TWI811302B - Polyester Film for Dry Film Resist Substrates - Google Patents

Polyester Film for Dry Film Resist Substrates Download PDF

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TWI811302B
TWI811302B TW108105213A TW108105213A TWI811302B TW I811302 B TWI811302 B TW I811302B TW 108105213 A TW108105213 A TW 108105213A TW 108105213 A TW108105213 A TW 108105213A TW I811302 B TWI811302 B TW I811302B
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coating layer
film
particles
coating
polyester film
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TW201940565A (en
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中山慧美
棟泰人
川崎泰史
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日商三菱化學股份有限公司
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Priority claimed from JP2019025486A external-priority patent/JP7290034B2/en
Priority claimed from JP2019025488A external-priority patent/JP7290036B2/en
Priority claimed from JP2019025485A external-priority patent/JP7290033B2/en
Priority claimed from JP2019025487A external-priority patent/JP7290035B2/en
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    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers

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  • Architecture (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Structural Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Materials For Photolithography (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Abstract

本發明提供一種於製作可撓性印刷配線板等之乾式膜抗蝕劑步驟中可用作基材膜之乾式膜抗蝕劑基材用聚酯膜。本發明之乾式膜抗蝕劑基材用聚酯膜之特徵在於：於聚酯膜之至少單面具有塗佈層，塗佈層中之抗靜電劑之含量為45質量%以下，該塗佈層中含有粒子，相對於對該塗佈層之表面進行觀察時之該塗佈層表面中所占之粒子之面積合計，粒徑為30～80 nm之粒子AS之面積比率為60～99.9%之範圍內，粒徑為100～400 nm之粒子AL之面積比率為0.1～15%之範圍內，且實質上不含粒徑超過1 μm之粒子。The present invention provides a polyester film for a dry film resist base material that can be used as a base material film in a step of producing a dry film resist for a flexible printed wiring board or the like. The polyester film for a dry film resist base material of the present invention is characterized in that it has a coating layer on at least one side of the polyester film, and the content of the antistatic agent in the coating layer is 45% by mass or less. The coating layer The layer contains particles, and the area ratio of particles AS with a particle diameter of 30 to 80 nm is 60 to 99.9% relative to the total area of particles occupying the surface of the coating layer when the surface of the coating layer is observed. Within the range, the area ratio of particles AL with particle diameters of 100 to 400 nm is within the range of 0.1 to 15%, and does not substantially contain particles with particle diameters exceeding 1 μm.

Description

乾式膜抗蝕劑基材用聚酯膜Polyester film for dry film resist substrates

本發明係關於一種可適當用作例如製作可撓性印刷基板等之乾式膜抗蝕劑步驟中之基材用膜等之膜。 The present invention relates to a film that can be suitably used, for example, as a film for a base material in a step of producing a dry film resist for a flexible printed circuit board or the like.

先前，聚對苯二甲酸乙二酯及聚萘二甲酸乙二酯所代表之聚酯膜具有機械強度、尺寸穩定性、平坦性、耐熱性、耐化學品性、光學特性等優異之特性，且成本績效優異，故而被使用於各種用途。 Previously, polyester films represented by polyethylene terephthalate and polyethylene naphthalate had excellent properties such as mechanical strength, dimensional stability, flatness, heat resistance, chemical resistance, and optical properties. Because of its excellent cost performance, it is used in various applications.

作為使用聚酯膜之用途例之一，可列舉製造可撓性印刷配線板時等所使用之乾式膜抗蝕劑步驟之膜。乾式膜抗蝕劑例如包含基材膜/感光性樹脂層/保護膜之3層構成。作為基材膜，使用機械性質、光學性質、耐化學品性、耐熱性、尺寸穩定性、平面性等優異之聚酯膜。若簡單地對使用例進行記載，則首先將保護膜剝離，使所露出之感光性樹脂層密接於貼附於基盤之導電性基材之上。繼而，使印刷有電路之玻璃板或膜(稱為光罩)密接於基材膜側，並自該光罩側照射光。該照射光通常使用紫外線。光通過印刷於光罩之電路之透明部分，感光性樹脂僅受到紫外線照射而進行曝光之部分反應。去除玻璃版與基材膜，並使用適當之溶劑等將感光性樹脂層中未經紫外線照射之未曝光部分去除。進而若使用酸等進行蝕刻，則感光性樹脂層被去除而作為電路形成導電性基材層。 An example of use of a polyester film is a film used in a dry film resist step when manufacturing a flexible printed wiring board. The dry film resist includes, for example, a three-layer structure of base film/photosensitive resin layer/protective film. As the base film, a polyester film excellent in mechanical properties, optical properties, chemical resistance, heat resistance, dimensional stability, planarity, etc. is used. To briefly describe the use example, first the protective film is peeled off, and the exposed photosensitive resin layer is brought into close contact with the conductive base material attached to the substrate. Next, a glass plate or film (called a photomask) on which a circuit is printed is brought into close contact with the base film side, and light is irradiated from the photomask side. Ultraviolet rays are usually used for this irradiation light. Light passes through the transparent part of the circuit printed on the photomask, and the photosensitive resin is only exposed to ultraviolet rays and undergoes a partial reaction during exposure. Remove the glass plate and base film, and use an appropriate solvent to remove the unexposed portion of the photosensitive resin layer that has not been exposed to ultraviolet rays. Furthermore, if etching is performed using acid or the like, the photosensitive resin layer is removed and a conductive base material layer is formed as a circuit.

近年來，因電子機器之小型化而要求可撓性印刷配線板之高清化，而形成於絕緣基板表面之電路圖案之進一步之細線化成為當務之 急。因此，亦對用作基材膜之聚酯膜要求高度之品質。於光阻膜中，於對感光性樹脂層進行曝光之情形時，如上所述，光通過基材膜。因此，若基材膜之透明性較低，則會產生感光性樹脂層未被充分地曝光或因光之散射而導致解析度變差等問題。因此，用作基材膜之聚酯膜之霧度較低且透明性高度優異較為重要。進而，於膜表面存在損傷之情形時，會產生使透過光散射而導致解析度變差等問題，故而要求膜表面不存在損傷。 In recent years, due to the miniaturization of electronic equipment, high-definition flexible printed wiring boards have been required, and further thinning of circuit patterns formed on the surface of insulating substrates has become an urgent task. urgent. Therefore, the polyester film used as a base film is also required to have high quality. In the photoresist film, when the photosensitive resin layer is exposed, light passes through the base film as described above. Therefore, if the transparency of the base film is low, problems such as insufficient exposure of the photosensitive resin layer or deterioration of resolution due to light scattering may occur. Therefore, it is important that the polyester film used as a base film has low haze and has high transparency. Furthermore, when there is damage on the film surface, problems such as scattering of transmitted light and deterioration of resolution may occur. Therefore, it is required that there be no damage on the film surface.

表面平滑而透明性較高、膜霧度較低之聚酯膜於膜之製造步驟、捲取步驟等中之操作性較差。若使用此種膜捲筒，則存在表面容易產生損傷、於捲取步驟中夾帶至膜之間之空氣不易逃逸而導致產生皺褶等問題。 A polyester film with a smooth surface, high transparency, and low film haze has poor operability in the film manufacturing process, winding process, etc. If this type of film roll is used, there are problems such as the surface being easily damaged, and the air entrained between the films during the winding step being difficult to escape, causing wrinkles.

為了使此種膜之操作性良好或為了使乾式膜抗蝕劑自身之操作性、捲繞特性良好，通常使用使聚酯膜中含有粒子而於表面形成微細突起之方法。然而若使聚酯膜中含有粒子，雖操作性、捲繞特性得到改良，但無法獲得高清化所需之等級之透明性。因此，尚未發現獲得同時滿足透明性、防受損性、平滑性之聚酯膜之方法。 In order to improve the handleability of such a film or to improve the handleability and winding characteristics of the dry film resist itself, a method of containing particles in the polyester film to form fine protrusions on the surface is generally used. However, if particles are contained in the polyester film, although the workability and winding characteristics are improved, the level of transparency required for high definition cannot be obtained. Therefore, no method has yet been found to obtain a polyester film that satisfies transparency, damage resistance, and smoothness at the same time.

作為維持膜之透明性並且改善平滑性之方法，提出有僅使聚酯膜之較薄之表面層含有粒子並將含量抑制為較低等級之方法(專利文獻1、2)。然而，於本方法中存在由於不具有塗佈層故而加工步驟中之防受損性較差之顧慮。 As a method of maintaining the transparency of the film and improving the smoothness, a method of containing particles only in a thin surface layer of a polyester film and suppressing the content to a low level has been proposed (Patent Documents 1 and 2). However, in this method, there is a concern that the damage resistance during the processing step is poor because there is no coating layer.

關於捲取步驟及加工步驟中之防受損，提出有於塗佈層中添加蠟劑之方法(專利文獻3)。然而，認為僅利用蠟劑賦予防受損性之性能並不充分。此外，本方法使用界面活性劑型抗靜電劑，存在因抗靜電劑之滲出等而導致產生之基材膜製造步驟及光阻膜製造步驟之污染之顧慮。 Regarding prevention of damage during the coiling step and processing step, a method of adding a wax agent to the coating layer has been proposed (Patent Document 3). However, it is considered that the performance imparted by the wax agent alone to provide anti-damage properties is not sufficient. In addition, this method uses a surfactant-type antistatic agent, and there is a concern of contamination in the substrate film manufacturing step and the photoresist film manufacturing step due to the bleeding of the antistatic agent.

[先前技術文獻] [Prior technical literature] [專利文獻] [Patent Document]

專利文獻1：日本專利特開2000-221688號公報 Patent Document 1: Japanese Patent Application Laid-Open No. 2000-221688

專利文獻2：日本專利特開2001-117237號公報 Patent Document 2: Japanese Patent Application Laid-Open No. 2001-117237

專利文獻3：日本專利特開2006-327158號公報 Patent Document 3: Japanese Patent Application Publication No. 2006-327158

本發明係鑒於上述實際情況而成者，其解決課題在於提供一種於製作可撓性印刷配線板等之乾式膜抗蝕劑步驟中可適當用作基材膜之乾式膜抗蝕劑基材用聚酯膜(以下，亦稱為「DFR基材用膜」)。 The present invention was made in view of the above-mentioned actual situation, and its problem to be solved is to provide a dry film resist base material that can be suitably used as a base film in the dry film resist production step of a flexible printed wiring board or the like. Polyester film (hereinafter also referred to as "film for DFR base material").

本發明者等人鑒於上述實際情況進行努力研究，結果瞭解若使用包含特定構成之積層聚酯膜，可容易地解決上述課題，從而完成本發明。 The present inventors conducted diligent research in view of the above-mentioned actual situation, and as a result found that the above-mentioned problems can be easily solved by using a laminated polyester film having a specific structure, and thus completed the present invention.

即，本發明之主旨在於一種乾式膜抗蝕劑基材用聚酯膜，其特徵在於：於聚酯膜之至少單面具有塗佈層，該塗佈層中之抗靜電劑之含量為45質量%以下，該塗佈層中含有粒子，相對於對該塗佈層之表面進行觀察時之該塗佈層表面中所占之粒子之面積合計，粒徑為30~80nm之粒子AS之面積比率為60~99.9%之範圍內，粒徑為100~400nm之粒子AL之面積比率為0.1~15%之範圍內，且實質上不含粒徑超過1μm之粒子。 That is, the gist of the present invention is a polyester film for a dry film resist base material, which is characterized in that: a coating layer is provided on at least one side of the polyester film, and the content of the antistatic agent in the coating layer is 45 Mass % or less, the coating layer contains particles, and the area of particles AS with a particle diameter of 30 to 80 nm relative to the total area of particles occupying the surface of the coating layer when the surface of the coating layer is observed The ratio is in the range of 60 to 99.9%, the area ratio of particles AL with a particle diameter of 100 to 400 nm is in the range of 0.1 to 15%, and does not substantially contain particles with a particle diameter of more than 1 μm.

本發明之主旨在於一種乾式膜抗蝕劑基材用聚酯膜，其特徵在於：於聚酯膜之至少單面具有塗佈層，該塗佈層中含有界面活性劑， 該塗佈層中含有粒子，相對於對該塗佈層之表面進行觀察時之該塗佈層表面中所占之粒子之面積合計，粒徑為30~80nm之粒子AS之面積比率為60~99.9%之範圍內，粒徑為100~400nm之粒子AL之面積比率為0.1~15%之範圍內，且實質上不含粒徑超過1μm之粒子。 The main purpose of the present invention is a polyester film for a dry film resist substrate, which is characterized in that: there is a coating layer on at least one side of the polyester film, and the coating layer contains a surfactant, The coating layer contains particles, and relative to the total area of the particles occupying the surface of the coating layer when the surface of the coating layer is observed, the area ratio of particles AS with a particle diameter of 30 to 80 nm is 60 to 60 Within the range of 99.9%, the area ratio of particles AL with a particle size of 100 to 400 nm is within a range of 0.1 to 15%, and does not substantially contain particles with a particle size exceeding 1 μm.

本發明之主旨在於一種乾式膜抗蝕劑基材用聚酯膜，其特徵在於：於聚酯膜之至少單面具有塗佈層，塗佈層中實質上不含無機鹽，該塗佈層中含有粒子，相對於對該塗佈層之表面進行觀察時之該塗佈層表面中所占之粒子之面積合計，粒徑為30~80nm之粒子AS之面積比率為60~99.9%之範圍內，粒徑為100~400nm之粒子AL之面積比率為0.1~15%之範圍內，且實質上不含粒徑超過1μm之粒子。 The main purpose of the present invention is a polyester film for a dry film resist substrate, which is characterized in that: a coating layer is provided on at least one side of the polyester film, and the coating layer does not substantially contain inorganic salts. The coating layer Contains particles, and relative to the total area of the particles occupying the surface of the coating layer when the surface of the coating layer is observed, the area ratio of particles AS with a particle diameter of 30 to 80 nm is in the range of 60 to 99.9% Within, the area ratio of particles AL with a particle size of 100 to 400 nm is in the range of 0.1 to 15%, and does not substantially contain particles with a particle size exceeding 1 μm.

本發明之主旨在於一種乾式膜抗蝕劑基材用聚酯膜，其特徵在於：於聚酯膜之至少單面具有塗佈層，該塗佈層中實質上不含聚醚化合物，該塗佈層中含有粒子，相對於對該塗佈層之表面進行觀察時之該塗佈層表面中所占之粒子之面積合計，粒徑為30~80nm之粒子AS之面積比率為60~99.9%之範圍內，粒徑為100~400nm之粒子AL之面積比率為0.1~15%之範圍內，且實質上不含粒徑超過1μm之粒子。 The main purpose of the present invention is a polyester film for a dry film resist substrate, which is characterized in that: a coating layer is provided on at least one side of the polyester film, and the coating layer does not substantially contain a polyether compound. The cloth layer contains particles, and relative to the total area of the particles occupying the surface of the coating layer when the surface of the coating layer is observed, the area ratio of particles AS with a particle diameter of 30 to 80 nm is 60 to 99.9%. Within the range, the area ratio of particles AL with particle diameters of 100 to 400 nm is within the range of 0.1 to 15%, and does not substantially contain particles with particle diameters exceeding 1 μm.

根據本發明，作為乾式膜抗蝕劑步驟中之基材膜，藉由同時滿足透明性、防受損性、防磨削性、空氣逃逸性、及平滑性，可進行極細線之電路形成。又，根據本發明，可提供如下DFR基材用膜，該DFR基材用膜由於平滑性及防受損性良好，故而可減小空氣洩漏指數，由於空氣逃逸性良好，故而於將膜捲繞成捲筒形態時吸入之氣體容易逃逸，可使膜彼此緊密接觸並捲緊，可防止保管中及搬送中之向卷芯方向之偏移而防止 因偏移而導致產生之損傷及磨削，從而不易產生表層皺褶。根據本發明，可提供具有更高品質之DFR基材用膜，其工業價值較高。 According to the present invention, as the base film in the dry film resist step, circuit formation of extremely fine lines can be performed by simultaneously satisfying transparency, damage resistance, grinding resistance, air escape properties, and smoothness. Furthermore, according to the present invention, it is possible to provide a film for a DFR base material that has good smoothness and damage resistance, so that the air leakage index can be reduced, and that has good air escape properties, so that it can be rolled When the film is wound into a roll, the inhaled gas can easily escape, allowing the films to be in close contact with each other and rolled tightly, thus preventing the film from deflecting toward the roll core during storage and transportation. Damage and grinding caused by offset make surface wrinkles less likely to occur. According to the present invention, a film for DFR substrates with higher quality can be provided, and its industrial value is high.

以下，對本發明之實施形態之一例詳細地進行說明。但是，本發明並不限定於以下要說明之實施形態例，可於不脫離本發明之主旨之範圍內任意變化後實施。 Hereinafter, an example of an embodiment of the present invention will be described in detail. However, the present invention is not limited to the embodiment examples described below, and can be implemented with any modification within the scope that does not deviate from the gist of the present invention.

本發明之實施形態之DFR基材用膜於聚酯膜之至少單面具有塗佈層，該塗佈層中之抗靜電劑之含量為45質量%以下，該塗佈層中含有粒子，相對於對該塗佈層之表面進行觀察時之該塗佈層表面中所占之粒子之面積合計，粒徑為30~80nm之粒子AS之面積比率為60~99.9%之範圍內，粒徑為100~400nm之粒子AL之面積比率為0.1~15%之範圍內，且實質上不含粒徑超過1μm之粒子。 The film for DFR base material according to the embodiment of the present invention has a coating layer on at least one side of the polyester film. The content of the antistatic agent in the coating layer is 45% by mass or less. The coating layer contains particles. When the surface of the coating layer is observed, the total area of the particles occupying the surface of the coating layer, the area ratio of particles AS with a particle diameter of 30 to 80 nm is in the range of 60 to 99.9%, and the particle diameter is The area ratio of particles AL between 100 and 400 nm is in the range of 0.1 to 15%, and does not substantially contain particles with a particle size exceeding 1 μm.

本發明之實施形態之DFR基材用膜由於在聚酯膜之至少單面具有含有粒子且可視需要含有抗靜電劑之塗佈層，故而可藉由該塗佈層於維持作為基材膜之透明性之情況下同時滿足防受損性、防磨削性、空氣逃逸性、及平滑性。又，於本發明之實施形態之DFR基材用膜之塗佈層中包含抗靜電劑之情形時，藉由使塗佈層中之抗靜電劑之含量較少為45質量%以下，可抑制抗靜電劑之滲出而防止因滲出而導致產生之DFR基材用膜之污染，並且可防止因灰塵等之吸附而導致產生之損傷。 The DFR base film according to the embodiment of the present invention has a coating layer containing particles and optionally an antistatic agent on at least one side of the polyester film. Therefore, the coating layer can be used to maintain the base film. While being transparent, it also meets the requirements of damage resistance, grinding resistance, air escape, and smoothness. Furthermore, when the coating layer of the DFR substrate film according to the embodiment of the present invention contains an antistatic agent, by reducing the content of the antistatic agent in the coating layer to 45% by mass or less, it is possible to suppress The exudation of antistatic agents prevents contamination of the DFR substrate film caused by exudation, and prevents damage caused by the adsorption of dust, etc.

本發明之實施形態之DFR基材用膜於聚酯膜之至少單面具有塗佈層，該塗佈層中包含界面活性劑，該塗佈層中含有粒子，相對於對該塗佈層之表面進行觀察時之該塗佈層表面中所占之粒子之面積合計，粒徑為30~80nm之粒子AS之面積比率為60~99.9%之範圍內，粒徑為100 ~400nm之粒子AL之面積比率為0.1~15%之範圍內，且實質上不含粒徑超過1μm之粒子。 The film for DFR base material according to the embodiment of the present invention has a coating layer on at least one side of the polyester film, the coating layer contains a surfactant, and the coating layer contains particles. When the surface is observed, the total area of the particles occupied by the surface of the coating layer, the area ratio of particles AS with a particle diameter of 30 to 80 nm is in the range of 60 to 99.9%, and the particle diameter is 100 The area ratio of ~400nm particles AL is in the range of 0.1~15%, and does not substantially contain particles with a particle size exceeding 1 μm.

本發明之實施形態之DFR基材用膜由於在聚酯膜之至少單面具有塗佈層，且該塗佈層中含有界面活性劑及粒子，故而可藉由該塗佈層於維持作為基材膜之透明性之情況下同時滿足防受損性、防磨削性、空氣逃逸性、及平滑性。又，本發明之實施形態之DFR基材用膜於塗佈層中包含界面活性劑，可藉由界面活性劑提高塗佈液對聚酯膜之潤濕性，抑制塗佈不均或塗佈液之收縮而使塗佈層之外觀良好。 The film for DFR base material according to the embodiment of the present invention has a coating layer on at least one side of the polyester film, and the coating layer contains a surfactant and particles. Therefore, the coating layer can be used to maintain the base material. While the material film is transparent, it also meets the requirements of damage resistance, anti-abrasion, air escape, and smoothness. In addition, the film for DFR substrates according to the embodiment of the present invention contains a surfactant in the coating layer. The surfactant can improve the wettability of the coating liquid to the polyester film and suppress uneven coating or coating The shrinkage of the liquid makes the appearance of the coating layer good.

本發明之實施形態之DFR基材用膜於聚酯膜之至少單面具有塗佈層，該塗佈層中實質上不含無機鹽，該塗佈層中含有粒子，相對於對該塗佈層之表面進行觀察時之該塗佈層表面中所占之粒子之面積合計，粒徑為30~80nm之粒子AS之面積比率為60~99.9%之範圍內，粒徑為100~400nm之粒子AL之面積比率為0.1~15%之範圍內，且實質上不含粒徑超過1μm之粒子。 The film for DFR base material according to the embodiment of the present invention has a coating layer on at least one side of the polyester film. The coating layer does not substantially contain inorganic salts. The coating layer contains particles. Compared with coating the When the surface of the layer is observed, the total area of the particles occupying the surface of the coating layer, the area ratio of particles AS with a particle diameter of 30~80nm is in the range of 60~99.9%, and the area ratio of particles with a particle diameter of 100~400nm The area ratio of AL is in the range of 0.1~15%, and does not substantially contain particles with a particle size exceeding 1 μm.

本發明之實施形態之DFR基材用膜由於在聚酯膜之至少單面具有含有粒子之塗佈層，故而可藉由該塗佈層於維持作為基材膜之透明性之情況下同時滿足防受損性、防磨削性、空氣逃逸性、及平滑性。又，本發明之實施形態之DFR基材用膜由於塗佈層中實質上不含無機鹽，故而由塗佈液中所包含之交聯劑等而形成之乳液不會被無機鹽破壞，可抑制塗佈液對聚酯膜之塗佈不均而使塗佈層之外觀良好。 The DFR base film according to the embodiment of the present invention has a coating layer containing particles on at least one side of the polyester film. Therefore, the coating layer can satisfy the requirements while maintaining the transparency of the base film through the coating layer. Damage resistance, grinding resistance, air escape, and smoothness. In addition, since the coating layer of the film for DFR base material according to the embodiment of the present invention does not substantially contain inorganic salts, the emulsion formed from the cross-linking agent etc. contained in the coating liquid will not be destroyed by the inorganic salts and can be It suppresses the uneven coating of the polyester film with the coating liquid and improves the appearance of the coating layer.

本發明之實施形態之DFR基材用膜於聚酯膜之至少單面具有塗佈層，該塗佈層中實質上不含聚醚化合物，該塗佈層中含有粒子，相對於對該塗佈層之表面進行觀察時之該塗佈層表面中所占之粒子之面積合 計，粒徑為30~80nm之粒子AS之面積比率為60~99.9%之範圍內，粒徑為100~400nm之粒子AL之面積比率為0.1~15%之範圍內，且實質上不含粒徑超過1μm之粒子。 The film for DFR base material according to the embodiment of the present invention has a coating layer on at least one side of the polyester film. The coating layer does not substantially contain a polyether compound, and the coating layer contains particles. Compared with the coating layer, The total area of the particles occupying the surface of the coating layer when the surface of the cloth layer is observed According to the calculation, the area ratio of particles AS with a particle diameter of 30~80nm is in the range of 60~99.9%, and the area ratio of particles AL with a particle diameter of 100~400nm is in the range of 0.1~15%, and does not substantially contain particles. Particles with a diameter exceeding 1 μm.

本發明之實施形態之DFR基材用膜由於在聚酯膜之至少單面具有塗佈層，故而可藉由該塗佈層於維持作為基材膜之透明性之情況下同時滿足防受損性、防磨削性、空氣逃逸性、及平滑性。又，本發明之實施形態之DFR基材用膜由於塗佈層中實質上不含聚醚化合物，故而耐水性、耐濕性優異，可提高經時性之耐受損性。 The DFR base film according to the embodiment of the present invention has a coating layer on at least one side of the polyester film. Therefore, the coating layer can maintain the transparency of the base film and at the same time satisfy the requirements of damage prevention. properties, anti-grinding properties, air escape properties, and smoothness. In addition, since the coating layer of the DFR substrate film according to the embodiment of the present invention contains substantially no polyether compound, it has excellent water resistance and moisture resistance and can improve the damage resistance over time.

本發明之實施形態之DFR基材用膜由於在塗佈層中於以塗佈層表面之面積比率計為60~99.9%之範圍內含有粒徑為30~80nm之粒子AS，故而可於維持透明性之情況下提高防受損性。又，本發明之實施形態之DFR基材用膜由於在塗佈層中於以塗佈層表面之面積比率計為0.1~15%之範圍內含有粒徑為100~400nm之粒子AL，故而可於維持防受損性之情況下提高防磨削性、空氣逃逸性及平滑性。進而，本發明之實施形態之DFR基材用膜由於塗佈層中實質上不含粒徑超過1μm之粒子，故而防磨削性提高。於本說明書中，將DFR基材用膜之塗佈層中所含有之粒子亦稱為粒子A。粒子A係指塗佈層中所包含之粒子。粒子A中包含粒徑為30~80nm之粒子AS及粒徑為100~400nm之粒子AL，亦可包含粒子AS及粒子AL以外之粒徑未達1μm之粒子(以下，亦稱為「其他粒子AE」)。 The film for a DFR base material according to the embodiment of the present invention contains particles AS with a particle diameter of 30 to 80 nm in the coating layer in the range of 60 to 99.9% based on the area ratio of the coating layer surface, so it can be maintained Improves damage resistance with transparency. In addition, since the film for DFR base material according to the embodiment of the present invention contains particles AL with a particle diameter of 100 to 400 nm in the range of 0.1 to 15% based on the area ratio of the coating layer surface, it can be Improves grinding resistance, air escape and smoothness while maintaining damage resistance. Furthermore, since the coating layer of the film for DFR base material according to the embodiment of the present invention does not substantially contain particles having a particle diameter exceeding 1 μm, the anti-wear properties are improved. In this specification, the particles contained in the coating layer of the film for DFR base materials are also referred to as particles A. Particle A refers to the particles contained in the coating layer. Particle A includes particle AS with a particle diameter of 30 to 80 nm and particle AL with a particle diameter of 100 to 400 nm. It may also include particles other than particle AS and particle AL with a particle diameter of less than 1 μm (hereinafter also referred to as "other particles"). AE").

聚酯膜 polyester film

本發明中之聚酯膜可為未延伸膜(片材)，亦可為延伸膜。其中，較佳為沿單軸方向或雙軸方向延伸之延伸膜。其中，就力學特性之平衡性及平 面性優異之方面而言，較佳為雙軸延伸膜。 The polyester film in the present invention can be an unstretched film (sheet) or a stretched film. Among them, a stretched film extending in a uniaxial direction or a biaxial direction is preferred. Among them, in terms of the balance and balance of mechanical properties In terms of excellent surface properties, a biaxially stretched film is preferred.

本發明中之聚酯膜可為單層構成，亦可為2層以上之多層，並無特別限定。於向聚酯層中添加粒子之情形時，就有效地賦予透明性及平滑性之觀點而言，較佳為3層以上，就成本之觀點而言，較佳為3層。又，於製成3層之情形時，就有效地賦予透明性及平滑性之觀點而言，較佳為兩表層含有粒子且中間層不含有粒子之2種3層、至少一表層含有粒子且中間層及另一表層不含有粒子之3種3層。 The polyester film in the present invention can be composed of a single layer or a multi-layer structure of two or more layers, and is not particularly limited. When adding particles to the polyester layer, three or more layers are preferred from the viewpoint of effectively imparting transparency and smoothness, and three layers are preferred from the viewpoint of cost. In addition, when forming three layers, from the viewpoint of effectively imparting transparency and smoothness, it is preferable to use two types of three layers in which both surface layers contain particles and the middle layer does not contain particles, and at least one surface layer contains particles and The middle layer and the other surface layer are 3 types of 3 layers that do not contain particles.

所謂本發明中所言之聚酯，作為構成聚酯之二羧酸成分，可例示：對苯二甲酸、間苯二甲酸、2,6-萘二甲酸、六氫對苯二甲酸、4,4'-二苯基二羧酸、己二酸、癸二酸、十二烷二羧酸等。尤其是就膜之機械性質之方面而言，較佳為對苯二甲酸、間苯二甲酸、2,6-萘二甲酸。作為構成聚酯之二醇成分，可例示：乙二醇、二乙二醇、丙二醇、1,3-丙烷二醇、1,4-丁二醇、新戊二醇、1,6-己二醇、環己烷二甲醇、聚乙二醇等。尤其是就膜之剛直性之方面而言，較佳為乙二醇。 The polyester in the present invention includes, for example, the dicarboxylic acid component constituting the polyester: terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, 4, 4'-diphenyldicarboxylic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, etc. In particular, in terms of the mechanical properties of the film, terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid are preferred. Examples of the glycol component constituting the polyester include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, and 1,6-hexanediol. alcohol, cyclohexanedimethanol, polyethylene glycol, etc. Especially in terms of the rigidity of the film, ethylene glycol is preferred.

上述聚酯可為使作為第3成分之上述二羧酸成分或者二醇成分進行共聚而成之共聚酯，亦可包含三官能以上之多元羧酸成分或者三官能以上之多元醇成分，所獲得之聚酯亦可為於實質上成為線狀之範圍(例如5莫耳%以下)內少量共聚而成之聚酯。作為本發明中所使用之聚酯，尤佳為聚對苯二甲酸乙二酯或2,6-萘二甲酸聚伸乙酯。該聚酯可藉由常規方法而製作，若聚酯之固有黏度(苯酚/四氯乙烷=50/50(重量比)，30℃)為0.45以上，則膜之撕裂性、剛性較大等而機械特性良好，故而較佳。 The polyester may be a copolyester obtained by copolymerizing the dicarboxylic acid component or diol component as the third component, or may contain a trifunctional or higher polycarboxylic acid component or a trifunctional or higher polyol component. The polyester obtained may be a polyester copolymerized in a small amount within a substantially linear range (for example, 5 mol% or less). As the polyester used in the present invention, polyethylene terephthalate or polyethylene naphthalate is particularly preferred. The polyester can be produced by conventional methods. If the inherent viscosity of the polyester (phenol/tetrachloroethane = 50/50 (weight ratio), 30°C) is 0.45 or above, the tearability and rigidity of the film will be greater. etc. and have good mechanical properties, so they are preferred.

作為聚酯之聚合觸媒，並無特別限制，可使用先前公知之 化合物，例如可列舉：銻化合物、鈦化合物、鍺化合物、錳化合物、鋁化合物、鎂化合物、鈣化合物等。該其中，鈦化合物及鍺化合物之觸媒活性較高，可以少量進行聚合，且殘留於膜中之金屬元素量較少，因此膜之透明性提高，故而較佳。 The polymerization catalyst for polyester is not particularly limited, and previously known catalysts can be used. Examples of the compound include antimony compounds, titanium compounds, germanium compounds, manganese compounds, aluminum compounds, magnesium compounds, calcium compounds, and the like. Among them, titanium compounds and germanium compounds are preferred because they have high catalytic activity, can polymerize in small amounts, and have a small amount of metal elements remaining in the film, thereby improving the transparency of the film.

於聚酯膜為2層構成之情形時，至少一層之厚度較佳為另一層之厚度之八分之一以下，更佳為十分之一以下，進而較佳為十二分之一以下，尤佳為十六分之一以下。於聚酯膜為3層以上之多層構成之情形時，至少一表層(最外層)之厚度較佳為表層以外之層之厚度(中間層之合計厚度)之八分之一以下，更佳為十分之一以下，進而較佳為十二分之一以下，尤佳為十六分之一以下。於聚酯膜為2層或3層以上之多層構成之情形時，若至少一表層之厚度為表層以外之層之厚度之八分之一以下之範圍，則即便於至少一表層中含有下述粒子B之情形時，亦可同時實現高度之透明性與良好之平滑性。 When the polyester film is composed of two layers, the thickness of at least one layer is preferably one-eighth or less of the thickness of the other layer, more preferably one-tenth or less, and still more preferably one-twelfth or less. Especially preferably, it is less than one sixteenth. When the polyester film is composed of three or more layers, the thickness of at least one surface layer (outermost layer) is preferably less than one-eighth of the thickness of the layers other than the surface layer (the total thickness of the intermediate layers), and more preferably One-tenth or less, more preferably one-twelfth or less, particularly preferably one-sixteenth or less. When the polyester film is composed of two or more layers, if the thickness of at least one surface layer is within the range of one-eighth or less of the thickness of layers other than the surface layer, then at least one surface layer contains the following: In the case of particle B, high transparency and good smoothness can also be achieved at the same time.

粒子B Particle B

於聚酯膜中，較佳為以賦予易滑性及各步驟中之防受損性為主要目的而含有粒子。於本說明書中，將聚酯膜中所含有之粒子稱為粒子B。於聚酯膜具有多層結構之情形時，粒子B較佳為含有於至少一層中。於聚酯膜為2層結構之情形時，粒子B較佳為含有於至少一層中。於聚酯膜為3層以上之多層結構之情形時，粒子B較佳為含有於至少一表層中，亦可含有於兩表面層中。 In the polyester film, it is preferable to contain particles for the main purpose of imparting slipperiness and damage prevention in each step. In this specification, the particles contained in the polyester film are called particles B. When the polyester film has a multilayer structure, the particles B are preferably contained in at least one layer. When the polyester film has a two-layer structure, the particles B are preferably contained in at least one layer. When the polyester film has a multilayer structure of three or more layers, the particles B are preferably contained in at least one surface layer, and may also be contained in both surface layers.

關於聚酯膜中所含有之粒子B之種類，只要為可賦予易滑性之粒子，則並無特別限定。作為具體例，可列舉：二氧化矽、氧化鋁、碳酸鈣、碳 酸鎂、碳酸鋇、硫酸鈣、磷酸鈣、磷酸鎂、高嶺土、氧化鋯、氧化鈦等無機粒子；丙烯酸系樹脂、苯乙烯樹脂、尿素樹脂、酚系樹脂、環氧樹脂、苯胍

Figure 108105213-A0305-02-0011-18
樹脂等有機粒子等。進而，於聚酯膜之製造步驟中，亦可使用使觸媒等金屬化合物之一部分沈澱並微分散之析出粒子。 The type of particles B contained in the polyester film is not particularly limited as long as it can impart slipperiness. Specific examples include inorganic particles such as silica, alumina, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, zirconium oxide, and titanium oxide; acrylic resin and styrene resin. , Urea resin, phenolic resin, epoxy resin, benzene guanidine
Figure 108105213-A0305-02-0011-18
Resin and other organic particles, etc. Furthermore, in the production process of the polyester film, precipitated particles in which a part of a metal compound such as a catalyst is precipitated and finely dispersed may be used.

若將粒子B添加至聚酯膜中而於聚酯膜表面形成突起，則存在於製造配線板時會產生因突起而導致之紫外線之曝光不良或於抗蝕劑表面產生凹陷，對近年來所要求之極細線之電路形成造成解像性降低或產生缺陷或導致膜之透明性降低之情形。該等之中，藉由使用氧化鋁粒子、有機粒子、二氧化矽粒子作為粒子B，可獲得聚酯膜之高度之透明性及防受損性且可減少電路之缺損。 If the particles B are added to the polyester film to form protrusions on the surface of the polyester film, poor exposure to ultraviolet rays due to the protrusions or depressions on the resist surface may occur during the manufacture of wiring boards, which is a problem for recent years. The formation of circuits with extremely fine lines required may result in reduced resolution or defects, or may result in reduced transparency of the film. Among them, by using alumina particles, organic particles, and silicon dioxide particles as particles B, high transparency and damage prevention properties of the polyester film can be obtained and circuit defects can be reduced.

