TW201037456A - Pellicle film, pellicle used with mask for tft liquid crystal panel production, and photomask containing the pellicle - Google Patents

Abstract

Disclosed is a pellicle which can prevent generation of a growable foreign material on a chromium hard mask during a photolithography process. Also disclosed are a pellicle film and a photomask containing the pellicle. The pellicle film contains an optical organic polymer as a main film material, and has an oxalic acid permeation rate converted as the value of a 1 [mu]m thick film at 70 DEG C in 72 hours of 1.0 10-3 mg/cm2 or less.

Description

201037456 VI. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a method for preventing foreign matter from adhering to an IC (integrated

Circuit ^ t^) > LSKlarge scale integrated circuit ^ A scale integrated circuit), TFT type LCD (Thin FUm

Crystai Display, thin film transistor liquid crystal display, etc. The reticle used in the lithography step or the film used in the film and film on the main mask, and the film containing the film. More particularly, the present invention relates to a film film which can be preferably used for patterning of a TFT liquid crystal type flat panel display, and a film film used in the film, and a photomask including the film. [Prior Art] First, when a semiconductor element pattern is formed on a wafer (hereinafter referred to as "day-day circle"), or when a pattern is formed on a flat panel display substrate such as a liquid crystal panel, it is usually called a film. The dustproof mechanism prevents foreign matter from adhering to the photomask (hereinafter also referred to as "mask"). The term "film" refers to a transparent polymer film (hereinafter referred to as a film film) having a thickness of 1 〇 or less, and then has a thickness of a few millimeters in a shape having a shape corresponding to the shape of the mask. The frame body (hereinafter, also referred to as "frame wood") has a top edge side and is formed by laminating an adhesive layer on the lower edge side of the frame. The film used in the manufacture of a liquid crystal panel or the like is a large-sized film as compared with the film used for the manufacture of a semiconductor element, and the area of the film film is cm or more and 30,000 cm2 or less. In the manufacturing method of the semiconductor device using the photolithography technique, the film forming step, the exposing step, the developing step, and the stripping step of the last step of the photoresist are performed by 144856.doc 201037456, (4) Into the component circuit. In each step of the photolithography, an organic solvent used to coat the photoresist is used, or a chemical solution for developing or stripping the photoresist, and a chemical reaction is used: Efficient production of component circuits. Therefore, in the atmosphere of the clothes, in the atmosphere, the chemical substances which are volatilized and scattered are slightly present due to the use of the above various organic solvents or chemical solutions. The chemical substances present in the atmosphere of the brothers sometimes pass through the mask, the film or the vent hole formed by the side surface of the frame on which the film film is unfolded, and reach the pattern forming surface of the mask, and the mask. The residue in the manufacturing step or other compound present on the surface of the mask reacts and solidifies to generate foreign matter. In the case of long-term use, since it is used for several years, it corresponds to the two use time and the exposure frequency, even if the initial amount of the foreign matter is meager: it will gradually accumulate and become large and grow into foreign matter ( ', called <long foreign body'). Further, if the growth foreign matter is generated in the ultraviolet ray transmissive portion of the pattern on the surface of the mask, it may become a cause of defective devices or defects. In recent years, with the LSI pattern being finer and more integrated, the light source of the device for exposure is from the g-line (436 _) and the i-line (36-plane) of the high-pressure mercury lamp to the KrF excimer laser (10). ...excimer laser (10)· : The wavelength of the neon. Since such a short-wavelength exposure light source has high energy and the density of the light is high in the infusion, it is easy to cause a photochemical reaction. The shorter the wavelength of the exposure light source in the industry, the more significant the growth of the above-mentioned growth foreign matter is. 144856.doc 201037456 之一 One of the reasons for the growth difference in the 甩m I soap produced by the use of short-wavelength exposure light, it is reported that after the manufacture of the mask, the sulphate fence is early, and the person* is in the mask. Surface ions (used to clean the mask) and the mask used in the atmosphere in the developing solution) due to the quasi-spinning of the pattern transfer, thereby generating ammonium sulfate, thereby becoming a history, ... Small ^ #This becomes a foreign object (refer to the non-patent literature! and

Yang Er!: Inferior report: used as the surface of the film of the alloy, the chemical film is mixed with acid such as sulfuric acid, acid, organic acid, and the acid is separated from the anodized film in the exposed soil. In the space between the film and the mask, the sulfuric acid compound, for example, ammonium sulfate, is produced by the short-wavelength ultraviolet ray at the time of exposure (see Patent Document 2). Therefore, even in the case of a mask having a good quality in a defect-free inspection after the manufacturing, there is a problem in that the excimer is irradiated by the exposure device, and the growth of the foreign matter is generated on the mask. A good pattern transfer image transferred to the wafer is obtained. As a countermeasure, it is proposed to suppress the generation of growth foreign matter by reducing the residual amount of sulfuric acid when the mask is produced, or removing the ammonia in the environment by using a chemical filter or the like, and sealing the space between the mask and the film. A method of introducing nitrogen into the inside, and a method of reducing the humidity of the environment in which the mask is used. PRIOR ART DOCUMENT PATENT DOCUMENT Patent Document 1: Japanese Patent Laid-Open No. Hei. No. 2006-11048 Patent Document 2: Japanese Patent Laid-Open Publication No. Hei No. Hei No. Hei. ,

