1358441 (1) 九、發明說明 【發明所屬之技術領域】 本發明爲關於一種具有脫模性之表面保護膜，以及表 面保護材料（薄膜、薄片），尤其是適合作爲於印刷基板· 之製作等步驟中，將具有黏著性之光阻進行曝光時之原稿 (光罩）的表面之表面保護膜，以及表面保護材料之技術 【先前技術】 一般而言’印刷電路板或樹脂凸板爲將液狀光阻等具 有黏著性之光阻以光罩（曝光用原稿）緊貼曝光的方法製 作。因此，若不在光罩表面施以任何處理時，則於曝光結 束，欲將光罩剝離光阻時，部分光阻將會附著於光罩表面 ，即使經過擦拭仍將殘存於光罩之上，而產生曝光精度低 下的問題。基於上述情事’以往於光罩上之與光阻爲對向 之面’即有設置具有脫模性的表面保護材料，以防止光阻 附著於光罩之技術。 前述光罩用的表面保護材料，例如已揭示有於塑膠薄 膜之一側面上具有脫模性之表面保護膜，另一側具有黏著 層之表面保護材料（參考日本特開平Η 一 7121號公報） 。但即使此表面保護材料，仍無法完全防止光阻附著於表 面保護膜之上’且爲除去這些殘留於表面保護膜之上的光 阻或其他灰塵等’必須定期以洗淨溶劑淸洗（擦拭步驟） 此表面保護膜之表面。因此，對於此表面保護材料，仍有 • 4 - (2) (2)1358441 要求即使於淸洗後亦需能維持防止光阻附著的脫模性。 基於上述理由’已揭示有即使於藉由洗淨溶劑淸洗後 ，亦能維持對於光阻之脫模性的表面保護材料之技術，而 事實上上述之表面保護材料，對於藉由低級醇等的洗淨溶 劑之淸洗可維持充分的脫模性（參考日本特開2000 -273412號公報）。但是近來的光阻之塗佈方式中，爲了提 高量產性而漸漸以噴霧塗佈或簾幕塗佈的方式取代往來之 網版印刷方式。因此光阻中所含有之溶劑的成分或含有量 產生變化’而由光阻中所含之多元醇或其衍生物等組成的 溶劑將逐漸地侵蝕表面保護膜，使得表面保護膜無法充分 維持對於光阻的脫模性。 又’用於光罩之上的表面保護膜除了耐溶劑性的問題 以外’還有因製作印刷電路板等的基礎之基板的通孔等之 凹凸，使得於緊貼曝光時會由凸部施以比平滑部更高的壓 力，而會產生每次重複曝光時逐漸削減表面保護膜的問題 【發明內容】 相對於前述現狀，本發明以提供一種不因洗淨溶劑之 淸洗而侵蝕，且也不因光阻中所含之多元醇或其衍生物等 組成的溶劑所侵蝕，且可對於光阻維持極高的脫模性之表 面保護膜，以及使用此表面保護膜所製造的表面保護材料 爲目的。 又，本發明以提供一種即使因爲每次重複曝光時造成 -5- (4) 1358441 . 對於表面保護材料的適用性以例示作一說明。 本發明之表面保護材料爲，於透明高分子薄膜之一側 面設有表面保護膜’而於另一側面設有黏著層所得者。 而透明高分子薄膜只要對於曝光時所使用的紫外線具 有較闻透光率者即可，例如可使用聚對苯二甲酸乙二醇酯 、聚對苯二甲酸丁二醇酯 '聚萘酸乙二醇酯、聚碳酸酯、 聚乙烯、聚丙烯、聚苯乙烯、三乙酸纖維素、丙烯酸酯' 聚氯乙烯等的具有優良透明性之高分子薄膜。特別是經二 軸延伸之聚對苯二甲酸乙二醇酯薄膜具有優良之機械性強 度、尺寸安定性等而適合使用，適合作爲設有適當的易黏 著層等的透明高分子薄膜。透明高分子薄膜之厚度，因會 影響解析度故一般以較薄者爲佳，但考慮處理的容易性時 ，則厚度的下限以1 ju m以上’較佳爲2 y m以上，更佳 爲4"m以上爲宜’上限以】〇〇μιη以下，較佳爲25//ϊη 以下’更佳爲12#m以下的範圍爲宜。 透明高分子薄膜中一側表面所設之具有脫模性之表面 保護膜爲由硬化性樹脂、可塑性樹脂所構成者，脫模性則 指具有因其表面能量較低而能夠防止光阻的附著，或者是 即使附著後亦能輕易地使其脫模的性質。提供此類脫模性 之方式例如將作爲脫性成分之以往公知的氟化合物或聚砂 氧油、聚砂氧脂、聚砂氧系梳型接枝聚合物、聚砂氧丙烧 酸酯等聚矽氧系化合物所製得之脫模劑與構成表面保護膜 的樹脂混合，或者於構成表面保護膜的樹脂之官能基中導 入表面張力大、接觸角較大的官能基，例如烷基、氟基等 (5)1358441 可顯現脫模性的基而實現》 於選擇以往公知的脫模劑時，較佳爲選擇可與硬化性 樹脂所使用之樹脂可產生交聯之反應性的脫模劑。1358441 (1) The present invention relates to a surface protective film having a release property, and a surface protective material (film, sheet), and particularly suitable for use as a printed substrate. In the step, the surface protective film of the surface of the original (mask) when the photoresist having the adhesiveness is exposed, and the technique of the surface protective material [Prior Art] Generally, the printed circuit board or the resin convex plate is a liquid Photoresistive photoresists such as photoresists are produced by adhering to a mask (exposure original). Therefore, if no treatment is applied to the surface of the mask, when the exposure is finished, when the mask is to be stripped of the photoresist, part of the photoresist will adhere to the surface of the mask, and will remain on the mask even after wiping. The problem of low exposure accuracy is generated. Based on the above-mentioned situation, "the surface which is conventionally opposed to the photoresist on the photomask" is provided with a surface protective material having mold release property to prevent the photoresist from adhering to the photomask. The surface protective material for the above-mentioned photomask, for example, has been disclosed as a surface protective film having a release property on one side of a plastic film, and a surface protective material having an adhesive layer on the other side (refer to Japanese Laid-Open Patent Publication No. 7111). . However, even with this surface protection material, it is impossible to completely prevent the photoresist from adhering to the surface protective film 'and to remove the photoresist or other dust remaining on the surface protective film, etc.' must be periodically washed with a cleaning solvent (wipe Step) The surface of this surface protective film. Therefore, for this surface protection material, there is still a need to maintain the mold release property of preventing the adhesion of the photoresist even after the rinsing. For the above reasons, a technique for maintaining a surface protective material capable of maintaining releasability against a photoresist even after washing with a cleaning solvent has been disclosed, and in fact, the above-mentioned surface protective material is used for a lower alcohol or the like. The washing of the washing solvent can maintain sufficient mold release property (refer