粒子B之平均粒徑通常為1.5μm以下、較佳為1.0μm以下、更佳為0.001~0.5μm、進而較佳為0.001~0.3μm之範圍。於平均粒徑超過1.5μm之情形時，聚酯膜之表面粗糙度變粗，故而可能會將聚酯膜之凹凸轉印至抗蝕劑。若抗蝕劑產生凹凸，則於利用酸蝕刻處理將抗蝕劑去除時，存在對蝕刻處理度造成影響導致電路產生缺陷之情況。關於粒子之平均粒徑，於粒子為粉體之情形時，可將使用離心沈降式粒度分佈測定裝置(島津製作所公司製造，SA-CP3型)對粉體進行測定所得之等效球形分佈中之累計體積分率50%之粒徑(d50)設為平均粒徑。關於膜或膜中之粒子之平均粒徑，例如可使用掃描式電子顯微鏡(日立高新技術股份有限公司製造，「S3400N」)對粉體或聚酯膜進行觀察，自所獲得之圖像資料中測定1個粒子之大小，將10點(10個粒子)之平均值設為平均粒徑。 The average particle diameter of the particles B is usually 1.5 μm or less, preferably 1.0 μm or less, more preferably 0.001 to 0.5 μm, and further preferably 0.001 to 0.3 μm. When the average particle diameter exceeds 1.5 μm, the surface roughness of the polyester film becomes rough, so the unevenness of the polyester film may be transferred to the resist. If the resist has unevenness, when the resist is removed by acid etching, it may affect the etching process and cause defects in the circuit. Regarding the average particle size of the particles, when the particles are powder, the equivalent spherical distribution obtained by measuring the powder using a centrifugal sedimentation particle size distribution measuring device (model SA-CP3, manufactured by Shimadzu Corporation) can be considered The particle diameter (d50) with a cumulative volume fraction of 50% is set as the average particle diameter. Regarding the average particle size of the film or the particles in the film, for example, a scanning electron microscope (manufactured by Hitachi High-Technology Co., Ltd., "S3400N") can be used to observe the powder or polyester film, and from the image data obtained The size of one particle is measured, and the average value of 10 points (10 particles) is taken as the average particle diameter.

粒子B之平均粒徑越小，聚酯膜之透明性越高，可減少電路之缺損，從而可應用於要求更細之極細線之電路之用途。平均粒徑相對 較小之粒子B(以下，有時稱為「粒子B-1」)之平均粒徑通常為0.001~0.1μm、較佳為0.001~0.08μm、更佳為0.001~0.06μm之範圍。為了維持聚酯膜之平滑性並且防止因平滑性之降低而產生之製膜步驟中之受損，亦可使用平均粒徑略大於粒子B-1之粒子B(以下，有時稱為「粒子B-2」)。藉由使用粒子B-2，亦可賦予聚酯膜之平滑性。粒子B-2之平均粒徑通常為0.1~1.5μm、較佳為0.1~1.0μm、更佳為0.1~0.5μm、進而較佳為0.1~0.3μm之範圍。進而，亦可將平均粒徑為0.001~0.1μm之範圍中所包含之粒子B-1與平均粒徑為0.1~1.5μm之範圍中所包含之粒子B-2之2種以上之粒子B併用，且亦可藉由併用，同時實現高度之透明性及良好之平滑性。 The smaller the average particle size of the particles B, the higher the transparency of the polyester film, which can reduce circuit defects and can therefore be applied to circuits that require thinner ultra-thin wires. Average particle size relative to The average particle diameter of the smaller particles B (hereinafter, sometimes referred to as "particles B-1") is usually in the range of 0.001 to 0.1 μm, preferably 0.001 to 0.08 μm, and more preferably 0.001 to 0.06 μm. In order to maintain the smoothness of the polyester film and prevent damage during the film-making step due to the decrease in smoothness, particles B (hereinafter sometimes referred to as "particles") whose average particle diameter is slightly larger than particles B-1 can also be used. B-2"). By using particles B-2, smoothness can also be imparted to the polyester film. The average particle diameter of the particles B-2 is usually in the range of 0.1 to 1.5 μm, preferably 0.1 to 1.0 μm, more preferably 0.1 to 0.5 μm, and further preferably 0.1 to 0.3 μm. Furthermore, two or more types of particles B including particles B-1 included in the range of average particle diameters of 0.001 to 0.1 μm and particles B-2 included in the range of average particle diameters of 0.1 to 1.5 μm may be used together. , and can also be used together to achieve high transparency and good smoothness at the same time.

聚酯膜中之粒子B之含量較佳為10000質量ppm以下、更佳為8000質量ppm以下、更佳為6000質量ppm以下、尤佳為4000質量ppm以下之範圍。於使用平均粒徑為0.1~1.5μm之粒子B-2之情形時，由於能以少量便有效地賦予平滑性，故而作為粒子B之聚酯膜中之含量，較佳為1000質量ppm以下、更佳為800質量ppm以下、進而較佳為500質量ppm以下之範圍。下限並無特別限制，不包含粒子B或為1質量ppm以上或2質量ppm以上。於聚酯膜中之粒子B含量較多之情形時，有霧度增大、於高解像之乾式膜抗蝕劑中紫外線之曝光變得不充分而導致產生電路之缺損或解析度之降低之虞。 The content of the particles B in the polyester film is preferably 10,000 ppm by mass or less, more preferably 8,000 ppm by mass or less, more preferably 6,000 ppm by mass or less, and even more preferably 4,000 ppm by mass or less. When using particles B-2 with an average particle diameter of 0.1 to 1.5 μm, since smoothness can be effectively imparted in a small amount, the content of particles B in the polyester film is preferably 1000 ppm by mass or less. More preferably, it is 800 mass ppm or less, and still more preferably, it is the range of 500 mass ppm or less. The lower limit is not particularly limited, but it is 1 mass ppm or more or 2 mass ppm or more excluding particle B. When the content of particle B in the polyester film is high, the haze may increase, and the exposure of ultraviolet rays in the high-resolution dry film resist may become insufficient, resulting in circuit defects or a reduction in resolution. The danger.

關於所使用之粒子之形狀，亦並無特別限定，可使用球狀、塊狀、棒狀、扁平狀等任一形狀。又，其硬度、比重、顏色等亦並無特別限制。 The shape of the particles used is not particularly limited, and any shape such as spherical, lumpy, rod-like, and flat shapes can be used. In addition, its hardness, specific gravity, color, etc. are not particularly limited.

該等一系列粒子可視需要將2種以上併用。 These series of particles may be used in combination of two or more types as necessary.

作為向聚酯膜中添加粒子之方法，並無特別限定，可採用先前公知之方法。例如，可於製造構成膜之聚酯之任意階段添加，較佳為於酯化或者酯交換反應結束後添加。 There is no particular limitation on the method of adding particles to the polyester film, and conventionally known methods can be used. For example, it can be added at any stage of producing the polyester constituting the film, but is preferably added after the completion of the esterification or transesterification reaction.

再者，於本發明中之聚酯膜中，除上述粒子以外，亦可視需要含有先前公知之抗氧化劑、抗靜電劑、熱穩定劑、紫外線吸收劑、潤滑劑、染料、顏料等。 Furthermore, in addition to the above-mentioned particles, the polyester film in the present invention may also contain previously known antioxidants, antistatic agents, heat stabilizers, ultraviolet absorbers, lubricants, dyes, pigments, etc., if necessary.

本發明中之聚酯膜之厚度只要為可作為膜來製膜之範圍，則並無特別限定，就機械強度、操作性及生產性等方面而言，較佳為1~300μm、更佳為5~50μm之範圍，進而較佳為8~25μm。 The thickness of the polyester film in the present invention is not particularly limited as long as it is within the range that can be formed as a film. In terms of mechanical strength, operability, productivity, etc., it is preferably 1 to 300 μm, and more preferably 1 to 300 μm. The range is 5~50μm, and more preferably 8~25μm.

作為聚酯膜之製膜方法，可採用通常所知之製膜法，並無特別限制。例如可列舉如下方法：於製造雙軸延伸聚酯膜之情形時，首先使用擠出機將上文中所述之聚酯原料自模嘴熔融擠出，並利用冷卻輥將熔融片材冷卻固化，而獲得未延伸片材。於該情形時，為了提高片材之平面性，較佳為提高片材與旋轉冷卻筒之密接性，可較佳地採用靜電施加密接法或液體塗佈密接法。 As a method of forming a polyester film, a generally known film forming method can be used and is not particularly limited. For example, the following method can be cited: when producing a biaxially stretched polyester film, first use an extruder to melt and extrude the polyester raw material described above from a die nozzle, and use a cooling roller to cool and solidify the molten sheet. An unstretched sheet is obtained. In this case, in order to improve the planarity of the sheet, it is better to improve the adhesion between the sheet and the rotating cooling cylinder. An electrostatic application adhesion method or a liquid coating adhesion method can be preferably used.

繼而，藉由滾壓或拉幅方式之延伸機使所獲得之未延伸片材沿一方向延伸。延伸溫度通常為70~150℃，較佳為80~140℃，延伸倍率通常為2.5~7倍，較佳為3.0~6倍。繼而，於通常70~170℃下以延伸倍率通常2.5~7倍、較佳為3.0~6倍沿與第一階段之延伸方向正交之方向延伸。接下來，於180~270℃之溫度下，於拉伸下或於30%以內之鬆弛下進行熱處理，而獲得雙軸配向膜。亦可採用於上述延伸中於兩個以上之階段中進行一方向之延伸之方法。於該情形時，較佳為以最終兩方向之延伸倍率分別成為上述範圍之方式進行。 Then, the obtained unstretched sheet is stretched in one direction by a rolling or tenter stretching machine. The extension temperature is usually 70~150°C, preferably 80~140°C, and the extension ratio is usually 2.5~7 times, preferably 3.0~6 times. Then, the film is extended in a direction orthogonal to the extending direction of the first stage at a temperature of usually 70 to 170° C. with an extension ratio of usually 2.5 to 7 times, preferably 3.0 to 6 times. Next, heat treatment is performed at a temperature of 180 to 270°C under stretching or relaxation within 30% to obtain a biaxial alignment film. It is also possible to adopt a method of extending in one direction in two or more stages in the above-mentioned extending. In this case, it is preferable to proceed so that the final stretch ratios in both directions fall into the above ranges.

塗佈層之形成 Formation of coating layer

對本發明中之塗佈層之形成進行說明，繼而，對形成塗佈層之塗佈液及塗佈層之構成進行說明。關於塗佈層之形成，可藉由於聚酯膜之製膜步驟中將塗佈液塗佈於膜表面之線內塗佈形成塗佈層，亦可藉由於體系外將塗佈液暫時塗佈於所製造之聚酯膜上之離線塗佈形成塗佈層。就加工容易性之方面而言，塗佈層較佳為藉由線內塗佈形成。 The formation of the coating layer in the present invention will be described, and then the coating liquid forming the coating layer and the structure of the coating layer will be described. Regarding the formation of the coating layer, the coating layer can be formed by applying the coating liquid within the line on the film surface during the film-making step of the polyester film, or by temporarily applying the coating liquid outside the system. Off-line coating on the produced polyester film forms a coating layer. In terms of ease of processing, the coating layer is preferably formed by in-line coating.

線內塗佈係於聚酯膜製造之步驟內形成塗佈層之進行塗佈液之塗佈之方法，具體而言，線內塗佈係於將聚酯熔融擠出後延伸然後進行熱固定並捲緊之前之任意階段中進行塗佈液之塗佈之方法。通常於熔融、急冷而獲得之未延伸片材、經延伸之單軸延伸膜、熱固定前之雙軸延伸膜、熱固定後捲緊前之膜之任一聚酯膜塗佈塗佈液。 In-line coating is a method of applying a coating liquid to form a coating layer during the polyester film manufacturing process. Specifically, in-line coating is based on melting and extruding the polyester, stretching it, and then heat-setting it. And the method of applying the coating liquid at any stage before rolling up. The coating liquid is usually applied to any polyester film obtained by melting and quenching the unstretched sheet, the stretched uniaxially stretched film, the biaxially stretched film before heat setting, or the film before winding after heat setting.

作為塗佈塗佈液之方法，例如可使用氣刀塗佈、刮刀塗佈、桿式塗佈、棒式塗佈、刮塗、擠壓塗佈、含浸塗佈、逆輥塗佈、轉移輥塗、凹版塗佈、接觸輥塗、拋光塗佈、噴塗、淋幕式塗佈、壓延塗佈、擠出塗佈等先前公知之塗佈方法。 As a method of applying the coating liquid, for example, air knife coating, blade coating, bar coating, bar coating, blade coating, extrusion coating, dip coating, reverse roll coating, transfer roll Coating, gravure coating, contact roller coating, polishing coating, spray coating, curtain coating, calendar coating, extrusion coating and other previously known coating methods.

並不限定於以下，例如於逐次雙軸延伸中，於沿尤其是長度方向(縱向)延伸之單軸延伸膜塗佈塗佈液後橫向延伸，形成聚酯膜具有塗佈層之DFR基材用膜之方法優異。根據該方法，可同時地進行聚酯膜之製膜與塗佈層之形成，故而於製造成本上存在優勢，又，由於係於塗佈後進行延伸，故而亦可藉由延伸倍率使塗佈層之厚度變化，與離線塗佈相比，可更容易地進行薄膜塗佈。進而，可使塗佈層之厚度更均勻。 It is not limited to the following. For example, in the sequential biaxial stretching, a uniaxially stretched film extending especially along the length direction (longitudinal direction) is coated with a coating liquid and then stretched laterally to form a DFR base material with a coating layer on the polyester film. The method of using membrane is excellent. According to this method, the polyester film can be formed and the coating layer can be formed at the same time, so it is advantageous in terms of manufacturing cost. In addition, since the stretching is performed after coating, the coating can also be made by stretching the magnification. The thickness of the layer changes, making thin film coating easier than offline coating. Furthermore, the thickness of the coating layer can be made more uniform.

又，藉由於延伸前於聚酯膜上設置塗佈層，可使塗佈層與 聚酯膜一起延伸，藉此，可使塗佈層與聚酯膜緊密地密接。進而，於雙軸延伸聚酯膜之製造中，藉由夾具等握持膜端部並使之延伸，藉此可於縱向及橫向上約束膜，於熱固定步驟中，可於不產生皺紋等而維持平面性之情況下施加高溫。 Furthermore, by providing a coating layer on the polyester film before stretching, the coating layer can be The polyester film is stretched together, whereby the coating layer and the polyester film can be tightly adhered to each other. Furthermore, in the production of biaxially stretched polyester films, the ends of the film are held and stretched by clamps, etc., thereby constraining the film in the longitudinal and transverse directions, and in the heat fixing step, wrinkles, etc. can be prevented. High temperature is applied while maintaining flatness.

因此，可製成塗佈後所實施之熱處理無法利用其他方法達成之高溫，故而可使塗佈層與聚酯膜更緊密地密接，進而，可製成牢固之塗佈層。 Therefore, the heat treatment performed after coating can be carried out to a high temperature that cannot be achieved by other methods, so that the coating layer and the polyester film can be more closely adhered, and a strong coating layer can be produced.

又，塗佈層不論係藉由離線塗佈形成抑或是藉由線內塗佈形成，均可視需要將熱處理與紫外線照射等活性能量線照射併用。為了改良形成塗佈層之塗佈液對聚酯膜之塗佈性、接著性，亦可於塗佈前對聚酯膜實施化學處理或電暈放電處理、電漿處理、臭氧處理、化學品處理、溶劑處理等表面處理。 In addition, whether the coating layer is formed by off-line coating or in-line coating, heat treatment and active energy ray irradiation such as ultraviolet irradiation may be used in combination as necessary. In order to improve the coating properties and adhesion of the coating liquid forming the coating layer to the polyester film, the polyester film can also be subjected to chemical treatment or corona discharge treatment, plasma treatment, ozone treatment, chemicals before coating. Treatment, solvent treatment and other surface treatments.

塗佈液 Coating liquid

形成塗佈層之塗佈液並不受所使用之溶劑限制。其中，較佳為使用將水作為溶劑之水性塗佈液，亦可含有少量有機溶劑。作為有機溶劑，可例示：乙醇、異丙醇、乙二醇、甘油等醇類；乙基溶纖素、第三丁基溶纖素、丙二醇單甲醚、四氫呋喃等醚類；丙酮、甲基乙基酮等酮類；乙酸乙酯等酯類；二甲基乙醇胺等胺類等。該等可單獨使用或者將複數種組合使用。存在可視需要藉由適當選擇該等有機溶劑並使水性塗佈液含有該有機溶劑而使塗佈液之穩定性、塗佈性良好之情形。 The coating liquid used to form the coating layer is not limited by the solvent used. Among them, an aqueous coating liquid using water as a solvent is preferably used, and may contain a small amount of organic solvent. Examples of organic solvents include: alcohols such as ethanol, isopropyl alcohol, ethylene glycol, and glycerol; ethers such as ethyl cellosolve, tert-butyl cellosolve, propylene glycol monomethyl ether, and tetrahydrofuran; acetone, methylethyl Ketones such as ketones; esters such as ethyl acetate; amines such as dimethylethanolamine, etc. These can be used individually or in combination of plural types. There may be cases where the stability and coating properties of the coating liquid can be improved by appropriately selecting these organic solvents and including the organic solvents in the aqueous coating liquid as necessary.

於塗佈液中以包含於由塗佈液形成之塗佈層中之方式含有粒子A。較佳為於塗佈液中含有選自由具有長鏈烷基之化合物、蠟、氟化 合物及聚矽氧化合物所組成之群中之至少一種脫模劑。又，亦可於塗佈液中含有交聯劑交聯而成之聚合物以外之下述各種聚合物。亦可視需要使塗佈液含有界面活性劑。 The coating liquid contains the particles A so as to be included in the coating layer formed from the coating liquid. Preferably, the coating liquid contains a compound selected from a compound having a long-chain alkyl group, wax, fluorinated At least one release agent from the group consisting of compounds and polysiloxane compounds. In addition, the coating liquid may contain various polymers described below in addition to the polymer cross-linked by a cross-linking agent. The coating liquid may also contain a surfactant if necessary.

交聯劑 Cross-linking agent

形成塗佈層之塗佈液中亦可含有交聯劑。於構成塗佈層之塗佈液中含有交聯劑之情形時，塗佈層可形成交聯密度較高之緻密之塗佈層，於乾式膜抗蝕劑步驟中，可賦予更適宜之防受損性。交聯劑並無特別限制，可使用先前公知之交聯劑。作為交聯劑，例如可列舉：三聚氰胺化合物、

Figure 108105213-A0305-02-0016-19
唑啉化合物、環氧化合物、異氰酸酯系化合物、碳二醯亞胺系化合物、矽烷偶合劑化合物等；該等之中，就耐久性之觀點而言，交聯劑較佳為三聚氰胺化合物或
Figure 108105213-A0305-02-0016-20
唑啉化合物，就防受損性之觀點而言，較佳為三聚氰胺化合物。又，該等交聯劑亦可將2種以上併用。再者，亦可使塗佈液中含有任意聚合性單體作為與該等交聯劑一起硬化之成分。 The coating liquid forming the coating layer may also contain a cross-linking agent. When the coating liquid constituting the coating layer contains a cross-linking agent, the coating layer can form a dense coating layer with a higher cross-linking density, which can provide more suitable protection during the dry film resist step. Damage. The cross-linking agent is not particularly limited, and conventionally known cross-linking agents can be used. Examples of the crosslinking agent include: melamine compounds,
Figure 108105213-A0305-02-0016-19
oxazoline compounds, epoxy compounds, isocyanate compounds, carbodiimide compounds, silane coupling agent compounds, etc.; among these, from the viewpoint of durability, the cross-linking agent is preferably a melamine compound or
Figure 108105213-A0305-02-0016-20
From the viewpoint of damage prevention properties, the oxazoline compound is preferably a melamine compound. Moreover, these cross-linking agents can also be used in combination of 2 or more types. Furthermore, the coating liquid may contain any polymerizable monomer as a component that hardens together with the cross-linking agent.

存在用以形成塗佈層之塗佈液中含有交聯劑而製成硬化性之塗佈層之情形。尤其是於應用於可形成極細線之電路之乾式膜抗蝕劑之情形時，若塗佈液中含有交聯劑，則可賦予更優異之表面平滑性。進而，如上所述，藉由使用特定之交聯劑而該效果變得更顯著。 The coating liquid for forming the coating layer may contain a cross-linking agent to form a curable coating layer. Especially when applied to a dry film resist capable of forming circuits with extremely fine lines, if the coating liquid contains a cross-linking agent, it can impart more excellent surface smoothness. Furthermore, as mentioned above, this effect becomes more remarkable by using a specific crosslinking agent.

所謂三聚氰胺化合物，係化合物中具有三聚氰胺骨架之化合物，例如可使用使醇與羥烷化三聚氰胺衍生物、羥烷化三聚氰胺衍生物反應而部分或者完全醚化而成之化合物、及該等之混合物。作為羥烷化，可列舉：羥甲化、羥乙化、異羥丙化、正羥丁化、異羥丁化等。該等之中，就反應性之觀點而言，較佳為羥甲化。又，作為用於醚化之醇，適當 使用甲醇、乙醇、異丙醇、正丁醇、異丁醇等。就提高塗膜強度從而提高塗佈層與基材之密接性之觀點而言，較佳為部分醚化而成之羥烷化三聚氰胺衍生物，更佳為利用甲醇醚化而成之醇。因此，作為更佳之形態，係具有羥甲基及甲氧基甲基之部分醚化三聚氰胺。經醚化之羥烷基相對於未經醚化之羥烷基，較佳為0.5~5當量，更佳為0.7~3當量。又，作為三聚氰胺化合物，可為單體或者二聚物以上之多聚物之任一者，或者亦可使用該等之混合物。進而，亦可使用使脲等與三聚氰胺之一部分共縮合而成者，為了提高三聚氰胺化合物之反應性，亦可使用交聯觸媒。 The melamine compound refers to a compound having a melamine skeleton among the compounds. For example, a compound obtained by reacting an alcohol with a hydroxyalkylated melamine derivative, a hydroxyalkylated melamine derivative and partially or completely etherified, and a mixture thereof can be used. Examples of hydroxyalkylation include hydroxymethylation, hydroxyethylation, isohydroxybutylation, n-hydroxybutylation, isohydroxybutylation, and the like. Among these, hydroxymethylation is preferred from the viewpoint of reactivity. Also, as the alcohol used for etherification, it is appropriate to Use methanol, ethanol, isopropanol, n-butanol, isobutanol, etc. From the viewpoint of improving the strength of the coating film and thereby improving the adhesion between the coating layer and the base material, a hydroxyalkylated melamine derivative obtained by partial etherification is preferred, and an alcohol obtained by etherification with methanol is more preferred. Therefore, a more preferable form is a partially etherified melamine having a hydroxymethyl group and a methoxymethyl group. The etherified hydroxyalkyl group is preferably 0.5 to 5 equivalents, and more preferably 0.7 to 3 equivalents relative to the non-etherified hydroxyalkyl group. In addition, the melamine compound may be a monomer or a polymer of a dimer or higher, or a mixture thereof may be used. Furthermore, what is obtained by co-condensing urea etc. with a part of melamine can also be used. In order to improve the reactivity of a melamine compound, a crosslinking catalyst can also be used.

所謂三聚氰胺之交聯觸媒，係用於提高熱硬化性樹脂之反應性。可使用各種公知之觸媒，例如可列舉：胺化合物、胺化合物之鹽類、對甲苯磺酸等芳香族磺酸化合物或磷酸化合物等有機酸類及其等之鹽、亞胺化合物、脒化合物、胍化合物、有機金屬化合物、硬脂酸鋅或肉豆蔻酸鋅或硬脂酸鋁或硬脂酸鈣等金屬鹽類等。該等之中，較佳為胺化合物、胺化合物之鹽類或對甲苯磺酸，更佳為胺化合物或胺化合物之鹽類。 The so-called melamine cross-linking catalyst is used to increase the reactivity of thermosetting resins. Various well-known catalysts can be used, for example, amine compounds, salts of amine compounds, aromatic sulfonic acid compounds such as p-toluenesulfonic acid, organic acids such as phosphoric acid compounds, and their salts, imine compounds, amidine compounds, Guanidine compounds, organic metal compounds, metal salts such as zinc stearate or zinc myristate, aluminum stearate or calcium stearate, etc. Among these, an amine compound, a salt of an amine compound, or p-toluenesulfonic acid is preferable, and an amine compound or a salt of an amine compound is more preferable.

所謂

Figure 108105213-A0305-02-0017-21
唑啉化合物，係分子內具有
Figure 108105213-A0305-02-0017-22
唑啉基之化合物，尤佳為含有
Figure 108105213-A0305-02-0017-23
唑啉基之聚合物，可藉由含有加成聚合性
Figure 108105213-A0305-02-0017-24
唑啉基之單體單獨製作或者藉由與其他單體之聚合製作。含有加成聚合性
Figure 108105213-A0305-02-0017-25
唑啉基之單體可列舉：2-乙烯基-2-
Figure 108105213-A0305-02-0017-26
唑啉、2-乙烯基-4-甲基-2-
Figure 108105213-A0305-02-0017-27
唑啉、2-乙烯基-5-甲基-2-
Figure 108105213-A0305-02-0017-28
唑啉、2-異丙烯基-2-
Figure 108105213-A0305-02-0017-29
唑啉、2-異丙烯基-4-甲基-2-
Figure 108105213-A0305-02-0017-30
唑啉、2-異丙烯基-5-乙基-2-
Figure 108105213-A0305-02-0017-31
唑啉等；可使用該等之1種或2種以上之混合物。該等之中，2-異丙烯基-2-
Figure 108105213-A0305-02-0017-32
唑啉於工業上亦容易獲取而較佳。其他單體只要為可與含有加成聚合性
Figure 108105213-A0305-02-0017-33
唑啉基之單體共聚之單體，則並無限制，例如可列舉：(甲基)丙烯酸烷基酯(作為烷基，為甲基、乙基、正丙基、異丙基、 正丁基、異丁基、第三丁基、2-乙基己基、環己基)等(甲基)丙烯酸酯類；丙烯酸、甲基丙烯酸、伊康酸、順丁烯二酸、反丁烯二酸、丁烯酸、苯乙烯磺酸及其鹽(鈉鹽、鉀鹽、銨鹽、三級胺鹽等)等不飽和羧酸類；丙烯腈、甲基丙烯腈等不飽和腈類；(甲基)丙烯醯胺、N-烷基(甲基)丙烯醯胺、N,N-二烷基(甲基)丙烯醯胺(作為烷基，為甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、2-乙基己基、環己基等)等不飽和醯胺類；乙酸乙烯酯、丙酸乙烯酯等乙烯酯類；甲基乙烯醚、乙基乙烯醚等乙烯醚類；乙烯、丙烯等α-烯烴類；氯乙烯、偏二氯乙烯、氟乙烯等含鹵素α,β-不飽和單體類；苯乙烯、α-甲基苯乙烯等α,β-不飽和芳香族單體等、可使用該等之1種或2種以上之單體。 so-called
Figure 108105213-A0305-02-0017-21
Oxazoline compounds have in the molecule
Figure 108105213-A0305-02-0017-22
Compounds of oxazoline base, especially those containing
Figure 108105213-A0305-02-0017-23
Oxazoline-based polymers can be obtained by containing addition polymerizability
Figure 108105213-A0305-02-0017-24
The oxazoline-based monomer is produced alone or by polymerization with other monomers. Contains addition polymerizability
Figure 108105213-A0305-02-0017-25
Examples of oxazolinyl monomers include: 2-vinyl-2-
Figure 108105213-A0305-02-0017-26
Oxazoline, 2-vinyl-4-methyl-2-
Figure 108105213-A0305-02-0017-27
Oxazoline, 2-vinyl-5-methyl-2-
Figure 108105213-A0305-02-0017-28
Oxazoline, 2-isopropenyl-2-
Figure 108105213-A0305-02-0017-29
Oxazoline, 2-isopropenyl-4-methyl-2-
Figure 108105213-A0305-02-0017-30
Oxazoline, 2-isopropenyl-5-ethyl-2-
Figure 108105213-A0305-02-0017-31
Oxazoline, etc.; one type or a mixture of two or more types of these can be used. Among these, 2-isopropenyl-2-
Figure 108105213-A0305-02-0017-32
Oxazoline is also easy to obtain industrially and is preferred. Other monomers can be used as long as they contain addition polymerizability
Figure 108105213-A0305-02-0017-33
The monomer for copolymerization of the oxazoline group monomer is not limited, and examples thereof include: (meth)acrylic acid alkyl ester (the alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl). base, isobutyl, tert-butyl, 2-ethylhexyl, cyclohexyl) and other (meth)acrylates; acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid , crotonic acid, styrenesulfonic acid and its salts (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.) and other unsaturated carboxylic acids; unsaturated nitriles such as acrylonitrile and methacrylonitrile; (methyl ) Acrylamide, N-alkyl(meth)acrylamide, N,N-dialkyl(meth)acrylamide (the alkyl group is methyl, ethyl, n-propyl, isopropyl , n-butyl, isobutyl, tert-butyl, 2-ethylhexyl, cyclohexyl, etc.) and other unsaturated amides; vinyl esters such as vinyl acetate, vinyl propionate; methyl vinyl ether, ethyl vinyl ether, etc. Vinyl ethers such as vinyl ether; α-olefins such as ethylene and propylene; halogen-containing α,β-unsaturated monomers such as vinyl chloride, vinylidene chloride, vinyl fluoride and other halogen-containing α,β-unsaturated monomers; styrene, α-methylstyrene, etc. α,β-unsaturated aromatic monomers, etc., one or more of these monomers can be used.

所謂環氧化合物，係分子內具有環氧基之化合物，例如可列舉表氯醇與乙二醇、聚乙二醇、甘油、聚甘油、雙酚A等之羥基或胺基之縮合物；有聚環氧化合物、二環氧化合物、單環氧化合物、縮水甘油胺化合物等。作為聚環氧化合物，例如可列舉：山梨糖醇聚縮水甘油醚、聚甘油聚縮水甘油醚、季戊四醇聚縮水甘油醚、二甘油聚縮水甘油醚、三縮水甘油基三(2-羥基乙基)異氰酸酯、甘油聚縮水甘油醚、三羥甲基丙烷聚縮水甘油醚；作為二環氧化合物，例如可列舉：新戊二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、間苯二酚二縮水甘油醚、乙二醇二縮水甘油醚、聚乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚、聚1,4-丁二醇二縮水甘油醚；作為單環氧化合物，例如可列舉：烯丙基縮水甘油醚、2-乙基己基縮水甘油醚、苯基縮水甘油醚；作為縮水甘油胺化合物，可列舉：N,N,N',N'-四縮水甘油基-間苯二甲胺、1,3-雙(N,N-二縮水甘油基胺基)環己烷等。 The so-called epoxy compound refers to a compound having an epoxy group in the molecule, for example, the condensate of epichlorohydrin and hydroxyl or amine groups of ethylene glycol, polyethylene glycol, glycerol, polyglycerol, bisphenol A, etc.; Polyepoxy compounds, diepoxy compounds, monoepoxy compounds, glycidylamine compounds, etc. Examples of the polyepoxy compound include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, and triglycidyl tris(2-hydroxyethyl). Isocyanate, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether; examples of diepoxy compounds include: neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, m Diphenol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, poly1,4-butylene glycol diglycidyl ether ; Examples of monoepoxy compounds include: allyl glycidyl ether, 2-ethylhexyl glycidyl ether, and phenyl glycidyl ether; examples of glycidyl amine compounds include: N, N, N', N '-Tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylamine)cyclohexane, etc.

所謂異氰酸酯系化合物，係異氰酸酯或者封端異氰酸酯所代表之具有異氰酸酯衍生物結構之化合物。作為異氰酸酯，例如可例示：甲苯二異氰酸酯、苯二甲基二異氰酸酯、亞甲基二苯基二異氰酸酯、伸苯基二異氰酸酯、萘二異氰酸酯等芳香族異氰酸酯；α,α,α',α'-四甲基苯二甲基二異氰酸酯等具有芳香環之脂肪族異氰酸酯；亞甲基二異氰酸酯、伸丙基二異氰酸酯、離胺酸二異氰酸酯、三甲基六亞甲基二異氰酸酯、六亞甲基二異氰酸酯等脂肪族異氰酸酯；環己烷二異氰酸酯、甲基環己烷二異氰酸酯、異佛酮二異氰酸酯、亞甲基雙(4-環己基異氰酸酯)、亞異丙基二環己基二異氰酸酯等脂環族異氰酸酯等。又，亦可列舉該等異氰酸酯之縮二脲化物、異氰尿酸酯化物、脲二酮化物、碳二醯亞胺改性體等聚合物或衍生物。該等可單獨使用，亦可將複數種併用。上述異氰酸酯之中，為了避免因紫外線而導致之黃變，相較於芳香族異氰酸酯，更佳為脂肪族異氰酸酯或脂環族異氰酸酯。 The so-called isocyanate compound refers to a compound having an isocyanate derivative structure represented by isocyanate or blocked isocyanate. Examples of the isocyanate include aromatic isocyanates such as toluene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate; α, α, α', α' - Tetramethylxylylene diisocyanate and other aliphatic isocyanates with aromatic rings; methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene Aliphatic isocyanates such as methyl diisocyanate; cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), isopropyl dicyclohexyl diisocyanate, etc. Alicyclic isocyanates, etc. In addition, polymers or derivatives such as biuret compounds, isocyanurate compounds, uretdione compounds, and carbodiimide-modified products of these isocyanates can also be cited. These can be used individually or in combination. Among the above isocyanates, in order to avoid yellowing caused by ultraviolet rays, aliphatic isocyanates or alicyclic isocyanates are more preferred than aromatic isocyanates.

於以封端異氰酸酯之狀態使用之情形時，作為其封端劑，例如可列舉：重亞硫酸鹽類、苯酚、甲酚、乙基苯酚等酚系化合物；丙二醇單甲醚、乙二醇、苄醇、甲醇、乙醇等醇系化合物；丙二酸二甲酯、丙二酸二乙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、乙醯丙酮等活性亞甲基系化合物；丁基硫醇、十二烷基硫醇等硫醇系化合物；ε-己內醯胺、δ-戊內醯胺等內醯胺系化合物；二苯基苯胺、苯胺、伸乙亞胺等胺系化合物；乙醯苯胺、乙酸醯胺之酸醯胺化合物、甲醛、乙醛肟、丙酮肟、甲基乙基酮肟、環己酮肟等肟系化合物；該等可單獨使用，亦可將2種以上併用。該等之中，尤其是就於加熱後剝離特性亦不易變化之觀點而言，較佳為活性亞甲基系化合物。 When used in the state of blocked isocyanate, examples of the blocking agent include: bisulfites, phenolic compounds such as phenol, cresol, and ethylphenol; propylene glycol monomethyl ether, ethylene glycol, Alcohol compounds such as benzyl alcohol, methanol, and ethanol; active methylene compounds such as dimethyl malonate, diethyl malonate, methyl acetyl acetate, ethyl acetate, and acetyl acetone; butyl Thiol-based compounds such as mercaptans and dodecylmercaptan; lactam-based compounds such as ε-caprolactam and δ-valerolactam; amine-based compounds such as diphenylaniline, aniline, and ethylideneimine ; Acetyl aniline, acetamide acid amide compounds, formaldehyde, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime and other oxime compounds; these can be used alone, or two types can be combined Use the above together. Among these, active methylene-based compounds are preferred especially from the viewpoint that peeling properties are not easily changed even after heating.

又，異氰酸酯系化合物可以單體形式使用，亦可作為與各種聚合物之混合物或結合物使用。就提高異氰酸酯系化合物之分散性及交聯性之意義而言，較佳為使用與聚酯樹脂或胺基甲酸酯樹脂之混合物或結合物。 In addition, the isocyanate-based compound can be used in a monomer form or as a mixture or combination with various polymers. In order to improve the dispersibility and crosslinkability of the isocyanate-based compound, it is preferable to use a mixture or combination with a polyester resin or a urethane resin.

所謂碳二醯亞胺系化合物，係具有碳二醯亞胺結構之化合物，用於提高塗佈層之耐濕熱性。碳二醯亞胺系化合物可利用先前公知之技術合成，一般使用二異氰酸酯化合物之縮合反應。作為二異氰酸酯化合物，並無特別限定，可使用芳香族系、脂肪族系之任一者，具體而言，可列舉：甲苯二異氰酸酯、二甲苯二異氰酸酯、二苯甲烷二異氰酸酯、伸苯基二異氰酸酯、萘二異氰酸酯、六亞甲基二異氰酸酯、三甲基六亞甲基二異氰酸酯、環己烷二異氰酸酯、甲基環己烷二異氰酸酯、異佛酮二異氰酸酯、二環己基二異氰酸酯、二環己基甲烷二異氰酸酯等。 The so-called carbodiimide compound is a compound having a carbodiimide structure and is used to improve the heat and moisture resistance of the coating layer. Carbodiimide compounds can be synthesized using previously known techniques, generally using the condensation reaction of diisocyanate compounds. The diisocyanate compound is not particularly limited, and either aromatic or aliphatic compounds can be used. Specific examples include toluene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, and phenylene diisocyanate. Isocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, dicyclohexyl diisocyanate, diisocyanate Cyclohexylmethane diisocyanate, etc.

