TWI418929B - Surface protection film - Google Patents
Surface protection film Download PDFInfo
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- TWI418929B TWI418929B TW095148240A TW95148240A TWI418929B TW I418929 B TWI418929 B TW I418929B TW 095148240 A TW095148240 A TW 095148240A TW 95148240 A TW95148240 A TW 95148240A TW I418929 B TWI418929 B TW I418929B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- 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
- G03F7/14—Production of collotype printing forms
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- 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
- G03F7/20—Exposure; Apparatus therefor
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- 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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
- G03F7/2014—Contact or film exposure of light sensitive plates such as lithographic plates or circuit boards, e.g. in a vacuum frame
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/748—Releasability
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- 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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- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
- Sealing Material Composition (AREA)
- Adhesive Tapes (AREA)
Description
本發明為一關於具備剝離性的表面保護薄膜，特別係適合用於在印刷基板製作步驟等中，具有黏著性的光阻劑曝光時之原稿(光刻掩膜photo mask)的表面之表面保護薄膜。The present invention relates to a surface protective film having releasability, and is particularly suitable for surface protection of a surface of an original (photomask) when an adhesive having an adhesive property is exposed in a printing substrate manufacturing step or the like. film.
通常，印刷配線板與樹脂凸板是藉著將光刻掩膜(曝光用原稿)緊密黏著於液狀之光阻劑等具有黏著性的光阻劑上，進行曝光來製作得出的。因此，若在光刻掩膜表面上不進行某些處理的話，曝光完了後，在從光阻劑上剝離光刻掩膜時，部份的光阻劑將會附著在光刻掩膜表面上，即使擦拭過後仍會殘留，將產生導致曝光準確度不良之問題。因為上述原因，一直以來都於相對光刻掩膜上的光阻劑之面上，設置具有剝離性之表面保護膜，來防止光阻劑附著在光刻掩膜上之情形。Usually, the printed wiring board and the resin convex plate are produced by adhering a photolithographic mask (exposure original) to an adhesive photoresist such as a liquid photoresist and exposing it. Therefore, if some processing is not performed on the surface of the lithography mask, after the lithographic mask is removed from the photoresist after the exposure is completed, part of the photoresist will adhere to the surface of the lithography mask. Even if it remains after wiping, there will be a problem that the exposure accuracy is poor. For the above reasons, a surface protective film having releasability has been conventionally provided on the surface of the photoresist on the photolithography mask to prevent the photoresist from adhering to the photolithography mask.
以一具有此般特性之光刻掩膜用的表面保護薄膜，被提出之有在塑膠薄膜之一面上具備剝離性的表面保護層，而另一面則係具有黏著層者(專利文獻一)。以一構成表面保護層之材料，通常使用矽類樹脂等具有剝離性之樹脂。A surface protective film for a photolithographic mask having such characteristics is proposed to have a peeling surface protective layer on one side of a plastic film and an adhesive layer on the other side (Patent Document 1). As a material constituting the surface protective layer, a resin having releasability such as a terpene resin is usually used.
然而即使是在這般的表面保護薄膜，也不能完全防止光阻劑附著在表面保護層；每當在表面保護層上反覆進行曝光時，會有光阻劑逐漸附著，將導致如曝光時的光被遮蔽，增加光散亂性等問題，成為曝光時的阻礙。另外，附著了的光阻劑之表面凹凸也將再轉印到基板(抗蝕)上，成為因表面缺陷而導致的不良品。However, even in such a surface protective film, the photoresist cannot be completely prevented from adhering to the surface protective layer; whenever the exposure is repeatedly performed on the surface protective layer, the photoresist is gradually attached, which may result in exposure, for example. Light is obscured, and problems such as light scattering are increased, which becomes an obstacle to exposure. Further, the surface unevenness of the adhered photoresist is also transferred to the substrate (resist) and becomes a defective product due to surface defects.
為了解決這樣的問題，也為了去除殘留在表面保護膜上之光阻劑與其他灰塵等等，需定期地使用清潔劑來清潔(除塵作業)表面保護膜之表面。(專利文獻二)然而這般的工作相當煩瑣，並且為了提高產量，希望能有減少清潔次數或者省去清潔工作的方法。In order to solve such a problem, in order to remove the photoresist and other dust remaining on the surface protective film, it is necessary to periodically clean the surface of the surface protective film by using a cleaning agent. (Patent Document 2) However, such work is rather cumbersome, and in order to increase the yield, it is desirable to have a method of reducing the number of cleanings or eliminating the cleaning work.
[專利文獻一]特開平11－7121號公報(申請專利範圍)[專利文獻二]特開2003－96409號公報(發明欲解決之課題)[Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei 11-7121 (Application No.) [Patent Document 2] JP-A-2003-96409 (Problem to be Solved by the Invention)
因此本發明之目的，在於提供對光阻劑具有持續極高度剝離性之表面保護薄膜。It is therefore an object of the present invention to provide a surface protection film which has a very high degree of releasability to a photoresist.
為了達成前述課題，深究後的結果發現，每當反覆曝光操作時，表面保護膜上之光阻劑會逐漸附著，逐漸喪失表面保護膜之剝離性。In order to achieve the above-mentioned problems, it has been found that the photoresist on the surface protective film gradually adheres to the peeling property of the surface protective film every time the reverse exposure operation is performed.
因此，本發明之發明者們，為了達成此般目的，在反覆深入研究後的結果，發現藉著使表面保護層達成含有以一剝離性成份，根據JIS R3257：1999標準之與水之接觸角度為100度以上之縮合反應型矽類樹脂，以及含有以一黏著劑成份，根據JIS R3257：1999標準之與水之接觸角度為90度以下的縮合反應型樹脂所構成後，即可以解決上述課題，完成本發明之宗旨。Therefore, the inventors of the present invention have found that, in order to achieve such a purpose, after repeated investigations, it has been found that by making the surface protective layer contain a peelable component, the contact angle with water according to JIS R3257:1999 The above reaction can be solved by a condensation reaction type oxime resin having a pressure of 100 degrees or more and a condensation reaction type resin having a contact angle with water of 90 degrees or less in accordance with JIS R3257:1999. The purpose of the present invention is completed.