to Japanese Laid-Open Patent Publication No. 2000-273412). However, in the recent coating method of photoresist, in order to improve mass productivity, the conventional screen printing method has been replaced by spray coating or curtain coating. Therefore, the solvent or the content of the solvent contained in the photoresist changes, and the solvent composed of the polyol or its derivative contained in the photoresist gradually erodes the surface protective film, so that the surface protective film cannot be sufficiently maintained. Release resistance of the photoresist. Further, in addition to the problem of solvent resistance, the surface protective film for use on the photomask has a concavity and convexity such as a through hole of a substrate on which a printed circuit board or the like is formed, so that the convex portion is applied when the exposure is adhered. With a higher pressure than the smoothing portion, there is a problem that the surface protective film is gradually reduced every time the repeated exposure is performed. SUMMARY OF THE INVENTION The present invention provides an environment which is not eroded by washing with a washing solvent, and A surface protective film which is not eroded by a solvent composed of a polyol or a derivative thereof contained in the photoresist, and which can maintain an extremely high releasability for the photoresist, and surface protection by using the surface protective film Materials for the purpose. Further, the present invention provides an explanation for the applicability of the surface protective material, even if it is caused by -5-(4) 1358441 each time the exposure is repeated. The surface protective material of the present invention is obtained by providing a surface protective film 'on one side of a transparent polymer film and an adhesive layer on the other side. The transparent polymer film may have a light transmittance for ultraviolet rays used for exposure, and for example, polyethylene terephthalate or polybutylene terephthalate 'polynaphthoate B may be used. A polymer film having excellent transparency such as a glycol ester, a polycarbonate, a polyethylene, a polypropylene, a polystyrene, a cellulose triacetate or an acrylate 'polyvinyl chloride. In particular, the polyethylene terephthalate film which is biaxially stretched is excellent in mechanical strength, dimensional stability, etc., and is suitable as a transparent polymer film provided with an appropriate adhesive layer or the like. The thickness of the transparent polymer film is generally thinner because it affects the resolution. However, when the ease of handling is considered, the lower limit of the thickness is preferably 1 μm or more, preferably 2 μm or more, and more preferably 4 & quot More than m is preferably 'upper limit' 〇〇μιη or less, preferably 25//ϊη or less. More preferably, the range of 12#m or less is suitable. The surface protective film having a release property provided on one surface of the transparent polymer film is composed of a curable resin or a plastic resin, and the release property means that the surface energy is low and the adhesion of the photoresist can be prevented. Or it is a property that can be easily released even after attachment. A method of providing such a mold release property is, for example, a conventionally known fluorine compound, polyoxalate oil, polyoxalate, polyxylene comb-type graft polymer, polyoxalate, or the like. The release agent obtained by the polyoxo compound is mixed with the resin constituting the surface protective film, or a functional group having a large surface tension and a large contact angle, such as an alkyl group, is introduced into a functional group of the resin constituting the surface protective film. In the case of selecting a conventionally known release agent, a fluorine-based group or the like (5) 1358441 can be used to obtain a mold release property. In the case of selecting a conventionally known release agent, it is preferred to select a release agent which can be crosslinked with a resin used for the curable resin. Agent.