作為矽烷偶合劑化合物，係1個分子中具有有機官能基與烷氧基等水解基之有機矽化合物。例如可列舉：3-縮水甘油氧基丙基甲基二甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷等含環氧基之化合物；乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷等含乙烯基之化合物；對苯乙烯基三甲氧基矽烷、對苯乙烯基三乙氧基矽烷等含苯乙烯基之化合物；3-(甲基)丙烯醯氧基丙基三甲氧基矽烷、3-(甲基)丙烯醯氧基丙基三乙氧基矽烷、3-(甲基)丙烯醯氧基丙基甲基二甲氧基矽烷、3-(甲基)丙烯醯氧基丙基甲基二乙氧基矽烷等含(甲基)丙烯酸基之化合物；3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、N-2-(胺基乙基)-3- 胺基丙基三乙氧基矽烷、N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基甲基二乙氧基矽烷、3-三乙氧基矽烷基-N-(1,3-二甲基亞丁基)丙基胺、N-苯基-3-胺基丙基三甲氧基矽烷、N-苯基-3-胺基丙基三乙氧基矽烷等含胺基之化合物；三(三甲氧基矽烷基丙基)異氰尿酸酯、三(三乙氧基矽烷基丙基)異氰尿酸酯等含異氰尿酸基之化合物；3-巰基丙基三甲氧基矽烷、3-巰基丙基三乙氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基甲基二乙氧基矽烷等含巰基之化合物等。 The silane coupling agent compound is an organosilicon compound having an organic functional group and a hydrolyzable group such as an alkoxy group in one molecule. Examples include: 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3 -Epoxy group-containing compounds such as glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethyl Oxysilane and other vinyl-containing compounds; p-styryltrimethoxysilane, p-styryltriethoxysilane and other styryl-containing compounds; 3-(meth)acryloxypropyltrimethoxy Silane, 3-(meth)acryloxypropyltriethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxysilane Compounds containing (meth)acrylic acid groups such as methylpropylmethyldiethoxysilane; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(amine ethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3- Aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-amino Propylmethyldiethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine, N-phenyl-3-aminopropyltrimethoxy Silane, N-phenyl-3-aminopropyltriethoxysilane and other amine-containing compounds; tris(trimethoxysilylpropyl)isocyanurate, tris(triethoxysilylpropyl) base) isocyanurate and other compounds containing isocyanurate groups; 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-Mercaptopropylmethyldiethoxysilane and other thiol-containing compounds.

上述化合物之中，就保持塗佈層之強度之觀點而言，更佳為含環氧基之矽烷偶合劑化合物、含乙烯基或(甲基)丙烯酸基等雙鍵之矽烷偶合劑化合物、含胺基之矽烷偶合劑化合物。 Among the above-mentioned compounds, from the viewpoint of maintaining the strength of the coating layer, more preferred are silane coupling agent compounds containing epoxy groups, silane coupling agent compounds containing double bonds such as vinyl groups or (meth)acrylic acid groups, and Amino-based silane coupling agent compound.

塗佈液中所包含之交聯劑可以於形成塗佈層時之乾燥過程及製膜過程中進行反應而提高塗佈層之性能之設計使用。可推測於由塗佈液形成之塗佈層中存在該等交聯劑之未反應物、反應後之化合物或者其等之混合物。 The cross-linking agent contained in the coating liquid can react during the drying process and film-making process when forming the coating layer to improve the performance of the coating layer. It is presumed that unreacted products of these cross-linking agents, reacted compounds, or mixtures thereof exist in the coating layer formed from the coating liquid.

塗佈液中之交聯劑之含量相對於塗佈液中之全部非揮發成分，較佳為5~85質量%，更佳為15~80質量%，進而較佳為25~70質量%，尤佳為30~50質量%。於交聯劑之含量相對於塗佈液中之全部非揮發成分為5~85質量%之情形時，由塗佈液形成之塗佈層之強度提高，可進一步提高防受損性，並且可同時滿足平滑性。進而，於塗佈層中視需要包含抗靜電劑之情形時，可抑制抗靜電劑自塗佈層中滲出，從而防止因滲出而導致產生之膜之污染。於交聯劑之含量相對於塗佈液中之全部非揮發成分未達5質量%之情形時，存在無法獲得充分之防受損性能之情形。 The content of the cross-linking agent in the coating liquid is preferably 5 to 85 mass %, more preferably 15 to 80 mass %, and further preferably 25 to 70 mass %, based on all non-volatile components in the coating liquid. Particularly preferred is 30 to 50% by mass. When the content of the cross-linking agent is 5 to 85% by mass relative to the total non-volatile components in the coating liquid, the strength of the coating layer formed from the coating liquid is increased, the damage resistance can be further improved, and the coating layer can be while satisfying smoothness. Furthermore, when the coating layer optionally contains an antistatic agent, the antistatic agent can be suppressed from seeping out of the coating layer, thereby preventing film contamination caused by seepage. When the content of the cross-linking agent is less than 5% by mass relative to the total non-volatile components in the coating liquid, sufficient damage prevention performance may not be obtained.

於塗佈液中視需要含有交聯觸媒之情形時，交聯觸媒之含 量相對於塗佈液中之非揮發成分，通常為0.4~10質量%，較佳為0.6~8質量%，更佳為0.8~5質量%。有若交聯觸媒之含量為0.4~10質量%，則可獲得具有理想之防受損性能之塗佈膜之傾向。 When the coating liquid contains a cross-linking catalyst as necessary, the content of the cross-linking catalyst The amount is usually 0.4 to 10% by mass, preferably 0.6 to 8% by mass, and more preferably 0.8 to 5% by mass relative to the non-volatile components in the coating liquid. If the content of the cross-linking catalyst is 0.4 to 10% by mass, a coating film with ideal damage prevention properties tends to be obtained.

塗佈液中含有粒子，將塗佈液中所包含且由塗佈液構成之塗佈層中所包含之粒子亦稱為粒子A。塗佈液中所包含之粒子A包含粒徑為30~80nm之粒子AS(以下，存在簡稱為「粒子AS」之情形)及粒徑為100~400nm之粒子AL(以下，存在簡稱為「粒子AL」之情形)。於塗佈液中，以相對於對由塗佈液形成之塗佈層之表面進行觀察時之該塗佈層表面中所占之粒子之面積合計，粒子AS之面積比率成為60~99.9%之範圍內且粒子AL之面積比率成為0.1~15%之範圍內之方式含有粒子AS及粒子AL。 The coating liquid contains particles, and the particles contained in the coating liquid and included in the coating layer composed of the coating liquid are also referred to as particles A. The particles A contained in the coating liquid include particles AS with a particle diameter of 30 to 80 nm (hereinafter, referred to as "particles AS") and particles AL with a particle diameter of 100 to 400 nm (hereinafter, referred to as "particles"). AL" situation). In the coating liquid, the area ratio of the particles AS is 60 to 99.9% relative to the total area of the particles occupying the surface of the coating layer when the surface of the coating layer formed by the coating liquid is observed. The particle AS and the particle AL are included so that the area ratio of the particle AL is within the range of 0.1 to 15%.

塗佈液中所包含之粒子A亦可包含粒子AS及粒子AL以外之粒徑未達1μm之粒子。較佳為於塗佈液中含有選自由具有長鏈烷基之化合物、蠟、氟化合物及聚矽氧化合物所組成之群中之至少一種脫模劑。又，於塗佈液中含有交聯劑之情形時，亦可含有交聯而成之聚合物以外之下述各種聚合物。 The particles A contained in the coating liquid may also include particles other than particles AS and particles AL having a particle diameter of less than 1 μm. It is preferable that the coating liquid contains at least one release agent selected from the group consisting of compounds having long-chain alkyl groups, waxes, fluorine compounds, and polysiloxane compounds. Furthermore, when the coating liquid contains a cross-linking agent, the following various polymers may be included in addition to the cross-linked polymer.

於塗佈液中，亦可以包含於由塗佈液形成之塗佈層中之方式，視需要以於塗佈層中成為45質量%以下之方式含有抗靜電劑。又，塗佈液亦可含有界面活性劑。 The coating liquid may also contain the antistatic agent in the coating layer formed from the coating liquid. If necessary, the antistatic agent may be contained in the coating layer in an amount of 45% by mass or less. Moreover, the coating liquid may contain a surfactant.

塗佈層 coating layer

本發明之DFR基材用膜之塗佈層較佳為藉由上述方法由塗佈液形成之塗佈層。 The coating layer of the film for DFR base material of the present invention is preferably a coating layer formed from a coating liquid by the above method.

DFR基材用膜之塗佈層於聚酯膜為多層構成之情形時，可為由塗佈於含有粒子之表層之塗佈液形成之塗佈層，亦可為由塗佈於不含粒子之表層之塗佈液形成之塗佈層。於多層構成之聚酯膜中之一表層包含粒子B且具有與包含該粒子B之表層相接之塗佈層之DFR基材膜藉由塗佈層而防受損性及平滑性良好，故而於加工步驟中容易操作，於乾式膜抗蝕劑步驟中，容易於不包含粒子B之層之側形成抗蝕劑層。於多層構成之聚酯膜中之一表層包含粒子B且具有與不包含粒子B之另一表層相接之塗佈層之DFR基材膜藉由塗佈層而防受損性及平滑性良好，故而於加工步驟中容易操作，於乾式膜抗蝕劑步驟中容易形成抗蝕劑層。 When the polyester film has a multi-layer structure, the coating layer of the film for DFR base material may be a coating layer formed by coating a coating liquid on a surface layer containing particles, or it may be a coating layer coated on a surface layer that does not contain particles. The coating layer formed by the coating liquid on the surface layer. A DFR base film in which one of the surface layers of a multi-layered polyester film contains particles B and has a coating layer in contact with the surface layer containing the particles B has excellent damage resistance and smoothness due to the coating layer. It is easy to operate in the processing step, and in the dry film resist step, it is easy to form a resist layer on the side of the layer that does not contain particles B. A DFR base film in which one surface layer of a multi-layered polyester film contains particles B and has a coating layer connected to another surface layer that does not contain particles B has excellent damage prevention and smoothness due to the coating layer , so it is easy to operate in the processing step and the resist layer is easy to form in the dry film resist step.

DFR基材用膜之塗佈層之厚度(以下，亦稱為「塗佈層之膜厚」)通常為0.001~1μm，較佳為0.002~0.5μm，更佳為0.005~0.2μm，進而較佳為0.008~0.15μm，尤佳為0.01~0.1μm，最佳為0.01~0.08μm。若塗佈層之厚度為0.001~1μm，則於用作DFR基材用膜之情形時，塗膜外觀亦良好，可獲得充分之曝光性，且可獲得充分之防受損性能。塗佈層之膜厚可藉由下述實施例所記載之塗佈層之膜厚之測定方法進行測定。若DFR基材用膜之塗佈層之膜厚為0.001~1μm，則於包含粒子AS及粒子AL之塗佈層中，藉由粒子AS，可維持透明性，並且獲得充分之防受損性能，從而進一步提高防磨削性，藉由粒子AL，可進一步提高空氣逃逸性及平滑性。此種厚度之塗佈層可藉由尤其是線內塗佈而較佳地設置。 The thickness of the coating layer of the DFR base material film (hereinafter also referred to as the "film thickness of the coating layer") is usually 0.001 to 1 μm, preferably 0.002 to 0.5 μm, more preferably 0.005 to 0.2 μm, and further preferably Preferably, it is 0.008~0.15μm, particularly preferably 0.01~0.1μm, and most preferably 0.01~0.08μm. If the thickness of the coating layer is 0.001~1μm, when used as a film for DFR substrates, the appearance of the coating film will be good, sufficient exposure can be obtained, and sufficient damage prevention performance can be obtained. The film thickness of the coating layer can be measured by the method for measuring the film thickness of the coating layer described in the following examples. If the film thickness of the coating layer of the DFR base material film is 0.001~1 μm, in the coating layer including particle AS and particle AL, transparency can be maintained by particle AS and sufficient damage prevention performance can be obtained , thereby further improving the anti-grinding property, and the air escape and smoothness can be further improved through the particles AL. A coating layer of this thickness can preferably be provided by in-line coating in particular.

抗靜電劑 antistatic agent

DFR基材用膜之塗佈層視需要包含抗靜電劑。於獲得具有所需之防 受損性與平滑性之塗佈層之情形時，塗佈層亦可不包含抗靜電劑。塗佈層中之抗靜電劑之含量並無限制，通常為45質量%以下，較佳為1~45質量%，更佳為5~40質量%，進而較佳為10~35質量%，尤佳為15~30質量%。若塗佈層中之抗靜電劑之含量為45質量%以下，則可抑制抗靜電劑自塗佈層滲出。又，若塗佈層中之抗靜電劑之含量為1質量%以上，則可降低塗佈層之表面電阻，防止因抗靜電劑自塗佈層滲出而導致產生之DFR基材用膜之污染，並且可抑制灰塵等之吸附。塗佈層中之抗靜電劑之含量例如可藉由元素分析、螢光X射線、NMR(nuclear magnetic resonance，核磁共振)等進行測定。塗佈液中之抗靜電劑之含量並無限制，相對於塗佈液中之非揮發成分，通常為45質量%以下，較佳為1~45質量%，更佳為5~40質量%，進而較佳為10~35質量%，尤佳為15~30質量%。 The coating layer of the film for DFR base material optionally contains an antistatic agent. to obtain the necessary protection In the case of a damaged and smooth coating layer, the coating layer may not contain an antistatic agent. The content of the antistatic agent in the coating layer is not limited, but is usually less than 45 mass%, preferably 1 to 45 mass%, more preferably 5 to 40 mass%, and more preferably 10 to 35 mass%, especially Preferably, it is 15~30% by mass. If the content of the antistatic agent in the coating layer is 45% by mass or less, bleeding of the antistatic agent from the coating layer can be suppressed. In addition, if the content of the antistatic agent in the coating layer is 1% by mass or more, the surface resistance of the coating layer can be reduced and contamination of the DFR base film caused by the antistatic agent bleeding out from the coating layer can be prevented. , and can inhibit the adsorption of dust, etc. The content of the antistatic agent in the coating layer can be measured, for example, by elemental analysis, fluorescent X-rays, NMR (nuclear magnetic resonance, nuclear magnetic resonance), and the like. The content of the antistatic agent in the coating liquid is not limited. It is usually 45 mass% or less, preferably 1 to 45 mass%, and more preferably 5 to 40 mass% relative to the non-volatile components in the coating liquid. Furthermore, 10-35 mass % is more preferable, and 15-30 mass % is especially preferable.

本發明之DFR基材用膜之塗佈層由於視需要含有抗靜電劑，故而塗佈層之表面電阻值較佳為1×1010Ω以上，更佳為5×1010~1×1015Ω，進而較佳為1×1011~1×1015Ω。於DFR基材用膜之塗佈層之表面電阻值未達1×1010Ω之情形時，必需大量抗靜電劑，而會產生抗靜電劑之滲出或塗佈液中之交聯劑之含量相對減少，故而防受損性可能會降低。 Since the coating layer of the DFR substrate film of the present invention contains an antistatic agent if necessary, the surface resistance value of the coating layer is preferably 1×10 10 Ω or more, and more preferably 5×10 10 ~1×10 15 Ω, and more preferably 1×10 11 ~1×10 15 Ω. When the surface resistance value of the coating layer of the DFR substrate film does not reach 1×10 10 Ω, a large amount of antistatic agent is necessary, which may cause the antistatic agent to bleed out or the content of the cross-linking agent in the coating liquid. Relatively reduced, so damage resistance may be reduced.

作為抗靜電劑，例如可列舉：四級銨鹽、吡啶鎓鹽、具有一~三級胺基等陽離子性官能基之陽離子系抗靜電劑、具有磺酸鹼基、硫酸酯鹼基、磷酸酯鹼基、膦酸鹼基等陰離子性官能基之陰離子系抗靜電劑、胺基酸系、胺基硫酸酯系等兩性抗靜電劑、多元醇系、聚甘油系、聚乙二醇系等具有非離子性官能基之抗靜電劑等各種高分子型抗靜電劑。又，亦可使用具有三級胺基或四級銨基且可藉由游離輻射進行聚合之單體或低聚物、例如N,N-二烷基(甲基)丙烯酸胺基烷基酯單體、其等之四級化 合物等聚合性抗靜電劑、進而聚苯胺、聚吡咯、聚噻吩等導電性聚合物等。該等之中，較佳為具有三級胺基或四級銨基之高分子型抗靜電劑。 Examples of antistatic agents include quaternary ammonium salts, pyridinium salts, cationic antistatic agents having cationic functional groups such as primary to tertiary amine groups, sulfonic acid bases, sulfate ester bases, and phosphate esters. Anionic antistatic agents with anionic functional groups such as bases and phosphonic acid bases, amphoteric antistatic agents such as amino acid-based and amino sulfate-based antistatic agents, polyol-based, polyglycerol-based, polyethylene glycol-based antistatic agents, etc. Various polymer antistatic agents such as antistatic agents with non-ionic functional groups. In addition, monomers or oligomers that have tertiary amine groups or quaternary ammonium groups and can be polymerized by ionizing radiation, such as N,N-dialkyl (meth)acrylic acid aminoalkyl ester monomers, can also be used. The fourth level of body, etc. Polymeric antistatic agents such as compounds, and conductive polymers such as polyaniline, polypyrrole, and polythiophene. Among these, a polymer-type antistatic agent having a tertiary amine group or a quaternary ammonium group is preferred.

界面活性劑 surfactant

DFR基材膜之塗佈層中亦可含有界面活性劑。塗佈層可藉由形成塗佈層之塗佈液中所含有之界面活性劑提高塗佈液對聚酯膜之潤濕性，抑制塗佈不均(塗佈層之不均勻度)或塗佈液之收縮，從而使塗佈層之外觀良好。塗佈層中之界面活性劑之含量通常為0.01質量%以上，較佳為0.01~10質量%，更佳為0.05~5.0質量%，進而較佳為0.10~3.0質量%，尤佳為0.10~1.0質量%，最佳為0.30~1.0質量%。若塗佈層中之界面活性劑之含量為0.01質量%以上，則可維持塗佈層之透明性、防受損性及平滑性之特性，並且可提高對聚酯膜之潤濕性，抑制塗佈不均或塗佈液之收縮，從而使塗佈層之外觀更良好。存在若塗佈層中之界面活性劑之含量未達0.01質量%，則難以改善潤濕性，若超過10質量%，則塗佈層之透明性降低而DFR基材膜之霧度之值增大之情形。推測塗佈層中之界面活性劑之含量與相對於塗佈液中之非揮發成分的界面活性劑之含量大致相等。塗佈液中之界面活性劑之含量相對於塗佈液中之非揮發成分，較佳為0.01~10質量%，更佳為0.05~5.0質量%，進而較佳為0.10~3.0質量%，尤佳為0.10~1.0質量%，最佳為0.30~1.0質量%。 The coating layer of the DFR substrate film may also contain surfactants. The coating layer can use the surfactant contained in the coating liquid that forms the coating layer to improve the wettability of the coating liquid to the polyester film and suppress uneven coating (unevenness of the coating layer) or coating The shrinkage of the cloth liquid makes the coating layer have a good appearance. The content of the surfactant in the coating layer is usually 0.01% by mass or more, preferably 0.01~10% by mass, more preferably 0.05~5.0% by mass, further preferably 0.10~3.0% by mass, especially 0.10~ 1.0% by mass, optimally 0.30~1.0% by mass. If the content of the surfactant in the coating layer is 0.01% by mass or more, the transparency, damage resistance and smoothness of the coating layer can be maintained, and the wettability of the polyester film can be improved, inhibiting Uneven coating or shrinkage of the coating liquid will make the appearance of the coating layer better. If the surfactant content in the coating layer is less than 0.01% by mass, it will be difficult to improve the wettability. If it exceeds 10% by mass, the transparency of the coating layer will decrease and the haze value of the DFR base film will increase. Big situation. It is estimated that the content of the surfactant in the coating layer is approximately equal to the content of the surfactant relative to the non-volatile components in the coating liquid. The content of the surfactant in the coating liquid relative to the non-volatile components in the coating liquid is preferably 0.01 to 10 mass %, more preferably 0.05 to 5.0 mass %, and further preferably 0.10 to 3.0 mass %, especially The preferred range is 0.10~1.0% by mass, and the optimum range is 0.30~1.0% by mass.

作為界面活性劑，可使用陰離子系界面活性劑、非離子系界面活性劑、陽離子系界面活性劑、兩性界面活性劑。該等之中，就與各種樹脂之相溶性之觀點而言，較佳為陰離子系界面活性劑、非離子系界面活性劑，尤佳為陰離子系界面活性劑。 As the surfactant, anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants can be used. Among these, from the viewpoint of compatibility with various resins, anionic surfactants and nonionic surfactants are preferred, and anionic surfactants are particularly preferred.

作為陰離子系界面活性劑，例如可列舉：烷基磺酸鹽、烷基芳基磺酸鹽、酯磺酸鹽等磺酸型；烷基磷酸酯或其鹽、聚氧伸烷基烷基醚磷酸酯或其鹽等磷酸型；烷基硫酸酯鹽、烷基醚硫酸酯鹽等硫酸酯型；烷基脂肪酸鹽等羧酸鹽型等。該等之中，就抗靜電性優異之觀點而言，較佳為磺酸型。 Examples of anionic surfactants include sulfonic acid types such as alkyl sulfonates, alkylaryl sulfonates, and ester sulfonates; alkyl phosphates or salts thereof, and polyoxyalkylene alkyl ethers. Phosphoric acid type such as phosphate ester or its salt; sulfate type such as alkyl sulfate ester salt, alkyl ether sulfate ester salt; carboxylate type such as alkyl fatty acid salt, etc. Among these, the sulfonic acid type is preferable from the viewpoint of excellent antistatic properties.

作為磺酸型陰離子系界面活性劑，例如可列舉：癸基磺酸鹽、十二烷基磺酸鹽、十四烷基磺酸鹽、十六烷基磺酸鹽、十八烷基磺酸鹽等烷基磺酸鹽；丁基苯磺酸鹽、己基苯磺酸鹽、辛基苯磺酸鹽、癸基苯磺酸鹽、十二烷基苯磺酸鹽、十四烷基苯磺酸鹽、十六烷基苯磺酸鹽、十八烷基苯磺酸鹽、二丁基萘磺酸鹽、三異丙基萘磺酸鹽等烷基芳基磺酸鹽；二丁基磺基琥珀酸酯鹽、二辛基磺基琥珀酸酯鹽、十二烷基磺基乙酸酯鹽、壬基苯氧基聚乙二醇磺基乙酸酯鹽等酯磺酸鹽。該等之中，就抗靜電性優異之觀點而言，烷基之碳數為8以上、較佳為10~22、進而較佳為12~18之範圍。又，作為鹽，較佳為金屬鹽，尤其更佳為鋰、鈉、鉀等鹼金屬鹽，進而較佳為鈉鹽。作為種類，就抗靜電性之觀點而言，較佳為烷基磺酸鹽。 Examples of sulfonic acid-type anionic surfactants include: decyl sulfonate, dodecyl sulfonate, tetradecyl sulfonate, hexadecyl sulfonate, and octadecyl sulfonate. Salts and other alkyl sulfonates; butyl benzene sulfonate, hexyl benzene sulfonate, octyl benzene sulfonate, decyl benzene sulfonate, dodecyl benzene sulfonate, tetradecyl benzene sulfonate Alkyl aryl sulfonates such as cetyl benzene sulfonate, octadecyl benzene sulfonate, dibutyl naphthalene sulfonate, triisopropyl naphthalene sulfonate; dibutyl sulfonate Ester sulfonates such as dioctyl sulfosuccinate salt, dioctyl sulfosuccinate salt, dodecyl sulfoacetate salt, nonylphenoxy polyethylene glycol sulfoacetate salt, etc. Among these, from the viewpoint of excellent antistatic properties, the number of carbon atoms in the alkyl group is 8 or more, preferably 10 to 22, and further preferably 12 to 18. Moreover, as a salt, a metal salt is preferable, an alkali metal salt such as lithium, sodium, and potassium is especially more preferable, and a sodium salt is even more preferable. As a type, from the viewpoint of antistatic properties, alkyl sulfonates are preferred.

作為磷酸型陰離子系界面活性劑，例如可列舉：磷酸丁酯、丁基磷酸酯鹽、磷酸己酯、己基磷酸酯鹽、磷酸辛酯、辛基磷酸酯鹽、磷酸癸酯、癸基磷酸酯鹽、磷酸月桂基酯、月桂基磷酸酯鹽、磷酸十四烷基酯、十四烷基磷酸酯鹽、磷酸十六烷基酯、十六烷基磷酸酯鹽、磷酸硬脂酯、硬脂基磷酸酯鹽等磷酸烷基酯或其鹽；聚氧乙烯丁基醚磷酸酯、聚氧乙烯丁基醚磷酸酯鹽、聚氧乙烯己基醚磷酸酯、聚氧乙烯己基醚磷酸酯鹽、聚氧乙烯辛基醚磷酸酯、聚氧乙烯辛基醚磷酸酯鹽、聚氧乙烯 癸基醚磷酸酯、聚氧乙烯癸基醚磷酸酯鹽、聚氧乙烯月桂醚磷酸酯、聚氧乙烯月桂醚磷酸酯鹽、聚氧乙烯十四烷基醚磷酸酯、聚氧乙烯十四烷基醚磷酸酯鹽、聚氧乙烯十六烷基醚磷酸酯、聚氧乙烯十六烷基醚磷酸酯鹽、聚氧乙烯硬脂基醚磷酸酯、聚氧乙烯硬脂基醚磷酸酯鹽、聚氧化丙烯辛基醚磷酸酯、聚氧化丙烯辛基醚磷酸酯鹽、聚氧化丙烯癸基醚磷酸酯、聚氧化丙烯癸基醚磷酸酯鹽、聚氧化丙烯月桂醚磷酸酯、聚氧化丙烯月桂醚磷酸酯鹽等聚氧伸烷基烷基醚磷酸酯或其鹽等。 Examples of the phosphoric acid-type anionic surfactant include butyl phosphate, butyl phosphate, hexyl phosphate, hexyl phosphate, octyl phosphate, octyl phosphate, decyl phosphate, and decyl phosphate. Salt, lauryl phosphate, lauryl phosphate, myristyl phosphate, myristyl phosphate, cetyl phosphate, cetyl phosphate, stearyl phosphate, stearyl phosphate Phosphate alkyl esters such as base phosphate ester salts or their salts; polyoxyethylene butyl ether phosphate ester, polyoxyethylene butyl ether phosphate ester salt, polyoxyethylene hexyl ether phosphate ester, polyoxyethylene hexyl ether phosphate ester salt, polyoxyethylene hexyl ether phosphate ester salt, Oxyethylene octyl ether phosphate, polyoxyethylene octyl ether phosphate, polyoxyethylene Decyl ether phosphate, polyoxyethylene decyl ether phosphate, polyoxyethylene lauryl ether phosphate, polyoxyethylene lauryl ether phosphate, polyoxyethylene tetradecyl ether phosphate, polyoxyethylene tetradecane Polyoxyethylene cetyl ether phosphate, polyoxyethylene cetyl ether phosphate, polyoxyethylene cetyl ether phosphate, polyoxyethylene stearyl ether phosphate, polyoxyethylene stearyl ether phosphate, Polyoxypropylene octyl ether phosphate, polyoxypropylene octyl ether phosphate, polyoxypropylene decyl ether phosphate, polyoxypropylene decyl ether phosphate, polyoxypropylene lauryl ether phosphate, polyoxypropylene laurel Polyoxyalkylene alkyl ether phosphates such as ether phosphate ester salts or their salts, etc.

該等之中，就作為界面活性劑之性能、抗靜電性能之觀點而言，較佳為烷基磷酸酯鹽或聚氧伸烷基烷基醚磷酸酯或其鹽。 Among these, from the viewpoint of performance as a surfactant and antistatic performance, an alkyl phosphate ester salt or a polyoxyalkylene alkyl ether phosphate or a salt thereof is preferred.

又，關於烷基磷酸酯鹽，烷基之碳數為4以上、較佳為4~22、進而較佳為6~12之範圍，關於聚氧伸烷基烷基醚磷酸酯或其鹽，烷基之碳數為4以上、較佳為6~22、進而較佳為8~18之範圍。又，作為鹽，較佳為金屬鹽或胺鹽，尤其更佳為鋰、鈉、鉀等鹼金屬鹽、烷基胺鹽、醇胺鹽，進而較佳為鈉鹽或單乙醇胺鹽。 Furthermore, regarding the alkyl phosphate ester salt, the carbon number of the alkyl group is 4 or more, preferably 4 to 22, and further preferably 6 to 12. Regarding the polyoxyalkylene alkyl ether phosphate ester or its salt, The number of carbon atoms in the alkyl group is 4 or more, preferably 6 to 22, and further preferably 8 to 18. Furthermore, as the salt, a metal salt or an amine salt is preferred, an alkali metal salt such as lithium, sodium, and potassium, an alkylamine salt, or an alcoholamine salt is particularly preferred, and a sodium salt or a monoethanolamine salt is further preferred.

作為非離子系界面活性劑，例如可列舉：甘油或糖類等多元醇與脂肪酸酯鍵結而成之酯型、聚氧乙烯烷基醚或聚氧乙烯烷基苯基醚等醚型、使環氧烷加成於脂肪酸或多元醇脂肪酸酯而成之酯-醚型、疏水基與親水基經由醯胺鍵結之脂肪酸烷醇醯胺等醯胺型等。該等之中，若考慮到耐熱性，則較佳為酯型、醚型、及酯-醚型，若考慮到抗靜電性能，則較佳為醚型。 Examples of the nonionic surfactant include ester type in which polyhydric alcohols such as glycerin or sugar are bonded to fatty acid esters, ether types such as polyoxyethylene alkyl ether or polyoxyethylene alkylphenyl ether, etc. The ester-ether type formed by adding alkylene oxide to fatty acid or polyhydric alcohol fatty acid ester, and the amide type such as fatty acid alkanol amide in which the hydrophobic group and the hydrophilic group are bonded through amide. Among these, when heat resistance is taken into consideration, ester type, ether type, and ester-ether type are preferable, and when antistatic performance is taken into consideration, ether type is preferable.

作為酯型或酯-醚型非離子系界面活性劑，例如可列舉：甘油單(二)月桂酸酯、甘油單(二)硬脂酸酯、甘油、甘油單(二)油酸酯、二甘油單(二)硬脂酸酯、三甘油單(二)硬脂酸酯等甘油脂肪酸酯；聚氧乙烯 甘油單(二)月桂酸酯、聚氧乙烯甘油單(二)硬脂酸酯、聚氧化丙烯甘油單(二)月桂酸酯、聚氧化丙烯甘油單(二)硬脂酸酯、聚氧化丁烯甘油單(二)月桂酸酯、聚氧化丁烯甘油單(二)硬脂酸酯等聚氧伸烷基甘油脂肪酸酯；聚氧乙烯單(二)月桂酸酯、聚氧乙烯單(二)硬脂酸酯、聚氧乙烯單(二)油酸酯、聚氧化丙烯單(二)月桂酸酯、聚氧化丙烯單(二)硬脂酸酯等聚氧伸烷基脂肪酸酯；山梨醇酐單(二)月桂酸酯、山梨醇酐單(二)棕櫚酸酯、山梨醇酐單(二)硬脂酸酯、山梨醇酐單(二)油酸酯等山梨醇酐脂肪酸酯；聚氧乙烯山梨醇酐單肉桂酸酯、聚氧乙烯山梨醇酐單棕櫚酸酯、聚氧乙烯山梨醇酐單硬脂酸酯、聚氧乙烯山梨醇酐三硬脂酸酯、聚氧乙烯山梨醇酐單油酸酯、聚氧乙烯山梨醇酐三油酸酯、聚氧化丙烯山梨醇酐單月桂酸酯、聚氧化丙烯山梨醇酐單硬脂酸酯等聚氧伸烷基山梨醇酐脂肪酸酯等。 Examples of ester type or ester-ether type nonionic surfactants include: glycerol mono(di)laurate, glycerol mono(di)stearate, glycerol, glycerol mono(di)oleate, di-oleate, Glyceryl fatty acid esters such as glyceryl mono(di)stearate and triglyceryl mono(di)stearate; polyoxyethylene Glyceryl mono(di)laurate, polyoxyethylene glyceryl mono(di)stearate, polyoxypropylene glyceryl mono(di)laurate, polyoxyethylene glyceryl mono(di)stearate, polyoxybutylene Polyoxyalkylene glycerol fatty acid esters such as glycerol mono(di)laurate and polyoxybutylene glycerol mono(di)stearate; polyoxyethylene mono(di)laurate, polyoxyethylene mono(di)laurate 2) Polyoxyalkylene fatty acid esters such as stearate, polyoxyethylene mono(di)oleate, polyoxypropylene mono(di)laurate, polyoxypropylene mono(di)stearate; Sorbitan fatty acids such as sorbitan mono(di)laurate, sorbitan mono(di)palmitate, sorbitan mono(di)stearate, sorbitan mono(di)oleate, etc. Esters; polyoxyethylene sorbitan monocinnamate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan tristearate, Polyoxyalkylene sorbitol such as ethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxypropylene sorbitan monolaurate, polyoxypropylene sorbitan monostearate, etc. Anhydride fatty acid esters, etc.

該等之中，就與聚酯之相溶性及抗靜電性之觀點而言，較佳為甘油脂肪酸酯、聚氧伸烷基甘油脂肪酸酯、聚氧伸烷基脂肪酸酯，更佳為作為具有甘油骨架之脂肪酸酯之甘油脂肪酸酯或聚氧伸烷基甘油脂肪酸酯。 Among these, from the viewpoint of compatibility with polyester and antistatic properties, glycerin fatty acid ester, polyoxyalkylene glycerin fatty acid ester, and polyoxyalkylene fatty acid ester are preferred, and more preferred It is a glycerin fatty acid ester or a polyoxyalkyleneglycerol fatty acid ester which is a fatty acid ester having a glycerin skeleton.

又，該等之中，就抗靜電性及相溶性優異之觀點而言，較理想為烷基之碳數為8以上、較佳為10~22、進而較佳為12~18之範圍者。 Moreover, among these, from the viewpoint of excellent antistatic properties and compatibility, those having the carbon number of the alkyl group are preferably 8 or more, preferably 10 to 22, and further preferably 12 to 18.

作為醚型非離子系界面活性劑，例如可列舉：聚氧乙烯月桂醚、聚氧乙烯異癸基醚、聚氧乙烯鯨蠟基醚、聚氧乙烯硬脂基醚、聚氧乙烯油基醚、聚氧乙烯辛基十二烷基醚、聚氧化丙烯月桂醚、聚氧化丙烯鯨蠟基醚、聚氧化丙烯硬脂基醚、聚氧化丙烯油基醚、聚氧化丁烯月桂醚、聚氧化丁烯鯨蠟基醚、聚氧化丁烯硬脂基醚、聚氧化丁烯油基醚等聚 氧伸烷基烷基醚；聚氧乙烯三苯基苯基醚、聚氧乙烯三苄基苯基醚、聚氧乙烯二苯乙烯苯基醚等聚氧伸烷基苯基醚等。 Examples of ether-type nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene isodecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether. , polyoxyethylene octyl lauryl ether, polyoxypropylene lauryl ether, polyoxypropylene cetyl ether, polyoxypropylene stearyl ether, polyoxypropylene oleyl ether, polyoxybutylene lauryl ether, polyoxyethylene Butylene cetyl ether, polyoxybutylene stearyl ether, polyoxybutylene oleyl ether, etc. Oxyalkylene alkyl ether; polyoxyethylene triphenyl phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene stilbene phenyl ether and other polyoxyalkylene phenyl ethers.

