WO2021090576A1 - Composition de résine non photosensible - Google Patents

Composition de résine non photosensible Download PDF

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Publication number
WO2021090576A1
WO2021090576A1 PCT/JP2020/034727 JP2020034727W WO2021090576A1 WO 2021090576 A1 WO2021090576 A1 WO 2021090576A1 JP 2020034727 W JP2020034727 W JP 2020034727W WO 2021090576 A1 WO2021090576 A1 WO 2021090576A1
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resin composition
photosensitive resin
formula
group
composition according
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PCT/JP2020/034727
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English (en)
Japanese (ja)
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安達 勲
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日産化学株式会社
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Priority to CN202410359132.7A priority Critical patent/CN118255920A/zh
Priority to CN202080074452.8A priority patent/CN114599694B/zh
Priority to JP2021554831A priority patent/JP7311846B2/ja
Priority to KR1020227013538A priority patent/KR102683968B1/ko
Publication of WO2021090576A1 publication Critical patent/WO2021090576A1/fr

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/26Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02Monomers containing only one unsaturated aliphatic radical
    • C08F212/04Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06Hydrocarbons
    • C08F212/08Styrene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02Monomers containing only one unsaturated aliphatic radical
    • C08F212/04Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06Hydrocarbons
    • C08F212/12Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041Lenses
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00Simple or compound lenses
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00Simple or compound lenses
    • G02B3/0006Arrays
    • G02B3/0012Arrays characterised by the manufacturing method
    • G02B3/0018Reflow, i.e. characterized by the step of melting microstructures to form curved surfaces, e.g. manufacturing of moulds and surfaces for transfer etching
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02Homopolymers or copolymers of hydrocarbons
    • C08J2325/04Homopolymers or copolymers of styrene
    • C08J2325/06Polystyrene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02Homopolymers or copolymers of hydrocarbons
    • C08J2325/16Homopolymers or copolymers of alkyl-substituted styrenes
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00Simple or compound lenses
    • G02B2003/0093Simple or compound lenses characterised by the shape

Definitions

  • the present invention relates to a non-photosensitive resin composition, and a cured film, a protective film, a flattening film, and a microlens formed from the non-photosensitive resin composition.
  • the non-photosensitive resin composition of the present invention is a composition that does not contain a photosensitizer such as a quinonediazide compound, and the copolymer contained in the non-photosensitive resin composition of the present invention is a compound having a protected carboxy group. It is thermally crosslinked to form a cured film.
  • Electronic devices such as liquid crystal displays and CCD / CMOS image sensors are exposed to chemicals such as acid or alkaline solutions and solvents, and to high temperatures such as sputtering, dry etching, and solder reflow in the manufacturing process. Is done.
  • a cured film having resistance to such a treatment is formed on the device as a protective film.
  • Such a protective film is required to have chemical resistance, high transparency, heat resistance and the like.
  • the cured film When the cured film is formed on a surface having irregularities such as a color filter, the cured film has high flattenability from the viewpoint of ensuring a process margin in the subsequent process and ensuring uniformity of device characteristics. Is required. Further, a microlens is also manufactured from such a cured film.
  • the etchback method is known as one of the methods for manufacturing a microlens for a CCD / CMOS image sensor (Patent Documents 1 and 2). That is, a resist pattern is formed on a resin film for a microlens formed on a color filter, and the resist pattern is reflowed by heat treatment to form a lens pattern. Using the lens pattern formed by reflowing this resist pattern as an etching mask, the resin film for microlenses under the lens pattern is etched back, and the shape of the lens pattern is transferred to the resin film for microlenses to form a microlens. To make.
  • Patent Documents 3 to 5 disclose resin compositions used for producing microlenses. However, all of them are photosensitive (radiation-sensitive) resin compositions, and cannot be said to be suitable materials for forming a microlens by the above-mentioned etchback method.