脫模劑之a有里’於全樹脂固體成分中，上限較佳爲 5重量％以下’更佳爲3重量％以下，下限較佳爲〇.5重 量％以上。將下限設爲0.5重量％以上之原因爲，若小於 〇. 5重量％則不易得到脫模效果。又，將上限設爲5重量 %以下之原因爲’若大於5重量％則脫模劑容易由表面溢 出，且即使大量添加也無法提高效果。 考 硬化性樹脂’例如可使用熱硬化性樹脂、電離放射線 硬化性樹脂等之以往公知的樹脂，但就隨著重複曝光而使 表面保護膜逐漸地削減等問題，以使用物理性磨耗較強之 電離放射線硬化性樹脂爲較佳。又，於電離放射線硬化性 樹脂中’尤以使用有機無機混合樹脂作爲表面保護膜時可 使表面硬度增加、增強其物理性磨耗等而爲更佳。藉由上 述樹脂所構成之表面保護膜，除可賦予表面保護膜表面硬 度外’亦可製得出不易受損之表面保護膜。 熱硬化性樹脂’例如可使用三聚氰胺系、環氧系、氨 基醇酸系 '氨基甲酸乙酯系、丙烯酸系、聚酯系、苯酚系 等之交聯性樹脂及其混合物所選出之一種以上的樹脂。 又’電離放射線硬化性樹脂，可使用會因電離放射線 (紫外線或者電子線）的照射而交聯硬化之環氧系丙烯酸 醋、聚酯系丙烯酸酯、聚氨基甲酸乙酯系丙烯酸酯、多元 醇系丙烯酸酯等之具有丙烯酸基的樹脂以及聚硫代多烯樹 -8- (6) 1358441 • · 脂等之光聚合性預聚物。其可單獨使用，或加入單官能丙 烧酸基單體等光聚合物單體以外’也可以添加如乙醯苯酮 、一苯甲酮、米希勒酮等之光聚合引發劑或紫外線增感劑 〇 有機無機混合樹脂，可使用有機單體或有機聚合物與 ’如烷基矽氧烷等之含有無機骨架之化合物經自由基共聚 ,所得的產物，以及將如烷氧基矽烷等無機官能基作爲側鎖 結合於有機聚合物，其後將其再予交聯之樹脂。 其次’可塑性樹脂，於表面保護膜硬化後之表面保護 膜逐漸產生削減之情形，爲使塗膜中之脫模性成分容易再 配向之目的而混入者》 雖然並無證明因實施上述事項而可持續維持脫模性的 證據，但於表面保護膜之表面形成配向之脫模性成分，於 表面保護膜被逐漸削減時，若僅以硬化性樹脂作爲表面保 護膜之構成成份時，則因保護膜的構成較爲緊密，所以無 法再形成配向’而導致於無法維持脫模性。相反地，藉由 硬化性樹脂與乙嫌基系高分子化合物作爲構成成分時，表 面保護膜之表面形成配向之脫模性成分，即使表面保護膜 被逐漸削減時，仍可以再形成配向，而使新配向之脫模性 成分產生脫模性，進而得以繼續維持脫模性。 上述可塑性樹脂例如含有乙烯基系高分子化合物作爲 構成成分之可塑性樹脂。乙烯基系高分子化合物爲含有乙 烯基的單體之聚合物或共聚物，具體而言，例如可由聚乙 酸乙烯基樹脂、聚乙烯丁縮醛樹脂、苯乙烯、丁二烧、聚 -9- (7) 1358441 . · 乙烯、聚丙烯、丙烯腈、氯乙烯、聚乙烯醇中任選一種以 上使用。就作爲表面保護膜時之耐溶劑性或膜的硬度、脫 模性成分形成再配向之難易度等觀點而言，以使用聚乙酸 乙烯基樹脂及/或聚乙烯丁縮醛樹脂《乙烯基系高分子化 合物以佔可塑性樹脂之50重量％以上爲佳，較佳爲7〇重 量％以上，更佳爲90重量％以上。 可塑性樹脂之混合比例，於全樹脂固體成分中，上限 以10重量％以下爲佳，更佳爲7重量％以下。下限以1 重量％以上爲佳，較佳爲2重量％以上，更佳爲4重量％ 以上。其原因爲全樹脂成分中之可塑性樹脂所佔比例越大 時’越不容易維持表面保護膜之硬度，故表面保護膜越容 易因物理性磨耗而被削減，因而可塑性樹脂所佔比例越小 時越不容易產生脫模性之效果。 表面保護膜之硬度’雖隨被層合物而異，一般以依 JIS K5400: 1990中之錐體磨耗硬度實驗前後的霧化値之 差（即，錐體磨耗硬度實驗後之霧化値減去錐體磨耗硬度 實驗前之霧化値的値，以下簡稱爲「△ Η」）以未達25爲 佳’更佳爲未達20。又於不阻礙脫模性成分再配向的範圍 時’以5以上爲佳’更佳爲1〇以上。上限於上述範圍時 ’即使重複進行曝光也不易使表面保護膜被削減。藉由上 述步驟’可在抑制因表面保護膜的物理性削減而降低表面 保護膜的脫模性的同時’抑制霧化値之上升，並防止解像 力的降低。又’因表面保護膜變爲不易受損，而可提高表 面保護膜的耐久性’進而可大幅增加可曝光的次數。 -10- (8) 1358441 . · 表面保護膜除上述樹脂以及脫模性成分以外，在不妨 礙前述效果的範圍內也可摻入其他樹脂。若在不妨礙前述 效果的範圍內，例如可使用含有滑劑、微粒子、螢光增白 劑、顔料、防靜電劑、難燃劑、抗菌劑、防霉劑、抗氧化 劑、可塑劑、平滑劑、流動調整劑、消泡劑、分散劑等各 種的添加劑。 設在透明高分子薄膜之另一側的黏著層，可使用二般 的丙烯酸系黏著劑、橡膠系黏著劑等之公知的透明黏著劑 。本發明之表面保護材料於用於保護畫像等時，黏著劑以 透明且本身具有較高的耐候性者爲佳。上述之黏著劑以氨 基甲酸乙酯交聯性或環氧交聯性之高分子量的丙烯酸系黏 著劑較爲合適。又，亦可使用具有防靜電等性能的黏著劑 。黏著劑的厚度，於不妨礙透明性（解像度），且能夠得 到適度的黏著性時，以0 · 5 μ m〜3 0 # m爲佳，較佳爲1 //m〜ΙΟμηι，更佳爲2/im〜4//m的範圍。又，黏著層爲 避免因其黏著性而導致處理該表面保護材料之容易性降低 ’可適當的於其表面貼以施有脫模處理之脫模薄膜。 上述之表面保護膜與黏著層，可配合各種的構成成分 或必要時所需配合之其他成分，使其溶解或分散於適當的 溶媒以調製塗佈液，並將該塗佈液以滾筒塗佈法、條狀塗 佈法、噴霧塗佈法 '氣刀塗佈法等公知的方法塗佈至透明 高分子薄膜上後，再採取適當的硬化方法使其硬化。 依上述本實施形態，於欲保護其表面的物體上，可藉 著貼附黏著層，則容易形成表面保護膜。 -11 - (9) (9)1358441 因此’可防止於印刷製版步驟中，原版、廣告、標誌 等各種印刷方法所製成之顯示物、照片等的表面變髒或者 受損。特別是，保有脫模性之表面保護膜也不爲溶劑所侵 蝕，即使於表面保護膜逐漸削減後，也能在維持表面保護 膜硬度的同時，而維持脫模性，而可使污垢不.易附著。 以上爲對本發明的實施形態的說明。於本發明的形態 中’爲以具有脫模性之表面保護層作爲表面保護材料的例 示說明’但適用於本發明之表面保護膜並非僅限定於此， 也可適用於複印用的表面保護膜。在此情況下，於具有脫 模性之基材上’可將上述表面保護膜以及黏著層依此順序 形成’再將表面保護膜藉由黏著層複印至被複印材料。又 ’也可直接將表面保護膜設於光罩上。 【實施方式】 以下，將說明本發明之實施例。其中「份」、「％」 等若無特別指定下，則指重量基準。 〔實施例一〕 於厚m之透明禹分子薄膜（魯米拉··東雷社）之 —側表面上’以條狀塗佈法塗佈具有下記組成之表面保護 膜用塗佈液，並使之乾燥’再藉由高壓水銀燈以紫外線照 射1〜2秒使之硬化，而形成膜厚約的表面保護膜。 又’於另一側表面塗佈具有下記組成之黏著層用塗佈液， 並使之乾燥’以形成厚約2//m之黏著層，而製成表面保 -12- (10) 1358441 .. 護材料。處理上，於黏著層上貼合厚25//m之聚對苯二甲 酸乙二醇酯脫模薄膜（MRB :三菱化學聚酯薄膜公司）。 又，脫模性成分則使用具有與電離放射性有機無機混合樹 脂的具有反應性之聚砂氧丙烧酸酯脫模劑。 <表面保護膜用塗佈液> •有機無機混合樹脂 3.8份 (迪索萊特7501 :固體成分50%、JSR公司） •聚矽氧烷丙烯酸酯脫模劑 〇.〇2份 •聚乙酸乙烯樹脂 〇」4份 (高塞尼爾M— 70 - Z4:固體成分70%、日本合成公司） •甲基乙基甲酮 3.0份 •異丙醇 3 · 0份 <黏著層用塗佈液> •丙稀酸酯共聚物 10.0份 (阿空塔客SCL- 2 00:固體成分40%、東亞合成化學公司） •甲苯 10_0份 •乙酸乙酯 10.0份 〔實施例二〕 於實施例一中，除了以具有下記組成之表面保護膜用 塗佈液取代原有表面保護膜用塗佈液以外，其他均依實施 例—之相同方法製得表面保護材料。 -13- (11) 1358441 <表面保護膜用塗佈液> •有機無機混合樹脂 3.8份 (迪索萊特7501:固體成分50%、JSR公司） •聚矽氧丙烯酸酯脫模劑. 〇.〇2份 •聚乙烯醇縮丁醛樹脂 0.1份The a part of the mold release agent is in the whole resin solid content, and the upper limit is preferably 5% by weight or less, more preferably 3% by weight or less, and the lower limit is preferably 5% by weight or more. The reason why the lower limit is made 0.5% by weight or more is that if it is less than 5% by weight, the release effect is not easily obtained. Further, the reason why the upper limit is made 5% by weight or less is that if it is more than 5% by weight, the release agent is likely to overflow from the surface, and the effect cannot be improved even if it is added in a large amount. For example, a conventionally known resin such as a thermosetting resin or an ionizing radiation curable resin can be used. However, the surface protective film is