TW202045649A - Pressure-sensitive adhesive sheet - Google Patents

Pressure-sensitive adhesive sheet Download PDF

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Publication number
TW202045649A
TW202045649A TW109101480A TW109101480A TW202045649A TW 202045649 A TW202045649 A TW 202045649A TW 109101480 A TW109101480 A TW 109101480A TW 109101480 A TW109101480 A TW 109101480A TW 202045649 A TW202045649 A TW 202045649A
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adhesive sheet
meth
acrylate
adhesive
adhesive layer
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TW109101480A
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Chinese (zh)
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仲野武史
片岡賢一
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日商日東電工股份有限公司
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Publication of TW202045649A publication Critical patent/TW202045649A/en

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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
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • 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]

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

This pressure-sensitive adhesive sheet 1 comprises: a substrate 2; and a pressure-sensitive adhesive layer 3 positioned on one surface of the substrate 2. The pressure-sensitive adhesive layer 3 comprises a polymerizable composition containing: a polymer; a photocuring agent having two or more polymerizable functional groups; and a photopolymerization initiator. The viscosity of the photocuring agent at 25 DEG C is at least 100 mPa·s. The shear storage modulus G' of the pressure-sensitive adhesive layer 3 at 25 DEG C after curing is at least 2.00*106 Pa.

Description

黏著片材Adhesive sheet

本發明係關於一種黏著片材，詳細而言係關於一種用以貼合於各種器件等之黏著片材。The present invention relates to an adhesive sheet, in detail, it relates to an adhesive sheet for bonding to various devices and the like.

已知，於進行電子器件等各種器件之組裝、加工、輸送等步驟之前，藉由對器件之表面暫時黏附黏著性膜，而謀求表面保護或賦予耐衝擊性。It is known that before the steps of assembling, processing, and transporting various devices such as electronic devices, an adhesive film is temporarily adhered to the surface of the device to seek surface protection or impart impact resistance.

作為此種黏著性膜，已知有一種包含塑膠膜與黏著層之積層體之應力分散膜(例如參照專利文獻1)。As such an adhesive film, a stress dispersion film including a laminate of a plastic film and an adhesive layer is known (for example, refer to Patent Document 1).

又，作為此種黏著性膜，已知有一種於加熱前或紫外線之照射前黏著力較弱，藉由加熱或照射紫外線而發揮黏著性之硬化性接著片材(例如參照專利文獻2)。Moreover, as such an adhesive film, there is known a curable adhesive sheet that has weak adhesive force before heating or ultraviolet irradiation, and exhibits adhesiveness by heating or ultraviolet irradiation (for example, refer to Patent Document 2).

又，作為此種黏著性膜，已知有於照射紫外線後，可無糊劑殘留地進行剝離之半導體基板加工用黏著帶(例如參照專利文獻3)。In addition, as such an adhesive film, there is known an adhesive tape for semiconductor substrate processing that can be peeled off without a paste remaining after irradiation with ultraviolet rays (for example, refer to Patent Document 3).

專利文獻3之半導體基板加工用黏著帶貼合於器件，於結束組裝或加工等步驟後藉由進行紫外線照射，可使黏著力降低，而可將其自器件剝離。 [先前技術文獻] [專利文獻]The adhesive tape for semiconductor substrate processing of Patent Document 3 is attached to the device, and after the steps of assembling or processing are completed, by irradiating with ultraviolet rays, the adhesive force can be reduced and the device can be peeled off. [Prior Technical Literature] [Patent Literature]

[專利文獻1]日本專利特開2017-132977號公報 [專利文獻2]日本專利特開2011-127054號公報 [專利文獻3]日本專利特開2005-050953號公報[Patent Document 1] Japanese Patent Laid-Open No. 2017-132977 [Patent Document 2] Japanese Patent Laid-Open No. 2011-127054 [Patent Document 3] Japanese Patent Laid-Open No. 2005-050953

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

另一面，就補強器件之觀點而言，期望不將暫時黏附之黏著性膜之一部分剝離而欲使其以貼合於器件之狀態殘存。On the other hand, from the viewpoint of reinforcing the device, it is desirable not to peel off a part of the temporarily adhered adhesive film, but to leave it in a state of being attached to the device.

但，專利文獻1之應力分散膜係以為了補強被黏著體而貼合之情況為前提，因此有黏著力較強而無法容易地僅將該應力分散膜之一部分去除之缺陷。However, the stress-dispersing film of Patent Document 1 is based on the premise that it is bonded to reinforce the adherend, and therefore has a defect that only a part of the stress-dispersing film cannot be easily removed due to its strong adhesive force.

又，關於專利文獻2之硬化性接著片材，若於加熱前或紫外線之照射前將硬化性接著片材之一部分切斷而去除，則有因黏著力較弱而於切斷部分之周邊產生***而發生剝離之缺陷。In addition, regarding the curable adhesive sheet of Patent Document 2, if a part of the curable adhesive sheet is cut and removed before heating or UV irradiation, the adhesive force is weak and there is generated around the cut portion. Defects caused by swelling and peeling.

又，專利文獻3之加熱剝離型黏著片材係以於上述步驟結束後被去除之情況為前提之工藝材料，並且以不會對器件產生糊劑殘留之方式調整了黏著力。In addition, the heat-peelable adhesive sheet of Patent Document 3 is a process material based on the premise that it is removed after the above-mentioned steps, and the adhesive force is adjusted so that no paste remains on the device.

因此，專利文獻3之加熱剝離型黏著片材就器件之補強之觀點而言，有黏著力不充分之缺陷。Therefore, the heat-peelable adhesive sheet of Patent Document 3 has the disadvantage of insufficient adhesive force from the viewpoint of device reinforcement.

本發明之目的在於提供一種具有充分之黏著性，並且於自被黏著體去除之情形時，可藉由光照射而使黏著力降低之黏著片材。 [解決問題之技術手段]The object of the present invention is to provide an adhesive sheet that has sufficient adhesiveness and can reduce the adhesive force by light irradiation when it is removed from the adherend. [Technical means to solve the problem]

本發明[1]係一種黏著片材，其具備基材、及配置於上述基材之一面之黏著層，且上述黏著層含有包含聚合物、具有2個以上聚合性官能基之光硬化劑、及光聚合起始劑之光硬化性組合物，上述光硬化劑於25℃下之黏度為100 mPa・s以上，光硬化後之上述黏著層於25℃下之剪切儲存模數G'為2.00×106 Pa以上。The present invention [1] is an adhesive sheet comprising a substrate and an adhesive layer arranged on one surface of the substrate, and the adhesive layer contains a light hardener containing a polymer and having two or more polymerizable functional groups, A photocurable composition with a photopolymerization initiator. The viscosity of the photocuring agent at 25°C is more than 100 mPa·s, and the shear storage modulus G'of the adhesive layer at 25°C after photocuring is 2.00×10 6 Pa or more.

本發明[2]包含如上述[1]所記載之黏著片材，其中光硬化後之上述黏著層之黏著力小於光硬化前之上述黏著層之黏著力。The present invention [2] includes the adhesive sheet as described in the above [1], wherein the adhesive force of the adhesive layer after photocuring is lower than the adhesive force of the adhesive layer before photocuring.

本發明[3]包含如上述[1]或[2]所記載之黏著片材，其中將光硬化前之上述黏著層以25℃貼合於聚醯亞胺膜並以剝離速度300 mm/分鐘藉由180度剝離試驗所測得之黏著力為5 N/25 mm以上。The present invention [3] includes the adhesive sheet as described in [1] or [2], wherein the adhesive layer before photocuring is bonded to a polyimide film at 25°C and a peeling speed of 300 mm/min The adhesion force measured by the 180 degree peel test is above 5 N/25 mm.

本發明[4]包含如上述[1]至[3]中任一項所記載之黏著片材，其中將光硬化後之上述黏著層以25℃貼合於聚醯亞胺膜並以剝離速度300 mm/分鐘藉由180度剝離試驗所測得之黏著力為4 N/25 mm以下。The present invention [4] includes the adhesive sheet as described in any one of [1] to [3], wherein the adhesive layer after photocuring is bonded to a polyimide film at 25°C and peeled off at a speed The adhesive force measured by a 180 degree peel test at 300 mm/min is 4 N/25 mm or less.

本發明[5]包含如請求項[1]至[4]中任一項所記載之黏著片材，其中上述光硬化劑具有4個以上之聚合性官能基。 [發明之效果]The present invention [5] includes the adhesive sheet as described in any one of claims [1] to [4], wherein the light curing agent has 4 or more polymerizable functional groups. [Effects of Invention]

本發明之黏著片材具備黏著層，該黏著層含有包含聚合物、具有2個以上聚合性官能基之光硬化劑、及光聚合起始劑之光硬化性組合物，且光硬化劑於25℃下之黏度為100 mPa・s以上。The adhesive sheet of the present invention includes an adhesive layer containing a photocurable composition containing a polymer, a photocuring agent having two or more polymerizable functional groups, and a photopolymerization initiator, and the photocuring agent is 25 The viscosity at ℃ is above 100 mPa·s.

因此，具有足以在貼合於被黏著體之狀態下殘存，而補強被黏著體之黏著性。Therefore, it has enough to remain in the state of being attached to the adherend, and strengthen the adhesion of the adherend.

又，光硬化後之上述黏著層於25℃下之剪切儲存模數G'為2.00×106 Pa以上。In addition, the shear storage modulus G'of the adhesive layer at 25°C after photocuring is 2.00×10 6 Pa or more.

因此，藉由光照射，可使黏著力充分地降低。Therefore, the adhesive force can be sufficiently reduced by light irradiation.

即，該黏著片材具有充分之黏著性，因此亦可以貼合於被黏著體之狀態殘存而補強被黏著體，亦可藉由光照射使初始黏著力降低而自被黏著體去除。因此，於黏著片材中，藉由對殘存之部分不照射光，對待去除之部分照射光，可使黏著片材之一部分殘存而補強被黏著體。That is, the adhesive sheet has sufficient adhesiveness, so it can also remain stuck to the adherend to reinforce the adherend, and can also be removed from the adherend by reducing the initial adhesive force by light irradiation. Therefore, in the adhesive sheet, by not irradiating the remaining part with light and irradiating the part to be removed with light, a part of the adhesive sheet can remain and the adherend can be reinforced.

參照圖1對本發明之黏著片材之一實施形態進行說明。An embodiment of the adhesive sheet of the present invention will be described with reference to FIG. 1.

1.黏著片材 如圖1所示，該黏著片材1包含具有規定厚度之膜形狀(包含片形狀)，沿與厚度方向正交之方向(面方向)延伸，且具有平坦之上表面及平坦之下表面。1. Adhesive sheet As shown in FIG. 1, the adhesive sheet 1 includes a film shape (including a sheet shape) having a predetermined thickness, extends in a direction (plane direction) orthogonal to the thickness direction, and has a flat upper surface and a flat lower surface.

具體而言，黏著片材1具備基材2、及配置於基材2之一面之黏著層3。Specifically, the adhesive sheet 1 includes a base 2 and an adhesive layer 3 arranged on one surface of the base 2.