  • Japanese Unexamined Patent Publication No. 1-1066 Japanese Unexamined Patent Publication No. 6-11459 Japanese Unexamined Patent Publication No. 2006-251464 Japanese Unexamined Patent Publication No. 2007-033518 Japanese Unexamined Patent Publication No. 2007-171572
  • the present invention has been made based on the above circumstances, and an object of the present invention is to provide a resin composition capable of forming a cured film having excellent chemical resistance, heat resistance, transparency and flattening property. is there. Another object of the present invention is to provide a microlens having excellent chemical resistance and transparency.
  • the present invention is a copolymer having a structural unit represented by the following formulas (1) and (2), and the following formula (3) of 5% by mass to 90% by mass with respect to 100% by mass of the copolymer.
  • R 0 independently represents a hydrogen atom or a methyl group
  • Y represents an aromatic hydrocarbon group
  • the aromatic hydrocarbon group is hydrogen.
  • R 1 is a divalent represented by the following formula (I), formula (II) or formula (III).
  • R 1 represents a divalent organic group represented by the following formula (I)
  • the carbonyl group in the above formula (I) is the main structural unit represented by the above formula (2). Bonded to a chain, R 2 represents an organic group with an epoxy group and R 3 represents an alkyl group.)
  • c represents an integer of 0 to 3
  • d represents an integer of 1 to 3
  • e represents an integer of 2 to 6 independently.
  • the structural unit represented by the formula (2) is, for example, a structural unit represented by the following formula (2-1) or formula (2-2).
  • R 0 independently represents a hydrogen atom or a methyl group
  • R 1 independently represents a divalent organic group represented by the above formula (I), formula (II) or formula (III), respectively. .
  • the weight average molecular weight of the copolymer is, for example, 1,000 to 100,000.
  • R 3 represents, for example, an alkyl group having 1 to 4 carbon atoms.
  • the non-photosensitive resin composition of the present invention can further contain a surfactant.
  • the non-photosensitive resin composition of the present invention does not have to contain additives other than the surfactant.
  • the non-photosensitive resin composition of the present invention is, for example, a resin composition for forming a protective film, a resin composition for forming a flattening film, or a resin composition for producing a microlens.
  • the present invention is also a cured film obtained from the non-photosensitive resin composition.
  • the present invention is a protective film, a flattening film or a microlens made from the non-photosensitive resin composition.
  • the microlens is manufactured by the etchback method. That is, a step of applying the non-photosensitive resin composition on a substrate and baking at a temperature of 80 ° C. to 200 ° C. to form a cured film, forming a resist pattern on the cured film, and heat-treating the resist.
  • a microlens is produced by a step of reflowing a pattern to form a lens pattern and a step of etching back the cured film using the lens pattern as a mask and transferring the shape of the lens pattern to the cured
  • the cured film is formed, for example, by baking at a temperature of 80 ° C. to 150 ° C. and then baking at a temperature of 160 ° C. to 200 ° C. in order to evaporate the solvent from the non-photosensitive resin composition.
  • the base material is, for example, a substrate on which a color filter is formed.
  • the cured film formed from the non-photosensitive resin composition of the present invention has excellent chemical resistance, heat resistance, transparency and flattening property.
  • the cured film is exposed to chemicals such as acid or alkaline solutions and solvents in the forming process or the forming process of peripheral devices such as wiring, and is exposed to high temperatures such as sputtering, dry etching, and solder reflow.
  • the possibility of deterioration or damage to the device can be significantly reduced when the exposed treatment is performed.
  • a protective film, a flattening film or a microlens is formed from the non-photosensitive resin composition of the present invention and a resist is applied thereto, or when an electrode / wiring forming step is performed, mixing with the resist is performed.
  • the non-photosensitive resin composition of the present invention contains a compound having a protected carboxy group, it is excellent in storage stability at room temperature.
  • a protective film, a flattening film or a microlens can be formed at a temperature of 80 ° C. to 200 ° C.
  • the non-photosensitive resin composition of the present invention does not require an additive other than a surfactant.