gradually reduced by repeated exposure, and physical wear is strongly used. An ionizing radiation curable resin is preferred. Further, in the ionizing radiation curable resin, it is more preferable to use an organic-inorganic hybrid resin as the surface protective film to increase the surface hardness and enhance the physical abrasion. By the surface protective film composed of the above resin, in addition to the surface hardness of the surface protective film, a surface protective film which is not easily damaged can be obtained. For the thermosetting resin, for example, one or more selected from the group consisting of a melamine-based, an epoxy-based, an aminoalkyric acid-urethane-based, an acrylic-based, a polyester-based, a phenol-based crosslinkable resin, and a mixture thereof can be used. Resin. Further, 'ionizing radiation curable resin, epoxy acrylate, polyester acrylate, polyurethane acrylate, or polyol which is crosslinked and hardened by irradiation with ionizing radiation (ultraviolet rays or electron beams) can be used. It is an acryl-based resin such as acrylate, and a photopolymerizable prepolymer such as polythiopolyene-8-(6) 1358441 • lipid. It may be used alone or in addition to a photopolymer monomer such as a monofunctional propyl sulphonate monomer. It may also be added with a photopolymerization initiator such as acetophenone, benzophenone or micholone or ultraviolet light. Sensible 〇 organic-inorganic hybrid resin, which can be obtained by radical copolymerization of an organic monomer or an organic polymer with a compound containing an inorganic skeleton such as an alkyl siloxane or the like, and an inorganic substance such as an alkoxy decane. The functional group is bonded as a side lock to the organic polymer, which is then re-crosslinked. In the case of the plastic resin, the surface protective film is gradually reduced after the surface protective film is cured, and it is mixed for the purpose of re-aligning the release component in the coating film. Evidence of the mold release property is maintained, but the release-removing component is formed on the surface of the surface protective film. When the surface protective film is gradually reduced, if only the curable resin is used as a component of the surface protective film, protection is caused. Since the composition of the film is relatively tight, the alignment cannot be formed again, and the mold release property cannot be maintained. On the other hand, when the curable resin and the B-based polymer compound are used as the constituent components, the surface of the surface protective film forms an alignment releasing component, and even if the surface protective film is gradually reduced, the alignment can be further formed. The releasability of the release component of the new alignment is released, and the release property is maintained. The above-mentioned plastic resin is, for example, a plastic resin containing a vinyl polymer compound as a constituent component. The vinyl polymer compound is a polymer or copolymer of a vinyl group-containing monomer, and specifically, for example, a polyvinyl acetate resin, a polyvinyl butyral resin, styrene, butyl bromide, poly-9- (7) 1358441 . • Any one or more of ethylene, polypropylene, acrylonitrile, vinyl chloride, and polyvinyl alcohol. The polyvinyl acetate resin and/or the polyvinyl butyral resin "vinyl type" is used in view of the solvent resistance of the surface protective film, the hardness of the film, and the ease with which the release component forms realignment. The polymer compound is preferably 50% by weight or more, preferably 7% by weight or more, and more preferably 90% by weight or more. The mixing ratio of the plastic resin is preferably 10% by weight or less, and more preferably 7% by weight or less, based on the total solid content of the resin. The lower limit is preferably 1% by weight or more, preferably 2% by weight or more, and more preferably 4% by weight or more. The reason is that the larger the proportion of the plastic resin in the total resin component is, the more difficult it is to maintain the hardness of the