Proc. of SPIE, Vol. 5645 (2005), pl 〇 9-113 SUMMARY OF THE INVENTION Problems to be Solved by the Invention However, in the manufacturing steps of a liquid crystal panel for a flat panel display, compared with the manufacturing steps of the semiconductor element The line width or pitch of the printed pattern is relatively large, so that it is not necessary to use the short-wavelength exposure beam having a higher energy density as described above, and the exposure area is wide, and the amount of exposure light is required, usually at a temperature of 15 ° C. In the above atmosphere, the mask pattern is transferred using a broadband exposure beam having a wavelength band of the 丨 line to the g line. Therefore, in the manufacturing steps of the liquid crystal panel for a flat panel display, there is almost no occurrence of a chemical substance generated by an exposure beam having a high irradiation energy as in the case of manufacturing a semiconductor article, and a foreign matter is generated on the mask. It will not become a serious problem. As described above, in the manufacturing process of the liquid crystal panel for a flat panel display, there is almost no occurrence of a chemical substance generated by an exposure beam having a high irradiation energy as in the case of manufacturing a semiconductor element, and a foreign matter is generated on the mask. However, the present inventors have found the following problem: in recent years, the use of a large mask for manufacturing a TFT liquid crystal panel using an exposure beam of a ray line 1 (for example, 365 to 436 nm) It also produces growth foreign matter on the pattern forming surface of the mask film due to the preservation or use of the mask for half a year to several times. As a result of research by the inventors of the present invention, it was found that the occurrence of the growth foreign matter is related to the storage environment, and the clear relationship with the number of exposures is not found. 144856.doc 201037456 If it is produced on a mask for the manufacture of semiconductor components, it is a growth foreign matter: because ammonium sulfate can be used to prevent the separation of sulfate ions in the closed space between the film and the mask. In addition, the inventors of the present invention have found that it is still in the hard chrome mask (usually on a substrate such as synthetic quartz). A growth foreign matter is generated on the mask in which the light-shielding film pattern containing chromium is formed. In other words, the inventors of the present invention have found that when a large-sized mask for TFT liquid crystal panel manufacturing is used, the growth foreign matter generated on the pattern forming surface is known to grow when a small mask for manufacturing a semi-body 7L member is used. If the nature of the foreign body is different, it is necessary to take different countermeasures to complete the invention. Therefore, the problem to be solved by the invention of the present invention is to provide a manufacturing step of a conductor device for an Ic (Integrated Circuit), an LSI (Large Scale Integrated Circuit), a TFT LCD (Thin Film Transistor Liquid Crystal Display), especially In the manufacturing process of the TFT liquid crystal panel, it is possible to suppress the film film used in the film film in which the above-mentioned growth foreign matter is generated on the hard chrome mask, and the photomask including the film. The inventors of the present invention have conducted intensive studies and found that the main cause of growth of foreign matter generated on the hard-surface mask surface in the manufacturing steps of the TFT liquid crystal panel product using photolithography is chromium oxalate. The complex compound 'Guhai Cao• Secret Complex is the reaction product of chromium or its compound contained in the environment for the production of oxalic acid and (4) the hard road mask and the light-shielding material of the towel. Further, it was found that the edge of the chrome-based light-shielding film which was patterned by the material length (four) W-turned (four) was grown by the edge of #巧任膘 as a starting point. According to 144856.doc 201037456, it has been found that ions of oxalic acid or a compound thereof which are present for some reason in a masked environment have some reaction with chromium used in the light-shielding film. In most cases, the growth foreign body has a size of about 兄μηι. Therefore, in the photomask of the above-mentioned use having a line width of 3 〇μπ or more and 5 〇〇μη or less as a light-shielding pattern, the growth foreign matter may become an obstacle in pattern transfer, which is a serious problem. . In the storage environment of the mask, the growth of the foreign matter is hardly observed. In the past, the film towel of the liquid crystal panel has not produced such a growth foreign matter. Therefore, it is estimated that the growth foreign material is owned by the liquid crystal panel manufacturer. The mask is grown in a storage environment or a change in the environment in which it is used. In the manufacture of a TFT liquid crystal panel, photolithography is used in the pattern formation of a (4) (10) 〜 to indium tin oxide electrode or a Zn0 (zinc oxide) electrode on a TFT substrate. Among them, in the step (4) at the time of pattern formation of the ITO electrode, hydrochloric acid was previously used as the surname liquid. However, in recent years, since the mainstream of the ruthenium electrode has become non-nucleus, oxalic acid has been used as the surname. +, Therefore, the inventors of the present invention considered that the generation of growth foreign matter generated on the hard chrome mask in the manufacturing process of the TFT liquid crystal panel, and the use of the above-mentioned manufacturing steps in the manufacturing step of the TFT liquid crystal panel are newly used as the etchant = acid. Furthermore, it is considered that there is a change in the manufacturing steps such as an increase in concentration even in the case of a moon which has an atmosphere in which oxalic acid ions are present. The inventors and the like conducted an effort to study, and as a result, it was found that oxalic acid produced a growth foreign matter due to the following mechanism. It is first cut in the atmosphere (manufacturing environment atmosphere) for manufacturing TFT liquid crystal panels. 144856.doc 201037456 There is a higher concentration of oxalic acid. However, there is a case where the atmosphere of the manufacturing environment changes due to the change of the step of manufacturing the panel described above, and the concentration of oxalic acid in the atmosphere of the manufacturing environment becomes high. The oxalic acid is present in the atmosphere of the manufacturing environment in the form of a gas, a fine particle powder or a mist, and reaches the surface of the hard chrome mask through the vent holes of the film film or the film frame, and other members. In the 步骤 Ο Ο 造 。 FT FT FT FT 液晶 液晶 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 ITO ITO ITO ITO ITO ITO ITO ITO ITO ITO ITO The above-mentioned oxalic acid which is present in the atmosphere of the ring mirror is attached to the surface of the hard-circuit mask and reacts with chromium or a compound thereof which is used as a light-shielding material for the surface of the hard mask to form a complex. This reaction is easy to form a growth foreign matter by hydrating, absorbing or absorbing water oxalic acid to become an oxalic acid ion and reacting it with chromium or a compound thereof. In particular, the reactivity of oxalic acid varies depending on the hygroscopic state of the acid, and it is easy to increase the humidity in the production environment (for example, when the humidity is 70% or more, and further, it is 嶋 or more), and oxalic acid becomes a state containing excessive moisture. Generate growth foreign bodies. Therefore, as a method of suppressing growth foreign matter, it is also effective to reduce the humidity of the manufacturing environment atmosphere to such an extent that electrostatic damage does not occur in the mask pattern, but it is difficult to adopt this method in the case where the TFT liquid crystal panel is used as a mask. The growth foreign matter is less likely to occur on the back surface or the periphery of the mask, and is likely to occur on the pattern formed on the roadway light-blocking film. In particular, it is easy to grow with the edge of the pattern as a starting point. This edge is obtained by patterning the edge obtained by patterning the chromium-based light-shielding film formed by the 贱 clock method. Large masks 144856.doc 201037456 The main component of the liquid to carry out the wet chrome etching is mainly by the use of nitric acid as a touch. ❹ However, it is usually not easy to cause metal...in the reaction of normal temperature. Therefore, it is generally considered that a chromium-based light-shielding film (or (four) light-shielding film = anti-reflection film) which is formed on a transparent substrate by a coating material has a relatively high activity ionized state of chrome plate+, 〇3+ 寻) exists with a certain probability that this chemical species is beginning to promote the reaction with environmental substances, thereby generating foreign matter or growing foreign bodies. Alternatively, it is considered that the green light-shielding film containing chromium, which is contained in the above-mentioned complex light-shielding film, is in contact with an environmental substance to produce a more active ionization network. Further, as described above, since the foreign matter is generated with the edge of the pattern as a starting point, it is presumed that the above-described tongue with a relatively high tongue is likely to be present on the cross section of the pattern to be etched, and ammonia promotes the growth of the growth foreign matter. Further, according to the study by the inventors of the present invention, it is possible to observe a large amount of growth foreign matter under high humidity (for example, 7% or more), and therefore it is understood that by contact with a high-humidity environmental substance, The ionized chromium is generated, so that it is easy to generate a growth foreign matter. In addition, it is considered that when the light-shielding film is formed by laminating a plurality of layers having different compositions, foreign matter is likely to be generated, so that ionization due to contact of a high-humidity dissimilar metal acts. In the present specification, 'the so-called "chromium oxalate complex" refers to a complex formed by the reaction of oxalic acid with a compound of chromium or complex, and an organic basic substance such as ammonia or an amine present in the complex and the atmosphere or contains A salt formed by reacting an inorganic basic substance such as Li, Na, K or Ca. 144856.doc • ]0- 201037456 The following discloses a salt that can be grown into a growing foreign body. Μ represents a monovalent cation or a divalent cation, and η represents an integer. Examples of the salt of the growth foreign material include tris(oxalate) chromium (III) acid salt M3 [Cr(C2〇4) 3] and a hydrate thereof, for example, (NH4)3 [Cr(C204)3]. 2H20, (ΝΗ4)3[(:γ((:2〇4)3]·3Η20, K3[Cr(C204)3] 3H20, Li3[Cr(C2〇4)3].5.5H20, Na3[Cr( C204)3].4.5H20, Na3(NH4)3[Cr(C204)3]2.7H20, K3(NH4)3[Cr(C204)3]2.5H20, Rb3[Cr(C2〇4)3]-3H2 〇' Na3Rb3[Cr(C2〇4)3]2-7H2〇' Ag3[Cr(C2〇4)3]-nH20 'K(C21H23N202)2[Cr(C2〇4)3].4H20, (C21H23N202) 3[Cr(C2〇4)3].llH2〇,

Ca3[Cr(C204)3]2.18H20, Ca3[Cr(C2〇4)3]2-36H20, CaK[Cr(C2〇4)3].3H20,

CaK[CrCC2〇4)3]-4H20 'Sr3[Cr(C2〇4)3]2 l2H2〇 'Sr(NH4)[Cr(C2〇4)3]-4H20 '

Sr(NH4)[Cr(C204)3].5H20, KSr[Cr(C2〇4)3].6H20, Ba3[Cr(C2〇4)3]2-6H20, Ba3[Cr(C204)3]2.7 H20, Ba3[Cr(C2〇4)3]2.12H20, BaK[Cr(C2〇4)3k2H20,

BaK[Cr(C204)3]2.3H20 and the like. Further, examples of the salt of the growth foreign matter include ethylenediamine bis(oxalate) chromium (III) acid M [Cr(C 2 〇 4) 2 (C 2 H 8 N 2 )] and a hydrate thereof, for example: (NH 4 ) [Cr (C204) 2 (C2H8N2) HNH4) HC204 H20 or the like. Further, examples of the salt of the growth foreign material include dihydrated (oxalate) chromic acid (M) (Cr(C204)2(H20)2] and a hydrate thereof, for example, K[Cr(C204) 2(H20)2].2H20, K[Cr(C204)2(H20)2].3H20, Na[Cr(C204)2(H20)2].5H20, (NH4)[Cr(C204)2( H20)2].3H20, Li[Cr(C204)2(H20)2], Rb[Cr(C204)2(H20)2] 'Cs[Cr(C204)2(H20)2], Mg[Cr( C204) 2 (H20) 2] 2

Ca[Cr(C204)2(H20)2]2, Sr[Cr(C2〇4)2(H2〇)2]2, Ba[Cr(C204)2(H20)2] and the like. Further, examples of the salt of the growth foreign matter include dihydrogen oxalate (oxalate) chromium (III) acid salt M3 [Cr(C2〇4) 2 (〇H) 2] and a hydrate thereof, for example: 144856 .doc • 11 - 201037456

Ag3[Cr(C204)2(〇H)2].3H2〇, Ca3[Cr(C204)2(〇H)2]2.4H20, K3[Cr(C204)2(〇H)2].6H20, Ag3 [Cr(C204)2(〇H)2], Pb3[Cr(C204)2(0H)2] and the like. Further, hydration (hydrogen) bis(oxalate) chromite (III) acid salt ivyCrCQC^OHXH^O)] and hydrates thereof may be mentioned, for example, (NH4)2[Cr(C204)2(〇 H) (H2〇)].H2〇, etc. Particularly preferred as a growth foreign material is an ammonium salt, among which, in particular, a tris(oxalate) chromium (111) acid salt M3 [Cr(C2〇4) 3] and a hydrate thereof, for example, (NH 4 ) 3 [Cr (C204) 3] _nH20. Most of the above-mentioned chromium oxalate complexes are hygroscopic, water-absorbing and/or deliquescent, and the shapes vary depending on the humidity, but they are crystalline or liquid, and the chromium oxalate complexes are used in the mask. In the environment, there is almost no sublimation, and it is accumulated as a growth foreign matter on a hard chrome mask. Further, the growth foreign matter including the chromium oxalate complex is also generated in the opening of the transfer pattern, and as a result, the exposure is not performed normally, so that the TFT liquid crystal panel is defective or defective. . The time until the exposure defect occurs is different depending on the shape or type of the mask pattern, t: the type of the pattern, and the step material, and the exposure defect has a time span, and in the case of a faster case, sometimes When the concentration of oxalic acid in the atmosphere is low in ~2 years, the time until the exposure defect occurs due to the occurrence of the foreign matter becomes long. Insights' and proceeding according to the following concept, the result = Ming, the above concept is to use the film with the following film ,, can inhibit the growth of the growth of foreign matter in the film, the oxalic acid or ammonium present in the film film The salt due to the second soil requires the ammonia to enter the dense I44856.doc 201037456 ❸ gas barrier. In Japanese Patent Laid-Open No. 2, No. 184822, there is no cause that acid ions (sulfuric acid ions, organic acid acids, etc.) caused by a film frame may cause foreign matter formation. On the other hand, in the environment in which the liquid crystal display device is manufactured, the surname engraving is used in the diagram (4) of the ITQ electrode, but the (iv) liquid is mainly hydrochloric acid, and is only caused by the growth of foreign matter in the manufacturing environment atmosphere. The extent of the extremely small amount of grasshoppers, this does not recognize the oxalic acid ions in the above ambient atmosphere to be specific

The above concentrations are present. Moreover, the oxalic acid present in the atmosphere of the manufacturing environment is not only regarded as a problem, but also the technical idea of using the film film having high gasity to reduce the occurrence of the above-mentioned growth foreign matter cannot be produced according to the prior art, and the present case & The invention is based on a completely different technical idea from the prior art. ~ That is, the present invention is as follows. [1] A film film which has a film thickness of 70X after being left for 72 hours, has a oxalic acid permeation amount of 1 Gxl ().3 mg/cm2 or less, and the main film material is an optical organic polymer. [2] A film film, 25 of which. (The ammonia permeability coefficient is 8. 〇xl 〇-9 cm3Tm/cm2_s_Pa or less, and the main film material is an optical organic polymer. [3] The film film of [2], which is placed at 70 ° C 72 The film thickness of 1 μΓη after the hour is 丨〇χ1〇_3 mg/cm2 or less. 144856.doc -13- 201037456 [4] A knee film film whose main film material is optical organic polymer And the film material contains a light stabilizer of 〇_1% by weight or more and 15% by weight or less based on the total weight of the optical organic polymer. [5] The film film of [4] wherein the above optical The organic polymer is a cycloolefin resin or a cellulose derivative. [6] The film film according to [4] or [5] wherein the light stabilizer is a hindered amine light stabilizer. [7] A film Including: the film film of the frame Π] to [6], the adhesive layer, the side of the upper edge of the frame and the side of the lower edge of the frame [8] as [ [7] The film [9] and the TFT liquid crystal panel manufacturing photomask together with the light stabilizer dissolved two = method 1 includes: making the optical organic high and from the polymerization =: agent The step of removing the organic solvent in the step of the polymer solution. The method of producing a film of the film of [9], a hydrocarbon, a gasified hydrocarbon, wherein the above organic solvent is a [n] 5 曰糸 compound or a ketone compound. 144856.doc 201037456 wherein the light stabilizer is a method for producing a film film according to [9] or [10], a hindered amine light stabilizer. [12] A method for producing a film film according to [11] at 25 ° C The method for producing a film film according to any one of [9] to U2, wherein the light is a liquid film.

