyrrole skeleton.

作為通式(1)所表示之陽離子之具體例，可列舉例如如下等：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。Specific examples of the cation represented by the general formula (1) include, for example, the following: 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3- Methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4 -Pyridinium cations such as methylpyridinium cations, 1-butyl-3,4-dimethylpyridinium cations, 1,1-dimethylpyrrolidinium cations; 1-ethyl-1-methylpyrrolidine cations Onium 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-dipropylpyrrolidine Pyrrolidinium cations such as 1-propyl-1-butylpyrrolidinium cation and 1,1-dibutylpyrrolidinium cation; 1-propylpiperidinium cation, 1-pentylpiperidinium cation Cation, 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1 -Amylpiperidinium 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-heptylpiperidium cation pyridinium cation, 1-propyl-1-butylpiperidinium cation, 1,1-dimethylpiperidinium cation, 1,1-dipropylpiperidinium cation, 1,1-dibutylpiperidium cation Piperidinium cations such as pyridinium cations; 2-methyl-1-pyrroline cations; 1-ethyl-2-phenylindole cations; 1,2-dimethylindole cations; 1-ethylcarbazole cation.

其中，就更能表現本發明之效果之方面而言，較佳為，列舉如下等：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，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 them, from the viewpoint of exhibiting the effects of the present invention more preferably, the following are preferred: 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethylpyridinium cation, etc. -3-methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octane Pyridinium cations such as base-4-methylpyridinium cation; 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butane pyrrolidinium 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 Cation, pyrrolidinium cation 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-pentylpiperidinium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidium cation Dividinium cation, 1-ethyl-1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl -Piperidinium cations such as 1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, 1-propyl-1-butylpiperidinium cation, etc., more preferably 1-hexylpyridinium cation Cation, 1-ethyl-3-methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, 1-methyl-1-propyl Pyrrolidinium cation, 1-methyl-1-propylpiperidinium cation.

作為通式(2)所表示之陽離子，可列舉例如：咪唑鎓陽離子、四氫嘧啶鎓陽離子、二氫嘧啶鎓陽離子等。As a cation represented by general formula (2), an imidazolium cation, an tetrahydropyrimidinium cation, a dihydropyrimidinium cation, etc. are mentioned, for example.

作為通式(2)所表示之陽離子之具體例，可列舉例如如下等：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。Specific examples of the cation represented by the general formula (2) include, for example, the following: 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methyl cation Imidazolium cation, 1-butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3- Methylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation Cation, imidazole such as 1-ethyl-2,3-dimethylimidazolium cation, 1-butyl-2,3-dimethylimidazolium cation, 1-hexyl-2,3-dimethylimidazolium cation, etc. Onium 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 Equal tetrahydropyrimidinium cation; 1,3-dimethyl-1,4-dihydropyrimidinium cation, 1,3-dimethyl-1,6-dihydropyrimidinium cation, 1,2,3-trihydropyrimidinium cation Methyl-1,4-dihydropyrimidinium cation, 1,2,3-trimethyl-1,6-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,4-di Dihydropyrimidinium cations such as hydrogen pyrimidinium cation and 1,2,3,4-tetramethyl-1,6-dihydropyrimidinium cation.

其中，就更能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 them, 1,3-dimethylimidazolium cations, 1,3-diethylimidazolium cations, 1-ethyl-3-methyl cations, and 1-ethyl-3-methyl cations are preferred from the viewpoint of exhibiting the effects of the present invention. Imidazolium cation, 1-butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methyl cation imidazolium cations such as base imidazolium cation, 1-dodecyl-3-methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, etc., more preferably, 1-ethyl-3- Methylimidazolium cation, 1-hexyl-3-methylimidazolium cation.

作為通式(3)所表示之陽離子，可列舉例如：吡唑鎓陽離子、吡唑啉鎓陽離子等。As a cation represented by general formula (3), a pyrazolium cation, a pyrazolinium cation, etc. are mentioned, for example.

作為通式(3)所表示之陽離子之具體例，可列舉例如如下等：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。Specific examples of the cation represented by the general formula (3) include, for example, the following: 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2-methylpyrazoline Onium cation, 1-ethyl-2,3,5-trimethylpyrazolium cation, 1-propyl-2,3,5-trimethylpyrazolium cation, 1-butyl-2,3, Pyrazolonium cations such as 5-trimethylpyrazolium cation; 1-ethyl-2,3,5-trimethylpyrazolinium cation, 1-propyl-2,3,5-trimethylpyridine Pyrazolinium cations such as oxazolinium cations and 1-butyl-2,3,5-trimethylpyrazolinium cations.

作為通式(4)所表示之陽離子，可列舉例如：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由烯基或烷氧基、進而環氧基取代者等。Examples of cations represented by the general formula (4) include tetraalkylammonium cations, trialkyl perionium cations, tetraalkylphosphonium cations, or a part of the above-mentioned alkyl groups consisting of an alkenyl group or an alkoxy group, and then an epoxy group. Substitutes etc.

作為通式(4)所表示之陽離子之具體例，可列舉例如：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, tetraheptylammonium cation Ammonium cation, triethylmethylammonium cation, tributylethylammonium cation, trimethylpropylammonium cation, trimethyldecylammonium cation, N,N-diethyl-N-methyl-N- (2-Methoxyethyl)ammonium cation, glycidyl trimethylammonium cation, trimethyl pericium cation, triethyl pericynium cation, tributyl pericynium cation, trihexyl pericynium cation, diethylmethyl pericium cation Cation, Dibutylethyl Phosphonium Cation, Dimethyl Decyl Phosphonium Cation, Tetramethyl Phosphonium Cation, Tetraethyl Phosphonium Cation, Tetrabutyl Phosphonium Cation, Tetrahexyl Phosphonium Cation, Tetraoctyl Phosphonium Cation, Triethyl Phosphonium Cation Methylphosphonium cation, tributylethylphosphonium cation, trimethyldecylphosphonium cation, diallyldimethylammonium cation, etc.

其中，就更能表現本發明之效果之方面而言，較佳為，列舉如下等：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-正丁酯銨陽離子、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-正丁酯銨陽離子、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-正丁酯-N-己基銨陽離子、N,N-二乙基-正丁酯-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-正丁酯-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，更佳為三甲基丙基銨陽離子。Among them, in terms of the aspect that the effect of the present invention can be more exhibited, the following are preferred: triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, diethyl ammonium cation, and the like. Asymmetric tetraoxane such as methyl perionium cation, dibutylethyl perionium cation, dimethyldecyl perionium cation, triethyl methyl phosphonium cation, tributylethyl phosphonium cation, trimethyldecyl phosphonium cation ammonium cation, trialkyl perionium cation, tetraalkyl phosphonium cation; or N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium cation, glycidyl trimethyl cation Ammonium cation, diallyldimethylammonium cation, N,N-dimethyl-N-ethyl-N-propylammonium cation, N,N-dimethyl-N-ethyl-n-butylammonium cation 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-butyl ammonium cation, N,N-dimethyl-N-propyl-N-pentylammonium cation, N,N-dimethyl-N-propyl cation -N-hexylammonium cation, N,N-dimethyl-N-propyl-N-heptylammonium cation, N,N-dimethyl-n-butyl ester-N-hexylammonium cation, N,N-di Ethyl-n-butyl ester-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-pentylammonium cation N-diethyl-N-methyl-N-heptylammonium cation, N,N-diethyl-N-propyl-N-pentylammonium cation, triethylpropylammonium cation, tripentylammonium cation cation, triethylheptylammonium cation, N,N-dipropyl-N-methyl-N-ethylammonium cation, N,N-dipropyl-N-methyl-N-pentylammonium cation, N,N-dipropyl-n-butyl ester-N-hexylammonium cation, N,N-dipropyl-N,N-dihexylammonium cation, N,N-dibutyl-N-methyl-N- Amylammonium cation, N,N-dibutyl-N-methyl-N-hexylammonium cation, trioctylmethylammonium cation, N-methyl-N-ethyl-N-propyl-N-pentane ammonium cation, 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，採用任意適當之氟有機陰離子。此種氟有機陰離子可完全氟化(全氟化)，亦可部分氟化。As the fluoroorganic anion that can constitute the ionic liquid, any appropriate fluoroorganic anion can be used within a range that does not impair the effects of the present invention. Such fluoroorganic anions can be fully fluorinated (perfluorinated) or partially fluorinated.

作為此種氟有機陰離子，可列舉例如：經氟化之芳基磺酸鹽、全氟烷磺酸鹽、雙(氟磺醯基)醯亞胺、雙(全氟烷磺醯基)醯亞胺、氰基全氟烷磺醯基醯胺、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、三氟乙酸鹽、全氟烷基化物、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 arylsulfonates, perfluoroalkanesulfonates, bis(fluorosulfonyl)imide, and bis(perfluoroalkanesulfonyl)imide. Amines, cyanoperfluoroalkanesulfonamides, bis(cyano)perfluoroalkanesulfonamides, cyano-bis-(perfluoroalkanesulfonamides), tris(perfluoroalkanesulfonamides) sulfonyl) methide, trifluoroacetate, perfluoroalkylate, tris(perfluoroalkanesulfonyl)methide, (perfluoroalkanesulfonyl)trifluoroacetamide and the like.

該等氟有機陰離子中，更佳為全氟烷基磺酸鹽、雙(氟磺醯基)醯亞胺、雙(全氟烷磺醯基)醯亞胺，更具體而言，例如為三氟甲磺酸鹽、五氟乙磺酸鹽、七氟丙磺酸鹽、九氟丁磺酸鹽、雙(氟磺醯基)醯亞胺、雙(三氟甲磺醯基)醯亞胺。Among these fluoroorganic anions, more preferred are perfluoroalkanesulfonates, bis(fluorosulfonyl)imide, bis(perfluoroalkanesulfonyl)imide, and more specifically, tris fluoromethanesulfonate, pentafluoroethanesulfonate, heptafluoropropanesulfonate, nonafluorobutanesulfonate, bis(fluorosulfonyl)imide, bis(trifluoromethanesulfonyl)imide .