也就是說，本發明的表面保護薄膜之特徵為：在透明高分子薄膜一面上設置有表面保護層的表面保護薄膜上，其表面保護層含有以一剝離性成份，根據JIS R3257：1999標準之與水之接觸角度為100度以上之縮合反應型矽類樹脂，並且由以一黏著劑成份，根據JIS R3257：1999標準之與水之接觸角度為90度以下之縮合反應型樹脂所構成。That is, the surface protective film of the present invention is characterized in that a surface protective film provided with a surface protective layer on one side of the transparent polymer film has a surface protective layer containing a peeling component according to JIS R3257:1999. The condensation reaction type oxime resin having a contact angle with water of 100 degrees or more is composed of a condensation reaction type resin having an adhesive composition in accordance with JIS R3257:1999 and having a contact angle with water of 90 degrees or less.
另外，本發明之表面保護薄膜之特徵為：作為一與前述水之接觸角度為90度以下之縮合反應型樹脂，含有縮合反應型矽類樹脂。Further, the surface protective film of the present invention is characterized in that the condensation reaction type resin which is a contact angle with the water of 90 degrees or less contains a condensation reaction type oxime resin.
另外，本發明之表面保護薄膜之特徵為：與前述水之接觸角度為100度以上的縮合反應型矽類樹脂之比例為：相對於前記黏著劑成份100重量份，其為1重量份~40重量份。Further, the surface protective film of the present invention is characterized in that the ratio of the condensation reaction type oxime resin having a contact angle with the water of 100 degrees or more is 1 part by weight to 40 parts by weight based on 100 parts by weight of the adhesive component. Parts by weight.
於本發明之表面保護薄膜之一樣態，為在透明高分子薄膜之另一面上設置有黏著層。In the same manner as the surface protective film of the present invention, an adhesive layer is provided on the other surface of the transparent polymer film.
另外，本發明之表面保護層用組成物之特徵為：含有根據JIS R3257：1999標準之與水之接觸角度為100度以上之縮合反應型矽類樹脂，以及根據JIS R3257：1999標準之與水之接觸角度為90度以下之縮合反應型樹脂。Further, the composition for a surface protective layer of the present invention is characterized in that it contains a condensation reaction type oxime resin having a contact angle with water of 100 degrees or more according to JIS R3257:1999, and water with a standard according to JIS R3257:1999. The condensation reaction type resin having a contact angle of 90 degrees or less.
另外，本發明之表面保護膜用組成物，前述縮合反應型樹脂含有根據JIS R3257：1999標準之與水之接觸角度為90度以下之縮合反應型矽類樹脂。在本發明之表面保護膜用組成物中，縮合反應型樹脂含有，例如：15重量%以上，70重量%以下之此縮合反應型矽類樹脂。Further, in the composition for a surface protective film of the present invention, the condensation reaction type resin contains a condensation reaction type oxime resin having a contact angle with water of 90 degrees or less according to JIS R3257:1999. In the composition for a surface protective film of the present invention, the condensation reaction type resin contains, for example, 15% by weight or more and 70% by weight or less of the condensation reaction type oxime resin.
藉由本發明可防止光阻劑附著在表面保護膜上，即使不進行清理工作，也可以維持對光阻劑之極高度剝離性。According to the present invention, the photoresist can be prevented from adhering to the surface protective film, and the extremely high releasability to the photoresist can be maintained even without performing the cleaning operation.
接著說明本發明之表面保護層用組成物與表面保護薄膜。Next, the composition for a surface protective layer of the present invention and a surface protective film will be described.
本發明之表面保護層用組成物為一含有：與水之接觸角度為100度以上之縮合反應型矽類樹脂，以及與水之接觸角度為90度以下之縮合反應型樹脂者。本發明之表面保護層用組成物可用於形成：在高分子薄膜等基底材料上設置表面保護層的表面保護薄膜之表面保護層，以及直接設置於應保護之表面的材料(例如：光刻掩膜)表面之表面保護膜。The composition for a surface protective layer of the present invention is a condensation reaction type oxime resin containing a contact angle with water of 100 degrees or more, and a condensation reaction type resin having a contact angle with water of 90 degrees or less. The composition for a surface protective layer of the present invention can be used for forming a surface protective layer of a surface protective film provided with a surface protective layer on a base material such as a polymer film, and a material directly disposed on a surface to be protected (for example, photolithography masking) Surface protective film on the surface of the film.
本發明之表面保護薄膜係一在透明高分子薄膜一面上設置表面保護層，另一面上則設置黏著層之表面保護薄膜；表面保護薄膜係由本發明之表面保護層用組成物所形成者。以下將說明有關本發明之表面保護薄膜之實施形態。The surface protective film of the present invention comprises a surface protective layer on one side of the transparent polymer film and a surface protective film on the other side of the adhesive layer; and the surface protective film is formed of the composition for a surface protective layer of the present invention. Embodiments of the surface protective film of the present invention will be described below.
以一透明高分子薄膜，若為曝光時所使用的紫外線穿透率高者為佳；並使用聚對苯二甲酸乙二酯(polyethylene terephthalate)、聚對苯二甲酸丁二酯(Poly butylenes terephthalate)、聚萘二甲酸乙二酯(polyethylene naphthalate)、聚碳酸酯、聚乙烯、聚丙烯、聚苯乙烯、三醋酸纖维素(triacetyl cellulose)、丙烯、聚氯乙烯等高透明性的高分子薄膜。特別是雙軸延伸之聚對苯二甲二乙酯薄膜，因為具有高機械性強度以及高尺寸安定性，因此特別適合使用。另外，在這些透明高分子薄膜上設置適宜易接著層等者也廣為使用。A transparent polymer film is preferred for use in exposure to ultraviolet light; and polyethylene terephthalate or polybutylene terephthalate is used. ), polyethylene naphthalate, polycarbonate, polyethylene, polypropylene, polystyrene, triacetyl cellulose, propylene, polyvinyl chloride, and other highly transparent polymers film. In particular, the biaxially stretched polyethylene terephthalate film is particularly suitable for use because of its high mechanical strength and high dimensional stability. Further, it is also widely used to provide a suitable adhesive layer on these transparent polymer films.
透明高分子薄膜之厚度，因為會影響到解像度，所以以薄者為佳；但是考慮到操作性，厚度的下限為1 μm以上，能為2μm以上更好，最好為4μm以上；其上限為100μm以下，能為25μm以下更好，最好能為12μm以下之範圍。The thickness of the transparent polymer film is preferably thin because it affects the resolution. However, in consideration of operability, the lower limit of the thickness is 1 μm or more, more preferably 2 μm or more, and most preferably 4 μm or more; Below 100 μm, it can be preferably 25 μm or less, and more preferably in the range of 12 μm or less.