又，如圖1所示，該黏著片材1可捲繞成卷狀。Moreover, as shown in FIG. 1, this adhesive sheet 1 can be wound into a roll shape.

以下，對各層進行詳細敍述。Hereinafter, each layer will be described in detail.

2.基材 基材2係黏著片材1之下層。基材2係確保黏著片材1之機械強度之支持層(支持材料)。又，基材2係用以補強被黏著體4(下述)之補強材料。又，基材2具有沿面方向延伸之膜形狀，且具有平坦之平面及平坦之下表面。2. Substrate The base material 2 is the lower layer of the adhesive sheet 1. The base material 2 is a support layer (support material) that ensures the mechanical strength of the adhesive sheet 1. In addition, the base material 2 is a reinforcing material for reinforcing the adherend 4 (described below). In addition, the substrate 2 has a film shape extending in the surface direction, and has a flat plane and a flat lower surface.

基材2包含可撓性塑膠材料。The substrate 2 includes a flexible plastic material.

作為此種塑膠材料，可列舉：例如聚對苯二甲酸乙二酯(PET)、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯等聚酯樹脂；例如聚甲基丙烯酸酯等(甲基)丙烯酸系樹脂(丙烯酸系樹脂及/或甲基丙烯酸系樹脂)；例如聚乙烯、聚丙烯、環烯烴聚合物(COP)等聚烯烴樹脂；例如聚碳酸酯樹脂、例如聚醚碸樹脂、例如聚芳酯樹脂、例如三聚氰胺樹脂、例如聚醯胺樹脂、例如聚醯亞胺樹脂、例如纖維素樹脂、例如聚苯乙烯樹脂、例如降𦯉烯樹脂之合成樹脂等。Examples of such plastic materials include polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate; for example, polymethacrylate. (Meth) acrylic resins (acrylic resins and/or methacrylic resins); for example, polyolefin resins such as polyethylene, polypropylene, and cycloolefin polymer (COP); for example, polycarbonate resins, such as polyether turpentine Resins, such as polyarylate resins, such as melamine resins, such as polyamide resins, such as polyimide resins, such as cellulose resins, such as polystyrene resins, synthetic resins such as norene resins, and the like.

詳情將於後文敍述，於自基材2側照射光而使黏著層3硬化之情形時，較佳為基材2具有對光之透明性。The details will be described later. When the adhesive layer 3 is cured by irradiating light from the side of the substrate 2, it is preferable that the substrate 2 has transparency to light.

就兼顧對光之透明性及機械強度之觀點而言，作為塑膠材料，較佳可列舉聚酯樹脂，更佳可列舉聚對苯二甲酸乙二酯(PET)。From the viewpoint of both light transparency and mechanical strength, as the plastic material, a polyester resin is preferable, and polyethylene terephthalate (PET) is more preferable.

基材2之厚度例如為4 μm以上，就補強被黏著體4(下述)之觀點而言，較佳為20 μm以上，更佳為30 μm以上，進而較佳為45 μm以上，又，例如為500 μm以下，就可撓性及處理性之觀點而言，較佳為300 μm以下，更佳為200 μm以下，進而較佳為100 μm以下。The thickness of the substrate 2 is, for example, 4 μm or more, and from the viewpoint of reinforcing the adherend 4 (described below), it is preferably 20 μm or more, more preferably 30 μm or more, and still more preferably 45 μm or more. For example, it is 500 μm or less, and from the viewpoint of flexibility and handleability, it is preferably 300 μm or less, more preferably 200 μm or less, and still more preferably 100 μm or less.

3.黏著層 黏著層3配置於基材2之一整面，且黏著層3為黏著片材1之上層。3. Adhesive layer The adhesive layer 3 is disposed on the entire surface of the substrate 2, and the adhesive layer 3 is the upper layer of the adhesive sheet 1.

黏著層3係用以使黏著片材1接著於被黏著體4(下述)之感壓接著層。又，黏著層3具有沿面方向延伸之膜形狀，且具有平坦之平面及平坦之下表面。The adhesive layer 3 is a pressure-sensitive adhesive layer for bonding the adhesive sheet 1 to the adherend 4 (described below). In addition, the adhesive layer 3 has a film shape extending along the surface direction, and has a flat plane and a flat lower surface.

黏著層3含有包含聚合物、光硬化劑、及光聚合起始劑之光硬化性組合物。The adhesive layer 3 contains a photocurable composition containing a polymer, a photocuring agent, and a photopolymerization initiator.

作為聚合物，例如可列舉丙烯酸系聚合物、聚矽氧系聚合物、胺基甲酸酯系聚合物、橡膠系聚合物等，就控制光學透明性、接著性及儲存模數之觀點而言，可列舉丙烯酸系聚合物。Examples of polymers include acrylic polymers, silicone polymers, urethane polymers, rubber polymers, etc., from the viewpoint of controlling optical transparency, adhesiveness, and storage modulus Examples include acrylic polymers.

丙烯酸系聚合物係藉由包含(甲基)丙烯酸烷基酯作為主成分之單體成分之聚合而獲得。The acrylic polymer is obtained by polymerization of monomer components containing alkyl (meth)acrylate as the main component.

(甲基)丙烯酸烷基酯為丙烯酸酯及/或甲基丙烯酸酯，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丙酯、(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)丙烯酸異戊酯、(甲基)丙烯酸新戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸辛酯、(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、(甲基)丙烯酸異三(十二烷基)酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸異十四烷基酯、(甲基)丙烯酸十五烷基酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸十七烷基酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸異十八烷基酯、(甲基)丙烯酸十九烷基酯、(甲基)丙烯酸二十烷基酯等直鏈狀或支鏈狀之(甲基)丙烯酸C1-20烷基酯等，較佳可列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸2-乙基己酯，更佳可列舉甲基丙烯酸甲酯、丙烯酸2-乙基己酯。Alkyl (meth)acrylate is acrylate and/or methacrylate, and examples include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, (meth) )Butyl acrylate, isopropyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate , Isoamyl (meth)acrylate, neopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (methyl) )Octyl acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, (meth)acrylate Base) undecyl acrylate, dodecyl (meth)acrylate, isotri(dodecyl) (meth)acrylate, tetradecyl (meth)acrylate, (meth) Isotetradecyl acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate Ester, isostearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate and other linear or branched (meth)acrylic acid C1 The -20 alkyl ester, etc., preferably include methyl (meth)acrylate and 2-ethylhexyl (meth)acrylate, and more preferably include methyl methacrylate and 2-ethylhexyl acrylate.

(甲基)丙烯酸烷基酯可單獨使用或併用兩種以上。The alkyl (meth)acrylate can be used alone or in combination of two or more.

作為(甲基)丙烯酸烷基酯，就調整玻璃轉移溫度及剪切儲存模數G'之觀點而言，較佳可列舉甲基丙烯酸甲酯與(甲基)丙烯酸C4-12烷基酯之併用，更佳可列舉甲基丙烯酸甲酯與丙烯酸2-乙基己酯之併用。As the alkyl (meth)acrylate, from the viewpoint of adjusting the glass transition temperature and the shear storage modulus G', preferably one of methyl methacrylate and C4-12 alkyl (meth)acrylate The combined use, more preferably, the combined use of methyl methacrylate and 2-ethylhexyl acrylate.

於併用甲基丙烯酸甲酯與(甲基)丙烯酸C4-12烷基酯作為(甲基)丙烯酸烷基酯之情形時，相對於甲基丙烯酸甲酯及(甲基)丙烯酸C4-12烷基酯之總量100質量份，甲基丙烯酸甲酯之調配比率例如為5質量份以上，又，例如為20質量份以下，又，(甲基)丙烯酸C4-12烷基酯之調配比率例如為80質量份以上，又，例如為95質量份以下。When methyl methacrylate and C4-12 alkyl (meth)acrylate are used together as alkyl (meth)acrylate, compared to methyl methacrylate and C4-12 alkyl (meth)acrylate The total amount of the ester is 100 parts by mass, the blending ratio of methyl methacrylate is, for example, 5 parts by mass or more, and, for example, 20 parts by mass or less, and the blending ratio of C4-12 alkyl (meth)acrylate is, for example, 80 parts by mass or more, and, for example, 95 parts by mass or less.

關於(甲基)丙烯酸烷基酯之調配比率，相對於單體成分，例如為50質量%以上，較佳為60質量%以上，又，例如為80質量%以下。Regarding the compounding ratio of the alkyl (meth)acrylate, relative to the monomer component, it is, for example, 50% by mass or more, preferably 60% by mass or more, and, for example, 80% by mass or less.

又，單體成分較佳為包含能夠與(甲基)丙烯酸烷基酯進行共聚之含官能基之乙烯基單體。In addition, the monomer component preferably contains a functional group-containing vinyl monomer copolymerizable with the alkyl (meth)acrylate.

作為含官能基之乙烯基單體，例如可列舉：含羥基之乙烯基單體、含羧基之乙烯基單體、含氮之乙烯基單體、含氰基之乙烯基單體、含縮水甘油基之乙烯基單體、含磺基之乙烯基單體、含磷酸基之乙烯基單體、芳香族乙烯基單體、乙烯酯單體、乙烯醚單體等。Examples of functional group-containing vinyl monomers include hydroxyl-containing vinyl monomers, carboxyl-containing vinyl monomers, nitrogen-containing vinyl monomers, cyano group-containing vinyl monomers, and glycidol-containing vinyl monomers. Vinyl monomers, vinyl monomers containing sulfo groups, vinyl monomers containing phosphoric acid groups, aromatic vinyl monomers, vinyl ester monomers, vinyl ether monomers, etc.

作為含羥基之乙烯基單體，例如可列舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯、(甲基)丙烯酸4-(羥基甲基)環己基)甲酯等，較佳可列舉(甲基)丙烯酸2-羥基乙酯，更佳可列舉丙烯酸2-羥基乙酯。Examples of hydroxyl-containing vinyl monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (meth) 6-hydroxyhexyl acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, 4-(hydroxymethyl)acrylate Cyclohexyl)methyl and the like, preferably 2-hydroxyethyl (meth)acrylate, and more preferably 2-hydroxyethyl acrylate.

作為含羧基之乙烯基單體，例如可列舉(甲基)丙烯酸、(甲基)丙烯酸2-羧基乙酯、羧基戊基(甲基)丙烯酸羧基戊酯、伊康酸、馬來酸、富馬酸、丁烯酸等。Examples of carboxyl group-containing vinyl monomers include (meth)acrylic acid, 2-carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, and Maleic acid, crotonic acid, etc.

又，作為含羧基之乙烯基單體，例如亦可列舉馬來酸酐、伊康酸酐等含酸酐基之單體。Moreover, as a vinyl monomer containing a carboxyl group, monomers containing an acid anhydride group, such as maleic anhydride and itaconic anhydride, can also be mentioned, for example.