該等之中，就抗靜電性之觀點而言，較佳為聚氧伸烷基烷基醚。又，就抗靜電性及相溶性優異之觀點而言，烷基之碳數為8以上、較佳為10~22、進而較佳為12~18之範圍。 Among these, from the viewpoint of antistatic properties, polyoxyalkylene alkyl ether is preferred. Furthermore, from the viewpoint of excellent antistatic properties and compatibility, the number of carbon atoms in the alkyl group is 8 or more, preferably 10 to 22, and further preferably 12 to 18.

作為陽離子系界面活性劑，例如可列舉：烷基銨鹽、烷基苄基銨鹽等四級銨鹽型；N-甲基雙羥基乙基胺脂肪酸酯-鹽酸鹽等胺鹽型等。該等之中，就抗靜電性優異之觀點而言，較佳為四級銨鹽型。 Examples of cationic surfactants include quaternary ammonium salt types such as alkylammonium salts and alkyl benzylammonium salts; amine salt types such as N-methylbishydroxyethylamine fatty acid ester-hydrochloride; and the like. . Among these, the quaternary ammonium salt type is preferable from the viewpoint of excellent antistatic properties.

作為四級銨鹽型陽離子系界面活性劑，例如可列舉：辛基三甲基銨鹽、癸基三甲基銨鹽、月桂基三甲基銨鹽、十四烷基三甲基銨鹽、十六烷基三甲基銨鹽、硬脂基三甲基銨鹽、辛基二甲基乙基銨鹽、癸基二甲基乙基銨鹽、月桂基二甲基乙基銨鹽、十四烷基二甲基乙基銨鹽、十六烷基二甲基乙基銨鹽、辛基三乙基銨鹽、月桂基三乙基銨鹽、十六烷基三乙基銨鹽、十二烷基二甲基銨鹽等烷基銨鹽；辛基二甲基苄基銨鹽、癸基二甲基苄基銨鹽、月桂基二甲基苄基銨鹽、十四烷基二甲基苄基銨鹽、十六烷基二甲基苄基銨鹽、硬脂基二甲基苄基銨鹽、三丁基苄基銨鹽、三己基苄基銨鹽等烷基苄基銨鹽等。 Examples of the quaternary ammonium salt type cationic surfactant include: octyltrimethylammonium salt, decyltrimethylammonium salt, lauryltrimethylammonium salt, tetradecyltrimethylammonium salt, Cetyltrimethylammonium salt, stearyltrimethylammonium salt, octyldimethylethylammonium salt, decyldimethylethylammonium salt, lauryldimethylethylammonium salt, ten Tetraalkyldimethylethylammonium salt, cetyltriethylammonium salt, octyltriethylammonium salt, lauryltriethylammonium salt, cetyltriethylammonium salt, Alkylammonium salts such as dialkyldimethylammonium salt; octyldimethylbenzylammonium salt, decyldimethylbenzylammonium salt, lauryldimethylbenzylammonium salt, tetradecyldimethyl Alkyl benzylammonium salts such as cetyl benzyl ammonium salt, cetyl dimethyl benzylammonium salt, stearyl dimethyl benzylammonium salt, tributyl benzylammonium salt, trihexyl benzylammonium salt, etc. wait.

該等之中，就作為界面活性劑之性能、抗靜電性能之觀點而言，較佳為烷基銨鹽。 Among these, from the viewpoint of performance as a surfactant and antistatic performance, an alkylammonium salt is preferred.

又，烷基之碳數最長，通常為4以上、較佳為6~22、進而較佳為8~18之範圍。又，作為銨基之抗衡離子(counter ion)，例如可列舉：鹵素離子、磺酸鹽、硫酸鹽、磷酸鹽、硝酸鹽、羧酸鹽等離子；該等之中，就抗靜電性良好之觀點而言，較佳為氯化物、磺酸鹽、硫酸鹽。 In addition, the alkyl group has the longest carbon number, which is usually 4 or more, preferably 6 to 22, and further preferably 8 to 18. In addition, examples of counter ions of the ammonium group include: halogen ions, sulfonates, sulfates, phosphates, nitrates, carboxylates and other ions; among these, from the viewpoint of good antistatic properties Specifically, chloride, sulfonate, and sulfate are preferred.

作為兩性界面活性劑，例如可列舉：烷基甜菜鹼等甜菜鹼型、烷基胺基脂肪酸鹽等胺基酸型、烷基氧化胺等氧化胺型等。該等之中，就抗靜電性能優異之觀點而言，較佳為甜菜鹼型。 Examples of amphoteric surfactants include betaine type surfactants such as alkyl betaines, amino acid types such as alkyl amino fatty acid salts, and amine oxide types such as alkyl amine oxides. Among these, the betaine type is preferable from the viewpoint of excellent antistatic properties.

作為甜菜鹼型兩性離子系界面活性劑，例如可列舉：辛基二甲基胺基乙酸甜菜鹼、癸基二甲基胺基乙酸甜菜鹼、月桂基二甲基胺基乙酸甜菜鹼、十四烷基二甲基胺基乙酸甜菜鹼、十六烷基二甲基胺基乙酸甜菜鹼、硬脂基二甲基胺基乙酸甜菜鹼、辛醯胺丙基甜菜鹼、癸醯胺丙基甜菜鹼、月桂醯胺丙基甜菜鹼、十四烷醯胺丙基甜菜鹼、十六烷醯胺丙基甜菜鹼、硬脂醯胺丙基甜菜鹼等。 Examples of betaine-type zwitterionic surfactants include: octyldimethylaminoacetate betaine, decyldimethylaminoacetate betaine, lauryldimethylaminoacetate betaine, tetradecane Alkyl dimethylaminoacetate betaine, cetyldimethylaminoacetate betaine, stearyldimethylaminoacetate betaine, octylamide propyl betaine, decylamide propyl betaine Alkali, laurylamide propyl betaine, tetradecylamine propyl betaine, cetylamide propyl betaine, stearylamine propyl betaine, etc.

作為本發明之DFR基材用膜之塗佈層之一態樣，可列舉實質上不含無機鹽之態樣。此處，所謂「塗佈層中實質上不含無機鹽」，可於無損本發明之效果之範圍內包含無機鹽，例如亦存在於用作塗佈液之溶劑之水中不可避免地包含無機鹽之情形。於本發明中，所謂塗佈層中實質上不含無機鹽，係指塗佈層中之無機鹽之含量以質量基準計較佳為500質量ppm以下，更佳為300質量ppm以下，進而較佳為200質量ppm以下，進而更佳為100質量ppm以下，下限值並無特別限制，若考慮到不可避免之無機鹽之混入，則實際上為10質量ppm以上。塗佈層中之無機鹽之含量例如可藉由元素分析、螢光X射線分析等進行測定。 An aspect of the coating layer of the film for DFR base material of the present invention includes an aspect that does not substantially contain inorganic salts. Here, the term "the coating layer does not substantially contain inorganic salts" means that inorganic salts may be included within a range that does not impair the effects of the present invention. For example, inorganic salts may also be inevitably included in water used as a solvent for the coating liquid. situation. In the present invention, the term "substantially no inorganic salt" in the coating layer means that the content of the inorganic salt in the coating layer is preferably 500 ppm by mass or less, more preferably 300 ppm by mass or less, and even more preferably on a mass basis. It is 200 mass ppm or less, more preferably 100 mass ppm or less. The lower limit is not particularly limited, but if the inevitable mixing of inorganic salts is taken into consideration, it is actually 10 mass ppm or more. The content of the inorganic salt in the coating layer can be measured, for example, by elemental analysis, fluorescence X-ray analysis, or the like.

此處，作為無機鹽，不包含上述金屬鹽之交聯觸媒、相當於無機鹽之粒子A。例如可列舉：氯化鈉、溴化鈉、硝酸鈉、氯化鉀、硝酸鉀、氯化鍶、硝酸鍶、氯化銫、氯化鎂、硝酸鎂、氯化鈣、硝酸鈣、氯化鐵(II)、溴化鐵(II)、硝酸鐵、六氰鐵(II)酸鉀、六氰鐵(III)酸鉀、氯化鈷(II)、溴化鈷(II)、沃化鈷(II)、硝酸鈷(II)、硫酸鈷(II)、氯化鎳(II)、溴化 鎳(II)、硝酸鎳(II)、硫酸鎳(II)、氯化鈀(II)鈉、氯化銅(II)、溴化銅(II)、硝酸銅(II)、硫酸銅(II)、硝酸銀、氯化鋅、硝酸鋅、氯化鋁、硝酸鋁、氯化銦(III)、硝酸銦(III)等。 Here, as the inorganic salt, the cross-linking catalyst of the above-mentioned metal salt is not included, and the particle A corresponds to the inorganic salt. Examples include: sodium chloride, sodium bromide, sodium nitrate, potassium chloride, potassium nitrate, strontium chloride, strontium nitrate, cesium chloride, magnesium chloride, magnesium nitrate, calcium chloride, calcium nitrate, ferric chloride (II ), iron(II) bromide, ferric nitrate, potassium hexacyanoferrate(II), potassium hexacyanoferrate(III), cobalt(II) chloride, cobalt(II) bromide, cobalt(II) chloride , cobalt(II) nitrate, cobalt(II) sulfate, nickel(II) chloride, bromide Nickel(II), nickel(II) nitrate, nickel(II) sulfate, sodium palladium(II) chloride, copper(II) chloride, copper(II) bromide, copper(II) nitrate, copper(II) sulfate , silver nitrate, zinc chloride, zinc nitrate, aluminum chloride, aluminum nitrate, indium (III) chloride, indium (III) nitrate, etc.

作為本發明之DFR基材用膜之塗佈層之一態樣，可列舉實質上不含聚醚化合物之態樣。此處，所謂「塗佈層中實質上不含聚醚化合物」，可於無損本發明之效果之範圍內包含聚醚化合物，存在於自塗佈液中形成塗佈層時之乾燥過程、製膜過程中未反應而殘留之未反應物、反應後之化合物或者其等之混合物中包含聚醚化合物之情形。於本說明書中，所謂聚醚化合物，係指直鏈狀存在2個以上之醚鍵之化合物。若塗佈層中含有聚醚化合物，則塗佈層變柔軟而會帶來防受損性變差之影響。 One aspect of the coating layer of the film for DFR base material of the present invention is an aspect that does not substantially contain a polyether compound. Here, the term "the coating layer does not substantially contain a polyether compound" means that the polyether compound may be included in the range that does not impair the effects of the present invention and is present in the drying process and preparation process when the coating layer is formed from the coating liquid. The situation in which polyether compounds are included in unreacted substances, compounds after reaction, or mixtures thereof that remain unreacted during the membrane process. In this specification, a polyether compound refers to a compound having two or more ether bonds in a linear chain. If the coating layer contains a polyether compound, the coating layer will become soft and damage resistance will be deteriorated.

於本發明中，所謂塗佈層中實質上不含聚醚化合物，係指塗佈層中之聚醚化合物之含量以質量基準計較佳為3000質量ppm以下，更佳為1000質量ppm以下，進而較佳為800質量ppm以下，進而更佳為500質量ppm以下，下限值並無特別限制，若考慮到不可避免之聚醚化合物之混入，則為10質量ppm以上。 In the present invention, the term "substantially no polyether compound" in the coating layer means that the content of the polyether compound in the coating layer is preferably 3,000 mass ppm or less, more preferably 1,000 mass ppm or less on a mass basis, and further It is preferably 800 ppm by mass or less, more preferably 500 ppm by mass or less. The lower limit is not particularly limited, but if the inevitable mixing of the polyether compound is taken into consideration, it is 10 ppm by mass or more.

此處，作為聚醚化合物，係直鏈狀存在2個以上之醚鍵之化合物，可列舉：聚乙二醇、聚丙二醇、聚1,4-丁二醇等聚伸烷基二醇；15-冠醚-5、18-冠醚-6等冠醚等。 Here, the polyether compound is a compound having two or more ether bonds in a linear chain, and examples thereof include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and poly1,4-butylene glycol; 15 -Crown ethers such as crown ether-5, 18-crown ether-6, etc.

此處，作為聚醚化合物，不包含上述多元醇系抗靜電劑、酯-醚型界面活性劑及醚型界面活性劑。 Here, the polyether compound does not include the polyol-based antistatic agent, ester-ether type surfactant and ether type surfactant mentioned above.

粒子A Particle A

為了維持DFR基材用膜之透明性，同時提高平滑性並進一步提高防 受損性、防磨削性及空氣逃逸性，塗佈層含有粒子A。粒子A並無特別限制，可使用先前公知之粒子。作為粒子A之具體例，可列舉：膠體二氧化矽、多孔質二氧化矽、氧化鋁、碳酸鈣、氧化鋯、氧化鈦等無機粒子；丙烯酸系樹脂、苯乙烯樹脂等有機粒子等。粒子A包含粒徑為30~80nm之粒子AS及粒徑為100~400nm之粒子AL，亦可包含粒子AS及粒子AL以外之粒徑未達1μm之粒子。 In order to maintain the transparency of the DFR substrate film, while improving the smoothness and further improving the anti- Damage resistance, anti-grinding property and air escape property, the coating layer contains particles A. The particles A are not particularly limited, and previously known particles can be used. Specific examples of the particles A include inorganic particles such as colloidal silica, porous silica, alumina, calcium carbonate, zirconium oxide, and titanium oxide; organic particles such as acrylic resin and styrene resin. Particle A includes particle AS with a particle diameter of 30 to 80 nm and particle AL with a particle diameter of 100 to 400 nm. It may also include particles other than particle AS and particle AL with a particle diameter of less than 1 μm.

為了維持塗佈層之透明性，同時進一步提高平滑性、防受損性、防磨削性及空氣逃逸性，以相對於對塗佈層之表面進行觀察時之該塗佈層表面中所占之粒子之面積合計而粒子AS之面積比率成為60~99.9%之範圍內、粒子AL之面積比率成為0.1~15%之範圍內之方式於塗佈層中含有粒子AS及粒子AL。此處，於對塗佈層之表面進行觀察時觀察到聚酯膜中所含有之粒子B之情形時，視為不包含該粒子B。 In order to maintain the transparency of the coating layer while further improving the smoothness, damage resistance, abrasion resistance and air escape properties, relative to the proportion of the surface of the coating layer when observing the surface of the coating layer The coating layer contains particles AS and particles AL such that the area ratio of particles AS falls within the range of 60 to 99.9%, and the area ratio of particles AL falls within the range of 0.1 to 15%. Here, when the particle B contained in the polyester film is observed when the surface of the coating layer is observed, it is considered that the particle B is not included.

塗佈層中所含有之粒子A之中，粒子AS、粒子AL及其他粒子AE可為同種粒子，亦可為異種粒子。粒子AS、粒子AL及其他粒子AE可為構成粒度分佈中之1個波峰中之各粒徑範圍之組份，亦可為構成粒度分佈中之不同波峰中之各粒徑範圍之組份。又，粒子AS、粒子AL及其他粒子AE與聚酯膜中所包含之粒子B可為同種粒子，亦可與粒子B為異種粒子。就形成塗佈層時之耐熱性及可廉價地獲取之方面而言，較佳為膠體二氧化矽、多孔質二氧化矽、有機粒子。 Among the particles A contained in the coating layer, the particles AS, the particles AL, and the other particles AE may be the same type of particles or different types of particles. Particle AS, particle AL and other particles AE may be components constituting each particle size range in one peak in the particle size distribution, or may be components constituting each particle size range in different peaks in the particle size distribution. In addition, the particles AS, the particles AL, and the other particles AE may be the same type of particles as the particle B contained in the polyester film, or they may be different types of particles from the particle B. From the viewpoint of heat resistance when forming the coating layer and availability at low cost, colloidal silica, porous silica, and organic particles are preferred.

粒子AS Particle AS

藉由以相對於對塗佈層之表面進行觀察時之塗佈層表面中所占之粒子之面積合計而粒子AS之面積比率成為60~99.9%之範圍內之方式於塗 佈層中含有粒子，可維持塗佈層之透明性，並且可進一步提高乾式膜抗蝕劑步驟中之平滑性，從而提高防受損性及防磨削性。粒子AS較佳為上述面積比率成為65~99.5%之範圍內，更佳為成為70~99.0%之範圍內。 The coating is applied in such a manner that the area ratio of the particles AS is within the range of 60 to 99.9% relative to the total area of the particles occupying the surface of the coating layer when the surface of the coating layer is observed. The cloth layer contains particles, which can maintain the transparency of the coating layer and further improve the smoothness during the dry film resist step, thereby improving damage resistance and grinding resistance. The particle AS preferably has the above-mentioned area ratio within the range of 65 to 99.5%, more preferably within the range of 70 to 99.0%.

關於粒子AS及粒子AL之粒徑，於粒子AS及粒子AL為粉體之情形時，可藉由使用離心沈降式粒度分佈測定裝置(島津製作所公司製造，SA-CP3型)對粉體進行測定所得之等效球形分佈進行測定。塗佈層中所包含之粒子AS及粒子AL之粒徑例如可使用掃描式電子顯微鏡(Scanning Electron Microscope：SEM，日本FEI股份有限公司製造，「NovaNanoSEM」)對塗佈層表面進行觀察，根據所獲得之圖像資料並使用圖像解析軟體(日本Roper股份有限公司製造，「Image-Pro Premier」)測定各粒子之粒徑。於圖像資料中粒子並非為圓形之情形時，測定該粒子之面積，並換算成具有相同面積之圓形後測定粒徑。 Regarding the particle diameters of the particles AS and the particles AL, when the particles AS and the particles AL are powders, the powder can be measured by using a centrifugal sedimentation particle size distribution measuring device (model SA-CP3, manufactured by Shimadzu Corporation). The obtained equivalent spherical distribution was measured. The particle diameters of the particles AS and AL contained in the coating layer can be observed on the surface of the coating layer using, for example, a scanning electron microscope (SEM, manufactured by Japan FEI Co., Ltd., "NovaNanoSEM"). The obtained image data was used to measure the particle size of each particle using image analysis software ("Image-Pro Premier" manufactured by Japan Roper Co., Ltd.). When the particles in the image data are not circular, measure the area of the particle, convert it into a circle with the same area, and then measure the particle diameter.

粒子AL Particle AL

藉由以相對於對塗佈層之表面進行觀察時之塗佈層表面中所占之粒子之面積合計而粒子AL之面積比率成為0.1~15%之範圍內之方式於塗佈層中含有粒子，可維持塗佈層之透明性，並且於乾式膜抗蝕劑步驟中提高空氣逃逸性，從而進一步提高平滑性，防磨削性亦得到維持。粒子AL較佳為上述面積比率成為0.2~15%之範圍內，更佳為成為1.0~10%之範圍內。 The particles are contained in the coating layer so that the area ratio of the particles AL is within the range of 0.1 to 15% relative to the total area of the particles occupying the surface of the coating layer when the surface of the coating layer is observed. , can maintain the transparency of the coating layer and improve air escape during the dry film resist step, thereby further improving smoothness and maintaining anti-grinding properties. The particle AL preferably has the above-mentioned area ratio within the range of 0.2 to 15%, more preferably within the range of 1.0 to 10%.

塗佈層實質上不含粒徑超過1μm之粒子。此處，所謂「塗佈層中實質上不含粒徑超過1μm之粒子」，具體而言，係指相對於對塗佈層之表面進行觀察時之塗佈層表面中所占之粒子之面積合計而粒徑超過1 μm之粒子之面積比率未達0.01%。實質上是否包含粒徑超過1μm之粒子可藉由與粒子AS相同之方法進行測定。若塗佈層中包含粒徑超過1μm之粒子，則存在塗佈層之透明性受到阻礙之情形，且由於相對於膜厚之粒徑增大，故而有於捲取及加工步驟中因塗佈層被擦拭而導致粒子容易脫落，從而產生因塗膜之剝落而產生之污染之虞。 The coating layer substantially does not contain particles with a particle size exceeding 1 μm. Here, "the coating layer does not substantially contain particles with a particle diameter exceeding 1 μm" specifically refers to the area of the particles occupying the surface of the coating layer when the surface of the coating layer is observed. The total particle size exceeds 1 The area ratio of μm particles does not reach 0.01%. Whether or not particles having a particle size exceeding 1 μm is substantially included can be determined by the same method as Particle AS. If the coating layer contains particles with a particle size exceeding 1 μm, the transparency of the coating layer may be hindered, and since the particle size relative to the film thickness increases, there may be problems due to coating during the coiling and processing steps. The particles will easily fall off when the coating is wiped, which may cause contamination due to peeling off of the coating.

塗佈層亦可包含粒子AS及粒子AL以外之大小且粒徑為1μm以下之其他粒子AE。具體而言，其他粒子AE例如可為粒徑為5nm以上且未達30nm之範圍之粒子，亦可為粒徑超過80nm且未達100nm之範圍內之粒子，亦可為粒徑超過400nm且未達1000nm之範圍內之粒子。於塗佈層中包含粒子AS及粒子AL以外之其他粒子AE之情形時，可以相對於對塗佈層之表面進行觀察時之塗佈層表面中所占至粒子之面積合計而其他粒子AE之面積比率成為0.1~25%之範圍內之方式使塗佈層中含有其他粒子AE The coating layer may also contain other particles AE having a size other than the particles AS and the particles AL and having a particle diameter of 1 μm or less. Specifically, the other particles AE may be, for example, particles with a particle diameter of 5 nm or more and less than 30 nm, particles with a particle diameter of more than 80 nm and less than 100 nm, or particles with a particle diameter of more than 400 nm and less than 100 nm. Particles in the range of 1000nm. When the coating layer contains particles AE other than particles AS and particles AL, the total area occupied by the particles in the surface of the coating layer when observing the surface of the coating layer can be compared with the other particles AE. The coating layer contains other particles AE so that the area ratio falls within the range of 0.1~25%.

為了防止產生DFR基材用膜之損傷及污染，塗佈層中所包含之粒子A之平均粒徑較佳為塗佈層之膜厚之0.5倍以上且5倍以下之範圍，更佳為塗佈層之膜厚之0.7倍以上且3.5倍以下之範圍。進而較佳為塗佈層之膜厚之1.0倍以上且3.0倍以下之範圍。於聚酯膜之塗佈層中，若相對於膜厚之粒子之平均粒徑較大，則存在如下顧慮：於捲取及加工步驟中因塗佈層被擦拭而導致粒子容易脫落，因而產生損傷或因塗膜之磨削而產生污染。於塗佈層中所包含之粒子A之平均粒徑為塗佈層之膜厚之0.5倍以上且5倍以下之範圍之情形時，可維持DFR基材用膜之透明性及良好之防受損性及防磨削性，同時賦予空氣逃逸性及平滑性。 In order to prevent damage and contamination of the DFR substrate film, the average particle diameter of the particles A contained in the coating layer is preferably in the range of 0.5 times to 5 times the film thickness of the coating layer, and more preferably The film thickness of the fabric layer is within the range of 0.7 times to 3.5 times. Furthermore, the range of 1.0 times or more and 3.0 times or less of the film thickness of the coating layer is more preferable. In the coating layer of a polyester film, if the average particle size of the particles relative to the film thickness is large, there is a concern that the particles may easily fall off due to the coating layer being wiped during the winding and processing steps, resulting in the occurrence of Damage or contamination caused by grinding of the coating film. When the average particle diameter of the particles A contained in the coating layer is in the range of 0.5 times to 5 times the film thickness of the coating layer, the transparency and good protection of the DFR base film can be maintained. Damage resistance and grinding resistance, while providing air escape and smoothness.

例如於在平均表面粗糙度(Ra)為1~3nm之範圍之聚酯膜 形成塗佈層之情形時，為了維持透明性同時賦予防受損性及平滑性，較佳為使用平均粒徑不同之2種以上之粒子A。於使用平均粒徑不同之2種以上之尺寸之粒子A之情形時，較佳為平均粒徑最大之尺寸之粒子A之粒徑為塗佈層之膜厚之0.5倍以上且5倍之範圍。 For example, a polyester film with an average surface roughness (Ra) in the range of 1 to 3 nm When forming a coating layer, in order to provide damage prevention and smoothness while maintaining transparency, it is preferable to use two or more types of particles A with different average particle diameters. When using two or more sizes of particles A with different average particle diameters, it is preferable that the particle size of the particle A with the largest average particle diameter is within the range of 0.5 to 5 times the film thickness of the coating layer. .

粒子A之平均粒徑越小，聚酯膜之透明性越高，可減少電路之缺損，從而可應用於要求更極細線之電路之用途，另一方面，粒子A之平均粒徑大至某種程度可賦予平滑性。粒子A之平均粒徑滿足塗佈層之膜厚之0.5倍以上且5倍以下之範圍，並且通常為0.001~1.0μm，較佳為0.005~0.5μm，更佳為0.01~0.1μm之範圍。若粒子A之平均粒徑為0.001~1.0μm之範圍，則可防止產生DFR基材用膜之損傷及污染，並且可賦予平滑性。關於平均粒徑，於粒子A為粉體之情形時，可將使用離心沈降式粒度分佈測定裝置(島津製作所公司製造，SA-CP3型)對粉體進行測定所得之等效球形分佈中之累計體積分率50%之粒徑(d50)設為平均粒徑。塗佈層中所包含之粒子A之平均粒徑例如可使用掃描式電子顯微鏡(Scanning Electron Microscope：SEM，日本FEI股份有限公司製造，「NovaNanoSEM」)對塗佈層表面進行觀察，根據所獲得之圖像資料並使用圖像解析軟體(日本Ropper股份有限公司製造，「Image-Pro Premier」)測定各粒子之粒徑，任意選擇2000個粒子，根據所選擇之粒子之粒徑資料算出粒度分佈(體積基準)，並將累計體積分率50%之粒徑(d50)設為平均粒徑。 The smaller the average particle size of Particle A, the higher the transparency of the polyester film, which can reduce defects in circuits and thus can be applied to circuits requiring finer wires. On the other hand, the average particle size of Particle A is as large as a certain This degree can impart smoothness. The average particle diameter of the particles A satisfies the range of 0.5 to 5 times the film thickness of the coating layer, and is usually 0.001 to 1.0 μm, preferably 0.005 to 0.5 μm, and more preferably 0.01 to 0.1 μm. If the average particle diameter of the particles A is in the range of 0.001 to 1.0 μm, damage and contamination of the DFR substrate film can be prevented and smoothness can be imparted. Regarding the average particle size, when the particle A is a powder, the cumulative equivalent spherical distribution obtained by measuring the powder using a centrifugal sedimentation particle size distribution measuring device (model SA-CP3, manufactured by Shimadzu Corporation) can be The particle diameter (d50) with a volume fraction of 50% is set as the average particle diameter. The average particle diameter of the particles A contained in the coating layer can be observed on the surface of the coating layer using, for example, a scanning electron microscope (SEM, manufactured by Japan FEI Co., Ltd., "NovaNanoSEM"). Image data and use image analysis software ("Image-Pro Premier" manufactured by Japan Ropper Co., Ltd.) to measure the particle size of each particle, randomly select 2000 particles, and calculate the particle size distribution based on the particle size data of the selected particles ( Volume basis), and the particle diameter (d50) with a cumulative volume fraction of 50% is set as the average particle diameter.

粒子A亦可使用平均粒徑不同之2種以上之粒子A。於使用2種以上之粒子A之情形時，一種粒子A(以下，亦稱為「粒子A-1」)之平均粒徑通常為0.001~0.06μm、較佳為0.005~0.06μm、更佳為0.01~ 0.06μm之範圍。粒子A-1中可包含粒子AS，亦可包含粒子AL。另一種粒子A(以下，亦稱為「粒子A-2」)之平均粒徑通常為0.06~1.0μm、較佳為0.06~0.5μm、更佳為0.06~0.3μm、進而較佳為0.06~0.1μm之範圍。粒子A-2中可包含粒子AS，亦可包含粒子AL。進而，藉由使用平均粒徑為0.001~0.06μm之範圍之粒子A-1與平均粒徑為0.06~1.0μm之範圍之粒子A-2之2種以上之粒子A，可同時實現更高度之透明性及良好之平滑性。 As the particles A, two or more types of particles A having different average particle diameters may be used. When two or more types of particles A are used, the average particle diameter of one type of particle A (hereinafter, also referred to as "particle A-1") is usually 0.001~0.06 μm, preferably 0.005~0.06 μm, and more preferably 0.01~ 0.06μm range. Particle A-1 may include particle AS or particle AL. The average particle diameter of the other particle A (hereinafter also referred to as "particle A-2") is usually 0.06~1.0 μm, preferably 0.06~0.5 μm, more preferably 0.06~0.3 μm, and still more preferably 0.06~ 0.1μm range. Particle A-2 may include particle AS or particle AL. Furthermore, by using two or more types of particles A, namely particles A-1 with an average particle diameter in the range of 0.001 to 0.06 μm and particles A-2 with an average particle diameter in the range of 0.06 to 1.0 μm, higher-level results can be achieved simultaneously. Transparency and good smoothness.

塗佈層中之粒子A之含量較佳為1~10質量%，更佳為1~8質量%，進而較佳為2~7質量%，尤佳為2~5質量%。若塗佈層中之粒子A之含量為1~10質量%之範圍，則可維持DFR基材用膜之透明性，同時賦予防受損性及更優異之平滑性。塗佈層中之粒子A之含量例如可藉由利用元素分析特定出構成塗佈層中之粒子之元素後，利用穿透式電子顯微鏡(TEM：Transmission Electron Microscope)對該粒子之尺寸及頻度進行觀察而測定。塗佈液中之粒子A之含量相對於塗佈液中之非揮發成分，較佳為1~10質量%，更佳為1~8質量%，進而較佳為2~7質量%，尤佳為2~5質量%。 The content of particle A in the coating layer is preferably 1 to 10 mass%, more preferably 1 to 8 mass%, further preferably 2 to 7 mass%, and particularly preferably 2 to 5 mass%. If the content of particle A in the coating layer is in the range of 1 to 10% by mass, the transparency of the DFR base film can be maintained while providing damage prevention and better smoothness. The content of particles A in the coating layer can be determined, for example, by using elemental analysis to identify the elements constituting the particles in the coating layer, and then using a transmission electron microscope (TEM: Transmission Electron Microscope) to measure the size and frequency of the particles. Measured by observation. The content of particle A in the coating liquid relative to the non-volatile components in the coating liquid is preferably 1 to 10 mass %, more preferably 1 to 8 mass %, further preferably 2 to 7 mass %, and particularly preferably It is 2~5% by mass.

脫模劑 Release agent

為了進一步提高DFR基材用膜之平滑性，塗佈層較佳為含有脫模劑。脫模劑較佳為選自由具有長鏈烷基之化合物、蠟、氟化合物及聚矽氧化合物之群中之至少一種脫模劑。其中，就污染性優異之觀點而言，脫模劑較佳為具有長鏈烷基之化合物或蠟。又，就防止受損之觀點而言，脫模劑較佳為蠟。該等脫模劑可單獨使用，亦可使用複數種。較佳為塗佈層中 含有蠟。 In order to further improve the smoothness of the DFR substrate film, the coating layer preferably contains a release agent. The release agent is preferably at least one release agent selected from the group consisting of compounds having long-chain alkyl groups, waxes, fluorine compounds, and polysiloxane compounds. Among them, the release agent is preferably a compound or wax having a long-chain alkyl group from the viewpoint of excellent stain resistance. Moreover, from the viewpoint of preventing damage, the release agent is preferably wax. These release agents can be used individually or in plural types. Preferably in the coating layer Contains wax.

塗佈層中之脫模劑之含量通常為1~10質量%，較佳為2~9質量%，更佳為3~8質量%。若塗佈層中之脫模劑之含量為1~10質量%，則可進一步提高DFR基材用膜之平滑性。推測塗佈層中之脫模劑之含量與相對於塗佈液中之非揮發成分之脫模劑之含量大致相等。用以形成塗佈層之塗佈液中之脫模劑之含量相對於塗佈液中之非揮發成分，通常為1~10質量%，較佳為2~9質量%，更佳為3~8質量%。 The content of the release agent in the coating layer is usually 1 to 10 mass%, preferably 2 to 9 mass%, and more preferably 3 to 8 mass%. If the content of the release agent in the coating layer is 1 to 10% by mass, the smoothness of the DFR base film can be further improved. It is estimated that the content of the release agent in the coating layer is approximately equal to the content of the release agent relative to the non-volatile components in the coating liquid. The content of the release agent in the coating liquid used to form the coating layer is usually 1 to 10 mass %, preferably 2 to 9 mass %, and more preferably 3 to 3 mass % relative to the non-volatile components in the coating liquid. 8% by mass.

蠟係選自天然蠟、合成蠟、調配有其等之蠟之中之至少一種蠟。 The wax is at least one selected from the group consisting of natural waxes, synthetic waxes, and waxes formulated with them.

所謂天然蠟，係植物系蠟、動物系蠟、礦物系蠟、石油蠟。作為植物系蠟，可列舉：堪地里拉蠟、巴西棕櫚蠟、米糠蠟、木臘、荷荷芭油。作為動物系蠟，可列舉：蜂蠟、羊毛脂、鯨蠟。作為礦物系蠟，可列舉：褐煤蠟、地蠟、地蠟精。作為石油蠟，可列舉：石蠟、微晶蠟、石蠟脂。 The so-called natural wax refers to plant wax, animal wax, mineral wax, and petroleum wax. Examples of plant-based waxes include candelilla wax, carnauba wax, rice bran wax, wood wax, and jojoba oil. Examples of animal-based waxes include beeswax, lanolin, and spermaceti. Examples of mineral wax include montan wax, ozokerite, and ozokerite. Examples of petroleum waxes include paraffin wax, microcrystalline wax, and paraffin wax.

作為合成蠟，可列舉：合成烴、改性蠟、氫化蠟、脂肪酸、酸醯胺、胺、醯亞胺、酯、酮。作為合成烴，有名的是Fischer-Tropsch wax(別名Sasol Wax)、聚乙烯蠟，此外，亦包含作為低分子量之高分子(具體而言，黏度數量平均分子量為500至20000之高分子)之以下之聚合物。即，有聚丙烯、乙烯-丙烯酸共聚物、聚乙二醇、聚丙二醇、聚乙二醇與聚丙二醇之封端或接枝結合體。作為改性蠟，可列舉：褐煤蠟衍生物、石蠟衍生物、微晶蠟衍生物。所謂此處之衍生物，係藉由精製、氧化、酯化、皂化之任一處理或其等之組合而獲得之化合物。作為氫化蠟，可列舉：氫化蓖麻油及氫化蓖麻油衍生物。 Examples of synthetic waxes include synthetic hydrocarbons, modified waxes, hydrogenated waxes, fatty acids, acid amides, amines, imines, esters, and ketones. As synthetic hydrocarbons, Fischer-Tropsch wax (also known as Sasol Wax) and polyethylene wax are well-known. In addition, low molecular weight polymers (specifically, polymers with a viscosity number average molecular weight of 500 to 20,000) and less are also included. of polymers. That is, there are polypropylene, ethylene-acrylic acid copolymer, polyethylene glycol, polypropylene glycol, and end-capped or grafted combinations of polyethylene glycol and polypropylene glycol. Examples of modified waxes include montan wax derivatives, paraffin wax derivatives, and microcrystalline wax derivatives. The derivative here refers to a compound obtained by any treatment of purification, oxidation, esterification, saponification, or a combination thereof. Examples of hydrogenated wax include hydrogenated castor oil and hydrogenated castor oil derivatives.

就可以少量而有效地賦予平滑性之觀點而言，較佳為聚乙烯蠟。 From the viewpoint that smoothness can be imparted effectively in a small amount, polyethylene wax is preferred.

所謂具有長鏈烷基之化合物，係具有碳數通常為6以上、較佳為8以上、進而較佳為12以上之直鏈或支鏈之烷基之化合物。作為烷基，例如可列舉：己基、辛基、癸基、月桂基、十八烷基、山崳基等。所謂具有烷基之化合物，例如可列舉：各種含長鏈烷基之高分子化合物、含長鏈烷基之胺化合物、含長鏈烷基之醚化合物、含長鏈烷基之四級銨鹽等。若考慮到耐熱性、污染性，則較佳為側鏈具有長鏈烷基之高分子化合物。 The compound having a long-chain alkyl group refers to a compound having a linear or branched alkyl group having a carbon number of usually 6 or more, preferably 8 or more, and further preferably 12 or more. Examples of the alkyl group include hexyl, octyl, decyl, lauryl, octadecyl, behenyl, and the like. The so-called compounds having alkyl groups include, for example: various long-chain alkyl group-containing polymer compounds, long-chain alkyl group-containing amine compounds, long-chain alkyl group-containing ether compounds, and long-chain alkyl group-containing quaternary ammonium salts. wait. In consideration of heat resistance and contamination resistance, a polymer compound having a long-chain alkyl group in the side chain is preferred.