The organic polymer used in the study is a cycloolefin resin or a cellulose derivative. [14] A type of photomask having a transfer pattern formed by patterning a light-shielding film containing chromium on a surface of a transparent substrate, and having a surface on a side of the transparent substrate having a transfer pattern For the manufacture of a liquid crystal display device of a film, the transparent substrate has an area of 1000 cm 2 or more, and the film thickness of the film film of a film is 0 5 μm or more and 8 or less and is placed in an atmosphere of 70 C for 72 hours. The oxalic acid permeation amount in terms of the film thickness i μηη of the film was 1.0 OxiO-Smg/cm 2 or less. [15] The photomask according to [4], wherein the transfer pattern of the light-shielding film is formed on the transparent substrate by a sputtering method, and has a pattern cross-section formed by etching. [16] A pattern transfer method in which an exposure beam having a wavelength range of a 丨 line to a g line is irradiated to an illuminant such as [14] or [1 5] in an atmosphere having a temperature of 15 or more. The above transfer pattern is transferred onto the transfer target. 144856.doc •15.201037456 [17] A method of manufacturing a TFT liquid crystal panel, comprising: a step of preparing a photomask such as [14] or [15]; passing the photomask with an ιτ〇 electrode and applying photosensitivity a step of performing photolithography on the TFT liquid crystal panel substrate; a step of developing the photosensitive photoresist; and a step of etching the germanium electrode by using oxalic acid. [18] A combination of film and TFT LCD panel manufacturing, 3

The film comprises a frame body, an adhesive layer laminated on the lower edge side of the frame body, and a film film which is unfolded on the upper edge side of the frame body, and the film thickness of the film film is W (four) or more and 8 _ or less, and The turmeric acid permeation amount of the slab film is 1×10 /-4 mg/cm 2 or less. [19] For the film of [18], the area of the above film film in the pot, in the middle, is above 1 cm 2 , and below 30000 cm 2 .胶片 For film of [18] or [19], the film film of Dan Y is made of a film material containing a cycloolefin resin. [21] For example, in [18] to [20], the film of the above-mentioned film is composed of ring-like soot resin and relative to 1 iSi咕μ & The total weight of the % olefin oxime resin is 〇1% by weight or more and 15% by weight. The film material of the light stabilizer described below, or a cycloolefin-based resin, is preferably a weight of 5% by weight or more based on the total weight of the oxime-based olefin. The stabilizer and 0.1% by weight or more and 1% by weight are formed of a film material of an antioxidant of 144856.doc 16·201037456. [22] The film of Ρ1], wherein the light stabilizer is liquid at normal temperature. 23] ° For the film of [18] to [2], the + or one of the two layers of the above film has a ring-shaped or linear fluorine-substituted fluoroalkyl group light-weight anti-reflection layer. [24] A method of manufacturing a TFT liquid crystal panel, comprising: attaching a film as in the above-mentioned item to a hard chrome mask via a film layer laminated on a lower edge side of the frame body; a step of exposing a TFT liquid crystal panel substrate having a tin-plated electrode and applying a photosensitive photoresist by the hard chrome mask; a step of developing the photosensitive photoresist; and using an etching solution containing oxalic acid a step of etching the ITO electrode. [25] A photomask attached to a transparent substrate A liquid crystal display device having a transfer pattern formed by patterning a light-shielding film containing chromium and having a film on a side of the transparent substrate having a transfer pattern, the transparent substrate having 1 〇〇〇cm2 or more, the film thickness of the film of δ hai film is below 05 μηη and 8 μηη, and the oxalic acid permeation amount of the film film after being placed in an atmosphere of 70 C for 72 hours is lxl〇 4mg/cm2 or less. [26] 144856.doc 17 201037456 The transfer pattern of the film is formed by sputtering and having a mask patterned by etching, such as [25], wherein the above-mentioned light-shielding method is used to form a film on the transparent substrate. [27] A mask according to [26], wherein the transfer pattern has a light-shielding pattern having a line width of less than 100 μm and a width of less than 500 μm. _ [28] A method of manufacturing a mask The method includes the steps of: forming a light-shielding ruthenium containing chromium on a transparent substrate by sputtering, and applying a photoresist film on the light-shielding ruthenium film to trace the desired rotation of the photoresist film. After printing the pattern, it is developed The photoresist pattern is used as a mask to engrave the light-shielding film, whereby the transfer pattern is patterned on the light-shielding film, and the photoresist pattern is peeled off, and then the transparent substrate is used. The patterned light-shielding-film-side mounting film; the film thickness of the film film of the film is 〇5 or more and 8 μηι or less, and the film film is placed at a temperature of 7 (after 72 hours in an atmosphere) The oxalic acid permeation amount is lx1 (r4 mg/cm2 or less. [29] Ο A pattern transfer method in an atmosphere having a temperature of 15 t or more, for a photomask according to any one of [25] to [27], Alternatively, the photoreceptor manufactured by the method for manufacturing a photomask according to [28] irradiates an exposure beam having a wavelength range of a twist line to a g line, thereby transferring the transfer pattern onto the object to be transferred. [30] A method of manufacturing a TFT liquid crystal panel, comprising: preparing to adhere to an adhesive layer laminated on a lower surface side of the frame body as in [18] to [23] 144856.doc • 18- 201037456 a step of hard chrome masking of the film of the item; a step of exposing the TFT liquid crystal panel substrate having the ITO electrode and applying the photosensitive photoresist by the hard chrome mask; developing the photosensitive photoresist a step; and a step of etching the ITO electrode with an etchant containing oxalic acid. Advantageous Effects of Invention The film of the present invention can be applied to a semiconductor such as an IC (integrated circuit), an LSI (large-scale integrated circuit), or a TFT-type LCD (thin-film liquid crystal display) by applying the film of the present invention to a hard chrome mask. In the manufacturing steps of the device, particularly in the manufacturing steps of the TFT liquid crystal panel, a top-grown foreign matter is generated on the hard chrome mask. [Embodiment] First, the reticle and the attachment of the film to the reticle will be described. The reticle used in the manufacture of a liquid crystal panel for flat panel display is used for forming a fine pattern on a transparent substrate including synthetic quartz glass or soda lime glass. Most of the transparent substrates used here have an area of 1000 em2 or more, and the latex mask and the hard chrome 遮 mask can be distinguished according to the precision of the pattern. The film of the present invention is preferably applied to a hard chrome mask formed on the surface of synthetic quartz or soda lime, especially a hard chrome mask formed on synthetic quartz glass. In the hard chrome mask, in addition to the chromium-based film, a mask portion formed by laminating a film having another composition may be used, and further, another film may be laminated after etching the chromium-based film, and further etching may be performed. Case. ^^ A hard chrome mask is formed by a reactive sputtering on a main surface of a transparent substrate to form a light-shielding metal film containing Cr (Chromium) as a main component. In the case where an antireflection film is formed at this time, first, only Cr is sputtered, and then oxygen is introduced into the plating gas of 贱144856.doc •19-201037456, whereby an antireflection film containing chromium oxide can be formed on the surface. Similarly, the composition of the metal film can be changed by introducing various gases, whereby a blank hard chrome mask in which a plurality of layers including the composition are laminated can be produced. The light-shielding metal film 'is a single-layer film containing a material such as an atmosphere, oxygen or carbon in a chromium monomer or chromium, or a laminated film of the film. In particular, the film of the present invention can be applied to a film having a plurality of layers of various compositions.涂 Applying a photoresist to the & gold alloy field on the blank hard chrome mask substrate, and drawing a fine pattern using a laser beam to develop, thereby forming a photoresist pattern. Then, the photoresist pattern is used as a mask, and the Cr metal film which is not subjected to the photoresist is removed by etching to form a desired transfer pattern (patterning). Thereafter, the photoresist is peeled off by the photoresist (4), and the residue remaining on the metal film is removed and cleaned, and inspected to form a hard mask. : Defense! To clean the hard cover again, use a film mount machine to attach the film to a film with a transfer pattern. For the purpose of reclamation, it is a foreign body. ...the method of suppressing the above-mentioned growth foreign matter is suppressed by the defect inspection machine as the method of suppressing the growth foreign matter, and the oxalic acid reading of the film of the brother and the moon, A w is considered as follows: making the oxalic acid J The method of lowering the method of making the liquid crystal panel, the method of reducing the degree of the cover, the method of protecting the surface of the hard mask, the pattern of the grass or the shading material, and the method of profiting does not occur. The space of the reactor is a method of replacing the gas between the reticle substrate and the film film, and a method of bringing the mask into contact with the dry air, 144856.doc -20-201037456, and the like. In the method of 3H, etc., a method of producing a long foreign matter by reducing the oxalic acid permeability of the film film is described. In the method of suppressing growth foreign matter, it is necessary to prevent the hard chrome from covering the chrome on the cover with oxalic acid or ammonia. Therefore, if a film film which is difficult to permeate oxalic acid or strontium is used, the hard chrome can be reduced. The amount of oxalic acid or ammonia on the chrome of the mask can suppress the growth of foreign matter, and can be extended to a time until the exposure is low. The time until the growth of the foreign matter and the occurrence of the exposure defect is related to the permeability of the film film, and is used in 70. (: A film film with a oxalic acid permeation of 丨〇χΐ〇3 mg/cm2 or less in a film thickness of i μηη after 72 hours of storage can maintain sufficient light transmission performance and can greatly suppress the growth of foreign matter. Therefore, the time until the exposure defect is generated can be greatly extended. The film thickness i' after 7 hours of placing it for 7 hours is better than 8. 〇Xl〇-4 mg/cm2 or less. Preferably, it is 1·6χ10·4 mg/cm2 or less, particularly preferably 5 〇χΐ〇_5 mg/cm2 to ❹. Further, if it is used at 70 ° C for 72 hours, the oxalic acid permeation amount is 1>< A film film of 1 〇·4 mg/cm2 or less can be greatly extended to a time when a growth property is generated and an exposure defect is generated, and the mask is not problematic in use. It is at 70. (: the amount of oxalic acid permeation after being placed for 5 hours is 5x10 5 mg/cm or less, preferably even if a light stabilizer, or a light stabilizer and an antioxidant are added, the oxalic acid permeation amount is 5χ1 ( Γ5 mg/cm2 or less. At 70. (: The oxalic acid permeation after 72 hours of placement is better 爻"ίο·5 mg/cm2 Further, it is particularly preferably 6.0x10-6 mg/cm2 or less. Further, by adding a light stabilizer (preferably a light stabilizer and an antioxidant) by 144856.doc 21 201037456, the oxalic acid permeation amount can be further effectively suppressed. In addition, when a film film having an ammonia permeability coefficient of 8 〇χ1 〇 -9 or less at 25 ° C is used for ammonia, sufficient light transmission performance can be maintained, and the growth of foreign matter can be greatly suppressed. Therefore, it can be greatly extended until the time when the exposure defect is generated. 25. The ammonia permeability coefficient of the underarm is 6.0X10-9 cm, m/cm2.s.pam, and more preferably UxiO-9 CmVn. /cm, .Pa or less, particularly preferably ι〇χΐ〇_9 cm3'gm/cm2.s.Pa or less. Including the case of the antireflection layer described below, the film thickness of the film film is better 〇_5 The above 8 (four) or less, more preferably 2 _ or more and 6 _ or less. The thicker the film thickness of the film film, the more the oxalic acid permeability can be suppressed, and the film strength can be increased, so it is preferably 0.5 _ or more. When it is thick, the light transmittance is lowered, so that it is preferably 8 μm or less in terms of light transmittance. As a film film, it is important The amount of oxalic acid permeate is small, but at the same time, it is such that the thickness of the film film has a suitable thickness. The viewpoint of film strength such as puncture strength or the suppression of growth foreign matter, preferably 05, (4) The film thickness of the film is preferably 疋0.5 _ or more, and the thicker the better, the better is 8 , the light transmission ^ θ / + h and the better the binding. The oxalic acid required for the film film is good for ΛΑB ^ ^ u /, and the films are balanced. The preferred ruthenium is used as the oxalic acid permeation amount of the film film, and the sputum film of the grass is called (10) or less after the acid permeation amount is lxio·4 / 2 and C is placed for 72 hours, and the right side is the mother early film. The amount of oxalic acid permeate is relatively high; the amount of oxalic acid permeation is inhibited, and the transmittance of the sheet can be improved: it can be sufficiently seasoned. Specifically, 144856.doc 201037456 is preferred as a film film having a oxalic acid permeation amount of a film film, a film thickness after 7 hours, and a oxalic acid permeation amount of ι〇χΐ〇.3; A film film that reduces oxalic acid permeability can be achieved by selecting a film material. As a film material which can be used for a film film, an inorganic material or an organic material can be produced, but in terms of workability, productivity, etc., it is preferred that the organic two molecules are

