WO2008035672A1 - Procédé de fabrication d'un film durci transparent en utilisant une couche de résine photosensible positive pendant une demie exposition - Google Patents

Procédé de fabrication d'un film durci transparent en utilisant une couche de résine photosensible positive pendant une demie exposition Download PDF

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Publication number
WO2008035672A1
WO2008035672A1 PCT/JP2007/068083 JP2007068083W WO2008035672A1 WO 2008035672 A1 WO2008035672 A1 WO 2008035672A1 JP 2007068083 W JP2007068083 W JP 2007068083W WO 2008035672 A1 WO2008035672 A1 WO 2008035672A1
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WIPO (PCT)
Prior art keywords
component
photosensitive resin
sensitivity
positive photosensitive
cured film
Prior art date
Application number
PCT/JP2007/068083
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English (en)
Japanese (ja)
Inventor
Tadashi Hatanaka
Original Assignee
Nissan Chemical Industries, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nissan Chemical Industries, Ltd. filed Critical Nissan Chemical Industries, Ltd.
Priority to KR1020097006060A priority Critical patent/KR101334753B1/ko
Priority to JP2008535354A priority patent/JP5083566B2/ja
Priority to CN2007800346563A priority patent/CN101517492B/zh
Publication of WO2008035672A1 publication Critical patent/WO2008035672A1/fr

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
    • G03F7/0043—Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor

Definitions

  • the present invention relates to a method for producing a transparent cured film obtained using a positive photosensitive resin layer.
  • the present invention relates to a method for producing a transparent cured film by exposing two positive photosensitive resin layers having different exposure sensitivities formed on a substrate and finally passing through a post-beta step.
  • the photosensitive resin layer having the above-described structure can be applied to a method for producing a reflection layer, a flat transmission layer, and a contact hole with any shape with high accuracy by half exposure, and in particular, semi-transmission.
  • the present invention relates to application to manufacturing of a liquid crystal display element.
  • a thin film transistor (TFT) type liquid crystal display element has a reflection type, a semi-transmission type, a transmission type structure, and the like, and is appropriately selected depending on a device to be used.
  • the transflective type which allows high-definition display both indoors and outdoors, day and night, is often used.
  • a flattening film is used for the purpose of flattening the TFT and widening the aperture ratio over such a transflective liquid crystal display element.
  • irregular irregularities are produced on the surface in order to provide the light scattering property of the reflection part and increase the reflection efficiency.
  • a metal such as aluminum or molybdenum is formed on the irregularities as a reflector and a pixel electrode.
  • a transparent electrode such as ITO is used as the pixel electrode in the transmissive part.
  • a contact hole is formed in the planarization film to make these pixel electrodes conductive with the common electrode.
  • the photosensitive material used here has excellent process resistance such as heat resistance and solvent resistance, good adhesion to the substrate, and high accuracy under various process conditions according to the purpose of use.
  • Various characteristics such as having a wide process margin capable of forming a pattern, high sensitivity and high transparency, and less film unevenness after development are required.
  • a photosensitive resin composition containing a naphthoquinone diazide compound has been widely used as the photosensitive material.
  • the conventional photosensitive resin material containing the naphthoquinonediazide compound described above has not been sufficiently satisfactory in terms of sensitivity.
  • This method has limitations, and dissolution of unexposed areas also occurs, resulting in a decrease in the remaining film ratio. This has the disadvantage that it causes film unevenness for large display substrates.
  • a radiation-sensitive resin composition containing an alkali-soluble resin and at least one of a specific polyhydroxy compound and a derivative thereof has been proposed! (See, for example, Patent Document 1), but naphthoquinone diazide Conventional photosensitive resin materials containing compounds have a lower exposure margin in the half-exposure area as the sensitivity increases in exposure through a half-tone mask. As a result, it was impossible to achieve both high sensitivity and improved exposure margin.
  • a protective group bond portion or an ether bond thermal bridge portion can be easily formed at a high temperature used for film curing or in the presence of a resist stripping solution. It was almost impossible to use as a permanent film that decomposed and had extremely low heat resistance and chemical resistance.
  • thermosetting in order to enable thermosetting, even if an epoxy-caminoplast cross-linking system is introduced into a chemically amplified resist, it is generated by a photoacid generator (hereinafter also referred to as PAG) in the resist by exposure. Due to the influence of the acid, the cross-linking of the exposed part proceeds and new problems such as disappearance of the dissolution contrast with the unexposed part occur. It was difficult.
  • PAG photoacid generator
  • Patent Document 1 Japanese Patent Laid-Open No. 4 211255
  • Patent Document 2 US Patent No. 5075199
  • an object of the present invention is to provide a method for producing a transparent cured film having a wide exposure margin while maintaining high sensitivity.
  • it can be applied to the production of TFT planarization films, It is an object of the present invention to provide a method for producing a transparent cured film for simultaneously forming contact holes and reflective irregularities by half exposure.
  • two positive photosensitive resin layers having different exposure sensitivities are formed on a base material, and a low sensitivity positive photosensitive resin layer is disposed between the base material and a high sensitivity positive photosensitive resin layer.
  • a method for producing a transparent cured film comprising a step of developing a photosensitive resin layer and a step of post-betaing the two positive photosensitive resin layers, wherein the low-sensitivity positive photosensitive resin layer comprises the following (A method for producing a transparent cured film, which is a positive photosensitive resin layer containing component A), component (B), component (C), and component (D).
  • (A) component alkali-soluble resin
  • Component (B) Compound having two or more butyl ether groups in one molecule
  • Component (C) Compound that crosslinks with component (A) by post-beta.
  • the method for producing a transparent cured film according to the first aspect wherein the exposure is half exposure.
  • the transparent cured film according to the first aspect or the second aspect in which the post-exposure heating is performed at a temperature of 80 ° C to 140 ° C and the post beta is performed at a temperature of 150 ° C to 270 ° C. Manufacturing method.
  • the high-sensitivity positive photosensitive resin layer is a positive photosensitive resin layer containing the following component (A), component (B), component (C) and component (D): The manufacturing method of the transparent cured film as described in any one of a 1st viewpoint thru
  • (A) component alkali-soluble resin
  • Component (B) Compound having two or more butyl ether groups in one molecule
  • Component (C) Compound that crosslinks with component (A) by post-beta.
  • the method for producing a transparent cured film according to any one of the first aspect to the fifth aspect which is a base material on which a base material STFT element is formed.
  • a TFT array planarizing film comprising a transparent cured film obtained by the manufacturing method according to any one of the first aspect to the fifth aspect.
  • a display element having a transparent cured film obtained by the production method according to any one of the first aspect to the fifth aspect.
  • a liquid crystal display element having a transparent cured film obtained by the manufacturing method according to one of the first aspect and the fifth aspect.
  • the transparent cured film obtained by the present invention has an effect of high sensitivity at the time of half exposure and a wide exposure margin.
