TWI437069B - Substrate mask - Google Patents

Substrate mask Download PDF

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Publication number
TWI437069B
TWI437069B TW096105885A TW96105885A TWI437069B TW I437069 B TWI437069 B TW I437069B TW 096105885 A TW096105885 A TW 096105885A TW 96105885 A TW96105885 A TW 96105885A TW I437069 B TWI437069 B TW I437069B
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TW
Taiwan
Prior art keywords
substrate
acid
group
film
weight
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TW096105885A
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Chinese (zh)
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TW200740949A (en
Inventor
Mitsushi Yamamoto
Kazuhito Okumura
Mikio Masuichi
Masafumi Kawagoe
Tsuyoshi Matsuka
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Nitto Denko Corp
Dainippon Screen Mfg
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Publication of TW200740949A publication Critical patent/TW200740949A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B12/00—Arrangements for controlling delivery; Arrangements for controlling the spray area
    • B05B12/16—Arrangements for controlling delivery; Arrangements for controlling the spray area for controlling the spray area
    • B05B12/20—Masking elements, i.e. elements defining uncoated areas on an object to be coated
    • B05B12/24—Masking elements, i.e. elements defining uncoated areas on an object to be coated made at least partly of flexible material, e.g. sheets of paper or fabric
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/13—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing
    • H10K71/135—Deposition of organic active material using liquid deposition, e.g. spin coating using printing techniques, e.g. ink-jet printing or screen printing using ink-jet printing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/60—Forming conductive regions or layers, e.g. electrodes
    • H10K71/611—Forming conductive regions or layers, e.g. electrodes using printing deposition, e.g. ink jet printing

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  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Adhesive Tapes (AREA)
  • Details Or Accessories Of Spraying Plant Or Apparatus (AREA)
  • Coating Apparatus (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Electroluminescent Light Sources (AREA)
  • Laminated Bodies (AREA)

Description

基板用遮罩帶Substrate mask

本發明係關於基板用遮罩帶，更詳細言之，係關於在有機電致發光(EL，即electroluminescence)用基板、液晶用基板、有機薄膜太陽電池用基板、電漿顯示器用基板、半導體晶圓、光碟用基板等各種基板上塗布有機電致發光材料、導電性材料、光阻劑等流動性材料而形成薄膜時所使用的基板用遮罩帶。The present invention relates to a mask for a substrate, and more particularly to a substrate for an organic electroluminescence (EL), a substrate for a liquid crystal, a substrate for an organic thin film solar cell, a substrate for a plasma display, and a semiconductor crystal. A mask tape for a substrate used for forming a film by applying a fluid material such as an organic electroluminescent material, a conductive material, or a photoresist to various substrates such as a disk or a substrate for a disk.

有機電致發光顯示器(OELD)，係因藉由自發光所得之高亮度、廣視角、高回應速度等，而使辨識度優良、薄型、輕量、低耗電率、低成本成為可能，故被視為最具期望的次世代顯示器。有機電致發光顯示器，一般而言，具有在玻璃基板上依序積層陽極(透明電極)、電洞傳輸層(HTL，即Hole Transport Layer)、發光層(EML，即Emitting Material Layer)、電子傳輸層(Electron Transport Lyaer)、及陰極而成的構造，各層的形成係適用薄膜形成技術，以相關之薄膜技術而言，例如已知有噴墨印刷法。The organic electroluminescent display (OELD) is characterized by excellent brightness, thinness, light weight, low power consumption, and low cost due to high brightness, wide viewing angle, and high response speed obtained by self-illumination. It is considered the most desirable next generation display. An organic electroluminescent display generally has an anode (transparent electrode), a hole transport layer (HTL), an embedding layer (EML), and an electron transport layer sequentially stacked on a glass substrate. The structure of the layer (Electron Transport Lyaer) and the cathode, and the formation of each layer is a film forming technique. For the related film technology, for example, an inkjet printing method is known.

噴墨印刷法，係例如將含有發光聚合物(R、G、B)之塗布液從噴嘴藉由ON/OFF而自由噴出，並在基板上依各個像素(pixel)分開塗布的方法，但液滴尺寸容易不規則變化，且可使用之塗布液的固體成分比或黏度有限制，更有液滴本身會中斷等問題存在。此外，容易因噴嘴尖端乾燥而引起堵塞，在維修性上亦有問題。In the inkjet printing method, for example, a coating liquid containing a light-emitting polymer (R, G, B) is freely ejected from a nozzle by ON/OFF, and is applied separately on each substrate by a pixel, but the liquid is applied. The droplet size is easily changed irregularly, and the solid content ratio or viscosity of the coating liquid which can be used is limited, and there are problems such as interruption of the droplet itself. In addition, it is easy to cause clogging due to drying of the nozzle tip, and there is also a problem in maintainability.

因此，近年來，從噴嘴連續將塗布液噴出而形成薄膜的噴嘴塗布法受到注目。噴嘴塗布法(nozzle coating method)，係將充填於瓶中的塗布液以分段式泵(Section pump)吸起並過濾後，送往噴出噴嘴，從噴嘴形成液柱並連續噴出至基板上，因此沒有噴墨印刷法中之上述問題，而有可不斷噴出幾乎相同流量之塗布液的優點(日本特開2004－89771號公報)。Therefore, in recent years, a nozzle coating method in which a coating liquid is continuously ejected from a nozzle to form a film has been attracting attention. The nozzle coating method is a method in which a coating liquid filled in a bottle is sucked up by a section pump and filtered, and then sent to a discharge nozzle to form a liquid column from the nozzle and continuously ejected onto the substrate. Therefore, there is no such problem as in the ink jet printing method, and there is an advantage that the coating liquid of almost the same flow rate can be continuously ejected (JP-A-2004-89771).

然而，在將塗布液連續性地以噴嘴塗布於基板上的方法中，因塗布液之噴出控制的回應性不高，以ON/OFF控制塗布液的噴出係困難。所以，由於在基板上使噴嘴掃描的期間難以用ON/OFF控制塗布液的噴出，故無法在掃描中僅選擇有必要塗布之區域以塗布塗布液。因此，在進行噴嘴塗布時，係將塗布液亦塗布於基板上不需塗布之區域後，必須要除去塗布於不需塗布之區域上的塗布液。例如，在基板的四個角落的末端部分即成為不需塗布的區域。在進行噴嘴塗布時，以從不需塗布區域除去塗布液的方法而言，有將不需塗布的區域藉由遮罩帶或遮罩材料而遮罩的方法。此外，以噴嘴塗布法，從一張基板製作複數張顯示用面板時，因相鄰的顯示用面板與顯示用面板之間亦會噴出塗布液，故無法將相鄰之顯示用面板間分開塗布。However, in the method of continuously applying a coating liquid onto a substrate by a nozzle, the responsiveness of the discharge control of the coating liquid is not high, and it is difficult to control the discharge of the coating liquid by ON/OFF. Therefore, since it is difficult to control the discharge of the coating liquid by ON/OFF during the scanning of the nozzle on the substrate, it is not possible to select only the region to be coated in the scanning to apply the coating liquid. Therefore, when the nozzle coating is performed, the coating liquid is also applied to the region on the substrate where the coating is not required, and the coating liquid applied to the region not to be coated must be removed. For example, the end portions of the four corners of the substrate become areas that do not need to be coated. In the case of performing nozzle coating, a method of removing a coating liquid from a region where no coating is required is a method of masking a region where no coating is required by a mask tape or a masking material. Further, when a plurality of display panels are produced from one substrate by the nozzle coating method, since the coating liquid is also ejected between the adjacent display panel and the display panel, the adjacent display panels cannot be separately coated. .

本發明者等，藉由噴嘴塗布法將流動性材料噴出到玻璃基板，在不需塗布之區域上貼附以往公知的遮罩帶，以相鄰之顯示用面板間不會被塗布液塗布之方式，作為對策而進行塗布時，遭遇到個別的顯示用面板內(應形成薄膜之區域)藉由塗布液所形成之薄膜的厚度，在遮罩帶的側部(側面附近)因塗布形狀之非期望性擴大而導致變厚的問題。當發生此等因流動性材料的塗布形狀非期望性的擴大而導致薄膜非期望性的厚度增加時，之後，例如在顯示面板內(應形成薄膜之區域)的兩端蒸鍍陰極用材料時，會有陰極在藉上述流動性材料所成之薄膜之塗布形狀非期望性擴大的部份上斷線，或無法藉由蒸鍍所形成之陰極而遮蔽來自外部的水分或氧氣等不良狀況之虞。The inventors of the present invention sprayed a fluid material onto a glass substrate by a nozzle coating method, and attached a conventionally known mask tape to a region where no coating is required, so that the adjacent display panels are not coated with the coating liquid. In the case of coating as a countermeasure, the thickness of the film formed by the coating liquid in the individual display panel (the area where the film should be formed) is encountered, and the coating is formed on the side portion (near the side surface) of the mask tape. Unexpected expansion leads to thickening problems. When such an increase in undesired thickness of the film due to an undesired expansion of the coating shape of the fluid material occurs, for example, when the cathode material is vapor-deposited at both ends of the display panel (the region where the film should be formed) The cathode may be broken at a portion where the coating shape of the film formed by the fluid material is undesirably expanded, or the cathode formed by vapor deposition may be shielded from moisture or oxygen from the outside. Hey.

有鑑於上述問題，本發明欲解決的課題，係提供一種遮罩帶，其係在將基板上不需塗布區域用遮罩帶遮罩後塗布由流動性材料所構成之塗布液而形成薄膜時，可防止遮罩帶周圍之薄膜(塗膜)產生非期望性的厚度增加。In view of the above problems, the problem to be solved by the present invention is to provide a mask tape which is formed by coating a coating liquid composed of a fluid material on a substrate without applying a masking region to a coating film. It can prevent an undesired increase in thickness of the film (coating film) around the mask tape.

本發明者等，為了解決上述的課題，在調查使用以往公知之遮罩帶時，於遮罩帶周圍之由流動性材料所構成之薄膜(塗膜)會產生非期望性厚度增加的原因時，得知若以噴嘴塗布法噴出流動性材料而形成薄膜，則會產生以下的現象。In order to solve the above problems, the inventors of the present invention have investigated the use of a conventionally known mask tape, and when a film (coating film) composed of a fluid material around the mask tape causes an undesired increase in thickness, It has been found that when a fluid material is ejected by a nozzle coating method to form a film, the following phenomenon occurs.

[1]附著於遮罩帶側面的流動性材料會形成彎月面(meniscus)。[1] The fluid material attached to the side of the mask strip forms a meniscus.

[2]經塗布於遮罩帶背面的流動性材料會脫落至遮罩帶側部的薄膜形成面。[2] The fluid material applied to the back surface of the mask tape may fall off to the film forming surface on the side of the mask tape.

因此，本發明者等，根據此等認知，從改善遮罩帶與薄膜形成材料(流動性材料)之間之濕潤性的觀點而進行研究，結果發現在遮罩帶背面(基材之黏著層非形成面)及遮罩帶側面(黏著層之側面)之水的接觸角分別為特定範圍時，則上述[1]會被抑制，且上述[2]會被消除，而可抑制遮罩帶周圍之藉流動性材料所成之薄膜(塗膜)的非期望性的厚度增加，得以完成本發明。Therefore, the present inventors have studied from the viewpoint of improving the wettability between the mask tape and the film forming material (flowable material) based on such knowledge, and found that the back surface of the mask tape (adhesive layer of the substrate) When the contact angle of the water on the side of the mask (the side of the adhesive layer) is a specific range, the above [1] is suppressed, and the above [2] is eliminated, and the mask strip can be suppressed. The present invention has been completed by increasing the undesired thickness of a film (coating film) formed by a fluid material.

亦即，本發明係有關：(1)一種基板用遮罩帶，其係於基材之一方之面具有黏著層的基板用遮罩帶，其中，在基材之另一方之面之水的接觸角為未達65°，黏著層之側面之水的接觸角為未達100°；(2)如上述(1)記載之遮罩帶，其中，黏著層之被黏面具有隔離膜(separator)；(3)如上述(1)或(2)記載之遮罩帶，其中，基材包括聚酯系薄膜；(4)如上述(1)至(3)中任一項記載之遮罩帶，其中，基材之另一方之面具有表面處理層；(5)如上述(1)至(4)中任一項記載之遮罩帶，其中，黏著層之側面具有表面處理層；(6)如上述(5)記載之遮罩帶，其中，表面處理層係經塗布光觸媒者；(7)如上述(1)至(6)中任一項記載之遮罩帶，其中，基板係玻璃基板；(8)如上述(1)至(7)中任一項記載之遮罩帶，其中，基板係有機電致發光用基板；(9)如上述(1)至(8)中任一項記載之遮罩帶，其係使用於藉由從噴嘴往基板塗布流動性材料之塗布法而形成薄膜時。That is, the present invention relates to: (1) a mask tape for a substrate, which is a mask tape for a substrate having an adhesive layer on one side of a substrate, wherein water on the other side of the substrate The contact angle is less than 65°, and the contact angle of the water on the side of the adhesive layer is less than 100°; (2) The mask tape according to the above (1), wherein the adhesive layer has a separator (separator) (3) The mask tape according to the above (1) or (2), wherein the substrate comprises a polyester film; (4) the mask according to any one of the above (1) to (3) And a masking tape according to any one of the above (1) to (4), wherein the side surface of the adhesive layer has a surface treatment layer; (6) The masking tape according to any one of (1) to (6), wherein the masking tape according to any one of the above (1) to (6), wherein (6) The mask tape according to any one of (1) to (7), wherein the substrate is a substrate for organic electroluminescence; (9) as in the above (1) to (8) a recorded mask strip that is used by Nozzle to substrate coating method of coating a fluid material while a thin film is formed.

在本發明中，所謂「流動性材料」，係意指可藉由噴嘴連續塗布在基板上而形成薄膜的材料，係液體、半液體、糊狀物、熔融物、溶液、分散液、懸濁液等型態之材料。In the present invention, the term "fluid material" means a material which can be continuously coated on a substrate by a nozzle to form a film, which is a liquid, a semi-liquid, a paste, a melt, a solution, a dispersion, and a suspension. Liquid type material.

本發明之基板用遮罩帶，由於其背面(基材之黏著層非形成面)及黏著層側面之水的接觸角分別成為特定範圍，表現特定之濕潤性，故在將其貼附於基板上的不需塗布區域(不應形成薄膜之區域)，塗布流動性材料而形成薄膜時，在遮罩帶側部(側面附近)形成之流動性材料的彎月面高度會變低，此外，會抑制塗布於遮罩帶背面的流動性材料往遮罩帶側部的脫落，使薄膜在基板上(非遮罩區域)不會產生非期望性的厚度增加而可安定地形成。所以，例如，將本發明之基板用遮罩帶貼附於有機電致發光用基板，在該基板上，劃分出複數個應形成薄膜的區域(顯示面板區域)，以噴嘴塗布法依序進行會成為各機能層之薄膜的形成，即使是在從一張基板製造複數張顯示面板(有機電致發光顯示器)時，亦可確實防止因陰極斷線所造成的導電不良、或是在陰極對來自外部之水分或氧氣的遮蔽不良等不佳狀態的發生，結果，可使生產效率提高，大幅縮減生產成本。In the mask for a substrate of the present invention, since the contact angles of the back surface (the non-formed surface of the adhesive layer of the substrate) and the water on the side surface of the adhesive layer are in a specific range, and the specific wettability is exhibited, the substrate is attached to the substrate. The coating area (the area where the film should not be formed) is not required, and when the fluid material is applied to form a film, the height of the meniscus of the fluid material formed on the side of the mask (near the side) becomes lower, and The detachment of the fluid material applied to the back surface of the mask tape to the side portion of the mask tape is suppressed, so that the film can be stably formed without causing an undesired increase in thickness on the substrate (non-mask region). Therefore, for example, the substrate mask tape of the present invention is attached to the substrate for organic electroluminescence, and a plurality of regions (display panel regions) on which the film is to be formed are divided on the substrate, and sequentially performed by nozzle coating method. It will form a film of each functional layer, and even when a plurality of display panels (organic electroluminescence displays) are manufactured from one substrate, it is possible to surely prevent conduction defects caused by cathode breakage, or at the cathode pair. The occurrence of poor conditions such as poor shielding of moisture or oxygen from the outside can result in an increase in production efficiency and a significant reduction in production costs.

以下，將本發明依照其適當之實施型態而加以詳細說明。另外，在圖式的說明中，於同樣的要素附加同樣的符號，省略重複的說明。此外，在圖式的方便上，圖式的尺寸比率與說明之物品並非一定相同。Hereinafter, the present invention will be described in detail in accordance with suitable embodiments thereof. In the description of the drawings, the same reference numerals will be given to the same elements, and overlapping description will be omitted. Moreover, in the convenience of the drawings, the dimensional ratio of the drawings is not necessarily the same as the illustrated articles.