surface protective film. Therefore, the surface protective film is more likely to be reduced by physical abrasion, so that the proportion of the plastic resin is smaller. It is not easy to produce the effect of mold release. Although the hardness of the surface protective film varies depending on the laminate, it is generally the difference between the atomization enthalpy before and after the cone abrasion hardness test in JIS K5400: 1990 (that is, the atomization reduction after the cone abrasion hardness test) The enthalpy of the atomization enthalpy before the cone wear hardness test, hereinafter referred to as "△ Η", is preferably less than 25's more preferably less than 20. Further, when it is not inhibited from re-alignment of the release component, it is preferably 5 or more, more preferably 1 or more. When the above range is limited to the above, it is difficult to reduce the surface protective film even if the exposure is repeated. According to the above step, it is possible to suppress the increase in the atomization enthalpy while suppressing the decrease in the release property of the surface protective film due to the physical reduction of the surface protective film, and to prevent the decrease in the resolution. Further, since the surface protective film is less likely to be damaged, the durability of the surface protective film can be improved, and the number of times of exposure can be greatly increased. -10- (8) 1358441 . · In addition to the above-mentioned resin and mold release component, the surface protective film may be blended with other resins insofar as the above effects are not impaired. If it does not hinder the aforementioned effects, for example, a lubricant, a microparticle, a fluorescent whitening agent, a pigment, an antistatic agent, a flame retardant, an antibacterial agent, an antifungal agent, an antioxidant, a plasticizer, a smoothing agent, or the like may be used. Various additives such as a flow regulator, an antifoaming agent, and a dispersing agent. As the adhesive layer provided on the other side of the transparent polymer film, a known transparent adhesive such as a two-dimensional acrylic adhesive or a rubber-based adhesive can be used. When the surface protective material of the present invention is used for protecting a portrait or the like, the adhesive is preferably transparent and has high weather resistance. The above-mentioned adhesive is preferably an acrylic adhesive having a high molecular weight cross-linking property or an epoxy cross-linking property. Further, an adhesive having an antistatic property or the like can also be used. The thickness of the adhesive is preferably from 0. 5 μ m to 3 0 # m, preferably from 1 //m to ΙΟμηι, without hindering transparency (resolution) and obtaining moderate adhesion. 2 / im ~ 4 / / m range. Further, the adhesive layer is designed to prevent the ease of handling the surface protective material from being lowered due to its adhesiveness. A release film having a release treatment can be suitably applied to the surface thereof. The surface protective film and the adhesive layer described above may be mixed with various constituent components or other components which are required to be mixed, if necessary, dissolved or dispersed in a suitable solvent to prepare a coating liquid, and the coating liquid is applied by a roller. A known method such as a method, a strip coating method, or a spray coating method, an air knife coating method, is applied to a transparent polymer film, and then cured by an appropriate curing method. According to the above embodiment, the surface protective film can be easily formed by attaching the adhesive layer to the object to be protected. -11 - (9) (9) 1394441 Therefore, it is possible to prevent the surface of the display, photographs, etc. made by various printing methods such as the original, advertisement, and logo from being dirty or damaged during the printing and plate making process. In particular, the surface protective film that retains the release property is not eroded by the solvent, and even after the surface protective film is gradually