作為離子性液體之具體例，可從上述陽離子成分與上述陰離子成分之組合適當選擇而使用。作為此種離子性液體之具體例，可列舉例如：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-正丁酯銨雙(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-正丁酯銨雙(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-正丁酯-N-己基銨雙(三氟甲磺醯基)醯亞胺、N,N-二甲基-正丁酯-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-正丁酯-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 and use suitably from the combination of the said cation component and the said anionic component. Specific examples of such ionic liquids include, for example, 1-hexylpyridinium bis(fluorosulfonyl)imide, 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)imide, 1-butyl-3 -Methylpyridinium bis(pentafluoroethanesulfonyl)imide, 1-octyl-4-methylpyridinium bis(fluorosulfonyl)imide, 1,1-dimethylpyrrolidinium Bis(trifluoromethanesulfonyl)imide, 1-methyl-1-ethylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyrrolidinium Bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyrrolidinium bis(fluorosulfonyl)imide, 1-methyl-1-butylpyrrolidinium bis( Trifluoromethanesulfonyl)imide, 1-methyl-1-pentylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-hexylpyrrolidinium bis(trifluoromethanesulfonyl)imide Fluoromethanesulfonyl)imide, 1-methyl-1-heptylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide fluoromethanesulfonyl)imide, 1-ethyl-1-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-pentylpyrrolidinium bis(trifluoromethanesulfonyl)imide Fluoromethanesulfonyl)imide, 1-ethyl-1-hexylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-heptylpyrrolidinium bis(trifluoromethanesulfonyl)imide Mesyl)imide, 1,1-dipropylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-propyl-1-butylpyrrolidinium bis(trifluoromethanesulfonyl) Acrylo)imide, 1,1-dibutylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-propylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-Pentylpiperidinium bis(trifluoromethanesulfonyl)imide, 1,1-dimethylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1- Ethylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1- Propylpiperidinium bis(fluorosulfonyl)imide, 1-methyl-1-butylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-pentyl Piperidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-hexylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-heptylpiperidine Dipyridinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-propylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-butylpiperidine Peridinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-pentylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-hexylpiperidine Onium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-heptylpiperidinium bis(trifluoromethanesulfonyl)imide, 1,1-dipropylpiperidinium bis (trifluoromethanesulfonyl)imide, 1- Propyl-1-butylpiperidinium bis(trifluoromethanesulfonyl)imide, 1,1-dibutylpiperidinium bis(trifluoromethanesulfonyl)imide, 1,1- Dimethylpyrrolidinium bis(pentafluoroethylsulfonyl)imide, 1-methyl-1-ethylpyrrolidinium bis(pentafluoroethylsulfonyl)imide, 1-methyl-1 - Propylpyrrolidinium bis(pentafluoroethylsulfonyl)imide, 1-methyl-1-butylpyrrolidinium bis(pentafluoroethylsulfonyl)imide, 1-methyl-1 - Amylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-hexylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-methyl-1- Heptylpyrrolidinium bis(pentafluoroethylsulfonyl)imide, 1-ethyl-1-propylpyrrolidinium bis(pentafluoroethylsulfonyl)imide, 1-ethyl-1- Butylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-pentylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1- Hexylpyrrolidinium bis(pentafluoroethylsulfonyl)imide, 1-ethyl-1-heptylpyrrolidinium bis(pentafluoroethylsulfonyl)imide, 1,1-dipropylpyrrole Dipyridinium bis(pentafluoroethylsulfonyl)imide, 1-propyl-1-butylpyrrolidinium bis(pentafluoroethylsulfonyl)imide, 1,1-dibutylpyrrolidinium Bis(pentafluoroethanesulfonyl)imide, 1-propylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-pentylpiperidinium bis(pentafluoroethanesulfonyl)imide Imine, 1,1-Dimethylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-Methyl-1-ethylpiperidinium bis(pentafluoroethanesulfonyl)imide , 1-methyl-1-propylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-butylpiperidinium bis(pentafluoroethanesulfonyl)imide , 1-methyl-1-pentylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-hexylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-Methyl-1-heptylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-propylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-Ethyl-1-butylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-pentylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-Ethyl-1-hexylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-heptylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1 , 1-Dipropylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-propyl-1-butylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1,1 -Dibutylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazolium heptafluorobutane acid salt, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl-3-methylimidazolium Nonafluorobutanesulfonate, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide Imine, 1-ethyl-3-methylimidazolium bis(pentafluoroethanesulfonyl ) imide, 1-ethyl-3-methylimidazolium tris(trifluoromethanesulfonyl) methide, 1-butyl-3-methylimidazolium trifluoroacetate, 1-butyl- 3-Methylimidazolium heptafluorobutyrate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium perfluorobutanesulfonate, 1- Butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-hexyl-3-methylimidazolium triflate, 1-hexyl-3-methylimidazolium bis (fluorosulfonyl)imide, 1,2-dimethyl-3-propylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-2,3,5-trimethyl pyrazolium bis(trifluoromethanesulfonyl)imide, 1-propyl-2,3,5-trimethylpyrazolium bis(trifluoromethanesulfonyl)imide, 1-butane yl-2,3,5-trimethylpyrazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-2,3,5-trimethylpyrazolium bis(pentafluoroethanesulfonate) Acrylo)imide, 1-propyl-2,3,5-trimethylpyrazolium bis(pentafluoroethanesulfonyl)imide, 1-butyl-2,3,5-trimethyl pyrazolium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-2,3,5-trimethylpyrazolium(trifluoromethanesulfonyl)trifluoroacetamide, 1- Propyl-2,3,5-trimethylpyrazolium (trifluoromethanesulfonyl)trifluoroacetamide, 1-butyl-2,3,5-trimethylpyrazolium (trifluoromethane Sulfonyl)trifluoroacetamide, trimethylpropylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-propylammonium bis(trifluoromethanesulfonyl)imide fluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-n-butyl ammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N- Ethyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-hexylammonium bis(trifluoromethanesulfonyl)imide , N,N-dimethyl-N-ethyl-N-heptylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-nonylammonium Bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N,N-dipropylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl- N-propyl-n-butylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-propyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide Imine, N,N-dimethyl-N-propyl-N-hexylammonium bis(trifluoromethanesulfonyl)imine, N,N-dimethyl-N-propyl-N-heptyl Ammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-n-butyl ester-N-hexylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl -N-butyl ester-N-heptylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-pentyl-N-hexylammonium bis(trifluoromethanesulfonyl)imide imine, N,N-dimethyl-N,N-dihexylammonium bis(trifluoromethanesulfonyl)imide, trimethylheptylammonium bis(trifluoromethanesulfonyl)imide, N,N-Diethyl-N-methyl-N-propylammonium bis(trifluoromethanesulfonyl)imide, N ,N-diethyl-N-methyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N,N-heptylammonium Bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-propyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide, triethylpropylammonium Bis(trifluoromethanesulfonyl)imide, Tripentylammonium bis(trifluoromethanesulfonyl)imide, Triethylheptylammonium bis(trifluoromethanesulfonyl)imide, N , N-dipropyl-N-methyl-N-ethylammonium bis(trifluoromethanesulfonyl)imide, N,N-dipropyl-N-methyl-N-pentylammonium bis( Trifluoromethanesulfonyl)imide, N,N-dipropyl-n-butyl ester-N-hexylammonium bis(trifluoromethanesulfonyl)imide, N,N-dipropyl-N, N-dihexylammonium bis(trifluoromethanesulfonyl)imide, N,N-dibutyl-N-methyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide, N , N-dibutyl-N-methyl-N-hexylammonium bis(trifluoromethanesulfonyl)imide, trioctylmethylammonium bis(trifluoromethanesulfonyl)imide, N- Methyl-N-ethyl-N-propyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide, 1-butylpyridinium(trifluoromethanesulfonyl)trifluoroacetamide , 1-butyl-3-methylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-ethyl-3-methylimidazolium (trifluoromethanesulfonyl) trifluoroacetamide , tetrahexylammonium bis(trifluoromethanesulfonyl)imide, diallyldimethylammonium triflate, diallyldimethylammonium bis(trifluoromethanesulfonyl)imide imine, diallyldimethylammonium bis(pentafluoroethanesulfonyl)imide, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium tris Fluoromethanesulfonate, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide, N,N-diethyl yl-N-methyl-N-(2-methoxyethyl)ammonium bis(pentafluoroethanesulfonyl)imide, glycidyltrimethylammonium triflate, glycidyl trifluoromethanesulfonate Methylammonium bis(trifluoromethanesulfonyl)imide, glycidyltrimethylammonium bis(pentafluoroethanesulfonyl)imide, diallyldimethylammonium bis(trifluoromethanesulfonyl) Acrylo)imide, diallyldimethylbis(pentafluoroethanesulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide imine, etc.

該等離子性液體中，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 plasma liquids, more preferred are 1-hexylpyridinium bis(fluorosulfonyl)imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl-3 -Methylpyridinium pentafluoroethanesulfonate, 1-ethyl-3-methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutanesulfonate, 1- Butyl-3-methylpyridinium triflate, 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide, 1-octyl-4-methylpyridine Onium bis(fluorosulfonyl)imide, 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl)imide, 1-methyl-1-propylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpiperidinium bis(fluoro Sulfonyl)imide, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl-3 - Methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide, 1-hexyl-3-methylimidazolium Bis(fluorosulfonyl)imide, trimethylpropylammonium bis(trifluoromethanesulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide base) imide.

離子性液體可使用市售者，亦可如下文所述進行合成。作為離子性液體之合成方法，只要能獲得目標離子性液體則無特別限定，一般而言，可使用如文獻「離子性液體-開發之前沿及未來-」(CMC出版(股)發行)中記載之鹵化物法、氫氧化物法、酸酯法、錯合法及中和法等。A commercially available ionic liquid can be used, or it can be synthesized as described below. The method for synthesizing the ionic liquid is not particularly limited as long as the target ionic liquid can be obtained. Generally, the method described in the document "Ionic Liquid-Development Frontier and Future-" (issued by CMC Publishing Co., Ltd.) can be used. The halide method, hydroxide method, acid ester method, complex method and neutralization method, etc.

以下，關於鹵化物法、氫氧化物法、酸酯法、錯合法及中和法，以含氮鎓鹽為例對其合成方法進行說明，對於其他含硫鎓鹽、含磷鎓鹽等其他離子性液體亦可藉由相同之方法獲得。Hereinafter, regarding the halide method, hydroxide method, acid ester method, complexation method and neutralization method, the synthesis method of nitrogen-containing onium salt will be described as an example. Ionic liquids can also be obtained by the same method.

鹵化物法係藉由如反應式(1)～(3)所示之反應進行之方法。首先，使三級胺與鹵烷反應而獲得鹵化物(反應式(1)，使用氯、溴、碘作為鹵素)。The halide method is a method carried out by the reactions shown in the reaction formulae (1) to (3). First, a halide is obtained by reacting a tertiary amine with an alkyl halide (reaction formula (1), using chlorine, bromine, and iodine as the halogen).

使獲得之鹵化物與具有目標離子性液體之陰離子結構(A -)之酸(HA)或鹽(MA，M為銨、鋰、鈉、鉀等與目標陰離子形成鹽之陽離子)反應而獲得目標離子性液體(R 4NA)。 The target anion is obtained by reacting the obtained halide with an acid (HA) or a salt (MA, M is a cation that forms a salt with the target anion such as ammonium, lithium, sodium, potassium, etc.) with the anion structure (A − ) of the target ionic liquid. Ionic liquid (R 4 NA).

[化2]

Figure 02_image003
[hua 2]
Figure 02_image003

氫氧化物法係藉由如反應式(4)～(8)所示之反應進行之方法。首先，使鹵化物(R 4NX)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(Ag 2O)之反應(反應式(6))而獲得氫氧化物(R 4NOH)(使用氯、溴、碘作為鹵素)。 The hydroxide method is a method carried out by the reactions shown in the reaction formulae (4) to (8). First, the halide (R 4 NX) is electrolyzed by an ion exchange membrane method (reaction formula (4)), an OH type ion exchange resin method (reaction formula (5)), or a reaction with silver oxide (Ag 2 O) ( Reaction formula (6)) to obtain hydroxide (R 4 NOH) (using chlorine, bromine and iodine as halogen).

針對所獲得之氫氧化物與上述鹵化法同樣地使用反應式(7)～(8)之反應，藉此獲得目標離子性液體(R 4NA)。 The target ionic liquid (R 4 NA) was obtained by using the reactions of the reaction formulae (7) to (8) in the same manner as the above-mentioned halogenation method with respect to the obtained hydroxide.

[化3]

Figure 02_image005
[hua 3]
Figure 02_image005

酸酯法係藉由如反應式(9)～(11)所示之反應進行之方法。首先，使三級胺(R 3N)與酸酯反應而獲得酸酯化物(反應式(9)，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作為酸酯)。 The acid ester method is a method carried out by the reactions 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), using esters of inorganic acids such as sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, and carbonic acid, or methanesulfonic acid, methanesulfonic acid, etc. esters of organic acids such as phosphonic acid, formic acid, etc. as acid esters).

針對所獲得之酸酯化物與上述鹵化法同樣地使用反應式(10)～(11)之反應，藉此獲得目標離子性液體(R 4NA)。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。 The target ionic liquid (R 4 NA) was obtained by using the reaction of the reaction formulae (10) to (11) in the same manner as the above-mentioned halogenation method with respect to the obtained acid ester. Moreover, an ionic liquid can also be obtained directly by using methyl trifluoromethanesulfonate, methyl trifluoroacetate, etc. as an acid ester.

[化4]

Figure 02_image007
[hua 4]
Figure 02_image007

中和法係藉由如反應式(12)所示之反應進行之方法。可藉由使三級胺與CF 3COOH、CF 3SO 3H、(CF 3SO 2) 2NH、(CF 3SO 2) 3CH、(C 2F 5SO 2) 2NH等有機酸反應而獲得。 The neutralization method is a method carried out by the reaction shown in the reaction formula (12). Tertiary amines 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 obtained.

[化5]

Figure 02_image009
[hua 5]
Figure 02_image009

上述反應式(1)～(12)中記載之R表示氫或碳數1～20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.

＜A-1-4.氟系化合物＞ 作為氟系化合物，可於不損害本發明之效果之範圍內，採用任意適當之氟系化合物。藉由使黏著劑組合物除了包含基礎聚合物之外，還包含氟系化合物及上述離子性化合物兩者，可提供一種充分地抑制剝離靜電壓而於剝離時不使該光學構件或該電子構件受損之表面保護膜，該表面保護膜代表性而言為包含黏著劑層之表面保護膜，其於光學構件或電子構件之製造步驟中，為了防止該光學構件或該電子構件之表面於加工、組裝、檢查、運輸等時受損而貼合於該光學構件或該電子構件之露出面。 <A-1-4. Fluorine Compounds> As the fluorine-based compound, any appropriate fluorine-based compound can be used within a range that does not impair the effects of the present invention. By making the adhesive composition contain both the fluorine-based compound and the above-mentioned ionic compound in addition to the base polymer, it is possible to provide the optical member or the electronic member that can sufficiently suppress the peeling electrostatic voltage without causing the optical member or the electronic member to be peeled off. Damaged surface protection film, which is typically a surface protection film containing an adhesive layer, in the manufacturing steps of optical members or electronic members, in order to prevent the surface of the optical member or the electronic member from being processed , assembling, inspecting, transporting, etc., and sticking to the exposed surface of the optical component or the electronic component.

氟系化合物可僅為1種，亦可為2種以上。Only one type of fluorine-based compound may be used, or two or more types may be used.

作為氟系化合物，可列舉例如選自含氟化合物、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。Examples of the fluorine-based compound include at least one selected from the group consisting of fluorine-containing compounds, hydroxyl-containing fluorine-based compounds, and crosslinkable functional group-containing fluorine-based compounds.

作為含氟化合物，可列舉例如：具有氟脂肪族烴骨架之化合物、使有機化合物與氟系化合物共聚而成之含氟有機化合物、包含有機化合物之含氟化合物等。作為氟脂肪族烴骨架，可列舉例如：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。The fluorine-containing compound includes, for example, a compound having a fluoroaliphatic hydrocarbon skeleton, a fluorine-containing organic compound obtained by copolymerizing an organic compound and a fluorine-based 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, fluorotert-butane, fluoropentane, and fluorohexane. -C10 alkanes, etc.

含氟化合物之較佳之實施方式係具有含氟基與親水性基及/或親油性基之低聚物(「特定氟系化合物」)。藉由包含(併用)離子性化合物與如上所述之「特定氟系化合物」兩者，能顯著地表現本發明之效果。推測其原因在於，如上所述，藉由在黏著劑組合物中，使能表現抗靜電效果之離子性化合物與氟系化合物(較佳為，特定氟系化合物)併存，而藉由與氟系化合物(較佳為，特定氟系化合物)之協同效應，使得離子性化合物偏集存在於黏著劑層之表面側(與被黏著體貼合之側)。作為含氟基，代表性而言可列舉含氟之烷基(例如，CF 3-等)及/或含氟之伸烷基(例如，-CF 2-CF 2-等)。親水性基係指具有親水性之基，親水性在英語中被譯為「hydrophilic」，意指「與水具有親和性」，此為業者所周知之特性(例如，參考McGraw-Hill科學技術用語大辭典(修訂第3版，日刊工業新聞社)等)。親油性基係指具有親油性之基，親油性在英語中被譯為「lipophilic」，意指「與油具有親和性」，此為業者所周知之特性(例如，參考McGraw-Hill科學技術用語大辭典(修訂第3版，日刊工業新聞社)等)。 A preferred embodiment of the fluorine-containing compound is an oligomer having a fluorine-containing group and a hydrophilic group and/or a lipophilic group ("specific fluorine-based compound"). The effect of the present invention can be remarkably exhibited by including (combining) both the ionic compound and the above-mentioned "specific fluorine-based compound". The reason for this is presumed to be that, as described above, the ionic compound capable of exhibiting an antistatic effect and the fluorine-based compound (preferably, a specific fluorine-based compound) coexist in the adhesive composition, and the fluorine-based compound The synergistic effect of the compound (preferably, a specific fluorine-based compound) makes the ionic compound segregated on the surface side of the adhesive layer (the side attached to the adherend). As a fluorine-containing group, a fluorine-containing alkyl group (for example, CF3- etc.) and/or a fluorine-containing alkylene group (for example, -CF2 - CF2- etc.) are mentioned typically. Hydrophilic group refers to a group with hydrophilicity, and hydrophilicity is translated as "hydrophilic" in English, which means "affinity with water", which is a well-known characteristic of the industry (for example, refer to McGraw-Hill Glossary of Science and Technology Great Dictionary (Revised 3rd Edition, Nikkan Kogyo Shimbun, etc.). A lipophilic group refers to a group with lipophilicity, and lipophilicity is translated as "lipophilic" in English, which means "affinity with oil", which is a well-known characteristic of the industry (for example, refer to McGraw-Hill Glossary of Science and Technology Great Dictionary (Revised 3rd Edition, Nikkan Kogyo Shimbun, etc.).