= The film film k is good, and the main film material is an organic polymer for optics. The term "mainly" means that the entire film material is 50% by weight or more. The term "optical" means a transmittance of, for example, a wavelength of 365 to 463 nm. It is 8〇% or more.纟 As an optical organic polymer that can be used for film films, it can be considered as cellulose acetate, cellulose acetate butyrate, cellulose diacetate, cellulose acetate propionate, Nitrocellulose, nitrocellulose, etc. 'other than this' can be exemplified: tetrafluoroethylene _ hexafluoropropylene copolymer 浚 tetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, poly 4 _ Pentene, polybutyl acrylate, polyvinyl acetate, polymethyl acrylate, I propylene, polymethyl methacrylate, polyvinyl butyl phthalate, polymethyl methacrylate, polyethylene glycol, polyamino carboxylic acid Ester, polyethylene formaldehyde, polyisobutylene, polyethylene, polybutylene, polybutadiene, polyvinyl chloride, polyacrylonitrile, polymethacrylonitrile polyisoprene, nylon 6' nylon 66, butadiene Styrene copolymer, gland-formaldehyde resin, epoxy resin, polychloroprene, polyphthalate, monoallyl, polystyrene, polyvinylidene chloride, polysulfone, phenol-make resin a fluoroalkyl group in which a part or all of a gas atom is replaced by a fluorine atom. 144856.doc -23 - 201037456趟, ring or chain type of fluorine, ρ 1 1 ρ ρ 曰 曰 曰 曰 曰 曰 曰 曰 ρ ρ ρ ρ ρ ρ ρ ρ ρ ρ ρ ρ ρ ρ ρ ρ ρ ρ ρ ρ ρ ρ ρ ρ ρ ρ ρ ρ ρ ρ ρ ρ ρ ρ ρ And [Comparative: at least one resin selected from the group consisting of cellulose derivatives (especially cellulose acetate propionate, nitrocellulose) n-type propylene (tetra) tree wax and material type gluten-lipid. Further, in the above-mentioned organic polymer for optics, the ammonia permeability coefficient is small, and the practicality of the film such as optical properties and mechanical properties is easy to manufacture, and it is preferable that it is selected from the viewpoint of being used as a cover. + > 乍 四 树 树 树 四 - 六 六 六 六 六 六 六 六 六 六 六 六 六 六 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 An atom-substituted fluoroalkyl group, a cyclic or a chain fluoro-substituted resin in a group consisting of a pyrene-based or alicyclic hydrocarbon resin. Among the materials, in particular, a material having a small amount of oxalic acid permeation and an ammonia permeation system is exemplified by a cycloolefin resin, preferably a polymer or copolymer of a pentene (including a hydride). For example, Apel (registered trademark K Mitsui Chemicals Co., Ltd.), TQpas (registered trademark) (manufactured by p_piastics Co., Ltd.), Ze0nex (registered trademark) or zeonor (registered trademark) (manufactured by Zeon A Division), and Arton (registered) (trademark) (manufactured by JSR Co., Ltd.), etc., as a cycloolefin-based resin suitable for a film film, in particular, ZeZnor (si brand) (manufactured by Japan (10) Co., Ltd.) has a small amount of oxalic acid permeation and a small ammonia permeability coefficient. The material is best. Among the film materials of the film film, a polymer solution obtained by dissolving a cycloolefin resin or a cellulose derivative in an organic solvent is preferably used. In particular, 144856.doc -24- 201037456 Ο 〇 In terms of oxalic acid permeation amount or ammonia permeation coefficient, it is preferred to use a polymer solution obtained by dissolving a cycloaliphatic resin in an organic solvent. The usable organic solvent may, for example, be a hydrocarbon-based compound, an aromatic compound, or a sulfonated hydrocarbon, an ester compound or a ketone compound. An organic solvent such as a saturated aliphatic hydrocarbon compound such as alicyclic smoke, an aromatic compound or a toothed hydrocarbon is used in a cellulose derivative, which is soluble in chlorinated tobacco, ah, vinegar, morphol, benzene. In a single or mixed organic solvent such as an alcohol, an organic solvent such as a chlorinated tobacco or a vinegar-based compound or a ketone-based compound can be mentioned as an example of the organic solvent. As the chlorinated hydrocarbon, dichloromethane can be preferably used. As the organic solvent of the ketone compound, it can be preferably used as a ketone compound organic solvent, such as methyl ethyl ketone or methyl isobutyl ketone. The use of acetic acid vinegar (acetic acid methyl acetate, ethyl acetate, butyl acetate, etc.), lactic acid δ (lactic acid f cool, lactic acid butyl 3, etc.), in addition to ethanol, methanol, cellosolve acetate vinegar, Carbitol and the like can also be used as an early one or a mixed solvent. The polymer solution of the material is formed by "forming". In order to increase the light transmittance of the film film and reduce the film film, the polymer solution used at this time is preferably 0.05 or less. In addition, the method of suppressing the oxalic acid permeation of the film film is carried out by Ming et al., and it is found that the use of the above-mentioned film material and the addition of a light stabilizer can very effectively inhibit the amount of oxalic acid permeation. In the film material of the film film, there is oozing out of the film, so no light stabilizer is added, but light resistance can be improved by adding a light stabilizer to the film material of the film film, and the knee can be greatly suppressed 144856.doc -25 * 201037456 Oxalic acid permeability of film film. As an added light stabilizer, it will be exposed to crystals on the hard path mask after oozing or volatilization, resulting in a compound that is not exposed, especially if the light stabilizer is abnormal. ^ Light stabilizer, can inhibit the appearance of light stabilizers:: special:: is the inclusion of ^,5,-tetramethyl-derivatives is particularly good is τΙΝυνΐΝ (registrars wrestle not. For example better The door knows 0 Limited billion