設置於與透明高分子薄膜的表面保護層面之相反面上之黏著層，可使用一般使用的丙烯系黏著劑、橡膠系黏著劑，胺甲酸酯(urethane)系黏著劑、矽類黏著劑等公知的透明黏著劑。本發明之表面保護薄膜，因為目的在於保護畫像等，因此黏著劑最好是透明的，並且其本身具有高度耐存性。以一此般黏著劑，以胺甲酸酯交聯性或環氧交聯性的高分子量之丙烯類的黏著劑較為適合。另外，亦可使用具備防止帶電等特性之黏著劑。The adhesive layer provided on the opposite surface to the surface protective layer of the transparent polymer film can be a commonly used propylene-based adhesive, a rubber-based adhesive, an urethane-based adhesive, an anthraquinone-based adhesive, or the like. A well-known transparent adhesive. The surface protective film of the present invention is preferably transparent in that it is intended to protect a portrait or the like, and is highly resistant to itself. A high-molecular-weight propylene-based adhesive which is a cross-linking or epoxy crosslinkable with a urethane is preferred as a binder. Further, an adhesive having characteristics such as prevention of charging can also be used.
或者亦可在透明高分子薄膜的帶電防止層之面上設置黏著層。Alternatively, an adhesive layer may be provided on the surface of the electrification preventing layer of the transparent polymer film.
為了不妨礙透明性(解像度)，並能獲得適度之黏著性，此黏著層之厚度之下限為0.5μm以上，能為1μm以上更好，最好能為2μm以上；其上限為30μm以下，能為15μm以下更好，最好能為7μm以下之範圍。In order not to impede transparency (resolution) and to obtain moderate adhesion, the lower limit of the thickness of the adhesive layer is 0.5 μm or more, more preferably 1 μm or more, and most preferably 2 μm or more; and the upper limit is 30 μm or less. More preferably, it is 15 μm or less, and preferably it is in the range of 7 μm or less.
另外，為了不讓其因黏著性而使表面保護薄膜之操作性降低，也可以適宜地在黏著層上貼合在表面實施過剝離處理的剝離薄膜。Further, in order to prevent the workability of the surface protective film from being lowered due to the adhesiveness, the release film which has been subjected to the release treatment on the surface may be suitably bonded to the adhesive layer.
設置在透明高分子薄膜另一方表面上之表面保護層，係由具有剝離性之表面保護層所組成，並由具有剝離性成份與黏著劑成份所構成者。The surface protective layer provided on the other surface of the transparent polymer film is composed of a peelable surface protective layer and is composed of a peeling component and an adhesive component.
剝離性成份為一對於光阻劑能給予高度剝離性之成份者，主要由根據JIS R3257：1999標準之與水之接觸角度為100度以上之縮合反應型矽類樹脂(以下亦稱高接觸角度縮合反應型樹脂)所組成。另外，黏著劑之成份為一對於透明高分子薄膜能給予高接著性之成份者，主要由根據JIS R3257：1999標準之與水之接觸角度為90度以下之縮合反應型樹脂(以下亦稱低接觸角度縮合反應型樹脂)所組成。The peeling component is a component capable of imparting high releasability to a photoresist, and is mainly a condensation reaction type oxime resin having a contact angle with water of 100 degrees or more according to JIS R3257:1999 (hereinafter also referred to as a high contact angle). The composition of the condensation reaction type resin). In addition, the component of the adhesive is a component capable of imparting high adhesion to a transparent polymer film, and is mainly a condensation reaction type resin having a contact angle with water of 90 degrees or less according to JIS R3257:1999 (hereinafter also referred to as low Composition of contact angle condensation reaction type resin).
使用含有這兩種縮合反應型樹脂之表面保護層用組成物，在基底材料上形成表面保護層時，在塗膜乾燥之過程中，高接觸角度縮合反應型樹脂會自律地偏在於表面側，而低接觸角度縮合反應型樹脂則會偏在於基底材料側。在兩者之界面上會因為剝離性成份與黏著劑成份進行縮合反應而結合。如此一來，藉由使用上述兩類型之縮合反應型樹脂，因為具備高度剝離性之剝離性成份高濃度地存在於表面保護層之表面上，因此可得到高度剝離性。另外因為高濃度地存在著剝離性成份之領域與高濃度地存在著黏著劑之領域，會因為構成兩成份之樹脂的縮合反應而結合，因此剝離性成份不會從塗膜上剝落，亦可維持剝離性。When a surface protective layer is formed on a base material using a composition for a surface protective layer containing the two types of condensation reaction type resins, the high contact angle condensation reaction type resin is autonomously biased on the surface side during drying of the coating film. The low contact angle condensation reaction type resin is biased on the side of the base material. At the interface between the two, the debonding component is combined with the adhesive component to carry out a condensation reaction. In this way, by using the above two types of condensation reaction type resins, since the peeling component having high releasability is present on the surface of the surface protective layer at a high concentration, high peelability can be obtained. In addition, since the field of the adhesive component exists in a high concentration and the adhesive agent exists in a high concentration, it is combined by the condensation reaction of the resin constituting the two components, so that the peeling component does not peel off from the coating film, and Maintain stripping.
另一方面，僅藉著以一黏著劑成份之低接觸角度縮合反應型樹脂係無法獲得剝離性的。另外，若只有以一剝離性成份之高接觸角度縮合反應型樹脂，其與透明高分子薄膜間的接著性不佳，另外機械性強度亦劣，與印刷基板接觸時的耐擦傷性亦不足。此外，高接觸角度縮合反應型矽類樹脂作為黏著劑成份，與非縮合反應型樹脂之樹脂組合時；或者低接觸角度縮合反應型樹脂作為剝離性成份，與非縮合反應型矽類樹脂之樹脂組合時，因為剝離性成份與黏著劑成份將無法結合，因此無法獲得持續剝離性。On the other hand, peelability cannot be obtained only by condensation of a reactive resin system at a low contact angle of an adhesive component. Further, if the reactive resin is condensed only at a high contact angle of a releasable component, the adhesion to the transparent polymer film is not good, and the mechanical strength is also inferior, and the scratch resistance in contact with the printed substrate is also insufficient. In addition, a high contact angle condensation reaction type oxime resin is used as an adhesive component in combination with a resin of a non-condensation reaction type resin; or a low contact angle condensation reaction type resin is used as a release component, and a resin of a non-condensation reaction type oxime resin When combined, since the peeling component and the adhesive component cannot be combined, continuous peeling cannot be obtained.