(第1實施型態)(first embodiment)

第1圖，係有關第1實施型態之基板用遮罩帶的斜視圖，第2圖(a)係有關第1實施形態之基板用遮罩帶之沿著I至I線而截取的剖面圖。Fig. 1 is a perspective view of a mask tape for a substrate according to a first embodiment, and Fig. 2(a) is a cross section taken along line I to I of the mask tape for a substrate of the first embodiment. Figure.

本發明之基板用遮罩帶，如該第1實施型態相關之基板用遮罩帶10所示，係具備基材1與形成於該基材1之一方之面的黏著層3者。黏著層3本身具有黏著性，由下述之黏著劑所構成。然後，基材1之另一方之面A(亦即該遮罩帶10之背面)之水的接觸角係未達65°，並且，黏著層側面B之水的接觸角係未達100°。The mask tape for a substrate of the present invention is provided with the substrate 1 and the adhesive layer 3 formed on one surface of the substrate 1 as shown in the mask tape 10 for a substrate according to the first embodiment. The adhesive layer 3 itself has adhesiveness and is composed of the following adhesive. Then, the contact angle of the water of the other side A of the substrate 1 (i.e., the back side of the mask tape 10) is less than 65°, and the contact angle of the water of the side B of the adhesive layer is less than 100°.

以下，詳細說明基板用遮罩帶的各構成要素，但基板用遮罩帶僅稱為遮罩帶。Hereinafter, each component of the mask tape for a substrate will be described in detail, but the mask tape for the substrate is simply referred to as a mask tape.

(基材)以基材1而言，只要是基材之另一方之面之水的接觸角為未達65°(宜為未達60°，更宜為未達50°)者即可無特別限制地使用。若接觸角為65°以上，則在形成薄膜時，遮罩帶背面中的濕潤性會變得不足，流動性材料會變得容易從遮罩帶背面脫落，而當流動性材料脫落至遮罩帶側部時，會成為薄膜非期望性厚度增加的原因。此外，亦會成為顆粒(particle)、飛濺(splatter)、污染(contamination)等污染的原因。(Substrate) In the case of the substrate 1, as long as the contact angle of the water on the other side of the substrate is less than 65° (preferably less than 60°, more preferably less than 50°) Use it with special restrictions. When the contact angle is 65° or more, when the film is formed, the wettability in the back surface of the mask tape becomes insufficient, and the fluid material becomes easy to fall off from the back surface of the mask tape, and when the fluid material falls off to the mask. When the side portion is provided, it causes a decrease in the undesired thickness of the film. In addition, it may also be a cause of contamination such as particles, splatters, and contamination.

另外，基材之另一方之面之水的接觸角下限雖未特別限制，但宜為5°以上，較宜為10°以上。Further, the lower limit of the contact angle of the water on the other side of the substrate is not particularly limited, but is preferably 5 or more, and more preferably 10 or more.

在本說明書中，所謂「水的接觸角」，係指以裝有內徑0.4mm不鏽鋼製針的玻璃製注射器將3μg的蒸餾水附著於被驗面，於附著後20秒內，在23℃×50%RH下使用接觸角計(商品名：CA－X型，協和界面科學股份公司製)依據θ/2法測定所得者。然後，在本發明中，選擇並使用如上述測定水的接觸角時為未達65°之基材。In the present specification, the term "contact angle of water" means that 3 μg of distilled water is adhered to the surface to be inspected by a glass syringe equipped with a stainless steel needle having an inner diameter of 0.4 mm, and within 23 seconds after attachment, at 23 ° C × A 50% RH was measured using a contact angle meter (trade name: CA-X type, manufactured by Kyowa Interface Science Co., Ltd.) according to the θ/2 method. Then, in the present invention, a substrate having a contact angle of water of not more than 65° as described above is selected and used.

以基材而言，適合使用例如塑膠膜，具體而言，可列舉如：聚乙烯、聚丙烯等聚烯烴系薄膜；聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯等聚酯系薄膜；尼龍等聚醯胺系薄膜；三乙酸纖維素薄膜；聚醯亞胺薄膜等。其中，從耐溶劑性、耐水性等觀點而言，宜使用聚酯系薄膜。聚酯系薄膜，係會特別容易得到水的接觸角在上述範圍者。此外，從耐熱性觀點而言，宜使用聚醯亞胺薄膜。亦即，當基材使用聚醯亞胺薄膜時，例如可在使遮罩帶維持著貼附於基板的狀態之下，將基板以例如250℃左右的溫度進行熱處理(烘烤)，故為較佳。另外，此等塑膠薄膜，可為無延伸薄膜及延伸(單軸延伸或雙軸延伸)薄膜中之任一者。此外，此等塑膠薄膜，雖然可直接使用沒有經過特殊的表面處理而因素材(塑膠)的特性使薄膜表面之水的接觸角會未達65°者，但並非如此者，則將成為基材之另一方之面的薄膜面進行親水化的表面處理(設置表面處理層)，使表面之水的接觸角變成未達65°。此外，即使是因素材(塑膠)的特性而使薄膜表面之水的接觸角未達65°者，亦可進行表面處理，使水的接觸角變得更小。就相關之用以親水化的表面處理而言，可列舉如抗靜電處理、電漿處理、電暈處理、易接著處理等。For the substrate, for example, a plastic film is suitably used, and specific examples thereof include a polyolefin film such as polyethylene or polypropylene; and polyethylene terephthalate or polybutylene terephthalate. Ester-based film; polyamine film such as nylon; cellulose triacetate film; polyimine film. Among them, a polyester film is preferably used from the viewpoints of solvent resistance, water resistance, and the like. In the polyester film, it is particularly easy to obtain a contact angle of water in the above range. Further, from the viewpoint of heat resistance, a polyimide film is preferably used. In other words, when the polyimide film is used as the substrate, for example, the substrate can be heat-treated (baked) at a temperature of, for example, about 250 ° C while the mask tape is attached to the substrate. Preferably. In addition, the plastic film may be any of an unstretched film and an extended (uniaxially stretched or biaxially stretched) film. In addition, although these plastic films can be directly used without special surface treatment and the characteristics of the material (plastic) make the contact angle of water on the surface of the film less than 65°, otherwise it will become the substrate. On the other side, the film surface was subjected to a hydrophilization surface treatment (a surface treatment layer was provided) so that the contact angle of water on the surface became less than 65°. Further, even if the contact angle of the water on the surface of the film is less than 65° due to the characteristics of the material (plastic), the surface treatment can be performed to make the contact angle of water smaller. Examples of the surface treatment for hydrophilization include antistatic treatment, plasma treatment, corona treatment, easy adhesion treatment, and the like.

上述之抗靜電處理、電暈處理及易接著處理，可適用於該技術領域中之周知的方法，但以抗靜電處理而言，可列舉出例如將使用聚乙烯基醇、聚酯、丙烯酸系聚合物、聚胺基甲酸酯(polyurethane)等作為黏合劑而成的界面活性劑進行塗布之處理；蒸鍍金屬氧化物或ITO(錫摻雜氧化銦)等而進行金屬氧化物薄膜之形成處理等。以易接著處理而言，可列舉出例如塗布聚乙烯基醇、聚酯、丙烯酸系聚合物、聚胺基甲酸酯等而進行處理。The antistatic treatment, the corona treatment, and the easy-to-treat treatment described above can be applied to a well-known method in the technical field, but examples of the antistatic treatment include polyvinyl alcohol, polyester, and acrylic. Coating with a surfactant such as a polymer or a polyurethane as a binder; forming a metal oxide film by vapor-depositing a metal oxide or ITO (tin-doped indium oxide) Processing and so on. The easy-to-treat treatment may be carried out by, for example, coating a polyvinyl alcohol, a polyester, an acrylic polymer, a polyurethane, or the like.

另外，以具有水的接觸角為未達65°之面的基材而言，商業上可取得例如T100N38、T100C38(以上為商品名，三菱化學聚酯股份公司製)。In addition, a substrate having a contact angle of water of less than 65° is commercially available, for example, T100N38 or T100C38 (trade name, manufactured by Mitsubishi Chemical Polyester Co., Ltd.).

此外，基材之一方之面(黏著層被形成面)，可企圖提升其與黏著層的接著性而進行表面處理。以表面處理而言，可列舉如電暈處理、易接著處理、抗靜電處理等。另外，相關之電暈處理、易接著處理及抗靜電處理，可適用於該技術領域中之周知的方法。基材的厚度，通常為10至300 μ m，從柔軟性等觀點而言，宜為20至100 μ m，較宜為25至50 μ m。Further, one side of the substrate (the surface on which the adhesive layer is formed) can be surface-treated by attempting to improve the adhesion to the adhesive layer. Examples of the surface treatment include corona treatment, easy adhesion treatment, antistatic treatment, and the like. Further, related corona treatment, easy adhesion treatment, and antistatic treatment can be applied to a well-known method in the technical field. The thickness of the substrate is usually from 10 to 300 μm, and from the viewpoint of flexibility and the like, it is preferably from 20 to 100 μm, more preferably from 25 to 50 μm.

(黏著層)以使用於形成黏著層的黏著劑而言，係選擇在形成黏著層時可再剝離，且可使黏著層側面之水的接觸角會未達100°(宜為未達90°，較宜為未達80°)之黏著劑。若相關之接觸角在100°以上，則與在遮罩帶側面中之薄膜形成材料之間的濕潤性會變得不足，無法使在遮罩帶側部(側面附近)形成之流動性材料的彎月面高度變低，而薄膜的厚度或塗布形狀會變得與期望的狀態不同。此外，若水的接觸角過小，則例如將塗布液塗布為條紋狀時，如果塗布液之相鄰圖案連接在一起，因塗布液會被過分拉往遮罩帶側部，故容易產生薄膜的厚度變得與期望狀態不同的不良狀況，從要消除像相關之不良狀況之觀點而言，期望為10°以上(宜為15°以上，較宜為20°以上)。(Adhesive layer) For the adhesive used for forming the adhesive layer, it is selected to be peeled off when the adhesive layer is formed, and the contact angle of the water on the side of the adhesive layer may be less than 100° (preferably less than 90°) , preferably less than 80 °) adhesive. If the relevant contact angle is 100° or more, the wettability with the film forming material in the side surface of the mask tape may become insufficient, and the fluid material formed on the side portion (near the side surface) of the mask tape may not be formed. The meniscus height becomes lower, and the thickness or coating shape of the film may become different from the desired state. Further, when the contact angle of water is too small, for example, when the coating liquid is applied in a stripe shape, if the adjacent patterns of the coating liquid are joined together, since the coating liquid is excessively pulled to the side of the mask tape, the thickness of the film is likely to occur. The problem that is different from the desired state is desirably 10° or more (preferably 15° or more, and preferably 20° or more) from the viewpoint of eliminating the problem associated with the problem.

另外，由於黏著層厚度為薄，故並不容易直接測定黏著層側面之水的接觸角，但因黏著層的被黏面及側面為同一種材料所構成，所以可推測黏著層的被黏面及側面之水的接觸角為相同。因此，於本發明中，將黏著層被黏面之水的接觸角，定為黏著層側面之水的接觸角。In addition, since the thickness of the adhesive layer is thin, it is not easy to directly measure the contact angle of the water on the side of the adhesive layer. However, since the adhesive surface and the side surface of the adhesive layer are composed of the same material, it is possible to estimate the adhesive surface of the adhesive layer. The contact angle of the water on the side is the same. Therefore, in the present invention, the contact angle of the water to which the adhesive layer is adhered is defined as the contact angle of the water on the side of the adhesive layer.

以相關之黏著劑而言，適合使用聚酯系黏著劑、丙烯酸系黏著劑。以聚酯系黏著劑而言，應提高濕潤性，宜為含有如下述之聚酯：以從聚碳酸酯二醇、聚己內酯二醇等中選出之二醇化合物(羥值宜為35至130KOHmg/g，較宜為45至120KOHmg/g)與從癸二酸(sebacic acid)、己二酸、壬二酸、鄰苯二甲酸等中選出之二元酸進行反應而獲得的聚酯。For the related adhesive, a polyester adhesive or an acrylic adhesive is suitably used. In the case of the polyester-based adhesive, the wettability should be improved, and it is preferably a polyester containing a diol compound selected from polycarbonate diol, polycaprolactone diol or the like (the hydroxyl value is preferably 35). a polyester obtained by reacting a dibasic acid selected from sebacic acid, adipic acid, sebacic acid, phthalic acid or the like to 130 KOHmg/g, preferably 45 to 120 KOHmg/g. .

此外，亦宜使用具有含烴基的側鏈，且數量平均分子量為5000以上的聚酯。此時，作為側鏈的含有烴基之基的含量比率並無特別限制，可因應黏著性、柔軟性、耐熱性或機械特性等各種特性作適當的選擇。聚酯可單獨或組合2種以上而使用。Further, it is also preferred to use a polyester having a side chain having a hydrocarbon group and having a number average molecular weight of 5,000 or more. In this case, the content ratio of the hydrocarbon group-containing group as the side chain is not particularly limited, and may be appropriately selected depending on various properties such as adhesion, flexibility, heat resistance, and mechanical properties. The polyester may be used singly or in combination of two or more.

作為側鏈的含有烴基之基(亦稱為「含烴基」)，只要是含有烴基的基即可，並無特別限制。以含烴基而言，可為僅由烴基所構成之基，亦可為透過二價的有機基而與烴基結合之型態的含烴基(例如，烴基－氧基、烴基－氧羰基等)。以含烴基而言，可適合使用僅由烴基所構成之基(亦即烴基)。聚酯通常在分子中擁有複數的含烴基。以此等複數的含烴基而言，可僅使用1種基，亦可使用2種以上的基。The hydrocarbon group-containing group (also referred to as "hydrocarbon-containing group") as a side chain is not particularly limited as long as it is a group containing a hydrocarbon group. The hydrocarbon-containing group may be a group composed only of a hydrocarbon group, or a hydrocarbon group having a type in which a divalent organic group is bonded to a hydrocarbon group (for example, a hydrocarbon group-oxy group, a hydrocarbon group-oxycarbonyl group, or the like). In the case of a hydrocarbon-containing group, a group composed only of a hydrocarbon group (that is, a hydrocarbon group) can be suitably used. Polyesters typically possess a plurality of hydrocarbon-containing groups in the molecule. In order to use such a plurality of hydrocarbon-containing groups, only one type of group may be used, or two or more types of groups may be used.

以上述烴基而言，可為烷基等脂肪族烴基、環烷基(例如，環己基等)等脂環族烴基、芳基(例如，苯基或萘基等)等芳香族烴基中之任一者，但宜為脂肪族烴基。以脂肪族烴基而言，適合使用烷基。以烷基而言，可列舉出例如甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、戊基、己基、庚基、辛基、壬基、癸基、十一基、十二基、十三基、十四基、十五基、十六基、十七基、十八基等碳數1至20的烷基。The hydrocarbon group may be an aliphatic hydrocarbon group such as an alkyl group or an aliphatic hydrocarbon group such as a cycloalkyl group (for example, a cyclohexyl group) or an aromatic hydrocarbon group such as an aryl group (for example, a phenyl group or a naphthyl group). One, but preferably an aliphatic hydrocarbon group. In the case of an aliphatic hydrocarbon group, an alkyl group is suitably used. The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group or an octyl group. An alkyl group having 1 to 20 carbon atoms such as an indenyl group, a fluorenyl group, an undecyl group, a dodecyl group, a thirteenth group, a tetradecyl group, a fifteen group, a hexadecyl group, a heptadecyl group and an octadecyl group.

另外，以含烴基之含量比率而言，能以聚酯或其交聯構造體的玻璃轉移溫度(Tg)會成為為－10℃以下、宜為－20℃以下(通常至－100℃為止)的方式，及/或以在23℃會得到透明且液狀之聚酯的方式，而適當選擇。Further, in the content ratio of the hydrocarbon-containing group, the glass transition temperature (Tg) of the polyester or the crosslinked structure thereof may be -10 ° C or lower, preferably -20 ° C or lower (usually until -100 ° C). The method and/or the method of obtaining a transparent and liquid polyester at 23 ° C is appropriately selected.

聚酯的數量平均分子量下限，例如為5000，宜為10000，較宜為11000，更宜為12000，尤宜為20000；其上限，例如為90000、宜為80000，較宜為70000，更宜為60000。若聚酯的數量平均分子量為5000以上，則作為黏著劑之機械性強度、重複功能性(rework)或耐熱性較不易降低。另一方面，若為90000以下(尤為80000以下)，則較容易形成黏著薄片。此外，聚酯的分散度(重量平均分子量/數量平均分子量)之下限，通常為0.5，宜為1；其上限，通常為25，宜為14，更宜為13。此處，數量平均分子量係藉由GPC(凝膠滲透層析儀)測定所得之值。The lower limit of the number average molecular weight of the polyester is, for example, 5,000, preferably 10,000, more preferably 11,000, more preferably 12,000, and particularly preferably 20,000; and the upper limit thereof is, for example, 90,000, preferably 80,000, more preferably 70,000, more preferably 60000. When the number average molecular weight of the polyester is 5,000 or more, the mechanical strength, rework, or heat resistance of the adhesive is less likely to be lowered. On the other hand, if it is 90,000 or less (especially 80,000 or less), it is easy to form an adhesive sheet. Further, the lower limit of the degree of dispersion (weight average molecular weight / number average molecular weight) of the polyester is usually 0.5, preferably 1; and the upper limit thereof is usually 25, preferably 14, more preferably 13. Here, the number average molecular weight is a value measured by GPC (gel permeation chromatography).