  • the unevenness of the TFT flattening film and the contact hole are simultaneously highly sensitive and highly sensitive. It can be applied to the production of a semi-transmission type liquid crystal display device that is accurately formed.
  • the present invention provides two positive photosensitive resin layers having different exposure sensitivities on a base material, and the low-sensitivity positive photosensitive resin layer is the base material and the high-sensitivity positive photosensitive resin layer. It is characterized in that it includes a step of exposing the positive photosensitive resin layer consisting of the two layers, post exposure bake (PEB), developing, and post-beta. It is the manufacturing method of transparency cured film.
  • PEB post exposure bake
  • a low-sensitivity positive photosensitive resin layer is formed on a substrate, and a high-sensitivity positive photosensitive resin layer is further laminated on the low-sensitivity layer, so that the exposure sensitivity differs on the substrate.
  • the step of laminating two layers of the positive photosensitive resin layer, the step of exposing the two laminated positive photosensitive resin layers, and the step of heating the two positive photosensitive resin layers after exposure A process for developing the two positive photosensitive resin layers, and a method for producing a transparent cured film comprising the step of post-betaing the two positive photosensitive resin layers.
  • Type photosensitive resin layer A method for producing a transparent cured film, which is a positive photosensitive resin layer containing the components (A), (B), (C) and (D).
  • (A) component alkali-soluble resin
  • Component (B) Compound having two or more butyl ether groups in one molecule
  • Component (C) Compound that crosslinks with component (A) by post-beta.
  • two layers of positive photosensitive resin layers having different exposure sensitivities are laminated on a substrate, so that when exposed through a halftone mask, a high sensitivity is obtained.
  • Different pattern shapes can be formed between a positive photosensitive resin layer (hereinafter referred to as a high sensitivity layer) and a low sensitivity positive photosensitive resin layer (hereinafter referred to as a low sensitivity layer).
  • a high sensitivity layer a positive photosensitive resin layer
  • a low sensitivity positive photosensitive resin layer hereinafter referred to as a low sensitivity layer.
  • different image shapes can be formed in a single exposure by using a halftone mask in the high-sensitivity layer and the low-sensitivity layer.
  • the low-sensitivity layer is laminated so as to be located between the base material and the high-sensitivity layer, the high-sensitivity layer and the low sensitivity remain as unexposed portions during development, and half exposure is performed.
  • the high-sensitivity layer is removed from the part, and the low-sensitivity layer remains.
  • the positive photosensitive resin layer (high-sensitivity layer and low-sensitivity layer) is completely removed, and the base material is exposed.
  • the half-exposure portion referred to here is a portion that can be developed with a smaller exposure amount than the complete exposure portion and can form a desired image.
  • the low-sensitivity layer when the low-sensitivity layer is formed, it is contained in the resin composition by applying a solution of a positive photosensitive resin composition that forms the layer and then pre-drying (heat treatment).
  • the components are crosslinked with each other, whereby a film hardly soluble in an organic solvent is formed on the substrate. Therefore, when a high-sensitivity layer is subsequently formed on the low-sensitivity layer, the low-sensitivity layer and the high-sensitivity layer do not intermix even if a solution of the photosensitive resin composition that forms the layer is applied. There is no waking.
  • the high-sensitivity layer and the low-sensitivity layer each cause a reduction in film thickness at the time of development when irradiation is performed with an amount of light that is smaller than the exposure amount necessary for the development to start, and the development starts. It is desired that development is performed promptly (high accuracy and high sensitivity) after irradiation with a necessary amount of light.
  • the half-exposure margin In order to obtain a highly accurate image, the half exposure margin is preferably 10 mJ or more.
  • the low sensitivity layer has a certain degree of sensitivity.
  • the sensitivity of the low-sensitivity layer will be reduced, leading to a decrease in throughput. by.
  • the low-sensitivity layer is preferably, for example, a highly sensitive chemical amplification type photosensitive layer.
  • the high-sensitivity layer is required to be a photosensitive layer with higher sensitivity than the high-sensitivity low-sensitivity layer, and a higher-sensitivity layer is preferred! / A chemical amplification type photosensitive layer is preferred! /.
  • the positive photosensitive resin layer used in the present invention is as described above, and a transparent cured film can be obtained by post-beta formation after forming a desired image.
  • the low-sensitivity layer used in the present invention comprises (A) an alkali-soluble resin, (B) a compound having two or more butyl ether groups in one molecule, (C) component (A) and component (A) by post-beta. It consists of a positive photosensitive resin composition containing a compound that undergoes a crosslinking reaction and a photoacid generator as component (D).
  • the low-sensitivity layer can be formed by dissolving the positive photosensitive resin composition described above in (E) solvent to form a solution, applying the solution to a substrate, and drying.
  • the component (A) is an alkali-soluble resin, and as a preferred one, a functional group capable of undergoing a thermal crosslinking reaction with the compound having a butyl ether group of the component (B) in the resin structure, and , Having a functional group for film curing that can undergo a thermosetting reaction between the component (A) and a compound that undergoes a crosslinking reaction by post-beta of component (C), and having a number average molecular weight of 2,000 to 50 , 000, an alkali-soluble resin.
  • the component (A) is an alkali-soluble resin
  • a thermal bridge reaction is performed with the compound having a butyl ether group of the component (B) by a prebeta during the resin structure.
  • a functional group for film curing that can crosslink with the component (C) by post-beta to form a thermosetting reaction, and the number average molecular weight is 2,000 to 50,000
  • An alkali-soluble resin that is:
  • the functional group for the thermal crosslinking reaction reacts with the butyl ether group in the (B) component compound at an elevated temperature (prebeta temperature) to form the (B) component compound.
  • a typical functional group thereof is at least one selected from the group consisting of a carboxyl group and a phenolic hydroxyl group.
  • the functional group for film curing is present in the thermally crosslinked product of the above components (A) and (B) (in the exposed part, in the decrosslinked product in which the thermally crosslinked product is further dissociated). ), A group that undergoes a crosslinking reaction with the compound of component (C) under a higher temperature (post-beta temperature) and can cure the film.
  • the functional group for film curing that the (A) component has is between the compound of the (C) component.
  • a crosslinking reaction occurs through the isocyanate group from which the broth moiety has been dissociated, and the film is cured.
  • a typical functional group as a functional group for film curing is at least one selected from the group of hydroxy groups other than phenolic hydroxy groups and amino groups having active hydrogen.
  • the amino group having active hydrogen means a primary or secondary amino group capable of releasing a proton by reaction. Therefore, the amide group does not correspond to an amino group having active hydrogen because it does not have active hydrogen.
  • the alkali-soluble resin of component (A) may be an alkali-soluble resin having such a structure, and is particularly limited depending on the type of main chain skeleton and side chain of the polymer constituting the resin. Not determined.