作為含氮之乙烯基單體，例如可列舉：N-乙烯基吡咯啶酮、甲基乙烯基吡咯啶酮、乙烯基吡啶、乙烯基哌啶酮、乙烯基嘧啶、乙烯基哌𠯤、乙烯基吡𠯤、乙烯基吡咯、乙烯基咪唑、乙烯基㗁唑、乙烯基𠰌啉、N-丙烯醯𠰌啉、N-乙烯基羧醯胺類、N-乙烯基己內醯胺等。Examples of nitrogen-containing vinyl monomers include: N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperidone, vinyl Pyridine, vinyl pyrrole, vinyl imidazole, vinyl azole, vinyl pyridine, N-acrylamide, N-vinyl carboxamides, N-vinyl caprolactam and the like.

作為含氰基之乙烯基單體，例如可列舉(甲基)丙烯腈等。Examples of the cyano group-containing vinyl monomer include (meth)acrylonitrile.

作為含縮水甘油基之乙烯基單體，例如可列舉(甲基)丙烯酸縮水甘油酯等。As a glycidyl group-containing vinyl monomer, glycidyl (meth)acrylate etc. are mentioned, for example.

作為含磺基之乙烯基單體，例如可列舉苯乙烯磺酸、烯丙基磺酸等。Examples of sulfo group-containing vinyl monomers include styrene sulfonic acid and allyl sulfonic acid.

作為含磷酸基之乙烯基單體，例如可列舉丙烯醯磷酸2-羥基乙酯等。Examples of the phosphoric acid group-containing vinyl monomer include 2-hydroxyethyl acrylate phosphate and the like.

作為芳香族乙烯基單體，例如可列舉：苯乙烯、對甲基苯乙烯、鄰甲基苯乙烯、α-甲基苯乙烯等。Examples of the aromatic vinyl monomer include styrene, p-methylstyrene, o-methylstyrene, α-methylstyrene, and the like.

作為乙烯酯單體，例如可列舉：乙酸乙烯酯、丙酸乙烯酯等。As a vinyl ester monomer, vinyl acetate, vinyl propionate, etc. are mentioned, for example.

作為乙烯醚單體，例如可列舉甲基乙烯醚等。As a vinyl ether monomer, methyl vinyl ether etc. are mentioned, for example.

含官能基之乙烯基單體可單獨使用或併用兩種以上。於調配交聯劑(下述)之情形時，就向聚合物導入交聯結構之觀點而言，較佳可列舉含羥基之乙烯基單體，又，就提高凝集力之觀點而言，較佳可列舉含氮之乙烯基單體，更佳為將含羥基之乙烯基單體與含氮之乙烯基單體併用。The functional group-containing vinyl monomer can be used alone or in combination of two or more. In the case of compounding a crosslinking agent (described below), from the viewpoint of introducing a crosslinked structure into the polymer, a vinyl monomer containing a hydroxyl group is preferably mentioned. In addition, from the viewpoint of increasing the cohesive force, it is more Preferably, a nitrogen-containing vinyl monomer is used, and it is more preferable to use a combination of a hydroxyl-containing vinyl monomer and a nitrogen-containing vinyl monomer.

於將含羥基之乙烯基單體及含氮之乙烯基單體併用之情形時，相對於含羥基之乙烯基單體及含氮之乙烯基單體之總量100質量份，含羥基之乙烯基單體之調配比率例如為40質量份以上，又，例如為60質量份以下，又，含氮之乙烯基單體之調配比率例如為40質量份以上，又，例如為60質量份以下。In the case of combining hydroxyl-containing vinyl monomers and nitrogen-containing vinyl monomers, relative to 100 parts by mass of the total amount of hydroxyl-containing vinyl monomers and nitrogen-containing vinyl monomers, hydroxyl-containing vinyl The compounding ratio of the base monomer is, for example, 40 parts by mass or more, and, for example, 60 parts by mass or less, and the compounding ratio of the nitrogen-containing vinyl monomer is, for example, 40 parts by mass or more, and, for example, 60 parts by mass or less.

關於含官能基之乙烯基單體之調配比率，相對於單體成分，例如為5質量%以上，較佳為10質量%以上，更佳為15質量%以上，又，例如為30質量%以下，較佳為20質量%以下。Regarding the blending ratio of the functional group-containing vinyl monomer, relative to the monomer components, it is, for example, 5 mass% or more, preferably 10 mass% or more, more preferably 15 mass% or more, and, for example, 30 mass% or less , Preferably 20% by mass or less.

並且，丙烯酸系聚合物係將上述單體成分進行聚合而成之聚合物。In addition, the acrylic polymer is a polymer obtained by polymerizing the aforementioned monomer components.

於使單體成分聚合時，例如將(甲基)丙烯酸烷基酯、與視需要而定之含官能基之乙烯基單體進行調配而製備單體成分，將該單體成分例如藉由溶液聚合、塊狀聚合、乳化聚合等公知之聚合方法進行製備。When polymerizing monomer components, for example, alkyl (meth)acrylate and optionally functional group-containing vinyl monomers are prepared to prepare monomer components, for example, by solution polymerization , Block polymerization, emulsion polymerization and other known polymerization methods.

作為聚合方法，較佳可列舉溶液聚合。As a polymerization method, solution polymerization is preferably mentioned.

於溶液聚合中，例如向溶劑中調配單體成分與聚合起始劑而製備單體溶液，然後對單體溶液進行加熱。In solution polymerization, for example, a monomer component and a polymerization initiator are prepared in a solvent to prepare a monomer solution, and then the monomer solution is heated.

作為溶劑，例如可列舉有機溶劑等。As a solvent, an organic solvent etc. are mentioned, for example.

作為有機溶劑，可列舉：例如甲苯、苯、二甲苯等芳香族烴系溶劑、例如二***等醚系溶劑、例如丙酮、甲基乙基酮等酮系溶劑、例如乙酸乙酯等酯系溶劑、例如N,N-二甲基甲醯胺等醯胺系溶劑，較佳可列舉酯系溶劑，更佳可列舉乙酸乙酯。Examples of organic solvents include aromatic hydrocarbon solvents such as toluene, benzene, and xylene; ether solvents such as diethyl ether; ketone solvents such as acetone and methyl ethyl ketone; and ester solvents such as ethyl acetate. For example, amine-based solvents such as N,N-dimethylformamide, preferably ester-based solvents, and more preferably ethyl acetate.

溶劑可單獨使用或併用兩種以上。The solvent can be used alone or in combination of two or more.

溶劑之調配比率相對於單體成分100質量份，例如為100質量份以上，較佳為200質量份以上，又，例如為500質量份以下，較佳為300質量份以下。The blending ratio of the solvent relative to 100 parts by mass of the monomer components is, for example, 100 parts by mass or more, preferably 200 parts by mass or more, and, for example, 500 parts by mass or less, preferably 300 parts by mass or less.

作為聚合起始劑，例如可列舉過氧化物系聚合起始劑、偶氮系聚合起始劑等。Examples of the polymerization initiator include peroxide-based polymerization initiators, azo-based polymerization initiators, and the like.

作為過氧化物系聚合起始劑，例如可列舉：過氧化碳酸酯、過氧化酮、過氧縮酮、過氧化氫、過氧化二烷基、過氧化二醯基、過氧酯等有機過氧化物。Examples of peroxide-based polymerization initiators include organic peroxides such as peroxycarbonate, ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, diacyl peroxide, and peroxyester. Oxide.

作為偶氮系聚合起始劑，例如可列舉：2,2'-偶氮雙異丁腈、2,2'-偶氮雙(2-甲基丁腈)、2,2'-偶氮雙(2,4-二甲基戊腈)、2,2'-偶氮雙異丁酸二甲酯等偶氮化合物。As the azo polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis (2,4-Dimethylvaleronitrile), 2,2'-Dimethyl azobisisobutyrate and other azo compounds.

作為聚合起始劑，較佳可列舉偶氮系聚合起始劑，更佳可列舉2,2'-偶氮雙異丁腈。The polymerization initiator preferably includes an azo polymerization initiator, and more preferably includes 2,2'-azobisisobutyronitrile.

聚合起始劑可單獨使用或併用兩種以上。The polymerization initiator can be used alone or in combination of two or more.

聚合起始劑之調配比率相對於單體成分100質量份，例如為0.05質量份以上，較佳為0.1質量份以上，又，例如為1質量份以下，較佳為0.5質量份以下。The blending ratio of the polymerization initiator relative to 100 parts by mass of the monomer components is, for example, 0.05 parts by mass or more, preferably 0.1 parts by mass or more, and, for example, 1 part by mass or less, preferably 0.5 parts by mass or less.

加熱溫度例如為50℃以上80℃以下，加熱時間例如為1小時以上8小時以下。The heating temperature is, for example, 50°C or more and 80°C or less, and the heating time is, for example, 1 hour or more and 8 hours or less.

藉此，將單體成分進行聚合而獲得包含丙烯酸系聚合物之丙烯酸系聚合物溶液。In this way, the monomer components are polymerized to obtain an acrylic polymer solution containing an acrylic polymer.

丙烯酸系聚合物溶液之固形物成分濃度例如為20質量%以上，又，例如為80質量%以下。The solid content concentration of the acrylic polymer solution is, for example, 20% by mass or more, and for example, 80% by mass or less.

丙烯酸系聚合物之重量平均分子量例如為100000以上，較佳為300000以上、500000以上，又，例如為5000000以下，較佳為3000000以下，更佳為2000000以下。The weight average molecular weight of the acrylic polymer is, for example, 100,000 or more, preferably 300,000 or more, and 500,000 or more, for example, 5,000,000 or less, preferably 3,000,000 or less, and more preferably 2,000,000 or less.

再者，上述重量平均分子量係藉由GPC(凝膠滲透層析)進行測定並藉由聚苯乙烯換算而算出之值。In addition, the said weight average molecular weight is the value calculated by the polystyrene conversion measured by GPC (gel permeation chromatography).

於光硬化性組合物中，聚合物之調配比率相對於聚合物、光硬化劑及光聚合起始劑之總量，例如為70質量%以上，又，例如為95質量%以下。In the photocurable composition, the blending ratio of the polymer relative to the total amount of the polymer, the photocuring agent, and the photopolymerization initiator is, for example, 70% by mass or more, and, for example, 95% by mass or less.

光硬化劑具有2個以上之聚合性官能基，具體而言，可列舉多官能(甲基)丙烯酸酯作為光硬化劑。The light curing agent has two or more polymerizable functional groups, and specifically, polyfunctional (meth)acrylate can be cited as the light curing agent.