聚酯，係藉由至少於單方成分擁有烴側鏈基之多元醇成分與多元羧酸成分進行酯化反應所得。多元醇與多元羧酸成分可單獨或組合2種以上而使用。The polyester is obtained by esterification of a polyol component having a hydrocarbon side chain group with at least a single component and a polyvalent carboxylic acid component. The polyol and the polyvalent carboxylic acid component may be used singly or in combination of two or more.

以具有含烴基之多元醇成分而言，可列舉出例如新戊二醇、2－甲基－1,3－丙二醇、2,2－二乙基－1,3－丙二醇、2－甲基－2－丙基－1,3－丙二醇、2－丁基－2－乙基－1,3－丙二醇、3－甲基－1,5－戊二醇、2－甲基－2,4－戊二醇、2,4－二乙基－1,5－戊二醇、1,3,5－三甲基－1,3－戊二醇、2－甲基－1,6－己二醇、2－甲基－1,8－辛二醇、2－甲基－1,9－壬二醇、二聚二醇(dimerdiol)、2－甲基－1,4－環己二醇等具有含烴基的二醇成分等。Examples of the polyol component having a hydrocarbon group include neopentyl glycol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, and 2-methyl- 2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentyl Glycol, 2,4-diethyl-1,5-pentanediol, 1,3,5-trimethyl-1,3-pentanediol, 2-methyl-1,6-hexanediol, 2-methyl-1,8-octanediol, 2-methyl-1,9-nonanediol, dimerdiol, 2-methyl-1,4-cyclohexanediol, etc. a diol component of a hydrocarbon group or the like.

以具有含烴基之多元羧酸成分而言，可舉出例如甲基丁二酸、乙基丁二酸、2,2－二甲基己二酸、2,3－二甲基己二酸、2,4－二甲基己二酸、3,3－二甲基己二酸、二聚酸、2－甲基－1,4－環己烷二甲酸、2－乙基－1,4－環己烷二甲酸等具有含烴基的二羧酸成分等。此外，以具有含烴基之多元羧酸成分而言，亦可使用此等多元羧酸的酸酐或低級烷基酯等多元羧酸衍生物。Examples of the polyvalent carboxylic acid component having a hydrocarbon group include methyl succinic acid, ethyl succinic acid, 2,2-dimethyl adipic acid, and 2,3-dimethyl adipic acid. 2,4-Dimethyladipate, 3,3-dimethyladipate, dimer acid, 2-methyl-1,4-cyclohexanedicarboxylic acid, 2-ethyl-1,4- A dicarboxylic acid component or the like having a hydrocarbon group such as cyclohexanedicarboxylic acid. Further, as the polyvalent carboxylic acid component having a hydrocarbon group, a polyvalent carboxylic acid derivative such as an acid anhydride or a lower alkyl ester of such a polyvalent carboxylic acid can also be used.

另外，此時，在可保持聚酯之耐熱特性、黏著性等的範圍(例如在聚酯或其交聯構造體之玻璃轉移溫度可調整至－10℃以下的範圍)內，使用其他多元醇成分或其他多元羧酸成分係重要。Further, in this case, other polyols are used in a range in which heat resistance, adhesion, and the like of the polyester can be maintained (for example, in a range in which the glass transition temperature of the polyester or the crosslinked structure thereof can be adjusted to -10 ° C or lower). The ingredients or other polycarboxylic acid components are important.

以其他多元醇成分而言，可列舉出例如乙二醇、1,3－丙二醇、1,4－丁二醇、1,5－戊二醇、1,6－己二醇、1,8－辛二醇、1,9－壬二醇、1,10－癸二醇、1,18－十八烷二醇(1,18－octadecanediol)等直鏈狀脂肪族二醇成分；或是1,2－環己二醇、1,3－環己二醇、1,4－環己二醇等脂環族二醇成分等。The other polyol component may, for example, be ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8- a linear aliphatic diol component such as octanediol, 1,9-nonanediol, 1,10-decanediol or 1,18-octadecanediol; or 1, An alicyclic diol component such as 2-cyclohexanediol, 1,3-cyclohexanediol or 1,4-cyclohexanediol.

以其他多元羧酸成分而言，可列舉出例如丁二酸、己二酸、壬二酸、癸二酸、1,12－十二酸(dodecanoic acid)、1,14－十四烷二酸(tetradecane diacid)等脂肪族二羧酸成分；或是1,2－環己烷二甲酸、1,3－環己烷二甲酸、1,4－環己烷二甲酸等脂環族二羧酸成分；或是鄰苯二甲酸、間苯二甲酸、對苯二甲酸、1,4－萘二甲酸(1,4－naphthalene dicarboxylic acid)、4,4’－聯苯二甲酸等芳香族二羧酸成分等。此外，以其他多元羧酸成分而言，亦可使用此等多元聚羧酸的酸酐或低級烷基酯等多元羧酸衍生物。Examples of the other polycarboxylic acid component include succinic acid, adipic acid, sebacic acid, sebacic acid, 1,12-dodecanoic acid, 1,14-tetradecanedioic acid. An aliphatic dicarboxylic acid component such as tetradecane diacid; or an alicyclic dicarboxylic acid such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid or 1,4-cyclohexanedicarboxylic acid Ingredients; or aromatic dicarboxylic acid such as phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalene dicarboxylic acid, 4,4'-diphenyl phthalic acid Acid components, etc. Further, as the other polycarboxylic acid component, a polyvalent carboxylic acid derivative such as an acid anhydride or a lower alkyl ester of such a polyvalent polycarboxylic acid can also be used.

其他多元醇成分與其他多元羧酸成分的使用量，可從例如相對於多元醇成分及多元羧酸成分總量之0至80重量%的範圍中進行選擇。The amount of the other polyol component and the other polycarboxylic acid component to be used can be selected, for example, from 0 to 80% by weight based on the total amount of the polyol component and the polyvalent carboxylic acid component.

另外，以多元醇成分而言，為了容易獲得目的之分子量之聚合物，亦可使用市面販售之聚酯二醇成分、聚醚二醇成分、聚己內酯二醇成分等。具體而言，以聚酯二醇成分而言，可列舉出使用例如以乙二醇、二乙二醇、1,4－丁二醇、新戊二醇、3－甲基－1,5－戊二醇、2－丁基－2－乙基－1,3－丙二醇、2,4－二乙基－1,5－戊二醇、1,8－辛二醇、1,9－壬二醇、2－甲基－1,8－辛二醇、1,8－癸二醇、十八烷二醇等二醇成分，與丁二酸、甲基丁二酸、己二酸、庚二酸、壬二酸、癸二酸、1,12－十二酸、1,14－十四烷二酸或是此等化合物的酸酐或低級烷基酯等二羧酸成分或其衍生物，在單獨或混合之狀態下進行脫水反應所獲得之聚酯二醇等；以市面販售商品為例，可列舉出商品名為「Kuraray Polyol P－510」、「Kuraray Polyol P－1010」、「Kuraray Polyol P－2010」「Kuraray Polyol P－3010」、「Kuraray Polyol P－5010」[以上為kuraray股份公司製]等由3－甲基－1,5－戊二醇與己二酸反應而產生之聚酯二醇。Further, in order to easily obtain a polymer having a molecular weight of interest for the polyol component, a commercially available polyester diol component, a polyether diol component, a polycaprolactone diol component, or the like may be used. Specifically, as the polyester diol component, for example, ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5- can be used. Pentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,8-octanediol, 1,9-anthracene a diol component such as an alcohol, 2-methyl-1,8-octanediol, 1,8-nonanediol or octadecanediol, and succinic acid, methyl succinic acid, adipic acid, and gem Acid, azelaic acid, sebacic acid, 1,12-dodecanoic acid, 1,14-tetradecanedioic acid or a dicarboxylic acid component or a derivative thereof such as an acid anhydride or a lower alkyl ester of such a compound A polyester diol obtained by a dehydration reaction in a state of being separately or mixedly; for example, a commercially available product is exemplified by "Kuraray Polyol P-510", "Kuraray Polyol P-1010", and "Kuraray". Polyol P-2010" "Kuraray Polyol P-3010" and "Kuraray Polyol P-5010" [above, manufactured by Kuraray Co., Ltd.] are produced by reacting 3-methyl-1,5-pentanediol with adipic acid. Polyester diol.

以聚醚二醇成分而言，可列舉出例如使環氧乙烷、環氧丙烷、四氫呋喃等進行開環聚合而成之聚乙二醇、聚丙二醇、聚四亞甲二醇(polytetramethylene glycol)，及將此等化合物共聚之共聚醚等，以市面販售商品為例，可列舉出商品名為「Adeka Polyether P－400」、「Adeka Polyether P－1000」、「Adeka Polyether P－2000」「Adeka Polyether P－3000」[以上為旭電化工業股份公司製]等在丙二醇加成環氧丙烷而成之聚醚二醇。The polyether diol component may, for example, be polyethylene glycol, polypropylene glycol or polytetramethylene glycol obtained by ring-opening polymerization of ethylene oxide, propylene oxide or tetrahydrofuran. And copolyethers which are copolymerized with these compounds, and the commercial products are exemplified as "Adeka Polyether P-400", "Adeka Polyether P-1000", "Adeka Polyether P-2000"" Adeka Polyether P-3000" [above, manufactured by Asahi Kasei Kogyo Co., Ltd.] is a polyether diol obtained by adding propylene oxide to propylene glycol.

以聚己內酯二醇成分而言，可列舉出例如藉由將ε－己內酯、σ－戊內酯等環狀酯單體進行開環聚合而得之己內酯系聚酯二醇等，以市面販售商品為例，可列舉出商品名為「PLACCEL L205AL」、「PLACCEL L212AL」、「PLACCEL L220PL」「PLACCEL L230AL」[以上為DAICEL化學工業股份公司製]等。The polycaprolactone diol component may, for example, be a caprolactone-based polyester diol obtained by subjecting a cyclic ester monomer such as ε-caprolactone or σ-valerolactone to ring-opening polymerization. For example, the products sold under the market name include "PLACCEL L205AL", "PLACCEL L212AL", "PLACCEL L220PL" and "PLACCEL L230AL" (the above is manufactured by DAICEL Chemical Industry Co., Ltd.).

在本發明之黏著劑組成物中，宜使用具有下述式表示之構造單位的脂肪族碳酸酯二醇成分。藉由使用下述二醇成分，而可得到耐熱性更優良之黏著劑組成物。下述式中，R為碳數2至20之直鏈狀或分枝狀烴基。In the adhesive composition of the present invention, an aliphatic carbonate diol component having a structural unit represented by the following formula is preferably used. By using the following diol component, an adhesive composition having more excellent heat resistance can be obtained. In the following formula, R is a linear or branched hydrocarbon group having 2 to 20 carbon atoms.

以此等脂肪族碳酸酯二醇成分之具體例而言，可列舉如：碳酸伸丙酯二醇(propylene carbonate diol)、碳酸六亞甲酯二醇(hexamethylene carbonate diol)、碳酸3－甲基戊烯酯二醇(3－methylpentene carbonate diol)等碳酸酯二醇成分；將包含乙二醇、二乙二醇、1,2－丙二醇、1,3－丙二醇、1,3－丁二醇、1,4－丁二醇、α－甲基丁二醇、α－二甲基丁二醇、1,5－戊二醇、2－甲基－2,4－戊二醇、3－甲基－1,5－戊二醇、1,6－己二醇、1,8－辛二醇、2－甲基－1,8－辛二醇、環丁烷－1,3－二(2－乙醇)、1,4－二羥基環己烷、環己烷－1,4－二甲醇、1,9－壬二醇、1,10－癸二醇、1,12－十二烷二醇(1,12-dodecane diol)、新戊二醇、含碳數為2至9個(宜為2至4個)之伸烷基的聚氧伸烷基二醇(polyoxyalkylene glycol)或聚四亞甲基醚二醇(polytetramethylene ether glycol)等的長鏈二醇及其衍生物等二醇類，與二氯化羰(phosgene)進行聚縮合反應所得的聚碳酸酯二醇成分；將上述二醇類與碳酸二甲酯、碳酸二乙酯、碳酸二丙酯、碳酸二異丙酯、碳酸二丁酯、碳酸乙基丁酯(ethyl butyl carbonate)、碳酸伸乙酯(ethylene carbonate)、碳酸伸丙酯、碳酸二苯酯、碳酸二苄酯(dibenzyl carbonate)等碳酸二酯類進行轉酯化縮合反應所得之聚碳酸酯二醇成分；將上述二醇類併用2種以上所得之共聚合聚碳酸酯二醇成分；將上述各種聚碳酸酯二醇成分與含羧基之化合物進行酯化反應所得之聚碳酸酯二醇成分；將上述各種聚碳酸酯二醇成分與含羥基之化合物進行醚化反應所得之聚碳酸酯二醇成分；將上述聚碳酸酯二醇成分與酯化合物進行轉酯化反應所得之聚碳酸酯二醇成分；將上述聚碳酸酯二醇成分與含羥基之化合物進行轉酯化反應所得之聚碳酸酯二醇成分；將上述各種聚碳酸酯二醇成分與二羧酸化合物進行聚縮合反應所得之變形聚酯系聚碳酸酯二醇成分；將上述各種聚碳酸酯二醇成分與環氧烷進行共聚合反應所得之共聚合聚醚系聚碳酸酯二醇成分等。以適合使用之聚碳酸酯二醇成分的市面販售商品為例，可列舉出商品名為「PLACCEL CD205」、「PLACCEL CD210」、「PLACCEL CD220」、「PLACCEL CD205PL」、「PLACCEL CD210PL」、「PLACCEL CD220PL」[以上為DAICEL化學工業股份公司製]或「PMHC－2050」、「PMHC－2070」、「PNOC－1000」、「PNOC－2000」[以上為kuraray股份公司製]。Specific examples of such an aliphatic carbonate diol component include propylene carbonate diol, hexamethylene carbonate diol, and 3-methyl carbonate. a carbonate diol component such as 3-methylpentene carbonate diol; comprising ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, and 1,3-butylene glycol, 1,4-butanediol, α-methylbutanediol, α-dimethylbutanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 3-methyl -1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, cyclobutane-1,3-di(2- Ethanol), 1,4-dihydroxycyclohexane, cyclohexane-1,4-dimethanol, 1,9-nonanediol, 1,10-nonanediol, 1,12-dodecanediol ( 1,12-dodecane diol), neopentyl glycol, polyoxyalkylene glycol or polytetramethylene having 2 to 9 (preferably 2 to 4) alkylene groups A glycol such as a long-chain diol such as polytetramethylene ether glycol or a derivative thereof, and phosgene a polycarbonate diol component obtained by a polycondensation reaction; the above diols and dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethyl butyl carbonate Polycarbonate obtained by transesterification condensation reaction of carbonic acid diesters such as (ethyl butyl carbonate), ethylene carbonate, propyl carbonate, diphenyl carbonate, and dibenzyl carbonate An alcohol component; a copolymerized polycarbonate diol component obtained by using the above diols in combination of two or more kinds; and a polycarbonate diol component obtained by esterifying the various polycarbonate diol components and a carboxyl group-containing compound; a polycarbonate diol component obtained by subjecting the above various polycarbonate diol components to a hydroxyl group-containing compound to etherification reaction; and a polycarbonate diol obtained by subjecting the above polycarbonate diol component to an ester compound by transesterification reaction a component; a polycarbonate diol component obtained by transesterification of the polycarbonate diol component and a hydroxyl group-containing compound; and the above various polycarbonate diol components and a dicarboxylic acid compound A modified polyester-based polycarbonate diol component obtained by a polycondensation reaction; a copolymerized polyether-based polycarbonate diol component obtained by copolymerizing the above various polycarbonate diol components with an alkylene oxide. For example, commercially available products of polycarbonate diol components suitable for use include "PLACCEL CD205", "PLACCEL CD210", "PLACCEL CD220", "PLACCEL CD205PL", "PLACCEL CD210PL", and "PLACCEL CD210PL". PLACCEL CD220PL" [The above is manufactured by DAICEL Chemical Industry Co., Ltd.] or "PMHC-2050", "PMHC-2070", "PNOC-1000", "PNOC-2000" [above is kuraray AG].

再者，在本發明的黏著劑中，以容易取得接著性與耐熱性之平衡為理由，亦可添加3官能基以上之多元醇成分或多元羧酸成分。In addition, in the adhesive of the present invention, a trifunctional or higher polyhydric alcohol component or a polyvalent carboxylic acid component may be added for the purpose of easily obtaining a balance between adhesion and heat resistance.

