TWI579354B - Mask mask - Google Patents

Mask mask Download PDF

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Publication number
TWI579354B
TWI579354B TW099139404A TW99139404A TWI579354B TW I579354 B TWI579354 B TW I579354B TW 099139404 A TW099139404 A TW 099139404A TW 99139404 A TW99139404 A TW 99139404A TW I579354 B TWI579354 B TW I579354B
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Taiwan
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weight
adhesive
film
meth
alkyl
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TW099139404A
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Chinese (zh)
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TW201130937A (en
Inventor
Kouhei Yano
Daiki Yamashita
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Asahi Kasei E-Materials Corp
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Priority claimed from JP2009263118A external-priority patent/JP5319500B2/en
Priority claimed from JP2009263119A external-priority patent/JP5319501B2/en
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Publication of TW201130937A publication Critical patent/TW201130937A/en
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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
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/62—Pellicles, e.g. pellicle assemblies, e.g. having membrane on support frame; Preparation thereof
    • 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
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/66—Containers specially adapted for masks, mask blanks or pellicles; Preparation thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0274—Photolithographic processes

Description

光罩護膜Photomask

本發明係關於一種製造LSI(large scale integration，大型積體電路)、超LSI等半導體裝置或液晶顯示板等時，為了防止異物附著於光罩而使用的微影用光罩護膜。尤其是關於一種使用需要高解像度之曝光所使用之準分子雷射的微影用光罩護膜。尤佳為關於一種200 nm以下之紫外光曝光所使用之微影用光罩護膜。In the case of manufacturing a semiconductor device such as an LSI (large scale integrated circuit) or a super LSI, or a liquid crystal display panel, the present invention relates to a photomask protective film used for preventing foreign matter from adhering to a photomask. In particular, it relates to a lithographic mask for a lithography using a pseudo-molecular laser used for exposure requiring high resolution. Optima is a lithographic mask for lithography used for exposure to ultraviolet light below 200 nm.

於半導體製造之光微影步驟中，為了於晶圓上形成與積體電路對應之光阻圖案，目前係使用步進機(縮小投影曝光裝置)等半導體製造裝置。光罩護膜係於具有框形狀之光罩護膜框之一端面鋪設有透明薄膜者，可防止因形成電路圖案而導致異物直接附著於光罩上的情況。因此，即便假設光微影步驟中有異物附著於光罩護膜上，由於該等異物於塗佈有光阻之晶圓上不會成像，因而可防止由異物之像引起的半導體積體電路之短路或斷線等，可提高光微影步驟之製造良率。In the photolithography step of semiconductor manufacturing, in order to form a photoresist pattern corresponding to an integrated circuit on a wafer, a semiconductor manufacturing apparatus such as a stepper (reduced projection exposure apparatus) is currently used. The mask film is provided with a transparent film on one end surface of the mask film frame having a frame shape, and it is possible to prevent foreign matter from directly adhering to the mask due to the formation of the circuit pattern. Therefore, even if foreign matter adheres to the mask film in the photolithography step, since the foreign matter is not imaged on the wafer coated with the photoresist, the semiconductor integrated circuit caused by the image of the foreign matter can be prevented. Short circuit or disconnection, etc., can improve the manufacturing yield of the photolithography step.

近年來，隨著半導體裝置之高積體化，光微影步驟中所使用之曝光光趨於短波長化。即，要求於晶圓上描繪積體電路圖案時可以更窄之線寬描繪微細電路圖案之技術。為了應對該要求，例如作為光微影用步進機之曝光光，自先前之g射線(波長436 nm)、i射線(波長365 nm)發展到使用KrF準分子雷射(波長248 nm)、ArF準分子雷射(波長193 nm)進而F2準分子雷射(波長157 nm)等更短波長之光。In recent years, with the high integration of semiconductor devices, the exposure light used in the photolithography step tends to be short-wavelength. That is, it is required to draw a fine circuit pattern in a narrower line width when an integrated circuit pattern is drawn on a wafer. In order to cope with this requirement, for example, exposure light as a stepper for photolithography has been developed from the previous g-ray (wavelength 436 nm), i-ray (wavelength 365 nm) to the use of KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm) and then F2 excimer laser (wavelength 157 nm) and other shorter wavelengths of light.

作為將光罩護膜固定於光罩上之方法，通常採用利用黏著劑以可剝離之方式進行固定的方法，作為用於固定之黏著劑，已知有丙烯酸系、橡膠系、聚丁烯系、聚胺基甲酸酯系、聚矽氧系等黏著劑(參照專利文獻1)。黏著劑層係形成在一端面鋪設有光罩護膜薄膜之光罩護膜框的另一端面，因此於光罩護膜薄膜或光罩被污染時，必需自光罩暫時剝離光罩護膜並除去污垢而再將光罩護膜重新貼在光罩上。又，為了消除曝光步驟中光罩護膜會自光罩脫落等問題，對上述黏著劑亦要求即使施加一定負重亦不會剝離之耐負重性。As a method of fixing the reticle film to the reticle, a method of detachably fixing with an adhesive is generally employed. As the adhesive for fixing, an acrylic, rubber, or polybutene system is known. An adhesive such as a polyurethane or a polyoxygen (see Patent Document 1). The adhesive layer is formed on the other end surface of the reticle film frame on which the reticle film is disposed on one end surface. Therefore, when the reticle film or the reticle is contaminated, the reticle film must be temporarily peeled off from the reticle. Remove the dirt and reattach the reticle to the reticle. Further, in order to eliminate the problem that the mask film is peeled off from the mask during the exposure step, the above-mentioned adhesive is also required to have no load-bearing resistance even if a certain load is applied.

另一方面，隨著上述曝光光之短波長化、高能量化，光罩護膜薄膜或光罩隨著曝光而產生污垢(稱為「霧化」)之頻率增高。On the other hand, as the exposure light is shortened in wavelength and energy is increased, the frequency of fouling (referred to as "atomization") of the photomask film or the mask due to exposure increases.

現認為曝光過程中自黏著劑所產生之有機氣體成分係導致隨著上述曝光光之短波長化、高能量化而發生霧化的原因之一。至今所使用之聚矽氧系黏著劑或橡膠系黏著劑在曝光過程中會產生較多氣體成分。作為降低自黏著劑產生之氣體成分的方法，眾所周知的是專利文獻2~4所揭示之技術，但尚未完全解決問題。It is considered that the organic gas component generated by the self-adhesive during exposure causes one of the causes of fogging due to the short-wavelength and high energy of the exposure light. Polyoxynoxy adhesives or rubber-based adhesives which have hitherto used generate more gas components during exposure. As a method of reducing the gas component generated by the self-adhesive agent, the techniques disclosed in Patent Documents 2 to 4 are known, but the problem has not been completely solved.

又，隨著上述曝光光之短波長化、高能量化，光罩護膜薄膜或光罩隨著曝光產生污垢之頻率增高，因此光罩護膜或光罩之替換之頻率亦增強。於上述狀況下，較理想的是穩定具有適當之黏著力並且替換時光罩上不產生殘膠之光罩護膜用黏著劑。尤其是使用波長短於200 nm之光的光微影步驟中，更易於發生上述霧化，因此更加要求將光罩護膜自光罩剝離時光罩上不殘留黏著劑殘膠之特質。另一方面，當前使用KrF準分子雷射(波長248 nm)之光微影步驟中，用作光罩護膜用黏著劑之聚矽氧系黏著劑存在光罩上易殘留黏著劑殘膠，及耐負重性不充分之問題。Further, as the exposure light is shortened in wavelength and energy is increased, the frequency at which the mask film or the mask is stained by exposure increases, and the frequency of replacement of the mask film or the mask is also increased. Under the above circumstances, it is desirable to stabilize the adhesive for the reticle film which has an appropriate adhesive force and which does not generate residual glue on the reticle. In particular, in the photolithography step using light having a wavelength shorter than 200 nm, the above-mentioned atomization is more likely to occur. Therefore, it is more desirable to leave the photoresist film on the photomask without leaving adhesive residue. On the other hand, in the current photolithography step using a KrF excimer laser (wavelength 248 nm), the polyoxygen-based adhesive used as an adhesive for the mask film has a residual adhesive residue on the mask. And the problem of insufficient bearing capacity.

作為改善剝離光罩護膜後殘留殘膠之方法，於專利文獻5中揭示有具有凝聚斷裂強度為20 g/mm2以上之黏著層的光罩護膜。然而，黏著劑之殘膠與耐負重性問題通常為取捨關係，會產生殘膠較少之黏著劑的耐負重性差，曝光過程中黏著劑會發生剝離的問題。As a method of improving the residual residual glue after peeling off the mask film, Patent Document 5 discloses a mask film having an adhesive layer having a cohesive breaking strength of 20 g/mm 2 or more. However, the problem of the adhesive residue and the load-bearing property of the adhesive is usually a trade-off relationship, and the adhesive having less residual adhesive is poor in load-bearing property, and the adhesive may be peeled off during the exposure.

又，隨著近年來曝光光之短波長化、高能量化，圖案趨於微細化，因此認為若光罩之平坦性差則會產生如下問題：於曝光時產生焦點偏移，燒接而成之圖案的精度變差。因此，對光罩之平坦性要求會比先前更加嚴格。In addition, with the short-wavelength and high energy of the exposure light in recent years, the pattern tends to be finer. Therefore, it is considered that if the flatness of the photomask is poor, there is a problem in that a focus shift occurs during exposure and is baked. The accuracy of the pattern deteriorates. Therefore, the flatness requirements for the reticle are more stringent than before.

現認為光罩護膜係使光罩之平坦性改變的因素之一，尤其是利用光罩黏著材料改變平坦性的方法，於專利文獻6、7中有揭示。It is considered that one of the factors for changing the flatness of the reticle by the reticle film, in particular, a method of changing the flatness by using the reticle adhesive material, is disclosed in Patent Documents 6 and 7.

[先前技術文獻][Previous Technical Literature] [專利文獻][Patent Literature]

[專利文獻1]日本專利特開平05-281711號公報[Patent Document 1] Japanese Patent Laid-Open No. Hei 05-281711

[專利文獻2]日本專利特開平10-171103號公報[Patent Document 2] Japanese Patent Laid-Open No. Hei 10-171103

[專利文獻3]日本專利特開2001-147518號公報[Patent Document 3] Japanese Patent Laid-Open Publication No. 2001-147518

[專利文獻4]國際公開第2004-046827號手冊[Patent Document 4] International Publication No. 2004-046827

[專利文獻5]日本專利特開2006-146085號公報[Patent Document 5] Japanese Patent Laid-Open Publication No. 2006-146085

[專利文獻6]日本專利特開2009-276504號公報[Patent Document 6] Japanese Patent Laid-Open Publication No. 2009-276504

[專利文獻7]日本專利特開2009-025560號公報[Patent Document 7] Japanese Patent Laid-Open Publication No. 2009-025560

本發明者等人經研究得知：自黏著劑產生之有機氣體成分中，以甲苯、乙酸乙酯為代表之有機溶劑成分係光罩上所產生之霧化的主要原因。The inventors of the present invention have found that the organic solvent component represented by toluene or ethyl acetate is the main cause of atomization generated on the mask by the organic gas component produced by the adhesive.

有機溶劑主要於溶液聚合時使用，尤其是甲苯、乙酸乙酯對黏著劑之溶解性較高，具有適度之沸點，因此為工業上非常易於使用之溶劑。然而，使用上述有機溶劑所製造之黏著劑中殘留有一定量之有機溶劑成分，其於曝光過程中會以氣體形式釋放。為了減少自黏著劑層所產生之氣體，通常採用將所使用之溶劑等低沸點成分於高溫下長時間乾燥，儘量減少黏著劑層所殘留之溶劑的方法。然而，長時間乾燥有損生產性，又，即便實施除去黏著劑中之有機溶劑成分之方法，亦必定會殘留一定量之有機溶劑成分，該有機溶劑成分揮發會導致霧化。The organic solvent is mainly used in solution polymerization, and in particular, toluene and ethyl acetate have high solubility to an adhesive and have a moderate boiling point, and thus are industrially very easy to use solvents. However, a certain amount of the organic solvent component remains in the adhesive produced by using the above organic solvent, which is released as a gas during the exposure. In order to reduce the gas generated from the adhesive layer, a method of drying the low-boiling component such as a solvent to be used at a high temperature for a long period of time to minimize the solvent remaining in the adhesive layer is usually employed. However, long-term drying impairs productivity, and even if a method of removing the organic solvent component in the adhesive is carried out, a certain amount of the organic solvent component is always left, and the organic solvent component volatilizes to cause atomization.

因此，本發明者等人經過努力研究，結果發現：藉由使光罩護膜所使用之黏著劑本身具有有機氣體吸附性能，可防止會導致霧化之有機氣體吸附在光罩上，從而完成本申請發明。Therefore, the inventors of the present invention have conducted diligent research and found that the organic gas adsorbing property of the reticle coating itself can prevent the atomized organic gas from being adsorbed on the reticle, thereby completing Invention of the present application.

本發明之目的在於提供一種具有有機氣體吸附性能優異之黏著劑的光罩護膜。An object of the present invention is to provide a photomask film having an adhesive having excellent organic gas adsorption performance.

本發明者等人經過努力研究，結果得知藉由以下發明可解決上述課題。As a result of intensive studies, the inventors of the present invention have found that the above problems can be solved by the following invention.

即，本發明如下：That is, the present invention is as follows:

1.一種光罩護膜，其係具有光罩護膜框，於該光罩護膜框之一端面具有光罩護膜薄膜且於另一端面具有黏著劑者，並且該黏著劑對甲苯之重量膨潤度為5倍以上。A reticle protective film comprising a reticle protective film frame, having a reticle film on one end face of the reticle cover film and having an adhesive on the other end face, and the adhesive is toluene The weight swelling degree is more than 5 times.

2.如上述1之光罩護膜，其中該黏著劑含有(甲基)丙烯酸烷基酯共聚物與硬化材料之反應生成物，並且該(甲基)丙烯酸烷基酯共聚物係具有碳數4~14之烷基之(甲基)丙烯酸烷基酯與含有與硬化材料具有反應性之官能基之單體的共聚物。2. The photomask film according to the above 1, wherein the adhesive contains a reaction product of an alkyl (meth) acrylate copolymer and a hardening material, and the alkyl (meth) acrylate copolymer has a carbon number A copolymer of an alkyl (meth) acrylate having 4 to 14 alkyl groups and a monomer having a functional group reactive with a hardening material.

3.如上述1或2之光罩護膜，其中該黏著劑藉由拉伸速度為30 mm/min之拉伸試驗所獲得之23℃下的300%模數值為50~350 mN/mm2。3. Support the photomask film 1 or 2, wherein the adhesive by a stretching speed of 300% modulus value at 23 ℃ 30 mm / min of tensile test of the obtained 50 ~ 350 mN / mm 2 .

4.如上述1或2之光罩護膜，其中該硬化材料係選自由多官能性環氧化合物及異氰酸酯系化合物所組成之群中之至少一種硬化材料。4. The photomask film according to the above 1 or 2, wherein the hardening material is at least one selected from the group consisting of a polyfunctional epoxy compound and an isocyanate compound.

5.如上述1或2之光罩護膜，其中該黏著劑係包含含有具備聚合起始末端之聚合物及聚合起始劑之黏著劑組合物者，該黏著劑中之聚合起始劑之總重量相對於黏著劑總重量為8 ppm以下。5. The photomask film according to the above 1 or 2, wherein the adhesive comprises an adhesive composition comprising a polymer having a polymerization starting end and a polymerization initiator, and a polymerization initiator in the adhesive The total weight is 8 ppm or less relative to the total weight of the adhesive.

