TW201708460A - Double-sided adhesive tape and method for manufacturing same - Google Patents
Double-sided adhesive tape and method for manufacturing same Download PDFInfo
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- TW201708460A TW201708460A TW105108802A TW105108802A TW201708460A TW 201708460 A TW201708460 A TW 201708460A TW 105108802 A TW105108802 A TW 105108802A TW 105108802 A TW105108802 A TW 105108802A TW 201708460 A TW201708460 A TW 201708460A
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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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
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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
- 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
- C09J2301/124—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 on both sides of the carrier, e.g. double-sided adhesive tape
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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
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
- C09J2400/24—Presence of a foam
- C09J2400/243—Presence of a foam in the substrate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本發明係關於一種使用於電子機器之零件固定用等之雙面黏著帶。 The present invention relates to a double-sided adhesive tape for use in fixing parts for electronic equipment.
攜帶資訊終端具有如下構造：包含殼體之影像顯示模組與玻璃板或丙烯酸板等透明之前面板藉由配置於其等相互對向之外周緣的雙面黏著帶貼合。此處，作為對此種雙面黏著帶之要求特性，除了接著性，還有可承受機器掉落衝撃之良好的耐衝撃性、可承受機器殼體之翹曲或變形、內部應力的應力緩和性、防水性等。 The portable information terminal has a structure in which an image display module including a casing and a transparent front panel such as a glass plate or an acrylic plate are attached by a double-sided adhesive tape disposed on a peripheral edge of the opposite direction. Here, as a required characteristic of the double-sided adhesive tape, in addition to the adhesiveness, there is a good impact resistance which can withstand the falling of the machine, a warpage or deformation which can withstand the machine casing, and a stress relaxation of the internal stress. Sex, water resistance, etc.
根據此等對雙面黏著帶所要求之特性，提出有一種雙面黏著帶，該雙面黏著帶於發泡體基材之雙面積層有使光硬化性丙烯酸系黏著劑組成物光硬化而得之黏著劑層(專利文獻1)。然而，此雙面黏著帶由於具有所使用之發泡體基材之氣泡的一部分會成為連續氣泡之缺點，故具有防水性下降之問題。因此，為了滿足耐衝擊性、防水性等要求特性，而考慮於雙面黏著帶之丙烯酸系黏著劑層摻合無機或有機物之微細中空粒子。 According to the characteristics required for the double-sided adhesive tape, there is proposed a double-sided adhesive tape having a double-layered layer on the foam substrate for photohardening the photocurable acrylic adhesive composition. Adhesive layer obtained (Patent Document 1). However, this double-sided adhesive tape has a problem that the water repellency is lowered because a part of the air bubbles having the foam base material to be used has a drawback of continuous air bubbles. Therefore, in order to satisfy the required characteristics such as impact resistance and water repellency, it is considered that the acrylic adhesive layer of the double-sided adhesive tape is mixed with fine inorganic particles of an inorganic or organic substance.
專利文獻1：日本特開2009-108314號公報 Patent Document 1: Japanese Patent Laid-Open Publication No. 2009-108314
近年來，影像顯示模組從畫面之有效利用的觀點或設計性的觀點，窄邊框化不斷發展，雙面黏著帶之寬度亦隨之窄小化(例如0.5~ 1.0mm)。因此，例如專利文獻1記載之技術，除了擔心基材容易伸長，於加工時發生不良情形外，且若氣泡變大，則會成為帶寬度以上之氣泡徑，喪失防水性能。又，隨著帶寬度之窄小化，於摻合有中空粒子之黏著帶，亦會有接著力(為基本性能)下降之虞。 In recent years, the image display module has been developed from the viewpoint of effective use of the screen or the design point of view, and the width of the double-sided adhesive tape has also been narrowed (for example, 0.5~ 1.0mm). Therefore, for example, in the technique described in Patent Document 1, in addition to the fact that the substrate is easily elongated, a problem occurs during processing, and if the bubble is increased, the bubble diameter is equal to or greater than the tape width, and the waterproof performance is lost. Further, as the width of the belt is narrowed, there is a possibility that the adhesion force (which is a basic property) is lowered in the adhesive tape in which the hollow particles are blended.
因此，本發明之目的在於提供一種於帶寬度經窄小化之情形時，亦具備接著強度及被要求作為雙面黏著帶特性之各種性能的雙面黏著帶，及其製造方法。 Accordingly, it is an object of the present invention to provide a double-sided adhesive tape which has a bonding strength and various properties required as a double-sided adhesive tape when the tape width is narrowed, and a method of manufacturing the same.
為了解決上述之課題，本發明之雙面黏著帶具有基材膜、形成於上述基材膜之一面含有中空粒子之第1黏著劑層及形成於上述基材膜之另一面含有中空粒子之第2黏著劑層，上述第1、第2黏著劑層之上述中空粒子偏存於上述基材膜側。 In order to solve the above problems, the double-sided adhesive tape of the present invention has a base film, a first adhesive layer formed on one surface of the base film, and a hollow particle formed on the other surface of the base film. In the adhesive layer, the hollow particles of the first and second adhesive layers are located on the side of the base film.
又，本發明之雙面黏著帶之製造方法，具有下述步驟：將黏著劑中含有中空粒子之含中空粒子之黏著劑層與不含有上述中空粒子之不含中空粒子之黏著劑層積層於基材膜之一面，形成第1黏著劑層的步驟；及將黏著劑中含有上述中空粒子之含中空粒子之黏著劑層與不含有上述中空粒子之不含中空粒子之黏著劑層積層於上述基材膜之另一面，形成第2黏著劑層之步驟；上述第1、第2黏著劑層之上述中空粒子偏存於上述基材膜側。 Moreover, the method for producing a double-sided adhesive tape according to the present invention has the steps of laminating an adhesive layer containing hollow particles containing hollow particles in an adhesive and an adhesive containing no hollow particles containing no such hollow particles. a step of forming a first adhesive layer on one surface of the base film; and an adhesive layer containing hollow particles containing the hollow particles in the adhesive; and an adhesive layer containing no hollow particles not containing the hollow particles The other surface of the base film is a step of forming a second adhesive layer; and the hollow particles of the first and second adhesive layers are biased on the base film side.
又，本發明之雙面黏著帶之製造方法，具有下述步驟：將不含有中空粒子之黏著劑塗佈於第1剝離膜之表面，形成第1不含中空粒子之黏著劑層的步驟；於上述第1不含中空粒子之黏著劑層表面，塗佈含有上述中空粒子之黏著劑且積層基材膜，形成第1含中空粒子之黏著劑層的 步驟；使上述第1含中空粒子之黏著劑層與上述第1不含中空粒子之黏著劑層硬化，藉此進行一體化，形成第1黏著劑層的步驟；於上述基材膜未形成有上述第1黏著劑層之面，塗佈含有上述中空粒子之黏著劑，形成第2含中空粒子之黏著劑層的步驟；於上述第2含中空粒子之黏著劑層表面，塗佈不含有上述中空粒子之黏著劑且積層第2剝離膜，形成第2不含中空粒子之黏著劑層的步驟；及使上述第2含中空粒子之黏著劑層與上述第2不含中空粒子之黏著劑層硬化，藉此進行一體化，形成第2黏著劑層的步驟。 Moreover, the method for producing a double-sided adhesive tape according to the present invention has the following steps: a step of applying an adhesive containing no hollow particles to the surface of the first release film to form a first adhesive layer containing no hollow particles; Applying an adhesive containing the hollow particles to the surface of the first adhesive layer containing no hollow particles, and laminating a base film to form a first hollow particle-containing adhesive layer a step of forming the first adhesive layer by curing the first hollow particle-containing adhesive layer and the first hollow particle-free adhesive layer, thereby forming the first adhesive layer; a step of applying an adhesive containing the hollow particles to form a second hollow particle-containing adhesive layer on the surface of the first adhesive layer; and applying the coating on the surface of the second hollow particle-containing adhesive layer a step of laminating a second release film to form a second adhesive layer containing no hollow particles, and an adhesive layer for the second hollow particles and the second adhesive layer containing no hollow particles The step of hardening is integrated to form a second adhesive layer.