作為3元以上之多元醇，可列舉如甘油、三羥甲基丙烷、1,2,4－丁三醇、1,2,5－戊三醇、1,2,6－己三醇、季戊四醇、二季戊四醇等脂肪族多元醇或此等化合物的衍生物。此外，作為3元以上之多元羧酸，可列舉如1,2,4－丁烷三甲酸(1,2,4－butane tricarboxylic acid)、1,2,5－己烷三甲酸(1,2,5－hexane tricarboxylic acid)、1,2,4－環己烷三甲酸(1,2,4－cyclohexane tricarboxylic acid)、內消旋(meso)－丙烷－1,2,3,4－四甲酸等脂肪族多元羧酸；苯偏三甲酸(trimellitic acid)、苯均四甲酸(pyromellitic acid)等芳香族多元羧酸；或此等化合物的酸酐或是低級烷基酯等。Examples of the polyhydric alcohol having 3 or more members include glycerin, trimethylolpropane, 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, and pentaerythritol. An aliphatic polyol such as dipentaerythritol or a derivative of such a compound. Further, examples of the polyvalent carboxylic acid having 3 or more members include 1,2,4-butane tricarboxylic acid (1,2,4-butane tricarboxylic acid) and 1,2,5-hexanetricarboxylic acid (1,2). ,5-hexane tricarboxylic acid), 1,2,4-cyclohexane tricarboxylic acid, meso-propane-1,2,3,4-tetracarboxylic acid An aliphatic polybasic carboxylic acid; an aromatic polycarboxylic acid such as trimellitic acid or pyromellitic acid; or an acid anhydride or a lower alkyl ester of such a compound.

此外，通常作為多元羧酸成分而使用之羧酸，係可列舉如脂肪族二羧酸或芳香族多元羧酸。具體而言，可列舉如丁二酸、甲基丁二酸、己二酸、庚二酸、壬二酸、癸二酸、1,12－十二酸、1,14－十四烷二酸、二聚酸等脂肪族二羧酸；或鄰苯二甲酸、1,4－萘二甲酸、4,4’－聯苯二甲酸等芳香族二羧酸；及此等化合物的酸酐或低級烷基酯等。Further, the carboxylic acid to be used as the polyvalent carboxylic acid component is usually an aliphatic dicarboxylic acid or an aromatic polycarboxylic acid. Specific examples thereof include succinic acid, methyl succinic acid, adipic acid, pimelic acid, sebacic acid, sebacic acid, 1,12-dodecanoic acid, 1,14-tetradecanedioic acid. An aliphatic dicarboxylic acid such as a dimer acid; or an aromatic dicarboxylic acid such as phthalic acid, 1,4-naphthalenedicarboxylic acid or 4,4'-diphenyl phthalic acid; and an acid anhydride or lower alkane of such a compound Base ester and the like.

3元以上之多元醇及/或3元以上之多元羧酸的使用量，以聚酯的分散度(重量平均分子量/數量平均分子量)會成為適當數值之方式，藉由其分子量或價數而選擇最適當的使用量。通常，相對於脂肪族二醇與二羧酸的合計量，為2至30重量%，更宜為4至15重量%的比率。若上述3元以上之多元醇及/或3元以上之多元羧酸的使用量未達2重量%，則聚酯的分散度容易變小，若超過20重量%，則聚酯的分散度會變得過大，在此等情形，容易造成如後述的問題。The amount of the polyhydric alcohol of 3 or more and/or the polyvalent carboxylic acid of 3 or more, and the degree of dispersion (weight average molecular weight / number average molecular weight) of the polyester may be an appropriate value, by its molecular weight or valence Choose the most appropriate amount of usage. Usually, it is a ratio of 2 to 30% by weight, more preferably 4 to 15% by weight, based on the total amount of the aliphatic diol and the dicarboxylic acid. When the amount of the above-mentioned trivalent or higher polyhydric alcohol and/or trivalent or higher polyvalent carboxylic acid is less than 2% by weight, the degree of dispersion of the polyester tends to be small, and if it exceeds 20% by weight, the degree of dispersion of the polyester will be It becomes too large, and in such a case, it is easy to cause a problem as mentioned later.

使用3元以上之多元醇及/或3元以上之多元羧酸時的聚酯，分散度(重量平均分子量/數量平均分子量)為2.2以上，宜為2.5以上，較宜為2.7以上。以上限而言，宜為25以下，較宜為20以下，更宜為14以下，尤宜為13以下。聚酯的分散度，如以上所述，可藉由3元以上之多元醇及/或3元以上之多元羧酸的使用量或數量平均分子量而進行調整，在上述範圍內，可因應用途目的而調整為適宜之分散度。當分散度未達下限值時，會有難以取得機械性強度與柔軟性之平衡，且無法使耐熱性與對於粗糙面之接著性同時成立的傾向。此外，當分散度過大時，聚酯會有變成高黏度、容易引起膠狀化、難以形成黏著薄片的傾向，故宜為在上述範圍內。When the polyester having a trihydric or higher polyhydric alcohol and/or a trivalent or higher polyvalent carboxylic acid is used, the degree of dispersion (weight average molecular weight/number average molecular weight) is 2.2 or more, preferably 2.5 or more, and more preferably 2.7 or more. The upper limit is preferably 25 or less, more preferably 20 or less, more preferably 14 or less, and particularly preferably 13 or less. The dispersity of the polyester can be adjusted by using the amount of the trihydric or higher polyhydric alcohol and/or the trivalent or higher polycarboxylic acid or the number average molecular weight as described above, and in the above range, it can be used for the purpose of use. Adjusted to the appropriate dispersion. When the degree of dispersion is less than the lower limit, it is difficult to obtain a balance between mechanical strength and flexibility, and the heat resistance and the adhesion to the rough surface cannot be simultaneously established. Further, when the degree of dispersion is too large, the polyester tends to have a high viscosity, tends to cause gelation, and it is difficult to form an adhesive sheet, and therefore it is preferably within the above range.

另外，重量平均分子量及數量平均分子量係藉由GPC(凝膠滲透層析儀)測定所得之值。Further, the weight average molecular weight and the number average molecular weight are values obtained by GPC (gel permeation chromatography).

藉由使用如此的多元醇成分與多元羧酸成分，使用適當的觸媒等使進行酯化反應而可獲得聚酯系黏著劑。在進行此反應時，多元醇成分與多元羧酸成分，以等莫耳反應為理想，但為了促進酯化反應，亦可過量使用任一方而進行反應。在此等黏著劑組成物中，藉由使聚酯進行交聯，可有效地顯現作為接著劑的功能。以使聚酯進行交聯的交聯處理方法而言，雖無特別限制，但可適宜採用例如在聚酯中添加具有能與羥基及/或羧基反應之官能基的化合物(例如聚異氰酸酯化合物、環氧化合物、氮丙啶(aziridine)化合物之交聯劑等)而使其進行交聯的方法，亦即所謂使用交聯劑的方法。以交聯劑而言，可列舉如上述之聚異氰酸酯化合物、環氧化合物、氮丙啶化合物等。但在其中，尤宜為使用聚異氰酸酯化合物。交聯劑可單獨或組合2種以上而使用。A polyester-based adhesive can be obtained by using such a polyol component and a polyvalent carboxylic acid component, and performing an esterification reaction using an appropriate catalyst or the like. In the case of carrying out the reaction, the polyol component and the polyvalent carboxylic acid component are preferably subjected to a molar reaction. However, in order to promote the esterification reaction, the reaction may be carried out in excess. In such an adhesive composition, by crosslinking the polyester, the function as an adhesive can be effectively exhibited. The crosslinking treatment method for crosslinking the polyester is not particularly limited, and for example, a compound having a functional group capable of reacting with a hydroxyl group and/or a carboxyl group (for example, a polyisocyanate compound, A method of crosslinking an epoxy compound, a crosslinking agent of an aziridine compound, or the like, that is, a method of using a crosslinking agent. The crosslinking agent may, for example, be a polyisocyanate compound, an epoxy compound or an aziridine compound as described above. Among them, it is particularly preferred to use a polyisocyanate compound. The crosslinking agent can be used singly or in combination of two or more.

以作為交聯劑之聚異氰酸酯化合物而言，例如可列舉如二異氰酸四亞甲酯(tetramethylene diisocyanate)、二異氰酸六亞甲酯(hexamethylene diisocyanate)等低級脂肪族聚異氰酸酯類；二異氰酸環伸戊酯(cyclopentylene diisocyanate)、二異氰酸環伸己酯(cyclohexylene diisocyanate)、異佛酮二異氰酸酯(isophorone diisocyanate)等脂環族異氰酸酯類；2,4－二異氰酸伸甲苯酯(2,4－tolylene diisocyanate)、4,4’－二苯基甲烷二異氰酸酯(4,4’－diphenylmethane diisocyanate)、二異氰酸伸茬酯(xylylene diisocyanate)等芳香族異氰酸酯類；(三羥甲基丙烷二異氰酸酯/二異氰酸伸甲苯酯)三聚體加成物(例如，商品名「CORONATE L」日本POLYURETHANE工業股份公司製)、(三羥甲基丙烷二異氰酸酯/二異氰酸六亞甲酯)三聚體加成物(例如，商品名「CORONATE HL」日本POLYURETHANE工業股份公司製)等異氰酸酯加成物等。The polyisocyanate compound as a crosslinking agent may, for example, be a lower aliphatic polyisocyanate such as tetramethylene diisocyanate or hexamethylene diisocyanate; Alicyclic isocyanate such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate; 2,4-diisocyanate An aromatic isocyanate such as 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate or xylylene diisocyanate; Trimethylolpropane diisocyanate / toluene diisocyanate) trimer adduct (for example, trade name "CORONATE L" manufactured by Japan POLYURETHANE Industries Co., Ltd.), (trimethylolpropane diisocyanate / diiso) An isocyanate adduct such as a hexamethylene cyanate) trimer adduct (for example, trade name "CORONATE HL" manufactured by Japan POLYURETHANE Co., Ltd.).

交聯劑之使用量，係依據應交聯之聚酯分子量的平衡，更依據作為黏著劑之使用用途等而作出適當選擇。以交聯劑的使用用途而言，一般而言，相對於聚酯100重量份，係0.5重量份以上。以交聯劑而言，其使用量宜以聚酯交聯處理後之溶劑不溶成分會成為10重量%以上(宜為20重量%以上)之方式而使用。另外，關於聚酯交聯處理後之溶劑不溶成分的詳細內容，將於後述。如此，在本發明中，為了使機械性強度與柔軟性兩者同時成立(或是為了使耐熱性與黏著性兩者同時成立)，並不需要嚴密地調整交聯劑使用量，而可容易地進行聚酯的交聯處理。The amount of the crosslinking agent used is appropriately selected depending on the balance of the molecular weight of the polyester to be crosslinked, and more depending on the use as the adhesive. The use of the crosslinking agent is generally 0.5 parts by weight or more based on 100 parts by weight of the polyester. The crosslinking agent is preferably used in such a manner that the solvent-insoluble component after the polyester crosslinking treatment is 10% by weight or more (preferably 20% by weight or more). In addition, the details of the solvent-insoluble component after the polyester cross-linking treatment will be described later. As described above, in the present invention, in order to simultaneously establish both mechanical strength and flexibility (or to establish both heat resistance and adhesion), it is not necessary to strictly adjust the amount of the crosslinking agent to be used, and it is easy to use. The cross-linking treatment of the polyester is carried out.

此外，以實質上的交聯劑而言，可使用電子束硬化型化合物(多官能單體)。該多官能單體，係在1分子中具有複數個不飽和鍵的化合物，其可藉由電子束等而產生交聯反應。以此等的多官能單體而言，可適宜使用(甲基)丙烯酸酯系多官能單體。該(甲基)丙烯酸酯系多官能單體中，包括例如聚乙二醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯(pentaerythritol tri(meth)acrylate)、季戊四醇四(甲基)丙烯酸酯(pentaerythritol tetra(meth)acrylate)、二季戊四醇單羥基五(甲基)丙烯酸酯(dipentaerythritol mono－hydroxy penta(meth)acrylate)、二季戊四醇六(甲基)丙烯酸酯(dipentaerythritol hexa(meth)acrylate)、四羥甲基甲烷四(甲基)丙烯酸酯(tetramethylolmethane tetra(meth)acrylate)、三羥甲基丙烷三(甲基)丙烯酸酯(trimethylolpropane tri(meth)acrylate)、1,4－丁二醇二(甲基)丙烯酸酯(1,4－butylene glycol di(meth)acrylate)、1,6－己二醇二(甲基)丙烯酸酯(1,6－hexanedioldi(meth)acrylate)等。多官能基單體可單獨或組合2種以上而使用。Further, as the substantially crosslinking agent, an electron beam curing type compound (polyfunctional monomer) can be used. The polyfunctional monomer is a compound having a plurality of unsaturated bonds in one molecule, which can cause a crosslinking reaction by an electron beam or the like. As such a polyfunctional monomer, a (meth)acrylate type polyfunctional monomer can be suitably used. Among the (meth) acrylate-based polyfunctional monomers, for example, polyethylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(methyl) tetra(methyl) )pentaerythritol tetra(meth)acrylate, dipentaerythritol mono-hydroxy penta(meth)acrylate, dipentaerythritol hexa(meth) Acrylate), tetramethylolmethane tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butyl 1, 4-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and the like. The polyfunctional monomer may be used singly or in combination of two or more.

上述多官能基單體的使用量，與交聯劑相同地，係依據與應交聯之聚酯分子量的平衡，更依據作為黏著劑之使用用途等而作出適當選擇。多官能單體的使用量，一般而言相對於聚酯100重量份，係1重量份以上，藉由在此比例下使用電子束進行交聯，而可使聚酯交聯處理後之溶劑不溶成分為10重量%以上(宜為20重量%以上)。如此，為了藉由聚酯之交聯而使作為黏著劑的功能變好，聚酯交聯處理後之溶劑不溶成分係以10重量%以上(宜為20重量%以上)為較理想。若聚酯交聯處理後之溶劑不溶成分為未達10重量%，則會有黏著劑的凝集力不足而使機械性強度變低，並無法得到足夠之耐熱性的情形。另外，若聚酯交聯處理後之溶劑不溶成分超過70重量%，則會損害到聚酯之交聯體的柔軟性，容易使黏著性變低，因此作為聚酯交聯處理後之溶劑不溶成分的上限以70重量%(宜為60重量%)為較理想。The amount of the above-mentioned polyfunctional monomer to be used is appropriately selected depending on the balance of the molecular weight of the polyester to be crosslinked, and the use as the adhesive, etc., in the same manner as the crosslinking agent. The amount of the polyfunctional monomer to be used is generally 1 part by weight or more based on 100 parts by weight of the polyester, and the solvent is insoluble after cross-linking treatment of the polyester by crosslinking with an electron beam at this ratio. The component is 10% by weight or more (preferably 20% by weight or more). As described above, in order to improve the function as an adhesive by cross-linking of the polyester, it is preferred that the solvent-insoluble component after the polyester cross-linking treatment is 10% by weight or more (preferably 20% by weight or more). When the solvent-insoluble component after the polyester cross-linking treatment is less than 10% by weight, the cohesive force of the adhesive may be insufficient to lower the mechanical strength, and sufficient heat resistance may not be obtained. In addition, when the solvent-insoluble component after the cross-linking treatment of the polyester exceeds 70% by weight, the flexibility of the crosslinked body of the polyester is impaired, and the adhesiveness is easily lowered. Therefore, the solvent after the cross-linking treatment of the polyester is insoluble. The upper limit of the component is preferably 70% by weight (preferably 60% by weight).

另外，以聚酯交聯處理後之溶劑不溶成分中的溶劑而言，可因應使用目的等而作適當選擇，可使用例如甲苯、二甲苯等芳香族烴類；己烷等脂肪族烴類；環己烷等脂環式烴類；甲醇、乙醇等醇類；乙酸乙酯等酯類；甲基乙基酮等酮類；乙二醇等二元醇(glycol)類；丙二醇單乙基醚等二元醇醚(glycol ether)類。In addition, the solvent in the solvent-insoluble component after the polyester cross-linking treatment can be appropriately selected depending on the purpose of use, and an aromatic hydrocarbon such as toluene or xylene or an aliphatic hydrocarbon such as hexane can be used; An alicyclic hydrocarbon such as cyclohexane; an alcohol such as methanol or ethanol; an ester such as ethyl acetate; a ketone such as methyl ethyl ketone; a glycol such as ethylene glycol; and a propylene glycol monoethyl ether; Equivalent glycol ethers.

此外，聚酯或經交聯處理之聚酯的玻璃轉移溫度，為－10℃以下(例如－100℃至－10℃)，宜為－20℃以下(例如－100℃至－20℃)。若聚酯或聚酯經交聯處理後的玻璃轉移溫度為超過－10℃時，則聚酯的交聯結構體會變硬而使柔軟度下降，黏著性下降。另外，以該玻璃轉移溫度而言，通常多採用聚酯交聯處理後的交聯結構體中之玻璃轉移溫度，本說明書亦以同樣方式採用。Further, the glass transition temperature of the polyester or the crosslinked polyester is -10 ° C or lower (for example, -100 ° C to -10 ° C), preferably -20 ° C or lower (for example, -100 ° C to -20 ° C). When the glass transition temperature of the polyester or polyester after the crosslinking treatment is more than -10 ° C, the crosslinked structure of the polyester becomes hard, and the softness is lowered, and the adhesiveness is lowered. Further, in terms of the glass transition temperature, the glass transition temperature in the crosslinked structure after the polyester cross-linking treatment is usually used, and the present specification is also employed in the same manner.