作為多官能(甲基)丙烯酸酯，可列舉：例如聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、聚四亞甲基二醇二(甲基)丙烯酸酯、雙酚A環氧乙烷改性二(甲基)丙烯酸酯、雙酚A環氧丙烷改性二(甲基)丙烯酸酯、烷二醇二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯等2官能(甲基)丙烯酸酯、例如乙氧化異三聚氰酸三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯等3官能(甲基)丙烯酸酯、例如二-三羥甲基丙烷四(甲基)丙烯酸酯、乙氧化季戊四醇四(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯等4官能(甲基)丙烯酸酯、例如二季戊四醇聚(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯等6官能(甲基)丙烯酸酯等。Examples of polyfunctional (meth)acrylates include polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polytetramethylene glycol di(meth)acrylate. , Bisphenol A ethylene oxide modified di(meth)acrylate, Bisphenol A propylene oxide modified di(meth)acrylate, alkanediol di(meth)acrylate, tricyclodecane two Difunctional (meth)acrylates such as methanol di(meth)acrylate, pentaerythritol di(meth)acrylate, neopentyl glycol di(meth)acrylate, glycerol di(meth)acrylate, etc. Trifunctional (meth)acrylates such as oxidized isocyanuric acid tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, such as di-trihydroxy 4-functional (meth)acrylates such as methylpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, for example, dipentaerythritol poly(meth)acrylate , Dipentaerythritol hexa(meth)acrylate and other 6 functional (meth)acrylates.

多官能(甲基)丙烯酸酯可單獨使用或併用兩種以上。The polyfunctional (meth)acrylate can be used alone or in combination of two or more.

光硬化劑就藉由光照射使黏著層3之黏著力充分地降低之觀點而言，較佳為具有4個以上之聚合性官能基。詳細而言，聚合性官能基之數量較佳為4以上，又，為6以下。The light curing agent preferably has 4 or more polymerizable functional groups from the viewpoint of sufficiently reducing the adhesive force of the adhesive layer 3 by light irradiation. Specifically, the number of polymerizable functional groups is preferably 4 or more, and 6 or less.

又，光硬化劑之官能基當量例如為50 g/eq以上，又，例如為500 g/eq以下。In addition, the functional group equivalent of the light curing agent is, for example, 50 g/eq or more, and for example, 500 g/eq or less.

作為此種光硬化劑，具體而言，可列舉4官能(甲基)丙烯酸酯、6官能(甲基)丙烯酸酯，更佳可列舉6官能(甲基)丙烯酸酯，進而較佳可列舉二季戊四醇六(甲基)丙烯酸酯，尤佳可列舉二季戊四醇六丙烯酸酯。As such a light curing agent, specifically, tetrafunctional (meth)acrylate and hexafunctional (meth)acrylate are exemplified, more preferably hexafunctional (meth)acrylate, and more preferably two The pentaerythritol hexa(meth)acrylate is particularly preferably dipentaerythritol hexaacrylate.

光硬化劑於25℃下之黏度例如為100 mPa・s以上，較佳為400 mPa・s以上，更佳為1000 mPa・s以上，進而較佳為3000 mPa・s以上，尤佳為4000 mPa・s以上，最佳為5000 mPa・s以上，進而最佳為6000 mPa・s以上，又，通常為8000 mPa・s以下。The viscosity of the light hardener at 25°C is, for example, 100 mPa·s or more, preferably 400 mPa·s or more, more preferably 1000 mPa·s or more, still more preferably 3000 mPa·s or more, particularly preferably 4000 mPa・S or more, preferably 5000 mPa·s or more, more preferably 6000 mPa·s or more, and usually 8000 mPa·s or less.

若光硬化劑於25℃下之黏度為上述下限以上，則可使初始黏著力(下述)變高。其結果為，可使該黏著片材1以貼合於被黏著體4(下述)之狀態殘存而補強被黏著體4(下述)。If the viscosity of the light hardener at 25°C is higher than the above lower limit, the initial adhesive force (described below) can be increased. As a result, the adhesive sheet 1 can be left in a state of being bonded to the adherend 4 (described below) to reinforce the adherend 4 (described below).

再者，上述黏度可藉由B型黏度計進行測定，具體而言，可使用東機產業 VISCOMETER(BH型)於測定溫度25℃、轉子3號、轉速10 rpm、測定時間5分鐘之條件下進行測定。Furthermore, the above-mentioned viscosity can be measured with a B-type viscometer. Specifically, Toki Sangyo VISCOMETER (BH-type) can be used under the conditions of measuring temperature 25℃, rotor No. 3, rotating speed 10 rpm, and measuring time 5 minutes Perform the measurement.

光硬化劑之分子量就相溶性之觀點而言，例如為1500以下，較佳為1000以下，又，例如為100以上。From the viewpoint of compatibility, the molecular weight of the light curing agent is, for example, 1500 or less, preferably 1000 or less, and for example, 100 or more.

又，光硬化劑較佳為選擇與聚合物相溶者。In addition, it is preferable to select a light hardener that is compatible with the polymer.

若光硬化劑與聚合物相溶，則可提高初始黏著力(下述)。If the light hardener is compatible with the polymer, the initial adhesion can be improved (described below).

具體而言，若聚合物之漢森溶解度參數(HSP)與光硬化劑之漢森溶解度參數(HSP)之差例如為4以下、較佳為3.5以下，則光硬化劑與聚合物相溶，其結果為可提高初始黏著力(下述)。Specifically, if the difference between the Hansen solubility parameter (HSP) of the polymer and the Hansen solubility parameter (HSP) of the light hardener is, for example, 4 or less, preferably 3.5 or less, the light hardener and the polymer are compatible, As a result, the initial adhesion can be improved (described below).

再者，聚合物之漢森溶解度參數(HSP)係基於構成聚合物之單體之漢森溶解度參數(HSP)而算出。Furthermore, the Hansen solubility parameter (HSP) of the polymer is calculated based on the Hansen solubility parameter (HSP) of the monomers constituting the polymer.

關於光硬化劑之調配比率，相對於聚合物100質量份，例如為10質量份以上，又，例如為50質量份以下，較佳為30質量份以下。The blending ratio of the light hardener is, for example, 10 parts by mass or more, for example, 50 parts by mass or less, and preferably 30 parts by mass or less with respect to 100 parts by mass of the polymer.

又，關於光硬化劑之調配比率，相對於聚合物、光硬化劑及光聚合起始劑之總量，例如為5質量%以上，又，例如為30質量%以下。In addition, the blending ratio of the light curing agent is, for example, 5% by mass or more, and, for example, 30% by mass or less with respect to the total amount of the polymer, light curing agent, and photopolymerization initiator.

光聚合起始劑促進光硬化劑之硬化反應，根據光硬化劑之種類等適宜選擇，可列舉：例如光陽離子起始劑(光酸產生劑)、例如1-羥基環己基苯基酮等羥基酮類、苯偶醯二甲基縮酮類、胺基酮類、醯基膦氧化物類、二苯甲酮類、含三氯甲基之三𠯤衍生物等光自由基起始劑、例如光陰離子起始劑(光鹼產生劑)等。The photopolymerization initiator promotes the curing reaction of the photocuring agent, and is appropriately selected according to the type of the photocuring agent. Examples include photocation initiators (photoacid generators), such as hydroxyl groups such as 1-hydroxycyclohexyl phenyl ketone. Light radical initiators such as ketones, benzil dimethyl ketals, amino ketones, phosphine oxides, benzophenones, trichloromethyl-containing trimethyl ketals, such as Photoanion initiator (photobase generator), etc.

光聚合起始劑可單獨使用或併用兩種以上。The photopolymerization initiator can be used alone or in combination of two or more.

此種光聚合起始劑中，於使用多官能(甲基)丙烯酸酯作為光硬化劑之情形時，較佳為採用光自由基起始劑，更佳為採用羥基酮類。Among such photopolymerization initiators, when a multifunctional (meth)acrylate is used as the photohardener, it is preferable to use a photoradical initiator, and more preferably to use hydroxyketones.

光聚合起始劑之光吸收區域例如為300 nm以上，又，例如為450 nm以下。The light absorption region of the photopolymerization initiator is, for example, 300 nm or more, and for example, 450 nm or less.

關於光聚合起始劑之調配比率，相對於聚合物100質量份，例如為0.01質量份以上，又，例如為1質量份以下，較佳為0.5質量份以下。The blending ratio of the photopolymerization initiator is, for example, 0.01 parts by mass or more, for example, 1 part by mass or less, and preferably 0.5 parts by mass or less with respect to 100 parts by mass of the polymer.

又，關於光聚合起始劑之調配比率，相對於聚合物、光硬化劑及光聚合起始劑之總量，例如為0.01質量%以上，又，例如為1質量%以下，較佳為0.5質量份以下。In addition, the blending ratio of the photopolymerization initiator is, for example, 0.01% by mass or more, and, for example, 1% by mass or less, and preferably 0.5, relative to the total amount of the polymer, photohardener, and photopolymerization initiator. Parts by mass or less.

並且，於製備光硬化性組合物時，將聚合物(於藉由溶液聚合而製備聚合物之情形時為聚合物溶液)、光硬化劑及光聚合起始劑以上述比率進行調配並加以混合。In addition, when preparing a photocurable composition, a polymer (a polymer solution in the case of preparing a polymer by solution polymerization), a photocuring agent, and a photopolymerization initiator are blended and mixed in the above ratio .

於光硬化性組合物中，就向聚合物導入交聯結構之觀點而言，較佳為調配交聯劑。In the photocurable composition, it is preferable to formulate a crosslinking agent from the viewpoint of introducing a crosslinked structure into the polymer.

作為交聯劑，例如可列舉異氰酸酯系交聯劑、環氧系交聯劑、㗁唑啉交聯劑、氮丙啶系交聯劑、碳二醯亞胺系交聯劑、金屬螯合物系交聯劑等，較佳可列舉異氰酸酯系交聯劑。Examples of the crosslinking agent include isocyanate-based crosslinking agents, epoxy-based crosslinking agents, azoline crosslinking agents, aziridine-based crosslinking agents, carbodiimide-based crosslinking agents, and metal chelate compounds. The crosslinking agent and the like preferably include an isocyanate crosslinking agent.

作為異氰酸酯系交聯劑，可列舉：例如伸丁基二異氰酸酯、六亞甲基二異氰酸酯等脂肪族二異氰酸酯、例如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等脂環族二異氰酸酯、例如2,4-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二異氰酸酯。Examples of the isocyanate-based crosslinking agent include aliphatic diisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, such as cyclopentyl diisocyanate, cyclohexyl diisocyanate, isophorone diisocyanate, etc. Alicyclic diisocyanates, for example, aromatic diisocyanates such as 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylylene diisocyanate.

又，作為異氰酸酯系交聯劑，亦可列舉上述異氰酸酯之衍生物(例如異氰尿酸酯改性體、多元醇改性體等)。In addition, as the isocyanate-based crosslinking agent, derivatives of the above-mentioned isocyanate (for example, an isocyanurate modified product, a polyol modified product, etc.) can also be cited.

作為異氰酸酯系交聯劑，可使用市售品，例如可列舉：Coronate L(甲苯二異氰酸酯之三羥甲基丙烷加成體，東梭製造)、Coronate HL(六亞甲基二異氰酸酯之三羥甲基丙烷加成體，東梭製造)、Coronate HX(六亞甲基二異氰酸酯之異氰尿酸酯體)、Takenate D110N(苯二甲基二異氰酸酯之三羥甲基丙烷加成體，三井化學製造)等。As the isocyanate-based crosslinking agent, commercially available products can be used, for example, Coronaate L (trimethylolpropane adduct of toluene diisocyanate, manufactured by Tosuo), Coronate HL (trihydroxymethyl of hexamethylene diisocyanate) Methyl propane adduct, manufactured by Toso), Coronaate HX (isocyanurate of hexamethylene diisocyanate), Takenate D110N (trimethylolpropane adduct of xylylene diisocyanate, Mitsui Chemical manufacturing) etc.