作為「特定氟系化合物」，就更能表現本發明之效果之方面而言，更佳為，含有含氟基、親水性基及親油性基之低聚物。若「特定氟系化合物」不含有親水性基或「特定氟系化合物」不含有親油性基，則有無法充分地表現本發明之效果之虞。As the "specific fluorine-based compound", an oligomer containing a fluorine-containing group, a hydrophilic group, and a lipophilic group is more preferable in that the effect of the present invention can be more exhibited. If the "specific fluorine-based compound" does not contain a hydrophilic group or the "specific fluorine-based compound" does not contain a lipophilic group, the effects of the present invention may not be sufficiently exhibited.

關於含氟化合物之較佳之實施方式，就更能表現本發明之效果之方面而言，較佳為於製成0.1%甲苯溶液之情形時表面張力為26.0 mN/m～27.0 mN/m之含氟化合物(甲苯之表面張力為27.9 mN/m)。如此，若含氟化合物之於製成0.1%甲苯溶液之情形時之表面張力處於26.0 mN/m～27.0 mN/m之極窄之特定範圍內，則更能表現本發明之效果，尤其是能表現出不論是對於玻璃之剝離靜電壓，還是對於樹脂之剝離靜電壓均能充分地抑制之意料外之顯著效果。尤其是，於假定本發明之較佳之實施方式中之表面保護膜為預定之用途即貼合於光學構件或電子構件之露出面之用途之情形時，能表現出不論是對於玻璃之剝離靜電壓，還是對於樹脂之剝離靜電壓均能充分地抑制之效果極為重要。As for the preferred embodiment of the fluorine-containing compound, from the point of view of better exhibiting the effects of the present invention, it is preferably a fluorine-containing compound having a surface tension of 26.0 mN/m to 27.0 mN/m when it is prepared as a 0.1% toluene solution. Fluorine compound (the surface tension of toluene is 27.9 mN/m). In this way, if the surface tension of the fluorine-containing compound in the case of making a 0.1% toluene solution is within a very narrow specific range of 26.0 mN/m to 27.0 mN/m, the effect of the present invention can be better exhibited, especially It exhibited an unexpectedly remarkable effect of sufficiently suppressing the peeling electrostatic voltage of glass and the peeling electrostatic voltage of resin. In particular, when it is assumed that the surface protection film in the preferred embodiment of the present invention is used for a predetermined purpose, that is, the purpose of attaching to the exposed surface of an optical member or an electronic member, it can exhibit a peeling electrostatic voltage regardless of whether it is a glass. , or the effect of sufficiently suppressing the peeling electrostatic voltage of the resin is extremely important.

含氟化合物之尤佳之實施方式係含有含氟基、親水性基及親油性基之低聚物，於製成0.1%甲苯溶液之情形時表面張力為26.0 mN/m～27.0 mN/m(甲苯之表面張力為27.9 mN/m)。若含氟化合物之尤佳之實施方式係含有含氟基、親水性基及親油性基之低聚物，且於製成0.1%甲苯溶液之情形時表面張力為26.0 mN/m～27.0 mN/m(甲苯之表面張力為27.9 mN/m)，則更能表現本發明之效果，尤其是，能表現出不論是對於玻璃之剝離靜電壓，還是對於樹脂之剝離靜電壓均能極充分地抑制之意料外之極為顯著之效果。尤其是，於假定本發明之較佳之實施方式中之表面保護膜為預定之用途即貼合於光學構件或電子構件之露出面之用途之情形時，能表現出不論是對於玻璃之剝離靜電壓，還是對於樹脂之剝離靜電壓均能極充分地抑制之效果極為重要。A particularly preferred embodiment of the fluorine-containing compound is an oligomer containing a fluorine-containing group, a hydrophilic group and a lipophilic group, and the surface tension is 26.0 mN/m～27.0 mN/m ( The surface tension of toluene is 27.9 mN/m). A particularly preferred embodiment of the fluorine-containing compound is an oligomer containing a fluorine-containing group, a hydrophilic group and a lipophilic group, and the surface tension is 26.0 mN/m～27.0 mN/ in the case of making a 0.1% toluene solution m (the surface tension of toluene is 27.9 mN/m), the effect of the present invention can be better exhibited, especially, the peeling electrostatic voltage of glass and the peeling electrostatic voltage of resin can be extremely sufficiently suppressed. Unexpected and very significant effect. In particular, when it is assumed that the surface protection film in the preferred embodiment of the present invention is used for a predetermined purpose, that is, the purpose of attaching to the exposed surface of an optical member or an electronic member, it can exhibit a peeling electrostatic voltage regardless of whether it is a glass. , it is also extremely important for the effect of extremely sufficient suppression of the peeling electrostatic voltage of the resin.

作為含氟化合物之市售品，可列舉例如以下所述者。As a commercial item of a fluorine-containing compound, the following are mentioned, for example.

DIC(股)製造之MEGAFAC Series： 代表性而言，「MEGAFAC F-114」、「MEGAFAC F-251」、「MEGAFAC F-253」、「MEGAFAC F-281」、「MEGAFAC F-410」、「MEGAFAC F-430」、「MEGAFAC F-444」、「MEGAFAC F-477」、「MEGAFAC F-510」、「MEGAFAC F-551-A」、「MEGAFAC F-553」、「MEGAFAC F-554」、「MEGAFAC F-555-A」、「MEGAFAC F-556」、「MEGAFAC F-557」、「MEGAFAC F-558」、「MEGAFAC F-559」、「MEGAFAC F-560」、「MEGAFAC F-561」、「MEGAFAC F-562」、「MEGAFAC F-563」、「MEGAFAC F-565」、「MEGAFAC F-568」、「MEGAFAC F-569」、「MEGAFAC F-570」、「MEGAFAC F-576」、「MEGAFAC R-01」、「MEGAFAC R-40」、「MEGAFAC R-40-LM」、「MEGAFAC R-41」、「MEGAFAC R-41-LM」、「MEGAFAC R-94」、「MEGAFAC RS-56」、「MEGAFAC RS-72-K」、「MEGAFAC RS-75-A」、「MEGAFAC RS-75-NS」、「MEGAFAC RS-78」、「MEGAFAC RS-90」等。 MEGAFAC Series manufactured by DIC (stock): Typically, "MEGAFAC F-114", "MEGAFAC F-251", "MEGAFAC F-253", "MEGAFAC F-281", "MEGAFAC F-410", "MEGAFAC F-430", "MEGAFAC F-281" -444", "MEGAFAC F-477", "MEGAFAC F-510", "MEGAFAC F-551-A", "MEGAFAC F-553", "MEGAFAC F-554", "MEGAFAC F-555-A", "MEGAFAC F-556", "MEGAFAC F-557", "MEGAFAC F-558", "MEGAFAC F-559", "MEGAFAC F-560", "MEGAFAC F-561", "MEGAFAC F-562", " MEGAFAC F-563, MEGAFAC F-565, MEGAFAC F-568, MEGAFAC F-569, MEGAFAC F-570, MEGAFAC F-576, MEGAFAC R-01, MEGAFAC R-40", "MEGAFAC R-40-LM", "MEGAFAC R-41", "MEGAFAC R-41-LM", "MEGAFAC R-94", "MEGAFAC RS-56", "MEGAFAC RS-72- K, "MEGAFAC RS-75-A", "MEGAFAC RS-75-NS", "MEGAFAC RS-78", "MEGAFAC RS-90", etc.

AGC清美化學(股)製造之Surflon Series： 代表性而言，「S-242」、「S-243」、「S-386」等。 Surflon Series manufactured by AGC Qingmei Chemical Co., Ltd.: Typically, "S-242", "S-243", "S-386", etc.

住友3M(股)製造之FC Series： 代表性而言，「FC-4430」、「FC-4432」等。 FC Series manufactured by Sumitomo 3M Co., Ltd.: Typically, "FC-4430", "FC-4432", etc.

NEOS(股)製造之FTERGENT Series： 代表性而言，「FTERGENT100」、「FTERGENT100C」、「FTERGENT110」、「FTERGENT150」、「FTERGENT150CH」、「FTERGENT250」、「FTERGENT400SW」等。 FTERGENT Series manufactured by NEOS (stock): Typically, "FTERGENT100", "FTERGENT100C", "FTERGENT110", "FTERGENT150", "FTERGENT150CH", "FTERGENT250", "FTERGENT400SW" and the like.

北村化學產業(股)製造之PF Series： 代表性而言，「PF-136A」、「PF-156A」、「PF-151N」、「PF-636」、「PF-6320」、「PF-656」、「PF-6520」、「PF-651」、「PF-652」、「PF-3320」等。 PF Series manufactured by Kitamura Chemical Industry Co., Ltd.: Typically, "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，可使用例如先前公知之樹脂，可列舉例如：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，可列舉例如：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。此外，還可列舉：含羥基化合物與具有經氟化之烷基之化合物的共聚物、含羥基化合物與含氟化合物共聚而成之含氟有機化合物、包含含羥基之有機化合物之含氟化合物等。作為此種含羥基之氟系化合物之市售品，可列舉例如：名為「Lumiflon」之商品(旭硝子(股)製造)、名為「CEFRAL COAT」之商品(中央硝子(股)製造)、名為「ZAFFLON」之商品(東亞合成(股)製造)、名為「ZEFFLE」之商品(大金工業(股)製造)等。As the hydroxyl group-containing fluorine-based compound, for example, known resins can be used, and examples thereof include International Publication No. 94/06870, Japanese Patent Laid-Open No. 8-12921, Japanese Patent Laid-Open No. 10-72569, Japanese Patent Laid-Open No. 10-72569, The hydroxyl group-containing fluororesin described in Japanese Patent Laid-Open No. 4-275379, International Publication No. 97/11130, International Publication No. 96/26254, and the like. Examples of other hydroxyl-containing fluororesins 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. Hei 8-12922 Fluoroolefin copolymers and the like described in the gazette and the like. In addition, copolymers of hydroxyl-containing compounds and compounds having a fluorinated alkyl group, fluorine-containing organic compounds obtained by copolymerization of hydroxyl-containing compounds and fluorine-containing compounds, fluorine-containing compounds containing hydroxyl-containing organic compounds, etc. . Examples of commercially available products of such a hydroxyl group-containing fluorine-based compound include a product named "Lumiflon" (manufactured by Asahi Glass Co., Ltd.), a product named "CEFRAL COAT" (manufactured by Chuo Glass Co., Ltd.), A product named "ZAFFLON" (manufactured by Toa Gosei Co., Ltd.), a product named "ZEFFLE" (manufactured by Daikin Industries, Ltd.), etc.

作為含交聯性官能基之氟系化合物，可列舉例如：如全氟辛酸等之具有經氟化之烷基之羧酸化合物、含交聯性官能基之化合物與具有經氟化之烷基之化合物之共聚物、含交聯性官能基之化合物與含氟化合物共聚而成之含氟有機化合物、包含含交聯性官能基之化合物之含氟化合物等。作為此種含交聯性官能基之氟系化合物之市售品，可列舉例如名為「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」之商品(DIC(股)製造)等。Examples of the crosslinkable functional group-containing fluorine-based compound include carboxylic acid compounds having a fluorinated alkyl group such as perfluorooctanoic acid, compounds having a crosslinkable functional group, and compounds having a fluorinated alkyl group. Fluorine-containing organic compounds obtained by copolymerization of cross-linkable functional group-containing compounds and fluorine-containing compounds, fluorine-containing compounds containing cross-linkable functional group-containing compounds, etc. Examples of commercially available products of such a crosslinkable functional group-containing fluorine-based compound include "MEGAFAC F-570", "MEGAFAC RS-55", "MEGAFAC RS-56", and "MEGAFAC RS-72- Products of "K", "MEGAFAC RS-75", "MEGAFAC RS-76-E", "MEGAFAC RS-76-NS", "MEGAFAC RS-78", "MEGAFAC RS-90" (manufactured by DIC Corporation) Wait.

能夠以市售品之形式獲取之含氟化合物中，作為相當於上述「具有含氟基與親水性基及/或親油性基之低聚物」者，代表性而言，可列舉DIC(股)製造之如下含氟化合物： 「MEGAFAC F-477」(含有含氟基、親水性基及親油性基之低聚物，於製成0.1%甲苯溶液之情形時表面張力＝26.4 mN/m)； 「MEGAFAC F-551-A」(含有含氟基及親油性基之低聚物，於製成0.1%甲苯溶液之情形時表面張力＝25.6 mN/m)； 「MEGAFAC F-553」(含有含氟基、親水性基及親油性基之低聚物，於製成0.1%甲苯溶液之情形時表面張力＝26.4 mN/m)； 「MEGAFAC F-554」(含有含氟基及親油性基之低聚物，於製成0.1%甲苯溶液之情形時表面張力＝25.0 mN/m)； 「MEGAFAC F-555-A」(含有含氟基、親水性基及親油性基之低聚物，於製成0.1%甲苯溶液之情形時表面張力＝20.4 mN/m)； 「MEGAFAC F-557」(含有含氟基、親水性基及親油性基之低聚物，於製成0.1%甲苯溶液之情形時表面張力＝26.3 mN/m)； 「MEGAFAC F-559」(含有含氟基、親水性基及親油性基之低聚物，於製成0.1%甲苯溶液之情形時表面張力＝26.1 mN/m)； 「MEGAFAC F-563」(含有含氟基及親油性基之低聚物，於製成0.1%甲苯溶液之情形時表面張力＝20.2 mN/m)； 「MEGAFAC F-569」(含有含氟基及親水性基之低聚物，於製成0.1%甲苯溶液之情形時表面張力＝19.7 mN/m)等。 Among the fluorine-containing compounds that can be obtained in the form of commercial products, DIC (stock ) manufactures the following fluorine-containing compounds: "MEGAFAC F-477" (oligomer containing fluorine group, hydrophilic group and lipophilic group, surface tension = 26.4 mN/m in the case of making a 0.1% toluene solution); "MEGAFAC F-551-A" (oligomer containing fluorine-containing group and lipophilic group, surface tension = 25.6 mN/m when prepared as a 0.1% toluene solution); "MEGAFAC F-553" (oligomer containing fluorine-containing group, hydrophilic group and lipophilic group, surface tension = 26.4 mN/m when made into 0.1% toluene solution); "MEGAFAC F-554" (oligomer containing fluorine-containing group and lipophilic group, surface tension = 25.0 mN/m when made into 0.1% toluene solution); "MEGAFAC F-555-A" (oligomer containing fluorine group, hydrophilic group and lipophilic group, surface tension = 20.4 mN/m in the case of making a 0.1% toluene solution); "MEGAFAC F-557" (oligomer containing fluorine group, hydrophilic group and lipophilic group, surface tension = 26.3 mN/m in the case of making a 0.1% toluene solution); "MEGAFAC F-559" (oligomer containing fluorine group, hydrophilic group and lipophilic group, surface tension = 26.1 mN/m in the case of making a 0.1% toluene solution); "MEGAFAC F-563" (oligomer containing fluorine-containing group and lipophilic group, surface tension = 20.2 mN/m when made into 0.1% toluene solution); "MEGAFAC F-569" (oligomer containing a fluorine-containing group and a hydrophilic group, surface tension = 19.7 mN/m in the case of a 0.1% toluene solution) and the like.