根據本發明，藉由使中空粒子偏存於基材膜側，而可使中空粒子不會露出於與被接著物接觸之第1、第2黏著劑層之表面，提升對被接著物之剝離強度(界面破裂強度)。 According to the present invention, by arranging the hollow particles on the side of the base film, the hollow particles can be prevented from being exposed to the surface of the first and second adhesive layers which are in contact with the object to be adhered, thereby promoting peeling of the adherend. Strength (interfacial fracture strength).
1‧‧‧雙面黏著帶 1‧‧‧Double adhesive tape
2‧‧‧基材膜 2‧‧‧Base film
2a‧‧‧一面 2a‧‧‧ side
2b‧‧‧另一面 2b‧‧‧The other side
3‧‧‧第1黏著劑層 3‧‧‧1st adhesive layer
4‧‧‧中空粒子 4‧‧‧ hollow particles
5‧‧‧第2黏著劑層 5‧‧‧2nd adhesive layer
6‧‧‧第1剝離膜 6‧‧‧1st release film
7‧‧‧第2剝離膜 7‧‧‧2nd release film
10‧‧‧含中空粒子之黏著劑層 10‧‧‧Adhesive layer containing hollow particles
10a‧‧‧第1含中空粒子之黏著劑層 10a‧‧‧1st adhesive layer containing hollow particles
10b‧‧‧第2含中空粒子之黏著劑層 10b‧‧‧2nd adhesive layer containing hollow particles
11‧‧‧不含中空粒子之黏著劑層 11‧‧‧Adhesive layer without hollow particles
11a‧‧‧第1不含中空粒子之黏著劑層 11a‧‧‧1st adhesive layer without hollow particles
11b‧‧‧第2不含中空粒子之黏著劑層 11b‧‧‧2nd adhesive layer without hollow particles
20‧‧‧膜積層體 20‧‧‧membrane layer
圖1係顯示應用本發明之雙面黏著帶的剖面圖。 BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a cross-sectional view showing a double-sided adhesive tape to which the present invention is applied.
圖2(A)係顯示積層含中空粒子之黏著劑層與不含中空粒子之黏著劑層之狀態的剖面圖，圖2(B)係顯示形成黏著劑層之狀態的剖面圖，該黏著劑層係藉由使含中空粒子之黏著劑層與不含中空粒子之黏著劑層同時硬化使兩層一體化而成。 Fig. 2(A) is a cross-sectional view showing a state in which an adhesive layer containing hollow particles and an adhesive layer containing no hollow particles are laminated, and Fig. 2(B) is a cross-sectional view showing a state in which an adhesive layer is formed, the adhesive The layer is formed by integrating the adhesive layer containing the hollow particles and the adhesive layer containing no hollow particles at the same time to form two layers.
圖3係顯示形成膜積層體之步驟之圖，該膜積層體於基材膜之一面積層有第1黏著劑層。 Fig. 3 is a view showing a step of forming a film laminate having a first adhesive layer on one of the substrate layers of the base film.
圖4(A)係顯示膜積層體之剖面圖，該膜積層體於第1剝離膜積層有第1不含中空粒子之黏著劑層與第1含中空粒子之黏著劑層與基材膜，圖4 (B)係顯示形成有第1黏著劑層之膜積層體的剖面圖，該第1黏著劑層係藉由使第1含中空粒子之黏著劑層與第1不含中空粒子之黏著劑層同時硬化使兩層一體化而成。 4(A) is a cross-sectional view showing a film laminate in which a first release layer is provided with a first adhesive layer containing no hollow particles and a first hollow particle-containing adhesive layer and a base film. Figure 4 (B) is a cross-sectional view showing a film laminate in which a first adhesive layer is formed, and the first adhesive layer is formed by using an adhesive layer of the first hollow particles and the first adhesive layer containing no hollow particles. Simultaneous hardening makes the two layers integrated.
圖5係顯示將第2黏著劑層積層於膜積層體之基材膜之另一面，形成雙面黏著帶之步驟之圖。 Fig. 5 is a view showing a step of forming a double-sided adhesive tape by laminating a second adhesive on the other surface of the base film of the film laminate.
圖6(A)係顯示於膜積層體之基材膜之另一面積層有第2不含中空粒子之黏著劑層與第2含中空粒子之黏著劑層與剝離膜的狀態之剖面圖，圖6(B)係顯示形成有第2黏著劑層之雙面黏著帶的剖面圖，該第2黏著劑層係藉由使第2含中空粒子之黏著劑層與第2不含中空粒子之黏著劑層同時硬化使兩層一體化而成。 6(A) is a cross-sectional view showing a state in which the second adhesive layer containing no hollow particles and the second hollow particle-containing adhesive layer and the release film are formed on the other surface layer of the base film of the film laminate. 6(B) is a cross-sectional view showing a double-sided adhesive tape in which a second adhesive layer is formed, and the second adhesive layer is adhered to the second hollow particle-containing adhesive layer and the second non-hollow particle-free adhesive layer. The agent layer is simultaneously hardened to form two layers.
以下，一邊參照圖式，一邊詳細說明應用本發明之雙面黏著帶及其製造方法。另，本發明並非僅限定於以下之實施形態，在不脫離本發明之精神的範圍內當然可做各種改變。又，圖式係示意性者，各尺寸之比率等有時會與實際不同。具體之尺寸等應參酌以下之說明加以判斷。又，圖式相互間當然亦包含彼此之尺寸關係或比率不同之部分。 Hereinafter, the double-sided adhesive tape to which the present invention is applied and a method for manufacturing the same will be described in detail with reference to the drawings. The present invention is not limited to the embodiments described below, and various changes can of course be made without departing from the spirit of the invention. Moreover, the drawings are schematic, and the ratio of each size may be different from the actual one. The specific dimensions and the like should be judged by considering the following instructions. Moreover, the drawings also of course include mutually different dimensional relationships or ratios.
[雙面黏著帶] [double-sided adhesive tape]
應用本發明之雙面黏著帶1如圖1所示，具有基材膜2、形成於基材膜2之一面2a且含有中空粒子4的第1黏著劑層3及形成於基材膜2之另一面2b且含有中空粒子4的第2黏著劑層5，第1、第2黏著劑層3、5的中空粒子4偏存於基材膜2側。又，雙面黏著帶1亦可於第1黏著劑層3積層有第1剝離膜6，於第2黏著劑層5積層有第2剝離膜7。 As shown in FIG. 1, the double-sided adhesive tape 1 of the present invention has a base film 2, a first adhesive layer 3 formed on one surface 2a of the base film 2 and containing hollow particles 4, and a base film 2 formed thereon. On the other surface 2b and the second adhesive layer 5 containing the hollow particles 4, the hollow particles 4 of the first and second adhesive layers 3 and 5 are biased on the side of the base film 2 . Further, in the double-sided adhesive tape 1, the first release film 6 may be laminated on the first adhesive layer 3, and the second release film 7 may be laminated on the second adhesive layer 5.
[基材膜] [Substrate film]
基材膜2於雙面支持第1、第2黏著劑層3、5。作為此種基材膜2，可採用公知者作為雙面黏著帶之基材。例如可較佳使用PET(聚對酞酸乙二酯)等之聚酯基材膜。另，基材膜2之厚度根據其適用對象等而不同，通常為5~100μm厚，較佳為10~50μm厚。 The base film 2 supports the first and second adhesive layers 3 and 5 on both sides. As such a base film 2, a known substrate can be used as a base material of a double-sided adhesive tape. For example, a polyester base film such as PET (polyethylene terephthalate) can be preferably used. Further, the thickness of the base film 2 varies depending on the object to be applied, etc., and is usually 5 to 100 μm thick, preferably 10 to 50 μm thick.