  • the non-photosensitive resin composition of the present invention containing no compound having an unprotected carboxy group does not impair the storage stability, and the additive emerges on the surface of the cured film at the time of baking to form the cured film. No out occurs, and no exudation of additives occurs when the formed cured film comes into contact with the solvent. Therefore, the non-photosensitive resin composition of the present invention is suitable as a material for forming a protective film, a flattening film and a microlens.
  • FIG. 1 is a schematic view showing a cured film formed by applying the non-photosensitive resin composition of the present invention on a stepped substrate and baking it.
  • the present invention is a non-photosensitive resin composition containing a copolymer, a compound having a protected carboxy group, and a solvent.
  • a non-photosensitive resin composition of the present invention containing a copolymer, a compound having a protected carboxy group, and a solvent.
  • the solid content of the non-photosensitive resin composition of the present invention excluding the solvent is usually 1% by mass to 50% by mass.
  • the copolymer contained in the non-photosensitive resin composition of the present invention is a copolymer having structural units represented by the formulas (1) and (2).
  • aromatic hydrocarbon group in the formula (1) examples include a phenyl group, a biphenylyl group, and a naphthyl group.
  • compound (monomer) forming the structural unit represented by the formula (1) include styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-tert-. Examples thereof include butylstyrene, 4-methoxystyrene, 4-cyanostyrene, 4-fluorostyrene, 4-chlorostyrene, 4-bromostyrene, 4-vinylbiphenyl, 1-vinylnaphthalene and 2-vinylnaphthalene. These compounds may be used alone or in combination of two or more.
  • the structural unit represented by the formula (2) is a structural unit represented by the formula (2-1) or the formula (2-2), and the structural unit represented by the formula (2-1) or the formula (2-2).
  • Specific examples of the compound (monomer) forming the structural unit represented by the following formulas are the following formulas (2-1-1) to (2-1-8) and formulas (2-2-1) to (2). Examples thereof include the monomers represented by -2-8). In addition, these monomers may be used individually by 1 type, or may use 2 or more types in combination.
  • the sum of the structural units represented by the formula (1) and the structural units represented by the formula (2) is 100 mol%.
  • the content of the structural unit represented by the formula (1) is 20 mol% to 95 mol%, preferably 50 mol% to 90 mol%, more preferably 65 mol% to 85 mol%, and the above formula (1).
  • the content of the structural unit represented by 2) is 5 mol% to 80 mol%, preferably 10 mol% to 50 mol%, and more preferably 15 mol% to 35 mol%.
  • the weight average molecular weight of the copolymer is usually 1,000 to 100,000, preferably 3,000 to 50,000.
  • the weight average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample.
  • the content of the copolymer in the non-photosensitive resin composition of the present invention is usually 1% by mass to 99% by mass based on the content in the solid content of the non-photosensitive resin composition. It is preferably 5% by mass to 95% by mass.
  • the method for obtaining the copolymer is not particularly limited, but in general, a compound (monomer) forming a structural unit represented by the formulas (1) and (2) is used as a polymerization initiator. It is usually obtained by carrying out a polymerization reaction in a solvent in the presence of a temperature of 50 ° C. to 120 ° C. The copolymer thus obtained is usually in a solution state dissolved in a solvent, and can be used in the non-photosensitive resin composition of the present invention without being isolated in this state.
  • the copolymer solution obtained as described above was put into a stirred poor solvent such as hexane, diethyl ether, methanol, and water to reprecipitate the copolymer, and the resulting precipitate was produced.
  • the copolymer can be made into a powder by drying at room temperature or heating under normal pressure or reduced pressure. By such an operation, the polymerization initiator and the unreacted compound coexisting with the copolymer can be removed.
  • the powder of the copolymer may be used as it is, or the powder may be redissolved in, for example, a solvent described later and used as a solution.
  • the solvent is not particularly limited as long as it dissolves the copolymer.
  • examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.