reduced, the mold release property can be maintained while maintaining the mold release film hardness, and the soil can be prevented. Easy to attach. The above is the description of the embodiments of the present invention. In the embodiment of the present invention, 'the surface protective layer having the mold release property is exemplified as the surface protective material'. However, the surface protective film to which the present invention is applied is not limited thereto, and is also applicable to a surface protective film for copying. . In this case, the surface protective film and the adhesive layer may be formed in this order on the substrate having mold release property, and the surface protective film may be copied to the material to be copied by the adhesive layer. Moreover, the surface protective film can also be directly disposed on the reticle. [Embodiment] Hereinafter, an embodiment of the present invention will be described. Where "parts", "%", etc., unless otherwise specified, refers to the weight basis. [Example 1] A coating liquid for a surface protective film having the following composition was applied by a strip coating method on a side surface of a transparent yttrium molecular film (Rumila·Donglei) having a thickness of m, and It is dried and then cured by ultraviolet light irradiation for 1 to 2 seconds by a high pressure mercury lamp to form a surface protective film having a film thickness of about 100 Å. Further, a coating liquid for an adhesive layer having the following composition was applied to the other side surface and dried to form an adhesive layer having a thickness of about 2/m, and the surface was made into a protective layer of -12-(10) 1358441. . Protective materials. For the treatment, a polyethylene terephthalate release film (MRB: Mitsubishi Chemical Polyester Film Co., Ltd.) having a thickness of 25/m was attached to the adhesive layer. Further, as the release component, a reactive polyoxalate-free mold release agent having an ionized radioactive organic-inorganic mixed resin is used. <Coating liquid for surface protective film> • 3.8 parts of organic-inorganic hybrid resin (Disolet 7501: solid content 50%, JSR) • Polyoxyalkylene acrylate release agent 〇. 2 parts • Polyacetic acid 4 parts of vinyl ruthenium (Germanil M-70-Z4: 70% solid content, Nippon Synthetic Co., Ltd.) • Methyl ethyl ketone 3.0 parts • Isopropyl alcohol 3 · 0 parts <Adhesive coating Liquid > • 10.0 parts of acrylate copolymer (Aktatta SCL-2: 00: solid content 40%, East Asian Synthetic Chemical Co., Ltd.) • Toluene 10_0 parts • Ethyl acetate 10.0 parts [Example 2] In the examples In the first place, a surface protective material was obtained in the same manner as in Example except that the coating liquid for a surface protective film having the following composition was replaced with a coating liquid for a surface protective film having the following composition. -13- (11) 1358441 <Coating solution for surface protective film> • 3.8 parts of organic-inorganic hybrid resin (Disolet 7501: solid content 50%, JSR) • Polyoxy acrylate release agent. 〇 .2 parts • polyvinyl butyral resin 0.1 parts
(艾斯雷客BL— 1 :固體成分100%、積水化學工業公司） •甲基乙基甲酮 2.9份 •異丙醇 3.0份 〔實施例三〕 於實施例一中，除了以具有下記組成之表面保護膜用 塗佈液取代原有表面保護膜用塗佈液以外，其他均依實施 例一之相同方法製得表面保護材料。(Aisleyke BL-1: 100% solid content, Sekisui Chemical Industry Co., Ltd.) • 2.9 parts of methyl ethyl ketone • 3.0 parts of isopropyl alcohol [Example 3] In the first embodiment, except that it has the following composition A surface protective material was obtained in the same manner as in Example 1 except that the coating liquid for a surface protective film was used instead of the coating liquid for a surface protective film.