[黏著劑層] [Adhesive layer]
於基材膜2之一面2a，積層有第1黏著劑層3，於另一面2b則積層有第2黏著劑層5。以下雖然說明第1黏著劑層3，但是第2黏著劑層5亦具有與第1黏著劑層3相同之構成。 The first adhesive layer 3 is laminated on one surface 2a of the base film 2, and the second adhesive layer 5 is laminated on the other surface 2b. Hereinafter, the first adhesive layer 3 will be described, but the second adhesive layer 5 also has the same configuration as the first adhesive layer 3.
[黏著劑組成物] [Adhesive composition]
第1黏著劑層3係將摻合有中空粒子之黏著劑組成物加以成膜，並使之硬化而成者。黏著劑組成物可使用被用作黏著帶之黏著劑組成物之公知的熱及/或光硬化性黏著劑組成物。其中，構成本發明之第1黏著劑層3之黏著劑組成物，較佳由光硬化性丙烯酸系黏著劑組成物形成。此種光硬化性丙烯酸系黏著劑組成物，含有成分(a)單官能(甲基)丙烯酸酯、成分(b)(甲基)丙烯酸、成分(c)丙烯酸系交聯劑及成分(d)光自由基聚合起始劑。此處，(甲基)丙烯酸酯之用語，為包含丙烯酸酯與甲基丙烯酸酯之用語。 The first adhesive layer 3 is obtained by forming a film of an adhesive composition in which hollow particles are blended and hardening it. As the adhesive composition, a known heat and/or photocurable adhesive composition which is used as an adhesive composition of an adhesive tape can be used. Among them, the adhesive composition constituting the first adhesive layer 3 of the present invention is preferably formed of a photocurable acrylic adhesive composition. The photocurable acrylic pressure-sensitive adhesive composition contains the component (a) a monofunctional (meth) acrylate, a component (b) (meth) acryl, a component (c) an acryl-based crosslinking agent, and a component (d). Photoradical polymerization initiator. Here, the term (meth) acrylate is a term including acrylate and methacrylate.
此等成分之較佳摻合比例，係相對於成分(a)單官能(甲基)丙烯酸酯100質量份，成分(b)(甲基)丙烯酸為2~20質量份，(c)丙烯酸系交聯劑為0.1~1.0質量份，及(d)光自由基聚合起始劑為0.1~1.0質量份。更佳之摻合比例，係相對於成分(a)單官能(甲基)丙烯酸酯100 質量份，成分(b)(甲基)丙烯酸為4~10質量份，(c)丙烯酸系交聯劑為0.2~0.5質量份，及(d)光自由基聚合起始劑為0.2~0.6質量份。 The preferred blending ratio of these components is 100 parts by mass based on the component (a) monofunctional (meth) acrylate, and the component (b) (meth)acrylic acid is 2 to 20 parts by mass, (c) acrylic acid. The crosslinking agent is 0.1 to 1.0 part by mass, and (d) the photoradical polymerization initiator is 0.1 to 1.0 part by mass. A more desirable blend ratio is based on the component (a) monofunctional (meth) acrylate 100 The mass fraction, the component (b) (meth)acrylic acid is 4 to 10 parts by mass, (c) the acrylic crosslinking agent is 0.2 to 0.5 parts by mass, and (d) the photoradical polymerization initiator is 0.2 to 0.6 mass. Share.
成分(a)之單官能(甲基)丙烯酸酯，為成為聚合物之基底的光聚合性單體，可使用任意之單官能(甲基)丙烯酸酯。從通用性及玻璃轉移點(Tg，較佳為-70~-10℃)低之方面而言，較佳使用選自由丙烯酸2-乙基己酯、丙烯酸丁酯、丙烯酸異辛酯、丙烯酸異十八酯(isostearyl acrylate)及丙烯酸乙基卡必醇酯組成之群中的至少一種。 The monofunctional (meth) acrylate of the component (a) is a photopolymerizable monomer which is a base of the polymer, and any monofunctional (meth) acrylate can be used. From the viewpoint of low versatility and glass transition point (Tg, preferably -70 to -10 ° C), it is preferably selected from the group consisting of 2-ethylhexyl acrylate, butyl acrylate, isooctyl acrylate, and acrylic acid. At least one of the group consisting of isostearyl acrylate and ethyl carbitol acrylate.
成分(b)之(甲基)丙烯酸係用以對聚合物賦予耐熱性、凝聚力之單體，為丙烯酸或甲基丙烯酸。 The (meth)acrylic acid of the component (b) is a monomer for imparting heat resistance and cohesive force to the polymer, and is acrylic acid or methacrylic acid.
成分(c)之丙烯酸系交聯劑係用以對聚合物賦予不會熱熔融之硬化性的單體，可使用公知之丙烯酸系交聯劑。較佳為於分子中具有2個以上之丙烯醯基或甲基丙烯醯基的多官能(甲基)丙烯酸酯。具體而言，可使用選自由新戊二醇二(甲基)丙烯酸酯、羥基三甲基乙酸新戊二醇二(甲基)丙烯酸酯、羥基三甲基乙酸新戊基二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、壬二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯及EO改質聚丙二醇二(甲基)丙烯酸酯組成之群中的至少一種。作為可於市場上取得之交聯劑，具有KAYARAD MANDA(日本化藥股份有限公司製)、Aronix M-270(東亞合成股份有限公司製)。 The acrylic crosslinking agent of the component (c) is a monomer which imparts curability to the polymer without being thermally melted, and a known acrylic crosslinking agent can be used. A polyfunctional (meth) acrylate having two or more acryl fluorenyl groups or methacryl fluorenyl groups in the molecule is preferred. Specifically, it can be selected from the group consisting of neopentyl glycol di(meth)acrylate, hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate, hydroxytrimethylacetate neopentyl di(methyl) Acrylate, polypropylene glycol di(meth)acrylate, decanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate And at least one of the group consisting of EO-modified polypropylene glycol di(meth)acrylate. As a cross-linking agent which is commercially available, KAYARAD MANDA (manufactured by Nippon Kayaku Co., Ltd.) and Aronix M-270 (manufactured by Toagosei Co., Ltd.) are available.
成分(d)之光自由基聚合起始劑係為了使成分(a)~(c)進行光聚合而必需之活性種源，可於不會損及本發明之效果的範圍，使用公知之光自由基聚合起始劑。較佳可使用選自由肟酯系光聚合起始劑、氧 化醯基膦(acyl phosphine oxide)系光聚合起始劑及苯烷基酮(alkylphenone)系光聚合起始劑組成之群中的至少一種光聚合起始劑。作為可於市場上取得之光自由基聚合起始劑，例如具有2-羥基-2-甲基-1-苯基-丙烷-1-酮(Darocur 1173，BASF日本公司製)。 The photoradical polymerization initiator of the component (d) is an active species source necessary for photopolymerization of the components (a) to (c), and a known light can be used without damaging the effects of the present invention. Free radical polymerization initiator. Preferably, it is selected from an oxime ester photopolymerization initiator, oxygen At least one photopolymerization initiator of the group consisting of acyl phosphine oxide photopolymerization initiator and alkylphenone photopolymerization initiator. The photoradical polymerization initiator which is commercially available has, for example, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur 1173, manufactured by BASF Japan).
[中空粒子] [hollow particles]
作為中空粒子4，可從玻璃、陶瓷等無機中空粒子；聚丙烯腈、聚乙烯、聚苯乙烯等有機中空粒子等公知之中空粒子中，根據雙面黏著帶1之使用目的等作適當決定。其中，就衝擊吸收性方面而言，可較佳地使用聚丙烯腈中空粒子。 The hollow particles 4 can be appropriately determined from known hollow particles such as inorganic hollow particles such as glass and ceramics, and organic hollow particles such as polyacrylonitrile, polyethylene, and polystyrene, depending on the purpose of use of the double-sided adhesive tape 1. Among them, in terms of impact absorption, polyacrylonitrile hollow particles can be preferably used.
