TW200947119A - Photosensitive resin laminate - Google Patents

Abstract

Disclosed is a photosensitive resin laminate which has excellent resolution and excellent adhesion to various bases such as polysilicon, amorphous silicon, copper, molybdenum, chromium and tungsten, while having good developability, excellent etching properties and excellent separability. Specifically disclosed is a photosensitive resin laminate wherein at least a supporting layer, at least one of a release layer (a), an alkali-soluble resin layer (b) and a water-soluble resin layer (c), and a photosensitive resin layer composed of a photosensitive resin composition are sequentially laminated. The photosensitive resin laminate is characterized in that the photosensitive resin composition contains 20-90% by mass of an alkali-soluble resin having a phenolic hydroxyl group, 0.01-5% by mass of a photoacid generator, 1-40% by mass of a compound having a group which is crosslinked by the action of an acid, and 1-40% by mass of a plasticizer.

Description

[Technical Field] The present invention relates to a photosensitive resin laminate which is useful for the production of an electrode pattern or a semiconductor pattern, and a method for producing an electrode pattern and a semiconductor pattern using the same. [Prior Art]

The photosensitive resin laminate is also known as a dry film, and has been widely used as a photoresist material for circuit formation such as a printed circuit board. The dry film is characterized in that a lamination step is carried out while laminating a photosensitive resin layer on a substrate. When the liquid photoresist is laminated on the substrate, the liquid photoresist must be applied to the substrate and dried, and then the film thickness is adjusted; however, if a dry film is used, only t will be A photosensitive resin layer having a uniform film thickness is laminated on a substrate to obtain a substrate in which a photosensitive resin layer is laminated. Since the above-mentioned laminating step does not require a solvent, the influence on the environment is small, and the human layer can be laminated on a large-area substrate, and the layer can be continuously laminated on a roll-shaped drum represented by a reel to reel method. On the long substrate. Due to such high productivity, it has recently been proposed not only to apply a dry film to a printed circuit board but also to apply it to various other microfabrication fields. For example, a lead frame, or a tape reel can be automatically combined (tape aut〇mated(10) to call), a film lithography package (chip 〇n Him), or the like. The dry film contains a test polymer called a binder polymer. If the dry film is exposed, the photopolymerization initiator will be cleaved to generate free radicals. When the monomer containing an unsaturated double bond starts to polymerize to harden the exposed portion, it becomes insoluble. Thereafter, the unexposed portion was developed to form a photoresist pattern 137650.doc 200947119. On the other hand, a thin film transistor (hereinafter referred to as TFT, Thin Film) is used as a switching element in a liquid crystal display or image sensing apparatus for image display or image ingestion. At present, TFT is manufactured by photolithography of a positive-type liquid photoresist in most cases (see, for example, the patent document). In a positive liquid photoresist, such as diazonaphthoquinone, it is called a photoactive compound (PAC, ph〇t〇a such as π. The diazonium coupling with a phenolic hydroxyl group under alkaline conditions (diazo) _PHng) becomes an exposure portion, and the light gas is converted into a K-smoke by photoreaction to become an alkali-soluble I. The light micro-machining method using a positive-type liquid photoresist is characterized in that the resolution is compared with the above-mentioned dry film. Preferably, when the aperture area of the TFT is large, the probability of dust and opening portion 4 on the reticle or substrate is higher, and the probability of generating photoresist residue in the positive photoresist is changed to 6 Further, since the PAC absorbs the active light, the film thickness becomes thick and the sensitivity is lowered. Further, as a negative-type toner having a better resolution, a chemically amplified negative-type liquid photoresist is also known (below ' Reference 2, Patent Document 3). In the manufacture of TFTs, for example, when used in liquid crystal displays, it is used to produce several panels on a large-area glass substrate and mass-produced due to the importance of productivity. Therefore, in the manufacture of a TFT, if a dry film can be used, It is possible to establish a manufacturing process with a very high productivity. [Patent Document 1] Japanese Patent Laid-Open No. 2006-72080, No. 137, 650, pp. SUMMARY OF THE INVENTION [Problem to be Solved by the Invention] An object of the present invention is to provide an excellent resolution and adhesion to various substrates such as polycrystalline germanium, amorphous germanium, steel, turn, chromium, tungsten, and buttons. Photoreceptor, which has excellent developability and excellent etchability and releasability. It is also an object of the present invention to provide productivity in terms of sensitivity, time of formation, and lamination steps. A method for producing an excellent photoresist pattern, a method for producing an electrode pattern, and a method for producing a semiconductor pattern. [Means for Solving the Problem] Recently, the inventors of the present invention have repeatedly conducted experiments and made efforts to solve the above problems. The above problem can be solved by using a photosensitive resin laminate having a specific composition, and the present invention is finally completed. [1] to [11]: [1] A photosensitive resin laminate which is characterized in that at least a support layer is sequentially laminated and a layer selected from the following (a) to (C) At least one of the layers ((a) release layer, (b) test-soluble resin layer, (c) water-soluble resin layer) and a photosensitive resin layer containing a photosensitive resin composition; The composition of the octagonal ruthenium composition contains 20 to 90% of the amount of the solvent-soluble resin containing the desired base, 0.01 to 5% by mass of the photoacid generator, and 1 to 4% by mass of the content contained by the action of the acid. The photosensitive resin layered body of the above-mentioned [1], wherein the photosensitive resin composition further contains an alkali-soluble property containing a carboxyl group, the photosensitive resin composition of the above-mentioned [1]. Polymer. [3] The photosensitive resin laminate according to the above [1] or [2] wherein the plasticizer is a compound represented by the following formula (I): [Chemical Formula 1]. -gas. ~〇丨十妙1七(1) ch3 {In the formula, the ruler and the ruler 2 are extended or extended propyl, and R1 and R2 are different from each other, and ml, nl, m2 and n2 are respectively 0 or more, and ml +nl +m2+n2 is 2 to 30; and the repeating structure of "(1)士^和·(〇_κ2)_ may be random or block, and any of the repeating structures may be on the diphenyl side }. [4] A method of producing a photoresist pattern, comprising the step of: contacting the photosensitive resin laminate according to any one of the above (1) to [3] with a layer in which the photosensitive resin layer is in contact with a substrate. Pressing on the substrate; performing light on the photosensitive resin layer; heating the exposed photosensitive resin layer; and developing the heated photosensitive resin layer. [5] The method for producing a photoresist pattern according to the above [4], wherein the step of exposing the photosensitive resin layer is a method of drawing active light. [6] A method of producing an electrode pattern, which comprises the step of wet-casting a portion of a substrate which is not covered by a photoresist pattern produced by the method of the above [4]. [7] A method of producing a semiconductor pattern, comprising the step of dry etching the portion covered by the photoresist pattern manufactured by the method of the above [4], for 137650.doc 200947119. [8] The method for producing a photoresist pattern according to the above [4] or [5] wherein the surface of the substrate in contact with the photosensitive resin layer is molybdenum. [9] The electrode pattern manufacturing method according to [6] above, wherein the surface of the substrate in contact with the photosensitive resin layer is molybdenum. [10] The method for producing a photoresist pattern according to the above [4] or [5] wherein the surface of the substrate which is in contact with the ❹ photosensitive resin layer is amorphous. [11] The method for producing a photoresist pattern according to the above [4] or [5] wherein the surface of the substrate in contact with the photosensitive resin layer is tantalum nitride. [Effects of the Invention] According to the present invention, it is possible to provide an excellent resolution and adhesion to various substrates such as polycrystalline germanium, amorphous germanium, copper, molybdenum, chromium, tungsten, and buttons, and has good developability and etching. Photosensitive sapphire layer excellent in properties and releasability. Further, according to the present invention, a method for producing a photoresist pattern excellent in productivity, a method for producing an electrode pattern, and a method for producing a semiconductor pattern in terms of sensitivity, a development time, a lamination step, and the like can be provided. [Embodiment] Hereinafter, the present invention will be described in detail. The photosensitive resin laminate of the present invention contains a support layer. In order to prevent agglomeration, the support layer usually contains a lubricant. The term "caking" refers to a phenomenon in which a gap or wrinkles are generated due to friction when the support layer or the photosensitive resin laminate is drawn or wound. As for the lubricant, 137650.doc 200947119: Organic or inorganic lubricants. As for the organic lubricant: fatty acid, higher alcohol, aliphatic hydrocarbon, aliphatic decylamine, fatty acid secondary salt, hydrazine fatty acid, etc., preferred are higher fatty acids or higher alcohols. As for = (, the system ' can be cited: tannic acid, dodecanoic acid, tetradecanoic acid: octadecanoic acid, behenic acid, hexamic acid, octadecanoic acid, thiric acid - hexadecanoic acid For example, as a specific example of the higher alcohol, pentanol, t-fermented: dodecanol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecanol, twenty-one, one. Twenty-six alcohol, heptadecyl alcohol, octadecyl--decyl alcohol, oleyl alcohol, sub-material, sub-linolenic alcohol, etc. As for inorganic lubrication: carbonic acid, acid acid, magnet dioxide, kaolin , talc, - titanium oxide, aluminum oxide, barium sulfate 'calcium fluoride, lithium fluoride, : chemical inorganic particles. In order to obtain a high degree of transparency, a good bismuth bismuth bismuth particles. The particle size is preferably 0·〇Η.2 μΓΠ. In terms of suppressing the particles from the coating layer, the sentence is good and the thickness of the coating layer after drying is less than 2 times. From the viewpoint of improving the effect of the winding, the average particle size is better than μιη. · The layer is heated at 2 沿 in the width direction (the heat shrinkage rate after heating for 3 minutes at rc is better than G.CU~4.00%) The heat shrinkage rate after heating for 3Q minutes in the 15th generation is better than that of 〇.(H~0.20%. The heat shrinkage rate after heating for 3Q minutes is Α1疋〇〇20·20. The support layer is along the width direction. The heat shrinkage ratio is preferably at least the above lower limit from the viewpoint of ease of production, and is preferably at least the above upper limit from the viewpoint of qualitativeity. The u support layer is heated at a temperature of 1 G 5 t for 3 G minutes in the longitudinal direction. The shrinkage rate is better than 137650.doc 200947119 is G.3G~0.6()%, more preferably Q35~G 55%. The heat shrinkage rate of the support layer is preferably heated at 150C for 3 minutes in the length direction. 〇〇~1.9G%. The support layer is heated at 2 (10) in the length direction. The heat shrinkage rate of the heating clock is 3.GG~6.5G%. The thermal shrinkage of the support layer along the length direction & From the viewpoint of the susceptibility, it is preferred that the above lower limit is more preferable in terms of dimensional stability at the time of lamination.