<表面保護膜用塗佈液> •有機無機混合樹脂 3.88份 (迪索萊特7501 :固體成分50%、JSR公司） •聚矽氧丙烯酸酯脫模劑 0.02份 •聚乙酸乙烯樹脂 0.09份 (高塞尼爾M-70-Z4:固體成分70% '日本合成公司） •甲基乙基酮 3 . 〇份 •異丙醇 3 · 〇份 -14- (12) (12)1358441 〔實施例四〕 於實施例一中，除了以具有下記組成之表面保護膜用 塗佈液取代原有表面保護膜用塗佈液以外，其他均依實施 例一之相同方法製得表面保護材料。 <表面保護膜用塗佈液> •有機無機混合樹脂 3 6份 (迪索萊特7501 :固體成分50%、JSR公司） •聚矽氧丙烯酸酯脫模劑 0.02份 •聚乙酸乙烯樹脂 0.29份 (咼塞尼爾M-70-Z4:固體成分70%、日本合成公司） •甲基乙基酮 3.〇份 •異丙醇 3 1沿 〔比較例一〕 於實施例一中’除了自表面保護膜塗佈液中除去聚乙 酸乙烯樹脂，並將有機無機混合樹脂改爲4.〇份以外，其 他均依實施例一之相同方法製得表面保護材料。 〔比較例二〕 於實施例一中’除了將表面保護膜用塗佈液中之聚乙 酸乙烯樹脂以丙烯酸樹脂（LMS-55:固體成分40%、三 菱化學公司）0.25份取代以外，其他均依實施例一之相同 方法製得表面保護材料。 -15- (13) (13)1358441 〔比較例三〕 於實施例一中’除了將表面保護膜用塗佈液中之聚乙 酸乙烯樹脂以聚酯樹脂（ER— 55:固體成分40%、大成 化工公司）0.25份取代以外，其他均依實施例一之相同方 法製得表面保護材料。 對於由實施例以及比較例得到之表面保護材料，以下 述實驗並評估其於進行重複曝光而使表面保護膜受到逐漸 削減的物理性磨耗之後，是否仍然能維持其高脫模性。又 ，同時評估其是否能不被光阻中所含之多元醇等溶劑所侵 蝕，並對光阻可維持較高的脫模性，又，評估表面保護膜 對重複曝光的耐磨耗性。其結果如表一所示。 (1 )初期脫模性之評估 於實施例1〜4、以及比較例1〜3中的表面保護材料 之具有表面保護膜之一側面貼付黏著膠布（尼特聚酯31b :日東電工公司），再以拉伸試驗機（TENSILON HTM — 1〇〇 :東洋波爾特維恩公司）測定於剝離速度3 00mm/ min 中之180 剝離力，並進行評估。評估方式爲，以剝離力 未達 20g/50mm者爲「◎」，介於 20g/50mm〜30g/ 50mm中者爲「〇」。 (2 )磨耗實驗後之脫模性的評估 磨耗實驗爲將實施例1〜4、以及比較例1〜3中的表 -16- (14) (14)1358441<Coating liquid for surface protective film> • 3.88 parts of organic-inorganic mixed resin (Disolelite 7501: solid content 50%, JSR) • Polyoxyethylene acrylate release agent 0.02 parts • Polyvinyl acetate resin 0.09 parts (Gausner M-70-Z4: solid component 70% 'Japan Synthetic Company') • Methyl ethyl ketone 3. 〇 • • Isopropyl alcohol 3 · 〇份-14- (12) (12) 1358441 [Implementation (Example 4) A surface protective material was obtained in the same manner as in Example 1 except that the coating liquid for a surface protective film having the composition of the surface protective film was replaced with the coating liquid for the surface protective film having the following composition. <Coating liquid for surface protective film> • 36 parts of organic-inorganic mixed resin (Disolet 7501: solid content 50%, JSR) • Polyoxypropylene acrylate release agent 0.02 parts • Polyvinyl acetate resin 0.29 Parts (咼塞尼尔 M-70-Z4: solid content 70%, Japan Synthetic Company) • Methyl ethyl ketone 3. 〇 part • Isopropyl alcohol 3 1 along [Comparative Example 1] In Example 1 A surface protective material was obtained in the same manner as in Example 1 except that the polyvinyl acetate resin was removed from the surface protective film coating liquid, and the organic-inorganic mixed resin was changed to 4. [Comparative Example 2] In the first embodiment, except that the polyvinyl acetate resin in the coating liquid for a surface protective film was replaced with 0.25 parts of an acrylic resin (LMS-55: solid content 40%, Mitsubishi Chemical Corporation), A surface protective material was obtained in the same manner as in Example 1. -15- (13) (13) 1394441 [Comparative Example 3] In the first embodiment, except that the polyvinyl acetate resin in the coating liquid for a surface protective film was used as a polyester resin (ER-55: solid content 40%, A surface protective material was obtained in the same manner as in Example 1 except that 0.25 parts of the Dacheng Chemical Company was substituted. With respect to the surface protective materials obtained in the examples and the comparative examples, the following experiment was conducted to evaluate whether or not the high mold release property can be maintained after the surface exposure film is subjected to repeated physical wear by repeated exposure. Further, it was evaluated whether it was not corroded by a solvent such as a polyol contained in the photoresist, and the mold release property was maintained, and the abrasion resistance of the surface protective film to repeated exposure was evaluated. The results are shown in Table 1. (1) Evaluation of initial mold release property Adhesive tape (Nite Polyester 31b: Nitto Denko Co., Ltd.) was attached to one side of the surface protective film of the surface protective materials of Examples 1 to 4 and Comparative Examples 1 to 3, Further, a 180 peeling force at a peeling speed of 300 mm/min was measured by a tensile tester (TENSILON HTM-1: Toyo Port Wien) and evaluated. The evaluation method is "◎" for those with a peeling force of less than 20g/50mm, and "〇" for those between 20g/50mm~30g/50mm. (2) Evaluation of mold release property after abrasion test The abrasion test was the same as in Examples 1 to 4 and Comparative Examples 1 to 3 -16-(14) (14) 1358441