縮合反應型矽類樹脂為一具備下式(1)般矽氧烷主鏈之矽類樹脂，包括：以一支鏈之有機官能團R以及/或者端基，將使生成矽醇基之水解性基，也就是水解後使矽醇基(Si－OH)再生，並且脫水縮合，在主鏈間形成矽氧烷結合之基，以及疏水性基。以一水解性基，可以舉出例如乙酸基、肟基、甲氧基、醯胺基、丙烯氧基等。另外，以一疏水性基，可以舉出如烷基、苯基、氟化烷基等。藉由適宜選擇導入這些構成有機官能團R之水解性基與疏水性基，可以調整縮合反應型矽類樹脂與水之接觸角度。具體來說，疏水性基之比例越高可以擴大接觸角度。另外越減少疏水性基之比例，增加水解性基，亦能縮小其接觸角度。The condensation reaction type oxime resin is an oxime resin having a main chain of the above formula (1), and includes a hydrolyzable group which forms a sterol group by an organic functional group R and/or a terminal group of a chain. The base, that is, the sterol group (Si-OH) is regenerated after hydrolysis, and is dehydrated and condensed to form a siloxane coupling group between the main chains, and a hydrophobic group. Examples of the hydrolyzable group include an acetate group, a mercapto group, a methoxy group, a decylamino group, a propyleneoxy group and the like. Further, examples of the hydrophobic group include an alkyl group, a phenyl group, a fluorinated alkyl group and the like. By appropriately introducing these hydrolyzable groups and hydrophobic groups constituting the organic functional group R, the contact angle of the condensation reaction type fluorene resin with water can be adjusted. Specifically, the higher the ratio of the hydrophobic groups, the larger the contact angle. In addition, the more the ratio of the hydrophobic group is decreased, the hydrolyzable group is increased, and the contact angle can be reduced.
以一高接觸角度之縮合反應型矽類樹脂，可使用例如：將二甲基聚矽氧烷以一基礎聚合物的支鏈以及/或者端基含有苯基、烷基、氟化烷基之者；就縮合反應性之觀點來說，生成矽醇基之水解性基，可以使用含有：例如乙酸基、肟基、甲氧基、醯胺基、丙烯氧基等者。For a condensation reaction type quinone resin having a high contact angle, for example, dimethyl polysiloxane can be used as a branch of a base polymer and/or a terminal group containing a phenyl group, an alkyl group, or a fluorinated alkyl group. In view of the condensation reactivity, a hydrolyzable group which forms a decyl group may be, for example, an acetate group, a mercapto group, a methoxy group, a decylamino group or a propyleneoxy group.
以一剝離性成分，在不妨礙塗膜機能之範圍內，可以添加上述縮合反應型矽類樹脂以外之剝離性成分。以一其他剝離性成分，例如，可以舉出一支鏈和端基不具有水解性之矽油等(二甲基聚矽氧烷)。在添加其他剝離性成分時，縮合反應型矽類樹脂在剝離性成分中所佔之比例最好在90%以上。The peelable component other than the above condensation reaction type oxime resin may be added as a peelable component insofar as it does not interfere with the film coating function. Examples of the other exfoliating component include, for example, an eucalyptus oil or the like (dimethylpolyoxane) in which one chain and terminal groups are not hydrolyzable. When a further exfoliating component is added, the ratio of the condensation-reactive fluorene-based resin to the releasable component is preferably 90% or more.
低接觸角度縮合反應型樹脂係以一黏著劑成分來發揮作用，其與水之接觸角度以在90度以下為佳，最好在85度以下。關於低接觸角度縮合反應型樹脂，也可以藉由適當調整構成支鏈有機官能團之水解性基以及疏水性基之比例來調整縮合反應型樹脂的與水之間之接觸角度。以一此類之樹脂，可以使用縮合反應型矽類樹脂，縮合反應型醇酸樹脂，縮合反應型密胺樹脂，縮合反應型丙烯樹脂，縮合反應型聚酯樹脂等等。The low contact angle condensation reaction type resin functions as an adhesive component, and its contact angle with water is preferably 90 degrees or less, preferably 85 degrees or less. In the low contact angle condensation reaction type resin, the contact angle of the condensation reaction type resin with water can be adjusted by appropriately adjusting the ratio of the hydrolyzable group and the hydrophobic group constituting the branched organic functional group. As such a resin, a condensation reaction type oxime resin, a condensation reaction type alkyd resin, a condensation reaction type melamine resin, a condensation reaction type propylene resin, a condensation reaction type polyester resin or the like can be used.
尤其，縮合反應型矽類樹脂，因在溶液狀態下與剝離性成分之有機矽類樹脂的相溶性好，故較為適宜，例如可以使用擁有生成矽醇基的水解性基之者。此外，縮合反應型樹脂中所含有的聚矽氧烷成分(矽類樹脂)之下限以15重量%以上為好，上限以70重量%左右為好。藉由控制在這樣的範圍內，在以一黏著劑成分之其他縮合反應型樹脂與以一剝離性成分之高接觸角度縮合反應型矽類樹脂之間，可以置入以一黏著劑成分之縮合反應型矽類樹脂使其相互結合，因此能提高與透明性高分子薄膜之附著性，亦能給予塗膜充分之固化性，以及賦予存在於光阻劑中的溶劑充分的機械強度和耐擦傷性。In particular, the condensation reaction type oxime resin is preferably compatible with the organic oxime resin of the releasable component in a solution state, and for example, a hydrolyzable group having a sterol group can be used. In addition, the lower limit of the polyoxane component (anthraquinone resin) contained in the condensation reaction type resin is preferably 15% by weight or more, and the upper limit is preferably about 70% by weight. By controlling within such a range, a condensation of an adhesive component can be placed between another condensation reaction type resin having an adhesive component and a high contact angle condensation reaction type resin with a peeling component. Since the reactive oxime resins are bonded to each other, the adhesion to the transparent polymer film can be improved, and the coating film can be sufficiently cured, and the solvent present in the photoresist can be sufficiently mechanically and scratch-resistant. Sex.