  • propylene glycol monomethyl ether propylene glycol monomethyl ether acetate, and propylene glycol from the viewpoint of improving the leveling property of the coating film formed by applying the non-photosensitive resin composition of the present invention on a substrate.
  • Monoethyl ether, propylene glycol monopropyl ether, 2-heptanone, ethyl lactate, butyl lactate, cyclopentanone and cyclohexanone are preferred.
  • the non-photosensitive resin composition of the present invention contains a compound having a protected carboxy group, which is excellent in terms of storage stability, for the purpose of forming a cured film.
  • the content thereof is 5% by mass to 90% by mass, preferably 15% by mass to 70% by mass, based on 100% by mass of the copolymer contained in the non-photosensitive resin composition. If the content of the compound having a protected carboxy group is less than 5% by mass, the film formed may be insufficiently cured and chemical resistance may not be obtained. If it exceeds 90% by mass, the film may be cured. During baking when forming a film, defects such as voids may occur due to the deprotected protecting group.
  • Examples of the compound having a protected carboxy group include a compound represented by the above formula (3) having three carboxy groups protected by an alkyl vinyl ether in the molecule.
  • the compound represented by the formula (3) is not particularly limited as long as the alkyl vinyl ether dissociates and the alkyl vinyl ether volatilizes when the non-photosensitive resin composition applied on the substrate is baked. ..
  • R 3 is an alkyl group having 1 to 4 carbon atoms (methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl).
  • a compound representing a group (group, tert-butyl group) is more preferable.
  • Examples of commercially available products of the compound represented by the formula (3) include the following products. Novcure® TN-1, TN-4, TN-5 (all manufactured by NOF CORPORATION).
  • the non-photosensitive resin composition of the present invention may also contain a surfactant for the purpose of improving coatability.
  • a surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, and polyoxy.
  • Polyoxyethylene alkylaryl ethers such as ethylene nonylphenyl ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan Polysorbate fatty acid esters such as tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc.
  • Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, Ftop [registered trademark] EF301, EF303, EF352 (all manufactured by Mitsubishi Materials Denshi Kasei Co., Ltd.), Megafuck [registered trademark] F-171 , F-173, R-30, R-40, R-40-LM (above, manufactured by DIC Co., Ltd.), Florard FC430, FC431 (above, manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard [Registered Trademarks] AG710, Surflon [Registered Trademarks] S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Co., Ltd.), FTX-206D, FTX-212D, FTX- 218, FTX-220D, FTX-230D, FTX-240D, FTX-212P, FTX-220P, FTX-228P, FT
  • the content of the surfactant in the non-photosensitive resin composition of the present invention is 0 based on the content in the solid content of the non-photosensitive resin composition. It is .0001% by mass to 3% by mass, preferably 0.001% by mass to 1% by mass, and more preferably 0.01% by mass to 0.5% by mass.
  • the non-photosensitive resin composition of the present invention does not have to contain a curing agent other than the above-mentioned compound having a protected carboxy group. Further, the non-photosensitive resin composition of the present invention does not have to contain additives such as a curing aid, an ultraviolet absorber, a sensitizer, a plasticizer, an antioxidant, and an adhesion aid.
  • the method for preparing the non-photosensitive resin composition of the present invention is not particularly limited, and for example, a copolymer having structural units represented by the formulas (1) and (2) and the above formula (3). Examples thereof include a method of dissolving the represented compound in a solvent to obtain a uniform solution.
  • a method for producing a cured film, a protective film and a flattening film using the non-photosensitive resin composition of the present invention will be described.
  • the present invention is used on a substrate (for example, a semiconductor substrate, a glass substrate, a quartz substrate, a silicon wafer, and a substrate on which various metal films or color filters are formed on the surface of the semiconductor substrate) by an appropriate coating method such as a spinner or a coater.
  • a heating means such as a hot plate or an oven to prepare a cured film, a protective film, or a flattening film.