面保護材料之具有表面保護膜之一側，使用加入300g荷 重的鋼絲棉（#〇〇〇〇 )，將進行50次磨耗步驟後之脫模性 進行與上述初期脫模性相同的測定。評估方式爲剝離力未 達初期測定値2倍者爲「◎ j ，2倍以上未達3倍者爲「 O j ，3倍以上未達4倍者爲「△」，4倍以上者爲「X (3 )耐溶劑性評估 將實施例1〜4、以及比較例1〜3中的表面保護材料 浸泡於丙二醇甲基乙醚中2小時後，將所得之表面保護材 料之具有表面保護膜之一側的脫模性進行與上述初期脫模 性相同的測定。評估方式爲剝離力未達初期測定値2倍者 爲「◎」，2倍以上未達3倍者爲「〇」，3倍以上未達4 倍者爲「△」，4倍以上者爲「X」。 (4 )耐磨耗性的評估 將實施例1〜4、以及比較例1〜3中的表面保護材料 之阻隔膜剝離，再貼合於聚對苯二甲酸乙二醇酯薄膜 188//m)後，依據JIS K5400: 1990基準，於表面保護材 料之具有保護膜之一側面進行磨耗輪CS — 10F、荷重5〇〇g 、旋轉速度7〇rpm、旋轉數]〇〇次的錐體磨耗實驗，並以 實驗後之霧化値減去實驗前之霧化値的値作爲△ Η。又， 霧化値爲以霧化値儀（NDH2000 :日本電飾公司）、依 •TISK7I 3 6 : 2000基準進行測定。評估方式爲以△ η未達5 -17- (16)1358441 劑配向性的效果較少’故脫模維持性相較於實施例1、實 施例2而言，則顯示出較差之結果。 又，實施例4之表面保護材料’雖然於耐磨耗性的評 估與實施例〗、實施例2爲相同程度，但因聚乙酸乙烯樹 脂之含量較多’較易造成物理性磨耗，故脫模維持性相較 於實施例1、實施例2而言’則顯示出較差之結果。The surface protective material had one side of the surface protective film, and the release property after the 50-time abrasion step was carried out using the steel wool (#〇〇〇〇) to which 300 g of the load was applied, and the same measurement as the initial mold release property was carried out. The evaluation method is that the peeling force is less than 2 times of the initial measurement, which is "◎ j, 2 times or more is less than 3 times, "O j , 3 times or more is less than 4 times, "△", and 4 times or more is " X (3) Solvent Resistance Evaluation After the surface protective materials of Examples 1 to 4 and Comparative Examples 1 to 3 were immersed in propylene glycol methyl ether for 2 hours, the obtained surface protective material was provided with one of the surface protective films. The mold release property of the side is the same as the above-mentioned initial mold release property. The evaluation method is that the peeling force is less than the initial measurement 値 2 times, it is "◎", and when the peeling force is less than 3 times, it is "〇", 3 times or more. Those who have not reached 4 times are "△", and those who are 4 times or more are "X". (4) Evaluation of abrasion resistance The barrier films of the surface protective materials of Examples 1 to 4 and Comparative Examples 1 to 3 were peeled off, and then bonded to a polyethylene terephthalate film 188 / / m After that, according to the JIS K5400: 1990 standard, the wear of the wear wheel CS-10F, the load of 5〇〇g, the rotational speed of 7〇rpm, and the number of revolutions of the surface protection material on one side of the protective film The experiment was carried out, and the enthalpy of the atomization enthalpy before the experiment was subtracted from the atomization enthalpy after the experiment as Δ Η. Further, the atomization crucible was measured by a nebulizer (NDH2000: Nippon Denshi Co., Ltd.) and a TISK7I 3 6 : 2000 standard. The evaluation method was that the effect of Δ η was less than 5 -17-(16)1358441 agent alignment was less. Therefore, the mold release maintenance was inferior to that of Example 1 and Example 2, and showed poor results. Further, the surface protective material of the fourth embodiment has the same degree of evaluation of the abrasion resistance as in the examples and the second embodiment, but the content of the polyvinyl acetate resin is more likely to cause physical abrasion. The mold maintainability showed a poor result compared to Example 1 and Example 2.
另一方面，比較例1之表面保護材料，雖然因不含可 塑性樹脂，使得表面保護膜的結構較爲緊密，而顯示出良 好的耐溶劑性及耐磨耗性，但於表面保護膜被逐漸侵蝕時 ，脫模性成分不易產生再配向，而使得脫模維持性較差。 又，比較例2、比較例3之表面保護材料，因不是以 乙烯基系高分子化合物作爲可塑性樹脂，所以雖然有良好 耐溶劑性，但因表面保護膜被逐漸侵蝕時，脫模性成分不 易產生再配向，而使得脫模維持性較差。On the other hand, in the surface protective material of Comparative Example 1, although the structure of the surface protective film was relatively tight due to the absence of the plastic resin, and the solvent resistance and abrasion resistance were exhibited, the surface protective film was gradually formed. When eroded, the release component is less likely to realign, and the release maintainability is poor. Further, in the surface protective materials of Comparative Example 2 and Comparative Example 3, since the vinyl polymer compound is not used as the plastic resin, although the solvent resistance is good, when the surface protective film is gradually eroded, the release component is not easily obtained. Realignment is produced, resulting in poor release maintenance.
又’於實施例'比較例中之表面保護材料皆顯示出良 好的耐溶劑性。 -19-Further, the surface protective materials in the comparative examples of the examples showed good solvent resistance. -19-