另外在不妨礙塗膜的機能之範圍內，還可以添加以一黏著劑成分之縮合反應型樹脂以外之樹脂。以一縮合反應型樹脂以外之樹脂，可以舉出例如，熱塑性丙烯樹脂，熱塑性環氧樹脂等等。在全部黏著劑成分中縮合反應型樹脂之比例以70重量%以上程度為下限。Further, in addition to the function of the coating film, a resin other than the condensation reaction type resin of an adhesive component may be added. The resin other than the condensation reaction type resin may, for example, be a thermoplastic propylene resin, a thermoplastic epoxy resin or the like. The ratio of the condensation reaction type resin in all the adhesive components is 70% by weight or more as a lower limit.
以一剝離性成分之縮合反應型矽類樹脂，相對於黏著劑成分100重量份，其上限為40重量份以下，能為20重量份以下更好，其下限為1重量份以上，能為2重量份以上更好。下限設為1重量份以上係因為若少於1重量份的話，將很難獲得剝離效果。另外上限設為40重量份以下係因為若多於40重量份，對於包含在光阻劑中之溶劑將很難獲得充分的機械強度和耐擦傷性，與透明性高分子薄膜之附著性也會惡化，而且即使多添加剝離性成分也不會得到改善。The condensation reaction type oxime resin having a detachable component has an upper limit of 40 parts by weight or less, more preferably 20 parts by weight or less, and the lower limit is 1 part by weight or more, and can be 2, based on 100 parts by weight of the adhesive component. More preferably in parts by weight. The lower limit is set to 1 part by weight or more because if it is less than 1 part by weight, it is difficult to obtain a peeling effect. Further, the upper limit is 40 parts by weight or less, because if it is more than 40 parts by weight, it is difficult to obtain sufficient mechanical strength and scratch resistance for the solvent contained in the photoresist, and adhesion to the transparent polymer film is also It deteriorates and does not improve even if more peeling components are added.
在本發明之表面保護層用組成物中，亦可含有促進與上述高接觸角度縮合反應型矽類樹脂以及低接觸角度縮合反應型樹脂之間的縮合反應之催化劑。以一催化劑，可以使用金屬脂肪酸鹽，金屬醇鹽等等公知的催化劑。具體上，可用錫化合物，鋯化合物，鈦系化合物等等者。The composition for a surface protective layer of the present invention may further contain a catalyst for promoting a condensation reaction with the above-mentioned high contact angle condensation reaction type oxime resin and low contact angle condensation reaction type resin. As the catalyst, a known catalyst such as a metal fatty acid salt, a metal alkoxide or the like can be used. Specifically, a tin compound, a zirconium compound, a titanium compound or the like can be used.
本發明之表面保護薄膜，可藉由縮合反應使各成分之結合，為此能使機械強度與耐擦傷性提高，並減少剝離性成分從塗膜上之脫落，也就是減少剝離性成分往印刷基板上的轉印，以及改善剝離持續性。The surface protective film of the present invention can combine the components by a condensation reaction, thereby improving mechanical strength and scratch resistance, and reducing the peeling of the peeling component from the coating film, that is, reducing the peeling component to the printing. Transfer on the substrate, as well as improved peel retention.
在表面保護層中，為了在表面保護層上形成凹凸，除這些樹脂以外，還可以添加無機顏料和樹脂珠等等微粒子。以一此般微粒子，可以使用碳酸鈣，碳酸鎂，硫酸鋇，矽石，氫氧化鋁，高嶺土，黏土，滑石等無機顏料者，以及丙烯樹脂粒子，聚苯乙烯樹脂粒子，聚胺甲酸脂樹脂粒子，聚乙烯樹脂粒子，苯三聚氰二胺樹脂粒子，環氧樹脂粒子等樹脂珠。這些微粒子之添加量，雖然因微粒子之種類，表面保護層之厚度而異而無法一概而論，不過通常佔構成表面保護層之全固體成分中之0.05重量%到9.5重量%程度之間。另外，這種微粒子之平均粒徑，雖因表面保護層之厚度而異，而無法一概而論，不過通常為0.1μm到10μm之間，最好在0.5μm到5μm之間。這般藉由形成凹凸，可以設置與光阻劑之適當的間隙，使密著曝光時的除氣性變好，進而能防止密著曝光時產生牛頓環。In the surface protective layer, in order to form irregularities on the surface protective layer, fine particles such as inorganic pigments and resin beads may be added in addition to these resins. For such fine particles, inorganic pigments such as calcium carbonate, magnesium carbonate, barium sulfate, vermiculite, aluminum hydroxide, kaolin, clay, talc, and the like, and propylene resin particles, polystyrene resin particles, and polyurethane resin can be used. Resin beads such as particles, polyethylene resin particles, benzene melamine resin particles, and epoxy resin particles. Although the amount of these fine particles added cannot be generalized depending on the type of the fine particles and the thickness of the surface protective layer, it is usually between 0.05% by weight and 9.5% by weight of the total solid content constituting the surface protective layer. Further, the average particle diameter of such fine particles differs depending on the thickness of the surface protective layer, and cannot be generalized, but is usually between 0.1 μm and 10 μm, preferably between 0.5 μm and 5 μm. By forming irregularities as described above, it is possible to provide an appropriate gap with the photoresist to improve the outgassing property during the adhesion exposure, and to prevent the Newton's ring from being generated during the adhesion exposure.
以一表面保護層之厚度，雖沒有特別限定，不過從不讓曝光時光掩膜之解像度低下之觀點來看，以薄者為佳，另外，因反複操作表面保護層之表面硬度，以及密著曝光而導致的表面保護層之削減，初期之剝離性以及剝離性之持續等觀點來看，具體上厚度為0.2μm到5μm之間為佳,最好為0.4μm到2.5μm之間。The thickness of the surface protective layer is not particularly limited, but it is preferably a thinner from the viewpoint of not lowering the resolution of the photomask during exposure, and the surface hardness and adhesion of the surface protective layer are repeatedly operated. The thickness of the surface protective layer due to the exposure, the initial peeling property, and the peeling property are preferably from 0.2 μm to 5 μm, preferably from 0.4 μm to 2.5 μm.
如上所述之表面保護層與黏著層，可因應各構成成分與必要性來搭配其他成分，然後溶解或分散於適當的溶媒後調製塗佈液，並將該塗佈液通過輥塗法，棒塗法，噴塗法，氣刀刮塗法等公知的方法塗敷在透明性高分子薄膜上，乾燥後使用恰當必要的固化方法使其固化來形成。The surface protective layer and the adhesive layer as described above may be combined with other components in accordance with the respective constituents and necessity, and then dissolved or dispersed in a suitable solvent to prepare a coating liquid, and the coating liquid is passed through a roll coating method. A known method such as a coating method, a spray coating method, or an air knife coating method is applied to a transparent polymer film, dried, and then cured by a suitable curing method.