  • the resin of component (A) has a number average molecular weight in the range of 2,000 to 50,000. If the number average molecular weight exceeds 50,000, the development residue is likely to be generated, and the sensitivity is greatly reduced. On the other hand, if the number average molecular weight is less than 2,000, and the development is too small, a considerable amount of film loss may occur in the exposed area, resulting in insufficient curing.
  • alkali-soluble resin of component (A) examples include acrylic resins, polyhydroxystyrene resins, polyimide precursors, and polyimides.
  • an alkali-soluble resin composed of a copolymer obtained by polymerizing a plurality of types of monomers (hereinafter referred to as a specific copolymer) is used as the component (A). You can also.
  • the alkali-soluble resin as the component (A) may be a blend of a plurality of types of specific copolymers.
  • the specific copolymer includes an alkali-soluble monomer, that is, a group of monomers having at least one of a carboxyl group and a phenolic hydroxy group, and at least one monomer selected as appropriate.
  • a monomer having a functional group for film curing that is, at least one monomer appropriately selected from the group of monomers having at least one of a hydroxy group other than a phenolic hydroxy group and an amino group having an active hydrogen, is essential.
  • the number average molecular weight and the weight average molecular weight of the above specific copolymer are measured using, for example, a GPC apparatus (Shodex (registered trademark) columns KF803L and KF804L) manufactured by JASCO Corporation, and the elution solvent tetrahydrofuran is supplied at a flow rate of lml / min. It can be measured under the condition that it is eluted by flowing through the column (column temperature 40 ° C).
  • the above-mentioned "monomer having at least one of carboxyl group and phenolic hydroxy group” includes a monomer having a carboxyl group, a monomer having a phenolic hydroxy group, and a carboxyl group and a phenolic hydroxy group. Have both Monomer. These monomers are not limited to those having one carboxyl group or phenolic hydroxy group, and may have a plurality thereof.
  • the above-mentioned "monomer having at least one of a hydroxy group other than a phenolic hydroxy group and an amino group having an active hydrogen” includes a monomer having a hydroxy group other than a phenolic hydroxy group, and active hydrogen.
  • These monomers are not limited to those having one hydroxyl group other than a phenolic hydroxy group or one amino group having an active hydrogen, and may have a plurality.
  • Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, N -(Carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide and the like.
  • Examples of the monomer having a phenolic hydroxy group include hydroxystyrene, N (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) maleimide and the like.
  • Examples of the monomer having a hydroxy group other than the phenolic hydroxy group include, for example, 2-hydroxy 6-hydroxynorbornene-1, 2-carboxyl-6-latatane, 2-hydroxyethyl metatalylate, 2-hydroxypropyl metatalylate 5 Methacryloyloxy 6-hydroxynorbornene 2 Carboxylic 6-latathone and the like.
  • examples of the monomer having an amino group having active hydrogen include 2-aminoethyl acrylate and 2-aminomethyl methacrylate.
  • the specific copolymer includes a monomer having a functional group for thermal crosslinking reaction and a monomer other than a monomer having a functional group for film curing (hereinafter referred to as other monomer) as structural units. It may be a formed copolymer.
  • Other monomers specifically include carboxyl groups and phenolic hydroxy groups. Any monomer that can be copolymerized with a monomer having at least one of the above and a monomer having at least one of a hydroxy group other than a phenolic hydroxy group and an amino group having an active hydrogen (A) is acceptable. There is no particular limitation as long as the properties of the components are not impaired.
  • Specific examples of other monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, and bur compounds.
  • Examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2, 2 , 2-Trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2 ethoxyethyl acrylate Furfuryl acrylate, 3-methoxy butyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl 2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate and 8-ethOne 8-tricyclodecyl Atari rate, and the like.
  • Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthrinole methacrylate, nonlinole methacrylate methacrylate.
  • Examples thereof include 2-propyl-2-adamantyl methacrylate, 8 methyl-8 tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate.
  • Examples of the bur compound include methyl butyl ether, benzyl butyl ether, 2-hydroxy ethino levino reetenole, phenino levino ree tenole, and propino vinyl ether.
  • Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene, and the like.
  • maleimide compound examples include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
  • the method for obtaining the specific copolymer used in the present invention is not particularly limited.
  • the group of monomers having at least one of a carboxyl group and a phenolic hydroxy group, and at least one monomer appropriately selected from At least one monomer appropriately selected from the group of monomers having at least one of a hydroxy group other than a phenolic hydroxy group and an amino group having an active hydrogen, and optionally a monomer other than the above monomers, and optionally polymerization initiation It can be obtained by polymerizing the agent in a solvent at a temperature of 50 to 110 ° C.
  • the solvent used is not particularly limited as long as it dissolves the monomer constituting the specific copolymer and the specific copolymer. Specific examples include the solvents described in (E) Solvent described later.
  • the specific copolymer thus obtained is usually in a solution state in which the specific copolymer is dissolved in a solvent.
  • the solution of the specific copolymer obtained as described above is re-precipitated by stirring with stirring such as jetyl ether or water, and the generated precipitate is filtered and washed, and then at normal pressure or reduced.
  • the powder of the specific copolymer can be obtained by drying at room temperature or under heat. By such an operation, it is possible to remove the polymerization initiator and unreacted monomer coexisting with the specific copolymer, and as a result, a purified powder of the specific copolymer can be obtained. If sufficient purification is not possible with a single operation, the obtained powder may be redissolved in a solvent and the above operation repeated.
  • the powder of the specific copolymer may be used as it is, or the powder may be redissolved in a solvent (E) described later and used as a solution.
  • polyamic acid polyamic acid ester
  • polyimide precursor such as partially imidized polyamic acid
  • polyimide such as carboxylic acid group-containing polyimide
  • the polyimide precursors and polyimides are within the range of 2,000 to 50,000 in terms of developability and solubility in the solvent used, and number average molecular weight (in terms of polyethylene oxide and polyethylene glycol).
  • the number average molecular weight and weight average molecular weight of the polyimide precursor and polyimide are, for example, as follows: GPC apparatus (Shodex (registered trademark) columns KD802, KD803, and KD804) manufactured by JASCO Corporation. It is possible to measure under the following conditions when lithium bromide N, N dimethylformamide solution is eluted at a flow rate of lml / min (column temperature 40 ° C).
  • the polyamic acid as a polyimide precursor can be generally obtained by polycondensation of (a) a tetracarboxylic dianhydride compound and (b) a diamine compound.
  • tetracarboxylic dianhydride compounds include, but are not limited to, pyromellitic dianhydride, 3, 3 ', 4, 4'-biphenyl tetracarboxylic dianhydride, 3, 3 ', 4, 4' monobenzophenone tetracarboxylic dianhydride, 3, 3 ', 4, 4'-diphenyl ether tetracarboxylic dianhydride, 3, 3', 4, 4 ' —Aromatic tetracarboxylic acids such as diphenylsulfone tetracarboxylic acid dihydrate, 1, 2, 3, 4 cyclobutane tetracarboxylic acid dihydrate, 1, 2 dimethinole 1, 2, 3, 4 Cyclofu, tan tetra Force norevon dianhydride, 1, 2, 3, 4 tetramethylolene 1, 2, 3, 4 cyclobutane tetra force norevon dianhydride,
  • diamine compounds are not particularly limited.