能夠以市售品之形式獲取之含氟化合物中，作為相當於上述「含有含氟基、親水性基及親油性基之低聚物，於製成0.1%甲苯溶液之情形時表面張力為26.0 mN/m～27.0 mN/m(甲苯之表面張力為27.9 mN/m)，含氟化合物」者，代表性而言，可列舉DIC(股)製造之如下含氟化合物： 「MEGAFAC F-477」(含有含氟基、親水性基及親油性基之低聚物，於製成0.1%甲苯溶液之情形時表面張力＝26.4 mN/m)； 「MEGAFAC F-553」(含有含氟基、親水性基及親油性基之低聚物，於製成0.1%甲苯溶液之情形時表面張力＝26.4 mN/m)； 「MEGAFAC F-557」(含有含氟基、親水性基及親油性基之低聚物，於製成0.1%甲苯溶液之情形時表面張力＝26.3 mN/m)； 「MEGAFAC F-559」(含有含氟基、親水性基及親油性基之低聚物，於製成0.1%甲苯溶液之情形時表面張力＝26.1 mN/m)等。 Among the fluorine-containing compounds that can be obtained in the form of commercial products, as the above-mentioned "oligomer containing fluorine-containing groups, hydrophilic groups and lipophilic groups, the surface tension is 26.0 when it is made into a 0.1% toluene solution. mN/m～27.0 mN/m (the surface tension of toluene is 27.9 mN/m), fluorine-containing compounds”, typically, the following fluorine-containing compounds produced by DIC (stock) can be listed: "MEGAFAC F-477" (oligomer containing fluorine group, hydrophilic group and lipophilic group, surface tension = 26.4 mN/m in the case of making a 0.1% toluene solution); "MEGAFAC F-553" (oligomer containing fluorine-containing group, hydrophilic group and lipophilic group, surface tension = 26.4 mN/m when made into 0.1% toluene solution); "MEGAFAC F-557" (oligomer containing fluorine group, hydrophilic group and lipophilic group, surface tension = 26.3 mN/m in the case of making a 0.1% toluene solution); "MEGAFAC F-559" (oligomer containing fluorine-containing group, hydrophilic group and lipophilic group, surface tension = 26.1 mN/m when prepared as a 0.1% toluene solution), etc.

＜A-1-5.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，含有任意適當之其他成分。作為此種其他成分，可列舉例如：樹脂成分、交聯促進劑、交聯觸媒、矽烷偶合劑、改性矽酮油等矽酮系添加劑、黏著賦予樹脂(松香衍生物、聚萜烯樹脂、石油樹脂、油溶性酚等)、防老化劑、無機填充劑、有機填充劑、金屬粉、著色劑(顏料或染料等)、箔狀物、紫外線吸收劑、抗氧化劑、光穩定劑、鏈轉移劑、塑化劑、軟化劑、導電劑、穩定劑、表面潤滑劑、防腐劑、耐熱穩定劑、聚合抑制劑、潤滑劑、溶劑、觸媒等。 <A-1-5. Other ingredients> The adhesive composition may contain any appropriate other components within the range that does not impair the effects of the present invention. Examples of such other components include resin components, cross-linking accelerators, cross-linking catalysts, silane coupling agents, silicone-based additives such as modified silicone oil, adhesion-imparting resins (rosin derivatives, polyterpene resins) , petroleum resin, oil-soluble phenol, etc.), anti-aging agent, inorganic filler, organic filler, metal powder, colorant (pigment or dye, etc.), foil, ultraviolet absorber, antioxidant, light stabilizer, chain Transfer agent, plasticizer, softener, conductive agent, stabilizer, surface lubricant, preservative, heat-resistant stabilizer, polymerization inhibitor, lubricant, solvent, catalyst, etc.

作為黏著劑組合物中之其他成分，代表性而言，可於不損害本發明之效果之範圍內包含改性矽酮油。藉由使黏著劑組合物包含改性矽酮油，能表現抗靜電特性之效果。尤其是，藉由與離子性液體併用，能更有效地表現抗靜電特性之效果。As other components in the adhesive composition, typically, modified silicone oil can be contained within a range not impairing the effects of the present invention. By including the modified silicone oil in the adhesive composition, the effect of antistatic properties can be exhibited. In particular, by using together with an ionic liquid, the effect of antistatic properties can be more effectively expressed.

於黏著劑組合物包含改性矽酮油之情形時，改性矽酮油之含有比率係相對於基礎聚合物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。藉由將改性矽酮油之含有比率調整至上述範圍內，能更有效地表現抗靜電特性之效果。When the adhesive composition contains the modified silicone oil, the content ratio of the modified silicone oil is relative to 100 parts by weight of the base polymer, preferably 0.001 parts by weight to 50 parts by weight, more preferably 0.005 parts by weight ~40 parts by weight, more preferably 0.007 parts by weight to 30 parts by weight, particularly preferably 0.008 parts by weight to 20 parts by weight, and most preferably 0.01 parts by weight to 10 parts by weight. By adjusting the content ratio of the modified silicone oil to the above range, the effect of antistatic properties can be more effectively exhibited.

作為改性矽酮油，可於不損害本發明之效果之範圍內，採用任意適當之改性矽酮油。作為此種改性矽酮油，可列舉例如能夠從信越化學工業(股)獲取之改性矽酮油。As the modified silicone oil, any appropriate modified silicone oil can be used within a range that does not impair the effects of the present invention. As such a modified silicone oil, the modified silicone oil available from Shin-Etsu Chemical Industry Co., Ltd. is mentioned, for example.

作為改性矽酮油，較佳為聚醚改性矽酮油。藉由採用聚醚改性矽酮油，能更有效地表現抗靜電特性之效果。As the modified silicone oil, polyether-modified silicone oil is preferred. By using polyether modified silicone oil, the effect of antistatic properties can be more effectively exhibited.

作為聚醚改性矽酮油，可列舉：側鏈型聚醚改性矽酮油、兩末端型聚醚改性矽酮油等。其中，就能充分地且更有效地表現抗靜電特性之效果之方面而言，較佳為兩末端型聚醚改性矽酮油。As the polyether-modified silicone oil, a side-chain type polyether-modified silicone oil, a double-terminal type polyether-modified silicone oil, and the like can be mentioned. Among them, two-terminal type polyether-modified silicone oil is preferable in that the effect of antistatic properties can be sufficiently and more effectively exhibited.

≪A-2.基材層≫ 基材層可僅為1層，亦可為2層以上。基材層可為延伸而成者。 ≪A-2. Substrate layer≫ The base material layer may be only one layer, or may be two or more layers. The substrate layer may be extended.

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 base material layer is preferably 4 μm to 450 μm, more preferably 8 μm to 400 μm, further preferably 12 μm to 350 μm, particularly preferably 16 μm to 250 μm.

對於基材層之未附設黏著劑層之面，出於形成容易退繞之捲繞體等目的，例如可於基材層添加脂肪醯胺、聚乙烯亞胺、長鏈烷基系添加劑等而進行離型處理，或者設置包含矽酮系、長鏈烷基系、氟系等任意適當之剝離劑之塗層。For the purpose of forming a winding body that is easy to unwind on the surface of the base material layer without the adhesive layer, for example, aliphatic amides, polyethyleneimine, long-chain alkyl-based additives, etc. can be added to the base material layer. Perform release treatment, or set up a coating containing any appropriate release agent such as silicone, long-chain alkyl, and fluorine.

作為基材層之材料，可根據用途採用任意適當之材料。可列舉例如：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。基材層可由1種材料構成，亦可由2種以上之材料構成。例如，可由2種以上之塑膠構成。As the material of the base material layer, any appropriate material can be adopted according to the application. For example, plastic, paper, metal film, nonwoven fabric, etc. are mentioned. Preferably it is plastic. That is, the base material layer is preferably a plastic film. The base material layer may be composed of one kind of material, or may be composed of two or more kinds of materials. For example, it may consist of two or more types of plastics.

作為上述塑膠，可列舉例如：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，可列舉例如：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，可列舉例如：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，具體可列舉例如：均聚丙烯；以乙烯成分作為共聚成分之嵌段系、無規系、接枝系等丙烯系共聚物；Reactor-TPO(反應器直接製備熱塑性聚烯烴)；低密度、高密度、線性低密度、超低密度等乙烯系聚合物；乙烯-丙烯共聚物、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-丙烯酸丁酯共聚物、乙烯-甲基丙烯酸共聚物、乙烯-甲基丙烯酸甲酯共聚物等乙烯系共聚物等。As said plastics, a polyester-type resin, a polyamide-type resin, a polyolefin-type resin, etc. are mentioned, for example. As polyester-based resin, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc. are mentioned, for example. As a polyolefin resin, the homopolymer of an olefin monomer, the copolymer of an olefin monomer, etc. are mentioned, for example. Specific examples of polyolefin-based resins include: homopolypropylene; propylene-based copolymers such as block-based, random-based, and graft-based copolymers using ethylene as a copolymerization component; Reactor-TPO (reactor for direct production of thermoplastic polyolefins) ); low density, high density, linear low density, ultra-low density and other ethylene polymers; ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer , ethylene-butyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer and other ethylene-based copolymers, etc.

基材層可視需要含有任意適當之添加劑。作為基材層中可含有之添加劑，可列舉例如：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、數量可根據目的而適當地進行設定。尤其是，於基材層之材料為塑膠之情形時，為了防止劣化等，較佳為含有上述添加劑中之若干個。為了提高耐候性等，作為添加劑，尤佳為列舉：抗氧化劑、紫外線吸收劑、光穩定劑、填充劑。The base material layer may contain any appropriate additives as needed. As an additive which can be contained in a base material layer, antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, a filler, a pigment, etc. are mentioned, for example. The kind 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, in order to prevent deterioration or the like, it is preferable to contain some of the above-mentioned additives. In order to improve weather resistance etc., as an additive, antioxidant, a ultraviolet absorber, a light stabilizer, and a filler are mentioned especially as an additive.

作為抗氧化劑，可採用任意適當之抗氧化劑。作為此種抗氧化劑，可列舉例如：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。關於抗氧化劑之含有比率，相對於基材層之基底樹脂(於基材層為摻合物之情形時該摻合物為基底樹脂)，較佳為1重量%以下，更佳為0.5重量%以下，進而較佳為0.01重量%～0.2重量%。As the antioxidant, any appropriate antioxidant can be used. Examples of such antioxidants include phenolic antioxidants, phosphorus-based processing heat stabilizers, lactone-based processing heat stabilizers, sulfur-based heat-resistant stabilizers, and phenol/phosphorus-based antioxidants. The content ratio of the antioxidant is preferably 1 wt % or less, more preferably 0.5 wt % with respect to the base resin of the base material layer (when the base material layer is a blend, the blend is the base resin) Hereinafter, 0.01 to 0.2 weight % is more preferable.

作為紫外線吸收劑，可採用任意適當之紫外線吸收劑。作為此種紫外線吸收劑，可列舉例如：苯并***系紫外線吸收劑、三嗪系紫外線吸收劑、二苯甲酮系紫外線吸收劑等。關於紫外線吸收劑之含有比率，相對於形成基材層之基底樹脂(於基材層為摻合物之情形時該摻合物為基底樹脂)，較佳為2重量%以下，更佳為1重量%以下，進而較佳為0.01重量%～0.5重量%。As the ultraviolet absorber, any appropriate ultraviolet absorber can be used. As such an ultraviolet absorber, a benzotriazole type ultraviolet absorber, a triazine type ultraviolet absorber, a benzophenone type ultraviolet absorber, etc. are mentioned, for example. The content ratio of the ultraviolet absorber is preferably 2 wt % or less, more preferably 1 wt % or less with respect to the base resin forming the base layer (when the base layer is a blend, the blend is the base resin). % by weight or less, more preferably 0.01% by weight to 0.5% by weight.

作為光穩定劑，可採用任意適當之光穩定劑。作為此種光穩定劑，可列舉例如：受阻胺系光穩定劑、苯甲酸酯系光穩定劑等。關於光穩定劑之含有比率，相對於形成基材層之基底樹脂(於基材層為摻合物之情形時該摻合物為基底樹脂)，較佳為2重量%以下，更佳為1重量%以下，進而較佳為0.01重量%～0.5重量%。As the light stabilizer, any appropriate light stabilizer can be used. As such a light stabilizer, a hindered amine light stabilizer, a benzoate light stabilizer, etc. are mentioned, for example. The content ratio of the light stabilizer is preferably 2 wt % or less, more preferably 1 wt % or less with respect to the base resin forming the base layer (when the base layer is a blend, the blend is the base resin). % by weight or less, more preferably 0.01% by weight to 0.5% by weight.

作為填充劑，可採用任意適當之填充劑。作為此種填充劑，可列舉例如無機系填充劑等。作為無機系填充劑，具體可列舉例如：碳黑、氧化鈦、氧化鋅等。關於填充劑之含有比率，相對於形成基材層之基底樹脂(於基材層為摻合物之情形時該摻合物為基底樹脂)，較佳為20重量%以下，更佳為10重量%以下，進而較佳為0.01重量%～10重量%。As the filler, any appropriate filler can be used. As such a filler, an inorganic type filler etc. are mentioned, for example. Specific examples of the inorganic filler include carbon black, titanium oxide, zinc oxide, and the like. The content ratio of the filler is preferably 20 wt % or less, more preferably 10 wt %, with respect to the base resin forming the base layer (when the base layer is a blend, the blend is the base resin). % or less, more preferably 0.01% by weight to 10% by weight.