又，中空粒子4可較佳地使用平均粒徑為20~40μm者。其原因在於：若為此範圍，則不會損及黏著劑之強度，可得到足夠之耐衝撃性能。平均粒徑之測量，例如可使用雷射光散射式粒度分佈測量裝置進行。 Further, as the hollow particles 4, those having an average particle diameter of 20 to 40 μm can be preferably used. The reason for this is that if it is in this range, the strength of the adhesive is not impaired, and sufficient punching resistance can be obtained. The measurement of the average particle diameter can be carried out, for example, using a laser light scattering type particle size distribution measuring device.
[含量] [content]
含中空粒子之黏著劑層中的中空粒子之含量，較佳為20~40體積%，更佳為25~35體積%。若為此範圍，則可得到足夠之耐衝撃性能，且亦不會損及黏著劑之強度。作為中空粒子之分散方法、成膜方法、光硬化方法，可於不會損及本發明之效果的範圍，可採用任意之手法。例如，可採用混合機、溶解器等之攪拌機作為分散方法。 The content of the hollow particles in the adhesive layer containing hollow particles is preferably from 20 to 40% by volume, more preferably from 25 to 35% by volume. If it is in this range, sufficient impact resistance can be obtained without impairing the strength of the adhesive. As the dispersion method of the hollow particles, the film formation method, and the photo-curing method, any method can be employed without impairing the effects of the present invention. For example, a mixer such as a mixer or a dissolver can be employed as the dispersion method.
[黑色顏料] [black pigment]
另，中空粒子亦可於其表面實施有黑色顏料附著處理。此處，所謂黑色顏料附著處理，係指使黑色顏料附著於中空粒子之表面的處理，只要不 會損及本發明之效果，可採用任意之方法。例如，可列舉使用罐磨機將中空粒子與黑色顏料混合，或混合機等。就處理操作之簡便性與黑色顏料附著處理效率高低之平衡而言，較佳可舉使用罐磨機將中空粒子與黑色顏料混合。 Further, the hollow particles may be subjected to a black pigment adhesion treatment on the surface thereof. Here, the term "black pigment adhesion treatment" refers to a process of attaching a black pigment to the surface of the hollow particles, as long as it is not Any method may be employed which may impair the effects of the present invention. For example, a hollow mill may be mixed with a black pigment using a pot mill, or a mixer or the like. In terms of the balance between the ease of handling operation and the efficiency of the black pigment adhesion treatment, it is preferred to use a pot mill to mix the hollow particles with the black pigment.
作為黑色顏料，可根據雙面黏著帶之使用目的等，從公知之無機黑色顏料、有機黑色顏料之中適當加以選擇。其中就通用性、成本之方面而言，可較佳地使用為無機黑色顏料之碳黑。 The black pigment can be appropriately selected from known inorganic black pigments and organic black pigments depending on the purpose of use of the double-sided adhesive tape or the like. Among them, carbon black which is an inorganic black pigment can be preferably used in terms of versatility and cost.
作為黑色顏料之平均粒徑，較佳為10~30nm，更佳為15~25nm。其原因在於：若為此範圍，則對樹脂之附著性良好，凝聚亦少。此平均粒徑之測量，例如亦可使用雷射光散射式粒度分佈測量裝置進行。 The average particle diameter of the black pigment is preferably 10 to 30 nm, more preferably 15 to 25 nm. The reason for this is that if it is in this range, the adhesion to the resin is good and the aggregation is small. The measurement of the average particle diameter can be carried out, for example, by using a laser light scattering type particle size distribution measuring device.
[於基材膜側之偏存] [Partial storage on the substrate side]
此處，於第1黏著劑層3中，中空粒子4偏存於基材膜2側。所謂中空粒子4偏存於基材膜2側之狀態，係指不包括中空粒子4分散於第1黏著劑層3之厚度方向的狀態或偏存於第1黏著劑層3之表面側的狀態，至少於使用雙面黏著帶1時，中空粒子4不存在於如緊臨與被接著物之界面的位置之狀態。 Here, in the first adhesive layer 3, the hollow particles 4 are scattered on the side of the base film 2 . The state in which the hollow particles 4 are located on the side of the base film 2 is a state in which the hollow particles 4 are not dispersed in the thickness direction of the first adhesive layer 3 or are deviated from the surface side of the first adhesive layer 3 At least when the double-sided adhesive tape 1 is used, the hollow particles 4 are not present in a state as close to the interface with the substrate.
[含中空粒子之黏著劑層/不含中空粒子之黏著劑層] [Adhesive layer containing hollow particles / Adhesive layer without hollow particles]
中空粒子4偏存於基材膜2側之第1黏著劑層3，可藉由下述方式形成：如圖2(A)所示，將黏著劑組成物中含有中空粒子4的含中空粒子之黏著劑層10與黏著劑組成物中未含中空粒子4的不含中空粒子之黏著劑層11加以積層，且將含中空粒子之黏著劑層10積層於基材膜2之一面2a後，如圖2(B)所示，使此等兩層之黏著劑組成物硬化而一體化。硬化方法可根 據黏著劑組成物之種類而選擇紫外線照射或加熱等。第2黏著劑層5亦可以相同方式形成。 The first adhesive layer 3 on the side of the base film 2 is formed by the hollow particles 4, and can be formed by containing hollow particles containing the hollow particles 4 in the adhesive composition as shown in Fig. 2(A). The adhesive layer 10 and the adhesive layer 11 containing no hollow particles containing the hollow particles 4 in the adhesive composition are laminated, and the adhesive layer 10 containing the hollow particles is laminated on one surface 2a of the base film 2, As shown in Fig. 2(B), the two layers of the adhesive composition were hardened and integrated. Hardening method can be rooted Ultraviolet irradiation or heating is selected depending on the type of the adhesive composition. The second adhesive layer 5 can also be formed in the same manner.
此種第1、第2黏著劑層3、5，係將使用相同種類之黏著劑組成物的含中空粒子之黏著劑層10與不含中空粒子之黏著劑層11加以積層，使兩層黏著劑組成物同時硬化。因此於雙面黏著帶1，含中空粒子之黏著劑層10與不含中空粒子之黏著劑層11的交聯反應在兩層中連續，藉此而一體化，貼合於被接著物後，於含中空粒子之黏著劑層10與不含中空粒子之黏著劑層11的界面亦不會產生剝離，可提升剝離強度(凝聚破裂強度)。 The first and second adhesive layers 3 and 5 are formed by laminating an adhesive layer 10 containing hollow particles using the same type of adhesive composition and an adhesive layer 11 containing no hollow particles. The composition of the agent hardens at the same time. Therefore, in the double-sided adhesive tape 1, the crosslinking reaction of the adhesive layer 10 containing the hollow particles and the adhesive layer 11 containing no hollow particles is continuous in the two layers, thereby integrating and bonding to the adherend. The interface between the adhesive layer 10 containing the hollow particles and the adhesive layer 11 containing no hollow particles is not peeled off, and the peel strength (cohesive fracture strength) can be improved.
又，雙面黏著帶1由於中空粒子4偏存於基材膜2側，故中空粒子4不會露出於與被接著物接觸之第1、第2黏著劑層3、5之表面，可提升對被接著物之剝離強度(界面破裂強度)。 Further, since the double-sided adhesive tape 1 is biased on the side of the base film 2, the hollow particles 4 are not exposed to the surfaces of the first and second adhesive layers 3 and 5 which are in contact with the substrate, and can be lifted. Peel strength (interfacial fracture strength) of the adherend.
因此，雙面黏著帶1，於例如摻合多達40體積%之中空粒子4的情形時，亦不會導致剝離強度(凝聚破裂/界面破裂)下降，可實現牢固之接著力。 Therefore, the double-sided adhesive tape 1 does not cause a drop in peel strength (agglomeration crack/interface crack) when, for example, a hollow particle 4 of up to 40% by volume is blended, and a firm adhesive force can be achieved.