  • the baking conditions are appropriately selected from a baking temperature of 80 ° C. to 260 ° C., preferably 80 ° C. to 200 ° C., and a baking time of 0.3 minutes to 60 minutes. Baking is preferably carried out in two or more steps because a flat film can be obtained. When the baking is carried out in two or more steps, the first baking is carried out to evaporate the solvent from the non-photosensitive resin composition applied on the substrate.
  • the film thickness of the film formed from the non-photosensitive resin composition of the present invention is, for example, 0.001 ⁇ m to 100 ⁇ m, preferably 0.01 ⁇ m to 10 ⁇ m.
  • the present invention is used on a substrate (for example, a semiconductor substrate, a glass substrate, a quartz substrate, a silicon wafer, and a substrate on which various metal films or color filters are formed on the surface of the semiconductor substrate) by an appropriate coating method such as a spinner or a coater.
  • a heating means such as a hot plate or an oven to prepare a cured film.
  • the baking conditions are appropriately selected from a baking temperature of 80 ° C. to 260 ° C., preferably 80 ° C. to 200 ° C., and a baking time of 0.3 minutes to 60 minutes. Baking is preferably carried out in two or more steps because a flat film can be obtained. When the baking is carried out in two or more steps, the first baking is carried out to evaporate the solvent from the non-photosensitive resin composition applied on the substrate.
  • the film thickness of the cured film formed from the non-photosensitive resin composition of the present invention is, for example, 0.1 ⁇ m to 100 ⁇ m, preferably 0.5 ⁇ m to 10 ⁇ m.
  • a resist is applied onto the produced cured film, exposed through a predetermined mask, and if necessary, heated after exposure (PEB), alkaline developed, rinsed, and dried to obtain a predetermined resist pattern.
  • PEB heated after exposure
  • alkaline developed, rinsed, and dried to obtain a predetermined resist pattern.
  • the exposure for example, g-line, i-line, KrF excimer laser, and ArF excimer laser can be used.
  • the resist pattern is reflowed to form a lens pattern.
  • a microlens is produced by etching back the cured film of the lower layer using this lens pattern as an etching mask and transferring the shape of the lens pattern to the cured film.
  • Example 1 50.0 g of the copolymer solution obtained in Synthesis Example 1 and Nofcure® TN-1 (PGMEA solution having a solid content concentration of 60% by mass) as the compound represented by the above formula (3) (Nichiyu (Nichiyu) 9.3 g (manufactured by DIC Co., Ltd.) and 0.01 g of Megafuck (registered trademark) R-30 (manufactured by DIC Co., Ltd.) as a surfactant were dissolved in 29.5 g of propylene glycol monomethyl ether acetate to prepare a solution. Then, the non-photosensitive resin composition was prepared by filtering using a polyethylene microfilter having a pore size of 0.10 ⁇ m.
  • Example 2 50.0 g of the copolymer solution obtained in Synthesis Example 2, Nofcure [registered trademark] TN-1 (PGMEA solution having a solid content concentration of 60% by mass) as the compound represented by the above formula (3) (Nichiyu (Nichiyu) 8.5 g (manufactured by DIC Co., Ltd.) and 0.01 g of Megafuck (registered trademark) R-30 (manufactured by DIC Co., Ltd.) as a surfactant were dissolved in 28.4 g of propylene glycol monomethyl ether acetate to prepare a solution. Then, the non-photosensitive resin composition was prepared by filtering using a polyethylene microfilter having a pore size of 0.10 ⁇ m.
  • TMAH tetramethylammonium hydroxide
  • Table 1 shows the cross-linking reaction rate calculated from the peak intensity at 906 cm -1.
  • the cross-linking reaction rate is defined as a reaction rate of 0% at a peak intensity of 906 cm-1 of a film formed by baking at 100 ° C. for 1 minute, and a peak intensity of 0 as a reaction rate of 100%, at 180 ° C. with respect to the film. It was calculated from the peak intensity at 906 cm -1 of the film obtained by baking for 5 minutes.