此外，以丙烯酸系黏著劑而言，宜含有丙烯酸系聚合物，該丙烯酸系聚合物含有(甲基)丙烯酸烷基酯與親水性單體作為單體單位。(甲基)丙烯酸烷基酯的烷基，其碳數宜為2至14，直鏈狀、分枝狀、環狀中任一者之型態皆可。以此等烷基而言，可列舉例如乙基、丙基、異丙基、丁基、異丁基、異戊基、己基、庚基、2－乙基己基、異辛基、異壬基、異癸基等。其中，宜為碳數2至10的烷基，較宜為丁基、2－乙基己基等碳數4至8的烷基。若碳數在上述範圍外時，則黏著力會變得不足，使其難以發揮黏著劑的功能。另外，上述(甲基)丙烯酸烷基酯，可以1種或組合2種以上而使用。Further, the acrylic adhesive preferably contains an acrylic polymer containing an alkyl (meth)acrylate and a hydrophilic monomer as a monomer unit. The alkyl group of the alkyl (meth)acrylate may have a carbon number of 2 to 14, and may be any of a linear form, a branched form, and a cyclic form. Examples of such an alkyl group include an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an isopentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an isooctyl group, and an isodecyl group. , different bases, etc. Among them, an alkyl group having 2 to 10 carbon atoms is preferable, and an alkyl group having 4 to 8 carbon atoms such as a butyl group or a 2-ethylhexyl group is preferred. When the carbon number is outside the above range, the adhesive strength becomes insufficient, making it difficult to function as an adhesive. In addition, the alkyl (meth)acrylate may be used alone or in combination of two or more.

以親水性單體而言，只要是在分子內具有羥基、胺基、醯胺基、磺酸基、羧基、酸酐基、醯亞胺基、磷酸基、環氧烷(alkylene oxide)基等親水性基者，便無特別限制。具體而言，可列舉如(甲基)丙烯酸2－羥乙酯(2－hydroxyethyl(meth)acrylate)、(甲基)丙烯酸2－羥丙酯(2－hydroxypropyl(meth)acrylate)、(甲基)丙烯酸2－羥丁酯(2－hydroxybutyl(meth)acrylate)、丙烯酸(4－羥基甲基環己基)甲酯((4－hydroxymethylcyclohexyl)methyl acrylate)、N－羥甲基(甲基)丙烯醯胺(N－methylol(meth)acrylamide)、乙烯基醇、烯丙基醇、2－羥基乙基乙烯基醚(2－hydroxyethyl vinyl ether)、4－羥基丁基乙烯基醚(4－hydroxybutyl vinyl ether)、二乙二醇單乙烯基醚(diethylene glycol mono－vinyl ether)、(甲基)丙烯酸3－羥丙酯(3－hydroxypropyl(meth)acrylate)、(甲基)丙烯酸4－羥丁酯、(甲基)丙烯酸2－羥己酯(2－hydroxyhexyl(meth)acrylate)、(甲基)丙烯酸6－羥己酯、(甲基)丙烯酸8－羥辛酯、(甲基)丙烯酸10－羥癸酯、(甲基)丙烯酸12－羥基月桂酯等含羥基單體；(甲基)丙烯酸二甲基胺基乙酯(dimethylaminoethyl(meth)acrylate)、(甲基)丙烯酸二乙基胺基乙酯(diethylaminoethyl(meth)acrylate)、(甲基)丙烯酸第三丁基胺基乙酯(t－butylaminoethyl(meth)acrylate)、(甲基)丙烯酸N,N－二甲基胺基丙酯(N,N－dimethylaminopropyl(meth)acrylate)等含胺基單體；(甲基)丙烯醯胺、N,N－二乙基(甲基)丙烯醯胺(N,N－diethyl(meth)acrylamide)、N,N－二甲基(甲基)丙烯醯胺(N,N－dimethyl(meth)acrylamide)、N－羥甲基(甲基)丙烯醯胺(N－methylol(meth)acrylamide)、N－甲氧基甲基(甲基)丙烯醯胺(N－methoxymethyl(meth)acrylamide)、N－丁氧基甲基(甲基)丙烯醯胺(N－butoxymethyl(meth)acrylamide)、N,N－亞甲基雙(甲基)丙烯醯胺(N,N－methylene bis(meth)acrylamide)、N－異丙基丙烯醯胺(N－isopropyl acrylamide)、N,N－二甲基胺基丙基丙烯醯胺(N,N－dimethylaminopropyl acrylamide)等含醯胺基單體；苯乙烯磺酸(styrene sulfonic acid)、烯丙磺酸(allyl sulfonic acid)、2－(甲基)丙烯醯胺基－2－甲基丙磺酸(2－(meth)acrylamido－2－methylpropane sulfonic acid)、(甲基)丙烯醯基丙磺酸((meth)acrylamido propane sulfonic acid)、(甲基)丙烯酸磺酸基丙酯(sulfo propyl(meth)acrylate)、(甲基)丙烯醯基氧基萘磺酸((meth)acryloyloxynaphthalene sulfonic acid)等含磺酸基單體；(甲基)丙烯酸、(甲基)丙烯酸羧乙酯(carboxyethyl(meth)acrylate)、(甲基)丙烯酸羧戊酯(carboxypentyl(meth)acrylate)、伊康酸(itaconic acid)、馬來酸(maleic acid)、富馬酸(fumaric acid)、巴豆酸(crotonic acid)等含羧基單體；馬來酸酐、伊康酸酐等含酸酐基單體；環己基馬來醯亞胺、異丙基馬來醯亞胺、N－環己基馬來醯亞胺、伊康醯亞胺(itaconimide)、N－苯基馬來醯亞胺(N－phenylmaleimide)等含醯亞胺基單體；2－羥乙基丙烯醯基磷酸酯(2－hydroxyethyl acryloyl phosphate)等含磷酸基單體；其他，如(甲基)丙烯腈、N－(甲基)丙烯醯基嗎福啉(N－(meth)acryloyl morpholine)、N－乙烯基－2－吡咯啶酮(N－vinyl－2－pyrrolidone)、N－乙烯基己內醯胺(N－vinyl caprolactam)等。這些化合物，可1種或組合2種以上而使用。The hydrophilic monomer has a hydrophilic group such as a hydroxyl group, an amine group, a mercapto group, a sulfonic acid group, a carboxyl group, an acid anhydride group, a quinone imine group, a phosphoric acid group or an alkylene oxide group. There is no special restriction on the basics. Specific examples thereof include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (methyl). ) 2-hydroxybutyl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl acrylate, N-methylol (meth) propylene hydride N-methylol(meth)acrylamide, vinyl alcohol, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether ), diethylene glycol mono-vinyl ether, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyhexyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxyl (meth)acrylate a hydroxyl group-containing monomer such as decyl ester or (meth)acrylic acid 12-hydroxylauryl ester; dimethylaminoethyl (meth)acrylate; Diethylaminoethyl (meth)acrylate, t-butylaminoethyl (meth)acrylate, (meth)acrylic acid N,N- An amine group-containing monomer such as N,N-dimethylaminopropyl(meth)acrylate; (meth)acrylamide, N,N-diethyl(meth)acrylamide (N, N-diethyl(meth)acrylamide), N,N-dimethyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide (N- Methylol (meth) acrylamide), N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide (N-butoxymethyl (N-butoxymethyl) Meth)acrylamide), N,N-methylene bis(meth)acrylamide, N-isopropyl acrylamide, N, N-N-dimethylamino propylamide (N, N-dimethylaminopropyl acrylamide) and the like; styrene sulfonic acid, allyl sulfonic acid, 2- (methyl) acrylamido-2-methylpropanesulfonic acid (2 (meth)acrylamido-2-methylpropane sulfonic acid), (meth)acrylamido propane sulfonic acid, sulfo propyl (meth)acrylate a sulfonic acid group-containing monomer such as (meth)acryloyloxynaphthalene sulfonic acid; (meth)acrylic acid (carboxyethyl methacrylate) , carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, etc. Monomer; anhydride-containing monomer such as maleic anhydride, itaconic anhydride; cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide, and iconimide Itaconimide), a N-phenylmaleimide-containing monomer such as N-phenylmaleimide; a phosphate-containing monomer such as 2-hydroxyethyl acryloyl phosphate; Others such as (meth)acrylonitrile, N-(meth)acryloyl morpholine, N-vinyl 2- pyrrolidone (N-vinyl-2-pyrrolidone), N- vinyl caprolactam (N-vinyl caprolactam) and the like. These compounds may be used alone or in combination of two or more.

此外，以含環氧烷基單體的氧伸烷基(oxyalkylene)單位而言，可列舉如具有碳數1至6之伸烷基者，例如可列舉如氧亞甲基(oxymethylene)、氧伸乙基(oxyethylene)、氧伸丙基(oxypropylene)、氧伸丁基(oxybutylene)等。氧伸烷基鏈的烴基可為直鏈，亦可為分枝。Further, examples of the oxyalkylene unit containing an epoxyalkyl group-containing monomer include those having a C 1 to 6 alkyl group, and examples thereof include oxymethylene and oxygen. Oxyethylene, oxypropylene, oxybutylene, and the like. The hydrocarbyl group of the oxygen alkyl chain may be a straight chain or a branch.

此外，以對於上述含環氧烷基單體的氧伸烷基單位之平均加成莫耳數而言，從與被黏體間之濕潤性的觀點來看，宜為3至40，較宜為4至35，尤宜為5至30。若上述之平均加成莫耳數大於3，則可獲得與被黏體更良好的濕潤性。此外，若上述之平均加成莫耳數大於40時，則對於被黏體之污染會有增加的傾向。另外，氧伸烷基鏈的末端，可維持為羥基或以其他官能基等所取代。再者，上述含環氧烷基單體宜為具有環氧乙烷基(ethylene oxide)之單體。藉由使用具有含環氧乙烷基單體的(甲基)丙烯酸單體，可容易地獲得與被黏體更良好的濕潤性。以(甲基)丙烯酸環氧烷附加物的具體例而言，可列舉出例如聚乙二醇(甲基)丙烯酸酯、聚丙二醇(甲基)丙烯酸酯、聚乙二醇－聚丙二醇(甲基)丙烯酸酯、聚乙二醇－聚丁二醇(甲基)丙烯酸酯、聚丙二醇－聚丁二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、乙氧基聚乙二醇(甲基)丙烯酸酯、丁氧基聚乙二醇(甲基)丙烯酸酯、辛氧基聚乙二醇(甲基)丙烯酸酯、月桂氧基聚乙二醇(甲基)丙烯酸酯(lauroxy polyethylene glycol(meth)acrylate)、硬脂氧基聚乙二醇(甲基)丙烯酸酯(stearoxy polyethylene glycol (meth)acrylate)、苯氧基聚乙二醇(甲基)丙烯酸酯、甲氧基聚丙二醇(甲基)丙烯酸酯、辛氧基聚乙二醇－聚丙二醇(甲基)丙烯酸酯等。Further, in terms of the average addition mole number of the oxygen-extended alkyl unit of the above epoxy group-containing monomer, it is preferably from 3 to 40 from the viewpoint of wettability with the adherend, preferably It is 4 to 35, particularly preferably 5 to 30. If the above average addition molar number is more than 3, better wettability with the adherend can be obtained. Further, if the average addition mole number described above is more than 40, the contamination of the adherend tends to increase. Further, the terminal of the oxygen-extended alkyl chain may be maintained as a hydroxyl group or substituted with another functional group or the like. Further, the above epoxy group-containing monomer is preferably a monomer having an ethylene oxide. By using a (meth)acrylic monomer having an oxiranyl group-containing monomer, it is possible to easily obtain better wettability with the adherend. Specific examples of the (meth)acrylic acid alkylene oxide addenda include, for example, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, and polyethylene glycol-polypropylene glycol (A). Acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, polypropylene glycol-polybutylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, B Oxypoly polyethylene glycol (meth) acrylate, butoxy polyethylene glycol (meth) acrylate, octyloxy polyethylene glycol (meth) acrylate, lauryl oxy polyethylene glycol (A Lauroxy polyethylene glycol (meth)acrylate, stearoxy polyethylene glycol (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate Ester, methoxypolypropylene glycol (meth) acrylate, octyloxy polyethylene glycol-polypropylene glycol (meth) acrylate, and the like.

為了製成可賦予使水之接觸角在上述範圍內之黏著層的丙烯酸系黏著劑，宜為含有例如以(甲基)丙烯酸烷基酯70至100重量份(宜為70至80重量份)與親水性單體1至30重量份(宜為20至30重量份)所得之丙烯酸系聚合物，此時，以親水性單體而言，宜為從(甲基)丙烯酸2－羥乙酯、N－(甲基)丙烯醯基嗎福啉、及(甲基)丙烯醯胺中選出之任一者之1種或組合2種以上而使用。此外，亦宜為含有以(甲基)丙烯酸2－乙基己酯70至80重量份與親水性單體20至30重量份所得之丙烯酸系聚合物，或宜為含有以丙烯酸丁酯90至100重量份與親水性單體1至10重量份所得之丙烯酸系聚合物。另外，聚合方法並無特別限制，可採用例如溶液聚合、乳化聚合等一般的聚合方法。此外，以聚合起始劑而言，可使用例如偶氮系起始劑、過氧化物系起始劑等周知的聚合起始劑。如此操作所得之丙烯酸系聚合物的重量平均分子量(Mw)，通常為30萬至200萬，宜為50萬至170萬。若Mw未達30萬時，則會變得難以獲得作為黏著劑的凝集力，有耐熱性或耐久性降低的傾向；另一方面，若超過200萬時，則會變為高黏度，而有使黏著薄片變得難以形成的傾向。In order to form an acrylic adhesive which can impart an adhesive layer having a contact angle of water within the above range, it is preferably contained in an amount of, for example, 70 to 100 parts by weight (preferably 70 to 80 parts by weight) based on the alkyl (meth)acrylate. 1 to 30 parts by weight (preferably 20 to 30 parts by weight) of the obtained acrylic polymer with respect to the hydrophilic monomer, and in this case, in the case of a hydrophilic monomer, it is preferably 2-hydroxyethyl (meth)acrylate And one or a combination of two or more selected from the group consisting of N-(meth)acryloyl fluorenyl porphyrin and (meth) acrylamide. Further, it is also preferably an acrylic polymer obtained by containing 70 to 80 parts by weight of 2-ethylhexyl (meth)acrylate and 20 to 30 parts by weight of the hydrophilic monomer, or preferably containing butyl acrylate 90 to 100 parts by weight of the acrylic polymer obtained from 1 to 10 parts by weight of the hydrophilic monomer. Further, the polymerization method is not particularly limited, and a general polymerization method such as solution polymerization or emulsion polymerization can be employed. Further, as the polymerization initiator, a known polymerization initiator such as an azo initiator or a peroxide initiator can be used. The weight average molecular weight (Mw) of the acrylic polymer obtained in this manner is usually from 300,000 to 2,000,000, preferably from 500,000 to 1.7 million. When the Mw is less than 300,000, it becomes difficult to obtain a cohesive force as an adhesive, and heat resistance and durability tend to be lowered. On the other hand, when it exceeds 2 million, it becomes a high viscosity, and there is The tendency to make the adhesive sheet difficult to form.

此外，製作遮罩帶後，為了使黏著層側面之水的接觸角變為未達100°，此外，為了使水的接觸角未達100°的黏著層側面之水的接觸角變得更小，可對遮罩帶的側面進行表面處理。以相關的表面處理而言，可列舉如易接著處理、親水性材料(例如，光觸媒)的塗布等。以光觸媒而言，可，列舉出例如二氧化鈦(TiO2 )、氧化鋅(ZnO)、二氧化錫(SnO2 )、鈦酸鍶(SrTiO3 )、三氧化鎢(WO3 )、三氧化二鉍(Bi2 O3 )、三氧化二鐵(Fe2 O3 )等光半導體，可將這些化合物1種或2種以上組合使用。另外，二氧化鈦有銳鈦礦型與金紅石型，在本實施態樣中可使用任一者，但以銳鈦礦型為較適合。使用此等光觸媒，基材的濕潤性會更加提高，而可更確實地獲得膜厚均一的薄膜。Further, after the mask tape is formed, in order to make the contact angle of the water on the side of the adhesive layer less than 100°, the contact angle of the water on the side of the adhesive layer in which the water contact angle is less than 100° is made smaller. The surface of the mask strip can be surface treated. Examples of the related surface treatment include, for example, easy adhesion treatment, application of a hydrophilic material (for example, photocatalyst), and the like. Examples of the photocatalyst include, for example, titanium oxide (TiO 2 ), zinc oxide (ZnO), tin dioxide (SnO 2 ), barium titanate (SrTiO 3 ), tungsten trioxide (WO 3 ), and antimony trioxide. An optical semiconductor such as (Bi 2 O 3 ) or a ferric oxide (Fe 2 O 3 ) may be used alone or in combination of two or more. Further, titanium dioxide has an anatase type and a rutile type, and any of the present embodiment may be used, but an anatase type is suitable. By using such a photocatalyst, the wettability of the substrate is further improved, and a film having a uniform film thickness can be obtained more surely.