The heat shrinkage rate of the support layer can be obtained by the following methods: • 5 test pieces of width 2 brewing and 150 lengths are taken from the length direction and the width direction of the film, respectively, and about 1 inch is set in the center of the test piece. The distance of _ is left as a gage mark, and the test piece is vertically (four) in a hot air circulating positive temperature sipe which is kept at the above temperature π, heated for 30 minutes, taken out, and left at room temperature for 3 minutes, and then measured. The distance between the punctuation is the contraction rate: , / I liter... AL (%) = (L-LO) / L 〇 x 100 (1) { where AL is the heat shrinkage rate (%), 7 is the distance between the punctuation points of the heating (mm) 'and l is the distance between the p-points of the selected machine b after heating (mm)}; and the average value is obtained. Furthermore, the heat shrinkage rate is eight

Γ9.1β 1Ωη, and other conditions in 疋 are based on JIS C2318-1997 (5.3_4 dimensional change). The photosensitive resin layer of the present invention is provided with at least one layer of the layer shown in the following (4) to (4) between the support layer and the photosensitive resin layer: (a) a release layer, (b) a base a soluble resin layer and (c) a water-soluble resin layer. 137650.doc 200947119 The following is a description of the layers shown in (a) to (c). The (4) release layer refers to a layer composed of a release agent (hereinafter, also referred to as a release agent) provided to improve the release property from the support layer; the treatment of the release layer on the support layer Also known as mold release treatment. The mold release treatment may, for example, be at least one selected from the group consisting of a silicone resin, a fluororesin, an acid alcohol resin, a long-chain alkyl resin, an acrylic resin, and a polyolefin resin. A release agent for a resin that is coated with a thin layer on the surface to enhance the chemical treatment of the release property. (a) The film thickness of the release layer is preferably Νπο nm. The viewpoint of the release effect is preferably 1 nm or more, and it is preferably 5 Å or less from the viewpoint of migration of the release agent to the photosensitive resin layer during transfer or storage.乍 is the Shixi oxygen tree 曰 曰 可 可 可 可 可 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石 石a condensation reaction type oxirane resin formed; or a dimethyl methoxy oxane methyl methoxide copolymer or a dimethyl methoxy olefin methyl methenyl decane copolymer and polymethyl hydrogen The addition reaction type of Shixia oxygen tree formed by the reaction of Shixi oxygen burning or ultraviolet curing by ultraviolet light or electron beam to harden propylene I poly 7 oxygen or epoxy group-containing polysulfide Type or electron beam hardening type oxime oxy-resin; or modified ♦ oxy-resin, for example: epoxy modified stone oxime tree (polyoxygen, oxygen), polyester modified oxime resin (polyoxyl- Polyester), acrylic modified beryllium oxy-resin (polyoxy-acrylic acid), phenol-modified oxirane resin (polyoxyl-phenol), acid-alcohol modified oxirane resin (polyoxyl-acid yeast), melamine modified An epoxy resin (polyoxyl-melamine) or the like. As the fluororesin, a fluororesin typified by an amorphous fluororesin may be mentioned. 137650.doc 200947119 As for the amorphous fluororesin, LUMIFLON manufactured by Asahi Glass Co., Ltd., and C YTOP manufactured by Asahi Glass Co., Ltd. may be mentioned. For the copolymerized oligomer containing a perfluoroalkyl group-containing (meth) acrylate and an alkyl (meth) acrylate as a main component, MODIPER F series manufactured by Nippon Oil & Fats Co., Ltd. and Daikin Industries Co., Ltd. UNIDYNE, MEGAFAC F470 series manufactured by Otsuka Ink Chemical Industry Co., Ltd., F480 series manufactured by Dainippon Ink Chemical Industry Co., Ltd., F110 series manufactured by Otsuka Ink Chemical Industry Co., Ltd., etc.; as a copolymerization, it is better to block polymerization. As the fluorine-based coating agent, EGC1700 manufactured by Sumitomo 3M Co., Ltd. can be cited. As for the fluorine-based surfactant, MEGAFAC F 114 manufactured by Otsuka Ink Chemical Industry Co., Ltd., F410 series manufactured by Dainippon Ink Chemical Industry Co., Ltd., 440 series manufactured by Dainippon Ink Chemical Co., Ltd., and manufactured by Dainippon Ink Chemical Co., Ltd. 450, 490 series made by Otsuka Ink Chemical Co., Ltd. Examples of the gas-based surface treatment agent containing an electron beam or an ultraviolet curing component include PolyFox PF-3320 manufactured by Omnova Solutions, and Cheminox FAMAC-8 manufactured by Unimatec. Examples of the fluorine-based surface treatment agent containing a thermosetting component include EGCl72® manufactured by Sumitomo 3M Co., Ltd., NH-10, NH-15 manufactured by Dainippon Ink Chemicals Co., Ltd., and the like. The fluorine-containing compound in the fluorine-containing compound layer may also be a mixture of a plurality of fluorine-containing compounds. From the viewpoint of light transmittance of the fluorine-containing compound layer, since it is amorphous, it has high ultraviolet transmittance (refer to Asahi Glass Research Report 55, 2005), and therefore an amorphous gas resin is preferable. Alkyd resin, also known as enzyme resin, is a modified product of a fatty acid or a fatty acid to a polycondensate of a polybasic acid and a multi-fermented yeast. From 137650.doc 200947119, sometimes the oxygen resin will be transferred to the photosensitive resin layer, so acid alcohol resin can be used in order to avoid the transfer of such polyfluorene oxide component... In terms of the balance between the coatability and the peelability of the layer, it is preferred that the release layer contains an acid alcohol resin. As the polybasic acid, for example, a saturated polybasic acid such as phthalic acid needle, terephthalic acid, succinic acid, adipic acid or sebacic acid; or cis-butane diacid or maleic acid; Unsaturated polybasic acid such as needle, fumaric acid, itaconic acid, citraconic acid anhydride; cyclopentadiene-maleic anhydride adduct, sterene-maleic anhydride adduct, rosin Maleic anhydride adduct. The polyhydric alcohol may, for example, be a glycol such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol or butylene glycol; a trihydric alcohol such as glycerin or di-alkane; Alcohols, for example, diglycerin, triglycerin, pentaerythritol, dipentaerythritol, mannitol, sorbitol, and the like. As the modifier, for example, soybean oil, linseed oil, tung oil, scallion oil, dehydrated sesame oil, raspberry oil, and the like, fatty acid, octadecanoic acid, oleic acid, linseed oleic acid, and linseed oil may be mentioned. Acids, eleostearic acid, banar alkyd, dehydrated maricin acid and other fatty acids, rosin, fossil gum, succinol, shellac and other natural resins, ester glue, phenol resin, urea resin, melamine resin Such as synthetic resin. Further, from the viewpoint of the balance between the coatability and the peelability, a hardened resin of an octadecanoic acid-modified acid alcohol resin and/or an octadecanoic acid-modified acrylic resin and an amine resin is also preferable. Long chain alkyl based resins can be any of those known in the art. Further, the acrylic resin may be any of those known in the art. The polyolefin-based resin may, for example, be an olefin-based thermoplastic elastomer, for example, 137650.doc -12-200947119 such as an ethylene-propylene copolymer or an ethylene-octene copolymer. The polyolefin resin may be used in combination with a polyethylene resin or the like. In the case of applying a release agent, it is preferred to coat as thin as possible within the limits of obtaining the release effect. The release agent may also be fixed to the support layer (film) by heat treatment or uv treatment after coating. As for the support layer which is subjected to the mold release treatment, as a commonly available person, for example, LS, 1〇31, i〇2〇, i〇i〇, 201〇, C, which are made by Lintec (share).