  • Diamine compounds having Also, p-phenylenediamine, m-phenylenediamine, 4,4'-methylenebis (2,6 ethenorea diphosphorus), 4,4 'methylene monobis (2 isopropyl-6-methylaniline), 4, 4'-methi Renbis (2, 6 diisopropylaniline), 2, 4, 6 trimethyl-1,3 phenylenediamine, 2, 3, 5,6 tetramethyl-1,4 phenylenediamine, o tolidine, m tolidine, 3, 3 ', 5, 5'-tetramethylbenzidine, bis [4— (3-aminophenoxy) phenol] sulfone, 2,2bis [4— (3aminophenoxy) phenol] propane, 2,2bis [4 1- (3-aminophenoxy) phenyl] hexafluoropropane, 4,4'-diamino-3,3'-dimethyldimethylcyclohexyl, 4,4'-diamin
  • the polyamic acid used in the present invention is produced from (a) a tetracarboxylic dianhydride compound and (b) a diamine compound, the compounding ratio of both compounds, that is, ⁇ (b) the total mole of the diamine compound
  • the number / (a) the total number of moles of tetracarboxylic dianhydride compound> is preferably 0.7 to 1.2.
  • the terminal amino group can be protected by reacting the terminal amino group of the remaining polyamic acid with a carboxylic acid anhydride.
  • carboxylic anhydrides include phthalic anhydride, trimellitic anhydride, anhydrous maleic acid, naphthalic anhydride, hydrogenated phthalic anhydride, methyl-5-norbornene-2,3 dicarboxylic anhydride Power, itaconic anhydride, tetrahydrophthalic anhydride, etc.
  • the reaction temperature of the reaction between the diamine compound and the tetracarboxylic dianhydride compound can be selected from any temperature of -20 to 150 ° C, preferably -5 to 100 ° C. it can.
  • the reaction temperature is appropriately selected within the range of 5 ° C to 40 ° C and the reaction time of 1 hour to 48 hours.
  • the reaction temperature when the terminal amino group is protected with an acid anhydride can be selected from -20 to 150 ° C, preferably 5 to 100 ° C.
  • the reaction of the diamine compound and the tetracarboxylic dianhydride compound can be carried out in a solvent.
  • Solvents that can be used include N, N dimethylformamide, N, N dimethylacetamide, N methyl pyrrolidone, N butyl pyrrolidone, N methyl caprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethy Nolesulphoxide, m Cresol, ⁇ -butyrolatatone, ethyl acetate, butyl acetate, ethyl lactic acid, methyl 3 methoxypropionate, methyl 2 methoxypropionate, 3 ethyl methoxypropionate, 2 ethyl methoxypropionate, 3 ethyl ethoxypropionate, 2-Ethoxypropionate, Ethylene glycol dimethyl ether, Diethylene glyconores,
  • the solution containing the polyamic acid thus obtained can be used as it is for the preparation of a solution of the positive photosensitive resin composition.
  • the polyamic acid can be used after being isolated by precipitation in a poor solvent such as water, methanol, or ethanol and recovered.
  • the polyamic acid thus obtained can be esterified with a carboxyl group and used as a polyamic acid ester.
  • the polyamic acid thus obtained may be used alone or at the same time as the alkali-soluble resin described above.
  • any polyimide can be used.
  • the polyimide used in the present invention is obtained by chemically or thermally immobilizing 50% or more of a polyimide precursor such as polyamic acid.
  • These polyimides include polyamideimides, polyetherimides and copolymers.
  • the polyimide in the positive photosensitive resin composition used in the present invention has a carboxyl group or a phenolic hydroxy group to impart alkali solubility, or a carboxylic acid or phenolic hydroxy group by the action of heat or acid. It preferably has a group that forms a group.
  • the method of introducing a carboxyl group or a phenolic hydroxy group into polyimide is a method using a monomer having a carboxyl group or a phenolic hydroxy group, or a method of sealing an amine end with an acid anhydride having a carboxyl group or a phenolic hydroxy group.
  • a method of making the imidization rate 99% or less when imidizing the polyimide precursor is used.
  • fever or an acid to a polyimide is the method using the monomer which produces
  • Action of heat or acid on carboxyl group or phenolic hydroxy group or carboxylic acid residue after imidization There is a method of reacting a group that dissociates by.
  • Such a polyimide can be obtained by synthesizing the above polyimide precursor and then performing chemical imidization or thermal imidization.
  • acetic anhydride and pyridine are added to a polyimide precursor solution and reacted at room temperature to 100 ° C.
  • a method for thermal imidization generally, a method in which a polyimide precursor solution is heated at a temperature of 180 ° C. to 250 ° C. without being dehydrated is used.
  • the polyimide thus obtained may be used alone or at the same time as other alkali-soluble resins (for example, specific copolymers) described above.
  • Component (B) is a compound having two or more butyl ether groups in one molecule. This is the type and structure of any compound that has two or more butyl ether groups in one molecule that can be thermally crosslinked with the alkali-soluble resin (A) at a conventional prebeta temperature! /, Not particularly limited!
  • the compound of component (B) is obtained by subjecting the component (A) to alkali-solubility due to the acid generated by exposure in the presence of a photoacid generator after thermal crosslinking with the alkali-soluble resin of component (A). After separation (decrosslinking) from the resin, development with an alkaline developer removes both the alkali-soluble resin (A). Therefore, as this type of compound, a bull ether compound generally used as a component of a bull ether type chemically amplified resist can be applied. The use of such a compound has the advantage that the formed image can be controlled by adjusting the thermal crosslinking density by changing the compounding amount of the compound.
  • the compounds represented by the formulas (1) and (2) are particularly developed without residual film in the exposed area. In terms, it is preferable.
  • n is an integer of 2 to 10
  • k is an integer of 1 to 10
  • R 1 represents an n-valent organic group.
  • n an integer of 2 to 10.
  • n represents the number of butyl ether groups in one molecule, and n is more preferably an integer of 2 to 4.
  • M in the formula (2) also represents the number of butyl ether groups in one molecule, and m is more preferably an integer of 2 to 4.
  • Specific examples of the compounds represented by the formula (1) and the formula (2) include bis (4 (vinyloxymethyl) cyclohexylmethyl) glutarate, tri (ethylene glycol) dibutyrenole, dibiadipate Cyclohexane dimethanol dibulle ethers such as ninoreestenole, diethyleneglyconoresininoreethenole, tristoate, bis (4 (vinyloxy) butyl isophthalate, and 1,4-cyclohexanedimethanol dibule ether Etc.