Adekastab LA series ("CHIMASS0RB (registered trademark) manufactured by ΑΜκα Co., Ltd. (Ciba Specialty Chemicals Co., Ltd.). In terms of oxalic acid permeation suppression effect, J, stabilizer combination optical = fruit: special Good. Also, about the photosynthetic ring _ tree two wide; no special restrictions, ... or cellulose derivatives (especially 疋 nucleoside light stabilizer), 〇 hindered amine Liguang cellulose) and light stabilizers (especially female When the stabilizer is first stabilized, the effect of oxalic acid permeation is greater. Further, the == oxalic acid permeation suppressing effect suppresses the light fastness of the light stabilizer. 2: The light stabilizer of the shape refers to the function of the transition of the aperture of 10 _, which can be appropriately selected. It is not to be added! 2 The light fastening effect of the stabilizer can also be combined with the light stabilizer: Good: 'The phenolic and phosphite esters of the oxidant. As an antioxidant, ruthenium does not cause 144856.doc -26· 201037456 photodefects due to crystallization on the mask after being introduced or volatilized. Among such compounds, as the phenolic antioxidant, for example, Adekastab AO series (manufactured by ADEKA Co., Ltd.) and IRGAN0X (registered trademark) (manufactured by Ciba Specialty Chemicals Co., Ltd.) are preferable. As the phosphite system, for example, IRGAF〇s (registered trademark) (manufactured by Ciba Specialty Chemicals Co., Ltd.) and Adekastab PEP series (manufactured by ADEKA Co., Ltd.) are preferred. When the light stabilizer is added to improve the light resistance, and it is added in an amount of 0.1% by weight or more and 15% by weight or less based on the total weight of the 0 organic polymer for optical use, bleeding can be suppressed and light resistance can be improved. Preferably, the ruthenium is added so as to be i% by weight or more and 10% by weight or less based on the total weight of the optical organic polymer. In order to obtain the light-improving effect, it is not added, and it is more preferably added in an amount of 2% by weight or more and 8% by weight or less based on the total weight of the optical organic polymer. Further, in the case where the girth of the optical enthalpy I is in the above range, bleeding does not occur, and the effect of suppressing the permeation of the grass can be obtained, and the absorbance of the solution can be made 〇 to be lower than Q. The antioxidant is more effective in light resistance improvement by the synergistic effect with the light stabilizer than the light stabilizer alone, so it is preferably 0.1% by weight relative to the total weight of the organic polymer. Above 10 weight. /. The addition is preferably carried out in such a manner that the total weight of the organic polymer for optical use is 5% by weight or more and 5% by weight or less. In order to enhance the 'multiplication effect, the absorbance of the solution is 0.05 or less and the bleeding does not occur, and it is more preferable to add it to 0.1% by weight or more and 3% by weight or less based on the total weight of the optical organic polymer. 144856.doc •27- 201037456 In the production of film, 'use a polymer solution made of optical organic polymer dissolving film=...to add light to the above polymer solution for further step-up of film formation~' Stabilizer =:, or use a solution with a light stabilizer and an antioxidant added. Examples of the organic solvent include saturated aliphatic hydrocarbons such as alicyclic hydrocarbons, δ, aromatic compounds, and halogenated hydrocarbons. The method for producing a film can be formed by preparing a polymer solution, followed by a gel: removing the organic solvent in the polymer solution after the film solution, and the polymer solvent stabilizer of the film material of the film film is finely and uniformly When dispersing in the J = case of film formation, the obstacle of ί ! 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用 使用Increase the amount added. Further, a light stabilizer is added to the polymer solution of the film material of the film film, and the bleed out of the stabilizer or the ά η of the first substance can also suppress the 辑 辑 ... 出 出 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此 因此method. In particular, it is used in a liquid form at room temperature. Two oxidizing agents are easy to prepare a solution of a uniform sentence, and are formed into a film. Further, it is easy to be uniformized. Therefore, it is possible to suppress the occurrence of oozing or foreign matter. In the event of oozing, it is also difficult to produce foreign matter that is an obstacle to exposure due to less inflammation. However, the crystallization is more effective than the uniform light stabilizer and the unevenly dispersed light stabilizer. Reducing the mechanical properties such as the puncture strength of the film film 144856.doc -28- 201037456 Further, the film film containing the uniformly dispersed light stabilizer can improve the light resistance and suppress the light resistance as an index The polymer is degraded. Since the film film directly receives light from the exposure light source (ultra-high pressure mercury lamp) at the time of exposure, the film material polymer of the film film is deteriorated by the ultraviolet light of the exposure light source. Due to this deterioration, the film material polymer of the film film becomes water absorbing. In the case of the moisture resistance test (4) and the like, the knee film comprising the uniformly dispersed light stabilizer can improve the moisture resistance with respect to the film which does not contain the light stabilizer which is uniformly dispersed. Among these, the material having a puncture strength of 015 Å/Å or more is excellent in film formability and mechanical properties, and therefore it is preferable from the viewpoint of manufacturing the film. When the film having a low strength is used for film formation, the film thickness of the film film has to be made thick, and as a result, the average light transmittance at the time of exposure is lowered. The puncture strength of Miaoyue film, the index of the strength of the film. The value of the puncture strength of the film is 0_075 Ν/μη1 or more, and it can be used as a film carefully, but the film film is better. The strength of the ~. The puncture force is more than °·2. The strength of the spur strength can be measured by fixing the film film to a holder having a hole of 6 mm in diameter and measuring it with a B ^ ^ puncture rod with a front end of 1 o. The maximum value (N) of the force at the time of puncture at a speed of 5 mm/min and a thickness of 2 faces. The film measured is preferably a large value.

^ _ ; c, relative humidity of 45% under the R (4) placed in 24 hm and then measured. Further, the average light transmittance is as a blank (light transmittance 144856.doc • 29 - 201037456 100%) as a blank film, and is expressed as an average light transmittance (%) having a wavelength of 350 to 7 Å. The lower the value, the lower the light transmittance, and the higher the value, the higher the light transmittance. The average light transmittance must be about 93% in the previous film film use, preferably 94% or more. The light transmittance can be measured by an ultraviolet visible spectroscope (for example, UV-2450 manufactured by Shimadzu Corporation). Further, in order to prevent optical reflection and to increase the average light transmittance, an antireflection material containing a material having a refractive material lower than that of the film # may be laminated as an antireflection layer on the surface or both sides of the film film. As the antireflection material, a cyclic or linear fluorine-substituted fluoroalkyl polyether can be preferably used. The antireflection layer can be formed by spin coating on the main film. The film thickness of the antireflection layer is 1 〇 nm or more and 5 Å or less. □ From the viewpoint of improving the antireflection effect, particularly preferably 汕 nm or more and 180 nm or less. The material of the frame may, for example, be aluminum or an alloy thereof, such as durium aluminum, or iron or an iron-based alloy, such as stainless steel, which is a well-known material for film. Among these, it is preferable to use lightweight and rigid if it is considered to increase the self-weight of the frame caused by the enlargement, and for example, it is preferably "or its alloy." As the adhesive for adhering the film film to the frame, a conventional user such as an ultraviolet curable adhesive or a fluororesin-based adhesive can be used. Further, as the adhesive for attaching the film to the mask, a known one can be used. Tong + Chang ' as a bonding material, can use styrene · ethylene. Dilute _ styrene, stupid - dilute - propylene benzene - gynecological, olefinic and other hot-adhesive bonding materials Adhesive, acrylic-based adhesive, including double-sided adhesion of a substrate such as a foamed film. For heat (4), it can be extruded by using a conventional J44856.doc -30-201037456 syringe or the like. It is disposed on the frame. Further, it is also possible to apply heat after the extrusion coating, press the surface with a forming plate such as a flat plate, etc. The accelerated test method simply confirms the growth foreign matter including the chromium oxalate complex. The method of generating 'supplied by the fact that the growth of the film of the present invention and the film used previously can be easily confirmed by the presence or absence of growth of foreign matter.