如上所述利用本實施形態，能因藉由黏著層黏貼上想要保護之表面，故可較容易地形成表面保護膜。此外，在保持表面保護膜之膜表面硬度的同時，能使污漬不容易沾上，因此對於光阻劑能維持極高的剝離性。According to the present embodiment as described above, the surface to be protected can be adhered by the adhesive layer, so that the surface protective film can be formed relatively easily. Further, while maintaining the surface hardness of the surface protective film, stains are less likely to be stained, so that extremely high peelability can be maintained for the photoresist.
另外，以一表面保護薄膜，如以上的實施形態所說明般，一般雖皆為具有黏著層者，不過在本發明之表面保護薄膜中，黏著層並非係必須之者，沒有黏著層之薄膜亦包含於本發明中。In addition, a surface protective film, as described in the above embodiments, generally has an adhesive layer, but in the surface protective film of the present invention, the adhesive layer is not essential, and the film without the adhesive layer is also It is included in the present invention.
以下通過實施例進一步說明一下本發明。另外，只要不做特別表示，「份」，「%」以重量為基準。The invention is further illustrated by the following examples. In addition, as long as it is not specifically indicated, "parts" and "%" are based on weight.
將下述組合之表面保護層用塗佈液通過棒塗法塗佈在厚度為6μm之透明性高分子薄膜(REMIRROR：東麗公司)之一表面上，在120℃下加熱5分鐘使其固化，形成厚度約為1μm之表面保護層。並且在另一面上塗佈下述組合之黏著層用塗佈液，乾燥後形成厚度約為2 μ m之黏著層，以製作表面保護薄膜。在黏著層上為方便操作，將與厚度為25μm之聚對苯二甲酸乙二酯離型薄膜(MRB：三菱化學聚酯薄膜公司)貼合。The surface protective layer coating liquid of the following combination was applied to one surface of a transparent polymer film (REMIRROR: Toray Industries, Inc.) having a thickness of 6 μm by a bar coating method, and cured by heating at 120 ° C for 5 minutes. A surface protective layer having a thickness of about 1 μm is formed. Further, a coating liquid for an adhesive layer of the following combination was applied to the other surface, and after drying, an adhesive layer having a thickness of about 2 μm was formed to prepare a surface protective film. For easy handling on the adhesive layer, a polyethylene terephthalate release film (MRB: Mitsubishi Chemical Polyester Film Co., Ltd.) having a thickness of 25 μm was attached.
<表面保護層用塗佈液>．縮合反應型矽類樹脂 4份(KS705F：信越化學工業，接觸角108度：固體成分30%)．縮合反應型矽類樹脂 60份(有機矽烷縮合物：密胺樹脂：醇酸樹脂＝10：3：7，接觸角80度：固體成分30%)．錫系固化催化劑 0.5份．顏料 0.1份(Nipsil SS－15：東曹．矽石)．甲基－乙基甲酮 20份．甲苯 20份<Coating liquid for surface protective layer>. Condensation reaction type terpenoid resin 4 parts (KS705F: Shin-Etsu Chemical Industry, contact angle 108 degrees: solid content 30%). Condensation reaction type terpene resin 60 parts (organic decane condensate: melamine resin: alkyd resin = 10:3:7, contact angle 80 degrees: solid content 30%). Tin-based curing catalyst 0.5 parts. Pigment 0.1 part (Nipsil SS-15: Tosoh. Meteorite). Methyl-ethyl ketone 20 parts. Toluene 20 parts
<黏著層用塗佈液>．丙烯酸酯共聚合物 10份(AKONTACK SCL－200：固體成分40%東亞合成化學)．甲苯 10份．乙酸乙酯 10份<Coating solution for adhesive layer>. Acrylate copolymer 10 parts (AKONTACK SCL-200: solid content 40% East Asian synthetic chemistry). Toluene 10 parts. Ethyl acetate 10 parts
除了將實施例1的表面保護層塗佈液更換成下述之表面保護層塗佈液以外，採用與實施例1之相同方法來製作表面保護薄膜。A surface protective film was produced in the same manner as in Example 1 except that the surface protective layer coating liquid of Example 1 was replaced with the surface protective layer coating liquid described below.
<表面保護層用塗佈液>．縮合反應型矽類樹脂 12份(KS705F：信越化學工業，接觸角108度：固體成分30%)．縮合反應型矽類樹脂 60份(有機矽烷縮合物：密胺樹脂：醇酸樹脂＝10：3：7，接觸角80度：固體成分30%)．錫系固化催化劑 0.5份．顏料 0.1份(Nipsil SS－15：東曹．矽石)．甲基－乙基甲酮 16份．甲苯 16份<Coating liquid for surface protective layer>. Condensation reaction type terpenoid resin 12 parts (KS705F: Shin-Etsu Chemical Industry, contact angle 108 degrees: solid content 30%). Condensation reaction type terpene resin 60 parts (organic decane condensate: melamine resin: alkyd resin = 10:3:7, contact angle 80 degrees: solid content 30%). Tin-based curing catalyst 0.5 parts. Pigment 0.1 part (Nipsil SS-15: Tosoh. Meteorite). Methyl-ethyl ketone 16 parts. Toluene 16 parts
除了將實施例1的表面保護層塗佈液更換成下述之表面保護層塗佈液以外，採用與實施例1之相同方法來製作表面保護薄膜。A surface protective film was produced in the same manner as in Example 1 except that the surface protective layer coating liquid of Example 1 was replaced with the surface protective layer coating liquid described below.
<表面保護層用塗佈液>．縮合反應型矽類樹脂 21份(KS705F：信越化學工業，接觸角108度：固體成分30%)．縮合反應型矽類樹脂 60份(有機矽烷縮合物：密胺樹脂：醇酸樹脂＝10：3：7，接觸角80度：固體成分30%)．錫系固化催化劑 0.5份．顏料 0.1份(Nipsil SS－15：東曹．矽石)．甲基－乙基甲酮 12份．甲苯 12份<Coating liquid for surface protective layer>. Condensation reaction type terpenoid resin 21 parts (KS705F: Shin-Etsu Chemical Industry, contact angle 108 degrees: solid content 30%). Condensation reaction type terpene resin 60 parts (organic decane condensate: melamine resin: alkyd resin = 10:3:7, contact angle 80 degrees: solid content 30%). Tin-based curing catalyst 0.5 parts. Pigment 0.1 part (Nipsil SS-15: Tosoh. Meteorite). Methyl-ethyl ketone 12 parts. Toluene 12 parts
除了將實施例1的表面保護層塗佈液更換成下述之表面保護層塗佈液以外，採用與實施例1之相同方法來製作表面保護薄膜。A surface protective film was produced in the same manner as in Example 1 except that the surface protective layer coating liquid of Example 1 was replaced with the surface protective layer coating liquid described below.