此外，在黏著劑中，因應必要可含有交聯劑或界面活性劑。以交聯劑而言，可使用該技術領域中通常使用之交聯劑，可列舉出例如異氰酸酯系交聯劑、環氧系交聯劑、唑啉(oxazoline)系交聯劑、氮丙啶系交聯劑、金屬鉗合物系交聯劑等。其中，以異氰酸酯系交聯劑、環氧系交聯劑較為適合。交聯劑的調配量，相對於上述聚合物100重量份(固體成分)，通常為0.01至10重量份，宜為1至6重量份。若交聯劑之調配量過低時，則會使交聯密度下降，而有難以獲得足夠強度的傾向；另一方面，若過多時，則會使黏著力下降，而有製造時之作業性變差的傾向。此外，以界面活性劑而言，可列舉如聚氧伸乙基聚氧伸丙基二醇(polyoXyethylene polyoxypropylene glycol)、聚氧伸乙基烷基醚(polyoxyethylene alkyl ether)、聚氧伸乙基烷基苯基醚(polyoxyethylene alkyl phenyl ether)、山梨醇酐脂肪酸酯(sorbitan fatty acid ester)、聚氧伸乙基脂肪酸酯等非離子界面活性劑。其中，從起泡少、可漂亮地形成糊面的觀點來看，以聚氧伸乙基聚氧伸丙基二醇較為合適，在商業上可取得EPAN(商品名，第一工業製藥股份公司製)。界面活性劑的調配量，相對於上述聚合物100重量份(固體成分)，通常為0.001至1重量份，宜為0.01至0.1重量份。Further, in the adhesive, a crosslinking agent or a surfactant may be contained as necessary. As the crosslinking agent, a crosslinking agent generally used in the technical field can be used, and examples thereof include an isocyanate crosslinking agent and an epoxy crosslinking agent. An oxazoline-based crosslinking agent, an aziridine-based crosslinking agent, and a metal-nose crosslinking agent. Among them, an isocyanate crosslinking agent or an epoxy crosslinking agent is suitable. The amount of the crosslinking agent to be added is usually 0.01 to 10 parts by weight, preferably 1 to 6 parts by weight, based on 100 parts by weight (solid content) of the above polymer. When the amount of the crosslinking agent is too low, the crosslinking density is lowered, and it tends to be difficult to obtain sufficient strength. On the other hand, if the amount is too large, the adhesion is lowered, and workability at the time of manufacture is caused. The tendency to change. Further, examples of the surfactant include polyoXyethylene polyoxypropylene glycol, polyoxyethylene alkyl ether, and polyoxyethylene alkylene oxide. Nonionic surfactants such as polyoxyethylene alkyl phenyl ether, sorbitan fatty acid ester, and polyoxyethylene fatty acid ester. Among them, from the viewpoint of less foaming and a beautiful formation of a paste, it is suitable to use polyoxyalkylene extended polypropyl propylene glycol, and commercially available EPPN (trade name, First Industrial Pharmaceutical Co., Ltd.) system). The amount of the surfactant to be added is usually 0.001 to 1 part by weight, preferably 0.01 to 0.1 part by weight, based on 100 parts by weight (solid content) of the above polymer.

再者，於黏著劑中，亦可因應必要而添加增黏劑、抗老化劑(age resister)、充填劑、顏料、著色劑等。以增黏劑而言，可列舉如松香系樹脂、萜烯系樹脂、脂肪族系石油樹脂、芳香族系石油樹脂、共聚系石油樹脂、脂環族系石油樹脂等。Further, in the adhesive, a tackifier, an age resister, a filler, a pigment, a colorant, or the like may be added as necessary. Examples of the tackifier include rosin-based resins, terpene-based resins, aliphatic petroleum resins, aromatic petroleum resins, copolymerized petroleum resins, and alicyclic petroleum resins.

(第2實施型態)(Second embodiment)

第2圖(b)係顯示第2實施型態相關之基板用遮罩帶的剖面圖。本實施型態相關之基板用遮罩帶20，在黏著層3的被黏面上形成隔離膜5這點，與上述第1實施型態之基板用遮罩帶10為相異，而基材1及黏著層3的構造則與上述實施型態中的說明相同。另外，隔離膜，可因應使用目的而適當裝設。以隔離膜而言，可列舉如在上述基材所示示之物。隔離膜的表面，為了提升從黏著層的剝離性，可因應必要而實施矽酮處理、長鏈烷基處理、氟處理等離型處理。此外，隔離膜的厚度，通常為10至300 μ m，宜為20至100 μ m，較宜為38至75 μ m。Fig. 2(b) is a cross-sectional view showing a mask tape for a substrate according to a second embodiment. The mask tape 20 for a substrate according to this embodiment differs from the mask tape 10 of the first embodiment described above in that the separator 5 is formed on the adherend surface of the adhesive layer 3, and the substrate is different from the substrate. 1 and the structure of the adhesive layer 3 are the same as those described in the above embodiment. Further, the separator may be appropriately installed depending on the purpose of use. Examples of the separator include those shown in the above substrate. In order to improve the peeling property from the adhesive layer, the surface of the separator may be subjected to a release treatment such as an anthrone treatment, a long-chain alkyl treatment, or a fluorine treatment as necessary. Further, the thickness of the separator is usually 10 to 300 μm, preferably 20 to 100 μm, and more preferably 38 to 75 μm.

其次，針對本發明之基板用遮罩帶的製造方法加以說明。基板用遮罩帶，一般而言，係可藉由將上述黏著劑塗布於基材上並乾燥以形成黏著層，或是將上述黏著劑塗布於剝離紙等其他基材上並乾燥以形成黏著層，然後將其貼合至基材上而製造。此外，如第1圖所示之基板用遮罩帶，係可藉由例如在基材之一方之面形成黏著層後，將黏著層的表面與基材之另一方之面重疊並捲成筒狀而製造。另外，在基材上塗布黏著劑時，慣用之塗布機，可使用例如凹版輥輪塗布機(gravure roll coater)、反轉輥輪塗布機(reverse roll coater)、接觸輥輪塗布機(kiss roll coater)、浸式輥輪塗布機(dip roll coater)、棒塗機(bar coater)、刀塗機(knife coater)、噴塗機(spray coater)、噴出擠壓式塗布機(fountain die coater)等。此時，乾燥後之黏著層厚度，通常以成為3至100 μ m，宜成為5至60 μ m，較宜成為10至40 μ m的方式而塗布黏著劑。Next, a method of manufacturing the mask tape for a substrate of the present invention will be described. A mask tape for a substrate is generally formed by applying the above-mentioned adhesive to a substrate and drying to form an adhesive layer, or applying the above adhesive to other substrates such as release paper and drying to form an adhesive. The layer is then fabricated by attaching it to a substrate. Further, the mask tape for a substrate as shown in FIG. 1 can be formed by, for example, forming an adhesive layer on one side of the substrate, and overlapping the surface of the adhesive layer with the other surface of the substrate and winding it into a can. Made in shape. Further, when the adhesive is applied to the substrate, a conventional coater may be, for example, a gravure roll coater, a reverse roll coater, or a contact roll coater (kiss roll). Coater), dip roll coater, bar coater, knife coater, spray coater, fountain die coater, etc. . At this time, the thickness of the adhesive layer after drying is usually applied in an amount of 3 to 100 μm, preferably 5 to 60 μm, and more preferably 10 to 40 μm.

本發明之基板用遮罩帶，係使用於：在例如將有機電致發光材料、導電性材料等流動性材料以例如噴嘴塗布法等依序塗布於有機電致發光用基板上並將薄膜重疊塗布而製作有機電致發光顯示器(顯示面板)的有機電致發光顯示器(顯示面板)製造工程中，於塗布流動性材料前，先貼附於基板上的不需塗布區域。The mask tape for a substrate of the present invention is used, for example, by applying a fluid material such as an organic electroluminescent material or a conductive material to a substrate for an organic electroluminescence in a stepwise coating method, for example, and overlapping the films. In an organic electroluminescence display (display panel) manufacturing process in which an organic electroluminescence display (display panel) is produced by coating, a coating region which is attached to a substrate before application of a fluid material is applied.

藉由使用本發明的基板用遮罩帶，而可使塗布於遮罩帶周圍(側部)的流動性材料之薄膜(塗膜)不會產生非期望性的厚度增加，並可避免以該薄膜(塗膜)之非期望性厚度增加為原因所導致的問題(例如，在有機電致發光顯示器的陰極斷線或是在陰極中對於來自外部之水分或氧氣的遮蔽性下降等)。By using the masking tape for a substrate of the present invention, a film (coating film) of a fluid material applied around the side (side portion) of the mask tape can be prevented from being undesirably increased in thickness, and can be avoided. The undesired thickness increase of the film (coating film) is a cause of the problem (for example, a cathode breakage of the organic electroluminescence display or a decrease in the shielding property of moisture or oxygen from the outside in the cathode, etc.).

上述之「有機電致發光材料」，係指例如聚對苯乙烯(poly(p－phenylene vinylene)，即PPV)、聚對苯乙烯衍生物、聚噻吩(polythiophene)、聚噻吩衍生物、聚茀(polyfluorene)衍生物、聚對苯(poly(p－phenylene)，即PPP)、聚對苯衍生物、咔唑(carbazole)衍生物、聚矽烷(polysilane)系聚合物等周知之發光聚合物分散或溶解於溶媒中而成的分散液或溶液；此外，「導電性材料」，係指聚乙烯二氧噻吩(polyethylenedioxythiophene，即PEDOT)－聚苯乙烯磺酸(poly styrene sulfonic acid，即PSS)、聚苯胺(polyaniline，即PA)－聚苯乙烯磺酸、PTPDES(亦即下述式所示之聚合物： )等周知之導電性聚合物分散或溶解於溶媒中而成的分散液或溶液。此等分散液或溶液，一般而言，含有至少0.1重量%以上，宜為0.5重量%以上，更宜為1重量%以上之濃度的發光聚合物或導電性聚合物。The above-mentioned "organic electroluminescent material" means, for example, poly(p-phenylene vinylene) (PPV), polyparaphenylene derivative, polythiophene, polythiophene derivative, polyfluorene. (Polyfluorene) derivatives, poly(p-phenylene) (PPP), polyparaphenylene derivatives, carbazole derivatives, polysilane polymers, etc. Or a dispersion or solution obtained by dissolving in a solvent; and "conductive material" means polyethylene dioxythiophene (PEDOT)-polystyrene sulfonic acid (PSS), Polyaniline (PA) - polystyrene sulfonic acid, PTPDES (also known as the following formula: A dispersion or solution in which a known conductive polymer is dispersed or dissolved in a solvent. Such dispersions or solutions generally contain at least 0.1% by weight, preferably 0.5% by weight or more, more preferably 1% by weight or more of the luminescent polymer or conductive polymer.

使用本發明之基板用遮罩帶製作有機電致發光顯示器時之一實施態樣係如下所述。One embodiment of the method of producing an organic electroluminescence display using the mask strip of the substrate of the present invention is as follows.

本態樣相關之有機電致發光顯示器，係具有：一對之對向電極、與配置於該電極間之一層以上之有機層。The organic electroluminescence display according to this aspect has a pair of counter electrodes and an organic layer disposed on one or more layers between the electrodes.

首先，準備基板。以基板而言，使用例如玻璃基板、塑膠基板等透明基板。此外，基板，亦可藉由例如氧化銦錫(ITO)等而經施行所指定之圖案成形(patterning)。其次，於室溫至80℃，以本發明之基板用遮罩帶將基板之不需塗布區域(非形成薄膜之區域)予以遮蔽。First, a substrate is prepared. For the substrate, a transparent substrate such as a glass substrate or a plastic substrate is used. Further, the substrate may be subjected to patterning as specified by, for example, indium tin oxide (ITO) or the like. Next, at room temperature to 80 ° C, the substrate-free masking tape of the substrate of the present invention is used to shield the uncoated region (the region where the film is not formed).

接下來，藉由噴嘴塗布法將以聚乙烯二氧噻吩－聚苯乙烯磺酸分散於水中所成的塗布液塗布於基板上，而形成厚度為50nm至100nm左右的均勻薄膜。Next, a coating liquid obtained by dispersing polyethylene dioxythiophene-polystyrene sulfonic acid in water is applied onto a substrate by a nozzle coating method to form a uniform film having a thickness of about 50 nm to 100 nm.

繼而，剝離基板用遮罩帶後將基板加熱乾燥，或是在將基板加熱乾燥後剝離基板用遮罩帶，而形成電洞傳輸層。Then, after peeling off the substrate mask tape, the substrate is heated and dried, or after the substrate is heated and dried, the substrate mask tape is peeled off to form a hole transport layer.

其次，於室溫或80℃，以本發明之基板用遮罩帶將基板之不需塗布區域(非形成薄膜之區域)予以遮蔽。Next, at room temperature or at 80 ° C, the substrate-free masking tape of the substrate of the present invention is used to shield the uncoated region (the region where the film is not formed).

接下來，藉由噴嘴塗布法將有機電致發光材料(R、G、B)塗布於基板上，剝離基板用遮罩帶後將基板加熱乾燥，或是在將基板加熱乾燥後剝離基板用遮罩帶，而形成厚度為60nm至80nm左右的均勻發光層。Next, the organic electroluminescent material (R, G, B) is applied onto the substrate by a nozzle coating method, the substrate is peeled off from the substrate, and the substrate is heated and dried, or the substrate is peeled off after heating and drying the substrate. The cover tape is formed to form a uniform light-emitting layer having a thickness of about 60 nm to 80 nm.

然後，將基板移至真空蒸鍍機中，藉由蒸鍍而在上述發光層上形成膜厚100至300nm左右的陰極。接下來，藉由接著劑而將基板用遮罩帶的貼附部分予以封裝。如此地操作，而獲得有機電致發光顯示器。Then, the substrate is transferred to a vacuum vapor deposition machine, and a cathode having a thickness of about 100 to 300 nm is formed on the light-emitting layer by vapor deposition. Next, the substrate is sealed with the attached portion of the mask tape by an adhesive. Operating in this way, an organic electroluminescent display is obtained.

本發明之基板用遮罩帶，並非限定使用於如上述之有機電致發光顯示器的製造流程中，亦可適用於液晶、有機薄膜太陽電池、電漿顯示器等的製造流程中。亦即，不僅於有機電致發光用基板，在液晶用基板、有機薄膜太陽電池用基板、電漿顯示器用基板、半導體晶圓、光碟用基板等各種基板上，當塗布形成流動性材料之薄膜(塗膜)時，可適宜使用於作為將基板上之不需塗布區域予以遮蔽的遮罩帶。The mask tape for a substrate of the present invention is not limited to use in the manufacturing process of the above-described organic electroluminescence display, and can be applied to a manufacturing process of a liquid crystal, an organic thin film solar cell, a plasma display or the like. In other words, a film forming a fluid material is applied to various substrates such as a substrate for a liquid crystal, a substrate for an organic thin film solar cell, a substrate for a plasma display, a semiconductor wafer, and a substrate for a disk. In the case of (coating film), it can be suitably used as a masking tape which shields the uncoated area on a board|substrate.

此外，本發明之基板用遮罩帶，尤適合於至少具有將由使用水系溶媒之溶液分散液所構成之流動性材料塗布至基板上之步驟的製造流程(有機電致發光顯示器、液晶、有機薄膜太陽電池、電漿顯示器等的製造流程)中。亦即，在將使用水系溶媒的流動性材料予以塗布以形成薄膜時，可特別有效地抑制經塗布於遮罩帶周圍(側部)的流動性材料薄膜(塗膜)中之非期望性厚度增加。又，此處所謂的「水系溶媒」，係意指水或以水為主體之溶媒，具體而言，可列舉如一般的水；純水；蒸餾水；或離子交換水等；或是相對於水以未達50重量%之範圍內而將碳數1至7(宜為碳數1至4)的脂肪族醇類、酮類等親水性有機溶媒予以混合者。Further, the mask tape for a substrate of the present invention is particularly suitable for a manufacturing process (organic electroluminescence display, liquid crystal, organic film) having at least a step of applying a fluid material composed of a solution dispersion using an aqueous solvent to a substrate. In the manufacturing process of solar cells, plasma displays, etc.). That is, when a fluid material using an aqueous solvent is applied to form a film, the undesired thickness in the film (coating film) of the fluid material applied to the periphery (side portion) of the mask tape can be particularly effectively suppressed. increase. In addition, the term "aqueous solvent" as used herein means water or a solvent mainly composed of water, and specific examples thereof include water, pure water, distilled water, or ion-exchanged water, or water. A hydrophilic organic solvent such as an aliphatic alcohol or a ketone having a carbon number of 1 to 7 (preferably having a carbon number of 1 to 4) is mixed in a range of less than 50% by weight.