進而，作為添加劑，為了賦予抗靜電性，亦較佳為列舉：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。尤其是，為了防止污染並維持黏著性，較佳為高分子量系抗靜電劑或碳。Furthermore, as additives, in order to impart antistatic properties, surfactants, inorganic salts, polyols, metal compounds, inorganic-based, low-molecular-weight and high-molecular-weight antistatic agents such as carbon are also preferably mentioned. In particular, in order to prevent contamination and maintain adhesiveness, a high molecular weight antistatic agent or carbon is preferable.

≪≪B.用途≫≫ 本發明之實施方式之表面保護膜能表現充分地抑制剝離靜電壓而於剝離時不使該光學構件或該電子構件破損之效果，代表性而言為於光學構件或電子構件之製造步驟中，為了防止該光學構件或該電子構件之表面於加工、組裝、檢查、運輸等時受損而貼合於該光學構件或該電子構件之露出面，且包含黏著劑層之表面保護膜。因此，適宜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合有本發明之表面保護膜者。本發明之電子構件係貼合有本發明之表面保護膜者。 [實施例] ≪≪B. Use≫≫ The surface protective film of the embodiment of the present invention can sufficiently suppress the peeling electrostatic voltage without damaging the optical member or the electronic member during peeling. Typically, in the manufacturing process of the optical member or the electronic member, In order to prevent the surface of the optical component or the electronic component from being damaged during processing, assembly, inspection, transportation, etc., it is attached to the exposed surface of the optical component or the electronic component, and includes a surface protection film of an adhesive layer. Therefore, it is suitable for surface protection of optical members or electronic members. The optical member of the present invention is bonded with the surface protection film of the present invention. The electronic component of the present invention is bonded with the surface protection film of the present invention. [Example]

以下，利用實施例具體地對本發明進行說明，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估方法如下所述。再者，於記載為「份」之情形時，只要未作特別說明則意指「重量份」，於記載為「%」之情形時，只要未作特別說明則意指「重量%」。Hereinafter, the present invention will be specifically described using examples, but the present invention is not limited by these examples at all. In addition, the test and evaluation method in an Example etc. are as follows. In addition, when describing as "parts", unless otherwise specified, it means "weight part", and when describing as "%", unless specified otherwise, means "weight %".

＜黏著劑層表面之對於二碘甲烷之表面自由能之測定＞ 將已剝離隔離件之表面保護膜切割成寬度50 mm、長度100 mm之尺寸，以黏著劑層表面為上表面固定於接觸角計(協和界面科學公司製造，型號「CA-X」)，於黏著劑層表面滴加2.0 μL之水，測定接觸角。其次，按相同之步序，滴加2.0 μL之二碘甲烷，測定接觸角。根據以上之兩種液體之接觸角之值，使用Owens-Wendt法算出黏著劑層表面之對於二碘甲烷之表面自由能。 <Measurement of the surface free energy of the surface of the adhesive layer with respect to diiodomethane> Cut the surface protective film of the peeled separator into a size of 50 mm in width and 100 mm in length, and fix it on a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., model "CA-X") with the surface of the adhesive layer as the upper surface. 2.0 μL of water was added dropwise to the surface of the adhesive layer to measure the contact angle. Next, according to the same procedure, 2.0 μL of diiodomethane was added dropwise to measure the contact angle. According to the above contact angle values of the two liquids, the Owens-Wendt method was used to calculate the surface free energy of the surface of the adhesive layer with respect to diiodomethane.

＜從玻璃板之剝離力(於溫度23℃下放置30分鐘後)之測定＞ 利用2 kg之手壓輥往返一次將已剝離隔離件之表面保護膜(寬度25 mm×長度140 mm)之黏著劑層側貼合於玻璃板(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。 利用拉伸試驗機測定以上述方式獲得之評估用試樣。作為拉伸試驗機，使用島津製作所公司製造之名為「Autograph AG-Xplus HS 6000 mm/min高速型號(AG-50NX plus)」之商品。將評估用試樣設置於拉伸試驗機，開始拉伸試驗。具體而言，測定將表面保護膜從上述玻璃板剝離時之負載，將此時之平均負載設為表面保護膜從玻璃板之剝離力。拉伸試驗之條件設為試驗環境溫度：23℃，剝離角度：180度，剝離速度(拉伸速度)：300 mm/分鐘。 <Measurement of peeling force from glass plate (after 30 minutes at a temperature of 23°C)> The adhesive layer side of the surface protective film (width 25 mm × length 140 mm) of the peeled separator was attached to a glass plate (soda lime glass, manufactured by Songnang Glass Industry Co., Ltd.) , placed at an ambient temperature of 23°C for 30 minutes. The evaluation samples obtained in the above-described manner were measured with a tensile testing machine. As the tensile tester, a product called "Autograph AG-Xplus HS 6000 mm/min high-speed model (AG-50NX plus)" manufactured by Shimadzu Corporation was used. The sample for evaluation was set in the tensile testing machine, 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 that time was defined as the peeling force of the surface protective film from the glass plate. The conditions of the tensile test were set as the test environment temperature: 23° C., the peeling angle: 180 degrees, and the peeling speed (tensile speed): 300 mm/min.

＜對玻璃之剝離靜電壓及對丙烯酸系樹脂板之剝離靜電壓之測定＞ 將已剝離隔離件之表面保護膜切割成寬度70 mm、長度100 mm之尺寸，以使表面保護膜之一個端部從玻璃之端伸出30 mm之方式，利用手壓輥壓接於玻璃(鈉鈣玻璃，松浪硝子工業股份有限公司製造)或丙烯酸系樹脂板(Acrylite，三菱化學股份有限公司製造)之表面。 將該樣品於23℃×50%RH之環境下放置1天，然後設置於高度20 mm之樣品固定台之規定位置。將從玻璃伸出30 mm之表面保護膜之端部固定於自動卷取機，以成為剝離角度150°、剝離速度30 m/min之方式進行剝離。藉由固定在距被黏著體之中央高度為30 mm之位置上之電位測定器(SHISHIDO靜電氣公司製造，型號「STATIRON DZ-4」)測定此時所產生之被黏著體表面之電位，設為對玻璃之剝離靜電壓或對丙烯酸系樹脂板之剝離靜電壓。測定係於23℃、50%RH之環境下進行。 <Measurement of peeling electrostatic voltage to glass and peeling electrostatic voltage to acrylic resin board> Cut the surface protective film of the peeled separator into a size of 70 mm in width and 100 mm in length, so that one end of the surface protective film protrudes 30 mm from the end of the glass, and is pressed to the glass ( Soda lime glass, manufactured by Matsunami Glass Co., Ltd.) or acrylic resin board (Acrylite, manufactured by Mitsubishi Chemical Corporation). The sample was placed in an environment of 23°C × 50% RH for 1 day, and then set at the prescribed position of the sample fixing table with a height of 20 mm. The end of the surface protection film protruding 30 mm from the glass was fixed to an automatic winder, and peeling was performed so that the peeling angle was 150° and the peeling speed was 30 m/min. The potential on the surface of the adherend generated at this time was measured by a potentiometer (manufactured by Shishido Electrostatic Gas Co., Ltd., model "STATIRON DZ-4") fixed at a height of 30 mm from the center of the adherend. It is the peeling electrostatic voltage to glass or the peeling electrostatic voltage to acrylic resin board. The measurement was carried out in an environment of 23°C and 50% RH.

＜對玻璃之殘存接著力之測定＞ 利用手壓輥將表面保護膜整面地貼合於玻璃板(松浪硝子製造，1.35 mm×10 cm×10 cm)，於溫度23℃、濕度55%RH之氛圍下保管24小時，然後以0.3 m/min之速度將表面保護膜剝離，於溫度23℃、濕度55%RH之氛圍下藉由2.0 kg輥往返一次而貼附切斷為長度150 mm之19 mm寬度之No.31B膠帶(日東電工(股)製造，基材厚度：25 μm)。於溫度23℃、濕度55%RH之氛圍下固化30分鐘，然後使用拉伸試驗機(島津製作所公司製造之名為「Autograph AG-Xplus HS 6000 mm/min高速型號(AG-50NX plus)」之商品)，以剝離角度180度、拉伸速度300 mm/min進行剝離，而測定黏著力。 另外，對於未進行如上所述之處理之玻璃板亦同樣地測定19 mm寬度之No.31B膠帶之黏著力，並利用下述式算出殘留接著率。 殘留接著率(%)＝(表面保護膜剝離後之對玻璃板之No.31B黏著力/對玻璃板之No.31B黏著力)×100 該對玻璃之殘留接著率係表面保護膜之黏著劑成分何種程度地轉印至被黏著體之表面並是否造成污染之指標。該對玻璃之殘留接著率之值越高，則表面保護膜對被黏著體造成污染之可能性越低，該對玻璃之殘留接著率之值越低，則表面保護膜對被黏著體造成污染之可能性越高。 <Measurement of residual adhesive force on glass> The surface protective film was adhered to the glass plate (manufactured by Matsunami Glass, 1.35 mm×10 cm×10 cm) over the entire surface using a hand pressing roller, and was stored for 24 hours in an atmosphere with a temperature of 23°C and a humidity of 55%RH. The surface protective film was peeled off at a speed of m/min, and the No.31B tape (Nitto) cut into a length of 150 mm and a width of 19 mm was attached with a 2.0 kg roller back and forth once in an atmosphere of temperature 23 °C and humidity 55% RH. Manufactured by Electrician (stock), substrate thickness: 25 μm). Cured for 30 minutes in an atmosphere with a temperature of 23°C and a humidity of 55% RH, and then used a tensile tester (“Autograph AG-Xplus HS 6000 mm/min high-speed model (AG-50NX plus)” manufactured by Shimadzu Corporation product), peeling was performed at a peeling angle of 180 degrees and a tensile speed of 300 mm/min, and the adhesive force was measured. Moreover, the adhesive force of No.31B tape of 19 mm width was similarly measured about the glass plate which did not carry out the above-mentioned process, and the residual adhesion rate was calculated by the following formula. Residual adhesion rate (%)=(No.31B adhesion force to glass plate after peeling of surface protective film/No.31B adhesion force to glass plate)×100 The residual adhesion rate to glass is an indicator of how much the adhesive component of the surface protection film is transferred to the surface of the adherend and whether it causes pollution. The higher the value of the residual adhesion rate to the glass, the lower the possibility that the surface protective film will contaminate the adherend, and the lower the value of the residual adhesion rate to the glass, the surface protective film will contaminate the adherend the higher the probability.

＜霧度之測定＞ 將於下述實施例及比較例中所獲得之黏著劑溶液，於下述實施例及比較例中所記載之條件下塗佈於單面經矽酮剝離處理之厚度75 μm之聚酯膜(商品名：DIAFOIL MRF75，三菱化學股份有限公司製造)的剝離處理面並進行乾燥，而製作黏著劑層。繼而，將單面經矽酮剝離處理之厚度75 μm之聚酯膜(商品名：DIAFOIL MRE75，三菱化學股份有限公司製造)，以上述膜之剝離處理面成為黏著劑層側之方式被覆於黏著劑層之表面，於常溫下進行5天老化。準備2張中央開有20 mm×20 mm之孔之50 mm×50 mm之厚紙，藉由手壓輥往返一次將試樣單獨貼合於其中一張厚紙，然後貼合另一張厚紙。利用村上色彩技術研究所公司製造之「HM-150N」測定以上述方式獲得之評估用試樣。 <Measurement of haze> The adhesive solutions obtained in the following examples and comparative examples were coated on a polyester film with a thickness of 75 μm ( Brand name: DIAFOIL MRF75, manufactured by Mitsubishi Chemical Co., Ltd.), the peeling-treated surface was dried to prepare an adhesive layer. Next, a polyester film with a thickness of 75 μm (trade name: DIAFOIL MRE75, manufactured by Mitsubishi Chemical Co., Ltd.) whose one side has been peeled off with silicone was coated on the adhesive layer so that the peeled side of the film was on the side of the adhesive layer. The surface of the agent layer was aged for 5 days at room temperature. Prepare 2 sheets of 50 mm × 50 mm thick paper with a hole of 20 mm × 20 mm in the center, and use the hand roller to go back and forth once to attach the sample to one of the thick papers, and then to the other thick paper. The evaluation sample obtained in the above-described manner was measured using "HM-150N" manufactured by Murakami Color Technology Laboratory Co., Ltd.