6.如上述1或2之光罩護膜，其中該黏著劑係含有(甲基)丙烯酸烷基酯共聚物100重量份與硬化材料0.05~3重量份之反應生成物者。6. The photomask film according to the above 1 or 2, wherein the adhesive contains 100 parts by weight of an alkyl (meth) acrylate copolymer and 0.05 to 3 parts by weight of a hardening material.

7.如上述4之光罩護膜，其中該多官能性環氧化合物係具有2~4個環氧基之含氮環氧化合物。7. The photomask film according to the above 4, wherein the polyfunctional epoxy compound is a nitrogen-containing epoxy compound having 2 to 4 epoxy groups.

8.如上述3之光罩護膜，其含有丙烯酸作為含有與該硬化材料具有反應性之官能基的單體，該丙烯酸之量相對於構成該(甲基)丙烯酸烷基酯共聚物之全部單體為0.1~5重量%。8. The photomask film according to the above 3, which comprises acrylic acid as a monomer having a functional group reactive with the hardening material, the amount of the acrylic acid being relative to all of the alkyl (meth)acrylate copolymer The monomer is 0.1 to 5% by weight.

9.如上述3之光罩護膜，其中該(甲基)丙烯酸烷基酯共聚物之重量平均分子量為70萬~250萬。9. The photomask film of the above 3, wherein the (meth)acrylic acid alkyl ester copolymer has a weight average molecular weight of 700,000 to 2.5 million.

10.一種光罩護膜，其係具有光罩護膜框，於該光罩護膜框之一端面具有光罩護膜薄膜且於另一端面具有黏著劑者，並且該黏著劑係包含含有具備聚合起始末端之聚合物及聚合起始劑之黏著劑組合物者，該黏著劑中之聚合起始劑之總重量相對於黏著劑總重量為8 ppm以下。10. A reticle film having a reticle film frame, having a reticle film on one end surface of the reticle film frame and having an adhesive on the other end surface, and the adhesive agent comprises In the adhesive composition having the polymer of the polymerization starting end and the polymerization initiator, the total weight of the polymerization initiator in the adhesive is 8 ppm or less based on the total weight of the adhesive.

11.如上述10之光罩護膜，其中該聚合起始劑為過氧化物系聚合起始劑或偶氮系聚合起始劑、或者烷基苯酮系聚合起始劑或醯基氧化膦系聚合起始劑。11. The photomask film according to the above 10, wherein the polymerization initiator is a peroxide polymerization initiator or an azo polymerization initiator, or an alkylphenone polymerization initiator or fluorenylphosphine oxide. It is a polymerization initiator.

12.如上述10或11之光罩護膜，其中該黏著劑含有(甲基)丙烯酸烷基酯共聚物與硬化材料之反應生成物，該(甲基)丙烯酸烷基酯共聚物係具有碳數4~14之烷基之(甲基)丙烯酸烷基酯與含有與硬化材料具有反應性之官能基之單體的共聚物。12. The photomask film according to the above 10 or 11, wherein the adhesive contains a reaction product of an alkyl (meth) acrylate copolymer and a hardening material, and the alkyl (meth) acrylate copolymer has carbon A copolymer of an alkyl (meth) acrylate having 4 to 14 alkyl groups and a monomer having a functional group reactive with a hardening material.

13.如上述10或11之光罩護膜，其中該黏著劑藉由拉伸速度為30 mm/min之拉伸試驗所獲得之23℃下的300%模數值為50~350 mN/mm2。The photomask 13 of the protective film 10 or 11, wherein the adhesive by a stretching speed of 300% modulus value at 23 ℃ 30 mm / min of tensile test of the obtained 50 ~ 350 mN / mm 2 .

14.如上述10或11之光罩護膜，其中該硬化材料係選自由多官能性環氧化合物及異氰酸酯系化合物所組成之群中之至少一種硬化材料。14. The photomask film according to the above 10 or 11, wherein the hardening material is at least one selected from the group consisting of a polyfunctional epoxy compound and an isocyanate compound.

15.如上述10或11之光罩護膜，其中該黏著劑對甲苯之重量膨潤度為5倍以上。15. The photomask cover according to the above 10 or 11, wherein the adhesive has a degree of swelling of toluene of 5 times or more.

16.如上述12之光罩護膜，其中該黏著劑係含有(甲基)丙烯酸烷基酯共聚物100重量份與硬化材料0.05~3重量份之反應生成物者。16. The photomask film according to the above 12, wherein the adhesive contains 100 parts by weight of an alkyl (meth) acrylate copolymer and 0.05 to 3 parts by weight of a hardening material.

17.如上述14之光罩護膜，其中該多官能性環氧化合物係具有2~4個環氧基之含氮環氧化合物。17. The photomask cover according to the above 14, wherein the polyfunctional epoxy compound is a nitrogen-containing epoxy compound having 2 to 4 epoxy groups.

18.如上述12之光罩護膜，其含有丙烯酸作為含有與該硬化材料具有反應性之官能基的單體，該丙烯酸之量相對於構成該(甲基)丙烯酸烷基酯共聚物之全部單體為0.1~5重量%。18. The photomask film according to the above 12, which comprises acrylic acid as a monomer having a functional group reactive with the hardening material, the amount of the acrylic acid being relative to all of the alkyl (meth)acrylate copolymer The monomer is 0.1 to 5% by weight.

19.如上述12之光罩護膜，其中該(甲基)丙烯酸烷基酯共聚物之重量平均分子量為70萬~250萬。19. The photomask film of the above 12, wherein the (meth)acrylic acid alkyl ester copolymer has a weight average molecular weight of 700,000 to 2.5 million.

20.一種黏著劑，其係含有(甲基)丙烯酸烷基酯共聚物100重量份與多官能性環氧化合物0.05~3重量份之反應生成物者，該(甲基)丙烯酸烷基酯共聚物係具有碳數4~14之烷基之(甲基)丙烯酸烷基酯與含有與環氧基具有反應性之官能基的單體的共聚物，並且該黏著劑對甲苯之重量膨潤度為5倍以上。An adhesive comprising a reaction product of 100 parts by weight of an alkyl (meth) acrylate copolymer and 0.05 to 3 parts by weight of a polyfunctional epoxy compound, which is copolymerized with an alkyl (meth) acrylate. The system has a copolymer of an alkyl (meth) acrylate having a carbon number of 4 to 14 and a monomer having a functional group reactive with an epoxy group, and the viscosity of the adhesive to toluene is More than 5 times.

本發明之光罩護膜係有機氣體吸附性能優異之光罩護膜，因此可有效地抑制光罩上所產生之霧化。The photomask film of the present invention is a photomask film having excellent organic gas adsorption performance, so that atomization generated on the photomask can be effectively suppressed.

以下，詳細說明用以實施本發明之形態(以下僅稱為「本實施形態」)。以下之本實施形態僅為用以說明本發明之例示，並非意在將本發明限定為以下內容。本發明可於其主旨之範圍內適當變形而實施。Hereinafter, the form for carrying out the present invention (hereinafter simply referred to as "this embodiment") will be described in detail. The following examples are merely illustrative of the invention and are not intended to limit the invention to the following. The present invention can be suitably modified within the scope of the gist of the invention.

本發明之光罩護膜所使用之黏著劑對甲苯之重量膨潤度為5倍以上。此處所謂膨潤，係指彈性凝膠吸收液體(溶劑)而使體積、重量增加的現象，重量膨潤度表示彈性凝膠吸收液體(溶劑)而使重量增加時之增加比例。The adhesive used for the photomask film of the present invention has a degree of swelling of toluene of 5 times or more. The term "swelling" as used herein refers to a phenomenon in which an elastic gel absorbs a liquid (solvent) to increase the volume and weight, and a weight swelling degree indicates an increase ratio when the elastic gel absorbs a liquid (solvent) and increases the weight.

若黏著劑之重量膨潤度較大，則可利用黏著劑吸附由光罩護膜與光罩所圍成之封閉空間中存在的以甲苯、乙酸乙酯為代表的有機氣體，可大幅度降低有機氣體與光罩接觸之頻率。結果可大幅度抑制霧化之產生。If the weight of the adhesive is large, the adhesive can adsorb the organic gas represented by toluene and ethyl acetate present in the enclosed space surrounded by the reticle film and the reticle, which can greatly reduce the organic The frequency at which the gas contacts the reticle. As a result, the generation of atomization can be greatly suppressed.

又，藉由增大重量膨潤度，不僅可吸附有機氣體，亦可降低所產生之氣體之量。具體而言，判明藉由控制製作黏著劑時所使用之溶劑及作為溶質之聚合物的重量膨潤度，即便溶劑殘留於聚合物中，溶劑亦不會自聚合物中以氣體形式釋放，而保留在聚合物中。藉由控制重量膨潤度可減少氣體產生的原因尚不明確，推測為藉由提高聚合物與溶劑之親和性，且控制聚合物之交聯網狀結構，而使殘留之溶劑滲入聚合物中。Further, by increasing the degree of swelling, it is possible to adsorb not only the organic gas but also the amount of gas generated. Specifically, it has been found that by controlling the weight of the solvent used in the production of the adhesive and the polymer as a solute, even if the solvent remains in the polymer, the solvent is not released from the polymer as a gas, but remains. In the polymer. The reason for reducing the gas generation by controlling the weight swelling degree is not clear, and it is presumed that the residual solvent is infiltrated into the polymer by increasing the affinity of the polymer to the solvent and controlling the crosslinked network structure of the polymer.

進而，若甲苯之重量膨潤度為5倍以上，則推測聚合物之交聯網狀結構之大小達到最適合吸附由光罩護膜與光罩所圍成之封閉空間中存在的以甲苯、乙酸乙酯為代表之有機氣體的大小，大幅度抑制霧化之產生。Further, if the degree of swelling of the toluene is 5 times or more, it is presumed that the size of the crosslinked network structure of the polymer is most suitable for the adsorption of toluene and acetic acid in the closed space surrounded by the reticle film and the reticle. The size of the organic gas represented by the ester greatly inhibits the generation of atomization.

基於以上原因，較佳為光罩護膜所使用之黏著劑對甲苯之重量膨潤度為5倍以上，較佳為7倍以上，更佳為9倍以上，尤佳為10倍以上。For the above reasons, it is preferred that the adhesive used for the mask film has a degree of swelling of toluene of 5 times or more, preferably 7 times or more, more preferably 9 times or more, and particularly preferably 10 times or more.

若本申請發明之光罩護膜所使用之黏著劑的重量膨潤度為5倍以上則無限定，尤其就與光罩之接著力充分且剝離後之殘膠較少之方面而言，較佳為包含含有(甲基)丙烯酸烷基酯共聚物與硬化材料之反應生成物而成之組合物的黏著劑，並且該(甲基)丙烯酸烷基酯共聚物係藉由使具有碳數4~14之烷基之(甲基)丙烯酸烷基酯(以下稱為「A成分」)、與含有與硬化材料具有反應性之官能基之單體(以下稱為「B成分」)中的至少兩種單體成分共聚合而獲得之共聚物。The adhesive used in the photomask coating of the present invention has a weight swelling degree of not less than 5 times, and is particularly preferably in terms of sufficient adhesion to the photomask and less residual adhesive after peeling. An adhesive comprising a composition comprising a reaction product of an alkyl (meth) acrylate copolymer and a hardening material, and the alkyl (meth) acrylate copolymer is obtained by having a carbon number of 4~ At least two of an alkyl (meth)acrylate (hereinafter referred to as "component A") having 14 alkyl groups and a monomer having a functional group reactive with a hardener (hereinafter referred to as "component B") A copolymer obtained by copolymerizing a monomer component.

烷基酯共聚物為A成分99~80重量%、B成分1~20重量%之單體混合物的共聚物時可表現出適度的與光罩之接著力，故而更佳。When the alkyl ester copolymer is a copolymer of a monomer mixture of 99 to 80% by weight of the A component and 1 to 20% by weight of the component B, it is more preferable because it exhibits an appropriate adhesion to the mask.

此處，將A成分之單體分為碳數4~14之烷基為直鏈狀者(以下稱為「A1成分」)與碳數4~14之烷基為支鏈狀者(以下稱為「A2成分」)之情形時，若上述(甲基)丙烯酸烷基酯共聚物係A2成分9~59%之單體混合物的共聚物，則黏著力優異，因而更佳。若為A1成分40~90重量%、A2成分9~59重量%、B成分1~20重量%之單體混合物之共聚物，則剝離後之殘膠減少，因而更佳。Here, the monomer of the component A is divided into a linear one having a carbon number of 4 to 14 (hereinafter referred to as "A1 component") and an alkyl group having 4 to 14 carbon atoms as a chain (hereinafter referred to as In the case of the "A2 component", the copolymer of the monomer mixture of 9 to 59% of the (meth)acrylic acid alkyl ester copolymer A2 component is more excellent in adhesion. When the copolymer of the monomer mixture of 40 to 90% by weight of the A1 component, 9 to 59% by weight of the A2 component, and 1 to 20% by weight of the component B is used, the residual rubber after the peeling is reduced, which is more preferable.

A1成分之丙烯酸酯系單體係烷基碳數為4~14之(甲基)丙烯酸烷基酯，具體可列舉：(甲基)丙烯酸丁酯、(甲基)丙烯酸己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸月桂酯等直鏈脂肪族醇之(甲基)丙烯酸酯。該等可單獨使用亦可併用2種以上。其中，(甲基)丙烯酸丁酯、(甲基)丙烯酸辛酯等具有碳數4~8之烷基之(甲基)丙烯酸烷基酯表現出適度之與光罩之接著性，因此可較好地使用。The acrylate-based single-system A1 component has an alkyl (meth) acrylate having 4 to 14 carbon atoms, and specific examples thereof include butyl (meth)acrylate, hexyl (meth)acrylate, and (methyl). A (meth) acrylate of a linear aliphatic alcohol such as octyl acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate or lauryl (meth) acrylate. These may be used alone or in combination of two or more. Among them, an alkyl (meth)acrylate having an alkyl group having 4 to 8 carbon atoms such as butyl (meth)acrylate or octyl (meth)acrylate exhibits a moderate adhesion to the mask, and thus can be compared. Good to use.

A2成分之丙烯酸酯系單體為具有支鏈狀烷基鏈者，具體可列舉：(甲基)丙烯酸異丁酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸異壬酯。該等可單獨使用亦可併用2種以上。其中，就共聚性方面而言，較佳為使用(甲基)丙烯酸異丁酯(例如丙烯酸異丁酯)或(甲基)丙烯酸2-乙基己酯(例如丙烯酸2-乙基己酯)。The acrylate monomer of the component A2 is a branched alkyl chain, and specific examples thereof include isobutyl (meth)acrylate, isoamyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. Ester, isooctyl (meth)acrylate, isodecyl (meth)acrylate. These may be used alone or in combination of two or more. Among them, in terms of copolymerizability, it is preferred to use isobutyl (meth)acrylate (for example, isobutyl acrylate) or 2-ethylhexyl (meth)acrylate (for example, 2-ethylhexyl acrylate). .

B成分之單體係可與上述A成分之單體共聚合的單體，且為與環氧基具有反應性的單體。例如為(甲基)丙烯酸、衣康酸、順丁烯二酸、丁烯酸等含羧基單體，或(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯等含羥基單體。該等可單獨使用亦可併用2種以上。其中，就共聚性、通用性等方面而言，較佳為使用(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸4-羥基丁酯等具有碳數2~4之羥基烷基之含羥基(甲基)丙烯酸酯，(甲基)丙烯酸等含羧基單體。尤其就殘膠方面而言，較佳為(甲基)丙烯酸，(甲基)丙烯酸之含量相對於構成(甲基)丙烯酸烷基酯共聚物之全部單體為0.1~5重量%，更佳為0.5~4重量%，更佳為0.8~3重量%。The monomer of the component B can be a monomer copolymerizable with the monomer of the above component A, and is a monomer reactive with an epoxy group. For example, a carboxyl group-containing monomer such as (meth)acrylic acid, itaconic acid, maleic acid or crotonic acid, or 2-hydroxyethyl (meth)acrylate or 3-hydroxypropyl (meth)acrylate, A hydroxyl group-containing monomer such as 2-hydroxypropyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate. These may be used alone or in combination of two or more. Among them, in terms of copolymerizability, versatility, and the like, it is preferred to use a hydroxyalkyl group having 2 to 4 carbon atoms such as 2-hydroxyethyl (meth)acrylate or 4-hydroxybutyl (meth)acrylate. A carboxyl group-containing monomer such as a hydroxyl group (meth) acrylate or (meth) acrylate. Particularly, in terms of residual adhesive, it is preferably (meth)acrylic acid, and the content of (meth)acrylic acid is 0.1 to 5% by weight, more preferably, based on all monomers constituting the alkyl (meth)acrylate copolymer. It is 0.5 to 4% by weight, more preferably 0.8 to 3% by weight.