交聯劑可單獨使用或併用兩種以上。The crosslinking agent can be used alone or in combination of two or more.

若於光硬化性組合物中調配交聯劑，則聚合物中之羥基等官能基與交聯劑進行反應，而向聚合物導入交聯結構。If a crosslinking agent is blended in the photocurable composition, functional groups such as hydroxyl groups in the polymer react with the crosslinking agent to introduce a crosslinking structure into the polymer.

交聯劑之官能基當量例如為50 g/eq以上，又，例如為500 g/eq以下。The functional group equivalent of the crosslinking agent is, for example, 50 g/eq or more, and for example, 500 g/eq or less.

關於交聯劑之調配比率，相對於聚合物100質量份，例如為0.1質量份以上，較佳為1.0質量份以上，更佳為1.5質量份以上，進而較佳為2.0質量份以上，又，例如為10質量份以下，較佳為5質量份以下，更佳為4質量份以下。Regarding the blending ratio of the crosslinking agent relative to 100 parts by mass of the polymer, for example, it is 0.1 parts by mass or more, preferably 1.0 parts by mass or more, more preferably 1.5 parts by mass or more, and still more preferably 2.0 parts by mass or more. For example, it is 10 parts by mass or less, preferably 5 parts by mass or less, and more preferably 4 parts by mass or less.

又，於在光硬化性組合物中調配交聯劑之情形時，亦可為了促進交聯反應而調配交聯觸媒。Moreover, when blending a crosslinking agent in the photocurable composition, a crosslinking catalyst may be blended in order to promote the crosslinking reaction.

作為交聯觸媒，例如可列舉：鈦酸四正丁酯、鈦酸四異丙酯、三乙醯丙酮鐵、氧化丁基錫、二月桂酸二辛基錫等金屬系交聯觸媒等。Examples of the crosslinking catalyst include metal-based crosslinking catalysts such as tetra-n-butyl titanate, tetraisopropyl titanate, iron triacetone acetone, butyl tin oxide, and dioctyl tin dilaurate.

交聯觸媒可單獨使用或併用兩種以上。The crosslinking catalyst can be used alone or in combination of two or more.

關於交聯觸媒之調配比率，相對於聚合物100質量份，例如為0.001質量份以上，較佳為0.01質量份以上，又，例如為0.05質量份以下。Regarding the blending ratio of the crosslinking catalyst, relative to 100 parts by mass of the polymer, it is, for example, 0.001 parts by mass or more, preferably 0.01 parts by mass or more, and, for example, 0.05 parts by mass or less.

又，於光硬化性組合物中，可於無損本發明之效果之範圍內視需要含有例如：矽烷偶合劑、黏著性賦予劑、塑化劑、軟化劑、抗劣化劑、填充劑、著色劑、基於螢光燈下或自然光下之穩定化之觀點的紫外線吸收劑、基於螢光燈下或自然光下之穩定化之觀點的抗氧化劑、界面活性劑、抗靜電劑等添加劑等各種添加劑。In addition, the photocurable composition may optionally contain a silane coupling agent, an adhesive agent, a plasticizer, a softener, an anti-deterioration agent, a filler, and a coloring agent within the range that does not impair the effects of the present invention. , UV absorbers based on the viewpoint of stabilization under fluorescent lamps or natural light, antioxidants, surfactants, antistatic agents and other additives based on the viewpoint of stabilization under fluorescent lamps or natural light.

藉此，獲得光硬化性組合物。Thereby, a photocurable composition is obtained.

關於聚合物之調配比率，相對於光硬化性組合物，例如為50質量%以上，較佳為80質量%以上，又，例如為90質量%以下。Regarding the blending ratio of the polymer, relative to the photocurable composition, it is, for example, 50% by mass or more, preferably 80% by mass or more, and, for example, 90% by mass or less.

關於光硬化劑之調配比率，相對於光硬化性組合物，例如為10質量%以上，又，例如為50質量%以下。Regarding the blending ratio of the photocuring agent, relative to the photocurable composition, it is, for example, 10% by mass or more, and, for example, 50% by mass or less.

關於光聚合起始劑之調配比率，相對於光硬化性組合物，例如為0.01質量%以上，又，例如為0.5質量%以下，較佳為0.1質量%以下。Regarding the blending ratio of the photopolymerization initiator, relative to the photocurable composition, it is, for example, 0.01% by mass or more, and, for example, 0.5% by mass or less, and preferably 0.1% by mass or less.

並且，藉由下述方法，由光硬化性組合物形成黏著層3。In addition, the adhesive layer 3 is formed from the photocurable composition by the following method.

黏著層3之厚度就黏著性之觀點而言，例如為5 μm以上，較佳為10 μm以上，更佳為15 μm以上，進而較佳為20 μm以上，又，就處理性之觀點而言，例如為300 μm以下，較佳為100 μm以下，更佳為50 μm以下，進而較佳為40 μm以下，尤佳為30 μm以下。The thickness of the adhesive layer 3 from the standpoint of adhesiveness is, for example, 5 μm or more, preferably 10 μm or more, more preferably 15 μm or more, and still more preferably 20 μm or more, and from the viewpoint of handling properties For example, it is 300 μm or less, preferably 100 μm or less, more preferably 50 μm or less, still more preferably 40 μm or less, and particularly preferably 30 μm or less.

4.黏著片材之製造方法 其次，參照圖2對製造該黏著片材之方法進行說明。4. Manufacturing method of adhesive sheet Next, a method of manufacturing the adhesive sheet will be described with reference to FIG. 2.

製造該黏著片材之方法包括：準備基材2之第1步驟、及於基材2之一面配置黏著層3之第2步驟。The method of manufacturing the adhesive sheet includes: a first step of preparing a substrate 2 and a second step of arranging an adhesive layer 3 on one surface of the substrate 2.

於第1步驟中，如圖2A所示，準備基材2。In the first step, as shown in FIG. 2A, the substrate 2 is prepared.

於第2步驟中，如圖2B所示，於基材2之一面配置黏著層3。In the second step, as shown in FIG. 2B, an adhesive layer 3 is disposed on one surface of the substrate 2.

於在基材2之一面配置黏著層3時，例如於基材2之一面塗佈上述光硬化性組合物，並根據需要將溶劑乾燥去除。When disposing the adhesive layer 3 on one surface of the substrate 2, for example, the above-mentioned photocurable composition is applied to one surface of the substrate 2, and the solvent is dried and removed as necessary.

作為光硬化性組合物之塗佈方法，例如可列舉：輥式塗佈、接觸輥式塗佈、凹版塗佈、反向塗佈、輥式刷塗、噴塗、浸漬輥式塗佈、棒式塗佈、刮塗、氣刀塗佈、淋幕式塗佈、模唇塗佈、模嘴塗佈等。Examples of the coating method of the photocurable composition include: roll coating, touch roll coating, gravure coating, reverse coating, roll brushing, spray coating, dipping roll coating, and bar coating. Coating, knife coating, air knife coating, curtain coating, die lip coating, die nozzle coating, etc.

作為乾燥條件，乾燥溫度例如為50℃以上，較佳為70℃以上，更佳為100℃以上，又，例如為200℃以下，較佳為180℃以下，更佳為150℃以下，乾燥時間例如為5秒以上，較佳為10秒以上，又，例如為20分鐘以下，較佳為15分鐘以下，更佳為10分鐘以下。As the drying conditions, the drying temperature is, for example, 50°C or higher, preferably 70°C or higher, more preferably 100°C or higher, and, for example, 200°C or lower, preferably 180°C or lower, more preferably 150°C or lower, drying time For example, it is 5 seconds or more, preferably 10 seconds or more, and for example, it is 20 minutes or less, preferably 15 minutes or less, and more preferably 10 minutes or less.

藉此，於基材2之一面形成黏著層3，而獲得具備基材2、及配置於基材2之一面之黏著層3之黏著片材1。Thereby, an adhesive layer 3 is formed on one surface of the substrate 2 to obtain an adhesive sheet 1 having a substrate 2 and an adhesive layer 3 arranged on one surface of the substrate 2.

再者，於光硬化性組合物包含交聯劑之情形時，在乾燥去除之同時、或溶劑之乾燥後(於黏著層3之一面積層有剝離膜5(下述)後)，較佳為藉由熟化使交聯進行。Furthermore, when the photocurable composition contains a crosslinking agent, it is preferably removed simultaneously with drying or after drying of the solvent (after the release film 5 (described below) is layered on one area of the adhesive layer 3), Cross-linking proceeds by aging.

熟化條件根據交聯劑之種類進行適宜設定，熟化溫度例如為20℃以上，又，例如為160℃以下，較佳為50℃以下，又，熟化時間為1分鐘以上，較佳為12小時以上，更佳為1天以上，又，例如為7天以下。The curing conditions are appropriately set according to the type of crosslinking agent. The curing temperature is, for example, 20°C or higher, and, for example, 160°C or lower, preferably 50°C or lower, and the curing time is 1 minute or longer, preferably 12 hours or longer. , More preferably 1 day or more, and, for example, 7 days or less.

光硬化前之黏著層3於25℃下之剪切儲存模數G'例如為6×104 Pa以上，較佳為7×104 Pa以上，又，例如為9×104 Pa以下，較佳為8×104 Pa以下。The shear storage modulus G'of the adhesive layer 3 before photocuring at 25°C is, for example, 6×10 4 Pa or more, preferably 7×10 4 Pa or more, and, for example, 9×10 4 Pa or less. Preferably, it is 8×10 4 Pa or less.

再者，關於上述剪切儲存模數G'，詳情將於下述實施例中進行敍述，其係藉由在頻率1 Hz、升溫速度5℃/分鐘、溫度範圍-50℃～150℃之條件下之動態黏彈性測定而測定。Furthermore, regarding the above-mentioned shear storage modulus G', the details will be described in the following embodiment, which is based on the conditions of a frequency of 1 Hz, a heating rate of 5°C/min, and a temperature range of -50°C to 150°C The following dynamic viscoelasticity measurement is determined.

光硬化前之黏著層3之黏著力(初始黏著力)例如為5 N/25 mm以上，較佳為8 N/25 mm以上，更佳為10 N/25 mm以上，進而較佳為12 N/25 mm以上。The adhesion (initial adhesion) of the adhesive layer 3 before photocuring is, for example, 5 N/25 mm or more, preferably 8 N/25 mm or more, more preferably 10 N/25 mm or more, and more preferably 12 N /25 mm or more.

再者，關於上述黏著力，詳情將於下述實施例進行敍述，其係藉由將黏著片材1以25℃貼合於聚醯亞胺膜並以剝離速度300 mm/分鐘進行180度剝離試驗而進行測定。Furthermore, regarding the above-mentioned adhesive force, the details will be described in the following example, which is performed by bonding the adhesive sheet 1 to the polyimide film at 25°C and peeling at a peeling speed of 300 mm/min for 180° peeling Test and measure.