＜實施例、比較例中使用之含氟化合物之說明＞ 作為含氟化合物，實施例、比較例中所使用者如下所述。 「MEGAFAC F-477」(DIC(股)製造，含有含氟基、親水性基及親油性基之低聚物，於製成0.1%甲苯溶液之情形時表面張力＝26.4 mN/m)； 「MEGAFAC F-551-A」(DIC(股)製造，含有含氟基及親油性基之低聚物，於製成0.1%甲苯溶液之情形時表面張力＝25.6 mN/m)； 「MEGAFAC F-553」(DIC(股)製造，含有含氟基、親水性基及親油性基之低聚物，於製成0.1%甲苯溶液之情形時表面張力＝26.4 mN/m)； 「MEGAFAC F-554」(DIC(股)製造，含有含氟基及親油性基之低聚物，於製成0.1%甲苯溶液之情形時表面張力＝25.0 mN/m)； 「MEGAFAC F-555-A」(DIC(股)製造，含有含氟基、親水性基及親油性基之低聚物，於製成0.1%甲苯溶液之情形時表面張力＝20.4 mN/m)； 「MEGAFAC F-557」(DIC(股)製造，含有含氟基、親水性基及親油性基之低聚物，於製成0.1%甲苯溶液之情形時表面張力＝26.3 mN/m)； 「MEGAFAC F-559」(DIC(股)製造，含有含氟基、親水性基及親油性基之低聚物，於製成0.1%甲苯溶液之情形時表面張力＝26.1 mN/m)； 「MEGAFAC F-563」(DIC(股)製造，含有含氟基及親油性基之低聚物，於製成0.1%甲苯溶液之情形時表面張力＝20.2 mN/m)； 「MEGAFAC F-569」(DIC(股)製造，含有含氟基及親水性基之低聚物，於製成0.1%甲苯溶液之情形時表面張力＝19.7 mN/m)。 <Description of Fluorine-Containing Compounds Used in Examples and Comparative Examples> As the fluorine-containing compound, those used in Examples and Comparative Examples are as follows. "MEGAFAC F-477" (manufactured by DIC Corporation, an oligomer containing fluorine, hydrophilic and lipophilic groups, surface tension = 26.4 mN/m when prepared as a 0.1% toluene solution); "MEGAFAC F-551-A" (manufactured by DIC Co., Ltd., an oligomer containing fluorine-containing groups and lipophilic groups, surface tension = 25.6 mN/m in the case of a 0.1% toluene solution); "MEGAFAC F-553" (manufactured by DIC Corporation, an oligomer containing a fluorine group, a hydrophilic group and a lipophilic group, surface tension = 26.4 mN/m when prepared as a 0.1% toluene solution); "MEGAFAC F-554" (manufactured by DIC Co., Ltd., an oligomer containing fluorine-containing groups and lipophilic groups, surface tension = 25.0 mN/m when prepared as a 0.1% toluene solution); "MEGAFAC F-555-A" (manufactured by DIC Corporation, an oligomer containing a fluorine group, a hydrophilic group and a lipophilic group, surface tension = 20.4 mN/m when prepared as a 0.1% toluene solution) ; "MEGAFAC F-557" (manufactured by DIC Corporation, an oligomer containing a fluorine group, a hydrophilic group and a lipophilic group, surface tension = 26.3 mN/m when prepared as a 0.1% toluene solution); "MEGAFAC F-559" (manufactured by DIC Co., Ltd., an oligomer containing fluorine group, hydrophilic group and lipophilic group, surface tension = 26.1 mN/m when prepared as a 0.1% toluene solution); "MEGAFAC F-563" (manufactured by DIC Corporation, an oligomer containing fluorine-containing groups and lipophilic groups, surface tension = 20.2 mN/m when prepared as a 0.1% toluene solution); "MEGAFAC F-569" (manufactured by DIC Corporation, an oligomer containing a fluorine-containing group and a hydrophilic group, surface tension = 19.7 mN/m when prepared as a 0.1% toluene solution).

[實施例1] 將作為多元醇之具有3個羥基之多元醇之PREMINOL S3011(旭硝子公司製造，Mn＝10000)85重量份、具有3個羥基之多元醇之SANNIX GP3000(三洋化成公司製造，Mn＝3000)13重量份、具有3個羥基之多元醇之SANNIX GP1000(三洋化成公司製造，Mn＝1000)2重量份；作為交聯劑之異氰酸酯化合物(Coronate HX：C/HX，Nippon Polyurethane公司製造)18重量份；作為觸媒之三乙醯丙酮鐵(日本化學產業公司製造)0.02重量份、氟系低聚物之MEGAFAC F-553(DIC公司製造)1重量份；作為離子性化合物之1-乙基-3-甲基咪唑鎓三(氟甲磺醯基)醯亞胺(AS110，第一工業製藥公司製造)1重量份，以整體之固形物成分成為35重量%之方式利用乙酸乙酯進行稀釋，而獲得胺基甲酸酯系黏著劑溶液。然後，將胺基甲酸酯系黏著劑溶液以乾燥後之厚度成為20 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，三菱化學股份有限公司製造)，於乾燥溫度130℃、乾燥時間2分鐘之條件下進行熟化並乾燥。繼而，將一個面實施了矽酮處理之厚度25 μm之包含聚酯樹脂之剝離片材(商品名「MRF25」，厚度25 μm，三菱化學股份有限公司製造)之矽酮處理面貼合於所獲得之黏著劑層之表面，從而獲得表面保護膜(1)。於常溫下進行5天老化，然後進行評估。剝離片材係於即將評估之前剝離。將結果示於表1中。 [Example 1] 85 parts by weight of PREMINOL S3011 (manufactured by Asahi Glass Co., Ltd., Mn=10000) as a polyol having three hydroxyl groups, and 13 parts by weight of SANNIX GP3000 (manufactured by Sanyo Chemical Co., Ltd., Mn=3000) of polyol having three hydroxyl groups parts, 2 parts by weight of SANNIX GP1000 (manufactured by Sanyo Chemical Co., Ltd., Mn=1000) of a polyol having 3 hydroxyl groups; 18 parts by weight of an isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent; 0.02 parts by weight of iron triacetate (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst, 1 part by weight of MEGAFAC F-553 (manufactured by DIC Corporation) as a fluorine-based oligomer; 1-ethyl-3 as an ionic compound -1 part by weight of methylimidazolium tris(fluoromethanesulfonyl)imide (AS110, manufactured by Daiichi Industrial Pharmaceutical Co., Ltd.), diluted with ethyl acetate so that the overall solid content becomes 35% by weight, and A urethane-based adhesive solution was obtained. Then, the urethane-based adhesive solution was applied to a substrate containing polyester resin (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), aged and dried at a drying temperature of 130° C. and a drying time of 2 minutes. Next, the silicone-treated surface of a release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) containing a polyester resin with a thickness of 25 μm, which had been silicone-treated, was attached to the surface. The surface of the obtained adhesive layer is obtained, thereby obtaining a surface protection film (1). After 5 days of aging at room temperature, evaluation was performed. The release sheet was released immediately prior to evaluation. The results are shown in Table 1.

[實施例2] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-569」，DIC製造)變更為0.25重量份，除此之外，與實施例1同樣地製作包含黏著劑組合物(2)之黏著劑層，從而獲得表面保護膜(2)。將結果示於表1中。 [Example 2] As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-569", manufactured by DIC) to 0.25 parts by weight in terms of solid content The adhesive layer of the agent composition (2) is formed, thereby obtaining a surface protection film (2). The results are shown in Table 1.

[實施例3] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-554」，DIC製造)變更為1重量份，除此之外，與實施例1同樣地製作包含黏著劑組合物(3)之黏著劑層，從而獲得表面保護膜(3)。將結果示於表1中。 [Example 3] As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-554", manufactured by DIC) to 1 part by weight in terms of solid content The adhesive layer of the agent composition (3) is formed, thereby obtaining a surface protection film (3). The results are shown in Table 1.

[實施例4] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-553」，DIC製造)變更為0.25重量份，除此之外，與實施例1同樣地製作包含黏著劑組合物(4)之黏著劑層，從而獲得表面保護膜(4)。將結果示於表1中。 [Example 4] As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-553", manufactured by DIC) to 0.25 parts by weight in terms of solid content The adhesive layer of the agent composition (4) is formed, thereby obtaining a surface protection film (4). The results are shown in Table 1.

[實施例5] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-553」，DIC製造)變更為0.25重量份，將離子性化合物(商品名「AS110」，第一工業製藥製)變更為0.5重量份，除此之外，與實施例1同樣地製作包含黏著劑組合物(5)之黏著劑層，從而獲得表面保護膜(5)。將結果示於表1中。 [Example 5] As shown in Table 1, a fluorine-based oligomer (trade name "F-553", manufactured by DIC) was changed to 0.25 parts by weight in terms of solid content, and an ionic compound (trade name "AS110", manufactured by Daiichi Industries A surface protective film (5) was obtained by producing an adhesive layer containing the adhesive composition (5) in the same manner as in Example 1, except that it was changed to 0.5 parts by weight. The results are shown in Table 1.

[實施例6] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-553」，DIC製造)變更為0.25重量份，將離子性化合物(商品名「AS110」，第一工業製藥製)變更為0.25重量份，除此之外，與實施例1同樣地製作包含黏著劑組合物(6)之黏著劑層，從而獲得表面保護膜(6)。將結果示於表1中。 [Example 6] As shown in Table 1, a fluorine-based oligomer (trade name "F-553", manufactured by DIC) was changed to 0.25 parts by weight in terms of solid content, and an ionic compound (trade name "AS110", manufactured by Daiichi Industries A surface protective film (6) was obtained by producing an adhesive layer containing an adhesive composition (6) in the same manner as in Example 1, except that it was changed to 0.25 parts by weight. The results are shown in Table 1.

[實施例7] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-555-A」，DIC製造)變更為0.25重量份，除此之外，與實施例1同樣地製作包含黏著劑組合物(7)之黏著劑層，從而獲得表面保護膜(7)。將結果示於表1中。 [Example 7] As shown in Table 1, it was produced in the same manner as in Example 1, except that the fluorine-based oligomer (trade name "F-555-A", manufactured by DIC) was changed to 0.25 parts by weight in terms of solid content. An adhesive layer comprising the adhesive composition (7) is obtained, thereby obtaining a surface protection film (7). The results are shown in Table 1.

[實施例8] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-559」，DIC製造)變更為0.25重量份，除此之外，與實施例1同樣地製作包含黏著劑組合物(8)之黏著劑層，從而獲得表面保護膜(8)。將結果示於表1中。 [Example 8] As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-559", manufactured by DIC) to 0.25 parts by weight in terms of solid content The adhesive layer of the agent composition (8) is formed, thereby obtaining a surface protection film (8). The results are shown in Table 1.

[實施例9] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-477」，DIC製造)變更為1重量份，除此之外，與實施例1同樣地製作包含黏著劑組合物(9)之黏著劑層，從而獲得表面保護膜(9)。將結果示於表1中。 [Example 9] As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-477", manufactured by DIC) to 1 part by weight in terms of solid content The adhesive layer of the agent composition (9) is formed, thereby obtaining a surface protection film (9). The results are shown in Table 1.

[實施例10] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-554」，DIC製造)變更為0.25重量份，除此之外，與實施例1同樣地製作包含黏著劑組合物(10)之黏著劑層，從而獲得表面保護膜(10)。將結果示於表1中。 [Example 10] As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-554", manufactured by DIC) to 0.25 parts by weight in terms of solid content The adhesive layer of the agent composition (10) is formed, thereby obtaining a surface protection film (10). The results are shown in Table 1.

[實施例11] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-553」，DIC製造)變更為0.1重量份，除此之外，與實施例1同樣地製作包含黏著劑組合物(11)之黏著劑層，從而獲得表面保護膜(11)。將結果示於表1中。 [Example 11] As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-553", manufactured by DIC) to 0.1 part by weight in terms of solid content The adhesive layer of the agent composition (11) is formed, thereby obtaining a surface protection film (11). The results are shown in Table 1.

[實施例12] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-477」，DIC製造)變更為0.25重量份，除此之外，與實施例1同樣地製作包含黏著劑組合物(12)之黏著劑層，從而獲得表面保護膜(12)。將結果示於表1中。 [Example 12] As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-477", manufactured by DIC) to 0.25 parts by weight in terms of solid content The adhesive layer of the agent composition (12) is formed, thereby obtaining a surface protection film (12). The results are shown in Table 1.

[實施例13] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-477」，DIC製造)變更為0.25重量份，將離子性化合物(商品名「AS110」，第一工業製藥製)變更為0.5重量份，除此之外，與實施例1同樣地製作包含黏著劑組合物(13)之黏著劑層，從而獲得表面保護膜(13)。將結果示於表1中。 [Example 13] As shown in Table 1, a fluorine-based oligomer (trade name "F-477", manufactured by DIC) was changed to 0.25 parts by weight in terms of solid content, and an ionic compound (trade name "AS110", manufactured by Daiichi Industries A surface protective film (13) was obtained by producing an adhesive layer containing an adhesive composition (13) in the same manner as in Example 1, except that it was changed to 0.5 parts by weight. The results are shown in Table 1.

[實施例14] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-477」，DIC製造)變更為0.25重量份，將離子性化合物(商品名「AS110」，第一工業製藥製)變更為0.25重量份，除此之外，與實施例1同樣地製作包含黏著劑組合物(14)之黏著劑層，從而獲得表面保護膜(14)。將結果示於表1中。 [Example 14] As shown in Table 1, a fluorine-based oligomer (trade name "F-477", manufactured by DIC) was changed to 0.25 parts by weight in terms of solid content, and an ionic compound (trade name "AS110", manufactured by Daiichi Industries A surface protective film (14) was obtained by producing an adhesive layer containing an adhesive composition (14) in the same manner as in Example 1, except that it was changed to 0.25 parts by weight. The results are shown in Table 1.

[實施例15] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-551-A」，DIC製造)變更為1重量份，除此之外，與實施例1同樣地製作包含黏著劑組合物(15)之黏著劑層，從而獲得表面保護膜(15)。將結果示於表1中。 [Example 15] As shown in Table 1, it was produced in the same manner as in Example 1, except that the fluorine-based oligomer (trade name "F-551-A", manufactured by DIC) was changed to 1 part by weight in terms of solid content. An adhesive layer containing the adhesive composition (15) is obtained, thereby obtaining a surface protection film (15). The results are shown in Table 1.

[實施例16] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-556」，DIC製造)變更為0.25重量份，除此之外，與實施例1同樣地製作包含黏著劑組合物(16)之黏著劑層，從而獲得表面保護膜(16)。將結果示於表1中。 [Example 16] As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-556", manufactured by DIC) to 0.25 parts by weight in terms of solid content The adhesive layer of the agent composition (16) is formed, thereby obtaining a surface protection film (16). The results are shown in Table 1.

[實施例17] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-551-A」，DIC製造)變更為0.25重量份，除此之外，與實施例1同樣地製作包含黏著劑組合物(17)之黏著劑層，從而獲得表面保護膜(17)。將結果示於表1中。 [Example 17] As shown in Table 1, it was produced in the same manner as in Example 1, except that the fluorine-based oligomer (trade name "F-551-A", manufactured by DIC) was changed to 0.25 parts by weight in terms of solid content. An adhesive layer containing the adhesive composition (17) is obtained, thereby obtaining a surface protection film (17). The results are shown in Table 1.

[實施例18] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-554」，DIC製造)變更為0.1重量份，除此之外，與實施例1同樣地製作包含黏著劑組合物(18)之黏著劑層，從而獲得表面保護膜(18)。將結果示於表1中。 [Example 18] As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-554", manufactured by DIC) to 0.1 part by weight in terms of solid content The adhesive layer of the agent composition (18) is formed, thereby obtaining a surface protection film (18). The results are shown in Table 1.