  • the compound of component (B) is used in a proportion of 1 to 80 parts by weight, preferably 5 to 40 parts by weight, per 100 parts by weight of component (A).
  • amount of the component (B) compound used is an excessive amount less than the lower limit of the above range, the reduction of the film in the unexposed area becomes remarkable and the formed relief pattern of the pattern becomes poor.
  • amount of the component (B) compound used exceeds the upper limit of the above range, the sensitivity of the film is greatly reduced, and residues between patterns are generated after development.
  • Component (C) is a compound that undergoes a cross-linking reaction with component (A) by post-beta, and preferably a compound having two or more block isocyanate groups in one molecule. This is either thermally cross-linked with the compound of component (B) or further de-crosslinked with (A) For example, if it is a compound having two or more block isocyanate groups in one molecule that can be thermally cured at a conventional post-beta temperature with respect to a film made of an alkali-soluble resin as a component, the kind and The structure is not particularly limited.
  • the compound of component (C) has two or more blocked isocyanate groups in which one or more isocyanate groups (one NCO) are blocked by an appropriate protecting group, and is heated at high temperature during thermal curing. Exposure to the functional group (for example, phenolic hydroxy group) for thermal curing in the alkali-soluble resin of component (A) via the generated isocyanate group. Other than the hydroxy group and the amino group having active hydrogen), the crosslinking reaction proceeds between, for example, the formula (3)
  • R 2 represents an organic group in the block part
  • this group may be the same or different from each other.
  • ! /, are included.
  • an appropriate blocking agent is allowed to act on a compound having two or more isocyanate groups in one molecule. With the power S to get.
  • Examples of the compound having two or more isocyanate groups in one molecule include, for example, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), and trimethyl hexane methacrylate.
  • Examples thereof include diisocyanate and the like, or dimers and trimers thereof, or a reaction product of these with diols, triols, diamines, and triamines.
  • Examples of the blocking agent include alcohols such as methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N, N-dimethylaminoethanol, 2-ethoxyethanol, and cyclohexanol.
  • alcohols such as methanol, ethanol, isopropanol, n-butanol, 2-ethoxyhexanol, 2-N, N-dimethylaminoethanol, 2-ethoxyethanol, and cyclohexanol.
  • the compound of component (C) has a force S that causes the thermal release of the block portion and a crosslinking reaction proceeds through the isocyanate group at higher temperatures such as the post-beta temperature, such as the force S and the pre-beta temperature.
  • the temperature of the thermal dissociation of the block portion is considerably higher than the prebeta temperature, for example, 120 ° C to 230 ° C (C) Especially preferred as a component compound!
  • Examples of the compound of the component (C) include the following specific examples.
  • Examples of such a compound that the compound (C) is more preferred from the viewpoint of heat resistance and coating properties include the following.
  • R in the following formula represents an organic group.
  • the compound of component (C) may be used alone or in combination of two or more.
  • the compound of component (C) is used in a proportion of 3 to 70 parts by weight, preferably 5 to 40 parts by weight, per 100 parts by weight of component (A).
  • the amount of the component (C) compound used is an excessive amount less than the lower limit of the above range, the thermosetting is insufficient and a satisfactory cured film cannot be obtained.
  • the amount of the compound (C) component used If the amount exceeds the upper limit of the above range, the development becomes insufficient and a development residue is generated.
  • Component (D) is a photoacid generator (also referred to as PAG). This is a substance that generates acids (sulfonic acids, carboxylic acids, etc.) directly or indirectly by the irradiation of light used for exposure. If it has such properties, its type and structure Etc. are not particularly limited.
  • Examples of the photoacid generator of component (D) include diazomethane compounds, onium salt compounds, sulfonimide compounds, disulfone compounds, sulfonic acid derivative compounds, nitrobenzyl compounds, benzoin tosylate compounds, iron arenes. Examples include complexes, halogen-containing triazine compounds, acetophenone derivative compounds, and cyano group-containing oxime sulfonate compounds. Any conventionally known or conventionally used photoacid generator can be applied in the present invention without any particular limitation. In the present invention, the photoacid generator of component (D) may be used alone or in combination of two or more.
  • photoacid generator examples include the following. However, these compounds are a few examples of a very large number of applicable photoacid generators, and of course are not limited thereto.
  • the photoacid generator of component (D) is 100 parts by mass of the alkali-soluble resin of component (A). And 0.5 to 50 parts by weight, preferably 1 to 30 parts by weight.
  • amount of the photoacid generator used as the component (D) is too small below the lower limit of the above range, from the alkali-soluble resin of the component (A) of the component of the component (B) that has been thermally bridged during exposure. If the amount of the photoacid generator used as the component (D) exceeds the upper limit of the above range, the positive photosensitive resin may not be obtained. The storage stability of the composition becomes inferior.
  • the positive photosensitive resin composition used in the present invention contains the components (A) to (D) described above, and usually a solution obtained by dissolving these components in the solvent (E) is applied to the positive photosensitive resin composition. Forming a layer.
  • the (E) solvent dissolves the components (A) to (D) and dissolves the component (F) to be added as required, and has such a dissolving ability.
  • it is a solvent, its type and structure are not particularly limited.
  • Such (E) solvents include, for example, ethylene glycol monomethyl ether, ethylene glycol monomethenoate ethere, methinorecero sonoleb acetate, ethenorecero sonolebate, diethylene glycol monomethyl ether, diethylene glycol monoester.
  • Chill etherenole propylene glycolate, propylene glycolenomonomethinoatenole, propylene glycolenomonomethinoatenoacetate, propylene glycolenopropenoatenoate acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclo Hexanone, 2-heptanone, ⁇ -butarate ratataton, 2-hydroxyethyl ethionate, 2-hydroxyethyl 2-methylpropionate, ethoxyethyl ethoxylate, hydroxyacetic acid Tyl, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate Butyl
  • solvents propylene glycol monomethyl ether, propylene glycol Nolemonomethylenoateolacetate, 2-heptanone, propyleneglycololepropynolether, propyleneglycolpropyletheracetate, ethyl lactate, butyl lactate and the like are preferable from the viewpoint of good coating properties and high safety.
  • solvents are generally used as solvents for photoresist materials.
  • Component (F) is a surfactant.
  • a surfactant may be further added for the purpose of improving the coating property as long as the effects of the present invention are not impaired.
  • the surfactant of the component (F) is not particularly limited, and examples thereof include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant.
  • a fluorine-based surfactant such as those manufactured by Sumitomo 3EM Co., Ltd., Dainippon Ink & Chemicals, Inc., or Asahi Glass Co., Ltd. can be used. These commercial products are convenient because they are readily available.
  • F-top EF301, EF303, EF352 manufactured by Gemco
  • MegaFuck F171, F173, R-30 manufactured by Dainippon Ink Chemical Co., Ltd.