[雙面黏著帶之製造方法] [Manufacturing method of double-sided adhesive tape]
接著，說明應用本發明之雙面黏著帶1的製造步驟。雙面黏著帶1之製造步驟具有：將黏著劑組成物中含有中空粒子4的含中空粒子之黏著劑層10與黏著劑組成物中未含中空粒子4的不含中空粒子之黏著劑層11積層於基材膜2之一面2a，形成第1黏著劑層3的步驟；及將黏著劑組成物中含有中空粒子4的含中空粒子之黏著劑層10與黏著劑組成物中未含中空粒子4的不含中空粒子之黏著劑層11積層於基材膜2之另一面2b，形成第2黏著劑層5的步驟。 Next, the manufacturing steps of the double-sided adhesive tape 1 to which the present invention is applied will be described. The manufacturing step of the double-sided adhesive tape 1 has the adhesive layer 10 containing hollow particles containing the hollow particles 4 in the adhesive composition, and the adhesive layer 11 containing no hollow particles containing no hollow particles 4 in the adhesive composition. a step of laminating one surface 2a of the base film 2 to form the first adhesive layer 3; and the adhesive layer 10 containing the hollow particles containing the hollow particles 4 in the adhesive composition and the adhesive composition containing no hollow particles The adhesive layer 11 containing no hollow particles of 4 is laminated on the other surface 2b of the base film 2 to form the second adhesive layer 5.
又，第1、第2黏著劑層3、5，較佳分別將黏著劑組成物中含有中空粒子4的含中空粒子之黏著劑層10與黏著劑組成物中未含中空粒子4的不含中空粒子之黏著劑層11積層後，進行硬化，藉此一體化而形成。 Further, the first and second adhesive layers 3 and 5 preferably contain the hollow particle-containing adhesive layer 10 containing the hollow particles 4 in the adhesive composition, and the adhesive composition does not contain the hollow particles 4, respectively. After the adhesive layer 11 of the hollow particles is laminated, it is cured and formed by integration.
具體而言，雙面黏著帶1之製造步驟如圖3所示，從剝離膜捲輪(release film roll)將第1剝離膜6捲出，於第1剝離膜6之表面塗佈不含中空粒子4之黏著劑，形成第1不含中空粒子之黏著劑層11a。 Specifically, as shown in FIG. 3, the manufacturing process of the double-sided adhesive tape 1 is performed by winding the first release film 6 from a release film roll, and coating the surface of the first release film 6 without hollow. The adhesive of the particles 4 forms the first adhesive layer 11a containing no hollow particles.
接著，於第1不含中空粒子之黏著劑層11a的表面塗佈含有中空粒子4之黏著劑，且進一步將基材膜2積層於其上，形成第1含中空粒子之黏著劑層10a。藉此，如圖4(A)所示，形成第1含中空粒子之黏著劑層10a及第1不含中空粒子之黏著劑層11a積層於基材膜2之一面2a的膜積層體20。作為第1不含中空粒子之黏著劑層11a及第1含中空粒子之黏著劑層10a的成膜方法並無特別特限定，例如，可採用使用輥塗機或棒塗機、缺角輪塗佈機(comma coater)、模塗機(die coater)等之方法。 Then, the adhesive containing the hollow particles 4 is applied onto the surface of the first hollow particle-free adhesive layer 11a, and the base film 2 is further laminated thereon to form the first hollow particle-containing adhesive layer 10a. As a result, as shown in FIG. 4(A), the first hollow particle-containing adhesive layer 10a and the first hollow particle-free adhesive layer 11a are laminated on the film laminate 20 of the one surface 2a of the base film 2. The film forming method of the first adhesive layer 11a containing no hollow particles and the first hollow particle-containing adhesive layer 10a is not particularly limited, and for example, a roll coater or a bar coater or a notch wheel can be used. A method such as a comma coater or a die coater.
另，較佳為，使第1含中空粒子之黏著劑層10a的塗佈厚度為50~100μm，第1不含中空粒子之黏著劑層11a的塗佈厚度為30~70μm，兩層全體之層厚為80~170μm。 Further, it is preferable that the thickness of the first hollow particle-containing adhesive layer 10a is 50 to 100 μm, and the thickness of the first hollow particle-free adhesive layer 11a is 30 to 70 μm, and both layers are entirely The layer thickness is 80~170μm.
接著，如圖4(B)所示，使第1含中空粒子之黏著劑層10a與第1不含中空粒子之黏著劑層11a硬化，藉此進行一體化，而形成第1黏著劑層3。作為硬化之方法，可藉由自基材膜2上照射紫外光之方式等來進行。 Next, as shown in FIG. 4(B), the first adhesive layer 10a containing the hollow particles and the first adhesive layer 11a containing no hollow particles are cured to be integrated, thereby forming the first adhesive layer 3. . The method of curing can be carried out by irradiating ultraviolet light from the base film 2 or the like.
藉此，可使第1含中空粒子之黏著劑層10a及第1不含中空粒子之黏著劑層11a一體化，且可形成中空粒子4偏存於基材膜2之一面 2a側的第1黏著劑層3。 Thereby, the first hollow particle-containing adhesive layer 10a and the first hollow particle-free adhesive layer 11a can be integrated, and the hollow particles 4 can be formed to be offset from one side of the base film 2 The first adhesive layer 3 on the 2a side.
接著，如圖5所示，將膜積層體20捲出，將含有中空粒子4之接著劑組成物塗佈於基材膜2未形成有第1黏著劑層3之另一面2b，形成第2含中空粒子之黏著劑層10b。並且，如圖6(A)所示，將不含中空粒子4之接著劑組成物塗佈於第2含中空粒子之黏著劑層10b表面，且進一步將第2剝離膜7積層於其上，形成第2不含中空粒子之黏著劑層11b。 Next, as shown in FIG. 5, the film laminate 20 is wound up, and the adhesive composition containing the hollow particles 4 is applied to the other surface 2b of the base film 2 where the first adhesive layer 3 is not formed, and the second surface is formed. The adhesive layer 10b containing hollow particles. Further, as shown in FIG. 6(A), the adhesive composition containing no hollow particles 4 is applied onto the surface of the second hollow particle-containing adhesive layer 10b, and the second release film 7 is further laminated thereon. The second adhesive layer 11b containing no hollow particles is formed.
另，較佳為，使第2含中空粒子之黏著劑層10b之塗佈厚度為50~100μm，第2不含中空粒子之黏著劑層11b之塗佈厚度為30~70μm，兩層全體之層厚為80~170μm。又，較佳使第1不含中空粒子之黏著劑層11a至第2不含中空粒子之黏著劑層11b的總厚度為200~300μm。 Further, it is preferable that the thickness of the second hollow particle-containing adhesive layer 10b is 50 to 100 μm, and the thickness of the second hollow particle-free adhesive layer 11b is 30 to 70 μm, and both layers are entirely The layer thickness is 80~170μm. Further, it is preferable that the total thickness of the first adhesive layer 11a containing no hollow particles to the second adhesive layer 11b containing no hollow particles is 200 to 300 μm.
然後，如圖6(B)所示，使第2含中空粒子之黏著劑層10b與第2不含中空粒子之黏著劑層11b硬化，藉此進行一體化，而形成第2黏著劑層5。作為硬化之方法，可藉由從第2剝離膜7上照射紫外線之方式等來進行。 Then, as shown in FIG. 6(B), the second adhesive layer 10b containing hollow particles and the second adhesive layer 11b containing no hollow particles are cured and integrated to form the second adhesive layer 5. . The method of curing can be carried out by irradiating ultraviolet rays from the second release film 7 or the like.
藉此，可使第2含中空粒子之黏著劑層10b及第2不含中空粒子之黏著劑層11b一體化，且可形成中空粒子4偏存於基材膜2之另一面2b側的第2黏著劑層5。 Thereby, the second hollow particle-containing adhesive layer 10b and the second hollow particle-free adhesive layer 11b can be integrated, and the hollow particles 4 can be formed on the other side 2b side of the base film 2 2 adhesive layer 5.