若初始黏著力為上述下限以上，則可以貼合於被黏著體4(下述)之狀態殘存而補強被黏著體4(下述)。If the initial adhesive force is greater than or equal to the above lower limit, the adherend 4 (described below) can be left in a state of being bonded to the adherend 4 (described below) to strengthen the adherend 4 (described below).

並且，若對黏著片材1中之黏著層3照射光，則黏著層3硬化。In addition, when light is irradiated to the adhesive layer 3 in the adhesive sheet 1, the adhesive layer 3 is hardened.

藉此，光硬化後之黏著層3變得比光硬化前之黏著層3更硬。Thereby, the adhesive layer 3 after photocuring becomes harder than the adhesive layer 3 before photocuring.

具體而言，光硬化後之黏著層3於25℃下之剪切儲存模數G'為2.00×106 Pa以上，較佳為2.50×106 Pa以上，更佳為3.0×106 Pa以上。Specifically, the shear storage modulus G'of the adhesive layer 3 after photocuring at 25°C is 2.00×10 6 Pa or more, preferably 2.50×10 6 Pa or more, more preferably 3.0×10 6 Pa or more .

並且，由於光硬化後之黏著層3於25℃下之剪切儲存模數G'為上述下限以上，故而光硬化後之黏著層3之黏著力會小於比光硬化前之黏著層3之黏著力。Moreover, since the shear storage modulus G'of the adhesive layer 3 after photocuring at 25°C is above the above lower limit, the adhesive force of the adhesive layer 3 after photocuring will be smaller than that of the adhesive layer 3 before photocuring force.

即，根據此種黏著片材1，於光硬化前，可使黏著片材1牢固地接著於被黏著體4(下述)，於光硬化後，可容易地自被黏著體4(下述)將黏著片材1去除。That is, according to this adhesive sheet 1, before photocuring, the adhesive sheet 1 can be firmly attached to the adherend 4 (described below), and after photocuring, it can be easily self-attached from the adherend 4 (described below) ) Remove the adhesive sheet 1.

因此，雖將於後文進行詳細敍述，但於黏著片材1中，藉由對殘存之部分不照射光，對待去除之部分照射光，可使黏著片材1之一部分殘存而補強被黏著體4(下述)。Therefore, although it will be described in detail later, in the adhesive sheet 1, by not irradiating the remaining part with light, and irradiating the part to be removed with light, a part of the adhesive sheet 1 can be left to strengthen the adherend 4 (below).

光硬化後之黏著層3之黏著力例如為4 N/25 mm以下，較佳為3 N/25 mm以下，又，通常為0.001 N/25 mm以上。The adhesive force of the adhesive layer 3 after light curing is, for example, 4 N/25 mm or less, preferably 3 N/25 mm or less, and usually 0.001 N/25 mm or more.

若光硬化後之黏著層3之黏著力為上述上限以下，則可容易地自被黏著體4將黏著片材1去除。If the adhesive force of the adhesive layer 3 after photocuring is below the above upper limit, the adhesive sheet 1 can be easily removed from the adherend 4.

又，如圖2C所示，黏著片材1亦可視需要於黏著層3之一面積層剝離膜5。In addition, as shown in FIG. 2C, the adhesive sheet 1 may also peel off the film 5 on an area of the adhesive layer 3 as needed.

於此種情形時，黏著片材1依序具備基材2、黏著層3及剝離膜5。In this case, the adhesive sheet 1 includes a substrate 2, an adhesive layer 3, and a release film 5 in this order.

作為剝離膜5，例如可列舉聚乙烯、聚丙烯、聚對苯二甲酸乙二酯、聚酯膜等可撓性塑膠膜。Examples of the release film 5 include flexible plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films.

剝離膜5之厚度例如為3 μm以上，較佳為10 μm以上，又，例如為200 μm以下，較佳為100 μm以下，更佳為50 μm以下。The thickness of the release film 5 is, for example, 3 μm or more, preferably 10 μm or more, and, for example, 200 μm or less, preferably 100 μm or less, and more preferably 50 μm or less.

對於剝離膜5，較佳為實施藉由聚矽氧系、氟系、長鏈烷基系、脂肪酸醯胺系等離型劑進行之離型處理、或藉由矽粉進行之離型處理。For the release film 5, it is preferable to perform a release treatment with a silicone-based, fluorine-based, long-chain alkyl-based, fatty acid amide-based release agent, or a release treatment with silicon powder.

5.黏著片材之使用方法 其次，參照圖3對該黏著片材1之使用方法之一例進行說明。5. How to use the adhesive sheet Next, an example of how to use the adhesive sheet 1 will be described with reference to FIG. 3.

該黏著片材1之使用方法包括：準備黏著片材1之第3步驟、將黏著片材1貼合於被黏著體4之第4步驟、及自被黏著體4去除黏著片材1之一部分之第5步驟。The method of using the adhesive sheet 1 includes: the third step of preparing the adhesive sheet 1, the fourth step of attaching the adhesive sheet 1 to the adherend 4, and removing part of the adhesive sheet 1 from the adherend 4 The fifth step.

於第3步驟中，如圖3A所示，準備黏著片材1。In the third step, as shown in FIG. 3A, the adhesive sheet 1 is prepared.

其次，於第4步驟中，如圖3B所示，以配置於基材2之一面之黏著層3與被黏著體4接觸之方式將黏著片材1貼合於被黏著體4。Next, in the fourth step, as shown in FIG. 3B, the adhesive sheet 1 is attached to the adherend 4 in such a manner that the adhesive layer 3 disposed on one surface of the base material 2 contacts the adherend 4.

被黏著體4係由黏著片材1補強之被補強體，例如可列舉光學器件、電子器件及其構成零件等。The adherend 4 is a reinforced object reinforced by the adhesive sheet 1, and examples thereof include optical devices, electronic devices, and their constituent parts.

其次，於第5步驟中，如圖3C所示，將貼合於被黏著體4之黏著片材1之一部分去除。Next, in the fifth step, as shown in FIG. 3C, a part of the adhesive sheet 1 attached to the adherend 4 is removed.

再者，於以下說明中，對將黏著片材1沿面方向三等分中使兩端部分之2個部位殘存之情形(換言之，為僅去除將黏著片材1沿面方向三等分中之中央部分之1個部位之情形)進行說明。In addition, in the following description, in the case where the adhesive sheet 1 is divided into three halves in the surface direction, the two end portions remain (in other words, only the center of the three halves of the adhesive sheet 1 in the surface direction is removed Part of the case of 1 part) will be explained.

於去除貼合於被黏著體4之黏著片材1之一部分時，首先，自黏著片材1中之基材2側僅對黏著片材1之一部分照射光。When removing a part of the adhesive sheet 1 attached to the adherend 4, firstly, only a part of the adhesive sheet 1 is irradiated with light from the side of the base material 2 in the adhesive sheet 1.

詳細而言，於黏著片材1中，對殘存之部分(以下稱為殘存部分6)不照射光，對待去除之部分(以下稱為去除部分7)照射光。Specifically, in the adhesive sheet 1, the remaining part (hereinafter referred to as the remaining part 6) is not irradiated with light, and the part to be removed (hereinafter referred to as the removed part 7) is irradiated with light.

具體而言，對去除部分7不配置遮罩8，對殘存部分6配置將光阻斷之遮罩8。Specifically, the mask 8 is not arranged on the removed part 7 and the mask 8 for blocking light is arranged on the remaining part 6.

藉此，對去除部分7中之黏著層3照射光，基於上述光之照射而使黏著力降低，另一方面，對殘存部分6中之黏著層3不照射光，而不會因上述光之照射發生黏著力之降低，且在仍保持強黏著力之狀態下殘留。By this, light is irradiated to the adhesive layer 3 in the removed part 7, and the adhesive force is reduced based on the above light irradiation. On the other hand, the adhesive layer 3 in the remaining part 6 is not irradiated with light, and the light is not affected by the light. The adhesive force decreases after irradiation, and it remains in a state where strong adhesive force is still maintained.

並且，於第5步驟中，如圖3D所示，自被黏著體4將黏著片材1中之去除部分7去除。In addition, in the fifth step, as shown in FIG. 3D, the removed part 7 of the adhesive sheet 1 is removed from the adherend 4.

具體而言，將殘存部分6及去除部分7例如藉由CO2 雷射等進行切割，然後僅將去除部分7以去除部分7之端部作為起點進行剝離。Specifically, the remaining portion 6 and the removed portion 7 are cut by, for example, a CO 2 laser or the like, and then only the removed portion 7 is peeled off with the end of the removed portion 7 as a starting point.

此時，去除部分7中之黏著層3之黏著力降低，因此可容易地自被黏著體4將去除部分7剝離。At this time, the adhesive force of the adhesive layer 3 in the removed part 7 is reduced, so the removed part 7 can be easily peeled from the adherend 4.

另一方面，殘存部分6中之黏著層3之黏著力未降低，具有上述較高之初始黏著力，因此殘存部分6殘存於被黏著體4。On the other hand, the adhesive force of the adhesive layer 3 in the remaining part 6 does not decrease, and has the above-mentioned higher initial adhesive force, so the remaining part 6 remains on the adherend 4.

又，殘存部分6具有上述較高之初始黏著力，因此即便將去除部分7剝離，亦可抑制與去除部分7相接之殘存部分6之端部發生***。In addition, the remaining portion 6 has the above-mentioned high initial adhesive force. Therefore, even if the removed portion 7 is peeled off, the end of the remaining portion 6 that is in contact with the removed portion 7 can be suppressed from bulging.

於是，殘存部分6可直接用於被黏著體4之補強。Therefore, the remaining part 6 can be directly used for the reinforcement of the adherend 4.

又，藉由殘存部分6而賦予適度之剛性，因此處理性提高。In addition, the remaining portion 6 imparts a moderate rigidity, so that the handling properties are improved.

尤其於被黏著體4為電子器件之情形時，電子器件有隨著高積體化、小型輕量化及構成零件之薄型化而電子器件之構成零件之厚度變小之傾向。因該薄型化，而容易於構成零件之積層界面產生起因於應力之彎曲或捲曲。又，因薄型化，而容易產生因自身重量導致之撓曲。Particularly when the adherend 4 is an electronic device, the electronic device tends to decrease in thickness as the electronic device becomes more integrated, smaller and lighter in weight, and thinner in component parts. Due to this thinning, bending or curling due to stress is likely to occur at the laminated interface of the constituent parts. Also, due to the thinning, it is prone to bend due to its own weight.

既便於此種情形時，根據該黏著片材1，亦可藉由殘存部分6對電子器件賦予剛性，因此可抑制因應力或自身重量等導致之彎曲、捲曲、撓曲等，從而提高處理性。Even in this case, according to the adhesive sheet 1, the remaining part 6 can also impart rigidity to the electronic device. Therefore, bending, curling, and bending caused by stress or its own weight can be suppressed, thereby improving handling .