上述(甲基)丙烯酸烷基酯共聚物中，上述A1成分之丙烯酸酯系單體之用量於單體混合物中為40~90重量%、較佳為45~80重量%。又，A2成分宜為9~59重量%，較佳為15~50重量%，B成分宜為1~20重量%，較佳為2~10重量%。In the alkyl (meth)acrylate copolymer, the amount of the acrylate monomer of the A1 component is 40 to 90% by weight, preferably 45 to 80% by weight based on the monomer mixture. Further, the component A2 is preferably 9 to 59% by weight, preferably 15 to 50% by weight, and the component B is preferably 1 to 20% by weight, preferably 2 to 10% by weight.

若(甲基)丙烯酸烷基酯共聚物之重量平均分子量為70萬以上、250萬以下，則黏著劑層之凝聚力、接著力達到適度之大小，成為不易殘留殘膠且具有充分之接著力、耐負重性的黏著劑，故而較佳。重量平均分子量較佳為90萬以上、230萬以下，更佳為100萬以上、200萬以下。關於重量平均分子量之控制方法，可藉由眾所周知之方法進行控制。具體而言，通常有如下傾向：聚合反應時之單體濃度越高則重量平均分子量越大，聚合起始劑量之量越少，且聚合溫度越低則重量平均分子量越大。When the weight average molecular weight of the (meth)acrylic acid alkyl ester copolymer is 700,000 or more and 2.5 million or less, the cohesive force and the adhesion force of the adhesive layer are appropriately increased, and it is difficult to leave residual glue and have sufficient adhesion. A load-resistant adhesive is preferred. The weight average molecular weight is preferably 900,000 or more and 2.3 million or less, more preferably 1,000,000 or more and 2,000,000 or less. The method for controlling the weight average molecular weight can be controlled by a well-known method. Specifically, there is usually a tendency that the higher the monomer concentration at the time of polymerization, the larger the weight average molecular weight, the smaller the amount of the polymerization starting dose, and the lower the polymerization temperature, the larger the weight average molecular weight.

上述(甲基)丙烯酸烷基酯共聚物之製造可適當選用溶液聚合、塊狀聚合、乳化聚合、各種自由基聚合等眾所周知之製造方法。又，所獲得之(甲基)丙烯酸烷基酯共聚物可為無規共聚物、嵌段共聚物、接枝共聚物等中任一種。再者，溶液聚合中，聚合溶劑例如可使用乙酸乙酯、甲苯等。As the above-mentioned (meth)acrylic acid alkyl ester copolymer, a well-known production method such as solution polymerization, bulk polymerization, emulsion polymerization, or various radical polymerization can be suitably used. Further, the obtained alkyl (meth)acrylate copolymer may be any of a random copolymer, a block copolymer, a graft copolymer and the like. Further, in the solution polymerization, for example, ethyl acetate, toluene or the like can be used as the polymerization solvent.

作為具體之溶液聚合例，於氮氣等惰性氣體氣流下，例如相對於單體總量100重量份添加偶氮雙異丁腈0.01~2.0重量份作為聚合起始劑，通常於50~70℃左右下反應8~30小時左右。自由基聚合所使用之聚合起始劑、鏈轉移劑、乳化劑等並無特別限定，可適當選擇使用。As a specific solution polymerization example, 0.01 to 2.0 parts by weight of azobisisobutyronitrile is added as a polymerization initiator, for example, at 50 to 70 ° C under an inert gas flow such as nitrogen, for example, 100 parts by weight based on 100 parts by weight of the total amount of monomers. The next reaction is about 8 to 30 hours. The polymerization initiator, the chain transfer agent, the emulsifier, and the like used in the radical polymerization are not particularly limited, and can be appropriately selected and used.

作為較佳之聚合起始劑，例如可列舉：偶氮系之2,2'-偶氮雙異丁腈、2,2'-偶氮雙-2-甲基丁腈、2,2'-偶氮雙(2-甲基丙酸甲酯)、4,4'-偶氮雙-4-氰基纈草酸等，或過氧化物系之過氧化苯甲醯等。Preferred examples of the polymerization initiator include azo-type 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, and 2,2'-couple. Nitrogen bis(2-methylpropionate), 4,4'-azobis-4-cyanoshikimate, or the like, or peroxide-based benzamidine peroxide.

本申請發明之光罩護膜所使用之黏著劑尤佳為包含含有(甲基)丙烯酸烷基酯共聚物與硬化材料之反應生成物而成之組合物的黏著劑。The adhesive used for the photomask film of the present invention is particularly preferably an adhesive comprising a composition containing a reaction product of an alkyl (meth)acrylate copolymer and a hardening material.

作為該硬化材料，可列舉：金屬鹽、金屬烷氧化物、醛系化合物、非胺基樹脂系胺基化合物、脲系化合物、異氰酸酯系化合物、金屬螯合物系化合物、三聚氰胺系化合物、氮丙啶系化合物等通常黏著劑所使用之硬化材料，就與(甲基)丙烯酸烷基酯共聚物所具有之官能基成分之反應性方面而言，較佳為選自由異氰酸酯系化合物及多官能性環氧化合物所組成之群中之至少一種硬化材料，更佳為多官能性環氧化合物。Examples of the hardening material include a metal salt, a metal alkoxide, an aldehyde compound, a non-amino resin-based amine compound, a urea compound, an isocyanate compound, a metal chelate compound, a melamine compound, and a nitrogen-based compound. The hardening material used for a usual adhesive such as a pyridine compound is preferably selected from an isocyanate-based compound and polyfunctionality in terms of reactivity with a functional group component of an alkyl (meth)acrylate copolymer. At least one hardening material in the group consisting of epoxy compounds is more preferably a polyfunctional epoxy compound.

具體而言，作為異氰酸酯系化合物，可列舉甲苯二異氰酸酯，作為多官能性環氧化合物，可列舉：新戊二醇二縮水甘油醚、聚乙二醇二縮水甘油醚、雙酚A二縮水甘油醚、雙酚F二縮水甘油醚、對苯二甲酸二縮水甘油酯、二聚酸二縮水甘油酯、異氰尿酸三縮水甘油酯、二甘油基三縮水甘油醚、山梨糖醇四縮水甘油醚、N,N,N',N'-四縮水甘油基間二甲苯二胺、1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷、N,N,N',N'-四縮水甘油基二胺基二苯基甲烷等。Specific examples of the isocyanate-based compound include toluene diisocyanate, and examples of the polyfunctional epoxy compound include neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and bisphenol A diglycidylglycerol. Ether, bisphenol F diglycidyl ether, diglycidyl terephthalate, dimer acid diglycidyl ester, triglycidyl isocyanurate, diglyceryl triglycidyl ether, sorbitol tetraglycidyl ether , N,N,N',N'-tetraglycidyl meta-xylene diamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N' , N'-tetraglycidyldiaminodiphenylmethane, and the like.

該等中，較佳為具有2~4個環氧基之含氮環氧化合物，就反應性方面而言，宜使用具有4個環氧基之含氮環氧化合物。若反應性良好，則於塗佈黏著劑後，交聯反應迅速結束，因此特性於短時間內穩定，於生產性方面優異。Among these, a nitrogen-containing epoxy compound having 2 to 4 epoxy groups is preferred, and in terms of reactivity, a nitrogen-containing epoxy compound having 4 epoxy groups is preferably used. When the reactivity is good, the crosslinking reaction is quickly completed after the application of the pressure-sensitive adhesive, and therefore the characteristics are stabilized in a short period of time and are excellent in productivity.

又，藉由調整硬化材料之含量，可控制重量膨潤度。所謂膨潤係指溶劑分子進入聚合物分子間，使擴大分子間距之力與交聯網狀結構之彈性取得平衡的狀態。膨潤的大小受溶劑與聚合物之親和性及聚合物之交聯度的影響，可藉由控制該等而控制甲苯之重量膨潤度。溶劑與聚合物之親和性較高者通常重量膨潤度會提高。作為親和性之標準，通常使用SP值(Solubility Parameter，溶解度參數)，提出SP值較近者彼此親和性較高之「POLYMERHANDBOOK(4th edition) WILEY-INTER SCIENCE P689-711」中有各種SP值之記載，甲苯為18.2(MPa1/2)，乙酸乙酯為18.6(MPa1/2)，為大致相同之值。因此，構成聚合物之單體成分的SP值接近於甲苯、乙酸乙酯使重量膨潤度提高。例如，作為丙烯酸系黏著劑之單體成分之丙烯酸丁酯為18.0(MPa1/2)，丙烯酸異丁酯為17.4(MPa1/2)，作為橡膠系黏著劑之單體成分的丁二烯為14.5(MPa1/2)，異丁烯為15.0(MPa1/2)，乙烯為15.76(MPa1/2)，丁烯為13.7(MPa1/2)，作為聚矽氧黏著劑之單體成分之二甲基矽氧烷為10.0~12.1(MPa1/2)。因此，就聚合物與溶劑之親和性之觀點而言，較佳為丙烯酸系黏著劑。Further, by adjusting the content of the hardened material, the degree of weight swelling can be controlled. The term "swelling" refers to a state in which a solvent molecule enters between polymer molecules to balance the force of expanding the molecular spacing with the elasticity of the cross-linked network structure. The size of the swelling is affected by the affinity of the solvent to the polymer and the degree of crosslinking of the polymer, and the weight swelling degree of toluene can be controlled by controlling these. Those with higher affinity for the solvent and the polymer generally have an increased degree of weight swelling. As a standard of affinity, a SP value (solubility parameter) is generally used, and various SP values are available in "POLYMERHANDBOOK (4th edition) WILEY-INTER SCIENCE P689-711" in which the SP values are relatively close to each other. It is described that toluene is 18.2 (MPa 1/2 ), and ethyl acetate is 18.6 (MPa 1/2 ), which is approximately the same value. Therefore, the SP value of the monomer component constituting the polymer is close to that of toluene or ethyl acetate to increase the degree of weight swelling. For example, butyl acrylate as a monomer component of an acrylic adhesive is 18.0 (MPa 1/2 ), isobutyl acrylate is 17.4 (MPa 1/2 ), and butadiene as a monomer component of a rubber-based adhesive is used. It is 14.5 (MPa 1/2 ), isobutylene is 15.0 (MPa 1/2 ), ethylene is 15.76 (MPa 1/2 ), butene is 13.7 (MPa 1/2 ), and it is used as a monomer component of polyoxyxide adhesive. The dimethyloxane is 10.0 to 12.1 (MPa 1/2 ). Therefore, from the viewpoint of affinity between the polymer and the solvent, an acrylic adhesive is preferred.

又，重量膨潤度亦取決於聚合物之交聯度。若交聯度過低，則溶劑分子不會滲入聚合物交聯網狀結構中，重量膨潤度降低。又，若交聯度過高，則不會進入聚合物交聯網狀結構，重量膨潤度減小。因此，可藉由適當控制聚合物之交聯度而控制重量膨潤度。Also, the degree of weight swelling depends on the degree of crosslinking of the polymer. If the degree of crosslinking is too low, the solvent molecules do not penetrate into the polymer network structure, and the weight swelling degree is lowered. Further, if the degree of crosslinking is too high, the polymer cross-linking structure does not enter, and the degree of weight swelling is reduced. Therefore, the degree of weight swelling can be controlled by appropriately controlling the degree of crosslinking of the polymer.

若硬化材料之含量相對於上述(甲基)丙烯酸烷基酯共聚物100重量份為0.05~3重量份，則甲苯或乙酸乙酯之重量膨潤度為5倍以上，成為較佳的光罩護膜用黏著劑。其中，若硬化材料之含量為0.05重量份~0.20重量份，則甲苯或乙酸乙酯之重量膨潤度進一步增大，成為更加的光罩護膜用黏著劑，抑制霧化之產生，變得不易殘留殘膠。進而，達到適度之交聯密度，因此成為不易對光罩之平坦性造成特別影響(尤其可抑制光罩之變形)的光罩黏著劑。認為其原因在於，若硬化材料之含量在0.20重量份以下，則交聯密度不會變得過大，因此黏著劑吸收對光罩施加之應力，緩和對光罩之平坦性的影響。另一方面，認為若為0.05重量份以上，則交聯密度不會變得過小，因此維持製造步驟中之操作性，不會產生自光罩剝離光罩護膜時殘留殘膠的問題。When the content of the hardening material is 0.05 to 3 parts by weight based on 100 parts by weight of the alkyl (meth)acrylate copolymer, the degree of swelling of toluene or ethyl acetate is 5 times or more, which is a preferable mask protection. Adhesive for film. In the case where the content of the hardening material is from 0.05 part by weight to 0.20 part by weight, the degree of swelling of the toluene or ethyl acetate is further increased, and the adhesive for the mask film is further prevented from being generated, which makes it difficult to produce fogging. Residual residue. Further, since a moderate crosslinking density is achieved, it becomes a mask adhesive which does not easily affect the flatness of the mask (especially, the deformation of the mask can be suppressed). The reason for this is considered to be that if the content of the hardening material is 0.20 parts by weight or less, the crosslinking density does not become excessively large, and therefore the adhesive absorbs the stress applied to the mask to alleviate the influence on the flatness of the mask. On the other hand, when it is 0.05 part by weight or more, the crosslinking density does not become too small, so that the workability in the production step is maintained, and there is no problem that residual glue remains when the mask is peeled off from the mask.

於含有上述(甲基)丙烯酸烷基酯共聚物及多官能性環氧化合物之組合物之情形時，可藉由將聚合物之交聯度控制為適度，而將重量膨潤度最大調整至15倍左右。尤其是若甲苯之重量膨潤度為8倍~14倍左右，則所吸附之甲苯或乙酸乙酯等有機氣體保留在黏著劑中之效果較大，故而較佳。認為其原因在於，若甲苯之重量膨潤度為8倍~14倍左右，則聚合物間之交聯網狀結構間隔達到適合捕獲甲苯及乙酸乙酯的大小。In the case of the composition containing the above (meth)acrylic acid alkyl ester copolymer and the polyfunctional epoxy compound, the weight swelling degree can be adjusted up to 15 by controlling the degree of crosslinking of the polymer to be moderate. Times around. In particular, if the degree of swelling of the toluene is about 8 to 14 times, the organic gas such as toluene or ethyl acetate adsorbed in the adhesive has a large effect, and therefore it is preferable. The reason for this is considered to be that if the degree of swelling of the toluene is about 8 to 14 times, the interlaced structure spacing between the polymers is such that it is suitable for capturing toluene and ethyl acetate.

用以獲得(甲基)丙烯酸烷基酯共聚物與多官能性環氧化合物之反應生成物的反應係藉由如下方式進行：稱量(甲基)丙烯酸烷基酯共聚物溶液與多官能性環氧化合物溶液，進行混合、攪拌以達到均勻混合，將溶劑加熱乾燥除去後，再進行加溫。The reaction for obtaining a reaction product of an alkyl (meth) acrylate copolymer and a polyfunctional epoxy compound is carried out by weighing a (meth)acrylic acid alkyl ester copolymer solution and polyfunctionality. The epoxy compound solution is mixed and stirred to achieve uniform mixing, and the solvent is heated and dried to remove it, followed by heating.