2080, 2090, 2100, E, 6040, 6010, X, SK-1, AL-5. Also, Teijin Dupont Films (share) A_ 60 A-70, Mitsubishi polyester film (Mitsubishi p〇lyester), T-100H, etc. can be mentioned. The (b) alkali-soluble resin layer is a resin layer containing a test compound having three carboxyl groups which are the same as the (four) polymer which is contained in the photosensitive film of the present invention. In addition to the alkali-soluble polymer having a carboxyl group, it is preferred to include a plasticizer from the viewpoint of flexibility. As the plasticizer, the same plasticizer as used in the photosensitive resin layer can be used. X, the test is mixed with the initiator component of the photosensitive (four) layer, and the starter component may be contained in the alkali-soluble resin layer. In this case, it is preferred to contain the same initiator as the initiator used in the photosensitive resin layer in the same mass ratio. (b) The film thickness of the solvent-soluble resin layer is preferably 30 μm or less from the viewpoint of developability and resolution, and is preferably 3 μη or more from the viewpoint of ensuring mold release property from the support layer. (4) The water-soluble resin layer can be obtained by diluting the water-soluble resin composition with water or another solvent depending on the film to be coated 137650.doc -13- 200947119 Thickness or viscosity, and then coating and drying it. If the analysis of the water-soluble resin composition is not carried out, other solvents may be used. From the viewpoint of coatability and dryness, it is preferred that the boiling point is lower than that of water, and it is preferred to use water in combination with such other solvents. Specifically, a mixed solvent of water and ethanol or decyl alcohol may be mentioned, and a mixed solvent of water and decyl alcohol is preferred. Further, since the water-soluble polymer containing at least vinyl alcohol as a copolymerization unit is often hardly dissolved in cold water, it is often easily mixed with a water-soluble plasticizer if it is dispersed in cold water to be heated and dissolved in advance. . Preferably, the water-soluble resin composition contains a water-soluble polymer containing vinyl alcohol as a copolymerization unit. Examples of the water-soluble polymer containing vinyl alcohol as a copolymerization unit include polyvinyl alcohol and a derivative thereof, and polyvinyl alcohol obtained by copolymerizing 1 to 20 mol% of an olefin. Polyvinyl alcohol is usually produced by subjecting polyvinyl acetate to alkali saponification. The weight average molecular weight of the polyvinyl alcohol is preferably from 1,000 to 100, 〇〇〇. The weight average molecular weight of the polyvinyl alcohol is more preferably from 5,000 to 50,000 in terms of oxidation inhibition and developability. The degree of saponification is preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably 80 mol% or more from the viewpoint of developability. Examples of such polyethylene glycols include PVA-103 > PVA-105, PVA-110, PVA-117 'PVA-124, PVA-203, PVA-205, and PVA-217 manufactured by Kuraray Co., Ltd. , PVA-220 ' PVA- 224 ' PVA-226, PVA-235, PVA-403, PVA-405, PVA- 420. 137650.doc -14- 200947119 The carboxylated polyvinyl alcohol described in JP-A-63-197942 is exemplified as a derivative of the polyvinyl alcohol. The polyvinyl alcohol in which 1 to 2% by mole of the olefin is kneaded is usually produced by copolymerizing a mother hydrocarbon with ethylene acetate and then saponifying the obtained copolymer. As for the rare hydrocarbons, there are mentioned: B, π, 匕, propylene, 丨_hexene, and the like. From the viewpoint of copolymerizability and solubility, ethylene is preferred. As far as the (four) nature is concerned, the copolymerization ratio of the lean hydrocarbon is 2 〇 mol% or less. As for this kind of

The polyvinyl alcohol copolymerized with 1 to 2 mol% of an olefin is exemplified by Eval (trade name) manufactured by Kuraray Co., Ltd. The water-soluble resin composition containing 50% by mass or more and 95% by mass or less of the vinyl alcohol as a copolymerization unit is preferably blended in the water-soluble resin composition. Furthermore, it is more preferable that the water-soluble high molecular weight of the water-soluble resin composition containing ethylene glycol as a copolymerization unit is 60% by mass or more and 9% by mass or less. From the viewpoint of the release property from the support layer, it is preferred that the water-soluble resin composition contains a water-soluble plasticizer. Examples of the water-soluble plasticizer include polyvinylpyrrolidone and its organism, water-soluble cellulose derivatives such as hydroxyethyl cellulose, polyoxyethylene, polyoxyethylene ester, and polyethylene oxide. Polyethylene oxide and its derivatives such as ether compounds, vinyl ether and maleic anhydride copolymers and water-soluble salts thereof, water-soluble salts of carboxyalkyl starch, polypropylene decylamine, polydecylamine, polyacrylic acid Water-soluble salts, gelatin, polypropylene glycol, and the like. Specific examples of the polyvinylpyrrolidone include κ-15 (weight average molecular weight: 40,000) and κ_3 〇 (weight average 137650.doc 15 200947119 molecular weight: 100,000) manufactured by Nippon Shokubai Co., Ltd., and Κ -85 (weight average molecular weight: 900,000), Κ-90 (weight average molecular weight: 10,000). Specific examples of the polyethylene oxide and the derivative thereof include polyethylene glycol having a number average molecular weight of 200 (PEG 200 manufactured by Nippon Oil & Fat Co., Ltd.) and polyethylene glycol having a number average molecular weight of 300 (Japanese oil month) PEG300), a polyethylene glycol having a number average molecular weight of 400 (PEG400 manufactured by Sakamoto Oil Co., Ltd.), a polyethylene glycol having a number average molecular weight of 600 (PEG600 manufactured by Nippon Oil & Fat Co., Ltd.), the number Polyethylene glycol having an average molecular weight of 1 曰 (PEG 1000 manufactured by Sakamoto Oil Co., Ltd.) or polyethylene glycol monoterpene ether having a number average molecular weight of 400 (Uniox Μ-400 manufactured by Sakamoto Oil Co., Ltd.), Polyethylene glycol monoterpene ether having a number average molecular weight of 550 (Uniox M-5 50, manufactured by Nippon Oil & Fat Co., Ltd.), and polyethylene glycol monoterpene ether having a number average molecular weight of 1000 (Uniox M manufactured by Nippon Oil & Fat Co., Ltd.) -1000) and so on. The weight average molecular weight of the water-soluble polymer is determined by GPC (Gel Permeation Chromatography) (pump: Gulliver, PU-1 5 80, column: Showa Denko (share) Two Shodex (registered trademark) (HFIP-805, HFIP-803) series, moving bed solvent: hexafluoroisopropanol, and polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Denko) The calibration curve was obtained as a weight average molecular weight (in terms of polystyrene). The film thickness of the water-soluble resin layer is preferably 0.1 μm or more from the viewpoint of mold release property, and is preferably 10 μm or less from the viewpoint of developability. When the photosensitive resin laminate is used in the form of a roll, it is 137650.doc -16· 200947119. The photosensitive resin layer having adhesiveness is prevented from being transferred to the support layer or dust or the like is adhered to the photosensitive resin layer. The protective layer can be laminated on the photosensitive resin layer and used. The maximum roughness (Ry) of the surface of the protective layer in contact with the photosensitive resin layer is preferably 2.0 μm or less. Sometimes the unevenness of the surface to be transferred due to the protective layer is not removed at the time of lamination to cause voids, thereby suppressing

From the viewpoint of this phenomenon, the maximum roughness (Ry) is preferably 2 〇 爪 or less, and 较好 〇 1 or more is preferable from the viewpoint of easiness of production. The maximum coarse chain ratio (Ry) was measured by JIS Β 0601. As the film used as the protective layer, a polyolefin film is preferred. A polyethylene film, a polypropylene film, etc. are mentioned. A polyolefin film generally used as a protective film is obtained by heating and melting a raw material, kneading, extruding, and biaxial stretching or casting. Further, in general, a protective film such as a polyolefin film contains an unmelted and thermally deteriorated material called a fisheye. Regarding the size of the fisheye, the diameter (Φ) is usually 30 to 600 μm, and the fisheye is protruded from the surface of the film at a height of 2 to 4 μm. The convex portion of the squid eye is transferred onto the photosensitive resin layer and a depression is generated on the photosensitive resin layer to cause an air gap (仏V〇id) on the laminated substrate. A gel called fisheye is usually present in the polyethylene film, but it is preferred that the gel is less. The film thickness of the protective layer is preferably in the case of reducing the fisheye when the protective layer is a polyethylene bake film, and it is preferably 20 it or more in terms of reducing the fish eye. The film thickness of the protective layer is preferably at most % from the viewpoint of volume increase or operability when wound into a roll. In the case where the protective layer is a polypropylene phase, the fisheye is very small, and there is no particular limitation on the film thickness; from the viewpoint of the function of the protective layer, it is preferable that the photosensitive resin 疋5 μηι or more suppresses the volume. It is preferably 25 μmη or less from the viewpoint of wrinkles of 137650.doc 200947119. As for the polyethylene film which can be obtained as a commercial item, Tamapoiy (share) _18, Shen _818, _ 858; as for the sale of poly propylene film which can be obtained as a commercial print, can be mentioned Out: Oji Paper (Shares) System