又，於在電子器件之製造步驟中藉由經自動化之裝置進行搬送或加工之情形時，存在電子器件之構成零件與搬送臂及銷等構件接觸，導致構成零件破損之情況。In addition, when the electronic device is transported or processed by an automated device in the manufacturing step of the electronic device, the component parts of the electronic device may come into contact with the components such as the transport arm and pins, causing the component parts to be damaged.

尤其於經高積體化、小型輕量化及薄型化之器件中，存在於搬送裝置等之接觸或切斷加工時產生因局部應力之集中導致之破損或尺寸變化之情況。Especially in devices that have been increased in size, size, weight, and thickness, there are cases where damage or dimensional changes due to local stress concentration occur during contact or cutting processing of conveying equipment.

既便於此種情形時，根據該黏著片材1，亦可藉由殘存部分6賦予適度之剛性，並且對應力加以緩和、分散，而抑制龜裂、破裂、剝落、尺寸變化等。Even in such a case, according to the adhesive sheet 1, moderate rigidity can be imparted to the remaining portion 6, and the stress can be relieved and dispersed, thereby suppressing cracks, cracks, peeling, dimensional changes, and the like.

再者，去除部分7之形狀並無特別限定，例如亦可為十字形(圖4)、圓形(圖5)。Furthermore, the shape of the removed portion 7 is not particularly limited, and for example, it may be a cross (FIG. 4) or a circle (FIG. 5).

於去除部分7為十字形(具體而言為包含黏著片材1之面之兩端之十字形狀)之情形時，如圖4A所示，於第5步驟中，與上述同樣地對殘存部分6(十字形以外之部分)配置遮罩8而阻斷光，另一方，對去除部分7(十字形)不配置遮罩8而照射光。In the case where the removed portion 7 is a cross shape (specifically, a cross shape including both ends of the surface of the adhesive sheet 1), as shown in FIG. 4A, in the fifth step, the remaining portion 6 is the same as the above. (Parts other than the cross shape) A mask 8 is arranged to block light, and on the other hand, the mask 8 is not arranged on the removed part 7 (cross shape) and light is irradiated.

藉此，僅殘存部分6中之黏著層3之黏著力降低。Thereby, only the adhesive force of the adhesive layer 3 in the remaining part 6 is reduced.

並且，於第5步驟中，如圖4B所示，將殘存部分6及去除部分7切斷，然後僅將去除部分7以去除部分7之端部作為起點進行剝離，藉此自被黏著體4將黏著片材1中之去除部分7去除。And, in the fifth step, as shown in FIG. 4B, the remaining part 6 and the removed part 7 are cut, and then only the removed part 7 is peeled off with the end of the removed part 7 as the starting point, thereby from the adherend 4 The removed part 7 in the adhesive sheet 1 is removed.

又，於上述說明中，在第5步驟中，以黏著片材1之端部作為起點將黏著片材1自被黏著體4剝離，但其中存在難以使黏著片材1之端部成為起點之情況。In addition, in the above description, in the fifth step, the adhesive sheet 1 is peeled from the adherend 4 with the end of the adhesive sheet 1 as the starting point. However, it is difficult to make the end of the adhesive sheet 1 the starting point. Happening.

具體而言，如圖5A所示，於去除部分7在黏著片材1中且在黏著片材1之中央部為圓形之情形時，去除部分不包含黏著片材1之面之端部，因此難以將去除部分7之端部作為起點而將去除部分7剝離。Specifically, as shown in FIG. 5A, when the removed portion 7 is in the adhesive sheet 1 and the center portion of the adhesive sheet 1 is circular, the removed portion does not include the end of the surface of the adhesive sheet 1, Therefore, it is difficult to peel off the removed portion 7 using the end of the removed portion 7 as a starting point.

但，於此種情形時，如圖5B所示，藉由在第5步驟中利用黏著滾筒9來黏著去除部分7，可將去除部分7剝離。However, in this case, as shown in FIG. 5B, by adhering the removed portion 7 with the adhesive roller 9 in the fifth step, the removed portion 7 can be peeled off.

如此，根據該黏著片材1，可將任意部分去除。 [實施例]In this way, according to the adhesive sheet 1, arbitrary parts can be removed. [Example]

以下，示出實施例及比較例，更具體地說明本發明。再者，本發明不受實施例及比較例任何限定。又，以下記載中所使用之調配比率(含有比率)、物性值、參數等具體數值可代替為上述「實施方式」中所記載之與其等對應之調配比率(含有比率)、物性值、參數等該記載之上限值(定義為「以下」、「未達」之數值)或下限值(定義為「以上」、「超過」之數值)。Hereinafter, examples and comparative examples are shown to explain the present invention more specifically. Furthermore, the present invention is not limited in any way by the examples and comparative examples. In addition, specific numerical values such as blending ratios (content ratios), physical property values, and parameters used in the following descriptions can be replaced with blending ratios (content ratios), physical property values, parameters, etc. corresponding to them described in the above-mentioned "embodiment" The upper limit (defined as "below" or "not reached") or lower limit (defined as "above" or "exceeding").

再者，「份」及「%」只要未特別提及，便為質量基準。Furthermore, "parts" and "%" are quality standards as long as they are not specifically mentioned.

1.成分之詳情 將各實施例及各比較例中所使用之各成分記載於以下。 Takenate D110N：苯二甲基二異氰酸酯之三羥甲基丙烷加成體之75%乙酸乙酯溶液，三井化學製造 A-DPH：二季戊四醇六丙烯酸酯；官能基當量96 g/eq APG700：聚丙二醇＃700(n＝12)二丙烯酸酯；官能基當量404 g/eq Irgacure 184：1-羥基環己基苯基酮，BASF製造1. Details of ingredients Each component used in each Example and each comparative example is described below. Takenate D110N: 75% ethyl acetate solution of trimethylolpropane adduct of xylylene diisocyanate, manufactured by Mitsui Chemicals A-DPH: Dipentaerythritol hexaacrylate; functional group equivalent 96 g/eq APG700: Polypropylene glycol #700 (n=12) diacrylate; functional group equivalent 404 g/eq Irgacure 184: 1-hydroxycyclohexyl phenyl ketone, manufactured by BASF

2.聚合物之製備 合成例1 向具備溫度計、攪拌機、回流冷卻管及氮氣導入管之反應容器中投入作為單體之甲基丙烯酸甲酯(MMA)9重量份、丙烯酸2-乙基己酯(2EHA)63重量份、丙烯酸2-羥基乙酯(HEA)13重量份、N-乙烯基吡咯啶酮(NVP)15重量份、作為聚合起始劑之偶氮雙異丁腈0.2重量份、以及作為溶劑之乙酸乙酯233重量份，通入氮氣，一面攪拌一面進行約1小時氮氣置換。然後，加熱至60℃，反應7小時而獲得重量平均分子量(Mw)為1200000之丙烯酸系聚合物之溶液。2. Preparation of polymer Synthesis example 1 9 parts by weight of methyl methacrylate (MMA), 63 parts by weight of 2-ethylhexyl acrylate (2EHA), and 2 parts by weight of acrylic acid were put into a reaction vessel equipped with a thermometer, a stirrer, a reflux cooling tube, and a nitrogen introduction tube. -13 parts by weight of hydroxyethyl (HEA), 15 parts by weight of N-vinylpyrrolidone (NVP), 0.2 parts by weight of azobisisobutyronitrile as a polymerization initiator, and 233 parts by weight of ethyl acetate as a solvent Then, let in nitrogen gas, and perform nitrogen replacement for about 1 hour while stirring. Then, it heated to 60 degreeC, and reacted for 7 hours, and obtained the solution of the acrylic polymer with a weight average molecular weight (Mw) of 1.2 million.

3.光硬化性組合物之製備 製備例1 向合成例1之丙烯酸系聚合物溶液添加相對於聚合物之固形物成分100重量份為2.5質量份之Takenate D110N(苯二甲基二異氰酸酯之三羥甲基丙烷加成體之75%乙酸乙酯溶液，三井化學製造)作為交聯劑，添加相對於聚合物之固形物成分100重量份為20質量份之A-DPH(二季戊四醇六丙烯酸酯)作為光硬化劑，添加相對於聚合物之固形物成分100重量份為0.1質量份之Irgacure 184(1-羥基環己基苯基酮，BASF公司製造)作為光聚合起始劑，並均勻地進行混合，而製備光硬化性組合物。3. Preparation of photocurable composition Preparation Example 1 To the acrylic polymer solution of Synthesis Example 1, 2.5 parts by mass of Takenate D110N (75% ethyl acetate of trimethylolpropane adduct of xylylene diisocyanate) was added to 100 parts by weight of the solid content of the polymer. Ester solution, manufactured by Mitsui Chemicals) As a crosslinking agent, 20 parts by mass of A-DPH (dipentaerythritol hexaacrylate) is added as a light hardening agent relative to 100 parts by weight of the solid content of the polymer, and 100 parts by weight of the solid content is 0.1 parts by mass of Irgacure 184 (1-hydroxycyclohexyl phenyl ketone, manufactured by BASF Corporation) as a photopolymerization initiator and uniformly mixed to prepare a photocurable composition.

製備例2 將光硬化劑變更為APG700(聚丙二醇＃700(n＝12)二丙烯酸酯)，除此以外，與製備例1同樣地製備光硬化性組合物。Preparation Example 2 Except having changed the photocuring agent to APG700 (polypropylene glycol #700 (n=12) diacrylate), a photocurable composition was prepared in the same manner as in Preparation Example 1.

4.黏著片材之製造 實施例1 將未經表面處理之厚度75 μm之聚對苯二甲酸乙二酯膜(東麗製造之「Lumirror S10」)作為基材，於該基材上將製備例1之光硬化性組合物以乾燥後之厚度成為25 μm之方式藉由槽輥進行塗佈。以130℃乾燥1分鐘而去除溶劑。藉此，於基材之一面形成黏著層。進而，於黏著層之一面貼合剝離膜(表面經聚矽氧離型處理之厚度25 μm之聚對苯二甲酸乙二酯膜)之離型處理面。然後，於25℃之氛圍中進行4天熟化處理，使聚合物與交聯劑進行交聯反應。藉此製造黏著片材。4. Manufacture of adhesive sheet Example 1 A 75 μm thick polyethylene terephthalate film (“Lumirror S10” manufactured by Toray) without surface treatment was used as a substrate, and the photocurable composition of Preparation Example 1 was dried on the substrate After the thickness becomes 25 μm, it is coated with a grooved roll. The solvent was removed by drying at 130°C for 1 minute. In this way, an adhesive layer is formed on one surface of the substrate. Furthermore, the release treatment surface of a release film (a polyethylene terephthalate film with a thickness of 25 μm on which a silicone release treatment is applied) was attached to one surface of the adhesive layer. Then, the aging treatment was carried out in an atmosphere of 25°C for 4 days to cause the polymer and the crosslinking agent to undergo a crosslinking reaction. In this way, an adhesive sheet is manufactured.

比較例1 將光硬化性組合物變更為製備例2之光硬化性組合物，除此以外，與實施例1同樣地製造黏著片材。Comparative example 1 Except having changed the photocurable composition to the photocurable composition of Preparation Example 2, the adhesive sheet was produced in the same manner as in Example 1.