若調節(甲基)丙烯酸烷基酯共聚物之平均分子量與硬化材料之含量，以使黏著劑藉由拉伸速度為30 mm/min之拉伸試驗所獲得的23℃下的300%模數值達到50~350 mN/mm2，則黏著劑之耐負重性優異，成為不易殘留殘膠之黏著劑，因此較佳。此處，所謂300%模數值係指於23℃、65%RH氣體環境下，使用自動立體測圖儀，將黏著層之厚度為0.2 mm且寬度為1.5 mm之黏著劑樣品以夾盤間距為10 mm、拉伸速度為30 mm/min之條件下進行拉伸時300%應變的每單位剖面積之應力。300%模數值主要藉由(甲基)丙烯酸烷基酯共聚物之重量平均分子量與硬化材料之含量控制。(甲基)丙烯酸烷基酯共聚物之重量平均分子量越大則300%模數值亦越大，多官能性環氧化合物之含量越多則300%模數值亦越大。If the average molecular weight of the alkyl (meth) acrylate copolymer and the content of the hardened material are adjusted so that the adhesive can obtain a 300% modulus value at 23 ° C by a tensile test at a tensile speed of 30 mm/min. When the temperature is 50 to 350 mN/mm 2 , the adhesive is excellent in load resistance and is an adhesive which does not easily leave residual glue, and therefore is preferable. Here, the so-called 300% modulus value refers to an adhesive sample with an adhesive layer thickness of 0.2 mm and a width of 1.5 mm at 23 ° C, 65% RH gas atmosphere using an autostereograph. The stress per unit sectional area of 300% strain at 10 mm and a tensile speed of 30 mm/min. The 300% modulus value is mainly controlled by the weight average molecular weight of the (meth)acrylic acid alkyl ester copolymer and the content of the hardening material. The larger the weight average molecular weight of the (meth)acrylic acid alkyl ester copolymer, the larger the 300% modulus value, and the more the polyfunctional epoxy compound content, the larger the 300% modulus value.

(甲基)丙烯酸烷基酯共聚物之重量平均分子量在可使300%模數值達到50~350 mN/mm2之範圍內即可，尤其是重量平均分子量為70萬以上、250萬以下時，黏著劑層之凝聚力、接著力達到適度之大小，成為不易殘留殘膠且具有充分之接著力、耐負重性之黏著劑，故而較佳。重量平均分子量較佳為90萬以上、230萬以下，更佳為100萬以上、200萬以下。The weight average molecular weight of the (meth)acrylic acid alkyl ester copolymer may be such that the 300% modulus value is in the range of 50 to 350 mN/mm 2 , especially when the weight average molecular weight is 700,000 or more and 2.5 million or less. The cohesive force and the adhesive force of the adhesive layer are moderately sized, and it is preferable because it is an adhesive which does not easily retain residual glue and has sufficient adhesive force and load resistance. The weight average molecular weight is preferably 900,000 or more and 2.3 million or less, more preferably 1,000,000 or more and 2,000,000 or less.

關於重量平均分子量之控制方法，可藉由眾所周知之方法控制。具體而言，通常有如下傾向：聚合反應時之單體濃度越高則重量平均分子量越大，聚合起始劑量之量越少，另外聚合溫度越低則重量平均分子量越大。The method for controlling the weight average molecular weight can be controlled by a well-known method. Specifically, there is usually a tendency that the higher the monomer concentration at the time of polymerization, the larger the weight average molecular weight, the smaller the amount of the polymerization starting dose, and the lower the polymerization temperature, the larger the weight average molecular weight.

硬化材料之含量在可使300%模數值達到50~350 mN/mm2之範圍內即可，尤其是相對於上述(甲基)丙烯酸烷基酯共聚物100重量份，較佳為0.05~3重量份，更佳為0.1~2.5重量份。更佳為0.15~2.0重量份。若硬化材料之含量在上述範圍內，則交聯密度達到適度之密度，成為不易殘留殘膠且具有充分之接著力、耐負重性之黏著劑。The content of the hardening material may be in the range of 300% modulus value of 50 to 350 mN/mm 2 , especially 0.05 to 3 parts by weight relative to the above alkyl (meth) acrylate copolymer, preferably 0.05 to 3 The parts by weight are more preferably 0.1 to 2.5 parts by weight. More preferably, it is 0.15 to 2.0 parts by weight. When the content of the hardening material is within the above range, the crosslinking density reaches an appropriate density, and the adhesive is less likely to remain in the residual rubber and has sufficient adhesion and load resistance.

上述(甲基)丙烯酸烷基酯共聚物之重量平均分子量與硬化材料之含量的範圍中，尤佳為黏著劑藉由拉伸速度為30 mm/min之拉伸試驗所獲得之23℃下之300%模數值為50~350 mN/mm2之範圍的值，更佳為80~300 mN/mm2，更佳為100~280 mN/mm2。若300%模數為50~350 mN/mm2，則具有充分之接著性、耐負重性，且剝離時之殘膠亦減少，故而較佳。In the range of the weight average molecular weight of the (meth)acrylic acid alkyl ester copolymer and the content of the hardening material, it is particularly preferable that the adhesive is obtained at 23 ° C by a tensile test at a tensile speed of 30 mm/min. The 300% modulus value is in the range of 50 to 350 mN/mm 2 , more preferably 80 to 300 mN/mm 2 , and even more preferably 100 to 280 mN/mm 2 . When the 300% modulus is 50 to 350 mN/mm 2 , it has sufficient adhesion and load-bearing property, and the residual rubber at the time of peeling is also reduced, which is preferable.

關於黏著劑中殘留之聚合起始劑，較佳為相對於黏著劑重量為8 ppm以下。若黏著劑中殘留之聚合起始劑相對於黏著劑總重量為8 ppm以下，則可大幅度抑制霧化之產生。關於藉由降低黏著劑層中殘留之聚合起始劑之量會改善光罩之霧化的原因尚不明確，現考慮如下。The polymerization initiator remaining in the adhesive is preferably 8 ppm or less based on the weight of the adhesive. If the polymerization initiator remaining in the adhesive is 8 ppm or less based on the total weight of the adhesive, the generation of atomization can be greatly suppressed. It is not clear why the atomization of the photomask is improved by reducing the amount of the polymerization initiator remaining in the adhesive layer, and it is considered as follows.

產生霧化之原因有多種，現認為其主要原因為：曝光氣體環境下存在之有機氣體成分藉由曝光光之能量而引起化學反應，其反應生成物會附著於光罩上而導致產生霧化。推測若黏著劑層存在某一定量以上之聚合起始劑，則該聚合起始劑會藉由曝光光之能量而開裂，引發有機氣體之化學反應，結果導致霧化之反應生成物之生成量大幅度增加。There are many reasons for the atomization. It is believed that the main reason is that the organic gas component existing in the exposed gas environment causes a chemical reaction by the energy of the exposure light, and the reaction product adheres to the reticle to cause atomization. . It is presumed that if a certain amount of the polymerization initiator is present in the adhesive layer, the polymerization initiator will be cracked by the energy of the exposure light, causing a chemical reaction of the organic gas, resulting in the formation of the atomized reaction product. increased badly.

基於以上原因，關於光罩護膜所使用之黏著劑中殘留的聚合起始劑的用量相對於黏著劑重量較佳為8 ppm以下，更佳為7 ppm以下，更佳為6 ppm以下。For the above reasons, the amount of the polymerization initiator remaining in the adhesive used for the reticle film is preferably 8 ppm or less, more preferably 7 ppm or less, still more preferably 6 ppm or less, based on the weight of the adhesive.

關於降低、控制黏著劑層中殘留之聚合起始劑的方法，有如下方法等：降低黏著劑聚合物聚合時之聚合起始劑量，或使用易於熱分解之聚合起始劑；又，藉由黏著劑之塗佈、乾燥步驟，長時間施加高溫，藉由乾燥步驟使聚合起始劑分解。The method for lowering and controlling the polymerization initiator remaining in the adhesive layer has the following methods, such as: reducing the polymerization initiation amount in the polymerization of the adhesive polymer, or using a polymerization initiator which is easily thermally decomposed; The coating and drying steps of the adhesive, high temperature application for a long period of time, and the polymerization initiator is decomposed by a drying step.

表示聚合起始劑之熱分解速度的指標有10小時半衰期溫度。所謂半衰期，係指聚合起始劑分解直至原來量之一半的時間，10小時半衰期溫度表示半衰期為10小時之溫度。10小時半衰期溫度較低之聚合起始劑易熱分解，因此不易殘留在黏著劑層上。尤佳為使用10小時半衰期溫度為80℃以下、較佳為75℃以下之聚合起始劑。An index indicating the rate of thermal decomposition of the polymerization initiator has a 10-hour half-life temperature. The term "half-life" refers to the time during which the polymerization initiator decomposes to one-half of the original amount, and the 10-hour half-life temperature represents a temperature at which the half-life is 10 hours. The polymerization initiator having a low 10-hour half-life temperature is easily decomposed and thus does not easily remain on the adhesive layer. It is especially preferred to use a polymerization initiator having a 10-hour half-life temperature of 80 ° C or lower, preferably 75 ° C or lower.

若上述聚合起始劑為偶氮系聚合起始劑，則可列舉：2,2'-偶氮雙(4-甲氧基-2,4-二甲基戊腈)(10小時半衰期溫度30℃)、2,2'-偶氮雙異丁腈(10小時半衰期溫度60℃)、2,2'-偶氮雙(2,4-二甲基戊腈)(10小時半衰期溫度51℃)、2,2'-偶氮雙(2-甲基丙酸甲酯)(10小時半衰期溫度66℃)、2,2'-偶氮雙(2-甲基丁腈)(10小時半衰期溫度67℃)，若為過氧化物系聚合起始劑，則可列舉：過氧化二苯甲醯(10小時半衰期溫度74℃)、過氧化二月桂醯(10小時半衰期溫度62℃)等，但並不限於此。When the polymerization initiator is an azo polymerization initiator, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (10-hour half-life temperature 30) °C), 2,2'-azobisisobutyronitrile (10-hour half-life temperature 60 °C), 2,2'-azobis(2,4-dimethylvaleronitrile) (10-hour half-life temperature 51 °C) , 2,2'-azobis(methyl 2-methylpropionate) (10-hour half-life temperature 66 ° C), 2,2'-azobis(2-methylbutyronitrile) (10-hour half-life temperature 67 °C), in the case of a peroxide-based polymerization initiator, examples include: benzoic acid peroxide (10-hour half-life temperature: 74° C.), and dilaurin peroxide (10-hour half-life temperature: 62° C.), but Not limited to this.

又，光聚合起始劑亦會導致產生霧化。作為降低、控制黏著劑層中殘留之光聚合起始劑之方法，可考慮如下方法：藉由加熱使之熱分解或乾燥、蒸發之方法，或照射紫外線而使光聚合起始劑分解之方法，使用藉由上述方法而易於分解之光聚合起始劑之方法等。作為藉由上述方法而易於分解之光聚合起始劑，可列舉：烷基苯酮系聚合起始劑或醯基氧化膦系聚合起始劑等。作為烷基苯酮系聚合起始劑，具體可列舉：2,2-二甲氧基-1,2-二苯基乙烷-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-甲基丙烷-1-酮、2-羥基-1-{4-[4-(2-羥基-2-甲基-丙醯基)-苄基]苯基}-2-甲基丙烷-1-酮、2-甲基-1-(4-甲基硫苯基)-2-嗎啉基丙烷-1-酮、2-苄基-2-二甲胺基-1-(4-嗎啉基苯基)-1-丁酮、2-(二甲胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基)苯基]-1-丁酮等。作為醯基氧化膦系聚合起始劑，可列舉：2,4,6-三甲基苯甲醯基-二苯基-氧化膦、雙(2,4,6-三甲基苯甲醯基)苯基氧化膦等。Also, the photopolymerization initiator also causes fogging. As a method for lowering and controlling the photopolymerization initiator remaining in the adhesive layer, a method of decomposing the photopolymerization initiator by thermal decomposition or drying, evaporation, or irradiation with ultraviolet rays may be considered. A method of using a photopolymerization initiator which is easily decomposed by the above method, and the like. The photopolymerization initiator which is easily decomposed by the above method may, for example, be an alkylphenone-based polymerization initiator or a mercaptophosphine oxide-based polymerization initiator. Specific examples of the alkylphenone-based polymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl-phenyl ketone, and 2- Hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropan-1-one, 2- Hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]phenyl}-2-methylpropan-1-one, 2-methyl-1-( 4-methylthiophenyl)-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone, 2 -(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone. Examples of the fluorenylphosphine oxide-based polymerization initiator include 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzylidene). Phenylphosphine oxide and the like.

為使黏著劑中殘留之聚合起始劑之總重量相對於黏著劑總重量為8 ppm以下，較佳為使用包含含有(甲基)丙烯酸烷基酯共聚物與硬化材料之反應生成物而成之組合物的黏著劑，該(甲基)丙烯酸烷基酯共聚物係藉由使具有碳數4~14之烷基之(甲基)丙烯酸烷基酯與含有與硬化材料具有反應性之官能基之單體中之至少兩種單體成分共聚合而獲得的共聚物。In order to make the total weight of the polymerization initiator remaining in the adhesive 8 ppm or less based on the total weight of the adhesive, it is preferred to use a reaction product containing a copolymer of an alkyl (meth)acrylate and a hardened material. The adhesive of the composition, the alkyl (meth)acrylate copolymer is obtained by reacting an alkyl (meth)acrylate having an alkyl group having 4 to 14 carbons with a compound having reactivity with a hardening material. A copolymer obtained by copolymerizing at least two monomer components of a monomer.

又，黏著劑組合物中除上述反應生成物以外亦可視需要含有填充劑、顏料、稀釋劑、抗老化劑、紫外線穩定劑等先前眾所周知之添加劑。該等添加劑可使用1種或2種以上。然而，較佳為適時設定添加量，以獲得所需物性。Further, the adhesive composition may contain a previously known additive such as a filler, a pigment, a diluent, an anti-aging agent, or a UV stabilizer, in addition to the above reaction product. These additives may be used alone or in combination of two or more. However, it is preferred to set the addition amount at a proper time to obtain desired physical properties.

本發明之光罩護膜例如可藉由以下方法適宜地製造。The photomask film of the present invention can be suitably produced, for example, by the following method.

首先，將上述(甲基)丙烯酸烷基酯共聚物溶液與多官能性環氧化合物溶液加以混合，獲得黏著劑前驅物組合物。於該情形時，為了塗佈特定厚度、寬度之光罩黏著劑層，進而利用溶劑將黏著劑前驅物組合物稀釋，調整溶液濃度(黏度)。基於溶解性、蒸發速度等觀點選擇用以稀釋之溶劑。作為溶劑之較佳具體例，可列舉：丙酮、乙酸乙酯、甲苯，但並不限定於該等。First, the above (meth)acrylic acid alkyl ester copolymer solution and a polyfunctional epoxy compound solution are mixed to obtain an adhesive precursor composition. In this case, in order to apply a mask adhesive layer of a specific thickness and width, the adhesive precursor composition is diluted with a solvent to adjust the solution concentration (viscosity). The solvent to be diluted is selected from the viewpoints of solubility, evaporation rate, and the like. Preferable specific examples of the solvent include acetone, ethyl acetate, and toluene, but are not limited thereto.