Arufun (registered trademark) E-200, E-200A. The photosensitive resin layer constituting the photosensitive resin laminate of the present invention is composed of a photosensitive resin composition containing an alkali-soluble resin containing a phenolic hydroxyl group, a photoacid generator, and an action by an acid. The compound which is crosslinked and the plasticizer. Hereinafter, the items will be described in order. Examples of the alkali-soluble resin containing a phenolic hydroxyl group include a novolak resin and a polyhydroxystyrene resin. As the novolak resin, it can be used as a material for forming a coating film in the conventional positive-type photoresist composition. The novolak resin is obtained by, for example, addition-condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter also referred to simply as "phenol") with an aldehyde in the presence of an acid catalyst. As for the phenols used at this time, for example, phenol, o-nonylphenol, dioxin, p-test, o-ethyl stupid, m-ethyl benzene, p-ethyl benzene, o-butyl Phenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2'4-monobenz, 2,5-methyl, 2,6-dimethyl, 3,4 - dimethyl stupid, 3,5--A test, 2,3,5-trimethyl benzene, 3,4,5-trimethyl phenol, p-phenylphenol, resorcinol, pair Streptophenol, p-benzoquinone monomethyl ether, pyrogallol, phloroglucinol, hydroxy phenyl, bisphenol A, gallic acid, gallic acid ester, ct-naphthol, β-naphthol . Further, as for the aldehydes, for example, 137650.doc 200947119 "T cites, bismuth, dimercaptoic acid, citric acid, benzophenone, nitrophenylhydrazine, acetaldehyde. The catalyst used in the addition condensation reaction is not particularly limited. For example, if it is an acid catalyst, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid or acetic acid can be used. As the alkali-soluble novolac resin, it is preferred that the weight average molecular weight of the low molecular region is 2, 〇〇〇 2 2 〇, and the range of 〇〇〇. In the case of considering the outline shape of the photoresist pattern, it is preferred to use a phenolic compound containing 30% by weight or more of m-cresol, and it is particularly preferable to obtain the following mixed phenolic compound. The mixed phenolic compound contains 55 to 75% by weight of cresol, and contains 45 to 25% by weight of at least one selected from the group consisting of a pair of azide, 2,5-monomethyl and 3,5-xylene. One is made as a residual component. Examples of the polyhydroxystyrene resin include polyhydroxystyrene, modified polyhydroxystyrene, hydrogenated polyhydroxystyrene, hydroxystyrene and styrene, (fluorenyl)acrylate, and cis-butene. a copolymer formed by an acid ester or the like. ❹ As for the modified polyhydroxystyrene, there may be mentioned, in the presence of a basic catalyst, a polyphenylene benzoate and, for example, a benzoquinone derivative, a naphthalene hydrazine derivative, a benzamidine chlorine derivative, A naphthoquinone chloride derivative or the like is formed by reaction. Specific examples of the above-mentioned sulfonium chloride derivative or carbonyl chloride derivative include acetaminophen benzene sulfonium chloride, sulfonium sulfonium, gas benzene, naphthylbenzene, and hydrazine. For acetaminophen benzamidine, benzamidine gas, p-benzophenone gas, naphthylbenzoquinone chloride, and the like. In this case, the above sulfonated chlorine derivative or the above vaporized carbonyl derivative can be usually used in an amount of 10 to 30 parts by weight, preferably 15 to 25 parts by weight, based on 100 parts by weight of the polyhydroxystyrene. Such a 137650.doc •19-200947119 may be 3,00 〇~5 〇, 〇〇〇, the weight average molecular weight of the modified polyhydroxystyrene is preferably in the range of 5,000 to 30,000. The weathered polybasic group is made of a hydrogenated benzene ring m which is modified by a substituent to modify the poly(phenylene) benzene and the benzene ring. The weight average molecular weight of the hydrogenated polyhydroxystyrene is usually selected from the range of 3,000 to 30,000, preferably 5, 〇〇〇 25, and 〇〇〇. The weight average molecular weight is preferably 3,000 or more from the viewpoint of mechanical properties or dry resistance, and is preferably 30,000 or less from the viewpoint of compatibility.

The blending amount of the test-reducing resin containing the desired property is preferably from 2 to 9 % by mass based on 100% by mass of the photosensitive resin composition. More preferably, it is 30 to 70% by mass. From the viewpoint of sensitivity, it is preferably at least 20% by mass, and from the viewpoint of developability, it is preferably 9% by mass or less. From the viewpoint of the surface state of the resist pattern obtained after the development, it is preferred to use a novolac resin or a polyhydroxystyrene resin as the alkali-soluble resin having a phenolic hydroxyl group.

From the viewpoint of the cross-sectional shape of the photoresist pattern obtained after development, a solvent having a versatile radical can be appropriately selected. For example, when the varnish is used, the cross-sectional shape tends to be dome-shaped, and when the polyacryl-based styrene resin is used, the cross-sectional shape tends to be rectangular. The photoacid generator is a compound which directly or indirectly generates an acid by irradiation with light, and specifically, 2,4_bis(trimethylmethyl)_6_[2_(2-furanyl)vinyl] is three Plough, 2,4-bis(trimethyl)methyl-6_[2·(5-methyl_2_furanyl) 337650.doc -20. 200947119 Ethylene base] three tillage, 2,4·double (three Gas methyl)-6-[2-(5-ethyl-2-furanyl)vinyl] is three-ploughed, 2,4-bis(trimethylsulfonyl)_6_[2_(5_propyl_2_ Furanyl) vinyl] three-till, 2,4_bis(trimethylmethyl)-6-[2-(3,5-dimethoxyphenyl)vinyl], three tillage, 2,4· Bis(trichloromethyl)_6_[2_(3,5-diethoxy.phenyl)vinyl] is three-pile, 2,4-bis(trichloroindenyl)_6-[2-(3,5 -dipropoxy-phenyl)vinyl;|all three tillage, 2,4_bis(trimethylmethyl)_6_[2_(3_methoxy-5-ethoxyphenyl)vinyl] Three tillage, 2,4-bis(trichloromethyl)-6-[2-(3-0 曱oxy-5-propoxyphenyl)vinyl] are three-plowed, 2,4_double (three Gas 曱)) 6-[2-(3,4-methylenedioxyphenyl)vinyl] is three-pile, 2,4_bis(trichloromethyl)-6-(3,4- Methylenedioxyphenyl Three tillage, 2,4·bis-triseodecyl-6-(3-bromo-4-methoxy)phenyl-all three tillage, 2,4_bis-trichloromethyl_6_(2_bromo Methoxy)phenyl-averaged, 2,4-bis-trichloromethyl-6-(2-bromo-4-indolyl)styrylphenyl-averaged, 2,4-double - tri-gas methyl-6-(3-bromo-4-indolyl)styrylphenyl_-three-plowed, 2_(4-methoxyphenyl)_4,6-bis (trioxanyl) -1,3,5_three tillage, 2_(4_decyloxynaphthyl)_4,6_bis (three gas 甲 base '^^ three P well, 2-[2-(2-furyl)ethylene Base]_4,6-bis(trichloroindenyl)-1,3,5-three tillage, 2_[2_(5•indolyl-2-furyl)vinyl]_4,6-bis(trichloroindenyl) )-1,3,5-three tillage, 2-[2-(3,5-dimethoxyoxyphenyl)vinyl]-4,6-bis(trimethyl)-1,3,5- Three-plowing, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trimethylmethyl) three-pile, 2-(3,4-methylenedioxy) Phenyl)-4,6-bis(trimethylsulfonyl) 4,3,5-three tillage, 2,4_trimethylmethyl (piperonyl)_ 6-triple P, tris(13-dibromopropyl) Base)-1,3,5-three tillage, tris(2,3-dibromopropyl)-1,3,5-dihed, etc. compounds containing halogens, and three (2,3_ Isocyanurate compound containing dentate such as dibromopropyl)isocyanurate. 137650.doc •21 · 200947119 Further, as the photoacid generator, a_(p-toluenesulfonyloxy group) may also be mentioned. Imino)phenylacetonitrile, α-(phenylsulfonyloxyimino)_2,4-dichlorophenylacetonitrile, a-(phenylsulfonyloxyiminodiphenylphenylacetonitrile, a-( 2_gas benzene cans, methoxyimino)-4-decyloxy acetonitrile, a-(ethylsulfonyloxyimino)-cyclopentyl acetonitrile, or the following formula (1丨) ) the compound represented:

N——O—S02R4 (II) rn {wherein, R is a monovalent to divalent organic group, and R4 represents a substituted or unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group or an aromatic compound group, and then η represents 1~ 3 natural number}. Here, the aromatic compound group refers to a group of a compound which exhibits a specific physical or chemical property in an aromatic compound, and examples thereof include an aromatic hydrocarbon group such as a stupid group or a naphthyl group, or a furyl group or a thienyl group. An aromatic heterocyclic group. The groups may also have more than one suitable substituent on the ring, such as an imine atom, an alkyl group, an alkoxy group, a nitro group, and the like. Further, R3 is particularly preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a mercapto group, an ethyl group, a propyl group and a butyl group. Among the compounds of the formula (II), a compound wherein R3 is an aromatic compound group and R4 is a lower alkyl group is particularly preferred. The photoacid generator represented by the above formula (1)) may, for example, be a compound in which R3 is a phenyl group, a fluorenylphenyl group or a methoxyphenyl group, and r4 is a methyl group; Specific examples thereof include: fluorenylmethyl oxyimino)+phenylacetonitrile, (methyl ethoxylated 137650.doc -22-200947119 ketimido)-1-(p-phenylene)acetonitrile, --(methylsulfonyl imido) (p-methoxyphenyl) acetonitrile. Further, examples of the photoacid generator include bis(p-toluenesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazononane, and bis(cyclohexyl-continuation- a sulfonyl diazomethane such as diazonium diamine or bis(2,4-dimethylphenylsulfonyl)diazepine; 2-nitrobenzyl p-toluenesulfonate, Toluene acid 2,6-dimercaptobenzyl ester, toluene acid benzyl vinegar, toluene dinitrobenzyl ester, nitrobenzyl sulfonate, nitrobenzyl carbonate, dinitrobenzyl carbonate, etc. Nitrobenzyl derivative; pyrogallol trimethanesulfonate, o-branched tridecyl sulfonate, benzyl benzene sulfonate, benzyl sulfonate, N_mercaptosulfonyloxybutane Imine, N-trismethylsulfonyloxybutaneimine, N-phenylsulfonyloxybutanedienimide, N-methyl ethoxylated phthalimide Sulfonate; diphenylsulfonate hexafluorophosphate, (4-methoxyphenyl)phenylsulfonium trifluoromethanesulfonate, bis(p-tert-butylphenyl)phosphonium trifluoride Methanesulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl) diphenyl锈 镔 镔 trifluoromethanesulfonate, (p-butylphenyl) diphenyl sulfonium trifluoromethanesulfonate and other rust salts; benzoin benzene sulfonate, α-methyl benzoin benzene sulfonate A benzoin tosylate of an acid ester or the like; other, a diphenylphosphonium salt, a triphenylsulfonium rust salt, a stupid diazonium salt, a benzyl carbonate or the like. In particular, the second-till compound has a high performance as a photo-acid generator, and the solubility is also good in the case of using a solvent, so that it can be preferably used. Among them, a three-cultivation compound represented by the following formula (111) and a three-till compound containing bromine are used: [Chemical 3] 137650.doc -23· 200947119