所謂側鏈具有長鏈烷基之高分子化合物，可使具有反應性基之高分子與具有可與該反應性基反應之烷基之化合物反應而獲得。作為上述反應性基，例如可列舉：羥基、胺基、羧基、酸酐等。 The polymer compound having a long-chain alkyl group in the side chain can be obtained by reacting a polymer having a reactive group with a compound having an alkyl group that can react with the reactive group. Examples of the reactive group include a hydroxyl group, an amine group, a carboxyl group, an acid anhydride, and the like.

作為具有該等反應性基之化合物，例如可列舉：聚乙烯醇、聚乙烯亞胺、聚乙烯胺、含反應性基之聚酯樹脂、含反應性基之聚(甲基)丙烯酸樹脂等。該等之中，若考慮到脫模性及操作容易性，則較佳為聚乙烯醇。 Examples of compounds having such reactive groups include polyvinyl alcohol, polyethyleneimine, polyethyleneamine, reactive group-containing polyester resin, reactive group-containing poly(meth)acrylic resin, and the like. Among these, polyvinyl alcohol is preferred in consideration of mold releasability and ease of handling.

所謂具有可與上述反應性基反應之烷基之化合物，例如可列舉：異氰酸己酯、異氰酸辛酯、異氰酸癸酯、異氰酸月桂酯、異氰酸十八烷基酯、異氰酸山崳酯等含長鏈烷基之異氰酸酯；己基氯、辛基氯、癸基氯、月桂基氯、十八烷基氯、山崳基氯等含長鏈烷基之醯氯；含長鏈烷基之胺、含長鏈烷基之醇等。該等之中，若考慮到脫模性及操作容易性，則較佳為含長鏈烷基之異氰酸酯，尤佳為十八烷基異氰酸酯。 Examples of the compound having an alkyl group that can react with the above reactive group include: hexyl isocyanate, octyl isocyanate, decyl isocyanate, lauryl isocyanate, and stearyl isocyanate. , behenyl isocyanate and other isocyanates containing long-chain alkyl groups; hexyl chloride, octyl chloride, decyl chloride, lauryl chloride, octadecyl chloride, behenyl chloride and other long-chain alkyl chlorides ; Amines containing long-chain alkyl groups, alcohols containing long-chain alkyl groups, etc. Among these, in consideration of mold releasability and ease of handling, long-chain alkyl group-containing isocyanates are preferred, and octadecyl isocyanate is particularly preferred.

又，側鏈具有長鏈烷基之高分子化合物亦可藉由長鏈(甲基)丙烯酸烷基酯之聚合物或長鏈(甲基)丙烯酸烷基酯與其他含乙烯基之單體之共聚而獲得。所謂長鏈(甲基)丙烯酸烷基酯，例如可列舉：(甲基) 丙烯酸己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸山萮酯等。 In addition, the polymer compound with a long-chain alkyl group in the side chain can also be produced by a polymer of a long-chain alkyl (meth)acrylate or a combination of a long-chain alkyl (meth)acrylate and other vinyl-containing monomers. Obtained by gathering together. Examples of long-chain (meth)acrylic acid alkyl esters include: (methyl) Hexyl acrylate, octyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, behenyl (meth)acrylate, etc.

所謂聚矽氧化合物，係分子內具有聚矽氧結構之化合物，可列舉：聚矽氧乳液、丙烯酸接枝聚矽氧、聚矽氧接枝丙烯酸、胺基改性聚矽氧、全氟烷基改性聚矽氧、烷基改性聚矽氧等。考慮到耐熱性，較佳為含有硬化型聚矽氧樹脂。作為硬化型聚矽氧樹脂之種類，可使用加成型、縮合型、紫外線硬化型、電子束硬化型等任一硬化反應類型。 The so-called polysilicone compounds are compounds with a polysilicone structure in the molecule. Examples include: polysilicone emulsion, acrylic acid-grafted polysiloxane, polysilicone-grafted acrylic acid, amine-modified polysiloxane, and perfluoroalkane modified polysiloxane, alkyl modified polysiloxane, etc. In consideration of heat resistance, it is preferable to contain a hardened polysiloxane resin. As the type of curable polysilicone resin, any curing reaction type such as addition type, condensation type, ultraviolet curing type, electron beam curing type, etc. can be used.

作為氟化合物，係化合物中含有氟原子之化合物。就線內塗佈之塗佈外觀之方面而言，可適當地使用有機系氟化合物，例如可列舉：含全氟烷基之化合物、含有氟原子之烯烴化合物之聚合物、氟苯等芳香族氟化合物等。就脫模性之觀點而言，較佳為具有全氟烷基之化合物。進而，亦可使用氟化合物中含有如下述之長鏈烷基化合物之化合物。 The fluorine compound is a compound containing a fluorine atom. In terms of the coating appearance of in-line coating, organic fluorine compounds can be suitably used. Examples include perfluoroalkyl group-containing compounds, polymers of olefin compounds containing fluorine atoms, and aromatic compounds such as fluorobenzene. Fluorine compounds, etc. From the viewpoint of mold releasability, compounds having a perfluoroalkyl group are preferred. Furthermore, a compound containing a long-chain alkyl compound as described below among the fluorine compounds may also be used.

所謂具有全氟烷基之化合物，例如可列舉：(甲基)丙烯酸全氟烷基酯、(甲基)丙烯酸全氟烷基甲酯、(甲基)丙烯酸2-全氟烷基乙酯、(甲基)丙烯酸3-全氟烷基丙酯、(甲基)丙烯酸3-全氟烷基-1-甲基丙酯、(甲基)丙烯酸3-全氟烷基-2-丙烯酯等含全氟烷基之(甲基)丙烯酸酯或其聚合物了；全氟烷基甲基乙烯基醚、2-全氟烷基乙基乙烯基醚、3-全氟丙基乙烯基醚、3-全氟烷基-1-甲基丙基乙烯基醚、3-全氟烷基-2-丙烯基乙烯基醚等含全氟烷基之乙烯基醚或其聚合物等。若考慮到耐熱性、污染性，則較佳為聚合物。聚合物可僅為單一化合物，亦可為複數種化合物之聚合物。又，就脫模性之觀點而言，全氟烷基較佳為碳原子數為3~11。進而，亦可為與具有如下述之長鏈烷基化合物之化合物之聚合物。又，就與基材之密接性之之觀點而言，較佳為與氯乙烯之聚合物。 Examples of the compound having a perfluoroalkyl group include: (meth)acrylic acid perfluoroalkyl ester, (meth)acrylic acid perfluoroalkyl methyl ester, (meth)acrylic acid 2-perfluoroalkylethyl ester, 3-Perfluoroalkylpropyl (meth)acrylate, 3-Perfluoroalkyl-1-methylpropyl (meth)acrylate, 3-Perfluoroalkyl-2-propenyl (meth)acrylate, etc. (Meth)acrylates or their polymers containing perfluoroalkyl groups; perfluoroalkyl methyl vinyl ether, 2-perfluoroalkyl ethyl vinyl ether, 3-perfluoropropyl vinyl ether, 3-Perfluoroalkyl-1-methylpropyl vinyl ether, 3-perfluoroalkyl-2-propenyl vinyl ether and other perfluoroalkyl-containing vinyl ethers or their polymers, etc. In consideration of heat resistance and contamination resistance, polymers are preferred. The polymer may be a single compound or a polymer of multiple compounds. Furthermore, from the viewpoint of mold releasability, the perfluoroalkyl group preferably has 3 to 11 carbon atoms. Furthermore, a polymer with a compound having a long-chain alkyl compound as described below may also be used. Furthermore, from the viewpoint of adhesion to the base material, a polymer with vinyl chloride is preferred.

各種聚合物 various polymers

為了提高塗佈層之外觀及DFR基材膜之透明性等，塗佈層亦可含有交聯劑交聯而成之聚合物以外之各種聚合物。 In order to improve the appearance of the coating layer and the transparency of the DFR base film, the coating layer may also contain various polymers other than polymers cross-linked by a cross-linking agent.

塗佈層中之使交聯劑交聯而成之聚合物以外之各種聚合物之含量通常為10~70質量%，較佳為20~65質量%，更佳為30~60質量%。若塗佈層中之使交聯劑交聯而成之聚合物以外之各種聚合物之含量為10~70質量%，則可進一步提高DFR基材用膜之塗佈層之外觀及透明性。推測塗佈層中之使交聯劑交聯而成之聚合物以外之各種聚合物之含量與相對於塗佈液中之非揮發成分之使交聯劑交聯而成之聚合物以外之各種聚合物之含量大致相等。用以形成塗佈層之塗佈液中所包含之使交聯劑交聯而成之聚合物以外之各種聚合物之含量相對於塗佈液中之非揮發成分，通常為10~70質量%，較佳為20~65質量%，更佳為30~60質量%。 The content of various polymers other than the polymer cross-linked with the cross-linking agent in the coating layer is usually 10 to 70 mass %, preferably 20 to 65 mass %, more preferably 30 to 60 mass %. If the content of various polymers in the coating layer other than the polymer cross-linked with the cross-linking agent is 10 to 70% by mass, the appearance and transparency of the coating layer of the DFR base film can be further improved. It is estimated that the content of various polymers other than the polymer cross-linked with the cross-linking agent in the coating layer and the various polymers other than the polymer cross-linked with the cross-linking agent relative to the non-volatile components in the coating liquid are estimated. The polymer contents are approximately equal. The content of various polymers other than the polymer obtained by cross-linking the cross-linking agent contained in the coating liquid used to form the coating layer is usually 10 to 70 mass % relative to the non-volatile components in the coating liquid. , preferably 20 to 65 mass%, more preferably 30 to 60 mass%.

作為各種聚合物之具體例，可列舉：丙烯酸系樹脂、聚乙烯醇、聚酯樹脂、胺基甲酸酯樹脂、聚伸烷基二醇、聚伸烷基亞胺、甲基纖維素、羥基纖維素、澱粉類等。該等之中，就提高防受損性能之觀點而言，較佳為丙烯酸系樹脂、聚酯樹脂。 Specific examples of various polymers include acrylic resin, polyvinyl alcohol, polyester resin, urethane resin, polyalkylene glycol, polyalkyleneimine, methylcellulose, hydroxyl Cellulose, starch, etc. Among these, acrylic resin and polyester resin are preferred from the viewpoint of improving damage prevention performance.

所謂丙烯酸系樹脂，係包含含有丙烯酸系、甲基丙烯酸系單體之聚合性單體之聚合物。該等可為均聚物或者共聚物、進而與丙烯酸系、甲基丙烯酸系單體以外之聚合性單體之共聚物之任一種。又，亦包含其等聚合物與其他聚合物(例如聚酯、聚胺基甲酸酯等)之共聚物。例如為封端共聚物、接枝共聚物。或者亦包含於聚酯溶液或聚酯分散液中使聚合性單體聚合而獲得之聚合物(視情形為聚合物之混合物)。同樣地，亦包含 於聚胺基甲酸酯溶液、聚胺基甲酸酯分散液中使聚合性單體聚合而獲得之聚合物(視情形為聚合物之混合物)。同樣地，亦包含於其他聚合物溶液或分散液中使聚合性單體聚合而獲得之聚合物(視情形為聚合物混合物)。又，為了進一步提高與基材之密接性，亦可含有羥基、胺基。 Acrylic resin refers to a polymer including polymerizable monomers containing acrylic and methacrylic monomers. These may be any of homopolymers, copolymers, and copolymers with polymerizable monomers other than acrylic and methacrylic monomers. In addition, copolymers of these polymers and other polymers (such as polyester, polyurethane, etc.) are also included. For example, they are blocked copolymers and graft copolymers. Alternatively, a polymer obtained by polymerizing a polymerizable monomer in a polyester solution or polyester dispersion (optionally a mixture of polymers) is included. Likewise, it also includes A polymer obtained by polymerizing a polymerizable monomer in a polyurethane solution or polyurethane dispersion (optionally a mixture of polymers). Similarly, polymers obtained by polymerizing polymerizable monomers in other polymer solutions or dispersions (polymer mixtures as the case may be) are also included. In addition, in order to further improve the adhesiveness with the base material, a hydroxyl group or an amine group may be included.

作為上述聚合性單體，並無特別限定，尤其是作為代表性之化合物，例如可列舉：如丙烯酸、甲基丙烯酸、丁烯酸、伊康酸、反丁烯二酸、順丁烯二酸、檸康酸之各種含羧基單體類、及其等之鹽；如(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、反丁烯二酸單丁基羥酯、伊康酸單丁基羥酯之各種含羥基單體類；如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸月桂酯之各種(甲基)丙烯酸酯類；如(甲基)丙烯醯胺、二丙酮丙烯醯胺、N-羥甲基丙烯醯胺或(甲基)丙烯腈等各種含氮化合物；如苯乙烯、α-甲基苯乙烯、二乙烯苯、乙烯基甲苯之各種苯乙烯衍生物、如丙酸乙烯酯之各種乙烯酯類；如γ-甲基丙烯醯氧基丙基三甲氧基矽烷、乙烯基三甲氧基矽烷等之各種含矽聚合性單體類；含磷乙烯系單體類；如氯乙烯、偏二氯乙烯之各種鹵化乙烯類；如丁二烯之各種共軛二烯類。 The polymerizable monomer is not particularly limited, and representative compounds include, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, and maleic acid. , various carboxyl-containing monomers of citraconic acid, and their salts; such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate Various hydroxyl-containing monomers such as ester, monobutyl hydroxy fumarate, and monobutyl hydroxy itaconate; such as (meth)acrylic acid methyl ester, (meth)ethyl acrylate, (methyl) Various (meth)acrylate esters such as propyl acrylate, (meth)butyl acrylate, and lauryl (meth)acrylate; such as (meth)acrylamide, diacetone acrylamide, and N-hydroxymethylacrylamide Various nitrogen-containing compounds such as amide or (meth)acrylonitrile; various styrene derivatives such as styrene, α-methylstyrene, divinylbenzene, and vinyltoluene; various vinyl esters such as vinyl propionate ; Various silicon-containing polymerizable monomers such as γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, etc.; Phosphorus-containing vinyl monomers; such as vinyl chloride, vinylidene chloride Various halogenated ethylenes; various conjugated dienes such as butadiene.

所謂聚酯樹脂，作為主要構成成分，例如可列舉包含如下述多元羧酸及多元羥基化合物者。即，作為多元羧酸，可使用：對苯二甲酸、間苯二甲酸、鄰苯二甲酸、苯二甲酸、4,4'-二苯基二羧酸、2,5-萘二甲酸、1,5-萘二甲酸、2,6-萘二甲酸、2,7-萘二甲酸、1,4-環己烷二羧酸、2-鉀磺基對苯二甲酸、5-鈉磺基間苯二甲酸、己二酸、壬二酸、癸二酸、十二烷二羧酸、戊二酸、琥珀酸、偏苯三甲酸、均苯三酸、均苯四甲酸、 偏苯三甲酸酐、鄰苯二甲酸酐、對羥基苯甲酸、偏苯三甲酸單鉀鹽及其等之酯形成性衍生物等；作為多元羥基化合物，可使用：乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丙二醇、1,4-丁二醇、1,6-己二醇、2-甲基-1,5-戊二醇、新戊二醇、1,4-環己烷二甲醇、對苯二甲基二醇、雙酚A-乙二醇加成物、二乙二醇、三乙二醇、聚乙二醇、聚丙二醇、聚四亞甲基二醇、聚(四亞甲基氧)二醇、二羥甲基丙酸、甘油、三羥甲基丙烷、二羥甲基乙基磺酸鈉、二羥甲基丙酸鉀等。自該等化合物之中分別適當選擇1種以上並藉由常規方法之縮聚反應合成聚酯樹脂即可。 The polyester resin includes, for example, the following polycarboxylic acid and polyhydric hydroxyl compound as main structural components. That is, as the polycarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, phthalic acid, 4,4'-diphenyldicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 1 ,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2-potassium sulfoterephthalic acid, 5-sodium sulfo-m- Phthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid, succinic acid, trimellitic acid, trimellitic acid, pyromellitic acid, Trimellitic anhydride, phthalic anhydride, p-hydroxybenzoic acid, trimellitic acid monopotassium salt and their ester-forming derivatives, etc.; as polyvalent hydroxyl compounds, ethylene glycol, 1,2- Propylene glycol, 1,3-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2-methyl-1,5-pentanediol, neopentyl glycol, 1, 4-Cyclohexane dimethanol, terephthalenedimethanol, bisphenol A-ethylene glycol adduct, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene Glycol, poly(tetramethylene oxide) glycol, dimethylol propionate, glycerin, trimethylol propane, sodium dimethylol ethyl sulfonate, potassium dimethylol propionate, etc. It is sufficient to appropriately select one or more types of each of these compounds and synthesize the polyester resin through a polycondensation reaction using a conventional method.

所謂聚乙烯醇，係具有聚乙烯醇部位之化合物，例如亦包含相對於聚乙烯醇而局部經縮醛化或丁醛化等之變性化合物，可使用先前公知之聚乙烯醇。聚乙烯醇之聚合度並無特別限定，通常為100以上、較佳為300~40000之範圍。於聚合度未達100之情形時，存在塗佈層之耐水性降低之情形。又，聚乙烯醇之皂化度並無特別限定，實際上通常使用70莫耳%以上、較佳為70~99.9莫耳%之範圍、更佳為80~97莫耳%、尤佳為86~95莫耳%之聚乙酸乙烯酯皂化物。 Polyvinyl alcohol refers to a compound having a polyvinyl alcohol moiety, and includes, for example, a denatured compound that is partially acetalized or butyralized with polyvinyl alcohol. Conventionally known polyvinyl alcohol can be used. The degree of polymerization of polyvinyl alcohol is not particularly limited, but is usually 100 or more, preferably in the range of 300 to 40,000. When the degree of polymerization is less than 100, the water resistance of the coating layer may decrease. In addition, the saponification degree of polyvinyl alcohol is not particularly limited. In fact, it is usually 70 mol% or more, preferably in the range of 70 to 99.9 mol%, more preferably 80 to 97 mol%, and particularly preferably 86 to 86 mol%. 95 mol% polyvinyl acetate saponified product.

所謂胺基甲酸酯樹脂，係分子內具有胺基甲酸酯樹脂之高分子化合物。通常胺基甲酸酯樹脂係藉由多元醇與異氰酸酯之反應而製作。作為多元醇，可列舉：聚碳酸酯多元醇類、聚酯多元醇類、聚醚多元醇類、聚烯烴多元醇類、丙烯酸多元醇類；該等化合物可單獨使用，亦可使用複數種。 The so-called urethane resin is a polymer compound having a urethane resin in the molecule. Usually urethane resin is produced by the reaction of polyol and isocyanate. Examples of polyols include polycarbonate polyols, polyester polyols, polyether polyols, polyolefin polyols, and acrylic polyols; these compounds may be used alone or in plural types.

乾式膜抗蝕劑基材用聚酯膜 Polyester film for dry film resist substrates

本發明之DFR基材用膜於聚酯膜之至少一單面具有塗佈層，該DFR 基材用膜之平均表面粗糙度(Ra)較佳為1~10nm，更佳為1~8nm，進而較佳為1~5nm。藉由使DFR基材用膜之平均表面粗糙度(Ra)處於1~10nm之範圍，可維持透明性。於平均表面粗糙度(Ra)超過10nm之情形時，DFR基材用膜之透明性降低，紫外線之曝光變得不充分，可能會導致電路缺損及解析度降低。另一方面，於平均表面粗糙度(Ra)未達1nm之情形時，平滑性變差，因此於步驟精確、尤其是製膜步驟中膜表面容易產生損傷，塗佈於該表面之抗蝕劑表面損傷，於抗蝕劑厚度較薄之高解析度之乾式膜抗蝕劑中可能會造成較大之影響。DFR基材用膜之平均表面粗糙度(Ra)可藉由下述實施例之測定方法進行測定。 The DFR base material film of the present invention has a coating layer on at least one side of the polyester film, and the DFR The average surface roughness (Ra) of the base film is preferably 1 to 10 nm, more preferably 1 to 8 nm, and still more preferably 1 to 5 nm. By setting the average surface roughness (Ra) of the DFR substrate film in the range of 1 to 10 nm, transparency can be maintained. When the average surface roughness (Ra) exceeds 10nm, the transparency of the DFR base film decreases and ultraviolet exposure becomes insufficient, which may cause circuit defects and lower resolution. On the other hand, when the average surface roughness (Ra) is less than 1 nm, the smoothness becomes poor, so the film surface is prone to damage during precise steps, especially during the film formation step, and the resist coated on the surface Surface damage may have a greater impact in high-resolution dry film resists where the resist thickness is thin. The average surface roughness (Ra) of the DFR substrate film can be measured by the measurement method in the following examples.

DFR基材用膜之最大表面高度(Rt)較佳為10~200nm，更佳為10~180nm。於DFR基材用膜之最大表面高度超過200nm之情形時，於乾式膜抗蝕劑產生凹陷，該凹陷部分可能會導致電路缺損及解析度降低。藉由使最大表面高度(Rt)處於該範圍，可獲得電路缺損較少且解析度良好之膜。DFR基材用膜之最大表面高度(Rt)可藉由下述實施例之測定方法進行測定。 The maximum surface height (Rt) of the film for DFR substrate is preferably 10~200nm, more preferably 10~180nm. When the maximum surface height of the DFR substrate film exceeds 200nm, dents will occur in the dry film resist, and the dents may cause circuit defects and lower resolution. By setting the maximum surface height (Rt) within this range, a film with fewer circuit defects and good resolution can be obtained. The maximum surface height (Rt) of the DFR substrate film can be measured by the measurement method in the following examples.

本發明之DFR基材用膜之霧度較佳為1.0%以下，更佳為0.7%以下。藉由使DFR基材用膜之霧度為1.0%以下，於高解像之乾式膜抗蝕劑中紫外線之曝光充分，可獲得不易產生電路缺損及解析度降低之乾式膜抗蝕劑基材用聚酯膜。DFR基材用膜之霧度之值越小越佳，通常為0.1%以上。DFR基材用膜之霧度可藉由下述實施例之測定方法進行測定。 The haze of the film for DFR substrates of the present invention is preferably 1.0% or less, more preferably 0.7% or less. By setting the haze of the film for the DFR base material to 1.0% or less and fully exposing the ultraviolet rays to the high-resolution dry film resist, a dry film resist base material that is less likely to cause circuit defects and lower resolution can be obtained. Use polyester film. The smaller the haze value of the DFR substrate film, the better, usually above 0.1%. The haze of the film for DFR substrates can be measured by the measurement method in the following examples.

本發明之DFR基材用膜之摩擦係數較佳為0.8以下，更佳為0.7以下。藉由使摩擦係數為0.8以下，可獲得捲取步驟時不易產生損傷之 DFR基材膜。關於摩擦係數，藉由向塗佈層中添加粒子，可於維持透明性之情況下賦予平滑性。摩擦係數越小越佳，DFR基材膜之摩擦係數通常為0.1以上。摩擦係數可藉由下述實施例之測定方法進行測定。 The friction coefficient of the film for DFR base material of the present invention is preferably 0.8 or less, more preferably 0.7 or less. By setting the friction coefficient to 0.8 or less, it is possible to obtain a material that is less likely to be damaged during the coiling step. DFR substrate film. Regarding the friction coefficient, by adding particles to the coating layer, smoothness can be imparted while maintaining transparency. The smaller the friction coefficient, the better. The friction coefficient of the DFR base film is usually above 0.1. The friction coefficient can be measured by the measurement method in the following examples.

本發明之DFR基材用膜依據JIS P8119所測得之空氣洩漏指數較佳為400000秒以下。DFR基材用膜之空氣洩漏指數更佳為350000秒以下，進而較佳為300000秒以下，尤佳為250000秒以下，最佳為200000秒以下。若DFR基材用膜之空氣洩漏指數為400000秒以下，則於將膜捲繞成捲筒形態時吸入之氣體容易逃逸，可使膜彼此緊密地接觸並捲緊，例如可防止保管中及搬送中之向卷芯方向之偏移，從而可防止因偏移等而產生之損傷。又，若DFR基材用膜之空氣洩漏指數為400000秒以下，則可獲得將膜捲成捲筒形態時之捲繞特性良好而不易產生表層皺褶之DFR基材用膜。DFR基材用膜之空氣洩漏指數越小越佳，若太小，則存在經捲繞之膜之密接性變得過高而加工性降低之情形。DFR基材用膜之空氣洩漏指數通常為8000秒以上，較佳為10000秒以上，更佳為30000秒以上。 The air leakage index measured according to JIS P8119 of the DFR substrate film of the present invention is preferably 400,000 seconds or less. The air leakage index of the DFR substrate film is more preferably 350,000 seconds or less, further preferably 300,000 seconds or less, particularly preferably 250,000 seconds or less, most preferably 200,000 seconds or less. If the air leakage index of the film for DFR base material is 400,000 seconds or less, the inhaled gas can easily escape when the film is rolled into a roll, and the films can be brought into close contact with each other and rolled tightly, which can prevent storage and transportation, for example. The deflection in the direction of the winding core can prevent damage caused by deflection, etc. Furthermore, if the air leakage index of the film for DFR base materials is 400,000 seconds or less, a film for DFR base materials that has good winding characteristics and is less prone to surface wrinkles when the film is rolled into a roll can be obtained. The smaller the air leakage index of the film for DFR substrates, the better. If it is too small, the adhesiveness of the rolled film may become too high and the processability may decrease. The air leakage index of the DFR substrate film is usually 8,000 seconds or more, preferably 10,000 seconds or more, and more preferably 30,000 seconds or more.

於本說明書中，空氣洩漏指數係依據JIS P8119，例如使用Digi-Bekk平滑度試驗機(DB-2，東洋精機製作所股份有限公司製造)，於溫度23℃、相對濕度50%RH之環境下使用加壓裝置之壓力100kPa、容積38mL之真空容器，測量1mL之空氣流過之時間、即容器內之壓力自50.7kPa變化至48.0kPa為止之時間(秒)，將所獲得之秒數之10倍設為空氣洩漏指數。測定用之樣品尺寸設為70mm×70mm，可以一片DFR基材用膜之樣品之塗佈層與另一片DFR基材用膜之聚酯膜重疊之方式將20片積層，並以空氣之逸出變得均勻之方式於所積層之膜之中央開設直徑5mm之孔而進行測定。 In this manual, the air leakage index is based on JIS P8119, for example, using a Digi-Bekk smoothness testing machine (DB-2, manufactured by Toyo Seiki Seisakusho Co., Ltd.) at a temperature of 23°C and a relative humidity of 50% RH. For a vacuum container with a pressure of 100 kPa and a volume of 38 mL, measure the time it takes for 1 mL of air to flow through, that is, the time (seconds) until the pressure in the container changes from 50.7 kPa to 48.0 kPa. Multiply the obtained number of seconds by 10 times. Set to air leakage index. The size of the sample for measurement is set to 70mm x 70mm. 20 pieces can be laminated in such a way that the coating layer of one DFR base film sample is overlapped with the polyester film of another DFR base film sample, and allow air to escape. In order to make the film uniform, a hole with a diameter of 5 mm was made in the center of the laminated film and measured.

進而，於無損本發明之主旨之範圍內，塗佈層亦可視需要含有消泡劑、塗佈性改良劑、增黏劑、有機系潤滑劑、紫外線吸收劑、抗氧化劑、發泡劑、染料、顏料等。 Furthermore, within the scope that does not detract from the gist of the present invention, the coating layer may optionally contain a defoaming agent, a coating property improver, a tackifier, an organic lubricant, an ultraviolet absorber, an antioxidant, a foaming agent, and a dye. , pigments, etc.

本發明之DFR基材用膜亦可於聚酯膜之至少單面具有塗佈層，且於聚酯膜之另一面設置功能層。功能層並無特別限定，可列舉防污染層、抗黏連層等。 The film for DFR base material of the present invention may also have a coating layer on at least one side of the polyester film, and a functional layer on the other side of the polyester film. The functional layer is not particularly limited, and examples thereof include anti-pollution layers, anti-adhesion layers, and the like.

本發明之DFR基材用膜藉由同時滿足透明性、防受損性、防磨削性、空氣逃逸性、及平滑性，可進行極細線之電路形成。因此，可應用於高精細之印刷配線板，具體而言，亦可適當地使用於最窄配線間隔為80μm以下之電路基板，進而亦可適當地使用於上述配線間隔為50μm以下、尤其是上述配線間隔為15μm以下之電路基板。最窄配線間隔之下限值並無限定，通常為0.1μm以上。又，於將上述「最窄配線間隔」改稱為「最窄配線(land)寬度」之情形時亦相同。本發明之DFR基材用膜可對如上述之印刷配線板實現進一步顯著之效果。 The film for DFR substrates of the present invention can form circuits with extremely fine lines by simultaneously satisfying transparency, damage resistance, grinding resistance, air escape properties, and smoothness. Therefore, it can be applied to high-definition printed wiring boards. Specifically, it can also be suitably used in circuit boards with a minimum wiring pitch of 80 μm or less. Furthermore, it can also be suitably used in circuit boards with a wiring pitch of 50 μm or less, especially the above-mentioned ones. A circuit board with wiring spacing of 15 μm or less. The lower limit of the narrowest wiring interval is not limited, but is usually 0.1 μm or more. In addition, the same is true when the above "narrowest wiring interval" is changed to "the narrowest wiring (land) width". The film for DFR base materials of the present invention can achieve further remarkable effects on printed wiring boards as described above.

乾式膜抗蝕劑 dry film resist

本發明之乾式膜抗蝕劑於本發明之DFR基材用聚酯膜之至少單面具有塗佈層，於與該塗佈層側相反之側具有感光性樹脂層。乾式膜抗蝕劑(以下，亦稱為「DFR」)可於本發明之DFR基材用膜之與塗佈層側相反側之單面塗佈感光性樹脂而形成感光性樹脂層，並藉由將本發明之DFR基材用聚酯膜進而加壓積層而貼合於該感光性樹脂層表面。具體而言，可使感光性樹脂層與2個DFR基材用聚酯膜之與塗佈層側相反之側接觸而製成被2個DFR基材用聚酯膜夾住之狀態，將2個DFR基材用膜用作感光性樹脂層 之保護膜。本發明之DFR於DFR基材用膜之至少單面具有塗佈層，藉由該塗佈層維持透明性，並且提高乾式膜抗蝕劑步驟中之平滑性、防受損性及防磨削性，因此可抑制於捲取及加工步驟中因塗佈層被擦拭而導致之粒子脫落或塗膜之磨削，從而可於感光性樹脂層形成更高精細化之導電圖案。 The dry film resist of the present invention has a coating layer on at least one side of the polyester film for a DFR base material of the present invention, and has a photosensitive resin layer on the opposite side to the coating layer side. The dry film resist (hereinafter also referred to as "DFR") can form a photosensitive resin layer by coating a photosensitive resin on one side of the film for DFR base material of the present invention on the side opposite to the coating layer side. The DFR base material of the present invention is laminated with a polyester film under pressure and bonded to the surface of the photosensitive resin layer. Specifically, the photosensitive resin layer can be brought into contact with the side of the two DFR base material polyester films opposite to the coating layer side to be sandwiched between the two DFR base material polyester films, and the two DFR base material polyester films can be sandwiched between the two DFR base material polyester films. A film for DFR substrate is used as a photosensitive resin layer protective film. The DFR of the present invention has a coating layer on at least one side of the DFR base film. The coating layer maintains transparency and improves smoothness, damage prevention and grinding resistance in the dry film resist step. Therefore, it can suppress the particle falling off or the grinding of the coating film caused by the coating layer being wiped during the rolling and processing steps, thereby forming a more refined conductive pattern on the photosensitive resin layer.

又，本發明之DFR亦可於DFR基材用膜之與塗佈層側相反之側具有感光性樹脂層，且於該感光性樹脂層貼合與本發明不同之DFR基材用膜。作為與本發明不同之DFR基材用膜，例如可列舉不具有本發明之塗佈層之DFR基材用聚酯膜、具有與本發明之塗佈層不同之層之DFR基材用膜。DFR例如亦可於本發明之DFR基材用膜之與塗佈層側相反之側具有感光性樹脂層，並將具有與本發明之塗佈層不同之功能層之DFR基材用膜之DFR基材用聚酯膜側或與本發明之塗佈層不同之功能層側加壓積層並貼合於感光性樹脂層。 Furthermore, the DFR of the present invention may have a photosensitive resin layer on the side of the DFR base film opposite to the coating layer side, and a DFR base film different from that of the present invention may be bonded to the photosensitive resin layer. Examples of films for DFR base materials that are different from the present invention include polyester films for DFR base materials that do not have the coating layer of the present invention, and films for DFR base materials that have a layer different from the coating layer of the present invention. For example, the DFR film for a DFR base material of the present invention may have a photosensitive resin layer on the side opposite to the coating layer side, and the DFR base material film may have a functional layer different from that of the coating layer of the present invention. The polyester film side of the base material or the functional layer side different from the coating layer of the present invention is press-laminated and bonded to the photosensitive resin layer.

作為感光性樹脂，可使用先前以來之組合物。通常作為乾式膜抗蝕劑用之感光性樹脂，使用負型感光性樹脂，主要包含含有具有聚合性不飽和基之單體、聚合物、光聚合起始劑等之組合物。感光性樹脂一般具有鹼水溶性，於乾式膜抗蝕劑加工步驟中經曝光之部分藉由顯影而形成電路，未曝光部分藉由顯影液而被去除。 As the photosensitive resin, a conventional composition can be used. Usually, as a photosensitive resin used in a dry film resist, a negative photosensitive resin is used, which mainly contains a composition containing a monomer, a polymer, a photopolymerization initiator, etc. having a polymerizable unsaturated group. Photosensitive resin generally has alkali water solubility. In the dry film resist processing step, the exposed part is developed to form a circuit, and the unexposed part is removed by using a developer.

作為具有聚合性不飽和基之單體，並無特別限定，可列舉：具有1個聚合性不飽和基之單體、具有2個聚合性不飽和基之單體、具有3個以上之聚合性不飽和基之單體；該等可單獨使用或適當併用後使用。 The monomer having a polymerizable unsaturated group is not particularly limited, and examples thereof include monomers having one polymerizable unsaturated group, monomers having two polymerizable unsaturated groups, and monomers having three or more polymerizable unsaturated groups. Unsaturated monomers; these can be used alone or in appropriate combination.

作為具有1個聚合性不飽和基之單體，例如可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯 酸丙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸2-苯氧基-2-羥基丙酯、鄰苯二甲酸2-(甲基)丙烯醯氧基-2-羥基丙酯、(甲基)丙烯酸3-氯-2-羥基丙酯、甘油單(甲基)丙烯酸酯、2-(甲基)丙烯醯氧基乙酸式磷酸酯、鄰苯二甲酸衍生物之半(甲基)丙烯酸酯、N-羥甲基(甲基)丙烯醯胺等。 Examples of the monomer having one polymerizable unsaturated group include: (meth)acrylic acid methyl ester, (meth)ethyl acrylate, (meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid Propyl acid, 2-hydroxypropyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate , 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, 2-(meth)acrylate acrylic acid acetate phosphate, phthalic acid derivatives of hemi(meth)acrylate, N-hydroxymethyl(meth)acrylamide, etc.

作為具有2個聚合性不飽和基之單體，例如可列舉：乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、環氧乙烷改性雙酚A型環氧樹脂二(甲基)丙烯酸酯、環氧丙烷改性雙酚A型環氧樹脂二(甲基)丙烯酸酯、環氧乙烷-環氧丙烷改性雙酚A型環氧樹脂二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、乙二醇二縮水甘油醚二(甲基)丙烯酸酯、二乙二醇二縮水甘油醚二(甲基)丙烯酸酯、丙二醇二縮水甘油基二(甲基)丙烯酸酯、鄰苯二甲酸二縮水甘油酯二(甲基)丙烯酸酯、羥基新戊酸改性新戊二醇二(甲基)丙烯酸酯等。該等之中，可尤佳地使用環氧乙烷改性雙酚A型環氧樹脂二(甲基)丙烯酸酯或環氧乙烷-環氧丙烷改性雙酚A型環氧樹脂二(甲基)丙烯酸酯。 Examples of the monomer having two polymerizable unsaturated groups include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate. ester, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate Meth)acrylate, ethylene oxide modified bisphenol A type epoxy resin di(meth)acrylate, propylene oxide modified bisphenol A type epoxy resin di(meth)acrylate, ethylene oxide Alkane-propylene oxide modified bisphenol A type epoxy resin di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol di(meth)acrylate acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, propylene glycol diglycidyl di(meth)acrylate, ortho Diglycidyl phthalate di(meth)acrylate, hydroxypivalic acid modified neopentyl glycol di(meth)acrylate, etc. Among these, ethylene oxide-modified bisphenol A-type epoxy resin di(meth)acrylate or ethylene oxide-propylene oxide-modified bisphenol A-type epoxy resin di(meth)acrylate can be particularly preferably used. Meth)acrylate.