  • Florard FC430, FC431 Fluorine surfactants such as Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SCI 06 (Asahi Glass Co., Ltd.), and the like.
  • surfactants can be used singly or in combination of two or more.
  • the content thereof is usually 0.2% by mass or less, preferably 0.1% by mass or less, in 100% by mass of the positive photosensitive resin composition solution. It is. Even if the amount of the surfactant (F) used is set to an amount exceeding 0.2% by mass, the effect of improving the coating property becomes dull and not economical.
  • the positive type photosensitive resin composition used in the present invention is, as long as it does not impair the effects of the present invention, adhesion aids such as rheology modifiers and silane coupling agents, pigments, dyes, and storage. It can contain stabilizers, antifoaming agents, or solubility promoters such as polyhydric phenols and polycarboxylic acids.
  • the silane coupling agent can be used for the purpose of improving the adhesion to the substrate. Specific examples thereof are as follows.
  • the positive photosensitive resin composition used in the present invention comprises an alkali-soluble resin as component ( ⁇ ), a compound having two or more butyl ether groups in one molecule of component ( ⁇ ), and a post-baking of component (C).
  • component (Ii) contains a compound that undergoes a crosslinking reaction with component (D) and a photoacid generator of component (D).
  • these components (i) to (D) are dissolved in (i) a solvent and used for forming a positive photosensitive resin layer in the form of a solution. Further, each of them may contain one or more of the surfactant (F) and other additives as desired.
  • component ( ⁇ ) Based on 100 parts by weight of component ( ⁇ ), 1 to 80 parts by weight of component ( ⁇ ), 3 to 70 parts by weight of component (C), and 0.5 to 50 parts by weight of (D) A positive photosensitive resin composition containing a component.
  • [2] A solution of a positive photosensitive resin composition in which the composition of [1] above is dissolved in (i) a solvent.
  • the ratio of the solid content in the solution of the positive photosensitive resin composition is not particularly limited as long as each component is uniformly dissolved in the solvent, and is, for example, 1 to 80% by mass. Also, for example, 5 to 60% by mass, or 8 to 50% by mass.
  • solid (E) Solvent is removed from all components of the positive-type photosensitive resin composition solution!
  • the method for preparing the positive type photosensitive resin composition solution is not particularly limited.
  • the component (A) (alkali-soluble resin) is dissolved in the solvent (E) and the solution is prepared.
  • B) component component (compound having two or more butyl ether groups in one molecule),
  • C) component component (compound that crosslinks with (A) component by postbeta),
  • D) component photoacid generator
  • F) Component (surfactant) is mixed at a predetermined ratio to make a uniform solution, or at the appropriate stage of this preparation method, other additives are further added as necessary and mixed.
  • a method is mentioned.
  • the solution of the specific copolymer obtained by the polymerization reaction in a solvent can be used as it is.
  • the component (A) When the solution (B), (C), (D) and the like are added to the solution in the same manner as described above, a solvent may be further added for the purpose of adjusting the concentration.
  • the solvent used in the process of forming the specific copolymer may be the same as or different from the solvent used for adjusting the concentration when preparing the solution of the positive photosensitive resin composition. May be.
  • the prepared positive photosensitive resin composition solution is preferably used after being filtered using a filter having a pore size of about 0.2 m.
  • the high-sensitivity layer used in the present invention is not particularly limited as long as it is a sufficiently high-sensitivity photosensitive resin layer compared with the sensitivity of the low-sensitivity layer described above.
  • a positive photosensitive resin composition is used as such a high-sensitivity layer.
  • the high-sensitivity layer used in the present invention may be the same type as the positive photosensitive resin composition used in the low-sensitivity layer. In this case, it is preferable because of high sensitivity and improved throughput, low pattern shape control, and suppression of film loss in unexposed areas during development! /.
  • the contents of the (B) component and the (C) component in the positive-type photosensitive resin composition of the high-sensitivity layer are set so that It is preferable that the content (mass) be less than the above.
  • the positive-type feeling of the high-sensitivity layer The component (B) and the component (C) in the photosensitive resin composition are 10 to 80% of the content (mass) of the component (B) contained in the positive photosensitive resin composition of the low sensitivity layer, In addition, the content (mass) of component (C) is preferably 30 to 70%.
  • the component (B) and the component (C) in the positive photosensitive resin composition of the high sensitivity layer are contained in the positive photosensitive resin composition of the low sensitivity layer. It is preferable that the content be 10 to 50% of the amount (mass) and 40 to 60% of the content (mass) of the component (C)! /,
  • the positive photosensitive resin composition used in the high-sensitivity layer is the above-described ⁇ Low Sensitivity Positive Photosensitive Resin Layer (Low Sensitivity Layer)> [Positive Photosensitive Resin Composition and Solution] can be obtained in the same manner.
  • the mixed solution containing the components (A) to (E) and, optionally, the component (F) is kept at a temperature higher than room temperature for a required period of time, thereby reducing the following heat.
  • Crosslinking reaction force S Some progress, positive photosensitive resin containing (A) component to (E) solvent, and optionally (F) component and (A) component and (B) component cross-linked product A solution of the composition is obtained. More preferably, by keeping the mixed solution at a temperature of 30 ° C. to 70 ° C. for 2 hours to 5 days, in addition to the components (A) to (E) and, optionally, the component (F), ( A solution of a positive photosensitive resin composition containing a cross-linked product of component A) and component (B) is obtained.
  • the homogeneity of the solution of the resulting resin composition is increased, and as a result, when the film is subjected to a subsequent film formation step, the photoacid generator is in the film.
  • the resulting film can be dispersed efficiently, leading to a dramatic improvement in the sensitivity of the resulting film.
  • the stirring temperature is higher than 70 ° C, the crosslinking reaction and curing reaction proceed and the composition solution becomes non-uniform, and the sensitivity of the resulting film is greatly reduced. The uniformity of the solution does not increase, and the sensitivity is not improved.
  • two positive photosensitive resin layers having different exposure sensitivities are disposed on the base material, and the low sensitivity positive photosensitive resin layer is disposed between the base material and the high sensitivity positive photosensitive resin layer.
  • the lamination force is not particularly limited.
  • a solution of a positive photosensitive resin composition for a low-sensitivity layer can be used in a semiconductor.
  • substrates for example, silicon / silicon dioxide coated substrates, silicon nitride substrates, substrates coated with metals such as aluminum, molybdenum, chromium, etc., glass substrates, quartz substrates, ITO substrates, etc. and devices such as transistors are formed on them.
  • Low-sensitivity by spin coating, flow coating, roll coating, slit coating, spin coating following slit, ink jet coating, etc., followed by preliminary drying in a hot plate or oven.
  • a layer can be formed.
  • the high-sensitivity layer is formed by applying a positive photosensitive resin composition solution for the high-sensitivity layer in the same manner as the low-sensitivity layer and pre-drying it with a hot plate or oven.