Particularly suitable for use: 2,4-bis-tris-methyl-6-(3-bromo-4-methoxy)phenyl-all three tillage, 2,4-bis-trisulphuryl _6_(3_ Bromo_4_decyloxy)styryl_-three-till, tris(2,3-dibromopropyl)isocyanurate. 1 〇〇 mass relative to the photosensitive resin composition. /0, which may be 1 to 5 mass%, preferably 0.05 to 1 mass in 〇 。. /. The better is 〇"~〇 5 quality. The photo-acid generator is contained in the range of /. The content of the photoacid generator is preferably 0.01 mass%/❶ or more in terms of sensitivity with respect to 1% by mass of the photosensitive resin composition, and is in terms of storage stability, resolution, and exposure range. More preferably, it is 5 parts by weight or less. As the compound having a group which is crosslinked by the action of an acid, an amine compound such as a melamine resin, a urea resin, a guanamine resin, a glycoluril-furfural resin, a succinimide-formaldehyde resin can be used. As the ethylene urea-formaldehyde resin, an alkoxythiolated amine-based resin such as an alkoxylated melamine resin or a methoxymethylated gland resin or the like is particularly preferably used. The above alkoxymethylated amine-based resin can be produced, for example, by the following method: a condensate obtained by reacting melamine or urea with formalin in a boiling aqueous solution, and methanol, ethanol, propanol, butanol, The lower alcohol such as propanol reacts to form an ether, and then the reaction liquid is cooled to precipitate. As the above alkoxylated amide-based resin, specifically, a fluorenyl thiolated melamine resin, an ethoxymethylated melamine resin, a propoxymethylated 137650.doc-24- 200947119 Melamine resin, butoxymethylated melamine resin, methoxylated urea resin, ethoxymethylated urea resin, propoxymethylated urea resin, butoxymethylated urea resin, and the like. The above alkoxymethylated amine resins may be used singly or in combination of two or more. In particular, the alkoxy-denylated melamine resin is preferred because it can form a resist pattern having a small dimensional change and a stable dimensional change with respect to the amount of radiation irradiation. Among them, a decyloxymethylated melamine resin, an ethoxymethylated melamine resin, a propoxymethylated melamine resin or a butoxymethylated melamine resin is preferred. As the alkoxymethylated melamine resin, there are mentioned: NIKALAC MX-750, NIKALAC MX-706, NIKALAC MX-101, NIKALAC MX-032, NIKALAC MX-708, NIKALAC MX-40, NIKALAC MX-31, NIKALAC MS-11, NIKALAC MW-22, NIKALAC MW-30, MW-30HM, MW-100LM, and NIKALAC MW-390 (all of which are manufactured by SANWA CHEMICAL Co., Ltd.). These may be used singly or in combination of two or more. As the alkoxymethylated urea resin, MX-290 (manufactured by SANWA CHEMICAL Co., Ltd.) can be mentioned. The compound having a group which is crosslinked by the action of an acid may be contained in an amount of from 1 to 40% by mass, preferably from 5 to 20% by mass, based on 100% by mass of the photosensitive resin composition. In the photosensitive resin composition, the content of the compound having a group which is crosslinked by the action of an acid is preferably 1 part by weight or more from the viewpoint of sensitivity and resistance to the survivability, and storage stability is obtained. The residue after development is preferably 40 parts by weight or less from the viewpoint of the residue after development. 137650.doc -25- 200947119 As for the plasticizer, phthalic acid acetonate such as diethyl phthalate, decyl o-toluenesulfonate, decyl p-toluenesulfonate, and butyl citrate may be mentioned. Vinegar, triethyl citrate, triethyl citrate triethyl citrate, acetaminophen citrate tri-n-propyl vinegar, acetamidine tri-n-butyl acrylate, polypropylene glycol, polyethylene glycol, polyethylene glycol 、, polypropylene glycol ether ether, polyethylene glycol polypropylene glycol 肷 'copolymer (also known as Pluronic plastic) and its dialkyl ether, single rhyme puzzle. Further, a plasticizer represented by the following formula (I) can be preferably used: [Chemical 4] ❹ CH3 (I)

Wherein R1 and R2 are exoethyl or exopropyl' and ... are different from ruler 2; 111, 1112 and 112 are respectively 0 or more, and 〇11+111_2+112 is 2 to 30; and then - (Of), the repeating structure of _(〇_r2)_ may be random or block 'and - (Saki and _( any biphenyl side in the repeating structure of __). In the formula (1), it is synthesized by adding ethylene oxide or oxidizing (4) of Aifu A. In order to obtain sufficient degree and adhesion, Gabha 2 is 3 G or less, which is in the photosensitive complex. The compatibility and the viewpoint of increasing the viscosity are as follows: Μ2 is better in terms of solution and adhesion: 2 to 20' and further preferably 2 to 10. Further, in terms of resolution, From the viewpoint of adhesion collection and developability, it is further preferred that R3 is an exoethyl 137650.doc 26·200947119 is a stretching propyl group, ml+m2 is 0, and nl+n2 is 2 to 10 The compound represented by the formula (I): Specific examples of the compound represented by the above formula (I) include: ADEKANOL (trademark jSDX-lSGqR1: exoethyl, R2: exopropyl, ml=m2= 0 » nl=n2=l] ' ADEKANOL( ^ # )SDX-1570 [Κ!: Ethyl, R2: propyl, ml=m2=0 'nl=n2=3], ADEKANOL (trademark PDX-ISTUR1: extended ethyl, R2 = propyl, ml=m2=0 » Nl=n2=5] ' ADEKANOL(^ # )SDX-479[R1 : #ethyl, R2 : propyl, ml=m2=5, nl=n2=0] (The above is manufactured by Asahi Kasei Co., Ltd.) , NEWPOL (trademark pPdSPtR1: extended ethyl, R2: propyl, ml = m2 = 0, nl = n2 = l), NEWPOL (trademark) BP-3P [R1: extended ethyl, R2: propyl, ml =m2=0, nl=n2 = 1.5], NEWPOL (trademark) BP-5PCR1: extended ethyl group, R2: propyl group, ml=m2=0, η1=η2=2·5], NEWPOL (trademark WPEJOTCR1: Ethyl, R2 = propyl, ml = m2 = l, nl = n2 = 0], NEWPOL (trademark) BPE-60 [R1: ethyl, R2: propyl, ml = m2 = 3, nl =n2=0], NEWPOL (trademark PPE-lOOfR1: extended ethyl, R2: extended propyl, ml=m2 = 5, nl=n2=0), NEWPOL (trademark ^PE-l&OtR1: extended ethyl, R2: propyl, ml=m2=9, nl=n2 = 0] (above is Sanyo Chemical (share) system), UNIOL (trademark PBdOOtR1: extended ethyl, R2: propyl, ml=m2=0, Nl=n2=l .5], UNIOL (trademark) DAB-800 [R1: extended ethyl, R2: extended propyl, ml=m2=6, nl=n2=4.5, -(R^-O)- And -(R2-O)- is random], UNIOL (trademark ^AdSOFtR1: extended ethyl, R2: extension 137650.doc -27- 200947119 propyl, ml=m2=ll, nl=n2=0], UNIOL ( Trademark) DA-400 [R1: Ethyl, R2: propyl, ml==m2=2, nl=n2=0], UNIOL (trademark) DA-7001R1: Ethyl, R2: propyl, Ml=m2 = 5, nl=n2 = 0] (above is Japanese fat (stock) system), BA-PAUfR1: extended ethyl, R2: extended propyl, ml=m2=0, nl=n2=2] GLYCOL BA-PSfR1: Elongyl, R2: propyl, ml=m2 = 0, nl = n2=4] GLYCOL (above is 曰 emulsifier (share)). The content of the plasticizer in 100% by mass of the photosensitive resin composition is preferably 1% by mass or more and 40% by mass or less. In view of the development speed and the resolution, it is preferably 1% by mass or more, and is preferably 40% by mass or less from the viewpoint of resin adhesion and adhesion. More preferably, it is 5 mass% or more and 30% by weight or less. The weight average molecular weight of the plasticizer is preferably from 100 to 5,000. It is 100 or more from the viewpoint of sublimation, and is 5,000 or less from the viewpoint of developability. More preferably, it is 100 to 3,000. The photosensitive resin composition may also contain the components described below. First, from the viewpoint of developability, it is preferred to contain an alkali-soluble polymer containing a carboxyl group. The amount of the carboxyl group of the alkali-soluble polymer is preferably from 100 to 600, more preferably from 250 to 450, in terms of acid equivalent. The acid equivalent means the mass of the alkali-soluble polymer having one equivalent of a carboxyl group. The weight average molecular weight of the alkali-soluble polymer having a carboxyl group is preferably from 5,000 to 50,000,000. The weight average molecular weight is preferably 500,000 or less from the viewpoint of resolution, and is preferably 5, from the viewpoint of the peelability of the support layer after lamination or after exposure, 137650.doc -28 - 200947119. 〇 Above. The weight average molecular weight is further preferably from 5,0 Å to 200,000, more preferably from 5 〇〇〇 to 1 〇〇. Further, the degree of dispersion (also referred to as molecular weight distribution) is obtained as a value obtained by dividing the weight average molecular weight by the number average molecular weight. If the dispersion degree is about 6 or so, the dispersion degree is preferably 1 to 4.