5.評價 (剪切儲存模數) 將各製備例之光硬化性組合物以乾燥後之厚度成為25 μm之方式塗佈於已實施離型處理之PET膜，然後進行乾燥及熟化，藉此獲得黏著層。以同樣順序準備60片黏著層，積層該黏著層，而製作1.5 mm之剪切儲存模數測定用樣品(光硬化前)。又，對於以上述方式所獲得之剪切儲存模數測定用樣品(光硬化前)，使用化學燈將照度5 mW/cm2 之紫外線照射360秒鐘，藉此製備剪切儲存模數測定用樣品(光硬化後)。5. Evaluation (shear storage modulus) The photocurable composition of each preparation example was applied to a PET film that had been subjected to a release treatment so that the thickness after drying became 25 μm, and then dried and cured, thereby Obtain an adhesive layer. In the same procedure, 60 adhesive layers were prepared, and the adhesive layers were laminated to prepare a 1.5 mm sample for measuring the shear storage modulus (before light curing). Also, for the sample for measuring the shear storage modulus obtained in the above manner (before photocuring), a chemical lamp was used to irradiate ultraviolet light with an illuminance of 5 mW/cm 2 for 360 seconds to prepare a sample for measuring the shear storage modulus. Sample (after light hardening).

對於剪切儲存模數測定用樣品(光硬化前)及剪切儲存模數測定用樣品(光硬化後)，使用Rheometric Scientific公司製造之「Advanced Rheometric Expansion System(ARES)」，藉由以下條件測定剪切儲存模數。將該結果示於表1。For the samples for measuring the shear storage modulus (before photocuring) and the samples for measuring the shear storage modulus (after photocuring), the "Advanced Rheometric Expansion System (ARES)" manufactured by Rheometric Scientific is used for measurement under the following conditions Shear storage modulus. The results are shown in Table 1.

(測定條件) 變形模式：扭曲 測定頻率：1 Hz 升溫速度：5℃/分鐘 測定溫度：-50～150℃ 形狀：平行板 8.0 mmϕ(Measurement conditions) Deformation mode: twist Measuring frequency: 1 Hz Heating rate: 5℃/min Measuring temperature: -50～150℃ Shape: parallel plate 8.0 mmϕ

(黏著力) 將厚度12.5 μm之聚醯亞胺膜(東麗杜邦製造之「Kapton 50EN」)經由雙面接著帶(日東電工製造之「No.531」)貼附於玻璃板，而獲得測定用聚醯亞胺膜基板。自切成寬25 mm×長100 mm之黏著片材去除剝離膜，使用手壓輥於25℃下將黏著片材與測定用聚醯亞胺膜基板貼合，而製備光硬化前之測定用試樣。(Adhesion) A polyimide film with a thickness of 12.5 μm ("Kapton 50EN" manufactured by Toray DuPont) was attached to a glass plate via a double-sided adhesive tape ("No.531" manufactured by Nitto Denko) to obtain a polyimide film for measurement. Amine film substrate. The adhesive sheet is cut into a width of 25 mm × length of 100 mm to remove the release film, and the adhesive sheet is bonded to the polyimide film substrate for measurement at 25°C using a hand roller to prepare the measurement before photocuring Sample.

另外，以與上述相同之順序製備光硬化前之黏著片材，自光硬化前之黏著片材之基材側照射紫外線而使黏著層光硬化，而製備光硬化後之測定用試樣。In addition, the adhesive sheet before photocuring was prepared in the same procedure as above, and ultraviolet rays were irradiated from the substrate side of the adhesive sheet before photocuring to photocur the adhesive layer to prepare a measurement sample after photocuring.

對該光硬化前之測定用試樣及光硬化後之測定用試樣分別測定黏著力。The adhesive force was measured on the measurement sample before light curing and the measurement sample after light curing.

具體而言，利用夾頭保持光硬化前之測定用試樣及光硬化後之測定用試樣之端部(黏著片材之端部)，以拉伸速度300 mm/分鐘實施補強膜之180°剝離，測定剝離強度。將該結果示於表1。Specifically, the end of the measurement sample before photocuring and the end of the measurement sample after photocuring (the end of the adhesive sheet) is held by the chuck, and the 180 of the reinforced film is implemented at a stretching speed of 300 mm/min. ° Peel off and measure the peel strength. The results are shown in Table 1.

[表1] 實施例、比較例No. 實施例1 比較例1 光硬化劑於25℃下之黏度(mPa・s) 6600 68 黏著力(N/25 mm) 光硬化前 13.47 1.30 光硬化後 2.79 19.57 剪切儲存模數G'(Pa) 光硬化前 7.85×104 6.65×104 光硬化後 3.43×106 2.17×105 HSP 3.25 4.97 [Table 1] Example, Comparative Example No. Example 1 Comparative example 1 Viscosity of light hardener at 25℃ (mPa·s) 6600 68 Adhesion (N/25 mm) Before light hardening 13.47 1.30 After light hardening 2.79 19.57 Shear storage modulus G'(Pa) Before light hardening 7.85×10 4 6.65×10 4 After light hardening 3.43×10 6 2.17×10 5 HSP 3.25 4.97

再者，上述發明係作為本發明之例示之實施形態而提供，但其僅為單純之示例，不應限定性地進行解釋。藉由該技術領域之從業者而明確可知之本發明之變化例包含於下述發明申請專利範圍中。 [產業上之可利用性]In addition, the above-mentioned invention is provided as an exemplary embodiment of the present invention, but it is only a mere example and should not be interpreted restrictively. Variations of the present invention that are clearly known by practitioners in this technical field are included in the scope of the following invention applications. [Industrial availability]

本發明之黏著片材可較佳地用於各種器件等之貼合。The adhesive sheet of the present invention can be preferably used for bonding various devices and the like.

1:黏著片材 2:基材 3:黏著層 4:被黏著體 5:剝離膜 6:殘存部分 7:去除部分 8:遮罩 9:黏著滾筒1: Adhesive sheet 2: substrate 3: Adhesive layer 4: adherend 5: Peel off the film 6: The remaining part 7: Remove part 8: Mask 9: Adhesion roller

圖1表示本發明之黏著片材之一實施形態之概略圖。 圖2係表示本發明之黏著片材之製造方法之一實施形態之概略圖，圖2A表示準備基材之第1步驟，圖2B表示於基材之一面積層黏著層之第2步驟，圖2C表示於黏著層一面積層剝離膜之步驟。 圖3係表示本發明之黏著片材之使用方法之一實施形態之概略圖，圖3A表示準備黏著片材之第3步驟，圖3B表示將黏著片材貼合於被黏著體之第4步驟，圖3C表示對黏著片材中之殘存部分不照射光，而對待去除部分照射光之第5步驟，圖3D表示於第5步驟中自被黏著體將去除部分去除之步驟。 圖4係表示去除部分為十字形之情形時之黏著片材之使用方法之概略圖，圖4A表示對黏著片材中之殘存部分不照射光，而對待去除部分照射光之第5步驟，圖4B表示於第5步驟中自被黏著體將去除部分去除之步驟。 圖5係表示去除部分為圓形之情形時之黏著片材之使用方法之概略圖，圖5A表示對黏著片材中之殘存部分不照射光，而對待去除部分照射光之第5步驟，圖5B表示於第5步驟中自被黏著體將去除部分去除之步驟。Fig. 1 shows a schematic view of an embodiment of the adhesive sheet of the present invention. Fig. 2 is a schematic diagram showing an embodiment of the method for manufacturing the adhesive sheet of the present invention. Fig. 2A shows the first step of preparing the substrate, and Fig. 2B shows the second step of layering an adhesive layer on an area of the substrate. Fig. 2C Shows the step of peeling off the film in an area of the adhesive layer. Figure 3 is a schematic diagram showing an embodiment of the method of using the adhesive sheet of the present invention. Figure 3A shows the third step of preparing the adhesive sheet, and Figure 3B shows the fourth step of attaching the adhesive sheet to the adherend 3C shows the fifth step in which light is not irradiated to the remaining part of the adhesive sheet but the part to be removed is irradiated. FIG. 3D shows the step of removing the removed part from the adherend in the fifth step. Figure 4 is a schematic diagram showing how to use the adhesive sheet when the removed part is cross-shaped. Figure 4A shows the fifth step of irradiating the remaining part of the adhesive sheet without light but irradiating the part to be removed. 4B represents the step of removing the removed part from the adherend in the fifth step. Fig. 5 is a schematic diagram showing how to use the adhesive sheet when the removed part is circular. Fig. 5A shows the fifth step of irradiating the remaining part of the adhesive sheet without light, but the part to be removed. 5B represents the step of removing the removed part from the adherend in the fifth step.

1:黏著片材 1: Adhesive sheet

2:基材 2: substrate

3:黏著層 3: Adhesive layer

Claims (5)

一種黏著片材，其特徵在於具備基材、及配置於上述基材之一面之黏著層，且 上述黏著層含有包含聚合物、具有2個以上聚合性官能基之光硬化劑、及光聚合起始劑之光硬化性組合物， 上述光硬化劑於25℃下之黏度為100 mPa・s以上， 光硬化後之上述黏著層於25℃下之剪切儲存模數G'為2.00×106 Pa以上。An adhesive sheet, which is characterized by having a substrate and an adhesive layer disposed on one surface of the substrate, and the adhesive layer contains a polymer, a photohardener having two or more polymerizable functional groups, and a photopolymerization layer. The light-curing composition of the starting agent, the viscosity of the light-curing agent at 25°C is more than 100 mPa·s, and the shear storage modulus G'of the adhesive layer at 25°C after light-curing is 2.00×10 6 Pa above. 如請求項1之黏著片材，其中光硬化後之上述黏著層之黏著力小於光硬化前之上述黏著層之黏著力。Such as the adhesive sheet of claim 1, wherein the adhesive force of the adhesive layer after photocuring is lower than the adhesive force of the adhesive layer before photocuring. 如請求項1或2之黏著片材，其中將光硬化前之上述黏著層以25℃貼合於聚醯亞胺膜並以剝離速度300 mm/分鐘藉由180度剝離試驗所測得之黏著力為5 N/25 mm以上。The adhesive sheet of claim 1 or 2, wherein the above-mentioned adhesive layer before photocuring is attached to the polyimide film at 25°C and the adhesion measured by a 180-degree peel test at a peeling speed of 300 mm/min The force is 5 N/25 mm or more. 如請求項1或2之黏著片材，其中將光硬化後之上述黏著層以25℃貼合於聚醯亞胺膜並以剝離速度300 mm/分鐘藉由180度剝離試驗所測得之黏著力為4 N/25 mm以下。The adhesive sheet of claim 1 or 2, wherein the light-cured adhesive layer is attached to the polyimide film at 25°C and the adhesion measured by a 180-degree peel test at a peeling speed of 300 mm/min The force is 4 N/25 mm or less. 如請求項1或2之黏著片材，其中上述光硬化劑具有4個以上之聚合性官能基。The adhesive sheet of claim 1 or 2, wherein the light curing agent has 4 or more polymerizable functional groups.
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