  • a heating temperature and a heating time appropriately selected from the range of a temperature of 70 ° C to 160 ° C and a time of 0.3 minutes to 60 minutes are employed.
  • the heating temperature and the heating time are preferably 80 ° C to 140 ° C, and 0.5 minutes to 10 minutes.
  • the solvent is removed, and the compound having a butyl ether group as the component (B) is crosslinked with the resin as the component (A), thereby forming a film hardly soluble in an alkali developer.
  • the temperature of the preliminary drying is lower than the lower limit of the above temperature range, a large amount of the solvent remains in the film and the target pattern is not formed, or the low sensitivity layer is applied when the high sensitivity layer is applied. Intermixing may occur, and thermal crosslinking may be insufficient, resulting in film loss in unexposed areas.
  • the film thickness of the positive photosensitive resin layer (the layer combining the low-sensitivity layer and the high-sensitivity layer) is, for example, 0.1 to 30 m, and for example, 0.2 to 10 m. Further, for example, 0 ⁇ 2 to 5 ⁇ m.
  • the film thicknesses of the low-sensitivity layer and the high-sensitivity layer can be arbitrarily selected as long as the effects of the present invention are not impaired.
  • the positive photosensitive resin layer obtained by the above method is exposed to light such as ultraviolet rays, ArF, KrF, and F laser light using a halftone mask having a predetermined pattern. Due to the action of the acid generated from the photoacid generator of component (D) contained in the di-type photosensitive resin layer Therefore, the exposed portion of the film becomes soluble in an alkaline developer.
  • the exposure is preferably performed with light having at least one wavelength of i-line, g-line, and h-line, or ArF, KrF, or F laser light.
  • heating conditions in this case, a heating temperature and a heating time appropriately selected from the range of a temperature of 80 ° C. to 140 ° C. and a time of 0.3 minutes to 60 minutes are employed.
  • alkaline developer examples include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, and choline.
  • Alkaline aqueous solutions such as aqueous solutions of quaternary ammonium hydroxide, amine solutions such as ethanolamine, propylamine, and ethylenediamine.
  • a surfactant or the like can be added to these developers.
  • a 0.1 to 2.38 mass% aqueous solution of tetraethylammonium hydroxide is generally used as a photoresist developer, and this alkaline developer is also used in the photosensitive resin composition of the present invention. Using this, it is possible to develop a good image without causing problems such as swelling.
  • V and displacement S such as a liquid filling method, a dating method, and a rocking dipping method.
  • the development time at that time is usually 15 seconds to 180 seconds.
  • the positive photosensitive resin layer is washed with running water, for example, for 20 to 90 seconds, followed by air drying with compressed air or compressed nitrogen or spinning. The top moisture is removed and a patterned film is obtained.
  • post-beta for thermosetting, specifically, by using a hot plate, an oven, etc. to heat resistance, transparency, and flattening.
  • the post-beta is generally at a heating temperature selected from the range of 150 ° C to 270 ° C, for 5 to 30 minutes on a hot plate, or in the oven. If treated for 30 to 90 minutes!
  • a coating film having a fine pattern with a wide half-exposure margin that has sufficiently high sensitivity and a very small film thickness reduction in an unexposed area during development can be obtained by the production method of the present invention. Can be formed.
  • PGMEA Propylene glycol monomethyl ether acetate
  • PAG 1 Ciba's Specialty. CGI 1397 (trade name) manufactured by Chemicals Co., Ltd./Compound name: 2-methyl- ⁇ — [5— [[(propylsulfonyl) oxy] imino] ichi (5H) —Cenilide N] benzeneacetonitrile (compound of formula (7))
  • PVE2 1,4-Cyclohexanedimethanonoresininoreatenore
  • NCO l Degussa AG VESTAGON (registered trademark) B 1065 (trade name) / Compound name: ⁇ One strength prolatatum block polyisocyanate (compound of formula (S-4))
  • the number-average molecular weight and weight-average molecular weight of the specific copolymer obtained according to the following synthesis example were measured using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF8034) manufactured by JASCO Corporation and the elution solvent tetrahydrofuran was flowed. The measurement was performed under the condition that elution was carried out through a column (column temperature 40 ° C) at 1 ml / min.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • MAA 19.4 g, CHMI 35.3 g, HEMA 25.5 g, and MMA 19.8 g are used as monomer components constituting the specific copolymer, and AIBN 5 g is used as a radical polymerization initiator, and these are used as solvent PGMEA 212
  • (B), (C), (D), and (E) solvent, and (F) component are mixed at a predetermined ratio with the solution of component (A).
  • ⁇ Composition Example 7> As an alkali-soluble resin solution, add 17.2 g of the specific copolymer solution (P2) obtained in Synthesis Example 2, 1.7 g of P200 as a 1,2-quinonediazide compound, and GT4 as an epoxy crosslinkable compound. 1. lg, R30 as surface active Tosei IJ R. 0039g, MPTS 0.25g as adhesion assistant IJ, PGMEA 6.5g as solvent, mix for 8 hours at room temperature, positive type photosensitive resin composition The product solution was prepared.
  • Comparative Examples 2 and 3 are photobleached at the stage after image formation and before post-beta.
  • PEB post-exposure heating
  • pre-beta After applying a solution of the positive photosensitive resin composition for the lower layer onto a quartz substrate using a spin coater, pre-beta was applied on a hot plate for 120 seconds at a temperature of 110 ° C to form a coating film with a film thickness of 2. ⁇ ⁇ . Formed. Next, after applying a positive photosensitive resin composition solution for the upper layer onto the coating film using a spin coater V, pre-beta was performed on a hot plate at a temperature of 110 ° C for 120 seconds to obtain a film thickness. 1. An Om coating was formed.
  • This coating film was immersed in a 0.4% aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH) for 60 seconds, and then washed with running ultrapure water for 20 seconds.
  • Post-beta was performed by heating at 230 ° C for 30 minutes at a temperature of 2! /, And a cured film having a film thickness of 2.4 ⁇ 111 was formed.
  • the initial transmittance of this cured film was measured at a wavelength of 400 nm using an ultraviolet-visible spectrophotometer (SHIMADZU UV-2550 model, manufactured by Shimadzu Corporation). Further, this coating film was heated at 250 ° C. for 30 minutes, and similarly, the transmittance was measured after heating at a wavelength of 400 nm.
  • the film thickness in this evaluation was measured using F20 manufactured by FILMETRI CS. [0141] ⁇ Comparative Example 1>
  • a positive photosensitive resin composition solution is applied onto a quartz substrate using a spin coater, and then pre-betated on a hot plate for 120 seconds at a temperature of 120 ° C to form a coating film with a thickness of 3. ⁇ ⁇ m did.
  • This coating film was immersed in a 0.4% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 20 seconds. After baking at 230 ° C for 30 minutes, a cured film with a thickness of 2.4! 11 was formed.