本發明之基板用遮罩帶，不僅使用於以噴嘴塗布法在基板上形成薄膜之情形，亦可適用於以噴墨印刷法或旋塗法等其他周知的方法在基板上進行形成薄膜的情形。The mask tape for a substrate of the present invention can be used not only for forming a film on a substrate by a nozzle coating method but also for forming a film on a substrate by other well-known methods such as an inkjet printing method or a spin coating method. .

實施例Example

以下，藉由實施例具體地說明本發明，但本發明不限定於此等實施例。Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples.

(黏著劑之調製)(modulation of adhesive) (製造例1)(Manufacturing Example 1)

在附有攪拌機、溫度計及反應副產物分離管的四口可分離式燒瓶(separable flask)中，置入聚碳酸酯二醇(商品名：PLACCEL CD220PL，羥值：55.1KOHmg/g，DAICEL化學工業股份公司製)200.0重量份、癸二酸19.8重量份、及作為觸媒的鈦酸四正丁酯(tetra－n－butyl titanate)0.1重量份，加入少量二甲苯以作為反應副產物之水的排出用溶劑。其次，攪拌反應液並升溫至180℃，於此溫度進行規則性的攪拌。過一段時間，辨識出水的流出分離，確認反應已經開始進行後，加熱攪拌約18小時。然後，獲得重量平均分子量49,000、分散度1.8的聚酯。Polycarbonate diol was placed in a four separable flask with a mixer, a thermometer and a reaction by-product separation tube (trade name: PLACCEL CD220PL, hydroxyl value: 55.1 KOHmg/g, DAICEL Chemical Industry) 200.0 parts by weight of the company, 19.8 parts by weight of sebacic acid, and 0.1 part by weight of tetra-n-butyl titanate as a catalyst, and a small amount of xylene was added as a by-product of water. Discharge solvent. Next, the reaction solution was stirred and heated to 180 ° C, and regular stirring was carried out at this temperature. After a while, the outflow separation of the water was recognized, and after confirming that the reaction had started, the mixture was heated and stirred for about 18 hours. Then, a polyester having a weight average molecular weight of 49,000 and a degree of dispersion of 1.8 was obtained.

繼而，相對於所得之聚酯100重量份，添加異氰酸酯系交聯劑(商品名：CORONATE HL，日本POLYURETHANE工業股份公司製)3.5重量份，而獲得聚酯系黏著劑。Then, 3.5 parts by weight of an isocyanate-based crosslinking agent (trade name: CORONATE HL, manufactured by Japan POLYURETHANE INDUSTRIAL CO., LTD.) was added to 100 parts by weight of the obtained polyester to obtain a polyester-based pressure-sensitive adhesive.

(製造例2)(Manufacturing Example 2)

在與製造例1相同的反應容器中，置入丙烯酸2－乙基己酯(2－EHA)75重量份、N－丙烯醯基嗎福啉(ACMO)25重量份、丙烯酸(AA)3重量份、丙烯酸2－羥乙酯(HEA)0.5重量份，進行一般之溶液(乙酸乙酯)聚合，獲得重量平均分子量1,100,000的丙烯酸系聚合物。In the same reaction vessel as in Production Example 1, 75 parts by weight of 2-ethylhexyl acrylate (2-EHA), 25 parts by weight of N-propylene decyl porphyrin (ACMO), and 3 parts by weight of acrylic acid (AA) were placed. A 0.5 part by weight of 2-hydroxyethyl acrylate (HEA) was subjected to polymerization in a usual solution (ethyl acetate) to obtain an acrylic polymer having a weight average molecular weight of 1,100,000.

其次，相對於所得之丙烯酸系聚合物95重量份，添加環氧系交聯劑(商品名：TETRAD C，三菱瓦斯化學工業股份公司製)1.5重量份、異氰酸酯系交聯劑(商品名：CORONATE L，日本POLYURETHANE工業股份公司製)2重量份、及非離子界面活性劑(商品名：EPAN7 10，第一工業製藥股份公司製)0.05重量份，而獲得丙烯酸系黏著劑(以下稱為「丙烯酸系黏著劑A」)。Next, 1.5 parts by weight of an epoxy-based crosslinking agent (trade name: TETRAD C, manufactured by Mitsubishi Gas Chemical Industries, Ltd.) and an isocyanate-based crosslinking agent (trade name: CORONATE) were added to 95 parts by weight of the obtained acrylic polymer. L, an amount of 0.05 parts by weight of a nonionic surfactant (trade name: EPAN7 10, manufactured by Dai-Il Pharmaceutical Co., Ltd.) was obtained in an amount of 0.05 parts by weight of a nonionic surfactant (manufactured by Japan POLYURETHANE INDUSTRIAL CO., LTD.) to obtain an acrylic adhesive (hereinafter referred to as "acrylic acid"). Adhesive A").

(製造例3)(Manufacturing Example 3)

在與製造例1相同的反應容器中，置入2－EHA90重量份、HEA3.5重量份，進行一般之溶液(乙酸乙酯)聚合，獲得重量平均分子量600,000的丙烯酸系聚合物。In the same reaction vessel as in Production Example 1, 90 parts by weight of 2-EHA and 3.5 parts by weight of HEA were placed, and a general solution (ethyl acetate) was polymerized to obtain an acrylic polymer having a weight average molecular weight of 600,000.

其次，相對於所得之丙烯酸系聚合物100重量份，添加入異氰酸酯系交聯劑(日本POLYURETHANE工業股份公司製，CORONATE HX)3.5重量份，而獲得丙烯酸系黏著劑(以下稱為「丙烯酸系黏著劑B」)。Then, 3.5 parts by weight of an isocyanate-based crosslinking agent (CORONATE HX, manufactured by Japan POLYURETHANE INDUSTRIAL CO., LTD.) was added to 100 parts by weight of the obtained acrylic polymer to obtain an acrylic adhesive (hereinafter referred to as "acrylic adhesive". Agent B").

(製造例4)(Manufacturing Example 4)

在固體成分60%的矽酮聚合物(商品名：X－40－3229，信越化學工業股份公司製)70重量份中，加入固體成分60%的矽酮聚合物(商品名：KR－3770，信越化學工業股份公司製)30重量份、固體成分5%的觸媒(商品名：CAT－PL－50T，信越化學工業股份公司製)0.5重量份、甲苯100重量份，而獲得矽酮系黏著劑。To 70 parts by weight of an anthrone polymer (trade name: X-40-3229, manufactured by Shin-Etsu Chemical Co., Ltd.) having a solid content of 60%, 60% by weight of an anthrone polymer (trade name: KR-3770, 30 parts by weight of a catalyst (trade name: CAT-PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) and 100 parts by weight of toluene (available from Shin-Etsu Chemical Co., Ltd.) to obtain an anthrone-based adhesive Agent.

(製造例5)(Manufacturing Example 5)

在與製造例1相同的反應容器中，置入丙烯酸丁酯(BA)95重量份、丙烯酸(AA)5重量份，進行一般之溶液(乙酸乙酯)聚合，獲得重量平均分子量600,000的丙烯酸系聚合物。In the same reaction vessel as in Production Example 1, 95 parts by weight of butyl acrylate (BA) and 5 parts by weight of acrylic acid (AA) were placed, and a general solution (ethyl acetate) was polymerized to obtain an acrylic acid having a weight average molecular weight of 600,000. polymer.

其次，相對於所得之丙烯酸系聚合物100重量份，添加環氧系交聯劑(商品名：TETRAD C，三菱瓦斯化學工業股份公司製)4.5重量份、異氰酸酯系交聯劑(商品名：CORONATE L，日本POLYURETHANE工業股份公司製)1重量份，而獲得丙烯酸系黏著劑(以下稱為「丙烯酸系黏著劑C」)。Next, 4.5 parts by weight of an epoxy-based crosslinking agent (trade name: TETRAD C, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and an isocyanate-based crosslinking agent (trade name: CORONATE) were added to 100 parts by weight of the obtained acrylic polymer. L, an epoxy adhesive (hereinafter referred to as "acrylic adhesive C") was obtained in an amount of 1 part by weight, manufactured by Japan POLYURETHANE INDUSTRIAL CO., LTD.

(實施例1)(Example 1)

在下述矽酮處理隔離膜之矽酮處理面，將製造例1所得之聚酯系黏著劑以厚度成為15 μ m之方式塗布，在130℃×3分鐘的條件下乾燥。在乾燥後之黏著面上，將一方之面具有抗靜電層且另一方之面具有電暈處理面的聚酯薄膜(商品名：T100N38，厚度38 μ m，三菱化學聚酯股份公司製)之電暈處理面貼合上，而得到遮罩帶。將所得之遮罩帶載置於平滑玻璃板上，從基材側以修整用刀片切割，作為樣本。另外，修整用刀片，使用過1次的刀刃就不再使用。The polyester-based pressure-sensitive adhesive obtained in Production Example 1 was applied to a ketone-treated surface of the following fluorenone-treated separator to a thickness of 15 μm, and dried at 130 ° C for 3 minutes. On the adhesive surface after drying, a polyester film (trade name: T100N38, thickness: 38 μm, manufactured by Mitsubishi Chemical Polyester Co., Ltd.) having an antistatic layer on one side and a corona-treated surface on the other side The corona-treated surface is attached to each other to obtain a mask tape. The obtained mask tape was placed on a smooth glass plate, and cut from a substrate side by a trimming blade as a sample. In addition, the trimming blade is no longer used when the blade is used once.

<矽酮處理隔離膜的製造>(離型塗布劑的製作)在聚二甲基矽氧烷(商品名：KS－3601，信越化學工業股份公司製)100重量份中，加入乙炔系反應控制劑(商品名：CAT PLR－1，信越化學工業股份公司製)2重量份、乙炔系反應控制劑(商品名：CAT PLR－2，信越化學工業股份公司製)1重量份、溶劑(商品名：正己烷，丸善股份公司製)、溶劑(商品名：正庚烷，東亞合成股份公司製)並攪拌20分鐘，再加入觸媒(商品名：CAT－PL－50T，信越化學工業股份公司製)5重量份並攪拌10分鐘，而獲得矽酮塗液。<Production of an anthrone treatment separator> (Preparation of a release coating agent) In 100 parts by weight of polydimethylsiloxane (trade name: KS-3601, manufactured by Shin-Etsu Chemical Co., Ltd.), acetylene reaction control was added. (product name: CAT PLR-1, manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by weight, acetylene-based reaction control agent (trade name: CAT PLR-2, manufactured by Shin-Etsu Chemical Co., Ltd.), 1 part by weight, solvent (product name) : hexane (manufactured by Maruzen Co., Ltd.), solvent (trade name: n-heptane, manufactured by Toagosei Co., Ltd.) and stirred for 20 minutes, and then added catalyst (trade name: CAT-PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd. 5 parts by weight and stirred for 10 minutes to obtain an anthrone coating solution.

(離型薄膜的製作)在單面電暈處理聚酯薄膜(商品名：S－105，厚50 μ m，東麗股份公司製)之電暈處理面上，以凹版印刷法塗布上述矽酮塗液，以140℃×1分鐘乾燥後，獲得離型聚酯薄膜(矽酮離型層之乾燥後重量為0.07g/cm2 )。(Production of Release Film) The above-mentioned anthrone was applied by gravure printing on a corona-treated surface of a single-sided corona-treated polyester film (trade name: S-105, thickness: 50 μm, manufactured by Toray Co., Ltd.). The coating liquid was dried at 140 ° C for 1 minute to obtain a release polyester film (the dry weight of the anthrone release layer was 0.07 g/cm 2 ).

(實施例2)(Example 2)

除了使用製造例2所得之丙烯酸系黏著劑A，並將黏著劑之乾燥條件變更為140℃×3分鐘以外，其餘藉由與實施例1同樣的方法而獲得遮罩帶。A mask tape was obtained in the same manner as in Example 1 except that the acrylic pressure-sensitive adhesive A obtained in Production Example 2 was used, and the drying conditions of the pressure-sensitive adhesive were changed to 140 ° C for 3 minutes.

(實施例3)(Example 3)

除了將聚酯薄膜(商品名：S－10，厚38μm，東麗股份公司製)作為貼合於黏著面之基材，並在遮罩帶背面上塗布表面處理劑(商品名：醇系表面處理劑，丸昌產業股份公司製)及光觸媒(商品名：M－5TYPE醇系溶劑，丸昌產業股份公司製)以外，其餘藉由與實施例2同樣的方法而獲得遮罩帶。A polyester film (trade name: S-10, thickness: 38 μm, manufactured by Toray Industries, Inc.) was used as a substrate to be adhered to the adhesive surface, and a surface treatment agent was applied on the back surface of the mask tape (trade name: alcohol-based surface). A masking tape was obtained in the same manner as in Example 2 except that the treatment agent (manufactured by Maruzen Co., Ltd.) and photocatalyst (trade name: M-5 TYPE alcohol solvent, manufactured by Maruzen Co., Ltd.).

(實施例4)(Example 4)

除了使用製造例3所得之丙烯酸系黏著劑B，將黏著劑的乾燥條件定為130℃×1分鐘，並與實施例1同樣地以修整用刀片切割後，在遮罩帶側面上塗布表面處理劑(商品名：醇系表面處理劑，丸昌產業股份公司製)及光觸媒(商品名：M－5TYPE醇系溶劑，丸昌產業股份公司製)以外，其餘藉由與實施例1同樣的方法而獲得遮罩帶。The acrylic adhesive B obtained in Production Example 3 was used, and the drying condition of the adhesive was set to 130 ° C for 1 minute, and after cutting with a dressing blade in the same manner as in Example 1, the surface treatment was applied to the side of the mask tape. The same procedure as in Example 1 was carried out except that the agent (trade name: alcohol-based surface treatment agent, manufactured by Maruzen Co., Ltd.) and photocatalyst (trade name: M-5 TYPE alcohol solvent, manufactured by Maruzen Co., Ltd.) were obtained. Mask tape.

(實施例5)(Example 5)

除了使用製造例5所得之丙烯酸系黏著劑C，將黏著劑之乾燥條件變更為140℃×3分鐘以外，其餘藉由與實施例1同樣的方法而獲得遮罩帶。A mask tape was obtained in the same manner as in Example 1 except that the acrylic adhesive C obtained in Production Example 5 was used, and the drying conditions of the adhesive were changed to 140 ° C × 3 minutes.

(比較例1)(Comparative Example 1)

除了使用製造例3所得之丙烯酸系黏著劑B，將黏著劑之乾燥條件定為130℃×1分鐘以外，其餘藉由與實施例1同樣的方法而獲得遮罩帶。A mask tape was obtained in the same manner as in Example 1 except that the acrylic pressure-sensitive adhesive B obtained in Production Example 3 was used, and the drying conditions of the pressure-sensitive adhesive were set to 130 ° C for 1 minute.

(比較例2)(Comparative Example 2)

除了在一方之面具有抗靜電層且另一方之面具有電暈處理面的聚酯薄膜(商品名：T100N38，厚度38 μ m，三菱化學聚酯股份公司製)之電暈處理面上，依序塗布下述之底塗劑與製造例4所得之矽酮系黏著劑，將底塗劑之乾燥條件定為120℃×2分鐘，將黏著劑之乾燥條件定為100℃×5分鐘，並將聚酯薄膜(商品名：S－10，厚38μm，東麗股份公司製)貼合於黏著面以外，其餘藉由與實施例1同樣的方法而獲得遮罩帶。A corona-treated surface of a polyester film (trade name: T100N38, thickness 38 μm, manufactured by Mitsubishi Chemical Polyester Co., Ltd.) having an antistatic layer on one side and a corona-treated surface on the other side The undercoating agent described below and the anthrone-based adhesive obtained in Production Example 4 were applied, and the drying conditions of the primer were set to 120 ° C for 2 minutes, and the drying conditions of the adhesive were set to 100 ° C × 5 minutes. A masking tape was obtained by the same method as in Example 1 except that a polyester film (trade name: S-10, thickness: 38 μm, manufactured by Toray Industries, Inc.) was bonded to the adhesive surface.

<底塗劑的調製>在固體成分30%的矽酮聚合物(商品名：X－40－3501，信越化學工業股份公司製)100重量份中，加入固體成分5%的觸媒(商品名：CAT－PL－50T，信越化學工業股份公司製)0.5重量份、己烷130重量份、及甲基乙基酮130重量份，而獲得底塗劑。<Preparation of a primer> A catalyst having a solid content of 5% (product name) is added to 100 parts by weight of an anthrone polymer (trade name: X-40-3501, manufactured by Shin-Etsu Chemical Co., Ltd.) having a solid content of 30%. : CAT-PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.5 parts by weight, 130 parts by weight of hexane, and 130 parts by weight of methyl ethyl ketone, to obtain a primer.

(比較例3)(Comparative Example 3)

除了將聚酯薄膜(商品名：S－10，厚38 μ m，東麗股份公司製)作為貼合於黏著面之基材以外，其餘藉由與實施例2同樣的方法而獲得遮罩帶。A masking tape was obtained in the same manner as in Example 2 except that a polyester film (trade name: S-10, thickness: 38 μm, manufactured by Toray Industries, Inc.) was used as the substrate to be bonded to the adhesive surface. .