若根據藉由此種製法所製得之雙面黏著帶1，則將使用相同種類之黏著劑組成物的含中空粒子之黏著劑層10與不含中空粒子之黏著劑層11積層後，使兩層之黏著劑組成物同時硬化，藉此而形成第1、第2黏著劑層3、5。因此，雙面黏著帶1之含中空粒子之黏著劑層10與不含中空粒子之黏著劑層11的交聯反應在兩層中連續，藉此而一體化，貼合於被接 著物後，於含中空粒子之黏著劑層10與不含中空粒子之黏著劑層11的界面亦不會產生剝離，可提升剝離強度(凝聚破裂)。 According to the double-sided adhesive tape 1 obtained by the above-described production method, the adhesive layer 10 containing the hollow particles using the same type of adhesive composition is laminated with the adhesive layer 11 containing no hollow particles, thereby The two-layer adhesive composition is simultaneously hardened, whereby the first and second adhesive layers 3 and 5 are formed. Therefore, the crosslinking reaction of the hollow particle-containing adhesive layer 10 of the double-sided adhesive tape 1 and the adhesive layer 11 containing no hollow particles is continuous in the two layers, thereby integrating and bonding to the bonded After the object is formed, the interface between the adhesive layer 10 containing the hollow particles and the adhesive layer 11 containing no hollow particles is not peeled off, and the peel strength (agglomeration cracking) can be improved.
又，雙面黏著帶1藉由使中空粒子4偏存於基材膜2側，而可使中空粒子4不會露出於與被接著物接觸之第1黏著劑層3之表面，提升對被接著物之剝離強度(界面破裂)。 Moreover, the double-sided adhesive tape 1 can prevent the hollow particles 4 from being exposed on the surface of the first adhesive layer 3 which is in contact with the object to be adhered, so that the hollow particles 4 are not biased on the surface of the base film 2, Then the peel strength of the object (interface crack).
實施例 Example
[實施例之雙面黏著帶之製造] [Manufacture of double-sided adhesive tape of the embodiment]
接著，說明本發明之實施例。於本實施例，係使用藉由上述製法所製成之雙面黏著帶，於SUS板貼合SUS箔，測量剝離強度。 Next, an embodiment of the present invention will be described. In the present embodiment, the SUS foil was bonded to the SUS plate by using the double-sided adhesive tape produced by the above-described production method, and the peel strength was measured.
(漿液之製備) (Preparation of slurry)
於具有擋板裝置之聚合反應裝置，裝入丙烯酸2-乙基己酯90質量份與丙烯酸10質量份，並且添加2-羥基-2-甲基-1-苯丙烷-1-酮(Darocur 1173，BASF日本公司製)0.015質量份作為光聚合起始劑，進行攪拌，且同時使之反應，預聚合至反應混合物之黏度(JIS Z 8803：2011)成為1000mPa‧s(25℃)。 In a polymerization reactor having a baffle device, 90 parts by mass of 2-ethylhexyl acrylate was charged with 10 parts by mass of acrylic acid, and 2-hydroxy-2-methyl-1-phenylpropan-1-one (Darocur 1173) was added. 0.015 parts by mass of a photopolymerization initiator was stirred and simultaneously reacted, and the viscosity of the prepolymerized to the reaction mixture (JIS Z 8803:2011) was 1000 mPa ‧ (25 ° C).
(不含中空粒子之黏著劑組成物之製作) (Production of adhesive composition without hollow particles)
對前述漿液溶液80質量份，添加丙烯酸2-乙基己酯20質量份、作為光聚合起始劑之2-羥基-2-甲基-1-苯丙烷-1-酮(Darocur 1173，BASF日本公司製)0.3質量份、作為丙烯酸系交聯劑之羥基三甲基乙酸新戊二醇二丙烯酸酯(KAYARAD MANDA，日本化藥股份有限公司製)0.2質量份，均勻地加以混合，於室溫製備液狀之紫外線硬化性不含中空粒子之黏著劑組成物。 To 80 parts by mass of the slurry solution, 20 parts by mass of 2-ethylhexyl acrylate was added, and 2-hydroxy-2-methyl-1-phenylpropan-1-one as a photopolymerization initiator (Darocur 1173, BASF Japan) 0.2 parts by mass of hydroxytrimethylacetic acid neopentyl glycol diacrylate (KAYARAD MANDA, manufactured by Nippon Kayaku Co., Ltd.) as an acrylic crosslinking agent, and uniformly mixed at room temperature A liquid ultraviolet curable adhesive composition containing no hollow particles is prepared.
(含中空粒子之黏著劑組成物之製作) (Production of adhesive composition containing hollow particles)
對前述漿液溶液75質量份，添加丙烯酸2-乙基己酯25質量份、作為光聚合起始劑之2-羥基-2-甲基-1-苯丙烷-1-酮(Darocur 1173，BASF日本公司製)0.3質量份、作為丙烯酸系交聯劑之聚丙二醇二丙烯酸酯(Aronix M-270，東亞合成股份有限公司製)0.3質量份、丙烯腈樹脂中空粒子(Matsumoto Microsphere F-80SDE，松本油脂製藥股份有限公司製，平均粒徑20~40μm，真比重0.03)1.5質量份(約30體積%)，均勻地加以混合，於室溫製備液狀之紫外線硬化性含中空粒子之黏著劑組成物。 To 75 parts by mass of the above slurry solution, 25 parts by mass of 2-ethylhexyl acrylate was added, and 2-hydroxy-2-methyl-1-phenylpropan-1-one as a photopolymerization initiator (Darocur 1173, BASF Japan) 0.3 parts by mass of polypropylene glycol diacrylate (Aronix M-270, manufactured by Toagosei Co., Ltd.) as an acrylic crosslinking agent, 0.3 parts by mass of acrylonitrile resin hollow particles (Matsumoto Microsphere F-80SDE, Matsumoto Oil) Manufactured by Pharmaceutical Co., Ltd., having an average particle diameter of 20 to 40 μm, a true specific gravity of 0.03), 1.5 parts by mass (about 30% by volume), uniformly mixed, and preparing a liquid ultraviolet curable hollow particle-containing adhesive composition at room temperature .
接著，將表面經聚矽氧系離型劑處理過之厚度150μm之剝離襯墊捲出，塗佈不含中空粒子之黏著劑組成物使厚度成為0.05mm。以將含中空粒子之黏著劑組成物重疊於其上之方式，塗佈成以總厚度計為113μm，並進一步於其上積層25μm厚之PET膜(lumirror810，東麗股份有限公司製)作為基材。然後自PET膜側照射紫外線，得到於PET膜之一面形成有第1黏著劑層的膜積層體。 Next, a release liner having a thickness of 150 μm which had been treated with a polyfluorinated release agent on the surface was taken up, and an adhesive composition containing no hollow particles was applied to have a thickness of 0.05 mm. A PET film (lumirror 810, manufactured by Toray Industries, Inc.) having a total thickness of 113 μm and having a thickness of 25 μm was applied thereto as a base, in a manner of superimposing the adhesive composition containing the hollow particles thereon. material. Then, ultraviolet rays were irradiated from the PET film side to obtain a film laminate in which the first adhesive layer was formed on one surface of the PET film.
接著，將此膜積層體捲出，於PET膜之另一面塗佈含中空粒子之黏著劑組成物。於其上塗佈不含中空粒子之黏著劑組成物使厚度成為0.05mm，調整成以總厚度計為250μm，並進一步於其上積層表面經聚矽氧系離型劑進行過剝離處理之PET膜(lumirror810，東麗股份有限公司製)。然後自剝離PET膜側照射紫外線，得到於基材PET膜之一面形成有第1黏著劑層，於另一面形成有第2黏著劑層的雙面黏著帶。 Next, the film laminate was taken up, and an adhesive composition containing hollow particles was applied to the other side of the PET film. The adhesive composition containing no hollow particles was coated thereon to have a thickness of 0.05 mm, adjusted to a total thickness of 250 μm, and further subjected to a peeling treatment of the surface of the laminated layer by a polyfluorene-based release agent. Membrane (lumirror 810, manufactured by Toray Industries, Inc.). Then, ultraviolet rays were irradiated from the side of the peeled PET film to obtain a double-sided adhesive tape in which a first adhesive layer was formed on one surface of the base PET film and a second adhesive layer was formed on the other surface.