<表面保護層用塗佈液>．加成聚合型有機矽系樹脂 30份(LTC750A：東麗道康寧矽，接觸角100度以上：固體成分30%)．鉑系固化催化劑 0.3份．顏料 0.05份(Nipsil SS－15：東曹．矽石)．甲苯 70份<Coating liquid for surface protective layer>. Addition polymerization type organic lanthanide resin 30 parts (LTC750A: Toray Dow Corning, contact angle 100 degrees or more: solid content 30%). Platinum curing catalyst 0.3 parts. Pigment 0.05 parts (Nipsil SS-15: Tosoh. Meteorite). Toluene 70 parts
除了將實施例1的表面保護層塗佈液更換成下述之表面保護層塗佈液以外，採用與實施例1之相同方法來製作表面保護薄膜。A surface protective film was produced in the same manner as in Example 1 except that the surface protective layer coating liquid of Example 1 was replaced with the surface protective layer coating liquid described below.
<表面保護層用塗佈液>．縮合反應型矽類樹脂 30份(KS705F：信越化學工業，接觸角100度以上)．錫系固化催化劑 0.6份．顏料 0.05份(Nipsil SS－15：東曹．矽石)．甲苯 70份<Coating liquid for surface protective layer>. Condensation reaction type bismuth resin 30 parts (KS705F: Shin-Etsu Chemical Industry, contact angle 100 degrees or more). Tin-based curing catalyst 0.6 parts. Pigment 0.05 parts (Nipsil SS-15: Tosoh. Meteorite). Toluene 70 parts
就實施例1－3，以及比較例1－2所獲得之表面保護薄膜，透過以下試驗，藉著反覆曝光來評價能否使表面保護層持續高剝離性。此外，亦對其是否不受光阻劑中所含有的多價醇等溶劑之侵犯而對光阻劑保持高的剝離性進行評價。此外，就表面保護層之耐擦傷性也進行評價，評價結果如表1所示。With respect to the surface protective films obtained in Examples 1-3 and Comparative Examples 1-2, it was evaluated by the following test whether the surface protective layer could be kept highly peelable by repeated exposure. Further, whether or not the photoresist is invaded by a solvent such as a polyvalent alcohol contained in the photoresist is evaluated, and the high removability of the photoresist is evaluated. Further, the scratch resistance of the surface protective layer was also evaluated, and the evaluation results are shown in Table 1.
<初期剝離性之評價>在有實施例1－3，以及比較例1－2之表面保護薄膜之表面保護層之面上，黏上寬18mm之黏著膠帶(NICHIBAN透明膠No.405：NICHIBAN公司)，用拉伸試驗機(TENSILON HTM－100：東洋Baldwin公司)測定在300mm/min之剝離速度下之180°剝離力。測定結果未滿50g/18mm之者表示為「◎」，50g/18mm~200g/18mm未滿之者表示為「○」，200g/18mm之以上者表示為「×」。<Evaluation of Initial Peelability> Adhesive tape having a width of 18 mm was adhered to the surface protective layer of the surface protective film of Examples 1-3 and Comparative Example 1-2 (NICHIBAN Clear Glue No. 405: NICHIBAN Co., Ltd. The 180° peel force at a peeling speed of 300 mm/min was measured by a tensile tester (TENSILON HTM-100: Toyo Baldwin Co., Ltd.). When the measurement result is less than 50 g/18 mm, it is indicated as "◎", and if it is less than 50 g/18 mm to 200 g/18 mm, it is indicated as "○", and those of 200 g/18 mm or more are indicated as "x".
<反覆曝光時的剝離性之評價>以一光阻劑(感光性樹脂)，使用乙氧化雙酚A二丙烯酸酯(A－BPE4：新中村化學)，於此再添加3重量%作為光聚合起始劑使用的苯乙酮系光游離基聚合起始劑(IRGACURE184：CIBASPECIALTYCHEMICALS公司)，然後用棒塗機將其在聚酯薄上塗成10μm厚以製作試驗片A。讓該試驗片A之感光性樹脂塗佈面，與具有實施例1－3以及比較例1－2之表面保護薄膜的表面保護層之面密著在一起，從具表面保護層之面的背面使用金屬鹵化物燈進行200mJ/cm2 之紫外線曝光後，將試驗片A剝離。同樣的操作進行100回後，在表面保護薄膜之有表面保護層之面上，黏上寬18mm之黏著膠帶(NICHIBAN透明膠No.405：NICHIBAN公司)，用拉伸試驗機(TENSILON HTM－100：東洋BALDWIN公司)測定在300mm/min之剝離速度下之180°剝離力。測定結果未滿50g/18mm之者表示為「◎」，50g/18mm~未滿200g/18mm之者表示為「○」，200g/18mm之以上者表示為「×」。<Evaluation of Peelability at Reversal Exposure> Using a photoresist (photosensitive resin), ethoxylated bisphenol A diacrylate (A-BPE 4: Shin-Nakamura Chemical Co., Ltd.) was used, and 3% by weight was further added thereto as photopolymerization. The acetophenone-based photoradical polymerization initiator (IRGACURE 184: CIBASPECIALTY CHEMICALS) was used as a starter, and then it was coated on a polyester sheet by a bar coater to a thickness of 10 μm to prepare a test piece A. The photosensitive resin-coated surface of the test piece A was adhered to the surface of the surface protective layer having the surface protective films of Examples 1-3 and Comparative Example 1-2, and the back surface of the surface having the surface protective layer was adhered. After the ultraviolet exposure of 200 mJ/cm 2 was performed using a metal halide lamp, the test piece A was peeled off. After the same operation was carried out for 100 times, an adhesive tape having a width of 18 mm (NICHIBAN Clear Glue No. 405: NICHIBAN) was adhered to the surface of the surface protective film with a surface protective layer, and a tensile tester (TENSILON HTM-100) was used. : Toyo BALDWIN Co., Ltd.) The 180° peel force at a peeling speed of 300 mm/min was measured. When the measurement result is less than 50 g/18 mm, it is indicated as "◎", and 50 g/18 mm to less than 200 g/18 mm is indicated as "○", and 200 g/18 mm or more is indicated as "X".