其次，將該黏著劑前驅物組合物塗佈至一端面具有光罩護膜薄膜之光罩護膜框之另一端面。塗佈方法並無特別限定，較佳為使用分注器進行塗佈。上述黏著劑前驅物組合物中之丙烯酸共聚物溶液(稱為含有溶劑與(甲基)丙烯酸烷基酯共聚物之溶液)的黏度並無特別限定，較佳為50 P以下，更佳為10~40 P，更佳為20~30 P左右(B型黏度計，25℃)。利用分注器進行塗佈時，利用溶劑進行稀釋，此時塗佈液之黏絲較少，容易調整為穩定之寬度、厚度。Next, the adhesive precursor composition is applied to the other end surface of the reticle film frame having the reticle film on one end. The coating method is not particularly limited, and it is preferably applied by using a dispenser. The viscosity of the acrylic copolymer solution (referred to as a solution containing a solvent and a (meth)acrylic acid alkyl ester copolymer) in the above adhesive precursor composition is not particularly limited, but is preferably 50 P or less, more preferably 10 ~40 P, more preferably about 20~30 P (B type viscometer, 25 ° C). When coating by a dispenser, it is diluted with a solvent, and at this time, the coating liquid has few adhesive filaments, and it is easy to adjust to a stable width and thickness.

再次，可藉由將所塗佈之黏著劑層加熱乾燥，而除去溶劑及/或殘留單體。進而，若(甲基)丙烯酸烷基酯共聚物所具有之官能基與硬化材料發生加熱反應而形成交聯結構，則光罩護膜框黏著劑組合物形成一體，而密著於光罩護膜框表面。Again, the solvent and/or residual monomer can be removed by heating and drying the applied adhesive layer. Further, when the functional group of the (meth)acrylic acid alkyl ester copolymer is heated and reacted with the hardening material to form a crosslinked structure, the photomask cover film adhesive composition is integrated, and is adhered to the photomask The surface of the membrane frame.

考慮到溶劑及殘留單體之沸點、(甲基)丙烯酸烷基酯共聚物之分解溫度，該乾燥溫度較佳為50~200℃，較佳為60~190℃。又，較佳為將黏著劑於充分乾燥之狀態下用於光罩護膜，以使黏著劑中所含溶劑於下述逸氣試驗中達到50 ppb以下。The drying temperature is preferably from 50 to 200 ° C, preferably from 60 to 190 ° C, in consideration of the boiling point of the solvent and the residual monomer and the decomposition temperature of the alkyl (meth)acrylate copolymer. Further, it is preferred that the adhesive is applied to the mask film in a sufficiently dried state so that the solvent contained in the adhesive reaches 50 ppb or less in the following outgassing test.

亦可於乾燥、交聯後，貼附用以保護黏著面之脫模片。脫模片通常使用聚酯等之厚度為30~200 μm左右之膜。又，若自黏著劑剝下脫模片時之剝離力較大，則有剝下時黏著劑發生變形之虞，因此可於與黏著劑接觸之膜表面進行聚矽氧或氟等之脫模處理而形成適當之剝離力。After drying and cross-linking, the release sheet for protecting the adhesive surface may be attached. As the release sheet, a film having a thickness of about 30 to 200 μm such as polyester is usually used. Further, if the peeling force is large when the release sheet is peeled off from the adhesive, the adhesive is deformed when peeled off, so that the release of the polysiloxane or fluorine can be performed on the surface of the film which is in contact with the adhesive. Treatment to form a suitable peel force.

可於貼附用以保護黏著面之脫模片後，施加負重，將黏著劑表面成型為大致平坦之表面。After attaching the release sheet for protecting the adhesive surface, a load is applied to form the surface of the adhesive into a substantially flat surface.

[實施例][Examples]

以下，藉由實施例及比較例進而具體說明本發明，但本發明並不受該等之任何限定。Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited thereto.

<實施例1><Example 1> (黏著劑前驅物組合物之製備)(Preparation of Adhesive Precursor Composition)

(甲基)丙烯酸烷基酯共聚物1係藉由眾所周知之方法製備。具體而言，於具備攪拌機、溫度計、回流冷卻器、滴加裝置、氮氣導入管之反應容器中放入乙酸乙酯(30重量份)，以30/66/1.5/2.5/1.0之重量比加入丙烯酸異丁酯/丙烯酸丁酯/丙烯酸/丙烯酸2-羥基乙酯/2,2'-偶氮雙異丁腈之混合物(32重量份)，於氮氣環境下，使該反應溶液於60℃下反應8小時。反應結束後，添加甲苯(38重量份)，獲得不揮發成分濃度為32重量%之丙烯酸共聚物溶液(重量平均分子量130萬)。於所獲得之丙烯酸共聚物溶液100重量份中添加0.3重量份多官能性環氧化合物(1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷，不揮發成分濃度為5%，甲苯溶液)，並進行攪拌混合，獲得黏著劑前驅物組合物。The alkyl (meth)acrylate copolymer 1 is prepared by a well-known method. Specifically, ethyl acetate (30 parts by weight) is placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, and is added in a weight ratio of 30/66/1.5/2.5/1.0. a mixture of isobutyl acrylate/butyl acrylate/acrylic acid/2-hydroxyethyl acrylate/2,2'-azobisisobutyronitrile (32 parts by weight), the reaction solution was allowed to stand at 60 ° C under a nitrogen atmosphere Reaction for 8 hours. After completion of the reaction, toluene (38 parts by weight) was added to obtain an acrylic copolymer solution (weight average molecular weight: 1.3 million) having a nonvolatile content of 32% by weight. 0.3 parts by weight of a polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane) was added to 100 parts by weight of the obtained acrylic copolymer solution, and the concentration of nonvolatile components was added. It was 5%, a toluene solution), and stirred and mixed to obtain an adhesive precursor composition.

(附帶黏著劑之光罩護膜之製作)(production of photomask film with adhesive)

其後，利用分注器將所調配之上述黏著劑前驅物組合物塗佈至一端面接著有光罩護膜薄膜之鋁合金製光罩護膜框(外徑113 mm×149 mm，內徑109 mm×145 mm，高度4.8 mm)之另一端面上。以2個階段對其進行加熱乾燥、固化(第1階段：100℃，8分鐘；第2階段：180℃，8分鐘)，獲得形成有含有上述黏著劑前驅物組合物之黏著劑層(厚度0.2 mm)的實施例1之光罩護膜。繼而，貼附經聚矽氧脫模處理之厚度為100 μm之聚酯製保護膜，於室溫(20±3℃)下熟化3天，使黏著力穩定化，製作附帶黏著劑之光罩護膜。藉由以下方法對所獲得之附帶黏著劑之光罩護膜進行評價。Thereafter, the prepared adhesive precursor composition is applied to an end face of the aluminum alloy reticle cover film with a mask film (with an outer diameter of 113 mm × 149 mm, inner diameter) by means of a dispenser. On the other end of 109 mm × 145 mm, height 4.8 mm). The film was heated and dried in two stages (first stage: 100 ° C, 8 minutes; second stage: 180 ° C, 8 minutes) to obtain an adhesive layer (thickness) formed with the above-mentioned adhesive precursor composition. 0.2 mm) of the reticle film of Example 1. Then, a polyester protective film having a thickness of 100 μm which was subjected to polysilicon deoxidation treatment was attached and aged at room temperature (20±3° C.) for 3 days to stabilize the adhesion, and a photomask with an adhesive was prepared. Protective film. The obtained visor film with an adhesive was evaluated by the following method.

(逸氣試驗)(Out of gas test)

自光罩護膜產生之逸氣可利用吸附材料進行捕獲而進行分析。於50 mL/min之氦氣流下，將實施例中獲得之光罩護膜於50℃下加熱處理30分鐘，並利用吸附劑進行捕獲。吸附劑係使用TENAX TA(GL Science製造)。樣品對GC裝置之導入係使用頂空進樣器，使吸附管於250℃下處理10分鐘，並進行熱脫附，藉由GC/MS(gas chromatography/mass spectroscope，氣相層析/質譜儀)對所產生之逸氣進行分析。GC/MS分析條件如下。The outgas generated from the mask film can be captured by the adsorbent material for analysis. The reticle film obtained in the example was heat-treated at 50 ° C for 30 minutes under a helium flow of 50 mL/min, and was captured by an adsorbent. As the adsorbent, TENAX TA (manufactured by GL Science) was used. The sample was introduced into the GC device using a headspace sampler, and the adsorption tube was treated at 250 ° C for 10 minutes and thermally desorbed by GC/MS (gas chromatography/mass spectroscope). ) Analyze the generated outgas. The GC/MS analysis conditions are as follows.

GC裝置：Agilent Technologies 7890A GC SystemGC unit: Agilent Technologies 7890A GC System

管柱：Agilent Technologies 19091J-413 HP-5(30 m×0.320 mm×0.25 μm)Column: Agilent Technologies 19091J-413 HP-5 (30 m × 0.320 mm × 0.25 μm)

溫度條件：30℃~280℃(10℃/min)Temperature condition: 30 ° C ~ 280 ° C (10 ° C / min)

MS裝置：JEOL Jms-Q1000GC K9MS device: JEOL Jms-Q1000GC K9

離子化：70 eVIonization: 70 eV

掃描範圍：m/z=10~500Scanning range: m/z=10~500

甲苯之定量係用根據絕對校準曲線求出之重量除以1片光罩護膜之重量而算出，並按照以下基準進行評價。The amount of toluene was calculated by dividing the weight obtained from the absolute calibration curve by the weight of one sheet of the mask film, and evaluated according to the following criteria.

10 ppb以下...◎10 ppb or less... ◎

50 ppb以下...○50 ppb or less...○

51 ppb以上...×51 ppb or more...×

(霧化測試)(Atomization test)

將實施例中所獲得之附帶黏著劑之光罩護膜剝下保護膜，利用簡易型貼合機(mounter)，於負重(30 Kgf，60秒)下將其貼附至6025石英空白基材上，獲得貼附有光罩護膜之基材。The protective film with the adhesive agent obtained in the examples was peeled off from the protective film, and attached to the 6025 quartz blank substrate under a load (30 Kgf, 60 seconds) using a simple type of mounter. On the top, a substrate to which a mask film is attached is obtained.

以0.7 mJ/cm2/pulse、頻率250 Hz，且以8小時、5000 J/cm2之照射量對所獲得之基材照射ArF準分子雷射。對照射後之基材及光罩護膜，目測有無產生霧化，按照以下基準進行評價。The obtained substrate was irradiated with an ArF excimer laser at an irradiation dose of 8 m, 5000 J/cm 2 at a frequency of 0.7 mJ/cm 2 /pulse at a frequency of 250 Hz. The substrate and the mask film after the irradiation were visually observed for the occurrence of fogging, and evaluated according to the following criteria.

○...基材及光罩護膜未產生霧化○...The substrate and the mask film are not fogged.

×...基材及光罩護膜產生霧化×...The substrate and the mask film are fogged

(剝離性評價)(peelability evaluation)

將實施例中所獲得之附帶黏著劑之光罩護膜剝下保護膜，利用簡易型貼合機，於負重(30 Kgf，60 sec)下將其貼附至6025附帶鉻之空白基材上，獲得貼附有光罩護膜之基材。將貼附有光罩護膜之基材，於室溫(20±3℃)下放置2小時後，將基材水平固定，利用拉伸試驗機，將光罩護膜之一角，沿著與光罩面垂直之方向，以5 mm/min之速度進行拉伸，而剝離光罩護膜。剝離性係觀察各黏附體表面之狀態，按照以下基準進行評價。The protective film with the adhesive agent obtained in the examples was peeled off from the protective film, and attached to a 6025 chrome-plated blank substrate under a load (30 Kgf, 60 sec) by a simple type laminating machine. A substrate to which a reticle film is attached is obtained. The substrate to which the photomask film is attached is placed at room temperature (20±3° C.) for 2 hours, and then the substrate is horizontally fixed, and a corner of the mask film is applied along the tensile tester. The mask surface is perpendicular to the direction of stretching at a speed of 5 mm/min, and the mask film is peeled off. The peeling property was observed on the surface of each of the adherends, and evaluated according to the following criteria.

◎：殘膠面積為整體貼附面積之0~5%◎: Residual rubber area is 0~5% of the total attached area

○：殘膠面積為整體貼附面積之6~20%○: Residual rubber area is 6~20% of the total attached area

×：殘膠面積為整體貼附面積之21~100%×: Residual rubber area is 21~100% of the total attached area

(耐負重試驗)(with load-bearing test)

將實施例中所獲得之附帶黏著劑之光罩護膜剝下保護膜，利用簡易型貼合機，於負重(30 Kgf，60 sec)下將其貼附至6025石英空白基材及6025附帶鉻之空白基材上，獲得貼附有光罩護膜之基材。於貼附有光罩護膜之基材上設置1 Kg之重物，並於室溫下放置。按照以下基準對光罩護膜自基材剝離為止之時間進行評價。The protective film with the adhesive agent obtained in the examples was peeled off from the protective film, and attached to a 6025 quartz blank substrate and 6025 by a simple type bonding machine under a load (30 Kgf, 60 sec). On the blank substrate of chrome, a substrate to which a mask film is attached is obtained. A weight of 1 Kg was placed on the substrate to which the reticle film was attached, and placed at room temperature. The time until the mask film was peeled off from the substrate was evaluated according to the following criteria.

◎：經過3天亦無氣道◎: There is no airway after 3 days.

○：經過1天後光罩護膜自基材脫落○: After one day, the mask film is peeled off from the substrate.

×：經過3小時後光罩護膜自基材脫落×: After 3 hours, the mask film peeled off from the substrate.

(分子量測定)(molecular weight determination)

將黏著劑試料真空乾燥，除去溶劑。於試料中添加溶離液，調整為1.0 mg/mL。利用0.5微米過濾器進行過濾，將濾液作為GPC試料。GPC之測定條件如下。The adhesive sample was vacuum dried to remove the solvent. The solution was added to the sample and adjusted to 1.0 mg/mL. Filtration was carried out using a 0.5 micron filter, and the filtrate was used as a GPC sample. The measurement conditions of GPC are as follows.

GPC　資料處理：Tosoh GPC-8020GPC Data Processing: Tosoh GPC-8020

裝置：Tosoh HLC-8220GPCDevice: Tosoh HLC-8220GPC

管柱：TSKgel SuperHZN-M(4.6 mmI.D.×15 cm)1根+TSKgel SuperHZ2000(4.6 mmI.D.×15 cm)1根Column: TSKgel SuperHZN-M (4.6 mmI.D. × 15 cm) 1 + TSKgel SuperHZ2000 (4.6 mmI.D. × 15 cm) 1

烘箱：40℃Oven: 40 ° C

溶離液：0.35 mL/min CHCl3 Dissolved solution: 0.35 mL/min CHCl 3

試料量：50 μl(1.0 mg/mL)Sample volume: 50 μl (1.0 mg/mL)

檢測器：RIDetector: RI

校準曲線：聚苯乙烯Calibration curve: polystyrene

(利用甲苯或乙酸乙酯之膨潤度測定)(Measured by the degree of swelling of toluene or ethyl acetate)

利用刮刀自實施例中所獲得之黏著劑層刮取約100 mg(重量A)之黏著劑，包在由尼龍網(網眼200 μm)中，於20℃之條件下於甲苯溶液或乙酸乙酯溶液中浸漬1周。其後，自溶液取出包裹體，測定剛自溶液中取出後之黏著劑未溶解部分的重量(重量B)。此時將以B/A算出之值作為甲苯或乙酸乙酯之重量膨潤度。Approximately 100 mg (weight A) of the adhesive was scraped from the adhesive layer obtained in the examples using a doctor blade, and wrapped in a nylon mesh (mesh 200 μm) at 20 ° C in toluene solution or acetic acid The ester solution was immersed for 1 week. Thereafter, the inclusions were taken out from the solution, and the weight (weight B) of the undissolved portion of the adhesive immediately after being taken out from the solution was measured. At this time, the value calculated by B/A was taken as the weight swelling degree of toluene or ethyl acetate.