[比較例之雙面黏著帶之製造] [Manufacture of double-sided adhesive tape of comparative example]
於丙烯酸正丁酯35質量份、丙烯酸2-乙基己酯62質量份、丙烯酸3 質量份及甲基丙烯酸2-羥基乙酯0.1質量份之混合物中，添加作為起始劑之2,2'-偶氮雙異丁腈0.1質量份，然後藉由溶液聚合法使之聚合，而得到重量平均分子量為45萬之丙烯酸酯共聚物97質量份，將該重量平均分子量為45萬之丙烯酸酯共聚物97質量份與作為增黏樹脂之軟化點110℃的松酯3質量份混合而得之混合物以非揮發成分成為50%之方式溶解於甲苯、乙酸乙酯之混合溶劑，將所得者作為黏著劑。 35 parts by mass of n-butyl acrylate, 62 parts by mass of 2-ethylhexyl acrylate, acrylic acid 3 0.1 parts by mass of 2,2'-azobisisobutyronitrile as a starter is added to a mixture of 0.1 parts by mass of 2-hydroxyethyl methacrylate and then polymerized by solution polymerization. 97 parts by mass of an acrylate copolymer having a weight average molecular weight of 450,000 was obtained, and 97 parts by mass of the acrylate copolymer having a weight average molecular weight of 450,000 was mixed with 3 parts by mass of pine ester as a softening point of the tackifying resin at 110 ° C. The obtained mixture was dissolved in a mixed solvent of toluene and ethyl acetate so that the nonvolatile content was 50%, and the obtained one was used as an adhesive.
於上述黏著劑溶液，相對於黏著劑固形物成分100質量份(丙烯酸酯共聚物97質量份與松酯3質量份)，添加5質量份(約30體積%)作為中空粒子之由丙烯腈共聚物構成之松本油脂製藥股份有限公司製Matsumoto Microsphere MFL-SEVEN(平均粒徑20~40μm，真比重0.14，被覆碳酸鈣粉體)，加以攪拌分散。 In the above adhesive solution, 5 parts by mass (about 30% by volume) is added as a hollow particle to the acrylonitrile copolymer with respect to 100 parts by mass of the adhesive solid content component (97 parts by mass of the acrylate copolymer and 3 parts by mass of the pine ester). The Matsumoto Microsphere MFL-SEVEN (average particle diameter: 20 to 40 μm, true specific gravity: 0.14, coated calcium carbonate powder) manufactured by Matsumoto Oil & Fat Pharmaceutical Co., Ltd. was stirred and dispersed.
於上述黏著劑溶液添加0.8質量份作為異氰酸酯系交聯劑之日本聚氨酯工業股份有限公司製coronate L55E(非揮發成分55%溶液)，塗佈於剝離襯墊(厚度120μm，附聚矽氧系離型劑層之聚乙烯層積道林紙(woodfree paper))上，以105℃4分鐘之條件加以乾燥，設置厚度60μm之含有中空粒子之黏著劑層，層積積層於作為支持體之厚度25μm經實施雙面電暈處理之聚酯膜的兩側。 0.8 parts by mass of coronate L55E (non-volatile component 55% solution) manufactured by Nippon Polyurethane Co., Ltd. as an isocyanate-based crosslinking agent was added to the above-mentioned adhesive solution, and applied to a release liner (thickness 120 μm, agglomerated oxygen-free system) The polyethylene layer of the coating layer was dried on a wood free paper at 105 ° C for 4 minutes, and an adhesive layer containing hollow particles having a thickness of 60 μm was provided, and laminated to a thickness of 25 μm as a support. Both sides of the polyester film subjected to double-sided corona treatment.
並且，於丙烯酸正丁酯45質量份、丙烯酸2-乙基己酯50質量份、丙烯酸5質量份及甲基丙烯酸2-羥基乙酯0.1質量份之混合物中，添加作為起始劑之2,2'-偶氮雙異丁腈0.1質量份，然後藉由溶液聚合法使之聚合，而得到重量平均分子量為43萬之丙烯酸酯共聚物90質量份，將該重量平均分子量為43萬之丙烯酸酯共聚物90質量份與作為增黏樹脂之軟化 點110℃的松酯10質量份混合而得之混合物以非揮發成分成為55%之方式溶解於甲苯、乙酸乙酯之混合溶劑，將所得者作為不含中空粒子之黏著劑。 Further, in a mixture of 45 parts by mass of n-butyl acrylate, 50 parts by mass of 2-ethylhexyl acrylate, 5 parts by mass of acrylic acid, and 0.1 part by mass of 2-hydroxyethyl methacrylate, 2 is added as a starter. 0.1 parts by mass of 2'-azobisisobutyronitrile, and then polymerized by solution polymerization to obtain 90 parts by mass of an acrylate copolymer having a weight average molecular weight of 430,000, and the acrylic acid having a weight average molecular weight of 430,000 90 parts by mass of ester copolymer and softening as a tackifying resin The mixture obtained by mixing 10 parts by mass of the terpene ester at 110 ° C was dissolved in a mixed solvent of toluene and ethyl acetate so that the nonvolatile content was 55%, and the obtained product was used as an adhesive containing no hollow particles.
於上述不含中空粒子之黏著劑溶液，添加1.9質量份作為異氰酸酯系交聯劑之日本聚氨酯工業股份有限公司製coronate L55E(非揮發成分55%溶液)，塗佈於剝離襯墊(厚度120μm，附聚矽氧系離型劑層之聚乙烯層積道林紙)上，以105℃4分鐘之條件加以乾燥，設置厚度30μm之不含中空粒子之黏著劑層，積層層積於上述含有中空粒子之黏著劑層雙面的更上部，而得到雙面黏著帶。 To the above-mentioned adhesive solution containing no hollow particles, 1.9 parts by mass of coronate L55E (non-volatile component 55% solution) manufactured by Nippon Polyurethane Co., Ltd. as an isocyanate crosslinking agent was added and applied to a release liner (thickness: 120 μm, The polyethylene layered forest paper of the agglomerated oxime release layer was dried at 105 ° C for 4 minutes, and an adhesive layer containing no hollow particles having a thickness of 30 μm was provided, and the laminate was laminated to the above hollow. The adhesive layer of the particles is further on both sides of the double layer to obtain a double-sided adhesive tape.
[黏著帶之特性評價] [Feature evaluation of adhesive tape]
將實施例及比較例之雙面黏著帶切成寬度20mm、長度80mm，將單面之剝離膜剝除，以粒度280號之研磨紙加以研磨後，貼合於經以甲苯擦拭過表面之SUS304板。於其上重疊厚度50μm之SUS箔基材，來回壓接2kg重之滾筒。將其接合體樣品於23℃放置1小時後，以拉伸試驗機對接著力進行了測量(90°揭膜(peel)，拉伸速度：300mm/min)。 The double-sided adhesive tapes of the examples and the comparative examples were cut into a width of 20 mm and a length of 80 mm, and the peeling film of one side was peeled off, and the paper was ground with a grinding paper of a size of 280, and bonded to SUS304 which was wiped with toluene. board. A SUS foil substrate having a thickness of 50 μm was superposed thereon, and a 2 kg heavy roller was crimped back and forth. After the bonded body sample was allowed to stand at 23 ° C for 1 hour, the adhesion was measured by a tensile tester (90° peel, tensile speed: 300 mm/min).