作為具有3個以上之聚合性不飽和基之單體，例如可列舉：三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基丙烷三羧基(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、三(甲基)丙烯醯氧基乙氧基三羥甲基丙烷、甘油聚縮水甘油醚聚(甲基)丙烯酸酯等。 Examples of the monomer having three or more polymerizable unsaturated groups include trimethylolpropane tri(meth)acrylate, trimethylolpropane tricarboxy(meth)acrylate, and neopentylerythritol. Tri(meth)acrylate, dineopenterythritol penta(meth)acrylate, tri(meth)acryloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly(meth)acrylic acid Ester etc.

又，除上述以外，亦可使用(甲基)丙烯酸環氧酯系化合物、(甲基)丙烯酸胺基甲酸酯系化合物、含磷元素之聚合性化合物等。 In addition to the above, a (meth)acrylic epoxy compound, a (meth)acrylic urethane compound, a polymerizable compound containing a phosphorus element, etc. can also be used.

作為具有聚合性不飽和基之單體，較佳為具有2個聚合性不飽和基且重量平均分子量為1500以下、較佳為300~1200者，其中，尤其適合使用環氧乙烷改性雙酚A型環氧樹脂二(甲基)丙烯酸酯、環氧乙烷-環氧丙烷改性雙酚A型環氧樹脂二(甲基)丙烯酸酯。若重量平均分子量超過1,500，則存在如下情形：交聯間距離變長而有時無法獲得充分之硬化，從而導致解像力降低、細線密接性降低。 As the monomer having a polymerizable unsaturated group, one having two polymerizable unsaturated groups and a weight average molecular weight of 1,500 or less, preferably 300 to 1,200 is preferred. Among them, ethylene oxide modified bis(ethylene oxide) is particularly suitable. Phenol A type epoxy resin di(meth)acrylate, ethylene oxide-propylene oxide modified bisphenol A type epoxy resin di(meth)acrylate. If the weight average molecular weight exceeds 1,500, the distance between crosslinks may become long and sufficient hardening may not be achieved, resulting in a decrease in resolution and thin wire adhesion.

作為感光性樹脂組合物中所包含之聚合物，並無特別限定，可列舉包含丙烯酸系、甲基丙烯酸系聚合性單體之聚合物。可為均聚物或者共聚物、進而與丙烯酸系、甲基丙烯酸系單體以外之聚合性單體之共聚物之任一種。作為聚合性單體，可列舉：丙烯酸、甲基丙烯酸、丁烯酸、順丁烯二酸、反丁烯二酸、伊康酸等含羧基單體或者其等之酐或半酯；(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸二甲胺基乙酯、(甲基)丙烯酸羥乙酯、(甲基)丙烯酸羥丙酯、(甲基)丙烯酸縮水甘油酯等(甲基)丙烯酸酯；丙烯醯胺、甲基丙烯酸醯胺、丙烯腈、甲基丙烯腈、苯乙烯、α-甲基苯乙烯、乙酸乙烯酯、烷基乙烯基醚等。 The polymer contained in the photosensitive resin composition is not particularly limited, and examples thereof include polymers containing acrylic or methacrylic polymerizable monomers. It may be a homopolymer, a copolymer, or a copolymer with a polymerizable monomer other than an acrylic or methacrylic monomer. Examples of polymerizable monomers include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid, or anhydrides or half-esters thereof; (methane Methyl acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate , cyclohexyl (meth)acrylate, benzyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, (meth)acrylate (meth)acrylates such as glycidyl acrylate; acrylamide, methacrylic acid amide, acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, alkylvinyl Ether etc.

上述聚合物之重量平均分子量較佳為5千~25萬、更佳為1萬~20萬之範圍。若重量平均分子量未達5千，則存在樹脂變得過柔而於作為光阻膜加工成捲筒形態時，產生樹脂滲出之現象之情形，若超過25萬，則存在解析度降低之情形。 The weight average molecular weight of the above-mentioned polymer is preferably in the range of 5,000 to 250,000, more preferably in the range of 10,000 to 200,000. If the weight average molecular weight is less than 5,000, the resin may become too soft and may bleed out when the photoresist film is processed into a roll form. If the weight average molecular weight exceeds 250,000, the resolution may decrease.

上述聚合物之玻璃轉移溫度(Tg)較佳為30~150℃之範圍。若玻璃轉移溫度未達30℃，則存在樹脂變得過柔而於作為光阻膜加工成捲筒形態時產生樹脂滲出之現象之情形，若超過150℃，則用作光阻膜時之對基板表面之凹凸之追隨性可能會降低。 The glass transition temperature (Tg) of the above-mentioned polymer is preferably in the range of 30 to 150°C. If the glass transition temperature is less than 30°C, the resin may become too soft and the resin may bleed out when processed into a roll form as a photoresist film. If it exceeds 150°C, it may not be used as a photoresist film. The ability to follow irregularities on the substrate surface may be reduced.

作為感光性樹脂組合物中所包含之光聚合起始劑，使用先前公知者。例如可列舉：二苯甲酮、P,P'-雙(二甲基胺基)二苯甲酮、P,P'-雙(二乙基胺基)二苯甲酮、P,P'-雙(二丁基胺基)二苯甲酮、3,3'-二甲基-4-甲氧基二苯甲酮等二苯甲酮衍生物；安息香、安息香甲醚、安息香***、安息香異丙醚、安息香正丁醚、安息香苯醚、安息香異丁醚等安息香衍生物；蒽醌、萘醌等之醌衍生物；2-氯9-氧硫

Figure 108105213-A0305-02-0049-34
、2-甲基9-氧硫
Figure 108105213-A0305-02-0049-35
、2,4-二乙基9-氧硫
Figure 108105213-A0305-02-0049-36
等9-氧硫
Figure 108105213-A0305-02-0049-37
衍生物；二氯苯乙酮、2,2-二乙氧基苯乙酮、2,2-二氯-4-苯氧基苯乙酮等苯乙酮衍生物；乙醛酸苯酯、α-羥基異丁基苯酮、二苯并環庚酮、1-(4-異丙基苯基)-2-羥基-2-甲基-1-丙酮、2-甲基-[4-(甲硫基)苯基]-2-嗎啉基-1-丙酮等丙酮衍生物；三溴苯基碸、三溴甲基苯基碸等碸衍生物；2,4,6-[三(三氯甲基)]-1,3,5-三
Figure 108105213-A0305-02-0049-38
、2,4-[雙(三氯甲基)]-6-(4'-甲氧基苯基)-1,3,5-三
Figure 108105213-A0305-02-0049-39
、2,4-[雙(三氯甲基)]-6-(4'-甲氧基萘基)-1,3,5-三
Figure 108105213-A0305-02-0049-40
、2,4-[雙(三氯甲基)]-6-(向日葵基)-1,3,5-三
Figure 108105213-A0305-02-0049-41
、2,4-[雙(三氯甲基)]-6-(4'-甲氧基苯乙烯基)-1,3,5-三
Figure 108105213-A0305-02-0049-42
等三
Figure 108105213-A0305-02-0049-43
衍生物；吖啶及9-苯基吖啶等吖啶衍生物；2,2'-雙(鄰氯苯基)-4,5,4',5'-四苯基-1,2'-聯咪唑、2,2'-雙(鄰氯苯基)-4,5,4',5'-四苯基-1,1'-聯咪唑、2,2'-雙(鄰氟苯基)-4,5,4',5'-四苯基-1,1'-聯咪唑、2,2'-雙(鄰甲氧基苯基)-4,5,4',5'-四苯基-1,1'-聯咪唑、2,2'-雙(對甲氧基苯基)-4,5,4',5'-四苯基-1,1'-聯咪唑、2,4,2',4'-雙[雙(對甲氧基苯基)]-5,5'-二苯基-1,1'-聯咪唑、2,2'-雙(2,4-二 甲氧基苯基)-4,5,4',5'-二苯基-1,1'-聯咪唑、2,2'-雙(對甲硫基苯基)-4,5,4',5'-二苯基-1,1'-聯咪唑、雙(2,4,5-三苯基)-1,1'-聯咪唑等或日本專利特公昭45-37377號公報所揭示之於1,2'-、1,4'-、2,4'-共價鍵結之互變異構物等六芳基聯咪唑衍生物等；又，此外可列舉：苯甲醯苯甲酸、苯甲醯苯甲酸甲酯、苯偶醯二苯基二硫醚、苯偶醯二甲基縮酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉丙烷-1-酮、2,2-二甲氧基-1,2-二苯乙烷-1-酮、1-羥基-環己基-苯基-酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、1-[4-(2-羥基乙氧基)-苯基]-2-羥基-2-甲基-1-丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮-1、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基-戊基氧化膦、2,4,6-三甲基苯甲醯基二苯基氧化膦、雙(η5-2,4-環戊二烯-1-基)-雙(2,6-二氟-3-(1H-吡咯-1-基)-苯基)鈦等。該等可單獨使用或將2種以上併用。該等之中，較佳為2,2-二甲氧基-1,2-二苯乙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁酮-1。 As the photopolymerization initiator contained in the photosensitive resin composition, a conventionally known one is used. Examples include: benzophenone, P,P'-bis(dimethylamino)benzophenone, P,P'-bis(diethylamino)benzophenone, P,P'- Benzophenone derivatives such as bis(dibutylamino)benzophenone, 3,3'-dimethyl-4-methoxybenzophenone; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isophenone Benzoin derivatives such as propyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzoin isobutyl ether, etc.; quinone derivatives such as anthraquinone and naphthoquinone; 2-chloro-9-oxosulfide
Figure 108105213-A0305-02-0049-34
, 2-Methyl 9-oxosulfide
Figure 108105213-A0305-02-0049-35
, 2,4-diethyl 9-oxosulfide
Figure 108105213-A0305-02-0049-36
Etc. 9-oxysulfur
Figure 108105213-A0305-02-0049-37
Derivatives; dichloroacetophenone, 2,2-diethoxyacetophenone, 2,2-dichloro-4-phenoxyacetophenone and other acetophenone derivatives; phenyl glyoxylate, α -Hydroxyisobutylphenone, dibenzocycloheptanone, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone, 2-methyl-[4-(methyl Thio)phenyl]-2-morpholinyl-1-propanone and other acetone derivatives; tribromophenyl terine, tribromomethylphenyl terine and other terine derivatives; 2,4,6-[tris(trichloro Methyl]-1,3,5-tri
Figure 108105213-A0305-02-0049-38
,2,4-[Bis(trichloromethyl)]-6-(4'-methoxyphenyl)-1,3,5-tri
Figure 108105213-A0305-02-0049-39
, 2,4-[bis(trichloromethyl)]-6-(4'-methoxynaphthyl)-1,3,5-tri
Figure 108105213-A0305-02-0049-40
, 2,4-[bis(trichloromethyl)]-6-(sunfloweryl)-1,3,5-tri
Figure 108105213-A0305-02-0049-41
, 2,4-[Bis(trichloromethyl)]-6-(4'-methoxystyryl)-1,3,5-tri
Figure 108105213-A0305-02-0049-42
Wait three
Figure 108105213-A0305-02-0049-43
Derivatives; acridine derivatives such as acridine and 9-phenylacridine; 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'- Biimidazole, 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,1'-biimidazole, 2,2'-bis(o-fluorophenyl) -4,5,4',5'-tetraphenyl-1,1'-biimidazole, 2,2'-bis(o-methoxyphenyl)-4,5,4',5'-tetraphenyl 1,1'-biimidazole, 2,2'-bis(p-methoxyphenyl)-4,5,4',5'-tetraphenyl-1,1'-biimidazole, 2,4 ,2',4'-bis[bis(p-methoxyphenyl)]-5,5'-diphenyl-1,1'-biimidazole, 2,2'-bis(2,4-dimethyl Oxyphenyl)-4,5,4',5'-diphenyl-1,1'-biimidazole, 2,2'-bis(p-methylthiophenyl)-4,5,4', 5'-diphenyl-1,1'-biimidazole, bis(2,4,5-triphenyl)-1,1'-biimidazole, etc. or those disclosed in Japanese Patent Publication No. Sho 45-37377 1,2'-, 1,4'-, 2,4'- covalently bonded tautomers and other hexaarylbiimidazole derivatives; and, in addition, benzoyl benzoic acid, benzyl Methyl benzoate, benzyl diphenyl disulfide, benzyl dimethyl ketal, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane- 1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-one, 2-hydroxy-2-methyl-1-benzene Propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-benzyl-2-di Methylamino-1-(4-morpholinylphenyl)-butanone-1, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6- Dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(eta5-2, 4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, etc. These can be used individually or in combination of 2 or more types. Among these, 2,2-dimethoxy-1,2-diphenylethane-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholine phenyl)-butanone-1.

感光性樹脂組合物中另外可添加三聚氰胺等胺基樹脂或異氰酸酯系化合物等熱交聯劑、結晶紫、孔雀綠、孔雀綠色澱、煌綠、專利藍、甲基紫、維多利亞藍、玫瑰苯胺、副品紅、乙烯紫等著色染料、密接性賦予劑、塑化劑、抗氧化劑、熱聚合抑制劑、溶劑、表面張力改質材、穩定劑、鏈轉移劑、消泡劑、阻燃劑等添加劑。 In addition, the photosensitive resin composition may be added with amine-based resins such as melamine or thermal cross-linking agents such as isocyanate compounds, crystal violet, malachite green, malachite green lake, brilliant green, patent blue, methyl violet, Victoria blue, rose aniline, Colored dyes such as fuchsin and ethylene violet, adhesion imparting agents, plasticizers, antioxidants, thermal polymerization inhibitors, solvents, surface tension modifying materials, stabilizers, chain transfer agents, defoaming agents, flame retardants, etc. Additives.

於在基材膜之上設置感光性樹脂組合物而製作感光性樹脂層之情形時，可列舉將有機溶劑以成為特定濃度之方式混合於感光性樹脂組合物中而使用之方法。作為有機溶劑，例如可列舉：丙酮、甲基乙基酮、甲醇、乙醇、異丙醇、甲苯、丙二醇單***、丙二醇單甲醚乙酸酯、乙酸乙酯、乙酸丁酯等。該等可單獨使用，亦可將2種以上併用。利用輥 式塗佈法或棒式塗佈法等方法將含有感光性樹脂組合物之混合物之塗佈液均勻地塗佈於載體膜之單面，於通常為50~130℃或者依次於溫度增大之烘箱中進行乾燥，形成感光性樹脂層，並捲取成捲筒狀，藉此製造感光性樹脂積層體(乾式膜抗蝕劑)。 When a photosensitive resin composition is provided on a base film to form a photosensitive resin layer, an organic solvent may be mixed with the photosensitive resin composition to a specific concentration and used. Examples of the organic solvent include acetone, methyl ethyl ketone, methanol, ethanol, isopropyl alcohol, toluene, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, and the like. These may be used individually or in combination of 2 or more types. Utilize roller The coating liquid containing the mixture of the photosensitive resin composition is evenly coated on one side of the carrier film by a method such as a formula coating method or a rod coating method, and the temperature is usually 50 to 130°C or as the temperature increases. It is dried in an oven to form a photosensitive resin layer, and is rolled into a roll to produce a photosensitive resin laminate (dry film resist).

[實施例] [Example]

以下，藉由實施例對本發明進而詳細地進行說明，本發明只要不越過其主旨，則並不限定於以下之實施例。又，本發明中使用之測定法及評價方法如下所述。 Hereinafter, the present invention will be further described in detail using examples. However, the present invention is not limited to the following examples as long as the gist of the invention is not exceeded. In addition, the measurement method and evaluation method used in the present invention are as follows.

(1)聚酯之極限黏度之測定方法 (1) Determination method of ultimate viscosity of polyester

準確稱量精秤將不與聚酯相溶之其他聚合物成分及顏料去除後之聚酯1g，添加苯酚/四氯乙烷=50/50(重量比)之混合溶劑100ml使之溶解，並於30℃下進行測定。 Accurately weigh 1g of polyester with a precision scale after removing other polymer components and pigments that are not compatible with polyester, add 100ml of a mixed solvent of phenol/tetrachloroethane = 50/50 (weight ratio) to dissolve it, and Measurement was performed at 30°C.

(2)粒徑及平均粒徑(d50)之測定方法 (2)Measurement method of particle size and average particle size (d50)

使用島津製作所股份有限公司製造之離心沈降式粒度分佈測定裝置(SA-CP3型)測定包含粉體之粒子A或粒子B之等效球形分佈，求出各粒徑範圍之累計體積分率。又，將對各粒子進行測定所得之等效球形分佈中之累計體積分率50%之粒徑設為平均粒徑d50。 The equivalent spherical distribution of particle A or particle B containing powder was measured using a centrifugal sedimentation particle size distribution analyzer (SA-CP3 model) manufactured by Shimadzu Corporation, and the cumulative volume fraction of each particle size range was calculated. In addition, the particle diameter at which the cumulative volume fraction in the equivalent spherical distribution measured for each particle is 50% is defined as the average particle diameter d50.

(3)平均表面粗糙度(Ra)之測定方法 (3)Measurement method of average surface roughness (Ra)

使用小阪研究所股份有限公司製造之表面粗糙度測定機(SE-3500)並以如下方式求出。即，自DFR基材用膜之試樣膜之塗佈層表面之剖面曲線 中沿其平均線之方向截取基準長度L(2.5mm)之部分，將該截取部分之平均線作為x軸、將縱倍率之方向作為y軸並以粗糙度曲線y=f(x)表示時，以[nm]表示由下述式(1)賦予之值。關於算術平均粗糙度，自試樣膜表面求出10條粗糙度曲線，並以根據該等粗糙度曲線求出之截取部分之算術平均粗糙度之平均值表示。再者，觸針之前端半徑設為2μm，負載設為30mg，臨界值設為0.08mm。 The surface roughness measuring machine (SE-3500) manufactured by Kosaka Laboratory Co., Ltd. was used and the surface roughness was determined as follows. That is, the cross-sectional curve of the coating layer surface of the sample film for DFR substrate film When a portion of the reference length L (2.5mm) is cut out along the direction of its average line, the average line of the cut-out portion is taken as the x-axis, the direction of the vertical magnification is taken as the y-axis, and expressed as a roughness curve y=f(x) , the value given by the following formula (1) is expressed in [nm]. Regarding the arithmetic mean roughness, 10 roughness curves were obtained from the surface of the sample film, and expressed as the average of the arithmetic mean roughness of the intercepted portions calculated based on these roughness curves. Furthermore, the tip radius of the stylus is set to 2 μm, the load is set to 30 mg, and the critical value is set to 0.08 mm.

Ra=(1/L)ʃL0｜f(x)｜dx (1) Ra=(1/L)ʃL0｜f(x)｜dx (1)

(4)最大表面高度(Rt)之測定方法 (4)Measurement method of maximum surface height (Rt)

針對測定DFR基材用膜之試樣膜之平均表面粗糙度(Ra)時所獲得之剖面曲線之截取部分，利用與其平均線平行之2直線夾住截取部分時，於剖面曲線之縱倍率之方向上測定該2直線之間隔，將利用微米(μm)單位對該值進行表示所得者作為截取部分之最大表面高度(Rt)。最大表面高度係自試樣膜表面求出10條剖面曲線，並由根據該等剖面曲線求出之截取部分之最大表面高度之平均值表示。 When measuring the average surface roughness (Ra) of the sample film for DFR substrate film, the intercepted part of the cross-sectional curve is sandwiched between two straight lines parallel to the average line, and the longitudinal magnification of the cross-sectional curve is The distance between the two straight lines is measured in the direction, and the value expressed in micron (μm) units is taken as the maximum surface height (Rt) of the intercepted portion. The maximum surface height is calculated from 10 profile curves on the surface of the sample film, and is expressed by the average value of the maximum surface height of the intercepted portions calculated based on these profile curves.

(5)塗佈層之膜厚測定方法 (5)Measurement method of film thickness of coating layer

利用RuO4對DFR基材用膜之試樣膜之塗佈層表面進行染色，並包埋於環氧樹脂中。其後，利用RuO4對藉由超薄切片法而製作之切片進行染色，使用日立高新技術股份有限公司製造之穿透式電子顯微鏡(Transmission Electron Microscope；TEM)(H-7650，加速電壓100kV)對塗佈層之剖面進行測定。 The surface of the coating layer of the sample film of the DFR substrate film was dyed with RuO 4 and embedded in epoxy resin. Thereafter, the sections prepared by the ultrathin sectioning method were stained with RuO 4 , and a Transmission Electron Microscope (TEM) manufactured by Hitachi High-Technology Co., Ltd. (H-7650, accelerating voltage 100 kV) was used. Measure the cross-section of the coating layer.

(6)塗佈層之外觀之評價方法 (6) Evaluation method of appearance of coating layer

對DFR基材用膜之試樣膜之塗佈層表面照射GENTOS股份有限公司製造之LED燈(GF-006)並進行目視觀察，將未出現塗佈不均之情況設為A，將略微出現塗佈不均之情況設為B，將出現少許塗佈不均之情況設為C，將整個面出現塗佈不均之情況設為D。 The surface of the coating layer of the sample film for DFR substrate film was irradiated with an LED lamp (GF-006) manufactured by GENTOS Co., Ltd. and visually observed. The case where uneven coating did not occur was regarded as A, and the case where uneven coating did not occur was regarded as A. The case where uneven coating occurs is designated as B, the case where there is slight uneven coating is designated as C, and the case where uneven coating occurs on the entire surface is designated as D.

(7)塗佈層之收縮之評價方法 (7) Evaluation method for shrinkage of coating layer

對DFR基材用膜之試樣膜之塗佈層表面照射GENTOS股份有限公司製造之LED燈(GF-006)並進行目視觀察，確認試樣膜表面有無塗佈層未被被覆之部位。將塗佈層未被被覆之部位、即未出現收縮之情況設為A，將略微出現收縮之情況設為B，將出現少許收縮之情況設為C，將整個面出現收縮之情況設為D。 The surface of the coating layer of the sample film of the DFR base material film was irradiated with an LED lamp (GF-006) manufactured by GENTOS Co., Ltd. and visually observed to confirm whether there were any uncoated parts of the coating layer on the surface of the sample film. Let the uncoated part of the coating layer, that is, no shrinkage, be designated as A. The case where there is slight shrinkage is designated as B. The case where there is slight shrinkage is designated as C. The case where the entire surface shrinks is designated as D. .

(8)膜霧度之測定方法 (8)Measurement method of film haze

針對DFR基材用膜之試樣膜，依據JIS-K7136並使用村上色彩技術研究所股份有限公司製造之測霧計(HM-150)測定膜霧度。 For the sample film of the DFR substrate film, the film haze was measured using a haze meter (HM-150) manufactured by Murakami Color Technology Research Institute Co., Ltd. in accordance with JIS-K7136.

(9)動摩擦係數之測定方法 (9)Measurement method of dynamic friction coefficient

將塗佈層作為上表面而將DFR用基材膜之試樣膜貼附於寬10mm、長100mm之平滑之玻璃板上，並將切取成寬18mm、長120mm之另一試樣膜以塗佈層彼此相接之方式積層於該塗佈層上。進而自另一試樣膜之上抵接於直徑8mm之金屬針，使金屬針沿玻璃板之長度方向以負荷30g、40mm/min滑動而測定摩擦力，將以10mm滑動時之摩擦係數設為動摩擦 係數。 Using the coating layer as the upper surface, attach the sample film of the DFR base film to a smooth glass plate with a width of 10mm and a length of 100mm, and cut another sample film of 18mm in width and 120mm in length for coating. The cloth layers are laminated on the coating layer in such a manner that they are connected to each other. Then, a metal needle with a diameter of 8mm is placed on another sample film, and the metal needle is slid along the length direction of the glass plate with a load of 30g and 40mm/min to measure the friction force. The friction coefficient when sliding at 10mm is set to dynamic friction coefficient.

(10)防受損性之評價方法 (10) Evaluation method of damage resistance

使用太平理化工業股份有限公司製造之摩擦測試機於DFR基材用膜之試驗膜之塗佈層表面往返摩擦5次，對經摩擦之部位照射GENTOS股份有限公司製造之LED燈：GF-006並進行目視觀察。將完全未出現塗佈層之受損之情況設為A，將雖有受損但受損面積相對於試驗膜之總面積為20%以下之情況設為B，將超過20%且50%以下之情況設為C，將超過50%之情況設為D。 Use the friction testing machine manufactured by Taiping R&D Co., Ltd. to rub the surface of the coating layer of the test film for DFR base material back and forth 5 times, and irradiate the rubbed area with the LED lamp: GF-006 manufactured by GENTOS Co., Ltd. Make visual observations. The case where there is no damage to the coating layer is designated as A, the case where there is damage but the damaged area is less than 20% of the total area of the test film is designated as B, the case where it exceeds 20% and is less than 50% The situation where it exceeds 50% is set as C, and the situation where it exceeds 50% is set as D.

(11)空氣洩漏指數之測定方法 (11)Measurement method of air leakage index

使用東洋精機股份有限公司製造之Digi-Bekk平滑度試驗機：DB-2，依據JIS P8119於溫度23℃、濕度50%RH之環境下進行測定。加壓裝置之壓力為100kPa，真空容器使用容積38ml之容器，測量1mL之空氣流過之時間、即容器內之壓力自50.7kPa變化成48.0kPa為止之時間(秒)，將所獲得之秒數之10倍設為空氣洩漏指數。DFR基材用膜之試驗膜之樣品尺寸設為70mm見方，以試驗膜之正反面(塗佈層側與聚酯膜側)重疊之方式將20片積層，並於以空氣之逸出變得均勻之方式積層之膜之中央開設直徑5mm之孔來進行測定。該空氣洩漏指數之值越大，空氣自膜彼此之間隙滲出越需要時間，因此表示膜彼此更緊密地相接。 The Digi-Bekk smoothness testing machine: DB-2 manufactured by Toyo Seiki Co., Ltd. was used to measure according to JIS P8119 in an environment with a temperature of 23°C and a humidity of 50% RH. The pressure of the pressurizing device is 100kPa, and the vacuum container uses a container with a volume of 38ml. Measure the time for 1mL of air to flow through, that is, the time (seconds) until the pressure in the container changes from 50.7kPa to 48.0kPa, and divide the obtained seconds into 10 times is set as the air leakage index. The sample size of the test film for DFR base material film was set to 70 mm square. 20 pieces were laminated in such a way that the front and back sides of the test film (the coating layer side and the polyester film side) were overlapped, and the air was allowed to escape. A hole with a diameter of 5 mm was opened in the center of the film laminated in a uniform manner for measurement. The larger the value of the air leakage index, the longer it takes for air to seep out from the gap between the membranes, indicating that the membranes are more closely connected to each other.

(12)表層皺褶之評價方法 (12) Evaluation method of surface wrinkles

將DFR基材用膜之試樣膜捲取成500m捲筒狀，並於溫度23℃、濕度 50%RH之環境下放置16小時。經過16小時後，對捲取成捲筒狀之狀態之膜之表層進行觀察。將表層未產生皺褶之情況設為A，將表層產生之皺褶之捲筒卷芯方向之寬度(以下，將皺褶之卷芯方向之寬度稱為「橫寬」)為1cm以下之情況設為B，將橫寬超過1cm且5cm以下之情況設為C，將橫寬超過5cm之情況設為D。 Roll the sample film of the DFR substrate film into a 500m roll, and store it at a temperature of 23°C and a humidity of Leave it in an environment of 50%RH for 16 hours. After 16 hours passed, the surface layer of the film rolled into a roll was observed. The case where no wrinkles are produced on the surface layer is defined as A, and the width of the wrinkles produced on the surface layer in the roll core direction (hereinafter, the width of the wrinkles in the roll core direction is referred to as the "horizontal width") is 1 cm or less. Set it as B, set it as C if the width exceeds 1cm and 5cm or less, and set it as D if the width exceeds 5cm.

(13)表面電阻值之評價方法 (13)Evaluation method of surface resistance value

使用三菱化學ANALYTECH股份有限公司製造之高電阻測定器：UX MCP-HT800，於23℃、50%RH之測定環境下對DFR基材用膜之樣品進行30分鐘調濕後，測定塗佈層表面之表面電阻值。 Using a high resistance tester: UX MCP-HT800 manufactured by Mitsubishi Chemical ANALYTECH Co., Ltd., the sample of the DFR substrate film was humidified for 30 minutes in a measurement environment of 23°C and 50% RH, and then the surface of the coating layer was measured. The surface resistance value.

(14)粒子AS及粒子AL之塗佈層表面之面積比率 (14) Area ratio of the coating layer surface of particle AS and particle AL

粒子AS及粒子AL之粒徑係使用掃描式電子顯微鏡(日本FEI股份有限公司製造，「NovaNanoSEM」)以5萬倍或10萬倍對塗佈層表面進行觀察，任意選擇可根據所獲得之圖像資料識別之2000個粒子，針對2000個粒子，使用圖像解析軟體(日本Ropper股份有限公司製造，「Image-Pro Premier」)測定各粒子之粒徑。對所測定之所有粒子之面積進行合計，對粒徑為30~80nm之粒子AS之面積進行合計，算出粒子AS相對於經測定之所有粒子之面積合計100%之面積比率。又，對圖像資料進行解析，對經測定之粒子之中粒徑為100~400nm之粒子AL之面積進行合計，算出粒子AL相對於經測定之所有粒子之面積合計100%之面積比率。 The particle diameters of particles AS and particles AL are determined by observing the surface of the coating layer using a scanning electron microscope (manufactured by Japan FEI Co., Ltd., "NovaNanoSEM") at 50,000 times or 100,000 times. The choice can be made based on the obtained image. The 2000 particles identified by the image data were used to measure the particle size of each particle using image analysis software ("Image-Pro Premier" manufactured by Japan Ropper Co., Ltd.). The areas of all measured particles were totaled, and the areas of particles AS having a particle diameter of 30 to 80 nm were totaled, and the area ratio of particles AS to 100% of the total area of all measured particles was calculated. Furthermore, the image data is analyzed, the areas of particles AL having a particle size of 100 to 400 nm among the measured particles are totaled, and the area ratio of particles AL to 100% of the total area of all measured particles is calculated.

於實施例及比較例中使用之聚酯係以如下方式準備。 The polyester used in Examples and Comparative Examples was prepared as follows.

<聚酯(A)> <Polyester(A)>

使用作為二羧酸成分之對苯二甲酸、作為多元醇成分之乙二醇，並利用常規方法之熔融聚合法獲得之極限黏度為0.65dl/g之聚酯(A)。 Polyester (A) with an ultimate viscosity of 0.65 dl/g was obtained by using terephthalic acid as a dicarboxylic acid component and ethylene glycol as a polyol component and using a conventional melt polymerization method.

<聚酯(B)> <Polyester(B)>

使用於聚酯(A)之製造方法中，除於熔融聚合前添加1.5重量份作為粒子B之平均粒徑0.05μm之氧化鋁粒子以外與聚酯(A)之製造方法相同之方法獲得之聚酯(B)。 Used in the production method of polyester (A), except that 1.5 parts by weight of alumina particles with an average particle diameter of 0.05 μm as particle B are added before melt polymerization, the polyester is obtained by the same method as the production method of polyester (A). Esters (B).

<聚酯(C)> <Polyester(C)>

使用於聚酯(A)之製造方法中，除於熔融聚合前添加0.5重量份作為粒子B之平均粒徑0.35μm之交聯苯乙烯樹脂粒子以外與聚酯(A)之製造方法相同之方法獲得之聚酯(C)。 The method used in the production method of polyester (A) is the same as the production method of polyester (A), except that 0.5 parts by weight of cross-linked styrene resin particles with an average particle diameter of 0.35 μm as particle B are added before melt polymerization. Obtained polyester (C).

<聚酯(D)> <Polyester(D)>

使用於聚酯(A)之製造方法中，除於熔融聚合前添加0.2重量份作為粒子B之平均粒徑2.0μm之二氧化矽粒子以外與聚酯(A)之製造方法相同之方法獲得之聚酯(D)。 Used in the production method of polyester (A), it is obtained by the same method as the production method of polyester (A), except that 0.2 parts by weight of silica particles with an average particle diameter of 2.0 μm as particle B are added before melt polymerization. Polyester(D).

用以形成塗佈層之塗佈液中所包含之化合物如下所述。 The compounds contained in the coating liquid for forming the coating layer are as follows.

交聯劑 Cross-linking agent

‧三聚氰胺化合物(I)：六甲氧基羥甲基三聚氰胺。 ‧Melamine compound (I): hexamethoxyhydroxymethylmelamine.

脫模劑 Release agent

‧聚乙烯蠟(II)： 以如下方式獲得之蠟乳液：向具備攪拌機、溫度計、溫度控制器之內容量1.5L之乳化設備中添加熔點105℃、酸值16mgKOH/g、密度0.93g/mL、平均分子量5000之氧化聚乙烯蠟300g、離子交換水650g及十甘油單油酸酯界面活性劑50g、48%氫氧化鉀水溶液10g並利用氮氣置換後進行密封，於150℃下高速攪拌1小時後冷卻至130℃，使高壓均質機於400氣壓下通過並冷卻至40℃。 ‧Polyethylene wax (II): The wax emulsion obtained in the following manner: Add oxidized polyethylene with a melting point of 105°C, an acid value of 16mgKOH/g, a density of 0.93g/mL, and an average molecular weight of 5000 into an emulsification equipment with an internal capacity of 1.5L equipped with a mixer, a thermometer, and a temperature controller. 300g of wax, 650g of ion exchange water, 50g of decaglycerol monooleate surfactant, and 10g of 48% potassium hydroxide aqueous solution were replaced with nitrogen and sealed. Stirred at high speed for 1 hour at 150°C and then cooled to 130°C. The homogenizer is passed through at 400 air pressure and cooled to 40°C.

粒子A Particle A

‧二氧化矽粒子(IIIA)：平均粒徑0.02μm之膠體二氧化矽(粒子A-1)。 ‧Silica particles (IIIA): colloidal silica (particle A-1) with an average particle size of 0.02μm.

根據於使用水作為溶劑之該二氧化矽粒子之分散液(固形物成分濃度10質量%)之狀態下利用粒徑測定裝置(大塚電子股份有限公司製造，「ELSZ-2000ZS」)所測得之粒徑算出之粒徑未達30nm之粒子之體積分率為77.3%，粒徑30~80nm之粒子AS之體積分率為22.0%。再者，於分散液之狀態下測得之二氧化矽粒子之粒度分佈與相對於對塗佈層之表面進行觀察時之塗佈層表面之粒子之面積合計的二氧化矽粒子之面積比率由於測定方法不同，故而不一致。 Measured using a particle size measuring device (manufactured by Otsuka Electronics Co., Ltd., "ELSZ-2000ZS") in the state of a dispersion of silica particles (solid content concentration: 10% by mass) using water as a solvent The calculated particle size indicates that the volume fraction of particles with a particle size less than 30 nm is 77.3%, and the volume fraction of particles AS with a particle size of 30 to 80 nm is 22.0%. Furthermore, the particle size distribution of the silica particles measured in the state of the dispersion liquid and the area ratio of the silica particles relative to the total area of the particles on the surface of the coating layer when the surface of the coating layer is observed are due to The measurement methods are different and therefore inconsistent.

‧二氧化矽粒子(IIIB)：平均粒徑0.045μm之膠體二氧化矽(粒子A-1)。 ‧Silica particles (IIIB): colloidal silica (particle A-1) with an average particle size of 0.045 μm.

根據於使用水作為溶劑之該二氧化矽粒子之分散液(固形物成分濃度10質量%)之狀態下使用粒徑測定裝置(大塚電子股份有限公司製造，「ELSZ-2000ZS」)所測得之粒徑而算出之粒徑30~80nm之粒子AS之體積分率為92.4%，粒徑100~400nm之粒子AL之體積分率為1.4%。 Measured using a particle size measuring device (manufactured by Otsuka Electronics Co., Ltd., "ELSZ-2000ZS") in a dispersion of silica particles (solid content concentration: 10% by mass) using water as a solvent. The calculated volume fraction of particles AS with a particle size of 30 to 80 nm is 92.4%, and the volume fraction of particles AL with a particle size of 100 to 400 nm is 1.4%.

‧二氧化矽粒子(IIIC)：平均粒徑0.07μm之膠體二氧化矽(粒子A-2)。 ‧Silica particles (IIIC): colloidal silica (particles A-2) with an average particle size of 0.07μm.