The resulting i' of the foreign matter can thus actually demonstrate the effect of the film of the present invention by the accelerated test method. The film of the present invention can be preferably used in a method of manufacturing a liquid crystal panel comprising the steps of: attaching a film to a hard chrome mask via an adhesive layer laminated on a lower edge of the frame; passing the hard chrome a step of exposing a TFT liquid crystal panel substrate having an ιτ〇 electrode and coating a photochromic green; a step of developing the photosensitive photoresist; and a step of etching the ITO electrode using an etching solution containing oxalic acid . In addition, it is considered that the film of the present invention is preferably used for a flat panel display substrate other than a TFT liquid crystal panel, for example, a substrate for a plasma display, as long as it has an ITO electrode layer and uses oxalic acid as the IT etchant. And a substrate for an organic EL (electroluminescence) display. In the TFT liquid crystal panel substrate, ιτο (indium tin oxide) or 211 〇 (zinc oxide) was used as a transparent and electrically conductive material for the electrode. Photolithography has also been used in the patterning of electrode layers containing germanium. However, as described above, oxalic acid has been used as an etching solution for germanium in recent years. Therefore, if a chromium mask is used for a long time, the TFT liquid crystal panel substrate is used. The manufacturing environment is an environment in which a growing foreign matter can be generated due to a trace amount of oxalic acid in the atmosphere, but the growth can be prevented by using a film for use in a mask for manufacturing a TFT liquid crystal panel as disclosed in Japanese Patent Publication No. 144856.doc 31 201037456. The foreign matter is generated, and the growth of the growth foreign matter can be delayed until the extent of use is not produced. EXAMPLES (Method for Measuring Oxalic Acid Permeability) Shape, size and film were taken in 1 hr using pure water at 50 ° C (outer frame dimensions, 149 mm in length, 113 mm in width, 4.2 mm in height, and frame width: 2 mm) Filter paper of the same size (N〇4A, Toyo Filter Co., Ltd.) within the frame was washed 3 times and dried. The filter paper is placed therein in a manner that completely covers the frame of the film, and the film is fixed to a glass plate having a thickness of 3 by a two-liquid mixed epoxy-based adhesive in a manner that maintains airtightness (longitudinal 152 „ ^><Round 152 mm). Under normal pressure, the film-fixed glass plate and 2 g of oxalic anhydride (manufactured by Wako Pure Chemical Industries, Ltd. and placed in a glass container (volume of 3·8 L) In the sealed state, it is treated at 7 ° C for 72 hours, so that the oxalic acid passing through the film film is adsorbed on the filter paper. After the above-mentioned treated filter paper is taken out, it is extracted with 4 〇χ:, 5 〇 mL of pure water. The amount of oxalic acid adsorbed on the filter paper, and the amount of oxalic acid in the water (mg) was determined by ion chromatography. The amount of oxalic acid was divided by the area of the film film (cm2) as oxalic acid after being placed at 7 ° C for 72 hours. The amount of permeation (mg/cm2). In addition, the thickness of the film used in the sputum is measured. It is assumed that the amount of oxalic acid permeation in the film thickness is 1 μηι. The amount of oxalic acid permeation when the film thickness of the film film is set to 1 μm. Adding oxalic anhydride to a closed glass container and no film film. Resent the amount of oxalic acid in the case of experiment with a frame with an adhesive. 144856.doc -32- 201037456 The result is 1 x 1 〇 '6 mg/cm2 or less. (Method for measuring ammonia permeability coefficient) The measurement of the ammonia permeability coefficient is carried out according to the gas phase chromatography (2006) of the second part (equal pressure) of JIS _7126. Set to 25t:, 〇%RH, the test area is set to 2〇mm, the atmospheric pressure during the test is set to 1 atm, the carrier gas flow rate is set to 30 ce/min, and the carrier gas type is set to He. The official column is ammonia. With the column, the column packing material is set to 0 900, the column length is set to 1 m, and the Teflon tube is used. The unit is converted by the transmittance system and used as the transmission coefficient (unit: cm^m/cm2 sec. Pa) (accelerated test method for growth of foreign matter) The accelerated test method for growing foreign matter is attached to a low-reflection type blank mask (manufactured by Clean Surface Technology Co., Ltd.: model number 'CQL6012BU' In the vertical 152.0 mmx horizontal 152.0 mmx thick 3· On the one side of the mm, a chrome oxide film was formed on the surface, and it was placed in a closed glass container (with a volume of 3.8 L) together with 2 g of oxalic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.). After treatment for 3 days, the film was removed, and the blank mask was placed in a closed glass container together with 50 cc of pure water, and stored for 24 hours. Further, the blank mask was placed in the addition. In a glass closed container with 10 g of 10% aqueous ammonia solution, at 70. (: Store for 2 hours (Refer to Figure 1). • Clean the part of the surface of the oxidized chrome surface of the blank mask that is protected by the film with water. After the cleaning water is recovered, it is dried at 70 °C. Further, in the case of obtaining a dried residue, Speetruml(R) (manufactured by PerkinElmer Japan Co., Ltd.) was used, and ATR method 144856.doc -33-201037456 (attenuated total reflectance method) was used for measurement. The IR spectrum (infrared spectrum) of the residue was confirmed by observing the peaks in all three parts of the IR spectrum of 1640 to 1670 cm-1, 1360 to 1390 cm'1, and 1240 to 1260 cm·1. The growth of a foreign matter containing a chrome-chrome complex is shown in Fig. 2. The IR spectrum of an example of a growth foreign matter containing a chromium oxalate complex is shown in Fig. 2. (Ultraviolet light irradiation method) Ultrahigh pressure mercury lamp (Ushio Motor Co., Ltd. limited) The company manufactures) as a light source' to illuminate light into a circular shape with a diameter of about 11 cm. The film film is placed in the circle without direct contact of the irradiated surface with any object, and the film film is illuminated. Ultraviolet light is emitted. The amount of exposure of the knee film is the following (J/crn2): The light receiver UV-SD35 (measured in the wavelength range of 31〇) using an ultraviolet illuminometer (manufactured by 0RC Manufacturing Co., Ltd.) The measurement is performed from nm to 385 nm, and the obtained illuminance (mW/cm2) is multiplied by the irradiation time (sec), and the obtained irradiation amount (mJ/cm2) is divided by the value obtained by 1 。. Stabilizer exudation test) Attach the transfer sheet (outside the frame size, 149 mm x 133 mm x height 4.2 mm, frame width 2 mm) to a fully cleaned quartz glass plate (length 3 mm, longitudinal) 152 mm x 152 mm), and placed in a closed glass container (volume 3.8 L) without being in contact with the film, sealed and sealed at 70. (: heating for 6 days. The film was observed with a microscope, And arbitrarily performing visual inspection under a spotlight and under monochromatic light, and comparing with the film surface before the treatment, thereby determining whether or not foreign matter is present. 144856.doc •34· 201037456 (moisture resistance test) on film (outside the frame) Dimensions, vertical 149 mmx width 113 mmx height 4·2 mm, frame width 2 mm, frameless In the center of the adhesive, a UV (ultraviolet) lamp (manufactured by ushi0 Electric Co., Ltd.) is used as a light source, and the light is irradiated into a circular shape having a diameter of about 丨丨cm. The light has been irradiated for 50,000 j. /cm2 film, which will be equal to the constant temperature and humidity device at a temperature of 22. (:, when the relative humidity is 45%)

The observation was carried out, and then the film wrinkles at the same temperature were increased for 2 minutes to increase the relative humidity to 97%. (Example 1) 1 〇g of Zeonor 060R (Zeon 〇r (registered trademark) manufactured by ZeZn & Division of Japan) was added to 90 g of citric acid (manufactured by Wako Pure Chemical Industries Co., Ltd.). The mixture was stirred at room temperature for 4 hours to be dissolved, and then stirred at 70 C for 4 hours to dissolve. This solution was added dropwise to a crucible wafer, and spin-coated at 3 rpm on a spin coater, and then dried by a heating plate of 14 〇〇c for 30 minutes to obtain a gel film. A solution containing amorphous fluororesin, Cytop CTX-8〇9SP2 (Asahi Glass) was added dropwise to the obtained membrane using perfluorodibutylamine (Fluorinert FC-43 Sumitomo 3M Co., Ltd., trade name). Manufactured, trade name) diluted to a solid content of 2. /. Then, after spin coating at 300 rPm on a rotary coater, at 120. (: It is dried to obtain a film film having a thickness of 4 μm. The film film is unfolded and attached to an aluminum frame coated with an adhesive on the upper edge surface (outer shape, 149 mm×110 mm×height) 4.2 mm, frame width is 2 mm), cut off the film film that removes the unnecessary part from the frame. Gu Hai I44856.doc -35- 201037456 The film has a oxalic acid permeation of 45χΐ after 72 hours of storage. 〇5 mg/cm2«thickness is 4·〇_, and the membrane acid thickness i _ converted oxalic acid permeation amount is 1.8^10 mg/cm2. X, the result of measuring the ammonia permeability coefficient is 3" Chuan 9