<實施例2><Example 2>

除了將多官能性環氧化合物(1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷，不揮發成分濃度為5%，甲苯溶液)變成0.2重量份以外，藉由與實施例1相同之方法製作光罩護膜樣品，並進行評價。In addition to the polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, the concentration of the nonvolatile component is 5%, and the toluene solution) is 0.2 parts by weight, A sample of the mask film was prepared and evaluated in the same manner as in Example 1.

<實施例3><Example 3>

(甲基)丙烯酸烷基酯共聚物2係藉由眾所周知之方法製備。具體而言，於具備攪拌機、溫度計、回流冷卻器、滴加裝置、氮氣導入管之反應容器中放入乙酸乙酯(30重量份)，以98/2/1之重量比加入丙烯酸丁酯/丙烯酸/2,2'-偶氮雙異丁腈之混合物(32重量份)，於氮氣環境下，使該反應溶液於60℃下反應8小時。反應結束後，添加甲苯(38重量份)，獲得不揮發成分濃度為32重量%之丙烯酸共聚物溶液(重量平均分子量170萬)。於所獲得之丙烯酸共聚物溶液100重量份中添加0.2重量份多官能性環氧化合物(1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷，不揮發成分濃度為5%，甲苯溶液)，並進行攪拌混合，獲得黏著劑前驅物組合物。其後藉由與實施例1相同之方式製作光罩護膜樣品，並進行評價。The (meth)acrylic acid alkyl ester copolymer 2 is prepared by a well-known method. Specifically, ethyl acetate (30 parts by weight) was placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, and butyl acrylate was added in a weight ratio of 98/2/1. A mixture of acrylic acid/2,2'-azobisisobutyronitrile (32 parts by weight) was reacted at 60 ° C for 8 hours under a nitrogen atmosphere. After completion of the reaction, toluene (38 parts by weight) was added to obtain an acrylic copolymer solution (weight average molecular weight: 1.7 million) having a nonvolatile content of 32% by weight. 0.2 parts by weight of a polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane) was added to 100 parts by weight of the obtained acrylic copolymer solution, and the concentration of nonvolatile components was added. It was 5%, a toluene solution), and stirred and mixed to obtain an adhesive precursor composition. Thereafter, a sample of the photomask film was prepared and evaluated in the same manner as in Example 1.

<實施例4><Example 4>

除了將多官能性環氧化合物(1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷變成甲苯二異氰酸酯之三羥甲基丙烷加成物0.45份以外，藉由與實施例1相同之方法製作光罩護膜樣品，並進行評價。By using a polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane to be 0.45 parts of a trimethylolpropane adduct of toluene diisocyanate A sample of the mask film was prepared and evaluated in the same manner as in Example 1.

<實施例5><Example 5>

(甲基)丙烯酸烷基酯共聚物3係藉由眾所周知之方法製備。具體而言，於具備攪拌機、溫度計、回流冷卻器、滴加裝置、氮氣導入管之反應容器中放入乙酸乙酯(50重量份)，以98/2/1之重量比加入丙烯酸丁酯/丙烯酸/2,2'-偶氮雙異丁腈之混合物(32重量份)，於氮氣環境下，使該反應溶液於65℃下反應8小時。反應結束後，添加甲苯(18重量份)，獲得不揮發成分濃度為32重量%之丙烯酸共聚物溶液(重量平均分子量60萬)。於所獲得之丙烯酸共聚物溶液100重量份中添加0.3重量份多官能性環氧化合物(1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷，不揮發成分濃度為5%，甲苯溶液)，並進行攪拌混合，獲得黏著劑前驅物組合物。其後藉由與實施例1相同之方式製作光罩護膜樣品，並進行評價。The (meth)acrylic acid alkyl ester copolymer 3 is prepared by a well-known method. Specifically, ethyl acetate (50 parts by weight) was placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, and butyl acrylate was added in a weight ratio of 98/2/1. A mixture of acrylic acid/2,2'-azobisisobutyronitrile (32 parts by weight) was reacted at 65 ° C for 8 hours under a nitrogen atmosphere. After completion of the reaction, toluene (18 parts by weight) was added to obtain an acrylic copolymer solution (weight average molecular weight: 600,000) having a nonvolatile content of 32% by weight. 0.3 parts by weight of a polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane) was added to 100 parts by weight of the obtained acrylic copolymer solution, and the concentration of nonvolatile components was added. It was 5%, a toluene solution), and stirred and mixed to obtain an adhesive precursor composition. Thereafter, a sample of the photomask film was prepared and evaluated in the same manner as in Example 1.

<實施例6><Example 6>

除了將多官能性環氧化合物(1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷，不揮發成分濃度為5%，甲苯溶液)變成2.0份以外，藉由與實施例1相同之方法製作光罩護膜樣品，並進行評價In addition to the polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, the concentration of the nonvolatile component is 5%, and the toluene solution) is changed to 2.0 parts. A mask film sample was prepared and evaluated in the same manner as in Example 1.

<實施例7><Example 7>

(甲基)丙烯酸烷基酯共聚物4係藉由眾所周知之方法製備。具體而言，於具備攪拌機、溫度計、回流冷卻器、滴加裝置、氮氣導入管之反應容器中放入乙酸乙酯(50重量份)，以30/66/1.5/2.5/1.0之重量比加入丙烯酸異丁酯/丙烯酸丁酯/丙烯酸/丙烯酸2-羥基乙酯/2,2'-偶氮雙異丁腈之混合物(50重量份)，於氮氣環境下，使該反應溶液於55℃下反應8小時。反應結束後，添加甲苯(20重量份)，獲得丙烯酸共聚物溶液(重量平均分子量為280萬)。於所獲得之丙烯酸共聚物溶液100重量份中添加0.3重量份多官能性環氧化合物(1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷，不揮發成分濃度為5%，甲苯溶液)，並進行攪拌混合，獲得黏著劑前驅物組合物。The alkyl (meth)acrylate copolymer 4 is prepared by a well-known method. Specifically, ethyl acetate (50 parts by weight) is placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, and is added in a weight ratio of 30/66/1.5/2.5/1.0. a mixture of isobutyl acrylate/butyl acrylate/acrylic acid/2-hydroxyethyl acrylate/2,2'-azobisisobutyronitrile (50 parts by weight), and the reaction solution was allowed to stand at 55 ° C under a nitrogen atmosphere. Reaction for 8 hours. After completion of the reaction, toluene (20 parts by weight) was added to obtain an acrylic copolymer solution (weight average molecular weight: 2.8 million). 0.3 parts by weight of a polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane) was added to 100 parts by weight of the obtained acrylic copolymer solution, and the concentration of nonvolatile components was added. It was 5%, a toluene solution), and stirred and mixed to obtain an adhesive precursor composition.

<比較例1><Comparative Example 1>

除了將多官能性環氧化合物(1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷變成0.02份以外，藉由與實施例1相同之方法製作光罩護膜，並進行評價。A mask film was produced in the same manner as in Example 1 except that the polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane was changed to 0.02 parts. And evaluate.

<比較例2><Comparative Example 2>

相對於聚矽氧黏著劑(Dowcorning(股)製造，SD4580(商品名)不揮發成分濃度為40%，甲苯/二甲苯溶液)100重量份添加0.9重量份硬化劑(Dowcorning(股)製造，SRX212)，獲得黏著劑前驅物組合物。其後藉由與實施例1相同之方式製作光罩護膜樣品，並進行評價。0.9 parts by weight of a hardener (manufactured by Dow Corning, SRX212) was added to 100 parts by weight of a polyoxyxylene adhesive (manufactured by Dow Corning, SD4580 (trade name) with a nonvolatile content of 40%, toluene/xylene solution). ), an adhesive precursor composition is obtained. Thereafter, a sample of the photomask film was prepared and evaluated in the same manner as in Example 1.

<比較例3><Comparative Example 3>

將苯乙烯-乙烯/丁烯-苯乙烯之橡膠系熱熔黏著劑塗佈於一端面接著有光罩護膜薄膜之鋁合金製的光罩護膜框(外徑113 mm×149 mm，內徑109 mm×145 mm，高度4.8 mm)之另一端面。其後藉由與實施例1相同之方式製作光罩護膜樣品，並進行評價A rubber-based hot-melt adhesive of styrene-ethylene/butylene-styrene is applied to a mask frame of an aluminum alloy film having an outer surface and a mask film (outer diameter: 113 mm × 149 mm, The other end of the diameter is 109 mm × 145 mm and the height is 4.8 mm. Thereafter, a sample of the mask film was prepared and evaluated in the same manner as in Example 1.

<實施例8><Example 8> (黏著劑前驅物組合物之製備)(Preparation of Adhesive Precursor Composition)

(甲基)丙烯酸烷基酯共聚物5係藉由眾所周知之方法製備。具體而言，於具備攪拌機、溫度計、回流冷卻器、滴加裝置、氮氣導入管之反應容器中放入乙酸乙酯(30重量份)，以48/48/1.5/2.5/1.0之重量比加入丙烯酸異丁酯/丙烯酸丁酯/丙烯酸/丙烯酸2-羥基乙酯/2,2'-偶氮雙異丁腈之混合物(32重量份)，於氮氣環境下，使該反應溶液於60℃下反應8小時。反應結束後，添加甲苯(38重量份)，獲得不揮發成分濃度為32重量%之丙烯酸共聚物溶液(重量平均分子量為120萬)。於所獲得之丙烯酸共聚物溶液100重量份中添加0.25重量份多官能性環氧化合物(1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷，不揮發成分濃度為5%，甲苯溶液)，並進行攪拌混合，獲得黏著劑前驅物組合物。The alkyl (meth)acrylate copolymer 5 is prepared by a well-known method. Specifically, ethyl acetate (30 parts by weight) is placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, and is added in a weight ratio of 48/48/1.5/2.5/1.0. a mixture of isobutyl acrylate/butyl acrylate/acrylic acid/2-hydroxyethyl acrylate/2,2'-azobisisobutyronitrile (32 parts by weight), the reaction solution was allowed to stand at 60 ° C under a nitrogen atmosphere Reaction for 8 hours. After completion of the reaction, toluene (38 parts by weight) was added to obtain an acrylic copolymer solution (weight average molecular weight: 1.2 million) having a nonvolatile content of 32% by weight. 0.25 parts by weight of a polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane) was added to 100 parts by weight of the obtained acrylic copolymer solution, and the concentration of nonvolatile components was added. It was 5%, a toluene solution), and stirred and mixed to obtain an adhesive precursor composition.

(附帶黏著劑之光罩護膜之製作)(production of photomask film with adhesive)

其後，利用分注器將所調配之上述黏著劑組合物塗佈至一端面接著有光罩護膜薄膜之鋁合金製的光罩護膜框(外徑113 mm×149 mm，內徑109 mm×145 mm，高度4.8 mm)之另一端面。以2個階段將其加熱乾燥、固化(第1階段：100℃，8分鐘；第2階段：180℃，8分鐘)，獲得形成有含有上述黏著劑前驅物組合物之黏著劑層(厚度0.2 mm)的實施例8之光罩護膜。繼而，貼附經聚矽氧脫模處理之厚度為100 μm之聚酯製保護膜，於室溫(20±3℃)下熟化3天，使黏著力穩定化，製作附帶黏著劑之光罩護膜。對所獲得之附帶黏著劑之光罩護膜進行上述評價，除此以外實施下述評價。Thereafter, the adhesive composition prepared by applying the above-mentioned adhesive composition to a single end face and then a mask film of an aluminum alloy film having a mask film (outer diameter 113 mm × 149 mm, inner diameter 109) The other end of mm × 145 mm, height 4.8 mm). It was heat-dried and solidified in two stages (first stage: 100 ° C, 8 minutes; second stage: 180 ° C, 8 minutes) to obtain an adhesive layer (thickness 0.2) formed with the above-mentioned adhesive precursor composition. Mm) The reticle film of Example 8. Then, a polyester protective film having a thickness of 100 μm which was subjected to polysilicon deoxidation treatment was attached and aged at room temperature (20±3° C.) for 3 days to stabilize the adhesion, and a photomask with an adhesive was prepared. Protective film. The following evaluation was performed on the obtained photomask film with an adhesive attached thereto, and the following evaluation was performed.

(模數測定)(modulus measurement)

使用自動立體測圖儀，將黏著層之厚度0.2 mm、寬度1.5 mm之黏著劑樣品以夾盤間10 mm、拉伸速度30 mm/min、23℃下進行拉伸，測定此時之力。The adhesive sample having a thickness of 0.2 mm and a width of 1.5 mm of the adhesive layer was stretched by 10 mm between the chucks, a tensile speed of 30 mm/min, and 23 ° C using an autostereograph, and the force at this time was measured.

用300%拉伸時之力除以試料之剖面積，將所得值設為300%模數值。The force at 300% stretching was divided by the cross-sectional area of the sample, and the obtained value was set to a 300% modulus value.

<實施例9><Example 9>

除了將多官能性環氧化合物(1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷，不揮發成分濃度為5%，甲苯溶液)變成0.15重量份以外，藉由與實施例8相同之方法製作光罩護膜樣品，並進行評價。In addition to the polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, the concentration of the nonvolatile component is 5%, and the toluene solution) is 0.15 parts by weight. A sample of the mask film was prepared and evaluated in the same manner as in Example 8.

<實施例10><Example 10>

除了將多官能性環氧化合物(1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷，不揮發成分濃度為5%，甲苯溶液)變成1.8重量份以外，藉由與實施例8相同之方法製作光罩護膜樣品，並進行評價。In addition to the polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, the concentration of the nonvolatile component is 5%, and the toluene solution) is 1.8 parts by weight, A sample of the mask film was prepared and evaluated in the same manner as in Example 8.

<實施例11><Example 11>

(甲基)丙烯酸烷基酯共聚物6係藉由眾所周知之方法製備。具體而言，於具備攪拌機、溫度計、回流冷卻器、滴加裝置、氮氣導入管之反應容器中放入乙酸乙酯(30重量份)，以99/1/1.0之重量比加入丙烯酸丁酯/丙烯酸/2,2'-偶氮雙異丁腈之混合物(32重量份)，於氮氣環境下，使該反應溶液於60℃下反應8小時。反應結束後，添加甲苯(38重量份)，獲得不揮發成分濃度為32重量%之丙烯酸共聚物溶液(重量平均分子量為180萬)。於所獲得之丙烯酸共聚物溶液100重量份中添加0.15重量份多官能性環氧化合物(1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷，不揮發成分濃度為5%，甲苯溶液)，並進行攪拌混合，獲得黏著劑前驅物組合物。其後藉由與實施例8相同之方式製作光罩護膜樣品，並進行評價。The alkyl (meth)acrylate copolymer 6 is prepared by a well-known method. Specifically, ethyl acetate (30 parts by weight) was placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, and butyl acrylate was added in a weight ratio of 99/1/1.0. A mixture of acrylic acid/2,2'-azobisisobutyronitrile (32 parts by weight) was reacted at 60 ° C for 8 hours under a nitrogen atmosphere. After completion of the reaction, toluene (38 parts by weight) was added to obtain an acrylic copolymer solution (weight average molecular weight: 1.8 million) having a nonvolatile content of 32% by weight. To 100 parts by weight of the obtained acrylic copolymer solution, 0.15 parts by weight of a polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, a concentration of a nonvolatile component is added It was 5%, a toluene solution), and stirred and mixed to obtain an adhesive precursor composition. Thereafter, a sample of the mask film was prepared and evaluated in the same manner as in Example 8.