<耐擦傷性評價>將具有實施例1－3以及比較例1－2之表面保護薄膜的表面保護層之面，用含有丙二醇一甲醚之紗布，施與100g/cm2 之載荷的同時，邊進行往復20回之摩擦後，對有表面保護層之面進行觀察。表面保護層上沒有變化發生者表示為「◎」，有擦過痕跡但表面保護層沒有脫落者表示為「○」，表面保護層有些許脫落者表示為「△」，表面保護層有明顯脫落者表示為「×」。<Evaluation of scratch resistance> The surface of the surface protective layer having the surface protective films of Examples 1-3 and Comparative Example 1-2 was applied with a gauze containing propylene glycol monomethyl ether while applying a load of 100 g/cm 2 . After rubbing back and forth for 20 times, the surface having the surface protective layer was observed. If there is no change in the surface protective layer, it is indicated as "◎", and if the surface protective layer is not peeled off, it is indicated as "○", and the surface protective layer is somewhat "OFF", and the surface protective layer is clearly peeled off. Expressed as "X".
實施例1－2，其剝離性成分，黏著劑成分都係通過縮合反應型矽類樹脂來形成表面保護層的，因此進行初期之剝離性，反覆曝光時的剝離性以及耐擦傷性中的任一評價時，都顯示了以一表面保護薄膜所具有足夠之性能。實施例3，和其他實施例一樣具有良好的初期剝離性以及反覆曝光時的剝離性，然而因為和其他實施例相比含有較多的剝離性成分，故其耐擦傷性較弱。In the example 1-2, since the peeling component and the adhesive component are formed into a surface protective layer by a condensation reaction type oxime resin, the initial peelability, the peeling property at the time of repeated exposure, and the scratch resistance are not included. At the time of evaluation, it was shown that a surface protective film had sufficient properties. In the third embodiment, as in the other examples, the initial peeling property and the peeling property at the time of the reverse exposure were good. However, since the peeling component was contained in a larger amount than the other examples, the scratch resistance was weak.
比較例1，因所使用的係被使用在以往的表面保護薄膜上之加成聚合型有機矽系樹脂，為此在進行反覆曝光時的剝離性之評價時，性能明顯低下。In Comparative Example 1, the addition polymerization type organic fluorene-based resin used in the conventional surface protection film was used, and the performance was remarkably lowered when the peeling property at the time of the reverse exposure was evaluated.
比較例2，因只使用以一剝離性成分之縮合反應型矽類樹脂來形成表面保護膜，所以表面保護層的耐擦傷性明顯很弱，表面保護層容易受損，故傷痕易對曝光產生妨礙，不耐使用。In Comparative Example 2, since the surface protective film was formed by using only a condensation-reactive type terpene resin having a releasable component, the scratch resistance of the surface protective layer was remarkably weak, and the surface protective layer was easily damaged, so that the flaw was easily exposed to the exposure. Obstruction, not tolerant use.
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| CN102612665B (en) * | 2009-11-26 | 2014-07-30 | 木本股份有限公司 | Thermosetting protective solution for glass mask, and glass mask |
| TWI500588B (en) * | 2009-12-07 | 2015-09-21 | Kimoto Kk | Protrusion of glass hood with thermal hardening and glass curtain |
| CN104145216A (en) * | 2012-04-19 | 2014-11-12 | 木本股份有限公司 | Heat-curable protective liquid for glass mask and glass mask |
| JP5651259B2 (en) * | 2013-03-25 | 2015-01-07 | 積水ナノコートテクノロジー株式会社 | LAMINATED FILM, FILM ROLL THEREOF, LIGHT TRANSMITTING CONDUCTIVE FILM OBTAINED FROM THE SAME, AND TOUCH PANEL USING THE SAME |
| JP5852998B2 (en) * | 2013-07-29 | 2016-02-09 | 藤森工業株式会社 | Surface protective film and optical component on which it is bonded |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5571569A (en) * | 1994-04-14 | 1996-11-05 | Kabushiki Kaisha Toyoda Jidoshokki Seisakusho | Thin-film forming method |
| US6485838B1 (en) * | 1999-05-21 | 2002-11-26 | Jsr Corporation | Coating composition, and a coated film and glass each having a coating layer comprised thereof |
| TWI287025B (en) * | 2004-08-31 | 2007-09-21 | Nippon Catalytic Chem Ind | Optical sheet form thermoplastic resin molded product |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS61215629A (en) * | 1985-03-22 | 1986-09-25 | Nippon Shokubai Kagaku Kogyo Co Ltd | Surface modifying composition |
| JP3034422B2 (en) * | 1994-04-04 | 2000-04-17 | 積水化学工業株式会社 | Adhesive film for photomask protection |
| JP3400148B2 (en) * | 1994-11-18 | 2003-04-28 | 株式会社豊田自動織機 | Method of forming water-repellent wear-resistant thin film |
| KR100200426B1 (en) * | 1996-08-29 | 1999-06-15 | 한형수 | Forming method of silicon release film |
| JP2000186246A (en) * | 1998-12-21 | 2000-07-04 | Toagosei Co Ltd | Resinous base material with protective coating |
| JP2000328001A (en) | 1999-05-21 | 2000-11-28 | Jsr Corp | Coating composition for film and coating film |
| JP2002214761A (en) * | 2001-01-16 | 2002-07-31 | Dainippon Printing Co Ltd | Photomask for photolithography and method for manufacturing the same |
| JP4891500B2 (en) * | 2001-09-20 | 2012-03-07 | 株式会社きもと | Surface protection film |
| US7179531B2 (en) | 2002-09-12 | 2007-02-20 | Rohm And Haas Company | Polymer particles having select pendant groups and composition prepared therefrom |
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| US5571569A (en) * | 1994-04-14 | 1996-11-05 | Kabushiki Kaisha Toyoda Jidoshokki Seisakusho | Thin-film forming method |
| US6485838B1 (en) * | 1999-05-21 | 2002-11-26 | Jsr Corporation | Coating composition, and a coated film and glass each having a coating layer comprised thereof |
| TWI287025B (en) * | 2004-08-31 | 2007-09-21 | Nippon Catalytic Chem Ind | Optical sheet form thermoplastic resin molded product |
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