Cm3, /C„^sec-Pa. The light transmittance of the film film was measured by π 2450 (manufactured by Shimadzu Corporation), and the average value of the light transmittance at a wavelength of 35 〇 to (10) was 94%. The film was irradiated with 10_J/cm2 of ultraviolet light, and the average transmittance was determined to be 94%. X, the oxalic acid permeation after being placed for 72 hours on the film irradiated with ultraviolet light was 4_4x1〇-5 _2 (film thickness) For 4 〇〇 pm), the oxalic acid permeation amount of the film thickness of 1 μηι is 丨8χΐ〇_4 called/cm2. Then, the accelerated contact method for producing a long foreign body is used to confirm the presence or absence of growth foreign matter, and the result is not obtained from the blank cover. Residue of the washing water obtained by the hood. (Example 2) Zeonor 060R (Zeonor (registered trademark) manufactured by Zee N & Japan) of ίο g as a cycloolefin polymer was added to 9 〇g of decalin ( The product was prepared by stirring at room temperature for 4 hours, and then dissolving by stirring at 70 ° C for 4 hours. The solution was added dropwise to a crucible wafer on a spin coater. After spin coating at 3 rpm, use i 6 〇. Heated plate drying 3 0 The film was obtained in order to obtain a film film. The solution containing amorphous fluororesin, that is, Cytop CTX-, was added dropwise to the obtained film by using perfluorotributylamine (Flu〇rinen FC43, manufactured by Sumitomo 3M Co., Ltd.). 809SP2 (Asahi Glass Co., Ltd. manufacture 'product name) diluted to a solid content of 2%, spin-coated at 300 rpm on a spin coater, and then dried at 12 (Tc 144856.doc -36- 201037456 Obtain a film film with a thickness of 4 μm. The film film is unfolded and attached to the frame with the adhesive coated on the upper edge surface (the shape 'longitudinal 149 mmx horizontal in mmx height 4.2 mm, frame width is 2 • mm), and cut off the film film that removes the unnecessary part from the frame. The oxalic acid permeation of the film after 72 hours at 70 C is 4 3χ1〇-5 mg/cm (the film thickness is 4.0 μηι), the oxalic acid permeation amount in terms of film thickness i μη1 is 1-7Χ10-4 mg/cm2. Further, the result of measuring the ammonia permeability coefficient is 3 2χΐ〇9 ❹ Cm3'/cm2-sec, Pa. The light transmittance is measured by the average value of the light transmittance at a wavelength of 35 〇 to 7 利用 using a grip 2450 (manufactured by Shimadzu Corporation). The result was 94%. The 忒 film was irradiated with 1 〇〇〇〇J/cm2 of ultraviolet light and the average light transmittance was measured, and the result was 94%. Further, after the film irradiated with ultraviolet light, it was placed after the J temple. The oxalic acid permeate amount is 4·5χ1〇-5 mg/cm2 (the film thickness is 4 〇(4)). The membrane acid thickness of 1 μπι conversion is 丨8xl〇_4mg/cm2. Then, the accelerated test method for growing foreign matter was used to confirm the presence or absence of growth 〇 1 growth foreign matter. As a result, the residue of the washing water obtained from the blank mask was not obtained. (Example 3) Preparation: g as Zeonor 〇 60R of J olefin oxime polymer (Zei 〇n〇r (5 main volume trademark) of Zeon Corporation of Japan) was added to 90 g of decalin (Kishida sinensis In the company's manufacture, it was dissolved at room temperature for four hours, and it was dissolved in 7Q C for 4 hours. To the solution was added 0_5 g of liquid: TINUV〗N292 (Ciba Refinery), and stirred at room temperature for 6 hours to make /, & The solution had an absorbance of 0.002 and the solution was a 144856.doc -37-201037456 clear solution. This solution was dropped onto a ruthenium wafer, and spin-coated at 300 rpm using a spin coater, and then dried using a 16 〇<t hot plate for 30 minutes to obtain a film film. On the obtained film, a solution containing amorphous fluororesin, that is, Cyt〇p CTX_8〇9Sp2 (manufactured by Asahi Glass Co., Ltd.) was added dropwise using perfluorotributylamine (Fluorinert FC-43 Sumitomo 3M (manufactured by the company). The product name was diluted to 2%, and after being spin-coated at 3 rpm on a spin coater, it was dried at 12 G ° C to obtain a film film having a thickness of 6 Å. The film film is unfolded and attached to an aluminum frame coated with an adhesive on the upper edge surface (outer shape, longitudinal 149 _ horizontal 113 mm x height 4.2 _, frame width 2 mm) _L cutting and removing the self-frame An undesired portion of the film film is stretched out. The amount of oxalic acid permeation after 72 hours of standing at 70 C was 4 4 χ 1 〇. The film was called 1) The amount of oxalic acid permeation in terms of film thickness i μηι was again measured as 30 x 10-9. The light transmittance of the film film is measured by UV_mg/cm2 (film thickness: 6.0 2·6 χ 10 5 mg/cm 2 • pm/cm Lsec. Pa 245 制造 (manufactured by Shimadzu Corporation) at a wavelength of 350 to 700 nm. The average of the light rate was 94%. The puncture strength was n-, with sufficient intensity 0 to illuminate 10000 J/cm2 of UV light, and the average light transmittance was 94%. The ultraviolet light film was placed at 7 〇t for 72 hours, and the oxalic acid permeation amount was 4.3χ1〇-6 mg/cm2 (the film thickness was 6.〇μηι), and the film thickness was changed. The converted oxalic acid permeation amount was 25. The tooth J uses an accelerated test method for growing foreign matter to confirm the presence or absence of a growth foreign matter. The result is that the residue of the washing water obtained from the blank mask is not obtained. 144856.doc -38- 201037456 Residue of the light stabilizer is performed. The test method was used to observe the film surface by micro-mirror, but no foreign matter was found. Moreover, it was visually observed under the spotlight and monochromatic light. The result of the observation was not found after heating, and the 'average transmittance was added to the heat.珂 was 94.8%, and after heating, it was 94.7%, no change was found. Further, visual observation of moisture resistance The occurrence of wrinkles in the central portion of the test towel was observed, and as a result, no occurrence of sensitization was observed between 45% and 97% relative humidity. 〇 (Example 4) ίο g was used as a ruthenium hydrocarbon polymer Ze 〇 N〇rl〇峨(3) The company's Zeonor (s main volume trademark) was added to 9〇g decalin (manufactured by Vision Huaxin. Co., Ltd.) for 4 hours at room temperature. Dissolve, and then dissolve it at 7G ° C for 4 hours to dissolve it. Add 0.5 g of liquid solution TINUVIN 292 (Ciba refined) at 25 ° C and ir 〇 g 5 g of irganoxlOlO (Ciba Refining), stirring at room temperature for 6 hours to dissolve. Ο The absorbance of the bath is 〇.002, and the solution is a transparent solution. The solution is added dropwise to the ruthenium wafer and spin coated. After the machine was applied at 300 卬m, it was dried by a hot plate at 60 ° C for 3 〇 minutes to obtain a film film. Perfluorotributylamine FC-43 Sumitomo 3M was added dropwise to the obtained film. (manufacturing, product name) will contain the solubility of amorphous fluororesin. Liquid is Cyt0P CTX-809SP2 (made by Asahi Glass Co., Ltd., trade name) Cheng, 2 / (), after spin coating at 3 rpm on a red transfer coater, 丨 2 〇. 〇 dry it to obtain a film film with a thickness of 6 μη. Attached to the upper edge of the aluminum coated 144856.doc 39· 201037456 frame (shape, medial 49 mm x width 113 mm x height 4.2 mm, frame width 2 mm) on and cut off The film film of the unnecessary portion protruding from the frame body is removed. 6 Xuansheng film is at 70. (: The oxalic acid permeation amount after leaving for 72 hours was 4.5 χΙΟ·5 mg/cm 2 (the film thickness was 6 〇 μιη), and the oxalic acid permeation amount of the film thickness of 1 μπι was 2.7 ΧΗΓ 5 mg/cm 2 . Further, the ammonia permeability coefficient was measured. The result was 3.〇χ1〇_9 cm μιη/cni 'sec'Pa. The light transmittance of the film film was measured by υν-245〇 (manufactured by Shimadzu Corporation) to determine the average light transmittance at a wavelength of 350 to 700 nm. The value was 94° /. The puncture strength was 〇25 Ν/μιη, which had sufficient strength. The film was irradiated with 10000 J/cm 2 of ultraviolet light, and the average light transmittance was measured, and the fruit was 94%. The oxalic acid permeation amount of the film irradiated with ultraviolet light at 70 ° C for 72 hours is 4 3 χ 1 〇 · 6 mg / cm 2 (film thickness is 6 〇 μ Π 1) 'film thickness 1 (four) conversion of oxalic acid permeation is 2, 6xl (T5mg/em2. Then, using the accelerated test method for growing foreign matter to confirm the presence or absence of growth foreign matter, the residue of the washing water obtained from the blank material was not obtained. Observing the film with a microscope {no foreign matter was observed. Visual observation under spotlight and monochromatic light As a result, the change after heating was not observed. The average light transmittance was 94.7% before heating and 94 7% after heating. [There was almost no change. Further, the purpose of (4) inspection of the endurance test towel film towel Wrinkles were produced, and no wrinkles were found between the relative humidity of 45% and 97%. (Example 5) 144856.doc • 40- 201037456 5 g of nitrocellulose (manufactured by Bargerac...) was dissolved in % In g-ethyl lactate, 'Turkey _25 g was added to the solution as liquid TINUVIN 292 (Ciba refined) at 25 ° C, and stirred at room temperature for 6 hours to dissolve - decompose. The polymer solution was pressurized to 0.01 MPa, and the solution obtained by filtration through a membrane filter having a diameter of 0.1 μm was applied dropwise to a stone wafer by spin coating: spin coating at 150 rpni using a spin coater. After that, the film was dried by using a hot plate of 60 (:: 30 minutes) to obtain a film film. The film obtained by using the perfluorotributylamine (Fluorinert FC-43 Sumitomo 3M (share), trade name) was added dropwise to the obtained film. A solution containing an amorphous fluororesin, namely cyt〇p CTX-809SP2 (Asahi Glass Co., Ltd.), The product name was diluted to 2%, spin-coated at 300 rpm on a spin coater, and dried at 12 ° C to obtain a film film having a thickness of 6 μm. It is attached to the frame (appearance, longitudinal 149 mmx, width 113 mmx height 4.2 mm, frame width 2 mm) coated with the adhesive agent on the upper edge surface and is cut off and removed from the frame. Part of the film film. Q The film has a oxalic acid permeation of 3 5xl〇-3 mg/cm2 (the film thickness is 6.0 μηι) after being placed at 70 ° C for 72 hours, and the oxalic acid permeation of the film thickness of 1 μηη is 2.1 X 1〇'2 mg. /cm2 ° (Comparative Example 1) A solution containing an amorphous fluororesin, Cyt〇p (manufactured by Asahi Glass Co., Ltd., trade name) CTX_8〇9SP2, was dropped on a tantalum wafer, and was applied on a spin coating machine. 300 rPm after spin coating 'at 70'. (: drying for 10 minutes, and then drying at 180 C for 40 minutes to obtain a film film having a thickness of 4 μm. The film film was unrolled and attached to the upper edge of the surface coated with an aluminum 144856.doc -41 201037456 The frame (shape, longitudinal 149 axis x width 113 mmx height 4.2 mm, frame width 2 mm) is cut and the film film which removes the unnecessary portion from the frame is cut off. The film is placed at 70 ° C. After 72 hours, the oxalic acid permeation amount was 5xl〇-4 mg/cm2 (the film thickness was 4〇μηι), and the membrane thickness i was converted into oxalic acid permeation amount of 2_〇xlO_3 mg/em2. Further, the result of measuring the ammonia permeability coefficient It is 9 ΐχΐ〇9 cm3^m/cm, ec, Pa. The light transmittance of the film film is measured by UV-245 〇 (manufactured by Shimadzu Corporation) to determine the average value of light transmittance at a wavelength of 350 to 700 nm. It is 94%. Then, an accelerated test method for growing foreign matter is used to confirm the presence or absence of growth foreign matter, and as a result, in the residue of the washing water obtained from the blank mask, the IR spectrum is 164 〇 to 167 〇 cm·1. All the 3, 1360 to 1390 cm·1, 1240 to 1260 cm·1 three peaks were observed to confirm the inclusion Production of a foreign body of a chromium oxalate complex (Reference Example 2) Zeonex 48〇R (a Zeonex manufactured by Zeon Corporation, Japan) was added as a cycloolefin polymer (registered trademark was added to 9〇g limonene (Wako Pure Chemical Co., Ltd.) Industrial Co., Ltd.) was stirred at room temperature for 4 hours to dissolve it, and then dissolved at 70 C for 4 hours to dissolve it. 0.5 g of Adekastab LA_62p (ADEKA shares) was added to the solution at 25 C powder. Co., Ltd.) 'Dissolved at room temperature for 6 hours to dissolve. The absorbance of the solution was 0.04 ' and the solution was a clear solution. The solution was added dropwise to the crucible wafer. 'Use a spin coater to 1 〇 After 旋转rprn was spin-coated, it was dried by a hot plate of i6〇°c for 45 minutes to obtain a film crucible. Perfluorodibutylamine (Flu〇rinert FC-43 Sumitomo 3M (share) was added dropwise to the obtained film. Manufacture, business] 44856.doc -42- 201037456 Product name) Diluted into a solid content of 2% of the solution containing amorphous fluororesin, namely Cytop CTX-809SP2 (asahi, ε 肖子(股), trade name) Spin coating at 300 rpm on a spin coater , i2 (TC makes it dry, and thus • obtains a film film with a thickness of 10.0 μηι.) • Spreads the film film and attaches it to an aluminum frame coated with an adhesive on the upper edge (shape 'Version 149 The mmx is 113 mm wide and 4.2 mm high, and the frame width is 2 mm). The film is removed from the unnecessary portion of the frame. ❹ It was confirmed that the film was slightly whitened and the average light transmittance was 85%. Further, an experiment of oozing out the light stabilizer was carried out, and the film surface was observed by a microscope. As a result, a small amount of foreign matter which was not found before heating was generated on the surface of the film. (Comparative Example 3) 5 g of nitrocellulose (degree of substitution of about 2 3) was dissolved in 95 § lactic acid ethyl acetate. The polymer solution was pressurized to 〇.〇丨MPa with nitrogen, and the solution obtained by filtration through a membrane filter having a diameter of 0.1 μm was applied dropwise to the ruthenium wafer by spin coating 'using spin coating After the machine was spin-coated at 丨50 rprn, it was dried by a hot plate of 0 6 〇C for 30 minutes to obtain a film film. A solution containing amorphous fluororesin, Cyt〇p CTX-809SP2 (Asahi Glass Co., Ltd.) was added to the obtained film by using perfluorotributylamine (Fluorinert FC-43 Sumitomo 3M Co., Ltd. L' trade name). The manufactured 'commodity name' is diluted to a solid content of 2 〇/〇. After being spin-coated at 3 rpm on a spin coater, it is dried at 12 ° C to obtain a thickness of 6 μηι. Film film. • The film film is unfolded and attached to an aluminum frame coated with an adhesive on the upper edge (the shape 'longitudinal 149 mm x width 113 mm x height 4.2 mm, frame width 2 mm) and cut off An undesired film film that protrudes from the frame. 144856.doc • 43· 201037456 The oxalic acid permeation amount of 5 χ1〇_3 mg/cm2 (film thickness is 6·〇μιη) after 72 hours of storage at 70 C, film thickness i _ converted oxalic acid permeation It is 3.3 χ 10 2 mg/cm2. This application. The s case is based on the application for the patent application (Japanese Patent Priority 2〇〇9_154176) and 2 (9) 8 years. In the case of the application for the application of the patent application, the contents of the applications are incorporated herein by reference. Industrial Applicability The film of the present invention can be preferably used in the field of manufacturing TFT liquid crystal panels. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an explanatory diagram of an accelerated test method for producing a foreign body of growth; and Fig. 2 is an example of an IR spectrum of a growth foreign matter containing a chromium oxalate complex. [Main component symbol description] 1 Blank mask with film attached 2 Blank mask for removing film 3 Closed container 4 Oxalic acid 5 Pure water 6 丨〇% ammonia solution 144856.doc • 44 -