The acid equivalent was measured by a potentiometric titration method using a flat biogas titration device (COM-555) manufactured by Hiranuma Industries Co., Ltd., and mGl/L. The molecular weight system is a gel permeation chromatograph (GPC) manufactured by Japan Seiko Co., Ltd. (Pump · Gulliver ' ρυ·158〇 type, pipe column: Shodex (registered trademark) manufactured by Showa Denko (share) (KF_8〇7, KF 8〇6m, kf_8〇6m, 802.5) 4 series of 'moving bed solvents: tetrahydroanthracene, using polystyrene standard sample (Showa Electric (share) Sh〇dex STANDARD sm_i〇5) calibration = curve) It is obtained as a form of a weight average molecular weight (in terms of polystyrene). © The testable polymer containing (4) is obtained by copolymerizing one or more of the following two types of monomers. A carboxylic acid or an acid anhydride containing a polymerizable unsaturated group in the first-system molecule. For example, (meth)propionic acid 'fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half vinegar, etc. are mentioned. In the present invention, (meth)propionic acid means propyl benzoate and/or mercapto propylene: the two monomers are non-acidic riders containing _ a polymerizable unsaturated group. It is selected so as to maintain the developability of the photosensitive resin layer, the etching resistance of 137650.doc •29·200947119, the resistance in the plating step, and the flexibility of the cured film. For the compound 'for example, (alkyl) acrylate, alkyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl acrylate (meth) acrylate, (mercapto) acrylic acid 2 _hydroxyethyl ester, 2-hydroxypropyl (meth) acrylate, (meth) acrylonitrile, (mercapto) acrylate, methoxybenzyl (meth) acrylate, ruthenium (meth) acrylate , (meth) acrylic acid decyl alcohol, (meth)acrylic acid tetrahydroanthracene vinegar, (mercapto)acrylic acid phenoxyethyl ester, (meth)acrylic acid phenyl ester, (mercapto)acrylic acid toluene ester, (a (aryl) aryl acrylate, such as naphthyl acrylate, containing phenyl A vinyl compound (for example, styrene) or the like is preferred from the viewpoint of compatibility with an alkali-soluble polymer containing a phenolic group, and is preferably a (meth)acrylic acid group. The soluble polymer is preferably synthesized by the following method: the formation of two knots by acetone and methyl ethyl ketone, and the absorption of benzophenone

mix. Further, a part of the mixture may be added dropwise to the reaction liquid to synthesize an alkali-soluble polymer containing a carboxyl group. Further, after the completion of the reaction, a solvent is further added to adjust the alkali-soluble polymer having a carboxyl group to a desired concentration. As the synthesis method, in addition to solution polymerization, blocking, suspension polymerization or emulsion polymerization may also be employed. Reductive polymer containing rebel based on photosensitive resin

The composition is further preferably a content of the photosensitive resin 137650.doc 30. 200947119, which is preferably 5 Å in terms of sensitivity. The following is preferable because the peeling property of the support film after lamination or after the exposure, the appearance of <*,>, the foreign property, and the residual property after development are preferably 5% by mass or more. ❹ ❹ In terms of resolution, the photosensitive resin composition may be further included and contains an ultraviolet absorber. As the ultraviolet absorber, for example, y: bisbenzimidazole, p-butylaminophenethylamine, p-didecylamine stupid: p-monomethylaminodibenzophenone, P, P, _bis(ethylamino)benzophenone, P,P'_bis(dimethylamino)benzophenone [micilene], bis(diethylamino)benzophenone, p, p, _ bis (dibutylamino) dimero _ and so on. It is also possible to control the photoresist industry by scraping the surface by adding an ultraviolet absorber. For example, when the cross-sectional shape of the photoresist pattern is dome-shaped, it is possible to add ρ, ρ·-bis(diethylamino) bismuth, etc., and the like, and the shape is close to a rectangular shape. Hereinafter, a method for producing the photosensitive resin laminate of the present invention will be described. In the first place, an alkali-soluble resin containing a phenolic hydroxyl group, a photoacid generator, a compound containing a group which crosslinks by an action of an acid, a plasticizer, and other components suitable for the desired properties are blended. A pre-sensitive resin composition was prepared. The suitable solvent to be used may, for example, be an alcohol such as methyl ethyl ketone (oxime), or an alcohol such as ethanol, isopropyl alcohol or the like. The photosensitive resin composition is applied onto a support layer by a knife coater, a bar coater, a roll coater or the like to form a photosensitive resin layer. In the case of producing a long photosensitive resin layer, a slit extrusion coater or a gravure coater can be used. In the case of the slit press coater of 137650.doc -31 - 200947119, it is preferred to adjust the viscosity so as to achieve a viscosity of 500 to 4,000 mPa · sec. In the case of using a gravure coater, it is preferred to let the viscosity reach a temperature of 1 to 200 mPa · sec. Next, the protective layer is laminated, whereby a photosensitive resin laminate can be produced. Further, another resin layer may be laminated on the support layer to apply a photosensitive resin composition. Exposure after the release of the support layer after the peeling of the support layer for the purpose of the step, or in order to eliminate the influence of the foreign matter on the support layer or the lubricant in the support layer, after exposure to the support layer, The other resin layer is provided for the purpose of isolating the alkali component in the air. X, in the helmet method, the photosensitive resin layer is thick enough, and (4) another resin layer is provided for the purpose of causing the photosensitive resin layer to follow the unevenness of the substrate. The thickness ' of the photosensitive resin layer' can be appropriately adjusted depending on the use. The resolution of the electrode is used when the thickness of the photosensitive resin layer is used for the formation of k. The preferred 疋1〇 μιη is 疋0.5 μηι or more in terms of resistance to buttoning. The thickness of the photosensitive resin layer is more preferably 1 _ up and 8 _ or less. More preferably, it is 1 μηι or more and 5 μηι or less. For example, an electrode for a TFT can be fabricated in the following manner. When the photosensitive resin layer is brought into contact with the substrate in such a manner that the photosensitive layer is laminated on the substrate with the protective layer on the can layer, the surface is peeled off and the heat roller is attached. The photosensitive layer of the photosensitive resin laminate is placed on the substrate, and the substrate is laminated on 11 wafers or glass. 137650.doc -32· 200947119 Molybdenum, aluminum, bismuth, chromium, tungsten, ruthenium, etc. Made of metal film. (2) Step of exposing the photosensitive resin layer The desired electrode pattern was projected onto the photosensitive resin laminate by a chrome glass mask, and the photosensitive resin laminate was exposed. As the active light source, one high-pressure mercury lamp, ultra-high pressure mercury lamp, ultraviolet fluorescent lamp, carbon arc lamp, and gas lamp can be cited. The exposure method includes a close-up method of projecting the reticle in a state of being tens of μπι from the substrate, and a mirror projection alignment illuminator using a concave mirror (Mirror Projection AHgne type, or smaller than The magnification reduction ratio of the equal magnification is performed by a stepwise division of the projection exposure by the lens, or the active light may be drawn on the photosensitive resin laminate in advance according to the stylized electrode pattern, and the photosensitive resin laminate may be exposed. As for the active light source, there are: semiconductor laser, semiconductor solid laser, ultra-high pressure mercury lamp, etc. As for the scanning method of the light, there are a polygon mirror (rigital mirror) and a digital mirror device (Digital Mirror Device). The support layer may be peeled off before the exposure step or peeled off after exposure. From the viewpoint of resolution, it is preferred to expose the photosensitive resin layer after peeling off the support layer. From the viewpoint of the above, it is preferred to peel off the support layer after exposure. (3) The step of heating the exposed photosensitive resin layer is performed by using an oven or The substrate after the exposure is heated by a hot plate, etc. The temperature or time can be adjusted according to the sensitivity. From the viewpoint of sufficiently curing the exposed photosensitive resin layer, the heating temperature is preferably 9 〇〇c or more. From the viewpoint of the resolution of the resolution and the heating step, the heating temperature is preferably 130 C or less. From the viewpoint of productivity, the heating time is preferably 137650.doc -33 - 200947119 minutes or less, and the resolution is From the viewpoint of stability, the heating time is preferably 15 seconds or more. (4) The step of developing the heated photosensitive resin layer is performed by dissolving or dispersing the photosensitive resin layer by an alkaline developing solution. In part, a hardened photoresist pattern is formed on the substrate. As the alkaline developer 1 in consideration of the influence on the semiconductor, it is preferred to use an organic aqueous solution such as tetramethyl hydroxide. (5) Wet The step of engraving or dry button engraving is in the wet type (4), spraying (four) engraving from above the formed photoresist pattern, and injecting (four) engraving on the substrate not covered by the photoresist pattern. Convergence, etc. When mixed with a mixture of acid, acid, phosphoric acid, acetic acid, etc., when the substrate is amorphous 7, polycrystalline ♦, nitrogen cut, etc., dry type engraving, active ion surname (reaetive i〇n) can be used. (4) The step of stripping is carried out. (6) The step of stripping is performed, and the photoresist pattern is removed from the substrate by an alkaline stripping solution. Organic amines such as monoethanolamine and triethanolamine may be used, and ethylene may be used. A stripping liquid of alcohol, water, etc. [Examples] In the following examples, preferred embodiments of the present invention are specifically described [Examples 1 to 7, Example 1 and Comparative Examples 1, 2] < 1. Preparation of Photosensitive Resin Composition> The compound shown in Table 1 was mixed to prepare a photosensitive resin composition 137650.doc-34-200947119 The values in Table 1 are solid content. The symbols in the table are as follows. A-1: 曱 龄 搭 搭 树脂 树脂 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' EP EP EP EP EP EP EP EP EP EP EP EP EP )) A-2 : a copolymer obtained by copolymerizing 80% by mass of benzyl methacrylate with 2% by mass of mercaptopropionate, and having a weight average molecular weight of 25, 〇〇〇