根據於使用水作為溶劑之該二氧化矽粒子之分散液(固形物成分濃度10質量%)之狀態下使用粒徑測定裝置(大塚電子股份有限公司製造，「ELSZ-2000ZS」)所測得之粒徑而算出之粒徑30~80nm之粒子AS之體積分率為65.8%，粒徑100~400nm之粒子AL之體積分率為16.5%。 Measured using a particle size measuring device (manufactured by Otsuka Electronics Co., Ltd., "ELSZ-2000ZS") in a dispersion of silica particles (solid content concentration: 10% by mass) using water as a solvent. The calculated volume fraction of particles AS with a particle size of 30 to 80 nm is 65.8%, and the volume fraction of particles AL with a particle size of 100 to 400 nm is 16.5%.

‧二氧化矽粒子(IIID)：平均粒徑0.14μm之膠體二氧化矽(粒子A-2)。 ‧Silica particles (IIID): colloidal silica (particles A-2) with an average particle size of 0.14μm.

根據於使用水作為溶劑之該二氧化矽粒子之分散液(固形物成分濃度10質量%)之狀態下使用粒徑測定裝置(大塚電子股份有限公司製造，「ELSZ-2000ZS」)所測得之粒徑而算出之粒徑100~400nm之粒子AL之體積分率為100%。 Measured using a particle size measuring device (manufactured by Otsuka Electronics Co., Ltd., "ELSZ-2000ZS") in a dispersion of silica particles (solid content concentration: 10% by mass) using water as a solvent. The volume fraction of particles AL with a particle size of 100~400 nm is 100%.

‧二氧化矽粒子(IIIE)：平均粒徑0.45μm之膠體二氧化矽(粒子A-2)。 ‧Silica particles (IIIE): colloidal silica (particles A-2) with an average particle size of 0.45μm.

根據於使用水作為溶劑之該二氧化矽粒子之分散液(固形物成分濃度10質量%)之狀態下使用粒徑測定裝置(大塚電子股份有限公司製造，「ELSZ-2000ZS」)所測得之粒徑而算出之粒徑超過400nm且1000nm以下之粒子之體積分率為100%。 Measured using a particle size measuring device (manufactured by Otsuka Electronics Co., Ltd., "ELSZ-2000ZS") in a dispersion of silica particles (solid content concentration: 10% by mass) using water as a solvent. The volume fraction of particles with a calculated particle diameter of more than 400 nm and less than 1000 nm is 100%.

各種聚合物 various polymers

‧丙烯酸系樹脂(IVA)： 以丙烯酸正丁酯/甲基丙烯酸正丁酯/丙烯酸乙酯/甲基丙烯酸乙酯=20/26/40/14(莫耳%)進行共聚而成之丙烯酸系樹脂。 ‧Acrylic resin (IVA): Acrylic resin copolymerized with n-butyl acrylate/n-butyl methacrylate/ethyl acrylate/ethyl methacrylate = 20/26/40/14 (mol%).

‧聚酯樹脂(IVB)： 以(酸成分)對苯二甲酸/間苯二甲酸/5-磺基間苯二甲酸鈉/(二醇成分)乙二醇/1,4-丁二醇/二乙二醇=56/40/4/70/20/10(莫耳%)進行共聚而成之聚酯樹脂水分散體。 ‧Polyester resin (IVB): With (acid component) terephthalic acid/isophthalic acid/sodium 5-sulfoisophthalate/(diol component) ethylene glycol/1,4-butanediol/diethylene glycol=56/40/ Aqueous polyester resin dispersion formed by copolymerization of 4/70/20/10 (mol%).

交聯觸媒 Cross-linking catalyst

‧三聚氰胺交聯觸媒(V)：2-胺基-2-甲基鹽酸鹽。 ‧Melamine cross-linking catalyst (V): 2-amino-2-methyl hydrochloride.

抗靜電劑 antistatic agent

‧抗靜電劑(VI)：包含下述式之結構單元且抗衡離子為甲磺酸根離子之具有三級胺基之數量平均分子量50000之聚合物。 ‧Antistatic agent (VI): a polymer with a number average molecular weight of 50,000 of tertiary amine groups that contains the structural unit of the following formula and the counterion is methanesulfonate ion.

Figure 108105213-A0305-02-0059-1
Figure 108105213-A0305-02-0059-1

界面活性劑 surfactant

‧界面活性劑(VIIA)：聚氧乙烯月桂醚。 ‧Surfactant (VIIA): polyoxyethylene lauryl ether.

‧界面活性劑(VIIB)：月桂基磺酸鈉。 ‧Surface active agent (VIIB): sodium lauryl sulfonate.

‧界面活性劑(VIIC)：甘油醚。 ‧Surfactant (VIIC): glyceryl ether.

無機鹽 Inorganic salt

‧氯化鈉(VIII)：和光純藥工業股份有限公司製造 特級試劑。 ‧Sodium chloride (VIII): Special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.

聚醚化合物 polyether compounds

‧聚醚化合物(IX)：15-冠醚-5之冠醚。 ‧Polyether compound (IX): 15-crown ether-5 crown ether.

實施例1： Example 1:

將聚酯(A)、(B)、(C)分別以75%、20%、5%之質量比率進行混合，將所得之混合原料作為最外層(表層)之原料，將聚酯(A)作為中間層之原料，分別供給至2台擠出機，分別於285℃下熔融後，以2種3層(表層/中間層/表層=1：14：1之噴出量)之層構成共擠出至設定為35℃之冷卻輥上進行冷卻固化，而獲得未延伸片材。繼而，利用輥周速差以膜溫度85℃於縱向上延伸3.2倍後，於該縱延伸膜之單面塗佈下述表1所示之調配之塗佈液5，導入拉幅機中，於橫向上以95℃延伸4.0倍，並於230℃下進行熱處理後，於橫向上鬆弛2%，獲得DFR基材用膜。所獲得之DFR基材用膜於厚度16μm之聚酯膜之單面具有乾燥後之膜厚為0.04μm之塗佈層，塗佈層表面之平均表面粗糙度(Ra)為4nm，塗佈層表面之最大表面高度(Rt)為100nm。將該膜之特性示於下述表2。如表2所示，實施例1之DFR基材用膜之膜霧度、動摩擦係數較低，維持塗佈層之透明性，並且平滑性良好，塗佈外觀、防受損性、表面電阻、空氣洩漏指數亦良好。 Mix polyester (A), (B), and (C) at mass ratios of 75%, 20%, and 5% respectively. The resulting mixed raw materials are used as the raw materials for the outermost layer (surface layer). Polyester (A) As the raw material for the middle layer, it is supplied to two extruders respectively. After being melted at 285°C, it is co-extruded into two types of three layers (surface layer/middle layer/surface layer = 1:14:1 discharge amount). The film was transferred to a cooling roller set at 35°C for cooling and solidification to obtain an unstretched sheet. Then, using the roller peripheral speed difference to stretch the film 3.2 times in the longitudinal direction at a film temperature of 85°C, the prepared coating liquid 5 shown in Table 1 below was applied to one side of the longitudinally stretched film and introduced into the tenter. After stretching 4.0 times in the transverse direction at 95°C and heat treatment at 230°C, the film was relaxed by 2% in the transverse direction to obtain a film for DFR substrates. The obtained DFR base material film has a coating layer with a film thickness of 0.04 μm after drying on one side of a polyester film with a thickness of 16 μm. The average surface roughness (Ra) of the coating layer surface is 4 nm. The maximum surface height (Rt) of the surface is 100 nm. The characteristics of this film are shown in Table 2 below. As shown in Table 2, the film haze and dynamic friction coefficient of the DFR substrate film of Example 1 are low, the transparency of the coating layer is maintained, and the smoothness is good, and the coating appearance, damage resistance, surface resistance, The air leakage index is also good.

實施例2、3： Examples 2 and 3:

將塗佈層之組成變更為表1所示之調配之塗佈液之組成，除此以外，以與實施例1相同之方式進行製造，獲得DFR基材用膜。如表2所示，實施例2、3之DFR基材用膜之膜霧度、動摩擦係數較低，維持塗佈層之透明性，並且平滑性良好，塗佈外觀、防受損性、表面電阻、空氣洩漏指數亦 良好。 Except for changing the composition of the coating layer to the composition of the prepared coating liquid shown in Table 1, the film was produced in the same manner as in Example 1 to obtain a film for a DFR base material. As shown in Table 2, the film haze and dynamic friction coefficient of the DFR substrate films of Examples 2 and 3 are low, the transparency of the coating layer is maintained, and the smoothness is good, and the coating appearance, damage resistance, surface Resistance and air leakage index are also good.

實施例4： Example 4:

將聚酯(A)、(B)分別以80%、20%之質量比率進行混合，將所得之混合原料作為最外層(表層)之原料，將聚酯(A)作為中間層之原料，分別供給至2台擠出機，分別於285℃下熔融後，以2種3層(表層/中間層/表層=1：14：1之噴出量)之層構成共擠出至設定為40℃之冷卻輥上進行冷卻固化，而獲得未延伸片材。繼而，利用輥周速差以膜溫度85℃於縱向上延伸3.2倍後，於該縱延伸膜之單面塗佈下述表1所示之調配之塗佈液5，導入拉幅機中，於橫向上以95℃延伸4.0倍，並於230℃下進行熱處理後，於橫向上鬆弛2%，獲得DFR基材用膜。所獲得之DFR基材用膜於厚度16μm之聚酯膜之單面具有乾燥後之膜厚為0.04μm之塗佈層，塗佈層表面之平均表面粗糙度(Ra)為2nm，塗佈層表面之最大表面高度(Rt)為70nm。將該膜之特性示於下述表3。如表3所示，實施例4之DFR基材用膜之膜霧度、動摩擦係數較低，維持塗佈層之透明性，並且平滑性良好，塗佈外觀、防受損性、表面電阻、空氣洩漏指數亦良好。 Mix polyester (A) and (B) at a mass ratio of 80% and 20% respectively. The resulting mixed raw material is used as the raw material for the outermost layer (surface layer), and polyester (A) is used as the raw material for the middle layer. Supplied to two extruders, each is melted at 285°C, and then co-extruded to a temperature of 40°C in the form of two layers of three layers (surface layer/middle layer/surface layer = 1:14:1 discharge volume). Cooling and solidification are performed on a cooling roll to obtain an unstretched sheet. Then, using the roller peripheral speed difference to stretch the film 3.2 times in the longitudinal direction at a film temperature of 85°C, the prepared coating liquid 5 shown in Table 1 below was applied to one side of the longitudinally stretched film and introduced into the tenter. After stretching 4.0 times in the transverse direction at 95°C and heat treatment at 230°C, the film was relaxed by 2% in the transverse direction to obtain a film for DFR substrates. The obtained DFR base material film has a coating layer with a film thickness of 0.04 μm after drying on one side of a polyester film with a thickness of 16 μm. The average surface roughness (Ra) of the coating layer surface is 2 nm. The maximum surface height (Rt) of the surface is 70 nm. The characteristics of this film are shown in Table 3 below. As shown in Table 3, the film haze and dynamic friction coefficient of the DFR substrate film of Example 4 are low, the transparency of the coating layer is maintained, and the smoothness is good, and the coating appearance, damage resistance, surface resistance, The air leakage index is also good.

實施例5~8： Embodiments 5~8:

將塗佈層之組成變更為表1所示之調配之塗佈液之組成，除此以外，以與實施例4相同之方式進行製造，獲得DFR基材用膜。如表3所示，實施例5~8之DFR基材用膜之膜霧度、動摩擦係數較低，維持塗佈層之透明性，並且平滑性良好，塗佈外觀、防受損性、表面電阻、空氣洩漏指數亦良好。 Except for changing the composition of the coating layer to the composition of the prepared coating liquid shown in Table 1, the film was produced in the same manner as in Example 4 to obtain a film for a DFR base material. As shown in Table 3, the film haze and dynamic friction coefficient of the DFR substrate films of Examples 5 to 8 are low, the transparency of the coating layer is maintained, and the smoothness is good, and the coating appearance, damage resistance, surface The resistance and air leakage index are also good.

比較例1： Comparative example 1:

不設置塗佈層，除此以外，以與實施例1相同之方式進行製造，獲得膜。對所獲得之膜進行評價，結果由於不具有塗佈層，故而如表2所示，為動摩擦係數或防受損性較差之膜。 Except that the coating layer was not provided, the film was produced in the same manner as in Example 1 to obtain a film. The obtained film was evaluated. As a result, since it did not have a coating layer, as shown in Table 2, it was a film with poor dynamic friction coefficient or damage resistance.

比較例2~4： Comparative examples 2~4:

將塗佈層之塗佈劑組成變更為表1所示之調配之塗佈液之組成，除此以外，以與實施例1相同之方式進行製造，獲得膜。對所獲得之膜進行評價，結果如表2所示，由於塗佈液17及18中不含交聯劑，故而比較例2及3之膜係雖塗佈外觀良好，但即便為具有塗佈層之膜，防受損性亦較差之膜。又，比較例4之膜由於塗佈液19中所含有之抗靜電劑超過45質量%，為64質量%而較多，故而表面電阻值未達1×1010Ω，會產生滲出導致塗佈外觀及膜霧度較差，由於塗佈液19中不含交聯劑，故而為防受損性較差之膜。 Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 1, the film was produced in the same manner as in Example 1 to obtain a film. The obtained films were evaluated, and the results are shown in Table 2. Since the coating liquids 17 and 18 did not contain a cross-linking agent, the films of Comparative Examples 2 and 3 had good coating appearance. It is a layer of film with poor damage resistance. In addition, in the film of Comparative Example 4, the antistatic agent contained in the coating liquid 19 was more than 45 mass %, which was 64 mass %, so the surface resistance value was less than 1×10 10 Ω, and bleeding occurred and the coating was The appearance and film haze are poor. Since the coating liquid 19 does not contain a cross-linking agent, it is a film with poor damage resistance.

比較例5： Comparative example 5:

將塗佈層之塗佈劑組成變更為表1所示之調配之塗佈液之組成，除此以外，以與實施例1相同之方式進行製造，獲得膜。對所獲得之膜進行評價，結果如表2所示，為如下膜：雖然塗佈液23中含有交聯劑，但由於包含粒徑超過1μm之粒子，故而存在產生磨削之情形，由於粒子AL之面積比率超過15%，故而防受損性較差。 Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 1, the film was produced in the same manner as in Example 1 to obtain a film. The obtained film was evaluated, and the results are shown in Table 2. Although the coating liquid 23 contains a cross-linking agent, it contains particles with a particle diameter exceeding 1 μm, so grinding may occur. Since the particles The area ratio of AL exceeds 15%, so the damage resistance is poor.

比較例6~8： Comparative examples 6~8:

將塗佈層之塗佈劑組成變更為表1所示之調配之塗佈液之組成，除此以外，以與實施例1相同之方式進行製造，獲得膜。對所獲得之膜進行評價，結果如表2所示，比較例6、8之膜雖然塗佈液4及16中含有交聯劑，但由於粒子AL之面積比率為0%，故而為塗佈外觀及防受損性較差之膜。比較例7之膜雖塗佈液6中含有交聯劑，但由於粒子AS之面積為0.3%，粒子AL之面積為98.3%，故而為塗佈外觀及防受損性較差之膜。 Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 1, the film was produced in the same manner as in Example 1 to obtain a film. The obtained films were evaluated, and the results are shown in Table 2. Although the films of Comparative Examples 6 and 8 contained a cross-linking agent in the coating liquids 4 and 16, the area ratio of the particles AL was 0%, so they were not coated. A film with poor appearance and damage resistance. Although the coating liquid 6 of the film of Comparative Example 7 contains a cross-linking agent, the area of particles AS is 0.3% and the area of particles AL is 98.3%, so it is a film with poor coating appearance and damage resistance.

比較例9： Comparative example 9:

不設置塗佈層，除此以外，以與實施例4相同之方式進行製造，獲得膜。對所獲得之膜進行評價，結果由於不具有塗佈層，故而如表3所示，為動摩擦係數及防受損性較差而產生橫寬較大之表層皺褶之膜。 Except that the coating layer was not provided, the film was produced in the same manner as in Example 4 to obtain a film. The obtained film was evaluated. As a result, since it did not have a coating layer, as shown in Table 3, it was a film with poor dynamic friction coefficient and damage resistance, and thus had surface wrinkles with a large horizontal width.

比較例10~11： Comparative Examples 10~11:

將塗佈層之塗佈劑組成變更為表1所示之調配之塗佈液之組成，除此以外，以與實施例4相同之方式進行製造，獲得膜。對所獲得之膜進行評價，結果如表3所示，為如下膜：由於塗佈液17及18中不含交聯劑，故而雖塗佈外觀良好，但即便為具有塗佈層之膜，防受損性亦較差。 Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 1, the film was produced in the same manner as in Example 4 to obtain a film. The obtained film was evaluated, and the results are shown in Table 3. The coating liquids 17 and 18 did not contain a cross-linking agent, so although the coating appearance was good, even if it was a film with a coating layer, Damage resistance is also poor.

比較例12： Comparative example 12:

將塗佈層之塗佈劑組成變更為表1所示之調配之塗佈液之組成，除此以外，以與實施例4相同之方式進行製造，獲得膜。對所獲得之膜進行評價，結果如表3所示，為如下膜：雖然塗佈液22中含有交聯劑，但由於粒 子AL之面積比率超過15%，故而防受損性亦較差。 Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 1, the film was produced in the same manner as in Example 4 to obtain a film. The obtained film was evaluated, and the results are shown in Table 3. Although the coating liquid 22 contains a cross-linking agent, the coating liquid 22 contains a cross-linking agent. The area ratio of sub-AL exceeds 15%, so the damage resistance is also poor.

比較例13~18： Comparative examples 13~18:

將塗佈層之塗佈劑組成變更為表1所示之調配之塗佈液之組成，除此以外，以與實施例4相同之方式進行製造，獲得膜。對所獲得之膜進行評價，結果如表3所示，比較例13~17之膜係雖然塗佈液1~4中含有交聯劑，但由於粒子AL之面積比率為0%，故而亦產生橫寬較大之表層皺褶之膜或塗佈外觀及防受損性亦較差之膜。比較例18之膜係雖然塗佈液6中含有交聯劑，但由於粒子AS之面積為0.3%，粒子AL之面積為98.3%，故而塗佈外觀及防受損性亦較差之膜。 Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 1, the film was produced in the same manner as in Example 4 to obtain a film. The obtained films were evaluated, and the results are shown in Table 3. Although the coating liquids 1 to 4 of the film systems of Comparative Examples 13 to 17 contained a cross-linking agent, since the area ratio of the particles AL was 0%, it also produced Films with large surface wrinkles or films with poor coating appearance and damage resistance. Although the coating liquid 6 of Comparative Example 18 contains a cross-linking agent, the coating appearance and damage resistance are poor because the area of particles AS is 0.3% and the area of particles AL is 98.3%.

Figure 108105213-A0305-02-0064-2
Figure 108105213-A0305-02-0064-2

Figure 108105213-A0305-02-0065-3
Figure 108105213-A0305-02-0065-3

Figure 108105213-A0305-02-0065-4
Figure 108105213-A0305-02-0065-4

實施例31： Example 31:

將聚酯(A)、(B)、(C)分別以75%、20%、5%之質量比率進行混合，將所得之混合原料作為最外層(表層)之原料，將聚酯(A)作為中間層之原料，分別供給至2台擠出機，分別於285℃下熔融後，以2種3層(表層/中間層/表層=1：14：1之噴出量)之層構成共擠出至設定為35℃之冷卻輥上進 行冷卻固化，而獲得未延伸片材。繼而，利用輥周速差以膜溫度85℃於縱向上延伸3.2倍後，於該縱延伸膜之單面塗佈下述表4所示之調配之塗佈液38，導入拉幅機中，於橫向上以95℃延伸4.0倍，並於230℃下進行熱處理後，於橫向上鬆弛2%，獲得DFR基材用膜。所獲得之DFR基材用膜於厚度16μm之聚酯膜之單面具有乾燥後之膜厚為0.04μm之塗佈層，塗佈層表面之平均表面粗糙度(Ra)為4nm，塗佈層表面之最大表面高度(Rt)為170nm。將該膜之特性示於下述表5。如表5所示，實施例31之DFR基材用膜於整個面均未出現塗佈層之不均及塗佈液之收縮，膜霧度、動摩擦係數較低，維持塗佈層之透明性，並且平滑性良好，塗佈外觀、防受損性、表面電阻、空氣洩漏指數亦良好。 Mix polyester (A), (B), and (C) at mass ratios of 75%, 20%, and 5% respectively. The resulting mixed raw materials are used as the raw materials for the outermost layer (surface layer). Polyester (A) As the raw material for the middle layer, it is supplied to two extruders respectively. After being melted at 285°C, it is co-extruded into two types of three layers (surface layer/middle layer/surface layer = 1:14:1 discharge amount). Exit to the cooling roller set at 35℃ and enter It is cooled and solidified to obtain an unstretched sheet. Then, using the roller peripheral speed difference to stretch the film 3.2 times in the longitudinal direction at a film temperature of 85°C, the prepared coating liquid 38 shown in Table 4 below was applied to one side of the longitudinally stretched film and introduced into the tenter. After stretching 4.0 times in the transverse direction at 95°C and heat treatment at 230°C, the film was relaxed by 2% in the transverse direction to obtain a film for DFR substrates. The obtained DFR base material film has a coating layer with a film thickness of 0.04 μm after drying on one side of a polyester film with a thickness of 16 μm. The average surface roughness (Ra) of the coating layer surface is 4 nm. The maximum surface height (Rt) of the surface is 170 nm. The characteristics of this film are shown in Table 5 below. As shown in Table 5, the DFR substrate film of Example 31 did not have uneven coating layer or shrinkage of the coating liquid on the entire surface. The film haze and dynamic friction coefficient were low, and the transparency of the coating layer was maintained. , and has good smoothness, coating appearance, damage resistance, surface resistance, and air leakage index.

實施例32、33： Examples 32 and 33:

將塗佈層之組成變更為表4所示之調配之塗佈液之組成，除此以外，以與實施例31相同之方式進行製造，獲得DFR基材用膜。如表5所示，實施例32、33之DFR基材用膜於整個面均未出現塗佈層之不均及塗佈液之收縮，膜霧度、動摩擦係數較低，維持塗佈層之透明性，並且平滑性良好，塗佈外觀、防受損性、表面電阻、空氣洩漏指數亦良好。 Except for changing the composition of the coating layer to the composition of the prepared coating liquid shown in Table 4, the film was produced in the same manner as in Example 31 to obtain a film for a DFR base material. As shown in Table 5, in the DFR substrate films of Examples 32 and 33, there was no uneven coating layer or shrinkage of the coating liquid on the entire surface. The film haze and dynamic friction coefficient were low, and the coating layer was maintained. It has good transparency and smoothness, as well as good coating appearance, damage resistance, surface resistance, and air leakage index.

實施例34： Example 34:

將聚酯(A)、(B)分別以80%、20%之質量比率進行混合，將所得之混合原料作為最外層(表層)之原料，將聚酯(A)作為中間層之原料，分別供給至2台擠出機，分別於285℃下熔融後，以2種3層(表層/中間層/表層=1：14：1之噴出量)之層構成共擠出至設定為40℃之冷卻輥上進行冷卻固 化，而獲得未延伸片材。繼而，利用輥周速差以膜溫度85℃於縱向上延伸3.2倍後，於該縱延伸膜之單面塗佈下述表4所示之調配之塗佈液40，導入拉幅機中，於橫向上以95℃延伸4.0倍，並於230℃下進行熱處理後，於橫向上鬆弛2%，獲得DFR基材用膜。所獲得之DFR基材用膜係於厚度16μm之聚酯膜之單面具有乾燥後之膜厚為0.04μm之塗佈層，且塗佈層表面之平均表面粗糙度(Ra)為2nm、塗佈層表面之最大表面高度(Rt)為40nm之DFR基材用膜。將該膜之特性示於下述表6。如表6所示，實施例34之DFR基材用膜於整個面均未出現塗佈層之不均及塗佈液之收縮，膜霧度、動摩擦係數較低，維持塗佈層之透明性，並且平滑性良好，塗佈外觀、防受損性、表面電阻、空氣洩漏指數亦良好。 Mix polyester (A) and (B) at a mass ratio of 80% and 20% respectively. The resulting mixed raw material is used as the raw material for the outermost layer (surface layer), and polyester (A) is used as the raw material for the middle layer. Supplied to two extruders, each is melted at 285°C, and then co-extruded to a temperature of 40°C in the form of two layers of three layers (surface layer/middle layer/surface layer = 1:14:1 discharge volume). Cooling and solidification on cooling roller to obtain an unstretched sheet. Then, using the roller peripheral speed difference to stretch the film 3.2 times in the longitudinal direction at a film temperature of 85°C, the prepared coating liquid 40 shown in Table 4 below was applied to one side of the longitudinally stretched film and introduced into the tenter. After stretching 4.0 times in the transverse direction at 95°C and heat treatment at 230°C, the film was relaxed by 2% in the transverse direction to obtain a film for DFR substrates. The obtained DFR substrate film has a coating layer with a film thickness of 0.04 μm after drying on one side of a polyester film with a thickness of 16 μm, and the average surface roughness (Ra) of the coating layer surface is 2 nm. The maximum surface height (Rt) of the cloth layer surface is 40nm for DFR substrate film. The characteristics of this film are shown in Table 6 below. As shown in Table 6, the DFR substrate film of Example 34 did not have uneven coating layer or shrinkage of the coating liquid on the entire surface. The film haze and dynamic friction coefficient were low, and the transparency of the coating layer was maintained. , and has good smoothness, coating appearance, damage resistance, surface resistance, and air leakage index.

實施例35、36： Examples 35 and 36:

將塗佈層之組成變更為表4所示之調配之塗佈液之組成，除此以外，以與實施例34相同之方式進行製造，獲得DFR基材用膜。如表6所示，實施例35、36之DFR基材用膜於整個面均未出現塗佈層之不均及塗佈液之收縮，膜霧度、動摩擦係數較低，維持塗佈層之透明性，並且平滑性良好，塗佈外觀、防受損性、表面電阻、空氣洩漏指數亦良好。 Except for changing the composition of the coating layer to the composition of the prepared coating liquid shown in Table 4, the film was produced in the same manner as in Example 34 to obtain a film for a DFR base material. As shown in Table 6, in the DFR substrate films of Examples 35 and 36, there was no uneven coating layer or shrinkage of the coating liquid on the entire surface. The film haze and dynamic friction coefficient were low, and the coating layer was maintained. It has good transparency and smoothness, as well as good coating appearance, damage resistance, surface resistance, and air leakage index.

比較例31： Comparative example 31:

不設置塗佈層，除此以外，以與實施例31相同之方式進行製造，獲得膜。對所獲得之膜進行評價，結果由於不具有塗佈層，故而如表5所示，為動摩擦係數及防受損性較差之膜。 Except that the coating layer was not provided, the film was produced in the same manner as in Example 31 to obtain a film. The obtained film was evaluated. As a result, since it did not have a coating layer, as shown in Table 5, it was a film with poor dynamic friction coefficient and damage resistance.

比較例32、33： Comparative Examples 32 and 33:

將塗佈層之塗佈劑組成變更為表4所示之調配之塗佈液之組成，除此以外，以與實施例31相同之方式進行製造，獲得膜。對所獲得之膜進行評價，結果如表5所示，比較例32之膜由於塗佈液44中不含交聯劑及各種聚合物，故而即便於不含界面活性劑之情形時，亦不會出現塗佈層之不均及塗佈液之收縮。然而，由於塗佈液44中不含交聯劑，故而為防受損性較差之膜。又，如表5所示，比較例33之膜含有交聯劑及各種聚合物，雖未出現塗佈層之不均，但由於塗佈液45中不含界面活性劑，故而於整個面出現塗佈液之收縮。 Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 4, the film was produced in the same manner as in Example 31 to obtain a film. The obtained film was evaluated, and the results are shown in Table 5. Since the coating liquid 44 of the film of Comparative Example 32 does not contain a cross-linking agent and various polymers, even if it does not contain a surfactant, it is not There will be uneven coating layer and shrinkage of the coating liquid. However, since the coating liquid 44 does not contain a cross-linking agent, it is a film with poor damage resistance. Furthermore, as shown in Table 5, the film of Comparative Example 33 contains a cross-linking agent and various polymers. Although unevenness in the coating layer does not occur, since the coating liquid 45 does not contain a surfactant, unevenness appears on the entire surface. Shrinkage of coating fluid.

比較例34： Comparative example 34:

將塗佈層之塗佈劑組成變更為表4所示之調配之塗佈液之組成，除此以外，以與實施例31相同之方式進行製造，獲得膜。對所獲得之膜進行評價，結果如表5所示，為如下膜：雖然塗佈液49中含有界面活性劑，但由於包含粒徑超過1μm之粒子，故而存在產生磨削之情形，由於粒子AL之面積比率超過15%，故而防受損性較差。 Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 4, the film was produced in the same manner as in Example 31 to obtain a film. The obtained film was evaluated, and the results are shown in Table 5. The coating liquid 49 contains a surfactant, but contains particles with a particle diameter exceeding 1 μm, so grinding may occur. Since the particles The area ratio of AL exceeds 15%, so the damage resistance is poor.

比較例35~37： Comparative examples 35~37:

將塗佈層之塗佈劑組成變更為表4所示之調配之塗佈液之組成，除此以外，以與實施例31相同之方式進行製造，獲得膜。對所獲得之膜進行評價，結果如表5所示，比較例35或37之膜係雖然塗佈液36或43中含有界面活性劑，但由於粒子AL之面積比率為0%，故而存在出現塗佈層之不均之情形，從而防受損性較差之膜。比較例36之膜係雖然塗佈液39中含有交 聯劑，但由於粒子AS之面積為0.3%，粒子AL之面積為98.3%，故而塗佈外觀及防受損性亦較差之膜。 Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 4, the film was produced in the same manner as in Example 31 to obtain a film. The obtained film was evaluated, and the results are shown in Table 5. Although the coating liquid 36 or 43 of the film system of Comparative Example 35 or 37 contained a surfactant, the area ratio of the particles AL was 0%, so there was a problem. The unevenness of the coating layer results in a film with poor protection against damage. Although the coating liquid 39 of the film system of Comparative Example 36 contains crosslinking Joint agent, but since the area of particles AS is 0.3% and the area of particles AL is 98.3%, the coating appearance and damage resistance are also poor.

比較例38： Comparative example 38:

不設置塗佈層，除此以外，以與實施例34相同之方式進行製造，獲得膜。對所獲得之膜進行評價，結果由於不具有塗佈層，故而如表6所示，為動摩擦係數及防受損性較差而產生橫寬較大之表層皺褶之膜。 Except that the coating layer was not provided, the film was produced in the same manner as in Example 34 to obtain a film. The obtained film was evaluated, and as a result, since it did not have a coating layer, as shown in Table 6, it was a film with poor dynamic friction coefficient and damage resistance, resulting in surface wrinkles with a large horizontal width.

比較例39、40： Comparative Examples 39 and 40:

將塗佈層之塗佈劑組成變更為表4所示之調配之塗佈液之組成，除此以外，以與實施例34相同之方式進行製造，獲得膜。對所獲得之膜進行評價，結果如表6所示，比較例39之膜由於塗佈液44中不含交聯劑及各種聚合物，故而即便於不含界面活性劑之情形時，亦不會出現塗佈層之不均及塗佈液之收縮。然而，由於塗佈液44中不含交聯劑，故而為防受損性較差之膜。又，如表6所示，比較例40之膜於塗佈液45中含有交聯劑及各種聚合物，雖未出現塗佈層之不均，但由於塗佈液45中不含界面活性劑，故而於整個面出現塗佈液之收縮。 Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 4, the film was produced in the same manner as in Example 34 to obtain a film. The obtained film was evaluated, and the results are shown in Table 6. The film of Comparative Example 39 did not contain a cross-linking agent and various polymers in the coating liquid 44, so even when it did not contain a surfactant, it was not There will be uneven coating layer and shrinkage of the coating liquid. However, since the coating liquid 44 does not contain a cross-linking agent, it is a film with poor damage resistance. In addition, as shown in Table 6, the film of Comparative Example 40 contains a cross-linking agent and various polymers in the coating liquid 45. Although unevenness of the coating layer does not occur, the coating liquid 45 does not contain surfactants. , so the coating liquid shrinks on the entire surface.

比較例41： Comparative example 41:

將塗佈層之塗佈劑組成變更為表4所示之調配之塗佈液之組成，除此以外，以與實施例34相同之方式進行製造，獲得膜。對所獲得之膜進行評價，結果如表6所示，為如下膜：雖然塗佈液48中含有界面活性劑及交聯劑，但由於粒子AL之面積比率超過15%，故而防受損性亦較差。 Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 4, the film was produced in the same manner as in Example 34 to obtain a film. The obtained film was evaluated, and the results are shown in Table 6. Although the coating liquid 48 contained a surfactant and a cross-linking agent, the area ratio of the particles AL exceeded 15%, so the damage prevention property was poor. Also worse.

比較例42~48： Comparative examples 42~48:

將塗佈層之塗佈劑組成變更為表4所示之調配之塗佈液之組成，除此以外，以與實施例34相同之方式進行製造，獲得膜。對所獲得之膜進行評價，結果如表6所示，比較例42~47之膜係雖然塗佈液31~35中含有界面活性劑，但由於粒子AL之面積比率為0%，故而平滑性亦較差而產生橫寬較大之表層皺褶之膜。比較例48之膜係雖然塗佈液39中含有界面活性劑及交聯劑，但由於粒子AS之面積為0.3%，粒子AL之面積為98.3%，故而塗佈層出現不均而防受損性較差之膜。 Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 4, the film was produced in the same manner as in Example 34 to obtain a film. The obtained films were evaluated, and the results are shown in Table 6. Although the coating liquids 31 to 35 of the film systems of Comparative Examples 42 to 47 contained surfactants, the area ratio of the particles AL was 0%, so the smoothness was poor. It is also poorer and produces a film with larger horizontal width of the surface wrinkles. Although the coating liquid 39 of the film system of Comparative Example 48 contains a surfactant and a cross-linking agent, the area of the particles AS is 0.3% and the area of the particles AL is 98.3%, so the coating layer is uneven and damaged. Poor membrane.

Figure 108105213-A0305-02-0070-5
Figure 108105213-A0305-02-0070-5

Figure 108105213-A0305-02-0071-7
Figure 108105213-A0305-02-0071-7

實施例61： Example 61:

將聚酯(A)、(B)、(C)分別以75%、20%、5%之質量比率進行混合，將所得之混合原料作為最外層(表層)之原料，將聚酯(A)作為中間層之原料，分別供給至2台擠出機，分別於285℃下熔融後，以2種3層(表層/中間層/表層=1：14：1之噴出量)之層構成共擠出至設定為35℃之冷卻輥上進行冷卻固化，而獲得未延伸片材。繼而，利用輥周速差以膜溫度85℃於縱 向上延伸3.2倍後，於該縱延伸膜之單面塗佈下述表7所示之調配之塗佈液65，導入拉幅機中，於橫向上以95℃延伸4.0倍，並於230℃下進行熱處理後，於橫向上鬆弛2%，獲得DFR基材用膜。所獲得之DFR基材用膜於厚度16μm之聚酯膜之單面具有乾燥後之膜厚為0.04μm之塗佈層，塗佈層表面之平均表面粗糙度(Ra)為4nm，塗佈層表面之最大表面高度(Rt)為100nm。將該膜之特性示於下述表8。如表8所示，實施例61之DFR基材用膜之膜霧度、動摩擦係數較低，維持塗佈層之透明性，並且平滑性良好，塗佈外觀、防受損性、表面電阻、空氣洩漏指數亦良好。 Mix polyester (A), (B), and (C) at mass ratios of 75%, 20%, and 5% respectively. The resulting mixed raw materials are used as the raw materials for the outermost layer (surface layer). Polyester (A) As the raw material for the middle layer, it is supplied to two extruders respectively. After being melted at 285°C, it is co-extruded into two types of three layers (surface layer/middle layer/surface layer = 1:14:1 discharge amount). The film was transferred to a cooling roller set at 35°C for cooling and solidification to obtain an unstretched sheet. Then, using the roller peripheral speed difference, the film temperature is 85°C in the longitudinal direction. After extending upward 3.2 times, apply the prepared coating liquid 65 shown in Table 7 below on one side of the longitudinally stretched film, introduce it into the tenter, extend it 4.0 times in the transverse direction at 95°C, and heat it at 230°C. After heat treatment, the film was relaxed by 2% in the transverse direction to obtain a film for DFR substrates. The obtained DFR base material film has a coating layer with a film thickness of 0.04 μm after drying on one side of a polyester film with a thickness of 16 μm. The average surface roughness (Ra) of the coating layer surface is 4 nm. The maximum surface height (Rt) of the surface is 100 nm. The characteristics of this film are shown in Table 8 below. As shown in Table 8, the film haze and dynamic friction coefficient of the DFR substrate film of Example 61 are low, the transparency of the coating layer is maintained, and the smoothness is good, and the coating appearance, damage resistance, surface resistance, The air leakage index is also good.