[實施例19] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-563」，DIC製造)變更為0.25重量份，除此之外，與實施例1同樣地製作包含黏著劑組合物(19)之黏著劑層，從而獲得表面保護膜(19)。將結果示於表1中。 [Example 19] As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-563", manufactured by DIC) to 0.25 parts by weight in terms of solid content The adhesive layer of the agent composition (19) is formed, thereby obtaining a surface protection film (19). The results are shown in Table 1.

[實施例20] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-477」，DIC製造)變更為0.1重量份，除此之外，與實施例1同樣地製作包含黏著劑組合物(20)之黏著劑層，從而獲得表面保護膜(20)。將結果示於表1中。 [Example 20] As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-477", manufactured by DIC) to 0.1 part by weight in terms of solid content The adhesive layer of the agent composition (20) is formed, thereby obtaining a surface protection film (20). The results are shown in Table 1.

[實施例21] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-553」，DIC製造)變更為2.0重量份，除此之外，與實施例1同樣地製作包含黏著劑組合物(21)之黏著劑層，從而獲得表面保護膜(21)。將結果示於表1中。 [Example 21] As shown in Table 1, a fluorine-based oligomer (trade name "F-553", manufactured by DIC) was changed to 2.0 parts by weight in terms of solid content The adhesive layer of the agent composition (21) is formed, thereby obtaining a surface protection film (21). The results are shown in Table 1.

[實施例22] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-553」，DIC製造)變更為4.0重量份，除此之外，與實施例1同樣地製作包含黏著劑組合物(22)之黏著劑層，從而獲得表面保護膜(22)。將結果示於表1中。 [Example 22] As shown in Table 1, a fluorine-based oligomer (trade name "F-553", manufactured by DIC) was changed to 4.0 parts by weight in terms of solid content The adhesive layer of the agent composition (22) is formed, thereby obtaining a surface protection film (22). The results are shown in Table 1.

[實施例23] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-553」，DIC製造)變更為6.0重量份，除此之外，與實施例1同樣地製作包含黏著劑組合物(23)之黏著劑層，從而獲得表面保護膜(23)。將結果示於表1中。 [Example 23] As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-553", manufactured by DIC) to 6.0 parts by weight in terms of solid content The adhesive layer of the agent composition (23) is formed, thereby obtaining a surface protection film (23). The results are shown in Table 1.

[實施例24] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-477」，DIC製造)變更為2.0重量份，除此之外，與實施例1同樣地製作包含黏著劑組合物(24)之黏著劑層，從而獲得表面保護膜(24)。將結果示於表1中。 [Example 24] As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-477", manufactured by DIC) to 2.0 parts by weight in terms of solid content The adhesive layer of the agent composition (24) is formed, thereby obtaining a surface protection film (24). The results are shown in Table 1.

[實施例25] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-477」，DIC製造)變更為4.0重量份，除此之外，與實施例1同樣地製作包含黏著劑組合物(25)之黏著劑層，從而獲得表面保護膜(25)。將結果示於表1中。 [Example 25] As shown in Table 1, a fluorine-based oligomer (trade name "F-477", manufactured by DIC) was changed to 4.0 parts by weight in terms of solid content The adhesive layer of the agent composition (25) is formed, thereby obtaining a surface protection film (25). The results are shown in Table 1.

[實施例26] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-477」，DIC製造)變更為6.0重量份，除此之外，與實施例1同樣地製作包含黏著劑組合物(26)之黏著劑層，從而獲得表面保護膜(26)。將結果示於表1中。 [Example 26] As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-477", manufactured by DIC) to 6.0 parts by weight in terms of solid content The adhesive layer of the agent composition (26) is formed, thereby obtaining a surface protection film (26). The results are shown in Table 1.

[實施例27] 如表1所示，以固形物成分換算計將異氰酸酯化合物(Coronate HX：C/HX，Nippon Polyurethane公司製造)變更為15.9重量份，除此之外，與實施例4同樣地製作包含黏著劑組合物(27)之黏著劑層，從而獲得表面保護膜(27)。將結果示於表1中。 [Example 27] As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 15.9 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 4. The adhesive layer of the object (27) is formed, thereby obtaining a surface protection film (27). The results are shown in Table 1.

[實施例28] 如表1所示，以固形物成分換算計將異氰酸酯化合物(Coronate HX：C/HX，Nippon Polyurethane公司製造)變更為14.1重量份，除此之外，與實施例4同樣地製作包含黏著劑組合物(28)之黏著劑層，從而獲得表面保護膜(28)。將結果示於表1中。 [Example 28] As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 14.1 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 4. The adhesive layer of the object (28) is formed, thereby obtaining a surface protection film (28). The results are shown in Table 1.

[實施例29] 如表1所示，以固形物成分換算計將異氰酸酯化合物(Coronate HX：C/HX，Nippon Polyurethane公司製造)變更為12.4重量份，除此之外，與實施例4同樣地製作包含黏著劑組合物(29)之黏著劑層，從而獲得表面保護膜(29)。將結果示於表1中。 [Example 29] As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 12.4 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 4. The adhesive layer of the object (29) is obtained, thereby obtaining a surface protection film (29). The results are shown in Table 1.

[實施例30] 如表1所示，以固形物成分換算計將異氰酸酯化合物(Coronate HX：C/HX，Nippon Polyurethane公司製造)變更為10.6重量份，除此之外，與實施例4同樣地製作包含黏著劑組合物(30)之黏著劑層，從而獲得表面保護膜(30)。將結果示於表1中。 [Example 30] As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 10.6 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 4. The adhesive layer of the object (30) is formed, thereby obtaining a surface protection film (30). The results are shown in Table 1.

[實施例31] 如表1所示，以固形物成分換算計將異氰酸酯化合物(Coronate HX：C/HX，Nippon Polyurethane公司製造)變更為8.8重量份，除此之外，與實施例4同樣地製作包含黏著劑組合物(31)之黏著劑層，從而獲得表面保護膜(31)。將結果示於表1中。 [Example 31] As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 8.8 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 4. The adhesive layer of the object (31) is obtained, thereby obtaining a surface protection film (31). The results are shown in Table 1.

[實施例32] 如表1所示，以固形物成分換算計將異氰酸酯化合物(Coronate HX：C/HX，Nippon Polyurethane公司製造)變更為15.9重量份，除此之外，與實施例12同樣地製作包含黏著劑組合物(32)之黏著劑層，從而獲得表面保護膜(32)。將結果示於表1中。 [Example 32] As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 15.9 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 12. The adhesive layer of the object (32) is formed, thereby obtaining a surface protection film (32). The results are shown in Table 1.

[實施例33] 如表1所示，以固形物成分換算計將異氰酸酯化合物(Coronate HX：C/HX，Nippon Polyurethane公司製造)變更為14.1重量份，除此之外，與實施例12同樣地製作包含黏著劑組合物(33)之黏著劑層，從而獲得表面保護膜(33)。將結果示於表1中。 [Example 33] As shown in Table 1, a composition containing an adhesive was prepared in the same manner as in Example 12, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane) was changed to 14.1 parts by weight in terms of solid content. The adhesive layer of the object (33) is formed, thereby obtaining a surface protection film (33). The results are shown in Table 1.

[實施例34] 如表1所示，以固形物成分換算計將異氰酸酯化合物(Coronate HX：C/HX，Nippon Polyurethane公司製造)變更為12.4重量份，除此之外，與實施例12同樣地製作包含黏著劑組合物(34)之黏著劑層，從而獲得表面保護膜(34)。將結果示於表1中。 [Example 34] As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 12.4 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 12. The adhesive layer of the object (34) is formed, thereby obtaining a surface protection film (34). The results are shown in Table 1.

[實施例35] 如表1所示，以固形物成分換算計將異氰酸酯化合物(Coronate HX：C/HX，Nippon Polyurethane公司製造)變更為10.6重量份，除此之外，與實施例12同樣地製作包含黏著劑組合物(35)之黏著劑層，從而獲得表面保護膜(35)。將結果示於表1中。 [Example 35] As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 10.6 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 12. The adhesive layer of the object (35) is formed, thereby obtaining a surface protection film (35). The results are shown in Table 1.

[實施例36] 如表1所示，以固形物成分換算計將異氰酸酯化合物(Coronate HX：C/HX，Nippon Polyurethane公司製造)變更為8.8重量份，除此之外，與實施例12同樣地製作包含黏著劑組合物(36)之黏著劑層，從而獲得表面保護膜(36)。將結果示於表1中。 [Example 36] As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 8.8 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 12. The adhesive layer of the material (36) is formed, thereby obtaining a surface protection film (36). The results are shown in Table 1.

[實施例37] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-557」，DIC製造)變更為0.25重量份，除此之外，與實施例4同樣地製作包含黏著劑組合物(37)之黏著劑層，從而獲得表面保護膜(37)。將結果示於表1中。 [Example 37] As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-557", manufactured by DIC) to 0.25 parts by weight in terms of solid content The adhesive layer of the agent composition (37) is formed, thereby obtaining a surface protection film (37). The results are shown in Table 1.

[實施例38] 如表1所示，以固形物成分換算計將異氰酸酯化合物(Coronate HX：C/HX，Nippon Polyurethane公司製造)變更為15.9重量份，除此之外，與實施例37同樣地製作包含黏著劑組合物(38)之黏著劑層，從而獲得表面保護膜(38)。將結果示於表1中。 [Example 38] As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 15.9 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 37. The adhesive layer of the object (38) is formed, thereby obtaining a surface protection film (38). The results are shown in Table 1.

[實施例39] 如表1所示，以固形物成分換算計將異氰酸酯化合物(Coronate HX：C/HX，Nippon Polyurethane公司製造)變更為14.1重量份，除此之外，與實施例37同樣地製作包含黏著劑組合物(39)之黏著劑層，從而獲得表面保護膜(39)。將結果示於表1中。 [Example 39] As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 14.1 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 37. The adhesive layer of the object (39) is formed, thereby obtaining a surface protection film (39). The results are shown in Table 1.

[實施例40] 如表1所示，以固形物成分換算計將異氰酸酯化合物(Coronate HX：C/HX，Nippon Polyurethane公司製造)變更為12.4重量份，除此之外，與實施例37同樣地製作包含黏著劑組合物(40)之黏著劑層，從而獲得表面保護膜(40)。將結果示於表1中。 [Example 40] As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 12.4 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 37. The adhesive layer of the object (40) is formed, thereby obtaining a surface protection film (40). The results are shown in Table 1.

[實施例41] 如表1所示，以固形物成分換算計將異氰酸酯化合物(Coronate HX：C/HX，Nippon Polyurethane公司製造)變更為10.6重量份，除此之外，與實施例37同樣地製作包含黏著劑組合物(41)之黏著劑層，從而獲得表面保護膜(41)。將結果示於表1中。 [Example 41] As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 10.6 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 37. The adhesive layer of the object (41) is obtained, thereby obtaining a surface protection film (41). The results are shown in Table 1.

[實施例42] 如表1所示，以固形物成分換算計將異氰酸酯化合物(Coronate HX：C/HX，Nippon Polyurethane公司製造)變更為8.8重量份，除此之外，與實施例37同樣地製作包含黏著劑組合物(42)之黏著劑層，從而獲得表面保護膜(42)。將結果示於表1中。 [Example 42] As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 8.8 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 37. The adhesive layer of the object (42) is formed, thereby obtaining a surface protection film (42). The results are shown in Table 1.

[實施例43] 如表1所示，以固形物成分換算計將異氰酸酯化合物(Coronate HX：C/HX，Nippon Polyurethane公司製造)變更為15.9重量份，除此之外，與實施例8同樣地製作包含黏著劑組合物(43)之黏著劑層，從而獲得表面保護膜(43)。將結果示於表1中。 [Example 43] As shown in Table 1, except having changed the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) to 15.9 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 8. The adhesive layer of the object (43) is formed, thereby obtaining a surface protection film (43). The results are shown in Table 1.

[實施例44] 如表1所示，以固形物成分換算計將異氰酸酯化合物(Coronate HX：C/HX，Nippon Polyurethane公司製造)變更為14.1重量份，除此之外，與實施例8同樣地製作包含黏著劑組合物(44)之黏著劑層，從而獲得表面保護膜(44)。將結果示於表1中。 [Example 44] As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 14.1 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 8. The adhesive layer of the object (44) is formed, thereby obtaining a surface protection film (44). The results are shown in Table 1.

[實施例45] 如表1所示，以固形物成分換算計將異氰酸酯化合物(Coronate HX：C/HX，Nippon Polyurethane公司製造)變更為12.4重量份，除此之外，與實施例8同樣地製作包含黏著劑組合物(45)之黏著劑層，從而獲得表面保護膜(45)。將結果示於表1中。 [Example 45] As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 12.4 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 8. The adhesive layer of the object (45) is formed, thereby obtaining a surface protection film (45). The results are shown in Table 1.

[實施例46] 如表1所示，以固形物成分換算計將異氰酸酯化合物(Coronate HX：C/HX，Nippon Polyurethane公司製造)變更為10.6重量份，除此之外，與實施例8同樣地製作包含黏著劑組合物(46)之黏著劑層，從而獲得表面保護膜(46)。將結果示於表1中。 [Example 46] As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 10.6 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 8. The adhesive layer of the material (46) is formed, thereby obtaining a surface protection film (46). The results are shown in Table 1.

[實施例47] 如表1所示，以固形物成分換算計將異氰酸酯化合物(Coronate HX：C/HX，Nippon Polyurethane公司製造)變更為8.8重量份，除此之外，與實施例8同樣地製作包含黏著劑組合物(47)之黏著劑層，從而獲得表面保護膜(47)。將結果示於表1中。 [Example 47] As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 8.8 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 8. The adhesive layer of the object (47) is formed, thereby obtaining a surface protection film (47). The results are shown in Table 1.