A-3: Poly(p-hydroxy) stupid ethylene, weight average molecular weight 2 〇, 〇〇〇, (Chemiway (share) 'MarukaLyncur MH-2P (SSg)) B-1. hexamethoxymethylated melamine resin, dried The reduction was i% by mass and the monomer was 96 mass. /. Above, (Sanwa Chemical (share) system, MW-390 (trade name)) Cl. 2,4-dimethylmethyl (piperonyl)·6_three plowing (made by Japanese company, Triazine PP ( Trade name)) C-2 : p,p|-bis(diethylamino)benzophenone D 1 · Compound having 3 moles of propylene glycol at both ends of bisphenol a, (Asahi Chemical Industry Co., Ltd. ), Polyether BPX_33 (trade name)) D-2: Polypropylene glycol (molecular weight: 2 Å) <2. Production of photosensitive resin laminate] The above-mentioned photosensitive resin composition was dissolved in a solvent (methyl group B) In the ketone), it was uniformly applied to the film shown in the center by a knife coater, and dried in a 95C drier to form a resin layer having a thickness of _. The film system shown in Table 1 was produced in the following manner. "A film having a release layer (5)) is a commercially available product (137650.doc -35-200947119 PET25X manufactured by Lindeke Co., Ltd.). The film (b-1) having a solvent-soluble resin layer is as follows. A ternary copolymer having a weight average molecular weight of 70,000% by mass of 75% by mass of decyl acrylate, 65% by mass of jasper, and 25% by mass of acrylic acid and 10% by mass of butyl acrylate. The acid equivalent is 344) and the mass of I5 is /, ^, 5. 5 mass% of ^, ", 15 quality ❶ /. The W mixture was mixed and dissolved in the f-ethyl group to prepare a composition solution each. The composition solution was uniformly applied to a polyester film having a thickness of 16 μm by a knife coater (manufactured by Toray Industries, Ltd., 16QS48 (on a level, dried in a dryer of 95 for 2 minutes, and a thickness of (10) was produced).碱μπι alkali-soluble resin layer. The film (ci) having a water-soluble resin layer is produced in the following manner: 9 〇 mass% of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., 乂8_2〇5) 1〇质量%1 Polyethylene glycol monomethyl ether (Uniox M-550, manufactured by Sakamoto Oil Co., Ltd.) having an average molecular weight of 550 was mixed, and the mixture was dissolved in hot water to prepare a uniform water-soluble resin solution. The water-soluble resin solution was uniformly applied to a polyester film (manufactured by Toray Industries, Ltd., 16QS48 (Level 3)) having a thickness of 16 μm 2 and dried in a desiccator of 95 C for 2 minutes to prepare a thickness of 2 The alkali-soluble resin layer of μπι. The film (d) in Table 1 is a commercially available 19 μΓη 2 polyester film (G2 manufactured by Teijin DuPont Co., Ltd.) as a support layer and coated on the support layer. Photosensitive tree layer. <3. Evaluation substrate Production > Substrate: As the substrate 'used based on a 5-inch silicon wafer laminate type Ν 300 Α thick 137650.doc 36- 200947119

A substrate made of a Mo film. Lamination: The photosensitive resin laminate having the peeled protective layer was laminated on the substrate by a bonding machine (MRR210 (trade name) manufactured by MCK). The conditions were set to laminating speed: 1.0 m/min, laminating roll temperature: I20t, drum pressure: 0 40 MPa 〇 Exposure: peeling the support layer, using a chrome glass mask, using an exposure machine with an ultrahigh pressure mercury lamp (projection Exposure apparatus UX2003SM-MS04: manufactured by Ushio Electric Co., Ltd.) Projection exposure of the evaluation substrate at an exposure amount of 30 mJ/cm 2 . In any of the above Examples 1 to 7 and the following Examples 8 and 9, the support layer was peeled off without any problem. The exposed portion here becomes a hardened photoresist. Heating after exposure: After exposure, the substrate was heated with a hot plate at 100 ° C for 30 seconds. Development: In the case of having a support layer, the support layer is removed from the obtained evaluation substrate, and 2 to 38% by mass of a tetramethylammonium hydroxide aqueous solution is used as an alkaline developer at a temperature of 30 ° C and a spray pressure of 0.25 MPa. The ejection development was carried out, whereby the unexposed portion of the photosensitive resin layer was removed, washed with tap water and dried to obtain a photoresist pattern. The developing device is a spin-off ping machine manufactured by Takizawa sangyo Co., Ltd. 〇 etching: 137650.doc -37- 200947119 Aluminium sulphate mixed with Wako Pure Chemical, at 4〇t, 3〇 seconds Under the condition, the substrate on which the photoresist pattern is formed is etched by the squeezing method. Peeling: The etched substrate was peeled off by a dipping method using 111 丨 (:1 with 11 Ep_1 〇 stripping solution at 65 C, 20 sec strips) using a Yokohama Oils and Fats Industry Co., Ltd. <4. Evaluation > The evaluation substrate was evaluated by the following method, and the results are summarized in the following Table 1. Evaluation of adhesion of the resin to the protective film · Preparation of a photosensitive resin laminated body 'Polyethylene film as a protective layer (D (10) 叩GF_858 (trade name D) was hand-laminated (haWate) and stored at room temperature for 3 weeks. The adhesion of the resin on the surface of the smear layer was evaluated in the _ protective layer, and classified as follows. - No adhesion of resin was observed Δ: adhesion of resin was observed on the surface of a part of the protective layer. X: Evaluation of minimum development time of resin adhering to the entire surface of the protective layer: Development of the substrate from the substrate laminated with the photosensitive resin laminate. The development is started until the surface of the substrate is exposed to be equalized. The display-time is as follows: • The minimum development time is within 60 seconds Δ: The minimum development time exceeds 60 seconds, within 3 minutes, 137650.doc -38 - 2009471 19 x : The minimum development time is 3 minutes or more resolution evaluation: a glass reticle with a line width and a line spacing of 1:1 is exposed and heated and developed. The minimum resist pattern will be resolved with the image. The corresponding mask width is evaluated as the value of the resolution. 〃 〇: The resolution is 4 jum or less.

Λ : Resolution is more than 4 μηη, 8 μϊη or less χ : Resolution is more than 8 μηη. Evaluation of adhesion: chrome glass light having a pattern of independent lines of various widths, and exposure and heating i. The mask width corresponding to the minimum photoresist pattern obtained by peeling off the crucible was evaluated as the value of the adhesion. 〇·Experience is 4 μηη or less △: Adhesion is more than 4 μηη, 8 μηι or less χ : Adhesion is more than 8 μηη Evaluation of etching property: For evaluation of the substrate obtained in the evaluation of the resolution, the leg is left.