<實施例12><Example 12>

(甲基)丙烯酸烷基酯共聚物7係藉由眾所周知之方法製備。具體而言，於具備攪拌機、溫度計、回流冷卻器、滴加裝置、氮氣導入管之反應容器中放入乙酸乙酯(50重量份)，以99/1/1.0之重量比加入丙烯酸丁酯/丙烯酸/2,2'-偶氮雙異丁腈之混合物(32重量份)，於氮氣環境下，使該反應溶液於65℃下反應8小時。反應結束後，添加甲苯(18重量份)，獲得不揮發成分濃度為32重量%之丙烯酸共聚物溶液(重量平均分子量為60萬)。於所獲得之丙烯酸共聚物溶液100重量份中添加0.25重量份多官能性環氧化合物(1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷，不揮發成分濃度為5%，甲苯溶液)，並進行攪拌混合，獲得黏著劑前驅物組合物。其後藉由與實施例8相同之方式製作光罩護膜樣品，並進行評價。The alkyl (meth)acrylate copolymer 7 is prepared by a well-known method. Specifically, ethyl acetate (50 parts by weight) is placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, and butyl acrylate is added in a weight ratio of 99/1/1.0. A mixture of acrylic acid/2,2'-azobisisobutyronitrile (32 parts by weight) was reacted at 65 ° C for 8 hours under a nitrogen atmosphere. After completion of the reaction, toluene (18 parts by weight) was added to obtain an acrylic copolymer solution (weight average molecular weight: 600,000) having a nonvolatile content of 32% by weight. 0.25 parts by weight of a polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane) was added to 100 parts by weight of the obtained acrylic copolymer solution, and the concentration of nonvolatile components was added. It was 5%, a toluene solution), and stirred and mixed to obtain an adhesive precursor composition. Thereafter, a sample of the mask film was prepared and evaluated in the same manner as in Example 8.

<比較例4><Comparative Example 4>

除了將多官能性環氧化合物(1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷變成3.2份以外，藉由與實施例8相同之方法製作光罩護膜樣品，並進行評價。A mask film was produced in the same manner as in Example 8 except that the polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane was changed to 3.2 parts. Samples were evaluated.

<比較例5><Comparative Example 5>

除了將多官能性環氧化合物(1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷變成0.03份以外，藉由與實施例8相同之方法製作光罩護膜，並進行評價。A mask film was produced in the same manner as in Example 8 except that the polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane was changed to 0.03 parts. And evaluate.

<比較例6><Comparative Example 6>

相對於聚矽氧黏著劑(Dowcorning(股)製造，SD4580(商品名)不揮發成分濃度為40%，甲苯/二甲苯溶液)100重量份添加0.9重量份硬化劑(Dowcorning(股)製造，SRX212)，獲得黏著劑前驅物組合物。其後藉由與實施例8相同之方式製作光罩護膜樣品，並進行評價。0.9 parts by weight of a hardener (manufactured by Dow Corning, SRX212) was added to 100 parts by weight of a polyoxyxylene adhesive (manufactured by Dow Corning, SD4580 (trade name) with a nonvolatile content of 40%, toluene/xylene solution). ), an adhesive precursor composition is obtained. Thereafter, a sample of the mask film was prepared and evaluated in the same manner as in Example 8.

<比較例7><Comparative Example 7>

將苯乙烯-乙烯/丁烯-苯乙烯之橡膠系熱熔黏著劑塗佈於一端面接著有光罩護膜薄膜之鋁合金製的光罩護膜框(外徑113 mm×149 mm，內徑109 mm×145 mm，高度4.8 mm)之另一端面。其後藉由與實施例8相同之方式製作光罩護膜樣品，並進行評價。A rubber-based hot-melt adhesive of styrene-ethylene/butylene-styrene is applied to a mask frame of an aluminum alloy film having an outer surface and a mask film (outer diameter: 113 mm × 149 mm, The other end of the diameter is 109 mm × 145 mm and the height is 4.8 mm. Thereafter, a sample of the mask film was prepared and evaluated in the same manner as in Example 8.

<實施例13><Example 13> (黏著劑前驅物組合物之製備)(Preparation of Adhesive Precursor Composition)

(甲基)丙烯酸烷基酯共聚物8係藉由眾所周知之方法製備。具體而言，於具備攪拌機、溫度計、回流冷卻器、滴加裝置、氮氣導入管之反應容器中放入乙酸乙酯(30重量份)，以48/48/1.5/2.5/1.0之重量比加入丙烯酸異丁酯/丙烯酸丁酯/丙烯酸/丙烯酸2-羥基乙酯/2,2'-偶氮雙異丁腈(AIBN)(10小時半衰期溫度60℃)之混合物(32重量份)，於氮氣環境下，使該反應溶液於60℃下反應8小時。反應結束後，添加甲苯(38重量份)，獲得不揮發成分濃度為32重量%之丙烯酸共聚物溶液(重量平均分子量為120萬)。於所獲得之丙烯酸共聚物溶液100重量份中添加0.25重量份多官能性環氧化合物(1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷，不揮發成分濃度為5%，甲苯溶液)，並進行攪拌混合，獲得黏著劑前驅物組合物。The alkyl (meth)acrylate copolymer 8 is prepared by a well-known method. Specifically, ethyl acetate (30 parts by weight) is placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, and is added in a weight ratio of 48/48/1.5/2.5/1.0. Mixture of isobutyl acrylate/butyl acrylate/acrylic acid/2-hydroxyethyl acrylate/2,2'-azobisisobutyronitrile (AIBN) (10 hour half-life temperature 60 ° C) (32 parts by weight) in nitrogen The reaction solution was allowed to react at 60 ° C for 8 hours under the environment. After completion of the reaction, toluene (38 parts by weight) was added to obtain an acrylic copolymer solution (weight average molecular weight: 1.2 million) having a nonvolatile content of 32% by weight. 0.25 parts by weight of a polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane) was added to 100 parts by weight of the obtained acrylic copolymer solution, and the concentration of nonvolatile components was added. It was 5%, a toluene solution), and stirred and mixed to obtain an adhesive precursor composition.

(附帶黏著劑之光罩護膜之製作)(production of photomask film with adhesive)

其後，利用分注器將所調配之上述黏著劑前驅物組合物塗佈至一端面接著有光罩護膜薄膜之鋁合金製的光罩護膜框(外徑113 mm×149 mm，內徑109 mm×145 mm，高度4.8 mm)之另一端面。以2個階段將其加熱乾燥、固化(第1階段：100℃，8分鐘；第2階段：180℃，8分鐘)，獲得形成有含有上述光罩護膜用黏著劑前驅物組合物之黏著劑層(厚度為0.2 mm)的光罩護膜。其後，將光罩護膜於130℃下加熱處理60分鐘，調整黏著劑層中殘留之2,2'-偶氮雙異丁腈(聚合起始劑)的量。繼而，貼附經聚矽氧脫模處理之厚度為100 μm之聚酯製保護膜，於室溫(20±3℃)下熟化3天，使黏著力穩定化，製作附帶黏著劑之光罩護膜。對所獲得之附帶黏著劑之光罩護膜，進行上述評價，除此以外實施下述評價。Thereafter, the prepared adhesive precursor composition is applied to a reticle cover film of an aluminum alloy having a mask film and a film having an outer diameter of 113 mm × 149 mm by means of a dispenser. The other end of the diameter is 109 mm × 145 mm and the height is 4.8 mm. It was heat-dried and solidified in two stages (first stage: 100 ° C, 8 minutes; second stage: 180 ° C, 8 minutes) to obtain an adhesive formed with the adhesive precursor composition containing the above-mentioned photomask film. Mask layer (0.2 mm thick). Thereafter, the mask film was heat-treated at 130 ° C for 60 minutes to adjust the amount of 2,2'-azobisisobutyronitrile (polymerization initiator) remaining in the adhesive layer. Then, a polyester protective film having a thickness of 100 μm which was subjected to polysilicon deoxidation treatment was attached and aged at room temperature (20±3° C.) for 3 days to stabilize the adhesion, and a photomask with an adhesive was prepared. Protective film. The above evaluation was carried out on the obtained photomask film with an adhesive attached thereto, and the following evaluation was carried out.

(聚合起始劑之殘留量測定)(Measurement of residual amount of polymerization initiator)

使用高效液相層析法(HPLC，high performance liquid chromatography)對黏著劑中殘留之聚合起始劑之殘留量進行分析。取黏著劑0.2 g置於20 mL螺旋管中，添加乙腈10 mL。利用浸透器，以120 r.p.m.，於25℃下攪拌8小時，以萃取定量成分。分析裝置、萃取條件設定如下。The residual amount of the polymerization initiator remaining in the adhesive was analyzed by high performance liquid chromatography (HPLC). 0.2 g of the adhesive was placed in a 20 mL spiral tube, and 10 mL of acetonitrile was added. The components were extracted by a penetrator at 120 r.p.m. for 8 hours at 25 °C. The analysis device and extraction conditions were set as follows.

分析裝置：Tosoh製造，HPL CCPMAnalytical device: manufactured by Tosoh, HPL CCPM

管柱：NuCLEOSLL 7C18(4.8 mmΦ×250 mm)Column: NuCLEOSLL 7C18 (4.8 mm Φ × 250 mm)

管柱壓力：41 Kg/cm2 Column pressure: 41 Kg/cm 2

管柱溫度：40℃Column temperature: 40 ° C

注入量：10 μLInjection volume: 10 μL

聚合起始劑之定量係用根據絕對校準曲線求出之重量除以1片光罩護膜之黏著劑重量而算出。The basis weight of the polymerization initiator was calculated by dividing the weight determined from the absolute calibration curve by the weight of the adhesive of one sheet of the mask film.

<實施例14><Example 14>

(甲基)丙烯酸烷基酯共聚物9係藉由眾所周知之方法製備。具體而言，於具備攪拌機、溫度計、回流冷卻器、滴加裝置、氮氣導入管之反應容器中放入乙酸乙酯(30重量份)，以99/1/1.0之重量比加入丙烯酸丁酯/丙烯酸/2,2'-偶氮雙異丁腈之混合物(32重量份)，於氮氣環境下，使該反應溶液於60℃下反應8小時。反應結束後，添加甲苯(38重量份)，獲得不揮發成分濃度為32重量%之丙烯酸共聚物溶液(重量平均分子量為180萬)。於所獲得之丙烯酸共聚物溶液100重量份中添加0.15重量份多官能性環氧化合物(1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷，不揮發成分濃度為5%，甲苯溶液)，並進行攪拌混合，獲得黏著劑前驅物組合物。其後藉由與實施例13相同之方式製作光罩護膜樣品，並進行評價。The alkyl (meth)acrylate copolymer 9 is prepared by a well-known method. Specifically, ethyl acetate (30 parts by weight) was placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, and butyl acrylate was added in a weight ratio of 99/1/1.0. A mixture of acrylic acid/2,2'-azobisisobutyronitrile (32 parts by weight) was reacted at 60 ° C for 8 hours under a nitrogen atmosphere. After completion of the reaction, toluene (38 parts by weight) was added to obtain an acrylic copolymer solution (weight average molecular weight: 1.8 million) having a nonvolatile content of 32% by weight. To 100 parts by weight of the obtained acrylic copolymer solution, 0.15 parts by weight of a polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, a concentration of a nonvolatile component is added It was 5%, a toluene solution), and stirred and mixed to obtain an adhesive precursor composition. Thereafter, a sample of the photomask film was prepared and evaluated in the same manner as in Example 13.

<實施例15><Example 15>

(甲基)丙烯酸烷基酯共聚物10係藉由眾所周知之方法製備。具體而言，於具備攪拌機、溫度計、回流冷卻器、滴加裝置、氮氣導入管之反應容器中放入乙酸乙酯(50重量份)，以99/1/2.0之重量比加入丙烯酸丁酯/丙烯酸/2,2'-偶氮雙異丁腈之混合物(32重量份)，於氮氣環境下，使該反應溶液於65℃下反應8小時。反應結束後，添加甲苯(18重量份)，獲得不揮發成分濃度為32重量%之丙烯酸共聚物溶液(重量平均分子量為60萬)。於所獲得之丙烯酸共聚物溶液100重量份中添加0.25重量份多官能性環氧化合物(1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷，不揮發成分濃度為5%，甲苯溶液)，並進行攪拌混合，獲得黏著劑前驅物組合物。其後藉由與實施例10相同之方式製作光罩護膜樣品，並進行評價。The alkyl (meth)acrylate copolymer 10 is prepared by a well-known method. Specifically, ethyl acetate (50 parts by weight) is placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, and butyl acrylate is added in a weight ratio of 99/1/2.0. A mixture of acrylic acid/2,2'-azobisisobutyronitrile (32 parts by weight) was reacted at 65 ° C for 8 hours under a nitrogen atmosphere. After completion of the reaction, toluene (18 parts by weight) was added to obtain an acrylic copolymer solution (weight average molecular weight: 600,000) having a nonvolatile content of 32% by weight. 0.25 parts by weight of a polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane) was added to 100 parts by weight of the obtained acrylic copolymer solution, and the concentration of nonvolatile components was added. It was 5%, a toluene solution), and stirred and mixed to obtain an adhesive precursor composition. Thereafter, a sample of the photomask film was produced and evaluated in the same manner as in Example 10.

<實施例16><Example 16>

除了將實施例13中獲得之附帶黏著材料層之光罩護膜的加熱處理條件自130℃下60分鐘變更成100℃下60分鐘以外，藉由與實施例13相同之方式製作光罩護膜樣品，並進行評價。A mask film was produced in the same manner as in Example 13 except that the heat treatment conditions of the mask film with the adhesive material layer obtained in Example 13 were changed from 60 minutes at 130 ° C to 60 ° C for 60 minutes. Samples were evaluated.

<比較例8><Comparative Example 8>

除了使實施例13中獲得之附帶黏著材料層之光罩護膜不進行130℃下60分鐘之加熱處理，而製作光罩護膜樣品以外，藉由與實施例13相同之方式，進行評價。The evaluation was carried out in the same manner as in Example 13 except that the mask film with the adhesive material layer obtained in Example 13 was heat-treated at 130 ° C for 60 minutes without producing a film of the mask film.

<比較例9><Comparative Example 9>

相對於聚矽氧黏著劑(Dowcorning(股)製造，SD4580(商品名)不揮發成分濃度為40%，甲苯/二甲苯溶液)100重量份添加0.9重量份硬化劑(Dowcorning(股)製造，SRX212)，獲得黏著劑前驅物組合物。其後藉由與實施例13相同之方式製作光罩護膜樣品，並進行評價。0.9 parts by weight of a hardener (manufactured by Dow Corning, SRX212) was added to 100 parts by weight of a polyoxyxylene adhesive (manufactured by Dow Corning, SD4580 (trade name) with a nonvolatile content of 40%, toluene/xylene solution). ), an adhesive precursor composition is obtained. Thereafter, a sample of the photomask film was prepared and evaluated in the same manner as in Example 13.

<比較例10><Comparative Example 10>

將苯乙烯-乙烯/丁烯-苯乙烯之橡膠系熱熔黏著劑塗佈於一端面接著有光罩護膜薄膜之鋁合金製的光罩護膜框(外徑113 mm×149 mm，內徑109 mm×145 mm，高度4.8 mm)之另一端面。其後藉由與實施例13相同之方式製作光罩護膜樣品，並進行評價。A rubber-based hot-melt adhesive of styrene-ethylene/butylene-styrene is applied to a mask frame of an aluminum alloy film having an outer surface and a mask film (outer diameter: 113 mm × 149 mm, The other end of the diameter is 109 mm × 145 mm and the height is 4.8 mm. Thereafter, a sample of the photomask film was prepared and evaluated in the same manner as in Example 13.