(比較例4)(Comparative Example 4)

除了將厚度40 μ m且單面施以電暈處理之聚丙烯．聚乙烯混合膜(聚丙烯：聚乙烯＝90：10(重量比))作為貼合於黏著面之基材，並使電暈處理面貼合於黏著劑以外，其餘藉由與實施例2同樣的方法而獲得遮罩帶。In addition to the thickness of 40 μ m and one side of the corona treated polypropylene. A polyethylene mixed film (polypropylene: polyethylene = 90:10 (weight ratio)) was attached to the base material of the adhesive surface, and the corona-treated surface was bonded to the adhesive, and the rest was the same as in Example 2. The method is to obtain a mask strip.

[評估試驗][evaluation test]

(1)水的接觸角在玻璃板上，使被驗面朝上並將遮罩帶放平固定住後，以裝有內徑0.4mm不鏽鋼製針的玻璃製注射器將3 μ g的蒸餾水附著於被驗面，於附著後20秒內，在23℃×50% RH下使用接觸角計(商品名：CA－X型，協和界面科學股份公司製)依據θ/2法測定接觸角。接觸角係測定出10個值，去除上下2個值後的平均值。另外，因黏著層側面厚度較薄而無法直接測定接觸角，當遮罩帶有隔離膜時，如上述般地測定隔離膜剝離後之黏著層被黏面的接觸角，以作為黏著層側面之水的接觸角。此外，當遮罩帶糊面接觸到遮罩帶背面而形成筒狀物時，測定從遮罩帶背面將遮罩帶剝離後之黏著層被黏面的接觸角，以作為黏著層側面之水的接觸角。在光觸媒塗布於遮罩帶側面之實施例4的情形中，於將隔離膜剝離後之被黏面上同樣塗布光觸媒，測定該面之接觸角以作為黏著層側面之水的接觸角。評估結果顯示於表1。(1) The contact angle of water is on the glass plate, and the face is facing up and the mask tape is flattened, and 3 μg of distilled water is attached to a glass syringe equipped with a stainless steel needle having an inner diameter of 0.4 mm. The contact angle was measured in accordance with the θ/2 method using a contact angle meter (trade name: CA-X type, manufactured by Kyowa Interface Science Co., Ltd.) at 23 ° C × 50% RH for 20 seconds after the adhesion. The contact angle was measured by 10 values, and the average value after removing the upper and lower values was removed. In addition, since the thickness of the side of the adhesive layer is thin, the contact angle cannot be directly measured. When the mask is provided with the separator, the contact angle of the adhesive surface of the adhesive layer after peeling off the separator is measured as described above, as the side of the adhesive layer. The contact angle of water. Further, when the masked paste surface contacts the back surface of the mask tape to form a tubular body, the contact angle of the adhesive layer of the adhesive layer after peeling off the mask tape from the back surface of the mask tape is measured as the water on the side of the adhesive layer. Contact angle. In the case of Example 4 in which the photocatalyst was applied to the side of the mask tape, the photocatalyst was also applied to the adherend surface after the separator was peeled off, and the contact angle of the face was measured as the contact angle of the water on the side of the adhesive layer. The evaluation results are shown in Table 1.

(2)遮罩帶側面之濕潤性實驗以使甲苯不會停留在玻璃(1.3mm×65mm×165mm的顯微鏡載玻片，MATSUNAMI股份公司製)之非錫接觸面之同一處的方式將玻璃傾斜，並以使甲苯不會碰觸到玻璃以外之部份的方式將甲苯倒出且洗淨，將遮罩帶貼上於自然乾燥面，以裝有內徑0.8mm不鏽鋼製針的玻璃製注射器將0.5 μ g之水分散液型之導電性材料(商品名：Bayer P VP CH 8000，Bayer股份公司製)附著於距離測定面為1mm之處。在23℃×50% RH下放置24小時，之後將遮罩帶剝離，測定於遮罩帶側面擴散之導電性材料的幅度。幅度係測定5個值的平均值。亦即，第3圖(a)係貼上遮罩帶T，滴下水分散液型之導電性材料32，在放置24小時後之時間點，從上方觀察玻璃板30之測定面31的模式圖。第3圖(b)為放置24小時後，已將遮罩帶T剝離之狀態的模式圖。上述「於遮罩帶側面擴散之導電性材料的幅度」，係指在第3圖(b)的狀態下，導電性材料32之與遮罩帶T接觸側之最大幅部(W1)的幅度。(2) Wetness test on the side of the mask strip so that the toluene does not stay in the same place as the non-tin contact surface of the glass (1.3 mm × 65 mm × 165 mm microscope slide, manufactured by MATSUNAMI Co., Ltd.) And toluene was poured out and washed in such a manner that toluene did not touch the glass, and the mask tape was attached to the natural dry surface to a glass syringe equipped with a stainless steel needle having an inner diameter of 0.8 mm. 0.5 μg of an aqueous dispersion type conductive material (trade name: Bayer P VP CH 8000, manufactured by Bayer AG) was attached to a distance of 1 mm from the measurement surface. After standing at 23 ° C × 50% RH for 24 hours, the mask tape was peeled off, and the width of the conductive material diffused on the side of the mask tape was measured. The amplitude is the average of 5 values determined. In other words, in Fig. 3(a), the mask tape T is attached, and the water-dispersion type conductive material 32 is dropped, and the pattern of the measurement surface 31 of the glass plate 30 is observed from above at a time point after standing for 24 hours. . Fig. 3(b) is a schematic view showing a state in which the mask tape T has been peeled off after being left for 24 hours. The above-mentioned "amplitude of the conductive material diffused on the side of the mask tape" means the amplitude of the maximum width (W1) of the conductive material 32 on the side in contact with the mask tape T in the state of Fig. 3(b). .

如此測定之流動性材料的幅度(W1)，係將大於3mm者判斷為良好，幅度為3mm以下者判斷為不良。The amplitude (W1) of the fluid material thus measured was judged to be good if it was larger than 3 mm, and was judged to be bad when the amplitude was 3 mm or less.

評估結果顯示於表1。The evaluation results are shown in Table 1.

(3)遮罩帶背面之濕潤性實驗在平滑的板上，使被驗面朝上並將遮罩帶固定住，以2ml之聚乙烯製滴管(商品名：Code No.1－4656－01，AS ONE股份公司製)將水分散液型之導電性材料(商品名：Bayer P VP CH 8000，Bayer股份公司製)滴下1滴於被驗面，依照以下的基準對於傾斜45°時導電性材料是否會滾落進行評估。評估結果顯示於表1。(3) Wetting test on the back side of the mask tape On a smooth plate, the face to be tested is facing up and the mask tape is fixed, and a 2 ml polyethylene dropper (trade name: Code No. 1-4656- 01, AS ONE Co., Ltd.) A water-dispersible conductive material (trade name: Bayer P VP CH 8000, manufactured by Bayer AG) was dropped by one drop on the surface to be inspected, and it was electrically conductive when tilted at 45° according to the following criteria. Whether the material will roll off for evaluation. The evaluation results are shown in Table 1.

良好(○)：不會滾落不良(×)：會滾落Good (○): It won't roll off badly (×): it will roll off

(4)遮罩帶側部之薄膜的高度使用以下的方法，測定遮罩帶側部之薄膜的高度。(4) Height of film on the side of the mask tape The height of the film on the side of the mask tape was measured by the following method.

首先，在玻璃基板或透明塑膠基板上形成ITO膜後，將ITO膜使用光微影(photolithography)技術進行圖案成形(patterming)，而形成複數條之條紋狀的第1電極。此第1電極相當於陽極。First, after forming an ITO film on a glass substrate or a transparent plastic substrate, the ITO film is patterned by photolithography to form a plurality of stripe-shaped first electrodes. This first electrode corresponds to the anode.

其次，使用光微影等形成電絕緣性的隔間壁(bank)，填入上述各第1電極間。作為隔間壁的材料，使用例如丙烯酸系樹脂、環氧樹脂、聚醯亞胺等有機材料或液狀玻璃等無機材料。Next, an electrically insulating partition wall is formed by using photolithography or the like, and filled between the first electrodes. As the material of the partition wall, an organic material such as an acrylic resin, an epoxy resin, or a polyimide, or an inorganic material such as liquid glass is used.

繼而，貼附遮罩帶於ITO膜上，然後，將水分散液型之導電性材料(商品名：Bayer P VP CH 8000，Bayer股份公司製)供給至各隔間壁之間。此時，將導電性材料往各隔間壁之間的供給，係使用日本特開2002－75640號公報所記載之塗布裝置而進行。Then, a mask was attached to the ITO film, and then an aqueous dispersion type conductive material (trade name: Bayer P VP CH 8000, manufactured by Bayer AG) was supplied between the partition walls. In this case, the supply of the conductive material to the respective partition walls is carried out by using a coating device described in JP-A-2002-75640.

在該塗布步驟後，以同裝置將電洞傳輸液供給至各隔間壁之間，從電洞傳輸液除去溶媒的的同時，於100℃施行5至10分鐘的後烘烤處理而形成電洞傳輸層。另外，設定導電性材料的塗布量，使電洞傳輸層之膜厚成為數十至數百nm。After the coating step, the hole transport liquid is supplied between the partition walls by the same apparatus, and the solvent is removed from the hole transport liquid, and the post-baking treatment is performed at 100 ° C for 5 to 10 minutes to form electricity. Hole transport layer. Further, the coating amount of the conductive material is set so that the film thickness of the hole transport layer is several tens to several hundreds nm.

然後，將遮罩帶剝離，使用段差．表面粗糙度．微細形狀測定裝置P－11(KLA－Tencor股份公司製，商品名)，測定面向電洞傳輸層之遮罩帶側面的剝離端部從ITO膜算起之高度。Then, peel off the mask strip and use the step difference. Surface roughness. The fine shape measuring device P-11 (manufactured by KLA-Tencor Co., Ltd., trade name) measures the height of the peeling end portion of the side surface of the mask tape facing the hole transport layer from the ITO film.

此高度為5 μ m以下即判定為良好(○)，大於5 μ m時則判定為不良(×)。When the height is 5 μm or less, it is judged to be good (○), and when it is more than 5 μm, it is judged to be defective (×).

有機電致發光元件，係藉由供給有機電致發光材料並在第1電極上透過電洞傳輸層形成有機電致發光層，在此等有機電致發光層形成完畢後，與第1電極垂直相交，且呈對向般地，用真空蒸鍍法等在基板上並列設置複數條或於全面以形成第2電極而製作。此處，當以CVD裝置蒸鍍第2電極時，電洞傳輸層的剝離端部要是沒有比CVD裝置之蒸鍍上限的5 μ m小，則電洞傳輸層的剝離端部就會比第2電極更為突出。因此，針對電洞傳輸層之剝離端部的高度是否為5 μ m以下進行評估。An organic electroluminescence device is formed by supplying an organic electroluminescent material and forming an organic electroluminescence layer through a hole transport layer on a first electrode. After the organic electroluminescent layer is formed, it is perpendicular to the first electrode. The intersections are made in the same manner, and a plurality of strips are arranged in parallel on the substrate by a vacuum deposition method or the like to form a second electrode. Here, when the second electrode is vapor-deposited by the CVD apparatus, if the peeled end portion of the hole transport layer is not smaller than 5 μm of the upper limit of the vapor deposition of the CVD apparatus, the peeled end portion of the hole transport layer is more than the first portion. 2 electrodes are more prominent. Therefore, it is evaluated whether or not the height of the peeling end portion of the hole transport layer is 5 μm or less.

另外，一般而言，由於電洞傳輸層的膜厚為數十nm至數百nm的極薄膜，此電洞傳輸層之剝離端部的高度宜為與電洞傳輸層的膜厚相同，或雖比電洞傳輸層的膜厚大但能越小越好。In addition, in general, since the film thickness of the hole transport layer is an extremely thin film of several tens nm to several hundreds nm, the peeling end portion of the hole transport layer is preferably the same as the film thickness of the hole transport layer, or Although it is larger than the film thickness of the hole transport layer, it can be as small as possible.

此外，針對上述電洞傳輸層形成後所形成之有機電致發光層(PPV)之剝離端部的高度亦進行評估。Further, the height of the peeling end portion of the organic electroluminescent layer (PPV) formed after the formation of the above-mentioned hole transport layer was also evaluated.

其結果，相對於比較例1至4，在實施例1至5中可確認到有機電致發光層之剝離端部的高度係相對地變小。As a result, with respect to Comparative Examples 1 to 4, it was confirmed in Examples 1 to 5 that the height of the peeled end portion of the organic electroluminescent layer was relatively small.

1．．．基材1. . . Substrate

3．．．黏著層3. . . Adhesive layer

5．．．隔離膜5. . . Isolation film

10、20、T．．．基板用遮罩帶10, 20, T. . . Substrate mask

30．．．玻璃板30. . . glass plate

31．．．測定面31. . . Measuring surface

32．．．導電性材料32. . . Conductive material

A．．．基材1之另一方之面A. . . The other side of the substrate 1

B．．．黏著層之側面B. . . Side of the adhesive layer

W1．．．幅度W1. . . Amplitude

第1圖係顯示本發明之基板用遮罩帶的一實施例的斜視圖。Fig. 1 is a perspective view showing an embodiment of a mask tape for a substrate of the present invention.

第2圖係顯示本發明之基板用遮罩帶的一實施例的剖面圖。第2圖(a)係顯示本發明之基板用遮罩帶的一實施例的剖面圖，第2圖(b)係顯示有關本發明之基板用遮罩帶的其他實施例的剖面圖。Fig. 2 is a cross-sectional view showing an embodiment of a mask tape for a substrate of the present invention. Fig. 2(a) is a cross-sectional view showing an embodiment of a mask tape for a substrate of the present invention, and Fig. 2(b) is a cross-sectional view showing another embodiment of the mask tape for a substrate of the present invention.

第3圖係說明遮罩帶側面的濕潤性試驗的圖。第3圖(a)係顯示將遮罩帶貼上，滴下水分散性導電材料，已放置24小時之狀態的圖，第3圖(b)係顯示放置24小時後，已將遮罩帶剝離之狀態的圖。Figure 3 is a diagram illustrating the wettability test on the side of the mask strip. Fig. 3(a) shows a state in which the mask tape is attached, a water-dispersible conductive material is dropped, and the state has been left for 24 hours, and Fig. 3(b) shows that the mask tape has been peeled off after being left for 24 hours. The map of the state.

1．．．基材1. . . Substrate

3．．．黏著層3. . . Adhesive layer

5．．．隔離膜5. . . Isolation film

10、20．．．基板用遮罩帶10, 20. . . Substrate mask

A．．．基材1之另一方之面A. . . The other side of the substrate 1

B．．．黏著層之側面B. . . Side of the adhesive layer

Claims (7)

一種基板用遮罩帶，其含有基材及黏著層，且於前述基材之一方之面具有前述黏著層，其中，在基材之另一方之面具有表面處理層，該面之水的接觸角為未達65°；而黏著層之側面之水的接觸角為未達100°；且前述黏著層為含有交聯劑之聚酯系黏著劑或丙烯酸系黏著劑所成，且係於藉由從噴嘴往基板塗布流動性材料之塗布法形成薄膜時使用。 A mask tape for a substrate, comprising a substrate and an adhesive layer, and having the adhesive layer on one side of the substrate, wherein the other side of the substrate has a surface treatment layer, and the water contact of the surface The angle of the water is less than 65°; and the contact angle of the water on the side of the adhesive layer is less than 100°; and the adhesive layer is made of a polyester-based adhesive or an acrylic adhesive containing a crosslinking agent, and is It is used when a film is formed by a coating method in which a fluid material is applied from a nozzle to a substrate. 如申請專利範圍第1項之遮罩帶，其中，黏著層之被黏面具有隔離膜。 The masking tape of claim 1, wherein the adhesive layer of the adhesive layer has a separator. 如申請專利範圍第1項之遮罩帶，其中，基材包括聚酯系薄膜。 The masking tape of claim 1, wherein the substrate comprises a polyester film. 如申請專利範圍第1項之遮罩帶，其中，黏著層之側面具有表面處理層。 The masking tape of claim 1, wherein the side of the adhesive layer has a surface treatment layer. 如申請專利範圍第4項之遮罩帶，其中，表面處理層係經塗布光觸媒者。 The masking tape of claim 4, wherein the surface treatment layer is coated with a photocatalyst. 如申請專利範圍第1項至第5項中任一項之遮罩帶，其中，基板係玻璃基板。 The masking tape according to any one of claims 1 to 5, wherein the substrate is a glass substrate. 如申請專利範圍第1項至第5項中任一項之遮罩帶，其中，基板係有機電致發光用基板。 The masking tape according to any one of claims 1 to 5, wherein the substrate is a substrate for organic electroluminescence.
TW096105885A 2006-02-28 2007-02-16 Substrate mask TWI437069B (en)

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