如表1所示，於實施例之接合體樣品，90°剝離強度為22N/20mm，相對於此，於比較例之接合體樣品，則為15N/20mm。其原因在於：於實施例之雙面黏著帶，分別積層使用相同種類之黏著劑組成物的含中空粒子之黏著劑層與不含中空粒子之黏著劑層作為第1、第2黏著劑層， 使兩層之黏著劑組成物同時硬化。因此，實施例之雙面黏著帶的含中空粒子之黏著劑層與不含中空粒子之黏著劑層一體化，於貼合在被接著物後，亦不會在含中空粒子之黏著劑層與不含中空粒子之黏著劑層的界面產生剝離，不會發生凝聚破裂。 As shown in Table 1, the 90° peel strength of the bonded body sample of the example was 22 N/20 mm, whereas the bonded body sample of the comparative example was 15 N/20 mm. The reason for this is that, in the double-sided adhesive tape of the embodiment, the adhesive layer containing hollow particles of the same type of adhesive composition and the adhesive layer containing no hollow particles are laminated as the first and second adhesive layers, respectively. The two layers of the adhesive composition are simultaneously hardened. Therefore, the adhesive layer containing the hollow particles of the double-sided adhesive tape of the embodiment is integrated with the adhesive layer containing no hollow particles, and is not bonded to the adhesive layer containing the hollow particles after being bonded to the adherend. The interface of the adhesive layer containing no hollow particles is peeled off, and aggregation cracking does not occur.
又，實施例之雙面黏著帶藉由使中空粒子偏存於成為基材之PET膜側，而可使中空粒子不會露出於與成為被接著物之SUS板及SUS箔接觸之第1、第2黏著劑層的表面，提升對被接著物之剝離強度(界面破裂)。因此，實施例之雙面黏著帶，於摻合多達30體積%之中空粒子的情形時，亦不會導致剝離強度下降，可實現牢固之接著力。 Further, in the double-sided adhesive tape of the example, the hollow particles are prevented from being exposed to the SUS plate and the SUS foil which are the substrates to be exposed, by displacing the hollow particles on the PET film side of the substrate. The surface of the second adhesive layer enhances the peel strength (interface crack) of the adherend. Therefore, in the case where the double-sided adhesive tape of the embodiment is blended with up to 30% by volume of the hollow particles, the peel strength is not lowered, and a firm adhesive force can be achieved.
另一方面，於比較例之雙面黏著帶，係於塗佈含有中空粒子之黏著劑組成物後，以105℃4分鐘之條件使之乾燥，形成含有中空粒子之黏著劑層，同樣地，於塗佈不含中空粒子之黏著劑組成物後，以105℃4分鐘之條件使之乾燥，形成不含中空粒子之黏著劑層，然後，對兩層進行層積。因此，含有中空粒子之黏著劑層與不含中空粒子之黏著劑層並無一體化，相較於實施例，剝離強度較差。又，若觀察經剝離之界面，則於含有中空粒子之黏著劑層與不含中空粒子之黏著劑層的界面，亦處處可見發生凝聚破裂之部位，可知黏著劑之凝聚力低。 On the other hand, in the double-sided adhesive tape of the comparative example, after applying the adhesive composition containing hollow particles, it was dried at 105 ° C for 4 minutes to form an adhesive layer containing hollow particles, and similarly, After coating the adhesive composition containing no hollow particles, it was dried at 105 ° C for 4 minutes to form an adhesive layer containing no hollow particles, and then the two layers were laminated. Therefore, the adhesive layer containing the hollow particles is not integrated with the adhesive layer containing no hollow particles, and the peel strength is inferior compared to the examples. Further, when the peeled interface was observed, the interface where the aggregation layer was formed at the interface between the adhesive layer containing the hollow particles and the adhesive layer containing no hollow particles was observed, and the cohesive force of the adhesive was low.
1‧‧‧雙面黏著帶 1‧‧‧Double adhesive tape
2‧‧‧基材膜 2‧‧‧Base film
2a‧‧‧一面 2a‧‧‧ side
2b‧‧‧另一面 2b‧‧‧The other side
3‧‧‧第1黏著劑層 3‧‧‧1st adhesive layer
4‧‧‧中空粒子 4‧‧‧ hollow particles
5‧‧‧第2黏著劑層 5‧‧‧2nd adhesive layer
6‧‧‧第1剝離膜 6‧‧‧1st release film
7‧‧‧第2剝離膜 7‧‧‧2nd release film
Claims (14)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2015061606 | 2015-03-24 | ||
| JPJP2015-061606 | 2015-03-24 |
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| TW201708460A true TW201708460A (en) | 2017-03-01 |
| TWI765849B TWI765849B (en) | 2022-06-01 |
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| TW105108802A TWI765849B (en) | 2015-03-24 | 2016-03-22 | Double-sided adhesive tape and method of making the same |
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|---|---|
| JP (1) | JP6801202B2 (en) |
| KR (1) | KR102156002B1 (en) |
| CN (1) | CN107709491A (en) |
| TW (1) | TWI765849B (en) |
| WO (1) | WO2016152787A1 (en) |
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| JP6674662B2 (en) * | 2016-09-30 | 2020-04-01 | ブラザー工業株式会社 | Adhesive tape cartridge |
| JP6729258B2 (en) | 2016-09-30 | 2020-07-22 | ブラザー工業株式会社 | Adhesive tape cartridge and adhesive tape roll manufacturing method |
| CN110461978B (en) * | 2017-03-31 | 2022-04-19 | 琳得科株式会社 | Adhesive sheet |
| CN108504296A (en) * | 2018-04-04 | 2018-09-07 | 宁国市千洪电子有限公司 | A kind of double faced adhesive tape and preparation method thereof for touch screen |
| US20220112403A1 (en) * | 2019-01-22 | 2022-04-14 | Sekisui Chemical Co., Ltd. | Adhesive tape and method for producing same |
| JP2021024907A (en) * | 2019-08-01 | 2021-02-22 | 日東電工株式会社 | Double-sided adhesive tape |
| KR102317843B1 (en) * | 2019-12-26 | 2021-10-26 | 주식회사 지오니어 | Tape for adhesiving battery of mobile terminal and method for manufacturing the same |
| WO2024095322A1 (en) * | 2022-10-31 | 2024-05-10 | 株式会社寺岡製作所 | Adhesive composition, adhesive sheet formed of said adhesive composition, and article using said adhesive sheet |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08259908A (en) * | 1995-03-20 | 1996-10-08 | Sekisui Chem Co Ltd | Double-side pressure-sensitive adhesive tape, laminate of double-side pressure-sensitive adhesive tape and production of double-side pressure-sensitive adhesive type |
| WO2009031421A1 (en) * | 2007-09-07 | 2009-03-12 | Dic Corporation | Double-sided adhesive tape |
| JP4623198B2 (en) | 2007-10-12 | 2011-02-02 | Ｄｉｃ株式会社 | Double-sided adhesive tape for waterproofing |
| JP5227658B2 (en) * | 2008-05-23 | 2013-07-03 | ニチバン株式会社 | Photopolymer layer with substrate and method for producing the same |
| KR101188769B1 (en) * | 2010-07-07 | 2012-10-10 | 국방과학연구소 | A Method for Improving Bonding Property Between Rubber and Epoxy-Composite |
| JP2012229358A (en) * | 2011-04-27 | 2012-11-22 | Nitto Denko Corp | Adhesive sheet |
| JP2013249367A (en) * | 2012-05-31 | 2013-12-12 | Hitachi Kasei Polymer Co Ltd | Double-sided pressure-sensitive adhesive tape |
| KR101510719B1 (en) * | 2013-05-29 | 2015-04-10 | (주)티엠에스 | Readhesive multi-layered double-sided tape and manufacturing method thererof |
-
2016
- 2016-03-18 WO PCT/JP2016/058722 patent/WO2016152787A1/en active Application Filing
- 2016-03-18 KR KR1020177018823A patent/KR102156002B1/en active IP Right Grant
- 2016-03-18 CN CN201680014114.9A patent/CN107709491A/en active Pending
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| Publication number | Publication date |
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| CN107709491A (en) | 2018-02-16 |
| JP2016180099A (en) | 2016-10-13 |
| KR20170094320A (en) | 2017-08-17 |
| KR102156002B1 (en) | 2020-09-15 |
| JP6801202B2 (en) | 2020-12-16 |
| TWI765849B (en) | 2022-06-01 |
| WO2016152787A1 (en) | 2016-09-29 |
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