實施例62、63： Examples 62 and 63:

將塗佈層之組成變更為表7所示之調配之塗佈液之組成，除此以外，以與實施例61相同之方式進行製造，獲得DFR基材用膜。如表8所示，實施例62、63之DFR基材用膜之膜霧度、動摩擦係數較低，維持塗佈層之透明性，並且平滑性良好，塗佈外觀、防受損性、表面電阻、空氣洩漏指數亦良好。 Except that the composition of the coating layer was changed to the composition of the prepared coating liquid shown in Table 7, the film was produced in the same manner as in Example 61 to obtain a film for a DFR base material. As shown in Table 8, the film haze and dynamic friction coefficient of the DFR substrate films of Examples 62 and 63 are low, the transparency of the coating layer is maintained, and the smoothness is good, and the coating appearance, damage resistance, surface The resistance and air leakage index are also good.

實施例64： Example 64:

將聚酯(A)、(B)分別以80%、20%之質量比率進行混合，將所得之混合原料作為最外層(表層)之原料，將聚酯(A)作為中間層之原料，分別供給至2台擠出機，分別於285℃下熔融後，以2種3層(表層/中間層/表層=1：14：1之噴出量)之層構成共擠出至設定為40℃之冷卻輥上進行冷卻固化，而獲得未延伸片材。繼而，利用輥周速差以膜溫度85℃於縱向上延伸3.2倍後，於該縱延伸膜之單面塗佈下述表7所示之調配之塗佈液65，導入 拉幅機中，於橫向上以95℃延伸4.0倍，並於230℃下進行熱處理後，於橫向上鬆弛2%，獲得DFR基材用膜。所獲得之DFR基材用膜於厚度16μm之聚酯膜之單面具有乾燥後之膜厚為0.04μm之塗佈層，塗佈層表面之平均表面粗糙度(Ra)為2nm，塗佈層表面之最大表面高度(Rt)為70nm。將該膜之特性示於下述表9。如表9所示，實施例64之DFR基材用膜之膜霧度、動摩擦係數較低，維持塗佈層之透明性，並且平滑性良好，塗佈外觀、防受損性、表面電阻、空氣洩漏指數亦良好。 Mix polyester (A) and (B) at a mass ratio of 80% and 20% respectively. The resulting mixed raw material is used as the raw material for the outermost layer (surface layer), and polyester (A) is used as the raw material for the middle layer. Supplied to two extruders, each is melted at 285°C, and then co-extruded to a temperature of 40°C in the form of two layers of three layers (surface layer/middle layer/surface layer = 1:14:1 discharge volume). Cooling and solidification are performed on a cooling roll to obtain an unstretched sheet. Then, after utilizing the roller peripheral speed difference to stretch the film 3.2 times in the longitudinal direction at a film temperature of 85°C, the prepared coating liquid 65 shown in Table 7 below was applied to one side of the longitudinally stretched film and introduced. In the tenter, the film was stretched 4.0 times in the transverse direction at 95°C, and after heat treatment at 230°C, it was relaxed by 2% in the transverse direction to obtain a film for DFR substrates. The obtained DFR base material film has a coating layer with a film thickness of 0.04 μm after drying on one side of a polyester film with a thickness of 16 μm. The average surface roughness (Ra) of the coating layer surface is 2 nm. The maximum surface height (Rt) of the surface is 70 nm. The characteristics of this film are shown in Table 9 below. As shown in Table 9, the film haze and dynamic friction coefficient of the DFR substrate film of Example 64 are low, the transparency of the coating layer is maintained, and the smoothness is good, and the coating appearance, damage resistance, surface resistance, The air leakage index is also good.

實施例65~68： Embodiments 65~68:

將塗佈層之組成變更為表7所示之調配之塗佈液之組成，除此以外，以與實施例64相同之方式進行製造，獲得DFR基材用膜。如表9所示，實施例65~68之DFR基材用膜之膜霧度、動摩擦係數較低，維持塗佈層之透明性，並且平滑性良好，塗佈外觀、防受損性、表面電阻、空氣洩漏指數亦良好。 Except for changing the composition of the coating layer to the composition of the prepared coating liquid shown in Table 7, the film was produced in the same manner as in Example 64 to obtain a film for a DFR base material. As shown in Table 9, the film haze and dynamic friction coefficient of the DFR substrate films of Examples 65 to 68 are low, the transparency of the coating layer is maintained, and the smoothness is good, and the coating appearance, damage resistance, surface The resistance and air leakage index are also good.

比較例61： Comparative example 61:

不設置塗佈層，除此以外，以與實施例61相同之方式進行製造，獲得膜。對所獲得之膜進行評價，結果由於不具有塗佈層，故而如表8所示，為動摩擦係數及防受損性較差之膜。 Except that the coating layer was not provided, the film was produced in the same manner as in Example 61 to obtain a film. The obtained film was evaluated. As a result, since it did not have a coating layer, as shown in Table 8, it was a film with poor dynamic friction coefficient and damage resistance.

比較例62、63： Comparative Examples 62 and 63:

將塗佈層之塗佈劑組成變更為表7所示之調配之塗佈液之組成，除此以外，以與實施例61相同之方式進行製造，獲得膜。對所獲得之膜進行評 價，結果如表8所示，由於塗佈液74中不含交聯劑，故而比較例62之膜塗佈外觀良好，但即便為具有塗佈層之膜，亦為防受損性較差之膜。又，比較例63之膜係由於塗佈液75中含有無機鹽，故而於製造膜之過程中鹽於膜表面析出而塗佈外觀及膜霧度較差、防受損性較差之膜。 Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 7, the film was produced in the same manner as in Example 61 to obtain a film. Evaluate the obtained film The results are shown in Table 8. Since the coating liquid 74 does not contain a cross-linking agent, the film of Comparative Example 62 has a good coating appearance. However, even if it is a film with a coating layer, it has poor damage resistance. membrane. In addition, the film of Comparative Example 63 contains inorganic salts in the coating liquid 75. Therefore, the salt precipitated on the film surface during the film manufacturing process, resulting in a film with poor coating appearance, film haze, and poor damage resistance.

比較例64： Comparative example 64:

將塗佈層之塗佈劑組成變更為表7所示之調配之塗佈液之組成，除此以外，以與實施例61相同之方式進行製造，獲得膜。對所獲得之膜進行評價，結果如表8所示，係雖然塗佈液79中含有交聯劑，但由於包含粒徑超過1μm之粒子，故而存在產生磨削之情形，由於粒子AL之面積比率超過15%，故而防受損性較差之膜。 Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 7, the film was produced in the same manner as in Example 61 to obtain a film. The obtained film was evaluated, and the results are shown in Table 8. Although the coating liquid 79 contains a cross-linking agent, it contains particles with a particle diameter exceeding 1 μm, so grinding may occur. Due to the area of the particles AL The ratio exceeds 15%, so the film has poor damage resistance.

比較例65、66： Comparative Examples 65 and 66:

將塗佈層之塗佈劑組成變更為表7所示之調配之塗佈液之組成，除此以外，以與實施例61相同之方式進行製造，獲得膜。對所獲得之膜進行評價，結果如表8所示，比較例65之膜係雖然塗佈液64中含有交聯劑，但由於粒子AL之面積比率為0%，故而塗佈外觀及防受損性亦較差之膜。比較例66之膜係雖然塗佈液66中含有交聯劑，但由於粒子AS之面積為0.3%，粒子AL之面積為98.3%，故而塗佈外觀及防受損性亦較差之膜。 Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 7, the film was produced in the same manner as in Example 61 to obtain a film. The obtained film was evaluated, and the results are shown in Table 8. Although the coating liquid 64 of the film system of Comparative Example 65 contained a cross-linking agent, the area ratio of the particles AL was 0%, so the coating appearance and protection were poor. It is also a membrane with poor damage properties. The film system of Comparative Example 66 contains a cross-linking agent in the coating liquid 66, but since the area of the particles AS is 0.3% and the area of the particles AL is 98.3%, the coating appearance and damage resistance are also poor.

比較例67： Comparative example 67:

不設置塗佈層，除此以外，以與實施例64相同之方式進行製造，獲得膜。對所獲得之膜進行評價，結果由於不具有塗佈層，故而如表9所 示，為動摩擦係數及防受損性較差之膜。 Except that the coating layer was not provided, the film was produced in the same manner as in Example 64 to obtain a film. The obtained film was evaluated and the results were as shown in Table 9 since it did not have a coating layer. shows that it is a film with poor dynamic friction coefficient and damage resistance.

比較例68、69： Comparative Examples 68 and 69:

將塗佈層之塗佈劑組成變更為表7所示之調配之塗佈液之組成，除此以外，以與實施例64相同之方式進行製造，獲得膜。對所獲得之膜進行評價，結果如表9所示，比較例68之膜由於塗佈液74中不含交聯劑，故而比較例68之膜係雖然塗佈外觀良好，但由於不含交聯劑，故而防受損性亦較差之膜。比較例69之膜係由於塗佈液75含有無機鹽，故而於製造膜之過程中鹽於膜表面析出，而塗佈外觀及膜霧度較差、防受損性較差之膜。 Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 7, the film was produced in the same manner as in Example 64 to obtain a film. The obtained film was evaluated, and the results are shown in Table 9. The film of Comparative Example 68 does not contain a cross-linking agent in the coating liquid 74. Therefore, although the film system of Comparative Example 68 has a good coating appearance, it does not contain a cross-linking agent. It is a membrane with poor protection against damage due to the combined agent. Since the coating liquid 75 of Comparative Example 69 contains inorganic salts, the salt precipitates on the film surface during the film manufacturing process, resulting in a film with poor coating appearance, film haze, and poor damage resistance.

比較例70： Comparative example 70:

將塗佈層之塗佈劑組成變更為表7所示之調配之塗佈液之組成，除此以外，以與實施例64相同之方式進行製造，獲得膜。對所獲得之膜進行評價，結果如表9所示，係雖然塗佈液78中含有交聯劑，但由於粒子AL之面積比率超過15%，故而防受損性亦較差之膜。 Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 7, the film was produced in the same manner as in Example 64 to obtain a film. The obtained film was evaluated. As shown in Table 9, the results showed that although the coating liquid 78 contained a cross-linking agent, the area ratio of the particles AL exceeded 15%, so the film had poor damage prevention properties.

比較例71~76： Comparative examples 71~76:

將塗佈層之塗佈劑組成變更為表7所示之調配之塗佈液之組成，除此以外，以與實施例64相同之方式進行製造，獲得膜。對所獲得之膜進行評價，結果如表9所示，比較例71~75之膜係雖然塗佈液61~64中含有交聯劑，但由於粒子AL之面積比率為0%，故而塗佈外觀及防受損性亦較差或亦產生橫寬較大之表層皺褶之膜。比較例76之膜係雖然塗佈液66中含有交聯劑，但由於粒子AS之面積為0.3%，粒子AL之面積為98.3%，故而塗 佈外觀及防受損性亦較差之膜。 Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 7, the film was produced in the same manner as in Example 64 to obtain a film. The obtained films were evaluated, and the results are shown in Table 9. Although the coating liquids 61 to 64 of the film systems of Comparative Examples 71 to 75 contained a cross-linking agent, the area ratio of the particles AL was 0%, so the coating was The appearance and damage resistance of the film are also poor or the surface wrinkles with large horizontal width are produced. Although the coating liquid 66 of the film system of Comparative Example 76 contains a cross-linking agent, the area of particles AS is 0.3% and the area of particles AL is 98.3%, so the coating It is a film with poor cloth appearance and damage resistance.

Figure 108105213-A0305-02-0076-10
Figure 108105213-A0305-02-0076-10

Figure 108105213-A0305-02-0076-11
Figure 108105213-A0305-02-0076-11

Figure 108105213-A0305-02-0077-13
Figure 108105213-A0305-02-0077-13

實施例81： Example 81:

將聚酯(A)、(B)、(C)分別以75%、20%、5%之質量比率進行混合，將所得之混合原料作為最外層(表層)之原料，將聚酯(A)作為中間層之原料，分別供給至2台擠出機，分別於285℃下熔融後，以2種3層(表層/中間層/表層=1：14：1之噴出量)之層構成共擠出至設定為35℃之冷卻輥上進行冷卻固化，而獲得未延伸片材。繼而，利用輥周速差以膜溫度85℃於縱向上延伸3.2倍後，於該縱延伸膜之單面塗佈下述表10所示之調配之塗佈液85，導入拉幅機中，於橫向上以95℃延伸4.0倍，並於230℃下進行熱處理後，於橫向上鬆弛2%，獲得DFR基材用膜。所獲得之DFR基材用膜於厚度16μm之聚酯膜之單面具有乾燥後之膜厚為0.04μm之塗佈層，塗佈層表面之平均表面粗糙度(Ra)為4nm，塗佈層表面之最大表面高度(Rt)為100nm。將該膜之特性示於下述表11。如表11所示，實施例81之DFR基材用膜之膜霧度、動摩擦係數較低，維持塗佈層之透明性，並且平滑性良 好，塗佈外觀、防受損性、表面電阻、空氣洩漏指數亦良好。 Mix polyester (A), (B), and (C) at mass ratios of 75%, 20%, and 5% respectively. The resulting mixed raw materials are used as the raw materials for the outermost layer (surface layer). Polyester (A) As the raw material for the middle layer, it is supplied to two extruders respectively. After being melted at 285°C, it is co-extruded into two types of three layers (surface layer/middle layer/surface layer = 1:14:1 discharge amount). The film was transferred to a cooling roller set at 35°C for cooling and solidification to obtain an unstretched sheet. Then, after utilizing the roller peripheral speed difference to stretch the film 3.2 times in the longitudinal direction at a film temperature of 85°C, the prepared coating liquid 85 shown in Table 10 below was applied to one side of the longitudinally stretched film and introduced into the tenter. After stretching 4.0 times in the transverse direction at 95°C and heat treatment at 230°C, the film was relaxed by 2% in the transverse direction to obtain a film for DFR substrates. The obtained DFR base material film has a coating layer with a film thickness of 0.04 μm after drying on one side of a polyester film with a thickness of 16 μm. The average surface roughness (Ra) of the coating layer surface is 4 nm. The maximum surface height (Rt) of the surface is 100 nm. The characteristics of this film are shown in Table 11 below. As shown in Table 11, the film haze and dynamic friction coefficient of the DFR substrate film of Example 81 are low, the transparency of the coating layer is maintained, and the smoothness is good. Good coating appearance, damage resistance, surface resistance and air leakage index are also good.

實施例82、83： Examples 82 and 83:

將塗佈層之組成變更為表10所示之調配之塗佈液之組成，除此以外，以與實施例81相同之方式進行製造，獲得DFR基材用膜。如表11所示，實施例82、83之DFR基材用膜之膜霧度、動摩擦係數較低，維持塗佈層之透明性，並且平滑性良好，塗佈外觀、防受損性、表面電阻、空氣洩漏指數亦良好。 Except for changing the composition of the coating layer to the composition of the prepared coating liquid shown in Table 10, the film was produced in the same manner as in Example 81 to obtain a film for a DFR base material. As shown in Table 11, the film haze and dynamic friction coefficient of the DFR substrate films of Examples 82 and 83 are low, the transparency of the coating layer is maintained, and the smoothness is good, and the coating appearance, damage resistance, surface The resistance and air leakage index are also good.

實施例84： Example 84:

將聚酯(A)、(B)分別以80%、20%之質量比率進行混合，將所得之混合原料作為最外層(表層)之原料，將聚酯(A)作為中間層之原料，分別供給至2台擠出機，分別於285℃下熔融後，以2種3層(表層/中間層/表層=1：14：1之噴出量)之層構成共擠出至設定為40℃之冷卻輥上進行冷卻固化，而獲得未延伸片材。繼而，利用輥周速差以膜溫度85℃於縱向上延伸3.2倍後，於該縱延伸膜之單面塗佈下述表10所示之調配之塗佈液85，導入拉幅機中，於橫向上以95℃延伸4.0倍，並於230℃下進行熱處理後，於橫向上鬆弛2%，獲得DFR基材用膜。所獲得之DFR基材用膜於厚度16μm之聚酯膜之單面具有乾燥後之膜厚為0.04μm之塗佈層，塗佈層表面之平均表面粗糙度(Ra)為2nm，塗佈層表面之最大表面高度(Rt)為70nm。將該膜之特性示於下述表12。如表12所示，實施例84之DFR基材用膜之膜霧度、動摩擦係數較低，維持塗佈層之透明性，並且平滑性良好，塗佈外觀、防受損性、表面電阻、空氣洩漏指數亦良好。 Mix polyester (A) and (B) at a mass ratio of 80% and 20% respectively. The resulting mixed raw material is used as the raw material for the outermost layer (surface layer), and polyester (A) is used as the raw material for the middle layer. Supplied to two extruders, each is melted at 285°C, and then co-extruded to a temperature of 40°C in the form of two layers of three layers (surface layer/middle layer/surface layer = 1:14:1 discharge volume). Cooling and solidification are performed on a cooling roll to obtain an unstretched sheet. Then, after utilizing the roller peripheral speed difference to stretch the film 3.2 times in the longitudinal direction at a film temperature of 85°C, the prepared coating liquid 85 shown in Table 10 below was applied to one side of the longitudinally stretched film and introduced into the tenter. After stretching 4.0 times in the transverse direction at 95°C and heat treatment at 230°C, the film was relaxed by 2% in the transverse direction to obtain a film for DFR substrates. The obtained DFR base material film has a coating layer with a film thickness of 0.04 μm after drying on one side of a polyester film with a thickness of 16 μm. The average surface roughness (Ra) of the coating layer surface is 2 nm. The maximum surface height (Rt) of the surface is 70 nm. The characteristics of this film are shown in Table 12 below. As shown in Table 12, the film haze and dynamic friction coefficient of the DFR substrate film of Example 84 are low, the transparency of the coating layer is maintained, and the smoothness is good, and the coating appearance, damage resistance, surface resistance, The air leakage index is also good.

實施例85、86： Examples 85 and 86:

將塗佈層之組成變更為表10所示之調配之塗佈液之組成，除此以外，以與實施例84相同之方式進行製造，獲得DFR基材用膜。如表12所示，實施例85、86之DFR基材用膜之膜霧度、動摩擦係數較低，維持塗佈層之透明性，並且平滑性良好，塗佈外觀、防受損性、表面電阻、空氣洩漏指數亦良好。 Except that the composition of the coating layer was changed to the composition of the prepared coating liquid shown in Table 10, the film was produced in the same manner as in Example 84 to obtain a film for a DFR base material. As shown in Table 12, the film haze and dynamic friction coefficient of the DFR substrate films of Examples 85 and 86 are low, the transparency of the coating layer is maintained, and the smoothness is good, and the coating appearance, damage resistance, surface The resistance and air leakage index are also good.

實施例87~88： Embodiment 87~88:

將塗佈層之組成變更為表10所示之調配之塗佈液之組成，除此以外，以與實施例84相同之方式進行製造，獲得DFR基材用膜。如表12所示，實施例87、88之DFR基材用膜之膜霧度、動摩擦係數較低，維持塗佈層之透明性，並且平滑性良好，塗佈外觀、防受損性、表面電阻、空氣洩漏指數亦良好。 Except that the composition of the coating layer was changed to the composition of the prepared coating liquid shown in Table 10, the film was produced in the same manner as in Example 84 to obtain a film for a DFR base material. As shown in Table 12, the film haze and dynamic friction coefficient of the DFR substrate films of Examples 87 and 88 are low, the transparency of the coating layer is maintained, and the smoothness is good, and the coating appearance, damage resistance, surface The resistance and air leakage index are also good.

比較例81： Comparative example 81:

不設置塗佈層，除此以外，以與實施例81相同之方式進行製造，獲得膜。對所獲得之膜進行評價，結果由於不具有塗佈層，故而如表11所示，為動摩擦係數及防受損性較差之膜。 Except that the coating layer was not provided, the film was produced in the same manner as in Example 81 to obtain a film. The obtained film was evaluated. As a result, since it did not have a coating layer, as shown in Table 11, it was a film with poor dynamic friction coefficient and damage prevention properties.

比較例82： Comparative example 82:

將塗佈層之塗佈劑組成變更為表10所示之調配之塗佈液之組成，除此以外，以與實施例81相同之方式進行製造，獲得膜。對所獲得之膜進行 評價，結果如表11所示，由於塗佈液94中含有聚醚化合物，故而即便為具有塗佈層之膜，亦為防受損性較差之膜。 Except that the coating agent composition of the coating layer was changed to the composition of the prepared coating liquid shown in Table 10, the film was produced in the same manner as in Example 81 to obtain a film. Conduct the obtained membrane As a result of the evaluation, as shown in Table 11, the coating liquid 94 contains a polyether compound, so even a film having a coating layer has poor damage resistance.

比較例83： Comparative example 83:

將塗佈層之塗佈劑組成變更為表10所示之調配之塗佈液之組成，除此以外，以與實施例81相同之方式進行製造，獲得膜。對所獲得之膜進行評價，結果如表11所示，係雖然塗佈液98中含有交聯劑，但由於包含粒徑超過1μm之粒子，故而存在產生磨削之情形，由於粒子AL之面積比率超過15%，故而防受損性較差之膜。 Except that the coating agent composition of the coating layer was changed to the composition of the prepared coating liquid shown in Table 10, the film was produced in the same manner as in Example 81 to obtain a film. The obtained film was evaluated, and the results are shown in Table 11. Although the coating liquid 98 contains a cross-linking agent, it contains particles with a particle diameter exceeding 1 μm, so grinding may occur. Due to the area of the particles AL The ratio exceeds 15%, so the film has poor damage resistance.

比較例84、85： Comparative Examples 84 and 85:

將塗佈層之塗佈劑組成變更為表10所示之調配之塗佈液之組成，除此以外，以與實施例81相同之方式進行製造，獲得膜。對所獲得之膜進行評價，結果如表11所示，比較例84之膜係雖然塗佈液84中含有交聯劑，但由於粒子AL之面積比率為0%，故而塗佈外觀及防受損性亦較差之膜。比較例85之膜係雖然塗佈液86中含有交聯劑，但由於粒子AS之面積為0.3%，粒子AL之面積為98.3%，故而塗佈外觀及防受損性亦較差之膜。 Except that the coating agent composition of the coating layer was changed to the composition of the prepared coating liquid shown in Table 10, the film was produced in the same manner as in Example 81 to obtain a film. The obtained film was evaluated, and the results are shown in Table 11. Although the coating liquid 84 of the film system of Comparative Example 84 contained a cross-linking agent, the area ratio of the particles AL was 0%, so the coating appearance and protection were poor. It is also a membrane with poor damage properties. Although the coating liquid 86 of the film of Comparative Example 85 contains a cross-linking agent, the area of the particles AS is 0.3% and the area of the particles AL is 98.3%, so the coating appearance and damage resistance are also poor.

比較例86： Comparative example 86:

不設置塗佈層，除此以外，以與實施例84相同之方式進行製造，獲得膜。對所獲得之膜進行評價，結果由於不具有塗佈層，故而如表12所示，為動摩擦係數或防受損性較差而產生橫寬較大之表層皺褶之膜。 Except that the coating layer was not provided, the film was produced in the same manner as in Example 84 to obtain a film. The obtained film was evaluated. As a result, since it did not have a coating layer, as shown in Table 12, it was a film with a poor dynamic friction coefficient or damage resistance, resulting in surface wrinkles with a large width.

比較例87： Comparative example 87:

將塗佈層之塗佈劑組成變更為表10所示之調配之塗佈液之組成，除此以外，以與實施例84相同之方式進行製造，獲得膜。對所獲得之膜進行評價，結果如表12所示，由於塗佈液94中含有聚醚化合物，故而即便為具有塗佈層之膜，亦為防受損性較差之膜。 Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 10, the film was produced in the same manner as in Example 84 to obtain a film. The obtained film was evaluated. The results are shown in Table 12. Since the coating liquid 94 contains a polyether compound, the film has poor damage resistance even if it has a coating layer.

比較例88： Comparative example 88:

將塗佈層之塗佈劑組成變更為表10所示之調配之塗佈液之組成，除此以外，以與實施例84相同之方式進行製造，獲得膜。對所獲得之膜進行評價，結果如表12所示，係雖然塗佈液97中含有交聯劑，但由於粒子AL之面積比率超過15%，故而防受損性亦較差之膜。 Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 10, the film was produced in the same manner as in Example 84 to obtain a film. The obtained film was evaluated. As shown in Table 12, the results showed that although the coating liquid 97 contained a cross-linking agent, the area ratio of the particles AL exceeded 15%, so the film had poor damage resistance.

比較例89~94： Comparative examples 89~94:

將塗佈層之塗佈劑組成變更為表10所示之調配之塗佈液之組成，除此以外，以與實施例84相同之方式進行製造，獲得膜。對所獲得之膜進行評價，結果如表12所示，比較例89~93之膜係雖然塗佈液81~84中含有交聯劑，但由於粒子AL之面積比率為0%，故而亦產生橫寬較大之表層皺褶之膜或塗佈外觀及防受損性亦較差之膜。比較例94之膜係雖然塗佈液86中含有交聯劑，但由於粒子AS之面積為0.3%，粒子AL之面積為98.3%，故而塗佈外觀及防受損性亦較差之膜。 Except for changing the coating agent composition of the coating layer to the composition of the prepared coating liquid shown in Table 10, the film was produced in the same manner as in Example 84 to obtain a film. The obtained films were evaluated, and the results are shown in Table 12. Although the coating liquids 81 to 84 of the film systems of Comparative Examples 89 to 93 contained a cross-linking agent, since the area ratio of the particles AL was 0%, it also produced Films with large surface wrinkles or films with poor coating appearance and damage resistance. Although the coating liquid 86 of the film of Comparative Example 94 contains a cross-linking agent, the area of the particles AS is 0.3% and the area of the particles AL is 98.3%, so the coating appearance and damage resistance are also poor.

Figure 108105213-A0305-02-0082-14
Figure 108105213-A0305-02-0082-14

Figure 108105213-A0305-02-0082-16
Figure 108105213-A0305-02-0082-16

Figure 108105213-A0305-02-0083-17
Figure 108105213-A0305-02-0083-17

[產業上之可利用性] [Industrial availability]

本發明之乾式膜抗蝕劑基材用聚酯膜例如可適當用作製造印刷配線板時等所使用之乾式膜抗蝕劑之基材膜。 The polyester film for a dry film resist base material of the present invention can be suitably used as a base film for a dry film resist used in the production of printed wiring boards, for example.

Claims (16)

一種乾式膜抗蝕劑基材用聚酯膜，其特徵在於：於聚酯膜之至少單面具有塗佈層，該塗佈層中之抗靜電劑之含量為45質量%以下，該塗佈層中含有粒子，相對於對該塗佈層之表面進行觀察時之該塗佈層表面中所占之粒子之面積合計，粒徑為30~80nm之粒子AS之面積比率為60~99.9%之範圍內，粒徑為100~400nm之粒子AL之面積比率為0.1~15%之範圍內，且實質上不含粒徑超過1μm之粒子。 A polyester film for a dry film resist base material, characterized in that: there is a coating layer on at least one side of the polyester film, and the content of the antistatic agent in the coating layer is 45% by mass or less, and the coating layer The layer contains particles, and the area ratio of particles AS with a particle diameter of 30 to 80 nm is 60 to 99.9% relative to the total area of particles occupying the surface of the coating layer when the surface of the coating layer is observed. Within the range, the area ratio of particles AL with a particle size of 100 to 400 nm is within the range of 0.1 to 15%, and does not substantially contain particles with a particle size exceeding 1 μm. 一種乾式膜抗蝕劑基材用聚酯膜，其特徵在於：於聚酯膜之至少單面具有塗佈層，該塗佈層中含有界面活性劑，該塗佈層中含有粒子，相對於對該塗佈層之表面進行觀察時之該塗佈層表面中所占之粒子之面積合計，粒徑為30~80nm之粒子AS之面積比率為60~99.9%之範圍內，粒徑為100~400nm之粒子AL之面積比率為0.1~15%之範圍內，且實質上不含粒徑超過1μm之粒子。 A polyester film for a dry film resist base material, characterized in that: there is a coating layer on at least one side of the polyester film, the coating layer contains a surfactant, and the coating layer contains particles. When the surface of the coating layer is observed, the total area of the particles occupying the surface of the coating layer, the area ratio of particles AS with a particle diameter of 30 to 80 nm is in the range of 60 to 99.9%, and the particle diameter is 100 The area ratio of ~400nm particles AL is in the range of 0.1~15%, and does not substantially contain particles with a particle size exceeding 1 μm. 一種乾式膜抗蝕劑基材用聚酯膜，其特徵在於：於聚酯膜之至少單面具有塗佈層，且塗佈層中實質上不含無機鹽，該塗佈層中含有粒子， 相對於對該塗佈層之表面進行觀察時之該塗佈層表面中所占之粒子之面積合計，粒徑為30~80nm之粒子AS之面積比率為60~99.9%之範圍內，粒徑為100~400nm之粒子AL之面積比率為0.1~15%之範圍內，且實質上不含粒徑超過1μm之粒子。 A polyester film for a dry film resist base material, characterized in that: a coating layer is provided on at least one side of the polyester film, and the coating layer does not substantially contain inorganic salts, and the coating layer contains particles, When the surface of the coating layer is observed, the area ratio of particles AS having a particle diameter of 30 to 80 nm is in the range of 60 to 99.9%, and the particle diameter is The area ratio of particles AL between 100 and 400 nm is in the range of 0.1 to 15%, and does not substantially contain particles with a particle size exceeding 1 μm. 一種乾式膜抗蝕劑基材用聚酯膜，其特徵在於：於聚酯膜之至少單面具有塗佈層，且塗佈層中實質上不含聚醚化合物，該塗佈層中含有粒子，相對於對該塗佈層之表面進行觀察時之該塗佈層表面中所占之粒子之面積合計，粒徑為30~80nm之粒子AS之面積比率為60~99.9%之範圍內，粒徑為100~400nm之粒子AL之面積比率為0.1~15%之範圍內，且實質上不含粒徑超過1μm之粒子。 A polyester film for a dry film resist base material, characterized in that: a coating layer is provided on at least one side of the polyester film, and the coating layer does not substantially contain a polyether compound, and the coating layer contains particles , relative to the total area of the particles occupying the surface of the coating layer when the surface of the coating layer is observed, the area ratio of particles AS with a particle diameter of 30 to 80 nm is in the range of 60 to 99.9%, and the particles The area ratio of particles AL with a diameter of 100 to 400 nm is in the range of 0.1 to 15%, and does not substantially contain particles with a diameter exceeding 1 μm. 一種乾式膜抗蝕劑基材用聚酯膜，其特徵在於：於聚酯膜之至少單面具有由含有交聯劑之塗佈液形成之塗佈層，該塗佈層中之抗靜電劑之含量為45質量%以下，該塗佈層中含有粒子A-1及粒子A-2，該粒子A-1之平均粒徑為0.001~0.06μm，該粒子A-2之平均粒徑為0.06~1.0μm。 A polyester film for a dry film resist base material, characterized in that at least one side of the polyester film has a coating layer formed of a coating liquid containing a cross-linking agent, and an antistatic agent in the coating layer The content is less than 45% by mass. The coating layer contains particles A-1 and particles A-2. The average particle size of particle A-1 is 0.001~0.06 μm, and the average particle size of particle A-2 is 0.06. ~1.0μm. 一種乾式膜抗蝕劑基材用聚酯膜，其特徵在於：於聚酯膜之至少單面具有由含有交聯劑之塗佈液形成之塗佈層，該塗佈層中含有界面活性劑， 該塗佈層中含有粒子A-1及粒子A-2，該粒子A-1之平均粒徑為0.001~0.06μm，該粒子A-2之平均粒徑為0.06~1.0μm。 A polyester film for a dry film resist base material, characterized in that at least one side of the polyester film has a coating layer formed of a coating liquid containing a cross-linking agent, and the coating layer contains a surfactant , The coating layer contains particle A-1 and particle A-2. The average particle diameter of particle A-1 is 0.001~0.06 μm, and the average particle diameter of particle A-2 is 0.06~1.0 μm. 一種乾式膜抗蝕劑基材用聚酯膜，其特徵在於：於聚酯膜之至少單面具有由含有交聯劑之塗佈液形成之塗佈層，該塗佈層中實質上不含無機鹽，該塗佈層中含有粒子A-1及粒子A-2，該粒子A-1之平均粒徑為0.001~0.06μm，該粒子A-2之平均粒徑為0.06~1.0μm。 A polyester film for a dry film resist base material, characterized in that at least one side of the polyester film has a coating layer formed of a coating liquid containing a cross-linking agent, and the coating layer does not substantially contain Inorganic salt, the coating layer contains particle A-1 and particle A-2, the average particle diameter of particle A-1 is 0.001~0.06 μm, and the average particle diameter of particle A-2 is 0.06~1.0 μm. 一種乾式膜抗蝕劑基材用聚酯膜，其特徵在於：於聚酯膜之至少單面具有由含有交聯劑之塗佈液形成之塗佈層，該塗佈層中實質上不含聚醚化合物，該塗佈層中含有粒子A-1及粒子A-2，該粒子A-1之平均粒徑為0.001~0.06μm，該粒子A-2之平均粒徑為0.06~1.0μm。 A polyester film for a dry film resist base material, characterized in that at least one side of the polyester film has a coating layer formed of a coating liquid containing a cross-linking agent, and the coating layer does not substantially contain Polyether compound, the coating layer contains particles A-1 and particles A-2, the average particle diameter of the particle A-1 is 0.001~0.06 μm, and the average particle diameter of the particle A-2 is 0.06~1.0 μm. 如請求項1至8中任一項之乾式膜抗蝕劑基材用聚酯膜，其中具有上述塗佈層之表面之平均表面粗糙度(Ra)為1~10nm之範圍內。 The polyester film for a dry film resist base material according to any one of claims 1 to 8, wherein the average surface roughness (Ra) of the surface with the above-mentioned coating layer is in the range of 1 to 10 nm. 如請求項1至8中任一項之乾式膜抗蝕劑基材用聚酯膜，其中具有上述塗佈層之表面依據JIS P8119所測得之空氣洩漏指數為400000秒以下。 The polyester film for a dry film resist base material according to any one of claims 1 to 8, wherein the air leakage index of the surface with the above-mentioned coating layer measured according to JIS P8119 is 400000 seconds or less. 如請求項1至8中任一項之乾式膜抗蝕劑基材用聚酯膜，其中上述塗佈層之厚度為0.001~1μm之範圍內。 The polyester film for a dry film resist substrate according to any one of claims 1 to 8, wherein the thickness of the coating layer is in the range of 0.001 to 1 μm. 如請求項1至8中任一項之乾式膜抗蝕劑基材用聚酯膜，其中上述塗佈層中含有蠟。 The polyester film for a dry film resist base material according to any one of claims 1 to 8, wherein the coating layer contains wax. 如請求項1至8中任一項之乾式膜抗蝕劑基材用聚酯膜，其中上述聚酯膜中含有可賦予易滑性之粒子B。 The polyester film for a dry film resist base material according to any one of claims 1 to 8, wherein the polyester film contains particles B that can impart slipability. 如請求項1至8中任一項之乾式膜抗蝕劑基材用聚酯膜，其中上述塗佈層係由塗佈液形成，該塗佈液含有交聯劑，該交聯劑係三聚氰胺化合物或
Figure 108105213-A0305-02-0087-44
唑啉化合物。 The polyester film for a dry film resist substrate according to any one of claims 1 to 8, wherein the coating layer is formed from a coating liquid, the coating liquid contains a cross-linking agent, and the cross-linking agent is melamine compound or
Figure 108105213-A0305-02-0087-44
oxazoline compounds. 如請求項14之乾式膜抗蝕劑基材用聚酯膜，其中相對於上述塗佈液中之全部非揮發成分之上述交聯劑之含量為5~85質量%。 As claimed in claim 14, the polyester film for a dry film resist base material, wherein the content of the cross-linking agent relative to all non-volatile components in the coating liquid is 5 to 85 mass %. 一種乾式膜抗蝕劑，其於如請求項1至15中任一項之乾式膜抗蝕劑基材用聚酯膜之與上述塗佈層側相反之側具有感光性樹脂層。 A dry film resist having a photosensitive resin layer on the opposite side to the coating layer side of the polyester film for a dry film resist base material according to any one of claims 1 to 15.
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