[實施例48] 將胺基甲酸酯預聚物A 100重量份、作為交聯劑之異氰酸酯化合物(Coronate HX：C/HX，Nippon Polyurethane公司製造)3重量份、作為抗氧化劑之Irganox1010(BASF公司製造)0.5重量份、氟系低聚物之MEGAFAC F-553(DIC公司製造)1重量份、作為離子性化合物之1-乙基-3-甲基咪唑鎓三(氟甲磺醯基)醯亞胺(AS110，第一工業製藥公司製造)1重量份，以整體之固形物成分成為49重量%之方式利用乙酸乙酯進行稀釋，而獲得胺基甲酸酯系黏著劑溶液。然後，將胺基甲酸酯系黏著劑溶液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，三菱化學股份有限公司製造)，於乾燥溫度120℃、乾燥時間3分鐘之條件下進行熟化並乾燥，而製作包含黏著劑組合物(48)之黏著劑層。繼而，將一個面經矽酮處理之厚度25 μm之包含聚酯樹脂之剝離片材(商品名「MRF25」，厚度25 μm，三菱化學股份有限公司製造)的矽酮處理面貼合於所獲得之黏著劑層之表面，而獲得表面保護膜(48)。於常溫下進行5天老化，然後進行評估。剝離片材係於即將評估之前剝離。將結果示於表1中。 [Example 48] 100 parts by weight of the urethane prepolymer A, 3 parts by weight of an isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane) as a crosslinking agent, and 0.5 parts by weight of Irganox 1010 (manufactured by BASF) as an antioxidant part, 1 part by weight of MEGAFAC F-553 (manufactured by DIC Corporation) as a fluorine-based oligomer, 1-ethyl-3-methylimidazolium tris(fluoromethanesulfonyl)imide (AS110) as an ionic compound , manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) 1 part by weight, diluted with ethyl acetate so that the entire solid content was 49% by weight to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a substrate containing a polyester resin (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Co., Ltd. production), aging and drying were carried out under the conditions of a drying temperature of 120° C. and a drying time of 3 minutes to produce an adhesive layer comprising an adhesive composition (48). Next, the silicone-treated surface of a release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) containing a polyester resin with a thickness of 25 μm treated with silicone was attached to the obtained surface. The surface of the adhesive layer is obtained to obtain a surface protection film (48). After 5 days of aging at room temperature, evaluation was performed. The release sheet was released immediately prior to evaluation. The results are shown in Table 1.

[實施例49] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-477」，DIC製造)變更為1.0重量份，除此之外，與實施例48同樣地製作包含黏著劑組合物(49)之黏著劑層，從而獲得表面保護膜(49)。將結果示於表1中。 [Example 49] As shown in Table 1, a fluorine-based oligomer (trade name "F-477", manufactured by DIC) was changed to 1.0 parts by weight in terms of solid content The adhesive layer of the agent composition (49) is formed, thereby obtaining a surface protection film (49). The results are shown in Table 1.

[實施例50] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-557」，DIC製造)變更為1.0重量份，除此之外，與實施例48同樣地製作包含黏著劑組合物(50)之黏著劑層，從而獲得表面保護膜(50)。將結果示於表1中。 [Example 50] As shown in Table 1, except that the fluorine-based oligomer (trade name "F-557", manufactured by DIC) was changed to 1.0 part by weight in terms of solid content The adhesive layer of the agent composition (50) is formed, thereby obtaining a surface protection film (50). The results are shown in Table 1.

[實施例51] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-559」，DIC製造)變更為1.0重量份，除此之外，與實施例48同樣地製作包含黏著劑組合物(51)之黏著劑層，從而獲得表面保護膜(51)。將結果示於表1中。 [Example 51] As shown in Table 1, a fluorine-based oligomer (trade name "F-559", manufactured by DIC) was changed to 1.0 parts by weight in terms of solid content The adhesive layer of the agent composition (51) is formed, thereby obtaining a surface protection film (51). The results are shown in Table 1.

[比較例1] 如表1所示，氟系低聚物(商品名「F-569」，DIC製造)以固形物成分換算計為0.25重量份，不使用離子性化合物(商品名「AS110」，第一工業製藥製造)，除此之外，與實施例1同樣地製作包含黏著劑組合物(C1)之黏著劑層，從而獲得表面保護膜(C1)。將結果示於表1中。 [Comparative Example 1] As shown in Table 1, a fluorine-based oligomer (trade name "F-569", manufactured by DIC) was 0.25 parts by weight in terms of solid content, and an ionic compound (trade name "AS110", manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) was not used. production), except that it carried out similarly to Example 1, produced the adhesive bond layer containing the adhesive composition (C1), and obtained the surface protection film (C1). The results are shown in Table 1.

[比較例2] 如表1所示，氟系低聚物(商品名「F-553」，DIC製造)以固形物成分換算計為0.25重量份，不使用離子性化合物(商品名「AS110」，第一工業製藥製造)，除此之外，與實施例1同樣地製作包含黏著劑組合物(C2)之黏著劑層，從而獲得表面保護膜(C2)。將結果示於表1中。 [Comparative Example 2] As shown in Table 1, a fluorine-based oligomer (trade name "F-553", manufactured by DIC) was 0.25 parts by weight in terms of solid content, and an ionic compound (trade name "AS110", manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) was not used. production), except that it carried out similarly to Example 1, produced the adhesive bond layer containing the adhesive composition (C2), and obtained the surface protection film (C2). The results are shown in Table 1.

[比較例3] 如表1所示，氟系低聚物(商品名「F-477」，DIC製造)以固形物成分換算計為0.25重量份，不使用離子性化合物(商品名「AS110」，第一工業製藥製造)，除此之外，與實施例1同樣地製作包含黏著劑組合物(C3)之黏著劑層，從而獲得表面保護膜(C3)。將結果示於表1中。 [Comparative Example 3] As shown in Table 1, a fluorine-based oligomer (trade name "F-477", manufactured by DIC) was 0.25 parts by weight in terms of solid content, and an ionic compound (trade name "AS110", manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) was not used. production), except that it carried out similarly to Example 1, and produced the adhesive bond layer containing the adhesive bond composition (C3), and obtained the surface protection film (C3). The results are shown in Table 1.

[比較例4] 如表1所示，氟系低聚物(商品名「F-551-A」，DIC製)以固形物成分換算計為0.25重量份，不使用離子性化合物(商品名「AS110」，第一工業製藥製造)，除此之外，與實施例1同樣地製作包含黏著劑組合物(C4)之黏著劑層，從而獲得表面保護膜(C4)。將結果示於表1中。 [Comparative Example 4] As shown in Table 1, the fluorine-based oligomer (trade name "F-551-A", manufactured by DIC) was 0.25 parts by weight in terms of solid content, and an ionic compound (trade name "AS110", the first Industrial Pharmaceutical Co., Ltd.), except that it carried out similarly to Example 1, and produced the adhesive agent layer containing the adhesive agent composition (C4), and obtained the surface protection film (C4). The results are shown in Table 1.

[比較例5] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-571」，DIC製造)變更為0.25重量份，除此之外，與實施例1同樣地製作包含黏著劑組合物(C5)之黏著劑層，從而獲得表面保護膜(C5)。將結果示於表1中。 [Comparative Example 5] As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-571", manufactured by DIC) to 0.25 parts by weight in terms of solid content The adhesive layer of the agent composition (C5) was obtained to obtain a surface protection film (C5). The results are shown in Table 1.

[比較例6] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-552」，DIC製造)變更為0.25重量份，除此之外，與實施例1同樣地製作包含黏著劑組合物(C6)之黏著劑層，從而獲得表面保護膜(C6)。將結果示於表1中。 [Comparative Example 6] As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-552", manufactured by DIC) to 0.25 parts by weight in terms of solid content The adhesive layer of the agent composition (C6) was obtained to obtain a surface protection film (C6). The results are shown in Table 1.

[比較例7] 如表1所示，不使用氟系低聚物，除此之外，與實施例1同樣地製作包含黏著劑組合物(C7)之黏著劑層，從而獲得表面保護膜(C7)。將結果示於表1中。 [Comparative Example 7] As shown in Table 1, except that the fluorine-based oligomer was not used, an adhesive layer containing the adhesive composition (C7) was produced in the same manner as in Example 1, thereby obtaining a surface protection film (C7). The results are shown in Table 1.

[比較例8] 如表1所示，不使用氟系低聚物，且不使用離子性化合物(商品名「AS110」，第一工業製藥製造)，除此之外，與實施例1同樣地製作包含黏著劑組合物(C8)之黏著劑層，從而獲得表面保護膜(C8)。將結果示於表1中。 [Comparative Example 8] As shown in Table 1, a combination containing an adhesive was prepared in the same manner as in Example 1, except that a fluorine-based oligomer and an ionic compound (trade name "AS110", manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) were not used. The adhesive layer of the product (C8) is obtained, thereby obtaining a surface protection film (C8). The results are shown in Table 1.

[比較例9] 如表1所示，不使用氟系低聚物，且不使用離子性化合物(商品名「AS110」，第一工業製藥製造)，除此之外，與實施例48同樣地製作包含黏著劑組合物(C9)之黏著劑層，從而獲得表面保護膜(C9)。將結果示於表1中。 [Comparative Example 9] As shown in Table 1, except that a fluorine-based oligomer was not used and an ionic compound (trade name "AS110", manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) was not used, a combination containing an adhesive was prepared in the same manner as in Example 48. The adhesive layer of the product (C9) was obtained, thereby obtaining a surface protection film (C9). The results are shown in Table 1.

[比較例10] 如表1所示，不使用氟系低聚物，且不使用離子性化合物(商品名「AS110」，第一工業製藥製造)，除此之外，與實施例49同樣地製作包含黏著劑組合物(C10)之黏著劑層，從而獲得表面保護膜(C10)。將結果示於表1中。 [Comparative Example 10] As shown in Table 1, a combination containing an adhesive was prepared in the same manner as in Example 49, except that a fluorine-based oligomer and an ionic compound (trade name "AS110", manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) were not used. The adhesive layer of the material (C10) was obtained, thereby obtaining a surface protection film (C10). The results are shown in Table 1.

[比較例11] 如表1所示，以固形物成分換算計將氟系低聚物(商品名「F-571」，DIC製造)變更為1重量份，除此之外，與實施例48同樣地製作包含黏著劑組合物(C11)之黏著劑層，從而獲得表面保護膜(C11)。將結果示於表1中。 [Comparative Example 11] As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-571", manufactured by DIC) to 1 part by weight in terms of solid content The adhesive layer of the agent composition (C11) was obtained to obtain a surface protection film (C11). The results are shown in Table 1.

[表1]

Figure 02_image011
[Table 1]
Figure 02_image011

[實施例52～103] 針對利用實施例1～51所獲得之表面保護膜(1)～(51)之各者，將隔離件剝離，使黏著劑層側貼合於作為光學構件之偏光板(日東電工股份有限公司製造之名為「TEG1465DUHC」之商品)，從而獲得貼合有表面保護膜之光學構件。 [Examples 52 to 103] For each of the surface protection films (1) to (51) obtained in Examples 1 to 51, the separator was peeled off, and the adhesive layer side was bonded to a polarizing plate (manufactured by Nitto Denko Co., Ltd.) as an optical member. The product named "TEG1465DUHC") to obtain an optical member with a surface protective film attached.

[實施例104～155] 針對利用實施例1～51所獲得之表面保護膜(1)～(51)之各者，將隔離件剝離，使黏著劑層側貼合於作為電子構件之導電性膜(日東電工股份有限公司製造之名為「ELECRYSTA V270L-TFMP」之商品)，從而獲得貼合有表面保護膜之電子構件。 [產業上之可利用性] [Examples 104 to 155] With respect to each of the surface protection films (1) to (51) obtained in Examples 1 to 51, the separator was peeled off, and the adhesive layer side was attached to a conductive film (Nitto Denko Co., Ltd.) which is an electronic member. The product named "ELECRYSTA V270L-TFMP" was manufactured) to obtain an electronic component with a surface protective film attached. [Industrial Availability]

本發明之表面保護膜可用於任意適當之用途。較佳為，本發明之表面保護膜可於光學構件或電子構件之領域中較佳地使用。The surface protective film of the present invention can be used for any appropriate purpose. Preferably, the surface protection film of the present invention can be preferably used in the field of optical components or electronic components.

1:基材層 2:黏著劑層 10:表面保護膜 1: substrate layer 2: Adhesive layer 10: Surface protection film

圖1係本發明之一實施方式之表面保護膜之概略剖視圖。FIG. 1 is a schematic cross-sectional view of a surface protection film according to an embodiment of the present invention.

1:基材層 1: substrate layer

2:黏著劑層 2: Adhesive layer

10:表面保護膜 10: Surface protection film

Claims (5)

一種表面保護膜，其係包含黏著劑層者，且 構成該黏著劑層之黏著劑由黏著劑組合物形成， 該黏著劑組合物包含基礎聚合物、多官能異氰酸酯、離子性化合物及氟系化合物， 該基礎聚合物為選自多元醇及胺基甲酸酯預聚物中之至少一種， 該氟系化合物相對於該基礎聚合物100重量份之含有比率為0.05重量份～1.5重量份， 該黏著劑層表面之對於二碘甲烷之表面自由能為6 mJ/m 2～30 mJ/m 2。 A surface protective film comprising an adhesive layer, and the adhesive constituting the adhesive layer is formed from an adhesive composition, the adhesive composition comprising a base polymer, a polyfunctional isocyanate, an ionic compound and a fluorine-based compound , the base polymer is at least one selected from polyols and urethane prepolymers, the content ratio of the fluorine-based compound to 100 parts by weight of the base polymer is 0.05 parts by weight to 1.5 parts by weight, the The surface free energy of the surface of the adhesive layer to diiodomethane is 6 mJ/m 2 to 30 mJ/m 2 . 如請求項1之表面保護膜，其中上述離子性化合物相對於上述基礎聚合物100重量份之含有比率為0.2重量份以上。The surface protective film of claim 1, wherein the content ratio of the ionic compound to 100 parts by weight of the base polymer is 0.2 parts by weight or more. 如請求項1或2之表面保護膜，其中將上述表面保護膜所包含之上述黏著劑層貼合於玻璃板並於溫度23℃下放置30分鐘，然後於溫度23℃下以剝離角度180度、剝離速度300 mm/分鐘將該表面保護膜從該玻璃板剝離，此時剝離力為0.005 N/25 mm～0.1 N/25 mm。The surface protective film of claim 1 or 2, wherein the above-mentioned adhesive layer contained in the above-mentioned surface protective film is attached to a glass plate and placed at a temperature of 23°C for 30 minutes, and then at a temperature of 23°C with a peeling angle of 180 degrees and peeling speed of 300 mm/min to peel off the surface protection film from the glass plate, and the peeling force at this time is 0.005 N/25 mm to 0.1 N/25 mm. 一種光學構件，其貼合有如請求項1至3中任一項之表面保護膜。An optical member to which the surface protection film of any one of claims 1 to 3 is attached. 一種電子構件，其貼合有如請求項1至3中任一項之表面保護膜。An electronic component with the surface protection film according to any one of claims 1 to 3 attached thereto.
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