  • Step flatness The non-photosensitive resin compositions prepared in Examples 1 and 2 were applied on a stepped substrate having a height of 0.5 ⁇ m, a line width of 10 ⁇ m, and a space between lines of 10 ⁇ m, respectively, using a spin coater, and placed on a hot plate. Baking was performed at 100 ° C. for 1 minute and further at 180 ° C. for 5 minutes to form a film having a film thickness of 2 ⁇ m. From h1 (step of the stepped substrate) and h2 (difference in film thickness of the cured film) shown in FIG. 1, the flattening rate was determined using "formula: (1- (h2 / h1)) x 100". The evaluation results are shown in Table 1.
  • the non-photosensitive resin compositions prepared in Example 1 and Example 2 were each applied on a silicon wafer using a spin coater, and baked on a hot plate at 100 ° C. for 1 minute and then at 180 ° C. for 5 minutes. , A film having a film thickness of 2 ⁇ m was formed. The dry etching rate of these films was measured using the etcher and the etching gas.
  • a resist solution (THMR-iP1800 (manufactured by Tokyo Ohka Kogyo Co., Ltd.)) is applied onto a silicon wafer using a spin coater, baked on a hot plate at 90 ° C. for 1.5 minutes, and has a film thickness of 1 ⁇ m. The resist film was formed and the dry etching rate was measured. Then, the dry etching rate ratio of the film obtained from the non-photosensitive resin compositions prepared in Examples 1 and 2 with respect to the resist film was determined. The evaluation results are shown in Table 1.
  • the film formed from the non-photosensitive resin composition of the present invention is a cured film having high chemical resistance, high transparency, and excellent curability with a cross-linking reaction rate of 70% or more. there were. The higher the cross-linking reaction rate, the more preferable. Further, the film formed from the non-photosensitive resin composition of the present invention had a step flattening property having a flattening rate of 70% or more. Further, in manufacturing a microlens by the etchback method, when the shape of the lens pattern is faithfully transferred to the resin film under the lens pattern, the dry etching rate X of the resist film and the dry resin film under the lens pattern are dried.
  • the film formed from the non-photosensitive resin composition of the present invention results in satisfying this. It was.
  • the film formed from the non-photosensitive resin composition prepared in Comparative Example 1 and Comparative Example 2 has an insufficient cross-linking reaction rate as compared with the film formed from the non-photosensitive resin composition of the present invention. It was found that the film properties are likely to change due to the treatment exposed to high temperature in the subsequent step, and it is not suitable for protective films, flattening films and microlenses.
  • Stepped substrate 2 Hardened film 3: Line width 4: Space between lines h1: Stepped substrate h2: Difference in film thickness of cured film

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Abstract

[Problème] Fournir une composition de résine thermodurcissable non photosensible. [Solution] Une composition de résine non photosensible qui contient : un copolymère qui a des motifs structuraux représentés par la formule (1) et la formule (2) ; un composé représenté par la formule (3) ; et un solvant. (Dans la formule (1), la formule (2) et la formule (3), chaque R0 représente indépendamment un atome d'hydrogène ou un groupe méthyle ; Y représente un groupe hydrocarboné aromatique dans lequel certains ou la totalité des atomes d'hydrogène peuvent être substitués par des groupes alkyle, des groupes alcoxy, des groupes cyano ou des atomes d'halogène ; R1 représente un groupe organique divalent qui est représenté par la formule (I), la formule (II) ou la formule (III) ; dans le cas où R1 représente un groupe organique divalent qui est représenté par la formule (I), un groupe carbonyle dans la formule (I) est lié à la chaîne principale du motif structural représenté par la formule (2) ; R2 représente un groupe organique qui a un groupe époxy ; et R3 représente un groupe alkyle. ) (Dans les formules, c représente un nombre entier de 0 à 3 ; d représente un nombre entier de 1 à 3 ; et chaque e représente indépendamment un nombre entier de 2 à 6. )
PCT/JP2020/034727 2019-11-06 2020-09-14 Composition de résine non photosensible WO2021090576A1 (fr)

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