Claims (1)

201037456 VII. Patent application scope: 1. A film film which is set to 丨〇xlo-3 mg/cm2 or less after 7 hours of rc placement for 72 hours, and the main film material is optical. Using organic polymer. 2- Film film, the ammonia permeability coefficient at 25〇c is below 8 〇χΐ〇·9 cm3々m/cm2.s.Pa, and the main film material is optical organic high. Molecular ❹ · 3· For example, the film film of the item 2, which is 7 〇. The film thickness after 1 hour of 〇 is 1-3 mg/cm 2 or less. The film film 'the main film material is an optical organic polymer, and the (4) material contains a light stabilizer of 〇.1 weight of 3:°/. or more and 15% by weight or less relative to the total weight of the optical material polymer. 5. The plastic polymer used in the above-mentioned item 4 is a cycloolefin oxime resin or a cellulose derivative. 6. If the rubber of the item 4 or 5 is only a wax stabilizer The above light stabilizer is a hindered amine system. 7. A film, the sentence bar. Λ Α In the item (1), == On the upper edge side of the frame, the adhesive film f film film, and the lower edge side of the remaining body 8. As in the film of claim 7, 9 · A film film manufacturing ^ and ^ LCD panel manufacturing light And the use of a light stabilizer to dissolve the organic solvent, and to prepare a polymer solution from the polymerization agent and the second agent. 10. The step of removing the organic solvent in the liquid. The method for producing the above-mentioned organic solvent is I44856.doc 201037456 alicyclic hydrocarbon, vaporized hydrocarbon, ester compound or ketone compound. 11. The method for producing a rubber film according to claim 9 or 10, wherein the light stable The agent is a hindered amine light stabilizer. The method for producing a film film according to claim 11, wherein the hindered amine light stabilizer is liquid at 25 ° C. 13. If any of the items 9 to 12 is clear The method for producing a film film according to the invention, wherein the optical organic polymer is a cycloolefin resin or a cellulose derivative. 14. A photomask having a light-shielding film containing chromium patterned on a surface of a transparent substrate Transfer pattern, and on the transparent substrate A manufacturer of a liquid crystal display device having a film attached to one side of a transfer pattern, the transparent substrate having a thickness of 1 〇〇〇cm 2 or more, and a film thickness of the film film of the film being 0.5 μηι or more and 8 μmη or less And the oxalic acid permeation amount of the film thickness i μηι of the film film after being left for 72 hours in an atmosphere of TC is 1〇xl〇·3 mg/cm2 or less. 15. The mask of claim 14 The transfer pattern of the light-shielding film is formed on the transparent substrate by a sputtering method, and has a pattern cross-section formed by etching. 16. A pattern transfer method in which an exposure beam having a wavelength range of a 丨 line to a 匕 line is irradiated to a reticle of claim 14 or 15 in an atmosphere having a temperature of 15 t or more, thereby transferring the above-mentioned transfer The pattern is transferred onto the transferred body. 17. A method of manufacturing a TFT liquid crystal panel, comprising: a step of preparing a photomask according to claim 14 or 15; and a TFT liquid crystal panel substrate having an IT germanium electrode and applying a photosensitive photoresist by the photomask The step of performing exposure is 144856.doc 201037456, the step of developing the photosensitive photoresist; and the step of etching the ITO electrode with an etching solution containing oxalic acid. 18. A film for use with a mask for manufacturing a TFT liquid crystal panel, the film comprising a frame, an adhesive layer laminated on a side of a lower edge of the frame, and/or a top surface of the frame The film film of the side film is 〇, 5 μm or more and 8 μηι or less, and the film has an oxalic acid permeation amount of 1×10 −4 mg/cm 2 or less after being left for 7 hours. The film of claim 18, wherein the area of the film film is one or more and 30,000 cm2 or less. 20. The film of claim 18 or 19, wherein the film film is formed of a film material comprising a cycloolefin resin. The film according to any one of claims 18 to 20, wherein the film film is made of a cyclic olefin-based resin and a total weight of the substrate is 0.1 weight. /. The film material of the light stabilizer of 15% by weight or less or the light stabilizer containing the cycloolefin resin and the total weight of the cycloolefin resin is 0.1% by weight or more and 15% by weight or less and 〇1% by weight The film material of the above 10% by weight or less of the antioxidant is formed. 22. The film of claim 21, wherein the light stabilizer is liquid-like at normal temperature. The film according to any one of claims 18 to 22, wherein an antireflection layer comprising a cyclic or linear fluorine-substituted fluoroalkyl polyether is laminated on one or both sides of the film film. A method of manufacturing a TFT liquid crystal panel, comprising: laminating a film (4) according to any one of claims 23 to 144856.doc 201037456 on the lower edge side of the frame to be attached to the hard layer a step of chrome masking; a step of exposing a TFT liquid crystal panel substrate having an ITO electrode and applying a photosensitive photoresist through the hard mask; a step of developing the photosensitive photoresist; and utilizing The step of etching the IT0 electrode by an etchant containing oxalic acid. 25. A gamma ray mask having a transfer (4) pattern formed by patterning a opaque film containing chromium on a surface of a transparent substrate, and mounting on a side surface of the permeable plate having a transfer pattern A manufacturer of liquid crystal display devices with film, . The transparent substrate has an area of 1000 cm 2 or more, and the film thickness of the film film of the film is 〇5 _ or more and 8 Å or less, and the temperature is 70. The oxalic acid of the film film after being left for 72 hours in an atmosphere is lxl 〇 -4 mg/cm 2 or less. 26. The reticle of claim 25, wherein the transfer pattern of the opaque film is by 贱A pattern is formed on the transparent substrate by a plating method, and has a pattern cross section formed by patterning. 27. The photomask of claim 25 or 26 wherein the transfer pattern has a line width of 30 μm or more a light-shielding pattern of 500 μm or less. 28. A method of manufacturing a photomask comprising the steps of: forming a light-shielding film containing chromium on a transparent substrate by sputtering; and on the mask film After coating the photoresist, the desired pattern of the pattern is formed on the photoresist film, and then developed to obtain a photoresist pattern, and the light-shielding film is etched by using the photoresist pattern as a mask. The transfer pattern is patterned, and after the photoresist pattern is peeled off, the film is mounted on the light-shielding film side of the transparent substrate, and the film thickness of the film film is 〇·5 μηι above 8 π „ , 79 , at a temperature of 70 The film film after being left for 72 hours in an atmosphere of °C is <early® 夂 through ϊ is lxl〇-4 mg/cm2 or less 0 29. Ο 30. A pattern transfer method, which is raised to /JBL degree In an atmosphere of 15 C or higher, the reticle of the reticle of the item of any of claims 25 to 27, or the reticle manufactured by the method of manufacturing the glaze of the claim 28 includes i line 〜g a method of manufacturing a transfer light beam having a wavelength of a line, thereby transferring the transfer pattern to a transfer-type TFT liquid crystal panel, comprising: preparing an adhesive material laminated on a lower surface side of the frame body And a step of attaching a hard chrome mask of the film of any one of claims 18 to 23; exposing the TFT liquid crystal panel substrate having the ιτο electrode and applying the photosensitive photoresist through the hard chrome mask a step of developing the photosensitive photoresist; and etching the IT germanium electrode with an etching solution containing oxalic acid 144856.doc