<實施例17><Example 17> (黏著材料組合物之製備)(Preparation of adhesive material composition)

(甲基)丙烯酸烷基酯共聚物11係藉由眾所周知之方法製備。具體而言，於具備攪拌機、溫度計、回流冷卻器、滴加裝置、氮氣導入管之反應容器中放入乙酸乙酯(30重量份)，以48/48/1.5/2.5/0.5之重量比加入丙烯酸異丁酯/丙烯酸丁酯/丙烯酸/丙烯酸2-羥基乙酯/2,2'-偶氮雙異丁腈之混合物(32重量份)，於氮氣環境下，使該反應溶液於回流溫度下反應8小時。反應結束後，添加甲苯(38重量份)，獲得不揮發成分濃度為32重量%之丙烯酸共聚物溶液(重量平均分子量為120萬)。於所獲得之丙烯酸共聚物溶液100重量份中添加0.05重量份多官能性環氧化合物(1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷，不揮發成分濃度為5%，甲苯溶液)，並進行攪拌混合，獲得黏著材料組合物。The alkyl (meth)acrylate copolymer 11 is prepared by a well-known method. Specifically, ethyl acetate (30 parts by weight) is placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, and is added in a weight ratio of 48/48/1.5/2.5/0.5. a mixture of isobutyl acrylate/butyl acrylate/acrylic acid/2-hydroxyethyl acrylate/2,2′-azobisisobutyronitrile (32 parts by weight), under a nitrogen atmosphere, the reaction solution was refluxed Reaction for 8 hours. After completion of the reaction, toluene (38 parts by weight) was added to obtain an acrylic copolymer solution (weight average molecular weight: 1.2 million) having a nonvolatile content of 32% by weight. To 100 parts by weight of the obtained acrylic copolymer solution, 0.05 parts by weight of a polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, a concentration of a nonvolatile component is added It was 5%, a toluene solution), and stirred and mixed to obtain an adhesive material composition.

(附帶黏著材料之光罩護膜之製作)(production of photomask film with adhesive material)

其後，利用分注器將所調配之上述黏著材料組合物塗佈至一端面接著有光罩護膜薄膜之鋁合金製的光罩護膜框(外徑113 mm×149 mm，內徑109 mm×145 mm，高度4.8 mm)之另一端面。以2個階段將其加熱乾燥、固化(第1階段：100℃，8分鐘；第2階段：180℃，8分鐘)，獲得形成有含有實施例17之光罩護膜用黏著材料組合物之黏著材料層(厚度0.2 mm)的實施例17之光罩護膜。繼而，貼附經聚矽氧脫模處理之厚度為100 μm之聚酯製保護膜，於室溫(20±3℃)下熟化3天，使黏著力穩定化，製作附帶黏著材料之光罩護膜。對所獲得之附帶黏著材料之光罩護膜進行上述評價，除此以外實施下述評價。Thereafter, the adhesive material composition prepared by applying the above-mentioned adhesive material composition to the one end surface and then the reticle film film of the reticle film is used (outer diameter 113 mm × 149 mm, inner diameter 109) The other end of mm × 145 mm, height 4.8 mm). This was heat-dried and solidified in two stages (first stage: 100 ° C, 8 minutes; second stage: 180 ° C, 8 minutes) to obtain an adhesive material composition containing the photomask cover film of Example 17. The reticle film of Example 17 of the adhesive material layer (thickness 0.2 mm). Then, a polyester protective film having a thickness of 100 μm which was subjected to polysilicon deoxidation treatment was attached and aged at room temperature (20±3° C.) for 3 days to stabilize the adhesive force, and a photomask with an adhesive material was prepared. Protective film. The above evaluation was performed on the obtained photomask film with an adhesive material, and the following evaluation was performed.

(光罩變形之評價)(evaluation of mask deformation)

光罩變形之評價係使用Tropel公司製造之FlatMaster 200進行測定。於貼附光罩護膜前測定光罩(6025石英)之平坦度，其後貼附光罩護膜，測定貼附光罩護膜後之平坦度(測定範圍：135 mm×110 mm)。將貼附前後之平坦度相減，算出因貼附光罩護膜導致6025石英發生何種程度之變形。The evaluation of the mask deformation was carried out using a FlatMaster 200 manufactured by Tropel. The flatness of the reticle (6025 quartz) was measured before attaching the reticle film, and then the reticle film was attached, and the flatness after attaching the reticle film was measured (measurement range: 135 mm × 110 mm). The flatness before and after the attachment was subtracted, and the degree of deformation of the 6025 quartz due to the attachment of the mask film was calculated.

利用簡易型貼合機，將光罩護膜貼附在石英(負重：30 Kgf，60 sec)上。Attach the mask to the quartz (load: 30 Kgf, 60 sec) using a simple laminator.

◎：由貼附光罩護膜引起之光罩之變形量為100 nm以下◎: The deformation of the mask caused by attaching the mask film is 100 nm or less.

○：由貼附光罩護膜引起之光罩之變形量為200 nm以下○: The amount of deformation of the mask caused by attaching the mask film is 200 nm or less

×：由貼附光罩護膜引起之光罩之變形量為200 nm以上×: The deformation amount of the reticle caused by attaching the reticle film is 200 nm or more

<實施例18><Example 18>

除了將多官能性環氧化合物(1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷，不揮發成分濃度為5%，甲苯溶液)變成0.1份以外，藉由與實施例17相同之方法製作光罩護膜樣品，並進行評價。In addition to the polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, the concentration of the nonvolatile component is 5%, the toluene solution) is changed to 0.1 part by A sample of the mask film was prepared in the same manner as in Example 17 and evaluated.

<實施例19><Example 19>

除了將多官能性環氧化合物(1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷，不揮發成分濃度為5%，甲苯溶液)變成0.2份以外，藉由與實施例17相同之方法製作光罩護膜樣品，並進行評價。In addition to the polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, the concentration of the nonvolatile component is 5%, and the toluene solution) becomes 0.2 part, A sample of the mask film was prepared in the same manner as in Example 17 and evaluated.

<比較例11><Comparative Example 11>

除了將多官能性環氧化合物(1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷，不揮發成分濃度為5%，甲苯溶液)變成0.24份以外，藉由與實施例17相同之方法製作光罩護膜樣品，並進行評價。In addition to the polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, the concentration of the nonvolatile component is 5%, and the toluene solution) is 0.24 parts, A sample of the mask film was prepared in the same manner as in Example 17 and evaluated.

<比較例12><Comparative Example 12>

除了將多官能性環氧化合物(1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷，不揮發成分濃度為5%，甲苯溶液)變成0.01份以外，藉由與實施例17相同之方法製作光罩護膜樣品，並進行評價。In addition to the polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, the nonvolatile content of 5%, the toluene solution) was changed to 0.01 part by A sample of the mask film was prepared in the same manner as in Example 17 and evaluated.

<實施例20><Example 20>

除了將多官能性環氧化合物(1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷，不揮發成分濃度為5%，甲苯溶液)變成甲苯二異氰酸酯之三羥甲基丙烷加成物0.15份以外，藉由與實施例17相同之方法製作光罩護膜樣品，並進行評價。In addition to the polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, the nonvolatile content of 5%, the toluene solution) becomes the toluene diisocyanate trihydroxyl A sample of the photomask film was prepared and evaluated in the same manner as in Example 17 except that 0.15 parts of the methyl propane adduct was used.

<實施例21><Example 21> (黏著材料組合物之製備)(Preparation of adhesive material composition)

(甲基)丙烯酸烷基酯共聚物12係藉由眾所周知之方法製備。具體而言，於具備攪拌機、溫度計、回流冷卻器、滴加裝置、氮氣導入管之反應容器中放入乙酸乙酯(30重量份)，以69/30/1/0.5之重量比加入丙烯酸2-乙基己酯/丙烯酸丁酯/丙烯酸/2,2'-偶氮雙異丁腈之混合物(32重量份)，於氮氣環境下，使該反應溶液於回流溫度下反應8小時。反應結束後，添加甲苯(38重量份)，獲得不揮發成分濃度為32重量%之丙烯酸共聚物溶液(重量平均分子量為150萬)。於所獲得之丙烯酸共聚物溶液100重量份中添加0.15重量份多官能性環氧化合物(1,3-雙(N,N-二縮水甘油基胺基甲基)環己烷，不揮發成分濃度為5%，甲苯溶液)，並進行攪拌混合，獲得黏著材料組合物。其後藉由與實施例17相同之方式製作光罩護膜樣品，並進行評價。The alkyl (meth)acrylate copolymer 12 is prepared by a well-known method. Specifically, ethyl acetate (30 parts by weight) is placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, and acrylic acid 2 is added in a weight ratio of 69/30/1/0.5. a mixture of ethyl hexyl acrylate/butyl acrylate/acrylic acid/2,2'-azobisisobutyronitrile (32 parts by weight), and the reaction solution was reacted at reflux temperature for 8 hours under a nitrogen atmosphere. After completion of the reaction, toluene (38 parts by weight) was added to obtain an acrylic copolymer solution (weight average molecular weight: 1.5 million) having a nonvolatile content of 32% by weight. To 100 parts by weight of the obtained acrylic copolymer solution, 0.15 parts by weight of a polyfunctional epoxy compound (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, a concentration of a nonvolatile component is added It was 5%, a toluene solution), and stirred and mixed to obtain an adhesive material composition. Thereafter, a sample of the mask film was prepared and evaluated in the same manner as in Example 17.

[產業上之可利用性][Industrial availability]

本發明之光罩護膜為逸氣產生量較少且有機氣體吸附性能優異之光罩護膜，因此可適宜地用於IC(integrated circuit，積體電路)、LSI(大規模積體電路)、TFT型LCD(thin-film transistor liquid crystal displayer，薄膜電晶體型液晶顯示器)等之微影步驟。The photomask film of the present invention is a photomask film having a small amount of outgas generation and excellent organic gas adsorption performance, and thus can be suitably used for an IC (integrated circuit) or an LSI (large-scale integrated circuit). A lithography step such as a TFT-type LCD (thin-film transistor liquid crystal display).

Claims (14)

一種光罩護膜，其特徵係具有光罩護膜框，於該光罩護膜框之一端面具有光罩護膜薄膜且於另一端面具有黏著劑者，該黏著劑對甲苯之重量膨潤度為5倍以上，該黏著劑含有(甲基)丙烯酸烷基酯共聚物與硬化材料之反應生成物，並且該(甲基)丙烯酸烷基酯共聚物係具有碳數4~14之烷基之(甲基)丙烯酸烷基酯與含有與硬化材料具有反應性之官能基之單體的共聚物。 A reticle protective film, which is characterized in that a reticle protective film frame has a reticle film on one end face of the reticle cover film and an adhesive on the other end face, and the adhesive swells the weight of the toluene The adhesive is more than 5 times, and the adhesive contains a reaction product of a (meth)acrylic acid alkyl ester copolymer and a hardening material, and the alkyl (meth)acrylate copolymer has an alkyl group having 4 to 14 carbon atoms. A copolymer of an alkyl (meth) acrylate and a monomer having a functional group reactive with a hardening material. 如請求項1之光罩護膜，其中該黏著劑藉由拉伸速度為30mm/min之拉伸試驗所獲得之23℃下的300%模數值為50~350mN/mm2。 The reticle film of claim 1, wherein the adhesive has a 300% modulus value of 23 to 350 mN/mm 2 at 23 ° C obtained by a tensile test at a tensile speed of 30 mm/min. 如請求項1之光罩護膜，其中該硬化材料係選自由多官能性環氧化合物及異氰酸酯系化合物所組成之群中之至少一種硬化材料。 The reticle film of claim 1, wherein the hardening material is at least one selected from the group consisting of a polyfunctional epoxy compound and an isocyanate compound. 如請求項2之光罩護膜，其中該硬化材料係選自由多官能性環氧化合物及異氰酸酯系化合物所組成之群中之至少一種硬化材料。 The reticle film of claim 2, wherein the hardening material is at least one selected from the group consisting of a polyfunctional epoxy compound and an isocyanate compound. 如請求項1~4中任一者之光罩護膜，其中該黏著劑進而包含聚合起始劑，且該黏著劑中殘留之聚合起始劑之總重量相對於黏著劑總重量為8ppm以下。 The photomask cover according to any one of claims 1 to 4, wherein the adhesive further comprises a polymerization initiator, and the total weight of the polymerization initiator remaining in the adhesive is 8 ppm or less based on the total weight of the adhesive. . 如請求項1之光罩護膜，其中該黏著劑係含有(甲基)丙烯酸烷基酯共聚物100重量份與硬化材料0.05~3重量份之反應生成物者。 The reticle film of claim 1, wherein the adhesive contains 100 parts by weight of an alkyl (meth) acrylate copolymer and 0.05 to 3 parts by weight of a reaction product of the hardened material. 如請求項5之光罩護膜，其中該黏著劑係含有(甲基)丙烯酸烷基酯共聚物100重量份與硬化材料0.05~3重量份之反應生成物者。 The reticle film of claim 5, wherein the adhesive contains 100 parts by weight of an alkyl (meth) acrylate copolymer and 0.05 to 3 parts by weight of a reaction product of the hardened material. 如請求項3之光罩護膜，其中該多官能性環氧化合物係具有2~4個環氧基之含氮環氧化合物。 The photomask film of claim 3, wherein the polyfunctional epoxy compound is a nitrogen-containing epoxy compound having 2 to 4 epoxy groups. 如請求項1之光罩護膜，其含有丙烯酸作為該含有與硬化材料具有反應性之官能基的單體，並且該丙烯酸之量相對於構成該(甲基)丙烯酸烷基酯共聚物之全部單體為0.1~5重量%。 The photomask film of claim 1, which contains acrylic acid as the monomer having a functional group reactive with the hardening material, and the amount of the acrylic acid is relative to all of the alkyl (meth)acrylate copolymer The monomer is 0.1 to 5% by weight. 如請求項5之光罩護膜，其含有丙烯酸作為該含有與硬化材料具有反應性之官能基的單體，並且該丙烯酸之量相對於構成該(甲基)丙烯酸烷基酯共聚物之全部單體為0.1~5重量%。 The photomask film of claim 5, which contains acrylic acid as the monomer having a functional group reactive with the hardening material, and the amount of the acrylic acid is relative to all of the alkyl (meth)acrylate copolymer The monomer is 0.1 to 5% by weight. 如請求項1之光罩護膜，其中該(甲基)丙烯酸烷基酯共聚物之重量平均分子量為70萬~250萬。 The photomask film of claim 1, wherein the (meth)acrylic acid alkyl ester copolymer has a weight average molecular weight of 700,000 to 2.5 million. 如請求項5之光罩護膜，其中該(甲基)丙烯酸烷基酯共聚物之重量平均分子量為70萬~250萬。 The photomask film of claim 5, wherein the (meth)acrylic acid alkyl ester copolymer has a weight average molecular weight of 700,000 to 2.5 million. 如請求項5之光罩護膜，其中該聚合起始劑為過氧化物系聚合起始劑或偶氮系聚合起始劑、或者烷基苯酮系聚合起始劑或醯基氧化膦系聚合起始劑。 The photomask film of claim 5, wherein the polymerization initiator is a peroxide polymerization initiator or an azo polymerization initiator, or an alkylphenone polymerization initiator or a fluorenylphosphine oxide system. Polymerization initiator. 一種黏著劑，其特徵為其係含有(甲基)丙烯酸烷基酯共聚物100重量份與多官能性環氧化合物0.05~3重量份之反應生成物者，該(甲基)丙烯酸烷基酯共聚物係具有碳數4~14之烷基之(甲基)丙烯酸烷基酯與含有與環氧基具有 反應性之官能基之單體的共聚物，並且該黏著劑對甲苯之重量膨潤度為5倍以上。An adhesive characterized by comprising 100 parts by weight of an alkyl (meth) acrylate copolymer and 0.05 to 3 parts by weight of a polyfunctional epoxy compound, the alkyl (meth) acrylate The copolymer is an alkyl (meth)acrylate having an alkyl group having 4 to 14 carbon atoms and having an epoxy group A copolymer of a reactive functional group monomer, and the viscosity of the adhesive to toluene is 5 times or more.
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