Scannmg Ε 1 (10) on Micr〇sc〇pe, scanning electron microscope) to observe whether there is peeling of the photoresist pattern. 〇: peeling of no photoresist pattern X. Evaluation of peeling of the photoresist pattern and peeling of the surface of the substrate: SEM confirmed from the evaluation of the substrate on the evaluation of the etchant _ Μ 137 137650.doc -39- 200947119 Whether there is photoresist residue on the surface of the substrate β 〇: no photoresist residue χ : Evaluation of the surface state of the photoresist photoresist pattern: The substrate evaluated by the SEM evaluation of the resolution is observed. Observe the flatness of the top and side of the photoresist pattern. 〇: The top of the photoresist pattern is uniform △ • A small number of irregularities X are seen on the top and side of the photoresist pattern. The unevenness is seen on the side of the photoresist pattern, and the linearity of the pattern is impaired [Example 8] In addition to the exposure step, 〇rb〇tech is used. A photoresist pattern was produced in the same manner as in Example 1 except that the company Paragon 9000 was drawn at an output of 8 W and an exposure amount of 30 mJ/cm 2 . The resolution and the adhesion are both 6 μπι. No peeling of the photoresist pattern after the engraving. No residue was observed after the photoresist was peeled off. [Example 9] A photosensitive resin laminate was produced and evaluated in the same manner as in Example 1 except that a stretched polypropylene film (Arufun® 200 Α (trade name) manufactured by Oji Paper Co., Ltd.) was used as the protective layer. . [Example 10] D-1: In addition to using D-2: polypropylene glycol (molecular weight: 2000), a compound containing 3 moles of propylene glycol at both ends of the double-prepared oxime (made by Asahi Kasei Co., Ltd., POLYETHER BPX) was used. A photosensitive resin laminate was produced and evaluated in the same manner as in Example 1 except for -33 (trade name). [Examples 11 and 12] 137650.doc • 40-200947119 The cross-sectional shape of the resist pattern was observed by Examples 11 and 12 (hereinafter, see Table 2). In the embodiment, a rectangular resist pattern is obtained by using A_3 alone. In Example 12, a rectangular resist pattern was obtained by adding c_2. [Examples 13 and 14] As the substrate, an a_Si substrate formed by laminating 15 μm thick non-crystalline germanium on a glass by a CVD (Chemical Vapor Deposition) method was used. In the same manner as in Example 11, a photoresist pattern was produced (Example 13). As the substrate, a SiN substrate obtained by laminating 3000 Å thick tantalum nitride on a glass by a cvd method was used, and a photoresist pattern was produced in the same manner as in Example ( (Example 丨 4). Both of them have the same resolution and adhesion as when using the m〇 substrate (see Table 3 below). [Examples 15 and 16] Using the photosensitive resin laminate used in Example 1, it was previously formed on a glass substrate to have a height of 3.5 μm, a width of 3 μm, a length of 5 mm, and a pitch of 30 Å. Straight step. The photosensitive resin laminate used in Example 1 was laminated on the substrate along a linear step to observe the generation of an air gap. Further, the linear pattern was exposed and developed in a straight line step, and the pattern was broken (Example 15). The same experiment (Example 16) was carried out by using the photosensitive resin laminate used in Example 2. In Example 15, the generation of the air gap was seen next to the step, and the broken line was seen in the formed pattern. In the embodiment 16, no air gap is present next to the step difference, and no broken line of the pattern is seen. [Comparative Example 3] 137650.doc • 41. 200947119 The photosensitive resin composition used in Example 1 was applied onto a substrate by a direct spin coating method. The substrate was the same as the substrate used in Example 1. In the case where the photosensitive resin laminate of Example i was used and laminated on a substrate, the time required for lamination was about 10 seconds. On the other hand, the photosensitive resin composition is applied by a spin coating method, and it takes about 5 minutes to dry. The volatilized solvent must be vented during spin coating or drying. Further, the photosensitive resin composition is embossed along the end portion of the substrate, so that unevenness is seen. The unevenness of the radial shape or the unevenness of the portion of the substrate that is adsorbed (smoothed) is also seen in the center portion of the rotation. 137650.doc •42- 200947119 [Id Comparative Example 2 Membrane (a-1) 52 in 〇85.5 Ph 〇XX 〇〇〇〇Comparative Example 1 Membrane (d) tn ο jq 100.5 Unable to peel off support layer 1 Example ίο Membrane ( A-1) ΙΛ Ο J2 100.5 CL, 〇 <1 〇< 〇〇〇|Example 9 Membrane (a-1) ΙΛ in ο 100.5 Oh 〇〇〇〇〇〇〇 Example 7 Membrane (a-1 % V) ΙΛ Ο in 100.5 阁 CLi 〇〇〇〇〇〇〇 Example 6 Film (a-1) ΙΛ \η ο 52 100.5 〇〇〇〇〇〇 < Example 5 丨 film (a-1) Ο un ΙΤ) ο 100.5 Oh 〇 < 〇〇〇〇〇 Example 4 Film (a-1) ΙΛ Ο IT) 100.5 cw < 〇〇〇〇〇〇 Example 3 丨 film (4) | ΙΛ ιη 9 !2 100.5 Pn o 〇〇〇〇〇〇|Example 2 Film (b-1) 1/1 ο 100.5 〇〇〇〇〇〇〇 Example 1 Film (a-1) ifi ο 100.5 〇〇〇〇〇〇〇 Film used in coating A-1 A-2 A-3 B-1 C-1 Dl D-2 |Total | Protective layer resin adhesion ¥ [μπι] | [μη>] Etching stripping photoresist pattern Film surface state photosensitive resin composition minimum development time resolution | Adhesion | -43 - 137650.doc 200947119 [Table 2] Example 1 Example 11 Example 12 Film used in coating (a-1) Film (a-1) Film (a-1) Photosensitive resin composition A-1 50 50 A-2 20 20 A-3 70 B-1 15 15 15 C-1 0.5 0.5 0.5 C-2 0.5 D-1 15 15 15 Total 100.5 100.5 100.5 Protective layer PE PE PE Resin adhesion 〇〇〇 Minimum development time [sec] 〇Ο 〇 resolution [μιη] 〇〇〇 adhesion [μπ»ΐ Ο 〇〇 etch 〇 〇 detachability 〇〇〇 photoresist pattern surface state 〇〇〇 photoresist pattern shape dome-shaped rectangular rectangle [Table 3] Example 11 Example 13 Example 14 Substrate Mo a-Si SiN Film used in coating (a- 1) Film (a-1) Film (a-1) Photosensitive resin composition A-1 A-2 A-3 70 70 70 B-1 15 15 15 C-1 0.5 0.5 0.5 C-2 D-1 15 15 15 Total 100.5 100.5 100.5 Protective layer PE PE PE Resin adhesion 〇〇〇 Minimum development time [sec] 〇〇〇 Resolution [μιη] 〇〇〇 Adhesiveness [μ»η] 〇〇〇137650.doc -44- 200947119 [Industrial Applicability] The present invention provides a variety of (four) for polycrystalline stone, amorphous stone, steel tungsten, group, and the like. Excellent (4) Resolution and good adhesion developability, light sensitivity, molybdenum, chromium, and a benign resin laminate. The photosensitive resin laminate can be suitably used for the production of TFT.

137650.doc 45·

Claims (1)

200947119, VII. Patent application scope: 1. A photosensitive resin laminate, characterized in that it is at least sequentially laminated with a support layer; at least one layer selected from the layers shown in the following (a) to (c); (a) a mold release layer, (b) a test resin layer, (c) a water-soluble resin layer, and a photosensitive resin layer containing a photosensitive resin composition, the photosensitive resin composition comprising 20 to 9碱% by mass of an alkali-soluble resin containing a phenolic hydroxyl group, 0.01 to 5% by mass of a photoacid generator, a compound having a base which is crosslinked by an action of an acid, and a mass% of 丨~仂Plasticizer. 2. The photosensitive resin laminate according to claim 1, wherein the photosensitive resin composition further contains an alkali-soluble polymer containing a carboxyl group. 3. The photosensitive resin laminate according to claim 1 or 2, wherein the plasticizer is a compound represented by the following formula (I): [Chemical Formula 1] ch3 呤-Riu°-R2t°O4^〇^~ (R2-Miao 1 七ch3 {wherein 'R1 and R2 are exoethyl or exopropyl., and 111 and 112 are different from each other', ml, ni, m2 and n2 are respectively 0 or more, and ml+nl+m2+ N2 is 2~30; then the repeating structure of -(O-R1)- and -(〇-R2)_ can be random or block, and _(〇_R2)_ is repeated 137650.doc 200947119 structure Any of them may be on the bisphenyl side. 4. 5. 6. A method for producing a photoresist pattern, comprising the steps of: forming a photosensitive resin layer as claimed in claim 1 or 2 to make the above-mentioned photosensitivity The resin layer is pressed against the substrate in contact with the substrate; the photosensitive resin layer is exposed; the exposed photosensitive resin layer is heated; and the heated photosensitive resin layer is developed. A method for producing a photoresist pattern in which the step of exposing the photosensitive resin layer is a method of drawing active light. A manufacturing method comprising the steps of: wet etching an underlying portion of a substrate not covered by a photoresist pattern produced by the method of claim 4; A method comprising: a step of dry-touching a portion of a substrate that is not covered by a photoresist pattern manufactured by the method of claim 4; 8. A method for fabricating a photoresist pattern according to claim 4 or 5, wherein The surface of the substrate in contact with the photosensitive resin layer is molybdenum. The electrode pattern manufacturing method according to claim 6, wherein the surface of the substrate in contact with the photosensitive resin layer is a key. Or a method for producing a photoresist pattern of 5, wherein the surface of the substrate in contact with the salty resin layer is amorphous. 11. The method for producing a photoresist pattern according to claim 4 or 5, wherein The surface of the above-mentioned substrate which is in contact with the photosensitive resin layer is tantalum nitride. 137650.doc 200947119 IV. Designation of representative drawings: (1) The representative representative of the case is: (none) (2) A brief description of the symbol of the representative figure Fifth, if the case of formula, please disclosed invention features most indicative of the formula: (None) 137650.doc