  • the initial transmittance of this cured film was measured at a wavelength of 400 nm using a UV-visible spectrophotometer (SHIMADZU UV-2550 model, manufactured by Shimadzu Corporation). Further, the coating film was heated at 250 ° C. for 30 minutes, and the transmittance was similarly measured after heating at a wavelength of 400 nm.
  • the film thickness in this evaluation was measured using F20 manufactured by FILMETRICS.
  • pre-beta was applied on a hot plate at a temperature of 1 10 ° C for 120 seconds to form a coating film with a thickness of 3. ⁇ ⁇ m. Formed.
  • This coating film was immersed in a 0.4% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 20 seconds.
  • the coated film Canon KK ultraviolet irradiation apparatus PLA - light intensity at 365nm by 600FA is irradiated with ultraviolet rays of 5.
  • Post-beta was performed by heating for 30 minutes to form a cured film with a film thickness of 2.4 ⁇ .
  • the initial transmittance of this cured film was measured at a wavelength of 400 nm using an ultraviolet-visible spectrophotometer (SHIMADZU UV-2550 model, manufactured by Shimadzu Corporation). Further, this coating film was heated at 250 ° C. for 30 minutes, and the transmittance was similarly measured after heating at a wavelength of 400 ⁇ m.
  • the film thickness in this evaluation was measured using F20 manufactured by FILMETRICS.
  • pre-beta was applied on a hot plate for 120 seconds at a temperature of 1 10 ° C. Low sensitivity layer) was formed. Subsequently, the positive photosensitive resin composition for the upper layer was applied onto the coating film using a spin coater, and then hot-pressed at a temperature of 1 10 ° C for 120 seconds. A pre-beta was applied on the sheet to form a coating film (high-sensitivity layer) having a thickness of 1 ⁇ ⁇ . The film thickness was measured using F20 manufactured by FILMETRICS.
  • This coating film was irradiated with UV light with a light intensity of 5.5 mW / cm 2 at 365 nm by a UV irradiation device PLA-600FA manufactured by Canon Inc. at various exposure doses, and then on a hot plate for 120 seconds at a temperature of 110 ° C. After the exposure, heating was performed. Thereafter, the film was developed by immersing it in a 0.4% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 20 seconds. Sensitivity was defined as the lowest exposure amount (mj / cm 2 ) at which no undissolved material remained in the exposed area! In addition, the amount of decrease in the film thickness in the unexposed area was reduced.
  • pre-beta was applied on a hot plate for 120 seconds at a temperature of 110 ° C. to form a coating film having a thickness of 3.0 ⁇ m.
  • the film thickness was measured using F20 manufactured by FILMETRICS.
  • the coating film by Canon KK ultraviolet irradiation apparatus PLA-600FA light intensity at 365nm was irradiated with ultraviolet rays of 5. 5 mW / cm 2 at various exposure amounts, following! /, In 120 seconds at 110 ° C Post-exposure heating was performed on the hot plate.
  • the film was developed by being immersed in a 0.4% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 20 seconds. Sensitivity was defined as the lowest exposure (mj / cm 2 ) at which no undissolved material remained in the exposed area. In addition, the amount of decrease in the film thickness in the unexposed area was defined as film reduction.
  • pre-beta was applied on a hot plate for 120 seconds at a temperature of 110 ° C. to form a coating film having a thickness of 3.0 ⁇ m.
  • the film thickness was measured using F20 manufactured by FILMETRICS.
  • the coating film by Canon KK ultraviolet irradiation apparatus PLA-600FA light intensity at 365nm was irradiated with ultraviolet rays of 5. 5 mW / cm 2 at various exposure amounts.
  • the film was developed by immersing it in a 0.4% TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 20 seconds. Sensitivity was defined as the lowest exposure (mj / cm 2 ) at which no undissolved portion remained in the exposed area.
  • the amount of decrease in the film thickness of the unexposed part was defined as film reduction.
  • Examples 1 to 4 a high-sensitivity layer is used as the upper layer and a low-sensitivity layer is used as the upper layer, so that a high transmittance can be maintained and development can be performed without film loss. An optical margin could be obtained.
  • Comparative Example 1 has a high sensitivity and the ability to develop without reducing the film. The half exposure margin was remarkably low.
  • Comparative Examples 2 and 3 are both less sensitive and less exposed in unexposed areas than Examples 1 to 4. From these results, the sensitivity of these single-layer systems increases as the sensitivity increases. A decrease in half exposure margin and transmittance was observed.
  • the transparent cured film obtained by the method for producing a transparent cured film of the present invention can be applied to the production of a TFT flattened film in a transflective liquid crystal display element, in particular, contact holes and reflective irregularities by half exposure. It is suitable as a material for forming a transparent cured film for simultaneously forming.

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Abstract

L'objet de l'invention est un procédé de fabrication d'un film durci transparent qui présente une importante marge d'exposition tout en maintenant un haut niveau de sensibilité, en particulier un procédé de fabrication d'un film durci transparent qui peut être appliqué à la fabrication d'un film aplatissant les TFT dans un élément d'affichage à cristaux liquides du type à semi-transmission et qui est notamment utilisé pour former simultanément des trous de contact et des surfaces concavo-convexes de réflexion par une demie exposition. Le procédé de fabrication d'un film durci transparent est caractérisé par l'empilement de deux couches de résine photosensible positive différentes l'une de l'autre à une sensibilité d'exposition sur un matériau de base de telle sorte que la couche de résine photosensible positive ayant une sensibilité moindre est située entre le matériau de base et la couche de résine photosensible positive ayant une sensibilité plus forte, l'exposition des couches de résine positive à la lumière, le chauffage des couches de résine positive exposées, le développement de l'ensemble et la cuisson ultérieure de l'ensemble. Un élément d'affichage comprenant un film durci transparent produit par le procédé présenté ci-dessus.
PCT/JP2007/068083 2006-09-20 2007-09-18 Procédé de fabrication d'un film durci transparent en utilisant une couche de résine photosensible positive pendant une demie exposition WO2008035672A1 (fr)

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US8168371B2 (en) 2007-01-22 2012-05-01 Nissan Chemical Industries, Ltd. Positive photosensitive resin composition
US8828651B2 (en) 2005-07-25 2014-09-09 Nissan Chemical Industries, Ltd. Positive-type photosensitive resin composition and cured film manufactured therefrom

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CN107409457B (zh) * 2015-03-11 2018-11-13 东丽株式会社 有机el显示装置及其制造方法

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JP2009282312A (ja) * 2008-05-22 2009-12-03 Nissan Chem Ind Ltd 感光性樹脂組成物

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CN101517492B (zh) 2012-04-18
JP5083566B2 (ja) 2012-11-28
JPWO2008035672A1 (ja) 2010-01-28
KR101334753B1 (ko) 2013-12-02
CN101517492A (zh) 2009-08-26
TWI431425B (zh) 2014-03-21
KR20090058530A (ko) 2009-06-09

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